1.

1
Abstract
Styrene was developed in the 1930s, as the popularity synthetic rubber saw a major increase in demand.
Nowadays styrene is mainly used to manufacture homopolymers and copolymers such as; polystyrene
(PS), expandable polystyrene (EPS), acrylonitrile-butadiene-styrene (ABS) resins, styrene-acrylonitrile
(SAN), acrylonitrile-styrene-acrylate (ASA), styrene-butadiene (SB) latexes, styrene-butadiene rubber
(SBR) and unsaturated polyester resins. (icis 2011)
50% of global styrene consumption is used in PS manufacture. Most of this production being for
Packaging applications and the other 50% of the market includes; electrical and electronic parts,
construction, domestic appliances, household goods/furnishings, toys and sporting goods. (icis 2011)
The objective of this project was to design a process plant for styrene production from ethylbenzene with
a 45000 tonne feed source of ethylbenzene. The plant was to be built in Brisbane Australia and so the
sources of employees and materials, location and local government legislation were taken into account.
The reaction and process chemistry was concluded and a flow diagram of the chosen process route was
created. A material and energy balance was also completed to show the overall flow in the process.

Introduction
Styrene is a liquid hydrocarbon which is an aromatic un- saturated monomer (C6H5CH=CH2) because of
the vinyl group it contains, styrene easily forms many copolymers and polymers which are clear,
multifunctional and inexpensive plastics. (icis 2011). The most common way to produce styrene is by
using ethylbenzene however there are two common ways to do this, by adiabatic dehydrogenation and
isothermal dehydrogenation. In this design selection process the two will be compared and the most
viable method will be chosen. The method will require a suitable catalyst, raw materials selection, a
suitable plant design with its specifications, the environmental implications of the plant and the risks of
health and safety in production.

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3.1/3.2
Environmental Implications

The size of the plant could be up to 400km2 including a safe parameter set up for civilisation that could be
within distance to the plant. This land development could affect the wildlife contain and surrounding the
area so an Environmental Impact Assessment (EIA) needs to be completed, this will be conducted by the
Environmental Protection Authority (EPA) Australia to determine the affect this plant will cause. (Anon
1986.)
Flue gas emissions from the steam super heater

The emissions to the air are NOx CO dust and VOCs however if the plant reuses process streams to use
alongside the fuel this can cause the amount of SO2 and NOx to increase as non-conventional fuel has a
different composition. (Falcke, H. et al 2017) The typical emissions from a standard steam superheater
and the recycled fuel steam super heater can be seen as follows (Falcke, H. et al 2017);

Standard Steam Super Heater

 Hydrocarbon content (vol%) 2.8

 NOx (mg/Nm3), dry 3% O2 <140
 CO (mg/ Nm3), dry 3% O2 <5
 Dust (mg/ Nm3), dry 3% O2 <5
 VOCs (mg/ Nm3), dry 3% O2 <5

Recycled Fuel Steam Super Heater

 CH4 1.3-2.3 g/tonne of SM

 SO2 0.8-4 g/tonne of SM
 NOx 39-83 g/tonne of SM
 CO 4-8 g/tonne of SM
 Dust 0.6-1.9 g/tonne of SM
 VOCs 0.5-2 g/tonne of SM

Many of the materials used or produced are hazardous according to; the National Occupational Health
and Safety Commission (NOHSC); the National Industrial Chemicals Notification and Assessment
Scheme (NICNAS) and the HSIS Safe Work Australia. These materials include benzene, toluene,
ethylbenzene and the styrene product. (Anon 2008.)

Eco-toxicity of these materials

Material Endpoint /species Toxicity (exposure time)

