Ethylbenzene CH2CH3

Capadtiës range f r o m 21

Processes

1. From benzene and ethyi

In the Monsanto-Lumir
drying column to rem(
alkylation reactor contai

FIGURE 55 ETHYLBEN:
Synonyms

ETHYLBENZENE phenylethane, ethylbenzol Benzene Alkylation C

drying reactor p
About 97% of ethylbenzene is produced by the alkylation of benzene with column ti
ethylene. There are two commercial routes i n use today: Re

• liquid-phase alkylation; ( 1
«Water
• vapour-phase alkylation. Nitrogen^

Liquid-phase processes based on an alumirvium chloride catalyst have been

developed by many compaiües and achieved great importance. One of the major Benzene
problems has been the disposal of waste aluminium chloride solution. I n an
attempt to reduce the quantity of catalyst required, ethyl chloride or hydrogen
chloride have been used as promoters.

Monsanto's discovery - that at higher reaction temperatures, alkylation proceeds

i n a single homogenous phase - led to a significant reduction i n the quantity of
Ettiylene
aluminium chloride required.
Ettiyl chloride Trans
Vapovir-phase processes were unable to. compete w i t h those based on aluminium in Benzene
chloride until the introduction of the Alcar process by UOP. Although some
plants stiU use this route, corrosion problems caused by traces of water on the The liquid catalyst con
boron trifluoride catalysts used have led to its demise. Mobil's vapour-phase hydrogen chloride. This
process, developed i n the 1970s, utilizes a synthetic zeolite catalyst to overcome which breaks down to h'
the corrosion difficulties. A n added advantage is the lack of waste disposal sulphur, toluene, xylene
problems due to the envirorunental inertness of the catalyst. Both vapour-phase they lead to unwanted b
processes can use feedstocks contaiiüng as little as 10% of ethylene.
A moisture-free ethylene
Ethylbenzene is also contained i n C8 aromatic streams arising f r o m catalytic unsaturated hydrocarbor
reforming, and absorption and distillation processes have been developed for rate. The reaction tempei
its recovery. Superfractionation involving multi-column, multi-stage technology maintain the reactants i
has been proposed, and several plants were built i n the 1960s. T o d a / s high maximize the productior
energy costs have made this route uncompetitive, so that now less than 3% of alkyl benzenes.
world ethylbenzene production is made by this route.
The alkylated liquid lea\
I n the non communist countries and the former Eastern bloc the liquid phase remove aluminium chlor
process accounts for nearly half of total ethylbenzene capacity. The Monsanto- is not recovered but ca
Lummus liquid phase and Mobil-Badger vapour technologies are the dominant ethylbenzene phase is w;
processes now i n use. being purified by fractior
 Ethylbenzene 161
CH2CH3
Capacities range f r o m 20,000-770,000 tonnes per year.

Processes

1. From benzene and ethylene by liquid-phase alkylation

I n the Monsanto-Lummus process, 99% pure benzene is passed through a

drying column to remove aU traces of moisture before being fed into an
alkylation reactor containing a catalyst. (See Figure 55)

FIGURE 5 5 E T H Y L B E N Z E N E F R O M B E N Z E N E A N D E T H Y L E N E B Y ALKYLATION
(UQUID-PHASE)

Benzene Alkylation Catalyst Vent gas Neutralization Benzene Ethylbenzene

drying reactor preparation scrubbing recovery ^^nywenzene
distillation
ation of beiizene w i t h column tank column
Recycle Benzene
Recycle Polyethylbenzene
Aluminium Chloride
Vent

