A Petroleum Prospecting Primer

Click on the numbers in the image below to learn about the tools Chevron uses in the quest for oil
and natural gas.

People have used petroleum products for nearly 5,000 years. The Babylonians caulked their
ships with asphalt, and the ancient Chinese lit their imperial palaces with natural gas. For these
early users, finding petroleum was a matter of guesswork and good luck. People simply looked
for oil seeps and hoped the source was nearby.
Today, petroleum prospecting is considerably less random. The goal is to find a convergence of
the geologic elements necessary to form an oil or gas field. These elements include a source rock
(1) to generate hydrocarbons, a porous reservoir rock (2) to hold them and a structural trap (3) to
prevent fluids and gas from leaking away. Traps tend to exist in predictable places - for example,
along faults (4) and folds (5) caused by movement of the Earth's crust or near subsurface salt
domes (6).
Finding these subterranean features requires a careful blend of science and art. For example,
structural geology involves gathering and interpreting information from above ground to deduce
what lies underground. Geologists (7) obtain this information by examining exposed rocks or,
when difficult terrain limits access, by examining images from satellites (8) and radar (9).
Subtle changes within the Earth's magnetic and gravitational fields also may signal the presence
of petroleum traps. To measure these changes, geophysicists use sensitive instruments called
gravity meters (10) or trail a magnetometer (11) from a plane in an aerial survey.
Seismic surveying involves sending sound waves underground and measuring how long it takes
subsurface rocks to reflect them back to the surface. These waves are made by pounding the
earth with a truck-mounted vibrator (12) or by exploding small charges on land or compressed air
guns (13) at sea. As the waves are reflected back, they're collected by listening devices called

geophones (14) and processed by computers. Earth scientists use the data to create threedimensional models of underground rocks.
Although sight and sound are the senses most frequently used in prospecting, smell also can
come into play. A sniffer (15) is a sort of high-tech "nose" that can detect traces of gaseous
hydrocarbons escaping from subsurface accumulations.
Geologic and geophysical clues are enticing, but drilling- both on land (16) and offshore (17) - is
the only way to confirm an oil or gas field's existence. Once a well is drilled, downhole logging
instruments (18) yield data on the types of rock and fluid present.
In the petroleum industry, the average U.S. wildcat well (an exploratory well drilled a mile or more
from existing production) has a one in 10 chance of striking hydrocarbons. A rank wildcat well,
drilled in an unproven, frontier area, stands a one in 40 chance. Thus, although today's
prospectors have better tools than their ancient counterparts, good luck still is a factor in the
search for petroleum.

What is crude oil?

Step right up. In this bottle is a remedy of wonderful efficacy. Its curative powers are
calculated to remove pain and alleviate human suffering and disease. Distilled 400 feet below the
earth's surface, this remarkable liquid is Mother Nature's bounteous gift of healing. It is my
pleasure - no, it is my duty - to bring this soothing restorative, this blessed ointment, this modernday balm of Gilead to the public.
There were few takers of the 19th century elixir that came to be called "snake oil." It was one of
the less successful uses of petroleum, but not the first to claim healing properties. Ancient
Persians, 10th century Sumatrans and pre-Columbian Indians all believed that crude oil had
medicinal benefits. Marco Polo found it used in the Caspian Sea region to treat camels for
mange, and the first oil exported from Venezuela (in 1539) was intended as a gout treatment for
the Holy Roman Emperor Charles V.
The mysterious oil that sometimes seeped to the earth's surface had other uses as well. In
Mesopotamia around 4000 B.C., bitumen - a tarry crude - was used as caulking for ships, a
setting for jewels and mosaics, and an adhesive to secure weapon handles. Egyptians used it for
embalming, and the walls of Babylon and the famed pyramids were held together with it. The
Roman orator Cicero carried a crude-oil lamp. And, in North America, the Senecas and Iroquois
used crude oil for body paint and for ceremonial fires.
Crude oil - as petroleum directly out of the ground is called - is a remarkably varied substance,
both in its use and composition. It can be a straw-colored liquid or tar-black solid. Red, green and

brown hues are not uncommon. The image of James Dean dripping with black oil from
his Texas gusher in the 1956 movie "Giant" may have been compelling, but it's not
descriptive of today's oil producers. For one thing, the days when a gusher signaled a
big discovery are long gone. Since the 1930s, oil producers have used blowout
preventers to stop gushers. In addition, not all crude oils behave in the Hollywood
manner. Some flow about as well as cold peanut butter.
Until the late 19th century, an oil find often was met with disinterest or dismay. Pioneers who
settled the American West dug wells to find water or brine, a source of salt; they were
disappointed when they struck oil.
Several historical factors changed that. The kerosene lamp, invented in 1854, ultimately created
the first large-scale demand for petroleum. (Kerosene first was made from coal, but by the late
1880s most was derived from crude oil.) In 1859, at Titusville, Penn., Col. Edwin Drake drilled the
first successful well through rock and produced crude oil. What some called "Drake's Folly" was
the birth of the modern petroleum industry. He sold his "black gold" for $20 a barrel.
Petroleum was prized mostly for its yield of kerosene until the turn of the century. Gasoline was
burned off, and bitumen and asphalt (the heavier parts of crude oil) were discarded. But gradually
rising in importance were the incandescent light and the internal combustion engine. The former
relied on oil-fired generating plants; the latter, on gasoline.
By the 1920s, crude oil as an energy source - not just as a curiosity - came into
its own. But to many, it's still as mysterious as it was to ancient man. Even in the
petroleum industry, most people never see crude oil.
Geologists generally agree that crude oil was formed over millions of years from
the remains of tiny aquatic plants and animals that lived in ancient seas. There
may be bits of brontosaurus thrown in for good measure, but petroleum owes its
existence largely to one-celled marine organisms. As these organisms died, they
sank to the sea bed. Usually buried with sand and mud, they formed an organicrich layer that eventually turned to sedimentary rock. The process repeated itself,
one layer covering another.
Then, over millions of years, the seas withdrew. In lakes and inland seas, a
similar process took place with deposits formed of non-marine vegetation.
In some cases, the deposits that formed sedimentary rock didn't contain enough
oxygen to completely decompose the organic material. Bacteria broke down the trapped and
preserved residue, molecule by molecule, into substances rich in hydrogen and carbon.
Increased pressure and heat from the weight of the layers above then caused a partial distillation
of the organic remnants, transforming them, ever so slowly, into crude oil and natural gas.
Although various types of hydrocarbons - molecules made of hydrogen and carbon atoms - form
the basis of all petroleum, they differ in their configurations. The carbon atoms may be linked in a
ring or a chain, each with a full or partial complement of hydrogen atoms. Some hydrocarbons
combine easily with other materials, and some resist such bonding.
The number of carbon atoms determines the oil's relative "weight" or density. Gases generally
have one to four carbon atoms, while heavy oils and waxes may have 50, and asphalts,
hundreds.
Hydrocarbons also differ in their boiling temperatures - a key fact for refiners who separate the
different components of crude oil by weight and boiling point. Gases, the lightest hydrocarbons,

boil below atmospheric temperature. Crude oil components used to make gasoline boil in the
range of 55 to 400 degrees Fahrenheit. Those used for jet fuel boil in the range of 300 to 550
degrees, and those for diesel, at about 700 degrees.
There are three essentials in the creation of a crude oil field:

First, a "source rock" whose geologic history allowed the formation of crude oil. This
usually is a fine-grained shale rich in organic matter.
Second, migration of the oil from the source rock to a "reservoir rock," usually a
sandstone or limestone that's thick and porous enough to hold a sizable accumulation of
oil. A reservoir rock that's only a few feet thick may be commercially producible if it's at a
relatively shallow depth and near other fields. However, to warrant the cost of producing
in more challenging regions (the Arctic North Slope, for example) the reservoir may have
to be several hundred feet thick.
Third, entrapment. The earth is constantly creating irregular geologic structures through
both sudden and gradual movements - earthquakes, volcanic eruptions and erosion
caused by wind and water. Uplifted rock, for example, can result in domelike structures or
arched folds called anticlines. These often serve as receptacles for hydrocarbons. The
probability of discovering oil is greatest when such structures are formed near a source
rock. In addition, an overlying, impermeable rock must be present to seal the
migrating oil in the structure.
The oldest oil-bearing rocks date back more than 600 million years; the youngest, about 1
million. However, most oil fields have been found in rocks between 10 million and 270
million years old.

Subsurface temperature, which increases with depth, is a critical factor in the creation of
oil. Petroleum hydrocarbons rarely are formed at temperatures less than 150 degrees
Fahrenheit and generally are carbonized and destroyed at temperatures greater than 500
degrees. Most hydrocarbons are found at "moderate" temperatures ranging from 225 to 350
degrees.
It is the particular crude oil's geologic history that is most important in determining its
characteristics. Some crudes from Louisiana and Nigeria are similar because both were formed in
similar marine deposits. In parts of the Far East, crude oil generally is waxy, black or brown, and
low in sulfur. It is similar to crudes found in central Africa because both were formed from
nonmarine sources. In the Middle East, crude oil is black but less waxy and higher in sulfur.
Crude oil from Western Australia can be a light, honey-colored liquid, while that from the North
Sea typically is a waxy, greenish-black liquid. Many kinds of crudes are found in the United States
because there is great variety in the geologic history of its different regions.
Crude oil is a surprisingly abundant commodity. The world has produced some 650 billion barrels
of oil, but another trillion barrels of proved reserves have yet to be produced. An additional 10
trillion barrels of oil resources await development, assuming the price of oil someday justifies
production. These resources include bitumen, shale oil and oil in existing fields that might be
produced through enhanced recovery methods.
Talk of crude oil oozes with superlatives. Not only was crude oil the basis of the world's first
trillion-dollar industry, it also is the largest item in the balance of payments and exchanges
between nations. And it employs most of the world's commercial shipping tonnage.
Crude oil may not be the panacea that snake oil claimed to be. But for 20th century industrialized
nations, it has proved to be more than good medicine.

What is a Refinery?
Inside a maze of silver towers and pipes is a fascinating factory that changes hydrocarbon
molecules to make gasoline.

A refinery is a factory. Just as a paper mill turns lumber into legal pads or a glassworks turns
silica into stemware, a refinery takes a raw material--crude oil--and transforms it into gasoline and
hundreds of other useful products.
A typical large refinery costs billions of dollars to build and millions more to maintain and upgrade.
It runs around the clock 365 days a year, employs between 1,000 and 2,000 people and occupies
as much land as several hundred football fields. It's so big and sprawling, in fact, that workers ride
bicycles from one station to another.
Chevron has five gasoline-producing "Factories" in the United States and another in Burnaby,
British Columbia. Chevron has refining capacities worldwide of over two million barrels per day.
These world class operations had surprisingly humble origins. In 1876, company pioneers used
wagons and mules to haul two primitive stills to a spot near Pico Canyon, Calif., the site of
California's first producing oil wells. The stills, each about the size of a garage, were used to heat
oil at the prodigious rate of 25 to 40 barrels a day. This "oil boiling" produced kerosene,
lubricants, waxes and gasoline--a clear, lightweight liquid that generally was discarded as a
useless byproduct. (Read more about Chevron's first refineries in the History section.)
Gasoline's lowly status rose quickly after 1892, when Charles Duryea built the first U.S. gaspowered automobile. From then on, the light stuff from crude oil became the right stuff.
Today, some refineries can turn more than half of every 42-gallon barrel of crude oil into gasoline.
That's a remarkable technological improvement from 70 years ago, when only 11 gallons of
gasoline could be produced. How does this transformation take place? Essentially, refining
breaks crude oil down into its various components, which then are selectively reconfigured into
new products.

This process takes place inside a maze of hardware that one observer has likened to "a
metal spaghetti factory." Employees regulate refinery operations from within highly
automated control rooms. Because so much activity happens out of sight, refineries are
surprisingly quiet places. The only sound most visitors hear is the constant, low hum of
heavy equipment.
The complexity of this equipment varies from one refinery to the next. In general, the
more sophisticated a refinery, the better its ability to upgrade crude oil into high-value products.
Whether simple or complex, however, all refineries perform three basic steps: separation,
conversion and treatment.

Separation: heavy on the bottom, light on the top

Modern separation--which is not terribly different from the "cooking" methods used at the Pico
Canyon stills--involves piping oil through hot furnaces. The resulting liquids and vapors are
discharged into distillation towers, the tall, narrow columns that give refineries their distinctive
skylines.
Inside the towers, the liquids and vapors separate into components or fractions according to
weight and boiling point. The lightest fractions, including gasoline and liquid petroleum gas (LPG),
vaporize and rise to the top of the tower, where they condense back to liquids. Medium weight
liquids, including kerosene and diesel oil distillates, stay in the middle. Heavier liquids, called gas
oils, separate lower down, while the heaviest fractions with the highest boiling points settle at the
bottom. These tarlike fractions, called residuum, are literally the "bottom of the barrel."
The fractions now are ready for piping to the next station or plant within the refinery. Some
components require relatively little additional processing to become asphalt base or jet fuel.
However, most molecules that are destined to become high-value products require much more
processing.

Conversion: cracking and rearranging molecules to

add value
This is where refining's fanciest footwork takes place--where fractions from the distillation towers
are transformed into streams (intermediate components) that eventually become finished
products. This also is where a refinery makes money, because only through conversion can most
low-value fractions become gasoline.
The most widely used conversion method is called cracking because it uses heat and pressure
to "crack" heavy hydrocarbon molecules into lighter ones. A cracking unit consists of one or more
tall, thick-walled, bullet-shaped reactors and a network of furnaces, heat exchangers and other
vessels.
Fluid catalytic cracking, or "cat cracking," is the basic gasoline-making process. Using intense
heat (about 1,000 degrees Fahrenheit), low pressure and a powdered catalyst (a substance that
accelerates chemical reactions), the cat cracker can convert most relatively heavy fractions into
smaller gasoline molecules.

Hydrocracking applies the same principles but uses a different catalyst, slightly
lower temperatures, much greater pressure and hydrogen to obtain chemical
reactions. Although not all refineries employ hydrocracking, Chevron is an
industry leader in using this technology to cost-effectively convert medium- to
heavyweight gas oils into high-value streams. The company's patented
hydrocracking process, which takes place in the Isocracker unit, produces mostly
gasoline and jet fuel.
Some Chevron refineries also have cokers, which use heat and moderate
pressure to turn residuum into lighter products and a hard, coallike substance
that is used as an industrial fuel. Cokers are among the more peculiar-looking refinery structures.
They resemble a series of giant drums with metal derricks on top.
Cracking and coking are not the only forms of conversion. Other refinery processes, instead of
splitting molecules, rearrange them to add value. Alkylation, for example, makes gasoline
components by combining some of the gaseous byproducts of cracking. The process, which
essentially is cracking in reverse, takes place in a series of large, horizontal vessels and tall,
skinny towers that loom above other refinery structures.
Reforming uses heat, moderate pressure and catalysts to turn naphtha, a light, relatively lowvalue fraction, into high-octane gasoline components. Chevron's patented reforming process is
called Rheniforming for the rheniumplatinum catalyst used.

Treatment: the finishing touch

Back when Chevron's founders boiled crude oil to get kerosene, they didn't have to worry about
customer specifications or government standards. Today, however, a major portion of refining
involves blending, purifying, fine-tuning and otherwise improving products to meet these
requirements.
To make Chevron gasoline, refinery technicians carefully combine a variety of streams from the
processing units. Among the variables that determine the blend are octane level, vapor pressure
ratings and special considerations, such as whether the gasoline will be used at high altitudes.
Technicians also add Techron, Chevron's patented performance additive, and dyes that
distinguish the various grades of fuel.
Refining has come a long way since the oil boiling days of Pico Canyon. By the time a gallon of
gasoline is pumped into a car's tank, it contains more than 200 hydrocarbons and additives. All
that changing of molecules pays off in a product that ensures smooth, high-performance driving.

A quick lesson in refinery economics

The ultimate operating variable is, of course, the price of crude oil. Crude oil quality is another key
variable. Heavy, high-sulfur crudes can cost up to one-third less than lighter, better crudes.
However, because high-sulfur crudes require more processing, refineries that buy primarily cheap
crudes incur more fixed expenses for equipment and labor.
Processing high-sulfur crudes also requires greater expenditures for energy. In fact, energy
accounts for roughly half the cost of running a refinery, which is the main reason Chevron has
cogeneration plants at most of its facilities. Cogeneration uses gases from refinery processing
units to generate electricity and steam.
Refinery location is yet another variable. The closer a refinery is to both crude oil sources and a
high demand market, the lower transportation costs are. Chevron's large and modern refinery in
Pascagoula, Miss., on the other hand, is not as close to major gasoline-buying markets. Thus,
Chevron must factor in the added cost of getting Pascagoula's products to market. Nevertheless,
the refinery has posted excellent profits, largely because it is well-equipped to run some of the
heaviest, cheapest crudes in the world.

Running a refinery is never simple, and Chevron works hard

to keep its facilities safe, flexible and compatible with the
environment

What is a
Refinery?
A Lesson in How to Make Gasoline
An oil refinery is a more than just a complicated maze of steel towers and
pipes. It is actually a factory that takes crude oil and turns it into gasoline
and hundreds of other products necessary for our modern society to
function.
A typical refinery these days costs billions of dollars ($$$) to build, and
millions more just to maintain and upgrade. Large refineries are complex
operations that run 365 days a year, employ as many as 2,000 people, and
may occupy as much land as several hundred football fields. Some are so big
and sprawling that workers need to ride bicycles just to get from one part
of the refinery complex to another.
Yet refineries of today had surprisingly humble origins. For example, Kern
County pioneers in the 1860's used mule-drawn wagons to haul a primitive
still to a spot near the modern intersection of Twissleman Road and Highway
33 to erect the Buena Vista refinery. This pioneer operation boiled a few
barrels a day of tarry oil, dipped by hand from shallow shafts that
represented Kern County's first oil wells, to produce kerosene for lamps,
lubricants for wagon wheels, waxes for candles, and gasoline--a clear,
lightweight liquid that was usually thrown away as a useless byproduct.
The lowly status of gasoline changed dramatically, when Charles Duryea in
1892 built the first gas-powered automobile in the United States. Within
just a few short years cars became engrained our society, and the light
stuff from crude oil became the right stuff. Today, refineries turn more
than half of every 42-gallon barrel of crude oil into gasoline. This is a

remarkable advance from 70 years ago when each barrel of crude yielded
only 11 gallons of gasoline.
How does this remarkable transformation take place? Actually, there are
three basic steps common to all refining operations, whether big or small,
simple or complex. First, the separation process separates crude oil into
various chemical components. Next, the conversion process goes a step
further by breaking these chemicals down into molecules called
hydrocarbons. Lastly, the treatment process combines and transforms
hydrocarbon molecules, and other chemicals called additives, to create a
host of new products.

Separation: Heavy on the

bottom, Light on the top
Separation starts by pumping crude
oil into pipes running through hot
furnaces and heating the oil to
vaporize it. The resulting vapors and
liquids are discharged into distillation
towers, the tall, narrow columns that
give refineries their distinctive
skylines. The process is basically the
same used at the old Buena Vista still
in the early days of the Kern County oil industry.
Inside the towers, the liquids and vapors separate into components or
fractions according to their density and boiling point. The lightest fractions,
including gasoline and liquid petroleum gas (LPG), vaporize and rise to the top
of the tower, where they condense back to liquids. Medium-weight liquids,
including kerosene and diesel oil, stay in the middle. Heavier liquids, called
gas oils, separate lower down. The heaviest fractions with the highest boiling
points settle at the bottom. These tar-like fractions, called residuum, are
literally the "bottom of the barrel."
The various fractions are then piped to different stations or plants within
the refinery. Some fractions require relatively little additional processing to

become road asphalt or jet fuel. However, fractions destined to

become high-value products, such as gasoline, typically require
much more additional processing.

Conversion: Cracking and rearranging molecules

Conversion is where fractions from the distillation towers are

transformed into streams (intermediate components) that eventually

become finished products. This also is where a refinery makes money,
because only through conversion can most low-value fractions become
gasoline.
The most widely used conversion method is called cracking, which uses heat
and pressure to literally "crack" heavy hydrocarbon molecules into lighter
ones. A cracking unit consists of one or more tall, thick-walled, bullet-shaped
containers, called reactors, and a network of furnaces, heat exchangers, and
other vessels.
Fluid catalytic cracking, or "cat cracking," is the basic gasoline-making
process. Using intense heat (about 1,000 degrees Fahrenheit), low pressure
and a powdered catalyst (a substance that accelerates chemical reactions),
the cat cracker can convert most relatively heavy fractions into smaller
gasoline molecules.
Hydrocracking applies the same principles but uses a different catalyst,
slightly lower temperatures, much greater pressure and hydrogen to obtain
chemical reactions. Although not all refineries employ hydrocracking,
Chevron is an industry leader in using this technology to cost-effectively
convert medium- to heavyweight gas oils into high-value streams. The
company's patented hydrocracking process, which takes place in the
Isocracker unit, produces mostly gasoline and jet fuel.
Some refineries also have cokers, which use heat and moderate pressure to
turn residuum into lighter products and a hard, coallike substance that is
used as an industrial fuel. Cokers are among the more peculiar-looking

refinery structures. They resemble a series of giant drums with metal

derricks on top.
Cracking and coking are not the only forms of conversion. Other refinery
processes, instead of splitting molecules, rearrange them to add value.
Alkylation, for example, makes gasoline components by combining some of
the gaseous byproducts of cracking. The process, which essentially is
cracking in reverse, takes place in a series of large, horizontal vessels and
tall, skinny towers that loom above other refinery structures.
Reforming uses heat, moderate pressure, and catalysts to turn naphtha, a
light, relatively low-value fraction of the oil, into high-octane gasoline.

Treatment: Adding the finishing touches

Treament is the final step before tanker trucks and railroad cars head out
of the refinery to deliver gasoline to our local gas station. Back when
workers at the Buena Vista refinery boiled crude oil to get kerosene, they
didn't worry about customer specifications or government standards. Today
is diffrerent, and a major part of modern refining involves blending,
purifying, fine-tuning and otherwise improving products to meet these
requirements.
To make gasoline, refinery technicians carefully combine a variety of
streams from the processing units. Among the variables that determine the
blend are octane level, vapor pressure ratings, and other special
considerations, such as whether the gasoline will be used at high altitudes.
Technicians also add patented performance additives, and dyes to
distinguish the various grades of fuel.
Refining has come a long way since the days of the Buena Vista refining still.
By the time a gallon of gas is pumped into a car, it contains more than 200
hydrocarbons and additives. All that changing of molecules pays off in a
product that ensures smooth, high-performance driving.

Contents
[hide]

1 Operation
2 Products of oil refineries
3 Safety and environmental concerns
4 Common process units found in a refinery
5 Specialty end products

6 Co-plant siting
7 History
8 See also
9 References
10 External links

An oil refinery is an industrial process plant where crude oil is processed and refined
into more useful petroleum products, such as gasoline, diesel fuel, asphalt base, heating
oil, kerosene, and liquefied petroleum gas.

Contents
[show]

[edit] Operation

Crude oil is separated into fractions by fractional distillation. The fractionating column is
cooler at the top than at the bottom so the vapours can condense more easily while
moving up the column. The heavier fractions that emerge from the bottom of the
fractionating column are often broken up (cracked) to make more useful products.
Raw oil or unprocessed ("crude") oil is not very useful in the form it comes in out of the
ground. Although "light, sweet" (low viscosity, low sulfur) oil has been used directly as a

burner fuel for steam vessel propulsion, the lighter elements form explosive vapors in the
fuel tanks and so it is quite dangerous, especially so in warships. For this and many other
uses, the oil needs to be separated into parts and refined before use in fuels and
lubricants, and before some of the byproducts could be used in petrochemical processes
to form materials such as plastics, and foams. Petroleum fossil fuels are used in ship,
automobile and aircraft engines. These different hydrocarbons have different boiling
points, which means they can be separated by distillation. Since the lighter liquid
elements are in great demand for use in internal combustion engines, a modern refinery
will convert heavy hydrocarbons and lighter gaseous elements into these higher value
products using complex and energy intensive processes.
Oil can be used in so many various ways because it contains hydrocarbons of varying
molecular masses, forms and lengths such as paraffins, aromatics, naphthenes (or
cycloalkanes), alkenes, dienes, and alkynes. Hydrocarbons are molecules of varying
length and complexity made of only hydrogen and carbon atoms. Their various structures
give them their differing properties and thereby uses. The trick in the oil refinement
process is separating and purifying these.
Once separated and purified of any contaminants and impurities, the fuel or lubricant can
be sold without any further processing. Smaller molecules such as isobutane and
propylene or butylenes can be recombined to meet specific octane requirements of fuels
by processes such as alkylation or less commonly, dimerization. Octane grade of gasoline
can also be improved by catalytic reforming, which strips hydrogen out of hydrocarbons
to produce aromatics, which have much higher octane ratings. Intermediate products such
as gasoils can even be reprocessed to break a heavy, long-chained oil into a lighter shortchained one, by various forms of cracking such as Fluid Catalytic Cracking, Thermal
Cracking, and Hydrocracking. The final step in gasoline production is the blending of
fuels with different octane ratings, vapor pressures, and other properties to meet product
specifications.

[edit] Products of oil refineries

Asphalt
Diesel fuel
Fuel oils
Gasoline
Kerosene
Liquid petroleum gas (LPG)
Lubricating oils
Paraffin wax
Tar

[edit] Safety and environmental concerns

MiRO refinery at Karlsruhe

Oil refineries are typically large sprawling industrial complexes with extensive piping
running throughout. The refining process releases numerous different chemicals into the
atmosphere; consequently, there are substantial air pollution emissions[1] and a notable
odor normally accompanies the presence of a refinery. Aside from air pollution impacts
there are also wastewater concerns,[2] upset risks of fire and explosion, and both
occupational noise and environmental noise health effects.
The public has demanded that many governments place restrictions on contaminants that
refineries release, and most refineries have installed the equipment needed to comply
with the requirements of the pertinent environmental protection regulatory agencies. In
the United States, there is strong pressure to prevent the development of new refineries,
and no major refinery has been built in the country since Marathon's Garyville facility in
1976. However, many existing refineries have been expanded during that time.
Environmental restrictions and pressure to prevent construction of new refineries have
also contributed to rising fuel prices in the United States[citation needed].
Environmental and safety concerns mean that oil refineries are sometimes located some
distance away from major urban areas. Nevertheless, there are many instances where
refinery operations are close to populated areas and pose health risks such as in Tenerife,
Spain [3], which is sited in a densely-populated city center and next to the only two major
evacuation routes in and out of the city. In California's Contra Costa County and Solano
County, a shoreline necklace of refineries and associated chemical plants are adjacent to
urban areas in Richmond, Martinez, California, Pacheco, Concord, Pittsburg, Vallejo and
Benicia, with occasional accidental events that require "shelter in place" orders to the
adjacent populations.

[edit] Common process units found in a refinery

Desalter Unit (washes out salt from the crude oil before it goes into the
atmospheric distillation unit)
Atmospheric Distillation Unit (distills crude oil into fractions)

Vacuum Distillation Unit (further distills residual bottoms after atmospheric

distillation)
Naphtha Hydrotreater Unit (desulfurizes naphtha from atmospheric distillation.
Must hydrotreat the naphtha before sending to a Catalytic Reformer Unit.)
Catalytic Reformer Unit (contains catalyst used to convert the naphtha-boiling
range molecules into higher octane reformate (reformer product). The reformate
has higher content of aromatics, olefins, and cyclic hydrocarbons). An important
byproduct of a reformer is hydrogen released during the catalyst reaction. The
hydrogen is used either in the hydrotreaters and hydrocracker.)
Distillate Hydrotreater Unit (desulfurizes distillate (diesel) after atmospheric
distillation)
Fluid Catalytic Cracking (FCC) Unit (upgrades heavier fractions into lighter,
more valuable products)
Hydrocracker Unit (upgrades heavier fractions into lighter, more valuable
products)
Coking unit (processes asphalt into gasoline and diesel fuel, leaving coke as a
residual product)
Alkylation unit (produces high octane component for gasoline blending)
Dimerization Unit
Isomerization Unit (converts linear molecules to higher octane branched
molecules for blending into gasoline or feed to alkylation units)
Steam reforming Unit (produces hydrogen for the hydrotreaters or hydrocracker)
Liquified gas storage units for propane and similar gaseous fuels at pressure
sufficient to maintain in liquid form - these are usually spherical or bullets
(horizontal cylinder with rounded ends).
Storage tanks for crude oil and finished products, usually cylindrical, with some
sort of vapor enclosure and surrounded by an earth berm to contain spills
Amine gas treater, Claus unit, and tail gas treatment for processing hydrogen
sulfide from hydrodesulfurization
Utility units such as cooling towers for circulating cooling water, boiler plants for
steam generation, and wastewater collection and treating systems to make such
water suitable for reuse or for disposal.

[edit] Specialty end products

These will blend various feedstocks, mix appropriate additives, provide short term
storage, and prepare for bulk loading to trucks, barges, product ships, and railcars.

Gaseous fuels such as propane, stored and shipped in liquid form under pressure
in specialized railcars to distributors.
Liquid fuels blending (producing automotive and aviation grades of gasoline,
kerosene, various aviation turbine fuels, and diesel fuels, adding dyes, detergents,
antiknock additives, oxygenates, and anti-fungal compounds as required).
Shipped by barge, rail, and tanker ship. May be shipped regionally in dedicated
pipelines to point consumers, particularly aviation jet fuel to major airports, or

piped to distributors in multi-product pipelines using product separators called

pipeline inspection gauges ("pigs").
Lubricants (produces light machine oils, motor oils, and greases, adding viscosity
stabilizers as required), usually shipped in bulk to an offsite packaging plant.
Wax, used in the packaging of frozen foods, among others. May be shipped in
bulk to a site to prepare as packaged blocks.
Sulfuric acid finishing and shipping. This is a useful industrial material, usually
prepared and shipped as the acid precursor oleum, a byproduct of sulfur removal
from fuels.
Bulk tar shipping for offsite unit packaging for use in tar-and-gravel roofing.
Asphalt unit. Prepares bulk asphalt for shipment.
Petroleum coke, used in specialty carbon products or as solid fuel.

[edit] Co-plant siting

Frequently a chemical plant will be sited adjacent to a refinery, utilizing intermediate
products as feedstocks for the production of specialized materials such as plastics or
agrichemicals.

[edit] History
The world's first oil refinery opened at Ploieti, Romania in 1856 [4]. Several other
refineries were built at that location with investment from United States companies
before being taken over by Nazi Germany during World War II. Most of these refineries
were bombarded by the US Air Force in Operation Tidal Wave, August 1, 1943. Since
then they have been rebuilt, and currently pose somewhat of an environmental concern.
Another early example is Oljen, now preserved as a museum at the UNESCO world
heritage site Engelsberg. It started operation in 1875 and is part of the Ecomuseum
Bergslagen.
It is difficult to exactly state which is largest oil refinery in the world. At one time this
was claimed to be Ras Tanura, Saudi Arabia, owned by Saudi Aramco. For most of the
20th century, the largest refinery of the world was that of Abadan in Iran. This refinery
suffered extensive damage in the IRAN/IRAQ war. The Guinness Book of World
Records now (October 2006) records the BP Amoco refinery in Texas City, USA, as the
refinery with the largest capacity (433,000 barrels/day which is approximately
15,143,482 Imperial Gallon).
Early US refineries processed crude oil to recover the kerosene. Other products (like
gasoline) were considered wastes and were often dumped directly into the nearest river.
The invention of the automobile shifted the demand to gasoline and diesel, which remain
the primary refined products today. Refineries pre-dating the EPA were very toxic to the
environment. Strict legislation has mandated that refineries meet modern air and water
cleanliness standards. In fact, obtaining a permit to build even a modern refinery with

minimal impact on the environment (other than CO2 emmissions) is so difficult and
costly that no new refineries have been built in the United States since 1976. As a result,
the US is becoming more and more dependent on the imports of finished gasoline, as
opposed to incremental crude oil.

