Chapter One Petroleum Analysis

INTRODUCTION
Petroleum, rock oil, is the term used to describe a myriadhydrocarbonrich fluids that have accumulated in subterranean reservoirs. Petroleum
(also called crude oil) varies dramatically in color,odor,and flow properties
that reflect the diversity of its origin (Table 1.1).

Petroleum products are any petroleum-based products that can beobtained

by refining and comprise refinery gas, ethane ,liquefied petroleum gas
(LPG), naphtha, gasoline, aviation fuel,kerosene, diesel fuel, distillate fuel
oil, residual fuel oil, gas oil, lubricants,white oil, grease, wax, asphalt, as
well as coke.

Thefour fractional types into which petroleum is subdivided are

paraffins,olefins, naphthenes, and aromatics (PONA). Paraffinic
hydrocarbons i nclude both normal and branched alkanes, whereas olefins
refer to normaland branched alkenes that contain one or more double or
triple carbonbonds. Naphthene(not to be confused with naphthalene) is a
termspecific to the petroleum industry that refers to the saturated cyclic
hydrocarbons(cycloalkanes). Finally, the term aromaticsincludes all
hydrocarbonscontaining one or more rings of the benzenoid structure.

Properties ofPetroleum Productes -University of Technology-Chemical Engineering Department---Dr.Intisar H.

Table 1.1. Illustration of the Variation in Composition (Residuum Content) and

Properties (Specific Gravity and API Gravity) of Petroleum

Although not directly derived from composition, the terms light and
heavyor sweet and sour provide convenient terms for use in descriptions.
For example, light petroleum(often referred to as conventional petroleum)is
usually rich in low-boiling constituents and waxy molecules whereasheavy
petroleumcontains greater proportions of higher-boiling, morearomatic, and
heteroatom-containing (N-, O-, S-, and metal containing)constituents.
Heavy oilis more viscous than conventional petroleum andrequires
enhanced methods for recovery. Bitumen is near solid or solid andcannot be
recovered by enhanced oil recovery methods.
Conventional (light) petroleum is composed of hydrocarbons together
with smaller amounts of organic compounds of nitrogen, oxygen, and
sulfurand still smaller amounts of compounds containing metallic
constituents,particularly vanadium, nickel, iron, and copper. The processes
by whichpetroleum was formed dictate that petroleum composition will
vary and besite specific, thus leading to a wide variety of compositional
difference.
Thus the purely hydrocarbon content may be higher than 90% by weightfor
paraffinic petroleum and 50% by weight for heavy crude oil and muchlower
for tar sand bitumen. The non-hydrocarbon constituents are
usuallyconcentrated in the higher-boiling portions of the crude oil.The
Properties ofPetroleum Productes -University of Technology-Chemical Engineering Department---Dr.Intisar H.

carbon and hydrogen content is approximately constant from crude oil to

crude oil even though the amounts of the various hydrocarbon types and of
the individual isomers may vary widely. Thus the carbon content of various
types ofpetroleum is usually between 83% and 87% by weight and the
hydrogen content is in the range of 1114% by weight.
General aspects of petroleum quality (as a refinery feedstock) areassessed
by measurement of physical properties such as relative density(specific
gravity), refractive index, or viscosity, or by empirical tests such aspour
point or oxidation stability that are intended to relate to behavior in service.
In some cases the evaluation may include tests in mechanical rigsand
engines either in the laboratory or under actual operating conditions.
The most importantproperties of a whole crude oil are its boiling-point
distribution, its density (or API gravity), and its viscosity. The boiling-point
distribution, boilingprofile, or distillation assay gives the yield of the
various distillation cuts, and selected properties of the fractions are usually
determined (Table 1.2).

Properties ofPetroleum Productes -University of Technology-Chemical Engineering Department---Dr.Intisar H.

Thus knowledge of the composition of petroleum allows the

refinertooptimize the conversion of raw petroleum into high-value
products.
Petroleum is now the worlds main source of energy and
petrochemicalfeedstock. Originally, petroleum was distilled and sold as
fractions withdesirable physical properties. Today crude oil is sold in the
form of gasoline,solvents, diesel and jet fuel, heating oil, lubricant oils, and
asphalts, orit is converted to petrochemical feedstocks such as ethylene,
propylene, thebutenes, butadiene, and isoprene. These feedstocks are
important, becausethey form the basis for the plastics, elastomer, and
artificialfiber industries. Modern refining uses a sophisticated combination
of heat,catalyst, and hydrogen to rearrange the petroleum molecules into
theseproducts. Conversion processes include coking, hydro-cracking, and
catalyticcracking to break large molecules into smaller fractions; hydrotreating toreduce heteroatom and aromatics, creating environmentally
acceptableproducts; and isomerization and reforming to rearrange
molecules intothose with high value, e.g., gasoline with a high octane
number.

2.Definition
Historically, physical properties such as boiling point, density (gravity),
odor, and viscosity have been used to describe oils. Petroleum may be
calledlight or heavy in reference to the amount of low-boiling constituents
andthe relative density (specific gravity). Likewise, odor is used to
distinguishbetween sweet (low sulfur) and sour (high sulfur) crude oil.
Viscosity indicatesthe ease of (or more correctly the resistance to) flow.
Petroleum is a naturally occurring mixture of hydrocarbons, generallyina
liquid state, which may also include compounds of sulfur, nitrogen,oxygen,
metals, and other elements.
In the crude state petroleum has minimal value, but when refined it
provideshigh-value liquid fuels, solvents, lubricants, and many other
products. The fuels derived from petroleum contribute approximatelyonethird to one-half of the total world energy supply and are used not onlyfor
transportation fuels (i.e., gasoline, diesel fuel, and aviation fuel,
amongothers) but also to heat buildings. Petroleum products have a wide
varietyof uses that vary from gaseous and liquid fuels to near-solid
machinerylubricants. In addition, the residue of many refinery
Properties ofPetroleum Productes -University of Technology-Chemical Engineering Department---Dr.Intisar H.

processes,asphaltis now a premium value product for highwaysurfaces,

roofing materials, and miscellaneous waterproofing uses.
Crude petroleum is a mixture of compounds boiling at different
temperaturesthat can be separated into a variety of different fractionsby
distillation .The terminology of these fractions has been bound by utility
and often bears little relationship to composition.
The molecular boundaries of petroleum cover a wide range of boilingpoints
and carbon numbers of hydrocarbon compounds and other
compoundscontaining nitrogen, oxygen, and sulfur, as well as metallic
(porphyrin)constituents. However, the actual boundaries of such a
petroleummap can only be arbitrarily defined in terms of boiling point and
carbonnumber (Fig. 1.1). In fact, petroleum is so diverse that materials from
differentsources exhibit different boundary limits, and for this reason
alone,it is not surprising that petroleum has been difficult to map in a
precisemanner.

