ASSESSMENT OF AROMATICS TO SATURATES RATIOS IN THREE DIFFERENT

NIGERIAN CRUDES

BY

EZUGWU, ONYEKACHUKWU KINGSLEY

PG/M.Sc/13/66387

DEPARTMENT OF PURE AND INDUSTRIAL CHEMISTRY

UNIVERSITY OF NIGERIA, NSUKKA

JULY, 2016
ASSESSMENT OF AROMATICS TO SATURATES RATIOS IN THREE DIFFERENT
NIGERIAN CRUDES

BY

EZUGWU, ONYEKACHUKWU KINGSLEY

PG/M.Sc/13/66387

BEING A RESEARCH PROJECT SUBMITTED IN PARTIAL FULFILLMENT OF

THE REQUIREMENTS FOR THE AWARD OF MASTER OF SCIENCE (M.Sc)
DEGREE IN FOSSIL FUEL CHEMISTRY

TO THE DEPARTMENT OF PURE AND INDUSTRIAL CHEMISTRY

UNIVERSITY OF NIGERIA, NSUKKA

SUPERVISOR: PROF. C.A. NWADINIGWE

JULY, 2016

i
 APPROVAL PAGE

Ezugwu, Onyekachukwu Kingsley, a postgraduate student in the Department of Pure and

Industrial Chemistry, University of Nigeria, Nsukka with Registration number:

PG/M.Sc/13/66387 has satisfactorily completed the requirements for research work for the

degree of Master of Science (M.Sc) in Fossil Fuel Chemistry.

Prof. C.A. Nwadinigwe Dr. A.E. Ochonogor

Date Date

EXTERNAL EXAMINER

Date

ii
 DEDICATION

This work is dedicated to Almighty God for his infinite mercies and to my parents, Prince and

Mrs. Edwin Ezugwu for their financial support in my educational career.

ACKNOWLEDGEMENTS
iii
I sincerely appreciate the effort of my supervisor, Prof. C.A. Nwadinigwe, who selflessly

guided me throughout the course of this work. His leniency and motivational criticisms led to

more effort being put to see to the success of this work. The contributions of my parents,

Prince and Mrs. Edwin Ezugwu throughout the course of this work cannot be over-

emphasized. I also wish to thank the following: Mrs. T.N. Alumona, who was always willing

to assist when necessary, Mr. E. Mbaoji, who provided the materials used for column

chromatography and to the management of Springboard Research Laboratory, Awka, where I

carried out the gas chromatography analysis. May God reward you all.

TABLE OF CONTENTS

iv
Title Page - - - - - - - - - - - i

Approval Page - - - - - - - - - - ii

Dedication - - - - - - - - - - - iii

Acknowledgements - - - - - - - - - iv

Table of Contents - - - - - - - - - - v

List of Tables - - - - - - - - - - x

List of Figures - - - - - - - - - - xi

Abstract - - - - - - - - - - xii

CHAPTER ONE

1.0 Introduction - - - - - - - - - 1
1.1. Statement of the problem - - - - - - - 3
1.2. Aims and Objectives - - - - - - - - 3
1.3. Justification of the study - - - - - - - 3

CHAPTER TWO

2.0. Literature Review - - - - - - - - 5

2.1. Chemistry of crude oil - - - - - - - - 5
2.2 Chemical composition of crude oil - - - - - - 5

2.2.1 Hydrocarbon components of crude oil - - - - - 7

2.2.1.1 Alkanes - - - - - - - - - 8
2.2.1.2 Alkenes - - - - - - - - - - 8
2.2.1.3 Naphthenes - - - - - - - - - 10
2.2.1.4 Aromatics - - - - - - - - - 11
2.2.2 Non-hydrocarbon components of crude oil - - - - - 11
2.2.2.1 Sulphur compounds - - - - - - - - 11
2.2.2.2 Nitrogen compounds - - - - - - - - 13
2.2.2.3 Oxygen compounds - - - - - - - - 14
2.2.2.4 Organo-metallic compounds - - - - - - - 14
2.2.2.5 Salts - - - - - - - - - - 15
2.2.2.6 Naphthenic compounds - - - - - - - 16
2.3 Types of crude oil - - - - - - - - 16
2.4 Classes of crude oil - - - - - - - - 17
2.4.1 Class A (Light, volatile oils) - - - - - - - 17

v
2.4.2 Class B (Non-sticky oils) - - - - - - - 17
2.4.3 Class C (Heavy, sticky oils) - - - - - - - 18
2.4.4 Class D (Non-fluid oils) - - - - - - - - 18
2.5 Characterization - - - - - - - - 18
2.5.1 Distillation method - - - - - - - - 19
2.5.2 Solubility based method - - - - - - - 21
2.5.3 SARA fractionation method - - - - - - - 22
2.5.4 Asphaltenes in Crude Oil - - - - - - - - 26
2.5.5 Sources of Asphaltenes - - - - - - - - 29
2.5.6 Structure of Asphaltenes - - - - - - - 31
2.6 Crude oil Analysis - - - - - - - - - 31
2.6.1 Chromatography as an Analytical Technique - - - - - 34
2.6.1.1 Classification of Chromatographic Methods - - - - - 35
2.6.1.2 Gas Chromatography - - - - - - - - 37
2.6.1.3 Column Adsorption Chromatography- - - - - - 43
2.7 The Impact of asphaltenes in petroleum refining - - - - 46
2.8 Prevention of Asphaltene Deposition - - - - - - 47
2.9 Some previous research on Nigerian crudes - - - - - 49

CHAPTER THREE

3.0 Experimentals - - - - - - - - - 51
3.1 Sample Collection - - - - - - - - - 51
3.2 Materials and reagents - - - - - - - - 52
3.3 Method - - - - - - - - - - 54
3.3.1 Physical Properties of the Crudes - - - - - - 54
3.3.2 Precipitation of Asphaltene - - - - - - - 54
3.3.3 Activation of the Silica gel - - - - - - 55
3.3.4 Chromatography procedure - - - - - - - 55
3.3.5 Gas Chromatography - - - - - - - - 56

CHAPTER FOUR

4.0 Results and Discussion - - - - - - - - 57

4.1 Density - - - - - - - - - 57
4.2 Viscosity - - - - - - - - 57
4.3 Results from Asphaltene Precipitation - - - - - 58
4.4 Elution Column Chromatography - - - - - - 59
4.5 Gas Chromatographic Analysis - - - - - - 61

CHAPTER FIVE

5.0 Conclusion - - - - - - - - - 67
5.1 Contributions to Knowledge - - - - - - - 67
5.2 Recommendations - - - - - - - - 68

vi
REFERENCES

APPENDIX

LIST OF TABLES

Table 2.1. Composition of crude oil 6

Table 2.2. Chemical composition of West Texas and Louisiana Asphaltene 28

Table 2.3. Summary of the classification of chromatographic methods 37

Table 4.1. Densities of the crudes 57

Table 4.2. API gravities of the crudes 57

Table 4.3. Viscosities of the crudes 57

Table 4.4. Asphaltene content of the various crudes 58

Table 4.5. Maltene content of the crudes 59

Table 4.6. Elution colour of the three fractions 60

Table 4.7. The Weights of the different fractions 60

Table 4.8a. The saturate hydrocarbons found in Kokori crude 61

Table 4.8b. The aromatic hydrocarbons found in Kokori crude 62

Table 4.9a. The saturate hydrocarbons found in Afiesere crude 62

Table 4.9b. The aromatic hydrocarbons found in Afiesere crude 63

Table 4.10a. The saturate hydrocarbons found in Nembe crude 63

vii
Table 4.10b. The aromatic hydrocarbons found in Nembe crude 64

Table 4.11. The total concentration of the saturate and aromatic hydrocarbons in

the crudes 64

Table 4.12. The ratios of aromatics to saturates in the crudes 65

LIST OF FIGURES

Fig. 2.1. Some alkanes present in crude oil 9

Fig. 2.2. Some cycloalkanes in crude oil 10

Fig. 2.3. Examples of Aromatics in crude oil 12

Fig. 2.4. Examples of non-hydrocarbon components of crude oil 15

Fig. 2.5. SARA separation scheme 23

Fig. 2.6. Proposed structures of resins 26

Fig. 2.7. Some Proposed structures of asphaltenes 31

Fig. 2.8. Schematic diagram of a typical gas chromatograph 39

Fig. 3.1. Map of Delta State 51

Fig. 3.2. Map of Bayelsa State 52

Fig. 4.1. Bar Chart showing the amount of asphaltenes 59

Fig. 4.2. Bar Chart showing the total concentration of aromatics and saturates 65

viii
Fig. 4.3. Bar Chart showing the aromatics to saturates ratios in the crudes 65

ABSTRACT

This study was designed to determine the aromatics to saturates ratios in three Nigerian Niger

Delta crude oils to ascertain the crude oil source with the highest asphaltene risk. Three crude

oil samples were collected from different locations: Kokori, Afiesere and Nembe in the Niger

Delta region, Nigeria. The physical properties of the crudes such as viscosity, density, API

gravity and kinematic viscosity were determined. Saturates, aromatics, resins, asphaltenes

(SARA) fractionation method was employed to separate the different components in the

crude oil. The composition and concentration of the saturates and aromatics hydrocarbon

fractions were determined using a gas chromatograph. Results showed that API gravities

ranged from 34⁰ to 39⁰ indicating that the three crudes are light. n-Heptane precipitation

showed that Kokori crude had the highest weight percent concentration of asphaltenes

(2.33%) and Afiesere crude, the least (1.91%). The gas chromatographic analysis of the

saturates and aromatics showed that the total concentrations (mg/L) of all the saturates in

Kokori, Afiesere, and Nembe were 871.26, 885.56, and 780.21 respectively while the total

concentration of all the aromatics in the crudes were 80.15, 89.73 and 75.11 respectively. The

aromatics to saturates ratios were computed and the results showed that this ratio decreased in

ix
the order Kokori crude < Nembe crude < Afiesere crude. This implies that Kokori crude with

the lowest ratio will cause most asphaltene deposition problems than the other crudes.

x
 CHAPTER ONE

1.0 INTRODUCTION

In refinery processing, the qualities of crude oils are the most vital part in determining

the cost of refining. Crude oils in general can be divided into three basic categories namely

light, medium and heavy. The criterion is based on the composition of the fractions derived

from crude oil refining. The analysis of crude oil is necessary to determine the properties that

can assist in resolving process problems as well as properties that indicate the function and

performance of the product1. Fuel properties are determined experimentally in the laboratory

on fluid samples taken from the process under study. It is necessary to analyse crude oils in

terms of their saturates, aromatics, resins, asphaltenes (SARA) composition in order to

address and mitigate process problems such as asphaltene precipitation that can clog wells,

pipelines, surface facilities and subsurface formations in the upstream operations, while in the

downstream refining of heavy crude oils, it can lead to coking, fouling and catalyst

deactivation. These problems are undesirable because they reduce productivity, limit fluid

flow and are costly, hence laboratory analysis can assist to remediate such problems.

The composition of crude oil can vary depending on many factors, like location and

age of the field. Crude oil mainly consists of several hydrocarbons and additional small

amounts of compounds containing nitrogen, oxygen, sulphur and metals 2. Petroleum products

are any petroleum-based products that can be obtained by refining and comprise of refinery

gas, liquefied petroleum gas (LPG), naphtha, gasoline, diesel fuel, distillate fuel oil, residual

fuel oil, gas oil, lubricants, white oil, grease, wax, asphalt as well as coke 1. Four main classes

of hydrocarbons present in crude oils can be identified and measured: saturates (alkanes and

cyclo-alkanes), aromatics (mono, di and polyaromatic), resins and asphaltenes3.

1
 The origin of crude oil has been debated for quite sometime; currently, there is a

general consensus among the geologists that crude oil was formed from the remains of plants

and animals buried millions of years ago. The organic matter underwent diagenesis, a process

in which it was subjected to several redox reactions particularly governed by microbes. This

resulted in the expulsion of methane, water and oxygen from the organic matter to form

complex organic hydrocarbons called kerogen. Kerogen is insoluble in common petroleum

solvents including carbon disulphide. Catagenesis of kerogen occurred in the deep subsurface

in relatively higher temperature and pressure conditions. During this phase, the kerogen

underwent thermal maturation to release crude oil and gas. The rate of thermal maturation

depends on several parameters; however, temperature was found to be the most crucial one.

In general, the thermal maturation of kerogen between 60⁰C and 120⁰C released natural gas.

