data book on hydrocarbons
DESCRIPTION
chemical engineering physical property handbook.TRANSCRIPT
DATA BOOK ON
HYDROCARBONSAPPLICA TION TO PROCESS ENGINEERING
by
J. B. MAXWELLNINTH PRINTING
•
ROBERT E. KRIEGER PUBLISHING COMPANYMALABAR, FLORIDA
ORIGINAL EDITION 1960REPRINTED 1977 FROM NINTH PRINTING 1968
Printed and Published byROBERT E. KRIEGER PUBLISHING COMPANY, INC.KRIEGER DRIVEMALABAR, FLORIDA 32950
© Copyright 1950 bySTANDARD OIL DEVELOPMENT COMPANYReprinted by Arrangement withVAN NOSTRAND REINHOLD CoMPANY
All rights reserved. No reproduction in any formof this book, in while or in part (except for briefquotation in critical articles or reviews), may bemade without written authorization frOm thepublisher.
PRINTED IN THE UNITED STATES OF AMERICA
Library of Congress Cataloging in Publication Data
Maxwell, J B 1902-Data book on hydrocarbons.
Reprint of the 9th printing published in 1968 by VanNostrand, Princeton, N. J., in The Esso series.
Includes bibliographies.1. Hydrocarbons. I. Title.
TP690.M35 1975 661'.81 74-30163ISBN 0-88275-257-X
PREFACEThe primary purpose of this book is to provide (1) basic data on hydro
carbons and petroleum fractions, (2) methods of applying these data to processengineering, including illustrative examples and some fundamental theory, and(3) applications of a few of the unit operations of chemical engineering uscdextensively in the petroleum industry.
Earlier editions of the present volume have been used in the Standard OilDevelopment Company and other affiliates of the Standard Oil Company (New.Jersey). Because this book has proved to be quite valuable to technical personnel,the Standard Oil Development Company has decided to make it available forpracticing engineers and students of petroleum technology.
The author is very much indebted to many associates in the preparation ofthis book and, in particular, to W. H. Hatch for invaluable assistance in editingthe text and preparing the charts for publication, to C. O. Rbys, Sr., for thederivation of the .Mollier diagrams and other charts, to C. J. Robrecht (orconstructive criticism and advice during the preparation of the manuscript. Furthermore, any list of acknowledgments would be incomplete without mentioningR. S. Piroomov who was responsible for the early development of a companydata book.
J. B. MAXWELL
Standard Oil Development CompanyLinden, New Jersey
•
CONTENTSPHYSICAL DATA
SElCTIOl\ PAGE
1. PHYSICAL CONSTANTS....................................... 1
Hydrocarbons, 2-Miscellaneous Organic Compounds, 6--MisceIlaneous Gases, 9
2. CHARACTERISTICS OF PETROLEUM FRACTIONS... . . . . . . . .. 10
Average Boiling Point, 14-Characterization Factor, Hi-Gravity, 18
3. MOLECULAR WEIGHT. . . . . . . . . . . . . . . . . .. . . . . .. ... ... . . . . . . . . . 19
Paraffins, 20-Petroleum Fractions, 21
4. VAPOH PRESSURE .
Paraffins and Olefins, 27-Diolefins and Acetylenes, 35-Aromatics, 37-Cycloparaffins, 39-Hydrocarbons, 40-Gasolines, 44
5. FUGACITY .
Fugacity Function of Individual Hydrocarbons, 49-Fugacity Function of Hydrogen, Ol-Fugacity of Hydrocarbon Vapors, 62-RelativeVolatility of LigM Hydrocarbons, 6~-Fugacity Correction Factor forLight Hydrocarbons in Absorber Oib, 67
24
45
6. CRITICAL PROPERTIES....................................... 68
Critical Temperature of Pure Hydrocarbons, 69-Critical Temperatureof Light Hydrocarbon Mixtures, 'i'O-Critical Pressure of Kormal Paraffins, 71-Critical Temperature and Pressure of Petroleum Fractions,72
7. THEHMAL PHOPERTlES .
Specific Heats of Gases and Vapors, 88-Enlhalpy-Presoure Relationship for Hydrocarbon Vapors, 92-Bpecifjr Heats of Liquid Hydrocarbons and Petroleum Fractions, 93-Latenl Ileat of Vaporization ofLight Hydrocarbons and Normal Paraffins, 94-Enthalpy of IndividualHydrocarbons, 98-Enthalpy of Petroleum Fractions, 114-MollierDiagrams for Light Hydrocarbons, 128
VII
75
viii
SECTION
CONTENTS
PAGE
8. DENSITy........................... . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
Conversion Charts for 0 API Gravity, 138-Specific Gravity of Saturated Hydrocarbon Liquids, 14o-Thermal Expamlion of LiquidPetroleum Fractions, 143-P-V-T Relations of Hydrocarbon Vapors,148
9. VISCOSITY. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
Conversion Charts, 158-Viscosity of Hydrocarbons and Crude Fractions, 161-Viscosity-Temperature Charts, 166--Viscosity Index ofLubricating Oils, 168-Viscosity Blending Index, 173-Viscosity ofHydrocarbon Vapors and Miscellaneous Gases, 174
10. COMBUSTION. . . 178
Heat of Combustion of Petroleum Fractions and Hydrocarbon Gases,18o-Enthalpy of Flue Gas Components, 182-Heat Available fromthe Combustion of Refinery Gases and Fuel Oils, 184-Properties ofFlue Gases, 189
UNIT OPERATIONS
11. FLOW OF FLUIDS............................................. 193
Friction Factor for Fluid Flow, 19B-Pressure Drop in CommercialPipes, 199-Equivalent Length of Fittings, 202-Friction Loss Dueto Contraction and Enlargement, 204-Discharge Characteristics ofWeirs, 205-Pressure Drop Across Tube Banks, 206
12. FLOW OF HEAT. . . . . . . . . . . . . . . . . . . . . . . . . . .. . . .. . 207
Heat Loss by Radiation and Natural Convection, 209-Heat Transferto Fluids Inside Tubes, 211-Heat Transfcr to Fluids Outside Tubes,212-Thermal Conductivity of Petroleum Fractions, Water, andGases, 213-Logarithmic Mean Temperatme Difference, 217
13. EQUILIBRIUM FLASH VAPORIZATION.. . . . . . . . . . . . . . . . . . . . . .. 222
14. FRACTIONATING TOWERS.. .. 230
Minimum Reflux Ratio and Theoretical Steps, 23O-Correlation ofTheoretical Steps with Reflux Ratio, 244-0verall Plate Efficiency,245-Packed Towcrs, 246
CONVERSIOX FACTORS. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 249
INDEX............................................................ 253
•
Section I
PHYSICAL CONSTANTS
In the following tables the more common physical constants are given forhydrocarbons, certain other organic series, and miscellaneous gases. While theseconstants, in general, are based upon reliable data, estimated "alues were includedin a few instances where available data were considered questionable. Where noreasonably good basis was available for either estimating or calculating the constants, they are omitted.
The density, boiling point, melting point, and heat of eo'mbustion for mostof the hydrocarbons are those given in the Burea1t of Standards Circular C461. 1
GENERAL REFERENCES
Annual Tables of Physical Constants, Nat. Research Council (19-11, 1942).Beattie, Poffenberger and Hadlock, J. Chem. Phys. 3, 96 (1935).Beattie, Simard and Su, J. Alii. Chem. Soc. 61, 24 (1939); 61,924 (1939).Cole and Cole, J. Chem. Phys. 9, 341 (1941).Doss, "Physical ~nstants of the Principal Hydrocarbons," 4th Edition, The Texas Co.,
New York, N.Y. (1943).Ginnings, J. Am. Cltell/. Soc. 62, 1923 (1940).Ginnings and Baum, J. Am. Chem. Soc. 59, 1111 (1937).Ingersoll, Thesis, ~Iass. Inst. Tech. (1930).International Critical Tables, Vols. I and III.Kay, Ind. Eng. Chem. 30, 459 (1938).Kharasch, J. Research Nat. Bur. Standards 2,359 (1929).Krase and Goodman, Ind. Eng. Chelll. 22, 13 (1930).Meyers, Scott, Brickwede and RAnds, Unpublished Data, Nat. Bur. Standards.Pickering, Bur. Standards Sci. Paper 511 (1926).Rintelen, Gross and Saylor, J. Am. Chelll. Soc. 62, 1923 (19-10).Tables anntlelles de wnstantes et dunnee nUllteriqlte, Vols. VII to XIII (1925-1939).
I' "Sclcdcd Values of Propertips of Hydrocarbons," Nal. Bur. ~lalldards Circular Cl,61(947).
1
PHYSICAL CONSTANTS OF HYDROCARBONS
DENSITY CRITICAL CONSTANTSHEAT OF COMBUSTION.
BOILING :.fELTING @ 60°F-BTU /IbMOLEC.FOR~tULA POINT POINT
WT. of of Sp Gr t P D°API60°/60° Lb/gal of Atm G/ml
Gross Net
NORMAL PARAFFINSMethane ................... CH, 16.0 -258.9 -296.5 340 0.30 2.50 -116.3 45.8 0.162 23,860" 21,500"Ethane .................... C,H. 30.1 -128.0 -297.8 247 .374 3.11 + 90.1 48.2 .203 22,300" 20,420-Propane ................... C,H, 44.1 - 43.8 -305.7 147 .508 4.23 206.3 42.0 .226 21,650" 19,930"Bu~no .................... C,H,o 58.1 + 31.1 -216.9 111 .584 4.86 306 37.4 .225 21,290' 19,670"
Pentane ................... C,H 12 72.1 96.9 -201. 5 92.7 .631 5.25 386.5 32.6 .232 21,070" 19,500"Hexane .................... C,H" 86.2 155.7 -139.5 81.6 .664 5.53 455.0 29.4 .234 20,780 19,240Heptane ................... C,H 16 100.2 209.2 -131. 1 74.2 .688 5.73 512.5 26.8 .234 20,670 19,160Octane ...... '" ........... C,H,s 114.2 258.2 - 70.3 6ti,{j .707 5.89 565 24.6 .233 20,590 19,100
Nonane .................... C,H,o 128.2 303.4 - 64.5 64.5 -.).) 6.01 612' 23" - 20,530 19,050. ,- ...Decane .................... C1oH" 142.3 345.2 - 21.5 61.3 .734 6.11 654' 22" - 20,480 19,020Undecane .................. C"H,. 156.3 384 .4 - 14.1 58.7 .744 6.19 695' 20" - 20,450 19,000Dodecane .... , ............. C12H " 170.3 421.3 + 14.7 56.4 ,753 6.27 731" lb' - 20,420 18,980
ISO-PARAFFINSIsobutane .................. C,H 1o 58.1 10.9 -255.0 120 .563 4.69 275 36 .234 21,240' 19,610"
2-Methylbutane (Isopentane), C,H 12 72.1 82.2 -255.5 94.9 .625 5.20 369.5 32.4 .234 21,030" 19,450"2,2-Dimeth:dpropane (~eo-
pentane). . .............. C,H" 72.1 49.0 + 2.1 105 .597 4.97 329" 35' - 20,960' 19,330"
2-Methylpentanc (Isohexane) , C,H" 86.2 140.5 -245 83.5 .658 5.48 437' 31' - 20,750 19,2103-Methylpcnt,ane, ........ C,H" 86.2 145.9 -180 80.0 ,669 5.57 443' 30" - 20,760 19,2202,2-Dimethylbutane ();eo-
hexane) . ' .. , ......... , ... C,H" 86.2 121.5 -147 6 84.9 .654 5.44 415' 31' - 20,700 19,1602,3-Dimethylbutane (Di-
isopropyl) ............... C.H" 86.2 136.4 -198.8 81.0 .666 5.54 441 31 . 241 20,740 19,200
2-Met,hylhexane (Isoheptane) . C,H I6 100.2 194.1 -180.8 75.i . 68:l 5.68 496 28" - 20,650 19,1403-Methylhexanc ............ C,H" 100.2 197.5 -182.9 73.0 .692 5.76 504 28.5" - 20,660 19,1503-Ethylpentane .... ...... (',H" 100.2 200.2 -181.5 69.ti .703 5.85 508' 28.5 - 20.670 19,1602,2-Dimethylpentane ....... ' (',H" 100.2 174.6 -190.8 77.'2 .678 5.64 475' 28.5 - 20,600 19,090
2,3·Dimethylpentane ........ C,H" 100.2 193.6 - 70.6 .700 5.83 498' 29 - 20,540 19,1302,4-Dimethylpentane ........ C,H" 100.2 176.9 -183.1 -- ') .678 5.54 477 28.5' - 20,620 19,110, I ._
3,3-Dimethylpentane ....... , C,H" 100.2 186.9 -211.0 71.2 .698 5.81 487' 28' - 20,620 19,110
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2,2,3-Trimethylbutane (Trip-tane) .................... C 7H 1S 100.2 177.6 - 13.0 72.1 0.695 5.78 480~ 29.5 - 20,620 19,110
2-Methylheptane (lsooctane) . CSH 18 114.2 243.8 -165.1 70.1 .702 5.84 549< 25~ - 20,570 19,0803-Ethylhexane .............. CsH 18 114.2 245.4 - 65.6 .718 5.98 551c 25" - 20,570 19,0802,5-Dimethylhexane (Di-
isobutyl) ................. CSHl~ 114.2 228.4 -130 71.2 .698 5.81 530 25 0.237 20,550 19,0602,2,4-Trimethylpentane ("lso-
octane") ................. C SH 18 114.2 210.6 -161. 2 71.8 .69u 5.79 515' 27" - 20,540 19.050
OLEFINSEthylene ........••......... C 2H. 28.0 -154.7 -272.5 2n . ;J;j 2.91 50 51 .22 21,640" 20,290Q
Propylene .......•.......... C 3H s 42.1 - 53.9 -301.4 140 .522 4.35 196.5 45.4 .2:~3 21,040Q 19,690Q
Butene-I ............. C,Hs 56.1 20.7 - 104 .601 5.00 293' 39" - 20,840" 19,490Q
Cis-Butene-2 ......•...... C.Hs 56.1 38.6 -218.0 94.2 .627 5.22 316' 37" - 20,780" 19,430Q
Trans-Butene-2 ............. C.Hs 56.1 33.6 -157.7 100 .610 5.08 310' 37" - 20,750" 19,400"Isobutene ........ , ...... C.Hs 56.1 19.6 -220.5 104 .600 4.99 292.5 39.5 .234 20,720" 19,370"
Pentene-1 (Amylene). CbH lO 70.1 86.2 -216.4 87.2 .647 5.38 385" 36" - 20,710Q 19,360"Cis-Pentene-2 ............ C;H1o 70.1 98.6 -290.2 82.6 .661 5.50 398' 35" - 20,660Q 19,310"
Trans-Pentene-2 ............ CbH lO 70.1 96.8 -211.0 84.9 .654 5.44 396' 35~ - ~O,640Q 19,290Q
2-Methylbutene-1 ........... C;H1o 70.1 88.0 - 84.5 .655 5.45 387" 36" - 20,610Q 19,260"3-Methylbutene-1 (lso-
amylene) .......... " ..... C;H lO 70.1 , 68.4 -292.0 92.0 . 6:~3 5.27 363' 37" - 20,660Q 19,310"2-Methylbutene-2 ........... C;H lO 70.1 101.2 -207.0 80.6 .667 5.55 401" 35" - 20,570" 19,220"
Hexene-1 ............. C 6H 12 84.2 146.4 -218.0 77.2 .678 5.64 463' 34" - 20,450 19,100Cis-Hexene-2 ............. C 6H 12 84.2 155.4 -231.0 73.9 .689 5.73 473' 34" - 20,420 19,070
Trans-Hexene-2 ............. C 6H 12 84.2 154.2 -207.0 75.7 .683 5.68 472' 34" - 20,400 19,050Cis-Hexene-3 ............. C SH l2 84.2 153.7 -211.0 75.4 .684 5.69 4i2' 34" - 20,420 19,070
Trans-Hexene-3 ......•...... C aH 12 84.2 154.6 -171 76.0 .682 5.68 473' 34" - 20,400 19,050
DIOLEFINSPropadiene .....•........... C 3H. 40.1 - 30.1 -213.0 106 .595 4.95 249 70 - 20,880Q 19,930"
Butadiene-l ,2 .............. C.H s 54.1 + 50.5 - 83.5 .658 5.48 343' - - - -Butad.iene-1,3 .............. C.H s 54.1 24.1 -1.64.0 94.2 .627 5.22 308 45 - 20,230" 19,180Q
Pentadiene-1.2 ..... : .. C;Hs 68.1 112.8 - 85.0 71.5 .697 5.80 420" - - - -Cis-Pentadiene- L3 ........ C;Hs 68.1 111.6 - 71.8 .696 5.79 420C - - 20,150" 19,040"
Trans-Pentadiene-l,3 ........ C;Hs 68.1 108.1 - 76.0 .682 5.68 415' - - 20,150Q 19,04QQ
Pentadiene-I,4 ....... CsHs 68.1 78.9 -234.0 81. 3 .665 5.53 350C - - 20,320Q 19,210Q3-Methylbutadiene-l,2 ....... CsHs 68.1 104 -184.0 82.9 .685 5.70 410" - - - -2-Methylbutadiene-l,3 (Iso-
prene) ................... C6H S 68.1 93.3 -231.0 74.8 .686 5.71 395' - - 20,060" 18,950Q
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Q Heat of combustion as a gas-otherwise as a liquid.• Estimated.
c Critical temperature-boiling point correlation." Vapor pressure curve or correlation.
* Mixture of cis- and trans-isomers.** Sublimes.
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PHYSICAL CONSTANTS OF HYDROCARBONS (Cont.)
DENSITY CRITICAL CONSTANTS HEAT OF COMBUSTIONBOILING MELTING @ 60°F-BTU libMOLEC.FORMULA POINT POINT
WT. OF OF Sp Gr t P D°API Lb Igal Gross Net600 /60 0 OF Atm G/rol
DIOLEFINS (Cont.)Hexadiene-1,2 .... : ..•.•.... CSHlO 82.1 172 - 64.5 0.722 6.01 495" - - - -Hexadiene-1,3* ..•.••....... CsH lO 82.1 163 - 67.8 .710 5.91 485" - - - -Hexadiene-l,4* ......•...•.. CaRlO 82.1 149 - 70.6 .700 5.83 470" - - - -Hexadiene-l.5 ...•.•••...... CSHlO 82.1 139.3 -221.4 71.8 .696 5.79 454 - - 20,130 18,980Hexadiene-2,3 ..... : .•...... CSH lO 82.1 154.4 - 75.1 .685 5.70 475' - - - -Hexadiene-2,4* ............. CsH lo 82.1 176 - 63.7 .725 6.03 500" - - - -3-Methylpentadiene-1,2 ...... CSH lO 82.1 158 - 65.0 .720 5.99 4W' - - - -4-Methylpentadiene-l,2 ...... CSH lO 82.1 158.0 - 67.0 .713 5.93 480" - - - -2-Methylpentadie:le-1,3* ..... CSH lO 82.1 169 - 63.9 .724 6.03 490" - - - -3-Methylpentadiene-l.3* ..... CSH 10 82.1 171 - 59.7 .740 6.16 495' - - - -4-Methylpentadiene-1,3 ...... CsH lo 82.1 169.3 - 94.0 63.9 .724 6.03 490" - - - -2-Methylpentadiene-1.4 ...... CSH IO 82.1 133 - 70.9 .699 5.82 445' - - - -2-Methylpentadiene-2,3 ...... ~HIO 82.1 162.0 - 66.1 .716 5.96 485' - - - -2,3-Diroethylbutadiene-1,3 ... CSH lO 82.1 155.7 -105 62.1 .731 6.08 475' - - 19,880 18.7302-Ethylbutadiene-1,3 ........ CaRlO 82.1 167 - 61.0 .735 6.12 490' - - - -
ACETYLENESAcetylene .................. CzHz 26.0 -119** -114 209 .416 3.46 103.5 62.0 0.231 21,47(}l1 20,74~
Methylacetylene ............ CaH. 40.1 - 9.8 -153 94.9 .625 5.20 275' 65~ - 20.810" 19.8W
Butyne-1 (Ethylacetylene) ... C.Hs 54.1 + 47.7 -188.5 86.2 .650 5.41 375 65~ - 20.65QQ 19,6oog
Butyne-2 (Dimethylacetylene) C.Hs 54.1 80.4 - 26.0 71.2 .698 5.81 420 60~ - 20.51QQ 19,46()Q
Pentyne-1 (Propylacetylene). CsHs 68.1 104.4 -159 71.8 .696 5.79 429 - - 20,550g 19,440g
Pentyne-2 .................. CsHs 68.1 132.8 -148 66.1 .716 5.96 460" - - 20,45QQ 19,340g
3-Methylbutyne-1 (Isopropyl-acetylene) ................ CsHs 68.1 82 - 79.7 .670 5.58 410" - - 20.5W 19,390"
Hexyne-1 (Butylacetylene) ... CsH lo 82.1 160.9 -205.6 65.0 .720 5.99 - - - - -Hexyne-2 .................. CSH lO 82.1 184.1 -126.4 60.8 .736 6.13 - - - - -Hexyne-3 ...............•.. CsHlO 82.1 179.2 -149.8 63.1 .727 6.05 - - - - -4-Methylpentyne-1 .......... CSHlO 82.1 142.1 -157.1 67.5 .711 5.92 - - - - -4-Methylpentyne-2.......... CSH lO 82.1 162 - 65.3 .719 5.98 - - - - -3,3-Diroethylbutyne-1 ....... CaRlO 82.1 100.0 -114.2 78.7 .673 5.60 - - - - -
OLEFINS-ACETYLENESButen-3-yne-1 (VinylAcety-
lene) .................•.. C.H. 52.1 42 - 73.9 .689 5.73 365" 75.; - - -
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Penten-l-yne-3 . ............ C.He 66.1 138.6 - 58.7 0.744 6.19 - - - - -Penten-l-yne-4 (Allylacety-
lene) . ................... C,He 66.1 107 - 49.4 .782 6.51 - - - - -2-Methylbuten·l-yne·3 . ..... CoHo 66.1 90 - - - - - - - - -Hexen-l-yne-3 . ............. C.H. 80.1 185 - 56.4 .753 6,27 - - - - -Hexen-l-yne-5 .. ............ CoHo 80.1 158 - 32.8 .861 7.17 - - - - -2-Methylpenten-l-yne-3 ..... CoHo 80.1 169 - - - - - - - - -3--Methylpenten-3-yne-l* ..... CoHo 80.1 156 - - - - - - - - -
AROMATICSBenzene ... ................. CoHo 78,1 176.2 41.9 28.6 .884 7.36 551.3 47.9 0.304 17,990 17.270
Toluene ..... ............... C,H. 92.1 231.1 -139.0 30.8 .872 7.26 609.1 41.6 .292 18,270 17,450
o-Xylene .... ............... C.H IO 106.2 292.0 - 13.3 28.4 .885 7,37 675 37 .288· 18.500 17,610m-Xylene .........•....... . CaHlo 106.2 282,4 - 54.2 31.3 .869 7.24 655· 36' .288· 18,500 17,610;p-Xylene . .............. , ... CaHlo 106.2 281.0 + 55.9 31.9 .866 7.21 652 35' .270' 18,430 17,540Ethylbenzene .... ........... CaHlo 106.2 277 .1 -138.9 30.8 .872 7.26 655 38 - 18,490 17.600
1,2,3-Trimethylbenzene . ..... C,Hu 120.2 349.0 - 13.8 25.7 .900 7.49 72C/' 32' - - -1,2,4-Trimethylbenzene (Pseu·
documene) . .............. C,Hu 120.2 336.5 - 47.3 29.1 .881 7.34 708' 33 - 18,570 17.6201,3,5·Trimethylbenzene (Me-
sitylene) . ................ C,H" 120.2 328.3 - 48.6 31.1 .870 7.24 700' 33 - 18,620 17,670
Propylbenzene . ............./'
C9H l2 120.2 318.6 -147,1 31.9 .866 7,21 690 34' - 18,660 17,710lsopropylbenzene (Cumene) .. C9Hn 120.2 306.3 -140.8 31.9 .866 7.21 68C/' 35' - 18.670 17,720I-Methyl-2-Ethylbenzene .... C,H" 120.2 329.2 -126,6 28.7 .883 7.35 702< 34' - - -I-Methyl-3-Ethylbenzene .... C,H" 120.2 322.7 - 31.1 .870 7.24 695' 34' - - -I-Methyl-4-Ethylbenzene .... C,R" 120.2 324.5 - 82.7 31.5 .868 7.23 696' 34' - - -
CYCLOPARAFFINSCyclopropane ... ............ C,H. 42.1 - 27.0 -196.6 98.6 .615 5.12 256 54 - - -Cyclobutane . ............... C.H. 56.1 + 54.7 - 58.0 74.8 .686 5.71 385' 50' - - -Cyclopentane . ...•.......... CeHlo 70.1 120,7 -136.7 56,9 .751 6.25 470' 46' - 20,350' OOסס.19
Methylcyc1opentane . ........ CtHn 84.2 161.3 -224.4 56.2 .754 6.28 520' 42' - 20,110 18.7601, I-Dimethylcyclopentane .... C,Hu 98.2 189.5 -105 54.7 .760 6.33 550' 42' - - -l,2··)imethylcyc1opentane-cis. C7Hu 98.2 210.7 - 62 50.4 .778 6.48 570' 40' - 20,020 18,6701,2-Dimethylcyclopentane-
trans . ................... C,Hu 98.2 197.4 -182 65.4 .757 6.30 560' 41' - 20.020 18,6701,3-Dimethylcyclopentane-
trans . ................... C7H 14 98.2 195.4 -213 57.2 .750 6.24 555' 41' - - -Ethylcyclopentane .......... C7H u 98.2 218.2 -217 52.0 .771 6.42 580' 40' - 20,110 18.760
Cyclohexane ................ CeRn 84.2 177.3 + 44 49.0 .784 6,53 538 40.4 .273 20.030 18.680Methylcyclohexane . ......... C7H 14 98.2 213.6 -195.6 61.3 .774 6.44 575 40' - 20.000 18.650
, Heat of combustion &8 a gas-otherwise &8 a liquid.• Estimated.
C Critical temperature-boiling point correlatioil.., Vapor pressure curve or correlation.
• Mixture of cis- and trans' isomers.•• Sublimes.
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PHYSICAL CONSTANTS OF ORGANIC COMPOUNDS
DENSITYCRITICAL HEAT OF COMBUSTION
MELT- HEAT OF @60°F-BTU /lbBOILING CONSTANTSMOLEC. ING VAPORIZ.
FORMULA POINTWT. of POINT Sp Gr t P D @B.P.
of 600 j600 Lb jgal of Atm Gjml BTU lib Gross Net
----ALCOHOLS
Methanol (Methyl Alcohol) .. CHaOH 32.0 148.1 -143.7 0.796 6.63 464.0 78.7 0.272 474 9760 8580
Ethanol (Ethyl Alcohol) ..... CHaCH20H 46.1 173.0 -174 .794 6.61 469.6 63.1 .275 361 12,780 11,550
Propanol-1 (Normal PropylAlcohol) ................. CHaCH2CH20H 60.1 207.0 -195 .808 6.73 506.7 50.0 .273 296 14,450 13,190
Propanol-2 (Isopropyl Alco-hoi) ........ , ............ (CHa),CHOH 60.1 180.2 -129 .789 6.57 - - - 289 14.350 13.090
Butanol-1 (Normal ButylAlcohol) ................. CHa(CH2hCH2OH 74.1 243.9 -129.6 .814 6.78 549 48 - 254 15.500 14,220
Butanol-2 (Sec. Butyl Alcohol) CHaCH2CH(OH)CHa 74.1 211.1 - .811 6.75 - - - 242 - -2-Methylpropanol-l (Isobutyl
,
Alcohol) ................. (CHahCHCH2OH 74.1 226.4 -162 .806 6.71 - - - 249 15.450 14.1702-Methylpropanol-2 (Tert.
Butyl Alcohol) ........... (CHa)aCOH 74.1 180.7 77.9 (.793) (6.60) - - - 235 15,290 14,010
Pentanol-1 (Normal AmylAlcohol) ................. CHa(CH2)aCH20H 88.1 280.4 -109.8 .819 6.82 - - - 223* 16,220 14,930
Pentanol-2 (Sec. Amyl Alco-hoi) ..................... CHa(CH2hCH(OH)CHa 88.1 247.1 - .814 6.78 - - - 213* -
Pentanol-3 (Diethyl Carbinol) (CH.CH2hCHOH 88.1 240 - .826 6.88 - - - 211* - ...2-Methylbutanol-l (Sec. Butyl
Carbinol) ................ CHaCH2CH(CHa)CHIOH 88.1 264 - .820 6.83 - - - 218* - -- .825 -6.87
2-Methylbutanol-2 (Tert.Amyl Alcohol) ........... CHaCH2C(OH) (CHah 88.1 215.8 15 .815 6.79 - - - 203* 16,030 14,740
3-Methylbutanol-1 (IsoamylAlcohol) ........ , ........ (CHahCHCH2CH t OH 88.1 269.2 -179 .814 6.78 - - - 216 16.150 14,860
3-Methylbutanol-2 (MethylIsopropyl Carbinol) ....... (CHahCHCH(OmCH. 88.1 233 - .825 6.87 - - - 209* - -
2.2-Dimethylpropanol-l (Tert.Butyl Carbinol) .......... (CHa)aCCH20H 88.1 236 120-125 - - - - - 210* - -
GLYCOLS AND GLYCEROLEthanediol-l,2 (Ethylene Gly-
col) ..................... CH2(OH)CH2OH 62.1 387.5 9 1.118 9.31 - - - 344 8250 7340- ..
0:.
tj>~tooo~
oZ:I:
~~o
§oZ00
Propanediol-1,2 (PropyleneGlycol) ................. CH3CH(OH)CH2OH 76.1 371 - 1.042 8.68 - - - 273* 10,350 9350
Propanediol-1,3 (Trimethy- CH2(OH)CH2CH2(OH) 76.1 850 - - - - - - 266* 10,450 9450lene Glycol) (appr .)
Propanetriol-1,2,3 (Glycerol). CH2(OH)CH(OH)CH2OH 92.1 554 65.0 1.265 10.53 - - - - 7760 6940
ETHERSMethyl Ether .............. CH,OCH3 46.1 -11.5 -217 - - 260 52 0.271 187 13,570u 12,340u
Ethyl Ether ............... CH,CH2OCH2CH, 74.1 94.1 -177 .3 0.719 5.99 381 35 .262 151 15,840 14,560
Propyl Ether .............. CH3(CH2)20(CH2)2CH3 102.2 194.2 -188 .752 6.26 - - - 129 16,930 15,630Isopropyl Ether ........ '.' .. (CH')2CHOCH(CH,)2 102.2 155.3 -122 .729 6.07 - - - 120 16,870 15,570
Butyl Ether ............... CH3(CH2)30(CH2)3CH3 130.2 288.0 -144 .773 6.44 - - - 115* 17,560 16,250Sec. Butyl Ether ........... [CH3CH2CH (CH,) 120 130.2 250 - .760 6.33 - - - 109* - -
ALDEHYDESMethanal (Formaldehyde) ... HCHO 30.0 - 3 -180 - - - - - 320* 8050U 7420U
Ethanal (Acetaldehyde) ..... CHaCHO 44.0 68.5 -190.3 .786 6.54 - - - 257* 11,400 10,540
Propanal lPropionaldehyde) CH,CH2CHO 58.1 120 -114 .812 6.76 - - - 215*' 13,400 12,420
Butanal (Butyraldehyde) .... CH3CH2CH2CHO 72.1 167.2 -144 .809 6.74 - - - 189* 14,640 13,5902-Methylpropanal (Isobuty-
raldehyde) ............... (CH3)2CHCHO 72.1 142 - 87 .799 6.65 - - - 180* 14,600 13,550
KETONESPropanone (Acetone) ....... CH3COCHa 58.1 133.0 -138.8 .795 6.62 - - - 220 13,260 12,280
Butanone (Methyl EthylKetone) ................. CH3COCH2CH, 72.1 175.5 -123.5 .810 6.74 - - - 190 14,540 13,490
Pentanone-2 (Methyl PropylKetone) ................. CH3COCH2CH2CH, 86.1 216.1 -108.0 .812 6.76 - - - 168* 15,430 14,330
Pentanone-3 (Diethyl Ketone) (CH3CH2hCO 86.1 215.2 - 40 .820 6.83 - - - 168* 15,380 14,2803-Methylbutanone-2 (Methyl
Isopropyl Ketone) ........ CH3COCH (CHa)2 86.1 200.7 -134 .820 6.83 - - - 165* 15,350 14,250
4-Methyl Pentanone-2(Methyl Isobutyl Ketone) . CH,COCH~H(CH,h 100.2 240.6 -119 .806 6.71 - - - 152* 15,980 14,840
~
P::~00......(1
>~
(1o~00~>Z;1
* Calculated or estimated with a probable accuracy of ±2%.u Heat of combustion as a gas-otherwise as a liquid.
..
"'-J
PHYSICAL CONSTANTS OF GASES
DENSITY CRITICAL CONSTANTSHEAT OF COMBUSTION
MOLEC.BOILING MELTING @ 60°F-BTU j1b
FOn~ULA POINT POINT
,~~WT. of of Sp Gr t P D°API 60°/60° Lb/gal of Atm G /ml Gross
Ammonia ............ NH3 17.0 - 28.1 -107.9 97.5 0.617 5.15 270.3 111.5 0.235 9670 8000
Carbon Dioxirle ...... COz 44.0 -109.3* - 69.9 '42.0 .815 6.78 88.0 73.0 .460 - -
Carbon Monoxirle .... CO 28.0 -312.7 -::137.0 - - - -220.4 34.5 .301 4345 4345
Chlorine ............. Ch 70.9 - 30 -151 - - - 291 76 .57 - -
Ethyl Chloride ....... CzH~CI 64.5 54.1 -214 25.5 .901 7.51 369 51.6 .33 - -
Hydrogen ........... Hz 2.0 -423.0 -434.5 - - - -400 12.8 .031 61,100 51,600
Hydrogen Chloride ... HCl 36.5 -121.0 -173.6 - - - 124.5 81.6 .42 - -
Hydrogen Sulfide ..... H 2S 34.1 - 76.5 -122.0 46.0 .797 6.64 212.7 88.9 - 7100 6550
Methyl Chloride ..... CH3Cl 50.5 - 11.6 -143.8 20.3 .931 7.76 289.6 65.8 .37 - -
Nitrogen ............ N2 28.0 -320.5 -346.0 - - - -232.8 33.5 .31 - -
Oxygen ............. Oz 32.0 -297.4 -362.0 - - - -181. 9 49.7 .43 - -
Sulfur Dioxide ....... S02 64.1 14.0 - 98.9 - 1.394 11.62 315.0 77.7 .52 - -
* .Sublimes.
..
"'tl~
~~o>~
oozU1"-3>Z"-3U1
~
Section 2
CHARACTERISTICS OF PETROLEUMFRACTIONS
Average Boiling Point of Petroleum Fractions
Many physical properties of pure hydrocarbons can be correlated with specificgravity and normal boiling point as independent variables. However, for use in thepetroleum industry, these correlations must also be applicable to petroleum fractions which are mixtures of a large number of components, usually having a widevariation in boiling points.