Because there is a wide variation in the properties of crude petroleum,

the proportions in which the different constituents occur vary with
origin.Thus some crude oils have higherproportions of the lower-boiling
components and others (such as heavyoil and bitumen) have higher
proportions of higher-boiling components(asphaltic components and
residuum).

Properties ofPetroleum Productes -University of Technology-Chemical Engineering Department---Dr.Intisar H.

Heavy oil (heavy crude oil) is more viscous than conventional crude oil
and has a lower mobility in the reservoir but can be recovered through a
well from the reservoir by the application of secondary or enhanced
recoverymethods. On the other hand, tar sandincludes the several rock
typesthat contain an extremely viscous hydrocarbonaceous material that is
notrecoverable in its natural state by conventional oil well production
methodsincluding currently used enhanced recovery techniques
The term bitumen(also, on occasion, referred to as native asphalt and
extra heavy oil) includes a wide variety of reddish-brown to black
materialsof semisolid, viscous to brittle character that can exist in nature
with nomineral impurity or with mineral matter contents that exceed 50%
byweight. Bitumen is frequently found filling pores and crevices
ofsandstone,limestone in which case the organic and associatedmineral
matrix is known as rock asphalt.
On the basis of the definition of tar sand (above), bitumen is a naturally
occurringhydrocarbonaceous material that has little or no mobility under
reservoir conditions and which cannot be recovered through a well by
conventionaloil well production methods including currently used
enhancedrecovery techniques; current methods for bitumen recovery
involve mining.
Because of the immobility of the bitumen, the permeability of thedeposit is
low and passage of fluids through the deposit is prevented.Bitumen is a
high-boiling material with little, if any, material boiling below350C
(660F), and the boiling range approximates the boiling range ofan
atmospheric residuum and has a much lower proportion of
volatileconstituents than a conventional crude oil
Synthetic crude oilis the hydrocarbon liquid that is produced frombitumen,
by a variety of processes that involve thermal decomposition.
Synthetic crude oil (also referred to as syncrude) is a marketable and
transportableproduct that resembles conventional crude oil. Synthetic crude
oil,although it may be produced from one of the less conventional fossil
fuelsources, can be accepted into and refined by the usual refinery system.

it is preferable to subdivide petroleumand related materials into three major

subgroups (Table 1.3):
Properties ofPetroleum Productes -University of Technology-Chemical Engineering Department---Dr.Intisar H.

1. Materials that are of natural origin;

2. Materials that are manufactured; and
3. Materials that are integral fractions derived from the natural
ormanufactured products.

1.3. HISTORICAL PERSPECTIVES

The word petroleum, derived from the Latin petraand oleum,means literally
rock oil and refers to hydrocarbons that occur widelyin the sedimentary
rocks in the form of gases, liquids, semisolids, orsolids.
Theoccurrence and use of petroleum, petroleum derivatives(naphtha), heavy
oil, and bitumen is not new. The use of petroleumand its derivatives was
practiced in pre-common era times and is knownlargely through historical
use in many of the older civilizations.The petroleumindustry is essentially a
twentieth-century industry, but to understandthe evolution of the industry, it
is essential to have a brief understanding ofthe first uses of petroleum.
Briefly, petroleum and bitumen have been used for millennia. Forexample,
the TigrisEuphrates valley, in what is now Iraq, was inhabited asearly as
4000 B.C. by the people known as the Sumerians, who establishedone of
the first great cultures of the civilized world.The Sumerians devisedthe
cuneiform script, built the temple-towers known as ziggurats, and
developedan impressive code of law, literature, and mythology. As the
culturedeveloped, bitumen or asphalt was frequently used in construction
and inornamental works.Thus the history of analysis of petroleum and its
Properties ofPetroleum Productes -University of Technology-Chemical Engineering Department---Dr.Intisar H.

products can only besuggested to have started during the second half of the
nineteenth century.

Early references to petroleum and its derivatives occur in the

Bible,although by the time the various books of the Bible were
written, the useof petroleum and bitumen was established.
Investigations at archeological sites have confirmed the use of
petroleum and bitumen in antiquity for construction, mummification
decorative jewelry, waterproofing, as well as for medicinal use.
Many other references to bitumen are found throughout the Greek
and Roman empires, and from that time to the Middle Ages early
scientists (alchemists) frequently referred to the use of bitumen. In
the late fifteenth early sixteenth centuries bothChristopher
Columbus and Sir Walter Raleigh have been credited with the
discovery of the asphalt deposit on the island of Trinidad and
apparently used the material to caulk their ships. There was also an
interest in the thermal product of petroleum (nafta;naphtha) when it
was discovered that this material could be used as an illuminant and
as a supplement to asphalt incendiaries in warfare.

For example, in 1857 several aromatic hydrocarbons from Burma

petroleumwere identified by the formation of the barium salts of
benzenesulfonic acids followed by fractional crystallization. In addition, an
analyticaldistillation of petroleum was carried out in the early 1870s
(Further developments of the analytical chemistry of petroleum continued
throughout the century.

