International Journal of Advancements in Research & Technology, Volume 3, Issue 4, April-2014
ISSN 2278-7763
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CRUDE OIL REFINERY BY POTASSIUM ALUM
By Ammineni Shyam Sundar, B.B.M, P.G.D.B.A,
Junior Assistant (Outsourcing),
Jawaharlal Nehru Technological University,
ANANTHAPURAMU – 515002,
A.P, INDIA.
E-mail: [email protected]
ABSTRACT
By refining Crude oil we get Liquified 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,
Sulfur etc. Due to various costly steps in Crude oil refinery and with the taxes
like FOB, Ocean Freight, Daughter Vessel Freight, Insurance, Ocean Loss, Port
charges, Custom Duty, Demurrage, and Entry Tax etc., the Price of Petrol and
Diesel, LPG etc., are increasing. If we reduce the cost of crude oil purification,
we can reduce the Price of Petrol and Diesel, LPG etc. By using Potassium
Alum in Crude oil purification we can do this. In general Potassium Alum is
used as a purifying factor for irrelevant objects that are found in drinking water,
as it melts with water thus producing Tri-Aluminum Ion which forms a
hydroxide with water having a foam –like quality that causes the irrelevant
objects in water to go down the water container, like this by putting Potassium
Alum in Crude Oil Refinery (may be by cracking) we can get LPG, Petrol,
Diesel etc. This will reduce the steps in oil refinery and by that the cost of
refinery.
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INTRODUCTION
The Oil Exploration and Refinery/Distillation are the major economic
activities to any country. The Crude Oil/Petroleum/Rock Oil is a naturally
occurring yellow to black liquid found in geologic formations beneath the
Earth’s surface, which is commonly refined into various types of fuels like
LPG, Petrol, Diesel, Kerosene etc. It consists of Hydrocarbons of various
molecular weights and other liquid organic compounds. Crude Oil Refinery
takes place in so many expensive steps like Desalter Unit, Atmospheric
distillation Unit, Vacuum distillation unit, Naphtha hydrotreater unit, Catalytic
reformer unit, Distillate hydrotreater unit, Fluid catalytic cracker Unit,
Hydrocracker unit, Visbreaking unit, Merox unit, Coking unit, Alkylation unit,
Dimerization unit, Isomerization unit, Steam reforming unit, Solvent refining
unit, Solvent dewaxing unit etc. To simplify above all the activities and by that
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International Journal of Advancements in Research & Technology, Volume 3, Issue 4, April-2014
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the expenses in the Crude Oil Refinery, in this experiment we are Cracking
Crude Oil by Potassium Alum to get LPG, Petrol, Diesel.
MATERIALS
1.
2.
3.
4.
CRUDE OIL
POTASSIUM ALUM
CRACKING
CRUDE OIL REFINERY
1. CRUDE OIL means all kinds of hydrocarbons in liquid form in their
natural state, formed by bacterial transformation of Organic matter by
decay in presence and/or absence of air. Crude Oil and gas are derived
almost entirely from decayed plants and bacteria. Energy from the sun,
which fuelled the plant growth, has been recycled into useful energy in
the form of hydrocarbon compounds - hydrogen and carbon atoms
linked together. The chemical composition of Crude Oil is,
S.NO.
1
2
3
4
5
6
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ITEM
CARBON
HYDROGEN
SULFUR
(Thiols, Sulphides, Cyclic
Sulphides, Disulphides,
Thiophenes,
Benzothiophenes,
Dibenzothiophenes,
Naphthobenzothiophenes)
NITROGEN
(Pyrrole, Indole,
Carbozole,
Benzocarbozole,
Pyridine, Quinoline,
Indoline, Benzoquinoline)
OXYGEN
(Alcohols/Ether/Cyclic
Ether/Furan, Carboxylic
acids, Naphthenic acids)
METALS
(Inorganic salts, Organic
Porphyrins (Ni, V, Mg
etc) in ppm
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PERCENTAGE
83.0% to 87.0%
10.0% to 14.0%
0.05% TO 6.0%
0.1% to 2.0%
0.05% to 1.5%
0.00% to 0.14%
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The main constituents of crude oils can be grouped into several broad
classes of compounds: saturates (including waxes), aromatics, resins, and
asphaltenes. Saturates are alkanes with structures of CnH2n+2 (aliphatics) or
CnH2n in the case of cyclic saturates (alicyclics). Small saturates (<C18) are the
most dispersible components of oils. Large saturates (waxes) can produce
anomalous evaporation, dispersion, emulsification, and flow behaviours.
