خصائص النفط والغاز

IVtUiUs
:acult>" of Petroleum & Mining Engineering

Department of Petroleum Refining Engineering
Oil & Gas Properties

Second Year
Lecture^
2015-2016
Definition of petroleum:
The term petroleum includes both oil and hydrocarbon gas. Petroleum is admixture of
hydrocarbons molecules and relatively small quantities of organic molecules containing
sulphur, oxygen, nitrogen, and some metals ^(e.g. iron, nickel, copper and vanadium).
^ y Petroleum-mayêxist in the solid, liquidôrjaseous statesêpendjng_iipo3ijb£_cjonditi
v P r e s s u r e m ^ t e m P e r a t u r e to which it is subjected.
ytîjy Liquid hydrocarbons are termed crude oil, to differentiate them from refined petroleum
products. The hydrocarbon gases include dry gas (methane) and the wet gases (ethane,
^ (~~ s propane, etc.). Condensates are hydrocarbons that are gaseous in the subsurface, but condense
"v^/ to liquid when they are cooled at the surface. The plastic hydrocarbons include asphalt and
related substances. Solid hydrocarbons include coal and kerogen.
/oS^ Natural__gas is defined as a mixture of hydrocarbons and varying quantities of
S^J ^ nonhydrocarbons that exists either in the gaseous phase or in solution with crude oil in
*$J^ natural underground reservoirs. \.
Natural gas is classified into dissolved, associated, andjionassociated gas. Dissolved gas is in
y solution in crude oil in the reservoir. Associated gas, commonly known as gas cap gas,
J overlies and is in contact with crude oil in the reservoir. Nonassociated gas is iBêservpir^N
that do not contain significant quantities of crude oil. Gases are classified as ary or Wet-^
according to the amount of liquid vapour that they contain. c— "
The chemistry of petroleum:

-'^Petroleum is a mixture of hydrocarbons and other organic compounds that together dictate its
chemical and physical properties. Hydrocarbons are molecules composed of hydrogen (H)
and carbon (C) bonded together. Petroleum also contains lesser quantities of organic
molecules that contain nitrogen (N), oxygen (O), sulphur (S), and metals (Fe, Ni, Cu, ...),
(Table 1).
The proportion of hydrocarbons in the mixture is highly variable and ranges from as much as
97% by weight in the lighter oils to as little as 50 % in the heavier oils and bitumen. The
proportion of chemical elements varies over narrow limits as follow:
U
r
The proportion of hydrocarbons in the mixture is highly variable and rangesfromas much
as 97% by weight in the lighter oils to as little as 50 % in the heavier oils and bitumen. The
proportion of chemical elements varies over narrow limits as follow:
Element Weight (%)
Carbon 83 - 87
Hydrogen 10-14
Sulfur 0.05 - 6
Oxygen 0.05-1.5
Nitrogen 0.1-2
Metals (Fe, Ni, Cu, V,...) <0.1
Table 1: The elementary composition of crude oil.
Thejjydrocarbons present in petroleum are classified into three general groups:

1- Paraffins or alkanes
. 2- Naphthenes or cycloparaffins
3- Aromatics
In addition, there is a fourth type/|d^m^,^&atis formed during processing by the
delrydrogenation of paraffins and naphthenes. *
1- Alkanes (paraffins)
Alkanes or paraffins are^jsarura^ or branched (jao))
^chains^ which contain only carboiijuidTylln^ the generm&aStt
/ j [ [ ^ ^ ^ ^ w h e r e n is me~whlrieimmb^^ They generally have from 1 to 60
carbon atoms per molecule.
The smallest molecules up to the formula C4H10 (butane) are gases ad
conditions (e.g., at the Earth's surface) of temperature and pressure. Liquid compounds at
4
room temperature range from C5H12 (pentane) to C16H34 (hexadecane). Larger molecules
have an increasing number of structural variations.
The simplest paraffin is methane, CH4, followed by the homologous series of ethane,
propane, ect. (Fig. 1).
H H H H H H H H H H CH,
I I I I I I I I I I I
H—C—H H—C—C—H H—C—C—C—H H—C—C—C—C —H CH,—CH—CH,
I I I I I I I I I I
H H H H H H H H H H
methane, CH 4 ethane, C->H6 propane. C,H S butane. C H
4 W isohutanc. C H
4 W
CH 3 CH3
CH3—CH2—CH2—CH2—CH3 CH-,—CH — C H 2 — CH 3 CH3—C—CH3
or H-fCHifcr-H CH,
j pcnlanc.CjHp isopenuwe. GjH,, neopemane. C 5 H,,
Figure 1: Chemical formula for alkanes (straight & branched chains), plus examples.
2- Naphthenes (cycloalkenes)
Nephthenes or cycloalkenes is the second major group of hydrocarbon found in crude oils.
This group has a ring structure, where the carbon atoms are linked in a ring, thereby reducing
the number of sites for bonding with hydrogen atoms (Fig. 2). The chemical formula for the
naphthenes is CnF£2n. Large naphthene molecules commonly have more than one ring. Some
related compounds have a series of rings with sraight-chain branches (Fig. 2). Unlike the
paraffins, all the naphthenes are liquid at normal temperatures and pressure. They make up
about 40% of both light and heavy crude oil.
Example of a typical Example of naphthene with same

srigte-ring naphthenic: chemical formula (C 0 H 5; ) but with
a different molecular structure:
f Methylcyclopentane (C 6 Hj;}
C«;iohesane
H H H
| | |
H - C - H
H— C — C — H
1
c
1 1
H - C - C - H C 1
I i
H H W /c\\- /c ^H
1 1
H H
\
H H H H
Figure 2: Naphthene, or ring, compounds have the chemical formula CnH2n.

3- Afomatics
Aromatics are unsaturated hydrocarbon ring compounds, which their molecular structure
is based on a ring of six carbon atoms. Benzene (C6H6) is the simplest compound (Fig. 3).
The simplest aromatics have a chemical formula CnH2n-6, but there are many complicated
compounds that combine the benzene, ring with naphthene and straight-chain branches to
produce a wide range of compounds. For example, toluene (C6H5CH3), in which one of the
hydrogen atoms has been substituted by a methlyl (CH3) branch chain (Fig. 3), is a common
constituent in aromatic crude oils.
Example o* simple Example of simple double-ring
aromatic compound: aromatic compound:
Senrene (C H ) g 6 Naphthalene (Cio Ha)
H H H H
i i
i i tt ii
c=c C-C
// ^
c c H-C C-H
\
c-c C= C
1 1H
H H-C
/ \
C-H
^ //
c-c
1 1
1 1
H H
Figure 3: Aromatic compounds with chemical formula CnHn. The simplest compound is
benzene (C6H6).
The aromatic hydrocarbons are liquid at normal temperatures and pressures. They are
present in relatively minor amounts (about 10%) in light oils, but increase in quantity to more
than 30% in heavy oils.
Uixrrcrshy of Mosul
Faculty of Petroleum & Mining Engineering
Department of Petroleum & Refining Engineering

Second Year
Lecture 2
Dr. Muneef Mahjoob Mohammed

2015-2016
Properties of crude oil
The physical and chemical properties of crude oils vary and are dependent on the
concentration of the various types of hydrocarbons and minor constituents present.
An accurate description of physical properties of crude oils is of a considerable
importance in the fields of both applied and theoretical science and especially in the solution
of petroleum reservoir engineering problems. Physical properties of primary interest in
petroleum engineering studies include:
• Crude oil gravity
• Specific gravity of the solution gas
• Oil density
• Gas solubility
• Crude oil viscosity
• Bubble-point pressure
• Oil formation volume factor
• Molecular weight
• Sulfur content
• Flash point
• Boiling point
• Pour point
• Aniline point
Data on most of these fluid properties are usually determined by laboratory experiments
performed on samples of actual reservoir fluids.
1- Crude oil density:
The crude oil density is defined as the mass of a unit volume of the crude at specified
pressure and temperature. It is usually expressed in pounds per cubic foot. The crude oil
density can be measured by using the following equation:
62.4 y„ +0.0136 Rsy:
where y„ = specific gravity of I he stock-lank oil

R s .= yas solubility. sci'/STB
Bo
p„ = oil density. Ib/IV1
2- Specific gravity
The crude oil density is defined as the mass of a unit volume of the crude at a specified
pressure and temperature. It is usually expressed in pounds per cubic foot.
The specific gravity of a crude oil is defined as the ratio of the density of the oil to that of
water. Both densities are measured at 60 °F and atmospheric pressure:
Yo = Po / Pw
Where:
Yo = specific gravity of the oil
po = density of the crude oil, lb/ft3
Pw = density of the water, lb/ft3
Oils with less than specific gravity 1.0 floats on water, whereas those with greater than
specific gravity 1.0 sinks in water. Majority of oils float on water. The density of the water is
approximately 62.4 lb/ft3.
3- API gravity
Although the density and specific gravity are used extensively in the petroleum industry,
the API (American Petroleum Institute) gravity is the preferred gravity scale. This gravity
scale is precisely related to the specific gravity by the following expression:
°API = 141.5 -131.5
T
The API gravities of crude oils usually range from 47° API for the lighter crude oils to 10°
API for the heavier asphaltic crude oils. Pure water has arbitrary API gravity of 10. Lighter
crude,are generally those with an API gravity over 40. Those with an API gravity below 40
are regarded as heavy.
There is an inverse relationship between API gravity and density; the higher the density the
lower the API gravity.
4- Gas solubility
tf The gas solubility Rs is defined as the number of standard cubic feet of gas that will dissolve
^3 in one stock-tank barrel of crude oil at a certain pressure and temperature. The solubility of a
natural gas in a crude oil is a strong function of the pressure, tempefature, APrgravity, and
'gas gravity.
The solubility increases with pressure until the saturation pressure is reached. At the
saturation pressure (bubble-point pressure) all the available gases are dissolved in the oil and
the gas solubility reaches its maximum value.
Rather than measuring the amount of gas that will dissolve in a given stock-tank crude oil as
the pressure is increased, it is customary to determine the amount of gas that will come out of
a sample of reservoir crude oil as pressure decreases.
A typical gas solubility curve, as a function of pressure for an undersaturated crude oil, is
shown in Figure 1. As the pressure is reduced from the initial reservoir pressure Pi to the
bubble-point pressure Pb, no gas evolves from the oil and consequently the gas solubility
remains constant at its maximum value of Rsb. Below the bubble-point pressure, the solution
gas is liberated and the value of Rs decreases with pressure.
r
CO
Pressure
Figure 1: Gas-solubility pressure diagram.

