Preview-9781466551503 A24034580

ChemiCal iNDUSTRieS/138
Refining Used
Lubricating Oils
James G. Speight • Douglas I. Exall
Refining Used
Lubricating Oils
CHEMICAL INDUSTRIES
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Refining Used
Lubricating Oils
James G. Speight • Douglas I. Exall
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Contents
Preface.................................................................................................................... xiii
Authors...................................................................................................................... xv
Chapter 1 Manufacture of Lubricating Oil............................................................1

1.1 Introduction................................................................................ 1
1.2 Base Oil Manufacture from Petroleum Sources......................... 2
1.2.1 Base Oil Manufacture...................................................2
1.2.1.1 Distillation..................................................... 3
1.2.1.2 Chemical Refining Processes........................ 6
1.2.1.3 Hydroprocessing............................................ 7
1.2.1.4 Solvent Refining Processes............................ 8
1.2.1.5 Solvent Dewaxing........................................ 10
1.2.1.6 Catalytic Dewaxing and
Hydroisomerization..................................... 11
1.2.2 Older Processes........................................................... 11
1.2.3 Finishing Processes..................................................... 13
1.3 Blending.................................................................................... 15
1.4 Composition and Properties..................................................... 17
1.5 Uses.......................................................................................... 19
1.6 Synthetic Lubricating Oil......................................................... 21
1.6.1 Poly Alpha-Olefins...................................................... 22
1.6.2 Poly Internal-Olefins................................................... 23
1.6.3 Poly-Butenes................................................................ 23
1.6.4 Organic Esters............................................................. 23
1.6.5 Polyglycols...................................................................25
1.6.6 Silicones......................................................................25
1.6.7 Blended Oils................................................................26
1.6.8 Biolubricants................................................................26
1.7 Base Oil Properties................................................................... 27
1.7.1 Aniline Point............................................................... 27
1.7.2 Cloud Point.................................................................. 27
1.7.3 Color............................................................................28
1.7.4 Density and API Gravity.............................................28
1.7.5 Distillation...................................................................28
1.7.6 Flash Point...................................................................28
1.7.7 Pour Point.................................................................... 29
1.7.8 Refractive Index and Refractivity Intercept................ 29
1.7.9 Viscosity...................................................................... 29
1.7.10 Viscosity–Gravity Constant........................................ 29
v
vi Contents
1.7.11 Viscosity Index............................................................ 30

1.7.12 Volatility...................................................................... 30
1.8 Additives................................................................................... 30
1.8.1 Antifoaming Agents.................................................... 32
1.8.2 Antioxidants................................................................ 32
1.8.3 Antiwear Additives...................................................... 33
1.8.4 Corrosion and Rust Inhibitors..................................... 33
1.8.5 Detergents and Dispersants.........................................34
1.8.6 Pour Point Depressants................................................ 35
1.8.7 Viscosity Index Improvement..................................... 36
1.9 Performance............................................................................. 37
References........................................................................................... 38
Chapter 2 Types and Properties of Lubricating Oils........................................... 43

2.1 Types of Lubricating Oils......................................................... 43
2.1.1 Lubricating Oils Derived from Mineral Oils..............44
2.1.2 Lubricating Oils Derived from Synthetic Sources......44
2.2 Solid Lubricants and Greases................................................... 45
2.2.1 Solid Lubricants.......................................................... 45
2.2.2 Greases........................................................................ 45
2.3 Use and Applications................................................................ 48
2.3.1 Automotive Engines.................................................... 48
2.3.2 Diesel Engines............................................................. 49
2.3.3 Tractors and Other Engines......................................... 50
2.3.4 Aviation Oils............................................................... 50
2.3.5 Turbine Oils................................................................. 51
2.3.6 Compressor Oils.......................................................... 53
2.3.7 Industrial Oils.............................................................. 53
2.3.8 Marine Oils................................................................. 54
2.4 Properties of Lubricating Oils.................................................. 55
2.4.1 Viscosity and Its Temperature Dependence................ 55
2.4.2 Viscosity Index............................................................ 58
2.4.3 Pressure Dependence of Viscosity.............................. 59
2.4.4 Density........................................................................60
2.4.5 Pour Point and Cloud Point.........................................60
2.4.6 Total Acid Number and Total Base Number...............60
2.4.7 Ash Formation............................................................. 61
2.4.8 Flash Point and Fire Point........................................... 62
2.4.9 Volatility or Noack Evaporation Loss......................... 62
2.4.10 PONA Analysis........................................................... 62
2.4.11 API Lubricant Base Stock Oil Groups........................ 63
2.4.12 Additives to Base Stock Oils....................................... 63
2.4.12.1 Antioxidant Additives..................................64
2.4.12.2 Viscosity Modifier Additives.......................64
Contents vii
2.4.12.3 Antiwear and Extreme Pressure Additives.... 65

2.4.12.4 Friction Modifiers........................................66
2.4.12.5 Detergents and Dispersants.........................66
2.4.12.6 Corrosion Inhibitors..................................... 67
2.4.12.7 Antifoaming Agents.................................... 67
2.4.12.8 Pour Point Depressants................................ 68
2.4.12.9 Demulsifiers and Emulsifiers....................... 68
2.4.12.10 Dyes............................................................. 68
2.4.13 SAE/API Classification............................................... 69
2.4.14 ILSAC Classification................................................... 69
2.4.15 Classification by the Association des
Constructeurs Européens d’Automobiles.................... 69
2.4.16 Original Equipment Manufacturers (OEM)
Classifications.............................................................. 70
2.5 Use of Test Data........................................................................ 70
References........................................................................................... 71
Chapter 3 Used Lubricating Oils......................................................................... 73

3.1 Introduction.............................................................................. 73
3.2 Causes of Oil Degradation....................................................... 76
3.3 Amount of Used Oils................................................................ 77
3.4 Collection................................................................................. 78
3.5 Types of Used Oils and Analyses.............................................80
3.6 Recycling and Re-Refining Capacities.....................................84
3.6.1 Re-Refining Capacities................................................84
3.6.2 Used Oil Management................................................. 85
3.7 Environmental Aspects of Used Oil Management................... 87
3.8 Converting Used Oil into Useable Oil...................................... 89
References...........................................................................................90
Chapter 4 Composition and Treatment................................................................ 91

4.1 Introduction.............................................................................. 91
4.2 Primary Treatment................................................................... 95
4.3 Separation.................................................................................96
4.3.1 Chemical Separation...................................................96
4.3.2 Physical–Chemical Separation....................................97
4.3.3 Physical Separation.....................................................97
4.4 Finishing................................................................................... 98
4.4.1 Clay Treatment............................................................ 98
4.4.2 Catalytic Processes.................................................... 100
4.5 Test Methods.......................................................................... 101
4.6 Environmental Aspects.......................................................... 107
References......................................................................................... 111
viii Contents
Chapter 5 Combustion of Used Engine Oil....................................................... 115

5.1 Introduction............................................................................ 115
5.2 Direct Combustion: Use as a Fuel.......................................... 118
5.3 Combustion Chemistry and Equipment................................. 119
5.3.1 Fuels.......................................................................... 120
5.3.2 Combustion Chemistry.............................................. 120
5.3.3 Combustion Equipment............................................. 122
5.3.3.1 Boilers........................................................ 123
5.3.3.2 Turbines..................................................... 124
5.3.3.3 Internal Combustion Engines.................... 124
5.4 Fuel Oil Properties................................................................. 125
5.4.1 API and Specific Gravity or Density......................... 125
5.4.2 Flash Point and Fire Point......................................... 125
5.4.3 Viscosity.................................................................... 126
5.4.4 Pour Point.................................................................. 126
5.4.5 Cloud Point................................................................ 127
5.4.6 Sediment and Water Content..................................... 127
5.4.7 Ash Content............................................................... 128
5.4.8 Carbon Residue......................................................... 128
5.4.9 Sulfur Content........................................................... 128
5.4.10 Distillation................................................................. 129
5.4.11 Corrosion................................................................... 129
5.4.12 Heat Content.............................................................. 129
5.4.13 Stability..................................................................... 130
5.4.14 Spot Test for Compatibility....................................... 131
5.5 Environmental Risks.............................................................. 131
5.6 Postcombustion Capture......................................................... 131
5.7 Used Oil Combustion............................................................. 132
5.7.1 Particulate Matter...................................................... 133
5.7.2 Sulfur Oxides............................................................ 133
5.7.3 Chlorinated Organics................................................ 133
5.7.4 Flue Gas Treatment................................................... 133
5.7.5 Control Technologies................................................. 134
5.8 Combustion with Heavy Fuel Oil........................................... 134
5.8.1 Particulate Matter Emissions.................................... 135
5.8.2 Sulfur Dioxide Emissions......................................... 135
5.8.3 Chlorinated Organic Emissions................................ 136
5.8.4 Other Organic Emissions.......................................... 136
5.8.5 Control Technologies................................................. 136
5.8.6 Conclusions............................................................... 136
5.9 Combustion in Cement Kilns................................................. 137
5.10 Combustion in Hot-Mix Asphalt Plants................................. 137
References......................................................................................... 138
Contents ix
Chapter 6 Alternative Processing Options......................................................... 141

6.1 Introduction............................................................................ 141
6.2 Refinery Processing................................................................ 144
6.2.1 General Options........................................................ 145
6.2.2 Conversion to Lubricating Oils................................. 145
6.3 Cogeneration........................................................................... 147
6.3.1 Diesel Engine Coupled with a Generator.................. 149
6.3.2 Gas Turbine-Steam Turbine...................................... 149
6.4 Regeneration Residues............................................................ 149
6.4.1 Analyses.................................................................... 150
6.4.2 Road Oiling and Asphalt Additive............................ 150
6.5 Environmental Management.................................................. 151
References......................................................................................... 153
Chapter 7 Refining Processes for Used Oil Recycling to Base Oils or Fuels.... 155
7.1 Introduction............................................................................ 155
7.2 The Acid/Clay Processes........................................................ 156
7.3 Simple Distillation and Predistillation Processes.................. 158
7.3.1 The Sotulub Process.................................................. 158
7.3.2 The Mohawk Pretreatment Process........................... 161
7.3.3 The Enprotec Process................................................ 162
7.4 Distillation/Clay Processes..................................................... 168
7.4.1 The Viscolube Italiana S.p.A. Process...................... 168
7.4.2 The Pesco-Beam Process.......................................... 171
7.5 Distillation and Hydrogenation Processes.............................. 175
7.5.1 The Mohawk and Chemical Engineering
Partners–Evergreen Processes.................................. 175
7.5.2 The Phillips Petroleum (PROP) Process................... 178
7.5.3 The Exxon/Imperial Oil Process.............................. 186
7.5.4 The Kinetics Technology International B.V.
(KTI) Process............................................................ 195
7.5.4.1 Version 1 with a Single Wiped Film
Evaporator.................................................. 197
7.5.4.2 Version 2 with Two Wiped Film
Evaporators................................................ 197
7.5.5 The Viscolube/Axens Revivoil Process..................... 198
7.6 Distillation/Solvent Extraction Processes..............................200
7.6.1 The Lubrizol Corporation Processes.........................200
7.6.2 The Bartlesville Energy Research Center
(BERC)/US Dept. of Energy (DOE) Process............ 201
7.6.3 The Snamprogetti Processes.....................................205
7.6.4 The Texaco Inc. Process............................................ 211
7.6.5 The Delta Central Refining Inc. Process................... 211
7.6.6 The Krupp Koppers Process..................................... 214
7.6.7 The Interline Hydrocarbon Inc. Process................... 218
x Contents
7.6.8 The Shell Upgrading Process.................................... 221

7.6.9 The Sener Ingenieria y Sistemas S.A./Interline
Process: The Ecolube Plant.......................................224
7.6.10 The Modified Sener Process..................................... 227
7.6.11 Further Modification to the Sener Process................ 231
7.6.12 Institut Français du Pétrole (IFP) Process................. 233
7.6.13 IFP/Snamprogetti Process......................................... 237
7.6.14 The Bechtel Process.................................................. 241
7.6.15 The Mineraloel-Raffinerie Dollbergen
GmbH Process........................................................... 242
7.7 Hydrogenation/Distillation Processes.................................... 245
7.7.1 The Universal Oil Products Hylube Process.............246
7.8 Distillation/Filtration/Hydrogenation Processes.................... 252
7.8.1 The Commissariat a l’Energie Atomique et
Compagnie Française de Raffinage Process............. 252
7.9 Processes Producing Primarily a Fuel Product and
Possibly a Base Oil Product.................................................... 257
7.9.1 Filtration Processes................................................... 257
7.9.1.1 The Ciora and Liu Processes..................... 258
7.9.2 Cracking and Coking Processes................................ 263
7.9.2.1 The Alphakat Process................................ 263
7.10 Other Processes......................................................................264
7.10.1 The CleanOil Ltd. Process........................................264
Patents............................................................................................... 265
References......................................................................................... 271
Chapter 8 Economics and Other Evaluation Criteria........................................ 273

