APPLICATION FOR ENVIRONMENTAL CLEARANCE...

APPLICATION FOR ENVIRONMENTAL CLEARANCE

ANNEXURE

For

“Proposed Manufacturing of Specialty Chemicalsand Agro Chemical Products”

BY

M/s. Crimsun Organics Private Limited (COPL)

at

SIPCOT Industrial Area

VILLAGE& PANCHAYAT: Kudikadu

TALUK: Cuddalore

DISTRICT: Cuddalore

STATE: Tami Nadu

Consultants:

M/s. Hubert Enviro Care Systems (P)LtdChennai

M/s. Eco Chem Services LtdSurat

June-2018

List of Annexure

A. No Annexure Name Page No.

1 Production and manufacturing processes 3

2CUSECS membership for STP treated water disposal(CETP for treated water disposal)

72

3 Water supply agreement letter. 86

4 STP & ETP Scheme 100

5 TSDF Agreement. 102

6 Scrubber design. 103

7TN govt. document for SIPCOT is declared industrialarea.

104

8 Land document 111

9 Water balance chart 189

10 Site layout plan 190

11 GSR products Ltd CFE 191

12 GSR products Ltd CFO 202

13 Crimsun Ltd CFO 216

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Note: Annexure 2, 3, 8, 11, 12 & 13 will be submitted as hard copy due to file size restriction

Crimsun Proposed Products’ Process

S. No. Products Name Quantity (MT/Month)

Speciality Chemical1 Parachlorobenzyl cyanide 20.002 Pyrazole 20.003 Meta –phenoxy benzaldehyde (MPB) 30.00

Fungicides4 Thiophanate Methyl 50.005 Hexaconazole 30.006 Propiconazole 30.007 Difenoconazole 15.008 Tricyclazole 50.009 Carbendazim 50.0010 Cyproconazole 30.0011 Trifloxystrobin 20.0012 Cymoxanil 20.0013 Pyroclostrobin 20.0014 Metalaxil 20.0015 Tebuconazole 20.0016 Boscalid 20.0017 Picoxystrobin 20.0018 Thifluzamide 20.00

Herbicides19 Pretilachlor 50.0020 Glyphosate 50.0021 Clodinafop-propargyl 20,0022 Bis-pyribac Sodium 20.0023 Quizalofop 20.0024 Propaquizalofop 20.0025 Mesotione 20.0026 Fluroxypyr 20.0027 Imazamox 30.0028 Pinoxaden 30.0029 Amytryn 30.0030 Tembotrione 20.0031 Topramezone 20.0032 Halosulfuron 20.0033 Penoxsulam 20.0034 Flucetosulfuron 20.0035 Pendimethalin 30.0036 Clorimuron 20.0037 Necosulfuron 20.0038 Metsulfuron 20.00

Insecticides39 Dichlor vos (DDVP) 50.00

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Annexure 1

40 Acephate 30.0041 Diafenthiuron 30.0042 Imidachloprid 30.0043 Buprofezin 30.0044 Thiamethoxam 30.0045 Cypermethrin 30.0046 Alphacypermethrin 20.0047 Fipronil 20.0048 Acetamiprid 30.0049 Propargite 30.0050 Indazocarb 20.0051 Dinotefuron 20.0052 Flonicamid 20.0053 Etoxazold 20.0054 Metaflumizone 20.0055 Spiromesifen 20.0056 Spirotetramate 20.0057 Chlorantraniliprole 20.0058 Sulfoxaflor 20.00

Total 1475

1. Parachlorobenzylcyanide (PCBCN)

1.1 Manufacturing Process

Parachlorotoluene will be chlorinated partially in the methyl group using chlorine at120C . The product parachlorobenzylchloride will be reacted with sodium cyanide inpresence of water and phase transfer catalyst. After completion of reaction, theaqueous will be separated, washed with water and the organic will be distilled torecover unreacted parachlorotoluene and finally the productparachlorobenzylcyanide (PCBCN) will be distilled.

1.2 Chemistry of Reaction

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1.3 Material Balance for 1000 Kgs PCBCN

Material Input Material OutputParachlorotoluene 3000 Kgs Parachlorotoluene 2128 kgsChlorine 465 Kgs PCBCN (Product) 1000 KgsPTC 50 kgs PTC 50 KgsSodium cyanide 387 Kgs Sodium cyanide 65 KgsWater 2500 Kgs Sodium chloride 384 Kgs

Water 2500 KgsOrganic Distillationtar 36 KgsHCL 239 Kgs

Total 6402 Kgs Total 6402 Kgs

Aqueous Waste PTC 50 Kgs +NaCN 65 Kgs +NaCl 384 Kgs +HCl 239 Kgs +Water 2500 Kgs

Total 3238 Kgs

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2. Pyrazole


4-Trifluoromethyl-2,6-dichloroaniline will be taken in acetic acid and cooled to 20C.At 20C, sulphuric acid and sodium nitrite acid mixture will be added and completethe diazotisation reaction. After the reaction ethyl 2,3-dicyanopropionate ,EDC,Acetic acid will be added and the pyrazole formation will be completed. Immediatelyafter the completion of the reaction, water will be added, the solution will beneutralized by 25% aqueous ammonia, layers will be separated, the organic will bewashed and finally the solvent will be partly distilled and the product will becrystallised and filtered,dried.


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2.3 Material balance for 1000 Kgs Pyrazole

In put Quantity(Kgs)

Ailine 754.00Acetic Acid 2000.00Sulphuric Acid 1750.00Sodium Nitrite 248.00

Ethyldicyanopropionate 500.00EDC 5000.00Water 8000.00NH3 25% 8000.00

Total 26252.00

3. Metaphenoxybenzaldehyde (MPB)


Step 1

In step 1, Benzaldehyde will be brominated in the meta position by dissolvingbenzaldehye in solvent EDC and complexing with anhydrous AlCl3 and reacted withbromine in presence of chlorine at 20C. After the reaction, the mass will be drownedin water, layers will be separated and the solvent will be distilled first followed byMetabromobenzaldehyde.

Step2

The Metabromobenzaldehyde prepared in step1 will be reacted withmonoethyleneglycol and will be reacted with potassium phenoxide in presence ofcatalyst cuprous chloride at 120C. The product metaphenoxybenzaldehyde formedwill be hydrolysed by dilute 1N sulphuric acid and fractionally distilled under vacuumto get pure Metaphenoxybenzaldehyde.

Out Put Quantity (Kgs)

EDC Loss

EDC Recovered

100.00

4900.00

Pyrazole 1000 Kgs

Aqueous Wastecontaining water,Ammonium Sulphate,

Sodium Sulphate

Ammonium Acetate

20152.00

Organic waste

Total

100.00

26252.00 Kgs

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3.2 Chemistry of reaction

Step1: MBB formation

Step 2 : MPB formation

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3.3 Material Balance for 1000 Kgs

Input OutputRaw material Weight

( Kgs)Items Weight (kgs)

Benzaldehye 715.00 EDC LossEDC Recovered

200.002900.00

AlCl3 1168.00 MPB 1000 KgsEDC 3100.00 Water Waste containing

SaltsBromine 538.00 Water 4000.00Chlorine 480.00 PTSA 20.00MEG 560 .00 CuCl 20.00PTSA 20.00 KBr 606.00Phenol 608.00 Kphenate 140.00KOH (88%) 415 .00 AlCl3 1168.00CuCl 15.00 HCl 247.00Sulphuric Acid 140.00 Sulphuric Acid 140.00

Total Aqueous 6341.00Toluene 2000.00 MEG 560.00Water 4000.00 Toluene Loss

Toluene Recovered220.001780.00

Distillation Tar 758.00

Total 13759.00 Total 13759.00

4. Thiophanate methyl


Thiophanate methyl will be manufactured starting from Sodiumthiocyanate.Sodiumthiocyanate will be suspended in EDC and will be reacted withmethychloroformate at 30C. The reaction product will be further reacted withOthophenylene diamine at 90C and the product will be filtered, washed with waterand will be dried to get thiophanate methyl

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4.3 Material balance ( for 1000 Kgs)

Input OutputRaw material (Kgs) Items Aqueous Waste

Sodiumthiocyanate

565.00 EDC LossEDC Recovered

200.002800.00

MCF 659.00 Thiophanatemethyl

1000.00

EDC 3000.00 Water WasteOPDA 359.00 Water 2500.00 2500.00Water 2500.00 Sodium Chloride 408.00 408.00

Organic Waste 175.00Total 7083.00 Total 7083.00 2908.00

5. Hexaconazole


Step1: Oxirane formation

In the manufacturing process, valerophenone will be added with DMS and thetemperature will be raised upto 42 deg C. At that temperature DMSO4 will be addedand will be reacted for 3 Hrs. After that KOH will be charged for 3 hours and will bereacted.. After the reaction, DMS will be distilled, water will be added and the saltswill be dissolved. The oxirane will be extracted in toluene and toluene will beconcentrated to get oxirane,

Step 2 ; Hexaconazole formation

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Oxirane will be dissolved in DMF and will be reacted at 120 deg C with 1,2,4-triazolein presence of K2CO3. After the reaction, the mass will be filtered, and the organiclayer will be concentrated to get crude Hexaconazole. This crude will be crystallisedin cyclohexane to get pure hexaconazole.