Standing (1981) introduced a mathematical formula for determining the gas solubility as a
function of pressure, gas specific gravity, API gravity, and system temperature.
I.204S
2
]
" / 11 \
Rs = yg P+ 1 . 4 10"
.vlX.2 /
wiih
x = O . O I 2 5 A P I - ().()()()o 1 ( T - 4 5 0 )
where t := i c n i p c r a i u r c . R
= system pressure . psia
V = solution gas specific gravity
5- Bubble-Point Pressure:
The bubble-point pressure (Pb) of a hydrocarbon system is defined as the highest pressure
at which a bubble of gas is first liberated from the oil.^This property can be measured
experirrfentally'Of by 'using the graphical arid mamematical correlations. These Correlations
are essentially based on the assumption that the bubble-point pressure is a strong function of
gas solubility Rs, gas gravity yg, oil gravity API, and temperature T.
6- Oil formation volume factor
The oil formation volume factor, B 0 , is defined as the ratio of the volume of oil ( plus the
gas m solution ) at the prevailing reservoir temperature and pressure to the volume of oil at
standard conditions.} B0 is always greater than or equal to unity. The oil formation volume
factor can be expressed mathematically as:
Where:
Bo: oil formation volume factor, bbl/STB
(V0)P,T: volume of oil underreservoir pressure P and Temperature T, bbl.
(V0)sc: volume of oil is measured under standard conditions, STB.
The relationship between the oil formation volume factor and pressure is illustrated in
Figure 2. As the pressure is reduced below the initial reservoir pressure Pi, the oil volume
increases due to the oil expansion. This behaviour results in an increase in the oil formation
volume factor and will continue until the bubble-point pressure is reached. At Pb, the oil
reaches its maximum expansion and consequently attains a maximum value of B0b for the oil
formation volume factor. As the pressure is reduced below Pb, volume of the oil and B0 are
decreased as the solution gas is liberated. When the pressure is reducgjL-to atmospheric
pressure and the temperature to 60°F, the value of B0 is equal to one.
NO
7- Crude oil viscosity.
The crude oil viscosity Is defined as the htema! resistance of the fluid to fiow.^The
viscosity is an important nhysical property that control and influences the flow of oil through
porous media and pipes. "
fhe_oii_yiscosityisa strong function of the temperature, pressure, oil gravity, gas gravity, and
I gas solubility. Accolutn^nrjThTpressure, me viscosity of crude oils can be classified into
a- Dead-oil viscosity J J>3 &

The dead-oil viscosity is defined as the viscosity of crude oil at atmospheric pressure (no
gas in solution) and system temperature.
b- Saturated-oil viscosity
The saturated (bubble-point)-oil viscosity is defined as the viscosity of the crude oil at the
bubble-point pressure and reservoir temperature.
c- Undersaturated-oil viscosity
The undersaturated-oil viscosity is defined as the viscosity of the crude oil at a pressure
above the bubble-point and reservoir temperature.
Estimating of the oil viscosity at pressure equal to or below the bubble-point pressure is a
two-step procedure:
Step 1: Calculate the viscosity of the oil without dissolved gas (dead oil), u0b, at the reservoir
temperature.
Step 2: Adjust the dead-oil viscosity to account for the effect of the gas solubility at the
pressure of interest.
At pressure greater than the bubble-point pressure of the crude oil, another adjustment
step, i.e., Step 3, should be made to the bubble-point oil viscosity, u0b, to account for the
compression and the degree of undersaturation in the reservoir. Several correlations are
widely used in estimating the oil viscosity in the above three steps.
7
Methods of calcination viscosity «f the dead 0JI
Several empirical methods are proposed to estimate the viscosity of the dead oil, including:
• Beai's correlation
• The Beggs-Robinson correlation
• Glaso's correlation
Beat's Correlation
From a total of 753 values for dead-oil viscosity at anil above lUO'F.
Beat (ls>46) developed a graphical correlation lor determining the viscos-
ity ol the dead oil as a function of temperature ami the API gravity of the
crude. .Standing ( ) expressed the proposed graphical correlation in a
mathematical relationship as follows:
V API A T - 2 6 0 J
witli
_ )()(<> 4.' + X . W A P h
where fi1Hl = viscosity of the dead oil as measured at 14.7 psia and
reservoir temperature, c p
T = temperature. R
The Beggs-Robinson Correlation K
B e g g s and Robinson (l°75) developed an empirical correlation lor

delemiiniiig the viscosity of the dead oil. T h e correlation originated from
analyzing 4Ml dead-oil viscosil) measurements, "ilk proposed relation
ship is expressed mathematically as follows:
pnd=K^-i (2-1171
where X = V (T - 4fM)r'
Y |= l() z
Z = 3.03J4 - 0.020J3 API
An average error o f - 0 . 0 4 ' ! with a standard deviation of l3.53 'V w a s
r
reported for the correlation when tested against the data used for its
development. Sutton and Farshad (l°S0) reported an error of 114.3'^
when the correlation was tested against 9 3 cases from the literature.
8
' t foist fijyiKjtJikKB ^*.?!sisis factor*.
B,
The total formation volume factor, denoted t is defined as the ratio of the total volume of
the hydrocarbon mixture (i.e. oil and gas, i f present),at the prevailing pressure and
temperature per unit volume of the stock-tank oil.
Because naturally occurring hydrocarbon systems usually exist in either one or two
phases, the term two-phase formation volume factor has become synonymous with the total
formation volume. v3-D^>f
Mathematically, Bt is defined by the following relationship:
(V ) , + (V ) T
(J - "'P-T g'p.T
' (V )
whore B, = lolal formal ion v o l u m e factor. b h l / S T B

( V0)p.t = v o l u m e of llie oil at p and T. bbl
(Vu'p.T = v o l u m e of the liberated g a s at p and T. bbl
(V„)sc = v o l u m e of the oil at standard c o n d i t i o n s . S T B
Above the bubble point pressure, no free gas exists and the expression is reduced to the
equation that describes the oil formation volume factor, that is:
(V ) _ + 0 (V ) _
B, v o ' p.T _ v o ' p,T _ g
9- Sulfur content:
Crude oil naturally contains sulphur compounds. Crudes are classified as sweet or sour
depending on their sulphur content. If a crude has less than 0.5% sulphur in it, it is considered
to be "sweet crude oil". If it has greater than 2.5% sulphur, it is "sour crude oil". A crude
with a sulphur content between these two endpoints is called "intermediate".
10- Aniline point:

The aniline point is defined as the lowest temperature at which an equal volume mixture of
the petroleum oil and aniline are miscible.)Since aniline is an aromatic compound, petroleum
fractions with high aromatic content will be miscible in aniline at ambient conditions.
9
r, if the oil has more paraffins, it will require a higher temperature and thus higher
i point in order to be miscible in aniline. This property is important for the specification
of diesel fuels.
5
11- Flash poinj:
The flash point of a liquid hydrocarbon is the lowest temperature at which sufficient vapours
are produced above the liquid. It is an important specification for gasoline and naphtha
related to safety in storage and transport in high temperature environments.
Flash point indicates the fire explosion potential of a fuel. A low flash point fuel is a higher
fire hazard.
12- Pour point:

QThe pour point is defined as the lowest temperature at which the oil will flow. It indicates
how_easyô£difficu^ It also indicates the
âTOnafiJcity~or tf^j^fjjniôr^^crudejil or the fraction. A lower pour point mjjnsjhat
the paraffin content is low.
13- Molecular weight:

The most suitable method for measuring the molecular weight is that based on freezing point
depression. Most crude oils and petroleum fractions have average molecular weights from
100 to 500.
University of Mosul
Second Year
Lectures 3 & 4
2015-2016
l
Properties of oil
14- Surface and interfacial tension
Surface tension is a measure of the force acting at a boundary between two phases.j I f the
boundary is between a liquid and a solid or between a liquid and a gas (air) the attractive
forces are referred to as surface tension, but the attractive forces between two immiscible
liquids are referred to as interfacial tension.
Temperature and molecular weight have a significant effecôn surface tension (table 1). For
example, in the normal hydrocarbc^jeries, a rise in temperature leads to a decrease in the
surface tension, but an increase in molecular weight increases the surface tension. The
surface tension of petroleum and petroleum products range between 24 - 38 dyn/cm, as
gasoline (26dyn/cm), kerosene (30dyn/cm), an(LJ.he lubricating fractions (34 dyn/cm).
However, it is generally acknowledged that nonhyarocarbon materials dissolved in the oil
reduce the surface tension. The effect is marked at low concentrations up to a critical value
beyond which further additions cause little change.
Temperature Surface Tension
°C °F dyn/cm mN/rn
21.1 70.0 35.3 35.3

23.3 74.0 34.7 34.7
30.0 86.0 30.1 30.1
43.3 110.0 27.3 27.3
51.7 125.0 28.0 28.0
65.6 150.0 25.4 25.4
73.9 165.0 22.5 22.5
82.2 180.0 21.0 21.0
87.8 190.0 18.9 18.9
95.6 204.0 20.0 20.0
104.0 219.0 19.2 19.2
123.9 255.0 18.2 18.2
Table 1: Effect of temperature on the surface tension of Athabasca bitumen.
Dynamic surface tension = 681.3/A'(1 - T}\ L 7 6 5 4 x 2-»250ji.2056

sg
Where K is the Watson characterization factor, (sg) is the specific gravity, and T is the
temperature in K.
Although petroleum products show little variation in surface tension, within a narrow range
the interfacial tension of petroleum, especially of petroleum products, against aqueous
solutions provides valuable information. The interfacial tension of petroleum is subject to the
same constraints as surface tension, that is, differences in composition, molecular weight, and
so on. When oil-water systems are involved, the pH of the aqueous phase influences the
tension at the interface; the change is small for highly refined oils, ,but increasing pH causes a
rapid decrease for poorly refined^contaminated, or slightly oxidized-oiis.
15- Metals content:
Heteratoms (nitrogen, oxygen, sulphur, and metals) are formed in every crude oil and the
concentrations have to be reduced to convert the oil to transportation fuel. The reason is that
if nitrogen and sulphur are present in the final fuel during combustion, nitrogen oxides (NO ) x
and sulphur oxides (SO ) form, respectively.

x
Heteroatoms do affect every aspect of refinhig. Sulfur is usually the most concentrated and is
. ^4^fairly easy to remove; many commerciafrataPysts ali¥avaIla¥Ie~tHat routinely remove 90% of
U the sulphur. Nitrogen is more difficult to remove than sulphur, and there are fewer catalysts
that are specific to nitrogen. Metals causlTpluHiculanjroblen^
used for sulphur and njtrojâjsnToyal as well as other processes such as catalytic cracking.
Thermal properties:
The volatility of a liquid or liquefied gas may be defined as its tendency to vaporize, that is, ^
to change from the liquid to the vapour or gaseous state^)Because one of the three essentials ^ J
for combustion in aflame is that the fuel be in the gaseous state, volatility is a primary
characteristic of liquid fuels.
The vaporizing tendencies of petroleum and petroleum products are the basis for the general
\ characterization of liquid petroleum fuels, such as liquefied petroleum gas, natural gaso;ine,
motor and aviation gasoline, naphtha, kerosene, gas oil, diesel fuel and fuel oil (ASTM
D2715).
For some purpose, it is necessary to have information on the initial stage of vaporization. To
supply this need, flash and fire, vapour pressure, and evaporation methods are available.
^ The flash point of petroleum or a petroleum product is the temperature to which the product
must be heated under specified conditions to give off sufficient vapour to form a mixture with
air that can be ignited momentarily by a specified flame (ASTM D56, D92, and D93).
y0f ^
The fire point is the temperature to which the product must be heated under the prescribed
// jJ conditions of the method to burn continuously when the mixture of vapour and air is ignited
, \ b y specified flame (ASTM.BQ2).
a
>ofê* (y
\jr From the viewpoint of safety, information about the flash point is of most significance at or
slightly above the maximum temperatures (30°C to 60°C, 86°F to 140°F) that may be
encountered in storage; transportation, and use of liquid petrojetrm products, in either closed
or open containers. In this temperature range, the relative fire and explosion hazard can be
estimated from the flash point. Flah points above 60°C (140°F) gradually lose their safety
significance until they become indirect measures of some other quality.
: , - ; /.
The flash point of petroleum products is also used to detect contamination. A substantially
) lower flash point than expected for a product is a reliable indicator that a product has become
, s . tn • contaminated with a more volatile product, such as gasoline. v •>'' - /
* A further aspect of volatility that, receives considerable attention is the vapour pressure of
petroleum and its constituent fractions. The vapour press^re^sjh^force exertea on the walls ^
of a closed container by the vaporised portion of a liquic^Conversely\t is the force that must
be exerted on the liquid to prevent it from vaporizing furtherjÂSTM D323). The vapour '^Zsigj )
pressure increaseswith temperaturejbr any given gasoline, liquefied petroleum gas, or other ^ _ ^ j \
product. The vapour pressure increases with temperature for any given gasoline, liquefied, r J
either a pure compound of a mixture of many compounds, equals 1 atm (14.7 psi, absolute) is
designated as the boiling point of the liquid.
In each homologous series of hydrocarbons, the boiling points increase wftn molecular
weight, and structure also has a marked influence since iHs a general rule that branched 7 \
paraffins isomers have lower boiling points than the corresponding «-alkane.
2-Liquefaction and solidification *^^^<~>Sb ~-*L> , ^ x
Petroleum and the majority of petroleum products areiliquids at ambient temperature, and
problems that may arise from solidification during normal use are not common. Nevertheless,
the melting point is a test (ASTM D87 and D127) that is widely used by suppliers of wax'and
by wax consumers; it is particularly applied to the highly paraffinic or crystalline waxes.
Quantitative prediction of the melting point of pure hydrocarbon is difficult, but the melting
point tends to increase qualitatively with the molecular weight and with symmetry of the
molecule. ~~
Unsubstituted and symmetrically substituted compounds (e.g. benzene, cyclohexane, and

