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Oil Refining and Products

CHAPTER DECEMBER 2004
DOI: 10.1016/B0-12-176480-X/00259-X

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1 AUTHOR:
Abdullah M. Aitani
King Fahd University of Petroleum and Miner
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Oil Refining and Products

ABDULLAH M. AITANI
King Fahd University of Petroleum and Minerals
Dhahran, Saudi Arabia

1.
2.
3.
4.
5.
6.
7.

Overview of Refinery Processing

Crude Oil and Products
Light Oil Processing
Heavy Distillate Processing
Residual Oil Processing
Treating Processes
Environmental and Future Issues

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.

Encyclopedia of Energy, Volume 4. r 2004 Elsevier Inc. All rights reserved.

octane number A measure of resistance to knocking of

gasoline under laboratory conditions that simulate city
driving conditions.
olefins Unsaturated hydrocarbons, such as ethylene and
propylene, that have a double carbon bond, with the
molecular formula CnH2n.
paraffins Saturated aliphatic hydrocarbons with the molecular formula CnH2n 2.
reforming A process for the transformation of naphtha
into products with higher octane number. Reforming
comprises isomerization, cracking, polymerization, and
dehydrogenation.
visbreaking A low-temperature cracking process used
to reduce the viscosity or pour point of straight-run
residues.

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

Oil Refining and Products

chemicals, catalysts, heat, and pressure to separate

and combine the basic types of hydrocarbon molecules naturally found in crude oil into groups of
similar molecules. The refining process also rearranges their structures and bonding patterns into
different hydrocarbon molecules and compounds.
Therefore, it is the type of hydrocarbon (paraffinic,
naphthenic, or aromatic) and its demand that
configure the refining industry. Petroleum refining
has evolved continuously in response to changing
demands for better and different products. The trend
in demand has also been accompanied by continuous
improvement in product quality, such as octane
number for gasoline and cetane number for diesel.
The original requirement was to produce kerosene
for household use, followed by the development of
the internal combustion engine and the production of
transportation fuels (gasoline, diesel, and fuels).
Refineries produce a variety of products including
many required as feedstocks for the petrochemical
industry. Early refining was the simple distillation
(fractionation) of crude oil followed by the development in the 1920s of the thermal cracking processes,
such as visbreaking and coking. The processes crack
heavy fuels into more useful and desirable products
by applying pressure and heat.
In the early 1940s, the catalytic processes were
developed to meet the increasing demand of gasoline
and higher octane numbers. Processes such as
catalytic cracking, alkylation, isomerization, hydrocracking, and reforming were developed throughout
the 1960s to increase gasoline yields and improve
antiknock characteristics. Some of these processes
also produced valuable feedstocks for the modern
petrochemical industry. In the 21st century, the
refinery uses an array of various catalytic and
noncatalytic processes to meet new product specifications and to convert less desirable fractions into more
valuable liquid fuels, petrochemical feedstocks, and
electricity. The refinery has shifted from only physical
separations to something close to a chemical plant.

1.2 Refinery Operations

Modern refineries incorporate fractionation, conversion, treatment, and blending operations and may
also include petrochemical processing. Most light
distillates are further converted into more usable
products by changing the size and structure of the
hydrocarbon molecules through cracking, reforming,
and other conversion processes, as discussed further
in this article. Figure 1 presents a typical scheme of a
high-conversion refinery.

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.

1.3 World Refining

World refining capacity reached 81.9 million barrels/
day in 2002 and is expected to increase by 4.3% per
year to 115 million barrels/day by 2020. Table I
presents a regional distribution capacity of major
refining processes. There are 722 refineries in 116
countries, with more than 200 refineries in AsiaPacific regions alone. The United States has maintained its leading position as the largest and most
sophisticated oil-refining region. Approximately
25% of worldwide refining capacity is located in
North America and another 25% is located in Asia
followed by 17% in Western Europe. Remaining
regions process approximately 33% of the worlds
crude oil in medium-type conversion refining
schemes. World capacities of various refining processes are presented in Table II. Hydrotreating alone
represents approximately 50% of total crude capacity, whereas all catalytic processes represent approximately 82% of crude capacity.
In general, the refining industry has always been
characterized as a high-volume, low-profit-margin
industry. World refining continues to be challenged
by uncertainty of supply, difficult market conditions,
government regulation, availability of capital, and
slow growth. Although shipping of refined products
has been increasing over the years, a close connection
remains between domestic markets and domestic

717

Oil Refining and Products

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

ATM Gas oil

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.

production. This explains the large differences in

refinery schemes from one country to another and
from one region to another.

