polysulfide preparationenvironmentclearance.nic.in/writereaddata/online/tor/0… · ·...

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HOIST

ERECTIONBAY

POS-0141(N)

POS-0143(N)

POS-0141POS-0191

POS-0151

POS-0153

POS-0141(S)

POS-0143(O)

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HOIST

POS-AR106 POS-1172(S)

HOT/COLD OILPUMP

POS-1132 POS-1131 POS-1172

V-1600 V-20POS-1161(O) POS-1191 POS-1161(S) POS-1181

TETA-2167DIMER

2166(O)TETA-2108 DIMER

2166(S)

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DRUM STORAGE AREA(EXISTING)12 m x 6 m

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DRUM STORAGE

ERECTIONBAY

POS

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STEA

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OR

DRUM STORAGE AREA

LOCKER ROOM &TEA SERVING POINT

3 m x 6 m

WASH ROOM3 m x 3 m

TOILET3 m x 4 m

MCC ROOM9 m x 3 m

MEZZ. FLOOR

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WATERCIRC.TANK

(AT 4 m ELE.)CONTROL&

PANEL ROOM

MCC ROOM(NEW)

MCC ROOM(NEW)

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POS T-1133CARDANOL TANK

(TO BE RELOCATED)

SS TANK(TO BE RELOCATED)

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Unauthorized disclosure to any third party or duplication is not permitted .This drawing is a property of Shroff And Associates (Engineers) Pvt. Ltd.

Title :

Rev Date

Project Name:

Drg. No.Scale

Plant:

Owner:

Description Name

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Approved

Location:

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Project No:

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ATUL LIMITED (Corporate SHE Dept.)

Division: Bulk Intermediate

Name of Product: Caustic soda lye

1. Lab Process details:

1.1

New Project – Lab Process Details

Date:

Brief process and flow diagram of process stage wise Salt & water is charged to prepare saturated brine solution, it is treated chemically with barium carbonate, sodium carbonate & NaOH in precipitation tank. It clarified by adding flocculent & suspended solids separated by filtration. Brine solution further purified in two steps of polishing filtration & ion exchange. Brine flows into anode chamber & weak caustic flows into cathode chamber. Chlorine is liberated at anode surface & hydrogen generated at cathode surface. Two phase mixture of NaOH & hydrogen gets separated at cathode header. 32% NaOH is further concentrated to 50% NaOH by evaporation. Depleted brine is dechlorinated. Chlorate destruction is done under influence of HCl. Chlorine is further treated with 98% sulfuric acid to get dry chlorine. Hydrogen is cooled & passed through filter for treatment.

1.2

Chemicals reactions with molecular weight stage wise

Brine Saturation NaCl

10% Barium carbonate solution Chemical Preparation

Clarification

Filtration

Sec. Brine Purification

Electrolysis

Catholyte system

Anolyte Dechlorination

Chlorate Destruction

Chlorine Treatment

Hydrogen Treatment

10% Sodium carbonate solution 32% NaOH solution

Flocculent

32% NaOH Hydrogen

Chlorine

32% HCl

98% H2SO4 78% H2SO4

Sodium Chloride

Mwt. 58.5

2NaCl(aq) + 2H2O(l) 2NaOH(aq) + Cl2(g) + H2(g)

Water Mwt. 18

Sodium Hydroxide Mwt. 40

Chlorine Mwt. 71

Hydrogen Mwt. 2

Caustic evaporation

32% CS Lye Dist. Water 50% CS Lye

Chlorine Chlorine

Sludge

1.3

S.N.

List of raw materials along with quantity per kg

Chemical name Consumption Kg/kg of 100% NaOH

1 NaCl (100%) 1.5250 2 Barium carbonate (100%) 0.0157 3 Sodium Carbonate (100%) 0.0058 4 HCl (100%) 0.0180 5 NaOH(100%) 0.0150 6 NaHSO3 (100%) 0.0004 7 Flocculating agent 0.00004 8 Precoat alfa cellulose 0.00035 9 Water 3.3000

10 Sulfuric acid (100%) 0.0150

1.4

Sr. No.

List of co-product per kg Chemical name kg /kg

1 Chlorine 0.886

2 Hydrogen 0.0239

1.5

S.No.

Complete Mass balance per kg: Input kg Output kg

1 NaCl (100%) 1.5250 50% NaOH (100%) 1.000 2 Barium carbonate (100%) 0.0157 Chlorine 0.886 3 Sodium Carbonate (100%) 0.0058 Hydrogen 0.0239 4 HCl (100%) 0.0180 Solid waste 0.090 5 NaOH(100%) 0.0150 Liquid effluent 1.0862 6 NaHSO3 (100%) 0.0004 Water in 50% NaOH 1.000 7 Flocculating agent 0.00004 Distilled water 1.260 8 Precoat alfa cellulose 0.00035 Sulfuric acid (78%) 0.01923 9 Water 3.7700

10 Sulfuric acid (100%) 0.0150 Total 5.3653 Total 5.3653

1.6

Complete Molecular balance

2NaCl(aq) + 2H2O(l) 2NaOH(aq) + Cl2(g) + H2(g)

1.7 Sr. No.

Complete Water balance Input Quantity

kg Output Quantity

kg 1 Water 3.770 water 3.386

2. Gas Emission:

Gas emission stage wise per kg: 5mg/nm3 Cl2

Identification

3. Water discharges:

Raw water consumption details per kg Waste water quantity and quality generated i.e. pH, COD TDS acidity, alkalinity etc per kg Stream wise quality of the effluent (Analysis reports | experimental results) per kg Proposed treatment method developed if any: No

Quantity /kg of Product

COD PPM

BOD PPM

TDS PPM

Color

Liquid effluent 1.0862 250 - 125000 colorless

4. Waste generation:

Solid waste generated per kg: 0.090Kg/Kg Solid waste characteristics and its proposed treatment developed if any.

5. Details of Hazardous chemicals:

Hazardous chemicals used and method of handling & disposal. Normal precautions in handling chemicals are to be followed. 6. Other Consideration:

Recycle & Reuse options in process. Solvent recovery details stage wise per kg. Acetone used as solvent & it is recovered & reused in the process.

7. Any other relevant information:

You may want to share about the product\process

Date: Project In-Charge G.M R & D

SULFUR BLACK

POLYSULFIDE PREPARATION

32 % NaOH LYE 6937 KG SULFUR 2905 KG

PHENOLATION

32 % NaOH LYE 2984.3 KG 2:4 DNCB 2415 KG WATER 4100

REDUCTION/COUPLING

THIONATION

FILTRATION

MIXING

WATER WASH

DRYER

NH₃ GAS

H₂S GAS

ML + WATER WASH

OXIDATION

WATER SCRUBBER

ALKALI SCRUBBER

AIR

WATER

5 % AMMONIA

25 % NaOH

27 – 30 % Na₂S

SULFUR BLACK

SODA ASH

SODIUM SULFIDE

MULTIPLE EFFECT EVAPORATOR

CONDENSATECONC. Na₂S₂O₃

Na₂S₂O₃ CRYSTALSSODIUM CHLORIDE

ATUL LIMITED

Name of Product: Anethole (p-Propenylanisole)

Lab Process details:


i) Brief process and flow diagram of process stage wise-

Step 1: Friedel Crafts Acylation (F.C Reaction)

Brief Process: Charge Anisole & EDC in glass reactor. Under stirring cool the reaction mixture.

Charge Aluminum chloride in reaction mass by maintaining temperature. Charge Propionyl chloride

in 3-4h by maintaining temperature. Once addition over continue stirring at same temperature for 2h.

Reaction monitored on GC instrument. After that do the work up. Separate Aqueous and organic

layer. Do the recovery of solvent and fractional distillation of organic material.

(1) Anisole(2) Propionyl Chloride(3)AlCl3 anhyd.(4)EDC

(16) HCl gas evaluation

(6) Ice-Cold water (7) Organic 1:

INPUT(11) Aquous 2: *

(9) EDC (12) Organic 2: (10) Water

(15) Aqueous 3:(14) 13% NaCl (16) Organic 3:

(16) Organic 3: (18) Aqueous 4:(17) 10% NaHCO3 (19) Organic 4:

(20) Recovered EDC(19) Organic 4: (21) ForeCut (tops)

(22) Intercut (tops)(23) Maincut 1(24) Maincut 2(25) % EDC Rec Loss(26) Residue *

(13) Organic 1+ Organic 2

FLOW DIAGRAM 4-MPP (STEP - I)

FC REACTION TIMECYCLE : 6-7 hrs

Stirring for 0.5 hrs

(27) 4-Methoxy propio-phenone

DISTILLATION (4-MPP) TIMECYCLE : 25 hr

Quenching timecycle: by mainting temp. 5-20 deg C: 3-4 hrs

(5) Reaction Mass

(8) Aqueous 1

Washing of organic mass with pH= 7-7.5

Washing of organic mass

Organic Mass for rec. of solvent & Fr. Distillation

Step 2: Hydrogenation

Brief Process: Charge 4-methoxy propiophenone, methanol, tri ethyl amine & catalyst, purge nitrogen

1-2Kg/cm2 in autoclave. After complete H2 consumption takes the sample & checks the conversion of

reaction mass by GC. Cool the mass & release the pressure from autoclave. Filter the reaction mass &

recover the catalyst which is to be recycled in next batch. After 5 times recycle spent catalyst for sell

as by-product/send for regeneration.

(1) Distilled 4-MPP(2) Raney Ni(3) Triethyl amine(4) MethanolHydrogen gas

Filter (7) Filtrate 4-MPP alcohol(8) Rec. R-Ni

(7) 4-MPP alcohol

Flow diagram Hydrogenation 4-MPP alcohol (Step-2)

Autoclave(5) Flush with N2 two times then

H2 two times

.

Step 3: Dehydration

Brief Process: Charge paraffin & potassium hydrogen sulphate in R.B flask. Charge 1-(4-

Methoxy phenyl) propyl-1-ol in RBF drop by drop through addition funnel. Check GC % Area of

crude Anethole for complete conversion of 4-MPP alcohol to cis & trans-Anethole. Workup done

separating crude Anethole and water. Take crude Anethole for fractional distillation.

Note: The Apparatus must be completely clean and dry.

(1) 4-MPP alcohol (5) Crude Anethol(2) KHSO4 (6) Water(3) Paraffin(4) High Vacuum

(7) Residue

Dehydration Assembly

Flow diagram Dehydration : crude Anethole (step 3)

Step 4: Fractional distillation of crude Anethole

Fractional distillation using 3 meter long packed (ss net) column with reflux divider.

(1) Crude Anethol (3) Forecut (tops)(2) Vacuum 1-2 mbar (4) Intercut (tops)

(5) Maincut (t-Anethole)(6) H.B *

(7) Residue *

FLOW DIAGRAM FOR ANETHOLE (STEP - 4)

Distillation Assembly

ii) Chemicals reactions with molecular weight stage wise Step 1: Acylation

O

H3COH3CO Cl

OAlCl3

EDC92.5 164

Anisole Pr-chloride 4-MPP108MW-

(133)

(99)


O

H3CO

OH

H3CO

H2

164

4-MPP

Methanol (32); R-Ni

1664-MPP alcohol

MW-

OH

H3CO H3CO H3CO

-H2O

t-Anethole cis-Anethole

Step 3: Dehydraation

166

4-MPP alcohol

KHSO4148 148MW- (136)

Step 4: Fraction distillation of Anethole isomer

H3CO H3CO

t-Anethole cis-Anethole148 148MW-

H3CO

t-Anethole148

iii) List of raw materials along with quantity per KG

1 Anisole 108 1.122 Propionyl chloride 92.5 1.0663 Aluminium Chloride (AlCl3) 133.5 1.374 Ethylene dichloride (EDC) 99.8 0.465 Sodium chloride 58.5 0.13

6Sodium bicarbonate (NaHCO3)

84 0.13

7 Ra-Ni- (Monarch ltd) 0.018 Methanol 32 0.1639 H2 gas 2 0.018910 N2 Gas 28 0.00211 Triethyl amine 101.5 0.001712 Paraffin Oil- Merck 0.07

13Potassium hydrogen sulphate (KHSO4)

120 0.04

Sr. No. Raw Materials MW (g)

Raw material consumption data for 1kg Anethole

Qty. req. kg/kg of product

.

iv) Complete Mass balance per KG

Material req. kg/kg Anethole Sr.No. Raw Materials Input Qty kg Sr.No Materials Output Qty kg

1 Anisole 1.04 1 Aqueous 2 6.790833 2 Propionyl Chloride 1.003 2 Aqueous 3 1.85956 3 AlCl3 1.34 3 Aqueous 4 1.299667 4 EDC 1.992 4 Recovered EDC 2.93455 5 Ice cold water 3.097 5 Tops step 1 0.075 6 EDC 1.097 6 Residue step 1 0.069922 7 Water 2.103 7 Rec. Methanol 1.125 8 13% NaCl 1.667 8 Rec. R-Ni 8030 0.034722 9 10% NaHCO3 0.764 9 Water 0.13944 10 Methanol 1.25 10 Residue 0.199556 11 R-Ni 8030 0.030889 11 Anethole 1 12 Tri ethyl amine 0.003089 Total output 15.52825 13 KHSO4 0.0125

14 Paraffin oil 0.054792

Mass balance: 98.73 %

Total input 15.728

v) Complete Molecular balance

Step 1: Acylation

O

H3COH3CO Cl

OAlCl3

EDC

92.5 164

Anisole Pr-chloride 4-MPP

108MW-

(133)(99)

HCl

36.5


O

H3CO

OH

H3COH2

164

4-MPP

Methanol; R-Ni

166

4-MPP alcohol

M.W- 2

OH

H3CO H3CO-H2O

Crude Anethole

Step 3: Dehydraation

166

4-MPP alcohol

KHSO4

148MW-

(136)H2O

18Water

Step 4: Fraction distillation of Anethole isomer

H3CO H3CO

Crude - Anetholecis-Anethole148MW-

H3CO

t-Anethole148

&

ATUL LIMITED

Name of Product: Avobenzone



Brief process and flow diagram of process stage wise Stage-1: Process for 4-t-butylbenzoicacid to Ester

Charge 4-t-butylbenzoicacid and add Methanol and start stirring. Slowly add H2SO4 and heat the mass to reflux. Stir the mass at reflux till the desire conversion. Recover methanol and allow to separate the layers. The bottom aq layer is to be recycled in the next batch. Wash the organic layer with sodium bicarbonate solution to recover & recycle the unreacted acid. Purify the product by vacuum distillation.

Stage-2: Process for Avobenzone

Charge toluene and heat the solution to reflux temp. Distill out some toluene to remove moisture. Cool the mass to 60oC. Add sodium methoxide and mixture of methyl 4-tert-butylbenzoate, 4-methoxyacetophenone and toluene. Stir the reaction mass at same temp and monitor on GC. Cool the mass, acidify with dilute acid and separate the layers. Wash the organic phase with water. Collect aqueous layer & washings for p-tert-butylbenzoic acid recovery. Recover toluene from organic layer under vacuum. Add methanol and stir the mass at reflux temp. Gradually cool the mass and stir for 15 min. Filter the slurry under vacuum and dry the product in vacuum oven.

