Petroleum Properties
1
Petroleum Definitions
Petroleum is a complex mixture of hydrocarbons that
occur in the sedimentary rocks in the form of gases
(natural gas), liquids (crude oil), semisolids (bitumen),
or solids (wax or asphaltite).
An underground reservoir that contains hydrocarbons is
called petroleum reservoir and its hydrocarbon contents
that can be recovered through a producing well is called
reservoir fluid.
2
Petroleum Definitions
Paraffins
Generally, hydrocarbons are divided into four groups:
paraffins, olefins, naphthenes and aromatics.
Paraffins are also called alkanes and have the general formula
of CnH2n+2, where n is the number of carbon atoms. Paraffins
from C1 to C40 usually appear in crude oil and represent up to
20% of crude by volume. Since paraffins are fully saturated
(no double bond), they are stable and remain unchanged over
long periods of geological time.
3
Petroleum Definitions
Olefins
Olefins are another series of noncyclic hydrocarbons but they
are unsaturated and have at least one double bond between
carbon-carbon atoms. Compounds with one double bond are
called monoolefins or alkenes. Monoolefins have a general
formula of CnH2n.
Olefins are uncommon in crude oils due to their reactivity with
hydrogen that makes them saturated; however, they can be
produced in refineries through cracking reactions.
4
Petroleum Definitions
Naphthenes
Naphthenes or cycloalkanes are ring or cyclic saturated
hydrocarbons with the general formula of CnH2n. Cyclopentane
(C5H10), cyclohexane (C6H12), and their derivatives such as n-
alkylcyclopentanes are normally found in crude oils.
Thermodynamic studies show that naphthene rings with five
and six carbon atoms are the most stable naphthenic
hydrocarbons. The content of cycloparaffins in petroleum may
vary up to 60%.
5
Petroleum Definitions
Aromatics
Aromatics are an important series of hydrocarbons found in
almost every petroleum mixture from any part of the world.
Aromatics are cyclic but unsaturated hydrocarbons that begin
with benzene molecule (C6H6) and contain carbon-carbon
double bonds.
Some of the common aromatics found in petroleum and crude
oils are benzene and its derivatives with attached methyl, ethyl,
propyl, or higher alkyl groups. This series of aromatics is
called alkylbenzenes and have a general formula of CnH2n-6
(where n ≥ 6).
6
Petroleum Definitions
Sulfur content
Sulfur is the most important heteroatom in petroleum and it
can be found in cyclic as well as noncyclic compounds such as
mercaptanes (R-S-H) and sulfides (R-S-R’), where R and R’ are
alkyl groups.
Sulfur in natural gas is usually found in the form of hydrogen
sulfide (H2S). Some natural gas contain H2S as high as 30% by
volume. The amount of sulfur in a crude may vary from 0.05 to
6% by weight.
7
Petroleum Definitions
Crude Oil
Crude density is commonly measured by API gravity
API gravity provides a relative measure of crude oil density.
The higher the API number, the lighter the crude
Sulfur content measures if a crude is sweet (low
sulfur) or sour (high sulfur)
Typically less than 0.5% sulfur content = sweet
Typically greater than 1.5% sulfur content = sour
High sulfur crudes require additional processing to meet
regulatory specs
8
Petroleum Fractions
Some of the petroleum fractions produced from distillation
columns with their boiling point ranges are given in Table
below. These fractions may go through further processes to
produce desired products.
9
Crude Oil Properties
The properties of crude oil vary widely
* The ratio of light:heavy components
* The amount of impurities
Specifications are needed to describe them
•API Gravity
•Flash Point & Fire Point
•Salt Content
•Sulfur Content
•Cloud Point & Pour Point
•Ash Content
10
Crude Specifications: API Gravity
American Petroleum Institute (API) Gravity
A rough measure of a crude’s composition
* Low API: Heavier crude
* High API: Lighter crude
API is defined as
141.5
API 131.5
60
SG o
60 F
60
SG o
Is the density of oil measured at 60oF divided by density of
60 F Water measured at 60oF. SG means specific gravity.
Petroleum Properties
Pour point
of a petroleum fraction is the lowest temperature at which the
oil will pour or flow when it is cooled without stirring under
standard cooling conditions.
Pour point represents the lowest temperature at which an oil
can be stored and still capable of flowing under gravity. When
temperature is less than pour point of a petroleum product it
cannot be stored or transferred through a pipeline. Test
procedures for measuring pour points of petroleum fractions
are given under ASTM D 97 and ASTM D 5985 methods.
12
Petroleum Properties
Cloud point is the lowest temperature at which wax crystals begin to
form by a gradual cooling under standard conditions. At this
temperature the oil becomes cloudy and the first particles of wax
crystals are observed. The standard procedure to measure the cloud
point is ASTM D 2500.
Low cloud point products are desirable under low-temperature
conditions. Wax crystals can plug the fuel system lines and filters,
which could lead to stalling aircraft and diesel engines under cold
conditions. Cloud points are measured for oils that contain paraffins
in the form of wax and therefore for light fractions (naphtha or
gasoline) no cloud point data are reported.
13
Petroleum Properties
Flash point
for a hydrocarbon or a fuel is the minimum temperature at
which vapor pressure of the hydrocarbon is sufficient to produce
the vapor needed for spontaneous ignition of the hydrocarbon
with the air with the presence of an external source, i.e., spark or
flame. The standard procedure to measure the Flash point is
ASTM D 93.
Flash point is an important parameter for safety considerations,
especially during storage and transportation of volatile
petroleum products (i.e., LPG, light naphtha, gasoline). The
surrounding temperature around a storage tank should always be
less than the flash point of the fuel to avoid possibility of
ignition.
