CATALYTIC CONVERSION PROCESS

• 1. Which change the carbon number

• Catalytic cracking, hydro cracking.
Polymerization
• 2. change carbon/hydrogen ratio
• Hydrogenation, dehydrogenation
• 3. which do neither
• isomerization
• Catalytic conversion process
• 1. cracking
• 2. hydro cracking
• 3. reforming
• 4. isomerization
• 5. alkylation
• 6. polymerization
Advantage of catalytic process
• Gasoline produced has a higher octane
number.
• Sulphur compounds are less
• More saturated products
• Yield is more
• Temp and pressure requirement is less
• Bottoms are less
• Carbonium ions mechanism
 Catalytic cracking
• Reaction mechanism
• Through carbonium ions, they are
hydrocarbon ions having a positive charge on
a carbon atom. Carbonium ions forms as
intermediate in the presence of an acid
catalyst either by the removal of a hydride ion
from a saturated hydrocarbon or by the
addition of a proton to an olefin or aromatic
nucleus. For the formation of ions, the
catalyst capable of accepting electron or
donating a proton.
• Carbonium ions once formed undergo a
number of reaction
• 1. Isomerisation
• 2. B-scission
• 3. Hydrogen transfer
• 4. Termination
 Catalyst for cracking
• I. Amorphous silica alumina
• 2. Aluminum silicate zeolite
• Silica by itself has no active sites, but by
adding aluminum, acidity begins to rise.
• The zeolite have all the desired properties
like high absorption capacity, high surface
area and acid sites
• Depending on SiO2 to Al2O3 ratio, the
Zeolite catalyst are divided into
• X type SiO2/Al2O3 =3, with 27% rare earth
• Y type SiO2/Al2O3 = 3-6, 16 % rare earth
Development of FCCU Catalyst
 Advantage of Zeolite catalysts
• More active sites, high adsorption capacity,
large surface area.
• High selectivity and activity
• Hydrogen transfer is very high
• Sieving capacity for certain molecule
• Micro porous crystalline aluminum silicate,
• Cracking with less deposition of carbon
 Catalytic crackers

