September 17, 2007
Annexure-I List of Products Sr. Name of Products Quantity No. (MT/Month) A Herbicides 1. Imazethapyr Technical 15 2. Pendimethalin Technical 10 3. Atrazine Technical 50 4. Metribuzine Technical 20 5. Glyphosate Technical 150 6. Clodinafop- Propargyl Technical 20 7. Pretilachlor Technical 50 8. Paraquat Dichloride Technical 20 9. 2,-4, Dichlorophenoxy Acetic Acid 200 10. Bispyribac Sodium 5 11. Dicamba Tech. 10 12. Isoprothiolane Tech 10 13. Oxyfluorfen Tech. 10 B Fungicides 14. Tricyclazole Technical 50 15. Hexaconazole Technical 50 16. Difenoconazole Technical 50 17. Propiconazole Technical 50 18. Myclobutanil Technical 15 19. Thiophenate Methyl 50 20. Tebuconazole Technical 50 21. Mancozeb Technical 300 22. Propineb Technical 50 C Insecticides 23. Thiamethoxam Technical 100 24. Buprofezin Technical 50 25. Daifenthiuron Technical 50 26. Imidacloprid Technical 100 27. Fipronil Technical 100 28. Chloropryiphos Technical 100 29. Metalaxyl Technical 50 30. Alpha Cypermethrin Technical 30 31. Cypermethrin Technical 50 32. Lambda Cyhalothrin Technical 50 33. Novaluron 50 34. Bifenthrin Technical 50 D Other Pesticide 35. Abamectin Technical 50 36. Emamectin Benzoate Technical 50 37. Azoxystrobin Technical 50 38. Deltamethrin Technical 20
M/s. Dhanuka Agritech Limited 1
39. Acetamiprid Technical 25 40. Trizophos Technical 30 41. Propargite Technical 25 E Intermediate Chemicals 42. Mono Chloro Acetic Acid 100 43. IDA 100 44. PMIDA 500 45. CMAC 200 46. MPBD 100 47. CCMP 100 48. Triazoles 50 Total 3415
M/s. Dhanuka Agritech Limited 2
List of Raw Materials Sr. No. Name of Raw Materials Quantity (MT/Month) Imazethapyr-15 MT 1 EPCA 12.27 2 DMMI 10.23 3 DMF 2.18 4 Catalyst 0.14 5 sodium carbonate 9.54 6 Methanol 0.29 Pendimethalin-10 MT 1 Dichloroethane 0.55 2 3,4-Xylidine 5.00 3 Pd/catalyst 0.25 4 Hydrogen 0.10 5 Nitric acid 10.50 6 Sulphuric acid 9.00 Atrazine-50 MT 1 Toluene 1.0 2 Cynuric chloride 45.25 3 isopropyl amine 21.00 4 Caustic lye 9.75 5 mono ethyl amine 16.05 6 soda ash 13.30 Metribuzine-20 MT 1 Sulphuric acid 24.90 2 Triazinone 20.00 3 Dimethyl sulphate 12.72 4 soda ash 37.64 Glyphosate-150 MT 1 FeSO4(10%) 44.85 2 PMIDA 298.50 3 Hydrogen Peroxide(50%) 111.90 4 Catalyst 1.50 5 caustic lye (48%) 107.40 Clodinafoppropergyl-20 MT 1 Acetonitrile 2.30 2 RHPPA (R(+)-2-[4-(5-chloro-3- fluoropyridin-2-yloxy) phenoxy] 10.30 propionic acid) 3 Potassium carbonate 17.00 4 CDFP 8.50 5 Propargyl chloride 5.00 Pretilachlor-50 MT 1 DEPA 35.15 2 Chloro Acetyl chloride 22.65
M/s. Dhanuka Agritech Limited 3
Sr. No. Name of Raw Materials Quantity (MT/Month) 3 Hexane 2.35 4 ammonia gas 2.75 Paraquate Dichloride-20 MT 1 4,4' bipyridine 18.88 2 Methyl iodide 15.12 3 Silver Chloride 17.12 2-4-Dicholorophenoxy Acetic Acid-200 MT 1 30% HCl 114.0 2 2,4 D sodium salt 240.0 Bispyribac Sodium-5 MT 1 2,6 hydroxy benzolic acid 12.50 2 4,6 Diethoxy2,Methyl sulfonyl 4.55 pyrimidine 3 TBAB 0.17 4 Caustic soda 1.28 5 Toluene 0.50 6 n-butanol|+ Ethyl acetate 0.50 Dicamba -10 MT 1 1,2,4 tricholoro benzene 5.08 2 Methanol 2.50 3 Sodium hydroxide flakes 1.00 4 HCl 30.34 5 NaOH 1.57 6 Xylene 2.07 7 48% KOH 5.66 8 Anhydrous potassium carbonate 6.50
9 CO2 gas feeding 2.53 10 NaOH solution 13.00 11 Dimethyl sulfate 4.58 Isoprothiolane -10MT NaOH 7.25
CS2 3.00 Di-isopropyl malonate 7.00 1,2 dicholoro ethane 1.00 n-Heptane 0.30 Oxyfluorfen-10MT 3-chlorophenol 4.31 Chloroethane 2.25
HNO3 2.30
H2SO4 3.20 4-trifloromethyl 2-chlorophenol 6.00 potassium salt Tricyclazole-50 MT 1 3-mythyl-(1,2)-benzothiazole 36.65
M/s. Dhanuka Agritech Limited 4
Sr. No. Name of Raw Materials Quantity (MT/Month) 2 KOH 33.35 3 DMF 4.35 4 1,2,4 Triazol 14.00
5 K2CO3 3.35 Hexaconazole-50 MT 1 2,4-DVP 41.40 2 Dimethyl sulphide 60.0 3 Dimethyl sulphate 35.85 4 KOH 35.85 5 DMF 4.15 6 1,2,4 Triazol 13.10
7 K2CO3 2.40 Difenconazole-50 MT 1 2-chloro-4-(4-chlorophenoxy) 46.35 benzyl chloride 2 4-methyl-1, 3-dioxolane 14.05 3 KOH 28.10 4 DMF 8.70 5 1,2,4 Triazol 11.80
6 K2CO3 2.80 Propiconazole-50 MT 1 2,4-dichloro benzyl chloride 42.25 2 4-propyl-1, 3-dioxolane 20.25 3 Dimethyl sulphide 58.80 4 KOH 33.80 5 DMF 4.05 6 1,2,4 Triazol 14.20
7 K2CO3 3.40 8 Iso Propanol 11.80 Myclobutanil-15 MT 1 Toluene 2.63 2 PCBCN 11.48 3 n-butyl bromide 10.88 4 NaOH 9.75 5 TEBAC 1.28 6 NaOH, 48% 16.50 7 Dibromomethane 11.63 8 DMF 1.50 9 1,2,4-triazole 5.03 Thiophenate methyl-50 MT 1 EDC 4.00 2 Sodium Thio cyanate 26.30 3 Methyl chloro formate 30.00 4 OPDA 17.50
M/s. Dhanuka Agritech Limited 5
Sr. No. Name of Raw Materials Quantity (MT/Month) Tebuconazole-50 MT 1 Dimethyl Sulfate 25.10 2 Sodium sulfide 1.30 3 Ketal 37.75 4 KOH 16.15 5 1,2,4-triazole 12.75 6 K2CO3 2.00 7 DMF 1.25 Mancozeb-300MT EDA 59.40 NaOH(48%) 171.00
CS2 154.50
MnSO4 25.50
MnSO4(27%) 537.0
ZnSO4(32%) 41.40 Propineb-50MT Carbon disulphide 28.75 Di-amino Propane 14.25 15% ammonia solution 95.00 Zinc sulphate 58.00 Thiamethoxam-100 MT 1 CCMT 77.10 2 MNIO 73.40 3 DMF 2.70
4 K2CO3 84.90 5 80% Methanol 36.70 Buprofezin-50 MT 1 1-isopropyl 3-t-butyl thiourea 25.00 2 N-chloromethyl -N-phenyl 32.00 carbamoyl chloride 3 MCB 1.00 4 Ammonium bicarbomate 120.0 5 Methanol 5.0 Daifenthiuron-50 MT 1 Xylene 3.90 2 DIPBA 41.30 3 NaSCN 13.35 4 HCl, 30% 19.20 5 tert-butylamine 10.95 Imidacloprid-100 MT 1 CCMP 85.60 2 N-NII 71.50 3 DMF 10.80 4 Na2CO3 67.10
M/s. Dhanuka Agritech Limited 6
Sr. No. Name of Raw Materials Quantity (MT/Month) 5 Methanol 1.90 Fipronil-100 MT
1 CF3COOH 10.00 2 Monochloro benzene 2.50
3 H2O2 14.00 4 Thiopyrazole derivative 250.0 Chlorpyriphos-100 MT 1 NaTCP 65.80 2 DETC 56.00 3 Catalyst 0.80 4 EDC 26.30 5 C. S. lye 48% 4.30 Metalaxyl-50 MT 1 N-(2,6- Dimethyl phenyl) 37.50 alanine-methyl ester 2 methoxy acetyl chloride 19.85 3 Catalyst 0.75 4 Toluene 5.40 5 C.S.Lye 48% 2.45 Alpha Cypermethrin-30 MT 1 MPBAD 21.42 2 CMAC +High Cis 25.05 3 NaCN 5.85 4 n-Hexane 14.76 5 Catalyst 3.00 6 Soda ash Soln. 5% 42.00 7 IPA + Solvent 18.93 8 10% Sodium hypochlorite 64.50 Cypermethrin-50 MT 1 CMAC 29.50 2 MPB 24.25 3 NaCN 7.25 4 PTC 0.30 5 Hexane 2.25 6 Hypochlorite 81.50 Lambda Cyhalothrin-50 MT 1 MPBAD 22.40 2 TP Acid Chloride 30.50 3 NaCN 6.10 4 n-Hexane 5.70 5 Soda ash Soln. 5% 47.60 6 IPA-Solvent 2.60 7 10 % Sodium hypochlorite 71.45 Novaluron-50 MT
M/s. Dhanuka Agritech Limited 7
Sr. No. Name of Raw Materials Quantity (MT/Month) 1 2,6-difluoro benzoyl isocyanate 16.05 2 2-chloro-4-amino phenoxy ether 39.70 3 Monochloro benzene 27.35 4 Toluene 0.80 Bifenthrin-50 MT 1 MTH Acid 31.45 2 BPC 28.40 3 DMF 3.95 4 K2 CO3 9.10 5 Hexane 8.30
6 10% NaHCO3 Solution 3.30 7 10% Methanol in Hexane 0.50 Abamectin-50 MT 1 Streptomycess avermemitis 27.80 2 Anthelminic 27.50 3 Acaricidal 28.50 4 Crude abamectin 83.35 5 Methanol 5.55 Emmamectin Benzoate-50 MT 1 Streptomycess avermemitis 22.75 2 Anthelminic 45.45 3 Acaricidal 45.45 4 Methyl amine 9.10 5 Methyl benzoate 11.35 6 Methanol 15.45 Azoxystrobin-50 MT 1 2,6-Dichloropyrimidine 20.55 2 DMF 5.40 3 MHPMP 28.65 4 Potassium carbonate 45.95 5 cyno phenol 16.40 6 Cuprus chloride 0.55 7 caustic soda 1.10 8 Hexane 4.30 9 MDC 2.15 Deltamethrin-20MT 1 Catalyst 3.60 2 DAC 11.00 3 CPBA 10.00 4 Benzene 12.00 5 NaOH 2.00 Acetamiprid-25MT 1 NCMA 13.00 2 CMAMP 17.50
M/s. Dhanuka Agritech Limited 8
Sr. No. Name of Raw Materials Quantity (MT/Month) 3 Methanol 1.25 Trizophos-30MT 1 1-phenyl 2-hydroxy-1,2,4 17.10 triazole 2 Triethylamine 11.70 3 EDC 2.10 4 Diethyl thiophoryl chloride 19.80 5 Caustic LYE(48%) 7.50 Propargite-25MT 1 1,2 –cyclohexane oxide 10.98 2 Potassium hydroxide(KOH) 7.25 3 Toluene 3.83 4 Thionyl chloride 26.05 5 Propargyl alcohol 5.90 6 p-teret. Butyl alcohol 15.83 7 Brine solution(15% NaCl) 80.35 Mono Chloro Acetic Acid-100 MT 1 Acetic Acid 87.00 2 Sulphur mono Chloride 3.75 3 Liq. Chlorine 90.00 4 Acetic Anhydride 1.35 IDA-100 MT 1 MCA 147.60 2 Calcium Hydroxide 114.60