Flow diagram

Stage-1:

Reflux

Recovered methanol

4-t-butylbenzoicacid

Distillation

Residue

Product

Organic layer M.L

Recovered acid

Methanol 98% H 2 SO 4

Methanol recovery

5% Na 2 CO 3 wash H 2 SO 4

Organic layer Spent acid layer

Aq layer

To be recycled

To be recycled

To ETP

To be incinerated

Toluene

Stage-2:

4-MAP + Ester+Toluene

Distillation Toluene

Reaction Distillation Toluene+methanol

Recovered Toluene

1 st crystallisation

2 nd crystallization

Workup 10% H 2 SO 4

Organic layer Water wash

Recovered acid

Aq. layer

Product

H 2 SO 4

M.L

M.L

Residue Methanol recovery

Recovered methanol

Aq. layer

Mixing

Toluene recovery

Aq. layer

Cooling

Methanol

Methanol

Drying

To be recycled

To be recycled

To ETP

To be incinerated

To be recycled

To be recycled

NaOMe


COOCH3

C12H16O2192.3

methyl 4-t-butylbenzoate

COOH

C11H14O2 178.2


+ CH3OH

Conc.H2SO4

CH4O32

Methanol

-H2O

Stage-1

COCH3

OCH3

+

COOCH3

CH3ONa

C9H10O2150.2

4-MAP

C12H16O2192.3


H3CO

O O

C20H22O3310.39

Avobenzone

Stage-2

List of raw materials along with quantity per KG

Complete Mass balance per KG

Input

Stage-1

g Output g

4-t-butylbenzoicacid 250 Aq. layer (spent acid) 53

Methanol 225.3 Recovered acid 3.2

98% H2SO4 30.6 Methyl-4-t-butylbenzoate 247

5% Na2CO3 100 Recovered methanol 158

Water 50 Aq.layer 142

Residue 8

Methanol loss 21

Water loss on drying 22

655.9 Total 654.2 Mass balance = 99.74%

Sr. No. Raw Materials Molecular weight

(g) Quantities

Practical kg/kg of Product 1 4-Methoxyacetophenone 150.2 0.730 2 4-tert-butylbenzoicacid 178.2 0.753 3 Sodium Methoxide 54 0.322 4 Toluene 92 0.454 5 Methanol 32 1.300 6 98% sulfuric acid 98 0.447 7 Sodium bicarbonate 84 0.019

Input

Stage-2

g Output g

4-methoxyacetophenone 112.5 Aq. layer 1157

Methyl-4-t-butylbenzoate 151.2 Recovered acid 35

Sodium methoxide 49.6 Recovered toluene 808

Toluene 850 Recovered methanol 675

Methanol 750 Avobenzone 154

10% H2SO4 504 Residue 52

Water 600 Methanol loss 75

Toluene loss 42


3017.3 Total 3008

Mass balance = 99.67%

ATUL LIMITED

Name of Product: Avobenzone



Brief process and flow diagram of process stage wise Stage-1: Process for 4-t-butylbenzoicacid to Ester

Charge 4-t-butylbenzoicacid and add Methanol and start stirring. Slowly add H2SO4 and heat the mass to reflux. Stir the mass at reflux till the desire conversion. Recover methanol and allow to separate the layers. The bottom aq layer is to be recycled in the next batch. Wash the organic layer with sodium bicarbonate solution to recover & recycle the unreacted acid. Purify the product by vacuum distillation.

Stage-2: Process for Avobenzone

Charge toluene and heat the solution to reflux temp. Distill out some toluene to remove moisture. Cool the mass to 60oC. Add sodium methoxide and mixture of methyl 4-tert-butylbenzoate, 4-methoxyacetophenone and toluene. Stir the reaction mass at same temp and monitor on GC. Cool the mass, acidify with dilute acid and separate the layers. Wash the organic phase with water. Collect aqueous layer & washings for p-tert-butylbenzoic acid recovery. Recover toluene from organic layer under vacuum. Add methanol and stir the mass at reflux temp. Gradually cool the mass and stir for 15 min. Filter the slurry under vacuum and dry the product in vacuum oven.

Flow diagram

Stage-1:

Reflux

Recovered methanol


Distillation

Residue

Product

Organic layer M.L

Recovered acid

Methanol 98% H 2 SO 4

Methanol recovery

5% Na 2 CO 3 wash H 2 SO 4

Organic layer Spent acid layer

Aq layer

To be recycled

To be recycled

To ETP

To be incinerated

Toluene

Stage-2:

4-MAP + Ester+Toluene

Distillation Toluene

Reaction Distillation Toluene+methanol

Recovered Toluene

1 st crystallisation

2 nd crystallization

Workup 10% H 2 SO 4

Organic layer Water wash

Recovered acid

Aq. layer

Product

H 2 SO 4

M.L

M.L

Residue Methanol recovery

Recovered methanol

Aq. layer

Mixing

Toluene recovery

Aq. layer

Cooling

Methanol

Methanol

Drying

To be recycled

To be recycled

To ETP

To be incinerated

To be recycled

To be recycled

NaOMe


COOCH3

C12H16O2192.3


COOH

C11H14O2 178.2


+ CH3OH

Conc.H2SO4

CH4O32

Methanol

-H2O

Stage-1

COCH3

OCH3

+

COOCH3

CH3ONa

C9H10O2150.2

4-MAP

C12H16O2192.3


H3CO

O O

C20H22O3310.39

Avobenzone

Stage-2



Input

Stage-1

g Output g

4-t-butylbenzoicacid 250 Aq. layer (spent acid) 53

Methanol 225.3 Recovered acid 3.2

98% H2SO4 30.6 Methyl-4-t-butylbenzoate 247

5% Na2CO3 100 Recovered methanol 158

Water 50 Aq.layer 142

Residue 8

Methanol loss 21


655.9 Total 654.2 Mass balance = 99.74%

Sr. No. Raw Materials Molecular weight

(g) Quantities

Practical kg/kg of Product 1 4-Methoxyacetophenone 150.2 0.730 2 4-tert-butylbenzoicacid 178.2 0.753 3 Sodium Methoxide 54 0.322 4 Toluene 92 0.454 5 Methanol 32 1.300 6 98% sulfuric acid 98 0.447 7 Sodium bicarbonate 84 0.019

Input

Stage-2

g Output g

4-methoxyacetophenone 112.5 Aq. layer 1157

Methyl-4-t-butylbenzoate 151.2 Recovered acid 35

Sodium methoxide 49.6 Recovered toluene 808

Toluene 850 Recovered methanol 675

Methanol 750 Avobenzone 154

10% H2SO4 504 Residue 52

Water 600 Methanol loss 75

Toluene loss 42


3017.3 Total 3008

Mass balance = 99.67%

ATUL LIMITED

Name of Product : OCTOCRYLENE

1. Lab Process details :


Brief process and flow diagram of process stage wise: In 1st step ester formed by the condensation of a Cyanoacetic acid with 2-ethylhexanol in presence of

PTSA as catalyst, which is worked up & fractionally distilled to get pure 2-Ehtyhexyl cyanoacetate (2-EHCA). In 2nd step 2-Ethylhexyl cyanoacetate (2-EHCA), Benzophenone (BP), ammonium acetate, acetic acid and Cyclohexane are mixed. The mixture is heated under stirring to reflux temperature and water is distilled out azeotropically. The reaction mass is cooled and worked up. Crude product is fractionally distilled to get pure Octacrylene.

2-ETHYLHEXYL-2-CYANOACETATE [2-EHCA] FLOW DIAGRAM OF STEP- I : OF OCTOCRYLENE

Fractional distillation

NITROGEN GAS

FLOW DIAGRAM OF STEP- II : OF OCTOCRYLENE

[OCR]

in 20 hrs.


Chemicals reactions with molecular weight stage wise:

R M for 1 kg OCTOCRYLENE

List of raw materials along with quantity per KG:

Sr. No. Raw Materials

Lab. Expt. Qty.

in (g)

Qty. for1 kg in (g)

Mol. wt Moles

1 Cyanoacetic acid 85 395 85 4.647 2 2-Ethylhexanol(consumed) 120 558 130.2 4.286 3 p-Toluene sulfonic acid 2.4 11 190 0.058 4 2-EHCA 176.3 820 197.3 4.156 5 Benzophenone(consumed) 120.2 559 182.2 3.068 6 Cyclohexane(consumed)in lit. 60 276 84.16 3.279 7 Glacial acetic acid 148 690 60.05 11.50 8 Ammonium acetate 43 200 77.08 2.595 9 Ground salt 15 70 58.5 11.97

10 Methanol (consumed) 77 360 32 11.25 11 Darco 16 75 - - 12 Hyflosupercell 4 19 - - 13 Anhydrous Glauber’s salt 4 19 - -

C C

C

C

O

N

O CH3

H3C

2-Propenoic acid, 2-cyano-3,3-diphenyl-, 2-ethylhexyl ester or Octocrylene CAS no.: 6197-30-4 M.Wt.:361

C=O

Ammonium acetate,Acetic acid & Cyclohexane , Heat to 94 - 105°C, distill mix. of water,

BenzophenoneCas no.:119-61-9M.wt. 182

HOC C N

O

Cyanoacetic acidCAS no.: 372-09-8M.wt.: 85

+

H3C OH

CH3

2-Ethylhexane-1-olCAS no.: 104-76-7M.Wt.: 130

H3C SO3H

Reflux for 3.5 hr., distill water,. at 104 - 125°C

2-Ethylhexyl -2-cyanoacetateCAS no.: 13361-34-7M.Wt.: 197

+

O

O

N

MATERIAL BALANCE FOR OCTOCRYLENE

Complete Mass balance per KG: (% Mass balance 99.856%)

Sr. no. INPUT Quantity

in (kg) OUTPUT Quantity in (kg)

1 Cyanoacetic acid 0.395 Middle cut of 2 - EHCA dist. 0.008

2 2 - Ethyl hexanol 0.678 Recovered Ethyl hexanol 0.125 3 p - Toluenesulfonic acid 0.013 Recoveed Cyclohexane 0.65 4 Water 3.098 Recovered Benzophenone 0.656 5 Benzophenone 1.218 Recovered 2 - EHCA 0.222 6 Acetic acid 0.853 Recovered MeOH 2.10 7 Ammonium acetate 0.247 Trap 0.11 8 Cyclohexane 0.685 Distillate 0.470 9 Methanol 2.340 Water wash 3.585

10 NaCl 0.085 Octocrylene 1.000 11 Darco 0.086 Darco sludge 0.149 12 Hyflowsupper cell 0.023 Organic solvent loss 0.500 13 Anhyd. Na2SO4 0.023 Handling loss 0.100 14

Residue 0.055

9.744

9.73

Molar calculation (2-EHCA)

Complete Molecular balance :

Sr. No. Raw Material Weight

in g M.wt. Moles Molar Ratio

1 2-Ethylhexanol 150 130.23 1.151808 1 2 Cyano acetic acid 85 85 1 0.8682 3 p-Toluene sulfonic acid.H2O 2.4 190 0.012632 0.010967 4 2-Ethylhexyl-2-cyanoacetate 176.3 197.3 0.893563 0.775791

Molar calculation (OCTOCRYLENE) Sr. No. Raw Material Weight

in g M.wt. Moles Molar Ratio

1 2-Ethylhexyl-2-cyanoacetate 177.8 197.3 0.901166 1 2 Benzophenone 213.3 182.2 1.170692 1.299086 3 Cyclohexane 117 84.16 1.390209 1.542679 4 Acetic acid (Glacial) 149.4 60.05 2.487927 2.760787 5 Ammonium acetate 43.2 77.08 0.560457 0.621924 6 Methanol 385 32 12.0312 13.3507 7 Darco 16 - - - 8 Hyflosuper cell 4 - - - 9 Anhydrous Na2SO4 4 142 - -

10 Salt 15 58.5 - -

Confidential & Restricted Circulation Page 1 of 5

ATUL LTD

Name of Product: Octyl Methoxy Cinnamate (OMC)




Step 1: Esterification

Brief Process: In 1st step ester formed by the condensation of P- Anisaldehyde (PAA) with

Ethyl acetate in presence of Sodium Methoxide powder as a catalyst, which is worked up and get

the mixture of 4-Methoxycinnamic acid ethylester (4-EMC) and 4-Methoxycinnamic acid

methylester (4-MMC).

Step 2: trans-esterification

Brief Process: In 2nd step, 4-Methoxycinnamic acid ethylester (4-EMC) and 4-Methoxycinnamic

acid methylester (4-MMC) react with 2-Ethyl hexanol in presence of liquid Sodium Methoxide.

The mixture heated under stirring at ambient temperature and vacuum to remove/distilled out

mixture of solvent. The reaction mass is cooled and worked up. Crude product fractionally

distilled to get pure Octyl Methoxy Cinnamate (OMC)


FLOW DIAGRAM- OMC


ii) Chemical Reactions with Molecular Weight Stage wise:

p-AnisaldehydeCAS 123-11-5C8H8O2MW 136

+

Ethyl acetateCAS 141-78-6C4H8O2MW 88

NaOMe+

4-Methoxycinnamic acidethylesterCAS no.: 1929-30-2MF : C12H14O3M.Wt.: 206

4-Methoxycinnamic acidmethylesterCAS no.: 832-01-9MF : C11H12O3M.Wt.: 192

OCH3

CHO

CH3COOC2H5

OC2H5

O

OCH3

OCH3

O

OCH3

Step – 1st

+

4-Methoxycinnamicacid ethylesterCAS no.: 1929-30-2MF : C12H14O3M.Wt.: 206

4-Methoxycinnamicacid methylesterCAS no.: 832-01-9MF : C11H12O3M.Wt.: 192

OH

-C2H5OH -CH3OH

2-Ethyl hexanolCAS 104-76-7C8H18OMW 130

2-Ethylhexyl-4-methoxycinnamateOctylmethoxy cinnamate (OMC)CAS no.: 5466-77-3MF : C18H26O3M.Wt.: 290

OC2H5

O

OCH3

OCH3

O

OCH3

NaOMe

OCH3

O

O

+

Step – 2nd


iii) List of Raw Materials along with quantity per Kg:

RAW MATERIALS CONSUMPTION FOR 1kg OMC

Sr./No. Raw Material Mol. Wt. Quantity (Kg)

1 P-Anisaldehyde 136.15 0.5913 2 Ethyl acetate 88.11 0.4391 3 Sodium Methoxide (98%) 54.02 0.2982 4 Phosphoric acid (85%) 98.00 0.0147 5 2-Ethylhexanol 130.23 0.6043 6 Sodium methoxide (30%) 54.02 0.0326 7 Formic acid 46.03 0.0097 8 Divyol 460 - 0.0815 9 Darco - 0.014

10 Hyflo supercell - 0.0059

iv) Mass Balance data for 1Kg OMC

Sr. no. INPUT Quantity

in (g) OUTPUT Quantity in (g)

1 p-Anisaldehyde 593 Recovered Ethyl acetate 1741 2 Ethyl acetate 2180 Recovered Ethyl hexanol 195 3 Ethyl hexanol 675 Ethanol/Methanol 270 4 Sodium methoxide powder 302 Aqueous for recovery 1620 5 Sodium methoxide solution 114 Water to be recycle 2000 6 Phosphoric acid 22.5 OMC 1000 7 Formic acid 6.5 OMC to be recycle (100%) 50 8 Divyol 460 108 Residue 152 9 Fresh Water 1620 Divyol 460 108

10 ml of OMC recycled 2000 Fraction-2 to be recycle 54 11 Fraction-2 54 Darco sludge 25 12 Darco 13 Distillate of MeOH/EtOH etc 320 13 Hyflo supercell 5.5 W/C of MMC/EMC recovered 65

7693.5 7600 Mass Balance – 99.00%


v) Complete Molecular Balance:

Sr.No. Raw Material M.Wt. Moles

1 P-Anisaldehyde 136.15 4.000

2 Ethyl acetate 88.11 22.87

3 Sodium Methoxide powder 54.02 5.083

4 Phosphoric acid 98.00 0.182

5 2 – Ethylhexanol 130.23 4.808

6 Sodium methoxide 54.02 0.583

7 Formic acid 46.03 0.128

8 Divyol 460 - -

9 Darco - -

ATUL LTD


Name of Product: p-Anisylpropanal

(1) Brief process and flow diagram of process stage wise

Step -1: Condensation of p-Anisaldehyde (PAA) & Propanaldehyde to form p-Anisylpropenal

(Step-1):

p-Anisaldehyde is condensed with propanaldehyde in presence of sodium hydroxide as a base and

Methanol as a solvent. Conversion is checked by GC analysis. reaction mass is neutralized with Sulfuric

acid followed by methanol recovery and extraction in toluene and organic layer is washed with water and

sodium bicarbonate. Toluene is recovered by distillation to generate crude. Finally product is obtained by

fractional distillation.

