Petroleum in View of its Classification, Assay and Analysis 978-93-84648-05-3.pdf · Petroleum in...

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Petroleum in View of its Classification, Assay and Analysis By Prof. Dr. Ashraf Yehia El-Naggar Prof. Dr. Abd El-Aziz Mustafa El-Fadly Prof. Dr. Yasser Mohammed Mustafa Dr. Mohammed Abd El-Salam Ebiad Ass. Researcher/Eman Saied A. Ibrahim International E – Publication www.isca.co.in , www.isca.me

Transcript of Petroleum in View of its Classification, Assay and Analysis 978-93-84648-05-3.pdf · Petroleum in...

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Petroleum in View of its Classification,

Assay and Analysis

By

Prof. Dr. Ashraf Yehia El-Naggar

Prof. Dr. Abd El-Aziz Mustafa El-Fadly

Prof. Dr. Yasser Mohammed Mustafa

Dr. Mohammed Abd El-Salam Ebiad

Ass. Researcher/Eman Saied A. Ibrahim

International E – Publication www.isca.co.in , www.isca.me

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Petroleum in View of its Classification,

Assay and Analysis

By

Prof. Dr. Ashraf Yehia El-Naggar Prof. of Analytical and Petroleum Chemistry

Chemistry Department, Science Faculty, Taif University,

Taif-Al-Haweiah-P.O. Box 888 Zip Code 21974, Kingdom Saudi Arabia.

Egyptian Petroleum Research Institute, Nasr City, Cairo, Egypt.

Prof. Dr. Abd El-Aziz Mustafa El-Fadly Prof. of Analytical and Petroleum Chemistry. Former Head of

Chromatographic Separation Division and Former Director of Analysis and Evaluation Department Egyptian Petroleum Research Institute.

Prof. Dr Yasser Mohammed Mustafa

Prof. of Analytical and Petroleum Chemistry.

Vice Director of Egyptian Petroleum Research Institute (EPRI)

Director of Central Analytical Lab and Quality Manager of ISO IEC 17025

Dr. Mohammed Abd El-Salam Ebiad

Dr. of Analysis and evaluation department and responsible in GC labs,

Egyptian Petroleum Research Institute

Ass. Researcher / Eman Saied Abdullah Ibrahim Member, gas chromatogarphic division and central analytical lab, Egyptian

Petroleum Research Institute

2014

International E – Publication www.isca.co.in , www.isca.me

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International E – Publication 427, Palhar Nagar, RAPTC, VIP-Road, Indore-452005 (MP) INDIA

Phone: +91-731-2616100, Mobile: +91-80570-83382, E-mail: [email protected], Website: www.isca.co.in

© Copyright Reserved 2014 All rights reserved. No part of this publication may be reproduced, stored, in a retrieval system or transmitted, in any form or by any means, electronic, mechanical, photocopying, reordering or otherwise, without the prior permission of the publisher. ISBN: 978-93-84648-05-3

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Petroleum in View of its Classification, Assay and Analysis iii

PREFACE

Petroleum is the most important substance consumed in modern

society. It provides not only raw materials for the ubiquitous plastics and

other products, but also fuel for energy, industry, heating and transportation.

The fuels that are derived from petroleum supply more than half of the

world’s total supply of energy. Petroleum was classified by hydrocarbon

resource or chemical composition or density or API or viscosity or carbon

distribution or pour point. An efficient assay is derived from a series of test

data that give an accurate description of petroleum quality and allow an

indication of its behavior during refining. Petroleum products are the basic

materials used for the manufacture and modern industry.

Petroleum analysis involves not only determining the composition of

the material under investigation but, more appropriately, determining the

suitability of the petroleum for refining or the product for use. In this sense,

the end product of petroleum analysis is a series of data that allow the

investigator to specify the character and quality of the material under

investigation.

Dr. Ashraf Yehia El-Naggar Prof. of Analytical and Petroleum Chemistry

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Petroleum in View of its Classification, Assay and Analysis iv

TABLE OF CONTENT

Preface iii

Table of Content iv

Chapter I: Introduction 1

(I-1) Petroleum and petroleum product 2

(I-2) Recovery and Refining of Petroleum 7

(I-3) Classification of Petroleum 9

(I-3.1) Classification as a hydrocarbon resource 9

(I-3.2) Classification by chemical composition 12

(I-3.3) Classification by density 13

(I-3.4) Classification by API gravity 15

(I-3.5) Classification by viscosity 16

(I-3.6) Classification by carbon distribution 17

(I-3.7) Classification by pour point 17

(I-4) Physical Properties of Petroleum Crude Oil 19

(I-5) Oilfield water 27

Chapter II: Petroleum Assay and Technical Fractions 30

(II-1) Petroleum constituents 32

(II-1.1) Carbon Residue and Asphaltene Content 32

(II-1.2) Density 35

(II-1.3) Distillation 38

(II-1.4) light Hydrocarbons 40

(II-1.5) Metallic Constituents 41

(II-1.6) Salt Content 42

(II-1.7) Sulfur Content 43

(II-1.8) Water and Sediment 49

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Petroleum in View of its Classification, Assay and Analysis v

(II-1.9) Wax Content 51

(II-1.10) Other Tests 52

Chapter III: Petroleum Products 56

(III-1) Gaseous Fuels 56

(III-1.1) Definition of Gaseous Fuels 56

(III-1.2) Composition of Gaseous Fuels 58

(III-2) Gasoline 59

(III-2.1) Definition of Gasoline 59

(III-2.2) Composition of Gasoline 59

(III-3) Kerosene 60

(III-3.1) Definition of Kerosene 60

(III-3.2) Composition of Kerosene 61

(III-4) Fuel oils 62

(III-4.1) Definition of Fuel oils 62

(III-4.2) Types of Fuel oils 63

(III-5) Lubricating oils 64

(III-5.1) Definition of Lubricating oils 64

(III-5.2) Composition of Lubricating oils 65

Chapter IV: Native Materials 66

(IV-1) Heavy oil 67

(IV-2) Bitumen 68

(IV-3) Wax 69

(IV-4) Natural Gas 69

Chapter V: Sampling and analysis using chromatographic methods 72

(V-1) Sampling 73

(V-2) Analysis and specifications 76

(V-2.1) High performance liquid chromatography 87

(V-2.2) Gas chromatography 89

(V-2.3) Gas chromatography-Mass spectrometry 91

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Petroleum in View of its Classification, Assay and Analysis vi

(a) Petroleum biomarker fingerprinting 91

References 94

About Authors 100

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Petroleum in View of its Classification, Assay and Analysis 1

CHAPTER I:

Introduction

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Petroleum in View of its Classification, Assay and Analysis 2

Chapter I: Introduction

(I-1) Petroleum and petroleum product

(Definition, origin and Composition)

Petroleum (also called crude oil) is a naturally mixture of hydrocarbons,

generally in the liquid state, that may also include compounds of sulfur,

nitrogen, oxygen, and metals and other elements [1-3]. Inorganic sediment

and water may also be present. A petroleum product is any product that is

manufactured during petroleum refining. Consequently, it is not surprising

that petroleum can vary in composition properties and produce wide

variations in refining behavior as well as product properties.

Petroleum means literally rock oil and refers to hydrocarbons that occur

widely in the sedimentary rocks in the form of gases, liquids, semisolids, or

solids. From a chemical standpoint, petroleum is an extremely complex

mixture of hydrocarbon compounds, usually with minor amounts of

nitrogen-, oxygen-, and sulfur-containing compounds as well as trace

amounts of metal-containing compounds [4-9].

The fuels that are derived from petroleum supply more than half of

the world’s total supply of energy. Gasoline, kerosene, and diesel oil provide

fuel for automobiles, tractors, trucks, aircraft, and ships. Fuel oil and natural

gas are used to heat homes and commercial buildings, as well as to generate

electricity. Petroleum products are the basic materials used for the

manufacture of synthetic fibers for clothing and in plastics, paints, fertilizers,

insecticides, soaps, and synthetic rubber. The uses of petroleum as a source

of raw material in manufacturing are central to the functioning of modern

industry [10].

Petroleum being processed in refineries is becoming increasingly heavier

(higher amounts of residuum) and higher sulfur content) [2, 3]. Market

demand (market pull) dictates that residua must be upgraded to higher-value

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Petroleum in View of its Classification, Assay and Analysis 3

products [11]. In short, the value of petroleum depends on its quality for

refining and whether or not a product slate can be obtained to fit market

demand. Thus process units in a refinery require analytical test methods that

can adequately evaluate feed stocks and monitor product quality. In addition,

the high sulfur content of petroleum and regulations limiting the maximum

sulfur content of fuels makes sulfur removal a priority in refinery processing.

Here again, analytical methodology is key to the successful determination of

the sulfur compound types present and their subsequent removal. Upgrading

residua involves processing (usually conversion) into a more salable, higher-

valued product. Improved characterization methods are necessary for process

design, crude oil evaluation, and operational control. Definition of the

boiling range and the hydrocarbon type distribution in heavy distillates and

in residua is increasingly important. Feedstock analysis to provide a

quantitative boiling range distribution (that accounts for noneluting

components) as well as the distribution of hydrocarbon types in gas oil and

higher-boiling materials is important in evaluating feedstocks for further

processing.

In the crude state petroleum has minimal value, but when refined it

provides high-value liquid fuels, solvents, lubricants, and many other

products [12]. The fuels derived from petroleum contribute approximately

one-third to one-half of the total world energy supply and are used not only

for transportation fuels (i.e., gasoline, diesel fuel, and aviation fuel, among

others) but also to heat buildings. Petroleum products have a wide variety of

uses that vary from gaseous and liquid fuels to near-solid machinery

lubricants. In addition, the residue of many refinery processes, asphalt a

once-maligned by-product is now a premium value product for highway

surfaces, roofing materials, and miscellaneous waterproofing uses.

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Petroleum in View of its Classification, Assay and Analysis 4

Composition

In all of these attempts at a definition or classification of petroleum, it must

be remembered that petroleum exhibits wide variations in composition and

properties, and these variations not only occur in petroleum from different

fields but may also be manifested in petroleum taken from different

production depths in the same well. The mixture of hydrocarbons is highly

complex. Paraffinic, naphthenic, and aromatic structures can occur in the

same molecule, and the complexity increases with boiling range of the

petroleum fraction. In addition, petroleum varies in physical appearance from

a light-colored liquid to the more viscous heavy oil. The near-solid or solid

bitumen that occurs in tar sand deposits is different from petroleum and

heavy oil, as evidenced by the respective methods of recovery [13].

Elemental analysis of petroleum shows that the major constituents are carbon

and hydrogen with smaller amounts of sulfur (0.1–8% w/w), nitrogen (0.1–

1.0% w/w), and oxygen (0.1–3% w/w), and trace elements such as

vanadium, nickel, iron, and copper present at the part per million (ppm)

level. Of the non-hydrocarbon heteroelements) elements, sulfur is the most

abundant and often considered the most important by refiners. However,

nitrogen and the trace metals also have deleterious effects on refinery

catalysts and should not be discounted because of relative abundance.

Process units with, for example, a capacity of 50,000 bbl/day that are in

operation continuously can soon reflect the presence of the trace elements.

The effect of oxygen, which also has an effect on refining catalysts, has

received somewhat less study than the other heteroelements but remains

equally important in refining. Petroleum suitability for refining (to produce a

slate of predetermined products) is determined by application of a series of

analytical methods [14] that provide information that is sufficient to assess

the potential quality of the petroleum as a feedstock and also to indicate

whether any difficulties might arise in handling, refining, or transportation.

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Petroleum in View of its Classification, Assay and Analysis 5

Such information may be obtained either by (1) a preliminary assay of

petroleum or (2) a full assay of petroleum that involves presentation of a true

boiling point curve and the analysis of fractions throughout the full range of

petroleum.

Due to its origin, crude oil is a complex mixture containing thousands

of different hydrocarbons (10,11) that can be separated into a variety of

different generic fractions by distillation .And the terminology of these

fractions has been bound by utility and often bears little relationship to

composition. The major components of petroleum are hydrocarbons,

compounds of hydrogen and carbon that display great variation in their

molecular structure. The simplest hydrocarbons are a large group of chain-

shaped molecules known as the paraffins. This broad series extends from

methane, which forms natural gas, through liquids that are refined into fuels,

to crystalline waxes. A series of ring-shaped hydrocarbons, known as the

naphthens, range from volatile liquids such as naphtha to high molecular

weight substances isolated as the asphalten fraction. Another group of ring-

shaped hydrocarbons is known as the aromatics; the chief compound in this

series is benzene, a popular raw material for making petrochemicals [10].

It is commonly accepted to group the different compounds present in

crude oils in different families according to their chemical structure

(paraffins, naphthenes and aromatics, PNA) or polarity (saturates, aromatics,

resins and asphaltens, SARA) [15].

The saturate fraction consists of a viscous whitish translucent liquid,

mainly composed of paraffins and diamondoids. This fraction is easily

distinguishable and separated from the rest of the oil due to the absence of π

bonds between saturate hydrocarbons molecules. The aromatic fraction is a

viscous reddish liquid composed of aromatic hydrocarbons with various

degrees of condensation, alkyl substitution, and heteroatom (i.e., sulfur,

oxygen, nitrogen) content forming a continuum regarding polarity, molecular

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Petroleum in View of its Classification, Assay and Analysis 6

weight, and other properties. The resin fraction is a dark brown colored, thick

viscous to semisolid liquid with a higher degree of condensation and

heteroatom content than the aromatics.

The asphalten fraction looks like a dark brown to black, amorphous

solid [16]. The nature of asphaltenes in petroleum has been extensively

studied [17-21], and there is a general consensus that asphalten precipitation

is closely related to the chemical structure of the most polar constituents of

crude oil (asphaltens and resins ) and to the compositions of its non-polar

constituents.

Although resins play a very important role in the colloidal stability of

petroleum, this fraction has not been studied as extensively as asphalten

fraction [22]. Petroleum resins, as well as the other three major hydrocarbon

fractions in petroleum (asphaltens, aromatics, and saturates) are defined

according to the method used for the separation, which also determine the

amount and nature of the material obtained (13,18,19). Resins are defined as the

fraction of deasphalted oil that is strongly adsorbed on surface-active

materials such as fullers earth, alumina, silica [23, 24] or modified silica (21,22),and that can only be desorbed with polar solvents such as pyridine,

chloroform, or a mixture of toluene and methanol [22].

Resins and asphaltenes have similar characterization; both are

aromatic hetero-compounds with aliphatic substitutions, but resins having

longer alkyl chains and smaller aromatic rings [17]. Resins provide a

transition between the most polar (asphaltens) and relatively non-polar

(aliphatic and aromatic, i.e. maltenes) fraction in petroleum.

Nonhydrocarbon constituents of petroleum include organic derivatives

of nitrogen, oxygen, sulfur, and the metals nickel and vanadium. Most of

these impurities are removed during refining.

The molecular boundaries of petroleum cover a wide range of boiling

points and carbon numbers of hydrocarbon compounds and other compounds

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Petroleum in View of its Classification, Assay and Analysis 7

containing nitrogen, oxygen, and sulfur, as well as metallic (porphyrinic)

constituents. In fact, petroleum is so diverse that materials from different

sources exhibit different boundary limits, and for this reason alone it is not

surprising that petroleum has been difficult to map in a precise manner.

Since there is a wide variation in the properties of crude petroleum

Table 1, the proportions in which the different constituents occur vary with

origin. Thus, some crude oils have higher proportions of the lower boiling

components and others (such as heavy oil and bitumen) have higher

proportions of higher boiling components (asphaltic components and

residuum).

Petroleum Specific Gravity API Gravity Residuum >1000 °F (% v/v)

U.S. Domestic

California 0.858 33.4 23.0

Oklahoma 0.816 41.9 20.0

Pennsylvania 0.800 45.4 2.0

Texas 0.827 39.6 15.0

Texas 0.864 32.3 27.9

Other Countries

Bahrain 0.861 32.8 26.4

Iran 0.836 37.8 20.8

Iraq 0.844 36.2 23.8

Kuwait 0.860 33.0 31.9

Saudi Arabia 0.840 37.0 27.5

Venezuela 0.950 17.4 33.6

Table 1. Typical variation in the properties of petroleum.

(I-2) Recovery and Refining of Petroleum

Geologic techniques can determine only the existence of rock

formations that are favorable for oil deposits, not whether oil is actually

there. Drilling is the only sure way to ascertain the presence of oil. With

modern rotary equipment, wells can be drilled to depths of more than 30,000

ft (9000 m). Once oil is found, it may be recovered (brought to the surface)

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Petroleum in View of its Classification, Assay and Analysis 8

by the pressure created by natural gas or water within the reservoir. Crude oil

can also be brought to the surface by injecting water or steam into the

reservoir to raise the pressure artificially, or by injecting such substances as

carbon dioxide, polymers, and solvents to reduce crude oil viscosity.

Thermal recovery methods are frequently used to enhance the production of

heavy crude oils, whose extraction is impeded by viscous resistance to flow

at reservoir temperatures [10].

The basic refinery process is distillation, which separates the crude oil

into fractions of differing volatility. After the distillation, other physical

methods are employed to separate the mixtures, including absorption,

adsorption, solvent extraction, and crystallization. After physical separation

into such constituents as light and heavy naphtha, kerosene, and light and

heavy gas oils, selected petroleum fractions may be subjected to conversion

processes, such as thermal cracking (i.e., coking and catalytic cracking) [10].

All petroleum samples, from crude oil to refined products, contain varying

amounts of compounds containing hetero-atoms. Of these, sulfur and

nitrogen are the most important. Sulfur can be present in high concentrations.

Depending on the origin of a crude oil, the total concentration of sulphur

may vary between less than 0.05 and 14% (m/m) [25]. The combustion of

petroleum products containing sulfur compounds leads to the formation of

SO2, which is a major source of air pollution and acid rain. For these reasons,

accurate determination of the concentrations and identities of the sulphur-

containing species in petroleum products is highly desirable.

In the last 10 years, the efforts to reduce the sulfur content of

petroleum products have greatly increased. Sulfur can be removed by

hydrogenation, either as an explicit aim in so-called hydrotreaters or as a

welcome bonus in hydrocrackers .The latter process combines a conversion

of residue to lighter products (mainly middle distillates, such as kerosene and

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Petroleum in View of its Classification, Assay and Analysis 9

diesel) with the effective removal of sulfur. The oil industry has a need to

determine sulfur content sand distributions both at high (before treatment)

and at low (after treatment) concentrations. In order to study and improve

sulfur-removal processes, different classes of compounds or individual

species must be studied. This calls for speciation, separation and selective

detection.

Nitrogen is naturally present in crudes, but at very much lower

concentrations (rarely exceeding a few thousand parts per million (ppm))

than sulfur. Therefore, nitrogen compounds are usually not considered to be

a major problem. However, there are situations in which either the total

nitrogen concentration or the distribution of nitrogen-containing compounds

as a function of (for example) the boiling point needs to be known.

Especially in the latter case extremely sensitive element-specific detection

will be required.

