PROCESS ECONOMICS

PROGRAM SRI INTERNATIONAL

Menlo Park, California

94025

Abstract

Process Economics Program Report No. 142

OIL FIELD CHEMICALS

(December 1980)

In this report, four chemicals useful in oil fields are evaluated

for their production economics: petroleum sulfonate, anionic polyacryl-

amide, Fe-Cr lignosulfonate, and xanthan gum. In the case of anionic

polyacrylamide, a solution process , an emulsion process, and a radia-

tion process are compared; it has been found that the radiation process

has a cost advantage.

Cellulose ether, polyacrylate, lignite, starch and derivatives,

guar gum, polyamines , and tannins are described.

A general discussion of the chemicals used in the oil fields, as

well as a fairly comprehensive listing of such chemicals mentioned in

the patent literature, is included.

PEP '79 YCY

-

0 Report No. 142

OILFIELD CHEMICALS

by YEN-CHEN YEN

contributions by CHAO-HA0 CHIEN

December 1980

A private report by the

PROCESS ECONOMICS PROGRAM

Menlo Park, California 94025

For detailed marketing data and information, the reader is

referred to one of the SRI programs specializing in marketing

research. The CHEMICAL ECONOMICS HANDBOOK Program covers

most major chemicals and chemical products produced in the

United States and the WORLD PETROCHEMICALS Program covers

major hydrocarbons and their derivatives on a worldwide basis.

In addition, the SRI DIRECTORY OF CHEMICAL PRODUCERS services

provide detailed lists of chemical producers by company, prod-

uct, and plant for the United States and Western Europe.

I

I 0

ii

CONTENTS

1 INTRODUCTION. .........................

2 SUMMARY ............................

General Aspects ........................ Petroleum Sulfonate ..................... Polyacrylamide. ....................... Lignosulfonate. ....................... Xanthan Gum ......................... Micelle Flooding. ......................

Technical Aspects ....................... Petroleum Sulfonate by Sulfonation of Gas Oil Using Liquid SO. Polyacrylamide

...................... by a Solution Process. ............

Polyacrylamide by an Emulsion Process ............ Polyacrylamide by a Radiation Process ............ Lignosulfonate from Spent Sulfite Liquor. .......... Xanthan Gum from Rice Grain by Fermentation .........

3 OIL FIELD OPERATIONS AND USE OF CHEMICALS ...........

Oil Field Operations. ..................... Drilling ........................... Completion. ......................... Cementing .......................... Stimulation. ........................ Fracturing. ........................ Acidizing .........................

Production. ......................... Secondary Oil Recovery; Water Flooding. ........... Polymer Flooding; Surfactant Flooding ............ Stimulation and Plugging Related to Flooding. ........ Micelle Flooding. ...................... Miscible Drive. ....................... Thermal Drive ........................ Alkaline Flooding ...................... Gas Drive .......................... Tertiary Oil Recovery .................... Water Treatment .......................

Chemicals Used in Oil Field Operations. ............

1

3

8 11 11 12 12 12

15

15 15 19 19 20 20 20 21 21 22 22 23 23 23 24 24 24 25 25

iii

CONTENTS

4 INDUSTRY STATUS. ....................... 31

Oil Field Chemicals in General ................ 31 Petroleum Sulfonates ..................... 36 Polyacrylamides ........................ 36 Lignosulfonates. ....................... 39 XanthanGum ......................... 39

5 PETRoLEUMsuLPoNATEs ..................... 43

Chemistry ........................... 44 Review of Processes. ..................... 45 Feed ............................. 48 Sulfonation Agent. ...................... 52 Reaction Conditions. ..................... 52 Products ........................... 53 A Process for Production of Petroleum Sulfonate Using Liquid Anhydrous Sulfur Trioxide ............... 55

Process Description. .................... 55 Process Discussion ..................... 63 Cost Estimates. ...................... 64

A Process for Making Petroleum Sulfonate Using In-situ Generated Sulfur Trioxide Gas ................ 69 Process Description. .................... 69 Process Discussion ..................... 77 Cost Estimates. ...................... 77

6 POLYACRPLAMIDES. .......................

Review of Processes. ..................... A Solution Process for Making Anionic PAA Having a Mel Wt of about 7-15 Million ................. An Emulsion Process for Making Anionic PAA Having a Mol Wt of about 10 Million. .................

