Origin of petroleum:

Petra means rock and oleum means oil. It is originated by decomposition of algae
and zooplankton which is present between sedimentary rocks .Petroleum was
available only in very small quantities from natural seepage of subsurface oil in
various areas throughout the world. However, such limited availability restricted
the uses for petroleum to medicinal and specialty purposes.

Composition:

Hydrocarbons:

Parafins; These are alkanes CnH2n+2

Olefins: These are alkenes

Olefins +diolefins= polemrization occur and gum produces

Naptha lene :

These are cycloalkenes .

Aromatics:

They produce frangrance they contain benzene ring.

Non hydro carbon:

It contain N2, O2 , S ,Ni , Cr.

Separation techniques:

Sorption :

Sorption is a physical or process in which we study both adsorption and

absorption .

Absorption

Absorption processes are employed to recover valuable light components such as

propane/propylene and butane/butylene from the vapours that leave the top of
crude-oil or process-unit fractionating columns within the refinery. These volatile
gases are bubbled through an absorption fluid, such as kerosene or heavy naphtha,
in equipment resembling a fractionating column. The light products dissolve in the
oil while the dry gases—such as hydrogen, methane, ethane, and ethylene—pass
through undissolved. Absorption is more effective under pressures of about 7 to 10
bars (0.7 to 1 megapascal [MPa]), or 100 to 150 psi, than it is at atmospheric

pressure.

The enriched absorption fluid is heated and passed into a stripping column, where
the light product vapours pass upward and are condensed for recovery as liquefied
petroleum gas (LPG). The unvaporized absorption fluid passes from the base of the
stripping column and is reused in the absorption tower.

Adsorption

Certain highly porous solid materials have the ability to select and adsorb specific
types of molecules, thus separating them from other materials. Silica gel is used in
this way to separate aromatics from other hydrocarbons, and activated charcoal is
used to remove liquid components from gases. Adsorption is thus somewhat
analogous to the process of absorption with an oil, although the principles are
different. Layers of adsorbed material only a few molecules thick are formed on
the extensive interior surface of the adsorbent; the interior surface may amount to
several hectares per kilogram of material.

Molecular sieves are a special form of adsorbent. Such sieves are produced by the
dehydration of naturally occurring or synthetic zeolites (crystalline alkali-metal
aluminosilicates). The dehydration leaves intercrystalline cavities that have pore
openings of definite size, depending on the alkali metal of the zeolite. Under
adsorptive conditions, normal paraffin molecules can enter the crystalline lattice
and be selectively retained, whereas all other molecules are excluded. This
principle is used commercially for the removal of normal paraffins from gasoline
fuels, thus impr++oving their combustion properties. The use of molecular sieves
is also extensive in the manufacture of high-purity solvents.

Distillation is used to purify a compound by separating it from a non-volatile or

less-volatile material. When different compounds in a mixture have different
boiling points, they separate into individual components when the mixture is
carefully distilled.

Fractional Distillations

Mixtures of liquids whose boiling points are similar (separated by less than 70°C)
cannot be separated by a single simple distillation. In these situations, a fractional
distillation is used. You can see photos of a fractional distillation set-up here.

Atmospheric Distillation Unit

Typical PFD for an Atmospheric Distillation Unit

Crude oil is sent to the atmospheric distillation unit after desalting and heating.
The purpose of atmospheric distillation is primary separation of various 'cuts' of
hydrocarbons namely, fuel gases, LPG, naptha, kerosene, diesel and fuel oil. The
heavy hydrocarbon residue left at the bottom of the atmospheric distillation
column is sent to vacuum distillation column for further separation of
hydrocarbons under reduced pressure.
As the name suggests, the pressure profile in atmospheric distillation unit is close
to the atmospheric pressure with highest pressure at the bottom stage which
gradually drops down till the top stage of the column.

The temperature is highest at the bottom of the column which is constantly fed with
heat from bottoms reboiler. The reboiler vaporizes part of the bottom outlet from
the column and this vapor is recycled back to the distillation column and travels to
the top stage absorbing lighter hydrocarbons from the counter current crude oil
flow. The temperature at the top of the column is the lowest as the heat at this
stage of the column is absorbed by a condenser which condenses a fraction of the
vapors from column overhead. The condensed hydrocarbon liquid is recycled back
to the column. This condensed liquid flows down through the series of column
trays, flowing counter current to the hot vapors coming from bottom and
condensing some of those vapors along the way.

Thus a reboiler at the bottom and a condenser at the top along with a number of
trays in between help to create temperature and pressure gradients along the
stages of the column. The gradual variation of temperature and pressure from one
stage to another and considerable residence time for vapors and liquid at a tray
help to create near equilibrium conditions at each tray. So ideally we can have a
number of different vapor-liquid equilibria at different stages of this column with
varying temperature and pressure conditions. This means that the hydrocarbon
composition also varies for different trays with the variation in temperature and
pressure.

