DIFFERENT MANUFACTURING PROCESSES

There are different manufacturing processes available for Ethylbenzene .Some these arelisted below:1)
1. Liquid phase aluminum chloride catalyst process2)
2. Vapour-phase zeolite catalyst process3)
3. Liquid phase zeolite catalyst process4)
4. Mixed Liquid-Vapour Phase zeolite Catalyst process
LIQUID PHASE ALUMINUM CHLORIDE CATALYST
PROCESS:
Introduction:
Liquid phase aluminum chloride processes have been the dominant source of Ethylbenzene since the
1930s to about 1980. Several companies have developed variations of this technology. Processes currently
in use include those of Dow chemical, BASF, Shellchemical, Monsanto and union carbide/ badger. The
Monsanto/Lummus technology is currently the most modern commercially licensed aluminium chloride
alkylation technology.
Description:
Alkylation of benzene with in the presence of an aluminum chloride catalyst complexis
exothermic (H=-114 kJ/mol). In the conventional AlCl3 process three phases are present in the reactor.
Aromatic liquid, ethylene gas, and a liquid catalyst complex phase (a reddishbrown material called red
oil). A mixture of catalyst complex, dry benzene, and recycled polyalkylbenzenes is continuously fed to
the reactor and agitated to disperse the catalyst complex phase in the aromatic phase. Ethylene and the
catalyst promoter are injected into the reaction mixture through spargers, and essentially 100% of the
ethylene is converted. Low ethylene: Benzene ratios are used to give optimum overall yield of
Ethylbenzene. Commercial plants typically operate at ethylene: because molar ratios of ca.0.3-0.35. As
theratio is increased, more side reactions, such as transalkylation and isomeric rearrangement,occur.
Further alkylation of Ethylbenzene leads to the reversible formation of lower molecular mass
polyalkylbenzenes. The loss in net yield due to residue is minimized by recycling this material to the
alkylation reactor. In addition, because the reaction occurscloseto thermodynamic equilibrium, the
traditional processes use a single reactor to alkylatebenzene and transalkylatepolyalkylbenzenes. The
liquid reactor effluent is cooled and discharged into a settler, where the heavy catalyst phase is decanted
from the organic liquid phase and recycled. The organic phase is washed with water and caustic to
remove dissolved AlCl3 and promoter. The aqueous phase from these treatment steps in first neutralized
and then recovered as a saturated aluminum chloride solution and wet aluminum hydroxide sludge. The
unreacted benzene is recovered by the first columns as an overhead distillate. The second column
separates the ethylbenzene product from the heavier polyalkylated components. The bottoms product of
the second column is fed to a final column, where the recyclable polyalkylbenzenes are stripped from non
recyclable high molecular mass residue compounds. The residue or flux oil, consisting primarily of
polycyclic aromatics, is burned as fuel.
VAPOUR -PHASE ZEOLITE CATALYST PROCESS:
Introduction:
Vapour-phase alkylation has been practiced since the early 1940s, but at that time processes were unable
to compete with liquid-phase aluminum chloride based technology.Thealkar process developed by UOP,
based on boron trifluoride catalyst, had modest success in the 1960s, but fell from favour because of high
maintenance costs resulting from the severecorrosion caused by small quantities of water. Nevertheless,
some Ethylbenzene units continue to use this process. The Mobil badger Ethylbenzene process

