Vous êtes sur la page 1sur 72

ABOUT THE COMPANY

Narmada Chematur Petrochemicals Limited (NCPL),


a joint venture company promoted by GNFC, Chemcatur Engineering
AB, Sweden & IBI Chematur, Mumbai, was established in the Year 1992
to produce 20,000 MTA (Revamped 25,000 MTA) of Aniline and 10,000
MTA of Toluene Di-iso cyanate (TDI) with environment friendly Dupont,
USA Technology. Aniline plant started commercial production in February
1995 whereas TDI plant in July 1998. While Aniline is the largest single
stream plant in the country, TDI is the only plant in entire ASSRC
countries. Both Aniline & TDI plants are being operated above 100 %
capacity utilization.
NCPL has exported its Aniline to Taiwan, Japan, Netherlands, Turkey,
and Belgium & South Africa. Companys TDI, being sold by brand name
of Narmada-Nate-80 is widely accepted in domestic and international
market and has been exported to Belgium, Dubai, China, Turkey, Hong
Kong & Nigeria.
NCPL has been accredited with ISO 9002 by LRQA for its products
viz.,Nitrobenzene, Aniline and TDI for the quality excellence up to
international standards. NCPL has also been awarded prestigious ISO
14000 Certificate under Environmental Management System (EMS) ISO
14000 for its efforts towards continual improvement in preservation of
environmental & pollution abatement. The Company has also bagged the
Best Environmental System & Awareness Award instituted by Society
of environmental Auditors & Consultants (SEAC).
The Company has commissioned its 6 MW Captive Power Plant based
on Natural Gas and Co-generation technology in the month of
November, 1999, which has been catering the entire power requirement
of the Company. This plant has been installed & commissioned in the
record period of only 10 months from zero date. The total project cost of
CPP is Rs. 30 crores.
The company has already spent around Rs. 40/- crores i.e. 10% of its
project Cost in setting up Effluent Treatment Plants, viz.,Nox absorption
unit, incinerator I & II to control generation of pollution and installation of
a LIST for the recovery of TDI , for preservation of environmental and
pollution abatement in the field of Air, Water & Solid Waste Generation.
NCPL is committed to environment protection and maintenance of
ecological balance. In its constant drive for better environment, sustained
efforts are made to create greenery in the factory premises. It has
planted around 26,000 nos. of trees of different varieties and developed
grassland on more than 37,000 m of areas. In the midst of the factory,
the Company has also developed a lotus-pond wherein one can find
ducks and fish, which is an evidence of NCPLs commitment to eco-
friendly environment.
SOMEWHAT MORE,
Share Capital (Paid up) : Rs. 16.19 million
Share Holders : Around 1,27,650 Nos.
Total Cost : Rs.4 billion
Captive Power Plant : 7.6 MW at 27 C
Plot Area : 65 Hectares
TDI (TOLUENE DI
ISOCYANATE) PLANT
INTRODUCTION
TDI is manufactured from MTD (Meta Toluene Diamine) and Phosgene.
These raw materials MTD and Phosgene we are producing in the
company itself.
SPECIFICATION
RAW MATERIAL(PHOSGENE)
CHLORINE
Chlorine 99.5 % min
Non- volatile matter 0.005 max
Moisture 0.005 max
Pressure chlorine can be delivered at
B/L with pressure of 12 bar a
Temperature sufficiently superheated to
eliminate possible condensate
formation

CARBON MONOXIDE
CO 98.3 min
Hydrogen 1 ppm max
Methane 1 ppm max
Nitrogen 0.53 %
Ar 1.17 % max
Pressure 13.3 bar a
Temperature 46 C

ACTIVATED CARBON
Coconut shell based activated carbon produced by high
temperature steam activation of specially selected coconut shell char
feed stock.
Particle size 5 % max + 4.76 mm
90 % min 4.76 to 2.38 mm
5 % max 2.38 mm
Surface area 950 m2 / gm
Density 540 560 kg / m3
Ash 3 % max
Moisture content 1 % max

RAW MATERIALS (TDI)


MTD (Meta Toluene Diamine)
MTD 97.5 %
OTD 0.26 %
Water 125 ppm
Other organics Balance
Phosgene
Chlorine 200 ppm
CO 1 % by vol. Min
ODCB (Ortho Di Chloro Benzene)
Apperance Clear water white liquid
Colour max. 25 on APHA scale
Moisture 0.015 % wt. Max.
Hydrolyzable Chlorine Max. eq. To 0.75 ml of silver nitrate
solution per 100 sample
Para dichloro Benzene 2 % wt Max.
Tri chloro benzene 0.1 % max.
Activated carbon (HCl Purification)
Apparent Density (G/L) 500
Moiusture as packed (%) 5
Ash content(% max) 1
Hardness 96
PH 6.7
Particle Size
> 20 (0.85 mm) 5
< 50 (0.30 mm) 5
< 60 (0.25 mm) 1
Surface area (m/g) 1100

Antioxidant
Tri Phenyl Phosphate (TPP)
Colour max. 50 on APHA scale
Free phenol 0.5 % max
Hydrolyzable Chlorine 0.010 % max.

PRODUCT SPECIFICATION(PHOSGENE)
PHOSGENE
Chlorine 200 ppm max
CO 1 % by vol min
Molecular wt 98.916gm / gmole
Melting point -118 C
Boiling point 7.54 C
Apperance colourless gas
Density 1402.15 kg / m3
TLV 0.1 ppm

FINISHED PRODUCT SPECIFICATION (TDI)


Composition
80/20 blend of 2,4 and 2,6 isomers Di Isocyanate.
Specific Gravity
1.22 +/- 0.02 at 25 C
Requirements
Property Specification limits
Form at 20C Clear liquid
Colour Water white to pale yellow
APHA colour rating 25 max.
Freezing point, C 14.0 +/- 1.0
Purity, % by wt 99.5 min.
Isomer content (% by wt)
2,4 TDI 80.0 +/- 1.0
2,6 TDI 20.0 +/- 1.0
Total acidity(% by wt) 0.004 max.
Hydrolyzable chlorine 0.006 % by wt
Total Chlorine (% by wt) 0.05 max

BY PRODUCT SPECIFICATION
HCl gas
The HCl gas produced equates to approx. 1030 kg/1000 kg of TDI
product.
Composition
HCl 90-97.5 % by wt
CO2 0.5 % by wt.
CO 1.5 % by wt.
N2 0.5 % by wt.
Discharge temperature 2 C
Discharge Pressure 2.3 bar abs

EFFLUENT SPECIFICATION
SALT CAKE
Quantity about 120 kg / 1000 kg product
Composition sodium oxides
Sodium sulphides
Sodium chlorides
Sodium sulphates
Sodium carbonates
MAIN STACK EXHAUST AIR
Quantity
Normal operation 3 m3 / kg product
Peak operation 11.5 m3/ kg product

Composition
ODCB 300 mg / m3 max
CCl4 65 mg / m3 max
HCl traces
Nox traces
TDA traces
TDI traces
Air balance
WASTE TREATING PLANT EXHAUST AIR
Quantity 8000 m3 / 1000 kg product
Composition
Nox as NO2 500 mg / m3
CO2 60 g / m3
CO traces
Water 300 g / m3
Air balance

UTILITY SPECIFICATION
PROCESS AIR
Pressure 3 bar a
Temperature ambient
Quality free from oil and dust
INSTRUMENT AIR
Pressure 4.5 bar abs
Temperature ambient
Dew point - 15 C
Quality oil and dust free
REFRIGERATION CARRIER
Delivery temperature - 17 C
Pressure 6.0 bar abs
Return temperature -8C
Pressure 3.0 bar abs
LP NITROGEN
Pressure 7 bar abs
Temperature ambient
Purity oxygen content 10 ppm
POWER
11 KV, 3 Phase, 3 wire, 50 Hz AC
3.3 KV, 3 Phase, 3 wire, 50 Hz AC
415 V, 3 Phase, 3 wire, 50 HZ AC
voltage variation within 10 %
frequency variation + 3 % to 6%
STEAM
Steam level pressure temperaure
HP superheated 25.5 bar a 340 C
HP saturated 25.5 bar a 225 C
MP saturated 14.7 bar a 197 C
LP saturated 4.0 bar a 143 C
PROCESS WATER
Delivery temperature 25 C
Pressure 5.0 bar a
Total alkalies 16.8
Total solids 938.2 mg/l
Total hardness 4.1 DH
DM WATER
PH 6.5 to 7.5
Conductivity 0.2 umhos/cm
Solica less than 0.02 ppm
Pressure 4 bar a min
Temperature ambient
COOLING WATER
Delivery temperature 33 C
Pressure 5.5 bar a
Return temperature 43 C
Pressure 3.5 bar a
PH 7.5
Conductivity 500 umhos/cm
Silica 20 60 ppm
CHILLED WATER
Delivery temperature 8 C
Pressure 5.5 bar a
Return temperature 13 C
Pressure 3.5 bar a
APPLICATIONS OF TOLUENE DI-
ISOCYNATE (TDI)