8.1 Introduction............................................................................ 273
8.2 Recycled Oil Collection Costs................................................ 274
8.3 Capital Costs of the Plant....................................................... 275
8.4 Operating Cost Considerations for the Plant.......................... 276
8.5 Economic Indicators............................................................... 276
8.5.1 Net Present Value...................................................... 276
8.5.2 Internal Rate of Return............................................. 277
8.6 Excel Spreadsheet for a Recycling Plant................................ 277
8.6.1 Capital Cost Varies as the Feedrate Varies...............284
8.6.2 Operating Costs Vary as the Feedrate Varies...........284
8.6.3 Assumed Inflation Rate............................................. 285
8.6.4 Earnings Before Interest, Taxes, Depreciation,
and Amortization...................................................... 285
8.6.5 NPV and IRR Functions in Excel............................. 285
8.7 Economic Evaluation of a Small and a Large Project............ 285
8.7.1 Example 1: Low Vacuum Distillation with
Subsequent Clay Treatment....................................... 285
Contents xi
8.7.2 Example 2: Re-Refining in a Hydrogen-Rich

Atmosphere............................................................... 286
8.8 Discussion of Some Results of the Economic Evaluation...... 287
8.9 Comparison of Re-Refining with Production from
Crude Oil................................................................................ 287
8.9.1 Life Cycle Assessments............................................. 287
8.9.2 Performance Criteria................................................. 289
8.9.3 The United Nations Environmental Program’s
Sustainability Assessment of Technologies
Evaluation.................................................................. 290
References......................................................................................... 290
Chapter 9 Choice of a Process Technology....................................................... 293

9.1 Introduction............................................................................ 293
9.2 Relevant Reports..................................................................... 294
9.2.1 Process Screening for a Plant in India...................... 294
9.2.2 Basel Convention Guidelines on Waste
Management.............................................................. 295
9.2.3 Process Screening for a Plant in Saudi Arabia.......... 296
9.2.4 Manual on Re-Refined Lubricants Use in
California.................................................................. 296
9.2.5 Used Oil Management in New Zealand.................... 298
9.2.6 Overview of Re-Refining from Poland..................... 299
9.2.7 Overview of Re-Refining from Spain....................... 301
9.2.8 Taylor Nelson Sofres Report and Life Cycle
Analysis Study on Re-Refining Processes................302
9.2.9 The UK Used Oils Market 2001...............................308
9.2.10 Process Simulation and Modeling............................. 312
9.2.11 Compendium of Regeneration Technologies............ 313
9.2.11.1 Implemented Processes............................. 314
9.2.11.2 The Other Prototype or Pilot Plant
Processes.................................................... 315
9.2.11.3 The Studies and Patents Processes............ 316
9.2.11.4 Fuel Production Processes......................... 317
9.2.11.5 Prototypes and Other Processes for Fuels.... 317
9.2.12 DEFRA Study on Used Oil Management in
Italy and Germany..................................................... 318
9.2.12.1 Italy............................................................ 318
9.2.12.2 Germany.................................................... 319
9.2.13 California LCA Study on Re-Refining and Use
as a Fuel..................................................................... 321
9.2.14 Preview of the Institut für Energie und
Umweltforschung 2005 LCA Study.......................... 324
9.2.15 Nigeria Pilot Study on Used Oils.............................. 325
xii Contents
9.2.16 Nigeria Workshop on Used Oil Management

in Africa.................................................................... 326
9.2.17 LCA Study of Re-Refining and Use as a Fuel........... 328
9.2.18 Improving Markets for Used Oils............................. 332
9.2.19 Critique of the Canadian UOMA Program
Review of 2005.......................................................... 334
9.2.20 Catalan Waste Agency Position on an LCA Study.... 336
9.2.21 Re-Refining Processes Viewed from India............... 337
9.2.22 Used Oil Management in Scotland........................... 338
9.2.23 API Perspective on Re-Refining............................... 339
9.2.24 Used Engine Oils: Re-Refining and Energy
Recovery....................................................................340
9.2.25 Design Data for a Re-Refining Plant.........................340
9.2.26 GEIR Statistics for Lubricants and Re-Refining
in the EU in 2006......................................................340
9.2.27 A Re-Refining Process from Iran.............................. 347
9.2.28 Emissions Data due to Used Lubricating Oils in
the UK....................................................................... 347
9.2.29 DOE Used Oil Re-Refining Study............................348
9.2.30 Case Study for Greece of Re-Refining Benefits........ 350
9.2.31 Processing Possibilities for Used Oil: Hungarian
Summary Part I......................................................... 350
9.2.32 Improving Used Oil Recycling in California............ 351
9.2.33 Processing Possibilities for Used Oil: Hungarian
Summary Part II........................................................ 353
9.2.34 Re-Refining in Europe.............................................. 354
9.2.35 Solvent Extraction Process Study in Pakistan........... 355
9.2.36 Policy and Technical Considerations for a
Potential Re-Refining Plant in Western Australia..... 356
9.2.37 Used Oil Recycling in Taiwan...................................360
9.2.38 GEIR Used Oil Statistics in Europe in 2006............ 361
9.2.39 Screening Process for a Re-Refining Plant in
Turkey...............................................................................361
9.2.40 Compendium of Recycling and Destruction
Technologies for Waste Oils...................................... 367
9.3 Future Developments.............................................................. 368
References......................................................................................... 369
Glossary................................................................................................................. 373
Appendix A............................................................................................................ 429
Appendix B............................................................................................................ 431
Appendix C............................................................................................................ 433
Preface
Used lubricating oil is a valuable resource. However, during service, lubricating oil
becomes contaminated by a number of additional components (from engine wear)
such as iron and steel particles, copper, lead, zinc, barium and cadmium (two highly
toxic metals), sulfur, water, and dirt. In addition, the organic constituents of lubri-
cating oil will also undergo changes in use and produce undesirable contaminants.
Because of these contaminants, disposal of used lubricating oil can be more environ-
mentally damaging than crude oil pollution.
Thus, lubricating oil becomes unfit for further use for two main reasons: accumu-
lation of contaminants in the oil and chemical changes in the oil. In addition, there
is a shortage of prime lubricating oils that is difficult to make up and requires use of
hard-to-replace petroleum for products other than fuels. Resource preservation and
issues related to oil disposal are priorities that dictate the expansion of the re-refining
option.
The economically and environmentally sound way to dispose of used lubricating
oil is to recycle the used oil to its original use. A second recycling option is to clean
up the used oil and use it as a fuel. In North America and Europe, as well as in other
countries in the world, legislation is being introduced that requires waste materials
to be recycled under a hierarchy of options that favor returning the materials to their
original use where this is practicable and moving to a lower level of recycling, which
includes energy recovery and could involve their disposal by destructive means such
as use as a fuel, where this can be justified. Although the definition of what is practi-
cable and what justifications are acceptable can be the subject of discussion, there is
no doubt that the re-refining of used lubricating oils is becoming more popular and
desirable.
Recent studies using life cycle assessment methods have highlighted the relative
merits of the used oil recycling methods and include analyses of the energy use in
recycling and in the original production of similar products from crude oil. Although
crude oil prices fluctuate from year to year, valuable energy resources can be con-
served by the use of recycled lubricating oil and fuel oil made from reclaimed motor
oil. The energy saved by collecting and recycling used motor oil can also help reduce
our dependence on foreign oil imports.
This book presents to the reader the properties of used lubricating oils and the
means by which such materials can be re-refined and converted once more into use-
ful lubricants as well as other products. This book will also strongly suggest the
feasibility of such action and leave the reader with the knowledge of the currently
feasible used lubricating oil recycling programs that are being introduced in many
parts of the world.
Finally, at a time when many nations of the world have undergone a transferal to
the metric system of measurement, there are still those disciplines that are based on
such scales as the Fahrenheit temperature scale as well as the foot measure instead
of the meter. Accordingly, and where appropriate, the text contains both the metric
xiii
xiv Preface
and nonmetric measures, but it should be noted that exact conversion is not often fea-
sible, and thus conversion data are often taken to the nearest whole number. Indeed,
conversions involving the two temperature scales—Fahrenheit and Celsius—are, at
the high temperatures quoted in the text, often rounded to the nearest 5 degrees,
especially when serious error would not arise from such a conversion.
Additional material is available from the CRC Web site: http://www.crcpress.
com/product/isbn/9781466551497.
James G. Speight, PhD, DSc

Douglas I. Exall, PhD, P.Eng.
Authors
Dr. James G. Speight, C. CChem., FRSC, FCIC, FACS, earned his BSc and PhD
degrees from the University of Manchester, U.K. He also holds a DSC degree in geo-
logical sciences (VINIGRI, St. Petersburg, Russia) and a PhD degree in petroleum
engineering (Dubna International University, Moscow, Russia). Dr. Speight is the
author of more than 50 books in petroleum science, petroleum engineering, and envi-
ronmental sciences. Formerly the CEO of the Western Research Institute (now an
independent consultant), he has served as an adjunct professor in the Department of
Chemical and Fuels Engineering at the University of Utah and in the Departments of
Chemistry and Chemical and Petroleum Engineering at the University of Wyoming.
In addition, he has also been a visiting professor in chemical engineering at the fol-
lowing universities: the University of Missouri–Columbia, the Technical University
of Denmark, and the University of Trinidad and Tobago.
Dr. Speight was elected to the Russian Academy of Sciences in 1996 and awarded
the Gold Medal of Honor that same year for outstanding contributions to the field
of petroleum sciences. He has also received the Scientists without Borders Medal
of Honor of the Russian Academy of Sciences. In 2001, the Academy also awarded
Dr. Speight the Einstein Medal for outstanding contributions and service in the field
of geological sciences.
Dr. Douglas I. Exall, P.Eng., is an engineering consultant with more than 40 years
of experience in oil and gas production and processing technologies with patents,
conference presentations, journal publications, industrial R&D reports, and teach-
ing experience in most areas of chemical engineering, including refinery operations,
process modeling and simulation, and economic analysis. He received his engi-
neering education at the University of Natal in South Africa and the Swiss Federal
Institute of Technology in Zurich, holding BSc, MSc, and PhD degrees in chemical
engineering from the University of Natal. He has worked as a research manager in
the oil and gas industry and Alberta Research Council in Canada, and as a profes-
sor or adjunct professor in the University of Calgary, the University of Regina, the
University of Natal, the University of Trinidad and Tobago, and the Universidad de
America in Colombia, as well as coordinating the petroleum engineering programs
at the Southern Alberta Institute of Technology in Calgary. He has taught courses
in petroleum refining, process modeling and simulation, and economic evaluation,
besides many of the chemical engineering courses covering heat, mass, and momen-
tum transfer with chemical reaction kinetics and transformations.
Since 2007, consulting work has included reviewing options for the re-refining of
lubricating oils, the available processes and technologies and their economic viabil-
ity, as well as modeling oil and gas production and field production economics.
xv
1 Manufacture of
Lubricating Oil
1.1 INTRODUCTION
The constant demand for products such as liquid fuels is the main driving force
behind the petroleum industry. Indeed, fuel products—for example, gasoline, kero-
sene, and diesel fuel—are the prime products of the current era. In addition, other
products, such as lubricating oils, waxes, and asphalt, have also added to the popu-
larity of petroleum as an important resource. Petroleum products are the basic mate-
rials used for the manufacture of synthetic fibers for clothing and in plastics, paints,
fertilizers, insecticides, soaps, and synthetic rubber. In fact, the use of petroleum
as a source of raw material in manufacturing is central to the functioning of mod-
ern industry (Speight and Ozum 2002; Hsu and Robinson 2006; Gary et al. 2007;
Speight 2014).
After kerosene, the early petroleum refiners produced paraffin wax for the manu-
facture of candles, and lubricating oil was, at first, a by-product of wax manufacture—
the preferred lubricants in the 1860s (at the dawn of the refining industry) were lard
oil (oil from pig fat), sperm oil (whale oil), and tallow (a rendered form of beef or
mutton fat, processed from suet, which is solid at room temperature). The demand
that existed for kerosene did not also exist for petroleum-derived lubricating oils,
and the demand for these high-boiling oils took time and market demand to develop,
although petroleum-derived lubricating oil was used to supplement the animal-
derived and vegetable-derived lubricating oils. However, industry evolved and the
trend to heavier machinery increased the demand for mineral lubricating oils and,
after the 1890s, petroleum displaced animal and vegetable oils as the predominant
source of lubricants.
Oils derived from petroleum sources (mineral oils) are often used as lubricating
oils but also have medicinal and food uses. A major type of hydraulic fluid is the
mineral oil class of hydraulic fluids, which are produced from higher-boiling petro-
leum distillates. Carbon numbers ranging from C15 to C50 occur in the various types
of mineral oils, with the higher-boiling distillates having higher percentages of the
higher–carbon number compounds.
Crankcase oil (motor oil) may be either mineral-based or synthetic. The mineral-
based oils are more widely used than the synthetic oils and may be used in automotive
engines, railroad and truck diesel engines, marine equipment, jet and other aircraft
engines, and most small two-stroke and four-stroke engines. The mineral-based
oils contain hundreds to thousands of hydrocarbon compounds but unfortunately
also include a substantial fraction of nitrogen-containing and sulfur-containing
compounds. The hydrocarbons are mainly mixtures of straight and branched chain
1
2 Refining Used Lubricating Oils
hydrocarbons (alkanes), cycloalkanes, and aromatic hydrocarbons. Polynuclear