Above 225⁰C, the kerogen did not contain any hydrocarbons4. The nature of organic matter

and the geological conditions that were present during the formation of crude oil determined

its physical properties. Bulk physical properties such as density, viscosity and boiling point

have been used to compare the quality of different crude oils. These properties are very useful

in determining proper conditions for drilling, transportation and refining of crude oils. Crude

oils can be fractionated into four different components, namely, Saturates, Aromatics, Resins

and Asphaltenes (SARA). A reliable compositional characterization of petroleum fractions is

important for the optimization of refining processes, products performance evaluation,

structure-property correlations, oil-source correlations and environmental issues.

Chromatographic techniques have been extensively used for hydrocarbons group type

determination, such as SARA fractionation. This study discusses parameters such as SARA

composition and asphaltene stability. Asphaltene stability of crude oils can be determined

from the ratio of aromatics to saturates in the crude oil 5 and this can be used to mitigate crude

oil fouling6.

2
1.1 Statement of the problem

The main parameter that controls the stability of asphaltene in a crude oil is the

aromatics to saturates ratio. If this ratio decreases, asphaltene will flocculate and form larger

aggregates. These asphaltene aggregates are highly notorious for the problems they cause as

solid deposits. These problems include obstruction of flow in the production system leading

to reduction in crude oil production as they can block the pores of reservoir rocks and can

also plug the wellbore tubing, flow lines, separators, pumps, tanks and other equipment. This

causes a barrier to the flow of oil.

1.2 Aims and Objectives

The aims and objectives of this research project are:

 To deasphalt each crude with n-heptane to obtain asphaltene free maltenes and compare

the yield of asphaltenes in the three crudes.

 To fractionate the resulting maltenes obtained after deasphalting for the purpose of

obtaining the aromatics and saturates components.

 To use gas chromatography to quantify the total content of aromatics and saturates in the

maltenes.
 To determine the ratios of aromatics to saturates in the different crudes.
 To compare the ratios of the aromatics to saturates in the different crudes.
1.3 Justification of the Study
Asphalthenes are important constituents in crude oil. They contribute significantly to

the high viscosity and the coking tendency of heavy oils. They cause solid deposits that

obstruct flow in petroleum production systems thereby causing reduction in crude oil

production.
The cost of remediation and loss in petroleum production resulting from organic

deposition in these operations increase and hence a lot of money and manpower is sunk into

potential remedial work. Any effort to better understand the precipitation phenomena and

forecast possible problems is very important. It is therefore necessary to develop a method

3
which will ascertain the crude oil with the highest amount of asphaltene before they are sent

to the refinery.

CHAPTER TWO

2.0 LITERATURE REVIEW

2.1 Chemistry of Crude Oil

4
 Crude oil or petroleum, which means “rock oil” in Latin, occurs as a dark, sticky and

viscous liquid. It is a mixture of gaseous, liquid and solid alkanes, alkenes, cycloalkanes,

aromatic hydrocarbons and others7. It can be said to be a collective term used to describe a

hydrocarbon rich mixture of compounds that is usually found as a subterranean deposit that

accumulated over millions of years8. It is a complex mixture of hydrocarbons from which

various petroleum products such as gasoline, kerosene, propane, fuel oil, lubricating oil, wax

and asphalt are derived9. Crude oil and its refined petroleum products consist largely of

hydrocarbons, which are chemicals composed solely of hydrogen and carbon in various

molecular arrangements10. It also contains other organic and inorganic compounds including

those containing atoms of sulphur, nitrogen and oxygen, as well as metals such as iron,

vanadium, nickel and chromium. Collectively, these other atoms are called heteroatoms11.

Crude oil is a liquid but may contain gaseous and/or solid compounds in solution. It also

contains lighter fractions as well as heavier tar or tar constituents 9. It varies in consistency

from a light volatile fluid to a semi solid. For instance, Nigerian crude oil is predominantly

aliphatic hydrocarbons and aromatics while the Middle East oil contains a greater proportion

of straight chain hydrocarbons12.

2.2 Chemical Composition of Crude Oil

The generation of crude oil is one of the stages in the alteration of certain types of

organic matter buried in sediments. It is formed through increasing burial and temperature;

and so is part of the general process of organic metamorphism.

Crude oils are largely carbon (about 75%), hydrogen (12%), oxygen (2%), nitrogen (1.5%)

and sulphur (9.5%) 8. Several hundred organic compounds have been recorded from natural

oil.

Table 2.1. Composition of crude oil

5
Fractions No of Carbon Boiling range(⁰C) Composition(%)

Gases 1-4 <0 2

Light naphtha 5-7 27-93

34

Heavy naphtha 6-10 93-177

Kerosene 10-15 177-293 11

Light gas oil 13-18 204-343

21

Heavy gas oil 16-40 315-565

Residuum >40 >565 32

Source: USEPA (1999)

The hydrocarbons are largely n-alkanes and aromatic hydrocarbons. The oxygen, nitrogen

and sulphur occur in such compounds as naphthenic, aromatic acid, pyridines, porphyrins,

thiols and thioalkanes. Low sulphur crude oil (<0.5%) is referred to as sweet oil whereas sour

oil has higher sulphur content (>0.5%). Solid and semi solid organic compounds, (asphalts)

are associated with petroleum and are composed of asphaltenes, resins and other oily

constituents13. Gas is invariably associated with crude oil occurring either in solution or as a

gas cap. Natural gas, which is not associated with oil also occurs and this gas consists

predominantly of methane14.

2.2.1 Hydrocarbon Components of Crude Oil

Crude oil consists of alkanes, cycloalkanes and aromatic compounds containing at

least one benzene ring, saturated normal alkanes (paraffins) and branched alkanes of the

general formula (CnH2n+2), with n ranging from 1-70. Above C13, the most important group

6
of branched compound is the isoprenoid hydrocarbons consisting of isoprene building blocks.

Pristane (C19) and Phytane (C20) are usually the most abundant isoprenoids and while the

C10-C20 isoprenoids are often major petroleum constituents, extended series of isoprenoids

(C20-C40) have been reported14. Many of the cycloalkanes or saturated ring structures such

as cycloparaffins or naphthenes consist of important minor constituents, which like the

isoprenoids, have specific animal or plant precursors (e.g. steranes, diterpanes and

triterpanes). These compounds serve as important molecular markers in oil spill and

geochemical studies.

Aromatic hydrocarbons are usually less abundant than the saturated hydrocarbons.

They contain one or more aromatic (benzene) rings connected as fused rings (e.g.

naphthalene) or lined rings (e.g. biphenyl). Petroleum contains many homologous series of

aromatic hydrocarbons consisting of unsubstituted or parent aromatic structures (e.g.

phenanthrene) and like structures with alkyl side chains that replace hydrogen atoms. Alkyl

substitution is more prevalent in one, two and three ringed aromatics, although the high

polynuclear aromatic compounds (>3 rings) do contain alkylated (1-3 carbons) side groups

such as polycyclic aromatic of pyrene and perylene structure. The naphtheno-aromatic

compounds consist of mixed structures of aromatic compounds and saturated cyclic rings.

This series increases in importance in the higher boiling fractions along with the saturated

naphthenic series. The naphtheno-aromatics appear related to resins, kerogen and sterols.

Petroleum generation usually involves the formation of some naphtheno-aromatic structures.

Crude oil is a mixture of hydrocarbon molecules which are organic compounds of

carbon and hydrogen atoms. The properties of hydrocarbons depend on the number and

arrangement of the carbon and hydrogen atoms in the molecules. The simplest hydrocarbon

molecule is one carbon linked with four hydrogen atoms (methane). All other variations of

7
petroleum hydrocarbons evolve from this molecule and they include other members of the

alkane or paraffin family, alkenes, naphthenes and aromatics.

2.2.1.1 Alkanes

The alkanes are a homologous series of saturated hydrocarbons of general formula

CnH2n+2. The simplest member of this series is methane (CH 4), followed by ethane (C2H6)

propane (C3H8) and butane (C4H10). In crude oil, all the normal alkanes from C1 to C40 (and a

few beyond C40) have been identified. On the average, crude oil contains between 15 to

20% of such compounds. However, this figure may rise to as high as 35% in very paraffinic

crude oils; or drop to zero in the case of heavily biodegraded oils15.

Alkanes found in gases and paraffin waxes are the lighter, straight chain alkanes like

methane, ethane, propane, butane, pentane and hexane. The branched chain paraffins are

usually found in heavier fractions of crude oil such as isobutene16.

2.2.1.2 Alkenes

Alkenes are mono-olefins with the general formula C nH2n. They are reactive

compounds and are thus fairly rare in crude oils. However, small quantities of n-hexene, n-

heptene, and n-octene have been identified. Alicyclic alkenes have also been observed in

crude oils. The remains of natural product species found in sediments may also contain

unsaturated rings.

8
 CH3CH2CHCH2CH3
n-hexane
CH3
3-methylpentane

CH3
CH3CCH2CH3
CH3 CH3
CH3
CH3CH CHCH3
2,2-Dimethylbutane
2,3-Dimethylbutane

pristane

Pristane

Phytane

Fig 2.1. Some alkanes present in crude oil

9
2.2.1.3 Naphthenes (Cycloalkanes)

Naphthenes are another group of hydrocarbon in crude oils. They are arranged in the

form of closed ring (cyclic) with or without substituents. The smallest of these compounds is

cyclopropane, which has three carbon atoms. Naphthenes are found in all types of crude oil

except the very lightest16. Single-ring naphthenes (monocycloparaffins) with five and six

carbon atoms predominate. Occasionally a few have rings with seven carbon atoms; but the

three- and four-member rings are very reactive due to bond angle strain. The two-ring

naphthenes (di-cycloparaffins) are found in the heavier ends of naphtha. Most of the

cycloparaffins below C10 are single-ring compounds. For alicyclics above C10, about 50%

are mono- or di-cyclic compounds with alkyl chains as substituents. The normal combination

is one long chain and several methyl or ethyl groups 17. The remainders of the cycloparaffins

are compounds with three or five rings of five or six members each. The compounds with

three rings can be less than 20% of the total cycloparaffin content of oil. The naphthene

fractions of crude oils are often analysed by mass spectroscopy to identify the percentage of

compounds with one, two, three, four, and five rings. This information can be used in

maturation level assessment14.

CH3

CH3

Cyclopentane Methylcyclopentane
CH3
Dimethylcyclopentane
CH3
CH3

CH3
Cyclohexane Methylcyclohexane Dimethylcyclohexane

Fig 2.2. Some cycloalkanes in Crude oil

10
2.2.1.4 Aromatics

The aromatic or benzene series of compounds are so named because many members

have a strong aromatic odour (Greek, aroma – “fragrant smell") and all are derivatives of

benzene. They are unsaturated ring type (cyclic) compounds which react readily because they

have carbon atoms that are deficient in hydrogen. All aromatic hydrocarbons contain at least

one benzene ring (a single-ring compound characterized by three double bonds alternating

with three single bonds between six carbon atoms) as part of their molecular structure.

However, naphthalenes are fused double-ring aromatic compounds. The most

complex aromatics, polynuclear (three or more fused aromatic rings) are found in the heavier

fractions of crude oil. Therefore, the general formula can be said to depend on the number of

rings15.

The alkyl derivatives of benzene e.g. toluene and the xylenes, are the most common aromatic

compounds in crude oils and occur in greater amounts than the parent compound benzene.

The other derivative of benzene forms a part of naphthalenes, which is a di- or tri-aromatic

such as phenanthrenes or more rarely, anthracenes.

2.2.2 Non-hydrocarbon Components of Crude Oil

The non-hydrocarbon petroleum constituents can be grouped into six classes namely sulphur,

nitrogen, oxygen, organometallic compounds, salts and naphthenic compounds18.

2.2.2.1 Sulphur Compounds

Sulphur compounds are the most important group of non-hydrocarbon constituents.

Most sulphur present is organically bound e.g. the heterocyclics. The organosulphur

compounds consist of thiols, disulphides, sulphides and cyclic sulphides (e.g.

thiocyclohexane and thiophenes).

