CHAPTER I

Introduction

Styrene is one of the most important monomers produced by the chemical

industry today. Styrene monomer is a basic building block of the plastics industry. It is a
liquidhydrocarbon that is important primarily due to its marked tendency to undergo
polymerization (a process in which individual molecules are linked to produce extremely
large, multiple-unit molecules). It is employed in the manufacture of polystyrene, an
important plastic, as well as a number of specialty plastics, fiberglass, latex and
synthetic rubbers. It occurs naturally in some fruits, vegetables, meats, nuts, and
beverages.Cigarette smoke and vehicle exhaust also contain styrene.
(https://toxtown.nlm.nih.gov/chemicals-and-contaminants/styrene)

The polymerization of styrene has been known since 1839, when German
pharmacist Eduard Simon reported its conversion into a solid later named metastyrol.
There is littlecommercial use for the polymer even until 1930 since it had been found that
the polymer is brittle and crazing (minute cracking), which were caused by impurities that
brought about the cross-linking of the polymer chains. On 1937, American chemist
Robert Dreisbach and others at the Dow Chemical Company's physics laboratory
obtained purified styrene monomer through the dehydrogenation of ethylbenzene and
developed a pilot polymerization process. It was being produced commercially by 1938.
It quickly became one of the most important modern plastics, due to its low cost of
producing large volumes of styrene monomer, the ease of shaping the melted polymer in
injection-molding operations, and the optical and physical properties of the material.
(Encyclopædia Britannica, 2014)

Styrene alone has a wide range of applications of insulation, food containers,

toys, shoes and even automobile parts. The most important products are solid
polystyrene (PS), expandable polystyrene (EPS), styrene butadiene latex (SBL),
acrylonitrile-butadiene-styrene/terpolymer (ABS), unsaturated polyester resins (UPR),
and styrene-butadiene rubber (SBR). Some of styrene’s markets include polystyrene,
ABS, styrene acrylonitrile and styrene-based polyesters of which are described
hereafter.

Polystyrene is primarily used in packaging, disposables and low-cost consumer

products. Expandable polystyrene beads are primarily used in food and beverage
packaging, insulation and cushion packaging. Improved grades of resins are used in
higher performance applications, such as home electronics and appliances. ABS and
styrene acrylonitrile (SAN) have many uses in the consumer durables market.Styrene-
based polyesters enjoy long service life in both indoor and outdoor applications, e.g.,
polyester boats typically last longer than boats made from conventional materials.
Thermoplastic elastomers are directly replacing natural and traditional synthetic rubbers
in many established applications and entering new markets. Other applications include
carpet backing (SBL), production of tires (SBR) and castings for textiles and paper.
Many products made from styrene are recyclable. Chevron Phillips Chemical along with
other polystyrene producers formed the National Polystyrene Recycling Company
(NPRC) to recycle post-consumer polystyrene. Recycled polystyrene is used in
packaging, construction materials, office supplies and other useful
products.(http://www.cpchem.com/bl/aromatics/en-us/pages/styrenemonomer.aspx)

Styrene is one of the raw materials used in petrochemical industry besides

ethylene, propylene and others. The Association of Petrochemical Manufacturers of the
Philippines (APMP), like the name itself is a group of manufacturers related to the
petroleum industry. In the Philippines, for the production of polystyrene (PS), a product
from styrene, the two active producers are Chemrez Technologies (D & L Industries, Inc)
and SMP, Inc. (non-member) but the raw material, styrene came from Taiwan. This
means that there is no production plant of styrene in the Philippines since we need to
import our raw materials from other countries. (The Philippine Petrochemical Industry
Profile, 2017).

Many products made from styrene are recyclable. The National Polystyrene
Recycling Company (NPRC) was formed to recycle post-consumer polystyrene. It was
founded by Chevron Phillips Chemical and other polystyrene producers. Recycled
polystyrene is used in packaging, construction materials, office supplies and other useful
products.(http://www.cpchem.com/bl/aromatics/en-us/pages/styrenemonomer.aspx)
Objectives of the Study

General Objective

This project seeks to design a manufacturing plant which makes use of Oxidative
Dehydrogenation of 1,3-Butadiene for the production of styrene.

Specific Objective

Specifically, it aims to

 Determine the uses, products and demand markets of styrene

 Evaluate different processes used to produce styrene monomer
 Conduct material and energy balances of selected unit operation or process unit
involve in the production of Styrene
 Design a full scale mass production industrial plant of styrene from ethyl
benzene.
 Determine the process specifications on the following unit operation and process
equipment: heat exchangers, mixer, distillation column, catalytic reactors
 Determine the safety, health, environmental and economic implications relating
to the design of the plant

Importance and Economic Value

Importance of Styrene

Styrene is one of the most important monomers worldwide, and its polymers and
copolymers are used in an increasingly wide range of applications. The major uses are
in plastics, latex paints and coatings, synthetic rubbers, polyesters and styrene-alkyd
coatings. Among the top 50 chemicals worldwide, styrene was twentieth in 1994 with
production of 11 270 million pounds. Styrene occurs naturally as a degradation product
in cinnamic acid containing plants, and as a by-product of fungal and microbial
metabolism.

