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2

Feedstocks and Products of Crude Oil


and Natural Gas Refineries
M.R. Riazi1 and Semih Eser2

2.1 Nature and ConstituENTS of


Petroleum Fluids

As discussed in Chapter 1, petroleum fluids are mixtures


of various hydrocarbons that may exist as gas or liquid in
a petroleum reservoir. The principal elements of petroleum
are carbon (C), hydrogen (H), and small quantities of heteroatoms of sulfur (S), nitrogen (N), and oxygen (O). It is
generally believed that the petroleum hydrocarbons have
been derived from the conversion of organic compounds
in some aquatic plants and animals. The most important factors that affect conversion of organic compounds
to petroleum hydrocarbons are (1) heat and pressure,
(2)radioactivity such as gamma rays, and (3) catalytic reactions. Vanadium and nickel species are the most effective
catalysts in the formation of petroleum and are needed for
the conversion reactions. For this reason, these metals may
be found in small quantities in petroleum fluids. Occasionally traces of radioactive isotopes such as uranium and
potassium can also be found in petroleum. The conditions
required for converting organic compounds into petroleum are (1) geological time frame in millions of years,
(2)pressure up to 17 MPa (~2500 psi), and (3) temperature
not exceeding 100120 C (~ 210250 F). In some cases,
bacteria may have severely biodegraded the oil, destroying
the light hydrocarbons. An example of such a case would
be the large heavy oil accumulations found in Venezuela.
Petroleum is a mixture of thousands of different identifiable hydrocarbons that are discussed in the next section.
Once petroleum is accumulated in a reservoir or in various sediments, hydrocarbon compounds may be converted
from one form to another with time and varying geological
conditions. The main difference between various oils from
different fields around the world is the difference in their
composition of hydrocarbon compounds and impurities [1].
Compounds that only contain elements of carbon
and hydrogen are called hydrocarbons, and they form the
largest group of organic compounds found in petroleum.
There might be as many as several thousand different
hydrocarbon compounds in petroleum reservoir fluids.
Hydrocarbon compounds have a general closed formula
of CxHy, where x and y are integer numbers. The lightest
hydrocarbon is methane (CH4), which is the main component in natural gas. Methane is from a group of hydrocarbons called paraffins. Hydrocarbons are generally divided
into four groups: (1) paraffins, (2) olefins, (3) naphthenes,
and (4) aromatics. Paraffins, olefins, and naphthenes are
sometimes called aliphatic versus aromatic compounds.
1
2

The International Union of Pure and Applied Chemistry (IUPAC), a nongovernmental organization, provides
standard names, nomenclature, and symbols for chemical
compounds, including hydrocarbons [2].
Paraffins are also called alkanes and have the general
formula of CnH2n+2, where n is the number of carbon atoms
in a given molecule. Paraffins are divided into two groups
of normal and isoparaffins. Normal paraffins or normal
alkanes are simply written as n-paraffins or n-alkanes,
and they are open, straight-chain saturated hydrocarbons.
Paraffins are the largest series of hydrocarbons found in
petroleum and begin with methane, which is also shown
by C1. Figure 2.1 shows several lighter paraffins found in
petroleum fluids [3]. For example, the open formula for
n-butane, n-C4, can be shown as CH3-CH2-CH2-CH3, and for
simplicity in drawing, only the carbon-carbon bonds are
drawn and most C-H bonds are omitted.
The second group of paraffins is called isoparaffins,
which are branched-type hydrocarbons and they begin with
isobutane (also called methylpropane), which has the same
closed formula as n-butane (C4H10). Compounds of different
structures with the same closed formula are called isomers.
As shown in Figure 2.1, there are two isomers for butane,
three for pentane, and five isomers for hexane (only four are
shown in Figure 2.1.) Similarly, octane (C8H18) has 18 and
dodecane (C12H26) has 355 isomers, whereas octadecane
(C18H38) has 60,523 and C40 has 62 1012 isomers. The number of isomers rapidly increases with the number of carbon
atoms in a molecule because of the rapidly rising number of
their possible structural arrangements, as shown in Figure
2.2 [1]. It should be noted that many of these isomers may
not be found in petroleum because they are not thermodynamically stable. For the paraffins in the range of C5C12 the
number of isomers is more than 600, although only approximately 200400 of them have been identified in petroleum
mixtures. Isomers have different physical and chemical
properties. The same increase in number of isomers with
molecular weight applies to other hydrocarbon series. As an
example, the total number of hydrocarbons (from different
groups) having 20 carbon atoms is more than 300,000 [5].
Under standard conditions of temperature and pressure (STP), the first four members of the alkane series
(methane, ethane, propane, and butane) are in gaseous
form, from C5H12 (pentane) to n-heptadecane (C17H36) are
liquids, and n-octadecane (C18H38) or heavier compounds
exist as wax-like solids at STP. Paraffins from C1 to C40 usually appear in crude oil and represent up to 20 % of crude

Kuwait University, Kuwait


The Pennsylvania State University, University Park, PA, USA

21

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22

Petroleum Refining and Natural Gas Processing

have the general formula of CnH2n. If there are two double


bonds, the olefin is called a diolefin (or diene), such as
butadiene (CH2=CH-CH=CH2). Unsaturated compounds are
more reactive than saturated hydrocarbons (without double
bond). Olefins are uncommon in crude oils because of their
reactivity with hydrogen that saturates them; however, they
can be produced in refineries through cracking reactions.
Olefins are valuable products of refineries and are used as
feedstocks for petrochemical plants to produce polymers
such as polyethylene. Similarly compounds with triple
bonds such as acetylene ( CH CH ) are not found in crude
oils because of their tendency to become saturated [1].
Naphthenes or cycloalkanes are ring or cyclic saturated
hydrocarbons with general formula of CnH2n. Cyclopentane
(C5H10), cyclohexane (C6H12), and their derivatives such
as n-alkylcyclopentanes are normally found in crude oils.
Three types of naphthenic compounds are shown below.