Benzene LC50 /fish 1 eco mg/l (96 h)
EC50/ daphnia 10 mg/l (48h)
EC50 /algae 100 mg/l (72 h)
Toluene LC50 /fish 56-64 mg/l (96 h)
EC50/ daphnia 318 mg/l (24 h)
EC50 /algae ~
Ethylbenzene LC50 /fish 7 mg/l (24 h)
EC50/ daphnia 2.4 mg/l (48h)
EC50 /algae 4.6 mg/l (72h)
Styrene LC50 /fish 4. 02mg/l (96h)
EC50/ daphnia 4. 7mg/l (48h)
ErC50 /algae 4. 9mg/l (72h)
Figure - shows the ecotoxicity of benzene toluene ethylbenzene and styrene to aquatic life (NIS 2016,
Labtech 2013, Carlroth 2019,Nuplex 2015.)
Benzene as a Priority Existing Chemical
National Industrial Chemicals Notification and Assessment Scheme NICNAS
Benzene (CAS No. 71-43-2) was declared a Priority Existing Chemical on 7 April 1998, a response to
occupational and public health concerns. (NICNAS 2001)
Benzene is listed in the NOHSC List of Designated Hazardous Substances with the classifications:
‘Flammable’, ‘Carcinogen, Category 1’ and ‘Toxic: Danger of serious damage to health by prolonged
exposure through inhalation, in contact with skin and if swallowed’. The NICNAS report concluded that
benzene meets the NOHSC Approved Criteria for Classifying Hazardous Substances as a skin, eye and
respiratory system irritant. (NICNAS 2001)
Emission Precautions
Emission points of materials in the process
 The vents
 the benzene/toluene tray column
 the ethylbenzene recycle tray column
 the emergency vent in the styrene finishing column
 Storage leaks
 equipment leaks (from pumps, seals, process valves, sampling connections and safety relief
valves)
Equipment for Environmental protection
Condenser fouling can cause increased emissions to air and a loss of efficiency, so a cooling water supply
is effective in the prevention of this. Continuous leak detection and repair for VOC and Benzene leakage
is done with fugitive emissions sensors. These are put on the piping, sensors, valves and other possible
points of leakage. (Falcke, H. et al 2017);
A system to manage the catalyst to prevent heavy tar by products, this can also increase the catalysts
lifetime. This is done with the use of sensors for bed and effluent temperature and control sampling and
testing of the catalyst. (Falcke, H. et al 2017);
Accidental Release Measures
Do not allow run off to enter surface water or drains. Remove all sources of ignition. Provide adequate
ventilation. Apply Inert absorbent material to liquid spill e.g.: sand, earth, vermiculite or powdered
limestone. Collect material in suitable closed containers for disposal, these containers must be labelled.
Stop leak if safe to do so. Material Delivered to the approved waste disposal company. If sewers or
waterways are contaminated, advise the local emergency services and local water and waste management
authorities (NIS 2016, Labtech 2013, Carlroth 2019,Nuplex 2015.)
Waste
The follow wastes are produced per tonne of styrene at 99.9% purity;

 Spent catalyst waste – up to 0.45 kg

 Tar – up to 10.5-12.9kg
 Gums, oligomers of polystyrene – up to 1.5kg
 Spent solvents 1.5 -6 kg
The amount of tar waste can be decreased with the addition of an inhibitor (approx 0.58kg per tonne of
Styrene). The catalyst life is around 18 to 24 months and is prolonged with the addition of an alkali metal
as a stabilizer. (Falcke, H. et al 2017);
Waste treatment - Australian Government Regulation
The waste produced on site will be transferred to a local waste disposal service that is in accordance with
the waste disposal regulations set by the Australian Government Environment Protection Agency (EPA).
To adhere to EPA regulations following must be under taken to dispose of the hazardous and liquid waste
produced (NSW Environment & Heritage 2019);

 Licensing - licensing is required for the material being disposed or treated

 Chemical control orders (CCO)- The waste may have a chemical control order given by the
Environmentally Hazardous Chemicals Act 1985.
 Waste tracking - The waste must be tracked throughout its transport to its destination.
 Immobilization approvals - Recycling and reprocessing must be attempted as the first option but
where this isn't an option, an immobilization approval is needed from the EPA to enable landfill
disposal
 Liquid waste levy – certain liquid waste that are potentially dangerous this levy applies to illegal
disposal, exceeding the authorized amount of waste and stockpiling waste onsite for more than 12
months
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7
Process method – Adiabatic Dehydrogenation
The Yield depends on the catalytic conversion of ethylbenzene to styrene. To achieve a high yield a high
temperature is needed to encourage this catalytic conversion however this means that excessive thermal
cracking occurs, to combat this the reaction is thermodynamically limited to 50-60% conversion which
means a high amount of recycle. (Falcke, H. et al 2017);The separation of ethyl benzene and styrene is
problematic as they both have a boiling points of 136°C and 1458°C respectively(Falcke, H. et al 2017);
Materials specification
Raw materials

 Ethylbenzene
 Catalyst - Shell 105 (84.3% Fe2O3 , 2.4% Cr2O3 , 13.3% K2CO3)
 Alkali metal compound added to the reactant stream to stop decomposition of catalyst
Raw materials specification
This is the product specification on ethylbenzene focused on styrene production, with the levels of
cumene, n-propylbenzene, ethyltoluenes and xylenes in ethylbenzene controlled, to meet the styrene
purity specification.

 purity, 99.5 wt% min.;

 benzene, 0.1–0.3 wt%;
 toluene, 0.1–0.3 wt%;
 ortho-xylene and cumene, 0.02 wt% max.;
 meta-xylene and para-xylene, 0.2 wt% max.;
 Allylbenzene, n-propylbenzene and ethyltoluene, 0.2 wt% max.;
  diethylbenzene, 20 mg/kg max.;
 total chlorides (as chlorine), 1–3 mg/kg max.;
 and total organic sulfur, 4 mg/kg max.
Product specifications

 Purity 99.9% min.