5.3 Material Balance ( for 1000 Kgs)

Input Out putRaw materials (Kgs) Items (Kgs) Aqueous WasteDMS 1300 DMS Loss

Recovered2001100

2,4-Dichlorovalerophenone 865Water 3000 Water 3000 30001,2,4-Triazole 274 54 54KOH (88%) 304 KOH 102 102

MethylKsulphate 549 549K2CO3 150 K2CO3 150 150DMSO4 602 DMSO4 201 201DMF 1500 DMF Loss

Recovered2001300

Methanol 1200 Methanol lossRecovered

300900

Hexaconazole 1000Organic Waste 139

Total 9195 Total 9195 4056

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6. Propiconazole


Step1: Bromoketal formation

2,4-Dichloroacetophenone (DICAP) will be mixed with cyclohexane, pentane-1,2-diol(PDL) and Paratoluene sulphonic acid (PTSA) and the reaction water will be distilledout azeotropically at 110 deg C. The product acetal will be brominated in the sidechain and the product Bromoketal will be isolated and will be taken for step2

Step 2 : Propiconazole formation

The Bromoketal prepared in the step 1 will be reacted with Potassium triazole insolvent DMSO at 125 deg C and after completion of the reaction, DMSO will bedistilled and the crude will be washed with water and the organic will be distilled toget pure propiconazole.


Step 1

Step 2

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Input OutputRaw materials (Kgs) Item (kgs) Aqueous

DICAP 735.00 CyclohexaneLossRecovered

200.00

1400.00Pentane1,2-diol 420.00 Pentane diol 75.00 75.00Cyclohexane 1600.00DMSO 2400.00 DMSO Loss

Recovered150.002250.00

Toluene 1500.00 Toluene LossRecovered

200.001300.00

Bromine 410.00 HBr 415.00 415.001,2,4-Triazole 330.00 Triazole waste 130.00 130.00PTSA 15.00 PTSA 15.00 15.00KOH 309.00 KBr 339.00 339.00Water 2000.00 Water 2000.00 2000.00

Organic waste 236.00Propiconazole 1000.00

Total 9710.00 Total 9710.00 2974.00

7. Difenoconazole


Step1

2-Chloro-4-(4’-chlorophenoxy)acetophenone(CCPA) will be reacted with Bromineand Propane-1,2-diol in presence of PTSA in solvent cyclohexane under reflux. Afterthe reaction, the organic will be washed with water, layers will be separated and thesolvent will be distilled out. The product bromoketal will be taken for next reaction.

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Step2

The intermediate bromoketal will be reacted with Potassiumtriazole in solventDMSO. After completion of the reaction, the solvent will be recovered by distillation,and the product will be extracted with toluene, washed with water and toluene will bedistilled out. The crude will be crystallised in IPA-HCl and washed with water dried toget the required quality product.


Step1: Bromoketal formation

Step 2: Difenoconazole Formation

Difenoconazole

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7.3 Material Balance ( for 1DMSO000 Kgs)

Input OutputRaw Material (Kgs) Items (Kgs) Aqueous

CCPA 755.00 Difenoconazole 1000.00Propane-1,2-diol 342.00 HBR 218.00 218.00Bromine 439.00 PTSA 25.00 25.00PTSA 25.00 Cyclohenaxe Loss


Cyclohexane 2000.00 KBr 319.00 319.00DMSO 2500.00 DMSO Loss


Triazole 200.00 IPA.HCl 2500.00KOH 153.00 Organic Waste 254.00IPA.HCl 2500.00Water 2000.00 Water 2098.00 2098.00Toluene 2000.00 Toluene Loss


Total 12914.00 Total 12914.00 2660.00

8. Tricyclazole

8.1 Manufacturing process

HMBT (2-Hydrazino-4-methylbenzothiazole) will be suspended in excess formic acid.Under stirring, gradually the temperature will be raised and the mass will be broughtinto reflux. After refluxing for about 2 hours, the excess formic acid will be distilledand the product will be suspended in water, adjusted the pH to 6.5 , filtered, driedand will be packed.


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Input OutputRaw material (Kgs) Item (Kgs) Aqueous

HMBT 978.00 Tricylazole 1000.00Xylene 2000.00 Formic Acid 1350.00Formic Acid (85%) 1600.00 Xylene Loss


Water 2500.00 Water 2696.00 2696.00NaHCO3 40.00 Sodium Formate 32.00 32.00

Carbondioxide 21.00Residue 19.00

Total 7118.00 Total 7118.00 2728.00

9. Carbendazim

9.1 Manufacruting Process

Calcium Cyanamide will be suspended in water and will be agitated. Under stirringMethylchloroformate will be added at 35 deg C for 1 hour and maintained stirring for2 hours. After confirming the completion of reaction, the reaction mass will be filteredand the filtrate will be mixed with Orthophenylene diamine and will be heated to 90deg C maintaining pH 4.5 by the addition of HCl. After completion of reaction, thereaction mass will be cooled to 60 deg C and filtered, washed and dried to getcarbendazim.


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Input OutputRaw material ( Kgs) Item (Kgs) Aqueous

Calcium Cyanamide(50%)

1022.00Carbendazim 1000.00

Methylchloroformate 679.00 Calcium Chloride 709.00 709.00Orthophenylenediamine 596.00 Ammonium

chloride495.00 495.00

Con.HCL 1340.00 Soiled Waste 495.00Water 3200 Water 4138 4138

6837.00 6837.00 5342

10. Cyproconazole


Cyproconazole will be manufactured by reacting 1-(4-chlorophenyl)-2-cyclopropylpropan-1-one (CPCP) with DMSO4 in presence of KOH and DMS. Aftercompletion of the reaction, the product oxirane formed will be reacted with 1,2,4-triazole in solvent DMF. After work up, the product will be crystallised in methanoland dried to get Cyproconazole


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10.3 Material Balance ( 1000 Kgs )

Inout OutputRaw material ( Kgs) Item (Kgs) Aqueous

CPCP 793.00 K(CH3)SO4 770.00 770.00DMSO4 647.00DMS 2500 DMS ( Loss )


KOH 327 Organic Residue 109.00Toluene 2000 Toluene (Loss)

Receovered200.001800.00

DMF 3000 DMF (Loss)Recovered

200.002800.00

K2CO3 150.00 K2CO3 150.00 150Methanol 1500.00 Methanol ( Loss)


1.2,4-Triazole 354 Triazole 92.00 92.00Water 3000.00 Water 3000.00 3000.00

Cyproconazole 1000.00

Total 14271.00 Total 14271.00 4012.00

11. Trifloxystrobin


The intermediate methylphenylethylidenehydroxylamine (MPEH) will be reacted withMethyl chloromethylphenylmethoxyimino-oxopropanoate (MCPO) in presence ofsodium methoxide in solvent methanol at 50 deg C. After the reaction, the mass willbe filtered, solvent will be distilled and the product will be isolated.

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Input OutputRaw Material ( Kgs) Items (kgs) Aqueous

MPEH 524.00 MPEH 37.00MCPO 623.00 MCPO 44.00Sodiummethoxide

146.00 SodiumMethoxide

7.00 7.00

Methanol 3000.00 Methanol LossRecovered

250.002750.00

SodiumChloride 151.00 151.00

Water 1000.00 Water 1000.00 1000.00Organic Waste 34.00Trifloxystrbin 1000.00

Total 5293.00 Total 5293.00 1158.00

12. Cymoxanil


2-Ethyl-2’-cyanoacetylurea will be dissolved in water and at 30 deg C PTSA andNaNO2 will be added to get the oxime. After the reaction, potassium carbonate andDMSO4 will be added and after completion of the reaction, the reaction mass will becooled to 20 deg C and will be filtered, washed with water and dried.

12. 2 Chemistry of Reaction

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12.3 Material Balance ( for 1000 kgs)

Input OutputRaw material ( Kgs) Item (kgs) Aqueous

Ethylcyanoacetylurea 860.00 Cymoxanil 1000.00NaNO2 377.00 KCH3SO4 757.00 757.00PTSA 896.00 KHCO3 448.00 448.00K2CO3 679.00 NaPTSA 1011.00 1011.00DMSO4 636.00 Inorganic Waste 232.00 232.00Water 4000.00 Water 4000.00 4000.00

Total 7448.00 Total 7448.00 6448.00

13. Pyroclostrobin

13.1 manufacturing Process

The process will start with Parachlorophenylhyrazine. Parachlorophenylhyrazine willbe reacted with ethylacrylate in presence of solvent propanol and hydrogenperoxide. After the reaction, the product will be isolated and will be reacted with 2-nitrobenzylchloride in presence of solvent dioxane and catalyst sodium methoxide.After, the reaction, the reaction mass will be reacted with hydrogen and then withDMSO4 and MCF to get Pyroclostrobin/


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Input OutputRaw material (Kgs) Item (Kgs) AqueousParachlorophenylhydrazine 459.00 Ethanol 148.00Ethylacrylate 322.00 NaCl 335.00 335.00H2O2 (50%) 116.00 NaCH3SO4 403.00 403.00Propanol 1500.00 Propanol Loss


2-Nitrobenzylchloride 491.00 Methanol 89.00Sodium Methoxide 162.00 ConsumedDMSO4 361.00 ConsumedMCF 271.00 Consumed

OrganicWaste

276.00

NaOH (98%) 229.00 Product 1000.00Dioxane 2000.00 Dioxane Loss


Water 2000.00 Water 2160.00 2160.00

Total 7911.00 Total 7911.00 2898.00

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14. Metalaxyl


Methyldimethylanilinopropanoate (MPX) will be reacted with Methoxyacetyl chloride(MAC) in presence of sodium carbonate in solvent toluene. After the reaction, theorganic will be washed with water, layers will be separated and the organic will beconcentrated to get the product metalaxyl



Input OutputRaw Material (Kgs) Item (kgs) Aqueous

MPX 862.00 Metalaxyl 1000.00MAC 500.00 Sodium Chloride 154.00 154.00DMF 30.00 DMF 30.00 30.00Toluene 2000.00 Toluene Loss


Sodium Carbonate 140.00 CO2 58.00Organic Waste 266.00

Water 2200 Water 2224.00 2224.00

Total 5732.00 Total 5732.00 2408.00

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15.Tebuconazole


1-(4-Chlorophenyl)-4,4-dimethylpentane-3-one (CPMP) will be reacted withdimethylsulphate in presence of dimethylsulphide and KOH in solvent toluene at 40deg C. After the reaction, Dimethylsulphide will be distilled and the salts will bedissolved in water, layers will be separated and the organic will be subjected torecovery of toluene. The product oxirane will be then taken in potassium carbonatein DMF and reacted with 1,2,4-triazole. The product wll be finally isolated andcrystallised in cyclohexane to get pure tebuconazole.


