Date : 01/04/2008...Para toluene sulphonic acid and solvent. Later it is reacted with bromine at 20 C in solvent and the Bromo Ketal product is isolated after distillation of solvent

Annexures

of Form-1

M/s. Bios Cropcare Pvt. Ltd.

D/2/CH-128, GIDC Dahej,

Tehsil: Vagra,

Dist.: Bharuch-392110, Gujarat.

Proposed Project for Manufacturing of

Fungicides and Insecticides (500 TPM)

Project Activity: 5(b), Category: A

M/s. Bios Cropcare Pvt. Ltd. 1

Annexure-I

List of Products

Sr.

No

Name of

Products

CAS No. LD50

mg/kg

Quantity

(MTPM)

(A) Fungicide

1. Difenoconazole 119446-68-3 1,453 400

2. Hexaconazole 79983-71-4 612

3. Metconazole 125116-23-6 1,459

4. Propiconazole 60207-90-1 1,517

5. Prothioconazole 178928-70-6 >6,200

6. Tebuconazole 107534-96-3 1,700

7. Tricyclazole 41814-78-2 250

8. Azoxystrobin 131860-33-8 >5,000

9. Picoxystrobin 117428-22-5 5,000

10. Pyraclostrobin 175013-18-0 >5,000

11. Trifloxystrobin 141517-21-7 >5,000

12. Carbendazim 10605-21-7 6,400

13. Cymoxanil 57966-95-7 1,100

14. Metalaxil 57837-19-1 566

15. Thiophanate Methyl 23564-05-8 6,640

(B) Insecticide

16. Acetamiprid 135410-20-7 146 100

17. Imidacloprid 138261-41-3 410

18. Profenophos 41198-08-7 620.5

19. Thiamethoxam 153719-23-4 1,563

Total 500


Annexure-II

Manufacturing process with Mass balance

1. Difenaconzole

Manufacturing process:

1,3-Dichloro Benzene is reacted with Acetyl Chloride, Aluminum Chloride

and EDC to get 2,4-Dichloro Acetophenone.

2,4-Dichloro Acetophenone further reacted with 4-Chloro Phenol,

Potassium Hydroxide, DMF to get 2-Chloro-4-(4-Chlorophenoxy)

Acetophenone.

2-Chloro-4-(4-Chlorophenoxy) Acetophenone further reacted with

Bromine to get 2-(Bromomethyl)-2-[4-(4-chlorophenoxy)-2-

chlorophenyl]-2-methyl-1,3-dioxolane (Bromoketal).

1H-1,2,4-triazole is reacted with Bromoketal in N,N-dimethyl formamide

in presence of potassium iodide at 145-150°C to give Difenoconzole.

Chemical Reaction:


Mass Balance:

IN PUT Kg OUT PUT Kg

1,3-Dichloro Benzene 385Acetyl Chloride 202 EDC Recovery 1130

Aluminum Chloride 420 Residue 70

EDC 1200Water 800

4-Chloro Phenol 360 DMF Recovery 1410

Potassium Hydroxide 240 Residue 90

Bromine 415 Effluent 1100DMF 1500

1H-1,2,4-triazole 200

KOH 220

Water 1200 Effluent 2017

Drying Loss 325

Difenoconazole 1000

Total 7142 7142

Drying & Packing

MASS BALANCE OF DIFENCONAZOLE

Intermediate

Intermediate

Difenoconzole

Washing


2. Hexaconazole

Manufacturing process

Di Methyl sulfate is charged in Di Methyl Sulfide at 330C to form Trimethyl

sulfonium sulfate.

2,4 Di Chloro Valerophenone is reacted with Trimethyl sulfonium sulfate

in presence of potassium Hydroxide to form Oxirane. Solvent Di Methyl

sulfide is recovered by distillation and product (Oxirane) is separated

from Potassium Hydrogen sulfate water is added to dissolve salt and back

extracted with Methylene dichloride and then Aqueous is transferred to

ETP.

