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BHARAT RASAYAN LIMITED – MOKHRA
BHARAT RASAYAN LTD. 1
Annexure List
Annexures Subject
Annexure-1. Product List
Annexure-2. Site Location Map
Annexure-3. Site Layout
Annexure-4. Manufacturing Process
Annexure-5. Raw Material & Products Storage Details
Annexure-6. Waste Water Generation
Annexure-7. Waste Water Treatment
Annexure-8. Water Consumption
Annexure-9. Fuel Consumption
Annexure-10. Hazardous Waste Generation
Annexure-11. Stack Details
BHARAT RASAYAN LIMITED – MOKHRA
BHARAT RASAYAN LTD. 2
Annexure -1 Product List
Product List
Sr. No.
Name of Product Quantity in MT/Year
Existing After Product Mix
1 Alpha Cypermethrin Technical 0 100
2 Bifenthrin Technical 0 120
3 Clodinafop Technical 0 100
4 Cypermethrin Technical 600 350
5 Fenvalerate Technical 900 300
6 Fipronil Tech. 0 100
7 Lambda Cyhalothrin Tech. 0 300
8 Metaphenoxy Benzaldehyde 960 1800
9 Permethrin Tech. 0 100
10 Safener (Cloquintocet Mexyl) 0 30
11 Thiamethoxam 0 300
12 Diafenthiroun Tech. 0 150
13 Difenconazole Tech. 0 50
14 Propanil Tech. 0 50
15 Pyrazosulfuron Tech. 0 20
16 Para Chloro Phenyl isopropyl Acetic acid 0 200
17 Para chloro benzyl cyanide 480 100
18 Myclobutanil Technical 0 15
19 Tebuconazole Technical 0 50
20 Imiazethapyre Technical 0 25
Total 2940 4260
By Product List
Sr. No. Byproducts Quantity in MT/Year
Existing After Product Mix
1 Alum 5086.08 9536.4
2 Pot. Chloride 2001.6 5036.5
3 Spent acid 1125.9 824.95
4 Hydrochloric Acid 28% 1946.58 2212.31
5 Sodium sulphite 1523.7 1403.8
6 Potassium bromide (soln.) 1850.88 3726.7
7 Sodium Bromide (soln.) 948.6 758.6
Total 14483.34 23499.26
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Annexure: Site Location Map
Figure 1: Site Location Map in Haryana
Annexure - 2
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Annexure – 3 ( Site Lay out )
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Annexure:4 Manufacturing Process
Existing
1. Cypermethrin Technical
Process Description
Meta phenoxy Benzaldehyde & cypermethric acid chloride reacted with aqueous sodium cyanide in
presence of a catalyst & produce Cypermethrin .Hexane & ethylene dichloride is used as a solvent . recovered hexane ethylene dichloride is reused.
1. Fenvalerate Technical
Process Description
Stage – 1
Parachloro Toluene reacted with Chlorine in presence of a catalyst and produced para chlorobenzylchloride. This para chlorobenzyl chloride reacted with Aqueous sodium cyanide and produced
para chlorobenzyl cyanide. A catalyst is used in this reaction.
Stage-2
Para chlorobenzyl cyanide reacted with Isopropyl bromide, caustic soda and a phase transfer catalyst and
produced 2-(4-chlorophenyl)-methyl butyro nitril (CPIN).
Stage – 3
CPIN is hydrolyzed in dil. sulphuric acid to get CPIA. CPIA reacted with Thionyl chloride in presence of
Hexane & EDC solvent and produced parachloro phenyl iso valeryl chloride. Para chloro phenyl iso valeryl
chloride and meta phenoxy benzaldehyde reacted with Aqueous sodium cyanide a phase transfer catalyst to used in this reaction. Soda ash is used as pH booster & recovered hexane & EDC is reused.