• 1. Fixed bed – Houdry

• 2. Moving bed – Air lift, Thermofor, Houdri
• 3. Fluidized bed – U.O.P, Texaco , Kellogg,
Esso
• Reaction variable-
• Quality of feed, Feed rate, Feed temp,
Reactor temp, Reactor pre, Stripping steam
rate, Catalyst to oil ratio, residence time,
Catalyst condition
 Advancement in Catalytic cracking
Technology
• Petro FCCU
• Resid FCCU
• Deep CCU
• Milli Second FCCU
• Select component Cracking.
• Propylene max technolgy by ABB LUMMAS,
MAXFIN Process by Kellog, Superflex
advanced catalytiic cracking by KBR,Indmax
technology by IOC.
 Feed stock characteristics
• Specific gravity- (higher is better)
• Boiling range-
• Carbon residue-0.2% wt
• Metals- max 0.5ppm
• Sulphur
• Water content- 0.2%
• Asphaltene content- below 0.4% wt
Flow diagram of Catalytic cracking
 Process description
• The different sections of a catalytic
cracker units are
• 1. reactor and regenerator
• 2. flue gas energy recovery
• 3. fractionation
• 4. gas conversion
• The reactor temp is kept in the range of 480 to
540C to control the degree of conversion. The
spent catalyst which contain about 1% wt coke,
collects at the base of the reactor and is made
to pass through a stripper to remove the
entrained HC vapour by a counter current flow of
steam.
• In the regenerator, the catalyst gets fluidized with
air and the coke is burnt off. The regenerated
catalyst then move through a control valve to the
base of the riser to complete the cycle.
• Cyclone separators (two stages) are used
both in the reactor as well as in the
regenerator to remove the entrained
catalyst. Reactor product vapours then
moves to the fractionation and gas
concentration section , while the flue gas
after energy recovery goes through the
stack.
 Process variables- Reactor section
• Fresh feed rate-Kg/hr of feed/Kg of catalyst
• Fresh feed temp
• Reactor temp-470 to 490C
• Reactor level
• Reactor pre (1.7 Kg/cm2)
• Stripping steam rate
• Catalyst oil ratio
• Recycle rate
• Recycle temp
• Catalyst activity
 Process variables-Regeneration
section
• The function of the regenerator is to burn
the coke of the catalyst returned from the
reactor, and provide the heat necessary for
the operation of the unit.
• After burning
• Dense phase temp
• Regenerator pre (2.2 Kg/cm2)
• Catalyst circulation rate (20t/hr)
• Regeneration air rate
• Air distribution
KELLOG ORTHOFLOW DESIGN
ESSO MODEL
Fixed bed catalytic cracker
 Process description
• There are three reactors in parallel in this
system (1,2,3). At the bottom of each
reactor there are four connections (V1,V2,
V3 and V4) provided through a rotary disc.
Only one line at a time is to be connected to
the reactor. At the start, charge of oil
vapour will enter the reactor through valve
V1. After cracking, the vapours escape
through the reactor outlet as product and
go to the fractionator through line a1.
• Immediately the reactor is disconnected
and connected with steam line (from top)
through line a3 and exhausted through the
bottom (V4). Oil vapours from this exhaust
are condensed and steam is allowed to
leave the separator. Soon after the steam
purging, preheated air is sent in to the
reactor 1, through valve V2 and flue gas
goes off through line a2 at the top of the
reactor.
• After regeneration steam purging from top
to bottom is again conducted and exhaust
steam is taken out through valve V3 from
the bottom of reactor.
• Rotary valves with interlocking system
conducts smooth automatic cycling of
reactors. Molten salt is circulated to
reactor, from the reactor under
regeneration, to supply necessary heat.
• Cyclic operation consits of
• On stream 10 minutes.
• Downward purging of steam to recover
HC- 5minutes.
• Regeneration by blowing hot air through
bottom of the reactor – 10 min
• Steam purge downward – 5 min
• Reactor temp – 450-520C
• Operating pre- 1 to 2 Kg/cm2
• Regeneration temp – 520C
• Catalyst – beads/pellets.
• Composition – Si-Al
Moving Bed(Houdri) catalytic
cracker
• Reactor is placed above the regenerator in a
single shell. The regenerated catalyst is
carried by pneumatic lift to disengager,
from where the catalyst can either go into
reactor or auxiliary storage. The system
works on self heat balance. Usually
operations are conducted in temp range of
450 to 520C at pre of 1.5 to 2 atm. A
conversion of 90% can be obtained with
recycling.
Moving bed (Thermofor)
 Process description
• Catalyst shape in these units may be
spherical or beads. Catalyst and oil move
cocurrently from top to bottom in the reactor.
Reactor is stacked directly over the
regenerator. In between reactor and
regenerator there is a constriction, where
steam purging is done. This helps firstly in
removing HC from the surface of catalyst,
secondly steam prevents the reactor
products from going downward into
regenerator.
• Spent catalyst is regenerated by air
blowing. The flue gas passing through
cyclone separators, leaving catalyst dust,
if any, in the out going stream. At the
bottom of the regenerator, there is a
cooling section to cool the catalyst. The
catalyst collected from the regenerator is