Cyclopentane
(C5H10)

Figure 2.1Lighter paraffin hydrocarbons present in


petroleum and natural gas [3].

by volume. Because paraffins are fully saturated (no double


bond) they are stable and remain unchanged over long periods of geological time.
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 mono-olefins or alkenes and include
ethene (also named ethylene; CH2=CH2) and propene (or
propylene; CH2=CH-CH3). In addition to the structural isomerism connected with the location of double bond, there is
another type of isomerism called geometric isomerism that
indicates the way atoms are oriented in space. The configurations are differentiated in their names by the prefixes cisand trans-, such as cis- and trans-2-butene. Mono-olefins

Number of isomers

1.0 1015

1.0 1010

1.0 105

1.0 100

10

20
30
Number of carbon atoms

40

Figure 2.2Number of possible alkane isomers [1].

50

Methylcyclopentane
(C6H12)

Ethylcyclohexane
(C8H16)

If there is only one alkyl group from n-paraffins (i.e.,


methyl, ethyl, propyl, n-butyl, etc.) attached to a cyclopentane hydrocarbon, the series is called n-alkylcyclopentanes,
such as the two hydrocarbons shown above where on each
junction of the ring there is a CH2 group, except on the alkyl
group juncture, where there is only a CH group. Naphthenic
hydrocarbons with only one ring are also called monocycloparaffins or mononaphthenes. In heavier oils, saturated
multirings attached to each other called polycycloparaffins or
polynaphthenes may also be available. 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 %. Generally,
any petroleum mixture that has hydrocarbon compounds
with five carbon atoms also contains naphthenic compounds.
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 with alternating double bonds that begin with a
benzene molecule (C6H6). The name aromatic refers to
the fact that such hydrocarbons commonly have fragrant
odors. A group of lighter aromatic hydrocarbons is shown
in Figure 2.3. Although benzene has three carbon-carbon
double bonds, it has a unique arrangement of electrons with
resonance structures of the double bonds (aromaticity) that
allow benzene to be relatively stable. However, benzene is
known to be a cancer-inducing compound. For this reason,
the amount of benzene allowed in petroleum products such
as gasoline or fuel oil is limited by government regulations
in many countries. Under standard conditions, benzene,
toluene, and xylene are in liquid form whereas naphthalene
is in a solid state.
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 compounds in
this homologous group of hydrocarbons have the general

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Chapter 2 n Feedstocks and Products of Crude Oil and Natural Gas Refineries

23

Figure 2.4An example of asphaltene molecule [6].

Figure 2.3Lighter aromatic hydrocarbons present in


petroleum and natural gas [3].

formula of CnH2n-6 (where n 6). Generally, an aromatic


series with only one benzene ring is also called monoaromatics or mononuclear aromatics. Naphthalene and
its derivatives that have only two unsaturated rings are
sometime called diaromatics. Crude oils and reservoir
fluids all contain aromatic compounds. However, heavy
petroleum fractions and residues contain unsaturated multirings with many benzene and naphthene rings attached to
each other. Such aromatics that are in solid form are also
called polyaromatic hydrocarbons (PAHs) or polynuclear
aromatics (PNAs). In this chapter, the terms of mono- and
polyaromatics are used. Heavy crude oils usually contain
more aromatics than light crudes. The amount of aromatics in coal liquids is usually high, and it could reach as high
as 98 % by volume. It is common to have compounds with
naphthenic and aromatic rings side by side, especially in
heavy fractions. Monoaromatics with one naphthenic ring
have the formula of CnH2n-8. There are many combinations
of alkylnaphthenoaromatics [4,5].
Normally, high-molecular-weight polyaromatics contain several heteroatoms such as sulfur, nitrogen, or oxygen,
but these compounds are still called aromatic compounds
because their electronic configurations maintain the aromatic character. Two types of these compounds are shown
below [1].
S

2.2 Reservoir FluidsCrude Oil


and Natural Gas
N
H

Dibenzothiophene

Such heteroatoms in multiring aromatics are commonly found in asphaltene compounds, as shown in
Figure 2.4, where, for simplicity, carbon and hydrogen
atoms are not marked on the rings or on the paraffinic
chains attached to the ring systems.
Sulfur is the most important heteroatom in petroleum
and it can be found in cyclic (e.g., thiophenes) and noncyclic
compounds such as mercaptans (R-S-H) and sulfides (R-SR), where R and R are alkyl groups. Sulfur in natural gas is
usually found in the form of hydrogen sulfide (H2S). Some
natural gases contain H2S as high as 30 % by volume. The
amount of sulfur in a crude oil may vary from 0.05 to 6 % by
weight. The presence of sulfur in finished petroleum products is harmful. For example, the presence of sulfur in gasoline can promote corrosion of engine parts. The amounts
of nitrogen and oxygen in crude oils are usually less than
the amount of sulfur by weight. In general, for petroleum
oils the elemental composition varies within fairly narrow
ranges, as shown below on a weight basis [5,6]:
Carbon (C), 83.087.0 %
Hydrogen (H), 10.014.0 %
Nitrogen (N), 0.12.0 %
Oxygen (O), 0.051.5 %
Sulfur (S), 0.056.0 %
Metals (nickel, vanadium, and copper), <1000 ppm (0.1 %)
Generally, in heavier oils (with lower API gravity) the
proportions of carbon, sulfur, nitrogen, and oxygen elements
increase, but the hydrogen content and the overall quality
decrease. A further discussion on the chemistry of petroleum and the types of compounds found in petroleum fractions is provided by Speight [6]. Vanadium concentrations
of greater than 2 ppm in fuels can lead to severe corrosion
in turbine blades and deterioration of refractory in furnaces.
Nickel, vanadium, and copper can also severely affect the
activities of catalysts and result in lower quality products.
The metal content may be reduced by solvent extraction
with organic solvents. Organometallic compounds are concentrated in the asphaltenes and residues. Some major
low-molecular-weight impurities in crude oil include carbon
dioxide (CO2), H2S, metal oxides [aluminum oxide (Al2O3),
iron(III) oxide (Fe2O3), silicon dioxide (SiO2), etc.], nitrogen
(N2), oxygen (O2), salts [sodium chloride (NaCl), calcium
carbonate (CaCO3), etc.], sulfur, and water (H2O) [3].

