Академический Документы
Профессиональный Документы
Культура Документы
PETROLEUM INDUSTRY
What is Petroleum?
The name petroleum covers both naturally occurring unprocessed crude oil
and petroleum products that are made up of refined crude oil.
History of Petroleum
Petroleum, in one form or another, has been used since ancient times, and
is now important to society, including in economy, politics and technology. The
rise in importance was due to the invention of the combustible engine, the rise in
commercial aviation and the importance of petroleum to industrial organic
chemistry, particularly the synthesis of plastics, fertilizers, solvents, adhesives
and pesticides.
More than 400 years ago, asphalt was used in the construction of the walls
and towers of Babylon; there were oil pits near Babylon, and a pitch spring on
Zacynthus. By 347 AD, oil was produced from bamboo-drilled wells in China.
In 1847, the process to distill kerosene from petroleum was invented by
James Young. The petroleum from which he distilled a light thin oil suitable for
use as a lamp oil, and a thicker oil suitable for lubricating machinery. In 1848,
Young set up a small business refining crude oil. Young found that by slow
distillation he could obtain multiple useful liquids from petroleum, one which he
named paraffinne oil because when congealed it resembles paraffin wax.
In 1851, the first true commercial oil-works in the world was established at
Bathgate by E.W Binney & Co. which was a partnership between Young &
Meldrum and Edward William Binney.
Petroleum 1
Heavy crude is less than 30API, while light crude is greater than 30API.
1 For example, a typical crude oil may begin to boil at 104 F to produce petroleum gas
used for heating and making plastics, and finish boiling at greater than 1112 F to
produce residuals such as petroleum coke, asphalt and tar.
Petroleum 3
Crude oil is found in geologic formations beneath the earths surface. It is formed
when large quantities of dead organisms 2 are buried underneath sedimentary rock
and subjected to intense heat and pressure.
Petroleum is recovered mostly through oil drilling. This comes after the studies
of structural geology (at the reservoir scale), sedimentary basin analysis, and
reservoir characterization.3
Oil reserves are the amount of technically and economically recoverable oil.
Reserves may be for a well, for a reservoir, for a field, for a nation, or for the world.
Different classifications of reserves are related to their degree of certainty.
The total estimated amount of oil in an oil reservoir, including both producible
and non-producible oil, is called oil in place. However, because of reservoir
characteristics and limitations in petroleum extraction technologies, only a fraction
of this oil can be brought to the surface, and it is only this producible fraction that
is considered to bereserves. The ratio of reserves to the total amount of oil in a
particular reservoir is called the recovery factor. Determining a recovery factor for a
given field depends on several features of the operation, including method of oil
recovery used and technological developments.
Based on data from OPEC4 at the beginning of 2013 the highest proved oil
reserves including non-conventional oil deposits are in Venezuela (20% of global
reserves), Saudi Arabia (18% of global reserves), Canada (13% of global reserves),
and Iran (9%). (OPEC Annual Statistical Bulletin, 2013)
2 Usually zooplankton and algae
3
4 Organization of the Petroleum Exporting Countries is an international organization and economic cartel whose mission is to coordinate the
policies of the oil-producing countries.
Petroleum 4
Range
Average
15 60 %
30 %
30 60 %
49%
Aromatics
3 30 %
15 %
Asphaltics
remainder
6%
n
Alkanes
(paraffins)
Naphthenes
Composition by Weight
Element
Percent Range
Carbon
83 - 85 %
Hydrogen
10 14 %
Nitrogen
0.1 2 %
Petroleum 6
Oxygen
Sulfur
Metals
0.05 1.5 %
0.05 6.0 %
< 0.1 %
form
oil
reservoirs.
The
"classic"
method
includes
making
an
from the upper to the lower parts where the wells are located. Recovery
factor during the primary recovery stage is typically 5-15%.
While the underground pressure in the oil reservoir is sufficient to
force the oil to the surface; all that is necessary is to place a complex
arrangement of valves (the Christmas tree) on the well head to connect
the well to a pipeline network for storage and processing. Sometimes
pumps, such as beam pumps and electrical submersible pumps (ESPs),
are used to bring the oil to the surface; these are known as artificial lift
mechanisms.
Secondary recovery
Over the lifetime of the well the pressure will fall, and at some
point there will be insufficient underground pressure to force the oil to
the surface. After natural reservoir drive diminishes, secondary
recovery methods are applied. They rely on the supply of external energy
into the reservoir in the form of injecting fluids to increase reservoir
pressure, hence replacing or increasing the natural reservoir drive with
an artificial drive. Secondary recovery techniques increase the
reservoir's pressure by water injection, natural gas reinjection and gas
lift, which injects air, carbon dioxide or some other gas into the bottom
of an active well, reducing the overall density of fluid in the wellbore.
