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Crude OilChemistry

Vastly SimanzhenkovUniversity Duisburg-Essen

Duisburg, Germany

Raphael IdemUniversity of Regina

Regina, Saskatchewan, Canada

Copyright © 2003 by Marcel Dekker, Inc. All Rights Reserved.

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Preface

This book is devoted to students as well as scientists and process engineers in-

volved in petroleum science, refining and engineering. Part I of the book gives a

historical overview of the origin of petroleum . The first chapter shows how crude

oil is l inked with human civilization. In this chapter i t is also shown that the en-

ergy used to run most of today's machinery derives from petroleum. It also pro-

vokes our im aginat ion on how the var ious m oving parts of m achinery would oper-

ate wi thou t m inera l oil or lubricating oil , both of which are also produced from

crude oil. The first chapter also provides insight into the problems that have arisen

as a result of ap plyin g different standards by different countries to similar crude oil

products and how these problem s are tackled.

The second chapter of Part I deals with m odern analytica l m ethods used in crude

oil chemistry. Modern and classical methods of petroleum and petroleum product

characterization are explained. This chapter is an essential chapter for present and

potential crude oil chemists since analytical chemistry constitutes an important

part of crude oil chem istry. Besides, crude oil products have so m an y special

properties that are impor tan t for the industry . The need to determine these proper-

ties gives r ise to the use of very many analytical methods in the petroleum indus-

try.

Part II (i.e. chapters 3 and 4) shows th e geopolit ical and economic nature of pe-troleum chemistry. In this chapter, the initial stages of development of various

petro leum companies are shown. I t g ives a h istor ical run-down on how smal l

com panies of the past have blossom ed into g iant m ul t inat ional com panies of

wo rldwide repute. For readers, i t is especially interesting to learn the history of the

development of the Eastern Bloc companies, especially the Russian companies. In

this chapter , it is sh o w n how the polit ical situation in this country has had a great

influence on the economic development of all Russian industr ies in general and

th e petroleum industry in particular. It is also shown how it has been possible for

th e big Russian petroleum concerns to be formed in less than twenty years during

th e diff icult t imes of polit ical and economic reforms.

Chapters 5 and 6 of Part III of the book introduce th e reader to the science of crude

oil ref in ing. An illustration of the com plete process schem e that starts from crude

oil all the way to final products is g iven . In particular , th e process route of crude

oil from the well to the gas station and indeed the car tank is provided. These

chapters also present the techniques and technologies involved in most of the im-

portant processes used in modern petro leum ref iner ies for processing light and

heavy distil late fractions. Chapter 7 in Part III looks at ecological problems that


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arise in the crude oil industry. The chapter also shows that, in order to develop an

appropriate technology for crude oil treatment, not only are economically rational

decisions required, but also, ecologically acceptably decisions are needed. This

chapter looks at our environm ent as a very sensitive system that must be protected

with respect to the man y processes that take place in the petroleum refining indus-

try.

Good quality crude oil is often defined in term s of high API gravity and low sulfur

content. However, reserves of this type of oil are disappearing, giving rise to in-

creasing contributions from oil of lower API gravity and higher sulfur content. Is

th e chemistry of processing of the two types of oil different? This question is an-

swered in Part IV of this book. The chapter also introduces th e presence of asphal-

tenes in crude oil. A list of problems that occur during oil production, transporta-

tion, and processing that could be attributed to asphaltene presence in crude oil is

presented. New concepts and approaches that aid in the processing of crude oilswith sign ificant am ounts of asphaltenes are introduced. Part IV also looks at future

processes that may be introduced in the petro leum ref inery. These are hybrid fuel

production processes that involve combining th e well-known modern cracking

process with th e recycling of waste plastics or bio-fuels. The advantages than can

be derived from co-processing of asphaltene-containing crude oils with plastics or

biomass materials are given. Part IV also presents some analytical techniques that

could be used by petroleum engineers and chemists to better understand th e nature

of heavy crude oil and residues, and possible ways to positively influence their

processing. In all , Part IV presents crit ical material that can contribute towards

further development of the petroleum industry. This is especially true for the non-conventional petroleum industry, and it can be particularly important for North

America, since Canada has the largest reserves of non-conventional petroleum in

the world.