1,2,4 1H Triazole and Potassium Carbonate is charged in Di Methyl

formamide solvent and Previously prepared Oxirane is added at elevated

temperature to form Hexaconazole.

After completion of reaction, organic phase is separated by filtration.

Carbonate sludge is washed with DMF and collected with organic filtrate.

Sludge is transferred to solid waste DMF is distilled out from reaction

mass first at atmospheric distillation and then by vacuum distillation.

Hexaconazole is isolated from molten mass with help of water. Slurry is

filtered, centrifuged and dried.

Chemical Reaction


Mass Balance:


2,4-DVP 900

Dimethyl sulphide 800 Effluent 3200

Dimethyl sulphate 650

KOH 800

Water 1350

DMF 1800

1,2,4 Triazol 350

K2CO3 85

DMF Recovery 1715

Residue 85

Water washing 1200 Effluent 1690

Heptane 950

Haptane Recovery 900

Residue 50

Drying Loss 245

Hexaconazole 1000

Total 8885 8885

Drying

MASS BALANCE OF HEXACONAZOLE

Oxirane Formation

Hexaconazol

Formation

DMF Recovery

Washing

Chilling & Filteration


3. Metconazole

Manufacturing Process:

Methyl-33,-Dimethyl-2-Oxo-Cyclopentane Carboxylate reacts with 4-Chloro

Benzyl Chloride in presence of Solvent and catalyst to give 1-(4-Chloro

Benzyl)Methyl-3,3-Methyl-2-Oxo Cyclopentane Carboxylate, which

undergoes rearrangement reaction on heating with catalyst gives the

intermediate.

Intermediate finally reacts with 1,2,4-Triazole in presence of solvent as

well as catalyst to give the final product Metconazole.

Chemical Reaction:

C

C

C

O O

O C +

C

Cl

Cl

Methyl 3,3 dimethyl 2 oxo cyclopentane carboxylate

4-Chloro Benzyl

Chloride

Heat

Catalyst

C

CC Cl

O

N

N

N

1,2,4 Triazole

N

N

N

C

C

C

OH

Metconazole

+

C

C

C

OO

O C

C Cl

Cl


Mass Balance:

INPUT KG OUTPUT KG

Methyl-33,-Dimethyl-2-Oxo-

Cyclopentane Carboxylate

380

4-Chloro Benzyl Chloride 548 Effluent 2150

Catalyst 20

Toluene 2200

1, 2,4-Triazole 350

Water 2000

Toluene Recvoey 2125

Water 1500 Residue 75

Effluent 1423

Drying loss 225

Metconazole 1000

TOTAL 6998 6998

Drying

MASS BALANCE OF METCONAZOLE

Reaction

Washing

Filteration &

Centrifuhe


4. Propiconazole

Manufacturing process

1,3-dichlorobenzene is reacted with acetyl chloride in presence of AICI3 at

10-15°C under stirring to produce 2,4-dichloroacetophenone.

After reaction is complete add KOH flakes slowly. Maintain the reaction

mass for 4 hrs. until the reaction is complete.

The intermediate product is reacted with 1,2-pentanediol in presence of

Para toluene sulphonic acid and solvent.

Later it is reacted with bromine at 20°C in solvent and the Bromo Ketal

product is isolated after distillation of solvent.

Sodium salt of 1,2,4-Trizole in solvent DMF is reacted with the Bromo ketal

and the product Propiconazole is isolated by filtration and distillation.

Chemical Reaction:


Mass balance

INPUT Kg OUTPUT Kg

1,3 Di Chloro Benzene 380

Acetyl Chloride 330 EDC recovery 1580

Aluminum Chloride 410 Residue 20

EDC 1600 Effluent 1200

Water 1000

1,2 Pentanediol 540 Toluene recovery 1960

PTSA 10 Residue 40

Toluene 2000 Effluent 1700

Water 1000

Bromine 675 HBr 350

Water 1000

1,2,4-Trizole 285

DMF 1800

DMF Recovery 1760

Residue 40

Effluent 2215

Water for washing 1200 Drying loss 365

Propiconazole 1000

Total 12230 12230

Mass balance of Propiconazole

Reaction-1

Reaction-2

DMF Recovery

Washing &

Drying

Reaction-3


5. Prothiconazole

Manufacturing Process

The desired quantities of Thiosemicarbazide derivative, Isobutylformate and

formic acid are charged in to the reactor and the reaction mass is heated at

desired temperature until reaction is over.

