PETROLEUM PROCESSING

Products of Petroleum and Petroleum Refining

A Written Report by Patrick Earl J. Berino

CLASSIFICATIONS OF PETROLEUM PRODUCTS

Petroleum products are classified as light, intermediate, heavy distillates, and

residues. Light distillates include aviation gasoline, motor gasoline, naphthas, petroleum,
solvents, jet-fuel, and kerosene. Any given refinery rarely makes all of them. Gasoline is the
most important product, and around 45 percent of the crude processed now ends up as
gasoline. When the compression ratio of a motor is relatively high, the fuel can detonate in
the cylinder causing noise (knock), power loss and ultimately engine damage. Branched
chain and aromatic hydrocarbons greatly reduce the tendency of a fuel to cause knocking.
n-Heptane knocks very readily; 2,2,4-trimethyl pentane (formerly known as iso-octane) is an
extremely antiknock fuel. The octane number, a measure of the suitability of a fuel for high-
compression engines, is the percentage of iso-octane which, when added to n-heptane,
knocks in a special test engine to the same degree as the fuel being tested. Substances such
as tetraethyl lead (TEL) can be added to gasoline in very small quantities to raise the octane
number dramatically. Because of doubts concerning the safety of lead in the environment,
these additives are now restricted or limited.
When the Environmental Protection Agency (EPA) reduced the lead (as TEL)
allowable in some gasoline and required its absence from most, refineries faced a difficult
problem. The amount of branched chain and aromatic constituents in regular gasoline had
to be increased to keep the antiknock high after the lead was removed. The problem was
resolved by utilizing more severe cracking, by adding octane boosters such as methyl
tertiary butyl ether (MTBE), methanol and ethanol. This continues to be a problem for
gasoline suppliers.
Intermediate distillates include gas oil, light and heavy domestic furnace oils, diesel
fuels, and distillates used for cracking to produce more gasoline. These distillates are used
mainly for transportation fuels in heavy trucks, railroads, small commercial boats, standby
and peak-shaving power plants, farm equipment, and wherever diesels are used to produce
power.
Heavy distillates are converted into lubricating oils, heavy oils for a variety of fuel
uses, waxes, and cracking stock. Lubricating oils of high quality can readily be made from
paraffin-base oils, but most oils are mixed or naphthene base, and solvent refining is
required to produce quality lubricants. Additives (antioxidants, detergents, antifoams, etc.)
are used extensively to improve the quality of lubricants. Heavy distillates are used for
bunker fuel for ships and in large stationary power plants but all uses of heavy distillates are
declining and the tendency is to use them as cracking stock. Sulfur content is a major
determinant of the value of heavy distillates, it must be low if the product is to be readily
salable.
Residues are constituents that are simply not volatile enough to be distilled, even
under vacuum. These include asphalt, residual fuel oil, coke, and petrolatum. These
difficulty salable materials are by-products of the refining process, and while many are
extremely useful, most are difficult to dispose of and are relatively unprofitable. Petroleum
coke is used in making electrodes. Asphalt is used as a road-paving material, for
waterproofing structures, and in roofing material. The properties of asphalt are markedly
changed by heating it and partly oxidizing it by blowing air through it. The resulting material
is more viscous and less resilient than ordinary asphalt.
Production of some of these products is very large, and over 1000 organic chemicals
are derived from petroleum. Examples are butadiene, styrene, ethylene glycol, polyethylene
and many more.

Processing or Refining of Petroleum

PRECURSORS OF PETROCHEMICALS
 Precursors are reactive materials usually made by breaking down larger molecules
called feedstocks. For example, ethylene is currently being made from liquefied nitrogen gas
(LNG), naphtha, gas oil, diesel fuel, ethane, propane, and butane, with coal a possibility
soon to be explored, and some testing of liquefied coal already completed. The principal
precursors are: ethylene, acetylene, propylene, butene, benzene, toluene, xylenes and
naphthalene.