FLEXIBLE POLYURETHANE FOAM (FLEXI PUF)


Mattresses, Pillows, Quilts
Furniture
Automobiles : Seats, Linings, Sun Visors
Padding & Lining: Garments, Shoes, Diaries, Carpets, Brief cases,
Bags, Purses etc.
Acoustic Insulation
Industrial Gaskets
Protective pads for sports & Medical uses
Industrial, Automobiles & Household filters
Paint Rollers
Packing : Electronic Items, Frozen Foods, Medicines, Audio Video
Computer CDs
Applicators : Shampoos, Wax, Shoe Polish, Household chemicals
Cleaning tools for pipelines & tubes
Miscellaneous: Toys, Rakhi etc.
Any type of Cushioning

CASE
Coatings
Adhesives
Sealant
Elastomers

PROCESS
DESCRIPTION
PHOSGENE PLANT
Phosgene is the raw material for the production of the TDI. Chlorine is
reacted with carbon monoxide ( 3 mole percent excess over theory ) in
the presence of an activated coconut charcoal catalyst to form
phosgene. The feed gases are metered to the primary reactor, where the
bulk of the chlorine is reacted to form phosgene. The off gases from the
primary reactor passes through the secondary reactor and clean up
tower, where the chlorine content is reduced to less than 0.03 mole
percent. The product gas from the clean up towr is fed to the fresh
phosgene disperser in the phosgenation reaction loop.
The rate of phosgenation production is dictated by phosgene
consumption in the phosgenation step in the TDI plant. Since no
intermediate storage facilities provided, the phosgene equipment will be
operated only during the time the phosgenation facilities require
phosgene. Feed gas flows will be determined by phosgene usage in the
production of TDI

CHEMISTRY OF THE PROCESS


MAIN REACTION
CO + Cl2 ------- COCl2
BY-PRODUCT FORMATION
H2O + CO +Cl2 ----- 2HCl + CO2
H2O + C + HEAT ---- CO + H2
H2 + Cl2 ---- 2HCl + HEAT
CH4 + 4 Cl2 --- CCl4 + 4HCl + HEAT

NH3 + 3Cl2 --- NCl3 + 3 HCl

COMMENTS:
The reaction of water and carbon to carbon monoxide and
hydrogen results in catalyst loss.
The carbon tetrachloride produced from methane and chlorine is TDI
plant taken out as a slip stream, concentrated and incinerated in waste
treating department, to prevent accumulation in the phosgene loop.
The nitro chloride from the reaction of ammonia and chlorine explosive.

DETAILED DESCRIPTION
FEED SYSTEM
Chlorine is obtained by a pipeline from chlorine bullet and fed to the
chlorine carbon mix tee.
Carbon monoxinde is obtained by pipeline from CO recovery plant. In
CO recovery unit. the feed gas comes from GNFC, Bharuch.

The composition of the feed gas is as follows:


Hydrogen 5-7 mol %
Nitrogen 8-12 mol %
CO 42-48 mol %
Ar 10-15 ol %
CH4 25-35 mol %

The compositionof the product gas is as follows:


CO min 98 % (mol)
CH4 1 ppm
Hydrogen 1 ppm
Nitrogen 2 % max( mol)
Capacity - 450 NM3 / hr
Technology supplied by LINDE AG, Germany

Before feeding the gas stream to the phosgene plant oil and moisture, if
any, are removed in the filters.

PRIMARY REACTION
The primary reaction consists of two identical reactors in parallel, each
reactor containing tubes packed with activated charcoal, arranged as a
shell and tube heat exchanger. Heat of reaction is removed by a closed
cooling water system comprising a recycle water cooler, a recycle water
heater, a recycle water expansion vessel and a recycle water pump.
The mixed gases consisting of chlorine and carbon monoxide (3 mole
percent over theory) are fed to the top of the reactors, react in passing
through the bed of the activated charcoal, and leave the reactor bottom.
Most of the chlorine is converted to phosgene in the primary reactor.

One of the two reactors is a stand by so that full capacity can be reached
using one reactor while the second is repacked with fresh catalyst.

SECONDARY REACTION
The secondary reactor consists of two identical reactors in parallel(one
stand by) packed with activated charcoal. The cooling system is the
same as used for the primary reaction

The partially reacted gases from the primary reactor, consisting


principally if phosgene with small amount of unreacted chlorine and
carbon monoxide, are fed to the top of the secondary reactor tubes and
pass downward through the carbon bed leave at the bottom.

CLEAN-UP REACTION
The clean up tower consists of a single vessel packed with a bed of
activated charcoal. No cooing is provided. Gases pass downward
through the packed bed. No reaction should occur in the clean up tower
under normal conditions, it is provided to assure that the final phosgene
will have less than 0.03 mole percent chlorine. High temperature at the
exit of the clean up tower indicates that the unreacted chlorine is getting
past the secondary banks and reacting in the clean up tower.

Phosgene gas leaves the clean up tower and is fed to the fresh
phosgene disperser in the posgenation loop. Phosgene manufacturing
rate is set for desired TDI production rate thus avoiding any storage of
phosgene.

PROCESS
DESCRIPTION
TDI PLANT
The following are the main steps during the manufacture of TDI (Toluene
Di Iso-cyanates)

1. MTD/ODCB SOLUTION DRYING


2. REACTOR FEE SYSTEM
3. PHOSGENATION REACTION
4. DEGASSING
5. HCl STRIPPING
6. PHOSGENE RCOVERY AND PURIFICATION
7. PRIMARY ODCB RECOVERY
8. TAR CONCENTRATIN AND TDI RECOVERY

In Detail,

MTD/ ODCB SOLUTION DRYING


The MTD/ODCB solution drying provides the precautionary step to
ensure the water and ammonia content of the feed solution up to 0.04 %
and nill respectively.
The equipments are
Packed drying column
A reboiler
A pump
A MTD/ODCB feed pump
A condenser
A decanter
An acumalator
A vacuum system, which comprise of a vacuum pump, a cooler
and a separator.
MTD fro storage tanks is fed to a primary mix-tee where ODCB is added
to form 75 % solution of MTD in ODCB. The solution is then fed to the
drying column. Boil-up is supplied by the circulation column bottoms with
the pump through the external steam heated reboiler back to drying
column. Overhead vapours are condensed and cooled in the condenser.
Non condensables containing ammonia passes to the vacuum system.
Condensate from the condenser flows by gravity to decanter. Water
continuously separates from ODCB to an accumulator. This water is
drawn off to the vent scrubber sump. ODCB from decanter flows
continuously by gravity to the drying column as total reflux. A part of the
column bottoms are withdrawn and pumped to the secondary mix tee
and further to the MTD dispersor nozzles in the pipeline reactor.

REACTOR FEED SYSTEM


Dry MTD/ODCB from the bottom of the drying column is pumped to the
secondary mix tee where the solution is diluted up to 15 % MTD and fed
to the MTD dispersion nozzles in the pipeline reactor

Gaseous Phosgene is produced in the Phosgene manufacturing area


and piped o the disperser located in the reactor recirculating loop ,
between the reactor recycle heater and the pipeline reactor.
Phosgene /ODCB solution from the Phosgene absorber is recycled to
the disperser located between the recirculation pump and heater.Thus
we are keeping excess phosgene in the phosgenation loop.

PHOSGENATION REACTION
TDI is produced by the reaction of MTD in ODCB solution with 100 %
excess phosgene in a continuous reaction. Phosgene/ODCB solution is
fed to the recirculation line. MTD/ODCB solution is fed to the MTD
dispersion nozzles in the pipeline reactor. Reaction takes place in the
pipeline reactor and the products of reaction are separated in a gas
liquid separator.

The equipments are,


Reactor separator
Recycle pump
Phosgene disperser
Recycle heater
MTD dispersers
TDI pipeline reactor
Condenser
Off gas separator
Crude TDI/ODCB solution form the reactor separator is recirculated.
Recycle phosgene-ODCB solution is mixed with the recirculating stream
in a disperser to give 100 % excess phosgene over what is
stochiometrically required to react with MTD.
Reaction takes place rapidly and the stream is fed in to the reactor
separator. A mixture f gas containing by product HCl and excess
phosgene is removed overhead and liquid consisting of crude
TDI/ODCB solution plus some dissolved phosgene and HCl is removed
as a slip stream from the bottom by the reactor recycle pump to the
degassing system.