2. CRUDE OIL AND PRODUCTS

2.1 Type and Composition of Crude Oils
Crude oil is a mixture of hydrocarbon compounds
such as paraffins, naphthenes, and aromatics plus

small amounts of organic compounds of sulfur,

oxygen, and nitrogen, in addition to small amounts
of metallic compounds of vanadium, nickel, and
sodium. Although the concentration of nonhydrocarbon compounds is very small, their influence on
catalytic petroleum processing is large. There are a
large number of individual components in a specific
crude oil, reaching approximately 350 hydrocarbons
and approximately 200 sulfur compounds. A specific
crude oil can comprise a very large number of

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Oil Refining and Products

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.

World Refining Processes and Their Share of Crude Oil Capacity

Capacity (million
barrels/day)

% 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

2.2 Crude Oil Processing

As a first step in the refining process, water, inorganic
salts, suspended solids, and water-soluble trace metal
contaminants are removed by desalting using chemical or electrostatic separation. This process is usually
considered a part of the crude distillation unit. The
desalted crude is continuously drawn from the top of
the settling tanks and sent to the crude fractionation
unit. Distillation of crude oil into straight-run cuts
occurs in atmospheric and vacuum towers. The main
fractions obtained have specific boiling-point ranges
and can be classified in order of decreasing volatility
into gases, light distillates, middle distillates, gas oils,
and residue. The composition of the products is
directly related to the characteristics of the crude
processed. Desalted crude is processed in a vertical
distillation column at pressures slightly above atmospheric and at temperatures ranging from 345 to
3701C (heating above these temperatures may cause
undesirable thermal cracking). In order to further
distill the residue from atmospheric distillation at
higher temperatures, reduced pressure is required to
prevent thermal cracking. Vacuum distillation resembles atmospheric distillation except that larger
diameter columns are used to maintain comparable
vapor velocities at the reduced pressures.

2.3 Transportation Fuels

Major oil products are mainly transportation fuels
that represent approximately 52% of total worldwide oil consumption. Gasoline and diesel are the
main concern, along with a large number of special

Oil Refining and Products

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

Boiling point (1C)

Volume (%)

719

portant qualities for gasoline are octane number

(antiknock), volatility (starting and vapor lock),
vapor pressure, and sulfur content (environmental
control). Additives are often used to enhance gasoline
performance and to provide protection against
oxidation and rust formation. Table V presents some
typical data for current and future specifications for
gasoline in Europe.
2.3.2 Diesel Fuel
Diesel fuel is usually second in volume next to
gasoline. Diesel blend consists of cuts from atmospheric distillation, hydrocracking, FCC light cycle oil,
and some products obtained from visbreaking and
coking. The main property of diesel fuel for automotive engine combustion is cetane number, which is a
measure of engine start-up and combustion. Diesel fuel
and domestic heating oils have boiling point ranges of
approximately 2003701C. The desired properties of
these distillate fuels include controlled flash and pour
points, clean burning, and no deposit formation in
storage tanks. Sulfur reduction and cetane improvement have been extensively investigated to produce
ultralow-sulfur diesel (ULSD). Meeting future specifications for ULSD of 1015 ppm sulfur will require
significant hydrotreating investment. Table VI presents
some typical data for current and future specifications
for diesel fuel in Europe.
2.3.3 Jet Fuel (Kerosene)
Jet fuel is the third most important transportation fuel.
It is a middle-distillate product that is used for jets
(commercial and military) and is used around the
world in cooking and heating (kerosene). When used
as a jet fuel, some of the critical qualities are freeze

Light naphtha

1090

Heavy naphtha

90200

21

Kerosene

200260

11

TABLE V

Gas oil

260345

15

Current and Future Specifications for Gasoline

Residue

345

45
Year

TABLE IV

Specificationa

2000

2005

Typical Refined Products Derived from Arabian Light Crude Oil

(Medium-Conversion Refinery)

Sulfur (ppm)

150

3050

Product name
Gases
Gasoline
Kerosene/jet
Fuel oil
Residue

Carbon no.