Process Description, .................... Process Discussion, .................... Cost Estimates. ......................

A Radiation Process for Making Anionic PAA Raving a Mol Wt of about 20 Million .................. Process Description ...................... Process Discussion ..................... Cost Estimates. ......................

Canparison of the Three Processes. ..............

81

81

104

105 105 116 117

117 117 128 129 129

iV

CONTENTS

7 LIGNOSULFONATE. ........................ 133

Chemistry ........................... 134

Review of Processes ...................... 136

Feed ............................. 136 Separation. ......................... 144 Base Exchange ........................ 146

Oxidation .......................... 146 Other Modifications ..................... 147 Products ...................... 147

A Process for Production of Ferro-Chrome Lignosulfonate from Spent Sulfite Liquor Using Three-Stage Lime Precipitation. ...................... 149 Process Description ..................... 149 Process Discussion. ..................... 158

Cost Estimates. ....................... 160

8 XANTHAN GUM........................................... 169

Chemistry ........................... 169 Application of Xanthan Gum in Oil Fields. ........... 171 Review of Processes ...................... 171 Raw Material. ........................ 171 Bacteria ........................... 171 Nutrients .......................... 177 Fermentation Conditions ................... 178 Batch or Continuous ..................... 178 Equipment .......................... 179 Separation. ......................... 179 Product ........................... 179

Evaluation of a Process for Making Xanthan Gum. ........ 179 Process Description ..................... 179 Process Discussion. ..................... 188 Cost Estimates. ....................... 188

9 OTHER IMPORTANT OIL FIELD CHEMICALS .............. 193

Cellulose Derivatives ..................... 193 Polyacrylate and Other. .................... 193 Lignite ............................ 193 Starch and Derivatives. .................... 194 Guar Gum (or Similar Gums) and Derivatives. .......... 194 Polyamines and Derivatives. .................. 194 Tannins ............................ 194

V

CONTENTS

APPENDIX A DESIGN AND COST BASIS. . . . . . . . . . . . . . . . 199

APPENDIX B CHEMICALS USEFUL IN OIL FIELDS BASED ON THE PATENT LITERATURE . . . . , . . . . . . . . . 203

APPENDIX C SOME PROPERTIES OF SURFACTANTS . . . . . . . . . . . 249

APPENDIX D MICELLE SOLUTIONS . . . . . . . . . . . , . . . . . 251

APPENDIX E COST ANALYSIS AND ITS APPLICATIONS TO THE STUDY OF MICELLE FLOODING . . . . . . . . . . 255

CITED REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . 257

PATENT REFERENCES BY COMPANY. . . . . . . . . . . . . . . . . . . . 315

vi

ILLUSTRATIONS

l 3.1

5.1

a 5.2

5.3

5.4

5.5

6.1

6.2

6.3

6.4

7.1

0 7.2

7.3

7.4

Oil Field Operation. . . . . . . . . . . . . . . . . .

Petroleum Sulfonate from Gas Oil and Liquid Sulfur Trioxide - 150 MM lb/yr Flow sheet....................................

Petroleum Sulfonate from Liquid SO Effect of Operating Level and Plan 9 Capacity on Production Cost . . . . . . . . . . . . . . . . . .

Petroleum Sulfonate from Liquid SO Effect of Operating Level and Plan 9 Capacity on Product Value . . . . . . . . . . . . . . . . . . .

Petroleum Sulfonate from Crude Oil and In Situ Generated Sulfur Trioxide Gas Flow sheet....................................

Petroleum Sulfonate from Crude Oil and In Situ Generated SO Gas Effect of Operating Leve1 and Plant Capacity on Production Cost . . . . . . . . . . . . . . . . . .

Polyacrylamide Effect of Operating Level and Plant Capacity on Production Cost . . . . . . . . . . . . . . . . . .

Polyacrylamide Effect of Operating Level and Plant Capacity on Product Value . . . . . . . . . . . . . . . . . . .

Emulsion Process for Making Anionic Polyacrylamide . .

Radiation Process for Making Anionic Polyacrylamide. .

