Oil refinery

From Wikipedia, the free encyclopedia

Anacortes Refinery (Tesoro), on the north end of March Point southeast of Anacortes,
Washington

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.[1][2] Oil refineries are
typically large sprawlingindustrial complexes with extensive piping running
throughout, carrying streams of fluidsbetween large chemical processing units.

Contents
[hide]

• 1 Operation
• 2 Major products of oil refineries
• 3 Common process units found in a refinery
o 3.1 Flow diagram of typical refinery
• 4 Specialty end products
• 5 Siting/locating of petroleum refineries
• 6 Safety and environmental concerns
• 7 Corrosion problems and prevention
• 8 History
o 8.1 Oil refining in the United States
• 9 See also
• 10 References

• 11 External links
[edit]Operation

Crude oil is separated into fractions byfractional distillation. The fractions at the top of
thefractionating column have lower boiling points than the fractions at the bottom. The heavy
bottom fractions are often cracked into lighter, more useful products. All of the fractions are
processed further in other refining units.

Raw or unprocessed crude oil is not 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,detergents, solvents, elastomers, and fibers such
as nylon and polyesters. 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.
The oil refinery in Haifa, Israel is capable of processing about 9 million tons (66 million barrels)
ofcrude oil a year. Its two cooling towers are landmarks of the city's skyline.

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 (orcycloalkanes), 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 short-chained 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.

Oil refineries are large scale plants, processing from about a hundred thousand to
several hundred thousand barrels of crude oil per day. Because of the high capacity,
many of the units are operated continuously (as opposed to processing in batches)
at steady state or approximately steady state for long periods of time (months to
years). This high capacity also makes process optimization and advanced process
control very desirable.

[edit]Major products of oil refineries

Most products of oil processing are usually grouped into three categories: light
distillates (LPG, gasoline, naphtha), middle distillates (kerosene, diesel), heavy
distillates and residuum (fuel oil, lubricating oils, wax, tar). This classification is based
on the way crude oil is distilled and separated into fractions
(called distillates and residuum) as can be seen in the above drawing.[2]

 Liquid petroleum gas (LPG)

 Gasoline (also known as petrol)
 Naphtha
 Kerosene and related jet aircraft fuels
 Diesel fuel
 Fuel oils
 Lubricating oils
 Paraffin wax
 Asphalt and Tar
 Petroleum coke

[edit]Common process units found in a refinery

The number and nature of the process units in a refinery determine its complexity
index.

 Desalter unit washes out salt from the crude oil before it enters the atmospheric
distillation unit.
 Atmospheric Distillation unit distills crude oil into fractions. See Continuous
distillation.
 Vacuum Distillation unit further distills residual bottoms after atmospheric
distillation.
 Naphtha Hydrotreater unit uses hydrogen to desulfurize naphtha from
atmospheric distillation. Must hydrotreat the naphtha before sending to a
Catalytic Reformer unit.
 Catalytic Reformer unit is used to convert the naphtha-boiling range molecules
into higher octane reformate (reformer product). The reformate has higher
content of aromatics and cyclic hydrocarbons). An important byproduct of a
reformer is hydrogen released during the catalyst reaction. The hydrogen is used
either in the hydrotreaters or the hydrocracker.
 Distillate Hydrotreater unit desulfurizes distillates (such as diesel) after
atmospheric distillation.
 Fluid Catalytic Cracker (FCC) unit upgrades heavier fractions into lighter, more
valuable products.
 Hydrocracker unit uses hydrogen to upgrade heavier fractions into lighter, more
valuable products.
 Visbreaking unit upgrades heavy residual oils by thermally cracking them into
lighter, more valuable reduced viscosity products.
 Merox unit treats LPG, kerosene or jet fuel by oxidizing mercaptans to
organic disulfides.
 Coking units (delayed coking, fluid coker, and flexicoker) process very heavy
residual oils into gasoline and diesel fuel, leaving petroleum coke as a residual
product.
 Alkylation unit produces high-octane component for gasoline blending.
 Dimerization unit converts olefins into higher-octane gasoline blending
components. For example, butenes can be dimerized into isooctene which may
subsequently be hydrogenated to form isooctane. There are also other uses for
dimerization.
 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 vessels or bullets
(horizontal vessels with rounded ends.
 Storage tanks for crude oil and finished products, usually cylindrical, with some
sort of vapor emission control and surrounded by an earthenberm to contain
spills.
 Amine gas treater, Claus unit, and tail gas treatment for converting hydrogen
sulfide from hydrodesulfurization into elemental sulfur.
 Utility units such as cooling towers for circulating cooling water, boiler
plants for steam generation, instrument air systems for pneumatically
operated control valves and an electrical substation.
 Wastewater collection and treating systems consisting of API
separators, dissolved air flotation (DAF) units and some type of further treatment
 (such as an activated sludge biotreater) to make such water suitable for reuse or
for disposal.[3]
 Solvent refining units use solvent such as cresol or furfural to remove unwanted,
mainly asphaltenic materials from lubricating oil stock (or diesel stock).
 Solvent dewaxing units remove the heavy waxy constituents petrolatum from
vacuum distillation products.