2. Metaphenoxy Benzaldehyde
Process Description
Stage-1
Benzaldehyde reacted with bromine and chlorine in presence of Aluminum chloride, Ethylene di chloride is
used as a solvent in above reaction. The Brominated mass quenched in water and washed. After washing organic mass is distilled and recovered Ethylene di chloride is reused in bromination. Distilled meta bromo
benzaldehyde taken for second stage reaction.
Stage-2
Metabromo benzaldehyde reacted with Mono ethylene glycol and produced meta bromo Benzal acetal.
This meta bromo benzalacetal react with KOH and phenol in presence of Toluene solvent and produce
metaphenoxy benzalacetal which on hydrolysis with sulphuric acid and water give Meta phenoxy Benzaldehyde and MEG water is neutralized with caustic lye and recovered water and mono ethylene
glycol is recycle in next batch.
3. Prachloro Benzyl Cyanide
Process Description
Stage – 1
Parachloro Toluene reacted with Chlorine in presence of a catalyst and produced para chlorobenzyl chloride. This para chlorobenzyl chloride reacted with aqueous sodium cyanide and produced para
chlorobenzyl cyanide. A catalyst is used in this reaction
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1. Alpha Cypermethrin Technical
Process Description
Meta phenoxy Benzaldehyde & cypermethric acid chloride reacted with aqueous sodium cyanide in presence of a catalyst & produce Cypermethrin .Hexane & ethylene dichloride is used as a solvent .
recovered hexane ethylene dichloride is reused. Cypermethrin reacted with a tri ethyl amine & produced
Alpha cypermethrin, which is acidified with acid &crystallized in hexane. Solvent is filtered & product dried in drier. Recovered Hexane, & TEAS is reused.
Process flow diagram of Alpha Cypermethrin
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CHEMICAL REACTION OF ALPHACYPER METHRIN
H3C CH3
C CHO
H COCl + + NaCN + H2O CH C CMAC MPB Cl MW=227.5 MW=198 Cl H3C CH3
C
Cl H C=HC COO C + NaCl+NaCN +H2O Cl CN
Cypermethrin Technical
MW = 416.3
H3C CH3
C
Cl H C=HC COO C + CH3COOH+TEA Cl CN Acetic acid
Cypermethrin Technical
MW = 416.3
H3C CH3
C
Cl H C=HC COO C + TEA Acetate Cl CN
Alpha Cypermethrin Technical
MW = 416.3
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Material Balance of Alphacypermethrin
S. No. Input/Ton of Product Total Consumption to
produce 1KG. of Alpha
Cypermethrin Technical Raw Materials
1 Metaphenoxy Benzaldehyde 0.71
2 Cypermethic Acid Chloride 0.83
3 Sodium cyanide 0.20
4 Catalyst 0.02
5 Ethylene Dichloride (Fresh + Recovered) 0.08
6 Hexane (Fresh + Recovered) 3.62
8 Soda Ash 0.02
9 TEA (Fresh + Recovered) 0.13
10 Acetic acid 0.109
11 Caustic Lye 47% 0.176
12 Sodium hypochlorite for washing 0.183
12 Water 4.855
Total 10.934
S. No.
Output in Ton /Ton of Product Disposals / ETP
Offsite Recycling Item Liquid
Effluent
Air
Emission Recovery
Solid
Waste
1 Alpha
Cypermethrin - - 1 - Product
2 Rec Ethylene
Dichloride - - 0.08 - Recovered for Reuse
3 Rec Hexane - - 3.46 - Recovered for Reuse
4 Rec Cyper. - - 0.39 - Recovered for Reuse
5 Rec. TEA - - 0.08 - Recovered for Reuse
6 EDC - 0.00 - - Loss
7 Hexane - 0.08 - - Loss
8 Operation Loss - 0.08 - - Loss
9 Spent Cyanide
Aq. 1.813 - - -
To ETP through detoxification
10 Water+acetic
acid +salt 3.775 - - - To ETP
11 Ventury soln 0.176 To ETP
Total
(Ton)
5.764 0.16 5.01
10.934
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2. Bifenthrin Technical
Process Description
Bifenthrin alcohol is reacted with thionyl chloride to form bifenthrin chloride which was further reacted
with lambda cyhalothric acid [2-(IR, S)-cis-2,2-dimethyl-3-(2,2-chloro,3,3,3-trifloro-1-propargyl) cyclopropane Carboxylic acid] to form Bifenthrin (T) Product is purified in suitable solvent.