Step -2: Hydrogenation of p-Anisyl propenal (Step-1) to form p-Anisylpropanal (Step-2)

p-Anisyl propenal is hydrogenated with hydrogen gas in Autoclave in presence of 5% Pd/C as

catalyst and Sodium carbonate. Methanol is used as solvent. After hydrogenation, catalyst is recovered by

filtration followed by Methanol recovery. Finally the product is purified by fraction distillation. Note: The

autoclave must be completely clean and dry.

Process flow diagram of Step-1:

Process flow diagram of Step-2:

p-Anisaldehyde (PAA)Propionaldehyde Rec. Methanol Recycle

Methanol 35% NaOH solutionH2SO4

Water (1st wash) Toluene 5% NaHCO3 soln (2nd) Aq-3* (Recycle)Water (3rd wash)

Rec. Toluene Recycle

Rec.PAA Recycle

Divyol Oil (460) Intercut Recycle B.H.T.

Highers Recycle

Residue Co-product


p-Anisylpropenal

Washing and separation

Aq-1 & 2 (For effluent)

Toluene recovery

Reaction and Methanol recovery

p-Anisylpropenal (Step-1)Methanol Sodium CarboanteWater5% Palladium Carbon

Methanol Rec. Catalyst Recycle

Rec. Methanol Recycle

Forecut (Recycle)B.H.T.

Residue Co-productFractional distillation

p-Anisylpropanal

Hydrogen gas

Hydrogenation

Methanol recovery

Catalyst filtration

(2) Chemicals reactions with molecular weight stage wise:

Step-1: Condensation

H3CO

CHO

p-Anisaldehyde (PAA)

Mol.Wt=136 g/mol

+ CH3

O

Propanaldehyde

Mol.Wt=58 g/mol

NaOH (40 g/mol) Methanol (32 g/mol)

H3COCH3

O

p-Anisylpropenal (Step-1)

Mol.Wt=176 g/mol

+ H2O

Step-2: Hydrogenation

H3COCH3

O

p-Anisylpropanal (Step-2)

Mol.Wt=178 g/mol

H3COCH3

O


Mol.Wt=176 g/mol

5% Pd/CMeOH (32 g/mol)

H2 gas

(3) List of raw materials along with quantity per KG

Raw materials consumption data for 1kg p-Anisyl propanal

Sr. No. Raw Materials Molecular

Weight (g) Quantities

kg/1kg of Product 1 p-Anisaldehyde* 136 1.0143 2 Propanaldehyde 58 0.5102 3 Sodium hydroxide 40 0.0154 4 Sodium bicarbonate 84 0.0220 5 Sodium carbonate 106 0.0224 6 Sulfuric acid 98 0.0132 7 Methanol* 32 0.2890 8 Toluene* 92 0.0788 9 5% Pd/C (5T 756) Dry Basis** 0.0002

10 Hydrogen gas 2 0.0159 11 Butylated Hydroxy Toluene 220 0.0045 12 Divyol Oil (460) 0.0220 13 Nitrogen gas 14 0.004

* All the quantity based on consumed Raw materials. **Actual consumption (1+5 recycle)

(4) Complete Mass balance per KG

Input Output Remarks

Sr. No. Charged Qty (Kg) Sr. No. Obtained Qty

(Kg) 1 p-Anisic aldehyde 1.79 1 Aq-1 0.495 2 Propanaldehyde 0.51 2 Aq-2 0.497 3 Sodium hydroxide 0.0154 3 Aq-3 0.501 Recycle in next batch 4 Methanol 4.62 4 Rec. PAA 0.78 Recycle in next batch 5 Sulfuric acid 0.0132 5 Rec. Methanol 4.6 Recycle in next batch 6 sodium bicarbonate 0.022 6 Recovered Toluene 1.49 Recycle in next batch 7 Sodium carbonate 0.0224 7 Rec. Pd/C 0.0122 Recycle in next batch 8 Toluene 1.5 8 Residue (Step-1) 0.214 Sold as Co-product 9 5% Palladium Carbon 0.0143 9 Residue (Step-2) 0.08 Sold as Co-product 10 Water 1.33 10 Canthoxal 1 11 Divyol Oil 0.022 11 12 BHT 0.0035 9.8628 9.6692 Mass balance 98.03707

(5) Complete Molecular balance

H3CO

CHO

p-Anisaldehyde (PAA)Mol.Wt=136 g/mol

+ CH3

O

PropanaldehydeMol.Wt=58 g/mol

NaOH (40 g/mol) Methanol (32 g/mol)

H3COCH3

O

p-Anisylpropenal (Step-1)Mol.Wt=176 g/mol

+ H2O

WaterMol.Wt=18 g/mol

Step-1: Condensation:

H3COCH3

O

p-Anisylpropanal (Step-2)

Mol.Wt=178 g/mol

H3COCH3

O


Mol.Wt=176 g/mol

5% Pd/CMeOH (32 g/mol)

H2 (2 g/mol)

Step-2: Hydrogenation:

ATUL LTD

Name of Product: Raspberry Ketone

Lab Process details:-


1. Step-1 Oxidation and condensation :

Charge methanol, p-cresol, Cobalt acetate, cupric oxide, and sodium hydroxide in autoclave. Purge Oxygen

gas and complete the reaction. Filter the reaction mass followed by methanol recovery. Take the material

for condensation with acetone. Complete the reaction; the reaction mass take for neutralization with

Hydrochloric acid followed by filtration and water wash.

2. Step-2 Hydrogenation

Charge 4-Hydroxybenzyledene acetone, Ra-Ni, tri ethylamine & methanol in autoclave & start stirring.

Purge hydrogen gas and complete the reaction followed by filtration and methanol recovery. Crude

product is taken for flash vacuum distillation with paraffin oil followed by crystallization with methanol

and obtained the final product Raspberry ketone.

p-CresolMethanol

Sodium HydroxideCobalt acetateCopper oxide

Oxygen

Water Catalyst Methanol Recycle

Methanol Rec.Recycle

AcetoneWater

Hydrochloric acid

Water Filterate

Ra-NiTEA

MethanolHydrogen Ra-Ni

Recycle

Methanol Recycle

Crude RBK

Crude RB Rapid mainParaffin oil Residue*

Paraffin oil

Rapid Main Crop-lMethanol Crop-ll

Crop-IIIMethaol rec.

Condensation

Process flow digram of Raspberry Ketone

Oxidation

Filteration

Filterate

Reaction mass

Crystall ization

Neutralization

Hydroxy benzylidene acetone

Hydrogenation

Filteration

Metanol Recovery

Disti l lation

Chemicals reactions with molecular weight stage wise Step-1 Oxidation and condensation:

Step-2 Hydrogenation:

CHO

ONa.2H2O

CH3CH2OCH3(58)

CH=CHCOCH3

OH

p-Hydroxybanzaldehyde1-(4-hydroxyphenyl)-3-butanone

180 162

C7H9O4Na C10H10O2

-H2O(18)

CH3

OH

108

C7H8O

p-Cresol

Co(Ac)2(249)CuO(79)

O2

(40

(32)

CH=CHCOCH3

OH

CH2CH2COCH3

OH

Ra-NiH2

1-(4-hydroxyphenyl)-3-butanone Raspberry ketone162 164

C10H10O2C10H12O2

i) List of raw materials along with quantity per KG

p-cresol to Raspberry ketone

RM Consumption /Kg

sr. no. Raw materials Mw Ratio Kg/kg

1 p-cresol 108 1.3

2 NaOH (flaks) 40 1.68

3 Methanol 32 .03

4 Cobalt acetate 249 .02

5 Copper oxide 79 0.0048

6 oxygen 32 0.5

7 Acetone 58 1.05

8 HCl 36.5 2.75

9 Ra-Ni (1961) - 0.013

10 Hydrogen 2 0.03

11 water 18 4.5 12 Triethyl amine 101.19 0.0158

13 Divyol oil - .05

ii) Complete Mass balance per KG

Material req. kg/kg Raspberry Ketone

Sr.No. Raw Materials Input Qty kg Sr.No Materials Output Qty kg

1 p-cresol 1.3 1 Catalyst 0.48 2 NaOH (flaks) 1.68 2 Methanol 7.97 3 Methanol 8.08 3 Filtrate 13.43 4 Cobalt acetate 0.02 4 Ra-Ni 0.02 5 Copper oxide 0.0048 5 By-product 0.17 6 Oxygen 0.5 6 RBK Crop-I 0.42 7 Acetone 1.2 7 RBK Crop-II 0.384 8 30%HCl 2.75 8 RBK Crop-III 0.202

9 Ra-Ni (1961) 0.013 9 Recover acetone + water 0.7

10 Hydrogen 0.03 10 Divyol oil 0.05 11 Water 9

12 Triethyl amine 0.0158 Total output 23.83 13 Divyol oil 0.05

Total input 24.64 % Mass balance = 96.74

iii) Complete Molecular balance

Step-1 Oxidation and condensation:

Step-2 Hydrogeantion

CH3COCH3

CH=CHCOCH3

OH

1-(4-hydroxyphenyl)-3-butanone162

C10H10O2

CH3

OH

108

C7H8O

p-Cresol

O2

(32)

+ +

(58)

+ 2H2O

(18)

Oxygen Acetone Water

CH=CHCOCH3

OH

CH2CH2COCH3

OH

Ra-NiH2

1-(4-hydroxyphenyl)-3-butanoneRaspberry ketone162

164

C10H10O2C10H12O2

+

Hydrogen(2)

ATUL LIMITED

Name of Product: 1,3-Cyclohexanedione (1,3-CHD)


1.1


Brief process and flow diagram of process stage wise 1,3-CHD is manufactured by catalytic hydrogenation of Resorcinol in the presence of caustic soda in aqueous medium. Hydrogenated mass is acidified using Hydrochloric acid to get out 1,3-CHD.

Hydrogenation Catalyst

Resorcinol Hydrogen

Work-up

Filtration

1,3 CHD Drying

Filtration Catalyst

ML

Water Caustic soda flakes

HCl

1.2

1.3


S.N.


Chemical name Consumption /kg

1 Resorcinol 1.056 2 Caustic soda flakes 0.384 3 Hydrogen 0.021 4 Catalyst 0.0093 5 HCl (36%) 1.056 6 Water 1.320

1.5

S.No.

Complete Mass balance per kg: Input

Input kg Output kg 1 Resorcinol 1.056 1,3-Cyclohexanedione 1.000 2 Caustic soda flakes 0.384 Mother Liquor 2.837 3 Hydrogen 0.021 Catalyst 0.0093 4 Catalyst 0.0093 5 HCl (36%) 1.056 6 Water 1.320 Total 3.846 Total 3.846

1.6

C6H6O2 + H2 + NaOH + HCl C6H8O2 + H2O + NaCl


ATUL LIMITED

Name of Product: Anisole


1.1


Brief process and flow diagram of process stage wise Anisole is manufactured by methylation of Phenol in the presence of caustic soda with Dimethyl sulfate. Crude Anisole is further purified by vacuum distillation.

1.2


Methylation Reaction Phenol

Di-methyl Sulfate

Water CS Lye

Work-up Aq. Layer

Distillation Anisole

Residue

1.3

S.N.



1 Phenol 0.91 2 Di-methyl Sulfate 0.83 3 CS Lye (48%) 0.98 4 Water 1.31

1.5

S.No.


Input kg Output kg 1 Phenol 0.907 Anisole 1.000

Di-methyl Sulfate 0.834 Aq. Layer 2.993 3 CS Lye (48%) 0.979 Residue 0.036 4 Water 1.315 Distillation Loss 0.006 Total 4.034 Total 4.034

1.6

C6H6O +NaOH + ½ C2H6SO4 C7H8O + H2O+½ Na2SO4


CHEMICAL REACTION OF EPOXY RESIN (BLR)

HO C OH

CH3

CH3

2 CH2 CH CH2

O Cl

+ 2NaOH+

+ 2NaCl + 2H2O

Bisphenol A288

EPICHLOROHYDRINE

92.5 40

RESIN

340

BPA: 0.68 kg

ECH: 2.08 kg

DISTILLATION

Eff. To ETP: 4.51 kg

REACTION

Steam: 0.098 kg

ECH: 1.41 kg

DISTILLATION

FLOW DIAGRAM WITH MASS BALANCE OF EPOXY RESIN (BLR)

Caustic: 0.489 kg

IPA: 0.01 kg

Wash water: 3 kg

Wash water: 0.8 kg

ECH: 0.113 kg

Residue: 0.037 kg

Recycled water: 0.098 kg

PURIFICATION

Caustic: 0.011 kg

FILTRATION

Distilled water: 0.13 kg

RESIN: 0.978 kg

Water: 1 kg

Steam: 0.1 kgEff. To ETP: 1.01 kg

Filter cake: 0.009 kg

ATUL LIMITED

Name of Product: Thiamethoxam



Brief process and flow diagram of process stage wise

2-chloro-5-chloromethyl thiazole (CCMT) is reacted with 3-methyl-4-nitroimino perhydro-1,3,5-oxadiazine(NII)in presence of Dimethyl carbonate (DMC) as solvent and potassium hydroxide as base. After completion of reaction, DMC is recovered, water added and product is filtered, washed with water and purified in ethanol. Finally product dried at 60°c.