Crude Distillation
Distillation is the first step in the processing of crude oil and it takes place in a tall steel
tower called a fractionation column. The inside of the column is divided at intervals by
horizontal trays. The column is kept very hot at the bottom (the column is
insulated) but as different hydrocarbons boil at different
temperatures, the temperature gradually reduces towards the
top, so that each tray is a little cooler than the one below.

The crude needs to be heated up before entering the fractionation column and this is done
at first in a series of heat exchangers where heat is taken from other process streams
which require cooling before being sent to rundown. Heat is also exchanged against
condensing streams from the main column. Typically, the crude will be heated up in this
way upto a temperature of 200 - 280 0C, before entering a furnace.
As the raw crude oil arriving contains quite a bit of water and salt, it is normally sent for
salt removing first, in a piece of equipment called a desalter. Upstream the desalter, the
crude is mixed with a water stream, typically about 4 - 6% on feed. Intense mixing takes
place over a mixing valve and (optionally) as static mixer. The desalter, a large liquid full
vessel, uses an electric field to separate the crude from the water droplets. It operates best
at 120 - 150 0C, hence it is conveniently placed somewhere in the middle of the preheat
train.

Part of the salts contained in the crude oil, particularly magnesium chloride, are
hydrolysable at temperatures above 120 0C. Upon hydrolysis, the chlorides get converted
into hydrochloric acid, which will find its way to the distillation column's overhead
where it will corrode the overhead condensers. A good performing desalter can remove
about 90% of the salt in raw crude.
Downstream the desalter, crude is further heated up with heat exchangers, and starts
vaporising, which will increase the system pressure drop. At about 170 -200 0C, the crude
will enter a 'pre-flashvessel', operating at about 2 - 5 barg, where the vapours are
separated from the remaining liquid. Vapours are directly sent to the fractionation
column, and by doing so, the hydraulic load on the remainder of the crude preheat train
and furnace is reduced (smaller piping and pumps).

Just upstream the preflash vessel, a small caustic stream is mixed with the crude, in order
to neutralise any hydrochloric acid formed by hydrolysis. The sodium chloride formed
will leave the fractionation column via the bottom residue stream. The dosing rate of
caustic is adjusted based on chloride measurements in the overhead vessel (typically 10 20 ppm).
At about 200 - 280 0C the crude enters the furnace where it is heated up further to about
330 -370 0C. The furnace outlet stream is sent directly to the fractionation column. Here,
it is separated into a number of fractions, each having a particular boiling range.
At 350 0C, and about 1 barg, most of the fractions in the crude oil vapourise and rise up
the column through perforations in the trays, losing heat as they rise. When each fraction
reaches the tray where the temperature is just below its own boiling point, it condenses
and changes back into liquid phase. A continuous liquid phase is flowing by gravity
through 'downcomers' from tray to tray downwards. In this way, the different fractions
are gradually separated from each other on the trays of the fractionation column. The
heaviest fractions condense on the lower trays and the lighter fractions condense on the
trays higher up in the column. At different elevations in the column, with special trays
called draw-off trays, fractions can be drawn out on gravity through pipes, for further
processing in the refinery.
At top of the column, vapours leave through a pipe and are routed to an overhead
condenser, typically cooled by air fin-fans. At the outlet of the overhead condensers, at
temperature about 40 0C, a mixture of gas, and liquid naphtha exists, which is falling into
an overhead accumulator. Gases are routed to a compressor for further recovery of LPG
(C3/C4), while the liquids (gasoline) are pumped to a hydrotreater unit for sulfur
removal.
A fractionation column needs a flow of condensing liquid downwards in order to provide
a driving force for separation between light and heavy fractions. At the top of the column
this liquid flow is provided by pumping a stream back from the overhead accumulator
into the column. Unfortunately, a lot of the heat provided by the furnace to vaporise
hydrocarbons is lost against ambient air in the overhead fin-fan coolers. A clever way of
preventing this heat lost of condensing hydrocarbons is done via the circulating refluxes
of the column. In a circulating reflux, a hot side draw-off from the column is pumped
through a series of heat exchangers (against crude for instance), where the stream is
cooled down. The cool stream is sent back into the column at a higher elevation, where it
is been brought in contact with hotter rising vapours. This provides an internal
condensing mechanism inside the column, in a similar way as the top reflux does which
is sent back from the overhead accumulator. The main objective of a circulating reflux
therefore is to recover heat from condensing vapours. A fractionating column will have
several (typically three) of such refluxes, each providing sufficient liquid flow down the
corresponding section of the column. An additional advantage of having circulating
refluxes is that it will reduce the vapour load when going upwards in the column. This
provided the opportunity to have a smaller column diameter for top sections of the tower.
Such a reduction in diameter is called a 'swage'.

The lightest side draw-off from the fractionating column is a fraction called kerosene,
boiling in the range 160 - 280 0C, which falls down through a pipe into a smaller column
called 'side-stripper'. The purpose of the side stripper is to remove very light
hydrocarbons by using steam injection or an external heater called 'reboiler'. The
stripping steam rate, or reboiled duty is controlled such as to meet the flashpoint
specification of the product. Similarly to the atmospheric column, the side stripper has
fractionating trays for providing contact between vapour and liquid. The vapours
produced from the top of the side stripper are routed back via pipe into the fractionating
column.
The second and third (optional) side draw-offs from the main fractionating column are
gasoil fractions, boiling in the range 200 - 400 0C, which are ultimately used for blending
the final diesel product. Similar as with the kerosene product, the gasoil fractions (light
and heavy gasoil) are first sent to a side stripper before being routed to further treating
units.
At the bottom of the fractionation column a heavy, brown/black coloured fraction called
residue is drawn off. In order to strip all light hydrocarbons from this fraction properly,
the bottom section of the column is equipped with a set of stripping trays, which are
operated by injecting some stripping steam (1 - 3% on bottom product) into the bottom of
the column.

Hydrotreating
The objective of the Hydrotreating prococess is to remove suplur as well as other unwanted
compunds, e.g. unsaturated hydrocarbons, nitrogen from refinery process streams.
Until the end of World War 2, there was little incentive for the oil industry to pay significant
attention to improving product quality by hydrogen treatment. However, soon after the war the
production of high sulphur crudes increased significantly, which gave a more stringent demand on
the product blending flexibility of refineries, and the marketing specifications for the products
became tighter, largely due to environmental considerations. Furthermore, the catalyst used in
the Platforming process can only handle sulfur in the very low ppm level, so hydrotreating of
naphtha became a must. The necessity for hydrotreating of middle distillates (kerosene/gasoil)
originates from pressure to reduce sulfur emissions into the environment. Overall, this situation
resulted in an increased necessity for high sulphur removal capability in many refineries.
As catalytic reforming gives hydrogen as a byproduct, it gave additional momentum to the
development of sulphur removal process by hydrogen treatment. In this treatment, the sulphur
compounds are removed by converting them into hydrogen sulphide by reaction with hydrogen in
the presence of a catalyst. This results in high liquid product yields, since only sulphur is
removed. Furthermore, the hydrogen sulphide produced can be easily removed from the product
gas stream, for example by an amine wash. In this way, hydrogen sulphide is recovered as a

higly concentrated stream and can be further

converted into elemental sulphur via the "Claus"
process.
Hydrodesulphursiation has been extensively used
commercially for treating naphtha as feedstock for
catalytic reformers to meet the very stringent sulphuir
specification of less than 1 ppm wt to protect the
platinum catalyst. It has also been widely used for
removal of sulphur compounds from kerosine and
gasoils to make them suitable as blending
components. In cases where products are from
catalytic or thermal crackers, hydrogen treatment is
used to improve product quality specifications like
colour, smoke point, cetane index, etc.
For Hydrotreating, two basic processes are applied,
the liquid phase (or trickle flow) process for kerosine
and heavier straight-run and cracked distillates up to vacumn gas oil and the vapour phase
process for light straight-run and cracked fractions.

Both processes use the same basic configuration: the feedstock is mixed with hydrogen-rich
make up gas and recycle gas. The mixture is heated by heat exchange with reactor effluent and
by a furnace and enters a reactor loaded with catalyst. In the reactor, the sulphur amd nitrogen
compounds present in the feedstock are converted into hydrogen sulphide and ammonia
respectively. The olefins present are saturated with hydrogen to become di-olefins and part of the
aromatics will be hydrogenated. If all aromatics needs to be hydrogenated, a higher pressure is
needed in the reactor compared to the conventional operating mode.
The reactor operates at temperatures in the range of 300-380 0C and at a pressure of 10-20 bar
for naphta and kero, as compared with 30-50 bar for gasoil, with excess hydrogen supplied. The
temperature should not exceed 380 0C, as above this temperature cracking reactions can occur,
which deteriorates the colour of the final product. The reaction products leave the reactor and,
after having been cooled to a low temperature, typically 40-50 0C, enter a liquid/gas separation
stage. The hydrogen-rich gas from the high pressure separation is recycled to combine with the
feedstock, and the low pressure off-gas stream rich in hydrogen sulphide is sent to a gas-treating
unit, where hydrogen sulphide is removed. The clean gas is then suitable as fuel for the refinery
furnaces. The liquid stream is the product from hydotreating. It is normally sent to a stripping
column where H2S and other undesirable components are removed, and finally, in cases where
steam is used for stripping, the product is sent to a vacumn drier for removal of water. Some
refiners use a salt dryer in stead of a vacuum drier to remove the water.
The catalyst used is normally cobalt, molybdenum and nickel finely distributed on alumina
extrudates. It slowly becomes choked by coke and must be renewed at regular
intervals (typically 2-3 years). It can be regenerated (by burning off the coke) and reused typically
once or twice before the breakdown of the support's porous
structure unacceptably reduces its activity. Catayst regeneration is,
nowadays, mainly carried out ex- situ by specialised firms. Other
catalysts have also been developed for applications where denitrification is the predominant
reaction required or where high stauration of olefins is necessary.

A more recent development is the application of Hydrotreating for pretreatment of feedstcok for
the catalytic cracking process. By utilisation of a suitable hydrogenation-promoting catalyst for
conversion of aromatics and nitrogen in potential feedstocks, and selection of severe operating
conditions, hydrogen is taken up by the aromatic molecules. The increased hydrogen content of
the feedstock obtained by this treatment leads to significant conversion advantages in
subsequent catalytic cracking, and higher yield of light products can be achieved.
Hydrotreatment can also be used for kerosine smoke point improvement (SPI). It closely
resembles the conventional Hydrotreating Process however an aromatic hydrogenation catalyst
consisting of noble metals on a special carrier is used. The reactor operates at pressure range of
50-70 bar and temperatures of
260-320 0C. To restrict temperature rise due to the highly exothermic aromatics conversion
reactions, quench oil is applied between the catalysts beds. The catalyst used is very sensitive to
traces of sulphur and nitrogen in the feedstock and therefore pretreatment is normally applied in a
conventional hydrotreater before kerosine is introduced into the SPI unit. The main objective of
Smoke Point Improvement is improvement in burning characteristics as the kerosine aromatics
are converted to naphthenes.
Hydrotreatment is also used for production of feedstocks for isomersiation unit from pyrolysis
gasoline (pygas) which is one of the byproducts of steam cracking of hydrocarbon fractions such
as naphtha and gasoil.
A hyrotreater and a hydrodesulphuriser are basically the same process but a hydotreater termed
is used for treating kerosene or lighter feedstock, while a hydodesulhuriser mainly refers to gasoil
treating. The hydrotreatment process is used in every major refinery and is therefore also termed
as the work horse of the refinery as it is the hydrotreater unit that ensures several significant
product quality specifications. In most countries the Diesel produced is hydrodesulhurised before
its sold. Sulphur specifications are getting more and more stringent. In Asia, countries such as
Thailand, Singapore and Hong Kong already have a 0.05%S specification and large
hydrodesulphurisation units are required to meet such specs.
The by-products obtained from HDT/HDS are light ends formed from a small amounts of cracking
and these products are used in the refinery fuelgas pool. The other main by-product is Hydrogen
Sulphide which is oxidized to sulphur and sold to the chemical industry for further processing
In combination with temperature, the pressure level (or rather the partial pressure of hydrogen)
generally determines the types of components that can be removed and also determines the
working life of the catalyst. At higher (partial) pressures, the desulphurisation process is 'easier',
however, the unit becomes more expensive for instance due to larger compressors and heavier
reactors. Also, at higher pressure, the hydrogen consumption of the unit increases, which can be
a signficant cost factor for the refinery. The minimum pressure required typically goes up with the
required severity of the unit, i.e. the heavier the feedstock, or the lower levels of sulphur in
product required.

Platforming
Motor gasoline (Mogas) production starts with the distillation of crude oil. One of the products out
of that process is a fraction of low octane gasoline, normally referred to as naphtha, typically
boiling in the range 100 - 160 0C. Other gasoline fractions are produced as a result of secondary
processes like catalytic cracking, isomerisation, alkylation and platforming. Petrol is then

produced by blending a variety of these gasoline components of different qualities to meet a

series of product specifications.
One very important property of Mogas is the octane number, which influences "knocking" or
"pinking" behaviour in the engine of cars. Traditionally lead compounds have been added to
petrol to improve the octane number. Over the past years, in many countries legislation has been
implemented aimed at reducing the emission of lead from exhausts of motor vechiles and this,
calls for other means of raising the octane number.
The role of a platformer is to pave the way for this by a process which reforms the molecules in
low octane naphtha to produce a high octane gasoline component. This is achieved by employing
a catalyst with platinum as its active compound; hence the name Platformer. For many refinery
catalyst applications, a promoter is used, and in the platforming process, it is a chloride promoter
which stimulates the 'acidity' of the catalyst and thereby the isomerisation reactions. Often, a
bimetallic catalyst is used, i.e. in addition to the platinum, a second metal, for instance Rhenium is
present on the catalyst. The main advantage is a higher stability under reforming conditions. The
disadvantage is that the catalyst becomes more sensitive towards poisons, process upsets and
more susceptible to non-optimum regenerations.

Chemistry:
The main reactions of platforming process are as follows:

Dehydrogenation of naphthenes, yielding aromatics and hydrogen

Dehydro-isomerisation of alkyl cyclopentanes to aromatic and hydrogen
Isomerisation of paraffins and aromatics
Dehydrocyclisation of paraffins to aromatics and hydrogen
Hydrocracking of paraffins and naphthenes to ligher, saturated paraffins at the expense
of hydrogen

The process literally re-shapes the molecules of the feed in a reaction in the presence of a
platinum catalyst. Normally it is the hydrocarbon in the C6-C10 parafins that get converted to
aromatics.

The above reactions takes place concurrently and to a large extent also sequentially. The
majority of these reactions, involve the conversion of paraffins and naphtenes and
result in an increase in octane number and a nett production of hydrogen. Characteristic of the
total effect of these reactions is the high endothermicity, which
requires the continuous supply of process heat to maintain
reaction temperature in the catalyst beds. That is why the process
is typically done in four reactors in series with furnaces in between, in order to remain sufficiently
high reactor temperatures.
The reactions takes place at the surface of the catalyst and are very much dependent, amongst
other factors, on the right combination of interactions between platinum, its modifiers or
activators, the halogen and the catalyst carrier. During operating life of the catalyst, the absolute
and relative reaction rates are influenced negatively by disturbing factors like gradual coke
deposition, poisons and deterioration of physical characteristic of the catalyst (surface area
decline).
The process of platforming:
The feedstock of the platformer is drawn from the refinery's distillation units. This is first treated by
passing the feedstock together with hydrogen over a catayst, in a process called 'hydrotreating, to
convert the sulphur and nitrogen compunds to hydrogen sulphide and ammonia, in order to
prevent poisoning of the expensive platformer catalyst. After hydrotreating, ,the reactor effluent
moves on through a stabiliser column to remove the gases formed (hydrogen sulphide, ammonia
and fuel gas). In a second column, the C5 and some of the C6 is removed in a separate fraction
called 'tops'. The reason to remove C5/C6 is that this component will crack in the platformer to
produce fuel gas, while C6 gets converted into benzene, which can only be allowed in limited
amount into the mogas because of its toxicity. From the bottom of the splitter column, the naphtha
stream is produced, which is the feed for the Platforming section.
At the heart of the Platformer process are the four reactors, each linked to furnaces to sustain a
suffiently high reaction temperature, about 500 0C at the inlet of the reactors.
Over time, coke will build up on the catalyst surface area, which reduces the catalyst activity. The
catalyst can be easily regenerated however, by burning the coke off with air. After coke burning,
the catalyst needs to be reconditioned by a combined treatment of air and HCl under high
temperature. This regeneration step is called 'oxy-chlorination'. After this step the catalyst is
dryed with hot nitrogen and subsequently brought in its active condition by reducing the surface
with hot hydrogen. The refinery will therefore regulary have to take out one of the reactors to
undergo this regeneration process. This type of process is therefore called semi-regen
platforming.
During the regeneration process, the refinery will suffer production loss, which is the reason why
UOP developed a major process enhancement by making the regeneration possible
continuously, in a Continous Catalytic Reformer, CCR. In the CCR unit, the reactors are cleverly
stacked, so that the catalyst can flow under gravity. From the bottom of the reactor stack, the
'spent' catalyst is 'lifted' by nitrogen to the top of the regenerator stack. In the regenerator, the
above mentioned different steps, coke burning, oxychlorination and drying are done in different
sections, segregated via a complex system of valves, purge-flows and screens. From the bottom
of the regenerator stack, catalyst is lifted by hydrogen to the top of the reactor stack, in a special
area called the reduction zone. In the reduction zone, the catalyst passes a heat exchanger in
which it is heated up against hot feed. Under hot conditions it is brought in contact with hydrogen,
which performs a reduction of the catalyst surface, thereby restoring its activity. In such a
continuous regeneration process, a constant catalyst activity can be maintained without unit

shutdown for a typical runlength of 3 - 6 years. After 300 - 400 cycles of reaction/regeneration,
the surface area of the catalyst will have dropped to a level (120 - 130 m2/g) that it becomes
more difficult to maintain catalyst activity and at such a time normally the catalyst will be replaced
by a fresh batch. The batch of 'spent' catalyst is then sent for platinum reclaim to recover the
valuable precious metals.
For economic reasons, the design capacities of Platformer units vary from 1000 - 4500 t/d;
operating pressures can vary over a wide range, units with from 3.5 barg up to 30 barg can be
found, whereby the latest generation CCR's are typically at the lower pressure range. A lower
pressure enhances the endothermic reactions, which gives less cracking reactions and thereby a
higher liquid yield. However, at a lower reactor operating pressure, the hydrogen partial pressure
will be lower as well, which favours coke formation. The reason why semi regen platformers will
not operate at a too low pressure, otherwise the cycle length between regenerations becomes to
short. A second disadvantage of operating at a lower pressure is that a larger compressor will be
required to boost the pressure of the hydrogen up to the normal pressure of the hydrogen system
(about 20 barg). Typical design reformate octane numbers are in the 95-104 range. The reactor
temperature is in a region of 450-530 0C.
At the outlet of the last reactor the product is still well above 400 0C. It is cooled down against
cold feed in massive heat exchanger, either a so called 'Texas Tower' or a Packinox plate-pack
heat exchanger. The special design of those heat exchangers ensures that minimum heat loss
occurs in order to minimise the fuel consumption of the furnaces. After passing the feed/effluent
exchanger, the reaction products are cooled in air/water coolers and routed to a product
separator, where the hydrogen is the main gaseous product. Part of the hydrogen produced is
recycled back (via a compressor) to the feed, in order to maintain a high enough hydrogen partial
pressure in the reactors. The remainder of the gases are compressed and brought in contact
again with the liquid from the product separator. This is step is called 'recontacting' and is done in
order to recover as much as possible hydrocarbons from the hydrogen produced. The reactor
product, now in liquid form, goes on to the platformer stabiliser which removes Liquid Petroleum
Gas ( LPG) and other gases to leave a liquid high octane gasoline component called platformate,
ready for blending into the refinery mogas pool. Summarising, the Platformer unit produces about
85% liquid platformate, 10% hydrogen and 5% LPG.
The Continuous Catalytic Reforming unit or better known as CCR Platformer is licensed by UOP,
Universal Oil Products, based in USA. More recently, other technology vendors have copied the
concept, one of the main competitors for UOP in this field is IFP from France.
Main Equipment in a CCR Platformer:
A CCR typically contains a feed/effluent heat exchanger (Texas Tower or Packinox), 4 furnaces,
4 reactors, a regenerator, overhead recontacting section, net gas compressor, recycle gas
compressor and a stabiliser column.

Isomerization
The isomerisation process involves the transformation of one molecular structure into another
(isomer) whose component atoms are the same but arranged in a different geometrical structure.
Since isomers may differ greatly in physical and chemical properties, isomerisation offers the
possibility of converting less desirable compounds into isomers with desirable properties, in
particular to convert n-paraffins into iso-paraffins, thereby increasing the octane of the
hydrocarbon stream. The main fields of application of isomerisation are:

ISOMERISATION of normal butane into isobutane

ISOMERISATION of pentanes and hexanes into higher- branched isomers

Since branched isomers have a higher antiknock quality than the corresponding linear paraffins,
this form of isomerisation is important for the production of motor fuels.
In addition to the above applications, isomerisation is applied for the conversion of ortho-xylene
and meta- xylene into para- xylene, used for the manufacturing of polester fibres.
Isomerisation of low molecular weight paraffins has been commercially applied for many years.
After extensive laboratory work had been carried out during the 1930s, World War 2 prompted the
development of the laboratory processes into full- scale commercial units in order to meet the
demand for isobutane necessary for the manufacture of large amounts of alkylate. While the first
butane isomerisation unit went on stream in late 1941, by the end of the war nearly 40 butane
isomerisation units were in operation in the USA and the Caribbean. Two pentane and two light
naphtha isomerisation units also came on stream towards the end of the war to provide an
additional source of blending aviation gasoline.

Though butane isomerisation has maintained its importance, present day interest isomerisation is
specially focussed on the upgrading of fractions containing C5 Pentane
and C6 Hexane for use as motor gasoline components. This application has been prompted by
the world drive to remove the lead additives gradually from motor
gasoline in order to reduce air pollution. The octane loss caused
by the removal or reduction of lead antiknock additives can be
compensated for by isomerisation of pentane/hexane paraffin fraction of the light gasoline
fractions.
Isomerisation technology has also improved substantially due to the hard work of many
technologist. In order to achieve the low temperature necessary to obtain an acceptable yield of
isomers, the Catalyst systems used in the early units were based on aluminium chloride in some
form. These catalyst systems, however, had the drawback of being highly corrosive and difficult
to handle. In recent years, catalyst of a different type have come in use. These are solid catalysts
consisting of a support having an acidic carrier and a hydrogenation function, frequently a noble
metal. Modern isomerisation units utilise these dual- function catalysts and operate in the vapour

phase and the presence of hydogen. For these reasons, these process are called hydroisomerisation processes.
The first hydro- isomerisation unit was introduced nin 1953 by UOP, followed in 1965 by the first
BP one, while in 1970 the first Shell hydro-isomerisation (HYSOMER) unit was started up. At
present the following hydro-isomerisation processes are commercially available:

UOP BUTAMER for butane isomerisation

UOP PENEX for pentane/hexane isomerisation
BP C4 isomerisation for butane isomerisation
BP C5/C6 isomerisation for pentane/hexane isomerisation
SHELL Hysomer for pentane/hexane isomerisation

All these processes takes place in the vapour phase on a fixed bed catalyst containing platinum
on a solid carrier.
As an example, the Shell Hysomer process will be briefly described. The liquid feedstock is
pentane/hexane from light naphtha. naphtha splitters are widely used to split light naphtha, heavy
naphtha and also LPG. The light naphtha (C5/C6) is combined with the recycle gas/ fresh gas
mixture. The resultant combined reactor feed is routed to a feed/ effluent heat exchanger, where
it is heated and completely vaporised by the effluent of the reactor. The vapourised combined
reactor feed is further heated to the desired reactor inlet temperature in the reactor charge heater.
The hot charge enters the Hysomer reactor at the top and flows downwards through the catalyst
bed, where a portion of normal and mono- branched paraffins is converted into higher branched
(high octane) components. Temperature rise from the heat of reaction release is controlled by a
cold quench gas injection into the reactor. Reactor effluent is cooled and subsequently separated
in the product separator into two streams: a liquid product (isomerate) and a recycle gas stream
returning to the reactor via the recycle gas compressor.
The catalyst is a dual function catalyst consisting of platinum on a zeolite basis, highly stable and
regenerable.
Temperatures and pressure vary in a range of 230 - 285 0C and 13-30 bar, C5/C6 content in
product relative to that in feed is 97% or better, and octane upgrading ranges between 8 and 10
points, depending on feedstock quality. The Hysomer process can be integrated with catalytic
reformer, resulting in substantial equipment savings, or with iso-normal separation processes
which allows for a complete conversion of pentane/hexane mixtures into isoparaffin mixtures. An
interesting application in this field is the total isomerisation process (TIP) in which the
isomerisation is completely integrated with a Union Carbide molecular sieve separation process
or the naphtha IsoSiv Process by UOP.
Highlights of TIP
The following are some of the highlights of the TIP process:
A. TIP has been in commercial operation since 1975
B. UOP manufacturers both the zeolite isomerisation catalyst and the IsoSiv Grade Molecular
Sieve adsorbent.
C. UOP's zeolite catalyst will tolerate sulfur and/or water upsets, the effects of which are usually
reversible, either with time or by in situ regeneration (which minimises any down time).
D. The expected life of the catalyst and adsorbent is 10 years or more.
F. The combination of zeolite isomerisation and IsoSiv molecular separation is possible because
each station has similar operating conditions of temperature, pressure and environment. This
eliminates the need for a second compressor, intermediate stabilisation and the costs associated

with cooling, purifying and reheating the recylce normal paraffins.

G. TIP and IsoSiv separation permits maximum flexibility in changing the C5/C6 ratio and
iso/normal ratio of the feed.
Conclusion:
Nowadays many refiners are looking into the isomerisation processes to add potential extra value
and complimentary to the platforming process. Directly both the platforming and isomerisation
process work hand in hand in several ways. C5 paraffins tend to crack away in the platformer, but
give high upgrading in the isomerisation unit. C6 components convert nicely to benzene in the
platformer, but nowadays the specs on aromatics and benzene are tightening, which makes
conversion of these components to C6 isomers preferred. Furthermore, benzene is hydrogenated
in the isomerisation unit. By adjusting the cutpoint between the light and heavy naphtha, i.e. the
cutpoint between the feed to the isomerisation feed and the platformer feed, the refiner has the
flexibility to control the benzene content of its gasoline pool.

Hydrocracking

Introduction
The need for gasoline of a higher quality than that obtained by catalytic cracking led to the
development of the hydrocracking process. The history of the process goes back to the later
1920s when a plant for the commercial hydrogenation of brown coal was commissioned at Leuna
in Germany. Tungsten sulphide was used as a catalyst in this one-stage unit , in which high
reaction pressures, 200-300 bar, were applied. The catalyst displayed a very high hydrogenation
activity: the aromatic feedstock, coal and heavy fractions of oil, containing sulphur, nitrogen and
oxygen, was virtually completely converted into paraffins and isoparaffins. The result of the Leuna
plant - loss of octane number from aromatic hydrogenation of impurities in the feedstock, notably
nitrogen compounds, followed by a hydrocracking step. In 1939, ICI developed the second-stage
catalyst for a plant that contributed largely to Britain's supply of aviation gasoline in the
subsequent years.
During World War II, two stage processes were applied on a limited scale in Germany, Britain and
USA. In Britain, feedstock were creosote from coal tar and gas oil from petroleum. In the USA,
Standard Oil of New Jersey operated a plant at Baton Rouge, producing gasoline from a
Venezuelan kerosine/light gasoil fraction. Operating conditions in those units were comparable:
approximate reaction temperature 400 0C and reaction pressures of 200-300 bar.

After the war, commercial hydrocracking was stopped because the process was too expensive.
Hydocracking research, however, continued intensively. By the end of the 1950s, the process had
become economic, for which a number of reasons are identified.
The development of improved catalyst made it possible to operate the process at considerably
lower pressure, about 70-150 bar.
This in turn resulted in a reduction in equipment wall thickness, whereas simultaneously,
advances were made in mechanical engineering, especially in the field of reactor design and heat
transfer. These factors, together with the availability of relatively
low cost hydrogen from steam reforming process, brought
hydrocracking back on the refinery scene. The first units of the second generation were built in
USA to meet the demand for conversion of surplus fuel oil in the gasoline-oriented refineries.
Now, hdyrocracking is well established process from many licensors.

Basis for the Choice of Conversion Route

Refiners are continuously faced with trends towards increased conversion, better product
qualities and more rapidly changing product patterns. Various processes are available that can
meet the requirements to a greater or lesser degree: coking, visbreaking/thermal cracking,
catalytic cracking and hydrocracking.
The type of process applied and the complexity of refineries in various parts of the world are
determined to a greater extent by the product distribution required. As a consequence, the
relatively importance of the above process in traditionally fuel-oil dominated refineries such as

those in Western Europe will be quite different from those of gasoline-oriented refineries in, for
instance, the USA.
An important aspect of the coking, thermal cracking and catalytic cracking process is that they
operate at low pressures. This gives advantages in the fields of capital, matallurgy and
engineering.
A particular feature of the hydrocracking process, as compared with its alternatives, is its flexibility
with respect to product outturn and high quality of its products. In the areas where quantitative
imbalance exists of lighter products, middle distillates and fuel, hydrocracking is a most suitable
process for correction. Moreover, the hydrocracker does not yield any coke or pitch byproduct:
the entire feedstock is converted into the required product range, an important consideration in a
situation of limited crude oil availability. The development of the low-pressure catalytic reforming
process, which produces relatively cheap, high quality hydrogen, has continued substantially to
the economic viability of hydrocracking. On the whole, hydrocracking can handle a wider range of
feedstock than catalytic cracking, although the latter process has seen some recent catalyst
developments which narrowed the gap. There are also examples where hydrocracking is
complementary rather than alternative to the other conversion process; an example, cycle oils,
which cannot be recycled to extinction in the catalytic cracker, can be processed in the
hydrocracker.
Notwithstanding many extensive comparisons between the various processes, the experince
shows the generalisation with respect to the optimum conversion route still cannot be made.

Process Description
All hydrocracking process are characterised by the fact that in a catalytic operation under
relatively high hydrogen pressure a heavy oil fraction is treated to give products of lower
molecular weight.
Hydrocracking covers widely different fuels, ranging from C3/C4 production from naphta, on the
other hand, to luboil manufacture from deasphalted oils, on the other.
Most hydrocrackers use fixed beds of catalyst with downflow of reactants. The H-Oil process
developed by Hydrocarbon Research Corp and Cities Service R & D employs an ebullient bed
reactor in which the beds of particulate catalyst are maintained in an ebullient or fluidised
condition in upflowing reactants.
When the processing severity in a hydrocracker is increased, the first reaction occuring leads to
saturation of any olefinic material present in feedstock. Next comes the reaction of
desulphurisation, denitrogenation and de-oxygenation. These reactions constitute treating steps
during which in most cases, only limited cracking takes place. When the severity is increased
further, hydrocracking reaction is initiated. They proceed at various rates, with the formation of
intermediate products (eg. saturation of aromatics), which are subsequently cracked into lighter
products.