naphthalene) melt at higher temperatures relative to the paraffin compounds of similar
molecular weight.
Unsaturation affects the melting point principally by its alteration of symmetry; thus ethane
(-172°C, - 278°F) and ethylene (-169.5°C, -273°F) differ only slightly, but the melting points
of cyclohexane (6.2°C, 21°F) and cyclohexane (-104°C, -155°F) contrast strongly.
Although the melting points of petrofeum and petroleum products are of limited usefulness,
except to estimate the purity or perhaps the composition of waxes, the reverse process,
)
solidification, has received attention in petroleum chemistry. Solidification of petroleum and

petroleum products has been differentiated into four categories, namely, freezing point,
congealing point, cloud point, and pour point. ^Vwi'
J
Petroleum becomes more or less a plastic solid when cooled to sufficientlyrlow temperature. ^~ , <
This is due to the congealing of the various hydrocarbons that constitute 'the oil^Jhe cloud
point of petroleum oil (is the temperature at which paraffin wax or other solidifiable
compounds present in the oil appear as a haze when the oil is chilled under definitely
prescribed conditions ÂSTM D2500 and ASTM D3117). As cooling is continued, all
petroleum oils become more and more viscous and flow becomes slower and slower. The
pour point of petroleum oil is the lowest temperature at which the oil pours or flows under
definitely prescribed conditions, when it is chilled without disturbance at a standard rate
(ASTMD97). . £)^)Pr-
The solidification characteristics of a petroleum product^depend on its grade or kind^For
grease, itre'Temperature of interest is that at which ffuiSity occurs, commonly known as the
dropping point. The dropping point dfgrease is the temperature at which the grease passes
from a plastic solid to a liquid state and begins to flow under the conditions of the test
(ASTM D566 and ASTM D2265). For another type of plastic solid, including petrolatum and
microcrystalline wax, both melting point and congealing point are of interest.
j j The melting point of wax is the temperature'at which the wax becomes sufficiently fluid to
^J- J drop from the thermometer. The con'geanng point is the temperature at which melted
petrolatum ceases to flow when allowed to cool under definitely prescribed conditions
(ASTM D938)?y*
For paraffin wax, the solidification temperature is of interest. The melting point of paraffin
wax is the temperature at which the melted paraffin wax begins to solidify. For pure
hydrocarbons, the solidification temperature is the fre^lSgôint, the temperature at which a
hydrocarbon passes from a liquid to a solid state (ASTM D1015 and ASTM D1016).
The cloud point of petroleum or a petroleum product is the temperature at which paraffin
wax or other solidifiable compounds present in the oil appear as a haze when the sample is
chilled under definitely prescribed conditions (ASTM D2500, ASTM D3117).
3- Carbon residue
Petroleum products are mixture of many compounds that differ^w^ddy in their physical and
chemical properties. Some of them^may be vaporized in the absence of air at atmospheric
pressure without leaving an "appreciable residue. Other non-volatile compounds leave a
^.carbonaceous residue when destructively distilled under such conditions. This residue is
^ known as carbon residue when determined in accordance with prescribed procedure.
There are two older methods for determining the carbon residue of a petroleum or petroleum
product: the Conradson method (ASTM D189) and the Ramsbottom method (ASTM D524).
Both are applicable to the relatively non-volatile portion of petroleum and petroleum
products, which partially decompose when distilled at a pressure of 1 atmosphere. However,
crude oil that contains ash-forming constituents will have high carbon residue by either
method, unless the ash is first removed from the oil.
J
4- Aniline point ""
The aniline point of a liquid was originally defined as the critical solution temperature of the
two liquids, that is, the minimum temperature at which they are miscible in all proportions.
The term now most generally applied to the temperature at which exactly equal parts of the
two liquids are miscible.
The aniline point is of considerable value in the characterization of petroleum products. For
oils r>f a giwnTypsHt i^^n.'r^Hightjy-wttfi molecjLlair
weight it increases rapidly with inixcasing paralflnic character.
5- Specific heat
Specific heat is defined as the quantity of heat required to raise a unit mass of material
through one degree of temperature (ASTM D2766). Specific heats are extremely important
"\ engineering quantities in refinery practice, because thev are used in all calculations on
heating andô^TnTg^petroleum products. Many measurements have been made on various
hydrocarbon materials^ but the data for most purposes may be summarized by the general
equation:
l/d (0.388 + 0.00045^
C is the specific heat at f¥ of an oil whose specific gravity 60/60°F is d; thus, specific heat
increases with temperature and decreases with specific gravity.
6- Laten heat
There are two properties that represent phase transformations: the laten heat of fusion and
the laten heat of vaporization. The laten heat of fusion, (defined as the quantity of heat
necessary to change a unit weight of solid to a liquid without any temperature change^For
hydrocarbos, laten heats of fusion commence at approximately 15 cal/g for methane, rising to
40 cal/g for octane, then gradually approaching a limiting value of 55 cal/g. Branched
paraffins usually have a lower laten heat of fusion than the normal isomers; paraffin wax has
a laten heat of fusion Jn the range 50 to 60 cal/g.
j The laten heat of vaporization,{defined as the amount of heat required to vaporize a unit
^weight of a liquid at its atmospheric boiling point^The laten heat of vaporizationât the
atmospheric boiling point generally increases with increasing molecular weight and, for the
nSoTtnaTparaffins, generally decreases with increasing temperature and pressure.
6
y
7- Enthalpy or heat content
Enthalpy is the heat energy necessary to bring a system from a reference state to a given state.
The usual reference temperature is 0°C (32°F). Enthalpy or heat content can be measured by
the following equation:
H = 1 /rf(0.388 + 0.000225/ - 12.65)

2
8- Thermal conductivity
The thermal conductivity K of hydrocarbons (in cgs units) is given by the equation:
K = 0.28 fd{l - 0.00054) x 10" 3
Where d is the specific gravity. The value for solid paraffin wax is about 0.0056, nearly
independent of temperature and wax type.
9- Heat of combustion
The gross heats of combustion of crude oil and its products are given with fair accuracy by
the equation:
Q= 12,400 -2100c/ 2
Where d is the 6O/6O0F specific gravity.
The range for crude oil is 10,000 to 11,600 cal/g and the heat of combustion of heavy oil and
tar sand bitumen is considerably higher. For gasoline, the heat of combustion is 11,000 to
11,500 cal/g and for kerosene (and diesel fuel) it falls in the range 10,500 to 11,200 cal/g.
Classification of petroleum
Crude petroleum is^^rr^tûreô^ cpmrûndj^boiling at different temperatures that can be

separated into a variety of different generic fractions by distillation. There is a wide variation
in the properties of crude petroleum. Some crude oils have higher proportions of the lower
boiling compounds and other (such as heavy oil and bitumen) have higher proportions of
higher boiling components (asphaltic components and residuum).
Since there is a wide variation in the proportions of crude petroleum, where 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 and related materials can be classified into three major classes
(Table 1):
1 - Materials that are of natural origin.
2- Materials that are manufactured.
3- Materials tnat&re integral fractions derived from natural or manufactured products.
1- Native materials
1.1 Petroleum
Petroleum and the equivalent term crude oil cover a wide assortment of materials consisting
of mixtures of hydrocarbons and other compounds containing variable amounts of sulphur,
nitrogen, and oxygen, which may vary ^ ^ j y n P ^ gravity and viscosity. Because
s e c c
petroleum is a mixture of widely varying constituents and proportions, its physical properties
also vary widely and the colour from colourless to black.
Natural Materials Derived Materials Manufactured Materials
Natural gas Saturates Synthetic crude oil

Petroleum Aromatics Distillates
Heavy oil Resins Lubricating oils
Bitumen" Asphaltenes Wax
Asphaltite Carbenes b Residuum
Asphaltoid Carboids" Asphalt
Ozocerite (natural wax) Coke
Kerogen Tar
Coal Pitch
Table 1: Subdivision of petroleum and similar materials into various subgroups.
Petroleum occurs underground, at various pressures depending on the depth. BeâusjLiiCjhe

pressure, it contains considerable natural gas in solution. Petroleum underground is much
O 8
more fluid than it is on the surface and is generally mobi]| underjeservoir conditions because
the elevated temperatures (the geothermal gradient) in subterranean formations decrease the
viscosity. The geothermal gradient is generally 25°C to 30°C/km.
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 froJKl series extends from
methane, which forms natural gas, through liquids that are refined into gasoline, to crystalline
waxes. A series of ring-shaped hydrocarbons, known as the naphthenes, range from volatile
liquids such as naphtha to high molecular weight substances isolated as the asphaltene
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.
Nonhydrocarbon constituents of petroleum include organic derivatives of nitrogen, oxygen,

sulphur, and the metals nickel and vanadium. Most of these impurities are removed during
refining.
Crude oil is transported to refineries by pipelines, which can often carry more than 500,000
barrels per day, or by ocean-going tankers. 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 to break the large
molecules of heavier gas oils into the smaller molecules that form the lighter, more valuable
naphtha fractions.
Reforming changes the structure of straight-chain paraffin molecules into branched-chain iso-
paraffins and ring-shaped aromatics. This process is widely used to raise the octane number
of gasolie obtained by distillation of paraffinic crude oils. , v.s i"rv » u 1
1.2 Heavy oil
There are 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 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
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. Heavy oils are
9
$ considered to be those crude oils that had gravity less than 20° API, generally falling into the
? API gravity range 10° to 15°.
Heavy oils have a much higher viscosity (and lower API gravity) than conventional
pptrnlftnm^ and primary recovery of these petroleum types usually requires thermal
stimulation of the reservoir. The generic term heavy oil is often applied to a crude oil that has
less than 20o API and usually, but not always, a sulphur content higher than 2% by weight.
Further, in contrast to conventional crude oils, heavy oils are darker in colour and may even
y&o •
The term heavy oil has also been used to describe both the heavy oils that require thermal
stimulation of recovery from the reservoir and the bitumen in bituminous sand formations
from which the heavy bituminous material is recovered by mining operation.
Extra heavy oils are materials that occur in the solid or near-solid state and are generally
incapable of free flow under reservoir conditions (e.g. bitumen).
1.3 Bitumen
The term bitumen (also referred to as native asphalt, and extra heavy oil) includes a wide
variety of radish browji to black materials of semisolid, viscous to bVrttle character that can
exist in nature with no rrfiHeral impurity or with mineral matter contents that exceed 50% by
weight. Bitumen is frequently found filling the pores and crevices of sandstone and
limestone, in which case the organic and associated mineral matrix is known as rock asphalt.
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 material boiling
below 350oC (660oF) and the boiling range approximates the boiling range of an
atmospheric residuum.
Tar sand have been defined as the several rock types that contain an extremely viscous
hydrocarbon which is not recoverable in its natural state by conventional oil well production
methods including currently used enhanced recovery techniques. The hydrocarbon-bearing
rocks are variously known as bitumen-rocks oil, impregnated rocks, oil sands, and rock
asphalt.
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 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.
10
1.4 Wax
Naturally occurring wax, often referred to as mineral wax, occurs as yellow to dark brown,
solid substance that is composed largely of paraffins. Fusion points vary from 6O0C (140oF)
to as 95oC (203oF). They are usually found associated with considerable mineral matter, as
filling in veins and fissssures or as an interstitial material in porous rocks. The similarity in
character of these native products is substantiated by the fact that, with minor exceptions
where local names have prevailed, the original term ozokerite (ozocerite) has served without
notable ambiguity for mineral wax deposits.
Ozokerite (ozocerite), from the Greek meaning odoriferous wax, is a naturally occurring
hydrocarbon material composed chiefly of soloid paraffins and cycloparaffins (i.e.,
hydrocarbons). Ozocerite usually occurs as stringers and veins that fill rock fractures in
tectonically disturbed areas. It is predominantly paraffinic material (containing up to 90%
nonnaromatic hydrocarbons) with a high content (40% to 50%) of normal or slightly
branched paraffins as well as cyclic paraffin derivatives. Ozocerite contains approximately
85% carbon, 14% hydrogen, and 0.3% each of sulphur and nitrogen and is, therefore,
predominantly a mixture of pure hydrocarbons; any nonhydrocarbon constituents are in the
minority. ^ .
Ozocerite is soluble in solvents that are commonly employed for the dissolution of petroleum
derivatives, e.g., toluene, benzene, carbon disulfide, chloroform, and ethyl ether.
1.5 Asphaltoid
Asphaltoids are a further group of brown to black, solid bituminous materials of which the
members are differentiated from the asphaltites by their infusibility and low solubility in
carbon disulfide.^These substances have also been designated asphaltic pyrobitumen, as^they^
<Z_J^-z& decompose on heating into bitumen-like materials. '
Pyrobitumen is a naturally occurring solid organic substance that is distinguishable from