Benzocarbazole (C16H11N)

The word fluid refers to a pure substance or a mixture of


compounds that are in the form of gas, liquid, or a mixture
of liquid and gas (vapor). Reservoir fluid is a term used for the
mixture of hydrocarbons found in a geological petroleum reservoir or the stream leaving a producing well. Three factors

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24

Petroleum Refining and Natural Gas Processing

Table 2.1Types and Characteristics of Various Reservoir Fluids [1]


Reservoir Fluid Type

GOR (scf/stb)

CH4 (mol %)

C6+ (mol %)

API Gravity of STO

Black oil

<1000

50

30

< 40

Volatile oil

10003000

5070

1030

4045

Gas condensate

300050,000

7085

310

45

Wet gas

50,000

75

<3

>50

Dry gas

100,000

90

<1

No liquid

API gravity of STO refers to the API gravity of sto produced at the surface facilities at standard conditions (289 K and 1 atm).

determine if a reservoir fluid is in the form of gas, liquid, or


a mixture of gas and liquid. These factors are (1) composition of reservoir fluid, (2) temperature, and (3)pressure. 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 standard
conditions in standard cubic feet (scf) to the amount of liquid
oil produced at the standard condition in stock tank barrels
(stb). Other units of GOR and its calculation methods are
discussed in Chapters 1 and 10 of ASTM Manual 50 [1]. Reservoir fluids are generally categorized into four or five types,
the characteristics of which are given in Table 2.1. These five
fluids in the direction of increasing GOR are black oil, volatile
oil, gas condensate, wet gas, and dry gas.
A natural gas is called dry gas if it does not produce
any liquid hydrocarbons after the surface separator under
standard conditions. A natural gas that produces liquid
hydrocarbons after production at the surface facilities
is called wet gas. The word wet refers to the presence
of hydrocarbon liquids in a natural gas that condense at
surface conditions. In dry gases no liquid hydrocarbon is
formed at the surface conditions. Volatile oils have also
been called high-shrinkage crude oil and near-critical oils
because the reservoir temperature and pressure are very
close to the critical point of such oils, but the critical temperature is always greater than the reservoir temperature
[1]. Gases and gas condensate fluids have critical temperatures that are less than the reservoir temperature. Black
oils contain heavier compounds; therefore, the API gravity
of stock tank oil is generally lower than 40 and the GOR is
less than 1000 scf/stb. The specifications given in Table2.1
for various reservoir fluids, especially at the boundaries
between different types, are somewhat arbitrary and may
vary from one source to another. It is possible to have a
reservoir fluid type with properties outside of the corresponding limits given above. Determination of a type of
reservoir fluid by the above rule of thumb on the basis of
the GOR, the API gravity of stock tank oil, or its color is
not possible for all fluids. In general, oils produced from
wet gas, gas condensate, volatile oil, and black oil increase
in specific gravity (decrease in API gravity and quality) in
the same order. Liquids from black oils are viscous and
black in color, whereas the liquids from gas condensates
or wet gases are clear and colorless. Volatile oils produce
brown with some red/green color liquid. Wet gas contains
less methane than a dry gas but a larger fraction of C2C6
components. The main difference between these reservoir
fluids is obviously found in their molecular composition.
An example of the composition of different reservoir fluids
is given in Table 2.2 [1].

In this table, C7+ refers to all hydrocarbons having seven


or more carbon atoms; this group is called the heptane-plus
fraction. C6 refers to a group of all hydrocarbons with six
carbon atoms (hexanes) that exist in the fluid. M7+ and SG7+
are the molecular weight and specific gravity, respectively,
at 15.5 C (60 F) for the C7+ fraction of the mixture. It
should be noted that molecular weight and specific gravity
of the whole reservoir fluid are less than the corresponding
values for the heptane-plus fraction. For example, for the
crude oil sample in Table 2.2, the specific gravity of whole
crude is 0.871, or an API gravity of 31. Details of such
calculations are discussed in ASTM Manual 50 [1]. These
compositions have been determined from a recombination
of the compositions of the corresponding separator gas and
stock tank liquid, which have been determined by various
analytical tools (i.e., gas chromatography, mass spectrometry, etc.). Composition of reservoir fluids varies with the
reservoir pressure and reservoir depth. In a producing oil
field, the sulfur and amount of heavy compounds generally
increase with production time. However, it is important
to note that within an oil field, the concentration of light
hydrocarbons and the API gravity of the reservoir fluid
increase with the reservoir depth, whereas its sulfur and
C7+ contents decrease with the depth [6]. The lumped C7+
fraction in fact is a mixture of many hydrocarbons up to C40
or higher. As an example, the number of pure hydrocarbons
from C5 to C9 detected by chromatography tools in a crude
oil from North Sea reservoir fluids was 70 compounds.
Most recently, Mansoori has suggested that naturally found
hydrocarbon petroleums can be categorized into seven
groups, including two semi-solid forms of tar sands and oil
shale [3]. The molecular weight distribution of these petroleum fluids is shown in Figure 2.5.
Reservoir fluids from a producing well are introduced
to two- or three-stage separators that reduce the pressure
and temperature of the stream to atmospheric pressure
and temperature. The liquid leaving the last stage is called
stock tank oil (sto) and the gas released in various stages
is called associated gas. The liquid oil after necessary field
processing is called crude oil. The main factor in operation
and design of an oil-gas separator is to find the optimum
operating conditions of temperature and pressure so that
the amount of produced liquid (oil) is maximized. Such
conditions can be determined through phase behavior calculations, which are discussed in detail in ASTM Manual
50 [1]. Reservoir fluids from producing wells are mixed
with free water. The water is separated through gravitational separators on the basis of the difference between
densities of water and oil. The remaining water from crude
can be removed through dehydration processes. Another

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Chapter 2 n Feedstocks and Products of Crude Oil and Natural Gas Refineries

25

Table 2.2Composition (mol %) and Properties of Various Reservoir Fluids and a Crude Oil [1]
Component

Dry Gas (1)

Wet Gas (2)

Gas Condensate (3)

Volatile Oil (4)

Black Oil (5)

Crude Oil (6)

