Refining Review—A Look Behind the Fence

One end product of production activity is crude oil. Produced crude gains significantly
in value once it is converted into finished products. Like upstream activities, refining
involves operation at extreme conditions and application of advanced technology.

David Allan Drilling and production are only the beginning— producers hold the attention of the public. The
Consultant complex refining processes, often conducted at crude oil from this effort disappears behind
Houston, Texas, USA extreme temperatures and pressures, are refinery fences at some 658 locations worldwide.
required to turn produced crude oil into the These plants range from a Venezuelan facility
Paul E. Davis products that power a global society. From running 149,000 m3/d [940,000 bbl/d] to loca-
Chevron multibillion-dollar deepwater platforms to drag- tions running less than 160 m3/d [1,000 bbl/d].1
Richmond, California, USA lines scooping oil sands from permafrost, oil Despite the huge disparity in size, these
For help in preparation of this article, thanks to Dr. Douglas
Harrison, Louisiana State University, Baton Rouge, USA.

Biofuels
Other

120 Natural gas liquids Recoverable

resources
Oil sands
100 Crude and condensate Oil sands,
651 billion bbl
Oil equivalent, million bbl/d

80 Liquids
demand
Heavy oil,
60 434 billion bbl

40
Conventional oil,
20 952 billion bbl

0
1980 1990 2000 2010 2020 2030
Year
>Global liquids supply and demand. Global liquids demand (transportation, industrial, residential,
commercial and power generation) is expected to rise from the current 13.5 million m3/d [85 million bbl/d]
to about 18.3 million m3/d [115 million bbl/d] in 2030 (left). Most of this demand will be satisfied by
crude and condensate. As conventional crude reserves become scarce, increasing reliance will be
placed on heavy oil to meet liquids demand. Recoverable heavy oil (22°API or less) (right) is nearly
50% of conventional oil reserves. Contributions from oil sands will grow throughout this period,
increasing from about 320,000 m3/d [2 million bbl/d] to nearly 1.1 million m3/d [7 million bbl/d] in 2030.
(Global liquids demand adapted with permission from ExxonMobil’s Energy Outlook, 2006, reference 2.
Recoverable resources adapted from Meyer and Attanasi, reference 2.)