represents the lates tand most successful vapour phase technology to be introduced. The process was
developed in the 1970s around.
Description:
The reactor typically operates at 400-4500C and 2-3 MPa (20-30 bars). At this temperature>99% of the
net process heat input and exothermic heat of reaction can be recovered as steam. The reaction section
includes two parallel multi bed reactors, a fired heater, and heat recovery equipment. The high-activity
catalyst allows transalkylation and alkylation to occur simultaneously in a single reactor. Because the
catalyst slowly deactivates as a result of coke formation and requires periodicre generation, two reactors
are included to allow uninterrupted production: one is on stream while the other is regenerated.
Regeneration takes 36 hrs and is necessary after 6-8weeks of operation. The catalyst is less sensitive to
water, sulphur, and other poisons than the Lewis acid catalysts. The reactor effluent passes to the
purification section as a hot vapour. This steam is used as the heat source for the first distillation column,
which recovers the bulk of the unreacted benzene for recycle to the reactor. The remaining benzene is
recovered from a second distillation column. The Ethylbenzene product is taken as the overhead product
from the third column. The bottoms product from this column is sent to the last column, where the
recyclable alkylbenzenes and polyalkylbenzenes are separated from heavy no recyclable residue.
LIQUID PHASE ZEOLITE CATALYST PROCESS:
Introduction:
The EBMax process offered by Mobil/badger is a liquid phase alkylation reaction using a catalyst based
on the MCM-22. A commercial plant based on the EBMaxtechnologywas commissioned in 1955 at Chiba
Styrene Monomer Company.
Description:
A typical EBMax based plant flow diagram is shown below. The alkylation reactor is maintained in liquid
phase and uses multiple bed catalyst beds ethylene injection. The ethylene conversion is essentially 100%
in the alkylator reactors and the reactor nearly operates adiabatically. The exothermic heat of reaction is
recovered and used to producesteams or as heat duty in the distillation columns. The transalkylator reactor
in an EB Max plant can be either vapour phase or liquid phase. More recently, the transalkylation reactor
has been designed as liquid phase because of its improved energy efficiency .The transalkylation reaction
is conducted in the liquid phase using Mobil TRANS-4 catalyst. The alkylation and transalkylation
reactor effluent stream are sent to the distillation section which consist of primarily of three distillation
columns .The first column is a benzene column and it separates unconverted benzene into the overhead
stream for recycle to the reactors. The benzene column bottom stream feeds the EB column. The EB
column recoversthe EB product in the overhead stream and the bottom stream of the EB column feeds the
PEB column where PEB is fractionated overhead and recycle to the transalylation reactor.The bottom
stream of the PEB column is removed as the residue stream and is generally used as fuel in an integrated
styrene.
MIXED LIQUID-VAPOUR PHASE ZEOLITE CATALYSTPROCESS:
Introduction:
The CDTECH process is based on mixed liquid-vapour phase alkylation reactor section. The design of
commercial plant is similar to the liquid phase technologies except for the design of the alkylation reactor
which combines catalytic reaction with distillation into a single operation.
Description:
The CDTECH alkylation reactor consist of two main sections a catalytic distillation section and a
Standard distillation section as shown in figure. Benzene is feed to the top of alkylation Reactor and
Ethylene is fed as a vapour below the Catalytic Distillation Section creating a counter current flow of the
Alkylation reactants through the catalytic distillation section throughout the catalytic distillation section a
vapour liquid equilibrium is established is largely concentrated in the vapour phase. The Ethylene that
dissolves into the liquid phase rapidly alkylates benzene on the catalyst active sites to produces EB. The
rapid reaction of Ethylene in the liquid phase creates a driving force for additional Ethylene to dissolve
into the liquid phase where the alkylation reaction occurs on the catalyst active site. The exothermic heat
of reaction creates the vaporisation necessary to effect distillation the alkylation reaction product, mainly

EB, Diethylbenzene and similar amounts of other byproducts are continuously fractioned and removed
from the catalytic distillation section in the lower section of alkylation reactor standard distillation occurs
and the bottom stream contains primarily EB,PEB and other high boiling by-products.
PROCESS SELECTION
Ethylbenzene is manufactured commercially by four processes as described
ADVANTAGES:
Liquid Phase Aluminum Chloride Catalyst Process:
The aluminium chloride present in alkylation reactor effluent catalyst transalkylation reaction.

Reaction is very fast in presence of Aluminum chloride &produces almost stoichiometric yields
of Ethylbenzene.

Essentially 100% of ethylene is converted

Use of zeolite catalyst that eliminated issues associated with corrosion and waste disposal of
aluminiumchloride

The original vapour phase design accomplished the alkylation and transalkylation reactions in
single reactor.

The third generation technology is capable of achieving EB yield greater than99%.