 Ethylbenzene 80 ppm max.
 Benzene 1.0 ppm max.
 Toluene 1.0 ppm max.
 Polymer 10 ppm max.
 Colour, Pt-Co 10 max.
 Aldehydes (as Benzaldehyde) 0.01% max.
 Peroxides (as H2O2) 0.01% max.
 Chlorides (as Cl) 0.001% max.
 Sulfur (as S) 0.0005% max.
 Specific gravity 0.908 min.
 Density (60ºF) 7.586
 Melting Point -30.6 c
 Odor penetrating odor Refractive Index 1.546 (20 c)
 Molecular weight 104.15
 Colour colourless to yellowish oily liquid

Specification data
Styrene (apcbkk 2019, Chemicals Technology 2014)
Ethylbenzene (Coty, R. and Milne, L. 1996, Chemicals Technology 2014)
Key operating conditions
In the reactors the temperature across both reactors cannot drop below 500°C the Pressure of streams is
also limited to a 0.75-2.5 bar range. The catalyst is a big expense in the production process as a large
quantity is required (160-180m3 or 25,000kg for a 45000t/year capacity). The catalyst cannot exceed
1000k and the addition of an alkali metal is needed to prevent the decomposition of the catalyst. The
Styrene product temperature cannot reach 125°C to avoid polymerization and the purity of styrene
product needs to be at 99.9 wt.% ( Falcke, H. et al 2017);
Process control
Reaction vessels -purified ethylbenzene is preheated with steam to 160°C by heat exchangers to 520°C
and then by super-heated steam at 720°C, this supplies the require reaction temperature of (550-620°C).
1-1.8kg of steam is needed to sufficiently heat each kilogram of ethylbenzene. (Luyben, W. 2011.)
Temperature control - A bypass system is used where the total steam flow rate is maintained with variable
speed pumps, both the hot and cold streams can be increased and decreased with speed. Both streams can
also be bypassed around the heat exchanger, which almost immediately affects the mixed temperature in
the heat exchanger and reaction vessel, this gives tight control of the temperature needed. (Luyben, W.
2011.)
LLV separator – This contains a flow measurement system that uses turbine meters and electronic gas
measurement systems with sampling point to test the material. It is also equipped with pneumatic
regulators that will maintain constant pressure and liquid level, using control valves on all three outlets.
Liquids in the gas line and gas in the liquid could affect the flow rate measurements, to prevent this the
separator is fitted with a mist extractor, a removable and serviceable effluent diverter tube, a vortex
breaker and a weir plate. (MISWACO 2009)
Distillation – Steam ejector systems are used to maintain vacuum at the top of the tower. Column top
pressure is 100 to 400 mbar. The internal design is made to minimize liquid blocking, reduce the towers
overall pressure drop and reduce the bottom of the column’s temperature/liquid residence time. (Faessler,
P. et al 2005.) Improvements in inhibitor formulation means that the tower pressure can be increased, this
can increase heat recovery and capacity. Distillation columns use high-capacity structured packing with 5-
7 bed which require well working liquid collectors and distributors. (Faessler, P. et al 2005.)
Design optimization for production rate
Using more process steam, lowers the production of undesirable by products by driving the reaction to the
right, this means that less ethylbenzene product is needed to create a desired yield, however this increase
in steam reaches a peak where eventually more ethylbenzene feed is needed and this cost out ways the
benefits the increased amount of steam first provided, the optimum level of steam is around 2860kmol/hr.
(Luyben, W. 2011.)
A decrease in temperature is not desired even though it may save on fuel cost. This is because the cost of
the extra ethylbenzene required to keep the same yield at a decreased temperature, is a much higher cost
than the expenses saved on fuel. (Luyben, W. 2011.)
Reactor size can be optimized with reactor length, where the optimum reactor length is 8m. An increase
in reactor length is not desired because of the increase in byproducts, which reduces the amount of
recycled ethylbenzene. This causes an increase in ethylbenzene consumption. With two reactors the yield
increases in proportion to the cost, with three reactors the cost of the energy required doesn’t justify the
extra yield. Therefore, the number of reactors should be kept at two. (Luyben, W. 2011.)
Product quality - Process Gas Chromatographs
To ensure product quality, the styrene plant needs to be equipped with measuring and control
instrumentation. The most common way to test styrene quality is using process gas chromatography, this
instrumentation can also test for; the measurement of the ethyl benzene purity at the feed point to test for
m-Xylene o-Xylene benzene and toluene levels; the recycled ethylbenzene and the levels of benzene
toluene and styrene; the styrene product stream and the levels of Ethylbenzene m-Xylene p-Xylene
Benzene and toluene. (Harald, M. 2016).

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