acetylene sri 16 a 1981
DESCRIPTION
TRANSCRIPT
PROCESS ECONOMICS
PROGRAM SRI INTERNATIONAL
Menlo Park, California 94025
Abstract
Process Economics Report No. 16A
ACETYLENE
(November 1981)
Three processes for making acetylene are evaluated in detail: the
manufacture of calcium carbide in an electric furnace, and its hydra-
tion to acetylene; the partial oxidation of natural gas or naphtha; and
the electric arc process using natural gas or C-4 gas. The manufacture
of calcium carbide by the thermal process and the recovery of heat in
the partial oxidation process are also covered. At present costs, the
partial oxidation of natural gas with heat recovery 4s the most econom-
l ical. But as the price of.gas is likely to increase faster than the
price of electricity, the arc process and the carbide process will
probably become more economical.
The arc process using coal dust feed and the submerged flame pro-
cess using heavy residue have economic advantages, but are not yet
commercialized. The thermal cracking process, once widely used., is no
longer economic. The recovery of acetylene in an ethylene plant Is
economically attractive, but the quantity of acetylene produced is
limited. The Kureha/UCC process for producing both ethylene and
acetylene, may become economical once the ethylene price is out of its
present depressed state.
The report also compares the competitive position of acetylene
with those of ethylene and propylene as a chemical feedstock.
‘0 PEP'81 YCY
-
Report No. 16A
I I
a cl m
ACETYLENE
SUPPLEMENT A
by YEN-CHEN YEN
November 1981
A private report by the
PROCESS ECONOMICS PROGRAM
Menlo Park, California 94025
For detailed marketing data and information, the reader is
referred to one of the SRI programs specializing in marketing
research. The CHEMICAL ECONOMICS HANDBOOK Program covers
most major chemicals and chemical products produced in the
United States and the WORLD PETKOCHEMICALS Program covers
major hydrocarbons and their derivatives on a worldwide basis.
In addition, the SRI DIRECTORY OF CHEMICAL PRODUCERS services
provide detailed lists of chemical producers by company, prod-
uct, and plant for the United States and Western Europe.
ii
CONTENTS
1
2
3
4
INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . 1
SUMMARY . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
General Aspects . . . . . . . . . . . . . . . . . . . . . . . 3 Technical Aspects . . . . . . . . . . . . . . . . . . . . . . 7 Calcium Carbide Manufacture in Electric Furnaces . , . . . . 7 Acetylene from Calcium Carbide in a "Dry" Generator . . . . 9 Acetylene by Partial Oxidation, without Heat Recovery. . . . 9 Acetylene by Partial Oxidation, with Heat Recovery . . . . . 9 Acetylene by a Submerged Flame Process . . . . . . . . '. . . 10 Acetylene from Natural Gas by the Arc Process . . . . . . . 10 Acetylene from Coal by the Arc Process . . . . . . . . . 11 Recovery of Acetylene in an Ethylene Plan; . . . . . . . . . 12
INDUSTRY STATUS . . . . . . . . . . . . . . . . . . . . . . . 13
CALCIUM CARBIDE ........................ 19
Chemistry .......................... 19 Raw Materials ........................ 22 Lime ............................ 22 Carbon ........................... 23
Electrothermal Process for Making Calcium Carbide ...... 24 Furnace .......................... 24 Handling of Calcium Carbide ................ 28 Effluents from Carbide Furnaces .............. 31
Other Processes for Making Calcium Carbide .......... 31 Evaluation of an Electrothermal Process for Making Calcium Carbide ....................... 37 Process Description .................... 37 Process Discussion ..................... 43 Cost Estimates ....................... 44
A Brief Evaluation of an Oxythermal Process for Making Calcium Carbide .................. 53 Process Description .................... 53 Process Discussion ..................... 55 Cost Estimates ....................... 55
A Brief Evaluation of a Thermal Process Using CO as a Heating Medium for Making Calcium Carbide .......... 60 Process Description .................... 60 Process Discussion ..................... 61 Cost Estimates. ...................... 61
iii
CONTENTS
5 ACETYLENE FROM CALCIUM CARBIDE ................
Evaluation of a Process for Producing Acetylene from Calcium Carbide ....................
Process Description .................... Process Discussion .................... Cost Estimates ......................
Integrated Production of Acetylene from Calcium Carbide Made by Electrothermal Process ................ Recycle of Carbide Lime .. i ................ Integrated Production of Acetylene from Calcium Carbide Made by Oxythermal Process ...................
6 REVIEW OF PROCESSES FOR PRODUCING ACETYLENE FROM HYDROCARBONS ......................
Cracking by Partial Oxidation ................ Arc Processes Usfng a Gaseous Feed ; . .'. .......... Arc Processes Using Liquid or Solid Feed ........... Heat by Combined Effect of Electric Discharge and Combustion. ....................... Thermal Cracking by a Combustion Gas ............. Thermal Cracking Through Indirect Heat Transfer ....... Recovery of the Products ................... Removal of Carbon Black ................... Removal of Heavier Acetylenes and Higher Hydrocarbons .... Removal of C02, H2S, and H20 ................. Recovery of Acetylene .................... Acetylene Purification .................... Acetylene in Ethylene Industry ................
7 ACETYLENE BY PARTIAL OXIDATION OF HYDROCARBONS ........
Acetylene from Natural Gas by a Partial Oxidation Process Based on BASF Technology ...................
Process Description .................... Process Discussion .................... Cost Estimates ......................
Variation of the Preceding Process with Recovery of Heat ... Process Description .................... Process Discussion .................... Cost Estimates ......................
Acetylene from Naphtha by Partial Oxidation .........
67
78 78 83 83
89 89
95
99
99 104 113
113 118 118 118 124 124 137 137 138 138
141
141 141 153 153 159 159 164 164 168
Acetylene by Submerged Flame Process . . . . . . . . . . . . . 172
iV
CONTENTS
8 ACETYLENE BY TBE ELECTRIC ARC PROCESS ............. 177
Acetylene by an Arc Process Based on Huels Technology ..... 177 Process Description .................... 177 Process Discussion ..................... 189 Cost Estimates
Use of Other Feedstocks ..................... 189
Possible Improvements in the Process .......................... 194 196
Arc Process with Simplified Recovery Procedures ........ 196 Acetylene from Coal by the Avco Arc Process .......... 197
9 ACETYLENE BY THERMAL CRACKING . . . . . . . . . . . . . . . . . 203
10 ACETYLENE AS A BY-PRODUCT IN ETHYLENE PRODUCTION ....... 207
Recovery of Acetylene in an Ethylene Plant .......... 207 Ethylene and Acetylene from Crude Oil by the Kureha/UCC Process ................... 216
11 COMPETITIVE POSITION OF ACETYLENE AS A CHEMICAL FEEDSTOCK . . 219
Competitive Position of Acetylene as Against Ethylene or Propylene . . . . . . . . . . . . . . . . . . . . . 219 The Effect of Oil Price . . . . . . . . . . . . . . . . . . . . 223
APPENDIX A DESIGN AND COST BASIS . . . . . . . . . . . . . . . . 231
APPENDIX B PHYSICAL PROPERTIES . . . . . . . . . . . . . , . . . . 233
APPENDIX C ESTIMATING INVESTMENT FOR INCREMENTAL UTILITIES . . . . 237
CITED REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . 239
PATENT REFERENCES BY COMPANY . . . . . . . . . . . . . . . . . . . . 261
V
ILLUSTRATIONS
a 4.1
4.2 .
4.3
a 4.4
4.5
5.1
5.2
5.3
7.1
7.2
7.3
7.4
8.1
8.2
Zones in an Electric Oven . . . . . . . . . . . . . . . . . 26
Calcium Carbide by Electrothermal Process Flow Sheet . . . . . . . . . . . . . . . . . . . . . . . . 267
Calcium Carbide by Electrothermal Process Effect of Operating Level and Plant Capacity on Production Cost and Product Value . . . . . . . . . . . 52
Reactors in the Oxythermal Process for Making Calcium Carbide . . . . . . . . . . . . . . . . 54
Reactors in the Thermal Process Using CO as Heating Medium for Making Calcium Carbide . . . . . . . 65
Acetylene from Calcium Carbide Flow Sheet . . . . . . . . . . . . . . . . . . . . . . . . 269
Acetylene from Calcium Chloride Integrated Production Effect of Operating Level and Plant Capacity on Production Cost and Product Value . . . . . . . . . . . 93
Effect of Recycle of Carbide Lime on Product Value of Acetylene . . . . . . . . l . l l . l l
97
Acetylene by Partial Oxidation of Natural Gas Flow Sheet . . . . . . . . . . . . . . . . . . . . . . . . 271
Route of the By-Produced Gas . . . . . . . . . . . . . . . 145
Acetylene by Partial Oxidation of Natural Gas Effect of Operating Level and Plant Capacity on Production Cost and Product Value . . . . . . . . . . . 158
Acetylene from Natural Gas Partial Oxidation Process Using Oil Quenching for Heat Recovery, Reaction Section Flow Sheet . . . . . . . . . . . . . . . . . . . . . . . . . 275
Acetylene from Natural Gas by Arc Process Flow Sheet . . . . . . . . . . . . . . . . . . . . . . . . 277
Acetylene from Natural Gas by Arc Process Effect of Operating Level and Plant Capacity on Production Cost and Product Value . . . . . . . . . . . 193
Vii
ILLUSTRATIONS
10.1 Acetylene Recovery in Ethylene Plant Flow sheet........................ 283
11.1 Competitive Position of Acetylene as Against Ethylene or Propylene . . . . . . . . . . . . . 222
11.2 Competitive Position of Acetylene for VC Manufacture Against Ethylene from Ethane . . . . . . . . . 226
11.3 Competitive Position of Acetylene for VA Manufacture Against Ethylene from Ethanol . . . . . . . . ,227
11;4 Competitive Position of Acetylene for Acrylic Acid Manufacture . . . . . . . . . . . . . . . . . 229
B.l Bunsen Solubility Coefficients for Gases in M-Pyrol®Solvent . . . . . . . . . . . . . . . . . . . 236
.
Viii
2.1
2.2
2.3
3.1
3,.2
3.3
4.1
4.2
4.3
4.4
4.5
4.6
4.7
4.8
4.9
4.10
4.11
a 4.12
TABLES
Cost Features of Commercial Acetylene Processes ........ 4
Cost Features of Potential Acetylene Processes ........ 6
Acetylene as By-Product of Ethylene .............. 8
Producers of Acetylene for Chemical Synthesis ......... 14
Estimated World Production of Acetylene in 1979 ........ 17
Historical and Projected Acetylene Consumption in the United States ..................... 18
Calcium Carbide by Electrothermal Process Patent Summary ..... . .................. 29
Calcium Carbide by Processes Other Than the Conventional Electrothermal Process Patent Summary ........................ 33
Calcium Carbide by Electrothermal Process Design Bases and Assumptions ................. 37
Calcium Carbide by Electrothermal Process Stream Flows ......................... 40
Calcium Carbide by Electrothermal Process Major Equipment ...................... i . 41
Calcium Carbide by Electrothermal Process Utilities Summary ... .:.' .................. 42
Calcium Carbide by Electrothermal Process Capital Investment ...................... 46
Calcium Carbide by Electrothermal Process Capital Investment by Section ................. 47
Calcium Carbide by Electrothermal Process Production Costs ....................... 48
Calcium Carbide by Electrothermal Process Direct Operating Costs by Section ............... 50
Calcium Carbide by Electrothermal.Process Cost Effects of Adopting a Variable Operating Schedule .... 51
Calcium Carbide by Oxythermal Process Design Bases and Assumptions ................. 53
IX
TABLES
4.13 Calcium Carbide by Oxythermal Process Capital Investment . . . . . . . . . . . . . . . . . . . . .
4.14 Calcium Carbide by Oxythermal Process Production Costs . . . . . . . . . . . . . . . . . . . . . .
4.15 Calcium Carbide Processes Production of Cost Comparisons . . . . . . . . . . . . . . .
4.16 Calcium Carbide by Thermal Process Using CO as Heating Medium Design Bases and Assumptions . . . . . . . . . . . . . . . .
Calcium Carbide by Thermal Process Using CO as Heating Medium, Capital Investment . . . . ; . . . . . . . . . . . . . . . .
Caicium Carbide by Thermal Process Using CO as Heating Medium
4.17
4.18
5.1 Acetylene Generators
5.2
5.3
Patent summary........................
Utilization of Waste Streams from Acetylene Generation Patent Summary.......................
Purification of Acetylene Made from Carbide Patent. Summary . . . . . . . . . . . . . : . . . . . . . . . .
Other Processes for Making Acetylene from Carbide Patent summary.......................
Acetylene from Calcium Carbide
5.4
5.5
5.6
5.7
5.8
5.9
5.10
56
57
59
60
62
Production Costs . . . . . . . . . . . . . . . . . . . . . . 63
68
72
74
77
Design Bases and Assumptions . . . i . . . . . . . . . . . . 78
Acetylene from Calcium Carbide Stream Flows........................
Acetylene from Calcium Carbide Major Equipment . . . . . . . . '. . . . . . . . . . . . . . .
Acetylene from Calcium Carbide Utilities. Summary . . . . . . . . . . . . . . . . . . . . .
Acetylene from Calcium Carbide Capital Investment . . . . . . . . . . . . . . . . . . . . .
Acetylene from Calcium Carbide Capital Investment by Section '. . . . . . . . . . . . . . .
80
81
82
84
85
X
TABLES
-
a
5.11 Acetylene from Calcium Carbide Production Costs . . . . . . . . . . . . . . . . . . . . . . 86
5.12 Acetylene from Calcium Carbide Direct Operating Costs by Section . . . . . . . . . . . . . 88
5.13 Acetylene via Calcium Carbide Integrated Production Capital Investment . . . . . . . . . . . . . . . . . . . . . 90
5.14 Acetylene via Calcium Carbide Integrated Production Production Costs . . . . . . . . . . . . . . . . . . . . . . 91
5.15 Effect of Recycle of Carbide Lime to Electrolytic Furnace on the Costs of Acetylene . . . . . 96
5.16 Integrated Production of Acetylene from Calcium Carbide Made by the Oxythermal Process . . . . 96
6.1 Reactors for Producing Acetylene by Partial Oxidation PatentSummary....................... 100
6.2 Acetylene by Partial Oxidation or by Cracking in a Combustion Gas Patent summary....................... 105
6.3 Submerged Combustion Process Patent summary..... .................. 106
6.4 Acetylene by Electric Arc Process Patent Summary....................... 107
6.5 Acetylene from Coal or Liquid Hydrocarbon by Electric Processes Patent Summary....................... 114
6.6 Acetylene by Combined Combustion and Electric Discharge Patent Summary. . . . . . . . . . . . . . . . . . . . . . . 117
6.7 Reactors for Producing Acetylene by Cracking in a Combustion Gas Patent Summary....................... 119
6.8 Acetylene by Thermal Cracking with Indirect Heat Transfer Patent Summary. . .'. . ;'. . . . . . . . . . . . . . . . . 121
6.9 Composition of Cracked Gas from Various Processes . . . . . 123
6.10 Purification and Separation of Cracked Gas Patent Summary....................... 125
Xi
TABLES
7.1 Acetylene by Partial Oxidation of Natural Gas Design Bases and Assumptions . . . . . . . . . . . . . . . . 142
7.2 Acetylene by Partial Oxidation of Natural Gas (Without Heat Recovery) Stream Flows . . . . . . . . . . . . . . . . . . . . . . . 148
7.3 Acetylene by Partial Oxidation of Natural Gas (Without Heat Recovery) Major Equipment . . . . . . . . . . . . . . . . . . . . . . 150
7.4 Acetylene by Partial Oxidation of Natural Gas (Without Heat Recovery) Utilities Summary . . . / . . . . . . . . . . . . . . . . . 152
7.5 Acetylene by Partial Oxidation of Natural Gas (Without Heat Recovery) Capital Investment . . . . . . . . . . . . . . . . . . . . . 154
7.6 Acetylene by Partial Oxidation of Natural Gas (Without Heat Recovery) Production Costs . . . . . . . . . . . . . . . . . ,. . . . . 155
7.7 Acetylene by Partial Oxidation of Natural Gas (With Heat Recovery) Stream Flows . . . . . . . . .'. . . . . . . . . . . . . . 160
7.8 Acetylene by Partial Oxidation of Natural Gas (With Heat Recovery) Major Equipment of Reaction Section . . . . . . . '. . . . . 161
7.9 Acetylene by Partial Oxidation of Natural Gas (With Heat Recovery) Utilities Summary . . . . . . . . . . . . . . . . . . . . . 162
7.10 Acetylene by Partial Oxidation of Natural Gas (With Heat Recovery) Capital Investment . . . . . . . . . / . . . . . . . . . . . 165
7.11 Acetylene by Partial Oxidation of Natural Gas (With Heat Recovery) Production Costs . . . . . . . . . . . . . . . . . . . . . . 166
7.12 Acetylene by Partial Oxidation of Naphtha Capital Investment . . . . . . . . . . . . . . . . . . . . . 169
7.13 Acetylene by Partial Oxidation of Naphtha Production Costs . . . . . . . . . . . . . . . . . . . . . . 170
7.14 Acetylene 'from Residual Oil by Submerged Flame Process Production Costs . . . . . . . . . . . . . . . . . . . . . . 174
a -
a -
a Xii
a
a
a
TABLES
8.1 Acetylene from Natural Gas by Arc Process Design Bases and Assumptions , . . . . . . . . . . . . . . . 178
8.2 Acetylene from Natural Gas by Arc Process Stream Flows........................ 179
8.3 Acetylene from Natural Gas by Arc Process Major Equipment . . , . . . . . . . . . . . . . . . . . . . 181
8.4 Acetylene from Natural Gas by Arc Process Utilities Summary . . . . . . . . . . . . . . . . . . . . . 183
8.5 Acetylene from Natural Gas by Arc Process Capital Investment . . . . . . . . . . . . . . . . . . . . . 190
8.6 Acetylene from Natural Gas by Arc Process Production Costs . . . . . . . . . . . . . . . . . . . . . . 191
8.7 Comparison of SRI's Evaluation with Huels Data . . . . . . . 195
8.8 Acetylene from Coal by Arc Process Using Water Quenching Production Costs . . . . . . . . . . . . . . . . . . . . . . 199
.8.9 Acetylene from Coal by Arc Process Using Hydrocarbon Quenching Production Costs . . . . . . . . . . . . . . . . . . . . . . 201
9.1 Acetylene from Ethane by the Wulff Process Production Costs . . . . . . . . . . . . . . . . . . . . . . 204
10.1 Hydrogenation of Acetylene Major Equipment . . . . . . . . . . . . . . . . . . . . . . 208
10.2 Hydrogenation of Acetylene Utilities Summary . . . . . . . . . . . . . . . . . . . . . 209
10.3 Acetylene Recovery in Ethylene Plant Major Equipment . . . . . . . . . . . . . . . . . . . . . . 211
10.4 Acetylene Recovery in Ethylene Plant Utilities Summary . . . . . . . . . . . . . . . . . . . . . 211
10.5 Acetylene in Ethylene Plant Capital Investment . . . . . . . . . . . . . . . . . . . . . 212
10.6 Acetylene By-Produced in Ethylene Production Production Costs . , . . . . . . . . . . . . . . . . . . . 214
10.7 Ethylene by Kureha/UCC Process with Acetylene By-Production Production Costs . . . . . . . . . . . . . . . . . . . . . 217
a Xiii
TARLES
11.1
11.2
11.3
i
i
1 ':,
.:. _b
. "
Manufacture of Vinyl Chloride, Vinyl Acetate, Acrylic Acid by Acetylene Process and Competing Processes . . . . . . . . . . . . . . . . . ., . . 220
Price Required for Acetylene to Make it Competitive with Ethylene and Propylene . . . . . . . . . . . . . . . . 221
Percentage of. Oil-Related Items in Product Value of Acetylene and Ethylene . . . . . . . . 223
I
.
xiv
1 INTRODUCTION
-
a
In recent years, because of the pressure exerted on the cost of
ethylene by the ever-increasing price of oil, interest in the long-
dormant subject of acetylene production has been renewed. This report
supplements the original PEP report on the subject, Report 16, Issued
In 1966.
The present report treats the calcium carbide process (including
the manufacture of calcirma carbide) and the arc process, neither of
which was included in the earlier report. The partial oxidation pro-
cess described in the original report was based on SRA Chimie technol-
ogy; the present report features MSF technology, which is now used
comerciallym Also in this report, SRI evaluates the technology of
recovering the acetylene that is by-produced in ethylene production
and compares the economics of recovery with that of hydrogenation.
The thermal cracking process for producing acetylene, once widely
used, has been abandoned. The submerged flams process was only used
for a few years, in one plant. The coal arc process is still in the
early developPent stages. The Kureha/UCC process is in the pilot
stage- These four processes are briefly evaluated in this report, on
the basis of data from earlier PEP reports or from the relevant com-
panics .
The competitive position of acetylene relative to ethylene in
vinyl chloride and vinyl acetate production and relative to propylene
in acrylic acid production is described.
Ruels aud BASF supplied valuable information about the latest
aspects of their technologies, and allowed the author to visit their
acetylene plants. The Formosa Plastic Corporation allowed the author
to visit its carbide plant and commented on the report section on
carbide manufacture. Aerzener Maschfnenfabrik and Mycom Corporation
supplied price quotations. To all of them we express our sincere
gratitude.
2
2 SUMMARY
General Aspects
Until the 19408, acetylene was the building block for organic chem-
ical syntheses. Its replacement by petrochemicals, especially ethyl-
ene, increased as the petroleum industry developed. The consumption of
acetylene for chemicals in the United States fell from a maximum of
1,054 million lb in 1965 to 282 million lb in 1979; a similar propor-
tional decrease occurred in Western Europe and elsewhere. In 1980 the
U.S. consumption Increased to 286 million lb.
The above numbers do not include the consumption of acetylene for
metal cutting and welding, which has been 100 million lb/yr in the
United States ever since the 19606, and probably will remain at this
magnitude.
Three processes are used commercially for producing acetylene:
the calcium carbide route, with the carbide being made by an electrical
process; the arc process; and the partial oxidation process using natu-
ral gas. The cost features of these processes are given in Table 2.1.
SRI used two capacities in these evaulatloas: 300 million lb/yr for
operations aiming at production of vinyl chloride, and 100 million
lb/yr for operations aiming at production of vinyl acetate, et al.
Acetylene, being unsuitable for piping long distances, has to be pro-
duced In quantities tailored for a captive user or a customer next
door. This is a disadvantage as a chemical feedstock as compared with
ethylene.
In Table 2.1, data are given for two versions of the partial oxlda-
tion process: one without heat recovery, another with heat recovery.
The former is used in most partial oxidation plants In the world. The
latter, an improved version, is practiced by BASF now.
3
PEP cost index: 360
Qpwity (dllim lb/yr) 8attory lidta iovutwnt (dllion $1 forA find upiul (million $)
Roduotiw owt (c/lb) mu1 labor
mtrria1r Cob. 3.5cllb Limwtow, O.Sc/lb lturd gas, 9.49dlb 2utmwm. l&/lb mm, l.lc/lb otlmrr
Total utmrialm
uti2itiw Rum, $6.4/1.000 lb Llwtrfcity. 3.zc/kwb othw~
Total uti1itien
PlamL onrhud hprwi~tiw. tuw. ad iwurww WA. ulw. wd rwurcb
Totml prodmctiw cwt
credit cu.$4/millirnBt. WWSJO, SC.Pc/lb Bthylama, UC/lb Qrbn b&k. l%/lb other*
LC produotiw w*t 25X pwtu Nturn am TFC
Roduot wlw
vari~tiw of tin pmc..a
Cmmf idmu ratily n H B+ B+
Cmrbida Roww
::6 300 lW.3
64.3 151.8
5.03 2.40
6.80 6.80 2.45 2.45
--
2.46 1.96 -- 11.73 11.23
- 14.67 14.a7 0.13 0.13 -- 15.00 15.06
4.06 1.96 7.72 6.07 3.00 3.00 -- 46.54 39.66
iG ZG 16.07 12.65 -- 62.6 52.3
Uud uid.17.
InrLudOfrui~ dwtrieity, ul- ciw carbide cw k pmdmwd thuw11y. TNa pr0c.u. omc. ummd by 9699 in pilot plant rule, wuld give btter .ewoq if co *.. owh8uwdu chnie~l feed.
Pwtial Oxidation Pwtlal OLidwion uithout ibat Rwovory uith l&at awow~
100 300 47.8 104.2 63.2 138.7
2.74 1.56
--
30.07 - 39.07 --
5.65 5.65 2.91 2.44 -- 47.43 46.96
100 300 45.7 95.2 56.3 121.3
2.90 1.65
--
-- 1.50 1.50
2.19 1.27
::: 5.54 3.00
64.44 59.85
-17.20 -17.20 --
w- --
38.87 a.sT mm
5.65 5.65 4.66 4.10 -- 49.16 46.62
-3.40 -3.40
0.25 0.25 -- -3.15 -3.15
2.32 1.32 4.85
::z 3.00
61.25 56.29
-17.11 -17.11
-0.37 -0.37 -- 46.67 42.26 15.86 11.56 -- 62.7 53.6
Uud in wny plwtm.
- -5.21 -2.34 -2.34 -- 41.% 36.64 14.57 10.11 -- 56.4 47.0
owd hy %sF.
hadstock CAII bm luphtlm. but th monoq uoold be inferior.
Are Pmw*I
::5 300 169.6
90.3 218.3
4.07 2.50
-- -- 15.64 15.64 9.36 9.36
3.01 - 2.34 -- 29.01 27.34
1.35 1.35 20.15 20.15 0.34 0.34 -- 21.% 21.84
3.26 2.W 11.80 6.74
).M)- 3.00
71.98 65.42
- -16.92 -16.92 -7.34 -7.34 -5.21 -5.21 -3.62 -3.82 -- 30.69 32.13 24.57 18.19 -- 63.3 50.3
owd by Ibela. but with diffarent nemcry pro- wduru .
1. Fwd~took cm be.ly hydrocmbm 6~ or l ri1y wifiad liq- uid.
2. Lqrovewllta in dewlqmwt mtaga ." (1) nunrry of hwt (2) rooyola of bydro- mwtad N&u acet71elmm.
3. If bydro6en is not l parited, Lh ptad- uct vmlcu would be h-r by 6-lc/lb.
4
-
At both production rates the partial oxidation process with heat
recovery gives the lowest product value.
The above, however, is based on present costs of feedstock and
electricity. If the price of natural gas increases faster than the
price of electricity (as it is very likely to do in the future), the
arc process and the carbide process will become more economical than
the partial oxidation process.
With the product value shown in Table 2.1, acetylene can be com-
petitive, though'barely, with ethylene in production of vinyl chloride
and vinyl acetate, but not with propylene in acrylate production. If
the price of oil increases faster than that of electricity, the competi-
tive position of acetylene by the arc process and the carbide process
will be stronger. (For details of the analysis, see Section 11 of this
report.)
A.thermal cracking process was once the most prevalent process,
but It is no longer used. A submerged flame process using residual
oil, a special version of partial oxidation, was used in Italy for a
few years. The coal arc process is in the development stage. The cost
features of these three processes are given in Table 2.2.
A submerged flame process with recovery of acetylene by freeeing
has favorable economics. But recovery by freezing is hazardous, and
has never been used on a large scale. (The Italian plant used a par-
tial recovery scheme.) Using conventional recovery procedures would
considerably increase the capital investment, and hence the product
value. Furthermore, the economics of the process depend too heavily on
by-product credit, which is generally not considered desirable from a
management point of view.
The coal arc process has some advantage over the conventional arc
process using hydrocarbon feed, when compared on an equitable basis
(1 .e., both with hydrogen as fuel).
In the production of ethylene by steam cracking of hydrocarbons,
some acetylene is by-produced. It can be hydrogenated to ethylene in
5
n%crfala &boa. 9cllb Praidul oil. 5.5dlb ~; :;e~Cb
. Prop& 9&b Otbtrm
utilitk~ Elwttioity. 3.2clW1 tIMa. $6.4/1.000 lb otlmn
Plant owrhwd umprwfuiw, wan. iwu. WA, UIW. l 111 rowuch
Total pwdrtiw comt
credit Ethylmmm. 24dlb otbrm
w prodwtiw ewt 252 protw rotnrnwTcF
Pmduct *Jr
-id l 0r.U
vuktionof tr proe."
91.5
300 141.6
163.7
3.19 1.96
29.70 29.70
2.54 2.00
32.24 31.10
8.W a
9.36
2.55 9.78 3.00
60.12
8.% 0.60
).)6
1.57 7.34
).oQ
54.93
-1.16 -I.u
59.96 53.77 m 15.)1
79.3 69.1
hpkthaouk uwd u hcd. but moot folvtioll will ba rrfwn.
300 126.5
90.2 166.7
3.51 1.w
60.39 60.39 11.50' 11.50
2.29 1.46
15.17- 73.33
4.24 4.24 -1.54 -1.56 0.32 0.32
3.017%
2.61 1.50 10.62 6.74
-kE- 3.00
97.33 89.47
-27.60 -27.66 -51.82 -51.92
17.91 10.05 22.55 14.06 -- 40.5 24.1
ououdioa1to1iaplat (be with iwoploto ruovuy).
CaI~ouachi~
300 162.1
106.5 224.3
4.24 2.46
3.13 3.13
16.30 15.53
11.73 11.73 3.51 3.51 0.35 0.35 -- 15.59 15.59
3.40 12.76 X 3.00 J.00
55.32 47.56
4.w 4.60 -11.39 -11.39 --
6
the process, or it can be separated and recovered. The value of the
acetylene from this source is the value of the ethylene that would have
resulted from hydrogenation, minus the cost of the hydrogen for the
hydrogenation, plus adjustments for changes in utilities consumption
and capital investment. The economics of acetylene production evalu-
ated In this way are presented in Table 2.3. Also given in Table 2.3
are the economics of acetylene as a by-product of ethylene in the
Kureha/UCC process of heavy or crude oil cracking. The Kureha/UCC
process can yield a higher acetylene/ethylene ratio, thus making acetyl-
ene a main product and ethylene a by-product, as In the conventional
arc process; but this would not be an economical operation.
Fram Table 2.3 we see that by-production of acetylene in the ethyl-
ene plant is quite economically viable; in other words, acetylene in
such plants should preferably be recovered Instead of hydrogenated, if
the acetylene produced can be sold to an acetylene user, such as for
production of acetylenic chemicals. The Kureha/UCC process per se is
an economical process, but is not economical at the present depressed
price of ethyelene.
Technical Aspects
Calcium Carbide Manufacture in Electric Furnaces
Lime is obtained by burning limestone, with gas from the electric
furnace serving as fuel, in a continuous shaft kiln. Coke is dried by
the exhaust gas from the lime kiln. Both the lime and the coke are
screened. Pieces smaller than 0.25 inch are fed to the furnace through
the hollow space of the Mderberg electrodes (electrodes formed In situ
from carbonaceous paste), pieces larger than 0.25 inch are fed to the
furnace directly. The electric arc between the electrodes causes the
coke and lime to react to form calcium carbide and carbon monoxide.
The latter is piped to the limestone kiln for use as fuel. The molten
calcium carbide is cast into ingots. The ingots are broken, the
carbide is screened, and the ferrosillcon and ferric oxide particles
are removed magnetically.
Table 2.3
ACETYLENE AS BY-PRODUCT OF ETHYLENE
Plant Capacity: 1,000 Million lb/yr Ethylene PEP Cost Index: 360
Acetylene production (million lb/yr)
Battery limits investment (million $)
Total fixed capital (million $)
Total production cost (c/lb)
Credit, ethylene at 24ojlb
Net production cost
Steam Cracking Ethylene
10
2.5
4.8 312.0
39.5 211.0
- -203.4
39.5 7.6
In Kureha/ UCC Process
118
217.0
25Wyr pretax return on TPC 12.0 66.1
Product value (c/lb) 51.5 73.7
Confidence rating B- B-
Remarks Investment refers to If ethylene is cred- that incremental ited at 26e/lb, part of plant for acetylene would have acetylene recovery a product value of as compared with 56.8c/lb. hydrogenation. See the text.
8
Acetylene from Calcium Carbide In a "Dry" Generator
Calcium carbide and a limited amount of water react in the genera-
tor. The sludge is continuously removed. The acetylene gas is cooled,
treated with dilute sulfuric acid and sodium hypochlorite (made from
caustic soda and chlorine) to remove impurities, and then dried by re-
frigerant cooling.
Acetylene by Partial Oxidation, Without Heat Recovery
Preheated natural gas and oxygen are reacted in burners. The prod-
uct is quenched with water before leaving the burner, further scrubbed
with water in a scrubber and then scrubbed by a moving coke bed.
Carbon black by-produced during partial oxidation is thus removed. The
gas is pretreated with N-methylpyrrolidone (WMP) to remove the easily
polymerieable substances. It is then compressed to 10 atm, and ab-
sorbed in NMP. The NMP solution containing acetylene Is stripped in a
column by a stream of acetylene to remove ethylene, carbon monoxide,
and other gases at the top, and acetylene gas at the middle. To the
solution leaving the bottom of the column is added an NMP-water solu-
tion recovered In various washing steps- The resulting solution is
degassed at atmospheric pressure to get acetylene for use in stripping,
and then is degassed under vacuum to remove heavy acetylene. The NMF
is then recycled.
Part of the gas leaving the IMP absorption column is used for drlv-
lag the compressor and as fuel in the preheaters; the balance is a by-
product. Part of the WMP in circulation is evaporated for purifica-
tion.
Acetylene by Partial Oxidation, with Heat Recovery
The gas from partial combustion of preheated natural gas and oxy-
gen is quenched with a stream of residual oil, instead of water. The
gas is further cooled In an oil column, with a light aromatics stream
(benxene-toluene-xylene, or BTX) being added at the top, and a residual
oil stream being added at the middle. Oil is withdrawn and circulated
9
outside through two waste heat boilers and a waste heat hot water
heater. The gas from the oil column Is treated with water in a column
to remove BTX. From here on, it is processed in the same way as de-
scribed before, under "Acetylene by Partial Oxidation, Without Heat
Recovery". Part of the oil is withdrawn from the bottom of the oil
colrman to be distilled to recover BTX at the top, a residue oil at the
middle (recycled to oil column), and an oil containing 40% carbon at
the bottom. The carbon-containing oil is heated in a petroleum coke
bed to recovery residual oil for recycling, and coke as a by-product.
Acetylene by a Submerged Flame Process
A residual oil is cracked and partially oxidized in an oxygen-fed
flame below the surface of the oil. The product is Immediately
quenched by the surrounding oil. The oil is cooled by circulating
through a waste heat boiler. Part of the 011 is withdrawn to limit the
carbon accumulation. The gas is scrubbed with oil, cooled by water,
treated with diethanolamine to remove CO2 and H$5, and then
refrigerant-cooled to separate ethylene and acetylene. This C2 frac-
tion is washed with toluene to remove C3+ hydrocarbons, and then
treated with NMP to recovery acetylene.
Acetylene from Natural Gas by the Arc Process
Natural gas is cracked in an electric arc generated by high volt-
age DC. Butanes serve as a secondary feed and as a quenching medium.
The cracked product is further quenched by water In the reactor. The
carbon produced during the cracking is removed by a cyclone, then a
water scrubber, and finally an oil scrubber. The oil also removes some
aromatic compounds and Cs+ hydrocarbons. The oil from the scrubber is
distilled to recover by-produced pyrolysis gasoline and pyrolysis
residue.
The cracked gas from scrubbing is compressed to 8 atm and treated
with methanol for absorption of higher acetylenes and light aromatics.
The methanol solution is stripped by off-gas, and finally rectified.
10
In this my, higher acetylenes are carried by off-gas for recycling to
reactorr, and light aromatics and methanol are recovered.
The gas is further compressed to 16 atm and treated with octane to
absorb C3+ hydrocarbon8. The C3+ hydrocarbons are recovered by strip-
ping and are recycled to the reactors. Finally, the gas is treated
with a solvent consisting of 85% NMP and 15% methanol. Acetylene is
recovered from the solution by flashing.
Throughout the absorption by methanol, octane, and M-methanol,
and the related desorption, proper temperatures are maintained by re-
frigeration, heat-exchanging, and heating.
Gas leaving the acetylene absorption column is treated by molecu-
lar sieves to remove carbon dioxide and methanol, compressed to 27 atm,
and deep-cooled to condense ethylene, ethane, and part of the methane.
This liquid hydrocarbon is distilled to remove methane (demethanized)
and fractionated to recover ethylene as a by-product. Uncondensed gas
fra the ethylene/mthane condensation is processed to recover hydrogen
by pressure-awing adsorption. An off-gas stream and a small part of
the hydrogen are used as a stripping agent and are eventually recycled
to the reactore. Streirma containing mainly methane and ethane are recy-
cled to the reactors.
Refrigerants for the process are ethylene and propylene.
Acetylene from Coal by the Arc Process
Coal with a high volatile8 content is fluidleed in hydrogen
obtained from the process, and charged Into a direct current arc.
Additional hydrogen is also recycled to the arc. The cracked gas is
quenched by a stream of hydrocarbon in the reactor. It is then
scrubbed to remove carbon, comprersed to 3 atm, and treated with NMP to
remove H2S and UCN, and with caustic soda to remove Cog. !l’hen It is
compressed to 15 atm, and treated with NMP in stages to absorb CSp and
acetylene. Finally, the gas is processed for recovery of ethylene in a
way similar to that described before.
11
Recovery of Acetylene in an Ethylene Plant
The cracked gas after compression, caustic scrubbing, dehydration,
and chilling is treated with dimethylformamide (DIG’). The’ DMF- solution
containing acetylene is stripped’by gentle heating in the presence of a
down-floting DMF liquid to remove gases other than acetylene, and then
is heated to recover the acetylene.
. .
12
3 INDUSTRY STATUS
For decades after the turn of the century, acetylene was the pre-
dominant building block of the industrial organic chemicals. Acetylene
consumption expanded very rapidly in the 30s and 408, especially in
Germany during World War II. Vinyl chloride, vinyl acetate, vinylidene
choride, acetaldehyde, chlorinated hydrocarbons, acrylate, acryloni-
trile, butadiene, and even ethylene in the war years, were produced
from acetylene. The calcium carbide process was the sole route for
making acetylene until the late 19308, when the processes using methane
and other hydrocarbons began to evolve. The arc process, the partial
oxidation process, and the regenerative thermal cracking process were
established. But the carbide route remained the main route for some
time.
The hydrocarbon acetylene processes grew in the 1940s and the en-
suing two decades, replacing the calcium carbide process as the main
route. Meanwhile, however, the rapid development of the petrochemical
industry gave rise to a cheap and ample supply of ethylene, which began
to vie with acetylene as a raw material for making chemicals and inter-
mediates for rubber and plastics. The climax of acetylene production
in the United States occurred in the 19608, and in Germany in the early
1970s. Since then, its production has decreased steadily. Acetylene
was replaced by ethylene and propylene in the manufacture of acetalde-
hyde and acrylonitrile. Acetylene also lost ground in the manufacture
of chlorinated solvents, neoprene, isoprene, acrylates, vinyl acetate,
and vinyl chloride. (For the manufacture of ethylene and butadiene,
the acetylene process had become obsolete long before.)
Today, the United States and West Germany are the two largest pro-
ducers of acetylene, mostly from hydrocarbons. Next are Italy and
Japan, the former using hydrocarbon processes, the latter mainly the
carbide process. Table 3.1 lists the companies producing acetylene for
chemical synthesis in the United States, Western Europe, and Japan, as
13
kladlom Inc. Dim. Lk
Ed00 c8rMdo &drift. XI
6*otorn aluom
hotrio
Donoualmlo arm&l
rrouo
Prodolts Qimlquu D@u Eablmm la-am
nhono-mulou, mrdioo Potroc~eolo ah
mw. Eat
MSI
Qdacbo ihko mola
6rdoolcllnio mwl
mahot
IurJ &iC
nmItod1000
lktllarlmld8 slNllYtbarlad Qmd*
50
16
10
Is0
50-55
1*20
lo-15
IS20
2
lo-15
Qlciu u&i& kety1mic chadcalm (CAF). vinyl flrorida (ml Font)
my-podsctofr~&r Icrylic rid (MS?)
Calciu urbidm Aeot~louic l lcollo1m and tboa to vltmlao
mtural6a prtiol vinyl eblori& (aordm), oxidotial, Mw 1,4-butMedio1 (MSI
6yMdotto)
Lt.uml ga partial Acrylic storm oxldotiom. Mw
ay-product of l t~loao ad ~rowoco procooo
ryqroductof*thyloM
I
&ot~laic cbriulr (OAF) ad bottled ocot~loa
mroduct of l thyl*u
ay-produt of l tbylan
sy-product of l tbgloa &otylono block
6 Coleim arbidm Chloriutd kydroarba
22
66
caleil arbido
hrtial widotioa, BA8C
hrtly to ocotyloa black
vlmyl ocototo
176 Itural gu pmtiml oxi- dotion. us? brylic l otor, botomdlol.
ludugobofa
lkrl
bill
BwrtClupuct
etc. 13 6-t of l tbylnm
264 Lflafy#as. bmlaarc vc md btawdiol P-m
30 ay-produt of l tbylom
14 calciu cubida kotyIou block
132 Mkamtos6I VA, vo, and iooprao
1% lhtuol m, partial oai- VC dAtia. mntoatinL
lhrdijk 20 viny1 l mtoro
lattord~omio 6
mu& 30 ~lcim urbi& VA
Id&II 40 Cutid aidotiom, &otylonic olcolml (for lbotoutiml WiUUO)
14
Table 3.1 (Concluded)
w-w ComMY Loatioa (1II Pmurr APPlieation
266 Caleiu earbida VC. VA. acetylene black. and Ilapr.lw
1-m Elaetric I&wry
Klyoua Csr Chaical Industry
616 Cdciu carbide Atatylmu black
55 ?artial mid~tioo, 6A6y VA (for vinylon)
brcria 6achia lortsnti
Li~ritchnrk 77 lhturrl gpm partial oxida- tion. USF
&ah Africa
Africm 6xplwinm
20 Calcium urbidm
110 Cnlcim carbide
vc
15
as a few producers in other countries. There must be many more acet-
ylene producers using calcium carbide in other countries (especially
East Germany and India).
All the listed acetylene producers using the carbide process (in
Table 3.1) make their own calcium carbide. In addition, there are
plants producing calcium carbide either for making bottled acetylene,
or for supplying small independent producers of bottled acetylene.*
The bottled acetylene is used for metal welding and cutting, and
illumination. Such acetylene plants are not included in Table 3.1.
Statistics on acetylene production are very scanty. The Chemical
Economics Uandbook (SRI International) has made estimates for the
United States, Western Europe, and Japan. We have added some educated
guesses and come up with 1.9 billion lb/yr as the total world produc-
tion in 1979. See Table 3.2.
As shown in Table 3.1, acetylene is now used in making vinyl chlo-
ride, vinyl acetate, acrylic acid and esters, acetylene black, and the
so-called acetylenic chemicals. The last named includes 1,4-butanediol
(for polyurethane and polybutylene terephthalate resin), tetrahydro-
furan (solvent), gamma-butyrolactone (solvent), N-methylpyrrolidone
(solvent), N-vinylpyrrolidone (polymerized to form gum, which is used
as an additive in cosmetics, pharmaceuticals, textiles, and food),
methylbutynol, and isophytol (for making vitamins A and E), propargyl
alcohol (corrosion inhibitor), vinyl esters (anesthetic, and for copoly-
mers with vinyl acetate), and vinyl esters other than vinyl acetate
(for copolymer with vinyl acetate). For making these chemicals,.the
acetylene route is either the only commercial process or the predomi-
nant process. For vinyl chloride and vinyl acetate, acetylene competes
with ethylene; and for acrylic acid and esters, with propylene. In
these applications, acetylene has lost ground to ethylene and propylene
and would have lost even more in recent years had it not been for the
continued increase of oil prices.
*In some regions some calcium carbide is made into calcium cyanamide.
16
Table 3.2
ESTIMATED WORLD PRODUCTION OF ACETYLENE IN 1979 (Million lb/yr)
Chemical Use Industrial Use Total
United States 282 114 396
Western Europe 814 (2W (1,014)
Japan (106) (100) 206
Others
Total
(200) (150) (350)
(1,402) (504) (1,906)
Source: Chemical Economics Handbook, SRI International, except the values in parentheses, which were estimated by the author of this report.
The last coluam of Table 3.3 is the 1984 consumption of acetylene,
projected by SRI's Chemical Economics Uandbook. This estimate is based
on the present situation, including the production facilities. How-
ever, as detailed in Section 11, as the oil price further increases,
the cmpetitive position of acetylene a8 against ethylene for making
vinyl chloride and vinyl acetate will improve; at some point, VC or VA
made by the acetylene process will have a lover product value than that
made by the ethylene process. In the long term, SRI expects the use of
acetylene in paking these products to increase. Meanwhile, acetylene
for making acetylenic chemical8 vi11 continue to increase at a rate
equivalent to the growth in demand for these chemicals. Some of these
chemicals, such as butanediol, may have a phenomenal growth. On the
basis of the above arguments, we believe there will be effort6 in the
coming years to increase acetylene production capacity, and the produc-
tion will increase correspondingly sometims after 1985.
17
Table 3.3
HISTORICAL AND PROJECTED ACETYLENE CONSUMPTION IN THE UNITED STATES
Chemical we
Vinyl chloride mmomer
Acetylenic chemicals
Vinyl acetate monomer
Acetylene black
Acrylic acid and esters
Chlorinated solvents
Neoprene
Acrylonitrile
Other
Industrial use for metal cuttiug and welding
Total
1965
1,054
339
147
41
92
220
196
19
100
1,154
(Million/lb)
1970
849
268
41
158
--
70
91
169
42
10
169
66
70
-
100
15
0
0
9
109
538
1976
384
120
66
64
110
15
0
0
9
106
490
1977
312
1979
282
1980
286
120 110 110
72 80 85
45 52 50
4 19 20
56 16 16
10 0 0
0 0 0
0 0 0
5 5 5
114
396
1984
297
110
115
44 0 23
0
0
0
0
5
402 l Source : :- Chemical Economics Baudbook, SRI International.
'..
18
4 CALCIUM CARBIDE
l Chemistry
The reaction between CaO and C at high temperature to form CaC2 is
represented stolchiometrlcally by equation (1):
caO(s) + 3C(s)- cq(s) + co
Hr - 111.2 kcal (endothemic)
(1)
This reaction, being fourth order, cannot be elewntary. According to
most researchers, the reaction proceeds in two steps:
caO(s) + C(s)- ws, 1) + CO(e) (2)
ca(s, 1) + ZC(s)- ~Cz(s)
a
(3)
Ikeaction (2) Is strongly endothermic, 125.3 kcal/aol for Ca as a solid.
It occurs mainly near the electrode. l&action (3) is mildly exother-
tic, 14.1 kcal/mol for Ca as a solid.
In addition, reaction (4) may occur at high temperature:
CaCz(s) + ZCaO(s)- 3Ca(s, 1) + 2co (4)
The Ca formed imuld then react as in equation (3).
Kmous et al. studied the free energy change of these reactlons,
and all other possible reactions (19 In total) between CaO, C, CaC2,
CO, and CO2 (302345, 302349). They concluded that reaction (3) Is
possible at ell temperatures between 5000K and 26OWK, and that reac-
tion (2) is possible above 25ooOK, and reaction (4) above 26OOoK.
19
Emons also calculated the theoretical yield of CaC2,
thermodynamic equilibrium of equation (1). The result is
(X of theoretical yield):
based on the
as follows
Initial mol ratio of C to CaO Temp. (OK) 2.50 2.75 3.00 3.25 P - P -
2073 36 39 42 44
2173 47 50 '54 57
2273 55 59 63 67
2373 61 66 70 75
2473 67 72 77 82
2573 70 76 81 86
Experimental results for the temperature range 2073-22730K are
quite in line with the above. Those at higher temperature fall below
the calculated value, because of the decomposition of CaC2 according to
reaction (4). The experimental results below 2073OK would also be
expected to be below the calculated values, because equilibrium is not
attained.
Because the yield is always much below 1002, the finished product
always contains substantial amounts of CaO and some C.
In commercial operation, neither the CaO nor the C is supplied in
pure form. Impurities commonly present are compounds of Si, Fe, Kg,
Al, S, Na,K, As,and N. The complexity of the reactions is illus-
trated by the fact that 82 reaction equations are possible for the ox-
ides of Ca, Si, Fe, Kg, and Al alone (302349). The important reactions
of impurities during the production of CaC2 are as follows (compounds
underlined are usually found in the finished product as impurities):
l Silicon--
CaSI03 -CaO + SiO7
sio2 + 2c. *si + 2co
Si + Fe -SiFe
(5)
(6)
(7)
20
si + c -sic
Fe + S -Fe8
0 Iron--
FeqOq + 4C -3Fe + 4C0
FepOg + 3C -3Fe + 3CO
Fe + Si -FeSl
l Aluminum--
CaWO2)2- cao + Al7Op
Al203 + 3C -2Al + 3co -
4Al + 3C -Al&p
l Uagnesiun-
!!&+c -Mg+co
0 Sul.fur--
PCO- caSO& + cao + so2 + co2
CaSOq- CaO + SO2 + 0.502
so2 + PC- 20 + 0.5 s2
o-%2 + CaO + CO-
CaS + PC- CaC2 + 8
0 Phoephorulii-
~3@‘04)2 + x -3Cao+2P+5Co
3Ca + 2P- CaqP2
(8)
(9)
00)
(11)
(7)
(12)
(13)
(14)
05)
06)
(17)
08)
(19)
(20)
(21)
(22)
21
l Nitrogen-- h
Ca + N organic- s23i.2
CaC2 + N2 -CaCN, + C
(23)
(24)
0 Arsenic-
ti3(AS04)2 + 5c -3 CaO + 2As + 5C0 (25)
3ca + 2A8-cag82 (26)
In addition, the raw material CaO contains a little 03 '(unburnt
limestone), and the C contains a Tuttle mter. CaC03 decanposes to CaO
and CO2, and the presence of wter leads to the vater gas reaction:
CaC03- CaO + CO2 (27)
H-JO + C&XC02 + H2 (28)
Commercial CaC2 often contains 79-83X CaC2; 7-14X CaO; 0.4-3X C;
0.6-3X SiO2, FeS, and SIC; 0.2-0.3X Fe203; 0.2-2X CaS; 0.2-0.4X CaS04;
0.2-1X CaCN2; 1.5-4X Al, Al4C3, and Al2O3; and small amounts of Mg8,
Ca, Ca3N2, Ca3P2, and Ca3As2. The purity of CaC2 is usually specified
as liters of acetylene (at 15oC and 760 mm Hg) generated from one kg of
CaC2; For pure CaC2 this number is 368.
Raw Materials
Lime
For CaO, lime is used. Most carbide plants make their own lime by
calcination of limestone in a horizontal rotary kiln or a vertical sta-
tionary kiln, fired by gaseous or liquid fuel. The rotary kiln gives a
more uniform product. But the vertical kiln as pioneered by Union
Carbide Is well engineered and less expensive to install and to operate
(449738). The old type of vertical kiln with alternate layers of coke
(as fuel) and limestone is now used only In small plants. Fluidieed
22
bed calciners (302538), are not used because the resulting lime parti-
cles are too small for efficient use in electric furnaces.
The limestone should be of high quality, preferably 97-981 CaC03.
Magnesium, which invariably accompanies the limestone, should be
present in as low a percentage as possible. In the electric furnace
MgO is reduced by C to Mg; the Mg is then oxidized in a cooler part of
the furnace; and finally the MgO is reduced again. Thus the consump-
tion of both C and electricity is excessive. According to one source,
1% MgO in the lime increases the power consumption for carbide produc-
tion by 1.9%. Another source gave an even higher number: 1% MgC
increases the energy requirement by 60-120 kcal/kg of carbide (i.e.,
2-4X) and requires 4 g extra C. Each percent of SiO2 increases the
power consumption by about 0.5% (B-43).
The burning of limestone should be 98-991 complete. Each 1% CO2
In the lime consumes 1% more electric power In the carbide furnace. P
and S in the carbide show up In the acetylene end-product as PH3, H2S,
and mercaptans. The specification for P in lime Is usually "lees than
0.01x;."
Calcium sources other than lime are occasionally mentioned; one
such is coal ash (302499).
Lime fed to the carbide furnace should be 3 mm and larger, pref-
erably 6 mm and larger, but modern furnaces provided with hollow
electrodes can use up to 15% lime fines (smaller than 6 mm, mostly
smaller than 3 mm). The limestone calcination temperature does not
significantly affect the reactivity of the lime (302528).
Carbon
The carbon used in making calcium carbide is usually coke made
from coal. Petroleum coke, which is more pure, was used until it
became too expensive. Anthracite is used in Europe, often mixed with
coke. It has the same amount of fixed carbon as does coke, slightly
less ash, and slightly more volatile matter. Charcoal can be used,
but its friability increases carbon loss. It is occasionally used in
23
mixtures with coke. Other materials suggested are shale tar coke
(which has a high C content but also is high in S), peat coke, and
carbonized lignite mixed with coke.
By far the most commonly used carbon source is metallurgical coke,
containing up to 90% C, 2% moisture and bonded water, up to 2X, vola-
tiles, 6-9X ash (usually), and less than 1% S. It is screened so that
80% consists of 10-20 mm particles, and 90% consists of 6-25 mm parti-
cles. Modern furnaces, which have hollow electrodes, can be fed as
much as 25% carbon fines (smaller than 6 mm, mostly smaller than 3 mm).
Impurities in the coke, besides water and volatiles, include
mainly SiO2, Fe203, and Al2O3; smaller amounts of S, MgO, Na20, and
K20; and still smaller amounts of P2O5 and N compounds. Some carbon
materials contain CaO, which of course is useful in making calcium car-
bide. Sl in the furnace charge is not significantly harmful if it does
not exceed 4%. Fe by itself is harmful, but it may counteract the
effect of Sl if the latter is present in excessive amounts (302497).
Different kinds of carbon, even different grades of coke, have
different reactivities in the furnace. Since the reaction is between
solids, porosity and surface conditions are very important to the
reaction rate. Furthermore, as shown in equations (1) and (2), the
presence of CO retards the reaction. The pores in the coke facili-
tate the removal of CO.
Electrothermal Process for Making Calcium Carbide
Furnace
The reaction of lime and carbon takes place In an electric fur-
nace, which is a steel bowl (usually circular, but it may be
rectangular, triangular, or hexagonal), lined with firebrick, and
covered on the bottom with carbon blocks. It has three electrodes
operating on 3-phase AC. The furnace may be open, covered (semi-
closed), or closed. In the open furnace, CO is burnt to form a flame
over the furnace surface, and the exhaust gas is drawn off through a
24
hood. The covered furnace recovers part of the CO; the closed furnace
recovers practically all the CO.
l
a
The electrodes may be prebaked, or made from a paste and baked in
situ in a steel shell above the furnace. The electrodes gradually
10-r into the charge. The electrode baked in situ is known as the
SCIderberg electrode. It has the advantage of having no butt because it
is effectively endless. It also has a significant cost advantage over
the prebaked electrode. A part of the feed coke and lime, in the form
of fines, can be fed through hollow cores in the electrodes (prebaked
or SBderberg). This device enables the use of coke fines and lime
fines, generated during preparation of lime and coke. It also reduces
electrode consumption by about 33%'(302334).