While the average specific gravity is a property of the petroleum fractionwhich can be measured directly, just as in the case of pure compounds, there is notan analogous average normal boiling point for a mixture. By integrating or averaging its distiUation curve (temperature vs. liquid volume percent distilled), avolume average boiling point can be determined for the mixture. However, asWatson and Nelson! and Smith and Watson 2 have pointed out, this has no specialsignificance as a true average boiling point and many physical properties can bebetter correlated by the use of some other average boiling point, i.e., weightaverage, molal average, etc. Consequently, in all correlations involving boilingpoints of petroleum fractions, the proper average should be used. For the following physical properties, these are:
Average Boiling Point Physical Property
Volume average ViscosityLiquid specific heat
Weight average True critical temperature
Molal average Pseudo-critical temperatureThermal expansion of liquids
Mean average Molecular weightCharacterization factorSpecific gravityPseudo-critical pressureHeat of combustion
1 Watson and Nelson, Ind. Eng. Chem. 26, 880 (1933).2 Smith and Watson, Ind. Eng. Chem. 29,1408 (1937).
10
,.
CHARACTERISTICS OF PE'l'ROLEUM FRACTIONS 11
Since a distillation curve is usually available and a volume average boilingpoint is readily obtained therefrom, the other average boiling points are given asa function of these data. The chart on page 14 is based on an assay (True BoilingPoint) distillation 3 of the whole crude, while the chart on page 15 refers to the1070 (or ASTM) distillation of the fraction itself.
The chart on page 14 was derived empirically from crude assay fractions of anumber of crudes. For narrow boiling fractions, all of the average boiling pointsapproach each other and the volume average boiling point may be used for any ofthe others. Then, by appropriately combining the volume average boiling points ofthe narrow cuts, the various average boiling points of wider cuts were determined.The weight and molal average boiling points of the wider cuts were calculateddirectly by combining the narrow cuts on the basis of their weight and mole fractions, respectively. The mean average boiling point could not be calculated in thesame manner since it is not a direct average or integral of its fractional parts. Asused herein, mean average boiling point is defined as the boiling point which bestcorrelates the molecular weight of petroleum fractions. Consequently, the meanaverage boiling point for wider cuts was determined indirectly from the generalizedmolecular weight chart on page 21.
Although Smith and Watson proposed a cubic average boiling point for thecorrelation of characterization factor, specific gravity-boiling point relations forthe different crudes indicate that the present mean average boiling point can beused for correlating gravity, and consequently characterization factor. Smith andWatson also used cubic average boiling point for correlating viscosity, but thepresent data indicate that the volume average is the proper boiling point.
Since these boiling point correlations were developed directly from crudeassay distillations, this chart should always be used 4 if an assay is available.Otherwise, the 10% (or ASTM) distillation of the fraction may be used in conjunction with the other chart. The latter was derived from the crude assay chartand an empirical correlation between the two types of distillation curves. Thedifference between the two sets of curves at zero slope represents the thermometerstem corrections for the 10% distillations.
In the case of light hydrocarbon mixtures, where the analysis is known, thevolume, weight, and molal average boiling points can be calculated directly fromthe boiling points of the components and their volume, weight, and mole fractions,respectively. On the oth~r hand, the mean average boiling point must be determined indirectly from the average molecular weight of the mixture. Up to an
3 Approximately 15 theoretical plates and 5 to 1 reflux ratio.4 Below slopes of 2°F/% for low boiling fractions (V.A.B.P. < 500°F) and 3°F/% for
high boiling fractions (V.A.B.P. > 500°F), the volume average may be used for the otheraverage boiling points with very little error.
12 DATA BOOK ON HYDROCARBONS
average molecular weight of 80, the molecular weight-boiling point relation fornormal paraffins (page 20) may be used for this purpose, but for higher molecularweights the generalized chart on page 21 should be employed.
Characterization Factor
Watson and Nelson 1 introduced characterization factor as an index of thechemical character of pure hydrocarbons and petroleum fractions. The characterization factor of a hydrocarbon is defined as the cube root of its absoluteboiling point in oR divided by its specific gravity (60°F/60°F), or
Characterization Factor = ytTB/Sp Gr
Characterization factor is given on page 16 as a function of gravity in °APIand boiling point in of for hydrocarbons and petroleum fractions.
That characterization factor is only an approximate index of the chemicalnature of hydrocarbons is indicated by its variation with boiling point both formembers of a homologous series and for fractions from the same crude (page 17).However, it has considerable value in that it can be applied to the entire boilingrange of a crude and it has been generally accepted by the petroleum industry.
Typical Crude Fractions
For approximate use when there are insufficient data, several correlations havebeen developed for typical crude fractions grouped according to characterizationfactor and viscosity index. 5 These groups are numbered in order of decreasingparaffinicity and each may be considered representative of the crude fractionswithin its characterization factor or viscosity index range. The five groups werearbitrarily selected as follows:
GroupI .II .III .IV .v .
CharacterizationFactor
12.1-12.611.9-12.211.7-12.011.5-11.811.3-11. 6
Viscosity Index ofLube Fraclions6
80-10060-8040-6020-400-20
Fractions from some of the more common crudes are cla5sifil'd in the followingtable:
lS See page 156.6 Dewaxed to +20°F pour.
CHARACTERISTICS OF PETROLEUM FRACTIONS 13
TYP.lCAL GROUP
CRUDE White Gas OilsProducts and Heavier
Pennsylvania I IRodessa. . . . . . . . . . . . . . . . . . . . . . . . . . . .. I IPanhandle . . . . . . . . . . . . . . . . . . . . . . . . . . . II IMid-Continent . . . . . . . . . . . . . . . . . . . . . .. II IIKuwait I-II II-III
Iraq IIIranian IIEast Texas IIISouth Louisiana. . . . . . . . . . . . . . . . . . . . .. IIIJusepin III
West Texas . . . . . . . . . . . . . . . . . . . . . . . . .. IIITia Juana (Med. and 102) IIIColombian IVLagunillas . . . . . . . . . . . . . . . . . . . . . . . . . .. V
II-IIIII-IIIIIIIIII
IIIIVIVV
Since, in the case of some crudes, the lower boiling fractions belonged in adifferent group than the higher boiling fractions, they were classified separatelythat is, into white prorlucts having an average boiling point less than 500°F, andgas oils and heavier having an average boiling point greater than 500°F.
2 3 4 5 6 7 9 10+40
+ 30WEIGHT ·AVERAGE·
+20Ii •
iJ+'0
~
- AVERAGE BOILING POINT0 OF PETROLEUM FRACTIONS ~
CRUDE ASSAy DISTILLATION i
- 10
- 20 MEAN AVERAGE
-30
-40
-50
-60
-705 6 7 8 9 102 4
MOLAL AVERAGE
ty =to+4t.50+tIOO6
FOR WHOLE CRUDES:t y =ho t t,50+ teo
* THE CUT RANGE MAY BE USED FORTHE SLOPE AND THE 50% POINT FORTHE VOL. AV. B.P. UNLESS THEDISTILLATION FOR THE FRACTIONDEVIATES APPRECIABLY FROM ASTRAIGHT LINE. !N THE LATTEREVENT THE FOLLOWING FORMUI ASSHOULD BE USED:
_ t7O-t10S - 60
0
-20
-40 -
-60In..V> -80
cr-'00....
('~
-120
-'403 4 5 6
14
7 8 9 10
t40
WEIGHT AVERAGE
+20
,.L
0
,~ t . t·-20
2 4 5 6 7 8
i:J...~t-L_; of i ....... .ly.......H-t~.
MEAN AVERAGE AVERAGE BOILING POINT+20
OF PETROLEUM FRACTIONS,.
0 10 % (A.5.tM.) DISTILLATION
-20IF AVAILABLE, THE CRUDE ASSAY
DISTILLATION SHOULD BE USED FOR-40 DETERMINING AVERAGE BOILING POINTS.
r -60
r-l/}
< -eo3 4 5 6 7 82
?cr
(.f-MOLAL AVERAGE
+-20
*THE SLOPE AND AV. B.P. SHOULD
0 BE DETERMINED FROM THE FOLLOWINGFORMULAS:
S=t,,70 - tlO
(
-20 60 ;.,
tv =tlo+2t50 +t9O
4-40
IF THERE ARE INSUFFICIENT DATATHE 50% POINT MAY BE USED FOR
-60 THE VOL. AV. B.P.
FOR WHOLE CRUDES:-80
t30+t.50+t70tv: 3-100
-120
'.-1403 5 6 7 82 4
15
13.0
12.0
_ 11.0~
10.0
90
CHARACTERIZATION FACTOR
VS BOILING POINT AND GRAVITY
14.0
13.0
12.0
11.0
10.0
9.0
100 200 300 400 500 600 700
..800 900 1000
I100 200 300 400 500 600 700 800 900 1000..
CRUDE TYPICAL GROUP . .,
13.6WHITE GAS OILS CHARACTERIZATION FACTOR ;.t~ 1 I:n __
PRODUCTS a HEAVIER. .-!{ ~~ili
13.6PENNSYLVANIA I I ~ BOILING POINTRODESSA I I .1%1+I.l-++J.1=:+I::t1+134HHH1 PANHANDLf II I ~ r 13.4
• MID' CONTINENT II II TVPICAL CRUDE FRACTIONS ~mKUWAIT I-II II-III
IRAO II II-III T· 13.213.2EEHHl IRANIAN II II- IIIEAST TEXAS III IIS.LOUISIANA III II
1 m:aE .lUSEPIN III III >- r 13.03.0WEST TEXAS liI IIITIA .lUANA (NED. a 102) III IVCOLOMBIAN IV IV -... • 12.812.1:) a:m:a LAGUNILLAS v V
12.6 :i '. >- 12.6, .I' .
-12.4, 12.4
~ ,.of:
12.2 12.2.~
12.0 12.0
11.8 11.8
11.6 r 11.6II ~ ,J;tt
H
11.4r TIT " " 1/.4
r-. i ,
r i ' 1->- _Ir H-I" ;'++1+1-++1 11.211.2 d~ ..,.+1-~ -I r
.t I ., . I· . .,:
/00 200 300 400 500 600 700 800 900 1000
I..i. _
~
100 200 300 400 500 600 700 800 1300 JOOO
GRAVITY~ BOILING POINTTYPICAL CRUDE FRACTIONS
70
60 60
50 IHB111lHlIIII1l1l1J 1111 II tlHIIJIlJI IlIllIIlIIlIHt"KINI!'N:"lIIJilJIIH1I1lIlit11J»111 1111111111111111 111I111l"KlOIIJ II i1II1III1II1IJIIJLLIUHlIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII11II11111111 flll150
....00
40 40CRUDE TYPICAL GROUP
WHITE GAS OILSPRODUCTS a HEAVIER
PENNSYLVANIA I IRODESSA I. IPANHANDLE II % II tlllllllllI11tllltul1tlJIlItn1'W"~1i\IM1t1n&J~IIIIIIIIIIIIIIIIIIITI't'l+l>lilJ FEIBHtlilMIllllllllllll13030 I:fI::i::l:!:1I MID· CONTINENT II IIKUWAIT I·II II·III
IRAO II II·IIIIRANIAN II II-U.IEAST TEXAS III IIS. LOUISIANA III II.IUSEPIN III In
20~ II1II111111 i1IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIImmmiiIII III IlrmUWOU1l11I1't'ffi!lratJUI:I!li1ln'iJmBTBI20WEST TEXAS III nITIA JUANA (MED. a 102) III. IVCOLOMBIAN IV I1I'LAGUNILLAS V V
1010J 200 300 400 500 600 700 .. 800 900 1000
L
Section 3
MOLECULAR WEIGHT
The molecular weight chart for pet.roleum fractions on page 21 was derivedfrom an empirical correlation of molecular weight and the function, T,,Jso.4o,·where T m i" the mean avcrage boiling point of the fraction in oR, and s, the specific ~
gravity at 60°F/60°F. The ayerage deviation for about one hundred petroleumfractions from 75 to 500 molecular weight is +20/0.
Up to a molecular weight. of about 300 this correlation applies equally wellto pure hydrocarbons, with the exception of normal paraffins, which have lowermolecular \\'eights than predicted by the chart. Above 300 molecular weight mostpure hydrocarbons for which data are available deviate from the correlation inthe same direction as the normal paraffins. An explanation of this incongruitymay be that these particular high molecular weight compounds have relativelylong chains and consequently should fall somewhere between the normal paraffinsand the multibranched and multicyclic hydrocarbons in petroleum fractions.
The molecular weight of crude fractions is given as an independent functionof mean average boiling point, page 22, and also of gravity, page 23, for approximate use when only one of these variables is known. Examination of these chartsshows that the boiling point chart is much less susceptible to variations with typeof crude than the gravity chart and, consequently, will usually give a betterapproximation than the latter. However, in general, gravity rather than theboiling point will be available.
GENERAL REFERENCES
API Research Project 42.Bridgeman, Proc. API 10, No.2, p. 124 (1929).Doss, "Physical Properties of the Principal Hydrocarbons," 4th Edition, The Texas Co.,
New York, N.Y. (1943).Fitz imons and Thiele, Ind. Eng. Chem. (Anal. Ed.) 7, 11 (1935).Francis and Wood, J. Chem. Soc. 48, 1420 (1926).Kay, Ind. Eng. Chem. 28, 1014 (1936).Mail' and Schicktanz, J. Research Nat. Bur. Standards 17, 909 (1936).Mail' and Willingham, .T. Research Nat. Bur. Standards 21, 535, 565, 581 (1938).Rosenbaum, J. Chern. Phys. 9, 295 (1941).Shepard, J. Am. Chern. Soc. 53, 1948 (1931).
19
400 500 600 700 800 900 1000 1100
600
500
400
MOLECULAR WEIGHT n BOILING POINT
NORMAL PARAFFINS AND ISOPARAFFINS
600
. 500
400
I - AVERAGE OF ISOMERS CONTAININGA SINGLE METHYL OR ETHYL BRANCH
2 - AVERAGE OF ALL OTHER ISOMERS
200
120
100
80
60
40
20
-100 a
20
100 200
200
180
160
140
120
100
80
60
40
20
300 400
MOLECULAR WEIGHTYo! BOILING POINT AND GRAVITY
600 PETROLEUM' FRACTIONS
700 800 900 1000 1100 1200
500
400
300 300
280
200 260
240
220
200 200
180 180
160 160
140 140
120 120
100 100
80 eo
100 200 300 400 500 600 700 aoo21
200 300 400 500 600· 700 800 900
460 460
.MOLECULAR WEIGHT~ BOILING POINT440 TYPICAL CRUDE FRACTIONS 440
420 420
400 400
CRUDE TYPICAL GROUP
380 WHITE GAS 01LS 380'RODUCTS a HEAV lEA
PENNSYLVANIA I I.,
RODESSA I I360 PANHANDLE II I. 360
MID - CONTINENT II IIKUWAIT I-II II-III
340 IRAQ II II-III 340IRANIAN II II-IIIUST TEXAS nI IIS. LOUISIANA III II
320 JUSEPIN III In 320WEST TEXAS UI InTIA JUANA (NED. a 102) III IV
300 COLOMBIAN IY IV 300LAGliNILLAS Y Y
280 280
260 260
240 240
220 220
CHARACTERIZATION VISCOSITY INDEX200 GROUP FACTOR OF LUBE FRACTIONS· 200
1 12.1 -12.6 SO-IOO
,eo II 11.9 -12.2 60-S0 180III 11.7-12.0 40-60
IV 11.5 - II.S 20-40160 y 11.3-11.6 0-20 160
* DEWAXEO TO +20o F POUR
140 140
120 120
100 100
200 300 400 500 600 700 800 900
22
10 20 30 40 50 60 70 BO
460 MOLECULAR WEIGHT ~ GRAVITY 460
TYPICAL CRUDE FRACTIONS
440 440
CRUDE TYPICAL GROUP
420 'WHITE GAS OILS420PRODUCTS a HEAVIER
PENNSYLVANIA I ~RODESSA ~ I
400 PANHANDLE II % 400MID' CONTINENT IX :IIKUWAIT I-U lI-nI
380 IRAO II II-%II 380IRANIAN II II-XIIEAST TEXAS Dr II ~
S. LOUISIANA III II360 .lUSEPIN :III III 360
. WEST TEXAS UI DITIA .lUANA (NEO. a 102) XII IV
340 COLOM81AN IV IV 340LAGUNILLAS v y
320 CHARACTERIZATION VISCOSITY INDEX 320GROUP FACTOR OF LU8E FRACTIONS *
I 12.1 -'2.6 80-100300 11 11.9 -12.2 60-80 300
III 11.7 - 12.0 40-60
280 IV 1/.5-11.8 20-40 2BOy 1/.3-11.6 0-20 .
260 * DEWAX£O TO +20o F POUR 260
240 240
220 220
200 200
180 180
160 160
140 140
120 120
100 100
110 20 30 40 50 60 70 80
23f.Jo-;n'i L
PIA If" . .JJ, \) _,_ t. I.,.
PABLO 1VI0T'l'A
Section 4
VAPOR PRESSURE
In developing the vapor pressure curves for most of the individual hydrocarbons, the reciprocals of the absolute temperatures were plotted against those of areference compound (ethane, butane, or hexane) at the same vapor pressures. 1 Withone or two exceptions, this relation was linear over the entire range of the data,but if a slight curvature was indicated, as in the case of benzene vs. hexane, astraight line was not imposed upon the data. The vapor pressure curves formethane and the reference compounds were developed directly from the data byplotting vapor pressures against reciprocal temperatures. Most of the reliabledata fell within -I- 1OF of the correlations, and this may be considered as aboutthe accuracy of solid portions of the vapor pressure curves. Normal boiling pointsin all cases were taken from "Selected Values of Properties of Hydrocarbons."2
While vapor pressure is meaningless above the critical temperature, thecurves were extrapolated beyond this point so that other properties in the liquidphase could be calculated in the absence of any other data. For example, theseextrapolated curves may be used to make rough approximations of the fugacity,density, and enthalpy of hydrocarbon vapors in solutions at temperatures abovethe critical.
The generalized vapor pressure charts for hydrocarbons were also derivedfrom the linear reciprocal temperature relation with hexane used as the referencecompound. The pressure scales correspond to the vapor pressure of hexane as afunction of reciprocal temperature. The temperature scales were based on thereciprocal relation up to 700°F, but above 700°F it was necessary to modify thescale to secure better agreement with data on high boiling hydrocarbons andpetroleum fractions. 3
The slopes of the normal boiling point lines on the rectilinear chart and thecorresponding points on the alignment charts were based on normal paraffins.However, with the exception of some of the lowest boiling members of the variousseries, there is a good indication that these charts apply to hydrocarbons ingeneral. In API Research Project 42, the boiling points of a large number of
1 This is the most nearly linear of the simple vapor pressure relations, with the exceptionof a similar one where the reciprocal temperatures are plott.ed at the same reduced vaporpressures.
2Nat. Bur. Standards Circular C461 (1947).3 Beale and Docksey, J. lnst. Petro Tech. 21, 860 (1935).
24
-----------
VAPOR PRESSURE 25
different high boiling hydrocarbons were determined at 0.5 mm, 1.0 mm, and 760mm, and these were checked against the low-pressure alignment chart. Theaverage deviation was about 2°F over an average extrapolation of around 400°F,and there was no trend between the paraffins and other hydrocarbons.
Thc cxtrapolation of the vapor pressure scale below the hexane data has beenchecked indirectly by the Clapeyron equation using thermal data on hexane atlow tempcratures. Also, low-prcssure data (below 0.001 atm) on petroleum fractions are in good agrecment with this correlation.
GENERAL REFERENCES
Aston, Kennedy and Schumann, J. Am. Chem. Soc. 62, 2059 (1940).Aston and Messerly, J. Am. Chem. Soc. 62,1917 (1940).Beale, J. Inst. Petro Tech. 22, 311 (1937).Beattie, Hadlock and Poffenberger, J. Chem. Phys. 3, 93 (1935).Beattie, Poffenberger and Hadlock, J. Chem. Phys. 3, 96 (1935).Bea.ttie, Simard and Su, J. Am. Chem. Soc. 61, 24 (1939).Bea.ttie. Su and Simard, J. Am. Chem. Soc. 61, 924 (1939).Bekhedahl, Wood and Wojciechowski, J. Research Nat. Bur. Standards 17, 883 (1936).Benoliel, Thesis, Pelillsylvania State College (1941).Benson, Ind. Eng. Chern., Anal. Ed. 13, 502 (1941).Brown and Coa.ts, Univ. of Mich. Res. Circ. Series 2 (1928).Comrp.unication from The ::\1. W. Kellogg Co., New York, N.Y.Dana., Jenkins, Burdick and Timm, Refrig. Eng. 12, 387 (1926).Doss, "Physical Constants of the Principal Hydrocarbons," 4th Edition, The Texas Co.,
New York, N.Y. (1913).Ega.n and Kemp, J. Am. Chem. Soc. 59, 1264 (1937).Francis and Robbins, J. Am. Chem. Soc. 55, 4339 (1933).Frolich and Copson, Ind. Eng. Chern. 21, 111G (1929).Garner, Adams anu Stuchell, Refiner 21, 321 (1942).Hei ig, J. Am. Chern. Soc. 55, 230-:1: (1933).Heisig anu Davis, J. Am. Chem. Soc. 57, 339 (1935).Heisig and Hurd, J. Am. Chem. Soc. 55,3485 (1933).Ingersoll, Thesis, Mass. Inst. Tech. (1930).Intel'l1ationa.l Critical T:1bles, Vol. III.Kassel, J. Am. Chem. Soc. 58, 670 (193G).Kay, Ind. Eng. Chem. 30, 459 (1938).Kisti:1kowsky and Ricc, J. Chem. Phys. 8, 610 (1940).Kistiakowsky, Ruhoff, Smith and Vaughan, J. Am. Chem. Soc. 57,876 (1935); 58,146 (1936).Krase and Goodman, Ind. Eng. Chem. 22, 13 (1930).Lamb and Roper, J. Am. Chern. Soc. 62, 806 (1940).Kinuer, J. Phys. Chem. 35, 531 (1931).Livingston and Heisig, J. Am. Chem. Soc. 52,2409 (1930).Loomis and Walters, J. Am. Chem. Soc. 48, 2051 (1926).Maxwell, Ind. Eng. Chem. 24, 502 (1932).Morehouse and Maass, Can. J. Research 5, 307 (1931); .11, G37 (1934).
26 DATA BOOK ON HYDROCARBO S
•
Nieuwland, Calcott, Downing and Carter, J. Am. Chem. Soc. 53,4197 (1931).Pitzer and Scott, J. Am. Chem. Soc. 65, 803 (1943).Rintelen, Saylor and Gross, J. Am. Chem. Soc. 59, 1129 (1937).Sage, Lacey and Schaafsma, Ind. Eng. Chem. 26, 214, 1218 (1934).Sage, Webster and Lacey, Ind. Eng. Chem. 29, 658 (1937).Schmidt, Thesis, Paris (1934:).Stuckey ll,nd Saylor, J. Am. Chem. So:;. G2, 2J~ (1940).Vaughan, J. Am. Chem. Soc. M, 3863 (1£::>2).Vaughan and Graves, Ind. Eng. Chem. 32, 12.;>2 (1940).Wiebe and Brcevoort, J. Am. Chem. Soc. 52, 622 (1930).Wiebe, Hubbard and Breevoort, J. Am. Chem. Soc. 52, 611 (1930) .
HH-
_~: 4
.-- - ::l
-_.~
-;-
'!' --
807060
50
40
30
20
-300 -200
27
o 100 200
- -- ~.-
l--:r. ~
-2'50 -200 -150
.8.1.6
.5
.4
.3
.2
-100
~..-,~
VAPOR PRESSURE OF
ETHANE AND ETHYLENE
200
.08.07
.06.()5
.04 .-
.O~
.02
807060
50
40
30
20
IIall',gr
,
.1 _. ...-~
4
3
2
-200 -tOO o28
100 200 300 400
-'
VAPOR PRESSURE OFPROPANE AND PROPYLENE
=-, ,
-100 -50- ,-;;.,,", ::T:-E.=:io€-~:ff-' le"", '~7,k ,,,="i- ~ ::ri..:r--,~f.':'=j-:', ,c.:.~3':!..J
=
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--H
.2 200
.1~
.09
.08
.07
.06
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.03
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r= _
'''''
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" -!CA_~{~!
-,.!~
-t-t=f
10090
7060
50
40
30
20
.009,008.001
IXXJ
.005
=r
II-'I=.:f.: "
1098
-' 7
6
5
4
3
2
To 100 200 300 400 500
29
50
·5
.4
..3
.2
I II. II II
.01 ~-====47 -
1I /I
- VAPOR PRESSURE
OF BUTANES AND 8UTENES
:II+-_~,200
30
I I V V 1/o tOO
I
200
30
300 400 500
VAPOR PRESSURE OF
PENTANE AND ISOPENTANE
t.O.9 p.
~.5
.3
.2
-roo o 50
: ::r=tfel. ·-:-r-·:~-.g: -I'
-- ~ ...::T'
'200
.07 1=l;.T:,:
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.05
.()4
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11 I
.€ ==':.f"_-=I:: :t=:!-~:. _ 90
!:::f 807060
50
40
30
20
I
.01 .-.OOQ -',--. -
-:.,008 -.007.006 - H
.005
.004
- _..003
- I::±l
.002
I Q'
, . :~ ± .§'.: - ":'::. - .
- l:±-
-- 8
,=: 76
5
4
2
It ..00IU-J....l....L.LLL.JLJ...,U.I-......AJ...J...Iu1t.U./-l..'~~I~J.:..z.J,;.W-l...l-J...J.-l...J..J..1..J..J...J...L..J...J..J..J..J...J...IW-L...J.-l....J.-l...J..J..u..J-U...J...J..J..J..1..J..J...J...L-U
100 200 300 400 500 600
31
l--. .-.---------
';-..:: T.~: ': '.':~:
="=±
-100.9.8..,.5
.4
.a
-50 0 50
-1Iftij- -.:.~
VAPOR PRESSUREOF HEXANE
. : .....
100 ISO-
200
I~
.1.09
.07
.06
.05
.04
-t... . -fl :.~,"'f> :. 'c:
:::'.-:x':~ ::~-,.
-17 . n-
"_. '--J-;,' "c't._',_ . ~ ,.. -,-V-FFl 100
::t~ :'':' - _"':4'_ .•••.-.t . r-- ~-;:=::;=:I 90--. :r.' ,-- '-,-, =- __ --7l~: ' -I:' ' =l:
, 'f--X:==, T.:i::-'~==1':::. .- . 80.- ~, .. -'-+- ,- 70
60
50
40
.03
.02
r .'
30
20
.008
.OOf
.006
.00
.003
- -,
I /
;=;=. ~ 11.,,':.. '.,~':'1. ,~f:~T ~.~:~I
£ .'f=:£:i=E j~ --!' _:. ,_ ,. ~ - '
.''=8, !E::-l,=.:l3:: ' ,-J.'
--:=;::1:'. :t+= 'r: ~t:.:~1-.. -- -,~.
- - 10, . . ,.. =.-1-=!iiC:l 9= -
976
5
4
3
2
II II .•
I I I ;.,
32
200
.1-'-.
~t:
200
H
VAPOR PRESSUREOF HEPTANE
.4
.2
.3
-50 0 50 100 150
.8 . =-= ::::.C ·=--==~~-:'~';'_~c~"=§=:l~F-=~.. _--< =:h:b-~-
~=t=t::= ~=;::.5
~~"'~~'t:g~E~ 'fg-= . .: ~." 70
=t...: 60
50
40
30
20
H-H-++-H-t--t-++-t-f-fH--f-+-HH-+++!
3
10:;:::=.;. 9
,..:::::: 8
76
5
4
tH--
.·+--'---~"'H _.-.Xt__1-- .. !-' .;.
. '--.-1-1- ..
=f:'~= ~", ~::.~f ~;; -:~-=:.= 'C, E.: ~! :t+' -§j:, =~ - -. '._. ... .-
f-:-. :-'~"'-""::l: .= ...i=i= I/.·~ . '-;- 1-.; ':-i-:'- .1=;""<- H
.::t± t':i::~. ::-J: :.l::::tl" ~- ..... :
..:p. ";J-
. c;::::=
c-F-¥+'·~f-C.,....=· I-:=±:r- _ L:.I .. '-.q::--l-
.008
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.006'
.005
.0
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.002_J
2
33
1.0.9.8.7.6
50 100 ISO 200 250
=I-·,~-,,::'~,':7~,£::I-,-:.-~:: -~~ =F~:::l~+:- ..: .- -f-
.5
:4
.2
VAPOR PRESSURE
OF OCTANE~'. --;
-I- ' ':,::J
,'+'++++++++++++++++H-J-H
.01.06
.05
.04
:
"
...:' - t - •100
_ 90
7060
IJ-+-tft-t-H-t-t
f-
.0/.009.009.007DOG
.005
'I
," ,
A-1---J---~--1-I-I-
"
i I
200 300 400
34
500i
600 700' 800
300
:1..-=
-l-+
VAPOR PRESSUREOF C3 UNSATURATES
_I-~-~.
to t-:~-~I= --,..~ -:1#r' ., -
.1-/ j-++
3 ,~-. -'-" -,. - '-~:j=~~ -Ej
·2++y.j
WI W
1- 1
200
.J
I l'io
.1'".
III
100I I
200
I1l'I
300 41)0 500
35
o
00
o
00ooooo
40
30
_'00 -!'>("} () 50 -.:: VAPOR PRESSURE
OF C4 UNSATURATES,-I
2
I ~
''1I r I.~ -a,-, ~-~r/~ _I
I l" I" -I:.- - - =Z:~-E§,.;:. t'- ~ ~ .,'" : )/: ..~, ~----. -:'E -~ -~: 'ill = _.
~_. _.-. . - ~--
-:J 7;:::t::T-
-- - 6~ t- -,
t-:;t 5,
_.
- -_.-
-~, Il"l-II
I II m ~
III I I I ~ ~ I. - . 9~ .B.P. CRITICAL PT.
8~ - COMPOUND of of ATM.
71,3 BUTADIENE 24.1 308 45 .
6
11 VINYLACETYLENE 42 365* 75v5
ETHYL ACETYLENE 47.7 375 65v
DIMETHYL ACETYLENE 80.4 420 60 v 4
* ESTIMATED v VAPOR PRESSURE CURVE 3
2
I
III
.3
.2
1.0.9.8.7.6
.5
.03
.1.09.08.07
.06
.os
.04
.02
.01
o 100 200 300 400 500
36
...
o
o
o
00oooooo
700600500400300200
. 100 150 200 ..=r-_0- .... .. 0_
. - ...• 0
VAPOR PRESSURE OF . ---
BENZENE AND TOLUENEo~ . --
~=
-
I.- I I I
ti I.. .
9. '-1": 8
...7
,~f ~'0
. .6
o. :t=l=,
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. ...- 1-4-
- 3·i-r~-
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1-'
. I1/ I I I
- '=' . 9. ..
.8. ..0-
.70
0-
6
0
4
-Hi 3. -ti-
I
, 2
I
I -, I I oir:'1I I : I Ie . I I.
.2
.t.09.08.07.06
.05
.04
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.~
-1.0,9.8.7.6
.5
.4
.01009.008.007.006
.005
.004
.003
.002
.001
37
o
o
2
4
3
o9A
7
6
5
30
0090ooooo
300o50 100
M150 2 0 250
W~. - - ..
- .. '. '--.- -
.- . .. .. . -~-
-_. . VAPOR PRESSUREOF Ce AROMATICS i=1-1=l=1=!.
..
- =). .. --r-' :+COMPOUND B.P. CRITICAL POINT ~ r .
~ ~ ..AItL=.l
--ETHYL8ENZENE 271.1 655 38p-XYLENE 281.0 652 35 V - --J
m-XYLENE 282.4 655" 36 Vo -XYLENE 292.0 675 37
*ESnMAlD1 V- VAPOR PRESSURE CURVE, . .." ..--.. ,
I I I I I I I I I I I I I I I L I , II I I I I I I I I I I I I I I I I I1'Y I I..
87
5t+
- 4
..
- 2:.t:
.. -l-I- ~
. i+,.. -Ie;
IIi ... !-1-+- I
.. Vl-1- .. .. - .. -1 +c -' . ~=T= .. - . - 7 ~_ ~'=T::
~'ffJ$I j . 'j' ~'I.'1;: o.:,~ : .- :.- ''1.-= rot·:j;· 1_ " -.a:- I- ... -:. .. . - .. . ,·tf·L.~",t--T-i'-= :g..... ,,-:::, - til' 't:- '~ ~;/ .f-'i F= F.[-~ -E-:-~;=.s. - . -- . ~ -- -= -.' -=to -:- ;: . j:_-;...~-':'l:LL--.. ..
.. . _.. ~r ;- ·,~"-I:·:-:.fil-#- ' ::':1':=1:2' '.:\=-1--:: B="-=i::t~::.m --. -- -, 1::: _I::-j,r~. %.-! '-.=t=
..:j~Ii'Jl i,; 0- J: :'i,i £1 .... -+,+ H::- . :!-r: f.£ -.. .. -' , ...~ ~'1..:';_:" - =l " .... --,4···
.,.. !=1 - .. ,}--r:R::l=f*~ ':', -, ~::IS=.$ ,. - .. . .' - 1-=1-:1=
- -l, . - .-
....:",~
, VAPOR PRESSURE OF P - XYLENE- - .- - , .. -- EQUALS VAPOR PRESSURE OF.. ..
.. ETHYLBENZENE MULTIPLIED BY .950~--l
='
II II '1 J -I .1 I '1
300 00 500 600 700 eo
.2
.1
.09
.08
.07
.06
.05
.04
.3
1.0.9.8.7.6
.5
.4
.03
.02
.00
.003
.01.009.008.001.006
.005
.004
.002
38
VAPOR PRESSUREOF CYCLOPARAFFlNS
100
.9
.8
.7
.6.f"!--1-:
.5~: ,H
-50
.' - 50 too~~...
.3 ~.
- .'.
.2. r--
II
++-l-l--JTf·-++-J.,l;~I)ll-HH-I++-H-++++-H-H-IH-l++++-t++-H-
*EsrIMATED V- VAPOR PRESSURE CURVE4
2
3
.I~00
807060
50
4 0
30
20
• ..1_ I 109
,g: 8CRITICAL POINT~ ATM. 7
470* 46 V 6
520* 42 V 5538 40.4
( I
COMPOUND B. P.of.
CYCLOPENTANE I 2 0 .7
tt1'CYCLOPENTANE 161. 3CYCLOHEXANE 177.3
Ii
.''1
.08
.07
.06
.05
,04
.03
.02
.002
·003
:01.009.006.007.OO6~
,005
004
39
.00001
1200 VAPOR PRESSURE OF HYDROCARBONS 01
1100 LOW PRESSURE RANGE, 0.00001-1.0 ATMOSPHERES .00002
021000 .00003
.00004 .Q3900
.04.00006
800 .00008 .06.0001 .08
700 - 0.1
.0002 ~
600\'2-00
0.2.0003
.0004 03
04500 .0006
.0008 06.001 08
1.0
400.002
u.0 2.00 .003
3.0 ~ I350 I ~
w ~ .0040=::> I w
~ w 4.0 ~0= .006 (j)
300 0= u- ::> (j)w 0 (f)6.0 ~0.. \ (f) .008
~
~W Q.W 0= .01 8.0 a::f- a 0..
0... 0= 10 ~250 19 0~~ 0..