One process for which both sulfur and nitrogen distributions are

relevant is hydrocracking. Both organic sulfur and organic nitrogen species

can poison the catalyst used in the second stage of a hydrocracker. The

amounts of these species must therefore be greatly reduced during the first

stage. Reforming changes the structure of straight-chain paraffin molecules

into branched-chain iso-paraffins and ring-shaped aromatics. The process is

widely used to raise the octane number of gasoline obtained by distillation of

paraffinic crude oils [10].

I.3. Classification of Petroleum

I.3.1. Classification as a hydrocarbon resource

Petroleum is referred to generically as a fossil energy resource and is

further classified as a hydrocarbon resource, coal and oil shale kerogen have

also been included in this classification. However, the inclusion of coal and

oil shale under the broad classification of hydrocarbon resources has required

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Petroleum in View of its Classification, Assay and Analysis 10

(incorrectly) that the term hydrocarbon be expanded to include the

macromolecular non-hydrocarbon hetero-atomic species that constitute coal

and oil shale kerogen. Use of the term organic sediments would be more

correct (Fig. 1).

The inclusion of coal and oil shale kerogen in the category

hydrocarbon resources is due to the fact that these two natural resources

(coal and oil shale kerogen) will produce hydrocarbons on high temperature

processing. Therefore, if coal and oil shale kerogen are to be included in the

term hydrocarbon resources, it is more appropriate that they be classed as

hydrocarbon-producing resources under the general classification of organic

sediment. Thus, fossil energy resources divide into two classes: (1) naturally

occurring hydrocarbons (petroleum, natural gas, and natural waxes), and (2)

hydrocarbon sources (oil shale and coal) which may be made to generate

hydrocarbons by the application of conversion processes. Both classes may

aptly be described as organic sediments.

In summary, the classification of petroleum and natural gas as

naturally occurring mixtures of hydrocarbons occurs by virtue of the fact that

they can be separated into their original hydrocarbon constituents that have

not been altered by any applied process. The hydrocarbon constituents,

separated from petroleum and natural gas, are the hydrocarbon constituents

that existed in the reservoir. Naturally occurring hydrocarbons are major

contributors to the composition of petroleum and natural gas. Coal and

kerogen do not enjoy this means of separation and methods of thermal

decomposition must be applied before hydrocarbons are produced. These

hydrocarbon products, generated by the thermal process, are not naturally

occurring hydrocarbons [10].

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Petroleum in View of its Classification, Assay and Analysis 11

Fig. 1 Subdivision of earth organic sediments.

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Petroleum in View of its Classification, Assay and Analysis 12

I.3.2. Classification by chemical composition

Composition refers to the specific mixture of chemical compounds that

constitute petroleum. The composition of these materials is related to the

nature and mix of the organic material that generated the hydrocarbons.

Composition is also subject to the influence of natural processes such as

migration (movement of oil from source rock to reservoir rock),

biodegradation (alteration by the action of microbes), and water washing

(effect of contact with water flowing in the subsurface) upon that

composition. Thus, petroleum is the result of the metamorphosis of natural

products as a result of chemical and physical changes imparted by the

prevailing conditions at a particular locale.

The composition of petroleum obtained from the well is variable and

depends not only on the original composition of the oil in situ but also on the

manner of production and the stage reached in the life of the well or

reservoir. In general terms, petroleum (conventional crude oil) ranges from a

brownish green to black liquid having a specific gravity (at 60 oF, 15.6 oC)

that varies from about 0.75 to 1.00 (57o to 10o API), with the specific gravity

of most crude oils falling in the range 0.80 to 0.95 (45o to 17o API). The

boiling range of petroleum varies from about 20oC (68 oF) to above 350 oC

(660 oF), above which active decomposition ensues when distillation is

attempted. Petroleum can contain from 0 % to 35 % or more of gasoline, as

well as varying proportions of kerosene hydrocarbons and higher boiling

constituents up to the viscous and nonvolatile compounds present in

lubricant oil and in asphalt.

Thus, petroleum varies in composition from one oil field to another,

from one well to another in the same field, and even from one level to

another in the same well. This variation can be in both molecular weight and

the types of molecules present in petroleum. Petroleum may well be

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Petroleum in View of its Classification, Assay and Analysis 13

described as a mixture of organic molecules drawn from a wide distribution

of molecular types that lie within a wide distribution of molecular weight.

Petroleum is a naturally occurring hydrocarbon insofar as it contains

compounds that are composed of carbon and hydrogen only [6, 8] which do

not contain any heteroatoms (nitrogen, oxygen, and sulfur as well as

compounds containing metallic constituents, particularly vanadium, nickel,

iron, and copper). The hydrocarbons found in petroleum are classified into

the following types:

1. Paraffins, i.e., saturated hydrocarbons with straight or branched

chains, but without any ring structure

2. Cycloparaffins (naphthenes), i.e., saturated hydrocarbons

containing one or more rings, each of which may have one or more

paraffin side-chains (more correctly known as (alicyclic

hydrocarbons).

3. Aromatics, i.e., hydrocarbons containing one or more aromatic

nuclei such as benzene, naphthalene, and phenanthrene ring systems

that may be linked up with (substituted) naphthalene rings or paraffin

side-chains.

On this basis, petroleum may have some value in the crude state but,

when refined, provides fuel gas, petrochemical gas (methane, ethane,

propane, and butane), transportation fuel (gasoline, diesel fuel, aviation fuel)

solvents, lubricants, asphalt, and many other products. In addition to the

hydrocarbon constituents, petroleum does contain heteroatomic

(nonhydrocarbon) species but they are in minority amounts.

A widely used classification of petroleum distinguishes between crude

oils either on a paraffin base or on asphalt base .The presence of paraffin wax

is usually reflected in the paraffin nature of the constituent fractions, and a

high asphaltic content corresponds with the so-called naphthene properties of

the fractions. As a result, the misconception that paraffin-base crude oils

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Petroleum in View of its Classification, Assay and Analysis 14

consist mainly of paraffins and asphalt-base crude oils mainly of cyclic (or

naphthene) hydrocarbons has arisen. In addition to paraffin- and asphalt-base

oils, a mixed base had to be introduced for those oils that leave a mixture of

bitumen and paraffin wax as a residue by nondestructive distillation.

In practice, a distinction is often made between light and heavy crude oils

(indicating the proportion of low-boiling material present), which, in

combination with the preceding distinction (paraffin, asphaltic, and so on),

doubles the number of possible classes.

Crude should be called asphaltic if the distillation residue contained less than

2% wax. A division according to the chemical composition of the 250 oC to

300 oC (480 oC to 570 oF) fraction has also been used Table 2.

Composition of 250 °C-300 °C (480 °F- 570 °F)

Paraffin Naphthene Aromatic Wax Asphalt

(%) (%) (%) (%) (%) Crude Oil Classification

>46, <61 >22, <32 >12, <25 <10 <6 Paraffin

>42, <45 >38, <39 >16, <20 <6 <6 Paraffin-naphthene

>15, <26 >61, <76 >8, <13 0 <6 Naphthene

>27, <35 >36, <47 >26, <33 <1 <10 Paraffin-naphthene-aromatic

<8 >57, <78 >20, <25 <0.5 <20 Aromatic

Table 2. Classification according to chemical composition.

I.3.3. Classification by density

Density (specific gravity) has been, since the early years of the

industry, the principal, and often the only specification of crude oil products

and was taken as an index of the proportion of gasoline and, particularly,

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Petroleum in View of its Classification, Assay and Analysis 15

kerosene present. As long as only one kind of petroleum was in use, the

relations were approximately true, but as crude oils having other properties

were discovered and came into use, the significance of density measurements

disappeared. Nevertheless, crude oils of particular types are still rated by

gravity, as are gasoline and naphtha within certain limits of other properties.

The use of density values has been advocated for quantitative

applications using a scheme based on the American Petroleum Institute

(API) gravity of the 250 oC to 275 oF (480 oF to 525 oF, 1760 mm) and the

275 oC to 300 oC (525 oF to 570 oF, 40 mm) distillation fractions Table 3.

Indeed, investigation of crude oils from worldwide sources showed that 85 %

fell into one of the three classes: paraffin, intermediate or naphthene base. It

has also been proposed to classify heavy oils according to characterization

gravity.

I.3.4. Classification by API gravity

Table 3. Classification according to API gravity

Fraction 250°C-300°C (480°F-570°F) 250°C-300°C (480°F-570°F) API Gravity Type API Gravity Type Classification

>40.0 Parrafin >30.0 Paraffin Paraffin

>40.0 Parrafin 20.1-29.9 Intermediate Paraffin-intermedite

33.1-39.9 Intermediate >30.0 Paraffin Intermediate-paraffin

33.1-39.9 Intermediate 20.1-29.9 Intermediate Intermediate

33.1-39.9 Intermediate <20.0 Naphthene Intermediate-naphthene

<33.0 Naphthene 20.1-29.9 Intermediate Naphthene-intermediate

<33.0 Naphthene <20.0 Naphthene Naphthene

>40.0 Parrafin <20.0 Naphthene Paraffin-naphthene

33.0 Naphthene >30.0 Paraffin Naphthene-paraffin

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Petroleum in View of its Classification, Assay and Analysis 16

Conventional crude oil and heavy oil have also been defined very

generally in terms of physical properties. Classification of petroleum

according to API gravity was given in Table 3. For example, heavy oils were

considered those petroleum-type materials that had gravity somewhat less

than 20o API, with the heavy oils falling into the API gravity range of 10o to

15o (e.g., Cold Lake crude oil =12o API) and bitumen falling into the 5o to

10o API range (e.g., Athabasca bitumen = 8o API). Residua vary depending

on the temperature at which distillation is terminated. Atmospheric residual

are usually in the 10o to 15o API range of, and vacuum residua are in the

range of 2o to 8o API [26, 27].

I.3.5. Classification by viscosity

At the same time, and in concert with the use of API gravity, the line

of demarcation between petroleum and heavy oil vis-à-vis tar sand bitumen

has been drawn at 10,000 centipoises.

Briefly, materials having viscosity less than 10,000 centipoises (cp) are

conventional petroleum and heavy oil, whereas tar sand bitumen has a

viscosity greater than 10,000 cp. Use of such a scale requires a fine line of

demarcation between the various crude oils, heavy oils, and bitumen to the

point where it would be confusing to differentiate between a material having

a viscosity of 9950 cp and one having a viscosity of 10,050 cp. Further, the

inaccuracies (i.e., the limits of experimental error) of the method of

measuring viscosity also increase the potential for misclassification.

The viscosity of tar sand bitumen is usually in excess of 50,000 cp and

higher than 100,000 cp. But even using a higher line of demarcation does not

circumvent the use of one physical property and the difference between a

material having viscosity equal to 49,900 and 50,100 cp (or 99,900 and

100,100 cp). Cleary, the use of one physical parameter be it API gravity or

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Petroleum in View of its Classification, Assay and Analysis 17

viscosity is inadequate to the task of classifying conventional petroleum,

heavy oil, and tar sand bitumen.

I.3.6. Classification by carbon distribution

A method for the classification of crude oils can only be efficient, first,

if it indicates the distribution of components according to volatility, and

second, if it indicates the characteristic properties of the various distillate

fractions. The distribution according to volatility has been considered the

main property of petroleum, and any fractionating column with a sufficient

number of theoretical plates may be used for recording a curve in which the

boiling point of each fraction is plotted against the percentage by weight.

However, for the characterization of the various fractions of petroleum, the

use of the n.d.M method ( n = refractive index, d = density, M = molecular

weight; is suggested. This method enables determination of the carbon

distribution and thus indicates the percentage of carbon in aromatic structure

(%CA), the percentage of carbon in naphthene structure (%CN), and the

percentage of carbon in paraffin structure (%CP).

A high value of %CA at 500oC (930oF) boiling point usually indicates a high

content of asphaltenes in the residue, whereas a high value of %CnP at 500oC

(930oF) boiling point usually indicates a waxy residue.

I.3.7. Classification by pour point

Tar sand bitumen is a naturally occurring material that is immobile in

the deposit and cannot be recovered by the application of enhanced oil

recovery technologies, including steam –based technologies. On the other

hand, heavy oil is mobile in the reservoir and can be recovered by the

application of enhanced oil recovery technologies, including steam -based

technologies.

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Petroleum in View of its Classification, Assay and Analysis 18

Since the most significant property of tars and bitumen is its immobility

under the conditions of temperatures and pressure in the deposit, the inter

related properties of API gravity (ASTM D-287) and viscosity (ASTM D-

445) may present an indication of the mobility of oil or immobility of

bitumen, but in reality these properties only offer subjective descriptions of

the oil in the reservoir. The most pertinent and objective representation of

this oil or bitumen mobility is the pour point (ASTM D-97).

By definition, the pour point is the lowest temperature at which oil will

move, pour, or flow when it is chilled without disturbance under definite

conditions (ASTM D-97). In fact, the pour point of oil when used in

conjunction with the reservoir temperature gives a better indication of the

condition of the oil in the reservoir than the viscosity. Thus, the pour point

and reservoir temperature present a more accurate assessment of the

condition of the oil in the reservoir, being an indicator of the mobility of the

oil in the reservoir. Indeed, when used in conjunction with reservoir

temperature, the pour point gives an indication of the liquidity of the heavy

oil or bitumen and, therefore, the ability of the heavy oil or bitumen to flow

under reservoir conditions. In summary, the pour point is an important

consideration because, for efficient production, additional energy must be

supplied to the reservoir by a thermal process to increase the reservoir

temperature beyond the pour point.

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Petroleum in View of its Classification, Assay and Analysis 19

I.4. Physical Properties of Petroleum Crude Oil

Petroleum exhibits a wide range of physical properties and several

relationships can be made between various physical properties [28]. Whereas

properties such as viscosity, density, boiling point, and color of petroleum

may vary widely, the ultimate or elemental analysis varies, as already noted,

over a narrow range for a large number of petroleum samples. The carbon

content is relatively constant, while the hydrogen and heteroatom contents

are responsible for the major differences between petroleum samples.

Coupled with the changes brought about to the feedstock constituents by

refinery operations, it is not surprising that petroleum characterization is a

monumental task.

Petroleum refinery processes can be conveniently divided into three

different types

1. Separation: division of the feedstock into various streams

(or fractions) depending on the nature of the crude material

2. Conversion: that is, the production of saleable materials

from the feedstock by skeletal alteration, or even by alteration of the

chemical type of the feedstock constituents

3. Finishing: purification of the various product streams by a

variety of processes that remove impurities from the product.

In some case, a fourth category can be added and includes processes

such as the reforming (molecular rearrangement) processes. For the purposes

of this text, reforming processes are included in the finishing processes

because that is precisely what they are: processes designed to finish various

refinery streams and render them ready for sale as defined products.

The separation and finishing processes may involve distillation or treatment

with a wash solution. The conversion processes are usually regarded as those

processes that change the number of carbon atoms per molecule (thermal

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Petroleum in View of its Classification, Assay and Analysis 20

decomposition), alter the molecular hydrogen–carbon ratio (aromatization,

hydrogenation), or even change the molecular structure of the material

without affecting the number of carbon atoms per molecule (isomerization).

Evaluation of petroleum for use as a feedstock usually involves an

examination of one or more of the physical properties of the material. By this

means, a set of basic characteristics can be obtained that can be correlated

with utility. To satisfy specific needs with regard to the type of petroleum to

be processed, as well as to the nature of the product, various standards

organizations, such as the American Society for Testing and Materials in

North America and the Institute of Petroleum in Britain, have devoted

considerable time and effort to the correlation and standardization of

methods for the inspection and evaluation of petroleum and petroleum

products.

Physical properties of the almost limitless variety of crude oils are

generally correlated with aspects of chemical composition.

I.4.1. API gravity

This is the most common measurement performed on petroleum

products; density is expressed in terms of API gravity. This measurement

determines the weight of a crude oil per unit volume at 60°F, normally

measured by the Hydrometer method ASTM D-287.

I.4.2. Aniline point

This point is defined as the lowest temperature at which aniline is

soluble in a specified amount of sample. This measure is used to determine

the solvency of the hydrocarbons. Typically paraffinic hydrocarbons have

higher aniline points than aromatic hydrocarbons. This method is usually

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Petroleum in View of its Classification, Assay and Analysis 21

performed under the guidelines of ASTM D-611. Aniline point can be used

to determine the quality of ignition in diesel cuts.

I.4.3. Cloud point

This is defined as the temperature at which a haze appears in a sample

which is attributed to the formation of wax crystals. Cloud point data is used

to determine the tendency of small orifices to plug in cold operating

temperatures, normally measured on middle distillate cuts. This property can

be measured manually by utilizing ASTM D-2500, since many laboratories

utilize similar equipment to perform pour points. With the development of

new analytical equipment many laboratories are now utilizing phase

technology and are performing ASTM D-5773 which is less labor intensive

and more robust.

I.4.4. Freeze point

The temperature at which crystal start to form in hydrocarbon liquids

and then disappear when the liquid is heated is the freeze point. Normally

performed by ASTM D-2386, this method like cloud point is done by ASTM

D-5972 by phase technology.

I.4.5. Metals content

The metals concentration in crude can range from a few to several

thousand ppm. Low values of certain elements such as nickel and vanadium

can severely affect catalyst activity. In the past metals were determined by

Atomic Absorption, but now most metals are determined by Inductively

Coupled Plasma Emission Spectroscopy ICPCES. X-ray fluorescence can be

a viable technique depending on the concentration.

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I.4.6. Mercaptan sulfur

Mercaptan Sulfur species are undesirable in crude oils, and in some

cases are toxic. These species are normally attributed to sour crudes.

Analysis is normally based on UOP-163 or ASTM D-3227, a potentiometric

titration method. A hydrocarbon sample is added to a solution of isopropyl

alcohol containing a small amount of ammonium hydroxide. The solution is

then titrated with a solution of silver nitrate.

I.4.7. Micro carbon residue

The carbon residue of a petroleum crude oil is proportional to the

asphalt content, normally measured by Conradson Carbon ASTM D-189. In

most cases the lower the carbon residue, the higher the value that can be

placed on the crude oil.

I.4.8. Nitrogen

Nitrogen species in crude oils can cause catalyst poisoning. ASTM D-

3228 or ASTM D-4629 normally determines nitrogen content. Either a

syringe inlet or boat inlet analyzes distillate cuts by Oxidative Combustion

and Chemiluminescence detection. Whole crude, atmospheric and vacuum

residues are analyzed by Kjeldahl methodology, a labor intensive method

involving digestion/distillation and finishing up with a titration.

I.4.9. Pour point

The lowest temperature at which a hydrocarbon fraction is observed to

pour when cooled under prescribed conditions. The pour point of a sample is

determined to be 3 degrees Celsius above the point at which a sample can be

horizontally held and no movement occurs for five seconds. The most

frequently utilized method for this test is ASTM D-97, which can be used for

all assay fractions/ blends. For whole crudes that have pour points greater

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Petroleum in View of its Classification, Assay and Analysis 23

than -36°C, a new method has been developed (ASTM D-5853). Also for

fractions that contain wax, a new method utilizing phases technology ASTM

D-5949. Normally low pour points are due to low paraffin content and high

aromatics.

