Answer 2) We are going to discuss about two chemical components

1) STYRENE
2) NITRIC ACID

STYRENE
Styrene is a colorless liquid aromatic monomer with a sweetish smell. It plays a vital role in the
production of rubber and plastic components. Styrene is commonly manufactured from petroleum, it
also occurs naturally in certain plants, for instance, vegetables, fruits and nuts. Its molecular formula
is C8H8, meaning that it consists entirely of the elements carbon and hydrogen. Styrene has other
names like - vinylbenzene, phenylethylene, cinnamene, styrolene, styrol, and styropol.

MAJOR LICENSORS OF STYRENE

Global styrene supply and demand The main licensors of styrene production processes are
Styrolution (Joint venture between BASF (Baden Aniline and Soda Factory) and INEOS (INspec
Ethylene Oxide and Specialities)), Total Petrochemicals, China National Petroleum Corporation
(CNPC), Shell, LyondellBasell Chemical Co, Formosa Chemicals and Fibre Corp (FCFC), Formosa,
Saudi Petrochemical Co (Sadaf) and Americas Styrenics.

INDIAN MARKETS SCENARIO AND CAPACITY

The Indian Styrenics Market was of 526 KT in 2015. The demand of Styrene has been continuously
increasing in Indian plastics market from past few years. The end segment with high styrene
consumption was automobiles, packaging, building and constructions, consumer products, medical
devices and others. Indian styrene market is segmented into three subcategories as polystyrene, ABS
(Acrylonitrile Butadiene Styrene), and SAN (Styrene Acrylonitrile).

In 2015, Polystyrene amounting to 241 KT, which covered a share of 45.8% of the Indian styrene
market followed by Acrylonitrile Butadiene Styrene which is accounted 183 KT and covered 34.7%
market share. The Styrene Acrylonitrile accounted for 19.5% of market share, which in terms of
volume was 102KT. The demand of SAN was due to its excellent properties of weatherability, stress,
barrier and crack resistance. The demand growth for polystyrene has been relatively moderate
while ABS and SAN have been witnessing healthy growth from the consumer electronics,
appliances, and automotive sector.

The key major producers of styrenes are Supreme Petrochem Limited (SPL), INEOS
Styrolution India Limited, LG Polymers and Bhansali Engineering Polymers Limited. The
production capacity of the key manufacturers is Supreme Petrochem with a 272,000 tonne/year
capacity and LG Polymers India with an 80,000 tonne/year capacity.

Further, it is expected that market will see a favorable styrene demand growth because of low crude
oil prices and roll out of Goods and Service Tax (GST) in the Indian market.
STYERE CONSUMPTION, USAGE AND BENEFITS

Styrene helps in creating remarkably strong, flexible, and light-weight products. Probably the most
recognizable material is polystyrene, often encountered as expanded polystyrene foam (EPS). Other
styrene-based materials include acrylonitrile-butadiene styrene (ABS), styrene-acrylonitrile (SAN),
and styrene-butadiene rubber (SBR). Styrene is also used as a diluent and reactive cross-linker for
thermoset polyester resin, which is combined with a reinforcement (such as glass fiber) to form
composite materials such as fiberglass. In order to provide feedstock for these products, styrene
utilization rates will grow rapidly in next few years and are expected to reach ~95% .

ROUTES TO PRODUCE STYRENE

Production of Styrene Many different techniques have been investigated for the manufacture of
styrene monomer. Of these, the following methods have been used and seriously considered for
commercial production

1. Dehydrogenation of ethyl benzene.

2. Oxidation of ethyl benzene to ethyl benzene hydro peroxide, which reacts with propyleneoxide,
after which the alcohol is dehydrated to styrene.
3. Oxidative conversion of ethyl benzene to α-phenyl ethanol via acetophenon and subsequent
dehydration of alcohol.
4. Side-chain chlorination of ethyl benzene followed by dechlorination.
5. Side-chain chlorination of ethyl benzene, hydrolysis to the corresponding alcohols, followed by
dehydration.
6. Pyrolysis of petroleum recovery from various petroleum processes.

