Introduction of Catalytic Reforming Process: The aim of this process is to improve the octane number of a naphtha feedstock by changing

its
chemical composition.
Catalytic reforming is considered the key process for obtaining benzene, toluene, and xylenes
(BTX). These aromatics are important intermediates for the production of many chemicals.
Hydrocarbon compounds differ greatly in their octane ratings due to differences in structure.
In general, aromatics have higher octane ratings than paraffins and cycloparaffins.
Increasing the octane number of a low-octane naphtha fraction is achieved by changing the
molecular structure of the low octane number components.
The feed to a catalytic reformer is normally a heavy naphtha fraction produced from
atmospheric distillation units.
The naphtha must be hydro treated to saturate the olefins and to hydrodesulfurize and
hydrodenitrogenate sulfur and nitrogen compounds.
Olefinic compounds are undesirable because they are precursors for coke, which deactivates the
catalyst. Sulfur and nitrogen compounds poison the reforming catalyst.
Feeds with a high naphthene content are easier to aromatize than feeds with a high ratio of
paraffins.
Feeds with higher end points (200C) are favorable because some of the long-chain molecules
are hydrocracked to molecules in the gasoline range.
The catalysts generally used in catalytic reforming are dual functional to provide two types of
catalytic sites, hydrogenation-dehydrogenation sites and acid sites.
The former sites are provided by platinum and the latter is provided by an alumina carrier.
The two types of sites are necessary for aromatization and isomerization reactions.
Bimetallic catalysts such as Pt/Re have better stability, increased catalyst activity, and selectivity.
Trimetallic catalysts of noble metal alloys are also used.
These catalysts can tolerate higher sulfer naphtha feeds (>1 ppm)
Many reactions occurs in the reactors.
aromatization reactions, which produce aromatics.
Isomerization reactions, which produce branched paraffins.
Hydrocracking, these is not directly involved in aromatics formation.

Reactions of Catalytic Reforming Unit:1.) Aromatization

The two reactions directly responsible for enriching naphtha with aromatics are:a) Dehydrogenation of naphthenes

b) Dehydrocyclization of paraffins to aromatics

2.) Isomerization
Isomerization reactions may occur on the platinum catalyst surface or on the acid
catalyst sites.
Most isomerization reactions, however, occur through formation of a carbocation.
The formed carbocation could rearrange through a hydride-methide shift that would
lead to branched isomers.
Example: the isomerization of n-heptane to 2-methylhexane through 1,2-methide
hydride shifts.

Isomerization of alkylcyclopentanes may also occur on the platinum catalyst surface

or on the silica/alumina.

3.) Hydrocracking
Hydrocracking is a hydrogen-consuming reaction that leads to higher gas production
and lower liquid yield.
hydrocracking long-chain molecules can produce C6, C7, and C8 hydrocarbons that are
suitable for hydrodecyclization to aromatics.

FLUIDIZED CATALYTIC CRACKING (FCC)

During 80's with increased processing of the North Gujarat and Bombay High Crudes, the
production of LSHS had gone up. This increased production of LSHS should have been suitably
disposed off to enable the refinery to operate at its maximum throughput for meeting
requirements of the petroleum products. This LSHS, which is presently being supplied as Fuel
for burning, has a good potential of being refined into high priced distillates, which are in great
deficit in our country. The steep increase in the prices of Crude Oil and Petroleum Products in
the past few years and Governments Policy of conservation of Petroleum energy has changed
the situation totally and it became necessary to review the utilization of LSHS more
economically and profitably .Based on the above consideration, the various alternatives of
Secondary Processing Schemes were examined and it was decided to install Fluid Catalytic
Cracking Unit (FCC) at Gujarat Refinery.In 1982 Gujarat Refinery FCC Unit was commissioned with a
capacity of 1 MMTPA.
HISTORY OF FLUIDIZED CATALYTIC CRACKER:Cracking is a phenomenon by which large oil

molecules are decomposed into small

lower boiling molecules. At the time certain of these molecules, which are reactive,
combine with one another to give even larger molecules than those present in the
original stock. The more stable molecules leave the system as cracked gasoline and
reactive ones polymerize forming fuel oil and even coke. Although primary objective in
development of the cracking process had been to get more and more of gasoline, all
other oils having boiling ranges intermediate between fuel oil and gasoline is also
produced.The originally developed process of cracking was Thermal Cracking. Use

of catalyst for cracking was first investigated by HOUDRY in 1927.Catalytic cracking

has many advantages over Thermal cracking viz.
1.