CO2

3.70

0.00

0.18

1.19

0.09

0.00

N2

0.30

0.00

0.13

0.51

2.09

0.00

H2S

0.00

0.00

0.00

0.00

1.89

0.00

C1

96.00

82.28

61.92

45.21

29.18

0.00

C2

0.00

9.52

14.08

7.09

13.60

0.19

C3

0.00

4.64

8.35

4.61

9.20

1.88

iC4

0.00

0.64

0.97

1.69

0.95

0.62

nC4

0.00

0.96

3.41

2.81

4.30

3.92

iC5

0.00

0.35

0.84

1.55

1.38

2.11

nC5

0.00

0.29

1.48

2.01

2.60

4.46

C6

0.00

0.29

1.79

4.42

4.32

8.59

C7+

0.00

1.01

6.35

28.91

30.40

78.23

100.00

100.00

100.00

100.00

100.00

100.00

GOR (scf/stb)

69,917

4428

1011

855

M7+

113

143

190

209.8

266

SG7+ (at 15.5 C)

0.794

0.795

0.8142

0.844

0.895

46.7

46.5

42.1

36.1

26.6

API7+

surface operation is the desalting process, which is necessary to remove salt from crude oils. Separation of oil, gas,
and water from each other and removal of water and salt
from oil and any other process that occurs at the surface
are called surface production operations and are discussed
in Chapter 11.
In addition to the impurities (hetoroatoms and metals)
discussed earlier, some impurities may result from compounds that have been added to petroleum fluids for vari-

natural gas

gas condensate
(NGL)

light crude

ous reasons during their production, transportation, and


storage. These include but are not limited to acids, alcohols,
aromatic hydrocarbons, detergents, and polymers. Furthermore, petroleum fluids often contain compounds that
result from the physical association with hydrocarbons;
these may include colloids, crystalline solids, flocs, and
slugs [3].
The crude oil produced from the atmospheric separator has a composition different from the reservoir fluid

intermediate
crude

heavy oil

tar sand

oil shale

Figure 2.5Various categories of natural gas and liquids naturally occurring in petroleum fluids and their approximate
hydrocarbon molecular weight distributions according to their carbon numbers [3,4].
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26

Petroleum Refining and Natural Gas Processing

obtained from a producing well. The light gases are separated, and crude oils usually have almost no methane and
a small C2C3 content whereas its C7+ content is higher than
the original reservoir fluid. As an example, the composition
of a crude oil produced through a three-stage separator
from a reservoir fluid is also given in Table 2.2 in the last
column. Actually this crude is produced from a black oil
reservoir fluid, the composition of which is also given in
Table 2.2 (column 5).
Two important characteristics of a crude oil that determine its quality are the API gravity (specific gravity) and
sulfur content. Generally, a crude with an API gravity of
less than 20 (specific gravity > 0.934) is called a heavy crude,
and a crude with an API gravity of greater than 40 (specific
gravity < 0.825) is called a light crude [1,5]. Crudes with an
API gravity of less than 10 are considered as extra heavy oil,
such as bitumen. Similarly, if the sulfur content of a crude
is less than 0.5 wt % it is called sweet oil. On the other
hand, the term sour oil refers to crudes that have more than
0.5 wt % sulfur. It should be noted that these ranges for the
gravity and sulfur content are relative and may vary from
one source to another. Further classification of crude oils
will be discussed in Chapter 4.

2.3 Refining Processes and Products


from Crude Oil Refineries

A crude oil produced after necessary field processing and


surface operations is transferred to a refinery for processing and conversion into various useful products. Petroleum
refining (or crude oil refining in more precise terms) has
evolved from simple batch distillation in the late 19th century to todays complex processing schemes in modern refineries. Refining processes can be generally divided into three
major types: (1) separation, (2) conversion, and (3) finishing.
Separation is a physical process that is carried out by
using different techniques to fractionate crude oil or its
derivatives. The most important separation process is distillation, which occurs in a distillation column to separate the
constituent compounds on the basis of differences in their
boiling points. Other major physical separation processes
include absorption, stripping, and solvent extraction. In the
gas plant of a refinery, absorption by a liquid solvent retains
C3+ hydrocarbons from a gas mixture and allows methane
and ethane to be sent overhead as fuel gas. The solvent is
then regenerated in a stripping unit. The conversion processes involve chemical changes that occur with hydrocarbons in reactors. The purpose of such reactions is to change
the molecular weight and convert hydrocarbon compounds
from one type to another. The most important reaction
in modern refineries is cracking, which converts heavy
hydrocarbons to lighter and more valuable hydrocarbons.
Catalytic cracking and thermal cracking are commonly
used for this purpose. Other types of reactions such as
reforming, isomerization, and alkylation are used to produce
high-octane-number gasoline. Finishing processes achieve
the purification of various product streams by processes
such as desulfurization or acid treatment to remove impurities and stabilize the fuels. Finishing processes that also
include blending ensure that the refinery products meet the
specifications dictated by performance characteristics and
environmental regulations [68].
Crude oil in a refinery upon the desalting process enters
the atmospheric distillation column where compounds are