aromatic hydrocarbons (and the corresponding alkylated derivatives) and metal-
containing constituents are components of motor oils and crankcase oils, with the
used oils typically having higher concentrations of these substances than the new
unused oils.
As a general note, lubricating oils produced from petroleum represent the major-
ity of lubricating oils used each year in the United States. The use of synthetic lubri-
cating oil is increasing in popularity and the market for synthetic lubricating oils is
expanding because of their interesting properties, such as (1) high viscosity index
due to the absence of aromatic compounds, (2) low volatility, (3) high thermal stabil-
ity, and (4) low-temperature flow behavior.
In the current context, the major forces driving change in the automotive lubri-
cant industry are higher fuel economy, smaller engines operating at higher rota-
tional speeds, further low-temperature improvements, longer drain intervals, and
emission control system durability. Increased use of lighter-viscosity multigrade oils
to achieve better fuel economy and low-temperature performance has made base oil
properties key factors in lubricant design. Currently, the more severe demand for
volatility and low temperature properties requires the full integration of base oils
and formulation technologies. Conventional mineral-based oils alone are no longer
adequate to meet the top requirements among North American and European speci-
fications, especially regarding volatility.
1.2 BASE OIL MANUFACTURE FROM PETROLEUM SOURCES

Base oil is the base stock or blend of base stocks used in American Petroleum
Institute (API)-licensed oil and a base stock slate is a product line of base stocks that
have different viscosities but are in the same base stock grouping and are from the
same manufacturer.
Base oil (the raw material for lubricants) is the name given to lubrication grade
oils initially produced from refining crude oil (mineral base oil) or through chemi-
cal synthesis (synthetic base oil). Base oil is typically defined as oil with a boiling
point range between 300°C (550°F) and 565°C (1050°F), consisting of hydrocarbons
with 18 to 40 carbon atoms. This oil can be either paraffinic or naphthenic in nature
depending on the chemical structure of the constituent molecules.
Like many petroleum products, there are no longer many (if any) processes that
are responsible for the direct manufacture of base oil. The base oil is typically
a blend of products from several streams to which additives are added to adjust
the properties to meet specifications and desired service life (Pillon 2007, 2010;
Rudnick 2013).
1.2.1 Base Oil Manufacture

Lubricating oil manufacture was well established by 1880, and the method depended
on whether the crude petroleum was processed primarily for kerosene or for lubri-
cating oils. Usually, the crude oil was processed for kerosene, and primary distilla-
tion separated the crude into three fractions, naphtha, kerosene, and residuum. To
Manufacture of Lubricating Oil 3
increase the production of kerosene, the cracking distillation technique was used,
and this converted a large part of the gas oils and lubricating oils into kerosene. The
cracking reactions also produced coke products and asphalt-like materials, which
gave the residuum a black color and, hence, it was often referred to as tar (Speight and
Ozum 2002; Hsu and Robinson 2006; Gary et al. 2007; Speight 2014).
The rapid evolution of lubricating oil manufacture and use occurred during the
early decades of the twentieth century. Petroleum-based oils first became available
and as the demand for automobiles grew, so did the demand for better lubricants. By
1923, the U.S. Society of Automotive Engineers (SAE) classified engine oils by vis-
cosity as light, medium, and heavy lubricating oils. However, engine oil contained
no additives and had to be replaced every 800 to 1000 miles. In the 1920s, more
lubrication manufacturers started “processing” base oils to improve their perfor-
mance. Three popular processing routes were: (1) clay treatment, (2) acid treatment,
and (3) sulfur dioxide treatment (Kramer et al. 2001).
Clay treatment was used to soak up and remove some of the worst undesirable
components in the petroleum base oil. These compounds were usually aromatic and
highly polar compounds containing sulfur and nitrogen (Speight and Ozum 2002;
Hsu and Robinson 2006; Gary et al. 2007; Speight 2014).
Acid treatment with concentrated sulfuric acid was used to react with the worst
components in the base oil and convert them into a sludge that could be removed.
Although this process effectively cleaned up the oil, it was expensive and the tech-
nology is no longer used in many refineries due to environmental concerns about the
acid and the acid sludge (a thick viscous material that separates when petroleum or
petroleum products are treated with sulfuric acid) formed in the process (Speight and
Continuous acid treatment involves the same steps as batch refining with the
exception that (1) the acid and feedstock oil and neutralizing agent are mixed with
pumps or static mixers, (2) excess acid and sludge and excess neutralizing agent and
soaps are removed using centrifuges or centrifugal extractors, (3) water washing is
conducted using centrifugal extractors, and (4) drying of the oil is conducted in con-
tinuous strippers. The advantages for the continuous process over the batch process
are (1) higher yields of oil, (2) lower chemical consumption, and (3) a reduction in
air and water pollution.
Sulfur dioxide treatment was a primitive extraction process to remove the worst
components in the lubricating oil using a recyclable solvent which, unfortunately,
was highly toxic. Although it also has been virtually phased out, it was a useful
stepping stone to conventional solvent extraction (Speight and Ozum 2002; Hsu and
Robinson 2006; Gary et al. 2007; Speight 2014).
Currently, catalytic dewaxing and solvent dewaxing (the most prevalent) are
processes commonly in use—older technologies include cold settling, pressure fil-
tration, and centrifuge dewaxing (Sequeira 1994; Kramer et al. 2001; Speight and
1.2.1.1 Distillation
Within a naphthenic or paraffinic type, base stocks are distinguished by their vis-
cosities and are produced to certain viscosity specifications. Because viscosity is
approximately related to molecular weight, the first step in manufacturing is to sepa-

rate out the lube precursor components that have the correct molecular weight range.
Lower-boiling fuel products of such low viscosities and volatilities, which have no
application in lubricants—naphtha, kerosene, jet, and diesel fuels—are distilled off
in an atmospheric pressure distillation tower. The higher molecular weight com-
ponents, which do not vaporize at atmospheric pressure, are then fractionated by
distillation at reduced pressures of from 10 to 50 mm Hg (i.e., vacuum fractionation).
The constituents of the base oil are extracted from crude oil, which undergoes a
preliminary purification process (sedimentation) before it is pumped into fraction-
ating towers (Speight and Ozum 2002; Hsu and Robinson 2006; Gary et al. 2007;
Speight 2014). A typical high-efficiency fractionating tower, 25 to 35 ft. in diameter
and up to 400 ft. tall, is constructed of high-grade steels to resist the corrosive com-
pounds present in crude oils. The tower internals consist of an ascending series of
condensate collecting trays (Figure 1.1).
Within the first tower (atmospheric distillation tower), the constituents of petro-
leum are separated from each other (fractional distillation; Speight and Ozum 2002;
Hsu and Robinson 2006; Gary et al. 2007; Speight 2014). As the vapors rise up
through the tower, the various fractions cool, condense, and return to liquid form at
different rates determined by their respective boiling points (the lower the boiling
point of the fraction, the higher it rises before condensing).
Gas
Gas (butane and lighter)
+
Gasoline (light naphtha)
Gas Heavy naphtha

separator
Atmospheric
fractionation
Kerosene
Gasoline Light gas oil
Heavy gas oil
Desalter Residuum
Furnace
Crude
oil
Pump
FIGURE 1.1 An atmospheric distillation unit. (From OSHA Technical Manual, Section
IV, Chapter 2: Petroleum Refining Processes. http://www.osha.gov/dts/osta/otm/otm_iv/otm_
iv_2.html.)
Thus, the atmospheric residuum (bottoms) from the atmospheric tower are fed
to the vacuum tower, in which intermediate product streams such as light vacuum
gas oil and heavy vacuum gas oil are produced. These may be either narrow cuts of
specific viscosities destined for a solvent-refining step or broader cuts destined for
hydrocracking to lubes and fuels.
The nonvolatile material from the atmospheric distillation tower is reheated and
pumped into this second tower (vacuum distillation tower) wherein vacuum pressure
lowers the residual oil’s boiling point so that it can be made to vaporize at a lower
temperature. The higher–molecular weight constituents with higher boiling points,
such as residuum which contains inorganic contaminants originally in the crude oil,
remain for further processing (Figure 1.2).
However, the nonvolatile residuum from the vacuum tower (vacuum tower bot-
toms) may contain valuable high-viscosity lube precursors (boiling point >510°C,
>950°F) and these are separated from asphaltic components (nonvolatile highly aro-
matic components that are difficult to refine) in a deasphalting unit.
Deasphalting units separate asphalt from deasphalted oil using solubility differ-
ences, and this is usually soluble in propane, and further refining of the deasphalted
oil by dewaxing and solvent refining or by hydrotreatment produces bright stock,
which is a heavy (very viscous) base stock that is a residue (i.e., it is not a distillate
overhead). The deasphalted oil can also be part of the feedstock to a lube hydro-
cracker to produce heavier base stocks.
To vacuum system
Vacuum
gas oil
Vacuum
tower
Lubricating oils
Residuum Vacuum
residuum
Furnace
FIGURE 1.2 A vacuum distillation unit. (From OSHA Technical Manual, Section IV,
Chapter 2: Petroleum Refining Processes. http://www.osha.gov/dts/osta/otm/otm_iv/otm_
iv_2.html.)
The waxy distillates and deasphalted oil require three further processing steps to
obtain acceptable base stock: (1) the viscosity–temperature relationship of the base
stock (improvement of the viscosity index) has to be enhanced by the removal of
aromatics to meet industry requirements for paraffinic stocks; (2) oxidation resis-
tance and performance must be improved by the removal of aromatics, particularly
polynuclear aromatic compounds, nitrogen-containing constituents, and some of
the sulfur-containing compounds; and (3) the temperature at which the base stock
“freezes” due to the crystallization of wax must be lowered by wax removal so that
lubricated equipment can operate at winter temperatures.
After further processing to remove unwanted compounds, the lubricating oil
fraction that has been collected in the two fractionating towers is passed through
several ultrafine filters, which remove remaining impurities. Aromatics, one such
contaminant, contain six carbon rings that would affect the lube oil’s viscosity
undesirably if they were not removed by solvent extraction. Solvent extraction is
possible because aromatics are more soluble in the solvent compared with the lube
oil fraction. When the base oil is treated with the solvent, the aromatic constituents
dissolve and the insoluble fraction (aromatic constituents) is recovered by separa-
tion from the solvent.
1.2.1.2 Chemical Refining Processes

