Professional Documents
Culture Documents
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
21
Copyright by ASTM Int'l (all rights reserved); Wed Dec 10 04:33:39 EST 2014
Downloaded/printed by
Intertek Testing Services NA (Intertek Testing Services NA) pursuant to License Agreement. No further reproductions authorized.
AST-MNL58-11-0801-002.indd 21
3/12/13 12:37 PM
22
Cyclopentane
(C5H10)
Number of isomers
1.0 1015
1.0 1010
1.0 105
1.0 100
10
20
30
Number of carbon atoms
40
50
Methylcyclopentane
(C6H12)
Ethylcyclohexane
(C8H16)
Copyright by ASTM Int'l (all rights reserved); Wed Dec 10 04:33:39 EST 2014
Downloaded/printed by
Intertek Testing Services NA (Intertek Testing Services NA) pursuant to License Agreement. No further reproductions authorized.
AST-MNL58-11-0801-002.indd 22
3/12/13 12:37 PM
Chapter 2 n Feedstocks and Products of Crude Oil and Natural Gas Refineries
23
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)
Copyright by ASTM Int'l (all rights reserved); Wed Dec 10 04:33:39 EST 2014
Downloaded/printed by
Intertek Testing Services NA (Intertek Testing Services NA) pursuant to License Agreement. No further reproductions authorized.
AST-MNL58-11-0801-002.indd 23
3/12/13 12:37 PM
24
GOR (scf/stb)
CH4 (mol %)
C6+ (mol %)
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).
Copyright by ASTM Int'l (all rights reserved); Wed Dec 10 04:33:39 EST 2014
Downloaded/printed by
Intertek Testing Services NA (Intertek Testing Services NA) pursuant to License Agreement. No further reproductions authorized.
AST-MNL58-11-0801-002.indd 24
3/12/13 12:37 PM
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
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
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
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].
Copyright by ASTM Int'l (all rights reserved); Wed Dec 10 04:33:39 EST 2014
Downloaded/printed by
Intertek Testing Services NA (Intertek Testing Services NA) pursuant to License Agreement. No further reproductions authorized.
AST-MNL58-11-0801-002.indd 25
3/12/13 12:37 PM
26
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.
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
Copyright by ASTM Int'l (all rights reserved); Wed Dec 10 04:33:39 EST 2014
Downloaded/printed by
Intertek Testing Services NA (Intertek Testing Services NA) pursuant to License Agreement. No further reproductions authorized.
AST-MNL58-11-0801-002.indd 26
3/12/13 12:37 PM
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
C4C10
1 to 200
30390
C4C11
1 to 205
30400
Jet fuel
C9C14
150255
300490
Kerosene
C11C14
205255
400490
Diesel fuel
C11C16
205290
400550
C14C18
255315
490600
C18C28
315425
600800
Wax
C18C36
315500
600930
Lubricating oil
>C25
>400
>750
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.
Copyright by ASTM Int'l (all rights reserved); Wed Dec 10 04:33:39 EST 2014
Downloaded/printed by
Intertek Testing Services NA (Intertek Testing Services NA) pursuant to License Agreement. No further reproductions authorized.
AST-MNL58-11-0801-002.indd 27
3/12/13 12:37 PM
28
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
Copyright by ASTM Int'l (all rights reserved); Wed Dec 10 04:33:39 EST 2014
Downloaded/printed by
Intertek Testing Services NA (Intertek Testing Services NA) pursuant to License Agreement. No further reproductions authorized.
AST-MNL58-11-0801-002.indd 28
3/12/13 12:37 PM
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.
29
Copyright by ASTM Int'l (all rights reserved); Wed Dec 10 04:33:39 EST 2014
Downloaded/printed by
Intertek Testing Services NA (Intertek Testing Services NA) pursuant to License Agreement. No further reproductions authorized.
AST-MNL58-11-0801-002.indd 29
3/12/13 12:37 PM
30
Oil
Commercial
Energy
Gas
Kerosene
and Gas Oil
Residue
Bitumen,
Lube Oil, etc,
Vinyl Chloride
n-alkanes
/alkenes
Petrochemical
Industry
C4
Ethylene
Ethylene Oxide
Carbohydrate
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
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
Tetrahydrofuran
3/12/13 12:37 PM
Chapter 2 n Feedstocks and Products of Crude Oil and Natural Gas Refineries
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].
Copyright by ASTM Int'l (all rights reserved); Wed Dec 10 04:33:39 EST 2014
Downloaded/printed by
Intertek Testing Services NA (Intertek Testing Services NA) pursuant to License Agreement. No further reproductions authorized.
AST-MNL58-11-0801-002.indd 31
3/12/13 12:37 PM
32
References
Copyright by ASTM Int'l (all rights reserved); Wed Dec 10 04:33:39 EST 2014
Downloaded/printed by
Intertek Testing Services NA (Intertek Testing Services NA) pursuant to License Agreement. No further reproductions authorized.
AST-MNL58-11-0801-002.indd 32
3/12/13 12:37 PM