lifted into catalyst disengager, placed at a
height more than the reactor.
 Comparison of Thermal and
catalytic cracking
Thermal Cracking Catalytic cracking
1 Free radical mechanism Carbonium ion
2 Heat alone Heat + catalyst
3 Cracking alone Cracking + dehydrogenation
4 Gasoline produced has less Gasoline produced has less octane
octane number contain more number contain more branched
olefin and diolefin paraffin, Cyclo parffin and aromatics
5 Stability of products is less More stable products
6 Sulphur content high in Sulphur content less
products
7 High amount of residue Lesser amount of residue
8 More C2 hydrocarbon More c4 hydrocarbon
9 Carbon formation is high Carbon formation is less
10 Any feed can be handled Feed preparation is must
Hydro cracking
• Hydro cracking is a two stage process
combining catalytic cracking and
hydrogenation.
• Feed stocks are characterized by high
polycyclic aromatic content.
• Sulphur and Nitrogen are major catalyst
poison.
 Process description
• Fresh charge stock along with the recycle H2
are heated to the desired reaction
temperature by HE and then contacted with
catalyst in the reactor.
• The reactor effluent is heat exchanged and
passed to a HP separator. H2 rich gases are
recycled along with the fresh make up H2. HP
separator liquid is flashed into low pressure
drum where most of the dissolved gases are
removed from the liquid product. The flash
drum liquid is fed to a fractionator for
separation into the desired products.
 Hydrocracking
• Reduce the coke formation
• Enhance the yield of lower boiling
components.
• Cycle oils, coker distillates are the feed.
• Ability to break down high boilng aromatic
stocks produced by catalytic cracking and
coking.
• Very low sulphur and N2 in the products.
• Two types of hydro cracking
• 1. Distillate hydro cracking
• 2. Residue hydro cracking
• Catalysts - metal + acid (si/Al)
• Pre – 100 -200 kg/cm2
• Temp – 300 to 450 C
• Hydro cracking means cracking in the
presence of Hydrogen. Presence of
hydrogen during a thermal reaction of a
petroleum feed stock terminates many of
the coke forming reaction and enhance the
yield of lower boiling components.
• This process actually a combination of
catalytic cracking and catalytic
hydrogenation at high hydrogen pre using
dual function catalysts.
 Operating Variables
• Hydrogen Partial Pressure
• Reaction Temp
• Space Velocity
• Hydrogen recycle ratio
• Feed stock characterestics.
 Reactions in hydrocracking
• 1. catalytic cracking produce an olefin from a big
paraffin molecule, hydrogen saturating the olefin
molecule.
• 2. unsaturation in straight chain as well as in ring
structure is gradually eleminated.
• 3.Detachment of side chains and isomerisation
reaction are very frequent with ring structure.
• 4. Isomerisation takes place in all types of
components.
• 5. Cracking of Naphthenes
• 6. supplimentary reactions like removal of S,N2,O2
 Feed stock requirement of
hydrocracker
• Asphaltenes- Max 0.5 ppm
• Metal content- max 0.5 ppm
• Nitrogen content- max 960 ppm
• CCR- 0.5 wt %
 Comparison of HC and FCC
• FCC;- Carbon rejection, reactor regenerator
configuration, LPG and gasoline is the
major products, product rich in
unsaturated components.
• HCU:- Hydrogen addition, Down flow
packed bed, Kerosene and Diesel, Few
aromatics, Low S and N in products.
Costly operation.
 Recent development in HCU
• Mild hydro cracking:- produce low Sulphur
Diesel. MHC allow increasing diesel
production through VGO hydro conversion.
• Single stage Hydro cracking Process
• Two stage Hydro cracking Process
 Hydro Cracking Technology
• Chevron – Isocracking
• UOP – Unicracking
• IFP – Hydrocracking
• BP – Hydrocracking
• Shell – Hydrocracking
• Standard oil – Ultra cracking
• Linde - Hydrocracking
 Catalytic reforming
• Reforming is a process carried out to raise
the octane number to a level required for
high octane motor gasoline. Such octane
number boost up is achieved mainly by the
conversion of non aromatics into aromatic
components through the process of
reforming.
• Catalytic reforming is conducted in the
presence of H2 over catalyst. Catalytic
reforming helps to get reformate with
octane number of 90 -95
 Catalyst for reforming
• Dual function catalyst, metal function,
platinum, promote dehydrogenation and
hydrogenation reaction.
• Acidic sites required for isomerization,
dehydrocyclization, is produced by silica –
alumina.
• Monometallic reforming catalyst- Platinum
• Bimetallic catalyst – Pt-Rh (Rh improve
stability of reforming catalyst)
• Mono metallic catalyst usually contain platinum
in the range 0.25 to 0.8% by weight.
• Pt above this level cause naphthenic rings to
open and demethylation to occur while at Pt less
than 0.25% wt the catalyst become less resistant
to the attack of poison.
• Bi metallic catalyst, the Pt requirement has
comedown heavily to the range 0.2 to 0.4% by wt.
• The acid activity is obtained by incorporating
halogens or silica in the alumina base.
• Majority of the catalyst make use of chlorine in
the range 0.8 to 1.2% by weight.
 Advantage of bimetallic catalysts