[edit]Flow diagram of typical refinery

The image below is a schematic flow diagram of a typical oil refinery that depicts the
various unit processes and the flow of intermediate product streams that occurs
between the inlet crude oil feedstock and the final end products. The diagram depicts
only one of the literally hundreds of different oil refinery configurations. The diagram
also does not include any of the usual refinery facilities providing utilities such as
steam, cooling water, and electric power as well as storage tanks for crude oil
feedstock and for intermediate products and end products.[1][4][5][6]
Schematic flow diagram of a typical oil refinery

There are many process configurations other than that depicted above. For example,
the vacuum distillation unit may also produce fractions that can be refined into
endproducts such as: spindle oil used in the textile industry, light machinery oil,
motor oil, and steam cylinder oil. As another example, the vacuum residue may be
processed in a coker unit to produce petroleum coke.
[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 (paraffin), used in the packaging of frozen foods, among others. May be
shipped in bulk to a site to prepare as packaged blocks.
 Sulfur (or sulfuric acid), byproducts of sulfur removal from petroleum which may
have up to a couple percent sulfur as organic sulfur-containing compounds. Sulfur
and sulfuric acid are useful industrial materials. Sulfuric acid is usually prepared
and shipped as the acid precursor oleum.
 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.
 Petrochemicals or petrochemical feedstocks, which are often sent to
petrochemical plants for further processing in a variety of ways. The
petrochemicals may be olefins or their precursors, or various types
of aromatic petrochemicals.

[edit]Siting/locating of petroleum refineries

The principles of finding a construction site for refineries are similar to those for other
chemical plants:

 The site has to be reasonably far from residential areas.

 Facilities for raw materials access and products delivery to markets should be
easily available.

 Processing energy requirements should be easily available.

 Waste product disposal should not cause difficulties.

For refineries which use large amounts of process steam and cooling water, an
abundant source of water is important. Because of this, oil refineries are often
located (associated to a port) near navigable rivers or even better on a sea shore.
Either are of dual purpose, making also available cheap transport by river or by sea.
Although the advantages of crude oil transport by pipeline are evident, and the
method is also often used by oil companies to deliver large output products such as
fuels to their bulk distribution terminals, pipeline delivery is not practical for small
output products. For these, rail cars, road tankers or barges may be used.

It is useful to site refineries in areas where there is abundant space to be used by the
same company or others, for the construction of petrochemical plants, solvent
manufacturing (fine fractionating) plants and/or similar plants to allow these easy
access to large output refinery products for further processing, or plants that produce
chemical additives that the refinery may need to blend into a product at source
rather than at blending terminals.

[edit]Safety and environmental concerns

MiRO refinery at Karlsruhe

The refining process releases numerous different chemicals into the atmosphere;
consequently, there are substantial air pollution emissions[7] and a
notable odornormally accompanies the presence of a refinery. Aside from air pollution
impacts there are also wastewater concerns,[3] risks of industrial accidents such as
fire and explosion, and noise health effects due to industrial noise.

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'sGaryville, Louisiana facility in 1976. However, many existing
refineries have been expanded during that time. Environmental restrictions and
pressure to prevent construction of new refineries may have also contributed to rising
fuel prices in the United States.[8] Additionally, many refineries (over 100 since the
1980s) have closed due to obsolescence and/or merger activity within the industry
itself. This activity has been reported to Congress and in specialized studies not
widely publicised.

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 the Campo de Gibraltar, a CEPSA refinery near the towns of Gibraltar, Algeciras, La
Linea, San Roque and Los Barrios with a combined population of over 300,000
residents within a 5-mile (8.0 km) radius and the CEPSA refinery in Santa Cruz on the
island of Tenerife, Spain[9] 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, Pacheco,Concord, Pittsburg, Vallejo and Benicia, with
occasional accidental events that require "shelter in place" orders to the adjacent
populations.

