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Chapter 3 : Process Selection

1.0 Summary
The dehydrogenation of ethylbenzene achieved in 1930s where it became the
commercial processes for production of styrene. The need for synthetic styrene
butadiene rubber (StyreneButadiene Rubber (E-SBR)) during the World War II provided
the impetus for large-scale production. After several years, this capacity became available
for the manufacture of a high-purity monomer that could be polymerized to a stable,
clear, colorless, and cheap plastic (Polystyrene and Styrene Copolymers). As a basis for
this study, the dehydrogenation of ethyl benzene produces crude styrene, unreacted ethyl
benzene, benzene, and toluene. Hydrogen gas that is produced in the reactor is assumed
to be fully separated in the separator prior entering the first distillation column of this
study. In the first distillation column, the separation of benzene + toluene from other
components are presumed to be fully removed from the system. The bottom product of
that first column feeds the second distillation column, where the unreacted ethyl benzene
is recycled back into the reactor. The bottom product is then fed into the final distillation
column, where styrene monomer is separated from the heavy compounds. Second process
is the process for producing styrene by using alkylation process, benzene is alkylated
with ethylene to produce ethylbenzene and at least some of the ethylbenzene is
dehydrogenated to produce styrene, together with benzene and toluene as by-products. At
least part of the benzene by-product is passed through a bed of an adsorbent comprising
at least one of an acidic clay, alumina, an acidic ion exchange resin and an acidic
molecular sieve to remove basic nitrogenous impurities there from and produce a purified
benzene by-product, which is then recycled to the alkylation step.
2.0 Introduction
2.1 Dehydrogenation of ethylbenzene
Styrene (ST) is industrially produced by direct dehydrogenation of ethylbenzene
(EB) using steam at 580-630 C. The process suffers from high energy consumption due
to low conversion per pass because of equilibrium limitations and the high temperatures
required for the endothermic reaction. However, many research groups and companies
have investigated alternative styrene production processes. Oxidative dehydrogenation
process is one of the most important ones.
The big advantage of oxidative dehydrogenation is that the process can be operated
at lower temperatures. There is no need for the co-feeding of superheated steam, and it is
free of thermodynamic limitations regarding the conversion of ethylbenzene. Thus, high
conversion per pass can be achieved. However, various pitfalls in the oxidative
dehydrogenation of ethylbenzene to styrene still exist. These aspects are discussed as well
as alternative dehydrogenation processes, economic and environmental aspects of styrene
production and the thermodynamics of the styrene chemistry.
Most of the commercial styrene is produced by direct dehydrogenation of
ethylbenzene (85-90%). The remaining part (10-15%) is obtained as a by-product in the
production process of propylene oxide . Styrene plants run their reactors under isothermal
or adiabatic conditions with flow rates that ensure short contact times in order to prevent
polymerization of St [2]. The equilibrium EB conversion at 600C and 0.1 bar pressure is
~ 83% [6], and conversions between 50 and 60% are obtained in technical reactors.
In the dehydrogenation section, ethylbenzene is dehydrogenated over potassium
promoted iron catalyst in an adiabatic fixed bed reactor. More than one reactor is used
since the temperatures drop in a theoretical adiabatic reactor under 100% ethylbenzene
(theoretical) conversion is ~330C. A temperature drop is undesirable for a good
performance of the dehydrogenation reaction.
2.2 Toluene Alkylation with Methanol to form Styrene Monomer
In 1958, UOP developed a new process for alkylation of benzene with ethylene at
presence of aluminium chloride catalyst. This resulted in production of ethyl benzene
which is the feed for production of styrene monomer. Ethyl benzene is a colorless liquid
with a smell similar to that of gasoline and a quantity of less than 2 pmm in air. Ethyl
benzene exists in crude oil with a small quantity and in addition to styrene, it is used in
the production of acetone, diethyl benzene, cellelouse acetate, etc. The need to ethyl
benzene has a growth of 4.3% per year. Requisition for this material reached 25 million
tons in 2003.
Generally benzene alkylation process, for the production of ethyl benzene, consists
of the following three steps which are Alkylation step, in which benzene reacts with
ethylene, second is Trans alkylation step, in which poly ethyl benzenes (generally Diethyl
benzene and three ethyl benzene) at presence of benzene are converted to ethyl benzene
on a reverse alkylation process. Lastly, Separation step, in which unreacted benzene, poly
ethylbenzenes and other components are separated from each other and high purity ethyl
benzene is produced. The applied catalyst in this process (aluminium chloride) is highly
corrosive, and hence expensive equipment which are resistant against acid are required.
To develop this process, a simulating software can be of great importance. Using
such a software, it will be possible to investigate the system behaviour against process
variables which can be used in the design of new pilots and units. Of course this process
has been formerly simulated by some researchers but their simulation can not be applied
to all industrial units because of the type of kinetics and catalyst theyve used. So a
dedicated software had to be developed for the existing ethyl benzene unit in an Iranian
Petrochemical Complex which is unique in production of ethyl benzene in Iran. This
software has been developed for this unit and is now under operation.
3.0 Process Description
3.1 Dehydrogenation of ethylbenzene
The styrene monomer purification is conducted to obtain the pure styrene monomer
which will be used in the manufacture of resins and plastics. Styrene monomer is
produced by the dehydrogenation of ethyl benzene. The ethyl benzene is mixed with
superheated steam and passed over a bed of a suitable catalyst so as to dehydrogenate the
ethyl benzene to styrene monomer (King, 1975). Benzene, toluene and some heavy
compounds are the by-products that are produced through dehydrogenation of the ethyl
benzene.
To obtain pure styrene monomer, crude styrene effluent from the reaction section
which includes styrene, benzene, toluene, ethyl benzene and heavy compounds must be
fractionated or distilled to get the desired product. The entire purification section is
composed of three vacuum distillation columns in series, in which each of the column
will separate the entire components according to their relative volatility. The benzene and
toluene are separated from ethyl benzene and styrene in the first distillation column,
where the overhead, consisting of benzene and toluene, is sent to a benzene-toluene
splitter to recover benzene and toluene.
The bottom stream, on the other hand, is sent to the ethyl benzene recycle column,
which is designed and operated so as to effect separation of the feed into an overhead
fraction consisting almost wholly of unreacted ethyl benzene, and a bottoms fraction rich
in styrene and polystyrene residue (heavy compounds) (King, 1975). The unreacted ethyl
benzene overhead fraction is recovered and preferably is recycled back to the
dehydrogenation reactor (Tarafder, 2004). The separation of ethyl benzene from styrene
in the second column is difficult due to their extremely close boiling point, which is
136C (ethyl benzene) and 145C (styrene) and requires high efficiency, low-pressure
distillation column with a large number of distillation stages (70-100).
Then, as the final distillation, the styrene monomer is separated from the heavy
compounds as the top product. The heavy compounds usually consists mostly of styrene
polymers which boil at a higher temperature than styrene monomer, plus higher boiling
aromatic compounds and polymerization inhibitors which are added to the
dehydrogenation reaction effluent to limit styrene polymerization (King, 1975).
Figure 1 Process Flow Diagram of Styrene Monomer Purification