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Input OutputRawmaterial (Kgs) Item (Kgs) Aqueous

CPMP 912.00 Tebuconazole 1000.00DMSO4 537.00 KCH3SO4 609.00 609.00DMS 265.00 DMS 265.00KOH(88%) 258.00 Organic Impurities 21.00Toluene 2000.00 Toluene Loss


Water 2500.00 Water 2577.00 2577.00DMF 2000.00 DMF 2000.00K2CO3 150.00 K2CO3 150.00 150.00Cyclohexane 2000.00 Cyclohexane Loss


Total 10622.00 Total 10622.00 3336.00

16. Boscalid


2-Chloropyridine-3-carboxylic acid will be converted into acid chloride bythionylchloride in solvent toluene. After the reaction, the product acid chloride will beisolated by distillation.

The distilled product will be reacted with 2-amino-4’-chlorobiphenyl in presence ofTriethylamine and potassium carbonate in solvent toluene. Immediately after thereaction, the product will be separated by work up and isolated.


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Input OutputRaw Materials (Kgs) Item (Kgs) Aqueous

2-chloropyridineCarboxylic acid

497.00Boscalid 1000 .00

Thionyl chloride 421.00 Nacl 207.00 207.00NaOH 283.00 Sodiumbisulphite 538.00 538.00TEA 325.00 TEA 325.00K2CO3 222.oo KCl 239.00 239.00Aminochlorobiphenyl 867.5 CO2 71.00Toluene 2000.00 Organic waste 185.5Water 3000.00 Toluene 2000.00

Water 3050 3050

Total 7615.5 Total 7615.5 4034.00

167.Picoxystrobin


Dihydrobenzopyranone (DHBP) will be reacted with trimethoxymethane in presenceof HCl. The reaction product will be further reacted with thionylchloride and methanolwhich will be isolated by work up and concentration of toluene. The crude productwill be taken in solvent THF and will be reacted with Sodium hydride and coupledwith Trifluotomethylpyridinol at reflux temperature. Finally the reaction mass will bedrowned in water, and filtered and crystallised in ethylacetate to get the product.


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17.3 Material Balance (For 1000 Kgs product)

Input OutputRaw material ( Kgs) Item (Kgs) Aqueous

DHBP 537.00 Picoxystrobin 1000.00Ttrimethoxymethane 412.00 Organic waste 754.00Con.HCl 330.00 Nacl 200.00 200.00Toluene 3000.00 Toluene Loss


Thionyl chloride 437.00 Hcl 143.00 143.00Methanol 300.00 SO2 235.00 235.00Trifluoromethylpyridinol 554.00 Trifluoromethyl

pyridinol89.00

Sodium Hydride 136.00 Paraffin 55.00THF 2400.00 THF 2400.00Water 3000.00 Water 3230.00 3230.00

Total 11106.00 Total 3808.00

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18.Thifluzamide


Thiazole acid will be converted into thiazole acid chloride by thionylchloride. Aftercompletion of the reaction, the solvent toluene will be distilled out and the acid will bereacted with dibromotrifluoromethoxyaniline in actonitrile. After the reaction,acetonitrile will be distilled out and the product will be washed with water, dried andpacked.

18,2 Chemistry of Reaction

18.3 Material Balance

Input OutputRaw Material (Kgs) Item (Kgs) Aqueous

Thiazole Acid 420.00 Thifluzamide 1000.00SOCl2 285.00 SO2 153.00 153.00Dibromotrifluoromethoxyaniline

654.00 HCL 156.00 156.00

Organic Waste 50.00Toluene 2000.00 Toluene Loss


Acetonitrile 1800.00 Acetonitrile 1800.00Water 1500.00 Water 1500 1500

Total 6659.00 6659.00 1809.00

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19. Pretilachlor


Excess 2,6-Diethylaniline (DEA) will be reacted at 120 deg C with 1-Chloro-2-propoxyethane (CPE) until all the CPE will be consumed. After the reaction, themass will be neutralised with caustic soda and the layers will be separated and theunreacted will be distilled and the reaction product N-propoxyethyl-2,6-diethylaniline(PEDA) will be distilled under vacuum.

Peda will be reacted with chloroacetylchloride and the product pretilachlor will beisolated .


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Input OutputRaw material (Kgs) Item (kgs) Aqueous

DEA 559.00 Pretilachlor 1000.00CPE 459.00 NaCl 219.00 219.00Caustic Soda (98%) 150.00 HCL 129.00 129.00CAC 400.00 Organic waste 153.00Water 1500.00 Water 1567.00 1567.00

Total 3068.00 Total 3068.00 1915.00

20. Glyphosate


PMIDA will be oxidised by hydrogen peroxide and the oxidised product will bereduced to get glyphosate. After the reaction, the product will be filtered and dried toget the final product.


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20.3 Material Balance (For 1000 Kgs)


PMIDA 1600.00 Glyphosate 1000.00H2O2 (50%) 576.00 Acetic Acid 422.00 422.00Tungsten Sulphate 9.00 Tungston sulphate 9.00 9.00vanadylsulphate 1.00 Vanadyl sulphate 1.00 1.00Water 1500.00 Water 1944 1944.00

Waste 310.00 310.00

Total 3686.00 Total 3376.00 2686.00

21.Clodinafop-propargyl


Clodinafop Propargyl manufacture will start from the intermediate RHPPA. This willbe taken in solvent DMF and K2CO3 and will be reacted with DCFP at elevatedtemperature. The reaction will be done for 8 hours to complete the reaction.Thereafter , propargyl chloride will be added for 2 hours and carried out the reactionto completion. Afterwards, the mass will be filtered to remove the solids and theliquid part will be taken for distillation and the solvent will be recovered. The crudewill be extracted in DCM and washed with water and the solvent will be recovered.The crude will be crystallized in methanol-water and filtered , dried to get theproduct.


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2. Chemistry of Reaction

OH

O

CH3

O

OH

RHPPA

+N F

FCl

DFCP

K2CO 3

DMF

N

O

F

Cl

O

CH3

O

OH

Propargyl Chloride

Work Up

N

O F

Cl

O

CH3

O

O

CHCLODINAFOP PROPARGYL


Input outputRaw material (Kgs) Item (Kgs) Aqueous

DMF 2700.00 DMF LossRecovered

200.002500.00

CDFP 759.00 Clodinafop-propargyl 1000.00K2CO3 1125.00 KCl 756.00PHPPA 816.00 K2CO3 414.00Propargyl Chloride(50% in Toluene)

825.00 Toluene 413.00

DCM 2400.00 DCM LossRecovered

200.002200.00

Methanol-water 2400.00 Methanol-water 2400.00Solid Waste 942.00 942.00

Water 2400.00 Water 2400.00 2400.00

13425.00 Total 13425.00 3342.00

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22. Bis-pyribac sodium


2-Chloro-4,6-dimethoxypyrimidine ( CDMP) will be reacted with 3,5-dimethoxybenzoic acid (DMBA) in presence of catalyst TBAB, Sodium tungstatedehydrate, hydrogen peroxide, sodium methoxide. After, the reaction, the productwill be isolated by work up.


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CDMP 858.00 Bis-pyribac sodium 1000.00DMBA 378.00 Sodium Chloride 268.00 268.00Sodium Methoxide 408.00 Sodium Sulphonic

acid540.00 540.00

Chlorobenzene 2500.00 Chlorobenzene LossRecovered

100.002400.00

Sodium mercaptide 344.00 Water 2390.00 2300.00H2O2 (30%) 557.00 Other impurities 3.00Water 2000.00

Total 6701.00 Total 6701.00 5198.00

23. Quizalofop


2,6-Dichloroquinoxaline ( DCQ) will be reacted with 2-(4-Hydroxyphenoxy)propionate(HPP) in presence of sodium methoxide and solvent methyl isobutyl ketene (MIBK)

After the reaction, the salts will be dissolved in water, layers will be separated andsolvent will be distilled and the product will be isolated.