11
12
Fig. 2.3. Examples of Aromatics in Crude oil

The benzothiophenes and dibenzothiophenes are important constituents of the higher

molecular weight aromatic fractions of environmental samples, with the tetra-methyl

dibenzothiophenes apparently having the highest molecular weight of the sulphur

heterocyclic19. Many sulphur compounds including thiols, sulphides, and thiophenes occur in

crude oils; and sulphur is fairly evenly distributed over the medium and heavy fractions of

crude oils. All sulphur compounds are foul, evil smelling, lachrymatory and corrosive and

lower the value of crude oil. Not only will the handling of the oil be more difficult, but total

removal of sulphur compounds is needed, otherwise the products may be corrosive, foul

smelling, and dangerous when used. Most of these sulphur compounds can be considered as

derivatives of hydrogen sulphide (H2S), which in itself is very corrosive, highly poisonous

and foul smelling. In high sulphur crude oil, a lot of sulphur is released as hydrogen sulphide

during distillation, indicating also that the sulphur was either present in the crude oil as

dissolved hydrogen sulphide or in compounds which decompose under the condition of

distillation. It is worth noting that these types of compounds, as with many others in crude

oil, are found in other situations to which one is more accustomed. For example,

CH3CH2CH2SH or n-propyl mercaptan, is the chemical which gives the onion its distinctive

aroma and which causes one to shed tears when peeling onions and CH 2=CHCH2-S-

CH2CH=CH2 is the chemical which is found in garlic 15. Other examples of sulphur

compounds include other mercaptans and disulphides.

2.2.2.2 Nitrogen Compounds

Nitrogen is present in all crude oils in compounds such as pyridines, quinolines,

benzoquinolines, acridines, pyrole, indoles, carbazole and benzcarbazoles. The porphyrins

are nitrogen-containing compound derived from chlorophyll and consisting of four-linked

13
pyrole rings. Porphyrins occur as organometallic complexes of vanadium and nickel. The

nitrogen content of crude oil can be as low as 0.01 percent or as high as 0.9 percent by

weight, most of this appearing in distillates boiling above 400 ⁰C. Nitrogen is found in lighter

fractions of crude oil as basic compounds in form of pyridines, quinolines or

benzoquinolines20 while it is found in heavier fractions of crude oil as non-basic compounds

that may also include trace metals such as copper, vanadium and/or nickel. This non-basic

compounds include pyroles, indoles, carbazoles and benzcarbazoles16. Most of these

compounds of nitrogen have made nitrogen compounds undesirable in crude oil as they are

responsible for the poisoning of catalysts and the formation of gums in fuel oils21.

2.2.2.3 Oxygen Compounds

Oxygen compounds in crude oil are found primarily in distillation fractions above

400⁰C and consist of phenols, carboxylic acids, ketones, esters, lactones and ether. The most

important oxygen compounds in crude oils are the organic acids and they are especially

common in young and immature crude oils15. These acids range in size from carbon 1 to

carbon 30 and include some isoprenoid structures. Cyclic aliphatic acids also occur, but in

smaller amounts in most oil; sometimes they are in the form of naphthenic-aromatic acids. In

addition to acids, there is evidence of alcohols, phenols, ketones, esters, and anhydrides 21.

The oxygen content of crude oil increases with boiling point and, like other heteroatoms, the

greater part of petroleum oxygen is found in distillates boiling above 400⁰C.

If bacteriological modification of plant remains under anaerobic conditions, it is an

important process in crude oil formation22. Therefore, the presence of oxygen containing

compounds in petroleum may be difficult to explain. On the other hand acidic materials seem

14
to be widespread in sediments and formation waters and these may be a potential source of

oxygen compounds, particularly during the migration and accumulation stages23.

2.2.2.4 Organo-metallic Compounds

Organo-metallic compounds are often found in crude oils in small quantities and are

therefore sometimes referred to as trace metals. Most crude oils contain these metals,

normally in porphyrin complexes, derived from chlorophyll and haemoglobin 15. Vanadium

and nickel are the most abundant metallic constituents of crude petroleum, sometimes

reaching thousands of part per million. They are primarily present in porphyrin complexes

and other organic compounds of crude oil. However, copper and iron; and a wide variety of

other metals in lesser amounts have been reported16.

15
16
 N N
N N
Pyridine Quinoline Isoquinoline Acridine
OH OH

R
N N N
Cresylic acid
H H H
H
Pyrrole Indole
Carbazole Benzocarbazole Phenol

S
S
O
O
Thiophene Benzothiophene
Furan Benzofuran

Fig. 2.4. Examples of non-hydrocarbon components of crude oil

2.2.2.5 Salts

Crude oil often contains inorganic salts such as sodium chloride, magnesium chloride

and calcium chloride in suspension or dissolved in entrained water (lime). These salts must be

removed before processing to prevent catalyst poisoning, equipment corrosion and fouling.

Salt corrosion is caused by the hydrolysis of some metal chloride to hydrogen chloride (HCl)

and the subsequent formation of hydrochloric acid when crude is heated. Hydrogen chloride

may also combine with ammonia to form ammonium chloride (NH 4Cl), which causes fouling

and corrosion.

2.2.2.6 Naphthenic Compounds

17
 Naphthenic compounds occur principally in crude oil in two ranges of carbon

numbers C6 to C12 and C14 to C19. The lower range contains chiefly cyclopentyl and

cyclohexyl, carboxylic acids with several short (C1 to C12) substituents, which often include

a methyl pair. Little is known about the higher ranges, although these appear to be monobasic

acids with an average of 2 to 3 rings per molecule. Some crude oils contain naphthenic acids,

which may become corrosive at temperatures above 4500⁰F when the acid value of the crude

is above a certain level.

Types of Crude Oil

i. Light Crude and Very Light Crude oil: This is liquid petroleum that has low density

and flows freely at room temperature. It has low viscosity, low specific gravity and

high API gravity (34⁰-39⁰) due to the presence of a high proportion of light

hydrocarbon fractions. It generally has a low wax content. Very light crude is defined

with API gravity above 40⁰.(24)

ii. Medium Crude oil: This is any liquid petroleum with an API gravity within 22⁰-33⁰.
iii. Heavy Crude oil and Extra Heavy Crude oil: This is any type of crude oil which does

not flow easily. It is referred to as “heavy” because its density or specific gravity is

higher than that of light crude oil. Heavy crude oil is defined as any petroleum with an

API gravity less than 20⁰. Heavy oil is aliphatic and contains asphalthenes and resins.

It is heavy (dense and viscous) due to high composition of aromatics and naphthenes,

high amounts of Nitrogen, Sulphur, Oxygen, and heavy metals25. Extra heavy crude is

defined as crude oil with API gravity below 10⁰ (i.e. with density greater than

1000kg/m3 or equivalently with a specific gravity greater than 1)26.

2.4 Classes of Crude Oil

18
 Because oils from different geographical areas have unique properties, crude oil has

been classified according to geographical sources e.g. Alaska North Slope crude oil,

Venezuelan crude oil and Nigerian crude oil because. They can vary in consistency from a

light volatile fluid to a semi-solid. Therefore, the classification based on geographical

location is not generally accepted as it offers little information about general toxicity,

physical state as well as changes that occur with time and weathering. According to USEPA

(2004), four classes of crude oil can be distinguished namely light volatile oils, non-sticky

oils, heavy sticky oils and non-fluid oils27.

2.4.1 Class A (Light, Volatile Oils)

Class A oils are highly fluid, often clear, spread rapidly on solid or water surface, have a

strong odour, a high evaporation rate and are usually flammable. They penetrate porous

surfaces; however flushing with water generally removes them. This class of oil may be

highly toxic to man, fish and other biota. Most refined products and many of the highest

quality light crude can be included in this class.

2.4.2 Class B (Non-Sticky Oils)

Non-sticky oils are characterized by their waxy or oily feel. They are less toxic and adhere

more firmly to surfaces than class A oils, although they can be removed from surfaces, by

vigorous flushing. Their tendency to penetrate porous substrates increases as temperature

rises and they can be persistent. Evaporation of volatiles may lead to a class C or D residue.

A very good example is the medium to heavy paraffin-based oils.

2.4.3 Class C (Heavy, Sticky Oils)

19
Class C oils are characteristically viscous, sticky or tarry, and brown or black in colour.

Flushing with water will not readily remove this material from surface, but the oil does not

readily penetrate porous surfaces because of their heavy and sticky nature. Toxicity is low,

but wildlife can be smothered or drowned when contaminated. The density of class C oils

may be near that of water and they often sink. Weathering or evaporation of volatiles may

produce solid or tarry class D oil. This class includes residual fuel oils.

2.4.4 Class D (Non- fluid Oils)

Class D oils are relatively non-toxic. They do not penetrate porous substrates and are usually

black or dark brown in colour. When heated, Class D oils may melt and coat surfaces making

clean up very difficult. Examples of oils in this group include residual oils, heavy crude oils,

some high paraffin oils and some weathered oils.

2.5 Characterization

For effective design and optimization of crude oil processing, adequate

characterization of the fluid is essential for phase behaviour modelling. Characterization is

intended to represent the distribution of properties within the crude oil and entails the division

of the complex multi- component crude oil into various pure components and pseudo-

components of known or correlated properties. Analytically determining the composition of

all pure components in crude oil is difficult so the general procedure is to segregate the

constituents according to molecular size and molecular type28.

The most common compositional representation of crude oils is to lump components

into groups of similar properties (pseudo-components) based on their chemical composition

(such as H/C content, carbon distribution, heteroatom content), physical properties (such as

boiling point, density, molecular weights, viscosity, refractive index) and chemical-function

families (as in Paraffins, Naphthenes and Aromatics - PNA, Saturates, Aromatics, Resins and

20
 29
Asphaltenes – SARA) . Techniques that have been employed to separate crude oil into

fractions or pseudo-components include gas chromatography, distillation, adsorption

chromatography (e.g., PNA, SARA), mass spectrometry, solvent treatments, and chemical

methods. The choice of fractionation method depends on the nature and composition of the

crude oil, the effectiveness of the process, its compatibility with the other separation

procedures to be employed and the required fractions or pseudo-components properties.

Typically, separation of the light and volatile constituents of crude oil (N 2, He, H2S, C1 to C5)

can be achieved with gas chromatography and distillation. However, as the volatility

decreases and the complexity of the constituents increase with increasing molecular weight, it

becomes very difficult to apply these techniques to higher boiling petroleum constituents 30.

Other techniques are applied to characterise the heavier components. The characterisation

techniques that have been used are outlined below.

2.5.1 Distillation Method

In refineries, conventional oils are typically characterised using distillation where the

constituents are separated into fractions, or distillation cuts, based primarily on their

differences in vapour pressure or boiling points. The vapour pressure of a compound is

inversely proportional to its boiling point, molecular weight, aromaticity and polarity.

Therefore, over a boiling point range, similar constituents (in terms of volatility) are

separated from the oil and collected as distillation cuts. The properties of these pseudo-

components can be measured. Distillation curves which are plots of boiling temperature

versus volume of distillates present a distribution of the species in a particular crude oil by

their volatilities. Distillation can be performed at atmospheric pressure or at reduced pressure

depending on the type of crude oil.

21
Crude oils boil over a range of temperatures from about 20 ⁰C to above 344⁰C, beyond which

thermal decomposition (cracking) occurs31. Compounds boiling above approximately 350⁰C

are called residuum and are removed from the bottom of the atmospheric distillation column

and sent to the vacuum distillation column 28. Vacuum distillation is usually adapted to obtain

higher-boiling distillates from the residuum at lower temperatures and reduced pressure

without the risk of decomposition. The minimum obtainable pressure for vacuum distillation

is around 3.5 to 7 kPa. The highest temperature that can be measured at this pressure for most

crude oils is in the range of 496 to 526 ⁰C when corrected to atmospheric pressure32. Vacuum

distillation is also applied to heavier oils.

The distribution of the various compound types throughout the petroleum vary with

type of crude28, but for a given family of hydrocarbons, the molecular weights, complexity,

density, aromaticity and polarity increase monotonically with increasing boiling points.

Generally, the residuum contains the highest concentrations of high- molecular weight

organic compounds (with sulphur, nitrogen, oxygen, metals and other non-hydrogen species),

as well as high-molecular weight hydrocarbons, including condensed-ring aromatics 33. The

higher boiling distillation cuts also contain a broader distribution of components with

corresponding properties. However, for practical reasons, distillation cuts are commonly

treated as pseudo-components each with a unique boiling point, molecular weight, density,

refractive index and critical properties.