bitumen by being infusible and insoluble. When heated, pyrobitumen generates, or transforms CPjpLL^L*
into, bitumen-like liquid and gaseous hydrocarbon compounds. Pyrobitumen may be either^,^^^. ^/yJ <
asphaltic or nonasphaltic. The asphaltic pyrobitumen, derived from petroleum, is relatively ** *

hard, and has a specific gravity below 1.25. fy^^/faêtf
\6 Bitumenous rock and Bituminous sand
Bituminous rock and bituminous sand are those formations in which the bituminous material
is found as a filling in veins and fissures in fractured rocks or impregnating relatively shallow
sand, sandstone, and limestone strata. The deposits contain as much as 20% bituminous
material, and i f the organic material in the rock matrix is bitumen, it is usual to refer to the
deposit as rock asphalt to distinguish it from bitumen that is relatively mineral free. A
11
standard test (ASTM, 2005a) is available for determining the bitumen content of various
mixtures with inorganic materials.
If the material is of the asphaltite-type or asphaltoid-type, the corresponding term, rock

asphaltite or rock ashaltoid, should be used. Bituminous rocks generally have a coarse,
porous structure, with the bituminous material in the voids.
A special class of bituminous rocks that has achieved some importance is the so-called oil
shale. These are argillaceous, laminated sediments of generally high organic content that can
be thermally decomposed to yield appreciable amounts of oil, commonly referred to as shale
oil. Oil shale does not yield shale oil without the application of high temperatures and the
ensuing thermal decomposition that is necessary to decompose the organic material (kerogen)
in the shale.
1.7 Natural gas:
Natural gas generally contains high proportions of methane (a single carbon hydrocarbon
compound, CH4) and some of the higher molecular weight higher paraffins (CnH2n+2)
generally containing up to six carbon atoms may also be present in small quantities (Table 2).
Name Formula Voi.%
Methane CH 4 >85
Ethane CaHg 3-8
Propane C H
3 8 1-5
Butane C HK)
4 1-2
Pentane" C5H12 15
Carbon dioxide C0 2 12
Hydrogen sulfide HS 2 1-2
Nitrogen N2 1-5
Helium He <0.5
Table 2: Constituents of natural gas.
There are several general definitions that have been applied to natural gas. 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 sulphide whereas sweet gas
contains very little hydrogen sulphide. Residue gas is natural gas from which the higher
molecular weight hydrocarbons have been extracted.^\p£*> \
To further define the term dry and wet in quantitative measures, the term dry natural gas
indicates that there is less than 0.1 gallon (1US gallon=264.2 m ) of gasoline vapour (higher
3
12
molecular weight paraffins) per 1000 ft (1 ft3=0.028 m ). The term wet natural gas indicates
3 3
that there are such paraffins present in the gas, in fact more than 0.1 gal / 1000 f t .
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! ~"
2- Manufactured materials
2.1 Wax
The term paraffin wax is restricted to the colorless, translucent, highly crystalline material
obtained from the light lubricating fractions of paraffinic crude oils (wax distillates). The
commercial products melt in the approximate range of 50 °C to 65 °C (120 °F to 150 °F).
The waxes are composed of fine crystals and contain, in addition to n-paraffins, appreciable
amounts of iso-paraffins and cyclic hydrocarbon compounds substituted with long-chain
alkyl groups.
2.2 Residuum (Residua)
A residuum is the residue obtained from petroleum after non-destructive distillation has
removed all the volatile materials. The temperature of the distillation is usually maintained
below 350 °C (660 °F). ^ , ^ ^
Residua are black, viscous materials and are obtained by distillation of a crude oil under
atmospheric "pressure or under reduced pressure (vacuum residuum). They may be liquid at
room temperature or almost solid depending on the nature of the crude oil. When a residuum
is obtained from a crude oil and thermal decomposition has commenced, it is more usual to
refer to this product as pitch.
The chemical composition of a residuum from an asphaltic crude oil is complex. Physical
methods of fractionation usually indicate high proportions of asphaltenes and resins, even in
amounts up to 50% (or higher) of the residuum. In addition, the presence of ash-forming
metallic constituents, including such organometallic compounds as those of vanadium and
nickel, is also a distinguishing feature of residua and the heavier oils.
, Asphalt is manufactured from petroleum and is a black or brown material that has a
^5 consistency varying from a viscous liquid to a glassy solid. When the asphalt is produced
simply by the distillation of an asphaltic crude oil, the product can be referred to as residual
asphalt or straight run asphalt.
13
Feedstock
n-Heptane
Silica or
Alumina
Insolubles
Carbon Disulfide (3) Benzene- (2) Benzene or (1) Heptane

or Pyridine Methanol Tolune
Carboids Resins
(Insolubles) (Peters)
Figure 1: Simplified representation of the fractionation of petroleum.
3.2 Resins and oils
The portion of petroleum that is soluble in, for example, pentane or heptanes is often reffered
to as maltenes (malthenes). A more strongly adsorbed, red to brown semisolid material
known as resins remains on the adsorbent until desorbed by a solvent such as pyridine or a
benzene / methanol mixed solvent (Figure 1). The oil fraction can be further subdivided into
\
an aromatics fraction and a saturates faction.
The resin fraction and the oil (maltenes) fraction have also been referred to collectively as
petrolenes. In the petroleum chemistry, the term petrolenes may be applied to that part of the
n-pentane-soluble (or n-heptane soluble) material that is low boiling_f<300 ° Q and can-be
distilled without thermal decompositiorK The term~maltenes~lsassigned to the pentane-
"s^HuljIeprjfrlon^^ isTelatively high boiling (> 300 °C).
16
Asphalt softens when heated and is elastic under certain conditions. The mechanical
properties of asphalt are of particular significance when it is used as a binder or adhesive. The
principal application of asphalt is in road surfacing, which may be done in a variety of ways.
Other important applications of asphalt include canal and reservoir lining, dam facings, and
sea works. The asphalt so used may be a thin, sprayed membrane, covered with earth for
protection against weatTiermg and mechanical damage, or thicker surfaces, often including
riprap (crushed rock). Asphalt is also used for roofs, coatings, floor tiles, soundproofing,
water proofing, and other building-construction elements and in a number of industrial
products, such as batteries.
2.4 Tar and pitch
Tar is a product of the destructive distillation of many bituminous or other organic materials
and is a brown to black, oily, viscous liquid to semisolid material. Tar is most commonly
produced from bituminous coal and is generally understood to refer to the product from coal,
although it is advisable to specify coal tar if there is possibility of ambiguity.
The most important factor in determining the yield and character of the coal tar is the
carbonizing temperature. Three general ranges are recognised, and the products have
j\ acquired the designations:
7 ^ Low - temperature tar (approximately 450 °C to 700 °C).
Mid - temperature tar (approximately 700 °C to 900 °C).
High - temperature tar (approximately 900 °C to 1200 °C).
Tar released during the early stages of the decomposition of the organic material is called
^ primary tar since it represents a product that has been recovered without the secondary
J alteration that results from prolonged residenceôf the vapour in the heated zone. The residue
left following removal of the heavy oil, or^distilfcfte^ is pitch which is a black, hard, and
highly ductile material. In the chemical-process industries, pitch is the black or dark brown
residue obtained by distilling coal tar, wood tar, fats, fatty acids, or fatty oils.
^Coal tar pitch is a soft to hard and brittle substance containing chiefly aromatic resinous
/compounds along with aromatic and other hydrocarbons and their derivatives. It is used
chiefly as road tar, in waterproofing roofs and other structures, and to make electrodes. Wood
^,tar pitch is a bright, lustrous containing resin acids. It is used in the manufacture of plastics
and insulating materials and in caulking seams. Pitch derived from fats, fatty acids, or fatty
oils by distillation is usually a soft substance contains polymers and decomposition products.
It is used chiefly in varnishes and paints and in floor coverings.
Coke is the solid carbonaceous material produced from petroleum during thermal processing.
It is often characterised by its high carbon content (95%) and a honeycomb type of
appearance. The colour varies from gray to black, and the material is insoluble in organic
solvents.
2.6 Synthetic.crude oil:
Coal, oil shale, bitumen, and heavy oil can be upgraded through thermal decomposition by a
variety of processes to produce a marketable and transportable product. These products vary
\ in nature, but the principal product is a hydrocarbon that resembles conventional crude oil:
^ hence the use of the terms synthetic crude oil and syncrude. The synthetic crude oil can
actually be refined by the usual refinery system.
By comparison, the unrefined synthetic crude oil from bitumen will generally resemble
petroleum more closely than either the synthetic crude oil from coal or the synthetic crude oil
from oil shale. Unrefined synthetic crude oil from coal can be identified by a high content of
phenolic compounds, whereas the unrefined synthetic crude oil from oil shale will contain
high proportions of nitrogen-containing compounds.
3- Derived materials: *
7
3.1 Asphaltens, carbenes, and carboids
Treatment of petroleum, residua, heavy oil, or bitumen with a low-boiling liquid hydrocarbon
results in the separation of brown to black powdery materials known as asphaltenes (Figure
1). Asphaltenes separated from petroleum, residua, heavy oil, and bitumen dissolve readily in
benzene, carbon disulfide, chloroform, or other chlorinated hydrocarbon solvents. However,
in the case of the higher molecular weight native materials or petroleum residua that have
been heated intensively or for prolonged periods, the n-pentane-insoluble or n-heptane-
insoluble fraction may not dissolve completely in the aforementioned solvents.
Definition of the asphaltene fraction has therefore been restricted to that of the n-pentane or
n-heptane insoluble material that dissolves in such solvents as benzene.
The benzene- or toluene-insoluble in carbon disulfide (or pyridine), but insoluble in benzene
is defined as carbenes. By different solvents that might be used in place of benzene, it is
advisable to define the carbenes (or carboids) by prefixing them with the name of the solvent
used for the separation.
15
Faculty o f Petroleum & M i n i n g Engineering
Department o f Petroleum & Refining Engineering
O i l & G a s Properties
Second Y e a r
Lectures 5 & 6
2015-2016
Classification of petroleum
1- Classification as a hydrocarbon resource:
Petroleum is referred to generically'as a fossil energy resource and is further classified as a ^ | -