Benzene content (vol%, maximum)

Aromatics (vol%, maximum)

42

35

Olefins (vol%, maximum)

18

15

Boiling point (1C)

Volume (%)

14

4040

510

40200

45

RVP (kPa)

1016
2070

150260
200345

5
25

RON/MON (minimum)

470

4345

20

Oxygen (wt%, maximum)

2.7

2.3

60

50

95/85

95/85

a
RVP, Reid vapor pressure; RON, research octane number;
MON, motor octane number.

720

Oil Refining and Products

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

point, flash point, and smoke point. Commercial jet

fuel has a boiling point range of approximately 190
2751C and that of military jet fuel is 552851C.
Kerosene, with less critical specifications, is used for
lighting, heating, solvents, and blending into diesel
fuel. n-Paraffins in the range C12C14 may be extracted
from kerosene for use in the production of detergents.

2.4 Other Oil Products

2.4.1 Refinery Gases
Refinery gases are the lightest hydrocarbons containing a mixture of gases from methane to liquefied
petroleum gas (LPG) and some pentanes. The gases
are processed to separate LPG, which consists
principally of propane and butane. Other refinery
gases include lighter paraffins, unsaturates, and
hydrogen sulfide. LPG is used as fuel and as an
intermediate in the manufacture of olefins and selected
petrochemical feedstocks. Butanes are also used in the
manufacture of ethers and to adjust the vapor pressure
of gasoline. LPG is also used in transportation and in
domestic and household applications.
2.4.2 Petrochemical Feedstocks
Light olefins from FCC and benzene, toluene, xylenes
(BTX) aromatics from naphtha reforming are the
main petrochemical feedstocks derived from refineries. These products are the basis for integrating
refining and petrochemical operations. Olefins include propylene and butanes, whereas benzene and
xylenes are precursors for many valuable chemicals
and intermediates, such as styrene and polyesters.
2.4.3 Residual Fuel Oil
Residual fuel oil is the least valuable of the refiners
products, selling at a price below that of crude oil.

Residual fuels are difficult to pump and may be

heavier than water; they are also difficult to disperse
and are likely to form tar balls, lumps, and
emulsions. Many marine vessels, power plants,
commercial buildings, and industrial facilities use
residual fuels or combinations of residual and
distillate fuels for heating and processing. The two
most critical properties of residual fuels are viscosity
and low sulfur content for environmental control.
2.4.4 Coke and Asphalt
Petroleum coke is produced in coking units and is
almost pure carbon with a variety of uses from
electrodes to charcoal briquets. Asphalt is a semisolid
material produced from vacuum distillation and is
classified into various commercial grades. It is used
mainly for paving roads and roofing materials.
2.4.5 Lubricants
Vacuum distillation and special refining processes
produce lube-oil base stocks. Additives such as
antioxidants and viscosity enhancers are blended
into the base stocks to provide the characteristics
required for motor oils, industrial greases, lubricants,
and cutting oils. The most critical quality is a high
viscosity index, which provides for greater consistency under varying temperatures.

3. LIGHT OIL PROCESSING

3.1 Catalytic Naphtha Reforming
Catalytic naphtha reforming combines a catalyst,
hardware, and processing to produce high-octane
reformate for gasoline blending or BTX aromatics
for petrochemical feedstocks. Reformers are also the
source of much needed hydrogen for hydroprocessing operations. Reforming reactions comprise cracking,
polymerization,
dehydrogenation,
and
isomerization, which take place simultaneously.
Universal Oil Products (UOP) and Axens-Institut
Francais du Petrole (IFP) are the two major licensors
and catalyst suppliers for catalytic naphtha reforming. Reforming processes differ in the mode of
operation [semiregenerative or continuous catalyst
regenerative (CCR)], catalyst type, and process
engineering design. All licensors agree on the
necessity of hydrotreating the feed to remove
permanent reforming catalyst poisons and to reduce
the temporary catalyst poisons to low levels. There
are more than 700 reformers worldwide, with a total
capacity of approximately 11.2 million barrels/day.
Approximately 40% of this capacity is located in