Gases from the reactor separator area cooled from about 150 C to
40C in the reactor condenser. ODCB condensed from the gas stream is
returned to the reactor separator and the cooled gasses are fed to the
phosgene absorber.

DEGASSING
The liquid product stream from the phosgenation reaction system
contains ODCB, phosgene, TDI, HCl, residue and solids (mostly amine
hydrochloride). The main function of the degassing system is to TDI and
HCl. In addition, about 60 % dissolved phosgene and HCl is removed.
The equipments are,
A degasser
A recycle pump
A heater
A condenser
A circulation pump
A degasser compressor
The product stream from the reactor is fed in to the recirculating loop
ahead of the degasser heater. Sufficient residence time is provided in the
degasser for converting the amine hydrochloride formed in the reactor to
TDI and HCl.

Vapors from the degasser are fed to the degasser condenser.


Condensed ODCB from the condenser containing dissolved phosgene is
recycled back to the phosgenation reaction circulating loop. Cooled gas
(mainly phosgene and HCl) from the condenser is fed to the degasser
compressor.
A recirculation line for the outlet stream form the compressor goes to the
condenser for suction pressure control. The remainder of the gas is
mixed with the main off gas stream before it enters the phosgene
absorber. ODCB is purged from the compressor separator and is fed to
the degasser recycle pump. From the circulation pump a slipstream is
taken out to feed the HCl stripping system.

HCl STRIPPING
Liquidf from the degassing system contains ODCB dissolved phosgene.,
TDI and dissolved HCl. The function of HCl stripping column is to remove
the remaining HCl from the product stream. Most of the phosgene, some
ODCB and traces of TDI are also removed.

The equipments are,


A filter
A feed separator
A packed HCl stripping column
A level tank
A pump
A reboiler

The feed stream is pumped through the filters and the feed separator
entering the top of the packed column. Liquid form the column bottom is
fed to the level tank and is then recirculated by the pump through the
stripper reboiler back to ht column.

The product from the HCl stripping column, containing ODCB, residue,
TDI a small amount of dissolved phosgene and traces of HCl, is fed to
the primary ODCB distillation. The vapors from the stripper are mixed
with the degasser vapors just before the degasser condenser.

PHOSGENE RECOVERY AND


PURIFICATION
Phosgene is recovered from the TDI reactor off- gas, which contains
phosgene, HCl and traces of ODCB, by absorption in the ODCB. The
solution of phosgene in ODCB is recycled to the TDI reactor while
gaseous HCl is sent to BL.
The equipment consists of,
A precooler
A chiller cooler
A plate type cooler
A phosgene absorber
A bottoms cooler
A pump
A phosgene recycle pump
The absorber is provided with a demister at the top.
ODCB from one of the ODCB storage tank is cooled in the absorber
precooler, chiller cooler and plate type cooler before entering the
column.The last cooler is operated with refrigeration carrier. ODCB
passing down through the absorber preferentially absorbs phosgene
from the phosgene/HCl gas mixture. The absorber bottom liquid is
circulated through a cooler to maintain the bottom temperature

Off-gas from phosgenation, degassing and HCl stripping are fed to the
bottom of the phosgene absorber. Phosgene/ODCB solution from the
absorber bottom is fed to the TDI reactor with the phosgene recycle
pump. HCl passes up through the absorber. From the top of the
absorber the gas, containing HCl and organic compounds, is sent to
the absorption columns. The organic content is reduced to a
minimum. From the absorption columns the HCl normally leaves as a
gas to BL. If there is no need for HCl gas,it is absorbed in the water to
produce 30% hydrochloric acid.

HCL ABSORPTION SYSTEM


HCl coming from phosgene absorption column is fed to the organic
absorber. There are two organic absorbers to absorb organic of HCl gas.
One absorber remains in line while other in regeneration.
After organic absorber HCl gas fed to the exchanger and then to
absorber to absorb the gas. From here we are preparing 33% HCl which
is stored in storage tanks.
Vent gases from tanks are fed to the scrubbing system and these are
also going to vent scrubber. The scrubbing system for vent gases from
tanks and tanker loading is consists of one tank with absorber at top and
two circulation pumps with ejectors. These eliminates extra load on vent
scrubber.

PRIMARY ODCB RECOVERY


The primary ODCB column concentrates the crude TDI/ODCB solution.
The quipment consists of,
The primary column
Reboiler,
Pump
Condenser
Vent condenser
Vacuum system
Reflux pump
Reflux tank
The ODCB surge tank
ODCB surge pump
ODCB cooler
Crude TDI/ODCB solution is pumped from the stripper level tank to the
primary column. Boil up is supplied by circulating bottoms with the pump
through the reboiler back to the column.

Overhead vapors are condensed and cooled in the primary condenser,


further cooled in the vent condenser and treated in the ccl 4 removal
system. Non-condensables pass to the vacuum pump, which maintains
column top pressure. Condensate from the condenser is collected in the
condensate tanks.

Distilled ODCB is removed as a liquid side stream a number of trays from


the top of the column, collected in the ODCB surge tank and pumped by
the ODCB surge pump through the ODCB cooler, where the temperature
is reduced and returned to the ODCB storage.

Concentrated HCl, phosgene and carbon tetrachloride leave together


with small amounts of ODCB from the column top to the condenser.
From the primary condenser non-condensables are taken to the vent
condenser and the CCL4 removal system.

Concentrated crude TDI/ODCB solution is transferred from the bottom of


the primary ODCB column to the tar concentrator.

TAR CONCENTRATION AND TDI


RECOVERY
Bottoms from the primary ODCB column are pumped to the tar
concentrator. TDI/residue mixture (about 50/50 % wt) from the tar
concentrator bottom is pumped to the TDI recovery unit.

The concentrator reboiler have an installed standby reboiler as the


viscous bottoms co-product is difficult to handle and can cause plugging.
Recovered TDI/ODCB distillate is directly fed to the secondary ODCB
column.

The TDI recovery unit consists of LIST reactor where TDI is stripped off
from the tar solution. The bottom stream is pumped to the tar burner .
Both of these tar concentrator and TDI recovery units are operated under
vacuum.

SECONDARY ODCB RECOVERY


The secondary ODCB column removes the remainder of the ODCB from
the crude TDI/ODCB solution coming from the tar concentrator.
The equipment consists of,
The secondary column
Reboiler
Pump
Condenser
Vent condenser
The vacuum system
Crude TDI/ODCB solution is fed to the secondary column. Boil up is
supplied by circulating bottoms back to the column through the
secondary reboiler. Over head vapors are condensed in the two
condensers. Non condensables are pass to the vacuum pump which
maintains the column top pressure at 25 mmHg. Condensate from the
secondary condenser is collected and fed to the secondary reflux pump
and spit in to two streams.
One part is returned to the top of the column and the remainder is
recycled to the HCl stripper. Crude TDI product form the bottom of the
secondary column , containing a small amount of residue, is fed to the
TDI purification column.

TDI PURIFICATION
Crude TDI from the secondary ODCB column containing trace amounts
of HCl, a small amount of residue and high boiling components is
distilled to improve product quality.
The equipment consists of,
A purification column
A reboiler
A pump
A condenser
A vent condenser
A reflux pump
A TDI surge tank
A TDI pump
A cooler
A condensate tank
A condensate pump
Crude TDI is pumped from the bottom of the secondary column to the
purification column. Boil up is supplied by circulating column bottoms
through the reboiler back to the column. Distilled TDI is removed as a
liquid side stream a number of trays from the top of the column and
collected in the surge tank. The TDI is cooled and sent to the TDI product
day receiver. Overhead vapors are condensed in the condenser and vent
condenser. Non condensables pass to the vacuum system maintaining
the column top pressure. Some of the condensate is returned to the top
of the column as reflux.

A small nitrogen stream is fed in to the column to help controlling product


acidity by removing HCL through the vacuum system. High boilers and
decomposition products accumulated in the bottom of the purification
column are fed to the tar concentrator as a mixture of TDI residue.