Process Configuration
When the treating step is combined with the cracking reaction to occur in one reactor, the process
is called a SINGLE-STAGE PROCESS.
SINGLE-STAGE PROCESS: In this simplest of the hydrocracker configuration, the lay out of the
reactor section generally resembles that of hydrotreating unit. This configuration will find

application in cases where only moderate degree of conversion (say 60% or less) is required. It
may also be considered if full conversion, but with a limited reduction in molecular weight, is
aimed at. An example is the production of middle distillates from heavy distillate oils. The catalyst
used in a single-stage process comprises a hydrogenation function in combination with a strong
cracking function. The hydogenation function is provided by sulphided metals such as cobalt,
molybdenum and nickel. An acidic support, usually alumina, attends to the cracking function.
Nitrogen compounds and ammonia produced by hydrogenation interfere with acidic activity of the
catalyst. In the cases of high/full conversion is required, the reaction temperatures and run
lenghts of interest in commercial operation can no longer be adhered to. It becomes necessary to
switch to a multi-stage process, in which the cracking reaction mainly takes place in an added
reactor. With regard to the adverse effect of ammonia and nitrogen compounds on catalyst
activity, two versions of the multi stage hydrocracker have been developed: the TWO STAGE
HYDROCRACKER and SERIES FLOW HYDROCRACKER.
In the first type, the undesirable compounds are removed from the unconverted hydrocarbons
before the latter are charged to the cracking reactor. This type is called the TWO STAGE
PROCESS. The other variety is ofen referred to as SERIES FLOW HYDROCRACKER. This type
uses a catalyst with an increased tolerance towards nitrogen, both as ammonia and in organic
form.
TWO STAGE CONFIGURATION: Fresh feed is preheated by heat exchange with effluent from
the first reactor. It is combined with part of a not fresh gas/recycle gas mixture and passes
through a first reactor for desulphurisation/denitrogenation step. These reactions, as well as those
of hydrocracking, which occurs to a limited extent in the first reactor, are exothermic. The catalyst
inventory is therefore divided among a number of fixed beds. Reaction temperatures are
controlled by introducing part of the recycle gas as a quench medium between beds. The ensuing
liquid is fractionated to remove the product made in the first reactor. Unconverted, material, with a
low nitrogen content and free of ammonia, is taken as a bottom stream from the fractionation
section. After, heat exchange with reactor effluent and mixing with heated recycle gas, it is sent to
the second reactor. Here most of the hydrocracking reactions occur. Strongly acidic catalyst with
a relatively low hydrogenation activity (metal sulphides on, for example, amorphous silicaalumina) are usually applied. As in the first reactor, the exothermicity of the process is controlled
by using recycle gas as quench medium the catalyst beds. Effluent from the second reactor is
cooled and joins first stage effluent for separation from recycle gas and fractionation. The part of
the second reactor feed that has remained unconverted is recycled to the reactor. Feedstock is
thereby totally converted to the product boiling range.
SERIES FLOW CONFIGURATION: The principal difference is the elimination of first stage
cooling and gas/liquid separation and the interstage ammonia removal step. The effluent from the
first stage is mixed with more recycle gas and routed direct to the inlet of the second reactor. In
contrast with the amorphous catalyst of the two-stage process, the second reactor in series flow
generally has a zeolitic catalyst, based on crystalline silica-alumina. AS in the two stage process,
material not converted to the product boiling range is recycled from the fractionation section.

Conclusion
Both two stage and series flow hydrocracking are flexible process: they may yield, in one mode of
operation, only naphtha and lighter products and, in a different mode, only gasoil and lighter
products. In the naphtha mode, both configurations have comparable yield patterns. In modes for
heavier products, kerosine and gasoil, the two stage process is more selective because product
made in the first reactor is removed from the second reactor feed, In series flow operation this
product is partly overcracked into lighter products in the second reactor.

Catalytic Cracking

Introduction
Already in the 30's it was found that when heavy oil fractions are heated over clay type materials,
cracking reactions occur, which lead to significant yields of lighter hydrocarbons. While the search
was going on for suitable cracking catalysts based on natural clays, some companies
concentrated their efforts on the development of synthetic catalyst. This resulted in the synthetic
amorphous silica-alumina catalyst, which was commonly used until 1960, when it was slightly
modified by incorporation of some crystalline material (zeolite catalyst). When the success of the
Houdry fixed bed process was announced in the late 1930s, the companies that had developed
the synthetic catalyst decided to try to develop a process using finely powdered catalyst.
Subsequent work finally led to the development of the fluidised bed catalytic cracking (FCC)
process, which has become the most important catalytic cracking process.
Originally, the finely powdered catalyst was obtained by grinding the catalyst material, but
nowadays, it is produced by spray-drying a slurry of silica gel and aluminium hydroxide in a
stream of hot flue gases. Under the right conditions, the catalyst is obtained in the form of small
spheres with particles in the range of 1-50 microns.
When heavy oil fractions are passed in gas phase through a bed of powdered catalyst at a
suitable velocity (0.1-0.7m/s), the catalyst and the gas form a system that behaves like liquid, i.e.
it can flow from one vessel to another under the influence of a hydrostatic pressure. If the gas
velocity is too low, the powder does not fluidise and it behaves like a solid. If velocity is too high,
the powder will just be carried away with the gas. When the catalyst is properly fluidised, it can be
continously transported from a reactor vessel, where the carcking reactions take place and where
it is fluidised by the hydrocarbon vapour, to a regenerator vessel, where it is fluidised by the air
and the products of combustion, and then back to the reactor. In this way the proces is truly
continous.
The first FCC unit went on stream in Standard Oil of New Jersey's refinery in Baton Rounge,
Louisiana in May 1942. Since that time, many companies have developed their own FCC process
and there are numerous varieties in unit configuration.

FCC Process Configuration

: Hot feed, together with some steam, is introduced at the bottom of the riser via special
distribution nozzles. Here it meets a stream of hot regenerated catalyst from the regenerator
flowing down the inclined regenerator standpipe. The oil is heated and
vaporised by the hot catalyst and the cracking reactions commence. The vapour, initially formed
by vaporisation and successively by cracking, carries the catalyst up the riser at 10-20 m/s in a
dilute phase. At the outlet of the riser the catalyst and hydrocarbons are quickly separated in a
special device. The catalyst (now partly deactivated by deposited
coke) and the vapour then enter the reactor. The vapour passes
overhead via cyclone separator for removal of entrained catalyst
before it enters the fractionator and further downstream equipment for product separation. The
catalyst then descends into the stripper where entrained hydrocarbons are removed by injection
of steam, before it flows via the inclined stripper standpipe into the fluidised catalyst bed in the
regenerator.
Air is supplied to the regenerator by an air blower and distributed throughout the catalyst bed.
The coke deposited is burnt off and the regenerated catalyst passes down the regenerator
standpipe to the bottom of the riser, where it joins the fresh feed and the cycle recommences.
The flue gas (the combustion products) leaving the regenerator catalyst bed entrains catalyst
particles. In particular, it entrains "fines", a fine dust formed by mechanical rubbing of catalyst
particles taking place in the catalyst bed. Before leaving the regenerator, the flue gas therefore
passes through cyclone separators where the bulk of this entrained catalyst is collected and
returned to the catalyst bed.
Normally modern FCC is driven by an expansion turbine to mimimise energy consumption. In this
expansion turbine, the current of flue gas at a pressure of about 2 barg drives a wheel by striking
impellers fitted on this wheel. The power is then transferred to the air blower via a common shaft.
This system is usually referred to as a "power recovery system". To reduce the wear caused by
the impact of catalyst particles on the impellers (erosion), the flue gas must be virtually free of
catalyst particles. The flue gas is therefore passed through a vessel containing a whole battery of
small, highly efficient cyclone separators, where the remaining catalyst fines are collected for
disposal.
Before being disposed of via a stack, the flue gas is passed through a waste heat boiler, where its
remaining heat is recovered by steam generation.
In the version of the FCC process described here, the heat released by burning the coke in the
regenerator is just sufficient to supply the heat required for the riser to heat up, vaporise and
crack the hydrocarbon feed. The units where this balance occurs are called " heat balanced"
units. Some feeds caused excessive amounts of coke to be deposited on the catalyst, i.e. much
more than is required for burning in the regenerator and to have a "heat balanced" unit. In such
cases, heat must be removed from the regenerator, e.g. by passing water through coils in the
regenerator bed to generate steam. Some feeds cause so little coke to be deposited on the
catalyst that heat has to be supplied to the system. This is done by preheating the hydrocarbon
feed in a furnace before contacting it with the catalyst.

Main Characteristics

A special device in the bottom of the riser to enhance contacting of catalyst and
hydrocarbon feed.

The cracking takes place during a short time (2-4 seconds) in a riser ("short-contact time
riser") at high temperatures ( 500-540 0C at riser outlet).
The catalyst used is so active that a special device for quick separation of catalyst and
hydrocarbons at the outlet of the riser is required to avoid undesirable cracking after the
mixture has left the riser. Since, no cracking in thereactor is required, the reactor no
longer functions as a reactor; it merely serves as a holding vessel for cyclones.
The regenerator takes place at 680-720 0C. With the use of special catalysts, all the
carbon monoxide (CO) in the flue gas is combusted to carbon dioxide (CO2) in the
regenerator.
Modern FCC includes a power recovery system for driving the air blower.

Equipment in FCC

Large storage vessels for catalyst (fresh and equilibrium)

Regenerator
Reactor
Main Fractionator
Product Work Up section (several distillation columns in series
Product treating facilities

Feedstock & Yield

Before the introduction of residues, vacumn distillates were used as feedstock to load the
Catalytic Cracker fully. These days, even residues are used to load the cracker. The term used
for this type of configuation is Long Residue Catalytic Cracking Complex. The only modification or
addition needed are a residue desalter and a bigger and more heat resistent reactor.
The yield pattern of an FCC unit is typically as follows:

Product
C3 & C4
Gasoline
Heavy Gas Oil
Coke

% wt on fresh feed
15
40-50
10
5

Conclusion
The FCC Unit can a real margin improver for many refineries. It is able to convert the residues
into high value products like LPG , Butylene, Propylene and Mogas together with Gasoil. The
FCC is also a start for chemical production (poly propylene). Many FCC's have 2 modes: a
Mogas mode and a Gasoil mode and FCC's can be adapted to cater for the 2 modes depending
on favourabale economic conditions. The only disavantage of an FCC is that the products
produced need to be treated (sulfur removal) to be on specification. Normally Residue FCCs act
together with Residue Hydroconversion Processes and Hydrocrackers in order to minimise the
product quality give away and get a yield pattern that better matches the market specifications.
Via product blending, expensive treating steps can be avoided and the units prepare excellent
feedstock for eachother: desulfurised residue or hydrowax is excellent FCC feed, while the FCC
cycle oils are excellent Hydrocracker feed.

In the near future, many refiners will phase the challenge how to desulfurise cat cracked gasoline
without destroying its octane value. Catalytic destillation appears to be one of the most promising
candidate processes for that purpose.

Thermal Cracking

Introduction
Thermal cracking is the oldest and, in a way, the simplest cracking process. It basically aims at
the reduction of molecular size by application of heat without any additional sophistication such
as catalyst or hydrogen. At a temperature level of 450-500 C, the larger hydrocarbon molecules
become unstable and tend to break spontaneously into smaller molecules of all possible sizes
and types. By varying the time, temperature and pressure under which a particular feedstock
remains under cracking conditions, the desired degree of cracking (conversion) can be controlled.
Temperature and time (residence time) are important process variables pressure plays a
secondary role.
Obviously, the cracking conditions to be applied and the amount and type of cracked products will
depend largely on the type of feedstock. In practice, the feedstock for thermal cracking is a
mixture of complex heavy hydrocarbon molecules left over from atmospheric and/or vacuum
distillation of crude. The nature of these heavy, high molecular weight fractions is extremely
complex and much fundamental research has been carried out on their behaviour under thermal
cracking conditions. However, a complete and satisfactory explanation of these reactions that
take place cannot be given, except for relatively simple and well-defined types of products. For
instance, long chain paraffinic hydrocarbon molecules break down into a number of smaller ones
by rupture of a carbon-to-carbon bond (the smaller molecules so formed may break down
further). When this occurs, the number of hydrogen atoms present in the parent molecule is
insufficient to provide the full complement for each carbon atom, so that olefins or "unsaturated"
compounds are formed. The rupturing can take place in many ways, usually a free radical
mechanism for the bond rupture is assumed.
However, paraffinic hydrocarbons are usually only a small part of the heavy petroleum residues,
the rest being cyclic hydrocarbons, either aromatic or naphthenic in character. In these, the
rupture takes place in the paraffinic side-chain and not in the ring. Other side reactions also take
place. In particular, the condensation and polymerisation reactions of olefins and of the aromatics
are of considerable practical importance, since they can lead to undesirable product properties,
such as an increase in the sludge or tar content. Hence, in practice, it is very difficult to assess
the crackability of various feedstocks without plant trials. The final products consist of gas, light
hydrocarbons in the gasoline and gasoil range and heavier products. By selection of the type of
unit, feedstock and operating conditions, the yields and quality of the various products can, within
limits be controlled to meet market requirements.
The maximum conversion that can be obtained will be determined by the quality of the bottom
product of the thermal cracker, thermally cracked residue. This stream is normally routed to the
fuel oil blending pool. When the cracking has taken place at a too high severity, the fuel can
become 'unstable' upon blending with diluent streams (see below). Normally, the refinery
scheduler will assess what the maximum severity is that the thermal cracking unit can operate on,
without impacting on the stability of the refinery fuel blending pool.
When thermal cracking was introduced in the refineries some 80 years ago, its main purpose was
the production of gasoline. The units were relatively small (even applying batch processing), were
inefficient and had a very high fuel consumption. However, in the twenties and thirties a
tremendous increase in thermal cracking capacity took place, largely in the version of the famous

DUBBS process, invented by UOP. Nevertheless, thermal cracking lost ground quickly to catalytic
cracking (which produces gasoline of higher octane number) for processing heavy distillates with
the onset of the latter process during World War II. Since then and up to the present day, thermal
cracking has mostly been applied for other purposes : cracking long residue to middle distillates
(gasoil), short residue for viscosity reduction (visbreaking), short residue to produce bitumen, wax
to olefins for the manufacture of chemicals, naphtha to ethylene gas (also for the manufacturing
of chemicals), selected feedstocks to coke for use as fuel or for the manufacture of electrodes.
In modern oil refineries there are three major applications of the thermal cracking process:

VISBREAKING
THERMAL GASOIL PRODUCTION
COKING

Visbreaking
Visbreaking (i.e. viscosity reduction or breaking) is an important application of thermal cracking
because it reduces the viscosity of residue substantially, thereby lessening the diluent
requirements and the amount of fuel oil produced in a refinery. The feed, after appropriate
preheat, is sent to a furnace for heating to the cracking temperature, at about 450-460 degrees C.
The cracking takes place to a small extent in the furnace and largely in a soaker (reaction
chamber) just downstream of the furnace. At the soaker outlet, the temperature is lower than at
the furnace outlet (soaker inlet) because the cracking reactions are endothermic. The products
are quenched at the soaker outlet to stop the cracking reaction (to prevent excessive coke
formation). After that, the products enter the fractionator at a temperature level of 300- 400
degrees C and from here onward the processing is similar to any normal distillation process. The
products are separated into gas, gasoline, kero, gasoil and residue. The residue so obtained has
a lower viscosity that the feed (visbreaking), which leads to a lower diluent requirement to make
the fuel on specification for viscosity. The up-flow soaker provides for a prolonged residence time
and therefore permits a lower cracking temperature than if the soaker was not used. This is
advantageous as regards cost in furnace and fuel. Modern soakers are equipped with internals so
as to reduce back mixing- effects , thus maximising the viscosity reduction. Since only one
cracking stage is involved, this layout is also named one-stage cracking. The cracking
temperature applied is about 440-450 degree C at a pressure of 5-10 barg in the soaker. The
fractionator can be operated at 2-5 barg, depending on furnace constraints, condenser
constraints and fuel cost.

Thermal Gasoil Production

This is a more elaborate and sophisticated application of thermal cracking as compared with
visbreaking. Its aim is not only to reduce viscosity of the feedstock but also to produce and
recover a maximum amount of gasoil. Altogether, it can mean that the viscosity of residue
(excluding gasoil) run down from the unit is higher than that of the feed.
In the typical lay out is the first part of the unit quite similar to a visbreaking unit. The visbroken
residue is vacuum-flashed to recover heavy distillates, which are then sent back to a thermal
cracking stage, together with heavy distillate recovered from the fractionator, in a second furnace
under more severe cracking conditions ( temperature 500 degrees C; pressure 20-25 barg) .
More severe conditions are necessary because the feedstock has a smaller molecular size and is
therefore more difficult to crack than the larger residue molecules in the first stage. This layout is
referred to as tow-stage cracking.

Delayed Coking
This is an even more severe thermal cracking application than the previous one. The goal is to
make a maximum of cracking products - distillates - whereby the heavy residue becomes so
impoverished in hydrogen that it forms coke. The term "delayed" is intended to indicate that the
coke formation does not take place in the furnace (which would lead to a plant shutdown) but in
the large coke drums after the furnace. These drums are filled/emptied batch-wise (once every 24
hours), though all the rest of the plant operates continuously. A plant usually has two coke drums,
which have adequate capacity for one day's coke production (500-1500 m2). The process
conditions in the coke drum are 450-500 degrees C and 20 - 30 bar. Only one coke drum is online; the other is off line, being emptied or standing by. Only the vapour passes from the top of the
coke drums to the fractionator, where the products are separated into the desired fractions. The
residue remains in the coke drum to crack further until only the coke is left. Often the heaviest
part of the fractionator products is recycled to feed.

Product Quality
Thermally cracked products - distillates - are not suitable for commercial use as produced in other
units; they require further refinement or treatment in order to improve their quality, particularly
sulfur and olefins content. Formerly, wet treating processes, for example treatment with caustic or
an other extraction medium, were applied to remove or "sweeten" the smelly sulfur products, but
nowadays the catalytic hydrotreating is employed almost without exception, both for gasoline and
for gas oil range products. Of course, the gases too have to be desulphurised before being used
as fuel gas within the refinery.
The residual products from thermal cracking are normally not treated any further, except for coke,
which may be calcined if the specifications require it to be treated. The cracked residue is
normally disposed of as refinery or commercial fuel. Here a very important aspect of the process
is the stability of the cracked residues or of the final fuels after blending with suitable diluents.
Residue contains asphaltenes,which are colloidally dispersed uniformly in the oil in a natural way.
In the cracking process, the character of the asphaltenes as well as of the oil changes, and if the
cracking is too severe the natural balance of the colloidal system can be affected to the extent
that part of the asphaltenes precipitates in the equipment or in the storage tanks, forming sludge.
If the sludge formation is excessive, i.e. above a certain specified limit, the product (fuel) is
considered to be unstable.

Plant Operations/Decoking
A practical aspect of operation of thermal cracking units is that, in spite of good design and
operating practice, furnaces, and sometimes also other equipment, gradually coke up, so that the
unit has to be shut down and decoked. Furnaces can be decoked by " turbining" (using special
rotary tools to remove coke from inside furnace pipes) or by steam-air decoking process. In the
latter case, the coke is burnt off in a carefully controlled decoking process in which air and steam
are passed through the tubes at elevated temperatures. Air serves to burn coke, where as the
steam serves to keep the burning temperatures low so that they do not exceed the maximum
tolerable temperatures.
More recently, a new decoking method using studded 'pigs' propelled with water, is getting more
popular. The plastic pigs have a size slightly smaller than the tube inside diameter and are
equipped with metal studs. When the pigs are pumped through the furnace pipes, they move
around in a rotating fashion, thus scraping the cokes from the inside of the furnace tubes.
Other coked equipment is usually cleaned by hydrojetting techniques. Owing to these
unavoidable stops for decoking, the on-stream time i.e. on stream days per annum, for thermal
cracking units is slightly shorter than for most other oil processes.

Vacuum Distillation

Introduction
To recover additional distillates from long residue, distillation at reduced pressure and high
temperature has to be applied. This vacuum distillation process has become an important chain
in maximising the upgrading of crude oil. As distillates, vacuum gas oil, lubricating oils and/or
conversion feedstocks are generally produced. The residue from vacuum distillation - short
residue - can be used as feedstock for further upgrading, as bitumen feedstock or as fuel
component. The technology of vacuum distillation has developed considerably in recent decades.
The main objectives have been to maximise the recovery of valuable distillates and to reduce the
energy consumption of the units.
At the place where the heated feed is introduced in the vacuum column - called the flash zone the temperature should be high and the pressure as low as possible to obtain maximum distillate
yield. The flash temperature is restricted to about 420 0C, however, in view of the cracking
tendency of high-molecular-weight hydrocarbons. Vacuum is maintained with vacuum ejectors
and lately also with liquid ring pumps. Lowest achievable vacuum in the flash zone is in the order
of 10 mbar.
In the older type high vacuum units the required low hydrocarbon partial pressure in the flash
zone could not be achieved without the use of "lifting" steam. The steam acts in a similar manner
as the stripping steam of crude distillation units. This type of units is called "wet" units. One of the
latest developments in vacuum distillation has been the deep vacuum flashers, in which no steam
is required. These "dry" units operate at very low flash zone pressures and low pressure drops
over the column internals. For that reason the conventional reflux sections with fractionation trays
have been replaced by low pressure- drop spray sections. Cooled reflux is sprayed
via a number of specially designed spray nozzles in the column
countercurrent to the up-flowing vapour. This spray of small
droplets comes into close contact with the hot vapour, resulting in
good heat and mass transfer between the liquid and vapour phase.
To achieve low energy consumption, heat from the circulating refluxes and rundown streams is
used to heat up the long residue feed. Surplus heat is used to produce medium and/or lowpressure steam or is exported to another process unit (via heat integration). The direct fuel
consumption of a modern high-vacuum unit is approximately 1% on intake, depending on the
quality of the feed. The steam consumption of the dry high-vacuum units is significantly lower
than that of the "wet" units. They have become net producers of steam instead of steam
consumers.
Three types of high-vacuum units for long residue upgrading have been developed for
commercial application:

FEED PREPARATION UNITS

LUBOIL HIGH- VACUUM UNITS
HIGH - VACUUM UNITS FOR BITUMEN PRODUCTION

Feed Preparation Units

These units make a major contribution to deep conversion upgrading ("cutting deep in the
barrel"). They produce distillate feedstocks for further upgrading in catalytic crackers,

hydrocrackers and thermal crackers. To obtain an optimum waxy distillate quality a wash oil
section is installed between feed flash zone and waxy distillate draw-off. The wash oil produced is
used as fuel component or recycled to feed. The flashed residue (short residue) is cooled by heat
exchange against long residue feed. A slipstream of this cooled short residue is returned to the
bottom of the high-vacuum column as quench to minimise cracking (maintain low bottom
temperature).

Luboil High-Vacuum Units

Luboil high vacuum units are specifically designed to produce high-quality distillate fractions for
luboil manufacturing. Special precautions are therefore taken to prevent thermal degradation of
the distillates produced. The units are of the "wet" type. Normally, three sharply fractionated
distillates are produced (spindle oil, light machine oil and medium machine oil). Cutpoints
between those fractions are typically controlled on their viscosity quality. Spindle oil and light
machine oil are subsequently steam- stripped in dedicated strippers. The distillates are further
processed to produce lubricating base oil. Short residue is normally used as feedstock for the
solvent de-asphalting process to produce deasphalted oil, an intermediate for bright stock
manufacturing.

High-Vacuum Units for Bitumen Production

Special vacuum flashers have been designed to produce straight-run bitumen and/or feedstocks
for bitumen blowing. In principle, these units are designed on the same basis as the previously
discussed feed preparation units, which may also be used to provide feedstocks for bitumen
manufacturing.

Bitumen Blowing
Asphaltic bitumen, normally called "bitumen" is obtained by vacuum distillation or vacuum
flashing of an atmospheric residue. This is " straight run" bitumen. An alternative method of
bitumen production is by precipitation from residual fractions by propane or butane- solvent
deasphalting.
The bitumen thus obtained has properties which derive from the type of crude oil processed and
from the mode of operation in the vacuum unit or in the solvent deasphalting unit. The grade of
the bitumen depends on the amount of volatile material that remains in the product: the smaller
the amount of volatiles, the harder the residual bitumen.
In most cases, the refinery bitumen production by straight run vacuum distillation does not meet
the market product quality requirements. Authorities and industrial users have formulated a
variety of bitumen grades with often stringent quality specifications, such as narrow ranges for
penetration and softening point. These special grades are manufactured by blowing air through
the hot liquid bitumen in a BITUMEN BLOWING UNIT. What type of reactions take place when a
certain bitumen is blown to grade? Bitumen may be regarded as colloidal system of highly
condensed aromatic particles (asphaltenes) suspended in a continuous oil phase. By blowing, the
asphaltenes are partially dehydrogenated (oxidised) and form larger chains of asphaltenic
molecules via polymerisation and condensation mechanism. Blowing will yield a harder and more
brittle bitumen (lower penetration, higher softening point), not by stripping off lighter components
but changing the asphaltenes phase of the bitumen. The bitumen blowing process is not always
successful: a too soft feedstock cannot be blown to an on-specification harder grade.

The blowing process is carried out continuously in a blowing column. The liquid level in the
blowing column is kept constant by means of an internal draw-off pipe. This makes it possible to
set the air-to-feed ratio (and thus the product quality) by controlling both air supply and feed
supply rate. The feed to the blowing unit (at approximately 210 0C), enters the column just below
the liquid level and flows downward in the column and then upward through the draw-off pipe. Air
is blown through the molten mass (280-300 0C) via an air distributor in the bottom of the column.
The bitumen and air flow are countercurrent, so that air low in oxygen meets the fresh feed first.
This, together with the mixing effect of the air bubbles jetting through the molten mass, will
minimise the temperature effects of the exothermic oxidation reactions: local overheating and
cracking of bituminous material. The blown bitumen is withdrawn continuously from the surge
vessel under level control and pumped to storage through feed/product heat exchangers.

I.

INTRODUCTION.
A.

The petroleum industry began with the successful drilling of the first commercial oil well in 1859,
and the opening of the first refinery two years later to process the crude into kerosene. The evolution of
petroleum refining from simple distillation to today's sophisticated processes has created a need for
health and safety management procedures and safe work practices. To those unfamiliar with the
industry, petroleum refineries may appear to be complex and confusing places. Refining is the
processing of one complex mixture of hydrocarbons into a number of other complex mixtures of
hydrocarbons. The safe and orderly processing of crude oil into flammable gases and liquids at high
temperatures and pressures using vessels, equipment, and piping subjected to stress and corrosion
requires considerable knowledge, control, and expertise.

II.

B.

Safety and health professionals, working with process, chemical, instrumentation, and metallurgical
engineers, assure that potential physical, mechanical, chemical, and health hazards are recognized
and provisions are made for safe operating practices and appropriate protective measures. These
measures may include hard hats, safety glasses and goggles, safety shoes, hearing protection,
respiratory protection, and protective clothing such as fire resistant clothing where required. In
addition, procedures should be established to assure compliance with applicable regulations and
standards such as hazard communications, confined space entry, and process safety management.

C.

This chapter of the technical manual covers the history of refinery processing, characteristics of
crude oil, hydrocarbon types and chemistry, and major refinery products and by-products. It
presents information on technology as normally practiced in present operations. It describes the
more common refinery processes and includes relevant safety and health information. Additional
information covers refinery utilities and miscellaneous supporting activities related to hydrocarbon
processing. Field personnel will learn what to expect in various facilities regarding typical materials
and process methods, equipment, potential hazards, and exposures.

D.

The information presented refers to fire prevention, industrial hygiene, and safe work practices, and
is not intended to provide comprehensive guidelines for protective measures and/or compliance with
regulatory requirements. As some of the terminology is industry-specific, a glossary is provided as
an appendix. This chapter does not cover petrochemical processing.

OVERVIEW OF THE PETROLEUM INDUSTRY.

A.

BASIC REFINERY PROCESS: DESCRIPTION AND HISTORY. Petroleum refining has evolved
continuously in response to changing consumer demand for better and different products. The
original requirement was to produce kerosene as a cheaper and better source of light than whale oil.
The development of the internal combustion engine led to the production of gasoline and diesel
fuels. The evolution of the airplane created a need first for high-octane aviation gasoline and then
for jet fuel, a sophisticated form of the original product, kerosene. Present-day refineries produce a
variety of products including many required as feedstock for the petrochemical industry.

1.

Distillation Processes. The first refinery, opened in 1861, produced kerosene by simple
atmospheric distillation. Its by-products included tar and naphtha. It was soon discovered
that high-quality lubricating oils could be produced by distilling petroleum under vacuum.
However, for the next 30 years kerosene was the product consumers wanted. Two significant
events changed this situation: (1) invention of the electric light decreased the demand for
kerosene, and (2) invention of the internal combustion engine created a demand for diesel
fuel and gasoline (naphtha).

2.

Thermal Cracking Processes. With the advent of mass production and World War I, the

number of gasoline-powered vehicles increased dramatically and the demand for gasoline
grew accordingly. However, distillation processes produced only a certain amount of gasoline
from crude oil. In 1913, the thermal cracking process was developed, which subjected heavy
fuels to both pressure and intense heat, physically breaking the large molecules into smaller
ones to produce additional gasoline and distillate fuels. Visbreaking, another form of thermal
cracking, was developed in the late 1930's to produce more desirable and valuable products.

3.

Catalytic Processes. Higher-compression gasoline engines required higher-octane gasoline

with better antiknock characteristics. The introduction of catalytic cracking and
polymerization processes in the mid- to late 1930's met the demand by providing improved
gasoline yields and higher octane numbers.
Alkylation, another catalytic process developed in the early 1940's, produced more highoctane aviation gasoline and petrochemical feedstock for explosives and synthetic rubber.
Subsequently, catalytic isomerization was developed to convert hydrocarbons to produce
increased quantities of alkylation feedstock. Improved catalysts and process methods such as
hydrocracking and reforming were developed throughout the 1960's to increase gasoline
yields and improve antiknock characteristics. These catalytic processes also produced
hydrocarbon molecules with a double bond (alkenes) and formed the basis of the modern
petrochemical industry.

4.

Treatment Processes. Throughout the history of refining, various treatment methods have
been used to remove nonhydrocarbons, impurities, and other constituents that adversely
affect the properties of finished products or reduce the efficiency of the conversion processes.
Treating can involve chemical reaction and/or physical separation. Typical examples of
treating are chemical sweetening, acid treating, clay contacting, caustic washing,
hydrotreating, drying, solvent extraction, and solvent dewaxing. Sweetening compounds and
acids desulfurize crude oil before processing and treat products during and after processing.
Following the Second World War, various reforming processes improved gasoline quality and
yield and produced higher-quality products. Some of these involved the use of catalysts
and/or hydrogen to change molecules and remove sulfur. A number of the more commonly
used treating and reforming processes are described in this chapter of the manual.
TABLE IV: 2-1. HISTORY OF REFINING

Year

Process name

Purpose

By-products, etc.

1862

Atmospheric distillation

Produce kerosene

Naphtha, tar, etc.

1870

Vacuum distillation

Lubricants (original)
Cracking feedstocks (1930's)

Asphalt, residual
coker feedstocks

1913

Thermal cracking

Increase gasoline

Residual, bunker fuel

1916

Sweetening

reduce sulfur & odor

Sulfur

1930

Thermal reforming

Improve octane number

Residual

1932

Hydrogenation

Remove sulfur

Sulfur

1932

Coking

Produce gasoline basestocks

Coke

1933

Solvent extraction

Improve lubricant viscosity

index

Aromatics

1935

Solvent dewaxing

Improve pour point

Waxes

1935

Cat. polymerization

Improve gasoline yield

& octane number

Petrochemical
feedstocks

1937

Catalytic cracking

Higher octane gasoline

Petrochemical
feedstocks

1939

Visbreaking

reduce viscosity

Increased distillate,tar

1940

Alkylation

Increase gasoline octane &

yield

High-octane aviation
gasoline

1940

Isomerization

Produce alkylation feedstock

Naphtha

1942

Fluid catalytic cracking

Increase gasoline yield &

octane

Petrochemical feedstocks

1950

Deasphalting

Increase cracking feedstock

Asphalt

1952

Catalytic reforming

Convert low-quality naphtha

Aromatics

1954

Hydrodesulfurization

Remove sulfur

Sulfur

1956

Inhibitor sweetening

Remove mercaptan

Disulfides

1957

Catalytic isomerization

Convert to molecules with

high octane number

Alkylation feedstocks

1960

Hydrocracking

Improve quality and reduce

sulfur

Alkylation feedstocks

1974

Catalytic dewaxing

Improve pour point

Wax

1975

Residual hydrocracking

Increase gasoline yield from

residual

Heavy residuals

B.

BASICS OF CRUDE OIL.