Aromatics are compounds that have at least one benzene ring as part of their
chemical structure. The small aromatics (one and two rings) are fairly soluble in
water, but also evaporate rapidly from spilled crude oil. Larger aromatics show
neither of these behaviours to any extent. Resins and asphaltenes are similar in
many ways. Asphaltenes can be thought of as large resins. Both groups are
thought to be composed of condensed aromatic nuclei which may carry alkyl
and alicyclic systems containing heteroatoms such as nitrogen, sulphur, and
oxygen. Metals such as nickel, vanadium, and iron are also associated with
asphaltenes. Both groups do not appreciably evaporate, disperse, or degrade,
and both groups stabilize water-in-oil emulsions when they are present in
quantities greater than 3%. Waxes are predominantly straight-chain saturates
with melting points above 20°C. Asphaltenes are precipitated from n-pentane.
To separate saturates, aromatics, and resins, deasphaltened oil (maltenes) is
placed on an open silica column, and eluted sequentially with solvents of
increasing polarity. Waxes can be precipitated from the maltenes with a mixture
of methyl ethyl ketone and dichloromethane at -32°C.
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2. POTASSIUM ALUM, potash alum or Tawas is the potassium double sulfate
of aluminium. Its chemical formula is Kal (So4 )2 and it is commonly found in
its dodecahydrate form as Kal (So 4 )2·12(H 2 O). Alum is the common name
for this chemical compound, given the nomenclature of potassium aluminum
sulfate dodecahydrate. It is commonly used in water purification, leather
tanning, dyeing, fireproof textiles, and baking powder. It also has cosmetic
uses as a deodorant, as an aftershave treatment and as a styptic for minor
bleeding from shaving.
CHARACTERISTICS
Potassium alum crystallizes in regular octahedra with flattened corners, and is
very soluble in water. The solution reddens litmus and is an astringent. When
heated to nearly a red heat it gives a porous, friable mass which is known as
"burnt alum." It fuses at 92 °C in its own water of crystallization. "Neutral
alum" is obtained by the addition of as much sodium carbonate to a solution of
alum as will begin to cause the separation of alumina. Alum finds application as
a mordant, in the preparation of lakes for sizing handmade paper and in the
clarifying of turbid liquids. It can also be used as fire proof material and in
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preparation of many fire proof clothing. Molar Mass is 258.21 g/mol. Boiling
Point is 200 °C. Melting Point is 92-93 °C. Density is 1.76 g/cm³. Odorless.
Solubility in Water is 14.00 g/100 Ml (20 °C), 36.80 g/100 mL (50 °C).
Refractive Index (nD): 1.4564.
MINERAL FORM AND OCCURRENCE
Potassium alum or alum-(K) is a naturally occurring sulfate mineral which
typically occurs as encrustations on rocks in areas of weathering and oxidation
of sulfide minerals and potassium-bearing minerals. In the past, alum was
obtained from alunite, a mineral mined from sulfur-containing volcanic
sediments source. Alunite is an associate and likely potassium and aluminium
source. It has been reported at Vesuvius, Italy, east of Springsure, Queensland,
Alum Cave, Tennessee, Alum Gulch, Santa Cruz County, Arizona and the
Philippine island of Cebu. A related mineral is kalinite, a fibrous mineral with
formula KAl(SO4)2·11(H2O).
