FINAL YEAR PROJECT PROPOSAL REPORT

A PLANT DESIGN REPORT ON PRODUCTION OF 100,000 MTPY OF

STYRENE

SUPERVISOR: -
DR. FAHAD REHMAN

BY:

ABUBAKAR SALEEM SP15-CHE-059

MUHAMMAD HUMZA SP15-CHE-053
IRFAN RIAZ SP15-CHE-061
UMAIR SHOAIB SP15-CHE-041
M.NOMAN SAEED SP15-CHE-017

DEPARTMENT OF CHEMICAL ENGINEERING

COMSATS INSTITUTE OF INFORMATION AND TECHNOLOGY, LAHORE
Contents
HISTORY……………………………………
INTRODUCTION
PHYSICAL PROPERTIES
APPLICATIONS
MANUFACTURING PROCESS
 Catalytic Dehydrogenation of ethyl benzene
 Side-chain chlorination of ethyl benzene followed by
dechlorination
 Side-chain chlorination of ethyl benzene hydrolysis to the
corresponding alcohols followed by dehydration
 Pyrolysis of petroleum recovery from various petroleum
processes
 Oxidation of ethyl benzene to ethyl benzene hydroperoxide
which reacts with propylene oxide after which the alcohol is
dehydrated to styrene

PROCESS SELECTION
PEOCSS FLOW DIAGRAM
PROCESS DISCRIPTION
MARKET ANALYSIS
HAZARDS ASSOCIATED
SCOPE
REFERENCE
ONE PAGE PROJECT DISCRIPTION
Styrene, also known as ethenylbenzene, vinylbenzene, and phenylethene, is an organic
compound with the chemical formula C6H5CH=CH2. Styrene is derivative of benzene and is a
colorless oily liquid that evaporates easily and has a sweet smell, although high concentrations
have a less pleasant odor. Styrene is the precursor to polystyrene and several copolymers.
Styrene is a chemical used to make latex, synthetic rubber, and polystyrene resins. These resins
are used to make plastic packaging, disposable cups and containers, insulation, and other
products. Styrene is also produced naturally in some plants. This project is to design a plant that
is capable of producing 100,000 tons per year of styrene.
There are many methods in producing Styrene which are: -
 Catalytic Dehydrogenation of ethyl benzene.
 Oxidation of ethyl benzene to ethyl benzene hydroperoxide which reacts with
propylene oxide after which the alcohol is dehydrated to styrene.
 Side-chain chlorination of ethyl benzene followed by dechlorination.
 Side-chain chlorination of ethyl benzene hydrolysis to the corresponding alcohols
followed by dehydration.
 Pyrolysis of petroleum recovery from various petroleum processes.
Selected method is Catalytic Dehydrogenation of ethyl benzene because process reaction is
equilibrium limited and with the addition of steam the process can be controlled moreover steam
(used to vaporize ethyl benzene) is recycled. So, this process is economical. Other processes
such as Side-chain chlorination of ethyl benzene followed by dechlorination & Side-chain
chlorination of ethyl benzene hydrolysis to the corresponding alcohols followed by dehydration
generally suffers from high cost of raw materials and from the chlorinated contaminants in the
monomer. Pyrolysis of petroleum recovery from various petroleum processes is not used due to
unavailability of raw material and carbon also poisons catalyst.
The reaction is carried out at 600 to 650 C with a contact time of about 1 second between the
feedstock and the catalyst (usually iron oxide or cadmium oxide).
The main aim of this project is to conduct conceptual design for100,000 MTPY styrene
production to reduce/eliminate the importing costs. It will involve:
Selection of an existing commercial process
Material and energy balances.
Design of major equipments.
Proposing process instrumentation diagram for the selected equipments.
Economic feasibility
Hazard and operability study (HAZOP)
HISTORY
In 1839, the German apothecary Eduard Simon isolated a volatile oil from the resin
(called storax or styrax) of the American sweetgum tree (Liquidambar styraciflua).
He called the oil "Styrol" (now: "styrene"). He also noticed that when Styrol was
exposed to air, light, or heat, it gradually transformed into a hard, rubber-like
substance, which he called "Styroloxyd" (styrol oxide, now: "polystyrene"). By 1845,
the German chemist August Hofmann and his student John Blyth (1814 –1871) had
determined Styrol's empirical formula: C8H8. They had also determined that Simon's
"Styroloxyd" which they renamed "Metastyrol" had the same empirical formula as
Styrol.
The modern method for production of styrene by dehydrogenation of ethylbenzene
was first achieved in the 1930s. The production of styrene increased dramatically
during the 1940s, when it was used as a feedstock for synthetic rubber. Because
styrene is produced on such a large scale, ethylbenzene is in turn prepared on a
prodigious scale.