3 NH3 Solution 79.60 4 HCl 32% 268.90 PMIDA-500 MT 1 IDA-HCl 510.00 2 Phosphorous acid 346.50 3 HCl 32% 292.00 4 Formaldehyde solution 396.00 5 Caustic solution 30% 782.00 CMAC-200 MT 1 CTC 297.60 2 CAN 101.00 3 Acetonitrile 7.20 4 Dea. HCl 3.80 5 Catalyst 1 3.80 6 H2SO4 369.00 7 SOCl2 391.20 8 IB 119.0 9 Hexane 852.40 10 TEA 126.00 11 10% NaHCO3 165.20
M/s. Dhanuka Agritech Limited 9
Sr. No. Name of Raw Materials Quantity (MT/Month) 12 Caustic lye 97.60 13 Catalyst 2 1.8 14 DMF 0.40 MPBD-100 MT 1 Benzaldehyde 74.80
2 AlCl3 123.00 3 EDC 12.00 4 Br 55.00 5 Cl2 25.80 6 Formic Acid 2.00 7 MEG 38.20 8 Toluene 10.50 9 KOH 33.50 10 Phenol 56.20
11 H2SO4 79.00 CCMP-100 MT 1 6-Chloro nicotinic Acid 109.40 2 Phosphorus oxychloride 105.60 3 Phosphorus Penta Chloride 144.40 4 Sodium boro hydride 25.60 5 Thionyl Chloride 75.60 6 Toluene 11.10 Triazoles-50 MT 1 Formic acid 85% 100.0 2 Ammonia gas 35.0 3 Hydrazine hydrate 60.0
M/s. Dhanuka Agritech Limited 10
Annexure -II Manufacturing Process 1. Imazethapyr Manufacturing Process Stage 1 5-ethyl-3-pyridine carboxylic acid (EPCA) is reacted with 4,5 Dihydro-4 methyl 4 (1 methyl ethyl)-5-oxo-1 H-imidazoline in present of catalyst and DMF solvent. The Hydrochloric acid, which is formed during the reaction, is scavenged by putting Sodium carbonate as acid scavenger. Stage 2 The resulting mass is diluted by water and filtered to remove the salts of Sodium Chloride (NaCl) & Sodium bicarbonate. The organic mass is then treated with water and finally solvent is removed by distillation. Stage 3 The concentrated mass is then crystallized to get pure product – Imazethapyr technical. Stage 4 Finally toxic effluent, which contains traces of pesticides, is taken to hydrolysis stage for detoxification. Where aqueous mass is treated at high temperature by Alkali for the rapid hydrolysis of pesticides to simpler non-toxic compounds. Chemical Reaction:
M/s. Dhanuka Agritech Limited 11
Mass Balance
Mass balance of Imazethapyr IN PUT Kg OUT PUT Kg EPCA 818 Recovered solvent DMF 1855 DMMI 682 STAGE 1 Residue 100 DMF 2000 CONDENSATION AND Catalyst 9 SOLVENT RECOVERY Sodium Carbonate 636
Water 909 Effluent 1765 STAGE 2 WATER WASH
Methanol 364 STAGE 3 Recovered Methanol 345 CRYSTALIZATION Residue 50 FILTRATION & Drying loss 303 DRYING Imazethapyr 1000
Total 5418 5418
M/s. Dhanuka Agritech Limited 12
2. Pendimethalin Manufacturing Process Step-I: Preparation of 3,4-dimethyl N(1-Ethylpropyl) Benzene amine3,4-xylidine and solvent charged in a reactor then add catalyst and diethyl ketone at 40-45°C in 3 hrs and reductive amination by hydrogen gas in 3 hrs. Then still off the solvent up to 85°C under vacuum. Step-II: Preparation of Pendimethalin Charge 3,4-dimethyl N (1-ethylpropyl) Benzene amine and sulphuric acid in a reactor. Then cool the reaction mass at 5-10°C. Start addition of nitric acid at 5-10°C and competed in 3 hrs. Then maintain for 2 hrs at 25-30°C. After completion of reaction, cool the reaction mass at 0-5°C then filter the material and dry.
M/s. Dhanuka Agritech Limited 13
Flow diagram with Mass Balance
MASS BALANCE OF PENDIMETHALIN INPUT KGS OUTPUT KGS Dichloroethane 750 Reaction 1 3,4-xylidine 500 effluent 74 Imine reaction Diethylketone 360
Pd/C catalyst 25 Reaction 2 Hydrogen 10 Hydrogenation
Nitric acid 1050 Nitration mixture (Aq-1) 1660 Reaction 3 Sulfuric acid 900 Pd/C catalyst (recovery) 25 Nitration
Water 1000 Effluent 1046 Washing
Dichloroethane (recovery) 695 Crystallization Organic residue 95 Distillation Pendimethalin 1000
TOTAL 4595 4595
M/s. Dhanuka Agritech Limited 14
3. ATRAZINE Manufacturing Process First Toluene is taken in rector then Cynauric Chloride is charged in to the solvent and is dissolved completely. Then isopropyl amine is added slowly. Then Sodium Hydroxide is added to neutralize the liberated hydrochloride acid. Then again mono ethyl amine is added slowly. Again sodium hydroxide or soda ash is added to neutralize the mixture. Then solvent is recovered by steam distillation. Atrazine is filtered off. Centrifuged, dried and pulverized. Pulverized Atrazine is then packed according to the requirement. ATRAZINE 50% WP Measured quantity of Technical is taken and blander. Then weighted quantity of dispersing agent, wetting agent, precipitated silica and china clay are added in it under stirring as per recipe. Blending is carried out for three hours to make it homogeneous. Then micro pulverized to get fine particle size. Then it is packed in various sizes according to customers requirements. Chemical Reaction:
Flow diagram & Mass Balance:
ATRAZINE T
INPUT KG OUTPUT KG Toluene 7000 Cyanuric chloride 905 Isopropyl amine 420 Toluene Recovery 6980 Caustic lye 195 CO2 losses 108 Mono ethyl amine 321 REACTION effluent 241 Soda ash 266 Water with caustic 195 Water for soda + caustic 3000 Steam 4800
effluent 11000 DISTILLATION
FILTRATION
Water washing 2650 WASHING
Drying Loss 423 DRYING Product 1000
Total 19752 19752
M/s. Dhanuka Agritech Limited 15
4. Metribuzine Process Description Triazinone is charged slowly in Sulfuric acid in 4 hours. Temperature is raised to 450C and Di Methyl sulfate is charged. Maintain temperature for 10 hours time. When reaction shows completion of methylation, quench in 20% Soda ash solution. Finally adjust pH 10 with NaOH lye. Filter, centrifuged and dry the wet cake. Pulverise and pack suitably. Chemical Reaction O O O S H C H C 3 HO S OH 3 NH2 1/2 HN NH O + H O H3C N O 2 CH3 + NH + H C + 2 3 sulfuric acid O Pivaloyl Cyanide Thiocarbohydrazide acetic anhydride 49 18 111 106 102
CH O H C 3 3 O NH2 N (NH ) SO 2 1/2 4 2 4 H3C + + N HO CH3 N SH 66 Triazinone 120 200
Mass Balance
METRIBUZINE T
Input kg Output kg sulfuric acid 1245 Triazinone 1000 REACNTION Dimethyl sulfate 636
Soda ash 1882 Water 4909 Inorgsnic Salt 3582 FILTRATION
Water 3636 WASHING Effluent 8244
Drying loss 482 DRYING Metribuzin 1000
Total 13308 Total 13308
M/s. Dhanuka Agritech Limited 16
5. GLYPHOSATE Manufacturing Process: PMIDA react with Hydrogen Peroxide in presence of Catalyst and cooler after Oxidation, reaction mass treat with Ferrous Sulphate solution get Glyphosate in slurry form during this formaldehyde generates is converted to Foric Acid. Slurry filtered and washes with water. Wet cake dry to get Glyphosate Tech of 95% purity.Finaly Toxic Effluent which contains traces of Pesticides is taken to Hydrolysis stage for detoxification. Where Aq. Mass is treated at high temp.by Alkali for the rapid hydrolysis of presticides to simpler non-toxic compounds. Chemical Reactions:
Glyphosate (TECH)
O CH COOH HO 2 Catayst P - CH - N + H2O2 2 CH COOH HO 2
PMIDA Hydrogen Peroxide
(MW- 227) (MW- 34)
O HO CH COOH + P - CH2 - N 2 + HCHO CO2 + H2O HO
Glyphosate M.W.- 30 M.W.- 44 M.W.- 18 (MW- 169)
M/s. Dhanuka Agritech Limited 17
Flow diagram & Mass Balance:
Glyphosate INPUT KG OUTPUT KG
FeSO4 (10%) 299 PMIDA 1990 H2O2(50%) 746 GLYPHOSATE PREPARATION Water 995 Catalyst 10
Water Wash 199 FILTRATION
TEE Org. Residue 199
WATER + FORMIC ACID
C.S. Lye 48% 716 Effluent 2061 DETOXIFIN. BY HYDROLYSIS & Salt mix to TSDF 1078 TEE DIST. Effluent 247
DRYING Drying Loss 370 Glyphosate 95% 1000
TOTAL 4955 TOTAL 4955
M/s. Dhanuka Agritech Limited 18
6. Clodinafop Propergyl Manufacturing Process Step-I Preparation of potassium salt of R(+)-2-[4-(5-chloro-3-fluoropyridin-2-yloxy) phenoxy] propionic acid. 5-chloro-2,3-difluoropyridine (I) is reacted with R(+)-2-(4- hydroxy phenoxy) propionic acid (II) in presence of alkali and solvent to yield potassium salt of R(+)-2-[4-(4-chloro-3-fluoropyridin-2-yloxy) phenoxy] propionic acid (III).
