UNIT-III

Processing of olefinic C4 and C5 Cut

from Steam cracking and Fluid
catalytic cracking
 Contents
Introduction
FCC
Various Petroleum Products from FCC and their uses
Product profile of C5 Hydrocarbons
Description of FCC and FCC gases as petrochemical
feedstock
Processing of C4 stream from stream cracker and FCC
(Separation of C4 hydrocarbons from FCC and Steam
Cracker plants)
Oxygenates from refinery C4 & C5 stream
Methyl tertiary butyl ether
Tertiary amyl methyl ether
Upgrading Of C5 Cuts For Recovery Of C5 Chemicals
 Introduction
With the rising demand of ethylene and
propylene, there has been a tremendous
growth in the steam cracking of hydrocarbons
during the last four decades.

Similarly, FCC (Fluid Catalytic Cracking) has

developed into a major upgrading process in
the petroleum refinery industry for the
conversion of heavy fuel oil into more valuable
products ranging from light olefins to naphtha
and middle distillate.
 Large amounts of C4 and C5 compounds are
produced along with the production of ethylene in
steam cracking and gasoline in FCC.
C4 & C5 streams are an important source of
feedstock for synthetic rubber and many
chemicals.
With increasing demand of C5 hydrocarbons and
oxygenates, upgrading of C4 and C5 streams from
steam crackers and catalytic cracker is important
to the economic performance of the above
processes.
The quantity and composition of the C4 and C5
stream depends on the severity of the steam
cracker operation and feedstock processed.
Importance of utilization of C4 stream can be
realized from the fact that global demand for
butadiene, isobutylene, and 1-butene, three major
C4 olefins will climb to 11.2, 18.8,1.7 million tones
by 2010..
global demand for butadiene over the long term
will grow 3.3percencent per year on an average as
compared to 4.9 percent per year for ethylene.
The main C5 compounds like isoprene, n-pentenes,
2-methyl-2-butene, Cyclopentene and
cyclopentadiene.
C5 hydrocarbons are present with pyrolysis
gasoline obtained after separation of C4 stream in
the butanizer.
 Fluid catalytic cracking
Although FCC is an important petroleum refining
process, and FCC gases are important
petrochemical feedstock for production of LPG
which can be converted to aromatics and C3, C4
andC5 hydrocarbons, i.e. propylene, butene,
isobutene, pentene, etc.
Cracking one of the important secondary
processes is conversion of a longer hydrocarbon
molecule to small one either by thermal or
catalytic cracking.
To control reactions in order to avoid too much
coke formation or the formation of very small
molecules, industrial cracking of petroleum heavy
fractions are aided by catalyst.
With the advent of fluidized technology, fluidized
bed reactors found commercial application in
Various Petroleum Products from
FCC and their uses
Product profile of C5 Hydrocarbons
C5 hydrocarbons are an important source of synthetic rubber,
solvents, chemical intermediate, MTBE, plasticizers, TAME,
rubber chemicals, herbicides, lube oil additives,
pharmaceuticals.
 Description of FCC
FCC unit can be divided into two sections: (i). The reactor
and regenerator system and (ii) the fractionation column.
The feed to the unit along with the recycle streams is
preheated to a temperature of 365-370 0C and enters the
riser where it comes in contact with hot regenerated
catalyst at a temperature of about 630-650 0C.