separated with respect to their boiling points. Hydrocarbons in a crude have boiling points ranging from 160 C
(boiling point of methane) to more than 600 C (1100 F),
which is the boiling point of the heaviest distillable compounds in the crude oil. However, the carbon-carbon bond
in paraffinic hydrocarbons breaks down at temperatures
near 350 C (660 F). This process is called cracking and
it is undesirable during the distillation process because
it changes the chemical composition of the crude feed.
For this reason, compounds having boiling points above
350 C (660 F), constituting the residuum fraction, are
removed from the bottom of the atmospheric distillation
column and sent to a vacuum distillation column. Because
by distillation it is not possible to completely separate the
constituent compounds of the crude oil, a distillation column does not produce pure hydrocarbon streams. Instead,
distillate f ractions are produced as defined according to
the boiling point of the lightest and heaviest compounds in
the mixtures of hydrocarbons. The lightest product of an
atmospheric column is a mixture of methane and ethane
(but mainly ethane), which has a boiling range of 180 to
80 C (260 to 40 F) corresponding to the boiling points
of methane and ethane, respectively. This mixture, referred
to as fuel gas in a refinery, is the lightest petroleum fraction. Fractions with a wider range of boiling points contain
a greater number of hydrocarbons. All fractions from a
distillation column have a known boiling range, except the
residuum, the upper boiling point of which is not usually
known. The boiling points of the heaviest components in a
crude oil are not really known because many of them would
undergo cracking or other chemical reactions at temperatures lower than their boiling points. Identification of the
structure and determining the properties of the heaviest
compounds found in crude oils and petroleum residuum
still present a difficult challenge to researchers. Theoretically, it can be assumed that the boiling point of the heaviest compound in a crude oil is infinity. Atmospheric residue
contains compounds with carbon numbers greater than 25,
whereas vacuum residue has compounds with a carbon
number greater than 50 (M > 800). Table 2.3 lists some
petroleum fractions produced from distillation columns
along with their boiling point ranges and applications. In
this table, the boiling points and equivalent carbon number
ranges are approximate and they may vary according to the
desirable properties of specific products. For example, the
light gas fraction consists mainly of a mixture of ethane,
propane, and butane; however, some heavier compounds
(C5+) may also exist in this fraction. The fraction is further
fractionated to obtain ethane (a fuel gas), propane, and
butane (petroleum gases). The petroleum gases are liquefied under pressure to produce liquefied petroleum gas
(LPG) that can be used as fuel for heating and cooking in
dwellings or as autogas [http://www.worldlpgas.com/]. In
addition, butane may be separated from the gas mixture
to be used for improving the vapor pressure characteristics
(volatility) of gasoline in cold weather. Petroleum fractions
separated by distillation may undergo further processing to
produce the desired products. For example, gas oil may go
through a cracking process to produce more gasoline. The
principal refinery processes are discussed in Chapter 5 of
this manual. Because distillation is not a perfect separation
process, the initial and final boiling points for each fraction are not exact and especially the endpoints represent

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Chapter 2 n Feedstocks and Products of Crude Oil and Natural Gas Refineries

27

Table 2.3Some of the Petroleum Fractions Produced from Distillation Columns [1]
Approximate Boiling Range

Petroleum Fraction

Approximate
Hydrocarbon Range

Light gases

C2C4

90 to 1

130 to 30

Gasoline (light and heavy)

C4C10

1 to 200

30390

Naphthas (light and heavy)

C4C11

1 to 205

30400

Jet fuel

C9C14

150255

300490

Kerosene

C11C14

205255

400490

Diesel fuel

C11C16

205290

400550

Light gas oil

C14C18

255315

490600

Heavy gas oil

C18C28

315425

600800

Wax

C18C36

315500

600930

Lubricating oil

>C25

>400

>750

Vacuum gas oil

C28C55

425600

8001100

Residuum

>C55

>600

>1100

approximate values. Fractions may be classified as narrow or wide depending on their boiling point range. As an
example, the fractionation of an Alaskan crude oil into various products by distillation is graphically shown in Figure
2.6. The weight and volume percentages for the products
are close to each other. It can be seen in Figure 2.6 that
more than 50 % of the crude is processed in the vacuum
distillation unit. The vacuum residuum consists mainly of
resin- and asphaltene-type compounds containing highmolecular-weight multiring aromatics. The vacuum residuum may be further processed for upgrading or mixed with
lighter petroleum fractions to obtain saleable products.
Distillation of a crude oil can also be performed in the
laboratory to divide the mixture into many narrow boiling
point range fractions with a boiling range of approximately
10 C. Such narrow range fractions are sometimes referred
to as petroleum cuts. When boiling points of all of the cuts
in a crude are known, then the boiling point distribution
(distillation curve) of the whole crude can be obtained. In
a petroleum cut, hydrocarbons of various types are lumped
together in four groups of paraffins (P), olefins (O), naphthenes (N), and aromatics (A). For olefin-free petroleum
cuts, the composition is represented by the PNA content.
Crude oils are generally free of olefins.
As mentioned earlier, the petroleum fractions presented in Table 2.3 are not the final products of a refinery.
They go through further separation (physical), conversion
(chemical), and finishing processes to achieve the product
specifications set by the market and government regulations. Through refining processes (discussed in Chapter 5),
the petroleum fractions shown in Table 2.3 are converted
to petroleum products. The terms petroleum fraction,
petroleum cut, and petroleum product are usually used
interchangeably, but this is not appropriate because each
term has a specific meaning that is different from the other
two. In general, the petroleum products that are obtained
in a refinery can be divided into two groups fuel products and nonfuel productsas discussed in the following
sections.

2.3.1 Petroleum Fuel Products


The major petroleum fuel products of a refinery are LPG,
gasoline, jet fuel, diesel and heating oil, residual fuel oil, and
petroleum coke as described below [1,710]. The specifications of these fuels are discussed in Chapter 4 of this manual.
1. LPGs are mainly used for domestic heating and cooking (50 %), industrial fuel (clean fuel requirement)
(15 %), feedstock for steam cracking (25 %), and as a
motor fuel (autogas) for spark ignition engines (10 %).
LPG is produced by crude oil refining or natural gas
fractionation. The estimated world production in 2005
was 250 million tons per year (8 million bbl/day) [10].
LPG consists mainly of a mixture of propane (C3H8)
and n-butane (C4H10), but it may also include ethane
(C2H6), ethylene (C2H4), propylene (C3H6), butylene
(C4H8), isobutane, and isobutylene in small concentrations. Propane, butane, or propane/butane mixtures can be liquefied at ambient temperature under
moderate pressure. LPGs are considered ideal fuels
because they can be transported and stored in liquid
form and used as a gas or a liquid. Propane can be safely used at ambient temperatures from approximately
40C (104F) to 45C (113F), whereas butane can be
used at temperatures from 0C (32F) to approximately
110C (230F) [8]. They have high energy density, low
sulfur content, and they burn cleanly.
LPGs have been used increasingly as auto fuel
under the generic name autogas. The composition
of autogas varies depending on the prevailing ambient
temperatures in the countries it is used. At moderate
ambient temperatures, it consists of 6070 % propane
and 3040 % butane [9]. The advantages of using LPG
compared with gasoline and diesel include lower fuel
and maintenance cost and lower engine emissions. See
Chapter 4 for specifications on autogas and variations
in specifications in different countries.
2. Gasoline is perhaps one of the most important products of a refinery. In the United Kingdom it is referred
to as petrol. Gasoline is obtained by blending various