Step-II Preparation of propynyl R(+)-2-[4-(4-chloro-3-fluoropyridin-2-yloxy)-phenoxy] propionate (ClodinafopPropargyl). Potassium salt of R(+)-2-[4-(5-chloro-3- fluoropyridin-2-yloxy) phenoxy] propionic acid (III) resulted from step-I is reacted with propargyl chloride (IV) in solvent to yield and product Propynyl R(+)-2-[4-(5- chloro-3-fluoropyridin-2-yloxy) phenoxy] propionate (V). Crude product thus obtained is filtered. Crude product is crystallized by methanol to give ClodinafopPropargyl of 93% min. Purity.
M/s. Dhanuka Agritech Limited 19
Flow diagram with Mass Balance
MASS BALANCE OF CLODINAFOP PROPARGYL
INPUT KGS OUTPUT KGS
Acetonitrile 2000 RHPPA 515 Reaction 1 Potassium carbonate 850
CDFP 425 Propargyl chloride 250 Reaction 2 Carbon dioxide 250
Filtration Inorganic salt 790
Acetonitrile (recovery) 1885 Distillation Residue 115 Clodinafop propargyl 1000
TOTAL 4040 4040
M/s. Dhanuka Agritech Limited 20
7. Pretilachlor Manufacturing Process Charge DEPA and Hexane into the reactor with agitation at 300C temperature and charge chloroacetyle chloride slowly in the reaction mass at 300C. When the reaction is over, cool the material and neutralize with ammonia gas till pH-8. Wash the material with water. After washing organic layer, take it to distillation vessel for hexane recovery under vacuum upto 800C. Cool it to 200C. Filter the Pretilachlor for packing. Chemical Reaction:
Mass Balance
Mass balance of Pretilachlor
IN PUT Kg OUT PUT Kg
DEPA 703 HCl gas 156 STAGE 1 PRETILACHLOR Chloro acetyle chloride 453 FORMATION Hexane 1094
Ammonia gas 55 STAGE 2 NEUTRALIZATION
Water washing 1563 STAGE 3 WASHING effluent 1618
Hexane Recovery 1047 Residue 47 STAGE 4 HEXAN RECOVERY Pretilachlor 1000
Total 3868 3868
M/s. Dhanuka Agritech Limited 21
8. Paraquat Dichloride Technical Stage 1 Charge 4, 4’bipyridine in the reactor and stir for 30 minute. Charge methyl iodide slowly in the reaction mass 2-3 hrs at 1050C and maintain the temperature for 3 hrs and check the sample for reaction complete. Stage 2 Charge crude paraquate in the reactor and a two-fold excess of barium chloride is added to promote ion exchange. Wash the reaction mass with water to get pure paraquate technical. Chemical Reaction
N N NCH NCH 2 IH + ICH3 3 3 +
Hydrogen Iodide 4,4-bipyridene Methyl Iodide Crude Paraquate
CH N CH N+ N+CH 2 Ba+ 3 NCH3 + BaCl2 3 3 + Cl- Cl-
Crude Paraquate Barium chloride Paraquate Dichloride
Mass Balance
Mass balance of Paraquat IN PUT Kg OUT PUT Kg
4,4' bipyridine 944 STAGE 1 PROCESS Methyl iodide 756
Silver Chloride 856 effluent 2667 Water 1111 Filtration Paraquate 1000
Total 3667 3667
M/s. Dhanuka Agritech Limited 22
9. 2,4-Dichlorophenoxyacetic acid (2,4-D Acid) Manufacturing Process: In the manufacturing process, 2,4-D Sodium Salt and water are charged in a rubber lined reactor. Now Hydrochloric acid (HCl) is added slowly with constant stirring for proper reaction. The addition of HCl is continued till the pH of the materials reaches to 2. In the reactor, HCl reacts with 2,4-D Sodium salt to form 2,4-D Acid (Tech.). Neither excess temperature nor catalyst is necessary in this reaction. The product is separated from the mother liquor in a rubber lined centrifuge and subsequently dried in a dryer. The dried product is ground with a Pulverizer and packed in HDPE bags. Although the mother liquor (wastewater) is rich in HCl, its recycle to the reactor is prohibited by high concentration of NaCl. The mother liquor is, therefore, sent to the ETP for treatment and disposal. Chemical Reaction: Cl Cl
Cl O-CH2-COONa + HCl Cl O-CH2-COOH + NaCl
2,4-D Sodoum Salt Hydrochloric 2,4-D Acid Sodium Acid Chloride
Mass balance and Process Flow Diagram:
2,4-D Acid
Input Kg Output Kg
30% HCl 570 2,4-D Sodium salt 1200 REACTOR Water 300
Effluent 770 CENTRIFUGE
Drying Loss 300 DRYER Product 1000
Total 2070 2070
M/s. Dhanuka Agritech Limited 23
10. Bispyribac Sodium Manufacturing Process Toluene, TBAB Caustic soda and 2,6 Dihydroxy Benzoic acid is charged in reactor and followed by addition of 4,6 Dimethoxy 2 Methoxy Sulfonyl Pyrimidine. The reaction mass is heated for several hours to complete the reaction. After completion of reaction mass is cooled and filtered. Crude is crystallized using n Butanol, ethyl acetate and water. After filtration wet cake is dried to get BisPyribac Sodium. Chemical Reaction O O OH H3C S N O CH3 O HO OH Na OH N + 2 +
O CH3 4,6 Dimethoxy 2 methyl Sulfonyl Pyrimidine 2,6 Dihydroxy Benzoic acid 218 40 154
Na O O O CH3 H C S H + H2O O 2 3 N O O N O O CH3 N N + 160 18 O O H C 3 H3C
452 Bis Pyribac Sodium
M/s. Dhanuka Agritech Limited 24
Mass balance & Flow diagram with Mass Balance
BISPYRIBAC SODIUM
INPUT KG OUTPUT KG
2,6 hydroxy Benzoilc Acid 2400 4,6 Diethoxy 2, Methyl 893 Solfonyl Pyrimidine REACTION TBAB 33 Effluent 2133 Caustic Soda 255 Toluene 4000
Toluene Recovery 3900 FILTRATION Residue 748
Mixture of n Butanol and n-Butanol 4500 5900 Ethyl Acetate CRYSTALIZATION Ethyl Acetate 1500 (Reuse)
Water 4600 FILTRATION Effluent 4200
Drying Loss 300 DRYING Product 1000
TOTAL 18181 18181
M/s. Dhanuka Agritech Limited 25
11. Dicamba Tech. Process Description Step-1 The desired quantities of Methanol, 1,2,4- Trichlorobenzene and sodium hydroxide flakes are added in to the reactor. The stirred mixture is heated to reaction temperature and pressure till the whole reactants reached to desired level. Once the reaction is over, the mass is cooled. The reaction mass pH is adjusted with HCl & Water. Then layers are separated. The aqueous layer is neutralized with NaOH and methanol is recovered for recycling. The Product is recovered from organic layer by fractionation and is taken for further processing. Step-2 The desired quantities of Xylene, 48% aq. KOH are charged along with product from step-1 (2,5 dichloro phenol) in to the reactor. The stirred mixture is heated to reflux temperature and water is removed during reaction, the mass is cooled. Potassium
carbonate and CO2 is added to the reaction mass at desired temperature and pressure till the whole reactants reached to desired level. Once the reaction is over, the water and HCl is added to isolate the product which is then cooled, filtered & dried and taken for further processing. Step-3 The desired quantities of Xylene and 30% aq. NaOH are charged along with Dimethyl sulfate and step-2 product in to the reactor. The stirred mixture is heated to reaction temperature till the whole reactants reached to desired level. Once the reaction is over layers are separated. The solvent is recovered from organic layer for re-cycling and NaOH solution is added in left over mass. The stirred mixture is then heated to reflux temperature and reaction generated methanol is distilled out. Then the mass is cooled and the reaction mass pH is adjusted with HCl & Water to isolate the product. The wet product is dried as a finished product. Chemical Reaction
M/s. Dhanuka Agritech Limited 26
Mass Balance
DICAMBA T
INPUT KG OUTPUT KG
Methanol 3998 1,2,4- Trichlorobenzene 508 Sodium Hydroxide Flakes 100 Methanol 3748 REACTION STEP 1 Water 2082 Residue 181 HCl 1041 Effluent 3430 NaOH 157
Xylene 2915 48% KOH 566 Anhydrus potassium Carbonte 650 Xylene 2770 REACTION STEP 2 CO2 Gas Feeding 253 Effluent 2865 Water 1249 HCl 1182
Xylene 1249 NaOH Solution 1300 Xylene 1187 Water 2215 REACTION STEP 3 Residue 158 Dimethyl Sulfate 458 Effluent 4920 HCl 811
Drying Loss 475 DRYING Product 1000
TOTAL 20734 20734
M/s. Dhanuka Agritech Limited 27
12. Isoprothiolane Tech
Flow Diagram & Mass balance
ISOPROTHIOLANE
INPUT KG OUTPUT KG
NaOH 725 CS2 300 CONDENSATION & LAYER 1,2-Dichlororethane Recovery 675 Di-Isopropyl malonate 700 SEPARATION Effluent 855 1,2- Dichloroethane 775
n- Haptane 2250 n-Haptane Recovery 2220 RECTIFICATION Product 1000
TOTAL 4750 4750
M/s. Dhanuka Agritech Limited 28
13. Oxyfluorfen Tech. 3-Chlorophenol, potassium salt of 4-Trifloromethyl-2-Chloro Phenol is reacted with chloroethane and nitric acid in presence of sulfuric acid at 50 – 55°C to form the crude Oxyfluorfen. After washing it with water, mass is centrifuged and dried to form technical grade Oxyfluorfen. Chemical Reaction:
Mass Balance:
OXYFLUORFEN T
INPUT KG OUTPUT KG
3-Chlorophenol 431 Chloroethane 225 HNO3 230 Spent Acid Recycle 300 REACTOR H2SO4 320 4-Trifloromethyl-2-Chlorophenol 600 Potassium Salt
Wash Water 800 Spent Acid To Effluent 850 FILTRATION & DRYING Drying loss 456 Product 1000
TOTAL 2606 2606
M/s. Dhanuka Agritech Limited 29
14. TRICYCLAZOLE Manufacturing process Stage 1 Charge solvent in the reactor and add 3-methyl-(1,2)-benzothiazole Chloride slowly in the reaction mass for 2-3 hrs and maintain the temperature for 3 hrs. Add KOH flakes slowly. Maintain the reaction mass for 4 hrs until the reaction is complete. Stage 2 Charge intermediate Dimethyl Formamide, 1,2,4-Trizole and K2CO3 in the reactor and maintain the reaction for 3 hrs at high temperature until the reaction is complete. Stage 3 Recover DMF under vacuum partially. Stage 4 Wash the reaction mass with water. Dry the wet cake of tricyclazole in drier. Chemical Reaction:
Mass Balance:
Mass balance of Tricyclazole T
IN PUT Kg OUT PUT Kg
3-mythyl-(1,2)-benzothiazole 733 Water 1333 Organic effluent 1933 STAGE 1 INTERMEDIATE KOH 667
DMF 1760 1,2,4 Triazol 280 STAGE 2 TRICYCLAZOLE K2CO3 67
DMF Recovery 1673 STAGE 3 DMF RECOVERY Residue 87
effluent 2147 Water for washing 2000 STAGE 4 WASHING Tricyclazole 1000
Total 6840 6840
M/s. Dhanuka Agritech Limited 30
15. Hexaconazole Manufacturing Process Stage 1 Charge 2,4-Dichloro valero phenol and Dimethyl sulphide in the reactor and stir for 30 minute and charge Dimethyl sulphate slowly in the reaction mass in 2-3 hrs. Maintain the temperature for 5 hrs and check the sample for reaction for Valero phenol content. After reaction is complete, add KOH flakes slowly. Maintain the reaction mass for 4 hrs until the reaction is complete. Stage 2
Charge oxarine, Dimethyl formamide, 1,2,4-Trizole and K2CO3 in the reactor and maintain the reaction for 3 hrs at high temperature until the reaction is complete. Stage 3 Recover DMF under vacuum partially. Stage 4 Wash the reaction mass with water. Stage 5 Add heptane in the crude Hexaconazole and stir for 2 hrs. Cool the reaction mass and filter the Hexaconazole. Stage 6 Dry the product Hexaconzole in drier. Chemical Reaction:
M/s. Dhanuka Agritech Limited 31
Mass Balance
Mass balance of Hexaconazole
IN PUT Kg OUT PUT Kg
2,4-DVP 828 Dimethyl sulphide 1200 Organic effluent 2772 Dimethyl sulphate 717 OXIRAIN FORMATION KOH 717 Water 69
DMF 1821 1,2,4 Triazol 262 HEXACONAZOLE FORMATION
K2CO3 48
DMF Recovery 1738 DMF RECOVERY Residue 83
Water washing 828 effluent 897 Heptane 910 WASHING
Hexaconazole 1000 CHILLING & FILTRATION Haptain Recovery 810
Hexaconazole Wet 1034 Drying Loss 134 DRYING Hexaconazole 1000
Total 8434 8434
M/s. Dhanuka Agritech Limited 32
16. Difenconazole Manufacturing process Stage 1 Charge 4-methyl-1, 3-dioxolane in the reactor and stir for 30 minute and charge 2- chloro-4-(4-chlorophenoxy) benzyl chloride slowly in the reaction mass for 2-3 hrs and maintain the temperature for 3 hrs and check the sample for reaction complete. After reaction is complete add KOH flakes slowly. Maintain the reaction mass for 4 hrs until the reaction is complete. Stage 2 Charge intermediate, Dimethyl Formamide, 1,2,4-Trizole and K2CO3 in the reactor and maintain the reaction for 3 hrs at high temperature until the reaction is complete. Stage 3 Recover DMF under vacuum partially. Stage 4 Wash the reaction mass with water. Dry the wet cake of difenoconazole in drier.