The flowchart below shows the manufacture from refinery gas with the analysis (in
percent): methane, 25; hydrogen, 19; ethane, 15; ethylene, 7; propane, 12; and propylene,
6, with the remainder N 2, CO, CO2, H2S, and higher hydrocarbons. LPG, high-run gasoline,
and ethylene recycle may be added to this.
 Refining is a low-cost operation compared with most chemical processing. Crude cost
was formerly far lower than now, but the Organization of Petroleum Exporting Countries
(OPEC) raised the price approximately tenfold.
Refining involves two major branches, separation processes and conversion
processes. Particularly in the field of conversion, there are literally hundreds of processes in
use, many of them patented. Early refineries separated petroleum components into salable
fractions by some type of distillation. Some chemical or heat treatment often followed to
improve the quality of the crude product obtained.
The unit operations used in petroleum refining are the simple usual ones, but the
interconnections and interactions may be complex. Most major units are commonly referred
to as stills. A crude still consists of heat exchangers, a furnace, a fractionating tower, steam
strippers, condensers, coolers, and auxiliaries. There are usually working tanks for
temporary storage at the unit; frequently there are treating tanks, used for improving the
color and removing objectionable components, particularly sulfur; blending and mixing
tanks; receiving and storage tanks for crude feed; a vapor recovery system; spill and fire
control systems; and other auxiliaries. For the refinery as a whole, a boiler house and
usually an electrical generating system are added. A control room with instruments to
measure, record and control, thus keeping track of material which permits heat and material
balances forms the heart of the system. One of the major functions of the instruments is to
permit accurate accounting of the materials and utilities used. Many control systems are
now connected to computers which do many calculations routinely.
The following unit operations are used extensively in the separative section:
1. Fluid flow. Fluid flow is an operation that must not permit any unexpected failure
because fire and explosion might occur.
2. Heat transfer. Transfer coefficients change daily as fouling occurs. Cooling towers
become less effective with time. Modern plants check the condition of the
exchangers daily against computer records.
3. Distillation. When the difference in volatility between components is too small for
separation in a reasonably sized tower, modifications of simple distillation are used.
When a solvent of low volatility is added to depress the volatility of one of the
 components, the separation is known as extractive distillation. Butenes are separated
from butanes using this principle with furfural as the extractant. When a high-
volatility entrainer is used, the process is called azeotropic distillation.
4. Absorption. Generally used to separate high-boilers from gases. Gas oil is to absorb
natural gasoline from wet gases. Gases which are expelled from gas storage tanks as
a result of solar heating are also sent to an absorption plant for recovery. Steam
stripping is generally used to recover the absorbed light hydrocarbons and restore
the absorption capacity of the gas oil.
5. Adsorption. Used for recovering heavy materials from gases. Adsorbents such as
activated charcoal and molecular sieves are used.
6. Filtration. Filtration is used to remove wax precipitated from wax-containing
distillates.
7. Crystallization. Before filtration, waxes must be crystallized to suitably sized crystals
by cooling and stirring. Waxes undesirable in lubes are removed and become the
microcrystalline waxes of commerce. For most purposes, this operation is both slow
and expensive.
8. Extraction. Extraction is removal of a component by selectively dissolving it in a
liquid. This procedure is very important in preparing high-quality lube oil. Low-
viscosity index materials (those whose viscosity changes rapidly with temperature),
waxes, color bodies, and sulfur compounds are removed in this way. If a proper
solvent is available, the mixture separates into two layers, one called the extract,
which is usually solvent-rich and contains the impurities; the other called the
raffinate, which should contain the desirable constituents and little solvent.

CONVERSION PROCESSES

Petroleum distillates undergo different conversion process. But most of these

processes are used over and over again to suffice the desired product.

1. Desulfurizing or amine sweetening. This process removes two gases, hydrogen

sulfide and carbon dioxide, from the refinery light gases. The removal of these two
gases is important for two reasons. First, H 2S and CO2 would react with the
atmosphere to form acidic compounds potentially harmful to the environment.
Second their presence would interfere with and damage some other chemicals used
in the refinery process.
2. Polymerization. Two or more alkene light gases are combined in the presence of a
phosphoric acid catalyst to form a larger alkene molecule, a liquid, called polymer
gasoline, which is added to make gasoline.
3. Alkylation. Two light gases one an isoparaffin, the other an alkene are combined
in the presence of a hydrofluoric or sulfuric acid catalyst to form a larger branched
isoparaffin known as alkylate, a liquid, which is added to make gasoline.
4. Hydrotreating. This process removes impurities like sulfur, metals, and nitrogen that
exists in either elemental form or bound to hydrocarbon molecules. Hydrotreating
involves the addition of hydrogen atoms to molecules without actually breaking the
molecule into smaller pieces. In the hydrotreating process, the entering feedstock is
 mixed with hydrogen gas and heated. Catalysts are involved in the process,
including; nickel, palladium, platinum, cobalt, and iron. The reactor is also loaded
with a catalyst which promotes several reactions:
Hydrogen combines with sulfur to form hydrogen sulfide (H2S)
Nitrogen compounds are converted to ammonia (NH 3)
Any metals contained in the oil are deposited on the catalyst
Hydrocarbon molecules that had sulfur or nitrogen removed have
hydrogen atoms put in their place to satisfy the bonding needs of the
molecule
5. Isomerization. Isomerization is achieved by mixing a certain petroleum distillate with
a little hydrogen gas and the catalysts to form isoparaffins. In the isomerization
process, straight-chain hydrocarbons (paraffins) and the ringed naphthenes
(cycloparaffins) are convered to branced molecules (isoparaffins). This is done
because the isoparaffins improve the octane rating in gasoline.
6. Deasphalting. This chemical process is used to separate the residue into a solid
fraction and a liquid fraction. Propane (or hexane) is used as a solvent and mixed
with the residue.