VACUUM SYSTEMS
All distillation columns are operating under vacuum. In all cases liquid
ring pumps instead of ejectors avoiding unnecessary contamination of
water, as well as suckbacks generate the vacuum. To rationalize the
operation and reduce the quantity of equipment, most of the columns are
connected in pairs to one common vacuum system.
DRYING VACUUM SYSTEM
The operating pressure of the drying column is 266-mbar abs. The
column is alone served by the drying column vacuum pumps. The
sealing liquid is recycled through the cooler. Make up liquid is
ODCB but as the gas contains moisture ODCB will be
contaminated with water. The overflow from the separator runs to
the start up tank to collect the contaminated ODCB.
PRIMARY VACUUIM SYSTEM
The operating pressure of the primary column is 200 mbar abs.
The column is alone served by a vacuum pump. The seal liquid
ODCB,is recycled and cooled in the heat exchanger. Gas and
liquid are separated in the separator. The ODCB overflows to the
vent condensate tank and is fed to forward by the condensate
pump to the reactor separator.
TDI RECOVERY VACUUM SYSTEM
The operating pressure is between 15 and 33 mbar abs. The
column alone served by the vacuum pump and its ejector. The seal
liquid is ODCB, which is recycled ad cooled in the heat exchanger.
The cooling medium is chilled water to get as low vapor pressure of
the ODCB as possible. The liquid is bled off from the separator by
overflow to the condensate surge tank and is fed forward to the
feed separator.
SECONDARY VACUUM SYSTEM
The operating pressure is between 20 and 33 mbar abs.the
vacuum of the secondary column and the vacuum pump and its
ejector maintain the TDI purification column. The seal liquid ODCB
is recycled and cooled in the same way as in the TDI recovery
vacuum system.

SCRUBBER SYSTEM
The main function of the ventilation and caustic scrubber system is to
remove poisonous substances such as phosgene, chlorine,carbon
monoxide and organics from the vent and process gases before
discharge into atmosphere.
Two caustic scrubbers serving the TDI plant and the phosgene plant.after
scrubbing the gas leaves the plant via main stack. A system for addition
of steam to the main stack during exceptional circumstances is included.
Detail description
The equipment consists of,
Two caustic tanks
A caustic pump
A dilute caustic tank
A dilute caustic pump
A caustic srcubber
Two caustic sumps
A caustic circulation pump
A cooler circulation pump
A caustic cooler
A vent scrubber
Two caustic vent sumps
Two caustic vent pumps
A vent sump cooler
A vent cooler pump
A stack
Three stack fans
There are three types of gases that must be sent to the scrubbers. The
first type is process gases, mainly from the vacuum pumps, which is sent
to the vent scrubber. The second type is gases from the rupture discs
and relief valves which load the caustic scrubber only during emergency
conditions. All of these gases come from the dry part of the TDI and
phosgene manufacturing areas. The third type of gases consists of
ventilation gases and also gases from the TDI storage and drumming,
which is sent to the vent scrubber. Ventilation ducts are connected to
several pieces of equipments which could release phosgene under
unusual conditions. They are connected to a main pipe running to the
vent scrubber.
Caustic soda is received in the caustic tank. Caustic from the caustic
tank and process water are charged to the dilute caustic tank over a mix
to in quantities to produce the desired caustic concentration. The dilute
caustic is circulated through the caustic cooler and back to the tank.
When the caustic concentration in the caustic scrubber sump has
dropped to 9 % or if the interlocking system is activated, the circulation
back to the dilute caustic tank stops and the caustic is fed to the
scrubber system.
Caustic solution, in both scrubber system, is circulated by a caustic
circulation pump from the sump, down through the scrubber and back to
the sump. If the caustic circulation pump stops, the stand by pump will
start/ If caustic circulation is not re-established within a certain time, the
phosgene manufacturing and TDI phosgenation are automatically
interlocked down.
The sodium hydroxide solution make-up for the caustic scrubber is 18 %
wt. When concentration has dropped to 9 % wt NaOH in the operating
caustic sump, there is a switch to the other caustic sump, where fresh
NaOH 18 % wt solution is stored for standby. With this system in
operation, the diluted caustic sump (with NaOH 9%wt) is emptied and
the solution is transferred to the caustic vent sump for further use as a
scrubbing liquid in the vent scrubber thus reducing NaOH consumption.
When the NAOH is used up in the caustic vent scrubber :the solution is
pumped to waste treating.
Exhaust points over sampling valves and elephant trunks are normally
closed in order to reduce the gas load on the vent scrubber and not to
reduce the efficiency of the ventilation system. To maintain good
continuous suction and healthy atmosphere in the plant only the exhaust
points that are used are opened. In case the exhaust fans or caustic
circulation pumps stop. the standby fan or pump will start automatically.
Emergency power must be available within 2 minutes for this equipments
and they shall start automatically when the emergency power is
available.
Normally there is only a small gas flow through the caustic scrubber. In
case of a rupture disc failure, relief valve release or on manual venting
from any equipment containing phosgene,HCL or chlorine the gases will
enter the bottom of the caustic scrubber. They will react with the
circulating caustic and form sodium chloride, Sodium carbonate and
sodium hypo chloride. Inert gas principally air, is discharged from the top
of the caustic scrubber column to the exhaust fan and then to the stack.
An inline analyzer continuously monitors the concentration of NaOH and
Na2CO3 in the scrubbing liquid for the caustic scrubber in order to ensure
that the concentration of the NaOH is kept above 9we%.
Occasionally, the combined sodium chloride and sodium carbonate
content rises to such a level that it could cause deposition of solids in the
fume scrubber. This requires draining of the partially spent solution and
replacing it with fresh caustic and process water.
WAER TREATING
Liquid waste water from the different plants are sent via separate storage
tanks to the waste water mixing tank. From that tank the water pumped
via preconcentrati9n step to an intermediate tan. The water mixture from
the intermediate tank is fed to the burner chamber where the organic
impurities burn on the walls and in the bottom.
Tar form the TDI plant, OTD from the TDA plant as well as fuel oil can be
used as fuels. The tar and the OTD are pumped from the plants to the
fuel storage tanks before being incineration
Inorganic salts in the waste waters, which melt in the bottom of the
incineration chamber will leave through an orifice and flow down to a
water chilled mould. The solid salt blocks are transported to deposit,.
The combustion gases are evacuated by a fan placed in the top of the
tower and pass through demister to remove particles before they exit to
the atmosphere.
Detailed description

INCINERATION
The system consists of,
Waster water mixing tank
Overflow tank
Wastewater pump
Spent caustic buffer tank
Spent caustic pump
Organic trap tank
] Intermediate tank
Different fuel tank
Washing tower with its feed pump
Incinerator chamber with its feed pump
Burner chamber with a burner.
The yellow and red wash waters from the DNT manufacture the amine
water form the catalyst wash and wt scrubbers together with the excess
hydrogenation water, all from the TDA plant are sent to the waster water
mixing tank. If required the pH is adjusted with fresh caustic solution.
The water is pumped to the intermediate tank, where it is mixed with the
predconcentrated liquid recycled from the washing tower. A stream from
the tank is pumped through the washing tower where the liquid is
preconcentrated by the heat form the combustion gases and from a
steam heater in the tower. The concentrated stream is returned to the
intermediate tank.
Liquid form the intermediate tank is fed to the incinerator chamber where
th organic impurities burn on the walls and the bottom of the chamber.
The heat is achieved by burning tar, OTD or oil in the burning chamber
with the provided burner.

COMBUSTION PRODUCTS
The inorganic salts which melt in the bottom of incinerator will leave the
chamber through an orifice and flow down to a water chilled mould .
when a mould is filled it will be replaced by an empty one and the full
one will be transported to a place near by to be further r cooled. The
mould is emptied and the solid ,hard salt block willl be transported to
deposit.
The combustion gases are evacuated by a fan placed in the top of the
washing tower. The gases preconcentrate the waste water and also pass
through demister to take care of small particles on their way through the
tower. They are finally release to the atmosphere.

EMERGENCY
PREPAREDNESS
ODCB SPILLAGE /ODCB TANK
Property:
Colorless liquid with characteristic odour with TLV:50 ppm. Lower
explosive limit of same is 2.2% by volume and upper explosive limit is
9.2% by volume.
Health hazard:

Avoid body contact. May cause CANCER. Prolonged exposure can


cause damage to liver and kidney.
Fire and reactivity hazard:

Keep away from all sparks, flames, heat. Wear full protection. Use water
spray, CO2 DCP type foam.
First aid :

In case of inhalation, remove victim to fresh air. Give artificial respiration.


In case of eye or skin contact wash with plenty of water and remove
contaminated clothing and shoe. In case of swallowing wash
Source out mouth with water.:

1. Leakage /spillage from ODCB tank.


Cause :

1. Weld/pinhole/ leakage.
2. Pump seal leakage. flange joints
3. Catastrophic failure of storage tanks.
Identification :

1. By observing spillage area.


2. By characteristic odour of ODCB.
Remedy:

Isolate the leakage by wearing personnel protective equipments.