14 Oilfield Review
refineries share a common goal of converting
crude oil into valuable and usable finished
products. That makes the refining story an
important one—economically and technologi-
cally. It is also a story of scientific achievement
and continuous improvement.
Refining is a vital link in the world economy.
Rising income levels and growing populations
exert continuous pressure on transportation fuels
and all chemical products made from oil (previous
page).2 This pressure to produce a growing supply
of fuels and chemicals coincides with
increasingly stringent worldwide environmental
standards. To meet these demands, refiners are
literally digging deeper into the bottom of each
barrel and processing more heavy oils as
conventional crude supplies become scarce.
This article discusses refining and its
evolution from simple beginnings using batch
equipment to today’s highly automated plants
operating around the clock. We will also examine
the growing presence of heavy oils in refinery
feedstocks and the trend toward achieving nearly
zero contaminant levels in transportation fuels.
Summer 2007
From Simple Beginnings to
a Key Global Industry
Although historians have noted the use of
petroleum and tar in ancient times, the first
reported refinery was built in 1860 in Titusville,
Pennsylvania, USA, at a cost of $15,000. 3 Then,
as now, the refiner’s challenge was to convert
high-boiling-point viscous crude oil into lower-
boiling-point products. Early refiners employed
batch rather than continuous systems and used
thermal cracking as the conversion process (see
“Refining Glossary,” next page). In this type of
cracking, large oil molecules are thermally
decomposed to molecules of lower-boiling-point
substances. The lower-boiling-point materials
that are stable leave the system as cracked gas,
gasoline and distillate in the kerosene-diesel
boiling range. Other components that are less
stable polymerize to form products heavier than
the original crude.
Thermal cracking to produce motor gasoline,
or petrol, was the primary conversion process
during the first part of the 20th century. Use of
thermal processes peaked in the 1930s and
subsequently declined as fluid-bed catalytic
cracking was introduced during World War II.
Catalytic cracking eventually displaced thermal
cracking as the primary conversion process,
although mild thermal cracking is still in use at
many small refineries. This displacement of the
thermal process is due to catalytic cracking’s
greater yields of high-octane gasoline with less
of the heavy fuel oil and no coke by-product.
Following the war, refining continued to mature
and expand through use of sophisticated cata-
lysts and automated process control. These
improvements increased conversion levels and
improved selectivity to desired products.
1. “Global Refining Capacity Increases Slightly in 2006,”
Oil & Gas Journal 104, no. 47 (December 2006): 56–60.
McKetta JJ Jr (ed): Petroleum Processing Handbook.
New York City: Marcel Dekker, 1992.
2. ExxonMobil’s Energy Outlook 2006. http://www.exxonmobil.
co.uk/Corporate/Citizenship /Imports/Energy Outlook06
/slide_9.html (accessed February 10, 2007).
Meyer RF and Attanasi ED: “Heavy Oil and Natural Bitu-
men—Strategic Petroleum Resources,” USGS (August
2003), http://pubs.usgs.gov/fs/fs070-03/fs070-03.html
(accessed February 10, 2007).
3. Nelson WL: Petroleum Refinery Engineering, 4th ed.
New York City: McGraw-Hill, 1958.
15
 Refining Glossary Refiners today confront the same challenge
Aromatics—a general term for petroleum hydrocarbons containing at least one ring with alternating double bonds.
that their predecessors faced over a hundred
years ago—refinery products must match
Batch processing—a production method in which the ingredients are mixed in a vessel and the required
marketplace demands. The current market
conditions applied; after a designated amount of time, the process is shut down and the vessel emptied.
demands a transportation-fuel product that boils
Bubble cap—a slotted cap placed on top of a vapor riser in a distillation column to promote vapor-liquid contact. below 345°C [650°F] with nearly zero sulfur
The bubble cap-riser assemblies are arranged on horizontal trays in the column. Other common tray-contacting content. The problem is that crude oil rarely
assemblies in the refinery include sieve trays and valve trays.
occurs in that form. Light, sweet crude such as
Coke—a carbonaceous material formed by condensation reactions at high temperatures. Brent and West Texas Intermediate with sulfur
Coking—a severe thermal cracking process on vacuum resid to produce coke and lighter products. levels below 1.0% by weight have become scarce
The most common variant is delayed coking in which long residence times at high temperature are used to and expensive as the market has moved toward
drive the process to nearly complete conversion. heavier crude with sulfur levels in the range of
Continuous processing—a production method with the ability to produce a product without interruption. 1.0 to 3.0% by weight. Increased use of heavy oil
with sulfur levels above 3.0% by weight has put
Cracking—splitting a carbon-carbon bond either by thermal means (coking) or with the aid of a catalyst
(catalytic cracking, hydrocracking).
