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Gujarat Narmada Valley

Fertilizer Co.Ltd

( Aniline-TDI complex)
WEST
GATE
Water Cooling Control AN Aniline
sump Tower room substation Plant
Tech. Sub ETP
Building station

PFB
Canteen Utility TDI MTD DNT
Plant pump/Bunker
CPP PHOSGENE NB SAC
Plant unit
Pond
Incinerator
Flare OHC Chlorine Chlorine Acid &
stack Scrubber tonner DNT Aniline
and plant T/F
Fire Bullet CO
station TDI, HCL Tank farm

Ware ODCB Benzene &


House storage Toluene Tank
farm

N
MAIN
LAY OUT PLAN OF GNFC GATE NH No. 8

(Ani-TDI complex)
Aniline Plant

Technology supplied by :- M/S Dupont of U.S.A.

Basic engineering is done by :- M/S Chematur Engg. AB,


Sweden.

Detailed engineering is done by :- M/S IBI Chematur Engg. AB,


Bombay
Raw Materials & Utilities for
Aniline Plant
Raw Materials Major Utilities
Benzene Steam
Sulfuric acid Water
Nitric acid Nitrogen
Hydrogen Power
Pd/Pt based catalyst Chilled water
ANILINE PLANT: BLOCK DIAGRAM

Conc. Nitric
Benzene Acid Hydrogen

Conc. Nitro
Aniline
Sulphuric Acid Benzene Purification
Reactor
Plant

70% Sulphuric Catalyst


Acid ANILINE
PRODUCT
Spent Acid
Conc. Concentration
Sulphuric Acid Unit
TDI Plant
Technology supplied by :- M/S Dupont of U.S.A.

Basic engineering is done by by :- M/S Chematur Engg. AB,


Sweden.

Detailed engineering is done by by :- M/S IBI Chematur Engg. AB,


Bombay

Raw Materials & Utilities for


TDI Plant
Raw Materials Major Utilities
Toluene Steam

Sulfuric acid Water


Nitric acid Nitrogen
Hydrogen Power
Chlorine Chilled water
CO Chilled Brine
BLOCK DIAGRAM FOR TDI GROUP OF PLANTS
CL2 Bullet
Tail Gas Cold Box CO

CO Evaporator
CO From A.A Cl2

Phosgene Unit ODCB


H2
NaOH TDI
CNA Cat. Slurry
Cat.Prep Storage
Toluene TDI

DNT PlantDNTTDA PlantMTD TDI Plant HCl Gas

SA
OTD Crude TDI TDI

NOx Unit LIST UNIT HCl Unit


INCINERATORS
WNA
Vent TA HCl
Dil.SA R
Solid waste Flue Gases (30%)
Plant safety
Sr.No Plant Hazardous Present In-Built Safety Facilities
Activity
1 NB Nitration of Safest technology, sprinkler provided at reactor/distillation
benzene section to mitigate an emergency during run away reaction.
Interlock provided for safe shut down of plant from DCS
2 Aniline Hydrogenati Sprinkler provided at reactor/ Hydrogen handalling area to
on of Nitro mitigate an emergency during run away reaction. Interlock
Benzene provided for safe shut down of plant from DCS. Hydrogen vent
line modified as suggested by M/S EIL to avoid fire.
3 DNT Nitration of Safest technology, interlock provided for safe shut down of
Toluene plant from DCS
4 MTD Hydrogenati Sprinkler provided at reactor/ Hydrogen handalling area to
on of DNT mitigate an emergency during run away reaction. Interlock
provided for safe shut down of plant from DCS.Catch tank &
Emergency flare seal pot system installed to handle safe
venting / draining & s
5 Phosgene Phosgene No storage of pure phosgeneIn, Cl2 & Phosgene plants
generation minimum flange joints (Tongue &groove type) & high
schedule pipe rating helped in preventing leakages.Online CO
/ Cl2 analyzer in phosgene synthesis
6 TDI Phosgenatio Online analyser of Phosgene / HCl in TDI synthesis.Multiple
n of MTD in interlocking system to cutoff feed automatically on any
presence of process deviation e.g.Temperature / pressure / flow ..etc
ODCB
Safety seatures at Tankfarm area
Sr. Hazardous Storage Hazardous Present In-Built Safety Facilities
No Materials Capacity Properties
Toxic Flamm
able,
Raw Materials
1 Benzene 1300 M t T ank design as per CCE, emergency vent provided
* * to avoid pressurisation of tank, FLA provided to
avoid back fire. Sprinkler & foam system is
installed. Sniffer provided for early detection.
Earthing interlock provided while unloading
tankers.