Typical recovery factor from water-flood operations is about 30%,
depending on the properties of oil and the characteristics of the
reservoir rock. On average, the recovery factor after primary and
secondary oil recovery operations is between 35 and 45%.
Enhanced recovery
Enhanced, or Tertiary oil recovery methods increase the mobility
of the oil in order to increase extraction.
Petroleum 8
Petroleum 9
Petroleum 1
0
The problem with crude oil is that it contains hundreds of different types of
hydrocarbons all mixed together. You have to separate the different types of
hydrocarbons to have anything useful. Fortunately there is an easy way to separate
things, and this is what oil refining is all about.
Different hydrocarbon chain lengths all have progressively higher boiling
points, so they can all be separated by distillation. This is what happens in an oil
refinery - in one part of the process, crude oil is heated and the different chains are
pulled out by their vaporization temperatures. Each different chain length has a
different property that makes it useful in a different way.
In a refinery, crude is converted into finished products using rigorous
processes involving three types of operations (separation, conversion, upgrading):
Separation processes
The first stage involves separating the molecules through atmospheric
distillation (i.e. normal atmospheric pressure), according to their molecular weight.
This process, also known as topping, consists of heating the oil to 350/400C,
causing it to evaporate at the base of a 60-meter-high distillation tower.
The crude vapors rise inside the tower while the heaviest molecules, or heavy
residue, remain at the bottom without evaporating. As the vapors rise the
temperature progressively drops causing the molecules to condense into liquids, the
heaviest first followed by gases that alone reach the top of the tower, where the
temperature is now only 150C. There are outlets located at different levels to collect
these liquids, which become increasingly light up along the tower. Each outlet
corresponds to a fractional distillation, also known as a petroleum cut, beginning
with bitumen (highly viscous hydrocarbons) all the way to gases.
Petroleum 1
1
The heavy residue from this distillation still contains many mid-density
products. This residue is placed in another tower and distilled again to recover
mid-range products (heavy fuel and diesel).
Conversion processes
After separation, the proportion of heavy hydrocarbons is still too high. To meet
demand for lighter products, these heavy molecules are broken up into two or more
lighter molecules. This conversion process, carried out at 500C, is also known as
catalytic cracking because it uses a catalyst (a substance that accelerates and
facilitates chemical reactions). 75% of heavy products subjected to conversion are
converted into gas, gasoline and diesel this way.
The result can be improved by adding hydrogen (hydrocracking) or using carbon
extraction methods to recover more light molecules (deep conversion). So, all heavy
hydrocarbons can be converted into light hydrocarbons but the more complex the
operation the more it costs and the more energy it uses. The ongoing aim of refiners
is to find a balance between the degree and the cost of the conversion!
Upgrading processes
These involve significantly reducing or eliminating corrosive or environmentally
harmful molecules particularly sulfur. EU sulfur emission standards are strict:
since January 1, 2009, gasoline and diesel containing more than 10 ppm (10
mg/kg) of sulfur may not be used in Europe. The purpose of these measures is to
improve the ambient air quality by optimizing the effectiveness of catalytic exhaust
gas treatment technologies. Diesel is desulfurized at 370C, at a pressure of 60 bars
and in the presence of hydrogen: under these conditions, the sulfur atoms break off
Petroleum 1
2
from the hydrocarbon molecules and combine with hydrogen atoms to form
hydrogen sulfide (H2S). This is then processed to extract sulfur, a substance used in
industry.
Kerosene - fuel for jet engines and tractors; starting material for making other
products
Petroleum 1
3
o liquid
o mix of alkanes (10 to 18 carbons) and aromatics
o boiling range = 350 to 617 degrees Fahrenheit / 175 to 325 degrees
Celsius
Gas oil or Diesel distillate - used for diesel fuel and heating oil; starting
material for making other products
o liquid
o alkanes containing 12 or more carbon atoms
o boiling range = 482 to 662 degrees Fahrenheit / 250 to 350 degrees
Celsius
Heavy gas or Fuel oil - used for industrial fuel; starting material for making
other products
o liquid
o long chain (20 to 70 carbon atoms) alkanes, cycloalkanes, aromatics
o boiling range = 700 to 1112 degrees Fahrenheit / 370 to 600 degrees
Celsius
Residuals - coke, asphalt, tar, waxes; starting material for making other
products
Petroleum 1
4
o solid
o multiple-ringed compounds with 70 or more carbon atoms
o boiling range = greater than 1112 degrees Fahrenheit / 600 degrees
Celsius
Apart from these features and basic uses, each refinery markets its own finished
products, obtained by mixing various products and additives. Oil companies offer
a range of different fuels that are more environmentally-friendly and that ensures
engines work better and have a longer life. (Petroleum)
Fluid catalytic cracking (FCC) unit: Upgrades the heavier, higher-boiling fractions from
the crude oil distillation by converting them into lighter and lower boiling, more
valuable products.