hydrocarbon resource. The coal and o i l shale kerogen can be included in the category } ^1^,
c
hydrocarbon resources due to these two natural resources (coal and oil shale kerogen) w i l l c r x ^ 3
produce hydrocarbons on high-temperature processing.
1 > The hydrocarbon resources or fossil energy resources are divided into two classes, (Figure 1):
;^ k v
J - S\\- Naturally occurring hydrocarbons (petroleum, natural gas, and natural waxes).
"—'
^ \- Hydrocarbon sources (oil shale and coal) which may be made to generate hydrocarbons by
/ ^ the application o f conversion processes.
Both classes may be described as organic sediments.
f Gas Natural G a s
Naturally occurring
hydrocarbons
Associated G a s
Organic / Crude Oil
Liquid -i> Petroleum
Sodiments \ H e a v y Oil
T a r S a n d Bitumen
Lignite . C o n v e r s i o n required
Subbituminous > to p r o d u c e
Coal hydrocarbons
Bituminous
Us* r
V^SoIid i Anthracite '
Oil S h a l e
Figure 1: Classification o f the earth's organic sediments according to hydrocarbon

occurrence and production.
The classification o f petroleum and natural gas as naturally occurring mixtures o f

hydrocarbons occurs due to that they can be separated into their original hydrocarbon
~ coris^mi&^hst-tvivsT^t
L been altered by any applied processTTjie hydrocarbon constituents,
separated from petroleum and natural gas, are the hydrocarbon cbnstituentsjhat existed i n the
reservoir. Foj^tbe-coaLandJcejxtgen, the separation and thermal decomposition methods must
be applied before hydrocarbons are j^roGlIceQpThe hydrocarôlTproducts, generated by the
thermal process, are not naturally occurring hydrocarbons.
^ 2 - Oassificatioa by chemical composition:
Composition refers to the specific mixture o f chemical compounds that const&ute petrolewm.
The composition o f these materials is related t o the nature and mix o f the organic material
that generated the hydrocarbons. "
C o m p o s i t i o n of 2 5 ( f C - 3 0 0 ° C (480°F-570°F) F r a c t i o n
Paraffin Napbthene Aromatic Wax Asphalt
(%) (%) (%) <%) (%) C r u d e O i l Classification
> 4 6 , <61 >22, < 3 2 >12, < 2 5 <10 <6 Paraffin

>42, <45 >38, < 3 9 >16. < 2 0 <6 <6 Paraffin-naphthene
>15,<26 >61, <76 >8,<13 0 <6 Naphthene
>27, <35 >36, < 4 7 >26, < 3 3 <1 <I0 Paraffin-naphthene-aromatic
<8 >57, < 7 8 >20, < 2 5 <0.5 <20 A r o m a lie
Table 1: Classification by chemical composition
I n tiris type o f classification, the term "base" is used, where the residuum have taken after o i l
rj distillation and tested to divide the crudes into following terms:
a-"Asphaltic base:
I f the residuum contain 20% or less o f paraffinic series (after distillation), the crude oil is
classified as an asphaltic base.
b- Paraffinic-Asphaltic base (mixed base):
I f the percent o f paraffinic compounds varies from 2 0 % to 50% in the residuum, the crude
oil is expressed as paraffinic-asphahic base (mixed).
c- Paraffinic base:
t
I f the residuum with greater than 50% paraffin, the crude oil is classified as paraffinic base,
d- Hyb^^>ase:
In this case, the residuum is containing naphthenes and small percent of wax paraffin.
\
Fraction
2 5 0 * C - 2 7 0 C (48p°F-520°F)
o 275°C-300°C (52S°F-570°F)
APt G r a v i t y Type API Gravity Type Classification
>40.0 Paraffin >30.0 Paraffin Paraffin

>40.0 Paraffin 20.1-29.9 Intermediate Paraffin-intermediate
33.1-39.9 Intermediate" " >30.0 ParafTin mtermediate-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 Naphlhene-intermediate
<33.0 Naphthene <20.0 Naphthene Naphthene
>44.0 Paraffin <20.0 Naphthene Paraffin-naphthene
33.0 Naphthene >30.0 Paraffin Naphthene-paraffin
Table 2: Classification according to API gravity.
5- Sulfur content:
Sulfur content and API gravity are two properties which have great influence on the vaiue o f
crude o i l The sulphur content is expressed as percent sulphur by weight and varies from less
than 0.1 % to greater than 5%. The crude o i l is classified as a sweet o r sour based upon the
sulphur content. The c*ude o i l is considered sweet i f it contains less than 0.5% sulphur. I f the
sulphur content is greater than 0.5%, the crude o i l is classified as a sour.
6- Carbon distribution:
A method for the classification o f crude oils can only be efficient, first i f it indicates the
properties o f the various distillate fractions.
For the characterization o f the various fractions o f petroleum, the use o f the n.d.M method (n
= refractive index, d = density, M = molecular weight) is suggested. This method enables
determination o f the carbon distribution and thus indicates the percentage o f carbon in
aromatic structure (%C ), the percentage o f carbon in naphthene structure ( % C N ) , and the
A
percentage o f carbon in paraffin structure (%Cp).
Also, it is possible to extrapolate the carbon distribution to the gasoline range on the one hand
and to the residue on the other hand. A high value of % C A at 5 0 0 ° C (930 F)j3qilirjê-Tnt
o
usually indicates a high content o f asphaltenes in the residue, whereas a high value o f % C - a t r
5 0 0 C (930°F) boTTmgomt usually indicates a waxy residue.

— -v
5
7- U O P characterization
This factor is defined by the following formula:
K -"- fl'n) ' / d

1 3
(1)
Where T B is the average boiling point in degree Rankine (°F + 460) and d is the specific
gravity 60° / 60°F. It was originally devised to show the thermal cracking characteristics o f
heavy oils; thus, hjghiyparaffins oils have K in the range 12.5 to 13.0 and cycHcJnaphthene)^
oils have K in the rangel0.5 to 12.5.
Refining processes Z=u^«^W
Petrojeum refming is the sêparation,of p e ^ l e u m into fractions and the subsequent treating o f
these fractions to yield marketable products. Crude oil, once refined, yields three basic groups
o f products that are produced when it is broken down into cuts or fractions (Table 1).
The gas and gasoline cuts form the lower-boiling products and are usually more valuable than
the higher-boiling fractions and provide gas (liquefied petroleum gas), naphtha, aviation fuel,
motor fuel and feedstocks, for the petrochemical industry. Naphtha, a precursor to gasoline
and solvents, is extracted from both the light and middle range o f distillate cuts and is also
used as a feedstock for the petrochemical industry. The middle distillates refer to products
from the middle boiling range o f petroleum and include kerosene, diesel fuel, distillate fuel
oil, and light gas oil. Waxy distillate and lower boiling lubricating oils are sometimes
included in the middle distillates. The reminder o f the crude oil includes the higher-boiling
lubricating oils, gas oil, and residuum (the non-volatile fraction o f the crude oil). The
residuum can also produce heavy lubricating oils and waxes, but is more often used for
asphalt production.
J o convert crude oil into desired products in an economically feasible and environmentally
acceptable manner, refinery processes for crude oil are generally divided" into three
categories:
7S>
1- Separation processes, o f which distillation is the prime example.
2- Conversion process, o f which coking and catalytic cracking are prime examples.
3- Finishing processes, o f which hydrotreating to remove sulphur is a prime example.

Boiling Range*
Fraction °C °F
Light naphtha -1 150 30 300

Gasoline -1-180 30-355
Heavy naphtha " 1 5 0 - 2 0 5 300 400"
Kerosene 205-260 400-500
L i g h t gas o i l 260-315 400-600
H e a v y gas o i l 315-425 600-800
Lubricating oil >400 >750
V a c u u m gas o i l 425-600 800-1100
Residuum >510 >950
Table 1; Crude petroleum is a mixture o f compounds that can be separated into different
generic boiling fractions-
The simplest refinery configuration is the topping refinery, which is designed to prepare
feedstocks for petrochemical manufacture or for the production o f industrial fuels in remote
oil-produetion areas. The topping refinery consists o f tankage, a distillation unit, recovery
0? facilities for gases and light hydrocarbons, and the necessary utility systems (steam, power,
and water-treatment plants). Topping refineries produce large quantities o f unfinished oils
and are highly dependent on jpcal markets. /
t^sy r Jhe^yrelds ancTquality W refined petroleum products producedJ>y arjy„given o i l refinery

depends on the mixture o f crude oil used as feedstock and the^configuration j > f t n e refinery—
ilities. Light or sweet crude oil is generally more expensive and has great yields o f higher
Vf / val
value low-boiling products such naphtha, gasoline, jet fuel, kerosene, and diesel fuel. Heavy
sour crude oil is generally less expensive and produces greater yields o f lower value higher-
boiling products that must be converted into lower-boiling products.
The configuration o f refineries may vary from refinery to refinery. Some refineries may be
more oriented toward the production o f gasoline (large reforming and catalytic cracking),
whereas the configuration o f other refineries may be oriented toward the production o f
middle distillates such as jet fuel and gas oil.
I - Dewatering and desalting: v. »
The § ° ^ ^ f ^ i e dewatering and desalting is to remove water and the constituents o f the brine
that accompany the crude oil from the reservoir to the wellhead during recovery operations.
Petroleum is recovered from the reservoir mixed with a variety o f substances: gases, water,
and dirt (minerals).
7
Field separation, which occurs at a field site near the recovery operation, is the first attempt to
remove the gases, water, and dirt that accompany crude o i l coming from the ground. The
separator may be no more than a large vessel that gives a quieting zone for gravity separation
— -_— into three phases: gases, crude oiL and water containing entrained dirt.
Desalting is a water-washing operation perfolrmed at the production field and at the refinery
site for additional c r r i o T o i f i ^ n u p (Figure 1), 11' the pc.uvk.mu Hum the separators tsontains
water and dirt, water washing can remove much o f the water-soluble minerals and entrained
solids. I f these crude o i l contaminants are not removed, they can operating_jgQJ2leBas
during refinery processing, such as equipmenrplugging "and c o r r o ^ i t a g ^ w e l l as catalyst
deactivation] ~ " " S j ^ l J$J
Electrical
Process
power
v/ater
< 3
Desalted
Alternate
crude
Unrefined
crude Gravity
J> settler
Effluent
water
Heater Emulsifier
Figure 1: An electrostatic desalting unit."
2- Distillation:
Distillation refers complete operation in which heating, vaporization, condensation,

« /^fractionation and cooling are practical]) It is widely used method for separating mixtures based
r(rs ' on differences in the conditions required to change the phase o f components o f the mixture.
2.1 Atmospheric distillation:
The present-day petroleum distillation unit is a collection o f distillation units (Figure 2).
8
Gas
i G a s (butane and fighter)
Gasoline flight naphtha)
Gas Heavy naphtha

separator
0 c
~= o Kerosene
a> ~
JC. as
CL C
Gasoline •*- Light gas oil
§1 Heavy gas oil