2 T oluene 700 M t T ank design as per CCE, emergency vent provided


* * to avoid pressurisation of tank, FLA provided to
avoid back fire. Sprinkler & foam system is
installed.

3 Chlorine 300 M t Bullet design as per CCE, emergency vent


(effective * scrubber provided to mitigate any emergency
storage 175 leakage. Emeregncy standby bullet available and
Mt) in bullet to be lined up from DCS. ( 4th bullet will be installed
& 200 to mitigate an emrgency when one bullet is under
tonner maintanace.)

4 Nitric Acid 350 M t Pressure / vaccum seal pot provided to avoid


* pressurisation / vaccum while loading / unloading.

5 Ortho Di- 90 M t Nitrogen blanketting provided to avoid ingression


Chloro * * of oxygen.
benzene

6 Carbon No storage Sniffer installed for early detection, excessive CO


Monoxide * * will be burn at flare / incinerator.
Safety features at Tankfarm area
Sr. Hazardous Storage Hazardous Present In-Built Safety Facilities
No Materials Capacity Properties
Toxic Flamm
able,
Intermediates
1 Nitro 500 Mt Dyke wall provided for catchment of leakage. Safest
Benzene * * technology for nitration.
2 DNT (Di- 50 Mt ( 65% Storage as per CCE approval, bunker provided for the
Nitro water) * * handalling of pure DNT. Safest technology for nitration
Toluene) system.
3 MTD ( Meta 350 Mt Dyke wall provided for catchment of leakage, reactor is
Toluene * * protected by sprinkler system to mitigate an emergency.
Diamine)
4 Phosgene No storage Caustic scrubber system to evacuate hold up volume of
* cl2/phosgene & any leakages in plant through elephant
trunk in case of emergency, sniffer provided in plant for
early detection. Ammonia sprinkler system installation is
under progress.
Safety features at Tankfarm area
Sr. Hazardous Storage Hazardous Present In-Built Safety Facilities
No Materials Capacity Properties
Toxic Flamm
able,
Products
1 Aniline 4000 Mt Dyke wall provided for catchment of leakage, PVRV &
* * PCV provided to avoid pressurisation & vacuum.
2 TDI (80:20) 1450 Mt Dyke wall provided for catchment of leakage ,Tank vents
* * are lined up with an emergency scrubber.
3 HCl (30%) 1150 Mt Dyke wall provided for catchment of leakage ,Tank vents
* are lined up with a scrubber.
Plants Set-up :
Aniline Plant
Design Capacity 20,000 MTPA
Revamped capacity @ 35,000 MTPA

Toluene Di-Isocyanate (TDI)


Design Capacity 10,000 MTPA
Revamped capacity @ 14,000 MTPA
Reaction Chemistry
1) Nitration of Benzene to Nitrobenzene
H2SO4
C6H6 + HNO3 ------------- C6H5NO2 +H20+Heat
Nitro benzene
By Products formation : Di-nitro Phenol, Di-nitro Benzene