1.4. MODERN PERSPECTIVES

The modern petroleum industry began in 1859 with the discovery
andsubsequent commercialization of petroleum in Pennsylvania.During the
6,000 years of its use, the importance of petroleum has progressedfrom the
relatively simple use of asphalt from Mesopotamianseepage sites to the
present-day refining operations that yield a wide varietyof products and
Properties ofPetroleum Productes -University of Technology-Chemical Engineering Department---Dr.Intisar H.

petrochemicals . However, what is morepertinent to the industry is that

throughout the millennia in which petroleumhas been known and used, it is
only in the twentieth century thatattempts were made to formulate and
standardize petroleum analysis.
As the twentieth century progressed, there was increased emphasis and
reliance on instrumental approaches to petroleum analysis. In
particular,spectroscopic methods have risen to a level of importance that is
perhapsthe dream of those who first applied such methodology to petroleum
analysis.Potentiometric titration methods also evolved, and the procedures
havefound favor in the identification of functional types in petroleum and
itsfractions.

Spectrophotometers came into widespread use beginning around 1940,

and this led to wide application in petroleum analysis. Ultraviolet
absorptionspectroscopy, infrared spectroscopy, mass spectrometry,
emission spectroscopy,and nuclear magnetic resonance spectroscopy
continue to makemajor contributions to petroleum analysis.

Chromatography is another method that is utilized for the most part in

the separation of complex mixtures. Ion exchange materials, long known
inthe form of naturally occurring silicates, were used in the earliest types
ofregenerative water softeners. Gas chromatography, or vapor-phase
chromatography,found ready applications in the identification of the
individualconstituents of petroleum. It is still extremely valuable in the
analysisof hydrocarbon mixtures of high volatility and has become an
importantanalytical tool in the petroleum industry. With the development of
hightemperaturecolumns the technique has been extended to mixtures oflow
volatility, such as gas oils and some residua.

1.5. ANALYSIS AND SPECIFICATIONS

Petroleum exhibits wide variations in composition and properties, and
theseoccur not only in petroleum from different fields but also in oils taken
fromdifferent production depths in the same well. Historically, physical
propertiessuch as boiling point, density (gravity), and viscosity have been
Properties ofPetroleum Productes -University of Technology-Chemical Engineering Department---Dr.Intisar H.

used todescribe petroleum, but the needs for analysis are even more
extensive(Table 1.4).

*
Conradson carbon residue or microcarbon residue.

Because of the differences in petroleum composition, the importance ofthe

correct sampling of crude oil that contains light hydrocarbons cannotbe
overestimated. Properties such as specific gravity, distillation profile,vapor
pressure, hydrogen sulfide content, and octane number of gasolineare
affected by the light hydrocarbon content so that suitable cooling orpressure
sampling methods must be used and care taken during the
subsequenthandling of the oil to avoid the loss of any volatile constituents.
Inaddition, adequate records of the circumstances and conditions during
samplingmust be made. For example, sampling from oil field separators,
thetemperatures and pressures of the separation plant, and the
atmospherictemperature 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 thesampling
protocols that were used to obtain the sample. Without strictsampling
protocols, variation and loss of accuracy (or precision) must beanticipated.
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For example, correct sampling of the product in storage orcarrier tanks is

important to obtain a representative sample for thelaboratory tests that are
essential in converting measured quantities to the
standard volume.
Elemental analyses of petroleum show that it contains mainly carbonand
hydrogen. Nitrogen, oxygen, and sulfur (heteroelements) are presentin
smaller amounts, and trace elements such as vanadium, nickel, etc, arealso
present. Of the heteroelements, sulfur is the most important. The mixture of
hydrocarbons is highly complex. Paraffinic, naphthenic, andaromatic
structures can occur in the same molecule, and the complexityincreases
with boiling range. The attempted classification of crude oils in terms of
these three main structural types has proved inadequate.
In the main, the refiner is not concernedwith the actual chemical nature of
the material but in methods ofanalysis that would provide information
sufficient to assess the potentialquality of the oil, to supply preliminary
engineering data, and also to indicatewhether any difficulties might arise in
handling, refining, or transportingpetroleum or its products. Such
information may be obtained in one oftwo ways:
1. Preliminary assay-inspection data.
2. A full assay involving the preparation of a true boiling point curveand the
analysis of fractions and product blends throughout the fullrange of the
crude oil.
The preliminary assay provides general data on the oil and is based
onsimple tests such as distillation range, water content, specific gravity,
andsulfur content that enable desirable or undesirable features to be
noted.This form of assay requires only a small quantity of sample and is
thereforeparticularly useful for the characterization of oil field samples
producedfrom cores, drill stem tests, or seepages.
A fullassay 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
thestraight-run products, covering light hydrocarbons, light, middle, and
heavydistillate, lubricants, residual fuel oil, and residuum. Often, the
middleground is reached between the preliminary assay and the full assay,
but therequirements may also be feedstock dependent (Table 1.4).
A feedstock specification or product specification provides the data that
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give adequate control of feedstock behavior in a refinery or product

quality.Thus a specification offers the luxury of predictability of feedstock
behaviorin a refinery or predictability of product quality (therefore,
productbehavior) relative to market demand. Ultimately, feedstock behavior
and/orproduct quality is judged by an assessment of performance. And it is
performancethat is the ultimate criterion of quality. It is therefore
necessaryto determine those properties, the values of which can be
established preciselyand relatively simply by inspection tests in a control
laboratory, thatcorrelate closely with the important performance properties.
Sometimes the inspection tests attempt to measure these properties,
forexample, the carbon residue of a feedstock that is an approximation ofthe
amount of the thermal coke that will be formed during refining or aresearch
octane number test devised to measure performance of motor fuel.
In fact, the efficiency of a specification should be judged by the extentto
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; and
5. Offer rapid response to refinery and laboratory demands.
Petroleum analysis has been greatly augmented in recent years by
applicationof a wide variety of instrumental techniques to studies of the
hydro-petroleum analysiscarbon composition of crude oils and their
products. Before this, hydrocarbon type analyses (percent
paraffin's,naphthenic, olefins, and aromatics) were derived from
correlations basedon physical data. The advent of instrumental techniques
has led to twomajor developments:
1. Individual component analysis;
2. The variouscompound types that occur in the higher-boiling ranges of
petroleumdistillates.
Of these instrumental techniques, gas/liquid chromatography and mass
spectrometry are the most important in providing the hydrocarbon
compositiondata in crude oil assay work. By gas chromatographic analysis,
itis now possible to determine routinely the individual methane (CH4)
toheptane (C7H16) hydrocarbons and the individual aromatics that boil
below165C (330F) and also obtain a complete normal paraffin
distribution upto C50. In addition, with a microcoulometric detector specific
to sulfur, thesulfur compound distribution can be obtained throughout the
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distillaterange. Gas chromatographic analysis can also be used to provide

