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It consists of the following important sub-processes:

1. Crude desalte

2. Furnace

3. Pre-flash column
4. Crude distillation column supplemented with side columns. These columns produce the desired
products
5. Pump around heat exchanger units
6. Heat exchanger network that facilitates energy recovery from hot product and reflux streams to
heat the crude oil.

Furnace

The furnace is an important constituent in the crude distillation unit

Here, fuel oil and fuel gas (heavier products) obtained from the refining process itself are burnt to
increase the crude oil temperature.
Typically in refineries, the crude oil is heated to a temperature that enables overflash conditions in
the main crude distillation column.
The concept of overflash is that the crude is heated to such a temperature that enables an
additional 5 % vaporization with respect to the residue product. In other words, the residue fraction
vapors amounting to 5 % of the total volume of the crude oil are desired.
Depending upon the quality of the crude, the desired temperature for the crude oil is about 600 700F.
5.1.3 Pre-flash column

The crude oil enters the pre-flash column after leaving the furnace

The pre-flash tower separates the lighter fractions of the already heated crude oil.
The heavier fractions of the crude oil leave from the bottom section of the pre-flash tower.
Both lighter and heavier streams emanating from the pre-flash tower are fed to the main crude
distillation column at various sections

Pre-flash column enables better refluxes in the main column by distributing the streams effectively
between various processing zones of the crude oil.
Pre-flash column may or may not be included i.e., it is optional. In other words, the pre-flash
column can be avoided and the heated crude oil from the furnace can be fed to the main column
directly.
5.1.4 Main and Secondary distillation columns
Live steam is also used in the recent designs. The live steam is usually at about 50 psig.
The basic principle of using live steam stems out from several facts. Firstly, upon condensation, oil
and water are very easy to separate. Secondly, steam can take significant amount of heat in terms of
enthalpy. Thirdly, steam enables enhancement in relative volatility, a principle that is used in steam
distillation laboratory experimental set ups. These principles together are anticipated to provide
good dividends technically.

Crude oil distillation consists of atmospheric and vacuum distillation. The heavier fraction of crude oil obtained
from atmospheric column requires high temperature. In order to avoid cracking at higher temperature the
heavier fraction are fractionated under vacuum.

CRACKING
Cracking of heavy residue is most commonly used method for upgradation of residues. This involves
of decomposition of heavy residues by exposure to extreme temperatures in the presence or
absence of catalysts. Therefore, in principle cracking generates lighter hydrocarbons constituting
paraffins, olefins and aromatics. In other words, high boiling low octane number feed stocks are

converted to low boiling high octane number products. Cracking is a gas phase reaction. Therefore,
entire feedstock needs to be vaporized.
THERMAL CRACKING
Cracking at elevated temperatures in the absence of catalyst eg: Visbreaking, delayed coking, Fluid
coking etc.
CATALYTIC CRACKING
Cracking in presence of catalyst eg: FCC , Hydrocracking, DCC
Visbreaking

In Visbreaking operation, a mild thermal cracking is carried out.

Visbreaking produces Naphtha, Gasoil and a residue. The residue has lower viscosity and
pour point and hence can easily meet the requirements of the fuel oil specifications in the
fuel oil blending pool.

Visbreaking basically breaks the long paraffinic side chains attached to aromatic structures.
Due to this the residue pour point and viscosities are considerably reduced.

Two classes of reactions occur during visbreaking

1. Cracking of side chained aromatic compounds to produce short chained aromatics and paraffins
2. Cracking of large molecules to form light hydrocarbons
Soaker Visbreaking Process:
Objective: To lower the viscosity of heavy residues under relatively milder cracking condition than
the conventional cracking processes. Feed Atmospheric residues: To get gasoline and diesel oil
Vacuum residues: To reduce viscosity
typical yield pattern may be gas 1-2%, naphtha 2-3%, gas oil 5-7%, furnace oil 90-92%
Advantages:
15% reduction in fuel oil
Larger running time between two decoking operations.
coke deposit rate 3-4 times slower than in conventional units.
Better selectivity towards gas and gasoline productivity.
Coil Visbreaker:
In coil visbreaking process the desired cracking is achieved in the furnace at high temperature and
the products of cracking are quenched and distilled in a downstream fractionator. Advances in
visbreaker coil heater design now allows for the isolation of one or more heater passes for decoking,