(2) Hydrogenation of Nitrobenzene to Aniline


Catalyst Pd-Pt
C6H5NO2 + 3H2 -----------------------C6H5NH2 +2H20+Heat

Aniline
By Products formation : Tar
Reaction Chemistry
(1) Nitration of Toluene to Di- Nitro toluene
H2SO4
C6H5 CH3 +2 HNO3 C6H3-CH3-(NO2) 2 +2H20+Heat
DNT
(2) Hydrogenation of Di Nitro toluene to Meta Toluene Di Amine (MTD)
Catalyst PdCl2
C6H3-CH3-(NO2) 2 + 6H2 C6H3-CH3-(NH2)2+ 4H20 + Heat
MTD
(3) Phosgene Gas Synthesis
CO + CL2 COCL2
Phosgene
(4) Phosgenation of (MTD) to Toluene Di Isocyanate (TDI)

C6H3-CH3-(NH2)2 + 2COCl2 C7H6(N-CO)2 + 4HCl


TDI
Safety features of
Aniline/TDI plants
SAFETY FEATURES OF ANILINE PLANTS (Engineering control)
1. Safest Nitration pump technology used for NB nitration.
2. Emergency draining system is installed in NB plant.
3. Scrubbing system installed for scrubbing of organic & acidic
fumes from equipments / intermediate & Product tanks.
4. Water sprinkler system installed surrounding Aniline Reactor &
all organic handling area to mitigate any fire hazards.
5. H2 vent line modified as suggested by M/S EIL, India
6. Sniffer installed at NB plant & Benzene storage tank for early
detection of leakage.
7. Rupture disc followed by Safety valve installed at various
equipment handling hazardous chemicals.
8. Multiple interlocking system to cutoff feed automatically on any
process deviation e.g.Temperature / pressure / flow ..etc
9. Required Antidotes ( Methylene Blue) kept at OHC
10.Earthling interlocks installed while loading/ unloading of
organic materials in/from tankers.
11.Foam chamber & water curtain system installed in Benzene /
Toluene storage tanks/ tanker area as per CCE .
SAFETY FEATURES OF TDI PLANTS (Engineering controls)
1. Safest Nitration pump technology used for DNT formation
2. Metering pump used for safe operation of nitration.
3. DNT stored in emulsion form (I.e. 33% DNT & rest is water in
continuously suspension form by circulating pump having
emergency power backup).
4. Emergency draining system is installed below Ground level.
5. Pure DNT handling pump kept inside bunker having 1 Mtr thick
wall of RCC and is 45 Mtr. away from DNT plant. The maximum
inventory of pure DNT is 100 Kg at a time.
6. Water sprinkler system installed surrounding MTD H2-Reactor
to mitigate any fire hazards.
7. Catch tank & Emergency flare seal pot system installed to
handle safe venting / draining & scrubbing of H2.
8. Wet scrubbing system installed to scrub release of inert from
intermediate / Product tank.
9. SAFER system Installed to guess the extent of leakage after
manual entry of data.
SAFETY FEATURES OF TDI PLANTS (Engineering controls)
10. No storage of pure phosgene
11. In Cl2 & Phosgene plants minimum flange joints (Tongue &groove
type) & high schedule pipe rating helped in preventing leakages.
12. Online CO / Cl2 analyzer in phosgene synthesis & Phosgene / HCl
analyzer in TDI synthesis.
13. Multiple interlocking system to cutoff feed automatically on any
process deviation e.g.Temperature / pressure / flow ..etc
14. Rupture disc followed by safety valve installed in all hazardous
chemicals handballing equipments.
15. Caustic scrubber system to evacuate hold up volume of cl2/phosgene
& any leakages in plant through elephant trunk in case of emergency.
16. Sniffer for detecting CO,Cl2,Phosgene are installed at various location
to identify leakage at the earliest and plant can be stopped from C/R &
field immediately.
17. Ammonia Curtaining system installed surrounding phosgene plant to
contain leakage.
18. To the extent magnetic driven pumps used to avoid exposure on
account of seal leakage
19. Emergency power backup given to critical motor for scrubber &
evacuation system
Hazardous property of Chemicals used in Aniline / TDI plants

