Gujarat Cleaner Production Centre - ENVIS CENTRE

Petrochemical Industry

CLEANER PRODUCTI
PRODUCTION
OPPURTUNITIES

IN

PETROCHEMICAL INDUSTRIES

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Introduction to Petrochemical Industry

India is having 3.17 million square kilometers land mass and over 1.22 billion population and is
one of the fastest growing economies in the world. It has well
well-developed
developed Process Industry. India
has petroleum refining capacity of over 194 Million Tones per Annum (MTPA). The world's
largest grass
ass root refinery with 32 MTPA capacities is located in India. It has a number of gas
cracker complexes with downstream facility producing 8 MTPA plastics and polymers.

The petrochemical industry in India has been one of the fastest growing industries in the
t country.
Since the beginning, the industry has shown an enviable rate of growth. Indian petrochemical
industry grew at a rate of ~11% in 2010
2010-11. The outlook for 2011-12 12 is also stable and the
chemicals market is expected to grow at 11
11-13% p.a. over the next five years

Petrochemicals are the derivatives of crude oil and natural gas. Olefins (ethylene, propylene &
butadiene) and Aromatics (benzene, toluene & xylenes) are the major building blocks from
which most Chemicals and Petrochemicals are produced. They are used in dyes, synthetic fibres,
rubbers, plastics, pharmaceutical bulk drugs, industrial appliances, packaging industry,
detergents (surfactants).

Highlights of processes for different Petrochemicals.

The adjacent diagram schematically depicts the major hydrocarbon sources used in producing
petrochemicals are:

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• Methane, ethane,, propane and butanes:: Obtained primarily from natural gas
processing plants..
• Naphtha obtained from petroleum refineries.
• Benzene, toluene and xylenes, as a whole referred to as BTX and primarily
obtained from petroleum refineries by extraction from the reformate produced in
catalytic reformers
reformers.
• Gas oil obtained from petroleum refineries.

Methane and BTX are used directly as fee

feedstocks
dstocks for producing petrochemicals. However, the
ethane, propane, butanes, naphtha and gas oil serve as optional feedstocks for steam-assisted
steam
thermal cracking plants referred
red to as steam crackers that produce these intermediate
petrochemical feedstocks:

• Ethylene
• Propylene
• Butenes and butadiene
• Benzene

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C1 compounds (with one carbon atom in their molecule) manufactured at petrochemical plants
include methanol, formaldehyde, and halogenated hydrocarbons. Formaldehyde is used in the
manufacture of plastic resins, including phenolic, urea, and melamine resins. Halogenated
hydrocarbons are used inn the manufacture of silicone, solvents, refrigerants, and degreasing
agents.
Olefins (organics having at least one double bond for carbon atoms) are typically manufactured
from the steam cracking of hydrocarbons such as naphtha. Major olefins manufactured include
ethylene (C2, since it has two carbon atoms),propylene (C3), butadiene (C4), and acetylene. The
olefins manufactured are used in the manufacture of polyethylene, including low-density low
polyethylene (LDPE) and high--density polyethylene (HDPE), and for or polystyrene, polyvinyl
chloride, ethylene glycol (used along with dimethyl terphthalate, DMT, as feedstock to the
polyester manufacturing process), ethanol amines (used as solvents), polyvinyl acetate (used in
plastics), polyisoprene (used for synthetic rubber manufacture), ), polypropylene, acetone (used as
a solvent and in cosmetics), isopropanol (used as a solvent and in pharmaceuticals
manufacturing), acrylonitrile (used in the manufacture of acrylic fibers and nitrile rubber),
propylene glycol (used inn pharmaceuticals manufacturing), and polyurethane. Butadiene is used
in the manufacture of polybutadiene rubber (PBR) and styrene butadiene rubber (SBR). Other C4
compounds manufactured
factured include butanol, which is used in the manufacture of solvents such as
methyl ethyl ketone.
The major aromatics (organics having at least one ring structure with six carbon atoms)
manufactured include benzene, toluene, xylene, and naphthalene. Other aromatics manufactured
include phenol, chlorobenzene, styrene, phthalic and maleic anhydride, nitrobenzene, and
aniline.Benzene is generally recovered from cracker
streams at petrochemical plants and is used for the manufacture of phenol, styrene, aniline,
nitrobenzene, sulfonated detergents, pesticides such as hexachlorobenzene, cyclohexane (an
important
portant intermediate in synthetic fiber manufacture), and caprolactam, used in the manufacture
of nylon. Benzene is also used as a solvent. The main uses of toluene are as a solvent in paints,
rubber, andd plastic cements and as a feed stock ck in the manufacture of organic chemicals,
explosives, detergents, and polyurethane foams.
Xylenes (which exist as three isomers) are used in the manufacture of DMT, alkyd resins, and
plasticizers. Naphthalene is mainly used in the manufacture of dyes, pharmaceuticals,
armaceuticals, insect
repellents,
pellents, and phthalic anhydride (used in the manufacture of alkyd resins, plasticizers, and
polyester).
The largest userr of phenol in the form of ther
thermosetting
mosetting resins is the plastics industry. Phenol is
also used as a solvent and inn the manufacture of intermediates for pesticides, pharmaceuticals,
and dyestuffs. Styrene is used in the manufac
manufacture
ture of synthetic rubber and polystyrene resins.
Phthalic anhydride is used in the manufacture of DMT, alkyd resins, and plasticizers such as
phthalates.
Maleic anhydride is used in themanufacture of polyesters and, to some extent, for alkyd
resins.Minor uses include the manufacture of malathion and soil conditioners.

