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1 AUTHOR:
Abdullah M. Aitani
King Fahd University of Petroleum and Miner
109 PUBLICATIONS 763 CITATIONS
SEE PROFILE
1.
2.
3.
4.
5.
6.
7.
Glossary
alkylation A process using sulfuric acid or hydrofluoric
acid as a catalyst to combine light olefins and isobutane
to produce a high-octane product known as alkylate.
1API gravity A scale of liquid specific gravity (SG) that
indicates the lightness or heaviness of hydrocarbons,
defined by [(141.5/SG) 131.5].
catalytic cracking A process for the breaking-up of heavier
hydrocarbons into lighter hydrocarbon fractions by the
use of heat and catalysts.
cetane number A measure of ignition quality for kerosene,
diesel, and heating oil, using a single-cylinder engine.
coking A process for thermally converting and upgrading
heavy residues into lighter products and by-product
petroleum coke.
crude oil A complex mixture of hydrocarbons containing
low percentages of sulfur, nitrogen, and oxygen compounds and trace quantities of many other elements.
deasphalting A process for removing asphaltic materials
from reduced crude, using liquid propane to dissolve
nonasphaltic compounds.
hydrocracking A process used to convert heavier feedstock
into lower boiling point, higher value products. The
process employs high pressure, high temperature, a
catalyst, and hydrogen.
hydrodesulfurization A catalytic process for the removal of
sulfur compounds from hydrocarbons using hydrogen.
isomerization A catalytic process for the conversion and
skeletal rearrangement of straight-chain hydrocarbons
into branched-chain molecules of higher octane number.
methyl tertiary butyl ether (MTBE) An ether added to
gasoline to raise octane number and enhance combustion.
This article discusses the various aspects of petroleum refining and oil products as a primary energy
source and as a valuable feedstock for petrochemicals. The main objective of refining is to convert
crude oils of various origins and different compositions into valuable products and fuels having the
qualities and quantities demanded by the market.
Various refining processes, such as separation, conversion, finishing, and environmental protection, are
presented and briefly discussed. The ever-changing
demand and quality of fuels, as well as environmental issues and the challenges facing the refining
industry, are also highlighted. Environmental regulations have played a significant role in the progress of
the refining industry and may even change the
competition between petroleum and other alternative
energy sources.
1. OVERVIEW OF REFINERY
PROCESSING
1.1 Introduction
Refining is the processing of crude oil into a number
of useful hydrocarbon products. Processing utilizes
715
716
Various streams are subjected to various separation processes, such as extraction, hydrotreating, and
sweetening, to remove undesirable constituents and
improve product quality. In general, petroleum
refining operations can be grouped as follows:
Fractionation (distillation) is the separation of
crude oil in atmospheric and vacuum distillation
towers into groups of hydrocarbon compounds of
differing boiling-point ranges called fractions or
cuts.
Light oil processing prepares light distillates
through rearrangement of molecules using isomerization and catalytic reforming or combination
processes such as alkylation and polymerization.
Heavy oil processing changes the size and/or
structure of hydrocarbon molecules through thermal
or catalytic cracking processes.
Treatment and environmental protection processes involve chemical or physical separation, such
as dissolving, absorption, or precipitation, using a
variety and combination of processes including
drying, solvent refining, and sweetening.
717
LPG
Gas plant
Polymerization
Olefins
Gas
Gas from other units
Alkylation
C4
Treater
Lt Naph
Atmospheric
crude
distillation
H2
Hydrotreater
Hv Naph
Reformer
Aromatic
extraction
Gasoline
Aromatics
Hydrotreater
Kerosene
Kerosene
Crude
desalter
Crude oil
Hydrotreater
Fuel oils
Hydrotreater
Vac
Gas oil
Cat cracker
To lube plant
Lube
Vacuum
crude
distillation
Asphalt
To asphalt blowing
Coke
Coker
FIGURE 1 Schematic diagram of a high-conversion refinery. Cat cracker, catalytic cracker; Hv Naph, heavy naphtha; Lt
Naph, light naphtha; LPG, liquefied petroleum gas; Vac gas oil, vacuum gas oil; ATM gas oil, atmospheric gas oil.