Once the reaction is completed, cool the mass and Ethyl acetate is added, the

reaction mass is washed with 40% ammonium chloride solution and layers are

separated.

Solvent from organic layer is recovered and recycled and product is isolated by

filtration.

Re-crystallization of the crude product in Toluene is carried out to reach final

product after filtration, wet cake is dried.

Solvent is recovered and recycled.

Chemical Reaction

Cl OH

ClN

NH2

S

NH2

Thiosemicarbazide derivative

HCOOH

-2H2O

Cl OH

Cl

N

NH

NS

Prothioconazole

MF= C13

H17

Cl2N

3OS

FW= 334.26458

MF= C14

H15

Cl2N

3OS

FW= 344.2594

Mass Balance

INPUT KG OUTPUT KG

Thiosemicaebazide derivative 1000Isobutyl Formate 2200

Formic Acid 250

Ethylacetate 3000 Ethyl Acetate 3150

Aq. Ammonium Chloride 2400 Iso butyl Formate 1800


Toluene 2120

Toluene 2200 Residue 80

Drying loss 350

Prothioconazole 1000

TOTAL 13050 13050

Mass Balance of Prothioconazole

Recrystalization &

Drying

Distillation

Reaction


6. Tebuconazole


Dimethyl sulfate is reacted with aqueous solution of Sodium sulfide at 75

- 800C, to form dimethyl sulfide. The Product is condensed and collected

in receiver.

Then nitrogen is purged into the reactor to get maximum possible

dimethyl sulfide recovery. Spent liquor containing sodium sulfate is then

transferred to ETP.

1-(4-Chlorophenyl)-4, 4’-dimethyl-pent-3- one (CPDP) is made to react

with dimethyl sulphate and potassium hydroxide in presence of dimethyl

sulfide to give tebuoxirane.

The solvent dimethyl sulfide is recovered by distillation and then the

intermediate product (tebuoxirane) separated from the reactor. Then

water is added in the reactor to dissolve salt formed during the reaction

and transferred to ETP.

In dimethyl formamide, potassium carbonate, 1, 2, 4-triazole is added

and then above prepared oxirane is added at reflux temperature. After

completion of the reaction the mass is filtered and then solvent DMF is

distilled out. Then the product Tebuconazole is isolated by adding water.

The slurry is filtered, centrifuged & dried. The filtered potassium

carbonate sludge is washed with DMF to recover the product. Treated

sludge is then transferred to solid waste. The mother liquor is transferred

to ETP.

Chemical Reaction:

(CH3)2SO4 + Na2S +H2O = (CH3)2S + Na2SO4 + H2O

CH2Cl CH

2COC(CH

3)3

CH2Cl CH

2-C-C(CH

3)3

CH2

O

+ (CH3)2SO4 + 2 KOH

DMS

1-(4-CHLOROPHENYL)-4,4'-DIMETHYL-PENT-3-ONE (CPDP)

+ K2SO4 + H2O

Oxirane


CH2Cl CH

2-C-C(CH

3)3

CH2

N

NN

H

K2CO

3

CH2Cl CH

2-C-C(CH

3)3

OH

CH2

N

NN

K2CO

3

O

Oxirane1H-1,2,4-

Triazole

+ +DMF

Tebuconazole

+

Mass Balance:

INPUT KG OUTPUT KG

Dimethyl Sulfate 420

Sodium sulfide 25

Ketal 720

KOH 330 DMF Recovery 1400

1,2,4-triazole 260 Residue 100

K2CO3 45

DMF 1500

Water 4850

Effluent 5150

Solid waste 85

Drying Loss 415

Tebuconazole 1000

Total 8150 8150

MASS BALANCE OF TEBUCONAZOLE

Reaction

Filtration

Drying

Separation


7. Tricyclazole


2- Hydrazino -4-Methyl BenzoThiazol is charged in formic acid at 90-100 c

in four hours time. Temperature is raised to complete the reaction. After

completion of reaction formic acid is distilled out along with some water.