USES
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Potassium alum is an astringent/styptic and antiseptic. For this reason, it can be
used as a natural deodorant by inhibiting the growth of the bacteria responsible
for body odor. Use of mineral salts in such a fashion does not prevent
perspiration. Its astringent/styptic properties are often employed after shaving
and to reduce bleeding in minor cuts and abrasions, nosebleeds, and
hemorrhoids. It is frequently used topically and internally in traditional systems
of medicine including Ayurveda, where it is called phitkari or saurashtri, patika
in Telugu language and Traditional Chinese Medicine, where it is called Ming
fan. It is also used as a hardener for photographic emulsions (films and papers),
usually as part of the fixer, although modern materials are adequately hardened
and this practice has fallen out of favor. It is also used in tanning of leather.
Aftershave: In rock form, alum is used as an aftershave, due to its astringent
property. It can be rubbed on freshly shaved face, and its astringent property
helps in preventing and reducing bleeding caused due to minor cuts.
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3. CRACKING, In petroleum geology and chemistry, cracking is the process
whereby complex organic molecules such as kerogens or
heavy hydrocarbons are broken down into simpler molecules such as light
hydrocarbons, by the breaking of carbon-carbon bonds in the precursors.
Cracking is the breakdown of a large alkane into smaller, more
useful alkanes and alkenes. Hydrocarbon cracking is the process of breaking a
long-chain of hydrocarbons into short ones. Cracking is used to describe any
type of splitting of molecules under the influence of heat, catalysts and solvents,
such as in processes of destructive distillation or pyrolysis. Fluid catalytic
cracking produces a high yield of gasoline and LPG, while hydrocracking is a
major source of jet fuel, diesel, naphtha, and LPG. The same principle is
adopted in this experiment with Potassium Alum without any heat.
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A large number of chemical reactions take place during the cracking process,
most of them based on free radicals. The main reactions that take place include:
Initiation
In these reactions a single molecule breaks apart into two free radicals.
CH3 CH3 → 2 CH3 •
Hydrogen abstraction
In these reactions a free radical removes a hydrogen atom from another
molecule, turning the second molecule into a free radical.
CH3 • + CH 3 CH3 → CH 4 + CH3 CH2 •
Radical decomposition
In these reactions a free radical breaks apart into two molecules, one an alkene,
the other a free radical. This is the process that results in alkene products.
CH3 CH2 • → CH 2 =CH2 + H•
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Radical addition
In these reactions, the reverse of radical decomposition reactions, a radical
reacts with an alkene to form a single, larger free radical. These processes are
involved in forming the aromatic products that result when heavier feedstocks
are used.
CH3 CH2 • + CH2 =CH2 → CH3 CH 2 CH 2 CH 2 •
Termination
In these reactions two free radicals react with each other to produce products
that are not free radicals. Two common forms of termination are recombination,
where the two radicals combine to form one larger molecule,
and disproportionation, where one radical transfers a hydrogen atom to the
other, giving an alkene and an alkane.
CH3 • + CH 3 CH2 • → CH3 CH 2 CH3
CH3 CH2 • + CH3 CH2 • → CH 2 =CH2 + CH3 CH3
4. CRUDE OIL REFINERY, is done by the following processes
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1. Desalter unit washes out salt from the crude oil before it enters the
atmospheric distillation unit.
2. Atmospheric distillation unit distills crude oil into fractions.
3. Vacuum distillation unit further distills residual bottoms after atmospheric
distillation.
4. Naphtha hydrotreater unit uses hydrogen to desulfurize naphtha from
atmospheric distillation.
5. 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.
6. Distillate hydrotreater unit desulfurizes distillates (such as diesel) after
atmospheric distillation.
7. Fluid catalytic cracker (FCC) unit upgrades heavier fractions into lighter,
more valuable products.
8. Hydrocracker unit uses hydrogen to upgrade heavier fractions into lighter,
more valuable products.