~ ~ .02~
20-l .03200 ~ 30
~.04
40.06
.08 60150 0.1 80
100
0.2
100 2000.3
0.4 300
4000.6
0.8 600
50 1.0
40
VAPOR PRESSURE OF HYDROCARBONS0.1 1.01200
1100 HIGH PRESSURE RANGE, 0.1-100.0 ATMOSPHERES20
1000 \'(..00
900 \ \QO 0.2 3.0
800\000
40900 0.3
5.0700
0.4 60
0.5 7.0~
8.0600 0.6 90~ 0.7 10"\
08~ 0.9500 '6
1.0c-~':)
20Q(p
(f) ui-a w en0:: <l400
~ w ~
~5: 2.0 30 c;(f) (f)u..0 "-0
~ vi350 It- 40 enw<l3.0 ..J0::I I::J
W 50 wt-o:: 0::
<l0::
~4.0 60 ::J300(f)
w(f)
a..(f)~ w 70 wg: 5.0 0::
w80 a..t-
~6.0 900::0250
~ 7.0 100 a..;;> 8.0
~
9.010
200
200
150 20 300
40030
500
40 60010070050800
60 90070 1000
sJ 8090
100 1500
41
fOO&> ' , toe 150 200 250 ~O 350 400 450 500 550 600 650'700 aoo 900 1000 1100~80 T PEn'Ll-TURE - OF , . . '!-t _ : ,~_ .,: ,~ 80
60 . VAPOR PRESSURE . I, -tY.~ "~..." . ' , . 60
40 OF HYDROCARBONS 1 -ll' I 40;-r;30, Y . . I 30
. ,20 lA' ~ 'I I '''' " • I I I •• , " I 20
lliJd1.LLJL!1t-nIlIVi 1
.~
I 0 I ..-r I ,.A' I , " , ".A' I I 1/, J 117.r I 'f' TVi T T ;/1 I 0
ao I • " " , ao60 ' , '" ., ~ ,-,... 60
I I, ,
I t .1 I I
40 ,~I I , I : + f7t; ~ '~ 4.03.0 I I 1./ I r 1 I. ' /i I I 3.0
1"-: I I ' L ~ ~ I • i
2.0 .L. I ~' ! ... t 1 J f~ 'I - -1 l J....L.. i: LI'_' I 1. : t I 2.0;1;
::E+-~L--r+-+-'- +-
1.01'- ~~.8 ::!",~_,-::: ~ I-l-~.6
'
'';'''= ~ ~ jJ ~.gH-t+I-IIdjctti+b~"'" -+-~., '7'<~ LL x'-< " ' , , ,~ ~<-~_ • . .>' ~ ~ W "A I ,t+.4~-::± _ . ~~ _~ '. ' , m I4+t=1;~J ~;, ~rTTTTT~ '+-<- =i=rc .., ~,' ,L ' , +,#tT 7f<r 'P-~~ -++ '"' ~ ,~_,.'YO "" 14-' ' ". rtr"fo r++ttl~ L -' ' '-' ~ • ' ........ Jc.l" U-tdc
2 0,1=+,.±'-- ,~ ~ '- H-+J,:"* = 2 Tt++" - ~ ' 144 """I " :frh+l>H+-be§! >--L ' ' crT f-H,f' ....,m L! ~ ' ,- "i:1' , ,vII m l'l~--WL ' " 0 1-+- zt:---T"'"7Eff± JZ '-'....~' ' L l±!=J' '.,<.I. ,
I
~ ' " r ' tT ",- 7fF1 ,-i--;..:,t-,--
, ~' ' ,~ I
.oaE1=!=8- ,+,,' ~ "~~,~-'-"- '.Q6.... ' ' ~ LtA--- _, ~ _ =' , ' >!'H+f!-if :, ',l1'tzj-;· +~ =<±+-' ~ . ' +l-t:-H-l -rttT:--'" COf tl; , ' _' ~ " te ,-of+!-' ' ,~v~..d'-=''- -++- " 7'---' " . ' , " '"= ,-L' ", ._c-'- IW
_,_ ~--i:-.""'~~" " ,~,A ~' ,,~. ,=.t~::::a: 0::rCoL ' ,,__' = ' I' .'" ,TT-' -,''''= p,
+-+-: II 17fiiT~.2f=+_",~ . ~ ~::::;::;=z=.:'L-[A.i ~ ~~K~ ~I/r::'iIi- s..:x 4.. ~ ~~o.., = '. = ==t-r~__ " =-=-'-'- I'm, +..rm.;w!t%' ~,47!' -r~I ' , ~...::->f-----, " ~ !fffR"~ '---'-'- ~.. _, ... .. =,~ :ttl! <1, , --H-A' =" - e=~" ' n>,, '~" " ~£":2i" ' ~II" T - - _.~~.~-. --- I+~,'- ' ' .7' T .. -"o.c _-;,7,E-"'-~ ~ = ~ ""OB_ ~ '.L~'--+++-- ;:;. ..I~,!-r~r.-t ,.,." L:...:..CJ .06
~
.008
.006
.004
.003
.002
TE~PERATURE -OF400 450 500 550 ----600 650 700 800 900 1000 1100 120050
v100 150 200 250 300 350
A '/ tt1 -" i I I " I
t. ,, .". I i,
NORMAL BOILING POINT
Y! BOILING POINT AT 10 MM
.1.-
"!
1100
1000
900
800
700
600
500
400
r
100 200 300 400 ·500 600 700 900
43r)H,T 1r~T _ TJ)
oPI ~i tV/l. \. J .)
PABLO MOTTA
VAPOR PRESSURE OF GASOLINES180 .7
.8 40
170 .91.0 50
160 60
70* SLOPE OF DISTILLATION + LOSS 1.5 80150 CURVE (A.S.T.M.). ° F@ 15'>'. - of ~ 5°4
10 90IN THE ABSENCE OF DISTILLATION 2.0 100
140 DATA THE FOLLOWING AVERAGE y
SLOPES MAY 8E USED:
°F/'>'.SLOPE *LIGHT NAPHTHAS (F.B.P.-300°F) 2.5
130 NAPHTHAS (F.B.P.-400°F) 4 01234AVIATION GASOLINES 2
~ 3.0 150MOTOR GASOLINES 3 2
120 0 2en
ci"- ~ 200(Ij 3 4.0 J:3
110Q) d u....J
~0
I
;;: 4. 4 en 5.0 ~• 5 CD ~100 l&. 0 5 -J• 2 I
I 6 I 300L&J
....6 l&J 6.0 w
0: UJ 7 0: It:::> Q:" 8 7 :::> ;:)
90~
:> (J) (/)
en 9 (J) (/)
8 w0: en 10 l&J ItL&J UJ II 9 0: 400 Q.0.. f 12 10
0.. 8.080 ::E
l&.I 14 II 0: It... Q:" 0 00 16 12 0.. Q.Q. ~ 500 ~70 § 18 14
2016 L&J II us
0 :::> ;:)
W 18 0: 600 It
60 a: ... 12 I-20 13
EXAMPLE: DETERMINE THE TRUE 14 700
50 VAPOR PRESSURES AT 32°F. 100°FAND 15Q°F OF THE FOLLOWING 15GASOLINE: 16 800
REID VAPOR PRESS. - 9.0 LBS./SO. IN. 1740 DISTILLATION + LOSS, 5'>'. ~ 120 OF
18900
15'>'. (! 160 OF19 1000
SLOPEc 160-120 .4.00 F/'Y. 2030 10
TRUE VAPOR PRESSURES CORRE-SPONDING TO A R.V.P. OF 9.0 LBS./
20so. IN. AND A SLOPE OF 4.0°F/'>'.ARE READ FROM THE CHART ASFOLLOWS:
TEMPERATURE TRUE VAPOR PRESS.
10OF LBs/sa. IN.32 2.8 30
100 9.9150 21.4
0
REFERENCE: COORDINATING RESEARCH COUNCIL (CRC) HANDBOOK. PP. 244-254 (1946)
44
(1 )
(2)
Section 5
FUGACITYRaoult's Law
If two or more compounds form an ideal solution in the liquid phase, and ifthe saturated vapors of the individual components are perfect gases, the system hasbeen termed an ideal system.! For such a system the partial vapor pressure ofany component may be calculated from the composition of the liquid phase byRaoult's Law and from the composition of the vapor phase by Dalton's Law. Anequation of these two expressions gives the liquid-vapor equilibrium relation forany component, i where i = 1, 2, ... , n:
Pi = PiXi = 7rYi
or yi/Xi == P i /7r = Ki
where Pi = partial pressure of i
Pi = saturated vapor pressure of i
Xi = mole fraction of i in the liquid phase
Yi = mole fraction of i in the vapor phase
7r = total (vapor) pressure of the system
Ki = vapor-liquid equilibrium constant for i at the temperature and pressureof the system
The above equation, usually referred to as the Raoult's Law relation, is trueonly for ideal systems, ,as defined above. However, it is usually a good approximation for mixtures of homologues and, in general, for mixtures of chemically similarcompounds, if none of the saturated 'vapors at the equilibrium temperature deviatetoo greatly from a perfect gas.
Up to moderate pressures (several atmospheres) hydrocarbon mixtures frequently fall within the scope of the Raoult's Law relation. However, its application to these mixtures is rather limited because of the wide differences usuallyencountered between the boiling points of the most volatile and least volatilecomponents. This results in equilibrium temperatures at which the saturatedvapors of the lowest boiling components deviate considerably from a perfect gas,even though the equilibrium pressure of the system may be relatively low.
I Gamson and Watson, Nat. Petroleum News} Technical Section 36, R-258 (1944).
45
46 DATA BOOK ON HYDROCARBONS
Fugacity Functions
In order to improve the accuracy in predicting vapor-liquid cquilibrium constants for hydrocarbons at higher pressures, Lewis and Luke 2 and other investigators replaced the pressures in equations (1) and (2) by -analogous fugacities forany component, i, whereby:
or
Ii = fpiXi = fnYi
Yi/Xi = fpdf.Tri = K i
(3)
(4)
where fi = fugaci·ty of i in either phase of the system
fpi = fugacity of i as a pure saturated liquid (or vapor) at its vapor pressurecorresponding to the equilibrium temperature of the system
f-rri = fugacity of i as a pure vapor at the equilibrium temperature and pressureof the system
Generalized correlations have been developed for the r-atio of fugacity topressure for pure hydrocarbons as a function of reduced temperature and reducedpressure. A correlation of this type (pages 62 and 63) was used in conjunctionwith the vapor pressure charts to develop the fugacity function charts for individual hydrocarbons. 3 The fugacity function given by these charts, 7rfp/!-rr, maybe considered a corrected vapor pressure and used in place of the latter in ~ny
equation pertaining to liquid-vapor equiiibrium such as equations (1) and (2).
These simple fugacity relations greatly extend the pressure range for whichliquid-vapor equilibria for hydrocarbon systems may be predicted with confidence, and can be used up to equilibrium pressures of 20 to 25 atm with a fair degree of accuracy. Beyond these pressures and especially as the critical point of themixture is approached, serious deviations from true equilibrium conditions areencountered. Under these circumstances, the assumptions of ideal mixtures nolonger hold and the fugacities of the individual compounds are dependent uponthe compositions of the liquid and vapor phases as well as temperature andpressure.
In the region where the simple fugacity relations no longer apply and consequently beyond the scope of the present charts, there are data in the literature ona number of specific binary and multicomponent hydrocarbon systems. Also, TheM. W. Kellogg 00. 4 has published an excellent correlation for lig~1t paraffin andolefin hydrocarbons in which the fugacities of the individual compounds aregiven as a function of the molal average boiling points of the liquid and vapor
2 Lewis and Luke, Trans. Am. Soc. M echo Engrs. 54, 55 (1932).a This method was actually used only up to the critical temperature of each compound.
Beyond this point values were calculated from more general fugacity correlations developedby The M. W. Kellogg Co. to avoid using extrapolated vapor pressure curves.
4"Liquid-Vapor Equilibria in Mixtures of Light Hydrocarbons," The M. W. KelloggCo., New York, N. Y. (1950).
phases in addition to the equilibrium temperature and pressure. The Kelloggcorrelation was derived from the application of exact thermodynamic relations toa comprehensive equation of state for pure hydrocarbon vapors and liquids andtheir mixtures. 5
If, in addition to hydrocarbon v-apors, other gases (air, H 2 , CO2 , etc.) arepresent in the vapor phase, it is recommended that an effective pressure, equal tothe product of the total pressure multiplied by the square root of the mole fractionof the entire hydrocarbon portion of the vapor, or 7r-VV;;;, be used in determiningthe fugacities of the individual hydrocarbons. Fragmentary data have indioatedthat this effective pressure gives better results than either the total pressure, 7r,or partial hydrocarbon pressure, 7r'YHC, for determining individual fugacities. Then,after the fugacities or fugacity functions have been read from the charts, the totalpressure is again used as a basis for all equilibl:ium calculations. The followingexample illustrates the application of the fugacity function charts when othergases are present in the vapor phase:
Example 1. Determine the pressure and composition of the liquid phase inequilibrium with a vapor of the following composition at gO°F:
FUGACITY 47
1st Trial 2nd Trial InterpolationVapor. 1l' = 25 atm 11" = 20 I1tm
11" = 21.8 atmComponent Mole Fract. 1I"e = 21.5 atm 1I"e = 17.2 atm
F, atm x F, atm x xAir 0.040 * - * - -H2 .220 * - * - -CH4 .280 180 0.039 180 0.031 0.034C2H6 .175 38.0 .115 36.0 .097 .104C3Hs .160 13.5 .296 12.7 .252 .269C4H1O .125 4.9 .637 4.4 .[;68 .593
1.000 1.087 0.948 1.000
• In this example, the fugacity functions of air and H2 are considered to be infinite.
where 7r = total equilibrium pressure7re = 7rVO.740 = effective pressure used to determine fugacity functionsF = 7rfp/!1I" = fugacity function for pure hydrocarbonsx = 7rY/F
~ Relative VolatilitySince relative volatility is quite useful in fractionation problems, curves for
the relative volatilities of light unsaturates and isoparaffins to the correspondingnormal paraffins are given on pages 64 to 66. The curves for the C4 unsaturates
IS Benedict, Webb and Rubin, J. Chem. Phys. 8, 334 (1940); 10, 7474 (1942).
48 DATA BOOK ON HYDROCARBONS
inay also be used in conjunction with the normal butane fugacity chart to predictfugacity functions for these compounds.
Except for butadiene and the normal butenes, these relative volatility curveswere derived from the Kellogg fugacity correlation. Composition was indirectlytaken into account to some extent since the fugacities for each pair of compoundswere read at the same liquid and vapor molal average boiling points as well asat the same temperatures and pressures.
In general, the relative volatility charts may be considered to have a somewhat greater range of applicability than the simple fugacity charts. They may beused up to 25 atm, irrespective of the composition of the liquid and vapor phases ~
of the mixture; beyond this pressure their application is limited to systems inwhich there is a difference of at least 75°F between the molal average boilingpoints of the two phases, but under no circumstancel? should the curves be extrapolated. While all of the curves may be considered to be accurate within 25% forthe relative volatility minus one (0; - 1), deviations from the solid curves rarelyexceed 15% for this difference.
Chemical Structure and Liquid Activity Coefficients
When components in a hydrocarbon mixture are quite dissimilar chemically,the liquid phase may deviate appreciably from an ideal solution. This effect ofchemical structure is not taken into account in any of the fugacity correlationsheretofore considered. It has been mentioned that in correlations of the Kelloggtype, fugacity is a function of the liquid and vapor compositions, but only withrespect to components of similar chemical structure.
To correct for chemical dissimilarity in solutions of light hydrocarbons inabsorber oils, liquid activity coefficients are given for these light hydrocarbons onpage 67. Within the range of the data these activity coefficients were practicallyindependent of temperature (100°F and 220°F) and pressure (500 psia and 1000psia) .
GENERAL REFERENCES
Brown, Souders and Smith, Ind. Eng. Chem. 24, 513 (1932).Dean and Tooke, Ind. Eng. Chem. 38, 389 (1946).Hadden, Chem. Eng. Progress 44, 37 (1948).Kay, Chem. Revs. 29, 501 (1941).Lewis, Ind. Eng. Chem. 28, 257 (1936).Lewis and Kay, Oil and Gas J. 32, 40 (1934). .Lewis and Randall, "Thermodynamics," pp. 190-198, McGraw-Hill Book Co. (1923).Nelson and Bonnell, Ind. Eng. Chem. 36, 204 (1943).Sage and Lacey, Ind. Eng. Chem. 30, 1296 (1938).
·~- ..-t-t
oj-or
~T:~
_. t
r
FUGACITY FUNCTION 1mOF METHANE
-l- .
200
. ':.;= ~:-:.:F-~:-~-
-;':~i:£ J:-
'I i v. I-. -::-± .• -~
10 I::f.;=+
_100908070
60
50
40
30
20
I
: :.-;;! j. p-L~-t.: :~-. _~/J::.1~·_-,2? ~E§= -~:.,~
=~~~-'- :.=;-
=:=.
,..::~
-300 -200
- • .j... -
-100
49
o 100 200
10987
6
5
4
3
300
&I ... F~~~CITY FUN~TI~NI
OF ETHYLENE r+-
-
-
..
••
I-- ~ 10090807060
50
40
30
20
_I~
87
6
5
4
-200 -100
50
o 100 200 300
~
-~= - ~ --- -- - - -- --
=FUGACITY FUNCTION ==OF ETHANE
=== ~-
- - -
• -- - -- -- -- - I- - - - - - - -
- ~t a - - ---- - -
- - --
-- - - -
~
~/
- -- - -rl=Fl-- -'--
00
00908070
60
50
40
30
20
10987
6
5
4
3
2
-zoo -100 o 100 zoo 300
51
4
10987
6
5
30
20
0090807060
50
40
o-100-200-- - . -.=a=::-
/M FUGACITY-c
FUNCTIONOF PROPYLENE
- -
I~
/1AI
II If I I
...
I-
-,I I IJ
iiiII
0.2
1.00.90.80.7
0.6
0.5
0.4
0.1
0.3
3
2
-100 o 100 200 300 400
52
4
30
2
3
20
109876
5
00908070
60
50
40
o-100-200 -,0:;
FUNCTION.i FUGACITYOF PROPANE -::
-- . -. -+-+-l
-
..~ i I
-
11-(
If
VI
iW II'.
- •,
• I
-+-
~
l.
-l-, , .
- I
"'T I J I ,
i,""'" I-ir-I
I I L~!..ll If .-L~ c.:.'__,- I__.x.
0.2
0.3
0.1
1.00.90.80.7
0.6
0.5
0.4
-j(jO o 100 200 300 400
53
0.2- r
t
__:T"-~
,- FUGACITY FUNCTIO:lI"-
OF ISOBUTANE ::~,
"1J;:,f-;t--l+++H Ifl+I-I-/HI-H+-I--+, I
~l--
=3...J-. ~l='- ,-
___ t:::t:::t:=t=J:
'II ElIOO
~ 90807060
50
40
30
20I.
~t;-
o r+- -H-lH+I--t+H+t++-H+-H+-l-H-++++H+H-I-+-1-++I-I4-IA+:I4-jll--W-+-I-l--!-l-l--+-W-!-W~-I--l1
I~:-:- 3:,-'=i-- -i-:-(=F" ""--
.!- '7 -...t.~ ~-- .~~.l -- --t.-
-I- -
=- - ..;
It
-~Ig876
5
4
3
I
-tOO
1/1111/
o
54
tOO 200 300 400
0.2
o 100
·i-tll- f:.Tfl~aii--~f~"':::-l_ -~
-,r:
-f- I--
-!!III~---.-.--r=..t= :.
8+FUGACITY FUNCTION [~I--
OF BUTANE §i=-I- ffP-i' -:-.:~. '- Ii §
_,.-,_-r-F ~~ H-".IEI:- ~=8::=--=+:~-
- --'-+-
'--4-=1=
1111I
I--l.-r·~· - ..:->-.-
1/
j:-t-;' 100--. 90±:'--;
7 ..-f~- 3f~80--
,.J~ 51~70
=t--+=!'- ~~:t- 60
I !_-l,~ 50
f---
...::;C :-I.,~ i7 40
30.-
20
=. ---:::-:~-_.
-. ~r_ ~_r=-- ~~ -~_
... , .-1'\)-f-
.. • r-. . ..- -~E::: :;=. :7t ;-~
j-,.. 10
91=I
8j:::f 7
6
5
4
3
I II
H--i-I -H-+-t-l---H-++-+-+-+-IH-+++-t--HH-++-+-+--HH- 'I - -LIl-lH--H..j-+-HH--H-++-HH--H-++-H-+-H-++-H-+-~--H-j
I-100 o
55
100 200 300 400
0.90.60.7
0.6
0.5
0.4
0.3
0.2
II
-100 a
t I I
100
~ FUGACITY FUNCTION ~.-OF ISOPENTANE ~
:
40
30
20
4
3
I
IjjjT±-;1-±±ttttjjjttt::t:t:tttttlltJzt~~:tt:t1tttt:!i!~~~~:t;;'tr~t'ttt:r~;r~11!!!t:!=1o 100 200 300 400 500
56
H-++++-H-++--H-t-f-+-t--H1't+t-i-:+t+' -"1f-f-+-1
H--H-+t-H-t-f-+-H-+t+t-H-t-f-+-H-+t+t-Hf-f-t-I-t-t--H-H-Hf-f-t., I
--:
50
= 40
... 30
. • 1 I~ :¥T 117'
17'If
11 ,It .+-H-H-H-H-i+H-H-H-H-H-H-H-H-H-++++++++++-hI"'H-T+-H'-H'<H-++++Tt-++++--H~t-H
20
. I - !/II
," ::E- o- ,-:=_~c:~~'% .)e;d _.
~~~ :-r' '. ';: ~~. E'.~'~-- r-+-'
/~ :-='/--::- r:t=-1=' '~.:i=d-. ~ ,.-..,;-
1=, ,
-:!=.::l~·::r!.::-+- ~~.~!-:. -..e.;-::!::C-- 1""- -
1-1-
I -:::c.J' :~~ 10
987
6
5
4
H- 3
2
a 100
57
200 300 400 500
.... .
::E;'?:::f ~i=ft. -I/~~ ± .~E .E'-=H'
(
(
•::::=.....
I....:_!c·~.CE1. FF' .::t::;::
,:: ~FUGACITY FUNCTION
OF HEXANE
200
= ......
100
:t
~/~ ...
:~ :4'; i'c
o0.90.80.70.6
0.5
0.4
0.3 t-
,--'
0.2
II
c.., ~ ..£ '. ~-."'--:- ......
- • - ~t-- _ "- --4-
... ..=l=E ~--::-"'::: ........ ~'-, - '-!-
_., .... ''-=..-_"- """T
-!--,-
~IOO~90
807060
50
I -"'-r--
o ._
40
30
20
Ii
II I
- :t:-.t=: _ :-~ .;:~ •. ::..: '-i-:;:-_
.: ;:::;:-~. ::H:~;:-: . =r-r :-E~.·U·~· "-r . '1:';=1....".[ .:~t""e§::l=::±: -0-- :t=t:: ...c.. r=::::t:::::t=t:
=r- =j---:-'
,t:b::
.I
.I~e7
~~ 6
5
4
3
2
... 1/- - V! ,I I I I
0 100 200 300 400 500
58
=-
ClhHH-+-++++-++-H-Il--JI+-H--H--I-HH-+-++-
o
I.O~O.9~
0.80.7
0.6
0.5
0.4
0.3
0.2
'T
0.09 '0.08
0.07
0.06
0.05
II
100 200 300
I
;::. I=l=I§ FUGACITY FUNCTION~~ OF HEPTANE
~. --->-,- ~ -'f
-8 -
-o 0.04
0.03
o 0.02
~ ..
!/1I
100 200 300
59
20
4
3
2
400 500
0.80.7
0.6
0.5
0.4
100 200 300
0.3
0.2
0.080.07
0.06
0.05
0.04
0.03
0.02
I
~ FUGACITY FUNCTION1E OF OCTANE ~
:
I
30
20
-+--I--t-+-t-+++-+-+-+4 '
++++H-H··t-H-+-++ I-f--H-H-+'++++++-++I-I-f--H-+--J----I--++++++-hj£.j-I-I-hjoq~
- f:::j:. - -',-, .
• +-t-
100
GO
200
-t'i-"'Fff J.-1:- .-'-= +ie,'}l
. t= I. t=:± =Lfi.f- f-L - F.'r1 ::-~ ...
& I-~
~- ~~rj'
~ ±-l-I' -
II II
300 400
4
3
2
500
FUGACITY FUNCTION
OF HYDROGEN
p::; THE FUGACITY FUNCTION OF HYDROGEN. IT"fplfll'' IS BASED ON AP PARAFFIN SOLVENT HAVING A MOLECULAR WEIG HT OF 114 (OCTANE).~ FOR OTHER SOLVENTS MULTIPLY THIS FUGACITY FUNCTION BY THE..... CORRECnON FACTORS, A, FOR MOLECULAR WEIGHT, AND e. FORtHw CHARACTERIZATION FACTOR OF THE SOLVENT~
THIS CHART DOES NOT APPLY AT TEMPERATURES GREATER THAN0.95 TIMES THE PSEUDO-CRITICAL TEMPERATURE* (OR) OF THELIQUID PHASE. *Tpc: XH (60) + X HC (THC)
I I I I I I I . I -r 2000
o
3
K:l 50
. - - _.. , ==- ,__ ··_··-0 -- - ._. -~.
~
-
100 150 200 250 300
1.0
0.9
0.8
61
0.7
0.640 60 80 100
.... I
120 140 IGO
.9
.8
.7
.6
.5
.2 .3 .4
=
.5 .6
..
.1 .8 9 10 11 12
T-
131~.O
9
.8
.6
.5
A - -fLr =
II-fp IP VS PIPe FOR LIQUID PHASE
flT/IT VS IT/Pc FOR VAPOR PHASE
"':~-:. -~~ .
+.-!
RE~ERENCE: LEWIS AND KAY. OIL AND GAS J. 32. NO. 45, 40 (MARCH 29, 1934)
.2
i'
FUGACITY OF HYDROCARBON VAPORS
-,
,6.. -;fu.~ tl:f.1·...,;....+..........." ~
It
lJ
h
.S
.1
•o .1 .2 .~ .5 .6 .7
62.8 .9 1.0 J.2 1.3 1.4
.40I.
.9
.8
.7
.6
.5
',4 1.6
.7
.6
A
J
ot.4 1.6
1.8 2.0 2.2 l.4 2.6 2.8 3.0 32 3.4 3.6 3.8
FUGACITY OF HYDROCARBON VAPORS
. ~ ..
1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 16 18 4.063
.9
.7
.6
.5
.4
.2
o
RELATIVE VOLATILITY<-
OF LIGHT HYDROCARBONS
2.00
400300200
ETHYLENE (ETHANE
- ,
:r100
, -_l
1.80
1.70
.-++- .~
1.60
1.50 -::1:; .
1.40::l"-
~+
1.30
1.20
1.10
1.00-100 0
:h
1.40
1,30
Ir.1.20
1 ~, -.
1,10
1.00• -100 0 100
PROPYLENE/PROPANE
200 4C0
RELATIVE VOLATILITY
;OF LIGHT HYDROCARBONS
1.30
1,20
1I0
I J
ct'I-
ISOSUTENE/SUTANE
FOR BUTENE °l/BUTANEMULTIPLY BY 0,980
1.00 o 100 200 300 400
TRANS-SUTENE-2/SUTANE
.901... r
1+= J..~
o 100 200 300 400
CIS - BUTENE- 2/SUTANE
1.00
•.90
.eo0 100 200 300 400
1.3-SUTADIENE/SUTANE
tOO
LIO
tOO
.90 0 100 200 300 400
65
RELATIVE VOLATILITY
••1
. ".
+
, :'-' -!:-i1-
I.IO....~o ~O 1410101
,.801111
66
=
8 9
~~~~'I:
FUGACITY CORRECTION FACTOR
LIGHT HYDROCARBONS IN ABSORBER OILS
2.5
2.0
1.5
_ t- .
- ~ L:9..
MULTIPLY FUGACITY FUNCTIONS
(OR VAPOR PRESSURES) OF LIGHT
HYDROCARBONS BY CORRECTIONFACTOR WHICH IS INDEPENDENT
OF TEMPERATURE AND PRESSURE
*CHARACTERIZATION FACTOR OF THE LIQUIDPHASE IS A WEIGHT FRACTION AVERAGE OFTHE CHARACTERIZATION FACTORS OF THEABSORBER OIL a DISSOLVED HYDROCARBONS.
REFERENCE: COMMUNICATION FROM lHE M.W. KELLOGG CO .. NEW YORK. N.Y.
,-..
8 9 10 " 12 13
67
Section 6
CRITICAL PROPERTIESAnalogous to PUl'C substanccs, thc true critical point of a milltUl'c is a uni'lUC
point on thc phase cnvelope where thc dcnsitJy and composition of the vaporphase arc identical with those of the liquid phase. Sincc the compositions of thetwo phascs arc the samc, fractionation of a mixturc is impossible at the criticalpoint. Conscqucntly, the dcgrec of approach to thc critical point of a mixtuTe sometimes serves as a rough guide to thc fcasibility of separating thc components byfractionation.
For PUl'C hydrocarbons, it has been found that a number of physical propcrtiesmay bc correlated by reduced tcmperature, TITe, and reduccd prcssure, PIPe.Various data have shown conclusively that none of these correlations apply tomixtures if the truc critical temperature and pressure of the mixture are uscd todetermine the "edueed conditions. This difficulty has bccn overcomc by thc introduction by Kayl of thc concept of pseudo-critical tcmpcrature and pressure. Byusing thc pseudo-critical tempcrature and pressure to predict the reduccd conditiuns, Kay found that compressibility data on pure hydrocarbons could be appliedto mixtures. Although Kay determined the pseudo-critical point by averaging thecritical properties directly for known mixtures and from the averagc molecularweight for pctrolcum fractions, it has been found that much bcttcr results can beobtained by using the average boiling point method proposed by Smith andWatson. 2
As Smith and Watson pointed out, the true and pseudo-critical points mustapproach each other as thc boiling rangc of a fraction approaches zero and mustcoincidc for purc compounds. These conditions arc fulfilled by the charts in thissection applying to petroleum fractions. Smith and Watson's relation betweent11C true and pseudo-critical pressurcs on page 74 has been checkcd by the truecritical data of Kay on ethane-hcptanc3 and cthane-butane· systems. These dataconfirm Smith and Watson's eurvc well into thc region of their recommendedextrapolation.
GENERAL REFERENCES
Doss, "Phyaical Properties of the Principal Hydrocarbons," 4th Edition, The Texas Co.,Nel\' York, N.Y. (1943).
Internationnl Critical Tables, Vol. III.Roess, J. Insl. Pelr. Tech. 22, 665 (1936).
'l{ay, Ind. Eng. Chem. 20, 1014 (1936).2 Smith and Watson, Ind. Enu. Chern. 29,1408 (1937) .• Kay, hId. Eng. Chern. 3D, 459 (1938) .• Kay, Ind. Eng. Chern. 32, 353 (1940).
68
,
1000900800 ._mIlffim
I~m
II~JI ' I • •m j~ r ~; 111' ,· tlftfi, •
CRITICAL TEMPERATURE
I OF PURE HYDROCARBONS , Iim1,.m11 ~
Hm1 ~
!WJI • IlOOl
"0 iMj 11m! rnu:
l1m1 ,·
t .
'I,
mitIHI mrr
I,
IIWJ.I
1 Ill~. " .<i1 i- t1 ' .I ,J 1 .
:i' "I~ , r t ,, ·°illii !
r (1 · ,. ,I mm,,' ,. ,
f m,L f I ,.. I · ,
I ,. , I I II' II I i
, f! I 1 I" it
f I" I ' J j' ! I,
t•"
r; I i i . 1!II I . , I ! i IJ 'i , j ., .
'J 11 I • , I j 1ti;. I
,. ·rYl·j ~! I I
f r I,, IIIlI ,
!l .1.: I' . I .11 j , I , .. J! J! I I I i " , •,j'" I . 't ::' , , • I I r- 1-1' .In 1m I II inl ! I j f I t ! i' ill dlj!1! liid!!tl! Jfi10 • I , ,
I, HI,
'I I' Iii i'l: i' rr"l 'l1 t lt-f r:. : .. :-1"' .
':: IJ I f ~ ~:; ,. iI! :-!, ~.1. ;~: I r,I! tl . , , !I ,j" 1 II ." , ,.. ,. T' ", ill ,'f· 'lil!1 ''I ! ' 1.I '1 ' f 1 . i jiPi ' :. 1111["1 " I!PI : t ,I , .'II- r ljl' ~ .. , :-1'; ;, !, 1. It!; I :.•L 1!. , ., ' .. I ", .. , fH. ,,' !' r_1
'. I," , ! I ' l.Hli' , : ! fl lill Ijl illlit! iu,1 liP il ! 'I" :1:: : 1tI1f I 1 1 1'01, I t:tl . t: ,. • t.I"., t. ,•.:r I . ·, 'II!, IllliQ,HHlii!!: III li1
It IIU11 HI' , I tubI
70
800
900
500
600
1200
1100
100
100 200 300 400 500 600 700 80069
80-220 -200 -190 -160 -140
. ,60 440
CRITICAL TEMPERATURE
40 OF LIGHT HYDROCARBONS 420q,PURE COMPOUNDS AND MIXTURES
.f!:[20 - -. - ,- 400+ 'l* t"
i , ... ' .-u
0 390
...L,-20 360
-40 340
-60 320
-80 300
·100 290
-120 260
r 240j.
220[,
.. I I .. In200
1r THE BASE CURVE REPRESENTS CRiTICALI TEMPERATURE VS. BOILING POINT fOR PURE
"I" HYOROCARBONS ANO PSEUOO-CRIT'CAL TEhIP- 190I i: _I 1 ERATURE vs. MOLAL AVERAGE BOILING POINT
I J I t II ,
FOR MIXTURES.THE GRAVITY CURVES REPRESENT TRIJE 160
I CRITICAL TEMPERATURE YS. WEIGHT AVERAGEBOILING POINT FOR MIXTURES. fOR ALL HYDRO-
I CARBONS THE PARAFFIN GRAVITY OF THE 140I SAWE BOILING POINT 5H:XJLO BE USED INCOMPUTING THE GRAVITY OF THE MIXTURE.
. , .fiT • 120t; ~ 1h .l I ~
I .. II 100If I~ I [ f ,I· II ., ,
: ill j -,_i¥-1
80
-140 -120 -100 -80 -60 -40 -20 0 20 40 60 80 100 120 140
70
/
20
40
50
280260240220200180160
!mI ~ --
~
CRITICAL PRESSUREOF NORMAL PARAFFINS
20 40 60 80 100 120
'~i
Ii
THE PSEUDO-CRITICAL PRESSURE OfLIGHT HYDROCARBON MIXTURES HAVING
AN AVERAGE MOLECULAR WT. LESS THANBO CAN BE DETERMINED FROM THIS CURVE.
--.-: .-:- ...
I
I
.-
-.
J-
- - -I t+: r -
Iii L - .
i~- ~i
15
40
10140
20
30
71
1300
1000900
t .... ..=r::
':Ct8<i5-2' -:-' >:.~.....,...., _.- -1
800 §
~
"
. --
1100 -
800 ...
700
.~
=,-
... ",.. , .~".'- "-J :....
, ..
,- ~
'1'=: •.::r; ":-1.ir
.... ..
,-
... -..
;.~r:$·
:$. • t "...