Hydrocracker unit: Uses hydrogen to upgrade heavier fractions from the crude oil
distillation and the vacuum distillation units into lighter, more valuable products.
Visbreaker unit upgrades heavy residual oils from the vacuum distillation unit by
thermally cracking them into lighter, more valuable reduced viscosity products.
Delayed coking and fluid coker units: Convert very heavy residual oils into endproduct petroleum coke as well as naphtha and diesel oil by-products.
Petroleum 1
7
or extracted from oil or gas streams as they emerge from the ground. It was first
produced in 1910 by Dr. Walter Snelling, and the first commercial products
appeared in 1912. It currently provides about 3% of the energy consumed, and
burns cleanly with no soot and very few sulfur emissions, posing no ground or water
pollution hazards. LPG has a typical specific calorific value of 46.1 MJ/kg compared
with 42.5 MJ/kg for fuel-oil and 43.5 MJ/kg for premium grade petrol (gasoline).
However, its energy density per volume unit of 26 MJ/l is lower than either that of
petrol or fuel-oil.
Large quantities of propane and butane are now available from gas and
petroleum industries. These are often employed as fuel for tractors, trucks, and
buses and mainly as a domestic fuel. They are gases under ordinary pressure.
Because of the low boiling point (-44 to 0C) and high vapor pressure of these gases,
their handling as liquids in pressure cylinders is necessary. Thus, they can be easily
liquefied under pressure. The petroleum gas, which has been liquefied under
pressure is called Liquefied petroleum gas (LPG).
Petroleum gas is supplied in liquid form so that a cylinder of even small
volume may contain an appreciable amount of the gas. A domestic gas cylinder
whose main constituent is butane, contains about 14 kg of LPG. A strong smelling
substance (Ethyl mercaptan C2H5SH) is added to LPG gas cylinders to help in the
detection of gas leakage. The gas used for domestic cooking is called Liquefied
Petroleum Gas (LPG) because it is present in liquid form in the cylinders and is
commonly used for domestic heating purposes.
Owing to demand from industry for butane derivatives, LPG sold as fuel for
automobiles is made up largely of propane. This is because,
Petroleum 1
9
LPG leaves little or no engine deposit in the cylinders when it burns, a factor
Manufacturing Process
Desalting
Crude oil introduced to refinery
processing
contains
undesirable
impurities,
many
such
as
polymer,
byproduct,
etc.
corrosion
The
salt
When a mixture
Crude oil passes through the cold preheat train and is then pumped to the desalters
by crude charge pumps. The recycled water from the desalters is injected in the
crude oil containing sediments and produced salty water. This fluid enters in the
static mixer which is a crude/water disperser, maximizing the interfacial surface
area for optimal contact between both liquids.
The wash water shall be injected as near as possible emulsifying device to avoid a
first separation with crude oil. Wash water can come from various sources including
relatively high salt sea water, stripping water, etc. The static mixers are installed
upstream the emulsifying devices to improve the contact between the salt in the
crude oil and the wash water injected in the line.
The oil/water mixture is homogenously emulsified in the emulsifying device. The
emulsifying device (as a valve) is used to emulsify the dilution water injected
upstream in the oil. The emulsification is important for contact between the salty
production water contained in the oil and the wash water. Then the emulsion enters
the Desalters where it separates into two phases by electrostatic coalescence.
The electrostatic coalescence is induced by the polarization effect resulting from an
external electric source. Polarization of water droplets pulls them out from oil-water
emulsion phase. Salt being dissolved in these water droplets, is also separated along
the way. The produced water is discharged to the water treatment system (effluent
water). It can also be used as wash water for mud washing process during operation.
Petroleum 2
1
Gas
Separation
Liquid
fractions are
drawn from
the
trays
and
removed. In
this way the light gases, methane, ethane, propane and
butane pass out the top of the column, petrol is formed in
the top trays, kerosene and gas oils in the middle, and fuel
oils at the bottom.
The atmospheric fractionator normally contains 30 to 50
fractionation trays. Separation of the complex mixtures of crude is relatively easy
and generally 5 to 8 trays are needed for each side stream product plus the same
number above and below the feed plate.