Mass Balance
Mass balance of Difenoconazole
IN PUT Kg OUT PUT Kg
2-chloro-4-(4-chlorophenoxy) 927 benzyl chloride Organic effluent 702 4-methyl-1, 3-dioxolane 281 Reaction-1 KOH 562
DMF 1483 1,2,4 Triazol 236 Reaction-2
K2CO3 56
DMF Recovery 1309 DMF RECOVERY Residue 174
effluent 1000 Water washing 1123 WASHING & Drying Drying Loss 483 Difenoconazole 1000
Total 4668 4668
M/s. Dhanuka Agritech Limited 33
17. Propiconazole Manufacturing process Stage 1 Charge 4-propyl-1, 3-dioxolane and Dimethyl Sulphide in the reactor and stir for 30 minute and charge 2,4-dichloro Benzyl Chloride slowly in the reaction mass for 2-3 hrs and maintain the temperature for 3 hrs and check the sample for reaction complete. After reaction is complete add KOH flakes slowly. Maintain the reaction mass for 4 hrs until the reaction is complete. Stage 2 Charge intermediate, Dimethyl Formamide, 1,2,4-Trizole, K2CO3 and Iso propanol in the reactor and maintain the reaction for 3 hrs at high temperature until the reaction is complete. Stage 3 Recover DMF under vacuum partially. Stage 4 Wash the reaction mass with water. Dry the wet cake in drier. Mass Balance
Mass balance of Propiconazole
IN PUT Kg OUT PUT Kg
2,4-dichloro benzyl chloride 845 4-propyl-1, 3-dioxolane 405 Organic effluent 1676 Reaction-1 Dimethyl sulphide 1176 KOH 676
DMF 1784 1,2,4 Triazol 284
K2CO3 68 Reqaction-2 Iso Propanol 236
DMF Recovery 1703 DMF Recovery Residue 81
effluent 2020 Water for washing 1351 Washing & Drying Drying loss 345 Propiconazole 1000
Total 6825 6825
M/s. Dhanuka Agritech Limited 34
18. Myclobutanil Manufacturing Process Step 1: Reaction Charge toluene, TEBAC and PCBCN in the reactor and stir for 30 minute. Then charge n-butyl bromide slowly in the reaction mass in 2-3 hrs and maintain the temperature for 3 hrs and check the sample for reaction complete. After reaction is complete add NaOH flakes slowly. Maintain the reaction mass for 4 hrs until the reaction is complete. Step 2: Washing Add toluene to the reaction mass as the mixture becomes thick and add water for washing. Separate the organic layer and send the aqueous layer to ETP. Step 3: Charge intermediate, Dibromomethane, TEBAC and NaOH 48% with water in the reactor and maintain the reaction for 3 hrs at high temperature until the reaction is complete. Separate the organic layer and send the aqueous layer to ETP. Toluene is recovered with distillation. Step 4: Charge intermediate, Dimethyl Formamide, 1,2,4-Trizole and NaOH in the reactor and maintain the reaction for 3 hrs at high temperature until the reaction is complete. Recover DMF under vacuum partially. Step 5: Wash the reaction mass with water and purify myclobutanil with toluene. Recover toluene by distillation. Chemical Reaction:
M/s. Dhanuka Agritech Limited 35
Flow diagram with Mass Balance:
MASS BALANCE OF MYCLOBUTANIL
INPUT KG OUTPUT KG
Toluene 425 PCBCN 750 n-butyl bromide 725 Reaction 1 NaOH 450 TEBAC 35
Water 2300 Washing Effluent 3430 Toluene 2500
NaOH, 48% 1100 Dibromomethane 775 Reaction Effluent 4470 TEBAC 50 Washing Toluene (recovery) 2875 Water 2500 Distillation Residue 220
1,2,4-triazole 335 Reaction DMF (recovery) 1900 NaOH 200 Distillation Residue 150 DMF 2000
Toluene (recovery) 1875 Toluene 2000 Residue 125 Reaction Water 2000 Effluent 2100 Distillation Myclobutanil 1000
TOTAL 18145 18145
M/s. Dhanuka Agritech Limited 36
19. Thiophenate methyl Manufacturing Process Ethylene dichloride is taken into a reactor provided with gear – motor agitator and distillation column – condenser assembly. Sodium Thiocyanate is added in Ethylene dichloride. Then is reacted with Methyl chloroformate in the ratio of 1 mol: 1 mol at temp. < 5 0 C and Methyl Thiocyanateformate is formed. Step: 2 In above ethylene dichloride layer, solution of O -PhenyleneDiamine prepared in EDC is added and after addition the reaction mass is heated to reflux for 3.0 hrs and then Reaction product is filtered off, washed with water and then dried and pulverized and packed as Thiophanate Methyl Technical. Filtrate and washes are collected and distilled to recover EDC. Final aqueous layer is then sent to ETP.
CHEMICAL REACTIONS:- 0 - 5 0 C CH OOCNCS NaCl CH3OCOCl + NaSCN 3 +
Methyl Chloro Sodium Methyl - Thiocynate Formate Formate
NH CSNHCOOCH 2 1. 0 - 5 0 C NH 3 + 2 CH3OOCNCS 2. 80 0 C NH 2 NH CSNHCOOCH3 O-Phynelene Thio PhanateMethyl Diamine
M/s. Dhanuka Agritech Limited 37
Flow diagram & Mass Balance:
THIOPHENATE METHYL
INPUT KG OUTPUT KG
EDC 2000 Sodium Thio cyanate 526 Methyl chloro formate 600 Reaction OPDA 350 EDC Recovery 1920 Water 3100
Filtration Liquid effluent 3000
Separation Process waste 378
Drying Loss 278 Drying & Packing Product 1000
Total 6576 6576
M/s. Dhanuka Agritech Limited 38
20. Tebuconazole Manufacturing Process Step: - 1Process for the preparation of Dimethyl Sulfide (Solvent) Dimethyl sulfate is reacted with aqueous solution of Sodium sulfide at 75 - 800C, to form dimethyl sulfide. The Product is condensed and collected in receiver. Then nitrogen is purged into the reactor to get maximum possible dimethyl sulfide recovery. Spent liquor containing sodium sulfate is then transferred to ETP.
(CH 3 ) 2 SO4 + Na 2 S +H 2 O = (CH 3 ) 2 S + Na2 SO4 + H 2 O Step: - 2Process for the preparation of Oxirane 1-(4-Chlorophenyl)-4, 4’-dimethyl-pent-3- one (CPDP) is made to react with dimethyl sulphate and potassium hydroxide in presence of dimethyl sulfide to give tebuoxirane. The solvent dimethyl sulfide is recovered by distillation and then the intermediate product (tebuoxirane) separated from the reactor. Then water is added in the reactor to dissolve salt formed during the reaction and transferred to ETP. TEBU OXIRANE SYNTHESIS
DMS + Cl CH2 CH2COC(CH3)3 (CH3)2SO4 + 2 KOH
1-(4-CHLOROPHENYL)-4,4'- DIMETHYL-PENT-3-ONE (CPDP) O CH2
+ K2SO4 + H2O Cl CH2 CH2-C-C(CH3)3
Oxirane Step: - 3CONDENSATION In dimethyl formamide, potassium carbonate, 1, 2, 4-triazole is added and then above prepared oxirane is added at reflux temperature. After completion of the reaction the mass is filtered and then solvent DMF is distilled out. Then the product Tebuconazole is isolated by adding water. The slurry is filtered, centrifuged and dried. The filtered potassium carbonate sludge is washed with DMF to recover the product. Treated sludge is then transferred to solid waste. The mother liquor is transferred to ETP.