INTRODUCTION:

Styrene is a colorless oily liquid that evaporates easily and has a sweet smell,
although high concentrations have a less pleasant odor; melts at -30.6°C. Post-world
war period witnessed a boom in styrene demand due to its application in the
manufacture of synthetic rubber. This led to a dramatic increase in styrene capacity.
Styrene has wide application in producing plastic and synthetic rubber industry. It is
mostly used in manufacturing of polystyrene (PS), acrylonitrile-butadiene-styrene
(ABS), styreneacrylonitrile (SAN), styrene-butadiene rubber (SBR) and lattices,
unsaturated polyester resins (UP resins) and miscellaneous uses like textile
auxiliaries, pigment binders polyester resin, aromatics and intermediate industries.

PHYSICAL PROPERTIES:
Various physical properties of styrene are listed in Tables
 Table 1 Physical Properties of styrene

Melting point: -33 °C to -30.6°C Form: Liquid

Boiling point: 145°C Solubility 0.24g/l
Density: 0.906 g/mL at 20 °C Sensitive Air sensitive
Vapor density: 3.6 (vs air) Color Colorless
Vapor pressure: 12.4 mm Hg (37 °C) Stability Stable, but may
polymerize upon
exposure to light
Storage temp: 2-8 °C Refractive index 1.5469
Flash Point: 88 °F

APPLICATIONS
Applications of styrene are as:
 Styrene is mainly used as raw material for polystyrene, synthetic rubber, plastics, ion
exchange resins, etc.
 The most important use of styrene is as monomer for synthetic rubber and plastics, it
is used to produce styrene-butadiene rubber, polystyrene, polystyrene foam; it is also
used as other copolymerizable monomers to manufacture many different applications
of engineering plastics.
 Styrene is used for the preparation of copper brightener, and has effect of leveling
and bright.
 Styrene is used in table food, cake food, condiments, desserts, snacks, all kinds of
canned food, candy. Variety of drinks, especially yogurt, lactic acid bacteria drin ks,
carbonated drinks and other acidic beverages.
 Styrene is used for electron microscopic analysis, organic synthesis.

MANUFACTURING METHODS:
 Catalytic Dehydrogenation of ethyl benzene.
 Oxidation of ethyl benzene to ethyl benzene hydroperoxide which reacts with
propylene oxide after which the alcohol is dehydrated to styrene.
 Side-chain chlorination of ethyl benzene followed by dechlorination.
 Side-chain chlorination of ethyl benzene hydrolysis to the corresponding alcohols
followed by dehydration.
 Pyrolysis of petroleum recovery from various petroleum processes.
  Pyrolysis of petroleum recovery from various petroleum processes:
In this process styrene is separated from thermally cracked petroleums. In the process of
this invention thermally cracked petroleum is initially distilled to recover the fraction
boiling between 120 oC and 160 oC. This fraction is then subjected to extractive distillation
with an organic polar solvent containing a nitrite polymerization inhibitor in which the
styrene is soluble. The solvent is removed and the styrene containing fraction is thereafter
treated with nitric acid after which it is scrubbed with water or alkali. The resulting
product is fractionated to recover styrene of high purity which is substantially colorless.
 This process is not favorable due to the unavailability of raw material.
 Due to carbon in petroleum catalyst can also be poisoned.

 REGIOSELECTIVITY CARBOXYLATION OF PHENOL

Salicylic acid can be prepared by carboxylation of phenol with carbon dioxide in the
presence of Lewis acid catalyst at normal temperature
(20-80C). Aluminum bromide can also be used as a catalyst. To get better results the
reaction condition can be changed
 This method is clean, mild, efficient, easy to use for the preparation of Salicylic
Acid
 But it gives high regioselectivity into substitution of carboxyl group in Ortho
situation