In chemical refining processes, constituents with chemical structures unsuitable
for lubes are wholly or partially converted to acceptable base stock components.
These processes all involve catalysts acting in the presence of hydrogen (cata-
lytic hydroprocessing). Examples are the hydrogenation and ring opening of poly-
nuclear aromatic systems to polycyclic naphthenes with the same or fewer rings
and the isomerization of wax components to more highly branched isomers with
lower freezing points. Furthermore, the chemical properties of existing useful con-
stituents may be simultaneously altered such that even better performance can be
achieved.
Acid-alkali refining, also called wet refining, is a process in which lubricating
oils are contacted with sulfuric acid followed by neutralization with alkali. The
process is conducted in a batch or in a continuous manner. In older batch pro-
cesses, the oil to be treated is pumped to a treating agitator and mixed with acid
of the desired strength. The oil and acid are mixed by mechanical means or by air
blowing and water may be added to assist in the coagulation of the acid sludge.
The sludge is removed or the oil decanted after settling for a period of several
hours. Additional acid is added and the process is repeated as needed. The acidic
oil (sour oil) from this operation is then neutralized using an aqueous or alcoholic
neutralizing agent followed by water washing and drying. The main difference in
acid finishing as compared with acid refining is that the quantity of acid used is
usually lower in comparison to the larger quantity used in the acid refining pro-
cesses. More modern variations of the process are conducted in totally enclosed
treating vessels, which eliminate the air pollution associated with the older open
treating units.
Acid-clay refining, also called dry refining, is similar to acid-alkali refining with
the exception that clay and a neutralizing agent are used for neutralization. This
process is used for oils that form emulsions during neutralization. Neutralization
with aqueous and alcoholic caustic, soda ash lime, and other neutralizing agents,
is used to remove organic acids from some feedstocks. This process is conducted
to reduce organic acid corrosion in downstream units or to improve the refining
response and color stability of lube feedstocks.
1.2.1.3 Hydroprocessing
Hydroprocessing (hydrotreating) was developed in the 1950s and first used in base
oil manufacturing in the 1960s. It was used as an additional purification step after a
conventional solvent refining process. In the process, hydrogen is added to the base
oil at elevated temperatures in the presence of a catalyst to stabilize the most reactive
components in the base oil, improve color, and increase the useful life of the base
oil. This process removes some of the nitrogen-containing and sulfur-containing
species but the process was not sufficiently severe to remove a significant amount of
aromatic molecules.
Hydrocracking is a more severe form of hydroprocessing and requires higher
temperatures and pressures than hydrotreating (Figure 1.3). Feedstock molecules
are cracked (thermally decomposed) into lower molecular weight products. Most of
the sulfur, nitrogen, and aromatics are removed and the molecular alteration of the
remaining saturated species occurs as naphthenic rings are opened and paraffin iso-
mers are redistributed, and driven by thermodynamics with reaction rates facilitated
by catalysts.
Fresh
gas
Quench
gas Products
Recycle gas
compressor
Fractionation
1st 2nd
stage stage HP
separator
LP
separator Recycle
Feedstock
FIGURE 1.3 Two-stage hydrocracking. (From OSHA Technical Manual, Section IV,
Chapter 2: Petroleum Refining Processes. http://www.osha.gov/dts/osta/otm/otm_iv/otm_
iv_2.html.)
Hydroprocessing, which has been generally replaced with solvent refining, con-
sists of lube hydrocracking as an alternative to solvent extraction, and hydrorefining
to prepare specialty products or to stabilize hydrocracked base stocks. Hydrocracking
catalysts consist of mixtures of cobalt, nickel, molybdenum, and tungsten on an alu-
mina or silica–alumina-based carrier. Hydrotreating catalysts are proprietary, but
usually consist of nickel–molybdenum on alumina. The hydrocracking catalysts are
used to remove nitrogen, oxygen, and sulfur, and convert polynuclear aromatics and
polynuclear naphthenes to mononuclear naphthenes, aromatics, and isoparaffins,
which are typically desired in lube base stocks. Feedstocks consist of unrefined dis-
tillates and deasphalted oils, solvent-extracted distillates and deasphalted oils, cycle
oils, hydrogen refined oils, and mixtures of these hydrocarbon fractions.
In the first stage of the catalytic hydrogenation process, part of the feedstock
aromatic constituents are saturated by hydrogenation to form cycloparaffins. The
process also promotes significant molecular reorganization by carbon–carbon bond
breaking to improve the rheological (flow) properties of the base stock (by improving
the viscosity index).
Typically, in this stage, feedstock sulfur and nitrogen are both essentially elimi-
nated. Some of the carbon–carbon bond breaking produces overhead (distillable,
volatile) products in the form of low-sulfur gasoline and middle distillates. The
fractionated waxy lube streams, usually those boiling at approximately higher than
370°C (700°F), are then dewaxed, either by solvent dewaxing or more frequently by
catalytic hydroprocessing (in which wax is either cracked to gasoline or isomerized
to low melting point isoparaffins in high yields and which has a positive effect on the
viscosity index).
The final step in the conversion processes is usually catalytic hydrogenation to
saturate most of the remaining aromatics to make base stocks stable for storage and
to improve their performance. Base stocks produced by this route are frequently
water white, whereas solvent extracted stocks retain some color.
Lubricating oil hydrogenating processes are used to stabilize or improve the qual-
ity of lube base stocks from lube hydrocracking processes and for the manufacture
of specialty oils. Feedstocks are dependent on the nature of the crude source, but
generally consist of waxy or dewaxed solvent–extracted or hydrogen-refined paraf-
finic oils and refined or unrefined naphthenic and paraffinic oils from some selected
crude oils.
1.2.1.4 Solvent Refining Processes

As refinery processes evolved in the 1930s, solvent processing emerged as a viable
technology for improving base oil performance using a fairly safe, recyclable solvent
and the solvent processes continues to be widely used in refineries.
In the process, the two main processing steps are (1) aromatics removal and
(2) wax removal chilling, with subsequent precipitation of the wax, in the presence
of a different solvent.
Aromatics are removed by solvent extraction to improve the lubricating quality of
the oil. Aromatics make good solvents but they make poor quality base oils because
they are among the most reactive components in the lubricating oil boiling range.
Oxidation of aromatics can start a chain reaction that can dramatically shorten the
useful life of base oil. The viscosity of aromatic components in base oil also responds
relatively undesirably to changes in temperature.
Lubricants are often designed to provide a viscosity that is low enough for good
cold weather starting and high enough to provide adequate film thickness and
lubricity in hot, high-severity service. Therefore, when hot and cold performance is
required, a small response to changes in temperature is desired, which is measured
by the viscosity index—a higher viscosity index indicates a smaller, more favor-
able response to temperature. Correspondingly, many turbine manufacturers have a
minimum viscosity index specification for their turbine oils. Base oil selection is the
driver for meeting this specification because turbine oil additives do not normally
contribute positively to the viscosity index in turbine oil formulations.
Aromatics are removed by feeding the raw lube distillate (vacuum gas oil) into
a solvent extractor in which it is contacted countercurrently with a solvent, such
as furfural, N-methyl-2-pyrrolidone (NMP), and DUO-SOL. Phenol was another
popular solvent but it is rarely used today due to environmental concerns. Solvent
extraction typically removes 50% to 80% of the impurities (aromatics, polar constit-
uents, sulfur-containing and nitrogen-containing species). The second step is solvent
dewaxing in which wax is removed from the oil to keep the lubricating oil from gell-
ing (through wax deposition) at low temperatures (Figure 1.4). In the process, wax
is removed by first diluting the raffinate with a solvent to lower its viscosity improv-
ing low-temperature filterability. Popular dewaxing solvents are methyl-ethyl ketone
(MEK)/toluene, MEK/methyl-isobutyl ketone, or (rarely) propane. The diluted oil is
then chilled to −10°C to −20°C (14°F to −4°F). Wax crystals form, precipitate, and
are removed by filtration (Kramer et al. 2001).
After the undesirable chemical compounds (e.g., polynuclear aromatic constitu-
ents) are removed using the solvent-based separation process (solvent refining), the
by-products (extracts) represent a yield loss in producing the base stock. The base
Solvent
Wash
solvent
evaporator
Slack wax
Heater
Rotary filter
Chiller
Dewaxed oil
evaporator
Heat exchanger
Steam heater Heater
Feedstock
Dewaxed oil Stack wax
FIGURE 1.4 Solvent dewaxing. (From OSHA Technical Manual, Section IV, Chapter 2:
Petroleum Refining Processes. http://www.osha.gov/dts/osta/otm/otm_iv/otm_iv_2.html.)
stock properties are determined by the chemical composition of the crude oil because
the molecular species in the final base oil are unchanged from those in the feedstock.
Feedstocks for solvent-refining processes consist of paraffinic distillate, naph-
thenic distillate, hydrogen-refined distillates, deasphalted oil, cycle oil, and dewaxed
oil. The products are refined oils destined for further processing or finished lube
base stocks. The by-products are aromatic extracts, which are used in the manufac-
ture of rubber, carbon black, petrochemicals, catalytic cracking feedstock, fuel oil,
or asphalt. The major solvents in use are NMP and furfural, with phenol and liquid
sulfur dioxide used to a lesser extent.
The solvents are typically recovered in a series of flash towers. Steam or inert gas
strippers are used to remove traces of solvent, and a solvent purification system is
used to remove water and other impurities from the recovered solvent.
1.2.1.5 Solvent Dewaxing
Solvent dewaxing is a variation of the solvent refining processes describe above
(Speight and Ozum 2002; Hsu and Robinson 2006; Gary et al. 2007; Speight 2014)
and consists of the following steps: crystallization, filtration, and solvent recovery. In
the crystallization step, the feedstock is diluted with the solvent and chilled, solidify-
ing the wax components. The filtration step removes the wax from the solution of
dewaxed oil and solvent. Solvent recovery removes the solvent from the wax cake
and filtrate for recycling by flash distillation and stripping. The major process in use
today is the ketone dewaxing process.
Other processes that are used to a lesser degree include the dimethyl ketone pro-
cess Di/Me process and the propane dewaxing process. The most widely used ketone
processes are the Texaco solvent dewaxing process and the Exxon Dilchill Process.
Both processes consist of diluting the waxy feedstock with solvent while chilling at
a controlled rate to produce a slurry. This slurry is then filtered using rotary vacuum
filters and the wax cake is washed with a cold solvent. The filtrate is used to chill the
feedstock and solvent mixture. The primary wax cake is diluted with additional sol-
vent and filtered again to reduce the oil content in the wax. The solvent is recovered
from the dewaxed oil and wax cake by flash vaporization and recycled back into the
process.
The Texaco solvent dewaxing process (also called the MEK process) uses a mix-
ture of MEK and toluene as the dewaxing solvent, and sometimes uses mixtures
of other ketones and aromatic solvents. The Exxon Dilchill dewaxing process uses
a direct cold solvent dilution-chilling process in a special crystallizer in place of
the scraped surface exchangers used in the Texaco process. The Di/Me dewaxing
process uses a mixture of dichloroethane and methylene dichloride as the dewaxing
solvent. The propane dewaxing process is essentially the same as the ketone process
except for the following: propane is used as the dewaxing solvent and higher pressure
equipment is required, and chilling is done in evaporative chillers by vaporizing a
portion of the dewaxing solvent. Although this process generates a better product
and does not require crystallizers, the temperature differential between the dewaxed
oil and the filtration temperature is higher than for the ketone processes (higher
energy costs), and dewaxing aids are required to get good filtration rates.
1.2.1.6 Catalytic Dewaxing and Hydroisomerization