Oil Refining and Products

North America, followed by 20% each in Western

Europe and Asia-Pacific regions.
3.1.1 Reforming Processes
Reforming processes are generally classified into
semiregenerative, cyclic, and CCR. This classification
is based on the frequency and mode of regeneration.
The semiregenerative process requires unit shutdown
for catalyst regeneration, whereas the cyclic process
utilizes a swing reactor for regeneration in addition
to regular reactors. The continuous process permits
catalyst replacement during normal operation. Globally, the semiregenerative scheme dominates reforming capacity at approximately 57%, followed by the
continuous regenerative process at 27% and the
cyclic process at 11%. Most grassroots reformers are
designed to use continuous catalyst regeneration.
The semiregenerative process is a conventional
reforming process that operates continuously over a
period of up to 1 year. Conversion is kept more or less
constant by raising the reactor temperatures as catalyst
activity declines. The cyclic process typically uses five
or six fixed catalyst beds, similar to the semiregenerative process, with one additional swing reactor, which
is a spare reactor. CCR is characterized by high
catalyst activity with reduced catalyst requirements,
more uniform reformate of higher aromatic content,
and high hydrogen purity. Figure 2 presents a schematic diagram of a CCR process. The continuous process represents a step change in reforming technology
compared to semiregenerative and cyclic processes.
3.1.2 Reforming Catalysts
Since the 1950s, commercial reforming catalysts
have been essentially heterogeneous monometallic

compounds and are composed of a base support

material (usually chlorided alumina) on which
platinum metal was placed. These catalysts were
capable of producing high-octane products; however,
because they quickly deactivated as a result of coke
formation, they required high-pressure, low-octane
operations. In the early 1970s, bimetallic catalysts
were introduced to meet increasing severity requirements. Platinum and another metal (often rhenium,
tin, or iridium) account for most commercial
bimetallic reforming catalysts. The catalyst is most
often presented as 1/16, 1/8, or 1/4 in. Al2O3
cylindrical extrudates or beads, into which platinum
and other metal have been deposited. In commercial
catalysts, platinum concentration ranges between 0.3
and 0.7 wt% and chloride is added (0.11.0 wt%) to
the alumina support (Z or g) to provide acidity.

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

Net H2-rich gas

Net gas
compressor

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

722

Oil Refining and Products

formation of isobutane is a necessary step to produce

alkylate gasoline or methyl tertiary butyl ether
(MTBE). The extent of paraffin isomerization is
limited by a temperature-dependent thermodynamic
equilibrium. For these reactions, a more active
catalyst permits a lower reaction temperature and
that leads to higher equilibrium levels. Isomerization
of paraffins takes place under medium pressure
(typically 30 bar) in a hydrogen atmosphere.
C4 isomerization produces isobutane feedstock for
alkylation. Platinum or another metal catalyst,
alumina chloride, is used for the higher temperature
processes. In a typical low-temperature process where
only aluminum chloride is used, the feed to the
isomerization unit is n-butane or mixed butanes
combined with hydrogen (to inhibit olefin formation).
C5/C6 isomerization increases the octane number of
the light gasoline components n-pentane and nhexane, which are found in abundance in straightrun gasoline. The basic C5/C6 isomerization process is
essentially the same as butane isomerization.

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.

3.5 Polymerization and Dimerization

Catalytic polymerization and dimerization in petroleum refining refer to the conversion of FCC light
olefins, such as ethylene, propylene, and butenes, into
higher octane hydrocarbons for gasoline blending.
Polymerization combines two or more identical olefin
molecules to form a single molecule, with the same
elements being present in the same proportions as in
the original molecules. Light olefin feedstock is
pretreated to remove sulfur and other undesirable

Oil Refining and Products

compounds. In the catalytic process, the feedstock

either is passed over a solid phosphoric acid catalyst
on silica or comes into contact with liquid phosphoric
acid, where an exothermic polymeric reaction occurs.
Another process uses a homogenous catalyst system
of aluminum-alkyl and a nickel coordination complex. The hydrocarbon phase is separated, stabilized,
and fractionated into LPG and oligomers or dimers.

