CHEMICALS FROM FCC AND STEAM

CRACKER
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.
It also provides a rich resource of reactive molecules, which forms the backbone of the synthetic rubber
industry. The quantity and composition of the C4 and C5 stream depends on the severity of the steam
cracker operation and feedstock processed.

Product Profile of C4 and C5 Hydrocarbons

PRODUCT PROFILE OF C5 HYDROCARBON
C5 hydrocarbons –are an important source of synthetic rubber, solvents, chemical intermediate,
MTBE, plasticisers, TAME, rubber chemicals, herbicides, lube oil additives, pharmaceuticals.

C5 Isoprene Polyisoprene, as the cross linking agent in Butyl rubber

Hydrocarbon As co-monomer in stryrene-isoprene copolymers
Isopentane Solvent, Chlorinated derivative, blowing agent for
Polystyrene
1-Pentene Organic Synthesis, blending agent for high octane fuel
2-Pentene Polymerisation inhibitor, organic synthesis
CycloPentene Organic synthesis, polyolefins,epoxies cross linking
agent
2- Methyl-1-Butene Synthetic mark, anyl benzene hydrogen synthetic mark,
anyl benzene hydrogen peroxide catalyst, 2,4-diamyl
phenol (photographs colour complex), pinacolone (Crop
protection chemicals)
3- Methyl-1-Butene Monomer for specialty homo-polymer
Cyclopentadiene Chlorinated insecticides, Chemical intermediate,
Antiviralagent
Piperylene Polymers, maleic anhydride,chemical intermediate

Fluid catalytic cracking (FCC)

Various thermal cracking processes are:

1. Visbreaking
2. Delayed coking
3. Flexicoking and
4. Fluid coking

To avoid coke formation 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 (catalytic
cracking). During the 1940s, Fluid catalytic cracking (FCC) was commercially introduced in
petroleum Industries, It has proved to be the most efficient process available for the conversion of
gas oil and residues into more valuable product.

Fluid catalytic cracking (FCC) converts low value crude oil into a variety of higher value
products which include gasoline, diesel, heating oil and valuable gases containing LPG,
 propylene and C4 and C5 gases. Various products from fluid catalytic cracking and their uses are
given in Table 3.

Product Composition and Uses

Light gases Primarily H2, C1 and C2s, ethylene can be recovered
LPG C3s and C4s containing light olefins suitable for

Gasoline alkylations
C5+ high octane component for gasoline pool or light

Light cycle oil (LCO) fuel

Blend component for diesel or light fuel
Heavy cycle oil Fuel oil or cutter oil

(HCO)
Clarified oil Carbon black feedstock
Coke Used in regenerator to provide the reactor heat demand

FCC gases have now become important petrochemical feedstock for production of LPG which can
be converted to aromatics and C3, C4 and C5 hydrocarbons. FCC units are versatile and can be
operated in three main modes which are aimed at maximizing middle distillate, gasoline, or olefins
respectively by means of the adequate combination of various parameters such as catalyst type,
catalyst to oil ratio, rise of outlet temperature and recycle of fractionators bottom. FCC is the second
largest source of propylene supplied for petrochemical application.

 Conventional FCC 4-7% propylene and 1-2 % Ethylene

 High Severity FCC:10% propylene
 Petro FCCTM (UOP): Ethylene 6%, Propylene 20-22%, Higher aromatics (18%)
in Naphtha
 Higher C4-8 olefins yield which can be cracked to yield lower olefins by
Total Petrochemicals ATOFINA/UOP Olefin cracking Process
 Product distribution from FCC depends

• Reactor temp
• Feed preheat temperature
• Catalyst activity
• Catalyst circulation rate
• Catalyst activity
• Recycle rate

FCC Pretreatment
FCC feedstock is very important in order to meet stringent environmental regulations for reducing
SOx emissions and in achieving better product quality. It consists of desulfurization, denitrogenation,
aromatic saturation and metal removals.

FCC Process

Fig 5.1

Propylene Recovery from FCC: FCC gases has important source of propylene
from refinery and now FCC units are being operated both in gasoline mode and propylene
mode. Propylene from FCC may be as high as 25% with new FCC based propylene technologies.
Increased production of olefins from FCC units has been achieved through changes in operations,
base cracking catalyst and additive catalysts and in hardware designs.

UPGRADING OF C4 and C5 Streams

C4 and C5 Streams from Steam Cracker and FCC contains C4 and C5 hydrocarbons recovery of
which has become important steps for improving the overall economy of these processes. Some
of the important C4 streams from Cracker and FCC butadiene (from cracker plant only) ,butene-

1, 2- butane, isobutylene, mixed n-butene, isobutene.C4 stream of steam cracker contains

appreciable amount of butadiene which is being recovered from naphtha cracker plants. Typical
composition of C4 stream of naphtha cracker and FCC is given in Table.
The distribution product will depend on the feed stock, cracking severity and catalyst in case of
FCC.
 Typical Composition of C4 fraction
Component FCC Steam Cracking
Isobutane 37.0 2.0
Isobutene 24.0 26.0
1-Butene 15.0 13.6
1,3-Butadiene 0.2 36.0
2-Butenes (cis and 11.0 12.0
trans)
n-Butane 12.0 9.8
others balance Balance