I.4.10. Refractive index (n)

Refractive index is a ratio technique that takes the velocity of light in

air at a specific wavelength and compares that to the velocity in the sample

tested. Normally this is performed under the guidelines of ASTM D-1218.

This test method can be performed at various temperatures. The refractive

index can be used to estimate the distribution of PNA molecules in oil

fractions.

I.4.11. Reid Vapor Pressure (RVP)

RVP is measurement of the volatility of a liquid hydrocarbon.

Normally this is performed by ASTM D-323. This measurement is normally

used to predict gasoline performance, normally expressed in pounds per

square inch (psi). This is normally an inspection that is performed on Whole

Crudes having relatively high API’s.

I.4.12. Salt content

The salt content is measured by ASTM D-3230 to determine the

corrosiveness of a Crude oil. It is this conductivity method that measures a

sample of crude oil dissolved in water and compares that to reference

solutions of salt.

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I.4.13. Smoke point

Performed by ASTM D-1322, this test determines the maximum flame

height in a lamp without smoke forming. Normally high values represent

clean burning fuels. In normally practice this test is performed on jet fuels

and kerosene cuts.

I.4.14. Sulfur content

The sulfur content of crude oils is normally in the range of 0.1-5.0 wt

%. Sulfur is normally measured by an x-ray technique such as ASTM D-

4294 or D-5291. These methods have large dynamic ranges and allow

analysis to be completed in about 3-5 min. Samples having sulfur contents

greater than 5.0 % are measured by methods such as ASTM D-1552, a

combustion technique. For extremely low levels an ultraviolet fluorescence

(UV) technique is employed (ASTM D-5453). Again most of these methods

are very robust, but can be influenced by not having a representative sample.

Crudes are determined to be sweet or sour based on the amount of dissolved

hydrogen sulfide.

I.4.15. Total Acid Number (TAN)

The industry standard for this test is based on ASTM D-664. Normally

expressed as Neutralization Number, this test predicts the acidity of an

oil/distillate fraction. The sample normally dissolved in Toluene/Isopropyl

alcohol / Water is titrated with potassium hydroxide and the results are

expressed as mg KOH per gram of sample. Crude Oils having high acid

numbers are purchased cautiously due to possible corrosion problems in the

refineries. Crudes typically have TAN values form 0.05-6.0 mg KOH/gm of

sample. While whole crudes are outside the scope of this titration method, it

is the only recognized method in the industry.

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I.4.16. Viscosity

Viscosity is a measurement of a fluid resistance to flow. Most

measurements use the force of gravity to produce the flow through a small

capillary tube called a viscometer; thus the measurement is known as

kinematic viscosity having a unit of centistoke (cSt). The viscosity of a fluid

is always reported with a temperature, since viscosity will vary inversely

with temperature. Most viscosity measurements follow the guidelines of

ASTM D-445. Normally in an inspection grid the viscosity will be measured

at three different temperatures and then plotted on semi-log graph paper. If

all measurements are performed properly a straight line will result.

I.4.17. Water & Sediment

Sediment and water values in crude oils are critical parameters as to

whether problems will occur in the processing in the refinery. In many cases,

desalting equipment may be required in order to handle a given crude slate.

I.4.18. Molecular weight

The most widely used method of determining the molecular weight

of an unknown petroleum mixture is by the cryoscopy method, which is

based on freezing point depression. The freezing point of a solution is a

measure of the solution's concentration. As the concentration of the solute

increases, the freezing point of the solution will be lower.

The relation between freezing point depression and concentration is

linear. For organic hydrocarbons, benzene is usually used as the solvent.

Special care should be taken when working with benzene [29]. Calibration

curves can be prepared by measuring the freezing points of different solute

concentrations with a known solute and a known solvent. A cryoscope can

measure the freezing point depression with an accuracy of about 0.001 °C

The relation to obtain molecular weight of a sample is [29].

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where Kf is molal freezing point depression constant of the solvent

and is about 5.12 C/mole T is the freezing point depression and the reading

from the cryoscope, m1 is the mass of solute and m2 is the mass of solvent

both in grams. It generally consists of refrigerator, thermometer and the

apparatus to hold the sample.

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I.5. Oilfield water

The oil field waters generally have characteristic physicochemical

properties, including pH value, density, specific gravity, electrical

conductivity or resistivity, total dissolved solid, salinity and hardness.

Physicochemical properties

I.5.1. pH value

The pH value of water is the logarithm of the reciprocal of the

hydrogen-ion activity. The determination of pH of water is an indication of

its acidic or alkaline tendency; the pH measurement is an important factor in

determining the corrosive action of water and assessing water treatment

practices for industrial processes. It is also used to assess the extent of

pollution in precipitation [30].

Most ground waters have pH values ranging from about 5.5 to slightly

over 8, natural water with pH values lower than about 4.5 may contain free

mineral acids added by volcanic gases or oxidation of sulphides, or may

contain salts which on hydrolysis tend to give an acid reaction, ferric salts

and aluminum salts are likely to make water acidic. Some water contain

organic matter may have rather low pH values owing to the presence of

organic acids [31. The Ph value can be determined with a pH-meter

according to the ASTM D-1293 and D-5128 [30], APHA 4500-H+ [32] and

API [33] methods.

I.5.2. Density and specific gravity

Specific gravity is a relative density, i.e. the ratio of the mass of a

given volume of liquid at 15 oC (or 60 oF) to the mass of an equal volume of

pure water at the same temperature [30].

Pure water weighs 1 gm/ml or 1000 kg/m3. Thus, a specific gravity

greater than 1.0 means that the water sample is more dense. Since petroleum-

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associated water contains dissolved matter (ions, compounds, gases), they

are always more dense than pure water and therefore have a specific greater

than 1.0 [34].

The magnitude of the specific gravity is a direct indicator of the total

amount of solids dissolved in the water. Therefore, comparison of the

specific gravities of several waters give a rapid estimate of the relative

amounts of solids dissolved in the waters [35]. The density and specific

gravity can be determined by the ASTM D-1429 [30], APHA 2710-F [32]

and API [33] methods.

I.5.3. Electrical conductivity or resistivity

Electrical conductivity is the reciprocal of the resistance in ohms

measured between opposite faces of a centimeter cube of an aqueous solution

at a specific temperature [30].

Conductivity is a numerical expression of the ability of an aqueous solution

to carry an electric current; this ability depends on the presence of ions, their

total concentration, mobility, valence and relative concentrations and on the

temperature of measurement [32].

The resistivity of petroleum-associated water is used in electric log

interpretations, and for such use the values must be adjusted to the formation

temperature. Electrical conductivity and resistivity is determined by the

ASTM D-1125 and D 4159 [30], APHA 2510 [32].

I.5.4. Total Dissolved Solids (TDS)

Total solid is the term applied to the material residue left in the vessel

after evaporation of a sample and its subsequent drying in an oven at defined

temperature. The dissolved solids determination is used to estimate the

accuracy of the resistivity determination. The specific gravity determination

and the evaporation method are used to double check the calculated total

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Petroleum in View of its Classification, Assay and Analysis 29

dissolved solids [35]. TDS are determined by ASTM D-1888 [30], APHA

2540 [32] methods.

I.5.5. Hardness

Total hardness is defined as the sum of the calcium and magnesium

concentrations, both expressed as calcium carbonate, in milligrams per liter.

Hardness is caused by any polyvalent cations but those other than Ca and Mg

are seldom present in more than trace amounts [30] When hardness is

numerically greater than the sum of carbonate and bicarbonate alkalinity, that

amount of hardness equivalent to the total alkalinity is called "bicarbonate

hardness", the amount of hardness in excess of this is called "non carbonate

hardness" [32]. Hardness salts in water are the primary cause of tube and

pipe scaling, which frequently causes failures and loss of process efficiency

due to clogging or loss of heat transfer, or both [30]. Hardness is determined

by methods of ASTM D-1126 [30] and APHA 2340 B [32].

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Petroleum in View of its Classification, Assay and Analysis 30

Chapter II:

Petroleum Assay and Technical

Fractions

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Petroleum in View of its Classification, Assay and Analysis 31

Chapter II: Petroleum Assay and Technical Fractions

An efficient assay is derived from a series of test data that give an

accurate description of petroleum quality and allow an indication of its

behavior during refining. The first step is, of course, to assure adequate

(correct) sampling by use of the prescribed protocols (ASTM D-4057).

Thus, analyses are performed to determine whether each batch of crude oil

received at the refinery is suitable for refining purposes. The tests are also

applied to determine if there has been any contamination during wellhead

recovery, storage, or transportation that may increase the processing

difficulty (cost). The information required is generally crude oil dependent or

specific to a particular refinery and is also a function of refinery operations

and desired product slate. To obtain the necessary information, two different

analytical schemes are commonly used and these are: (1) an inspection assay

and (2) a comprehensive assay.

Inspection assays usually involve determination of several key bulk

properties of petroleum (e.g., API gravity, sulfur content, pour point, and

distillation range) as a means of determining if major changes in

characteristics have occurred since the last comprehensive assay was

performed.

For example, a more detailed inspection assay might consist of the

following tests : API gravity (or density or relative density), sulfur content,

pour point, viscosity, salt content, water and sediment content, trace metals

(or organic halides). The results from these tests with the archived data from

a comprehensive assay provide an estimate of any changes that have

occurred in the crude oil that may be critical to refinery operations.

Inspection assays are routinely performed on all crude oils received at a

refinery.

On the other hand, the comprehensive (or full) assay is more complex (as

well as time consuming and costly) and is usually performed only when a

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Petroleum in View of its Classification, Assay and Analysis 32

new field comes on stream, or when the inspection assay indicates that

significant changes in the composition of the crude oil have occurred. Except

for these circumstances, a comprehensive assay of a particular crude oil

stream may not (unfortunately) be updated for several years. A full

petroleum assay may involve at least determinations of (1) carbon residue

yield, (2) density (specific gravity), (3) sulfur content, (4) distillation profile

(volatility), (5) metallic constituents, (6) viscosity, and (7) pour point, as well

as any tests designated necessary to understand the properties and behavior

of the crude oil under examination.

Using the data derived from the test assay, it is possible to assess

petroleum quality and to acquire a degree of predictability of performance

during refining. However, knowledge of the basic concepts of refining will

help the analyst understand the production and, to a large extent, the

anticipated properties of the product, which in turn is related to storage,

sampling, and handling the products.

II.1.Petroleum Constituents

II.1.1. Carbon Residue, Asphaltene Content

The carbon residues of petroleum and petroleum products serve as an

indication of the propensity of the sample to form carbonaceous deposits

(thermal coke) under the influence of heat.Tests for Conradson carbon

residue (ASTM D-189, IP 13), Ramsbottom carbon residue (ASTM D-524,

IP 14), the microcarbon carbon residue (ASTM D4530, IP 398), and

asphaltene content (ASTM D-893, ASTM D-2006, ASTM D-2007, ASTM

D-3279, ASTM D-4124, ASTM D-6560, IP 143) are sometimes included in

inspection data on petroleum. The data give an indication of the amount of

coke that will be formed during thermal processes as well as an indication of

the amount of high-boiling constituents in petroleum.

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The determination of the carbon residue of petroleum or a petroleum product

is applicable to relatively nonvolatile samples that decompose on distillation

at atmospheric pressure. Samples that contain ash-forming constituents will

have an erroneously high carbon residue, depending on the amount of ash

formed. All three methods are applicable to relatively nonvolatile petroleum

products that partially decompose on distillation at atmospheric pressure.

Crude oils having a low carbon residue may be distilled to a specified residue

with the carbon residue test of choice then applied to that residue. In the

Conradson carbon residue test (ASTM D-189, IP 13), a weighed quantity of

sample is placed in a crucible and subjected to destructive distillation for a

fixed period of severe heating. At the end of the specified heating period, the

test crucible containing the carbonaceous residue is cooled in a desiccator

and weighed and the residue is reported as a percentage (% w/w) of the

original sample (Conradson carbon residue).

In the Ramsbottom carbon residue test (ASTM Test Method D524, IP 14),

the sample is weighed into a glass bulb that has a capillary opening and

petroleum assay 35 is placed into a furnace (at 550°C, 1022°F). The volatile

matter is distilled from the bulb and the nonvolatile matter that remains in the

bulb decomposes to form thermal coke. After a specified heating period, the

bulb is removed from the bath, cooled in a desiccator, and weighed to report

the residue (Ramsbottom carbon residue) as a percentage (% w/w) of the

original sample. In the icrocarbon residue test (ASTM D4530, IP 398), a

weighed quantity of the sample placed in a glass vial is heated to 500°C

(932°F) under an inert (nitrogen) atmosphere in a controlled manner for a

specific time and the carbonaceous residue [carbon residue (micro)] is

reported as a percentage (% w/w) of the original sample. The data produced

by the microcarbon test (ASTM D4530, IP 398) are equivalent to those by

the Conradson carbon residue method (ASTM D- 189 IP 13). However, this

microcarbon test method offers better control of test conditions and requires

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a smaller sample. Up to 12 samples can be run simultaneously. This test

method is applicable to petroleum and to petroleum products that partially

decompose on distillation at atmospheric pressure and is applicable to a

variety of samples that generate a range of yields (0.01% w/w to 30% w/w)

of thermal coke. As noted, in any of the carbon residue tests, ash-forming

constituents (ASTM D-482) or nonvolatile additives present in the sample

will be included in the total carbon residue reported, leading to higher carbon

residue values and erroneous conclusions about the coke-forming propensity

of the sample.

The asphaltene fraction (ASTM D-893, ASTM D-2006, ASTM D-2007,

ASTM D-3279, ASTM D-4124, ASTM D-6560, IP 143) is the

highestmolecular- weight, most complex fraction in petroleum. The

asphaltene content gives an indication of the amount of coke that can be

expected during processing [3, 11]. In any of the methods for the

determination of the asphaltene content, the crude oil or product (such as

asphalt) is mixed with a large excess (usually >30 volumes hydrocarbon per

volume of sample) of low-boiling hydrocarbon such as n-pentane or n-

heptanes. For an extremely viscous sample, a solvent such as toluene may be

used before the addition of the low-boiling hydrocarbon but an additional

amount of the hydrocarbon (usually >30 volumes hydrocarbon per volume of

solvent) must be added to compensate for the presence of the solvent. After a

specified time, the insoluble material (the asphaltene fraction) is separated

(by filtration) and dried. The yield is reported as percentage (% w/w) of the

original sample. It must be recognized that, in any of these tests, different

hydrocarbons (such as n-pentane or n-heptane) will give different yields of

the asphaltene fraction and if the presence of the solvent is not compensated

for by use of additional hydrocarbon the yield will be erroneous. In addition,

if the 36 petroleum and petroleum products hydrocarbon is not present in

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large excess, the yields of the asphaltene fraction will vary and will be

erroneous.

The precipitation number is often equated to the asphaltene content, but there

are several issues that remain obvious in its rejection for this purpose. For

example, the method used to determine the precipitation number (ASTM D-

91) advocates the use of naphtha for use with black oil or lubricating oil and

the amount of insoluble material (as a % v/v of the sample) is the

precipitation number. In the test, 10ml of sample is mixed with 90ml of

ASTM precipitation naphtha (which may or may nor have a constant

chemical composition) in a graduated centrifuge cone and centrifuged for

10min at 600–700rpm. The volume of material on the bottom of the

centrifuge cone is noted until repeat centrifugation gives a value within

0.1ml (the precipitation number). Obviously, this can be substantially

different from the asphaltene content.

II.1.2. Density (Specific Gravity)

For clarification, it is necessary to understand the basic definitions that are

used: (1) density is the mass of liquid per unit volume at 15°C; (2) relative

density is the ratio of the mass of a given volume of liquid at 15°C to the

mass of an equal volume of pure water at the same temperature; (3) specific

gravity is the same as the relative density and the terms are used

interchangeably.

Density (ASTM D-1298, IP 160) is an important property of petroleum

products because petroleum and especially petroleum products are usually

bought and sold on that basis or, if on a volume basis, then converted to mass

basis via density measurements. This property is almost synonymously

termed as density, relative density, gravity, and specific gravity, all terms

related to each other. Usually a hydrometer, pycnometer, or more modern

digital density meter is used for the determination of density or specific

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gravity. In the most commonly used method (ASTM D-1298, IP 160), the

sample is brought to the prescribed temperature and transferred to a cylinder

at approximately the same temperature. The appropriate hydrometer is

lowered into the sample and allowed to settle, and, after temperature

equilibrium has been reached, the hydrometer scale is read and the

temperature of the sample is noted. Although there are many methods for the

determination of density because of the different nature of petroleum itself

and the different products, one test method (ASTM D-5002) is used for the

determination of the density or relative density of petroleum that can be

handled in a normal fashion as liquids at test temperatures between 15 and

35°C (59 and 95°F). This test method applies to petroleum products with

high vapor pressures petroleum assay 37 provided appropriate precautions

are taken to prevent vapor loss during transfer of the sample to the density

analyzer. In the method, approximately 0.7 ml of crude oil sample is

introduced into an oscillating sample tube and the change in oscillating

frequency caused by the change in mass of the tube is used in conjunction

with calibration data to determine the density of the sample. Another test

determines density and specific gravity by means of a digital densimeter

(ASTM D-4052, IP 365). In the test, a small volume (approximately 0.7 ml)

of liquid sample is introduced into an oscillating sample tube and the change

in oscillating frequency caused by the change in the mass of the tube is used

in conjunction with calibration data to determine the density of the sample.

The test is usually applied to petroleum, petroleum distillates, and petroleum

products that are liquids at temperatures between 15 and 35°C (59 and 95°F)

and have vapor pressures below 600mmHg and viscosities below about

15,000 cSt at the temperature of the test. However, the method should not be

applied to samples so dark in color that the absence of air bubbles in the

sample cell cannot be established with certainty. Accurate determination of

the density or specific gravity of crude oil is necessary for the conversion of

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Petroleum in View of its Classification, Assay and Analysis 37

measured volumes to volumes at the standard temperature of 15.56°C (60°F)

(ASTM D-1250, IP 200, Petroleum Measurement Tables). The specific

gravity is also a factor reflecting the quality of crude oils. The accurate

determination of the API gravity of petroleum and its products is necessary

for the conversion of measured volumes to volumes at the standard

temperature of 60°F (15.56°C). Gravity is a factor governing the quality of

crude oils. However, the gravity of a petroleum product is an uncertain

indication of its quality. Correlated with other properties, gravity can be used

to give approximate hydrocarbon composition and heat of combustion. This

is usually accomplished though use of the API gravity, which is derived from

the specific gravity:

API gravity (degrees) = (141.5/sp gr 60/60°F) – 131.5 and is also a critical

measure for reflecting the quality of petroleum. API gravity or density or

relative density can be determined using one of two hydrometer methods

(ASTM D-287, ASTM D-1298). The use of a digital analyzer (ASTM D-

5002) is finding increasing popularity for the measurement of density and

specific gravity. In the method (ASTM D-287), the API gravity is

determined using a glass hydrometer for petroleum and petroleum products

that are normally handled as liquids and that have a Reid vapor pressure of

26 psi (180 kPa) or less. The API gravity is determined at 15.6°C (60°F), or

converted 38 petroleum and petroleum products to values at 60°F, by means

of standard tables. These tables are not applicable to non-hydrocarbons or

essentially pure hydrocarbons such as the aromatics. This test method is

based on the principle that the gravity of a liquid varies directly with the

depth of immersion of a body floating in it. The API gravity is determined

with an hydrometer by observing the freely floating API hydrometer and

noting the graduation nearest to the apparent intersection of the horizontal

plane surface of the liquid with the vertical scale of the hydrometer after

temperature equilibrium has been reached. The temperature of the sample is

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determined with a standard test thermometer that is immersed in the sample

or with the thermometer that is an integral part of the hydrometer

(thermohydrometer).