3.2 Toluene Alkylation with Methanol to form Styrene Monomer


In this process benzene feed from storage tank is mixed with recycled benzene from
separation unit, and after heating and mixing with ethylene, enters the first reactor (R-
101). Ethylene is completely converted in the reactor. Outlet from the first reactor warms
up the feed of the second reactor while cooling down and after mixing with ethylene
enters the second reactor (R-102). The outlet from the second reactor is then sent to
benzene tower in separation unit. The reaction between poly ethyl benzene with ethyl
benzene (trans-alkylation) will be carried out in trans-alkylation reactor (R- 103). The
feed to this reactor is a mixture of benzene stream taken from benzene tower and recycled
poly ethyl benzene stream. This feed is first heated by reactor outlet stream and furnace
before entering the reactor. The outlet stream of transalkylator reactor is then sent to
benzene tower in separation unit.
3.2.1 Reactors
The reactor unit is comprised of alkylation and transalkyaltion sections. The
alkylation reactors are in series and have got two catalytic beds. The transalkylator
reactor is larger than each alkylator and has got three catalytic beds. Stream direction in
reactors is from bottom to top. Figure 1 illustrates a simple schematic diagram of the
reactors.

Figure 2: Simple Schematic of Ethyl Benzene Reactors


The manufacture of EB involves the alkylation of benzene with ethylene to yield a
mixture of alkylated benzenes and excess benzene. This mixture is distilled to recover
EB, recycle benzene, and higher ethylated benzenes. The latter are transalkylated with
benzene to form additional EB. The recycle benzene is sent back to the alkylator and
transalkylator reactor vessels, and the EB product is sent to the dehydrogenation section
of the styrene unit.
The major reactions in the manufacture of SM are the dehydrogenation of EB to SM
and hydrogen. Process Description Dehydrogenation side reactions produce benzene and
toluene and some light compounds. The catalytic dehydrogenation reaction is
endothermic, with reaction heat supplied by a super heater. The reactor effluent is cooled
by generating steam. The off gas stream is compressed and used as fuel in the steam
super heater. The dehydrogenated mixture is distilled to recover SM product, recycle EB,
as well as benzene and toluene by-products
4.0 Advantages and Disadvantages of Dehydrogenation and Alkylation
4.1 Dehydrogenation of ethylbenzene
Advantages
1. Increases energy savings
2. Reduces investment
3. Reduces downtime
4. Lower production cost
5. Allows optimization of operations using a personal computer