One type of closed furnace is the Elkem rotating furnace (302568).
The rotation is very slow, one revolution in 6 to 96 hours. Alterna-
tively, the furnace may turn slowly back and forth in a 600 arc. This
motion prevents the formation of a crater in the reacting mass.
Carbide furnaces are rated in kva. The largest furnace reported
is 70,000 kva. However, this does not necessarily mean that larger
furnaces cannot be built. The voltage varies from 100 to 250 volts.
The power useful in the furnace (measured in kw) is the product of kva
and the power factor. The power factor, which depends on the electric
system, varies from 0.80 to 0.98 (commonly 0.90-0.98 for modern
plants).
Molten calcium carbide is drawn off from one or more (up to 6)
e
tapholes, Intermittently from each hole but the draw-off may be virtu-
ally continuous for a large furnace. In some large furnaces there is a
separate, lower hole for tapping ferrosilicon.
Conditions in the calcium carbide furnace have been studied by VEB
Werke Buna of East Germany (302335-6, 302338-42) as well as by several
East German researchers (302343-4, 302346, 302348, 302356, 302435).
The furnace may be thought of as having three regions: main reaction
(A), preheating (B), and neutral (C), as shown in Figure 4.1. The main
25
-.
Figure 4.1
ZONES IN AN ELECTRIC OVEN
Ektrodes
Tapping fiole
Al, A2 Main Reaction Zones
B Pretmating Region
C Neutral Region
D Arczone
E Transition Zone
F Melting Zone
26
reaction region, in turn, may be subdivided into several zones. A
small part at the tip of the electrode is the arc zone, where the tem-
perature reaches 270WK and higher. Below this is main reaction zone
1, in which is a molten phase of CaO and CaC2, containing suspended
particles of CaO. Further below is main reaction zone 2, In which is a
molten phase containing no solid CaO. The temperature of the main reac-
tion zones is 2200-27000K. The melting zone is at the bottom; here,
with the temperature at 2100-2400°K, the reaction subsides and the mol-
ten mass Is ready to be tapped. In the preheating region, CO gas com-
ing from the main reaction zones at 2200-2600°K, heats the cold feed.
The neutral region has a temperature of 800-20000K. The transition
zone has a temperature of 2OOO-210wK; here, the solid becomes a
viscous liquid.
Note the sharp temperature gradient In the neutral region; the
solid charge, with its poor conductivity, acts as an insulator and
protects the furnace walls.
In one example, the main reaction zone 1 has a temperature of
2500-2600O~ and produces 73.6% of ths carbide produced In the furnace,
and the main reaction sane 2 has a temperature of 2300-25OOoK, and
produces 26.4% of the carbide (302344).
The electricity passes from each electrode by the following route
to the furnace bottom: arc-main reaction zones -melting
zone-bottom. The electricity flowing through the preheating
region between the electrodes is negligible. For a high current, as in
the carbide furnace, the voltage across an arc is constant, while the
voltage across the main reaction zones and the melting zone is propor-
tional to the specific resistance and the current. The carbide
furnace, therefore, essentially performs as an electric resistance
furnace. For data on the electrical resistance (or conductivity) of
the molten mass in the carbide furnace, see reference 302338.
Efforts to size the carbide furnace on a theoretical basis
(302339) have not led to any useful results.
27
The electric power added to a closed carbide electric furnace is
consumed approximately as follows (302453; B-43, p. 180):
Percent
Beaction heat 51
Heat In molten carbide 27
Heat in gas 2.5
Heat for reduction of other oxides 8
Electric losses 2
Heat loss to surroundings (through cooling water) 9.5
Handling of Calcium Carbide
The molten calcium carbide flows from the furnace into crucibles,
which are carried by cranes to a cooling hall. The crucibles are left
for about 40 hours in the cooling hall until the calcium carbide
therein has cooled to about 2OoOC. The carbide blocks (0.8 to 5 tons)
are emptied from the crucibles, and crushed. This coarsely crushed
calcium carbide is loaded on a belt and carried to a fine crushing
machine. The product is then screened, and ferrosilicon is removed by
a magnetic separator.
The above is the way calcium carbide Is handled in most plants.
Another way is to use vertical cooling conveyers (302550).
An improved procedure saving substantial labor is described in a
Knapsack patent (302093). Calcium carbide is received in trucks on
rails. After 4 hr, when the surface temperature of the calcium carbide
block in the truck is about 6OoOC, the upper part of the truck Is
raised by a crane, and the block is transferred to an inclined plane,
and from there to a conveyor. After another 14 hr, the surface of the
block is 2OCPC, and the block is ready for crushing.
Table 4.1 lists the patents on the manufacture of calcium carbide
in electric furnaces. With one exception (reference 302583, on feeding
through a hollow electrode), only patents issued after 1965 are
28
Table 4.1
CALCIUM CARBIDE BY ELECTROTHERMAL PROCESS
Reference Wumber
302583
Aeelgnee
IJCC
First Application
Date
11/21/58
Fine feed added to the furnace through the hollow electrode.
302093
---- ---- -11 ----B-B
Knapsack l/11/72
Device for cooling calcirr carbide from furnace.
302369
-- ------------ --1ss-1---
Boeenka, J., et al. 4/7/73
Semicloeed furnace, with part of gae being removed froo lovrr layers of mixture through tuber extending into the charge. The upper layers of the charge are treated ufth cool CO2 or #2.
302288 Singer, We, et al. 2121176
Uee of coke mede from coal pkmticlee containing lime; 5% lime in the coke increaeee the furnace capecftp by 7-13X, and decreaeee power ueage by l-2%.
302413
-- ------- ---1-1B-1-M -m--m
llenki Kegaku 3124 j77
Cob and lime charged through the electrodes into the furnece dth capreread 12.
302385 U8SB 4/4/77
Iron added to the furnace to combine with the eulfur in the lime feed. ---- --m---------- --e-1----
302412 Denki Kegaku 5/U/77
Lime sod coal coaprreed to fore pellets and used ae feed. --- ---------- 1--B------ -e-----
302287 VEB 8uaa 5/18/77
Pulverieed coking coal ie mixed dth finely divided Ce(Oli)2 and compreeeed into cakee which are coked at 1300oC for 26 hr. The reeulting coke ie dried, mixed dth lime, and charged to the furnace.
302292 MB Buna 7/18/77
Powdered broun coel ie mixed wfth Ce(OH)2 and dried mete eulfite liquor, briquetted, coked, and ground; ueed ae raw material together dth lime and coke.
29
Table 4.1 (Concluded)
CALCIUM CARBIDE BY ELECTROTHERMAL PROCESS
geference Rqmb& Amsignee
Firet Application
Bate
302290 Eellmond, IL, et al. 11/2/77
Carbon dioxide ueed a8 carrier gee to tramsport the raw meterial.through the hollow electrodeo.
-m--- -- -- -m----
30228; Frattcher, W., et al. 6 /29/78
Eat gas ummd to preheat and deco&e raw materiale, including the decapoeltion of ca(OH)2 to lime.
-w------I___--------- --- -1-w----
302398 Danki Kagaku .11/7/78
Lim, coke, and 1.5% hydrocarbon eolution in cBC15 are briquetted and used ae feed.
--- ---- --- ---me
302608 Hitachi Shipbuilding a/19/80
A mymta for recovering heat from hot calclm carbide granules, with a circulating air stream; the heat ir transferred through a heat exchanscr to a working plant driviw a turbine for pover generation.
--- ----I_ IS -1--m---------1--
r
30
included. All the important information in patents before 1965 has
been covered in the celebrated work of Miller (B-43).
Effluents from Carbide Furnaces
Gas from a closed furnace is mainly CO, with some H2, and is
highly contaminated with ash. After the dust is removed, the CO is
used for fuel or other purposes. About one-half of the gas from a
semiclosed furnace Is collected.
In an open furnace, the CO is burnt at the surface. The resulting
combustion gas leaves the furnace room through a hood. This large
amount of gas (about 50 times the volume of gas from a closed furnace
of the same capacity, because of the air sucked in), highly laden with
dust, is a serious pollution problem. It cannot be successfully han-
dled by electrostatic precipitation. Bag filtration is satisfactory,
but is quite expansive. The solution of this pollution problem has
always been difficult and expensive (302352, 302537, 302541).
The wastewater formed during the scrubbing of gas from the furnace
and lime kiln contains finely divided coal, limestone, and Mg(OH)2.
The solids have to be allowed to settle before the water is discharged.
There has been an effort to utilize the recovered dust by slurrying it
and reacting it with flue gas to get MgO (302445).
Other Processes for Making Calcium Carbide
The heat necessary for forming calcium carbide may be generated by
combustion of coke. Oxygen instead of air is desirably used, In order
to attain a high temperature and also to minimize the blowing effect of
the gas stream. Assuming that (1) there Is no heat loss, (2) pure CaO
aud C are used to make 82% CaC2 at 1970°C, and (3) CO leaves at the low
temperature of 25oOC, the heat balance corresponds to the following
stoichiometrlc equation (B-43, p. 215):
1.22CaO + 8.7C + 2.8502 -0.22CaO + CaC2 + 6.7CO
31
In the above equation, the C-to-CaO weight ratio Is 1.5 instead of
0.63 as in the electrothermal process. Because not all the above-
mentioned assumptions are achievable, the ratio would be significantly
higher. In one instance, the material balance is as follows (302549):
Input output
2,000 kg coke (80% C) 1,000 kg calcium carbide
1,100 kg lime (92% CaO) 315 kg dust
1,785 kg 02 (98% pure) 3,500 kg gas (95.5% CO, 2% H2, 2% N2)
4,885 kg total 70 kg loss
4,885 kg total
The gas produced is more than 7 times that produced in the electro-
thermal process; its amount is more than that of calcium carbide.
Hence, this process, in a sense, produces CO and coproduces calcium
carbide.
BA8P pioneered this process as early as 1949 and once operated a
100 tons carbide/day pilot plant (302512, 302518). Patents grouped
under A in Table 4.2 relate to such a process.
The endothermic heat for making calcium carbide can also be
supplied by a heating medium such as CO. The CO is heated in a regen-
erative furnace, which in turn is heated by combustion (302405-6). An
inexpensive fuel can be used Instead of coke, and air can be used
instead of oxygen. Patents grouped under B in Table 4.2 relate to such
prowesses.
Patents grouped under C in Table 4.2 are for processes for making
calcium carbide in the presence of compounds other than CaO and C, or
as a by-product.
32
Table 4.2
CALCIUM CARBIDE BY PROCESSES OTHER THAN THE CONVENTIONAL ELECTROTHERMAL PROCESS
PATENT SUMMARY
Reference Number krignee Earliest pilin8 Date
Ib. Oxythemal proceea, combustion heet l upplied by burning coke
302104 302098 '
7/4/50 2/L6/54
Shaft klln burni- coke and lime with air or oxygen.
302110 I&cknr Chede 11/25/52
Hydrated lima aml ground coke ue mixed with water and a rall amount of tar, molded into particles, and heated irr a l baft kiln tith coke and air or oxygen.
---
302106 Stamicubon 10/26/54
Vertical furnace for malriqg celciu carbide from limertona and coke.
302109 Texaco 5/ 9/57
Lima ad coke srupenddlnoxy~nreact to fomcalclumcubide.
302108 Texaco
Coke, lime, fuel ~8, and oxygen react to fom calciu carbide.
S/9/58
I-- ----- --
302118 Enya, B. a/10/70
Li~etone,coke, foelgae,and oxygen react to form calcium cubidc. -- ---
---I_------ ---
B. Oxytheaal procams, heated and supplied fra outride oource
302416 mlkl Eagaku 302415
I&me, coke, aad pitch are pelletired and heated to 19ooOC in Co.
l/31/77 l/31/77
- -I- ---
33
Table 4.2 (Continued)
CALCIUM CARBIDE BY PROCESSES OTHER THAN THE CONVENTIONAL ELECTROTHERMAL PROCESS
PATENT SUMMARY
Reference Muxber Assignee Earliest piling Date
B. Orythemal process, heated aud supplied from outside source (Continued)
302414 De&i Kagaku 3/24/77
Liw, coke, and pitch are pelletiaed, heated to 1300oC in CC, and further heated to 19OoOC in a coxbuatlon gas.
362284 Taxers, M. A.
Lixe and coke heated on a xolten iron surface.
4120177
302411 Denkt Kagaku 6/l/77
Lim, coke, and 5-15X powdered iron or iron oxide are briquetted and heated in Ar at 19oooc.
--p---1--- --I--------- ------I_-
302409 Ds~K.I Kagaku 6115177
Lirc and petroleux coke are lmeaded dth tar pitch, pelletiaed, aud heated to 19OoOC by a coxbutvtion gar formed by burning oil in oxygen-enriched air.
-__I_------- ----I---------- --I---
302407 De&i Kagaku 714177
Lixestone ie calclnd at 19OoOC, lixe obtained is imediately mixed uith coke and heated 200C°C.
-------1I--1---1---1- -1-11-11-1-1
302406 Danki Kagaku 7/a/77 302405 11/15/77
Lima and coke are heated by hot CC In a shaft kiln at 2000°C; CC la heated In a regenerator.
--- -1--------- ------------------l_--I-I---------
302404 Denki Kagaku 12114177
Lixe and coke are heated in a vertical shaft kiln by a cabuation gas frou burning heavy oil ulth air preheated tith exlaauet gas*
302403 TDK Electronics 3/15/78
-
a -
a
Lixeatone is calcined in an inner cylinder in a double wlled rotary furnace; coke is added to the outer cylinder and mixed ufth the lixe at the middle of the cylinder.
34
Yable 4.2 (Continued)
CALCIIRI CARBIUE BY PRUCSS8E8 UTE8P TEAN Tm 00NvENT10uAL lm CTRGTBERMAL PRucESs
PAl’88T8lJMfAgY
Reference 8umber Aaalgnee Eullert Pilin8 Date
B. Oxythemal process, heatad and supplied fra outside source (Continuad)
302400 Dank% Kagaku 617178
Lim and coke are haatad to 20W°C and higher by a cabuation gaa fra burning a fuel dth oxygen or enricbad air; axhauat gas ir uaed for etam genaration.
302401 Dankl Kagaku 617178
Similar to l bwe, exhaust gaa rued for preheatiag of air for cabuation.
302399 Danki Kagaku g/4/78
8lud8a fra acetylene 8eneration. add powder coka and pitch, pellatiaed, celcinad at LOW%, aId than heated by a cabuation pa fra burobg heavy oil.
---- ---m---e-
C. Procaaua Startim uith Carbonaceous 8ubatanca Otbar Than Coke, and Proceaaea UsIn a third Ca~nanL.
302086 Granier , L. 4174141
Lim, carbon dioxide, and nitrogen react in an electric furnace to form CaC2 and c8clQ.
-- A----- --
302113 &ppelin l/26/55
Liu, coke, and hydrogen are heated to 18OoOC to form calcium carbide.
302082 UCC 2126159
glectrol~aia of a molten Cm salt in preunce of C. ---II_-- --------
302115 U8S8 10/S/60
Matbane is burnt dth enriched air in presence of lima, calcium chloride, and carbon black to foa calci\n carbide.
--em- ---w--- -------
302102 Ureatom, G. 1. 10/31/60
Calcium carbide by-produced In Mg production.
35.
Table 4.2 (Concluded)
CALCI~CARBIDB BYPEOCBSSBS tYfRERTBMTBE CommYIOuAL SIB- PROCE88
PAYlWY8UMHAEY
Refertie Rumha ka~nae Earliest Fililps Date
C. Procaaua starti- with carbonaceous substance other tbam coke, aad proceaaea using a third caponent (Contimed).
320388 U88R g/10/73
Refinery gee (hydrocerbon and H2) p8aua through a heatad layer of lima.
8ea ala0 articles:
302499-Finaly divided lime ad CQ (or coal in Hz) pass tbrotqh a rotary arc reactor.
302533--&int production of CaC2 and P fra calciu plmapbeta.
30251~Production in a plasma fluidiacd bad.
30253~Umatou raacta with m to form CaC2, CaO, and H@.
36
Evaluation of an Electrothermal Process for Making Calcium Carbide .
Process Description
SBI has conceived a process for producing calcium carbide in an
electric furnace having a capacity of 300 million lb/yr. The design
bases and assumptions are given In Table 4.3. The flow sheet is given
in Figure 4.2 (foldout at end of report). The flow streams marked in
Figure 4.2 are described in Table 4.4. The major equipment list and
utilities supp~~~ry are given in Tables 4.5 and 4.6 respectively.
Table 4.3
CALCIUM CARBIDE BY ELECTROTHERMAL PROCESS
-
a
DESIGN BASES AND ASSUMPTIONS
Beferences B-43, 302037, 302093, 302568, 416042
Lint Vertical, gas-fired lime kiln; limestone 98% C&O3
coke 85% C, dried by gas from lime kiln
Electric furnace AC, three phase, closed type, pouer factor 0.85; S8derberg electrodes, fine feed through hollow core
Roduct 82% Cat+
Limestone in 1 to 5 inch lumps'is loaded into the built-in bins of
a vertical lilre kiln. In a preheating cone, It is heated by a gas con-
sisting wetly of carbon dioxide. It then falls into a calcination
zone, where fuel gas enters through pipes and burns with air flowing in
at the bottom. Tbe kiln operates at 14OoOC. The limestone decomposes
to lime aad carbon dioxide. Lime falls to a cooling zone, to be cooled
by the Incoming air. The lime discharges at the bottom through chutes
onto a belt conveyor, which takes it to a vibrating screen. The lime
Is separated into plus l/4 inch and minus l/4 inch sizes, and stored in
bins.
37
The gas from the kiln, at about 260-300°C, passes through a multi-
cyclone to remove the dust and then passes to a coke drier. In the
inclined rotary drier, coke and the hot gas flow downward. At the
bottom end, the coke discharges to a vibrating screen, where it is
separated into plus l/4 inch and minus l/4 inch sizes, and then it is
stored in bins. The gas from the rotary drier, at 130-14oOC, passes
through a cyclone and goes to a stack.
The electric furnace used for making calcium carbide is a closed
type, with three hollow SCfderberg electrodes. Lime fines and coke
fines (minus l/4 inch) are fed through the hollow space of the elec-
trodes. The balance of the lime and coke is fed through the furnace
top. Rail-trucks receive the molten calcium carbide from tapping holes
in the furnace. The tapping is done by a portable electrode, which gen-
erates an arc and melts the frozen calcium carbide at the hole. The
truck moves slowly along the rails from the furnace room to the carbide
room, being pushed along by the next truck. After about 5 hr, the
ingot solidifies on the outside and shrinks. A crane lifts the upper
part of the truck, and the ingot falls onto an inclined plane (M-401)
and slides onto a long belt conveyer (M-402). The Ingot continues to
cool on the belt and finally freezes to the core. The carbide is then
crushed in a primary jaw crusher to minus 4 inch pieces, further
crushed in a secondary jaw crusher to minus 2 inches, passed through a
magnetic separator to remove FeSi and Fe203, elevated, screened on a
multideck screen to separate it into several grades, and stored In
bins.
The SBderberg electrodes are made in situ. Coke fines, anthra-
cite, tar, and pitch are kneaded hot (heated by a small stream of fur-
nace gas in the jacket) and poured into a sheet steel casing. The heat
from the furnace bakes the mass in the casing into a solid electrode,
which gradually descends into the furnace to replace the burnt-out por-
tion. The steel casing burns with the electrode, and new sections are
added at the top as the electrode is lowered.
38
-
l -
Gas from the furnace passes through a settling duct, bag filters,
and a blower, on its way to the lime kiln to be used as fuel. A small
part of the gas stream flows through the electrode mass kneader, where
it releases some sensible heat before it rejoins the streem to the
kiln.
To accommodate the fluctuation of operation rates of the electric
furnace and the lime kiln, the furnace gas pay be stored in a gas
holder. In this case, the gas is cooled in E-501 before storing.
Optionally, a gas-producer may be provided for start-ups.
Each bag filter is a vertical cylinder containing fifty 20-foot
long tubes made of ceramic fiber. The bags are cleaned occasionally by
mechanical shaking.
The solid waste from the settling duct and the bag filter may
contain a trace of cyanide. For disposal, it is desirable to treat the
waste with a solution of an iron salt, to convert the cyanide Into a
harmless complex salt.
39
Table 4.4
CALCIUM CARBIDE BY ELECTROTHERMAL PROCESS
STREAM FLOW
Plant Capacity: 300 Million lb/yr (136,000 Metric Tom/Jr) Calcium Carbide
at 0.90 Strer Factor
84 756 1,730 3,393 30,536
2,836
-
-
Calcim carbonate Qlcilm oxida Carbon Anthracita Tar Pitch Calciu carbide Cmrbonmnoxide mr*en, metbane, et al. Carbon dioxide
QYS- 8itrogen Water Othera
Totals, lbfhr Lg/h
Totala, lbrol/hr kS-=Ol/k
100.0 63,842 56.0 - 12.0 - 400.0 - 400.0 - 400.0 - 64.0 - 28.0 -
4::: -- - 32.0 - 28.0 - 18.0 - So.0 2.300
66,142 30,001
6& 303
16,800 - -
-
-
-
- - 67 443
3,346 1,518
246 111
- 3,196 3.080
26,206 11,887
1,877 851
383 1,283 2.527
2,083 3,624 32,575 945 1,644 14,776
35 63 569 16 29 258
19,710 8.940
1,453 659
Ho1 Stream Flowe (lb&)
- J.@ (9)* (10) (11) (12)* (13)T m
Calcim carbonate 100.0 Calcium oxide 56.0 Carbon 12.0 Anthracite 400.0 Tar 400.0 Pitch 400.0 Calciu carbide 64.0 Carbon monoxide 28.0 Hydrogen, methane, et al. 8.0 Carbondioxide 44.0 QYS- 32.0 Uitrogen 28.0 Water 18.0 Other6 80.0
4,566 380
- 1,150 720
- 196 228 57 57
-
-
32 - 570 259
18 8
Totale, lb/hr b/b=
Totale, lbrol/hr k8-mol/hr
- -
31,448
14,880 52,080
- 66,375 2,490 52,080 18,144 Preeent
17,861 66,960 139,089 8,102 30,372 63,089
675 2,325 4,454 306 1,055 2,020
a 1.658 1.650
38,052 3,520 17,260 1,597
625 101 284 46
*Other0 are eilica, HgCO3, alumina, CaSO4, iron oxide, and eodium capounda.
tOthera are eilica, alumina, CeSOq, iron oxide, k@O, volatiler, aad IUa, I, and S compounde.
SOthere are rilica, alumina, CaS, Sic, Al-carbide, Al-nitride.
40
Table 4.5
CALCIUM CARBIDE BY ELECTROTHERMAL PROCESS
MAJOR EQUIPMENT
K-101 K-301
U-501
T-101 T-102 MO1 T-202 -203 ?-2oI T-301 t-3@ T-303 T-304 MO5 T-306 T-307 NOIA-B T-551A,9
l-lOlA-D
9-201 S-5OlA.B
w101 N-102 n-103 ~104 n-105 N-106 *107 I+201 l&202 S203 B&204 N-205 lk206
is: n-302 le303 n-304 n-305 u-306 MO7 n-401 MO2 u-403 It404 n-405 N-406 It407 u-ms
Plant Capacity: 300 million lb/yr (136,000 Metric Tons/yr) Calcium Carbide
at 0.90 stream Factor
sin Material of Caautnlction
140 bhp 120 bhp
mu lad umtwia1 of caMtrlutiom gel rtr/hr) St, 6lnll hrbu
VOltr (ml) Ilrt*rial of Cmstructiom
Cmbm l tnl cub08 st*e1 Carbon arm1 Carborn mm1 carbm mud Carbon at-1
Carbaa l m1 carbon l w1 ☺Ukued. cubon rtad Cubm awl
tirbom a**1
brbon *em1 Carbon *teal
Comtaioily 16 epdowm .ach 9 in. din.
Coathh6 50 earric fiber bqy 6 in. dia 20 ft lo-.
C&a drier Vibtmtin act-
100 ft 10 in. 0 60 ft 30 .q It loo It, 12 x 7 x 7.5 LB. 100 ft. 6 x 4 x 4.5 ia. 60 ft w it 40 ft. 6 x 4 x 4.5 in. 6 ft dia 36 ft loq 30 mq fC 46 ft. 6 I 4 x 4.5 la. 60 ft. 6 x 4 x 4.5 in. 40 ft. 6 I 4 x 4.5 lo. 60 ft. 6 x 4 x 4.5 in. 20 fL 6 in. x 20 It 6 in. x 20 ft 660 tt loop 2.7 er ft 50 It loq. 14 ft dir
20 et 0 200 ft widm SD0 ft x 36 in. 120 hp 30 It 35 hp
loo ft. 6 x 5 x 7 in. 40 .q fC triple
Cubon l trl Cubon wed cubon l Wl Cubm l trl Corbm aed
Cuban l tad Cub00 steel Carbon awl Carbon l tnl CUlKm an1 carboo l tca1 Carbon *teal cubon a-1 linbrict Virmbriek Cuban me81 cubon l t*d Carbon at-1 Carbon *tad Cuba l tal
carbon l ~Rl
41
Table 4.5 (Concluded)
Plant WpacitJ: 3W nillioa lb&r (136,WO lhtric Tone&t) Calcium Carbide
at 0.90 stream Factor
m&y’ Iim She Material of Comtwtion PurLa
Prkape Dnita
PAM01 ur kiln 4 ft I 65 ft wrk. bt ucc type? PM-301 BleefxiC furmace 70,oM)o KVA Blkim type. 220 volt. 3 phuc,
claand, hollow S6derberS electrode with traarfoaer.
PAC-501 cm prodocmr 5M!lStlJ/br
Table 4.6
CALCIlIRlCASSI~ STBLECTROTHXSMAL PpocSSS
IITILITIIM SUIHARY
Plmt capuity: 300 Nillioa lb/yr (136.000 Ifetrie To.a/yr) Cal&u Carbide
at 0.90 strmn Factor
Sattery Limit* LW 200 300 400 500 Total sectioa sectiom &ctiw &ctiw saction ---
Awrw cmuuption ceolillg lmtm! (spr) 555 -- 550 - 5
Blctricity (kwh) 56,122 177 32 57,700 160 33
Inertp.,laprumre(mcfb) 7.000 -- - - 7.060 -
Pa& dumd
coolicy nter (gpm) 1,040 me 660 - 380
42
Process Discussion
The equipment specified in Table 4.5 can produce the target produc-
tion of 300 million lb/yr calcium carbide (82% CaC2) with a stream
factor of 0.86 for the furnace and 0.90 for other equipment. The
stream factor 0.86 depends on the electricity supply being reliable
throughout the year; the remaining time is for furnace maintenance. If
the power is not reliable throughout the year, a larger furnace, or
preferably two furnaces of higher kva should be provided. The furnace
capacity should be further increased if daily off-peak power or sea-
sonal power is to be used. Occasionally a reduced power tariff makes
the additional investment worthwhile.
In the design case, = assumed the coke to be 86.6% fixed carbon,
dry basis, which is readily available in most regions of the world. In
some localities, there are better grades, with a C content as high as
91-922. Use of such a premium coke would lead to production of calcium
carbide of higher purity, with lower power consumption and lower coke
usage. Use of such a premium grade coke is especially desirable when
recycled "carbide lime" or "carbide sludge" is used. We will discuss
this further in Section 5. The Harestone used Is a high calcium grade.
This is a must for carbide manufacture. It is available in most
countries.
Variations are possible in the equipment and arrangement used in
the process (rotary kiln instead of vertical kiln for lime burning,
prebaked electrodes instead of Mderberg electrodes, multicyclone
instead of bag filter, alternative way of handling the ingots, and so
on). We believe that the scheme we used in the design case Is well
suited to large scale production. All devices except the ceramic-fiber
bag filter are believed to be used in existing carbide plants. The
ceramic-fiber bag filter was recently developed in the United States to
handle coal dust (302604). We believe it Is excellent for the present
purpose.
There is a huge amount of heat in the calcium carbide ingots die-
charged from the electric furnace. One simple way of recovering part
43
of the heat is to pass the ingot trucks through a tunnel in which air
is blown through countercurrently. The hot air is then used to heat a
steam boiler. Depending on the efficiency, 0.4-0.7 lb steam can be
generated in conjunction with the production of 1 lb of carbide.
Cost Estimates
The estimated capital investment and production cost are given in
Tables 4.7 through 4.10. Production cost and product value at differ-
ent levels of-operation are given in Figure 4.3. In this process, a
100% operation level is possible only if the electric power is 100%
reliable. The stream factor for the electric furnace allows for
maintenance, but not for power failure. In some localities the power
is not. reliable, and the operating level would be lower. Alterna-
tively, one may have to install a furnace of higher capacity.
As pointed out under Process Discussion, heat in the calcium car-
bide ingot can be partially recovered by generating 0.4-0.7 lb steam
per lb calcium carbide. This corresponds to a 0.2-0.4c/lb reduction in
production cost or product value.
Screened coke breeee is coke with particles less than 1 inch but
free from fines. With coke (plus 2 inch) now sold at $lOO-120/tori and
breeee at $5+60/tan, a price of $7O/ton (3.5c/lb) for screened breeze
seems to be fair. However, in real life there might not be sufficient
screened breeze for a large carbide plant. If regular coke at $lOO/ton
(5c/lb) has to be used, the net production cost and product value of
the carbide muld have to be increased by about lc/lb.
The electricity is the largest cost Item. A change of lc/kwh
would change the production cost by as much as 1.53c/lb.
The present market price of calcium carbide in the United States
is $315 per short ton. It Is evident from the numbers in Tables 4.9
and 4.10 and Figure 4.3, that this price reflects a situation In which
either the producer is getting cheap power, or the plant has already
been largely amortized.
44
-
Arrangements are sometimes made between the carbide producer and
the power supplier to utilize daily off-peak electricity or seasonal
power, the latter being due to the generation of hydroelectricity in
some months. To cope with this situation, however, the carbide plant
has to install additional electric furnaces. Whether this would be
beneficial for the carbide producer depends on the individual sltua-
tion.
The following is an example of an operating schedule to use the
daily fluctuation rate:
Power Supplier's Scheduled Furnace Time Load Condition Power Rate Operation Rate
6-9 a.m. 6 5-8 p.m. Peak load 233% 50% of load
10 p.m.-6 a.m. Low load 33% 100% of load
9 a.m.-5 p.m. & 8-10 p.m. Normal load 100% 80% of load
Fran the above schedule it can be calculated that the maxlmtrm furnace
capacity should be at least 25% greater than the average capacity. If
instead of a 70,000 kva furnace, an 88,000 kva furnace or two 44,000
kva furnaces have to be installed, it can further be calculated from
the schedule that the average power rate throughout the day Is 92.8% of
the normal rate. The cost features can then be estimated, as In Table
4.11.
From Table 4.11 it is seen that the variable operation scheme has
a slight econanic advantage for an 88,000 kva furnace, but it Is quite
uneconomical if two 44,000 kva furnaces have to be installed. Whether
It is economically beneficial to the carbide producer to adopt a varia-
ble operating schedule to suit the load situation of the power supplier
depends on the power rate structure, but even more on the effect this
schedule has on capital investment. In general, such a schedule would
not be economically beneficial if It leads to an increase In the number
of electric furnaces.
45 (Text continues on page 53.)
Table 4.7
CALCIUM CARBIDE BY ELECTROTHERMAL PROCESS
CAPITAL INVESTMENT
Plant Capacity: 300 Million lb/yr (136,000 Metric Tons/yr) Calcium Carbide
at 0.90 Stream Factor PEP Cost Index: 360
Battery limits equipment, f.o.b. Vessels and tanks Exchangers Compressors Separators Miscellaneous equipment
Total
Lime kiln Electric furnace Process buildings
Battery limits equipment installed Contingency, 25%
BATTERY LIMITS INVESTMENT
Off-sites, installed Cooling tower Inert gas Tankage
Utilities and storage General service facilities Waste treatment
Total Contingency, 25%
OFF-SITES INVESTMENT TOTAL FIXED CAPITAL
cost
Capacity Exponent
up Down
$ 630,400 17,700 64,800 442,800 856,100
$ 2,012,OOO 0.72 0.67
5,061,600 5,800,OOO 4,968,OOO
$27,463,000 6,867,OOO
$34,330,000 0.90 0.52
$ 353,900 139,300
2,247,500
$ 2,741,OOO 0.87 0.65 6,041,OOO 1,510,000
$10,292,000 2,573,OOO
$12,865,000 0.89 0.56 $47,193,000 0.90 0.53
-
a
a
46
CAPITAL INVESTMENT BY SECTION
-
a -
a
Plant Capacity: 300 Million lb/yr (136,000 Metric Tons/yr) Calcium Carbide
at 0.90 Index Factor PEP Cost Index: 360
latteq liaitr aquipuot. f.o.b. Vwwlm ala tMkI 0 64,800 0.60 0.60 $ 142.200 0.60 0.60 (I 77.800 0.75 0.60 Escbamgata - - - - - - - - - captwatr 36.000 0.95 0.61 - - - 211,SOO 0.95 0.61 &pmMotm 57,600 0.95 0.95 25,200 0.W 0.1 360.000 0.70 0.70 nirelhmus equipmnt 106.600 0.07 0.70 174.600 0.70 0.70 109.700 0.81 0.74
Sattarp lidtm l qulpnrt. f.o.b. vem~eh and tank* Excbal&eta ccaptcmot~ sepatatotr nira1laneour aquipmmt
Total Lima kll0 l3lactrlc fumma Ptoecra buildlraSn
nattety 1hltm l quipmt lnmtalhd co0t1gll*ncy, 252
MrrEuY LMITS ISvSSTlmwc off-altel, iwtalhd CoolinS tom= Inert *.. TallkUa
uti1itim aId .totw.
$ 265,006 4,S96,000
$7.972.000 1.993.000
$9.965.000
6 -
0.u 0.71 0.95 0.50 - - - -
0.93 0.46 0.93 0.40
0.93 0.41)
- - - - - -
- -
8 345,600
-- 3S5.200
$ 730,sOo
4.320.000 6.314,OW 1.579.060
$7.893,ooo
0.60 0.60 - - - - - -
0.72 0.69
0.66 0.65 -- - - -
0.w 0.60 0.90 0.55 0.90 0.55
0.90 0.55
- - - 139.300 0.53 0.53
- - -
$ 139.000 0.53 0.53
$342.000
$1,034,W0 259.ooo
$1,293,W0
6 -
0.67 0.67 - - - - - -
1.03 0.23 1.03 0.23
1.03 0.23
- - - - - -
- -
$ ---
17,700 0.43 0.37 - - - - I - - - -
$ 17,700 165,600
284,000 71.000
$ 355,Ooa
129.300
2.247.506
$2.377.o00
0.43 0.37 0.05 0.05 - - - -
0.75 0.74 0.75 0.74
0.75 0.74
0.37 0.20 - -
0.95 0.73
0.92 0.70
$ 656.300
5.sw.000 64S.000
$11.859.000 2.965.000
$14.824,000
224.600
$ 225.OW
0.75 0.69 - -
0.95 0.54 0.80 0.00 0.88 0.54 0.0 0.54
0.W 0.54
0.37 0.2s - - - -
0.37 0.2s
47
Table 4.9
CALCIUM CARBIDE BY ELECTROTHERMAL PROCESS
PRODUCTION COSTS
PEP Cost Index: 360
Variable costs unit cost Consumption/lb C/lb
Rsw msterials
Limestone coka Pitch Anthracite Tar coal
Groee raw materials
Utilities
Cooling mter Electricity Inert gas, lo p
Total utilities
O.Sc/lb 3.5c/lb W/lb Wlb &/lb 1.5c/lb
1.686 lb 0.674 lb 0.0015 lb 0.006 lb 0.0015 lb 0.0435 lb
0.84 2.36 0.02 0.02 0.01 0.07
3.32
Unit Cost Consumption/lb Cousumption/kg c/lb
5.25~/1,000 gal 0.875 gal 3.2c/kwb 1.53 kwb 70C/l,OOC scf 0.184 ecf
7.3 liters 3.36 kwh 10.9 liters
&8l 4.88 0.01
4.89
48
a
l
l
a
Table 4.9 (Concluded)
CALCIUM CARBIDE BY ELlDXROTRgRMAL PROCESS
PRODUCTION COSTS
PEP Cost Index: 360
Capacity (million lb/yr)* 150 300t 600
Investment ($ million)
Battery limits Off-sites
Total fixed capital
Scaling exponents
Production costs (c/lb)
Raw materials Utilities
Variable costs
24.0 34.3 64.2 8.7 12.9 23.8
32.7 47.2 88.0
0.53 0.90
Operaticg labor, 8/shiftS, $15.4O/hr Maintenance labor, 3Xlyr of BL iw Control lab labor, 20% of op labor
Labor costs
Maintenance materials, 3%/yr of BL im? Operating supplies, 10% of op labor
Total direct costs
Plant overhead, 80% of labor costs Taxes and insurance, 2%/yr of TPC Depreciation, lO%/yr of TPC
Plant gate cost G&A, sales, research (5% of sales)
Net production cost ROI before taxes, 25%/yr of TPC
Product value
3.32 3.32 3.32 4.89 4.89 4.89
8.21 8.21 8.21
0.67 0.36 0.20 0.48 0.34 0.32 0.13 0.07 0.04
1.28 0.77 0.56
0.48 0.34 0.32 0.07 0.04 0.02
10.04 9.36 9.11
1.03 0.62 0.45 0.44 0.31 0.29 2.18 1.57 1.47
13.69 11.86 11.32 0.77 0.77 0.77
14.46 12.63 12.09 5.45 3.93 3.67
19.91 16.56 15.76
*Of calcium carbide.
tBase case.
OFor base case only; may be different for other capacities.
49
Table 4.10
CALCIUM CARBIDE BY ELECTROTHERMAL PROCESS
DIRECT OPERATING COSTS BY SECTION (Thousand $/yr)
Plant Capacity: 300 Million lb/yr (136,000 Metric Tons/yr) Calcium Carbide
at 0.90 Stream Factor
Raw materials
Limestone coke Pitch Anthracite Tar coal
Total by-products
Utilities
Cooling water Electricity Inert gas, lo p
Total utilities
Labor
Operating Maintenance Control laboratory
Total labor
Maintenance materials Operating supplies
PEP Cost Index: 360
100 Section
2,529 - - -
-
,2,529
-
45
45
202 299 40
541
299 20
Total direct costs ?*,434
200 Section
300 Section
- -
7,014 63 - 45 - 72 -- 36 - --
400 Section
-
-
-- --
7,014
-
8 -
216
14 14,544
8 14,558
45 39
84
67 270 472 39 445 237 13 54 94
119 769 803
39 445 237 7 27 47
7,187 16,015 1,171
-
500 Section
-
-
-
196
196
-
8
8
67 11 13
91
11 7
313
50
Table 4.11
CALCIUM CARBIDE BY ELECTROTHERMAL PROCESS
COST EFFECTS OF ADOPTING A VARIABLE OPERATING SCHEDULE
Furnace (kva) 88,000 2 x 44,000
Imeatment ($1,000)
cost 6,900 8,800
Cost of 70,000 kva furnace 5,800 5,800
Change In equipment cost +1,100 +3,000
Change in battery limits investmmt +1,900 +5,300
ChanBe in total fixed capital +2,300 +6,300
Production cost chaages (c/lb)
Maintenance
Depreciation, taxes, insurance
Electricity
Net production cost
25% ROI
Total change
+0.05 +O.ll
ul.09 $0.25
-0.35 -0.35
-0.21 +O.Ol
MI.19 +0.73
-0.02 +0.74
51
40
38
36
5 34
16
Figure 4.3
CALCIUM CARBIDE BY ELECTROTHERMAL PROCESS EFFECT OF OPERATING LEVEL AND PLANT CAPACITY
ON PRODUCTION COST AND PRODUCT VALUE
I I I Production Cost
-m- Product Value
Million Ib/yr \
\ 150
5-+-l-i-
0.5 0.6 0.7 0.8 0.9
OPERATING LEVEL, fraction of design capacity
Present - Price
Level
52
A Brief Evaluation of an Oxythermal Process for Making Calcium Carbide
Process Description
A process using the heat from the combustion of coke and oxygen
for making calcium carbide from coke and lime is briefly evaluated.
Our design bases and assumptions are given in Table 4.12. The flow
diagram for the reactors and related equipment are given in Figure 4.4.
The other parts are the same as in Figure 4.2. Coke and lime are added
to the reactors to maintain a total hearth depth of 22 ft, consisting
of an 8 ft preheating zone, an 8 f t reaction zone, aud a 6 ft calcium
carbide melting zone* Preheated oxygen is sparged into the reaction
zone. Gas is discharged at the top, passed through a duct and filters,
and then carried by a blower to the gas holders. This Is 95% CO, and
can be used for carbonylation or other uses, probably with only some
purification steps to remove S. Alternatively, it can be used as fuel.
A small pert Is used for calcination of limestone.
Table 4.12
CALCIUM CARBIDE BY OXYTHERMAL PROCESS
DESIGN BASES AND ASSUMPTIONS
References 302549; B-43, pp. 215-6
Reactor Coke:llme = 2O:ll (weight); combustion by oxygen; coke and lime, larger than 0.25 inch
Other sections same as in Table 4.3.
The lime section is the same as that for the electrothermal pro-
cess described earlier. The coke section is the same, but the capacity
is larger by a factor of 3.3. The carbide section (the handling of the
Ingots and the crushing, and so forth) Is also the same. Despite the
enormous amount of gas available, a gas producer is still needed for
producing lims for starting up. Alternatively, purchased lfme may be
53
Figure 4.4
REACTORS IN THE OXYTHERMAL PROCESS FOR MAKING CALCIUM CARBIDE
P-3
Cyclone
2700 ft2
To Gas Holdor V
1800 ft2 eae Gas Blower
- Filters (8) 200 hp
Dust
Preheating Zone
-Reaction 2hle
Carbide
Molten Carbide Zone
Reactors (3) 13’ x 13’ x40’ high
-
a -
-
used in starting up. The equipment list and utilities summary tables
are omitted.
Process Discussion
The reactors are so sized that the total volume of the reaction
zone is approximately the same as the reaction zone in a 70,000 kva
furnace. We chose a low hearth depth so that the gas flow would be low
velocity. This helps to reduce the entrainment of coke and lime
particles. Even with such provisions, we believe the coke and lime
must be free from fines.
A possible disadvantage of this process is that the calcium car-
bide cannot be of very high grade, because it contains the ash from the
larger amount of coke used as raw material.
Cost Estimates
The estimated investment and production cost are given In Tables
4.13 and 4.14 respectively. In Table 4.14, the gas is credited at its
fuel value. The gas is 95% CO, with the impurities mainly being H2 and
W2* It can be used as a feed for carbonylatioa, probably with the
removal of the trace of S. In this case, it can be credited at a much
higher value, egg*, at 3.5c/lb, corresponding to $8.5 per million Btu.
From Table 4.15 one sees that, as compared with the conventional,
electrothermal process, the oxythermal process is more economical, when
the CO can be utilieed as a chemical feed, but is less economical when
the gas is usable only as fuel. In the former case, the process can be
considered as one for generation of CO from coke and oxygen, with the
heat of reaction being removed by formation of calcium carbide as a
slag. As one would expect, the cheaper the coke, the more favorable
the oxythermal process. Wote, however, that the oxythermal process
requires more coke than the electrothermal process does, and there is
more likelihood that the lower cost screened coke breeze cannot be used
in the former case than in the latter.
55
Table 4.13
CALCIUM CARBIDE BY OXYTHERMAL PROCESS
CAPITAL INVESTMENT
Plant Capacity: 300 Million lb/yr (136,000 Metric Tons/yr) Calcium Carbide
at 0.90 Stream Factor PEP Cost Index: 360
Battery limits equipment, f.o.b. Reactors Vessels and tanks Exchangers Compressors Separators Miscellaneous equipment
Total Lime kiln Process buildings
.Battery limits equipment installed
Contingency, 25%
BATTERY LIMITS IIWESTMEIVT
Off-sites, installed Cooling tower Inert gas Tankage
Utilities and storage
General service facilities Waste treatment
Total
Contingency, 25%
OFF-SITES IBVESTMEBT
TOTAL FIXED CAPITAL
cost
$ 5,040,000 771,100 45,600 540,000
1,522,800 1,375,800
$9,295,000 5,061,600 4,968,OOO
$40,517,000
10,130,000
$50,647,000
$ 522,300 139,300
16,760,400
$17,421,000
11,588,OOO 2,897,OOO
$31,907,0OU
7,977,ooo
$39,884,000
$90,530,000
Capacity Exponent
up- Down
0.86
0.87
0.88
0.88
0.87
0.82
0.63
0.84
0.77
0.69
56
Table 4.14
,O
CALCIUM CARBIDE BY OXYTHERMAL PROCESS
PRODUCTION COSTS
PEP Cost Index: 360
Variable coete unit Coat Consumption/lb c/lb
Baw material8
Lheetone O.SC/lb 1.854 lb 0.93 coke 3.5cllb 2.2 lb 7.70 Ow4en l.Sc/lb 1.78 lb 2.67
Groee raw materials 11.30
By-products
Fine lime %/lb 4.11 lb 4.55 Fine coke 2c/lb -0.067 lb -0.13 Gas 0.4~/1,000 Btu -13,700 Btu -5.48
Total by-products -6.16
Utilitiee
Cooling water Electricity Inert lo gas, p
Total utilities
unit Coat Coneumption/lb Coneumptionhcg c/lb
5.25c/l,OOO gal 33.9 liters 0.02 3.2clkwh
4.07 gal 0.02 kwh 0.044 kuh 0.06
7*/1,000 rcf 0.184 ecf 10.9 liters 0.01
0.09
57
Table 4.14 (Concluded)
CALCIUMCARBIIE BYORYTRRRML PROCESS
Capacity (nillion lb/yr)* 150 300+ 600
PRODUCTION COSTS
PEP Cost Index: 360
Investmellt '($ million)
Battery lixita Off-sites
Total fixed capital
Sceling exponents
Production coats (c/lb)
Raw materials By-products Utilities
Variable costs
Operating labor, S/shifts, $15.4O/hr Maintenance labor, 3%&r of BL inv Control lab labor, 20% of op labor
Labor costs
Maintenance materials, 3X&r of BL inv Operatiug supplies, 10% of op labor
Total direct costs
Plant overhead, 80% of labor costs Taxes aud insurance, 2%/yr of TX Depreciation, LO%& of TPC
Plant gate coet
GM, sales, research (5% of sales)
Net production cost
ROI before taxes, 25%/yr of TFC
Product value
32.7 50.6 23.4 39.9
56.1 90.5
11.30 . 11.30 11.30 -6.16 -6.16 -6.16 0.09 0.09 0.09
5.23 5.23 5.23
0.72 0.40 0.25 0.65 0.51 0.46 0.14 0.08 0.05
1.51 0.99 0.76
0.65 0.51 0.46 0.07 0.04 0.02
7.46 6.77 6.47
1.21 .0.79 0.61 0.75 0.60 0.55 3.74 3.02 2.76
13.16 11.18 10.39
0.77 0.77 0.77
13.93 11.95 11.16
9.35 7.54 6.90
23.28 19.49 18.06
0.69 0.87
*Of calcium carbide.
+Base case.
SFor baee case only; may be different for other capacities.
58
92.3 73.2
165.5
Table 4.15
CALCIUM CARBIDE PROCESSES
PRODUCTION COST COMPARISONS
Plant (136,000
Capacity: 300 Million lb/yr Metric Tons/yr) Calcium Carbide at 0.90 Stream Factor PEP Cost Index: 360
Electrothermal Oxythermal Process Process
CO credit as Chemical feed Fuel at 3.5&b at $4/million Btu -
Credit (c/lb product) 11.55 5.45
Production cost* (c/lb) 5.37 12.65 13.87
(8.67) (15.95) (14.87)
Product value* (c/lb) 12.05 20.19 17.80
(15.35) (23.49) (18.80)
"Coke at 3.5$/lb; numbers in parentheses are for coke at Se/lb.
59
A Brief Evaluation of a Thermal Process Using CO as a Heating Medium for Making Calcium Carbide
Process Description
We briefly evaluated a thermal process for making calcium carbide
from lime and coke through the use of CO as a heating medium. The
design bases and assumptions are given in Table 4.16. The flow sheet
of the reaction section is given in Figure 4.5. The major equipment
list is omitted, because the sizes of major equipment different from
those in Figure 4.2 and Table 4.5 are given in Figure 4.4. We are also
omitting the utilities summary table.
One of the regenerators is heated by firing a heavy oil, while car-
bon monoxide is heated in another regenerator. These two regenerators
are used in shifts. The hot carbon monoxide gas is carried by blowers,
to three shaft reactors. Each reactor has a hearth depth of 70 ft; a
10 ft melt zone, a 30 ft reaction eone, and a 30 ft preheating sone.
Gas leaves the reactors, passes through the cyclones and filters, and
the blower. Part of the gas goes to the lime kiln, and the balance
returns to the regenerator to be heated for recycling.
Table 4.16
CALCIUM CARBIDE BY THERMAL PROCESS USING CO AS HEATING MEDIUM
DESIGN BASES AND ASSUMPTIONS
References 302405-6
Reactor Shaft kiln; CO as heating medium; coke:lime - 1:1.59; coke and lime larger than 0.25 inch
Regenerator Heavy oil as fuel (0.35 liter/kg 82% carbide)
Other sections same as in Table 4.3.
60
Process Discussion
The bloers must be constructed of a heat-resistant alloy.
Instead of heavy oil, other fuels may be used. Coal is cheaper,
but elaborate facilities must be provided to clean the combustion gas.
Cost Estimates
The estimated capital iuvestment and production cost are given in
Tables 4.17 and 4.18 respectively.
As compared with the conventional electrothermal process, this
process has a lower production cost but practically the same product
value.
61
Table 4.17
CALCIUM CARBIDE BY THERMAL PROCESS USING CO AS HEATING MEDIUM
Plant (136,000
CAPITAL INVESTMENT
Capacity: 300 Million lb/yr Metric Tons/yr) Calcium Carbide at 0.90 Stream Factor PEP Cost Index: 360
Capacity Exuonent
Battery limits equipment, f.o.b.
Vessels and tanks Exchangers Furnaces Cofopreseers Separators Miscellaneous equipment
Total
Lime kiln Reactor Process buildings
Battery limits equipment installed
Contingency, 25%
BATTERY LIMITS INVESTMENT
Off-sites, installed
Cooling touer Inert gas Tankage
Utilities and storage
General service facilities Waste treatment
Total
Contingency, 25%
OFF-SITES INVESTMENT
TOTAL FIXED CAPITAL
cost Down Up
$ 610,200 51,800 568,100 547,200 442,800 827,300
$ 3,047,OOo 0.73 0.65
5,061,600 14,688,OOO 4,968,OOO
$42,706,000
10,677,OOO
$53,383,000 0.90 0.70
$ 266,800 139,300
2,247,500
$ 2,653,OOO 0.88 0.67
9,072,ooo 2,268,OOO
$13,994,000
3,498,OOO
$17,492,000 0.90 0.69
$70,875,000 0.90 0.70
62
Table 4.18
CALCIUM CARBIDE BY THERMAL PROCESS USING CO AS HEATING MEDIUM
PRODUCTION COSTS
PEP Cost Index: 360
Variable costs
Raw materials
Limestone coke coal
Gross raw materials
By-products
Fine lima Fine coke
Total by-products
Utilities
Electricity Fuel oil Inert gas, lo p
Total utilities
unit coot Consumption/lb C/lb
0.5&b 1.854 lb 0.93 3.5C/lb 0.735 lb 2.57 1.5&b 0.0435 lb 0.07
3.57
%/lb %/lb
-0.11 lb -0.2 lb
unit coot Coneumptionl lb Consumption/kg c/lb
3.2cJka 0.179 kwb 0.394 kwh 0.57 $4.0OJmf Btu 5,466 Btu 3,037 liters 2.19 7OcJ1,OOO ecf 0.184 ecf 10.9 liters 0.01
2.77
63
Table 4.18 (Concluded)
CALCIUM CARBIIE BY TEERMAL PROCESS USING CO AS BEATING Ml3DIUM
Capacity (million lbJyr)* 150 300t 600
Investment ($ million)
Battery limits Off-sites
Total fixed capital
Scaling exponents
Production costs (c/lb)
Rew materials By-products Utilities Variable costs a
32.9 53.4 99.7 10.8 17.5 32.5
43.7 70.9 132.2
0.70 0.90
PRODUCTION COSTS
PEP Cost Index: 360
Operating labor, 8Jshift3, $15.4OJbr 0.67 0.36 Maintenance labor, XJyr of BL inv 0.66 0.53 Control lab labor, 20% of op labor 0.13 0.07
Labor costs 1.46 0.96
Maintenance materials, 3XJyr of BL inv 0.66 0.53 Operating supplies, 10% of op labor 0.07 0.04
Total direct costs 7.58 6.92
Plant overhead, 80% of labor costs 1.17 0.77 Taxes and insurauce, 2%/yr of TPC 0.58 0.47 Depreciation, 10XJyr of TPC 2.92 2.36
Plant gate cost 12.25 10.52
G&A, sales, research, (5% of sales) 0.80
Net production cost
ROI before taxes, 25XJyr of TPC
Product value
*Of calciuu carbide.
tBase case.
13.05 11.32
20.33 17.23
SFor base case only; may be different for other capacities.
0.20 0.50 0.04
0.74
0.50 0.02
6.65
0.59 0.44 2.20
9.88
0.80
10.68
5.51
16.19
64
Figure 4.5
REACTORS IN THE THERMAL PROCESS USING CO AS HEATING MEDIUM FOR MAKING CALCIUM CARBIDE
l-201 T-2aQ
Cdco Bin W Limo Bin -001 mgal M-201
bOOtiOUlZOllO.
I =%2- IB
M-2016202 RdOlA,R&C K-301& R&C s-conwpn Ga Blowon
6’x2o’long 12’ dim% hi& 2400 hp aach
- To Ga Holdm and Limo Kiln
To stocls
ri E-301
1600# h h
[ 1 V
Air r+ Hoovy Oil
I
F-2olA6B
2Y-r
3
K-aA&B Air Blowon 23ohpoluh
5 ACETYLENE-FROM CALCIUM CARBIDE
Calcirrm carbide reacts with water readily to forx acetylene, as
shown by the following equation:
CaC2 + 2H20 -ca(OH)p + C2H2
**r - -31.0 kcal/xol (exothermic)
The rate of reaction varies with the particle size, as well as
with the structure of the carbide. Thus, carbide solidified by fast
cooling has a fine crystalline structure, and therefore generates
acetylene more slowly than does slowly cooled carbide, which has large
crystals with definite cleavage planes.