1. Crude oils are complex mixtures containing many different hydrocarbon compounds that vary
in appearance and composition from one oil field to another. Crude oils range in consistency
from water to tar-like solids, and in color from clear to black. An "average" crude oil contains
about 84% carbon, 14% hydrogen, 1%-3% sulfur, and less than 1% each of nitrogen,
oxygen, metals, and salts. Crude oils are generally classified as paraffinic, naphthenic, or
aromatic, based on the predominant proportion of similar hydrocarbon molecules. Mixedbase crudes have varying amounts of each type of hydrocarbon. Refinery crude base stocks
usually consist of mixtures of two or more different crude oils.
2. Relatively simple crude oil assays are used to classify crude oils as paraffinic, naphthenic,
aromatic, or mixed. One assay method (United States Bureau of Mines) is based on
distillation, and another method (UOP "K" factor) is based on gravity and boiling points. More
comprehensive crude assays determine the value of the crude (i.e., its yield and quality of
useful products) and processing parameters. Crude oils are usually grouped according to
yield structure.
3. Crude oils are also defined in terms of API (American Petroleum Institute) gravity. The higher
the API gravity, the lighter the crude. For example, light crude oils have high API gravities
and low specific gravities. Crude oils with low carbon, high hydrogen, and high API gravity
are usually rich in paraffins and tend to yield greater proportions of gasoline and light
petroleum products; those with high carbon, low hydrogen, and low API gravities are usually
rich in aromatics.

4.

Crude oils that contain appreciable quantities of hydrogen sulfide or other reactive sulfur
compounds are called "sour." Those with less sulfur are called "sweet." Some exceptions to
this rule are West Texas crudes, which are always considered "sour" regardless of their H2S

content, and Arabian high-sulfur crudes, which are not considered "sour" because their sulfur
compounds are not highly reactive.

TABLE IV: 2-2. TYPICAL APPROXIMATE CHARACTERISTICS AND

PROPERTIES AND GASOLINE POTENTIAL OF VARIOUS CRUDES
(Representative average numbers)

Crude
source

C.

Sulfur
API
Paraffins Aromatics Naphthenes (%
gravity
(% vol)
(% vol)
(% vol)
wt)
(approx.)

Napht.
yield
Octane
(%
no
vol)
(typical)

Nigerian
-Light

37

54

0.2

36

28

60

Saudi
-Light

63

19

18

34

22

40

Saudi
-Heavy

60

15

25

2.1

28

23

35

Venezuela
-Heavy

35

12

53

2.3

30

60

Venezuela
-Light

52

14

34

1.5

24

18

50

USA
-Midcont.
Sweet

0.4

40

USA
-W.
Texas
Sour

46

22

32

1.9

32

33

55

North Sea
-Brent

50

16

34

0.4

37

31

50

BASICS OF HYDROCARBON CHEMISTRY. Crude oil is a mixture of hydrocarbon molecules, which

are organic compounds of carbon and hydrogen atoms that may include from one to 60 carbon
atoms. The properties of hydrocarbons depend on the number and arrangement of the carbon and
hydrogen atoms in the molecules. The simplest hydrocarbon molecule is one carbon atom linked with
four hydrogen atoms: methane. All other variations of petroleum hydrocarbons evolve from this
molecule.
Hydrocarbons containing up to four carbon atoms are usually gases, those with 5 to 19 carbon
atoms are usually liquids, and those with 20 or more are solids. The refining process uses 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) rather than its specific
chemical compounds that is significant in the refining process.

1.

Three Principal Groups or Series of Hydrocarbon Compounds that Occur Naturally in

Crude Oil.
a. Paraffins. The paraffinic series of hydrocarbon compounds found in crude oil have the
general formula CnH2n+2 and can be either straight chains (normal) or branched chains
(isomers) of carbon atoms. The lighter, straight-chain paraffin molecules are found in gases
and paraffin waxes. Examples of straight-chain molecules are methane, ethane, propane,
and butane (gases containing from one to four carbon atoms), and pentane and hexane
(liquids with five to six carbon atoms). The branched-chain (isomer) paraffins are usually
found in heavier fractions of crude oil and have higher octane numbers than normal
paraffins. These compounds are saturated hydrocarbons, with all carbon bonds satisfied, that
is, the hydrocarbon chain carries the full complement of hydrogen atoms.
FIGURE IV:2-1. TYPICAL PARAFFINS.
Example of
Examples of straight chain paraffin molecule (Butane)
simplest
and branched paraffin molecule (Isobutane) with same
HC molecule chemical formula (C4H10):
(CH4):
METHANE
(CH4)

BUTANE (C4H10)

ISOBUTANE (C4H10)

2.
b. Aromatics are unsaturated ring-type (cyclic) compounds which react readily because
they have carbon atoms that are deficient in hydrogen. All aromatics have at least one
benzene ring (a single-ring compound characterized by three double bonds alternating with
three single bonds between six carbon atoms) as part of their molecular structure.
Naphthalenes are fused double-ring aromatic compounds. The most complex aromatics,
polynuclears (three or more fused aromatic rings), are found in heavier fractions of crude oil.
c. Naphthenes are saturated hydrocarbon groupings with the general formula CnH2n,
arranged in the form of closed rings (cyclic) and found in all fractions of crude oil except the
very lightest. Single-ring naphthenes (monocycloparaffins) with five and six carbon atoms
predominate, with two-ring naphthenes (dicycloparaffins) found in the heavier ends of
naphtha.

3.

Other Hydrocarbons.
a. Alkenes are mono-olefins with the general formula CnH2n and contain only one carboncarbon double bond in the chain. The simplest alkene is ethylene, with two carbon atoms
joined by a double bond and four hydrogen atoms. Olefins are usually formed by thermal and
catalytic cracking and rarely occur naturally in unprocessed crude oil.

FIGURE IV:2-2. TYPICAL AROMATICS.

Example of simple aromatic
compound:

Examples of simple double-ring

aromatic compound:

BENZENE (C6H6)

NAPTHALENE (C10H8)

4.
FIGURE IV:2-3. TYPICAL NAPHTHENES.
Example of typical singlering naphthene:

Examples of naphthene with same

chemical formula (C6H12) but different
molecular structure:

CYCLOHEXANE (C6H12)

METHYL CYCLOPENTANE (C6H12)

5.
FIGURE IV:2-4. TYPICAL ALKENES.
Simplest Alkene
(C2H4):
ETHYLENE (C2H4)

Typical Alkenes with the same chemical formula

(C4H8) but different molecular structures:
1-BUTENE (C4H8)

ISOBUTENE (C4H8)

6.
b. Dienes and Alkynes. Dienes, also known as diolefins, have two carbon-carbon double
bonds. The alkynes, another class of unsaturated hydrocarbons, have a carbon-carbon triple
bond within the molecule. Both these series of hydrocarbons have the general formula CnH2n2. Diolefins such as 1,2-butadiene and 1,3-butadiene, and alkynes such as acetylene, occur in
C5 and lighter fractions from cracking. The olefins, diolefins, and alkynes are said to be
unsaturated because they contain less than the amount of hydrogen necessary to saturate all
the valences of the carbon atoms. These compounds are more reactive than paraffins or
naphthenes and readily combine with other elements such as hydrogen, chlorine, and
bromine.
FIGURE IV:2-5. TYPICAL DIOLEFINS AND ALKYNES.
Simplest Alkyne:
(C2H2):
ACETYLENE (C2H2)

Typical Diolefins with the same chemical formula

(C4H6) but different molecular structures:
1,2-BUTADIENE (C4H6)

1,3-BUTADIENE (C4H6)

7.

8.

Nonhydrocarbons.
a. Sulfur Compounds. Sulfur may be present in crude oil as hydrogen sulfide (H2S), as
compounds (e.g. mercaptans, sulfides, disulfides, thiophenes, etc.) or as elemental sulfur.
Each crude oil has different amounts and types of sulfur compounds, but as a rule the
proportion, stability, and complexity of the compounds are greater in heavier crude-oil
fractions. Hydrogen sulfide is a primary contributor to corrosion in refinery processing units.
Other corrosive substances are elemental sulfur and mercaptans. Moreover, the corrosive
sulfur compounds have an obnoxious odor.
Pyrophoric iron sulfide results from the corrosive action of sulfur compounds on the iron and
steel used in refinery process equipment, piping, and tanks. The combustion of petroleum
products containing sulfur compounds produces undesirables such as sulfuric acid and sulfur
dioxide. Catalytic hydrotreating processes such as hydrodesulfurization remove sulfur
compounds from refinery product streams. Sweetening processes either remove the
obnoxious sulfur compounds or convert them to odorless disulfides, as in the case of
mercaptans.
b. Oxygen Compounds. Oxygen compounds such as phenols, ketones, and carboxylic acids
occur in crude oils in varying amounts.

c. Nitrogen Compounds. Nitrogen is found in lighter fractions of crude oil as basic

compounds, and more often in heavier fractions of crude oil as nonbasic compounds that
may also include trace metals such as copper, vanadium, and/or nickel. Nitrogen oxides can
form in process furnaces. The decomposition of nitrogen compounds in catalytic cracking and
hydrocracking processes forms ammonia and cyanides that can cause corrosion.
d. Trace Metals. Metals, including nickel, iron, and vanadium are often found in crude oils
in small quantities and are removed during the refining process. Burning heavy fuel oils in
refinery furnaces and boilers can leave deposits of vanadium oxide and nickel oxide in
furnace boxes, ducts, and tubes. It is also desirable to remove trace amounts of arsenic,
vanadium, and nickel prior to processing as they can poison certain catalysts.
e. Salts. Crude oils often contain inorganic salts such as sodium chloride, magnesium
chloride, and calcium chloride in suspension or dissolved in entrained water (brine). These
salts must be removed or neutralized before processing to prevent catalyst poisoning,
equipment corrosion, and fouling. Salt corrosion is caused by the hydrolysis of some metal
chlorides to hydrogen chloride (HCl) and the subsequent formation of hydrochloric acid when
crude is heated. Hydrogen chloride may also combine with ammonia to form ammonium
chloride (NH4Cl), which causes fouling and corrosion.
f. Carbon Dioxide. Carbon dioxide may result from the decomposition of bicarbonates
present in or added to crude, or from steam used in the distillation process.
g. Naphthenic Acids. Some crude oils contain naphthenic (organic) acids, which may
become corrosive at temperatures above 450 F when the acid value of the crude is above a
certain level.

D.

MAJOR REFINERY PRODUCTS.

1.

Gasoline. The most important refinery product is motor gasoline, a blend of hydrocarbons
with boiling ranges from ambient temperatures to about 400 F. The important qualities for
gasoline are octane number (antiknock), volatility (starting and vapor lock), and vapor
pressure (environmental control). Additives are often used to enhance performance and
provide protection against oxidation and rust formation.

2.

Kerosene. Kerosene is a refined middle-distillate petroleum product that finds considerable

use as a jet fuel and around the world in cooking and space heating. When used as a jet fuel,
some of the critical qualities are freeze point, flash point, and smoke point. Commercial jet
fuel has a boiling range of about 375-525 F, and military jet fuel 130-550 F. Kerosene,
with less-critical specifications, is used for lighting, heating, solvents, and blending into diesel
fuel.

3.

Liquified Petroleum Gas (LPG). LPG, which consists principally of propane and butane, is
produced for use as fuel and is an intermediate material in the manufacture of
petrochemicals. The important specifications for proper performance include vapor pressure
and control of contaminants.

4.

Distillate Fuels. Diesel fuels and domestic heating oils have boiling ranges of about 400700 F. The desirable qualities required for distillate fuels include controlled flash and pour
points, clean burning, no deposit formation in storage tanks, and a proper diesel fuel cetane
rating for good starting and combustion.

E.

III.

5.

Residual Fuels. 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 specifications of residual fuels are viscosity and low sulfur
content for environmental control.

6.

Coke and Asphalt. Coke is almost pure carbon with a variety of uses from electrodes to
charcoal briquets. Asphalt, used for roads and roofing materials, must be inert to most
chemicals and weather conditions.

7.

Solvents. A variety of products, whose boiling points and hydrocarbon composition are
closely controlled, are produced for use as solvents. These include benzene, toluene, and
xylene.

8.

Petrochemicals. Many products derived from crude oil refining, such as ethylene,
propylene, butylene, and isobutylene, are primarily intended for use as petrochemical
feedstock in the production of plastics, synthetic fibers, synthetic rubbers, and other
products.

9.

Lubricants. Special refining processes produce lubricating oil base stocks. Additives such as
demulsifiers, antioxidants, and viscosity improvers are blended into the base stocks to
provide the characteristics required for motor oils, industrial greases, lubricants, and cutting
oils. The most critical quality for lubricating-oil base stock is a high viscosity index, which
provides for greater consistency under varying temperatures.

COMMON REFINERY CHEMICALS.

1.

Leaded Gasoline Additives. Tetraethyl lead (TEL) and tetramethyl lead (TML) are additives
formerly used to improve gasoline octane ratings but are no longer in common use except in
aviation gasoline.

2.

Oxygenates. Ethyl tertiary butyl ether (ETBE), methyl tertiary butyl ether (MTBE), tertiary
amyl methyl ether (TAME), and other oxygenates improve gasoline octane ratings and
reduce carbon monoxide emissions.

3.

Caustics. Caustics are added to desalting water to neutralize acids and reduce corrosion.
They are also added to desalted crude in order to reduce the amount of corrosive chlorides in
the tower overheads. They are used in some refinery treating processes to remove
contaminants from hydrocarbon streams.

4.

Sulfuric Acid and Hydrofluoric Acid. Sulfuric acid and hydrofluoric acid are used primarily
as catalysts in alkylation processes. Sulfuric acid is also used in some treatment processes.

PETROLEUM REFINING OPERATIONS.

A.

INTRODUCTION. Petroleum refining begins with the distillation, or fractionation, of crude oils into
separate hydrocarbon groups. The resultant products are directly related to the characteristics of the
crude processed. Most distillation products 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 in this chapter. These converted products are then
subjected to various treatment and separation processes such as extraction, hydrotreating, and

sweetening to remove undesirable constituents and improve product quality. Integrated refineries
incorporate fractionation, conversion, treatment, and blending operations and may also include
petrochemical processing.

B.

REFINING OPERATIONS. Petroleum refining processes and operations can be separated into five
basic areas:

1.

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."

2.

Conversion processes change the size and/or structure of hydrocarbon molecules. These
processes include:

Decomposition (dividing) by thermal and catalytic cracking;

Unification (combining) through alkylation and polymerization; and
Alteration (rearranging) with isomerization and catalytic reforming.

3.

Treatment processes are intended to prepare hydrocarbon streams for additional processing
and to prepare finished products. Treatment may include the removal or separation of
aromatics and naphthenes as well as impurities and undesirable contaminants. Treatment
may involve chemical or physical separation such as dissolving, absorption, or precipitation
using a variety and combination of processes including desalting, drying, hydrodesulfurizing,
solvent refining, sweetening, solvent extraction, and solvent dewaxing.

4.

Formulating and Blending is the process of mixing and combining hydrocarbon fractions,
additives, and other components to produce finished products with specific performance
properties.

5.

Other Refining Operations include: light-ends recovery; sour-water stripping; solid waste
and wastewater treatment; process-water treatment and cooling; storage and handling;
product movement; hydrogen production; acid and tail-gas treatment; and sulfur recovery.
Auxiliary operations and facilities include: steam and power generation; process and fire
water systems; flares and relief systems; furnaces and heaters; pumps and valves; supply of
steam, air, nitrogen, and other plant gases; alarms and sensors; noise and pollution
controls; sampling, testing, and inspecting; and laboratory, control room, maintenance, and
administrative facilities.
FIGURE IV:2-6. REFINERY PROCESS CHART.

TABLE IV:2-3. OVERVIEW OF PETROLEUM REFINING PROCESSE

Process name

Action

Method Purpose

Feedstock(s)

Product(s)

FRACTIONATION PROCESSES
Atmospheric distillation Separation Thermal
Vacuum distillation

Separation

Thermal

Separate fractions Desalted crude oil

Ga

Separate w/o Atmospheric tower

cracking
residual

Gas oi

CONVERSION PROCESSED--DECOMPOSITION
Catalytic cracking

Alteration

Catalytic

Upgrade
gasoline

Gas oil, coke distillate

Gasolin
feedsto

Coking

Polymerize

Thermal

Convert
vacuum
residuals

Gas oil, coke distillate

Gasolin
feedsto

Hydro-cracking

Hydrogenate

Catalytic

Convert to
lighter HC's

Gas oil, cracked oil,

residual

Lighter
produc

*Hydrogen steam
reforming

Decompose

Thermal/ catalytic

Produce
hydrogen

Desulfurized gas, O2,

steam

Hydrog

*Steam cracking

Decompose

Thermal

Crack large
molecules

Atm tower hvy fuel/

distillate

Cracke
residua

Visbreaking

Decompose

Thermal

reduce
viscosity

Atmospheric tower
residual

Distilla

CONVERSION PROCESSES--UNIFICATION
Alkylation

Combining

Catalytic

Unite olefins Tower isobutane/ cracker Iso-oc

& isoparaffins olefin

Grease compounding Combining

Thermal

Combine
soaps & oils

Lube oil, fatty acid, alky

metal

Lubrica

Polymerizing

Catalytic

Unite 2 or
more olefins

Cracker olefins

High-o
petroc

Polymerize

CONVERSION PROCESSES--ALTERATION OR REARRANGEMENT

Catalytic reforming

Alteration/
dehydration

Catalytic

Upgrade low- Coker/ hydro-cracker

octane
naphtha
naphtha

High o
aroma

Isomerization

Rearrange

Catalytic

Convert
Butane, pentane, hexane Isobut
straight chain
hexane
to branch

TREATMENT PROCESSES
*Amine treating

Treatment

Absorption

Remove
Sour gas, HCs w/CO2 &
acidic
H2S
contaminants

Acid fr

Desalting

Dehydration

Absorption

Remove
Crude oil
contaminants

Desalt

Drying & sweetening Treatment

Abspt/ therm

Remove H2O Liq Hcs, LPG, alky

& sulfur
feedstk
cmpds

Sweet

*Furfural extraction

Absorption

Upgrade mid Cycle oils & lube feeddistillate &

stocks
lubes

High q
oil

Catalytic

Remove
High-sulfur residual/ gas Desulf
sulfur,
oil
contaminants

Solvent extr.

Hydrodesulfurization Treatment

Hydrotreating

Hydrogenation Catalytic

Remove
Residuals, cracked HC's
impurities,
saturate HC's

Cracke

*Phenol extraction

Solvent extr.

Abspt/ therm

Improve visc. Lube oil base stocks

index, color

High q

Solvent deasphalting Treatment

Absorption

Remove
asphalt

Vac. tower residual,

propane

Heavy

Solvent dewaxing

Treatment

Cool/ filter

Remove wax Vac. tower lube oils

from lube
stocks

Dewax

Solvent extraction

Solvent extr.

Abspt/ precip.

Separate
unsat. oils

Gas oil, reformate,

distillate

High-o

Sweetening

Treatment

Catalytic

Remv H2S,
convert
mercaptan

Untreated
distillate/gasoline

High-q
distilla

* Note: These processes are not depicted in the refinery process flow chart.

IV.

DESCRIPTION OF PETROLEUM REFINING PROCESSES AND RELATED HEALTH AND SAFETY

CONSIDERATIONS.

A.

CRUDE OIL PRETREATMENT (DESALTING).

1.

Description.
a. Crude oil often contains water, inorganic salts, suspended solids, and water-soluble trace
metals. As a first step in the refining process, to reduce corrosion, plugging, and fouling of
equipment and to prevent poisoning the catalysts in processing units, these contaminants must
be removed by desalting (dehydration).
b. The two most typical methods of crude-oil desalting, chemical and electrostatic separation,
use hot water as the extraction agent. In chemical desalting, water and chemical surfactant
(demulsifiers) are added to the crude, heated so that salts and other impurities dissolve into the
water or attach to the water, and then held in a tank where they settle out. Electrical desalting is
the application of high-voltage electrostatic charges to concentrate suspended water globules in
the bottom of the settling tank. Surfactants are added only when the crude has a large amount of
suspended solids. Both methods of desalting are continuous. A third and less-common process
involves filtering heated crude using diatomaceous earth.
c. The feedstock crude oil is heated to between 150 and 350F to reduce viscosity and surface
tension for easier mixing and separation of the water. The temperature is limited by the vapor
pressure of the crude-oil feedstock. In both methods other chemicals may be added. Ammonia is
often used to reduce corrosion. Caustic or acid may be added to adjust the pH of the water wash.
Wastewater and contaminants are discharged from the bottom of the settling tank to the
wastewater treatment facility. The desalted crude is continuously drawn from the top of the
settling tanks and sent to the crude distillation (fractionating) tower.
TABLE IV:2-4. DESALTING PROCESS.
Feedstock From
Crude

Process Typical products . . . To

Storage Treating Desalted crude . . . Atmospheric distillation tower

Waste water . . . . . Treatment

2.

3.

FIGURE IV:2-7. ELECTROSTAITC DESALTING.

4.

5.

Health and Safety Considerations.

V.

OTHER REFINERY OPERATIONS.

A.

HEAT EXCHANGERS, COOLERS, AND PROCESS HEATERS.

1.

Heating Operations. Process heaters and heat exchangers preheat feedstock in distillation
towers and in refinery processes to reaction temperatures. Heat exchangers use either steam or
hot hydrocarbon transferred from some other section of the process for heat input. The heaters
are usually designed for specific process operations, and most are of cylindrical vertical or boxtype designs. The major portion of heat provided to process units comes from fired heaters
fueled by refinery or natural gas, distillate, and residual oils. Fired heaters are found on crude
and reformer preheaters, coker heaters, and large-column reboilers.

2.

Cooling Operations. Heat also may be removed from some processes by air and water
exchangers, fin fans, gas and liquid coolers, and overhead condensers, or by transferring heat to
other systems. The basic mechanical vapor-compression refrigeration system, which may serve
one or more process units, includes an evaporator, compressor, condenser, controls, and piping.
Common coolants are water, alcohol/water mixtures, or various glycol solutions.

3.

Health and Safety Considerations.

a. Fire Protection and Prevention. A means of providing adequate draft or steam purging is
required to reduce the chance of explosions when lighting fires in heater furnaces. Specific startup and emergency procedures are required for each type of unit. If fire impinges on fin fans,
failure could occur due to overheating. If flammable product escapes from a heat exchanger or
cooler due to a leak, fire could occur.
b. Safety. Care must be taken to ensure that all pressure is removed from heater tubes before
removing header or fitting plugs. Consideration should be given to providing for pressure relief in
heat-exchanger piping systems in the event they are blocked off while full of liquid. If controls
fail, variations of temperature and pressure could occur on either side of the heat exchanger. If
heat exchanger tubes fail and process pressure is greater than heater pressure, product could
enter the heater with downstream consequences. If the process pressure is less than heater
pressure, the heater stream could enter into the process fluid. If loss of circulation occurs in
liquid or gas coolers, increased product temperature could affect downstream operations and
require pressure relief.
c. Health. Because these are closed systems, exposures under normal operating conditions are
expected to be minimal. Depending on the fuel, process operation, and unit design, there is a
potential for exposure to hydrogen sulfide, carbon monoxide, hydrocarbons, steam boiler feedwater sludge, and water-treatment chemicals. Skin contact should be avoided with boiler
blowdown, which may contain phenolic compounds. Safe work practices and/or appropriate
personal protective equipment against hazards may be needed during process maintenance,
inspection, and turnaround activities and for protection from radiant heat, superheated steam,
hot hydrocarbon, and noise exposures.

B.

STEAM GENERATION.

1.

Heater and Boiler Operations. Steam is generated in main generation plants, and/or at
various process units using heat from flue gas or other sources. Heaters (furnaces) include
burners and a combustion air system, the boiler enclosure in which heat transfer takes place, a
draft or pressure system to remove flue gas from the furnace, soot blowers, and compressed-air
systems that seal openings to prevent the escape of flue gas. Boilers consist of a number of

tubes that carry the water-steam mixture through the furnace for maximum heat transfer. These
tubes run between steam-distribution drums at the top of the boiler and water-collecting drums
at the bottom of the boiler. Steam flows from the steam drum to the superheater before entering
the steam distribution system.

2.

Heater Fuel.
a. Heaters may use any one or combination of fuels including refinery gas, natural gas, fuel oil,
and powdered coal. Refinery off-gas is collected from process units and combined with natural
gas and LPG in a fuel-gas balance drum. The balance drum provides constant system pressure,
fairly stable Btu-content fuel, and automatic separation of suspended liquids in gas vapors, and it
prevents carryover of large slugs of condensate into the distribution system. Fuel oil is typically a
mix of refinery crude oil with straight-run and cracked residues and other products. The fuel-oil
system delivers fuel to process-unit heaters and steam generators at required temperatures and
pressures. The fuel oil is heated to pumping temperature, sucked through a coarse suction
strainer, pumped to a temperature-control heater, and then pumped through a fine-mesh
strainer before being burned.
b. In one example of process-unit heat generation, carbon monoxide boilers recover heat in
catalytic cracking units as carbon monoxide in flue gas is burned to complete combustion. In
other processes, waste-heat recovery units use heat from the flue gas to make steam.

3.

Steam Distribution. The distribution system consists of valves, fittings, piping, and connections
suitable for the pressure of the steam transported. Steam leaves the boilers at the highest
pressure required by the process units or electrical generation. The steam pressure is then
reduced in turbines that drive process pumps and compressors. Most steam used in the refinery
is condensed to water in various types of heat exchangers. The condensate is reused as boiler
feedwater or discharged to wastewater treatment. When refinery steam is also used to drive
steam turbine generators to produce electricity, the steam must be produced at much higher
pressure than required for process steam. Steam typically is generated by heaters (furnaces) and
boilers combined in one unit.

4.

Feedwater.
a. Feedwater supply is an important part of steam generation. There must always be as many
pounds of water entering the system as there are pounds of steam leaving it. Water used in
steam generation must be free of contaminants including minerals and dissolved impurities that
can damage the system or affect its operation. Suspended materials such as silt, sewage, and oil,
which form scale and sludge, must be coagulated or filtered out of the water. Dissolved gases,
particularly carbon dioxide and oxygen, cause boiler corrosion and are removed by deaeration
and treatment. Dissolved minerals including metallic salts, calcium, carbonates, etc., that cause
scale, corrosion, and turbine blade deposits are treated with lime or soda ash to precipitate them
from the water. Recirculated cooling water must also be treated for hydrocarbons and other
contaminants.
b. Depending on the characteristics of raw boiler feedwater, some or all of the following six
stages of treatment will be applicable:

Clarification;
Sedimentation;
Filtration;
Ion exchange;
Deaeration; and

5.

Internal treatment.

Health and Safety Considerations.

a. Fire Protection and Prevention. The most potentially hazardous operation in steam
generation is heater startup. A flammable mixture of gas and air can build up as a result of loss
of flame at one or more burners during light-off. Each type of unit requires specific startup and
emergency procedures including purging before lightoff and in the event of misfire or loss of
burner flame.
b. Safety. If feedwater runs low and boilers are dry, the tubes will overheat and fail.
Conversely, excess water will be carried over into the steam distribution system and damage the
turbines. Feedwater must be free of contaminants that could affect operations. Boilers should
have continuous or intermittent blowdown systems to remove water from steam drums and limit
buildup of scale on turbine blades and superheater tubes. Care must be taken not to overheat
the superheater during startup and shut-down. Alternate fuel sources should be provided in the
event of loss of gas due to refinery unit shutdown or emergency. Knockout pots provided at
process units remove liquids from fuel gas before burning.
c. Health. Safe work practices and/or appropriate personal protective equipment may be
needed for potential exposures to feedwater chemicals, steam, hot water, radiant heat, and
noise, and during process sampling, inspection, maintenance, and turnaround activities.

C.

PRESSURE-RELIEF AND FLARE SYSTEMS.

1.

Pressure-Relief Systems. Pressure-relief systems control vapors and liquids that are released
by pressure-relieving devices and blow-downs. Pressure relief is an automatic, planned release
when operating pressure reaches a predetermined level. Blowdown normally refers to the
intentional release of material, such as blowdowns from process unit startups, furnace
blowdowns, shutdowns, and emergencies. Vapor depressuring is the rapid removal of vapors
from pressure vessels in case of fire. This may be accomplished by the use of a rupture disc,
usually set at a higher pressure than the relief valve.

2.

Safety Relief Valve Operations. Safety relief valves, used for air, steam, and gas as well as for
vapor and liquid, allow the valve to open in proportion to the increase in pressure over the
normal operating pressure. Safety valves designed primarily to release high volumes of steam
usually pop open to full capacity. The overpressure needed to open liquid-relief valves where
large-volume discharge is not required increases as the valve lifts due to increased spring
resistance. Pilot-operated safety relief valves, with up to six times the capacity of normal relief
valves, are used where tighter sealing and larger volume discharges are required. Nonvolatile
liquids are usually pumped to oil-water separation and recovery systems, and volatile liquids are
sent to units operating at a lower pressure.

3.

Flare Systems. A typical closed pressure release and flare system includes relief valves and
lines from process units for collection of discharges, knockout drums to separate vapors and
liquids, seals, and/or purge gas for flashback protection, and a flare and igniter system which
combusts vapors when discharging directly to the atmosphere is not permitted. Steam may be
injected into the flare tip to reduce visible smoke.

4.

Pressure Relief Health and Safety Considerations.

a. Fire Protection and Prevention. Vapors and gases must not discharge where sources of
ignition could be present.
b. Safety. Liquids should not be discharged directly to a vapor disposal system. Flare knockout
drums and flares need to be large enough to handle emergency blowdowns. Drums should be
provided with relief in the event of overpressure.
Pressure relief valves must be provided where the potential exists for overpressure in refinery
processes due to the following causes:

Loss of cooling water, which may greatly reduce pressure in condensers and increase the
pressure in the process unit.

Loss of reflux volume, which may cause a pressure drop in condensers and a pressure
rise in distillation towers because the quantity of reflux affects the volume of vapors
leaving the distillation tower.

Rapid vaporization and pressure increase from injection of a lower boiling-point liquid
including water into a process vessel operating at higher temperatures.

Expansion of vapor and resultant over-pressure due to overheated process steam,

malfunctioning heaters, or fire.

Failure of automatic controls, closed outlets, heat exchanger failure, etc.

Internal explosion, chemical reaction, thermal expansion, or accumulated gases.

Maintenance is important because valves are required to function properly. The most common
operating problems are listed below.

Failure to open at set pressure, because of plugging of the valve inlet or outlet, or
because corrosion prevents proper operation of the disc holder and guides.
Failure to reseat after popping open due to fouling, corrosion, or deposits on the seat or
moving parts, or because solids in the gas stream have cut the valve disc.
Chattering and premature opening, because operating pressure is too close to the set
point.

c. Health. Safe work practices and/or appropriate personal protective equipment may be
needed to protect against hazards during inspection, maintenance, and turnaround activities.
D.

E.

WASTEWATER TREATMENT.

1.

Description. Wastewater treatment is used for process, runoff, and sewerage water prior to
discharge or recycling. Wastewater typically contains hydrocarbons, dissolved materials,
suspended solids, phenols, ammonia, sulfides, and other compounds. Wastewater includes
condensed steam, stripping water, spent caustic solutions, cooling tower and boiler blowdown,
wash water, alkaline and acid waste neutralization water, and other process-associated water.

2.

Pretreatment Operations. Pretreatment is the separation of hydrocarbons and solids from

wastewater. API separators, interceptor plates, and settling ponds remove suspended
hydrocarbons, oily sludge, and solids by gravity separation, skimming, and filtration. Some oil-inwater emulsions must be heated to assist in separating the oil and water. Gravity separation
depends on the specific gravity differences between water and immiscible oil globules and allows
free oil to be skimmed off the surface of the wastewater. Acidic wastewater is neutralized using

ammonia, lime, or soda ash. Alkaline wastewater is treated with sulfuric acid, hydrochloric acid,
carbon dioxide-rich flue gas, or sulfur.

3.