Sr. Name TLV Special PPE Remarks


No of limit in other than
Chemic ppm Safety
als helmets,
shoes,
1 Benzen 0.5 goggles, vapor
Organic hand Proven carcinogenic
e gloves may
respirator compound having sweet
be worn smell, flammable, explosive
and non conductive
2 Toluen 100,th Organic vapor Flammable, Explosive,
e e odor respirator may Suspected carcinogen
thresh be worn
old
0.17
3 CNA ppm
2 Corrosive, Emits toxic fumes
with water, Moderate fire
hazard with organic
compound (Violently react
with Aromatic compound)
4 Sulfuri 1 Highly corrosive, causes
c Acid mg/m severe burns, no fire hazard
Hazardous property of Chemicals used in Aniline / TDI plants

5 DNT 1.5 Organic vapor Poisonous & explosive


mg/m respirator may
be worn
6 TDA/ Not Handle spills Toxic, confirmed Carcinogen,
MTD availab with butyl Flammable Evacuate area in
le rubber hand the event of spillage and
gloves, sweep the solidified material
respirators in to a plastic bag for safe
suitable for disposal. Use DAP/ FOAM for
TDA vapors / TDA fires.
7 CO 50 online
Wear air mask. Highly toxic, Color less, odor
respirators / less anesthetic gas, highly
airline mask explosive and flammable.
during plant
round / job.
Carry
8 Cl2 1 Wear
dosimetersuitable Highly toxic and corrosive
respirators
during round. / gas with pungent smell.
airline mask. Place Elephant Trunk on
leaky point to suck and divert
chlorine vapors to scrubber.

Hazardous property of Chemicals used in Aniline / TDI plants

9 Phosg 0.1, Wear Highly toxic gas with


ene the respirators / "CHIKOO" like smell, Short but
odour airline mask. heavy exposure may be fatal.
thresh Place Elephant Trunk on leaky
old 0.5 point to suck and divert
ppm Phosgene vapors to scrubber.

10 ODCB 2 ppm Wear suitable Suspected carcinogen,
(Orth respirators / Flammable color less liquid.
o Di- airline mask. Use water spray / DAP/ FOAM
Chlor for ODCB fires
o
Benze
ne)
11 HCl 5 ppm Avoid body Vapor highly toxic and
contact. Wear corrosive.
respirators.
12 Hot Always wear Hot molten issuing out from
molte face shield / incinerator is at >600C.
n safety Ensure that molten salt does
Goggles, proper not get spread here & there
hand gloves, while handling &
safety shoes transportation to minimize
and helmet environmental impact.
Hazardous property of Chemicals used in Aniline / TDI plants
13 TDI 0.005 Wear positive
The pressure self- TOXIC; inhalation, ingestion or
odor contained contact (skin, eyes) with vapors,
thresho breathing dusts or substance may cause
ld is 0.4 apparatus severe injury, burns, or death.
ppm: (SCBA). Wear Reaction with water or moist air
chemical will release toxic, corrosive or
protective flammable gases. Reaction with
clothing, which is water may generate much heat,
specifically which will increase the
recommended by concentration of fumes in the air.
the manufacturer. Fire will produce irritating,
Structural corrosive and/or toxic gases.
firefighters' Runoff from fire control or
protective dilution water may be corrosive
clothing is and/or toxic and cause pollution.
recommended for
fire situations
ONLY; it is not
effective in spill
situations.
Hazardous property of Chemicals used in Aniline / TDI plants
14 Aniline 2 Chemical
protection suit Effects of exposure
Including self- The substance is irritating
contained to the eyes and the skin.
breathing The substance may cause
apparatus. effects on the blood,
resulting in the formation
of methaemoglobin.
Exposure at high levels may
result in death. Prolonged
contact may cause skin
sensitization. Use Antidotes
Methylene Blue in case of
Aniline exposure. .
15 NB 1 Organic vapor May be fatal if swallowed,
respirator may inhaled or absorbed
be worn through skin. May cause
methemoglobinemia.
Affects, blood, liver,
kidneys, and reproductive
system. Causes irritation to
eyes and skin. Confirmed
animal carcinogen with
unknown relevance to

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