The generators used for comercial production of acetylene from
carbide are of two broad types-wet and dry4iffering in the amount of
water in the generator. Wet generators can be subdivided into batch
or continuous; portable or stationary; low pressure (below 2.5 psig,
usually 10 to 14 in. water), medium pressure (2.5 to 9 pslg), or high
pressure (9 to 22 psig); carbide-to-water or water-to-carbide; and
carbide imxeraion or water displacement. Wet generators are always
used to produce acetylene for use as fuel gas on-site or for coxpres-
sion into cylinders. The larger wet generators are usually carbide-
to-water type. Table 5.1 smmariees patents on acetylene generators.
For producing acetylene on a large scale as a chemical raw mate-
rial, wet generators (continuous, carbide-to-water type) are sometimes
used, but dry generators are preferred. Dry generators can use all
siees of calcimn carbide, including fines. The ratio of water to car-
bide is only about 1.13-1.35 to 1. Part of the water reacts with the
carbide; the balance is evaporated by the heat of reaction, leaving
calcim hydroxide containing about 5% water ("carbide lime").
67
Table 5.1
PATENT SUMMARY
Reference limber Assignee Karlieat Filing Date
302305 Continental Licht u. Apparatbau
Wet, batch, water-to-carbide generator.
8/2/51
302316 UGG 7/7/53
Wet, continuous, carbide to -tar generator; with ocrew feeder slanted upward to enable the generator to be howed la a onertory building.
----- ----I---
302304 BUM AG 11/29/57
Dry, contlmwue, acetylene generator, with screw feeder for CaC2 and raterin p-p for water.
BP-- --- -1-1-m
302309 Texaco 3/U/57
Calcium carblde and mater react in the pPresence of a reridwl oil to generate acetylene; the residual amulrion 161 beated to 90+92oOF ti coked in a fluidlzed bed; the rerultisg coke and lirc ia used in carbide furnace; vapor fra tba cokllgg ir fractionated; *rt of he8vy 0i.l ir recycled to acetylene generator.
302311 Shawinigan Chemical0
Dry, contlnuour generator; horizontal chamber with agitator.
12/13/57
--s-m--- --a---- ------,--I ---mu--
302314 Knapsack-Grierheim 3/14/59
Feeding &vice for a dry, continuour Benerator, with rtorage tank, control tank, aad feeding screw.
-I---------- ---- --- ---s-
302306 Autogen Ehdress M: 10/18/61
Wet, high prerrure, batch, mterto-carbide gaaerator, dth a device to prevent backflowin of 8as to waterpipe.
~~-~-~---------------1-----11-----1--- PI------
302378 Romania Balanta Plant 2114163
Wet, batch generator with a basket filled tith carbide; reaction stops as writer level falls (because of accmulation of gas).
--------------------_1____1___1_1_11___ --s--m --em-
302365 WSSR 4/11/63
Wet generator consirtiqg of horizontal cylinder with rotating drum and screw conveyor for hydrated lima sludge.
--------1---------B- ----------1---------_---- --m--1-----1--
68
Table 5.1 (Continued)
ACRTYLRW8 QM8lWGRS
Reference Rmber
302376
Aaa'ignee
VJIB HeacNeeanfabrik
IIarlieat Piling Data
2/28/64
Wet, generator dth l pacial faediq l yata for cerbide.
302366 USSR
---
10/10/64
Wet, high vreaaure generator, with eddition of kerosene aod an entifoemisg egent. --- -------m
302394 VSB Wachinenfabrik 5/18/65
Wet, high pressure generator dth automatic sludge velre.
--- --
302313 Romeniur Iniatry of Industry 6/15/65
Wet, carbideto-mter generator with egitator; uaea powdered calciu cerbide.
302357 Rmenlm Muletry of Industry
Generator for uairy 2-80 I calcite carbide.
5/25/66
302308 U88R g/9/66
Wet, imaraion type betch generator; with liquid circulation.
---- ----
302325 Air Reduction 8/7/67
Dry gmarator ufth part of acatylena beiq recycled; hydreted lime separated lo cyclone.
--- B-1-1
302374 Rotlmao, 8. l/2/68
Wet, iuraioo typa generator.
302220 Air Rodocta & Chrlcala 8/6/71
Wet generator, uith water recwered from slurry for recycling. -I------
302574 u88R a/29/72
Wet generator dth sludge dieharga control.
Teble 5.1 (Concluded)
llefareuke Umber Aebignee Earliest Filing Data
302360 USSR 12/24/74
tiet gcacrator caniiatig of a ceaa and a pedorated beak&t vlth rdial plates in tha case; IWdlea finely divided carbide.
--- ---- -B-P-
302364 USSR 6/l/76
Wet geoerator with reaction part, dlaplacing dwice, aad rarahi~ device.
302383 USSR 6/21/76
Ganaritu ~oiraiatilyl of a carbide taok, a reactor vaaael, and a cover with a dwice to mdoca leekega.
w------m --------P----I
302396 VEBBWUI 12/7/76
Dry geiiefator, uith 11~ aludgevatar added directly to carbide hoppar and a variable amant of pure unker added to the poatraactioo rooe.
-----------s---m--
302423 Sot. Francaise de 1’Acetylene 12/7/76
Wet immkraioo type generator.
302397 Arnold, A. 6/99/77
Fe(OH)3 sludge fra vltar treatmeot plants and the chemical industry are used in piece of -tar for making acetylene from carbide. The apaot dry (Fa(OB)3 + Ca(OH)2 is tired as a Ximaatoo& aubetitute for pig iroo ercitillg in a bleat furimce.
--I_- 1-1--------1~-- --------I-
302513 (article) : Addition of a little organic eubatance to get smooth acetylene geoaration.
i0
This carbide lime can be used as a fertllieer, as an antiacid in
soil, and for making mortar and cement. It can be calcined and com-
pressed into briquettes, with or without up to 20% coke powder, for
recycle to the carbide furnace to replace part of the lime.
The waste product from a wet generator is a 10 to 20% aqueous
slurry that cannot be discharged directly into sewers because of its
high alkalinity, its high sulfur content, and the presence of traces of
cyanide, and because it would plug the lines by forming calcium car-
bonate. Even the liquid remaining after settling or filtering may be
objectionable for disposal in sewage in some localities. The solids
portion (“carbide sludge”) is wet and weighs 2 to 3 times as much as
the original calcium carbide. Calcined and briquetted it may be used
to replace lime in making calcium carbide. It is also suitable as a
mortar, as a neutralizer for acid waste liquor, as a drilling mud for
oil wells (302477), and for numerous other purposes (B-43, pp.
324-326). Table 5.2 summarizes some recent patents on the use of car-
bide sludge. However, because of its wtness, carbide sludge Is less
convenient to use than the carbide lime produced by the dry generator.
The above considerations on waste disposal are the reason most large
acetylene producers use dry generators.
If all the carbide lime or carbide sludge was brlquetted and re-
cycled to the carbide furnace, fresh lime would not be needed.
However, accumulating impurities from the coke would increase the
electricity consumption and finally make the operation Impossible.
If seawater is used instead of fresh uater in generating acetylene
from calcim carbide, magnesium hydroxide can be recovered from the
sludge (302517).
Acetylene made from calcium carbide is 99 to 99.8% pure (dry
basis); the remaining 0.2 to 1% Is N2, 02, CH4, H2, Ar, CO, and “other
impurities.” The other impurities constitute 0.1 to 0.2X, and consist
mainly of PH3, H2S, divinylsulfide, and vinyl acetylene. Minute quan-
titles of dlvlnylacetylene, mercaptans, acetaldehyde, NIi3, AsH3, buta-
dienylacetylene, diacetylene, and hexadyne may also be present.
7.1
Table 5.2
UTILIZATION OF WASTE STREAMS FROM ACETYLENE GENERATION
Uefareoce Uumber Assignee Earliest Mlisg kte
302099 Columbia-Southern Chemical 7129157
8103~ is raectad uith t&Cl solution in tha Solvay procerr for recovery of Nli3; the lima otberwiaa oaeded for reacting with NlQCl to maka calcium carbide is thus releud. The ramlt is an integrated production of lJn2cO3 and C& fra CaC03, UeCl, l ml coke.
302372 Danki Kagako g/14/77
81&y is palletlsed and lwated with mate gas fro8 carbide furnace and oxygen to form lou density CaCO3, especially useful as daaulfuriratioo accelerator for lolteo pig iron.
302371 Kan8, T. H. g/22/77
Sludge mixad rrith aodium silicate, ati debydratad, used as a coating material.
302244 WB Buna 9120177
Acetylana generated by the dry process is washed with rnter; the vapor deaorbed from tha wah mter is sucked by an iojactor into #ter, which is uaed for uahing.
302395
-m ------1--------e-
VEB Bona 3120178
Sludge uda into graoolar lima fertilirer.
72
The purpose of the purification step is to remove PH3, AsH3, H2S,
and organic sulfur compounds. Such removal is essential regardless of
whether the acetylene is for chemical use or for mlding and other
uses. Durlug the purification, other compounds are also partially
elininated .
Purification is effected by reaction with one of the following:
ferric chloride, cupric chloride, mercuric chloride, chromic acid
(sodium bichromate and sulfuric acid), sulfuric acid, iodine-
hydroiodide, chlorine, or hypochlorite. Table 5.3 summarizes selected
patents on acetylene purification. See also B-43, pp. 334-340.
Table 5.4 lists patents on acetylene-producing processes that
iuvolve calcium carbide, which, homver, is not isolated. These pro-
cesses avoid the formation of carbide liw or carbide sludge. Ionics
has announced a cyclic process using barium carbide (302540). probably
based on the patent identified here as reference 302101. However, in
this and in another process based on barium carbide, calcium carbide
cau be used just as well. Indeed, since it is the carbon that is con-
sumed, not the calcium or barium, the hey issue is the purity of the
carbon. Whether the calcirn is replaced by barium is Irrelevant. One
possible exception is described In reference 302116; the bariux hydrox-
ide in this case is used in sugar rceftniug and therefore is not recy-
cled . The markets for barium hydroxide in sugar manufacture, homver,
are only sufficient to absorb the output from small calcium carbide
operations and certainly are not applicable in the production of
acetyleue as a chemical raw material.
73
Table 5.3
PURIFICATION OF ACETYLENE MADE FROM CARBIDE
Reference mlmber Auignee Barliert Plllng lkte
302569 saint Gohin 8/2/51
Raificat%oa bJr colructiq with eqmour .eolutlon of mdirn chlorite at a pH of 6, uintained by addip acetate l o buffer.
302180 L'Air Liquide 3/14/61
Puriflc~tlon by l ulfuric rid.
302273 Kwpuck s/e/a1
Sprm4 l .Ca(OB)2wter mlurry to mve drut, tlmn mahing with wter, md truting dth cl2 and moa.
302246 Barton, t. l/11/63
,P?p’ “th diu gd Ututatd with tietyleae; rllic8 gel ir r~weuted by dry .
----~- ---_- ~~.
302215 USSR .
But.ia -rdth a bmic ion-excha~e rerin and then ath ECl.
7/20/63
ibaoii Japm a7uen 9/i4/66
Addition of BtOB to u&e liquor coatainisg PeClCuCl2+Cl em&lee it to be rewed.
302214 QBSR 5/11;67
Tkutiq with an 4uwau wlutioon containiv RI 0.3-3X, I 0.1-0.5X, E3P04 O-132.
302037 Wwker-Chede 9/ 28167
Dryiau with rilica gel, with cooling; l ilica gel 18 regenerated by pawi- hot acetylene over it.
302362 lssp S/2/68
Yreatig with an 4wour eolntlon cont8ini~ IVaBr 0.032, l8aQ 52, @SO4 0.2%. ~504 0.002%. ad H2SO4 1Y.
-
a -
.?4
Table 5.3 (Continued)
PIRUFICATION OF ACRTYUNE MADE FROM CARBIDE
-
a -
a
a
PATENTSLIMMRY
Reference Number krignee Rerliaet Filing Bate
302390 OSSR 11/16/70
Treatlag with an aqueous solution containing Fe2(504)3*9H20 7-10x, Hcl 28.5-30.032, and NaI 0.5-1X; PR3 and H2S are removed.
-------m---m -s-----e- -----m a-1-s--1-------
302218 USSR 3/13/72
TreatI% with an aqueous eolutioa containfag CuCl2, BgCl2, and HCl.
-s---v---- -~1~1---11-~----------~-----~
3023Sl USSR S/25/72
Treatlag with H2SO4 (82-963) containing 0.0002-0.002% CuBr2 removes 82s and PIi3. -1-1-- 1-B-1 ------------------________I_-
302380 USSR 9/10/72
Treating with an aqueous eolution containing NaCl 25-35%. Na2Cr204-5X, E2SO4 S-10%, and CuSO4 0.1-0.2X, for removal of Pa3 and H2S.
-------1~-----1-~-~ --------------1-------_-------1-1-1-
302389 USSR 2112174
Treating with an aqueous eolution containing FeCl2 36-40%, CuC12 0.5-0.3X, &Cl2 0.01-0.03X, and HCl 4-5.5X.
302422 Ibiden Engineering 4/21/75
A solution of CuC12, PaCl2, and Fe203 in HCl used for PR3 removal.
1-------------------1-11-1-11---1-1--------------------------------------
302373 Ibiden Engineering 4/21/75
An aqueous solution of CuCl2, FeC12, and FeC13 in HCl used for purification; when the FeCl3 content ir decreased almost to zero, air is blown in to rcgeaerate the FeC13 to 10%.
302421 Nichigo Acetylene Co. 6124175
An aqueous eolution containing (xIC12, FeC13, RCl, and lQCl2 is ueed for removing PH3. The resulting eolution containing PO45 Is treated with chlorine type anion exchange resin to rewve Poqz and reused.
--------------------I___________________-------------------------------------
302420 rn-nd Engineering 9/20/75
Treating with Ca(OH)2 suspended in water to resnove H2S. --------------------________11__1_1_1___-------------------------------------
75
Table 5.3 (Concluded)
PURIFICATIOIoOFACETTLENEMADE FROMCARBIIIE
PATENTSUNHARY
Reference Number
302265
Aaeignee
hewann, 1.
Urlieet Filing Date
11/4/75
Washing with concentrated H2SO4 in two toware to remove H2S, PEG, ~t13, and Ae~3.
--- ---- --
302419 Ibiden Eq#naaring 4/17/76
Treat@ with an equeoue eelution mede from 50% CuCl2 25 pert., 40% FeCl3 6 pert., reduced iron 0.06 parts, EC1 1.5 pert., wetar 1.5 parts; pH3 end 825 are removed.
-
302250
Similar to 302265.
-11-B
Leeemann,E.
---I--
6/3/76
Article 302523
Anion exchange in polyiodide form uead for purification of acetylena.
Article 302598
Bryiag with eeolite.
--e-1_---- ----
76
a
a
Table 5.4
OTHER PROCESSES FOR MAKING ACETYLENE FROM CARBIDE
PATENT SUMMARY
Reference Number A8eignaa
302112 lbkumku Pulp Induetriae
IWO3 (or CaC03) + -B&2 + MO2 (Nl c8tdyM)
EM2 + 2&o----c WOE)? + C282
h(oa)2 + co2-+ lkcoj+ as
A 07clic prucaee.
Emrlieat Piling Ilrte
5/4/53
302103 brrel. P. 6/11/55
Slag (contafnf~ 50x CaO) fra coke reacts with coke & 02 to foa CO and CeC2. Yhe molten ela6 contain5~ CeC2 is diecharged and reacts with star at l@C to form c2*2*
302116 Battietini, 6. 7/6/56
UC2 fra CbO; BaC2 -C#2 + Ba(OH)t; nk(oa)2 used in l tqar manufacture.
302107 TeUCO 6/24/56
Lim and coke dispersed in steam reacts uith 02 at 45OtPP to form liquid CaC2 and a 87ntlmeie Pm; the reection product 18 q-n&ad dth a hjrdrocarbon; the oll-CaC2 l lurr7 is contacted with -tar to foa C2a2; the lime ad oil are separated and recycled.
I--
302101 Ionic8 Inc. 10/26/61
Da0 (or CaO) and natural gas reacts at 15OlPC in a fluidleed bed to form the carbide, uhich reacts uith -tar to form C&; the Re(OQ is dehydrated and racyclad.
302282 Taun, LA. 10/20/75
LlC2 fra CO and LiO, thee C2E2 fra LiC2. --- --
77
Evaluation of a Process for Producing Acetylene from Calcium Carbide
Process Description
The design bases and assumption are- given in Table 5.5. The
flowsheet is given in Figure 5.1 (foldout at end of report). The
compositions of streams marked on Figure 5.1 are tabulated in Table
5.6. The list of major equipment and the utilities summary are given
in Tables 5.7 and 5.8 respectively.
Table 5.5
ACETYLENE FROM CALCIUM CARBIDE
DESIGN BASES AND ASSUMPTIONS
References 302273; 302355; B-43, pp. 314, 341-342.
Generation Griesheim type
Purification Dilute sulfuric acid and sodium hypochlorlte; drying by silica gel
Overall loss 2% of gas
Calcium carbide from the hopper is fed by a screw conveyor to the
inside of a perforated cylinder in a horizontal cylindrical shell.
Water is sprayed onto the perforated cylinder. Acetylene, generated by
the reaction of the water and the calcium carbide, passes upstream
through the screw conveyor to a scrubber column. A water spray in the
column catches most of the entrained solids. The residual lime, and
impurities from the carbide, Is withdrawn by a screw conveyor to lime
sludge receiver T-102. Three such acetylene generators are provided
for a production of 1,000 million lb/yr acetylene.
Acetylene from the generators is cooled to 50°F to condense most
of the water (which may be used as feedwater in the generators). Then
it enters baffled column C-201, where it contacts dilute sulfuric acid.
Here any calcium hydroxide carried out of the scrubber by the gas and
any ammonia that forms from the aluminum nitride in the calcium carbide
78
are neutralized and removed in mete stream 6. The acetylene gas is
further purified by a hypochlorite solution in packed column C-202.
Phosphine and sulfur compounds are oxidized and removed in waste stream
10. Ths hypochlorite solution Is made in column C-203 by bubbling
chlorine Into a trickling dilute caustic soda solution.
The acetylene gas is then chilled to 34OP by refrigeration in
E-201 to remove water. Acetylene thus recovered contains 0.4% water,
and is acceptable for most applications. For VCM production it may be
desirable to further reduce the water to as low as 0.01%. This can be
achieved by adsorption, with silica gel, alumina, or seollte as the
adsorbent. Such an operation is more conveniently carried out in the
VCM plant, because the regeneration of the adsorbent needs high pres-
sure steam, which Is available in the VCM plant but not in an acetylene
plant or a carbide plant.
lo
79
Table 5.6
ACETYLENE FROM CALCIUM CARBIDE
.-,
Cslcirn carbide calcium oxide Othen Water Cslciur hydroxide Acetylene S capounds as H2S Amollis Phosphine Calciu sulfate Ammnium milfate Sulfuric acid Chlorine &dim hypochlorite Sodiu hydroxide Sodium salts
Totals, lbfhr 4th
Totals, lb-molfhr kgrOl/ht
Calciu csrbide Calclue oxide Others Water Calcium hydroxide Acetylene S compounds as R2S Amonia Phosphine Calcium sulfate Ammium sulfate Sulfuric acid Chlorine Sodim hypocblorite Sodium hydroxide Sodium salts
Totals, lbfbr kg/ hr
Totals, lb-mlfhr kE-mol/hr
64.0 56.0 60.0 18.0 74.0 26.0 34.0
* 17.0 34.0 138.0 132.0 98.0 71.0 74.5 40.0 70.0
MO1 wt
Plant capacity: 100 Million lb/yr (45,000 Metric Tons/yr) Acetylene
at 0.90 Stream Factor
Stream Flows (lbfhr) 0" (2) (317 (4) --- o-- (6) (7)
31,532 3,580 2,051
-
--
43,124
--
--
1,960 2,126 42,441
60
- -
-- 10
21,736 70
12,750 44 7 25 -
--
27,500 - -- - - - - MB - - - - -
129 27 103
40,000 -
80 --
Trace 2,160 8,000
- - - -
0 -
37,163 16,857
43,124 19,561
46,607 21,140
34,642 15,713
27,500 12,474
673 305
50,240 22,788
409 186
591 2,396 727 1,701 1,528 25 2,323 268 1,087 330 772 693 11 1,054
Stream Flows (lbfhr)
El (14) EL (10) (11) (I21 (13)
23 10
64.0 56.0 60.0 18.0 74.0 26.0 34.0 17.0 34.0 138.0 132.0 98.0 71.0 74.5 40.0 70.0
-- - -- 3 -- - - -- - --
103 - - - - - 106 48
1 0.55
- me --
24,180 --
20 -
--
-- 17 95 674
24,986 11,333
1,356 615
- -- -- - - 700 - -- - - -- - - -- - - - - 480 - - - 700 -- - -- 480 1,400 218 635
7 56 3 26
9,306 -- -- me
--
--
9,306 4,221
517 235
- -
60 --
12,684 -- -- -- --
12,744 5,781
491 223
-- - 550 -
Trace
-- -- -- -- -- -- -- -- - - 550 249
31 14
%thers are C, hS, SiO2, Ca3P2, Ca2l3, Al2O3, FeSi, Fe203, Al4C3, sic, and Leo.
tOthers are C, SiO2, Al2O3, PeSi, Fe203, SIC, blg(OH)2, et. al.
80
K401
Oewronon uewr
Pleat hpoeitp: 1007~11200 lb/p (45.6m~ttle-IYe) kom.-
et 0.90 uru Poetor
4&T’
K-10164
b NW Imorie2 or coMttueuoe mrbo
Kneton &et~lom #moreton 7 IL 6im. 15 tt t Y Qrboe l teol orieobio Cm, wltil eoolor
oerubhor. oenv tedor. Cod bmkor.
K-101 2-201
T-101 T-102 -103
z: MO)
v-201 v402 v405
c-101 Mel
zt
Keet oxohmmn coolor 10,066 17.w)
210 0.61
1.400 5w 100
Corboe l tool
llmtmr%a106caatrwtiom sboll Tehoo
Cuhoe l tool cerboo rod corbo l teol Corboe l tool
Cuhoe eteol cerbeo at-1 Corbo otool PKP catbmntwl corbm l trl
zoo l tnl Oerboe l tael
lbt l w la flmo.
tmorlel of ooeetreet1on 6h.11 PoebioB
Cnrbmmtnl PIP Lffhd Carbmmtwl SW-9 2S It of 1 lrb Sorl p&t-. carbaammal s- 20 It of 1 irb Sorl prkiq.
1OOLctlom: 4, imtldiy 2 oparmtim2.2 l porri 21 oyrmtiy bbp 2oQ Soctioo: 6,imeldlql6o~~ti~. 3oporoo; Soporetilybhp
81
Table 5.8
ACETYLENE FROM CALCIUM CARBIDE
UTILITIES SUMMARY
Plant Capacity: 100 Million lb/yr (45,000 Metric Tons/yr) Acetylene
at 0.90 Stream Factor
Battery Limits Total
Average consumption
Cooling water (gpm)
Electricity (kwh)
Refrigeration, OOP (tons)
Process water (gpm)
2,650 2,500 150
2,700 2,500 200
1,580 1,500 80
105 85 20
100 Section
200 Section
82
Process Discussion
The generator described is a Griesheim type. Other types, such as
the Shawinigan or Lonza are equally suitable (B-43 pp* 312-317).
For purification, other chemicals such as ferric chloride, chromic
acid, or concentrated sulfuric acid may also be used. The use of hypo-
chlorite may cause the acetylene to be slightly contaminated with
chlorine. Thie is generally not considered to be harmful in most
applications. If the presence of chlorine is harmful, a small amount
of boric acid can be added to T-202 to prevent the reaction of hypo-
chlorite with acetylene.
Our design is for large scale production of acetylene for chemical
use. For producing cylinder acetylene dissolved in acetone, the capac-
ity may be smaller, and wet generators may be used. This is outside
the scope of the present study and therefore not described.
Cost Estimates
The capital investment and production cost are given in Tables 5.9
through 5.12. The carbide price in Table 5.10 was the list price In
early 1981.
83
Table 5.9
ACETYLENE FROM CALCIUM CARBIDE
CAPITAL INVESTMENT
Plant Capacity: 100 Million lb/yr (45,000 Metric Tons/yr) Acetylene
at 0.90 Stream Factor PEP Cost Index: 360
Capacity Exponent
Mttery limits equipment, f.o.b.
Reactors columns Vessels and tanks Exchangers Compressors -Pa
Total
Battery limits equipment installed
Contingency, 25%
BATTERY LIMITS INVESTMENT
Off-sites, installed
Cooling tomr Process water treatment Refrigeration
Utilities and storage
General service facilities Waste treatment
Total
Contingency, 25%
OFF-SITES INVESTMENT
TOTAL FIXED CAPITAL
cost
$ 1,080,OOO 146,200 131,500 105,300 5,400
32,800
$ 1,501,000
7,461,OOO
1,866,OOO
$ 9,327,ooo
547,200 22,500
3,307,300
$ 3,877,OOO
2,268,OOO 567,000
$ 6,712,OOO
1,678,OOO
$ 8,390,OOO
$17,716,000
up Down
0.88 0.82
0.81 0.74
0.88 0.86
0.86 0.83
0.83 0.78
84
Table 5.10
Plant capacity: 100 Million lb/yr (45,000 Metric Tons/yr) Acetylene
at 0.90 Stream Factor PEP Cost Index: 360
Reaction m=m Exponent
Coat J!LE!!?!
Battary lidtr, equipment, f.o.b.
Reactorsi ColUnlU Veraeh and tank0 Bxcbangerr Caprertmrr
Rupm
Total
Battery limits equipment iwtalled
Contingency, 25%
BATrERYLIMITs1NVBs~
$1,080,000 0.95 0.95 61,300 0.77 0.58 79,500 0.61 0.42 93,900 0.95 0.79
13,100 0.46 0.35
$1,327,800 0.92 0.88
$6.645.000 0.85 0.80
1.664,OOO 0.85 0.80
$8,318,000 0.85 0.80
Off-ritea, inmtalled
Cooling toiwr Proceam water treatment Refrigeration Utilitier and 8torage
515,300 0.62 0.44 18,200 0.77 0.77
3.138.800 0.91 0.94 $3,672,000 0.88 0.86
Purif f cation w=-w Exponent
Coot
8 - 84,900 52,000 11,400 5,400 19.700
$ 173,400
$ 807,000
202.000
$1,~9,~
0.57 0.51 0.51 0.45 0.39 0.29 0.65 0.65 0.20 0.14
0.50 0.43
0.40 0.35
0.40 0.35
0.40 0.35
31,900 0.62 0.44 4.300 0.77 0.77
168&M 0.91 0.95 $ 205,000 0.87 0.86
85
Variable Coats
Raw materials
Calcium carbide Sulfuric acid Caustic soda Chlorine
Groee raw materials
Variable Costa
Utilities
Cooling water 'Process water Electricity
Total utilities
Table 5.11
ACETYLENE FROM CALCIUM CARBIDE
PRODUCTION COSTS
PEP Cost Index: 360
unit Coat Consumption/lb
15.5cjlb 4c/ lb 7.5cllb 7.2b/lb
2.907 lb 0.0084 lb 0.0552 lb 0.0377 lb
unit coat Coneumption/lb
5.25~/1,000 gal 12.1 gal 6Oc/l,OOO gal 0.497 gal 3.2clkwh 0.213 kwh
c/lb
45.06 0.03 0.41 0.27
45.77
Conmmption/lrg c/lb
101 liters 0.06 4.14 liters 0.03 0.4! kwh 0.68
0.77
86
Capacity (million lb/yr)
Investment ($ million)
Battery limits Off-sites
Total fixed capital
Scaling exponents
Production coete (c/lb)
Raw materiale Utilities
Variable costs
Operating labor, Z/shift, $15.40 hr Maintenance labor, 3%/yr of BL inv Control lab labor, 20% of op labor
Labor coats
Maintenance materials, 3X/yr of BL inv Operatiug euppliee, 10% of op labor Total direct costs
Plant overhead, 80% of labor costs Taxes and insurance, 2Xjyr of TFC Depreciation, lO%/yr of TPC
Plant gate cost
GbA, sales, research (5% of sales)
Net production coat
ROI before taxes, 25Xlyr of TFC
Product value
*Base csse.
Table 5.11 (Concluded)
ACRTTLRNRFBonCAWIUMCARBIlE
PRODUCTION COST8
PEP Cost Index: 360
50
g
10.3
45.77 0.77
46.54
0.54 0.33 0.11
0.98
0.33 0.06 47.91 0.83 0.41 2.06
51.21
3.40
54.61
5.15
59.76
100*
9.3 8.4
17.7
0.78
45.77 0.77
46.54
0.27 0.28 0.05
0.60
0.28 0.03 47.45 0.52 0.35 1.77
50.09
3.40
53.49
4.42
57.91
22.6 21.5
44.1
0.83
45.77 0.77
46.54
0.09 0.23 0.02
0.34
0.23 0.01 47.12 0.30 0.29 1.47
49.18
3.40
52.58
3.67
56.25
87
Table 5.12
ACETYLENE FROM CALCIUM CARBIDE
DIRECT OPERATING COSTS BY SECTION (Thousand $/yr)
Plant Capacity: 100 Million lb/yr (45,000 Metric Tons/yr) Acetylene
at 0.90 Stream Factor PEP Cost Index: 360
Raw materials
Calcium carbide Sulfuric acid Caustic soda Chlorine
Total by-products
Utilities
Cooling water Process water Electricity
Total utilities
Labor
Operating Maintenance Control laboratory
Total labor
Maintenance materials Operating supplies
Total direct costs
100 Section
45,058
45,058
-
34 414 273
721
60 4 24 6
632 51
200 Section
716 61
135 135 297 33 27 27
459 195
297 33 14 14
46,544 1,024
88
-
Integrated Production of Acetylene from Calcium Carbide Made by Electrothermal Process
For large scale production of acetylene from calcium carbide, it
Is desirable that the operation be integrated. Tables 5.13 and 5.14
give the capital investment and production cost of acetylene for such
an operation. Figure 5.2 gives the production cost and product value
at different levels of operation.
On comparing the costs in Tables 5.14 and 5.12, one sees that
there is no advantage in integration unless the plant is very large
(approaching 300 million lb/yr) . Uowever, this is actually because the
unit price of calcium carbide in Table 5.12 at 15.5c/lb is too low.
This price, which is the present market price of calcium carbide, does
not include an adequate return on investment.
Recycle of Carbide Lime
In an integrated operation, it is only logical to endeavor to use
part of the carbide lime as feed to the electric furnace. The impact
of this practice is analyzed as follovs.
First, facilities would be needed to convert the carbide lime to
calcium oxide. The procedures for treating the carbide slurry from wet
generators are described in reference 302514. For carbide lime from
the dry generators, the procedures are conceivably simpler. The car-
bide lime is first heated in a rotary kiln at 2000°F. Gas from the
electric furnace is burnt with air to supply the heat. Lime from the
kiln is air cooled in a tubular cooler to 350°F. The product is
screened and then passed through a magnetic separator to remove iron
particles. Then the coke is briquetted in extrusion machines and
stored in bins, ready for conveying to the furnace room.
Second, the recycling of carbide lime causes an accumulation of
impurities in the electric furnace, and hence an increase in power con-
sumption. Using a material balance relationship and the known energy
89
Table 5.13
ACETYLENE VIA CALCIUM CARBIDE INTEGRATED PRODUCTION
CAPITAL INVESTMENT
Plant Capacity: 100 Million lb/yr (45,000 Metric Tons/yr) Acetylene
at 0.90 Stream Factor PEP Cost Index: 360
Battery limits equipment, f.o.b.
Reactors Columns Vessels and tanks Exchangers Compressors Special equipment Hiscellaneous equipment Pumps
Total
Lime kiln Electric furnace Process buildings
Battery limits equipment installed
Contingency, 25%
BATTERY LIMITS INVESTMENT
Off-sites, installed
Cooling tower Process water treatment Refrigeration Inert gas Tankage
Utilities and storage
General service facilities Waste treatment
Total
Contingency,'25%
OFF-SITES INVESTMENT
TOTAL FIXED CAPITAL
90
cost
$ 1,080,OOO 146,200 761,900 123,000 64,800
442,800 856,100 32,800
$ 3,508,OOO
5,061,600 5,800,OOO 4,968,OOO
$34,850,000
8,713,OOO
$43,563,000
$ 581,100 22,500
3,307,300 137,100
2,247,500
$ 6,295,OOO
8,229,OOO 2,057,OOO
$16,581,000
4,145,ooo
$20,727,000
$64,289,000
Capacity Exponent
up Dowu
0.79 0.73
0.76 0.62
0.90 0.80
0.83 0.70
0.78 0.64
Table 5.14
ACETYLENE VIA CALCIUM CARBIDE INTEGRATED PRODUCTION
Variable Costs unit Coat
Raw materials
Limestone
coke
Anthracite
Pitch
Tar
Sulfuric acid
Caustic soda
Chlorine
0.5cllb
3.5cilb
Wlb
lOc/lb
8cllb
h/lb
7.5cllb
7.25c/lb
Gross raw materials
PRODUCTION COSTS
PEP Cost Index: 360
Consumption/lb
4.901 lb
1.9437 lb
0.017 lb
0.0073 lb
0.0009 lb
0.0084 lb
0.0552 lb
0.0377 lb
Variable Costs unit Cost Consumption/lb Consumption/kg c/lb
Utilities
Cooling wter Process water Electricity Inert gas, lo p
5.25~/1,000 gal 12.1 gal 6Od1,OOO gal 0.497 gal 3.2c/kwh 4.65 kuh 70~/1,000 scf 0.536 scf
Total utilities
91
c/lb
2.45
6.80
0.07
0.07
0.01
0.03
0.41
0.27
10.11
101 liters 0.06 4.14 liters 0.03 10.2 kuh 14.87 31.7 liters 0.04
15.00
Table 5.14 (Concluded)
ACETTLRNR VIA CALCIUM CARBIDR INTEGRATED PRODUCTION
PRODUCTION COSTS
PEP Cost Index: 360
Capacity (million lb/yr)
Inveetment ($ million)
Battery limits Off-sites
Total fixed capital
Scaling exponents
Production costs (c/lb)
Raw materials Utilities
Variable costs
Operating labor, 23/ehiftt, $15.40 hr Maintenance labor, 3Xlyr of BL iuv Control lab labor, 20% of op labor
Labor costs
Maintenance materials, 3X/yr of BL inv Operating supplies, 10% of op labor
Total direct costs
Plant overhead, 80% of labor costs
Taxes and insurance, 2%/yr of TPC
Depreciation, lO%/yr of TPC
Plant gate cost
G&A, sales, research (5% of sales)
Net production cost
ROI before taxes, 25Xlyr of TFC
Product value
*Base caee.
50 100"
28.4 12.8
41.2
0.64
10.11 10.11 10.11 15.00 15.00 15.00
25.11 25.11 25.11
5.13 3.10 1.17 1.71 1.31 1.00 1.02 0.62 0.23
7.86 5.03 2.40
1.71 1.31 1.00 0.51 0.31 0.12
35.19 31.76 28.63
6.32 4.06 1.96
1.65 1.29 1.01
8.24 6.43 5.06
51.40 43.54 36.66
3.00 3.00 3.00
54.40 46.54 39.66
20.60 16.07 12.65
75.00 62.61 52.31
43.6 20.7
64.3
300
100.3 51.5
151.8
0.78
tFor base case only; may be different for other capscities.
92
115
110
106
100
5%
;
$90 >
b!5 a
$2 &80
i5
g 75
: 0 70 c v
a65 0 E
Iii60 Z
55
50
45
40
Figure 5.2
ACETYLENE FROM CALCIUM CHLORIDE INTEGRATED PRODUCTION EFFECT OF OPERATING LEVEL AND PLANT CAPACITY
ON PRODUCTION COST AND PRODUCT VALUE
-w- Product Value
0.5 0.6 0.7 0.8 0.9 1.0
OPERATING LEVEL, fraction of design capacity 93
balance of the electric furnace under once-through operation (i.e, no
recycling), the following approximate relation is established:
*I = (a + bF) A P I1
I1 + I2
where R is the fraction of carbide lime to be recycled; Ei is the in-
crease of power consumption due to recycling, expressed as percentage
of power consumption in once-through operation; 11 and I2 are the impur-
ities in carbide originating from the coke and the lime respectively; P
is the fraction of Fe and FeSi in the impurities; a is the fraction of
power consumed in a once-through operation due to the sensible heat of
impurities; b is the fraction of power consumed in a once-through
operation due to reaction of impurities; and F is a fraction less than
1, depending on the percentage of oxides and Mg in the recycled
impurities.
In the present design case, using the data in material and energy
balances in Section 4*, we have:
II/(11 + 12) = 0.7
a = 0.02
b = 0.08
P = 0.95 (assumed)
F = 0.3 (assumed)
Hence, we get the following:
R El
l/2 2.9
213 5.9
3/4 8.7
*Hore exact data can be derived from the energy balance in reference 302606, but this is not necessary for the present purpose.
94
Note that the power consumption increases very slightly when
R 50.5, but accelerates with larger increments of recycle.
We adjusted 'the power consumption of the electric furnace accord-
1~ to the above. We then estimated the cost of facilities for treat-
ing the carbide lime, and took into account the decrease in the size of
the kiln seeded for supplying the fresh lime. Table 5.15 sunxaarizes
the cost features for two cases, R - l/2 and R = 2/3.
It is seen from Table 5.15 that recycling up to 2/3 of the lime
causes only a very slight change in the final product value of acet-
ylene. Because of the accelerated power consumption as R approaches 1,
the econamics would suffer at higher R's. While the above is derived
from the specific case of the evaluated design, it is always true that
the effect of recycling on the product value of acetylene can be
depicted as in Figure 5.3. The curve will shift a bit to the right or
left, depending mainly on the quality of coke. If a premium grade coke
is used, the recycle may be resorted to without significant economic
penalty even at R - 3/4. If some means can be devised to reject the
impurities accumulated in the carbide lime (possibly by flotation or
classifying), the recycle can be further increased.
The recycle of carbide lime should be considered more as an
economic my of disposing of the mste (which, in large scale produc-
tion, becomes very important) rather than as an improvement in the
economics of acetylene production.
Integrated Production of Acetylene from Calcium Carbide Made by Oxythermal Process
We showed in Section 4 that calcium carbide by the oxythermal pro-
cess with by-pruduction of carbon monoxide as a chemical feedstuff can
be potentially cheaper than electrothermal calcium carbide. Table 5.16
gives the product value for integrated production of acetylene from oxy-
thermal carbide. If the by-product carbon monoxide can be utilized as
a chemical feed, the acetylene product value can be as low as 42e/lb.
.
95
Table 5.15
EFFECT OF RECYCLE OF CARBIDE LIME TO ELECTROLYTIC FURNACE ON THE COSTS OF ACETYLENE
Recycle Fraction, R 0 l/2 213 ---
Installed cost of relevant items ($1,000)
Lime kiln Air blower Rotary kiln Extrusion machines Conveyors, bin, magnetic separator
Total installed cost
Corresponding battery limits
Corresponding total fixed capital
Changes in production cost, B - 0 as basis ($/lb)
Limestone at 0.5c/lb Fwl Power Maintenance Depreciation, taxes, insurance
Net production cost
ROI
Product value
4,896 127 0 0 0
5,023
8,800
10,600
3,460 3,009 85 67
1,053 1,245 849 1,128 520 650
5,967 6,099
10,500 10,700
12,600 12,900
-1.22 -1.63 -0.28 -0.50 iC.73 +1.27 Ml.10 i8.11 +0.24 M.28
-0.43 -0.47
+0.50
iC.07
iC.58
+0.11
Table 5.16
INTBCRATBD PRODUCTIONOP ACETYLENE FROM CALCIUMCARBIDB NADE BYTRB OXYTRERMAL PROCESS
PRODUCT VALUE
capacity (million lb/yr) 100 300
Product value (c/lb)*
Coke at 3.5c/lb
Coke at 5c/lb
51.8 42.0
55.1 45.3
*@produced CO at 3.5c/lb.
96
Figure 5.3
EFFECT OF RECYCLE OF CARBIDE LIME ON PRODUCT VALUE OF ACETYLENE
97
6 REVIEW OF PROCESSES FOR PRODUCING ACETYLENE FROM HYDROCARBONS
All processes for producing acetylene from hydrocarbons are based
on pyrolysls. They differ only in the means of generating and transfer-
ring the heat for the pyrolysis. Broadly, these processes can be
classified into four groups:
l Partial combustion (i.e ., part of the hydrocarbon is burnt to supply the heat to pyrolyee the remainder.)
l Electric arc.
l Fueled, with the combustion gas not contacting the hydrocarbon to be cracked.
l Fueled, with the combustion gas contacting the hydrocarbon to be cracked and eventually mixing with the cracked gas.
The reactors for these processes differ radically, but the pro-
cesses are more or less similar in the ways of separation, purifica-
tion, and recovery of the components of the cracked gas. Indeed, the
procedures on separation, purification, and recovery described in many
patents are often applicable to various processes. The procedures In
the commercial processes often differ from each other because of the
option selected by the process developer rather than because of the
particular reaction. Therefore, in this section we review all the
processes for making acetylene from hydrocarbons.
Cracking by Partial Oxidation
Table 6.1 lists patents (received at SRI after the issue of PEP
Report 16) on reactors for mating acetylene by partial combustion of
hydrocar bona. The reactor is usually a slender vessel consisting of a
mixing chamber (or a diffuser, if feed hydrocarbon and oxygen have
already been mixed outside of the reactor), a distributor block, a
reactor chamber, and a quenching chamber. The patents under Table 6.lA
deal with the variations on the construction details of the reactor.
Under Table 6.1B are patents dealing with other types of reactors.
These are not used commercially.
99
Table 6.1
REACTORS FOR PRODUCING ACETYLENE BY PARTIAL OXIDATION
PATENT SUMMARY
Baference Bumber Assignee Xarllest Filicg Date
A. ConventIonal Types of Burners
302303 R4SF 8/3/57
Part of the water for quenching is Introduced through atomizing mstles, and part through jets to the main body of gas.
302231 Monsanto 815157 302232 10/g/57
Oxygen is introduced laterally and methane is introduced radially into a co&al mixing dumber; the rixture passes through the channels of a distributor block into a reaction chambsr; water is sprayed from noxrles on a ring along the wall of the reaction chamber; rapid and uniform cooling is achieved.
-- --- ---- -I----
3C2210 Societe Beige 1'Azote 418158
Betweeu a conical mixing chamber and a cylindrical combustion chamber is a distributor block, with passages for the gas mixture; auxiliary oxygen is added through opsnlngs in the block.
302268 Ziwer l/30/60
The distributor block has channels for a methane-oxygen mixture, and a porous plate on the combustion chamber side, with water or air on the other ride of the porous plate; soot formation on the distributor block is reduced.
302207 Diamond Alkali 12/27/63
Ths distributor block has a cooling device on the side facing the combustion chamber.
302209 Xonsanto l/28/66
Oxygen and hydrocarbon are mixed in a chamber and passed through channels of the distributor block; the channels provide a swirling motion.
--------------------_I______------- --a-1-------w-----
302201 Japanese Ceon 7/4/66
Oxygen and hydrocarbon added proportionally. Steam added radially to the combustion chamber.
s-----m- ---------------1------------1_ 1--1-1--1--s-
302158 BASP 7127166
Oxygen and hydrocarbon are mixed in a chsmber and passed through channels in a distributor block, to the reacting chamber.
100
Table 6.1 (Continued)
RMCTGBS FORpBODDCINGACl3TYLg~ BY PARTIALOXIDATION
PATgNTSllMWRY
gaference Nuxber Assignee Earliest Filing Date
a
302036 Monsanto g/25/66
Oxygen and hydrocarbon are xixed in e cone-shaped chamber and passed through channels of a distributor block to the reaction chsxber; auxiliary oxygen is added through other ckannels in the block.
302041 BASF 3125167
Auxiliary oxygen is added to the cabustioa chamber around the circuxference at an augle of 60-800.
302159 MSF 5120167
The burner has a device for xonitoriug ths luxinosity in the reaction chaxber.
I- ---------------
302051 BA8F 7/7/67
Tim upper part of the distributor block is cermic, lined with Cr-Ni steel.
302005 Mmnd Shamrock 7/31/67
Similar to 302207.
302391 USSR l/22/68
The distributor is xade of concentric cylindrical blocks; a vortex form in the annular space between the blocks.
302042 Maxond Shllnrock 11/l/68
Besides auxiliary oxygen, auxiliary gas (recycled purified product gas) Is added through the distributor into the reaction chauber; useful in a process operating under pressure.
-----1-1---1---1-B-- --------------------___1________1___1
302254 BASF 7/10/69
The distributor has 19 channels that are conical at the bottom; auxiliary oxygen is added both through the diffuser, and radially into the reaction chauber.
-----1-11---1------ -------------------____I__________
302075 BA8F 9128170
Sixilar to 302051.
101
Table 6.1 (Continued)
EMCYOBS FOR PRODUCINGACEYYLSNF: BYPABTUL OXIDATTCN
PATRNT SUNNARY
Refermce Number Assignace Barlieet Filing lkte
358160 Degussa 10/27/70
A distributor with concentric holes; hydrocarbon passes through the center hole and aryg8n paseer through the 8~n11h18.
I-- 1--1----- ---m----w--
302370 Po1itechnik8 Wrolswsk8 12/21/72
A p8rforated plate is used a8 the distributor.
302368 Zaklady Asotorre 717173
Quenching 18 provided in the first stage by 8 gas at 16oOC and 12-24 ah, and in the second stage by mater.
B. Othsr Typ88 of Burners
302271 Dr. c. Otto & co. 12/22/59
Eydrocarbon 8nd oxygen enter a regenerative Lone, then an oxidi8ing soa filled with cat8lyst. where tk reaction takes place; the reaction product enters operating regenerative 801~ and leaves the reactor= The flow is reversed periodically.
302227 Toa KagakuKogyo I/8/62
IS’burner consisting of a small reactor chamber follomd by a larger one.
I--I -m----m-----
302276 Hue18 l/8/63
A burner containing mnerous noarle8 for oxygen and hydrocarbon; each nozzle screened fra others by partitions.
-- -m--1--- ---------------- ---1---s
3022’05 BMF 6/i8/65
Hydrocarbon is added through an annular space end oxygen is added through a center pipe provided with an adjustable twist device; different hydrocarbons can be processed in this type of burner.
.302163 L'air Liquide 2/14/66 302164 5123166
Part of the gas product is drawn frcm the core of the flame, and recycled.
102
Table 6.1 (Concluded)
REACTORS FOB PRODUCINGAGETYLENE BY PARTIALOXIDATION
PATgH’f SIlkMARY
Reference Wumber Assignee
302364 I1858
Esrliest Filing hte
7/28/66
he mixing chamber is an annular no88le or toroidal cavities in the critical reaction, and the combustion ch8mber is cone-shape aad is equipped with tmgential tlSlIId8.
302363 U88R 7128166
Similar to above, with a preccmbustion chamber and a conical slotted fire barrier.
302323 BA8F 915166
Hydrocarbon (2C) and oxygen dscaposed in presence of 8 nickel catalyst on alpha-Al203.
------ --111-1 --- ------ ----I_
302324 BA8F 8/2/68
Upstream of the flams is 8 fluidised bed of incabustible solid.
-- - --------_I-
302151 USSR 6/ 5/75
A mixture of hydrocarbop and oxygen and a stream of oxygen are added to a burner with cooling jade t .
-ll-----l_-------l-----l ---e----1- -s---1-
302359 u88R l/4/76
A mixture of hydrocarbon and oxyBen and 8 stream of oxpeen are added through spiral tubes into a burner.
103
Table 6.2 lists patents, received by SRI after the issue of PEP
Report 16, on the partial oxidation processes.
The only partial oxidation process now in commercial use is the
BASF process. Processes once used but now discontinued are that of
Societe Belge 1'Axote and that of Montecatini. These were described in
detail in PEP Report 16. The BASF process is evaluated in Section 7 of
this report.
The submerged flame process Is a special type of partial oxidation
process. This process was developed by BASF and was once used in an
Italian plant. Table 6.3 lists the patents on the submerged combustion
process. The Russians have reported on the submerged combustion af
kerosene, diesel fuel, or vacuum oil to produce acetylene (302462).
Arc Processes Using a Gaseous Feed
Table 6.4 lists.patents, received by SRI after the issue'of PEP
Report 16, on electric arc processes.
In one of the two broad types of electric arc reactors the hydro-
carbon is fed into the arc. In the second type, hydrogen (or other
gas) is fed to the arc to form a plasma, into which the hydrocarbon is
fed.
In Part A of Table 6.4, the ordinary arc reactors are again subdi-
vided Into two types. The first type is, In essence, a slender verti-
cal chamber with a rod.shaped cathode at the top, facing an annular
anode; the hydrocarbon is fed fran the top. The reaction product flows
downward, and is quenched. The Hue18 reactor and the Uu Pont reactor
are of this type. These two reactors differ in the means of stabiliz-
ing the arc: In the 'Huels reactor the arc is stabilized by swirling
the feed gas around the arc. The Uu Pont reactor uses a rotating
magnetic field. The second type of ordinary arc reactor is the
Westinghouse reactor; which operates either on UC or AC current. It
has horizontally oriented annular electrodes, generating a rotating
arc.
104 (Text continues on page 112.)
Table 6.2
-
ACETYLENE BY PARTIAL OXIDATION OR BY CRACKING IN A COMBUSTION GAS
PATENT SUMMARY
Beference Number A8signee Earliest Filing lhte
302274 Montecatini 12131159
Feed and oxygen are saturated with rater vapor and added to a burner operating at lo-20 am.
-- -- ------------
324184 BA8F l/12/62
Feed gas is preheated to 6OoOC; preignition is avoided by maintaining proper velocities.
---- -------------------------1-1-1--------------
302011 Xureha Xagaku 3/U/63
Hydrogen is added to ths fe8d hydrocarbon to make the R:C ratio - 3 to 6; oxygen is added at a 02:C ratio - 1.3 to 1.5; feed is preheated to 500°C; reaction takes place at lOOO-18000C; product has a high C282 content (X02) and a low C2E4 content (<1X); acetylene yield on C - 42-432.
42857 Es80 lks8arch & Engineering 6129164
Yield of C2E2 and C2li4 is increased by adding chlorine to the feed; preheating is not needed.
302208 Phillips Petroleum 6/15/65
Bydrocarbon feed, steam, a fuel, and air are sdded to the resctor. For the recovery feature, see this reference number in Table 6.10.
302002 BASF 4/22/66
Carbon dioxide is added to the feed or oxygen; function of carbon black is reduced.
105
Table 6.3
SUBMERGED COMBUSTION PROCESS
Reference Wumber
302301
Asdgnee Earliert Filing Dnte
11/U/57
Sukargsd cabuotioa reactor, wfth burner, cyclone, ctiewer, and rparator.
324182 12/23/66
Automatic device for flurhisg the space wer the liquid in the reactor with nitrogen to prevent expl~~lon due to 02/vapor Prixture in the spece.
-1-m-
106
Table 6.4
ACETYLENE BY ELECTRIC ARC PROCESS
Reference Wumber Aeeignee Eerlieet Pllin8 Date
A. Elect& Arc Reector
302560 weir, B. w. 3113156
Three DC arcs genereted (three paire of electrodee on e plane), 8ae feed (with eue- pended eolide) added tuylentielly. The arc poeitioo ie controlled magnetically.
-- ---m-------m---
302223 Du Pont 7/19/62
Cathode rod, aed annular anode -11 cooled by water jacket; hydrocarbon (Cii4) vapor feed enter8 radially near the top pert; arc ie rotated by e magnetic field; eupplemen- tary hydrocarbon (propene) injected after the arc cone; quenchiag further beneath. Temperature 2OOW26OoOC in the arc, and 16OOoC at the point of propene injection. Potrer conermption 5.3-7 krrh/lb C2E2; yield to acetylene 70-80X of C.
302270 Ilu Pout
Similar conetruction ae above, with ecraper to remove C depoelt.
12/17/62
m--- m- ---- --------11-1---1-----1--
302173 ml Post l/26/63
C depoeit on enode eurface raored by tllter epray.
302563 Du Pont 8/18/64
A risg etructure on the eurface of the annular anode, end 8 ecreper for remwiug C deporit.
302085 Romanian 2Unletry of Induetry l/20/64
A reectioo chamber between a cathode at top and eo ennular enode at lolmr end.
---I__----- ---------
302259 Ibapeack 12/15/64
AC; rotatable electrode6 to minimiee eroeion; arc edjuetablc.
107
Yeble 6.4 (Continued)
ACBTYLENE BYEIXTRIC ARC PROCESS
PATENT SUMMARY
Reference Number Aeeiguee Earliest Filing Date
302178 Westinghouse 4/6/65
Tw DC arcs eeergieed by the opposing phases of a single AC source; flame from one is elternately cooler than the other and acts es a quench.
302179 Westinghouse 3/16/66
Anmlar shaped electrodes; 8ee through the center; C2li2 yield 52-741 of C, 2.6-9.9 keh/lb.
100316 Diemond Alkali 4/14/66
Hydrogen maps along the ulle of the reactor to provide a sheath around the reactor eone; 65% C2E2 from C, end 4.2-4.3 kuh/lb.
-1 -1-1 ---- ------------11-I
302080 USSR 717167 302257 7/19/67
Met-eheped rotating electrodes dth pert of their surfaces facing eech other; a scraper shaper the outer pert of the surface.
-- ~--~--~--l------~--~l_ll-l---l-ll--~~~-~--~~
302013 Weetinghouee 8/2/67
Rotary arc, annular electrodes; 82, CB4, end N2 as feed; produces C282 and HCN.
302086 oS= g/25/67
Rod cathode, jacketed annular anode, Cii4 added both et top around the anode and radially at the bottca pert of the reaction &ember; quenching water added laterally at center.
313868 Phillips Petroleum 2124169
AC or DC arc, Cli4 feed d&d to arc, Nii3 added after that; product from the reactor cooled in e fluidieed bed; C282 end acrylonitrile are produced.
---m -1-1 -------------- --------1-------1
302071 Westinghouse 10/24/69
&muler electredee opposite each other; rotating arc; 5 kuh/lb.
---m--1------- --------------------_-11-11-1-11-------------------
108
mblc 6.4 (Continued)
ACETYMNE BYEIZCYEICAZ PEOCg88
PAYENYSUMARY
Eefereace Number Assignee Berlieet Filing Bate
302291 Popweki, J.
Bod-shaped vertical electrodes with tipe opposite each othar; between them is the arc ad reaction chmber; feed enters both et top and at bottom, aad whirls around the two electrodee to reect in the reaction chamber, and leaves fra outlets on the circuference.