simulatedtrue boiling point (TBP) curves, and developments in preparative
scalegas/liquid chromatography have made possible the preparation of
fractionsin quantities sufficient not only for extensive spectrometric
analyses butalso for the normal inspection type tests to be undertaken.
Mass spectrometry offers a very rapid method for obtaining
hydrocarbontype analyses on a wide range of fractions up to and including
heavygas oils.The information obtained on a routine basis subdivides the
hydrocarbonsinto the various groups. The technique can also be used
inconjunction with separation procedures such as gas/liquid
chromatography,molecular distillation, thermal diffusion, or selective
adsorption to providemore detailed analyses where necessary, even on
fractions in the lubricating oil range.
1.6. SAMPLING

The value of any product is judged by the characteristics of the sample

asdetermined by laboratory tests.The sample used for the test(s) must be
representative of the bulk material, and the type and cleanlinessof sample
containers are important: If the container is contaminated or ismade of
material that either reacts with the product or is a catalyst, the testresults
may be wrong.
Thus the importance of the correct sampling of any product destined
foranalysis should always be overemphasized. Incorrect sampling
protocolscan lead to erroneous analytical data from which performance of
theproduct in service cannot be accurately deduced. For example,
propertiessuch as specific gravity, distillation yield, vapor pressure,
hydrogen sulfidecontent, and octane number of the gasoline are affected by
the content oflow-boiling hydrocarbons so that suitable cooling or pressure
samplingmethods must be used and care must be taken during the
subsequent handlingof the sample to avoid the loss of any volatile
components. In addition,adequate records of the circumstances and
conditions during samplingmust be made; for example, in sampling from
storage tanks, the temperaturesand pressures of the separation plant and the
atmospheric temperaturewould be noted.
At the other end of the volatility scale, products that contain, or are
composedof, high-molecular-weight paraffin hydrocarbons (wax) that are
alsoin a solid state may require judicious heating (to dissolve the wax) and
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agitation(homogenization, to ensure thorough mixing) before sampling.

Ifroom-temperature sampling is the modus operandi and product
coolingcauses wax to precipitate, homogenization to ensure correct
sampling is alsonecessary.

Once the sampling procedure is accomplished, the sample containershould

be labeled immediately to indicate the product, time of sampling,location of
the sampling point, and any other information necessary for thesample
identification. And, if the samples were taken from different levelsof the
storage tank, the levels from which the samples were taken and theamounts
taken and mixed into the composite should be indicated on thesample
documentation.
So sampling records for any procedure must be complete andshould
include, but are not restricted to, information such as:
1. The precise (geographic or other) location (or site or refinery orprocess)
from which the sample was obtained.
2. The identification of the location (or site or refinery or process) byname.
3. The character of the bulk material (solid, liquid, or gas) at the timeof
sampling.

4. The protocols that were used to obtain the sample.

5. The date and the amount of sample that was originally placed
intostorage.
6. Any chemical analyses (elemental analyses, fractionation by
adsorbentsor by liquids, functional type analyses) that have been
determinedto date.
7. Any physical analyses (API gravity, viscosity, distillation profile)
thathave been determined to date.
8. The date of any such analyses included in items 4 and 5.
9.The methods used for analyses that were employed in items 5&6.
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10. The analysts who carried out the work in items 5 and 6.
11. 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.

1.7. MEASUREMENT
The predominant methods of measuring the properties of
petroleumproducts are covered by approximately seven test methods that
are used inthe determination of bulk quantities of liquid petroleum and its
products(ASTM D-96,ASTM D-287,ASTM D-1085,ASTM D-1086,ASTM
D-1087,ASTM D-1250, ASTM D-1298).

Testing for suspended water and sediment (ASTM D-96) is used

primarilywith fuel oils, where appreciable amounts of water and sediment
maycause fouling of facilities for handling the oil and give trouble in
burnermechanisms. Three standard methods are available for this
determination.The centrifuge method gives the total water and sediment
content of thesample by volume, the distillation method gives the water
only, volumetrically,and the extraction method gives the solid sediment in
percentage byweight.

The determination of density of specific gravity (ASTM D-287, ASTM

D-1298) in the measurement and calculation of volume of petroleum
productsis important because gravity is an index of the weight of a
measuredvolume of the product.Two scales are in use in the petroleum
industry, specificgravity and API gravity, the determination being made in
each case bymeans of a hydrometer of constant weight displacing a variable
volume ofoil.The reading obtained depends on both the gravity and the
temperatureof the oil.

Gauging petroleum products (ASTM D-1085, discontinued in 1996 but

still in use) involves the use of procedures for determining the liquid
contentsof tanks, ships and barges, tank cars, and tank trucks. Depth of
liquidis determined by gauging through specified hatches or by reading
gauge petroleum analysisglasses or other devices. There are two basic types
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of gauges, innage andoutage. The procedures used depend on the type of

tank to be gauged, itsequipment, and the gauging apparatus.