Typical C5 cuts from steam cracking contain C4 (1%), n-pentene (26%), isopentane (24%), n-
pentenes (4.5%), methyl butenes (12%), cyclopentenes (1.5%), isoprene (13.5%), pentadiene
(piperylene) (9.0%), cyclopentadiene (7.5%), C6+ (1%). Cyclopentadiene is easily dimerised to
higher boiling dicyclopentadiene and separated from C5 stream by simple distillation. Typical
composition of C5 cuts from catalytic cracking may be C4 (2%), n-pentane (5.5%), isopentane
(31.5%), n-pentenes (22.5%), methyl butenes (37.5%), C6+ (1%) Naphtha feed gives higher yield
of C4 (8-10%) than ethane feed (2-3%)

 Upgrading of C4 Olefins
 The production of chemical intermediates
 Butene-1, isobutylene, mixed n-butene
 Production of motor fuel component (alkylate, dimate, MTBE)

Processing of C4 cut from Steam Cracker and FCC

There is not much difference in the processing of C4 streams after the recovery of butadiene from
the steam cracker and C4 streams from the FCC. C4 stream Butadiene f romC4 stream of naphtha
cracker/ gas cracker is first recovered, followed by separation Isobutylene, isobutanee, butane,
butane-1 and butene-2 from C4 stream/ FCC and cracker using various process like
etherification, hydrolysis, cracking, adsorption distillation etc.

C4 cut from steam cracker and FCC is shown in Figure

Isobutene recovery includes either hydration of the C4 stream and subsequent decomposition
or etherification with 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 hydro- isomerisation and subsequent distillation for separation
of isobutene and 2-butene.

After separation of butadiene, the C4 streams from cracking and FCC is processed for
production of n-butene, 1-butene, 2-butene, and isobutene.
BUTADIENE

Butadiene is important raw material for production of a larger number of synthetic rubber and
polymers such as styrene butadiene rubber (SBR), poly butadiene, chloroprene rubber, nitrile
rubber, acrylonitrile butadiene styrene plastic. Other fastest growing use is in the manufacture of
adiponitrile used in the manufacture of Nylon 66, Steam cracker and catalytic dehydrogenation
of butenees are the two major sources of butadiene. Butenes can be recovered from C4 stream or
produced by dehydrogenation of butanes.

According to SRI consulting global production and consumption of butadiene in 2009

was approximately 9.2 million tones and 9.3 million tones respectively. Butadiene is expected to
average growth of 4.9 per year from 2009-2014. Styrene –butadiene rubber accounted for more

than 33% of global butadiene consumption in 2009 and butadiene rubber for about 25%.

Polymerisation Grade Butadiene

1,3 Butadiene % min
Butenes ppm max 99.6%
4000
Methyacetylenes ppm.max. 25
Vinyl acetate ppm max 200

C5 dimers ppm max 2000

Carbonyl compounds (as aldehyde) max. 50
Inhibitor (p-tertiobutyl catechol) 100- 200
Non-volatile residue ppm 2000

There are four major routes for production of butadiene:

 Steam cracking of naphtha

 Catalytic dehydrogenation of butenes

 Catalytic dehydrogenation of butanes

 Dehydrogenation-dehydration of ethanol (molasses route)

UPGRADING OF C5
CUTS
The steam cracker C5 stream is a rich resource of olefins and diolefins which can be
upgraded to produce elastomers, resins and fine chemical intermediates. In steam crackers
during cracking process along with ethylene, propylene, C4 stream, aromatics and pyrolysis
gasoline bare also formed. Apart from aromatics, Pyrolysis gasoline stream also contains
C5 stream. The quantity and composition of the stream depend on the nature of the cracked
product and severity of cracker operation C5 stream.
Various Steps in the recovery of C5 chemicals are

 Separation of C5 stream from pyrolysis gasoline by

distillation
 Separation of cyclopentadiene: In first stage
cycolpentadine is dimerised to dicyclopentadiene
followed by cracking of dicylopentadiene to
cyclopentadiene.
 Extractive distillation of cyclopentadiene free C5
stream produce isoprene-piperylene stream.
Distillation removes the light aceyelenes
 Separation of isoprene and piperylene extract by
distillation
 Absorption at atmospheric pressure in the presence of
NMP
 Purification of Isoprene rich paraffin
 Periodic regeneration of solvent

Solvents used in extraction of isoprene are Acetonitrile,

N - methylpyropedone, Dimethylformalnide.

OXYGENATES FROM REFINERY C4 AND C5

STREAM
Several oxygenated fuel components have figured prominently in refinery reformulated
gasoline planning. Methyl tertiary butyl ether (MTBE), tertiary amyl methyl ether (TAME)
and ethyl tertiary butyl ether (ETBE). All oxygenated fuels reduce hydrocarbons in the
automobile exhaust. MTBE was considered one of the most important oxygenates used in
the production of lead free gasoline and was used produced on a large scale throughout the
world. There has been because of environmental problem. The oxygenated MTBE and ETBE
are produced by the reaction of methanol/ethanol and isobutylene.
METHYL TERTIARY BUTYL ETHER
(MTBE)

MTBE is one of the important oxygenates and originally its use started as a
substitute of tetraethyl lead. 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.

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/cm2g. Catalytic cracking butylenes and field butanes are additional possible source
of isobutylene.

TERIARY AMYL METHYL ETHERTAME

TAME is produced by etherification of isoamylenes recovered from C5 stream of FCC and

steam crackers. Two reactive components of iosmaylenes are 2-Methyl butene-1 and 2-
Methyl butene-2, Catalytic distillation process is used for the manufacture of TAME.