1. .Plaeme Reactor
302228 Phfllipe Petrols- 10/22/62
Crrked gas from ethane cracking at 15OWF is added to a hydrogen plasma produced by electric arc; the reactor is a horieontal cylinder followed by cylindrical quenching chamber. Oxygen end beat carrier (Al203 particlee, et al.) optionally eddad to the reactor.
302168 Hue18 4128163
A vertical, jacketed anmlar cathode facing a vertical, jacketed annular anode, Ii2 introduced into the arc between them and tiltlad around; CH4/B2 eddd into the bollou center of cethode flon dounuard, through the hydrogen plasma, end leaver the hollow center of the anode to a quenching chamber; volt/current - 8-12, C/E - 6-25.
-- --- -1-1
302084 hapsack 8/S/64
Three AC electrodes at top, B2 added along the electrodes and at the top rim of tbe arc chmber; main part of hydrocarbon feed addad at tbe upper rim of the reaction chamber and a eaall part added at the upper rim of the poet-reaction &ember; a quenchiqg chember folloue the poet-reaction chamber.
---- 1---s----- ------------------------
302083 ltnapeeck 8/U/64
8idlar to abwe, but feed hydrocarbon is added to form a conic flow with downward apex; e recycled cracked gas is added radially at tbe upper rim of the poet-reaction chamber.
-- --~~1-~---~~~--~-~1-1---~~---1-
324936 Shin Meiwa Kogyo 2/23/65
Several hydrogen plaeme arc heetere form an annular or conical flame in a cylindrical reactor; hydrocarbon feed is addad radially near tbe flm.
109
Table 6.4 (Continued)
ACETYLENE BYELECTRIC AW WOCBSS
PATgNT SUMUAgY
Beferenca Number Aeeignee Earlieet Filing Date
324318 Shin Meiwa Kogyo 413/ 65
Verticel rod electrode faces a nozzle electrode, follorred by a reaction chamber with a refractory pipe within it; 82 flovll around the rod electrode, and through the arc ad heats the refractory pipe.
324319 Shin Meiwa Kogyo 4/3/65
Similar to abwe, but no refractory pipe and H2 flovm around the pleeme.
-1-s-- ----------
302166 Phillipe Petroleum 4119165
Borieontel rod cathode facing a horieontal extended annular anode, arc rotating by megnetic field; Ii2 enters et cathode side, and hydrocarbon feed enters radielly to the UC; no quenchfag; C2H2, IiCN, end carbon black produced.
-w---m -s-1_ ---B----1- -------I---
302171 Diamond shamrock 6/6/66
2.5-10 arm, preheated H2 iid Cl&; H:C - 1.7, 26OOOC to llOO°C, 0.25 millieec reaction time, 3.7 kuh/lb.
----- ---- ---------1--1------------~
302061 Zwetani Kogyo 7/21/66
Gas fra arc expended through a nozzle end rapidly cooled; the yield is enhanced. Aleu eae article 302337.
------ --------11--------11-------------------
302025 Crueco, F. l/8/68
,Verticel rod anode facing a cylindrical cathode; ii2 added at upper rim, hydrocarbon feed at lowar rim; quenching stream (recycled hydrocarbon) added in the quenching chambar beneath.
302162 USSR 4112168
liydrocerbon + 0.2-2X 02 to a plaema.
302578 Aeahi chemical 3/11/72
liydrocarbon is introduced through a amall opening, into a plaema at 1200°C in a reactor having an annular anode and a rod cathode, both of graphite.
----a- ---s-- -----1-------1-1--------I-I- ---------
110
Table 6.4 (Concluded)
ACETYLENE BYELWTBIC AE PBOCgSS
PATgNTStlMAgY
lteference Number Assignee Eerlieet Pilieg Date
302131 AGA 10/13/72
Reactant and coolant eddad radially through a noeele form a vortex in a reactor containing a hydrogen plaema.
302382 USSR 11/18/74
Hydrocarbon pyrolyeed in a hydrogen plaeme et 1300-14OoOC for 70-200 millieeconde.
302424 USSR 3/14/75
A cylindricel anode and a rotating rod-like cathode; rotating arc; hydrocarbon feed added to a hydrogen pleeme.
302285 us8R 3/20/75
Hydrogen heated by en electric arc; hydrocarbon dded to tbe plaeae; a rotating arc prwidee further heating; C2H2 yiald, 85% C; 6 kubtlb.
302379 USSR 6/l/76
Pyrolyeie in a plaeme reactor, and quenching unit water vapor jet end water jet.
-- __I-- ------~---------- ----I ---
See also articles 302144, 302332, 302350, 302446, 302450, 302460, 302612-16, 302618-19, 302471, 302480, 302489-93, 302507, 302586-7.
111
The Huels process is still in operation. The Du Pont process has
been shut down. The Westinghouse reactor has never been used on a
large scale, although numerous experiments have been made in 1,000 Icw
and 3,000 kw reactors, with methane, propane, and butane feeds
(302157).
Table 6.4 Part B, lists patents on plasm8 reactors for making acet-
ylene . In a plasma reactor a carrier gas (generally hydrogen) is
heated by an electric arc to form a plasma. The plasm8 proceeds in the
reactor and the hydrocarbon feed is injected into it and is cracked. A
modified Huels process and the Uoechst WLP (Wasserstoff Lichtbogen
Pyrolysis, i.e., hydrogen arc pyrolysis) process are examples.
Knapsack once operated a WLP process (302458, 302472, 302495, 302544).
As compared with an arc reactor, a plasm8 reactor produces far less
carbon deposit, but the electrode has to bear very severe attack by
local. high temperature, and its life would be very limited.
There are two types of arc. One is the “high voltage** arc, with a
voltage/ampere ratio much greater than one (in the Huels arc, it is
6-7); it is distinguished by.a wide gap between the electrodes, and a
long arc. The other type is the “high intensity” arc, with a voltage/
ampere ratio less than 1; it Is a short arc (small gap between elec-
trades). The latter type has the advantage of being able to use either
AC or DC electricity, but suffers the disadvantage of short life of the
electrodes . The former typ8 usually operates on DC. Use of AC in this
type has the difficulty that, at the moment of zero current, the plasma
cools and all charged particles disappear, hence the arc will extln-
qtish unless the voltage is further increased (say, 100 kv or higher),
or a special ignition device is provided, both of these approaches in-
crease the cost. Another device, the use of extremely high frequency
(such as several kilocycle per second), is obviously uot practical be-
cause of high capital requirements. The commercial Hue18 process u8es
a high voltage DC arc. The WLP once used by Uoechst (302458, 302544)
and a Czechoslovakian plant (302547) use8 an AC arc. The bl88ian8 and
Rmanian8 have also developed arc processes for acetylene production
(302478).
112
-
a -
a
a
The use of a epeclal concentric core cathode for producing plaema
fraPa the feedstock ha8 been etudied (302350). There ha8 also been
research on a glow discharge proceae for making acetylene from liquid
or gaseous hydrocarbon8 (302003, 302067, 302486). The glow discharge
is produced at 1,000-4,000 volts under 10-60 mm Eg pressure. The
distinction between an arc discharge and a glow discharge Is discussed
in reference 302588.
The Huels arc process 18 evaluated in Section 8 of this report.
Arc Processes Using Liquid or Solid Feed
Table 6.5 lists patent8 on processes to crack liquid or solid feed
in an electric arc to produce acetylene. Part A of Table 6.5 liete
such processes using an electric arc fn an elongated reactor (302109),
or Westinghouse type (302138) or other epecial shapee. Table 6.5 Part
B, lists processes uelng high frequency high voltage pulsating dis-
charge. The pulsating electricity has the advantage of long-lived
electrodes, but the equipment ie very expensive.
The use of intermittent arca wfthin a liquid hydrocarbon was
invented by Von Ediger. It ha8 been demonstrated but it ha8 not been
commercialized (302300, 302443; E-43, pa 403).
Since the early 19708, the Avco Corporation has been developing a
process for making acetylene from coal by an arc process (302508,
394000, 394002, 416049). A.1 megawatt reactor has been constructed for
testing and develo-nt. Research and development on coal arc pro-
cessas has also been undertaken in Germany, Japan, England, France, and
India (302431, 302436, 302464, 302496, 449734).
Heat by Combined Effect of Electric Discharge and Combustion
Table 6.6 list8 patent8 on processee in which an electric dis-
charge occur8 In a flame formed by combustion. Internorth (Northern
Natural Gae) ha8 done 8ome developppent work along thie line.
113
Table 6.5
ACETYLENE FROM COAL OR LIQUID HYDROCARBON BY ELECTRIC PROCESSES
PATENT SUMMARY
Reference Number Afmignee Barlielrt Filing Date
A. Comentional Arc
302558 Standard Oil Development 12/29/M
Coal dust suspended in CE4 or C2E4, produces acetylene in an electric arc.
--- ---
302300 Technical &met6 Inc. 6117148
Intermittent arc diechargee generated between carbon particleo euspeaded in liquid hydrocarbon, the latter 16 decomposed to form acetylenes.
302559 Weir, Ii. M.
8olid particles (ouch a8 coke or coal) added to an electric arc-
2/28/51
---- ------------I-
302169 Avco Corp. 7/22/63
A vertical rod-lib anode faces a hole in a horixontal-plate cathode; methane and carbon fed to a reaction chamber containing the above-deecrlbed electrodes; the cracked gas partmao doummrd through the hole on the cathode,and is quenched by a coolant.
--- M--B ---------- -----m-1----
302177 UCC 3/24/65
Eeavy oil or kerosene ie aprayed ar a mist into a reactor with Q electrode8 conelrting of a high presmue (So-120 peig) Ug jet directed to a & pool muraintained at nqatlve potential.
a----- -----m ---------------~--11------
302418 Yanagixawa, E. 11/20/65
A hydrocarbon oil Is cracked by an arc generated between electrodes ineerted in 011 containing carbon particlea.
302410 Yanagizawa, E. U/20/65
Three AC electrodes are placed ia a coke bed soaked with kexosene; C2g2 and pitch are prodUCad.
302417 Yanagizawa, E. 317166
Three AC electrode8 are placed in kerosene with a floatirrg carbon layer.
--- ------ ------s--1-
-
0 -
114
Table 6.5 (Continued)
ACRTYLENE FMlM COAL OR LIQUID HIDBOCANON BY BUCTRIC PMCgSSg8
PATg8T SDMMMY
Reference Number krignee IEarliert Filing Date
302238 ugine Ruhlmann 2/7/68
Cracking of hydrocarbon in liquid phaw by a eulnerged electric arc between rtationary electrode6 and movable electroder operating on AC.
302217 BASP l/22/74
Cracking of hydrocarbon by a plurality of arcr burning under the surface of a liquid; C2E2 and carbon black are fozmed.
B-1-w-11 I--- ----1---------_--1111---~-~-
302573 g/13/74
Similar to above, with liquid electrodes.
302138 Wsrtiqghouse 8/11/75
Three AC electrodes ue arranged in a triangular; the electrode8 are hollou and each is rplit into two aectionr, dth a gap for introduction of a gar (CIi4, et al.); coal powder or oil is added through the hollow rpace of the electrode@; the arc rotate6 at 1,000 rpr by the ragnctic field wt up by a coil in the electrodes.
302243 302286
U~egel, G., et al. 12/12/75 213176
A heated hydrogen plasma jet 10 diroctad auto a hydrocarbon ourface; hydrocarbon ie pumped through a ring nozzle at the top of the reactor; the rerulting conic hydrocarbon film l nclouea the plasma jet.
-I_--
302240
----- ------------------------I-
Uertinghouee 719176
Similar to 302138, but the feed coal powder or oil is introduced at the top of the reactor and above the three electrodea; it partwe downward through the arc; the chamber wall flares outuardly to minimise the deposit of soot; golid 1s collected at bottom of the reactor, am well am ia a cyclone beyoml the reactor.
-s-m- -------m--- -------------1---1_____l__l___
302611 Akademie de+ Wireenscbaften der DDS 11/3/78
Moontan YLX in plaemm-pyrolyzed at 100 Tort to get a gas containing 18% C2g2 and 13.5% C2H4-
115
Table 6.5 (Concluded)
ACETYLEBE FRDM COAL OR LIQUID RYDRCCARBOR BY ELHXRIC PROCESSES
PAYRRYSUl48ARY
Reference Ruuber Assignee Earliest Filing Date
B. Pulaatixg Discharge
324313 1-m s-BY0 8/25/64
Pulsating electric discharge between t'(lo electrodes imeraed in carbon particles aoahed uith hydrocarbon; 20-60 kilocycle, 10,000 volts.
302176 1-m ~agyo
Similar to above, except the bed is fluidiaed.
11/6/64
302031 Iwatani& Capany S/18/65
Pulsating electric discharge between two electrodes iureed in a mixture of hydrocarbon and carbon particles.
m-----1-- -I--~-----------------------------
324314 Iwateni k Capauy 9127165
Pulsating electric discharge between two electrodes imeraed in hydrocarbon in a reactor vessel with the bottom lined with iron filings.
Uote : Article 302241 la alao about pulsating discharge, but with a gaseous feed. Refer also to article 302446.
Reference 302170'1n Table 6.8 deals with production of C2H2 fra coal by a thermal proceaa~
116
-.
Table 6.6
.
10
l
I.
ACETYLENE BY COMBINED COMBUSTION AND ELECTRIC DISCHARGE
PATENT SUMMARY
l4eferencel?umber kalgnee garlieat Filing Date
302225 Combustion 6 Ibploaivea gaaearch 6/7/6O
Supulmpoaiqg a high voltege electric discharge on a flaw formed by cmbuation of fuel.
-----
302160 gaao Research 6 gngineering 11/l/65
Applying a single-phaaa high voltege AC on a flam formed by cabuation, with one electrode in tha center of flora, end another aurrotmding it.
302048 Rorthern l&Ural &a 12127168
lhthane or other geaeoua hydrocarbon burnt incapletely with 02, wfth the tempera-
ture aw-ntd b an electric arc; 02lC2I12 - 6.7, cH4/c2tI2 - 7.9.. 4.0 kuh/lb c2n2.
117
Thermal Cracking by a Combustion Gas
In a RTP (high’temperature pyrolysis) process used by Roechst in
the 608, the heat from the combustion of a fuel is used to crack a
hydrocarbon feed in direct contact. The Roechst plant used light hydro-
carbons, but crude oil could also be used (90236, 302442, 302473,
302506). Patents on this process and similar approaches are listed in
Table 6.7.
The Kureha/UCC process In emience la
purpose is to make ethylene, and the feed
distillate. This has been covered in PEP
in Section 10 of this report.
similar, except that the main
ie a crude 011 or a<1050oC
Review 78-l-l. It Is updated
Therma1 Cracking Through Indirect Heat Transfer
Table 6.8 lists patents on producing acetylene by thermal cracEring
through indirect heat transfer, or, in short, thermal craclring, as it
is usually called. The Wulff process, once widely used, belongs to
this category. Patents listed in Part A of Table 6.8 relate to the
Wulf f process, and similar processes using regenerated furnaces; i.e.,
heat for pyrolysis is supplied by contacting the hydrocarbon with hot
solid particles which have previously been heated by combustion of
fuel. Patents listed in Part B relate to other thermal cracking
processes.
The Wulff process was evaluated In PRP Report 16. It is updated
and revised in Section 9 of this report.
Recovery of the Products
Table 6.9 gives the typical composition of the gas from the differ-
ent processes l Note that with the exception that S compounds are
formed when heavy oil is used as feed, and significant amounts of HCN
forms in the coal arc process, the compositions of gas from all pro-
cesses are very slmllar qualitatively. The following discussions are
therefore relevant to the cracked product from all processes.
118
Table 6.7
REACTORS FOR PRODUCING ACETYLENE BY CRACKING IN A COMBUSTION GAS
PATENT SUMMARY
Reference Number Assignee Earliest Filing Date
Eydrogen and oxygen enter tangentially into a cylindrical portion of a vertical reactor, atea is added to the top of a conical portion below the cylindrical part, hydrocarbon la added to the bottom of the conical portion; beneath the conical part is a cylinder lined with ceramic meterial; further beneath is a water spray for quenching, and a gas outlet.
302272 Roechat 8/4/56
Similar to ebove; but foe1 gas and oxygen are introduced radially, and supplementary fuel gas 10 introduced at the top.
302319 Societe Beige l’&ote 2/l/61
Naphtha injected into a flame produced by burning hydrogen and oxygen.
302088 lioechet 6/21/60
Hydrogen aad oxygen are introduced radially into the upper part of the cylindrical portion of a first-stage cmbuation chamber, eteem la added at lower put of the cylinder; beneath the cylindrical portion is a conic portion and a emaller cylindri- cal portion; feed hydrocarbon la introduced at upper part of this emeller cylindrical portion; superheated ateca enters through a ring around the top of the 2nd stage ccnbuetion chamber, which la also cylindrical; below its 2nd stage cambuation chamber is the quenching chamber.
324316 KuraaNN Rayon 10/27/60
The burner has a noaale plate with outer concentric noazlea inclined invardly for fuel gas, and inner nozzles inclined outwardly for oxygen; a cylindrical flame is formed in the combustion chamber, uhlch is separated from the reactor chamber by a throat section; propane as feed la introduced at the throat.
302235 Research Aeaociation of Polymer Baw Materiala
12/6/61
Fuel and oxygen pass through orificea to a combustion chamber (the fuel nozzle la adjustable); a hydrocarbon feed la edded at the bottom part of the combustion chamber.
119
Table 6.7 (Concluded)
REACTORS FOR PRODUCING ACETYLEUE BY CRACKING IN A COHBUSTION GAS
PATgNT SlIMMARY
ReferenceNumber Aeeignee
302222 Megyon Aevanyolaj
Earliest Filing Date
614164
A mixture of hydrocarbons (feed for cracking), fuel gas (e.g., Ii2), and oxygen pnea from a diffueer through a distributor to the combustion &ember.
324315 Kogyo Kaibatau Kenkyueho 7/29/64 324321 g/7/64
Fuel gas (e.g., natural gas) and air are added at top, and auxiliary air aud feed hydrocarbon are added radially; the cracked product is C2Rq (major) and C2R2 (minor).
358899
---I -------I- -------- -we---
Ibreha Kogyo 8124164
A fuel gas and 02 are added at top of a cabuation chamber; the hydrocarbon feed is added near the bottom of the chamber; a quenching water atrean la added laterally.
302161 Chepoe Zavody Chemickeho 10/14/66
Oxygen and a fuel (e.g., Hp) are added at top of a cabuetion chamber; the hydrocarbon feed is added to a subsequent mixing section, then to a jacketed reaction chamber, and a quenching chamber.
----I_ --------------------_---11------1---1------------1--
302579 Ajinomoto 6123168
A mixture of fuel and 02, and a stream of euppl~ntary 02 (together making up 60-90X 02 needed for caplets combustion) are burnt, and diluted to a temperature of 1500-25000C; hydrocarbon feed is then added for cracking.
---- --1----1-11-------1-11-11-11---------------------
302072 Lindetrom, 0. B. 1117169
Hydrocarbon feed in droplets la added to a hydrogen-oxygen flame.
-I--------- ----1-- ------
302142 USSR 3/S/76
Natural gas (ae feed), 02, and an incomplete combustion product of 82 and 02 (obtained by injecting 02 into a centric jet, and A2 through a concentric annular jet into a combustion apace) are delivered to a reaction zone.
-1------------------_---11------1-------------------------------------- -s--s---
120
Table 6.8
ACETYLENE BY THERMAL CRACKING WITH INDIRECT HEAT TRANSFER
PATENT SUMMARY
Bcference Number Aaaignae Earliest Filing Date
A. Ragenerative Furnaces
302057 lAmmua 4129163
Heat in combustion pa fraP a Uulff furnece is used for vaporialng hydrocarbon feed.
100101 mua 4115165
Part of the crude oil in a pipeline la fed to a plant, where it is partially vaporiaed; the vapor is cracked by the Wulff process ; the heavy oil recovered during quenching and purification la recycled to the pipeline.
100832 UCC
Inprwement in the conetruction of a Wulff furnece.
8131165
302012 UCC 317167 302256 9/26/68
Wgenerative furnace, with cooling gea passing through the burner aoaale during the period when no fuel la injected. The life of noaale is increased.
302029 Uaratlum Oil 12129167
Increasing the feed rate and decreasing the steam/feed ratio in a Wulff process maintains a good perforunce.
B--B--- ---~---~~-~~~1-~~~~--1~_---1--------1-----1~-~~~~~
302065 Uarathon Oil 12129169
A Uulff furnece with baffles in tha combustion chamber to reduce local overheating.
302073 Marathon Oil 2/l/71
A Wulff furnace to minimize plugging of conduits.
--m-------1--- --I------------------------__________l_l___
302074 Merathon Oil 9113171
Improvement of the fuel injector in a Wulff proceea.
1-1 ------------ -----------------------1----1----
B. Others.
324157 UOP 6/13/61
Cracking of a hydrocarbon in a fluidiaed bed heated by combustion.
---------------- --------------------I---------------------------------
121
Table 6.8 (Concluded)
ACETYLENE BYT88RMAL C8ACKINGGT8 INDIRBCT PEAT T8AN8FER
PAT8NT8lJMMARY
Reference Number Aseignee 8srliest Filing Date l 302267 Socony Mobil Oil 10/31/67
A thermal cracldng reactor in which a hydrocarbon is preheated, craclced, and cooled by heat transfer through a circular surface.
s--L--- -1-1-----------1------ --11111s- ---------
302170 Coal Industry, Ltd. 3/l/63
A carrier gas (X2 or steam) sweeps through coal heated to 9OoOC; the gas, in a few ulllisecondr, passes through a craching tube externally heated to 1400°C, and then is queuched.
~~~----l_~l~--~---~--~~~_I----I -------------_-------
302165 Vickere-Ziwer 4127163
A reactor dth channels heated electrically.
-- 1----- --e-s- --------------------
302199 =ppel, J., and Kramer, L. 4129164
Pyrolyslo of methane at 145W to 2OlWC, and quenching with a dry, 02-free gas.
302167
Equipment lined with 8iO2IZrO2.
Wechet 10/7/65
302279 Iiappel, J. aud Krauer, L. 11/9/65
Cracking of hydrocarboos (1 to 7C) in presence of hydrogen, at 1600-170C°C and 1 atm.
302202 Solvay
Crachiug of propane, with benzene or stern as diluent.
11/24/66
358230 Mitrui Shipbuildiag 11/29/69
Eydrocarbon crached aver a molten metal bath heated by caabwtion gas.
--s----s- ---------~~~-~~~~~-~_-I-1---1------------
302034 UCC 5/14/73 302136 12113174
A reactor (shaped lihe circular couvex lens) useful for craching various feedstochs in presence of steau.
-- ----------1---------_------------1-1---1--------------------------
122
-
a -
a -
a -
a
Table 6.9
COMPOSITION OF CRACKED GAS FROM VARIOUS PROCESSES
42.3
2.1
b.b
2.2
18.2
0.1
12.b
134
0.1
0.1
1.b
0.3
w.1
1.0
2b.3
3.1
4.7
0.b
7.8
40.1 29.3
1.2 0.b
23.b bl.2
3.3 7.0
8.8 4.0
0.3 0-S
2.2 b.3
a.# 7.0
0.1 0.)
so.1 (2.0)
0.8 (2.7)
0.7 (0.8)
- I
17.0 (33.4)
1.2 (10.2)
7.1 (1.7)
IS.0 (1.2)
0.0 (7.3)
0.9 (2.3) 2.3 (13.3) I
2.b 0.1)
- -
75.3
0.5
0.1
b.1
0.1
1S.b
0.S
74.0
3.6
0.1
1.0
5.2
Il.5
-
a 123
Removal of Carbon Black
To avoid plugging troubles in operations for separating the com-
ponents, it.is necessary first to remove the solid carbon black in the
hot gas stream from the reactor. This is achieved by water scrubbing,
oil scrubbing, cyclone separation, electrostatic separation, filtra-
tion, or moving bed .adsorption. Water scrubbing is effective, but the
heat in the gas cannot be recovered this way. Oil scrubbing can be
accompanied with heat recovery, but there are difficulties in relating
to fouling and emulsion formation. The carbon-rich oil bled from cir-
culation in scrubbing may be disposed of as fuel, or treated to sepa-
rate carbon.
Cyclone separation can remove only part of solid carbon. Electro-
static separation entails problems of clogging and short-circuiting-due
to carbon deposit, and Is thus expensive to operate. Adsorption and
filtration are practical only for treating the presence of small quanti-
ties.
Fluid bed quenching with solid carbon removal at the same time has
been suggested (302154).
Table 6.10, Part A, lists patents relating to the removal of
carbon black.
Removal of Heavier Acetylenes and Higher Hydrocarbons
Methylacetylene, vinylacetylene, diacetylene, and to a lesser ex-
tent, phenylacetylene, divinylacetylene, and trlacetylene are formed as
impurities. A small part of these impurities may be removed during the
011 scrubbing operation for removal of carbon black. Some higher hydro-
carbons, especially the aromatics, may also be partially removed during
the oil scrubbing for removal of carbon black. However, the bulk of
heavier acetylene and higher hydrocarbons (meaning hydrocarbons with 4
C's) often have to be removed by absorption, after the oil scrubbing.
Such absorption may precede another absorption for acetylene; or the
124
(Text continuous on page 137.)
Table 6.10
PURIFICATION AND SEPARATION OF CRACKED CA8
PATENT SUMMARY
a Reference Number Aseignse Iiarliert Filing Date
l
A. Remval of Tar and Carbon Black, and Related Operations
302297 &IS18 7/27/55
cracked 8as- cyclose for rcnoral major part of dust -water rcrubbiug~oil scrubbing (temperature properly controlled In the stages).
302263 1. 0. de Bataafache Petroleum Hsatschappig
0126157
a
Bleck suspension in uter obtained by scrubbing of cracked gas with rater is agitated dth 1.2-1.5 parts oil. Carbon black separated from oil by a screen.
-- ---m-s- 1-1-s
302211 Toy0 Noatsu 12/10/58
Crrbd gas at 140+145oOC is quenched with water to 9OoOC, then cooled indirectly to 320-33oOC by generating stern in cooling coils, with mineral oil flowing over the outside the coils to inhibit the decapositlon of C2D2 catalysed by steel.
--- ---m---
302580 4/15/61
QuencNaq uith an araatic oil.
---mm----- -1-11
302277 MetalIgesellschaft 8/3/62
Generating steam by passing cracked gas through the tubes of boiler at high velocity.
302076 Montecatini 8/31/62
QuencNng by water, tlsa suspension thus fomed is separated in a cyclone to remove tar and carbon black.
a
302081 Knapsack 12/29/62
Crrked PS is -rubbed titha paraffinbase fusloil to remwe soot,withthe circulating oil geseratisg steam; the gas is further cooled by fuel oil, coapressed, chillsd by refrigerant to -6tPC to -80%; and msbed with feed hydrocarbon. (Additional feeturer of the patent in Part B of this table.)
--m--I__ ---------B-I-------------
302077 Societe Belge 1'Asote l/11/63
Scrubbing first by oil and then by highly turbulent water; the 011 recovered In the sacold acrubbiug is partly recycled to the first scrubbing.
125
Table 6.10 (Continued)
PDRIFICATION ADD 88PAlUTION Q C8AClED CA8
PAT8NT S-Y
Paferemce Number Assignee Earliest Filing Ihte
302203 BASF
Naphthaleue used as a scrubbing medium.
2116163
302204 BA8P 1217163
8ara as above, uith saphthalene spray sossle shaped as a hollow cylinder.
302582 317164
Crecked -8 passes through tubes of a quench boiler at greater than 50 k&/sec and tube vmll kept higher than 310°C; deposition of C is preveuted.
302206 Mawd Alkali 1214164
T& gas from the burner (after queschiug in the burner) goes to a primary quenching to-r asd a secondary quenching tower; defoamisg sgeot (polyalkylese emlse), vetting west (rlkylarylsulfonate) aud dispersast (alkali cellulose ether) are added to the water ia pp awuutr; fouling of tomr is prevested.
302183 Chemical Construction Corp. 4/l/65
Scrubbing with heavy arsmatlc 011; the resulting oil is mixed with a light oil; C rswvsd by ceutrifuging, and light oil and heavy oil are separated by distillation asd recycled.
302208 Phillips Petroleum 6115165
The gea is quenched with mter; then an oil stream is added, and cooled indirectly to generate steam; finally it is cooled by a circulating stream of oil.
s-s I---- -------- ---
100526 BASF 9/l/65
8crubbiog by naphthalene, and regenerating the naphthalene by N2 blowing; C recwsred a8 coke.
302050 Kobs Steel 319166
Ges from .thermal cracking under superatmospheric preesure is expasded (energy is wed to compress 02 or air for cracking), cooled in a Wste heat boiler to generate steau, further cooled in an exchanger to evaporate the feed hydrocarbon, and ffually sprayed with mmter to r-e C..
---
Article 302527: Quenching in a fluidised bed.
-11-B-----
-
a -
a -
a
a 126
-
a
Table 6.10 (Continued)
PDRIPICATION ADD SIIPAMTION OP CRACI(BD GM
PATgNTSlDMARY
Reference Number Asrignee Earliest Piliug lhte
100134 4126166
&r from themel cra&iug furuece pmses through an losiring sose, with electricity discharged by electrodes, ose of which is mtted by a uouaqueous carbon fluid.
302009 'Nippon Geou 613167
Queuchieg by traseversely injected rter, ad psriodically cleaning the injection jets with needles.
--- --- -- ----w
302122 Marathon Oil l/4/68
Gas from thermal crachiug furuace is quenched with gas 011, ths carbowladen oil is coked ad fractioaated; the naphtha end gas oil obtained are recyclsd.
m----1--
302239 Monteoatini Mlsos U/7/68
At the top of the serubblng touer em speced rods, that fom films of rcrubbing liquid.
--- -- ----- ------
302571 BASP 4123169
Araatic oil contalniqg uephthalene io wed to scrub ths gas to rsmwe carbon black; pert of tba circulatlsg oil Is evaporated in a vessel containlog petroleu cohe. The vessel im ~wided uith an @tator, and hes protrumioss os its -11.
302054 Doechst 2/18/70
&rubbing by oil folloued by indirect heat transfer to a steam generator.
302066 Merathon Oil 314170
Gas fra thermal crachisg furauce is first scrubbed with oil end then dth wster; cmbustlou gas for heating the regeuerative oven is also scrubbed and the discharged liquid added to the first scrubbing of the crachd gas.
--m--1_
302408 NipponGeou 314171
Ges from thermal cracNqg fursace is scrubbed with oil-water emulsion. I_- --- - -------1-B
302119 Kraer, L., l sd Eappel, J. 2114172
Iajectioa hydrogen or steam hotter thsu 75oOC before quenching; forsation of cohe is reduced.
127
Table 6.10 (Continued)
PDRIPICATIOil AND SEPARATION OF CRACRID GAS
Refer-e Number Assignee Earllemt Piling hte
302120
Similar to 302066.
bhratlum Oil 6/14/72
b. Reuwal of Ei8ber Acetylenea and Eeivier Bydrocarbonm (C greater than 4x
324082 mU6 3/30/!57
Solvent abmorption of diacetylene and itm recovery and recycle to thm reactor. (See alma thim reference mmber in Part D of thir table.)
302299 Knapsack 4123160
Cracked pm im umhed with naphtha in coolerm while being chilled by a refrigerant; It im furthet wamhed wfth naphtha lo a colrrm uith ethylene reflux at thm top and a reboiler at tha bottom; higher acatylenem and higher hydrocarbonm are abeorbed in thm napbtba and recycled.
-- --
302081 Knapmaik 12/29/62
Similar to above. (Other feature of thim patent under A.) '
-- -w-m m-B-
30.2121 Ebechmt 3114170
Crecked gam im rmhed dth ater, thmn with cold CaCl2 molution, ad finally uith circulated cold CaCl2 molution; pert of CaC12 molutfon im continuously reuwed from the cycle; mubmtancem readily polymerfrable are rammed.
302253 Hoechmt 10/5/70
Nmphtba im mtabilised (by rcroviq9 rater and C3 and C4 capoundm) and meparated into light naphtha and heavy naphtha; theme two fractions are added to a mcrubbing tower af different locatiow of the touar; heavy hydrocarbonm (C greater than 4) are remwed from the cracked gam without carryiag light coqonentm fraDl the oaphtha.
I_------
Sea almo 302295, 302069-70, 302247, 302251, 302425 under F.
----
c. E0muv4l of CO2, II& and Ii20
302024 12/U/67
U-oval of Co2 and 82s by abmorption with potammiuP-Nlcthgl-alpha-aminopropionate l olution.
-__I----- --- -------1---------I--
128
l
l
Table 6.10 (Continued)
PDRIFICATIONlNDSNPANATIONOF -DUS
PATBHYSDMARY
Befercnce Rambar kmignae lkrliamt Piling kte
302017 10/27/67
Mater in the pair rmnmd by rcrPbWngdthrsthraol;~thmnolvepor curled war in ttm gem im condenmmd by chilling, rectified to rmmve 1iSht hydrocarbonm, and au-ted by #ter; uater & rthanol are #parated by dirtfllation.
358345 Linda A0 5/10/69
Abmorption of CO2 and H2S by an alkali molution; a rump vemmel at the bottom of thm l bmorption touar raovem any oil in thm aqueoum molutlon; remirr precurmorm are momtly rawed; tha balance of remin precurmorm im rewved in mtripping.
302249 s/3/71
Abeorption of cracked gam by a rixtura of ethanolrlnm and N-mthylpyrrolidone; thm molution im demorbed to mt CO2 and acetylene.
D. 8eparatioa of Acetylene and Ethylene fra 8,. CO, and CtI&
324082 Lumum 3/30/57
8eparation of C2E2, and C2H4 frar ll2, Co, and CR4 by abmorption in naphtha (mea other featurem of thim pmtent under B).
----I___--
302007 M8F 8/31/65 302023 8/12/66 302056 8/U/67 .302060 5/16/68 416047 5/3/71
After bei- waehed to raove CO2 end B2S and being dried by CE3OH (mea patentm under C), the pm im cooled by refrigeration ffrmt to -20%. and thmn to -llO°C; the uncoDdenmed gam im mcrubbed to remove C3+ hydrocarbonm; thim leaver mixture of 82, CO, and CE4; the codenmate during cooling, togethar wfth CJ+ molution, im rectifiad to get C3 end C2 hydrocarbonm (C2H2 + C2E4).
-II_--
302047 Made A0 2/13/67
llultimtwa fractional coPdeumatiun of a 8am conmimtiog of 1-5 C hydrocarbonm and H2, CO, and N2, to recover acetylene.
Sem almu uticle 302463. -- -----_I -1-11-1-1
129
l&b18 6.10 (Continued)
PDRIFICATION AND SEPUATION OF CRACKSD GM
PATENTSIJHMARY
Reference Number Amt3ignede Ikrliaet Filing Date
1. Abmorption of Acetylene by a Solvent from a Gsm Containing CO2
302570 mu8 l/21/64
Succammive abmorption to re!move diacetylene, C3+ capoundm, acetylene (two columnm dth a capremmor before thm mecod one) and ethylene.
302186 lbntecatini S/29/65
Abeorption by N-8ethylpyrrolidine to reject C2H4, CQ2 et al; the absorbed molution im mtrippmd dth C2H2 to recover pure C21I2 am a mide mtreaa, and C$q, Co2 et al. at the top for recycle; the mtripped molution ie again demorbed to get C2Ii2 (for mtripplng) at thm top and higher acetylenes am a ride mtream.
I- --- ---- -----1--m
302182 Dimnond Shamrock 12114166
Treating dth ethanol, before abmorption with methanol for recovery of C284, to remove oil carried over during quenching.
382016 Eoechmt l/30/68 302058 l/16/69
Abmorption of C2B2 by acetone to reject C2H4, et al.; the abmorbed molution, after fhmhiw off a mtrema containi~ C284, im demorbed to recover C282 and CO2, rhich are meparatad by abmorption in dimethylformtide.
302055
-----I_ --- --I__--
Eoechmt S/21/69
Abmorption by dinethylfotide; CO2 and C2H4 are demorbed fra DtQ molution before the final otripplng.
---
Alma 302249 under C.
-- ---I- -----
--m----m ---v--m-
F. Abmor#tion of Acetylene by a Solvent froa a Gmm Containing Little or ISO COP,; ~ncovery
and Separation of Acetylene and Ethylene
302320 Linde*m Eimmamchinen 4/28/55
Vamhing with liquid ethane to remove C2%, ard abmorption of C2H2 by acetone at a taperatura near the liquefaction point of the gas.
130
lkbla 6.10 (Continued)
PAYBmY8lJMARY
l Referencelhmber Ammignee ~rliamt Fill* Dmta
0
324014 Llde AC 10/12/61
Acetone molutfon fra l bmorption of C2E2 and C2H4 ir heated to releame rolla C2~4 and C2E6 for recycle m l bmorption calm, and thmn damorbed in two l uccemmive colmnm to recover C2E4 and C2H2.
3Oi200 Phillfpm Petroleum 10/l/62
Abmorption by dimthylformnida to reject 82, CO, and CE4; tk abmorbmd molution im damorbed to racwar C$l2, C2E4, and C3 pmem: thir mixture im fractionated to gmt C2E2 and C2tI4, which 18 l eparated by l bmorption.
0
302189 Kuramhiki Bayon 4/9/63 302261 4/16/63
AhUtption bY acetone at 2-10 at8 to recwer C2ll2, and at 45 at8 and -30% to recwer ‘?A*
302258 mum l/21/64
Succe8mive abmotptionm to r-e -her acatylenem and retylene. --
51238 UCC 8/6/65
Iepmatfon of C282/C@4 by extraction dimtillation in premmnce of acetune.
302295 Unde'm Eimamchinen 2/l/64
A gam im firmt scrubbed with uthalrol to rmove diacetylene, then mcrubbed with octane to raove C3 capoundm, ard finally, mcrubbed with methanol to rmcwer C2H2.
--- --
324991 Linda AG 3117167
Similar to 302200, but different molvent (e.g.. acetone) and different opmrating coLditionm.
--
302069 BASF 2/21/69 302070 7/7/69
Abmorptlon to get a crude C2Ii2 (76%). which lm chilled and umhed with toluena to r-e 3-4 C hydrocarbunm.
---
131
'l&able 6.10 (Continued)
PDRIFICATION AND SEPADATION OF CDACKED GAS
PATENTSDMMARY
Reference Bkmber Assignee Darliaet Filing Data
416047 s/3/71
C2E2 and C2H4 are coodeneed by chilli~ a cracbed ~a frou &ich 02, 828, and H20 have ken rwed; C$i2 and C2E4 mewrated by rectification.
302252 Linda A6 l/17/72
A gem cQntaln%q C&3 and C2H4 Is cooled to reject C3+ capound?, deep cooled to reject II2 and CD4, and ramhed with DCCF to ruwer C2H2. (The main theme of this patent ii to treat gamem frm an acetylene plant and an ethylene plant. The abwe-rantioned gas containing C2li2 and C2D4 ia obtained by blending gas frou the ethylene plant uith a crude acetylene obtained by DMP-wamhiug of gas 'frao the acetylene pyrolymim reactor.)
-- ---- ------------
302251 AMAB 10/23/72
C& end C& la gm are muccammively abmorbad by solvent at different prammurem.
302387 USSR
Abmorption and mtepdmm demorption to recwer C2E2.
12/18/72
302247 Ehermann, H. 8127174
The gam pmmmem rucce~mively through three abmorberm; the abmorbed molution from each mtage 1m deeorbed In i cole, to get a recycle to the abmorber, end the* stripped in another column to get c2a2, Cg'm + C@l2, and C2H4 rempectipely.
---B-I-B--- -1------------
302425 USSR 4128175
N03 abmorption of higher acatylenem and acetylene in two mtageo.
6. Solvent for Abmorption of Acetylene
302197 BASF S/7/63
Dimtill*tion of part of the circulating solvent fOT Teuwal of polgrers.
--- -- -1------1-----------
302198 BASF 4/6/64
Pouliqo of equipcnt dum to polyumr formation in the solvent ie prevented by adding NaOH to the solvent.
m-m B---1-1- I_-- ---- ---B--B
0
-
a 132
Table 6.10 (Continued)
PDRIFICBION AND WPARATION OP CBACKED GM
PATEm SUMMARY
Neference Nuder Auignee Earliemt Filing Date
302318 10/30/64
8odirPoleylmulfate aqueoum molution dded to &rathylpyrrolidone to prevent polymar depomition.
------- --
302212 Bordan company 3/7/65
Sidlar to 302198, dth medium acetate, l odirn mtaarata, modirn carbonate, et al. am additiva.
324311
lHletiglpiperarina a8 molvent.
8houa lknko 12/g/65
a
302193 BASF 11/6/67 302260 U/10/67
A rall part of the circulating molvent im dimtilled to get a polymer, which im wamhed with xmter to recwer molvent and dimcarded.
---v
302028 lbnranto 10/25/67
Rewval of polymric l ubmtancem in a fouled molvent by addizq high boiling oil (Cl3+) and dimtilling it to recover the oolvent, the bottom product fra dirtillation im wed a8 a fuel.
302064 knapmack
Diwthylphomphine oxide or itm homologumm am molvent.
10/24/69
302248 Kiman, W., et al. 2/11/72
a N-Alkyl-epmilopcaproloctone am molvent.
Ii. Purification of lbcovued Acetylene
302278 Sicedimon So&eta per Asoni S/29/58
HembinS with cone. H2SO4 containing at laut 0.001% Al2(SO4)3.
-- -----
133
Table 6.10 (Continued)
PDRIFICATIONAMD SEPARATION OF CRACKBD GAS
PATENTSoE+uBY
Reference Numbar Ammigpee Barliemt Filing Date
,
302187 Uontecatiui Ediwn 12129163
WamMq tith 98% E2SO4 under pemmure to reduce minute quantitiem of unmaturrted C3+ hydrocarbona to trace quantitier.
------
302294 DSSR 812165
Eigher retylenem ramrod by abwrptlon with alkylwrpholine under premmura.
302216 USSR 812165
Sam am above, but tith an N-mubmtitutad beta-diketone am wlvent.
302190 Ds8R
8a& aa.abwe, hut vlth cyclohexanona am molvent. --
302393 USSR .
Sua am-above, but with vinyl acetate am solvent.
812165
10/14/66
302245 Ku&n, IL, et al. 916167
Acetylene im caprammed in a pump with cold aqueoum liC1 am a meal, and pammed through i l ttippisg column end a drying calm; dry ECl im then ummd in vinyl chloride produc- tion.
302091 BMF
Remidual CO2 in acetylene remwad by uamhing dth diethanolamine.
4/S/71
302361 IJSSR 7128171
Acetylene homologuem in acetylene removed by activated C.
- -m --m----e---
See alw article 302468.
--a--- -------m--
I. Other Pateptm.Ralating to the Recovery Procedurem in an Acetylene Plant
302184 Phllllpm Petrolem 1219163
Cracked #jam fra arc procemm is filtered through a C filter, and pmmmed into an abmorber containisg eta-almina to admorb acetylene, which im dewrbed by pamming hydro8an through the abrorber.
---
134
able 6.10 (Continued)
a
PlRIFICATION ADD 8EpAUTION CF ClUCWD CM
Rmferewelhder Assignee liarliemt Filing Data
324194 Marathon Oil S/3/65
After thm hydrocarbon mm is qumnched, tart-bury1 catechol im added to inhibit thm forsation of a varnish-lib l ubmtanoe.
-
3=576 USSR 1113166
Water fra ecatylene purification im treated dth polyacrylauide and iron malt.
302255 Nmtallgemellmchaft 12/S/68
By-product pm containi~ 82 and Co im converted to CQ in the follouing mtagem: addition of l tea, shifting of CO to CC2 + 82, rmmoval of CC2, l ud wthylation of CC and &to CQ;CHqthncanbt3recyclmd for crwking.
- w--v-
302152 Borden Capany 3/20/75
6am conmimtiqs of H2 and CO im pamrd through a bed of & catalymt to rmmova C2R2, 02, l nd .C2114.
--
302264 i&+1, F. 7126176
C2ll~2 caa bm meparatad fra q by pamsin the mixture through a diverging nossle at l upmrmonic l peed.
---
J. Becwery of Acetylene in gthylene.
302623 Ibnmanto 3/g/56 l
Threm cohmnm (abmorber, abmorbarmtrippar, and demorher) merve to abmorb acetylene fra au ethylene mtraaw
302230 Phlllipm Petrolara 11/26/56
Abmorption by dimthylfotide in a columa uith reflux of liquid ethylene at thm top; thm l bmorbai molutlon lm flamhd, l ud l tripped to recwer acetylene.
--I-
302275 Cik l/31/61
Sepmratlon of acetylene by toluena containing NbClg and tart-BuNII2.
135
Table 6.10 (Concluded)
PIMPICATIONAND SEPAIM'IONOF CMCXIZDCAS
PATDDTSDNDARY
Rmference Nu8ber Ammlgnme Earliemt Filing Date
302052 Metallgeeellecbaft l/31/69
Ethylene ckmtrinin& a emall percentage of acetylene ie treated with acetonitrile under premmure to abmorb all the acetylene, and some ethylene and ethane; theme are all releard by releasing the presmre and etripping with ethane; the gas ie again capreamed ad abmorbed vith acetonitrile; the solution is relearnad in pressure to drive o&f all the ethylene, with mome ethane, and la finally heated or stripped with athane to rwwer acetylene.
302123 7/15/71
Acetylene in an ethylene straQ im recovered by ume of three coluenm: in the firmt coluka operating ptesmure, liquid ethylene is reflused at the top, a molvent for C2E2 (e.g., diubthylforuauide) is added a fev platem fra the top, feed enters at the sidd&, and a.molution of C2E2 vith Borne C2g4 leavea fra the bottou at a reboiler; thim mticiti is cooled, released in presmure, and enterm at the middle of the second calm, shich ham a muall auount of molvent added at the top, and a reboiler at the bottom; all thi ethylene leavem at the top; the bottom solution im stripped in the third coluun to rwwer C2H2.
302133 Lewim, J. D. 11121172
Absorption of C2H2 under imothermal conditionm under excemm reflus of C2g4.
302327 302326
Standard Oil of Ind. S/12/72 2/S/75
Separation of C2lI4 and C2E2 by perueetion through milicone rubber film covered with CuCl-1oB4Cl aqueous solution.
302610 ucc 3128180
Recwery of acetylene fra a gam steau containing ethylene and acetylene by absorp- tion, umisg heat es&angers between the solvent mtremmm and the recycle mtreapl to .reduce energy conmuuption.
See alma article 302331.
136
- .-
-
a
impurities may be absorbed together with acetylene, and subsequently
separated by deeorbing or other separation method.
Table 6.10, Part B, lists patents related to the removal of
heavier acetylenes and higher hydrocarbons.
Removal of 07, H7S, and H70
Table 6.10, Part C, lists patents related to removal of CO2, H2S,
and H20. Carbon dioxide can be removed by washing with a solution of
alkali or a salt of an amino acid or ethanol&nine, or left In the final
by-produced gas, which is H2 + CC + CH4. Hydrogen disulfide, whenever
present, is removed together with CO2 at an early stage of treatment.
Water vapor is often incidentally removed during C2H2 absorption.
However, if C2H2 is to be removed by refrigeration (see below), the
bulk of the H20 must be removed beforehand. This is usually achieved
by a methanol treatment (302017). Other methods for removing water are
adsorption and extraction by diethylene glycol.
Recovery of Acetylene
The comrentional way of recovering acetylene is by a selective
solvent absorption. The solvents which have been studied are water,
acetone, aummia, dimethyl formamide, N-methylpyrrolidone, butyrolac-
tone, hexamethylphoephoramide, tetrahydrofuryl acetate, trimethyl
phosphate, tri-u-propyl phosphate, acetylacetone, l-formyl pyrrolidone,
l-acetyl pyrrolidone, l-fonnyl piperidine, l-acetyl piperldine, dlethyl
oxalate, triac.etylene glycol dimethyl ether, trialkyoxyalkyl phosphate,
dialkyl phoaphites, acetaldehyde, ethanol, cyclohexanone, diethyl
carbouate, methyl ethyl ketone, diethylene glycol and its monomethyl
ether and its monoethyl ether, and glycol ethers (B-43, pa 408, 302511,
324311). Those actually used are water, acetone, ammmia, methanol,
dimethylformamide, and N-methylpyrrolidone.
In the conventional method, the cracked gas has to undergo several
treatments to remove heavier acetylenes and higher hydrocarbons, to
recwer acetylene, and then to separate ethylene. A huge gas volume
137
has to be handled throughout the process. This is a disadvantage,
especially if C2H2-C2H4 content is low. An alternative way advocated
by BASF is to separate C2H2 and C284 from the other components by
refrigeration. This procedure reduces the amount of gas to be handled
at an early stage and would presumably be more economical. But it
entails the hazardous handling of solidified acetylene, and has never
been used in any large scale plant. A Lummus patent advocating the use
of naphtha (presumably a large quantity) to absorb C2H2 and C2H4, thus
separating them from H2, CO, and CH4, which Is a gas to be used as fuel
or to be recycled (324082). This method of separation, however, is not
sharp; the C2H2 and C2H4 thus produced would be of low purity.
Part D of Table 6.10 lists patents relating to the separation of
C2H2 and C2H4 from H2, CO, CH4, et al. by refrigerating as mentioned
before. Part E of Table 6.10 lists patents relating to the solvent ex-
traction of C2H2 from a gas containing CO2. Table 6.10, Part F, lists
patents for similar operations but from a gas with little or no CO2.
Part G of Table 6.10 lists patents relating to solvents used for absorp-
tion of C2H2 and the ways to overcome the fouling of equipment due to
the formation of resin from residual heavier acetylenes accumulated in
the recycling solvent. Heavier acetylenes, especially those with 6 C
atoms, easily polymerize to form troublesome deposits (302062).
Acetylene Purification
Table 6.10, Part H, lists patents relating to the purification of
acetylene
Part
acetylene
to the desired purity of 99.8%+.
I of Table 6.10 lists miscellaneous patents connected with
production.
Acetylene in Ethylene Industry
In a plant producing ethylene by cracking, the cracked gas con-
tains a small amount of acetylene. This acetylene is usually converted
138
to ethylene by a hydrogenation. But it can also be removed and recov-
ered as a by-product. Patents on this topic are sumnarited in Table
6.10, Part J.
In Section 10 of this report, the recovery of acetylene in ethyl-
ene production is described, and its economics evaluated.
139
7 ACETYLENE BY PARTIAL OXIDATION OF HYDROCARBONS
Among the various partial oxidation processes (refer to Section 6
for review of processes) for making acetylene, the BASF process has
been the most widely adopted, and to our best knowledge, all of the
plants now operating on this technology use natural gas as the raw
material. Hence in this section, we evaluate the BA!W process that
uses natural gas= Economics for the same process using naphtha are
also briefly presented for comparison. The other partial oxidation pro-
cesses (SBA, Montecatini, et al.) are believed to have similar econom-
its.
BA!Z's submerged flame process, although not used at present, has
some unique features. They are presented briefly at the end of this
section.
Acetylene from Natural Gas by a Partial Oxidation Process Based on BASF Technology
Process Description
The design bases and assumptions are given in Table 7.1. The flow
sheet is shown in Figure 7.1 (foldout at end of report). The streams
marked on Figure 7.1 are &scribed in Table 7.2. The major equipment
list and utilities sumamy are given in Tables 7.3 and 7.4 respec-
tively.
As acknowledged in Table 7.1, SRI received valuable information
from BASF. The main scheme as described below generally follows the
BMF process. However, the detailed procedures, the compositions of
streams, and sires of equipment were developed by SRI. They represent
neither the BASF operation, nor the BASF license.
141
Oxygen and natural gas, preheated In direct fired heaters H-101
and B-102 respectively to 12OOoF, are charged to the burners. Each
burner consists of a mixing xone at the top, a venturi-shaped diffuser,
a combustion block with numerous channels, a reaction zone, and a
quenching soneD Natural gas and 99% of the oxygen enter the mixing
chamber; 1% of the oxygen enters at a point near the combustion block
to facilitate the combustion. The gas mixture burns and causes part of
the methane to crack to acetylene. The stream leaving the reaction
zone, at 2730-28700F (1500-lSSOoC), is rapidly quenched with water to
170-1800F. Part of the carbon black formed by decomposition of acetyl-
ene during the reaction descends with the water. The gas goes to a
scrubber, where a large stream of water further cools it to lOOoF, and
carries away a major portion of the carbon black. The gas, saturated
with water vapor, and still containing a little carbon black, then
passes to a coke scrubber, where it contacts a bed of wet coke. The
residual carbon black is absorbed by the wet coke. The coke slowly
moves down in the scrubber, and is discharged into a separator, where
it is washed with water to remove the carbon black, and is then carried
by a water stream to the top of the scrubber.
Table 7.1
ACETYLENE BY PARTIAL OXIDATION OF NATURAL GAS
DESIGN BASES AND ASSUMPTIONS
References 4446, 302193, 302260, 302501, 302504; B-43, p. SO; private communications from BASF.
Reaction Preheating to 1200oF, quenching by water to 176oF, gas contains-8% C2H2.
Carbon removal Scrubbing by water, to lOOoF, filtratfon through coke.
Absorption By N-methylpyrrolidone as solvent at 10 atm; higher acetylenes separated by vacuum and steam stripping; solvent partially evaporated to remove accumulated polymers.
142
-
There are six trains of oxygen preheater, natural gas preheater,
burner, water scrubber, and coke scrubber. Water from these burners
and water scrubbers flows to carbon skimmer M-101-a large, covered
shallow tank. Because it has gas attached to it, the carbon black
floats on the surface; it is skimmed and overflows to another carbon
ski-r, M-102. The overflow from M-102 contains 5% carbon black,
which is separated by filtration In M-103. Water from M-101, M-102,
and M-103 is scrubbed by air in C-103 to remove hydrocarbons before
being recycled to the cooling tower. Exhaust air from C-103 is used as
combustion air in H-101, H-102, or the boiler.
The gas from the six trains enters gas holder T-102 and then Is
treated in the recovery section.
The recovery method is essentially an absorption by N-methyl-
pyrrolidone (NMP) under pressure. To avoid fouling in the turbocompres-
sor (see Process Mscussion for the reason for this option), the gas
has to be pretreated before compression. This is done by absorption in
pretreating column C-201 with a chilled stream of NMP. The NMP solu-
tion from C-201 is scrubbed in C-202 by off-gas to remove acetylene,
which is recycled for absorption in C-201. The NMP solution from C-202
is stripped in C-208, to be described later.
The cracked gas from C-201, now reduced in higher acetylenes con-
tent, is compressed in K-201 to 10 atm in three stages. Intercoolers
E-201 and E-202 and cooler E-203 cool the gas and condense the water,
which contains NMP and is combined with other water-NMP streams and
sent to C-206.