The first catalytic dewaxing and wax hydroisomerization technologies were com-
mercialized in the 1970s (Kramer et al. 2001). Catalytic dewaxing was a desirable
alternative to solvent dewaxing especially for conventional neutral oils because
it removed n-paraffins and waxy side chains from other molecules by catalyti-
cally cracking them into smaller molecules. This process lowered the pour point
of the base oil so that it flowed at low temperatures, like solvent dewaxed oils.
Hydroisomerization also saturated most of the remaining aromatics and removed
most of the remaining sulfur and nitrogen species.
In 1993, the first modern wax hydroisomerization process was commercialized
and was an improvement over earlier catalytic dewaxing because the pour point of
the base oil was lowered by isomerizing (reshaping) the n-paraffins and other mol-
ecules with waxy side chains into very desirable branched compounds with superior
lubricating qualities rather than cracking them away. Hydroisomerization was also an
improvement over earlier wax hydroisomerization technologies because it eliminated
the subsequent solvent dewaxing step, which was a requirement for earlier generation
wax isomerization technologies to achieve adequate yield at standard pour points.
Current wax hydroisomerization processes yield products with exceptional purity
and stability due to an extremely high degree of saturation. They are very distinctive
because, unlike other base oils, they typically have no color.
Because solvent dewaxing is relatively expensive for the production of low pour
point oils, various catalytic dewaxing (selective hydrocracking) processes have been
developed for the manufacture of lube oil base stocks. The basic process consists of
a reactor containing a proprietary dewaxing catalyst followed by a second reactor
containing a hydrogen finishing catalyst to saturate olefins created by the dewaxing
reaction and to improve stability, color, and to mitigate emulsion formation by the
finished lube oil during service.
1.2.2 Older Processes
Older processes are those which were the prime means of lubricating oil and wax
production—some of which are occasionally reported as still being operational in
present-day refineries.
In older refineries, there was often cracking in the primary (atmospheric) distilla-
tion at the high temperatures used in the process, and the gas oil used as the precur-
sor to the lubricating oil contained dark-colored, sludge-forming asphaltic materials.
These undesirable materials were removed by treatment with sulfuric acid followed
by lye washing (Speight and Ozum 2002; Speight 2014). This was followed by sepa-
ration of the wax from the acid-treated paraffin distillate, which was achieved by
chilling and filtration. The chilled, semisolid paraffin distillate was then squeezed
in canvas bags in a knuckle or rack press (similar to a cider press) so that the oil
would filter through the canvas, leaving the wax crystals in the bag. Later devel-
opments saw chilled paraffin distillate filtered in hydraulically operated plate and
frame presses, and the use of these continued almost to the present time (Speight and
Ozum 2002; Speight 2014).
The oil from the press (pressed distillate) was subdivided into three fractions
by re-distillation. Two overhead fractions of increasing viscosity, the heavier with
an SAE viscosity of approximately SAE 10 (paraffin oils) and the residue in the still
(viscosity equivalent to a light SAE 30) was known as red oil. All three fractions
were again acid-treated and lye (alkali)–treated and then washed with water. The
treated oils were pumped into shallow pans in the bleacher house, where air was
blown through the oil and exposure to the sun through the glass roof (of the bleacher
house or pan) removed cloudiness or made the oils bright—with no obvious signs of
sediment or other impurities.
Further treatment of the paraffin oil produced pale oil; thus, if the paraffin oil
was filtered through bone charcoal, fuller’s earth, clay, or similar absorptive mate-
rial, the color changed from a deep yellow to a pale yellow. The filtered paraffin oil
was called pale oil to differentiate it from the nonfiltered paraffin oil, which was
considered of lower quality.
The wax separated from paraffin distillate by cold-pressing contained approxi-
mately 50% oil (slack wax), which was melted and cast into cakes that were pressed
in a hot or hard press. This squeezed more oil from the wax (scale wax) which, by a
process known as sweating, was subdivided into several paraffin wax products with
different melting points.
In contrast, crude petroleum processed primarily as a source of lubricating oil
was handled differently from crude oils processed primarily for kerosene. The pri-
mary distillation removed naphtha and kerosene fractions, but without using tem-
peratures high enough to cause cracking. The yield of kerosene was thus much lower,
but the absence of cracking reactions increased the yield of lubricating oil fractions.
Furthermore, the residuum was distilled using steam, which eliminated the need for
high distillation temperatures, and cracking reactions were thus prevented. Thus,
various overhead fractions suitable for lubricating oils and known as neutral oils
were obtained; many of these were so light that they did not contain wax and did not
need dewaxing; the more viscous oils could be dewaxed by cold-pressing.
If the wax in the residual oil could not be removed by cold-pressing, it was
removed by cold settling. This involved admixture of the residual oil with a large
volume of naphtha, which was then allowed to stand for as long as necessary in a
tank exposed to low temperatures, usually climatic cold (winter). This caused the
waxy components to congeal and settle to the bottom of the tank. In the spring, the
supernatant naphtha–oil mixture was pumped to a steam still, in which the naphtha
was removed as an overhead stream; the bottom product was known as steam-refined
stock. If the steam-refined stock is filtered through charcoal or a similar filter mate-
rial, the improvement in color caused the oil to be known as bright stock (a high-
viscosity base oil, which is refined from paraffinic crude oil and widely used in
marine oil, mono-grade motor oil, gear oil, and grease; Haycock and Hiller 2004).
Mixtures of steam-refined stock with the much lighter paraffin, pale, red, and neutral
oils produced oils of any desired viscosity.
The wax material that settled to the bottom of the cold settling tank was crude
petrolatum. This was removed from the tank, heated, and filtered through a vessel
containing clay, which changed its red color to brown or yellow. Further treatment
with sulfuric acid produced white grades of petrolatum.
If the crude oil used for the manufacture of lubricating oils contained asphalt, it
was necessary to acid treat the steam-refined oil before cold settling. Acid-treated,
settled steam-refined stock was widely used as steam cylinder oils.
The crude oils available in North America until about 1900 were either paraf-
fin base or mixed base; hence, paraffin wax was always a component of the raw
lubricating oil fraction. The mixed-base crude oils also contained asphalt, and this
made acid treatment necessary in the manufacture of lubricating oils. However, the
asphalt-base crude oils (also referred to as naphthene-base crude oils) that contained
little or no wax yielded a different kind of lubricating oil. Because wax was not pres-
ent, the oils would flow at much lower temperatures than the oils from paraffin- and
mixed-base crude oils even when the latter had been dewaxed. Hence, lubricating
oils from asphalt-base crude oils became known as low cold-test oils; furthermore,
these lubricating oils boiled at a lower temperature than oils of similar viscosity
from paraffin-base crude oils. Thus, higher-viscosity oils could be distilled from
asphalt-base crude oils at relatively low temperatures, and the low cold-test oils were
preferred because they left less carbon residue in gasoline engines.
The development of vacuum distillation led to a major improvement in both par-
affinic and naphthenic (low cold-test) oils. By vacuum distillation, the more viscous
paraffinic oils (even oils suitable for bright stocks) could be distilled overhead and
could be separated completely from residual asphaltic components. Vacuum distil-
lation provided the means of separating more suitable lubricating oil fractions with
predetermined viscosity ranges and removed the limit on the maximum viscosity
that might be obtained in distillate oil.
However, although vacuum distillation effectively prevented residual asphaltic
material from contaminating lubricating oils, it did not remove other undesirable
components. The naphthenic oils, for example, contained components (naphthenic
acids) that caused the oil to form emulsions with water. In particular, naphthenic oils
contained components that caused oil to thicken excessively when cold and become
very thin when hot. The degree to which the viscosity of an oil is affected by tem-
perature is measured on a scale that originally ranged from 0 to 100 and is called
the viscosity index (Speight 2014). Oil that changes the least in viscosity when the
temperature is changed has a high viscosity index. Naphthenic oils have viscosity
indices of 35 or lower, compared with 70 or higher for paraffinic oils.
1.2.3 Finishing Processes
By combining three catalytic hydroprocessing steps (hydrocracking, hydroisomer-
ization, and hydrotreating), molecular constituents with poor lubricating qualities
are transformed and reshaped into higher quality base oil molecules. Pour point,
viscosity index, and oxidation stability are controlled independently. All three steps
convert undesirable constituents into desirable product, rather than having one, two,
or all three steps rely on subtraction. Among the many benefits of this combination
of processes is greater crude oil flexibility; that is, less reliance on a narrow range of
crude oils from which to make high-quality base oils. In addition, the base oil per-
formance is exceptionally favorable and substantially independent of crude source,
unlike solvent-refined base oil.
The process consists of fixed bed catalytic reactors that typically use a nickel–
molybdenum catalyst to neutralize, desulfurize, and denitrogenate lube base stocks.
These processes do not saturate aromatics or break carbon–carbon bonds as in other
hydrogen finishing processes. Sulfuric acid treatment is still used by some refiners
for the manufacture of specialty oils and the reclamation of used oils. This process is
typically conducted in batch or continuous processes similar to the chemical refining
processes with the exception that the amount of acid used is much lower than that
used in acid refining.
Clay contacting involves mixing the oil with fine bleaching clay at elevated tem-
perature followed by separation of the oil and clay. In the process, the clay is mixed
intimately with the oil at elevated temperatures for a short period followed by sepa-
ration of the oil and clay. This process may be used alone or in combination with an
acid treating process for the finishing and neutralization of lube base stocks.
The process is an adsorption process used to remove polar compounds from lubri-
cating oils thus improving color and the chemical, thermal, and color stability of the
lube base oil. The process variables include the type of clay, clay dosage, and high
treatment temperatures (150°C–370°C, 300°F–700°F). Clay contacting has been
replaced with hydrogen finishing in the manufacture of base oils with the exception
that some manufacturers use the process for manufacturing specialty oils. This pro-
cess improves color and chemical, thermal, and color stability of the lube base stock,
and is often combined with acid finishing.
Clay percolation (a cyclic process consisting of adsorption and regeneration cycles)
is a static bed adsorption process used to purify, decolorize, and finish lube stocks
and waxes. It is still used in the manufacture of refrigeration oils, transformer oils,
turbine oils, white oils, and waxes. Clay percolation has, in large part, been replaced
by hydrogen finishing but is still in limited use for the manufacture of refrigeration
oils, transformer oils, turbine oils, white oils, and waxes. Although Attapulgus clay
can be used, the most frequently used clay is activated bauxite. The process variables
include temperature, flow rate, throughput and type of clay.
Attapulgus clay is a hydrous magnesium-aluminum silicate and belongs to the
naturally active class of adsorbents, that is, adsorptive properties are developed by
thermal treatment alone. The degree of activity is determined by the amount of water
of hydration retained after thermal treatment. Attapulgus clay may be used to decol-
orize and neutralize any petroleum oil. Due to the relatively large pores in Attapulgus
clay, it is well adapted to the removal of high–molecular weight sulfonates, resin con-
stituents, and asphaltene constituents. It is moderately effective in removing odorous
compounds and trace metals, but does not strongly adsorb aromatics.
Activated bauxite is composed primarily of hydrated aluminum oxide (bauxite)
with minor amounts of silica, titania (titanium dioxide, titanium oxide), kaolinite,
and hematite. Like Attapulgus clay, activated bauxite belongs to the class of adsor-
bents activated by heat alone. In addition to decolorization, activated bauxite reduces
organic acidity, affords oils of improved demulsibility, often improves oxidation sta-
bility, and deodorizes. It is a good refining agent for turbine and transformer oils. A
major advantage in using activated bauxite is that although the efficiency declines
with successive adsorption–regeneration cycles, it eventually reaches a constant value
(typically 60%–70% of the new clay efficiency). Once this equilibrium efficiency
is obtained, no additional reduction in efficiency occurs with further regeneration.

Conversely, Attapulgus clay does not attain equilibrium efficiency. The efficiency of
Attapulgus clay continues to decline with each successive adsorption–regeneration
cycle.
Hydrofinishing processes (hydrorefining processes) have largely replaced the acid
and clay finishing processes. Hydrofinishing processes are mild hydrogenation pro-
cesses used to improve the color, odor, thermal, and oxidative stability, as well as
the demulsibility of lube base stocks. Chemically, these processes do not saturate
aromatics or break carbon–carbon bonds as in other hydrogen processes. Sulfuric
acid treating is still used by some refiners for the manufacture of specialty oils and
the reclamation of used oils.
The operating conditions are dependent on feedstock composition (related to
crude source as well as type and severity of prior processing), catalyst, and product
specifications. The effects of hydrogen finishing temperature and pressure are highly
dependent on the quality of the feedstock, product specifications, and the type of
catalyst used. An increase in temperature or pressure will generally improve desul-
furization, denitrification, product color, and product stability (Speight and Ozum
2002; Hsu and Robinson 2006; Gary et al. 2007; Speight 2014). However, increasing
the temperature above some maximum that is related to the catalyst and feedstock
quality will degrade the color, color stability, oxidation stability, and other properties
of the base oil.
Finally, although an increase in temperature will usually lead to an improvement
in color, excessively high temperatures will darken the oil much like excessive acid
contact time or high contact temperature leads to color degradation. Use of exces-
sively high temperature will also lead to cracking (hydrocracking) of the feedstock.
On the other hand, an increase in pressure will improve the color of the base oil.
1.3 BLENDING
In a blending operation, the base oil is mixed with other base oil fractions and with
additives to give it the desired physical properties (such as the ability to withstand
low temperatures). At this point, the product (lubricating oil) is subjected to a variety
of quality control tests that assess its viscosity, specific gravity, color, flash and fire
points. Oil that meets quality standards is then packaged for sale and distribution.
Most applications of lube oils require that they be nonresinous, pale-colored,
odorless, and oxidation-resistant. Common physical tests and chemical tests used to
classify and determine the grade of lubricating oils include measurements for viscos-
ity, specific gravity, and color, whereas typical chemical tests include those for flash
and fire points.
However, of all the properties, viscosity is often considered to be the most impor-
tant property. The application and operating temperature range are key factors
in determining the proper viscosity for lubricating oil. For example, if the oil is
too viscous, it offers too much resistance to the metal parts moving against each
other. On the other hand, if it is not viscous enough, it will be squeezed out from
between the mating surfaces and will not be able to lubricate them sufficiently. The
Saybolt Standard Universal Viscometer is the standard instrument for determining
the viscosity of petroleum lubricants between 70°F and 210°F (21°C and 99°C).
Viscosity is measured in the Saybolt universal second (SUS), which is the time
in seconds required for 50 mL of oil to empty out of a Saybolt viscometer cup
through a calibrated tube orifice at a given temperature (ASTM D2161, ASTM
2012).
The specific gravity of oil depends on the refining method and the types of addi-
tives present, such as lead, which give the lubricating oil the ability to resist extreme
mating surface pressure and cold temperatures. The color of the lubricating oil indi-
cates the uniformity of a particular grade or brand. The oil’s flash and fire points
vary with the crude oil’s origin. The flash point is the temperature to which an oil has
to be heated until sufficient flammable vapor is driven off so that it will flash when
brought into contact with a flame. The fire point is the higher temperature at which
the oil vapor will continue to burn when ignited.
Common engine oils are classified by viscosity and performance according to
specifications established by the U.S. SAE. Performance factors include wear pre-
vention, oil sludge deposit formation, and oil thickening.
The consistent performance of hydrocarbon lubricant base oils is a critical factor
in a wide variety of applications such as engine oils, industrial lubricants, and met-
alworking fluids (ASTM D6074). In addition, in many of these applications, humans
are exposed to the base oils as a component of a formulated product such that health
or safety considerations may need to be addressed. This guide suggests a compila-
tion of properties and potential contaminants that are understood by those knowl-
edgeable in the manufacture and use of hydrocarbon lubricants to be of significance
in some or all applications.
Potential sources of base oil variation include the raw material, manufacturing
process, operating conditions, storage, transportation, and blending. The test meth-
ods, base oil properties, and potential contaminants suggested are those that would
likely be useful in many common situations, although it is recognized that there are
specific applications and situations that could have different requirements.
Some lubricants are incompatible because of differences in additive chemistry
that lead to undesirable chemical reactions. If these oils are mixed, insoluble mate-
rial may form and then deposit onto sensitive machine surfaces. For a hydraulic
fluid, this could lead to lubricant starvation, valve failure, or increased wear. A
second form of lubricant incompatibility is more difficult to handle because no
visible changes occur when the products are mixed. The problem appears only
after the mixture is used in a piece of equipment that consequently fails or loses
performance. Optimum performance requires carefully balanced frictional and
antiwear properties in the finished product that are upset when the lubricants are
mixed.
Some incompatible lubricant mixtures may also affect synthetic rubber seals.
Lubricants are formulated to be neutral to seals or cause them to swell slightly. Too
much seal swell, seal shrinkage, or chemical deterioration may occur with some
combinations of lubricants. Engine oils formulated with certain types of dispersants
attack fluorocarbon seals.
Lubricant incompatibility is a chemistry problem—two oils made by the
same manufacturer may be incompatible. The most common cause of lubricant
incompatibility that results in the formation of harmful solids is the reaction of an

