Post on 18-Feb-2022
Cheminova India Limited-Technical Division-Panoli
- 1 -
Annexure-I
Size of the Project
Name of Product Existing
TPA
Proposed
TPA
Total
TPA
Monocrotophos Technical 1500 0 1500
Dichlorvos Technical 300 0 300
Chlorpyriphos Technical 10 0 10
Imidacloprid Technical 150 0 150
Quinalphos Technical 600 0 600
Triazophos Technical 150 0 150
Acephate Technical 1040 660 1700
Sulphonyl Ureas Technical 50 0 50
Triazols Technical 100 0 100
Profenophos Technical 100 0 100
Thiacloprid Technical 25 0 25
Natural Gas Based CPP 2.042 MW 0 2.042 MW
Phosalone 00 300 300
Azoxystrobin 00 300 300
Dimethomorph 00 60 60
Buprofezin 00 50 50
Pyridalyl 00 50 50
Fenpyroximate 00 50 50
Propargite 00 100 100
Fipronil 00 100 100
Total 4025 2460 5695
Cheminova India Limited-Technical Division-Panoli
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Annexure-II
Manufacturing Process
1. PHOSALONE
PROCESS DESCRIPTION:
Step 1: Reaction of 6-Cl Box with Formaldehyde in presence of Et OH as
solvent gives HMCB.
Step 2: Reaction of HMCB with Dry HCl gas using water as reaction
media yields CMCB as an intermediate.
Step 3: Reaction of DETA with sodium hydroxide solution formed Na-
DETA, which further reacts with step–1 CMCB in dichloride methane as a
solvent yields phosalone.
Separation: Separate the organic and aqueous phases by washing and
recover the solvent.
Drying: Drying of the separated solid material in dryer. The dried
material is packed in a bags and the water goes to the waste water
treatment.
CHEMICAL REACTION:
STEP 1 6-Cl-BOX TO HMCB
NH
O
O
6-chloro benzoxazolone
Cl
C7H4ClNO2
Mol. Wt.: 169.57
+
N
O
O
Cl
CH2OH3-Hydroxymethyl-6-chloro benzoxazolone
C8H6ClNO3Mol. Wt.: 199.59
(HMCB)
(6-Cl-BOX)
HCHO
STEP 2 HMCB TO CMCB
N
O
O
Cl
CH2OH3-Hydroxymethyl-6-chloro benzoxazolone
C8H6ClNO3Mol. Wt.: 199.59
+ HCl (gas)
N
O
O
Cl
CH2Cl
3-Chloromethyl-6-chloro benzoxazoloneC8H5Cl2NO2
Mol. Wt.: 218.04(CMCB)
Cheminova India Limited-Technical Division-Panoli
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STEP 3 CMCB TO PHOSALONE
N
O
O
Cl
CH2Cl3-Chloromethyl-6-chloro benzoxazolone
C8H5Cl2NO2
Mol. Wt.: 218.04
+ P
SOC2H5
OC2H5SH
C4H11O2PS2Mol. Wt.: 186.23
DETA
NaOH or KOHAcetone30°C / 6 hrs N
O
O
Cl
CH2 S P
S OC2H5
OC2H5PHOSALONE
C12H15ClNO4PS2Mol. Wt.: 367.81
(CMCB)
Material Balance:
Cheminova India Limited-Technical Division-Panoli
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2. AZOXYSTROBIN:
PROCESS DECRIPTION:
STEP A:
In the reaction vessel, MDC and TiCl4 is charged at room temperature.
Methyl formate is added in the reaction mixture at 20°C within half an
hour. Reaction mass cooled up to 5°C and DMA + MDC solution is added
within half an hour. Reaction mass stirred for 30 min and tri ethyl amine
is added within two hours. Reaction mass stirred for 2-3 hrs. until DMA
content in reaction mass is below 2%. Reaction mass is quenched with
dilute HCl and layers are separated. Water wash is given to organic phase
and clear organic phase is taken for step B.