The cracked gas at 10 atm is contacted with a chilled stream of
NMP in absorber C-203. Practically all the acetylene and higher acetyl-
enes is absorbed. Gas from C-203 is scrubbed by water in C-204 to
remove NMP. The scrubbed gas has a composition of 61.4% H2, 28.6% CO,
4.6% CHq, 0.3% C2H4, 0.3% 02, 4% CO2, 0.8% N2, and a trace of C2H2. A
small part of the gas is used for stripping in C-202 and for carrying
higher acetylene in K-203 (to be described later). Another part of
scrubbed gas is burnt with air in a turbine which drives compressor
143
K-201. Part of the exhaust gas from the turbine is used as fuel in pre-
heaters H-101 and H-102, and as boiler fuel. Aside from that for
scrubbing and for turbine gas, there Is still a substantial amount of
scrubbed gas which can be used for other processes. gee Figure 7.2 for
the energy b&lance of gas.
In C-203, NMP absorbs practically all the acetylene, all the
higher acetylenes and benzene and its homologues which have not been
absorbed in C-201, and a small amount of carbon dioxide, ethylene, and
carbon monoxide. This NMP solution enters stripper C-205 at 20 psia.
Acetylene gas (from C-206) enters near the bottom of C-205 to serve as
a stripping agent. All the carbon dioxide, ethylene, and carbon monox-
ide, and a small portion of the acetylene, escape at the top of C-205
and return to the inlet of compressor K-201 for recycling. The main
part of the acetylene leaves at an intermediate point in C-205. The
stream leaving C-205 at the bottom is an NMP solution of acetylene,
higher acetylenes, and benzene and its homologues.
This NMP solution from C-205, combined with all the NW-water mix-
tures recovered in the process (from C-201 and C-202, as well as from
C-209, C-211, and V-211, described later), is heated in exchanger E-204
and heater E-205, to 200oF. It is degassed in C-206. Because of the
heat, and because of a gas stream from C-207, acetylene gas is released
from C-206; it goes to C-205 as a stripping agent. Liquid from C-206
flows down to vacuum degasser C-207. Reboiler E-206 heats the bottom
of C-207 to 2400F. Because of the water vapor evolving from the re-
boiler and because of the vacuum, all dissolved compounds (acetylene,
higher acetylenes, and benzene and homologues) vaporize. At a point in
the column where the concentration of higher acetylenes and benzene and
Its homologues is the highest, a vapor stream is withdrawn and sent to
C-208. Ihe vapor from the top of C-207 is compressed and then flows to
C-206 as a stripping agent.
In C-208, which is under a vacuum of 200 lllpl Hg, a NMP solution of
higher acetylenes from C-202 meets the vapor from C-207, which acts as
a stripping agent. The liquid leaving C-208 is NMP, which can be
144
Figure 7.2
ROUTE OF THE BY-PRODUCED GAS
Gar from Process 634.9 million Btu/hr
159 million Btu/hr to Gas Turbine
153.9 million Btu/hr 5.1 million Btu/yr from Turbine used in the Turbine
[ + j+zq 56 million Btu/hr to Boiler
Y-
546.3 million Btu/hr Credit to the Process
4 \
reused for absorption. The vapor from C-208 is scrubbed with hot water
in C-209 to remove IVMP. The water-NMP mixture thus formed is heated
and added to C-206 as described earlier.
The vapor from C-209 is cooled in C-210 by direct contact with
cooling water. The water from C-210 is stripped in C-103 and then
returned to the cooling tower* The vapor from C-210 Is removed by a
V8CUUm pump, diluted by off-gas, and used as fuel.
Acetylene gas from C-205 Is not yet pure enough for making VCM or
VAM, or for many other synthesis uses. It has to be purified. It is
first scrubbed with water to remove NMP and then cooled by refrigerant
at 4OoF in E-209 to reduce the water content. Next it is scrubbed with
sulfuric acid in C-212 and C-213. The acid is CirCUl8ted and main-
tained at about 770F by cooling with refrigerant in E-210 and E-211.
The acid concentration is 72% in C-212 and 94% in C-213. Acetylene
from C-213 is scrubbed by a dilute caustic soda solution (10%) and
cooled by gOF refrigerant to reduce the moisture content. This is the
product.
The analysis of the gas before and after the acid and alkali
treatments is as follows:
Acetylene
Propadlene
Methylacetylene
Vinylacetylene
Butadiene
Pentanes
CO2
N2
Before
98.42%
0.43
0.75
0.05
0.05
0.01
0.10
0.30
After
99.7%
0.017
trace
0
0
0.01
0
0.30
NMP from C-207 is cooled in heat exchanger E-204 and cooler E-207,
chilled in E-208, and recycled for absorption. NMP from vacuum
146
stripping in C-208 and from cleaning of IWP in V-209, and makeup IMP
are added to the cycle.
As IWP circulates in the system, small amounts of Impurities
accumulate. If these are not removed, there is a tendency to form a
crust and to foul the equipment. To overcome this tendency, a small
stream of NMP is periodically withdrawn and evaporated batchwise in
v-209. A little caustic soda is added to n&ralire the trace of
organic acids formed during the natural gas oxidation. The residue
from V-209 is diluted with water and transferred to filter M-201. The
filtrate is transferred to another evaporator, V-211, and evaporated to
a thick residue. The vapor from V-209 Is condensed and recycled to the
NHPtank. The condensed vapor from V-211 is an NW-water mixture; it
is added to other NW-water mixtures for recycling to C-206. The solid
from X-201 and the thick residue from V-211 are incinerated.
147
Table 7.2
ACETYLENE BY PARTIAL OXIDATION OF NATURAL GAS (WITHOUT HEAT RECOVERY)
STEAM FLOWS
Plant capacity: 1OO Million lb/yr (45,000 Metric Tons/yr) Acetylene
at 0.90 strean Factor
Stream Plow (lbk) 2' (1) (2) (3) (4) (5) (6)" AL (8) 0
nethane Etlune Prop ButMe Carbon dioxide OrJrlr- Witrogen, argon Uter wros- Carbon monoxide Acetylene carbon U-tkthylpyrrolidone lkhylene lli&er acetylene0 and SC8 Salwene8udbomoloppes
16.0 45,523 30.0 3,560 44.0 1,452 58.0 263 44.0 1.362 32.0 - 28.0 - 18.0 -
2::: - 26.0 - 12.0 - 99.0 - 28.0 - 50.0 - So.0 -
4,342 - 4,495
- 10.536 611
- 3,405 576 160 4,136
- 6,998 - 46,329 - 12,755
576 - 17 - 65,000 -
10 -
62,659 3,298
10,586 592
3.298 72,248 6.761 44,736 12,760
192 576
518 800 450
Sulfuric ecid 98.0 - - - Sodiu hydroxide 40.0 - - - ---- --- Totala. lb/k 52,160 65,957 120,000 157.283 3,100,OOO 2.970.576 1,162 65,160 90,182
Lg/hr 23,659 29,917 54,431 71,342 1,406,129 1,347,424 527 29,556 40.906
titals, lb-mol/hr 3,032 2,076 6,667 lO.LS7 172,222 165,048 SO 665 6,552 tg-mol/hr 1,375 942 3,024 4,621 78,118 74,864 36 302 2,972
Stream Flown lb/h (ID)
16.0 30.0 44.0 58.0 44.0 32.0 28.0 18.0 2.0 28.0 26.0 12.0 99.0 28.0 50.0 SO.0 98.0 40.0
nethane Ethane Ropam Butane Cabon dioxide QFs- liitro~n, argon Water Wroem Carbon mmoxide Acetylene Carbon H4eth~lpyrrolidone Bthylene Wigher acetylenes and EC8 BellxeaeaudbumoloSaeo Sulfuric acid Sodimbydroxide
Total.. lb/br b/hr
Totala. lbrol/hr b-ml/h+
- - 3,659 - - - - - - - - I - -
1.600
1,500
900 15,350
649,900
6t 300
14
600 6,2W 6,200
12,750
140
300
7,560 Trace
652,400 WfJo
300 300 300 300
8.998 457
1,600 576 2,536 376
5,605 37,617
120
650,000 64,420
150 150
- - - - - - --------- 670,170 651,600 2,900 59,768 5,302 13,804 666,760 8,800 65,296 303.932 295,559 1,315 27,110 2,405 6,261 302,436 3,992 29,618
7,323 6,655 161 4,724 178 531 7,235 374 688 3,322 3,018 73 2,143 81 241 3,282 170 312
148
Table 7.2 (Couchdad)
ACETYLENE BY PARTUL OXlDATlOM OP lWORAL GM (UITIDUT IWT RECOVERY)
STBEAU YLWS
Plaut Capacttyr 100 Nillion lb/ye (45.000 UDtric lkm/yr:) k~tylma
8t 0.90 strmm Pactor
MO1 Strum Flow (lb/br) ut m m (21) (22) (23) (24) (25) (26) (27) (26) (2Wt
16.0 - 30.0 - 44.0 - 58.0 - 44.0 - 32.0 - 2s.o - 18.0 2,000
2.0 - 28.0 - 26.0 - 12.0 - 99.0 - 20.0 - 50.0 - 80.0 - 98.0 - ._ -
40
98
190
:" 1
119 797
552
3
7.200
33 60
- 12,670
S
1,620 -
a - -
- - -
a - -
- - -
- - I
- - -
- - -
500 b,ooo - - - - - - - - - - - - -
- 6,700 - - - - - 30 - - - - - -
sodiu hpdnntda ,&O - - - - - - - - - - - --m-------m
Totah, lbhu w= 40 2.136 2,000 9,000 9,200 1,653 12,738 1,000 4,000 6.730 blhr 907 18 969 907 4,002 4,173 750 5,770 b54 1,814 3.053
Totah. lbrol/Iu 111 0.40 115 111 173 119 1s 491 40 222 6a IueWhr 50 0.1s 52 50 79 54 8 223 1s 101 31
Stnu Plan (lb/W
n8tIuue Itham prom= htaw Carbon dioxide ms- Mitrom, argou U8ter W-w= Carbon mnoai& Acetylam tirbon Hlrthylpyrrolidow Bthylaw Efgbr acmty1anRs amd Rcs hnsena and haologuM Sulfuric acid
-- - -- - -- - -- - -- - -- I
1.~ 10 1,000 -- - -- -
- - - - - - - - - -
:
- - 500 3.210 - - - -
: 2
mm -
6,400
: 9
-- -
- I 280 -- - -- -
tram - - - - 580 - -
-- - - -
-- - - - - -
Sodim bydrorida 40.0 - - 10 - 10 - 350 - - - -m-me----- Totah, lb&r 6,400 1,000 20 1,2Sa 40 2.24s 3,500 500 3.790 350
blat 2,903 45b 9 5Sl 18 1,020 1,588 227 1.721 177
Tomb, lbrol/hr 65 56 0.11 58 1 57 184 28 1u 4 &ml/hr 29 25 0.37 26 0.46 26 83 13 84 2
b-209 l d V-211 oporata htchwir, rata @van lr neragm. %Containlng organho, mu modim hydroxldm u th mlfate.
149
Table 7.5
ACETYLENE BY PARTIAL OXIDATION OF NATURAL GAS (WITHOUT HEAT RECOVERY)
Plant Capacity: 100 Mllion lb/yr (45,OOD metric Tons/yr) Acetylene
at 0.90 stream Factor
K-IOU-I
K-101 K-201 K-202 K-203 K-204
K-205
lhteriel of ColutNction %rrlu Sire
33 ft lg, 2-4 it dim CIrbon steel
Sire (bhp)
350 0
120 120 30 20
HaterhI of cmutruction Shell luum
SiZe matbad {aa PL) @I mdhr)
K-201 K-202 K-203 ~204 K-205 lMD6 K-207 K-208 L-209 g-210
5.300 6.50
x2 4.50
1o:OOo 3.50
20.00 1,500 7.00
900 7.50 4.700 4.40 3,600 6.50
380 .6s 120 .20 120 .20
carbon at-1 t%rbon aeel carbon mteel Carbon steel Carbon l tael carboll l ua1 tarboo l teel
g-211 coolar g-212 Coola K-213 CDoler
120 .20 170 .50
g-214 Condeemet g-215 coddeesar g-216 CoIldeM~r
so 1.50 170 1.10 50 0.10
carbon mtacl carbon ateel
nateria1 of coe~tructios
PuremCC8
oqlcn prdeaterr I&tur*l gu preheater8
II-1olkP 8-102A-F
2.6 l . Carbon ateel 7.2 ct. Carbon steel
usins Off-gm" fuel. OIing 0ff-gar " fuel.
VOl (gal)
T-101 T-102 T-201 T-202 T-203 P204 r-203
30,000 1.900.000
50,wo lO.WO 12,wo 12.000 12.wo
Dilute acid tank
Alkali tmt
carbon ate01 Carbon #tee1 carbon mtwl Albali tank
v-lOlA-P v-201 v-202 v-203 v-204 v-205 V-206 V-207 V-206 v-209 v-210 v-211 v-212 V-213
5,wo . . MO Mu MO 40
E 700 SD
1,wo 900 MO 300 1w
Carbon mteel carbon ateel
Carbon atael carbon steel Carbon rteel carbon l trl carbon ace1 Carboe rtael Carbon atmel
10 hp agitator.
5 bp agitator.
1.50
c-1olA-I c-102A-I c-103 c-201 c-202 c-203 c-204 c-205 c-206 C-207 c-2011 c-209 c-210 *211 c-212 C-213 c-214
n-101 n-102 IHO3 IcZO1
lhbla 7.3 (Concluded)
ACKTTLKSKSTPAKTIALOKIDATIolOFIWUSAX.GAS (WITHOUfRBATRECOVlRY)
scrubkrm colu l crubbmr~ atrippim2 colmm mtrutiy calm Aceylma rtripper Ahaorkr Cnr Scrubbar 9tripp.r Tkermalbpumr vacum dagamar vacuu atripper bt uatar rcrubber Dedw~r Uatmr l crubbnr
Add celun AtidcoluD AlhI eollmm
Mimc*llaluoun lmiment
cmrbm dtimr Qrbm l - Ti1mt liltmr
Plant Cspmcitp, 100 nillion lb&r (45.060 htric lbedyr) ketylem
.t 0.w strum Pactor
might Diwur (to (ft)
36 . . 11.0 26 u 7.0 50 12.0
ii t :8 94 12.0 25 5.0 76 5.5
ii ::t 20 4.0 20 2.5
it 4.0 2.5 :3 4.0
25 ::"o
5U ft dia. 10 ft ht 26 ft dia. 10 ft bt
naterla1 of Conrtnretion Shell Trays
oarboa mu1
stolmwarn st-CL 9tozmwarm tirhl ate*1 Clrbee ate81 carboll wee1 carbon steel carbon *ted
lark00 mtcml 14 valve tr.,.. 12 in. mpaciq&. stouwuc IS ft of 1 in. rim9 pmzking. stmeuare 16 ft of 1 in. riq packin&+ stolumr* 16 fL Of 1 in. rim9 packin6.
lhtarial of Conrtructfon
fhrbml l teel carbmx wad csrkm rtael lArkon et.el
100 l *ctioe - 10. includiq 5 operatim& 5 ‘par”. 275 operatin bhp. 200 mctioe - 37. inchdi~ 19 oparaticiK, 19 295 operatiq bhp. l pare.,
15 ralrt tr.,,. 20 in. apacing.
40 ft of 1 in. riw packing. 40 IL Of 1 in. rim MckiIIP. 30 ft of 1 ill. ril; &Linii. 32 valve trap. 24 in. spacing. 12 sieve trayn. I8 in. BpaCing. 32 valve traym. 16 in. rpaci116. 8 valve traye. 24 in. qmciop. 24 valve tr.,., 24 in. txpaeing.
151
Table 7.4
ACETYLENE BY PARTIAL OXIDATION OF NATURAL GAS (WITHOUT HEAT RECOVERY)
UTILITIES SUMMARY
Plant Capacity: 100 Million lb/yr (45,000 Metric Tons/yr) Acetylene
at 0.90 Stream Factor
Average consumption
Cooling water (gpm)
Refrig. at 60oF (tons)
Refrig. at -O°F (tons)
Refrig. at 40°F (tons)
Process water (gpm)
Electricity (k97j
Steam at 150 psi (lb/hr)
Steam at 50 psi (lb/hr)
Battery Limits Total
9,100 6,800 2,300
540 0 540
42 0 42
91 0 91
6 0 6
1,190 520 670
3,000 0 3,000
16,000 0 16,000
100 Section
200 Section
152
Process Discussion
In the present design, every effort is made to save energy.
Hence, the by-produced gas is used as fuel in a closed-cycle turbine
for driving the compressor. Because of this, a single large centri-
fugal compressor is wed. Such an arrangement necessitates a pretreat-
ment of the cracked gas.
An alternative is to use several electrically driven screw com-
pressors in parallel. In this case, since screw compressors are less
liable to be fouled, the pretreatmsnt can be either after the canpres-
sion or before it.
Instead of the coke filter, an electrostatic filter can be used.
Accordiug to reference 302004, the oxygen usage can be reduced by
recycling part of the by-produced gas to the burners. Wowever, this
may cause preignition and is not recomnended.
l Cost Estimates
The capital investment and production cost are estimated aud given
in Tables 7.5 and 7.6.respectively.
In Table 7.6, the dilute sulfuric acid (stream 35) is not credited
with any value. Thie acid is highly contaminated with organic com-
pounds'and is foul-smelling. It might be useful in a few ways, such as
to replace a part of the comrmercial grade sulfuric acid in superphoe-
phate manufacture.
a
The material usages in Table 7.6 coincide well with data in the
literature (4446, 302504). They are higher than is indicated in some
patents (e.g., 302254). We believe that the data in the patents refer
to small scale experiments rather than plant size operations.
According to BASF, 3 lb ateem per lb acetylene is required in its
plant operation, instead of 1.5 lb/lb as estimated by SRI. This would
increase the production cost by 0.96c/lb acetylene.
153
Table 7.5
ACETYLENE BY PARTIAL OXIDATION OF NATURAL GAS (WITHOUT HEAT RECOVERY)
Plant Capacity: 100 Million lb/yr (45,000 Metric Tons/yr) Acetylene
at 0.90 stream Factor PEP Cost Index: 360
Betury liritr aquipant, f.o.b.
mactou ColuDl Vmmmelm and tukm axchaegea hunaces CapLWW?rm Mireelh- equi~nt mm Total
Lttety liritr l quipent installed
Contimgmcy, 252
MYTmY LRlIYg ImwiTmrn
Off-aite9,iMUllad
cooling tar Proem water treaml!~t stu g4aer~tioo ~frig~r~timl
Dtilitie~ and l toraga
amera wrvice facllitie8 Yaatetrutmmt
Total
thtilyeney. 252
O?P-gITE IuvggTimT
TOTAL PI2gD CAPITII,
Tvul
m--Y Expmeet
-A comt E!E
6 518.4W 1,726,OOO 1.074.8Do 524,300
1,302.500 3.745.800 135,700 217.900
( 9,245.DDu 0.73 0.w
$3&279,WO
9.570.000
$47,049.WO 0.71 0.61
1,188,9DO 2,500
41)9*wo 469.100
$ 2.150,OW 0.84 0.72
0,086,WD 2.021.OOD
$12,257,0QO
3.064.OW
$15,322,0OD 0.74 0.64
$63,17O,WO 0.72 0.62
Keactiml capacity Bxpoeent
-ALL- coat -
$ 518.4W 976,600 fl53.5w
1.302.500 72,000 133,ZW 91.400
s 3,947.6w
$15,024.DW
3.756.OW
$18,78O,OOD
0.60 0.60 0.94 0.91 0.71 0.70 - -
0.95 0.95 0.60 0.60 0.60 0.60 0.80 0.64
0.84 0.81
0.87 0.75
0.87 0.75 --
0.87 0.75
908.900 0.90 0.68 280,WO 0.90 0.68 - - - 2.500 0.75 0.80 - - - 489.000 0.82 0.82 - - - 469.100 0.70 0.70
$ 909,uml 0.90 0.68 $ 1.241,WD 0.79 0.74
KOCOVery capacity Bxpcmmt
-a Coat E!E
g --- 749,400 0.77 0.63 221.300 0.56 0.42
524JOD 0.77 0.59 - - -
3.673.800 0.60 0.60 2.500 0.60 0.60
126.500 0.61 0.42
$ 5,297.wll 0.64 0.59
$23.255.DDO 0.58 0.53
5.814.OOD 0.58 0.53
$29,069,0W 0.58 0.53
154
Table 7.6
ACETYLENE BY PARTIAL OXIDATION OF NATURAL GAS (WITHOUT HEAT RECOVERY)
l Variable coats
Raw materiale
Natural gas Oxygen (95%) N-Methylpyrrolidone coke Caustic soda (50%) Sulfuric acid
Gross raw materials
By-product6
Gas Carbon BTX
Total by-products
Utilitiee
Cooling water Steam Process water Electricity
Total utilities
PRODUCTION COSTS
PEP Cost Index: 360
Unit Cort Coneumption/lb c/lb
9.48c/lb 4.1 lb 38.87 l.lc/lb 5.14 lb 5.65 Ql.lO/lb 0.00314 lb 0.35 k/lb 0.015 lb 0.06 6.5c/lb 0.057 lb 0.37 4.5c/lb 0.13 lb 0.58
45.88
$4.OO/MM Btu -0.043 EM Btu -17.20 0.4c/lb -0.03 lb -0.01 12c/lb -0.03 lb -0.36
-17.57
Unit Coot Consumption/lb Comumptiodlq c/lb
5.25$/1,000 gal 45.5 gal 380 liters 0.24 $6.40/1,000 lb 1.5 lb 1.5 kg 0.96 6Oc/l,OOO gal 0.028 gal 0.237 liters m3l 3.24c/kwh 0.093 kwh 0.206 kwh 0.30
1.50
155
Table 7.6 (Concluded)
ACETYLENE BY PARTIAL OXIDATION OF NATURAL CAS (WITHOUT flgAT DIZCOVEBY)
PRODUCTION COSTS
PEP Cost Index: 360
Capacity (million lb/yr)*
Inveetment ($ million) Battery limits Off-sites
Total fixed capital Scaling exponents
Productions costs (c/lb) l&w materials By-products Utilities
Variable costs
Operating labor, S/shifts, $15.40/hr Maintenance labor, 3X/yr of BL iuv Control lab labor, 20% of op labor
Labor costs
Maintenance materials, 3X& of Bl inv Operating supplies, 10% of op labor
Total direct costs
Plant overhead, 80% of labor costs Taxes and insurance, 2Xlyr of TPC Depreciation, 10%&r of TPC
Plant gate cost
G&A, sales, research (5% of sales)
Net production cost
ROI before taxes, 25Xlyx of TPC
Product value
*Of acetylene.
base case.
50 lOOf 300
31.2 47.8 9.9 15.4
41.1 63.2 0.62 0.72
104.2 34.5
138.7
45.88 45.88 45.88 -17.57 -17.57 -17.57 1.50 1.50 1.50
29.81 29.81 29.81
1.89 1.08 0.45 1.87 1.44 1.04 0.38 0.22 0.09
4.14 2.74 1.58
1.87 1.44 1.04 0.19 0.11 0.04
36.01 34.10 32.47
3.32 2.19 1.27 1.64 1.26 0.92 8.22 6.32 4.62
49.19 43.87 39.28
3.00 3.00 3.00
52.19 46.87 42.28
20.55 15.80 11.56
72.74 62.67 53.84
SFor base case only; may be different for other capacities.
156
Ae said before, the compressor can be motor driven instead of gas
driven. It can aleo be steam driven. This explains the discrepancy
between the utilities usages given in Table 7.6 and those reported in
some of the literature (4446, 302504).
Figure 7.3 gives the production cost and product value at
different levels of operation.
157
lQ5
95
Figure 7.3
ACETYLENE BY PARTIAL OXIDATION OF NATURAL GAS EFFECT OF OPERATING LEVEL AND PLANT CAPACITY
ON PRODUCTION COST AND PRODUCT VALUE
I \ I I
- Production Cost -- Product Value I
- Production Cost --- Product Value
Million Ib/yr
0.5 0.6 0.7 0.8
OPERATING LEVEL, fraction of design capacity
0.9
158
Variation of the Preceding Process with Recovery of Heat
Process Description
In the above-evaluated process, the heat taken up by water in
quenching is lost. BASF has several patents describing the use of
naphthalene for quenching, with recovery of heat for steam generation
(100526, 302203-4, 302580, 302582). This was once practiced by RAW.
In recent years, BASF has shifted to the use of a heavy aromatic
residual oil as a quenching medium. The following is our evaluation of
such a process. Figure 7.4 is the flow sheet of the reaction section.
(The recovery section is the same as that in Figure 7.1.) Table 7.7
gives the composition of the stream6 marked in Figure 7.4. Table 7.8
lists the major equipment of the reaction section. Table 7.9 gives the
utilities of that section.
Referring to Figure 7.4, the gas in the burner is quenched rapidly
to 480oF (25OW) by a circulating stream of oil. The gas, carrying oil
as well as its decomposition products, goes to the bottom of a high
quenching column, C-101, and rises therein. From this column, an oil
stream from the bottom passe6 through waste heat boiler E-102 and re-
turns to the reactor- In the middle of the columns are two circulating
streams, one passing through waste heat boiler E-103, and the other
through E-104 to heat water for feeding the boilers. In this way, the
heat in the gas is recovered. Three stream6 are added to the column:
residual oil is added to the bottom, a stream of multinuclear aromatic
compounds (stream 10) is added to the middle, and a BTX stream is added
to the top. The last stream serves to prevent multinuclear aromatic
compounds from leaving the column with the gas.
In the circulating 011 stream at the bottom of the column, carbon
is accumulated to a 25% concentration. To prevent further accumulation
of carbon , part of the oil is withdrawn, passed into cyclone M-101 to
separate big particles of coke, and then treated in oil column C-102.
In C-102, heater E-105 heats the oil circulating at the bottom. Multi-
nuclear aromatic compound6 leave at the middle and go to the middle of
c-101. BTX evolve6 at the top, condenses in E-106, and is recovered.
159
Table 7.7
ACETYLENE BY PARTIAL OXIDATION OF NATURAL GAS (WITH HEAT RECOVERY)
STREAM FLOWS
Plant Capacity: 100 Million lb/yr (45,000 Metric Tons/yr) Acetylene
at 0.90 Stream Factor
Residual oil Multinuclear aromatics Benzene-toluene-xylenes Carbon Water
Totals, lb/hr kg/hr
Totals, lb-mol/hr kg-mol/hr
gesidual oil Multinuclear aromatics Benrene-toluene-xylenes Carbon Water
Totals, lb/hr Whr
Totals, lb-mol/hr kg-mol/hr
Mol wt
300.0 150.0 92.0 12.0 18.0
MO1 wt
300.0 150.0 92.0 12.0 18.0
Stream Flows (lb/hr) (1) (2)* (3) (4)* (5)
3,806
--
9,366 -- -
3,122
3,806 1,726
13 6
12,488 5,664
291 132
624
1,624 738
62 25
4,683
3,122
- --
12,300
7,805 3,540
276 125
12,300 5,579
134 61
(6) Stream Flows (lb/hr) (7) (8) (9) (10)
-- --
- Resent -- - 200 trace
--
107,500 101,200 102,200 1,000
107,500 101,200 102,400 101,200 48,761 45,903 46,448 45,903
5,972 5,622 5,680 5,622 --
2,709 2,550 2,582 2,550
*Total of 6 streams in 6 trains.
160
Table 7.8
ACETYLENE BY PARTIAL OXIDATION OF NATURAL GAS (WITH HEAT RECOVERY)
MAJOR EQUIPMENT OF REACTION SECTION
Plant capacity: 100 Million lb/yr (45,000 Metric Tons/yr) Acetylene
at 0.90 stream Factor
%iE’
I-101A-I
x-101 c-1026-P I-103kP L-IOU-P PAOSA-? S-106 S-107 x-1oS S-109
II-lOlA-9 6-1026-P II-IOU-P
2-101 T-102 T-103
v-101 V-1024-P v-103 v-104 v-105
liNerid of CotutNction
lmerial of construction Shell Tubem
SIZE mat laod Jmq ft) pm mu/hd
500 0.41 150 pmi$$, 3.8 tolu per hour. 50 pmi& 3.8 tona per hour.
bated by flue ~a‘ from H-103.
1.200 a. 7.20 " 2.aOo u 7.09 . . i;ooo e. 2.40 u
50 . . 0.10 . . 20 0.12
4.m 4.30 40 0.20 20 0.20
Carbon rtecl carboo ate*1 cmrboa area1
Natarid of ConmtNetion
3.100 -1 kettla Imated by ~a. by-produced in the proms..
2.6 " 4.5 aa 0.4 . .
Vol (ul)
Talk8
Oil tank BTX tank Cu bolder
65.000 carboa rtecl 12,000 Whoa steel
1.900.000 carbon l t*el
30 100 "
20,000 11,000
50
HaiSbt Diawtar Material of Construction crt1 (ft) Shell TNY,
c-lOlA-F fJlmu?hi~ col\nm C-LOU-P Oil eoltau c-103 Water l xubber C-104 vatmr *trippt
50 e. 4.0 8 fL of 1 in. riq packillS. s valve Cr.,.. 12 in. l paciq. 20 ft of 1 in. rlm~ peti-.
12 IL of 1 in. rilQ pubill&
36 u 1.5
ii 5.0 4.5
E!Ez loo wction- 46. imcludl~ 24 operatin& 22 .pm..i 20 opcrati~ bhp.
161
Table 7.9
ACETYLENE BY PARTIAL OXIDATION OF NATURAL GAS (WITH HEAT RECOVERY)
UTILITIES SUMMARY
Plant Capacity: 100 Million lb/yr (45,000 Metric Tons/yr) Acetylene
at 0.90 Stream Factor
Average consumption
Cooling water (gpm)
Refrig. at 600F (tons)
Refrig. at +PP (tons)
Refrig. at 400F (tons)
Process water (gpm)
Electricity (kv)
Steam used at 150 psig (lb/hr)
Steam used at 50 psig (lb/hr)
Steam made at 150 psig (lb/hr)
Steam made at 50 psig (lb/hr)
Inert' gas, low pressure (scfh)
Battery Llmlts 100 200 Total Section section
2,760 460 2,300
540 0 540
42 0 42
451 360 91
6 0 6
1,210 540 670
3,600 600 3,000
16,200 200 16,000
44,000 44,000 0
44,000 44,000 0
400 400 0
162
In this way, carbon in 011 at the bottom of C-102 becomes concentrated
to 40%. A part is withdrawn to coke kettle H-103. This is a stainless
steel kettle with a ribbed inside surface. It is loaded with a bed of
petroleum coke, provided with a paddle agitator, and heated on the out-
, side by direct firing. The residual oil is sprinkled on the hot coke
bed, vaporized, and returned to the bottom of column C-101. The carbon
that was In the oil becomes petroleum coke, and Is withdrawn through a
screw conveyor to receiver V-102, where it is transferred pneumatically
by nitrogen to a coke bin.
In this plant, which has a design capacity of 100 million lb/yr
acetylene, there are six trains, each consisting of an oxygen pre-
heater, a natural gas preheater, a burner, a column, waste heat boiler
E-102 generating 150 psia steam, waste heat boiler E-103 generating 50
psig steam, waste heat feedwater heater E-104, cyclone M-101, oil
column C-102 with heater E-105, coke kettle H-103 with screw conveyor
M-102, and coke receiver V-102. The coke bin, BTX condenser E-106,
receiver V-101, residual oil tank T-101, and heater H-101 are common to
all six trains.
Gas from all columns C-101 goes to water scrubber C-103, where a
stream of chilled water condenses the BTX. BTX and water are separated
in decanter V-104. Water is stripped in C-104 by heating to get an
areotrope at the top. The azeotrope is condensed and separated In
decanter V-105 to recover BTX. The wastewater from C-104 contains only
a trace of organica and can be discharged. BTX collected and stored in
T-102 is partly recycled to column C-101, and partly withdrawn as a
by-product.
Gas from C-103 is cleaned-up cracked gas. It is processed in ways
similar to those in the process evaluated before.
163
Process Discussion
In the BASF oil-quenching process used until recent years, naph-
thalene was the quenching medium. The high cost of naphthalene was a
drawback. The present process follows the same basic principle, but
the multinuclear compounds (naphthalene and homologues) are generated
in situ from residual oil. The amount of residual oil added may vary.
In our design, a minimum amount is added--just sufficient for quench-
ing* If more is added, multinuclear aromatic compounds will be by-
produced (i.e., stream 10 from C-102 will partly be withdrawn as a
by-product) and there vi11 be more by-production of BTX and coke.
The separation of coke in a ribbed kettle is based on a BASF
patent (302571). Other devices,. such as a centrifugal decanter or an
ordinary kettle as mentioned in reference 301010, are less eatlefac-
tory.
Cost Estimates
Tables 7.10 and 7.11 give the estimated capital investment and pro-
duction cost of acetylene made by partial oxidation of natural gas,
with heat recovery. A comparison of Table 7.6 and 7.8 shows that the
heat recovery results in an advantage of 5c/lb in product value. This
is a significant saving.
164
Table 7.10
ACETYLENE BY PARTIAL OXIDATION OF NATURAL GAS (WITH HEAT RECOVERY)
CAPITAL INVESTMENT
Plant Capacity: 100 Million lb/yr (45,000 Metric Tons/yr) Acetylene
at 0.90 stron hcmr
?waotIda: 3w
$ s19.4DO 1,07~.700 1.093.020 wm- 1.734,sDD 3,b73,9DD
45,100 193.m
$ 9.747.a oJ3 040
o(I~.ooQ
9.l34.oDo
9a5*670,ooo 0.67 0.u
9 u0.m 3,lDD
150,5w 49.2aD
$ 793,09D 0.H 0.47
7.4woQo 1.966.DDD
9lo,113,ooo
2.%0.wo
$12,642,0DD oabb 0.u
959,312.DDO 0.67 0.61
9 s10,4a 329,399
2z 1,724:slm
43.2DD (1.700
.4#9.7QO
913*7Y,mD
3.439.oa
917.190,ooo
Lb0 0.10 0.92 0.09 044 0.u 0.u 0.10 0.97 0.95 - -
0.9s 0.95 049 0.69
0.02 0.79
0.01 0.77
0.91 0.77
0.n 0.77
$ 111.2DO o.s7 0.37 00 0.62 1.01 - - -
49.220 0.22 0.22
$ 161.ooo 0.49 0.P
) --- 749,42D 0.77 0.0 219,la 0.w 0.u %b.ow 0.77 0.59
- - - 3.673.9w 0.w 0.60
2,sDD 0.a 0.60 l2b.5W 0.61 0.42
9 u97.100 044 0.59
422,794,ooO 0.57 0.53
5.b9b.ooo 0.17 0.))
$l..400*ow 0.57 0.53
$ WI.%0 0.56 0.39 2,)oo 0.76 0.79
uoo.500 0.69 0.70 - - -
$ 622,OOD 0.61 0.51
165
Table 7.11
ACETYLENE BY PARTIAL OXIDATION OF NATURAL GAS (WITH HEAT RECOVERY)
Variable toe te
Raw materials
Natural gas Oxygen. (95%) N-Methylpyrrolidoue Residual oil. Sulfuric acid Caustic soda (50X)
Gross raw materials
By-products
Gas Petroleum coke BTX lZc/lb
Total by-products
Utilities
Coollng water Steam Process water Electricity Inert gas, low pressure
Total utilities
PEP Cost Index: 360
unit Cost Conswption/lb c/lb
9.48c/lb l.lC/lb $l.lO/lb 5.5C/lb 4.5c/lb 6.5c/lb
4.1 lb 5.14 lb 0.00314 lb 0.3 lb 0.13 lb 0.057 lb-
38.87 5.65 0.35 1.65 0.58 0.37
47.47
4.00 $/MM Btu -0.0428 I@f Btu -17.11 %/lb -0.35 lb -1.75 -0.049 lb -0.59
-19.45
Unit Cost Consumption/lb Consumption/kg C/lb
5.25c/l,OOO gal 7.90 gal 65.9 liters 0.04 $6.40/1,000 lb -5.3 lb -5.3 kg -3.40
6Oc/l,OOO gal 0.038 gal 0.316 liters @JWl 3.2c/lcwb 0.064 kwh 0.141 kwh 0.21 70c/1,000 scf 0.032 scf 1.86 liters Negl
-3.15
166
Table 7.11 (Concluded)
ACRlYLENE BY PARTIAL OXIDATION OF NATURAL GAS (WITU URAT RECOVERY)
PRODUCTION COSTS
PEP Cost Index: 360
Capacity (million lb/yr)*
Investment ($ million) Battery limits Off-sites
Total fixed capital
Scaling exponents
Production costs (c/lb) Raw materials By-products Utilities
Variable costs
29.8 45.7 95.2 8.3 12.6 26.1
38.1 58.3 121.3
0.61 0.67
47.47 47.47 47.47 -19.45 -19.45 -19.45 -3.15 -3.15 -3.15
24.87 24.87 24.87
Operating labor, a/shifts, $15.40/hr 2.16 1.08 Maintenance labor, 3.5Xlyr of BL inv 2.09 1.60 Control lab labor, 20% of op labor 0.43 0.22
Labor costs 4.68 2.90
Mainteuance materials, 3.5X/yr of BL inv 2.09 1.60 Operating supplies, 10% of op labor 0.22 0.11
Total direct costs 31.86 29.48
Plant overhead, 80% of labor costs 3.75 2.32 Taxes and Insurance, 2%/yr of TFC 1.53 1.17 Depreciation, lO%/yr of TFC 7.63 5.83
Plant gate coet 44.77 38.80
G&A, sales, research (5% of sales) 3.00 3.00
Net production cost 47.77 41.80
ROI before taxes, 25%/yr of TPC 19.05 14.57
Product value 66.82 56.37
*Of acetylene.
tBase case.
SFor base case only; may be different for other capacities.
0.45 1.11 0.09
1.65
1.11 0.04
27.67
1.32 0.81 4.04
33.84
3.00
36.84
10.11
46.95
167
Acetylene from Naphtha by Partial Oxidation
Instead of natural gas, naphtha may be used as feedstock. In this
case, the preheating is only to 6620F (350%); a higher temperature
might lead to preignition. The acetylene-making capacity of the same
burner is 20% higher than when natural gas is used. Pence five trains,
each consisting of a burner and associated equipment, are used instead
of six as in the case of natural gas. The acetylene content in the gas
is 9% instead of 8%; thus, the total quantity of gas is smaller and the
compressors can be smaller. The amount of carbon, however, is much
larger, about 6 times as much as when natural gas is used as feed in
the case of water quenching, and 1.8 times as much as with natural gas
in the case of oil quenching.
With the major equipment modified in accordance with the changes
described above, and with the material usages given in reference
302504, the estimated capital investment and production costs are given
in Table 7.12 and 7.13 respectively for the water quenching case. Note
that the process is definitely less economical, at present naphtha
prices.
A few BA!ZF patents aim to improve the process for partial oxida-
tion of naphtha to produce acetylene. Thus, adding CO2 to the feed
reduces carbon formation (302002); also, modifying the burner to
shorten the residence time enables a higher preheating temperature (up
to 6OoOC) without preignition, and thereby a higher output (324184).
From a check of numbers in Table 7.10, it is evident that any such
improvements would still not make this process economical; the main
problem is the high cost of naphtha.
168
Table 7.12
ACETYLENE BY PARTIAL OXIDATION OF MAPHTHA
CAPITAL INVESTMENT
Sottory limita oquimt, f.o.b.
hectors CUl- vuulo d tubs bcbsqors 9wouu Ooqrrusors WlmwllaMmNmuiMt
off-sitms. ilut~llmd
coouqltanr 9mcou utoc tuumsot stsa puration ssLrlput100
tltilitiu so6 sror~
cmeral urvica facilitiw uuto trsotnot
TOta1
Csoti~. 252
oev4In9 Isvssm
TOTAL VIIW WVITU
Plant Capacity: 100 Million lb/yr (45,000 Metric Tons/yr) Acetylene
l t 0.w scum hctor
w9cutIo6u: 360
$ 432.ooO 1.578.996 l,OY,lW 495.009 439.9W
3,470,4W 125,7w 217.W6
( 7.615.906
~3.952,006
m8woo
(42,415,006
$ 452,000 642.909 629,606
459,900 72,066 122,200 691.406
6.71 0.65 $ 2.640.500
(11,676.OW
2.%9).906
0.69 0.w 614,645,6w
0.w 0.60 0.94 0.90 0.70 0.69 - -
0.95 0.95 0.60 0.w 0.60 0.60 040 0.64
O&O 0.76
- -
- - - -
0.W 0.72
8 - 736.006 217.1W 495.w9
3.3W.400
2,- 126.500
) 4.975.509
$22.056,006
5.514.6W
627,570.OW
- - 0.77 0.63 0.56 0.42 0.71 0.59 - -
0.60 0.60 0.60 0.60 0.61 0.42
0.64 0.59
- -
- -
0.59 0.54
1.207.200 904,406 0.w 0.6s 302.SOO 0.69 0.69 2.= - - - 2.500 0.75 0.80
469,WO - - - 489).800 0.s2 0.62 469.100 - - - 469.100 0.70 0.70
$ 2.169.ooO 0.84 0.72 $ W4,909 0.W 0.W $ 1.264,OW 0.79 0.74
7.220.000 1.w5.000
$11.194.006
2.7W.ooO
$13,W2,WLl 0.73 0.69
896.497.ooQ 0.70 0.w
169
Table 7.13
ACETYLENE BY PARTIAL OXIDATION OF NAPHTHA
PRODUCTION COSTS
PEP Cost Index: 360
Variable costs
Raw materials
Wapbtha 12.7c/lb 4.3 lb 54.61 Coke " k/lb 0.015 lb 0.06 olcrsen (5%) l.lc/lb 4.61 lb 5.07 N-Methylpyrrolidone $l.lO/lb 0.00314 lb 0.35 Sulfuric acid 4.5c/lb 0.099 lb 0.45 Caustic soda 6.5c/lb 0.079, lb 0.51
Gross raw materials -21.04
By-products
Gas Carbon
Total by-products
Utilities Cooling water Steam Process water Electricity
Total utilities
Unit cost Consumption/lb C/lb
0.4c/l,OOO Btu -39.400 Btu 0.4cllb -32.2 lb
unit cost Consumption/lb Consumption/kg c/lb
S.ZSc/l,OOO gal 39 gal $6.40/1,000 lb 1.3 lb 6Oc/l,OUO gal 0.024 gal 3.24c/kwh 0.07 kwh
-15.76 -5.28
-21.04
321 liters 1.3 kg 0.2 liters 0.154 kwh
0.20 0.83
0.23
1.26
170
Table 7.13 (Concluded)
ACETYLENB BY PARTIAL OXIDATION OF NAPRTRA
Capacity (million lb/yr)* 50 1UCt 300
PRODUCTION COSTS
PEP Cost Index: 360
Investment ($ million) Battery limits Off-sites
Total fixed capital Scaling exponents
Productiou costs (c/lb) Raw materials By-products Utilities
Variable costs
Operating labor, I/shiftS, $15.40/hr Maintenance labor, 3X/yr of BL inv Control lab labor, 20% of op labor
Labor costs
Maintenance materials, 3X/yr of BL inv Operating supplies, 10% of op labor
Total direct costs
Plant overhead, 80% of labor costs Taxes and insurance, 2Xlyr of TPC Depreciation, lO%/yr of TPC
Plant gate cost
G6A, sales, research (5% of sales)
Net production cost
ROI before taxes, 25%/yr of TPC
Product value
28.0 9.2
37.2
42.4 90.5 14.0 31.2
56.4 121.7 0.60 0.70
61.05 61.05 61.05 -21.04 -21.04 -21.04
1.26 1.26 1.26
41.27 41.27 41.27
1.89 1.08 0.45 1.68 1.27 0.90 0.38 0.22 0.09
3.95 2.57 1.44
1.68 1.27 0.90 0.19 0.11 0.04
47.09 45.22 43.65
3.16 2.05 1.16 1.49 1.13 0.81 7.44 5.64 4.06
59.18 54.04 49.68
3.00 3.00 3.00
62.18 57.04 52.68
18.60 14.10 10.14
80.78 71.14 62.82
*Of acetylene.
tBase case.
&or base case only; may be different for other capacities.
171
Acetylene by Submerged Flame Process
A submerged flame process was developed by BASE’. A liquid hydro-
carbon (crude oil or residual oil) is cracked and partially oxidieed in
an oxygen-fed flame below the surface of a pool of the hydrocarbon.
The products are iaxnediately quenched by the surrounding liquid. The
gas from the reactor contains 6-7X (volume) each of acetylene and ethyl-
ene . A commercial plant in Italy employing the process was operated in
1968 but shut down In 1974. The capacity was 110 million lb/yr acetyl-
ene, with no ethylene recovery.
The process was evaluated in PEP Report 109, Section 8, on the
basis of information supplied by BASE’. Table 7.14 Is an update of that
evaluation, converted to present cost bases. From this table, it seems
that this process would give acetylene at a product value lower than
any other process. This was indeed the conclusion of PEP Report 109.
However, the above is based on a separation scheme which radically
departs from that used in any commercial process. The cracked gas,
after removal of carbon, 02, H2S, and water, is compressed and refrig-
erated to separate ethylene, acetylene, and all heavier hydrocarbons,
which are then separated by absorption and fractionation. This ingen-
ious device minimizes the handling of large volumes of gas in the ab-
sorption process, which otherwise would be used, and hence reduces
considerably the capital investment and possibly also the utilities
costs. This process, however, entails the handling of low temperature
liquefied hydrocarbons containing a high percentage of acetylene. This
might be expected to give a solid acetylene precipitate, which is
considered to be hazardous. BASF had the safety of handling such mlx-
tures investigated in the laboratory and was apparently satisfied that
the operation is not hazardous. Nevertheless, nobody has ever prac-
ticed this approach. The Italian plant used the acetylene absorption
procedure without recovery of ethylene.
If, instead of the abovelnentioned refrigeration process to sepa-
rate acetylene and ethylene, one uses the conventional path, i.e.,
separation of acetylene first and then recovery of ethylene by
172
refrigeration, the capital investment would be considerably Increased.
By analogy with the recovery procedures In other processes, we roughly
estimated that the capital investment would be increased by 40-50X.
This means the product value of acetylene at 100 million lb/yr produc-
tion would have to increase by about 16020c/lb, Le., to 56060c/lb.
This would then only be slightly lower than that by the partial oxida-
tion process.
173
Table 7.14
ACETYLENE FROM RESIDUAL OIL BY SUBMERGED FLAME PROCESS
PRODUCTION COSTS
PEP Cost Index: 360
Variable costs Unit Cost
gaw materials
Residual oil
Oxygen Diethanolamine caustic soda Toluene N-Methypyrrolidoae Methanol
Gross raw materials
By-products
Ethylene
Leaa g- c3+ Fuel oil
Total by-products
Utilities
Cooling water Steam Process water Electricity
S.Sc/lb l.Sc/lb 53.5dlb lZc/lb 18.8dlb lldlb 11.4dlb
24c/lb 0.4~/1,000 Btu 9cllb S.SC/lb
unit cost
5.25c/l,OOO gal $6.40/1,000 lb 6Oc/l,OOO gal 3.24dkwh
Consumption/lb c/lb
10.98 lb 60.39 7.67 lb 11.50 0.001 lb 0.05 0.0011 lb 0.01 0.0005 lb 0.01
0.0001 lb bgl 0.0025 lb 0.03
71.99
-1.15 lb -27.60 -64,000 Btu -25.60 -1.3 lb -11.70 -2.64 lb -14.52
-79.42
Consumption/lb Consumption/kg c/lb
48 gal 401 liters 0.25 -2.4 lb -2.4 kg -1.54 1.2 gal 10 liters 0.07 1.31 kh 2.89 kwh 4.24
3.02 Total utilities
174
Table 7.14 (Concluded)
ACETYLENE FRON RMIDUAL OIL BY SWMERCED FLAME PEocgss
Capacity (million lb/yr)*
Investment ($ million) Battery limits Off-sites
Total fixed capital Scaling exponents
Production costs (c/lb) Raw uaterials By-products Utilities
Variable costs
PRODUCTION COSTS
PEP Cost Index: 360
50
46.3 14.5
60.8 0.57
71.99 -79.42
3.02
-4.41
loot
58.7 21.5
90.2
71.99 -79.42 3.02
-4.41
Operating labor, S/shifts, $15.40/hr 2.16 1.21 Maintenance labor, 3%&r of BL iuv 2.78 2.06 Control lab labor, 20% of op labor 0.43 0.24
Labor costs 5.37 3.51
Maintenance materials, 3%&r of BL inv 2.78 2.06 Operating supplies, 10% of op labor 0.22 0.12
Total direct costs 3.96 1.28
Plant overhead, 80% of labor costs 4.29 2.81 Taxes and insurance, 2%&r of TPC 2.43 1.80 Depreciation, lO%/yr 12.15 9.02
Plant gate cost 22.83 14.91
C&A, sales, research (5% of sales) 3.00 3.00
Net production cost 25.83 17.91
ROI before taxes, 25%/yr of TFC 30.40 22.55
Product value 56.23 40.46
*Of acetylene.
base case-
SFor base case only; may bs different for other capacities.
300
128.5 40.2
168.7 0.57
71.99 -79.42 3.02
-4.41
0.49 1.29 0.10
1.88
1.29 0.05
-1.19
1.50 1.12 5.62
7.05
3.00
10.05
14.06
24.11
175
-
a
8 ACETYLENE BY THE ELECTRIC ARC PROCESS
Processes using an electric arc for making acetylene are reviewed
in Section 6. Arc processes now are used commercially only in a Buels
plant in West Germany, and a mall plant in Rumania. The Rue18 plant,
as it is currently operated, uses the water absorption process for
recovery of acetylene. This process was developed in the 1940s and has
been used ever since. Meanwhile, Wuels, together with Linde, has
developed a new and better separation and recovery scheme and will use
that process in any future licensing. In this section, we evaluate the
Wuels process using this new scheme of separation.
An arc process using coal as the raw material is now under develop-
ment. This process Is briefly evaluated here also.
Acetylene by an Arc Process Based on Hue18 Technology
Process Description
The &sign bases and assumptions are given in Table 8.1.
The flow sheet is shown in Figure 8.1 (foldout at end of report).
The compositions of the streams marked in Figure 8.1 are shown in Table
8.2. The major equipment list and utilities summary are given in
Tables 8.3 and 8.4 respectively.
As acknowledged in Table 8.1, SRI received valuable information
from Chemische Werke Buels. The main scheme described below is based
on this information. However, the detailed procedures of the process,
the composition of streams, and the size of equipment were developed by
SRI. These details do not necessarily represent Buels or Llnde
technology.
As shown in Figure 8.1, production of 100 million lb/yr acetylene
requires six electric arc reactors. A slender 4 ft high tube serves as
177 (Text continuous on page 184.)