acidic component in one oil with a basic component in another oil.
Base oil testing helps ensure that quality is maintained throughout the refining,
blending, transportation, and storage process. Expertise in chemical analysis tech-
niques is also available to help with tough problem-solving, troubleshooting, formu-
lation, and trace contamination issues. Performance testing related to the specific
application should serve as the basis for identifying any contaminants and proving
the acceptability of the oil (ASTM 2012). And this is particularly true of any blended
products.
1.4 COMPOSITION AND PROPERTIES

Base stocks are classified into two broad types: (1) naphthenic and (2) paraffinic
depending on the crude types they are derived from. Naphthenic crudes are char-
acterized by the absence of wax or have very low levels of wax so they are largely
cycloparaffinic in nature and aromatic in composition. Therefore, naphthenic lube
fractions are generally liquid at low temperatures without any dewaxing. On the
other hand, paraffin-base petroleum contains wax, consisting largely of n-paraffins
and isoparaffins, which have high melting points. Waxy paraffinic distillates have
melting or pour points too high for winter use; therefore, the paraffins have to be
removed by dewaxing. After dewaxing, the paraffinic base stocks may still solidify,
but at higher temperatures compared with naphthenic ones because their molecular
structures have a more paraffinic character.
Lubricating oils are distinguished from other fractions of crude oil by their usu-
ally high (>400°C, >750°F) boiling point, as well as their high viscosity. Materials
suitable for the production of lubricating oils are comprised principally of hydro-
carbons containing from 25 to 35 or even 40 carbon atoms per molecule, whereas
residual stocks may contain hydrocarbons with 50 or more (up to 80 or so) carbon
atoms per molecule. The composition of lubricating oil may be substantially dif-
ferent from the lubricant fraction from which it was derived because wax (normal
paraffins) is removed by distillation or refining by solvent extraction, and adsorption
preferentially removes nonhydrocarbon constituents as well as polynuclear aromatic
compounds and the multiring cycloparaffins (Speight and Ozum 2002; Hsu and
Robinson 2006; Gary et al. 2007; Speight 2014).
Normal paraffins up to C36 have been isolated from petroleum, but it is difficult to
isolate any individual hydrocarbon from the lubricant fraction of petroleum. Various
methods have been used in the analysis of products in the lubricating oil range,
but the most successful procedure involves a technique based on the correlation of
simple physical properties, such as refractive index, molecular weight or viscosity,
and density. Results are obtained in the form of carbon distribution and the methods
may also be applied to oils that have not been subjected to extensive fractionation.
Although they are relatively rapid methods of analysis, the lack of information con-
cerning the arrangement of the structural groups within the component molecules is
a major disadvantage.
Nevertheless, there are general indications that the lubricant fraction contains a
greater proportion of normal and branched paraffins than the lower boiling portions
of petroleum. For the poly-cycloparaffin derivatives, a good proportion of the rings

appear to be in condensed structures, and both cyclopentyl and cyclohexyl nuclei are
present. The methylene groups appear principally in unsubstituted chains at least
four carbon atoms in length, but the cycloparaffin rings are highly substituted with
relatively short side chains.
Mononuclear, dinuclear, and trinuclear aromatic compounds seem to be the main
constituents of the aromatic portion, but material with more aromatic nuclei per
molecule may also be present. For the dinuclear aromatic constituents, most of the
material consists of naphthalene types. For the trinuclear aromatic constituents, the
phenanthrene type of structure predominates over the anthracene type. There are
also indications that the greater part of the aromatic compounds occur as mixed
aromatic–cycloparaffin compounds.
Base oils come from distillation or other refinery processes carried out on cer-
tain types of crude oil, and selected according to the characteristics required of the
lubricants. During the process, paraffin wax is removed from the base oil because of
the tendency of the wax to foul the base oil and render the lubricating oil unsuitable
for the designated service use. The wax is not a waste product but is used to make
a wide range of products such as candles. Paraffin wax is an inert, impermeable,
shiny, and biodegradable product that burns without harmful or corrosive fumes
being given off.
Once the purification process has been performed, base oils can be conveniently
subdivided into five categories (API 1509 2012, Appendix E):
1. Group I base stocks contain less than 90% v/v saturated constituents or
greater than 0.03% w/w sulfur and have a viscosity index greater than or
equal to 80 and less than 120—the temperature range for the use of these
oils is from 0°C to 65°C (32°F–150°F) and the base oils of this group are
prepared by solvent refining and tend to be the cheapest base oils on the
market.
2. Group II base stocks contain greater than or equal to 90% v/v saturated
constituents and less than or equal to 0.03% w/w sulfur and have a viscos-
ity index greater than or equal to 80 and less than 120—these base oils are
often manufactured by hydrocracking, which is a more complex process
than what is used for Group I base oils and because all of the hydrocarbon
constituents of these oils are saturated, Group II base oils have better anti-
oxidation properties; they also have a clearer color and cost more in com-
parison to Group I base oils. Group II base oils are becoming very common
on the modern market and are priced very close to Group I oils.
3. Group III base stocks contain greater than or equal to 90% saturates and less
than or equal to 0.03% w/w sulfur and have a viscosity index greater than or
equal to 120—these oils are refined to a greater extent than Group II base
oils and generally are severely hydrocracked (higher pressure and heat)—
this more severe process is designed to achieve a purer base oil. Although
made from petroleum, Group III base oils are sometimes described as syn-
thesized hydrocarbons. Like Group II base oils, these oils are also becom-
ing more prevalent on the modern market.
4. Group IV base stocks are composed of poly α-olefins (PAO)—these syn-

thetic base oils have a much broader temperature application range and are
very suitable for use in extreme cold conditions and high heat applications.
5. Group V base stocks, initially included all other base stocks not included
in Groups I, II, III, and IV, but the group has been expanded to include base
oils such as those produced from silicone polymers, phosphate ester, poly-
alkylene glycol, polyol-ester, and oils made from biomass sources (Speight
2008, 2011). These base oils are at times mixed with other base stocks to
enhance the properties of the base oil. An example would be PAO-based
compressor oil that is mixed with a polyol-ester. Esters are common Group
V base oils used in different lubricant formulations to improve the proper-
ties of the existing base oil. Ester oils can take more abuse at higher temper-
atures and will provide superior detergency compared with PAO synthetic
base oil, which in turn increases the hours of use.
To summarize again, almost every lubricant used in plants today started off as
base oil. The API has categorized base oils into five categories. The first three groups
are refined from petroleum crude oil. Group IV base oils are fully synthetic (PAO)
oils. Group V is for all other base oils not included in Groups I through IV. Before
all the additives are added to the mixture, lubricating oils begin as one or more of
these five API groups.
On the other hand, the SAE (SAE International) viscosity grades constitute a
classification for engine lubricating oils in rheological terms only and are intended
for use by engine manufacturers in determining the engine oil viscosity grades to
be recommended for use in their engines and by oil marketers in formulating and
labeling their products.
Finally, it is noteworthy that the use of base oils in modern systems has changed
dramatically in comparison to those in use two decades ago. For example, modern
Group II base oils are the most commonly used base oils and make up 47% v/v of
the plant capacity compared with 21% v/v for both Group II and III base oils two
decades ago. Currently, Group III base oils account for less than 1% v/v of the plant
capacity and Group I base oils, which previously made up 56% v/v of the plant
capacity, now account for 28% v/v of modern plant capacity.
1.5 USES
Lubricating oils may be divided into many categories according to the types of ser-
vice they are intended to perform. However, there are two main groups: (1) oils used
in intermittent service, such as motor and aviation oils, and (2) oils designed for
continuous service, such as turbine oils. Lubricating oil is distinguished from other
fractions of crude oil by a high boiling point (>400°C, >750°F), as well as a high
viscosity and, in fact, lubricating oil is identified by viscosity.
This classification is based on the SAE J 300 specification. The single-grade oils
(e.g., SAE 20) correspond to a single class and have to be selected according to
engine manufacturer specifications, operating conditions, and climatic conditions.
At −20°C (68°F), multigrade lubricating oil such as SAE 10W-30 possesses the
viscosity of a 10W oil and at 100°C (212°F) the multigrade oil possesses the viscos-
ity of an SAE 30 oil.
Oils used in intermittent service must show the least possible change in viscosity
with temperature; that is, their viscosity indices (Speight 2014) must be high. These
oils must be changed at frequent intervals to remove the foreign matter collected
during service. The stability of such oils is therefore of less importance than the sta-
bility of oils used in continuous service for prolonged periods without renewal. Oils
used in continuous service must be extremely stable, but their viscosity indices may
be low because the engines operate at fairly constant temperature without frequent
shutdown.
The pour point is an indicator of the ability of lubricating oil to flow at cold oper-
ating temperatures. The pour point of a fluid can be lowered with additives, called
pour point depressants, also known as cold flow improvers. As the lube oil sample
is cooled, small wax crystals form, the temperature at which this occurs is the cloud
point. As the sample is cooled further, the crystals agglomerate and grow in size
until the entire sample solidifies. Most pour point depressants do not alter the initial
formation temperature of the crystals and, thus, they do not generally affect the
cloud point. Rather, they inhibit the crystals from combining and growing to a size
large enough to plug filters.
Many researchers have tried to find a universal mechanism to explain the change
of the wax crystals in habit and particle size, from which the product design of
pour point depressants according to different kinds of diesel oils would benefit.
Adsorption, co-crystallization, nucleation, and improved wax solubility have been
accepted as the most widely used theories in explaining the mechanism (Zhang
et al. 2004; Chen et al. 2010). Many kinds of polymers that can be used as pour
point depressants have been developed to influence the behavior of paraffin crys-
tallite formation (Zhang et al. 2003; Soldi et al. 2007; Al-Sabagh et al. 2009; Chen
et al. 2009). Common pour point depressants include wax-alkylated naphthalene
derivatives, phenol derivatives, polymethacrylate derivatives, and styrene–ester
copolymers.
The most important single property of lubricating oil is its viscosity. Selected
chemicals (Nehal 2008), could be blended with the lubricating oils to impart to them
certain specific properties. Resistance of a lubricant to viscosity change with temper-
ature is determined by its viscosity index, which is an arbitrary number calculated
from the observed viscosities at two widely separated temperatures. The normal
range of viscosity index is from 0 up to 100. Oils of high viscosity index could resist
excessive thinning at high temperatures, whereas those of low viscosity index expe-
rience an extreme thinning at high temperatures.
The viscosity index is very important because it indicates the suitability of an oil
to lubricate properly at the elevated temperature of the engine. At the same time,
lubricating oil should be moderately viscous for operating during starting. Poly-
isobutylene and polymethacrylate are used as viscosity index improvers for lubricat-
ing oil.
Viscosity index improvers can be regarded as the key to high-performance mul-
tigrade oil. They are generally oil-soluble polymers, and oils containing viscosity
index improvers can achieve a viscosity index up to 150. Three major families of
viscosity index improvers are known: (1) olefin copolymers, (2) hydrogenated diene
copolymers, and (3) acrylic acid–based copolymers.
1.6 SYNTHETIC LUBRICATING OIL