additional demands on refineries.4 The quality
difference between light and heavy oil shows up
Deasphalting—using a light hydrocarbon to bring asphalt out of solution.
in the marketplace price that refiners pay for
Distillate—a refinery stream that has been vaporized and condensed. feedstock. The price differential between light
Distillation—the separation of components based on differences in their volatility.
crude (>40°API) and heavy oil (<20°API) varies
with the market, with $9.00 per bbl being a
Endothermic reaction—a chemical reaction that absorbs heat.
typical value.5 With high demand for light
Fouling—restricted flow in refinery lines or vessels as a result of coke formation, sludge accumulation or transportation fuels, 70 to 90% of the product
particle accumulation. barrel now boils below 345°C.6
Fractionation—a separation process based on concentration gradients. Refiners have met these challenges by
installing more conversion and product-finishing
Fuel oil—a broad classification for liquid fuels produced in the refinery that range from distillates to heavy fuel oil.
capacity. In this article, we will examine how a
Gas oil—any distillate stream having a boiling point higher than that of heavy naphtha. refinery takes crude and converts it to finished
Heavy oil—heavy, high-sulfur oil. Heavy oils are difficult to refine due to high levels of sulfur, condensed aromatics products for the market.
(asphaltenes) and metals. There is no universal definition for heavy oils but sulfur values are usually higher than 3.0%
by weight, and gravity is usually at or below 20 to 22°API. Separation Is the First Step
Isomerization—transformation of a molecule into another form (the isomer) with the same molecular weight but All refineries have three primary sections:
a different structural arrangement. separation, conversion and finishing.7 Before
Naphtha—a distillation cut in the range of 32 to 220°C [90 to 430°F]; naphthas are usually classified according to processing crude, refiners must physically sepa-
process and boiling range. rate it into various molecular-weight ranges. This
allows for tailored and selective conversion steps
Naphthenes—a general term for petroleum hydrocarbons containing at least one saturated ring.
to operate efficiently. Products from these con-
Octane number—a measure of the resistance to autoignition (knocking) of the fuel. The octane number is the version steps are then treated in several finishing
volume percentage of iso-octane in a mixture of n-heptane and iso-octane that has the same knock characteristics
as the fuel in question. 4. Dealing with heavy oil has presented producers with
additional challenges as well. Heavy-oil physical
Olefin—a general term for petroleum hydrocarbons containing at least one carbon-to-carbon double bond. properties make most varieties very difficult to transport
to the refinery by conventional means. Producers must
Paraffin—a general term for saturated petroleum hydrocarbons that contain no rings and have a carbon number decide whether to prepare heavy oil for shipping by
greater than about 20. dilution or by partial or full upgrading on site.
5. Davis NC: “Overview of Domestic Petroleum Refining
Petrochemicals—the generic name given to a broad range of products produced using by-product refinery streams and Marketing,” (February 5, 2007), http://www.eia.doe.
as feed. Petrochemical building blocks such as ethane may come directly from refinery streams or be produced by a gov/emeu/finance/usi&to/downstream/update/index.html
process such as naphtha cracking. (accessed February 13, 2007).
6. Davis P,Reynolds J, O’Neal A and Simmons K: Crude Oil
Silica-alumina—the name given to the amorphous catalytic cracking catalyst base material. Silica-alumina for and Its Refining. Richmond, California, USA: Chevron
cracking catalyst is synthetically produced by combining sodium silicate, sodium aluminate and sodium hydroxide. Technical University, 2005.
7. The terms product treating and finishing are often used
Steam ejection—the passage of steam through a jet ejector to generate a vacuum. interchangeably.
8. Speight JG: The Desulfurization of Heavy Oils and
Straight run—refinery fluid streams cut directly from the crude oil. Residua. New York City: Marcel Dekker, 2000.
Three-way catalytic converter—a canister in automobile exhaust systems used to reduce emissions. Gary JH and Handwerk GE: Petroleum Refining
Technology and Economics, 4th ed. New York City:
The converter acts by reduction of nitrogen oxides to nitrogen and oxygen, oxidation of carbon monoxide to carbon Marcel Dekker, 2001.
dioxide and oxidation of unburned hydrocarbons to carbon dioxide and water. 9. In a reference to early refinery operations when thermal
cracking was prevalent, these distillation units are still
Vacuum resid—the bottom or heaviest stream from the crude-oil vacuum distillation tower. called the atmospheric and vacuum pipestills in many
refining publications.
Visbreaking—mild thermal cracking.
10. Hsu CS and Robinson PR (eds): Practical Advances in
Zeolite—a silica-alumina mineral that has an open porous structure. Zeolites usually undergo further treatment by Petroleum Processing. New York City: Springer, 2006.
exchange with rare earths to produce the desired catalytic cracking catalyst properties.