Table 8.1
ACETYLENE FROM NATURAL GAS BY ARC PROCESS
DESIGN BASES AND ASSUMPTIONS
References 302295, 302297, 302474, 302502, 302535, 302609, and private communication from Ruels
Feed Natural gas (primary)
Butanes (secondary and quenching)
Reactor 8 kv, 1.25 ka direct current
Carbon black removal Water scrubbing and oil scrubbing
Absorption Methanol absorption at 117.6 psia to remove high acetylenes, octane absorption at 235 psia to remove C3+ hydrocarbons, N-methylpyrrolidone (85X)-methanol (15%) to recover acetylene
Ethylene recovery By "cold box"
Hydrogen recovery By pressure-swing absorption
178
Table 8.2
ACETYLENE FROM NATURAL GAS BY ARC PROCESS
STREAM FLOWS
Plant capacity: 100 Million lb/yr (45,006 metric Tons/yr) Acetylene
at 0.90 stream Factor
16.0 lS.2S2 - - - - -- -- - 9.996 30.0 ii.0
50.0 44.0 10.0 12.0
120.00 27.0 26.6 28.0 42.0 56.0
1.421 506 104 544
--
--
-602 401 562
3,552 2.376 SW
s75.060 3.110
-- --
700 --
--
--
--
--
--
--
--
12,747 3.900 1.925 655 200 40
5:: 170 9S0 40
7: 451
5,569
- -
- -
- -
a -
- -
- -
- --
- 317 - - - - - - - - - - - - - -
900 - - - - - - -
z - - - - - - - - - - - - -
- -
- -
-- -
- -
me -
-- 2.S46 - -- - - -- - - 10 - - - - - - - - -- - - -
- Trace - Tmce - Trace - - -- - - - -- - -- - -- -
- Trace - -
634 - --
634 2,656 286 1.295
3 156 1 72
--
a
a
--
em
-
96.0 2s.o 20.0
- - - - - - --- ----------- Totals, lb/k 21,242 9,132 71,000 3,552 3,264 660,000 660.000 075.7110 42,709 1,960 317
balhr 9,635 4.142 35.300 1.611 1.4Sl 299,369 299,369 397,245 19.372 S62 I44
Toorals, lkol/hC 1,221 157 4,333 296 266 36,667 5,500 41.640 4,393 24 3 llrolhr 557 71 1.966 134 93 16,632 2,495 22.063 1.993 11 1
Wol Stream Plaw (lb/br) lit (14) m (16) m (II) u (20) (21) (222 (23) m m m m
84.0 5.0 '4.0 s.0 2.0 I.00 17.0 i6.6 i6.0 12.0 16.0 l4.0 '9.0 '4.0 IO.0 0.0 0.0 'S.0 16.0 !S.O !O.O 2.0 12.0 .4.0 19.1
-- --
--
- - 3.206 3.200 - - -- - - - - - - 3*ooS - - - - - - - - - - - - - - - - - - - - - - - - - - 40 - 20 - - - - - - - - - 16 - - -
100 4
--
4
--
540 160 900
166 166 30 30 6 6
- -- - - -- - - -- - - - -- - -- -- - 3,264 - - - - - - - - -- -- - - - a - - - - - - -- - - - -- - -- -- - - -- - - - - - - - -- - - - - I -- - - - - - - - - - -
165 Tram - - - 46.620 - -- - - - -
--- 165 3,264 46.620 75 1.401 21.146
46 46 6.069 6,lSS -
600
- Prwmt - PnmmIt - Re8mnt - Prw.ot - Plum*at - Pr**mt - R,aant --
-- 43 43 4 350 23
--
16 --
-- a
- 400 - - 560 - - - - a - - -- - -
-- - -- - -
-- - 10 - -- - 1.925 - - 655 - - 200 -
40 - 40 Raw 5 Trace 10 Trace
I - - - - -- -- - - 315 466 - 56 116 - 11 92i - - - -
15 1.349 I - -
Pyrolyoim ruldu 200.0 LZLLL Total& lbibr 12.002 76 3.000 5.1116 3.406
Clhr 5,444 34 1,361 2,352 1,545
- - - - - ---- 462 1.070 6.461 11.542 1,349 210 409 2.931 5,235 612
Tocalm. lklhr 375 O.S6 167 250 210 : 101 409 160 203 390 951 12 bs--ol/hr 170 0.39 76 113 95 112 105 s2 92 1Sl 432 5
179
able 8.2 (Concluded)
AcEnl,EnE FROM lummAL GAS BY ARC Fwwss
Plant cnp~eity: LOO Million lblyr (45,Wo mtrie lbdyr) Acetylene
at 0.90 stmu Factor
X01 Stream Flow lbfbr (281 m wt (35) (54) ( (3s: B (37) (38) (39) m (30) (31) (32)
16.0
20"
10,042 602
8
--
--
me
--
12,622 30
10,042 608 9,268 602 - 602
Trmx
--
- l-mea -- --
-- - --
-- I
--
-- -
--
1 3,900 - Tmce -- -
-- -- -
-- --
-- -- - - -- - - -
562 481
58.0 44.0
Voter carbon Ahotption oil sydrogm cyanide Acmty1em Ethylene Ropylene Suty1elu wutadiem ROtaon aId -r other c5+ SC8 lutbyl~utylacu
18.0 12.0
120.00 27.0 26.6 28.0 42.0 56.0
-- --
--
--
VW
--
--
--
--
--
--
-- 5,899 Tmca
25
-- mm
--
--
--
1,197 474 305 86
- - 5,919 I - - -- - - 5.919 4.638 17 - 12.ow Tmce 17.550 15.060 Tmec - - - -- - - 76 - - -- - - - --- - - - - -- - 99.450 85.000 - - - 13 - - --
54.0 79.0 74.0 40.0 52.0 50.0 78.0 96.0 28.0 28.0 2.0 32.0 114.0 99.1 200.0 --e--- - - - ------- - - - - - - -
33 76 12.000 22,134 117JM.l lOO.WO 305 5.WO 12.685 13 22,133 6,114 14,354 15 34 5,445 10.040 53.070 45.559 138 2,268 5.754 6 10,039 2.773 6.511
17 0.67 575 3.806 1,552 1,326 11 192 488 0.13 3.806 2,388 767 7 0.30 170 1.726 704 602 5 07 221 0.06 1,726 1.083 348
HO1 Stream Flowa (lb/k)
yc (42) (43) (54) (45) Iss) (47) (48) (49) (50) m mf
mthaoc 16.0 wlanc 30.0 60:
l-- - Trace 602 - --
- --
- --
- --
- -- -- -- -
- - - - _- -
2 3.881 4 -- -- - - -- -- - -- - -- - -- - - -- - -- - - -- - -- - -- - --
1
-- -- -- --
--
560 120 47 - -- -- --
- -
--
--
- -
--
--
-- -- -
--
-- -- -- --
-- --
- -
-- -
- -
I -
- -
- -
I -
--
--
518 281 726 --
--
111 60
914
- -
I -
- -
44 -
24 -
62 --
- 1.628 1.625 - - -
- 9,226 - 9.200 - -
-A--
177 lO,S54 1,625 9.200 80 4,923 737 4.173
36 144 51 93 16 65 23 42
--
26
-
26
12
0.26
0.12
RODW 44.0 Ttmx
wutioe 56.0 -
Carbon dioxide 44.0 -
water 18.0 - cmrbml 12.0 - Ahorption oil 120.00 - ilydr&n cydde 27.0 -
Acatylmu 26.6 -
SLbylme 28.0 3.687
RopylcaLa 42.0 Tmca
SutylCM 56.0 -
wlltadimc . 54.0 - a 79.0
74.0 40.0
52.0
50.0
70.0
96.0
28.0 28.0
3:::
114.0 99.1 200.0
--
4.490
2.037
159 72
Carbon mnoxihc Hitrosen
Hydra& 1ctbmo1 octmw S+kthylpyrrolidom Pyrolymie reaidme
- - - Trace - - - 3.816 - -- - - - - - -- - -- - - -- - - _
-we---
3 %881 606 3.817 2.085 1.205 1 1,760 275 1.731 946 547
0.13 139 20 1,908 427 471 0.06 63 9 865 193 213
180
Table 8.3
Plant Capacity: 100 Million lb/yr (45,000 Metric Tons/yr) Acetylene
et 0.90 Stream Factor
Equf pment hmber
I-1olA-r
ume
~ectore
Reectore
Cmvr*e*or*
K-101 Air bloom K-201 Ccqau*or K-202 Cmpreeeor K-203 mreeeor K-204 Secycle blower K-205 Ueycle blawr K-206 ketylema blowr K-301 Compr*eeor K-401 Ethylene capreeeor K-402 Ropylem coqm***r
X-101 E-102 E-103 a-104 E-105 t-201 K-202 B-203 C-204 E-205 &2C6 MO7 E-200 B-209 E-210 E-211 E-212 6213 L-214 E-215 L-216 E-217 L-216 L-219 r-220 E-221 L-222 E-223 IS-224 E-301 K-362 K-303 t-304 x-305 K-306 K-307 K-506 X-401 K-402
bcheoser Ceoler cadee*er Wodeoeer Chiller Int*rcool*r Cooler IbtheDol condeeaer Reboiler Cooler Cooler hboiler
R&e&r Cooler Cmdeneer Cooler Cooler Cooler
Cooler Ekchaopr Excheqer Reboiler kchenger Cooler
Keboiler Condenser
Cooler
Keboiler coo&ne*r Keboiler weet*r Ethylene cooler Ethylems cooler
Sire Hmteri*l of Conetructioa KeurkP
10 ISI, (1.1 W. 1.25 KA, DC
Cerboe #reel Uith reetifim-trmefomer.
Sire (bhp)
Carbon *tee1 Carbon *reel Carbon *tee1 Cmrboo l teel Cerboo mteel carboe *tee1 Cerboe ace1 Cerbm rteel la, teeP acne1 Cab00 Lee1
2;2OC 50 340 30
1,E W’3’J
she lbet Loed Unterlel of Cowtruction jeq ft) pl stu/hr~ Shell Tube,
1.700 470 50 loo
20,ooC 2.400 2.400 6.900
Xi 2:000
5.0: 2.400 600 270 270 270 220
2.900 2.900 2.600 2.000
E 600
1.200 1.400 170
1,200 400
10,OW 4.100 4ao
1,300 520
4.60 3.20 0.20 0.40 20.00 5.10 5.10 12.20 12.20 4.20 3.90 6.70 2.90 1.40 0.80 0.70 0.36 0.36 0.34 3.90 3.90 4.90 7.110 12.30 0.50 0.90 3.40 3.63 2.92 3.20 0.40 6.90 3.30 4.00 3.50 2.60
1.- 1.40 3.300 7.20
Wrbon aeel
Wrbon et**1
tirboa we*1 Cerboo *tee1
Carbon steel
Cerbcm ace1 Cerboa *reel Cerbon *reel Orben ace1 Cerbon *reel Cerbon *tee1 Cerbon l t*cl Cerboo *reel Qrbom et**1 Qrbm *tee1 ~rboe *tee1 brboa *reel tirboa wee1
Cmrba *reel Cerhon *reel
Carbon *reel
Wrbon *tee1 Carboo *reel
Cerbon *tee1
brboa *tee1 Carbon *reel tirboo ateel Cerbon *reel cerbes ateel Carbon *reel Qrboo *reel Qrboo *reel Qrboa mteel Cerhoo weal Cerboo awl Carbon *reel
Cerbm *tee1 Qrboo *tee1 Cerbm et**1 Urban wee1 tArbe *reel Qrboe *tee1 Carbon steel Carbon ateel Cerbon steel Cab00 ateel Carbon l teel Cab00 *tee1 Csrboo l t*el
Wrbon *tee1 Cerbcm *reel Urboa *tee1 Cerkoo l te*l Wrbm *reel Carbon ateel cerbon a**1 Lou temp et**1 Carbon ateel brboo *tee1 Cerboo *reel la temp *tee1 la temp atI La tcrp mtml _ Lou teep et**1
raw te9P mteel - Eew *tee1 Qrboo item1 Qrbom &oel Cerbeo aeel Lou temp *tee1 ~rben wee1 Qrbon l teel
Cerboa *tee1 carbon l tce1 cerboa et**1 la telp 8teel
bet Iaed @I4 Btu/hr)
4.4
lleteriel of Construction
Cab00 *tee1 n-101
Y*CMC**
Reboiler
181
hble 8.3 (Continued)
ACEfTLEW PROM WiNML OAS 8Y MC PROCESS
Equipmnt lhbmr liem?
2-101 Cmoline tenk F-102 Oil tenk T-103 Reeldee oil ted T-104 l&ret tank T-105 Cracked mm holder T-151 GneoliM etorwe T-152 Reeldoe oil rtorese T-u)1 mtkeoe1teak T-202 octene tank x-M3 &Avant tenk x-204 l3-&thylpyrrolidooe
Remmum ~eeee1e
v-lOlA-P F-102 v-201 V-202 V-203 V-204 V-205 V-206 V-207 V-206 V-209 V-210 v-211 v-3olA.B v-302 V-303 V-304 v-305 V-306A.B v-401 v-402 v-403 F404 v-405
&ttliq veeeele loflux dru Comdenaete receiver Ceedeeeete nceiver Deceeter Reflur dru Reflur dru Bydro~eetor Seperetor Adamber Enflux dnm -flux drm Cmdmuete receiver Adaorbere Seperetor Emflux dru Receiver Beflux dru Receimrm Etkylene fleeb dru Ethylene fleeh dru Propylene fleeh dru Propylene flaeh dru Propyleee Clada dru
C-lOlA-F c-102 C-103 C-104 e-105 C-106 c-201 C-202 C-203 *204 C-205 C-2176 C-207 C-206 C-209 C-210 C-211 c-212 C-213 C-214 *301 C-302
Plant Wpecityt 100 Uillioe lb&r (45.000 lktric Tomlyr) Acetyleoe
at 0.90 Stream Factor
Sire Voleme (ml)
Coo1106 eO1e.ee Oil l erobbios colem Water l erebcr ArLroutle~ l crubbet Atoutics colmn Uter l tripper Cooler-•crubber Cooler-ecrubber I*tkenol merubber Stripper l&tbenolcolun C3+ l bmorber 4cetylmm mtripper C* dmorbor I*tkenol ecrubber Acetyleoe l crubber Ltbylem l trimmer mp&ation 00iA
Acetylene demorber Methend-mP coleme Deeetbmizer 9 eplitter
3.000
5o;wo 1.500
16O;WO 1.600.000
4o.WC 11,000 8.000 4,wo 30,000
600
1,000 me 140 loo 100
l.WO -300 250 loo 60 loo 100
1.m 50
2.500 ma so0
4.wo wo
l.WO 2,000 ma 160 160
1,100 3.600 2.400
lblght Diemeter (it) (ft)
80 4.5 50 7.0 30 7.0 60 3.0 30 4.5 40 12.0 10 1.5 10 1.5 10 2.5 20 2.0 56 6.0
: 3.5 5.0
30 5.0 8 1.5 30 5.0 30 6.0 18 6.0 30 6.0 14 2.0 40 10.0 122 3.0
Meteriel of Cautruction 8emrke
Cerbon *tee1 Carbon area1 carbon ateel Carbon *teal cntbon rteel Cerbm ateel Csrbm steel brbon wee1 Wrbm *reel Carbon *reel Carbon at-1
Carbon steel Wrbm etwl Carbon at-1 Carbon eteel Carbon et-1 Carbon *reel tkrboa ateel Who0 eteel cerbon at-1 tkrboo ateel tarhI w.eel Carbon l teel Carbon steel Carbon l teel hrbon l teel law tee eteel Law temp eta01 Wrbmkeel Carbon *reel Lov temp steel Lov teep steel Lou tap l teel Cerbon et**1 Qrbm steel
Meteriel of Ceeetrectiee Skell Treya
Carbon *reel Carbon et**1 carbon et-1 Cmrbon *tee1 Cerboo et**1 Cerboe rteel Carbon eteel Cerboa et**1 carbon et-1 Carbon at-1 Cerkoo et**1 Carbon steel Carbon et**1 Carbon l teel thrhon steel Cmbon et-1 Carbon ateel Carbon eteel Carbon l teel Q&on tsteel Lar temp l teel t%rben ateel
Stommre 60 ft of 1 in. Berl packivq. Stoaeoere 30 ft of 1 in. Berl pecking. Stonemre 22 ft of 1 in. tier peckiry. st.Memre 50 ft of 1 in. rirrg packin&
Carbon steel 3 velre treya. 12 in. epaeing.
Stooemre carbon atee stoneuare St-r* Qrbon ate*1 Stoneare &don l tml
\
Stonmue
304 s. Carbon l teel Qrbon ateel
W0tAmm 00 flow sheet. Wet l houo oo flow sheet.
14 ft of 1 in. ring pecking. 20 velve traye. 24 in epeciog. 16 ft of 1 la. riq peeklo& 20 ft of 1 in. rioS puking. 14 velre treye. 24 in. l pecio.9. 5 ft of 3/4 in. riw pecking. 10 valve treya, 24 in. epeciry.
12 it of 1 in. ring pa.kin&
30 velve treye, 24 in. l pecieg. 110 velve treye, 12. in *pacing.
182
Tcblo 0.3 (Comcludd)
ACBTTUW Tllg lMW4L 04S BY ARC PWOISS
Plrt Capacity: 100 wlllioo lb/v (45.000 lrtric TommlTr) 6cetylefm
et 0.90 strum Tct%or
n-201 Eoporctor n-301 Epoodor
140 l q ft
la0 soctiom - 23. inlmdi~14 opmreiy.9 l pru; 221opmrdq bbp. 200 soctioo - 44. includicy 24 opwatl~. 20 ‘pa”.; 226 oporatim bbp. BW aoetioo - 12. inclodiy 6 opmatlw, 6 r-r..; 21 operatlw thp.
hblm a.4
ACEVVUW TWM IliTOML CM BT 4RC RWKBS
Plmt Cm-city: 100 llilliom lb/m (45,aoO lhtt1c Tcmc/yr) 4cetyleIu
et 0.90 Btrum Pactor
rtmryLutm 100 206 300 400 TOtCl soctioo Bcctloo &ctioo soctioo ----
Aworogo coMrptio0
cooli~ mt*r (gpm) 4,410 380 4.100 0 0
Lhctricity (kW) 79.050 65.500 7.400 25 5.900
Star l t 50 pm* (lb/br) 22,OOO 0 22.000 0 0
star l 3w 9mi9(1b/hr) 4,aw 0 4.aw 0 0
Betmel (rillion Btolk) ac. 7 7 0 0 0
183
an anode. On top of this is a whirl chamber (2.5 ft diameter and 1 ft
high) through which natural gas passes. On top of the whirl chamber is
a bell shaped cathode. An arc about 3 ft long (8,000 volts and 1,250
amps) rapidly decomposes the gas. In the upper part of the anode tube,
the cracked gas is quenched by a stream of liquid butanes. Further
down, near the exit of the reactor, the gas is quenched by water.
The gas from each reactor enters cyclone M-101. A major part (80-
85%) of the carbon formed during the cracking settles. The gas next Is
cooled by a large stream of water in cooling column C-101. More carbon
settles and Is separated from the water in carbon settler V-101. Gas
from C-101 enters venturi M-102, where it meets a stream of scrubbing
oil. Up to this point there are six trains, corresponding to six
reactors.
The mixture of oil and gas from the six venturis M-102 enters oil
scrubbing column C-102, to be scrubbed by a countercurrent oil stream.
This oil scrubbing removes the residual carbon suspended in the 011; it
also removes a part of the aromatic components and C5+ hydrocarbons in
the gas. The gas from C-102 is scrubbed with water In venturi M-103
and water scrubber C-103, and finally scrubbed with 011 in C-104. The
resulting gas is virtually free of carbon particles, HCN, and heavy
aromatics, and has a greatly reduced content of C5+ hydrocarbons and
light aromatics. It is stored in gas holder T-105, ready for acetylene
‘recovery procedures.
Oil discharged from C-104 is heated in exchanger E-101 and then
distilled in C-105, which has a direct-fired reboiler at the bottom, to
get pyrolysis gasoline as the distillate at the top and a residue at
the bottom, and to recover the scrubbing oil from the middle section.
The recovered scrubbing oil is cooled in E-101 and E-102 and recycled
for scrubbing. The pyrolysis gasoline and pyrolysis residue are
by-products.
The water stream from C-103 and V-101 is deaerated in C-106 to
cool and to remove hydrogen cyanide and organic volatile matter. The
184
a -
a -
a
water is then chilled by 50oF refrigerant to 60-80°F and recycled to
c-101. The organic-containing air stream from C-106 is used as combus-
tion air In the boiler.
The cracked gas from the gas holder is compressed to 117.6 psia
(7 bars) in two stages by screw compressors with intercoolers and con-
densate receivers. The condensate returns to C-103.
The compressed gas enters successively C-201, C-202, and C-203.
Methanol flows down in C-203 and absorbs the higher acetylenes. The
methanol solution formed In C-203 flows into parallel columns C-201 and
C-202 and dissolves the water and benzene and homologues contained in
the gas. C-201 and C-202 are cooled by two streams (in coils), a crude
hydrogen stream and an off-gas stream, generated during the separation
and recovery of ethylene, as described later. C-203 is cooled by a
-5OoP refrigerant in a collm In this way, all the higher acetylenes,
beneene and homologues, and water are dissolved in methanol, without
the danger of freezing in the equipment. This solution from C-201 and
C-202 is released In pressure in C-204. An off-gas stream (from ethyl-
ene separation, to be described later) is blown in at the bottom of
C-204, and water is added at the top of C-204. In this way, all the
higher acetylenes are carried by the off-gas and leave C-204 at the
top. The gas recycles to the reactors. The liquid from the bottom of
C-204 is a mixture of methanol, water, and benzene and homologues.
Because of the presence of water, the benzene and homologues form a
separate phase, which is separated from the water-methanol phase in
decanter V-203. The benzene-and-homologues stream Is recycled to C-105
for distillation. The methanol-water solution is distilled in C-205 to
recover methanol at the top and water at the bottom. The water is
treated in C-106.
Gas from C-203 Is further compressed in screw compressors to 235
psla (15 bars). The compressed gas is cooled by cooling water in E-205
and a refrigerant In E-206, to OoP. It is then scrubbed by chilled
octane in C-206. All hydrocarbons with more than 3 carbons, Including
a little methylacetylene, which is the one higher acetylene that may
185
have escaped complete absorption in C-203, are dissolved by octane. A
little acetylene is also dissolved. The solution from C-206 is re-
leased in pressure in C-207, and stripped by a crude hydrogen stream
(22). The gas from C-207, containing some acetylene and some C3+ hydro-
carbons, is recycled to the inlet of K-201. The solution from C-207,
thus freed of acetylene, is heated in exchangers and then stripped by
gas in C-208. The gas used for stripping is an off-gas stream (24) and
a crude hydrogen stream (47), in a total molal quantity sufficient to
boll octane and to evaporate all dissolved C3+ hydrocarbons at a temper-
ature of about 182*F maintained by a reboiler. The vapor leaving at
the top of C-208 Is chilled by a refrigerant in E-211; the condensate
(mainly octane) is refluxed. The gas, consisting of C3+ hydrocarbons,
is recycled to the reactors. The stream from the bottom of C-208 is
octane. It is cooled in exchangers (giving up heat to the feed to
C-208), boosted to 235 psia, further chilled by refrigerant to -4oOF,
and recycled to C-206 for absorption.
About 3% of the octane Is withdrawn and treated with hydrogen
under 200 psia in a fixed catalyst bed in V-206 to remove any accumu-
lated unsaturated compounds. Gas and liquid are separated in V-207.
Gas is recycled to the inlet of K-203. The liquid from C-208 contacts
active carbon In V-208 and returns to the circulation. The purpose of
treatment by active carbon is to remove any heavy oil formed during
hydrogenation ("green oil," as it is called in the ethylene industry).
The amount of green oil is so trivial that the carbon in V-208 may be
used without regeneration for a year or so and then discarded.
Gas from C-206 is essentially a mixture of hydrogen, methane,
acetylene, ethylene, ethane, carbon monoxide, and nitrogen. The small
amount of octane is removed by scrubbing with methanol in C-209. The
methanol from C-209 is used for scrubbing in C-203. Any octane thus
carried over eventually appears in stream 15, and becomes a component
in the absorbent oil.
Gas from C-209 is then scrubbed by a solvent consisting of 85%
N-methylpyrrolidone (NMP) and 15% methanol in C-210 for absorption of
186
-
a -
a
acetylene. The solution containing acetylene is released in pressure
and enters C-211, where a stream of pure acetylene gas enters at the
bottom, and a stream of chilled methanol flows down from the top. The
column bottom is heated to 32OF by recycled methanol liquid. The
column top is chilled by refrigerant to -4OOF. In this way, any
ethylene dissolved in NW-methanol is stripped and recycled to the
inlet of compressor K-201, while all but a very small amount of the
acetylene is kept in solution. The solution, now practically contain-
ing only acetylene, is heated in exchanger E-217, and flashed in C-212
to separate part of the acetylene. The solution is further heated in
exchanger E-218 and the acetylene is desorbed in column C-213, which is
heated by a reboiler at the bottom. Because of a water-cooled coil at
the top of the column and a cooled reflux stream entering the top of
the column, the acetylene vapor leaving the top of C-213 contains only
a small quantity of methanol. The vapor is driven by a blower. Part
of it goes to C-211 for stripping of ethylene; the balance is cooled in
exchanger E-220 and cooler E-221 to condense the methanol, which is
recycled to C-213. The acetylene gas, warmed in E-220, becomes the
plant product.
A small part of the solvent is distilled in C-214 to recover
methanol at the top, and NMP near the bottom. The bottom stream is
evaporated in scraped-surface evaporator M-201 to recover the remaining
NMP; the residue is incinerated.
Gas from C-210 is essentially a mixture of hydrogen, methane,
ethylene, ethane, carbon monoxide, and nitrogen, with traces of pro-
pane, propylene, carbon dioxide, and methanol. The last two compounds
would cause trouble in the separation of ethylene by freezing; hence
they are removed by adsorption with molecular sieves in V-301. The
molecular sieves are regenerated by the following successive proce-
dures: blowing down to a pressure of 30 psia, injecting a small stream
of hot off-gas (heated by electricity) until the molecular sieves reach
4700F, and admitting cold off-gas until the temperature drops to 12OoF.
187
The gas from V-301, now free of carbon dioxide and methanol, is
compressed by K-301 to 400 psia and cooled by refrigerants in E-301 and
E-302, ultimately to -1200F. In E-303, the temperature is further
reduced to -280°F. At this point, practically all the ethylene and
ethane, and a substantial part of the methane condense to a liquid,
which is separated from the gas in V-302. The liquid is fractionated
in demethanlzer C-302 to produce liquid ethylene and ethane at the
bottom, and a vapor containing methane, CO, Hz, and N2 at the top. The
vapor is expanded from 395 psia to 25 psia, with recovery of power.
The expanded gas at -294OF is used in E-303 as a refrigerant, and then
further used as a refrigerant in C-202 and C-201. Finally, it is used
as a stripping agent in C-204 and C-208.
The liquid from C-301, ethylene containing ethane and a trace of
methane, is fractionated in C-2 splitter C-302. A small stream is
taken overhead and blended with the methane stream to form stream 24,
used for stripping in C-208. Ethylene is withdrawn at the middle-upper
part of the column. It is collected in V-306, and pumped through coils
in C-201 as a refrigerant, and then piped as a by-pro+ct. Leaving the
bottom of C-302 is ethane containing a little ethylene and a trace of
C3's; it is recycled to the reactors.
The gas separated in V-302 is an impure hydrogen at -280OF. It is
used as a refrigerant, first in E-303, then in C-202. At this point
stream 22 is withdrawn, to be used as a stripping agent in C-207. The
main stresm is further used as a refrigerant, in C-201. Then part of
it is used as a stripping agent in C-208. The balance of the gas is
treated in a set of pressure-swing adsorbers, Pat-301, for separation
into pure hydrogen and an off-gas. (For details on the pressure-swing
adsorber, refer to PEP Report 123.) A small part of the pure hydrogen
is used for hydrogenation in V-206; the main part, stream 45, is a
by-product.
The -150°F and -lOOoF refrigerants are ethylene at 15 psia and 60
psia. The refrigerants at -5OoF, -lOoF, and 50oF are propylene at 10
psia, 40 psia, and 113 psia.
188
Process Discussion
As shown in Table 8.3, each reactor is provided with a duplicate
spare, connected to the same set of rectifier units. This would facili-
tate changing the anodes every 200-300 hours, and the cathodes every
1,000 hours. The alternative of providing one spare reactor for the
six trains, and having it connectable at will to any one of the six
rectifiers, is difficult to arrange physically.
In Huels' operation, the cracked gas is compressed from 14.7 psia
to 117.6 psia in three stages. We used two stage compression because
we believe an exit temperature of 125OF is tolerable.
In the design case, the methane stream from the demethanizer is
all used for stripping and is eventually recycled to the reactors.
Crude hydrogen separated from liquid Cl-2 hydrocarbons is used for
stripping, only to the extent of supplementing the methane gas; the
main part is recovered as pure hydrogen. Such an arrangement, aimed at
enhancing the value of the by-products, is possible because the use of
natural gas as feedstock does not require high recycling of hydrogen.
As a refrigerant at -SOoF and higher, ammonia can be used instead
of propylene.
The separation of ethylene can be effected at a pressure lower
than 400 psia, but methane refrigerant has to be used.
Cost Estimates
The estimated capital investment and production cost are given in
Tables 8.5 and 8.6. Production costs and production values at differ-
ent operation levels are given in Figure 8.2.
According to Huels' experience, carbon black recovered in this
process is suitable for the rubber industry. Presumably some treatment
is necessary. We credited it at 60% of the market price of rubber-
grade carbon black.
A hydrogen credit of 56.2c/lb ($3.13/1,000 scf or llc/Nm3) is
reasonable for the pure gas. Hydrogen produced by partial oxidation of
189
Battery limitm equipme. f.o.b.
%actorc CO1mIU Verrclr md twkm Exc~~rr mrwcw cwpnwora lltr~llmmour equipwnt
-Pa
rota1
Rwwrcwi~ abwrbw
Battety IfdtB equipment inrtalled
Conti~cnty. 252
DAfTEM LIMITS INVESl?lEST
Off-ait.,, ioat8lled
Coolinp tarr StW. BWWLtiW
Tmk*~*
Utilities ati ltm~c
ci!ncral YrviCC faellftier uwte trwtwllt Total
Coatirqwcy. 25Z
OFF-SITES INVESlMlNI
TOTAL PIZCD CAPITAL
Rcs~ure-svlng abwcber
I*ttery limitm cqulpcnt Inmtalled
CmtIngmncy. 252
BATTIIRY LIMITS INVESlMENI
Table 8.5
ACETYLENE FROM NATURAL GAS BY ARC PROCESS
CAPITAL INVESTMENT
Plant capacity: 100 Milllon lb/yr (45.000 Metric Tons/yr) Acetylene
at 0.90 stream Factor
PEP Cost Index: 360
Total capacity Fapownt
cost J&L- -
8 2.700.000 1.64s.300 1,9a4,200 2.487.7W
w).m 6.656.100
342.000
235.200
$16,1O4,WO 0.77 0.67
1.245.6OO
561.166,WO
15.295.000
$76.419.W0 0.72 0.62
799,wo a33.200 104.6W
S 1.736.WO 0.79 0.67
12.5ao.000 3.145.000
$1?.461,OW
4.365.000
$21.a26.w0 0.73 0.63
698.284.000 0.73 0.63
Ethylene Recovery w=itY ,bQOn+nt
cost JL Dovn
S -- - -- 463,CW 0.86 0.71 203.3W 0.65 0.64
1,389,9w 0.69 0.65 -- -- --
263.900 0.76 0.76 64.1100 0.70 0.70
23.800 0.28 0.20
$2.429.100 0.73 0.67
-- -- -
$7,016,000 - -
1.755,wo -- -
ss,773,wcl 0.70 0.63
$ 2.7OO.OW 733,900
1,191,100 249.500 50,500 lao,ow 111.600 66,700
$ 5.703.7w
1.245.600
422.830.000
5.208.000
$28.538,000
0.60 0.60
::Ei 8::‘: o.a5 O.Sl 0.79 0.79 0.60 0.60 0.95 0.95 - --
0.70 0.65
0.60 0.60
- -
- -
0.63 0.58
61.000 0.76 0.55 -- - -
104.6W 0.60 0.35
S 166,OW 0.66 0.42
6 -
72,200 97,ow
--
3.100,000
--
$ 3,349,2W
s13.479,ow
3.37o.ow
516.a49.wo
- - -- -
0.59 0.58 0.70 0.54 I --
0.85 0.76 -- --
0.64 0.75
- --
- --
0.78 0.70
Acetylene Rccovcry m=ity Exponent
-l!ri Co*t E!!E
6 --
431,wo 117.200 751.300
3.032.2W 165.6OO 124.700
$ 4.622.000
617.S46.OW
4.462.000
522.309.oOO
-- - 0.63 0.50 0.52 0.39 0.66 0.52 - -
0.93 0.75 0.66 0.66 0.44 0.32
0.84 0.66
- --
- -
- -
0.80 0.62
737.000 0.75 0.57
833.200 0.82 0.82 - - --
$ 1.5?0,000 0.79 0.70
a 190
Table 6.6
ACETYLENE FROM NATURAL GAS BY ARC PROCESS
PRODUCTION COSTS
PEP Cost Index: 360
Variable costs
Eaw materials
Natural gas Butanes Scrubbiog oil Octane Methanol N-Methylpyrrolidone
Gross raw materials
By-products
Ethylene Pyrolysis residue Uydrogen Carbon black Pyrolysis gasoline Fuel gas
Total by-products
Utilities
Cooling water Steam Electricity Natural gas
Total utilities
unit cost
9.48cllb 13c/lb W/lb 2Wlb 10.8c/lb $l.lO/lb
24c/lb 4c/lb 56.2c/lb lSc/lb 13.3c/lb 0.4c/l,OOO Btu
Unit Coet
5.25c/l,OOO gal $6.40/1,000 lb 3.24clkwh $4.OO/MM Btu
Consumption/lb c/lb
1.65 lb 15.64 0.72 lb 9.36 0.025 lb 0.20 0.006 lb 0.12 0.013 lb 0.14 0.001 lb 0.11
25.57
-0.306 lb -7.34 -0.05 lb -0.20 -0.301 lb -16.92 -0.3476 lb -5.21 -0.1498 lb -1.99 -4,082 Btu -1.63
-33.29
Consumption/lb Consumption/kg $/lb
21 gal 177 liters 0.11 2.11 lb 2.11 kg 1.35 6.22 kwh 13.7 kwh 20.15 578 Btu 321 kcal 0.23
21.84
191
Table 8.6 (Concluded)
ACETYLENE FBOM NATUBAL CA8 BY AEC PEOCESS
PEODUCTION COSTS
PEP Cost Index: 360
Capacity (million lb&r)*
Investment ($ million) Battery limits Off-sites
Total fixed capital
Scaling exponents
Production costs (C/lb)
Eav materials By-products Utilities
Variable costs
Operating labor, ll/shiftS, $15.40/hr Maintenance labor, 3Xlyr of BL inv Control lab labor, 20% of op labor
Labor costs
Mainteuace materials, 3Xlyr of BL inv Operating supplies, 10% of op labor
Total direct costs
Plant overhead, 80% of labor costs Taxes and insurance, 2%/yr of TFC Depreciation, lO%/yr of TFC
Plant gate cost
GbA, sales, research (5% of sales)
Net production cost
EOI before taxes, 25Xlyr of TFC
Product value
*Of acetylene.
base case.
50 1OOt 300
49.6 14.1
63.7
76.5 21.8
98.3
0.63
169.6 48.7
218.3
0.73
25.57 25.57 25.57 -33.29 -33.29 -33.29 21.84 21.84 21.84
14.12 14.12 14.12
2.70 1.48 0.67 2.98 2.29 1.70 0.54 0.30 0.13
6.22 4.07 2.50
2.98 2.29 1.70 0.27 0.15 0.07
23.59 20.63 18.39
4.97 3.26 2.00 2.55 1.97 1.46 12.74 9.83 7.28
43.85 35.69 29.13
3.00 3.00 3.00
46.85 38.69 32.13
31.85 24.57 18.19
78.70 63.26 50.32
SFor base case only; may be different for other capacities.
192
Figure 8.2
ACETYLENE FROM NATURAL GAS BY ARC PROCESS EFFECT OF OPERATING LEVEL AND PLANT CAPACITY
ON PRODUCTION COST AND PRODUCT VALUE
155
150 r ‘40 t 130 r
\, ‘1
\ 120 ’
110
t-
‘\ 100
7
60
50
E
I I Production Cost
- Product Value
ii%++
0.6 0.7 0.8 0.9
OPERATING LEVEL, fraction of design capacity
1.0
193
residual oil, would cost 50c/lb at the huge capacity of 176 million
lb/yr (refer to PEP Yearbook 1980, p= l-155). However, if there is no
application for hydrogen in the vicinity of the acetylene plant, it
might have to be used as fuel. With the hydrogen credited at 0.4c/
1,000 Btu (equivalent to 20.65c/lb), the production cost and product
value of acetylene would be increased by 7.67c/lb. Adjusting for the
reduction of capital related costs due to the omission of pressure-
swing absorption, the net Increase in production cost would be 7.27c/lb
of acetylene and the net increase in product value would be 6.70c/lb.
Table 8.7 compares the essential numbers in Tables 8.5 and 8.6
with those Huels released to SRI. The materials usages are fairly
consistent, and the discrepancy in the utilities usages and capital
investments is not beyond what would be expected in a preengineering
design. The difference in battery limits investment between SRI's and
Huel's estimates is mainly in the recovery and refrigeration sections.
Also Huels uses a capacity exponent of 0.65 instead of SRI's 0.73,
which leads to a significantly lower investment for a 300 million lb/yr
plant. The labor force estimated by SRI Is based on the U.S. situation
for a newly constructed facility that is highly instrumented and
automated. If Huels' Investment and usages are used instead of SRI's
in Table 8.6, the production cost and product value would be as shown
in the last two lines of Table 8.7. The numbers in parentheses are the
production costs and product values if hydrogen is not separatedeas a
pure gas but is used as fuel.
Use of Other Feedstocks
The above-described arc process can use various hydrocarbons as
feedstock. Huels uses refinery gas and exhaust gases from various
units in the complex. With the addition of a vaporizer, liquid hydro-
carbons (such as naphtha and butanes) can be used as feedstock. The
yields and usages change with the feedstock. Hue18 has released some
data on using butanes as feedstock. These data are also given in Table
8.7, along with the production cost and product value we calculated on
these bases.
194
Table 8.7
l COMPARISON OF SRI'S EVALUATIOIN WITH HUELS DATA
Plant capacity:
-
-
IIsterials ussge (lb/lb scetylene) N8tureI gsr Butsner Scrubbing oil N8thsno1 c&an8 lm
1.65 1.63 (mathsne) 0.72 0.72 0.025 0.025 0.013 0.013 0.006 0.006 0.001 ht &TCnl
2.45 0.020 0.010 0.005 not given
By-productr (lb/lb acetylene) Bthylene Hpdroa- C8rbun bl8ck PyrOly818 g88OliIm Pyrolyrir reridue Fuel 888 (Mu/lb)
0.306 0.30 0.48 0.301 0.301 0.188 0.3476 0.35 0.41 0.1498 0.15 0.13 0.05 0.05 0.04 4.082 4.049 4.049
Utilitie8 wage (par lb acetylene) lSlectricity (kwh) 8tmm (lb) C001illg wter (gal)
6.22 6.32 5.41 2.11 4.1 4.3 21 7.2 6.6
Lsbor Norkerrlrhfft 11 15* 15*
86tt8ty limit8 ilWe8hallt (dlliOll a$)* 76 71 69
Fruduction cost ($/lb acetylene) 38.5 (45.2) 39.5 (46.2) 41.5 (48.2)
Product vslua (c/lb acetylene) 63.0 (69.7) 61.6 (68.3) 63.0 (69.7)
*Converted fror data for a larger plant.
hcludiag 25% contingency.
100 Million lb/yr
y8ed8tOCk Nstural Ges imd C6 SRI hIti8
C4r ihId
195
As shown in Table 8.7, the use of butanes as the feedstock gives a
slightly higher production cost and product value if pure hydrogen is
recovered, but the same production cost and a slightly lower product
value if the hydrogen is not separated. However, this is based on the
assigned unit prices. At different unit prices, the relative merit may
be different.
Possible Improvements in the Process
Huels is now working on two improvements in the arc process. The
first is recovery of the heat of reaction. The second is hydrogenation
of the higher acetylenes before recycling.
The heat recovery can be achieved by using oil quenching instead
of water quenching near the exit of the reactor. Hue18 has a test unit
(8.5 mu). By analogy with the evaluation in Section 7, SRI believes
the net saving might be as much as 6c/lb of acetylene.
The higher acetylenes, on recycling to the reactors, are decom-
posed to carbon and hydrogen. By hydrogenating them to saturated
hydrocarbons or olef ins and then recycling, soxe acetylene is produced
therefrom. The difference between the value of the additional acetyl-
ene produced and the reduced by-production of hydrogen and carbon black
(adjusted for the effects of equipment alterations and increased power
usage) would be the net cost effect.
Arc Process with Simplified Recovery Procedures
As pointed out in Section 6, acetylene recovery procedures are not
inherently related to the acetylene production processes. One may use
the arc process for generating acetylene, and use a recovery process
similar to that used in the BASF partial oxidation process. Indeed,
this is the case in the Rumanian acetylene plant mentioned earlier. In
this plant, methane is used as feed in an arc reactor, presumably with-
out a secondary feed; the resulting gas is treated to remove carbon,
196
and then processed in a way similar to that described in Section 7, to
recover acetylene. The remaining gas (including ethylene, hydrogen,
and other compounds) is credited as fuel. A brief evaluation shows
that such an arrangement would be preferred to the regular procedures
described in the evaluated process, only in a very small operation,
e.g., a plant with one or two burners.
Acetylene from Coal by the Avco Arc Process
The Avco Corporation has successfully cracked coal in a laboratory
arc reactor to obtain a cracked gas containing acetylene. Avco has
erected a 1,000 kw reactor with coal preparation facilities to enable
operation longer than 1 to 2 hours, which is the longest operation
hitherto attained In the laboratory reactor. This facility will be
tested in 1982.
Avco is cooperating with CAP in studying the separation of the
crackhg product. The process, as contemplated by Avco/CAP, is as
follows : Coal, preferably one having a high volatile8 content, is
fluidized in hydrogen (an Impure stream, obtained from the recycle) and
charged into a direct current arc in a reactor. Additional hydrogen is
also recycled to the arc. The reaction takes place immediately below
the arc sane, and is then quenched either by a stream of water or by a
stream of hydrocarbon. The cracked gas is scrubbed to reuove carbon.
Next, it is compressed to 30 psig, and treated with 5% N-methylpyr-
rolidone to absorb H2S and HCN, which are separated by stripping. The
II@ is absorbed in a diethanolamlne solution and eventually converted
to sulfur. The cracked gas is then treated with caustic soda to reuove
coz* Next It is compressed to 210 psig and treated with N-methylpyr-
rolidone in stages to absorb cS2 and then C2H2. In the case of
hydrocarbon quenching, ethylene is next recovered by low temperature
cooling. Finally, the gas undergoes a water-gas shift reaction and a
CO2 absorption. A major part of the gas is recycled; the remainder Is
withdrawn as a by-product.
197
Tables 8.8 and 8.9 are cost estimates based on data supplied by
Avco and <;AF. Table 8.8 Is for water quenching, Table 8.9 for hydro-
carbon quenching. In the estimates, the hydrogen is credited as fuel.
On comparing these results with the costs for the arc process using a
hydrocarbon as feed and hydrogen as a fuel, one sees that the coal arc
process using water quenching gives approximately the same product
value as the methane arc process does, while the coal arc process using
hydrocarbon quenching gives a product value lower by about 6C/lb. How-
ever, it must be kept in mind that the evaluation of the coal arc
process is based on data extrapolated or inferred from laboratory
results; no pilot plant operation from reaction to recovery has been
undertaken yet. According to Huels, who is also developing a coal arc
process, both the capital investment and the power consumption given in
Tables 8.8 and 8.9 are too low.
198
,
Table 8.8
ACETYLENE FROM COAL BY ARC PROCESS USING WATER QUENCHING
PRODUCTION COSTS
PEP Cost Index: 360
Variable costs Unit cost Consumption/lb c/lb
Raw materials
Coal 1.25c/lb 3.3333 lb 4.17 N-Methylpyrrolidone $l.lO/lb 0.0065 lb 0.71 Methanolamine 53c/lb 0.005 lb 0.26 Caustic soda 7.5C/lb 0.0025 lb 0.02 Catalyst et al. 0.33
Gross raw materials 5.49
By-products
Char and carbon black l.ZSc/lb -1.5 lb -1.88 Gee 0.4c/l,OOO Btu -7,193 Btu -2.88 tlydrogen cyanide 37C/lb -0.1 lb -3.70 Carbon dlsulfide 12.8C/lb -0.061 lb -0.78
Total by-products -9.24
Utilities
Cooling water Steam Electricity Inert gae, lo p
Total utilities
unit cost Coneumption/lb Consumption/~ c/lb
5.25~/1,000 gal 60 gal 501 liter6 0.31 $6.40/1,000 lb 5 lb 6kg 3.20 3.24c/kwh 4 8 kwh 10.6 kwh 15.55 70~/1,000 ecf 0:7 scf 44 liter8 0.05
19.11
199
Table 8.8 (Concluded)
ACETYLENE FROM COAL BY ARC PROCESS USING WATER QUENCHING
PRODUCTION COSTS
PEP Cost Index: 360
Capacity (million lb/p)*
Investaent ($ million)
Battery limits Off-sites
Total fixed capital
Scaling exponents
Production costs (c/lb)
Raw materials By-products Utilities
Variable costs
Operating labor, 12/shifte, $15.40/hr Maintenance labor, 3X&r of BL inv Control lab labor, 20% of op labor
Labor costs
Mainteuace materials, 3X/yr of BL inv Operating supplies, 10% of op labor
Total direct costs
Plant overhead, 80% of labor costs Taxes and insurance, 2%/yr of TPC Depreciation, 10X& of TPC
Plant gate cost
GbA, sales, research (5% of sales)
Net production cost
DO1 before taxes, 25%&r of TPC
Product value
*Of acetylene.
bane case.
50
0.50
5.49 5.49 5.49 -9.24 -9.24 -9.24 19.11 19.11 19.11
15.36 15.36 15.36
2.97 1.62 0.72 3.26 2.31 1.62 0.59 0.32 0.14
6.82 4.25 2.48
3.26 2.31 1.62 0.30 0.16 0.07
25.74 22.08 19.53
5.46 3.40 1.99 3.02 2.13 1.50 15.08 10.66 7.50
49.30 38.27 30.52
3.00 3.00 3.00
52.30 41.27 33.52
37.70 26.65 18.75
90.00 67.92 52.27
loot
76.9 29.7
106.6
0.68
300
162.3 62.7
225.0
SFor base case only; may be different for other capacities.
200
Table 8.9
ACETYLENE PROM COAL BY ARC PROCESS USING HYDROCARBON QUENCHING
PRODUCTION COSTS
PEP Cost Index: 360
Variable costs unit cost Consumption/lb c/lb
Raw materials
Coal 1.25cflb 2.5 lb 3.13 N-Mathylpyrrolidone $l.lO/lb 0.01 lb 1.10 Propane %/lb 1 lb 9.00 Diethanolamiue 53c/lb 0.005 lb 0.26 Caustic soda 7.5c/lb 0.0025 lb 0.02 Catalyst et al. 0.33
Gross raw materials 13.84
By-products
' Uydrogen cyanide 37Cllb -0.1 lb -3.70 Ethylene 24c/lb -0.4 lb -9.60 Carbon dieulfide 12.8c/lb -0.0445 lb -0.57 Char and carbon black 1.25c/lb -1.15 lb -1.44 Gas 0.4c/l,OOO Btu -14,200 Btu -5.68
Total by-products -20.99
Utilities
Cooling water Steam Electricity Inert gas, lo p
Total utilities
Unit Cost Consumption/lb Consumption/kg c/lb
5.25c/l,OOO gal 59 gal 491 liters 0.31 $6.40/1,000 lb 5.48 lb 5.48 kg 3.51 3.24c/kwh 3.62 kwh 7.98 kwh 11.73 70c/1,000 scf 0.57 scf 36 liters 0.04
15.59
201
Table 8.9 (Concluded)
ACETYLENE FROM COAL BY ARC PROCRSS USING RTDROCARBON QUENCHING
PRODUCTION COSTS
PEP Cost Index: 360
Cepacity (million lb&)*
Investment ($ million)
Battery limits Off-sites
Total fixed capital
Scaling exponents
Production costs (c/lb)
Raw materials By-products Utilities
Variable costs
Operating labor, 12/shiftS, $15.40/hr Mnintenance labor, 3%/yr of BL inv Control lab labor, 20% of op labor
Labor costs
Maintenace materials, 3%/yr of BL inv Operating supplies, 10% of op labor
Total direct costs
Plant overhead, 80% of labor costs Taxes and insurance, 2%/yr of TFC Depreciation, lO%/yr of TFC
Plant gate cost
GM, sales, research (5% of sales)
Net production cost
ROI before taxes, 25Xlyr of TFC
Product value
*Of acetylene.
base case.
so . 1OOt 300
54.3 76.8 162.1 21.0 29.7 62.7
75.3 106.5 224.8
0.50 0.68
13.84 -20.99 15.59
8.44
2.97 3.26 0.59
6.82
3.26 0.30
18.82
5.46 3.01 15.06
42.35
3.00
45.35
37.65
83.00
SFor base case only; may be different for other capacities.
202
13.84 -20.99 15.59
8.44
1.62 0.72 2.30 1.62 0.32 0.14
4.24 2.48
2.30 1.62 0.16 0.07
15.14 12.61
3.40 1.99 2.13 1.50 10.65 7.49
31.32 23.59
3.00 3.00
34.32 26.59
26.63 18.73
60.95 45.32
13.84 -20.99 15.59
8.44
a
9 ACETYLENE BY THERMAL CRACKING
The Wulff process for making acetylene from naphtha by thermal
cracking was evaluated in PEP Report 16. It was once a very popular
process. Plants using it, however, had problems of high soot formation
and, as the price of naphtha increased, they became uneconomic. Now,
practically all such plants have closed down. Nevertheless, as this
process is based on indirect transfer of heat, an approach fundamen-
tally distinct from the partial oxidation process and the arc process,
we believe that treating it briefly is still worthwhile.
In the Wulff process, the feed hydrocarbon is heated by refractor-
ies which have previously been heated by a combustion gas. The hydro-
carbon is cracked, and then quenched outside of the reactor. Due to
construction constraints, the quenching cannot be as immediate as that
in the partial oxidation process or the arc process. Hence the tend-
ency of soot formation is serious. This is inherent in any process
using indirect heat transfer.
The trouble of soot formation could be alleviated by using a light
feed, i.e., a hydrocarbon containing a high proportion of hydrogen.
However, the indirect heat transfer limits the rate of heat input. For
example, the conversion of methane, which needs high heat energy for
decomposition, is very low (refer to pm 47 of PEP Report 16). Hence
methane cannot be used economically.
Theoretically, the best feed for the Wulff process is ethane or
propane. This has actually been the experience of the trade (private
communication) l Using the basic information given In PEP Report 16, we
evaluated a process for making acetylene by the Wulff process, with
ethane as the raw material. The production costs are shown in Table
9.1. Note that the product value of acetylene at 79c/lb (100 million
lb/yr production) is substantially higher than the product value of
acetylene made by the processes described in Sections 5, 6, and 7.
203
Table 9.1
ACETYLENE FROM ETHANE BY THE WULFF PROCESS
PRODUCTION COSTS
PEP Cost Index: 360
Variable Carte unit Cost Consumption/lb $/lb
gaw materials
Bthane DUP &monSa cauetic lmda Pd catalyst Activatad alumina Flocculent
Gross raw material0
9dlb 3.3 lb 29.70 55C/lb 0.0061 lb 0.34 7.8dlb 0.0027 lb 0.02 llc/lb 0.0028 lb 0.03 950c/lb 0.00011 lb 0.10 16c/lb 0.0025 lb 0.04 $1.70/lb 0.00007 lb 0.01
30.24
By-products
FWl 0.4~/1,000 Btu -2,900 Btu -1.16
Total by-producta -1.16
unit Cost Consumption/lb Consumption/kg c/lb
Utilftie8
Cooling wntet Steam Process water Blectricity
Total utilities
5.25~/1,000 gal 42 gal 350 liter 0.22 $6.40/1,000 lb 14 lb 14 b 8.96 6Oc/l,OOO gal 0.023 gal 0.192 liters - 3.2clkwh 0.057 kwh 0.126 kwh 0.18
9.36
204
Table 9.1 (Concluded)
ACETYLENE F'ROMETHAN% BY THE WULFF PROCESS
PRODUCTION COSTS
PEP Coat Index: 360
Capacity (xillion lb/yt)* 50 loot 300
Investxent ($ million)
Battery lixite Off-sites
Total fixed capital
Scaling exponents
39.3 11.6
50.9
0.68
Production costs (c/lb)
Raw xaterials By-products Utilities
variable caste
Operating labor, 8/shiftS, $15.40 hr Maintenance labor, 3X/yr of BL inv Control lab labor, 20% of op labor
Labor costs
Maintenance materials, 3Xlyr of BL inv Operating supplies, 10% of op labor
Total direct costs
Plant overhead, 80% of labor costs
Taxes and insurance, 2%/yr of TFC
Depreciation, 1OXlyr of TX
Plant gate cost
C6A, sales, research (5% of sales)
Net production cost
ROI before taxes, 25%/yr of TFC
Product value
30.24 30.24 30.24 -1.16 -1.16 -1.16
9.36 9.36 9.36
38.44 38.44 38.44
1.89 1.08 0.45 2.36 1.89 1.42 0.38 0.22 0.09
4.63 3.19 1.96
2.36 1.89 1.42 0.19 0.11 0.04
45.62 43.63 41.86
3.70 2.55 1.57
2.03 1.63 1.22
10.17 8.15 6.12
61.52 55.96 50.77
3.00 3.00 3.00
64.52 58.96 53.77
25.45 20.38 15.31
89.97 79.34 69.08
62.9 141.8 18.6 41.9
81.5 183.7
0.74
*Of acetylene.
base case.
SFor base case only; may be different for other capacities.
205
10 ACETYLENE AS A BY-PRODUCT IN ETHYLENE PRODUCTION
In the conventional ethylene production of ethylene, a small
amount of acetylene (0.5 to 2.5%) occurs as a constituent in the orig-
inal cracked gas. The acetylene is often hydrogenated during puriflca-
tion of the cracked gas, but it can also be recovered. This section
evaluates a scheme for recovery of acetylene in an ethylene plant.
Kureha/UCC developed a cracking process that, when using a heavy
distillate as feed, produces a gas containing substantial quantities of
acetylene but, at optimum operating conditions, ethylene is still the
main product. This process is also briefly evaluated.
Recovery of Acetylene in an Ethylene Plant
Ethylene production by steam cracking of a hydrocarbon is the sub-
ject of PEP Reports 29, 29A, and 29B. The cracked gas, after compres-
sion, caustic scrubbing, further compression, dehydration, and
chilling, is subjected to hydrogenation to convert the acetylene
therein to ethylene. The relevant equipment, as shown in Figure 6.1
(Sheet 5) in Report 29B, is listed here in Table 10.1. (The equipment
numbers are those of the original report.) The usages of utilities are
given in Table 10.2.
If acetylene is to be recovered, the scheme shown in Figure 10.1
should be used instead. The chilled gas Is treated with dimethylform-
amide in column C-101 under a pressure of 370 psig. Practically all
the acetylene, and a small amount of other gases, is absorbed. The IIMF
solution is released to a low pressure (0.7 psig), and stripped by gen-
tle heating in the lower part of column C-102, to remove other gases.
In the upper part of C-102, a stream of dimethylformamide flows down to
absorb the acetylene in the upgoing gas stream. The gas from C-102 is
compressed to 375 psig and recycled to C-101. In this way, the gas
207
Table 10.1
HYDROGENATION OF ACETYLENE
Plant Capacity: 10 Million (4,500 Metric Tons/yr) at 0.90 Stream Factor
lb/yr
-bar Size (bhp) Material of Conetructlon
K-101
g-115 E-117A.B
P-101
T-101
Comprer8or8
Air coeprerror
Beat exch~en
Beed beater Intercoolere
FMnacaB
Air heater
Tanke
Green oil tank
100 Oarbon steel
Area liarbad Material of Conetruction (MM Btu/hr) (aq it) Shell Tubae
18,500 40.10 Carbon rteel ~rhon steel 8,700 ea 4.76 ea Carbon steel Gnrbun steel
Heat-d (m Btu/hr) Naterial of Construction
10.0 cr/Mo wee1
v01uM (gal)
200 Carbon ateel
Vessel0
v-109 Knockout dru 500 V-1OlA.B Acetylene convertare 7,600 ea
Diameter Eelght (ft) (ft)
ColW
C-lo&B AdLdrorbera 4.0 20 ea
Carbon steel Cerbon eteel
Carbon steel
prnps 100 &CtiOD: 2, including 1 operating, 1 spare.
208
a -
a -
a -
a
Table 10.2
HYDROGENATION OF ACETYLENE
UTILITIES SUMMARY
Plant Capacity: 10 Million lb/yr (4,500 Metric Tons/yr) at 0.90 Stream Factor
Average consumption
Cooling water (gpm)
Electricity (kwh)
Natural gas (million Btu/hr)
Peak demand
Cooling water (gpm)
209
Battery Limits Total
380
83
17
460
leaving C-101 is practically free of acetylene, while the DMF solution
from C-102 dissolves practically only acetylene. The DMF solution is
desorbed by heat in C-103. The DMF is recycled. The acetylene from
C-103 is chilled to reflux DMF.
The above scheme Is based mainly on a Monsanto patent (500623),
except that, instead of using pure acetylene from C-103 as the
stripping agent in C-102 as advocated by Monsanto, we use heating as
advocated by Linde (358785). This permits using a smaller recycle
compressor. The process of Lummus (358697) is also quite similar to
that of Monsanto and that of Llnde.
The major equipment for this operation is listed in Table 10.3.
The utilities usages are listed in Table 10.4.
Strictly speaking, there is another difference between the oper-
ations of hydrogenation and absorption. The pressure drop of gas across
the absorption system is smaller than that across the hydrogenation
system; hence to achieve the same pressure in the splitter, the pres-
sure in the absorber can be lower than that in the acetylene con-
verters, and the cracked gas may be compressed to a correspondingly
lower pressure. We neglected this difference in our comparison.