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28

Petroleum Refining and Natural Gas Processing

60

Vacuum
Residuum

50

- 455

30
Atmospheric Distillation 46.9 %

Heavy
Gas Oil

Boiling Point, C

Vacuum
Gas Oil

40

Carbon Number

- 655

- 345

20

Light
Gas Oil
- 205
Kerosene

10

Naphtha
Vacuum Distillation 53.1 %
- -90

0
0

20

40

60

80

100

Volume Percent
Light Gases

Light Gasoline

Figure 2.6Products and composition of Alaska crude oil [1].

streams obtained from different refinery operations,


including crude oil distillation, catalytic cracking, and
catalytic reforming. It contains hydrocarbons from C4
to C11 (molecular weight of ~100110). It is used as a
fuel for cars with spark-ignition engines. Its main characteristics include anti-nock (octane number), volatility
(distillation data and vapor pressure), stability, and
density. The main evolution in gasoline production has
been the introduction of nonleaded gasoline (referred
to as unleaded gasoline, which excludes using tetraethyl lead as an additive to increase the octane number)
in many parts of the world and the use of reformulated
gasoline (RFG) in the United States. The RFG has less
butane, less aromatics, and more oxygenates. Sulfur
content of gasoline should not exceed 0.03 % by weight.
Further properties and characteristics of gasoline will
be discussed in Chapter 4. The U.S. gasoline demand
in 1964 was 4.4 million bbl/day and increased from 7.2
to 8.0 million bbl/day in a period of 7 years from 1991
to 1998 [1]. In the 1990s, gasoline was approximately

one-third of the refinery products in the United States,


whereas in July 2007 gasoline production was approximately 9.33 million bbl/day, or 37.5 % of total products
according to the API report.
3. Kerosene is a distillate fraction of crude oil that boils
between 150C and 250C and is primarily used for
producing jet fuel to power gas turbine or jet engines.
To a much smaller extent, kerosene is used as fuel for
lighting and cooking, particularly in rural areas where
access to natural gas, LPG, and electricity is limited.
Jet fuel, which is also called aviation turbine fuel,
is a premium fuel that has shown a faster increase in
demand than any petroleum fuel because of expanding
civil and military aviation. In 2007, an estimated consumption for jet fuel was 205 million t [10]. The main
characteristics of jet fuel include sulfur content, cold
resistance (more stringent performance for military jet
fuel), density, aromatics content, and ignition quality.
ASTM and the International Air Transport Association
(IATA) have issued specifications for commercial (e.g.,

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Chapter 2 n Feedstocks and Products of Crude Oil and Natural Gas Refineries

Jet A, Jet A-1, the Russian TS-1) and military jet fuel
(JP-8) that differ only in freezing point [9].
4. Diesel and heating oil are used for motor fuel and
domestic purposes. Diesel is obtained from fractional
distillation of crude oil between 200C and 350C.
The main characteristics are ignition (for diesel oil),
volatility, viscosity, cold resistance, density, sulfur content (corrosion effects), and flash point (safety factor).
There are basically three kinds of diesel fuel: No. 1,
No. 2, and No. 4. Diesel No. 1 is for use in farm and
city buses, whereas diesel No. 2 is for use in automobile, truck, and railroad vehicles. Diesel No. 4 is for use
in railroad, marine, and stationary engines [9]. Diesel
fuels used in city buses have a lower endpoint, lower
sulfur content, and higher cetane number.
5. Residual fuel oil is used for industrial fuel, thermal production of electricity, and motor fuel (low speed diesel
engines). Its main characteristics are viscosity (good
atomization for burners), sulfur content (corrosion),
stability (no decantation separation), cold resistance,
and flash point (for safety). Basically there are five types
of fuel oils in commercial use: No. 1, No. 2, No. 4, No. 5,
and No. 6. Fuel oil No. 1 is used for stoves and farms,
fuel oil No. 2 is for home heating uses, No. 4 is used for
light industrial uses, No. 5 is used for medium industrial
applications, and No. 6 is used for heavy industrial and
marine applications [9]. Fuel oil No. 1 has the lowest
density, boiling point, flash point, pour point, viscosity,
and sulfur content, whereas fuel oil No. 6 is the heaviest
fuel oil, with high sulfur content and high viscosity.
6. Petroleum coke, which is a solid byproduct obtained
from delayed coking or fluid coking of vacuum distillation residue, may be used as industrial fuel depending
on its sulfur and metal contents [11]. It contains less
than 1 %wt ash, but it needs to be burned in industrial
furnaces with strict controls on emissions. Important
properties of fuel coke include grindability, volatile
matter content, sulfur content, and nickel and vanadium contents. Nonfuel uses of petroleum coke are
described in the next section.

2.3.2 Nonfuel Petroleum Products


The major nonfuel petroleum products include solvents,
naphthas, petrochemical feedstocks, lubricating oils,
waxes, asphalts, and petroleum cokes [1,79,11]. Brief
descriptions of the nonfuel products and their uses are
given below.
1. Solvents are light petroleum cuts in the C4C14 range
that have numerous applications in industry and
agriculture. For example, white spirits that have boiling point ranges between 135 and 205 C are used as
paint thinners. The main characteristics of solvents are
volatility, purity, odor, and toxicity. Benzene, toluene,
and xylenes (BTX) are used as solvents for glues and
adhesives. Naphthas constitute a special category of
petroleum solvents with boiling ranges corresponding
to those of white spirits. Similar to BTX, naphthas may
be used as raw materials for producing petrochemical
feedstocks, as described below. Therefore, naphthas
are considered to be industrial intermediates that are
subject to commercial specifications
2. Petrochemical feedstocks that are produced in the
refinery include C6 to C8 aromatics (BTX and ethyl