4. HEAVY DISTILLATE PROCESSING

4.1 Catalytic Hydrotreating
Catalytic hydrotreating is a hydrogenation process
used to remove approximately 90% of contaminants,
such as nitrogen, sulfur, oxygen, and metals, from
liquid petroleum fractions. These contaminants, if
not removed from the petroleum fractions as they
travel through the refinery processing units, can have
detrimental effects on the equipment, the catalysts,
and the quality of the finished product. In addition,
hydrotreating converts olefins and aromatics to
saturated compounds. World capacity of all types of
hydrotreating stands at approximately 38.3 million
barrels/day. Hydrotreating is used to pretreat catalytic reformer feeds, saturate aromatics in naphtha,
desulfurize kerosene/jet and diesel, saturate aromatics, and pretreat catalytic cracker feeds. It also
includes heavy gas oil and residue hydrotreating as
well as posthydrotreating of FCC naphtha.
Hydrotreating for sulfur or nitrogen removal is
called hydrodesulfurization or hydrodenitrogenation. Hydrotreating processes differ depending on
the feedstock available and the catalysts used. Mild
hydrotreating is used to remove sulfur and saturate
olefins. More severe hydrotreating removes nitrogen
and additional sulfur and saturates aromatics. In a
typical catalytic hydrotreater unit, the feedstock is
mixed with hydrogen, preheated in a fired heater
(3154251C), and then charged under pressure (up to
68 atm) through a fixed-bed catalytic reactor. In the
reactor, the sulfur and nitrogen compounds in the
feedstock are converted into H2S and NH3. Hydrodesulfurized products are blended or used as catalytic
reforming feedstock. Hydrotreating catalysts contain
cobalt or molybdenum oxides supported on alumina
and less often nickel and tungsten.

4.2 Fluid Catalytic Cracking

Catalytic cracking is the largest refining process for
gasoline production, with a global capacity of more

723

than 14.2 million barrels/day. The process converts

heavy feedstocks such as vacuum distillates, residues,
and deasphalted oil into lighter products that are rich
in olefins and aromatics. There are several commercial FCC processes that are employed in world
refineries with major differences in the method of
catalyst handling. FCC catalysts are typically solid
acids of fine particles, especially zeolites (synthetic Yfaujasite), aluminum silicate, treated clay (kaolin),
bauxite, and silica-alumina. Zeolite content in
commercial FCC catalysts is generally in the range
of 520 wt%, whereas the balance is a silica-alumina
amorphous matrix. Additives to the FCC process
make up no more than 5% of the catalyst and they
are basically used as octane enhancers, metal
passivators, and SOx reducing agents and are used
in CO oxidation and for gasoline sulfur reduction.
The FCC unit comprises a reaction section,
product fractionation, and a regeneration section.
In principle, the reactor (riser) and the regenerator
form the catalyst circulation unit in which the
fluidized catalyst is continuously circulated using
air, oil vapors, and steam as the conveying media.
Figure 3 presents a schematic of a typical FCC
process. The operating temperatures of the FCC unit
range from 500 to 5501C at low pressures. Hydrocarbon feed temperatures range from 260 to 4251C,
whereas regenerator exit temperatures for hot
catalyst range from 650 to 8151C. Several operating
parameters, mainly temperature, affect overall conversion and it is essential to determine which product
slate is needed so that process conditions are appropriately selected.
4.2.1 Reaction Section (Riser)
A typical FCC unit involves mixing a preheated
hydrocarbon charge with hot, regenerated catalyst
as it enters the riser leading to the reactor. Major
process variables are temperature, pressure, catalyst/
oil ratio, and space velocity. Hydrocarbon feed is
combined with a recycle stream within the riser,
vaporized, and raised to reactor temperature by
the hot regenerated catalyst. As the mixture moves
up the riser, the charge is cracked at approximately
110 kPa and the residence time is on the order of
1 s. In modern FCC units, almost all cracking
occurs within the riser. The cracking continues until
the oil vapors are separated from the catalyst in the
reactor cyclones.
Cracking reactions are endothermic; the energy
balance is obtained by the burning of catalystdeposited coke in the regenerator. Both primary
and secondary reactions take place during catalytic

724

Oil Refining and Products

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.

cracking. Primary reactions are the result of the

cracking of paraffins, alkyl naphthenes, and alkyl
aromatics. In general, all cracking reactions are
characterized by the production of appreciable
amounts of corresponding olefins. During the reactions, however, approximately 40% of the sulfur in
the FCC feed is converted to H2S, which is easily
removed. Much of the ongoing research is directed to
the removal of the remaining sulfur in FCC gasoline.