N

SCl

Cl HN N

O

NNO2

CH3

N

SCl

N N

O

NNO2

CH3

2-chloro-5-chloromethyl thiazole

M.W.-168 g/m3-methyl-4-nitroimino-perhydro-1,3,5-oxadiazine

M.W.-160 g/m

Thiamethoxam

M.W.-291.5 g/mM.F.-C8H10ClN5O3S

M.F.-C4H3Cl2NS M.F.-C4H8O3N4

KOH

DMC

MW:56 g/m

+ KCl + H2OMW:74.5 MW:18


Sr. No.


Chemical name Norms

1 2-chloro-5-chloro methyl thiazole

0.780

2 3-methyl-4-nitroimino perhydro-1,3,5-oxadiazine

0.760

3 Potassium hydroxide 0.200

4 DMC 0.200

5 Ethanol 0.340

Sr. No.

Complete Mass balance per KG Input

Input Quantity kg

Output Quantity in kg

1 2-chloro-5-chloro methyl thiazole

0.780 Thiamethoxam 1.0

2 3-methyl-4-nitroimino perhydro-1,3,5-oxadiazine

0.760 Aq layer 8.28

3 Potassium hydroxide 0.200

4 Dimethyl carbonate 0.200

5 Ethanol 0.340

6 Water 7

Total 9.28 9.28

C4H3NCl2S + C4H8N4O3 + KOH C8H10ClN5O3S + KCl + H2O


ATUL LIMITED

Name of Product: Quizalofop-ethyl



1.1 Brief process and flow diagram of process stage wise

2,6-Dichloro quinoxaline is reacted with ethyl-2-(4-hydroxy phenoxy)propionate in presence of Dimethyl formamide as solvent and potassium carbonate as base. After completion of reaction, DMF is recovered, water added and product is filtered, washed with water and purified in ethanol. Finally product dried at 60°c.

1.2

+

2,6-Dichloro quinoxaline Ethyl-2-(4-hydroxy phenoxy)-Propionate

OHC

CH3

C OC2H5

O

HON

N

Cl

Cl

N

NCl

OHCCH3

C OC2H5

OO

M.W.-199 g/mM.W.-210 g/m

R/S Quizalofop-ethyl

1/2

MW-138 g/m

potassium carbonate

1/21/2 H2O

Potassium chloride carbon dioxide

K2CO3

KCl CO2

M.W.-372.5 g/mM.W.-74.5 g/m


1.3

Sr. No.


Chemical name Norms kg

1 Ethyl-2-(4-hydroxy phenoxy) -propionate 0.602

2 2,6-dichloro quinoxaline 0.662

3 Potassium carbonate 0.45

4 DMF 0.606

5 Ethanol 0.5

1.5

Sr. No.

Complete Mass balance per kg

Input Quantity kg

Output Quantity kg

1 Ethyl-2-(4-hydroxy phenoxy) -propionate 0.602 Quizalafop ethyl 1.0

2 2,6-dichloro quinoxaline 0.662 CO2 0.13

3 Potassium carbonate 0.45 Aqueous layer 8.68

4 DMF 0.606

5 Ethanol 0.5

6 Water 7

Total 9.82 9.81

1.6

C8H4N2Cl2 + C11H14O4 + ½ K2CO3 C19H17N2O4Cl + KCl + ½ CO2 + ½ H2O


ATUL LIMITED


Name of Product: Pyrazosulfuron ethyl


1.1


1-methyl-4-ethoxycarbonyl pyrazole sulfonamide is reacted with Phenyl-N-(4,6-dimethoxy)pyrimidine-2-carbamate n presence of acetonitrile as solvent and triethyl amine as base. After completion of reaction, water added and reaction mass acidified with HCl. Product is filtered, washed with water followed by methanol and dried.

1.2

NN

N

N

NN

N

N

COOC2H5

SO2NH2

CH3

+

OCH3

OCH3

HNC

O

O

Pyrimidine Carbamate

COOC2H5

CH3

SO2NH

OCH3

OCH3

HNC

O

ethyl 5-[(4,6-dimethoxypyrimidin-2-ylcarbamoyl)sulfamoyl]- 1-methylpyrazole-4-carboxylate

+

OH

Phenol

MW:233 g/m MW:275 g/m

MW:414 g/mMW:94 g/m


1.3

S.N.



1 Acetonitrile 2.941

2 Phenyl-N-(4,6-dimethoxy)pyrimidine-2-carbamate 0.694

3 1-methyl-4-ethoxycarbonyl pyrazole -5-sulfonamide.amide 0.588

4 Triethyl amine 0.388

5 Methanol 1.176

1.5

S.No.


Input kg Output kg 1 Acetonitrile 2.941 Pyrazosulfuron ethyl 1.0 2 Pyrimidine carbamate 0.694 Aqueous layer 19.787

3 1-methyl-4-ethoxycarbonyl pyrazole -5-sulfonamide

0.588

4 TEA 0.388 5 Methanol 1.176 6 Water 15 Total 20.787 Total 20.787

1.6

C7H11N3O4S + C13H13N3O4 C14H18N6O7S + C6H6O


CHEMICAL REACTION OF DCDPS

+ SO3 CH3O SO2 OCH3SO2O + SO3

Pyrosulfate206

CH3O SO2 OCH3SO2O

Pyrosulfate206

Cl

+

MCB112.5

2

Cl ClSO2 + 2CH3O SO2 OH

DCDPS287

Methyl Hydrogen Sulfate112

+SO3

STAGE: 1

STAGE: 2

Cl

2 CH3O SO2 OH


CH3O SO2 OCH3

Di Methyl Sulfate126

+ H2SO4

CH3O SO2 OCH3SO2O

Pyrosulfate206

Cl

+

MCB112.5

2 Cl SO2 + CH3O SO2 OH

Comp. 1206.5


OCH3

DI METHYL SULFATE RECOVERY:

DMS: 1053 kg

SO3 : 1337 kg

CO2 (g): 298.15 kg

REACTIONMCB: 1881 kg

SO3 (g) to scrubber: 226.1 kg

Eff. To MEE: 12098.10 kg

Methanol recovered : 3380

REACTION

Water: 10273 kg

DMS: 855 kg

FILTRATION&

WASHING

FLOW DIAGRAM WITH MASS BALANCE OF DCDPS

Na2CO3: 1053 kg

DIGESTIONMethanol (fresh + recovered): 3670 kg

ML to Methanol recovery: 4007 kg DISTILLATION

Dist. Loss: 70 kg

Residue : 557 kgDRYING Drying loss: 204.2 kg

DCDPS: 1578.85 kg


Division: CP R&D

Name of Product: Metribuzin



Date: 25/02/2015


Brief Process:

Brief process and flow diagram of process stage wise Charge 98% Sulfuric acid and 4-amino-6-tertiary-butyl-3-mercapto-1,2,4-triazinone in flask. Add Methanol in reaction mass and cook mass for 10 hrs at 55°c. Quench reaction mass in to water at 10°c. Stir mass for 2 hrs and neutralize reaction mass with 48% caustic lye to pH 7. Filter Metribuzin and wash with water. Dry Metribuzin at 75°c. Recover water from mother liquor, filter sodium sulfate and recycle water back in the process.

ii) Chemicals reactions with molecular weight stage wise

+ CH3OH + H2SO4 + 2NaOH + Na2SO4 + 3H2O

4-amino-6-tertiary butyl-3-mercapto-1,2,4-triazin-5-one

MW-200g/m

MW-32g/m MW-98g/m MW-40g/m

MW-214g/m

MW-18g/mMW-142g/m

N

CH3

SH

CH3

N

N SH

NH2

N

CH3

SH

CH3

N

NH2

N

SH

Metribuzin


Sr. No. Raw Materials Purity MW Norms

kg/kg

1

4-amino-6-tertiary-butyl-3-mercapto-1,2,4-triazinone

98% 200 1.05

2 98% Sulfuric acid 98% 98 1.68

3 Methanol 99% 0.21

4 48% Caustic lye 48% 40 2.95

iv) List of co-product per KG Sodium sulfate: 2.38

v) Complete Mass balance per KG

Sr. No. Input

Kg

%Purity Sr. No.

Output Kg %Purity

1

4-amino-6-tertiary-butyl-3-mercapto-1,2,4-triazinone

1.05 98 1 Metribuzin 1.04 97

2 98% Sulfuric acid 1.68 98 2 Aqueous-1 13.0 NA

3 Methanol 0.21 99 3 Aqueous-2 2.0 NA

4 48% Caustic lye 2.95 48

5 Water 10.52

Total

16.42 Total

16.04

vi) Complete Molecular balance C7H12OSN4 + CH3OH + H2SO4 + 2NaOH C8H14OSN4 + Na2SO4 + 3H2O

200 32 98 80 214 142 54

vii) Complete Water balance

Material req. kg/kg Metribuzin

Sr. No. Raw Materials Input

Qty kg

Sr. No Materials Output

Qty kg

1 98% Sulfuric acid 1.68

1 Aqueous 1 13.0

2 48% Caustic lye 2.95

2 Aqueous 2 2.0

3 Water 10.52

Total input 15.15 Total output 15.0

2. Gas Emission: Gas emission stage wise per KG: Nil 3. Water discharges: Water is recovered by distillation from aqueous -1 &2 and is to be recycled back in the process.

4. Waste generation: Solid waste generated per KG: Nil Solid waste characteristics and its proposed treatment developed if any.NA

5. Details of Hazardous chemicals: Hazardous chemicals used and method of handling & disposal.

1) 4-amino-6-tertiary-butyl-3-mercapto-1,2,4-triazinone: Refer MSDS. 2) 98% Sulfuric acid: Refer MSDS

6. Other Consideration:

Recycle & Reuse options in process.

1. Water: Recover from aqueous-1&2 and reuse in the next batch. 7. Any other relevant information:

You may want to share about the product\process: NA

Dr. Jayesh Parekh Dr Palaniappan. R

Date: 25/02/2015 Project In-Charge G.M R & D

CHEMICAL REACTION OF ISOPROTHIOLANESTAGE: 1

CS2

Di Isopropoyl MalonateDi Sodium salt of Di Iso propoxy

Carbonyl ketone mercaptide

188 308

+ + 2H2O

Carbon Disulfide76

CH2

COOCH(CH3)2

COOCH(CH3)2

2NaOHC

COOCH(CH3)2

COOCH(CH3)2

CNaS

NaS

STAGE: 2

Di Sodium salt of Di Iso propoxyCarbonyl ketone mercaptide

308

+ + 2NaBrCCOOCH(CH3)2

COOCH(CH3)2

CNaS

NaSCH2 CH2

Br Br

Ethylene Dibromide188

CCOOCH(CH3)2

COOCH(CH3)2

CS

S

CH2

CH2

ISOPROTHIOLANE290.4

Di Isopropyl Malonate: 0.95 kg

CS2: 0.46 kg

DISTILLATION

REACTION

Eff. To Incinerator: 1.58 kg

FLOW DIAGRAM WITH MASS BALANCE OF ISOPROTHIOLANE

ISOPROTHIOLANE: 1.04 kg

Acetone: 2.8 kg

NaOH: 1 kg

N-Hexane: 2.11 kg

Vapor loss: 0.25 kg

TBAB: 0.01 kg

Ethylene Dibromide: 0.88 kg

CS2 recovered : 0.18 kg

NaBr: 0.82 kg

N-Hexane recovered : 2 kg

Acetone recovered: 2.66 kg

CHEMICAL REACTION OF PYRIDINE BASED INSECTICIDES & HERBICIDES CHEMICAL IMIDACLOPRIDSTAGE: 1

STAGE: 2

STAGE: 3

H2SO4

Guanidine Nitrate Nitroguanidine122 104

C NHHNO3

NH2

NH2

C NH

NO2

NH2

NH

KOH

Nitroguanidine104

C NH

NO2

NH2

NH+

CH2 CH2

NH2 NH2

NH NO2

NH N + NH3

Ethylene Diamine60

2-[Nitroimino] imidazolidine130

Ammonia17

+

NH NO2

NH N

2-[Nitroimino] imidazolidine130

2-Chloro-5-Chloromethyl Pyridine162

CH2Cl

Cl N

NH NO2

N NCH2

Cl N

+ HCl

Imidacloprid

255.5

H2SO4: 50 kg

Guanidine Nitrate: 65 kg

REACTION

EDA: 131.4 kg

REACTION

FLOW DIAGRAM WITH MASS BALANCE OF PYRIDINE BASED INSECTICIDES & HERBICIDES CHEMICAL IMIDACLOPRID

IMIDACLOPRID: 100 kg

HCl: 800 kg

KOH: 500 kg

Effluent to ETP: 1847.36 kg

Residue: 13.32 kg

Water: 740 kg

Eff. To Incinerator: 675 kg

Water: 300 kg

NH3 (g) to scrubber: 13.21 kg

REACTION&

DISTILLATION

2-chloro-5-methylchloro-pyridine : 74.6 kg

Sodium Methoxide: 40 kg

DMF: 112.5 kg Effluent to ETP: 1167.37 kg

Water: 1125 kg

Distillation loss: 5.97 kg

Methanol recovered : 11.5 kg

DMF recovered : 104.7 kg

CHEMICAL REACTION OF GLYPHOSATE

Name: N-Phosphonomethyl iminodiacetic acid Hydrogen peroxide Glyphosate Carbon dioxide Formaldehyde Water

MW 227 34 169 44 30 18

(OH)2-P-CH2-N-(CH2COOH)2

O

(OH)2-P-CH2-NH-CH2COOH

O

+ H2O2 + CO2 + HCHO + H2O

Water: 1000 kg

PMIDA: 2000 kg

PRECIPITATION&

DRYING

CO2 (g) : 375.09 kg

REACTION

Eff. To Incinerator: 2347.95 kg

FLOW DIAGRAM WITH MASS BALANCE OF GLYPHOSATE

GLYPHOSATE: 1447.95 kg

Sodium tung state : 6 kg

H2O2: 700 kg

10% FeSO4 : 300 kg

Water: 300 kg

Vapor loss: 135 kg

STEP-1

Input Qty in Kg Output Qty in Kg

o-CRESOL 1389.096 SO2 815.00

SO2Cl2 1726.812 HCl 465.00

AlCl3 6.372

DPS 6.372

TOTAL 3128.652 FRACTIONAL DISTILLATION

CRUDE PCOC 1848 1ST CUT 142.30

1848.00 MIDCUT 60.98

PRODUCT 1459.92

RESIDUE 184.80

TOTAL 1848.00 OUTPUT 1848.00INPUT

STAGE-3

SO2 815.00 SO2Cl2 1719.14

Cl2 904.1406 wastecarbon 0.17

SULFURYL CHLORIDE PREPARATION

PREPARATION OF 4-CHLORO-2-METHYL PHENOL (PCOC)

Reaction stage-1

Chlorination of o-cresol

Reaction stage-2

FractionalDistillation

Reaction stage-3

Sulfuryl chloride preparation

Active carbon 0.171OUTPUT 1719.31

TOTAL 1719.31INPUT

Step-1

INPUT QTY PURITY REAL M.Wt MOLE % EXCESSo-CRESOL 1389.096 100% 1382.151 108.5 12.74 1

SO2Cl2 1726.812 100% 1726.812 135 12.7912 1.00AlCl3 6.372 100% 6.372 133 0.04791DPS 6.372 100% 6.372 186 0.034258Cl2 904.14 100% 904.1406 71 12.73438

Active Carbon 0.17 100% 0.171TOTAL 4032.964

OUTPUT Kg1st cut 142.302nd cut 60.98

PRODUCT 1459.92RESIDUE 184.80

HCl 465.00SO2Cl2 1719.14

waste carbon 0.17TOTAL 4032.31

4-Chloro-2-Methyl Phenol ( PCOC)

To be scrubbed in waterTo be used in process

RemarksTo be recycle in stage-1To be recycle in stage-2To be taken for MCPA preparationTo be sent for incineration

STEP-2

WT IN KG WT IN KG

WATER 345.244652MCA 1338.91

TOTAL 1684.15465

30% NaOH 1418.93PCOC 1459.9230%NaOH 2537.3

WATER 6081.69 13181.9947 AQ LAYER

TOTAL 13181.9947 13181.9947

STEP-2

WATER 101530%HCl 2129.37AQ LAYER 13181.9947

TOTAL 16326.3647

REAN MASS 2787 WET CAKEWATER WASH 6081.7 12989 6493.52 ML+WML

ML WMLTOTAL 22408.0647 22270

WET CAKE 2787 1952 DRY CAKE

TOTAL 2787 1952

ACIDIFICATION

PREPARATION OF MCPA

R-2

MS

R-3MSGL

BRIEF PROCESS OF 4-CHLORO-2-METHYL PHENOXY ACETIC ACID ( MCPA)

STEP-1 PREPARATION OF 4-CHLORO-2-METHYL PHENOL(PCOC)

Chlorination of o-cresol carried out using sulfuryl chloride as chlorinating agent and Aluminium chlorideand Diphenyl sulfide as catalyst. 4-chloro-2-methyl phenol was separated from crude mass by fractional distillationand used for MCPA preparation.