An innage gauge is the depth of liquid in a tank measured from the

surface of the liquid to the tank bottom or to a datum plate attached to the
shell or bottom.The innage gauge is used directly with the tank
calibrationtable and the temperature of the product to calculate the volume
of theproduct (ASTM D-1250). On the other hand, an outage gauge is the
distancebetween the surface of the product in the tank and the reference
pointabove the surface, which is usually located in the gauging hatch.The
outagegauge is used either directly or indirectly with the tank calibration
table andthe temperature of the product to calculate the volume of product.
Theamount of any free water and sediment in the bottom of the tank is
alsogauged so that corrections can be made when calculating the net
volumeof the crude oil or petroleum product.
The liquid levels of products that have a Reid vapor pressure of 40 lb or
more are generally determined by the use of gauge glasses, rotary or
sliptubegauges, tapes and bobs through pressure locks, or other types of
gauging equipment.The type of gauging equipment depends on the size
andtype of the pressure tank.
There are also procedures for determining the temperatures of petroleumand
its products when in a liquid state. Temperatures are determinedat specified
locations in tanks, ships and barges, tank cars, and tank trucks.
For a nonpressure tank, a temperature is obtained by lowering a tank
thermometerof proper range through the gauging hatch to the specified
liquidlevel.After the entire thermometer assembly has had time to attain the
temperatureof the product, the thermometer is withdrawn and read
quickly.This procedure is also used for low-pressure tanks equipped with
gauginghatches or standpipes and for any pressure tank that has a pressure
lock.For tanks equipped with thermometer wells, temperatures are obtained
byreading thermometers placed in the wells with their bulbs at the
desiredtank levels. If more than one temperature is determined, the
averagetemperature of the product is calculated from the observed
temperatures.Electrical-resistance thermometers are sometimes used to
determine bothaverage and spot temperatures.
In general, the volume received or delivered is calculated from the
observed gauge readings. Corrections are made for any free water and
sedimentas determined by the gauge of the water level in the tank.The
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resultantvolume is then corrected to the equivalent volume at 15.6C (60F)

byuse of the observed average temperature and the appropriate volume
correctiontable (ASTM D-1250).When necessary, a further correction is
madefor any suspended water and sediment that may be present in
materialssuch as crude petroleum and heavy fuel oils.
For the measurement of other petroleum products, a wide variety of testsis
available. In fact, approximately three hundred and fifty tests (ASTM,2000)
are used to determine the different properties of petroleum products.Each
test has its own limits of accuracy and precision that must be adheredto if
the data are to be accepted.

1.8. 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 accuracycan 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
isknown.

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PETROLEUM& PETROLEUM PRODUCT

Part -One-

2.1.1 Petroleum Definition:

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 (ASTM D-4175)
Inorganic sediment and water may alsobe present. Thus, for the purposes of
this text, a petroleum product is anyproduct that is manufactured during
petroleum refining and, as a consequence,petrochemical products are not
included in this definition or in thistext.
Attempts have been made to define or classify petroleum based onvarious
distillation properties when combined with another property suchas density.
It has been suggested that a crude should be called asphaltic ifthe
distillation residue contained less than 2% wax and paraffinic if it
containedmore than 5%. A division according to the chemical composition
ofthe 250300C (480570F) fraction has also been suggested (Table 2.1).

Difficulties arise in using such a classification in that in the fractions

boilingabove 200C (390F) the molecules can no longer be placed in one
groupbecause most of them are of a typically mixed nature. Purely
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naphthenic oraromatic molecules occur very seldom; cyclic compounds

generally containparaffinic side chains and often even aromatic and
naphthenic rings side byside. More direct chemical information is often
desirable and can be suppliedby means of the correlation index (CI).
The correlation index is useful in evaluating individual fractions from crude
oils. The CI scale is based upon straight-chain paraffins having a CI value
of 0 and benzene having a CI value of 100. The CI values are not
quantitative, but the lower the CI value, the greater the concentrations of
paraffin hydrocarbons in the fraction; and the higher the CI value, the
greater the concentrations of naphthenes and aromatics [3].
CI = 473.7d 456.8 + 48,640/K
whered is the specific gravity and K is the average boiling point of the
petroleum fraction as determined by the standard distillation method
(ASTM D-86, ASTM D-1160).
Another derived number, the UOP characterization factor, is also a
widely used method for defining petroleum; the Characterization Factor is
derived from the formula:
Kw=

whereTB is the average boiling point in degrees Rankine (F + 460) and dis
the specific gravity (60/60F).

The Watson characterization factor ranges from less than 10 for highly
aromatic materials to almost 15 for highly paraffinic compounds. Crude oils
showa narrower range of KW and vary from 10.5 for a highly naphthenic
crude to 12.9for a paraffinic base crude.

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Figure 2.1.Reference data for the correlation index

whered is the specific gravity and K is the average boiling point of the
petroleum fraction as determined by the standard distillation method
(ASTM D-86, ASTM D-1160).
Values for the index between 0 and 15 indicate a predominance of
paraffinichydrocarbons in the fraction. A value from 15 to 50 indicates
predominanceof either naphthenes or mixtures of paraffins, naphthenes,
andaromatics. An index value above 50 indicates a predominance of
aromaticspecies. However, it cannot be forgotten that the data used to
determinethe correlation index are average for the fraction of feedstock
under studyand may not truly represent all constituents of the feedstock,
especiallythose at both ends of a range of physical and chemical properties.
Another derived number, the UOP characterization factor, is also a
widely used method for defining petroleum; the Characterization Factor is
derived from the formula:
K =
whereTB is the average boiling point in degrees Rankine (F + 460) and dis
the specific gravity (60/60F). This factor has been shown to be additiveon
a weight basis. It was originally devised to show the thermal
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crackingcharacteristics of heavy oil. Thus, highly paraffinic oils haveK =