Other key characterization parameters (e.g., critical properties, solubility parameters,

etc.) of the distillable fractions required for modeling fluid behaviour can be correlated to the

measured properties. Critical properties can be estimated using Vetere-Watson, Lee–Kesler or

Riazi– Dauber correlations34. The solubility parameter can be calculated through its definition

with the enthalpy of vaporization which in turn is correlated to the critical properties. Heavy

oil and bitumen cannot be fully characterized by distillation because these fluids contain large

22
amount of high molar mass components that decompose before they boil. The non- distillable

fractions of heavy oils and bitumen can make up as much as 60% by weight of the original

oil, which limits the characterization of heavy oils by distillation alone due to the inability to

determine properties of higher-boiling cuts24. Even with vacuum distillation, a significant

fraction of the oil (about 50 wt %) remain as residual fraction that does not boil 35. Therefore,

these high-boiling distillates and heavy feedstocks are often characterized according to their

molecular weight distribution (gel permeation chromatography), chemical family, or

28
solubility classes (adsorption chromatography) . The most common methodology to

characterize the heavy oils and bitumen is based on solubility classes.

2.5.2 Solubility Based Method

This method is based on the affinity of petroleum components to solvents and

adsorbents and separates petroleum into groups of molecules with similar solubility. A typical

solubility-based characterization method is SARA fractionation which is a systematic

extraction that separates the crude oil into saturates, aromatics, resins, and asphaltenes

(SARA) fractions following the ASTM D2007 method as shown in figure 2.5

Heavy oils have been characterized using SARA analysis. This method involves the initial

separation of asphaltenes from oil before contacting the feedstock with the adsorbents.

Asphaltenes are a true solubility class and include all the materials that are insoluble in a

paraffinic hydrocarbon (i.e., n-pentane or n-heptane), but soluble in an aromatic hydrocarbon

such as toluene. The remaining SAR (maltenes) fractions are adsorption classes. Saturates are

not adsorbed on polar adsorbents and are recovered with n-pentane as the initial eluent from a

silica gel/attapulgus clay adsorption column. Aromatic compounds are adsorbed on a column

packed with silica gel and are eluted using a mixture of n-pentane/toluene and by Soxhlet

extraction with toluene. Resins are adsorbed on an attapulgus clay-packed column and are

23
eluted with a mixture of acetone/toluene. The asphaltene and resin contents of heavy oil

exceeds 40 wt/wt %, significantly higher than in conventional oils.

2.5.3 SARA Fractionation Method

Crude oil consist of thousands or millions of different structures and compounds, and

a separation of all these is impossible. A dividing of the crude oil into smaller fractions

depending on size, polarity and aromaticity is a beneficial approach. The most common

fractionation of the crude oil is the SARA fractionation 36-42. This method divides the crude

into Saturates (S), Aromatics (A), Resins (R) and Asphaltenes (A). These four fractions differ

in their polarity, aromaticity and solubility in a hydrocarbon medium. Jewell et al. presented

in 1972 separation of heavy-end petroleum distillates into acid, base, neutral-nitrogen,

saturate and aromatic fractions36. The study was the first to divide the crude into these

fractions by chromatographic separation. The technique included both anion – and cation

exchange chromatography, coordination chromatography and adsorption chromatography.

The separation technique has later been modified to include separation of the polar

constituents into resins and asphaltenes, and more sophisticated preparative HPLC methods

have made these separation automatic and less time-consuming 37-38. A typical separation is

shown schematically in the figure 2.5. The first step in the SARA fractionation is

precipitation of the most polar and aromatic part of crude oil – the asphaltenes. Upon addition

of a light hydrocarbon, such as n-pentane or n-heptane, the asphaltenes will precipitate as a

brown to black solid material. In some cases, an additional pre-precipitation with an aromatic

solvent like toluene (which solubilises all SARA fractions) might be feasible, if necessary to

remove solid, inorganic particles from the solution 39-40. The three remaining fractions are

separated by HPLC, using a combined system composed of an amino pre-column and silica

column. Saturates are easily eluted with hexane as mobile phase through both columns, and

the aromatics are subsequently collected by using a back-flushing mechanism. Resins are

24
adsorbed to the amino column, but desorbed with dichloromethane and back-flushing. The

amount of each fraction is finally determined gravimetrically.

Crude Oil

Dilute with n-alkane

Precipitate
Maltenes

Adsorb on silica

elute with

n-alkane toluene dichloromethane/methanol

Saturates Aromatics Resins Asphaltenes

Fig. 2.5. SARA-separation scheme for separation of crude oil into saturate, aromatic, resin
and asphaltene (SARA) components

SARA fractionation has been used on numerous crude oils from all over the world.

However, several SARA fractionation methods have been used. First of all, the asphaltenes

may be precipitated by different hydrocarbons, e.g. pentane and heptane. In a comparison

study, Kharrat et al. showed that the choice of precipitation medium could be highly crucial

for some crude oils regarding the amount of asphaltene precipitated 41. For one of the crude

oils, the solvent effect of asphaltene precipitation gave a ratio of precipitated asphaltenes

depending on the medium, % asphaltenes C5/C7, as high as 263. For all 5 crude oils tested,

the lowest ratio was higher than 1.5. And, the asphaltene C5/C7 ratio will thus influence the

amounts of the other fractions. In addition, volatile compounds give a low total recovery.

Sample topping, that is evaporation of volatile compounds, should always be included in the

25
SARA fractionation to give a high total recovery (~100%) and correct amounts of the four

fractions.

Another SARA fractionation method is by use of thin layer chromatography, TLC, in

42
combination with an automated flame ionization detector (FID) . The separation of the

fractions is carried out with much the same eluents as for the HPLC method, but at a smaller

scale. The TLC-FID detection can be a good alternative to the HPLC method, but lacks

accuracy because of underestimating the saturate fraction due to evaporation from the TLC

rod. Thus, TLC-FID have mostly been applied to determine hydrocarbon types in various

high-boiling materials with initial boiling points at or above 260 ⁰C, and less suitable for crude

oils with high amounts of volatiles.

Saturates: The saturates (aliphatic) are non-polar hydrocarbons, without double bonds, but

including straight-chain and branch alkenes as well as cycloalkanes. Cycloalkanes contain

one or more rings, which may have severely alkyl side chain. The proportion of saturates in a

crude oil normally decrease with increase in molecular weight fraction. Thus, saturates

generally are the lightest fraction of the crude oil. Wax is a sub-class of the saturate,

consisting primarily of straight-chain alkenes, mainly ranging from C 10 to C30. Distribution of

n–alkanes has been used to differentiate the petrogenic and biogenic contribution in complex

environmental samples. Usually the n–alkanes with an odd number of carbon atoms are found

in higher concentrations if the crude oil is derived from a biogenic source. On the other hand,

the concentration of n–alkanes decreases with an increase in the carbon number if it is

derived from a petrogenic source. The distribution of n-alkanes in crude oils can be used to

indicate the organic matter source43. Generally, short and medium chain odd carbon numbered

compounds of aliphatic hydrocarbons with carbon numbers between n-C15 and n-C25 are

associated with aquatic sources, where shorter derivatives originates from lacustrine algae in

26
contrast to mainly macrophyphic plants as sources of the longer chain derivatives44. Hector et

al., reported n-alkanes range from C10 -C35 with slight odd-over- even predominance,

maxima at n-C15 - C20 and ratios n-C12-C31 /n-C15 -C20 indicating a moderate wax

content45. Akinlua et al., identified saturated hydrocarbons ranging from n–alkanes (C8 –

C40), hopanes and steranes in north-western Niger Delta oils, Nigeria46.

Aromatic: The term aromatic refers to benzene and the structural derivatives. Aromatics are

common to all petroleum and by far the majority of the aromatics contain alkyl chains and

cycloalkane rings, along with additional aromatic rings. Aromatic are often classified as

mono, di-, and tri-aromatics depending on the number of aromatic rings present in the

molecule. Polar, higher molecular weight aromatics may fall in the resin or asphaltene

fraction. Crude oil contains a wide variety of aromatic hydrocarbons ranging from mono

aromatics hydrocarbons such as benzene to poly aromatic hydrocarbons (PAHs) with many

fused aromatic rings. More than 85% of the aromatic hydrocarbons in crude oil contain one

or more alkyl substituent on their aromatic rings. Aromatic compounds containing sulphur

and nitrogen atoms in the ring e.g. (thiopenes) are also very common in crude oil 47. Aromatic

hydrocarbons are important constituents of petroleum and extract of both recent and ancient

sediments. PAHs are not synthesized in living organisms and almost absent in natural organic

matter. The majority of PAHs in petroleum are the products of complex chemical

transformations of naphthenic and/or olefinic biological ancestors during diagenesis and

catagenesis. Abundance of certain aromatic hydrocarbons in crude oils and sediments such as

1,2,5–trimethylnaphthalene, 1,2,5,6–tetramethylnaphthalene, 9-methylphenanthrene, 1,7–

dimethylphenanthrene originate from diterpeniod and triterpenoid natural products. The most

useful application of aromatic hydrocarbons is evolution of thermal maturity of organic

matter48.

27
Resins: This fraction comprised of polar molecules often containing heteroatoms such as

nitrogen, oxygen or sulphur. The resin fraction is operationally defined as the fraction soluble

in light alkanes such as pentane and heptane, but insoluble in liquid propane. Since the resins

are defined as a solubility class, overlap both to the aromatic and the asphaltene fraction is

expected. Despite the fact that, the resin fraction is very important with regard to crude oil

properties, little work has been reported on the characteristics of the resins, compared to for

instance the asphaltenes. However, some general characteristics may be identified. Resins

have a high H/C ratio than asphaltenes, 1.2 - 1.7 compared to 0.9 - 1.2 for the asphaltenes.

Resins are structurally similar to asphaltenes, but smaller in molecular weight (>1000 g/mol).

Naphthenic acids are commonly regarded as part of the resin fraction 44.

OH

Fig. 2.6. Proposed structures of resins44

2.5.4. Asphaltenes in Crude Oil

Asphaltenes are the most important asphaltic compounds of petroleum and it is in the

form of colloidally dispersed particles. The central part of the asphaltene miscelle consists of

high molecular weight compounds surrounded and peptized by neutral resins of aromatic

hydrocarbons49.

28
 Asphaltenes are today widely regarded as soluble, chemically altered fragments of

kerogen which migrated out of the source rock of the oil, during oil catagenesis. Asphaltenes

had been thought to be held in solution in oil by resins. The classic definition of asphaltenes

is based on the solution properties of petroleum in various solvents. In modern terms, it is

conceptually defined as the n-alkane insoluble and benzene-soluble fraction, whether it is

derived from coal or petroleum.

According to Nellensteyn, the asphaltene fraction is insoluble in low boiling point

paraffin hydrocarbons, but soluble in carbon tetrachloride and benzene 50. It has also been

defined as the fraction insoluble in n-heptane but soluble in toluene 51. There is a close

relationship between asphaltenes, resins and high molecular weight polycyclic hydrocarbons.

In nature, asphaltenes are hypothesized to be formed as a result of oxidation of neutral resins.

On the contrary, the hydrogenation of asphaltic compound products containing neutral resins

and asphaltene produces heavy hydrocarbon oils, i.e. neutral resins and asphaltenes are

hydrogenated into polycyclic aromatic or hydro aromatic hydrocarbons. However, they differ

from polycyclic aromatic hydrocarbons by the presence of oxygen and sulphur in varied

amounts.

The colour of crude oils and residues is due to the combined effect of neutral resins

and asphaltenes. The black colour of some crude oils and residues is related to the presence of

asphaltenes which are not properly peptized. Thus, asphaltenes are believed to exist in oil

partly dissolved in colloidal and/or micellar form. Whether the asphaltene particles are

dissolved in crude oil in steric colloidal state or in micellar form, depends to a large extent, on

the presence of other particles (paraffins, aromatics, resins, e.t.c.) in the crude oil52.

The amounts of carbon and hydrogen in asphaltenes usually vary over a narrow range,

corresponding to a hydrogen-to-carbon ratio of 1.15 ± 0.5%.1 It is in the heteroatom content

29
 the asphaltenes differ significantly from the crude oil. They contain substantial amounts of

nitrogen, oxygen and sulphur, in addition to trace amounts of nickel and vandadium.

As previously discussed, crude oil composition can vary from field to field, and this will be

reflected in the asphaltene fractions as well. Only between these two samples, the amount of

several heteroatoms differs significantly. The amount of for instance oxygen and sulphur can

vary from 0.3 to 4.9% and 0.3 to 10.3%, respectively. The nitrogen can give an asphaltene

molecule both basic and neutral behaviour, depending on if the nitrogen is a part of a

quinolines or a carbazole moiety54. Oxygen atoms are believed to mainly originate from

phenolic, hydroxylic or carboxylic functionalities. Sulphur can be both a part of the aromatic

core as thiophenes or in the aliphatic chains as sulphide derivatives, or in some cases as

sulphur bridges55. Transition metals as vanadium and nickel are believed to be an element of

porphyrin structures in the asphaltenes56.