STEP B:
In the organic phase obtained in step A, charge di methyl sulphate, aq.
Na2CO3 solution and catalyst. The resulting mixture is stirred till no raw
material present in the reaction mixture. Layers are separated. Sodium
thiosulphate treatment is given to organic phase. Organic phase is
washed with water and MDC is recovered from organic phase. In the
resulting concentrated mass, MeOH is added and product is crystallised,
filtered and dried in the dryer.
CHEMICAL REACTION:
N N
O O
OMe
O
CN
TiCl4, MeFormate
N-Et3, MDC
Me2SO4,
MDC, H2O
N N
O O
OMe
O
CNO
N N
O O
OMe
O
CNMeO
Des-Methoxy Azoxy
(DMA)
Des-methyl Azoxy
Azoxystrobin
Cheminova India Limited-Technical Division-Panoli
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3. DIMETHOMORPH:
PROCESS DESCRITION:
N – Acetyl morpholine and 4 – Chloro – 3, 4’ –Dimethoxy benzophenone
are condensed in the presence of NaH base, t - BuOH and n – Heptane
solvents. During reaction H2 gas is evaluated. During reaction water is
generated and it is parallel separated by dean Starks apparatus. Reaction
is completed in 25 – 30 hrs at reflux temperature.
Reaction mixture is poured in to water. Product is filtered and washed
with water. It is dried and analyzed.
Filtrate is separated. Organic layer is evaporated till dryness. Recovered
solvent is recycled in the process after moisture removal. Aqueous layer
is separated and sent it for further treatment at ETP and or recycled.
Organic reside is sent for incineration.
CHEMICAL REACTION:
Cl
C
O
O
N
+
C
CH3
O
Cl
C
CH
C O
N
O
i) Solvent
ii) Base
iii) Catalyst
iv) Reflux
OCH3
OCH3
OCH3
OCH3
+ H2O
CDMBP N – Acetyl Morpholine Dimethomorph
CAS no. [116412 – 83 – 01] [1696 – 20 – 4] [110488 – 70 – 5]
Cheminova India Limited-Technical Division-Panoli
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4. BUPROFEZIN:
PROCESS DESCRIPTION:
Step-1 Charge PNNCC, Toluene, and lime in the reaction vessel. Stir the
reaction mass for 2-3 hours. Charge Thiourea slowly in the reaction mass
in 2-3 hours and stir the reaction mass at higher temperature until raw
material is totally consumed.
Step-2 After completion of reaction, Filter the reaction mass to isolate
inorganic solid.
Step-3 Wash inorganic solid with toluene. Recover toluene under vacuum
from clear organic phase.
Step-4 Add EDC in the crude solid. Charge TEA slowly at room
temperature and stir the reaction mass for 3 hours.
Step-5 Reaction mass is washed with water. Separate the layers.
Recover EDC under vacuum partially.
Step-6 Cool the conc. mass slowly and filter the crystals. Dry the wet
product at 50 - 65%.
CHEMICAL REACTION:
N
CH2Cl
C
O
NO2
+ CS
NH
NH
i-Pr
t-Bu
S
N
N i-Pr
N t-Bu
p - Nitrophenyl N - Chloromethyl Carbamate
N-isopropyl- N-tert-butyl Thiourea
BUPROFEZIN
O
Cheminova India Limited-Technical Division-Panoli
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5. PYRIDALYL:
PROCESS DESCRIPTION:
Step 1: Charge 2-chloro-5-trifluoromethylpyridine (CTFMP) with 3-(4-(3,
3-dichloroallyloxy)-2, 6-dichlorophenoxy) propan-1-ol (DCDPP) in
presence of NaH and Hexane as solvent in a reactor for reaction
process.
Step-2: After completion of the reaction organic layer is separated as a
salt from a reaction mass.
Step-3: The separated mass is then washed with water to get separate
organic and aqueous layer.
Step-4: The organic layer separated is further processed to recover a
solvent as product pyridalyl.