~12.513.0
and cyclic (naphthenic) oils have K = ~10.512.5.
Again, because of the use of average data and the output of a value that
falls (in this case) within a narrow range, it is questionable whether or not
this
characterization
factor
offers
realistic
or
reliable
information.Determiningwhether or not a feedstock is paraffinic is one
issue, but one mustask whether there is a real difference between feedstocks
when the characterizationfactor is 12.4 or 12.5 or even between feedstocks
having characterizationfactors of 12.4 and 13.0. As the complexity of
feedstocks
increases from petroleum to heavy oil and beyond to tar sand bitumen,
especially with the considerable overlap of compound types, there must
be serious questions about the reliability of the number derived by this
method.
2.1.2. Composition
In all of these attempts at a definition or classification of petroleum, it
mustbe remembered that petroleum exhibits wide variations in composition
andproperties, and these variations not only occur in petroleum from
differentfields but may also be manifested in petroleum taken from different
productiondepths in the same well. The mixture of hydrocarbons is
highlycomplex. Paraffinic, naphthenic, and aromatic structures can occur in
thesame molecule, and the complexity increases with boiling range of
thepetroleum fraction. In addition, petroleum varies in physical
appearancefrom a light-colored liquid to the more viscous heavy oil. The
near-solid orsolid bitumen that occurs in tar sand deposits is different from
petroleumand heavy oil, as evidenced by the respective methods of
recovery .
Elemental analysis of petroleum shows that the major constituents are
carbon and hydrogen with smaller amounts of sulfur (0.18% w/w),
nitrogen(0.11.0% w/w), and oxygen (0.13% w/w), and trace elements
such asvanadium, nickel, iron, and copper present at the part per million
(ppm)level. Of the non-hydrocarbon (heteroelements) elements, sulfur is
the mostabundant and often considered the most important by refiners.
However,nitrogen and the trace metals also have deleterious effects on
refinery catalystsand should not be discounted because of relative
abundance. Processunits with, for example, a capacity of 50,000 bbl/day
that are in operationcontinuously can soon reflect the presence of the trace
elements.The effectof oxygen, which also has an effect on refining
catalysts, has received somewhatless study than the other heteroelements
but remains equally importantin refining.
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Petroleum suitability for refining (to produce a slate of predetermined

products) (Table 2.2) is determined by application of a series of analytical
methods that provide information that is sufficient to assessthe potential
quality of the petroleum as a feedstock and also to indicatewhether any
difficulties might arise in handling, refining, or transportation.
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.

2.3. PETROLEUM ASSAY

An efficient assay is derived from a series of test data that give an
accuratedescription of petroleum quality and allow an indication of its
behaviorduring refining. The first step is, of course, to ensure adequate
(correct)sampling by use of the prescribed protocols (ASTM D-4057).
Thus analyses are performed to determine whether each batch of crudeoil
received at the refinery is suitable for refining purposes. The tests arealso
applied to determine whether there has been any contamination
duringwellhead recovery, storage, or transportation that may increase the
processingdifficulty (cost). The information required is generally crude
oildependent or specific to a particular refinery and is also a function of
refineryoperations and desired product slate.
To obtain the necessary information, two different analytical
schemes arecommonly used.These are (1) an inspection assay and
(2) a comprehensiveassay.
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Inspection assays usually involve determination of several key

bulkproperties of petroleum (e.g., API gravity, sulfur content, pour point,
and
distillation range) as a means of determining whether major changesin
characteristics have occurred since the last comprehensive assay was
performed.
For example, a more detailed inspection assay might consist of the
followingtests: 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 froma comprehensive assay provide an estimate of any changes that
haveoccurred in the crude oil that may be critical to refinery operations.
Inspectionassays 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 only performed
onlywhen a new field comes on stream, or when the inspection assay
indicatesthat significant changes in the composition of the crude oil have
occurred.Except for these circumstances, a comprehensive assay of a
particular crudeoil stream may not (unfortunately) be updated for several
years.
2.3.1. Carbon Residue, Asphaltene Content
The carbon residues of petroleum and petroleum products serve as an
indicationof the tendency of the sample to form carbonaceous deposits
(thermal coke) under the influence of heat.
Tests for Conradson carbon residue (ASTM D-189, IP 13),
Ramsbottomcarbon residue (ASTM D-524, IP 14), the microcarbon carbon
residue(ASTM D4530, IP 398), and asphaltene content (ASTM D-893,
ASTMD-2006, ASTM D-2007, ASTM D-3279, ASTM D-4124, ASTM D6560, IP143) are sometimes included in inspection data on petroleum.The
data givean indication of the amount of coke that will be formed during
thermalprocesses as well as an indication of the amount of high-boiling
constituentsin petroleum.
The determination of the carbon residueof petroleum or a petroleum
product is applicable to relatively nonvolatile samples that decompose on
distillation at atmospheric pressure. Samples that contain ash-forming
constituentswill have an erroneously high carbon residue, depending on
theamount of ash formed. All three methods are applicable to relatively
nonvolatilepetroleum products that partially decompose on distillation at
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atmospheric pressure. Crude oils having a low carbon residue may be

distilledto a specified residue with the carbon residue test of choice then
applied to that residue.
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 .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-boilinghydrocarbon such as n-pentane or n-heptane. For an extremely
viscoussample, a solvent such as toluene may be used before the addition of
thelow-boiling hydrocarbon but an additional amount of the
hydrocarbon(usually >30 volumes hydrocarbon per volume of solvent)
must be addedto compensate for the presence of the solvent. After a
specified time, theinsoluble material (the asphaltene fraction) is separated
(by filtration) anddried. The yield is reported as percentage (% w/w) of the
original sample.
2.3.2. Density (Specific Gravity)
It is necessary to understand the basic definitions that areused: (1)
densityis the mass of liquid per unit volume at 15C; (2) relativedensityis
the ratio of the mass of a given volume of liquid at 15C to themass 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 areusually
bought and sold on that basis or, if on a volume basis, then converted to
mass basis via density measurements.This property is almost termed as
density, relative density, gravity, and specific gravity, all terms
related to each other. Usually a hydrometer, pycnometer, or more
moderndigital density meter is used for the determination of density or
specificgravity.
Accurate determination of the density or specific gravity of crude oil is
necessary for the conversion of measured volumes to volumes at the
standardtemperature of 15.56C (60F) (ASTM D-1250, IP 200,
PetroleumMeasurement Tables). The specific gravity is also a factor
reflecting thequality of crude oils.
The accurate determination of the API gravity of petroleum and its
productsis necessary for the conversion of measured volumes to volumes at
thestandard temperature of 60F (15.56C). Gravity is a factor governing
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thequality of crude oils. However, the gravity of a petroleum product is