• 1. High stable liquid yield

• 2. Higher octane C5 components
• 3. Increased Hydrogen production
• 4. Operation at low pressure
• 5. Operation at low Hydrogen to feed ratio
• 6. Long run between regeneration
• 7. Good temp stability
 Reaction
• 1. Dehydrogenation of naphthene to give
aromatics and hydrogen.
• 2. Isomerization of paraffins and
naphthenes
• 3. Dehydrocyclisation of paraffins to cyclic
compound.(cyclohexane, benzene)
• 4. Hydro cracking
• 5. Dealkylation- Higher aromatics lose the
side chain to give lower aromatics.
• Catalytic reforming, the quantity and quality
of the reformate obtained depends on the
naphthenicity of the feed stock. Higher the
naphthene content , easier the conversion ,
and higher the reformate yield.
• On the other hand , the paraffinic feed stock,
which depends more on dehydrocyclization,
isomerization, hydrocracking reactions,
need more severe operating conditions but
give only lower reformate yield.
 Catalyst Development
• 1935 - Cr and Mo oxides
• 1949 – Monometallic catalyst (Pt)
• 1962- Bimetallic (Pt-Rh), (Pt more)
• 1988 – High density bimetallic (Rh more)
• Acidic function – Chlorinated aluminium
with 0.1% chlorine. (Hydrogel).
• Metallic function – Pt
• Stability of metallic catalyst improved by
Rhenium.
 Process variable
• 1. Temp -470 – 540C
• 2. Space velocity – volume of oil processed per
hour per volume of catalyst is called space
velocity.
• 3. Pressure – 27.5 -41.5 bar (mmc)
8.6- 20 bar (bmc)
4. H2/hydrocarbon ratio – 5-10 (mmc)
3.5- 7 (bmc)
5. Water content –water content (10 to 30ppm) in
the recycle gas and small quantities of propylene
chloride are added periodically to replenish the
chloride removed by water.
 Process
• 1. Semi regenerative
• 2. Cyclic regeneration
• 3. Continuous catalytic reforming
Naphtha Hydrotreating & Cat. Reforming

Naphtha

Impurities: S,N,
Metals Naphtha
Hydrotreating
Risk of poisoning Hydro treated
CCR catalyst Naphtha

Impurities:
Nil or low

No Risk of
poisoning
CCR catalyst
Reformate
High Octane Low octane
Number: 102 number
Continuous
Catalytic
Reforming
Hydrogen
Rich gas
 OBJECTIVE OF CCR UNIT

• To process 0.304 MMTPA CCR feed to produce 0.2733 MMTPA

reformate.

• To Produce high octane ( 102 ) reformate from low octane heavy

Naphtha that has 90 to160°C distillation range.

• To co produce Hydrogen rich gas

• Limit benzene content to 1ppm wt in reformate.

• Eliminate impurities in the feed stock.

 Process licensors
• Platforming – UOP
• Power reforming- Exxon Mobil
• Ultra forming – BP
• Reforming – IFP (Institut Francais du
Petrole)
• Rheinforming - Chevron
Continuous Catalytic Reforming or
Platforming
• Instead of arranging the reactors side by
side as in conventional reformer, they are
stacked one on top of the other to make
catalyst flow easier. In the actual process,
the freshly regenerated catalyst flows by
gravity from top to the first reactor, then to
the second and so on until it reaches the
bottom of the reactor. The coked catalyst is
then lifted to the regeneration system to
burn off the carbon.
• Thus in the CCR techniques, the activity of
the catalyst remain close to that of the
fresh one at all time giving a constant
quality reformate and H2 rich excess gas
at high yield.
• Max reformate yield
• Low pre operation
• Low recycle gas rate
• Catalyst requirement is Min
• Min pre drop
Catalytic reforming with semi
regeneration
 Process description
• The feed is mixed with H2- containing
recycle gas, first by heat exchange with
reactor effluent and then in a fired heater
before sending to the first reactor.
• The process operating conditions are,
reaction pre 10 to 40 bar, temp 460 to 540C,
H2 to HC mol ratio 2:1- 8:1. Naphthene
dehydrogenation takes place in the first
reactor. This reaction being endothermic,
the temp drops rapidly.
• The effluent from the first reactor is
reheated in a inter heater before sending to
the second reactor. Furthur
dehydrogenation and paraffin
dehydrocyclisation occur in this reactor,
again dropping the reaction temp.
• The effluent from the second reactor is
again reheated in an heater and send to the
third reactor where major reactions are
hydrocracking and paraffin isomerisation.
• Usually design is made in such a way that first
reactor is small (naphthenic dehydrogenation take
place rapidly and at high space velocity). The second
reactor is larger than the first and the third reactor is
still large.
• the product effluent from this final reactor are heat
exchanged with fresh feed, cooled and send to
separation vessel to separate the liquid products
from the recycle gas which is compressed and
recycled. The liquid product from the separator is
then allowed to enter a distillation column called
stabilizer to remove C4 and lighter material. The
stabilized reformate is used for gasoline blending.
Reactor internal arrangement