4.2.2 Product Fractionation

Cracked hydrocarbons are separated into various
products. The resultant product stream from the
reaction section is charged to a fractionating column,
where it is separated into fractions, and some of the
heavy oil is recycled to the riser. The main FCC
products are LPG, the gasoline fraction, and light cycle
oil. By-products include refinery gases, residue (slurry),
and coke. Since the FCC unit is the major source of
olefins in the refinery (for the downstream alkylation

unit or petrochemical feedstock), an unsaturated gas

plant is generally considered a part of it.
4.2.3 Regeneration Section
Spent FCC catalyst is regenerated by burning off
deposited coke to carbon dioxide The catalyst flows
through the catalyst stripper to the regenerator,
where most of the coke deposits burn off in the
presence of preheated air. The carbon content of the
regenerated catalyst is generally kept at the lowest
level to achieve selectivity benefits. Catalyst circulation and coke yield determine the temperature at
which the regenerator is operated. Maximum regenerator temperatures are limited by mechanical
specifications or sometimes by catalyst stability.
The temperature in the regenerator reaches almost
6501C due to the exothermic nature of coke-burning
reactions. Spent catalyst is continuously removed
and fresh catalyst is added as makeup to optimize the
cracking process. This added catalyst is in effect the
main determinant of catalyst activity. The typical

Oil Refining and Products

catalyst makeup requirement is approximately 0.1 kg

per barrel of total 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,

725

and platinum, or by a combination of molybdenum

and tungsten. The conventional catalysts of catalytic
hydrocracking are made up of weak acid supports.
These systems are more particularly used to produce
middle distillates of very good quality and also, if
their acidity is very weak, oil bases. Amorphous
silica-aluminas serve as supports with low acidity.
These systems have a very good selectivity in middle
distillates and the products formed are of good
quality. The low-acid catalysts among these can also
produce lubricant bases.

5. RESIDUAL OIL PROCESSING

5.1 Solvent Deasphalting
Solvent deasphalting (SDA) is a separation process
that represents a further step in the minimization of
residual fuel. Figure 4 presents a schematic diagram
of a typical SDA process. The process takes
advantage of the fact that maltenes are more soluble
in light paraffinic solvents than asphaltenes. This
solubility increases with solvent molecular weight
and decreases with temperature. There are constraints with respect to how deep an SDA unit can
cut into the residue or how much deasphalted oil
(DAO) can be produced. These constraints are
related to the DAO quality specifications required
by downstream conversion units and the final highsulfur residual fuel oil stability and quality.
SDA has the advantage of being a relatively lowcost process that has the flexibility to meet a wide
range of DAO qualities. The process has very good
selectivity for asphaltenes and metals rejection, some
selectivity for carbon rejection, and less selectivity for
sulfur and nitrogen. It is most suitable for the more
paraffinic vacuum residues as opposed to the highasphaltene-, high-metal-, high-concarbon-containing
vacuum residues. The disadvantages of the process
are that it performs no conversion, produces a very
high viscosity by-product pitch, and where highquality DAO is required, SDA is limited in the quality
of feedstock that can be economically processed.

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

Oil Refining and Products

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

Schematic diagram of a typical solvent deasphalting process.

residual fuel oil. Visbreaking reduces the quantity of

cutter stock required to meet fuel oil specifications
and, depending on fuel oil sulfur specifications,
typically reduces the overall quantity of fuel oil
produced by 20%. In general, visbreakers are
typically used to produce vacuum residues.
The process is available in two schemes: coil cracker
and soaker cracker. The coil cracker operates at high
temperatures during a short residence time of approximately 1 min. The soaker scheme uses a soaking drum
at 30401C at approximately 1020 min residence
time. The residue is rapidly heated in a furnace and
then cracked for a specific residence time in a soaking
zone under proper conditions of pressure and temperature. The soaking zone may be within the heater
or in a separate adiabatic soaking drum. The cracked
residue leaves the soaking zone after the desired degree
of reaction is reached and is quenched with gas oil
to stop the reaction and prevent coking.

thermal cracking schemes for residue upgrading in

many refineries, mainly in the United States. The
process provides essentially complete rejection of
metals and concarbon while providing partial or
complete conversion to naphtha and diesel. World
capacity of coking units is 4.2 million barrels/day
(approximately 54% of this capacity is in U.S.
refineries) and total coke production is approximately 172,000 tons/day. New cokers are designed to
minimize coke and produce a heavy coker gas oil that
is catalytically upgraded. The yield slate for a
delayed coker can be varied to meet a refiners
objectives through the selection of operating parameters. Coke yield and the conversion of heavy coker
gas oil are reduced, as the operating pressure and
recycle are reduced and, to a lesser extent, as temperature is increased.