Ferro-Chrome Lignosulfonate from Spent Sulfite Liquor - 150 MM lb/yr Flow sheet....................................

Recovery of Organic Acid Salts . . . . . . . . . . . .

Ferro-Chrome Lignosulfonate from Spent Sulfite Liquor Effect of Operating Level and Plant Capacity on Production Cost . . . . . . . . . . . . . . . . . .

Ferro-Chrome Lignosulfonate from Spent Sulfite Liquor Effect of Operating Level and Plant Capacity on Product Value . . . . . . . . . . . . . . . . . . .

. . . 16

. . . 333

. . . 67

. . . 68

. . . 335

. . . 80

. . . 108

. . . 109

. . . 115

. . . 127

337 . . .

. . . 159

. . . 164

. . . 165

Vii

ILLUSTRATIONS

8.1 Structure of Xanthan Gum. . . . . . . . . . . . . . . . . . . 169

8.2 Xanthan Gum from Hydrolysis and Fermentation of Rice Grains Capacity = 10 Million lb/yr Flow sheet....................................339

8.3 Xanthan Gum from Hydrolysis and Fermentation of Rice Grains Effect of Operating Level and Plant Capacity on Production Cost. . . . . . . . . . . . . . . . . . . . . . 191

8.4 Xanthan Gum from Hydrolysis and Fermentation of Rice Grains Effect of Operating Level and Plant Capacity on-Product Value. . . . . . . . . . . . . . . . . . , . . . . 192

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0

Viii

TABLES

2.1

2.2

2.3

2.4

2.5

3.1

3.2

3.3

4.1

4.2

4.3

4.4

4.5

4.6

4.7

5.1

5.2

5.3

5.4

5.5

Petroleum Sulfonate Cost Features. ....................... 4

Polyacrylamide Cost Features. ....................... 6

Fe-Cr Lignosulfonate Cost Features. ....................... 7

Kanthan Gum Cost Features. ....................... 9

Cost Components for Micelle Flooding ............ 10

Various Kinds of Drilling Fluids .............. 17

Functional Agents Used in Oil Field Operations ....... 26

Important Materials Used in Oil Field Operations ...... 28

U.S. Consumption of Oil Field Chemicals in 1978. ...... 32

Estimated U.S. Consumption of Selected Oil Field Chemicals. .................... 33

U.S. Major Supply and Service Companies for Oil Field Chemicals ................... 34

Chemical Potentials for Enhanced Oil Recovery. ....... 35

U.S. Producers of Petroleum Sulfonate. ........... 37

U.S. Producers of Polyacrylamides. ............. 38

U.S. Producers of Lignosulfonates. ............. 41

Petroleum Sulfonate - Mahogany Sulfonates Patent Smmary ....................... 46

Petroleum Sulfonate for Oilfields Patent Summary ....................... 49

Alkane Sulfonate from Petroleum Patent Summary ....................... 51

Reactors for Continuous Organic Sulfonation Patent Summary ....................... 51

Production of Petroleum Sulfonate from Gas Oil and Liquid Sulfur Trioxfde Design Bases and Assumptions ................ 57

IX

TABLES

5.6 Petroleum Sulfonate from Gas Oil and Liquid Sulfur Trioxide Stream Flows. . . , . . . . . . . . . . . . . . , . . . . . 58

5.7 Petroleum Sulfonate from Gas Oil and Liquid Sulfur Trioxide Major Equipment. . . . . . . . . . . . . . . . . . . . . . 60

5.8 Petroleum Sulfonate from Gas Oil and Liquid Sulfur Trioxide Utilities Summary , . . . . . . . . . , . . . , . . . . . . 62

5.9 Petroleum Sulfonate from Gas Oil and Liquid Sulfur Trioxide Total Capital Investment. . . . . . . . . . . . . . . . . . 65

5.10 Petroleum Sulfonate from Gas Oil and Liquid Sulfur Trioxide Production Costs. . . . . . . . . . . . . . . . . . . . . . 66

5.11 Production of Petroleum Sulfonate from Crude Oil and In Situ Generated Sulfur Trioxide Gas Design Bases and Assumptions. . . . . . . . . . . . . . . . 71