Process gas

Catalyst in

Scallops

Central pipe

Scallops

Scallops arrangement

Catalyst out
Gap between scallop
Process gas
Representation of Catalyst after various stages of operation
• Reaction pre =10 to 40 bar
• Temp = 460 to 540 C
• Hydrogen – HC ratio=2:1 to 8:1
• Space velocity =1 to 3/hr.
• Usually first reactor is small, naphthenic
dehydrogenation take place rapidly and at
high space velocity.
• Second reactor, dehydrogenation and
paraffin dehydrocyclization occur
• Third reactor hydro cracking and paraffin
isomerization.
 Process variables
• Reactor inlet temp-520C
• Reactor pre-pre increases hydrocracking
and decreases aromatization reaction,
however low pre favours coke formation
as hydrgen partial pre is reduced.(30 to 40
Kg/cm2)
• Space velocity-1.5 to 3/hr.
• Hydrogen recycle to feed ratio.
 Cyclic regeneration
• Catalyst is subjected to more severe operating
conditions leading to rapid catalyst deactivation.
• Process require lower pressure and lower
recycle gas rate giving additional advantages of
• 1. higher reformate yield
• 2. higher hydrogen yield
• 3, lower temp in furnace, lower make up gas
power requirements.
• Four reactors in series, one in regenerator mode
and other three in operation.
 ALKYLATION
• Alkylation refers to a process carried out
for producing high octane motor fuel by
combining light olefin with isobutane.
• Paraffin + Olefin – Alkylate
• Process is exothermic
• Ratio of isobutane to olefin 8-15 :1 and
recycling excess isobutane
• Reaction proceeds through carbonium ion
mechanism
• Isobutane + isobutene – 2,2,4 trimethyl pentane
(iso octane)
• The octane number of the alkylate is depends on
the nature of olefin
• Alkylation becomes a major tool in the hands of
the refiner for octane improvement after the phase
out of leaded additive from motor gasoline.
• Alkylate has both excellent stability and high
octane number. In addition it has high heat of
combustion, low V.P, low cost butane to be put
into gasoline.
 Chemistry of reaction
• Alkylation reaction proceeds through the
formation of a carbonium ion chain reaction.
• Initiation reaction- carbonium ion is
generated by adding a proton to an isobutene
molecule in the presence of a strong acid.
• Isobutene + Proton – T-butyl carbonium ion
• Addition reaction-
• T-butyl carbonium ion + Isobutene – C8
carbonium ion
• Propagation reaction-
• C8 carbonium ion + Isobutene – 2,2,4
trimethyl pentane + t butyl carbonium ion.
• Termination-
• T butyl carbonium ion – isobutene +
hydrogen.
 Catalyst for alkylation process
• Aluminium Chloride
• Sulphuric acid
• Hudrofluoric acid
• Solid Acid catalyst - Zeolite
• 60% of alkylation is done by sulphuric acid
and rest is done by HF.
 Process variables
• Reaction temp-
• Acid strength
• Isobutane concentration (15 :1)
• Olefin space velocity- contact time for HF
alkylation ranges from 5 to 25 min and for
sulphuric acid alkylation 5 to 40 min.
 Alkylation feed stock
• Olefin and isobutane are the feed stock.
• Chief sources of olefin are catalytic
cracking and coking operation.
• Hydrocrackers, catalytic crackers and
isomerization produce a great deal of
iso butane.
• Reformer also produce isobutane.
 Process licensors
• Philips petroleum-HF
• UOP-HF
• Exxon Mobil- H2SO4
• Kellog- H2SO4
• Solid acid catalyst by Philips and UOP
Sulphuric acid Alkylation process
• Fresh 98-99% sulphuric acid is to be added
periodically to maintain the acid strength.
• High viscosity of sulphuric acid and the large
diff in density of the acid part and the
reactants makes vigorous mechanical
agitation to get the required degree of mixing.
• The acid consumption for butene feed stock
in the range of 35 to 60 kg/m3 of alkylates.
• The acid consumption can also get adversely
affected by H2S and mercaptan sulphur.
• Temp – 3 to 12 C (to minimize oxidation reaction)
• High iso paraffin/olefin ratio (15 :1 ) are used to minimize
polymerization and increase product octane.
• Concentrated sulphuric acid catalyst
• Hydrogen Fluoride Alkylation
• Temp – 25 to 45 C
• Cost is less
• Environmental problem of sludge disposal is avoided