5.4 Residue Hydrotreating and

Residue FCC
5.3 Coking
Approximately 90% of coke production comes from
delayed coking. The process is one of the preferred

Refineries that have a substantial capacity for

visbreaking, solvent deasphalting, or coking are faced
with large quantities of visbreaker tar, asphalt or

Oil Refining and Products

coke, respectively. These residues have high viscosity

and high organic sulfur content (46 wt%), with
primary consequences reflected in the potential for
sulfur emissions and the design requirements for a
sulfur removal system. Sulfur content is also important from the standpoint of corrosion, which
requires proper selection of design materials and
operating conditions. Other properties of residues
include their high heating value due to the high level
of fixed carbon that results in a higher yield of syngas
per ton of residue processed. Moreover, residues have
low volatile matter and ash content as well as little to
no oxygen content, resulting in low reactivity.
Residue hydrotreating is another method for
reducing high-sulfur residual fuel oil yields. Atmospheric and vacuum residue desulfurization units are
commonly operated to desulfurize the residue as a
preparatory measure for feeding low-sulfur vacuum
gas-oil feed to cracking units (FCC and hydrocrackers), low-sulfur residue feed to delayed coker units,
and low-sulfur fuel oil to power stations. Two
different types of processing units are used for the
direct hydrotreating of residues. These units are either
a down-flow, trickle phase reactor system (fixed
catalyst bed) or a liquid recycle and back-mixing
system (ebullating bed). Economics generally tend to
limit residue hydrotreating applications to feedstocks
containing less than 250 ppm nickel and vanadium.
Residue FCC (RFCC) is a well-established approach for converting a significant portion of the
heavier fractions of the crude barrel into a highoctane gasoline-blending component. In addition to
high gasoline yields, the RFCC unit produces
gaseous, distillate, and fuel oil-range products. The
RFCC units product quality is directly affected by its
feedstock quality. In particular, unlike hydrotreating,
RFCC redistributes sulfur, but does not remove it
from the products. Consequently, tightening product
specifications have forced refiners to hydrotreat
some, or all, of the RFCCs products. Similarly, in
the future, the SOx emissions from an RFCC may
become more of an obstacle for residue conversion
projects. For these reasons, a point can be reached
where the RFCCs profitability can economically
justify hydrotreating the RFCCs feedstock.

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

727

saturation of aromatics and olefins will accelerate the

demand for hydrogen within the refinery. Catalytic
naphtha reforming alone is not able to meet refinery
hydrogen requirements. A survey on world refining
indicated that the capacity of supplementary refinery
hydrogen, produced mainly by steam reforming of
methane, reached 337 million m3/day (11,880 million
ft3/day-MMcfd) in 2002 compared to 110 million m3/day in 1990. There is a growing recognition
that there will be a significant future shortage of
refinery hydrogen supply. Specific hydrogen production units, such as steam methane reformers or those
carrying out partial oxidation of heavy residues, will
have to be built.

6.2 Residue Gasification

The gasification of refinery residues into clean syngas
provides an alternative route for the production of
hydrogen and the generation of electricity in a
combined turbine and steam cycle. Compared to
steam-methane reforming, gasification of residues can
be a viable process for refinery hydrogen production
when natural gas price is in the range of $3.754.00/
million British thermal units (MMBtu). The largest
application of syngas production is in the generation
of electricity power by the integrated gasification
combined cycle (IGCC) process. Consumption of
electricity in the modern conversion refinery is
increasing and the need for additional power capacity
is quite common, as is the need to replace old capacity.
The design of a residue gasification plant requires a
careful matching and integration of the various
process steps to ensure optimum performance of the
whole system. In general, the IGCC plant consists of
several steps: gasification, gas desulfurization, and a
combined cycle. The technologies of the gasification
and the combined cycle are well known; the innovation, however, is their integration in order to
maximize the overall IGCC efficiency.

6.3 Aromatics Extraction

BTX aromatics are high-value petrochemical feedstocks produced by catalytic naphtha reforming and
extracted from the reformate stream. Whether or not
other aromatics are recovered, it is sometimes
necessary to remove benzene from the reformate in
order to meet mandated specifications on gasoline
composition. Aromatics production in refineries
reached 1.2 million barrels/day in 2002. Most new
aromatic complexes are configured to maximize the
yield of benzene and paraxylene and sometimes
orthoxylene. The solvents used in the extraction of

728

Oil Refining and Products

aromatics include dimethylfrmamide, formylmorpholine, dimethylsulfoxide, sulfolane, and ethylene glycols.