Responsibility:

Spilled ODCB to be washed off with water to pit and resultant effluent to
be diverted to incinerator for incineration by operating personnel. In case
of pump seal leakage, pump to be changed over; if stand by is available,
if not then to be isolated with wearing personnel protective equipments
by operating personnel with consultant with shift engineer. After closely
draining pump, pump to be attended. In case of catastrophic failure of
tank, after isolating all inputs maximum material of failed tank to be
transferred to stand by one . As maximum inventory level in each tank is
only 50%. So stand by tank will take care of entire inventory of failed
tank.

ODCB FIRE/ODCB TANK FARM.


Source:

Spillage from ODCB tanks or connected piping /pumps.


Cause:

1. Sparks form hot work job going on near by.


2. Fire from any near by fire/explosion.
Remedy:

1. Fire extinguisher DCP type.


2. Water.
Responsibility:

Operating personnel shall isolate the leakage form source.


operating Area personnel shall act according to the magnitude of fire.
Operating personnel try to extinguish the fire with proper fire
extinguisher/water. In the event of heavy fire, Fire and Safety dep. Shall
be contacted for necessary action.

CAUSTIC SPILLAGE/CAUSTIC TANKFARM


Property :

Colourless, corrosive liquid with density 2.13


Health hazard :
It is very dangerous to eyes and skin. Destroys skin tissues and causes
severe chemical burns. In halation of dust/mist can cause serious injury
to respiratory tract. Ingestion can injure the digestive system.
Fire and health hazard :

Heat is evolved when the material is dissolved in water. Cold water must
be used for this purpose.
First aid :

In case of skin contact wash with plenty of water and remove


contaminated clothing immediately. Get treatment for burns. In case of
eye contact wash with water atleast for 15min. In case of inhalation
remove victim to fresh air. In case of ingestion, drink large quantity of
water or milk followed by diluted vinegar or fruit juice.
Source :

1 Leakage /spillage from caustic tank.


Cause:

1. Weld/pinhole/flange joints leakage.


2. Pump seal leakage.
3. Catastrophic failure of storage tanks.
Identification:

1. By observing spillage area.


Remedy:

Isolate the leakage by wearing personnel protective equipments.


Responsibility:

Spilled caustic to be washed off with water to pit and resultant effluent to
be diverted to incinerator for incineration by operating personnel. In case
of pump seal leakage, pump to be changed over if stand by is available,
if not then to be isolated wearing personnel protective equipments by
operating personnel in consultation with shift engineer. After closely
draining pump, pump to be attended. In case of catastrophic failure of
tank, after isolating all inputs maximum material of failed tank to be
transferred to stand by one.

TDI SPILLAGE /TDI TANK FARM AREA


Property :

TDI is colourless liquid with characteristic odour. Vapour density of same


is 6.0. Lower explosive limit is 0.9% by volume and upper explosive limit
is 9.5% by volume. TLV:0.005 ppm.
Health hazard :

Dangerous if absorbed through the skin or inhaled expoure to slight


vapour can be fetal. Wear full protective clothing, goggles, gloves and
self -contained respirator.

Fire and reactivity hazard :

Fire hazard is moderate emits toxic fumes. Under fire condition thermal
decomposition may produce carbon monoxide. Water may be used to
overcome fire.
First aid :

In case of inhalation remove victim to fresh air and give artificial


respiration. In case of skin and eye contact wash with plenty of water.
Get medical help quickly.
Source :

Leakage /spillage from TDI tanks or connected piping /pumps/drums


leakage/TDI storage tank or drum buckling or bursting.
Cause :

1. Weld/pinhole/flange joints leakage.


2. Pump leakage.
3. Catastrophic failure of storage tank.
4. During drumming activity.
5. Bursting of TDI drums.
Identification:

1. By characteristic odour of TDI.


2. By observing spillage/leakage area.
Remedy:

An effective decontaminating solution can be made as follows.


20% aqueous ammonia solution - 1 part by volume.
Isopropyl alcohol - 1 part by volume.
Water - 18 part by volume.
Above solution should be kept ready.

Responsibility :

Area operator shall act as according to the magnitude of leakage. The


leakage shall be tried to arrest on line with wearing personnel protective
equipment by mechanical personnel, or by isolating part of equuipments
or piping by operating personnel. In case of heavy leakage plant shall be
shut down with consultation with shift engineer and leakage shall be then
attended.
Leakage shall be isolated first by wearing personnel protective
equipments by operating personnel. Spilled TDI to be cover with saw
dust or other absorbed media then with help of shovel shall be collected
in to drum. Collected sawdust shall be incinerated in incinerator.
Decontaminating solution shall be spread on the spillage area and wash
out the flooring. The washed effluent to be diverted to incinerator through
pit pump. In case of frozen spill, solvent containing 50% isopropyl alcohol
and 50% perchloroethelene should be used.
In case of pump seal leakage pump to be changed over; if stand by is
available otherwise pump to be stopped with consultant with shift
engineer and to be closely drained for attending purpose by operating
personnel.
In case of catastrophic failure of tank maximum material of failed tank to
be transferred to stand by one or any other empty tank then leakage to
be attended.
In case of leakage from TDI filled drums maximum possible material from
failed drums to be transferred to another fresh one with help of barrel
pump.

HCl (g) LEAKAGE / TDI PLANT.


Property :

HCl is clear fuming liquid with pungent odour with density 1.639
Health hazard :

Cause severe and painful burns. Do not breath vapour. When there is
danger of breathing vapour, wear approved respirator. When there is
danger of contacting the liquid wear approved respirator and full
protective clothing. Area must be ventilated.
Fire and reactivity hazard :

Contact with some metal produces explosive hydrogen gas. Large


amount of heat is generated on contact with alkaline materials.
First aid:

In case of inhalation, remove victim to fresh air and give artificial


respiration if not breathing. Administer oxygen if coughing persists.
In case of eye or skin contact wash with plenty of water. Remove
contaminated clothing immediately. Treat for burns. In case of swallowing
do not induce vomiting. Get medical treatment quickly.
Source :

Leakage/from HCl(g) line going from E-6654/S-6655 to HCl tank farm.


Cause :

1. Weld /pinhole/flange joing leakage


2. Failure of bellow seals of control valves/isolation valves.
3. Threaded joints of instruments or its connections.
. Remedy :

As HCl(g) can be easily scrubbed with help of caustic solution, for this
purpose vent and emergency scrubber as well as ET network have been
provided in TDI plant, to over come any HCl(g) leakage.
Identification :
1. By characteristic odour
2. By observing white fumes.
3. Ammonia torch for exact leaky point.
Responsibility :

Area operating personnel shall act according to the magnitude of


leakage. The leakage shall be tried to arrest on line or isolating a part of
pipeline / equipment with wearing personnel protective equipment.
Otherwise plant shall be shutdown in consultation with shift engineer and
then leakage shall be attended.
The hold up of HCl (g) inside the system shall be scrubbed in scrubber
via ET network in order to make system HCl free for attending the
leakage.
Rescue :

In the event of heavy HCl leakage, the area shall be evacuated. All the
persons shall be shifted towards upwind direction. Operating personnel
shall cordon the area having HCl(g) leakage for unauthorized entry. The
trapped persons shall be rescued and affected persons shall be given
medical attention

HCl SPILLAGE /HCl TANK FARM


Property :

HCl is clear fuming liquid with punget odour with density 1.639
Health hazard :

Cause severe and painful burns. Do not breath vapour. When there is
danger of breathing vapour, wear approved respirator. When there is
danger of contacting the liquid wear approved respirator and full
protective clothings. Area must be ventilated.
Fire and reactivity hazard :

Contact with some metal produces explosive hydrogen gas. Large


amount of heat is generated on contact with alkaline materials.
First aid:

In case of inhalation, remove victim to fresh air and give artilficial


respiration if not breathing. Administer oxygen if coughing perisits.
In case of eye or skin contact wash with plenty of water. Remove
contaminated clothing immediately. Treat for burns. In case of swallowing
do not induce vomiting. Get medical treatment quickly.
Source :

Leakage/spillage from HCl storage tank or connected piping/pumps or


buckling/bursting of storage tank.
Cause :

1.Weld /pinhole/flange joing leakage


2.Pump/equipments leakage.
3.Catastrophic failure of storage tank.
Identification :

1.By characteristic odour


2.By observing white fumes.
3.By observing spillage or leakage area.
Remedy :

1. Lime powder.
2. Caustic solution.
3. Water.
Responsibility :

Area operator shall act as according to the magnitude of leakage. The


leakage shall be tried to arrest on line with wearing personnel protective
equipment by mechanical personnel, or by isolating part of equuipments
or piping by operating personnel. In case of heavy leakage plant shall be
shut down with consultation with shift engineer and leakage shall be then
attended.
Spilled HCl to be cover with lime powder and then with help of shovel
shall be collected to drum. Caustic solution shall be used for neutralizing
purpose of spilled HCl and resultant effluent to be diverted to incinerator
through pit pump.
In case of pump seal leakage pump to be changed over; if stand by is
available otherwise pump to be stopped with consultation with shift
engineer and to be closely drained for attending purpose by operating
personnel.
In case of catastrophic failure of tank maximum material of failed tank to
be transferred to stand by one or any other empty tank, and leakage to
be attended.
PHOSGENE LEAKAGE/ PHOSGENE PLANT
Property :

Phosgene is colourless highly toxic gas with suffocating odor, with


vapour density 1.4. TLV of phosgene is 0.1 ppm.
Health hazard :

Deadly poisonous. Exposure to slight vapours can be fatal.