The hot catalyst vaporizes the feed and the cracking
reaction takes place in the riser.
This vaporization fluidizes the catalyst up the riser to the
disengaging T-section at the top of the riser.
The cracked hydrocarbons exit from the reactor through a
cyclone to the fractionation column where overheated FCC
gases including LPG and gasoline are removed as vapour.
The extruded catalyst is collected in the cyclone and
returned to the reactor. The spent catalyst flows through
the regenerator where the coke is burnt off.
In the fractionator, the reactor vapors are
fractionated into recycle gas oils which are
released to the riser for further cracking
and converted to following products such as
clarified slurry, heavy cycle oil, cracked light
cycle oil, unstabilized gasoline and wet gas.
Unstabilized gasoline separated from the
lighter products is sent to debutanizer for
separation of C3 and C4 as overhead
products.
The main column bottom is sent to slurry
setter where settled slurry containing
catalyst is recycled.
Water and gasoline vapors are withdrawn
The function of the stripper-absorber section is separate the
main fractionator overhead product into a dispropanized fuel
gas product and a liquid feed to the debutanizer of low
ethane content.
The fractionator overhead product enters the stripper-
absorber section as both a liquid stream and a vapor stream.
The various products from the stripper-absorber section are:
LPG, light naphtha, C3 & C4 gases and heavy naphtha.
Important variables for spent catalyst stripper performance
are temperature, pressure, steam rate, steam and catalyst
distribution, diameter and height of the stripper.
The coke on the catalyst is drawn off in the regenerator
mainly depends on temperature, pressure O2 Conc.,
superficial air velocity, residence time of the catalyst and air
in the regenerator.
Unstabilized gasoline from the bottom of the primary
absorber unit is sent to stripper where light
components are removed and then it proceeds to
debutanizer where C3 and C4 are removed overhead
as LPG.
LPG is treated with amine by Merox Process to
remove sulphur compounds and then sent to LPG
pool as a feedstock to propylene recovery unit.
Propylene is recovered from cracked LPG which is a
mixture of propane, propylene , butane and butylene.
First a mixture of propane and propylene is obtained
from splitter, which is further fed to a splitter from
where propylene is obtained as a separate stream.
There has been a steady increase in Zeolite content of FCC
catalysts from 10% in the 1960s to over 35% today.
Some of todays FCC catalysts contain up to 50% zeolite.
The catalysts are the heart of the FCC process and they
provide:
low coke yield and effective carbon rejections
high selectivity to derived products (light olefins and gasoline)
enhancement of desired properties such as octane number
in-situ control of emissions such as SOx.
ZSM-5 which is crystalline aluminosilicate substance has
been used as an additive to increase octane number and
light olefins yield.
Most of the Indian refineries are used to ZSM-5 catalyst
instant of amorphous silica-alumina catalyst , which has
resulted in increase in LPG yield, increase in propylene
content in LPG from 5.6(wt%) to 15-19(wt%) in octane
number and reduction in coke.
 Indias first RFCC has been commissioned in the Panipat refinery
with a capacity of 0.7 MPTA Licensed by Stone and Webster.