Chemical Reaction
M/s. Dhanuka Agritech Limited 39
H O CH2 N DMF CH -C-C(CH ) N K CO Cl CH2 2 3 3 + + 2 3 N 1H-1,2,4- Oxirane Triazole
OH
CH CH -C-C(CH ) Cl 2 2 3 3 + K2CO3
CH2
N N N
Tebuconazole
Flow diagram & Mass Balance:
TEBUCONAZOLE
INPUT KG OUTPUT KG Dimethyl Sulfate 502 Sodium sulfide 26 Ketal 755 KOH 323 DMF Recovery 1395
1,2,4-triazole 255 REACTION Residue 25 K2CO3 40 DMF 1420 Water 7750
effluent 9547 Filtration
Solid waste 49 Separation
Drying Loss 475 Drying Tebuconazole 1000 Total 11071 11071
M/s. Dhanuka Agritech Limited 40
21. Mancozeb Technical Manufacturing Process: Stage 1 Carbon Disulphide and Ethylene Diamine and Sodium Hydroxide are reacted in the presence of water to form the Di Sodium salt of Ethylene BisDithio Carbamate Hexa hydrate (DBH). Stage 2 Di Sodium salt of Ethylene BisDithio Carbamate Hexa hydrate is reacted with manganese sulphate to form manganese salt of Bis-Dithio Carbamate. Stage 3 The manganese salt further reacts with Zinc Sulphate to convert into Mancozeb. Slurry is initially spray dried and subsequently vacuum dried for Mancozeb powder formulation. Chemical Reaction Stage 1
Stage 2
Stage 3
M/s. Dhanuka Agritech Limited 41
Mass Balance
MANCOZEB
INPUT KG OUTPUT KG
EDA 198 Water 200 SODIUM SALT FORMATION NaOH (48%) 570 CS2 515
STRIPPING
Water 25 WASHING
MnSO4 85 Water 450 MANCOZEB SALT FORMATION MnSO4 (27%) 1790
Water 210 HOMONIZATION ZnSO4 (32%) 138
Water 1180 WASHING & FILTRATION Effluent 3951
Drying Loss 410 DRYING Product 1000
TOTAL 5361 5361
M/s. Dhanuka Agritech Limited 42
22. Propineb Technical Carbon disulfide is charged into reactor with diaminopropane. Mass is allowed to react at controlled operating conditions (20 – 25°C). 15% ammonia solution is dropped in the reactor gradually. After cooking the mass for 2 hrs, at the same temperature the reaction mass is reacted with zinc sulfate solution in presence of water. Crude mass is then centrifuged, washed with water and dried to get technical grade Propineb.
Chemical Reaction:
Flow Diagram & Mass Balance
PROPINEB T
INPUT KG OUTPUT KG
Carbon Disulfide 717 CS2 Recycle 142 Di-Amino Propane 285 REACTOR Residue 325 15% Ammonia Solution 1900
Zinc Sulphate 1160 REACTOR Water 5700
Water Washing 4500 Effluent 12771 CENTRIFUGE, WASHING & Drying Loss 324 DRYING Product 1000
TOTAL 14262 14562
M/s. Dhanuka Agritech Limited 43
23. Thiamethoxam
Manufacturing Process Step-I:
CCMT and MNIO are reacted in DMF media using K2CO3 as catalyst and reaction mass thus obtained is taken for water washing. Step-II: Organic mass obtained in step-I is of crude thiamethoxam and is purified with methanol and is dried. Chemical Reaction:
Flow diagram with Mass Balance
MASS BALANCE OF THIAMETHOXAM
INPUT KG OUTPUT KG
CCMT 771 MNIO 734 Stage 1 DMF 697 Reaction K2CO3 850
Stage 2 Water 1628 DMF Recovery 670 Filtration Effluent 2376
Effluent 973 Purification by 80% Methanol 1600 Methanol Recovery 1261 Crystalization Thiamethoxam Tech. 1000
Total 6280 6280
M/s. Dhanuka Agritech Limited 44
24. Buprofezin
Manufacturing Process: Step-1 Charge PNNCC, Toluene, and lime in the reaction vessel. Stir the reaction mass for 2-3 hours. Charge Thiourea slowly in the reaction mass in 2-3 hours and stir the reaction mass at higher temperature until raw material is totally consumed. Step-2 After completion of reaction, Filter the reaction mass to isolate inorganic solid. Step-3 Wash inorganic solid with toluene. Recover toluene under vacuum from clear organic phase. Step-4 Add EDC in the crude solid. Charge TEA slowly at room temperature and stir the reaction mass for 3 hours. Step-5 Reaction mass is washed with water. Separate the layers. Recover EDC under vacuum partially. Step-6 Cool the conc. mass slowly and filter the crystals. Dry the wet product at 50 – 65%.
CHEMICAL REA CTION:
CH2Cl O i-Pr N t-Bu N C NO 2 NH S N i-Pr + S C NH N O t-Bu
p - Nitrophenyl N - Chloromethyl N-isopropyl- N-tert-butyl BUPROFEZIN Carbamate Thiourea
M/s. Dhanuka Agritech Limited 45
Flow diagram & Mass Balance:
Mass balance of Buprofezin
IN PUT Kg Kg OUT PUT
1-isopropyl 3-t-butyl thiourea 500 N-chloromethyl -N-phenyl 640 carbamoyl chloride Reactor MCB 2400 Ammonium bicarbomate 2400 Water 2000
4500 Effluent Separation
2380 MCB recovery Distillation
Methanol 1400 Crystallization
1300 Methanol Recovery Filtration & Drying 160 Drying loss 1000 Buprofezin
Total 9340 9340
M/s. Dhanuka Agritech Limited 46
25. Daifenthiuron Technical Manufacturing Process 2,6-Diisopropyl-4-phenoxylbenzeamine reacted with hydrochloric acid to give 2,6- Diisopropyl-4-phenoxylbenzeamine hydrochloride, which reacts with NaSCN in the presence of xylene as solvent to give 1-(2,6-diisopropyl-4-phenoxyphenyl)-thioures. This is heated to reflux to yield 1,3-dissopropyl-2-isothiocyanato-5-phenoxybenzene. Finally condensed with tert-butyl amine to give Diafenthiuron Technical. Chemical Reaction:
Flow diagram with Mass Balance
MASS BALANCE OF DIAFENTHIURON
INPUT KGS OUTPUT KGS
Xylene 1237 DIPBA 826 Reaction 1 NaSCN 267 HCl, 30% 384
Water 1051 Effluent 1603 Washing
tert-butylamine 219 Reaction Diafenthiuron 1000 Filtration
Xylene (recovery) 1159 Distillation Xylene (loss) 78 Organic residue 144
TOTAL 3984 3984
M/s. Dhanuka Agritech Limited 47
26. Imidacloprid Technical MANUFACTURING PROCESS 2 – Chloro, 5 – Chloro methyl Pyridine (CCMP) is reacted with N – Nitro iminoIdmidazolidine (N-Nll) in present of catalyst and solvent. The Hydrochloric acid, which is formed during the reaction, is scavenged by putting Sodium carbonate as acid scavenger. The resulting mass is diluted by water and filtered to remove the salts of Sodium Chloride (NaCl) & Sodium bicarbonate. The organic mass is then treated with water and finally solvent is removed by distillation. The concentrated mass is then crystallized to get pure product – Imidacloprid (Tech). Finally Toxic Effluent which contains traces of Pesticides is taken to Hydrolysis stage for detoxification. Where aqueous mass is treated at high temperature. By Alkali for the rapid hydrolysis of pesticides to simpler non-toxic compounds. CHEMICAL REACTION
N-NO2 CATALYST CH2Cl + SOLVENT + Na2CO3 + HH--NN N-H CL N
CCMP N-NII M.W.162
N-NO2
CH2 - N N-H + NaCl + NAHCO3
CL N IMIDACLOPRID
M/s. Dhanuka Agritech Limited 48
Flow diagram & Mass Balance:
IMIDACLOPRID
INPUT KG OUTPUT KG
CCMP 856 N-NII 715 Recovered solvent DMF 1983 CONDENSATION & SOLVENT DMF 2091 DMF loss 67 RECOVER Catalyst 10 Na2CO3 671
Water 951 WATER WASH Effluent 1846
Recovered Methanol 361 Methanol 380 CRYSTALLIZATION, FILTRATION & Residue 20 DRYING Drying Loss 397 Imidacloprid Tech. 1000
Total 5674 5674
M/s. Dhanuka Agritech Limited 49
27. Fipronil Process Description Fipronil Pyrazole and Ammonium Thiocyanate are condensed in the presence of oxidant Oxone® and MeOH as solvent. Reaction is completed in 3.0 hrs at 39 – 40 °C. An inorganic salt is filtered, washed with MeOH and dried. MeOH is recovered from filtrate partially under reduced pressure. Recovered MeOH is recycled. Partially concentrated mass is dumped in to water at RT. Stirred for 3 – 4 Hrs at RT. Product (FPT) is filtered at RT and washed with water. Product (FPT) is dried at 50 °C till constant weight is obtained. Fipronil Thiocyanate and CF3Br are reacting in the presence of SO2 (g), Sodium formate and DMF as solvent. Reaction is carried out under pressure in Auto clave at 70°c. Reaction mixture is cooled down at 40 °C. The pressure in autoclave is released and scrubbed in 7 % NaOCl soln. Reaction mass is transferred to mixture of water + Isopropyl acetate solution and stirred for ½ hrs at RT. Organic and Aq. phases are separated. Aq. phase is extracted with IPAc and then treated with NaOCl solution and incinerated. Combined organic phase is washed with water. Washed organic phase taken for partial IPAc recovery under reduced pressure. Recovered IPAc is recycled. Partial concentrated mass is taken for crystallization. Product is crystallized out and filtered out and dried. Mother liquor is subjected for isopropyl acetate recovery. Reco. IPAc is recycled and organic residue is incinerated. Des-Oxy Fipronil, Trifluoro acetic acid and chloro benzene are mixed at RT.
H2O2 is added for 30 min. at low temperature. After completion of reaction chloro benzene is charged and CF3COOH is distilled out. Product is crystallized out in Ethanol and water, filtered and dried.