 KOLBE-SCHMITT PROCESS

The first suitable method was introduced by Kolbe in 1874. The process involves the
reaction of sodium phenolate with carbon dioxide under high temperature and
pressure. The drawback of Kolbe was the yield was not more than 50% and separation
of by byproducts was difficult.
Schmitt introduced the new temperature range from 120-140 C. Which increased the
yield of process The reaction of carbon dioxide on the phenol which give an
intermediate phenyl carbonate which rearrange itself to give O-sodium salicylate this
method is known is Kolbe-Schmitt
Process
 It is still the only industrial process that is available for manufacturing
salicylic acid in bulk

Process Selection
Today the production of salicylic acid is commercially done by Kolbe-Schmitt Process.
The reason for the selection of this process is that it is the only process that can be done on
industrial scale. Secondly the Kolbe-Schmitt process is a very efficient process that yields
about 82-88% of the product.
PROCESS FLOW DIAGRAM

HEAT EXCHANGER HEAT EXCHANGER HEAT EXCHANGER REACTOR HEAT EXCHANGER HEAT EXCHANGER
MIXER MIXER

CONDENSER

BOILER
HEAT EXCHANGER

CONDENSER

SEPARATOR

VALVE
HEAT EXCHANGER

BOILER
FLASH TANK

CONDENSER

PUMP

HEAT EXCHANGER

BOILER
PUMP

PROCESS DISCRIPTION
Salicylic acid is manufactured by the reaction of caustic soda with Phenol and from the
treatment of sodium phenolate produced with CO 2 and acidifying the end product with
H2SO4.Phenol and caustic soda are feed to a mixer in an equimolar proportion. The mi xed
solution is then heated 130 C temperature and then evaporated to dryness in a stirred
autoclave.
Dry CO2 is absorbed and product of autoclave is dissolved in water in an equal amount and
then filtered. Filtrate is precipitated and then dried. The pure product is obtained the crude
sodium salicylate solution decolorized with the activated carbon containing the zinc and then
filtered.
The filtrate is then acidified with excess of H 2 SO4 to precipitate the salicylic acid which is
centrifuged and dried to give the high grade salicylic

MARKET ANALYSIS
Salicylic aid is an organic white crystalline solid which is highly soluble in water. It is derived
from the metabolism of salicin which is an anti-inflammatory agent extracted from willow
bark. Salicylic acid is mainly used in manufacturing of aspirin and other personal care
products consumption of aspirin is increasing in emerging economies of Asia which has
resulted in growth of salicylic acid market at an annual growth rate of 8% in recent past
The globe salicylic acid market is classified on the basis of the following segments
 Pharmaceuticals
 Cosmetics
 Food and preservatives

HAZORDS ASSOCIATED
The hazards problems related to Salicylic acid are given in the table below:

Types of Acute Hazards Prevention

Hazards

Fire Combustible No open flame

Explosion Finally dispersed particles from Prevent deposition of dust ; closed

explosion mixtures in air system ,dust explosion-proof
electrical equipment and lighting
Inhalation Cough, Sore throat Local exhaust or breathing protection

Skin Redness Protected gloves

Eyes Redness and pain Safety goggles or eye protection in

combination with breathing
protection
Ingestion Nausea. Vomiting, Do not eat, drink, or smoke during
Ear ringing. work
Exposure Prevent dispersion of dust
SCOPE:
The global salicylic acid market is expected to reach USD 547.5 million by 2024, according to
a new report by Grand View Research. Salicylic acid demand in food & preservative application
was valued at over USD 90.0 million in 2015. Asia Pacific is expected to witness the highest
growth as compared to other regions, growing at over 9.0% from 2016 to 2024.

REFERENCE:

i. https://www.britannica.com/science/salicylic-acid
ii. https://www.ukessays.com/essays/biology/history-of-salicylic-acid-biology-
essay.php
iii. https://www.thesisscientist.com/docs/EdwardCage/3e955573-2a08-4ff7-b9dc-
382502a5d76e.pdf
iv. http://www.chemicalbook.com/ChemicalProductProperty_EN_CB1680010.htm
v. http://www.chemicalland21.com/specialtychem/finechem/SALICYLIC%20ACID.ht
m
vi. ‘GEORGE H.ANDEREWS,PLANT REQUIREMENTS FOR MANUFACTURE OF
SALICYLIC ACID,INTERNATIONAL COOPERATION ADMISTRATION
WASHIGTON,D.C.,SEPTERBER 1961
vii. E. Golub, D. Hanesian, H. Hsieh and A. J. Perna, The Siting and Design of a
Manufacturing Facility, New Jersey Institute of Technology, 1997