Table 2: Chemical composition of West Texas and Louisiana Asphaltene Samples. The data

are taken from Wattana et al.53

Parameter West Texas Asphaltene Louisiana Asphaltene

Elemental analysis (wt%)

Carbon 85.78 86.24

Hydrogen 7.16 6.78

Nitrogen 1.19 1.23

Sulphur 2.71 0.65

Oxygen 1.34 3.19

Metal Content(ICP) (ppm)

Vanadium 190 13

Nickel 260 63

Iron 178 526

2.5.5. Sources of Asphaltenes

30
 High molecular weight constituents of crude oils usually contain nitrogen, sulphur and

oxygen (N, S, and O). They are referred to as resins and asphaltenes. They constitute the

heavy ends of petroleum.

They are today widely recognized as soluble, chemically altered fragments of kerogen

which migrated out of the source rock for the oil, during oil catagenesis. Asphaltenes are the

heaviest and most polar fractions found in crude oil. The characteristics of the asphaltenes

and the amount of them in oil depend to a greater extent on the crude source. During refining

of crude oil, asphaltenes will end up in a high percentage in the residual fuels as the light

fractions (gasoline, jet fuel, e.t.c.) are removed from the oil through cracking and visbreaking.

Asphaltenes are found in immature heavy oils resulting from an early breakdown of

high sulphur kerogen, with the associated high sulphur and nitrogen content of crude oil.

Most heavy oils originate from normal, fluid crude oils which have been subsequently

degraded in the reservoir by one or several of the following processes; biodegradation, water

washing, loss of volatiles, inorganic oxidation. These processes result in a decrease of the

light ends of the crude oil, and also of the alkanes and low molecular weight alkyl benzenes,

and an increase of the more resistant benzothiophene derivatives, poly aromatics, resins and

asphaltenes. Furthermore, at certain conditions, sulphur extracted from sulphate by anaerobic

bacteria may react with hydrocarbons to increase the sulphur content of the abundance of

heavy constituents such as asphaltenes. The result of this type of alteration is a heavy, highly

viscous oil.

2.5.6. Structure of Asphaltenes

Asphaltenes are very complex molecules believed to consist of associated systems of

polyaromatic sheets bearing alkyl side chains. The heteroatoms; oxygen, nitrogen and sulphur

as well as the metals; vanadium, nickel and iron are also present in asphaltenes. The exact

31
molecular structure of asphaltenes is not known today because of the complexity of the

asphaltene molecules.

The molecular weight of asphaltene has been an issue of debate and has annoyed

many researchers throughout the years. The reason behind the troublesome analysis and

determination of asphaltene molecular weight is that asphaltene tend to self-associate, even at

low concentrations (~0.1 g/L in toluene) 57. Thus, when first starting to analyze asphaltene

samples one typically measured the size of the aggregates and not the monomeric

asphaltenes.

Standard methods such as Vapor Pressure Osmometry (VPO) and Size Exclusion

Chromatography (SEC) have yielded molecular weights of 4000 and ~ 10000 g/mol,

respectively58. The most promising techniques today are the laser desorption ionization –

mass spectrometry59 (LDI-MS), fluorescence correlation60 and depolarization spectroscopy.

These highly sensitive techniques show average asphaltene molecular weights smaller than

the values obtained with VPO and SEC, and the currently accepted value of asphaltene

average molecular weight now seems to range from 500 to 1000 g/mol, with an average of

750 g/mol. The number of aromatic rings in each molecule is estimated to be in the range

from 4 to 10 fused aromatic rings. It should be emphasized that, due to the polydisperse

nature of asphaltenes, the asphaltene molecular weight is always given as an average

molecular weight of the whole distribution.

In addition to the controversy regarding molecular weight, there has also been a

debate on if the asphaltenes are comprised of only one fused, aromatic core, surrounded by

aliphatic chains or that more than one fused, aromatic core can exist in one asphaltene

molecule where the fused cores are interconnected through aliphatic chains61-64.

32
 Figure 2.7. Some Proposed Structures of Asphaltenes64

2.6 Crude Oil Analysis

Various methods have been introduced and developed for a complete characterization

of the components in a crude oil and its fractions. This is because of the extreme complexity

of the composition of petroleum and petroleum products, no single analytical method can be

33
used to measure all the components in an environmental sample. For example, methods

suitable for sampling and analysis of the volatile paraffinic (alkanes) hydrocarbon

components are not directly applicable to the high molecular weight aromatic and polar

fractions or to metals. Moreover, because petroleum is a complex and labile mixture, the

composition of a sample released into the environment begins to change almost immediately.

Fractionation and separation of components begins to take place by evaporation (or

condensation), dissolution (e.g., of more polar components into water) and adsorption/

absorption (e.g., into soils, sediments or biological tissues). Chemical, photochemical and

biochemical reactions occur, leading to further selective changes and the appearance of

degradation products and metabolites.

The higher the boiling point of a fraction, the more difficult it is to analyse its composition

due to the increased complexity. Higher molecular weight species found in higher boiling

point fractions have more carbon atoms per structure and therefore the number of structural

rearrangements increases rapidly65. A single analytical technique can be applied to determine

molecular composition of low boiling fractions, which have reduced complexity 66, 67
.

Conversely, the complexity of higher boiling fractions pushes the analytical techniques to

their limits in order to elucidate compositional information. A variety of analytical techniques

have been employed to examine the structure of crude oil constituents. Examples of these

techniques include: gas chromatography (GC)68-70, two-dimensional gas chromatography (GC

X GC)71, gas chromatography/mass spectrometry (GC/MS)72, different liquid

chromatographic (LC) techniques (such as high performance liquid chromatography (HPLC)

with different stationary phases73-75, gel permeation chromatography (GPC)76 , near-infrared

spectroscopy (NIR)77, fluorescence spectroscopy78, nuclear magnetic resonance (NMR)79 and

X-ray scattering techniques; such as X-ray absorption near edge structure (XANES) and X-

ray photoelectron spectroscopy (XPS)80-82. Boduszynski et al published a series of papers with

34
comprehensive characterization of heavy crude oils by a variety of analytical methods

including HPLC, 13C NMR, vapor pressure osmometry (VPO), and field ionization mass

spectrometry (FIMS) 83-86. Unlike the majority of analytical techniques, high resolution mass

spectrometry nowadays is well suited for the analysis of complex mixture such as crude oil,

because the number of mass spectral peaks per analyte is of order one, in other words; by

using soft ionization methods that avoids fragmentation, each analyte has one signal 87. Early

mass spectrometers based on a magnetic sector had a mass resolving power of about 10,000,

which was not sufficient for the characterization of crude oil species. Various mass analyzers

have been developed throughout the last century such as quadrupole, ion trap, time-of-flight

(TOF), Fourier transform ion cyclotron resonance (FT-ICR) 88, and Orbitrap89. Only FT-ICR

and long-transient-Orbitrap mass spectrometers are capable to provide the peak capacity

needed to resolve individual components of a complex data matrix in combination with the

necessary accuracy90, 91. Another significant factor in analyzing heavy crude oil samples and

fractions using mass spectrometry is the ionization efficiency of large molecules with

different ionization sources. Therefore, several methods have been developed to identify

whole ranges of compounds (polar and non-polar). For the characterization of lighter

fractions from crude oil, the electron ionization technique (EI) was employed as the method

of choice at the early years of crude oil analysis. For the ionization energy a lower voltage

was applied in order to avoid fragmentation of the analytes. Since the introduction of low-
92
voltage electron ionization (LVEI) , it has been most frequently used in the crude oil

industry. For instance, the speciation of neutral and basic nitrogen compounds from an off-

shore Californian crude oil was achieved with LVEI as a source for ions93. However, the

experiments were performed on a double focusing magnetic sector instrument with a

resolution of 10,000. In another attempt to characterize nitrogen and sulphur compounds in

gas oil and kerosene samples, an ammonia chemical ionization (CI) was implemented

35
enabling selective speciation of these heterocycles 94. Chemical formulas of nitrogen, oxygen

and sulphur containing compounds found in crude oil distillates were identified by coupling

the LVEI source to an FT-ICR mass spectrometer 95. Field desorption/field ionization was used

for the characterization of heavy crude oil fractions and residues 96. A vast number of

nonpolar components from crude oil samples were determined by an FT-ICR mass

spectrometer interfaced with a field desorption ion source97. Other ionization techniques such

as thermospray98 and matrix assisted laser desorption ionization 99, 100 were applied on a small

scale in the field of crude oil analysis. However, samples in the previously mentioned

ionization techniques are introduced to the mass spectrometer under vacuum. On the other

hand, atmospheric pressure ionization (API) methods nowadays are more frequently used in

the field of crude oil analysis. The most common API sources used in the analysis of crude oil

samples are electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI),

atmospheric pressure photo ionization (APPI) and atmospheric pressure laser ionization

(APLI). The applicability of the mentioned ionization techniques depends on the polarity of

the analyte.

2.6.1 Chromatography as an Analytical Technique

Chromatography is the most widely used, the most powerful and the most effective of

the separation techniques. It is not a single separation method, but consists of a group of

related methods that have common features. Chromatography has been extensively used in

the analysis of various kinds of materials in organic, inorganic, biochemical and medical

science laboratories. It can also be used in the determination of physical parameters,

thermodynamic and kinetic quantities and for preparative purposes101. Chromatography is

used to separate crude oil samples into their components of aliphatic hydrocarbons, aromatic

hydrocarbons, nitrogen and sulphur compounds on large columns of powdered fullers

36
earth102. The chromatographic methods of analysis is also used in SARA method of analysis

and also in the analysis of n-alkanes after extracting with deparaffination method103, 104.

Modern chromatography encompasses a diverse group of separation methods which

are based on components partitioning between a stationary phase and a mobile phase 105.

Keulemans defined chromatography as a physical method of separation in which the

components to be separated are distributed between two phases, one of these phases

constituting a stationary bed of large surface area, the other being a fluid that percolates

through or along the stationary bed. It is the responsibility of the mobile phase to carry the

sample components through the stationary phase, that is, solutes phase. The fraction of time a

solute spends in each phase is determined by its distribution coefficient, which must be

different from those of the other solutes if a separation is to occur.

2.6.1.1 Classification of Chromatographic Methods

The diversity of chromatographic methods makes classification difficult using a single

set of criteria. Chromatographic methods can be subdivided according to the manner in which

it is immobilized.

It can also be subdivided according to the mechanism phases. Partition is a bulk phase

distribution process in which solute forms homogenous solutions in each phase. Adsorption

involves interactions at a surface or fixed sites on a normally solid stationary phase.

Exclusion relies on the ability of a porous solid stationary phase to discriminate on the basis

of size by admitting small molecules to its pores but excluding large ones.

Another very broad method of classification is based on the physical configuration of

the stationary phase. In most chromatographic methods, the stationary phase is held in a

column through which the mobile phase is pushed under pressure or drawn by gravity.

Column chromatography is divided into two types according to how the stationary phases are

37
immobilized. Packed columns use a stationary phase of small solid particles (often coated

with a thin layer of liquid) contained in an open tube. Open tubular or capillary columns are

made by forcing a liquid through a small diameter tube. A thin layer of the liquid coats the

inside wall of the tube and is held there by capillary forces or by chemical bonding to the

surface. In planar chromatography, the stationary phase is a flat strip of paper or a solid

coated onto a glass plate. The liquid mobile phase pass through the stationary phase by

capillary wetting or a combination of wetting and gravity. This type of chromatography has

limited applications in quantitative analysis

Another classification is made according to how the sample is introduced to the

stationary phase and moves through it. In frontal chromatography, the sample is fed onto the

column continuously and acts as the mobile phase. Sample components emerge from the

columns as fronts. Displacement chromatography is characterized by a mobile phase that is

strongly attracted to the stationary phase, causing the sample components to be pushed

through the column by the advancing solvent. The displacement technique generally produces

poorer separations than elution, but can tolerate larger samples, thereby making it more useful

in preparative and industrial scale separations. In elution chromatography, the sample

components are carried along the column by a mobile phase, and separations is as a result of

their spending different fractions of time in that phase. In addition to producing good

separations, elution chromatography has the considerable advantage of leaving the column in

its original condition, ready for another sample24.