Synthetic lubricating oil is a lubricant consisting of chemical compounds that are
artificially synthesized, rather than occurring naturally as petroleum constituents
(Rudnick and Shubkin 1999). Synthetic oils may cover a wide range of chemicals
but are generally found within the following categories: (1) synthetic hydrocarbons,
(2) hydrocarbon esters, (3) phosphate esters, (4) glycols, (5) chlorinated hydrocar-
bons, and (6) silicone oils. Synthetic hydrocarbons are similar in composition to
those found in petroleum base oils, but they are synthesized using chemical pro-
cesses in which basic carbon and hydrogen compounds are combined. Generally,
they are incorporated into oils to impart to the finished product enhanced levels of
the properties possessed by the petroleum distillate feedstocks.
Synthetic oils were originally designed for the purpose of having very pure base
oils with excellent properties. Thus, synthetic lubricating oil can be manufactured
using chemically modified petroleum constituents rather than whole crude oil, but
can also be synthesized from other raw materials. Synthetic lubricating oil is used as
a substitute for lubricating oil produced from petroleum when operating in extremes
of temperature because, in general, it provides superior mechanical and chemical
properties than those found in traditional mineral oil. Aircraft jet engines, for exam-
ple, require the use of synthetic oils, whereas aircraft piston engines generally do
not.
Synthetic lubricating oils provide a more advanced fluid option, giving greater
performance and reliability through more enhanced mechanical and chemical prop-
erties than traditional mineral oils. Several types of synthetic oils exist, all contain-
ing organic compounds or synthetic hydrocarbons. Contrary to what most people
believe, engines that run with synthetic oils require as much maintenance as engines
running with nonsynthetic oils.
Synthetic lubricating oils consist of the following classes of lubricants:
(1) PAO—API Group IV base oils; (2) synthetic esters—API Group V base oils
(non-PAO) synthetics such as diesters, polyol-esters, alkylated naphthalene deriva-
tives, and alkylated benzenes; and (3) hydrocracked/hydroisomerized—API Group
III base oils prepared by processes involving the catalytic conversion of feedstocks
under pressure in the presence of hydrogen into high-quality mineral lubricating
oil.
Semisynthetic lubricating oils (synthetic blends) are blends of mineral oil with
less than 30% v/v synthetic oil and are designed to have many of the benefits of syn-
thetic oil without matching the cost of pure synthetic oil. Lubricating oils that have
synthetic base stocks even lower than 30% v/v, and high-performance additive packs
consisting of esters can also be considered synthetic lubricants. In general, the ratio
of the synthetic base stock to mineral oil base stock is used to define commodity
codes among the customs declarations for tax purposes.
Group II and Group III–type base stocks help formulate more economic type
semisynthetic lubricants. Groups I, II, II+, and III–type mineral-based oil stocks
are widely used in combination with additive packages, performance packages, and
esters or Group IV PAOs to formulate semisynthetic-based lubricants. Group III
base oils are sometimes considered synthetic, but they are still classified as highest-
top-level mineral-based stocks.
High-performance synthetic oils—technologically advanced motor fluids for
enhanced performance in the most extreme conditions—contain customized addi-
tives that add to the engine performance. Friction modifiers, for example, provide
more horsepower at better fuel economy. The resistance of the fluid to breakdown
(from oxidation) and the formation of deposits make these oils effective lubricants
that also protect the engine. In preparing the perfect high-performance synthetic oil,
oil manufacturers have tried different compositions of additives and synthetic fluids
to get the mixture with the most desirable attributes, modifying high-performance
oils for viscosity grade and other engine dynamics by adding or subtracting these
additives from the base fluid.
1.6.1 Poly Alpha-Olefins
PAOs are the most popular synthetic lubricants—the chemical structure and proper-
ties are similar to those of mineral oils. PAOs (synthetic hydrocarbons) are manu-
factured by polymerization of hydrocarbon molecules (α-olefins) in the presence of
a catalyst.
A polyolefin (poly-alkene) is a polymer that is produced from a simple olefin
(alkene, CnH2n) as a monomer. A more specific type of olefin is a PAO, a polymer
made by polymerizing an α-olefin, which is an alkene where the carbon–carbon
double bond starts at the α-carbon atom, that is, the double bond is between the
#1 and #2 carbons in the olefin molecule. Furthermore, with increasing options of
catalytic processes available, it is now possible to produce tailor-made PAOs and
thus control the properties of the end products, such as viscosity and the viscosity
index.
Many PAOs have flexible alkyl branching groups on every other carbon of
their polymer backbone chain. These alkyl groups, which exist in numerous three-
dimensional conformations (molecular shapes), make it very difficult for the polymer
molecules to align themselves side-by-side in an orderly way. Therefore, many PAOs
do not crystallize or solidify easily and are able to remain oily, viscous liquids even
at lower temperatures. Because of this property, low–molecular weight PAOs are
useful as synthetic lubricants such as synthetic motor oil for vehicles used in a wide
range of temperatures (Ray et al. 2012).
The hydrogenated PAOs result from the oligomerization of decene-1 (C10H20,
CH3CH2CH2CH2CH2CH2CH2CH2CH=CH2) as well as from dodecene-1 (C12H24,
CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH=CH2), which are obtained by the
polymerization of ethylene (CH2=CH2). The resulting oligomers are hydrogenated
and distilled in different fractions. In terms of manufacture, these base oils are com-
pletely paraffinic in nature and do not contain aromatics or various heteroatoms.
They are characterized by a high viscosity index, ease of adjusting volatility by dis-
tillation, and good cold-flow behavior. In fact, with regard to the manufacture of
conventional base oils, synthetic oils are tailor-made.
1.6.2 Poly Internal-Olefins
Poly internal-olefins are long-chain hydrocarbons, typically a linear backbone with
some branching randomly attached and are obtained by oligomerization of internal
n-olefins (e.g., R1CH=CHR2, where R1 and R2 are various alkyl groups; Corsico et
al. 1999; Rudnick 2013).
The poly internal-olefins have good thermal and oxidative stability and are used
extensively in synthetic lubricating oil formulations. Poly-internal olefins offer simi-
lar performance to PAO oils and are a high-quality base stock for modern lubricant
formulations.
1.6.3 Poly-Butenes
Poly-butene is typically made from the C4 stream (butene-1, butene-2, and isobu-
tylene) from a catalytic cracker after the stream is treated to remove sulfur (Speight
and Ozum 2002; Hsu and Robinson 2006; Gary et al. 2007; Speight 2014). The
ethylene steam cracker C4 stream is also used as supplemental feedstock for the pro-
duction of poly-butene. On the other hand, poly-isobutylene is produced from pure
isobutylene made in the petrochemical complex of a major refinery. The presence of
isomers other than isobutylene can have several effects including: (1) lower reactiv-
ity due to steric hindrance at the terminal carbon in, for example, the manufacture
of poly-isobutenyl succinic anhydride dispersant manufacture; (2) the molecular
weight–viscosity relationships of the two materials may also be somewhat different
(Decroocq and Casserino 2005).
The reaction is an acid-catalyzed carbocation polymerization typically using alu-
minum chloride (AlCl3) or a hydrogen halide acid such as hydrofluoric acid. The
repeat unit in case of 1-butene is [–CH2CH(CH2CH3)–]n and the repeat unit in case
of 2-butene is [–CH(CH3)CH(CH3)–]n. One of the end units in the polymer chain
contains a double bond, allowing reactivity with other compounds to provide func-
tional chemistry mainly for lubricant additives for engine oils, fuels, and greases
(Rudnick 2013).
1.6.4 Organic Esters
An ester oil is a synthetic base oil that has been chemically synthesized. Esters
are derived from carboxylic acids (which contain the −COOH functional group) in
which the hydrogen atom in the carboxylic acid group is replaced by a hydrocarbon
group. This could be an alkyl group like methyl or ethyl, or one containing a benzene
ring such as the phenyl group (C6H5–). Esters have been used successfully in lubrica-
tion for more than 60 years and are the preferred stock in many severe applications
in which their benefits solve problems or bring value.
Ester oils are produced by the reaction of acids and alcohols with water. Ester oils
are characterized by very good high-temperature and low-temperature tolerance.
There are many types of esters including polyolesters and complex esters. Esters
are often used in jet engine lubrication due to their low temperature flow properties
with clean, high-temperature capacity. Ester oils are often used in combination with
PAO lubricating oils in fully synthetic motor oils—ester content varies from 5% to
25% w/w depending on the ester and the desired properties. The high-performance
properties and custom design versatility of esters is ideally suited to problem solving
in the industrial arena. These oils are available in a wide range of viscosities and
are more generally used under high temperatures (maximum from 180°C to 230°C,
355°F to 445°F; Rudnick 2013).
Ester lubricants are a broad and diverse family of synthetic lubricant base oils,
which can be custom-designed to meet specific physical and performance proper-
ties. The inherent polarity of esters improves their performance in lubrication by
reducing volatility, increasing lubricity, providing cleaner operation, and making
the products biodegradable. A wide range of available raw materials allow an ester
lubricant designer the ability to optimize a product over a wide range of variables to
maximize the performance and value to the client. They may be used alone in very
high-temperature applications for optimum performance or blended with PAOs or
other synthetic base stocks in which their complementary properties improve the
balance of the finished lubricant. The application of ester lubricants continues to
grow as the drive for efficiency makes operating environments more severe. Because
of the complexity involved in the design, selection, and blending of an ester base
stock, the choice of the optimum ester should be left to a qualified ester engineer who
can better balance the desired properties.
The primary structural difference between ester-based lubricating oil and
petroleum-based lubricating oil (including PAO lubricating oils) is the presence
of oxygen in the hydrocarbon molecules in the form of multiple ester linkages
(COOR), which impart polarity to the constituent molecules of the lubricating oil.
As a result, this affects the manner in which esters behave as lubricants, such as
in the following properties: (1) volatility, (2) lubricating behavior, often referred
to as lubricity, (3) detergent properties and ability to act as a dispersant, and
(4) biodegradability.
In terms of volatility, the polarity of the ester molecules causes an intermolecular
attraction (through hydrogen bonding) causing them to be attracted to one another,
and this intermolecular attraction requires more energy (heat) for the esters to transfer
from a liquid to a gaseous state. Therefore, at a given molecular weight or viscosity,
the ester-based lubricating oils will exhibit a lower vapor pressure, which translates
into a higher flash point and a lower rate of evaporation for the lubricant. Generally,
the more ester linkages in a specific ester, the higher its flash point and the lower its
volatility.
The lubricating behavior of ester-based lubricating oils is also subject to the polar
effect of the ester group. Polarity also causes the ester moieties to be attracted to
positively charged metal surfaces. As a result, the molecules tend to line up on the
metal’s surface, creating a film that requires additional energy (load) to wipe off. The
result is a stronger film, which is reflected in better lubricating behavior and lower
energy consumption in lubricant applications.
The polar nature of esters also introduces detergent and dispersant properties,
which makes the ester-based oils good solvents and dispersants. This allows the
esters to solubilize or disperse oil degradation by-products, which might otherwise
be deposited as sludge, and is manifested as cleaner operation and improved additive