29

benzene) and C2 to C4 olefins. In petrochemical plants,


these feedstocks are used to produce plastics and resins, pharmaceuticals, antifreeze agents, detergents,
solvents, dyes, and agricultural chemicals such as
fertilizers, pesticides, and herbicides. BTX and ethyl
benzene are produced in refineries [in fluid catalytic
cracking (FCC) and catalytic reforming units] and in
petrochemical plants through reforming of naphtha.
The C3 to C4 olefins are produced in FCC units, and C2
and C3 olefins are produced by coking processes in a
refinery and steam cracking of naphtha or gas oils in
petrochemical plants.
3. Lubricants are composed of a main base stock obtained
from dearomatized and dewaxed vacuum gas oils for
controlling the viscosity and freezing point and are
combined with additives to obtain the desired performance characteristics. Among the most important characteristics of lubricants are thermal stability, viscosity,
and the viscosity index, which reflects the change of
viscosity with temperature. Aromatics are usually eliminated from lubricants to improve their viscosity index.
Lubricants consist mostly of isoparaffinic compounds.
Additives used for lubricants include viscosity index
additives such as polyacrylates and olefin polymers,
antiwear additives (i.e., fatty esters), antioxidants (i.e.,
alkylated aromatic amines), corrosion inhibitors (i.e.,
fatty acids), and antifoaming agents (i.e., polydimethylsiloxanes). Lubricating greases constitute another class
of lubricants that are semisolid. The specifications for
lubricants include viscosity index, freezing points, aniline point (indication of aromatic content), volatility,
and carbon residue (indication of thermal stability).
4. Petroleum waxes are of two types: the paraffin waxes in
petroleum distillates and the microcrystalline waxes in
petroleum residua. In some countries such as France,
paraffin waxes are simply called paraffins. Paraffin
waxes have high melting points; they are removed by
dewaxing of vacuum distillates to control the pour
points of lubricating oil base stocks. Paraffin waxes are
mainly straight-chain alkanes (C18 to C36) with a very
small proportion of isoalkanes and cycloalkanes. Their
freezing point is between 30 and 70 C, and the average
molecular weight is approximately 350. When present, aromatics appear only in trace quantities. Waxes
from petroleum residua (microcrystalline form) are
less defined aliphatic mixtures of n-alkanes, isoalkanes,
and cycloalkanes in various proportions. Their average
molecular weights are between 600 and 800, their carbon number range is C30 to C60, and the freezing point
range is 6090 C. Paraffin waxes (when completely
dearomatized) have applications in food industry and
food packaging. They are also used in the production of
candles, polishes, cosmetics, and coatings [6,8]. Waxes
at an ordinary temperature of 25 C are in solid states,
although they contain some hydrocarbons in liquid
form. When melted, they have relatively low viscosity.
5. Asphalt is produced from vacuum distillation residues
by solvent deasphalting. Asphalts contain nonvolatile
high-molecular-weight polar aromatic compounds such
as asphaltenes and cannot be distilled even under very
high vacuum conditions. In some countries asphalt is
called bitumen, although this is not a strictly correct use
of the term bitumen. Asphaltic materials (containing

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30

Petroleum Refining and Natural Gas Processing

residue can be specified as sponge, or shot cokes,


depending on their microstructure [11]. Sponge cokes
that have low ash, low sulfur, and low metal contents
can be used for making carbon anodes that are used
in electrolysis of alumina to manufacture aluminum.
Shot cokes that are much harder than sponge cokes
have a niche application for producing titanium dioxide [11]. Delayed coking of FCC decant oils produces
a special coke called needle coke that is used to produce graphite electrodes for electric-arc furnaces for
recycling scrap iron and steel. Important properties of
calcined needle cokes include density, ash content, and
the coefficient of thermal expansion [11].
In general, more than 2000 petroleum products within
some 20 categories are produced in refineries in the United
States [6,8]. Some of these products obtained from a

asphaltenes and resins) are used as binders for paving


the roads. The major properties of asphalt that determine its quality include flash point (for safety), composition (wax content), viscosity, softening point, weathering properties (resistance to oxidation or degradation),
specific gravity, and stability or chemical resistance.
6. There are some other products such as white oils (used
in pharmaceuticals or in the food industry), aromatic
extracts (used in the paint industry or the manufacture
of plastics), and coke (as a fuel or to produce carbon
electrodes for aluminum refining). Aromatic extracts
are black materials composed essentially of condensed
PNAs and heterocyclic nitrogen or sulfur compounds,
or both. Because of this highly aromatic structure, the
extracts have a good solvent power. Petroleum cokes
produced by delayed coking of vacuum distillation

Oil
Commercial
Energy

Gas
Kerosene
and Gas Oil

Residue

Gas and Naphthas


Heavy Gasoline

Bitumen,
Lube Oil, etc,
Vinyl Chloride

n-alkanes
/alkenes

Petrochemical
Industry

C4
Ethylene

Ethylene Oxide

Carbohydrate

n-alkyl carboxylic acids, e.g., acetic acid


Rubbers

Vinyl Acetate

HO(CH2)2OH

Car Fuel

Aviation
Fuel

Butadiene

-CH2Cyclohexane

Ethanol

CO

H2

HCOOH

CH3OH

Cyclohexanone
Adipic Acid

Ethyl
Chloride

CH3X
Oxalic
Acid

Hexanediamine

Adiponitrile

Caprolactone

Various Methyl Esters


e.g., Methyl Methacrylate
Phenol

CH4

HCON(CH3)2

Chloronated
Methanes

HCOOCH3

HCONH2

HCN
Fluoronated
Methanes

H3CCOOH

Acetic
Anhydride

CH3NH2

Ethyl
Acetate

CH3(CH)nOH

HCHO

C(CH2OH)4

H2NCO2(CO)NH

ClCN

Cyanuric Chloride

C2H2

Melamine1
Vinyl
Chloride

Vinyl
Acetate

HO(CH2)4OH

Butyrolactam
Butyrolactone

NMP & NVP

Tetrahydrofuran

Figure 2.7Some products produced from crude oil processing [12].