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TABLE I
Regional Distribution of Refining Operations Worldwide
Regional capacity
Region
No. of refineries
million barrels/day
North America
160
20.3
24.8
South America
Western Europe
69
105
6.7
14.6
8.2
17.8
Eastern Europe
95
10.6
12.9
202
20.2
24.7
Middle East
46
6.3
7.7
Africa
45
3.2
722
81.9
Asia
Total
3.9
100
TABLE II
proportions of gasoline and light petroleum products; those with high carbon, low hydrogen, and
low API gravities are usually rich in aromatics.
Crude oils can be classified in many different
ways, generally based on their density (API), sulfur
content, and hydrocarbon composition. Condensate
ranks highest, with densities reaching more than 501
API, whereas densities of heavy crudes may reach as
low as 101 API. In general, refinery crude base stocks
consist of mixtures of two or more different crude
oils. There are more than 600 different commercial
crude oils traded worldwide. In 2002, world oil
production reached 66 million barrels/day, 40% of
which is produced by members of the Organization
of Petroleum Exporting Countries. Despite all energy
alternatives, crude oil will remain the worlds
primary energy source, constituting approximately
40% of world energy up to the year 2020.
% of crude
capacity
26.7
32.6
Coking
4.2
5.1
Visbreaking
3.7
4.5
Catalytic cracking
14.2
17.3
Naphtha reforming
11.2
13.7
Process
Vacuum distillation
Hydrocracking
4.4
5.4
Hydrotreating
Alkylation
38.4
1.9
46.9
2.3
Polymerization
0.2
0.2
Aromatics production
1.2
1.5
Isomerization
1.5
1.8
Oxygenates
0.3
0.4
compounds that are not easily identifiable or quantifiable. Most of these compounds have a carbon
number less than 16 and these form a relatively high
proportion of crude oil.
The elemental composition of crude oils depends
on the type and origin of the crude; however, these
elements vary within narrow limits. The proportions
of these elements in a typical crude are 84.5%
carbon, 13% hydrogen, 13% sulfur, and less than
1% each of nitrogen, oxygen, metals, and salts. The
physical properties of crude oils vary within a wide
range. Crude oils are defined in terms of API
(American Petroleum Institute) gravity: the higher
the API gravity, the lighter the crude. Crude oils with
low carbon, high hydrogen, and high API gravity are
usually rich in paraffins and tend to yield greater
petroleum-based products. Crude oil type and refining configuration determine the quantity and quality
of oil products. Tables III and IV present some
typical data on the volume of atmospheric distillate
cuts and refined products derived from the processing
of Arabian light crude oil. For example, approximately 8085 vol% of the refined products produced
in a medium-type conversion refinery have a boiling
temperature lower than 3451C compared to an
amount of 55 vol% found in Arabian crude oil (see
Tables III and IV). Almost half of the products are
gasoline and lighter distillates. The demand for
transportation fuels and petrochemical feedstocks
has been increasing steadily compared to the
decreasing demand for heating fuels and residual
fuel oil, which are being replaced by natural gas.
2.3.1 Gasoline
Motor gasoline is the highest volume refinery
product, having a mixture of hydrocarbons with
boiling points ranging from ambient temperature to
approximately 2051C. It flows easily, spreads quickly,
and may evaporate completely in a few hours under
temperate conditions. It is highly volatile and
flammable. Gasoline is made up of different refinery
streams, mainly straight-run naphtha, isomerized
C5/C6 paraffins, reformate, hydrocracking, fluid
catalytic cracking (FCC) gasoline, oligomerate, alkylate, and ethers. The most environmentally friendly
gasoline comes from branched paraffins. The imTABLE III
Atmospheric Distillates Derived from Arabian Light Crude Oil
Product name
Volume (%)
719
Light naphtha
1090
Heavy naphtha
90200
21
Kerosene
200260
11
TABLE V
Gas oil
260345
15
Residue
345
45
Year
TABLE IV
Specificationa
2000
2005
Sulfur (ppm)
150
3050
Product name
Gases
Gasoline
Kerosene/jet
Fuel oil
Residue
Carbon no.