solubility in service.
Although ester-based oils have enhanced stability (compared with petroleum-
based oils) against oxidative and thermal breakdown, the ester linkage provides a
vulnerable site for microbes and the rate of biodegradability of the ester-based oils
is enhanced.
However, as with any product, there are also disadvantages to the use of ester-
based lubricating oils. The most important issue is the compatibility of the ester base
stocks with the elastomer material used in the machinery seals. Esters (and there are
few if any exceptions) will swell and soften most elastomer seals but, fortunately, the
degree to which the seals swell can be controlled through proper selection. When
used as the exclusive base stock, the ester should be designed for compatibility with
seals or the seals should be changed to those types that are more compatible with
esters.
Another potential disadvantage with esters is their ability to react with water or
hydrolyze under certain conditions. Generally this hydrolysis reaction requires the
presence of water and heat with a relatively strong acid or base to act as a catalyst.
Because esters are usually used in very high temperature applications, high amounts
of water are usually not present and hydrolysis is rarely a problem in actual use.
Where the application environment may lead to hydrolysis, the ester structure can
be altered to greatly improve its hydrolytic stability and additives can be selected to
minimize any effects.
1.6.5 Polyglycols
Polyglycols are produced by the oxidation of ethylene and propylene. The oxides
are then polymerized, resulting in the formation of polyglycols, which are water
soluble. Polyglycols are characterized by very low coefficients of friction. They
are also able to withstand high pressures without extreme pressure additives
(Rudnick 2013).
1.6.6 Silicones
Silicones are a group of inorganic polymers, molecules of which represent a backbone
structure built from repeated chemical units (monomers) containing Si=O moieties.
Two organic groups are attached to each Si=O moiety: for example, methyl + methyl
[(CH3)2], methyl + phenyl (CH3+ C6H5), phenyl + phenyl [(C6H5)2]. The most popular
silicone is polydimethylsiloxane—the monomer is (CH3)2SiO. Polydimethylsiloxane
is produced from silicon and methyl chloride. Other examples of silicones are poly-
methylphenylsiloxane and polydiphenylsiloxane.
The viscosity of silicones depends on the length of the polymer molecules and on
the degree of cross-linking. Short non–cross-linked molecules make fluid silicones,
whereas long cross-linked molecules result in elastomeric silicones. Silicone lubri-
cants (oils and greases) are characterized by a broad temperature range: −73°C to
300°C (−100°F to 570°F; Rudnick 2013).
1.6.7 Blended Oils
Blended oils (compounded oils) are lubricating oils in which the properties are improved
by the addition of additives. Additives enhance certain desirable properties of the base
lubricating oil or give it new desired properties. Additives that improve oiliness include
fatty acids, castor oil, and coconut oil. Antioxidant additives include phenolic com-
pounds and amino compounds. Antifoaming agents that are added to lubricating oils
include glycerol and glycols, emulsifying additives include sulfuric acid and sodium
salts, and viscosity index–improving additives include compounds with high molecu-
lar weights, such as hexanol (C6H13OH; n-hexanol, boiling point 158°C, 315°F).
However, modern high-performance lubricants are specifically formulated with
a carefully selected balance of performance additives and base stocks to match the
lubrication requirements of the equipment in which they are used. Thus, blend-
ing oils should be performed with extreme care—when lubricants are mixed, this
balance is often upset. Mechanical problems leading to shorter equipment life can
occur, sometimes catastrophically.
A general rule is that lubricants made with synthetic base stocks should not
be mixed with products made with mineral oil, even if they are designed for the
same application. The limited exceptions include some PAO and ester-based prod-
ucts. Even then, compatibility is often concentration-dependent. Deposits may form
because of additive incompatibility or seal compatibility may be compromised.
1.6.8 Biolubricants
Vegetable lubricants are based on soybean, corn, castor, canola, cottonseed, and
rapeseed oils. Vegetable oils are an environmentally friendly alternative to mineral
oils because they are biodegradable. Lubrication properties of vegetable base oils are
identical to those of mineral oils. The main disadvantages of vegetable lubricants are
their low oxidation and temperature stabilities.
Animal lubricants are produced from animal fat. There are two main animal fats:
hard fats (stearin) and soft fats (lard). Animal fats are mainly used for manufactur-
ing greases. Animal oils and vegetable oils are extracted from animal and vegetable
sources. They are typically triglycerides—the chains of fatty acids that are bound
with a single molecule of glycerol. Animal and vegetable oils are high in viscosity
and provide good lubrication. Animal oils include seal oil, whale oil, and lard oil.
Vegetable oils include cottonseed oil, olive oil, mustard oil, and palm oil.
Animal and vegetable oils have some disadvantages: they oxidize easily to form
acidic products, they are expensive, and they get hydrolyzed easily in the presence of
moist air or another aqueous medium. Chemical additives are added to animal and
vegetable oils to improve the properties.
Vegetable oils as new renewable raw materials for industrial applications such as
lubricants have been of great importance because of the emphasis on environmen-
tally friendly lubricants, and are attractive due to the rapid depletion of world fos-
sil fuel reserves and increasing concern for environmental pollution from excessive
mineral oil use (Chauhan and Chhibber 2013).
Vegetable oils with high oleic contents are considered to be the best alternative
for substituting conventional mineral oil–based lubricating oils and synthetic esters.
Vegetable oils are preferred over synthetic fluids because they are more ecofriendly,
renewable resources and cheaper too. The properties of vegetable oils, fatty esters,
chemically modified esters, and synthetic esters are relevant for performance as
lubricants in various industrial applications such as hydraulic oils, refrigeration oils,
chainsaw lubricants, metal-working fluids, engine oils, and two-stroke engine oils
(Chauhan and Chhibber 2013).
Advantages such as high lubricity, appropriate viscosity–temperature relation-
ship, low lubricant consumption, and energy efficiency combined with suitable public
health, safety, and environmental contamination records, more than offset the dis-
advantages of initial costs in most of these applications. It has been suggested that
modified and stabilized oils from wastes of forest origin and other nonedible oils and
their chemically modified derivatives can be produced at relatively cheaper cost than
similar oils marketed in the developed world and can be introduced in India with
immense environmental and performance benefits.
1.7 BASE OIL PROPERTIES

Base oils are manufactured to specifications that place limitations on their physical
and chemical properties, and these in turn establish parameters for refinery opera-
tions (Bartz 1993; Sequeira 1994). Because of the differences in petroleum composi-
tion and subtle differences in refining process parameters (Speight and Ozum 2002;
Hsu and Robinson 2006; Gary et al. 2007; Speight 2014), base stocks from different
refineries will generally not be identical, although they may have some properties
(e.g., viscosity at a particular temperature) in common. At this point, it is worth
briefly reviewing what measurements are involved in these specifications, what they
mean, and where in the process they are controlled.
The various properties are listed below in alphabetical order for the convenience
of the reader.
1.7.1 Aniline Point
The aniline point is a measure of the ability of the base stock to act as a solvent and
is determined from the temperature at which equal volumes of aniline and the base
stock are soluble (ASTM D611). High aniline points imply a paraffinic base stock,
whereas low aniline points (<100°C) imply a naphthenic or aromatic stock.
1.7.2 Cloud Point
The cloud point is the temperature at which wax crystals first form as a cloud of micro-
crystals. It is therefore higher than the pour point, at which crystals are so numerous
that flow is prevented. The long-standing ASTM method is D2500, with three new
automated methods being ASTM D5771, ASTM D5772, and ASTM D5773. Many
base stock inspection sheets no longer provide cloud points. Cloud points can be 3°C
to 15°C above the corresponding pour points.
1.7.3 Color
Solvent-extracted/solvent-dewaxed stocks will retain some color as measured by
ASTM D1500. Hydrocracked stocks, when hydrofinished at high pressures, are usu-
ally water white and their color is best measured on the Saybolt color scale (ASTM
D156, ASTM 2012).
1.7.4 Density and API Gravity

Knowledge of density is essential when handling quantities of the stock and the
values can also be seen to fit with the base stock types. An alternative measure is the
API gravity scale where:
API gravity = (141.5/specific gravity) − 131.5
Density increases with viscosity, boiling range, and aromatic and naphthene content,
and decreases as isoparaffin levels increase and as the viscosity index increases.
1.7.5 Distillation
At one time, this would have been carried out using an actual physical distillation
using either ASTM D86, a method performed at atmospheric pressure and applicable
to very light lubes, or by vacuum distillation according to ASTM D1160, for heavier
ones. Neither of these methods is employed much for base stocks nowadays because
of their time and manpower requirements. Distillation today is usually performed
using gas chromatography and the method is commonly called either simulated dis-
tillation (SimDist) or gas chromatographic distillation using ASTM D2887. This
method is capable of excellent accuracy, repeatability, and fast turnaround times and
is normally automated. It is applicable to samples with final boiling points of less
than 538°C (1000°F).
1.7.6 Flash Point
The flash point is the temperature at which there is sufficient vapor above a liquid sam-
ple to ignite when exposed to an open flame and is a significant feature in product appli-
cations in which it is used as a common safety specification. Flash points are a reflection
of the boiling point of the material at the front end of the base stock’s distillation curve.
Flash points generally increase with viscosity grade and a high flash point for a given
viscosity is desirable. Careful fractionation so that undesirable constituents are rejected
and increased viscosity index of the base stock favor higher flash points. The Cleveland
Open Cup test method (ASTM D92) is the most often cited for North American base
stocks, although the Pensky–Martens test (ASTM D93) is sometimes used.
1.7.7 Pour Point
The pour point measures the highest temperature at which a base stock no longer
flows, and for paraffinic base stocks, pour points are usually between −12°C (10°F)
and −15°C (5°F), and are determined by operation of the dewaxing unit. For spe-
cialty purposes, pour points can be much lower. The pour points of naphthenic base
stocks, which can have a very low wax content, may be much lower (−30°C to −50°C,
−22°F to −58°F). For very viscous base stocks such as bright stocks, pour points may
actually reflect a viscosity limit.
The pour point is measured traditionally by ASTM D97, but three new automated
equivalent test methods are the “tilt” method (ASTM D5950), the pulse method
(ASTM D5949), and the rotational method (ASTM D5985).
1.7.8 Refractive Index and Refractivity Intercept

The refractive index is used to characterize base stocks, with aromatic ones having
higher values than paraffinic ones. The value increases with molecular weight.
The significance of refractive index data is the relationship between the refractive
index (n) and the density (d) of hydrocarbons. Thus,
Refractivity intercept = n − d/2
This is characteristic of each hydrocarbon series and has been shown to represent a
more constant relationship between the density and refractive index of the members
of a homologous series of hydrocarbons than the usual equations for refractivity.
This is a means of characterizing the composition of the sample—values range from
1.03 to 1.047.
1.7.9 Viscosity
Base stocks are primarily manufactured and sold according to their viscosities at either
40°C (104°F) or 100°C (212°F), using kinematic viscosity. Viscosity grades are now
defined by kinematic viscosity in centistokes (cS) at 40°C (104°F); formerly, they were
established on the SUS scale at 38°C (100°F). Higher viscosity base stocks are pro-
duced from heavier feedstocks (e.g., a 100 cS at 40°C oil is produced from heavy
vacuum gas oil and cannot be made from a light vacuum gas oil because the molecular
precursors are not present). As viscosity increases, so does the distillation midpoint.
1.7.10 Viscosity–Gravity Constant
The viscosity–gravity constant is an indicator of base stock composition and sol-
vency that is calculated from the density and viscosity according to ASTM D2501;
it usually has a value between 0.8 and 1.0. High values indicate higher solvency
and therefore greater naphthenic or aromatic content. This is usually of interest for
naphthenic stocks.

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ChemiCal iNDUSTRieS/138

MOST RECENTLY PUBLISHED

Refining Used Lubricating Oils, James Speight and Douglas I. Exall

Boca Raton London New York

CRC Press is an imprint of the

© 2014 by Taylor & Francis Group, LLC

No claim to original U.S. Government works

International Standard Book Number-13: 978-1-4665-5150-3 (eBook - PDF)

and the CRC Press Web site at

Chapter 1 Manufacture of Lubricating Oil............................................................1

1.7.11 Viscosity Index............................................................ 30

Chapter 2 Types and Properties of Lubricating Oils........................................... 43

2.4.12.3 Antiwear and Extreme Pressure Additives.... 65

Chapter 3 Used Lubricating Oils......................................................................... 73

Chapter 4 Composition and Treatment................................................................ 91

Chapter 5 Combustion of Used Engine Oil....................................................... 115

Chapter 6 Alternative Processing Options......................................................... 141

7.6.8 The Shell Upgrading Process.................................... 221

Chapter 8 Economics and Other Evaluation Criteria........................................ 273

8.7.2 Example 2: Re-Refining in a Hydrogen-Rich

Chapter 9 Choice of a Process Technology....................................................... 293

9.2.16 Nigeria Workshop on Used Oil Management

James G. Speight, PhD, DSc

hydrocarbons (alkanes), cycloalkanes, and aromatic hydrocarbons. Polynuclear

1.2 BASE OIL MANUFACTURE FROM PETROLEUM SOURCES

1.2.1 Base Oil Manufacture

approximately related to molecular weight, the first step in manufacturing is to sepa-

Gas Heavy naphtha

Heavy gas oil

1.2.1.2 Chemical Refining Processes

1.2.1.4 Solvent Refining Processes

Steam heater Heater

1.2.1.6 Catalytic Dewaxing and Hydroisomerization

is obtained, no additional reduction in efficiency occurs with further regeneration.

i­ncompatibility that results in the formation of harmful solids is the reaction of an

1.4 COMPOSITION AND PROPERTIES

of petroleum. For the poly-cycloparaffin derivatives, a good proportion of the rings

4. Group IV base stocks are composed of poly α-olefins (PAO)—these syn-

1.6 SYNTHETIC LUBRICATING OIL

be deposited as sludge, and is manifested as cleaner operation and improved additive

1.7 BASE OIL PROPERTIES

1.7.4 Density and API Gravity

API gravity = (141.5/specific gravity) − 131.5

1.7.8 Refractive Index and Refractivity Intercept

Refractivity intercept = n − d/2

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1.2 BASE OIL MANUFACTURE FROM PETROLEUM SOURCES

1.2.1 Base Oil Manufacture

1.2.1.2 Chemical Refining Processes

1.2.1.4 Solvent Refining Processes

1.2.1.6 Catalytic Dewaxing and Hydroisomerization

incompatibility that results in the formation of harmful solids is the reaction of an

1.4 COMPOSITION AND PROPERTIES

1.6 SYNTHETIC LUBRICATING OIL

1.7 BASE OIL PROPERTIES

1.7.4 Density and API Gravity

1.7.8 Refractive Index and Refractivity Intercept