~.
ct= •
800
100 200 300 400 500 600 700 800
72
00
00
300
1000900
100 200 WO 400 500 100 7('. r-
PSEUDO- CRITICAL PRESSURE •OF PETROLEUM FRACTIONS-
-
II-~2
2,
I
--- ~~ -
tqJ~,. . .- ~ '. I ,IIIII11 t-..l ahr,f-h---- -- FfttlIMmiI - -
I
250
100
300
500
400
100800
200
I 600
73
TRUE CRITICAL PRESSUREOF HYDROCARBON MIXTURES
-
!l.0.. 1.18 1.20 1.2.2. 1.2.4 1.2.6M
- - - -4.0 4.0
-
3.0
2.5
2.0
DETERMINED BY MULTIPLYING ITS PSEUDO-CRITICALPRESSURE BY THE RATIO OF TRUE TO PSEUDO-
, CRITICAL PRESSURE, PTC/Ppc. THIS RATIO ISGIVEH BY THE CURVE AS A FUNCTIOH OF THE RATIOOF TRUE TO PSEUDO CRITICAL TEMPERATURE. TTCl1l'l;.l
. ""1l1i"
t:J+lJ
2.5
2.0
'.5 H-t-t+t-H-t++t-H-t+'~ mI.5
REFERENCE: SMITH AND WATSON. IND. ENG. CHEM, 29. 140B (1937)
1.02 1.04
74
1.08
Section 7
THERMAL PROPERTIESSpecific Heat
Since hydrocarbon vapors deviate considerably from a perfect gas, except atlow pressures, their specific heats arc a function of pressure as well as temperature. However, vapor specific heats at higher pressures have limited application asenthalpy correlations may be more readily used for thermal calculations. For thisreason, the specific heat chart~ for gases and vapors (pages 88 to 91) arc givenonly for low pressuros (0-1 atm) where deviations from a perfect gas are sosmall that specific heat may be considered to be a function of temperature alone.The specific heat of a mixture of two or more gases at low pressures may becalculated from either their weight fraclions multiplied by their specific heat~ ortheir mole fractions by their molal heat capacities (MC.).
Two charts are given for the specific heat of. petroleum vapors, one on page 90for crude fractions and another on page 91 of more general application to bothpure hydrocarbons and petroleum fractions.' The chart for crude fractions is amodification of the Bahlke and Kay eorrelation 2 and the other the same type asa chart developed by Fallon and Watson. 3 Both ehart~ are believed to be somewhat morc accurate than the previous correlations and arc also representativeof additional data.
The change in enUlalpy of hydrocarbon vapors with pressure at constanttemperature may be calculated from the chart on page 92. While the ordinaterefers to the difference in enthalpy from the vapor at infinite dilution, this may beconstrued as any low pressure (0-1 atm). This chart was used to compute theenthalpy of hydroearbon 4 and petroleum vapors at elevated pressures in thedevelopment of the enthalpy charts. Since the change in enthalpy at constant
1 These correlations {or petroleum fmctions nrc not quite consistent with the additiverule for mixtures. Since these curves apply directly to mixtures, the additive rule would holdonly if the specific heals eit,1).cr were independent. of the liquid specific gravity or \'aricdlillcnrly with its reciprocal (directly with 0 API). With neither of these conditions fulfilled, thepetroleum vapor correlations have a fundamental inconsistency but the resulting errors areimperceptible as far as the data are concerned.
2 Bahlke and Kay, Ind. Eng. Chem. 21, 042 (1929).3 Fallon and Watson, Nat. Petroleum News, 'l'echnical Section, R-372 (1944).4. For the light hydrocarbons below hexane, there was a slight trend with molecular weight
in the change of enthalpy with pressure at constant. temperature. This was taken into accountby the use of other unpublished correlations by Gilliland (sce reference on the chart OD
page 92) for these low-boiling hydrocarbons.
75tottlGl"N" A.L.)
CO?l A \1i'1B.·::1 \. .)
PABLO M01.'"l'A
76 DATA BOOK ON HYDROCARBONS
temperature can be read directly from the latter charts, this generalized chart haslittle direct application but is included as one of the fundamental correlations.
The chart for the specific heat of hyd!"Ocarbon liquids was developed" directlyfrom liquid specific heat data on pure hydrocarbons and petroleum fractions.Since liquid specific heats were not used in the development of the enthalpy charts,this chart is independent of and not necessarily consistent with the latter correlations." For the sake of consistency, thc enthalpy charts usually will be used inpreferencc to this spccific heat chart but, at the samc time, it is desirable to includean independent correlation of such a fundamental thermal property.
Latent Heat of Vaporization
The latent heat of vaporization of any compound is the din'erence in enthalpybetween its saturated vapor and its saturated liquid at constant temperature andmay be expressed either as a function of temperature or as a function of vaporpressure. The latent heats of low-boiling hydrocarbons and, also, higher-boilingnormal paraffins of even boiling point arc plotted again t vapor pressure on pages94 to 97. While the use of temperature instead of vapor pressure as the correlatingvariable would have advantages, it would also result in the curves crossing eachother, thus making the plots difficult to reae!.
The latent heat charts were derived by using a direct proportionality betweenthe molal heats of vaporization of any two hydrocarbons at the same reducedpressures.' For the lower boiling hydrocarbons, the latent heat data were smoothedout and extrapolated by the use of a reference compound (ethane, butane, orhexane). Where no data were available, as in the case of a few of the light hydrocarbons and all of the higher-boiling normal paraffins, the latent heats were calculated directly from this reduced pressure relationship. The slope or proportionality constant was predicted from the normal boiling point of the hydrocarbon.
The latent heat of vaporization of other hydrocarbons may be calculatedfrom the normal paraffin cun'es by the usc of this same relation. That is, theunknown compound will have the same molal heat of vaporization as a paraffinof the same normal boiling point at the same reduced pressure. In the case ofpetroleulll fractions, the mean average boiling point is used for the normal boilingpoint and the reduced pres ure i computed f!"Om the pseudo-critical pressure ofthe mixture. The "vapor pressure" of thc fraction corresponds to that of a pure
• A modificatIOn ot a correlatIOn oy Tne M. W. Kellogg Co., New York, N.Y.• The enthalpy eharls were derived from: (J) the vapor specific heaL eo",elnlions (0-1
aIm); (2) lhe generalized chart for change of enthalpy with pressure; and (3) the latent heatrelations. Inasmuch as the inaccuracies of all three correlations accumulate in Lhe jjqu;:!enthalpics 01' specific heals, the agreement wit.h the liquid specific heat chart may be ~nnsidcrcd
quite good as average deviations between the two are around ±3% wlt.h a maxImum ofabout 6%.
7 Maxwell, Ind. Eng. Chem. 24, 502 (1932).
THERMAL PROPERTIES 77
hydrocarbon of the same normal boiling point at tbe temperature of the fractionand ""ver relers to the bubble point, dew pofnt, or operating pressure 01 the system.
Since the difference in enthalpy between the liquid and the saturated vapor ofa pctroleum fraction always involves change of enthalpy of the vapor at constanttemperature in addition to latent heat, except at low pressures, the enthalpy correlations are much more convenient to use than these individual therm,.l properties.
Thc following examples illustrate the usc of the latent heat charts:
Example 1. Compute the latent heat of benzene at 1 atm.
The boiling point of benzene is 176.2°F and its critical pressure is 47.9 atm.The molceular weight of a normal paraffin boiling at 176.2°F is 91.5 and its criticalpressure 28.3 atm. The vapor pressure of the normal paraffin corresponding to areduccd pressure of 1/47.9 ( - 0.0209) is 0.0209 X 28,3 - 0.59 atm.
The molal heat of vaporization of the normal paraffin at 0.59 atm is 91." X(146 BTU/lb) - 13,360 BTU/mole.
The latent heat of benzene at 1 atm is then equal to 13,360 BTU/malo or171 BTU/lb. The Bureau 01 Standards Circular C461 gives 169.3 BTU/Ii> '.s thelatent heat of vaporization of benzene at 1 atm.
Example 2. Determine the latent heat of vaporization of the following ga9oil at 500°F.
10% Distillatioll
10% @ 430°F50% @ 540°F70% @ 605°F90% @ 680°F
Gravity
35°API
Vol. Av. B.P. = 547°F; Slope = 2.9°F/%Mean Av. B.P. = 547 - 9 = 538°FMolec. wt. = 211Vapor pressure (538°F normal B.P.) = 0.63 atm. at 500°FPseudo-critical pressure = 266 psia co 18.1 atm
I'l'lolee. wt. of normal paraffin (538°F normal B.P.) = 222Critical pressure of normal paraffin = 15.0 atmVapor pressure of normal paraffin = (l5.0/18.1)0.63 = 0.52 !!.tmLatent heat of normal paraffin = 104 BTU/lb
Latent heat of vaporization of the gll3 oil!!.t 500°F
= 22Z X 104 = 108 B1'Ulib214
78 DATA BOOK ON HYDROCARBONS
Enthalpy of Light Hydrocarbons
The enthalpy 8 or heat content of low-boiling paraffins, olefins, and aromaticsis given by the chart.s on pages 98 to 113. These charts can be applied to mixturesof light hydrocarbons on the basis of the following assumptions:
1. The entha!pies of individual components of a mixture are additive inthe !iquid phase, that is, the mola! heat content of the mixtttre equals the sumof the products of the mo!al heat contents of the components by their mo!efractions.
2. The entha!pies of individua! components are additive in the vapor phaseat !ow pressures (0-1 atm).
3. The change in enthalpy of the vapor with pressure at constant temperature is the same for a mixture as for a sing!e compound having the same mo!ecularweight as the mixture.
The first assumption is substantially true for hydrocarbon mixtures (especially for homologous series) at temperatures below the critical regions of allcomponents. At temperatures near to or above the critical temperatures of any ofthe components, the liquid mixture is no longer an ideal solution of its componentsand there is some deviation from the rule of additive heat contents. However, sincethese deviations arc not too serious, and since no other simple method has beendeveloped for determining the heat content of a liquid mixture, the rule of additiveenthalpies should be used for all hydrocarbon mixtures irrespective of the criticaltemperatures and chemical composition of the components.
The second assumption is strictly true only for vapor mixtures at infinite dilution (0 atm) but is a very close approximation for pressures up to 1 atm.
The third assumption is empirical but has been shown indirectly to give quiteaccurate rcsults for mixtures of homologous series and petroleum fractions. Also,the usc of the average molecular weight to determine the change of enthalpy withpressure is the simplest average which can be used.
Above thc critical temperature a dashed line is shown for the heat content ofthe gas in solution. This line was based on the assumption that thc gas in solutionat any temperature would have the same partial density and enthalpy as the purecompound at a pressure corresponding to an extrapolation of its vapor pressurecurve above the critical point. Obviously, this is only a rough approximation sinceboth a vapor prcssure curve and an ideal liquid solution arc meaningless in thisregIOn.
E:rample 3. Determine the difference in enthalpy bctween the liquid at100°F and the vapor at iiOO°F and 20 atm for a mixture having the followingcomposition:
8 Based on on entholpy of zero for the saturated liquid 01, -200"F.
THERMAL PROPERTIES 79
Component
C,H.CsH.C,H lO
C,H,CsH.
Mole Fraclioll
0.100.500.100.050.250
1.000
or
The enthalpy of the mixture as a liquid at 100°F and as a vapor at 500°F and0-1 atm is computed from the individual components as tabulated below:
Enthalpy of Liquid Enthalpy of Vapor
Com- Molel\lolcr, Wt. lOO°F 5OQ°F and 0-1 elm
poncnt Fract.Lb/Mole
of Mixture BTU 1~lole BTU ll\lolcBTU lIb
of MixtureBTU lIb of J\'lixture
CzH s 0.100 3.0 239 720 553 1660CaH s .500 22.0 171 3760 530 11660C4H 1O .\00 5.8 159 920 525 3040C2H 4 .050 1.4 223 310 506 710C3H, .250 10.5 169 1770 508 5330
42.7 7480 22400
li y (500°F, 0-1 atm) - liL = 22,400 - 7480 = 14,920 BTU/mole
The change of enthalpy of the vapor at 500°F betwecn 0-1 atm. and 20 atm.is computed by interpolating between C,H. and CsH.:
C,H.:1f,,(500°F, 20 atm) - liy (500°F, 0-1 atm) = 30(546 - 553) = -210 BTU/mole
CsH.:H y (5OO°F, 20 atm) - li y (500°F, 0-1 atm) = 44(522 - 530) = -350 BTU/mole
Mixture:42.7 - 30
li y (500°F, 20 atm) - liy (500°F, 0-1 atm) = -210 + H _ 30 {-350 - (-21O)J
= -340 BTU/mole
Therefore,
li y (500°F, 20 atm) - liL(100°F) = -340 + 14,920 = 14,580 BTU/mole
14,580 = 849 BTU/Ib42.7
The foregoing procedure can hc simplificd, with a loss of accuracy which doesnot usually exceed 5%, by interpolating on a basis of molecular wcight and total
so DATA BOOK ON HYDROCARBONS
l
•
olefin content between the initial and final states:
CaHs:H v (500°F, 20 atm) - Ih(IOO°F) = 44(522 - 171) = 15,440 BTU/mole
CZH4 :
H v (500°F, 20 atm) - Ih(lOO°F) = 28(500 - 223) = 7750 BTU/moleCaHe:
H v (500°F, 20 atm) - HL(lOO°F) = 42(500 - 169) = 13,900 BTU/mole
Since the average molecular weight of the paraffin portion of the mixture is 44, thepropane values can be used directly, making interpolation unnecessary.
The average molecular weight of the olefin portion is 39.7; hence the enthalpydifference between the initial and final states will be:
7750 + 3:;7_-2~8 (13,900 - 7750) = 12,880 BTU/mole
Interpolating between the paraffin and olefin portions,
Hv(500°F, 20 atm) - HL(lOO°F) = 0.70 X 15,440 + 0.30 X 12,880
= 14,670 BTU/mole14,670
or 42.7 = 344 BTU/lb vs, 342 BTU/lb by the longer method.
Enthalpy of Petroleum Fractions
The enthalpyO of petroleum fractions is given by the charts on pages 114 to127 for both paraffinic stocks, having a characterization factor of 12.0, and nonparaffinic stocks, having a characterization factor of 11.0 over a mean average boiling point range from 200°F to 800°F. Theoretically, these chartsrepresent pure hydrocarbons of the designated characterization factor and boilingpoint, but they may be applied to petroleum fractions if the following assumptionis made in addition to the three previous ones pertaining to light hydrocarbonmixtures:
4. 'The avemge difference between the enthalpy of the vapor at low preSSU1'es(0-1 atm) and the enthalpy of the liquid, at constant temperature, is the same f01'a rni.'l:ture of chemically similar hyd1'Ocarbons as for a single compound of thesct'1ne molecular weight (or mean avemge boiling point).
\\'hile this assumption is empirical, it is accurate \\'ithin a few percent excrptin the region of the pseudo-critical temprrature \\'here the enthalpy of the liquidis subject to variation depending upon the true criticaltemperatUl'e of the mixtUl'e.Since the dashed line starting at the pseudo-critical point applies only to a purecompound in solution above its critical point, another dashed line was arbitrarilydrawn for mixtUl'es, joining the satUl'aled liquid line below the pseudo-critical
9 Based on all enthalpy of zero for the saturated liquid at 00 F .
THERMAL PROPERTIES 81
Ipoint with the pure compound line about 50°F above the pseudo-critical tempera
_ ture. This is more representative of a mixture and should be used in preferenceto the pure compound line.
These charts may be interpolated and extrapolated linearly with bothcharacterization factor and mean average boiling point. Occasionally, in inter·polating between two adjacent boiling point chart~ the pressure and temperatureof the vapor will be such that they fall inside of the "dome" of the higher boilingpoint chart.. Since it is impossible to use the charts in this region, it is recommended that the two adjacent lower boiling point char'" be extrapolated upward.
Following are two examples illustrating the use of these charts:
Exan,ple 4. Determine the ditTcrence in enthalpy between the liquid at 500°Fand the vapor at 775°F and 25 psig for the following refined oil fraetion:
Crude Assay DistillatiOlt
I.RP. 300°F50% 440°FF.B.I'. 580°F
Grauity
400 API
Vol. Av. RP. = 440°F
81 f t} d· '11 . 580 - 300ope 0 Ie Istl atlOn eurve = 100 = 2.80 F/%
Mean Av. B.P. = 440 - 6 = 434°FCharacterization Factor = 11.65hI' = Enthalpy of the vapor at 775°F and 2.7 atm (25 psig)hL = Enthalpy of the liquid at 500°F
Mean Au. B.P. -400°FCh. Factor = 12: h" - hL = 567 - 286 = 281 BTU/lbCb. Factor ~ II: hv :- hL = 538 - 263 ~ 275 BTU/lbCb. Faetor = 11.65: hI' - hL = 275 + 0.65(281 - 275) = 279 BTU/lb
Mean Au. B.P. -500°FCh. Faetor = 12: hI' - hL = 556 - 273 = 283 BTU/lbCh. Factor = II: hI' - hL ~ 534 - 255 ~ 279 BTU/lbCh. Faetor = 11.65: hI' - hi = 279 + 0.65(283 - 279) ~ 282 BTU/lb
Mean Au. B.P. - 434°FCb. Factor = 11.65: hI' - hL = 279 + 1.'..(282 - 279) =.280 BTU/lb
If the char'" for 300°F and 400°F Mean Av. B.P.'s had been extrapolated, theresult would have been essentially the same, 281 BTU/lb.
Example 5. Determine the difference in enthalpy between the liquid at 425°Fand the vapor at 925'F and 350 psig for the following gas oil:
,
Gravity
15.5°API
DATA BOOK ON HYDROCARBONS82
10% Distillation10% @ 455°F50% @ 560°F70% @ 620°F90% @ 695°F
V I A B.P 455 + 2 X 560 + 695o . v. . = = 5670F
4
SI f di t 'II . 620 - 455ope 0 B I ation curve = 69 = 2.8°F/%
Mean Av. B.P. = 567 - 5 = 562°FCharacterization Factor = 10.48
hv - hL = 662 - 233 = 429 BTU/lbhv - h L = 622 - 216 = 406 BTU/lbhv - hL = 406 - 0.52(429 - 406) = 394 BTU/lb
hv - hL = 642 - 224 = 418 BTU/lbhv - ltL = 606 - 208 = 398 BTU/Ibhv - hL = 398 - 0.52(418 - 398) = 388 BTU/lb
hv = Enthalpy of the vapor at 925°F and 24.8 atm (350 psig)hL = Enthalpy of the liquid at 425°F
Mean Av. B.P.-400°FCh. Factor = 12:Ch. Factor = 11:Ch. Factor = 10.48:
Mean Av. B.P.-500°FCh. Factor = 12:Ch. Factor = 11:Ch. Factor = 10.48:
Mean Av. B.P.-562°FCh. Factor = 10.48: ltv - hL = 388 - M(394 - 388) = 385 BTU/Ih
MollieI' Diagrams
The MollieI' diagrams for the individual light hydrocarbons are of essentiallythe same type as the familiar one for steam. To minimize confusion and to makethe charts as easily usable as possible, lines of constant volume are omitted andlines of constant temperature replace lines of constant superheat in the superheated vapor region. These charts will be used principally for adiabatic compressions and expansions.
In applying the MollieI' diagrams to hydrocarbon mixtures, the mixtureshould be treated as a single compound of the average molecular weight. Anempirical study of the diagrams indicates that successive charts of the sameseries (paraffin or olefin) may be interpolated (or extrapolated) by assuming alinear relation exists between melecular weight and (1) isentropic change ofmolal enthalpy with pressure and (2) the product of the square root of themolecular weight and the isentropic ehange of temperature with pressure.
If both paraffins and olefins are present in the mixture, the charts of each
•
THERMAL PROPERTIES 83I
series are interpolated (or extrapolated) to the average molecular weight of t.hetotal mixture. These values corresponding, respectively, to a 100% paraffin mixtureand a 100% olefin mixture are used for linear interpolation to the actual olefincontent of !lie mixture.
The following example illustrates the application of the MollieI' diagrams to ahydrocarbon mixture:
Exmnple 6. Determine the work of compression 1 0 and final temperature whenthe following mixture is compressed adiabatically from atmospheric pressure and60°F to 50 psig:
AverageComponent M ok Fraction Molee. WI.
CH, . ....... . 0.050 0.8C,H, ........ .100 2.8C2H• ....... . .150 4.5C3H. .100 4.2C3Hs ..... - .. .200 8.8C,Hs .100 5.6C.H, 0 .200 11.6C.H,, ....... .100 7.2-- --
1000 45.5
Values corresponding to adiabatic compression from 1 aIm and 60°F to 4.4atm were read from the individual charls and arc tabulated below:
Compound S
C,B, 0.763C~HIO .680C2H.. .935C3He .780
BTU/lbI,
6fl
'F M(h, - h,) 61VMh, 112 BTU/mole
301.5 338 1M 1610 625295 321 135 1510 570300.5 363.5 221 1760 850303 3!2 164 16iO 675
By interpolation, lif{ = 1600 BTU/mole and litVM = 620 for a saturated hydrocarbon mixture of 45.5 malec. wt.
By extrapolation, li.H ~ 1610 BTU/mole and li/V,lf = 632 for an unsaturatedhydrocarbon mixture of 45.5 molec. wI.
By interpolation, li.H ~ 1603 BTU/mole and litVM = 6z.t for a hydrocarbonmixture of 45.5 malec. wt. containing 30% unsaturates.
10 Change in enthalpy which includes the difference between the work of expulsion andwork of admission.
84 DATA BOOK ON HYDROCARBONS
:. The theoretical work of compression is 35.2 BTU/lb and the final tempera.tureis 152°F.
If other gases (H2 , O2 , H 2 0, etc.) are present in a mixture, it is recommendedthat effective IJressures equal to 7rVYlfC be used to determine the total work ofcompression and final temperature of the hydrocarbon portion of the mixture.The inert g&ses usually may be assumed to be ideal and the w'ork of comprestlionand final temperature for this portion of the mixture calculated by the adiabaticcompression formulas for perfect gases. The work of compression for the mixtureis then evaluated by combining the change of heat content for the hydrocarbonportion with that for the inert gases on the basis of their mole fractions. In determining the final temperature of the mixture, it is assumed that the ch.ange inenthalpy of each portion from its final temperature to that of the mixture isequal and opposite in sign to the other. This method is illustrated by the followingexample:
Example 7. Determine the work of compression and final temperature whenthe following mixture is compressed adiabatically from 25 psig and 0°1" to 150 psig:
Hydrocarbon Portion
Component Mole FractionAverage Molec.
Wt. Average Molec.Mole Fraction
Wt.
H, 0.500 1.0 - -CH, .100 1.6 0.200 3.2C,H. .ISO 4.5 .300 9.0C,H. .250 11.0 .500 22.0
1.000 18.1 1.000 34.2
The effective pressuras to be used for the hydrocarbon portion of the mixtureare:
25 + 14.77rei = 14.7 vO.500 = 1.91 atm
150 + 14.7 --7r.2 = vO.500 = 7.91 atm
14.7
Values read from the ethane and propane charts are tabulated below:
BTU/lb t, 6.H MvMCompound S OF M(h, - hi)h, h,
C,H. 0.837 294 340 121 1385 663
CaR. 0.686 278 307 92 1280 610
THERMAL PROPERTIES 85
By interpolation, UTi = l35~ BTU/mole and t:.tVM = 6-1.7 for a saturated hydrocarbon mixture of 3-1.2 molee. wt. The corresponding final temperature forthe hydrocarbon portion of the mixture is 111°F.
For the H 2 portion of the mixture, the work of compression and final tcm.pera~
ture arc calculated as follows:
-. 6.97MCp = 2.016 X 3.46 ~ 6.96; K = 99 1.40
6.97 - I.
UTi =~R1'[("2)K~' - IJJ( - I "1
40 [(1647)1.40-' J= I. X 1.99 X 460 __. 1.40 - I1.40 - I 39.7
= 3200(1.502 - I) = 1610 BTU/moleI.fO -1
7'2 = (164.7)1:<0 X 460 ~ 691°R <> 231°F39.7
For the mixture, the work of compression = 0.500 X 1354 + 0.500 X 1610= 1482 BTU/mole <> 8f! BTU/Ib
The final temperature of the mixture is assumed to be the temperature I, atwhich
0.500[Ji Jre (t, 7.91 atm) - Jilfc(l1l°F, 7.91 atm)J~ 0.500[Ji Il (23I°F) - flll(t)] = 0.500 X 6.97(231 - t)
Since it is necessary to use enthalpy for evaluating UTi lie, t will be determinedby trial and error.
Assume t = 140°F.
Interpolating between the charts on pages 99 and 100,
0.500 X 34.2[3·12 - 328J = 0.500 X 6.971231 - 140]
240 "" 317Assume t = 148°F.
0.500 X 34.2[346 - 328J = 0.500 X 6.971231 - 148]
:l08 "" 290
By interpolation, the final temperature is I/.7°F.
While the foregoing procedure permits the ~follicr diagrams to be used formixtures of hydrocarbons and inert gases, the method of combining the cnthalpicsand the temperatures of the two portions of the mixture is theoretically incorrect.In this procedure it is assumed that if two gases, ha,-ing different thermal propcries, arc compressed individually from the same initial temperature and pressure
86 DATA BOOK ON HYDROCARBONS
to the same final pressure and then mixed, the resulting thermodynamic propertiesof the mixture will be the same as if the gases were mixed initially and then compressed. This assumption is not quite correct and will always lead to small positiveerrors in the work of compression and temperature rise. The errors usually willnot exceed a couple of percent with a maximum of about 50/0 if the averagemolecular weight of thc hydrocarbons is not greater than 50 and the compressionratio is not greater than 5: 1.
As an alternative to this method, the equations for an ideal gas may beapplied to the entire mixture, provided the gas law correction facwr for the hydrocarbons, P-YC, is not less than 0.05. In arriving at an average molal specific heatat constant pressure for the mixture, the molal specific heats of the individualcomponents at 0-1 atm should be used irrespective of the initial and final pressuresof the compression. The following equations apply to this alternative method:
Il .. = (y HCIlIlC + Yalla + Ybllb + ... )(MCP)m = YlIc(MCp)llc + y.(MCp). + Yb(MCph + ...
K = (MCp ).,
(MCp) .. - 1.99
K [(7I'z)K;: 1 ]AU = 1l.,R1" - - 1
K - 1 71'1
Tz = (::) \-1 T1
where Il = correction factor for deviation from the ideal gas law at initial conditionsY = mole fraction of any component
MCp
= molal specific heat at constant pressure (0-1 atm) and at the average
temperatureMCp
K=-MCv d' b t' compression = work ofAH = change in enthalpy during an a la a IC
compression . 0
7", Pz = initial and final temperatures m R71' = initial and final pressures
71'1'UC = subscript referring to the ~otal hydrocarbons
b t = subscripts referring to mdlvldual mert gasesa, J e c.
Example 7 will be recalculated by the alternative method:
For the hydrocarbon portion:460 . = 1.91 = 0.041; 1l1IC = 0.966
T = - = 0.80e, <fer 472r 575 .
MCp(700 F) = 34.2 X 0.410 = 14.0
For the hydrogen:
THERMAL PROPERTIES
I' = 1.000; MOp = 6.97
87
For the mixture:
I'm = 0.500 X 0.966 = 0.500 X 1.000 = 0.983MOp = 0.500 X 14.0 + 0.500 X 6.97 = 10.5
K = 10.5 _ •10.5 - 1.99 - 1.230
1 235 [( 6 ) •.2356H = 9:235 X 0.983 X 1.99 X 460 1
39\7 1.235 - 1]
~ 4740[1.311 - 1] = 1470 BTU/mole as compared with 1482 BTU/molepreviously calculated.
T, = 1.311 X 460 = 603°R "" 143°F as compared with 147°F by the firstmethod.
IC desired, this alternative method may also be applied to hydrocarbon mixturesif I' at tbe initial conditions is ?!at less than 0.95.
GENERAL REFERENCES
Communication from The M. 'V. }{ellogg CO'l New York, N.Y.Gary, Rubin and Ward, 11ld. E1lg. Chem. 25, 178 (1933).Gilliland l Unpublished data, Mass. Inst. Tech.Keenan and Keys. "Thermodynamic Properties of Steam1 " John \Viley &; SODS (1936).Misc. Publicatio1l of Bur. Standards, No. 97 (1929).Nat. Bm. Statuiards Circular C461 (1947).Sage, Webster a-od Lacey, Ind. E1lg. ahem. 29, 1309 (1937).Weir and Eaton, Ind. E1lg. Chem. 24, 211 (1932).
'i
0.60
1200
12001000
1000
l~n'd
800
800
NAT. BUR, STDS, CIRCULAR C461 (1947)KEENAN AND KEYES. 'THEfNODYNAMIC PROPERTIES OF STEAM' JOHN WILEY AND SONS ~O.46( 1936)
c",
600
.,.,
I"
400
--'400
",'I
11,,11,'",
'1-···..0-1 ATMOSPHERES
SPECIFIC HEAT OFMISCELLANEOUS GASES
..~, ..... ;
·f,.I~:;t+
tU"
·"l.IP
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.. '
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200
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",,~-.;", "·,'tT',..... t·
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!i
0.26
0.22
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gJ
.....9
1.2
1,0
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"200
89
300
.8
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o
+f~-l.J..Ht+Ji '-.r;
THIS CHART APPLIES TO PARAFFIN BASE
CRUDE FRACTIONS AND FOR OTHER
PETROLEUM FRACTIONS THE FOLLOWINGMULTIPLYING FACTORS SHOULD BE USED:
.7
TIfflI
I
'UlIJ[1fI"!
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SPECIFIC HEAT OFPETROLEUM VAPORS~
CRUDE FRACTIONS. 0-1 ATMOSPHERES 1tI111 Ufl II IIH II 11 H4 II$!
Ji
I
rn1
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.9B
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lit
I
MIXED BASE CRUDE FRACTIONS
ASPHAlT" to ..
.7
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eoo100
100 200 300 400 500 600 700
...... ~ : ,. ,.. .
'111111111 HEAT OF HYDROCARBON e +:'~ ~,: ._~ _. H" ..... - ", .,PARAFFINS,
.5
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4
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HYDROCARBON VAPORS; MOLEC. WEIGHT ~ 75
I I
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AT CONSTANT TEMPERATURE4
6 8 10
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06
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INST . TECH..Ql
3 42.6 .8
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92
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90
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180
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LATENT HEAT OF VAPORIZATIONOF LOW BOIUNG HYDROCARBONS 'J.ll',
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LATENT HEAT OF VAPORIZATIONOF LOW BOILING HYDROCARBONS
140
130
120
110
100
90 90
80 eo
70 70
60 60
50 50
40 40
30 30
20 20
10 10
14 16 18 20 22 24 26 :10 34 36
95
190
.002 .003 .004 .006 .008 .01 .02 .03 .04 .06 .08 0.1 0.2 0.3 0.4 0.6 08 1.0180 I I I I I , I I'! u:rrENT HEAT OF VAPORIZATION
180
170 I 1 1 I I 1I I 11111111111111 iHllliilil iii: :111 11111111: Ii ilillllll I I I 1 I I I I I11I fR ,i;i1111 ill:!l±ll Ulfl' , W, ; OF PARAFFIN HYDROCARBONS _170
I 1ij ,I'il VAPOR PRESSURES BEl.DW I-AllIIOSPHERE
, ",' 20' t It 11 ' 'I ttl 'J 'Ii 11 ' 1'1, - - "160 II 1I1,II!i 160
I . I', '
150 ' , , , , I 'I 1 1!~ti III fTtll.g;,,:jIIII:liliil I 1IIlTi'ti+;;±llllllllllllillil150ij II
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'140~. j hlHIIlIIlIHi11 1111'111111111111111111111
130 I-<t I 'III I II I' , ' "II , ,"II 130,
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ENTHALPY OF PROPANE
600
700
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600
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900t
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400
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700
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103
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:; 1\1: 11;' lL.. 1'1 WI "'.1\ ~~' I ~!l;~ :;;j 0 Ui ttl tl..:.'X '.,;
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o"ili .,' I W ,:1/1;1; '"I " 1111 X" :\I. I 11 111 h .dltil! I.l .... :__ HI: l::l HT .l~ 1- I·,' I .. ~ ,... ,\.j\.:" ~ ! 11 f t:j rr.(I)" , I . ",' j ,. I' . I'" I "1' I,··,,, 'I '''I lJ.'II I.", .[., 'Wfl.'"FJ. ,ll I.. . I '''1;' 1';"~". 'u ,:m".1.. +l:..l " .f. !H! :l:~' j . ":~~N.l I'U:~
t I I I ; j i;:i:Tn .~! iTI1~ri t Ii ". :ttf ..t 'l.'\I'J\Jrl 1'1 nn' ., T I ., , .. , I" II" '.I, t Iii· II:' i'/ 1tL,,~~N II ;1, II lib.
oj··· , . ~ 'LL~ ~t ~ L~ 1·, :......1 I .,1 '1t.\i.. r I I ·n' ~I~!'-
105
300
100
o500
1200
,--
,,
400
-t+t-;-, HilH1
300
i
100o-100-aoo
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f " f. , ,. u
. t~ ~T.:
800 • , +-:.I ..:t: "~ • it:· .
, ..,j ...rz:i .:-: _.1 1
100 600
It
600 500
,t 1
1500 400
~
400
106
107QR1G1N A.1.,\
CO PI A (FIR ';1 "cD:) i
PABl.,O 1'.1OT['.'\
500 600 700 900 1000 1100 1200
900
800+
700
~oo
ENTHALPY OF ETHYLENE
JJ•
±~ T
I~ 1 •
~ l~rqT."
+
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. :II "r-' .~l.<f' ,
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:~. 400
1±1Iiti
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108
200 300 400 500
~200 -100, o 100
109200 300
.'
400
100
00
500
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400
1100
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r- r ... _
7E ~--::;:-+ • .;,.......~
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ENTHALPY OF ISOBUTENE AND BUTENE-I
~-
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.~. .I-:!.',e:.~_ .... ._~_r::::-::"" . .... "ffi=.::£i.f ,=:,;::::::, :1:=~ .. =.'-'. -
900
800
1000
110
1000
800
-100 o 100
111
200 300 400 500
o700
I
I I ,1'i ,-i' 200
-1- f ' t ::;:II, I
600
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I 'tIT I' ,• I If:.
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I :" . I )1~ . •. ~ ill ; J II
l.
- t I I. - t 1I
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500
600 -ffiEHffi
400
112
o 100
900
200 300113
400 500 600
600
500
400
111300
200
100
a700
!§
500
900
600 'too 800 iiOO]"If{ 9 001000 1100
iJ ,
I
'iH, " , t, I' 'I' ijf1'lt"'",I~ I IX, ',"'!l', ifl",i,j Ill- _ .l t ~ t ii r! • .• l~. Kif.; l':.rt'I1'"!.Jo", • rH :U~.
700 " II t .' '. 1f":Jt If I "" v"" J::IX:.- 1 I ,.' ". t- .. 1". t ~ . t; ni.f ;:-, Ill: .~ I . f~! :- I
• ,It t 'L: .h h!] mt " c:- V/- i },1- till •. ,. Y,:/.'lt I
'4,. '"#~~li~:~;j J'.-"I, 'b'lfat'lH!llI .. ·l·Y9~,', '
:~ ,:<- t I +:!,~.- tJ, it ,
j t
500
±
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400" • II~, '
400
100
, 300
..
Hr· ,1
1 •
:1 . Ii" 1H l-fi1 . I
, ,,l'il ,.