Avoid exposure to vapour completely. If there is danger of
contact/exposure wear full protective clothing, goggles, eye gloves and
self contained respirator or breathing apparatus.
Fire and reactivity hazard :

Non flammable gas. Negligible fire hazard when exposed to heat or


flame. Do not use water for extinguishing purpose. Moist phosgene is
very corrosive. Thermal decomposition may release toxic/ hazardous
gases.
First aid :

In case of inhalation, remove the victim to fresh air. Give artificial


respiration, if not breathing. In case of skin contact warm affected skin in
warm water at a temp. of 107 degree F. In case of eye contact wash with
plenty of water and get medical help quickly.
Source :

Any leakage from phosgene plant.


Cause

1. Weld/pinhole/flange joint leakage form piping/equipment.


2. Failure of bellow seals of control valves or isolation valves.
3. Any leakage from phosgene reactor.
Identification :

1. A total of eleven sniffers are installed at different points in Plant.


Based on alarm indication on local panel in control room from any of
the sniffers, phosgene leakage shall be identified. Simultaneously,
hooter will get blown in the plant area, which shall warn the operating
personnel present in the field.
2. With help of portable phosgene dosimeter during plant round taken by
operating personnel.
3. With help of phosgene indicating paper badge, during plant round.
4. By observing characteristic odor like CHIKU.
Remedy :

As phosgene can be easily scrubbed with help of caustic solution, for this
purpose vent and emergency scrubber as well as ET network have been
provided in TDI plant, to over come any phosgene leakage.
Responsibility :

1. Area operating personnel shall act according to the magnitude of


leakage. The leakage shall be tried to arrest on line or isolating a part of
pipeline / equipment with wearing personnel protective equipmetns.
Otherwise plant shall be shut down in consultation with shift engineer
and then leakage shall be attended.
The hold up of phosgene inside the system shall be scrubbed in order to
make system phosgene free for attending the leakage.
2. In case of failure of bellow seals of control valves / isolation valves:
Such valves should be isolated and Elephant trunk should be placed on
such valves to suck leakage by operating personnel with wearing
personnel protective equipment. Valve should be attended /replaced by
mechanical personnel by wearing personnel protective equipment.
3. Explosion of phosgene reactor may be due to over-pressurizing or
corrosion or catastrophic failure. In case of any leakage from phosgene
reactor plant shall be shutdown by shift engineer and operating
personnel shall try to attend arrest the leakage by positive isolation with
wearing personnel protective equipment. In case of heavy phosgene
leakage emergency shall be declared by shift engineer in consultation
with fire and safety dep. Shift engineer will look after evacuation of area
towards up wind direction and cordoning of area to prevent unauthorized
entry & rescue of trapped person with help of personnel protective
equipment.
Rescue :

In the event of heavy phosgene leakage, the area shall be evacuated. All
the persons shall be shifted towards upwind direction. Operating
personnel shall cordon the area having chlorine leakage for unauthorized
entry. The trapped persons shall be rescued and affected persons shall
be given medical attention.

TDI SPILLAGE OR LEAKAGE/TDI PLANT.


Property :
TDI is colourless liquid with characteristic odour. Vapour density of same
is 6.0. Lower explosive limit is 0.9% by volume and upper explosive limit
is 9.5% by volume. TLV:0.005 ppm.
Health hazard :

Dangerous if absorbed through the skin or inhaled exposure to slight


vapour can be fetal. Wear full protective clothing, goggles, gloves and
self contained respirator.
Fire and reactivity hazard :

Fire hazard is moderate emits toxic fumes. Under fire condition thermal
decomposition may produce carbon monoxide. Water may be used to
overcome fire.
First aid :

In case of inhalation remove victim to fresh air and give artificial


respiration. In case of skin and eye contact wash with plenty of water.
Get medical help quickly.
Source :

Any TDI leakage from TDI plant block no.140


Cause :

1 Weld/pinhole/flange joint leakage from piping or equipment.


2 Any leakage from control valves or isolation valves.
3 Any pump leakage.
Identification:

1 By characteristic odour of TDI.


2 By observing spillage/leakage area.
Remedy:
An effective decontaminating solution can be made as follows.
20% aqueous ammonia solution - 1 part by volume.
Isopropyl alcohol - 1 part by volume.
Water - 18 part by volume.
Above solution should be kept ready.
Responsibility :

Area operator shall act as according to the magnitude of leakage. The


leakage shall be tried to arrest on line with wearing personnel protective
equipment by mechanical personnel, or by isolating part of equipment or
piping by operating personnel. In case of heavy leakage plant shall be
shut down with consultant with shift engineer and leakage shall be then
attended.
Leakage shall be isolated first by wearing personnel protective
equipment by operating personnel. Spilled TDI to be cover with saw dust
or other absorbing media then with help of shovel shall be collected in to
drum. Decontaminating solution shall be spread on the spillage area and
wash out the flooring. The washed effluent to be diverted to incinerator
through pit pump. In case of frozen spill, solvent containing 50%
isopropyl alcohol and 50% perchloroethylene should be used.
Contaminated saw dust shall be incinerated.
In case of pump seal leakage pump to be changed over; if stand by is
available otherwise pump to be stopped with consultant with shift
engineer and to be closely drained for attending purpose by operating
personnel.
In case of catastrophic failure of any equipment maximum material of
failed equipment shall be transferred to GPT or other sections if TDI is
leaking and leakage to be attended. The spilled material shall be handled
as stipulated above. In the case of heavy leakage, emergency shall be
declared by shift engineer in consultation with F&S dept.
Communication to the higher authority shall be made from engineer at
the control room for further communication to near by community and
local governing authorities in the event of emergency.
Rescue :

In the event of heavy TDI leakage, the area shall be evacuated. All the
persons shall be shifted towards upwind direction. Operating personnel
shall cordon the area having TDI leakage for unauthorized entry. The
trapped persons shall be rescued and affected persons shall be given
medical attention.

CO LEAKAGE-CO PLANT
Property :
Colourless, odourless gas with vapour density 0.97
TLV of same is 50 ppm. Lower explosive limit is 12.5% by volume and
upper explosive limit is 74.2% by volume.
Health hazard :
An anesthetic action. Symptoms are depression, restlessness,
unconsciousness, disturbance in vision, dizziness, vomiting and
headache. Skin sensation of heaviness and coldness. State of weakness
of limbs. Central nervous system gets demaged permanently.
Fire and reactivity hazard :
Highly dangerous when exposed to heat, spark or friction.
First aid :
Remove victim to fresh air. The area should be free from CO gas and
comfortably warm. Give artificial respiration if not breathing. In case of
skin or eye contact wash with plenty of water immediately. It is extremely
important to see patient warm. Blanket may be used to maintain body
temperature.
Source :
1. Any leakage from cold box or compressor.
Cause :
1. Weld/pinhole/flange joint leakage
2. Failure of bellow seals of control valves
3. Seal leakage from expander turbine.
4. Leakage from threaded joints of instruments and accessories.
Identification :
1. A total of eight sniffers are installed at different points in Plant. Based
on alarm indication on local panel in control room from any of the
sniffers, CO leakage shall be identified. Simultaneously, hooter will get
blown in the plant area, which shall warn the operating personnel present
in the field.
2. With help of portable CO dosimeter during plant round taken by
operating personnel.
Remedy :
Since CO is both toxic and explosive, and since it cant be scrubbed,
leakage has to be isolated and duly attended by wearing personnel
protective equipment.
Responsibility :
Area operating personnel shall act according to the magnitude of
leakage. The leakage shall be tried to arrest on line or isolating a part of
pipeline / equipment. Otherwise plant shall be shutdown in consultation
with shift engineer and then leakage shall be attended.
The hold up of CO inside the system shall be flared and purged with
nitrogen in order to make system CO free for attending the leakage.
Rescue :
In the event of CO leakage, the area shall be evacuated. All the persons
shall be shifted towards upwind direction. Operating personnel shall
cordon the area having CO leakage for unauthorized entry. The trapped
persons shall be rescued and affected persons shall be given medical
attention.