16 Oilfield Review
steps to make them ready for sale. All these steps
operate in concert to turn crude into thousands
of products (below).8
The first step in any refinery is separation of
the crude oil into component streams in a
distillation unit. Crude oil contains thousands of
individual compounds and at atmospheric
pressure these components can boil anywhere
between 0°C [32°F] to more than 540°C
[1,000°F]. Distillation is used to separate the
crude into different boiling-range fractions for
efficient conversion and cleanup downstream.
Modern conversion refineries typically have two
distillation towers in series—a tower operating
close to atmospheric pressure followed by a
vacuum unit.9 These large towers often have the
highest feed rate of any unit in the refinery. A
large unit can process 32,000 m3/d [200,000 bbl/d]
or more of crude oil. The towers contain trays or
structured packing for vapor-liquid contacting,
and heights of 45 m [150 ft] are common.10

Refining Operations Petrochemical Operations

Separation Conversion Finishing Products Products

Liquefied petroleum Ink

Gas gas, fuel gas,
Butanes, butylenes Paintbrushes
plant Alkylation petrochemical feedstock
Telephones
Hydrotreating Gasoline Fishing lures
Deodorant
320°F Reformer Floor wax
Hydrogen
Electrical tape
320 to 450°F
Hydrotreating Food preservatives
Crude Kerosene
oil Atmospheric 450 to 580°F Safety glass
Hydrocracking
distillation
Synthetic rubber
580 to 650°F Hydrotreating Kerosene,
mid-distillate Vitamin capsules
Petrochemical
Catalytic cracking Naphtha, kerosene feedstock Insect repellant
650°F
(gas, naphtha) Paint
Heating oil
Fuel oil Beach umbrellas

Hydrocracking Gasoline, kerosene, Garden hoses

diesel oil Nail polish
Visbreaking Fuel oil Antihistamines
Tennis shoes
660 to 880°F Catalytic cracking Light ends False teeth
Vacuum
Naphtha, kerosene Shoe polish
distillation
Fan belts
Hydrotreating Gasoline, kerosene
Aspirin
1,050°F
880 to 1,050°F

Coking Coke Lipstick

Parachutes
Insoluble
Deasphalter Asphalt
Toothpaste
Soluble Yarn
Solvent Anesthetics
Aromatic oil
Extraction
Ballpoint pens
Lubricating oil,
wax, grease Heart valves

Refinery products Petrochemical products

100s to 1,000s > 10,000
>Typical refinery process flow showing separation, conversion and finishing sections with end products (left). The products from most refineries number
in the hundreds and may number in the thousands from conversion refineries if lubricating oil, wax and grease production are present. In some facilities,
refinery gas and naphtha are sent to petrochemical plants for further upgrading—where the eventual end products number in the tens of thousands
(right). (Adapted with permission from Speight, reference 8.)

Summer 2007 17
 The flow scheme through the atmospheric
and vacuum towers is straightforward. After
water and salt are removed, the crude oil is fed to
the atmospheric tower (left). In the atmospheric
tower, it is separated into several component
streams—gas, naphtha, distillate and residue.
The residue from this unit is sent to the vacuum
distillation tower to recover additional liquids in
the higher boiling-point ranges that will be used
as feed for the critical conversion units. Vacuum
distillation towers use steam ejection to generate
a vacuum of 50 to 100 mm of mercury. This keeps
temperatures low enough to avoid fouling on the
internal sections of the tower. Although all
refineries have distillation as the primary
separation process, some locations have
additional separation steps such as deasphalting

LIQUID
and other extraction steps.11
V A P O R
The units downstream of the towers trans-
Bubble caps Bubble caps form the separated fractions into products; this
is where the real work takes place. Some units
use sophisticated catalysts while others do their
work using brute-force thermal methods.
Liquid Temperatures in these units range from 4°C
Tray [40°F] in an alkylation reactor to 700°C
[1,300°F] in a catalytic cracking regenerator
vessel. Pressures may be as high as 20.7 MPa
LIQUID