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DCQ 531.00 Product 1000.00HPP 590.00 Sodium Chloride 173.00 173.00Sodium Methoxide 159.00 Methanol 91.00 91.00MIBK 2500.00 MIBK Loss


Water 2000.00 Water 2000.00 2000.00Impurities waste 16.00

Total 5780.00 Total 5730.00 2264.00

24.Propaqunizalofop


Lactic Acid will be reacted with ethylene oxide and acetone oxime in presence ofPTSA as catalyst and toluene as solvent. After the reaction over, the solvent will berecovered by distillation under vacuum and the product PAOHP will be reacted with2,6-dichloroquinoxaline in presence of sodium methoxide and solvent dioxane. Aftercompletion of the reaction, the solvent will be recovered and the product will beisolated .


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Input OutputRaw Material (Kgs) Item (Kgs) Aqueous2,6-Dichloroqunioxaline

472.00 Propaquizalofop 1000.00

Lactic Acid 225.00 PTSA 50.00 50.00Ethylene oxide 110.00 NaCl 138.00 138.00Hydroquinone 275.00 Hydroquinone 27.00Acetone oxime 183.00 Methanol 81.00 81.00PTSA 50.00Toluene 1800.00 Toluene Loss


Sodium Methoxide 141.00 Organic Waste 19.00Dioxane 2500.00 Dioxane Loss


Water 2000 Water 2000.00 2000.00

Total 7615.00 Total 7615.00 2269.00

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25. Mesotione


4-Methylsulphonyl-2-nitrobenzoic acid (MSNBA) will be taken in solvent toluene andwill be reacted with thionyl chloride at 60 degC. After completion of the reaction, thesolvent and the residual SOCl2 will be distilled out and the crude acid chloride will bereacted with 1,3-cyclohexanedione (CHDO) in EDC solvent in presence of catalyticquantity of acetone cyanohydrins and TEA. The product will be isolated throughwater wash, acidic wash and will be dried.


25.3 Material Balance ( for 1000 Kgs product)


MSNBA 850.00 Mesotrione 1000.00CHDO 367.00 CHDO 37.00

Organic Waste 340.00Acetone cyanohydrin 30.00 Acetonecyanohydrin 30.00 30.00TEA 374.00 TEA 374.00SOCl2 495.00 NaCl 243.00 243.00NaOH (98%) 340.00 NaHSO3 432.00 432.00Water 2500.00 Water 2500.00 2500.00Toluene 2200.00 Toluene Loss


EDC 3000.00 EDC LossRecovered

200.002800.00

Total 10156.00 Total 10156.00 3205.00

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26.Fluroxypyr


3,5-Dichloro-2,6-difluoro-4-aminopyridine (DCDFAP) will be hydrolysed with Causticsoda solution and 120 deg C and the product 3,5-dichloro-6-fluoro-4-amino-2-pyridinol sodium salt will be reacted with Chloroacetic acid and the product will beisolated by acidification, filtration and dried.


26.3 Material Balance ( For 1000 Kgs Product )


DCDfAP 867.00 Fluroxypyr 1000.00MCA 421.00 NaCl 450.00 450.00NaOH (98%) 350.00 Catalyst 30.00 30.00Catalyst 30.00 Organic waste 38.00EDC 2500.00 EDC Loss


Water 3000.00 Water 3150.00 3150.00

Total 7168.00 Total 7130.00 3630.00

27. Imazamox


Imazamox will be manufactured starting from Dimethyl 5-(methoxymethyl)-2,3-pyridinedicarboxylate taken in toluene to make 25%solution, and then adding 2-amino-2,3-dimethylbutyramide and 98% sodium methoxide. Then the reaction mixture will be heatedunder constant stirring for 4 hours. Sodium salt of 2-(5-isopropyl-5-methyl-4-oxoimidazolin-2-yl)-5-Methyl-3-pyridinecarboxylic acid precipitates in the form of a dense crystal slurry.The mixture is then cooled to room temperature and, after addition of water, stirring will bedone. The layer separation will be done and the pH of aqueous phase will be adjust to pH 2-3by addition of 30% hydrochloric acid solution. Crude product will be filtered out and thenrecrystallization will be done in methanol and then it will dried to get Imazamox.

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27.3 Material balance (for 1000 Kgs)

Input OutputRaw material (Kgs) Items Aqueous WasteDimethyl 5-(methoxymethyl)-2,3-pyridinedicarboxylate

235.2 Toluene LossTolueneRecovered

69.21314.8

95% 2-amino-2,3-dimethylbutyramide

592.7 Methanol LossMethanolRecovered

678.422713.68

98% sodiummethoxide

474.9 Water Waste

Toluene 1384.0 Water 3891.42 3891.42

28. Pinoxaden Technical


Pinoxaden will be prepared by the reaction of 8-(2,6-Diethyl-4-methylphenyl)tetrahydro-7H-

pyrazolo[1,2-d][1,4,5]oxadiazepine-7,9(8H)-dione (oxadiazepine compound) and pivaloyl

chloride in the catalytic presence of 4-dimethylaminopyridine and triethylamine in

tetrahydrofuran (THF). The mixture will stirred at a temperature of 0 °C to 25 °C. After

reaction THF will distilled out and the reaction mass will be diluted with tert-butyl methyl

ether (MTBE), which then poured intosaturated aqueous sodium chloride solution. Further

layer separation and crystallization result into the desired product Pinoxaden Technical.


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Input OutputRaw material (Kgs) Items Aqueous

WasteOxadiazepine compound 934.5 THFLoss

THFRecovered350.0650.0

Pivaloyl chloride 458.0 MTBE LossMTBERecovered

300.0700.0

4-dimethylaminopyridine(4-DMAP)

18.6 Water Waste

Triethylamine 607.5 Water 1000.0 1000.0Tetrahydrofuran (THF) 1000.0 Salt 60.0tert-butyl methyl ether (MTBE) 1000.0 Organic waste 408.620% Sodium chloride solution(NaCl solution)

250.0

Water 200.0 Pinoxaden 1000.00Total 4468.6 Total 4468.6 1000.0

29. Ametryne Technical


Ametryne will be synthesis from the reaction of Atrazine and sodium methyl mercaptanin

water and tetrahydrofuran as solvent at reflux temperature. After reaction tetrahydrofuran will

be removed under reduced pressure. The residue will then added to water and extracted by

dichloromethane. The combined organic extract will washed with saturated brine. The filtrate

will then concentrated under reduced pressure. The residue was purified by recrystallization

from a mixture of methanol and water to afford Ametryne Technical.


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N

N

N

NHCl

NH

+ CH3SHNa N

N

N

NH

NH

SCH3


Input OutputRaw material (Kgs) Items Aqueous WasteAtrazine 1511.0 THFLoss

THFRecovered350.0650.0

20% aq. Sodium methylmercaptan

22222.0 MDC LossMDCRecovered

535.0965.0

Methylene dichloride (MDC) 1500.0 Methanol LossMethanolRecovered

200.0800.0

Methanol 1000.0 Water WasteTetrahydrofuran (THF) 1000.0 Water 21700.0 21700.02% Sodium chloride solution(NaCl solution)

1000.0 Organic waste 2533.0

Water 500.0 AmetryneTechnical

1000.0

Total 28733.0 Total 28733.0 21700.0

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30. Tembotrione

31.Topramezone


Topramezone will be synthesis by the reaction from 2-methyl-3-(4, 5-

dihydroisoxazol-3-yl)-4-methanesulfonyl-benzoic acid by first reaction it with thionyl

chloride and 1 drop of pyridine in toluene. After that heating for 3h. After reaction the

solvent and excess of thionyl chloride will distilled out. The obtained residue will be

dissolve in anhydrous dioxane which will be added to 1-methyl-5-hydroxy pyrazole

and anhydrous dioxane solution to which further, triethylamine will be added. After

reaction the reaction mass will be filtered and again heated in the presence of

potassium carbonate. The solvent will distilled out and then the residue will treated

with 10% dilute hydrochloric acid to adjust pH to 2-3. The product will then extracted

with ethyl acetate, from which TopramezoneTC will obtained by crystallization.


SOCl2Toluene, Dioxane

Pyridine, Et3NK2CO3, 10% HCl

SOO

O

OH

NO

+N

N

OH

SOO

ONO

NN

OH



2-methyl-3-(4,5-dihydroisoxazol-3-yl)-4-methanesulfonyl-benzoic acid (Benzoicacid)

957.4 TolueneLossTolueneRecovered

50.00950.0

Toluene 1000 Organic Waste 705.42Pyridine 63.8 Pyridine 63.8Thionyl Chloride(SOCl2)

978.7 SOCl2Recovered 450.00

Dioxane 1500 Dioxane LossDioxaneRecovered

150.01350.0

1-methyl-5-hydroxypyrazole

372.3 Ethyl acetateLossEthylacetateRecovered

50.0950.0

Triethylamine 404.2 TEA 404.20

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Potassium carbonate 394.0 KCl 363.00 363.0010% dilutehydrochloric acid

1000.0 Water 1900.0 1900.0

Water 1000.0 Topramezone 1000.00Ethyl acetate 1000.0 SO2 284.00 284.00Total 8670.42 Total 8170.42 2547.00

32. Halosulfuron


Halosulfuron-methyl will be synthesis from 3-chloro-1-methyl-5-sulfonamide group-4-

pyrazole carboxylic acid methyl ester which will reacted with n-butyl isocyanate in p-

xylene as solvent and tri ethylene diamine as catalyst. At 140 °C add trichloromethyl

chloroformate drop wise. After reaction distil p-xylene to obtain the residue. This

residue will dissolve in acetonitrile and added then4, 6-dimethoxy-2-pyrimidinamine

drop wise at 20-25 °C, after stirring for 24 h, filter out the cake and wash with chilled

acetonitrile, which will on drying result in Halosulfuron-methyl TC.