From the data In Tables 10.1 through 10.4, we estimated the capi-
tal investment for the two cases, hydrogenation and acetylene recovery,
as shown in Table 10.5. In this table, the utilities investment is the
same as the investment for these operations in the ethylene plant. The
method of estimation is given in Appendix C. The difference between
the capital investment for acetylene recovery and that for hydrogena-
tion Is considered to be the investment for the production of acety-
lene. The usages of materials and utilities were similarly derived.
From these, the production cost of acetylene was calculated as shown in
Table 10.6.
The product value of this process at 10 million lb/yr is Sic/lb.
It compares favorably with any other process for producing acetylene at
100 million lb/yr or even 300 million lb/yr. Furthermore, in the above
evaluation the capital investment and utilities consumption are all
210
lbdar mm
caPrumor~
x-101 caprumr E-102 capr*mor
B-101 B-102 6-10s 1-104 s-105 B-1oI E-107 L-102 E-109
T-101 T-102
l-101
c-101 c-102 c-103
E!!E hmorbu Stripper-abmorbar Ouorbu
Table 10.3
Plant Capacity: 10 Million lb/yr (4,500 Metric Tons/yr) at 0.60 Stream Factor
MU (bhp)
100 106
70 0.20 120 0.30
2: C.SO 3.20
4w 41,000 z::P, 4,306 2.66 2.m 5.10 11,000 7.60
2,~ 1200.0W
500
oiwtu ri&t (tt) 0
t:: ii 6.0 60
Wrbm *t-l Cuba eta*1
Mataria of Camtruttim Shdl 2abu
Carbon au1 brbn l ad Carbon at-1 Cub0 at**1 Carbon l twl Cub00 aa*1 cubml *ted wrbm mtul Cub00 rtml Carbon mtml Carbon at-1 cuhm am91 Carbon au*1 cubn rtml Carbon at-1 Carbon mtrl hrbm l t**l Carbon wed
mtaia1 Of coouNctioo
cuhm stwl carboa an1
carbon atml
Tab& 10.4
ACBTfUIIWCOlUT1*ETUtLEWPLUI
IJf2LITIEs s-
Plut cmpu1ty: 10 lullion lb/v (4,500 mtric zoulpr) at 0.90 Stru Iactor
Bmttuy Llmitm rota1
211
Table 10.5
ACETYLENE IN ETHYLENE PLANT
CAPITAL INVESTMENT
Plant Capacity: 10 Million (4,500 Metric Tons/yr) at 0.90 Stream Factor PEP Cost Index: 360
lb/yr
Eattcry limits equipment, f.o.b.
ColUWW Verrele and tanks Excbangere Furnacea Coapresaors
-PJ
Total
Battery limltrr equipment inetalled
Contingency, 25%
BATTgRYLIMITSIgVl3sTngm
Off-eitee, installed
Cooling tower Steam generation Refrigeration
Utilitier and storage
General service facilities
Total
Contingency, 25%
OFF-SITES INwSTwBrn
TOTAL FI%EU CAPITAL
liydrogenatlon of Acetylene
Coat
$ 57,700 118,800 509,900 169,700 100,800 2,700
$ 960,000
$3,080,000
770,000
$3,850,000
28,000 --
28,000
672,000
$ 650,000
162,000
812,000
$4,662,000
Capacity Exponent
J!LE!E!
0.76 0.67 0.64 0.64 0.95 0.85 0.82 0.82 0.65 0.65 0.08 0.05
0.85 0.78
0.76 0.69
0.28 0.28
0.28 0.28
0.63 0.55
0.73 0.67
212
-
a -
a -
a
Table 10.5 (Concluded)
ACF.TYLRNRlN BTRYLENE PLANT
CAPITAL INVRSTMENT
Plant Capacity: 10 Million (4,500 Mstrlc Toas/yr) at 0.90 Stream Factor PEP Cost Index: 360
lb/yr
Acetylene By-Produced in Ethylene Plant Difference
Capacity Capacity Exponent Exponent
cost l!L- cost A!LIkwa
Battery limits equipment, f.o.b.
Columns $ 283,600 0.71 0.65 Vessels and tanks 167,800 0.64 0.63 Exchangers 811,100 0.84 0.81 Compressors 155,300 0.76 0.76 Pumps 61,400 0.71 0.60
Total $1,479,000 0.78 0.74
Battery limits equipment Installed $5,071,0OC
Contingency, 25% 1,268.OOO
BATTgRYLIMITS INVESTMRNT $6,339,000 0.71 0.67 $2,489,000 0.63 0.64
Off-sites, Installed
Cooling tower 109,000 0.49 0.32 Steam generation 301,200 0.82 0.82 Refrigeration 836,000 0.60 0.60
Utilities and storage 1,246,OOO 0.64 0.63
General service facilities 1.263.000
Total $2,509,000
Contingency, 25% 627,000
OFF-SITES INVESTNENT $3,136,000 0.65 0.64
TOTAL FIXgD CAPITAL $9,475,000 0.69 0.66 $4,812,000 0.67 0.67
a
213
Table 10.6
ACETYLENE BY-PRODUCED IN ETHYLENE PRODUCTION
Variable Caste
Raw material8
Ethylene Dim catalyst
Gross raw materials
By-products
Hydrogen
Total by-products
Utilities
Cooling water Steam gtectricity Natural gas
Total utilities
PRODUCTION COSTS
PEP Cost Index: 360
unit Coat
24c/lb $l.lO/lb
Coxmuaption/lb $/lb
1 lb 24.00 0.0026 lb 0.29
3.00
27.29
20.6cjlb -0.12 -2.47
-2.47
Unit Coet Consumption/lb Consumption/kg C/lb
5.25c/l,OOO gal 48 gal 396 liters 0.25 $6.40/1,000 lb 8.28 lb 8.28 kg 5.30 3.2c/kuh 1.13 kuh 2.5 kwh 3.63 $4.OO/MM Btu -13,400 Btu -7,445 kcal -5.36
3.82
214
Table 10.6 (Concluded)
-
a
a -
a
ACETYLENE BY-PRODUCED IN ETHYLENE PRODUCTION
Capacity (million lb/yr)* 5 lot 20
PRODUCTION COSTS
I.
PEP Cost Index: 360
Investment ($ million)
Battery limits Off-sites
Total fixed capital
Scaling exponents
Production costs ($/lb)
Baw materials By-products Utilities
Variable costs
Operating labor Maintenance labor, 3X& of BL lnv Control lab labor, 20% of op labor
Labor costs
Maintenance materials, 3X& of BL lnv Operating supplies, 10% of op labor
Total direct costs
Plant overhead, 80% of labor costs
Taxes and insurance, 2%lyr of TFC
Depreciation, lO%lyr of TPC
Plant gate cost
G6A, sales, research (5% of sales)
Net production coat
ROI before taxes, 25%/yr of TFC
Product value
1.6 2.5 3.9 1.4 2.3 3.7
3.0 4.8 7.6
0.67 0.67
27.29 27.29 27.29 -2.47 -2.47 -2.47 3.82 3.82 3.82
28.64 28.64 28.64
Negl Negl ml 0.96 0.75 0.58 Negl Negl Negl
0.96 0.75 0.58
0.96 0.75 0.58 Negl Negl Negl
30.56 30.54 29.80
0.77 0.60 0.46
1.21 0.96 0.76
6.03 4.80 3.82
38.57 36.50 34.84
3.00 3.00 3.00
41.57 39.50 37.84
15.00 12.00 9.50
56.57 51.50 47.34
*Of acetylene.
tBase case.
215
conservatively estimated. Therefore, it may be concluded that the
recovery of acetylene in an ethylene plant is a viable operation.
Linde compared recovery and hydrogenation of acetylene, for this
same production rate of of ethylene (302617). The conclusion was
generally the same as ours: recovery is more economical.
Ethylene and Acetylene from Crude Oil by the Kureha/UCC Process
The Kureha/UCC process for producing ethylene and acetylene
directly from crude oil was evaluated in PEP Review 78/3/l. We have
updated the evaluation, as shown in Table 10.7. Note that the base
capacity is 1,000 million lb/yr ethylene with coproduction of 118
million lb/yr acetylene and the production cost refers to 1 lb ethyl-
ene. With acetylene credited at 50c/lb, the value of ethylene is
26.8c/lb. This number is approximately the product,value of ethylene
from ethane (PEP Yearbook 1980, p. l-121), and lower than the value of
ethylene from naphtha or gas oil. Alternatively, if ethylene is cred-
ited at 24c/lb, which is the present sale price, and is used in the
evaluation of the arc process, the resulting acetylene would have a
product value of 73.7c/lb, much higher than that by the present commer-
cial acetylene process. Thus, the Kureha/UCC process would be econow
ical under more normal circumstances, but is not economical when the
price of ethylene is depressed as it is now.
216
Table 10.7
ETHYLENE BY KUREHA/UCC PROCESS WITH ACETYLENE BY-PRODUCTION
By-products
Acetylene Propylene Cg's Gasoline Puel oil Heavy fuel oil Vacuum residue
Total by-products
PRODUCTION COSTS
PEP Cost Index: 360
Variable costs unit comt Consumption/lb c/lb
Itaw materials
Crude oil 9.4cllb 3.358 lb 31.57 Oryeen 1.5~/lb 1.744 lb 2.62 Catalyst and chemicals 0.70
Gross raw materials 34.89
%/lb 19C/lb 24dlb 14c/lb
4.118 lb -5.90 -0.275 lb -5.22 -0.153 lb -3.67 -0.427 -5.98 -0.442 -3.45 -0.13 -0.87 -0.2 -1.14
-26.23
Utilities
Cooling tatter Steam Electricity
Total utilities
unit Coat Consumption/lb Consumption/kg e/lb
5.25c/l,OOO gal 50 gal 417 liter 0.26 $6.40/1,000 lb 1.62 lb 1.62 kg 1.04 3.2c/kwh 0.046 kwh 0.101 kwh 0.15
1.45
217
Table 10.7 (Concluded)
ETRYLRNR BY RURllRA/UCC PROCESS WITR ACETYLENE BY-PRODUCTION
PRODUCTION COSTS
PEP Cost Index: 360
Capacity (million lb&r)*
Inveetment ($ million)
Battery limits Of f-sites
Total fixed capital
Scaling exponents
Production costs (c/lb)
Raw materials By-products Utilities
Variable costs
Operating labor, ll/shiftg, $15.40 hr Maiuteuauce labor, 3Xlyr of BL inv Control lab labor, 20% of op labor
Labor costs
Mainteuauce materials, 3Xlyr of BL inv Operating supplies, 10% of op labor
Total direct costs
Plant overhead, 80% of labor costs
Taxes and ineurance, 2%/yr of TFC
Depreciation, lO%/yr of TPC
Plant gate cost
G&A, sales, research (5% of sales)
Net production cost
ROI before taxes, 25Xlyr of TPC
Product value
*Of ethylene.
base caee.
500 1,oOOt 2,000
133.6 217.0 352.5 58.5 95.0 154.3
192.1 312.0 506.8
0.70 0.70
34.89 -26.23 1.45
10.11
0.30 0.80 0.06
1.16
0.80 0.03
12.10
0.93
0.77
3.84
17.64
3.00
20.64
9.60
30.24
34.89 -26.23 1.45
10.11
0.15 0.65 0.03
0.83
0.65 0.01
11.60
0.66
0.62
3.12
16.00
3.00
19.00
7.80
26.80
34.89 -26.23 1.45
10.11
0.07 0.53 0.01
0.61
0.53 0.01
11.26
0.49
0.51
2.53
14.79
3.00
17.79
6.33
24.12
SFor base case only; may be different for other capacities.
218
-
a
11 COMPETITIVE POSITION OF ACETTLENE AS A CHEMICAL FEEDSTOCK
In the preparation of some acetylenic chemicals, vie., 1,4-butane-
diol, tetrahydrofuran, pyrrolidone, vinyl ether, vinyl esters other
than vinyl acetate, or acetylenic alcohols, processes starting from
acetylene are the dominant or sometimes the only commercial processes.
Acetylene-based processes for making acetaldehyde and acrylonitrile,
howver, are no longer used , are not likely to be revived, under normal
circumstances. For the manufacture of vinyl chloride, vinyl acetate,
and acrylic acid and its esters, acetylene processes are being used,
but their popularity has been declining in the past decade. This
section examines the competitive position of acetylene in these
applications.
Competitive Position of Acetylene as Against Ethylene or Propylene
For making vinyl chloride and vinyl acetate, acetylene must
canpete with ethylene. For making acrylic acid and its esters,
acetylene must compete with propylene. Table 11.1 lists the capital
investment and product value, as well as the usage of the feedstock
(acetylene, ethylene, or propylene) in the relevant processes. From
these data, SRI has derived the following equations:
For vinyl chloride A = l.lOE + 19 (11.1)
For vinyl acetate A = 1.23E + 18 (11.2)
For acrylic acid or ester A - 1.74P + 10.2 (11.3)
where E is ethylene price
P is propylene price
A is the acetylene price at which the product (VC, VA, acrylic acid or ester) will have a value equal to the value of that made from ethylene or propylene.
219
Table 11.1
MANUFACTURE OF VINYL CHLORIDE, VINYL ACETATE, ACRYLIC ACID BY ACETYLENE PROCESS AND COMPETING PROCESSES
PEP Coat Index: 360
Battery limite ($ million)
Total fired capital ($ lnillioa)
Feedatock usage (lb/lb)
Production coat excluding feedatock (c/lb)
Product value excluding cost of feedstock (c/lb)
Battery limits ($ million)
Total fixed capital ($ million)
Feedatock ueage (lb/lb)
Production tOBt excluding feedatock (c/lb)
Product value excludiog coat of feedetock (C/lb)
Vinyl Chloride, 600 Million lb/yr
Ethylene Proceee Acetylene by Balanced Proceee (b) ChlOrinatiOQ (a)
28.1 58.1
44.8 103.1
0.43 0.475
9.11 14.46
10.61 18.76
Acrvlic Acid. 200 Million 1b;yr
Acetylene Propylene Process (a) Procees (a)
29.3 80.3
64.9 107.4
0.4i6 0.724
16.68 17.75
30.11 25.86
Vinyl Acetate, 300 Million lb/yr
Acetylene Ethylene Proceee (a) Proceee (a)
31.7 41.6
50.4 69.3
0.32 0.393
24.96 32.36
29.16 34.94
Sources: (a) PEP Yearbook 1980, adjusted for capacity change.
(b) PEP Report 109, updated (original data from Duels).
220
At present, the selling price of ethylene is 24c/lb but this is a
depressed price: product value (production cost plus 25% ROI) of ethyl-
ene at 1 billion lb/yr production is 26.8c/lb from ethane-propane, and
33.8C/lb from gas oil (PEP Yearbook 1980). The selling price of pro-
pylene is 19e/lb. We calculated the acetylene prices corresponding to
these prices for ethylene and propylene by equations (11.1) to (11.3).
See Table 11.2.
Table 11.2
PRICE REQUIRED FOR ACETYLENE TO MAKE IT COMPETITIVE WITH ETHYLENE AND PROPYLENE
(c/lb)
Ethylene Price
24 (“lb) 26.8 33.8 ---
For vinyl chloride 45.4 48.5 56.2
For vinyl acetate 47.5 51.0 59.6
For acrylic acid or ester - - -
Propylene Price, 19c/lb
--
Various processes for making acetylene are evaluated in earlier
sections of this .report. Product values by the carbide process, the
partial oxidation process using natural gas as feed (with and without
heat recovery), and the arc process are compared with the numbers in
Table 11.2 in a scale diagram in Figure 11.1. Note that acetylene pro-
duced at 100 million lb/yr generally is not competitive. One exception
is that acetylene by the partial oxidation process with heat recovery
competes with ethylene produced from naphtha and gas oil for making
vinyl acetate , and also (barely) for making vinyl chloride. At 300
million Ib/yr production , acetylene by the partial oxidation process
with no beat recovery and acetylene by the carbide process compete with
ethylene from gas oil or naphtha (in making VA or VC), but not with
ethylene from ethane. Arc process acetylene competes with ethylene
from ethane in VA production, but not in VC production. Acetylene by
221
Figure 11.1
COMPETITIVE POSITION OF ACETYLENE AS AGAINST ETHYLENE OR PROPYLENE
Acetylene Price at which it wilj be competitive with
Ethylene or Propylene Product Value of Acetylene i
Arc, 100
Carbide, 100
Naphtha or Gas Oil Partial Oxidation, Na Heat Recovery, 100
Competitive with Ethylene from
Naphtha or Gas Oil
Competitive with Ethvlene from Ethane
Partial Oxidation, Heat Recovery, 100
Partial Oxidation, No Heat Recovery, 300
Carbide, 300
,
Competitive with @ t- Arc, 300
- Ethylend fr6m Ethane
Competitive with
Ethylene at Mar&et Price
Competitive with
Ethylene at Market Price
Competitive with Propylene for
LEGEND: Acrylic Acid
@For VA
@For VC
Partial Oxidation, H&at Recovery, 300
I I
222
the partial oxidation process with heat recovery, at 300 million lbjyr
production, canpetes with ethylene from any source (in VA and VC manu-
facture). Homver, a 300 million lb/yr acetylene plant is too large
for most vinyl acetate plauts. There has to be captive production of
other acetylene products to sustain the acetylene plant because acety-
lene cannot be piped long distances. None of the processes can produce
acetylene to compete with propylene in acrylic acid manufacture.
The above analysis is based on average conditions. Individual
cases may vary, depending on local cost factors.
The Effect of Oil Price
The preceding analysis is based on a definite set of cost fea-
tures. A change of any cost factor will of course affect the result.
Since the competing feedstock, ethylene or propylene, is an oil
product, the effect of oil price is especially interesting.
We aualyeed the cost of ethylene aud the cost of acetylene by the
partial oxidation process to find the percentage of the sum of oil-
related cost items in the product values. The results are shown in
Table 11.3.
Table 11.3
PERCENTAGE OF OIL-RELATED ITEMS IN PRODUCT VALUE OF ACETYLENE AND ETHYLENE
Acetylene by Partial Oxidation Ethylene
Capacity Without Heat With Heat From From Naphtha (million lb/yr) Recovery Recovery Ethane or Gas Oil
100 40 38 - -
300 46 44 - -
1,000 - - 46 65
223
By further using equation (11.1) and (11.2), it can be seen that,
if theoil price increases, the competitive position of acetylene made
by the partial oxidation process, as against ethylene made from
naphtha, will improve. The competitive position of acetylene at 300
million lb/yr production, as against ethylene made from ethane, will
change little, while that of acetylene at 100 million lb/yr production
will improve slightly. All these changes are relative to the present
position shown in Figure 11.1. Such changes would be minor for an oil
price change of, say, 50% or less. In other uords, the relative
position of acetylene by partial oxidation, as against ethylene, in
Figure 11.1 would not change significantly, if the price change is 50%
or less.
In the above analysis, we have tacitly assumed all oil-related
items increase at same rate. This is approximately correct because the
partial oxidation process uses natural gas, and ethylene is made from
ethane, which is related to natural gas. However, if in the future the
price of natural gas increases drastically because of decontrol, ethyl-
ene then would be more economically produced from gas oil or naphtha.
Acetylene by partial oxidation of naphtha, as shown in Section 5, has a
high cost because of the high usage of naphtha feed. In that situa-
tion, acetylene by the partial oxidation process would become signifi-
cantly less economical than ethylene as a chemical feed.
The effect of oil price on competition with propylene is more
significant. If oil price increases by 36X, acetylene made by partial
oxidation with heat recovery, at 300 million lb/yr production, would be
competitive with propylene for making acrylic acid. For the partial
oxidation process without heat recovery to produce acetylene
competitive with propylene, the oil price has to more than double.
For the arc process and the carbide process, the cost of elec-
tricity is very high and the conventional calculation of making an
arbitrary breakdown of the electricity costs, into a fixed percentage
of oil-related costs, capital-related, costs, etc. (which is valid only
224
for one circumstance of power generation) is not justified. A better
analysis entails treating the price of electricity as a parameter.
Using the data in Table 11.1 and equation (ll.l), as well as the
data in Sections 8 and 5, we constructed Figure 11.2. The lines give
the prices of natural gas and electricity at which acetylene by the
denoted process at the denoted capacity can make vinyl chloride with a
product value the same as the product value of vinyl chloride made from
ethylene that in turn is made from ethane. Any point below the line
represents gas and electricity prices at which the acetylene process
for making vinyl chloride gives a lower product value. Any point above
the line represents gas and electricity prices at which the acetylene
process would be noncompetitive.
P in Figure 11.2 represents the present basis of 9.48c/lb and
3.2c/kwh. Pa represents the future trend line, if the price of elec-
tricity increases at 10% of the rate of increase of the gas price; Pb
represents the trend line if the electricity increases at 50% of the
rate of Increase of the gas price. The actual trend line will vary
with the source of energy for electricity generation (oil-fired, coal-
fired, hydro, or nuclear) and other factors. Figure 11.2 shows that
both the arc process and the carbide process at 300 million lb/yr
production will become competitive in the near future, with a slight
increase of gas price. At 100 million lb/yr production, both the arc
process and the carbide process will become competitive only if the
trend line is fairly flat (i.e., the electricity rate increases slowly
as the gas price increases), and at a gas price much beyond double the
present price.
Figure 11.3 similarly depicts the competitive position of acetyl-
ene for vinyl acetate manufacture. In this case, acetylene from the
arc process at 300 million lb/yr 1s already more econanic than ethylene
from ethane. (But, as noted earlier, a 300 million lb/yr acetylene
plant is too large for most vinyl acetate plants.) The carbide process
at 300 million lb/yr production will become competitive if the gas
price increases slightly. There is a good prospect that the two
225
0
RA
TE
OF
E
LE
CT
RIC
ITY
, *h
4 h)
o
- P
I I
I I
I I
I I
I I
I I
I I
I I
I I.
1 I
I I
\ \ 9)
I I
I I
I I
I I
I I
I I
I I
I I
I I
I I
I I
Figure 11.3
COMPETITIVE POSITION OF ACETYLENE FOR VA MANUFACTURE AGAINST ETHYLENE FROM ETHANOL
,b
1 I I I I I I I 1 I I I I I I I I I 1
0 10 20 30
PRlCE OF NATURAL GAS, C/lb
227
acetylene processes at 100 million lb/yr capacity will be economic as
the gas price increases.
In the above analysis, the arc process uses natural gas as feed.
The process can use any hydrocarbon gas feed, as long as it can be
easily vaporized, with only minor effect on the economies (see Section
819 If the natural gas is decontrolled and its price increases draeti-
tally, the most economic feed for the arc process might be some C-4
fraction from a refinery (such as n-butane, or raffinate from butadiene
extraction). Since such a fraction is derived from petroleum, just as
is the naphtha or the gas oil used in ethylene production, the remerka
made before on the effect of natural gas decontrol on the partial oxida-
tion process do not apply here. In other words, the analysis on the
effect of the prices of oil and electricity on the arc process uould
not ba affected by the decontrol of natural gas.
Figure 11.4 depicts the competitive position of acetylene for
acrylic acid manufacture, as against propylene. Neither the arc pro-
.ceea nor the carbide process IS competitive. Only if the trend line is
. 'relatively flat, (i.e., the electricity price increases much slower
then the gas price) will the processes may become competitive.
-
By forecasting the price of gas and electricity, we can predict
the competitive position of acetylene.
228
Figure 11.4
COMPETITIVE POSITION OF ACETYLENE FOR ACRYLlC ACID MANUFACTURE
I I I I I I I I I I I I I I I I b I 1 .
a c-
I
10 20 30
PRICE OF PROPYLENE, C/lb
229
Appendix A
DESIGN AND COST BASIS l Design Conditions
Design calculations were based on the general assumption of a
location at Houston, Texas. Particular assumptions were:
Dry bulb air temperature lOoOF (380C)
Wet bulk air temperature 800F (270C)
Ground water temperature 800F (270C)
Cooling water temperature 850F (300C)
Cooling water range A2OoF (AlloC)
a -
a -
a
Cost Basis
Capital Investment
Equipment costs were estimated primarily from correlations In the
literature, but the costs of special equipment items were obtained from
vendors l Where necessary, these costs were corrected to a PEP Cost
Index of 360.
Direct costs In battery limits capital investment were calculated
by the method of Hirsch and Glazier (289). Indirect costs in capital
investment were about 35%-40X of direct costs* Investment in utilities
was computed for the entire plant and allocated to each major operation
according to use. General service facilities not directly associated
with process operations were assumed to be 20% of total of battery
limits plus utilities and storage investment.
Production Costs
Operating labor wages were based on those estimated to be the pre-
vailing rates in Houston, Texas. The effective rate at $15.40 per hour
231
was derived from U.S. national average rates in industrial chemical
plants, corrected to the Houston area on a relative basis for produc-
tion workers, adjusted to include fringe benefits, shift overlap, work-
ing foremen, and average overtime and shift premimum. The operating
labor requirements were estimated subjectively on the basis of the
number of major equipment items in the process.
Unltiss stated otherwise in the text, total maintenance costs were
assumed ‘to be 6Xlyr of battery limits investment. In each case, a
50-50 split between inaterials and labor was also assumed.
The major rati ‘materials costs and the value or price of most of
the other materials were based on listed ‘market prices (either pub-
lished or obtained from sales representatives).
Plant overhead was arbitrarily assumed to be 80% of total labor.
It includes all staff personnel located at the plant site and services
directly associated with operations and maintenance.
The cost of G&A, sales (including technical eervice), and research
was calculated ai a 5% of sales.
The cost of taxes and Insurance was calculated on the basis of
2Xlyr of fixed capital. Depreciation was based on lO%/yr of fixed capi-
tal. The charges for utilities exclude depreciation. Refrigeration,
when used, was charged to the operating cost as cooling water and
power.
232
Appendix B
PHYSICAL PROPERTIES
Properties of Higher Acetylenes (302535)
BP (oC) (OC) HP
Vapor Pressure at -8oOC (MM Hg)
Hcthylacetylene -27.5
Ethylacetylene 8.5
Vinylacetylene 5.5
Macetylene 9.5
I4thyldiacetylene 55
Ethyldiacetylene 87
Triacetylene 70-80
Phenylacetylene 143
-104.7
-137
-36
K-80
<-80
>o
-46
40
Crrl
1.3
-0.5
<O.l
X0.1
X0.01
233
Solubllity of Acetylene in Methanol (g/kgk (B 43, p 91; 302621)
Total Pressure (atn) Temp (oC) 3.9 6.8 9.7 12.6 ----
10 80.3 141.7 211 306
0 122.4 208 306 390
-10 170 271 427 573
At 200 to -3OW and pressure 59 atm or r-10oC and pressure 519 atm, the
relationship is as follows:
log a, = A/T - B
where cr is solubility in standard cu m per cu m, T is temperature in OK
and A and B are as follows:
P (atm)
0.5
1
3
5
7
9
11
13
15
17
19
A B
950 2.48
975 2.27
1000 1.93
1020 1.80
1060 1.80
1100 1.80
1120 1.76
1200 1.96
1250 2.07
1350 2.35
1420 2.51
234
a
l
Benzene-Methanol System (B-44, p. 11137)
Solubillty A (mol%) A
0.00
4.93
7.07
9.86
13.67
16.45
19.39
22.98
27.18
31.00
36.67
42.56
49.39
57.32
63.08
75.00
84.22
92.16
100.0
B
100.0
95.07
92.93
90.14
86.33
83.55
80.16
77.02
72.82
69.00
63.33
57.43
50.61
42.68
36.92
25.00
15.78
7.84
0.00
Mp
-94.0
-67.0
-46.0
-23.0
-17.0
-11.5
-9.7
-7.6
-4.9
-3.2
-1.35
-0.1
1.4
1.85
2.10
2.40
3.00
3.25
5.40
Solublllty of Gases la N-methylpyrrolidone
8ee Figure B.l.
More data in B-45, B.1. pp. 117-169; 302620.
235
Appendix C
ESTIMATING INVESTMENT FOR INCREMENTAL UTILITIES
Sometimes it is necessary to evaluate a small part of a large oper-
ation, such as the case of the treatment of acetylene in an ethylene
plant in Section 10 of this report. If one estimates the utilities in-
vestment on the basis of the utilities usage, the result may be out-
rageously wrong. A precise, but tedious procedure is to estimate the
utilities costs both with and without this part, and take the differ
ence. The following formula derived from the above principle makes the
calculation very simple:
a where C is the capital Investment for a plant with utilities requlre-
ment A, AC is the Incremental investment for the part of the plant with
utilities requirement AA, and n la the capacity exponent of the capital
investment of that particular utility item.
237
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302066
302069
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Sennewald, K., et al., (to Knapsack), "Recovery of Acetylene from Gas Mixtures," US 3,642,929 (Feb. 15, 1972)
Oleszko, T. J., et al. (to Warathon Oil), "Pyrolysis Furnace and Baffle Means," US 3,649,212 (March 14, 1972)
Oleszko, T. J., et al. (to Marathon Oil), "Quenching Process for Pyrolytically Cracked Hydrocarbons," US 3,674,890 (July 4. 1972)
BASF, "Production of Acetylene," British 1,289,757 (Sept. 20, 1972)
Brunner, E., et al. (to BASF), "Production of Acetylene," US 3,686,344 (Aug. 22, 1972)
Maniero, D. A., et al. (to Westinghouse Electric), "Production of Acetylene with an Arc Heater," US 3,697,612 (Oct. 10, 1972)
Lindstrom, 0. B., "Pyrolysis of Eydrocarbons," US 3,704,332 (Nov. 28, 1972)
Walker, L. P. (to Warathon Oil), "Pyrolysis Furnace Having Transverse Mixing Weans in the End Stacks," US 3,723,067 (March 27, 1973)
Luetaelschwab. W. E. (to Warathon Oil), "Furnace Having Cyclically Waving Flames," US 3,721,728 (Warch 20, 1973)
Busch B., et al. (to BASF), 'Process for Smooth Operation of Burner in Production of Acetylene-Containing Gas," US 3'689,586 (Sept. 5. 1972)
Billi. W. (to Wontecatini), "Process and Device for Quenching and Removing Tars and Carbon Black from a Pyrolysis Gas Obtained in the Production of Acetylene," US 3.315.005 (April 18, 1967)
Societe Belge de 1'Aaote et des Produits Chimiques, "Purification of Pyrolysis Gas," British 1,013,509 (July 7, 1964)
Woskovsky Inetitut Tonkoi Khimicheakoi Tekhnologii Imeni MV Lomonosova, 'Reactor," French 1.530.871 (July 17, 1968)
Kandler, J., et al. (to Knapsack), "Purification of Crude Gas Obtained by Thermal Arc Splitting of Hydrocarbons,' US 3,283,026 (Nov. 1, 1966)
Sennewald, K., et al. (to ICnapsack), 'Process for Cracking Hydrocarbons with an Electric Arc,” US 3.377.402 (April 9, 1968)
Sennewald, If.. et al. (to Knapsack), "Process and Apparatus for Cracking Hydrocarbons with an Electric Arc,” US 3.409.695 (Nov. 5, 1968)
Minieterul Industriei Petrolului SI Chimiei, British 1.041.943 (Sept. 7, 1966)
"Reactor for the Manufacture of Alkvnes,"
241
302086 Khudyakov, G. N., et al. (to Energetichesky Institut Imeni G.M. Krzhizhanovekogo), "Improvements in or Relating to Methods of and Apparatus for Producing Acetylene from Natural Gas," British 1,146,090 (March 19, 1969)
302088 Hoechst, "Hydrocarbon Cracking," German 1.250.424 (Sept. 21, 1967)
302091 Duembgen, G., et al. (to BASF), "Process for Removing Carbon Dioxide from Acetylene,” US 3,775.507 (Nov. 27, 1973)
302092 Finn, J. M., Jr., et al. (to Union Carbide), "Electrolytic Preparation of Calcium Car- bide," US 2.952,591 (Sept. 13, 1960)
302093 Krause, J., et al. (to Knapsack), “Installation for Cooling Calcium Carbide Run Off In- to Vessels," US 3,741,414 (June 26, 1973)
302096 Granier, L. F., "Manufacture of Calcium Carbide with the Carbon Extracted from the Carbon Dioxide Proceeding from Combustion Furnaces,” French Addition 52,308 (Feb. 1, 1944)
302098 Hamprecht, G., et al. (to BASF), "Method of Carrying Out Eigh Temperature Reactions in Shaft Furnaces," US 2,863,730 (Dec. 9, 1958)
302099 Neubauer, J. A., et al. (to Columbia-Southern Chemical), "Process for Waking Sodium Carbonate and Acetylene," US 2.845'329 (July 29, 1958)
302101 Gutoff, E. B. (to Ionics), "Production of Acetylene," British 979,717 (Jan. 6, 1965)
302102 Kirsebom. G. 19.. "Improved Process for the Production of Wagnesium," British 922,300 (Narch 27, 1963)
302103 Rummel, R., "Gasification of Fuels and Decomposition of Gases," British 841,569 (July 20, 1960)
302104 BASF, "ImproveaKnte in the Production of Calcium Carbide," British 700,123 (Nov. 25, 1953)
302106 Van Loon, W. (to Stamicarbon), "Furnace Suitable for Use in Performing Reduction Pro- cesses at High Temperatures," US 2,814.478 (Nov. 26, 1957)
302107 Eastman, D. B. (to Texaco), "Calcium-Carbide Process," US 3.017.259 (Jan. 16. 1962)
302108 Atwell, H. V. (to Texaco), "Oxy-Thermal Process," US 3,017,244 (Jan. 16, 1962)
302109 Sage. B. 8. (to Texaco), "Calcium Carbide Process," US 3.044.858 (July 17, 1962)
302110 Wacker-Chemie, "Process for the Manufacture of Calcium Carbide," British 776,271 (June 5, 1957)
302112 Okada, G., et al. (to Kokusaku Pulp), "Acetylene," Japanese 30-2283 (April 5, 1955)
302113 Ruosch, S., et al., "Process for Production of Calcium Carbide," German 1,203,743 (Oct. 28, 1965)
302115 Artyukhov, I. n., "Bigh-Temperature Conversion of Hydrocarbons," USSR 132,352 (Oct. 5, 1960)
302118 Enya, R., "A Method of and Apparatus for Waking Calcium Carbide," British 1.298'545 (Dec. 6, 1972)
302119 Kramer, L., et al., "Limitation of Coke Formation in the Pyrolysis of Hydrocarbons to Acetylene and Hydrogen," French 2,172,148 (Sept. 28, 1973)
302120 Oleszko, T. J.. et al. (to Marathon Oil), "Quenching Process for Pyrolytically Cracked Hydrocarbons," US 3.793'389 (Feb. 19. 1974)
242
302121
302122
302123
302131
302133
302136
302138
302142
302144
302151
302152
302154
302157
302158
302159
302160
302161
302162
302163
302164
302165
302166
302167
Gunther, K., et al. (to Hoechst), "Process for the Separation of Impurities from Crude Gas," US 3.710,545 (Jan. 16, 1973)
Starzeiski. B. R., et al. (to Marathon Oil), "Combined Wulff Process and Coking Process," US 3,796,768 (March 12, 1974)
Lummus “A Process for the Separation and Purification of High Purity Acetylene," British 1,346,033 (Feb. 6, 1974)
Mogensen, P., et al. (to AGA), "Arrangeasnt in a Reactor for Plasma-Chemical Processes," US 3,891,562 (June 24, 1975)
Lewis, J. D., "Separation of Acetylene from Ethylene-Bearing Gases," US 3,837,144 (Sept. 24, 1974)
Albright, C. W., et al. (to Union Carbide), "Process for Cracking," US 3,959,401 (May 25, 1976)
Fey, H. G., et al. (to Westinghouse Electric), “Process for Converting Naturally Occur- ing Hydrocarbon Fuels into Gaseous Products by an Arc Heater"' US 4.010.090 (March 1, 1977)
Shevchuk, V. U., et al., "Method of Producing Acetylene"' British 1,472,739 WY 4. 1977)
Ibberson. V. J., "Plasma Jet Reactor Design for Hydrocarbon Processing," Trans. Inst. chew Eng., 54, 4 (1976). 265-75
Shevchuk, V. U., et al., “A Reactor for Use in the Production of Acetylene from Hydro- carbons.” British 1,482,975 (Aug. 17, 1977)
Krueger, B. 0. (to Borden), "Removal of Oxygen from Gas Stream with Copper Catalyst," US 4.034.062 (July 5, 1977)
Donsi. G., et al., "Fluid Bed Quenching of Premixed Methane - Oxygen Flames," Ins. Fuel Symp. Ser. (1975), London
Fey, M. G., "Arc Water Pyrolysis of Hydrocarbons," paper presented at the 88th National Meeting of the AIChE, June 8-12, 1980, Philadelphia, PA, No. 35C
BASF, "Acetylene-Containing Gas," French 1.487.875 (July 7, 1967)
BASF, "Control of C2H2 Manufacture," Belgian 715,322 (May 20, 1967)
Esso Research 6 Engineering, "Flm Characteristics,” Belgian 689,144 (Nov. 1, 1965)
Chepos Zavody Chemick - Eko A Potravinarskeho Strojirenstvi Brno Oborovy Podnik, "Pyrolytic Process," French 1,555,656 (Jan. 31. 1969)
Ganz, S. N., et al. "Acetylene," USSR 254,505 (Oct. 17, 1969) (Abstract)
Claude, G. (to S.A. Pour L'Etude et L'gxploltation des Procedes George6 Claude), "Crack- ing Hydrocarbons, " French Addition 89,711 (Aug. 4, 1967)
Claude, G. (to S.A. Pour L'Etude et L'Exploitation des Procedes Gaorges Claude), "Crack- ing Hydrocarbons," French 1.444.021 (May 23, 1966)
Vickers-Eiwer, "Reactor Furnace," German 1.281.406 (Oct. 31, 1968)
Bjornsou. G. (to Phillips Petroleum), "Method and Apparatus for Performing Chemical Re- actions by Means of an Electric Arc,” US 3.376'211 (April 2, 1968)
Hoechst, "High Temperature Treatment of Hydrocarbons," US 1,141,909 (Feb. 5, 1969)
243
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302203
302204
302205
302206
302207
302208
302209
302210
302211
302212
302214'
302215
302216
302217
302218
302220
302222
302223
302225
302227
Solvay, "Production of Acetylene," British 1,142.559 (Feb. 12, 1969)
Buschmann, K., et al. (to BASF), "Production of Acetylene," US 3.287.435 (Nov. 22, 1966)
Teltechik, W. (to BASF), "Production of Acetylene," US 3,255,270 (June 7, 1966)
BASF, "Apparatus for Autothermal Flamelees Cracking of Hydrocarbons," British 1,141,888 (Feb. 5, 1969)
Keckler, D. P., et al. (to Diamond Alkali), "Process for the Production of Acetylene," US 3.338.984 (Aug. 29, 1967)
Loeffler, J. E., Jr., et al. (to Diamond Alkali), "Cooling Chamber Design," US 3,285,707 (Nov. 15, 1966)
Dollinger, R. E., et al. (to Phillips Petroleum), "Heat Recovery in Thermal Conversion Process," US 3,347,949 (Oct. 17, 1967)
Knapp, S. L. (to Monsanto), "Process and Apparatus for Partial Combustion of Hydrocar- bons," US 3,399,245 (Aug. 27, 1968)
Braconier, F. F. A., et al. (to Societe Belge de 1'Asote et des Produits Chimiquee), "Solid Metal Block Reaction Furnace for Treatment of Hydrocarbons," US 3,121,616 . (Feb. 18, 1964)
ohtsuka, E., et al. (to Toyo Roatsu Industries), "Method of Recovering Heat from Acet- ylene-Producing Furnace," Japanese 39-15659 (Aug. 4, 1964)
Borden h U.S. Rubber, "Improvements in the Recovery of Acetylene," British 1.124,750 (Aug. 21, 1968)
Vulikh, A. I., et al., "Acetylene Purificati0n.w USSR 223,248 (Aug. 2, 1968) (Abstract)
Vulikh, A. I., et al., "Purification of Acetylene," USSR 193,666 (March 13, 1967) (Abstract)
Bushinskii, V. I., et al. (to State Scientific-Research and Design Institute of the Nitrogen Industry and of Products of Organic Synthesis), "Purification of Acetylene from Its Higher Homologs, w USSR 193,665 (March 13, 1967)
Trieschmann, H. G., et al. (to BA8F), "Process and Apparatus for the Manufacture of a Gas Mixture Containing Acetylene, Ethylene, Methane and Hydrogen, by Thermal Cracking of Liquid Nydrocarbons," US 3.992,277 (Nov. 16, 1976)
Sokolsky, D. V., et al., "Process for Liquid Phase Purification of Carbide Acetylene and Compositions Therefor, w US 3,974,085 (Aug. 10, 1976)
Baker, G. H. (to Air Products 6 Chemicals), "Acetylene Generating System," US 3,743,487 (July 3, 1973)
Freund, M., et al. (to Magyar Asvanylolai Foldg), "Method for Thermally Decomposing Saturated Hydrocarbons to Produce Unsaturated Hydrocarbons Employing Oxygen along with a Fuel Gas," US 3.499.055 (March 3, 1970)
Cichelli, M. T., et al. (to Du Pont), 'Manufacture of Acetylene by Two Stage Pyrolysis Under Reduced Pressure with the First Stage Pyrolysis Conducted in a Rotating Arc,” US 3,168,592 (Feb. 2, 1965)
Karlovitr, B. (to Combustion 6 Explosives Research), "Method and Apparatus for the Pro- duction of High Gas Temperatures," US 3,004,137 (Oct. 10, 1961)
Tsutsumi, S., et al. (to Toa Kagaku Kogyo Kabushiki Kaisha), "Process for the Production of Acetylene-and Ethylene-Containing Gases by the Incomplete Combustion of Liquid Hvdro- carbons," US 3,270,077 (Aug. 30, 1966)
245
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302231
302232
302235
302238
302239
302240
30224 1
302243
302244
302245
302246
302247
302248
302249
302250
30225 1
302252.