CHLORINE LEAKAGE FROM CHLORINE HANDLING SYSTEM


Property :
Chlorine is greenish yellow gas with liquid or rhombic crystals. Vapour
density of 2.49 kg/m3 and TLV of same is 1ppm.
Health hazard :
It is extremely irritant to eyes, nose and throat. Its vapour can cause
headache, coughing, pain in the chest. In extreme cases, breathing
difficulty may reach the point where death is possible by suffocation.
Fire and reactivity hazard :
Fire hazard is moderate, it can react to cause fire and explosion on
coming contact with turpentine lather, ammonia and hydrocarbons, Shut
off the outlet of leakage, if it is safe to do so. Increase ventilation. When it
is heated, it emits dangerous fumes of HCl. DO NOT SPRAY ANY
WATER ON CHLORINE LEAKS AS CHLORINE REACTS WITH
WATER TO PRODUCE HCL, WHICH IS CORROSIVE
First aid :
In case of inhalation, remove victim to fresh air and give artificial
respiration, if not breathing. Incase of eye or skin contact wash with
plenty of water. Remove contaminated clothing, and get medical help
quickly.
Source :
1. Chlorine leakage form chlorine tonner shed.
2. Chlorine leakage form chlorine bullet area.
3. Chlorine leakage from chlorine scrubber area.
4. Unscrubbed chlorine from vent of chlorine scrubber.
Identification :
1. Chlorine leakage can be easily identified by its characteristic odour
and amber (greenish-yellow) colour.
2. A total eight no. of sniffers are installed at different location of the
plant and based on alarm generated on local /DCS panel in side
control room, leakage shall be easily identified.
3. With help of portable chlorine dosimeter during plant round by
operating personnel.
4. Exact leaky point shall be identified with help of ammonia torch.

Remedy :
As chlorine can be easily scrubbed with help of caustic solution. For this
purpose chlorine scrubber system having one working and one stand by
scrubber, two caustic sumps, two caustic circulation pumps and two
exhaust blowers has been provided. To absorb heat of neutralization,
separate chilled water system has been provided to chill the circulating
caustic.
1 Chlorine leakage form chlorine tonner shed.
Possible leakages from chlorine tonner shed are as follows.
1. Passing of valve mounted on tonner.
2. Leakage from the shell of tonner.
3. Residual chlorine inside flexible copper tubing.
4. Passing of valves from chlorine transferring header.
5. Weld/pinhole/flange joints leakage of piping/equipment.
6. Failure of bellow seals of control valves or isolation valves.
Responsibility :
1. In case of passing of valves mounted on tonner, valves of such tonner
should be attended first with wearing personnel protective equipment
by mechanical personnel, otherwise such tonner should be unloaded
first with wearing personnel protective equipment by operating
personnel. Elephant trunk should be placed on leaky point till such
tonner placed for unloading on unloading platform gets fully unloaded.
If such tonner not getting unloaded because of jamming of isolation
valve which is passing too, isolation valve shall be clamped to isolate
the leakage. (Such clamps are lying in the emergency kit, kept in
chlorine tonner shed). External chlorine experts shall be contacted to
attend such valves.
2. In case of leakage from shell of chlorine tonner shed.
If leakage is minor, elephant trunk shall be placed on such leaky
point. If leakage is heavy, specially designed FRP hood shall be
placed on tonner to cover it completely. The vent of this hood should
be connected to the scrubber via elephant trunk by operating
personnel.
3. Residual chlorine inside flexible copper tubing
Elephant trunk shall be placed by operating personnel to suck residue
chlorine, if left after depressurising it in to the chlorine vent header.
4. In case of passing of valves from chlorine transferring header, the
leakage should be scrubbed in to the chlorine scrubber through
chlorine vent header or through elephant trunk. Valves should be
attended/blinded/replaced by wearing personnel protective
equipments by mechanical personnel.
5. In case of weld/pinhole/flange joint leakage of pipes/equipments
The leakage shall be tried to arrest on line by providing clamping
Or by isolating a part of pipe/ equipments . Isolating portion should be
depressurised in to the scrubber by elephant trunk in order to make the
system chlorine free, prior to attend the leakage.
6. In case of failure of bellow seals of control valves/isolation valves.
Such valves should be isolated and Elephant trunk should be placed
on such valves to suck leakage by operating personnel with wearing
personnel protective equipmetns. Valve should be attended /replaced
by mechanical personnel by wearing personnel protective
equipments.
2. Chlorine leakage form chlorine bullet area.
Possible leakages from chlorine bullet area are as follows.
1. Weld/pinhole/flange joint leakage on piping/equipments.
2. Failure of bellow seals of control valves or isolation valves.
3. Explosion of bullet
Responsibility:
1. In case of weld/pinhole/flange joint leakage of pipes/equipments
The leakage shall be tried to arrest on line by providing clamping
Or by isolating a part of pipe/ equipments. Isolating portion should be
depressurized in to the scrubber by elephant trunk in order to make
the system chlorine free, prior to attend the leakage. In case of pin
hole or immediate flange joint leakage on chlorine bullet, which could
not possible to isolate, all chlorine quantity inside the bullet shall be
transferred to stand by bullet and bullet should be depressurized in
chlorine scrubber to make bullet chlorine free for attending leakage
mean while elephant trunk should be placed on leakage point to
prevent chlorine exposure to the atmosphere.
2. In case of failure of bellow seals of control valves or isolation valve,
. such valves should be isolated and Elephant trunk should be placed
on such valves to suck leakage by operating personnel with wearing
personnel protective equipments. Valve should be attended
/replaced by mechanical personnel by wearing personnel protective
equipments.
3. In case of explosion of bullet.
Explosion of bullet may be due to overpressurising or corrosion or
catastrophic failure. Emergency shall be declared by shift enginner in
consultation with fire and safety dep. Shift engineer will look after
evacuation of area towards up wind direction and corderning of area
to prevent unauthorized entry & rescue of trapped person with help
of personnel protective equipments. Shift-engineer will infrom higher
authority for further action like informing near by community , local
authority etc.
Chlorine leakage form chlorine scrubber area.
Possible leakages from chlorine scrubber area are as follows
1. Weld/pinhole/flange joint leakage on piping/equipments
2. Failure of bellow seals of controlvalves or isolation valve
3. Unscrubbed chlorine form vent of chlorine scrubber.
Responsibility:
In case of failure of bellow seals of control valve/isolation valve
. Such valves should be isolated and Elephant trunk should be placed
on such valves to suck leakage by operating personnel with wearing
personnel protective equipments. Valve should be attended /replaced
by mechanical personnel by wearing personnel protective
equipments.
1. In case of weld/pinhole/flange joint leakage -piping/equipment
The leakage shall be tried to arrest on line by providing clamping
Or by isolating a part of pipe/ equipments. Isolating portion should be
depressurized in to the scrubber by elephant trunk in order to make
the system chlorine free, prior to attend the leakage.
2. Unscrubbed chlorine from vent of chlorine scrubber.
Release of unscrubbed chlorine from vent of scrubber results from
inefficient scrubbing eilther because of poor vacuums or because of
exhausted circulating caustic solution. In case of poor vacuums
exhaust blower shall be changed over and if still problem of poor
vacuums persists, then it may resulting from chocking of packing
inside the scrubber and in such event chlorine scrubber should be
changed over. In case of exhausted circulating caustic solution ,
fresh caustic sump to be taken in line by operating personnel.
PHOSGENE LEAKAGE IN TDI PLANT
Property :

Phosgene is colourless highly toxic gas with suffocating odor, with


vapour density 1.4 . TLV of phosgene is 0.1 ppm.
Health hazard :

Deadly poisonous. Exposure to slight vapours can be fatal.


Avoid exposure to vapour completely. If there is danger of
contact/exposure wear full protective clothing, goggles, eye gloves and
self contained respirator or breathing apparatus.
Fire and reactivity hazard :

Non flamable gas. Negligible fire hazard when exposed to heat or flame.
Do not use water for extinguishing purpose. Moist phosgene is very
corrosive. Thermal decomposition may release toxic/ hazardous gases.
First aid :

In case of inhalation, remove the victim to fresh air. Give artificial


respiration, if not breathing. In case of skin contact warm affected skin in
warm water at a temp. of 107 degree F. In case of eye contact wash with
plenty of water and get medical help quickly.
Source :

Any leakage from TDI plant (block 140).