Secondary Treatment Operations. After pretreatment, suspended solids are removed by

sedimentation or air flotation. Wastewater with low levels of solids may be screened or filtered.
Flocculation agents are sometimes added to help separation. Secondary treatment processes
biologically degrade and oxidize soluble organic matter by the use of activated sludge, unaerated
or aerated lagoons, trickling filter methods, or anaerobic treatments. Materials with high
adsorption characteristics are used in fixed-bed filters or added to the wastewater to form a
slurry which is removed by sedimentation or filtration. Additional treatment methods are used to
remove oils and chemicals from wastewater. Stripping is used on wastewater containing sulfides
and/or ammonia, and solvent extraction is used to remove phenols.

4.

Tertiary Treatment Operations. Tertiary treatments remove specific pollutants to meet

regulatory discharge requirements. These treatments include chlorination, ozonation, ion
exchange, reverse osmosis, activated carbon adsorption, etc. Compressed oxygen is diffused into
wastewater streams to oxidize certain chemicals or to satisfy regulatory oxygen-content
requirements. Wastewater that is to be recycled may require cooling to remove heat and/or
oxidation by spraying or air stripping to remove any remaining phenols, nitrates, and ammonia.

5.

Health and Safety Considerations.

a. Fire Protection and Prevention. The potential for fire exists if vapors from wastewater
containing hydrocarbons reach a source of ignition during treatment.
b. Health. Safe work practices and/or appropriate personal protective equipment may be
needed for exposures to chemicals and waste products during process sampling, inspection,
maintenance, and turnaround activities as well as to noise, gases, and heat.

F.

COOLING TOWERS.

1.

Description. Cooling towers remove heat from process water by evaporation and latent heat
transfer between hot water and air. The two types of towers are crossflow and counterflow.
Crossflow towers introduce the airflow at right angles to the water flow throughout the structure.
In counterflow cooling towers, hot process water is pumped to the uppermost plenum and
allowed to fall through the tower. Numerous slats or spray nozzles located throughout the length
of the tower disperse the water and help in cooling. Air enters at the tower bottom and flows
upward against the water. When the fans or blowers are at the air inlet, the air is considered to
be forced draft. Induced draft is when the fans are at the air outlet.

2.

Cooling Water. Recirculated cooling water must be treated to remove impurities and dissolved
hydrocarbons. Because the water is saturated with oxygen from being cooled with air, the
chances for corrosion are increased. One means of corrosion prevention is the addition of a
material to the cooling water that forms a protective film on pipes and other metal surfaces.

3.

Health and Safety Considerations.

a. Fire Prevention and Protection. When cooling water is contaminated by hydrocarbons,
flammable vapors can be evaporated into the discharge air. If a source of ignition is present, or if
lightning occurs, a fire may start. A potential fire hazard also exists where there are relatively dry
areas in induced-draft cooling towers of combustible construction.

b. Safety. Loss of power to cooling tower fans or water pumps could have serious consequences
in the operation of the refinery. Impurities in cooling water can corrode and foul pipes and heat
exchangers, scale from dissolved salts can deposit on pipes, and wooden cooling towers can be
damaged by microorganisms.
c. Health. Cooling-tower water can be contaminated by process materials and by-products
including sulfur dioxide, hydrogen sulfide, and carbon dioxide, with resultant exposures. Safe
work practices and/or appropriate personal protective equipment may be needed during process
sampling, inspection, maintenance, and turnaround activities; and for exposure to hazards such
as those related to noise, water-treatment chemicals, and hydrogen sulfide when wastewater is
treated in conjunction with cooling towers.

G.

ELECTRIC POWER.

1.

Description. Refineries may receive electricity from outside sources or produce their own power
with generators driven by steam turbines or gas engines. Electrical substations receive power
from the utility or power plant for distribution throughout the facility. They are usually located in
nonclassified areas, away from sources of vapor or cooling-tower water spray. Transformers,
circuit breakers, and feed-circuit switches are usually located in substations. Substations feed
power to distribution stations within the process unit areas. Distribution stations can be located in
classified areas, providing that classification requirements are met. Distribution stations usually
have a liquid-filled transformer and an oil-filled or air-break disconnect device.

2.

Health and Safety Considerations.

a. Fire Protection and Prevention. Generators that are not properly classified and are located
too close to process units may be a source of ignition should a spill or release occur.
b. Safety. Normal electrical safety precautions including dry footing, high-voltage warning signs,
and guarding must be taken to protect against electrocution. Lockout/tagout and other
appropriate safe work practices must be established to prevent energization while work is being
performed on high-voltage electrical equipment.
c. Health. Safe work practices and/or the use of appropriate personal protective equipment may
be needed for exposures to noise, for exposure to hazards during inspection and maintenance
activities, and when working around transformers and switches that may contain a dielectric fluid
which requires special handling precautions.

H.

GAS AND AIR COMPRESSORS.

1.

Description. Both reciprocating and centrifugal compressors are used throughout the refinery
for gas and compressed air. Air compressor systems include compressors, coolers, air receivers,
air dryers, controls, and distribution piping. Blowers are used to provide air to certain processes.
Plant air is provided for the operation of air-powered tools, catalyst regeneration, process
heaters, steam-air decoking, sour-water oxidation, gasoline sweetening, asphalt blowing, and
other uses. Instrument air is provided for use in pneumatic instruments and controls, air motors
and purge connections.

2.

Health and Safety Considerations.

a. Fire Protection and Prevention. Air compressors should be located so that the suction does
not take in flammable vapors or corrosive gases. There is a potential for fire should a leak occur
in gas compressors.
b. Safety. Knockout drums are needed to prevent liquid surges from entering gas compressors.
If gases are contaminated with solid materials, strainers are needed. Failure of automatic
compressor controls will affect processes. If maximum pressure could potentially be greater than
compressor or process-equipment design pressure, pressure relief should be provided. Guarding
is needed for exposed moving parts on compressors. Compressor buildings should be properly
electrically classified, and provisions should be made for proper ventilation.
Where plant air is used to back up instrument air, interconnections must be upstream of the
instrument air drying system to prevent contamination of instruments with moisture. Alternate
sources of instrument air supply, such as use of nitrogen, may be needed in the event of power
outages or compressor failure.
c. Health. Safe work practices and/or appropriate personal protective equipment may be
needed for exposure to hazards such as noise and during inspection and maintenance activities.
The use of appropriate safeguards must be considered so that plant and instrument air is not
used for breathing or pressuring potable water systems.

I.

MARINE, TANK CAR, AND TANK TRUCK LOADING AND UNLOADING.

1.

Description. Facilities for loading liquid hydrocarbons into tank cars, tank trucks, and marine
vessels and barges are usually part of the refinery operations. Product characteristics,
distribution needs, shipping requirements, and operating criteria are important when designing
loading facilities. Tank trucks and rail tank cars are either top- or bottom-loaded, and vaporrecovery systems may be provided where required. Loading and unloading liquefied petroleum
gas (LPG) require special considerations in addition to those for liquid hydrocarbons.

2.

Health and Safety Considerations.

a. Fire Protection and Prevention. The potential for fire exists where flammable vapors from
spills or releases can reach a source of ignition. Where switch-loading is permitted, safe practices
need to be established and followed. Bonding is used to equalize the electrical charge between
the loading rack and the tank truck or tank car. Grounding is used at truck and rail loading
facilities to prevent flow of stray currents. Insulating flanges are used on marine dock piping
connections to prevent static electricity buildup and discharge. Flame arrestors should be
installed in loading rack and marine vapor-recovery lines to prevent flashback.
b. Safety. Automatic or manual shutoff systems at supply headers are needed for top and
bottom loading in the event of leaks or overfills. Fall protection such as railings are needed for
top-loading racks where employees are exposed to falls. Drainage and recovery systems may be
provided for storm drainage and to handle spills and leaks. Precautions must be taken at LPG
loading facilities not to overload or overpressurize tank cars and trucks.
c. Health. The nature of the health hazards at loading and unloading facilities depends upon the
products being loaded and the products previously transported in the tank cars, tank trucks, or
marine vessels. Safe work practices and/or appropriate personal protective equipment may be
needed to protect against hazardous exposures when loading or unloading, cleaning up spills or
leaks, or when gauging, inspecting, sampling, or performing maintenance activities on loading
facilities or vapor-recovery systems.

J.

TURBINES.

1.

Description. Turbines are usually gas- or steam-powered and are typically used to drive pumps,
compressors, blowers, and other refinery process equipment. Steam enters turbines at high
temperatures and pressures, expands across and drives rotating blades while directed by fixed
blades.

2.

Health and Safety Considerations.

a. Safety. Steam turbines used for exhaust operating under vacuum should have safety relief
valves on the discharge side, both for protection and to maintain steam in the event of vacuum
failure. Where maximum operating pressure could be greater than design pressure, steam
turbines should be provided with relief devices. Consideration should be given to providing
governors and overspeed control devices on turbines.
b. Health. Safe work practices and/or appropriate personal protective equipment may be
needed for noise, steam and heat exposures, and during inspection and maintenance activities.

K.

PUMPS, PIPING AND VALVES.

1.

Description.
a. Centrifugal and positive-displacement (i.e., reciprocating) pumps are used to move
hydrocarbons, process water, fire water, and wastewater through piping within the refinery.
Pumps are driven by electric motors, steam turbines, or internal combustion engines. The pump
type, capacity, and construction materials depend on the service for which it is used.
b. Process and utility piping distribute hydrocarbons, steam, water, and other products
throughout the facility. Their size and construction depend on the type of service, pressure,
temperature, and nature of the products. Vent, drain, and sample connections are provided on
piping, as well as provisions for blanking.
c. Different types of valves are used depending on their operating purpose. These include gate
valves, bypass valves, globe and ball valves, plug valves, block and bleed valves, and check
valves. Valves can be manually or automatically operated.

2.

Health and Safety Considerations.

a. Fire Protection and Prevention. The potential for fire exists should hydrocarbon pumps,
valves, or lines develop leaks that could allow vapors to reach sources of ignition. Remote
sensors, control valves, fire valves, and isolation valves should be used to limit the release of
hydrocarbons at pump suction lines in the event of leakage and/or fire.
b. Safety. Depending on the product and service, backflow prevention from the discharge line
may be needed. The failure of automatic pump controls could cause a deviation in process
pressure and temperature. Pumps operated with reduced or no flow can overheat and rupture.
Pressure relief in the discharge piping should be provided where pumps can be overpressured.
Provisions may be made for pipeline expansion, movement, and temperature changes to avoid

rupture. Valves and instruments that require servicing or other work should be accessible at
grade level or from an operating platform. Operating vent and drain connections should be
provided with double-block valves, a block valve and plug, or blind flange for protection against
releases.
c. Health. Safe work practices and/or appropriate personal protective equipment may be
needed for exposure to hazards such as those related to liquids and vapors when opening or
draining pumps, valves, and/or lines, and during product sampling, inspection, and maintenance
activities.

L.

TANK STORAGE.

1.

Description. Atmospheric storage tanks and pressure storage tanks are used throughout the
refinery for storage of crudes, intermediate hydrocarbons (during the process), and finished
products. Tanks are also provided for fire water, process and treatment water, acids, additives,
and other chemicals. The type, construction, capacity and location of tanks depends on their use
and materials stored.

2.

Health and Safety Considerations.

a. Fire Prevention and Protection. The potential for fire exists should hydrocarbon storage
tanks be overfilled or develop leaks that allow vapors to escape and reach sources of ignition.
Remote sensors, control valves, isolation valves, and fire valves may be provided at tanks for
pump-out or closure in the event of a fire in the tank, or in the tank dike or storage area.
b. Safety. Tanks may be provided with automatic overflow control and alarm systems, or manual
gauging and checking procedures may be established to control overfills.
c. Health. Safe work practices and/or appropriate personal protective equipment may be
needed for exposure to hazards related to product sampling, manual gauging, inspection, and
maintenance activities including confined space entry where applicable.

INTRODUCTION
The petroleum industry began with the successful drilling of the first commercial oil well in 1859,
and the opening of the first refinery two years later to process the crude into kerosene. The
evolution of petroleum refining from simple distillation to today's sophisticated processes has
created a need for health and safety management procedures and safe work practices. To those
unfamiliar with the industry, petroleum refineries may appear to be complex and confusing places.
Refining is the processing of one complex mixture of hydrocarbons into a number of other complex
mixtures of hydrocarbons. The safe and orderly processing of crude oil into flammable gases and
liquids at high temperatures and pressures using vessels, equipment, and piping subjected to stress
and corrosion requires considerable knowledge, control, and expertise.
___________________________________________________________________
Safety and health professionals, working with process, chemical, instrumentation, and metallurgical
engineers, assure that potential physical, mechanical, chemical, and health hazards are recognized and
provisions are made for safe operating practices and appropriate protective measures. These measures
may include hard hats, safety glasses and goggles, safety shoes, hearing protection, respiratory protection,
and protective clothing such as fire resistant clothing where required. In addition, procedures should be
established to assure compliance with applicable regulations and standards such as hazard
communications, confined space entry, and process safety management.
This chapter of the technical manual covers the history of refinery processing, characteristics of crude oil,
hydrocarbon types and chemistry, and major refinery products and by-products. It presents information on
technology as normally practiced in present operations. It describes the more common refinery processes
and includes relevant safety and health information. Additional information covers refinery utilities and
miscellaneous supporting activities related to hydrocarbon processing. Field personnel will learn what to
expect in various facilities regarding typical materials and process methods, equipment, potential hazards,
and exposures.
The information presented refers to fire prevention, industrial hygiene, and safe work practices, and is not
intended to provide comprehensive guidelines for protective measures and/or compliance with regulatory
requirements. As some of the terminology is industry-specific, a glossary is provided as an appendix. This
chapter does not cover petrochemical processing.

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B. OVERVIEW OF THE PETROLEUM INDUSTRY
_____________________________________________________________________
BASIC REFINERY PROCESS -- DESCRIPTION AND HISTORY
Petroleum refining has evolved continuously in response to changing consumer demand for better and
different products. The original requirement was to produce kerosene as a cheaper and better source of light
than whale oil. The development of the internal combustion engine led to the production of gasoline and
diesel fuels. The evolution of the airplane created a need first for high-octane aviation gasoline and then for
jet fuel, a sophisticated form of the original product, kerosene. Present-day refineries produce a variety of
products including many required as feedstocks for the petrochemical industry.

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DISTILLATION PROCESSES
The first refinery, opened in 1861, produced kerosene by simple atmospheric distillation. Its by-products
included tar and naphtha. It was soon discovered that high-quality lubricating oils could be produced by
distilling petroleum under vacuum. However, for the next 30 years kerosene was the product consumers
wanted. Two significant events changed this situation: (1) invention of the electric light decreased the

demand for kerosene, and (2) invention of the internal combustion engine created a demand for diesel fuel
and gasoline (naphtha).

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THERMAL CRACKING PROCESSES
With the advent of mass production and World War I, the number of gasoline-powered vehicles increased
dramatically and the demand for gasoline grew accordingly. However, distillation processes produced only a
certain amount of gasoline from crude oil. In 1913, the thermal cracking process was developed, which
subjected heavy fuels to both pressure and intense heat, physically breaking the large molecules into
smaller ones to produce additional gasoline and distillate fuels. Visbreaking, another form of thermal
cracking, was developed in the late 1930s to produce more desirable and valuable products.

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CATALYTIC PROCESSES
Higher-compression gasoline engines required higher-octane gasoline with better antiknock characteristics.
The introduction of catalytic cracking and polymerization processes in the mid- to late 1930s met the
demand by providing improved gasoline yields and higher octane numbers.
Alkylation, another catalytic process developed in the early 1940s, produced more high-octane aviation
gasoline and petrochemical feedstocks for explosives and synthetic rubber. Subsequently, catalytic
isomerization was developed to convert hydrocarbons to produce increased quantities of alkylation
feedstocks. Improved catalysts and process methods such as hydrocracking and reforming were developed
throughout the 1960s to increase gasoline yields and improve antiknock characteristics. These catalytic
processes also produced hydrocarbon molecules with a double bond (alkenes) and formed the basis of the
modern petrochemical industry.

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TREATMENT PROCESSES
Throughout the history of refining, various treatment methods have been used to remove nonhydrocarbons,
impurities, and other constituents that adversely affect the properties of finished products or reduce the
efficiency of the conversion processes. Treating can involve chemical reaction and/or physical separation.
Typical examples of treating are chemical sweetening, acid treating, clay contacting, caustic washing,
hydrotreating, drying, solvent extraction, and solvent dewaxing. Sweetening compounds and acids
desulfurize crude oil before processing and treat products during and after processing.
Following the Second World War, various reforming processes improved gasoline quality and yield and
produced higher-quality products. Some of these involved the use of catalysts and/or hydrogen to change
molecules and remove sulfur. A number of the more commonly used treating and reforming processes are
described in this chapter of the manual.

HISTORY OF REFINING
_____________________________________________________________________
Year

Process name

Purpose

By-products, etc.

1862

Atmospheric
distillation

Produce kerosene

Naphtha, tar, etc.

Lubricants (original)
Cracking feedstocks
(1930s)

Asphalt, residual
coker feedstocks

Thermal cracking

Increase gasoline

Residual, bunker

1916

Sweetening

Reduce sulfur & odor

1930

Thermal reforming

Improve octane number

Residual

1932

Hydrogenation

Remove sulfur

Sulfur

1932

Coking

Produce gasoline
basestocks

Coke

1933

Solvent extraction

Improve lubricant
viscosity index

Aromatics

1935

Solvent dewaxing

Improve pour point

Waxes

1935

Cat. polymerization

Improve gasoline
yield & octane
number

Petrochemical
feedstocks

1937

Catalytic cracking

Higher octane
gasoline

Petrochemical
feedstocks

1939

Visbreaking

Reduce viscosity

Increased
distillate, tar

1940

Alkylation

Increase gasoline
octane & yield

High-octane aviation
gasoline

1940

Isomerization

Produce alkylation
feedstock

Naphtha

1942

Fluid catalytic
cracking

Increase gasoline
yield & octane

Petrochemical
feedstocks

1950

Deasphalting

Increase cracking
feedstock

Asphalt

1952

Catalytic reforming

Convert low-quality
naphtha

Aromatics

1954

Hydrodesulfurization

Remove sulfur

Sulfur

1956

Inhibitor sweetening

Remove mercaptan

Disulfides

1957

Catalytic
isomerization

Convert to molecules
with high octane

Alkylation
feedstocks

1870

1913
fuel

Vacuum
distillation

Sulfur

number
1960

Hydrocracking

Improve quality and

reduce sulfur

Alkylation
feedstocks

1974

Catalytic dewaxing

Improve pour point

Wax

1975

Residual
hydrocracking

Increase gasoline
yield from residual

Heavy residuals

_____________________________________________________________________

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BASICS OF CRUDE OIL
Crude oils are complex mixtures containing many different hydrocarbon compounds that vary in appearance
and composition from one oil field to another. Crude oils range in consistency from water to tar-like solids,
and in color from clear to black. An average crude oil contains about 84% carbon, 14% hydrogen, 1-3%
sulfur, and less than 1% each of nitrogen, oxygen, metals, and salts. Crude oils are generally classified as
paraffinic, naphthenic, or aromatic, based on the predominant proportion of similar hydrocarbon molecules.
Mixed-base crudes have varying amounts of each type of hydrocarbon. Refinery crude base stocks usually
consist of mixtures of two or more different crude oils.
Relatively simple crude-oil assays are used to classify crude oils as paraffinic, naphthenic, aromatic, or
mixed. One assay method (United States Bureau of Mines) is based on distillation, and another method
(UOP K factor) is based on gravity and boiling points. More comprehensive crude assays determine the
value of the crude (i.e., its yield and quality of useful products) and processing parameters. Crude oils are
usually grouped according to yield structure.

Table III:2-2.

TYPICAL APPROXIMATE CHARACTERISTICS AND PROPERTIES

AND GASOLINE POTENTIAL OF VARIOUS CRUDES
(Representative average numbers)
_____________________________________________________________________
Crude
source

Paraffins Aromatics
(% vol) (% vol)

Naphth- Sulfur
API
enes
gravity
(% vol) (% wt) (approx.)

Naph.
Octane
yield
number
(% vol) (typical)

Nigerian
-Light

37

54

0.2

36

28

60

Saudi
-Light

63

19

18

34

22

40

Saudi
-Heavy

60

15

25

2.1

28

23

35

Venezuela
-Heavy

35

12

53

2.3

30

60

Venezuela
-Light

52

14

34

1.5

24

18

50

USA
-Midcont.
Sweet

0.4

40

USA
46
-W. Texas
Sour

22

32

1.9

32

33

55

North Sea
50
16
34
0.4
37
31
50
-Brent
_____________________________________________________________________

Crude oils are also defined in terms of API (American Petroleum Institute) gravity. The higher the API
gravity, the lighter the crude. For example, light crude oils have high API gravities and low specific gravities.
Crude oils with low carbon, high hydrogen, and high API gravity are usually rich in paraffins and tend to yield
greater proportions of gasoline and light petroleum products; those with high carbon, low hydrogen, and low
API gravities are usually rich in aromatics.
Crude oils that contain appreciable quantities of hydrogen sulfide or other reactive sulfur compounds are
called sour. Those with less sulfur are called sweet. Some exceptions to this rule are West Texas crudes,
which are always considered sour regardless of their H(2)S content, and Arabian high-sulfur crudes, which
are not considered sour because their sulfur compounds are not highly reactive.

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BASICS OF HYDROCARBON CHEMISTRY
Crude oil is a mixture of hydrocarbon molecules, which are organic compounds of carbon and hydrogen
atoms that may include from one to 60 carbon atoms. The properties of hydrocarbons depend on the
number and arrangement of the carbon and hydrogen atoms in the molecules. The simplest hydrocarbon
molecule is one carbon atom linked with four hydrogen atoms: methane. All other variations of petroleum
hydrocarbons evolve from this molecule.
Hydrocarbons containing up to four carbon atoms are usually gases; those with five to 19 carbon atoms are
usually liquids; and those with 20 or more are solids. The refining process uses 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) rather than its specific chemical compounds that is significant in the refining
process.
THREE PRINCIPAL GROUPS OR SERIES OF HYDROCARBON COMPOUNDS THAT OCCUR
NATURALLY IN CRUDE OIL
PARAFFINS
The paraffinic series of hydrocarbon compounds found in crude oil have the general formula C(n)H(2n+2)
and can be either straight chains (normal) or branched chains (isomers) of carbon atoms. The lighter,
straight-chain paraffin molecules are found in gases and paraffin waxes. Examples of straight-chain
molecules are methane, ethane, propane, and butane (gases containing from one to four carbon atoms),
and pentane and hexane (liquids with five to six carbon atoms). The branched-chain (isomer) paraffins are

usually found in heavier fractions of crude oil and have higher octane numbers than normal paraffins. These
compounds are saturated hydrocarbons, with all carbon bonds satisfied, that is, the hydrocarbon chain
carries the full complement of hydrogen atoms.
AROMATICS
Aromatics are unsaturated ring-type (cyclic) compounds which react readily because they have carbon
atoms that are deficient in hydrogen. All aromatics have at least one benzene ring (a single-ring compound
characterized by three double bonds alternating with three single bonds between six carbon atoms) as part
of their molecular structure. Naphthalenes are fused double-ring aromatic compounds. The most complex
aromatics, polynuclears (three or more fused aromatic rings), are found in heavier fractions of crude oil.
NAPHTHENES
Naphthenes are saturated hydrocarbon groupings with the general formula C(n)H(2n), arranged in the form
of closed rings (cyclic) and found in all fractions of crude oil except the very lightest. Single-ring naphthenes
(monocycloparaffins) with five and six carbon atoms predominate, with two-ring naphthenes
(dicycloparaffins) found in the heavier ends of naphtha.
OTHER HYDROCARBONS
ALKENES
Alkenes are mono-olefins with the general formula C(n)H(2n) and contain only one carbon-carbon double
bond in the chain. The simplest alkene is ethylene, with two carbon atoms joined by a double bond and four
hydrogen atoms. Olefins are usually formed by thermal and catalytic cracking and rarely occur naturally in
unprocessed crude oil.
DIENES AND ALKYNES
Dienes, also known as diolefins, have two carbon-carbon double bonds. The alkynes, another class of
unsaturated hydrocarbons, have a carbon-carbon triple bond within the molecule. Both these series of
hydrocarbons have the general formula C(n)H(2n-2). Diolefins such as 1,2-butadiene and 1,3-butadiene,
and alkynes such as acetylene occur in C(5) and lighter fractions from cracking. The olefins, diolefins, and
alkynes are said to be unsaturated because they contain less than the amount of hydrogen necessary to
saturate all the valences of the carbon atoms. These compounds are more reactive than paraffins or
naphthenes and readily combine with other elements such as hydrogen, chlorine, and bromine.
NONHYDROCARBONS
SULFUR COMPOUNDS
Sulfur may be present in crude oil as hydrogen sulfide (H(2)S), as compounds (e.g., mercaptans, sulfides,
disulfides, thiophenes, etc.), or as elemental sulfur. Each crude oil has different amounts and types of sulfur
compounds, but as a rule the proportion, stability, and complexity of the compounds are greater in heavier
crude-oil fractions. Hydrogen sulfide is a primary contributor to corrosion in refinery processing units. Other
corrosive substances are elemental sulfur and mercaptans. Moreover, the corrosive sulfur compounds have
an obnoxious odor.
Pyrophoric iron sulfide results from the corrosive action of sulfur compounds on the iron and steel used in
refinery process equipment, piping, and tanks. The combustion of petroleum products containing sulfur
compounds produces undesirables such as sulfuric acid and sulfur dioxide. Catalytic hydrotreating
processes such as hydrodesulfurization remove sulfur compounds from refinery product streams.
Sweetening processes either remove the obnoxious sulfur compounds or convert them to odorless
disulfides, as in the case of mercaptans.
OXYGEN COMPOUNDS

Oxygen compounds such as phenols, ketones, and carboxylic acids occur in crude oils in varying amounts.
NITROGEN COMPOUNDS
Nitrogen is found in lighter fractions of crude oil as basic compounds, and more often in heavier fractions of
crude oil as nonbasic compounds that may also include trace metals such as copper, vanadium, and/or
nickel. Nitrogen oxides can form in process furnaces. The decomposition of nitrogen compounds in catalytic
cracking and hydrocracking processes forms ammonia and cyanides that can cause corrosion.
TRACE METALS
Metals including nickel, iron, and vanadium are often found in crude oils in small quantities and are removed
during the refining process. Burning heavy fuel oils in refinery furnaces and boilers can leave deposits of
vanadium oxide and nickel oxide in furnace boxes, ducts, and tubes. It is also desirable to remove trace
amounts of arsenic, vanadium, and nickel prior to processing as they can poison certain catalysts.
SALTS
Crude oils often contain inorganic salts such as sodium chloride, magnesium chloride, and calcium chloride
in suspension or dissolved in entrained water (brine). These salts must be removed or neutralized before
processing to prevent catalyst poisoning, equipment corrosion, and fouling. Salt corrosion is caused by the
hydrolysis of some metal chlorides to hydrogen chloride (HCl) and the subsequent formation of hydrochloric
acid when crude is heated. Hydrogen chloride may also combine with ammonia to form ammonium chloride
(NH(4)Cl), which causes fouling and corrosion.
CARBON DIOXIDE
Carbon dioxide may result from the decomposition of bicarbonates present in or added to crude, or from
steam used in the distillation process.
NAPHTHENIC ACIDS
Some crude oils contain naphthenic (organic) acids, which may become corrosive at temperatures above
450 degrees F when the acid value of the crude is above a certain level.

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MAJOR REFINERY PRODUCTS
GASOLINE
The most important refinery product is motor gasoline, a blend of hydrocarbons with boiling ranges from
ambient temperatures to about 400 degrees F. The important qualities for gasoline are octane number
(antiknock), volatility (starting and vapor lock), and vapor pressure (environmental control). Additives are
often used to enhance performance and provide protection against oxidation and rust formation.
KEROSENE
Kerosene is a refined middle-distillate petroleum product that finds considerable use as a jet fuel and around
the world in cooking and space heating. When used as a jet fuel, some of the critical qualities are freeze
point, flash point, and smoke point. Commercial jet fuel has a boiling range of about 375-525 degrees F, and
military jet fuel 130-550 degrees F. Kerosene, with less-critical specifications, is used for lighting, heating,
solvents, and blending into diesel fuel.
LIQUEFIED PETROLEUM GAS (LPG)

LPG, which consists principally of propane and butane, is produced for use as fuel and is an intermediate
material in the manufacture of petrochemicals. The important specifications for proper performance include
vapor pressure and control of contaminants.
DISTILLATE FUELS
Diesel fuels and domestic heating oils have boiling ranges of about 400-700 degrees F. The desirable
qualities required for distillate fuels include controlled flash and pour points, clean burning, no deposit
formation in storage tanks, and a proper diesel fuel cetane rating for good starting and combustion.
RESIDUAL FUELS
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 specifications
of residual fuels are viscosity and low sulfur content for environmental control.
COKE AND ASPHALT
Coke is almost pure carbon with a variety of uses from electrodes to charcoal briquets. Asphalt, used for
roads and roofing materials, must be inert to most chemicals and weather conditions.
SOLVENTS
A variety of products, whose boiling points and hydrocarbon composition are closely controlled, are
produced for use as solvents. These include benzene, toluene, and xylene.
PETROCHEMICALS
Many products derived from crude oil refining such as ethylene, propylene, butylene, and isobutylene are
primarily intended for use as petrochemical feedstocks in the production of plastics, synthetic fibers,
synthetic rubbers, and other products.
LUBRICANTS
Special refining processes produce lubricating oil base stocks. Additives such as demulsifiers, antioxidants,
and viscosity improvers are blended into the base stocks to provide the characteristics required for motor
oils, industrial greases, lubricants, and cutting oils. The most critical quality for lubricating-oil base stock is a
high viscosity index, which provides for greater consistency under varying temperatures.
COMMON REFINERY CHEMICALS
LEADED GASOLINE ADDITIVES
Tetraethyl lead (TEL) and tetramethyl lead (TML) are additives formerly used to improve gasoline octane
ratings but are no longer in common use except in aviation gasoline.
OXYGENATES
Ethyl tertiary butyl ether (ETBE), methyl tertiary butyl ether (MTBE), tertiary amyl methyl ether (TAME), and
other oxygenates improve gasoline octane ratings and reduce carbon monoxide emissions.
CAUSTICS

Caustics are added to desalting water to neutralize acids and reduce corrosion. They are also added to
desalted crude in order to reduce the amount of corrosive chlorides in the tower overheads. They are used
in some refinery treating processes to remove contaminants from hydrocarbon streams.
SULFURIC ACID AND HYDROFLUORIC ACID
Sulfuric acid and hydrofluoric acid are used primarily as catalysts in alkylation processes. Sulfuric acid is
also used in some treatment processes.

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PETROLEUM REFINING OPERATIONS
INTRODUCTION
Petroleum refining begins with the distillation, or fractionation, of crude oils into separate hydrocarbon
groups. The resultant products are directly related to the characteristics of the crude processed. Most
distillation products 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 in
this chapter. These converted products are then subjected to various treatment and separation processes
such as extraction, hydrotreating, and sweetening to remove undesirable constituents and improve product
quality. Integrated refineries incorporate fractionation, conversion, treatment, and blending operations and
may also include petrochemical processing.
REFINING OPERATIONS
Petroleum refining processes and operations can be separated into five basic areas:
FRACTIONATION
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.

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CONVERSION
Conversion processes change the size and/or structure of hydrocarbon molecules. These processes
include:

decomposition (dividing) by thermal and catalytic cracking

unification (combining) through alkylation and polymerization, and

alteration (rearranging) with isomerization and catalytic reforming

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TREATMENT
Treatment processes are intended to prepare hydrocarbon streams for additional processing and to prepare
finished products. Treatment may include the removal or separation of aromatics and naphthenes as well as
impurities and undesirable contaminants. Treatment may involve chemical or physical separation such as

dissolving, absorption, or precipitation using a variety and combination of processes including desalting,
drying, hydrodesulfurizing, solvent refining, sweetening, solvent extraction, and solvent dewaxing.

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FORMULATING AND BLENDING
Formulating and blending is the process of mixing and combining hydrocarbon fractions, additives, and other
components to produce finished products with specific performance properties.