STEP-2 PREPARATION OF 4-CHLORO-2-METHYL PHENOXY ACETIC ACID

Condensation of PCOC carried out with chloroacetic acid in prsence of caustic lye to give sodium salt of MCPA.Which on acidification with 30%HCl give 4-chloro-2-methyl phenoxy acetic acid.

Step-3 Preparation of Sulfuryl chloride

Sulfur dioxide reacted with Chlorine gas in presence of active carbon as catalyst to give sulfuryl chloride.

GLYPHOSATE ( N-PHOSPHONOMETHYL GLYCINE)

INPUT OUTPUTKG KG

DM water 2700

PMIDA 2000 350 CO2

Sodium Tungstate 6

50%H2O2 700

TOTAL INPUT 5406

5056

Reaction mass 5056

10%FeSO4 300

TOTAL INPUT 5356

1000 1600 wet productDM water 3800 MLReaction mass 5356 956 WML

TOTAL INPUT 6356 6356 OUTPUT

Wet product 1500 1440 GLYPHOSATE

SN Name Qty Purity Real MW Mole1 DM water 3700 100% 3700 18 205.55562 PMIDA 2000 99% 1980 227 8.7224673 50%H2O2 700 50% 350 34 10.294124 Na-Tungstat 6 99% 5.94 330 0.0185 10%FeSO4 300 10% 30 152 0.197368

6706

SN Name Qty Purity Real MW Mole1 Na-Tungstat 6 90% 5.4 18 0.32 ML 3800

Reaction massSodium tungstate

7% HCHO,0.7%FeSO4,92% water

INPUT

OUTPUT

Stage-1

Main reaction

Filtration

Stage-2

Precipitation

Filtration

Drying

3 WML 9564 CO2 350

Glyphosate 14406552

98%water,0.5% max HCHO

99% Purity

GLYPHOSATE BRIEF PROCESS:

Oxidation of Phosphonomethyl iminodiaceticacid carried out with Hydrogen peroxide usingSodium tungstate as catalyst in water.Ferrous sulfate added and precipitated Glyphosate se filtration and washed water.Generated effluent was treated chemically to decompose formaldehyde before discharging t

eparated by

to ETP.


Division: CP R&D

Name of Product: Diafenthiuron



Date: 25/02/2015


Brief Process:

Brief process and flow diagram of process stage wise Charge Toluene and 4-phenoxy-2, 6-diisopropyl phenyl isothiocyanate in the flask. Add Tertiary butyl amine in reaction mass and cook mass for 2 hrs. Recover toluene and add n-hexane to the reaction mass. Cool reaction mass to 10°C.Filter solid Diafenthiuron and wash with hexane. Recover n-hexane from ML and send residue for incineration.

ii) Chemicals reactions with molecular weight stage wise


Sr. No. Raw Materials

Purity MW Norms kg/kg

1

4-phenoxy-2, 6-diisopropyl phenyl isothiocyanate

96% 311 0.912

2 Tertiary butyl amine 99% 73 0.675

3 Toluene 99% 0.03

4 Hexane 99% 0.09

O

CH

CH

NH

CH3

CH3

CH3

CH3

NH

S CH3

CH3

CH3

CH

CH

N=C=S

CH3

CH3

CH3

CH3

ONH2

CH3

CH3

CH3+

Toluene

4-phenoxy-2,6-diisopropyl phenyl isothiocyanateTertiary butyl amine

M.W--311g/mM.W.-73.11g/m

DiafenthiuronM.W.-384g/m

iv) List of co-product per KG No co-product formed in Diafenthiuron process

v) Complete Mass balance per KG

Sr. No. Input

Kg

%Purity Sr. No.

Output Kg %Purity

1

4-phenoxy-2, 6-diisopropyl phenyl isothiocyanate

0.912 96

1

Diafenthiuron 1 98

2 Tertiary butyl amine 0.214 99

2 Rec. Toluene 0.68 99

3 Toluene 0.72 99

3 Rec. Hexane 1.73 99

4 Hexane 1.82 99

4 Residue 0.256 NA

Total

3.666 Total 3.666

vi) Complete Molecular balance C19H21ONS + C4H11N - C23H32ON2S

4-phenoxy-2, 6-diisopropyl phenyl isothiocyanate Tertiary butyamine Diafenthiuron

MW 311 73 384

vii) Complete Water balance Water is not used in Diafenthiuron process

2. Gas Emission: Gas emission stage wise per KG : Nil 3. Water discharges: Water is not used in Diafenthiuron process

4. Waste generation: Solid waste generated per KG : 0.256 Solid waste characteristics and its proposed treatment developed if any.NA

5. Details of Hazardous chemicals: Hazardous chemicals used and method of handling & disposal.

1) 4-phenoxy-2, 6-diisopropyl phenyl isothiocyanate: Refer MSDS. 2) Tertiary butyl amine: Refer MSDS


Recycle & Reuse options in process.

1. Toluene and n-hexane: Recover from process and use in next batch as a solvent. Solvent recovery details stage wise per KG.

Materials Output Qty kg (purity, % ) Recover toluene 0.68 99.5

Recover hexane 1.73 99.40 7. Any other relevant information:

You may want to share about the product\process: NA

Dr. Jayesh Parekh Dr Palaniappan. R



Division: Crop protection

Name of Product: Indoxacarb: ( (S)-methyl-7-chloro-2,5-dihydro-2-[[methoxycarbonyl)[4-(trifluoromethoxy)phenyl]amino]carbonyl]indenol[1,2-e][1,3,4]oxadiazine-4a(3H)-carboxylate



Date: 10-03-2015


Synthetic scheme of Tech. Indoxacarb:

Part-A:

O

Cl

O

Cl

O

O O

Cl

O

OCinchonine & TBHP OH

Phenylmethyl hydrazine carboxalate

N

Cl

O

OOH

NHCO2CH2PhCelite/ P2O5

EDClCl

NN

O

CO2CH2Ph

O

O

Cl

NHN

O

O

O

(1) (2) (3)

(4) (5) (6)

5% Pd/C / H2

Methyl acetate

Toluene EDClToluene

NaOCH3

Part-B:

OCF3

NH2MCF /NaHCO3

H2O

OCF3

NHCO2CH3COCl2 / NaH / DME

DCM

OCF3

NCO2CH3

COCl

PART A +B

Cl

NHN

O

O

O

( 6)

+

OCF3

NCO2CH3

COCl

Methyl acetateCl

NN

O

O

O

NOCO2CH3

OCH3

( 9 ) ( 10 )

( 7 ) ( 8 ) ( 9 )

NaOH

5-chloro indanone (1) was carbomethoxylated with dimethylcarbonate in the presence of sodium methoxide and solvent toluene which afforded methyl-5-chloro-1-oxo-2, 3-dihydroindene-2-carboxtlate (2).

Enantioselective catalytically hydroxylation of (2) with chiral base (cinchonine) and t-butyl hydroperoxide to gave (+) hydroxyl indanone (3) in 42 % ee. Reaction of (3) with benzyl carbazate furnished Cbz-protected hydrazone (4) and which was condensed with methylal in the presence of phosphorus pentoxide to gave oxadiazine (5).

Debenzylation by hydrogenation using catalyst Pd/C was accompanied by decarboxylation and the resulting oxadiazine (6) was immediately coupled with carbonyl chloride (9) to afford the derived Indoxacarb (10)

The synthesis (9) from 4-(trifluoromethoxy) aniline (7) involves reaction with methylchloroformate in the presence of base followed by condensation of the sodium salt of its methyl carbamate(8) with excess phosgene gave (9).

Stage-A1:

flow diagram of process stage wise

Step-I

1) 778 g Toluene 4) 168 g Indanone 2) 83.4 g NaOMe + 520 g Toluene+ 180 g DMC 3) 90 g DMC

5) Distillation of MeOH+DMC+Toluene (365 g)

1) 1000 g Water 2)above 3) 160 g 35% HCl

Slurry 4) 150 g NaHCO3 Soln

5)2×200 g Waterwash

Distillation 1)aq.layer seaparation

(touene 370 g) Org layer (1275 g) Aq phase

i)1172 g ii) 195 g iii) 402 g

104˚C-109˚C

10˚C

922 g A1 Soln

Stage: A2:

Step-2

1)30.5 g Cinchonine 2) 116 g TBHP

25 g Toluen Filter

Dryed 150-151 g A2 !st Crop

1)872 g 35 % HCl ML 50˚C

2) 100 g Water

Separate layers

Distillation-Org lyr Aq.layer 125 g 32 % NaOH

656 g Toluene

0

10 g Toluene Filter 300 g Water filter

Dry at Dry at 28 g Cinchonine

50˚C 50˚C

28.0 g A2 2nd Cro 76.0 g Distilled Toulene

48.0 g Residue

922 g A1 Soln i)10-15˚C

ii)40-45˚C iii)0-5˚C

Wet Cake

25-30˚C

1038 g 0-5 ˚C

820 g

W.C. W.C.

ML

Stage: A3 &A4:

1)345 g EDcl 5) 5.5 g Water 2) 78.2 g A2 3) 58.0 g BCZ 4) 4.2 g PTSA

1)346 g EDcl 2) 111.6 g Hylfow 3) 111.6 g P2O5 5) A3 RM 4) 143.6 g

Methylal

3×63 g EDcl

Filter

1)235 g IPA Distillation 801 g EDcl

2×8 gm IPA Filter

Dry

50˚C

80˚C

65-70˚C

198 g Sludge

Filtrate 80-85˚C

Wet Cake 102 g A4

Stage: A5& A6 6) ZnBr2 3) DM Water

7)5% pd/C 4) Citric acid

2) A4 5)C.S.flaks

1) MA 8) H2

9) B2

Filter

NaHCO3 +H2O

Water

Separation

Organic layer Rec. of MA

Silica

Aq .Layer Hexane

Filter

Recycle ML

10-150C

5% pd/C

600C Org.layer 10-150c

Tech.Indoxacarb

Organic Layer

Indoxacarb

Step-I


O

Cl

C OCH3

O

H3CO

Cl

O

CO2CH3

CH3OH CH3ONa

M.W: 224.5g/m

M.W:32 g/m M.W: 54g/m

M.W:166.6g/m

M.W:54g/m

M.W:90g/m

Sodium methoxide

5-Cl-1-indanoneDimethyl carbonate

CH3ONa

Toluene

A1

Step-II

Cl

O

CO2CH3

Cl

O

M.W: 240.5g/m

OH

CO2CH3

Tertiary butanol

M.W: 74g/m

A1

tertbutyl hydroperoxide

M.W: 224.5g/m

M.W: 90.0g/m

A2

Toluene

Cinchonine

(CH3)3COOH

(CH3)3COH

Step-III

Cl

O

M.W: 240.5g/m

OH

CO2CH3

HN

NH2

O

O

Benzyl carbazate

Cl

N

M.W: 388.5g/m

OH

CO2CH3

NHCO2CH2Ph

H2O

A3

A2

M.W: 18 g/m

M.W: 166.0g/mEDC

PTSA

Step-IV

Cl

N

M.W: 388.5g/m

CO2CH3

NHCO2CH2Ph

A3Cl

N

CO2CH3

A4

2CH3OHCH2

N

CH2(OCH3)2

Methylal

CO2CH2Ph

M.W: 400.5g/m2(32)

M.W: 76.0g/m

EDC

P2O5

OOH

If SOP followed there is no run away reaction

Step-V

M.W: 400.5g/m

H2

Cl

NO

CO2CH3

A5

CH2

N

H

M.W: 266.5g/mM.W: 44.0g/m M.W: 92.0g/m

Carbon dioxide

CH3

Toluene

C OOMethylacetate

Cl

NO

CO2CH3

A4

CH2

N

CO2CH2Ph

5% Pd/C

Hydrogen gas

M.W:2 g/m

714 g for 1kg indoxa78 g / 1kg of indoxa carb

Step-VI

Cl

N

CO2CH3

A5

N

H

M.W: 266.5g/m

O N

COCl

CO2CH3

B2

M.W: 297.5g/m

Cl

N

A6

N

M.W: 527.5g/m

OCF3N

H3CO2C

O

C

F

F

F

Methyl acetate

O

CO2CH3

HCl

M.W: 36.5g/m

O

Inndoxacarb

Indoxacarb B1

NH2

OCF3

O

OClCH3

Methyl chloroformatePTFMA

M.W. 177.0g/m

NHCOOCH3

OCF3

sodium bicarbonate

Sodium chloride Water

M.W. 58.5g/m M.W. 18.0g/m

B1

M.W. 235.0g/mM.W.:94.5 g/m

HO

HNaCl

NaHCO3

If SOP followed there is no run away reaction

Indoxacarb B2

NHCOOCH3

OCF3

B1

M.W. 235.0g/m

NaH

M.W. 24.0g/m

Sodium hydride

O

Cl

Cl

Carbonyl chloride

M.W. 99.0g/m

N

OCF3

B2

M.W. 297.6 g/m

COOCH3

Sodium chloride

M.W. 58.5 g/m

H2

M.W. 2.0g/m

NaCl

Hydrogen

DCM

Cl

O

Benzyl carbazate

Step-I

C O

C2H5O

C2H5O

2HO

Benzyl alcohol

OO

O

Dibenzyl carbonate

2C2H5OH

2(46)