MERITS AND DEMERITS

The first two methods are commercially utilized routes in the production of styrene. Method 3 was
practiced by M/s. Union-Carbide Corporation but later was replaced with a dehydrogenation process.
In methods 4 & 5, involvement of chlorine is necessary. These methods demand high cost raw
materials. Another disadvantage is the presence of chlorinated contaminants in the monomer. In
method 6, manufacture of styrene is directly obtained from petroleum streams and it is difficult and
costly.

ROUTES IN DETAIL
1. Epoxidation of propene route Most of the styrene is produced via dehydrogenation. A
fraction, ca. ~10%, is produced via the SMPO or POSM process that also produces propene
oxide (SM = styrene monomer, PO = propene oxide). Depending on the company that
operates it, the most important product is named first.
The main drawback of a SMPO process is that it has limited product flexibility. Styrene and propene
oxide are always produced together in a mass ratio of around 2.1 (SM:PO, the molar ratio is ~1),
while the market demand is often different. Recently, the technology has been successfully
commercialized to produce PO without a hydrocarbon by-product and this was named as HPPO
process (DOW/BASF technology). Therefore, there is no need to construct new SMPO plants for the
expansion of ST production.

2. Dehydrogenation of ethylbenzene route Several licensed processes are available for the
conversion of ethylbenzene to styrene. Although all such processes share the catalytic
dehydrogenation of ethyl benzene to styrene in the presence of steam, there are two distinct
approaches to the reaction section design: the adiabatic process and the isothermal process. As
the dehydrogenation reaction is endothermic, heat must be supplied. In the adiabatic process,
steam is superheated to 1073-1223 K. This is mixed with preheated ethyl benzene (EB) feed
prior to exposure to the catalyst. The isothermal process takes place in Plug Flow Reactor
(PFR) and reaction heat is provided by indirect heat exchange between the process fluid and a
suitable heat transfer medium, e.g., flue gas (BASF technology).
The conversion of EB into ST is equilibrium limited. Therefore, it is operated at high temperature and
the EB partial pressure should be as low as practically possible, which can be achieved by dilution
with H2O. Usually two reactors are used side by side with additional heating in between, to increase
the EB conversion up to around 60-65% and selectivity of styrene up to 96%.

Problems in ethylbenzene dehydrogenation

The main problems in the actual ethylbenzene dehydrogenation process are

The dehydrogenation of EB to styrene (ST) is equilibrium limited and highly endothermic reaction (∆H°298k
= 28.1 kcal/mol).

The industrial process is highly energy consuming because of the excess steam usege and the high
endothermicity of the reaction.

The reversibility of the dehydrogenation process thermodynamically hinders maximum yields of styrene.

The technical EB conversion is limited below 60%, to keep an acceptable high selectivity to styrene. A slight
irreversible deactivation of the catalyst (the lifetime is usually about two years).

Coke deposition Careful review of the literature data indicates that a steady layer of coke is always present
during typical styrene synthesis conditions.

Loss or redistribution of promoters the alkali metals are important promoters for the gasification of
carbonaceous deposits. The important promoter in styrene synthesis is potassium, which as mentioned earlier
plays many roles in this process. Potassium migrates from the exterior to the core of the catalyst pellet due to a
temperature gradient resulting from the endothermicity of the reaction .
NITRIC ACID (HNO3)
Nitric acid is a colorless liquid that is used in the manufacture of inorganic and organic nitrates
and nitro compounds for fertilizers, dye intermediates.

Nitric Acid is a pale yellow to reddish brown liquid generating red-brown fumes and having a
suffocating odor.

a) Methods of manufacturing Nitric Acid

1. CHILE SALTPETRE METHOD by NaNO3
2. BRIKLAND EYDE’S METHOD by USING AIR
3. OSTWALD METHOD BY AMMONIA SOLVAY PROCESS

1) CHILE SALTPETRE METHOD by NaNO3

It is the first commercial process of manufacture of nitric acid from sodium nitrate
extracted from Chile saltpeter. The process is now become obsolete since 2nd decade of
19th century and requires huge amount of energy.

