PROCESS ECONOMICS PROGRAM

SRI INTERNATIONAL Mrnlo Park, California 94025 Abstract

Process Economics Program Report No. 157

LDRRICATING OIL ADDITIVES

(Nay 1983)

Lubricating oil additives impart new properties to an oil or re- inforce desirable properties already possessed by the oil. Without additives, petroleum oils would not be satisfactory lubricants for high-performance gasoline or diesel engines. They are used to prevent sludge and varnish deposits in engines, to inhibit rust and corrosion, and to minimize wear and friction. The trend toward increased power a- from lighter and smaller engines has required increased concentrations of additives in lubricating oils.

Most oil additives are complex organic chemicals or mixtures eval- uated by their performance rather than their composition or purity. They are the basis for a multimilllon dollar industry conducted by some of the major oil companies and by a few independent companies.

This report contains process designs, economic evaluations, patent summaries, and a brief discussion of process chemistry for the follow- ing additives: a polyalkenyl succinimide dispersant; a einc dialkyl- dithiophosphate multifunctional antioxidant, corrosion inhibitor, and extreme-pressure additive; a magnesium alkylsulfonate detergent; an ethylene-propylene copolymer multifunctional viscosity index improver- dispersant; and a calcium alkylphenate detergent.

PEP'81 GEK -

6 Report No. 157

LUBRICATING OIL ADDITIVES

by GRANT E. RUSSELL a

May 1983

A private report by the PROCESS ECONOMICS PROGRAM - Menlo Park, California 94025

0 For detailed marketing data and information, the reader is referred to one of the SRI programs specializing in marketing research. The CHEMICALECONOMICS 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.

ii CONTENTS

1 INTRODUCTION ...... 1

2 SUMMARY ...... 7 Process for Polyisobutenyl Succinimide ...... 10 Process for Zinc Dialkyldithiophosphates ...... 10 Process for Overbased Magnesium Sulfonates ...... '10 Process for Ethylene-Propylene Copolymer ...... 11 Process for Overbased Calcium Phenate ...... 11 SuHmlaryofCosts ...... 12

3 INDUSTRY STATUS ...... 15

4 POLYALRENYL SUCCINIMIDES .... ; ...... 27 SunmmryofPatents ...... 28 Chemistry ...... 31 Process Description ...... 34 Process Discussion ...... 43 Cost Estimates...... 45

5 ZINC DIALRYLDITHIOPHOSPHES ...... 51 SunmaryofPatents ...... 52 Chemistry ...... 54 Process Description ...... 58 Process Discussion ...... 66 Cost Estimates ...... 69

6 SULFONATES ...... 81 Summary of Patents ...... 84 Chemistry ...... 87 Sulfonation ...... 87 Neutralization and Overbasing ...... 88 Process Description ...... 93 Process Discussion ...... 104 Cost Estimates ...... 108

iii CONTENTS

7 ETHYLENE-PROPYLENE COPOLYMERS ...... 115 SummaryofPatents ...... 119 Chemistry 120 Process Des&t;on ...... 122 Process Discussion ...... 127 Cost Estimates ...... 129

8 PHENATES ...... 135 Summary of Patents ...... 136 Chemistry ...... 138 Process Description ...... 141 Process Discussion ...... 147 Cost Estimates ...... 148

APPENDIX DESIGN AND COST BASES ...... 1 155

PATENTSUMMARYTABLES ...... 161

CITEDREFERENCES ...... 193

PATENTREFERENCES BY COMPANY . . . . . , ...... 207

iV ILLUSTRATIONS

3.1 U.S. Production of Lube Oil and Lube Oil Additives . . . . 20 3.2 Pounds of Oil Additives Produced Per Barrel of Lube Oil in U.S...... 21 4.1 Manufacture of Polyisobutenyl Succinimide Flowsheet...... 211 4.2 Manufacture of Polyisobutenyl Succinimide Effect of Plant Capacity on Total Fixed Capital . . . . . 47 4.3 Manufacture of Polyisobutenyl Succinimide Effect of Operating Level and Plant Capacity On Production (50% Concentration) ...... 50 5.1 U.S. Production of Phosphorodithioates ...... 53 5.2 Manufacture of Zinc Dialkyl Dithiophosphate Flowsheet...... 213 5.3 Manufacture of Zinc Dialkyl Dithiophosphates Effect of Plant Capacity on Total Fixed Capital . . . . . 71 5.4 Manufacture of Zinc Di(Isobutyl-Amyl) Dithiophosphate Effect of Operating Level and Plant Capacity On Production Cost (100% Basis) ...... 80 6.1 Oil Soluble Petroleum Sulfonates Total U.S. Production Rate ...... 85 6.2 Manufacture of Overbased Magnesium Sulfonate Flowsheet...... 215 6.3 Manufacture of Overbased Magnesium Sulfonate Effect of Production Capacity on Total Fixed Capital . . . 111 6.4 Manufacture of Overbased Magnesium Sulfonate (60% Concentration in Oil) Effect of Operating Level and Plant Capacity On Production Cost ...... 114 7.1 Typical Viscosity-Temperature Relationship For an SAE low-30 Motor Oil ...... 118 7.2 Manufacture of EPDM VI Improver-Dispersant a Flowsheet...... 217 a V ILLUSTRATIONS