5.12 Petroleum Sulfonate from Crude Oil and In Situ Generated Sulfur Trioxide Gas Stream Flows. . . . . . . . . . . . . . . . . . . . . . . . 72

5.13 Petroleum Sulfonate from Crude Oil and In Situ Generated Sulfur Trioxide Gas Major Equipment . . . . . . . . . . . . . . . . . . . . . . 74

5.14 Petroleum Sulfonate from Crude Oil and In Situ Generated Sulfur Trioxide Gas Utilities Summary . . . . . . . . . . . . . . . . . . . . . 76

5.15A Petroleum Sulfonate from Crude Oil and In' Situ Generated Sulfur Trioxide Gas Total Capital Investment.................. 78

5.15B Petroleum Sulfonate from Crude Oil and In Situ Generated Sulfur Trioxide Gas Capital Investment by Section . . . . . . ; . . . . . . . . 78

5.16 Petroleum Sulfonate from Crude Oil and In Situ Generated Sulfur Trioxide Gas Production Costs. . . . . . , . . . . . . . . . . . . . . . 79

X

6.1

6.2

6.3

6.4

6.5

6.6

6.7

6.8

6.9

6.10

6.11

6.12

6.13

6.14A

6.14B

6.15

6.16

TABLES

Applications of PAA (Polyacrylamide) and Derivatives in Oil Fields. . . . . . . . . . . . . . . . .

Solution Polymerization of Acrylamide Patent Summary....................................

Drying Patent Summary...................................

Emulsion Polymerization Patent Summary...................................

Polymerization of Acrylamide by Radiation or Photoinitiation Patent Summary...................................

Copolymers Containing Acrylamide Patent Summary...................................

Hydrolysis of PAA Patent Summary...................................

PAA Derivatives Patent Summary...................................

Stabilizers Added to PAA Patent Summary...................................

Treatment of PAA Gels or Powder Patent Summary...................................

Preparation of PAA Water Solution Patent Summary...................................

Polyacrylamide from Acrylonitrile or Polyacrylonitrile Patent Summary...................................

Acrylamide Polymerized In Situ Patent Summary...................................

Solution Process for Making Anionic Polyacrylamide Total Capital Investment . . . . . . . . . . . . . . . . .

Solution Process for Making Anionic Polyacrylamide Capital Investment by Section. . . . . . . . . . . . . . .

Solution Process for Making Anionic Polyacrylamide Production Costs . . . . . . . . . . . . . . . . . . . . .

Emulsion Process for Waking Anionic Polyacrylamide Design Bases Assumptions . . . . . . . . . . . . . . . . .

84

87

90

91

94

96

97

98

99

100

101

103

103

106

106

107

111

Xi

6.17

6.18

6.19

6.2OA

6.2OB

6.21

6.22A

6.22B

6.23

6.24

6.25

6.26

6.27

6.28A

6.28B

6.29

Emulsion Process for Making Anionic Polyacrylamide Stream Flows........................

Emulsion Process for Making Anionic Polyacrylamide Major Equipment. . . . . . . . . . . . . . . . . . . . . .

Emulsion Process for Making Anionic Polyacrylamide Utilities Summary. . . . . . . . . . . . . . . . . . . . .

Emulsion Process for Making Anionic Polyacrylamide Total Capital Investment. . . , . . . . . . . . . . . . . .

Emulsion Process for Making Anionic Polyacrylamide Capital Investment by Section . . . . . . . . . . . . . . .

Emulsion Process for Making Anionic Polyacrylamide Production Costs . . . . . . . . . . . . . . . . . . . . .

Emulsion Process @sing Acrylic Acid) for Anionic Polyacrylamide Total Capital Investment. . . . . . . . . . . . . . . . . .

Emulsion Process (Using Acrylic Acid) for Anionic Polyacrylamide Capital Investment by Section . . . . . . . . . . . . . . .

Emulsion Process (Using Acrylic Acid) for Anionic Polyacrylamide Production Costs . . . . . . . . . . , . . . . . . . . . .

Radiation Process for Making Anionic Polyacrylamide Design Bases and Assumptions. . , . . . . . . . . . . . . .

Radiation Process for Making Anionic Polyacrylamide Stream Flows . . . . . . . . . . . . . . . . . . . . . . .