eliminating the need of shut the entire visbreaker down for furnace decoking. Integration of the coil
visbreaking process with vacuum units is also being considered in many areas of the world.
After cracking, the products are at high temperatures (480 C for coiled furnace case or 430 C for
the soaker)
After cracking, the products are cooled using quenching operation.
Quenching is a direct heat transfer mechanism in which a hot stream is cooled with a hydrocarbon
or water to reduce the temperature of the system drastically.
After quenching, the mixture is fed to a distillation column supplemented with a side column and a
partial condenser.
From partial condenser, water, naphtha and gas are produced. Naphtha liquid stream is sent as a
reflux for the column.
The side column is fed with steam and produces gas oil. Steam enhances hydrocarbon volatility as
explained before in the lecture devoted towards crude distillation process.

Coking: Coking refers to extreme thermal cracking process.


Coking is a batch reaction. Feed is heated to 480 510C and left for some time so that coke and
lighter products form.
Since coking is a batch reaction, there can be different ways to carry out coking.
There are two types of refinery coking processes namely delayed coking and fluid coking.
DELAYED COKING
Delayed coking process is used to crack heavy oils into more valuable light liquid products with less
valuable gas and solid coke as byproduct Delayed coking consists of thermal cracking of heavy
residue in empty drum where deposition of coke takes place. The product yield and quality depends
on the typed feedstock processed.
Typical delayed coking consists of a furnace to preheat the feed, coking drum where the
fractionation of the product takes place. The feed is first preheated in furnace where the desired
cooking temperature is achieved and fed to the coking drums normally installed in pairs where the
cracking reaction takes place and the coke is deposited in the bottom of the reactor. The coke drums
overhead vapour flows to the fractionating column where they are separated into overhead streams
containing wet gas LPG and naphtha and two side gas oil streams. Recycled stream from the
fractionating column combines with the fresh feed in the bottom of the column and is further
preheated in coke heaters and flows to the coke drums.
The process is called delayed coking because in this process the coal is heated using a much more
complex system , and it consists of multiple furnaces or coke drums. Usually the coal is heated at a

lower temperature for shorter periods of time , which removes water and other by products more
slowly than the conventional process, thereby increasing the overall time span.
Fluid coking: The heated feed is fed to a fluidized bed where coke particles with finer particle sizes
would aid fluidization. After coking, lighter products are withdrawn as overhead vapour and coke
thus formed is removed continuously. The fluid coker also has an additional scrubber which will
remove heavier compounds from the vapour (if any) and send them back with the feed stream. The
coke after coking reaction is cold coke. Therefore, to generate hot coke, a burner unit is used to heat
the coke using exothermic CO2 reaction. The offgases from the burner are sent to cyclones,
scrubbing and then to the vent. The hot coke thus obtained is recycled back to the fluidized bed or
taken out as a net coke product.

What is flexicoking?
Ans: In flexi coking, coke is fed to a gasifier to react with air and steam. Eventually, the coke
produces hydrogen, CO, CO2, N2, H2O and H2S. The gas thus obtained is used as a fuel gas in the
refinery itself for various furnace operations. Therefore, flexicoking refers to flexibly alter the coking
process to produce additionally gas using an extra gasification unit.
CATALYTIC CRACKING
The feed stock for catalytic cracking is normally light gas oil from vacuum distillation column.
Catalytic cracking cracks low value high molecular weight hydrocarbons to more value added
products (low molecular weight) like gasoline, LPG Diesel along with very important petrochemical
feedstock like propylene, C4 gases like isobutylene, Isobutane, butane and butane.
Main reactions involved in catalytic cracking are Cracking, Isomerisation, Dehydrogenenation,
Hydrogen transfer, Cyclization, Condensation, Alkylation and dealkylation
FLUID CATALYTIC CRACKING
Vacuum gas oil (VGO), Hydro-treated VGO, Hydro-cracker bottom, Coker gas oil (CGO), Deasphalted
oil (DAO), Reduced crude oil (RCO), Vacuum residue (VR). Typical feedstock consists of Vacuum and
Atmosphere gas oil but may include other heavy stream.
Process Steps
Three basic functions in the catalytic cracking process are:
Reaction: Feedstock reacts with catalyst and cracks into different hydrocarbons;
Regeneration: Catalyst is reactivated by burning off coke; and recerculated to reactor
Fractionation: Cracked hydrocarbon stream is separated into various products like LPG and gasoline,
like light cycle oil and heavy cycle oil are withdrawn as side stream
Reactor and Regenerator Section: Catalyst section consists mainly of the reactor and regenerator