7.3 Manufacture of EPDM VI Improver-Dispersant Effect of Production Capacity on Total Fixed Capital . . . . 131 7.4 Manufacture of EPDM VI Improver-Dispersant Effect of Operating Level and Plant Capacity Cn Production Cost ...... ; . 134 8.1 Manufacture of Cverbased Sulfurized Calcium Alkylphenate FlowSheet...... 219 8.2 Manufacture of Cverbased Calcium Alkylphenate Effect of Plant Capacity on Total Fixed Capital ...... 151 8.3 Manufacture of Cverbased Calcium Alkylphenate Effect of Operating level and Plant Capacity On Production Cost ...... 154

Vi TABLES

1.1 Summary of Major Lube Oil Additives and their Functions . . 2 2.1 World Market Shares of U.S. Lube Oil Additive Producers . . 8 2.2 Lube Oil Additives Cost Summary ...... 13 3.1 U.S. Consumption of Additives by Lubricant Type ...... 16 3.2 U.S. Consumption of Major Additives by Functional Type . . 17 3.3 U.S. Production of Lube Oil and Lube Oil Additives . . . . 19 4.1 Polyalkenyl Succinic Anhydride PatentSummary ...... 162 4.2 Polyalkenyl Succinimide Patent Summary ...... 163 4.3 Polyisobutenyl Succinimide Bases and Assumptions ...... 36 4.4 Polyisobutenyl Succinimide Major Equipment and Utilities Summary ...... 38 4.5 Polyisobutenyl Succinimide Stream Flows ...... 40 4.6 Polyisobutenyl Succinimide Summary of Waste Products ...... 42 4.7 Properties of Polybutenes ...... 44 4.8 Polyisobutenyl Succinimide Total Capital Investment ...... 46 4.9 Polyisobutenyl Succinimide Production Costs ...... , ...... 48 5.1 Zinc Dihydrocarbyldithiophosphates Patent Summary ...... 166 5.2 Zinc Di(Isobutyl-Amyl)Dithiophosphate Bases and Assumptions ...... 59 5.3 Zinc Di(Isobutyl-Amyl)Dithiophosphate Major Equipment and Utilities Summary ...... 62 5.4 Zinc Di(Isobutyl-Amyl)Dithiophosphate Stream Flows ...... 64

Vii TABLES

5.5 Zinc Di(Isobutyl-Amyl)Dithiophosphate Summary of Waste Products ...... 65 5.6 Zinc Di(Isobutyl-Amyl)Dithiophosphate Total Capital Investment (No.H2S Treatment) ...... 72 5.7 Zinc Di(Isobutyl-Amyl)Dithiophosphate Total Capital Investment (With H2S Treatment) ...... 74 5.8 Zinc Di(Isobutyl-Amyl)Dithiophosphate Production Costs (Without H2S Treatment) ...... 76 5.9 Zinc Di(Isobutyl-Amyl)Dithiophosphate Production Costs (With H2S Treatment) ...... 78 6.1 Range of Sulfonate Additive Properties ...... 84 6.2 Sulfonates PatentSummary ...... 170 6.3 Overbased Magnesium Sulfonate Bases and Assumptions ...... 95 6.4 Overbased Magnesium Sulfonate Major Equipment and Utilities Summary ...... 99 6.5 Overbased Magnesium Sulfonate StreamFlows ...... 101 6.6 Overbased Magnesium Sulfonate Summary of Waste Products ...... 103 6.7 Overbased Magnesium Sulfonate Total Capital Investment ...... 109 6.8 Overbased Magnesium Sulfonate Production Costs ...... 112 7.1 Ethylene-Propylene Copolymers PatentSunmnary ...... 182 0 7.2 EPDM VI Improver-Dispersant Bases and Assumptions ...... 123 7.3 EPDM VI Improver-Dispersant Major Equipment ...... 125 7.4 EPDM VI Improver-Dispersant Stream Flows ...... 126

Viii TABLES

7.5 EPDM VI Improver-Dispersant Total Capital Investment . . . . , ...... 130 7.6 EPDM VI Improver-Dispersant Production Costs ...... 132 8.1 Alkylphenates Patent Susnnary...... 188 8.2 Overbased Sulfurized Calcium Alkylphenate Bases and Assumptions ...... 142 8.3 Cverbased Calcium Alkylphenate Major Equipment and Utilities Summary ...... 144 8.4 Cverbased Sulfurized Calcium Alkylphenate Stream Flows ...... 145 8.5 Overbased Sulfurized Calcium Alkylphenate Summary of Waste Products ...... 146 8.6 Cverbased Calcium Alkylphenate

Total Capital Investment ...... l . l l 9 l l l . l 150 8.7 Overbased Calcium Alkylphenate

Production Costs ...... l l l . l l l l l . l l 152

IX