Process Flow Diagram
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CHEMICAL REACTION BIFENTHRIN
+ SOCl2 + SO2 + HCl
Thionyl chloride [119] [64] [36.5]
CH3 CH2OH CH3 CH2Cl
Bifenthrin Alcohol [198 ] Bifenthrin Chloride
[216.5 ]
Cl
+ C = CH COOH Catalyst
CF3 +K2CO3 + TBAB
CH3 CH2Cl CH3 CH3 Pot.Carbonate [138]
Bifenthrin Chloride Cyhalothric Acid
[216.5] [242.5]
Cl
C = CH C O
CF3 O CH2 + HCl + KCl
CH3 CH2 Hydrochloric Acid Pot. Chloride
CH3 [ 36.5 ] [ 74.5 ]
Bifenthrin [ 422.5 ]
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Material Balance of Bifenthrin
S. No. Input/Ton of Product Total Consumption to
produce 1KG. of Bifenthrin Technical Raw Materials
Propargyl alcohol reacted with thionyl chloride & produced Propargyl chloride.
Stage-2
5-chloro-2,3 di chloro pyridine, potassium carbonate, 2-(4-hydroxyphenoxy propionic acid) and propargyl chloride reacted and produced Clodinafop propargyl tech. DMF is used for reaction in above reaction and
Methanol is used as a solvent for crystallization. Recovered DMF & methanol reused in process.
Meta phenoxy Benzaldehyde & cypermethric acid chloride reacted with aqueous sodium cyanide in presence of a catalyst & produce Cypermethrin .Hexane & ethylene dichloride is used as a solvent .
recovered hexane ethylene dichloride is reused.
Process Flow Diagram of Cypermethrin
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CHEMICAL REACTION OF CYPERMETHRIN
H3C CH3
C
CHO
H COCl + + NaCN + H2O
Cl CH
C Cypermethric Acid chloride sodium cyanide
Cl MW=227.5 [49 ]
MPB
198
H3C CH3
C O
H
Cl
C HC COO C + (NaCl+ NaCN +water)
Cl Spent Sod. Cyanide
CN
Cypermethrin Technical
MW=416.3
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Material Balance of Cypermethrin
S. No. Input/Ton of Product Total Consumption to produce
1 KG. of Cypermethrin
Technical Raw Materials
1 Metaphenoxy Benzaldehyde 0.503
2 Cypermethic Acid Chloride 0.585
3 Sodium cyanide 0.146
4 Catalyst 0.014
5 Ethylene Dichloride (Fresh + Recovered) 0.06
6 Hexane (Fresh + Recovered) 1.248
7 Sodium Hypo Chlorite 0.05
8 Soda Ash 0.02
9 Water 2.107
Total (Ton) 4.733
S. No.
Output in Ton /Ton of Product Disposals / ETP
Offsite Recycling Item Liquid
Effluent Air
Emission Recovery
Solid Waste
1 Cypermethrin - - 1 - Product
2 Recovered Ethylene
Dichloride
- - 0.058 - Recovered for Reuse
3 Recovered
Hexane - - 1.190 - Recovered for Reuse
4 Ethylene Dichloride
- 0.002 - - Loss
5 Hexane - 0.058 - - Loss
6 Spent Cyanide 1.225 - - - To ETP through
Detoxification
7 Water +hypo 1.200 - - - To ETP
Total
(Ton)
2.425 0.06 2.248 0.00
4.733
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5. Fenvalerate Technical
Process Description
Stage – 1
Parachloro Toluene reacted with Chlorine in presence of a catalyst and produced para
chlorobenzylchloride. This para chlorobenzyl chloride reacted with Aqueous sodium cyanide and produced
para chlorobenzyl cyanide. A catalyst is used in this reaction.