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OTHER REFINING OPERATIONS
Other refinery operations include light-ends recovery, sour-water stripping, solid waste and wastewater
treatment, process-water treatment and cooling, storage, and handling, product movement, hydrogen
production, acid and tail-gas treatment, and sulfur recovery.
Auxiliary operations and facilities include steam and power generation; process and fire water systems;
flares and relief systems; furnaces and heaters; pumps and valves; supply of steam, air, nitrogen, and other
plant gases; alarms and sensors; noise and pollution controls; sampling, testing, and inspecting; and
laboratory, control room, maintenance, and administrative facilities.

Table III:2-3 OVERVIEW OF PETROLEUM REFINING PROCESSES

_____________________________________________________________________
Process
name

Action

Method

Purpose

Feedstock(s) Product(s)

FRACTIONATION PROCESSES
Atmospheric
distillation

Separation

Thermal

Separate
fractions

Desalted
crude oil

Vacuum
distillation
residual

Separation

Thermal

Separate
w/o

Atmospheric

cracking

tower
residual

Gas, gas oil,

distillate,
residual
Gas oil, lube
stock,

CONVERSION PROCESSES-DECOMPOSITION
Catalytic
Alteration
cracking
petrochemical

Catalytic

Upgrade
Gas oil,
gasoline coke

Coking
gas oil,

Thermal

Convert

distillate feedstock
Residual,
Naphtha,

vacuum
residuals
Convert
to oil,

heavy oil,
tar
Gas oil,
cracked

Hydrocracking
quality

Polymerize

Hydrogenate

Catalytic

Gasoline,

coke
Lighter,
higher-

*Hydrogen
CO,
Steam
Reforming

Decompose

Thermal/
cat.

*Steam
Decompose
naphtha,
Cracking
coke,residual

Thermal

Visbreaking
tar

Thermal

Decompose

lighter
HCs
Produce

residual

products

Desul-

Hydrogen,

hydrogen
Crack

furized
gas, O(2),
steam
Atm tower

large

hvy fuel/

CO(2)
Cracked

molecules distillate
Reduce
Atmospheric Distillate,
viscosity tower
residual

CONVERSION PROCESSES-UNIFICATION
Alkylation

Combining

Catalytic

Grease
compounding

Combining

Thermal

Polymerization

Polymerize

Catalytic

Unite
Tower
Iso-octane
olefins
isobutane/ (alkylate)
&
crckr
isoparolefin
affins
Combine
Lube oil,
Lubricating
soaps
fatty acid, grease
& oils
alky metal
Unite 2
Cracker
High-octane
or more
olefins
naphtha,
olefins
petrochemical stocks

CONVERSION PROCESSES-ALTERATION or REARRANGEMENT

Catalytic
reforming

Alteration/
dehydration

Catalytic

Upgrade
lowocta

Coker/hydro- High oct.

cracker
reformate/

Back to Top
CRUDE OIL PRETREATMENT (DESALTING).
Description
a. Crude oil often contains water, inorganic salts, suspended solids, and water-soluble trace metals. As a
first step in the refining process, to reduce corrosion, plugging, and fouling of equipment and to prevent
poisoning the catalysts in processing units, these contaminants must be removed by desalting (dehydration).
b. The two most typical methods of crude-oil desalting, chemical and electrostatic separation, use hot water
as the extraction agent. In chemical desalting, water and chemical surfactant (demulsifiers) are added to the
crude, heated so that salts and other impurities dissolve into the water or attach to the water, and then held
in a tank where they settle out. Electrical desalting is the application of high-voltage electrostatic charges to
concentrate suspended water globules in the bottom of the settling tank. Surfactants are added only when
the crude has a large amount of suspended solids. Both methods of desalting are continuous. A third and
less-common process involves filtering heated crude using diatomaceous earth.

c. The feedstock crude oil is heated to between 150 and 350F to reduce viscosity and surface tension for
easier mixing and separation of the water. The temperature is limited by the vapor pressure of the crude-oil
feedstock. In both methods other chemicals may be added. Ammonia is often used to reduce corrosion.
Caustic or acid may be added to adjust the pH of the water wash. Wastewater and contaminants are
discharged from the bottom of the settling tank to the wastewater treatment facility. The desalted crude is
continuously drawn from the top of the settling tanks and sent to the crude distillation (fractionating) tower.
TABLE IV:2-4. DESALTING PROCESS.
Feedstock

From

Process

Typical products

To

Crude

Storage

Treating

Desalted crude

Atmospheric distillation tower

Waste water

Treatment

FIGURE IV:2-7. ELECTROSTAITC DESALTING.

2. Health and Safety Considerations

a. Fire Prevention and Protection. The potential exists for a fire due to a leak or release of crude from
heaters in the crude desalting unit. Low boiling point components of crude may also be released if a leak
occurs.
b. Safety. Inadequate desalting can cause fouling of heater tubes and heat exchangers throughout the
refinery. Fouling restricts product flow and heat transfer and leads to failures due to increased pressures and
temperatures. Corrosion, which occurs due to the presence of hydrogen sulfide, hydrogen chloride,
naphthenic (organic) acids, and other contaminants in the crude oil, also causes equipment failure.
Neutralized salts (ammonium chlorides and sulfides), when moistened by condensed water, can cause
corrosion. Overpressuring the unit is another potential hazard that causes failures.
c. Health. Because this is a closed process, there is little potential for exposure to crude oil unless a leak or
release occurs. Where elevated operating temperatures are used when desalting sour crudes, hydrogen
sulfide will be present. There is the possibility of exposure to ammonia, dry chemical demulsifiers, caustics,
and/or acids during this operation. Safe work practices and/or the use of appropriate personal protective
equipment may be needed for exposures to chemicals and other hazards such as heat, and during process
sampling, inspection, maintenance, and turnaround activities.
Depending on the crude feedstock and the treatment chemicals used, the wastewater will contain varying
amounts of chlorides, sulfides, bicarbonates, ammonia, hydrocarbons, phenol, and suspended solids. If
diatomaceous earth is used in filtration, exposures should be minimized or controlled. Diatomaceous earth
can contain silica in very fine particle size, making this a potential respiratory hazard.

Back to Top
CRUDE OIL DISTILLATION (FRACTIONATION)
1. Description. The first step in the refining process is the separation of crude oil into various fractions or
straight-run cuts by distillation in atmospheric and vacuum towers. The main fractions or "cuts" obtained
have specific boiling-point ranges and can be classified in order of decreasing volatility into gases, light
distillates, middle distillates, gas oils, and residuum.
2. Atmospheric Distillation Tower.
a. At the refinery, the desalted crude feedstock is preheated using recovered process heat. The feedstock
then flows to a direct-fired crude charge heater where it is fed into the vertical distillation column just above
the bottom, at pressures slightly above atmospheric and at temperatures ranging from 650 to 700 F
(heating crude oil above these temperatures may cause undesirable thermal cracking). All but the heaviest
fractions flash into vapor. As the hot vapor rises in the tower, its temperature is reduced. Heavy fuel oil or
asphalt residue is taken from the bottom. At successively higher points on the tower, the various major
products including lubricating oil, heating oil, kerosene, gasoline, and uncondensed gases (which condense
at lower temperatures) are drawn off.
b. The fractionating tower, a steel cylinder about 120 feet high, contains horizontal steel trays for separating
and collecting the liquids. At each tray, vapors from below enter perforations and bubble caps. They permit
the vapors to bubble through the liquid on the tray, causing some condensation at the temperature of that
tray. An overflow pipe drains the condensed liquids from each tray back to the tray below, where the higher
temperature causes re-evaporation. The evaporation, condensing, and scrubbing operation is repeated
many times until the desired degree of product purity is reached. Then side streams from certain trays are
taken off to obtain the desired fractions. Products ranging from uncondensed fixed gases at the top to heavy
fuel oils at the bottom can be taken continuously from a fractionating tower. Steam is often used in towers to
lower the vapor pressure and create a partial vacuum. The distillation process separates the major
constituents of crude oil into so-called straight-run products. Sometimes crude oil is "topped" by distilling off
only the lighter fractions, leaving a heavy residue that is often distilled further under high vacuum.
TABLE IV:2-5. ATMOSPHERIC DISTILLATION PROCESS
Feedstock

From

Process

Typical products

Crude

Desalting Separation Gases

To
Atmospheric distillation tower

Naphthas

Reforming or treating

Kerosene or distillates

Treating

Gas oil

Catalytic cracking

Residual

Vacuum tower or visbreaker

FIGURE IV:2-8. ATMOSPHERIC DISTILLATION.

3. Vacuum Distillation Tower. In order to further distill the residuum or topped crude from the atmospheric
tower at higher temperatures, reduced pressure is required to prevent thermal cracking. The process takes
place in one or more vacuum distillation towers. The principles of vacuum distillation resemble those of
fractional distillation and, except that larger-diameter columns are used to maintain comparable vapor
velocities at the reduced pressures, the equipment is also similar. The internal designs of some vacuum
towers are different from atmospheric towers in that random packing and demister pads are used instead of
trays. A typical first-phase vacuum tower may produce gas oils, lubricating-oil base stocks, and heavy
residual for propane deasphalting. A second-phase tower operating at lower vacuum may distill surplus
residuum from the atmospheric tower, which is not used for lube-stock processing, and surplus residuum
from the first vacuum tower not used for deasphalting. Vacuum towers are typically used to separate
catalytic cracking feedstock from surplus residuum.
4. Other Distillation Towers (Columns). Within refineries there are numerous other, smaller distillation
towers called columns, designed to separate specific and unique products. Columns all work on the same
principles as the towers described above. For example, a depropanizer is a small column designed to
separate propane and lighter gases from butane and heavier components. Another larger column is used to
separate ethyl benzene and xylene. Small "bubble" towers called strippers use steam to remove trace
amounts of light products from heavier product streams.
5. Health and Safety Considerations.
a. Fire Prevention and Protection. Even though these are closed processes, heaters and exchangers in
the atmospheric and vacuum distillation units could provide a source of ignition, and the potential for a fire
exists should a leak or release occur.
b. Safety. An excursion in pressure, temperature, or liquid levels may occur if automatic control devices fail.
Control of temperature, pressure, and reflux within operating parameters is needed to prevent thermal
cracking within the distillation towers. Relief systems should be provided for overpressure and operations
monitored to prevent crude from entering the reformer charge.
The sections of the process susceptible to corrosion include (but may not be limited to) preheat exchanger
(HCl and H2S), preheat furnace and bottoms exchanger (H2S and sulfur compounds), atmospheric tower

and vacuum furnace (H2S, sulfur compounds, and organic acids), vacuum tower (H2S and organic acids),
and overhead (H2S, HCl, and water). Where sour crudes are processed, severe corrosion can occur in
furnace tubing and in both atmospheric and vacuum towers where metal temperatures exceed 450 F. Wet
H2S also will cause cracks in steel. When processing high-nitrogen crudes, nitrogen oxides can form in the
flue gases of furnaces. Nitrogen oxides are corrosive to steel when cooled to low temperatures in the
presence of water.
Chemicals are used to control corrosion by hydrochloric acid produced in distillation units. Ammonia may be
injected into the overhead stream prior to initial condensation and/or an alkaline solution may be carefully
injected into the hot crude-oil feed. If sufficient wash-water is not injected, deposits of ammonium chloride
can form and cause serious corrosion. Crude feedstock may contain appreciable amounts of water in
suspension which can separate during startup and, along with water remaining in the tower from steam
purging, settle in the bottom of the tower. This water can be heated to the boiling point and create an
instantaneous vaporization explosion upon contact with the oil in the unit.
c. Health. Atmospheric and vacuum distillation are closed processes and exposures are expected to be
minimal. When sour (high-sulfur) crudes are processed, there is potential for exposure to hydrogen sulfide in
the preheat exchanger and furnace, tower flash zone and overhead system, vacuum furnace and tower, and
bottoms exchanger. Hydrogen chloride may be present in the preheat exchanger, tower top zones, and
overheads. Wastewater may contain water-soluble sulfides in high concentrations and other water-soluble
compounds such as ammonia, chlorides, phenol, mercaptans, etc., depending upon the crude feedstock
and the treatment chemicals. Safe work practices and/or the use of appropriate personal protective
equipment may be needed for exposures to chemicals and other hazards such as heat and noise, and
during sampling, inspection, maintenance, and turnaround activities.
TABLE IV:2-6. VACUUM DISTILLATION PROCESS
Feedstock

From

Process

Residuals

Atmospheric tower Separation Gas oils

FIGURE IV:2-9. VACUUM DISTILLATION.

Typical products

To
Catalytic cracker

Lubricants

Hydrotreating or solvent

Residual

Deasphalter, visbreaker, or coker

Back to Top
SOLVENT EXTRACTION AND DEWAXING
1. Description. Solvent treating is a widely used method of refining lubricating oils as well as a host of other
refinery stocks. Since distillation (fractionation) separates petroleum products into groups only by their
boiling-point ranges, impurities may remain. These include organic compounds containing sulfur, nitrogen,
and oxygen; inorganic salts and dissolved metals; and soluble salts that were present in the crude
feedstock. In addition, kerosene and distillates may have trace amounts of aromatics and naphthenes, and
lubricating oil base-stocks may contain wax. Solvent refining processes including solvent extraction and
solvent dewaxing usually remove these undesirables at intermediate refining stages or just before sending
the product to storage.
2. Solvent Extraction.
a. The purpose of solvent extraction is to prevent corrosion, protect catalyst in subsequent processes, and
improve finished products by removing unsaturated, aromatic hydrocarbons from lubricant and grease
stocks. The solvent extraction process separates aromatics, naphthenes, and impurities from the product
stream by dissolving or precipitation. The feedstock is first dried and then treated using a continuous
countercurrent solvent treatment operation. In one type of process, the feedstock is washed with a liquid in
which the substances to be removed are more soluble than in the desired resultant product. In another
process, selected solvents are added to cause impurities to precipitate out of the product. In the adsorption
process, highly porous solid materials collect liquid molecules on their surfaces.
b. The solvent is separated from the product stream by heating, evaporation, or fractionation, and residual
trace amounts are subsequently removed from the raffinate by steam stripping or vacuum flashing. Electric
precipitation may be used for separation of inorganic compounds. The solvent is then regenerated to be
used again in the process.
c. The most widely used extraction solvents are phenol, furfural, and cresylic acid. Other solvents less
frequently used are liquid sulfur dioxide, nitrobenzene, and 2,2'-dichloroethyl ether. The selection of specific
processes and chemical agents depends on the nature of the feedstock being treated, the contaminants
present, and the finished product requirements.
TABLE IV:2-7. SOLVENT EXTRACTION PROCESS
Feedstock

From

Process

Typical products

To

Naphthas, distillates,
kerosene

Atm.
tower

Treating/
blending

High octane
gasoline

Storage

Refined fuels

Treating and blending

Spent agents

Treatment and blending

FIGURE IV:2-10. AROMATICS EXTRACTION.

3. Solvent Dewaxing. Solvent dewaxing is used to remove wax from either distillate or residual basestocks
at any stage in the refining process. There are several processes in use for solvent dewaxing, but all have
the same general steps, which are: (1) mixing the feedstock with a solvent, (2) precipitating the wax from the
mixture by chilling, and (3) recovering the solvent from the wax and dewaxed oil for recycling by distillation
and steam stripping. Usually two solvents are used: toluene, which dissolves the oil and maintains fluidity at
low temperatures, and methyl ethyl ketone (MEK), which dissolves little wax at low temperatures and acts as
a wax precipitating agent. Other solvents that are sometimes used include benzene, methyl isobutyl ketone,
propane, petroleum naphtha, ethylene dichloride, methylene chloride, and sulfur dioxide. In addition, there is
a catalytic process used as an alternate to solvent dewaxing.
TABLE IV:2-8. SOLVENT DEWAXING PROCESS
Feedstock

From

Process

Lube basestock Vacuum tower Treating

FIGURE IV:2-11. SOLVENT DEWAXING.

Typical products

To

Dewaxed lubes

Hydrotreating

Wax

Hydrotreating

Spent agents

Treatment or recycle

Note: Diagrams in Figures IV:2-10, 11, 12, 13, 15, and 20 reproduced with permission from Shell
International Petroleum Company.
4. Health and Safety Considerations.
a. Fire Prevention and Protection. Solvent treatment is essentially a closed process and, although
operating pressures are relatively low, the potential exists for fire from a leak or spill contacting a source of
ignition such as the drier or extraction heater. In solvent dewaxing, disruption of the vacuum will create a
potential fire hazard by allowing air to enter the unit.
b. Health. Because solvent extraction is a closed process, exposures are expected to be minimal under
normal operating conditions. However, there is a potential for exposure to extraction solvents such as
phenol, furfural, glycols, methyl ethyl ketone, amines, and other process chemicals. Safe work practices
and/or the use of appropriate personal protective equipment may be needed for exposures to chemicals and
other hazards such as noise and heat, and during repair, inspection, maintenance, and turnaround activities.
Back to Top
THERMAL CRACKING
1. Description.
a. Because the simple distillation of crude oil produces amounts and types of products that are not
consistent with those required by the marketplace, subsequent refinery processes change the product mix
by altering the molecular structure of the hydrocarbons. One of the ways of accomplishing this change is
through "cracking," a process that breaks or cracks the heavier, higher boiling-point petroleum fractions into
more valuable products such as gasoline, fuel oil, and gas oils. The two basic types of cracking are thermal
cracking, using heat and pressure, and catalytic cracking.
b. The first thermal cracking process was developed around 1913. Distillate fuels and heavy oils were
heated under pressure in large drums until they cracked into smaller molecules with better antiknock
characteristics. However, this method produced large amounts of solid, unwanted coke. This early process
has evolved into the following applications of thermal cracking: visbreaking, steam cracking, and coking.
2. Visbreaking Process. Visbreaking, a mild form of thermal cracking, significantly lowers the viscosity of
heavy crude-oil residue without affecting the boiling point range. Residual from the atmospheric distillation
tower is heated (800-950 F) at atmospheric pressure and mildly cracked in a heater. It is then quenched

with cool gas oil to control overcracking, and flashed in a distillation tower. Visbreaking is used to reduce the
pour point of waxy residues and reduce the viscosity of residues used for blending with lighter fuel oils.
Middle distillates may also be produced, depending on product demand. The thermally cracked residue tar,
which accumulates in the bottom of the fractionation tower, is vacuum flashed in a stripper and the distillate
recycled.
TABLE IV:2-9. VISBREAKING PROCESS.
Feedstock

From

Process

Typical products To

Residual

Atmospheric tower &

Vacuum tower

Decompose

Gasoline or
distillate

Hydrotreating

Vapor

Hydrotreater

Residue

Stripper or recycle

Gases

Gas plant

FIGURE IV:2-12. VISBREAKING.

3. Steam Cracking Process. Steam cracking is a petrochemical process sometimes used in refineries to
produce olefinic raw materials (e.g., ethylene) from various feedstock for petrochemicals manufacture. The
feedstock range from ethane to vacuum gas oil, with heavier feeds giving higher yields of by-products such
as naphtha. The most common feeds are ethane, butane, and naphtha. Steam cracking is carried out at
temperatures of 1,500-1,600 F, and at pressures slightly above atmospheric. Naphtha produced from
steam cracking contains benzene, which is extracted prior to hydrotreating. Residual from steam cracking is
sometimes blended into heavy fuels.
4. Coking Processes. Coking is a severe method of thermal cracking used to upgrade heavy residuals into
lighter products or distillates. Coking produces straight-run gasoline (coker naphtha) and various middledistillate fractions used as catalytic cracking feedstock. The process so completely reduces hydrogen that
the residue is a form of carbon called "coke." The two most common processes are delayed coking and
continuous (contact or fluid) coking. Three typical types of coke are obtained (sponge coke, honeycomb
coke, and needle coke) depending upon the reaction mechanism, time, temperature, and the crude
feedstock.
a. Delayed Coking. In delayed coking the heated charge (typically residuum from atmospheric distillation
towers) is transferred to large coke drums which provide the long residence time needed to allow the

cracking reactions to proceed to completion. Initially the heavy feedstock is fed to a furnace which heats the
residuum to high temperatures (900-950 F) at low pressures (25-30 psi) and is designed and controlled to
prevent premature coking in the heater tubes. The mixture is passed from the heater to one or more coker
drums where the hot material is held approximately 24 hours (delayed) at pressures of 25-75 psi, until it
cracks into lighter products. Vapors from the drums are returned to a fractionator where gas, naphtha, and
gas oils are separated out. The heavier hydrocarbons produced in the fractionator are recycled through the
furnace.
After the coke reaches a predetermined level in one drum, the flow is diverted to another drum to maintain
continuous operation. The full drum is steamed to strip out uncracked hydrocarbons, cooled by water
injection, and decoked by mechanical or hydraulic methods. The coke is mechanically removed by an auger
rising from the bottom of the drum. Hydraulic decoking consists of fracturing the coke bed with high-pressure
water ejected from a rotating cutter.
b. Continuous Coking. Continuous (contact or fluid) coking is a moving-bed process that operates at
temperatures higher than delayed coking. In continuous coking, thermal cracking occurs by using heat
transferred from hot, recycled coke particles to feedstock in a radial mixer, called a reactor, at a pressure of
50 psi. Gases and vapors are taken from the reactor, quenched to stop any further reaction, and
fractionated. The reacted coke enters a surge drum and is lifted to a feeder and classifier where the larger
coke particles are removed as product. The remaining coke is dropped into the preheater for recycling with
feedstock. Coking occurs both in the reactor and in the surge drum. The process is automatic in that there is
a continuous flow of coke and feedstock.
TABLE IV: 2-10. COKING PROCESSES.
Feedstock

From

Process

Typical products

To

Residual

Atmospheric & vacuum

catalytic cracker

Decomposition

Naphtha, gasoline,
column,blending

Distillation

Clarified oil Catalytic cracker

Coke

Shipping, recycle

Tars

Various units

Gas oil

Catalytic cracking

Wasteater
(sour)

Treatment

Gases

Gas plant

FIGURE IV:2-13. DELAYED COKING.

5. Health and Safety Considerations.

a. Fire Protection and Prevention. Because thermal cracking is a closed process, the primary potential for
fire is from leaks or releases of liquids, gases, or vapors reaching an ignition source such as a heater. The
potential for fire is present in coking operations due to vapor or product leaks. Should coking temperatures
get out of control, an exothermic reaction could occur within the coker.
b. Safety. In thermal cracking when sour crudes are processed, corrosion can occur where metal
temperatures are between 450 and 900 F. Above 900 F coke forms a protective layer on the metal. The
furnace, soaking drums, lower part of the tower, and high-temperature exchangers are usually subject to
corrosion. Hydrogen sulfide corrosion in coking can also occur when temperatures are not properly
controlled above 900 F.
Continuous thermal changes can lead to bulging and cracking of coke drum shells. In coking, temperature
control must often be held within a 10-20 F range, as high temperatures will produce coke that is too hard
to cut out of the drum. Conversely, temperatures that are too low will result in a high asphaltic-content slurry.
Water or steam injection may be used to prevent buildup of coke in delayed coker furnace tubes. Water
must be completely drained from the coker, so as not to cause an explosion upon recharging with hot coke.
Provisions for alternate means of egress from the working platform on top of coke drums are important in the
event of an emergency.
c. Health. The potential exists for exposure to hazardous gases such as hydrogen sulfide and carbon
monoxide, and trace polynuclear aromatics (PNA's) associated with coking operations. When coke is moved
as a slurry, oxygen depletion may occur within confined spaces such as storage silos, since wet carbon will
adsorb oxygen. Wastewater may be highly alkaline and contain oil, sulfides, ammonia, and/or phenol. The
potential exists in the coking process for exposure to burns when handling hot coke or in the event of a
steam-line leak, or from steam, hot water, hot coke, or hot slurry that may be expelled when opening cokers.
Safe work practices and/or the use of appropriate personal protective equipment may be needed for
exposures to chemicals and other hazards such as heat and noise, and during process sampling,
inspection, maintenance, and turnaround activities. (Note: coke produced from petroleum is a different
product from that generated in the steel-industry coking process.)
Back to Top
CATALYTIC CRACKING
1. Description.
a. Catalytic cracking breaks complex hydrocarbons into simpler molecules in order to increase the quality
and quantity of lighter, more desirable products and decrease the amount of residuals. This process
rearranges the molecular structure of hydrocarbon compounds to convert heavy hydrocarbon feedstock into
lighter fractions such as kerosene, gasoline, LPG, heating oil, and petrochemical feedstock.
b. Catalytic cracking is similar to thermal cracking except that catalysts facilitate the conversion of the
heavier molecules into lighter products. Use of a catalyst (a material that assists a chemical reaction but
does not take part in it) in the cracking reaction increases the yield of improved-quality products under much
less severe operating conditions than in thermal cracking. Typical temperatures are from 850-950 F at
much lower pressures of 10-20 psi. The catalysts used in refinery cracking units are typically solid materials
(zeolite, aluminum hydrosilicate, treated bentonite clay, fuller's earth, bauxite, and silica-alumina) that come
in the form of powders, beads, pellets or shaped materials called extrudites.
c. There are three basic functions in the catalytic cracking process:

Reaction: Feedstock reacts with catalyst and cracks into different hydrocarbons;
Regeneration: Catalyst is reactivated by burning off coke; and
Fractionation: Cracked hydrocarbon stream is separated into various products.

d. The three types of catalytic cracking processes are fluid catalytic cracking (FCC), moving-bed catalytic
cracking, and Thermofor catalytic cracking (TCC). The catalytic cracking process is very flexible, and
operating parameters can be adjusted to meet changing product demand. In addition to cracking, catalytic
activities include dehydrogenation, hydrogenation, and isomerization.

TABLE IV: 2-11. CATALYTIC CRACKING PROCESS

Feedstock

From

Process

Typical products

To

Gas oils

Towers,
coker

Decomposition,
alteration

Gasoline

Treater or blend

Gases

Gas plant

Middle distillates

Hydrotreat, blend, or recycle

Petrochem
feedstock

Petrochem or other

Residue

Residual fuel blend

visbreaker

Deasphalted
oils

Deasphalter

Back to Top
FLUID CATALYTIC CRACKING
1. Description.
a. The most common process is FCC, in which the oil is cracked in the presence of a finely divided catalyst
which is maintained in an aerated or fluidized state by the oil vapors. The fluid cracker consists of a catalyst
section and a fractionating section that operate together as an integrated processing unit. The catalyst
section contains the reactor and regenerator, which, with the standpipe and riser, forms the catalyst
circulation unit. The fluid catalyst is continuously circulated between the reactor and the regenerator using
air, oil vapors, and steam as the conveying media.
b. A typical FCC process involves mixing a preheated hydrocarbon charge with hot, regenerated catalyst as
it enters the riser leading to the reactor. The charge is combined with a recycle stream within the riser,
vaporized, and raised to reactor temperature (900-1,000 F) by the hot catalyst. As the mixture travels up
the riser, the charge is cracked at 10-30 psi. In the more modern FCC units, all cracking takes place in the
riser. The "reactor" no longer functions as a reactor; it merely serves as a holding vessel for the cyclones.
This cracking continues until the oil vapors are separated from the catalyst in the reactor cyclones. The
resultant product stream (cracked product) is then charged to a fractionating column where it is separated
into fractions, and some of the heavy oil is recycled to the riser.
c. Spent catalyst is regenerated to get rid of coke that collects on the catalyst during the process. Spent
catalyst flows through the catalyst stripper to the regenerator, where most of the coke deposits burn off at
the bottom where preheated air and spent catalyst are mixed. Fresh catalyst is added and worn-out catalyst
removed to optimize the cracking process.

FIGURE IV:2-14. FLUID CATALYTIC CRACKING

2. Moving Bed Catalytic Cracking. The moving-bed catalytic cracking process is similar to the FCC
process. The catalyst is in the form of pellets that are moved continuously to the top of the unit by conveyor
or pneumatic lift tubes to a storage hopper, then flow downward by gravity through the reactor, and finally to
a regenerator. The regenerator and hopper are isolated from the reactor by steam seals. The cracked
product is separated into recycle gas, oil, clarified oil, distillate, naphtha, and wet gas.
3. Thermofor Catalytic Cracking. In a typical thermofor catalytic cracking unit, the preheated feedstock
flows by gravity through the catalytic reactor bed. The vapors are separated from the catalyst and sent to a
fractionating tower. The spent catalyst is regenerated, cooled, and recycled. The flue gas from regeneration
is sent to a carbon-monoxide boiler for heat recovery.
4. Health and Safety Considerations.
a. Fire Prevention and Protection. Liquid hydrocarbons in the catalyst or entering the heated combustion
air stream should be controlled to avoid exothermic reactions. Because of the presence of heaters in
catalytic cracking units, the possibility exists for fire due to a leak or vapor release. Fire protection including
concrete or other insulation on columns and supports, or fixed water spray or fog systems where insulation
is not feasible and in areas where firewater hose streams cannot reach, should be considered.
In some processes, caution must be taken to prevent explosive concentrations of catalyst dust during
recharge or disposal. When unloading any coked catalyst, the possibility exists for iron sulfide fires. Iron
sulfide will ignite spontaneously when exposed to air and therefore must be wetted with water to prevent it
from igniting vapors. Coked catalyst may be either cooled below 120 F before it is dumped from the reactor,
or dumped into containers that have been purged and inerted with nitrogen and then cooled before further
handling.
b. Safety. Regular sampling and testing of the feedstock, product, and recycle streams should be performed
to assure that the cracking process is working as intended and that no contaminants have entered the
process stream. Corrosives or deposits in the feedstock can foul gas compressors. Inspections of critical
equipment including pumps, compressors, furnaces, and heat exchangers should be conducted as needed.
When processing sour crude, corrosion may be expected where temperatures are below 900 F. Corrosion
takes place where both liquid and vapor phases exist, and at areas subject to local cooling such as nozzles
and platform supports.
When processing high-nitrogen feedstock, exposure to ammonia and cyanide may occur, subjecting carbon
steel equipment in the FCC overhead system to corrosion, cracking, or hydrogen blistering. These effects

may be minimized by water wash or corrosion inhibitors. Water wash may also be used to protect overhead
condensers in the main column subjected to fouling from ammonium hydrosulfide. Inspections should
include checking for leaks due to erosion or other malfunctions such as catalyst buildup on the expanders,
coking in the overhead feeder lines from feedstock residues, and other unusual operating conditions.
c. Health. Because the catalytic cracker is a closed system, there is normally little opportunity for exposure
to hazardous substances during normal operations. The possibility exists of exposure to extremely hot (700
F) hydrocarbon liquids or vapors during process sampling or if a leak or release occurs. In addition,
exposure to hydrogen sulfide and/or carbon monoxide gas may occur during a release of product or vapor.
Catalyst regeneration involves steam stripping and decoking, and produces fluid waste streams that may
contain varying amounts of hydrocarbon, phenol, ammonia, hydrogen sulfide, mercaptan, and other
materials depending upon the feedstock, crudes, and processes. Inadvertent formation of nickel carbonyl
may occur in cracking processes using nickel catalysts, with resultant potential for hazardous exposures.
Safe work practices and/or the use of appropriate personal protective equipment may be needed for
exposures to chemicals and other hazards such as noise and heat; during process sampling, inspection,
maintenance and turnaround activities; and when handling spent catalyst, recharging catalyst, or if leaks or
releases occur.
Back to Top
HYDROCRACKING
1. Description.
a. Hydrocracking is a two-stage process combining catalytic cracking and hydrogenation, wherein heavier
feedstocks are cracked in the presence of hydrogen to produce more desirable products. The process
employs high pressure, high temperature, a catalyst, and hydrogen. Hydrocracking is used for feedstocks
that are difficult to process by either catalytic cracking or reforming, since these feedstocks are
characterized usually by a high polycyclic aromatic content and/or high concentrations of the two principal
catalyst poisons, sulfur and nitrogen compounds.
b. The hydrocracking process largely depends 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 (1,000-2,000 psi) and fairly high temperatures (7501,500 F), in the presence of hydrogen and special catalysts. When the feedstock has a high paraffinic
content, the primary function of hydrogen is to prevent the formation of polycyclic aromatic compounds.
Another important role of hydrogen in the hydrocracking process is to reduce tar formation and prevent
buildup of coke on the catalyst. Hydrogenation also serves to convert sulfur and nitrogen compounds
present in the feedstock to hydrogen sulfide and ammonia.
c. Hydrocracking produces relatively large amounts of isobutane for alkylation feedstock. Hydrocracking also
performs isomerization for pour-point control and smoke-point control, both of which are important in highquality jet fuel.
2. Hydrocracking Process.
a. In the first stage, preheated feedstock is mixed with recycled hydrogen and sent to the first-stage reactor,
where catalysts convert sulfur and nitrogen compounds to hydrogen sulfide and ammonia. Limited
hydrocracking also occurs.
b. After the hydrocarbon leaves the first stage, it is cooled and liquefied and run through a hydrocarbon
separator. The hydrogen is recycled to the feedstock. The liquid is charged to a fractionator. Depending on
the products desired (gasoline components, jet fuel, and gas oil), the fractionator is run to cut out some
portion of the first stage reactor out-turn. Kerosene-range material can be taken as a separate side-draw
product or included in the fractionator bottoms with the gas oil.

c. The fractionator bottoms are again mixed with a hydrogen stream and charged to the second stage. Since
this material has already been subjected to some hydrogenation, cracking, and reforming in the first stage,
the operations of the second stage are more severe (higher temperatures and pressures). Like the outturn of
the first stage, the second stage product is separated from the hydrogen and charged to the fractionator.
TABLE IV: 2-12. HYDROCRACKING PROCESS.