II.1.3. Distillation

The distillation tests give an indication of the types of products and the

quality of the products that can be obtained from petroleum, and the tests are

used to compare different petroleum types through the yield and quality of

the 300°C (572°F) residuum fraction. For example, the waxiness or viscosity

of this fraction gives an indication of the amount, types, and quality of the

residual fuel that can be obtained from the petroleum. In this respect, the

determination of the aniline point (ASTM D-611, IP 2) can be used to

determine the aromatic or aliphatic character of petroleum. Although not

necessarily the same as the wax content, correlative relationships can be

derived from the data. The basic method of distillation (ASTM D-86) is one

of the oldest methods in use because the distillation characteristics of

hydrocarbons have an important effect on safety and performance, especially

in the case of fuels and solvents. The boiling range gives information on the

composition, the properties, and the behavior of petroleum and derived

products during storage and use. Volatility is the major determinant of the

tendency of a hydrocarbon mixture to produce potentially explosive vapors.

Several methods are available to define the distillation characteristics of

petroleum and its various petroleum products. In addition to these physical

methods, other test methods based on gas chromatography are also used to

derive the boiling point distribution of a sample (ASTM D-2887).

In the preliminary assay of petroleum the method of distillation is often used

to give a rough indication of the boiling range of the crude (ASTM D-2892,

IP 123). The test is carried out at atmospheric pressure and is stopped at

300°C (572°F) to avoid thermal decomposition. The distillate and the

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residuum can be further examined by tests such as specific gravity (ASTM

D-1298, IP 160), sulfur content (ASTM D-129, IP 61), and viscospetroleum

assay 39 ity (ASTM D-445, IP 71). In fact, the use of a method (ASTM D-

2569) developed for the determining the distillation characteristic of pitch

allows further examination of residua.

In addition to the whole crude oil tests performed as part of the inspection

assay, a comprehensive or full assay requires that the crude be fractionally

distilled and the fractions characterized by the relevant tests. Fractionation of

the crude oil begins with a true boiling point (TBP) distillation using a

fractionating column with an efficiency of 14–18 theoretical plates and

operated at a reflux ratio of 5 :1 (ASTM D-2892). The TBP distillation may

be used for all fractions up to a maximum cut point of about 350°C

atmospheric equivalent temperature (AET), but a low residence time in the

still (or reduced pressure) is needed to minimize cracking.

It is often useful to extend the boiling point data to higher temperatures than

are possible in the fractionating distillation method previously described, and

for this purpose a vacuum distillation in a simple still with no fractionating

column (ASTM D-1160) can be carried out. This distillation, which is done

under fractionating conditions equivalent to one theoretical plate, allows the

boiling point data to be extended to about 600°C (1112°F) with many crude

oils. This method gives useful comparative and reproducible results that are

often accurate enough for refinery purposes, provided significant cracking

does not occur. Usually seven fractions provide the basis for a reasonably

thorough evaluation of the distillation properties of the feedstock:

1. Gas, boiling range: <15.5°C (60°F)

2. Gasoline (light naphtha), boiling range: l5.5–149°C (60–300°F)

3. Kerosene (medium naphtha), boiling range: 149–232°C (300–450°F)

4. Gas oil, boiling range: 232–343°C (450–650°F)

5. Light vacuum gas oil, boiling range: 343–371°C (650–700°F)

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6. Heavy vacuum gas oil, boiling range: 371–566°C (700–1050°F)

7. Residuum, boiling range: >566°C (1050°F)

From 5 to 50 liters of crude oil are necessary to complete a full assay,

depending on the number of fractions to be taken and the tests to be

performed on the fractions.

A more recent test method (ASTM D-5236) is seeing increasing use and

appears to be the method of choice for crude assay vacuum distillations.

Wiped-wall or thin-film molecular stills can also be used to separate the

higher-boiling fractions under conditions that minimize cracking. In these

units, however, cut points cannot be directly selected because vapor

temperature in the distillation column cannot be measured accurately under

petroleum and petroleum products operating conditions. Instead, the wall

(film) temperature, pressure, and feed rate that will produce a fraction with a

given end point are determined from in-house correlations developed by

matching yields between the wiped-wall distillation and the conventional

distillation (ASTM D-l160, ASTM D-5236). And wiped-wall stills are often

used because they allow higher end points and can easily provide sufficient

quantities of the fractions for characterization purposes.

II.1.4. Light Hydrocarbons

The amount of the individual light hydrocarbons in petroleum (methane to

butane or pentane) is often included as part of the preliminary assay.

Although one of the more conventional distillation procedures might be used,

the determination of light hydrocarbons in petroleum is best is carried out

with a gas chromatographic method (ASTM D-2427).

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II.1.5. Metallic Constituents

Petroleum, as recovered from the reservoir, contains metallic constituents but

also picks up metallic constituents during recovery, transportation, and

storage. Even trace amounts of these metals can be deleterious to refining

processes, especially processes in which catalysts are used. Trace

components, such as metallic constituents, can also produce adverse effects

in refining either (1) by causing corrosion or (2) by affecting the quality of

refined products. Hence, it is important to have test methods that can

determine metals, both at trace levels and at major concentrations. Thus test

methods have evolved that are used for the determination of specific metals

as well as the multielement methods of determination using techniques such

as atomic absorption spectrometry, inductively coupled plasma atomic

emission spectrometry, and X-ray fluorescence spectroscopy.

Nickel and vanadium along with iron and sodium (from the brine) are the

major metallic constituents of crude oil. These metals can be determined by

atomic absorption spectrophotometric methods (ASTM D-5863, IP 285, IP

288, IP 465), wavelength-dispersive X-ray fluorescence spectrometry (IP

433), and inductively coupled plasma emission spectrometry (ICPES).

Several other analytical methods are available for the routine determination

of trace elements in crude oil, some of which allow direct aspiration of the

samples (diluted in a solvent) instead of time-consuming sample preparation

Procedures such as wet ashing (acid decomposition) or flame or dry ashing

(removal of volatile/combustible constituents) (ASTM D-5863).

Among the techniques used for trace element determinations are conductivity

(IP 265), flameless and flame atomic absorption (AA) spectrophopetroleum

assay 41tometry (ASTM D-2788, ASTM D-5863), and inductively coupled

argon plasma (ICP) spectrophotometry (ASTM D-5708).

Inductively coupled argon plasma emission spectrophotometry (ASTM D-

5708) has an advantage over atomic absorption spectrophotometry (ASTM

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D-4628,ASTM D-5863) because it can provide more complete elemental

composition data than the atomic absorption method. Flame emission

spectroscopy is often used successfully in conjunction with atomic

absorption spectrophotometry (ASTM D-3605). X-ray fluorescence

spectrophotometry (ASTM D-4927, ASTM D-6443) is also sometimes used,

but matrix effects can be a problem. The method to be used for the

determination of metallic constituents in petroleum is often a matter of

individual preference.

II.1.6. Salt Content The salt content of crude oil is highly variable and results principally from

production practices used in the field and, to a lesser extent, from its

handling aboard the tankers bringing it to terminals. The bulk of the salt

present will be dissolved in coexisting water and can be removed in

desalters, but small amounts of salt may be dissolved in the crude oil itself.

Salt may be derived from reservoir or formation waters or from other waters

used in secondary recovery operations. Aboard tankers, ballast water of

varying salinity may also be a source of salt contamination.

Salt in crude oil may be deleterious in several ways. Even in small

concentrations, salts will accumulate in stills, heaters, and exchangers,

leading to fouling that requires expensive cleanup. More importantly, during

flash vaporization of crude oil certain metallic salts can be hydrolyzed to

hydrochloric acid according to the following reactions:\

2NaCl + H2O -------------- 2 HCl + Na2O

MgCl2 + H2O --------------- 2 HCl + MgO

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The hydrochloric acid evolved is extremely corrosive, necessitating the

injection of a basic compound, such as ammonia, into the overhead lines to

minimize corrosion damage. Salts and evolved acids can also contaminate

both overhead and residual products, and certain metallic salts can deactivate

catalysts. Thus knowledge of the content of salt in crude oil is important in

deciding whether and to what extent the crude oil needs desalting.

The salt content is determined by potentiometric titration in a nonaqueous

solution in which the conductivity of a solution of crude oil in a polar solvent

is compared with that of a series of standard salt solutions in 42 petroleum

and petroleum products the same solvent (ASTM D-3230). In this method,

the sample is dissolved in a mixed solvent and placed in a test cell consisting

of a beaker and two parallel stainless steel plates. An alternating voltage is

passed through the plates, and the salt content is obtained by reference to a

calibration curve of the relationship of salt content of known mixtures to the

current. It is necessary, however, to use other methods, such as atomic

absorption, inductively coupled argon plasma emission spectrophotometry,

and ion chromatography to determine the composition of the salts present. A

method involving application of extraction and volumetric titration is also

used (IP 77).

II.1.7. Sulfur Content

Sulfur is present in petroleum as sulfides, thiophenes, benzothiophenes, and

dibenzothiophenes. In most cases, the presence of sulfur is detrimental to the

processing because sulfur can act as catalytic poisons during processing. The

sulfur content of petroleum is an important property and varies widely within

the rough limits 0.1% w/w to 3.0% w/w, and sulfur content up to 8.0% w/w

has been noted for tar sand bitumen. Compounds containing this element are

among the most undesirable constituents of petroleum because they can give

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rise to plant corrosion and atmospheric pollution. Petroleum can evolve

hydrogen sulfide during distillation as well as low-boiling sulfur compounds.

Hydrogen sulfide may be evolved during the distillation process either from

free hydrogen sulfide in the feed stocks or because of low-temperature

thermal decomposition of sulfur compounds; the latter is less likely than the

former. Generally, however, the sulfur compounds concentrate in the

distillation residue, the volatile sulfur compounds in the distillates being

removed by such processes as hydrofining and caustic washing. The sulfur

content of fuels obtained from petroleum residua and the atmospheric

pollution arising from the use of these fuels is an important factor in

petroleum utilization, so that the increasing insistence on a low-sulfur-

content fuel oil has increased the value of low-sulfur petroleum.

Sulfur compounds contribute to corrosion of refinery equipment and

poisoning of catalysts, cause corrosiveness in refined products, and

contribute to environmental pollution as a result of the combustion of fuel

products. Sulfur compounds may be present throughout the boiling range of

crude oils although, as a rule, they are more abundant in the higher-boiling

fractions. In some crude oils, thermally labile sulfur compounds can

decompose on heating to produce hydrogen sulfide, which is corrosive and

toxic. A considerable number of tests are available to estimate the sulfur in

petroleum or to study its effect on various products. Hydrogen sulfide

dispetroleum assay 43 solved in petroleum is normally determined by

absorption of the hydrogen sulfide in a suitable solution that is subsequently

analyzed chemically (Doctor Method) (ASTM, D-4952, IP 30) or by the

formation of cadmium sulfate (IP 103).

The Doctor test measures the amount of sulfur available to react with

metallic surfaces at the temperature of the test. The rates of reaction are

metal type-, temperature-, and time dependent. In the test, a sample is treated

with copper powder at 149°C or 300°F. The copper powder is filtered from

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Petroleum in View of its Classification, Assay and Analysis 45

the mixture. Active sulfur is calculated from the difference between the

sulfur contents of the sample (ASTM D-129) before and after treatment with

copper. Sulfur that is chemically combined as an organic constituent of crude

is usually estimated by oxidizing a sample in a bomb and converting the

sulfur compounds to barium sulfate that is determined gravimetrically

(ASTM D- 129, IP 61). This method is applicable to any sample of

sufficiently low volatility (e.g., a residuum or tar sand bitumen) that can be

weighed accurately in an open sample boat and that contains at least 0.1%

sulfur. In this method, the sample is oxidized by combustion in pressure

vessel (bomb) containing oxygen under pressure. The sulfur in the sample is

converted to sulfate and from the bomb washings is gravimetrically

determined as barium sulfate. However, the method is not applicable to

samples containing elements that give residues, other than barium sulfate,

that are insoluble in dilute hydrochloric acid and would interfere in the

precipitation step. In addition, the method is also subject to inaccuracies that

arise from interference by the sediment inherently present in petroleum. Until

recently, one of the most widely used methods for determination of total

sulfur content has been combustion of a sample in oxygen to convert the

sulfur to sulfur dioxide, which is collected and subsequently titrated

iodometrically or detected by nondispersive infrared (ASTM D- 1552). This

method is particularly applicable to heavier oil and fractions such as residua

that boil above 177°C (350°F) and contain more than 0.06% w/w sulfur. In

addition, the sulfur content of petroleum coke containing up to 8% w/w

sulfur can be determined. In the iodate detection system, the sample is

burned in a stream of oxygen at a sufficiently high temperature to convert the

sulfur to sulfur dioxide. The combustion products are passed into an absorber

that contains an acidic solution of potassium iodide and starch indicator. A

faint blue color is developed in the absorber solution by the addition of

standard potassium iodate solution and as combustion proceeds, bleaching

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Petroleum in View of its Classification, Assay and Analysis 46

the blue color, more iodate is added. From the amount of standard iodate

consumed during the combustion, the sulfur content of the sample is

calculated.

In the infrared detection system, the sample is weighed into a special ceramic

boat that is then placed into a combustion furnace at 1371°C 44 petroleum

and petroleum products (2500°F) in an oxygen atmosphere. Moisture and

dust are removed with traps, and the sulfur dioxide is measured with an

infrared detector. The lamp combustion method (ASTM D-1266, IP 107) and

the Wickbold combustion method (IP 243) are used for the determination of

sulfur in petroleum and as trace quantities of total sulfur in petroleum

products and are related to various other methods (ASTM D-2384,ASTM D-

2784, ASTM D-2785, ASTM D-4045) In the lamp method (ASTM D-1266,

IP 107), a sample is burned in a closed system using a suitable lamp and an

artificial atmosphere composed of 70% carbon dioxide and 30% oxygen to

prevent formation of nitrogen oxides. The sulfur oxides are absorbed and

oxidized to sulfuric acid (H2SO4) by means of hydrogen peroxide (H2O2)

solution that is then flushed with air to remove dissolved carbon dioxide.

Sulfur as sulfate in the absorbent is determined acidimetrically by titration

with standard sodium hydroxide (NaOH) solution. Alternatively, the sample

can be burned in air and the sulfur as sulfate in the absorbent determined

gravimetrically as barium sulfate (BaSO4) after precipitation. If the sulfur

content of the sample is less than 0.01% w/w, it is necessary to determine

sulfur in the absorber solution turbidimetrically as barium sulfate.

The older, classic techniques for sulfur determination are being supplanted

by two instrumental methods (ASTM D-2622,ASTM D-4294,IP 447). In the

first method (ASTM D-2622), the sample is placed in an X-ray beam, and

the peak intensity of the sulfur Ka line at 5.373Å is measured. The

background intensity, measured at 5.190Å, is subtracted from the peak

intensity, and the resultant net counting rate is then compared with a

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Petroleum in View of its Classification, Assay and Analysis 47

previously prepared calibration curve or equation to obtain the sulfur

concentration in % w/w.

The second method (ASTM D-4294, IP 477) uses energy-dispersive Xray

fluorescence spectroscopy, has slightly better repeatability and

reproducibility than the high-temperature method, and is adaptable to field

applications but can be affected by some commonly present interferences

such as halides. In this method, the sample is placed in a beam emitted from

X-ray source. The resultant excited characteristic X radiation is measured,

and the accumulated count is compared with counts from previously

prepared calibration standard to obtain the sulfur concentration. Two groups

of calibration standards are required to span the concentration range; one

standard ranges from 0.015% to 0.1% w/w sulfur and the other from 0.1% to

5.0% w/w sulfur. 2.2.8. Viscosity and Pour Point Viscosity and pour point

determinations are performed principally to ascertain the handling (flow)

characteristics of petroleum at low temperatures. Petroleum assay 45 there

are, however, some general relationships of crude oil composition that can be

derived from pour point and viscosity data. Commonly, the lower the pour

point of a crude oil the more aromatic it is, and the higher the pour point the

more paraffinic it is.

Viscosity is usually determined at different temperatures (e.g., 25°C/77°F,

and 100°C/212°F) by measuring the time for a volume of liquid to flow

under gravity through a calibrated glass capillary viscometer (ASTM D-445).

In the test, the time for a fixed volume of liquid to flow under gravity

through the capillary of a calibrated viscometer under a reproducible driving

head and at a closely controlled temperature is measured in seconds.

The kinematic viscosity is the product of the measured flow time and the

calibration constant of the viscometer. Conversion of the kinematic viscosity

in centistokes (cSt) at any temperature to Saybolt Universal viscosity in

Saybolt Universal seconds (SUS) at the same temperature and for converting

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Petroleum in View of its Classification, Assay and Analysis 48

kinematic viscosity in centistokes at 122 and 210°F to Saybolt Furol

viscosity in Saybolt Furol seconds (SFS) at the same temperatures (ASTM

D-2161) is available through formulae.

The viscosity index (ASTM D-2270, IP 226) is a widely used measure of the

variation in kinematic viscosity due to changes in the temperature of

petroleum between 40°C and 100°C (104°F and 212°F). For crude oils of

similar kinematic viscosity, the higher the viscosity index the smaller is the

effect of temperature on its kinematic viscosity. The accuracy of the

calculated viscosity index is dependent only on the accuracy of the original

viscosity determination.

The pour point of petroleum is an index of the lowest temperature at which

the crude oil will flow under specified conditions. The maximum and

minimum pour point temperatures provide a temperature window where

petroleum, depending on its thermal history, might appear in the liquid as

well as the solid state. The pour point data can be used to supplement other

measurements of cold flow behavior, and the data are particularly useful for

the screening of the effect of wax interaction modifiers on the flow behavior

of petroleum.