Styrene is so widely used today because it enables a multitude of products to

deliver many benefits that are highly valued by consumers. These benefits include
strength, durability, comfort and safety. Styrene-based products cushion bicycle helmets,
strengthen military armor, create wind power turbines, reduce coal plant emissions, and
enhance components that make cars and trains lighter and more fuel-efficient. They also
enable manufacturing high-performance and cost-effective recreational products such as
boats and other watercraft, and reduce dependence on costly natural resources such as
tropical hardwoods used in boats and marble and granite used in homes and buildings

Economic Value of Styrene

Styrene is a commodity aromatic chemical produced mainly from ethylbenzene-

(EB-) based technology; it is easily polymerized to make plastics and resins. The major
markets for styrene are polystyrene, acrylonitrile-butadiene-styrene (ABS)/styrene-
acrylonitrile (SAN) resins, styrene-butadiene (S/B) copolymer latexes, SBR elastomers
and latexes, and unsaturated polyester resins (UPR).

About 80% of the world’s styrene capacity is based on the conventional process.
The first step is to use ethylene and benzene to produce ethylbenzene (EB); the EB is
then dehydrogenated to produce styrene. Much of the remaining global styrene capacity
is based on a process to coproduce propylene oxide (PO) and styrene monomer (SM) in
which EB is reacted with propylene in a PO/SM plant. It is important to understand these
two major feedstocks, as they outline the styrene supply worldwide. Benzene, an easily
transportable liquid, constitutes approximately 80% of the styrene molecule by mass and
is an important component of the cost of styrene. By comparison, ethylene is only about
30% of the styrene molecule by mass, but it is a gas and is difficult to transport. For this
reason, styrene plants are typically, but not always, located close to ethylene crackers.

Over the last five years, global styrene consumption grew at an average rate of
1.5% per year. Consumption declined in the United States, Western Europe, South
America, and Southeast Asia during 2012–17, while the other major players saw minimal
increases, aside from China. Northeast Asia (China, Japan, South Korea, and Taiwan)
remains the dominant player in the styrene industry, driven by China, and China will
continue to be the fastest-growing market in the region. The Middle East and Africa will
be the fastest-growing regions among the smaller markets, with expected average
annual growth rates of nearly 8% and more than 20%, respectively, over the next five
years, following the new expansions in styrene derivative capacity. Overall, styrene
consumption is forecast to stay relatively flat, growing at an average rate of 2% per year
in 2017–22.

Polystyrene drives styrene consumption worldwide. Of the total amount of

styrene consumed in 2017, nearly 36% went into general-purpose/high-impact (GP/HI)
polystyrene production and 21% went into expandable polystyrene (EPS) production.
GP/HIPS is the largest demand segment in most regions; in China and Central Europe,
expandable polystyrene has the largest market share. Polystyrene consumption
continues to come under pressure from polypropylene and PET from both a cost and
performance perspective, especially in packaging, the largest global market for
GP/HIPS; global consumption remains below prerecession levels. EPS consumption
was severely impacted by the economic downturn, but has grown steadily as
construction markets have recovered. In construction markets, EPS is increasingly used
as concrete forms and insulation, where higher energy-efficiency standards are driving
demand.
 Styrene consumption into ABS resins, UPR, and SBR is expected to see the
highest annual growth rates through the forecast period. ABS, the third-largest styrene
derivative, is the largest-volume engineering thermoplastic resin in the world. ABS is
used in many consumer-related end-use applications including appliances,
electronics/electrical, building and construction, and transportation. Consumption of
styrene into ABS resins is particularly strong in Southeast Asia and Northeast Asia. The
ABS market is projected to grow at an average rate exceeding 4% per year over the next
five years.

Styrene is one of the highest-volume commodity chemicals traded, with about

30% of global annual production traded internationally. In 2017, global styrene trade was
down from a peak in 2014–15. This decline in trade volumes reflects the increase in
capacity in the traditional importing areas such as Asia and South America. Northeast
Asia is by far the largest importing region, driven by China. China currently accounts for
nearly 38% of global trade; however, by 2022, Chinese imports will fall closer to 21% of
global trade, as the country becomes more self-sufficient.

After a large amount of restructuring and rationalization since 2008, the global
styrene industry has continued the long, slow process of recovery from the previous
decade’s recession. Despite the improved performance and improving outlook for the
global styrenics industry, low underlying demand remains a fundamental weakness.
Consumption growth rates remain stubbornly below GDP growth on a global basis and
this is unlikely to change. In 2017, styrene capacity exceeded consumption, and growth
in capacity will continue to increase at a faster rate than consumption growth.

Safety, Health and Environmental Considerations

In every industry, securing the health, safety and environment are important. Its
significance is not less than the importance of the profitability of the factory. So it is
preferable to know more about HSE of the intermediate and final product.