The unit is designed to process a blend of 85.7(wt%)hydrocracker

bottoms and 14.3(wt%) vacuum residue as well as 100%
hydrocracker bottoms.
 FCC Gases as Petrochemical feedstock
FCC off gases are considerable importance as feed stock for
petrochemicals.

Some of the important building blocks, which can be derived from

FCC are:
dilute ethylene stream, LPG, Propylene, and C4 streams containing
butane/butylene.
Typical composition of C4 streams form FCC
with available quantities for 1 MPTA and 0.6
MPTA capacities.
Components Boiling Wt% Avg. Wt%
point(0C) range
Isobutane -11.4 35-36 35.5
Isobutene -6.9 15-17 16
1-Butene -6.3 10-14 11.5
n-Butane 0.5 11-14 13
Cis-Butene-2 3.7 9-16 9.5
Trans-Butene- 0.9 13-16 14.5
2

The LPG as well off gases for the FCC unit are
in olefins. The former contain up to 20-30%
propylene while the latter could have 5-10%
ethylene.
 Processing of C4 stream from
stream cracker and FCC
The processing of C4 streams after the recovery of
butadiene form the stream cracker and from FCC.
C4 cut from the steam cracker is first sent for
butadiene recovery which include selective
hydrogenation of acetylenic in the presence of
palladium catalyst, then separation of butadiene by
solvent extraction.in this process get the high yield of
butadiene by using suitable solvent.
solvent used for separation of butadiene are furfural,
dimethyl formamdie (DMF), n- Methyl
pyrrolidone(NMP) and dimethyl acetamide.
After separation of butadiene the C4 streams from
cracking and FCC are processed for production of n-
butene, 1-butene, 2-butene and isobutene.
Isobutene recovery includes either hydration
of the C4 stream and subsequent
decomposition or etherification of methanol
to yield MTBE, which is cracked to give
isobutene.
Separation of 1-butene is done by selective
hydrogenation followed by adsorption for
separation of 1-butene and further
processing for separation of isobutene and
2-butene by distillation.
Separation of 2-butene involves
hydroisomerization and subsequent
distillation for separation of isobutene and 2-
Separation of C4 hydrocarbons from FCC
and Steam Cracker plants
Separation of C4 hydrocarbons from FCC
and Steam
Cracker plants
OXYGENATES FROM REFINERY C4 & C5 STREAM
The oxygenates from refinery streams are MTBE, TAME and
ETBE.
all oxygenated fuels reduce hydrocarbons in the automobile
exhaust.
MTBE is one of the most important oxygenates used in the
production of lead free gasoline.
the oxygenated MTBE and ETBE are produced by the reaction
of methanol/ethanol and isobutylene.
TAME are produced by etherification of isoamylenes.
isobutylene and isoamylene can be removed from C4 and C5
Streams of stream crackers.
Till recently MTBE was a major additive in reformulated
gasoline, however due to recent concern over the potential
water pollution problems caused by leaking underground
gasoline storage tanks, more US state governments are
adopting legislation to either phase out MTBE or restrict the
MTBE usage as a gasoline additive.
METHYL TERTIARY BUTYL ETHER
MTBA is an excellent front end octane supplier with
no compatibility problems with hydrocarbons.
it is the most widely used octane enhancer in the
current gasoline pool.
MTBE is one of the important oxygenate.
MTBE increases the oxygen content of gasoline
results in the reduction of harmful emissions.
MTBE which is made by etherification of C4 gases
from cracker and FCC is also used for production of
polymer grade isobutylene for synthetic rubber.
The catalyst is a macro reticular ion exchange resin
based on sulphonate styrene divinyl bezene
copolymer.
MTBE is produced by the reaction of methanol with
isobutylene contained in C4 streams from thermal crackers
in the presence of ion exchange resin at 40-90 oC and a
pressure of 5 to 10 kg/cm2.