The third generation technology offered significant benefits in purity ,capital cost
Liquid Phase Zeolite Catalyst Process:

The liquid phase zeolite catalyst process operates at substantially lower temperature decreased
side reactions dramatically resulting in ultra high purity EB product

The plant achieves high on stream efficiency often greater than 99% which results in low
turnaround & maintenance cost.

EBZ-500 catalyst has operating length of more than 8year without catalyst regeneration.

The regeneration is mild carbon burn procedure that is relatively inexpensive.

Mixed Liquid Vapour Phase Zeolite Catalyst Process:

The exothermic heat of reaction creates vapourisation necessary to effect distillation

Capable of using dilute ethylene feed e.g. Off gas from a fluid catalyticcracking plant or dilute
ethylene from steam cracker.

In general ethylene feed streams containing significant amounts of hydrogen,methane or ethane

DISADVANTAGES:

Liquid Phase Aluminum Chloride Catalyst Process:

Handling and disposal of aluminium chloride catalyst and waste has become increasingly more
costly and complicated because of environmental considerations.

Equipment and piping corrosion and fouling along with related environmental issues led to
development of EB process based on solid acid heterogeneous catalysts.

Major equipment pieces needed to replaced on regular schedule because of corrosion which
results in extensive turnarounds poor plant on-stream efficiency and thus are primary contributors
to the high operating costs associated with aluminium chloride

Vapour Phase Zeolite Catalyst Process:

The significant extent of isomerisation reactions and catalyst deactivation by deposition of

The length of time between regeneration can vary from as little as 2months to slightly more than
1 year depending on specific plant design and operating conditions.

Because the reactors must be taken off line for regeneration ,on-stream efficiency can be low
resulting in high operating costs for vapour phase plant

Additional equipment may be required for regeneration procedure depending on specific plant
design which adds capital cost to plant Liquid phase zeolite catalyst process (EB-MAX) &
Liquid-Vapour phase zeolite catalyst process (CDTech EB) both dont have disadvantages.

On the basis of above comparison, we selected mobil abadger process for the roduction of ethyl
benzene,which is a key raw material in the production of styrene. Ti is produced by ethylaton reacton of
ethylene and benzene is in catalytic environment. The tyicall purity of benzene feed is 99.9% and typicall
purity of ethylene feed is would be above 99.9 mol%.
INTRODUCTION:
Alkylation process can be done in homogenous and heterogeneous medium, in liquid or vapor phases.
Today, liquidhomogeneous alkylation covers more than 24% of the ethylbenzene (EB) production. About
40% of worldwide EB production is carried out in the vapor-heterogeneous medium. The rest of EB is
produced in the heterogeneous liquid-phase [1]. Several alkylation processes had been proposed to
enhance the benzene alkylation processes [2]. For example, Mobil-Badger process uses the ZSM-5 zeolite
catalyst in order to increase the EB diffusion while it prevents the polyethylbenzene (PEB) to diffuse
through the catalyst. In this process, the benzene to ethylene molar ratio is about 816 which increases the
needed energy in the fraction unit for the separation of EB from benzene and transethylbenzene [3,4]. In
1995 Mobil Co. introduced the Mobil-Raytheon EBMax process for the liquid-heterogeneous alkylation.
They used MCM-22 catalyst which increases the operational time to about 3 years. In this process the
benzene to ethylene molar ratio is about 35 which increases the process yield by reducing the benzene
recycled stream. Also, as the process works in the lower temperature, there is a significant decrease in the
xylene production [5,6]. In 1994 the CDTech process was introduced in order to increase the selectivity
and operational time. In this process, the countercurrent streams help to minimize the production of PEB
and other undesired products. So, it does not need a distinct reactor for EB and PEB separation [7].
Lummus/UOP Co. proposed a new approach for EB production from the liquid phase to recuperate the

