Ref: M.R.

Riazi, Characterization and Properties of Petroleum

Fractions, ASTM, 2005
 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.
 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.
 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.
 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%.
 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).
 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.
 Petroleum Definitions
Gas-to-Oil Ratio
The most important characteristic of a reservoir fluid in
addition to specific gravity (or API gravity) is its gas-to-
oil ratio (GOR), which represents the amount of gas
produced at SC in standard cubic feet (scf) to the amount
of liquid oil produced at the SC in stock tank barrel (stb).
Generally, reservoir fluids are black oil, volatile oil, gas
condensate, wet gas, and dry gas.
 Petroleum Definitions
Crude Oil
The crude oil produced from the atmospheric separator
has a composition different from the reservoir fluid from a
producing well. Two important characterisitics of a crude
that determine its quality are the API gravity (specific
gravity) and the sulfur content.

Generally, a crude with the API gravity of less than 20-22

is called heavy crude and with API gravity of greater than
33-40 is called light crude. Similarly, if the sulfur content
of a crude is less than 0.5 wt% it is called a sweet oil.
 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.
 Petroleum Standards
There are a number of international standard organizations
that recommend specific characteristics or standard
measuring techniques for various petroleum products.
Some of these organizations are as follows:

1. ASTM (American Society for Testing and Materials) in

the United States
2. ISO (International Organization for Standardization),
which is at the international level
3. IP (Institute of Petroleum) in the United Kingdom
4. API (American Petroleum Institute) in the United States
 Petroleum Properties
Distillation curves
For a crude oil or a petroleum fraction of unknown
composition, the boiling point may be presented by a curve
of temperature versus vol% (or fraction) of mixture
vaporized.
There are several methods of measuring and reporting
boiling points curves of crude oil and petroleum fractions:
1- ASTM D 86
2- True Boiling Point (TBP)
3- Simulated Distillation by GC (ASTM D 2887)
4- Equilibrium Flash Vaporization (EFV)
5- Distillation at Reduced Pressures (ASTM D 1160)
 Petroleum Properties
ASTM D 86
ASTM D 86 is one of the simplest and oldest methods of
measuring and reporting boiling points of crude oil and
petroleum fractions. The test is conducted at atmospheric
pressure with 100 mL of sample and the result is shown as
a distillation curve with temperatures at 0, 5, 10, 20, 30,
40, 50, 60, 70, 80, 90, 95, and 100% volume vaporized.

For crudes and heavy products, temperatures are reported

at maximum of 90, 70, or even 50% volume vaporized.
This is due to the cracking of heavy hydrocarbons at high
temperatures.
Petroleum Properties
ASTM D 86
 Petroleum Properties
True Boiling Point
ASTM D 86 distillation data do not represent actual
boiling point of components in a petroleum fraction.
Atmospheric true boiling point (TBP) data are obtained
through distillation of a petroleum mixture using a
distillation column with 15-100 theoretical plates at
relatively high reflux ratios (1-5 or greater).

The high degree of fractionation in these distillations gives

accurate component distributions for mixtures. The lack of
standardized apparatus and operational procedure is a
disadvantage, but variations between TBP data reported by
different laboratories for the same sample are small.
 Petroleum Properties
True Boiling Point
The IBP from TBP curve is less than the IBP from ASTM
D 86 curve, while the FBP of TBP curve is higher than that
of ASTM curve. Therefore, the boiling range based on
ASTM D 86 is less than the actual true boiling range.
 Petroleum Properties
ASTM D 2887
A distillation curve produced by GC is called a simulated
distillation (SD) and the method is described in ASTM D
2887 test method. Simulated distillation method is simple,
consistent, and reproducible and can represent the boiling
range of a petroleum mixture without any ambiguity.

Distillation curves by SD are presented in terms of boiling

point versus wt% of mixture vaporized because in gas
chromatography composition is measured in terms of wt%
or weight fraction. SD curves are very close to actual
boiling points shown by TBP curves.
 Petroleum Properties
ASTM D 1160
For products such as heavy gas oils that contain heavy
compounds and may undergo a cracking process during
vaporization at atmospheric pressure, distillation data are
measured at reduced pressures, 1, 2, 10, or 50 mmHg. The
experimental procedure is described in ASTM D 1160 test
method.

ASTM D 1160 distillation data are measured more

accurately than ASTM D 86 since it is conducted at low
pressure. For this reason ASTM D 1160 curves are closer
to TBP curves at the same pressure base.
 Petroleum Properties
The Watson characterization factor (Kw) is one of the
oldest characterization factors originally defined by
Watson et al. of the Universal Oil Products (UOP) in mid
1930s. For this reason the parameter is sometimes called
UOP characterization factor and is defined as

Tb1/ 3
Kw  where Tb  normal boiling point oR
SG

The naphthenic hydrocarbons have Kw values between

paraffinic and aromatic compounds. In general, aromatics
have low Kw values while paraffins have high values.
 Petroleum Properties
Reid vapor pressure (RVP) is the absolute pressure exerted
by a mixture at 100 oF and a vapor-to-liquid volume ratio of
4. The RVP is one of the important properties of gasolines
and jet fuels. The standard test of RVP is ASTM D 323.