NN

Cl

SO

O

NH2

O

O + NN

NH2

OO

CO N

ClCO2CCl3

NN

NH

O

OO

NHSO

O

N N

Cl

OO



3-Chloro-1-methyl-5-sulfamoyl-1H-pyrazole-4-carboxylic acidmethyl ester(Ester compound)

726.6 p-xylene lossp-xylenerecovered

16.61316.7

4,6-dimethoxy-2-pyrimidinamine

433.33 Acetonitrile lossAcetonitrilerecovered

363.33269.7

n-butyl isocyanate 276.66 Residue 1286.55Triethylene diamine 16.66trichloromethylchloroformate

833.3

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p-xylene 1333.3Acetonitrile 3633.0

Halosulfuron-methyl TC

1000.00

Total 7252.85 Total 7252.85

33. Penoxsulam


Penoxsulam will be prepared by adding substituted benzene sulphonylchloride to themixture of trizolopyrimidine amine, DMSO and pyridine. The reaction mixture willthen stirred for 8h. After completion of reaction DMSO will be distilled outcompletely.To the crude mixture, water will be added, stirred and filtered. Filtrate will be driedcompletely toafford desired product as Penoxsulam.




Trizolopyrimidineamine

404 DMSOLossDMSORecovered

90.01930

Sulphonylchloride

672

Pyridine 164DMSO 2020 Water 1000.00 1000.00Water 1000 Pyridine HCl Salt 240.00 240.00

Penoxsulam 1000.00Total 4260 Total 4260 1240

34. Flucetosulfuron


Flucetosulfuron will be synthesis from 2-methoxy-1-[3-(aminosulfonyl)-2-pyridinyl]-2-

fluoropropyl acetic acid ester by its reaction with phenyl (4,6-dimethoxypyrimidin-2-

yl)carbamate and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) solution in acetonitrile.

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After reaction Dichloro methane will be added and the reaction mass will be treated

with 5% HC1 aqueous solution and then with water. Layer separation will be done.

Dichloromethane will recovered and

Finally, the residue will crystallizedfrom n-hexane to give Flucetosulfuron Technical.


N F

O

OO

S OONH2

+

N

N

O

O NH

O O

DBU, ACN

N F

O

OO

S OONHO

NH

N

N

O

O +OH



Waste2-methoxy-1-[3-(aminosulfonyl)-2-pyridinyl]-2-fluoropropylacetic acidester(Ester compound)

765.0 Phenol 193.00

Phenyl(4,6-dimethoxypyrimidin-2-yl)carbamate

725.0 MDC LossMDCRecovered

150.02850.0

1,8-

diazabicyclo[5.4.0]undec-7-ene (DBU)

60.0 n-Hexane Lossn-HexaneRecovered

100.0900.0

Acetonitrile 2295.0 Acetonitrile LossRecovered

125.002170.00

Dichloro methane 3000.0 Water 2375.0 2375.00n-Hexane 1000.0 Organic Waste 457.005% HC1 solution 500.0 Flucetosulfuron 1000.00Water 2000.0 HCl 25.00 25.00Total 10345.0 Total 9545.0 2400.0

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35. Pendimethalin


Pendimethaline TC will be prepared by the following process

Hydrogenation StepMixture of 4 NOX (4-Nitro Ortho Xylene), Di Ethyl Ketone and Platinum on carbon as

catalyst will charged in autoclave. Hydrogen Gas will then purged. After completion

of reaction, reaction mass will filtered to recover the platinum on carbon catalyst,

which will used in next batches.

Nitration StepMixed acid will prepared by adding nitric acid to Sulphuric acid and water in reactor

at below room temperature. NOX and EDC will mixed in reactor. Maintain

temperature for few hours to complete the reaction. After completion of reaction

spent acid will be separated as bottom layer. Apply water wash to organic layer and

separate organic layer.

Denitrososation StepReaction mass will then treated with acetone and Hydrochloric acid at elevated

temperature. After completion of reaction neutralize excess hydrochloric acid with

caustic lye and then washed with water. Aqueous phase will be separated. Distilled

out EDC from organic mass to obtain crude Pendimethalin. Crude product will be

purified by n-hexane to get pure Pendimethalin techinal as product.


Hydrogenation

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Input Output

Raw material (Kgs) Items Aqueous Waste

4-Nitro Ortho

Xylene

600 DEK Loss

DEK Recovered

80.0

820.0

Di Ethyl Ketone

(DEK)

900 EDC Loss

EDC Recovered

140.0

1060.0

Platinum/C 18 n-Hexane Loss

n-Hexane

Recovered

115.0

785.0

Hydrogen gas 50 Platinum/C 17.0

Sodium hydroxide

(Caustic lye)

450

Ethylene dichloride

(EDC)

1200 Salt (NaHSO4 +

NaCl)

588.00 588.00

n-Hexane 900 Organic waste 137.00

Acetone 300 Acetone 300.00 300.00

Hydrochloric acid 60 Water 3186.0 3186.0

Nitric acid 775

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Sulfuric acid 375

Water 2600 Pendimethaline 1000.0

Total 8228.0 Total 8228.0 4074.0

36. Chlorimuron


Chlorimuron TC will be synthesis from benzoyl-2-sulfonyl isocyanate by reacting it

with 2-amino-4-chloro-6-methoxypyrimidine in dichloromethane as solvent and

triethanolamine as catalyst at 40 °C. After reaction the crystallize product will filtered

out and will dried to obtain Chlorimuron-ethyl TC


+ NN

NH2

OCl N(CH2CH2OH)3

SO

O

NCO

O

O

MDC

N

N

NH O

Cl

O

NHS

O

OOO



WasteEthyl-2-(isocyanatosulfonyl)benzoate(Ester compound)

615.00 DichloromethanelossDichloromethanerecovered

100.00

1400.00

2-amino-4-chloro-6-methoxypyrimidine

423.0 Triethanolamine 15.00

Dichloromethane (MDC) 1500.00 Residue 38.00Triethanolamine 15.0

Chlorimuron-ethyl

TC

1000.00

Total 2553.00 Total 2553.00

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37. Nicosulfuron


Nicosulfuron will be prepared by the reaction of N, N-dimethyl-2-sulfamoylpyridine-3-

carboxamide and Ethyl chloroformatein the presence of anhydrous potassium

carbonate in acetonitrile medium. After reaction acetonitrile will be distilled out to

obtain reaction mass. To this mas water will be added and treated with 36%

hydrochloride to precipitate crystals of amide derivative.

This amide derivative further reacted with 4, 6-dimethoxy pyrimidin-2-amine in

toluene at reflux temperature. After distillation of ¾ toluene, desired Nicosulfuron will

be obtained by crystallization.


N

SNH2

O

OON

+ Cl

O

O

NN

NH2

O O

ACNK2CO3

Toluene

N

ON

SO O

NH O

NH

N

N

O

O


Input OutputRaw material (Kgs) Items Aqueous WasteN,N-dimethyl-2-sulfamoylpyridine-3-carboxamide

587.0 AcetonitrileLossAcetonitrileRecovered

150.02850.0

Ethylchloroformate


176.03324.0

Acetonitrile 3000.0 Water WastePotassiumcarbonate

460.0 Water 2991.0 2991.0

4,6-dimethoxypyrimidin-2-amine

399.0 Salt (KCl) 297.0 297.0

Toluene 3500.00 Carbon dioxide 146.036% hydrochloricAcid

142.0

Water 2900.00 Organic waste 336.0.

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Nicosulfuron 1000.00Total 11270.00 Total 11270.0 3288.0

38. Metsulfuron Technical


Metsulfuron will be prepared by addition reaction of O-Sulfoisocyante Methyl

Benzoate and 2-Amino 4-Methoxy 6-Methyl-1, 3, 5-Triazine in presence of Toluene.

On cooling, crystal are formed which will then filtered out to obtain Metsulfuron

technical as product.


O

O

S OONCO

+ N

N

N

NH2CH3

OCH3Toluene

O OCH3

SO

O NH

O

NH N

N N

OCH3

CH3


Input Output

Raw material (Kgs) Items Aqueous Waste

O-Sulfoisocyante

Methyl Benzoate

640.0 Toluene Loss

Toluene

Recovered

47.5

902.5

2-Amino 4-Methoxy

6-Methyl-1, 3, 5-

Triazine


Toluene 950 Metsulfuron 1000.00

Total 1960.0 Total 1960.0

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39. Dichlor vos (DDVP)


Chloral will be taken in a reactor and Trimethylphosphite (TMP) will be added slowlyat 40 deg C. After the addition, the product will be heated to 60 deg C and will bekept for 2 hours and finally the product will be cooled and will be packed.