THE REFINING PROCESS OF PETROLEUM

In this discussion, we will assume that the processing of crude oil or petroleum will
start at the refinery. The crude oil undergoes the following processes: cracking or pyrolysis,
reforming, coking, chemical treatment, and waste treatment.

1. Cracking or pyrolysis. When sufficient heat, preferably in the presence of a catalyst,

is applied to a paraffin hydrocarbon, it breaks into two (or more) fragments, and one
of them is always an olefin. The size of the fragments produced always include all
the possibilities, so the product will be a mixture. All cracking reactions are
endothermic and the energy involved is usually high. The reactions are sufficiently
complicated to make accurate calculation of reaction heats difficult to impossible.
Cracking conserves fuel because it makes possible efficient use of virtually all the
crude. Essentially all present-day cracking is done in the presence of catalysts which
is called as catalytic cracking. First the catalyst was moved mechanically; later the
fluid catalytic process took over.

2. Reforming. Reforming means just what the name implies forming new molecules of
a size similar to the original ones. Because the octanes of straight run gasolines,
napththas, and natural gasolines are low, these fractions are subjected to a high-
temperature catalytic treatment, frequently in the presence of hydrogen, designed to
preserve their present molecular size, but convert them into branched-chain and
aromatic compounds with high antiknock ratings. This expensive process has
become essential since the Environmental Protection Agency adopted the phase-out
rules for lead. Without lead, enough high-octane motor fuel simply cannot be made
without reforming a combination of isomerization and cracking. One of the
reforming methods, the catalytic reforming involves the conversion of other
hydrocarbons into aromatic compounds. Because of the high octane rating of
 aromatic compounds and the proved practicability of the process, catalytic reforming
has now almost completely replaced the thermal reforming. Catalysts such as
platinum on alumina or silica-alumina and chromia on alumina are used.
3. Coking. Lighter oils can be produced from very heavy ones by a solely thermal
cracking process. The feed is usually a vacuum residue and considerable coke is
formed. Another process known as Flexicoking takes the coke made and converts it
into clean fuel gas by gasifying it with steam and air or oxygen. The coking unit uses
heat to break the large molecules in the residue into smaller molecules and coke,
which is almost pure carbon.
4. Chemical Treatment. Some type of chemical treatment to remove or alter the
impurities in petroleum products is usually necessary to produce marketable
material. Depending upon particular treatment used, one or more of the following
purposes are achieved:
a. Improvement of color
b. Improvement of odor
c. Improvement of stability to light and air
d. Improved susceptibility to additives
e. Removal of sulfur compounds
f. Removal of gums, resins and asphaltic materials
Of these, removal of sulfur and improvement of stability are the factors usually
governing the treatment employed. With the discovery that the use of catalytic
converters causes the emission of sulfuric acid vapors from automobile exhausts,
pressure to remove or reduce sulfur in motor fuel has developed. Sulfur may be
reduced by: (1) hydrogenation (which also removes metals and nitrogen), (2)
treatment with caustic soda, (3) treatment with caustic soda plus a catalyst, and (4)
treatment with ethanolamines.
5. Waste Treatment. Sulfur compounds in stack gases and a variety of extracts and
wastes found in refinery waste waters must be disposed of in accordance to
environmental laws and policies.

References:

Austin, George T. "Shreve's chemical process industries." (1984)

Hydrocracking. (2013, October 26). Retrieved June 21, 2016, from

http://en.citizendium.org/wiki/Hydrocracking

Petroleum products chart. Retrieved June 20, 2016, from http://2.bp.blogspot.com/-

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Petroleum refining diagram. Retrieved June 20, 2016, from

https://sites.lafayette.edu/es101-10-fa13/files/2013/10/Petroleum-Refining-
Diagram.png

Oil refining: a closer look. Retrieved June 22, 2016, from

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