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, 2methyl-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 chemical petroleum and petrochemical
industries.
During 1940, FCC was introduced in petroleum industries for the
conversion of gas oils and residue into more valuable product.

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 365-3700C and enters the riser where it comes in
contact with hot regenerated catalyst at a temperature of about 6306500C.
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 from the top of the
fractionator and further separated in stripper and absorber.

 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 point(0C)

Wt% range

Avg. Wt%

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-2

0.9

13-16

14.5

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 2butene.

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 40-90oC 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-2butene are reactive while 3-methyl-1-butene is nonreactive.

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.

TAME Manufacture by Conventional Fixed Bed Technology

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 --1.5%;
isoprene-13.5%; pentadiene(piperylene)-9%;
cyclopentadiene-7.5%; and C6+ ---1%.

 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 >1200C 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 1,4pentadiene.
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

(4). Debutanizer
(5). Stripper
(6). Absorber
(8) & (9). Execrative Distillation columns.

(3). Distillation of extract

(7). Solvent stripper

Processing of C5 Stream