After most of formic acid is distilled out water is charged in to the reactor

and residual acid is neutralized with Caustic soda lye. Slurry is filtered out,

centrifuged and dried. Filtrate is sent to ETP.

Chemical Reaction

Mass Balance:


HMBT 950

Formic acid 650 Formic acid recovery 450

Caustic lye 70

Water 3500

Wastewater 3605

Drying loss 115

Tricyclozole 1000

Total 5170 5170

Mass balance of Tricyclozole

Reaction

Filtration

Drying


8. Azoxystrobin


2,6 Dichloro Pyrimidine and anhydrous Potassium carbonate is charged in

DMF. Solution of Methyl- 2-(2 Hydroxy phenyl)-3 methoxyPropenoate in

DMF is charged to above solution.

When addition is over, warm the reaction mass to complete the reaction.

Charge 2 cyano Phenol to the reaction mass and add catalytic amount of

Cuprous Chloride and heat the reaction mass to 1000C for few hours.

Filter the reaction mass to remove inorganics and distilled out DMF from

reaction mass. Add hexane and wash the reaction mass with dilute caustic

to remove unreacted cyano phenol from the reaction mass.

Crystallize the crude with ether/dichloromethane and n Hexane, precipitate

is filtered, centrifuged and dried to get technical grade white crystalline

solid.

Chemical Reaction


Mass Balance:

INPUT KG OUTPUT KG

2,6 Diachloro Pyrimidine 450

DMF 5000

MHPMP 585

Potassium Carbonate 600

Cyano Phenol 350

Cuprus Chloride 25


DMF Recovery 4850

Residue 150

Caustic Soda 35


Hexane 3200

MDC Recovery 1920

Dichloro Methane 2000 Hexane Recovery 3080

Residue 200

Azoxystorbin 1000

TOTAL 15445 15445

Mass balance of Azoxystrobin

Crystallization &

Solvent Recovery

Reaction

Filtration

Distillation

Washing & Separation


9. Picoxystrobin


3-isochromanone is dissolved in a mixture of toluene and methanol to

which thionyl chloride is added at a temperature not exceeding 10 deg C.

HCl and SO2 formed during reaction is scrubbed in caustic scrubber.

At the end of reaction, the reaction mixture is wasted with 0.5 N sodium

bicarbonate solution, toluene is recovered under vacuum and the residue is

taken to the next step without further purification

To a solution of 2-hydoxy-6-trifluoromethyl pyridine in toluene, sodium

methoxide in methanol is added and stirred at room temperature for

completion of reaction. At the end of reaction, methanol is removed as

azeotrope with toluene.

To this mixture, the product obtained from previous step in toluene

solution is added and stirred at room temperature until completion of

reaction. The reaction mixture is filtered and solvent is removed under

vacuum. The residue is recrystallized from methanol and dried.

The product from previous step is dissolved in dimethyl formamide (DMF)

and anhydrous potassium carbonate is added to it. While keeping the

temperature below 10 deg C, dimethyl sulphate (DMS) is added over a

period of time.

After completion of reaction, the reaction mixture is filtered and filtrate is

concentrated under vacuum to recover the solvent. The residue is dissolved

in ethylene dichloride (EDC) and washed with water. EDC is removed under

vacuum.

The residue is dissolved in methanol and recrystallized and dried to obtain

Picoxystrobin technical.