The heaviest hydrocarbons are taken out as liquid flow from the partial reboiler at
bottom and the lightest hydrocarbons are taken out from the partial condenser at
the column overhead. For the in between trays or stages, the hydrocarbons become
lighter as one moves up along the height of the column. Various other cuts of
hydrocarbons are taken out as sidedraws from different stages of the column.
 Starting from LPG at the top stages, naptha, kerosene, diesel and gas oil cuts are
taken out as we move down the stages of atmospheric column.
The heaviest hydrocarbon residue taken out from partial reboiler is sent to the
vacuum distillation column for further separation under reduced pressure. The
different cuts of hydrocarbons taken out at this stage are the result of primary
separation and undergo further processing before being transformed to end
products.

Crystallization is the (natural or artificial) process of formation of

solid crystals precipitating from a solution, melt or more rarelydeposited directly
from a gas. Crystallization is also a chemical solid–liquid separation technique, in
which mass transfer of a solute from the liquid solution to a pure solid crystalline
phase occurs. In chemical engineering crystallization occurs in a crystallizer.
Crystallization is therefore an aspect of precipitation, obtained through a variation
of the solubility conditions of the solute in the solvent, as compared to
precipitation due to chemical reaction.

Forced Circulation (FC) Crystallizer

Operation principle
In a Forced Circulation evaporator, the solution to be evaporated / crystallized is
circulated by circulation pump through the heat exchanger tubes with high velocity
from bottom to the top. High slurry density in the boiling surface and sufficient
retention volume in the body ensure minimum nucleation and the growth of
required crystal size.

Advantages
 Economic alternative when the product size is less important
Applications
 When evaporation rate is dominant
 Used for salt solutions where solubility is less dependent of temperature
Solvent Extraction
 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.

 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.

Conversion process :

Cracking

Reforming

Conversion of high hydro carbon into low hydrocarbon.

Reforming, in chemistry, processing technique by which the molecular structure of
a hydrocarbon is rearranged to alter its properties. The process is frequently
applied to low-quality gasoline stocks to improve their combustion
characteristics. Thermal reforming alters the properties of low-grade naphthas by
converting the molecules into those of higher octane number by exposing the
materials to high temperatures and pressures. Catalytic reforming uses a catalyst,
usually platinum, to produce a similar result. Mixed with hydrogen, naphtha is
heated and passed over pellets of catalyst in a series of reactors, under high
pressure, producing high-octane gasoline.

Four steps from lecture .

Semiregenerative A semiregenerative catalytic reforming process usually has three
or four reactors in series with a fixed-bed catalyst system and operates
continuously (cycle length) from six months to one year. During this period, the
activity of the catalyst diminishes due to coke deposition, provoking a decrease in
aromatics yield and in hydrogen gas purity. To minimize the catalyst deactivation
rate, the semiregenerative units operate at high pressure (200 to 300 psig). To
compensate for catalyst activity decline and to keep conversion more or less
constant, the reactor temperatures are increased continuously. When the end- of-
cycle reactor temperatures are reached, the unit is shutdown and the catalyst is in
situ regenerated. A catalyst cycle ends when the reforming unit is unable to meet
its process objectives: octane and yield reformate. Catalyst regeneration is carried
out with air as the source of oxygen. A catalyst can be regenerated five to ten times
before it is removed and replaced.
Cyclic Regeneration Apart from the catalytic reforming reactors, the cyclic
regeneration process has an additional swing reactor, which is used when the
fixed-bed catalyst of any of the regular reactors needs regeneration. The reactor
with the regenerated catalyst then becomes the spare reactor. By this means, the
reforming process maintains continuous operation. Operating at lower pressure (-
200 psig) allows the cyclic regeneration process to achieve higher reformate yield
and hydrogen production. Compared with the semire-generative type, in the cyclic
regeneration process the overall catalyst activity varies much less with time, so
that conversion and hydrogen purity are kept more or less constant during the
entire operation. The main disadvantage of this type of catalytic reforming is the
complex nature of the reactor switching policy, requiring high safety precautions.
Also, to make switches between reactors possible, they need to be of the same
maximal size.
Figure 4.1. Reaction section of the catalytic reforming processes.
Continuous Regeneration The deficiencies in cyclic regeneration reforming are
solved by a low-pressure (50 psig) continuous regeneration process, which is
characterized by high catalyst activity with reduced catalyst requirements,
producing more uniform reformate of higher aromatic content and high hydrogen
purity. This type of process uses moving-bed reactor design, in which the reactors
are stacked. The catalyst bed moves by gravity flow from top to bottom of the
stacked reactors. The spent catalyst is withdrawn from the last reactor and sent to
the top of the regenerator to burn off the coke. The transport of catalyst between
reactors and regenerator is done by the gas lift method. During normal operation,
small quantities of catalyst are withdrawn continuously. Fresh or regenerated
catalysts are added to the top of the first reactor to maintain a constant inventory
of catalyst.
Atmospheric Distillation Unit
 Typical PFD for an Atmospheric Distillation Unit

Crude oil is sent to the atmospheric distillation unit after desalting and heating.
The purpose of atmospheric distillation is primary separation of various 'cuts' of
hydrocarbons namely, fuel gases, LPG, naptha, kerosene, diesel and fuel oil. The
heavy hydrocarbon residue left at the bottom of the atmospheric distillation
column is sent to vacuum distillation column for further separation of
hydrocarbons under reduced pressure.
As the name suggests, the pressure profile in atmospheric distillation unit is close
to the atmospheric pressure with highest pressure at the bottom stage which
gradually drops down till the top stage of the column.