• Viscosity of HF is less
• HF is volatile liquid
• High temp octane number is less
• It can be handled in carbon steel only in anhydrous state.
• Net acid consumption in HF process is considerably lower
than sulphuric acid process.
HF Alkylation
Sulphuric Acid alkylation
 Process description
• Multistage cascade reactor system ( fitted
in each stage with a mixer) employed. HC
and acid pass from one stage to other
cascading serially, olefin is split and
introduced into each cascade. The formed
alkylate is taken out from the top of
cascade reactor, cooled and fractionated.
Iso butane from the fractionator is mixed
with the incoming feed and sent into reactor.
• Acid from the bottom of the reactor is
taken and kept in circulation, necessary
fresh addition of acid is also continued.
Propane evaporation causes self
refrigeration and maintain the temp of
alkylation at required level.
HF alkylation
 Process description
• Olefin and iso butane feed (1:5 ) is dried and
mixed with recycling acid. The mixture is
passed into reactor, the reactor acts as settler
also. After reaction is completed mixture is
allowed to settle into two liquid layers. Acid
layer is removed from the bottom of the
settler, cooled and recycled. Fresh acid is
supplemented. A part of acid is stripped to
remove water and polymer products. Acid
free from this is again mixed with the
circulating acid.
• HC layer removed from the top of the acid
settler contain unreacted constituents and
alkylate along with small amount of acid.
The components are separated by
fractionation and iso butane is circulated
into the reactor.
• Alkylate from the bottom is again syabilized
to separate isobutane. Isobutane leaving
from these column is fed back to the
reactor.
 Comparison of sulphuric acid and
HF
Sulphuric acid HF
Low temp (less than 15C to prevent 35 C
oxidation of the products) 3 to 12 C
Fresh acid(95%) gives low yield of Make up requirement is very less.
alkylate, circulating acid give improved
yield.
Some additives are also added to Availability is also less.
decrease the consumption of acid and
increase the yield of alkylate.
Reactions are exothermic hence heat Capital and operating cost is less.
removal is essential.
 Isomerization
• The process of converting straight chain
compounds into branched ones is called
isomerization.
• Converting n-butane into isobutane which
can be alkylated in a second step.
• Increasing the octane number of the paraffin
boiling in the gasoline range by converting
some of the n- paraffins into isoparaffin
• N- pentane has octane number of 62 and
isopentane has a rating of 92.3
• N hexane to 2- methyl pentane, 3- methyl
pentane, 2,2 dimetyl butane, 2,3 dimethyl
butane.
• Isomerization take place in vapour phase or
in liquid phase with dissolved catalysts.
• Aluminum chloride catalysts employed. This
catalysts can be used in fixed bed or in liquid
contactors.
• Noble metal catalysts(Platinum supported on
silica alumina) are generally employed in fixed
beds only.
• Some hydrocracking occurs during reactions,
results in a production of light gas.
• First generation- aluminium chloride
catalyst
• Second generation – metal support
bifunctional catalyst.
• Third generation- metal support
bifunctional catalyst with halogenation of
acidic support.
• Fourth generation- zeolite with metal
support.
Fixed bed isomerization of butane
• Aluminum chloride catalyst promoted with
hydrochloric acid at a temp of 100C
• Undesirable side reactions are avoided by
adding inhibitors to the feed or by carrying
out the reaction in the presence of
hydrogen.
Isomerization with fixed bed
aluminium chloride catalyst
 Process description
• Desulphurised and moisture free feed stock
(C5 and C6) with recycled n- paraffin is mixed
with H2 and heated. This mixture with
recycled HCl gas enters the reactor(1), where
catalyst is spread on alumina in fixed bed.
• The effluents are passed through a catalyst
recovery system(2) and then through a
pressure releaser(4). The effluent is given
caustic wash (5) and finally sent into
fractionator(6) to separate iso paraffin and n-