CHEMICAL REACTION:
2-chloro-5-trifluoromethylpyridine
N F
F
FCl
C6H3ClF3NMol. Wt.: 181.54
OHO
OCl
Cl
Cl
Cl
3-(4-(3,3-dichloroallyloxy)-2,6-dichlorophenoxy)propan-1-ol
+
C12H12Cl4O3Mol. Wt.: 346.03
NaH
Hexane
OO
OCl
Cl
Cl
Cl
N
CF3
C18H14Cl4F3NO3
Mol. Wt.: 491.12
2-(3-(4-(3,3-dichloroallyloxy)-2,6-dichlorophenoxy)propoxy)-5-(trifluoromethyl)pyridine
PYRIDALYL
Cheminova India Limited-Technical Division-Panoli
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MATERIAL BALANCE:
Input Quantity,
Kg
Pyridalyl
Output Quantity,
Kg
CTFMP 554
DCDPP 1056 Reaction Mass
NaH 80
H2 gas
7 To
scrubber
Hexane 5544
1) Reaction
Reaction
Mass
Organic
layer
2970
recovered
2) Separation
Salt
150 to
incineration
Organic Layer
Solvent
loss
170 to
scrubber
Water 1920
Organic
layer
2500
recovered
3) Washing/
Draining Aqueous
layer
1880 for
recycle
Organic layer
Organic
residue
390 to
incineration
4) Recovery
Product 1087
Total 9154 9154
Cheminova India Limited-Technical Division-Panoli
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6. FENPYROXIMATE:
PROCESS DESCRIPTION:
Step-1: Charge H- pyrazole-4-carboxaldehyde, 1, 3-dimethyl-5-phenoxy-
oxime (PCDPO) and tertiary butyl-4-(chloro methyl benzoate
(TBCMB) in presence of KOH as base and DMF as solvent in a vessel
for carrying a reaction.
Step-2: After completion of the reaction organic layer is separated as a
salt from a reaction mass.
Step-3: The separated mass is then washed with water to get separate
organic, recovery of solvent and aqueous phase.
Step-4: The organic mass is again washed with water which after
processing get recovered a solvent as product Fenpyroximate.
CHEMICAL REACTION:
N
N
CH3HC
PhO
CH3
N
HO
CH2Cl
OO
C12H15ClO2Mol. Wt.: 226.7
C12H13N3O2
Mol. Wt.: 231.25
tert-butyl 4-(chloromethyl)benzoate
+KOH
N
N
CH3HC
PhO
CH3
N
O
O
O
C24H27N3O4
Mol. Wt.: 421.5
FENPYROXIMATE
1H-Pyrazole-4-carboxaldehyde,1,3-dimethyl-5-phenoxy-oxime
DMF
Cheminova India Limited-Technical Division-Panoli
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MATERIAL BALANCE:
Fenpyroximate
Input Qty, Kg Output Qty,
Kg
PCDPO 939
TBCMB 921 Reaction Mass
KOH 249
DMF 7800
1) Reaction
Reaction
Mass
Organic
layer
3500
recovered
2) Separation
Salt
309 to
incineration
Organic Layer
Solvent
loss
160 to
scrubber
Organic
layer
4140
recovered
3) Recovery &
draining
Aqueous
layer
1780 for
recycle
Organic layer
Organic
residue
750 to
incineration
Water 1800 4) Washing Product 1070
Total 11709 11709
Cheminova India Limited-Technical Division-Panoli
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7. PROPARGITE:
PROCESS DESCRIPTION:
STEP – I: 1,2 – Cyclo hexane oxide is converted in to its K –Salt of diole
in the presence of KOH at 175°C for 6 hrs and pressure 1.7 MPa. Then it
reacts with Thionyl chloride in the presence of toluene as solvent gives 1
– Chloro 2 – hydroxy cyclo hexane K – Salt.
STEP – II: Propargyl alcohol is reacts with Thionyl chloride at 27°C for 7
hrs and gives Propargyl sulfonyl chloride.