42
35
18
15
Volume (%)
14
4040
510
40200
45
RVP (kPa)
1016
2070
150260
200345
5
25
RON/MON (minimum)
470
4345
20
2.7
2.3
60
50
95/85
95/85
a
RVP, Reid vapor pressure; RON, research octane number;
MON, motor octane number.
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TABLE VI
Current and Future Specifications for Diesel Fuel
Year
Specification
Sulfur (ppm)
Specific gravity (maximum)
API (minimum)
Cetane number
Distillation T95 (1C, maximum)
Polycyclic aromatic hydrocarbons
(PAH wt%, maximum)
2000
350
0.845
36
2005
50
0.825
40
51
54
360
360
11
3.2 Isomerization
Isomerization is an intermediate, fed preparation-type
process. There are more than 200 units worldwide,
with a processing capacity of 1.5 million barrels/day
of light paraffins. Two types of units exist: C4
isomerization and C5/C6 isomerization. A C4 unit
will convert normal butane into isobutane, to provide
additional feedstock for alkylation units, whereas a
C5/C6 unit will isomerize mixtures of C5/C6 paraffins,
saturate benzene, and remove naphtenes.
Isomerization is similar to catalytic reforming in
that the hydrocarbon molecules are rearranged, but
unlike catalytic reforming, isomerization just converts normal paraffins to isoparaffins. The greater
value of branched paraffins over straight paraffins is
a result of their higher octane contribution. The
Stacked
reactor
Combined
feed
exchanger
Catalyst
regenerator
721
Fuel gas
LPG
Fresh
catalyst
Fire heaters
Naphtha feed
FIGURE 2 Flow scheme of a continuous catalyst regenerative naphtha reformer. LPG, liquefied petroleum gas.
Reformate
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3.3 Alkylation
Alkylation is the process that produces gasolinerange compounds from the combination of light C3
C5 olefins (mainly a mixture of propylene and
butylene) with isobutene. The highly exothermic
reaction is carried out in the presence of a strong acid
catalyst, either sulfuric acid (H2SO4) or hydrofluoric
acid (HF). The world alkylation capacity stands at
1.9 million barrels/day and new grassroots units have
been constructed in many refineries worldwide,
especially those with FCC units. The alkylate
product is composed of a mixture of high-octane,
branched-chain paraffinic hydrocarbons. Alkylate is
a premium clean gasoline blend, with octane number
depending on the type of feedstocks and operating
conditions. Research efforts are directed toward the
development of environmentally acceptable solid
superacids capable of replacing HF and H2SO4.
Much of the work is concentrated on sulfonated
zirconia catalysts.
3.3.1 Sulfuric Acid Process
In H2SO4-based alkylation units, the feedstock
(propylene, butylene, amylene, and fresh isobutane)
enters the reactor and contacts the concentrated
sulfuric acid catalyst (in concentrations of 8595%).
The reactor effluent is separated into hydrocarbon
and acid phases in a settler and the acid is returned to
the reactor. The hydrocarbon phase is hot water
washed with a caustic compound for pH control
before being successively depropanized, deisobutanized, and debutanized. The alkylate obtained from
the deisobutanizer can then go directly to motor
gasoline blending.
3.3.2 Hydrofluoric Acid Process
In a typical HF process, olefin and isobutane feedstock
are dried and fed to a combination reactor/settler
system. The process is operated at temperatures
attainable by cooling water and at higher pressures
to keep fluid in the liquid state. The reactor effluent
flows to a separating vessel, where the acid separates
from the hydrocarbons. The acid layer at the bottom
of the separating vessel is recycled. Propane with a
trace amount of HF goes to an HF stripper for HF
removal and is then defluorinated, treated, and sent to
storage. Isobutane is recycled to the reactor/settler and
the alkylate is sent to gasoline blending.
3.4 Etherification
Etherification results from the selective reaction of
methanol or ethanol to isobutene. The ether products, such as MTBE or other oxygenates, are used as
components in gasoline because of their high octane
blending value. The refinery capacity of oxygenate
units is approximately 266,000 barrels/day, with
almost all units associated with alkylation processes.