14
Petroleum Properties
Flash point
should not be mistaken with fire point, which is defined as the
minimum temperature at which the hydrocarbon will continue
to burn for at least 5 s after being ignited by a flame.
Autoignition temperature is the minimum temperature at
which hydrocarbon vapor when mixed with air can
spontaneously ignite without the presence of any external
source. Values of autoignition temperature are generally
higher than flash point. This is particularly important from a
safety point of view when hydrocarbons are compressed.
Standard test is ASTM D 2155.
15
Petroleum Properties
To have a combustion, three elements are required: fuel
(hydrocarbon vapor), oxygen (i.e., air), and a spark to initiate
the combustion. One important parameter to have a good
combustion is the ratio of air to hydrocarbon fuel. The
combustion does not occur if there is too much air (little fuel)
or too little air (too much fuel). This suggests that combustion
occurs when hydrocarbon concentration in the air is within a
certain range. This range is called flammability range and is
usually expressed in terms of lower and upper volume percent
in the mixture of hydrocarbon vapor and air.
16
Crude Specifications: Ash Content
Ash Content
The amount of metallic constituents in a
crude
Considerations
* Form corrosive acids
* Form soaps
* Poison catalysts – vanadium and nickel
Why is it called the Ash Content?
Metals are left as ash when oil is burned
Crude Specifications: Sulfur Content
Sulfur Content
The amount of sulfur in the crude.
Considerations
* Affects the commercial value
Sulfur smells when burned
Harms engines
* Sulfur is easily converted to H2S
Hydrotreating!!
Crude Specifications: Salt Content
Salt Content
The amount of salt (NaCl) in the crude.
Expressed as mg/L or lbs/barrel.
Considerations
* Salt is undesired
Causes corrosion and plugs equipment
* Salt content must be < 10 lb/1000 barrels
Petroleum Properties
Octane number is a parameter defined to characterize
antiknock characteristic of a fuel (gasoline and jet fuel) for
spark ignition engines. Octane number is a measure of fuel's
ability to resist auto-ignition during compression and prior to
ignition. Higher octane number fuels have better engine
performance.
The octane number of a fuel is measured based on two
reference hydrocarbons of n-heptane with an assigned octane
number of zero and isooctane (2,2,4-trimethylpentane) with
assigned octane number of 100.
20
Petroleum Properties
For diesel engines, the fuel must have a characteristic that
favors auto-ignition. The ignition delay period can be
evaluated by the fuel characterization factor called cetane
number (CN). The shorter the ignition delay period the
higher CN value.
The cetane number is defined as:
CN = vol% n-cetane + 0.15(vo1% HMN)
Where n-cetane (n-C16H34) has a CN of 100, and
heptamethylnonane (HMN) has a CN of 15. The cetane
number of a diesel fuel can be measured by the ASTM D 613
test method.
21
Petroleum Properties
Higher cetane number fuels reduce combustion noise and
permit improved control of combustion resulting in increased
engine efficiency and power output. Higher cetane number
fuels tend to result in easier starting and faster warm-up in cold
weather and can cause reduction in air pollution.
The product distributed in France and Europe have CN in the
range of 48-55. In the United States and Canada the cetane
number of diesel fuels are most often less than 50. Cetane
number of diesel fuels can be improved by adding additives
such as 2-ethyl-hexyl nitrate or other types of alkyl nitrates.
22
Petroleum Properties
Aniline point for a hydrocarbon or a petroleum fraction is
defined as the minimum temperature at which equal volumes of
liquid hydrocarbon and aniline are miscible.
The aniline point is important in characterization of petroleum
fractions and analysis of molecular type. The aniline point is
also used as a characterization parameter for the ignition quality
of diesel fuels. It is measured by the ASTM D 611 test method.
Aromatics have very low aniline points in comparison with
paraffins, since aniline itself is an aromatic compound (C6H5-
NH2) and it has better miscibility with aromatic hydrocarbons.
23
Petroleum Properties
When a petroleum fraction is vaporized in the absence of air at
atmospheric pressure, the nonvolatile compounds have a
carbonaceous residue known as carbon residue (CR).
Therefore, heavier fractions with more aromatic contents have
higher carbon residues while volatile and light fractions such
as naphthas and gasolines have no carbon residues.
There are three different test methods to measure carbon
residues, Ramsbottom (ASTM D 524), the Conradson (ASTM
D 189) and microcarbon (ASTM D 4530). In most cases
carbon residues are reported in wt%.
24
Petroleum Properties
The smoke point (SP) is a maximum flame height at
which a fuel can be burned in a standard wick-fed lamp
without smoking. It is expressed in millimeters and a high
smoke point indicates a fuel with low smoke-producing
tendency. Measurement of smoke point is described under
ASTM D 1322.
Smoke point is a characteristic of aviation turbine fuels and
kerosenes and indicates the tendency of a fuel to burn with a
smoky flame. Higher amount of aromatics in a fuel causes a
smoky characteristic for the flame and energy loss due to
thermal radiation.
25
Quality of Petroleum Products
The quality of a petroleum product depends on certain
specifications or properties of the fuel to satisfy required
criteria set by the market demand. These characteristics are
specified for best use of a fuel (i.e., highest engine
performance) or for cleaner environment.
These specifications vary from one product to another and
from one country to another. Standard organizations such as
ASTM give such specifications for various products. For
example: ASTM D 4814 for gasoline, ASTM D 975 for diesel
fuel, ASTM D 3699 for kerosene and ASTM D 6615 for jet
fuel.
26
Crude Oil Distillation
27
Crude Oil Distillation
28