anuncertain indication of its quality. Correlated with other properties,
gravitycan be used to give approximate hydrocarbon composition and heat
of combustion.
This is usually accomplished though use of the API gravity, whichis
derived from the specific gravity:
API gravity (degrees) = (141.5/sp gr 60/60F) -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 oneof
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.
2.3.3. 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
equalityof the 300C (572F) residuum fraction. For example, the waxiness
or viscosityof this fraction gives an indication of the amount, types, and
qualityof 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 todetermine the aromatic or aliphatic character of petroleum. Although
notnecessarily the same as the wax content, correlative relationships can
bederived 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
havean important effect on safety and performance, especially in the case
offuels and solvents.The boiling range gives information on the
composition,the properties, and the behavior of petroleum and derived
products duringstorage and use. Volatility is the major determinant of the
tendency of ahydrocarbon mixture to produce potentially explosive vapors.
Severalmethods are available to define the distillation characteristics of
petroleumand its various petroleum products. In addition to these physical
methods,other test methods based on gas chromatography are also used to
derivethe boiling point distribution of a sample (ASTM D-2887, ASTM D2887).
Fractionation of the crude oil begins with a true boiling point (TBP)
distillationusing a fractionating column with an efficiency of 1418
theoreticalplates and operated at a reflux ratio of 5 :1 (ASTM D-2892).
TheTBP distillation may be used for all fractions up to a maximum cut
pointof about 350C atmospheric equivalent temperature (AET), but a
lowresidence time in the still (or reduced pressure) is needed to minimize
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cracking.It is often useful to extend the boiling point data to higher

temperaturesthan are possible in the fractionating distillation method
previously described,and for this purpose a vacuum distillation in a simple
still withno fractionating column (ASTM D-1160) can be carried out. This
distillation,which is done under fractionating conditions equivalent to one
theoreticalplate, allows the boiling point data to be extended to about
600C(1112F) with many crude oils. This method gives useful
comparative andreproducible 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: <15.5C (60F)
2. Gasoline (light naphtha), boiling range: l5.5149C (60300F)
3. Kerosene (medium naphtha), boiling range: 149232C (300450F)
4. Gas oil, boiling range: 232343C (450650F)
5. Light vacuum gas oil, boiling range: 343371C (650700F)
6. Heavy vacuum gas oil, boiling range: 371566C (7001050F)
7. Residuum, boiling range: >566C (1050F)
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
performedon the fractions.
A more recent test method (ASTM D-5236) is seeing increasing use
andappears to be the method of choice for crude assay vacuum
distillations.Wiped-wall or thin-film molecular stills can also be used to
separate thehigher-boiling fractions under conditions that minimize
cracking.
2.3.4. Light Hydrocarbons
The amount of the individual light hydrocarbons in petroleum (methane
tobutane 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
carriedout with a gas chromatographic method (ASTM D-2427).
2.3.5. Metallic Constituents
Petroleum, as recovered from the reservoir, contains metallic
constituentsbut also picks up metallic constituents during recovery,
transportation, andstorage. Even trace amounts of these metals can be
deleterious to refiningprocesses, especially processes in which catalysts are
used. Trace components,such as metallic constituents, can also produce
adverse effects inrefining either (1) by causing corrosion or (2) by affecting
the quality ofrefined products.
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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
themulti-element methods of determination using techniques such as
atomicabsorption 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
determinedby atomic absorption spectrophotometric methods (ASTM D5863, IP 285,IP 288, IP 465), wavelength-dispersive X-ray fluorescence
spectrometry (IP433), and inductively coupled plasma atomic

emissionspectrometry (ICPES).
2.3.6. Salt Content
The salt content of crude oil is highly variable and results principally
fromproduction 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
waterof 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,
leadingto fouling that requires expensive cleanup. More importantly,
duringflash vaporization of crude oil certain metallic salts can be
hydrolyzed tohydrochloric acid according to the following reactions:
2NaCl + H2O 2 HCl+ Na2O
MgCl2+ H2O 2 HCl + MgO
The hydrochloric acid evolved is extremely corrosive, necessitating the
injection of a basic compound, such as ammonia, into the overhead lines
tominimize corrosion damage. Salts and evolved acids can also
contaminateboth overhead and residual products, and certain metallic salts
can deactivatecatalysts.
Thus knowledge of the content of salt in crude oil is important indeciding
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 apolar
solvent is compared with that of a series of standard salt solutions in42
petroleum and petroleum productsthe same solvent (ASTM D-3230). In this
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method, the sample is dissolvedin a mixed solvent and placed in a test cell
consisting of a beaker and twoparallel stainless steel plates. An alternating
voltage is passed through theplates, and the salt content is obtained by
reference to a calibration curveof the relationship of salt content of known
mixtures to the current.
It is necessary, however, to use other methods, such
atomicabsorption,inductively coupled argon plasma emission

spectrophotometer, andion chromatography to determine the composition of

the salts present. Amethod involving application of extraction and
volumetric titration is alsoused (IP 77).