39.3 Material Balance (for 1000 Kgs)

Input OutputRaw material ( Kgs ) Item ( Kgs ) AqeousChloral 681.00 DDVP 1000.00TMP 572.00 Methyl chloride 240.00

Evaporation Loss 13.00

Total 1253.00 Total 1253.00

40. Acephate


Acephate will be manufactured by isomerising first with Dimethylsulphate in solventDichloromethane at 45-50 deg C and the isomerised product will be acetylated by

acetic anhydride at 55 deg C. After completion of the reaction, the mass will be takenin water, neutralised with aqueous ammonia and the product Acephate will beextracted in DCM, concentrated and crystallised in Ethylacetate.

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40.3 Material Balance ( For 1000 Kgs Product)

Input OutputRaw material (Kgs) Item (Kgs) AqueousDMPAT 1070.00 Acephate 1000.00DMSO4 120.00 DMSO4 120.00 120.00Acetic Anhydride 766.00 Ammonium Acetate 578.00 578.00Ammonia (25%) 600.00 Water from Ammonia 450.00 450.00

Organic Waste 408.00DCM 5000.00 DCM Loss


Water 1000.00 Water 1000.00 1000.00Ethyl acetate 1500.00 Ethyl acetate loss


Total 10056.00 Total 10056.00 2148.00

41. Diafenthiuron


Diafenthiuron manufacture starts with 4-phonoxy-2,6-diisopropylaniline (PIPA). PIPAwill be reacted with sodiumthiocyanate at 90 deg C in presence of HCl in solventtoluene. After the reaction, the reaction mass will be filtered washed and dried. The

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thiourea derivative will be further heated and reacted with tertiary butylamine insolvent acetonitrile to get the product.


41.3 Material Balance ( For 1000 Kgs Product)

Input OutputRaw materials (Kgs) Item ( Kgs) Aqueous

PIPA 874.00 Diafenthiuron 1000.00NaCNS 300.00 NaCl 217.00 217.00HCl (30%) 452.00 Water from HCl 316.00 316.00Toluene 2000.00 Toluene Loss


Acetonitrile 1500.00 Acetonitrile LossRecovered

220.001280.00

t-Butylamine 211.00 T-Butylamine 18.00Water 1500.00 Water 1500.00 1500.00

Organic Waste 304.00

Total 6837.00 Total 6837.00 2033.00

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42. Imidacloprid


Imidaclopridwill be prepared by the reaction of 2 – Chloro, 5 – Chloromethyl Pyridine(CCMP) with N-Nitro IminoImidazolidine (NIIA) in presence of Sodium Hydroxide andDimethyl Formamide as solvent.After completion of the reaction the slurry will befiltered to remove the salts of Sodium Chloride.The solvent will then remove bydistillation from the reaction mass. The residual mass will then diluted with water andthe resultant slurry will filtered to remove crude Imidacloprid. Which will be treatedwith water and then crystallize in Ethyl alcohol to obtain desired product Imidacloprid.


NH

N

NHNO

O +N Cl

ClNaOH, DMF

N

NH

NN

O

O

N

Cl



WasteDMF 1500 DMF Loss

DMFRecovered

1201380

2-Chloro-5-chloromethylpyridine(CCMP)

634 Ethyl AlcoholLossEthyl AlcoholRecovered

80

1320

2-Nitroiminoimidazolidine(NIIA)

630 OrganicWaste

40.00

Sodium Hydroxide flakes 250.00 Water 862 862Ethyl Alcohol 1400Water 750 Salt NaCl 362.00 362

Imidacloprid 1000.00

Total 5164.00 Total 5164.00 1224.00

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43. Buprofezin


Buprofezin manufacture will start with N-methylaniline. N-Methylaniline will bereacted with formic acid and the reaction product will be chlorinated by chlorine inCCl4. The chlorinated product will be reacted with N-t-butyl-N’-isopropylthiourea insolvent CCl4 in presence of NaOH. After completion of the reaction, the product willbe washed with water, filtered and dried to get buprofezine.


43.3 Material Balance


N-Methylaniline 438.00 Buprofezine 1000.00Chlorine 465.00 HCl 239.00 239.00Formic acid (85%) 277.00 NaCl 425.00 425.00Catalyst 35.00 Catalyst 35.00CTC 2000.00 CTC Loss


T-Butyl-Isopropylthiourea


NaOH (98%) 291.00Water 1000.00 Water 1131.00 1131.00

Total 5139.00 Total 5139.00 1795.00

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44. Thiamethoxam

44.1 Manufacturing process.

2-Chloro-5-chloromethylthiazole (CCMT) and N-(3-methyl-1,3,5-oxadiazinan-4-ylidene)nitramide (MNPO) will be mixed in solvent DMF. Maintaining temeperature30 degC, sodium hydroxide flakes will be charged and stirred for 2 hours to completethe reaction. After analysis, the mass will be filtered to remove sodium chloride. Theclear organic will be distilled and DMF will be recovered. The crude product will bewashed with water and will be crystallised in methanol-water and dried to get theproduct.

44,2 Chemistry of Reaction

44.3 Material Balance (For 1000 Kgs Product)


CCMT 640.00 Thiamethoxam 1000.00MNPO 565.00 MNPO 10.00NaOH 152.00 NaCl 222.00 222.00DMF 2000.00 DMF Loss


Methanol 1500.00 Methanol LossMethanol Recovered

200.001300.00

Water 1000.00 Organic Waste 57.00Water 1068.00 1068.00

Total 5857.00 Total 5857.00 1290.00

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45. Cypermethrin


Cypermethric Acid Chloride (CMAC) and Metaphenoxybenzaldehyde (MPB) will bemixed in solvent hexane –water medium. Sodium cyanide solution will be added at15-30 deg C for 2 hours and the reaction will be completed at 30 deg C. Aftercompletion of the reaction, the mass will be heated to 50 deg C and the aqueouslayer will be separated. The organic layer will be washed with Water and will beconcentrated to get cypermethrin.


45.3 Material Balance (For 1000 Kgs product)


CMAC 563.00 Cypermethrin 1000.00MPB 485.00 Sodium Cyanide 22.00 22.00NaCN 140.00 Sodium Chloride 140.00 140.00PTC 20.00 PTC 20.00 20.00Hexane 1600.00 Hexane Loss


Organic Waste 26.00 26.00Water 1500.00 Water 1500 1500.00

Total 4308.00 Total 4308.00 1708.00

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46. AlphaCypermethrin


Alpha cypermethrin will be the epimerized product of cypermethrin. Cypermethrin willbe taken in N-Hexane and will be stirred with Triethylamine for 48 hours. Afterepimerization, the product will be filtered, washed with N-hexane and dried to getAlpha-cypermethrin.


Cypermethrin epimerized into alphacypermethrin

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46.3 Material Balance (For 1000 Kgs)

Input OutputRaw materials (Kgs) Item (kgs) Aqueous

Cypermethrin 1176.00 Alphacypermethrin 1000.00N-Hexane 2000.00 Crude Cypermethrin 176.00

TEA 30.00TEA 30.00 N-Hexane loss


Total 3206 Total 3206.00

47. Fipronil


Pyrazole will be taken in chlorobenzene and will be mixed with PTSA-DMA complex.Maintaining temperature 30 deg C, Trifluoromethanesulfinyl chloride will be addedfor 2 hours and stirred for 12 hours. After completion of the reaction, the mass will bedrowned in water, adjusted pH and will be filtered, dried and crystallised in toluene toget the product.


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47.3 Material Balance ( For 1000 Kgs)

Input OutputRaw material (Kgs) Item (kgs) Aqueous

Pyrazole 1049.00 Fipronil 1000.00Trifluoromethanesulfinylchloride

581.00 Organic Waste 480.00 489.00

PTSA-tosylate 744.00 PTSA-tosylate 744.00 744.00Chlorobenzene 1600.00 Chlorobenzene Loss


Toluene 1200.00 Toluene LossRecovered

200.001000.00

Water 3500.00 Water 3570.00 3570.00NaOH 155.00 NaCl 226.00 226.00

Total 6829.00 Total 6829.00 5029.00

48. Acetamiprid


1-(6-Chloropyridin-3-yl)-N-methylmethanamine (CPMMA) will be reacted withMethyl-N-methylethanimidate (MMEI) in solvent Methanol at 40-50 deg C. Aftercompletion of reaction the solvent will be distilled out and the product will beCrystallised in water to get pure product.


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48.3 Material Balance ( For 1000 Kgs product)

Input OutputRaw Material (Kgs) Product (Kgs) AqueousCPMMA 781.00 Acetamiprid 1000.00MMEI 444.00 Impurirites 86.00 86.00Methanol 1500.00 Methanol 1639.00Water 1500.00 Water 1500.00 1500.00

Total 4225 Total 4225.00 1589.00

49. Propargite


2-(4-t-Butoxyphenoxy)cyclohexanol ( BPCH) will be reacted with thionyl chloride at20 deg C in solvent toluene. The generated HCl will be neutralised in NaOH solution.The reaction product will be further reacted with propargyl alcohol in presence ofTEA. After completion of reaction, the organic will be washed with water and theproduct will be recovered from the organic by distillation.


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49.3 Material Balance ( for 1000 Kgs Product)

Input OutputRaw material (Kgs) Product (Kgs) Aqueous

BPCH 786.00 Propargite 1000.00Thionyl Chloride 386.00 NaCl 379.00 379.00Propargyl Alcohol 200.00 Propargyl Alcohol 40.00 40.00TEA 327.00 TEA 327.00NaOH (98%) 260.00 Organic Waste 96.00Toluene 2200.00 Toluene Loss


Water 2000.00 Water 2117.00 2117.00

Total 6159.00 Total 6159.00 2536.00

50. Indoxacarb


The Intermediate BICB will be reacted with MCIC and then with MCF in presence ofK2CO3 and solvent chlorobenzene. After the reaction, the reaction mass will bewashed with water and crystallised to get the product.