Chemical Reaction:


Mass Balance:

INPUT KG OUTPUT KG

3-isochromanone 500

Thionyl Chloride 380

Methanol 2200 Methanol Recovered 2120

2-hydroxy-6-trifluromethyl 580 Residue 80

Sodium Methoxide 270 HCl + SO2 to Scrubber 135Dimethyl Sulfide 450

Toluene 5500 Toluene Recovered 5350


Potassium Carbonate 410 EDC recovered 1990

Ethylene Dichloride (EDC) 2100 DMF Recovered 2380

Dimethyl Foramamide (DMF) 2500 Residue 230

Methanol 2200 Inorganic salts 435


Methanol Recovered 2120

Residue 80

Effluent 2570

Picoxystrobin 1000

Total 21190 21190

Crystalization,

Filtration & Drying

Reaction

Layer Separation

Reaction & Purification

Mass balance of Picoxystrobin


10. Pyraclostrobin


Charge desired quantities of 1, 4 Dichloro Benzene reacts with 3-Chloro Pyrazole

in presence of catalyst & Xylene and stirred at Desired temperature until reaction

is over and 3-Chloro 4-Chloro Phenyl Pyrazole is obtained.

Charge 2-Chloro Benzyl Alcohol with N-MethoxyCarbamate to form N-methoxy, N-

(2-Oxymethyl Phenol) Carbamate.

Condense 3-Chloro 4-Chloro Phenyl Pyrazole and N-methoxy, N-(2-Oxymethyl

Phenol) Carbamate to get Pyraclostrobin.

Once the reaction is completed, Filtered the reaction mass and cake is washed

with water & dried. Solvent is recovered and recycled.

Chemical Reaction:


Mass Balance:

INPUT KG OUTPUT KG

1, 4 Dichloro Benzene 4353-Chloro Pyrazole 280

2-Chloro Benzyl Alcohol 365

N-MethoxyCarbamate 275

Catalyst 10Xylene 3000

Xylene recovery 2940


Effluent 2440

Drying loss 125

Pyraclostrobin 1000

Total 6565 6565

Filtration &

Distillation

Drying

Mass balance of Pyraclostrobin

Reaction


11. Trifloxystrobin


2-Methyl Aniline is reacted with Sodium Nitrite and Hydrochloric acid to get

2-Methyl benzene Diazonium salt by diazotization.

2-Methyl Benzene Diazonium salt is reacted with Glyoxylic Acid methyl

ester Oxime at 30 – 35°C to yield 2-Methyl phenyl glyoxalin acid methyl

ester Oxime.

2-Methyl Phenyl Glyoxylic Acid methyl ester Oxime is reacted with

Dimethyl sulfate with Sodium Hydroxide at 45 – 50°C to get 2-Methyl

Phenyl Glyoxylate-o-methyl Oxime.

2-Methyl Phenyl Glyoxylate-o-methyl Oxime further on chlorination with

chlorine gas in EDC at 45 – 50°C to get 2-Chloromethyl phenyl Glyoxylate-

o-methyl Oxime.

2-Chloromethyl Phenyl Glyoxylate-o-methyl Oxime is reacted with Sodium

[-1- [3-(Trifluoromethyl) Phenyl ] Ethylidene]Amine] Oxidamine in DMF at

75– 80°C to give crude Trifloxystrobin.

The solvent is distilled out under vacuum, the residual mass is taken in

water, centrifuged and dried to get Trifloxystrobin Technical.


Chemical Reaction:


Mass Balance:

INPUT KG OUTPUT KG

2 Methyl Aniline 285

Sodium nitrite 210

HCl 350H2SO4 280

Glyoxylix Acid Methyl

Ester Oxim300 Nitrogen Gas 55

Water for Washing 1500 Effluent 2450

DMSO4 180

NaOH 290 Effluent 290

EDC 1200

HCl 110

Chlorine 250 EDC Recovery 1120

Residue 80

Oxidamine 550

DMF 1500

DMF Recovery 1410

Water for washing 1500 Residue 90

Effluent 1790

Trifloxystrobin 1000

Reactor

Filtration, Drying &

Solvent recovery

Mass balance of Trifloxystrobin

Reactor

Reaction & Filtration

Reactor

Reaction & Solvent

Recovery


12. Carbendazim


Thiourea reacts with methyl Dimethylsulfate, MCF in presence of catalyst

and water to get Methyl fomate of Thiourea.