The temperature is highest at the bottom of the column which is constantly fed with
heat from bottoms reboiler. The reboiler vaporizes part of the bottom outlet from
the column and this vapor is recycled back to the distillation column and travels to
the top stage absorbing lighter hydrocarbons from the counter current crude oil
flow. The temperature at the top of the column is the lowest as the heat at this
stage of the column is absorbed by a condenser which condenses a fraction of the
vapors from column overhead. The condensed hydrocarbon liquid is recycled back
to the column. This condensed liquid flows down through the series of column
trays, flowing counter current to the hot vapors coming from bottom and
condensing some of those vapors along the way.

Thus a reboiler at the bottom and a condenser at the top along with a number of
trays in between help to create temperature and pressure gradients along the
stages of the column. The gradual variation of temperature and pressure from one
stage to another and considerable residence time for vapors and liquid at a tray
help to create near equilibrium conditions at each tray. So ideally we can have a
number of different vapor-liquid equilibria at different stages of this column with
varying temperature and pressure conditions. This means that the hydrocarbon
composition also varies for different trays with the variation in temperature and
pressure.

The heaviest hydrocarbons are taken out as liquid flow from the partial reboiler at
bottom and the lightest hydrocarbons are taken out from the partial condenser at
the column overhead. For the in between trays or stages, the hydrocarbons become
lighter as one moves up along the height of the column. Various other cuts of
hydrocarbons are taken out as sidedraws from different stages of the column.
Starting from LPG at the top stages, naptha, kerosene, diesel and gas oil cuts are
taken out as we move down the stages of atmospheric column.
The heaviest hydrocarbon residue taken out from partial reboiler is sent to the
vacuum distillation column for further separation under reduced pressure. The
different cuts of hydrocarbons taken out at this stage are the result of primary
separation and undergo further processing before being transformed to end
products.

Octane no. :
%age volume of iso octane in a mixture of iso octane and n-heptane where given
same intensity of knocks as a fuel under test.

Example ;

Fuel

Iso octane=70%

Paraffins =30%

So,

Octane number will be 70.

Refineries vary by complexity; more complex refineries have more secondary

conversion capability, meaning they can produce different types of petroleum
products. Fluid catalytic cracking (FCC), a type of secondary unit operation, is
primarily used in producing additional gasoline in the refining process.
Unlike atmospheric distillation and vacuum distillation, which are physical
separation processes, fluid catalytic cracking is a chemical process that uses a
catalyst to create new, smaller molecules from larger molecules to make gasoline
and distillate fuels.
The catalyst is a solid sand-like material that is made fluid by the hot vapor and
liquid fed into the FCC (much as water makes sand into quicksand). Because the
catalyst is fluid, it can circulate around the FCC, moving between reactor and
regenerator vessels (see photo). The FCC uses the catalyst and heat to break apart
the large molecules of gas oil into the smaller molecules that make up gasoline,
distillate, and other higher-value products like butane and propane.
After the gas oil is cracked through contact with the catalyst, the resulting effluent
is processed in fractionators, which separate the effluent based on various boiling
points into several intermediate products, including butane and lighter
hydrocarbons, gasoline, light gas oil, heavy gas oil, and clarified slurry oil.
The butane and lighter hydrocarbons are processed further to separate them into
fuel gas (mostly methane and ethane), propane, propylene, butane, and butene for
sale, or for further processing or use. The FCC gasoline must be desulfurized and
reformed before it can be blended into finished gasoline; the light gas oil is
desulfurized before blending into finished heating oil or diesel; and the heavy gas
oil is further cracked in either a hydrocracker (using hydrogen and a catalyst) or a
coker. The slurry oil can be blended with residual fuel oil or further processed in
the coker.
Carbon is deposited on the catalyst during the cracking process. This carbon,
known as catalyst coke, adheres to the catalyst, reducing its ability to crack the oil.
The coke on the spent catalyst is burned off, which reheats the catalyst to add heat
to the FCC process. Regeneration produces a flue gas that passes through
environmental control equipment and then is discharged into the atmosphere.

Alkylation, in petroleum refining, chemical process in which light, gaseous

hydrocarbons are combined to produce high-octane components of gasoline. The
light hydrocarbons consist of olefins such as propylene and butylene and
isoparaffins such as isobutane. These compounds are fed into a reactor, where,
under the influence of a sulfuric-acid or hydrofluoric-acid catalyst, they combine
to form a mixture of heavier hydrocarbons. The liquid fraction of this mixture,
known as alkylate, consists mainly of isooctane, a compound that lends excellent
antiknock characteristics to gasolines.
Alkylation units were installed in petroleum refineries in the 1930s, but the process
became especially important during World War II, when there was a great demand
for aviation gasoline. It is now used in combination with fractional distillation,
catalytic cracking, and isomerization to increase a refinery’s yield of automotive
gasoline.