Disadvantages
1. High energy demands
2. Low equilibrium conversion
3. High capital cost

4.2 Toluene Alkylation with Methanol to form Styrene Monomer


Advantages
1. Minimizes plant downtime
2. Insignificant amounts of xylenes are produced, providing highest product quality
3. Minimizes production cost
4. Reduces investment

Disadvantages
1. Too low molecular weight
2. Non processable solid
3. Hard to process or transport
5.0 Human Health, Toxicology Evaluation and Safety
5.1 Styrene
A particularly offensive contaminant associated with such undesirable properties in
polystyrene is unreacted vinyl aromatic monomer, usually styrene monomer. One of the
causes of unreacted monomer is directly related to the presence of phenyl acetylene in the
styrene feed stock going into the polymerization reactor system. Basically, styrene is a
suspected carcinogen and creates undesirable taste, odour, and health hazards, when
present in small amounts in polystyrene (Merrill, 2004)
Styrene is a very reactive monomer. If not properly inhibited, it will polymerize
rapidly via a free radical mechanism at elevated temperatures typically encountered in the
styrene purification process. The polymerisation reaction is self-initiating; no initiators
such as peroxides are required to initiate the reaction process. The amount of polymer
formed in a specific production unit is a function not only of the process temperature, but
also of the residence time and styrene monomer concentration in the distillation towers.
Higher process temperatures result in increased rates of polymerisation (Xu, 2012).

5.2 By-Products
One major by-product is carbon dioxide. The carbon produced in the reactor is
incorporated into the iron oxide catalyst, the catalyst becomes self-cleaning (through
enhancement of the reaction of carbon with steam to give carbon dioxide, which is
removed in the reactor vent gas). The other by-products consist of heavy hydrocarbons.
These are incinerated when possible and treated when they cannot be incinerated. As
explained in the previous topics, by recycling the heavy compounds into the reactor and
distillation columns, it has been found they could increase the production rate of the
reaction as well as the separation in the column. Water being generated from the
combustion of hydrogen is sent for treatment as well.
5.3 Chemical Hazards
Safety precaution should be taken when dealing with several compounds in the
process. Styrene monomer should not have contact with the skin. If it does, the skin
should be washed with water thoroughly. Styrene is extremely flammable and can travel
or move in a considerable distance to an ignition source and should be put out using a dry
chemical, alcohol foam or carbon dioxide. Pure styrene has a penetrating odour
(Anonymous, 2010).
The precursor to styrene, ethyl benzene, is also dangerous. It should never be inhaled
and CPR may be needed after doing so. It is labelled as a severe fire hazard and the same
method of fire fighting used for styrene should be applied to ethyl benzene. Benzene is an
eye irritant and causes nausea, unconsciousness, and a change in blood composition when
breathed in. It is also a fire hazard, and should be put out with the same method as styrene
and ethyl benzene. The flammability limits are from 1.3 vol% to 7.9 vol%. A self-
contained breathing apparatus should always be used when around benzene that could
enter the surrounding air (Anonymous, 2007).
5.4 Safety Hazards
Safety is a primary concern in all areas of the process. There are three major
variables that affect equipment safety. They are the operating pressures, temperatures, and
the chemicals present. Choosing the appropriate materials of construction reduces the
dangers associated with temperature and certain chemicals. This is taken into account as a
pressure factor used when costing equipment. The flammability of each stream is also
taken into consideration. All other streams operate well above the upper flammability
limits. Using pressure, temperature, level, and flow controllers the streams can be kept
within the designated safety ranges. 28
5.5 Health Hazard
a) Acute Health Effects
Irritation in the eyes, nose, throat and skin can occur immediately or shortly after
exposure to styrene monomer. Higher levels can cause dizziness, lightheaded, and
passing out. Very high levels could cause brain and liver damage and death.

b) Chronic Health Effects


The following chronic (long term) health effects can occur at some time after
exposure to Styrene monomer and can last for months or years.