Diethyl carbonate

M.W: 118 g/m 2(108)M.W: 242.4 g/m

Ethanol

Step-II

OO

O

Dibenzyl carbonate

M.W: 242.4 g/m

NH2NH2.OH

Hydrazine hydrate

M.W: 50.0 g/m

HN

NH2

O

O

Benzyl carbazate

M.W: 166.0 g/m

HO

Benzyl alcohol

M.W: 108.0 g/m

HO

Hwater

M.W: 18.0g/m


No Name of raw material Quantity (Kg) Quantity (Kg) Consumption(Lab) Consumption(Plant)

1 5-chloro-1-indanone 0.515 0.74 2 Sodium methoxide 0.256 0.36 3 Dimethyl carbonate 0.622 0.91 4 Toluene 1.025 1.77 5 HCl(35 %) 0.705 1.34 6 Sodium bi carbonate 0.364 0.691 7 Cinchonine 0.0076 0.03 8 tert-butylhydrogenperoxide 0.356 0.47 9 Sodium hydroxide 0.3 0.647

10 Ethylene di chloride 0.948 1.43 11 Benzyl alcohol 0.58 0.803 12 Diethyl carbonate 0.455 0.63 13 Hydrazine hydrate(80%) 0.243 0.337 14 Chlorobenzene 0.373 0.518 15 P-toluene sulfonic acid 0.029 0.04 16 Hyflow 0.778 0.56 17 Phosphorous pentoxide 0.778 0.72 18 Dimethoxy methane 1.004 0.98 19 Isopropanol 0.349 0.72 20 Methylacetate 1.534 2.38 21 Citric acid 0.56 0.58 22 D. M water 2.14 2.14 23 Pd/ C( 5%) 0.0357 0.004 24 Zinc bromide 0.023 0.02 25 H2 gas 0.006 0.02

26 P-trifluoromethoxy aniline 0.318 0.42

27 Methyl chloroformate 0.266 0.26

28 Methylene di chloride NA 2.73 29 1,2-dimethoxy ethane(Monoglyme) NA 0.338 30 Phosgene 0.551 2.42 31 n-Hexane 1.7 1.74 32 Soda ash 0.038 0.62 33 Sodium hydride NA 0.105 34 Silica 0.176 0.177

List of co-product per KG

Stages In put Qty Co-product Qty Stage-A1 5-chloro-1-Indanone 515 g Methanol 197.89 g NaCl 180.8 g Stage-A2 A1 624.4 g Tert- butanol 205.8 g Stage- A3 A2 520 g Nil Nil Stage- A4 A3 756 g Methanol 124.5 g Stage-A5 A4 714 g Toluene 164 g Stage-A6 A5 475 g NaCl 104 g BCZ-1 Diethyl carbonate 630 g Ethanol 491 g BCZ Dibenzyl carbonate 1294 g Benzyl alcohol 576.6 g B1 PTFMA 318 g NaCl 105 g B2 B1 409 g NaCl 101 g


I

INPUT

N

OUTPUT

D Sr.No. Raw Materials Quantity[kg.] O Sr.No. Materials Quantity[kg.]

1 5-chloro-1-indanone 0.232 X 1 Indoxacarb S Isomer 0.3138 2 Sodium methoxide 0.113 A 2 Recovered Toluene 4.008 3 Dimethyl carbonate 0.676 C 3 Recovered Methanol 0.133 4 Toluene 4.76 A 4 Recovered Ethylene dichloride 1.387 5 HCl(35 %) 0.421 R 5 Recovered Isopropyl alcohol 0.687 6 Sodium bi carbonate 0.234 B 6 Recovered Dichloromethane 3.447 7 Cinchonine 0.037 7 Recovered Hexane 0.712 8 tert-butylhydrogenperoxide 0.147 T 8 Recovered Methyl acetate 1.2 9 Sodium hydroxide 0.099 E 8 Solvent Vapor loss 5.25

10 Ethylene di chloride 1.94 C 10 Recovered Cinchonine 0.0325 11 Benzyl alcohol 0.477 H 11 Organic/Aqueous phase effluents with 4.39 12 Diethyl carbonate 0.2 salts

13 Hydrazine hydrate(80%) 0.106

14 Chlorobenzene 0.679

15 P-toluene sulfonic acid 0.012 Total 21.5603 16 Hyflow 0.176

17 Phosphorous pentoxide 0.226 18 Dimethoxy methane 0.308 19 Isopropanol 0.968 20 Methylacetate 1.89 21 Citric acid 0.18 22 D. M water 0.672 23 Pd/ C( 5%) 0.004 24 Zinc bromide 0.006 25 H2 gas 0.006 26 N2 gas 0.003 27 P-trifluoromethoxy aniline 0.132 28 Methyl chloroformate 0.081 29 Methylene di chloride 5.03 30 Sodium hydride 0.0341 31 1,2-Dimethoxy ethane 0.11 32 Phosgene 0.194 33 n-Hexane 1.575 34 Silica 0.053

21.78


Already given in above schemes

Complete Water balance Stage-1: A1: Water input for work up: 8.189 kg Water out put as a effluent: 8.227 kg A2: Input: 7.286 kg Out put: 7.348 kg Stage: 2: A3: Input: Nil Out put from reaction: 0.046 kg A4: Input for work up: 3.432 kg Out put as a effluent: 3.582 kg Stage: 3: A5: Input for buffer solution: 2.14 kg Out put as a effluent or recycle: 3.5 kg A6: Input: 0.204 kg Out put: 0.250 kg Stage: 4

M.W: 400.5g/m

H2

Cl

NO

CO2CH3

A5

CH2

N

H

M.W: 266.5g/mM.W: 44.0g/m M.W: 92.0g/m

Carbon dioxide

CH3

Toluene

C OOMethylacetate

Cl

NO

CO2CH3

A4

CH2

N

CO2CH2Ph

5% Pd/C

Hydrogen gas

M.W:2 g/m

714 g for 1kg indoxa78 g / 1kg of indoxa carb

: B1: Input as a reaction water: 15.94 kg Out put as a effluent: 16.22 kg B2: Input for B1 recovery: 1.1 kg Output as a effluent: 1.15 kg

2. Gas Emission:

Gas emission stage wise per KG

Reaction scheme for B2: Gas emission per kg of indoxacarb

177 g/mole94.5 g/mole 84 g/mole 235 g/mole

58.5 g/ mole 44 g/ mole 18 g/mole398 g 99 g/ 1 kg indoxa

235 g/mole 24 g/mole 297. 5 g/mole

58.5 2 g/mole511 g

4.3 g/1 kg indoxa

3. Water discharges:

Raw water consumption details per KG Waste water quantity and quality generated i.e. pH, COD TDS acidity, alkalinity etc per KG Stream wise quality of the effluent (Analysis reports | experimental results) per KG Proposed treatment method developed if any.

4. Waste generation:

Solid waste generated per KG Solid waste characteristics and its proposed treatment developed if any.

Pl. refer As per given above table

As per above requirement we mentioned in below table as per stage wise of 1 kg tech. Indoxa carb Effluent / solid waste generated stage wise for 1 kg tech. Indoxacarb

Sr Stage Effluent Solid waste

Qty / kg of Indoxacarb

pH COD BOD TDS Remark

1 Step-1(A1)

Aqueous - 3.583 2.3 24000 7142.8 80430 To be treated in ETP as current practice

Step-1(A1)

Aqueous 1.726 8.1 5680 1200 11540

2 Step-2(A2)

Aqueous 4.01 12.1 4570 800 52470

Step-2(A2)

- Organic residue

0.147 - - - - To be incenerated

3 Step-3&4(A3 & A4)

Aqueous 3.188 8.1 ETP

Step-3&4 )A3 &A4)

Hyflow sludge

1.381 To be incenerated

Step-3&4(A3 &A4)

Organic residue

0.419 To be incenerated

4 Step-5&6 (A5&A6)

Aqueous 1.7 2.8 166536 88500 To be recycle and use in next batch

Step-5&6 (A5&A6

Aqueous 0.9 ETP

5 B1 Aqueous 0.29 8 17881.6 108510 ETP Aqueous 1.276 7 5852 22410 ETP B2 Aqueous 1.31 6 8388.5 18100 ETP Aqueous 1.31 6 58390.4 12300 ETP

5. Details of Hazardous chemicals:

Hazardous chemicals used and method of handling & disposal.

Pl. refer below table for above requirement


Recycle & Reuse options in process.—Most of the solvent we recover and reuse Solvent recovery details stage wise per KG. Pl. refer below table for solvent details

Solvent consumption for 1Kg Tech. Indoxacarb-

Stagewise R&D Plant

No Stages Name of solvents Consume qty(Kg)

Usages qty(Kg)

Recovery (%)

Consume qty(Kg)

Usages qty(Kg)

Recovery (%)

1 A1 & A2 Toluene (NEW TTD) 0.366 4.025 91 2.39

15.14 kg 84.22

2 Dimethyl carbonate (NEW TTD) 0.303 0.819 66 1.305 2.15 39.24

3 A3 & A4 Ethylene di chloride(NEW TTD) 0.948 6.355 85 1.97 6.91 71.53

4 Isopropanol (NEW TTD) 0.349 1.757 80 0.89 3.08 71

5 A5 & A6 Methylacetate -Normal 1.534 6.334 75 2.22 6.02 63.51

6 Hexane-Normal 1.63 3.35 51 1.44 2.61 45.16

7 B1 & B2 Dichhloro methane-OLD 1.51 7.55 80 5 16 69.13

8 Hexane-OLD 0.236 0.786 70 1.4 2.4 42

9 BCZ Benzyl alcohol-OLD 0.298 1.023 71 0.27 on DBC 1.52 on DBC

82 On DBC

10 Mono chloro benzene-OLD 0.245 0.816 70 1.05 2.16 51.65

Sr. No Hazrdous chemical Handling Disposal 1

NaOCH3(Sodium methoxide

Use PPE and use nitrogen while charging .In detail please refer MSDS

In detail please refer MSDS

2 Phosphorous pentoxide(P2O5)

Use PPE and use nitrogen while charging .In detail please refer MSDS


3 5% palladium on carbon Use PPE and use nitrogen while charging .In detail please refer MSDS


4 Methyl chloroformate Use PPE .In detail please refer MSDS


5 Phosgene Use PPE .In detail please refer MSDS


7. Any other relevant information:

You may want to share about the product\process


RJP / UBP R. Pallaniappan

ATUL LIMITED

Name of Product: Bispyribac sodium


1.1



2, 6-Dihydroxy benzoic acid is reacted (2,6-DHBA) with 4,6-dimethoxy-2- methylsulfonyl pyrimidine (4,6-DMMSP) in presence of THF as solvent and sodium hydride as base. After completion of reaction, THF is recovered, water added and product is filtered, washed with water and dried.

1.2

COOH

OHHO3NaH

COONa

ONaNaO3H2

COONa

ONaNaON

N SO2CH3

OCH3

H3COCOONa

OO

N

N

H3CO

H3CO

N

N

OCH3

OCH3

2SO2CH3Na

2,6-DHBAMW-154 g/m MW-220 g/m

MW-218 g/m

2

MW-102 g/m

MW-452 g/m

Bispyribac-sodium

MW-24 g/m

MW-220 g/m


1.3

S.N.


Chemical name Kg/kg 1 THF 2.1 2 2,6-Dihydroxy benzoic acid (2,6-DHBA) 0.486 3 4,6-Dimethoxy 2-methylsulfonyl pyrimidine (4,6-DMMSP) 0.973 4 Sodium hydride 0.413

1.5

S.N.

Complete Mass balance per kg:

Input kg Output kg 1 THF 2.1 Bispyribac sodium 1.0 2 2,6-DHBA 0.486 Sodium methane sulfonate 0.900 3 4,6-DMMSP 0.973 Aqueous layer 22.06 4 Sodium hydride 0.413 Hydrogen 0.019 5 Water 20

Total 23.972 Total 23.972 1.6

C7H6O4 + 3NaH C7H3Na3O4 + 3H2


C7H3Na3O4 + 2C7H10N2O4S C19H17N4NaO8 + 2SO2CH3Na

ATUL LIMITED

Name of Product: Azoxystrobin


1.1 Brief process and flow diagram of process stage wise: (E)-Methyl 2-[2-(6-chloropyrimidin-4-yloxy)phenyl]-3-methoxyacrylate is reacted with 2-cyanophenol in presence of base potassium carbonate and catalyst DABCO in DMF and toluene mixture at 80°c. Once reaction completed, crude product is isolated. The crude product obtained is purified with methanol to get technical Azoxystrobin.

Process flow diagram:

Project – Lab Process Details

Preparation of Azoxystrobin (MW: 403.4)

(1) 135g. Toluene (2)

97.1 g. CPOPMA

(3) 44 g. 2-Cyanophenol

(6) 0.7 g. DABCO in 10 g DMF

Layer separation

Recovery

105 g. Methanol

Filter

Distill 138 g. Methanol

(5) 62.8 g. K2CO3

Toluene layer

Recovered Toluene 299 g

Azoxystrobin 108.1 g

Methanol ML

Crude product

2x 30 g Methanol wash

Product wet cake Drying

20 g. DMF

(4)

Reaction mass

(7) 350 ml water

100 ml water

1.2 Chemicals reactions with molecular weight stage wise:

Cl O

N N

CO2CH3

+

CN

OH

DABCO in DMF

(E)-methyl 2-[2-(6-chloropyrimidin-4-yloxy)phenyl]-3-methoxyacrylate

2-cyanophenol

Anhy. K2CO3

TolueneDMF

M.W: 320.5M.W: 119

[CPOPMA]

H3CO

N N

O

CH3OCH CO2CH3CN

O

Methyl (E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate

AZOXYSTROBIN][

M.W: 403.4 1.3 List of raw materials along with quantity per kg: (consumption norms per kg of product)

Sr.No. Raw materials Consumption kg/kg

1. CPOPMA 0.898

2. 2-Cyanophenol 0.407

3. Toluene 0.333

4. Anhydrous K2CO3 0.581

5. Dimethylformamide 0.277

6. Methanol 0.250

7. 1,4-Diazabicyclo[2.2.2]octane (DABCO) 0.007

1.5 Complete Mass balance per kg Sr. no.

Raw materials Input(kg) Sr. no.