The exothermic reaction is conducted in liquid phase
at 85901C over a highly acidic ion-exchange
polystyrene resin catalyst. The reaction is very rapid
and equilibrium is limited under typical reaction
conditions. A combination of catalytic distillation is
applied to remove the product as vapor, thereby
driving the reaction to almost 100% conversion. The
etherification process is needed to supply oxygenates
to meet the specifications of reformulated gasoline
(minimum 2.7 wt% oxygenate content). In general,
MTBE is the preferred oxygenate because of its low
production cost and convenient preparation route
relative to those of other ethers.
723
724
Reactor
product
Flue gas
Stripping
section
Spent
catalyst
Regenerator
Riser
reactor
Regenerated
catalyst
Preheater
VGO feed
FIGURE 3
Schematic diagram of fluid catalytic cracking process. VGO feed, vacuum gas oil feed.
4.3 Hydrocracking
Catalytic hydrocracking of heavy petroleum cuts is
an important process for the production of gasoline,
jet fuel, and light gas oils. Some hydrocracking
processes also allow the production of a highly
purified residue, which can be an excellent base for
oils. The process employs high pressure, high
temperature, a catalyst, and hydrogen. In contrast
to FCC, the advantage of hydrocracking is that
middle distillates, jet fuels, and gas oils of very good
quality are provided. In general, hydrocracking is
more effective in converting gas oils to lighter
products, but it is more expensive to carry out.
Hydrocracking is used for feedstocks that are
difficult to process by either catalytic cracking or
reforming, since these feedstocks are usually characterized by a high polycyclic aromatic content and/
or high concentrations of the two principal catalyst
poisons, sulfur and nitrogen compounds. These
feedstocks include heavy gas oils, FCC cycle oils,
deasphalted oil, and visbreaker or coke gas oil. The
process depends largely on the nature of the feedstock and the relative rates of the two competing
reactions, hydrogenation and cracking. Heavy aromatic feedstock is converted into lighter products
under a wide range of very high pressures (70
140 atm) and fairly high temperatures (4008201C),
in the presence of hydrogen and special catalysts.
4.3.1 Hydrocracking Process
Hydrocracking is a two-stage process combining
catalytic cracking and hydrogenation, wherein heavier
feedstocks are cracked in the presence of hydrogen.
The reaction typically involves a reactor section, gas
separator, scrubber for sulfur removal, and product
fractionator. The reactor section contains a multicatalyst bed that can be of the fixed-bed or ebullatedbed type and some employ on-stream catalyst
addition and withdrawal to maintain catalyst activity.
4.3.2 Hydrocracking Catalysts
The catalysts used in hydrocracking are all of the
bifunctional type, combining an acid function and a
hydrogenating function. The acid function is carried
by supports with a large surface area and having a
superficial acidity, such as halogenated aluminas,
zeolites, amorphous silica-aluminas, and clays. The
hydrogenating function is carried either by one or
more transition metals, such as iron, cobalt, nickel,
ruthenium, rhodium, palladium, osmium, iridium,
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5.2 Visbreaking
Visbreaking is the most widespread process for
noncatalytic mild conversion of residues, with a
world capacity of 3.7 million barrels/day. The
process is designed to reduce the viscosity of
atmospheric or vacuum residues by thermal cracking. It produces 1520% of atmospheric distillates
with proportionate reduction in the production of
726
Exchanger
Solvent
Exchanger
Compressor
Deasphalted oil
separation
Recycled solvent
Heater
Exchanger
Exchanger
Heater
Solvent
Stripping column
Solvent
Flash column
Deasphalting
step
Feed
Steam
Solvent drum
Steam
Deasphalted oil
Solvent makeup
Recycled solvent
Asphalt conditioning
FIGURE 4
6. TREATING PROCESSES
6.1 Hydrogen Production
Refineries are experiencing a substantial increase in
hydrogen requirements to improve product quality
and process heavy sour crudes. Hydroprocessing and
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728
6.4 Sweetening
Sweetening is the removal of contaminants such as
organic compounds containing sulfur, nitrogen, and
oxygen; dissolved metals and inorganic salts; and
soluble salts dissolved in emulsified water from
petroleum fractions or streams. A variety of intermediate and finished products, including middle
distillates, gasoline, kerosene, jet fuel, and sour gases,
are sweetened. Treating can be accomplished at an
intermediate stage in the refining process or just before
the finished product is sent to storage. Choices of a
treating method depend on the nature of the petroleum
fractions, the amount and type of impurities in the
fractions to be treated, the extent to which the process
removes the impurities, and end-product specifications. Treatment materials include acids, solvents,
alkalis, oxidizing agents, and adsorption agents.
