annexure-i size of the project name of product existing

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


- 2 -

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)


- 3 -

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:


- 4 -

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


- 5 -

MATERIAL BALANCE:


- 6 -

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]


- 7 -

MATERIAL BALANCE:


- 8 -

4. BUPROFEZIN:


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


- 9 -

MATERIAL BALANCE:


- 10 -

5. PYRIDALYL:


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


- 11 -

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


- 12 -

6. FENPYROXIMATE:


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


- 13 -

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


- 14 -

7. PROPARGITE:


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


- 15 -

MATERIAL BALANCE


- 16 -

8. ACEPHATE:


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


- 17 -

MATERIAL BALANCE:


- 18 -

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.


- 19 -

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

+


- 20 -

MATERIAL BALANCE:


- 21 -


- 22 -


- 23 -

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


- 24 -

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)


- 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.


- 26 -

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)


- 27 -

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


- 28 -

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 -


- 29 -

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

annexure-i size of the project name of product existing

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