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Nitrobenzene is used in the manufacture of aniline, benzidine, and dyestuffs and as a solvent
sol in
polishes.
es. Aniline is used in the manu
manufacture
facture of dyes, including azo dyes, and rubber chemicals
such as vulcanization accelerators and antioxidants.

List of significant petrochemicals and their derivatives

The following is a partial list of the major commercial petrochemicals and their derivatives:

Ethylene - the simplest olefin; used as a chemical feedstock and ripening stimulant. Following
chart shows the ethylene and itss Derivatives

Propylene - used as a monomer and a chemical feedstock. Following chart shows the propylene
and its Derivatives

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Benzene - the simplest aromatic hydrocarbon. Following chart shows the propylene and its
Derivatives

Toluene - methylbenzene; canan be a solvent or precursor for other chemicals. Following chart
shows the toluene and its Derivatives.

Mixed xylenes - any of three dimethylbenzene isomers, could be a solvent but more often
ofte
precursor chemicals. Following chart shows the mixed xylene and its Derivatives.

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Emissions in Petrochemical Industry

Air Emission

In the petrochemical and refinery sector large amount of hydrocarbons are handled.
Even if diffuse emissions represent 0.1% of the throughput, handling 10 million tonnes of
crude oil will amount to 10.000 tonnes of VOC which has a large environmental burden
and also a significant cost.

The very high number of potential diffuse emissions from:

• Filling and emptying of storage tanks
• The expansion of the contents of storage tanks due to heating and cooling throughout the day
• The vacuum pumps used for a variety of processes
• Literally thousands of pipe and equipment joints.
• Sources are spread over a very large area some of them are high above ground
• Some potential leaking points are tight when installed but will leak eventually.

Water Emission

Petrochemical
al units generate wastewaters from process operation such as:
• Vapour condensation
• Cooling tower Blow down
• Storm water run off
If barometric condensers are used in vacuum distillation, significant amounts of oily waste water
can be generated. Oily sour water is also generated in the fractionators.

Solid Waste
cal plants also generate solid waste and sludges. Some of which may be considered
Petrochemical
hazardous because of the presence of toxic organics and heavy metals. Spent caustic and other
hazardous wastes such as distillation residues associated with units handling acetaldehyde,
acetonitrile, benzyl chloride, carbon tetra cchloride,
hloride, cumene phallic anhydride,nitrobenzene,
methyl pyridine, toluene di-isocyanate,
isocyanate, tricholoro ethane , tricholoro ethylene, aniline,
chlorobenzenes, dimethyl hydrazine, ethylene dibromide, toluenediamine, epichorohydrin, ethyl
chloride, ethylene dichloride
oride and vinyl chloride may be generated in significant quantities.

Environmental Issues in Petrochemical Industry and CP options

• Simple techniques such as the use of infra

infra-red photography from a light aero plane can be
used to identify significant emiss
emission
ion points from a refinery or petrochemical complex. Other
techniques such as light detection and ranging techniques (LIDAR) and the use of Solar
Occultation Flux which uses the absorption of solar infra red by the plume of VOC may also
be used.