STEP – III: Intermediates are obtained in step – I & II are reacting with
p–tert. Butyl phenol in the presence of toluene under controlled condition
gives Propargite.
CHEMICAL REACTION:
O + KOH + SOCl2
Ph-CH3
Cl
OK
STEP - I
STEP - II
1,2 - Cyclohexene Pottasium Hydroxide
Thionyl Chloride 1-Chloro 2 - hydroxy
Cyclohexane - K - Salt
HC C CH2OH + SOCl2
Ph-CH3HC C CH2 - O - S - Cl
O
Propargyl Alcohol Thionyl Chloride
STEP - III
Cl
OK
+
Bu - t
OH
+ HC C CH2 - O - S - Cl
OPh-CH3
O S C
O
C CH
O
Bu - t
Propargite
H
H
[286 - 20 - 4]
[107 - 19 - 7]
[98 - 54 - 5]
[2312 - 35 - 8]
p - tert. Butyl Phenol
Cheminova India Limited-Technical Division-Panoli
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8. ACEPHATE:
PROCESS DESCRIPTION:
Step-1: Dimethyl Thio Phosphoramide (DMPAT) in MDC as solvent is
rearranged in presence of Dimethyl Sulphate (DMS) as catalyst, to form
the intermediate monitor.
Step-2: The intermediate is then reacted with Acetic Anhydride to form
Acephate.
Step-3: The reaction mixture is neutralizes with liquor ammonia, and the
MDC is recovered from the organic phase for reuse.
Step-4: Acephate is crystallized by addition of Ethyl Acetate in the
separated organic phase. The organic mother liquor is reused in the
process.
CHEMICAL REACTION:
CH3O S CH3 O
P + (CH3)2SO4 P + (CH3)2SO4
CH3O NH2 CH3S NH2
DMPAT DMS MONITOR DMS
CH3O O CH3 O
P + (CH3CO)2O P + CH3COOH
CH3S NH2 CH3S NH2
MONITOR AC2O ACEPHATE ACETIC ACID
Cheminova India Limited-Technical Division-Panoli
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9. FIPRONIL
CAS No-[120068 – 37 - 3]
PROCESS DESCRIPTION
STEP – I: Fipronil Pyrazole to Fipronil Thicyanate (FPP to FPT):
Fipronil Pyrazole and Ammonium Thiocyanate are condensed in the
presence of oxidant Oxone® and MeOH as solvent.
Reaction is completed in 3.0 hrs at 39 – 40°C.
An inorganic salt is filtered, washed with MeOH and dried.
MeOH is recovered from filtrate partially under reduced pressure.
Recovered MeOH is recycled.
Partially concentrated mass is dumped in to water at RT. Stirred for 3 – 4
Hrs at RT.
Product (FPT) is filtered at RT and washed with water.
Product (FPT) is dried at 50°C till constant weight is obtained.
STEP – II: Fipronil Thicyanate to Desoxy Fipronil (FPT to DOF):
Fipronil Thiocyanate and CF3Br are reacting in the presence of SO2 (g),
Sodium formate and DMF as solvent.
Reaction is carried out under pressure in Auto clave at 70°C.
Reaction mixture is cooled down at 40°C.
The pressure in autoclave is released and scrubbed in 7% NaOCl soln.
Reaction mass is transferred to mixture of water + Isopropyl acetate
solution and stirred for ½ hrs at RT.
Organic and Aq. phases are separated. Aq. phase is extracted with IPAc
and then treated with NaOCl solution and incinerated.
Combined organic phase is washed with water. Washed organic phase
taken for partial IPAc recovery under reduced pressure. Recovered IPAc is
recycled. Partial concentrated mass is taken for crystallization.
Product is crystallized out and filtered out and dried.
Mother liquor is subjected for isopropyl acetate recovery. Reco. IPAc is
recycled and organic residue is incinerated.