[3,000 psi] in a hydrocracker to near

atmospheric level in a delayed-coking unit.
V A P O R

The Conversion Workhorse

Among the unique collection of elements in a
refinery, the most crucial are the conversion
units—for catalytic cracking, hydrocracking and
Liquid coking. These units convert the high molecular-
weight oil fractions from separation into com-
Tray ponents that become finished products. Of these
conversion units, the premier process is fluid
LIQUID

catalytic cracking (FCC). Catalytic cracking was

V A P O R catalyst; Exxon commercialized the first fluid-
>Distillation process. Crude-oil distillation is a thermal, physical separation
into product boiling-range components. In an atmospheric crude-oil
distillation unit, the feedstock is heated in exchangers and furnaces to about
370°C [700°F] (top). At this temperature, a significant portion of the crude
vaporizes and moves up the distillation column, while the remaining liquids
move down toward the bottom of the column. Vapors that escape to the top of
the column are condensed to a liquid, and a portion is returned to the column
as reflux. Throughout the column, liquid and vapors are in contact—internal
elements such as trays or packing assist in making that contact (bottom).
Inside the column, thermal layers are established that match the boiling-point
ranges of the product streams. These product streams are withdrawn as side
streams. Nitrogen level in the crude affects the color of the product streams.
From the top of the column down, these product streams start as clear fluids
and become progressively darker in color. The bottom stream from the
atmospheric crude distillation tower is sent to a vacuum tower if that tower is
present. (Adapted from Davis et al, reference 6.)
discovered in the 1920s using treated clay as a
bed unit at its Baton Rouge, Louisiana, refinery in
1942.12 Since then, catalytic cracking has become
the most widely used process for converting
higher boiling fractions into gasoline and
other products.13
The catalytic cracking process has a toler-
ance for a wide variety of feeds. A common feed
is a nominal 340 to 540°C [650 to 1,000°F]
fraction from the vacuum distillation tower. The
FCC feed is preheated and injected into a moving
stream of fluid catalyst from the regenerator at
the reactor entrance (next page).14 The tempera-
ture of the catalyst stream is about 700°C
[1,300°F] and cracking reactions happen
quickly. The kinetics for breaking carbon-carbon

18 Oilfield Review
 bonds are complex and may involve multiple
pathways and several secondary reactions. As a
result of the various reactions, the catalyst
leaving the reactor is deactivated from
carbon deposition.
The temperature at the top of the reactor
outlet is typically in the range of 480 to 550°C [900
to 1,020°F].15 Operators control this temperature
carefully, as it has an important effect on product
distribution; lower temperatures favor distillate
yield, while higher temperatures favor gasoline
and light olefins. Although secondary reactions Products
can be controlled to some degree by quenching at
the top of the reactor, enough occur that the
catalyst leaving the reactor is deactivated from Disengaging
carbon deposition. vessel
After separation, the deactivated catalyst Flue gas