Later Methyl fomate of Thiourea is reacted with O-phenylenediamaine at

about 50 – 60°C in presence of formic acid to get crude carbendazim.

Crude product is centrifuged and washed with water followed by drying to

form Carbendazim technical.

Chemical Reaction:


Mass Balance

IN PUT KG OUT PUT KG

Thiourea 425

Dimethoxysulfoxide 480

Catalyst 10

C.S lye 450 Effluent 1300

Water 1200

Methyl chloro formate 485

Formic acid 320

O-phenylene diamine 510


Drying Loss 275

Carbendazim 1000

Total 5380 5380

Reaction

Washing &

Filtration

Drying & Packing

Mass balance of Carbendazim

Reaction


13. Cymoxanil


1-Cyano Acetyl 3-Ethyl Urea reacts with sodium nitrite solution (40%) in

water to give Nitroso salt of 1-(Cyano Acetyl) Ethyl Urea.

Nitroso derivative of 1-(Cyano Acetyl) Ethyl Urea undergoes Methylation

reaction by Dimethyl Sulphate in presence of sodium bicarbonate to give

the final product Cymoxanil.

Crude product is centrifuged and washed with water followed by drying to

form Cymoxanil technical.

Chemical Reaction:

Mass Balance:

INPUT KG OUTPUT KG

1-Cyanoacetyl-3-Ethylurea 785

NaNO2 350

P-TSA 35

Water 1200

DMS 300

Sodium Bi carbonate Salt 100 Inorganic salts 140

Effluent 4910

Water 3500 Drying loss 220

Cymixanil 1000

Total 6270 6270

Nitrosation

Methylation

Filteration &

Drying

Mass balance of Cymoxanil


14. Metalaxyl

Process Description

MDMPA (Methyl-2-[(2,6 dimethyl phenyl) amino] propionate) is charged

in n-Hexane and Methoxy acetyl chloride is charged slowly at reflux

temperature.

HCl formed is taken out by applying mild vacuum and scrubbed by water

and Caustic soda lye. Residual acid is neutralized by alkali and aqueous

phase is separated out.

Product is filtered out, centrifuged and dried. Hexane is recovered from

Mother Liquor.

Chemical Reaction

Mass Balance:

INPUT KG OUTPUT KG

Methoxy Acetyl Chloride 550

MDMPA 1200

Toluene 1250

Caustic soda 125

Water 800

Hexane recovery 1200

Residue 50

Washing 1200 Waste Water 2760

Drying Loss 115

Metalaxyl 1000

Total 5125 5125

Distillation

Filtration

Drying & Packing

Reaction

Mass balance of Metalaxil


15. Thiophenate methyl


Sodium Thiocyanate is added in Ethylene dichloride. Then it is reacted

with Methyl Chloro formate and Methyl Thiocyanate formate is formed.

In ethylene dichloride layer, solution of O-Phenylene Diamine prepared

and after addition the reaction mass is heated to reflux and then

Reaction product is filtered off, washed with water and then dried and

pulverized and packed as Thiophanate Methyl Technical.

Chemical Reaction:

Mass Balance:

INPUT KG OUTPUT KG

EDC 2100

Sodium Thio cyanate 550 EDC Recovery 2010

Methyl chloro formate 650 Residue 90

OPDA 425

Dimethyl Amine 40

Water 3200


Solid waste 180

Drying Loss 285

Thiophenate Methyl 1000

Total 8165 8165

Mass Balance of Thiophenate methyl

Reaction

Filtration & Washing

Separation

Drying & Packing


16. Acetamiprid


N-Cyano methyl Acetamidate (NCMA) is reacted with 2-Chloro 5-(methyl

amino methyl) Pyridine (CMAMP) in methanol.

After the reaction is completed the product is filtered and solvent recovered

and recycled again.