Cause :

1. Weld/pinhole/flange joint leakage form piping/equipment.


2. Failure of bellow seals of control valves or isolation valves.
3. Any leakage from pumps.
Identification :
1. A total of twenty sniffers are installed at different points in Plant. Based
on alarm indication on DCS panel in control room from any of the
sniffers, phosgene leakage shall be identified. Simultaneously, hooter
will get blown in the plant area, which shall warn the operating
personnel present in the field.
2. With help of portable phosgene dosimeter during plant round taken by
operating personnel.
1. With help of phosgene indicating paper badge, during plant round.
2. By observing characteristic odor like CHIKU.
Remedy :

As phosgene can be easily scrubbed with help of caustic solution, for this
purpose vent and emergency scrubber as well as ET network have been
provided in TDI plant, to over come any phosgene leakage.
Responsibility :

1. Area operating personnel shall act according to the magnitude of


leakage. The leakage shall be tried to arrest on line or isolating a part of
pipeline / equipment with wearing personnel protective equipment.
Otherwise plant shall be shut down in consultation with shift engineer
and then leakage shall be attended.
The hold up of phosgene inside the system shall be scrubbed in order to
make system phosgene free for attending the leakage. N2 purging shall
be done.
2. In case of failure of bellow seals of control valves/isolation valves.
Such valves should be isolated and Elephant trunk should be placed on
such valves to suck leakage by operating personnel with wearing
personnel protective equipment. Valve should be attended /replaced by
mechanical personnel by wearing personnel protective equipment.
3. In the event of explosion of any equipment due to over pressurizing or
corrosion or catastrophic failure, plant shall be shutdown by shift
engineer and operating personnel shall try to attend arrest the leakage
by positive isolation with wearing personnel protective equipment. In
case of heavy phosgene leakage, emergency shall be declared by shift
engineer in consultation with fire and safety dept. Shift engineer will look
after evacuation of area towards up wind direction and cordoning of area
to prevent unauthorized entry & rescue of trapped person with help of
personnel protective equipment.
Rescue :

In the event of heavy phosgene leakage, the area shall be evacuated. All
the persons shall be shifted towards upwind direction. Operating
personnel shall cordon the area having phosgene leakage for
unauthorized entry. The trapped persons shall be rescued and affected
persons shall be given medical attention.

FLASH VESSEL(STEAM) EXPLOSION/ TDI PLANT


Source :

Flash vessel of steam. T-50473


Cause :
Over pressurization of flash vessel because of mal-functioning of
pressure controller valve or indicating instruments /safety valve.
Responsibility :

Area operating personnel shall immediately isolate all inputs to the flash
vessel. Inform the shift engineer in control room for further
communication.
Rescue :

In the event of heavy explosion, the area shall be evacuated. All the
persons shall be shifted towards upwind direction. Operating personnel
shall cordon the area having explosion, for unauthorized entry. The
trapped persons shall be rescued and affected persons shall be given
medical attention.
TDI-TAR SPILLAGE /TDI PLANT
Source :

Any leakage/spillage from piping /pump of 72 section of TDI plant.


Cause :

1 Weld/pinhole/flange joint leakage from piping or equipment.


2 Seal leakage from pump.
3 Spillage during draining of TDI-TAR in drums/drum tilting/drum
leakage.
Identification :

1. By physical observation of any spillage/leakage.


2. Characteristic pungent odor of TDI.
Remedy:

An effective decontaminating solution can be made as follows.


20% aqueous ammonia solution -1 part by volume
Isopropyl alcohol -1 part by volume
Water -18 part by volume
Above solution should be kept ready.
Responsibility :

Area operator shall act as according to the magnitude of leakage. The


leakage shall be tried to arrest on line with wearing personnel protective
equipment by mechanical personnel, or by isolating part of equipment or
piping by operating personnel. In case of heavy leakage plant shall be
shut down with consultant with shift engineer and leakage shall be then
attended.
Leakage shall be isolated first by wearing personnel protective
equipment by operating personnel. Spilled TDI/TAR to be cover with saw
dust or other absorbed media then with help of shovel shall be collected
in to drum. Decontaminating solution shall be spread on the spillage area
and wash out the flooring. The washed effluent to be diverted to
incinerator through pit pump. In case of frozen spill, solvent containing
50% isopropyl alcohol and 50% perchloroethylene should be used.
In case of pump seal leakage pump to be changed over; if stand by is
available otherwise pump to be stopped with consultant with shift
engineer and to be closely drained for attending purpose by operating
personnel.
Rescue :

In the event of heavy TDI/TAR leakage, the area shall be evacuated. All
the persons shall be shifted towards upwind direction. Operating
personnel shall cordon the area having TDI/TAR leakage for
unauthorized entry. The trapped persons shall be rescued and affected
persons shall be given medical attention pertaining personnel.
TDI FIRE /TDI PLANT
Source :

Any TDI spillage in TDI plant (block-140)


Cause :

Spark form any hot work job going on.


Fire and reactivity hazard :

Fire hazard is moderate emits toxic fumes. Under fire condition thermal
decomposition may produce carbon monoxide. Water may be used to
overcome fire.
Remedy :

1. Fire extinguisher type foam or DCP type.


2. Water
Responsibility :

Area operating personnel shall act according to the magnitude of fire.


Operating personnel shall try to isolate the leakage by wearing personnel
protective equipment and extinguish the fire with proper fire extinguisher/
water and inform control room for further communications. In the event of
heavy fire, Fire and Safety dept. shall be contacted for necessary action.
Rescue :

In the event of heavy TDI fire, the area shall be evacuated. All the
persons shall be shifted towards upwind direction. Operating personnel
shall cordon the area having TDI fire for unauthorized entry. The trapped
persons shall be rescued and affected persons shall be given medical
attention
ORGANIC SPILLAGE-LEAKAGE/TDI PLANT.
Source :

Any organic spillage or leakage from TDI plant (block 140).


Identification:

1. By any characteristic odour.


2. By observing spillage/leakage area.
Responsibility :

Area operator shall act as according to the magnitude of leakage. The


leakage shall be tried to arrest on line with wearing personnel protective
equipment by mechanical personnel, or by isolating part of equipment or
piping by operating personnel. In case of heavy leakage plant shall be
shut down with consultant with shift engineer and leakage shall be then
attended.
Leakage shall be isolated first by wearing personnel protective
equipment by operating personnel. Spilled organic material to be cover
with saw dust or other absorbing media then with help of shovel shall be
collected in to drum. Wash out the flooring with water /hot water/steam.
The washed effluent to be diverted to incinerator through pit pump.
Rescue :

In the event of heavy organic leakage, the area shall be evacuated. All
the persons shall be shifted towards upwind direction. Operating
personnel shall cordon the area having organic leakage for unauthorized
entry. The trapped persons shall be rescued and affected persons shall
be given medical attention.
CHEMISTRY OF THE PROCESS
(TDI PLANT)
PHOSGENATION
MAIN REACTIONS

Reaction to carbamyl chloride


CH3 CH3
NH2 NHCOCL
2COCL2

- 2HCL
NH2 NHCOCL
MTD CARBAMYL
CHLORIDE

Reaction from carbamyl chloride to TDI

CH3 CH3
NHCOCL NCO

- 2 HCL
NHCOCL NCO
CARBAMYL
CHLORIDE TDI

Reaction to diamine hydrochloride


CH3 CH3
NH2 NH2HCL
+ 2HCL

NH2 NH2HCL
MTD DI AMINE
HYDROCHLORIDE

Reaction from diamine hydrochloride to TDI

CH3 CH3
NH2HCL NCO
2COCL2
- 6 HCL

NH2HCL NCO

TDI
DI AMINE
HYDROCHLORIDE
YIELD LOSS REACTIONS

C7H6(NH2)2 + C7H6(NCO)2 ------- C7H6NH2-NHCONH-C7H6NCO

C7H6(NH2)2+C7H6(NHCOCl)2------- C7H6NH2-NHCONH-C7H6NCO

C7H6(NCO)2 + H2O ------ C7H6NH2NCO + CO2(g)

C7H6NH2NCO+ C7H6(NCO)2 ------ C7H6NCO-NHCONH-C7H6NCO

CAUSTIC SCRUBBING

COCL2 + 4NaOH(aq) ---------- Na2CO3 + 2NaCl + 2H2O + Heat

HCl + NaOH(aq) -------- NaCl + H2O + Heat

Cl2 + 2NaOH(aq) ------ NaOCl + NaCl + H2O

CO2 + 2NaOH(aq) ------ Na2CO3 +H2O

CO + NaOH(aq) ----- No Reaction