1 2
Desaiter
WW Residuum
Furnace
b-
Pump
-* Crude oil
Figure 2: A n atmospheric distillation unit.
2.2 Vacuum distillation:
Vacuum distillation evolved because o f the need to separate the less volatile products, such as
h^catjng^jalsT-Ji^^ productsjo^
cracking_conditions. When the feedstock is required for the manufacture o f lubricating oils,
further fractionation without cracking is desirable and this can be achieved by distillation
under vacuum conditions.
Operation conditions for vacuum distillation (Figure 3) are usually 50 to 100 mm o f mercury
(atmospheric pressure = 760 mm o f mercury). In order to minimize large fluctuations in
pressure in the vacuum tower, the units are necessaryôTaT
atmospheric limfs; ~
9
T o vacuum system
Vacuum
g a s oil
li
si Lubricating oils
>
Residuum
A/VW Vacuum
residuum
Furnace
Figure 3: A vacuum distillation unit.
hernial methods:
3,1 Thermal cracking
One o f the earliest conversion processes used in the petroleum industry^ is the thermal
decomposition o f higher-boiling materials mtoJmver-boHing products^ This process is known
âsTêffHar-eracking. The heavier oils producedby crackln^reTIglvtand heavy oils as well as
a residual oil which could also be used as heavy fuel oil. Gas oils from catalytic cracking
were suitable for domestic and industrial fuel oils or as diesel fuels when blended with
straiglit-run gas oils.
The majority o f the thermal cracking processes use temperatures o f 4 5 5 ° C to 5 4 0 ° C and

pressures o f 100 to 1000 psi.
10
7
12 Visbreaking
Visbreaking (viscosity breaking) is essentially a process was initially introduced as a mild

thermal cracking operation that could be used to reduce the viscosity o f residua to allow the
products to meet fuel o i l specificationZ)Altetnatively, the visbroken residua could be blended
. withlighter product oils to produce fuel oils o f acceptable viscosity. „ _ _.„
:
In a typical visbreaking operation (Figure 4), a crude o i l residuum is passed through a

furnace where it is heated to a temperature o f 480°C, under an outlet pressure o f about 100
psi.
Gas +
gasoline
u
o
4J Gas o i
rd
C
O
SQiisn.cn -ri
-U
U
fl3
u
InternaSp
for reducing — u V
M
backmixing m
o
Cracked c
Furnace visbroke
residue
Feed
Figure 4 : A soaker visbreaker.
The heating coils in the furnace are arranged to provide a soaking section o f low heat density,
where the charge remains until the visbreaking reactions are completed and the cracked
products are then passed into a flash-distillation chamber. The overhead material from this
chamber is then fractionated to produce a low-qualify gasoline as an overhead product and
light gas oil as bottom.
11
University of Mosul

A A,
Second Year
Lecture 7
2015-2016
i
3- Thermal methods:
3.1 Thermal cracking
3.2 Visbreaking
3.3 Coking
Coking is a thermal process for the continuous conversion of heavy, low-grade oils into
lighter products. Unlike visbreaking, coking involves complete thermal conversion of the
feedstock into volatile products and coke. The feedstock is typically a residuum and the
products are gases, naphtha, fuel oil, gas oil, and coke. J ^ J ^ J^P^J^^J-^K^^
4- Catalytic methods
4.1 Catalyst cracking:
The catalytic crackingJs^baîcally the same as thermal cracking, but differs by the use of a
catalyst, which is not consumed in the process, and directs the course of the cracking
reactions to produce more of the desired higher-octane hydrocarbon products. r>U tS^. -îS (f"" 0
Catalytic ci^kirighas a number ot advantages over thermal cracking:
a-The gasoline produced has a higher octane number. ,xj6^js>
b- The csjalytically cracked gasoline consists largely of iso-paraffins and aromatfcs, which
have high octane numbers and greater quantities in thermally cracked gasoline.
c- Sulfur content of catalytically cracked gasoline is lower than in thermally cracked gasoline.
d- Catalytic cracking produces less heavy residual or tar and more of the useful gas oils than
does thermal cracking.
The catalytic cracking involves contacting a gas oil fraction with an active catalyst under
suitable conditions of temperature, pressure, and residence time, so that a substantial part
(>50%) of the gas oil is converted into gasoline and lower-boiling products, usually in a
single-pass operation.
The cracking of crude oil fractions occurs over many types of catalytic materials, but high
yields of desirable products are obtained with hydrated aluminium silicates. The catalysts are
porous and highly adsorptive and their performance is affected markedly by the method of
preparation.
2
5- Hydroprocesses:
The use of hydrogen in thermal process is perhaps the single most significant advance in
refining technology during the twentieth century. The process uses the principle that the
presence of hydrogen during a thermal reaction ofjyjetroleum feedstock will terminate many
o£tiiejcok^formuTg7reactions and enhance tKe yields of the lower-boiling components such
as gasoline, kerosene and jet fuel. ' ~ " ~
Hydrogenation processes for the conversion of petroleum fractions and petroleum products
may be classified as destructive and noH^de^nfctive. Destructive hydrogenation is
characterised by the conversion of the higher molecular weight constituents in a feedstock to
lower-boiling products. Nondestructive is .generally used for the purpose of improving
product quality without appreciable^ alterafTon of the boiling range. Mild processing
conditions are employed so that only the more unstable materials are attacked. Nitrogen,
sulphur, and oxygen compounds undergo reaction with the hydrogen to remove ammonia,
hydrogen sulphide, and water, respectively.
Hydrotreating is carried out by charging the feed to the reactor, together with hydrogen in the
presence of catalysts, (Figure 1). The temperature employed is in the range of 260°C to
345°C, while the hydrogen pressure is about 500 to 1000 psi.
Hydrofining is a process that can be applied to lubricating oils, naphtha, and gas oils. The
feedstock is heated in a furnace and passed with hydrogen through a reactor containing a
suitable metal oxide catalyst, such as cobalt. Reactor operating conditions range from 205°C
to 425°C, and from 50 to 800 psi, and depend on the kmuOTreedôck and the degree of
treating required. Higher-boiling feedstocks, high sulphur content, and maximum sulphur
removal require higher temperatures and pressures.
Reactor High pressure Stripper

separator
{ Hydrogen
j make-up Hydrogen recycle
Off gas
Feed
Figure 1: A distillate hydrotreater for hydrodesulfurization.

After passing through the reactor, the treated oil is cooled and separated from the excess
hydrogen which is recycled through the reactor. The treated oil is pumped to a stripper tower
where hydrogen sulphide, formed by the hydrogenation reaction, is removed by steam,
vacuum, or flue gas, and thefinishedproduct leaves the bottom of the stripper tower.
The reaction generally takes place in the vapour phase but, depending on the application, may
be a mixed-phase reaction. Generally, it is more economical to hydrotreat high-sulfur
feedstocks prior to catalytic cracking than to hydrotreat the products from catalytic cracking.
Tjieadvantages are that (1) sulphur is removed from the catalytic cracking feedstock, and
corrosion is reduced in the cracking unit, (2) carbon formation during cracking is reduced so
that higher conversions result, and (3) the cracking quality of the gas oil fraction is improved.
6- Reforming:
6.1 Thermal reforming:
Thermal reforming was developed to improve the octane number of gasoline. Thermal
reforming was a natural development from older thermal cracking processes; cracking
converts heavier oils into gasoline, whereas reforming converts (reforms) gasoline into
higher-octane gasoline. The equipment for thermal reforming is essentially the same as for
thermal cracking, but higher temperatures are used.
The products of thermal reforming are gases, gasoline, and residual oil or tar, the latter being
formed in very small amounts (about 1%). The amount and quality of the gasoline, known as
reformate, is very dependent on the temperature. A general rule is: the higher the reforming
temperature, the higher the octane number, but the lower the yield of reformate.
6.2 Catalytic reforming:
Like thermal reforming, catalytic reforming converts low-octane gasoline into high-octane
gasoline (reformate). Catalytic reforming produces reformate with octane numbers on the
order of 90 to 95. Catalytic reformer feeds are saturated materials; in the majority of cases
that feed may be a straight-run naphtha, but other byproduct low-octane naphtha (e.g. coker
naphtha) can be processed after treatment to remove olefins and other contaminants.
Catalytic refonning is usually carried out by feeding a naphtha and hydrogen mixture to a
furnace, where the mixture is heated to the desired temperature, 450oC to 520oC, and then
passed through fixed-bed catalytic reactor at hydrogen pressures of 100 to 1000 psi (7 to 68
arm), (Figure 2).
Reactor Reactor
Feedstock
Furnace Furnace
Light
hydrocarbons
Hydrogen
Recycle
>
Seperator
Reformate - «
Figure 2: Catalytic reforming.
5
Properties of Natural gas
Oilfield water
Second Year
Dr. Mimeef Mahjoob Mohammed

r
N a t u r a l gas
Natural gas is defined as gas obtained from a natural underground reservoir. Natural gas is
called a fossil fuel due to i t has been formed from by the degradation o f organic matter which
accumulated i n the sedimentary rocks before millions years ago. Natural gas exists i n the
subsurface reservoirs under pressure, either as a free gas, or i n conjunction with and dissolved
in the heavier hydrocarbons and water. f ? ^ \^>> i C '
Two main mechanisms are responsible for this degradation: Biogenic and thermogenic.
cAss^ • ^?HS"P~
Biogenic gas is formed at shallow depths and l o w temperatures by the anaerobic bacterial
decomposition o f sedimentary organic matter. In contrast, therm genie gas is formed at deeper
depths by: ' vf*-'
1- Thermal cracking o f sedimentary organic matter into hydrocarbon liquids and gas
(primary thermogenic gas).
2- Thermal cracking o f oil at high temperatures into gas (secondary thermogenic gas).
Biogenic gas consists almost entirely o f methane. In contrast, thermogenic gas can also
contain i n addition o f methane, significant concentrations o f ethane, propane, butanes, and
heavier hydrocarbons.
Figure 1: World's largest natural gas reserves.
2
Figure 2: Natural gas uses (2013).
Sources of natural gas ^ ' ^
f atural gas produced from geological formations comes in a wide array of compositions. The
varieties of gas compositions can be broadly categorized into two distinct groups:
1- Conventional gas
2- Unconventional gas
1- Conventional gas:
Conventional natural gas generally occurs in deep reservoirs, either associated with crude oil
(associated gas) or in reservoirs that contain little or no crude (non-associated gas).
3
Associated gas is the gas that is associated w i t h crude oil. It is produced during crude oil
production, and separated at the casinghead or wellhead. Gas produced i n this fasion is also
referred to as casinghead gas, oil well gas, or dissolved gas.
Crude oil cannot be produced without producing some o f its associated gas, which comes out
o f solution as the pressure is reduced on the way to and on the surface.
1.2 Non-associated gas:
Non-associated gas (sometimes called 'gas well gas' or 'dry gas ) is produced from
r
geological formations that typically do not contain much higher boiling hydrocarbons (gas
liquids) than methane. Non-associated gas can contain nonhydrocarbon gases such as carbon
dioxide and hydrogen sulphide. Non-associated gas is directly controlled by the producer.
One just turns the valves, the gas flow up the w e l l under its own energy, through the wellhead
control valves, and along the flow line to the treatment plant.
2- Unconventional gas:
The term unconventional gas is widely used, but it refers more to the geological setting and
rock type rather than to the gas itself, which is nearly all methane. The most common, "tight
gas", formed i n sandstones or carbonates, refers to l o w permeability formations. In such tight
reservoirs, it is êssentially not possible for much o f the gas to f l o w naturally. Massive
(. Ihed methane refers to methane gas is found adsorbed i n many berried coalbed deposits.
Weils drilled i n these deposits are hydraulically fractured and allow for the production o f
absorbed methane. In 2007, about 9% o f US natural gas was produced from C B M .
Finally, shale gas is gas found i n organic shale rocks, which exist i n relative abundance i n the
• •'* - l i d States. Because these reservoirs have virtually no permeability, the choice o f well
completions has been horizontal wells w ; i multiple hydraulic fractures.
; i
£ s composition:
Natural gas is a complex mixture o f hydrocarbon and non-hydrocarbon constituent ..nd

exists as a gas under atmospheric conditions. The principal ûustiiucnu o f natural ga^ is
methane. Other constituents are paraffmic hydrocarbons such as ethane, propane, and ;he
butanes. Many natural gases contain nitrogen as well as carbon dioxide and hydrogen
sulphide. Trace quantities o f argon, hydrogen, and helium may also be present, (Table 1).
4
.r
Natural gas is consideredjdrv^ when it is amiost pure methane. When other Irydroearhons are
present, the natural gas is^wet'. The composition o f natural gas varies depending on the field,
reservoir from which i t is extracted. ~ T~T~~~ —
Name formula volume
N lemane CH 4 - S5
Eihano C':H h
Propane (Ml. l ~ _
K i
BllUme f . H • .•
t
Penume a H i :
Carbon diox tie ( <)_ \1