In the original (and still widely used) test for pour point (ASTM D-97, IP

15), a sample is cooled at a specified rate and examined at intervals of 3°C

(5.4°F) for flow characteristics. The lowest temperature at which the

movement of the oil is observed is recorded as the pour point. A later test

method (ASTM D-5853) covers two procedures for the determination of the

pour point of crude oils down to –36°C. One method provides a measure of

the maximum (upper) pour point temperature. The second method measures

the minimum (lower) pour point temperature. In these methods, the test

specimen is cooled (after preliminary heating) at a specified rate and

examined at intervals of 3°C (5.4°F) for flow character- 46 petroleum and

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Petroleum in View of its Classification, Assay and Analysis 49

petroleum products istics. Again, the lowest temperature at which movement

of the test specimen is observed is recorded as the pour point.

In any determination of the pour point, petroleum that contains wax produces

an irregular flow behavior when the wax begins to separate. Such petroleum

possesses viscosity relationships that are difficult to predict in pipeline

operation. In addition, some waxy petroleum is sensitive to heat treatment

that can also affect the viscosity characteristics. This complex behavior limits

the value of viscosity and pour point tests on waxy petroleum. However,

laboratory pumpability tests (ASTM D-3245, IP 230) are available that give

an estimate of minimum handling temperature and minimum line or storage

temperature.

II.1.8. Water and Sediment

Considerable importance is attached to the presence of water or sediment in

petroleum because they lead to difficulties in the refinery, for example,

corrosion of equipment, uneven running on the distillation unit, blockages

in heat exchangers, and adverse effects on product quality.

The water and sediment content of crude oil, like salt, results from

production and transportation practices. Water, with its dissolved salts, may

occur as easily removable suspended droplets or as an emulsion. The

sediment dispersed in crude oil may be comprised of inorganic minerals from

the production horizon or from drilling fluids and scale and rust from

pipelines and tanks used for oil transportation and storage. Usually water is

present in far greater amounts than sediment, but, collectively, it is unusual

for them to exceed 1% of the crude oil on a delivered basis. Like salt, water

and sediment can foul heaters, stills, and exchangers and can contribute to

corrosion and to deleterious product quality. Also, water and sediment are

principal components of the sludge that accumulates in storage tanks and

must be disposed of periodically in an environmentally acceptable manner.

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Petroleum in View of its Classification, Assay and Analysis 50

Knowledge of the water and sediment content is also important in accurately

determining net volumes of crude oil in sales, taxation, exchanges, and

custody transfers. The sediment consists of finely divided solids that may be

drilling mud or sand or scale picked up during the transport of the oil or may

consist of chlorides derived from evaporation of brine droplets in the oil. The

solids may be dispersed in the oil or carried in water droplets. Sediment in

petroleum can lead to serious plugging of equipment, corrosion due to

chloride decomposition, and a lowering of residual fuel quality.

Water may be found in the crude either in an emulsified form or in large

droplets and can cause flooding of distillation units and excessive

accumulation of sludge in tanks. Refiners generally limit the quantity, and

although steps are normally taken at the oil field to reduce the water content

as much petroleum assay 47 as possible, water may be introduced later

during shipment. In any form, water and sediment are highly undesirable in a

refinery feedstock, and the relevant tests involving distillation (ASTM D-95,

ASTM D-4006, IP 74, IP 358), centrifuging (ASTM D-96,ASTM D-4007),

extraction (ASTM D-473, IP 53), and the Karl Fischer titration (ASTM D-

4377, ASTM D-4928, IP 356, IP 386, IP 438, IP 439) are regarded as

important in petroleum quality examinations. Before the assay it is

sometimes necessary to separate the water from a petroleum sample. Certain

types of petroleum, notably heavy oil, often form persistent emulsions that

are difficult to separate. On the other hand, in testing wax-bearing petroleum

for sediment and water care must be taken to ensure that wax suspended in

the sample is brought into solution before the test; otherwise it will be

recorded as sediment.

The Karl Fischer test method (ASTM D-1364, ASTM D-6304) covers the

direct determination of water in petroleum. In the test, the sample injection in

the titration vessel can be performed on a volumetric or gravimetric basis.

Viscous samples can be analyzed with a water vaporizer accessory that heats

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Petroleum in View of its Classification, Assay and Analysis 51

the sample in the evaporation chamber, and the vaporized water is carried

into the Karl Fischer titration cell by a dry, inert carrier gas. Water and

sediment in petroleum can be determined simultaneously (ASTM D-96,

ASTM D-4007, IP 359) by the centrifuge method. Known volumes of

petroleum and solvent are placed in a centrifuge tube and heated to 60°C

(140°F). After centrifugation, the volume of the sedimentand- water layer at

the bottom of the tube is read. For petroleum that contains wax, a

temperature of 71°C (160°F) or higher may be required to completely melt

the wax crystals so that they are not measured as sediment.

Sediment is also determined by an extraction method (ASTM D-473, IP 53)

or by membrane filtration (ASTM D-4807). In the former method (ASTM D-

473, IP 53), an oil sample contained in a refractory thimble is extracted with

hot toluene until the residue reaches a constant mass. In the latter test, the

sample is dissolved in hot toluene and filtered under vacuum through a 0.45-

mm-porosity membrane filter. The filter with residue is washed, dried, and

weighed.

II.1.9. Wax Content

Petroleum with high wax content presents difficulties in handling and

pumping as well as producing distillate and residual fuels of high pour point

and lubricating oils that are costly to dewax. All the standard methods for the

determination of wax involve precipitating the wax from solvents such as

methylene chloride or acetone under specified conditions of solvent-to-oil

ratio and temperature. The wax appearance point (ASTM D-3117) may be

determined by cooling of a sample under prescribed conditions with stirring.

The temperature at which the wax first appears is the wax appearance point.

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Petroleum in View of its Classification, Assay and Analysis 52

II.1.10. Other Tests

The inspection assay tests discussed above are not exhaustive but are the

ones most commonly used and provide data on the impurities present as well

as a general idea of the products that may be recoverable. Other properties

that are determined on an as-needed basis include, but are not limited to, the

following: (1) vapor pressure (Reid method) (ASTM D-323, IP 69, IP 402),

(2) total acid number (ASTM D-664, IP 177), and chloride content (ASTM

D-4929, IP 244). The Reid vapor pressure test method (ASTM D-323, IP 69)

measures the vapor pressure of volatile petroleum. The Reid vapor pressure

differs from the true vapor pressure of the sample because of some small

sample vaporization and the presence of water vapor and air in the confined

space. The acid number is the quantity of base, expressed in milligrams of

potassium hydroxide per gram of sample, which is required to titrate a

sample in this solvent to a green/green-brown end point, using p-

naphtholbenzein indicator solution. The strong acid number is the quantity of

base, expressed as milligrams of potassium hydroxide per gram of sample,

required to titrate a sample in the solvent from its initial meter reading to a

meter reading corresponding to a freshly prepared nonaqueous acidic buffer

solution or a well-defined inflection point as specified in the test method

(ASTM D- 664, IP 177). To determine the acid number by the color indicator

method (ASTM D- 974, IP 139), the sample is dissolved in a mixture of

toluene and isopropyl alcohol containing a small amount of water and the

resulting single-phase solution is titrated at room temperature with standard

alcoholic base or alcoholic acid solution, respectively, to the end point

indicated by the color change of the added p-naphtholbenzein solution

(orange in acid and green brown in base).To determine the strong acid

number, a separate portion of the sample is extracted with hot water and the

aqueous extract is titrated with potassium hydroxide solution, using methyl

orange as an indicator. To determine the acid number by the potentiometric

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Petroleum in View of its Classification, Assay and Analysis 53

titration method (ASTM D-664, IP 177), the sample is dissolved in a mixture

of toluene and isopropyl alcohol containing a small amount of water and

titrated potentiometrically with alcoholic potassium hydroxide using a glass

indicating electrode and a calomel reference electrode. The meter readings

are plotted petroleum assay 49 manually or automatically against the

respective volumes of titrating solution, and the end points are taken only at

well-defined inflections in the resulting curve. When no definite inflections

are obtained, end points are taken at meter readings corresponding to those

found for freshly prepared nonaqueous acidic and basic buffer solutions. The

acid numbers obtained by this color indicator test method (ASTM D-974, IP

139) may or may not be numerically the same as those obtained by the

potentiometric titration method (ASTM D-664, IP 177). In addition, the color

of the crude oil sample can interfere with observation of the end point when

the color indicator method is used. Determination of the acid number is more

appropriate for various petroleum products. The test method for the

determination of the acid number by the color indicator titration method

(ASTM D-3339, IP 431) measures the acid number of oils obtained from a

laboratory oxidation test (ASTM D-943) using smaller amounts of samples

than those used in other acid number tests (ASTM D-664, ASTM D-974, IP

139, IP 177).

In this test, the sample is dissolved in a solvent mixture of toluene, isopropyl

alcohol, and a small amount of water and the solution is titrated at room

temperature under a nitrogen atmosphere with standard potassium hydroxide

(KOH) in isopropyl alcohol to the stable green color of the added indicator p-

naphtholbenzein. Dark-colored crude oils (and crude oil products) are more

difficult to analyze by this method because of the difficulty in detecting color

change. In such cases, the potentiometric titration method (ASTM D-664, IP

177) may be used if sufficient sample is available.

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Petroleum in View of its Classification, Assay and Analysis 54

The acid numbers will not provide the data essential to determining whether

specific petroleum or a blend with other crude oils will yield the desired

product slate. Such data can only be generated when a comprehensive

petroleum assay is performed and the data from several tests are taken in

relation to each other. The aniline point (or mixed aniline point) (ASTM D-

611, IP 2) has been used for the characterization of crude oil, although it is

more applicable to pure hydrocarbons and in their mixtures and is used to

estimate the aromatic content of mixtures. Aromatics exhibit the lowest

aniline points and paraffin the highest aniline points. Cycloparaffins and

olefins exhibit values between these two extremes. In any hydrocarbon

homologous series the aniline point increases with increasing molecular

weight. With the data derived from the test assay, it is possible to assess

petroleum quality to acquire a degree of predictability of performance during

refining. However, knowledge of the basic concepts of refining will help

the analyst understand the production and, to a large extent, the anticipated

properties of the product, which in turn are related to storage, sampling, and

handling of the products. Petroleum products are introduced in the following

Table 4.

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Lower Carbo

n Limit

Upper Carbo

n Limit

Lower Boiling Point (°C)

Upper Boiling Point (°C)

Lower Boiling Point (°F)

Upper Boiling

Point (°F)

Product

Refinery gas C1 C4 -161 -1 -259 31 Liquefied petroleum gas

C3 C4 -42 -1 -44 31

Naphtha C5 C17 36 302 97 575

Gasoline C4 C12 -1 216 31 421

Kerosene/diesel fuel C8 C18 126 258 302 575

Aviation turbine fuel C8 C16 126 287 302 548

Fuel oil C12 >C20 216 421 >343 >649

Lubricating oil >C20 >343 >649

Wax C17 >C20 302 >343 575 >649

Asphalt >C20 >343 >649

Coke C50a >1000a >1832a

aCarbon number and boiling point difficult to assess; inserted for illustrative purposes only.

Table 4. Petroleum products.

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Petroleum in View of its Classification, Assay and Analysis 56

Chapter III

Petroleum Products

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III. Petroleum Products

III.1 Gaseous fuels

(III-1.1) Definition of gaseous fuels

Natural gas, which is predominantly methane, occurs in underground

reservoirs separately or in association with crude oil. The principal types of

gaseous fuels are oil (Distillation) gas, reformed natural gas, and reformed

propane or LPG. LPG is the term applied to certain specific hydrocarbons

and their mixtures, which exist in the gaseous state under atmospheric

ambient conditions but can be converted to the liquid State under conditions

of moderate pressure at ambient temperature. These are the light

hydrocarbon fractions of the paraffin series, derived from refinery processes,

crude oil stabilization plants, and natural gas processing plants comprising

propane(CH3CH2CH3), butane (CH3CH2CH2CH3), iso-butane

[CH3CH(CH3)CH3] and to a lesser extent propylene (CH3CH=CH2), or

butylene (CH3CH2CH=CH2).

The most common commercial products are propane, butane, or amixture of

the two compounds and they are generally extracted from natural gas or

crude petroleum, the properties of propane and butane was given in Table 5.

Propylene and butylene result from cracking other hydrocarbons in a

petroleum refinery and are two important chemical feedstock’s. Mixed gas is

a gas prepared by adding natural gas or LPG to a manufactured gas, giving a

product of better utility and higher heat content or Btu value.

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Petroleum in View of its Classification, Assay and Analysis 58

Propane Butane

Formula C3H8 C4H10

Boiling point, °F -44° 32

Specific gravity-gas (air = 1.00) 1.53 2

Specific gravity-liquid (water = 1.00) 0.51 0.58

Ib / gallon-liquid at 60 °F 4.24 4.81

BTU / gallon-gas at 60 °F 91,690 102,032

BTU / Lb-gas 21,591 21,221

BTU / ft3-gas at 60 °F 2516 3280

Flash point, °F -156 -96

Ignition temperature in air, °F 920-1020 900-1000

Maximum flame temperature in air, °F 3595 3615

Octane number (iso-octane = 100) 100+ 92

Table 5. Properties of propane and butane

(III-1.2) Composition of gaseous fuels

The principal constituent of natural gas is methane (CH4). Other

constituents are paraffinic hydrocarbons such as ethane (CH3CH3), propane

(CH3CH2CH3), and the butanes [CH3CH2CH2CH3 and (CH3)3CH]. Many

natural gases contain nitrogen (N2) as well as carbon dioxide (CO2) and

hydrogen sulfide (H2S). Trace quantities of argon, hydrogen, and helium may

also be present. Generally, the hydrocarbons having a higher molecular

weight than methane, carbon dioxide, and hydrogen sulfide are removed

from natural gas before to its use as a fuel. Gases produced in a refinery

contain methane, ethane, ethylene, propylene, hydrogen, carbon monoxide,

carbon dioxide, and nitrogen, with low concentrations of water vapor,

oxygen, and other gases.

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Petroleum in View of its Classification, Assay and Analysis 59

III.2. Gasoline

(III-2.1) Definition of gasoline

Gasoline, also called gas (United States and Canada), or petrol (Great

Britain) or benzene (Europe) is a mixture of volatile, flammable liquid

hydrocarbons derived from petroleum and used as fuel for internal

combustion engines. It is also used as a solvent for oils and fats. Originally a

by-product of the petroleum industry (kerosene being the principal product),

gasoline became the preferred automobile fuel because of its high energy of

combustion and capacity to mix readily with air in a carburetor.

Gasoline is a mixture of hydrocarbons that usually boil below 180 oC (355oF

or, at most, below 200oC (390oF). The hydrocarbon constituents in this

boiling range are those that have 4 to 12 carbon atoms in their molecular

structure and fall in to three general types: paraffins (including the cyclo

paraffins and branched materials), olefins, and aromatics.

Gasoline is still in great demand as a major product from petroleum. The

network of interstate high ways that links towns and cities in the United

States are dotted with frequent service centers where motorists can obtain

refreshment not only for themselves but also for their vehicles.

(III-2.2) Composition of gasoline

Automotive gasoline typically contains about almost 200 (if not

several hundred) hydrocarbon compounds. The relative concentrations of the

compounds vary considerably depending on the source of crude oil, refinery

process, and product specifications .Typical hydrocarbon chain lengths range

from C4 through C12 with a general hydrocarbon distribution consisting of

alkanes (4–8%), alkenes(2–5%), iso-alkanes25–40%, cycloalkanes (3–7%),

cycloalkenes (l–4%) and aromatics (20–50%). However, these proportions

vary greatly.

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Petroleum in View of its Classification, Assay and Analysis 60

The majority of the members of the paraffin, olefin, and aromatic

series (of which there are about 500) boiling below 200oC (390oF) have been

found in the gasoline fraction of petroleum. However, it appears that the

distribution of the individual members of straight-run gasoline (i.e., distilled

from petroleum without thermal alteration) is not even.

Highly branched paraffins, which are particularly valuable constituents of

gasoline(s), are not usually the principal paraffinic constituents of straight-

run gasoline. The more predominant paraffinic constituents are usually the

normal (straight-chain) isomers, which may dominate the branched isomer(s)

by a factor of 2 or more. This is presumed to indicate the tendency to

produce long uninterrupted carbon chains during petroleum maturation rather

than those in which branching occurs. However, this trend is somewhat

different for the cyclic constituents of gasoline, that is, cycloparaffins

(naphthenes) and aromatics. In these cases, the preference appears to be for

several short side chains rather than one long substituent.

The octane number is the most important property in gasoline. The aromatic

hydrocarbons have the highest octane number, while the paraffinic

hydrocarbons have the lowest octane number which increases by

isomerization. The olefinic hydrocarbons lie between that of normal and

branched chain hydrocarbons. Naphthenes are lower than the straight chain

olefins of the same number of carbon atoms.

III.3 Kerosene

(III-3.1) Definition of kerosene

Kerosene (kerosine), also called paraffin or paraffin oil, is a flammable

pale-yellow or colorless oily liquid with a characteristic odor. It is obtained

from petroleum and used for burning in lamps and domestic heaters or

furnaces, as a fuel or fuel component for jet engines, and as a solvent for

greases and insecticides.

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Petroleum in View of its Classification, Assay and Analysis 61

Kerosene is intermediate in volatility between gasoline and gas/diesel oil. It

is medium oil distilling between 150oC and 300oC (300oF to 570oF).

Kerosene has a flashpoint of about 25oC (77oF) and is suitable for use as an

illuminant when burned in a wide lamp. The term kerosene is also often

incorrectly applied to various fuel oils, but a fuel oil is actually any liquid or

liquid petroleum product that produces heat when burned in a suitable

container or that produces power when burned in an engine.

Kerosene was the major refinery product before the onset of the automobile

age, but now kerosene can be termed one of several secondary petroleum

products after the primary refinery product gasoline. Kerosene originated as

a straight-run petroleum fraction that boiled between approximately 205oC

and 260oC (400oF to 500oF) [36].

(III-3.2) Composition of kerosene

Chemically, kerosene is a mixture of hydrocarbons; the chemical

composition depends on its source, but it usually consists of about 10

different hydrocarbons, each containing from 10 to 16 carbon atoms per

molecule; the constituents include n-dodecane (n-C12H26), alkylbenzenes, and

naphthalene and its derivatives. Kerosene is less volatile than gasoline; it

boils between about 140oC (285oF) and 320oC (610oF).

Kerosene, because of its use as burning oil, must be free of aromatic and

unsaturated hydrocarbons, as well as free of the more obnoxious sulfur

compounds. The desirable constituents of kerosene are saturated

hydrocarbons, and it is forth is reason that kerosene is manufactured as a

straight-run fraction, not by a cracking process.

Although the kerosene constituents are predominantly saturated materials,

there is evidence for the presence of substituted tetrahydronaphthalene.

Dicycloparaffins also occur in substantial amounts in kerosene. Other

hydrocarbons with both aromatic and cycloparaffin rings in the same

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Petroleum in View of its Classification, Assay and Analysis 62

molecule, such as substituted indan, also occur in kerosene. The predominant

structure of the dinuclear aromatics appears to be that in which the aromatic

rings are condensed, such as naphthalene whereas the isolated two ring

compounds, such as biphenyl, are only present in traces, if at all.