Catalytic cracking gives more stable products.

2.

For corresponding yield and quality of gasoline, catalytic cracking unit

operates under less severe conditions.

3.

Catalytic cracking gives high-octane gasoline (viz.91-94 octane).

4.

It yields less gas viz. Methane, Ethane and Ethylene.

BATCH PROCESS:
The first Commercial Catalytic Cracking Unit was put into operation in 1936. It was a
Fixed-bed Catalytic Cracking Unit. It consists of a series of chamber / reactors, wherein
one of them is on-stream, the others will be in the process of cleaning, regeneration etc.
This type of process has a disadvantage of being an intermittent process having a high
initial investment and operating cost.

CONTINUOUS PROCESS:

The advantages of continuous process led to the development of the idea of a moving bed
catalyst. Examples of this type are Thermofor Cracking; Thermofor Cat Cracking and
Houndry Airlift processes. In the Thermofor Cat cracking, the Palletized Catalyst was
conveyed between the Reactor and regenerator by means of Bucket Elevators. Higher
investment by capacity limitations of Elevators/Air lift systems together with other
Engineering and process difficulties led to the development of latest concept in moving bed
catalytic cracking i.e. Fluidized Catalytic Cracking.
FLUIDIZED CATALYTIC CRACKING:
The radical development was made by Standard Oil Co., New Jersey, M.W.Kellogg and UOP in
early 1940s in which the Catalyst in the form of fine powder was held in suspension in Gas
Stream. It was found that by carefully controlling the Catalyst particle size and the velocity of

gas moving through it, a Fluidized bed of Catalyst would form which has the properties of liquid.
In the fluidized system, finely Powdered Catalyst is lifted into the Reactor by incoming oil, which
immediately vaporizes upon contact with the Hot Catalyst and after reaction is complete, it is
lifted into the regeneration zone. Cat Crackers using Powdered Catalyst in this way are known
as FLUID CAT CRACKING UNITS.

FEED:- VGO and VR from FPU. The feed is characterized by following:

1).Carbon Residue:- Carbon residue of the feed stock is determined by CCR and it indicates the
coke forming tendency to feed. Valued for good cracking feed stock are 0.2 % wt or less.
2).Metal Content:- Most crude oil contain metallic compound which can enter the catalytic
cracker either by entertainment or because the compounds are themselves volatile and actually
distilled in the feed preparation units Ni, Fe, C u are particularly harmful. Cleanliness of a charge
stock with respect to metals is judged by its metal factor.
3). Sulphur :- It is undesirable in catalytic cracker charge as it is in the feed to any refining unit
since it causes corrosion of the equipment. Also it increases difficulty of treating products and
lower lead response of catalytic cracker gasoline.

Catalytic Cracking Reactions:

Catalytic cracking reaction produce unsaturated short chains like ethylene, excellent high
octane components like benzene ans isooctane and lower molecular weight gas oil like cetane.
During cracking, apart from basic reaction of breaking of big molecules to small ones, other
reaction like isomerization, cyclization, alkylization, polymerization etc also take place.
Cracking Catalyst:
The catalyst used in catalytic cracking process as a fine powder made up primarily of alumina
and silica. Basically there are two types of catalyst amorphous and zeolite. Zeolite catalyst
contains molecular sieves and varying quantities of rear earths. These are formed through
reaction of reactive forms of alumina and silica.
Products:
The FCC unit catalytically cracks the vacuum gas oil(VGO) from vacuum distillation unit(VDU)
and feed preparation unit (FPU) to various high priced hydrocarbons. These hydrocarbon vapor
are separated by into the following products in the fractionating and gas concentration section:
a) Fuel gas
b) LPG
c) Gasoline of high octane number