M/s. Dhanuka Agritech Limited 50
Chemical Reaction:
Flow diagram & Mass Balance:
Mass balance of Fipronil
IN PUT Kg Kg OUT PUT CF3COOH 2500 2400 CF3COOH recovery Monochloro benzene 1500 1475 MCB recovery Oxidation H2O2 1040 1165 Solid waste Thiopyrazole derivative 2500
Water 3500 4625 Effluent Washing
375 Drying Loss Drying & Packing 1000 Fipronil
Total 11040 11040
M/s. Dhanuka Agritech Limited 51
28. Chlorpyriphos MANUFACTURING PROCESS Sodium Salt of trichloroPyridinol (NaTCP) is reacted with Diethyl ThioPhosphoryl Chloride (DETC) in presence of catalyst and solvent to get Chlorpyrifos Tech. of 94% purity. Recovered solvent is recycled in next batch. Finally Toxin Effluent which contains traces of pesticides is taken to Hydrolysis stage for detoxification. Where Aqueous Mass is treated at high temp. By Alkali for the rapid hydrolysis of pesticides to simpler non- toxic compounds. CHEMICAL REACTION
Cl S Cl OC2H5 + Cl P + EDC + CATALYST Cl ONa OC2H5 N
Cl Cl S OC2H5 + NaCl O P Cl N OC2H5
Flow diagram & Mass Balance:
Mass balance of Chlorpyrifos
INPUT KG OUTPUT KG
NaTCP 658 Recovered solvent- EDC 2496 DETC 560 Stage 1 EDC loss 276 Water for Reaction 655 CPP effluent 3230 Water for washing 2716 Preparation Drying loss 354 Catalyst 8 Chlorpyrifos 1000 EDC 2759
Aqueous effluent 3530 Stage 2 C. S. lye 48% 43 Alkali Wet cake NaTCP 30 Hydrolysis
Stage 3 Distilled Water 3322 TEE Detoxified Aq. Mass 184 Distillation Water loss 37
Total 10929 10929
M/s. Dhanuka Agritech Limited 52
29. Metalyxyl MANUFACTURING PROCESS N-(2, 6 – Dimethyl Phenyl) Alanine – Methyl Ester reacts with Methoxy Acetyl Chloride in presence of catalyst and solvent to get Metalaxyl solution. This solution is then wasted with water & solvent is distilled out to get Metalaxyl (Tech). Finally Toxic Effluent which contains traces of Pesticides is taken to Hydrolysis stage for detoxification Where Aqueous Mass is treated at high temp. By Alkali for the rapid hydrolysis of pesticides to simpler non-toxic compounds. CHEMICAL REACTION
CH3
CH3
CH-COOCH3 CATALYST N + CH3-0CH2COCl H TOLUENE +WATER
CH3
CH3 CH3
CH-COOCH3 N + HCl C-CH2OCH3
CH3 O METALXYL
Flow diagram & Mass Balance:
METALAXYL
INPUT KG OUTPUT KG
N-(2,6- Dimethyl phenyl) 750 alanine-methyl ester Stage 1 methoxy acetyl chloride 397 Aqueous Effluent 78 Catalyst 15 Preparation 30% HCl solution 438
Toluene 2206 Water for washing 49 Water for HCl scrubbing 306
Stage 2 Solvent Recovered solvent 2098 recovery Solvent loss 108 Metalaxyl Tech. 1000
Aqueous Effluent 78 Stage 3 Alkali Detoxified Aqueous mass 128 C.S.Lye 48% 49 Hydrolysis (Detoxification)
Total 3850 3850
M/s. Dhanuka Agritech Limited 53
30. Alpha Cypermethrin Manufacturing Process: Metaphenoxy Benzaldehyde is reacted with sodium cyanide to form Metaphenoxy Benzaldehyde cyanohydrin as intermediate. This on Reaction with Cyprmethric acid chloride (CMAC) of high cis> 96% form the product Alpha-Cypermethrin oil. In this process n-Hexane is used as solvent along with phase transfer catalyst. The reaction is washed by Soda-ash solution and plane water. The n-Hexane is then stripped off to get pure Alpha-Cypermethrin oil in Racemic form which is epimerised by catalyst in presence of IPA- solvent to form the final product Alpha Cypermethrin of >95% Purity. Aqueous layers of reaction as well as washing which contains traces of sodium cyanide is treated by sodium hypochlorite 8% solution to kill cyanide up to 0.2 PPM level, which is ten mixed up with main effluent treatment streams (ETP) and after further treatment drained to gutter. Chemical Reaction:
M/s. Dhanuka Agritech Limited 54
Flow diagram & Mass Balance:
Alpha - Cyperrmethrin Tech.
INPUT KG OUTPUT KG
MPBAD 714 CMAC +High Cis 835 Effluent 3022 NaCN 195 Recovered Hexane 3908 Condensation Water 1428 & Residue 210 n-Hexane (F) 492 Washing n-Hexane (R) 3808 Catalyst 14 NaCN layer Soda ash Soln. 5% 1400 Water for Washings 1400
IPA-Solvent (F) 351 IPA Recovery 1375 IPA-Solvent (R) 1098 Residue 351 Catalyst 86 Epimerisation Catalyst 86
IPA + Solvent (F) 280 Recover IPA 1105 IPA + Solvent (R) 860 Crystalization Resdue 56 Alph Cypermethrin 1000
NaCN layer
10% Sodium Detoxification Hypochlorite 2150 Detoxified Effluent 3998
TOTAL 15111 TOTAL 15111
M/s. Dhanuka Agritech Limited 55
31. Cypermethrin Manufacturing Process Meta Phenoxy Benzaldehyde is reacted with Sodium Cyanide to form Meta Phenoxy Benzaldehyde Cyanohydrin as an intermediate. This on reaction with Cypermethric Acid Chloride forms the final Product Cypermethrin. In this process n-Hexane is used as solvent along with phase transfer Catalyst. The reaction mass of Cypermethrin is washed by Soda Ash solution & Water. Finally n-Hexane is stripped off to get pure Cypermethrin. Aqueous layer which contain traces of Sodium Cyanide is detoxified by the treatment of Sodium Hypochlorite 8 – 10% Solution to < 0.2 ppm Level. Chemical Reaction
M/s. Dhanuka Agritech Limited 56
Mass Balance
Mass balance of Cypermethrin
INPUT KG OUTPUT KG
CMAC 590 effluent 2406 MPB 485 NaCN 145 Condensation PTC 6 Water 350 Hexane 1090
Hypochlorite 1430 Cyanide detoxification
Water 200 Washing Hypochlorite 200
Hexane recovery 1045 Residue 45 Distillation Product 1000
Total 4496 4496
M/s. Dhanuka Agritech Limited 57
32. Lambda Cyhalothrin Manufacturing Process Meta Phenoxy Benzaldehyde is reacted with Sodium Cyanide to form Meta Phenoxy Benzaldehyde Cyanhydrin as an intermediate. This on reaction with FluoroPropenyl Acid Chloride (TFP Acid Chloride) form the Product Cyhalothrin. in this process n - Hexane is used as solvent along with phase transfer catalyst. The reaction mass of Cyhalothrin is washed by Soda Ash solution as well as water. Solvent n-Hexane is stripped off toget pure Cyhalothrin oil. Finally Cyhalothrin oil is epimerised to give Lambda Cyhalothrin of 85%. An aqueous layer which contains traces of Sodium Cyanide is detoxified by the treatment of Sodium Hypochlorite Solution (8-10%) up to < 0.2 ppm level. Then it is mixed up with main ETP stream for further treatment & finally drained to gutter. Chemical Reaction:
Lambda Cyhalothrin
CH H C 3 O O F C 3 3 n-Haxene C = CH - CH - CH - C - Cl + NaCN + C Catalyst Cl H O
Cyhalothrin Sodium Cyanide (MW- 449.9) Meta Phenoxy (MW- 49.1) Benzaldehyde (MW- 198)
CH H3C 3 O CN F3C C = CH - CH - CH - C - O - C Epimerization IPA, Catalyst Cl H O
Cyhalothrin + NaCl (MW- 449.9) Sodium Chloride
(MW- 58.5)
CH H3C 3 O CN F3C C = CH - CH - CH - C - O - C
Cl H O
Lambda Cyhaloyhrin
(MW- 449.9)
M/s. Dhanuka Agritech Limited 58
Flow diagram & Mass Balance:
Lambda Cyhalothrin INPUT KG OUTPUT KG
MPBAD 448 TP Acid Chloride 610 Effluent 1934 NaCN 122 Water for Rexn 448 Recovered Hexane 2276 Condensation, Washing n-Hexane (F) 114 & Residue 114 n-Hexane (R) 2267 Distillation Catalyst 10 NaCN layer Soda ash Soln. 5% 952 Water for Washings 952
IPA loss 52 IPA-Solvent (F) 52 Recovered IPA 948 IPA-Solvent (R) 948 Epimerisation Recovered Catalyst 152 Catalyst - 2 152 Lambda Cyhalothrin 1000
NaCN layer
8-10 % Sodium Hypochlorite1429 Detoxification Detoxified Effluent 2028
TOTAL 8504 TOTAL 8504
M/s. Dhanuka Agritech Limited 59
33. Novaluron Manufacturing Process 1. Novaluron technical is prepared by reaction of 2,6-difluoro benzoyl isocyanate with 2-chloro-4-amino phenoxy ether in presence of monochloro benzene as a solvent. 2. After completion of the reaction, the reaction mass is cooled, filtered and washed with water. 3. Novaluron wet cake is then recrystallised with toluene, filtered and dried to get Novaluron technica.l Mass Balance
Mass balance of Novaluron
IN PUT Kg OUT PUT Kg
2,6-difluoro benzoyl isocyanate 321 2-chloro-4-amino phenoxy ether 794 Stage 1 Reaction Monochloro benzene 547
Stage 2 Cooled & Filtered Mother liquor 548
Stage 3 Water 968 Water washing effluent 1098
Recovered toluene 887 Toluene 903 Stage 4 Novaluron 1000 Crystalisation
Total 3533 3533
M/s. Dhanuka Agritech Limited 60
34. Bifenthrin Manufacturing Process for Bifenthrin Step-I: Charge DMF, 2-Methyl 3-biphenyl methyl chloride (BPC), Cyhalothric acid (MTH-Acid),
K2CO3 in presence of catalyst (TBAB) under stirring. Heat it to 60°C and maintain. Remove DMF from the reaction mixture. (8 hrs). Step-II: Add water to the reaction mass and extract with n-Hexane. Take the organic layer by
discarding aqueous layer and wash the organic layer with 10% NaHCO3. Finally wash the organic layer with water. Remove hexane by distillation. (4 hrs) Step-III: The crude Bifenthrin was finally crystallized with 10% methanol in n-Hexane to obtain the pure Bifenthrin (4 hrs).