passes to the regenerator vessel where the Spent

carbon deposits are burned off in controlled
fluidized combustion using air or oxygen-
enriched air. The regenerated catalyst passes
from the regenerator to the reactor to begin the
process again.
Temperatures in cracking regenerators can
approach 730°C [1,350°F], and the vessel walls
must be lined with refractory material to protect
the steel shell. Large vessel diameters keep gas
velocities low to minimize entrainment of the
fine catalyst particles in the flue gas. The energy
present in the regenerator flue gas is too
valuable for discharge to the atmosphere. It is
typically used to generate steam in a carbon
monoxide boiler.
Catalytic cracking units are heat balanced—
the combustion of the carbon on the spent
catalyst provides the energy required to preheat
the feed and supply the endothermic reaction.
Typically, about 70% of the energy from the
combustion is required for feed preheating and
the reaction. The other 30% is consumed by heat
losses, preheating air to the regenerator and
steam generation. A large catalytic cracking unit
can have 545 tonnes [600 tons] of catalyst
circulating at mass rates of tons per second.
Tuning of the simultaneous mass and energy
balances is the key to successful operation.
Although the catalytic cracking process has
seen many improvements during the last
75 years, none has had more effect than
improvements in the catalyst itself. The key
property of any cracking catalyst is the presence
of an active acid site on a solid surface. Early
FCC catalysts were synthetic silica-alumina.
These catalysts had a random distribution of
catalyst pores, and pore diameters were much
larger than molecular sizes.
catalyst
Steam
Regenerator
Reactor
Air, or air + O2
Steam
Regenerated
catalyst
Feed
>Fluid catalytic cracking unit at a Chevron refinery (left). The process uses a catalyst with an average
particle size of about 70 microns—similar in size to flour or talcum powder. The catalyst is fine enough
that it behaves as a fluid when aerated by a gas. In a typical operation (right), feed is injected into a
stream of fluidized catalyst from the regenerator and the resultant mass moves through the reactor.
The reaction is fast and the products, spent catalyst and unconverted feed move into the disengaging
vessel where hydrocarbons and catalyst are separated. Products and unconverted feed go to
fractionation. The spent catalyst goes to the regenerator vessel, and regenerated hot catalyst moves
through a large slide valve to the feed injection point where the process begins again. (Adapted from
Davis et al, reference 6.)
The breakthrough discovery in cracking matic compounds to be excluded, thereby reduc-
catalysis occurred in the 1960s with the ing undesirable reactions to carbon. These
introduction of zeolites to the silica-alumina improvements sharply increased catalyst activity
catalyst base. Zeolites allowed preparation of and improved selectivity to desirable products.
catalysts with a controlled three-dimensional Additional improvements to cracking catalyst
structure having molecule-sized pores.16 Control activity and selectivity continue to the
of pore size allows high molecular-weight aro- present day.
11. Some refineries use light hydrocarbons such as propane Magee JS and Dolbear GE: Petroleum Catalysis in
to precipitate asphaltenes in a solvent extraction step. Nontechnical Language. Tulsa: PennWell Publishing
The resultant deasphalted oil may be used in conversion Company, 1998.
steps or to produce lubricants. 13. Gary and Handwerk, reference 8.
12. The first use of treated clays to catalytically crack 14. Gary and Handwerk, reference 8.
petroleum fractions to gasoline is attributed to Eugene
Hsu and Robinson, reference 10.
Houdry. Commercial implementation during the late
1930s employed a bead catalyst that shuttled between 15. Hsu and Robinson, reference 10.
the reactor and the regenerator (moving beds). 16. Venuto PB and Habib ET Jr: Fluid Catalytic Cracking with
Zeolite Catalysts. New York City: Marcel Dekker, 1979.