Chemical Reaction

Mass Balance:

INPUT KG OUTPUT KG

NCMA 480

CMAMP 720

Methanol 2200

Acetamiprid 1000

Methanol for washing 250

Methanol recovery 2330

Residue 320

Total 3650 3650

Mass Balance of Acetamipirid

Condensation

Filtration &

Drying

Distillation of ML


17. Imidacloprid

MANUFACTURING PROCESS

2 – Chloro, 5 – Chloro methyl Pyridine (CCMP) is reacted with N – Nitro

iminoIdmidazolidine (N-Nll) in present of catalyst and solvent.

The Hydrochloric acid, which is formed during the reaction, is scavenged

by putting Sodium carbonate as acid scavenger. The resulting mass is

diluted by water and filtered to remove the salts of Sodium Chloride

(NaCl) & Sodium bicarbonate.

The organic mass is then treated with water and finally solvent is

removed by distillation. The concentrated mass is then crystallized to get

pure product – Imidacloprid (Tech).

Finally Toxic Effluent which contains traces of Pesticides is taken to

Hydrolysis stage for detoxification. Where aqueous mass is treated at

high temperature. By Alkali for the rapid hydrolysis of pesticides to

simpler non-toxic compounds.

CHEMICAL REACTION


Mass Balance:

INPUT KG OUTPUT KG

CCMP 890

N-NII 835 DMF Recoverd 2090

DMF 2200 Residue 110

Catalyst 10Na2CO3 750

Water 1200 Recovered Water 1990

C.S. Lye 100 Mix Salt 795

Methanol 3200 Imidacloprid 1000

Methanol Recovered 2850

Residue 350

Total 9185 9185

Condensation &

Solvent Recovery

Water Wash &

Filteration

Crystalization

Mass Balance of Imidacloprid


18. Profenofos


O-chlorophenol and MCB is added along with bromine gas into vessel.

Mass is heated at 1150C. Then add trimethyl amine, Propyle bromide and

Di ethyl thio chloro phosphate.

4-bromo -2-chlorophenyl diethyl thiophosphate (PEA) is reacted with salt

of dimethyldithiocarbamate (Na-DMDT) in presence of catalyst and

solvent –Toluene to form Na-PEA.

After solvent recovery and layer separation of Ethyl ester of

dimethyldithiocarbamate (E-DMDT) taken to Incineration and crude Na-

PFA directly taken to Profenofos preparation.

Crude Na-PFA is reacted with n-Propyl Bromide in presence of catalyst to

give Profenofos Tech.

The organic mixture of profenofos is washed to remove Sodium bromide

salt in water.

After n-Propyl bromide recovery, recycle it to get Profenofos Technical of

89% Purity.

Finally Toxic Effluent which contains traces of Pesticides is taken to

Hydrolysis stage for detoxification where, aqueous mass is treated at high

temperature by Alkali for the rapid hydrolysis of pesticides to simpler

non-toxic compounds.


Chemical Reaction:


Mass Balance

INPUT KG OUTPUT KG

O chlorophenol 390

MCB 2200 HBr 210Br2 550

Tri methyl amine 210Di ethyl thio chloro

phosphate610

C.S lye 300Water 800 MCB Recovery 2100Toluene 1600 Toluene Recovery 1530

Propyle bromide 374 Residue 170Catalyst 10

Profenophos 1000

Water 1600 Effluent 3350Drying loss 284

Total 8644 8644

Reaction

Reaction

Filtration &

Drying

Mass Balance of Profenofos


19. Thiamethoxam


2 Chloro 5 chloromethylthiazole (CCMT) and 3-Methyl-4-

Nitroiminoperhydro- 1,3,5- Oxadiazine (MNTO) are reacted in DMF media

using K2CO3 as catalyst and reaction mass thus obtained is taken for

water and HCl (30%) washing.

Organic mass obtained contains crude thiamethoxam which is purified

with methanol and is dried.