III.4 Fuel oils

(III-4.1) Definition of fuel oils

Fuel oils are classified in several ways but generally may be divided into two

main types: distillate fuel oil and residual fuel oil.

Distillate fuel oil is vaporized and condensed during a distillation process

and thus has a definite boiling range and does not contain high-boiling

constituents. A fuel oil that contains any amount of the residue from crude

distillation of thermal cracking is a residual fuel oil. The terms distillate fuel

oil and residual fuel oil are losing their significance, as fuel oil is now made

for specific uses and may be either distillates or residuals or mixtures of the

two. The terms domestic fuel oil, diesel fuel oil, and heavy fuel oil are more

indicative of the uses of fuel oils. Domestic fuel oil is fuel oil that is used

primarily in the home. This category of fuel oil includes kerosene, stove oil,

and furnace fuel oil; they are distillate fuel oils.

Diesel fuel oil is also a distillate fuel oil that distills between180oC and

380oC (356oF to 716oF). Several grades are available depending on their

uses: diesel oil for diesel compression ignition (cars, trucks, and marine

engines) and light heating oil for industrial and commercial uses.

Heavy fuel oil comprises all residual fuel oils (including those obtained by

blending). Heavy fuel oil constituents range from distillable constituents to

residual (non-distillable) constituents that must be heated to 260oC (500oF) or

more before they can be used. The kinematic viscosity is above 10 cst at

80oC (176oF). The flash point is always above 50oC (122oF) and the density

is always higher than 0.900. In general, heavy fuel oil usually contains

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Petroleum in View of its Classification, Assay and Analysis 63

cracked residua, reduced crude, or cracking coil heavy product, which is

mixed (cut back) to a specified viscosity with cracked gas oils and

fractionator bottoms. For some industrial purposes in which flames or flue

gases contact the product (ceramics, glass, heat treating, and open hearth

furnaces) fuel oils must be blended to contain minimum sulfur contents, and

hence low-sulfur residues are preferable for these fuels.

(III-4.2) Types of fuel oils

No.1 fuel oil is a petroleum distillate that is one of the most widely

used of the fuel oil types. It is used in atomizing burners that spray fuel in to

a combustion chamber where the tiny droplets burn while in suspension. It is

also used as a carrier for pesticides, as a weed killer, as a mold release agent

in the ceramic and pottery industry, and in the cleaning industry. It is found

in asphalt coatings, enamels, paints, thinners and varnishes. No.1fuel oil is

petroleum distillate (straight-run kerosene) consisting primarily of

hydrocarbons in the range C9 - C16. Fuel oil No.1 is very similar in

composition to diesel fuel; the primary difference is in the additives.

No.2 fuel oil is a petroleum distillate that may be referred to as

domestic or industrial. The domestic fuel oil is usually of lower boiling and a

straight-run product. It is used primarily for home heating. Industrial

distillate is a cracked product or a blend of both. It is used in smelting

furnaces, ceramic kilns, and packaged boilers. No. 2 fuel oil is characterized

by hydrocarbon chain lengths in the C11-C20 range. The composition consists

of aliphatic hydrocarbons (straight chain alkanes and cycloalkanes) (64%),

unsaturated hydrocarbons (alkenes) (1% to 2%), and aromatic hydrocarbons

(including alkyl benzene sand 2-ring, 3-ring aromatics) (35%) but contains

only low amounts of the polycyclic aromatic hydrocarbons (<5 %;).

No.6 fuel oil (also called Bunker Coil or residual fuel oil) is the

residuum from crude oil after naphtha gasoline, No.1fuel oil, and No.2fuel

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Petroleum in View of its Classification, Assay and Analysis 64

oil have been removed. No.6 fuel oil can be blended directly to heavy fuel oil

or made in to asphalt. Residual fuel oil is more complex in composition and

impurities than distillate fuels. Limited data are available on the composition

of No.6 fuel oil. Polycyclic aromatic hydrocarbons (including the alkylated

derivatives) and metal containing constituents are components of No.6 fuel

oil.

III.5. Lubricating oil

(III-5.1) Definition of lubricating oil

Mineral oils are often used as lubricating oils but also have medicinal

and food uses. A major type of hydraulic fluid is the mineral oil class of

hydraulic fluids. The mineral based oils are produced from heavy end crude

oil distillates. Hydrocarbon numbers ranging from C15 to C50 occur in the

various types of mineral oils, with the heavier distillates having higher

percentages of the higher carbon number compounds.

Crankcase oil (motor oil) may be either mineral based or synthetic.

The mineral based oils are more widely used than the synthetic oils and may

be used in automotive engines, railroad and truck diesel engines, marine

equipment, jet and other air craft engines, and most small 2- and 4-stroke

engines. The mineral based oils contain hundreds to thousands of

hydrocarbon compounds, including a substantial fraction of nitrogen and

sulfur containing compounds.

The hydrocarbons are mainly mixtures of straight and branched chain

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

nuclear aromatic hydrocarbons (and the alkyl derivatives) and metal

containing constituents are components of motor oils and crankcase oils,

with the used oils typically having higher concentrations than the new

unused oils. Typical carbon number chain lengths range from C15 to C50.

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Petroleum in View of its Classification, Assay and Analysis 65

Lubricating oil is distinguished from other fractions of crude oil by

their usually high (>400 °C, >750 °F) boiling point, as well as their high

viscosity. Materials suitable for the production of lubricating oils are

comprised principally of hydrocarbons containing from 25 to 35 or even 40

carbon atoms per molecule, whereas residual stocks may contain

hydrocarbons with 50 or more (up to 80 or so) carbon atoms per molecule.

(III-5.2) Composition of lubricating oil

The composition of lubricating oil may be substantially different from

the lubricant fraction from which it was derived, as wax (normal paraffins) is

removed by distillation or refining by solvent extraction and adsorption

preferentially removes non hydrocarbon constituents as well as poly nuclear

aromatic compounds and the multiring cycloparaffins.

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Petroleum in View of its Classification, Assay and Analysis 66

Chapter IV.

Native materials

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Petroleum in View of its Classification, Assay and Analysis 67

Chapter IV. Native materials

IV.1. Heavy oil

There are also other types of petroleum that are different from

conventional petroleum in that they are much more difficult to recover from

the subsurface reservoir. These materials have a much higher viscosity (and

lower API gravity) than conventional petroleum, and primary recovery of

these petroleum types usually requires thermal stimulation of the reservoir.

When petroleum occurs in a reservoir that allows the crude material to be

recovered by pumping operations as a free-flowing dark to light-colored

liquid, it is often referred to as conventional petroleum.

Heavy oils are more difficult to recover from the subsurface reservoir

than light oils. The definition of heavy oils is usually based on the API

gravity or viscosity, and the definition is quite arbitrary although there have

been attempts to rationalize the definition based on viscosity, API gravity,

and density.

For many years, petroleum and heavy oil were very generally defined

in terms of physical properties. For example, heavy oils were considered to

be that crude oil that has gravity somewhat less than 20o API, generally

falling into the API gravity range 10o to 15o. For example, Cold Lake heavy

crude oil has API gravity equal to 12o and extra heavy oils, such as tar sand

bitumen, usually have an API gravity in the range 5o to 10o. Residue would

vary depending on the temperature at which distillation was terminated but

usually vacuum residues are in the range 2o to 8o API [27].

The generic term heavy oil is often applied to crude oil that has less

than 20 API and usually, but not always, sulfurs content higher than 2% by

weight [27]. The term heavy oil has also been arbitrarily used to describe

both the heavy oils that require thermal stimulation of recovery from the

reservoir and the bitumen in bituminous sand (q.v., tar sand) formations from

which the heavy bituminous material is recovered . Extra heavy oils are

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Petroleum in View of its Classification, Assay and Analysis 68

materials that occur in the solid or near-solid state and are generally

incapable of free flow under reservoir conditions (q.v., bitumen.)

IV.2. Bitumen

The term bitumen (also, on occasion, referred to as native asphalt, and

extra heavy oil) includes a wide variety of reddish brown to black materials

of semisolid, viscous to brittle character that can exist in nature with no

mineral impurity or with mineral matter contents that exceed 50% by weight.

Bitumen is frequently found filling the pores and crevices of sandstone,

limestone, or argillaceous sediments, in which case the organic and

associated mineral matrix is known as rock asphalt [37, 38].

Bitumen is a naturally occurring material that is found in deposits

where the permeability is low and passage of fluids through the deposit can

only be achieved by prior application of fracturing techniques. Tar sand

bitumen is a high-boiling material with little, if any, material boiling below

350oC (660oF) and the boiling range approximates the boiling range of an

atmospheric residuum.

The recovery of the bitumen depends to a large degree on the

composition and construction of the sands. Generally, the bitumen found in

tar sand deposits is an extremely viscous material that is immobile under

reservoir conditions and cannot be recovered through a well by the

application of secondary or enhanced recovery techniques.

The expression tar sand is commonly used in the petroleum industry to

describe sandstone reservoirs that are impregnated with a heavy, viscous

black crude oil that cannot be retrieved through a well by conventional

production techniques. However, the term tar sand is actually a misnomer;

more correctly, the name tar is usually applied to the heavy product

remaining after the destructive distillation of coal or other organic matter

[39].

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Petroleum in View of its Classification, Assay and Analysis 69

The bitumen in tar sand formations requires a high degree of thermal

stimulation for recovery to the extent that some thermal decomposition may

have to be induced. Current recovery operations of bitumen in tar sand

formations involve use of a mining technique.

IV.3. Wax

Naturally occurring wax, often referred to as mineral wax, occurs as

a yellow to dark brown, solid substance that is composed largely of paraffins

[40]. Fusion points vary from 60oC (140oF) to as high as 95oC (203oF). They

are usually found associated with considerable mineral matter, as a filling in

veins and fissures or as an interstitial material in porous rocks.

IV.4. Natural gas

The generic term natural gas applies to gases commonly associated

with petroliferous (petroleum-producing, petroleum-containing) geologic

formations. Natural gas generally contains high proportions of methane (a

single carbon hydrocarbon compound, CH4) and some of the higher

molecular weight higher paraffins (CnH2n) (generally containing up to six

carbon atoms may also be present in small quantities Table 6. The

hydrocarbon constituents of natural gas are combustible, but nonflammable

non-hydrocarbon components such as carbon dioxide, nitrogen, and helium

are often present in the minority and are regarded as contaminants.

In addition to the natural gas found in petroleum reservoirs, there are

also those reservoirs in which natural gas may be the sole occupant. The

principal constituent of natural gas is methane, but other hydrocarbons, such

as ethane, propane, and butane, may also be present.

Carbon dioxide is also a common constituent of natural gas. Trace

amounts of rare gases, such as helium, may also occur, and certain natural

gas reservoirs are a source of these rare gases. Just as petroleum can vary in

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Petroleum in View of its Classification, Assay and Analysis 70

composition, so can natural gas. Differences in natural gas composition

occur between different reservoirs, and two wells in the same field may also

yield gaseous products that are different in composition [9].

Name Formula Vol.%

Methane CH4 >85

Ethane C2H6 3–8

Propane C3H8 1–5

Butane C4H10 1–2

Pentane a C5H12 1–5

Carbon dioxide CO2 1–2

Hydrogen sulfide H2S 1–2

Nitrogen N2 1–5

Helium He <0.5 aPentane and higher molecular weight hydrocarbons, including

benzene and toluene.

Table 6. Constituents of natural gas

There are several general definitions that have been applied to natural

gas. Thus, lean gas is gas in which methane is the major constituent. Wet gas

contains considerable amounts of the higher molecular weight hydrocarbons.

Sour gas contains hydrogen sulfide whereas sweet gas contains very little, if

any, hydrogen sulfide. Residue gas is natural gas from which the higher

molecular weight hydrocarbons have been extracted and casing head gas is

derived from petroleum, but is separated at the separation facility at the well-

head . To further define the terms dry and wet in quantitative measures, the

term dry natural gas indicates that there is less than 0.1 gallon (1 US

gallon=264.2 m3) of gasoline vapor (higher molecular weight paraffins) per

1000 ft3 (1 ft3=0.028 m3). The term wet natural gas indicates that there are

such paraffins present in the gas, in fact more than 0.1 gal/1000 ft3.

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Petroleum in View of its Classification, Assay and Analysis 71

Associated or dissolved natural gas occurs either as free gas or as gas

in solution in the petroleum. Gas that occurs as a solution in the petroleum is

dissolved gas whereas the gas that exists in contact with the petroleum (gas

cap) is associated gas.

Other components such as carbon dioxide (CO2), hydrogen sulfide

(H2S), mercaptans (thiols; R-SH), as well as trace amounts of other

constituents may also be present. Thus, there is no single composition of

components which might be termed typical natural gas. Methane and ethane

constitute the bulk of the combustible components; carbon dioxide (CO2) and

nitrogen (N2) are the major noncombustible (inert) components.

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Petroleum in View of its Classification, Assay and Analysis 72

Chapter V:

Sampling and Analysis Using

Chromatographic Methods

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Petroleum in View of its Classification, Assay and Analysis 73

Chapter V: Sampling, Analysis Using Chromatographic Methods

V.1. Sampling

The value of any product is judged by the characteristics of the sample as

determined by laboratory tests. The sample used for the test must be

representative of the bulk material, or data will be produced that are not

representative of the material and will, to be blunt, be incorrect no matter

how accurate or precise the test method is. In addition, the type and

cleanliness of sample containers are important: If the container is

contaminated or is made of material that either reacts with the product or is a

catalyst, the test results may be wrong.

Thus the importance of the correct sampling of any product destined for

analysis should always be overemphasized. Incorrect sampling protocols can

lead to erroneous analytical data from which performance of the product in

service cannot be accurately deduced. For example, properties such as

specific gravity, distillation yield, vapor pressure, hydrogen sulfide content,

and octane number of the gasoline are affected by the content of low-boiling

hydrocarbons so that suitable cooling or pressure sampling methods must be

used and care must be taken during the subsequent handling of the sample to

avoid the loss of any volatile components. In addition, adequate records of

the circumstances and conditions during sampling must be made; for

example, in sampling from storage tanks, the temperatures and pressures of

the separation plant and the atmospheric temperature would be noted.

At the other end of the volatility scale, products that contain, or are

composed of, high-molecular-weight paraffin hydrocarbons (wax) that are

also in a solid state may require judicious heating (to dissolve the wax) and

agitation (homogenization, to ensure thorough mixing) before sampling. If

Room-temperature sampling is the modus operandi and product cooling

causes wax to precipitate, homogenization to ensure correct sampling is also

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Petroleum in View of its Classification, Assay and Analysis 74

necessary.

Representative samples are prerequisite for the laboratory evaluation of any

type of product, and many precautions are required in obtaining and handling

representative samples (ASTM D-270, ASTM D-1265). The precautions

depend on the sampling procedure, the characteristics (low-boiling or high-

boiling constituents) of the product being sampled, and the storage tank,

container, or tank carrier from which the sample is obtained. In addition, the

sample container must be clean, and the type to be used depends not only on

the product but also on the data to be produced.

The basic objective of each procedure is to obtain a truly representative

sample or, more often, a composite of several samples that can be considered

to be a representative sample. In some cases, because of the size of the

storage tank and the lack of suitable methods of agitation, several samples

are taken from large storage tanks in such a manner that the samples

represent the properties of the bulk material from different locations in the

tank and thus the composite sample will be representative of the entire lot

being sampled. This procedure allows for differences in sample that might

result from the stratification of the bulk material because of tank size or

Temperature at the different levels of the storage tank. Solid samples require

a different protocol that might involve melting (liquefying) of the bulk

material (assuming that thermal decomposition is not induced) followed by

homogenization. On the other hand, the protocol used for coal sampling

(ASTM D-346, ASTM D-2013) might also be applied to sampling of

petroleum products, such as coke, that are solid and for which accurate

analysis is required before sale. Once the sampling procedure is

accomplished, the sample container should be labeled immediately to

indicate the product, time of sampling, location of the sampling point, and

any other information necessary for the sample identification. And, if the

samples were taken from different levels of the storage tank, the levels from

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Petroleum in View of its Classification, Assay and Analysis 75

which the samples were taken and the amounts taken and mixed into the

composite should be indicated on the sample documentation. Although the

above text is focused on the acquisitions of samples from storage tanks,

sampling records for any procedure must be complete and should include,

but are not restricted to, information such as:

1. The precise (geographic or other) location (or site or refinery or process)

from which the sample was obtained.

2. The identification of the location (or site or refinery or process) by name.

3. The character of the bulk material (solid, liquid, or gas) at the time of

sampling.

4. The means by which the sample was obtained.

5. The protocols that were used to obtain the sample.

6. The date and the amount of sample that was originally placed into storage.

7. Any chemical analyses (elemental analyses, fractionation by adsorbents or

by liquids, functional type analyses) that have been determined to date.

8. Any physical analyses (API gravity, viscosity, distillation profile) that

have been determined to date.

9. The date of any such analyses included in items 5 and 6.

10. The methods used for analyses that were employed in items 5 and6.

11. The analysts who carried out the work in items 5 and 6.

12. A log sheet showing the names of the persons (with the date and the

reason for the removal of an aliquot) who removed the samples from storage

and the amount of each sample (aliquot) that was removed for testing, there

must be a means of identifying the sample history as carefully as possible so

that each sample is tracked and defined in terms of source and activity.

Thus the accuracy of the data from any subsequent procedures and tests for

which the sample is used will be placed beyond a reasonable doubt.

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Petroleum in View of its Classification, Assay and Analysis 76

V.2. Analysis and Specifications

Petroleum exhibits wide variations in composition and properties, and these

occur not only in petroleum from different fields but also in oils taken from

different production depths in the same well. Historically, physical properties

such as boiling point, density (gravity), and viscosity have been used to

describe petroleum, but the needs for analysis are even more extensive.

Petroleum analysis involves not only determining the composition of the

material under investigation but, more appropriately, determining the

suitability of the petroleum for refining or the product for use. In this sense,

the end product of petroleum analysis or (testing) is a series of data that

allow the investigator to specify the character and quality of the material

under investigation. Thus a series of specifications are determined for

petroleum and its products.

Because of the differences in petroleum composition, the importance of the

correct sampling of crude oil that contains light hydrocarbons cannot be

overestimated. Properties such as specific gravity, distillation profile, vapor

pressure, hydrogen sulfide content, and octane number of gasoline are

affected by the light hydrocarbon content so that suitable cooling or pressure

sampling methods must be used and care taken during the subsequent

handling of the oil to avoid the loss of any volatile constituents. In addition,

adequate records of the circumstances and conditions during sampling must

be made. For example, sampling from oil field separators, the temperatures

and pressures of the separation plant, and the atmospheric temperature

should be noted.

Hence, the production of data focuses on (1) measurement, 2) accuracy, (3)

precision, and (4) method validation, all of which depend on the sampling

protocols that were used to obtain the sample. Without strict sampling

protocols, variation and loss of accuracy (or precision) must be anticipated.