38
 Table 2.3: Summary of the Classification of chromatographic methods

According to According to According to According to According to

mobile phase stationary phase mechanism of physical sample

retention configuration development

Gas Liquid Partition Column Frontal

Gas Solid Adsorption Planar Displacement

Liquid Liquid Exclusion Elution

2.6.1.2 Gas Chromatography

Martin proposed the technique of gas chromatography in their original paper on partition

chromatography101.

In gas chromatography, the mobile phase is a gas. The technique is good for

separating those substances which are volatile and do not decompose at the operating

temperature. The stationary phase can either be a solid [gas-solid chromatography (GSC)] or

a liquid film spread on the surface of a solid support [gas-liquid chromatography (GLC)].

Gas-solid chromatography separations depend upon the adsorption of the solutes from a

mobile gas onto the surface of the stationary solid. The technique is used mainly for the

separation of low molecular weight gases and does not have many applications in analytical

chemistry. In Gas-liquid chromatography, its retention is based on the solubility of a solute in

a liquid stationary phase. GLC has experienced phenomenal growth since its inception in the

1950s and certainly it is among the most powerful and often used tools available for

separation and analysis.

39
 The primary difference between GLC and the other forms of chromatography is that

the mobile phase is a gas instead of a liquid. Since the viscosity of gases is considerably

lower than the viscosity of liquids, the gases can be forced to flow through the column at

extremely rapid rates. Flow rates between 50 and 100 cc/min routinely are used 102, much

faster than the 1 to 3 ml/min used in classical liquid chromatography methods. Successful

separation using such rapid flow rates are possible only because of the exceedingly rapid rate

of establishment of partition equilibrium between a gaseous mobile and stationary phase.

Separation Efficiency

One criterion used to measure the efficiency of a gas chromatographic column is called the

HETP which is the height equal to theoretical plate. For successful separators, there should be

as many stages or equilibrium steps per unit column length as possible. Also, for successful

separations and efficient column operation, a low numerical value for HETP is required.

The value of the HETP is obtained by dividing the length of the chromatographic

column (L) by the number of theoretical plates in the column, n.

HETP = L/n

The number of theoretical plates required for a particular solute is given by the expression;

n = 16 (tR/wb)2

Where wb is the width of the chromatographic peak at its base. The width is measured by

extending the tangent to the inflection points on each side of the peak until each intersects the

base line.

It is also very important to know the experimental parameters and operating conditions can be

adjusted to optimize the efficiency of the column operation (HETP).thus, Van Deemter

equation has been derived as;

40
 HETP = A + B/V + Cv

Where V is the average velocity of the gas flow through a column; A, B and C are constants

for a particular system. This three-term equation states that the efficiency of a gas

chromatography depends upon the length of the various parts along which the gaseous

molecules move (A), the diffusion of the molecules within the gas phase (B), and the transfer

of solute from the gas to the liquid phase and back again (C).

A, the multiple path length term, represents the effect on the column efficiency (peak

spreading) due to the molecules travelling along its own pathway among the particles packed

in the column.

Fig. 2.8: The schematic diagram of a typical gas chromatograph.

Carrier gas: Elution analysis is the normal mode of operation for gas chromatography. Since

the eluting agent is a gas, it is called the carrier gas. The carrier gas must be inert to the

column material, as well as the liquid and stationary phases. The sample must not interact

chemically with the carrier gas (for example, hydrogenation or reduction). It should facilitate

the detection of the eluted solutes. The most commonly used carrier gases are hydrogen,

nitrogen, helium, and argon, all of which can be obtained commercially in adequate purity in

pressurized cylinders.

41
 The detection system used determines the carrier gas. The widely detector is thermal

conductivity. Successful thermal conductivity requires that the thermal conductance of the

carrier gas be greatly different from that of the solutes.

Injection Port: Most gas chromatographic samples are liquid. For a clean chromatographic

separation, the sample must be introduced as a narrow concentrated band at the top of the

chromatographic column. Consequently, it is necessary to vaporize the samples completely,

and rapidly, before they enter the column.

The injection port consists of a heated metal chamber of very small volume that is

placed in the gas train just before the beginning of the column. The opening to the outside is

capped by a self-sealing rubber septum; through which the sample is injected by means of a

hypodermic syringe. The temperature of the injection port is usually set at or just slightly

above the boiling point component of the mixture to the separated. At this temperature, the

liquid is vaporized instantly. Since the injection port is the gas train, the gaseous sample now

is swept by the carrier gas onto the top of the column.

The Columns: Gas Chromatographic columns consist of long tubes filled with the solid

packing. In order for the packed columns to fit conveniently into the air thermostats (ovens),

they are coiled into spirals or bent into a U or a W shape. U-shapes are used for columns up

to 10 feet in length, W-shapes for columns up to 20 feet long, and coils for columns of any

length. Columns frequently are packed with the tubing straight and then bent or coiled, so as

to prevent gaps and ensure a more uniform packing.

Supports: Gas chromatographic columns are filled with finely powdered solids. The function

of this powdered solid is to provide a support for the thin film of liquid. Since gas

chromatographic columns are run above room temperature, thermal stability of the support

material is necessary. Porosity must be high in order to minimize the pressure drop as the

42
carrier gas is forced rapidly through the packed columns. The most commonly used support is

diatomaceous earth, although powdered glass, sand, graphite, powdered Teflon, detergent

powders, and other inert materials can be used.

The Detectors: Martin and James pointed out that it is easier to detect changes in the

composition of gaseous mixtures than of liquid mixtures. After separating a mixture of low

molecular weight carboxylic acids, they monitored the concentration changes in the eluate by

means of automatic acid-base titrations105. Times have changed such that of the twenty

detectors listed by Hartmann106, only two are based on chemical reactions, all the rest depend

upon measurement of some physical property of the eluate.

The sensing device on a gas chromatograph ought to possess the following

characteristics:

1. It must measure concentration changes in binary (or ternary) mixtures of gases, where

the solute concentration is 0.001M or less.

2. It should give a response that is linear with concentration, to enable calibration without

unnecessary elaborate procedures.

3. It should respond rapidly, since the elute emerges from the column at fast flow rates. To

facilitate quick response, the volume of the detector should be kept very small.
4. It should be versatile, that is, it should respond to as wide a variety of solutes as possible.

Since the chemical identity of all components in mixtures separated by gas

chromatography cannot be predicted in advance, the detector must be capable of

responding to unsuspected components. To achieve versatility, detectors should respond

to some general property of molecules, rather than to some functional group or specific

property.
5. It should give a sensitive response, that is, it should be capable of giving a signal for

extremely small quantities of solute. The signal produced should change appreciably for

slight changes in concentration.

43
6. It should be stable, that is, the extent of the response should not change over either short

or long period of time. The signal obtained from a given amount of solute should be

reproducible.
7. It should not destroy the sample. The detector should be capable of withstanding attack

by a large number of chemical reactive substances.

There are a variety of detection systems used in gas chromatography. Some of them are:

(a) Thermal Conductivity Detector: This type of detector compares the heat conducting

ability of the exit gas stream to that of a reference stream of pure carrier gas. To accomplish

this, the gas streams are passed over heated filaments in thermal conductivity cells, measures

changes in filament resistance of the cells, reflect temperature changes caused by increments

in thermal conductivity. This resistance change is monitored and registered continuously on a

recorder. Therefore, the response of a thermal conductivity detector depends upon the carrier

gas used, the temperature of the wire, and the temperature of the block. For maximum

response, a carrier gas with a high thermal conductivity should be used. Thermal conductivity

detectors are non-destructive and produce a differential signal.

(b) Flame Ionization Detector (FID): In flame ionization detector, the gaseous eluate is

mixed with hydrogen after it emerges from the chromatographic column. This mixture is

burned in a metal jet. The positive ions and electrons are produced in the flame when organic

substances are present. The ions are collected at electrodes and produces a small measurable

current.

The main advantage of the flame ionization detector is its great sensitivity. It is

capable of detecting as low as 2 x 10 -12 g/sec of solutes. The response is linear over a 10 6 fold

range of concentration. The major drawback of FID is the lack of applicability to all

compounds. Flame ionization is used primarily for detection of solutes containing only

44
hydrogen and carbon. The detector does not respond to gases such as oxides of nitrogen,

hydrogen sulphide, phosphorus or halogen atoms.

(c). The Electron Capture Detector: This has an extremely high sensitivity. The success of

the electron capture detector rests on the readiness of a compound to capture or take on an

electron, that is, its electron affinity. Molecules containing oxygen, sulphur, phosphorus, or

halogen give excellent response in the electron capture detector. Thus, electron capture is an

excellent detector for pesticides, lead alkyls and phosphates. There is almost no response for

hydrocarbons and only a slight response for aliphatic fluorocarbons107.

2.6.1.3 Column Adsorption Chromatography

The chromatographic separation of the components in a mixture by adsorption from a

moving liquid stream onto the surface of a powdered solid confined in a column adsorption

chromatography or simply adsorption chromatography. The chromatographic column is

plugged with glass wool to prevent the finely divided solid from running through, and then

packed with powdered solid to a height of about 20-30 cm. After placing the sample on the

column, the solvent called the eluent is poured through the column at a constant rate, washing

over the sample. The eluent may be a pure liquid or a mixture of liquids. As the eluent washes

over the narrow sample band, the sample will dissolve off the surface of the solid into the

moving liquid. The more soluble components of the sample will dissolve first. Since the

liquid is flowing, the dissolved components will move a little way down the column. The

more soluble a compound is in the eluting liquid, the longer the component will be dissolved

and since the liquid is flowing, the faster the solute will move down the column. A solute that

is completely insoluble in the eluting agent will remain in a narrow band at the top of the

column and not move, no matter how many litres of solvent are passed through.

45
 As the solutes move down the column, their rates are determined by the distribution

behaviour of the solute between the surface of the solid and the moving liquid. The partition

or adsorption equilibrium will determine the rate of movement. The process of separating the

components of a mixture into zones or bands of pure substance, each located at a different

place on the column is known as the development of the chromatogram. The process of

removing from the column and collecting each solute band is known as elution and the

solution containing each sample component is known as eluate.

The pertinent experimental factors that determine the success of a column adsorption

chromatographic separation are:

1. The nature of the adsorbent

2. The nature of the solvent used to elute the sample
3. The ratio of flow of solvent through the column
4. The geometry of the column containing the adsorbent (the sample-eluent system)
5. The temperature.

The feature that distinguishes an adsorbent from any other solid is the magnitude of

its surface area per unit weight. An adsorbent is defined as any finely divided solid

possessing an extremely large surface area that is capable of attracting molecules to its

surface. Large surface areas are those from 5 to 200 square metres/gram. The diameter of

the particles of a given weight of the adsorbent will determine the surface area. The

smaller the particle diameter, the more extensive the area per gram of solid available for

adsorption. The separation efficiency in adsorption chromatography increases with

decreasing particle size. The smaller the size of the adsorbent particles, the harder it is to

have the eluent flow through the column at a reasonable or even particles rate.

Techniques of Column Development

There are three different methods by which a column chromatogram can be

developed:

46
(a) Frontal analysis: This was one of earliest methods of column chromatography. In frontal

analysis, a mixture of solutes is fed continuously into a short chromatographic column which

is pre-saturated with the solvent is used. A very large volume of the sample solution is poured

continuously into the top of the column. The liquid emerging from the bottom of the column

is analysed continuously, and when its composition becomes identical to that of the sample

being poured in at the top of the column, the analysis is complete. The most weakly adsorbed

or partitioned component of the mixture emerges alone from the column first, allowed by a

sharp front separating it from a mixture of the second weakest and the weakest. This mixture

comes off the column until a second front is reached. The second front is followed by a

mixture of the three most weakly adsorbed or partitioned components and so on.

This type of analysis does not give effective separations. Only one solute of a mixture

can be obtained in a pure condition, but even the recovery of that solute is not 100%. This

also makes the resulting chromatogram to be very difficult to interprete.

(b) Elution analysis: This is much more widely used today than any other mode of operation

because the components of a mixture can be separated quantitatively and the column can be

used repeatedly for successive analysis.

In this technique, sample is introduced at the upstream and of the stationary phase and

pure solvent, called the eluent or developer, is allowed to flow through the system. This leads

to a differential migration of solutes according to their distribution between the two phases.

This is called the development of the chromatogram. The eluting liquid must be less strongly

adsorbed onto the column than any of the components in the sample. If the solutes have

sufficient retention factor (Rf) values, and do not spread appreciably, a separation is achieved

and the solutes elute in sequence from the end of the stationary phase.