2.3.7. Sulfur
The sulfur content of petroleum is an important property and varies
within the rough limits 0.1% w/w to 3.0% w/w, and a sulfur contentup to
8.0% w/w has been noted for tar sand bitumen. Compounds containingthis
element are among the most undesirable constituents of petroleumbecause
they can give rise to plant corrosion and atmosphericpollution. Petroleum
can evolve hydrogen sulfide during distillation as wellas low-boiling sulfur
compounds.
Hydrogen sulfide may be evolved during the distillation process either
from free hydrogen sulfide in the feedstocks or because of lowtemperaturethermal decomposition of sulfur compounds; the latter is less
likely thanthe former. Generally, however, the sulfur compounds
concentrate in thedistillation residue, the volatile sulfur compounds in
thedistillates being removed by such processes as hydrofining andcaustic
washing.
The sulfur content of fuels obtained from petroleumresidua and the
atmospheric pollution arising from the use of these fuels isan important
factor in petroleum utilization, so that the increasing insistenceon a lowsulfur-content fuel oil has increased the value of low-sulfurpetroleum.
Sulfur compounds contribute to corrosion of refinery equipment and
poisoningof catalysts, cause corrosiveness in refined products, and
contributeto environmental pollution as a result of the combustion of fuel
products.Sulfur compounds may be present throughout the boiling range of
crude oilsalthough, as a rule, they are more abundant in the higher-boiling
fractions.
In some crude oils, thermally labile sulfur compounds candecomposeon
heating to produce hydrogen sulfide, which is corrosive and toxic.
A considerable number of tests are available to estimate the sulfur in
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petroleum or to study its effect on various products. Hydrogen sulfide

dispetroleumassay 43solved in petroleum is normally determined by
absorption of the hydrogensulfide in a suitable solution that is subsequently
analyzed chemically(Doctor method) (ASTM, D-4952, IP 30) or by the
formation of cadmiumsulfate (IP 103).
2.3.8. Viscosity and Pour Point
Viscosity and pour point determinations are performed principally to
ascertainthe handling (flow) characteristics of petroleum at low
temperatures. There are, however, some general relationships of crude oil
compositionthat can be derived from pour point and viscosity data.
Commonly, thelower the pour point of a crude oil the more aromatic it is,
and the higherthe pour point the more paraffinic it is.
Viscosity is usually determined at different temperatures (e.g.,
25C/77F,and 100C/212F) by measuring the time for a volume of liquid
to flowunder gravity through a calibrated glass capillary viscometer
(ASTMD-445).In the test, the time for a fixed volume of liquid to flow
under gravitythrough the capillary of a calibrated viscometer under a
reproducibledriving head and at a closely controlled temperature is
measured in seconds.The kinematic viscosity is the product of the measured
flow time and thecalibration constant of the viscometer. Conversion of the
kinematic viscosityin centistokes (cSt) at any temperature to Saybolt
Universal viscosity inSaybolt Universal seconds (SUS) at the same
temperature and for converting
kinematic viscosity in centistokes at 122 and 210F to
SayboltFurolviscosity in SayboltFurol seconds (SFS) at the same
temperatures (ASTMD-2161) is avaibale through formulae.
The viscosity index(ASTM D-2270, IP 226) is a widely used measureof the
variation in kinematic viscosity due to changes in the temperature
ofpetroleum between 40C and 100C (104F and 212F). For crude oils
ofsimilar kinematic viscosity, the higher the viscosity index the smaller is
theeffect of temperature on its kinematic viscosity. The accuracy of the
calculatedviscosity index is dependent only on the accuracy of the original
viscositydetermination.
The pour pointof petroleum is an index of the lowest temperature at
which the crude oil will flow under specified conditions.The maximum
andminimum pour point temperatures provide a temperature window
wherepetroleum, depending on its thermal history, might appear in the
liquid aswell as the solid state.The pour point data can be used to
supplement othermeasurements of cold flow behavior, and the data are
particularly usefulfor the screening of the effect of wax interaction
modifiers on the flowbehavior of petroleum.
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In any determination of the pour point, petroleum that contains wax

producesan irregular flow behavior when the wax begins to separate.
Suchpetroleum possesses viscosity relationships that are difficult to predict
inpipeline operation. In addition, some waxy petroleum is sensitive to
heattreatment that can also affect the viscosity characteristics. This
complexbehavior limits the value of viscosity and pour point tests on waxy
petroleum.However, laboratory pumpability tests (ASTM D-3245, IP 230)
areavailable that give an estimate of minimum handling temperature
andminimum line or storage temperature.
2.3.9. Water
Considerable importance is attached to the presence of water or sedimentin
petroleum because they lead to difficulties in the refinery, for
example,corrosion of equipment, uneven running on the distillation unit,
blockagesin heat exchangers, and adverse effects on product quality.
The water and sediment content of crude oil, like salt, results from
productionand transportation practices. Water, with its dissolved salts,
mayoccur as easily removable suspended droplets or as an emulsion. The
sedimentdispersed in crude oil may be comprised of inorganic minerals
fromthe production horizon or from drilling fluids and scale and rust
frompipelines and tanks used for oil transportation and storage. Usually
wateris present in far greater amounts than sediment, but, collectively, it
isunusual for them to exceed 1% of the crude oil on a delivered basis.
Likesalt, water and sediment can foul heaters, stills, and exchangers and can
contributeto corrosion and to deleterious product quality. Also, water
andsediment are principal components of the sludge that accumulates in
storage tanks and must be disposed of periodically in an environmentally
acceptable manner. 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.
Water may be found in the crude either in an emulsified form or in
largedroplets and can cause flooding of distillation units and excessive
accumulationof sludge in tanks. Refiners generally limit the quantity, and
althoughsteps are normally taken at the oil field to reduce the water content
as muchas possible, water may be introduced later during shipment. In any
form,water and sediment are highly undesirable in a refinery feedstock, and
therelevant tests involving distillation (ASTM D-95, ASTM D-4006, IP 74,
IP358), centrifuging (ASTM D-96,ASTM D-4007), extraction (ASTM D473,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.
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2.3.10. Wax Content

Petroleum with a high wax content presents difficulties in handling and
pumping as well as producing distillate and residual fuels of high pour
pointand lubricating oils that are costly to dewax.
All the standard methods for the determination of wax involve
precipitatingthe wax from solvents such as methylene chloride or acetone
underspecified conditions of solvent-to-oil ratio and temperature.
Measurementssuch as these give comparative results that are often useful in
characterizing the wax content of petroleum or for investigating factors
involved inflow problems.
On the other hand, 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
appearancepoint.

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