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Petroleum in View of its Classification, Assay and Analysis 77

For example, correct sampling of the product in storage or carrier tanks is

important to obtain a representative sample for the laboratory tests that are

essential in converting measured quantities to the standard volume.

Elemental analyses of petroleum show that it contains mainly carbon and

hydrogen. Nitrogen, oxygen, and sulfur (hetero elements) are present in

smaller amounts, and trace elements such as vanadium, nickel, etc, are also

present. Of the hetero elements, sulfur is the most important. The mixture of

hydrocarbons is highly complex. Paraffinic, naphthenic, and aromatic

structures can occur in the same molecule, and the complexity increases with

boiling range. The attempted classification of crude oils in terms of these

three main structural types has proved inadequate. The value of a particular

crude to a refiner depends on its quality and whether he can economically

obtain a satisfactory product pattern that matches market demand (market

pull). In the main, the refiner is not concerned with the actual chemical

nature of the material but in methods of analysis that would provide

information sufficient to assess the potential quality of the oil, to supply

preliminary engineering data, and also to indicate whether any difficulties

might arise in handling, refining, or transporting petroleum or its products.

Such information may be obtained in one of two ways:

1. Preliminary assay-inspection data. 2. A full assay involving the

preparation of a true boiling point curve and the analysis of fractions and

product blends throughout the full range of the crude oil. The preliminary

assay provides general data on the oil and is based on simple tests such as

distillation range, water content, specific gravity, and sulfur content that

enable desirable or undesirable features to be noted. This form of assay

requires only a small quantity of sample and is therefore particularly useful

for the characterization of oil field samples produced from cores, drill stem

tests, or seepages. The tests in the preliminary assay are relatively simple and

can be completed in a short time and generally on a routine basis. This assay

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Petroleum in View of its Classification, Assay and Analysis 78

gives a useful general picture of the quality of petroleum, but it does not

cover the work necessary to provide adequate data, for example, for the

design of refinery equipment, nor does it produce a sufficient quantity of the

various products from the crude so that they can be examined for quality. A

full assay of petroleum is based on a true boiling point distillation of the

crude, and sufficient data are obtained to assess the yields and properties of

the straight-run products, covering light hydrocarbons, light, middle, and

heavy distillate, lubricants, residual fuel oil, and residuum. Often, the middle

ground is reached between the preliminary assay and the full assay, but the

requirements may also be feedstock dependent.

A feedstock specification or product specification provides the data that give

adequate control of feedstock behavior in a refinery or product quality. Thus

a specification offers the luxury of predictability of feedstock behavior in a

refinery or predictability of product quality (therefore, product behavior)

relative to market demand. Ultimately, feedstock behavior and/or product

quality is judged by an assessment of performance. And it is performance

that is the ultimate criterion of quality. It is therefore necessary to determine

those properties, the values of which can be established precisely and

relatively simply by inspection tests in a control laboratory, that correlate

closely with the important performance properties.

Sometimes the inspection tests attempt to measure these properties, for

example, the carbon residue of a feedstock that is an approximation of the

amount of the thermal coke that will be formed during refining or a research

octane number test devised to measure performance of motor fuel. In other

cases the behavior must be determined indirectly from a series of test results.

In addition, there are many instances in which interrelationships of the

specification data enable properties to be predicted from the measured

properties with as good precision as can be obtained by a single test. It would

be possible to examine in this way the relationships between all the analysis

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Petroleum in View of its Classification, Assay and Analysis 79

and specifications 15 specified properties of a product and to establish

certain key properties from which the remainder could be predicted, but this

would be a tedious task.

An alternative approach to that of picking out the essential tests in a

specification by using regression analysis is to examine at the specification

as a whole and to use the necessary component. This is termed principal

components analysis. In this method a set of data as points in

multidimensional space (n-dimensional, corresponding to n original tests) is

examined to determine the direction that accounts for the biggest variability

in the data (first principal component).The process is repeated until n

principal components are evaluated, but it must be determined which

components are of practical importance because some principal components

may be due to experimental error. The number of significant principal

components shows the number of independent properties being measured by

the tests considered.

The number of independent properties having been established, there exists a

natural basis for making the specification more efficient. In the long term, it

might be possible to obtain new tests of a fundamental nature to replace

existing tests. In the short term, selecting the best of the existing tests to

define product quality will be beneficial.

Finally, the analytical methods used to describe petroleum must be modified

for the characterization of tar sand bitumen in the same way that tests for

conventional petroleum have been modified and/or replaced by newer, more

relevant test methods. For example, what might appear to be a test of

minimal value for conventional petroleum might afford invaluable data for

determining the behavior of tar sand bitumen or the potential products from

each. In fact, it is because of behavior differences that research into text

methods for tar sand bitumen is continuing [41]. Clearly, for maximum

efficiency the tests that are specified for any feedstock or product should be

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Petroleum in View of its Classification, Assay and Analysis 80

as independent of each other as possible. In fact, the efficiency of a

specification should be judged by the extent to which the tests specified will:

1. Predict (control) feedstock behavior;

2. Predict (control) and product quality;

3. Measure independent properties;

4. Measure these properties with adequate precision;

5. Offer rapid response to refinery and laboratory demands.

Petroleum analysis has been greatly augmented in recent years by application

of a wide variety of instrumental techniques to studies of the hydro- 16

petroleum analysis carbon compositions of crude oils and their products.

Before this, hydrocarbon type analyses (percent paraffins, naphthenes,

olefins, and aromatics) were derived from correlations based on physical

data. The advent of instrumental techniques has led to two major

developments:

1. Individual component analysis;

2. An extension to, and more detailed subdivision of, the various compound

types that occur in the higher-boiling ranges of petroleum distillates. Of these

instrumental techniques, gas/liquid chromatography and mass spectrometry

are the most important in providing the hydrocarbon composition data in

crude oil assay work. By gas chromatographic analysis, it is now possible to

determine routinely the individual methane (CH4) to heptanes (C7H16)

hydrocarbons and the individual aromatics that boil below 165°C (330°F)

and also obtain a complete normal paraffin distribution up to C50. In

addition, with a microcoulometric detector specific to sulfur, the sulfur

compound distribution can be obtained throughout the distillate range. Gas

chromatographic analysis can also be used to provide simulated true boiling

point (TBP) curves, and developments in preparative scale gas/liquid

chromatography have made possible the preparation of fractions in quantities

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Petroleum in View of its Classification, Assay and Analysis 81

sufficient not only for extensive spectrometric analyses but also for the

normal inspection type tests to be undertaken.

Mass spectrometry offers a very rapid method for obtaining hydrocarbon

type analyses on a wide range of fractions up to and including heavy gas

oils.The information obtained on a routine basis subdivides the hydrocarbons

into the various groups. The technique can also be used in conjunction with

separation procedures such as gas/liquid chromatography, molecular

distillation, thermal diffusion, or selective adsorption to provide more

detailed analyses where necessary, even on fractions in the lubricating oil

range. Thus petroleum analysis is a complex subject involving a variety of

techniques, some of which have been mentioned above. But no single

technique should supercede the other. Petroleum analysis is a complex

discipline that needs a multidimensional approach. And the explanation of

the data that are obtained requires adequate interpretation.

a) Accuracy

The accuracy of a test is a measure of how close the test result will be to the

true value of the property being measured. As such, the accuracy can be

expressed as the bias between the test result and the true value.

However, the absolute accuracy can only be established if the true value is

known. In the simplest sense, a convenient method to determine a

relationship between two measured properties is to plot one against the other.

Such an exercise will provide either a line fit of the points or a spread that

may or may not be within the limits of experimental error. The data can then

be used to determine the approximate accuracy of one or more points

employed in the plot. For example, a point that lies outside the limits of

experimental error (a flyer) will indicate an issue of accuracy with that test

and the need for a repeat determination. Illustration of the general

relationship of petroleum properties However, the graphical approach is not

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Petroleum in View of its Classification, Assay and Analysis 82

appropriate for finding the absolute accuracy between more than two

properties. The well-established statistical technique of regression analysis is

more pertinent to determining the accuracy of points derived from one

property and any number of other properties. There are many instances in

which relationships of this sort enable properties to be predicted from other

measured properties with as good precision as they can be measured by a

single test. It would be possible to examine in this way the relationships

between all the specified properties of a product and to establish certain key

properties from which the remainder could be predicted, but this would be a

tedious task.

An alternative approach to that of picking out the essential tests in a

specification using regression analysis is to take a look at the specification as

a whole and extract the essential features (termed principal components

analysis).

Principal components analysis (see also p. 16) involves an examination of

set of data as points in n-dimensional space (corresponding to n original

tests) and determines (first) the direction that accounts for the biggest

variability in the data (first principal component).The process is repeated

until n principal components are evaluated, but not all of these are of

practical importance because some may be attributable purely to

experimental error. The number of significant principal components shows

the number of independent properties being measured by the tests

considered. Following from this, it is necessary to establish the number of

independent properties that are necessary to predict product performance in

service with the goals of rendering any specification more meaningful and

allowing a high degree of predictability of product behavior. For a long term

approach it might be possible to obtain new tests of a fundamental nature to

replace, or certainly to supplement, existing tests. In the short term, selecting

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Petroleum in View of its Classification, Assay and Analysis 83

the best of the existing tests to define product quality is the most beneficial

route to predictability.

b) Precision

The precision of a test method is the variability between test results obtained

on the same material using the specific test method. The precision of a test is

usually unrelated to its accuracy. The results may be precise but not

necessarily accurate. In fact, the precision of an analytical method is the

amount of scatter in the results obtained from multiple analyses of a

homogeneous sample. To be meaningful, the precision study must be

performed using the exact sample and standard preparation procedures that

will be used in the final method. Precision is expressed as repeatability and

reproducibility.

The intralaboratory precision or within-laboratory precision refers to the

precision of a test method when the results are obtained by the same operator

in the same laboratory using the same apparatus. In some cases, the precision

is applied to data gathered by a different operator in the same laboratory

using the same apparatus. Thus intralaboratory precision has an expanded

meaning insofar as it can be applied to laboratory precision.

Repeatability or repeatability interval of a test (r) is the maximum

permissible difference due to test error between two results obtained on the

same material in the same laboratory. r = 2.77 ¥ standard deviation of test

The repeatability interval r is, statistically, the 95% probability level, that is,

the differences between two test results are unlikely to exceed this

repeatability interval more than five times in a hundred.

The interlaboratory precision or between-laboratory precision is defined in

terms of the variability between test results obtained on the aliquots of the

same homogeneous material in different laboratories using the same test

method. The term reproducibility or reproducibility interval (R) is analogous

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Petroleum in View of its Classification, Assay and Analysis 84

to the term repeatability, but it is the maximum permissible difference

between two results obtained on the same material but now in different

laboratories. Therefore, differences between two or more laboratories should

not exceed the reproducibility interval more than five times in a hundred.

R = 2.77 ¥ standard deviation of test

The repeatability value and the reproducibility value have important

implications for quality. As the demand for clear product specifications, and

hence control over product consistency grows, it is meaningless to establish

product specifications that are more restrictive than the reproducibility/

repeatability values of the specification test methods.

c) Validation Method Method validation is the process of proving that an analytical method is

acceptable for its intended purpose. Many organizations, such as the ASTM,

provide a framework for performing such validations. In general, methods

for product specifications and regulatory submission must include studies on

specificity, linearity, accuracy, precision, range, detection limit, and

quantitation limit.

The process of method development and validation covers all aspects of the

analytical procedure, and the best way to minimize method problems is to

perform validation experiments during development. In performing

validation studies, the approach should be viewed with the understanding

that validation requirements are continually changing and vary widely

depending on the type of product under tested and compliance with any

necessary regulatory group.

In the early stages of new product development, it may not be necessary to

perform all of the various validation studies. However, the process of

validating a method cannot be separated from the actual development of the

method conditions, because the developer will not know whether the method

conditions are acceptable until validation studies are performed.

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Petroleum in View of its Classification, Assay and Analysis 85

The development and validation of a new analytical method may therefore be

an iterative process. Results of validation studies may indicate that a change

in the procedure is necessary, which may then require revalidation. During

each validation study, key method parameters are determined and then used

for all subsequent validation steps. The first step in the method development

and validation cycle should be to set minimum requirements, which are

essentially acceptance specifications for the method. A complete list of

criteria should be agreed on during method development with the end users

before the method is developed so that expectations are clear. Once the

validation studies are complete, the method developers should be confident

in the ability of the method to provide good quantitation in their own

laboratories. The remaining studies should provide greater assurance that the

method will work well in other laboratories, where different operators,

instruments, and reagents are involved and where it will be used over much

longer periods of time.

The remaining precision studies comprise much of what is often referred to

as ruggedness. Intermediate precision is the precision obtained when an

assay is performed by multiple analysts using several instruments on

different days in one laboratory. Intermediate precision results are used to

identify which of the above factors contribute significant variability to the

final result. The last type of precision study is reproducibility (q.v.), which is

determined by testing homogeneous samples in multiple laboratories, often

as part of interlaboratory crossover studies. The evaluation of reproducibility

results often focuses more on measuring bias in results than on determining

differences in precision alone. Statistical equivalence is often used as a

measure of acceptable interlaboratory results. An alternative, more practical

approach is the use of analytical equivalence, in which a range of acceptable

results is chosen before the study and used to judge the acceptability of the

results obtained from the different laboratories.

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Petroleum in View of its Classification, Assay and Analysis 86

Performing a thorough method validation can be a tedious process, but the

quality of data generated with the method is directly linked to the quality of

this process. Time constraints often do not allow for sufficient method

validation. Many researchers have experienced the consequences of invalid

methods and realized that the amount of time and resources required to solve

problems discovered later exceeds what would have been expended initially

if the validation studies had been performed properly.

Putting in time and effort up front will help any analyst to find a way through

the method validation maze and will eliminate many of the problems

common to inadequately validated analytical methods.

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Petroleum in View of its Classification, Assay and Analysis 87

(V-2.1) High Performance liquid chromatography (HPLC)

For the analysis of poly nuclear aromatic hydrocarbons

HPLC has found great utility in separating different hydrocarbon

group types and identifying specific constituent types [42-44].

carcinogenicity Structure PAHS compounds Aromatic

ring

-----

Naphtalene (Nap) 2- Ring

------

-----

----- -----

-----

Acenaphthylene(A)

Acenaphthene(Ace)

Phenanthrene(Phe)

Flourene(F)

Anthracene(Ant)

3-Ring

------

------ + ±

Fluoranthene(Flu)

Pyrene(Pyr)

Benzo{a}anthracen(BaA)

Chrysene(Chr)

4-Ring

++

--------

--------

+ ++

Benzo{b}fluoranthene(BbF)

Benzo{K}fluoranthene(BKF)

Benzo{a}Pyrene(BAP)

Dibenzo{a,h}anthracene(DahA)

5-Ring

-------

+

Benzo{ghi} perlyene(Bp)

Indeno{1,2,3-cd}perlyene(IP)

6-Ring

Table 7. Definition of each PAHs compounds in term of aromatic ring and

carcinogenicity. Note: ------ Not carcinogenic, + Carcinogenic, ++, +++ Strongly Carcinogenic, ±

Uncertain.

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Petroleum in View of its Classification, Assay and Analysis 88

The application of the HPLC technique used to the identification of the

molecular types in nonvolatile feed stocks such as residua. The molecular

species in the asphaltene fraction have been of particular interest (41,44-49)

leading to identification of the size of poly nuclear aromatic systems in the

asphaltene constituents.

HPLC methods were used as analytical tools for determination of poly

aromatic hydrocarbons (PAHs) which contain a class of compounds

composed of two or more aromatic rings. They are a component of crude and

refined petroleum and coal, and persist in soil and sediments. Hundreds of

PAHs have been identified and these usually are found as complex mixture

[45]. PAHs may also be generated as products of incomplete combustion

processes such as forest fires and volcanic eruption [46]. Most petroleum

fractions especially heavy petroleum fractions contain significant levels of

PAHs. PAHs are classified as environmentally hazardous organic compounds

due to their known or suspected carcinogenicity and are included in the

European Community (EC) and United States Environmental Protection

Agency (USEPA) priority pollutant list [47].

They are ubiquitous in the environment largely due to the extensive use of

fossil fuels. Several PAHs are known to be potential human carcinogens;

these include benz[a]anthracene, chrysene, benzo[b]flouranthene, benzo[a]

pyrene and benzo [ghi] perylene [48].

From the above, it has been found that PAHs were analyzed using Various

methods such as high performance liquid chromatography (HPLC) with

photometric (UV/VIS) or fluorimetric (FL) detection [49], gas

chromatography with flame ionization detection [50], micellar electro kinetic

capillary chromatography with ultraviolet (UV) detection [51] and as PAHs

are all volatilizable GC/MS is a viable analytical approach giving good

separation and identification of PAHs.

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Petroleum in View of its Classification, Assay and Analysis 89

(V-2.2) Gas chromatography (GC)

Gas Chromatography (GC) is a method for separating the volatile

components of various mixtures. It is in fact a highly efficient fractionating

technique and it is ideally suited to the quantitative analysis of mixtures

when the possible components are known and the interest lies only in

determining the amounts of each present. In this type of application GC has

taken over much of the work previously done by the other techniques. It is

now the preferred technique for the analysis of hydrocarbon gases,

condensates and heavy hydrocarbon fractions. Also, GC in-line monitors are

having increasing application in refinery plant control.

The evolution of GC has been a major factor in the successful

identification of petroleum constituents. It is, however, almost impossible to

apply this technique to the low volatile and low thermal stable compounds. It

is comparative lack of volatility in the higher molecular weight, asphaltic

constituents of petroleum that brought about another type of identification

procedure, namely, carbon-type analysis. GC technique has proved to be an

exceptional and versatile instrumental tool for analyzing mixtures of

compounds that can be volatilized without decomposition. The analysis

depends on the distribution of the components in vapor state between two

phases, the stationary phase and the mobile phase. GC also provides a simple

and convenient method for determining n-paraffin distribution throughout

the petroleum distillate range. In this method, the n-paraffins are first

separated by activated chemical destruction of the sieve with hydrofluoric

acid, and the identity of the individual paraffin is determined

chromatographically.

Marquart et al. [52] analyzed the n-paraffins separated by urea

adduction by GLC. The GC separation was carried out on a 9-ft column

packed with 2 % Carbowax 1000 on Chromosorb W. The column

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Petroleum in View of its Classification, Assay and Analysis 90

temperature was programmed from 75 oC to 250 oC at 6 oC min-1. They

recommended squalane as the internal standard.

Jokuty et al. [53] used GC-FID to analyze saturates, aromatics, resins,

asphaltenes and waxes in 30 crude oils. They also developed a method to

determine the oil adhesion to a test surface.