Hydrogen \ iflde H S :
• i
•- i
V _ i >
Nitrogen . N '
Helium Ho • 0.5
Table 1: Typical composition of natural gas.
Effect of impurities found in natural gas:
-> Fiejdjprocessing operations o f natural gas, which is classified as a part o f gas engineering,
generally include the following:
J r Removal o f water vapour, dehydration
[2- Removal o f acidic gases (HoS and CO2).
(3y Separation o f heavy hydrocarbons.
y ^ V j j>\s> ^f?*
The effect o f each o f these impurities has on the gas industry, as end use; is briefly outlined:
Water vapor H2S and C 0 2 Liquid hydrocarbons
It is a common impurity. I t is Both gases are harmful, Their presence is undesirable

not objectionable a? sucry, ^ especially H2S, which is in the gas used as a fuel.
toxic i f burned; i t gives S 0 2
(a) Liquid water: and So3 which are nuisance • The liquid form is
accelerates corrosion i n to consume^rsj^JJ -^j'jÂj- objectionable for burners
the presence o f H2S gas. designed for eas fuels.
« Both gases are corrosive i n
(b) Solid hydrates: the presence o f water. « For pipelines, i t is a serious
Made up o f water and problem to handle two-phase
hydrocarbons, plug « C 0 2 contributes a lower flow: liquid and gas.
valves, fittings i n heating value to the gas.
pipelines, and so forth.
/_ . .
^ Classification of natural gas
Natural gas are classified according to their liquids content as either lean or rich and
according to the sulphur content as either sweet or s o u r . ' "
1- Liquids content: -
Gas composition plays a critical role i n the~economics o f gas processing, i he more liquids i n
the gas, the "richer" the gas. Extraction o f these liquids produces a product that may have a
higher sales value than does natural gas.
To quantify the liquids content o f a natural gas mixture, the industry uses G P M , or gallons o f
liquids recoverable per 1000 standard cubic feet o f gas.
The rich and lean terms refer to the amount o f recoverable hydrocarbons present. The terms
are relative, but a lean gas w i l l usually be 1 G P M , whereas a rich gas may contain 3 or more
GPM.
2- Sulfur content:
Sweet and sour refer to the sulphur (generally LbS) content. A sweet gas contains negligible
amounts o f H2S, whereas a sour gas has unacceptable quantities o f H2S. which is both
odiferous and corrosive. When present with water. H2S is corrosive.
Generally, sweet means the gas contains less than 4 ppmv o f H2S. The amount o f H2S
allowable i n pipeline-quality gas is between 0.25 and 1.0 grains per 100 scf.
Natural gas properties
A gas is defined as a homogeneous fluid o f l o w viscosity and density that has no definite
volume but expands to completely fill the vessel i n which it is placed.
Generally, the natural gas is a mixture o f hydrocarbon and nonhydrocarbon gases. The
hydrocarbon gases that are normally found i n a natural gas are methanes, ethanes, butanes,
pentanes, and small amounts o f hexanes and heavier. The nonhydrocarbon gases include
carbon dioxide, hydrogen sulphide, and nitrogen.
Ideal and Real gas laws:
The volume o f a real gas is usually less than what the volume o f an idepl gas would b, and
hencr a real gas is said to be sapercompressible. The ratio o f the real volume to the ideal
yrilume^4u£hJâ_r^ the amount the gas deviates from perfect behaviour, is called
the supercompressibility factor or compressibility factor (Z). The gas deviation factor is the
ratio o f the volume actually occupied by a gas at a given pressure and temperature to the
volume it would occupy i f it behaved ideally.
6
PV=ZnRT 1
Where:
P : absolute pressure (psia).
V: volume (ft ). 3
T: absolute temperature (°R).
Z: compressibility. y
.3/
i? : universal gas constant, which for the above units, has the value 10.730 psia ft / l b - m o l e
A t standard or atmospheric conditions, the gas Z factor is always approximately 1. Therefore,

the ideal gas law is expressed mathematically by the following equation:
PV=nRT 2
The number o f pound-moles o f gas, i.e., n, is defined as the weight o f the gas m divided by
the molecular weight M , or:
ni
n — 3
Combined equation 2 w i t h 3 gives:
pV =i — iRT 4
where m - weight of gas. lb

M - siioleciihir weigla. Ih/lh-mol
Since the d^nsityjs^ defined as the mass per unit volume o f the substance, equation 4 can be
rearranged to estimate the gas density at any pressure and temperature:
m pM c
— - J — D
V RT
where p„ = density of use gas. Ib/tC
7
Knowledge o f pressure-volume-temperature (PVT) relationships and other physical and
chemical properties o f gases are essential for solving problems in natural gas reservoir
engineering. These properties include:
.y 1- Apparent molecular weight:
One o f the main gas properties that is frequently o f interest to engineers is the apparent
molecular weight. I f yi represents the mole fraction o f the ith component in a gas mixture, the
apparent molecular weight is defined mathematically by the following equation:
M. = I > . M .
w hero M., = apparent molecular weight of a gas mixture

M = molecular \\eight oj the uh component iu (he mixture
v, = mole fraction of component i in the mixture
2- Standard volume:
The standard volume is defined as the volume o f gas occupied by 1 l b - m o l o f gas at standard
conditions^! 4.7 tpsia~and 60 °F). The relationship between pressure, volume and temperature
for a given quantity o f moles o f gas n can be expressed by the following equation:
p V = nRT
where p = absolute pressure, psia

V = volume, ft"
T = absolute temperature. R
n — number o f moles o f gas. lb-mole

R - the universal gas constant, w h i c h , for the above units, has the
value !0.730 psia f t V l b - m o l e R
8
By applying the standard conditions to the above equation, the standard volume gives:
ihRT. il,(I0.73m520)
standard ->!urne. scf'th-m
• Hlai'i.i i eiluViai UiV. K

4;iiKlaru pressure, psia
3- Density:
The density is defined as the mass per unit volume o f the substance. A t any pressure and
temperature, the gas density can be estimated by the following equation:
in _ p M
o..
V ~ RT
where p,. = density ot lhe gas. ib/tr'
The density o f an ideal gas mixture is calculated by replacing the molecular weight o f the
pure component i n the equation above with the apparent molecular weight o f the gas mixture
to eive:
nM.
RT
where p„ = density of the gas mixture. Ib/tV

M , = apparent molecular weight
;
4- Specific volume:
The specific volume is defined as the volume occupied by a unit mass of the gas. For an ideal
gas, this property can be calculated by applying the following equation:
V RT
•2
Where v : specific volume, ft /lb
P : gas density, lb/ft

g 3
9
5- Specific gravity:
The specific gravity is defined as the ratio o f the gas density to that o f the air. Both densities
are measured at the same pressure and temperature. Commonly, the standard pressure P sc and
standard temperature T s c are used i n defining the gas specific gravity:
_ P-
' ~
L Pan-
Assuming that the behaviour o f both the gas mixture and the air is described by the ideal gas
equation, the specific gravity can then be expressed as:
RT,.
p M
I s-
L an
KI
M.
M J i r 2S.06
• "/. = g;iN specific gru\

p. iT — WVHMIN '.>! Pic an'
M = apparent molecular u eight «>f (he air = 2S.0(>
;ili
\ _ - apparent molecular weight of she gas

o . - sianeiarei pressure, psia
v
6- Gas formation volume factor:
The gas formation volume factor is defined as the actual volume occupied by a certain
amount of gas at a specified pressure and temperature, divided by the volume occupied by the
same amount < f gas at standard conditions, i.e., 60°F and 14.7 psia. The relationship is
expressed as:
where B„ = gn-. formal ion volume fuel or. iVVscf

V p= volume o f gas a! pressure p and lempe . iure. T. IV
r
V.,. = volume o f uas at standard coiiditiot's. scf
10
Applying the real gas equation-of-state,(pV = znRT), and substituting for the volume V ,
gives:
AII_RT
P 1 = 'V / T
,•.•!).»!•;• / - /.t'êusr :>! sKnuki'd f! ;iK!!! is M ;s — i n

, \ T \ ^ a k i a r J p r o c u r e :nul k a i i j v r a i m v
Assuming that the standard conditions are represented by Pse = 14.7 psia and Tsc = 520, the
above expression can be reduced to the following relationship:
.. _ __/T
0
where B„ = gas f o r m a t i o n v o l u m e factor. ft-Vsef

/ - gas compressibility factor
T •- temperature. R
The above equation can be expressed i n terms o f the gas density p i f combined with the g
following equation:
K r v /.RT
where v = s p e c i f i c v o l u m e . SVVIb
p „ = density, l b / f t 3
To give:
M vl
B, = 0.02S27—- = 0.002635—: ft" set'
r<P, p s
where p,_, = y.as d e n s i t y . i b / l V

- apparent m o l e c u l a r w e i g h ; o f <ra>.
11
In other field units, the gas volume factor can be expressed in bbl/scf to give:
/ i
B„ = 0.()()5u55- -54-
S i m i k t r l v . b u t t a t i o n 2-54 can be e x p r e s s e d in t e r m s of ihe eas density
M
B , = 0.00504-— - - ( ) . ( ) ( ) ( ) 4 6 9 — ; L bbl/scf
i o f the nas l u r i n a t i o n \ o i u n v e 1 a c t o r i<« c a l l e d the litis

•>lid is de i' H;ped bv {be sVpobid P
v T < >|\
-.d'/i'i
,T
E, = ^7C> !' It
In other units:
NK.n-^: Nci'/bblj -""O t
/ t
7- Gas viscosity:
The viscosity of a fluid is a measure of the into eialfluidfriction^x^resu^tance)to flow^ The

viscosity of a fluid is generally defined as the ratic of the shear force per unit area to the local
velocity gradient. Velocities are expressed in terms of poises, centipoises, or micropoises.
One poise equals a viscosity of 1 dyne-sec/cm2.
- The gas viscosity is not commonly measured in the laboratory because it can be estimated
precisely from empirical correlations. Viscosity of a natural gar is a function of pressure,
^X^^cS, t e m P e r a t u r e > a n a " composition.
Vv-v
8- Compressibility of natural gases:
Knowledge of the variability of fluid compressibility wim pressure and temperature is

essential in performing many reservoir engineering calculations. For a liquid phase, the
compressibility is small and usually assumed to be constant. For a gas phase, the
compressibility is neither small nor constant.
12
B y definition, the isothermal gas compressibility is the change i n volume per unit volume for
a unit change in pressure or, in equation form:
/ ;)v
V * r) P L
\\here c,, = isothermal gas compressibility, l/psi.
From the real gu.> equation-nt-state:
,. P.RTZ
Differentiating the above equation with respect to pressure at constant

temperature T gives:
nRT
U>p. t _ P \p J n-
Substituting into equation 1 produces the following generalized relationship:
H ' P Z ' P 'T