47
(c) Displacement analysis: In displacement analysis, the sample (small in volume) is placed

in a narrow band at the top of the chromatographic column. A second solution containing a

solute that is very strongly adsorbed or partitioned is slowly poured through the column. The

solution is called the displacement agent or the developer. As the developer passes through

the column, it displaces all of the components of the sample from their positions onto the

stationary phase, forcing them into the mobile liquid. At the same time, each of the

components of the sample begins to displace those other components more weakly adsorbed

or partitioned than it. As they move reluctantly through the column, the components

gradually separate into contiguous, sharp bands of pure components which eventually emerge

from the bottom of the column24.

2.7 The Impact of Asphaltenes in Petroleum Refining

In the activities of the oil industry, the deposition of organic compounds is frequent. Among

the deposits that cause operational problems, we can identify two predominant groups:

paraffins and asphaltenes. Therefore, it is necessary to determine the conditions under which

these deposits occur and the way in which they can be avoided in order to generate the least

possible damage to the process107. Deposits may occur in reservoir rock and source rock for

oil. This impairs the production of the well by causing the blocking of pores of the rock and

by changing a very important property of the reservoir rock, its wettability, which is the

tendency of a fluid to spread or adhere to a solid surface in the presence of non-miscible

fluids, and can be modified by adsorption of polar compounds and/or deposition of organic

material and thus affect the migration of oil. This is an extremely serious problem, since it

can lead to the loss of the well108-109.

The phenomenon of deposition can also occur on the production lines. It is known

that the use of any method, chemical (injection of solvents, for example) or mechanical

48
 (using scrapers), to remove this type of deposit is an expensive operation and requires a lot of

security because any accident can lead to line loss110.

The deposition of asphaltenes can also happen in separators during the final stage

depressurization of oil111, as well as in almost all stages of production, processing and

transportation of oil and is an extremely serious problem that affects significantly the costs of

oil industry. In refining, these constituents may lead to catalyst deactivation and the formation

of waste during the thermal and thermo-chemical processing of heavy residues of oil.

2.8. Prevention of Asphaltene Deposition

Asphaltenes can deposit anywhere in the production system, but perhaps the most

damaging place is in the near-wellbore region where asphaltene-blocked pores are difficult to

access for remediation. Flocculation and deposition of asphaltenes can be controlled through

better knowledge of the mechanisms that cause its flocculation in the first place. It can also

be controlled using various methods such as:

1. Production techniques: These include

i. Reduction of shear
ii. Elimination of incompatible materials from asphaltic crude streams
iii. Minimization of pressure-drops in the production facility
iv. Minimization of mixing of lean feedstock liquids into asphaltic crude streams.
2 Chemical treating techniques
i. Solvents
ii. Dispersants
iii. Oil/dispersant/solvents

Chemical inhibitors can be used to prevent asphaltene precipitation. The inhibitors must

be placed in the oil before asphaltene precipitation has taken place. In completion systems where

capillary tubing already exists, a continuous injection of an inhibitor can be used. Continuous

injection of an inhibitor into pipelined crude is straightforward, as well as the injection of

inhibitors immediately before the mixing of asphaltene in incompatible oils. Asphaltene inhibitors

can be squeezed into the formation, similar to inorganic-scale inhibitors. However, these

49
inhibitors are necessarily oil soluble, resulting in a short functional lifetime for the inhibitor.

Asphaltene inhibitors are, generally, resinous organic polymers. Their functional groups interact

with the asphaltenes in much the same way natural resins keep the asphaltenes dissolved. It is

claimed that the strength of the interaction is stronger than with natural resins, keeping the

asphaltene dissolved over a broader range of pressure and temperature. Given the variability in

the asphaltene structure, it is important that the polymer inhibitor be evaluated on the specific

crude in which it will be placed. In principle, it is possible that these polymers could also cause

formation damage by altering the wetting properties of the rock. It is obviously prudent to

evaluate this possibility on core samples before treatment.

Asphaltene deposits are generally removed manually, if present in readily accessible

equipment, such as separators and other surface equipment. For tubular and flowline deposits,

removal techniques involve chemical methods such as solvent soaks with or without dispersants.

Combining solvents and heating may also be effective. Physical methods can be used depending

on the hardness of the deposit (e.g., pigging, hydroblasting, and drilling). Pigging is appropriate

for removing pipeline deposits—often, mixtures of waxes and asphaltenes.

The traditional solvent of choice has been xylene. It is to be expected, given the

variability of asphaltene chemistry described, that the refinery-solvent mixture will have to be

tailored to the specific well—one mixture will not necessarily cure all. Terpenes (more-

expensive natural products) have been used effectively as solvents, replacing xylene because

of health, safety, and environment (HSE) considerations. Certain alkylbenzene compounds

will stabilize (dissolve or disperse) asphaltenes in simple aliphatic solvents (e.g., heptane).

2.9. Some previous Research on Nigerian Crudes

Past literature on Nigerian crudes show that there has not been much work done so far

compared to the developed countries. Among the published work is that of Nwadinigwe 112

50
who determined the levels of vanadium and nickel in some Nigerian crude as well as their

distillation residues. The result of the research showed that there was low concentration of

these elements as to make the added cost of removing them during crude oil processing

economically unprofitable. In addition to this, the same Nwadinigwe and Nwobodo 113 in their

study gave comparative performances of molecular sieve and urea adduction techniques, with

respect to the ranges and quantitative yield of n-paraffin extracted from two well-head crudes.

Additional work by Nwadinigwe and Achilike114 determined the metal contents of some

dewatered Nigerian crudes and the corresponding associated water.

Nwadinigwe and Maduka115 have worked on a qualitative and quantitative assessment

of classes of classes of nitrogenous compounds in some Nigerian crude. Anigbogu

investigated the comparative performance of using single solvent and mixed solvent to

precipitate asphaltenes from different Nigerian crudes116. Alumona determined the n-alkanes,

asphaltenes and resins present in different Nigerian crudes using urea adduction24.

Azogu has investigated the application of the ligand exchange reaction followed by

pyrolytic mass spectral analysis of the resulting complexes in the analysis of aromatics in

crude oil samples117.

Ofodile has worked on the urea adduction of n-paraffin in kerosene (boiling point 75-

265⁰C). He compared certain key properties such as flash point, smoke point, specific gravity

and the ASTM distillation profiles of the resulting raffinate with those of the original

kerosene118.

Other research activities on Nigerian crude oils include the joint work of Ekweozor,

Okogun, Ekong, Maxwell and Okoye who analysed shale samples and crude oil from the

Niger Delta area for triterpenoid derivatives 119 and also the work of Tedder, in which the

percentage weight composition of a Nigerian light naphtha (boiling point 65-164 oC) was

determined120. Idris determined the saturated hydrocarbons present in Nigerian crudes

51
selected from different oil wells121 while Muhammad determined the concentration levels of

some heavy metals in organic fractions of Nigerian crude oil122.

Although many research data have been published on Nigerian crudes that established

them to be largely light and sweet, low in sulphur and nitrogen (making them the sweetheart

of refiners), there is no published data on aromatics to saturates ratios. It is this important

literature gap that this research aims to address using Afiesere crude, Kokori crude and

Nembe crude as target samples.

CHAPTER THREE

3.0 Experimentals

3.1 Sample Collection

Three Nigerian crude oils namely Afiesere, Kokori and Nembe crudes were studied. They

were collected from Shell Petroleum Development Company (SPDC) located in Afiesere,

Delta State and in Nembe, Bayelsa State respectively and stored in plastic containers.

52
 Kokori
Afiesere
Fig 3.1: Map of Delta State (Indicating Kokori and Afiesere Locations)
Source: Niger Delta Diaspora Organisation Europe (www.nddoe.org)

53
 Nembe
Fig 3.2: Map of Bayelsa State Indicating Nembe Local Government Area

Source: Bayelsa State Tourism Development Agency (BSTDA)

3.2 Materials and reagents

N-heptane

Toluene

Dichloromethane

Methanol

Silica gel were all from Aldrich Company and were used without further purification.

54
 Other materials used were:

Magnetic stirrer

Weighing balance

Centrifuge (model no 80-2B with maximum speed of 4000 rpm)

Oven

Rotary evaporator

Laboratory burette (200 mL)

Graduated cylinders

Beakers

Reagent bottles

Spatula

Filter paper (Whatman number 2 filter paper with pore size of 2µm)

Cotton wool

Funnel

Gas Chromatograph (Buck Scientific Model 910).

Digital Viscometer (Sarchtech Model NDJ-5S),

55
3.3 Method

3.3.1 Physical Properties of the Crudes

Crude oil Density, Viscosity and API Gravity Measurements

The density of the crudes were calculated from the simple relationship between the

measured volumes of the crudes and the mass of the crudes using the equation;

Density = Mass of crude (g)

Volume of crude (ml)

The viscosity of the crudes were determined using Sarchtech Digital Viscometer while

the API Gravity was determined using the equation:

API Gravity = 141.5 _ 131.5

Specific gravity of the crude at 60⁰F

3.3.2 Precipitation of Asphaltene

The precipitation of asphaltenes was carried out at the Center for Energy Research and

Development, University of Nigeria, Nsukka.

n-Heptane (800 mL) was mixed with 20 g of each of the crudes at room temperature.

The mixture of the crude and the n-heptane solvent was agitated by using a magnetic stirrer

for 80 minutes and allowed to equilibrate for 48 hours before filtration.

Before filtration, the equilibrated mixture was centrifuged at a speed of 2000 rpm for

30 minutes. After this procedure, the supernatant (maltene) was decanted and kept separately

while the solid residue which is mainly composed of precipitated asphaltenes was washed

56
and dried in the oven at 80⁰C for 48 hours to ensure proper drying until no change in weight

was observed. The weights were recorded.

The maltenes obtained from the n-heptane solvent were fractionated into saturates,

aromatics and resins. The separation into these petroleum fractions was performed using a

chromatographic method. This was carried out in the Glass Blowing Room of the Department

of Pure and Industrial Chemistry, University of Nigeria, Nsukka.

3.3.3 Activation of the Silica gel

Silica (granulated) gel (200 g) was spread evenly on a tray and dried in an oven for 24 hours

at a temperature of 105⁰C. The dried silica gel (40 g) was packed in a column and used to

carry out the column chromatography and 50 ml of dichloromethane was added gradually in

order to prepare the slurry and also to wash off any trace of impurity in the silica gel. After

this procedure, the silica gel was ready for use in column chromatography.

3.3.4 Chromatography procedure

The maltene sample was added to the top of the activated silica gel (granulated) in the

column with the help of a funnel and allowed to percolate. After the entire sample had

entered the gel, n-heptane (100 mL) was added to maintain a liquid level well above the silica

gel until saturates were washed off from the adsorbent.

110 mL of n-heptane effluent (i.e. n-heptane + saturates) were collected from the column.

After the collection, the receiver was replaced with another receiver for the collection of the

aromatics. Immediately after all the heptane effluent had eluted, toluene (100 mL) was added

to the column through a separatory funnel. The column was allowed to drain and toluene

effluent was collected. At this point, resins have adsorbed on the gel.

57
 To recover the resins, a solvent mixture of dichloromethane and methanol (in the ratio of

50:50) to make up to 100 mL was charged slowly to the top of the gel column. At this point,

102 mL of dichloromethane + methanol effluent (resin + solvent) was collected. After all the

effluents had been collected for a particular crude, the silica gel was removed and replaced

with a fresh activated silica gel. This procedure was carried out for the maltenes in the three

crudes studied. Recovery of the various components of interest from the various effluents was

by rotary evaporation.

After the recovery, the aromatics and saturates fractions which are the fractions of

interest in this study were weighed and their ratios were calculated.

3.3.5 Gas Chromatography

Gas chromatographic analysis was carried out at Springboard Research Laboratory, Awka.

This was performed using Gas Chromatograph (Buck Scientific Model 910) and Restek 15

meter MXT-1 columns. The method of analysis was of the United States Environmental

Protection Agency (USEPA) 8270. Before running the analysis, the GC/FID was made free

from impurity by allowing all the peaks in the column to elute until a clear straight line on the

baseline was achieved. The saturates and aromatic hydrocarbons obtained from Restek’s ISO

9001 Registered quality was run for the calibration of the GC/FID instrument. This was done

to identify the particular peaks of interest in the sample.

Injection volume was 1µl with helium as the mobile phase, and flame ionization detector

(FID). Injection and detection temperatures were 250 ⁰C and 280⁰C respectively. The

corresponding peaks obtained from the standards were used to identify the particular peak of

each analyte in the samples. The same conditions were used for the saturates and aromatics in

the other crudes studied.