Lai and Song [54] determined temperature-programmed retention

indexes for over 150 pure compounds (alkanes, alkenes, naphthenes,

polycyclic aromatic hydrocarbons) using two capillary columns with

different stationary-phase polarities at three heating rates. Despite the high

resolving power and extended working range of modern capillary GC, a

substantial proportion (30-90%) of fresh and biodegraded crude oils is still

having unresolved percentage and chromatograms of crude oils often contain

“humps” or so-called unresolved complex mixtures (UCMs) under the peaks

represent of separated paraffinic hydrocarbons. A few attempts to

characterize hydrocarbon UCMs have been made recently [55-59].

(V-2.3) Gas chromatography-Mass spectrometry (GC-MS)

A more recent and very important development in gas chromatography

it is a combination with a mass spectrometer as the detector called (GC-MS).

It has proved to be a powerful tool for identifying many compounds at very

low levels in a wide range of boiling matrix. By the combination of the two

techniques in one instrument, the onerous trapping of fractions from the gas

chromatographic column is avoided and higher sensitivities can be attained.

In passing through the gas chromatographic column, the sample is separated

more or less according to its boiling point and then identified by passing

through mass spectrometry (MS).

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Petroleum in View of its Classification, Assay and Analysis 91

(a) Petroleum biomarker fingerprinting for oil characterization and

source identification

Definition of biomarkers

The biomarker within petroleum, also referred to as internal markers

by petroleum geochemists, are molecular fossils, having been derived from

formerly living organisms. Biomarkers are structurally complex components

of petroleum that possess little structural variations from their biological

molecular precursors. Upon burial, heat and pressure over geological time

(the combination of diagenesis, catagenesis, and metagenesis) transform

organic matter and incorporate parent molecules once present in living

organisms into fossil fuel. The biomarker profile of a crude oil is distinctive

and diagnostic, often allowing correlation of oil to its source rock. Many

biomarkers in crude oil are resistant to biodegradation and oil weathering

processes and, therefore, are used by petroleum geochemists to assess

relationships among oils and/or their source rocks, thermal maturity, and

biodegradation [60]. The resistance of biomarkers to degradation generally

increases in the following order: n-alkanes < isoprenoids < steranes <

hopanes/diasteranes < aromatic steroids < porphyrins [60, 61]. This sequence

has been used by petroleum geochemists to assign a biodegradation rank that

is based on the degree to which the biomarker composition of a petroleum is

altered [60, 62].

Biomarkers are used by petroleum geochemists for three reasons:

Biomarkers are ubiquitous in petroleum; 2) Biomarkers are much more

resistant to degradation and oil weathering processes than more labile oil

components; 3) Their distribution within petroleum is oil-specific and

diagnostic, acting as a fingerprint for the oil [63].

Typically, this biomarker pattern is analyzed using gas chromatography

/mass spectrometry (GC-MS) [64, 65]. Biomarker ratios can be calculated,

allowing correlation of oil to its source rock, maturation assessment,

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Petroleum in View of its Classification, Assay and Analysis 92

weathering assessment (including biodegradation) and determination of point

sources and biological input. Countless studies have used the specific

diagnostic characteristics of biomarker for these purposes.

Biomarker origin

Straight chain membrane lipids from algal, bacterial and higher plants

contribute to the formation of n-alkanes during crude oil maturation [60].

The transformation products of chlorophyll and chlorophyll related pigments

from photosynthetic prokaryotic and eukaryotic organisms include the

isoprenoids pristane and phytane, as well as the porphyrins [66-68].

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Petroleum in View of its Classification, Assay and Analysis 93

Fig. 2 During crude oil maturation (diagenesis, catagenesis, metagenesis) over the course of geological time, thermal stress and pressure transform the biological precursor chlorophyll-a into four biomarker compounds that are found extensively in most petroleums

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Petroleum in View of its Classification, Assay and Analysis 94

References

[1] ASTM D-4175. 2000. Standard terminology relating to petroleum,

petroleum products, and lubricants. In: Annual Book of Standards. American

Society for Testing and Materials. West Conshohocken , PA.Volume 05.02.

[2] JAMES G. SPEIGHT, Handbook of Petroleum Product Analysis,

Published by John Wiley & Sons, Inc., Hoboken, New Jersey. Published

simultaneously in Canada 2002.

[3] Speight, J.G. 1999b. The Desulfurization of Heavy Oils and Residua.

2nd Edition. Marcel Dekker, New York.

[4] Bestougeff, M. (1967). In Fundamental Aspects of Petroleum

Geochemistry. Nagy B. and Colombo U. eds. Elsevier, Amsterdam.

Chapter 3.

[5] A Master thesis “Study and Evaluation of Some Egyptian Crude Oils” by

I. A. El-sayed under Supervisors M. M. Mashaly, A. Y. El-naggar and R. I.

Abd-allah, Chemistry Department, Faculty of Science Damietta University,

Egypt, 2012.

[6] Hobson, G. D. and Pohl, W.1973. Modern Petroleum Technology, 4 the dn.

Applied Science Publishers, Barking, England.

[7]Thornton, D. P. Jr (1977). In Energy Technology Handbook. Considine

D. M., Ed. McGraw-Hill, New York.pp.3–12.

[8] Considine, D.M. and Considine, G.D. 1984. Encyclopedia of Chemistry,

4th edn. Van Nostrand Rein-hold Co., New York

[9] Speight,J.G.(1990). Fuel Science and Technology Handbook. Marcel

Dekker, New York.

[10] Speight J. G. The chemistry and technology of petroleum; Marcel

Dekker, Inc.:New York, 2006.

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Petroleum in View of its Classification, Assay and Analysis 95

[11] Speight, J.G., and Ozum,B. 2002.Petroleum Refining Processes. Marcel

Dekker,New York.

[12] Purdy,G.A. (1957). Petroleum: Prehistoric to Petrochemicals.

CoppClark Publishing, Toronto.

[13] Speight, J.G. 1990. In: Fuel Science and Technology Handbook. J.G.

Speight (Editor). Marcel Dekker, New York. Chapters 12–16.

[14] Speight, J.G. 2001. Handbook of Petroleum Analysis. John Wiley &

Sons, New York.

[15] Altgelt, K.H.; Boduszynski, M.M. Composition and Analysis of Heavy

Petroleum Fractions, Marcel Dekker: New York, 1994.

[16] Speight J. G. The chemistry and technology of petroleum; Marcel

Dekker, Inc.: New York, 1980.

[7] Speight J. G. The chemistry and technology of petroleum. 3rd ed. New

York: Marcel Dekker; 1999.

[18] Bunger JW and Li NC.; "Chemistry of asphaltenes". Advances in

chemistry series 195. Washington DC: American Chemical Society; 1981.

[19] Yen TF and Chilingarian GV.; " Asphaltenes and asphalt 1.

Developments in petroleum science 40." Amsterdam: Elsevier; 1994.

[20] Sheu EY and Mullins OC.; " Asphaltenes: fundamentals and

applications." NewYork: Plenum Press; 1996.

[21] Mullins OC and Sheu EY.; " Structures and dynamics of asphaltenes."

NewYork: Plenum Press; 1998.

[22] Andersen SI, Speight JG. Petroleum resins: separation, character, and

role in petroleum. Pet Sci Technol 2001; 19:1-34.

[23] Hammami A, Phelps CH, Monger-McClure Tand Little TM.;

"Asphaltene precipitation from live oils: an experimental investigation of

onset conditions and reversibility". Energy Fuels 2000; 14:14-18.

[24] Goual Land Firoozabadi A.; " Measurements of asphaltenes and resins

and dipole moment in petroleum fluids." AIChE J 2002; 48:2646-63.

Page 103: Petroleum in View of its Classification, Assay and Analysis 978-93-84648-05-3.pdf · Petroleum in View of its Classification, Assay and Analysis iii PREFACE Petroleum is the most

International Science Congress Association www.isca.in , www.isca.co.in , www.isca.net.co , www.isca.net.in

Petroleum in View of its Classification, Assay and Analysis 96

[25] Orr W.L., White C.M., Geochemistry of Sulphurin Fossil Fuels, in:

American Chemical Society, Washington, DC, 1990.

[26] Speight, J. G. 1986. Ann. Rev. Energy 11:253

[27] Speight,J.G. 2000. The Desulfurization of Heavy Oils and Residua, 2

nded. Marcel Dekker, NewYork.

[28][ Speight, J. G. 2001. Handbook of Petroleum Analysis. John Wiley &

Sons Inc., Hoboken, NJ.

[29] Cryette, W. R., Model 5009 Wide Range Cryoscope-Instruction Manual

Precision Systems Inc., Natick, MA, 1994.

[30] "Annual Book of ASTM Standard", Vols. 11.01 and 11.02, Am. Soc.

Test. Mater., Philadelphia, 1992.

[31] Hem, J. D., "Study and Interpretation of the Chemical Characteristics of

Natural Waters", U. S. Geol. Surv., Water Supply Paper 1973, 1959.

[32] "Standard Methods for the Examination of water and waste water",

Eaton, A.D., Clesceri, L.S., Greenberg, A.E., 19th Edn., APHA-AWWA-

WEF, Washington, 1995.

[33] "API Recommended Practice for Analysis of Oil-Field Water", APIRP

45, 2nd Edn., Am. Petrol. Inst., Dallas, 1968.

[34] Patton, C. C., "Applied Water Technology", Campbell Petroleum Series,

Norman, 1986.

[35] Collins, A. G., "Geochemistry of Oil-Field Waters", Elsevier,

Amsterdam, 1975.

[36] Walmsley, A.G. 1973.Modern Petroleum Technology. G. D. Hobson

and W. Pohl, eds. Applied Science Publishers Inc., Barking, Essex,

UK.Chapter17.

[37] Abraham, H. (1945). Asphalts and Allied Substances. Van Nostrand,

New York.

[38] Hoiberg, A. J. (1964).Bituminous Materials: Asphalts, Tars, and

Pitches. John Wiley and Sons, New York.

Page 104: Petroleum in View of its Classification, Assay and Analysis 978-93-84648-05-3.pdf · Petroleum in View of its Classification, Assay and Analysis iii PREFACE Petroleum is the most

International Science Congress Association www.isca.in , www.isca.co.in , www.isca.net.co , www.isca.net.in

Petroleum in View of its Classification, Assay and Analysis 97

[39] Speight, J.G. (1994).The Chemistry and Technology of Coal. 2 ndedn.

Marcel Dekker, New York.

[40] Wollrab, V. and Streibl, M. (1969). In Organic Geochemistry. Eginton

G., and Murphy M. T. J., eds. Springer-Verlag, New York.p.576.

[41] Wallace, D., and Carrigy, M.A. 1988. In: The Third UNITAR/UNDP

InternationalConference on Heavy Crude and Tar Sands. R.F. Meyer (Editor). Alberta Oil Sands Technology and Research Authority, Edmonton, Alberta, Canada. [42] Colin, J. M. and Vion, G. 1983. J.Chromatogr.280:152.

[43] Miller, R.L., Ettre, L.S., and Johansen, N.G. 1983. J. Chromatogr. 259:

393.

[44] Chartier, P., Gareil, P., Caude, M., Rosset, R., Neff, B., Bourgogno ,

H.F., and Husson, J. F. 1986. J. Chromatogr. 357: 381.

[45] Mottier, P., Parisod, R. J., Turesky, J., 2000. Quantitative determination

of poly cyclic aromatic hydrocarbons in barbecued meat sausages by gas

chromatography coupled to masss pectrometry. J. Agricult. Food Chem. 48,

1160–1166.

[46] Grova, N., Feidt, C., Crepineau, C.,Laurent, C., Lafargue, P.E.,

Hachimi, A., Rychen, G., 2002.Detection of poly-cyclic aromatic

hydrocarbon level in milk collected near Potential contamination sources. J.

Agricult. Food Chem. 50, 4640–4642.

[47] Nieva-Cano, M.J., Rubio-Barroso, S., Santos-Delgado, M.J., 2001.

Determination of PAH in foods a mples by HPLC with flourimetric detection

followings onication extraction without sample clean-up. The Analyst

126,1326–1331.

[48] Guillen, M. D., Sopelana, P., Partearroyo, M.A., 2000. Determination of

poly cyclic aromatic hydrocarbons in commercial liquid flavouring of

different compositions by gas chromatography–mass spectrometry. J.

Agricult. Food Chem. 48, 126–131.

Page 105: Petroleum in View of its Classification, Assay and Analysis 978-93-84648-05-3.pdf · Petroleum in View of its Classification, Assay and Analysis iii PREFACE Petroleum is the most

International Science Congress Association www.isca.in , www.isca.co.in , www.isca.net.co , www.isca.net.in

Petroleum in View of its Classification, Assay and Analysis 98

[49] Kiyali-Sayadi, M.N.,Rubio-Barroso,S., Cuesta-Jimenez, M.P., Polo-

Diez, L.M., 1999.Anew method for the determination of selected PAH in

coffee brew samples by HPLC with flourimetric detection and solid phase

extraction. J. Liquid Chromatogr.Relat.Technol. 22, 615–627.

[50] Guerin, T.F.J., 1999.The extraction of aged poly cyclic aromatic

hydrocarbon (PAH) residues from a clay soil using sonication and a soxhlet

procedure: a comparative study.Environ.Monit. 1, 63–67.

[51] Moy, T.W., Ferguson, P.L., Grange, A.H., Matchett, W., Kelliher, V.A.,

Brumley, W.C., Glassman, J., Farlay, J. W., 1998. Development of

separation systems for poly nuclear aromatic hydrocarbon

environmental contaminants using micellar electro kinetic

chromatography with molecular micelles and freezone electrophoresis.

Electrophoresis 19, 2090–2094.

[52] Marquqrt, J.R., Dellow, G.B., Freitas, E.R., Anal. Chem., 40, 1633 (1968).

[53] nJokuty, P., Whiticar, S., Fingas, M., Meyer, E., Knabel, C., Proc.

Environ. Canada AMOP Tech. Seminar, I., pp 1-19 (1995).

[54] Lai, W.C., Song, C., Fuel, 74, 1436 (1995).

[55] Killops S.D. and Al-Juboori M., Org. Geochem., 15 (1990) 147.

[56] Gough MA.and Rowland S.J., Nature, 344 (1990) 648.

[57] Gough M.A. and Rowland S.J., Energy Fuels, 5 (1991) 869.

[58] Revill A.T., Carr M.and Rowland S.J., J. Chromatogr., 589 (1992) 281.

[59] Sutton P.A., Lewis C.A., Rowland S.J., Org. Geochem. 36 (2005) 963.

[60] Peters, K. E., and Moldowan J. M.. 1993. The Biomarker Guide:

Interpreting Molecular Fossils in Petroleum and Ancient Sediments. Prentice

Hall. Englewood Cliffs, NJ. PP 40-45.

[61] Chosson, P., Connan J., Dessort D., and Lanau C.. 1992. In vitro

biodegradation of steranes and terpanes: a clue to understanding geological

situations. In: Biological Markers in Sediments and Petroleum (J. M.

Page 106: Petroleum in View of its Classification, Assay and Analysis 978-93-84648-05-3.pdf · Petroleum in View of its Classification, Assay and Analysis iii PREFACE Petroleum is the most

International Science Congress Association www.isca.in , www.isca.co.in , www.isca.net.co , www.isca.net.in

Petroleum in View of its Classification, Assay and Analysis 99

Moldowan, P. Albrecht, and R. P. Philip, eds.) Prentice Hall, Englewood

Cliffs. NJ. P.320-349.

[62] Volkman, J. K., Alexander R., Kagi R.I., and Woodhouse G. W.. 1983.

Demethylated hopanes in crude oils and their applications in petroleum

geochemistry. Geochimica et Cosmochimica Acta. 47:785-794.

[63] Whittaker, M., and Pollard S. J. T.. 1997. A performance assessment of

source correlation and weathering indices for petroleum hydrocarbons in the

environment. Environ. Toxicol. Chem. 16:1149-1158.

[64] McDonald, T. J., and Kennicutt M. C.. 1992. Fractionation of crude oils

by HPLC and quantitative determination of aliphatic and aromatic biological

markers by GC-MS with selected ion monitoring. LC-GC 10:935-38.

[65] Mills, M. A., McDonald T. J., Bonner J. S., Simon M. A., and

Autenrieth R. L.. 1999. Method for quantifying the fate of petroleum in the

environment. Chemosphere. 39:2563-2582.

[66] Bidigaire, R. R., Kennicutt M. C., Ondrusek M. E., Keller M. D., and

Guillard R. R. L.. 1990. Novel chlorophyll-related compounds in marine

phytoplankton: Distributions and geochemical implications. Energy and

Fuels. 4:653-657.

[67] Didyk, B. M., Simoneit B. R. T., Brassell S. C., and Eglinton G.. 1978.

Organic geochemical indicators of paleoenvironmental conditions of

sedimentation Nature. 272:216-222.

[68] Keely, B. J., Prowse W. G., and Maxwell J. R.. 1990. The Treibs

hypothesis: An evaluation based on structural studies. Energy and Fuels.

4:628-634.

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ABOUT AUTHORS

Prof. Dr. Ashraf Yehia El-Naggar

Prof. of Analytical and Petroleum Chemistry. He is erudite scholar and seasoned chemist scientist. He obtained his M. Sc degree and Ph. D. degree in analytical chemistry from Cairo University and Mansoura University, Egypt respectively. He obtained his Assistant Prof. and Prof. Degrees in analytical and petroleum chemistry from Egyptian Petroleum Research Institute (EPRI). He was a head of chromatographic Department and vice director of Central Analytical Lab., EPRI. Now he is Vice Director of chemistry Department, and head of Analytical Chemistry Division, Science Faculty, Taif University, Kingdom Saudi Arabia.

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Prof. Dr. Abd El-Aziz Mustafa El-Fadly

Prof. of Analytical and Petroleum Chemistry. Former Head of Chromatographic Separation Division and Former Director of

Analysis and Evaluation Department Egyptian Petroleum Research Institute.

-------------------------------------------------------------------------------------------- Prof. Dr Yasser Mohammed Moustafa

Prof. of Analytical and Petroleum Chemistry, Vice Director of Egyptian Petroleum Research Institute (EPRI), Director of Central Analytical Lab and Quality Manager of ISO IEC 17025. He has work team in environmental studies and instrumental analysis in petroleum field.

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Petroleum in View of its Classification, Assay and Analysis 101

Dr. Mohammed Abd El-salam Ebiad

Dr. of Analysis and evaluation department and central analytical lab. now he is responsible in GC labs, Egyptian Petroleum Research Institute. He was interisted in chromatographic separation in petroleum field and in catalysis areas. Bachelor's degree from Zagazig University, M.Sc. from Benha University and PhD in physicalChemistry from Mansoura University in 2009. He has many activities in thosefields, especially keen on integrating activities in the hydrogen production area

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PhD Student/ Eman Saied Abdullah Ibrahim She is an assistant researcher in Analytical and Petroleum Chemistry. She is a member at gas chromatogarphic division and central analytical lab, Egyptian Petroleum Research Institute. She received an M.Sc in petroleum chemistry from Al-Azhar University in 2009. Now she is finishing a PhD thesis in organic geochemistry under supervision of Prof. Dr Ashraf Yehia El-Naggar from Ain-Shams University.

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