The feed to unit along with recycle streams is preheated to temperature of 365oC-370Oc and enters
the riser where it comes in contact with hot regenerated catalyst ( at a temperature of about 640660oC. Finely divided catalyst is maintained in an aerated or fluidized state by the oil vapors. The
catalyst section contains the reactor and regenerator & catalyst re circulates between the two.
Spent catalyst is regenerated to get rid of coke that collects on the catalyst during the process. Spent
catalyst flows through the catalyst stripper to the regenerator, where most of the coke deposits
burn off at the bottom where preheated air and spent catalyst are mixed. Fresh catalyst is added
and worn-out catalyst removed to optimize the cracking process
Fractionation: Cracked hydrocarbon stream is separated into various products. LPG and gasoline are
removed overhead as vpour. Unconverted product like light cycle oil and heavy cycle oil are
withdrawn as side stream. Overhead product is sent to stabilsation section where stabilised gasoline
is separated from light products from which LPG is recovered
catalyst: Zeolite
Options for Clean Fuel: For upgrading FCC products into acceptable blending components following
three steps are being used
Severe hydro processing of feed to FCC
Treating each of the products in hydrotreater
Combination of both upstream and downstream processing
HYDROCRACKING
The development of upgrading technology for heavier stocks having high sulfur, nitrogen and heavy
metal (Ni, V) are becoming important. Hydrocracking is one of the most versatile processes for the
conversion of low quality feed stocks into high quality products like gasoline, naphtha, kerosene,
diesel, and hydrowax
Hydrocracking processes uses a wide variety of feed stocks like naphtha, atmospheric gas oil,
vacuum gas oils, coke oils, catalytically cracked light and heavy cycle oil, cracked residue,
deasphalted oils and produces high quality product with excellent product quality with low sulphur
contents.

Hydro-treatment & Hydrocracking Catalyst


Hydrocracking processes involved two types of catalyst: Hydro pretreatment catalyst, Hydrocracking
catalyst.
Hydrotreating (Pretreat) Catalyst
The main objective of pretreat catalyst is to remove organic nitrogen from the hydro cracker feed
allowing. Better performance of second stage hydrocracking catalyst, and The initiation of the
sequence of hydrocracking reactions by saturation of aromatic compounds
Hydrocracking Catalyst
Hydrocracking catalyst is a bi-functional catalyst and has a cracking function and hydrogenation
dehydrogenation function. The former is provided by an acidic support whereas the latter is
imparted by metals. Acid sites (Crystalline zeolite, amorphous silica alumina, mixture of crystalline
zeolite and amorphous oxides) provide cracking activity. Metals [Noble metal (Pd, Pt) or non noble
metal sulphides (Mo, Wo or Co , Ni)] provide hydrogenation dehydrogenation activity. Preheated
feed is first hydrotreated in a reactor for desulphurization and denitrogenation in presence of
pretreat catalyst followed by hydrocracking in second reactor in presence of strongly acidic catalyst
with a relatively low hydrogenation activity. In the first stage reactor the sulphur and nitrogen
compounds are converted to hydrogen sulphide and ammonia with limited hydrocarcking. The two
stages process employs interstage product separation that removes H2S and NH3. In case of two
stage process, hydrocracking catalyst works under low H2S and NH3.
ALKYLATION
In an alkylation process, olefins are reacted with isoparaffins to yield alkylate product. The basic
purpose of alkylation is to enhance the octane number of the feed stock.
Reaction conditions
To avoid olefin polymerization, high isobutane to olefin ratios are used.
Typical isobutene to olefin ratios are 5:1 to 15:1
Acid catalysts are used. Primarily sulphuric acid (H2SO4) or HF are used.
Depending on the acid catalysts choosed the process complexity varies. We present both process
technologies to indicate the pertinent process complexity.
Reaction operating temperature: 10 - 20C using H2SO4 and 25 40C using HF
Reaction temperature: 4.4 bar for H2SO4 and 7.8 bar for HF
When H2SO4 is used refrigeration is used.
When HF is used, refrigeration is not used.