d) HSD components
e) LDO
f) Fuel oil components

Process:
FCC consists of three section:
1) Catalyst section
2) Fractionating section
3) Gas concentration section
Catalyst section:
The Catalyst Section consists of the Reactor and Regenerator, which, together with the Stand
Pipes and Riser, form the Catalyst Circulation System. The catalyst circulates up the Riser to
the Reactor, down through the Stripper to the Regenerator across the Regenerator Standpipe,
and back to the Riser.Fresh feed and recycle streams, known as Combined Feed, are vaporized
and heated to the reactor temperature by the hot catalyst. This mixture of oil vapour and catalyst
travels up the Riser into the Reactor. The gas oil commences to crack immediately when it
contacts the hot catalyst in the Riser and continues until the oil vapours are disengaged from
the catalyst in the Reactor. The cracked products in the vapour phase goes from Reactor to the
fractionators through Reactor Vapour line.
Reactor:
The combined feed meets with hot catalyst from regenerator at the bottom of reactor riser. The
resulting catalyst-oil vapour mixture is raised to the desired reaction temperature by using
sensible heat of catalyst. Almost total cracking reaction takes place in the riser. Residence time
in the riser is around 3-5 seconds. Lift steam is also introduced at the bottom of the riser
through flow controller 2FC-7201 and 2FC-7202 to lift the catalyst/oil mixture inside the
riser.The oil vapours disengage from the catalyst as soon as they leave the VSS (Vortex
Separator System) and leave the reactor through 3 nos. single stage cyclone separators
suspended from reactor top head. The catalyst from the cyclones returns to the dense phase of
reactor, through cyclone dip legs.

Regenerator:
In the process of cracking in the riser / reactor, coke deposition takes place on the catalyst
surface. With the result, the active surfaces of catalyst reduce. To regenerate the catalyst, the
deposited coke is burnt off by air in the regenerator. The atmospheric air is taken though a
blower, 820-K-01, at ambient conditions and discharged to the regenerator at 220-250 oC. The
excess air is vented to atmosphere by 2FC 6819. This c/v controls the airflow through
regenerator depending upon the cyclone temperature set in the RMPC. The regenerated
catalyst leaves the regenerator through the regenerator standpipe. A slide valve (RCSV), which
is reset by 2TC 7316, controls the temperature of the reactor. An expansion joint is provided on
this standpipe. The regenerated catalyst goes to the bottom of the reactor riser and is lifted by
the lift steam/ VB naphtha. As the catalyst rises up the riser it mixes with the combined feed and
slurry recycle streams, which are injected through their respective nozzles. Thus catalyst
circulation is established between reactor and regenerator. Normal catalyst circulation rate is
16-22 MT/minute.
Orifice Chamber:
The coke is burnt in the regenerator to form a mixture of carbon monoxide and carbon
dioxide.The gases containing 6-8 % CO come out of 3 sets of two stage cyclones in
regenerator and leave from the top. A double disc slide valve (DDSV) located on the flue gas
line is reset by 2PDC 7346.

DDSV controls the differential pressure between the regenerator

and reactor. Gases are passed through an orifice chamber, 820-ME-3, where a series of
restriction orifices reduce the pressure of gases so that differential pressure across DDVS is
reduced which in turn reduced its erosion.The two-port slide valve located at the bottom of
orifice chamber routes the flue gases either to CO Boiler or to the stack bypassing CO
Boiler.A sacrificial sleeve is provided on the outlet nozzle or DDSV to protect the conical portion
of orifice chamber from erosion.
CO Boiler:
The Co boiler is just like any other convectional water tube boiler consisting of two drums and
one super heated disposed at the flue gas path. It is a front wall fired medium pressure (MP) &
Temperaure, natural circulation boiler. The upper drum, which is called stream drum but
essentially contains stream and water both, is fed with hot feed water(132-140 deg. C) supplied
through a feed control valve the colder water from the upper drum flows to lower water drum

through a bunch of a tubes called down comers which are disposed at the lower temperature
zone of the furnace. The water content in the furnace wall tubes or riser tubes is heated by the
heat releases in the furnace on combustion of fuel. The heated water in the riser tubes becomes
lighter and moves up into the upper stream. These riser tubes are disposed in such a fashion
that it makes a closed envelop of the furnace covering all the six sides of the furnace so as to
pick up maximum possible heat.