In 2008, twelve US states and the District of Columbia announced their intent to sue
the US Environmental Protection Agency to force that agency to begin
regulating greenhouse gases emitted from oil refineries. They want the EPA to
regulate all greenhouse gases, including carbon dioxide and methane from these
sources.[10]
[edit]Corrosion problems and prevention
Petroleum refineries run as efficiently as possible to reduce costs. One major factor
that decreases efficiency is corrosion of the metal components found throughout the
process line of the hydrocarbon refining process. Corrosion causes the failure of parts
in addition to dictating the cleaning schedule of the refinery, during which the entire
production facility must be shut down and cleaned. The cost of corrosion in the
petroleum industry has been estimated at US$3.7 billion.[11]

Corrosion occurs in various forms in the refining process, such as pitting corrosion
from water droplets, embrittlement from hydrogen, and stress corrosion cracking
from sulfide attack.[12] From a materials standpoint, carbon steel is used for upwards
of 80% of refinery components, which is beneficial due to its low cost. Carbon steel is
resistant to the most common forms of corrosion, particularly from hydrocarbon
impurities at temperatures below 205oC, but other corrosive chemicals and
environments prevent its use everywhere. Common replacement materials are low
alloy steels containing chromium and molybdenum, with stainless steels containing
more Chromium dealing with more corrosive environments. More expensive materials
commonly used are nickel, titanium, and copper alloys. These are primarily saved for
the most problematic areas where extremely high temperatures or very corrosive
chemicals are present.[13]

Corrosion is fought by a complex system of monitoring and careful use of materials.

Monitoring methods include both off-line checks taken during maintenance and on-
line monitoring collected in real time during normal plant operation. Off-line checks
measure corrosion after it has occurred, telling the engineer when equipment must
be replaced. On-line systems are a more modern development, and are
revolutionizing the way corrosion is approached. It allows process engineers to treat
corrosion as another process variable. Immediate responses to process changes allow
the control of corrosion mechanisms, so they can be minimized while also maximizing
production output.[14] Materials methods include selecting the proper material for the
application. In areas of minimal corrosion, cheap materials are preferable, but when
bad corrosion can occur, more expensive but longer lasting materials should be used.
Other materials methods come in the form of protective barriers between corrosive
substances and the equipment metals. These can be either a lining of refractory
material such as standard Portland cement or other special acid-resistant cements
that are shot onto the inner surface of the vessel. Also available are thin overlays of
more expensive metals that protect cheaper metal against corrosion without
requiring lots of material.[15]

[edit]History

The world's first oil refineries were set up by Ignacy Łukasiewicz near Jasło, Austrian
Empire (now in Poland) in the years 1854-56[16][17] but they were initially small as
there was no real demand for refined fuel. As Łukasiewicz's kerosene lamp gained
popularity the refining industry grew in the area.

The first large oil refinery opened at Ploieşti, Romania in 1856.[18] 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 heavily bombarded byUS Army Air Forces in Operation Tidal Wave,
August 1, 1943. Since then they have been rebuilt, and currently pose
somewhat[who?] of an environmental concern[citation needed].

Another early example is Oljeön, Sweden, now preserved as a museum at

the UNESCO world heritage site Engelsberg. It started operation in 1875 and is part
of the Ecomuseum Bergslagen.

At one time, the world's largest oil refinery 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 the Abadan refinery in Iran. This refinery suffered extensive damage
during the Iran-Iraq war. The world's largest refinery complex is the "Centro de
Refinación de Paraguaná" (CRP) operated by PDVSA in Venezuela with a production
capacity of 956,000 barrels per day (152,000 m³/d) (Amuay 635,000 bbl/d
(101,000 m³/d), Cardón 305,000 bbl/d (48,500 m³/d) and Bajo Grande 16,000
bpd). SK Energy's Ulsan refinery in South Korea with a capacity of 840,000 bbl/d
(134,000 m³/d) and Reliance Petroleum's refinery in Jamnagar, India with
660,000 bbl/d (105,000 m³/d) are the second and third largest, respectively.

[edit]Oil refining in the United States

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 US
Environmental Protection Agency (EPA) were not subject to any environmental
protection regulations. Today, national and state legislation requires refineries to
meet stringent air and water cleanliness standards. In fact, obtaining a permit to
build a modern refinery is perceived by many American oil companies to be so
difficult and costly that no new refineries have been built (though many have been
expanded) in the United States since 1976. As a result, some believe that this may be
the reason that the US is becoming more and more dependent on the imports of
finished gasoline, as opposed to incremental crude oil. On the other hand, studies
have revealed that accelerating merger activity in the refining and production sector
has reduced capacity further, resulting in tighter markets in the United States in
particular.