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50.3 Material Balance ( for 1000 Kgs product)

Input OutputRaw material (Kgs) Product (kgs) Aqueous

BICB 381.00 BICB 10.00MCIC 561.00 MCIC 8.00MCF 188.00 KCl 155.00 155.00K2CO3 288.00 KHCO3 208.00 208.00Monochlorobenzene 2000.00 Monochlorobenzene 2000.00Water 1500.00 Water 1500.00 1500.00

Indoxacarb 1000.00Organic Waste 47.00

Total 4918.00 Total 4918.00 1863.00

51. Dinotefuran


Dinotefuranwill be prepared from l, 3-dimethyl-2-nitroisourea andtetrahydrofurylmethyl] amine inmethanol. The reaction mixture will stirred for 3 hoursatroom temperature. An oily product obtained by concentratingthe reaction mixtureunder reduced pressure. The desired product will be obtained by drying after doingcrystallization in ethyl acetate.


O

NH2

+O

N

NH

N

O

O

MeOH

O

N

NH

NHN

O O + CH3OH


Input OutputRaw material (Kgs) Product (Kg) Aqueous

Wastel, 3-dimethyl-2-nitroisourea 694.4 Dinotefuran 1000Tetrahydrofuryl methyl]amine

632.0 MethanolLossMethanolRecovered

204.0816.0

Methanol 700.0 Ethyl acetateLossEthyl acetateRecovered

25

475

Ethyl acetate 500.0 Organic waste 6.4

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Total 2526.4 Total 2526.452. Flonicamid Technical


Flonicamidwill be synthesis by the reaction of 4-(trifluoromethyl) nicotinamide and2-

chloroacetonitrile in the presence of potassium carbonate in dimethyl sulfoxide

(DMSO) as solvent. After the reaction reaction mass will be filtered and DMSO will

be distilled out and the desired product will be obtained by fractional distillation as

pure Flonicamid Technical.


N

O

NH2

CF3

+ CH2ClCNN

O

NH

CF3

CN

K2CO3, DMSO



Waste4-(trifluoromethyl)nicotinamide

864.1 FlonicamidTechnical

1000.0

2-chloroacetonitrile 343.2 DMSO LossDMSORecovered

129.62462.7

Potassium carbonate 752.7 KCl 676.46Dimethyl sulfoxide (DMSO) 2592.3 Residue 283.54Total 4552.3 Total 4552.3

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53. Etoxazole


Etoxazole will be synthesis from the reaction of N-(2,6-difluorobenzoyl)-2-amino-2-

(2-ethoxy-4-tert-butylphenyl)ethanol and 2,6-Difluorobenzoyl chloride in the presence

of thionyl chloride and toluene as solvent. After reaction the excess of thionyl

chloride and toluene will distilled out. The reaction mass will be dissolve in ethyl

acetate and washed with aqueous sodium hydroxide solution and then with water.

The final compound Etoxazole TC will be obtained by crystallization in ethyl acetate.


SOCl2Toluene

F

F

O

Cl+

O NH2OH

F

F

N

OO


Input OutputRaw material (Kgs) Products (Kg) Aqueous WasteN-(2,6-difluorobenzoyl)-2-amino-2-(2-ethoxy-4-tert-butylphenyl)ethanol(Alcohol compound)

1444.4 Etoxazole TC 1000.00

2,6-Difluorobenzoylchloride


150.01350.0

Toluene 1500.0 Ethyl acetateLossEthyl acetateRecovered

300.01200.0

Thionyl chloride 724.0 SO2 389.48Ethyl acetate 1500.0 NaCl 710.14 710.14Water 2000.0 Water 2218.88 2218.88Sodium hydroxide 486.4 Residue 1410.7Total 8729.2 Total 8729.2 2929.0

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54. Metaflumizone Technical


Metaflumizone will be synthesis from the reaction of phenyl ester and 4-

trifluoromethylaniline in toluene at reflux temperature. After reaction toluene will

distilled out and the oily mass will be cooled and crystalized in methanol to obtain

desired Metaflumizone Technical.


NC

F3C

NNH

O

O +NH2

OCF3

Toluene

NC

F3C

NNH

O

NH

OCF3


Input Output

Raw material (Kgs) Products (Kg) AqueousWaste

Hydrazinecarboxylic acid,2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-, phenyl ester(Phenyl ester)

930.4 MetaflumizoneTechnical 1000.0

4-trifluoromethylaniline 456.0 Toluene LossToluene Recovered

232.54417.5

Toluene 4650 Methanol LossMethanol Recovered

232.52092.5

Methanol 2325 Organic waste 151.4Phenol 235.0

Total 8361.4 Total 8361.4

.

of 242

55. Spiromesifen Technical


Spiromesifenwill be synthesis by the reaction of 1-Oxaspiro[4.4]non-3-en-2-one, 4-

hydroxy-3-(2,4,6-trimethylphenyl)- and 3,3-dimethyl-Butanoyl chloride in methyl

cyclohexane as solvent in the presence of tri ethylamine at 25 °C-30 °C.After

reaction the reaction mass will be washed with sodium bicarbonate solution followed

by water wash. The crystallization of organic phase will be done to obtain

Spiromesifen Technical.


O

OH

O O

O

O

O+Cl

OEt3N

Methyl cyclohexane


Input OutputRaw material (Kgs) Products (Kg) Aqueous

Waste1-Oxaspiro[4.4]non-3-en-2-one, 4-hydroxy-3-(2,4,6-trimethylphenyl)-(Oxaspiro compound)

1050.0 Spiromesifen

Technical

1000.0

3,3-dimethyl-Butanoylchloride

518.9 Methyl cyclohexaneLossMethyl cyclohexaneRecovered

150.0

1350.0

Triethyl amine 390.13 Organic waste(Residue)

837.66

Methyl cyclohexane 1500.0 NaCl 221.92 221.92Sodium bicarbonate 323.4 Water 1576.2 1542.0

Water 1542.0 TEA in water 21.45 21.45

CO2 in water 167.2 167.2

Total 5324.43 Total 5324.43 1952.57

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56. Spirotetramat


of 242


O

OHSOCl2

O

Cl O

NH2

O

O

K2CO3O

NH

O

OO

NaOCH3, DMF

Ethyl chloroformateONH

O

OO

O

ONH

O

OH



WasteSpirotetramat TC 1000

2-(2,5-dimethylphenyl)acetic acid

572 Toluene LossToluene Recovered

1552945

Thionyl chloride 319 MDC LossMDC Recovered

12602340

cis-Cyclohexanecarboxylicacid, 1-amino-4-methoxy-methyl ester

645.5 ACN LossACN Recovered

4203780

Dimethylformamide 11.44 Methanol LossMethanol Recovered

1001900

Potassium carbonate 400.0 Methanol in reaction 108Sodium methoxide 188.2 Sulphur dioxide 171.4

4-DMAP 20.0 Hydrogen chloride 98.0

Ethyl chloroformate 378.1 Hydrogen 5.4Methylene dichloride(MDC)

3600 cis-Cyclohexanecarboxylic acid, 1-amino-4-methoxy-methyl ester

149.4

Acetonitrile (ACN) 4200 Residue 633.96Toluene 3100 Water 9520 3520Methanol 2000 DMF 11.44Water 3520 Salt 313.0 313.0

Sodium methoxide 43.6Total 18954.2 Total 18954.2 833.0

of 242

57. Chlorantraniliprole


Chlorantraniliprole will be prepared by reacting 2-amino-5-chloro-N,3-dimethylbenzamide in toluene with 3-bromo- 1-(3-chloro-2-pyridinyl)- 1H-pyrazole-5-carbonyl chloride in the presence of triethyl amine. After refluxing for 1 hour, thereaction mixture will cooled. Then Add water to the reaction mass and again heated,followed by layer separation.Toluene layer will be cooled to precipitate product whichbe isolated via filtration and & dried to obtain desired product Chlorantraniliprole.




Waste2-amino-5-chloro-N,3-dimethylbenzamide

456.5 Chlorantraniliprole

1000.00

Toluene 2282.5 Toluene LossTolueneRecovered

114.12168.4

3-bromo- 1-(3-chloro-2-pyridinyl)- 1H-pyrazole-5-carbonyl chloride

707.5 Methyl chloride(g)

116.0

Triethyl amine 233.0 Triethyl amine 233.0Water 2280.0 Water 2280.0 2280.0

Organic waste 48.0Total 5959.5 Total 5959.5 2280.0

of 242

58. Sulfoxaflor TC


Sulfoxaflorwill be prepared by dissolving Sulfilimine in dichloromethane and thenaqueous solution of sodium permanganate will be added at 3°C slowly in 2 h. Afteraddition water willbe added through the funnel at 3 °C to 11°C. After maintaining for1 h. 35% sodium metabisulfite will be added slowly. Maintain will be done for 2 hand the product is filtered, washed and dried to get the desired product Sulfoxaflor.



