lecture 4

Composition of crude oil

Shayma Hamza
Lecturer in Chemical Engineering
Duhok Polytechnic University

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Crude petroleum oil
• Main component is hydrocarbons (
compounds consisting mainly of Carbon
and hydrogen)
• Carbon 85-90%
• Hydrogen 10%-14%

• Non-hydrocarbons • Sulfur 0.2 -3 %

• Nitrogen < 1-2% • Oxygen 1-1.5%
• Organometallic compounds, in trace
amounts, of:
• Nickel
• Vanadium
• Arsenic
• lead
• Others
• Mineral salts originating from reservoir water or process water:
• Sodium Chloride
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 • Magnesium chloride
• others
Classification of hydrocarbons
Hydrocarbons are made up of only hydrogen and carbon.
Hydrocarbons are classified on the basis of the nature of the framework of the
carbon chain and the nature of the bond between carbon atoms

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 Paraffins Naphthenes Olefins Alkynes

Paraffins-Alkanes

Paraffins have the general formula CnH2n+2 where n = 1,2,3,…

• Only single covalent bonds

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 • Saturated hydrocarbons because they contain the maximum number of
hydrogen atoms that can bond with the number of carbon atoms in the
molecule

CH4 C2H6 C3H8

methane ethane propane

• Paraffins are considered as relatively stable compounds that undergo very
few chemical reactions at room temperature.

Paraffins-Alkanes
Paraffins have Structural isomers; molecules that have the
same molecular formula but different structures

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Number of branched or isomers increase with increasing carbon atoms in the
structure.

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Physical properties of some paraffins

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Naphthenes-Cycloalkanes
Alkanes whose carbon atoms are joined in rings are called

cycloalkanes. They have the general formula CnH2n where n =

3,4,…
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Naphthenes are desirable compounds for the production of aromatics
and good quality lube oil base stocks.

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Geometry of naphthenes

more stable

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Naphthenes like paraffins have saturated carbon bonds and are
relatively stable and inactive.

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Olefins
Olefins have the general formula CnH2n where n = 2,3,…
• Contain at least one carbon-carbon double bond and therefore called
unsaturated hydrocarbons
•Also called Alkenes

CH2 CH CH2

1-butene 2-butene

Cl Cl Cl H
C C C C
H H CH3 CH3 H Cl
CH
CH CH3
cis-dichloroethylene trans-dichloroethylene
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Olefins
Olefins are highly reactive
• React to themselves to form mono olefins
• React readily with acids, alkaline, halogens and oxidising agents

Olefins are determined by bromine or iodine number

Bromine number is the amount of bromine in grams absorbed by 100 grams of

a sample. The number indicates the degree of unsaturation.

The Bromine Number is useful as a measure of aliphatic unsaturation in gasoline

samples. Bromine number is the twice presence of unsaturated aliphatic compounds in
the sample Example:

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If we have sample with bromine number 30 =======> the olefins content is 15 Vol%
Olefins

Olefins are not present in crude oil, but they are produced by thermal and
catalytic decomposition or dehydrogenation of normal paraffins.

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 Like paraffins they can have isomers.

Aromatic hydrocarbons

Aromatics have the general formula CnH2n-6…

• They are hexagonal ring structure
• Also called benzenes
• Chemically very active compared to other groups of hydrocarbons

• In reaction with oxygen they form organic acids

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 • Lower aromatics such as toluene, benzenes and xylene are good solvents and
precursors for many petrochemicals

Complex hydrocarbons

Complex hydrocarbons do not fall into any of previous categories

• They are usually a combination of two or more classes of hydrocarbons

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• Usually contained within heavier fraction of crude oil
• Polynuclear aromatics (PNA) belong to this group
Petroleum
coke • PNAs are precursors of coke which form as thermal effect and quite hard to
decompose.

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Non-hydrocarbons or heteroatomic compounds

Organic compounds that contain one or more atoms other than

carbon and hydrogen.
• Common heteroatom are sulfur, oxygen, nitrogen and metallic atoms

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Non-hydrocarbons- Sulfur compounds
Sulfur compounds are present in crude oil as mercaptans, mono- and
disulfides.

R S R S S R1

R1
Mercaptan Monosulfides non- Disulfides
Corrosive Corrosive non-
Corrosive
Hydrogen sulfide H2S can also be found as dissolved gas
• Corrosive at high temperature in presence of moisture

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• Its concentration determine whether crude oil is classed as sour or sweet

• usually removed by amine solution scrubbing

Non-hydrocarbons- other compounds

Nitrogen compounds
• Usually found in the heavier part of crude oil

• Responsible for environmental pollution through formation of NOx compounds

• usually removed by catalytic hydrogenation

Oxygen compounds
• Usually found in crude oil as organic acids and alcohols, thus corrosive and excess
amounts can lead to explosion.

• Usually removed by catalytic hydrogenation

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Organometallic compounds
• Usually found in the heavier part of crude oil.