Chemical Reaction
M/s. Dhanuka Agritech Limited 61
Mass Balance
MASS BALANCE OF BIFENTHRIN
IN PUT KG OUT PUT KG
MTH Acid 629 BPC 568 Stage 1 DMF 1316 Reaction K2CO3 182
DMF Recovery 1237 Recovery Residue 79
Hexane 689 Water 689 Effluent 950 Washing 10% NaHCO3 Solution 66
Recovery Hexane Recovery 618 Residue 71
10% Methanol in Hexane 1974 Effluent 613 Methanol 158 Crystalization Hexane 1711 Water 395 Residue 71 Bifenthrin 1000
Recycle
Total 6508 6508
M/s. Dhanuka Agritech Limited 62
35. Abamectin Manufacturing process It is a mixture containing 80% avermectin-B1a (i) and 20% avermectin B1b (ii). It is isolated from fermentation of Streptomyces savermitis with an anthelminic and acaricidal. The molecular formula is as below: C48H72O14 (avermectin B1a) + C47H70O14 (avermectin B1b)
Chemical Reaction
M/s. Dhanuka Agritech Limited 63
Mass Balance
Mass balance of Abamectin
IN PUT Kg OUT PUT Kg
Streptomycess avermemitis 556 Anthelminic 550 FERMENTATION acaricidal 570 Water 5222
Crude abamectin 1667 ISOLATION effluent 5898
Crude abamectin 1667 Recovered Methanol 2111 Methanol 2222 PURIFICATION & Residue 111 CRYSTALIZATION Abamectin 1000
Total 10787 10787
M/s. Dhanuka Agritech Limited 64
36. Emmamectin Benzoate Technical Manufacturing process It is a composite mixture of 90% emamectin B1a and 10% emamectin B1b as their benzoate salts. It is isolated from fermentation of streptomycessavermitis with an anthelminic and acaricidal. Then methylamine is added in the mixture. Finally benzoate salt is prepared by reaction with methyl benzoate. The molecular formula is as below: C49H75NO13 (emamectin B1a) + C48H73NO13 (emamectin B1b)
Chemical Reaction
M/s. Dhanuka Agritech Limited 65
Mass Balance
Mass balance of Emamectin benzoate
IN PUT Kg OUT PUT Kg
Streptomycess avermemitis 455 Anthelminic 909 FORMENTATION acaricidal 909 Water 8182
Methyl amine 182 effluent 9182 ADDITION & ISOLATION
Methyl benzoate 227 BENZYLATION Water 5091 effluent 4136
Recovered Methanol 2418 PURIFICATION & Effluent 1819 Methanol 2727 CRYSTALIZATION Residue 127 Emamectin Benzoate 1000
Total 18682 18682
M/s. Dhanuka Agritech Limited 66
37. Azoxystrobin Process Description 2,6 Dichloro Pyrimidine and anhydrous Potassium carbonate is charged in DMF. Solution of Methyl- 2-(2 Hydroxy phenyl)-3 methoxy Propenoate in DMF is charged to above solution. When addition is over, warm the reaction mass to complete the reaction. Charge 2 cyano Phenol to the reaction mass and add catalytic amount of Cuprous Chloride and heat the reaction mass to 1000C for few hours. Filter the reaction mass to remove inorganics and distilled out DMF from reaction mass. Add hexane and wash the reaction mass with dilute caustic to remove unreacted cyano phenol from the reaction mass. Crystallize the crude with ether/dichloromethane and n Hexane, precipitate is filtered, centrifuged and dried to get technical grade white crystalline solid Chemical Reaction O CH O CH3 3 O O O O CH3 CH3 CH4 Cl Cl
OH + N N O Cl HCl + N N 208 149 320.5 36.5 O CH 3 O CH3 O O CH3 O O CH3
N N + Cl HO O O O + HCl
N N N N
Azoxy Strobin 320.5 119 403 36.5
O K CO H O 2 3 + 2 HCl 2 K Cl 2 + + O 138 36.5 74.5 18 44
M/s. Dhanuka Agritech Limited 67
Flow Diagram & Mass Balance :
AZOXYSTROBIN
INPUT KG OUTPUT KG
2,6 Diachloro Pyrimidine 411 DMF 5405 MHPMP 573 REACTION Potassium Carbonate 919 Cyano Phenol 328 Cuprus Chloride 11
Inorganic Salt 1131 FILTRATION
DMF Recovery 5297 DISTILLATION Residue 218
Caustic Soda 22 Water 541 WASHING & SEPERATION effluent 564 Hexane 4324
MDC Recovery 2119 Dichloro Methane 2162 Hexane Recovery 4238 CRYSTALIZATION & SOLVENT Residue 129 RECOVERY Product 1000
TOTAL 14696 14696
M/s. Dhanuka Agritech Limited 68
38. Deltamethrin Technical Take Deltametric Acid Chloride, Benzene and Catalyst in the rector. Add 2- cyno-3-phenoxy benzyl alcohol slowly at 20°C till reaction is completed. After completion transfer the reaction mass to another reactor and give water wash. Separate aqueous layer in other reactor and recover pyridine by caustic Soda washing and transfer acidic effluent to ETP for treatment. Organic layer is again wash with water in another reactor and separate out aqueous layer and organic layer. Transfer aqueous layer to ETP and organic layer to distillation unit. Separate out Benzene under vacuum and cool the mass. Pack Deltamethrin in drum for dispatch.
Chemical Reaction:
M/s. Dhanuka Agritech Limited 69
Mass Balance:
Deltamethrin
Input (KG) Output (KG)
Catalyst 180 DAC 550 Reaction CPBA 500 Benzene 600
NaOH 100 Washing/ Catalyst 180 Separation effluent 230
Washing/ effluent 300 Separation Water 350
Distillation Benzene 570 Product 1000
Total 2280 2280
M/s. Dhanuka Agritech Limited 70
39. Acetamiprid Technical Manufacturing Process N-Cyano methyl Acetamidate (NCMA) is reacted with 2-Chloro 5-(methyl amino methyl) Pyridine (CMAMP) in solvent media. After the reaction is completed the product is filtered and solvent is concentrated to yield more products as well as recover solvent which is recycled. Chemical Reaction
CH2NHCH3 H3C
C N CN + Cl H3C N
CH3
CH N C N CN 2 C + CH3OH C CH3
Cl C N C
ACETAMIPRID
Flow diagram &C Mass Balance C
C ACETAMIPIRID
C INPUT KG OUTPUT KG
NCMA 520 CMAMP 700 CONDENSATION Methanol 1800
Acetamiprid Tech. 1000 Methanol for washing 150 FILTRATION & DRYING
Methanol recovery 1900 DISTILLATION OF ML Residue 270
Total 3170 3170
M/s. Dhanuka Agritech Limited 71
40. Trizophos Technical Manufacturing Process: 1 Phenyl-3-hydroxy-1, 2, 4- triazole, Dichloroethane and Triethyl amine are heated to 40-42° C in the reactor. Then O, O–diethyl- thiophosphyoryl chloride is added slowly to the reaction mass. After completion of the reaction, mass is cooled and triethylamine hydrochloride is filtered off and send to recovery section. Solvent is recovered by distillation from filtrate. Product obtained is then packed in drum for dispatch. Chemical Reaction:
Mass Balance:
Triazophos
Input (KG) Output (KG)
1-phenyl-2-hydroxy-1,2,4 triazole 570 Triethylamine 390 Reaction EDC 1140 o,o diethylthiophoryl chloride 660
Water 2110 TEA recycle 330 Caustic Lye (48%) 250 Filtration Effluent 2720
Distillation EDC 1070 Triazophos 1000
M/s. Dhanuka Agritech Limited 72
41. Propargite Technical STEP-I: 1,2 – Cychlo hexane oxide is converted in to its K –Salt of diole in the presence of KOH at 175°C for 6 hrs and pressure 1.7 MPa. Then it reacts with Thionyl chloride in the presence of toluene as solvent gives 1 – Chloro 2 – hydroxy cyclo hexane K – Salt. STEP-II: Propargyl alcohol is reacts with Thionyl chloride at 27°C for 7 hrs and gives Propargyl sulfonyl chloride. STEP-III: Intermediates are obtained in step – I & II are reacting with p – tert. Butyl phenol in the presence of toluene under controlled condition gives Propargite. Chemical Reaction: STEP - I
Cl Ph-CH3 O + KOH + SOCl2 OK
1,2 - Cyclohexene Pottasium Thionyl Hydroxide Chloride 1-Chloro 2 - hydroxy Cyclohexane - K - Salt [286 - 20 - 4]
STEP - II
Ph-CH3 O HC C CH2OH + SOCl2 HC C CH2 - O - S - Cl
Propargyl Alcohol Thionyl Chloride
[107 - 19 - 7]
STEP - III Bu - t Bu - t Cl O Ph-CH3 O + + HC C CH2 - O - S - Cl H
OK O S C C CH OH O H p - tert. Butyl Phenol Propargite [98 - 54 - 5] [2312 - 35 - 8]
M/s. Dhanuka Agritech Limited 73
Flow Diagram & Mass Balance:
PROPARGITE
INPUT KG OUTPUT KG
1,2-Cyclohexene Oxide 439 Potassium Hydroxide (KOH) 290 CONDENSATION Toluene 1607
HCl to Scrubber 161 Thionyl Chloride (SOCl2) 523 STEP 1 CHLORONATION SO2 to Scrubber 281
Proporgyl Alcohol 236 Thionyl Chloride 525 STEP 2 SULFONYLATION HCl Scrubber 154 Toulene 1071
p - tert. Butyl Alcohol 633 HCl 153 STEP 3 CONDENSATION
Toluene recovery 2525 Brine Solution(15% NaCl) 3214 effluent 3845 SEPERATION & TOLUENE Residue 240 RECOVERY FILTRATION Drying Loss 179 Propargite 1000
TOTAL 8538 8538
M/s. Dhanuka Agritech Limited 74
42. Mono Chloro Acetic Acid (MCA): Manufacturing Process Charge Acetic Acid in the reactor. Heat the reactor to 100oC through hot water circulation and start chlorination. Acetic acid is converted into Mono chloro Acetic Acid in presence of suitable catalyst. During the process, HCl gas is generated, which is scrubbed through scrubber and dissolved in water to get 30% HCl liquor. After completion of reaction, the mass is transferred in buckets for crystallization where natural followed by induced cooling takes place. After about 70 hrs, pure MCA crystals are recovered. After centrifuging, MCA product is ready for packing. The Mother Liquor (ML) generated from centrifuge is separated out and sold as ML of MCA. Chemical Reaction:
CH3COOH + Cl2 ------> ClCH2COOH + HCl Acetic Mono chloro Hydrochloric Acid Chlorine acetic Acid Acid
Mass balance and process flow diagram:
Mono Chloro Acetic Acid
Input kg output kg
Acetic Acid 870 Sulphur mono Chloride 38 HCl(30%) 621 GLR Liq. Chlorine 900 Acetic Anhydride 14
Crystallization
Mother Liquor of MCA 200 Centrifuge Product 1000
TOTAL 1821 1821
M/s. Dhanuka Agritech Limited 75
43. IDA-HCl Stage 1 Charge DM water, Calcium hydroxide and Ammonia solution in the reaction vessel. Stir the reaction mass for 1 hour. Charge Mono Chloro acetic acid slowly in the reaction mass in 4-6 hrs and stir the reaction mass at 400C ±5 until reaction is complete and heat the reaction mixture at 700C temperature for acidification with HCl. Stage 2 After complete the reaction material, cool it at 100C and filter the IDA-HCl. Dry the wet product at 800C.
Chemical Reaction:
CaOH + 2 ClCH2COOH + NH3 COOH-CH2-NH-CH2-COOH●HCl
Calcium MCA Ammonia Imino diacetic acid Hydroxide
Flow Diagram & Mass Balance:
Mass balance of IDA-HCl
IN PUT Kg OUT PUT Kg
MCA 1476 Calcium Hydroxide 1146
NH3 Solution 796 Stage 1 IDA-HCl formation DM Water 1010 HCl 32% 2689
effluent 7117 Filteration
Drying & Packing Drying Loss 375 Product 1000
Total 7117 7117
M/s. Dhanuka Agritech Limited 76
44. PMIDA Stage 1 Charge DM water, IDA-HCl, Phosphorus acid and HCl in the reaction vessel. Stir the reaction mass for 1 hour. Charge Formaldehyde solution slowly in the reaction mass in 4 hrs and stir the reaction mass at 1000C until reaction is complete. Stage 2 After complete the reaction material, cool it at 300C and neutralize with 30% caustic solution. Stage 3 After neutralization cool it the material at 100C and filter and wash with water. Dry the wet PMIDA at 1000C. Mass Balance:
Mass balance of PMIDA
IN PUT Kg OUT PUT Kg
IDA-HCl 1020 DM water 475 Stage 1 Phosphorous acid 693 PMIDA HCl 32% 584 formation Formaldehyde solution 792
Caustic solution 30% 1564 Stage 2 Neutralization
Stage 3 effluent 3756 Fileration, Washing, Centrifuge
Drying Loss 372 Drying & Packing Product 1000
Total 5128 5128
M/s. Dhanuka Agritech Limited 77
45. CMAC Manufacturing Process CNB Formation: Carbonatetrachloride is reacted with acrilonitrile in MSGL reactor. Catalyst is used and solvent is acetonitrile. CBN Purification: CBN is purified by distillation, forecut is collected separately and pure CBN is sent down for further processing. CBA Formation: Pure CBN is hydrolyzed by dilute Sulfuric acid in MSGL reactor to yield CBA. CBC Reaction: CBA is reacted with Thionyl chloride. Hydrochloric acid gas and SO2 gas are generated during this reaction. These gases are scrubbed through a sequential scrubbing system. CBC Purification: Crude CBC and purified by vacuum distillation in MSGL reactor. Vacuum device used is rejector. 2CB Reaction: Pure CBC and Isobutylene are reacted in presence of Tri ethyl amine HCl in solvent Hexane Tri ethyl amine. HCl dissolved in water in the process is sent for Tri ethyl amine recovery. 2CB Purification and Crystallization:2CB reaction mass is transferred to crystallizer. Excess solvent is recovered and reaction mass is chilled below 50 and then centrifuged. 4CB Reaction: The 2CB crystals are charged in MSGL reactor and isomerized using Tri ethyl amine. Favorskireaction: The above mass is heated with caustic solution to get sodium salt of CMA. Dehydro-halogenation: The above mass is heated with caustic solution to get sodium salt of CMA. IsolatioN: This mass is acidified with sulphuric acid to get Cypermethric Acid (CMA) with Hexane as solvent. CMA Concentration: From the above mass excess Hexane is distilled out and CMA slurry is transferred for CMAC reaction. CMAC Reaction: CMA is reacted with Thionyl chloride. SO2 and HCl gas are generated in this process. These gases are scrubbed through a sequential scrubbing system. CMAC Purification: Crude CMAC is distilled out by vacuum distillation in MSGL purified CMAC is packed in lined drums as per requirement.