Chemical Reaction:

Mass Balance

INPUT KG OUTPUT KG

CCMT 620

MNTO 580

DMF 2200K2CO3 600

DMF Recovery 2115


30% HCl 440 Effluent 2840

Methanol 1750 Methanol Recovery 1650

Residue 100

Thiamethoxam 1000

Total 7790 7790

Reaction

Filtration

Purification by

Crystalization

Mass Balance of Thiamethoxam


Annexure-III

Water Balance Diagram

3.0

Water consumption 170 KLD (62 Fresh + 108 recycle)

Domestic 6.0

Process water

84

Washing 10

Utilities

60 Green belt

10

Boiler 20

Cooling

40

MEE 98

Recycle water

88+20=108

To soak pit 4.0

Water retained With RM

7 Drying/Evp. Loss 5

Condensate 88

10

Bleed off

10

To TSDF

Process

80

Lab 1.0

Scrubber

3.0

ETP-1 1 + 92 = 93

Salt 2.0

Blow down 2.0

ETP-2

3+10+10+2.0=25 KLD

RO 25

System loss

8.0

Reject-5

Permeate 20

1.0 92


Break up of water consumption and wastewater generation

Sr.

No.

Source Water

Consumption

(KLD)

Wastewater

Generation

(KLD)

I Domestic 6 4

II Gardening 10 0

III Industrial

a) Process 80 92

b) Scrubber 3 3

c) Washing 10 10

d) Boiler 40 10

e) Cooling 20 2

f) Lab 1 1

Total Industrial 154 118

Total (I+II+III) 170 122

Recycle water 108

Actual fresh water

requirement

62


Annexure-IV

Details of Hazardous waste

Sr.

No.

Name of

waste

Sources Category Qty.

Mt/Month

Disposal method

1. ETP sludge

MEE salt

ETP

MEE

35.3 15 MT/Month

52 MT/Month

Collection, Storage, Transportation,

Disposal at TSDF

site.

2. Process

Residue (Inorganic

Salts)

Process 29.1 34

MT/Month

Collection, Storage,

Transportation, Disposal at TSDF

site.

3. Distillation Residue

Purification of Solvent

36.1 57 MT/Month

Collection, Storage, Transportation,

Disposal at approved CHWIF or

for co processing in cement industries.

4. HBr solution Process 26.3 40

KL/Month

Collection, storage,

transportation and

sold to actual end

users under Haz

Waste Rules 9.

5. Spent Catalyst

Process 29.5 0.5 MT/Month

Collection, Storage and Send for

regeneration to suppliers.

6. Discarded

Containers

Linear/Bags

Raw

materials

33.1 Drum:500

Nos./month

Liner:0.4

MT/month


Decontamination, Transportation,

Disposal by selling

to Authorized Recycler.

7. Used Oil Driving

unit & D.G. set

5.1 0.5

KL/year


Transportation, Disposal by selling

to Registered Reprocess


Annexure-V

Details of Air Pollution

Sr.

No.

Stack

attached to

Fuel Type Stack

Height (m)

APC measures Probable

emission

Flue Gas Stacks

1 Boiler (4 T/hr.)

Coal 19 MT/day

26 Cyclone & Bag Filter

PM<150 mg/NM3 SO2<100 ppm

NOx<50 ppm

2 TFH

(15 lac KCal/hr.)

Coal

9 MT/day

21 Cyclone & Bag

Filter

3 D.G. set Stand by (250 KVA)

Diesel 60 lit/hr.

7

--

Process Gas stacks

1 Process vent – 1

-- 15 Two stage Water and Alkali scrubber

NOx<25 mg/NM3

HCl<20 mg/NM3

SO2<40 mg/NM3

HBr<30 mg/NM3

Br2 <2 mg/NM3

2 Process

vent – 2

-- 15 Water and alkali

scrubber

HCl<20 mg/NM3

SO2<40 mg/NM3

HBr<30 mg/NM3

3 Common vent

of FBDs

-- 11 Inbuilt Cyclone &

Bag Filter

PM<150 mg/NM3


Annexure-VI

Proposed TORs

Standard TOR prescribed for Category 5”b” by Ministry of Environment,

Forest and Climate Change


Annexure-VII

Plot allotment letter



Documents

Date : 01/04/2008...Para toluene sulphonic acid and solvent. Later it is reacted with bromine at 20 C in solvent and the Bromo Ketal product is isolated after distillation of solvent