Thus crude oil atmospheric fractionation tower with four liquid sidestream
drawoffs will require some 30 to 42 trays.
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.
Polymerization
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. 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.
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.
Treating and Blending
The refined gas was treated and blended with merox to form the final product,
the LPG. Merox is an acronym for mercaptan oxidation. It is a proprietary catalytic
chemical process developed by UOP used in oil refineries and natural gas processing
plants to remove mercaptans from LPG.
GASOLINE
Petroleum 2
3
Allow engines to start and run well in cold or hot weather - this is achieved by
controlling volatility.
Let engines run reliably and efficiently for a long time - this is achieved by
controlling stability and corrosiveness, and the tendency of the gasoline to
form residues and deposits in engines and fuel systems.
Able to benefit from new engine and emissions control technologies - this is
achieved by limiting sulfur content and controlling octane number and
volatility.
pipe
over
40
miles
from
Salt
Creek
to
Casper,
Wyoming.
Charles
lead was phased out. In 1990, the Clean Air Act created major changes on gasoline,
rightfully intended to eliminate pollution.
Raw Materials
Crude Oil
Additives
Additive
Anti-knocking agents
Anti-oxidants
Metal deactivators
Deposit modifiers
Surfactants
Freezing point
depressants
Function
Example
Improve octane ratings Tetraethyllead,
and
reduce
engine Methylcyclopentadienyl
knocking
manganese
tricarbonyl
(MMT),
Ferrocene,
Toluene, Isooctane
Inhibit gum formation Butylated
and improve stability
hydroxytoluene,
Ethylene diamine, pPhenylenediamine, 2,6Di-tert-butylphenol
Inhibit gum formation N,N-Disalicylidiene-1,2and improve stability
propanediamine,
Benzotriazole
Reduce deposits, spark- Ethylene dichloride,
plug fouling and preignition
Prevent icing, improve Long
chain
of
vaporization,
inhibit alkyldiamines,
deposits, reduce nitrate Alkylsuccinimides
of
emissions
diethylenetriamine
Prevent icing
T-Butanol
Petroleum 2
7
Corrosion inhibitors
Dyes
Prevent
gasoline DCI-4A, DCI-6A
corroding storage tanks
Product color for safety, Solvent Red 24, Solvent
or regulatory purposes
Red 26, Solvent Yellow
124, Solvent Blue 35
Petroleum 2
8
Cracking
Since
the
marketplace
establishes
product value, our competitive edge depends on
efficiently we can convert middle distillate, gas
residuum into the highest value products.
Heat and catalysts are used to convert
heavier oils to lighter products using three
"cracking" methods: fluid catalytic cracking
hydrocracking (Isomax), and coking (or
thermal-cracking).
2.
how
oil and
the
(FCC),
The Fluid Catalytic Cracker (FCC) uses high temperature and catalyst to crack
86,000 barrels (3.6 million gallons) each day of heavy gas oil mostly into gasoline.
Hydrocracking uses catalysts to react gas oil and hydrogen under high pressure and
high temperature to make both jet fuel and gasoline. Also, about 58,000 barrels (2.4
million gallons) of lighter gas oil is converted daily in two Isomax Units, using this
hydrocracking process.
Petroleum 2
9
3. Alkylation
While the cracking processes break most of the gas oil into gasoline and jet
fuel, they also break off some pieces that are lighter than gasoline. This process
takes the small molecules and recombines them in the presence of sulfuric acid
catalyst to convert them into high octane gasoline.
Petroleum 3
0
5. Reforming
Octane rating is a key measurement of how well a gasoline performs in an
automobile engine. Much of the gasoline that comes from the Crude Units or from
the Cracking Units does not have enough octane to burn well in cars.
The gasoline process streams in the refinery that have a fairly low octane
rating are sent to a Reforming Unit where their octane levels are boosted. These
reforming units employ precious-metal catalysts - platinum and rhenium and
thereby get the name "rheniformers." In the reforming process, hydrocarbon
molecules are "reformed" into high octane gasoline components. For example, methyl
cyclohexane is reformed into toluene.
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.
KEROSENE
Kerosene, also spelled kerosine, also called paraffin oil or coal oil is a
flammable yellow to colorless oily liquid with a not-unpleasant
smell. While can be extracted from coal or shale, kerosene is
primarily derived from petroleum. It is a distillate of petroleum
with boiling points ranging from 150 to 300 OC (300 to 575OF),
and therefore classified as so-called middle distillates along with
diesel oil. It primarily consists of mixtures of hydrocarbons with
12-15 carbon atoms. Kerosene is used as fuel for lamps,
furnaces, cooking stoves and jet engines, as a solvent for greases and also as an
insecticide.