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Flow Diagram & Mass Balance:
CMAC
INPUT KG OUTPUT KG
CTC 1696 CTC recycled 208 CAN 505 Residue 100 Acetonitrile 36 Effluent 401 CBN FORMATION Water 286 Catalyst 1 19 Dea. HCl 19
H2SO4 1610 Effluent 3360 CBA FORMATION Water 1903
SOCl2 1251 DMF Recycled 38 DMF 40 CBC FORMATION Gas stream 1089 residue 217
IB 595 Effluent 890 Hexane 1717 Hexane + IB refluxed 953 TEA 630 2CB Hexane recycled 1182 Water 1487 Effluent 2722 10% NaHCO3 826
Water 2975 Hexane recycled 2418 Caustic lye 488 Effluent 3727 H2SO4 235 CMA FORMATION Residue 127 Hexane 2545 Catalyst 2 9
SOCl2 705 Gas stream 614 CMAC FORMATION Residue 113
Drying Loss 418 Drying & Packing Product 1000
Total 19577 19577
M/s. Dhanuka Agritech Limited 79
46. MPBD Manufacturing process A. Chloro Bromination Bromination of Benzaldehyde is carried out in a glass-lined reactor in presence of Aluminum Chloride and in solvent EDC. The organic layer of this reaction mixture is drowned in water and given a water wash. The solvent is distilled out to given pure intermediate Meta BromoBenazaldehyde (MBB). B. MBB Condensation This intermediate reacts with Phenol is SS reactor in presence of Potassium hydroxide and a catalyst to give crude Metaphenoxyenzaldehyde (MPBD). This mass is fraction distilled under vacuum to yield the pure product, and subsequently packed indrums. Flow Diagram & Mass Balance:
MPBD
INPUT KG OUTPUT KG
Benzaldehyde 748 AlCl3 1230 Gas Stream 273 EDC 2200 Chloro-Bromination Br 550 Cl2 258
Formic Acid 20 Water 3500 Drowning AlCl3 Soln. 4791
Water 1500 Washing Effluent 1524
EDC loss 150 EDC EDC recycle 2050 Distillation Recovery 30 Residue 48
MEG 573 Acetal MEG Recycled 191 Formation Water Recycled 111
Toluene 2090 Condensation KOH 335 Phenol 562 &
Wash water 2525 Washing Cat 22 KBr Soln. 3383
H2SO4 790 Hydrolysis ML 1193
MPB Distillation Toluene Recycled 1985 Toluene loss 174 Product 1000
Total 16903 Total 16903
M/s. Dhanuka Agritech Limited 80
47. CCMP Manufacturing Process Stage 1 6-Chloronicotinic acid is converted to 6-Chloronicotinoyl chloride by treatment with phosphorus pentachloride and phosphorus oxychloride. Stage 2 6-Chloronicotinoyl chloride is then reduced to the corresponding alcohol using sodium borohydride. Stage 3 2-Chloro-5-hydroxy methyl pyridine is converted to 2-Chloro-5-Chloro methyl pyridine (CCMP) by using thionyl chloride. Mass Balance
Mass balance of CCMP
IN PUT OUT PUT Kg
6-Chloro nicotinic Acid 1094 Phosphorus oxychloride 1056 Stage 1 Acid effluent 2450 Phosphorus Penta Chloride 1444 Acid Chloride
Sodium boro hydride 256 Acidic effluent 500 Stage 2
Acidic effluent 400 Thionyl Chloride 756 RecoveredToluene 1056 Stage 3 CCMP formation Toluene 1167 Drying Loss 367 2-Chloro-5-Chloro 1000 methyl Pyridine
Total 5773 5773
M/s. Dhanuka Agritech Limited 81
48. Triazoles Manufacturing Process Stage 1 Charge Formic acid in the reaction mixture. Purse Ammonia gas slowly in the reaction mass in 3-4 hrs and stir the reaction mass at 300C temperature until reaction is complete. Stage 2 Charge Formamide in the reactor and react with Hydrazine hydrate at high temperature for 2-3 hrs until the reaction is complete. Stage 3 Cool the concentrate mass slowly and filter the 1,2,4-Triazol. Dry the wet product at 50-600C. Mass Balance Mass balance of 1,2,4-Triazol
IN PUT Kg OUT PUT Kg
Formic Acid 85% 2000 Ammonia gas 700 Stage 1 Formamide formation Aqueous effluent 1120
Stage 2 1, 2, 4-Triazol Ammonium Hydroxide 1300 formation Hydrazine hydrate 60% 1200
Ammonium Hydroxide 50 Stage 3 Centrifuge Drying Loss 430 & Drying 1, 2, 4-Triazol 1000
Total 3900 3900
M/s. Dhanuka Agritech Limited 82
Annexure-III Water Balance Water consumption 731 KLD (258 Fresh + 473 recycle)
Domestic Process water Washing Utilities Green belt 10 381 50 250 40
Cooling Boiler Lab Process Scrubber 50 2.0 376 3.0 130 120 Bleed off Blow down Water retained 30 15 With RM 3.0 Drying/Evp. 65 Loss 32 ETP To 2.0 Soak 3+50+30+15=98 KLD pit ETP primary & 9 Tertiary for MEE 411 RO
Reject-33 Salt MEE Condensate 7.5 444 408 Permeate 65
To TSDF System loss 28.5 Recycle water 408+65=473
M/s. Dhanuka Agritech Limited 83
Annexure-III (a) Break up of water consumption and waste water generation Sr. Sources Water Waste water No. consumption KLD generation KLD 1. Domestic 10.0 9.0 2. Gardening 40.0 - 3. Industrial (i Process 376.0 409.0 (ii Lab 2.0 2.0 (iii Scrubber 3.0 3.0 (iv Cooling 130.0 30.0 (v Boiler 120.0 15.0 (vi Washing 50.0 50.0 Total industrial 681.0 509.0 Total (1+2+3) 731.0 518.0 Less recycle 473.0 - Actual w/c & w/w 258.0 - generation
M/s. Dhanuka Agritech Limited 84
Annexure IV Effluent Treatment Plant Flow Diagram of ETP - Process effluent
Sr.No. Name of Unit 1. Equalization/Neutralization Tank 2. Flash Mixer 3. Flocculator 4. Lime Dosing Tank 5. Alum Dosing Tank 6. Poly Floc Dosing Tank 7. Primary Clarifier 8. Intermediates Holding Tank 9. Pressure Sand Filter 10. Activated Carbon Filter 11. Sludge sump 12. Filter press 13. Holding Sump 14. MEE
M/s. Dhanuka Agritech Limited 85
Flow Diagram of ETP - Utilities + washing
Sr.No. Name of Unit 1. Equalization Tank 2. Neutralization tank 3. Primary Settling tank 4. Lime Dosing Tank 5. Intermediates Holding Tank 6. Pressure Sand Filter 7. Holding Sump 8. Sludge sump 9. Filter press
M/s. Dhanuka Agritech Limited 86
Annexure V Details of Hazardous/Solid waste Sr. Type of Sources Category of Quantity Disposal facility No. Waste Waste as in MTPM per HWM Rules 2016 1. ETP Sludge & ETP 35.3 50 Collection, Storage, MEE salt MEE 190 Transportation & Disposal at TSDF site approved by GPCB. 2. Process Process 29.1 360 Collection, Storage, Residue incineration in our own incinerator. 3. Spent Process 29.5 3.5 Collection, Storage and Send catalyst for regeneration to suppliers 4. Discarded Process 33.1 Drum:2500 Being used for packing of ETP containers/ Nos./month sludge in case of excess it will liners Liner:1.5 be sold to approved recycler MT/month or traders. 5. Used Driving 5.1 1.0 Kl/Year Collection, Storage, Lubricating unit & Transportation & disposal by Oil D.G. set selling to Registered Recyclers
M/s. Dhanuka Agritech Limited 87
Annexure-VI Source of Air Emissions
Sr. Stack Fuel Type Stack APC measures Probable No. attached to Height emission Flue Gas Stacks 1 Boiler (5 T/hr) Briquette/ 30 Cyclone & Bag PM<150 mg/NM3
Coal-30 Filter SO2<100 ppm
T/Day NOx<50 ppm 2 Boiler (5 T/hr) 30 Cyclone & Bag PM<150 mg/NM3
Filter SO2<100 ppm
NOx<50 ppm 3 TFH (10 lac K Briquette/ 21 Cyclone & Bag PM<150 mg/NM3
Cal) Coal -8 Filter SO2<100 ppm
T/Day NOx<50 ppm
4 D.G. set (1000 Diesel-250 11 - PM<150 mg/NM3
KVA) lit/Hr SO2<100 ppm
NOx<50 ppm Process Gas stack 1 Process -- 15 Water Scrubber HCl< 20 mg/NM3 Reactor of followed by alkali Pretilachlor scrubber
2 Reactor of -- 15 Water Scrubber HCl< 20 mg/NM3 Metalaxyl followed by alkali scrubber 3 Reactor of -- 15 Soda Ash HCl< 20 mg/NM3 MCA Scrubber 4 Reactor of -- 15 Water Scrubber HCl< 20 mg/NM3 3 CMAC followed by alkali SO2<40 mg/NM scrubber 5 Reactor of -- 15 Water Scrubber HCl< 20 mg/NM3 MPBD followed by alkali HBr<5 mg/NM3 scrubber 6 Propargite 15 Water Scrubber HCl< 20 mg/NM3 3 followed by alkali SO2<40 mg/NM scrubber
M/s. Dhanuka Agritech Limited 88