I fl1! j I, mTIl
I r! 1fT) 11
" J f:lf', ,lJ ~ I +
a200
\ J
114
100
t
a
, 'I
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I r I Ij ,
,;Cl&'l' '
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200lillrlw,
300
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115
)
5 0, L
600
+
700rr
=800
~Ll1J900 1000 1100 I 00
~ , .~ ••• - '--rrl -....
j: ...1;1 :::-: :--::rl:z:::.s: '-;': ~.tr'- ........._t-""4-
.~
ENTHALPY OF PETROLEUM FRACTIONS r,;"-~"- ~~ ~IT_" _. __. .~ '''iFf''''.~-;:+.. '\1'--0-'-'" ..,.,...~ ... -. i2 .... ". -.... , ··f- --pi- -t-·-o-J--t,·· 4-0 -I..' '''''.'r--_ _ -0- • •••• • __
~ ..- - _ -_.. .-......... .. ..
, ,
400
~+
300 i
..::t: r' 'T- I"
•T ._ I :::-:-_ :::_.~- .::~~~ -~~
200100
--:1.. :.r"~ - -----r. "cil+= fO--
t.:z= :--' .. r:::::. _
o
T
,...- -r-'
ttL
~ MEAN AV. BOILING POINT 250 of ~"~""
CHARACTERIZATION FACTOR-II.O
,,'
",
r ': I 1:-
...... 1-
T
600
116
117
200
o500
, 300
1100
1100t
• '::1:- _ :.:-..•- .... :.r • -I~ I ,
I ~ ..-
400
~1 t. -:::r: if!"".' i
., IT
.1 tl, ,j ,
, , -4.;T ,I II
,"
1000
300
:
200
900
,·f 1, .
1 .' 1 .'.' 'lfJ ,1 ,
'f,. , , .'
1
ii·;:l
.,
l'
800700
, ,
ENTHALPY OF PETROLEUM FRACTIONS
i
fillI',J n
t j • ;
I
, 11,
. I .' .f> j
l'
500 6 0
500
600
700
•118
o 100
119200 300
I400
400
; lOG 1200
, . :-,J:!. :.;
"
r r ..
, ', ,
:;'.Lft:Il:1ffit!lj300
tlHlfFHH. ,.
PETROLEUM FRACTIONS
MEAN AV. BOILING POINT- 400°F
300 IlIDJmlI
..200
800
900'-
400
600
+
,J!
300 400
100
120
o 100
121
200 300 400o
500
400
300
o5 0
1000900
122
800700600
1IIIEGN!TiH~A~LPYOF PETROLEUM FRACTlONs~~~1111MEAN AV. 80lLlNG POINT-- 500°FCHARACTERIZATION FACTOR -11.0
500
700
,
300
600
400
200~1~.
400
300
_2.00
3002.00100o
, .. ,200
123
400
100
200
12001100
1"
300
1000
200
900800700600500
124
700
300
900
400
200 1ffifHlP"
500
8oolllllll~~ITIlilMEAN AV. BOILING POINT - 600' F
•
500
900
aoo
300
600 700 600
125
900 1100 IZOO
100
800 1000 1100 1200
Iii ENTHALPY OF PETROLEUM FRACTIONS
ill! I MEAN~OILiNG POINT - 800 ofCHARACTERIZATION FACTOR-II.O
I-I
100
o500,400
. ~
" I;t
.... , .~
...;, -$" - 200~
" - '. ., Cl~~ - . ""
300
< 400. ..
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;300
"- . ,
4 -.. ='! •
100 200
126
" .
::t::
o
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700" ..- - - -~ ..
600 ~
~
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,- --~,-.
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400 ,-. ~,~ ..
~ ..-t±:-:'~ :;EPi ~• ::T:_ • !:tt .
500 600 700 800 900 1000 1100 IZOO
127
oCD
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o'"'"
8'"
o<D.,.
o.,.<t.
o'"<t
o~
o<D
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o'"'"
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=
:
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o
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"~
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o 0<D <tlI') lI')
o
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oCDIII
o<DIII
o<tIII
o'"III
128
6 .7 8 9 1.0 1.1 12 1.3 14 15360 .......... , :l:tll
!~: ~ ~ ;. ~ ;;:.. , ;. "':'1": T···· ...... 1;'0'· ;1';.11' ~;;t,I''':Y If '/ ! i' 1.1' t 11 t.,....,... I r,.:.:l] ;n 360.. ~ : 1
:.. : ., .~"1: ~Z.b~. "j' ': . z usn :) I,. )--r--/.- ( .. ,I J;~.:.)r.:·:-:':':':':jr. u:: ).';~J±l;~ 340IJ
320
I .. .. 300..
.~_.~ - ....,. - ... .. , .. .........- 280.... '" ..._.Iil.n; ~:'::~'. 1 ,1' ... , ,•.~.".., ...... , __, 'J/ ,_H, /" .., ,.. _, ... .,-,' " ... ,···----11 260
240::1.":'J~:lnl
;;; 230-.<C
: .... '
'---....... .... 220
210
200
190
180
170-~+"ill. 160.6 .7 .8 .9 1.0 1.1 1.2 1.3 1.4 1.5
7 8 9 10 II 12
440
420
400 IlfIf1TH1- ±i
MOLLIER DIAGRAM
FOR ETHYLENE
130
___~1Lf'l-,
t-; -
•
I 440
420
1400
380
360
340
.86.84.80 .82.76 .78.74.72.70
•••__11340
.66 .68.64.62
290
I280 HffiH+/lI§~~*l'
520
~oo :
480
460
.14 .16 78 .80
. I',- IiI,.84 .86 .88
134
., , ,c
I !i 'I,
, , ,,
" . •. x1: • " •x. ",
JI • - ,, .,.
,
~ ( r, ,, • ,
• .-I ,
~
l. " '" , I
.92 .94 .96
28C
560
340
310
290
350
300
440
540
520
88
llEllE31 330
.86.84.82.80.7876
~._.400~ 380
.74.72.70.68.66
360 li!triffiiRflHl
310
380
340
330
320
.64
300
520
280
290__
440
560
540
400
.62 .64 .66 .66 .70 .72 .74 .76
135.78 .80 .82 .84 .66 .68 .90
.:-_~-~~-~-----~-------------------~
Section 8
DENSITYLow-Boiling Hydrocarbons
The specific gravity of the saturated liquid, from low temperatures to thecritical point, is given on pages 140 to 142 for a number of low-boiling hydrocarbons. A hydrocarbon mixture is assumed to be an ideal solution, and its specificgravity can be calculated by adding the products of the specific gravities of indi- •vidual components times their volume fractions. This assumption is essentiallytrue for members of a homologous series and is a good approximation for mixturescomposed of hydrocarbons £l'om different series as long as no component is in theregion of it-s critical temperature.
Thermal Expansion of Liquid Petroleum Fractions
The thermal expansions of liquid petroleum fractions at pressures up to 1500psig were derived from the thermal expansion and compressibility corrclations ofWatson, Nelson and Murphy.! As in the case of many physical propcrties ofpetroleum fractions, thermal expansion is more sensitive to averagc boiling pointthan it is to gravity, although both independent variables arc necessary to correlate the data properly. Up to 1.25 multiples of the volume at 60°F and 1 atm, itwas found that gravity could be neglected and that the thenpal cxpansion couldbe represented by the molal average boiling point alone. Above this expansion of1.25 volumes, gravity is introduced into the correlation in the form of characteri7,ation factor. For each average boiling point two lines are shown, one correspondingto a characterization factor of 12.0 and the other to 11.0. Interpolation and extrapolation may be made on the basis of characterization factor or, if preferred,gravity, which is also given for each curve.
P-V-T Relations of Hydrocarbon Vapors
A series of charts on pages 148 to 153 give I' ~ PVIRT, the correction factorto be applied to the ideal gas law for hydrocarbon and petroleum vapors. Thecorrection factor is plotted as a function of reduced temperature, TIT" andreduced pressure, PIP" where 7' and P arc the temperature and pressure of thevapor and T c and Pro its critical temperature and pressure. A explained in thescction on Critical Properties, the pseudo-critical, not the true critical, tempcraturc and pressure should always be used for hydrocarbon mixtures. This methodof using the pseudo-critical properties of the entire hydrocarbon mixture is notonly more accurate but more readily used than the application of either Amagat'sLaw or Dalton' Law to the individual components.
10;/ and Cas Jonma/35, 85 (1936).
136
DE"SITY 137
111'V'" = - (y "C""C + y,,,, + y,,,, + ... )
11'
Since there is c\'idcncc of ::omc lr('nel in p- with incr('a~c in molecular \\"eightfor T,. ;> J .00, there are thrC'c Ect~ of charts for the rq:rinn where T,. i~ {.!;I'cntcr than1.0, c-o\"('rinf.!: din'erent r:ln~c~ of ll1ol<.'('u]:lr ""('i,,rla. Bt'!o\\" 1',- = 1.0, Ihe data arcjn~llmcjcnllo take into account n similar trend, so a ~illglc chart 2 covers the entiremolecular \\'eight range.
if olher gases (1-1,,0,,1-1,0, clc.) arc present in a mixlUl'e 01 hydrocarbon
Yapors, an cfTccti\'c Jlrc~surc equal tn 7rV?!IIC E"hould be used to obtain the rcelutedpressure of the h~'drocarbon portion. Likcwi:::e, if it. is ncc(':;:sary to lake int.oaccount ~as Jaw dc\'iations for any of the oth,,1' gn::=c<:, p. should be determined forcarh of thc[o;(' g-ascs at an cO'celi\"(, Jln'.~:'llrc C''ll,lal to the total pressure multipliedby the square root of its muIr frnction. The molal \'oIUine is then calculated byAmilgnr~ Law,
\\-here I'm is the molal \'0Iu1l1e 01 the mixture, lhe subscript He relers lo lhe lolalhydrocarbon fraction, and the subscripts 0, b, et.c., rcfer to other gases. l.:'sua.JlyP-a/ jJ.ln etc., mar be taken as l.OO \\;ith ycry little error, sincc most of these gasesapproximate a perfect ~as at thc efl"ecti\'c pressures encountered. In the absence ofother data, the hydrocarbon charls may be u,ed lor these gases.
Cli It Ih-moleCu It/I h-moleCu It/lh-moleLiters, g-IllolcCu III Ih-moleLiters ~-molc
Cu It I"-mole
Pressure
Lhlsq in. absLb/sq It absALmAlmAtm;\1 m or IlgLb sq rl abs
VAl..UES OF GAS CONST.....~T--R
Temp.
'nOR'HOK0J{
OKOK
GENERAL REFERENCES
n10.7315450.73020.082051.31~
62.3G2781
l1e:l.ttie, IIar/lork :lIlrJ Poffenberger, J. Chem. Phys. 3, 93 (1935).Beattie, Ka.\' and I\:aminsky, J. Am. Chem. Soc. 59, lii~9 (I93i).l1entlie, Rim:lnl and ~u, J. Am. Chem. SQr. 61, 2li (103D).Tnlcl'n:llional Criticnl Tnhl('f:, Vol. lIT.Kay, /11'/. "ng. Chem. 28, IOI~ (1030); 30, ·1,,0 (J03S); 32, 3,;8 (l9~O).
J(cl~o:lnd FC'I!olinl!;. J. Am. Chem. Sn c,. 62/ 3132 (19-10).
L(>\\'i~, Inl/. Htl(l. ('hem. 28, 2.37 (I!l36).S.a~c :md L'l(,cy, Ind. Hllg. Choll. 30, (l7:~ (ID3R).Sal-!C'. Srh:t;lr"ma :,"d Lacey. hid. En9. ('Iu'm. 26. 121S (1!l~-I).
S:l~C, \\'C"h<.;tC'1' :inti Larcy. I nIl. [.,'lIq. r1l,.,.". 29, G;j.". II~S (193i).Smith, I3c:\ttic~nd K3~·. J. Am. Chl"-'. Soc. 59,1:')1;)7 (lfl:li).
;! COpC'. Lewis and Wcber, Ind. P;,IO. Chem. 23, 88i (931).
7.4.
7.0
5.8
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160 170 180 190 200 210
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THERMAL EXPA:N:S~,~o:N~~~1I1I1I1I1I1
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Seclion 9
VISCOSITY
Absolute Viscosity
]n the metric system the unit of viscosity is the poise which is equivalent to B
force of I dyne pcr sq cm shcaring a liquid at the ratc of I cm pcr sec per cm.By reduclion to minimum dimensionality, the poise becomes I g/(cm) (sec). Thecorrcsponding English unit is I Ibl (ft) (sec), or (pouodal) (sec) I (ft) 2, which isequal t.o 14.88 poises.
Howcvcr, the unit of viscosity most commonly used is the centipoisc (0.01poise), which happens t.o be the viscosity of water at almost cxactly 68°F. Thereforc, the absolute viscosity of any fluid in centipoises may bc considered to beoumerically equal to its viscosity relativc to water at 68°F.
Kinematic Viscosity
Since thc density of thc liquid involved in the measurement of viscosity by thestandard industrial viscometers, it is necessary to introduce kinematic viscosity,which is the absolutc viscosity of a fluid divided by its density at the temperatureunder consideration. The metric units of kinematic viscosity corresponding topoises and centipoises arc stokes and ccntistokes, of which the latter is more commonly used. The kinematic viscosity of water is I centistoke at just about 68°F.
Industrial Viscometers
The industrial viscometers which are widely used throughout the petroleumindustry in this country are the Saybolt Thermo for rcfined oils, the SayboltUniversal fur lubricating and gas oils, and the Saybolt Furol for crude residua andheavy fucl oils. The Redwood Standard and Engler viscomctcrs arc used mostlyabroad. Curves for the conversion of these standard viscometer measurementsto kinematic viscosity arc gi\'cn on pages 158 to 160.
Except for the EnglCl' instrument, these conversions arc slightly affected bythe tcmperature at which the viscosity is mcasured, but this effect has beenneglcctcd in thc prescnt convcrsion charts, While Saybolt Universal viscosity may'>e measured at anyone of several temperatures, lOO°F, 130°F, or 2lOoF, themaximum variation between the temperature extremes in the conversion tokinematic "is('o~ily is only 3% and, above kinematic viscosities of 5 crntislokes,it is Icss than 270. The va,'iation between the extremes of the Redwood Standardinstrument (70°F to 200°F) is appreciable at low viscosities but does not exceed3% above 10 centistokes. Saybo!t Thermo viscosity is normally measured at room
155
156 DATA BOOK ON HYDROCARBONS
temperature and Say bolt Furol at 122°F so that it is usually unnecessary toconsider conversions at any other temperatures for thcsc instruments.
Change of Viscosity with Temperature
Viscosity-temperature curvcs arc given for pure hydrocllrbons and crudefractions on pages 161 to 165. In the absence of other data, these curves may beused to approximate viscosity-temperature relations for othcr hydrocarbons andpetroleum fractions if the viscosity is known at only one temperature. However,if the viscosity is known at two or more temperatures, the charts on pages 166and 167 should be used for linear interpolation and extrapolation.
Viscosity Index
Viscosity index is a generally accepted criterion for evaluating lubricating oilswith respect to change of viscosity with temperature. The vi cosity index of anyoil may be read directly from the charts on pages 168 to 172 if its viscositics at100°F and 210°F arc known. If these particular viscosities are not available, butviscosities are known for two other temperatures, the viscosity-temperature chartson pages 166 and 167 may be used to find the values at 100°F and 210°F.
Viscosity Blending
To predict the viscosity of a blend of two or more fractions at any giventemperature, the blending index for each fraction is determincd from its viscosityat this temperature, using the chart on page 173. The blending indexes of theindividual fractions are additive by volume fraction and the resulting sum may beconverted to the viscosity of the mixture by referring to the blending chart again.If the viscosity of one or more of the components is not available at the desiredtemperature, it must be converted.to this temperaturc, since blending indexes arcadditive only at constant temperature.
The viscosity of a blend of two stocks may also be obtained graphically byusing the viscosity-temperature charts. A straight line eonnccting the viscosity ofthe lcss viscous stock on the 0°1" abscissa and the more viscous stock on the 100°Fabscissa reprcsents the locus of the viscosity of all blends of these stocks. Theordinate corresponding to the percentage of the more viscous stock-whcreby thetemperaturcs between 0°1" and 100°F are considcred per~entages-represents theviscosity of the blend. While thc blending indcx chart was derived from theordinate scales of the viscosity-temperature charts, the two methods will differslightly since thc tcmperature divisions vary between 0°1" and 100°F.
Viscosity of Gases
While pressure has very little effect on the viscosity of liquids except nearthe critical temperature, its effect on gases may be considerable, especially abovethe critical pressure. The change in viscosity of a gas or vapor with p1'essurc
,
VISCOSITY 157
may be predicted from the chart on page 177. By the use of reduced temperatureand pressure, this chart provides a generalized correlation of the ratio of \'iscosityat any temperature and pressure to the viscosity at the same temperature andatmospheric pressure.
The viscosity of a mixture of two or more gases at atmospheric pressure maybe computed by the following formula:
N,Z,v'M; + N2Z2VM; + ... + NnZ.VM:Z - -'---'------==----=-'-="'--''------'-----~==_----''
m - N,VM; + N2VM; + ... + N.-vMn
where Z... = the viscosity of the mixtureN" N 2, etc. = the mole fractions or moles of individual components
Z" Z2, etc. = the viscosities of the individual componentsM
"M2, etc. = the molecular weights of the iudividual components
The chart for change in viscosity with pressure may be applied to mixtures byusing the pseudo-critical properties of the mixture to determine reduccd temperature and pressure.
GENERAL REFERENCES
ASTM Standard Viscosity-Temperature Chart. for Liquid Petroleum Products (D341-39),Charts C and D.
Deale, "The Science of Petroleum," Vol. II, 1080, Oxrord University Press, New York,N.Y. (1938).
Comings and Egly, h,d. Eng. Che11l. 32, 714 (1940).Davis, Lapeyrouse and Dean, Oil Gas J. 30, No. 46, 92 (1932).Dean and Davis, Chem & Met. Eng. 36, 618 (1929).Edwards and Bonilla, !rId. Eng. Chem. 36, 1038 (1944).Etherington, Sc. D. Thesis, Mass. Inst. Tech. (1948).Evans, J. Insl. Pelroleum Tech. 24, 321 (1938).Forlch and Wilson, Ind. Eng. Chen!. 16, 789 (1924).I••ne nnd Dean, Ind. Eng. Chon. 16, 905 (1924).Lipkin, Duvi!'on and }(urtz, Ind. Eng. Chern. 34. 976 (19·12).Nat. Bur. Standards Circular CI,61 (1947).~age llnd Lacey, Ind. Bng. Chtm. 30, 829 (193 ).~llge, Yale and I.,cey, l1ul. Bng. Chem. 31, 223 (1939).Watson, Wiell and i\furphy, Ind. EnO. Chem. 28, 605 (1936).
CONVERSION TO
KINEMATIC VISCOSITY
600 800 1000101000
800
600
500
400
60
50
40
20
10 _
8 ~
6
5
4
-F_'':':
20
I
400
60 80 100
I600 800 1000
15!3
2000
300 400
,h 'i1 ~; 1!lIT"!Hl·~
4000
k':: ~#l :::., ....
I::: :~. il~! :il~·J.".i , •.• I·'
800
600
500
400
300
200
100
2000
1000
800
" 600- 500
400..
300
30
60
50
40
200
300
600
500
400
20
100
80
1000
800
60 80 10030 4020
10
8
6:r;
5
4
3
>
2
600 800 1000
4 G 8 1032
10
8.
6
~
4
3
t!
2 "
200
1000 - ::: cf
100 20010000 f,i -i.Jk.ti .q
8000 -=tot
6000
=11111
159
700
, .
600300
FROM SAYBOLT THERMO VISCOSITY
200
SAYBOLT THERMO VISCOSITY
-lOX (SAYBOLT THERMO TIME)
100
2
4
o
160
VISCOSITY OF NORMAL PARAFFINS
.1-100 o 100
161
200 300 400.I
1.8
11.6
1.4+-
I -: •
. ~±:=T._.
. -.. , ...,.._ _ -_r:r::
-VISCOSITY OF AROMATICS -
12::!..,
H·I-f
r ' -r+--r-'.-i- .-;...... -;- - ++-
- - -=1= - I'-L-., r
I
.-i--- ~..
± L..j _ ,. -- - ,.
- .
-
..,...
- -I
. --j - I
I lJiIllI I
.
0.20 50 100 150 200 250 300
162
- -ri
- I rt:'
,5:
KEYI 26,8' API RESIDUUM
2 33.2' API 527-572·F. AT 40"...3 35.0··API 482-527·F. AT 40M",4 36.~·API 437"462" AT 40"".5 38,2'API 392-437'F AT 40"M.6 39.2·API UP TO 39rF.AT 40""-7 43.~·API 482 - 527·F.8 46.0'API 437 -482·F.9 48,7'API 392 -437·F.
10 -i:!...:?!= r.l- 'i_: :;.'-=:'-~:... ;<ic --=.t:-~ 10 51.soAPI 347-392°F.
80_. ~~ t ~ti ~~~£~~ .~ .~ : ~ ~:..~:::~ ~~~=;~;:~7.0 _0 __ e\'=~ •;~:il'ii ft 4' ; :1.si?=a" 13 62.9·API 212 - 257°F.
6.01~i=LGl,{: -.M cFI..i.~:',r ;L,- lc l'!'=!o\2, ::EJ=L-" NOTE- 801LING POINTS OBTAINED IN A
I-W::-;:;\ :jeil- _til 1-. \1 .,='1: -~l-+" = HEMPEL COLUMN.T:~ ,---+-+ - .-~-t-t \.tr--l=
40
0.1 'i', .100
_' "-+i-L-i-tREFERENCE: LANE AND DEAN. IND. ENG. CHEM. 16. 905 (1924)
1+!r~r~I'
200 300 400 500 600 700
163
80 .•-;~ ... =.=t=<="70
60
50
VISCOSITY OF
MID CONTINENT OILS•
40
30.~
20
~ .... =~---
do'
KEYI l4~ 0 API RESIDUUM2 ~3. °API CYLINDER STOCK3 23.l oAPI HEAVY MOTOR OIL4 (lO5 SPGR) ROAO orL5 24.2°API RED OIL6 26.l oAPI LIGHT MOTOR O~.7 27.1 °API LIGHT PARAFFIN OIL8 32.8~PI WHITE OIL9 28.8°API LIGHT PARAFFIN OIL
10 3D.OoAPI PRESSED DiSTILLATEII 35.2°API CRUDE otL12 35.6°API MINERAL SEAL13 40.4°API KEROSENEI~ GASOLINE15 GASOLINE
L •4
• -,.,<i=-
3
2
I,~ _~c_o _ .•09,_- ... 5§". .. = .=
0.4
0.3 :.._-0-2
300200
REFERENCE, FORTCH AND WILSON. IND .. ENG. OlEM. 16. 789 (1924).
I II II II I II I I II II
400 500 600 7'00100
164
wo~ c
90 ~~...:-- __T";.
8070 - VISCOSITY OF CALIFORNIA60
50CRUDE FRACTIONS
40
30~
KEY20 I 18.7 'API 527-572'F. AT 40 MM.
2 20.3 'API 482 - 527'F. AT 40 MM., 3 22.8 'API 437- 482'F. AT 40 MM.
4 25.0 'API 392-437'F. AT 40 MM.
5 27.3 -API UP TO 392'F. AT 40 MM.
106 30.4 'API 482-527'F.7 33.0 'API 437-482'F.
8 8 38.2 'API 392 -437'F.
7 9 41.5 -API 347- 392'F.
610 44.3 'API 302- 347'F.II 49.5 'API 257-302'F.
5 12 54.5 'API 212 -257'F.
4 NOTE- BOILING POINTS OBTAINEDIN A HEMPEL COLUMN
3
2
REFERENCE: LANE AND DEAN. IND. ENG, CHEM. 16. 905 (1924)
0.1100 200 300 400 500 600 700
165
0010-:fl eo6.05.0
4.0
700600500
VISCOSITY - TEMPERATURE CHARTHYDROCARBONS AND PETROLEUM FRACTIONS
KINEMATIC VISCOSITY. LOW RANGE
30 I I I I I I I I I I I I I I I II I I I II III II1II II i III1II1 \1IIII11 i 111I1 11111 11I11 11111 11111 II!! 111111111111111111111111111 II I 11 III ITTTRRTlI I I I I I I I I i I m 3.0
20 I I I ! I I I I I I ! I ! ! I I I I I I II II ! ! I ! ! I ! I ! I I ! I I " i I II !III " III !! III 1!1111111 ! I I!I!!!!111111 111 !111 1!III!! I!!I!III !II I I I I I I ! ! I I I I ! ! I ! ! ! I I ! I I ! Ii! ! ! 12.0
1.501 I I ! ! I I I I ! ! I ! I I I I I I I I ! I I II I: II;! I : I ; ; I : 111!!11 ; 111111111: il! 1111111111: 111111111 illil I: illllIillliil iIi II I UE±lJ:±J±l1I££U Li LOll Llu i 1,50
1.00
0.90
0.80- 0.70~~~ 0.70
0.60~· '060I .
():j:;:
o.sOt~ J" I ! ! .0.50Zis;2i
0.40 ! ! ! ! ! 0.40~
0.30 I I I I I I I I I I I I i I I I I I I I II I I I II I I I i I : 1111 i II ; 1111 !l111 i 1111 ;11111111111111111111111111111111111111111 i 111111 i II I I I i I I I I 1I I i I I I I I i I I I I I I I I I I I 10.30
0.20 o o'"
oN
R~FERENCES: A.S.tM. STANDARD VISCOSITY - TEMPERATURE CHARTS 0341-39
NAT. BUR. STD5. CIRCULAR C 461 (1947)
WATSON, WIEN AND MURPHY, IND. ENG. tHEM. 28,605(1936)
"'MM I , ! , ! , ! :bx,,1 I I ! I I I J,M J ! ! ! ! ! JsMO.20
~
8 0
......... 199 1~9. 200N ,2~q"" ~ ~ 400 450 500 600 700 800'i' I,.
10,000,000 ..~VISCOSITY - TEMPERATURE CHART
1,000,000 HYDROCARBONS AND PETROLEUM FRACTIONS500,000
KINEMATIC VISCOSITY, HIGH RANGE200.000100,000 10C\OOO50,000
,50,000
20,000 20.00010,000 10,0005,000 5,000
2,000 - 2,000
1,000 (/) 1,000
500 ~ '""'h- 500~~4 ! , kb! , W'2ffi E' bt!-bikffi.::tt!"ttJ:tl'!ifl L141l114lWJtUifflfi±ltlitfilll!ifl J IIJ I !J btl ! I I I ! I I
I ! I! ! Ifu:'1200
zw<.)
I>-- 50~§0>...(/)
:><.)
201::~ I 1I I I II I I 1111111111 ! I: III! ! III! : I IIIIIIIIIII!! 11111' 11111 11111 11111 11111 III:! III I! 1111"IIIIIIIIIIIII!:1 ! ! I I I II I I I I I II! I I 1II I ! ! IJIIEJ 20::;;wzi:
10 10
8.0 8.0
60 6.0
5.0,
5.0
4.0 , , 4.0
• , , I REFERENCES: A.S. TM. STANDARD VI$CO$ITY- TEMPERATURE CHARTS 0341·393.03.01 1I 1I 11I I I I I I I I I I I I I I I I II 1111I11 , 111111111 , " IIIIIIIIIIII! 11111111111111111 NAT. BUR, STOS. CIRCULAR C 461 f'947)
WATSON. WIEN AND MURPHY, IND. ENG. CHEM. 28,605 (193G), , , ' , ,,TEMPERATUflE.~ .·.F. ,
2.0
,34
33 VISCOSITY INDEX ALIGNMENT CHART 140
32 2.0 TO 50 CENTISTOKES AT 210°F.
31 130
30
29 120
28
I"~27 110
26
25-"S 100
24
23 90
22u: )(0 w0 0
21Q ~ 80...
'" >-<tt:20 °Q l/ll/l0W C\J
19 '" <:> 700 ... l/l... q>18 !Q
§.-2:
17 wf2 60<:>
16 ;g$
15 050
14
13 40
12
II 30
10
9 20
B
7 10
6
5 0
168
~50440
430 -
420
410
400
390
380
370
360
350
340
330
320
310 "'300 ~290 ~
280 '"0z270 8
w260 '">-250 ..J
0
'"240 >-<l
230 '"220 -
210
200
190
180
170
160
150
140
130
120
110
100
90
VISCOSITY INDEX ALIGNMENT CHART40 TO 60 SAY80LT SECONDS AT 210"F.
6059
585;>
5655
s.,5,3
5f!
1G9
140
130
120
110
100
90
>< 80w0;;
>- 70>-iii8!!!
60>
50
40
30
20
10
0
20
40
o
30
10
100
110
120
130
140
90
!<.'° x~ w
C\i 0 80.... ~
'",,'" >-f--
t in0 70tJ:; <>
'"<fl:>....
(j' 60~
cJ
50
VISCOSITY INDEX ALIGNMENT CHART50 TO 120 SAY80LT SECONDS AT 210°F.
1650
1600
1550
1500
1450
1400
1350
1300
1250
1200
1150
1100u:
1050 °00
1000 f--<t
950 - Vl0z
900 0<>UI
850Vl
~800 0
m>-
750 <tVl
700
650
600
550
500
450
400
350
300
250
200
150 1.
170
3800
3700
3600
3500
3400t
::13100 -
3000+t
1900+
2800:1-t
2700tu:
2600 i "2500!
0Q
24COt~
'", 0T z
2300+ 0
"2200t
""'"2100 f :;
0al
T >-2000 <l
'"1900
1800
1700
1600 IT
1500+,1400+
+1300+
t1200+
+1100+
1000:1-
900t
800 1
VISCOSITY INDEX ALIGNMENT CHART80 TO 200 SAY80LT SECONDS AT 210"F.
171
130
120
110
100
90
80x""0:;;
>- 70!:::
'"0"'":; 60
50
40
30
20
10
0
7800 T
7600
1400
7200
1000
6800
6600
6400
6200
6000
5800
5600 u;
°5400 ~5200 ~
<f)
5000 0z0<.)
4800 w<Il
4600 ~
4400 16>-..<f)
4200
4000
3800
3600
3400
3200
3000
2800
2600
2400
2200
2000
1800
VISCOSITY INDEX ALIGNMENT CHART100 TO 350 SAYBOLT SECONDS AT 210°F.
172
130
120
20
10
o
I
200 300 400 500
~
35
30
25
20
15
10
10 20
0.2 0.3 0,4 0.5 2.0
2000 5000
80
60
40
10000
600400200o
.030 .030
.028 .028
.026 .026
.024 .024
.022 .022
.020 .020
.018 .018
.016 .016
.014 .014
;,
.012 ;+ .012~
.010 .010
.008 .008
.006 .006
.004 .004
.002 .002
174
100
80
~IIII-!!IIII20
10
.BEALE. THE SCIENCE OF PETROLEUM. VOL. 11. P.PRESS (1938)
. OXFORD UNIVERSITY
0.1 Io 100 200
175
300I
400 500
1200
.040
..038
.0.36
.034
.032
.030
.026
.026
024
.022
.020
•.018.,
" .016
.0/4
012
,
.010
1000
~ I.,l' fr ~ f
.0091+
it iJ. . ;:j~ ~r • •.006
800 1000 1200
800
600
600400200mtmm
200o
o
ABSOLUTE VISCOSITY OF
.014
.038
.040
.024
.018
.020
.026
.012
.034.
.032
.030 .•
.006
.008
TEMPERATURE - 0 F
176
7.0
4.0
3.0
6.0
2.0
10
9.0
8.0
1.5
1.05.0 6.0 7.0 80 9.0 104.0
4.0
3.0
3.0
2.01.5
1.5 H;tt+tttf+
H,,
"
11'i],11
1.0 T 11
.2 .3 .4 .5 .6 .7 .8 .9 1.0
.2 .3 .4 .5 .6 .7 .8 .9 1.010
9.0
8.0 ~~.,~,E~E~,£,~~~~,~,~~,IN.~~. ,.6:~"~, ,~~,;~~,~~~",r' "" "'~
7.0
6.0I :: i I I i i i I II II ! I i
VISCOSITY OF GASES AT HIGH PRESSURES
4.0
2.0
..,-.J 3.0
Section 10
COMBUSTION
Liquid Fuels
The heats of combustion of fuel oils and petroleum fractions are expressed asa funcLion of gravity by the chart on page 180. Both the high and low heatingvalues have becn correcLed for the average impurities other than water whichare usually prcsent in oils of various gravities. These average impurities, tabulatedon the chart, are fairly represcntative, although there may be appreciablc deviations for a given stock. In general, the heating valucs of average fuel oils arcwithin 1'i& of the curves.
The heat available from the combustion at 60°F of liquid fuels is given onpagcs 186 to 188 for fuel oils of 5°, 10° and 15°API. Because of the small variation betwecn these charts, interpolation is unnecessary and the available heat atany tempcrature and percent excess air may be read from the chart which mostnearly corresponds to the gravity of the fuel oil. If the impurities are known tobe appreciably difTerent from the average values tabulated on page 180, theavailable heat may be corrected in direct proportion to the bydrocarbon portion ofthe fuel with sulfur considercd as inert material.
Gaseous Fuels
Heats of combustion of paraffin and olefin gases arc given as a function ofmolecular weight by the chart on page 181. The paraffin curves on this chart wereused as a basis for deriving the charts on pages 184 and 185 for the heat availablefrom the combustion at 60°F of dry refinery gases having high heating valuesof 1000 and 1600 BTU/S.C.F. Allo\\·ance was made for average impurities of2.570 H 2 S and 2.5% inerts (equal parts CO2 and air) by volume. As in the case ofliquid fuels, the chart more nearly corresponding to the high heating value of thefuel gas may be used without interpolation with very little error. However, in correcting for variation in impurities, the available heat must be adj usted in proportionto the weight pm·cenlage of the hydrocarbon portion of the fuel gas. In makingan adjustment for thc H 2 S content of thc gas, its volume percent may be distributed equally between the inerts and hydrocarbon portion as a good approximation. The following table gives relevant information for refinery fuel gases of9.verage impurities:
\78
COMI3 S no"
Nominal HHV, BTU/S.C.F.-, .. _.•.... 1000 1200Wt. Percent Impurillc~... ~. 10.1 8.3~p G, of Fucl Gas ('-or - 1.0'-. 0.60 0.73M.W. of H)'drocarbon Poruon. 16.5 20.4Actual HHV of He Purthm-U rU/ti.C.F. ' 1037 1248
I Calcubtcu by the perfcct gas hw at GOoF and J atm.
14007.10.8624.31458
16006.2a.utl28.21609
1SOO5.41.1232.11879
179
20004.001.2b36.12090
Properties of Flue Gas
The CO2 content of flue gas and the lI'eight ratio of flue gas to fuel aregiven both for liquid and gaseous fuels as a function of excess air on pages 189<1nd 190. Since the effect of percent excess of air is almost imperceptible on theviscosity and thermal cunduetiyity uf flue gas, it has been ncglected entirely andeach of these properties is expressed as a function of temperature alone.
;e. ,.-
it ~
tit~~' Jif-...
- i.!,~
HEAT OF COMBUSTION OF FUEL OILS
AND PETROLEUM FRACTIONS
20000
19500
19000
* ,f'H-
.. ~":4_(,,!It. :::: :;t;:t!1 ".
IMPURITIES IN AVERAGE FUELS . ""A.P.I. I % S %INERTSI'M~Y,m'tVRESIDUAL FUEL OILS AND CRUDES
o 2.95 1.15 4.105 2.35 100 3.35
10 I. 80 .95 2.7515 I. 35 .85 2.2020 1.00 .75 1.75
CRUDE OILS25 .70 .70 1.4030 .40 .65 1.1035 .30 .60 .90.