20 Oilfield Review
 Another important refinery conversion process
is hydrocracking. Hydrocracking combines break-
ing of carbon-carbon bonds with the addition of
hydrogen. The process was originally developed
by I.G. Farben in 1927 to convert coal into
gasoline.17 Hydrocracking may take many forms
depending on the application. These range from
mild hydrocracking of heavy vacuum gas oils at
5.5 to 10.4 MPa [800 to 1,500 psi] hydrogen
partial pressure to severe hydrocracking of
residual oil at 20.7 MPa [3,000 psi].
Hydrocracking is a flexible process that can
be designed to maximize gasoline or diesel
production, to pretreat catalytic cracker feed, or
to produce base oils for manufacturing lubri-
cants. Regardless of the application, hydro-
cracking reactors typically use a shaped catalyst
loaded in downflow, fixed beds.18 Nearly all
hydrocracking catalysts use a silica-alumina base
with a metal component such as platinum or
palladium. The hydrocracking catalyst becomes
deactivated over time as carbon deposits build
up and cover active sites. This necessitates a
corresponding gradual increase in temperature
to maintain desired conversion targets. After two
or three years, hydrocracking catalyst activity
decreases to a point at which the unit must be
shut down and the catalyst regenerated or
replaced. Regeneration is accomplished by
burning off the carbon deposits in situ.
Hydrocracking catalysts may go through several
cycles before they must be replaced and precious
metals recovered.
Although hydrocrackers are expensive to
build, recent interest in them has been spurred
by high demand for light motor fuels and their
ability to produce specialty products such as
lubricant base oils. Environmental concerns
about refinery product contaminant levels have
also contributed to hydrocracking growth.
The last important refinery conversion
process is coking. Coking deals with the heaviest
part of the barrel—those components with
boiling points exceeding 540°C [1,000°F] known
as vacuum resid. Catalytic cracking can accom-
modate some vacuum resid, and direct sale of
fuel oil and asphalt is another outlet. However,
because of increased demand for light products
and more reliance on heavy oils, vacuum-resid
supply often exceeds demand. The refiner must
use a process like delayed coking to convert
the excess vacuum resid into useful products
(above right).
Unlike the majority of other refinery process
steps, no catalyst is used in coking. Time and
temperature are used to convert the vacuum
resid by means of two reaction pathways—
Summer 2007
Drilling water
Process gas
Light coker naphtha
Heavy coker naphtha
Coke
drums
Light coker gas oil
Residuum Heavy coker gas oil
feed
Furnace Coke
(+ water)
Feed plus recycle
Fuel
>Delayed coking unit at a Chevron refinery (top). Residuum feed plus
recycled material is heated to more than 480°C [900°F] in the feed preheat
furnaces (bottom). The temperature is high enough and residence time in
the furnaces long enough that thermal cracking of the feed occurs as the
discharge enters the coke drums. About 70% of the thermally cracked
product vaporizes; gas leaves the coke drum and moves to the product
fractionation tower. The other 30% undergoes condensation reactions and is
transformed into a solid, carbon-rich coke that eventually fills the drum. Pairs
of drums are employed and when a drum nears capacity, the drums are
switched and coke is physically removed. Initially, the drum is steam-stripped
to remove additional hydrocarbons and then quenched with water. When the
drum has cooled, the top and bottom heads are removed, and the coke is
drilled out using high-pressure water jets. Cycle time on delayed cokers is
usually 18 to 24 hours. The solid coke is discharged into a pit and handled as
a solid with grinders and a conveyor for moving the material to shipping.
(Adapted from Davis et al, reference 6.)
thermal cracking and condensation. Liquid Heavy, high-sulfur crudes tend to produce
products from a delayed-coking unit span the fuel-grade coke, a low-value solid fuel that can be
entire range from naphtha to heavy gas oil. blended with coal. Lower-sulfur crudes can
Because of the high concentration of olefins and produce higher-value anode-grade coke that is
other contaminants, coker product liquids must converted to anodes for aluminum manufac-
undergo hydrotreating so they can be blended turing. Although delayed coking is the most
into finished products. Depending on the feed common coking variant, some process capacity is
quality and coke-drum temperature, several installed as fluid coking—similar to fluid
varieties of solid coke may be produced. catalytic cracking but without the catalyst.
19
 2004 2005
built in the USA since 1976 despite a 45%
Australia
increase in gasoline usage over the same period.19
2004 USA 2008 Refiners have dealt with capacity constraints by
2004 Canada 2005 installing numerous debottlenecking projects. In
some cases, these projects are new construction
2004 Other EU 2005 in an existing refinery while others may add a
2004 Korea 2006 new catalyst or improved process control.
In addition to the challenges presented by
2004 Japan 2006
capacity constraints, refineries worldwide must
Germany 2004 now cope with greater quantities of heavy oil as
conventional sweet crude becomes scarce.
Gas oli ne- sulfur tar get,m
pp Refining heavy oil requires significantly more
1,000 100 10 1 severe conditions for a given set of product
>Gasoline-sulfur targets. Reduction of sulfur in motor gasoline is an important environmental goal.
specifications. This puts an additional strain on
Sulfur in gasoline is converted to sulfur dioxide in the automobile exhaust, and that acts as a poison