Cheminova India Limited-Technical Division-Panoli
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STEP – III: Des-oxy Fipronil to Fipronil (DOF to FP):
Des-Oxy Fipronil, Trifluoro acetic acid and chloro benzene are mixed at
RT.
H2O2 is added for 30 min. at low temperature.
After completion of reaction chloro benzene is charged and CF3COOH is
distilled out.
Product is crystallized out in Ethanol and water, filtered and dried.
CHEMICAL REACTION
NN
CN
H2N
Cl Cl
CF3
NN
CN
H2N
Cl Cl
CF3
SNC
NN
CN
H2N
Cl Cl
CF3
SF3C
NN
CN
H2N
Cl Cl
CF3
SF3C
O
Fipronil Pyrazol Fipronil Thiocyanate DOF Fipronil
Mol. Wt.: 321,09 Mol. Wt.: 378,16 Mol. Wt.: 421,15 Mol. Wt.: 437,15
Oxone
NH4SCN
MeOH CF3BrDMF
HCOONaSO2
CF3COOHH2O2
CH2Cl2
Fipronil Synthesis - Step 1 to 3 - and possible impurities
NN
CN
H2N
Cl Cl
CF3
S
NN
NC
NH2
ClCl
CF3
S
Fipronil Disulfide
Mol. Wt.: 704,28
NN
CN
H2N
Cl Cl
CF3
SF3C
O
Fipronil Sulfon
O
Mol. Wt.: 453,15
NNH2N
Cl Cl
CF3
SF3C
O O
NH2
Fipronil Amide
Mol. Wt.: 455,16
/MN
NN
CN
H2N
Cl Cl
CF3
HS
Mol. Wt.: 353,15
Fipronil Sulfide
+
Cheminova India Limited-Technical Division-Panoli
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Annexure-III (A)
Water Balance (Existing)
Water from GIDC 350
Process 50
Cooling tower 142
Evaporation Loss 132
Boiler
103
Process Steam 98
Blow Down 10
Blow Down 5
Septic
Tank
30
Drinking & Hand washing
5
Gardening 20
Effluent 45
Effluent Treatment Plant 90
Concentrated Effluent
5
Domestic 55
After treatment, underground drainage to BEAIL
Cheminova India Limited-Technical Division-Panoli
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Process
70
Cooling Tower
50
Effluent Treatment Plant 68
Water from GIDC
170
Boiler
35
Process
Steam 33
Domestic
15
Concentrated
Effluent 14
Effluent
56
Septic
Tank
8
Blow Down
2
Drinking water
2
Gardening
5
Bleed off
2
Evaporation
Loss 48
After treatment, underground drainage to BEAIL
Water Balance (Proposed addition)
Cheminova India Limited-Technical Division-Panoli
- 25 -
Annexure-III (B)
ETP details:
Brief description of Effluent Treatment Plant:
Waste water treatment:
Proposed to segregate various concentrated effluents at source containing high
COD and salt content and only treatable dilute effluent stream shall be taken to
ETP. Treatment plant has been designed based on the water consumption and
effluent generation for both the pesticides and intermediates.
Physico Chemical (Primary) & Biological treatment: As indicated by
characteristics of the untreated effluent, the effluent needs treatment for the
removal of colour, slight acidity, SS, O&G, phosphate, BOD and COD. It was
decided to give normal Physico-chemical treatment to the effluent followed by
the secondary (biological) treatment under aerobic condition as quantity and
quality of untreated effluent does not favour anaerobic treatment.
Tertiary Polishing treatment: The treated effluent is passed through sand
and finally a column fitted with granular activated carbon for the removal of
any residual toxicity. At the end the effluent is to be discharged into CETP.
Disposal of treated effluent: The treated effluent meeting the GPCB norms
can be safely drained into CETP – Panoli effluent drainage pipeline for further
treatment. The treated effluent from the CETP is disposed off into deep sea via
mega pipeline.
Treated effluent from final effluent pit is analyzed before disposal to GIDC
drainage, which will finally convey to BEAIL.