Raw materials Output(kg)

1 Toluene 3.238 1 Recovered Toluene 2.766

2 DMF 0.277 2 Recovered methanol 1.276

3 CPOPMA 0.898 3 Azoxystrobin technical 1.000

4 2-Cyanophenol 0. 407 4 Aqueous ML 5.187

5 K2CO3 0.581 5 Toluene distillation loss 0.472

6 DABCO 0.006 6 Methanol loss during distillation & drying 0.250

7 Methanol 1.526 7 Residue after toluene distillation 0.145

8 Water 4.163

Total 11.096 11.096

1.6 Complete Molecular balance C15H13ClN2O4 + C7H5ON --- C22H17N3O5 + HCl

ATUL LIMITED

Name of Product: Trans-4-MCHI


Brief process and flow diagram of process stage wise Step-1: Brief process: p-Cresol was hydrogenated in presence of Raney-Ni at 115-125°C and 10-12 kg pressure.


Flow diagram: Chemicals reactions with molecular weight:

OH

CH3 CH3

OH

MW: 108.14 MW: 114.19

Para Cresol 4-Methyl cyclohexanol

+ 3H2Ra-Ni catalyst


Sr. No.

Raw Material Qty (kg)

1. Para Cresol 1.081 2. Raney-Ni catalyst (Monarch Kalcat-3063) 0.06486

p-Cresol

Reaction

Filtration

4-Methyl cyclohexanol

Ra-Ni catalyst, H2

Catalyst recovery

Complete Mass balance per KG: Step: I

Input Kg Output Kg P-Cresol 1.081 Pure 4-Methyl cyclohexyanol 1.0 Ra-Ni catalyst [MONARCH KALCAT-3063]

0.06486

Ra-Ni catalyst wet cake 0.08648

Hydrogen gas -- Water from distillation of crude 4-Methyl cyclohexanol

0.054

Total Input 1.145 Total Output 1.140 Input – Output = 1.145 – 1.140 = 0.005 Kg loss

Step-2: Brief process: 4-Methyl cyclohexanol reacted with sodium hypochlorite and acetic acid at <0°C. Flow diagram: Chemicals reactions with molecular weight:

CH3

OH

MW: 114.19


+

CH3

O

MW: 112.17

4-Methyl cyclohexanone

NaOCl + +NaCl H2OCH3COOH

MW 74.5 MW 58.5 MW 18


Reaction

Isolation


NaOCl, AcOH


Sr. No.


1. 4-Methyl cyclohexanol 1.06 2. Acetic acid 0.85 3. Sodium hypochlorite solution (~14.3% w/w) 5.69 4. Sodium bisulphite solution (5%) 0.85 5. Caustic lye (48%) 0.765 6. 10% Brine solution 1.06

Complete Mass balance per KG: Step:II

Input Kg Output Kg 4-Methyl cyclohexanol 1.063 Crude 4-Methyl cyclohexanone 1.00 Glacial acetic acid 0.853 Aqueous layer 9.11 Sodium hypochlorite 14.3w/w solution 5.690 Sodium bisulphate 5% solution 0.851 Caustic lye 48%w/w 0.765 10% Brine solution 1.063 Total Input 10.27 Total Output 10.11

Input – Output = 10.27 – 10.11 = 0.17 kg loss Step-3: Brief process: 4-Methyl cyclohexanone reacted with hydroxylamine hydro chloride in presence of caustic lye at 70-75°C. Flow diagram:

Reaction

Isolation

4-Methyl cyclohexanone oxime

NH2OH.HCl, NaOH


Chemicals reactions with molecular weight:

CH3

NOH

MW: 127.18


NaOH + +NaCl

CH3

O

MW: 112.17


+ NH2OH.HCl

MW 69.5

MW 58.5 2 H2O

MW 18MW 40


Sr. No.


1. 4-Methyl cyclohexanone 1.054 2. Sodium hydroxide 0.801 3. Hydroxyl amine.HCl 0.784 4. Water 6.320

Complete Mass balance per KG: Step:III Input Kg Output Kg 4-Methyl cyclohexanone 1.054 4-Methyl cyclohexanone oxime 1.0 Sodium hydroxide 0.801 Aqueous layer 7.65 Hydroxyl amine.HCl 0.784 Water 6.320 Total Input 8.95 Total Output 8.65

Input – Output = 8.95 – 8.65 = 0.3 kg loss

Step-4: Brief process: 4-Methyl cyclohexanone oxime reacted with sodium metal in n-Butanol followed with con.HCl. Flow diagram:


Reactor

Pure 4-MCHA.HCl

n-Butanol

Acetone

Sodium metal

Separation

4-MCHA in Butanol

30% HCl

Butanol Distillation

Crude 4-MCHA.HCl

Acetone

Water Aq. ML


CH3

NH2.HCl

MW: 149.66

4-Methyl cyclohexylamine.HCl

Butanol MW 74 + +NaOH Butanol

CH3

NOH

MW: 127.18


+ HCl MW 36.5

Na

MW 23MW 40 MW 74


Sr. No.


1. 4-Methyl cyclohexanone oxime 1.26 2. Sodium metal 1.37 3. n- Butanol 20.5 4. Water 6.35 5. 30 % HCl 1.06 6. Acetone 10.6

Complete Mass balance per KG: Step:IV Input Kg Output Kg 4-Methyl cyclohexanone oxime 1.26 trans 4-methyl Cyclohexyl

Amine 1.0

Sodium metal 1.37 Aqueous layer 6.26 n- Butanol 20.5 Recover Butanol 14.35 Water 6.35 Residue 2.6 30 % HCl 1.06 Recovered Acetone 7.0 Acetone 10.6 Water -butanol 1.94 Total 41.14 Total 33.15

Input – Output = 41.14 – 33.15 = 7.99 kg loss

Step-5: Brief process: Trans -4- MCHA .HCl was taken in solvent (Toluene) and phosgene gas was

passed up to solution become clear at 80-85 o C, followed by distillation of toluene at reduced

pressure to get crude product which was further distilled to get pure T-4-MCHI.

Flow diagram:

T-4-MCHA.HCl Reaction Phosgen

Reaction Mass HCl gas/ Excess of Phosgene

Scrubbed in 10 % Caustic scrubber.

High Vaccum Distillation

Nitrogen Reaction Mass Remove Excess of Phosgene gas

Scrubbed in 10 % Caustic scrubber.

Crude Product

Residue Send to incineration

Toluene

Toluene Recovery To be used in next batch

High Vaccum Distillation

Product



Sr. No.


1. Trans-4-MCHA.HCl 1.162

2. Phosgene 1.744

3. Toluene 4.302

Input kg Output kg

Trans-4-MCHA.HCl 1.162 Trans-4-MCHI 1.00

Phosgene 1.744 Rec. Toluene 4.135

Toluene 4.302 Residue 0.0465

Total 7.208 5.181

Loss:508 gm ( 0.8488 kg HCl and 0.969gm phosgene gas and 0.128 gm toluene)

NH2.HCl

+

NCO

Trans-4-MethylcyclohexylisocyanateC8H13NO

Mol. Wt.: 139.19CAS No:35258-74-1

Trans-4-Methylcyclohexylamine.Hydrochloride

C7H16ClNMol. Wt.: 149.66

CAS No:33483-65-7

COCl2

PhosgeneCCl2O

Mol. Wt.: 99CAS No:75-44-5

+ 3HCl

ATUL LIMITED

Name of Product: RF Resin (Resoform P-20)


1.1



Resorcinol Tar is purified in Acetone. Resorcinol is polymerised with Styrene and purified Tar is added. Which is further polymerised with Formaldehyde in presence of Ethanol and CS Lye. Product is dehydrated by distillation and powerflex oil is added. Finished product is obtained by pastillation.

Purification Hyflo

Resorcinol

Acetone Reso-Tar

Distillation Acetone

Polymerization Water

Pastillation

37% Formaldehyde

Resoform P-20

Ethanol

Styrene Para Toluene Sulfonic Acid

CS Lye

1.2 Chemicals reactions with molecular weight stage wise -

1.3

S.N.



1 Acetone 0.005 2 Reso - Tar 0.045 3 Hyflo 0.008 4 Resorcinol 0.554 5 Formaldehyde 0.241 6 Powerflex Oil 0.010 7 Para toluene sulfonic acid 0.002 8 Styrene 0.352 9 Ethanol 0.015

10 CS Lye 0.001

1.5

S.No.


Input kg Output kg 1 Acetone 0.134 Resoform P-19 1.000 2 Reso - Tar 0.045 Acetone 0.129 3 Hyflo 0.008 Water 0.195 4 Resorcinol 0.554 Acetone loss in Distillation 0.005 5 Formaldehyde 0.241 Water loss in Distillation 0.025 6 Powerflex Oil 0.010 Hyflo 0.008 7 Para toluene sulfonic acid 0.002 8 Styrene 0.352 9 Ethanol 0.015

10 CS Lye 0.001 Total 1.362 Total 1.362

1.6 Complete Molecular balance -

ATUL LIMITED



1.1



Resorcinol Tar is purified in Acetone and Resorcinol is added to Tar and further polymerized with Formaldehyde to get Resoform P-19. Which is dehydrated by distillation and power flex oil is added. Finished product is obtained by Pastillation.

Purification Hyflo

Resorcinol

Acetone Reso-Tar



Pastillation

37%Formaldehyde

Resoform P-19

1.2 Chemicals reactions with molecular weight stage wise

-

1.3

S.N.



1 Acetone 0.035 2 Reso - Tar 0.357 3 Hyflo 0.008 4 Resorcinol 0.589 5 37% Formaldehyde 0.292 6 Powerflex Oil 0.010

1.5

S.No.


Input kg Output kg 1 Acetone 0.874 Resoform P-19 1.000 2 Reso - Tar 0.357 Acetone 0.839 3 Hyflo 0.008 Water 0.237 4 Resorcinol 0.589 Acetone loss in Distillation 0.035 5 37% Formaldehyde 0.292 Water loss in Distillation 0.012 6 Powerflex Oil 0.010 Hyflo 0.008 Total 2.131 Total 2.131


ATUL LIMITED



1.1



Resorcinol Tar is purified in Acetone and Resorcinol is added to Tar and further polymerized with Formaldehyde to get Resoform P-18. Which is dehydrated by distillation and power flex oil is added. Finished product is obtained by Pastillation.

1.2 Chemicals reactions with molecular weight stage wise -

Purification Hyflo

Resorcinol

Acetone Reso-Tar



Pastillation

Formaldehyde

Resoform P-18

1.3

S.N.



1 Acetone 0.018 2 Reso - Tar 0.177 3 Hyflo 0.008 4 Resorcinol 0.760 5 Formaldehyde 0.356 6 Powerflex Oil 0.010

1.5

S.No.


Input kg Output kg 1 Acetone 0.442 Resoform P-18 1.000 2 Reso - Tar 0.177 Acetone 0.424 3 Hyflo 0.008 Water 0.288 4 Resorcinol 0.760 Acetone loss in Distillation 0.018 5 Formaldehyde 0.356 Water loss in Distillation 0.015 6 Powerflex Oil 0.010 Hyflo 0.008 Total 1.752 Total 1.752


ATUL LIMITED


Name of Product: 4-Methoxybenzyl chloroformate


Brief process and flow diagram of process stage wise Brief process: 4-Methoxybenzyl alcohol is added to a mixture of phosgene and methylene chloride and stirred till the reaction is completed. The product is isolated after solvent recovery. Flow diagram:

MDC

Reactor

Reaction mass

Phosgene

4-Methoxybenzyl chloroformate

4-Methoxybenzyl alcohol

MDC recovery

Chemical reaction with molecular weight:

OH

OCH3

4-Methoxybenzyl alcohol 4-Methoxybenzyl chloroformate

MDC

O

OCH3

Cl

O

M. Wt. 138.16 M. Wt. 200.61

Cl Cl

O

+ HCl+Phosgene

M. Wt. 98.9

M. Wt. 36.5


Sr. No.

Raw Material Qty (g)

1. 4-Methoxybenzyl alcohol 0.725 2. Phosgene 0.65 3. MDC 0.24

Complete Mass balance per KG:

Input Kg Output Kg 4-Methoxybenzyl alcohol 0.725 4-Methoxybenzyl chloroformate 1.0 Phosgene 0.65 Recovered MDC 1.36 MDC 1.6 MDC vapor loss 0.24 HCl gas 0.19 Excess phosgene 0.13 Product loss 0.055 Total Input 2.975 Total Output 2.975

Complete Molecular balance: Input Output

4-Methoxybenzyl

alcohol

Phosgene 4-Methoxybenzyl

chloroformate

HCl

gas

Excess

phosgene

Loss (as

4-Methoxybenzyl

chloroformate)

Moles 0.353 0.441 0.335 0.353 0.088 0.018

Mole

Ratio

1.00 1.25 0.949 1.00 0.25 0.051

ATUL LIMITED

Name of Product: N, N- Disuccinimidyl Carnonate


Brief process and flow diagram of process stage wise : N-Hydroxy Succinimide is reacted with Phosgene in presence of tributyl amine in THF at 0-5°C to give the product. Mass Balance:


N-Hydroxy Succinimide

Phosgene

Tributyl amine

THF

Filter

N,N-Disuccinimidyl Carbonate Recoveries Gases

THF HCl trapped with

Tributyl Amine Tributyl amine

Reaction vessel

0-5°C

Chemicals reactions with molecular weight stage wise. Synthetic Scheme:

N

O

O

OH + Cl

O

Cl + N

CH3

CH3

CH3

Tributyl AmineMol. wt-185.35

PhosgeneMol wt-99

N-Hydroxy SuccinimideMol wt-115.08

THF

0-5 °C

N

O

O

O N

O

O

O

O

N

CH3

CH3

CH3

+ .HCl

N,N-Disuccinimidyl Carbonate

Mol wt-256.17

Tributyl Amine HCl

Mol wt-221.81 List of raw materials along with quantity per KG Raw Materials Quantity (Kg) Recoveries (%) N- Hydroxy Succinimide 1.01 Nil Tributyl Amine 0.19 90 Phosgene 0.55 Nil THF 2.00 80 Complete Mass balance per KG Input Quantities

(kg) Out Put Quantities

(kg) N- Hydroxy Succinimide 1.01 N,N-Disuccinimidyl Carbonate 1.00 Tribtyl Amine 1.875 Tributyl Amine 1.69 Phosgene 0.55 HCl 0.23 THF 10.00 Rec. THF 8.00 Total Input 13.43 Total Output 10.92

Complete Molecular balance - Two moles of N-Hydroxy Succinimide reactes with one mole of Phosgene in presence of two moles of tributyl amine to give one mole of N,N – Disuccinimidyl Carbonate and two moles of tributyl amine HCl.

ATUL LIMITED

Name of Product: HX-13059

1.Lab Process details:

Brief process and flow diagram of process stage wise Step 1: Synthesis of 1-(2,4-dichlorophenyl)-2,4-tiazole-5-one (intermediate A): 2,4-Dichloroaniline is converted to diazonium salt solution which is reduced to 2,4-dichlorophenylhydrazine. This hydrazine on reaction with formaldehyde forms corresponding hydrazone which is cyclized and then oxidized to afford 1-(2,4-dichlorophenyl)-2,4-tiazole-5-one (intermediate A) . Step 2. Synthesis of N-(2,4-difluorophenyl)-N-isopropycarbamoyl chloride (Intermediate B): 2,4-Difluoroaniline reacted with isopropyl bromide to prepare the N-isopropyl -2,4-difluoroaniline. This is further reacted with triphosgene to afford the product N-(2,4-difluorophenyl)-N-isopropycarbamoyl chloride (intermediate-B).