to the three-way catalytic converter. Reducing gasoline-sulfur content increases exhaust-gas refinery costs.
converter efficiency thereby decreasing toxic emissions. During the past few years, governmental Refineries prosper or fail on the profit margin
agencies worldwide have targeted motor gasoline as a candidate for large reductions in sulfur they make on each barrel of crude oil processed.
content. For example, Japan reduced sulfur in gasoline from 100 ppm in 2004 to 10 ppm in 2006, and
Germany achieved 10 ppm in 2004. The concept of low sulfur levels in gasoline is becoming the norm However, refineries are caught between the
rather than the exception. Sulfur levels in diesel fuel are following a similar path. (Adapted from Hsu desire of the public for low fuel prices and the
and Robinson, reference 10.) producers who want to sell their crude oil at the
highest price. Both the oil producers and the
Finishing Completes the Picture focus on molecular rearrangement processes— public believe that prices are set by the refinery
As important as the conversion units are to the reforming, alkylation and isomerization. This and that refinery profits are high. In reality,
refinery, the story does not end with them. Once rearrangement is necessary because the neither the producer nor the refiner sets the
the large molecules in the crude oil have been gasoline-boiling-range streams from conversion price, and average worldwide refining margins
converted to a range of smaller ones, they must and hydrotreating are rich in straight-chain are generally modest.20 Prices are set on the
undergo one or more finishing steps. The most paraffins and naphthenes that have low octane various worldwide financial exchanges that trade
widely used process in the finishing arsenal is numbers. Rearrangement transforms these low- contracts on crude oil and refined products.
hydrotreating—a generic name given to a wide octane components into higher octane branched Those prices are a minute-to-minute reflection of
range of hydrogenation or hydrogen-addition paraffins and aromatics. All of these processes how investors view future needs for energy and
steps. The most common reason for using are catalytic. Reforming and isomerization are petroleum products. All parties are at the mercy
hydrotreating on any refinery stream is sulfur conducted in the gas phase using either precious of those estimates.
removal. In addition to removing a substantial metals on alumina (reforming) or zeolite on Like crude-oil producers, refiners have also
amount of sulfur, hydrotreating may also target alumina (isomerization) as a catalyst. Alkylation, had to deal with the challenges presented by
other compounds containing metals and on the other hand, is conducted in the liquid environmental regulatory legislation. Environ-
nitrogen—and occasionally olefins and phase using either sulfuric or hydrofluoric acid mental regulations started to tighten in 1970,
aromatics may be hydrogenated. as a catalyst. and the trend has accelerated in recent years.
Hydrotreaters exhibit a wide range of The products produced in all of the conversion During this period, refineries have made
operating conditions. These units span the range and finishing steps are almost ready for sale. remarkable progress in cleaning up their direct
from simple kerosene units operating at 1.7 MPa Straight-run products may need additional and indirect emissions. Refineries have reduced
[250 psi] hydrogen partial pressure to units treating steps for drying and sulfur removal, and direct emissions by flue-gas scrubbing and
operating at 10.4 MPa [1,500 psi] and treating many products will require some blending and control systems, optimization of furnaces and
340 to 540°C [650 to 1,000°F] material. additives to meet final sales specifications. increased monitoring to reduce hydrocarbon
Hydrotreating can be used either in a stand- Depending on the location, gasoline usually emissions from valves and fittings.21 Refineries
alone mode to make a product ready for sale or requires additives for oxidation, metals and have also become more energy efficient, thereby
as a pretreatment for molecular rearrangement. corrosion inhibition plus anti-icing. Depending on reducing production of carbon dioxide. Nowhere
The demand for ever-increasing volumes of the complexity and product requirements, some has the environmental push been stronger than
high-quality motor gasoline has heightened the refineries may have units to produce asphalt, wax, the trend toward clean transportation fuels. This
lubricating oils and greases. trend has quickly spread worldwide (above left).
17. Gary and Handwerk, reference 8. Refiners are a vital part of the team that
18. Fixed-bed reactors are vertical, cylindrical vessels filled
with catalyst particles of controlled size, surface area Refining Present and Future converts crude oil into useful products. As more
and pore distribution. There has never been a more challenging of that crude oil comes from heavy oil and
19. Mouawad J: “No New Refineries in 29 Years, But Project higher-sulfur sources, refineries will have to
Tries to Find a Way,” The New York Times (May 9, 2005),
situation for refineries than the one they
http://select.nytimes.com/search/restricted/ currently face. Those that survived the profit continue to develop new technologies to supply
article?res=F30611FC39540C7A8CDDAC0894DD404482 margin collapse and capacity glut of the late the world with products that are both clean
(accessed January 31, 2007).
20. http://omrpublic.iea.org/refinerysp.asp (accessed 1980s and early 1990s now see their capacity and affordable. —DA
April 16, 2007). limits stretched. No new refineries have been
21. Hsu and Robinson, reference 10.

20 Oilfield Review