Fractionation section:
In the fractionation section, the Reactor vapours are fractionated into Wet Gas, Unstabilized
Gasoline, Heavy Naphtha, Light Cycle Oil (LCO), Heavy Cycle Oil (HCO) and Clarified Oil
(CLO).
The reaction product vapors (at 535 C and a pressure of 1.72 barg) flow from the top of the reactor to the bottom section of the
fractionator where they are distilled into the FCC end products of cracked naphtha fuel oil and offgas. After further processing for
removal of sulfur compounds, the cracked naphtha becomes a high-octane component of the refinery's blended gasolines.
The main fractionator offgas is sent to what is called a gas recovery unit where it is separated into butanes, butylenes,
propane, and propylene and lower molecular weight gases (hydrogen, methane, ethylene and ethane). Some FCC gas recovery
units may also separate out some of the ethane and ethylene.
Although the schematic flow diagram above depicts the main fractionator as having only one sidecut stripper and one fuel oil
product, many FCC main fractionators have two sidecut strippers and produce a light fuel oil and a heavy fuel oil. Likewise, many
FCC main fractionators produce a light cracked naphtha and a heavy cracked naphtha. The terminology light and heavy in this
context refers to the product boiling ranges, with light products having a lower boiling range than heavy products.
The bottom product oil from the main fractionator contains residual catalyst particles which were not completely removed by the
cyclones in the top of the reactor. For that reason, the bottom product oil is referred to as a slurry oil. Part of that slurry oil is recycled
back into the main fractionator above the entry point of the hot reaction product vapors so as to cool and partially condense the
reaction product vapors as they enter the main fractionator. The remainder of the slurry oil is pumped through a slurry settler. The
bottom oil from the slurry settler contains most of the slurry oil catalyst particles and is recycled back into the catalyst riser by
combining it with the FCC feedstock oil. The so-called clarified slurry oil or decant oil is withdrawn from the top of slurry settler for
use elsewhere in the refinery, as a heavy fuel oil blending component, or as carbon black feedstock.

Gas concentration section:

Compressed Wet Gas and Unstabilized Gasoline go to Gas Concentration Unit where they are
separated into Fuel Gas, LPG & Stabilized Gasoline, LPG and Gasoline are washed with
caustic in the treating section of Gas Concentration Unit. Amine treatment of LPG is done prior
to caustic wash.

Further Processing of Products:

The main products from FCC unit are gasoline and LPG. After these products are separated
through fractionation and stabilization section, they are given some chemical treatment like
caustic soda and water wash to remove the impurities still present.
Following chemicals are used in FCC:
1) Caustic soda:
Caustic soda is used for LPG and gasoline caustic wash. It removes H2S and lighter
mercaptans from these streams. Caustic with approximately 40-45 % strength is received
from LPG station through a 2 line into tank. This caustic is diluted to 10-15 % by adding
water to tank.
2) TRI Sodium Poshpate:
Tri-sodium poshhpate is added to MP steam generations. It helps in reducing scale
formation in the steam generation by forming sludge with scale forming scale forming salts.
This sludge goes out of the system during below down operations.
3) Hydrazine(N2H4) :
While major portion of dissolved oxygen is removed from boiler feed water is scavenges with
the help of hydrazine.
N2H4 + O2

2H2O + N2

4) Ahuralan:
It is an organic chemical, which acts as corrosion inhibitor by forming continuously
renewable monomolecular layer in the metal surface with corrosive elements, present in the
system.

Figure: Process Flow Diagram of FCC