Radiation Process for Making Anionic Polyacrylamide Major Equipment......................

Radiation Process for Making Anionic Polyacrylamide Utilities Summary. . . . . . . . . . . . . . . . . . . . .

Radiation Process for Making Anionic Polyacrylamide Total Capital Investment. . . . . . . . . . . . . . . . . .

Radiation Process for Making Anionic Polyacrylamide Capital Investment by Section . . . . . . . . . . . . . . .

Radiation Process for Making Anionic Polyacrylamide Production Costs . . . . . . . . . . . . . . . . . . . . .

112

113

114

118

118

119

120

120

121

123

124

125

126

130

130

131

Xii

7.1

7.2

7.3

7.4

7.5

7.6

7.7

7.8

7.9

7.10

7.11

8.1

8.2

8.3

8.4

8.5

8.6

TABLES

Lignosulfonates Patent Summary....................................

Lignosulfonates for Various Oilfield Applications Patent Summary....................................

Lignin Compounds Other than Lignosulfonates Patent Summary..........................................

Ferro-Chrome Lignosulfonate from Spent Sulfite Liquor Design Bases and Assumptions. . . . . . . . . . . . . . . .

Ferro-Chrome Lignosulfonate from Spent Sulfite Liquor Stream Flows......................................

Ferro-Chrome Lignosulfonate from Spent Sulfite Liquor Major Equipment , . . . , . . . . . , . . . . . . . . . . .

Ferro-Chrome Lignosulfonate from Spent Sulfite Liquor Utilities Summary . . . . . . . . . . . . . . . . . . . . .

Ferro-Chrome Lignosulfonate from Spent Sulfite Liquor Total Capital Investment. . . . . . . . . . . . . . . . . .

Ferro-Chrome Lignosulfonate from Spent Sulfite Liquor Production Costs. . . . . . . . . . . . . . . . . . . . . .

Ferro-Chrome Lignosulfonate from Spent Sulfite Liquor with Coproduction Total Capital Investment. . . . . . . . . . . . . . . . . .

Ferro-Chrcnne Lignosulfonate from Spent Sulfite Liquor with Coproduction Production Costs. . . . . . . . . . . . . . . . . . . . . .

Xanthan Gum Used in Oil Fields Patent Summary...........................................

Xanthan Gum Production Processes Patent Summary....................................

Xanthan Gum Manufacture Design Bases and Assumptions. . . . . . . . . . . . . . . .

Xanthan Gum from Hydrolysis and Fermentation of Rice Grain Stream Flows . . . . . . . . . . . . . . . . . . . . . . .

Xanthan Gum from Hydrolysis and Fermentation of Rice Grains Major Equipment. . . . . . . . . . . . . . . . . . . . . .

Xanthan Gum from Hydrolysis and Fermentation of Rice Grains Utilities Summary . . . . . . . . . , . . . . . . . . . . .

Xiii

137

142

143

151

152

155

157

161

162

166

167

172

173

182

183

185

187

TABLES

8.7 Xanthan Gum from Hydrolysis and Fermentation of Rice Grains Total Capital Investment. ................. 189

8.8 -than Gum from Hydrolysis and Fermentation of Rice Grains Production Costs ..................... 190

9.1 Cellulose and Derivatives for Oilfield Applications .... 195

9.2 Lignite and Derivatives, and Similar Products Patent Summary ...................... 196

9.3 Starch Derivatives and Modified Starch Patent Summary ...................... 197

9.4 Natural Gums and Derivatives Patent Summary ...................... 198

9.5 Tannins in Oilfields Patent Summary ...................... 198

B.l Anionic Surfactants .................... 205

B.2 Non-Ionic Surfactants ................... 209

B.3 Cationic Surfactants. ................... 212

B.4 Amphoteric Surfactants. .................. 214

B.5 Polymers ......................... 216

B.6 Natural Organic Materials and Derivatives Thereof ..... 221

B.7 Petroleum, Oil, Gas Fractions and Derivatives ....... 224

B.8 Organic Chemicals. .................... 225

B.9 Inorganic Chemicals .................... 241

B.10 Mineral Products ..................... 246

D.l Composition of Some Micelle Solutions ........... 253

xiv