Step 3. (HX-13059) [1-(2,4-dichlorophenyl)-2',4'-difluoro-1,5-dihydro-N-isopropyl-5-oxo-4H-1,2,4-triazole-4-carboxanilide: 1-(2,4-Dichlorophenyl)-1,2,4-traizol-5-one (Intermediate A) is reacted with N-(2,4-difluorophenyl)-N-isopropyl carbamoyl chloride (Intermediate B) in presence of NaOH and TBAB at 95-100 oC. Further purification with Toluene, Hexane and Methanol gives pure [1-(2,4-dichlorophenyl)-2',4'-difluoro-1,5-dihydro-N-isopropyl-5-oxo-4H-1,2,4-triazole-4-carboxanilide (HX-13059). Flow diagram for Int A :


Flow diagram for Int B:

Flow diagram for final HX-13059:

Balanced Chemical Equation:

INTERMEDIATE-A

NH2

Cl

Cl

+

2,4-dichloroaniline

2 HCl NaNO2+

N+

Cl

Cl

N

2,4-dichlorobenzenediazonium chloride

Cl-

+ +NaCl 2 H2O

MW=162.01

MW=72.84 MW=68.99

MW=209.45

MW=58.44 MW=36.02

N+

Cl

Cl

N

2,4-dichlorobenzenediazonium chloride

Cl-

+ 2 NaHSO3

N

Cl

Cl

NH

SO3Na

SO3Na

disodium 1-(2,4-dichlorophenyl)hydrazine-1,2-disulfonate

+ HCl

MW=209.45

MW=208.12

MW=381.12

MW=36.46

N

Cl

Cl

NH

SO3Na

SO3Na

disodium 1-(2,4-dichlorophenyl)hydrazine-1,2-disulfonate

+ 2 H2ONH

Cl

Cl

NH2

(2,4-dichlorophenyl)hydrazine

Na2SO4 H2SO4+ +

MW=381.12

MW=36.02

MW=177.03

MW=142.04 MW=98.07

NH

Cl

Cl

NH2

(2,4-dichlorophenyl)hydrazine

+ H H

O

formaldehyde

NH

Cl

Cl

N CH2

formaldehyde (2,4-dichlorophenyl)hydrazone

H2O+

MW= 177.03

MW=30.02

MW=189.04

MW= 18.01

NH

Cl

Cl

N CH2

+

MW=189.04

formaldehyde (2,4-dichlorophenyl)hydrazone

NaOCN

N

Cl

Cl

NH

NH

O

2-(2,4-dichlorophenyl)-1,2,4-triazolidin-3-one

NaCN+MW=65.00

MW=232.06

MW=49.00

N

Cl

Cl

NH

NH

O

2-(2,4-dichlorophenyl)-1,2,4-triazolidin-3-one

+

MW=232.06

NaOCl

N

Cl

Cl

N

NH

O

2-(2,4-dichlorophenyl)-2,4-dihydro-3H-1,2,4-triazol-3-one

MW=74.44+ +

MW=18.01 MW=58.44

MW=230.05

H2O NaCl

INTERMEDIATE-B

NH2

F

F

+CH3

CH3 Br

2-bromopropane

2,4-difluoroaniline

NH

F

F

CH3

CH3

+ HBr

2,4-difluoro-N-(propan-2-yl)anilineMW=129.10

MW=122.99

MW=171.18

MW=80.91

NH

F

F

CH3

CH3

+

2,4-difluoro-N-(propan-2-yl)aniline

MW=171.18

(Cl3CO)2CO

N

F

F

CH3

CH3 Cl

O

(2,4-difluorophenyl)propan-2-ylcarbamic chloride

2 COCl2+ + HCl

MW=233.64

MW=197.82MW=296.74

Triphosgene MW=36.46

FINAL STEP

N

F

F

CH3

CH3 Cl

O

(2,4-difluorophenyl)propan-2-ylcarbamic chloride

MW=233.64

N

Cl

Cl

N

NH

O

2-(2,4-dichlorophenyl)-2,4-dihydro-3H-1,2,4-triazol-3-one

+

MW=230.05

Intermediate - A Intermediate - B

N

Cl

Cl

N

N

O

N

F

F

CH3

CH3

O

1-(2,4-dichlorophenyl)-N-(2,4-difluorophenyl)-5-oxo-N-(propan-2-yl)-1,5-dihydro-4H-

1,2,4-triazole-4-carboxamideOR [HX-13059]

+ HCl

MW=427.23

MW=36.46


Sr No Raw Materials Consumption / 1Kg 1 2,4 Dichloroaniline 1.29 2 Toluene 1.29 3 35% HCl 13.875 4 H2O 7.31 5 NaNO2 (98.5%) 0.59 6 Na2SO3 (97%) 2.59 7 H2SO4 (95%) 0.08 8 48%NaOH 9.62 9 t-BUOH 7.96 10 37%HCHO 0.65 11 AcONa 0.03 12 AcOH 0.76 13 90%NaOCN 0.8 14 13%NaClO 3.75 15 Dichloroethane 7.32 Int A first step 1 2,4 Difluro aniline 0.97 2 IPBr 1.02 3 H2O 4 48%NaOH 0.69 5 Hexane 1.28 Int B Second step 1 2,4 Difluro aniline 0.62 2 N-Ipr-2,4 difluro aniline 0.18 3 IPBr 0.72 4 H2O 0.99 5 48%NaOH 0.51 6 Toluene 3.18 7 Triphosgene 0.60 Final HX-13059 step 1 Int A 0.76 2 Toluene 5.70 3 NaOH (96%) 0.13 4 nBu4NBr (98%) 0.20 5 int B 0.76 6 H2O 8.82 7 n-Hexane 0.13 8 MeOH 4.03

List of co-product per KG Complete Mass balance per KG Intermediate A

Process Input Kgs OutPut Kgs DI AZONIUM SALT PREPERATION - 2-4 Di chloro Aniline 1.1 Toln+product layer 10.2 NaNO2 0.5 Water 0.9 toluene 0.5 HCL 2.0 Water 5.1 10.2 Water 8.5 Toluene Layer 0.5 Na2SO3 2.1 Aquous Layer 20.9 H2SO4 0.1 Di Azo Salt 10.2 Total 20.9 Acid Hydrolysis / Product Isolation- aq layer 20.9 HCl (35%) 6.8 Reaction Mass 34.3 Caustic Solution (48%) 6.6 Total 34.3 filteration Reaction Mass 34.3 water wash 8.6 Wet Cake 1.3 Effluent 41.6 Slurry Wash to cake - Water 5.8 Cake 1.3 Cake 1.3 Water waste 9.5 Hydrazone Preperation Cyclization- Cake 1.3 Tert - Butanol 5.8 Water 6.4 Reaction Mass 20.6 37%HCHO 0.5 Sodium Acetate Acetic Acid Water 0.1 Sodium Cynate 0.7 Acetic Acid 0.6 Water 0.6 Cyclization 13% Hypochlorite Solution 3.4 NaOH flakes 0.5 Water 0.5

20.6 EDC Wash - Product Slurry 20.6 Tert Butanol Rec Tert Butanol 5.8 Distillation Residue 14.8 EDC extraction Distillation Residue 14.8 Aquous Layer 14.8 EDC Wash 1 3.0 EDC Wash 6.1 Intermediate A - Isolation - Aqueous Layer 14.8 HCl 2.6 Product Slurry 19.9 Water 2.6 Total 19.9 Product Slurry 19.9 Intermediate A 1 Water wash 1.3 Water 20.9

Intermediate B

Steps Reactants Kgs Output Kgs

Isopropylation 2,4-difluro aniline 0.57 Aq Layer 1.56

N-isopropyl -2,4-difluroaniline (91.75%)

0.17 Toluene layer 2.98

IPrBr 0.65 H2O 0.90 50% NaOH 0.46 Toluene 1.80 4.55 H2O 0.90 Aq layer 0.91 H2O 0.90 Aq layer 0.91 Toluene layer 2.96 Azeotropic distillation

Toluene laye r 887 H20 0.01

Phosgenation Triphosgene solution

Toluene rec 2.72 Triphosgene 0.55 Toluene 1.09 Toluene laye r 2.94 Distillation Product 1.00

HX-13059

Input Kgs OutPut Kgs

Toluene 3.810 Toln+product layer 4.833

1-(2-4-Dichlorophenyl) -5-one 0.694 Water(Azeotropic

Distillation) 0.129

Catlyst 0.189 96% NaOH 0.129 Water 0.129 4.961 Toluene 0.365 Int B solution 1.099 Int B 0.732 Toluene+ Int A 4.549 Reaction mass 5.647

N-(2,4-difluorophenyl)- chloride 1.099

Total 5.647 Reaction Mass 5.647 Toluene layer 5.427 water wash 5.139 water wash 5.138 Product 1.243 Slurry 8.090 Methanol 6.347 Toluene 0.250 Hexane 0.250 Slurry 8.090 Wet Cake 9.534

Water wash from R-201 2.550 Filtrate +Wash ML 6.847

Wet Cake 1.110 HX 13059 1.000 water Recovery 0.110


Division: R & D -PI

Name of Product: Di-t-butyl dicrbonate


Brief process: Solid Sodium-t-butoxide is reacted with gaseous carbon dioxide in a gas-solid phase reaction to obtain the corresponding carbonate salt. This carbonate salt is treated with phosgene and then triethyl amine to obtain the final product DIBOC or Boc. anhydride.

DI-TERT-BUTYL DICARBONATE (Boc. anhydride)

Date:

Flow diagram:

STAGE-I: Carbonylation of t-Butoxide (NaTBC)

STAGE-II: Di-t-butyl carbonate from NaT

5. Addition Time: 2h

4. Ethyl acetate (130 ml)

1. Ethyl acetate (200 ml)

2. Phosgene (35 g)

3. Na TBC (100 g)

1. Na-t-butoxide (100 g)

2. CO2 gas (45.88 g) 10L/min

6. Triethyl amine (130 ml)

11. Ethyl acetate (25 ml x 4)

8. Hyflo ( 100 ml)

Autoclave <50°C

19-20 hPress: 2 Kg/cm2

Na-TBC (Yield: 96.5 %)

PhosgenationTemp: -5-0°C

Time: 1 h

16. Crude (52.5 g)

PhosgenationTemp: -5-0°CTime: 30 min7. 25-30°CTime: 1 h

9. Filtration10. Org layer12. Washing ML

14. DistillationVac: 80-90 mmHg

Mass Temp: 40-45°CBath Temp: 50°C

13. Residue

15. Recovered Ethyl acetate (54 %)

17. Distillation18. Vac: 15 mmHgMass Temp: 40-45°C

Bath Temp: 50°C20. Vac: 1.2 mBarBath Temp: 75°C

19. Recovered Ethyl acetate

21. Distillate (As DIBOC)39 gYield: 50 % from NaTBCOverall Yield: 48.2 %

22. Residue (< 1 g)

Chemicals reactions:

Stage-I

+ CO2O O

Na

O

ONa

M.Wt 96 44 140

Stage-II

O ONa

O+ COCl2

O O

O

O O

O O+ 2 NaCl

M.Wt 140 99 262

O O

O

O O

O O

O O

O

O

O

TEA + CO2

M.Wt 262 218

Raw Material: Sr. No Raw Material Qty/Kg

1 Sodium-t-butoxide 1.82 2 Carbon dioxide gas 0.835 3 Ethyl acetate 2.05 4 Phosgene 0.89 5 Triethyl amine 0.34 6 Hyflo supercel 0.256

Complete Mass balance per KG: Input Kg Output Kg Stage-I Sodium-t-butoxide 1.82 Sodium-t-butyl carbonate 2.58 Carbon dioxide gas 0.835 Total 2.655 2.58 Stage-II Sodium-t-butyl carbonate 2.58 Crude DIBOC 0.955 Phosgene 0.89 Recovered ethyl acetate 5.23 Kg Ethyl acetate 9.87 Triethyl amine 0.33 Dist. DIBOC 1 Hyflo 0.258 Total 13.93 7.18

Annexure – 3 Google map of ATUL LTD.

Annexure – 4 Location map of ATUL LTD.

WATER (KL/DAY) BALANCE DIAGRAM (EXISTING)

RAW WATER 22569

DOMESTIC 937

INDUSTRIAL 21632

PROCESS16376

BOILER1170

COOLING2735

WASHING1351

PROCESS17403

BOILER805

WASHING1305

COOLING1944

Treated effluent discharged through Closed 4 km length pipeline

to tidal zone of river par

EFFLUENT21377

NORMALEFFLUENT

17283

High COD eff. To Incinerator

23

LOSS 791

TO EFFLUENT TREATMENT

PLANT

GARDEN 0

Septic tank/Soak pit

937

LOSS 365 LOSS 46

High TDS effluent to MEE

97

Water with Chemical 1027

WATER (KL/DAY) BALANCE DIAGRAM (PROPOSED)

RAW WATER 5788.70

DOMESTIC 2

INDUSTRIAL 5786.70

PROCESS1281.70

BOILER1958

COOLING2047

WASHING500

PROCESS1515.03

BOILER626

WASHING500

COOLING400

EFFLUENT1684.51

NORMALEFFLUENT

158.51

High COD eff. To Incinerator

57.57

LOSS 1647

TO EFFLUENT TREATMENT

PLANT

GARDEN 0

Septic tank/Soak pit

2

Water with Chemical 233.33 LOSS 1332 LOSS 0

High COD eff. To MEE

1298.95

Treated effluent discharged through Closed 4 km length pipeline

to tidal zone of river par

CHEMICAL SLUDGE

SUPERNATE RECYCLE

WASTE WATER FROM ATUL BIOSCIENCE LTD.

SLUDGE

GUARD POND

BIO-REACTORS (2 NOS.)

SURFACE AERATORS

WASTE WATER FROM ATUL PLANTS

MIXING CHAMBER (Hook Up Chamber)

ON LINE LIME SLURRY IN CHANNEL EQUALIZATION TANKS

(Pond No. 1, 3, 4) FLOCCULANTS /COAGGULANTS

HOLDING TANK

RECYCLE

CLARIFIER TANKS

TREATED EFFLUENT DISCHARGED TO PAR ESTUARY THROUGH 4 km PIPELINE

BLOCK DIAGRAM OF EFFLUENT TREATMENT PLANT

SLUDGE THIKENER

DISPOSAL / LANDFILL

PRIMARY CLARIFIER

NUTRIENTS

SLUDE DEWATERING BELT PRESS/

SLUDGE DRYING BEDS FILTRATE RECYCLE

PULSATOR (POLISHING TANK)

Annexure – 6 SCHEMATIC FLOW DIAGRAM OF EXISTING ETP

Annexure – 7 LOCATION OF FINAL DISCHARGE POINT OF TREATED EFFLUENT THROUGH PIPELINE IN RIVER PAR

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