After the treatment disposal of effluent by M/s. Bharuch Eco-Aqua Enviro
Infrastructure Ltd. (BEAIL), Bharuch, has been resolved, the effluent will be
disposed off through BEAIL pipeline.
Cheminova India Limited-Technical Division-Panoli
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Schematic Diagrams for Existing Effluent Treatment Plant
Details of ETP units
Sr.
No.
Name of Unit Indicative Size of
Unit
Capacity of
Unit
1 Oil and Grease trap 3 x 1.4x 1.5 (LD) 6.3
2 Equalization (02 Nos.) 8.6 x 4.3 x 3 (LD) 110.94
3 Primary Setting Tank 3.0 x 3.0 x 2.25 20.25
4 Aeration Tank 25 dia. x 3 (LD) 1471.87
5 Secondary Clarifier - I 5 dia. x 2.75 (SWD) 53.96
6 Secondary Clarifier - II 5 dia. x 2.75 (SWD) 53.96
7 Treated effluent collection sump 1.0 x 1.0 x 1.25 1.25
8 Activated carbon Filter - I 1 dia. x 2 (HOS) 1.5
9 Activated carbon Filter - II 1.8 dia. x 2.5 (HOS) 6.5
10 Sludge Drying Beds (04 Nos.) 9.0 x 6.0 ( Each ) 54
11 Incineration Ash & Solid waste
storage area with A.C. Sheet
Roof
14 x 7.5 105 (250 MT)
Cheminova India Limited-Technical Division-Panoli
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Annexure-IV
Hazardous wastes
Sr.
No.
Description of
Waste
Category
of Waste
Existing
Quantity
Proposed
Quantity
Mode of Disposal
1 ETP Waste 34.3 305 TPA 50 TPA Collection, Storage
Transportation, Disposal to TSDF site
operated by BEIL
2 Process Waste 29.2 2160 TPA 650 TPA Incineration facilities
operated by CHEMINOVA /GEPIL
3 Evaporation
Salt
34.4 525 TPA 175 TPA TSDF site SURAT operated by GEPIL
4 Used Lubricating Oil
5.1 0.360 TPA
0 Collection, Storage Transportation,
Disposal by selling to registered Re-refiners
5 Spent Solvent (MDC,
EA, Acetone, Ethyl Acetate
20.2 - 500 TPA Collection Storage recover/reuse within
the industrial unit
6 Drums & Containers
Bags & Liners
33.3 12780 Nos./A
32484 Nos./A
700 Nos./A
15000 Nos./A
Collection Storage and Decontamination
Cheminova India Limited-Technical Division-Panoli
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Annexure-V
Details of Air Emission
Sr.
No.
Stack
attached
to
Stack
height
(m)
Dia. of
Stack
(m)
Fuel
Used
APC
measures
Pollutants
Flue Gas Stack
1. Boiler 30 0.600 N.G. - PM<150 mg/NM3
SO2<100 ppm
NOx<50 ppm 2. Captive
Power Plant
30.5 0.500 N.G. -
3. DG
(stand by)
11 0.2 Diesel -
4.
Incinerator 45 0.800 N.G. - PM<150 mg/NM3
SO2<40 mg/NM3
NOx<25 mg/NM3
HCl<20 mg/NM3
Cl2<09 mg/NM3
Process Gas Stack
1. Vent of
Acephate
Plant
25 65 mm - Scrubber HCl<20 mg/NM3
Cl2<09 mg/NM3
2. Vent of MCP
Plant
28 75 mm -
Cheminova India Limited-Technical Division-Panoli
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Annexure-VI
Noise Survey
Sr.
No.
Location Result
dB(A)
1 Near Security cabin 70
2 Near material Gate 68
3 Near ETP area 72
4 Near Brine Chilling plant 80
5 Near Boiler 81
6 Near D. G. Sets 69
7 Near Water chilling plant 72
8 Near MCP Plant 68
9 Near ACP plant 71