Caustic wash: The feed mixture (olefin + C4 compounds) are first subjected to caustic
wash. During caustic wash, sulphur compounds are removed and spent caustic is recycled
back to the caustic wash. Fresh caustic solution is added to take care of the loss.

Refrigeration: The olefin feed enters a refrigeration unit to reduce the feedstock temperature.
Sulfuric acid based alkylation process technology
Alkylation reactor: The reactor is arranged as a series of CSTRs with acid fed in the first CSTR and
feed supplied to different CSTRs. This arrangement is for maximizing the conversion.
In the alkylation reactor it is important to note that the olefin is the limiting reactant and
isoparaffin is the excess reactant.
9.5 HF process technology (Figure 9.2)
ty issues make the
process complex.
The feed is first subjected to drying followed by pre-cooling.
After pre-cooling the reaction mixture the reaction mixture is fed to a reactor.
Unlike CSTRs in series here impeller reactors are used. The reactor consists of cooling tubes to
absorb the heat generated.
ISOMERISATION

The basic principle of Isomerization is to convert straight chain alkanes to side chain
paraffins. This enhances the octane number substantially

For instance, n-pentane has an octane number of 61.7 where as iso-pentane has an octane
number of 92.3
Usually light naphtha is used as a feed stock
Catalyst

Platinum base catalysts are used

AlCll3 is used as a promoter for the catalyst


During reaction, part of the AlCl3 gets converted to HCl
Therefore, completely dry conditions shall be maintained to avoid catalyst deactivation and
corrosion.
Catalytic reaction takes place in the presence of hydrogen to suppress coke formation
are totally dried and sent to an isomerisation reactor after
pre-heating the feed mixture in a heat exchanger
Reaction operating conditions: 150 200C and 17 28 barg

Typical conversions: 75 80 % for pentanes.


After reaction, AlCl3 is recovered from the product using condensation or distillation
The basic principle for AlCl3 recovery is that at the reactor operating conditions, the AlCll3 is in
volatile conditions and is soluble in hydrocarbons
After AlCl3 is recovered from the product, it is sent back to the reactor along with the make- up
AlCl3
Olefin Polymerization

Olefin polymerization to yield polymer gasoline is primarily carried out to obtain polymers
with good octane numbers.

The octane number of the polymer gasoline product is not greater than the octane number of the
products produced from reforming and alkylation. Instead, comparatively poor quality product is
obtained. But for the sake of enhancing octane number polymerization is carried out.
On the other hand, polymer gasoline has more vapour pressure than the corresponding alkylation
products. Therefore, in both ways, polymer gasoline product quality is lower than that obtained
from the alkylation unit.
Typical feedstocks for polymerization process are C3 and C4 olefins that are obtained from catalytic
cracking.
Catalysts used: Acid catalysts (H2SO4 ) are used.
Reforming
The catalytic cracking involves enhancing the octane number of the product
Heavy naphthas are used are typical feed stocks
The reaction is carried out on a catalyst
Reforming reaction produces hydrogen as a by product which is used elsewhere in the refinery
Usually Platinum supported on porous alumina is used as a catalyst
Catalyst activity enhanced using chloride
The reactions are endothermic. Therefore, heat needs to be supplied
Reactor temperature: 500 525C
H2/Hydrocarbon molar ratio: 2 3
Definitions of hydroprocessing, hydrotreating and hydrocracking

In hydroprocessing, feedstocks are sent to a catalytic reactor in the presence of hydrogen.

Depending upon the intensity of the hydroprocessing operation, the hydroprocessing is termed as
hydrotreating or hydrocracking.
During hydrotreating, sulphur and nitrogen concentration in the final products is reduced along
with the saturation of olefins and aromatics. However, boiling range of the final products will be
similar to that of the feed stock.
During hydrocracking, heavier molecules react with hydrogen to generate lighter hydrocarbons.
DESULPHURISATION PROCESSES AND RECOVERY OF SULPHUR