Convention process and catalytic distillation are the two

commercial processes.
The acidic ion exchange resin catalyst used for MTBE
production is susceptible to some impurities present in the
feedstock which include basic compounds, cations, nitrites,
and surface compounds. these poisons neutralize the acid
sites of the catalyst causing deactivation.
Acetonitrile is the most significant poison in FCC. These
impurities are removed by washing thoroughly with water.
After washing the feed is mixed with methanol and
fed to the reactor.
the inlet temperature and pressure of the reactor
is controlled and sufficient care to taken not to allow
any increase in the temperature of the reactor.
presence of butadiene in the feedstock also
reduces catalyst activity.
butadiene if present in high concentration in the
feedstock can result in isomerization of the
butadiene inside the matrix of the catalyst.
MTBE produced by conventional technology using
two fixed bed reactors in which the first reactor is
either a cycle or tubular reactor , which performs
most of the isobutylene conversion. The finishing
reactor which performs at low temperature.
MTBE from reaction mixture is separated in
distillation column.
In the Catalytic distillation process, the fixed bed
reactor provides the bulk of conversion and the finishing
reaction is done by installing catalyst in the column in a
special packing to provide simultaneous reaction and
distillation.
In this process, after the reaction, the equilibrium
converted reaction mixture is fed to the catalytic
distillation reaction column where the reaction is
continued and the product MTBE is separated from the
unreacted C4s in the catalytic distillation column.
The C4 distillation stream from the catalytic distillation
column is fed to the methanol extraction column where
water is used to separate methanol and water extract
containing methanol is sent to the methanol recovery
column for separation of methanol.
The C4 stream is recovered from the top of the exact
column.
MTBE by Catalytic Distillation
Process
 Tertiary amyl methyl
ether
TAME is another important oxygenate which is
produced by the reaction of methanol with
isoamylenes present in the FCC gases and
stream cracker C4 streams.
TAME has slightly low octane number, it
compares favorably for vapor pressure, boiling
point, density and water miscibility.
TAME is obtained when methanol reacts with
the isoamylenes.
Isoamylenes are 2-methyl-1-butene, 2-methyl-2-
butene are reactive while 3-methyl-1-butene is
non-reactive.
TAME
In the conventional two fixed bed reactor,
etherification process is accomplished in two
reactors using strong acid macro porous
palladium loaded ion exchange resins as a
catalyst.
the palladium resin selectively hydrogenates
dienes in the feed, ensuring a long etherification
catalyst life and a water white clear product.
further separation of TAME is accomplished in
the distillation column.
methanol from the top product of distillation is
recovered by water extraction followed by
distillation.
AME Manufacture by Conventional Fixed Bed Technolo
 Upgrading Of C5 Cuts For Recovery Of
C5 Chemicals
The C5 cut from stream cracker and FCC can be
processed for recovery of valuable C5
chemicals.
Stream cracker C5 cuts contain unsaturated
Hydrocarbons that can be upgraded,
particularly isoprene and pentadiene, as they
are present in high concentration when
naphtha feedstock is used.
Typical C5 cuts from steam cracking contains:
C4 -- 1%; n-pentene -- 26%;
isopentane -- 24%; n-pentenes-- 4.5%;
methyl butenes 12%; cyclopentenes
Dicyclopentadiene is formed of high boiling point and
separated from C5 stream by simple distillation.
Typical composition of C5 cuts from catalytic cracking:
C4 -- 2%; n-pentene 5.5%;
isopentane -- 31.5%; n-pentenes 22.5%;
methyl butenes 37.5%; and C6+ ---1%.
The raw C5 is separated from pyrolysis gasoline by
distillation.
Cyclopentadiene is typically removed in two stages as the
dimer dicyclopentadiene.
Tthe raw C5 Stream is heat isolated at a temperature >120 0C
causing the cyclopentadiene to dimerize.
The process conditions are chosen to ensure
dicyclopentadiene is produced with optimum selectivity.
Dicyclopentadiene is then separated from the remaining by
C5 stream distillation.
A high purity dicyclopentadiene concentrate of 93-94% can
be made this way.
Processing C5 streams:
The cyclopentadiene depleted C5 stream contains traces
of cyclopentadiene, which is dimerized completely by
using another dimerization and distillation.
The C5 stream, which is now virtually completely free of
cyclopentadiene is fed to the extractive distillation
column for isoprene recovery where dimethylformamide
is used as a solvent.
This yields an isoprene and pipeylene stream and a C5
raffinate stream containing C5 olefins and paraffins.
Light acetylenes from the isoprene- piperylene stream
are removed by distillation.
The isoprene and piperylene are separated by
distillation.
The isoprene monomer with purity >99% can be
produced. And Piperylene is usually obtained as
concentrate with 60-75% by weight.
Recovery of the C5 chemicals from C5 Stream involves
dimerization of cyclopentadiene, as well as extraction of di-
olefins and acetylenic compounds.
Raffinate from the extraction column contains pentanes,
pentenes and Dicyclopentadiene.
from the extraction column, the raffinate passes on to a
distillation column which contains the recovered light C4
components and 1,4-pentadiene.
The bottom portion from the distillation column goes to the
stripping section for recovery of the solvent, where as the
top portion from the stripping section goes to the absorption
column. Here piperylene and C5+ acetylenics are recovered
from the bottom.
The extract containing these hydrocarbons go from the
absorption column to two distillation columns for recovery of
piperylene and C2+ acetylenics compounds.
The absorption column top contains a purification section,
comprising two distillations in series for recovery of 2-butene
and isoprene.
1). Cyclopentadiene Isomerization (2). Extractor (3). Distillation of extract
4). Debutanizer (5). Stripper (6). Absorber (7). Solvent stripper
8) & (9). Execrative Distillation columns. Processing of C5 Stre