Raw Material
Basis: 1000kg Nitric Acid(95% yield)
Sodium Nitrate = 1420kg
Sulfuric Acid = 1638kg

Reaction:
NaNO3 + H2SO4  NaHSO4 + HNO3
 2) BRIKLAND EYDE’S METHOD(ARC METHOD)

Raw Material
Basis: 1000kg Nitric Acid(98% yield)
Air = 198kg
Water = 145kg

CO2 and dust free air is heated in an arc furnace at 3000C. Nitric Acid is formed. Gases coming
out from the furnace are cooled at 1000C by passing through cooler then gases are passed in a
boiler and cooled at 150C. Cold water is circulated around the boiler to cool the gases. Gaseous
mixture is now passed through aluminum tubes. The temperature of gaseous mixture becomes
50C.

Gaseous mixture is passed in oxidizing tower where NO is oxidized into NO2

2NO+ O2 2NO2

NO2 is absorbed in water in absorption tower then dilute HNO3 is obtained.

3NO2 + H2O  2HNO3 + NO

Now this method is not used in manufacture of HNO3 because of consumption of electricity is
very high to maintain the temperature 3000C. Even at this temperature 1% NO is formed.
 3) OSTWALD’S METHOD

Principle:

NH3 is oxidized into NO by air at 800C in presence of Pt(platinum) catalyst

Raw Materials

Basis: 1000kg nitric acid(100%)

Ammonia = 290kg ; Air = 300Nm3 ; Platinum = 0.001kg ; Water= 120000kg ; Steam credit =
1000kg @ 200psig ; Power = 10-30KWh

Process:

Mixture of NH3 and O2 in the ratio of 1:9 is passed through catalyst chamber containing Pt-
gauge. Temperature of the catalyst is kept at 800C. About 95% NH3 is converted into NO.

4NH3 + 5O2  4NO + 6H2O +21.6kcal

Heat liberated maintains the temperature of the catalyst. The gases coming out are cooled to
about 50C and mixed with more O2. This gaseous mixture is passed in oxidizing tower where
NO is oxidized to NO2.

2NO + O2  2NO2

NO2 is passed in absorption tower. The dilute solution of HNO3 is obtained.

3NO2 + H2O  2HNO3 + NO

S. No. Process Merits Demerits
1. Chile SaltPeter 1. 95% yield 1. Require huge amount
Method 2. Process doesn’t involve of energy.
several steps 2. Hot furnace gases
needs to be handled.
2. Brikland Eyde’s 1. Feed is easily available 1. Consumption of
Process 2. 98% yield electricity is more
2. Even at 3000C 1% NO
is formed.
3. Ostwald Process 1. Almost no by products 1. NH3 is expensive and
2. 100% yield dangerous.
3. No loss of catalyst 2. Risk of explosion.

b) MOST PREFERED ROUTE TO SYNTHESZIE NITRIC ACID

After discussing all the available steps and understanding their merits and demerits our
conclusion matches with the worldwide used method i.e. OSTWALD PROCESS is the
most preferred route.
Global Nitric Acid market is projected to grow upto 6899.7 kilotons by 2021, at a CAGR
of 3% having a share of 81% in fertilizers.

c) INDIAN SCENARIO
1) Ministry of Defence, Govt. of India in Bhandara with 20MTPD
2) Deepak Nitrite in Taloja with 35MTPD
3) Vijay Gas Industry with a capacity of 2300 metric tons per month
4) VBC Industries with 80MTPD in Hyderabad
5) Hindustan Fertilizer Corporation Ltd. haldia with a capacity of 500MTPD
6) Ministry of Defence, Govt. of India in Kirke with 20MTPD
7) Steel Authority of India Ltd. at Rourkela with a capacity of 820 MTPD