selectivity and increase the operational time. They used two alkylation and one transalkylation reactors
with Y type zeolite for their process [8]. IPCL Co. introduced Albene approach by using biomass as the
alkylation agent, and Dow Chemical Co. proposed a two-step alkylation process which uses stack gas as
the alkylation agent [9]. Liu et al. proposed a novel industrial process for the highly selective production
of EB and claimed that the polyalkylation reactor could be omitted in the new process [10]. Many other
attempts had been made to enhance the alkylation process and increase the EB production [1113]. The
effects of operational parameters and process variables were investigated by many researchers. For
instance, effects of temperature and feed composition on the catalytic activity and product distributions
were studied by Li et al. [14]. Cavani et al. investigated the effects of temperature, contact time, and feed
composition oncatalytic performance of transalkylation of diethylbenzenes with benzene [15].
Sharanappa et al. studied the selective alkylation and disproportionation of EB in the presence of other
aromatics [16]. Al-Kinany et al. have shown that triflic acid could be used for the transalkylation of odiethylbenzene with benzene to EB at low temperatures and atmospheric pressure [17]. In this paper, the
simulated EB production process is described. The simulation results are compared against five-day
operational data. The effect of feed temperature and benzene recycle ratio on the production of EB is
investigated. We also maximized the selectivity of EB by simultaneous optimization of reactors
temperature and ethylene flow rate. Comparison of energy consumption at calculated optimum condition
and real unit data shows the advantage of running unit at optimum condition in term of energy
consumption.

Flow sheet:

PROCESS DESCRIPTION
The simulated EB production unit is an industrial working unit. The unit provides the needed
ethylbenzene for the juxtapose styrene monomer unit. In this commercial process, the alkylation reactors
are designed for 100% conversion of ethylene. EB synthesis could be done based on the following
alkylation reaction: C6H6 + C2H4 C6H5 C2H5 H 298 = 114 kJ/mol (1) A complete benzene
alkylation could be occurring under the atmospheric pressure and at a temperature of 500 C [18].
However, side reactions, especially successive alkylation, causes for PEB production. By these
restrictions the industrial alkylation processes should be done in a catalytic bed and at low temperatures.
Fig. 1 shows a simple diagram of the EB production process in a real working unit. As it can be seen from
Fig. 1, the process encompasses three packed bed adiabatic reactors in series. The first two reactors (R-1
and R-2) both have two Y type zeolite packed beds as catalyst used for the alkylation of benzene. The
third reactor (R-3) with three packed beds is used for the transalkylation processes. Fraction unit has four
towers. The first one is the benzene column (T-1), which is used for the separation of benzene from the
EB. There is a benzene drag tower (T-2), for treatment of benzene from undesired lighter products. EB is
taken out from the thirdtower (T-3), where EB is separated from PEB and other undesired heavier
products. In the last tower (T-4), PEB is separated from the flux oil products and is recycled to the
transalkylation reactor for EB production. The flux oil contains heavy materials and variety of the side
alkylation reaction components. The heavier materials are the main poisons of the catalyst and they
should not be accumulated within the process. The main duties for the T-4 is to completely separate the
heavy products from DEB and TEB. Thereafter, the transalkylation reactor could produce EB from the
transethylbenzene. The input ethylene is ramified into four streams and each is fed to each bed of R-1 and
R-2. The R-1 outlet stream is cooled down to the R-2 feed temperature in a heat exchanger (E-1). The
input benzene is a mixture of fresh benzene and the recycled stream from the T-1 in the fraction unit. The
ratio of the recycled benzene to the benzene required for stoichiometric alkylation is 6:1. The excess
benzene helped to regulate the temperature and reduce the transalkylation reactions. Rate expressions are
vital for simulation, analysis, and design of chemical reactors. Therefore they should be selected carefully

for an accurate simulation. Reactions (1) through (3) and Eqs. (4) and (5) are the main reactions and
reaction rates in the alkylation of benzene with ethylene [19].

where r1 and r2 are the rates of reaction (1) and (2) respectively.
kr is the rate constant and kEB is the adsorption coefficient for EB.