9. Visbreaking unit upgrades heavy residual oils by thermally cracking them
into lighter, more valuable reduced viscosity products.
10. Merox unit treats LPG, kerosene or jet fuel by oxidizing mercaptans to
organic disulfides.
11. Alternative processes for removing mercaptans are known, e.g. doctor
sweetening process and caustic washing.
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12. 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.
13. Alkylation unit produces high-octane component for gasoline blending.
14. 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.
15. Isomerization unit converts linear molecules to higher-octane branched
molecules for blending into gasoline or feed to alkylation units.
16. Steam reforming unit produces hydrogen for the hydrotreaters or
hydrocracker.
17. Liquified gas storage vessels store propane and similar gaseous fuels at
pressure sufficient to maintain them in liquid form.
18. Storage tanks store crude oil and finished products, usually cylindrical, with
some sort of vapor emission control and surrounded by an earthen berm to
contain spills.
19. Amine gas treater, Claus unit, and tail gas treatment convert hydrogen
sulfide from hydrodesulfurization into elemental sulfur.
20. Utility units such as cooling towers circulate cooling water, boiler plants
generates steam, and instrument air systems include pneumatically operated
control valves and an electrical substation.
21. Wastewater collection and treating systems consist of API separators,
dissolved air flotation (DAF) units and further treatment units such as an
activated sludge biotreater to make water suitable for reuse or for disposal.
22. Solvent refining units use solvent such as cresol or furfural to remove
unwanted, mainly aromatics from lubricating oil stock or diesel stock.
23. Solvent dewaxing units remove the heavy waxy constituents petrolatum
from vacuum distillation products.
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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.
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PROJECT EXPERIMENT
By using Potassium Alum in Crude Oil purification, may be by cracking we get
the result. In my previous experiments with Potassium Alum, I noticed that, if
we kept 50 grams of Potassium Alum in liter Petrol and Diesel for one hour to 2
days, there is increase in Calorific value of Petrol and Diesel as the time
increasing, i.e., suppose at the starting stage the Petrol Calorific value is 48,000
kj/kg after keeping Potassium Alum one day, it is 48,500 and Diesel Calorific
value is 44,000 kj/kg after one day 44,500 kj/kg like that it is increasing. As the
Crude oil is a mixture of different hydrocarbons and is not compound with a
specific chemical formula, think for example it’s chemical formula as C 20 H 25
If we kept 50 grams of Potassium Alum in One liter Crude Oil for One hour,
C 20 H 25 + Kal (So 4 ) 2 . 12H2 O
CH + C 19 H 24 + Kal (So 4 ) 2 .12H 2 O
If we kept 50 grams of Potassium Alum in One liter Crude Oil for Two hours,
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C 20 H 25 + Kal (So 4 ) 2 . 12H2 O
CH+CH + C 18 H 23 + Kal (So 4 ) 2 .12H2 O
Like this by Cracking Crude Oil with Potassium Alum without any heat we can
get all the LPG, Petrol, Diesel etc., by time delay.
ACKNOWLEDGEMENTS
I, the Author dedicate my sincere gratitude to Jawaharlal Nehru
Technological University, Ananthapuramu.
REFERENCES
1. Wikipedia by Internet.
2. Samasta Vastu Guna Deepika, Ayurvedam.
4. Petrol & Diesel Pollution Control by Potassium Alum, research article by
Ammineni Shyam Sundhar. Paper Published in IJoART
Volume 2, Issue3, March, 2013 Edition (ISSN 2278-7763). (www.ijoart.org)
5. Green diesel by potassium alum, research article by Ammineni shyam sundar,
Paper Published in IJoART Volume 2, Issue4, April, 2013 Edition (ISSN
2278-7763). (www.ijoart.org)
6. Potassium Alum Effect on Performance and Emissions of Diesel in an I.C
Engine, research article by Ammineni Shyam Sundhar, Paper Published in
IJoART Volume 2, Issue 5, May,2013 Edition (ISSN 2278-7763).
(www.ijoart.org)
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