Sources of Styrene

Styrene has been detected in the atmosphere in many locations. Its presence in
air is principally due to emissions from industrial processes involving styrene and its
polymers and copolymers. Other sources of styrene in the environment include vehicle
exhaust, cigarette smoke and other forms of combustion and incineration of styrene
polymers

The concentration of styrene in urban air is relatively low compared with that of
aromatic hydrocarbons, such as toluene and xylene. This appears to be due to the ready
reactivity of styrene with ozone to yield benzaldehyde and peroxides, all of which are
irritants; one of the peroxides, peroxybenzyol nitrate, is a potent eye irritant. Styrene is
an active component of photochemical smog.

Occupational Exposure

Workers may be exposed in a number of industries and operations, including

styrene production, production of polystyrene and other styrene-containing polymer
resins, plastics and rubber products fabrication, fabrication of reinforced-polyester
plastics composites and use of products containing styrene, such as floor waxes and
polishes, paints, adhesives, putty, metal cleaners, autobody fillers and varnishes.
Highest exposures have been measured in the reinforced plastics industry. Average
exposure of workers to styrene in styrene production and polymerization factories has
been reported rarely to exceed 20 ppm (85 mg/m3 ), usually due to occasional bursts
and leakages of reactors, tubing and other equipment. Surveys conducted in United
States plants engaged in the development or manufacture of styrene-based products
between 1962 and 1976 showed that the average exposure of employees in all jobs was
below 10 ppm, with occasional peaks of up to 50 ppm. Occupational exposure to styrene
is most extensive, with respect to number of workers and levels of exposure, in the
fabrication of objects from glass fiber-reinforced polyester composite plastics, such as
boats, tanks, wall panels, bath and shower units and automotive parts. Styrene serves
as a solvent and a reactant for the unsaturated polyester resin, in which it constitutes
about 40% by weight. During lamination and curing, about 10% of the styrene may
evaporate into the workplace air. Several factors influence the level of styrene in
workplace air. The manufacture of objects with large surface areas such as boats, truck
parts, baths and showers by the open-mould process results in the highest exposure of
styrene. Data from 28 plants producing reinforced plastics products in the United States
showed that the average exposure to styrene in open-mould processes was two to three
times higher than that in press-mould processes: 24–82 ppm (102– 350 mg/m3 ) versus
11–26 ppm (47–111 mg/m3 ). In a detailed survey of 12 plants making fiberglass in
Washington State, 40% of 8-hour samples contained more than 100 ppm (426 mg/m3 ).
Chopper gun operators had the highest exposure, followed by laminators and gel-coat
applicators; boat-building involved higher exposures than any other sector. In an
extensive survey of the reinforced plastics industry in Finland, styrene levels in 77% of
respiratory zone measurements for laminators exceeded the hygienic standard of 20
ppm (85 mg/m3 ), and the mean 8-hour time-weighted average (TWA) was 43 ppm
(range 5–182 ppm).

Health Effects

Acute (short term) exposure to Styrene vapour in the workplace can cause
irritation to the throat, nose and lungs. It can also cause neurological effects such as
drowsiness, nausea and headaches. Chronic (long term) exposure affects the central
nervous system, can cause depression, hearing loss and peripheral neuropathy. Styrene
is readily absorbed and distributed throughout the body following exposure. It is
considered to be a possible carcinogen.

The level of Styrene in the workplace should be no more than 100 parts per
million (ppm) averaged over an 8-hour day. This is the maximum work exposure limit
(WEL). Styrene is a flammable substance and eventually ends up in the air. Controlling
vapour levels of Styrene depends on the manufacturing methods used, for example, the
amount of resin used, whether one is using a non-atomizing spray gun or not, whether
gel coating is used, the curing rate, the size of the workroom etc. The greatest exposure
is in industries using unsaturated polyester resins dissolved in Styrene. Dust from the
fibers of glass reinforced grinding can also cause health problems; possible control
measures are use of gloves and adequate local ventilation. Provided there is adequate
controls in place there should be no damage to peoples’ health.

Controlling the Exposure

Minimizing environmental exposure includes locating plants away from

residential areas. Efficient capture systems should be used to disperse emissions and
reduce ground-level concentrations. Styrene should not be stored next to other cargo
with temperatures above 30 degrees Celsius, otherwise the shelf life will be reduced and
there would be an increase in the risk of polymerisation in the cargo tank. Tanks carrying
or unloading Styrene polymer should not be exposed to chemicals that may react with it
such as caustic soda, gasoline or oils. Minimizing exposure to human health includes
providing good ventilation in the working area; this is critical to reduce inhalation. Gloves
should be used and rollers with splash guards used to control droplets. Lids should
always be replaced on containers. Ventilation may need to be supplemented
with respiratory protective equipment. All should be done in accordance with COSH
regulations. Facilities using styrene should have a response plan to include fire
prevention, spill detection methods, environmental protection, emergency procedures
and provisions for clean up in case of spills.