ide catalyst have been

tance. One of the major Benzene
hloride solution. I n an
/l chloride or hydrogen

ires, alkylation proceeds

iction i n the quantity of Residue

ose based on aluminium in Benzene

r UOP. Although some
y traces of water on the The liquid catalyst complex consists of aluminium chloride promoted by
Mobil's vapour-phase hydrogen chloride. This is supplied by ethyl chloride i n benzene as a diluent
ilite catalyst to overcome which breaks d o w n to hydrogen chloride during the reaction. The presence of
! lack of waste disposal sulphur, toluene, xylenes and paraffins i n the benzene feed are undesirable as
dyst. Both vapour-phase they lead to unwanted by-products.
4 of ethylene.
A moisture-free ethylene stream of 15-100 mole% purity, containing no other
is arising f r o m catalytic unsatiirated hydrocarbons, is sparged into the reactor at a carefuUy conti-oUed
lave been developed for rate. The reaction temperature is held at 160-180°C and the pressure at 1 bar to
I, multi-stage technology maintain the reactants i n the Uquid phase. Benzene is present i n excess to
the 1960s. Today's high maximize the production of ethylbenzene and reduce the formation of higher
hat now less than 3% of alkyl benzenes.

The alkylated Hquid leaving the reactor is cooled and washed w i t h water to
;r]-: '.MIC ;h^' l i q - j i u phase remove nli.ininiLim chloride and hydrogen chloride. The catalyst waste sta-eam
cacvcUv. r;ii- M()n-.anlo- Is not rcco\oroJ but can be sold for use i n water treatment. The organic
o l o d f i , are the dominant eth>lben.iene phase is washed w i t h alkali to remove any remaining a d d before
being purified by fractionation.
162 Handbook of Petrochemicals and Processes

The separation requires tiiree columns. Urureacted benzene is recovered overhead FIGURE 5S ETHYLBENZ

f r o m the first column, which is operated at slightly elevated pressure, and re-
cycled. I n the second column, which usually operates under reduced pressiue, Reactors Prefra
pure ethylbenzene is split f r o m the heavy organic products. These are fed into
Fresh Benzene
the third column where diethylbenzene and polyethylbenzenes are separated.
Ethylene
Residual organic compotmds are burnt as fuel.

Because of the low catalyst concentrations employed, recycle polyethylbenzenes

caimot be returned to the alkylation reactor, as i n high concentrations they
would terminate the reaction. Instead they pass to a separate reactor operating
at a temperature below 130°C where transaUcylation occurs. Aluminium chloride
is removed f r o m the reaction mixture before it joins the ethylbenzene stream i n
the separation section.

The advantages of the Monsanto process over other aluminium chloride

processes are a decrease i n the amotmt of catalyst used (because the reaction
takes place i n a single homogeneous phase instead of separated into a two-phase
system) and higher yields. Waste by-product aluminium chloride is reduced and
the higher heat of reaction can be used to generate low-pressure steam.

Reaction
operation that takes appr
Q H é + CH2 = CH2 C6H5C2H5 so that one can be used 1

Raw material requirements and yield The major advantages of

impurities, is non-hazar
Raw materials required per tonne of ethylbenzene: produced. No catalyst rec
Benzene 740kg Catalyst Small or spedal linings for react
Ethylene 265kg cost savings.
Yield 99%
2. From benzene and ethylene by vapour phase alkylation Yield 98-100%
3. From refinery gases
In the Mobil-Badger process, dry benzene, ethylene and recycle polyethylbenzene
are preheated and fed into a fixed multi-bed reactor containing a crystalline The Alcar vapomr-phase
aluminosilicate zeolite catalyst. Usually two reactors are employed so that the gas streams containing 8-
catalyst i n one can be regenerated while the other is i n production. The reaction
Dehydrated benzene anc
conditions are 400-450°C and a pressure of 20-30 bar. (See Figure 56)
and fed into a reactor. T I
The composition of the feed is adjusted to give a mole ratio of benzene.ethylene compounds. The alkylati
of 7.5:1. Ethylene feedstocks of 15-100% purity can be used. Transalkylation 25-^5 bar and i n the pre
and alkylation occur simultaneously, and the heat generated by the exothermic
Transalkylation of recycl
reaction is used to generate steam.
at a temperature of 180-2
Benzene is flashed off f r o m the hot reactor vapours i n the prefractionator and and fed into a benzene
recycled. A n y residual benzene is recovered i n the first column, and ethyl- recycled. The catalyst i '
benzene is separated f r o m the heavy orgarüc products i n the second column. I n benzene column bottoms
the third column, the heavy organics are distilled to separate polyethylbenzenes f r o m the third column ar
for recycle.
The major disadvantage
The catalyst is regenerated every 6-8 weeks to remove any coke formed, an can be incurred due to se
 Ethylbenzene 163