Feedstock

From

Process

Typical
products

To

High pour
point

Catalytic cracker,
atmospheric & vacuum
tower

Decomposition,
hydrogenation

Kerosene, jet
fuel

Blending

Gas oil

Vacuum tower, coker

Gasoline,
distillates

Blending

Hydrogen

Reformer

Recycle,
reformer gas

Gas plant

FIGURE IV:2-15. TWO-STAGE HYDROCRACKING.

3. Health and Safety Considerations.

a. Fire Prevention and Protection. Because this unit operates at very high pressures and temperatures,
control of both hydrocarbon leaks and hydrogen releases is important to prevent fires. In some processes,
care is needed to ensure that explosive concentrations of catalytic dust do not form during recharging.

b. Safety. Inspection and testing of safety relief devices are important due to the very high pressures in this
unit. Proper process control is needed to protect against plugging reactor beds. Unloading coked catalyst
requires special precautions to prevent iron sulfide-induced fires. The coked catalyst should either be cooled
to below 120 F before dumping, or be placed in nitrogen-inerted containers until cooled.
Because of the operating temperatures and presence of hydrogen, the hydrogen-sulfide content of the
feedstock must be strictly controlled to a minimum to reduce the possibility of severe corrosion. Corrosion by
wet carbon dioxide in areas of condensation also must be considered. When processing high-nitrogen
feedstock, the ammonia and hydrogen sulfide form ammonium hydrosulfide, which causes serious corrosion
at temperatures below the water dew point. Ammonium hydrosulfide is also present in sour water stripping.
c. Health. Because this is a closed process, exposures are expected to be minimal under normal operating
conditions. There is a potential for exposure to hydrocarbon gas and vapor emissions, hydrogen and
hydrogen sulfide gas due to high-pressure leaks. Large quantities of carbon monoxide may be released
during catalyst regeneration and changeover. Catalyst steam stripping and regeneration create waste
streams containing sour water and ammonia. Safe work practices and/or the use of appropriate personal
protective equipment may be needed for exposure to chemicals and other hazards such as noise and heat,
during process sampling, inspection, maintenance, and turnaround activities, and when handling spent
catalyst.
Back to Top
CATALYTIC REFORMING
1. Description.
a. Catalytic reforming is an important process used to convert low-octane naphthas into high-octane
gasoline blending components called reformates. Reforming represents the total effect of numerous
reactions such as cracking, polymerization, dehydrogenation, and isomerization taking place simultaneously.
Depending on the properties of the naphtha feedstock (as measured by the paraffin, olefin, naphthene, and
aromatic content) and catalysts used, reformates can be produced with very high concentrations of toluene,
benzene, xylene, and other aromatics useful in gasoline blending and petrochemical processing. Hydrogen,
a significant by-product, is separated from the reformate for recycling and use in other processes.
b. A catalytic reformer comprises a reactor section and a product-recovery section. More or less standard is
a feed preparation section in which, by combination of hydrotreatment and distillation, the feedstock is
prepared to specification. Most processes use platinum as the active catalyst. Sometimes platinum is
combined with a second catalyst (bimetallic catalyst) such as rhenium or another noble metal.
c. There are many different commercial catalytic reforming processes including platforming, powerforming,
ultraforming, and Thermofor catalytic reforming. In the platforming process, the first step is preparation of the
naphtha feed to remove impurities from the naphtha and reduce catalyst degradation. The naphtha
feedstock is then mixed with hydrogen, vaporized, and passed through a series of alternating furnace and
fixed-bed reactors containing a platinum catalyst. The effluent from the last reactor is cooled and sent to a
separator to permit removal of the hydrogen-rich gas stream from the top of the separator for recycling. The
liquid product from the bottom of the separator is sent to a fractionator called a stabilizer (butanizer). It
makes a bottom product called reformate; butanes and lighter go overhead and are sent to the saturated
gas plant.
d. Some catalytic reformers operate at low pressure (50-200 psi), and others operate at high pressures (up
to 1,000 psi). Some catalytic reforming systems continuously regenerate the catalyst in other systems. One
reactor at a time is taken off-stream for catalyst regeneration, and some facilities regenerate all of the
reactors during turnarounds.
2. Health and Safety Considerations.
a. Fire Prevention and Protection. This is a closed system; however, the potential for fire exists should a
leak or release of reformate gas or hydrogen occur.

b. Safety. Operating procedures should be developed to ensure control of hot spots during start-up. Safe
catalyst handling is very important. Care must be taken not to break or crush the catalyst when loading the
beds, as the small fines will plug up the reformer screens. Precautions against dust when regenerating or
replacing catalyst should also be considered. Also, water wash should be considered where stabilizer fouling
has occurred due to the formation of ammonium chloride and iron salts. Ammonium chloride may form in
pretreater exchangers and cause corrosion and fouling. Hydrogen chloride from the hydrogenation of
chlorine compounds may form acid or ammonium chloride salt.
c. Health. Because this is a closed process, exposures are expected to be minimal under normal operating
conditions. There is potential for exposure to hydrogen sulfide and benzene should a leak or release occur.
Small emissions of carbon monoxide and hydrogen sulfide may occur during regeneration of catalyst. Safe
work practices and/or appropriate personal protective equipment may be needed for exposures to chemicals
and other hazards such as noise and heat during testing, inspecting, maintenance and turnaround activities,
and when handling regenerated or spent catalyst.
TABLE IV: 2-13. CATALYTIC REFORMING PROCESS

Feedstock

From

Process

Typical
products

To

Desulfurized
naphtha

Coker

Rearrange,
dehydrogenate

High octane
gasoline

Blending

Aromatics

Petrochemical

Naphthene-rich
fractions

hydrocracker,
hydrodesulfur

Hydrogen

Recycle, hydrotreat, etc.

Straight-run
naphtha

Atmospheric
fractionator

Gas

Gas plant

FIGURE IV:2-16. PLATFORMING PROCESS.

Back to Top

CATALYTIC HYDROTREATING
1. Description. Catalytic hydrotreating is a hydrogenation process used to remove about 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.
Typically, hydrotreating is done prior to processes such as catalytic reforming so that the catalyst is not
contaminated by untreated feedstock. Hydrotreating is also used prior to catalytic cracking to reduce sulfur
and improve product yields, and to upgrade middle-distillate petroleum fractions into finished kerosene,
diesel fuel, and heating fuel oils. In addition, hydrotreating converts olefins and aromatics to saturated
compounds.
2. Catalytic Hydrodesulfurization Process. Hydrotreating for sulfur removal is called hydrodesulfurization.
In a typical catalytic hydrodesulfurization unit, the feedstock is deaerated and mixed with hydrogen,
preheated in a fired heater (600-800 F) and then charged under pressure (up to 1,000 psi) through a fixedbed catalytic reactor. In the reactor, the sulfur and nitrogen compounds in the feedstock are converted into
H2S and NH3. The reaction products leave the reactor and after cooling to a low temperature enter a
liquid/gas separator. The hydrogen-rich gas from the high-pressure separation is recycled to combine with
the feedstock, and the low-pressure gas stream rich in H2S is sent to a gas treating unit where H2S is
removed. The clean gas is then suitable as fuel for the refinery furnaces. The liquid stream is the product
from hydrotreating and is normally sent to a stripping column for removal of H2S and other undesirable
components. In cases where steam is used for stripping, the product is sent to a vacuum drier for removal of
water. Hydrodesulfurized products are blended or used as catalytic reforming feedstock.
3. Other Hydrotreating Processes.
a. Hydrotreating processes differ depending upon the feedstock available and catalysts used. Hydrotreating
can be used to improve the burning characteristics of distillates such as kerosene. Hydrotreatment of a
kerosene fraction can convert aromatics into naphthenes, which are cleaner-burning compounds.
b. Lube-oil hydrotreating uses catalytic treatment of the oil with hydrogen to improve product quality. The
objectives in mild lube hydrotreating include saturation of olefins and improvements in color, odor, and acid
nature of the oil. Mild lube hydrotreating also may be used following solvent processing. Operating
temperatures are usually below 600 F and operating pressures below 800 psi. Severe lube hydrotreating,
at temperatures in the 600-750 F range and hydrogen pressures up to 3,000 psi, is capable of saturating
aromatic rings, along with sulfur and nitrogen removal, to impart specific properties not achieved at mild
conditions.
c. Hydrotreating also can be employed to improve the quality of pyrolysis gasoline (pygas), a by-product
from the manufacture of ethylene. Traditionally, the outlet for pygas has been motor gasoline blending, a
suitable route in view of its high octane number. However, only small portions can be blended untreated
owing to the unacceptable odor, color, and gum-forming tendencies of this material. The quality of pygas,
which is high in diolefin content, can be satisfactorily improved by hydrotreating, whereby conversion of
diolefins into mono-olefins provides an acceptable product for motor gas blending.
TABLE IV: 2-14 HYDRODESULFURIZATION PROCESS

Feedstock

From

Process

Typical
products

To

Naphthas, distillates
sour gas oil,
residuals

Atmospheric & vacuum

tower, catalytic & thermal
cracker

Treating,
hydrogenation

Naphtha

Blending

Hydrogen

Recycle

Distillates

Blending

H2S,

Sulfure plant,

ammonia

treater

Gas

Gas plant

FIGURE IV:2-17. DISTILLATE HYDRODESULFURIZATION.

4. Health and Safety Considerations.

a. Fire Prevention and Protection. The potential exists for fire in the event of a leak or release of product
or hydrogen gas.
b. Safety. Many processes require hydrogen generation to provide for a continuous supply. Because of the
operating temperatures and presence of hydrogen, the hydrogen sulfide content of the feedstock must be
strictly controlled to a minimum to reduce corrosion. Hydrogen chloride may form and condense as
hydrochloric acid in the lower-temperature parts of the unit. Ammonium hydrosulfide may form in hightemperature, high-pressure units. Excessive contact time and/or temperature will create coking. Precautions
need to be taken when unloading coked catalyst from the unit to prevent iron sulfide fires. The coked
catalyst should be cooled to below 120 F before removal, or dumped into nitrogen-inerted bins where it can
be cooled before further handling. Special antifoam additives may be used to prevent catalyst poisoning
from silicone carryover in the coker feedstock.
c. Health. Because this is a closed process, exposures are expected to be minimal under normal operating
conditions. There is a potential for exposure to hydrogen sulfide or hydrogen gas in the event of a release,
or to ammonia should a sour-water leak or spill occur. Phenol also may be present if high boiling-point
feedstocks are processed. Safe work practices and/or appropriate personal protective equipment may be
needed for exposures to chemicals and other hazards such as noise and heat; during process sampling,
inspection, maintenance, and turnaround activities; and when handling amine or exposed to catalyst.
Back to Top
ISOMERIZATION
1. Description.
a. Isomerization converts n-butane, n-pentane and n-hexane into their respective isoparaffins of
substantially higher octane number. The straight-chain paraffins are converted to their branched-chain
counterparts whose component atoms are the same but are arranged in a different geometric structure.
Isomerization is important for the conversion of n-butane into isobutane, to provide additional feedstock for
alkylation units, and the conversion of normal pentanes and hexanes into higher branched isomers for

gasoline blending. Isomerization is similar to catalytic reforming in that the hydrocarbon molecules are
rearranged, but unlike catalytic reforming, isomerization just converts normal paraffins to isoparaffins.
b. There are two distinct isomerization processes, butane (C4) and pentane/hexane (C5/C6). Butane
isomerization produces feedstock for alkylation. Aluminum chloride catalyst plus hydrogen chloride are
universally used for the low-temperature processes. Platinum or another metal catalyst is used for the
higher-temperature processes. In a typical low-temperature process, the feed to the isomerization plant is nbutane or mixed butanes mixed with hydrogen (to inhibit olefin formation) and passed to the reactor at 230340 F and 200-300 psi. Hydrogen is flashed off in a high-pressure separator and the hydrogen chloride
removed in a stripper column. The resultant butane mixture is sent to a fractionator (deisobutanizer) to
separate n-butane from the isobutane product.
c. Pentane/hexane isomerization increases the octane number of the light gasoline components n-pentane
and n-hexane, which are found in abundance in straight-run gasoline. In a typical C5/C6 isomerization
process, dried and desulfurized feedstock is mixed with a small amount of organic chloride and recycled
hydrogen, and then heated to reactor temperature. It is then passed over supported-metal catalyst in the first
reactor where benzene and olefins are hydrogenated. The feed next goes to the isomerization reactor where
the paraffins are catalytically isomerized to isoparaffins. The reactor effluent is then cooled and
subsequently separated in the product separator into two streams: a liquid product (isomerate) and a recycle
hydrogen-gas stream. The isomerate is washed (caustic and water), acid stripped, and stabilized before
going to storage.
TABLE IV: 2-15. ISOMERIZATION PROCESSES
Feedstock

From

Process

Typical products

n-Butane

Various
Processes

Rearrangement Isobutane

To
Alkylation

n-Pentane

Isopentane

Blending

n-Hexane

Isohexane

Blending

Gas

Gas Plant

FIGURE IV:2-18. C4 ISOMERIZATION.

FIGURE IV:2-19. C5 AND C6 ISOMERIZATION.

2. Health and Safety Considerations.

a. Fire Protection and Prevention. Although this is a closed process, the potential for a fire exists should a
release or leak contact a source of ignition such as the heater.
b. Safety. If the feedstock is not completely dried and desulfurized, the potential exists for acid formation
leading to catalyst poisoning and metal corrosion. Water or steam must not be allowed to enter areas where
hydrogen chloride is present. Precautions are needed to prevent HCl from entering sewers and drains.
c. Health. Because this is a closed process, exposures are expected to be minimal during normal operating
conditions. There is a potential for exposure to hydrogen gas, hydrochloric acid, and hydrogen chloride and
to dust when solid catalyst is used. Safe work practices and/or appropriate personal protective equipment
may be needed for exposures to chemicals and other hazards such as heat and noise, and during process
sampling, inspection, maintenance, and turnaround activities.
Back to Top
POLYMERIZATION
1. Description.
a. Polymerization in the petroleum industry is the process of converting light olefin gases including ethylene,
propylene, and butylene into hydrocarbons of higher molecular weight and higher octane number that can
be used as gasoline blending stocks. Polymerization combines two or more identical olefin molecules to
form a single molecule with the same elements in the same proportions as the original molecules.
Polymerization may be accomplished thermally or in the presence of a catalyst at lower temperatures.

b. The olefin feedstock is pretreated to remove sulfur and other undesirable compounds. In the catalytic
process the feedstock is either passed over a solid phosphoric acid catalyst or comes in contact with liquid
phosphoric acid, where an exothermic polymeric reaction occurs. This reaction requires cooling water and
the injection of cold feedstock into the reactor to control temperatures between 300 and 450 F at
pressures from 200 psi to 1,200 psi. The reaction products leaving the reactor are sent to stabilization and/or
fractionator systems to separate saturated and unreacted gases from the polymer gasoline product.
NOTE: In the petroleum industry, polymerization is used to indicate the production of gasoline components,
hence the term "polymer" gasoline. Furthermore, it is not essential that only one type of monomer be
involved. If unlike olefin molecules are combined, the process is referred to as "copolymerization."
Polymerization in the true sense of the word is normally prevented, and all attempts are made to terminate
the reaction at the dimer or trimer (three monomers joined together) stage. However, in the petrochemical
section of a refinery, polymerization, which results in the production of, for instance, polyethylene, is allowed
to proceed until materials of the required high molecular weight have been produced.
2. Health and Safety Considerations.
a. Fire Prevention and Protection. Polymerization is a closed process where the potential for a fire exists
due to leaks or releases reaching a source of ignition.
b. Safety. The potential for an uncontrolled exothermic reaction exists should loss of cooling water occur.
Severe corrosion leading to equipment failure will occur should water make contact with the phosphoric acid,
such as during water washing at shutdowns. Corrosion may also occur in piping manifolds, reboilers,
exchangers, and other locations where acid may settle out.
c. Health. Because this is a closed system, exposures are expected to be minimal under normal operating
conditions. There is a potential for exposure to caustic wash (sodium hydroxide), to phosphoric acid used in
the process or washed out during turnarounds, and to catalyst dust. Safe work practices and/or appropriate
personal protective equipment may be needed for exposures to chemicals and other hazards such as noise
and heat, and during process sampling, inspection, maintenance, and turnaround activities.
TABLE IV: 2-16. POLYMERIZATION PROCESS
Feedstock

From

Process

Typical products

To

Olefins

Cracking
processes

Unification High octane naphtha Gasoline blending

Petrochem.
feedstock

Petrochemical

Liquefied petro. gas

Storage

FIGURE IV:2-20. POLYMERIZATION PROCESS.

Back to Top
ALKYLATION
1. Description. Alkylation combines low-molecular-weight olefins (primarily a mixture of propylene and
butylene) with isobutene in the presence of a catalyst, either sulfuric acid or hydrofluoric acid. The product is
called alkylate and is composed of a mixture of high-octane, branched-chain paraffinic hydrocarbons.
Alkylate is a premium blending stock because it has exceptional antiknock properties and is clean burning.
The octane number of the alkylate depends mainly upon the kind of olefins used and upon operating
conditions.
2. Sulfuric Acid Alkylation Process.
a. In cascade type sulfuric acid (H2SO4) alkylation units, the feedstock (propylene, butylene, amylene, and
fresh isobutane) enters the reactor and contacts the concentrated sulfuric acid catalyst (in concentrations of
85% to 95% for good operation and to minimize corrosion). The reactor is divided into zones, with olefins fed
through distributors to each zone, and the sulfuric acid and isobutanes flowing over baffles from zone to
zone.
b. 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 caustic for pH control before being
successively depropanized, deisobutanized, and debutanized. The alkylate obtained from the deisobutanizer
can then go directly to motor-fuel blending or be rerun to produce aviation-grade blending stock. The
isobutane is recycled to the feed.
3. Hydrofluoric Acid Alylation Process. Phillips and UOP are the two common types of hydrofluoric acid
alkylation processes in use. In the Phillips process, olefin and isobutane feedstock are dried and fed to a
combination reactor/settler system. Upon leaving the reaction zone, the reactor effluent flows to a settler
(separating vessel) where the acid separates from the hydrocarbons. The acid layer at the bottom of the
separating vessel is recycled. The top layer of hydrocarbons (hydrocarbon phase), consisting of propane,
normal butane, alkylate, and excess (recycle) isobutane, is charged to the main fractionator, the bottom
product of which is motor alkylate. The main fractionator overhead, consisting mainly of propane, isobutane,
and HF, goes to a depropanizer. Propane with trace amount of HF goes to an HF stripper for HF removal
and is then catalytically defluorinated, treated, and sent to storage. Isobutane is withdrawn from the main
fractionator and recycled to the reactor/settler, and alkylate from the bottom of the main fractionator is sent
to product blending.

4. The UOP process uses two reactors with separate settlers. Half of the dried feedstock is charged to the
first reactor, along with recycle and makeup isobutane. The reactor effluent then goes to its settler, where
the acid is recycled and the hydrocarbon charged to the second reactor. The other half of the feedstock also
goes to the second reactor, with the settler acid being recycled and the hydrocarbons charged to the main
fractionator. Subsequent processing is similar to the Phillips process. Overhead from the main fractionator
goes to a depropanizer. Isobutane is recycled to the reaction zone and alkylate is sent to product blending.
TABLE IV: 2-17. ALKYLATION PROCESS
Feedstock

From

Process

Typical products

To

Petroleum
gas

Distillation or
cracking

Unification

High octane
gasoline

Blending

Olefins

Cat. or hydro
cracking

n-Butane &
propane

Stripper or blender

Isobutane

Isomerization

FIGURE IV:2-21. SULFURIC ACID ALKYLATION.

FIGURE IV:2-22. HYDROGEN FLUORIDE ALKYLATION.

5. Health and Safety Considerations.

a. Fire Protection and Prevention. Alkylation units are closed processes; however, the potential exists for
fire should a leak or release occur that allows product or vapor to reach a source of ignition.
b. Safety. Sulfuric acid and hydrofluoric acid are potentially hazardous chemicals. Loss of coolant water,
which is needed to maintain process temperatures, could result in an upset. Precautions are necessary to
ensure that equipment and materials that have been in contact with acid are handled carefully and are
thoroughly cleaned before they leave the process area or refinery. Immersion wash vats are often provided
for neutralization of equipment that has come into contact with hydrofluoric acid. Hydrofluoric acid units
should be thoroughly drained and chemically cleaned prior to turnarounds and entry to remove all traces of
iron fluoride and hydrofluoric acid. Following shutdown, where water has been used the unit should be
thoroughly dried before hydrofluoric acid is introduced.
Leaks, spills, or releases involving hydrofluoric acid or hydrocarbons containing hydrofluoric acid can be
extremely hazardous. Care during delivery and unloading of acid is essential. Process unit containment by
curbs, drainage, and isolation so that effluent can be neutralized before release to the sewer system is
considered. Vents can be routed to soda-ash scrubbers to neutralize hydrogen fluoride gas or hydrofluoric
acid vapors before release. Pressure on the cooling water and steam side of exchangers should be kept
below the minimum pressure on the acid service side to prevent water contamination.
Some corrosion and fouling in sulfuric acid units may occur from the breakdown of sulfuric acid esters or
where caustic is added for neutralization. These esters can be removed by fresh acid treating and hot-water
washing. To prevent corrosion from hydrofluoric acid, the acid concentration inside the process unit should
be maintained above 65% and moisture below 4%.
c. Health. Because this is a closed process, exposures are expected to be minimal during normal
operations. There is a potential for exposure should leaks, spills, or releases occur. Sulfuric acid and
(particularly) hydrofluoric acid are potentially hazardous chemicals. Special precautionary emergency
preparedness measures and protection appropriate to the potential hazard and areas possibly affected need
to be provided. Safe work practices and appropriate skin and respiratory personal protective equipment are
needed for potential exposures to hydrofluoric and sulfuric acids during normal operations such as reading
gauges, inspecting, and process sampling, as well as during emergency response, maintenance, and
turnaround activities. Procedures should be in place to ensure that protective equipment and clothing worn
in hydrofluoric acid activities are decontaminated and inspected before reissue. Appropriate personal
protection for exposure to heat and noise also may be required.

Back to Top
SWEETENING AND TREATING PROCESSES.
1. Description.
a. Treating is a means by which contaminants such as organic compounds containing sulfur, nitrogen, and
oxygen; dissolved metals and inorganic salts; and soluble salts dissolved in emulsified water are removed
from petroleum fractions or streams. Petroleum refiners have a choice of several different treating
processes, but the primary purpose of the majority of them is the elimination of unwanted sulfur compounds.
A variety of intermediate and finished products, including middle distillates, gasoline, kerosene, jet fuel, and
sour gases are dried and sweetened. Sweetening, a major refinery treatment of gasoline, treats sulfur
compounds (hydrogen sulfide, thiophene and mercaptan) to improve color, odor, and oxidation stability.
Sweetening also reduces concentrations of carbon dioxide.
b. Treating can be accomplished at an intermediate stage in the refining process, or just before sending the
finished product to storage. Choices of a treating method depend on the nature of the petroleum fractions,
amount and type of impurities in the fractions to be treated, the extent to which the process removes the
impurities, and end-product specifications. Treating materials include acids, solvents, alkalis, oxidizing, and
adsorption agents.
2. Acid, Caustic, or Clay Treating. Sulfuric acid is the most commonly used acid treating process. Sulfuric
acid treating results in partial or complete removal of unsaturated hydrocarbons, sulfur, nitrogen, and oxygen
compounds, and resinous and asphaltic compounds. It is used to improve the odor, color, stability, carbon
residue, and other properties of the oil. Clay/lime treatment of acid-refined oil removes traces of asphaltic
materials and other compounds improving product color, odor, and stability. Caustic treating with sodium (or
potassium) hydroxide is used to improve odor and color by removing organic acids (naphthenic acids,
phenols) and sulfur compounds (mercaptans, H2S) by a caustic wash. By combining caustic soda solution
with various solubility promoters (e.g., methyl alcohol and cresols), up to 99% of all mercaptans as well as
oxygen and nitrogen compounds can be dissolved from petroleum fractions.
3. Drying and Sweetening. Feedstocks from various refinery units are sent to gas treating plants where
butanes and butenes are removed for use as alkylation feedstock, heavier components are sent to gasoline
blending, propane is recovered for LPG, and propylene is removed for use in petrochemicals. Some
mercaptans are removed by water-soluble chemicals that react with the mercaptans. Caustic liquid (sodium
hydroxide), amine compounds (diethanolamine) or fixed-bed catalyst sweetening also may be used. Drying
is accomplished by the use of water absorption or adsorption agents to remove water from the products.
Some processes simultaneously dry and sweeten by adsorption on molecular sieves.
TABLE IV: 2-18. SWEETENING AND TREATING PROCESSES.
Feedstock

From

Gases,
finished products, Various
intermediates

Process

Typical products

Treatment Butane & butene

To
Alkylation

Propane, distillates

Storage

Gasoline

Blending

Propylene

Petrochemical

FIGURE IV:2-23. MOLECULAR SIEVE DRYING AND SWEETENING.

4. Sulfur Recovery. Sulfur recovery converts hydrogen sulfide in sour gases and hydrocarbon streams to
elemental sulfur. The most widely used 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.
5. Hydrogen Sulfide Scrubbing. Hydrogen sulfide scrubbing is a common treating process in which the
hydrocarbon feedstock is first scrubbed to prevent catalyst poisoning. Depending on the feedstock and the
nature of contaminants, desulfurization methods vary from ambient temperature-activated charcoal
absorption to high-temperature catalytic hydrogenation followed by zinc oxide treating.
6. Health and Safety Considerations.
a. Fire Protection and Prevention. The potential exists for fire from a leak or release of feedstock or
product. Sweetening processes use air or oxygen. If excess oxygen enters these processes, it is possible for
a fire to occur in the settler due to the generation of static electricity, which acts as the ignition source.
b. Health. Because these are closed processes, exposures are expected to be minimal under normal
operating conditions. There is a potential for exposure to hydrogen sulfide, caustic (sodium hydroxide),
spent caustic, spent catalyst (Merox), catalyst dust and sweetening agents (sodium carbonate and sodium
bicarbonate). Safe work practices and/or appropriate personal protective equipment may be needed for
exposures to chemicals and other hazards such as noise and heat, and during process sampling,
inspection, maintenance, and turnaround activities.
Back to Top
UNSATURATED GAS PLANTS
1. Description. Unsaturated (unsat) gas plants recover light hydrocarbons (C3 and C4 olefins) from wet gas
streams from the FCC, TCC, and delayed coker overhead accumulators or fractionation receivers. In a
typical unsat gas plant, the gases are compressed and treated with amine to remove hydrogen sulfide either
before or after they are sent to a fractionating absorber where they are mixed into a concurrent flow of
debutanized gasoline. The light fractions are separated by heat in a reboiler, the offgas is sent to a sponge

absorber, and the bottoms are sent to a debutanizer. A portion of the debutanized hydrocarbon is recycled,
with the balance sent to the splitter for separation. The overhead gases go to a depropanizer for use as
alkylation unit feedstock.
TABLE IV: 2-19. UNSAT GAS PLANT PROCESS.
Feedstock

From

Process

Typical products

Gas Oils

FCC, TCC, delayed

coker

Treatment Gasoline
Gases

To
Recycle or treating
Alkylation

2. Health and Safety Considerations.

a. Fire Prevention and Protection. The potential of a fire exists should spills, releases, or vapors reach a
source of ignition.
b. Safety. In unsat gas plants handling FCC feedstock, the potential exists for corrosion from moist
hydrogen sulfide and cyanides. When feedstocks are from the delayed coker or the TCC, corrosion from
hydrogen sulfide and deposits in the high pressure sections of gas compressors from ammonium
compounds is possible.
c. Health. Because these are closed processes, exposures are expected to be minimal under normal
operating conditions. There is a potential for exposures to amine compounds such as monoethanolamine
(MEA), diethanolamine (DEA) and methyldiethanolamine (MDEA) and hydrocarbons. Safe work practices
and/or appropriate personal protective equipment may be needed for exposures to chemicals and other
hazards such as noise and heat, and during process sampling, inspection, maintenance, and turnaround
activities.
Back to Top
AMINE PLANTS
1. Description. 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 counterflowing
amine solutions (i.e., MEA, DEA, 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 action
and disposed of, and the amine is recycled.
2. Health and Safety Considerations.
a. Fire Protection and Prevention. The potential for fire exists where a spill or leak could reach a source of
ignition.
b. Safety. To minimize corrosion, proper operating practices should be established and regenerator bottom
and reboiler temperatures controlled. Oxygen should be kept out of the system to prevent amine oxidation.
c. Health. Because this is a closed process, exposures are expected to be minimal during normal
operations. There is potential for exposure to amine compounds (i.e. monoethanolamine, diethanolamine,
methyldiethanolamine), hydrogen sulfide and carbon dioxide. Safe work practices and/or appropriate
personal protective equipment may be needed for exposures to chemicals and other hazards such as noise
and heat, and during process sampling, inspection, maintenance and turnaround activities.
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SATURATE GAS PLANTS

1. Description. Saturate (sat) gas plants separate refinery gas components including butanes for alkylation,
pentanes for gasoline blending, LPG's for fuel, and ethane for petrochemicals. Because sat gas processes
depend on the feedstock and product demand, each refinery uses different systems, usually absorptionfractionation or straight fractionation. In absorption-fractionation, gases and liquids from various refinery
units are fed to an absorber-deethanizer where C2 and lighter fractions are separated from heavier fractions
by lean oil absorption and removed for use as fuel gas or petrochemical feed. The heavier fractions are
stripped and sent to a debutanizer, and the lean oil is recycled back to the absorber-deethanizer. C3/C4 is
separated from pentanes in the debutanizer, scrubbed to remove hydrogen sulfide, and fed to a splitter
where propane and butane are separated. In fractionation sat gas plants, the absorption stage is eliminated.
2. Health and Safety Considerations.
a. Fire Protection and Prevention. There is potential for fire if a leak or release reaches a source of ignition
such as the unit reboiler.
b. Safety. Corrosion could occur from the presence of hydrogen sulfide, carbon dioxide, and other
compounds as a result of prior treating. Streams containing ammonia should be dried before processing.
Antifouling additives may be used in absorption oil to protect heat exchangers. Corrosion inhibitors may be
used to control corrosion in overhead systems.
c. Health. Because this is a closed process, exposures are expected to be minimal during normal
operations. There is potential for exposure to hydrogen sulfide, carbon dioxide, and other products such as
diethanolamine or sodium hydroxide carried over from prior treating. Safe work practices and/or appropriate
personal protective equipment may be needed for exposures to chemicals and other hazards such as noise
and heat, and during process sampling, inspection, maintenance, and turnaround activities.
Back to Top
ASPHALT PRODUCTION
1. Description.
a. Asphalt is a portion of the residual fraction that remains after primary distillation operations. It is further
processed to impart characteristics required by its final use. In vacuum distillation, generally used to produce
road-tar asphalt, the residual is heated to about 750 F and charged to a column where vacuum is applied to
prevent cracking.
b. Asphalt for roofing materials is produced by air blowing. Residual is heated in a pipe still almost to its flash
point and charged to a blowing tower where hot air is injected for a predetermined time. The
dehydrogenization of the asphalt forms hydrogen sulfide, and the oxidation creates sulfur dioxide. Steam,
used to blanket the top of the tower to entrain the various contaminants, is then passed through a scrubber
to condense the hydrocarbons.
c. A third process used to produce asphalt is solvent deasphalting. In this extraction process, which uses
propane (or hexane) as a solvent, heavy oil fractions are separated to produce heavy lubricating oil, catalytic
cracking feedstock, and asphalt. Feedstock and liquid propane are pumped to an extraction tower at
precisely controlled mixtures, temperatures (150-250 F), and pressures of 350-600 psi. Separation occurs
in a rotating disc contactor, based on differences in solubility. The products are then evaporated and steam
stripped to recover the propane, which is recycled. Deasphalting also removes some sulfur and nitrogen
compounds, metals, carbon residues, and paraffins from the feedstock.
TABLE IV: 2-20. SOLVENT DEASPHALTING PROCESS.
Feedstock

From

Process

Typical products

To

Residual,
reduced
crude

Atmospheric tower
&
Vacuum tower

Treatment Heavy lube oil

Treating or lube blending

Asphalt

Storage of shipping

Deasphalted oil

Hydrotreat & catalytic cracker

Propane

Recycle

2. Health and Safety Considerations.

a. Fire Protection and Prevention. The potential for a fire exists if a product leak or release contacts a
source of ignition such as the process heater. Condensed steam from the various asphalt and deasphalting
processes will contain trace amounts of hydrocarbons. Any disruption of the vacuum can result in the entry
of atmospheric air and subsequent fire. In addition, raising the temperature of the vacuum tower bottom to
improve efficiency can generate methane by thermal cracking. This can create vapors in asphalt storage
tanks that are not detectable by flash testing but are high enough to be flammable.
b. Safety. Deasphalting requires exact temperature and pressure control. In addition, moisture, excess
solvent, or a drop in operating temperature may cause foaming, which affects the product temperature
control and may create an upset.
c. Health. Because these are closed processes, exposures are expected to be minimal during normal
operations. Should a spill or release occur, there is a potential for exposure to residuals and asphalt. Air
blowing can create some polynuclear aromatics. Condensed steam from the air-blowing asphalt process
may also contain contaminants. The potential for exposure to hydrogen sulfide and sulfur dioxide exists in
the production of asphalt. Safe work practices and/or appropriate personal protective equipment may be
needed for exposures to chemicals and other hazards such as noise and heat, and during process
sampling, inspection, maintenance, and turnaround activities.
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HYDROGEN PRODUCTION
1. Description.
a. High-purity hydrogen (95%-99%) is required for hydrodesulfurization, hydrogenation, hydrocracking, and
petrochemical processes. Hydrogen, produced as a by-product of refinery processes (principally hydrogen
recovery from catalytic reformer product gases), often is not enough to meet the total refinery requirements,
necessitating the manufacturing of additional hydrogen or obtaining supply from external sources.
b. In steam-methane reforming, desulfurized gases are mixed with superheated steam (1,100-1,600 F)
and reformed in tubes containing a nickel base catalyst. The reformed gas, which consists of steam,
hydrogen, carbon monoxide, and carbon dioxide, is cooled and passed through converters containing an
iron catalyst where the carbon monoxide reacts with steam to form carbon dioxide and more hydrogen. The
carbon dioxide is removed by amine washing. Any remaining carbon monoxide in the product stream is
converted to methane.
c. Steam-naphtha reforming is a continuous process for the production of hydrogen from liquid hydrocarbons
and is, in fact, similar to steam-methane reforming. A variety of naphthas in the gasoline boiling range may
be employed, including fuel containing up to 35% aromatics. Following pretreatment to remove sulfur
compounds, the feedstock is mixed with steam and taken to the reforming furnace (1,250-1,500 F) where
hydrogen is produced.
TABLE IV: 2-21. STEAM REFORMING PROCESS.