For a pure compound the freezing point is the temperature

at which liquid solidifies at 1 atm pressure. Similarly the
melting point is the temperature that a solid substance
liquefies at 1 atm. A pure substance has the same freezing
and melting points; however, for petroleum mixtures, there
are ranges of melting and freezing points versus percent of
the mixture melted or frozen.
 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.
 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.
 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.
 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.
 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.
 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.
 Petroleum Properties
There are two methods of measuring octane number of a
fuel in the laboratory; motor octane number (MON) and
research octane number (RON). The MON is indicative
of high-speed performance (900 rpm) and is measured
under heavy road conditions (ASTM D 357). The RON is
indicative of normal road performance under low engine
speed (600 rpm) city driving conditions (ASTM D 908).
The arithmetic average value of RON and MON is known
as posted octane number (PON).

Isoparaffins and aromatics have high octane numbers while

n-paraffins and olefins have low octane numbers.
 Petroleum Properties
Generally there are three kinds of gasolines: regular,
intermediate, and premium with PON of 87, 90, and 93,
respectively. Improving the octane number of fuel would
result in reducing power loss of the engine, improving fuel
economy, and a reduction in environmental pollutants and
engine damage. There are a number of additives that can
improve octane number of gasoline or jet fuels. These
additives are tetra-ethyl lead (TEL), alcohols, and ethers.
 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.
 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.
 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.
 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%.
 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.
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.
 Crude Oil Distillation
Ref: R. Smith, Chemical Process Design and Integration, Wiley, 2005.

In the first stage of processing crude oil, it is distilled

under conditions slightly above atmospheric pressure. A
range of petroleum fractions are taken from the crude oil
distillation.

Designs are normally thermally coupled. Most

configurations follow the thermally coupled indirect
sequence as shown in Figure (a). However, rather than
build the configuration in Figure (a), the configuration of
Figure (b) is the one normally constructed. Notice that the
two arrangements are equivalent.
Crude Oil Distillation
 Crude Oil Distillation
Unfortunately, a practical crude oil distillation cannot be
operated in quite the way shown in Figure (b), because:
 Extremely high temperature sources of heat would be
required. Steam is usually not distributed for process
heating at such high temperatures.
 High temperatures in the reboilers would result in
significant fouling of the reboilers from decomposition of
the hydrocarbons to form coke.
Therefore, in practice, some or all of the reboiling is
substituted by the direct injection of steam into the
distillation. The steam is condensed in the overhead and is
separated in a decanter from the hydrocarbons.
 Crude Oil Distillation
Another problem with the
arrangement in Figure (b) is that
as the vapor rises up the main
column, its flow rate increases
significantly.
This problem can be solved by
removing heat from the main
column at intermediate points by
pumparound. This corresponds
with introducing some
condensation of the vapor at the
top of intermediate columns.
 Crude Oil Distillation
Pumparound
In a pumparound, liquid is taken from the column, sub
cooled and returned to the column at a higher point.

By choosing the most appropriate flow rate and temperature

for the pumparound, the heat load to be removed can be
adjusted to whatever is desired.

The trays between the liquid draw and return in a

pumparound have more to do with heat transfer than mass
transfer. In addition to returning a sub cooled liquid to the
column, mixing occurs as material is introduced to a higher
point in the column.
 Crude Oil Distillation
Furnace
The crude oil entering the main column needs to be
preheated to around 400 ◦C. This is down by a furnace
(fired heater). Note that this temperature is higher than
decomposition limit, but a high temperature can be tolerated
in the furnace if it is only for a short residence time.

All of the material that needs to leave as product above the

feed point must vaporize as it enters the column. In addition
to this, some extra vapor over and above this flowrate must
be created that will be condensed and flow back down
through the column as reflux. This extra vaporization to
create reflux is known as overflash.
 Crude Oil Distillation
The distillation of crude oil under conditions slightly
above atmospheric pressure is limited by the maximum
temperature that can be tolerated by the materials being
distilled, otherwise there would be decomposition.

The residue from the atmospheric crude oil distillation is

usually reheated to a temperature around 400◦C or
slightly higher and fed to a vacuum column, which
operates under a high vacuum (about 50 mmHg) to
allow further recovery of material from the atmospheric
residue, as shown in the next Figure.
Crude Oil Distillation