302253
302254
302255
Pollock, L. W., et al. (to Phillips Petroleum), "Plasma Streams and Method for Utilie- ing Same,,' US 3.248.446 (April 26, 1966)
Koble, R. A. (to Phillips Petroleum), "Purification of Gases," US 2,907,409 (Oct. 6, 1959)
Burleeon, J. C., et al. (to Monsanto), "Quench SyStw,” Us 2'998,464 (Aug. 29, 1961)
Drummond, W. H., et al. (to Monsanto), "Quench System,” US 2,998,465 (Aug. 29, 1961)
Sogawa. T., et al. (to Research Association of Polymer Raw Materials), "Furnace for Cracking Hydrocarbons Having a Flame-Adjustable Burner,,' US 3,203,769) (Aug. 31, 1965)
Vialaron, A. (to Ugine Kuhlmann), "Device for Cracking Organic Products in Liquid Phase by Means of an Electric Arc, 'I US 3,607,714 (Sept. 21, 1971)
Stocchi, V., et al. (to Montecatini Edison), "Apparatus for Scrubbing Gases," US 3,611,592 (Oct. 12, 1971)
Fey, 1. G. (to Westinghouse Electric), "Arc Heater Apparatus for Producing Acetylene from Heavy Hydrocarbons," US 4,105,888 (Aug. 8, 1978)
Behlke, Il., et al. (to Akademie der Wiesenechaften der DDR; Zentralinstitut fuer Physikalische Chemie), "Plasma-Chemical Material Conversion,,' East German 125,875 (May 25, 1977)
Moegel,, G., et al., "Apparatus and Method for Carrying Gut Endothermic Chemical Reac- tions, Especially for the Nanufacture of Pyrolysis Gases Containing Unsaturated Hydro- carbons, Like Acetylene and Ethylene," East German 123,083 (Nov. 20. 1976)
Weiss, J., et al. (to VEB Chemische Werke Buna), "Recovery of Acetylene," East German 133,965 (Jan. 31, 1979)
Kuehn, E.. et al., "Compression and Drying of Acetylene," East German 65,434 (Nov. 5, 1969)
Barton, K., "Purifying, Compressing, and Drying Acetylene,,' East German 37,173 (April 26, 1965)
Ebermann, H., et al., "Highly Pure Acetylene and Ethylene," East German 113,342 (June 5, 1975)
Kiean, W., et al., "Accumulating and or Separating Acetylene from Industrial Gas Mlx- tures," East German 99,558 (April 12, 1974)
BASF, "Removal of Carbon Dioxide and Acetylene from Cracked Gases Containing Acetylene and Ethylene,,' British 1,379,055 (Jan. 2, 1975)
Lassmann, E. (to Linde), "Purification of Acetylene," German Offen. 2,625,039 (Dec. 15, 1977)
Mogensen, S. (to AGA),-"Separation of Acetylenes from Pyrolysis Gases,,, German 2,352,924 (May 9, 1974)
Ranke, G. (to Linde), "Acetylene and Ethylene Recovery,,' German 2.202.007 (Oct. 6, 1977)
Voigt, H., et al. (to Hoechat), "Separating Hydrocarbon8 from Pyrolysis G88eS." German 2,048,840 (Nov. 16, 1972)
Bartholome, II., et al. (to BASF), "Acetylene by Partial Combustion of Hydrocarbons,,' German Offen. 1,935,007 (Jan. 14, 1971)
Mueller, W. D., et al. (to ~tallgeSellSChaft), “Acetylene by the Partial Oxidation of Hydrocarbons," German Offen. 1,812,795 (June 18, 1970)
246
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302257
302258
302259
302260
302261
302263
302264
302265
302267
302268
302270
302271
302272
302273
302274 Fauser, G. (to Montecatinl. Sot. Gen Ind), "Production of Acetylene and Ethylene,,' German 2,217,363 (May 26, 1966)
302275 Daendliker, G. (to CIBA), "Separation of Acetylene from Gas Mixtures,,' German 1,189,067 (Nov. 18, 1965)
302276 Chemische Werke Hule, "Process and Reactor for the Thermal Cracking of Liquid Hydro- carbons," British 1,043,641 (Sept. 21, 1966)
302277 Metallgeeellschaft, "Cracking of Low Molecular Weight Hydrocarbons," British 1.043.693 (July 18. 1963)
302278 Patron, G. (to Sicedieon Societa per Aaoni), "Purification of Acetylene Obtained by Crack- ing Gaseous Hydrocarbons." German 1.093.788 (Dec. 1, 1960)
302279
302282
Happel, J., et al., "Pyrolysis of Hydrocarbons,,' British 1,097,555 (Jan. 3. 1968)
Taxers, M. A., “Method for Introducing Carbon into Evacuated or Pressurized Reaction Vessels and Reaction Products Therefrom," US 4,128,624 (Dec. 5, 1978)
Union Carbide, "Acetylene and/or Ethylene Preparation," German 1,793,491 (Nov. 23, 1972)
Pechuro, N. S., et al. (to Lomouosov, M. V., Institute of Fine Chemical Technology, Moscow), "Apparatus for Forming Acetyleue-, Low-Molecular-Weight Olefin-, and Hydrogen- Containing Gaseous kHxtaires by Electric Arc Discharge Decomposition,” German 1.668.370 (Jan. 31, 1974)
Bogart, M. J. P. (to Luwmus), "Process for Recovering Acetylene and Ethylene from a Gas Mixture," German 1,468,198 (Feb. 5, 1970)
Seuuewald, K., et al. (to Knapsack), "Electric Arc Cracker,” German 1.468.168 (March 28, 1974)
=F, "Preventing Formation of Polymer Deposits in the Separation of Acetylene from Gas Mixtures," British 1,194,738 (June 10, 1970)
Kurashiki Rayou, "Recovery of Acetylene and Ethylene," German 1,280,241 (Oct. 17, 1968)
Bataafse Petroleum, "Improvements in or Relating to Processes for the Removal of Carbon Black Particles from Suspension in an Aqueous Liquid,,' British 846,219 (Aug. 31, 1960)
Xori, F., "Method and Apparatus for Separating Mixed Gases," German Offen 2.733'738 (Feb. 2, 1978)
Lassmann, E. (to Linde), "Washing Out Impurities from Acetylene,,' German 2'549,399 (Dec. 22, 1977)
Socony Mobil Oil, "Thermal Conversion Process and Apparatus Therefor," British 1,028,028 (May 4, 1966)
Gaenssleu, H., et al. (to Zimaer Verfahrenste), "Acetylene," German 1,205,959 (June 23. 1966)
Doulms, G., et al. (to Du Pant), “Arc Furnace,"' German 1.293'152 (Jan. 29, 1970)
Haese, E. (to Dr. C. Otto 6 Co.), "Hydrocarbon Cracking Process," German 1.270'537 (June 20, 1968)
Relk&n, G., et al. (to Hoechst), "Hydrocarbon Cracking Process," German 1.237.095 (Nov. 30, 1967)
Carstensen, A., et al. (to Knapsack), "Process for Preventing Lime Crust Formation in Calcium Carbide Gasification and Acetylene Purification Plants," German 1.228'369 (Nov. 10, 1966)
247
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302285
302286
302287
302288
302289
302290
302291
302292
302294
302295
302297
302299
302300
302301
302302
302303
302304
302305
302306
302308
302309
Tamers, M. A., "Carbide Production Using Molten Wetals as Heat Source," US 4.137.295 (Jan. 30. 1979)
Dement'ev, V. V., et al., "Wethod of Heating Gas and Electric Arc Plasmochemical Reac- tor Realizing Same," US 4'144,444 (Warch 13, 1979)
Moegel, G., et al. (to VBB Chemische Werke Buna), "Endothermic Chemical Reactions, Ee- pecially for the Production of Acetylene and Ethylene," East German 127,002 (Feb. 23, 1976)
Budde, K., et al. (to VEB Chemische Werke Buna), "Coke with Reduced Electrical Conduc- tivity,” German Offen. 2,722,476 (Nov. 23, 1978)
Singer, W., et al. (to VEB Chemlsche Werke Buna), “Coke with Reduced Electrical Conduc- tivity," East German 139,948 (Jan. 30, 1980)
Fratrscher, W., et al., "Calcium Carbide,,' East Gerwn 136,824 (Aug. 1, 1979)
Hellmold, F., et al., "Lowering the Cyanide Content in Products from Calcium Carbide Production," East German 134,757 (March 21, 1979)
Popovski, J., "Direct Current Electric Arc Furnace,” German Offen. 2.748.893 (Aug. 7. 1980)
Singer, W.. et al. (to VEB Chemische Werke Buna), “Brown Coal High-Temperature Coke with Poor Electrical Conductivity, w East German 132,977 (Nov. 22, 1978)
Bushinskii, V. I., et al. (to State Scientific-Research and Design Institute of the Nitrogen Industry), "Removal of Higher Homologe from Acetylene," USSR 230,373 (Oct. 30, 1968) (Abstract)
Kruis, A., et al'. (to Linde Eismaschinen), "Process for Obtaining Pure Acetylene," US 3'405,192 (Oct. 8. 1968)
Haberl. K.. et al. (to Chemische Werke Huls), "Process of Separating Carbon Black from Gases," US 2'822,062 (Feb. 4, 1958)
Pohl, F., et al. (to Enapsack-Griesheim), "Process for Separating Higher Hydrocarbons from Gas Wixtures Containing Acetylene and/or Ethylene," US 3,152,194 (Oct. 6, 1964)
von Ediger, W. (to Technical Assets), "Process for the Production of Acetylene from Liquid Hydrocarbons," US 2,632,731 (March 24, 1953)
BASF. "Imprwements in the Cracking of Hydrocarbons," British 827,438 (Feb. 3, 1960)
Hoechst, "Process and Apparatus for Carrying Out Chemical Reactions at Righ Tempera- tures," British 834,419 (May 11, 1960)
Bartholome, E., et al. (to BASF), "Production of Acetylene by Thermal Cracking of Hy- drocarbons,', US 3,396,207 (Aug. 6, 1968)
List, H. W.. et al. (to Buss), "Process for Generation of Acetylene," German 1'123,793 (Aug. 30, 1962)
Continental Licht und Apparatebau, "Acetylene Generator," Swiss 295,610 (March 16, 1954)
Muller, P. (to Autogen Endress), "Acetylene High Pressure Generator," German 1,172,007 (June 11, 1964)
Shashkov, A. N., et al. (to Union Carbide), "Recuperation Furnace," French 1,491,926 (Aug. 11. 1967)
Dickens, 8. P. (to Texaco), "Acetylene Waklng and Heavy Oil Coking Process," US 2,944,960 (July 12, 1960)
248
302311
302313
302314
l 302316
302318
302319
302320
302323
302324
302325
302326
302327
302331
302332
302334
302335
302336
302338
302339
302340
302341
Murphy, M. A., et al. (to Shawinigan Chemicals), "Acetylene Generation," Canadian 565,926 (Nov. 11, 1958)
Ghita, D., et al. (to Bomania, Ministry of the Chemical Industry), "Acetylene by a Wet Method," French 1,494,803 (Sept. 15, 1967)
Pechtold, W., et al. (to ghapeack-Grleshelm), "Method for Charging Dry Gasifiere with Calcium Carbide," US 3,090,685 @lay 21, 1963)
Schepman, W. G., et al. (to Union Carbide 6 Carbon), "Acetylene Generating Apparatus," US 2.787.532 (April 2, 1957)
BASF, "Acetylene Production, w German 1,266,917 (Nov. 21, 1968)
Soc. Belge de 1'Aaote et des Produits Chimiquee, 'Unsaturated Bydrocarbons," German 1,214,215 (April 14, 1966)
Bottmayr, F. (to Llnde Eismaechinen), "Acetylene Purification," German 953,700 (Dec. 6, 1956)
BASF, "Flameless Dissociation of Gaseous Hydrocarbons,' Belgian 703,494 (Sept. 5, 1967) (Abstract)
BASF "Partial Combustion of Gas/Vapor Mixtures for Acetylene Manufacture," French 2,014,969 (April 24, 1970) (Abstract)
Foster, K. M. (to Air Beduction), "Acetylene Generation," US 3,498,767 (March 3, 1970) (Abstract)
Steigelmann. E. F., et al. (to Standard Oil, Indiana), 'Fluid Separation Process and Membrane,' US 4,015,955 (April 5, 1977) (Abstract)
Steilgelmann, E. F., et al. (to Standard Oil, Indiana), "Separation of Uneaturated Hy- drocarbons," US 3,758,603 (Sept. 11, 1973) (Abstract)
Rottmayr, F., et al., 'Separation and Recovery of Acetylenes from Tube Furnace Cracked Gas,' Chem.-Anlagen Verfahren, 10 (1972), 69-72, 75
Bischof, C., et al., 'Natural Gas aa a Baw Material Basis for Technical Monomer Synthe- ses," Chen. Tech., 24, 11 (1972), 667-71
Hochkirch, H., et al., 'Operating Experiences with Hollow Electrodes in Calcium Carbide Furnaces,' Chem. Tech. (Leipzig),28, 4 (1976), 214-17
Rettkowski, w., 'Problems in the Modeling of the Technical Calcium Carbide Process. Part II: Beat Transfer Behavior,' Chem Tech. (Leipzig),28, 5 (1976), 289-92
Rettkowski, W., et al., "Problems in Modeling the Technical Carbide Process. Part III: Flow Behavior,' Chem. Tech. (Lelpxig),28, 7 (1976) 411-12
Rettkowskl, W., et al., 'Problems In Modeling the Technical Calcium Carbide Process. Part IV: Electrical Conductivity of Calcium Carbide and Carbide Furnace Mixture,' Chem. Tech. (Leipzig)'28, 10 (1976). 588-9, 591
Rettkowski, W., 'Problems of Modeling the Technical Carbide Process. Part V. Sieing." Chem. Tech. (Leipelg), 28, 11 (1976)' 652-5
Rettkowski, W., et al., "Problems in Modeling the Induetrial Carbide Processes. Part VI. Electrical Simulator of the Calcium Carbide Reactor," Chem. Tech. (Leipeig), 28, 12 (1976), 729
Frateecher. W., et al., 'Problems in Modeling the Industrial Carbide Process. Part VII: Energy Economic Aspects," Chem. Tech. (Leipzig), 29, 4 (1977). 187-90
249
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302349
302350
302352
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302357
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302360
302361
302363
302364
302365
302366
302368
Rettkowski, W., et al., "Modeling Problems in Industrial Carbide Processes. Part VIII. Energy Change in the Calcium Carbide Furnace," Chem. Tech. (Leipzig), 29, 6 (1977), 331-2
Budde, II., et al., "Mathematical Modeling of Electrothermal Processee (Illustrated by the Calcium Carbide Process). Part II. Modeling of the Electric Current Flow Field in the Main Reaction Zone," Chem. Tech. (Leipzig), 30, 6 (1978), 287-9
Budde, K., et al., "Mathematical Modeling of Zlectrothermal Processes (Represented by the Process of Formation of Calcium Carbide). Part III. Modeling of Kinetic-Tranefor- mation in the Main Reaction Zone," Chem. Tech. (Leipelg), 30, 12 (1978). 617-20
Emons, H. H., et al., "Balancing of the Industrial Calcium Carbide Process. Part I. Setting of Problems and Practical Studies," Chem. Tech. (Leipzig), 31, 10 (1979), 506-10
Budde. K., et al., "Mathematical Modeling of Electrothermal Processes (Represented by the Calcium Carbide Process). Part IV. Modeling of Electrical and Physical Fractional Processes in the Neutral and Preheating Zone," Chem. Tech. (Leipzig), 31, 10 (1979)' 510-14
Budde, K., et al., "Mathematical Modeling of Electrothermal Processes (Represented in Calcium Carbide Process). Part V. Modeling of a Rectangular Carbide Reactor (Reactor Model)," Chem. Tech. (Leipzig), 32, 4 (1980), 181-3
Emons. H. H., et al., "Balances of the Industrial Calcium Carbide Process. Part II. Thermodynamic Calculations," Chem. Tech (Leipzig), 32, 4 (1980), 193-E
Barbier, M., et al., "Acetylene Production by Electric Means," Electrotechnology, 2 (1978), 293-333
Meintjes, J., "Control of Air Pollution at Rand Carbide Limited, Witbank," J. S. Afr. Inst. Min. Metall., 78, 1 (1977), l-7
Linke, D., "Production of Industrial Gases," Tech. Mitt., 69, 12 (1976), 604-9
Budde, K., et al., "Calculation of Concentration and Temperature Fields in the Electro- thermal Carbide Reactor," Wise. Z. Tech. Hochsch. "Carl Schorlemmer" Leuna-Merseburg, 21, 1 (1979), 72-81
Ghita, D., et al. (to Romania, Ministry of the Chemical Industry), "Acetylene Generating Apparatus," Romanian 50,791 (April 27, 1968) (Abstract)
Romanyuk, L. M., et al., "Reaction Chamber for Manufacturing Acetylene," USSR 710,609 (Jan. 25, 1980) (Abstract)
Fedotov, I. K., "Acetylene Generator," USSR 531,842 (Oct. 15, 1976) (Abstract)
Englin, A. L., et al., "Removal of Acetylene Homologs from Acetylene," USSR 441,027 (Aug. 30, 1974) (Abstract)
Popov, V. F., "High-Speed Tunnel Reactor for Thermal Gxidative Pyrolysis of Hydrocarbons to Acetylene," USSR 262,852 (May 30, 1979) (Abstract)
Popov, V. F. (to State Scientific-Research and Design Institute of the Nitrogen Indus- try) 1 "Reactor for Homogeneous Pyrolysis of Hydrocarbons for Preparing Acetylene or Ethylene," USSR 249,346 (May 30, 1979) (Abstract)
Danlchkin, A. P., et al.' "Acetylene Generator," USSR 191,736 (Jan. 10, 1967) (Abstract)
Shaehkov, A. N., et al. (to All-Union Scientific-Research Institute of Autogenous Machine Building), "Acetylene," USSR 173,748 (Aug. 6, 1965) (Abstract)
Seweryniak. M.. et al. (to Zaklady Azotowe im. Feliksa Dzierzynekiego), "Acetylene," Polish 89,788 (Aug. 30, 1977) (Abstract)
250
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l 302374
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302384
302385
302387
302388
302389
302390
302391
302392
Rozanka, J., et al. (to Zaklady Azotowe im. Pawla Findera), "Calcium Carbide," Polish 85,514 (Sept. 15, 1976) (Abstract)
Seweryniak, M., et al. (to Politecbnika Wroclaweka), "Burner for Partial Combustion of Gaseous Hydrocarbons," Polish 78,884 (Dec. 15, 1977) (Abstract)
Kang. T. II., "Coating Materials Baaed on Waste Calcium Hydroxide from Acetylene Manu- facture," Japanese Kokai 54-47725 (April 14, 1979) (Abstract)
Kaneko, S., et al. (to Denki Kagaku Kogyo), "Low-Density Calcium Carbonate," Japanese Kokai 54-43897 (April 6, 1979) (Abstract)
Sekiya, M.. et al. (to Ibiden Engineering), "Acetylene Refiner," Japanese Kokai 51-125305 (Nov. 1, 1976) (Abstract)
Rothmann, H., "Acetylene Generator," East German 65,626 (Feb. 20, 1969) (Abstract)
VEB Maschinenfabrik 6 Bleengieseeret Dessau, "Acetylene Generator," German 1,288,231 (Jan. 30, 1969)
Dudas. I., et al. (to Romania, "Balanta" Plant), "Acetylene Generator," Romanian 52,037 (Jan. 9, 1970) (Abstract)
Ivanov.. 0. R., et al., "Acetylene and Ethylene," USSR 689,994 @ct. 5, 1979) (Abstract)
Sokol'skil, D. V., et al. (to Institute of Organic Catalysis 6 Electrochemistry, Aca- demy of Sciences), "Solution for Removing Gaseous Phosphine and Hydrogen Sulfide from Acetylene," USSR 618,124 (Aug. 5, 1978) (Abstract)
Sokol'ekii, D. V., et al. (to Inetitute of Organic Catalysis & Electrochemistry, Aca- demy of Sciences), "Solution for Removing Gaseous Phoephine and Hydrogen Sulfide from Acetylene," USSR 618,123 (Aug. 5, 1978)
Polak, L. S., et al. (to Topchiev, A. V., Institute of Petrochemical Synthesis), "Ethy- lene and Acetylene," USSR 502,549 (Dec. 25, 1978) (Abstract)
Kalent'ev, V. I., et al. (to Bryanek Institute of Transportation Machine Building). "Acetylene Generator," USSR 635,121 (Nov. 30, 1978) (Abstract)
Ogurtsov, V. P., et al. (to All-Union Scientific-Research Institute of Portable Equip- ment Engineering), "Acetylene Generator," USSR 632,725 (Nov. 15, 1978) (Abstract)
Ershov, V. A., et al. (to Leningrad State Scientific-Research Institute of the Basic Chemical Industry; Leningrad Technological Institute), “Calcium Carbide," USSR 631.447 (Way 11, 1978) (Abstract)
Luzina, V. P., et al., "Separation of Acetylene from the Gaseous Producte of Hydrocar- bon Pyrolysis," USSR 589,239 (Jan. 25, 1978) (Abstract)
Golubenko, V. T., et al. (to Grozay Petroleum Institute), "Calcium Carbide," USSR 573,446 (Sept. 25, 1977) (Abstract)
Dorfman, Ya. A., et al. (to Institute of Organic Catalysis 6 Electrochemistry, Academy of Sciences), "Solution for the Removal of Phoephine and Hydrogen Sulfide from Acetyl- ene," USSR 570,386 (Aug. 30, 1977) (Abstract)
Sokol'ekli, D. V., et al. (to Inetitute of Organic Catalysis h Electrochemistry, Acad- emy of Sciences), "Oxidizing Solution for Purification of Gases, e.g., Acetylene, to Remove Phosphorus and Hydrogen Polysulfide," USSR 452.231 (Aug. 5. 1977) (Abstract)
Shevchuk. V. U., et al., "Burner for Producing Acetylene," USSR 292,364 (July 25, 1978) (Abstract)
Sokol'skii, D. V., et al. (to Kirov, S. Ii.. Acetylene from Carbide,"
Kazakh State University), "Purification of USSR 266,993 (April 1, 1970) (Abstract)
251
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302407
302408
302409
302410
302411
302412
302413
302414
302415
Kucherenko, L. A., et al. (to Severodonetek Chemical Combine), "Purification of Acetyl- ene,,, USSR 204,481 (Oct. 20, 1967) (Abstract)
VEB Maschinenfabrik & Eiaengieeeeret Deesau, "Acetylene Generator Sludge-off Valve,,, German 1,494,778 (Way 27, 1971) (Abstract)
Friedrich W., et al. (to VEB Chemieche Werke Buna), 'Granular Lime Fertilizers," East German 135,076 (April 11, 1979) (Abstract)
Richter, M., et al. (to VEB Chemische Werke Buna), 'Acetylene Production,,, East German 133,815 (Jan. 24, 1979) (Abstract)
Arnold, A., "Treatment of Iron Hydroxide Sludges,,' East German 133,255 (Dec. 20, 1978) (Abstract)
Denki Kagaku Kogyo, "Formed Raw Materials for Calcium Carbide Production,' Japanese Kokai 55-62811 (May 12, 1980) (Abstract)
Naito, H. , et al. (to Denki Kagaku Kogyo), "Calcium Carbide,,, Japanese Kokai 55-37426 (March 15, 1980)
Marada, H., et al. (to Denki Kagaku Kogyo), 'Calcium Carbide Production,' .?apanese Kokai 54-159400 (Dec. 17, 1979)
Naito, H., et al. (to Denki Kagaku Kogyo), "Calcium Carbide," Japanese Kokai 54-159399 (Dec. 17. 1979)
Yamagiehi, N., et al. (to TDK Electronics), "Calcium Carbide,,' Japanese Kokai 54-121299 (Sept. 20, 1979) (Abstract)
Yamagiehi, N., et al. (to Denkl Kagaku Kogyo), "Calcium Carbide, "Japanese Kokai 54-82400 (June 30, 1979)
Yama8ieh1, N., et al. (to Denki Kagaku Kogyo), "Calcium Carbide," Japanese Kokai 54-69599 (June 4, 1979)
Dakeno, 8. (to Denki Kagaku Kogyo), "Calcium Carbide Production by Gas Heating,', Japanese Kokai 54-21000 (Feb. 16, 1979)
Yamagishi. N.. et al. (to Denki Kagaku Kogyo), "Calcium Carbide Production and Apparatus,,, Japanese Kokai 54-14400 (Feb. 2, 1979)
w-1 s., et al. (to Nippon Zeoa), "Removal of Carbon Tars from Cracking Gases,' Japanese 54-7801 (April 10, 1979) (Abstract)
Harada, H., et al. (to Denkl Kagaku Kogyo), "Calcium Carbide Production,,, Japanese Kokai 54-5899 (Jan. 17, 1979)
Yanagisawa, E., "Concentration of Fuel Gas Bottom,,, Japanese 54-3845 (Feb. 27, 1979) (Abstract)
Kaneko, S. (to Denki Kagaku Kogyo), "Calcium Carbide,,, Japanese Kokai 53-149200 (Dec. 26, 1978)
Yamagishi, N., et al. (to Denki Kagaku Kogyo), "Briquet for Calcium Carbide Production," Japanese Kokai 53-139000 (Dec. 4, 1978) (Abstract)
Naito, IL, et al. (to Denkl Kagaku Kogyo), "Calcium Carbide,,, Japanese Kokal 53-117700 (Oct. 14, 1978) (Abstract)
Harada. H., et al. (to Denki Kagaku Kogyo), "Calcium Carbide,,, Japanese Kokal 53-117699 (Oct. 14, 1978)
Hanaoh, Y., et al. (to Denki Kagaku Kogyo), "Calcium Carbide,,, Japanese Kokai 53-95200 (Aug. 19, 1978)
252
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302435
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302442
302443
302445
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302450
302453
302458
302460
Nanaoka, Y., et al. (to Denkl Kagaku Kogyo), "Calcium Carbide,', Japanese Kokai 53-95199 (Aug. 19, 1978)
Yanagisawa, E., "Manufacture of Compressed Fuel Gases," Japanese 53-1285 (Jan. 18, 1978) (Abstract)
Yanagisawa, E., "Metal-Processing Fuel-Gas Generator," Japanese 53-1242 (Jan. 17, 1978) (Abstract)
Sato, 0. (to Ibiden Engineering), "Solution for Purification of Acetylene," Japanese Kokai 52-126686 (Oct. 24, 1977) (Abstract)
Tomisaki, K., et al. (to Diamond Engineering), "Removal of Hydrogen Sulfide from Acet- ylene," Japanese Kokai 52-39606 (March 28, 1977) (Abstract)
Niehlda, M., et al. (to Nichigo Acetylene), "Regeneration of Acetylene Scrubbing Solu- tion," Japanese Kokai 52-904 (Jan. 6, 1977) (Abstract)
Sekiya, N., et al. (to Ibiden Engineering), "Acetylene Refiner,,' Japanese Kokai 51-125306 (Nov. 1, 1976) (Abstract)
Societe Francaise de l'Acetylene, "Carbide Charge Unit for Acetylene Generators,,' French Demande 2,373,604 (July 7, 1978) (Abstract)
Institute of Heat and Mass Transfer, Academy of Sciences; State Scientific-Research and DeeQn Institute of the Nitrogen Industry; Topchiev, A. V., Institute of Petrochemical synthesis, "Plaswchemical Reactor with Electric Arc for Heating Gas," French Demande 2,304,243 (Oct. 8, 1976) (Abstract)
Babalov,,G. I(.. et al. (to Novomoskovek Chemical Combine; Leningrad Technological In- etitute) , "Isolation of Acetylene and D'iacetylene from Hydrocarbon Gases,', USSR 570,580 (Abstract)
Kawana, Y., "Manufacture of Acetylene from Hydrocarbons by Plasma Jet,,, Chem. Econ. Eng. Rev. ) 4, 1 (1972), 13-17
Budde, I., "Problems of the Intensification of Carbide Production," Chem. Sch., 26, 1 (1979), 8-17
Chakravartty, S. C., "Acetylene from Coal by Plasma Technique,,' Chem. Eng. World 14, 11 (1979). 65-8
Wirtz, 8.. et al. "The Reactions of Hydrocarbons in the High Temperature Pyrolysis,,, Erdoel and Kohle, Erdgas, Petrochemie Vereinigt with Brennstoff-Chemle, 15 (1962)' 977-82; available from NTC as 71-17064-07C
Schmidt, A., et al., "Cracking of Liquid Hydrocarbons by Electric Arcs,” Erdoel and Kohle-Erdgaa-Petrochmie, 16 (1963), 693-7; available from NTC as 69-12731-07A
Petrlc, B., et al., "Treatment of Waste Water of Electrothermal Industries and Reuse of Raw Materials,,' Gas-Waeserfach, Waseer - Abwasser, 119, 12 (1978)' 589-91
Borovik, E. S., et al., "Apparatus for the Production and Investigation of High-Pressure Heavy-Current Long Arcs,” High Temperature, 6, 6 (November/December, 1968), 1076-80
Holmen, A., et al., lene,"
"High-Temperature Pyrolysis of Hydrocarbons..' 2. Ind. Chem. Process. Des. Dev., 18, 4 (197g), 653-7
Naphtha to Acety-
Strauss, G.. "Acetylene from Calcium Carbide,,, Chemierohst. Kohle (1977), 57-66, 408
Gehrmann, K., et al., "Pyrolysis of Hydrocarbons Using a Hydrogen Plasma,,, Proceedings of the Eighth World Petroleum Congress, 1971, Moscow
Maklno, M., et al., "Acetylene Formation from Liquid Hydrocarbons with Hydrogen Plasma Jet,,, J. Chem. Sot. Japan, Ind. Chem. Sec., 73, 2 (February 1970)' 306-10
253
302462 Romanyuk, I. M., et al., "The Synthesis of Acetylene and Ethylene by Submersed Combus- tion,,' Soviet Chem. Ind., 8, 10 (1976), 765-8
302463 Kruis, A., et al., "Low Temperature Scrubbing for the Treatment of Crack Gases,,, pre- sented at the 11th International Congress of Refrigeration, Munich, West Germany, 1963
302464 Fauchais. P., et al., "Plasma Chemistry and Its Applications to the Synthesis of Acety- lene from Hydrocarbons and Coal,,' Intern. Chem. Eng., 20, 2 (April 1980), 289-305
302468 Azbel, I. Ya.. et al., "Fine Purification of Acetylene to Remove Moisture and Higher Alkynes and Dienes," Intern. Chem. Eng., 10, 1 (January 1970), 108-111
302471 Kozlov, G. I., et al., "Investigation of Acetylene Formation from Methane in a Hydrogen Plaza Jet ,‘I Intern. Chem. kg., 8, 2 (April 19681, 289-93
302472 “Arc Acetylene Process," Hydrocarbon Process., 50, 7 (June 1971), 133-6
302473 Kamptner, Il. K., et al., "ETF': After Five Years," Hydrocarbon Process., 45, 4 (April 1966), 187-93
302474 Gladisch, II., %ow Huele Makes Acetylene by DC Arc,,' Hydrocarbon Process., 41, 6 (June 1962), 159-64
302477 Nikitin, V. I., et al., "Use of Waste Products from an Oxygen-Acetylene Plant in Drill- ing Organizations," Axerb. left. Ehos., 7 (1978). 26-9 (Abstract)
302478 "Acetylene from Natural Gas by Arc Reactor,,, Brit. Chem. Eng., Processes in Europe (November 1969), 15
302480 "Acetylene Production from Gas Oil,,, Chem. Econ. Eng. Rev., 3, 42 (October 1971). 54
302486 Brooks, J. D., et al., "Formation of Acetylene in Electron-Activated Cracking of Liquid Hydrocarbons,,, J. Appl. Chem., 17. 8 (1967)' 225-38
302487 Ganz, 8. N., et al., "Preparation of Acetylene from Natural Gas in a Hydrogen Plasma,,, Khim. Tekuol. (Eharkov), 23 (1971)' 17-19
302489 Takahashi, T., et al., "The Thermal Decomposition of Hydrocarbons in a Plasma Jet. II. Effect of the Arc Voltage Drop on the Thermal Decompositions of Propane and n-Butane,,' Rogyo Eagaku Zasshi, 74, 5 (1971), 928-33
302490 Kawana, Y., et al., "Acetylene Formation from Lower Aliphatic Hydrocarbons in a Plasma Jet,,' Eogyo Ragaku Zasehi, 71, 4 (1968), 492-6
302491 Okabayasi, T., et al., "Acetylene Production by the Plasma Jet. I. Acetylene Produc- tion by the Hydrogen Plasma Jet Using Methane as the Raw Material,,, Rogyo Ragalcu Zaeehi, 74, 8 (1971), 1631-8
302492 Okabayasi, T., et al., "Production of Acetylene by a Plasma Jet. II. Production of Acetylene from Natural Gas and Naphtha Using a Mixed-Gas Plasma Jet which is Composed of Hydrogen and Methane," Rogyo Ragaku Zasehi, 74, 10 (1971)' 2057-62
302493 Okabayashi, T., et al., "Acetylene Production by Plasma Jets. III. Factors Affecting the Stability of Plasma Arcs and Acetylene Manufacturing Costs in the Production of Acetylene,,' Nippon Ragaku Raishi, 3, (1972). 609-15
302495 "Acetylene Production Using Hydrogen Plasma,,' Oil Gas J., March 12, 1973, 82
302496 Kawana, Y. , "Acetylene Formation from Coal by a Plasma Jet,,' Shinku Ragaku, 15, 2 (19671, 56-64
302497 Polubelova, A. S., et al., "Behavior of High-Silica Limes During Carbide Formation," Tekhnol. Neorg. Veshchestv, 1 (1975)' 76-80 (Abstract)
302499 Dubinskii, Yu. N., "Possibility of Using Ash of Ransk-Achinsk Coals for Production of Calcium Carbide and Cyanamide,,' Elektn Stn., 7 (1977). 24-5 (Abstract)
254
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302523
302527
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302530
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Dumbgen, G., et al. "Investigations on the Manufacture of Acetylene by Methane- and Light Petroleum Cleavage,,, Chem. Ing. Tech., 40, 20, Oct. 25, 1968, 1004-E
Gladisch, H., "Production of Acetylene in an Electric Arc,” Chem. Ing. Tech., 41, 4 (1969). 204-7
Fritz, H., "Recent Developments in the Nanufacture of Acetylene at BASF," Chem. Ing. Tech., 40, 20, Oct. 25, 1968, 999-1004
Bachmann, D., et al., "Technological Problems in the Development of High-Temperature Pyrolysis,', Chem. Ing. Tech., 37, 9 (1965). 886-92
Valibekov. Yu., V., et al., "An Investigation of the Process for Producing Acetylene, Its Homologe, and Technical Hydrogen from Natural Gas by the Plasma Jet Synthesis Nethod," Intern. Chem. Eng., 9, 4 (October 1969), 683-91
Wragg, J. G., et al., "Plasma-Arc Coal Chemicals," paper presented at the 88th National Meeting of the AIChE, Feedstock Alternatives Session, Philadelphia, PA, June 8-12. 1980
"Pierrefitte gave New Solvent for Acetylene,,' Chem. Age, Sept. 16, 1967
"BASF Gxy-Thermal Method for Calcium Carbide Uses Calcium, Coke and Oxygen," Chem. Age (February 1961), 327
Gibadlo, F. "Sink-Float Process Aids Acetylene Generation,,, Chem. Eng. (February 1957), 286
"Acetylene Producer Cuts Costs,,' Chem. Bng. News, Feb. 10, 1958, 49-51
"Plasma-Fluidieed Bed Feasible,,' Chem. Eng. News, Dec. 21, 1964, 44
Takaehima, S., et al., "On Production of Acetylene and Magnesium Hydroxide from Calcium Carbide and Sea Water or Bittern," Himeji Rogyo Daigaku Renkyu, 11 (1960), 123-33
"The Manufacture of Calcium Carbide In Germany,,' Journal du Four Electrique et des Industries Electrochimiques, 6 (1962), 184
Vulikh, A. I., et al.. "Purification of Acetylene from Phosphine by an Anion-Exchange Resin in the Polylodide Form,,, Khim. Prom., 43, 5 (1967)' 337-9
Glikin, M. A., et al., "Quenching of Pyrolysis Gases in a Fluidized Bed of Solid Heat- Transfer Agents,” Khim. Tekhnol. (Kiev), 1 (1977), 26-8 (Abstract)
Torikai, N., et al., "Study on the Reactivity of Quicklime for the Formation of Calcium Carbide in Molten Phase,', Kogyo Eagaku Zasshi, 69, 7 (1966), 1272-77 (Abstract)
Trofimov, N. G., et al., "Synthesis of Acetylene from Calcium Carbonate,,, Zhur. Prikl. Khim., 32 (1959), 399-404
Erehov, V. A., "Joint Preparation of Calcium Carbide and Phosphorus from Calcium Phoe- phate," Zh. Prikl. Rhim. (Leningrad), 49, 8 (1976), 1665-9 (Abstract)
Boguelavskii, E. A., et al., "Change In the Compositlon,and Activity of a Copper Chloride Chemisorbent During the Purification of Carbide-Process Acetylene,,, Zh. Prikl. Rhim. (Leningrad), 51, 8 (1978). 1783-6 (Abstract)
Zobel, F., "The Purification of the Arc-Process Acetylene,,, Angew. Chem. B20, 10 (1948), 260-l
,,A Case History of In-Plant Air Pollution Control,,, Chem. Eng. Prog., 55. 3 (1959). 106
Shafer, M., et al., "Lime Kiln Design-2 Hot Cyclone Development Improves Lime Yield,,' Chem. Eng. Prog., 59, 11 (1963), 95-8
255
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302573
302574
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302586
"There's Talk this Week About a New Low-Cost Route to Acetylene," Chem. Week, 86, 8 (1960), 72
Mayer, L., "Formation, Extent and Detection of Industrial Dusts," Chem. Ing. Tech., 32, 3 (19601, 207
Sennewald, K., et al., "Generation of Acetylene by Thermal Cracking of Hydrocarbons with High Temperature Hydrogen,,, Chem. Ing. Tech., 35, 1 (January 1963), l-72
Cagas, F., et al., "Economical Cracking of Paraffin Hydrocarbons in the Electric Arc,,' Erdol u. Eohle, 12 (October 1959)' 818-23
"Calcium Carbide by Thermal Oxidation Process,,, Festschrlft Carl Wurster (1960), 43-50
Rastens, M. L., et al., “A Staff-Industry Collaborative Report,,, Ind. Eng. Chem., 43, 5 (1951), 1020-33
Smyers, W. A. (to Standard Oil Development), "Manufacture of Acetylene,,, US 2,165,820 (July 11, 1939)
Weir, H. M., "Production of Compounds by Means of the Electric Arc,” US 2,731,410 (Jan. 17, 1956)
Weir, R. M., "Gas Phase Arc Conversion,', US 2'768,947 (Oct. 30, 1956)
Harris, A. T. (to Du Pant), "Electric Arc Furnace for the Preparation of Acetylene by Pyrolysis of Hydrocarbons," US 3,375,316 (March 26, 1968)
Ellefsen, T., "The Elkem Rotating Hearth Furnace for Electrothermic Process,,' Trans- actions of the Electrochemical Society, 89 (1946)' 307-16
Societe anon. des Manufactures des Glacea et Produits Chimiques de Saint-Gobain Chauny h Cirey," Purification of Hydrocarbons, " French 986,637 (Aug. 2, 1951), (Abstract)
Bogart, M. J. P. (to Lu'mous), "Purification of Acetylene and Ethylene,,, British 1,020,676 (Feb. 23, 1966)
BASF, "Process and Apparatus for Regenerating Hydrocarbons Containing Carbon Black,,, British 1,298,109 (Nov. 29, 1972)
BASF, "Thermal Cracking of Liquid Hydrocarbons to Gas Mixtures,,, German 2'443,868 (March 25, 1976) (Abstract)
Barten'ev, L. V., et al., Yontrol of Low-Pressure Acetylene Production by Changing the Sludge Discharge from the Gas Producer,,' USSR 662,537 (May 15. 1979) (Abstract)
Krivoi, B. A., et al. (to Raraganda Synthetic Rubber Plant), "Removal of Suspended Matter from Acetylene Industry Wash Waters,', USSR 247,866 (April 5, 1977) (Abstract)
Asahi Carbon, "Acetylene Production,,' Japanese 47-8524 (March 11, 1972) (Abstract)
Ajinomoto, "Thermal Decomposition of Hydrocarbon to Produce Acetylene,,, Japanese 45-18129 (June 22, 1970) (Abstract)
BASF, "Acetylene from Hydrocarbons,,' German 1,418,664 (Oct. 14, 1971) (Abstract)
BASF 8 Schmidt'eche Heissdampf, "C2H4 is Produced by Thermal Cracking,,, British 1,032,690 (March 5, 1965) (Abstract)
Kuhlmann, A. M. (to Union Carbide), "Calcium Carbide Production," US 2,996,360 (Aug. 15, 1961)
Mukai, O., "Manufacture of Acetylene by Alternating Arc,,, Chem. Econ. Eng. Rev., 5, 5 (May 1973), 41-5
256
302587 “Soviets Ammoniate to Purify Pyrolyrls Gas," Chem. Brig., 73, 3, Feb. 24, 1969, 58
302588 Dundas, P. H., et al., "Economics and Technology of Chemical Processing with Electric- Field Plasmas," Cbem. Eng., 76, 13, June 30, 1969, 123-8
l 302598 Chernykh. 8. P., et al., "Drying of Acetylene and Vinyl Chloride with NaA Zeolite,"
Khim. Prom., 44, 5 (1968), 347-8 (Abetract)
302604 Furlong, D. A., et al., "Fabric Filtration at Blgh Temperature,,, Chem. Eng. Progr., 77, 1 (January 1981), 89-91
302606 Emons, 8. Ii., et al., "Balances of the Industrial Calcium Carbide Process. Part III. Balance of Process, Standard Specifications for the Consumption of Materials and Energy," Chew Tech. (Lelpsig), 32, 7 (1980), 352-9
302608 Sasaki. K., et al. (to Ritachi Shipbuilding 6 Engineering), "Process and Apparatus for Beat Recovery from Finely to Coarsely Divided Bot Material,,' British 2,054,809A (Feb. 18, 1981)
302609 Kruis. A., et al., "Low Temperature Washing for Gas Separation II. Treatment of Crack- ed Gae," Linde, Berichte aue Technlk und Wiseenachaft, 17 (1964). 15-23
302610 Andresen. B. E., et al. (to Union Carbide), "Acetylene Recovery Process and Apparatus,,, US 4,274,841 (June 23, 1981)
302611 Behlke, 8.. et al., "Plaaa Synthemie of Acetylene from Brown Coal Components Based on a High-Temperature Pyrolysis,,, Eart German 144,533 (Oct. 22, 1980)
302612 "Plasma Chemical and Process Engineering,,' Ind. Eng. Chem., 61, 11 (November 1969), 48-61
a
302613 "3-Mill Power Where You Want It by Year 2000," Chem Week, March 15, 1969, 92-9
302614 Ammann, P. R., et al., "The Converrion of Methane in an Arc Reactor,', Am. Chem. Sot., DIV. of Fuel Chem., Prepr. Part2, 11, 2 (1967). 364-5
302615 Amouroux, J., "Production of Acetylene by Heavy Hydrocarbon and Carbon in a Plasma Re- actor,,, Informations Chimie, 210 (January-February 1981)' 137-141
302616 Nlshimura. Y., et al., "Pyrolysis of Propane In an Induction-Coupled Argon Plasma Jet,', Intern. Chem. Eng., 10, 1 (January 1970), 133-7
302617 Eohne, D. "Acetylene - Hydrogenation or Recovery? an Economic Comparison," Linde, Berichte aus Technlk und Wiasenschaft, (1979). 48-53
302618 Terasawa. E., et al., "Production of Acetylene from Methane Using a Plaema Jet (I), Effect of Anode Nozzle. Methane Feeding Holes and Spraying Water on Methane Conversion,,' Sikiyu Gakkai Shi, 10, 2 (1967). 124-9
@
302619 "The Production of Olefine and Acetylene as Raw Materials for Use in the Chemical In- duetry, " Panel Discussion at the proceedings of the 8th World Petroleum Con8reea. 4 (1971). 389-92
302620 Dedova, I. V., et al., "The Solubility of Acetylenic Hydrocarbons in n+lethylpyrrolidone- 2 and Its Aqueoue Solutions," Khlm. Prom. 41, 3 (1965), 186-8
302621 Bakhtyukova. G. 1.. et at., "Solubillty of Acetylene in Methanol at Elevated Pressure,,' Neftepererabotka i Neftekhim., Nauchn.-Tekhn. Sb., 5 (1965). 37-40 (Abstract)
302623 Hayes, E. 0. (to National Keeearch Development), "A Process for the Production of an Acetylene Ease Fuel Gas, the Products Obtained by this Process, a Liquid Activator to be Used In the Process and the Use of the Produced Acetylene Base Fuel Gas," European 21,748 (Jan. 7, 1981)
257
313868 Bjornson, G., et al. (to Phillips Petroleum), "Electric Arc Process for Making Hydrogen Cyanide, Acetylene and Acrylonitrile," US 3,674,668 (July 4, 1972)
324014 Rottmayr, F. (to Linde). "Acetylene and Ethylene,,, Get-men 1.418.870 (May 14, 1970)
324082 Bogart, I. J. P. (to Lummue), "Production of Ethylene and Acetylene by High-Temperature Pyrolysis of Hydrocarbons,,' German 1,298,983 (July 10, 1969)
324157 Watkins, C. H. (to Universal Oil Products), "Production of Unsaturated Hydrocarbons,,' German 1,275,530 (April 10, 1969)
324182 BASF, "Conversion of Liquid Hydrocarbons into Acetylene and/or Olefine," British 1,200,070 (July 29, 1970)
324184 Dane, W., et al. (to BASF), "Production of Acetylene, or Acetylene and Ethylene by Partial Gxidation of Hydrocarbons," US 3,301,914 (Jan. 31, 1967)
324194 Moriarty, F. C. (to Marathon Oil), "Preparation of Unsaturated Rydrocarbone by Pyroly- ale, and Related Compositiona,” US 3,366,702 (Jan. 30, 1968)
324311 Showa De&o, "Method for Recovering or Storing Acetylene,,, Japanese 43-26602 (Nov. 15, 1968)
324313 Iwaya Sangyo, "Acetylene and Ethylene,,, Japanese 42-13281 (July 28, 1967)
324314 Iwatani Sangyo, "Hydrocarbon Cracking," Japanese 43-21282 (Sept. 12, 1968)
324315 Kogyo Kaihateu Kenkyusho, "Ethylene and Acetylene," Japanese 42-14601 (Aug. 16, 1967)
324316 Kurashiki Rayon, "Acetylene and Ethylene,,, Japanese 43-11201 (May 11, 1968)
324318 Shin Meiwa egyo, "Apparatus for Cracking Hydrocarbon,,' Japanese 43-29721 (Dec. 20, 1968)
324319 Shin Melwa Kogyo, "Apparatus for Cracking Hydrocarbons,,' Japanese 43-29722 (Dec. 20, 1968)
324321 Kogyo Kaihateu Kenkyusho, "Acetylene and Ethylene,,, Japanese 42-14602 (Aug. 16, 1967)
324936 Shin Meiwa Kogyo, "Hydrocarbon Cracking Apparatus,', Japanese 44-4765 (Feb. 27, 1969)
324991 Banke, G. (to Linde), "Process and Apparatus for the Simultaneous Production of Acety- lene and Ethylene,,, US 3,557,529 (Jan. 26, 1971)
358160 Bockho~, H., et al. (to Deuteche Gold- und Silber-Scheideanstalt), "Process and Device for the Production of Acetylene-Ethylene Mixtures," US 3'741,736 (June 26, 1973)
358230 Yoehlda, F., et al. (to Miteui Shipbuilding 6 Engineering), "Apparatus for Continuously Decomposing Hydrocarbon in a Heating Medium Bath," US 3,729,297 (April 24, 1973)
358345 Rottmayr, F., et al. (to Linde), "Prevention of Resin Formation During Absorption of CO2 and/or H2S from Cracking Gases,,, US 3.911.082 (Oct. 7, 1975)
358697 Stork, K., et al., "Recover Acetylene in Olefine Plants,', Hydrocarbon Process., 55, 11 (November 1976). 151-4
358785 "Plants for the Production of Olefins, Acetylene, Gasoline and Aromatics,,' Linde AG Division TVT, Munich (May 1977)
358899 Sagawa, T., et al. (Dec. 31, 1968)
"Thermal Cracking Method of Hydrocarbons,,' US 3'419,632
394000 "Review and Evaluation of 300 MN Lbe/Yr Acetylene Plant AVCO Arc-Coal Process,,' Office of Coal Research Department of the Interior, Washington, D.C., OCR Contract No. 14-32-0001-1215, Nov. 30, 1971
394002 "AVCO Arc-Coal Process--Phase I-- Feasibility Report,,, Office of Coal Research Depart- ment of the Interior, Washington, D.C., OCR Contract No. 14-01-0001-193 (August 1968)
-
l
258
416042 "Calcium Carbide Production Furnaces,,' private correspondence received from Ministry of the Chemical Industry, Department of Cooperation with Foreign Lands, Feb. 26, 1976
416047 Pfeiffer, T., et al. (to BASF), "Joint Removal of a Acetylene and Ethylene from Crack- ed Gases," British 1,379,056 (Jan. 2, 1975)
416049 "Design and Modeling of an Arc-Coal Acetylene Reactor,,, presented at the 87th National Meeting of the AIChE, Boston MA., Aug. 19-22, 1979
449734 "Formation of Acetylene from Coal by Argon-Hydrogen and Hydrogen,,, J. Chem. Sot. Japan (Induetrlal Chemistry Section), 70 10 (October 1967)' 1657-61
449738 Roberts, J. E., "Lime Kiln Design-- 1, UCM'e Vertical Lime Kiln,,' Chem. Eng. Progr., 59, 10 (October 1963), 88-91
500623 Stanton, W. ?I. (to Monsanto Chemical), "Purification of Ethylene,,, US 2'805,733 (Sept. 10, 1957)
B-43 Miller, S. A., "Acetylene, Its Properties, Manufacture and Uses,,' Vol. 1, Ernest Benn Limited, London, 1965
B-44 Stephen, H., et al., eds., "Solubilitiee of Inorganic and Organic Compounds,,' Vol. 1. Binary Syeteme, Part 2; The Macmillan Co., New York, 1963
B-45 "M-Pyrol®, N-Methyl-2-pyrrolldone Handbook,', GAF Corp., Chemical Division, New York, 1972
259
-
l
Act . No. w--w-- 302131 302251 302220 302325 302579 302241 302356 302304 302397 302115 302576 302306 302169 302574 302246 30209 8 302 104 302017 302023 302024 30204 1 30205 1 302056 302060 302069 302070 302075 30209 1 302158 302 159 302 193 302197 302198 302203 302204 302205 302217 302249 302254 302260 302301 302303 302318 302323 302324 30257 1 302573 302580 324182 324184 416047 302193 302 203 302204 302254 302260 30267 1 302580 324184 302582 302582 302263 302611 302152 302212
Clmpter ------- f i f x 5
t
f
i
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ii
:
f
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f
:
t
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ii 6 6
66
f
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t
77
3
3
5
; 6
f 6
PATENT REFERENCES BY COMPANY
Comp8ny ------------------_-----,------
ACA AfiA AIR PRODUCTS & CHEMICALS AIR REDUCTION AJ I NOM010 AKADEMIE DER WISSENSCHAFTEN DER DDR; ZENTRALINSTITU ALL-UNION SCIENTIFIC-RESEARCH INSTITUTE OF AUTOCENO ALL-UNION SCIENTIFIC-RESEARCH INSTITUTE OF PORTABLE ARNOLD, A. ARTVUKHOV, I. M. ASAHI CARBON AUTOGEN ENDRESS AVCO BARTEN’EV, L. V., ET AL. BARTON, K. BASF BASF BASF BASF BASF BASF BASF BASF BASF BASF BASF BASF BASF BASF BASF BASF BASF BASF BASF 8ASF BASF BASF BASF 8ASF BASF BASF BASF BASF BASF BASF BASF BASF BASF BASF BASF BASF BASF BASF BASF BASF BASF BASF BASF BASF BASF & SCHMIDT’SCHE HEISSDAMPF BASF & SCHMIDT’SCHE HEISSDAMPF BATAAFSE PETROLEUM BEHLKE, H., ET AL. BORDEN BORDEN 0 U.S. RUBBER
261
PATENT REFERENCES BY COMPANY
Ace. No. --B-s-
302383 302304 302183 302168 302276 302297 302297 302161 302275
3E:;x 302305 302025 302365 302285 302398 302399 302 400 302401 302404 302405 302 406 302407 302 409 302411 302412 3024 13 312414 302415 302415 302372 358160 302171 302206 302207 302420 302042 302 182 30227 1 312173 302174 302223 302270 302563 302247 302086 30236 1 302118 302 160 302360 302289 302162 302096 302 170 382388 302199 302279 302290 302608 302016 302054 302055 302058
%%! 302167
Chapter --s-B--
3 6
: 6 8
t
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Company ------------------------------ BRYANSK INSTITUTE OF TRANSPORTATION MACHINE BUILDIN BUSS CHEMICAL CONSTRUCTION CHEMISCHE WERKE HULS CHEMI SCHE UERKE HULS CHEMISCHE WERKE HULS CHEMISCHE WERKE HULS CHEPOS ZAVODY CHEMICK - EKO A POTRAVINARSKEHO STROJ CIBA COLUMBIA-SOUTHERN CHEMICAL COMBUSTION & EXPLOSIVES RESEARCH ECW;;EN;AL LIGHT UND APPARATEBAU
DANICHiIN: A. P., ET AL. DEMENT’EV, V. V., ET AL. DENKI KAGAKU KOfiYO DENKI KAGAKU KOGYO DENKI KAGAKU KOGVO DENKI KAGAKU KOGVO DENKI KAGAKU KOGYO DENKI KAGAKU KOGVO DENKI KAGAKU KOGYO DENKI KAGAKU KOGYO DENKI KAGAKU KOGYO DENKI KAGAKU KOGYO DENKI KAGAKU KOGYO DENKI KAGAKU KOGYO DENKI KAGAKU KOGYO DENKI KAGAKU KOGYO DENKI KAGAKU KOGVO DENKI KAGAKU KOGVO DEUTSCHE 60LD- UND SILBER-SCHEIDEANSTALT DIAMOND ALKALI DIAMOND ALKALI DIAMOND ALKALI DIAMOND ENGINEERING DIAMOND SHAMROCK DIAMOND SHAMROCK DR. C. OTTO & CO. DU PONT DU PONT DU PONT DU PONT DU PONT EBERMANN, H., ET AL. ENERGETICHESKY INSTITUT IMENI G.M. KRZHIZHANOVSKOGO ENGLIN, A. L., ET AL. ENYA, R. ESSO RESEARCH & ENGINEERING FEDOTOV, I. K. FRATZSCHER, W., ET AL. GANZ, S. N., ET AL. GRANIER, L. F. GRIFFITHS, D. M. L., ET AL. GROZNY PETROLEUM INSTITUTE ;;;;;k bJKRAMER
ET AL. HELLMOiD;i., ET AL. HITACHI SHIPBUILDING & ENGINEERING HOECHST HOECHST
KEK HOECHST HOECHST HOECHST
262
PATENT REFERENCES BY COMPANY
Ace. No. ---w-B
302253 302272 302302 302264 302373 302414 302422 302424 302380 30238 1 302389 302390 302 101 302379 30203 1 30206 1 324314 302 176 324313 302201 302038 30237 1 302576 302392 302 102 302248 302093 302273 302064 30208 1 302083 302084 302259 302314 302299 302050 324315 324321 302112 302119 302245 302189 30226 1 324316 302188 302385 302133 302250 302265 30204 7 302252 324014 324991 358345 302295 302320
E:sx 302257
EiXS 302258 302570 324082 302387 302222
Chapter B-----B
t 6
Company --------------_--------------- HOECHST HOECHST HOECHST HORI, F. IBIDEN ENGINEERING IBIDEN ENGINEERING IBIDEN ENGINEERING INSTITUTE OF HEAT AND MASS TRANSFER, ACADEMY OF SC1 INSTITUTE OF ORGANIC CATALYSIS 81 ELECTROCHEMISTRY, INSTITUTE OF ORGANIC CATALVSIS & ELECTROCHEMISTRY, INSTITUTE OF ORGANIC CATALYSIS & ELECTROCHEMISTRY, INSTITUTE OF ORGANIC CATALYSIS 6 ELECTROCHEMISTRY, IONICS IVANOV, 0. R., ET AL. IWATANI INDUSTRIES IWATANI INDUSTRIES IWATANI SANGYO IWAVA SANGVO IWAVA SANGYO JAPAN GEON JAPAN OXYGEN KANG, T. H. KARAGANDA SYNTHETIC RUBBER PLANT KIROV, S. M., KAZAKH STATE UNIVERSITY KIRSEBOM, 6. N. KISAN, W., ET AL. KNAPSACK KNAPSACK KNAPSACK KNAPSACK KNAPSACK KNAPSACK KNAPSACK KNAPSACK-GRIESHEIM KNAPSACK-GRIESHEIM KOBE STEEL WORKS KOGVO KAIHATSU KENKYUSHO KOGYO KAIHATSU KENKYUSHO KOKUSAKU .PULP KRAMER, L., ET AL. KUEHN. E., ET AL. KURASHIKI RAYON KURASHIKI RAYON KURASHIKI RAYON L’AIR LIQUIDE LENINGRAD STATE SCIENTIFIC-RESEARCH INSTITUTE OF TH LEWIS, 3. 0. LINDE LINDE LINDE LINDE LINDE LINDE LINDE LINDE EISMASCHINEN LINDE EISMASCHINEN LINDE EISMASCHINEN LINDSTROM, 0. B. LOMONOSOV, M. V., INSTITUTE OF FINE CHEMICAL TECHNO L UMMUS L UMMUS LUMMUS LUMMUS LUMMUS LUZINA, V. P., ET AL. MAGYAR ASVANVLOLAI FOLD6
263
PATENT REFERENCES BY COMPANY
Act. No.
302029 302065 302066 30207 3 302074
::f: 9:
x: 302255 302277 302085 358230
xi 312036 302209 302231
35%%E 302076 302186 302187 302239 302274 302080 302623 30242 1 302408 30204 8 302425 302166 302184 302 200 302208 302228 302230 313868
312291 302235 302378
z:;
3a%E 302 103 302113 302163 302164 3#2393 302311 302142 302151 30239 1
Chapter -------
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f
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5
Company ------------------------------ MARATHON 0 I L MARATHON OIL MARATHON OIL MARATHON OIL MARATHON 01 L MARATHON OIL MARATHON OIL MARATHON 011 METALLGESELLSCHAFT METALLGESELLSCHAFT METALLGESELLSCHAFT MINISTERUL INDUSTRIEI PETROLULUI SI CHIMIEI MITSUI SHIPBUILDING i% ENGINEERING MOEGEL, G., ET AL. MONSANTO MONSANTO MONSANTO MONSANTO MONSANTO MONSANTO CHEMICAL MONTECATINI MONTECATINI EDISON MONTECATINI EDISON MONTECATINI EDISON MONTECATINI, SOC. GEN. IND. MOSKOVSKY INSTITUT TONKOI KHIMICHESKOI TEKHNOLOGII NATIONAL RESEARCH DEVELOPMENT NICHIGO ACETYLENE NIPPON ZEON NORTHERN NATURAL GAS NOVOMOSKOVSK CHEMICAL COMBINE1 LENINGRAD TECHNOLOCI PHILLIPS PETROLEUM PHILLIPS PETROLEUM PHILLIPS PETROLEUM PHILLIPS PETROLEUM PHILLIPS PETROLEUM PHILLIPS PETROLEUM PHILLIPS PETROLEUM t’~‘;;EC;NI~ WROCLAWSKA
POPOViKI: J: RESEARCH ASSOCIATION OF POLYMER RAW MATERIALS ROMANIA, ‘BALANTA’ PLANT ROMANIA, MINISTRY OF THE CHEMICAL INDUSTRY ROMANIA. MINISTRY OF THE CHEMICAL INDUSTRY ROMANVUK, L. M., ET AL. ROTHMANN, H. RUMMEL, R. RUOSCH, S., ET AL. S.A. POUR L’ETUDE ET L’EXPLOITATION DES PROCEDES GE S.A. POUR L’ETUDE ET L’EXPLOITATION DES PROCEDES GE SEVERODONETSK CHEMICAL COMBINE SHAWINIGAN CHEMICALS SHEVCHUK, V. U., ET AL. SHEVCHUK. V. U.. ET AL. SHEVCHUK; V. U.; ET AL. SHIN MEIWA KOGYO SHIN MEIWA KOGYO SHIN MEIWA KOGYO SHOWA DENKO SICEDISON SOCIETA PER AZONI SOC. BELGE DE L’AZOTE ET DES PRODUITS CHIMIQUES SOCIETE ANON. DES MANUFACTURES DES GLACES ET PRODUI SOCIETE BELGE DE L’AZOTE ET DES PRODUITS CNIMIQUES SOCIETE BELGE DE L’AZOTE ET DES PRODUITS CHIMIQUES SOCIETE FRANCAISE DE L’ACETVLENE ;O-s-;: M;BIL OIL
ET AL. SOKOLSiY,‘i. V., ET AL.
264
a -
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Ace. No. s-w-..- 302202
I:f:iX
::I::;
EE 302294 302364 302284 302282 302403 302 300 302 108 302109
3:5;:;
:zz;
33:z: 302238
%::x 302308 302012
3:E: 302177 302256 3026 10 302316 324157 302287 302288 302292 302244 302395
EXtt 302376 302394 302165
:tt f :: 30203 7 302110 302037 302559
::x 30207 1 302 138 302178 302179 302240 302410 302417 302418 302358 302369 302268
Chapter -m----s
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PATENT REFERENCES BY COMPANY
Company ------------------------------ SOLVAY STAMICARBON STANDARD OIL DEVELOPMENT STANDARD OIL, INDIANA STANDARD OIL, INDIANA STATE SCIENTIFIC-RESEARCH AND DESIGN INSTITUTE OF T STATE SCIENTIFIC-RESEARCH AND DESIGN INSTITUTE OF T STATE SCIENTIFIC-RESEARCH AND DESIGN INSTITUTE OF T STATE SCIENTIFIC-RESEARCH AND DESIGN INSTITUTE OF T TAMERS. M. A. TAMERS; M. A. TDK ELECTRONICS TECHNICAL ASSETS TEXACO TEXACO
TiKoO TEXACO TOA KAGAKU KOGVO KABUSHIKI KAISHA TOPCHIEV, A. V., INSTITUTE OF PETROCHEMICAL SVNTHES TOY0 KOATSU INDUSTRIES UGINE KUHLMANN UNION CARBIDE UNION CARBIDE UNION CARBIDE UNION CARBIDE UNION CARBIDE UNION CARBIDE UNION CARBIDE UNION CARBIDE UNION CARBIDE UNION CARBIDE 81 CARBON UNIVERSAL OIL PRODUCTS VEB CHEMISCHE WERKE BUNA VEB CHEMISCHE WERKE BUNA VEB CHEMISCHE WERKE BUNA VEB CHEMISCHE WERKE 8UNA VEB CHEMISCHE WERKE BUNA VEB CHEMISCHE WERKE BUNA VEB CHEMISCHE WERKE BONA VEB MASCHINENFABRIK & EISENGIESSERET DESSAU VEB MASCHINENFABRIK P EISENGIESSERET DESSAU VICKERS-ZIMMER VULIKH, A. I., ET AL. VULIKH. A. I., ET AL. WACKER-CHEMIE WACKER-CHEMIE ~~;~ER;;CH~MIE
WEIR: H: M: WESTINGHOUSE ELECTRIC WESTINGHOUSE ELECTRIC WESTINGHOUSE ELECTRIC WESTINGHOUSE ELECTRIC WESTINGHOUSE ELECTRIC WESTINGHOUSE ELECTRIC YANAGISAWA. E. YANAGISAWA, E. YANAGISAWA, E. ZAKLADY AZOTOWE IM. FELIKSA DZIERZYNSKIECO ZAKLADY AZOTOWE IM. PAWLA FINDERA ZIMMER VERFAHRENSTE
265
Figure 4.2
CALCIUM CARBIDE BY ELECTROCHEMICAL PROCESS
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I . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..."..".. m1-E SECTION . . . . . . . ..w.r...wr......u..u.u.ur....."."."~.~...."..........".....""..."..... C-IDE SsTK)N . . . . . ..".........................aa.~
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -I,ON SKT,ON . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
T-101 c-101 cmb~~ ss
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Figure 5.1
ACETYLENE FROM CALCIUM CARBIDE
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,“lllPKA,,ON SKTnN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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269
Figure 7.1 (Sheet 1 of 2)
ACETYLENE BY PARTIAL OXIDATION OF NATURAL GAS
)...............................................................................................“..........“..................... -,,o’.j SK,,ON . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..-............................................................ .
I
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Figure 7.1 (Sheet 2 of 2)
ACETYLENE BY PARTIAL OXIDATION OF NATURAL GAS
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Figure 7.4
ACETYLENE FROM NATURAL GAS PARTIAL OXIDATION PROCESS USING OIL QUENCHING FOR HEAT RECOVERY, REACTION SECTION
. . . . . . . . ..“.......................................................................................................................~~T.ON SKTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..“..........“.......................
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Figure 8.1 (Sheet I of 3)
ACETYLENE FROM NATURAL GAS BY ARC PROCESS
M-lOl(6)v I I
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Figure 8. 1 (Sheet 2 of 3)
ACETYLENE FROM NATURAL GAS BY ARC PROCESS
~................................................................................................“........................~~~ENE RECOVERY SKT,O,., . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
0 E-21, To K-201 t
Frm T-105
TOG2W
I K-201
t Tot-lob
TOO-IO) To E-101 I
zOlthw2w c-201B2o2 V-202 Hblm:~rr hmtu
c-2w Tkl C-204 C-2W Q-v-- cod- ktlmd khd cs+Abahr bntylmm ,_.'-3a?.
i : : 1 1 : 1 : : : : i : 1 :
: : 1
D
E-217 l- c I = 0 * I t To&O3
c-212 C-213 T-203 C-214 M-201
7!tEl? Amtylmm 2olmtTnL sdwnt BmDvmy OeJohu
E-r cdunn
l9Bl
279
Figure 8.1 (Sheet 3 of 3)
ACETYLENE FROM NATURAL GAS BY ARC PROCESS
V-JOIAAB K-221 c-201 ?K-ml elZW humlnBP
I..."............."......"....".............."..."...-............"..".".....""-..".~WUUI "Y . . . . . . . . . . . sse.W..."..."." . . . . . . Y.M.." . . . . . --"."--I . . . . . r-m . . . . urn . . . . -..-" . . . . . . UM.Y...U . . . . . --.."."..I
TOG2OB
K-261 E-Ml E-)(P
-I--r t-Y
.- 595pio o
I
K-4OlUimtSta~a) K-4OlbmndStqtd K-4( K-401
Wkr*~P--
E-211 E-216 E-221
r;m
E-4ap E-215 E-306
K-4020lh4Std
,................................~........-..”.......................................“..........“...“...“............ ~FQGEIUTION SKTION . ..“.....“...“U..“......“.-“-.“............~...................-.............................-”.”.......... 191)l
Figure 10.1
ACETYLENE RECOVERY IN ETHYLENE PLANT
K-101 K-l@
IO'FDMF
t -
L
/ la-109
E-105
I P
B&
5pio
J +J E-107 3
c-101 -
K-IOIIIPO c-lrn - *-
T-101 T-Ml DMFTmk oobldw
,...................................................~...“............-..“.....““..~...““.“.....”..............................~....”.......“......”..“..”“..~....”.”*...”.....“.”..-...................“....“....................-........--.. 1581
283