Both authors have worked extensively in the areas of petroleum science and engi-

neering. W e hope that this book will go a long way in introducing th e reader to the

fascinating world and concepts of the black gold of our planet.

Vasily Simanzhenkov

Raphael Idem


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Contents

Preface

Part I Classification and Characterizat ion of Crude Oil

1 Nature and Classificat ion of Crude Oil

1. History and nature of petroleum

1. .1 Origin of pet ro leum

1. .2 Oil form ation in the world's oceans

1. .3 M odern concept of fo rma t ion of petroleum

1. .4 Consequ ences of in tens ive ex tract io n and processing of oil

1. .4.1 Dang erous fogs1. .4.2 Black oceans

1.2 General propert ies and classifica t ion of petroleum :

comparison of petroleum from dif ferent countries

1.2.1 Fractions and chemical composition of petroleum

1.2.2 Che m ical classificat io n of petroleu m

1.2.3 Classifica t ion by de ns ity

1.2.4 Ch aracte rization by viscos i ty-gravi ty constant (vgc)

1.2.5 Tech nolog ical clas sific atio n of petroleum

1.3 Products f rom crude oil

1.3.1 Gasoline1.3.2 Je t fuel (kerosene)

1.3.3 Diesel

.3.4 Residual fuel

.3.5 Inte rna tion al standards for fuels

.4 Lubrica t ing o i l s and lubr icants

.4. Internat ional s tandards for lub ricat in g oi ls

.4. . 1 Industrial oi ls

.4. .2 Motor oi ls

.4. .3 Transmiss ion o i l s

.4. .4 Hydrau l i c oils

2 Modern Charac ter iza t ion and A nalys is Techniques fo r Crude Oil

2.1 Chrom a tograph ic m e thods

2.1.1 Gas chroma tography

2.1.2 High perfo rm ance l iquid chrom atography

2.1.3 Thin layer chrom atograph y

2.2 Spectroscopic methods

2.2.1 Infrared spectroscopy









































































































































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2.2.2 Ram an spectroscopy

2.2.3 Colorimetry and pho tome t ry2.2.4 Fluorescence and phosphorescence spectroscopy

2.2.5 A tom ic abso rption spectroscopy and atomic emission

spectroscopy

2.2.6 X-ray fluorescence spectroscopy

2.3 Other methods for e luc ida t ing th e structure of crude oil

2.3.1 Separation m etho ds

2.3 .2 Chem ical ana lys is m ethods of crude oil products:

de terminat ion of unsa tura ted com pounds

2.3.3 Struc tural bu lk analys is of heavy crude oil f rac t ions :

n-d-M method

2.4 Methods of charac ter iza t ion of collo idal properties of crude oil

an d its products

2.4.1 Direct m ethods

2.4.2 Indirect m ethods

2.5 De term inat ion of the ph ysic al propert ies of crude oil

2.5 .1 Den si ty de term inat ion

2.5.2 Viscosity dete rm inat io n

2.5 .3 Refrac t ive index de term inat ion

Bib l iography

Part II Regional Pe t ro leum Indust ry

3 Pe t ro l eum Produc ing Count r i e s : OPEC and Non-OPEC3.1 In t roduc t ion

3.1.1 Short back groun d on OPEC3.2 North America

3.2.1 U nite d States

3.2.2 Canada

3.3 Russia

3.3.1 The role of the pet ro leum indus t ry for Russia

3.3.2 Refo rm s in the Ru ssian oi l indu stry

3.3.3 Ru ssian petro leum and gas in the world market

3.3.4 Structure of the petro leum sector in Ru ssia3.4 Arabian Eas t

3.4.1 Oman

3.4.2 Iraq

3.4.3 Iran

3.4.4 Qatar3.4.5 Kuwait

3.4.6 Un ited Arab Em irates

3.4.7 Sau di A rab ia









































































































































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4 International Petroleum Companies