• ~ ......:...1-_ 1;-- ~ .. ~
.~ .~ ... -+--- ...:=+--~E-f, ~t
,
.,
- I
, .~ .,~.
..
fD ..18500 [I
+~.
~ :~11
+.il
r
~X·· -tE':-::~ \1:-T.r~."""· .,
•
18000
17500
17000
TI::;
~, '.,., .....
THESE VALUES REPRESENT AN AVERAGE 19OF CRACKED AND VIRGIN FUEL OIL DATAUP TO 20"API,AND THE CORRELATIONALLOWS FOR AVERAGE SULFUR AND INERTS(EXCLUDING WATER) FOUND IN AVERAGEFUELS. ABOVE 40"API THE CORRECTIONFOR IMPURITIES IS NEGLIGIBLE AND THECURVES REPRESENT PURE PETROLEUM
4- LIQUIDS.
, .
o 10 20 30180
40 50 60
4600
4409
4200
4000
341001.3200
2800
2600
2400
2200
2000
1800
1200
1000
10
181
900
800
700
600
500
,~.
+
ENTHALPY OFFLUE GAS COMPONENTS
0-1 ATM. B"· -<-.!.
~. Ii ;'If!- ~ ~ _:.:. -:t t
o200 400 600 800
1821000 1200 1400
2200
2000
1800
1600
1400 .
1000
600
400
200 .1600 1800 2000 2200
1832400 2600 2800 3000
HEAT AVAILABLE FROM THECOMBUSTION OF REFINERY GAS
r. :..
- j .~ •~. .
,
1000 B.T.U.I CF (60· F)
. ,:}:-
"j n r
1000
2000
3000
zoo 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000
184
14
400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000
186
..
==I .,~. .,..,
I ~= .
,. ,k
" . ;t ,
~
.~
~ ,
THE COMBUSTION OF50 API FUEL OIL
1
, -
r- ..:
. -r-r-- -
.,... ;
"'"tt -trt! ~
1- ,tl~. ,
.;in ,;
8000
9000
7000
Ii'!.
4000.,"
!.3000 ••
2000
1000
6000~~ ., ~ ~: ..... -+-l.';. _ .,...
.m:-. .::z::::5000 ; .. ,
l- • ••t:[ .....t
15000
12000
200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000
186
1200 1400 1600 1800 2000 2200 2400 2600 2800 3000800 1000600
+
200 400
4000
9000~
., - =-,~
9000~
~, -
7000 ---~.
6000 ,
H3000__
17000
J87
1000
200 400 600 800 1000 1200 1400 1600
188
16
15
1411113~
12~
"101111 ~
:» 9
'"8
7 rJiJf 'I I· TI'li:r
6
5~~q;;$~;;:!fl!;:m;=;;'I;jj~
4
3__
- 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400
o<t
oto
oNN
8
o<D
o<t
oN
8<t
gN
o~
o<D
'"
oN
'"
oill
o1li
gN
o"'"
ooo
No
"o'"
o...
t
I.Im
II MlW-
,
, , ,, -
t+
.j:
~a:.•$ I,,- ,
.' - ,t ,. ti 't
,j ....
~.t"· . , .'M1Iit !. f,. - ,
a: 1- 11
~<l
II r>(/) .. .~'7: (/) : :I41w w " T '1
I1
r: ::> 0 ~. 81 +, it ~ , .
W ,. , ,:~ u;
n!: "" I- :. ilL0 zIIi!
wp~
,(/) 0
",
. J "~; ; 0 a: , II - I
I i t~
~W r;
I J: 0-0
/ffil. ., I
~I0- .J
1 I . -
I' jI
, . I, f I I I i., , ! t
I I ", .1
~~ mf: S , ,!! I : , il! i , 1fIt\;,1
190
--_._--
191
<tq
~0
~(!)
IJJ::J..JLL.
LL. §0
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Section 11
FLOW OF FLUIDS
Friction Factor
The friction factor for turbulent flow of all fluids (liquids and vapors) isexpressed as a function of a modified Reynolds number (DUS/Z) by the chart onpage 198 for both commercial pipes and smooth tubes. In the unstable flow regionbetween values of DUS/Z of 0.135 and 0.390 (or approximately 1000 and 3000in consistent units for DUp/p.) the turbulent flow curves have been extended tothe stable streamline flow region. These extrapolated curves for turbulent flowgive maximum values of the friction factor in the unstable region and arerepresentative of the flow usually found in commercial pipes. For streamline flowthe pressure drop may be computed directly from either of the formulas given onthe chart, since the friction factor is incorporated in these formulas.
Pressure Drop in Commercial Pipes
To facilitate the determination of pressure drop for liquids in commercialpipe" the charts on pages 199 to 201 were derived from the friction factor curveand the formula for turbulent flow. The following example illustrates the application of these charts:
Exampte I. Determine the pressure drop for 21,800 gnl/hr of gasoline f1owin~
through 800 ft of standard 6-in. pipe. The kinematic viscosity of the gasoline is0.60 cs and its specific gravity is 0.750 at 100°F, which is the average temperatureof the gasoline in the pipe.
21,800 .Q/D = 6.065 = 3600 gal/hr/m.
By following the dotted lines on the chart on page 200 as indicated forQ/D ~ 3600 gal/hr/in. to a kinematic viscosity of 0.60 cs, then over to the insidepipe diameter of 6.065 in., the value of AP/S ~ .38Ib/sq in. per 100 ft.
The pressure drop for 800 ft of pipe will be:
t:.P = 0.38 X 0.750 X ~: = 2.3 Ib/sq in.
Equivalent Lengths of Fittings
Data on the frictional resistance of fittings are usually correlated by theequation Ah ~ Ku2/2g,·where K is a constant for each type of fitting. However,
193
194 DATA BOOK ON HYDROCARBONS
•
in problems of fluid flow it is more conycnicnt to express thesc resistanccs asequivalent lengths of straight pipe for use in thc gcneral friction factor equation.Since the latter is a function of Reynolds numbcr "'hile J( i" an independcntconstant, it is nccessary to corrcct the equivalent lengths for variation in Reynoldsnumber in inverse proportion to the friction factor. In the table on page 202 theequivalent lengths correspond to a Reynolds number of 10 and, for appreciablydifferent values of the latter, should be multiplied by the correction factor onpage 203.
Example (Liquid Flow). Kerosene at lOO°F is being pumpcd at a ratc of18,000 gal/hI' (gal/hr at 60°F) through 500 ft of standard steel 4 in. pipe inwhich there are eight standard elbows, one tee (side out) and two gate valves.Calculate the pressure drop through this line using the friction factor curve for the1I0w through the pipe and the "K" factors for the fittings; check the result usingthe pressure drop charts and equivalent lengths for the fittings. The kerosene hasan absolute viscosity of 1.5 cp at lOO°F, a specific gravity of 0.825 at 60°F, and avolumc cxpansion ratio of 1.025 at lOO°F relative to 60°F.
Q = 18,000 X 1.025 = 18,500 glll/hr at lOO°F
U - 0.00680 X 18,500 - 78 f I- (.1.026)2 -. t sec
,.. 0.825SpeCific GravIty at lOO°F = -- = 0.805
1.025
DUS 4.026 X 7.8 X 0.805----z- = 1.5 = 168; f = 0.0052
P (. ) _ 0.323 X 0.0052 X 0.805(7.8)2 X 500 _ 0 lbl .ti pipe - 4.026 - 1.2 sq Ill.
fi. (7.8)2 X 0.805
tiP (lttlllgS) = (8 X 0.45 + 1 X 0.90 + 2 X 0.19) 148.2
4.88 X (7.8)2 X 0.805 Ib/'= . = 1.6 sq Ill.148.2
Total pressure drop = 10.2 + 1.6 = 11.8 lblsq in.
Check
Uncorrected equiv. length of fittings = 8 X 6.6 + 13.2 + 2 X 2.8 = 71.6 ft
Correction factor (D~S= 16.8) = 1.1
Corrected equiv. lcngth of fittings = 1.1 X 71.6 = 79 ft
FLOW OF FLUIDS 195
Total equiv. length = 500 + 79 = 579 ft
Q 18,500 Z 1.5D = .1.026 = 4600; S = 0.805 = 1.9
tJ,: = 2.5 lb/tiq in./lOO ft
Total pressure drop = 2.5 X 0.805 X ~~~ = 11.7lb/sq in.
Example (Vapor Flow). Propane vapor at 90°F and an upstream pressureof 20 psig is flowing through 800 ft of 6 in. standard steel pipe at a rate of 25,000Ib/hr. Determine the pressure drop through this line assuming the ideal gas lawapplies to propane under these conditions. At 90°F the viscosity of propane vaporis 0.0095 cpo
Thc following cquation for isothermal flow of ideal gases and vapors can bederivcd by applying Bernoulli's theorcm to a diffcrential length of pipe and integrating thc rcsulting cquation between the limits, 0 and L:
JgI?T(P,' - 1'22)
U1
= [/L I' J2MP,2 - + In-'2m P 2
where U 1 = upstream velocity in ft/sec
PI = upstream pre ure in )b/sq ft abs
P 2 = downstream pressure in Ib/sq ft abs
T = absolute temperatme-OF + 460
L = Icngth of pipe in ft
m = hydraulic radius in ft = d/4 for pipes
I = friction factor
9 = gravitatioual constant = 32.2 ft/sec/sec
R = ideal gas law constant = 1545M = molecular weight
By substitution flnd rearrangement the abovc equation can be converted to amodified form of the equation for liquids, or
tJ,P = P - P = 21'\ [0.323 (If, + In P I /P2) S U 'J
I 2 PI + 1'2 D 24 . 1 I
where PI, P 2 = upstream and downstream pressures in Ib/sq in. abs
S 'fi . fl' I, 000 0 M1' II = speci c gravity 0 vapor re atlve 0 water = . 15 T
D = pipe diameter in inches
196 DATA BOOK ON HYDROCARBONS
•
Trial and error must be used in the solution of the above equation since P2 isunknown. The friction factor, I, is independent of the variation of pressure sincethe mass velocity term, US, in the Reynolds number remains constant, U varyinginversely and S directly with the pressure.
D = 6.065 in.
S = 0.00150 X 44 X (20 + 14.7) = 0.0041690 + 460
Density = 0.00416 X 62.4 = 0.259 Ib/cu ft
U - 25,000 X 144 X 4 _ 134 ft/sec, - 0.259 X 3600 X..- (6.065)2 -
DU,S, 6.065 X 134 X 0.00416Z = 0.0095 = 355; f = 0.0031
For the first trial assume P 2 = P,
P0.323 X 0.0031 X 800 X 0.00416(134)2 9 lb/ .
Ii = = 9. sq tn.6.065
For the second trial assume P2 = 24 Ib sq in.
liP = 2 X 34.7 [0.323 X (0.0031 X 800 + 0.37) X 0.00416 X (134)2]34.7 + 24 6.065 24
= 1.18[0.323 X-(0.409 + 0.015) X 74.5J = 12.1 lb/sq in.
A third trial would give a liP of 11?,4 lb/sq in.
In this example neither the initial velocity nor a contraction loss from alarger vcssel into the line was taken into account. If thc propane vapor wcrc flowing from a drum into the 6 in. line, it would be necessary to calculate an initialpressure drop as follows assuming isothermal flow:
RT In P /P = U,2 0.5U,2M 01 2g+2g
The first term on the right-hand side is the velocity head, and the second termis the actual contraction loss due to friction.
If the available head in the drum, Po, is 34.7 psia, PI is determined by trialand error and for the first trial U, is assumed to be 134 ft/sec.
1.5M 2 -6 2In Po/P, = 2RTg U, = 1.2 X 10 U,
In PO/PI = 1.2 X 10-6(134)" = 0.0216
PO/PI = 1.022PI = 34.0 psia
FLOW OF FLUIDS 197
Since the differential is so small, 0.7 lb/sq in., a second trial is unnecessary.If this loss had been considered at the beginning of the example, the latter wouldthen have been based on an upstream pressure of 34.0 instead of 34.7 psia.
GENERAL REFERENCES
Beij, J. Research Nat. Bur Standards 21, 1 (1938).Chilton and Colburn, Ind. Eng. Chern. 26, 1183 (1934).Crane Company, "Flow 01 Fluids Through Valves, Fittings, and Pipe" (1942).Drew and Genereaux, Trans. Am. Inst. Chern. Eng. 32, 17 (1936).Foster, Trans. Am. Soc. Mech. Engrs. 42, 647 (1920).Gourley, Proc. Inst. Civil Eng., p. 297 (1910, Part 2).Karl' and Schultz, J. Am. Soc. Naval Engrs. 52, 239 (1940).Schader and Vanderlip, Cornell Univ. Eng. Exp. Sla. Bull. No. 130 (1935).Walker, Lewis, McAdams and Gilliland, "Principles 01 Chemical Engineering," pp. 71,
87-89, McGraw-Hill Book Co., New York, N.Y. (1937).
003
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Ll.P'.323f SU2L-0-
'1.495 XIO'5fSQ2L05
~2.15 XIO'7r W2LSDS
Ll.p, 6.68 X 10'4 ZUL"[5Z
~4.55 XIO'6ZQLD4
WHERELl.P ~ PRESSURE DROP IN LBS.lSQ.IN.
0' PIPE DIAMETER IN INCHES
U ' LINEAR VELOCITY IN FT.lSEC.Z ~ ABSPLUTE VISCOSITY IN CENTIPQISESS ~ SPECIFIC GRAVITY RELATIVE TO WATER
L ~ LENGTH OF PIPE IN FEETQ~ QUANTITY OF FLUID IN GAL.lHR.W' WEIGHT OF FLUID IN LBS.lHR.U ~. 006BO Q /02
~.000816 W/SD2
PRESSURE DROP
STREAMLINE FLOW
II,1'1 _. ~' .. •
.,' Il'
H
FRICTION FACTORFOR FLUID FLOW~ IN CIRCULAR PIPES
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DROP IN COMMERCIAL PIPESTURBULENT FLOW
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-C>P'PRESSURE DROP IN LBS./SQ.IN./IOOFT.D' ACTUAL INSIDE DIAMETER IN INCHESQ' QUANTITY OF FLUID IN GAL.lHR.
Z' ABSOLUTE VISCOSITY IN CENTIPOISESS' SPECIFIC GRAVITY
Z/& KINEMATiC VISCOSITY IN CENTISTOKES
STREAMLINE FLOW
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ZIS- KINEMATIC VISCOSITY IN CENTISTOKES
STREAMLINE FLOW
.:I.P'4.55 X 10-4 ZQ
04
. , .. " ., ,," .PRESSURE DROP IN COMMERCIAL PIPES
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Z!S'KINEMATIC VISCOSITY IN CENTiSTOKES
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EQUIVALENT LENGTHS OF FITTINGS
Pipe size - Incbes Equivalent Lengths' - Feet
1.D. Vah'es Elbows Dends TeesNominal
Inside 0.0. Stand- Extra Stanrl- Long 00' 45°Close Side End
Run ofDiam. Globe! Galc Angle Return Stand-
ard Strong ard· Sweep RID = 6 = 1.5 = 1 Out Out ard-- -- ----Kt 10 .W 3 .45 .30 .25 .21 .75 .no 1.3 .30
~ 0.540 0.364 0.302 13.3 0.3 4.0 0.6 0.4 03 0.3 1.0 1.2 1.7 0.4)1 0.8·10 0.622 0.516 23. 0.4 6.8 1.0 07 0.6 0.5 1.7 2.0 3.0 0.7% 1.050 0.821 0.742 30. 0.6 n.o 1.3 o.n 0.7 0.6 2.3 2.7 3.9 0.9
1 1.315 1.04n 0.n57 38. 0.7 II .5 1.7 1.1 1.0 0.8 3.9 3.4 5.0 1.1
1)1 1 !l00 1.610 1.500 59. 1.1 17.6 2.6 1.8 1.5 1.2 4.4 5.3 7.7 1.82 2 375 2.067 1. 93!) 75. 1.4 23. 3.4 2.3 1.9 1.6 5.7 6.8 9.8 2.33 3.500 3.068 2.!l00 ll2. 2.1 34. 5.0 3 ..4 2.8 2.4 8.4 10.1 14.6 3.44 4.500 4.026 3.826 147. 2.8 44. 6.6 4.4 3.7 3.1 11.1 13.2 19.1 4.4
6 6 62.5 6.065 5.761 220. 4.2 66. 10.0 6.6 5.5 4.7 16.6 1!l.9 29. 6.68 8 625 7.981 7.625 290. 5.5 S7. 13.1 8.7 7.3 6.1 22. 26. 38. 8.7
10 10.75 10.020 9.750 360. 7.0 llO. 16.5 11.0 9.1 7.7 27. 33. 48. 11.012 12.75 12.000 II. 750 440. 8.3 131. 19.7 13.1 10.9 9.2 33. 40. 57. 13.1
14 14.00 13.25 - 480. 9.2 145. 22. 14.5 12.0 10.2 3(; . 44. 63. 14.516 16.00 15.25 - 560. 10.6 167. 25. 16.7 13.n 11.7 42. 50. 72. 16.7lS 18.00 17.18 - 630. 11.9 188. 28. 18.S 15.6 13.2 47. 56. 82. 18.820 20.00 19.18 - 700. 13.3 210. 32. 21. 17.5 11.7 53. 63. 91. 21.
• The equivalent lengths tabulated correspond to a value of D~S = 10.
on the opposi te page.XC;, S KC;'S
pP=-X- =--2q 2.31 148.2
: For swing che('k valve, usc ~~ or globe valve equivalent lengths.
J)[''iFor other values of - Z:"" , apply correction factor from the chart
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LOSS DUE TO ENLARGEMENT
F (U,-U2)2E· 64.3
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204
.5.4
:.T'/-:±±: .
FRICTION LOSS DUE TO SUDDEN
CONTRACTION AND ENLARGEMENTTURBULENT FLOW IN PIPES
- .~.~- i-'. .
A2' DOWNSTREAM AREAF • FRICTION LOSS, FT. OF LIOUIDK • FACTOR FROM CHARTU, • UPSTREAM LINEAR VELOCITY - FT. / SEC.Ue. DOWNSTREAM LINEAR VELOCITY • FT. / SEC.lip· PRESSURE DROP DUE TO FRICTION
LOSS - LBS./SO.IN.
S • SPECIFIC GRAVITY OF FLUID ATTEMPERATURE UNOER CONSIDERATION
.3
LOSS DUE TO CONTRACTION
(U2)2Fe' K64:3
,.
.2
.. WALKER. LEWIS. MC ADAMS ~D GILLILA~D. 'PRINCIPLES or CHEMICAL ENGINEERING.PP. 87·89. MC GRAW·HILL BOOK CO. (1937)u. r. •. .- •. 0 , y..l~:' •• l-!r..
.1
•1
.4
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.3.
3000
3400
3200
_72.
DISCHARGE CHARACTERISTICS OF
RECTANGULAR AND CIRCULAR WEIRS
o
2400
2200
.2000
1800
1600
1400
1200
1000
800
600
400
200
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205
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COLBURN. IND. ENG. CHEM. 26. 1183 (1934)
PRESSURE DROPACROSS TUBE BANKS
Ii .....L.,. N""('- ')2'(~) f'liP' 3B90 S GM Os •
"")' FOR TUBE ANO SHELL HEAT EXCHANGERSMULTIPLY 4P BY A BUNDLE FACTOR ASFOLLOWS;
0.'0 FOR SQUARE-TUBES IN LINES0.40 FOR SQUARE - TUBES AT 48·
GM IS EVALUATED AT CENTER ROW OF TUBES
20 30 40 5060 60 100
:: PRESSURE ,DROP ~ LB./SO. IN.
'NUMBER OF ROWS OF TUBES:: SPECIFIC GRAVITY OF FLUID RfLATIVE TO WATER t
,MAXIMUM MASS VELOCITY' LB'/SEC./SQ. FT.(THROUGH MINIMUM FREE CROSS-SECT. AREAl,
:: OUTSIDE TUBE DIAMETER· INCHES 1~
::; MINIMUM CLEARANCE BETWEEN TUBES-INCHES;
'FRiCTION FACTOR FUNCTION-; FILM VIS'COSllY - CENTlP<XSE$
liPNS
GM
DoOsf'ZF
.01 .0204
.03
.02REFERENCE,
.003 __
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206
18
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Section 12
FLOW OF HEAT
Heat Transfer
The film transfer cocfficient for liquids flowing inside tubes (page 211) isbased on the Sieder and Tatc corrclation l which is generally acceptcd as themost rcliable for this type of hcat transfcr.
Thc chart on pagc 212 for the outside film coefficien~ for flow across tubebundlcs was derived from a corrclation by Chilton and Colburn 2 with thc consistent units in the dimcnsionless terms replaccd by more common units. Comparison of limited data with this correlation has indicated that the film coefficientshould be multiplied by the "bundle factors" given on the chart when GM is takenas the mass velocity at the center row of tubes. Kon-uniformity of flow andby-passing bctween the tube bundle and shell appear to bc the principal reasonsfor this diffcrence.
Thermal Conductivity of Petroleum Liquids
Attempts to correlate thermal conductivity of petroleum liquids as a functionof gravity in addition to temperaturc havc resulted in contradictol'y trends with°API gravity.3.4 In view of this inconsistency and since Smith 5 has shown that,at 86°F, a single value represents the reliable data belter than either trend withgravity, the relabon for the thermal conductivity of petroleum fractions on page213 is shown as a function of temperature alone. This chart may also be used forpure hydrocarbons, although the data on low-boiling aromatics arc about 1070higher than the curve.
Thermal Conductivity of Hydrocarbon Gases
As most data on the thermal eondueti"ity of hydrocarbon gases were obtainedat room temperature, it is was necessary to find some means of extrapolation tohigher temperatures. This was done by using two different methods: (1) assumption that the Prandtl number is a constant independent of temperature and(2) employment of Sutherland's equation. As the results of the two methodsbecame more divergent with increasing temperature, it was a question of selectingeither one or the other or using an average of the two. An average was chosen
I Sieder and Tate, l1ul. Eng. Chem. 28, 1429 (1936).2 Chiltonllnd Colburn, Ind. Eng. Chem. 26, 1183 (l934).3 MUic. Publication 01 Bur. Sta>l(lards, No. 97, 24 (l929).4 Kaye and Higgins, Proc. Royal Soc. 117, 459 (1928).5 Smith, Trans. Am. Soc. Mech. Engrs. 68, 719 (l936).
207
208 DATA BOOK ON HYDROCARBONS
since, while it was felt that the Prandtl number was probably more relia~le, theSutherland equation gave lower and consequently more conservative values. Inview of the uncertainties of these extrapolations any refinement beyond the useof a straight line was unwarranted. Consequently, the chart on page 215 gives thethermal conductivity of hydrocarbon vapors as a linear function of temperaturefor various molecular weights.
Logarithmic Mean Temperature Difference
In the transfer of heat between two fluids, the log mean temperature differenceapplies to flow that is either entirely countercurrent or entirely concurrent. nderconditions where there is a combination of these two types of flow, such as a heatexchanger with more tube passes than shell passes, Nagle 6 has shown that acorrection factor should be applied to the log mean temperature difference. Thiscorrection factor is given herein by either one of two types of charts, the firston page 218 and the second on pages 219 to 221. The chart on page 218 may bemore convenient to use when the factors R and A do not approach unity. If thesefactors arc near to unity, it is necessary to use the other charts. The followingexample illustrates the application of these charts:
Example 1. Determine the correct temperature difference and the number ofshell passes required in the heat transfer between two fluids having the followinginlet and outlet temperatures:
Shell side: T I (inlet) = 400°F; T2 (outlet) = 300°FTube side: t l (inlet) = 275°F; t2 (outlet) = 320°F
R = T I - T 2 = 100 = 2.22t2 - t1 45
t2 - tl 45m = = - = 0.36
T I - t l 125
From the chart on page 219, it is seen that one shell pass is insufficient sinceF is close to O. With two shell pa scs F ~ 0.90, and this arrangement would appearto be satisfactory.7 The corrected log mean temperature difference is:
0.90(L.M.T.D.) = 0.90 X 47.3 = 42.6°F
The solution of this sample is also illustrated on the chart on page 218.
6 Nagle, Ind. Elly. Chern. 25, 604 (1933).7 While other faclors may enter into the number of shell passes selected for a given
design, allY arrangement which results in a correction factor of less than 0.80 should be rejected.
600500400
THE VALUES OBTAINED FROM THESE
CURVES ARE FOR IDEAL BLACK BODIESAND FOR OTHER MATERIALS MUST BE
EMISSIVITY.
300
HEAT LOSS BY RADIATION
200100
1.0
1.2
.8
1.8
1.4
1.6
COEFFICIENTMATERIAL Of EMISSIVITY
3.8 IRON OR STEELBRIGHT .20-.35OXIDIZED .60~70
3.6 HIGHLY OXIDIZED .90-.95COPPER
3.4 POLISHED .10OXIDIZED .70
BRASS3.2 BRIGHT .07-.10
DULL .25
3.0ZINC
BRIGHT .10DULL .20
ALUMINUM PAINT .50NON-METALLIC SURFACESBRICK,WOCO,CLOTH a PAINT .95
2.6
209
=
HEAT LOSS TO THE ATMOSPHEREBY NATURAL CONVECTION
j .T
1.5
l4= E1.31iiJ
1 ,
1 •
t t,1. I I.
" 1. , ,.I
I
. I,
1.6
1.5
1.4
1.3
8
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., 'IT" 1'1:.' 1,'..'1, '-1,.i';":+ Ii ;-rr.- .... ~ ri' _ •
, '.';!' Ttl-·· '-'1 '+ -f ·1-- ._.~ ~i~ ."., 9r::i+ tH± . :!~i ':*., ::It: ~il ltt. :{-E_ 1 ~ • ~:: ; .. _ • _ :~i !'~ ~ • i1T! ~ ipi~ t .-
I "f". .. ."~ -:: '" ~ Hi T ! itt 'I' .;. .
.8 ~~tl, ' :,If. ~ l'r. fl: ;'rittl Wlei, -:.. .r~t _%'f~~·fl.il 1m lit.. (, 1-"· ~"..Jl' ~f -~.~ _J _ •• !f (n1:i ~i i i ~i Ilr, ~ u.3:1
.7, ,-:"":J:> - :1•. ,. t " >I: ,Itij :Hi--., in !~J:r ·~t . t" -t. f • !tt., rtt ::tl::' I" _ ""'!'. '! ~J::J-'
- - l .tt t t _.- .- ~l H+ I'''''':''.t • • ... 1ii :F _ :1 ,t. -. t ~ •
• I t ~ t' I'- ...
VALUES FROM THE CHART ARE TOBE MULTIPLIED BY THE FOllOWINGSHAPE FACTORS:
At" VERTICAL PIPESHORIZONTAL PIPESVERT ICAl PLATESHORIZONTAL PLATES
FACING UPWARDS 2.0FACING DOWNWARDS 1.2
llIIJ;J _ 'HEILMNI.'TRANS·, M4. soc. MECH. ENG. 51, 287 (1929)_PP. 240·241. MIC.GmR~~W~'~H~ILiLIIlO~onKdCjOi'tt(~'rn9~42~)~11
100 200 300 400 500 600
1.1
1.2
1.0
210
4,000
eu5,ooo, 'Iii -£
40000 GOOOO
I' i
20000
I' •ItB'F
1 t,,1
H i 1 rI, ,
, ,
+ 'J '
: 'I 'I !
! ; I!I .. .r , ii llil
,I
2000 30004000 6000 10000,,
I,"'1.1 II 'I. 11 r
30
60
50
40
20
100
80
'poo800
-- 600- - - 500-- 400
- 300I--
200
-tiI_
f1: ;J' . f'+H+H HEATING AND COOLINGI I , . ...
IOPOO + 'I" ,11 _', f :II! l-8000 II I t II; I
I 111lJjtl" Ii I 1,- -I
III - I I I1. _. I,! II,Ii Ii! I I,"; I! ]SpOO ,. rm - . ,', ..,
- .--1:1 d 11'1:1) l, . 1'1 ,Ii! 1~r1":
-t~1~~'-Ttl!:t~~1"im!m::m':~lf;f~~H~g:IlI!m!I~11#R'~i'~!~t'-m~h~:~'~W'~I!~: ~,~'~'~~;i~~!;Hi~:I;t-mffi~liTtm~lllffiFcl!-i'IIi+!-1:¥.'-P'-;.'f,lfH1!j-'::lJJi!j-1:Im-:I4H-:;r,j;llii:::ljl-i·-81-m'++H,f-H-Hl-l1If+;"'!~:,ij,~! I i: i iIll . I:t I':- ::1 H::!:ii 1 ~j I Iii ."r~ \' 014
H+-\-H-j+i+l-r!-+-HtH-l-H-H-8If.lll+I+++I+H+f-'--H+!A:,04''1I',"·P!.. 'II-++J1+HJ- h = KO
(CKZ) 3(ZZW) • ¢ (OZG)
I-t+t" ,t" lli;l IIW _: ~ *I!iii100 r 'I I' , t. , ... ,:\_
80 ,., " "," , ...-r' .,. ""Ii' "WI!' 'oJ "lll 11111+" -t- l.J.. ',/1 t 0.\+ Ii'! 1 I II, 4 _j_ f ; 'rlt" h= FILM COEFFICIENT - a.l.U. /HR ./SQ. FT./ F.
60 j)- I 'I .iJ.rlI(i, j.rH i,' il? I :)-r:-- /" K' THERMAL CONDUCTIVITY - B.T.U.!HR/SO. FT.!(OF PER FT.l50 . II" :. ~ ,', L :HEATED TUBE LENGTH ·fEET40 j.: I-t lU fit1 "':,.i.f' 'I, Jl. I I,· L' :.J' I' 0' INSIDE TUBE DIAMETER· INCHES
U:- ITfW1 ,;; ,!:;.-H-; :;)0 1+ I I II!! r G,MASS VELOCITY -LB,/SEC /SO.FT.I~ n- ,::. ~"",n .. -r- II I -ii, 0-
30 , • I< . ""... 'i" , 'I:: ,: I ,. , . .: C' SPECiFIC HEAT OF FLUID AT AV, FLUID TEMP.-BT.U./LB.I,¥
~ r<::. i _::, :::: l:~: 0;:: ~ I+~ .+'1: :; t Z =ABSOLUTE VISCOSITY-CENTIP()SES AT AV. TEMP. OF FLUID
20 ·ll'f:.:.;.; 4;:, ;, i: iii I::: ; II: r.Til! 'ZW'ABSOLUTE VISCOSITY-CENTIPOlSES AT AV. TUBE WALL TEMP.
, iil"/ "~'I'ili!iril'I:Il;!'! II!: ".iUI HI! .l'i1I:!'I!1f:l:-:,:I::;:I:'.;.III:I':"-O:::J.,.rmillUCllI=II:liI:Jlilll::l-Tl+H:tt'ti'rtJ-I' ': ,I "I.! .;. REFERENCe: S I EDER AND TATE, I NO, ENG, CHEM, 28, 1429 (1936)
/0 - ilJI, iili [ I!;j Iii: 1111111 fiiUH1il~!Jl~il!H]liWltnrilllfH-'-lmrllllllif.lrrm 10
I 2 3 4 5 6 8 10 20 30 40 50 60 80 100 200 300400 GOO 800 1000
211
•
20
3000
800060005000
lEEEIEEm]4000
=-crlffil2000
.200#jffitl1ltm300
111,0080
6050
40
30
4000 60002000
HEAT TRANSFER TOFLUIDS OUTSIDE TUBES
-. -i
o.~o fOR SQUARE PITCH - TUBES IN LINE0.55 FOR SQUARE PITCH - TUBES AT 45°
MULTIPLY he BY A NeUNDLE FACTOR" ASFOLLOWS:
- r rI'26. 1183 (L934)
...,i::rn:;- LiC
200 300 400 600 800100060 80 100
"'0= OUTSIDE FILM COEFFICIENT· O:r.U./HR.lSQ.FTjOF
K :: THERMAL CONDUCTIVITY OF FLUID -atU'/SQ.FT.!HR./(OF PER FT.)
00= OUTSIDE TUBE DIAMETER - INCHES
C ::; SPECIFIC HEAT OF FLUID - 8.T.U.lLB./°F
Zr::; FILM VISCOSITY - CENTIPlEES
{THROUGH MINIMUM FREE CROSS-SECTIONAL A~EAl- +J-'-
200
300
600500
400
3ooo~mWi
1000
800
10
10000118000
6000 ~~# t~.:H:H. :~ ~;;1 l:-=l: ~5000 CH 1LTON AND COLBURN. IND. ENG. CHEM.4000 .,: -j- .... ::t" t::l -':" -r- .. , ---,..--<--
10.01 .02 .03 .04 .06 .08 .1 .2 .3 .4 .5.6 .8 2
103 4 5 6 8 10
212
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8 8
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o \00 200 300 «Xl 500 600 700 800 900 1000
s
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THERMAL CONDUCTIVITY •T 1 1- OF LIQUID WATER
1 I:I:H1I,f • •
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216
LOGARITHMIC MEAN TEMPERATURE DIFFERENCE
100 100 100
90 90 ~ 90
80 80 80
70 70 70
60 60 60
55 55 55w
50 !i 50 50w
45 ::i 45 45...40 5 40 40
w35 ~ 35 35
,:" ~ ..a: ~
30 <3 w 30 <l 30Q.~w
25 ~ 25 25z...w~
20 I.' 20 20:IEJ:t:
15 a: 15 15...'"0..J
10 10 10
5 5 5
M.T.D.: .0.TI- ATz
LOG .o.T,E ATZ
WHEN Ll.T, AND Ll.Tz ARE NOT WITHIN THE CHART RANGE,THESE VALUES MAY BE MULTIPLIED BY A FACTOR, AS 0.5,2,10, OR 100. ETC.
FOR EXAMPLE:GIVEN Ll. T, (ACTUAL): 200, AND Ll.TZ (ACTUAL): 20.USE 0.5 AS FACTOR, AND Ll.T,' , '00, AND .Ll.TZ: 10.FROM THE CHART, M.T. D." 39.5OR M.T.D. (ACTUAL): 0'.5 X 39.5' 79.
REFERENCE: POWER PLANT ENG. 35. 937 (1931)
217
.t
,H
:~
jf!I
'-~~1
:1
T
20
29
-_.... ,r,
MULTIPLIED
TI :: TEMPERATURE AT WHICH HOT FLUID ENTERS
T2 ' TEMPERATURE AT WHICH HOT FLUID LEAVES
t l • TEMPERATURE AT WHICH COLO FLUID ENTERS
'la II TEMPERATURE AT WHICH COLD FLUID LEAVES
F II CORRECTION FACTOR BY WHICH L~.T.O. IS
45678910
4 5 6 7 ~~.IO:;:C:I T
.6 B.3 .4
.3 4 S .6 .7.8.9'iJ+;:rorh; l,m
,'"
2
.2
EXAMPLE:
T2'300 T,'400
" '275 '2' 320 ..A' 300-275
400-320, 0.312
,,,
.04 D6 .08 .1.02
.02 04 .06 .08 J... r
'1" I
;
LOG MEAN TEMPERATUREIIIIIIIDIFFERENCE CORRECTION
FACTOR
.01
a
t.:>~
""
I SHELL PASS
2,4,6 ETC. TU8E PASSES2 SHEL L PASSES
4,8,12 ETC. TU8E PASSES
10.09.0ao7.0
6.0
5.0
4.0 -
3.0, "
i·
2.0 -
1.0'110.9~0.8.