f)
For an ideal gas. z = i and idz/Vjp j T = 0. (he re fore:
13 w
( vjlj\l gas p h a ^ behaviou^
Natural gas phase behaviour is a function o j pressure, jej^jOjerature, and volume. The natural
gas phase behaviour is a plot o f pressure versus temperature that determines whether the
natural gas "stream at a given pressure and temperature consists o f a single gas phase or two
phases: gas and liquid. The phase behaviour for natural gas with a given composition is
typically displayed on a phase diagram (Figure 3).
The natural gas phase behaviour is a function o f the composition o f the gas mixture and is
strongly influenced by the concentration o f the heavier hydrocarbons.
—f Bubble point curve: the curve that separates the pure liquid (oil) phase from the two-
phase (natural gas and oil) region. This means that at a given temperature, when
pressure decreases and below the bubble point curve, gas w i l l be emitted from the
liquid phase to the two-phase region. c -^"7_-
• Dew point curve: the curve that separates the pure gas phase from the two-phase
region. It is the connected points o f pressure and temperature at w h i c h the first liquid
droplet is formed out o f the aas phase.
" sl>3
• Critical point: the point on the phase envelope where the bubble point curve meets the
dew point curve. A t that given pressure and temperature, gas properties are identical^,
£ ^ to liquid properties and the distinction between gas and liquid properties disappears:
^ Jd The pressure and temperature at the critical point are called critical pressure and
temperature, respectively. ^
• Cricondentherm: the highest temperature at which liquid and vapour carr coexist. That
means the mixmre w i l l be gas irrespective o f pressure when the temperature is larger
than cricondentherm. «_/^ , J
• Cricondenbar: the highest pressure at which a liquid and vapour can coexist.
14
Xy^ On the basis of their phase diagram and the prevailing reservoir conditions, natural gases can
j be classified into four categories: ~ ~~~ ~~ J )
- ^ * » Retrograde gas-condensate t v ^
— • Near-critical gas-condensate
• Wet gas
• D r y gas
1- Retrograde gas-condensate reservoir:
I f the reservoir temperature T lies between the critical temperature T and cricondentherm T ,
c T
o f the reservoir fluid, the reservoir is classified as a retrograde gas-condensate reservoir.
2- Near-critical gas-condensate reservoir:
I f the reservoir temperature is near the critical temperature, the hydrocarbon rriixture is
classified as a near-critical gas-condensate.
15
the reservoir temperature is above the cricondentherm Tct o f the hydrocarbon mixture, the
reservoir is classified as a wet gas.
4• - TYrv-aaQ
" j
l o — -n—
wirvnir
The hydrocarbon mixture exists as a gas both i n the reservoir and i n the surface conditions.
<_S> Processing and p r i n c i p a l products:
The two primary uses for natural gas are as a fuel and as a petrochemicaj_feedstock ? and
, consequently, the three basic reasons for processing raw natural gas are the following:
s^y • \ ^ ^ P u r i f i c a t i o n : Removal o f materials, valuable or not, that inhibit useôf the gas as_ an
V
C/ industrial or residential fuel. . Cs \ ^ x 3 o ^ 5 /> V j V "
'"r>) Separation: Splittmg o u f o f components that have greater value as petrochemical

feedstocks, stand alone fuels (e.g. propane), or industrial gases (e.g. ethane, helium).
Liquefaction: Increase o f the energy density o f the gas for storage or transportation.
Depending on the situation^ a process may be classified as either separation or purification.

For example, i f a small amount o f is removed, incineratedT a^S vented to the
_ >
^ e atmosphere, the process is purification, but i f large amounts o f H2S are removed and
3 converted to elemental sulphur, often a low-prices commodity, the process is considered
separation. {j^j=^
The typical process operation modules are shown, i n Figure 4. Each module consists o f a
single piece or a group o f equipment performing a specific fur etion.
16
Fractionation
Figure 4: Simplified typical onshore treatment process.
Natural gas processing:
The purpose o f gas processing is to produce a gas stream that meets sales requirements and
specjîcatipn^ heating value and recovery o f maximum amount o f NGLs4(Natural
Gas Liquids). The processing o f wellhead natuial gas uiixt^V^^^^^^^^^W 5 ( -S-'
e
99.9 o methane) can be quite complex and usually involves several processing.
1- Natural gas and liquid separation:
Natural gas and liquid separation is usually performed i n the field immediately after the gas is
produced. A field separator is intenaed to remove solids and free liquid from the gas. In
addition, the separated gas and liquid from the vessel must be discharged without re-
„ i ;. t C',.. I 1 : -. . . . . . - . " I . . k l . - A ~ fl-.-.c^ / T - V I / H ON
17
Droplet Size Removed
D o w n t o oOO u m
• C e n tri ru ga 1 Se pa ra t o r D o w j ^ d K-li) um
M i s t E l i m i n a t o r i'ad D o w n to i d u m
Vane Separator D o w n t o K) urn
H i g h htticiencx i.o r ( oaiester D o w n to 0.1 urn
iabie 2: types o f liquid/gas separators
l^cjJ^Jl oo
The selection o f the separator type and size is dictated by different factors:
(>)Cjas and liquid flow rates
v%)fype o f natural gas as denoted by its specific gravity
V * > h e specifications ot the produced oil and water
© h e separator operating conditions (pressure and temperature)
( • } r h e oresence o f solids
^ > h e floor space availability such as on an offshore platform
C^Cost
2- Natural gas dehydration (water removal):
Water w i t h natural gas can generate a great no .her o f problems; therefore, water has to be
removed from natural gas before it is transported. These problems are:
(*>Water could form solid hydrates at certain pressures and temperatures, w h i c h can plug
facilities and pipelines. -— }
\5»)When pressure and temperature drop, water vapor condenses and can cause slug flow and
possible erosion and corrosion i n the system, especially when acid gases are present.
(•^Water vapour increases the total volume and decreases the heating value o f gas, which
subsequently, cannot meet gas stream specifications.
? e
18
is removed after the gas-liquid separation is at or near the wellhead.
' A c e are still small amounts o f water vapour associated with the main stream o f
I gas that requires further treatment to remove (dehydration).
2.1 Natural gas hydrates: "^ T°
Natural gas hydratei are solid crystalline compounds formed by the chemical combination o f
natural gas and water under pressure at temperature considerably above the freezing point o f
water.Jrhe chemical formulae for natural gas hydrates are:
.vi vi nan
(;, {-{ «,s | - j , ()
('.arbon I <io\ (;< > , » 7 H , 0
Hydrates tend to form when there is: i/^X^J^J i " VîA I? ^ ->' U J
• Free water present and temperature decreases below that o f hydrate-formation.
• Sudden pressure drop due to expansion
3- Natural gas sweetening (acid gases removal):
Gas sweetening processes remove the contaminants which are found i n natural gas such as
hydrogen sulphide (H2S), c arbon dioxide (CO2), and other contaminants so that the gas is
marketable and suitable for transportation. ™™ - '
19
Product specifications
specifications for salable products from gas processing are generally i n terms o f both
composition and performance criteria. For natural gas these criteria include Wobbe number,
heating value, total inerts, water, oxygen, and sulphur content. The first two criteria relate to
combustion characteristics. The latter three provide protection from pipeline plugging and
corrosion.
For liquid products, the performance specifications include Reid vapour pressure, water, oxygen,
H S, end total sulphur content.
2
( / T - Combustion characteristics: ys^jQ ( C^jJ

0 <3/>£>JMc3
flTpHeating value
Determination o f the heating value o f a fuel involves two standard states for the water
formed in the reaction: , „ r
a- A l l the water formed is a liquid (gross heating value, frequently called higher heating
value).
b- A l l the water formed is a gas (net heating value, frequently called lower heating value).
1.2 Wobbe number
Wobbe number is defined as the gross heatmg_ ya3jiej{Btu/'scf) o f the gas divided by the
,
sequare root o f the specific gravity^ (the ratio o f the density o f l E e gas divided^Bythe density
ot air; both densities evaluated at the same pressure and temperature). The Wobbe number
normally has a value between 1,100 and 1,400 .
s ' Properties of oilfield waters:
Extraction o f o i l and gas from underground reservoirs often is accompanied by water or

brine, which is referred to as produced water. Thus, a knowledge of the properties o f this
connate, or interstitial, or formation water is important to petroleum engineers.
AliVJon^^ solids, primarily sodium chloride. The water

sometimes is called, brine or saTrwalerTOiTfield waters contain much Mgher concentrations o f
solids than seawater does, i n addition to dissolved saits, microorganisms o f different species
and strains are usually present i n oilfield brines. These organisms contribute to corrosion i n
the wellbore and to plugging o f the formation during water-injection operations.
21
Figure 8: The relationship between brine viscosity and temperature. 1
3- Surface (interfacial) tension:
Surface tensionJinteriaciaLl^^ a measure of the attractbyjejforce acting at a boundary

between two phasesjlf the phase boundary separates a liquid and a gas or a liquid and a solid,
the attractive force at the boundary usually is called surface tension. The attractive force at
the interface between two liquids is called interfacial tension. At very low values of
interfacial tension, oil and water become miscible armbehave as a single phase. Interfacial
tension is an important factor in enhanced recovery, and also it determines the ease of
^sepjaratmnjo^^ it determines the size of the oil or water droplets^
P c>ve3/^ ( £ A 5 ^
23
1- Resistivity:
The resistivity o f formation water is a measure o f the resistance offered by the water to
electrical current.\jlt can be measured directly or calculated. The direct measurement method
Tsessentially theelectrical resistance through a 1-m cross-sectional area o f 1 m o f formation
2 3
water. Formation water resistivity is expressed i n units o f Q-m.
z.- viSCOsIty:
The viscosity o f formation water is a function of:
• Pressure ^ J^ ^
• Temperature j-y'ULiJ &

• Dissolved solids
I n general, brine viscosity increases w i t h :
• Increasing pressure (Figure 7).
• Increasing salinity
• Decreasing temperature (Figure 8).
Figure 7: The relationship between brine viscosity and pressure.
22-

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IVtUiUs

:acult>" of Petroleum & Mining Engineering

Oil & Gas Properties

The chemistry of petroleum:

Element Weight (%)

Metals (Fe, Ni, Cu, V,...) <0.1

Table 1: The elementary composition of crude oil.

Thejjydrocarbons present in petroleum are classified into three general groups:

Example of a typical Example of naphthene with same

Figure 2: Naphthene, or ring, compounds have the chemical formula CnH2n.

Oil & Gas Properties

Dr. Muneef Mahjoob Mohammed

• Oil formation volume factor

62.4 y„ +0.0136 Rsy:

where y„ = specific gravity of I he stock-lank oil

Figure 1: Gas-solubility pressure diagram.

a- Dead-oil viscosity J J>3 &

The Beggs-Robinson Correlation K

B e g g s and Robinson (l°75) developed an empirical correlation lor

whore B, = lolal formal ion v o l u m e factor. b h l / S T B

10- Aniline point:

12- Pour point:

13- Molecular weight:

Faculty of Petroleum & Mining Engineering

Department of Petroleum & Refining Engineering

Oil & Gas Properties

Dr. Muneef Mahjoob Mohammed

14- Surface and interfacial tension

Temperature Surface Tension

21.1 70.0 35.3 35.3

Table 1: Effect of temperature on the surface tension of Athabasca bitumen.

Dynamic surface tension = 681.3/A'(1 - T}\ L 7 6 5 4 x 2-»250ji.2056

15- Metals content:

and sulphur oxides (SO ) form, respectively.

2-Liquefaction and solidification *^^^<~>Sb ~-*L> , ^ x

Unsubstituted and symmetrically substituted compounds (e.g. benzene, cyclohexane, and

solidification, has received attention in petroleum chemistry. Solidification of petroleum and

l/d (0.388 + 0.00045^

7- Enthalpy or heat content

H = 1 /rf(0.388 + 0.000225/ - 12.65)

K = 0.28 fd{l - 0.00054) x 10" 3

Where d is the 6O/6O0F specific gravity.

Crude petroleum is^^rr^tûreô^ cpmrûndj^boiling at different temperatures that can be

1 - Materials that are of natural origin.

2- Materials that are manufactured.

3- Materials tnat&re integral fractions derived from natural or manufactured products.

Natural Materials Derived Materials Manufactured Materials

Natural gas Saturates Synthetic crude oil

Table 1: Subdivision of petroleum and similar materials into various subgroups.

Petroleum occurs underground, at various pressures depending on the depth. Be^ausjLiiCjhe

Nonhydrocarbon constituents of petroleum include organic derivatives of nitrogen, oxygen,

1.2 Heavy oil

Pyrobitumen is a naturally occurring solid organic substance that is distinguishable from

asphaltic or nonasphaltic. The asphaltic pyrobitumen, derived from petroleum, is relatively ** *

\6 Bitumenous rock and Bituminous sand

If the material is of the asphaltite-type or asphaltoid-type, the corresponding term, rock

1.7 Natural gas:

Name Formula Voi.%

Table 2: Constituents of natural gas.

2.2 Residuum (Residua)

Carbon Disulfide (3) Benzene- (2) Benzene or (1) Heptane

Figure 1: Simplified representation of the fractionation of petroleum.

3.2 Resins and oils

2.4 Tar and pitch

2-Liquefaction and solidification ^^^<~>Sb ~-L> , ^ x