58
 CHAPTER FOUR
Results and Discussion
4.1 Density

The main use of the density result is to characterize to an extent the quality of the

crude oil.

The densities of the crudes are shown in the table below:

Table 4.1: Density of the crudes in g/mL

Kokori Afiesere Nembe
0.854 0.836 0.828

The API gravities of the crudes were calculated and their values are given below
Table 4.2: API Gravities of the crudes in ⁰API
Kokori Afiesere Nembe
34.19 37.76 39.39

In general, crude oil with ⁰API of 40⁰ – 45⁰ are classified as very light crudes, 34⁰ -

39⁰ as light crudes, 22⁰ – 33⁰ as medium crudes and less than 22⁰ as heavy crudes.

4.2 Viscosity

Viscosity results can be used to give valuable information concerning the composition of

crude oils. Using the Sarchtech Digital viscometer (Model NDJ-5S), the following results

were obtained for the three crudes:

Table 4.3: Crude oil viscosities in Poise

Kokori Afiesere Nembe
8.64 6.40 4.48

The results of some physical properties of the three crudes are shown in the tables

above. The physical property of crude oils are useful for initial screening and tentative

identification of genetically related oils. Density gives an idea about the presence of light and

59
high molecular weight hydrocarbons. The lesser the density, the lighter the amount of

hydrocarbons in the petroleum123. Nembe crude had the lowest density than the other crude

samples. This implies that the hydrocarbon content of the Kokori and Nembe crudes will be

more than that of Nembe crude.

API gravity is the reverse of specific gravity and describes the nature of crude oils, i.e.

light or heavy. From the result, the API gravities of the three crudes were 34.19⁰, 37.76⁰ and

39.39⁰ respectively. This implies that all the three crudes are light crudes. Light crudes have

API gravities from 34⁰ and above.

Viscosity results can be used to give valuable information concerning the composition

of crude oils. From the results, we can say that Nembe crude is the lightest of the three crudes

and Kokori crude is the heaviest of the crude oil samples used for this experiment. But the

results from their API gravities showed that all of them are light crudes.

4.3 Results from Asphaltene Precipitation

Detailed result of the amount of asphaltene and the maltenes obtained from the three

crudes are shown in the tables below.

Table 4.4: Asphaltene content of the various crudes

Weight (g) % Weight

Kokori 0.403 2.36

Afiesere 0.205 1.23

Nembe 0.308 1.86

60
Weight (g)

Fig 4.1: Bar Chart showing the amount of asphaltenes

The filtrate (maltenes) obtained from the crudes are shown below;
Table 4.5: Maltene content of the various crudes
Weight of Volume of Density (g/ml)
maltenes (g) maltenes (ml)
Kokori 13.94 16.85 0.827

Afiesere 12.50 15.30 0.817

Nembe 11.25 14.20 0.792

4.4 Elution Column Chromatography

The colours and weights of the three fractions obtained from the elution column

chromatography of the various crudes are presented below.

Table 4.6: Elution Colour of the three fractions

61
 Saturates Aromatics Resins
Kokori Golden yellow Yellowish brown Deep brown
Afiesere Dark yellow Dark brown Black tar
Nembe Dark yellow Dark brown Black tar
From the table above, it was observed that the colour of each fraction

deepened.

Table 4.7: The weights of the three fractions obtained are also presented below;
Saturates (g) Aromatics (g) Resins (g)

Kokori 10.69 1.52 0.7

Afiesere 10.08 1.66 0.6

Nembe 9.55 1.44 0.19

4.5 Gas Chromatographic Analysis

62
 Gas chromatographic analysis data of the saturates and aromatics are presented in the

tables below and also at the back of the appendix.

Table 4.8a: The various saturate hydrocarbons found in Kokori crude

Component Concentration (mg/L)

C13 31.2727

C14 387.6675

C21 3.8459

C22 4.3517

C23 17.9165

C24 4.9533

C26 1.2466

C27 3.1105

C28 4.7219

C29 0.2150

C32 411.9498

Total 871.2589

Table 4.8b: The various aromatic hydrocarbons found in Kokori crude

63
 Component Concentration (mg/L)

Acenaphthene 0.0000

Acenaphthylene 2.0373

Anthracene 0.5760

Benzo(a)pyrene 7.8027

Indeno(1,2,3-cd)pyrene 69.7379

Total 80.1539

Table 4.9a: The various saturate hydrocarbons found in Afiesere crude

Component Concentration (mg/L)
C13 32.1785
C14 407.8653
C21 3.4835
C22 5.7214
C23 19.9217
C24 5.1842
C26 1.8269
C27 4.5207
C28 6.0517
C29 0.9549
C32 397.8518
Total 885.5606

Table 4.9b: The various aromatic hydrocarbons found in Afiesere crude

64
 Component Concentration (mg/L)

Naphthalene 1.4066

Acenaphthene 0.0000

Fluorene 2.3827

Phenanthrene 0.0010

Chrysene 0.2870

Benzo(a)pyrene 9.1250

Indeno(1,2,3-cd)pyrene 76.5287

Total 89.731

Table 4.10a: The various saturate hydrocarbons found in Nembe crude

Component Concentration (mg/L)
C13 29.1421
C14 329.6854
C21 3.4928
C22 4.1153
C23 15.8265
C24 3.2908
C26 0.9857
C27 2.1947
C28 4.2175
C29 0.8032
C32 386.4530
Total 780.207

65
Table 4.10b: The various aromatic hydrocarbons found in Nembe crude
Component Concentration (mg/L)

Naphthalene 0.0472

Acenaphthene 0.0000

Fluorene 1.8843

Pyrene 2.1588

Benzo(k)fluoranthene 1.3945

Benzo(a)pyrene 5.3428

Indeno(1,2,3-cd)pyrene 64.2824

Total 75.11

Table 4.11: The total concentration of the saturate and aromatic hydrocarbons
Crude oil Saturates (mg/L) Aromatics (mg/L)

Kokori 871.2589 80.1539

Afiesere 885.5606 89.731

Nembe 780.2070 75.11

66
 Series 1= saturates

Series 2 = aromatics

From the table above, the aromatics to saturates ratios were calculated using the
formula:
Total aromatics hydrocarbons
Total saturates hydrocarbons
Table 4.12: The ratios of aromatics to saturates in the crudes

Kokori Afiesere Nembe

0.092 0.101 0.096

67
From table 4.4, n-heptane precipitation showed that the crudes contained very small amount

of asphaltenes (between 1 to 2% weight). Even though these crude oil samples had low

asphaltene composition, adequate measures should be taken by the oil industry to ensure that

these asphaltenes do not get to the environment. This is because they contain heavy metals

which are hazardous and if not properly discarded, they can pose great danger to the soil.

Gas chromatographic analysis data of the saturates and aromatics are shown in tables 4.8a to

4.10b. Results showed that the total concentration of the saturate hydrocarbons in Kokori,

Afiesere and Nembe crudes were 871.2589 mg/L, 885.5606 mg/L and 780.2070 mg/L

respectively while the total concentration of the aromatic hydrocarbons were 80.1539 mg/L,

89.731 mg/L and 75.11 mg/L respectively.

From table 4.12 and figure 4.3, the values of the aromatics/saturate hydrocarbon ratios were

0.092, 0.101, 0.096 for Kokori, Afiesere and Nembe crudes respectively. It was observed that

Kokori crude oil had the lowest ratio of aromatics to saturates while Afiesere crude oil had

the highest ratio. As earlier discussed, when the aromatics to saturates ratio decreases,

asphaltene aggregation will be higher. This means that Kokori crude which has the lowest

aromatics to saturates ratio will cause more problems in the refinery than the other crudes.

68
This was also evident from the results got from asphaltene precipitation where the amount of

asphaltene precipitated was highest in Kokori crude.

CHAPTER FIVE

5.0 Conclusion

The assessment of the aromatics to saturates ratios in different crude oils have been

achieved in this project work. It was found that all the crudes studied are light crudes. It was

also found that when comparing different crude oils in terms of the amount of asphaltenes

present in them, using their aromatics to saturates ratios is a very efficient method. This is

because it is very difficult to precipitate out all the asphaltene content of crude oil.

Gas chromatographic analysis of the saturates and aromatics fractions showed that this

ratio decreased in the order Kokori crude < Nembe crude < Afiesere crude. Based on this

experiment, Kokori crude has the lowest aromatics to saturates ratios and hence highest

asphaltene content. Therefore, Kokori crude will cause more problems in the refinery than the

other crudes.

5.1 Contributions to Knowledge

69
This research project has contributed immensely to knowledge in the following ways.

 For the first time, the aromatics to saturates ratios have been determined in Kokori

crude, Afiesere crude and Nembe crude.

 Gas chromatographic analysis of the saturates and aromatics fractions showed that the

aromatics to saturates ratio decreased in the order Kokori crude < Nembe crude <

Afiesere crude.
 The API gravities of the Kokori crude, Afiesere crude and Nembe crudes were

determined and the values were 34.19⁰, 37.76⁰, and 39.39⁰ respectively, indicating

that all the crudes are light crudes.

These data had not been published and will be quite useful in the refining industry to

determine the crude oil that will pose greater danger to asphaltene precipitation.
5.2 Recommendations
In this present work, we have been able to establish the fact that determining the

aromatics to saturates ratios in crude oil helps to understand better the precipitation behaviour

of asphaltenes in crude oil.

The petroleum industry should endeavour to always identify the crude oil which

contains large amounts of asphaltenes before they are sent to the refinery so as to take proper

precautionary measures. This is because asphaltene problems are enormous and this can lead

to low production thereby leading to the breakdown of refinery equipment. This can also

cause the shutdown of the refinery.

70
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APPENDIX 1
Density/Specific Gravity of the Crudes in g/mL

Kokori Afiesere Nembe

0.854 0.836 0.828

Density = Weight of Crude (g)

Volume of Crude (mL)
Volume of the Crudes = 20 mL
Weight of Specific gravity bottle = 28.45 g

For Kokori Crude,

Weight of bottle + Crude = 45.53 g
Weight of Crude = 17.08 g

81
Density = 17.08 g
20 mL
= 0.854 g/mL

For Afiesere Crude,

Weight of bottle + Crude = 45.17 g
Weight of Crude = 16.72 g
Density = 16.72 g
20 mL
= 0.836 g/mL

For Nembe Crude,

Weight of bottle + Crude = 45.01 g
Weight of Crude = 16.56 g
Density = 16.72 g
20 mL
= 0.828 g/mL

APPENDIX 2
API Gravity of the Crudes in ⁰API
Kokori Afiesere Nembe
34.19 37.76 39.39

API Gravity = 141.5 _ 131.5

Specific Gravity at 60⁰F

For Kokori Crude,

API Gravity = 141.5 _ 131.5
0.854
= 34.19 ⁰API

82
For Afiesere Crude,
API Gravity = 141.5 _ 131.5
0.836
= 37.76 ⁰API

For Nembe Crude,

API Gravity = 141.5 _ 131.5
0.828
= 39.39 ⁰API

APPENDIX 3
Viscosity of the Crudes in Poise
Kokori Afiesere Nembe
8.64 6.40 4.48

Using Sarchtech Digital Viscometer, the values for the viscosity of the three crudes were 864
mPas, 640 mPas and 448 mPas respectively.
But 1mPas = 1 Centipoise
100 Centipoise = 1 Poise

For Kokori Crude,

Viscosity = 864 mPas
= 864 Centipoise
= 8.64 Poise

83
For Afiesere Crude,
Viscosity = 640 mPas
= 640 Centipoise
= 6.40 Poise

For Nembe Crude,

Viscosity = 448 mPas
= 448 Centipoise
= 4.48 Poise

APPENDIX 4
Percentage Weight of Asphaltenes from the Three Crudes
Weight (g) % Weight

Kokori 0.403 2.36

Afiesere 0.205 1.23

Nembe 0.308 1.86

Percentage Weight = Weight of Asphaltene (g) x 100%

Weight of Crude (g)

For Kokori Crude,

Percentage Weight = 0.403 g x 100%
17.08 g

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 = 2.36%

For Afiesere Crude,

Percentage Weight = 0.205 g x 100%
16.72 g
= 1.23%

For Nembe Crude,

Percentage Weight = 0.308 g x 100%
16.56 g
= 1.86%

85
APPENDIX 5: GAS CHROMATOGRAMS OF THE SATURATES AND AROMATICS

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