0.7t'lJI:Mm0.61;1;
0.5••
0.411
0.3
0.10.2 0.3 0.4 OS 0.6 0.8 1.0
219
02 0.3 0.4 OS 0.6 0.8 1.0
4.011"
3.0 ".
0.2 "
3 SHELL PASSES
6,12,18 ETC. TU8E PASSES
4 SHELL PASSES
8,16,24 ETC. TU8E PASSES
0.2 0.3 0.4 05 0.6 0.8 1.0
220
0.2 0.3 0.4 05 0.6 os LO
0.8 1.0
119331"
04 0.5 060.30.2
6 SHELL PASSES
III~ 12,24,36 ETC. TUBE PASSES JmllM
08 1.00.4 Q5 0.603020.1
2.0 ~FfHtttl*
4.0 lttl±Htl+ltt
3.01fm~m
I~.~ m~mw'''''""~~~~:HE~L~L:=;P~A;SS~E~S~~8.0 : 10,20,30 ETC. TUBE PASSES7.0
6.01115.0
221
Section 13
EQUILIBRIUM FLASH VAPORIZATION
The vapor-liquid equilibrium relations for hydrocarbon mixtures of knownanalysis can be determined by trial and error from the equilibrium relations ofthe individual components and a material balance. For any component, i(i = 1,2· .. n), ,
and
Yi = Kixi
Xi = xiL + y;(100 - L)
(1)
(2)
where Yi = mole fraction of i in the equilibrium vaporXi = mole fraction of i in the equilibrium liquid
Ki = equilibrium constant of iXi = total moles of i per 100 moles of total mixtureL = moles of equilibrium liquid per 100 moles of total mixture
Substituting Kixi for Yi in equation (2) and rearranging
XiXi = -L-+--'--K-
i("--l'""""OO---L-) (3)
At equilibrium, the sum of the mole fractions in the liquid phase, x, + X2 +... + x., must equal 1.00. While two variables, Land K" appear in the right-handmcmber of equation (3), there are actually three variables involved sinec K, is afunction of both pressure and temperature. To predict the equilibrium conditions,any two of these variables must be known and successive values oj the thirdassumed until the sum of the x's equals 1.00. Usually, temperature and pressureare the two variables specified, and then the trial and error involves L.
Flash Vaporization of Petroleum Fractions
Although the foregoing method applies to complex petroleum fractions aswell as to hydrocarbon mixtures of a comparatively few known components, it haslittle practical significance for petroleum fractions because of the laborious calculations ...required even when component analyses are available, which israrely the case. As a result, empirical correlations have been developed for predicting equilibrium flash vaporization curves from distillation data on crudes andpetroleum fractions. The flash vaporization curve is a plot of temperature againstliquid volume percent vaporized, the total vapor being in equilibrium with theunvaporized liquid at constant pressure.
222
/ :
EQUILIBRIUM FLASH VAPORIZATION 223
A number of empirical correlations for determining the atmospheric flashvaporization curve have appeared in the literature, but only a relatively simplecorrelation would seem to be justified in view of the discrepancies between the dataof various investigators. The present correllition is of the same general type asthose of Piroomov and Beiswenger l and Nelson z and applies to both petroleumfractions and whole crudes. For petroleum fractions, either the 100/0 (ASTM)distillation of the fraction itself or the portion of the crude assay (True BoilingPoint) distillation corresponding to the fraction may be used for predicting theflash curve. For whole crudes, the crude assay distillation should always be usedin preference to the 100/0 distillation. The latter should never be used if thedistillation curve flattens out below the 70'1'0 point in the neighborhood of 700°Fsince this is indicative of cracking.
In extrapolating the atmospheric flash curves to higher or lower pressures itis suggested that the parallel method proposed by Piroomov and Beiswenger beused up to pressures of 15 psig for whole crudes and wide cuts, and up to pressuresof 50 psig if the slope of the flash reference line of the fraction is not greater than2°F/ro. By this method the atmospheric flash curve is shifted parallel to itself by a temperature interval equal to the extrapolation of the 40'1'0 point3
on the flash reference line (FRL) as a pure compound on a vapor pressurechart.
This parallel method is unsatisfactory for higher pressures, since it is knownthat the flash curve becomes more horizontal with increasing pressure until itsslope is zero at the true critical pressure. Beyond the pressure limits recommendedin the preceding paragraph for parallel extrapolation, it is suggested that a variation of the method of Watson and Nelson' be used, since no very elaborate methodappears to be justified by the data. The 40'1'0 point on the FRL is extrapolated ona vapor pressure chart to a temperature 150°F above the critical temperature ofthe normal paraffin having the same boiling point as the 40'1'0 point. This extrapolated tempera:tur~ and corresponding vapor pressure is then used as a focalpoint through which straight lines are drawn on a redilinear vapor pressure chart(page 42) from the atmospheric flash temperatures for various percents vaporized. The flash curve at any pressure is determined from the temperatures atwhich the given pressure ordinate intersects these constant percent off (or quality)lines. These linear extrapolations do not apply if the true critical point of thefraction is approached since the copstant percent off lines become curved andconverge to the true critical temperature and pressure.
1 Piroomov and Beiswenger, Proc. API 10, No.2, Section II, 52 (1929).2 Nelson, "Petroleum Refinery Engineering," pp. 242-243, McGraw-Hill Book Co., New
York, N.Y. (1941).3This i3 a slight modification of the Piroomov and Beiswenger method as they use the
point of intersection between the flash and distillation curves for extrapolation.• Watson and Nelson, Ind. Eng. Chern. 26, 880 (1933).
224 DATA BOOK ON HYDROCARBONS
•
Reduced Crudes
Perhaps the most direct method of predicting the atmospheric flash curve ofa reduced crude (or .any reduced stock) which at the same time is reasonablyaccurate is the following:
(1) Construct an atmospheric flash curve for the original crudc.(2) Determine the number of moles of both original crude and reduced crude
per given volume of original crude.(3) At the dew point (lOOro vaporized) of the original crude, assume that the
reduced crude vapors are at their dew point at a partial pressure equal totheir mole fraction in the total vapors (moles of reduced crude/moles oforiginal crude) multiplied by 1 atm.
(4) Extrapolate the 40% point on that portion of the flash curve corresponding tothe yield of reduced crude from the partial pressure computed by (3) to 1 atm.
(5) If the reduced crude has been stripped of light ends, its atmospheric flashcurve is drawn through the extrapolated point parallel to the flash curve ofthe original crude between the abscissas corresponding to the yield ofreduced crude.
(6) If the reduced crude has not been stripped of light ends, a smooth curve isdrawn from the split point on the flash curve of the original crude to the 20%point on the flash curve constructed by (5) to approximate the front end ofthe flash curve of the reduced crude. Establishment of the 20ro point as thepoint above which unstripped light ends cease to affect the reduced crudeflash curve is, of course, entirely arbitrary but, at the same time, fairlyrepresentative.
While the method outlined above is empirical to a large extent, it does havesome theoretical justification. If all but one drop of reduced crude were flashed,this last drop of liquid would be in equilibrium with the reduced crude vaporsat 1 atm. It is then assumed that if 100% original crude were flashed at 1 atm, thelast drop of liquid would have the same composition as the last· drop ofreduced crude, and the latter vapors would be at a partial pressure corresponding to their mole fraction multiplied by one atmosphere. The basis forthis assumption is that the temperature difference between the boiling range ofthe last drop and 'that of the vapors romoved in reducing the crude is usually sogreat that these vapors can be considered the equivalent of steam or gas in so faras the equilibrium relations of the last drop is concerned. Making the flash curves·of reduced crudes parallel to the flash curves of their original crudes was originallysuggested by Piroomov and Beiswenger and appears to be fully justified bytheir data.
Example 1. Determine the atmospheric flash vaporization curves of an EastTexas crude and its 35% bottoms (both stripped and unstripped) from the following data taken from an assay workup of t.he crude:
EQUILIBRIUM FLASH VAPORIZATION 225
122177262350443538636752
(905)
Assay (T.B.P.) DistillationI.B.P., of
5%10%20%30%40%50%60%70%80%
CrudeOverhead (0-65%)Bottoms (65-100%)
Gravity°API
37.447.720.9
Lbs/Gal
6.986.577.73
752 - 177Slope of DRL* = 60 = 9.6°F/%
• DisLillaLion reference line-through 10% and 70% points.
50% Point (DRL) = 177 + (50 - 10)9.6 = 561°F
The slope and 50% point of the flash reference line are determined from thechart on page 228:
Slope (FRL) = 6.4°F/%; 50% Point (FRL) = 561 - 40 = 521°F
The atmospheric flash curve is derived from its reference line by lIsing therelation on page 229.
Percent Assay Distillation (OF) Ratio Flash Vaporization (F)
Vaporized Curve DRL t>t' of (t>t')'s t>t' FRL Curve
5 122 129 -7 0.40 -3 233 23010 177 177 - - - 265 26520 262 273 -11 .36 -4 329 32530 350 369 -19 .34 -6 393 38740 443 465 -22 .34 -7 457 45050 538 561 -23 .34 -8 521 51360 636 656 -20 .33 -7 585 57870 752 752 - - - 649 64980 (905) - 848. +57 .33 +19 713 .732
The flash reference line and the atmospheric flash curve of the original crudeare-shown on Figure 1. Proceeding from (1), the flash curve of the original crude,the atmospheric flash curves of the stripped and unstripped reduced crudes arederived by the method outlined in the text:
262 + 538 + 905 °(2) Vol. Av. B.P. of whole crude = 3 = 568 F
226 DATA BOOK ON HYDROCARBONS
Mean Av. B.P. of whole crude = 568 - 70 = 498°F (Section 2)
Molec. wt. of whole crude = 197 (Section 3)
203 + 373 + 558Vol. Av. B.P. of 65% overhead = 3 = 378°F
495 - 139Slope of DRL (65% overhead) = 60 = 5.9°F/%
Mean Av. B.P. = 378 - 38 = 340°FMolec. wt. of 65% overhead = 139
Per 100 Galof Crude
Moles of crude = (6.98 X 100)/197 = 3.55Moles of overhead = (6.57 X 65)/139 = 3.07
Moles of reduced crude 0.48
(3) Partial pressure of reduced crude at the dew point of the original crude0.48
= - X 1 = 0.135 atm.3.55
(4) The 40% point on the reduced crucle flash curve corresponds to 65 + 0.40X 35 = 79% or 722°F on the flash curve of the original crude.
By extrapolation from 0.135 atm. to 1 atm., the 40% point on theatmospheric flash curve of the reduced crude is 900?F.
(5) The atmospheric flash curve of the stripped reduced crude is drawn throughthe extrapolated point parallel to the 65-100% portion of the flash curveof the original crude. This reduced crude flash curve may be convertedto percent on reduced crude by proportioning the 65-100% yield onoriginal crude to 0-100% on reduced crude. Both curves are shown inFigure l.
(6) The front end of the atmospheric flash curve on the unstripped reducedcrude is constructed by drawing a smooth curve from the 65% point on theflash curve of the odginal crude to the 20% point on the flash curve of thestripped reduced crude as shown in Figure 1. This curve is also given onthe basis of 0-100% reduced crude.
GENERAL REFERENCES
Edmister and Pollock, Chem. E7l{J. Progress 44, 905 (1948).Katz and Brown, Ind. E7l{J. Chern. 26, 1373 (1933).Packie, Trans. Am. Inst. Chern. Engrs. 37, 51 (1941).
1100
1000
900
800
700
600
!lOO
400
300
EQUILIBRIUM FLASH VAPORIZATION 227
20010 20 30 40 50
FIGURE 1
60 70 80 90 100
7
3If i li
. FLASH AND DISTILLATION REFERENCELINES (FRL AND DRLl ARE STRAIGHTLI NES THROUGH THE 10% AND 70% 2
, POINTS. THE TEMPERATURES AT THE ~50% POINTS REFER TO THESE ~ m
- REFERENCE LINES. E I
.... ;~~ : ... RE~G~l~it!fI:~:':I~-'~ 1 .o
7 8 9 10 II 12632
PREDICTION OF FLASH REFERENCE LINEFROM DISTILLATION REFERENCE LINES
1--JfJ-
~ .. ~. gw.•r
I2
5
3
7
4
o
,,' t.~ I~ •
60
40
4
US
T
i ~If !'iii R,f;f,Et EN' ~...!; - . -
6 7 8 9 10 II 12
40 11-.. -
II
20
BI O
-20
-40
-602 3 5 6
-40
228
W 30 40 ~ 60 ro ~ 90 10010
tl±I
~. .,,
~
, ; ., : t
I tmI, , 1...Mm
1 c,
,
• PREDICTION OF FLASH CURVEtoo FROM ITS REFERENCE LINE
100 lm!l I1'-'-
I fmII mIl• tmn II.. ,
• 11UlI
_ 11$ CRUDE ASSAY (T.B.P.) DISTlLLATION, .
'gmj
II••11m! II 11m •," .t" ,p I:J±-, .
10 20 30 40 50 60 70 80 90 100
lEE ' I10% (A.s:tM.) DISTILLATION, .
·lmJU .JI#J: "* lIV IS THE DEPARTURE OF THE ACTUALFLASH AND D1STI LLATION CURVES FROMTHEIR RESPECTIVE REFERENCE LINES.
n5 WHILE THE INDIVIDUAL (lIl')'S MAY BEEITHER PLUS OR MINUS, THE RATIO IS
f:fk,'ll ALWAYS POSITIVE.
~,
~l'mIJ, ' '.
..Iflill
• .1·w_!l0
o
.80
.60
,20
.80
.60
1.00
.20
1.00
229
Section 14
FRACTIONATING TOWERSIn order to simplify the work involved in making stepwise calculations for
the rectification of binary and multieomponent systems, Gilliland' has presentedan empirical correlation between theoretical steps and reflux ratio. To use theGilliland correlation to predict the number of theoretical plates for a given refluxratio, the minimum number of steps at total reflex and the minimum reflux ratioare required.
Minimum Number of Theoretical Steps
When a separation is specified with respect to only two components of a multicomponent mixture, the lower boiling of these two components is designated thelight key component and the higher boiling the heavy key component, and theminimum number of steps can be calculated by the well-known Fenske equation 2
as follows: a
or
log (X LKD) (X HKlV)
8XLKlV XHKD
Af=log aLK
[aLK]SM = (X LK D) (X HKlV)XLKlV XHKV
(1)
(1a)
After equation (1) is solved for 8M , the latter may be substituted in thisequation along with the distribution of either key component to prcdict4 the distribution of the other components, or
Likewise,
(X ,.D) (X HKlV)log -X X = 8 M log aL
!-IV 11 K D
log (X lilY) (X LKD) = 8 M log (a LK)XlID XLKlV all
(2)
(3)
In any of the above equations, moles per 100 moles of feed may be replacedby total mo)es, or volume or weight units since in any of these conversions themultiplying factors cancel out.
1 Gilliland, Ind. Eng. Chern. 32, 1220 (1940).2 Fenske, Ind. Eng. Chern. 24, 482 (1932).S A table o( nomenclnture is given on page 243.• This equation may be used (or any pair o( component8.
230
FRACTIONATING TOWERS 2H1
When the dcgree of separation is specified for more than two components,equation (1) must be applied to all critical combinations of these components andthe maximum SJ/ determincd for the most difficult case. If the separation is specificd with respect to the total quantity of two or more components, as in thecase of Examplc 1, trial and eITor is required for thc solution of SjJ.
It should be pointed out that the concentrations calculated by equations(2) and (3) actually apply only to the separation at total rcflux and, with theexception of the two key components, there will be some variation of thc degrecof separation with the reflux ratio. As the rcflux ratio decreases, there is someimprovement in separation betwecn light and heavy componcnts boiling outsidethe range of the kcy components and some deterioration in the separation of components boiling intermediate bctween the kcy components. However, in so far asthe present procedure is concerned, the distillate and bottoms compositions forother reflux ratios are assumed to be thc Same as those calculated for total reflux.
Minimum Reflux Ratio
Gilliland 5 has proposed several diffcrent formulas for predicting minimum refluxratio and all have the disadvantage of being composcd of a number of complexterms in addition to requiring trial and error for solution. Although all theseequations appeal' to give satisfactory rcsults, the tcrms are so complcx that it isdifficult to bc ccrtain that therc arc no numerical crrors in thcir application.
In order to apply the Gilliland method with greater facility, the followingequation was developcd for predicting the minimum rcflux ratio of a multicomponent system:
(O/Dhf + 1= (aLKTf.FC + 1) (XLKD - XIIKD)('(LK - 1 ILK
(4)
(O/D)M can be calculated for two arbitrary states of feed vaporization:
1. "Liquid" feed, cOITesponding to vaporization of the feeu equivalcnt to thefraction of the feed lighter than the light key component. For the componentslighter than the light key, h = ZL/aL and for the light key and heavier components, ILK = ZLK, and III = Zfl.6
5 Gilliland, Ind. Eng. ehe",. 32, HOI (1940).8 ]£ components, intermediate between the two key components, are present, they are
considered ei her light or heavy componen'" depending upon which key their volatility morenearly approaches. In the case of "liquid" feed, I L = Zl. and I II = ZH for these intermediate components; in the case of "vapor" feed, I L = ZL/aL and I II = ZuaH/aLK.
232 DATA BOOK ON HYDROCARBONS
•
2. "Vapor" feed, corresponding to vaporization of the feed equivalent to thefraction of the fecd consisting of the hcavy key component and lighter. For thecomponents lighter than the heavy key, If_ = ZL/CtL and ILK = ZLK/aLK andfor the components heavier than the heavy key, 1/1 = ZI/.6
After the minimum reflux ratios have been calculated for "liquid" and "vapor"feeds, the minimum rcflux ratio for the actual vaporization of the feed can be calculated by direct interpolation or extrapolation. However, extrapolation beyond50% of the difference between "liquid" and "vapor" feed may lead to seriousdeviations.
The first term of the right-hand side of equation (4) is the same as for binarymixtures, and the equation reduces to the cquivalcnt of a binary mixture whonall light components other than the light key have infinite volatility and all heavycomponent other than the heavy key have zero volatility. Under these circumstances the equation is exact when hK is taken as the ratio of the two componentsin the liquid phase of the feed. That is, if the feed is introduced as a liquid at itsbubble point, hK = ZLK, which is the ratio of the two components in the feed;if the feed is introduced as a vapor at its dewpoint, hK = Z',K/OtLK, which is theratio of the two components in the cquilibrium liquid. For intermediate stagesof vaporization hK can be calculated from the flash vaporization formula, although direct intcrpolation of the minimum reflux ratio on the basis of percentagevaporization between thc sat urated liquid and saturated vapor feeds gives valuesonly slightly in error on the conservative side.
In the case of multicomponent mixturcs, equation (4) is semi-empirical sinceit was necessary to make simplifying approximations in its derivation. Furthermore, the exact values of the various 1's cannot be calculated directly from thecomposition and state of vaporization of the feed, since the liquid on the feedplatc is not identical to the liquid phase of the fecd as in the case of a binarymixture. As a result, it was necessary to define the 1's empirically for two statesof fced vaporization, arbitrarily choscn to simulate a binary mixture of the twokey components, and then intcrpolatc or extrapolatc to the minimum reflux ratiocorresponding to the actual vaporization of the fced.
Equation (4j has been checked for a number of multicomponent systems onwhich the minimum reflux ratio was determined by stepwise trial and error calculations. Generally, unusual systems were chosen with respect to composition andrelative volatility in order to reveal the maximum deviations ever likely to beencountercd in practice. The agrecment was quite satisfactory as the averagedeviation was less than -+-5% and the maximum about lOra. The latter occurred atthe limit of extrapolation relative to the arbitrary feed states.
FRACTIONATING TOWERS 233
Also, the minimum reflux ratio was calculated for these same systems by theColburn method 7 with about the same degree of accuracy. It should be pointedout that the latter gave better results than equation (4) when the relative volatilities and compositions were not so abnormal as the systems selected. However,under these circumstances both methods were quite accurate as the deviationsseldom exceeded a few percent, and the present equation has a distinct advantagein that it is explicit and does not require trial and error.
Both methods are quite sensitive to the selection of key components, andthe selection of the wrong key components can lead to a much greater error thanis inherent in either method. If the desired separation is between adjacent components, there is usually no doubt about selecting these as the key components.However, if there are additional specifications relative to other components, itmay be necessary to try two or more combinations of key components to makesure that the minimum reflux ratio is sufficient to fulfill all specified conditions.
Correlation of Theoretical Steps with Reflux Ratio
As mentioned at the beginning of this section, Gilliland correlated the resultsof a large humber of stepwise calculations on various binary and multicomponentmixtures by plotting
[S-SM) I[S+1] ~</> (S) against [(OlD) - (OID))f)/[OlD +1)-F(OlD)
and found that all points could be represented by a single curve irrespective of thetype or degree of separation. These points, along with about half again as manyadditional points, were replotted, and the best curve through them was essentiallythe same as Gilliland's original correlation.
In arriving at the coordinates for the additional points the minimum refluxratio was calculated by equation (4); therefore these points are a criterion of thepresent method as well as the curve itself. In no case did the deviations exceedeither 3 theoretical steps or 15%, and the average deviation was less than 1theoretical step and also less than +50/0. To take care of the maximum deviationit is recommended that in any design the number of theoretical steps predicted
~ from the correlation on page 244 be increased by either 3 theoretical steps or100/0, whichever is greater.
Plate Efficiency
Because of the large number of factors which undoubtedly influence theplate efficiency of a fractionating tower, any fundamental formula accountingfor even the most important variables must necessarily be quite involved. For thisreason, a simple empirical correlation of the limited data on hydrocarbon mixturesseemed to be the most promising method of predicting plate efficiency.
7 Colburn, Trans. Am. Inst. ehem. Engrs. 37, 805 (1941).
234 DATA BOOK ON HYDROCARBONS
Gunness 8 correlated the results of several tests on petroleum mixtures on thebasTs of vapor pressure of the liquid. As he points out, this is a method of indirectlycorrelating plate efficiency with liquid viscosity since viscosity of pure hydrocarbons and narrow boiling fractions is an approximate function of vapor pressureover a fai,rly wide range of vapor pressures.
In view of the consistent results obtained by Gunness, pla.te efficiency wasplotted directly against fluidity (reciprocal viscosity) for a number of tests oncommercial towers including those upon which Gunness based his curve. The curveon page 245 represents this correlation. While the overall plate efficiency exceeds10070 at fluidities greater than 9 Cp-1, this is not inconsistent as the flow of theliquid across the plates results in concentration gradients which may achieve agreater degree of fractionation than predicted by stepwise calculations in whichthe liquid is assumed to leave the plate in equilibrium with the composite vapor.Lewis9 has shown theoretically that different combinations of liquid and vaporconcentration gradients across the plate may give overall plate efficiencies ashigh as 200--300'10 when based on stepwise calculations.
There is no reason to believe that this correlation applies to mixtures otherthan hydrocarbons, and with the exception of alcohol-water mixtures there aretoo little data available to afford a comparison. Although there is considerablevariation in the alcohol-water data, there is some indication that plate efficienciesare somewhat greater than for hydrocarbons of the same viscosity.
Location of the Feed Plate
As a simple approximation for locating the feed plate, it may be assumed thatthe proportion of actual plates above the feed will be the same as that required toeffect the same separation between the key components at total reflux. That is, thenumber of theoretical steps at total reflux is calculated for the concentrationchange in the key components between the feed and distillate compositions. It isthen assumed that the ratio of this to the total number of theoretical steps at aninfinite reflux ratio is the same as the ratio of actual plates above the feed is tothe total number of plates. Application of this method is illustrated by Example 1.
In some cases where there are oritical components other than the two keycomponents, it may. be necessary to check the total reflux steps above and belowthe feed on the basis of these components, since the optimum location of thefeed plate will be different with each pair of components. Usually the separationof components other than the key components is so complete that only the latterneed be considered.
8 Gunness, Sc.D. Thesis, Mass. Inst. Tech. (1936).9 Lewis, Ind. Eng. Chern. 28, 399 (1936).
FRACTIONATING TOWERS 235
Packed Towers
The charts on pages 246 to 248 giving the H.E.T.P., capacity and pressuredrop in packed towers are self-explanatory. Since practically all of the H.E.T.P.data were on towers less than 12 in. in diameter, caution should be used in thedesign of larger towers. One of the greatest sources of inefficiency in a packed toweris poor liquid distribution. If good distribution can be achieved by efficient distributors, the extrapolations may be used for larger towers with reasonableassurance.
Example 1. At an operating pressure of 100 psig determine the number ofplates and reflux ratio required to separate the mixture given below so that thebottoms contain at least 90ro of the butenes-2 present in the feed and at thesame time have an isobutene content not greater than 5%:
Component
i-C,Hloi-C,Hs
C,Hs-1C.H IO
t-C,Hs-2c-C,Hs-2
Feed
(Mole %)40.020.015.05.0
10.010.0
100.0
(1) Dewpoint of Distillate and Bubble Point of Bottoms
In order to calculate the average volatilities, the dewpoint of the distillateand bubble point of the bottoms must be found by trial and error using assumedcompositions. These are tabulated below.
-Moles Per 100 Moles of Feed Mole Fraction
ComponentFeeti Distillate Bottoms Distillate Bottoms
i-C.H LO 40.0 39.3 0.7 0.530 0.027i-C.H, 20.0 18.7 1.3 .253 .050
C.H...1 15.0 13.0 2.0 .176 .077C.H,o 5.0 1.0 4.0 .014 .154
t-C.H,·2 10.0 1.5 8.5 .OW .327.,.C.H...2 10.0 0.5 9.5 .007 .365
100.0 74.0 26.0 1.000 1.000
As a first trial, assume the dewpoint of the distillate is 14tl°F at 7.8 atm (114.7psia) .
236 DATA BOOK ON HYDROCARBONS
First Trial
Component YD a'D· Pt :i;
HO°F 140°F "yiP
':"C,H IO 0.530 1.29 8.4 0.493i-C,H, .253 1.155 7.5 .263
C,H,-I .176 1.13 7.35 .187C,H,o .014 1.00 6.5 .017
t-C,H...2 .020 0.97 6.3 .025c-C,H...2 .007 0.91 5.9 .009
1.000 0.994
• Relative volatilities to C4H 10 or (0")'8 aTC used as a matter of convenience; then, the(a'.,.)'s are converted to (a••)'s, the relative volatilities to t-C,H,-2, which will be seleetcd asthe heavy key component.
t Computed from the fugacity function of butane multiplied by the relative volatilities.
Since the sum of the x's is 0.994 instead of 1.000, the assumed temperatureshould be lowered slightly, but the difference would be so small (less than l°F)that the change in the (a'Jl) 's would be imperceptible. Consequently, 140°F willbe used as the dewpoint of the distillate.
The bubble point of the bottoms is assumed to be 165°F at 8.0 atm 10 for thefirst trial.
First Trial Second Trial
Component XIVa'w· pt a'w· PtY165°F 165°F Pxl.. 160°F 160°F Y
i-C,H,o 0.027 1.26 10.7 0.036 1.265 10.25 0.035i-C,H, .050 1.14 9.7 .061 1.145 9.3 .058
C,H... I .077 1.115 9.5 .091 1.12 9.1 .088C,H,o .154 1.00 8.5 .164 1.00 8.1 .156
t-C,H ...2 .327 0.97 8.25 .337 0.97 7.85 .321c-C,H,-2 .365 0.915 7.8 .356 0.915 7.4 .338
1.000 1.045 0.996
• Relative volatilities to C~HIO or {«')'8 are used ns a mnttcr of convenience; then, the(a'av)'S are converted to (aU\')'s, the relative volatilities to t-C IH:;-2, which will be selected asthe heavy key component.
t Computed from the fugacity funet:on of hutane multiplied by the relative volatilities.
The bubble point of the bottoms wiil be taken as 160°F. The relativ~
volatilities are averaged and converted to t-C~H s-2 as the heavy key in the following table:
\0 After allowing 3 Ib/sq in. as the approximate pressure drop through the tower.
FRACTIONATING TOWERS 237
, , ,aD aw aA ,
Component 140°F 160°F 150°F a a.(a' Da'wa'.A.)~!l aa.
7.8 at.m 8.0 atm 7.9 atm
i-C,H ID 1.29 1.265 1.275 1.275 1.315i-C,H. 1.155 1.145 1.15 1.15 1.185
C,H.-l 1.13 1.12 1.125 1.125 1.16C,H ID 1.00 1.00 1.00 1.00 1.03
t-C,H8-2 0.97 0.97 0.97 0.97 1.00c-C,Hg-2 0.91 0.915 0.91 0.91 0.94
(2) Minimum Theoretical Steps (Total Reflu:t)
The minimum number of theoretical steps by which the desired separation canbe accomplished is calculated as follows:
Let t = moles of t-C4H s-2 in the distillate per 100 moles of feed10 - t = moles of t-C4H s-2 in the bottoms per 100 moles of feed
Since 90% of the butenes-2 must be.retained in the bottoms, the cis-butcne-2content of the distillate and bottoms will be:
(2 - t) moles in the distillate per 100 moles of feedand (8 + t) moles in the bottoms per 100 moles of feed
Using the previously assumed values of 18.7 moles of isobutene in the distillate and 1.3 moles in the bottoms, the following equations must be satisfied:
C1~;) CO t- t) = (1.185)8M
(18.7)(~) = (1.185)8
M
1.3 2 - t 0.94
A trial and error solution of these equations shows that they are satisfied bySM = 25.5 and t = 1.62.
The distribution of the other components can be calculated from SM and thedistribution of t-C4 H s-2.
i-C4H IO : Let u = moles of i-C4HIO in bottoms
( 40 - 1') (8.38) = (1.315)25.5 = 1075u 1.62
= 0.19 moles of i-C4H IO in the bottoms
C4Hs-1: Let v = moles of C4 Hs-1 in the bottoms
(15 - v) (838) = (1.16)25.5 = 44
v 1.62
v = 1.58 moles of C4Hs-2 in the bottoms
238 DATA BOOK ON HYDROCARBONS
C.H IO : Let w = moles of C.H IO in the bottoms
(5 - W)(8.38) = (1.03)25.5 = 2.12
W 1.62
W = 3.55 moles of C.H10 in the bottoms
The percentage of i-C.Hs in the bottoms will be:
(0.19 + 1.3 + 1.58 ~33.55 + 8.38 + 9.62) 100 = 5.3%
In order to meet a maximum of 5.0ro i-C4 Hs specified for the bottoms, it isnecessary to reduce the 1.3 moles to 1.22 moles in the bottoms. This would requirean increase in SM to 25.8 which would modify the distribution of the other components. However, the latter change is so slight that it can be neglected. Thecomposition of the overhead and bottoms will then be:
Moles Per 100 Moles of Feed Mole FractionComponent
Fecd Distillate Bottoms Distillate Bottoms
i·C,H,o 40.0 39.81 0.19 0.528 0.008i·C,H, 20.0 18.78 1.22 .249 .050
C,H..1 15.0 13.42 ·1.58 .178 .064C,H IO 5.0 1.45 3.55 .019 .145
/·C,H,-2 10.0 1.62 8.38 .021 .342.,.C,H..2 10.0 0.38 9.62 .005 .391
75.46 24.54 1.000 1.000
(3) Minimum Reflux RatioSince the critical separation is between isobutene and the butenes-2, the
former is naturally selected as the light key component and trans-butene-2, sinceit is more volatile than the cis-butene-2, as the heavy key component. Butene-l isconsidered a light intermediate component because of the proximity of its relativevolatility to that of isobutcne; normal butane is considered a heavy intermediatecomponent since its relative volatility is nearer to the heavy key than the lightkey. The following tabulation gives the necessary information for calculating theminimum reflux ratios for the two arbitrary states of feed vaporization:
Mole Fraction
Component Type "'BV HLiquidtl lIVapor"Feed Distillate Bottoms
Feed Feed
':-C,H,o L 0.400 0.528 0.008 1.315 3.04 3.04i-C,H, LK .200 .249 .050 1.185 2.00 1.69
C,H..1 L .150 .178 .064 1.16 1.50 1.29C,H IO H .050 .019 .145 1.03 4.00 3.48
t-C,H,.2 HK .100 .021 .342 1.00 - -.,.C,H..2 H .100 .005 .391 0.94 2.00 2.00
1.000 1.000 1.000
FRACTIONATING TOWERS 239
"Liquid" jeed-40% vaporized
(O/D) + 1 = 1.185 X 2.00 + 1.0 (0.249 _ . 1)M 1.185 _ 1.0 2.00 °02
+ 01.331
55 (0.528 - 3.04 X 0.021) + 1.16 (0.178 - 1.50 X 0.021)
. 1 0.16
1.03 (0.249 ) 0.94 (0.249 )+ 1.185 - 1.03 4.00 - 0.019 + 1.185 - 0.94 2.00 - 0.005
(O/Dhf = 1.88 + 1.94 + 1.07 + 0.29 + 0.46 - 1 = 4.64
"Vapor" jeed-90% vaporized
(O/D) 1.185 X 1.69 + 1.0 (0.249 )M + 1 = -- - 0.021
1.185 - 1.0 1.69
1.16 (+ 1.94 + 0.16 0.178 - 1.29 X 0.021)
1.03 (0.249 )+ 1.185 - 1.03 3.48 - 0.019 + 0.46
(O/D)M = 2.06 + 1.94 + 1.10 + 0.35 + 0.46 - 1 = 4.91
Assume that the feed is sufficiently preheated to vaporize a percentageequivalent to the distillate or 75.4670. By interpolation, the minimum reflux ratiocorresponding to this feed vaporization is:
(75.46 - 40)
(O/D)M = 4.64 + 90 _ 40 (4.91 - 4.64) = 4.83
(4) Theoretical Steps vs. Reflux Ratio
Using the values determined in preceding sections for minimum theoreticalsteps,. 25.8, and for minimum reflux ratio, 4.83, the number of theoretical stepsfor various reflux ratios can be predicted from the correlation on page 244:
OlD F(OID) </>(8) 8 Theoretical Platea-
4.83 - - .. ..5.25 0.067 0.570 61.3 60.35.75 .136 .502 52.7 51.76.50 .223 .430 46.0 45.07.50 .314 .366 41.3 40.3.. - - 25.8 24.8
- The reboiler i. considered the equivalent of one theoretical step. With a partial insteadof a total condenser, a second theoretical step also could have been deducted.
240 DATA BOOK ON HYDROCARBONS
n = 10.1
(5) Number of Actual Fractionating Plates
To predict the number of actual plates it is necessary to determine the averageviscosity of the liquid on the plates. Since the temperature difference between thetop and bottom of the tower is so small, the average viscosity may be taken asthe viscosity at the average temperature. For this purpose the viscosity of butaneat 150°F will be used.
Viscosity of C.H IO @ 150°F = 0.216 cs "" 0.216 X 0.523 = 0.113 cpFluidity = 1/0.113 = 8.9 Cp-l j Plate efficiency = 99%
Using a plate efficiency of 99% the number of actual plates is computed forvarious reflux ratios:
OlD S Theoretical Steps Actual Plates
4.83 ., ., .,5.25 61.3 60.3 60.95.75 52.7 51.7 52.26.50 46.0 45.0 45.57.50 41.3 40.3 40.7., 25.8 24.8 25.0
The number of actual plates is plotted against reflux ratio in Figure 1.
A reflux ratio of 6.50 to 1, or 1.35 times the minimum, is selected. The numberof actual plates corresponding to this reflux ratio is 45.5 so that a 50-plate towerwould be required.
(6) Location of the Feed Plate
The number of plates above the feed is based on the proportion of theoreticalsteps at total reflux which would be required to effect the change in concentrationof the key components between the feed and distillate. This proportion is appliedto the actual number of plates (including the reboiler) to determine the numberabove the feed plate.