7. ENVIRONMENTAL AND
FUTURE ISSUES
7.1 Environmental Issues
Refiners are faced with many environmental, economic, and operational issues. Environmental legislation is
a growing concern, driving changes in product specifications, product markets, and refinery operating practices. Strict product quality specifications and severe
emission and discharge limits have economic impact
on the average refiner. In the near future, the following
environmental trends will continue to grow, but they
will not create significant changes in oil consumption
patterns: (1) the production of clean transportation
fuels according to new specifications and (2) refinery
operation within strict emissions regulations.
The configuration of many refineries has changed
substantially, mainly due to the declining quality of
crude oil supply and environmental regulations. In
retrospect, refinery changes brought about by the
variations in crude supply and composition were
evolutionary, whereas environmental regulations were
revolutionary.
7.1.1 Clean Transportation Fuels
Since 1990, government agencies have imposed
strict environmental restrictions on transportation
fuels to improve product quality specifications. Fuel
reformulation is being discussed all over the world.
Automotive manufacturers are demanding lower
gasoline sulfur levels and lower driveability indices.
Refiners must improve air quality by delivering clean
products that minimize emissions of toxic and
hazardous hydrocarbons. Gasoline and diesel formulations have been already changed in many countries
and will change even more in the coming years.
Refining is faced with huge investments to meet
new stringent specifications for sulfur, aromatics, and
olefin content. Gasoline sulfur reduction is centered
around the FCC unit employing feed pretreatment or
gasoline posttreatment. The reduced demand for
ethers, such as MTBE in gasoline for oxygenate
content, necessitates the utilization of branched
paraffin isomer products of alkylation and isomerization. For diesel fuel, this means a sulfur content
729
Further Reading
Aitani, A. (1995). Reforming processes. In Catalytic Naphtha
Reforming (G. Antos et al., Eds.), pp. 409436. Dekker,
New York.
Farrauto, R., and Bartholomew, C. (1997). Fundamentals of
Industrial Catalytic Processes, pp. 519579. Blackie Academic
and Professional, London.
Gary, J., and Handwerk, G. (2001). Petroleum Refining
Technology and Economics. 4th ed. Dekker, New York.
Heinrich, G. (1995). Introduction to refining. In Petroleum
Refining (J. P. Wauquier, Ed.), pp. 365413. Editions Technip,
Paris.
Hoffman, H. (1992). Petroleum and its products. In Riegels
Handbook of Industrial Chemistry (J. Kent, Ed.), 9th ed.,
pp. 490496. Van Nostrand Reinhold, New York.
Le Page, J. P., Chatila, S., and Davidson, M. (1992). Resid and
Heavy Oil Processing. Editions Technip, Paris.
Maples, R. (2000). Petroleum Refinery Process Economics. 2nd
ed. PennWell Books, Tulsa, OK.
Martino, G., and Wechem, H. (2002). Current Status and Future
Developments in Catalytic Technologies Related to Refining
and Petrochemistry, Review and Forecast Paper, 17th World
Petroleum Congress, Rio de Janeiro, Brazil, September 2002.
Meyers, R. (1997). Handbook of Petroleum Refining Processes.
2nd ed. McGraw-Hill, New York.
Penning, T. (2001). Petroleum Refining: A Look at the Future,
Hydrocarbon Processing, February, pp. 4546.
Silvy, R. (2002). Global refining catalyst industry will achieve strong
recovery by 2005, Oil & Gas Journal, pp. 4856. September 2,
2002.
Speight, J., and Ozum, B. (2002). Petroleum Refining Processes.
Dekker, New York.
Stell, J. (2002). Worldwide refining survey. Oil & Gas Journal,
December 23, 2002, pp. 6870.