Input OutputRaw material (Kgs) Products (Kg) Aqueous WasteSulfilimine 968 Sulfoxaflor TC 1000.00Dichloromethane 7680.8 MDC Loss

MDC Recovered2688.34992.5

Sodiumpermanganate

524.56 Water 4336.15 4336.15

Sodiummetabisulfite

2828.9 Salt 1472.57 1472.57

Water 2497.36 Organic waste 10.0Total 14499.52 Total 14499.52 5808.72

of 242

NRV

PGPG

DISCHARGE

P-207BP-207A

TO HOLDING TANK T-204

P-208A/B

PG

PG PG

SERVICE WATER

PG

SERVICE WATER

SERVICE WATER

DISCHARGE

PGPG

DISCHARGE

PRESSURE GAUGE

PG

PG

PGPG

PG

LI

PG

LEVEL INDICATOR

PG0-4 kg/cm20-4 kg/cm2

0-4 kg/cm2

0-1 kg/cm2

0-4 kg/cm2 0-4 kg/cm2

0-4 kg/cm2

0-4 kg/cm2

0-4 kg/cm2

0-4 kg/cm2

0-4 kg/cm2

PG

0-4 kg/cm2

LIPG0-1 kg/cm2

0-4 kg/cm2

0-4 kg/cm2

0-4 kg/cm2

0-4 kg/cm2

0-4 kg/cm20-4 kg/cm2

0-4 kg/cm20-4 kg/cm2

PG0-1 kg/cm2PG0-1 kg/cm2

NRV

PG

M/GB

LI

LILI

LI

LI

SERVICE WATER PGPG

DISCHARGE

T-206

NRV NRV

P-205A/B

TAG.NO.

P-201A/B

SF-201

PC-201

SC-201

COLLECTION TANKOIL AND GREASE FILTER

SAND FILTER

NEAUTRALIZATION TANK

TAG.NO.

03.11.17

ASP-201

FP-201

INFLUENT

1 B.R.TMANISH B.R.T03.11.17 ISSUED FOR APPROVAL

MM

BL-202A

XL

P-206A P-206B

REUSE FORINDUSTRIAL PURPOSE

FILTER PRESS

T-205

HE-201

P-203A/B

T-202T-201

T-203

Project Name:

Drg. No.

Plant

Scale

Date

Name

Rev

CLIENT:-

Approved

36 M3/DAY MEE CONDESATE TREATMENT PLANT

ETP

Cad Code :

Project No:

Rev

Description

of

Sheet

Name

Lcation:-

Checked

-

BEIL RESEARCH & CONSULTANCY PVT.LTD

03.11.17

B.R.T

B.R.T

B.R.T

Appr.

Check

Date

Drawn

Title :

P-204A/B

C R I M S U N O R G A N I C S P V T L T D

MANISH B.R.TISSUED FOR APPROVAL

-

NTS

0 03.10.17

03.11.17 MANISH

O/F

PG

M/GB

BL-201A

XL M

BL-201B

XL

BL-202B

XL M

SOLID WASTE TO TSDF SITE

SLUDGE PIT

80NB MS

150NB MS

50NB MS

50NB MS40NB MS

40NB MS

40NB MS

40NB MS

LI

P-202A/B

SLUDGE PIT

40NB MS

50NB MS

T-204

50NB MS

50NB MS

STORAGE TANK

50NB MS

50NB MS

HOLDING TANK

SECONDARY CLARIFIER

50NB MS

MBBR-201

AERATION TANK

50NB MS

150NB MS

50NB MS

50NB MS

80NB MS50NB MS

50NB MS

40NB MS

50NB MS

50NB MS

50NB MS

PRIMARY CLARIFIER

CENTRALIZED COOLING TOWER

CT-201

CAPACITY = 2 M3/HR

CONSIDERED IN CAPTIVE CT

P-207A/B

CT-201

EQUIP . SIZE

NEW

NEW

-

NEW

NEW

NEAUTRALIZATION TANKT-203

4.5M X 4.5M X 6.0M HT +(0.3M FB)

EQUIP. NAME.

MBBRMBBR-201

6.8M X 6.4M X 4.6M HT +(0.3M FB)

COOLING TOWER

ASP-201 AERATION TANK

NEW

EXISTING

EXISTING

EXISTING

HOLDING TANK

3.9M X 1.3M X 2M HT

T-205

2000 KG/HR

10 KL HDPE

MEE PLANT

STORAGE TANK

7.0M SQ, AREA

REMARK

EXISTING

HE-201 HEAT EXCHANGER

EQUIP. SIZE

SF-201

DIA=2M,HT=2.5M+0.5M (FB)

3.5M X 4.0M X 2M HT

PRIMARY CLARIFIERPC-201

2.0M X 2.0M X 1.5M HT

COLLECTION TANK 5.6M X 2.9M X 2M HTT-202

OIL AND GREASE FILTER

-

T-201

EQUIP NAME

T-204 5 KL HDPE

SAND FILTER

COLLECTION PIT TO PSF /ACF

NEW

P-205A/B CAPACITY = 2 M3/HR

FILTER PRESS

NEW

BL-201A/B

FP-201 0.47M X 0.47M X 10 PLATES

NEW


NEW

NEW

STORAGE TANK TO H.E

CAPACITY = 20 M3/HRCOOLING WATER CIRCULATION PUMP

NEW

P-204A/B

NEW

FILTER PRESS INLET

5KL HDPE

NEWP-206B

CAPACITY = 2 M3/HRP-206A BIO MASS RECYCLE PUMP

CAPACITY = 2 M3/HR

T-206

MBBR

BL-202A/B

CAP. = 900 M3/HR PRE 0.7 Kg/Cm2

CAP. = 450 M3/HR PRE 0.56 Kg/Cm2AERATION TANK

NEWCOLLECTION PIT

NEW

NEW

HOLDING TANK TO MEE PLANT

CARBON FILTER

CAPACITY = 2 M3/HR

PRESSURE SAND FILTER

P-201A/B NEAUTRALIZ. INLET PUMPS

CAPACITY = 2 M3/HR

T-207

P-208A/B SF-201 TO T-204

ACF-201

SC-201 DIA = 2M , HT = 2.5M + (0.5M FB)

MBBR FEED PUMPS

RO-201

PSF-201 DIA = 0.47M ,HT = 1.6M

NEW

ROCHEM RO PLANT

SECONDARY CLARIFIERNEW

NEW

MODIFIED

NEW

MODIFIED


NEW

NEW

DIA = 0.47M ,HT = 1.6M

REJECT HOLD TANK

10KL HDPE

5KL HDPE

T-208 PERMATE HOLD TANK NEW

REMARK

NEW

NEW

40NB MS

40NB MS

MEE PLANT

Page 100 of 242

LenovoLap

Typewritten text

LenovoLap

Typewritten text

Annexure 4

SETTLING

M-T-1

SEWAGE I/L

10 LITCOAGULANT

M-T-2

10 LITFLOCCULANT

MBBR

CL2 TANK HTPSF ACF

SEWAGE O/L

SETTLINGTANK-2

750MM X 500MM X 1000MM HT

EQUIP. NAME.

01.

02.

MIXING TANK-1

SR.NO. EQUIP. .NO.

MIXING TANK-2 750MM X 500MM X 1000MM HT

03. CLARIFIER-1 1500MM X 1500MM X 2500MM HT

04. 3000MM X 2000MM X 2500MM HT

05.

MBBR REACTOR

1500MM X 1500MM X 2500MM HT

06.

CLARIFIER-2


07.

CL2 TANK


08.

HOLDING TANK

600MM DIA X 1800MM HT

600MM DIA X 1800MM HT

PSF

09. ACF

SLUDGE

TANK-1

CL2

P-101A/B P-102A/B

P-103A/B P-104A/B

P-101A/B 1 M3/HR

1 M3/HRFLOCCULANT INLET

1 M3/HR

1 M3/HR

MBBR INLET PUMP

PSF/ACF INLET

P-102A/B

P-103A/B

P-104A/B

COAGULANT INLET

25NB

25NB

25NB

25NB

PG PG PG PG

BACK WASH WATER

TO SKID

PG

P-105

-BACK WASH WATER TANK

BACK WASH PUMP

-

P-105 1 M3/HR

PG PG

PG

TREE WAY VALVE

TREE WAY VALVE

Page 101 of 242

of 242

LenovoLap

Typewritten text

Annexure 5

NaOH NaOH NaOH

Venturi

Scrubber

I Stage

Scrubber

II Stage

Scrubber

The Gas Scrubbing System

Page 103 of 242

LenovoLap

Typewritten text

Annexure 6

of 242

LenovoLap

Typewritten text

Annexure 7

of 242

Steam 11

Total Water565WATER BALANCE DRAWING

DomesticGreen Belt43 Process Softner187

Lab & R&D CoolingTower Floor Wash25 20 30 45 10 142 5

237

Boiler4+13

20

170ETP108

30 10 5 5

RO8

100

100Rejects

8MEE 41Distillate

STP 30

TSDF3.6 Salts

18 2

Fresh Water277 Reused / TreatedWater288

CONSULTANT:

IMO No.DATE SCALE REV

TITLE: CLIENT:

WATER BALANCE DIAGRAM18-06-18

HECS(P)Ltd, CHENNAIM/S. CRIMSONCUDDALORE.

NOTES :1. ALL UNITS ARE IN m3/day.41

Page 189 of 242

dell

Typewritten text

Annexure 9

of 242

dell

Typewritten text

Annexure 10

APPLICATION FOR ENVIRONMENTAL CLEARANCE...

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