e is recovered overhead FIGURE 56 ETHYLBENZENE FROM BENZENE A N D ETHYLENE BY ALKYLATION

rated pressure, and re- (VAPOUR-PHASE)

ader reduced pressure,
Reactors Prefractionator Vent gas Benzene Ethylbenzene^Diethylbenzene
icts. These are fed into scrubber recovery recovery recovery
enzenes are separated. Fresh Benzene column column column
Ethylbenzene

ycle polyethylbenzenes
j h concentrations they
)arate reactor operating
rs. Aluminium chloride
ethylbenzene stream i n

;r aluminium chloride Heater

d (because the reaction

larated into a two-phase
chloride is reduced and
-pressure steam.

operation that takes approxiinately 36 hours. Usually two reactors are available
so that one can be used while the other is being regenerated.

The major advantages of this process are that the catalyst is less sensitive to
impurities, is non-hazardous and non-corrosive and no waste streams are
produced. No catalyst recovery, waste treatment equipment, high-alloy materials
Small or spedal linings for reactor construction are required, thus effecting considerable
99% cost savings.
Yield 98-100%
3. From refinery gases
recycle polyethylbenzene
containing a crystalline The Alcar vapour-phase process is designed to utilize refinery and coke-oven
re employed so that the gas streams containing 8-10 mole% of ethylene.
production. The reaction
Dehydrated benzene and ethylene i n a mole ratio around 7.5:1 are preheated
(See Figure 56)
and fed into a reactor. The ethylene must be free f r o m oxygenates and sulphur
atio of berizene: ethylene compounds. The alkylation reaction is carried out at 100-150°C, a pressure of
)e used. Transalkylation 25-35 bar and i n the presence of a boron trifluoride catalyst on an inert base.
;rated by the exothermic
Transalkylation of recycled polyethylbenzene takes place i n a separate reactor
at a temperature of 180-230°C. Gases f r o m both reactors are combined, flashed
I the prefractionator and and fed into a benzene recovery column, where benzene is separated and
first column, and ethyl- recycled. The catalyst is removed and ethylbenzene is separated f r o m the
in the second column. I n benzene column bottoms i n the recovery column. Polyethylbenzene is recovered
larate polyethylbenzenes from the third column and recyded.

The major disadvantage of the Alcar process is the high maintenance cost which
ve any coke formed, an can be incurred due to severe corrosion caused by traces of water. Its advantage
164 Handbook of Petrochemicals and Processes

is that i t can accommodate ethylene streams containing 8-10% ethylene, eyes, skin and respirator
providing catalyst poisons are absent. protective clothing and i
4. From mixed xylene streams as ethylbenzene absorpti
leading to narcosis, k i d n
Ethylbenzene can be recovered from xylene concentrates coming f r o m catalytic
reforming which may contain up to 25% of ethylbenzene. I n order to separate It is normally stored i n ir
out the ethylbenzene, close fractionation k n o w n as superfractionation has to be be used. The use of r u
employed. This requires three 200-foot columns i n series containing a large attacks rubber and some
number of plates and high reflux ratios. This route is no longer competitive due benzene to heat, flames (
to the high cost of energy required. Spills should be containe
the product is toxic to f i
Properties vapours being heavier t
Colourless liquid w i t h an odour of xylene. Highly inflammable. Practically flashback. Carbon dioxid
insoluble i n water, but soluble i n ethyl alcohol, ether and benzene. fires. A water stream si
Firefighters must wear se
Molecular Wt 106.17 Flash Point Qosed Cup 15°C
Density at 20°C 0.867 Vapour Density (air=l) 3.7
Exposure Limit HSE 125 ppm
Ethylbenzene is highly ii
Melting Point -94.9°C
Boiling Point 136.2°C (EH/40) 10 minutes portation.
Autoignition 100 ppm
Temperature 460°C 8 hour
Exposiire Limit A C G I H 125 ppm Major plants
Explosive limits in air
lower 0.99 vol% TLV-STEL
upper 6.7 vol% 100 ppm Plants w i t h capacities gre
TLV-TWA
Daw Chemical Temeuzen
BASF Ludwigshafen
Grades American
Hoechst Bayport
Technical, styrene grade > 99.5% containing < 40mg/kg diethylbei\zene ARCO Channelview
Cosmar Carvüle
International classifications Dow Chemical Freeport