Feedstock

From

Process

Typical products To

Desufurized refinery Various treatment

Decomposition Hydrogen
gas
units

Processing

Carbon dioxide

Atmosphere

Carbon
monoxide

Methane

2. Health and Safety Considerations.

a. Fire Protection and Prevention. The possibility of fire exists should a leak or release occur and reach an
ignition source.
b. Safety. The potential exists for burns from hot gases and superheated steam should a release occur.
Inspections and testing should be considered where the possibility exists for valve failure due to
contaminants in the hydrogen. Carryover from caustic scrubbers should be controlled to prevent corrosion in
preheaters. Chlorides from the feedstock or steam system should be prevented from entering reformer tubes
and contaminating the catalyst.
c. Health. Because these are closed processes, exposures are expected to be minimal during normal
operating conditions. There is a potential for exposure to excess hydrogen, carbon monoxide, and/or carbon
dioxide. Condensate can be contaminated by process materials such as caustics and amine compounds,
with resultant exposures. Depending on the specific process used, safe work practices and/or appropriate
personal protective equipment may be needed for exposures to chemicals and other hazards such as noise
and heat, and during process sampling, inspection, maintenance, and turnaround activities.
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BLENDING
1. Description. Blending is the physical mixture of a number of different liquid hydrocarbons to produce a
finished product with certain desired characteristics. Products can be blended in-line through a manifold
system, or batch blended in tanks and vessels. In-line blending of gasoline, distillates, jet fuel, and kerosene
is accomplished by injecting proportionate amounts of each component into the main stream where
turbulence promotes thorough mixing. Additives including octane enhancers, metal deactivators, antioxidants, anti-knock agents, gum and rust inhibitors, detergents, etc. are added during and/or after blending
to provide specific properties not inherent in hydrocarbons.
2. Health and Safety Considerations.
a. Fire Prevention and Protection. Ignition sources in the area need to be controlled in the event of a leak
or release.
b. Health. Safe work practices and/or appropriate personal protective equipment may be needed for
exposures to chemicals and other hazards such as noise and heat; when handling additives; and during
inspection, maintenance, and turnaround activities.
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LUBRICANT, WAX, AND GREASE MANUFACTURING PROCESSES

1. Description. Lubricating oils and waxes are refined from the residual fractions of atmospheric and
vacuum distillation. The primary objective of the various lubricating oil refinery processes is to remove
asphalts, sulfonated aromatics, and paraffinic and isoparaffinic waxes from residual fractions. reduced crude

from the vacuum unit is deasphalted and combined with straight-run lubricating oil feedstock, preheated, and
solvent-extracted (usually with phenol or furfural) to produce raffinate.
2. Wax Manufacturing Process. Raffinate from the extraction unit contains a considerable amount of wax
that must be removed by solvent extraction and crystallization. The raffinate is mixed with a solvent
(propane) and precooled in heat exchangers. The crystallization temperature is attained by the evaporation
of propane in the chiller and filter feed tanks. The wax is continuously removed by filters and cold solventwashed to recover retained oil. The solvent is recovered from the oil by flashing and steam stripping. The
wax is then heated with hot solvent, chilled, filtered, and given a final wash to remove all oil.
3. Lubricating Oil Process. The dewaxed raffinate is blended with other distillate fractions and further
treated for viscosity index, color, stability, carbon residue, sulfur, additive response, and oxidation stability in
extremely selective extraction processes using solvents (furfural, phenol, etc.). In a typical phenol unit, the
raffinate is mixed with phenol in the treating section at temperatures below 400 F. Phenol is then separated
from the treated oil and recycled. The treated lube-oil base stocks are then mixed and/or compounded with
additives to meet the required physical and chemical characteristics of motor oils, industrial lubricants, and
metal working oils.
TABLE IV: 2-22. LUBRICATING OIL AND WAX MANUFACTURING PROCESSES.

Feedstock

From

Process

Typical
products

To

Lube feedstock
and additives

Vacuum tower, solvent dewaxing,

hydrotreating solvent extraction,
etc.

Treatment

Dewaxed
raffinate

Lube blend or
compound,
grease compounding

Wax

Storage or shipping

4. Grease Compounding. Grease is made by blending metallic soaps (salts of long-chained fatty acids)
and additives into a lubricating oil medium at temperatures of 400-600 F. Grease may be either batchproduced or continuously compounded. The characteristics of the grease depend to a great extent on the
metallic element (calcium, sodium, aluminum, lithium, etc.) in the soap and the additives used.
5. Safety and Health Considerations.
a. Fire Protection and Prevention. The potential for fire exists if a product or vapor leak or release in the
lube blending and wax processing areas reaches a source of ignition. Storage of finished products, both bulk
and packaged, should be in accordance with recognized practices.
While the potential for fire is reduced in lube oil blending, care must be taken when making metal-working
oils and compounding greases due to the use of higher blending and compounding temperatures and lower
flash point products.
b. Safety. Control of treater temperature is important as phenol can cause corrosion above 400 F. Batch
and in-line blending operations require strict controls to maintain desired product quality. Spills should be
cleaned and leaks repaired to avoid slips and falls. Additives in drums and bags need to be handled properly
to avoid strain. Wax can clog sewer or oil drainage systems and interfere with wastewater treatment.
c. Health. When blending, sampling, and compounding, personal protection from steam, dusts, mists,
vapors, metallic salts, and other additives is appropriate. Skin contact with any formulated grease or
lubricant should be avoided. Safe work practices and/or appropriate personal protection may be needed for
exposures to chemicals and other hazards such as noise and heat; during inspection, maintenance, and
turnaround activities; and while sampling and handling hydrocarbons and chemicals during the production of
lubricating oil and wax.
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HEAT EXCHANGERS, COOLERS, AND PROCESS HEATERS.

1. Heating Operations. Process heaters and heat exchangers preheat feedstock in distillation towers and in
refinery processes to reaction temperatures. Heat exchangers use either steam or hot hydrocarbon
transferred from some other section of the process for heat input. The heaters are usually designed for
specific process operations, and most are of cylindrical vertical or box-type designs. The major portion of
heat provided to process units comes from fired heaters fueled by refinery or natural gas, distillate, and
residual oils. Fired heaters are found on crude and reformer preheaters, coker heaters, and large-column
reboilers.
2. Cooling Operations. Heat also may be removed from some processes by air and water exchangers, fin
fans, gas and liquid coolers, and overhead condensers, or by transferring heat to other systems. The basic
mechanical vapor-compression refrigeration system, which may serve one or more process units, includes
an evaporator, compressor, condenser, controls, and piping. Common coolants are water, alcohol/water
mixtures, or various glycol solutions.
3. Health and Safety Considerations.
a. Fire Protection and Prevention. A means of providing adequate draft or steam purging is required to
reduce the chance of explosions when lighting fires in heater furnaces. Specific start-up and emergency
procedures are required for each type of unit. If fire impinges on fin fans, failure could occur due to
overheating. If flammable product escapes from a heat exchanger or cooler due to a leak, fire could occur.
b. Safety. Care must be taken to ensure that all pressure is removed from heater tubes before removing
header or fitting plugs. Consideration should be given to providing for pressure relief in heat-exchanger
piping systems in the event they are blocked off while full of liquid. If controls fail, variations of temperature
and pressure could occur on either side of the heat exchanger. If heat exchanger tubes fail and process
pressure is greater than heater pressure, product could enter the heater with downstream consequences. If
the process pressure is less than heater pressure, the heater stream could enter into the process fluid. If
loss of circulation occurs in liquid or gas coolers, increased product temperature could affect downstream
operations and require pressure relief.
c. Health. Because these are closed systems, exposures under normal operating conditions are expected to
be minimal. Depending on the fuel, process operation, and unit design, there is a potential for exposure to
hydrogen sulfide, carbon monoxide, hydrocarbons, steam boiler feed-water sludge, and water-treatment
chemicals. Skin contact should be avoided with boiler blowdown, which may contain phenolic compounds.
Safe work practices and/or appropriate personal protective equipment against hazards may be needed
during process maintenance, inspection, and turnaround activities and for protection from radiant heat,
superheated steam, hot hydrocarbon, and noise exposures.
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STEAM GENERATION
1. Heater and Boiler Operations. Steam is generated in main generation plants, and/or at various process
units using heat from flue gas or other sources. Heaters (furnaces) include burners and a combustion air
system, the boiler enclosure in which heat transfer takes place, a draft or pressure system to remove flue
gas from the furnace, soot blowers, and compressed-air systems that seal openings to prevent the escape
of flue gas. Boilers consist of a number of tubes that carry the water-steam mixture through the furnace for
maximum heat transfer. These tubes run between steam-distribution drums at the top of the boiler and
water-collecting drums at the bottom of the boiler. Steam flows from the steam drum to the superheater
before entering the steam distribution system.
2. Heater Fuel.
a. Heaters may use any one or combination of fuels including refinery gas, natural gas, fuel oil, and
powdered coal. Refinery off-gas is collected from process units and combined with natural gas and LPG in a
fuel-gas balance drum. The balance drum provides constant system pressure, fairly stable Btu-content fuel,

and automatic separation of suspended liquids in gas vapors, and it prevents carryover of large slugs of
condensate into the distribution system. Fuel oil is typically a mix of refinery crude oil with straight-run and
cracked residues and other products. The fuel-oil system delivers fuel to process-unit heaters and steam
generators at required temperatures and pressures. The fuel oil is heated to pumping temperature, sucked
through a coarse suction strainer, pumped to a temperature-control heater, and then pumped through a finemesh strainer before being burned.
b. In one example of process-unit heat generation, carbon monoxide boilers recover heat in catalytic
cracking units as carbon monoxide in flue gas is burned to complete combustion. In other processes, wasteheat recovery units use heat from the flue gas to make steam.
3. Steam Distribution. The distribution system consists of valves, fittings, piping, and connections suitable
for the pressure of the steam transported. Steam leaves the boilers at the highest pressure required by the
process units or electrical generation. The steam pressure is then reduced in turbines that drive process
pumps and compressors. Most steam used in the refinery is condensed to water in various types of heat
exchangers. The condensate is reused as boiler feedwater or discharged to wastewater treatment. When
refinery steam is also used to drive steam turbine generators to produce electricity, the steam must be
produced at much higher pressure than required for process steam. Steam typically is generated by heaters
(furnaces) and boilers combined in one unit.
4. Feedwater.
a. Feedwater supply is an important part of steam generation. There must always be as many pounds of
water entering the system as there are pounds of steam leaving it. Water used in steam generation must be
free of contaminants including minerals and dissolved impurities that can damage the system or affect its
operation. Suspended materials such as silt, sewage, and oil, which form scale and sludge, must be
coagulated or filtered out of the water. Dissolved gases, particularly carbon dioxide and oxygen, cause boiler
corrosion and are removed by deaeration and treatment. Dissolved minerals including metallic salts,
calcium, carbonates, etc., that cause scale, corrosion, and turbine blade deposits are treated with lime or
soda ash to precipitate them from the water. Recirculated cooling water must also be treated for
hydrocarbons and other contaminants.
b. Depending on the characteristics of raw boiler feedwater, some or all of the following six stages of
treatment will be applicable:

Clarification
Sedimentation
Filtration
Ion exchange
Deaeration
Internal treatment

5. Health and Safety Considerations.

a. Fire Protection and Prevention. The most potentially hazardous operation in steam generation is heater
startup. A flammable mixture of gas and air can build up as a result of loss of flame at one or more burners
during light-off. Each type of unit requires specific startup and emergency procedures including purging
before lightoff and in the event of misfire or loss of burner flame.
b. Safety. If feedwater runs low and boilers are dry, the tubes will overheat and fail. Conversely, excess
water will be carried over into the steam distribution system and damage the turbines. Feedwater must be
free of contaminants that could affect operations. Boilers should have continuous or intermittent blowdown
systems to remove water from steam drums and limit buildup of scale on turbine blades and superheater
tubes. Care must be taken not to overheat the superheater during startup and shut-down. Alternate fuel
sources should be provided in the event of loss of gas due to refinery unit shutdown or emergency.
Knockout pots provided at process units remove liquids from fuel gas before burning.

c. Health. Safe work practices and/or appropriate personal protective equipment may be needed for
potential exposures to feedwater chemicals, steam, hot water, radiant heat, and noise, and during process
sampling, inspection, maintenance, and turnaround activities.
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PRESSURE-RELIEF AND FLARE SYSTEMS.
1. Pressure-Relief Systems. Pressure-relief systems control vapors and liquids that are released by
pressure-relieving devices and blow-downs. Pressure relief is an automatic, planned release when operating
pressure reaches a predetermined level. Blowdown normally refers to the intentional release of material,
such as blowdowns from process unit startups, furnace blowdowns, shutdowns, and emergencies. Vapor
depressuring is the rapid removal of vapors from pressure vessels in case of fire. This may be accomplished
by the use of a rupture disc, usually set at a higher pressure than the relief valve.
2. Safety Relief Valve Operations. Safety relief valves, used for air, steam, and gas as well as for vapor
and liquid, allow the valve to open in proportion to the increase in pressure over the normal operating
pressure. Safety valves designed primarily to release high volumes of steam usually pop open to full
capacity. The overpressure needed to open liquid-relief valves where large-volume discharge is not required
increases as the valve lifts due to increased spring resistance. Pilot-operated safety relief valves, with up to
six times the capacity of normal relief valves, are used where tighter sealing and larger volume discharges
are required. Nonvolatile liquids are usually pumped to oil-water separation and recovery systems, and
volatile liquids are sent to units operating at a lower pressure.
3. Flare Systems. A typical closed pressure release and flare system includes relief valves and lines from
process units for collection of discharges, knockout drums to separate vapors and liquids, seals, and/or
purge gas for flashback protection, and a flare and igniter system which combusts vapors when discharging
directly to the atmosphere is not permitted. Steam may be injected into the flare tip to reduce visible smoke.
4. Pressure Relief Health and Safety Considerations.
a. Fire Protection and Prevention. Vapors and gases must not discharge where sources of ignition could
be present.
b. Safety. Liquids should not be discharged directly to a vapor disposal system. Flare knockout drums and
flares need to be large enough to handle emergency blowdowns. Drums should be provided with relief in the
event of overpressure.
Pressure relief valves must be provided where the potential exists for overpressure in refinery processes
due to the following causes:

Loss of cooling water, which may greatly reduce pressure in condensers and increase the pressure
in the process unit.
Loss of reflux volume, which may cause a pressure drop in condensers and a pressure rise in
distillation towers because the quantity of reflux affects the volume of vapors leaving the distillation
tower.
Rapid vaporization and pressure increase from injection of a lower boiling-point liquid including
water into a process vessel operating at higher temperatures.
Expansion of vapor and resultant over-pressure due to overheated process steam, malfunctioning
heaters, or fire.
Failure of automatic controls, closed outlets, heat exchanger failure, etc.
Internal explosion, chemical reaction, thermal expansion, or accumulated gases.

Maintenance is important because valves are required to function properly. The most common operating
problems are listed below.

Failure to open at set pressure, because of plugging of the valve inlet or outlet, or because
corrosion prevents proper operation of the disc holder and guides.
Failure to reseat after popping open due to fouling, corrosion, or deposits on the seat or moving
parts, or because solids in the gas stream have cut the valve disc.
Chattering and premature opening, because operating pressure is too close to the set point.

c. Health. Safe work practices and/or appropriate personal protective equipment may be needed to protect
against hazards during inspection, maintenance, and turnaround activities.
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WASTEWATER TREATMENT
1. Description. Wastewater treatment is used for process, runoff, and sewerage water prior to discharge or
recycling. Wastewater typically contains hydrocarbons, dissolved materials, suspended solids, phenols,
ammonia, sulfides, and other compounds. Wastewater includes condensed steam, stripping water, spent
caustic solutions, cooling tower and boiler blowdown, wash water, alkaline and acid waste neutralization
water, and other process-associated water.
2. Pretreatment Operations. Pretreatment is the separation of hydrocarbons and solids from wastewater.
API separators, interceptor plates, and settling ponds remove suspended hydrocarbons, oily sludge, and
solids by gravity separation, skimming, and filtration. Some oil-in-water emulsions must be heated to assist
in separating the oil and water. Gravity separation depends on the specific gravity differences between water
and immiscible oil globules and allows free oil to be skimmed off the surface of the wastewater. Acidic
wastewater is neutralized using ammonia, lime, or soda ash. Alkaline wastewater is treated with sulfuric
acid, hydrochloric acid, carbon dioxide-rich flue gas, or sulfur.
3. Secondary Treatment Operations. After pretreatment, suspended solids are removed by sedimentation
or air flotation. Wastewater with low levels of solids may be screened or filtered. Flocculation agents are
sometimes added to help separation. Secondary treatment processes biologically degrade and oxidize
soluble organic matter by the use of activated sludge, unaerated or aerated lagoons, trickling filter methods,
or anaerobic treatments. Materials with high adsorption characteristics are used in fixed-bed filters or added
to the wastewater to form a slurry which is removed by sedimentation or filtration. Additional treatment
methods are used to remove oils and chemicals from wastewater. Stripping is used on wastewater
containing sulfides and/or ammonia, and solvent extraction is used to remove phenols.
4. Tertiary Treatment Operations. Tertiary treatments remove specific pollutants to meet regulatory
discharge requirements. These treatments include chlorination, ozonation, ion exchange, reverse osmosis,
activated carbon adsorption, etc. Compressed oxygen is diffused into wastewater streams to oxidize certain
chemicals or to satisfy regulatory oxygen-content requirements. Wastewater that is to be recycled may
require cooling to remove heat and/or oxidation by spraying or air stripping to remove any remaining
phenols, nitrates, and ammonia.
5. Health and Safety Considerations.
a. Fire Protection and Prevention. The potential for fire exists if vapors from wastewater containing
hydrocarbons reach a source of ignition during treatment.
b. Health. Safe work practices and/or appropriate personal protective equipment may be needed for
exposures to chemicals and waste products during process sampling, inspection, maintenance, and
turnaround activities as well as to noise, gases, and heat.
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COOLING TOWERS

1. Description. Cooling towers remove heat from process water by evaporation and latent heat transfer
between hot water and air. The two types of towers are crossflow and counterflow. Crossflow towers
introduce the airflow at right angles to the water flow throughout the structure. In counterflow cooling towers,
hot process water is pumped to the uppermost plenum and allowed to fall through the tower. Numerous slats
or spray nozzles located throughout the length of the tower disperse the water and help in cooling. Air enters
at the tower bottom and flows upward against the water. When the fans or blowers are at the air inlet, the air
is considered to be forced draft. Induced draft is when the fans are at the air outlet.
2. Cooling Water. Recirculated cooling water must be treated to remove impurities and dissolved
hydrocarbons. Because the water is saturated with oxygen from being cooled with air, the chances for
corrosion are increased. One means of corrosion prevention is the addition of a material to the cooling water
that forms a protective film on pipes and other metal surfaces.
3. Health and Safety Considerations.
a. Fire Prevention and Protection. When cooling water is contaminated by hydrocarbons, flammable
vapors can be evaporated into the discharge air. If a source of ignition is present, or if lightning occurs, a fire
may start. A potential fire hazard also exists where there are relatively dry areas in induced-draft cooling
towers of combustible construction.
b. Safety. Loss of power to cooling tower fans or water pumps could have serious consequences in the
operation of the refinery. Impurities in cooling water can corrode and foul pipes and heat exchangers, scale
from dissolved salts can deposit on pipes, and wooden cooling towers can be damaged by microorganisms.
c. Health. Cooling-tower water can be contaminated by process materials and by-products including sulfur
dioxide, hydrogen sulfide, and carbon dioxide, with resultant exposures. Safe work practices and/or
appropriate personal protective equipment may be needed during process sampling, inspection,
maintenance, and turnaround activities; and for exposure to hazards such as those related to noise, watertreatment chemicals, and hydrogen sulfide when wastewater is treated in conjunction with cooling towers.
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ELECTRIC POWER
1. Description. Refineries may receive electricity from outside sources or produce their own power with
generators driven by steam turbines or gas engines. Electrical substations receive power from the utility or
power plant for distribution throughout the facility. They are usually located in nonclassified areas, away from
sources of vapor or cooling-tower water spray. Transformers, circuit breakers, and feed-circuit switches are
usually located in substations. Substations feed power to distribution stations within the process unit areas.
Distribution stations can be located in classified areas, providing that classification requirements are met.
Distribution stations usually have a liquid-filled transformer and an oil-filled or air-break disconnect device.
2. Health and Safety Considerations.
a. Fire Protection and Prevention. Generators that are not properly classified and are located too close to
process units may be a source of ignition should a spill or release occur.
b. Safety. Normal electrical safety precautions including dry footing, high-voltage warning signs, and
guarding must be taken to protect against electrocution. Lockout/tagout and other appropriate safe work
practices must be established to prevent energization while work is being performed on high-voltage
electrical equipment.
c. Health. Safe work practices and/or the use of appropriate personal protective equipment may be needed
for exposures to noise, for exposure to hazards during inspection and maintenance activities, and when
working around transformers and switches that may contain a dielectric fluid which requires special handling
precautions.
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GAS AND AIR COMPRESSORS.

1. Description. Both reciprocating and centrifugal compressors are used throughout the refinery for gas and
compressed air. Air compressor systems include compressors, coolers, air receivers, air dryers, controls,
and distribution piping. Blowers are used to provide air to certain processes. Plant air is provided for the
operation of air-powered tools, catalyst regeneration, process heaters, steam-air decoking, sour-water
oxidation, gasoline sweetening, asphalt blowing, and other uses. Instrument air is provided for use in
pneumatic instruments and controls, air motors and purge connections.
2. Health and Safety Considerations.
a. Fire Protection and Prevention. Air compressors should be located so that the suction does not take in
flammable vapors or corrosive gases. There is a potential for fire should a leak occur in gas compressors.
b. Safety. Knockout drums are needed to prevent liquid surges from entering gas compressors. If gases are
contaminated with solid materials, strainers are needed. Failure of automatic compressor controls will affect
processes. If maximum pressure could potentially be greater than compressor or process-equipment design
pressure, pressure relief should be provided. Guarding is needed for exposed moving parts on compressors.
Compressor buildings should be properly electrically classified, and provisions should be made for proper
ventilation.
Where plant air is used to back up instrument air, interconnections must be upstream of the instrument air
drying system to prevent contamination of instruments with moisture. Alternate sources of instrument air
supply, such as use of nitrogen, may be needed in the event of power outages or compressor failure.
c. Health. Safe work practices and/or appropriate personal protective equipment may be needed for
exposure to hazards such as noise and during inspection and maintenance activities. The use of appropriate
safeguards must be considered so that plant and instrument air is not used for breathing or pressuring
potable water systems.
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MARINE, TANK CAR, AND TANK TRUCK LOADING AND UNLOADING.
1. Description. Facilities for loading liquid hydrocarbons into tank cars, tank trucks, and marine vessels and
barges are usually part of the refinery operations. Product characteristics, distribution needs, shipping
requirements, and operating criteria are important when designing loading facilities. Tank trucks and rail tank
cars are either top- or bottom-loaded, and vapor-recovery systems may be provided where required.
Loading and unloading liquefied petroleum gas (LPG) require special considerations in addition to those for
liquid hydrocarbons.
2. Health and Safety Considerations.
a. Fire Protection and Prevention. The potential for fire exists where flammable vapors from spills or
releases can reach a source of ignition. Where switch-loading is permitted, safe practices need to be
established and followed. Bonding is used to equalize the electrical charge between the loading rack and the
tank truck or tank car. Grounding is used at truck and rail loading facilities to prevent flow of stray currents.
Insulating flanges are used on marine dock piping connections to prevent static electricity buildup and
discharge. Flame arrestors should be installed in loading rack and marine vapor-recovery lines to prevent
flashback.
b. Safety. Automatic or manual shutoff systems at supply headers are needed for top and bottom loading in
the event of leaks or overfills. Fall protection such as railings are needed for top-loading racks where
employees are exposed to falls. Drainage and recovery systems may be provided for storm drainage and to
handle spills and leaks. Precautions must be taken at LPG loading facilities not to overload or
overpressurize tank cars and trucks.

c. Health. The nature of the health hazards at loading and unloading facilities depends upon the products
being loaded and the products previously transported in the tank cars, tank trucks, or marine vessels. Safe
work practices and/or appropriate personal protective equipment may be needed to protect against
hazardous exposures when loading or unloading, cleaning up spills or leaks, or when gauging, inspecting,
sampling, or performing maintenance activities on loading facilities or vapor-recovery systems.
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TURBINES
1. Description. Turbines are usually gas- or steam-powered and are typically used to drive pumps,
compressors, blowers, and other refinery process equipment. Steam enters turbines at high temperatures
and pressures, expands across and drives rotating blades while directed by fixed blades.
2. Health and Safety Considerations.
a. Safety. Steam turbines used for exhaust operating under vacuum should have safety relief valves on the
discharge side, both for protection and to maintain steam in the event of vacuum failure. Where maximum
operating pressure could be greater than design pressure, steam turbines should be provided with relief
devices. Consideration should be given to providing governors and overspeed control devices on turbines.
b. Health. Safe work practices and/or appropriate personal protective equipment may be needed for noise,
steam and heat exposures, and during inspection and maintenance activities.
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PUMPS, PIPING AND VALVES
1. Description.
a. Centrifugal and positive-displacement (i.e., reciprocating) pumps are used to move hydrocarbons,
process water, fire water, and wastewater through piping within the refinery. Pumps are driven by electric
motors, steam turbines, or internal combustion engines. The pump type, capacity, and construction
materials depend on the service for which it is used.
b. Process and utility piping distribute hydrocarbons, steam, water, and other products throughout the
facility. Their size and construction depend on the type of service, pressure, temperature, and nature of the
products. Vent, drain, and sample connections are provided on piping, as well as provisions for blanking.
c. Different types of valves are used depending on their operating purpose. These include gate valves,
bypass valves, globe and ball valves, plug valves, block and bleed valves, and check valves. Valves can be
manually or automatically operated.
2. Health and Safety Considerations.
a. Fire Protection and Prevention. The potential for fire exists should hydrocarbon pumps, valves, or lines
develop leaks that could allow vapors to reach sources of ignition. Remote sensors, control valves, fire
valves, and isolation valves should be used to limit the release of hydrocarbons at pump suction lines in the
event of leakage and/or fire.
b. Safety. Depending on the product and service, backflow prevention from the discharge line may be
needed. The failure of automatic pump controls could cause a deviation in process pressure and
temperature. Pumps operated with reduced or no flow can overheat and rupture. Pressure relief in the
discharge piping should be provided where pumps can be overpressured. Provisions may be made for
pipeline expansion, movement, and temperature changes to avoid rupture. Valves and instruments that
require servicing or other work should be accessible at grade level or from an operating platform. Operating

vent and drain connections should be provided with double-block valves, a block valve and plug, or blind
flange for protection against releases.
c. Health. Safe work practices and/or appropriate personal protective equipment may be needed for
exposure to hazards such as those related to liquids and vapors when opening or draining pumps, valves,
and/or lines, and during product sampling, inspection, and maintenance activities.
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TANK STORAGE
1. Description. Atmospheric storage tanks and pressure storage tanks are used throughout the refinery for
storage of crudes, intermediate hydrocarbons (during the process), and finished products. Tanks are also
provided for fire water, process and treatment water, acids, additives, and other chemicals. The type,
construction, capacity and location of tanks depends on their use and materials stored.
2. Health and Safety Considerations.
a. Fire Prevention and Protection. The potential for fire exists should hydrocarbon storage tanks be
overfilled or develop leaks that allow vapors to escape and reach sources of ignition. Remote sensors,
control valves, isolation valves, and fire valves may be provided at tanks for pump-out or closure in the event
of a fire in the tank, or in the tank dike or storage area.
b. Safety. Tanks may be provided with automatic overflow control and alarm systems, or manual gauging
and checking procedures may be established to control overfills.
c. Health. Safe work practices and/or appropriate personal protective equipment may be needed for
exposure to hazards related to product sampling, manual gauging, inspection, and maintenance activities
including confined space entry where applicable.