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• In the petrochemical industry, where large volumes of chemical and oil products are stored in
tanks, a lot of experience has been gained on preventing and reducing emissions.
The following techniques are important [BREF on Storage]:
1. Tank design
2. Inspection, maintenance
intenance and monitoring
3. Floating, flexible and fixed covers
4. Domes
5. Tank colour to reflect sunlight
6. Solar shields
7. Natural tank cooling
8. External and internal floating roofs and the roof seals
9. Pressure and vacuum relief valves
10. Draining systems
11. Vapour balancingg and treatment, and
12. Mixing and sludge removal.
• By applying aboveground closed piping in new situations, leaks and spillage can be identified
quickly and action taken to stop leaks. Leak detection and repair (LDAR) is one of the BAT
conclusions in both cases and a programme of leak detection should be implemented using
sniffers to identify leaks from joints in equipment and pipework.
• Process optimisation and minimisation of emissions such as thermal or mechanical pre- pre
treatment of secondary material to miminimise
nimise organic contamination of the feed.
• The use of sealed process units to prevent fugitive emissions, allow heat recovery and allow
the collection of process gases for other use (e.g. CO as a fuel and SO2 as sulphuric acid) or to
be abated.
• The use of semi-sealed
sealed process units where sealed funits are not available.
• The minimisation of material transfers between processes.
• Where such transfers are unavoidable, the use of sealed pipelines.
• In some cases, restricting techniques to those that avoid material transfers would prevent the
recovery of some secondary materials that would otherwise enter the waste stream. In these
cases the use of secondary or tertiary fume collection is appropriate.
• Hooding and ductwork for the local exhaust ventilation equipment ddesigned esigned to capture the
gases produced
• Furnace or reactor enclosures may be required to prevent release of fume losses into the
atmosphere.
• Where primary extraction and enclosure are likely to be ineffective, then the furnace can be
fully closed and ventilation
tion air drawn off by extraction fans to a suitable treatment and
discharge system.
• Roofline collection of fume is very energy consuming and should be a last resort.
• An important established practice to achieve good extraction is the use of automatic controls
contr
for dampers so that it is possible to target the extraction effort to the source of fume without

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using too much energy. The controls enable the extraction point to be changed automatically
during different stages of the process. For example, charging aand nd tapping of furnaces do not
usually occur at the same time and so the charging and tapping points can be designed to be
close together so that only one extraction point is needed. The extraction point is also
designed to allow good access to the furnace and give a good rate of extraction. The hooding
is constructed robustly and is maintained adequately
adequately.
• Use nonchrome-basedbased additives in cooling water.
• Use long-life
life catalysts and regeneration to extend the cycle
cycle.
• Recycle cooling water and treated wastewater to the extent feasible.
• Recover and reuse spent solvents and other chemicals to the extent feasible.
• Segregate process wastewaters from storm water system
• Optimize the frequency of tank and equipment cleaning.
• Prevent solids and oily wastes from entering the drainage system.
• Establish and maintain an emergency preparedness and response plan.
• Petrochemical wastewaters often require a combination of treatment methods to remove oil
and other contaminants before discharge. Separation of different streams (such as stormwater)
is essential to minimize treatment requirements.
• Oil is recovered using separation techniques. For heavy metals, a combination of
oxidation/reduction, precipitation, and filtration is used.
• For organics, a combination of air or steam stripping, granular activated carbon, wet
oxidation, ion exchange, reverse osmosis, and electrodialysis is used. A typical system may
include neutralization, coagulation/flocculation, flotation/sedimentation/filtration,
biodegradation (trickling filter, anaerobic, aerated lagoon, rotating biological contactor, and
activated sludge), and clarification. A final polishing step using filtration, ozonation, activated
carbon, or chemical treatment
tment may also be required.
• Liquid effluents should be monitored at least once every eight hours for all the parameters
cited above except metals, which should be monitored at least monthly
monthly.
• Combustion (preceded in some cases by solvent extraction) of tox toxic
ic organics is considered an
effective treatment technology for petrochemical organic wastes. Steam stripping and
oxidation are also used for treating organic waste streams. Spent catalysts are generally sent
back to the suppliers. In some cases, the solid wastes may require stabilization to reduce the
leachability of toxic metals before disposal of in an approved, secure landfill.
• Each shipment of solid waste going for disposal should be monitored for toxics
• Monitoring data should be analyzed and reviewed at regular intervals and compared with the
operating standards so that any necessary corrective actions can be taken. Records of
monitoring results should be kept in an acceptable format. The results should be reported to
the responsible authorities and rerelevant parties, as required.
• Noise abatement measures should achieve either the levels given below or a maximum
increase in background levels of 3 decibels
decibels.

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Bibliography

1. National Petrochemicals Committee of FICCI – 2012-13

2. Bat Guidance Note – Diffuse Or Fugitive Emissions , CARDS 2004 project
3. Techno-Economic
Economic Study On The Reduction Measures, Based On Best Available
Technology, Of Industrial Emissions (Air, Water, Wastes) From The Basic
Petrochemical Industry
4. Chemical and Petrochemical
chemical sector potential of best practice technology and other
measures for improving energy efficiency IEA , information paper.
5. Pollution Prevention and Abatement Handbook, World Bank Group Effective July
1998
6. Multilateral Investment Guarantee Agen Agency Environmental
vironmental Guidelines for
Petrochemicals Manufacturing.
7. BREF Document
Website:

2. http://www.equitymaster.com/research
http://www.equitymaster.com/research-it/sector-info/petrochem/Petrochemicals
info/petrochem/Petrochemicals-
Sector-Analysis-Report.asp
Report.asp
3. http://en.wikipedia.org/wiki/Petrochemical

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