i. Cancer Hazard
Styrene monomer causes mutations. Such chemicals may have a cancer risk, and in
fact, there is limited evidence that it causes cancer of the lung in animals.
Many scientists believe there is no safe level of exposure to a cancer causing agent. Such
substances may also have the potential for causing reproductive damage in humans.

ii. Reproductive Hazard


Styrene Monomer may damage the developing fetus. There is limited evidence that it
may decrease fertility in females (Zlobina, 1975).
5.6 Fire Hazards
a) Flammability
Styrene monomer is classified by both OSHA 29 CFR 1910.26 and National Fire
Protection Association (NFPA) Code 30 as a Class IC flammable liquid. The National
Electric Code (NFPA 70) refers to styrene as a Class I, Group D material. Styrene will
burn and requires the same precautions against fire and explosion hazards that commonly
apply to other combustible and flammable liquids (Anonymous, 2010).

b) Explosive Mixtures
Styrene vapour is heavier than air and could travel considerable distances to an
ignition source and flash back to the source. It is important to prevent the formation of
explosive or combustible mixtures, and to take precautions to avoid ignition of any such
mixtures. Monomer handling areas should be well ventilated and motors must be
explosion proof.
Storage tanks and other containers that have been emptied of monomer must be
flushed out with steam, nitrogen, or water to remove monomer vapor. The tank
atmosphere should be tested before the tank is entered or worked on with welding
equipment. The dangers of fire and explosion are real because styrene can form explosive
mixtures in air at room temperatures. Precautions should be taken to assure that no
ignition of vapours can occur, especially where elevated temperatures are involved.
5.7 Environmental Hazards
a) Ecological Information
Styrene monomer is used to make plastics, synthetic rubber, and resins, and in the
production of insulators. It may enter the environment from industrial discharges,
municipal waste treatment plant discharges, or spills.

b) Acute Ecological Effects


Acute toxic effects may include the death of animals, birds, or fish, and death or low
growth rate in plants. Acute effects are seen two to four days after animals or plants come
in contact with a toxic chemical substance.

c) Chronic Ecological Effects


Chronic toxic effects may include shortened lifespan, reproductive problems, lower
fertility, and changes in appearance or behaviour. Chronic effects can be seen long after
first exposure to a toxic chemical. Styrene monomer has high chronic toxicity to aquatic
life.

d) Water Solubility
Styrene monomer is moderately soluble in water. Concentrations of between 1 to
1,000 milligrams will mix with a litre of water.

e) Distribution and Persistence in the Environment


Styrene monomer is non-persistent in water, with a half-life of less than 2 days. The
half-life of a pollutant is the amount of time it takes for one-half of the chemical to be
degraded. About 99% 30 of Styrene Monomer will eventually end up in air; about 0.85%
will end up in water; the rest will end up in terrestrial soils and aquatic sediments (Kline,
2012)
f) Distribution and Persistence in the Environment
Some substances increase in concentration, or bio accumulate, in living organisms as
they breathe contaminated air, drink contaminated water, or eat contaminated food. These
chemicals can become concentrated in the tissues and internal organs of animals and
humans. The concentration of styrene monomer found in fish tissues is expected to be
somewhat higher than the average concentration of styrene in the water from which the
fish was taken.
6.0 Conclusion
Based on the two processes that have be compared, the dehydrogenation of
ethylbenzene have been selected for the process of production of styrene. There are many
ways to produce styrene, but even despite the disadvantages of the conventional steam-
aided dehydrogenation process and the SMPO process, these are the only commercially
operating processes. Dehydrogenation in CO2, or dehydrogenation with O2 are
interesting alternatives because of their increased styrene yields, lower operating
temperatures, avoiding steam as a diluent and avoiding a large amount of co-product
formation. For both new processes, large improvements need to be made by catalyst
development and optimization, to be able to compete with the conventional process and
its extremely high styrene selectivity (>96%). For dehydrogenation in CO2, catalyst
stability is the largest issue to solve. For the oxidative dehydrogenation process the
styrene selectivity has to be increased. The SNOW process is a nice alternative that can
be competitive in areas where ethene is difficult to obtain. The coke that is initially
formed during reaction is responsible for the increased activity and selectivity for the
dehydrogenation reaction. After a certain point in time the increase in the amount of coke,
however, reduces the activity due to a loss in available surface area. Oxygen groups on
the coke seem not essential for dehydrogenation, but rather defects and edges of the
carbon deposits play a role in the reaction mechanism. The overall activity and selectivity
of the catalyst depends on its amount of coke, parent material and accessible surface area.
So, the hydrogenation has its own advantages where the production of styrene can be
occur.