paraffin. N- paraffin is recycled back.
• Temp -180 to 250C
• Pre – 20 to 50 ata
• H2 – 2 to 6 M3/bbl
• HCl- 4 to 5 wt%
Aluminum Chloride(liquid phase)
isomerization process
• Aluminum chloride when used in liquid
contactors is generally dissolved or made
into slurry in hydrocarbon liquid.
• These catalysts are capable of taking feeds
containing sulphur and water up to 35 and
50 ppm. Catalysts are regeneratable.
• Temp- 250 to 300C
• Pre- 15 to 30 atm
 Process description
• Paraffin feed is dried in a drier (2) and
heated to 60 to 100C in a HE (3). The feed
now passes into catalyst scrubber (4),
where it can remove the catalyst entrapped
in heavy sludge obtained in the process.
• The feed is then mixed with H2, and HCl
vapours and allowed to enter the agitator
reactor (5), where fresh/ recycle catalyst is
always present.
• The effluents are then washed with water/
alcohol to remove the catalyst in a wash
column (6). The light HC layer is fed into an
accumulator where H2 and HCl are
separated. Heavy settled HC layer
circulated back to wash column while some
products is taken to a stripper where
remaining HCl vapours are driven off. Light
paraffin recycled back, while iso paraffin
obtained at the bottom .
 Polymerization
• Convert propene and butene into liquid
condensation products of high octane number
suitable for gasoline blending.
• Can be carried out in either thermal (510-595C,
and 1200 to 2000 psi) or in presence of catalyst.
• Pelleted Kieselghur(diatomaceous earth)
impregnated with phosphoric acid.(reaction
temp 175 to 225C and 400 to 1200 psi
• Impurities like sulphur, ammonia must be
removed before process.
• Polymerization process helps the refiner
to convert olefin gases like propene and
butene in to liquid condensation product
of high octane number suitable for
gasoline blending.
• Water injection necessary to hydrate the
phosphoric acid catalysts.
• Exothermic reaction.
• Polymerization reaction is highly
exothermic and temp is controlled either by
injecting a cold propane quench or by
generating steam.
• Propane and butane in the feed act as a
diluents and a heat sink to help control the
temp. propane is also recycled to help
control the temp.
• IFP license a process to produce iso hexane
from propene using a homogeneous alkyl
catalyst.
Polymerization process
Polymerization process
• The feed stock consists of C3 and C4
olefins (40 to 60%) obtained from crackers.
• Catalyst is phosphoric acid deposited on
carriers of inert nature (quartz, Kieselguhr).
The reaction is exothermic and is controlled
by admitting cold feed stock into the
reactor.
• The off gas from the crackers are first
washed with caustic and water(1). The
gases are then passed through a drier(2),
enter the reactor (3).
• The effluent from the reactor enters through
a cooler into pressure releaser (4) where
condensed gasoline is collected and recycled
gas is separated. The liquid fractions are now
taken into fractionator(5) where polymer
gasoline is obtained from the bottom of the
column.
• Unreacted gas escape from the top of the
tower. The reactions can be conducted at low
pre or high pre. The life of the catalyst is less
when low pre is used. The polymer can give
an octane number of 94 to 97.
• Naphthenic stocks are preferred in
catalytic cracking, while paraffinic stocks
require hydrocracking.
• Thus hydrocracking has become a
powerful tool to the refiner in the
production of quality gasoline or mid
barrel products from heavy distillates or
fuel oil.
 Processing Units in Oil Refineries

• Primary Processing Units

– Distillation
– Blending
• Secondary Processing Units
– Catalytic Cracking
– Hydro-cracking
– Catalytic Reforming
– Isomerization / Alkylation, etc
• Bottom Upgradation Units
– Visbreaking
– Delayed Coking
• Treating Units
– Hydrotreating
 Assignment No:1
• Explain the chemistry of reaction, type of
catalyst and process parameters of the
following conversion process.
• 1. Thermal cracking- Visbreaking and Coking.
• 2. Catalytic cracking
• 3. Catalytic reforming
• 4. Isomerization
• 5 Alkylation
• 6. Polymerization
• 7. Hydrocracking.