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.

6.5 Sulfur Recovery

Sulfur recovery converts hydrogen sulfide in sour
gases and hydrocarbon streams to elemental sulfur.
Total sulfur production in world refineries reached
approximately 64,000 tons/day in 2002 compared to
approximately 28,000 tons/day in 1996, corresponding to a yearly growing recovery rate of 20%. In other
words, in 2002 an average refinery recovered 0.8 kg
sulfur from one processed barrel of crude oil
compared to less than 0.4 kg sulfur recovered in
1996. This indicates the increasing severity of operations to meet stringent environmental requirements.
The most widely used sulfur recovery system is the
Claus process, which uses both thermal and catalytic
conversion reactions. A typical process produces
elemental sulfur by burning hydrogen sulfide under
controlled conditions. Knockout pots are used to
remove water and hydrocarbons from feed gas
streams. The gases are then exposed to a catalyst to
recover additional sulfur. Sulfur vapor from burning
and conversion is condensed and recovered.

6.6 Acid Gas Removal

Amine plants remove acid contaminants from sour
gas and hydrocarbon streams. In amine plants, gas
and liquid hydrocarbon streams containing carbon
dioxide and/or hydrogen sulfide are charged to a gas
absorption tower or liquid contactor, where the acid
contaminants are absorbed by counterflow amine
solutions [i.e., monoethanol amine (MEA), diethanol

amine (DEA), methyl diethanol amine (MDEA)]. The

stripped gas or liquid is removed overhead and the
amine is sent to a regenerator. In the regenerator, the
acidic components are stripped by heat and reboiling
and are disposed of, and the amine is recycled.

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

Oil Refining and Products

less than 30 or even 15 ppm, an increase of the cetane

number, a reduction in polyaromatic content, and
T95 point limitation. To fulfill all these legislative and
regional requirements, refiners must either revamp
existing units or invest in new hydroprocessing and
hydrogen production units.
7.1.2 Refinery Emissions
Refiners must comply with various environmental
regulations to reduce all types of pollutants in their
waste gas as well as wastewater systems. Most
concerns involve the emissions of SOx, NOx, CO,
hydrocarbons, and particulates. The oxides are
present in flue gases from furnaces, boilers, and
FCC regenerators. Tail gas treatment and selective
catalytic reduction units are being added to limit SO2
and NOx emissions. Water pollutants include oil,
phenol, sulfur, ammonia, chlorides, and heavy
metals. New biological processes can be used to
convert H2S or SOx from gaseous and aqueous
streams. Spent catalysts and sludges are also of
concern to the refinery in reducing pollution. Some
spent FCC catalysts can be used in cement but other
catalysts that contain heavy metals need special
treatment before proper disposal.

7.2 Future Refining Issues

World refining has been adapting to ongoing product
changes and environmental challenges. Transportation fuels with approximately free sulfur will be
needed to satisfy the demand of the automotive
industry to reduce emissions from internal combustion engines. There will be an increased demand for
alkylate and isomerate gasoline as well as deepdesulfurized diesel. This will increase the hydrogen
content in gasoline, enhance combustion, and reduce
the levels of carbon dioxide emissions.
The introduction of fuel cells as a feasible way to
fuel zero-emission vehicles is a major challenge to oil
companies and refiners. Virtually every major automotive manufacturer has a fuel-cell program and
most claim production readiness by 2005. Refiners
need to adapt to this technology in the future,
especially regarding new fuels needed for fuel cells.
Fuel-cell vehicles need hydrogen generated on-board
or carried in either compressed or liquid form. The
latter calls for a global hydrogen infrastructure. The
use of hydrocarbons and specifically gasoline to
generate hydrogen offers many economic advantages

729

such as the availability of a ready-made global

fueling infrastructure.
The huge technological challenges associated with
the transfer to a hydrogen economy necessitate an
efficient and better use of hydrocarbon resources to
compete with renewable energy sources. Refiners
need to enhance and integrate their business with
chemical production and power generation. In the
long run, the refinery will produce not just fuels, but
also chemicals and electricity.

SEE ALSO THE

FOLLOWING ARTICLES
Coal Preparation  Oil and Natural Gas Drilling 
Oil and Natural Gas Exploration  Oil and Natural
Gas: Offshore Operations  Oil Pipelines  Oil
Recovery  Petroleum System: Natures Distribution
System for Oil and Gas

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.