U N Number 1175 Classification Flammable liquid Licensors

CAS Reg No 100-41-4 Packing Group n
E C Classification 601-023-00-4 Hazchem Code 3YE Mobil
Cosden Technology
Applications
Halcon-SD
The most important outlet for ethylberizene, accounting for almost 99% of total Union Carbide-Badger
demand, is as an intermediate for the manufacture of styrene. Unocal Corp
Other minor uses are as a solvent in the paint industry, i n the production of
dyes, and as the raw material for the manufacture of diethylbenzene and
acetophenone.

Future growth will depend on the demand for stjTene; forecasts for ethylbenzene
growth i n the period 1990-95 are i n the region of 3-3.5%. Because of their
interdependence, the production of ethylbenzene and styrene has become fully
integrated i n many compaiües.

Health & handling

Ethylbenzene is less toxic than benzene, but i t has an irritating effect on the
 Ethylbenzene 165

ning 8-10% ethylene. eyes, skin and respiratory tract. Care should be exercized when handling, and
protective clothing and goggles worn. Adequate ventilation must be provided
as ethylbenzene absorption can result i n chronic poisoning through inhalation
leading to narcosis, kidney and liver disease.
s coming from catalytic
It is normally stored i n mild steel containers but iron, copper or aluminium can
le. I n order to separate
be used. The use of rubber seals should be avoided because ethylbenzene
rfractionation has to be
attacks rubber and some plastics. Care should be taken not to expose ethyl-
ries containing a large
benzene to heat, flames or strong oxidizing agents.
longer competitive due
Spills should be contained to avoid contamination of streams or waterways as
the product is toxic to fish. Ethylbenzene is a dangerous fire hazard and the
vapours being heavier than air, can travel some distance w i t h the risk of
nflammable. Practically flashback. Carbon dioxide, dry chemical or alcohol foam can be used to fight
nd benzene. fires. A water stream should be avoided because i t could disperse the fire.
Firefighters must wear self-contained breathing apparatus.
.losed Cup 15°C
sity (air=l) 3.7 Ethylbenzene is highly inflammable and spedal regulations control its trans-
mit HSE 125 ppm
10 minutes portation.
100 ppm
8 hour
Major plants
nit ACGIH 125 ppm
TLV-STEL
100 ppm Plants w i t h capacities greater than 500,000 tormes/year:
TLV-TWA
Doio Chemical Temeuzen Netherlands Sterling
BASF Ludwigshafen Germany Chemicals Texas City US
American Asahi
Hoechst Bayport US Ciiemical Mizushima Japan
;g diethylbenzene ARCO Channelview US Mitsubishi Kashima Japan
Cosmar Carville US Petrochemicals Yokkaichi Japan
Daw Chemical Freeport US Sadaf Al JubaU Saudi Arabia

Flammable liquid Licensors

up n
ide 3YE Mobil Monsanto
Cosdeh Technology BASF
Halcon-SD Badger
g for almost 99% of total Union Carbide-Badger UOP
styrene. Unocal Corp hummus Crest

ry, i n the production of

of diethylbenzene and

orecasts for ethylbenzene

-3.5%. Because of their
styrene has become fully

n irritating effect on the

WSUÊÊm