In order to take into account any appreciable difference in relative volatilityabove and below the feed, the relative volatility used for calculating the steps attotal reflux between feed and distillate is the geometric mean of aD and a" or,
(1.155 1.15)~i
an = 0.97 X 0.97 = 1.19
The number of total reflux steps which would be required between the feedand distillate is calculated by the following equation:
( l8.78) (~) = 1.19n = 5.79'20 1.62 '
50
40
30
FRACTIO ATING TOWERS 241
4 5 6FIGUllE 1
7 8
Number of actual plates above the feed would then be:
10.1 (50 + 1) = 2025.8
The vaporization of the feed can be taken into account by adding the fractionvaporized to n since 10010 vaporization would be equivalent to a theoretical stepat total reflux. This would change the proportion of plates above the feed asfollows:
(10.1 + 0.75) (") I• 00 + 1 = 21.4 pates above the feed
20.8
Feed lines would probably be installed above the 2'!th, the 28th and 32ndplates from tile bottom of the tower.
242 DATA BOOK ON HYDROCARBONS
GENERAL REFERENCES
Atkins and Franklin, Refiner Natural Gasoline Mfgr. (Jan. 1936).Brown, Sanders, Nyland and Hesler, Ind. Eng. Chem. 27, 383 (1935).Brown and Souders, Oil and Gas J. 31, 34 (1932).Chilton llnd Colburn, Trans. Am. Inst. Chern. Engrs. 26, 178 (1931).Elgin and Weiss, Ind. Eng. Chem. 31, 435 (1939).Fenske, Lawroski llnd Tongberg, Ind. Eng. Chern. 30, 227 (1938).Fenske, Unpublished data, Pennsylvania State College.Gilliland, Ind. Eng. Chent. 32, 918, 1101, 1220 (1940).Gunness, Ind. Eng. Chern. 29, 1092 (1937).Lewis and Wilde, Trans. Am. Inst. Chern. Engrs. 21, 99 (1928).Perry, "Chemical Engineers' Handbook," pp. 829-832, McGraw-Hill Book Co., New York,
N.Y. (1941).Sherwood, Shipley and Holloway, Ind. Eng. Chem. 30, 765 (1938).White, Tram. Am. Imt. Chem. Engrs. 31, 390 (1935).
FRACTIONATING TOWERS 243
nm
aD
alV
LKHKLHDW
ZH
.vomenclatureX moles of any component in distillate or bottoms per 100 moles of feedx mole fraction of any component in liquidy mole fraction of any component in vaporD moles of distillate per 100 moles of feedo moles of reflux per 100 moles of feedOlD reflux ratio(OIDhl minimum reflux ratio corresponding to S = 00
S number of steps from still to distillate8,1/ minimum number of steps corresponding to OlD = 00
P number of theoretical plates; with a partial reboiler and partial condenser, P = S - 2, and with a partial reboiler and total condenser,P=S-lratio of mole fraction of any light component to heavy key componentin the feedratio of mole fraction of light key component to any heavy componentin feedrelative volatility of any component to heavy key at the dew point ofthe distillaterelative volatility of any component at the bubble point of the bottomsrelative volatility of any component at the arithmetic average tempera-ture of the dew point of the distillate and the bubble point of thebottomsmean relative volatility of any component, (aD' alV . a.4)fi
used as a subscript to refer to the light key componentused as a subscript to refer to the heavy key componentused as a subscript to refer to any light componentused as a subscript to refer to any heavy componentused as a subscript to refer to the distillateused as a subscript to refer to the bottomsused as a subscript to refer to the plates above the feedused as a subscript to refer to the plates below the feed
.1
1IIIriCORRELATION OF THEORETICALSTEPS WITH REFLUX RATIO
MULTICOMPONENT AND BINARY MIXTURES
244
.9
.8
.6
.5
.4
.3
.2
1201.11111100
90
80·
70
60
5040_::••ll!IIflE:IJffi
OVERALL PLATE EFFICIENCY vs.FLUIDITY OF LIQUID ON PLATES
ONLY DATA 00 HYDROCARBON MIXTURES WEREUSED IN THIS CffiRELATION, AND THERE WEREINSUFFICIENT DATA ON OTHER TYPES TO JUSTIFY A MORE GENERAL USE. HOWEVER, THEREWERE SOME EVIDENCE THAT THE CURVE IS ALITTLE CONSERVATIVE FOR ALCOHOL - WATER
MIXTURES.
120
110
100
90
80
70
60
50
40
30
20
10
_____'0
2 3 4 5 6 7 8 9 10 II 12 13 14
245
mIR~12ioll~3IoI14~oll~ 60 7'08090 I
HEIGHT EQUIVALENT
TO A THEORETICAL PLATE
(I) WHILE THIS CORRELATION WAS DE'
VELOPED fROM DATA ON RASHIG
RINGS AND 8ERL SADDLES, IT PR08
ABLY APPLIES TO OTHER SIMILAR
TYPES OF HOLLOW PACKING.
(2) VALUES OF H.E.lP. FROM THIS CHART
CORRESPOND TO THE MAXIMUM TOWER
CAPACITIES GIVEN BY THE CHART ON
THE OPPOSITE PAGE. FOR THE VALUESOF HE.T.P. AT CAPACITIES BETWEEN 80%AND 100% OF THE MAXIMUM, DIVIDEH.E.T.P. FROM CURVES BY THE FRACTIONOF ULTIMATE CAPACITY (.80-1.00) ATWHICH THE TOWER WILL OPERATE.
30.:_. :t';
204567891032
2
4a!f11i1
•
246
60
100
80
1000
800
600500
tI 400
300
" .200
'n
·r.... '· ....
"'.
••I"4T'~
,I';r.j
ltllllltltrTl1111
;~':+fTo"", .
.....···'11:;::;:1-0-""'-:1=
+
* USE VALUES OF S/F 3 FROM CUR\IE
FOR RASCHIG RINGS. BERL SADDLESW PACKING UP 10
2 INOiES IN SIZE. FOR SIZES GREATER'THAN 2 INCHES, USE INDIVIDUAL
VALUES OF SAND F.
lilt! 1) r r 1111 I 1 I'r-~
f"'";m.
rt~'·-I--t"""'
'it
~~i:-:'l:::.Jx·
jj
~-d
,.,.,~li
='J="~J';+:-j:,l
3
r,
2
. e:l3.f+ "t~
•., ! ·/+l!;I"·'." I' I .,
.3 .4.5.6.7.8.910
..mI·;,·;:; I ;'i-;t:;:-..J:,ENG. DiEM. 30. 765 (1930)~rF!¥:tJ~lii r:'~
.2
~MlrLEY AND HOLLOWAY. IND .
·1
SUPERFICIAL MASS vaoCITY OF VAPOR-L8SISEC/SO.FT.L- .. • n "llOUIO- "80 - reNSlTY OF VAPOR - LeS/CU· FT.8L - .. fl L1QUIO- "Uo-SUPERFICIAL VAPOR VELOCITY AT INITIAL FLOODING-FT/SEC.
S*-SURFACE AREA OF PACKING- SO. FT./CU.FT. TOWER VOLUMEF*-F'RACTION OF FREE VOLUME IN PACKING
.M -VISCOSITY OF LIQUID - CENTIPOISES9 -GRAVITY CONSTANT-32.2 FT./SEC~
-... _......
.OZ .03.04 .06 .08 .fO
SHERWOOu
.2
.1
.08
.06
.05
.04
001.01
.002,
~
· ~
1.5
1.01
AP/H <KFLA·15eo·85uI.85
DL50
.,I( < VISCOSITY OF VAPOR - CENT'POISESeo < DENSITY OF VAPOR - LBS.lCU. FT.U 'VAPOR VELOCITY - FT.lSEC.o < SIZE OF PACKING - INCHESFL "LIQUID RATE FACTORK <1.25 FOR BERL SADDLES
<I. 75 FOR RASCHIG RINGS
_1lI4.0
o
20
248
CONVERSION FACTORS
ox:°C + 273.2
(OF + 459.7)1.8°R/1.8
OR
1.8(OC) + 459.7of + 459.7
OF
1.8(OC) + 32
OR - 459.71.8("K) - 459.7
°C
(OF - 32)/1.8(OR - 491.7) /1.8
oK - 273.2
TEMPERATURETo ConvertFrom To°e .OF .oR .oK .
Centimeters .Meters __Inches .......................•......•..Feet.............•......•..............
LENGTHTo ConvertFrom To Cm Meters Inches Feet
Multiply By
1.000 0.0100 0.3937 0.03281100.0 1.000 :19.37 3.2812.540 0.0254 1.000 0.0833330.48 0.3048 12.00 1.000
Sq em......................•.Sqm .Sq in .Sq ft. ............•...........
·.0
AREATo ConvertFrom To Sqem
1.00010,0006.451929.0
Sq m Sq in.
M ullilJ/Y by
1.000 X10-4 O. J5501.000 1,5506.451 XIO-4 1.0000.09290 144.0
Sq ft
1.076 XI0-1
10.766.944 X10-1
1.000
:0
VOLUMETo ConvertFrom To Cu in. Cu ft US gal Imp g&~ eu em Liters Dbl (42's)
5
.0o
l>h,/liply by
Cu in 1.000 5.787 X10-4 4.329 X10-3 3.607 X10-3 16.39 0.01639 1.031 XIO-4Cu ft. 1,728 1.000 7.481 6.232 2.832XI04 28.32 0.1781'US gal 231.0 0.1337 1.000 0.8326 3,785 3.785 0.02381Imp gal. .. 277.3 0.160.~ 1.200 1.000 4,543 4.54a 0.02857Cu em 0.06102 3.531 XIO-' 2.642 X10-4 2.201 XIO-4 1.000 1.000 X10-3 6.290XIO-&Liters 61.02 0.03531. 0.2642 0.2201 1,000 1.000 6.290 X10-1
Bbl (42'S). 9,700 5.614 42.00 34.97 1.590XIO' 159.0 1.000
FORCETo ConvertFrom To
Poundals .Pounds .Dynes .Grams .
Poundals
1.00032.177.233XltJ'0.07093
Pounds Dynes
Multiply by
0.03108 Ia,8301.000 4.448 X10'2.248 X10-' 1.0002.205 X10-3 980.7
249
Grams
14.10453.61.020XltJ"1.000
250 DATA BOOK ON HYDROCARBONS
Sp gr .Lb/gal. .Lb/eu ft .
DENSITYTo ConvertFrom To Sp gr Lo/gal Lb/eu ft
Multiply by
1.000 8.3'17 62.430.1108 1.000 7.4810.01602 0.1337 1.000
PRESSURETo Convert
In. of Mmof Ftof H,OFrom To Lb/sq in. Lb/sq ft AIm Kg/sq em Hg Hg (60°F)
Multiply byLb/sq in... 1.000 144.0 0.06804 0.07031 2.036 51.70 2.307Lb/sq ft ... 6.944 X10-3 1.000 4.726XIo-' 4.882 XIO-' 0.01414 0.3592 0.01602Atm....... 14.70 2,116 1.000 1.033 29.92 760.0 33.90Kg/sq em.. 14.22 2,048 0.9678 1.000 28.96 735.5 32.81In. of Hg .. 0.4912 70.73 0.03342 0.03453 1.000 25.40 1.133Mm of Hg 0.01934 2.785 1.316 XlO-3 1.360 X10-3 0.03937 1.000 0.04461Ft of H,O 0.4335 62.43 0.02950 0.03048 0.8826 22.41 1.000
(60°F)
RATE OF FLOWTo Convert
Liters Gal Gal Cu ft Cu ft Cu ft Bbl BblFrom Toper min per hr per sec per min perhr per hr per dayper sec
M,diiply by
Liters/sec 1.000 15.85 951.2 0.03532 2.110 127.1Gal/min. 0.06308 1.000 60.00 2.228XIO-3 0.1337 8.010Gal/hr .. 1.052XI0-3 0.Ol667 1.000 3.713XIO-' 2.228 X 10-3 0.1337Cuft/see 28.30 448.9 2.693 XlO' 1.000 60.00 3,600Cuft/min 0.4717 7.481 448.9 0.01667 1.000 60.00Cu ft/hr. 7.862 X10-3 0.1246 7.481 2.778 X10-' 0.01667 1.000Bbl/hr .. 0.04415 0.6997 42.00 1.560 X10-3 0.09359 5.615Bbl/day. 1.840XlO-3 0.02917 1.750 6.498XlO-' 3.899XIO-3 0.2340
22.66 543.81.429 34.300.02382 0.5716641.1 1.538 XIO'10.69 256.50.1781 4.2721.000 24.000.04167 1.000
ENERGY. HEAT. AND WORKTo ConvertFrom To BTU Gm-cal Ft-Ib Hp-hr Kw-hr
Multiply by
BTU........... 1.000 252.0 777.5 3.928 X10-' 2.928 Xio-'Gm-eal ......... 3.968XlO-3 1.000 3.086 1.558 X 10-' 1.162 Xio-'Ft-lb ........... 1.286 X10-3 0.3241 1.000 5.050 X10-' 3.767 Xio-'Hp-hr.......... 2,547 6.417XIO' 1.980 XI0' 1.000 0.7457Kw-hr ......... 3,415 8.605XIO' 2.655XIO' 1.341 1.000
CONVERSION FACTORS 251
POWERTo Convert
BTU Ft-Ib Ft-Ib Kg-cal G-cal Tons ofFrom To per hr per min per sec Hp Kw per sec per sec refrig
Multiply by
BTU/hr .. 1.000 12.96 0.2160 3.928X1O-' 2.92SX10-' 6.999X1O- 5 0.06999 8.333X1o-'Ft-Ib/min 0.07715 1.000 0.01667 3.033X1O-5 2.260X1O-' 5.402X10-· 5.402X1O-' 6.431X1O-'Ft-Ib/sec 4.630 60.00 1.000 1.820X1o-' 1.356X10-3 3.241 X10-' 0.3241 3.858X1O-'Hp...... 2,547 33,000 550.0 1.000 0.7457 0.1782 178.2 0.2122Kw. . . . .. 3,415 44,250 737.6 1.341 1.000 0.2390 239.0 0.2845Kg-cal/sec 1.428X10' 1.851 X105 3,086 5.610 4.183 1.000 1,000 1.191G-cal/sec 14.28 185.1 3.086 5.610 X10-3 4.183 X10-3 0.0010 1.000 1.191 X1o-"Tons of 1.2ooX10' 1.555X105 2,592 4.712 3.514 0.8400 840.0 1.000refrig
INDEX
Acetylenes, physical constants of, 4Activity cOF!'f5cien~J 48
for light h)-d:ocubons b absorber oils, 67Adiabatic comp;'0mion of gases, 82-87Air, enthalp:i of, 182-183
specific }'ea.t cf, 88t,hermal conductivity of, 216viscosity of, 176
Alcohols, physical constants of, 6Aldehydes, physical constants of, 7Amagat's l,fr", 136-137Area, conversion table for, 249Aromati~s (see al~o individual compounds)
physicai constants of, 5specific gravity of saturated liquids, 142vapor pressure of Cs, 38viscosity of liquid, 162
A,S.T.M. distillation of petrolcum fractions,11
average boiling points frOID, 15equilibrium flash vaporir.ation curve
from, 223, 228·-229Avcrage boiling point3 of petrolcum frac
tions, 10-15from crude ass"y (T,B.P,) distilhtions,
11from 10% (or A.S.T.M.) distillations, i5
Benzene, enthalpy of, 112 I
latent heat of vaoorization of, 77physical constants of, 5specific gravity of the satnrated liql\id.
1·12vapor ?ressure of, 37viscosity of, Ift2
Berl saddles. 246-248Blending index, viscosity, 156, 173Boiling point, of hydrocarbons, 2-5
of miscellaneous gases, 9of miscellaneous organic compounds, 6-7of petroieum fractiallS, cubic average, 11
menu avern.ge, 10, 1<1-15molal average, 10, 14-15proper average for correlating physical
data, 10volume average, 10-11weight average, 10, 14-15
Bubble-cap towers (see also Fractionatingtowers)
overall plate efficiency, 233, 245Butadiene-1,3, physical constants of, 3
Butadiene-1,3, relative volatility of, 65spccific gmvity of the saturated liquid,
141v::.por pressure of, 36
Butane, enthalpy of, 101fugacity function of, 55latent heat of vaporization of, 94-95Mollier diagram for, 135physical constants of, 2relative volatility of C. hydrocarbons to,
65-66specific gravity of the saturated liquid,
140specific heat of vapor, 89vapor pressure of, 30viscosity of, 161
Butene-I, enthalpy of, 110physical constants of, 3relative volatility of, 65specific gravity of the saturated liquid,
141specific heat of vapor, 89vapor pressurc of, 30
Butene-2, cis- and trans-, enthalpy of, 111physical constants of, 3relative volatility of, 65specific gravity of the satur:l.ted liquid,
141specific heat of vapor, 89vapor pressure of, 30
Capacity of packed towers, 247Carbon dioxide, enthalpy of, 182-183
physical constants of, 9specific heat of, 88·~b.ermn.l conductivity of, 216viscosity of, 176
Cnrbon monoxide, enthalpy of, 182-183physical constants of, 9specific heat of, 88thermal conductivity oi, 216viscosity of, 176
Chn.racterization factor, definition, 12from gravity and boiling point, 16of typical crude fractions, 12, 17
Columns (see Fractionating towers)Combustion (see also Flue gas)
heat of, fuel oils, 178, 180hydrocarbons, 2-5miscellaneous gases, 9miscellaneous organic compounds, 0-7
253
254 INDEX
Combustion, heat of, paraffin and olefingases, 178, 181
petroleum fractions, 178, 180refinery gases, 178-179
heat available from, fuel oils, 186-188refincry gases, 184-185
Compressibility, of gases (see P-V-T relations)
of liquid petroleum fractions, 136, 143147
Compression, adiabatic, 82-87Conductivity, thermal (see Thermal con
ductivity)Constants, physical (see Physical constants)Contraction, friction loss in pipes uue to,
204Convection, heat 10SR by natural. 210Conversion, of °A.1'.I. to specific gravity
and pounds per I';allon, 138-139of °Engler to kinematic viscosi ty, 159of Redwood seconus to kinematic vis
cosity, 15Xof Saybolt Furol seconus to kineml\tic
viscosity, 15~-159
of Saybolt Thermo viscosity to kinelIultie viscosity, J60
of Saybolt Lniversal seconds to kinematic viscosity, 15X
tables [or, area, 2'19density, 250energy, heat, anel work, 250force (weight), 249lenl\th, 249power, 251pressure, 250rate of flow, 250temperatlll'e, 249volume, 249
Critical pressul'C, of hydrocarbons, 2-5, 74of miscellaneous gases, 9of miscellaneous organic compounds, 6-7of normal paraffins, 71pseudo-, of light hydrocarbon mixtllres,
71of petroleum frael-ions, 73
true, of pet.roleulll fractions, 74Critical telllpemture, of hydrocarbons. 2-5,
69-70of light hydrocarbons, 70of miscellaneous gases, 9of mis('ellaneous organic compounds, 6-7of petroleum fractions, 72
Crude assay distillation, definition, 1,average boiling points of petroleum frac
tions from, 14equilibrium flash vaporization curve
from, 223-229
Crude fractions, classification of various, 13typical, characteriz:Ltion factor of, 12, 17
gravity, °A.P.I., 1:·molecular weight of, 22-23viscosity index of lube fractions of, 12
Cubic average boiling of petroleum fractions, 11
Cyclohexane, physical constants of, 5vapor pressure of, 39
Cycloparaffins (see also individu:Ll compounds)
physical constants of, 5vapor pressure of, 39
Cyclopent:Lne, physical constants of, 5vapor preSSlll'e of, 39
Dalton's L:Lw, 45, 136Density (s('e also Specific gravity)
conversion table for, 250nitieal, hydrocarbons, 2-5
miscellaneous gases, 9miscell:Lneous oq;anic compounds, 6-7
Dimethylacetylene, physical const:Lnts of, 4vapor pressure of, 36
Diolefins (-,ee also individual compounds)physical constants of, 3-4specific 1\1'lwity of satumted liquids, 141
Distillation (see A.S.T.M., Crude assay,lind Tme boiling point distillations)
Efficiency of bubble-cap towers, 233, 245Emissivity, radiant heat coefficients of, 209Energy, conversion table for, 250En~lel', degrees, conversion to kinematic
visco!$ity, 159Elliargement, friction loss in p;pes due to,
201Enthalpy of, :IiI', 182-183
benzene, I 12butane, 101butene-I, 110butene-2, cis- and tl'ans-, IIIethane, 99ethylene, 10~
flue gas components, CO" CO, T, etc.,182-183
heptane, 104hexane, 103hydrocarbon vapors, eh:Lnge with pres-
sure, 92isobutane, 106isobutene, 110isopentane, 107methane, 98mixtures of light hydrocarbons, 78pentane, 102petroleum fractions, 80-82, 114-127
INDEX
Enthalpy of, propane, 100propylene, 109toluene, 113
Entropy (see ;\10Ilier diagrams)Equilibrium flash vaporization, of known
mixtures, 222of pctroleum fractions, 222-229
Ethanc, cnthalpy of, 99fugacity function of, 51latent heat of vaporization of, 94-95MollieI' diagram for, 131physical constants of, 2specific gravity of the saturated liquid,
140specific heat of vapor, 89vapor pressurc of, 28
Ethers, physical constants of, 7Ethylacetylcne, physical constants of, 4
vapor pressure of, 36Ethylene, cnthalpy of, 108
fugacity function of, 50latcnt hcat of vaporization of, 94-95Mollicr diagram for, 130physical constants of, 3specific gravity of the saturated liquid,
141specific heat of vapor, 89vapor prcssure of, 28
Feed pbtc, optimum, fractionating towers,234
Fenske cquation, mllumum theoreticalsteps at total reflux, 230
Fittings, equivalent lengths of, 193-194,202-203
Flash vaporization, equilibrium, of knownmixtures, 222 .
of petrolcum fractions, 222-229Flow of fluids, across wcirs, discharge
characteristics, 205friction factor for, 193, 198friction loss, contraction and enlarge-
ment, 204pressurc drop across tubc banks, 206streamlinc, prcssure drop in pipes, 198turbulent, equivalent Icngths of fittings,
202-203friction factor for, 193, 198pressurc drop in pipes, 193, 198-201
Flow of hcat (sec Heat tmnsfer)Flue gas, components, enthalpy of, 182-
183percent CO, in, 189pounds per pound of fuel, 190thcrmal conductivity of, 192viscosity of, 191
Force, convcrsion table for, 249
255
Fractionating towcrs (see also Fractiona-tion)
bubble cap, overall efficiency of, 233, 245optimum feed plate, 234packed, capacity of, 247
H.E.T.P., 2·16prcssurc drop in, 248
Fractionation, minimum reflux ratio, 231233
minimum theoretical steps (Fenske equation), 230-231
theoretical steps and reflux ratio, correlation of, 244
Francis formula for rectangular weirs,205
Friction factor, for flow of fluids in pipes,193, 198
Fuel oils, heat available from combustionof, 186-188
heat of combustion of, 178, 180Fugacity, of hydrocltJ'bon vapors, 62-63
of light hydrocarbons in absorber oils,activity cocfficient, 67
function of, butane, 55ethanc, 51ethylcnc, 50heptaue, 59hexane, 58hydrogcn, 61isobutanc, 54isopcntanc, 56mcthane, 49octane, 60pentane, 57propane, 53propylene, 52
Gas(es) (see also Fine gas, Refinery gas,and individual compounds)
miscellancous, enthalpy of, 182-183physical constants of, 9spccific hcat of, 88thermal conductivity of, 216viscosi ty of, 176
Gasolines, vapor prcssure of, 44Glycols, physical constants of, 6-7Gravity, convcrsion from °A.P.I. to specific
gravity and pounds per gallon, 138139
of typical crude fractions, 18specific (sec Specific gravity)
Heat, available from combustion (see Com.bustion)
capacity (see Spccific heat)content (see Enthalpy) .,latent (see Latent heat of vap0rlZatlon)
256 INDEX
•
Heat, loss, by no.tural convcction, 210by radiation, 209
transfer, to fluids insidc tubes, 211to fluids outside tubes, 212
Height equivalent to tI theoret,ir.otl phte,p:teked towers, 24(J
Heptane, enthalpy of, 10·1fugacity function of, 59latent hetlt of vaporization of, 94-95physical constants of, 2specific gravity of the saturated liquid,
140specific heat of vapor, 89vapor pressure of, 33viscosity of, 161
Hydroe:lrbon(s) (see also individual compounds an,l Arom"tics, Olefins, etc.)
critic"l temperature of, 69light, eritic"l temperature of, 70
latent heat of vaporization of, 94-95liquids, specific heat of, 93physical constants of, 2-5vapors, chauge in enthalpy with pressure,
92fugacity of, 62-63P-Y-T relations of, 136-137, 148
154specific hcat of, 89, 91
vapor IJre8sure of, 40 -·12Hydrogen, fugacity function of, 61
physical constants of, 9specific heat of, 88thermal conductivity of, 216viscosi ty of, 176
Isobutane, enthoJpy of, 106fugacity function of, 54latent heat of vaporization of, 94-95physical constants of, 2relative volatility of, 66specific gravity of the saturated liquid,
140vapor pressure of, 30
Isobutene, cnth:llpy of, 110physical constants of, 3relative volatility of, 65specific gravity of the satur:lted liquid,
141specific heat of vapor, 89vapor pressure of, 30
Isoparaffins (see also individual compounds)molecular weight of, 20physical constants of, 2-3
Isopenlane, enthalpy of, 107fugacity function of, 56lat~nt heat of vaporization of, 94-95pbysical constants of, 2
Isopen~ane, rel'!'tive volatility of, 66speCific gravIty of the saturated liquid
140 'vapor pressure of, 31
Ketones, physical constants of, 7Kinematic viscosity, blending index Irom,
173conversioll to, 15.1-156, 158--160definition of, 155temperature charts, 166-167
Latent heat of vtlporization, 76-77of hydrocarbons, 76-77of low boiling hydrocarbons, 94-95of miscellaneous organic compounds, 6-7of p"raffin hydroc:lrbons, 96-97of petroleum fractions, 76-77
Length, conversion t"ble fur, 249Log:lrithmie mean temperature diO'erence,
208, 217correction fotctors for lllulti-pas.~ ex
ch:lngers, 208, 218-221
Mean average boiling point, of pet,roleumfractions, 10-11, 14-15
Melting point, of hydroc:lrbons, 2-;;of inisr.ell,meous gases, 9of miscelbncous organic compounds,
6-7Methane, enth:llpy of, 98
fugacity function of, 49latent he:lt of v:lporiz:ltion or, U1-95MollieI' diagrams for, 128-129physic:ll constants of, 2specific gravity of thc satnrated liquid,
140specific heat of vapor, 89V:lpor pressure of, 27
Methy1:lcetylene, physical coustllnts of, 4v:lpor pressure of, 35
Methylcyclopentane, physical cOIl.;tants of,5
vapor pressure of, 39Minimum, reflux ratio, 231.-233
theoretical fmctionating steps, 230-231Molal avemge boiling point, of petroleum
fractions, 10-11, 14-15Molecular weight (see also Physical con-
stants)of p:lraffins, 20of petroleum fractions, 21of typical crude fractions, 22-23
Mollicr diagram (s) for, butane, 135ethane, 131ethylene, 130methane, 128-129
INDEX 257
Momer diallram(s) for, propane, 133-134propylene, 132, 134
Natural convection, heat loss to atmosphereby, 210
Nitrogen, enthalpy of, 182-183physical constants of, 9specific heat of, 88thcrmal conductivity of, 216viscosity of, 176
Octane, enthalpy of, 105fugacity function of, 60latent hcnt of vaporization of, 94-95physical constants of, 2specific gravity of the saturated liquid,
140specific hcat of vapor, 89vapor pressure of, 34viscosity of, 161
Oil(s) (sec also Crude fractions and Petroleum fractions)
fuel, heat "vailable from combustion of,186-1 8
hent of combustion of, 180lube, viscosity index of, 156, 168-172
Olefins (sec also Hydrocarbons and indi-vidunl compounds)
critical temperature of, 69hent of combustion of, 181physical constants of, 3specific gravity of, 141
Olefins-acetylenes, physical constants of,4-5
Optimum fccd point, fractionating towers,234 '
Organic compounds, miscellaneous, physical constants of, 6-7
Oxygen, enthalpy of, 182-183physical contitants of, 9specific hent of, 88thermal conductivity of, 216viscosity of, 176
Packed towers (see Fractionating towers,packed)
Paraffins (sec also Hydrocarbons and indi-vidual compouuds)
critical tcmperature of, 69heat of combustiou of, lSImolecular weight of, 20normal, critical pressure of, 71
latent heat of vaporization of, 96-97viscosity of, 16!
physical constants of, 2-3specific gravity of, 140
Pentane, enthalpy of, 102
Pentane, fugacity function of, 57latent heat of vaporizntion of, 94-95phYSICal constants of, 2specific gravity of the snturated liquid,
140specific heat of vapor, 89vapor pressure of, 31viscosity of, 161
Petroleum fractions (sce also Crnde frac-tions and Hydrocarbons)
average boiling points of, 10-11, 14-15critical temperature of, 72enthalpy of, 80-82, 11'1-127equilibrium 11,,"h vaporizntion of, 222-229hent of combustion of, 178, 180Intent heat of vaporization of, 76-77liquid, thermal conductivity of, 213
thermal ~xp:lllsion of, 136, 143-147pseudo-critical pressure of, 73pseudo-critical temperntuI'C nf, 72viscosit.y-temperature charts for, 166-167
Physicnl conRt'lnts of (sec also individualcompounds)
acetylenes, ,1alcohols, 6aillehydes, 7aromatics, 5cycloparaffins, 5diolefins, 3-4ethers, 7glycols, 6-7isoparaffins, 2-3ketones, 7normal paraflins, 2olefins, 3olcfins-ncetylcucs, 4-5
Pipe, steel, dimCllBions of, 202Plate efficiency of buhble-cap towers, 233,
245Power, conversion tahle for, 251Pressure, conversion tahle for, 250
critieat ('Pc Critic,d pres"ul'e)drop, across tube hanks, 206
due to fittings, 202for streamline flow in pipes, 198for turbulent flow in pipes, 198-201in commercial pipr.s, 193, 199-201
effect of, on enthalpy of hydrocarbonvapors, 92
on viscosity of gases, 177vapor (sec "apor.pressure)
Pl'Opadiene, physical constants of, 3specific gravity of the saturated liquid,
141vapor pressure of, 35
Propane, enthalpy of, 100fugacity function of, 53
258 INDEX
•
Propane, latent heat of vaporization of, 94-95
MollieI' diagrams for, 133-134physical constants of, 2specific gravity of the saturated liquid, 140specific heat of vapor, 89vapor pressure of, 29viscosity of, 161
Propylene, enthalpy of, 109fugacity function of, 52latent heat of vaporization of, 94-95Mollier diagrams for, 132, 134physical constants of, 3relative volatility of, 64specific gravity of the satumted liquid,
141specific heat of vapor, 89vapor pressure of, 29
Pseudo-critical pressure, 68of mixtures of light hydrocarbons, 71of petroleum fractions, 73
Pseudo-critical tempemture, 68of mixtures of light hydrocarbons, 70of petroleum fractions, 72
P-V-T rel:,tions of, hydrocarbon vapors,136-137, 148-154
mixtures of gases, 137
R, gas constant, numerical values of, 137Radiation, heat loss by, 209Raoult's Law, 45Raschig rings, 246-248Rate of flow, conversion table for, 250Rectification (see Fractionation)Redwood viscosity, conversion to kinematic
viscosity, 158Refinery gas, heat available from combus
tion of, 184-185heat of combustion of, 178-179
Reflux ratio (scc Fractionation)Reid vapol' pressure, conversion to true
vapor pressure, 4-1Relative volatility of, C, hydrocarbons,
65-66ethylene-ethane, 64isopentane-pentane, 66propylene-propane, 64
Reynold's number, e01'l'ection for equivalentlenl-(th of fittings from, 203
friction factor from, inside pipes, 198across tube banks, 206
heat trnnsfer film coefficient from, insidetubes, 211
across tube banks, 212
Saybolt, seconds Furol, conversion to kinematic viscosity, 158-159
Saybolt, seconds Universal, conversion tokinematic viscosity, 158
Thermo viscosity, conversion to kinematic viscosity, 160
Specific gravity, conversion from 0 \ PI138-139 , .. "
conversion to density, 250of aromatics, 5, 142of diolefins, 3-4, 141of hydrocarbons, miscellaneous gases and
organic compounds, 2-9of olefins, 3, 141of paraffins, 2-3, 140
Specific heat of, crude fmction vapors, 90hydrocarbon liquids, 93hydrocarbon and petroleum fraction
vapors, 91light hydrocarbon vapors, 89miscellaneous gases, 88
Steam, enthalpy of, 182-183specific heat of, 88thermal conductivity of, 216viscosity of, 176
Steel pipe, dimensions of, 202Streamline flow of fluids, pressure drop in
pipes, 198
Temperature, conversion table for, 249Theoretical stops, fractionating towers, 230,
233, 244Thermal conductivity of, flue gas, 192
hydrocarbon gases, 215liquid petroleum fractions, 213miscellaneous gases, 216water, 214
Thermal expansion of liquid petroleumfractions, 136, 143-147
Tolnene, enthalpy of, 113physical constants of, 5specific gravity of the saturated liquid, 142vnpor pre"sure of, 37viscosity of, 162
Towers (.,cc Fractionating towers)Tme boiling point distillation (<ee Crude
assay distillation)Tube banks, heat tmnsfer film coefficients,
212pressure drop ncross, 206
Turbulent flow of fluids (see Flow of fluids,turbulent)
Units, conversion of (see Conversion, tablesfor)
Valves, equivalent lengths of, 202Vapor pressure of, benzene, 37
bu tadiene-I ,3, 36
INDEX 259
Vapor pressure or. butane, 10butene-I, 30butene-2, cis- nnd trans-, 30cyclohexane, 39cyclopentane, 39dimethylacetylene, 36ethane, 28ethylacetylen~, 36ethylbenzene, 38ethylene, 28gasolines, 44heptane, 33hexane, 32hydrocarbons, 40-42isobutane, 30isobutene, 30isopentane, 31methane, 27methylacetylene, 35methylcyclopentane, 39octane, 34pentane, 31propadicne, 35propane, 29propylene, 29toluene, 37vinylncetylene, 36xylenes,38
Vaporizatiun, eqnilibrium flash (see Equilibrium flash vaporization)
latent he:lt of (see Latent heat of vaporizatiun)
Vinylacetylene, physical constants of,4
vapor pressure or, 36Viscosity, or aromatics, 162
of California crude fractions, 165conversion of (see Conversion)or flue gas, 191of gases at high pressures, 177of hydrocarbon vapors, 174-175of Mid-Continent oils, 164of miscellaneous gasf's, 176of normal paraffins, 161of Pennsylvania crude fractions, 163
Viscosity blending index, 156, 173Viscosity index of lube oils, 156, 168
172Viscosity-Temperature charts, 166-167Volume, conversion table for, 249
Water thermal conductivity ot, 214Weight, average boiling point of petroleum
fractions, 10-11, 14-15conversion table for, 249
Weirs dischal'i~e characteristics of, 205Work; converSIOn tables for, 250
Xylenes, ]lhysi~al constants of, 5specific grltvlty of the saturated liquid,
142vapor pressure of, 38viscosity of, 162