PRETREATMENT
The pretreatment step, which includes some proprietary Shell technology, is comprised of sweetening,
followed by removal of heavy materials. The sweetening entails diisopropanolamine addition to remove
sulfur compounds from the raw cracker offgas feeding the EB unit.
The gas composition after sweetening is shown in Table 3(12376 bytes).
Removal of heavy olefins (primarily propylene), which would otherwise alkylate benzene to form
una,anted by-products, is then accomplished in a refrigerated de-ethanizer unit. Propylene is removed to a
concentration of less than 50 ppm(vol) in the overhead offgas.
It is not necessary to remove ethane and lighter compounds, which are inert in the alkylation reactor.
Molecular sieve dryers are placed upstream of the de-ethanizer. These dryers are required to dehydrate the
feed gas to prevent formation of hydrate in the refrigerated sections.
All modern FCC units contain absorber/strippers followed by fractionation. These units recover most of
the propylene from the offgas--typically 90%. Installation of the pretreatment plant increases that

recovery to virtually 100% because the de-ethanizer bottoms can be recycled to the propylene recovery
unit.
EB UNIT
Pretreated dilute ethylene is mixed with excess benzene vapor in the reactor. The reactor effluent is
distilled overhead in the benzene recovery system, then recycled to the reactor.
The uncondensed offgas leaves the overhead of this system and is sent to an absorber for recovery of
benzene, and the offgas is returned to the refinery. Process residue from the back end of the process is an
acceptable absorbing medium.
This absorber is the only portion of the EB unit operation not required when processing polymer-grade
ethylene. Consequently, the cost of the EB unit is not substantially greater when using refinery offgas as
an ethylene source.
After benzene removal, EB product is recovered by fractionation in the EB recovery column. The heavy
materials from the column bottom consist primarily of diethylbenzene (DEB) and lesser amounts of
triethylbenzene, which are known collectively as polyethylbenzene or PEB. The bottoms are distilled to
recover PEB overhead.
This stream is recycled to the reactor, where DEB is transalkylated with benzene to recover additional
EB.
The net residue can be used as a fuel.
MOBIL-BADGER PROCESS:
Mobil badger process consists of two main steps
1. Alkylation
2. Separation
The fixed bed ZSM-5 catalyst promotes the same overall alkylation chemistry as those used in the other
processes; however, the reaction mechanism is different. Ethylene molecules are adsorbed onto the
Bronsted acid sites within the catalyst, which activates the ethylene molecule and allows bonding with
benzene molecules to occur. Hence, the range of higher alkylated aromatic byproducts formed by the
Mobil Badger process is somewhat different than that for the Friedel Crafts processes. These
components do not affect the ethylbenzene product purity and are recycled to the reactor for
transalkylation or dealkylation. The Mobil-Badger heterogeneous catalyst system offers several
advantages when compared to the other commercially available processes. The most important are that it
is noncorrosive and nonpolluting. The catalyst is essentially silica alumina, which is environmentally
inert. Because no aqueous waste streams are produced by the process, the equipment for waste treatment
and for catalyst recovery is eliminated. In addition, carbon steel is the primary material of construction,
high-alloy materials and brick linings are not required. The reactor typically operates at 400-4500 C and
2-3 Mpa (20-30 bar). At this temperature >99% of the net process heat input and exothermic heat of
reaction can be recovered as steam. The reaction section includes two parallel multibed reactors, a fired
heater, and heat recovery equipment. The high-activity catalyst allows transalkylation and alkylation to
occur simultaneously in a single reactor. Because the catalyst slowly deactivates as a result of coke
formation and requires periodic regeneration, two reactors are included to allow uninterrupted production:
one is on stream while the other is regenerated. Regeneration takes ca. 36h and is necessary after 6-8
weeks of operation. The catalyst is less sensitive to water, sulfur, and other poisons than the Lewis acid
catalysts. The reactor effluent passes to the purification section as a hot vapor. This steam is used as the
heat source for the first distillation column, which recovers the bulk of the unreacted benzene for recycle
to the reactor. The remaining benzene is recovered from a second distillation column. The ethybenzene
product is taken as the overhead product from the third column. The bottoms product from this column is

sent to the last column, where the recyclable alkylbenzenes and polyalkylbenzenes are separated from
heavy nonrecyclable residue. The low-viscosity residue stream, consisting mainly of diphenylmethane
and diphenylethane, is burned as fuel. The Mobil-Badger process also can use dispute ethylene
feedstocks. In semi commercial applications, the process has operated on streams containing as little as 15
mol% ethylene.
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