History
wax oil.
1848 James Young, a Scottish chemist who experimented and discovered dry
distillation of boghead oil that produces various products including the one he
in Bathgate in 1851.
1851 Samuel Martin Kier began selling kerosene to local miners, under the
name of Carbon Oil.
Petroleum 3
2
Mid 1850s Kerosene was used as a fuel for lamps but kerosene was then a
very expensive commodity was only used in many public venues and homes of
wealthy.
1860 Oil wells were discovered in Northwestern Pennsylvania and
Southwestern Ontario and that began the mass production of kerosene that
and furnaces.
Late 1890s and early 1900s Kerosene became the most important refinery
product.
1920 Kerosene surpassed gasoline as a fuel for internal combustion engine.
Raw Materials
Petroleum/ Crude Oil
Kerosene is extracted from petroleum chemicals found deep within the earth.
This mixture of petroleum chemicals is consists of oil, rocks, water and other
subterranean contaminants in the reservoir of sandstone and carbonate rocks. The
oil itself (crude oil) is come from decayed organisms of buried along with the
sediments of prehistoric eras. Over ten millions of years, organic residues came from
these organisms were converted into petroleum by means of chemical processes
called diagenesis and catagenesis. Diagenesis occurs on temperature below 122 OF
(50OC) that involves both microbial activity and chemical reactions such as
dehydration, condensation, cyclization and polymerization. Catagenesis occurs with
temperature
between
122OF
and
393OF
(50OC
and
200OC)
that
involves
Petroleum 3
3
are
three
ways
of
drilling
ocean floor.
Flushing
Once the drilling process breaks the reservoir, crude oil erupts from the
ground by the force of hydrocarbon gas. Flushing is done to have more to have
more oil recovery from beneath by pumping water into the well to push the oil
out. Addition of surfactant to the water will create higher recovery of oil. Water
is separated from oil after washing.
The oil obtained are now stored in tanks then delivered to refinery.
Petroleum 3
4
Separation
Distillation
Distillation is a process of separation of components of
crude oil by means of the difference of boiling points
among the components. The stream of crude oil is sent
to the bottom of the distillation column where it is
heated to vapor. Lighter hydrocarbons rise to the top of
the column and most of the high-boiling point
fractions are left at the bottom. The fraction condensed
and collected having the boiling points 302OF to 482OF
(150OC to 200OC) is the kerosene. To achieve higher
purity, refluxing or recycling of kerosene multiple times is done.
Petroleum 3
5
Purification
kerosene
containing
in
an
caustic
alkaline
soda
environment,
(NaOH).
This
1. Prewashing
The process operation starts with the water coalescence or the formation of
drain water layer from the aggregation of natural water droplets from
Petroleum 3
7
Packaging
Once the kerosene is fully refined, they are now placed in metal drums, tanks
or opaque plastic container and are now ready for shipment. Careful handling
is very necessary since the kerosene is highly flammable.
Quality Control
Testing the amount of unwanted components or hydrocarbons is conducted.
The result of the analysis of kerosene tells the efficiency of extraction and
distillation. Refluxing or repeated recycle of kerosene fraction helps to maximize the
Petroleum 3
8
REFERENCES
Alboudwarej.
(2006).
Highlighting
Heavy
Oil.
Retrieved
from
http://www.slb.com/~/media/Files/resources/oilfield_review/ors06/sum06/heavy_
oil.ashx
OPEC Annual Statistical Bulletin. (2013). Retrieved September 11, 2014, from OPEC
website: http://www.opec.org/opec_web/en/data_graphs/330.htm
Petroleum.
(n.d.).
Retrieved
September
http://en.wikipedia.org/wiki/Petroleum
Osha.
(2006).
Polymerization
in
11,
petroleum
2014,
refining.
from
Wikipedia:
Retrieved
from
http://www.eoearth.org/view/article/155306/
Binod Shrestha. (2005). Hydrocarbon from petroleum. Retrieved from http://chemguide.blogspot.com/2010/04/hydrocarbon-from-petroleum.html
Jrank.
(2003).
Kerosene.
Retrieved
from
http://www.madehow.com/Volume-
7/Kerosene.html.
Ali, M., et al. (2005). Handbook of industrial chemistry. USA: McGraw-Hills
Companies Inc.
Austin, G. (1984). Shreve's chemical process industries. USA: McGraw-Hills
Companies Inc.
Petroleum 3
9