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Chapter 2 n Feedstocks and Products of Crude Oil and Natural Gas Refineries

typical crude oil are shown in Figure 2.7 as presented by


de Jong et al. [12]. In this figure, fuel products directly
produced in refineries are marked in color, whereas many
chemicals may be produced in the follow-up processes in a
petrochemical plant. Blending techniques are used to make
multiple products according to the desired properties or to
improve product quality. The product specifications must
satisfy customers requirements for good performance and
government regulations for safety and environmental protection. Therefore, to be able to plan refinery operations,
the availability of a set of product quality prediction methods is very important [1].

2.4 Natural Gas and Its Products

The typical composition of natural gas is given in Table 2.2.


Usually natural gases contain CO2 and H2S known as acid
gases, but the main components are methane, ethane, and
propane, although hydrocarbons as heavy as C11 may be
present. Natural gases may also contain inert gases such
as nitrogen and helium. Pipeline gases containing mainly
nitrogen, helium, C1, C2, and C3 in liquefied form are called
LNG. The liquefied form of gases C2, C3, and C4 is called
LPG. Pentanes and heavier including isobutane can be
separated from natural gas as natural gasoline. Natural gas
liquids (NGLs) and light and heavy naphthas may also be
separated naturally from natural gas. At normal pressure
conditions, only C5 and heavier components are in liquid
form. Methane needs to be refrigerated to 259F to have it
as liquid. For storage of natural gas at normal temperatures
(above boiling point), it is necessary to compress it, which
is known as compressed natural gas (CNG). Liquid mixtures
of C3 and C4 are ideal fuel for many applications. They are
stable, high-energy content, relatively low sulfur, and clean
burning fuels that can be transported as liquid and used as
liquid or gas. LPG can be produced from natural gas and
crude oil. LPG is also a preferred feedstock for petrochemicals, gas cracking, and plastics. The first commercial use
of LPG from crude oil or natural gas was in 1912. Propane
used in LPG is not suitable for gasoline (it is very volatile) or
for use in natural gas (heavy component in natural gas pipeline), so its best application is in LPG. The ratio of C3C4 in
LPG mainly depends on the temperature because at high
temperatures (summer) more C4 and at low temperatures
(winter) more C3 is used in the mixture. Tanks containing
LPG should never be filled with liquids to allow space for
vapors and volume expansion for safety reasons [8].
Natural gas and NGLs are also the main feedstocks for
petrochemical plants. Through absorption processes, H2S
can be separated from natural gas, and upon oxidation of
H2S sulfur can be produced. Through distillation/extraction
processes, components such as C2, C3, C4, and heavier compounds are separated. Methane as the main component of
natural gas can be used through processes such as reforming and oxidation to produce a group of chemicals such
as CO2, hydrogen, ammonia,, methyl chloride, acetylene,
methanol, nitric acid, urea, acrylonitrile, vinyl chloride,
ethanol, propanol, butanol, formaldehyde, pharmaceuticals
and feeds to pharmaceutical industries, carbon tetrachloride, acetaldehyde, vinyl resins, etc.
The next main components of natural gas are ethane and propane. These components can be converted
to ethylene and propylene through cracking processes.
Ethylene can be used to produce many products such

31

as polyethylene, ethylene oxide, ethyl chloride, ethanolamine, ethylene glycol, acetaldehyde, styrene, ethyl
benzene, detergents, etc. Propylene is used to produce a
group of compounds through processes such as oxidation,
hydration, polymerization, and alkylation. These products
include cumene, polymers, isopropyl alcohol, allyl chloride,
acetone, glycerin, epoxy resins, isobutanol, acetic acid,
nitroglycerin, etc.
Butanes in natural gas may be in the form of isobutene
or n-butane, which can be separated through a distillation
process. These components can be converted to products
such as isobutylene, tert-butyl alcohol, butadiene, polybutadiene, nylon, methyl ethyl ketone, synthetic resins, lube
oil additives, tert-butyl phenol, etc., through dehydrogenation, polymerization, and copolymerization processes.

2.5 Biofuels

Biofuels represent a group of fuels derived from biomaterials such as vegetable oil or biomass. A good example of a biofuel is biodiesel, which is a cleaner fuel than petrodiesel and
can be produced from renewable sources such as vegetable
oil, palm oil, cooking oil, or animal fat. These oils undergo
a process called transesterification, in which they react with
an alcohol such as methanol or ethanol with sodium hydroxide or potassium hydroxide as catalyst [1316]. Transesterification converts fats and oils (triglycerides) into alkylesters of
fatty acids that have similar properties to those of petroleum
diesel. The process produces large quantities of glycerol as
a byproduct. Biodiesel does not contain any sulfur or aromatics. Therefore, in comparison to petroleum diesel, the
combustion of biodiesel results in a reduction in unburned
hydrocarbons, carbon monoxide, and particulate matter
emissions. Because it has a higher flash point it is safer to
store and to handle [1517]. Biodiesel can be used in its pure
form (B100) or in blends with petroleum diesel in a wide
range of concentrations (e.g., B2, B5, B20) in diesel engines.
Another group of biofuels comprises bioalcohols,
which are biologically produced alcohols. The most commonly used bioalcohols are ethanol, propanol, and butanol.
Butanol can be used directly in spark-ignition (gasoline)
engines without any alteration. Butanol can produce more
energy than ethanol and is less corrosive because it is less
soluble in water. However, ethanol is the most commonly
used biofuel in the world and in particular in Brazil. Ethanol can also be mixed with gasoline at any ratio, but use of
15 % bioethanol in gasoline (marked by E15) is common.
Mixtures of gasoline and ethanol produce less pollution
than gasoline upon combustion, especially in cold winters
and high altitudes. However, ethanol has a lower heating
value than gasoline [13].
Other types of biofuels include biogas and solid biofuels. Biogas is produced when organic material isanaerobically digested by anaerobes. Biogas consists of methane,
and landfill gas is created in landfills because of natural
anaerobic digestion. Charcoal and wood are examples of
solid biofuels. The combined processes of gasification,
combustion, and pyrolyis can produce syngas, which is a
biofuel. This syngas can be directly burned in internal combustion engines. Syngas can be used to create hydrogen and
methanol. Syngas can be transformed to a synthetic petroleum substitute using the FischerTropsch process. Finally,
a third-generation biofuel is produced from algae, which is
called oilage [13].

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32

Petroleum Refining and Natural Gas Processing

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