• Lead, Nickel, Arsenic and vanadium are most common. Forming organometallic
complexes called porphyrins.
• Cause damage to burners, lines and walls of combustion chamber

Physical properties of crude oil-API gravity

American Petroleum Institute API gravity is a measure of how heavy or light a
petroleum liquid is compared to water

141.5
API = −131.5
s
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 s specific gravity of the crude oil
Specific gravity is the ratio of the density of a substance to the density of a
reference substance

Classification API range Density kg/m3

Light crude oil API > 31 < 870
Medium oil 22.3 < API< 31 870-920
Heavy oil 22.3 > API 920-1000
Extra heavy oil 10 > API >1000

Physical properties of oil- Characterisation Factor CF

In addition to API gravity characterisation factor CF is used as

means for further characterising of crude oil an its components.
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 CF =TB1.3
s
s specific gravity of the crude oil
TB The mean average boiling point in Rankine
Classification CF
Paraffinic CF > 12.5
Naphthenic CF < 12.5
Aromatic CF < 10

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 Origins of hydrocarbons
Petroleum or “ Rock oil” is gas and/or liquid phases that can be found in
porous rock structures and are rich in carbon and hydrogen compounds known
as hydrocarbons.
• Usually found in the subsurface in porous rock known as sedimentary basin

• In majority of basins gas, oil and water coexist under pressure

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 Origins of hydrocarbons
Generally accepted that hydrocarbons are a result of decaying
microorganisms, dead plants and animals under conditions of high
temperature and pressure under the earth’s surface.

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• Usually found in the subsurface in porous rock known as sedimentary basin

• In majority of basins gas, oil and water coexist under pressure

Three types of oil reserve:

• Proven (economical)
• Probable ( 50% chance)
• Possible ( > 10 %)

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Petroleum exploration techniques

• Gravimetric method
• gravity = function ( depth, material)

• It senses tiny variation in the earth gravitation constant, which

could be interpreted into geological data.

• Magnetometric method
Based on the variation of Earth magnetic field which is a result in the change of

the geological composition.

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Petroleum exploration techniques

• Seismic Survey
• Uses sound signal reflection to locate prospective basin
structure.

• reflected waves = function ( density, porosity, type of

reflecting surface)

• Remote sensing method

Reflected solar radiation from Earth = function ( subsurface
properties)

Not applicable to surface that absorb most of solar radiation

such as ocean surface.

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Petroleum exploration techniques

in combination with Gravimetric, magnetic and seismic methods

creates an image of the subsurface using GIS Geological
Image Software

• Geochemical methods
• Measuring the total amount of carbon in the surface, shallow
or core samples and evaluation the organic content of carbon.

• Stratigraphy

Studying the rock layers ( strata) and layering stratification.

correlating data from wells, rocks, fossils and mud properties
before and during drilling operations for the final prediction.

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Resource Estimation

• Oil and/or gas in place

• The total amount of oil/gas in the reservoir pores.

• The amount that can be economically produced and marketed is called

Reserve.
• Volumetric oil in place ( million metric tons), following equation is
used:

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Important parameters in retrieving oil

Resource Estimation

• Volumetric gas in place ( million metric tons)

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• Pressure ( the most important parameter)

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Important parameters in retrieving oil
• High pressures causes a natural drive to retrieve oil without need
for any external pressurisation.

• High pressures also cause formation of methane hydrates which

can be damaging to the well. Usually, this problem is solved by
injecting methanol to disperse the hydrates in the water.

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Important parameters in retrieving oil

• Connate water
• Water present in the pore is called Connate or interstitial water.

• The greater amount of Connate water the lower is the

permeability of oil
• Connate water contains dissolved minerals. Improper selection of
injection walls results in larger water cut in production

• Temperature
• The geothermal gradient is the variation of temperature in the
subsurface as a function of depth.

• The greater the geothermal gradient the higher is the permeability

of oil.

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Important parameters in retrieving oil

• Viscosity
• Oil is visocoplastic fluid and not considered as a non-Newtonian
fluid

k is the consistency factor, and n < 1 for a viscoplastic fluid

• Production rate is dependent on

• The lower ratio, the higher is the oil cut and vice versa.

• This ratio increases with the age of well, hence increases the water
cut.

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Important parameters in retrieving oil

• Polymers and other high viscous compounds are injected to increase

the viscosity of water and lower this ratio.

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Crude oil conditioning and storage

• Crude oil is a homogenous mixture of gases, light and heavy hydrocarbons

in addition to sand, mud and water under pressure in reservoir
• Crude oil is treated at surface to separate these components

• Treatment involves
Gravity settling to Chemical treatment Crude conditioning
remove sand and to separate unit
water emulsified water

• Conditioning of oil

Separation of volatile Heating and mixing Storage under gases lighter than followed by cooling cycles

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pressure to prevent propane to homogenies crude oil gas separation

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