4.1 B ritish Petroleum

4.2 Castrol

4.3 ExxonMobi l

4.4 Neste/Fortum

4.5 Shell

4 .6 Total / F i n a / Elf

4.7 L U KO i l

4.8 Yukos

4.9 TN K

Bibl iography

Part III Main Processes in the Petroleum Refining Industry

5 Crude Oil Distil lation5.1 Petroleum and gas preparation

5.1.1 Formation of petro leum em ulsions and their basic p roperties

5.1.2 Separation of water-oil emuls ions

5.1.3 M echanical petroleum drying

5.1.4 Therm al petroleum drying

5.1.5 Chemical methods of petroleum drying

5.1.6 Therm al chem ical petroleum drying

5.1.7 Stabilization of petroleum

5.1.8 Techn ological schemes for petroleum preparation

5.1.9 Pressure extraction system5.2 Desalting

5.3 Atmospheric rectif ication

5.4 Vacu um recti f icat ion

5.5 Heat exchangers and separators

6 Processing of Light and He avy Distillates

6.1 Thermal cracking

6.2 Catalytic cracking

6.3 Visbreaking

6.4 Coking6.5 Hydroprocessing

6.6 Reforming

6.7 Isomerization

6.8 Alkyla t ion

6.9 Bl en d in g

7 Environmental Issues Facing th e Refining Industry

7.1 Introduction

7.2 M ethods of clean ing crude oil contam inated water and soil











































































































































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7.3 Methods of air and gas cleaning used in the crude oil indus t ry

7.4 Conclus ion to Part II I

Bib l iography

Part IV Heavy Oil Processing - Chemis t ry of Asphaltenes

8 Chemis t ry of Crude Oil Asphaltenes

8.1 Int roduct ion

8.2 Problems of crude oil residue treatment with respect

to asphaltenes

8.2.1 Coke for m ation and reduction of heavy metals

8.2.2 Treatm ent pos sibi l i t ies for crude oi l residues

8.2.2.1 Phy sical t reatmen t - deasphalt ing

8.2.2.2 Chemica l treatments

8.2.2.3 Visbreaking

8.2.2.4 Coking

8.2.3 Coke form ing reac tions d ur ing res idue t rea tment

8.2.3.1 Catalytic t reatment

8.2.3.2 Thermal t rea tment

8.3 Methods of analys is of crude oil residue

8.3.1 Methods and m a i n def in i t ions for the determinat ion

of coke form at ion tendency

8.3.2 A naly t ical characterizat ion of heavy oil residues and asphaltenes

8.3.2.1 So lut ion ana lysis

8.3.2.2 Coagula t ion analys is8.3.2.3 D ist i l lat ion m ethod

8.3.2.4 Chromatography

8.3.2.5B

C - N M R ana lys i s

8 .3 .2 .6 U l t im ate analys is

8.3.2.7 M olecular weight de terminat ion

8.3.3 Temperature in f luence on m olecular w eight de term inat ion

9 Processing of Heavy Crude Oils and Crude Oil Residues

9.1 Int roduct ion

9.2 Chemis t ry and reaction of asphaltenes during co-processingof c rude oil res idue and plastics

9.2.1 Change of asphaltene structure durin g therm al processing

9.2.2 Evaluat ion of poss ibi l i t ies of various asphaltene reactions based

o n th e r m o d y n a m i c s

9.2.3 Hydrogen t rans fer

9.3 Co-processing with cracked products

9.3.1 Co-processing w ith cracked products from aromatics con ta in ing

plastics (e.g. polystyrene)

9.3.2 Co-processing with cracked products from plast ics containing




























































































































































































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paraffin groups

9.3.3 Possibilities that exist for carrying out co-processing of heav y

crude oils and various co-feeds

9.3.4 Behavior of heavy metals during co-processing

9.3.5 Conclusions of co-processing of crude oil residue an d co-feed

9.4 Industr ial m ethods of crude oil residue treatm ent

9.4.1 Fluid cata lytic crac king

9.4.2 Hydrocracking

9.4.3 Coking

Bibl iography

Appendix A: Conversion Factors Important for Crude Oil Chemists

Appen dix B : Glossary



























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