Stage-2
Para chlorobenzyl cyanide reacted with Isopropyl bromide, caustic soda and a phase transfer catalyst and
produced 2-(4-chlorophenyl)-methyl butyro nitril (CPIN).
Stage – 3
CPIN is hydrolyzed in dil. sulphuric acid to get CPIA. CPIA reacted with Thionyl chloride in presence of
Hexane solvent and produced parachloro phenyl iso valeryl chloride. Para chloro phenyl iso valeryl chloride and meta phenoxy benzaldehyde reacted with Aqueous sodium cyanide a phase transfer catalyst
to used in this reaction. Soda ash is used as pH booster & recovered hexane & EDC is reused.
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CHEMICAL REACTION OF FENVALERATE
Stage – 1
CH3 CH2Cl
i
a) + Cl2 + Catalyst-I + HCl
AZDN Hydrochloric acid
Chlorine [36.5]
Cl Cl
Parachloro Toluene Para chlorobenzylchloride
MW=126.5 MW=161
CH2 – Cl CH2CN
b) + H2O + NaCN + Catalyst-II + NaCl
TEA Sod. Chloride
[58.5]
Cl Cl Para chlorobenzyl
Cyanide
Para chloroBenzylchloride + Sodium Cyanide (PCBCN)
2 Ethylene Di Chloride (EDC) (Fresh + Recovered) 3.730
3 Tri floro metthane sulfinyl chloride 0.492
4 Trmethyl amine hydrochloride 0.492
5 4- DMAP 0.033
6 Ammonia solution 0.003
7 Water 8.60
Total (Ton) 14.28
S. No.
Output in Ton /Ton of Product Disposals / ETP
Offsite Recycling Item Liquid
Effluent Air
Emission Recovery
Solid Waste
1 Fipronil - - 1 - Product
2 Ethylene Dichloride
- - 3.545 - Recovered reused
3 Ethylene
Dichloride - 0.185 - - Loss
4 Hydrochloric
acid -30% - - 0.3925 - Bi-product
5 Washing +salt 8.853 - - - To ETP
6 Residue - - - 0.3045 To Incineration
Total
(Ton)
8.85 0.19 4.94 0.30
14.28
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7. Lambda Cyhalothrin Technical
Process Description
Stage- 1
Lambda cyhalothric acid reacted with thionyl chloride & produced Lambda Acid Chloride.
Stage-2
Lambda acid chloride, meta phenoxy Benzaldehyde, Aq. Sodium cyanide and a catalyst reacted and
produced cyhalothrin technical. Hexane is used as a solvent in this reaction. Spent sodium cyanide is sent detoxification plant. Recovered hexane is reused then Cyhalothrin is epimerized with IPA and
Input/Ton of Product Total Consumption to produce 1KG. of Lambda Cyhalothrin
Technical Raw Materials
1 Lambda Acid 0.555
2 Thionyl chloride 0.290
3 Dimethyl Formamide (DMF) 0.002
4 Caustic Soda Lye 0.54
5 Metaphenoxy Benzaldehyde 0.44
6 Sodium Cyanide 0.124
7 Catalyst 0.01
8 Soda Ash 0.03
9 Hexane 2.60
10 Sodium Hypo Chlorite 0.490
11 Acetic Acid 0.115
12 Isopropyl Alcohol 0.79
13 Di isopropyl Amine 0.04
14 Lambda powder (seeding) 0.02
15 Sodium bicarbonate (NaHCO3) 0.01
16 Caustic Soda Flakes 0.098
17 Water 6.756
Total (Ton) 12.91
S.
No.
Output in Ton /Ton of Product Disposals / ETP
Offsite Recycling Item Liquid
Effluent Air
Emission Recovery
Solid Waste
1 Lambda
Cyhalothrin - - 1 - Product
2 Sodium Sulphite
Solution (22%)
- - 1.35 - Byproduct
3 Hydrochloric Acid (28%)
- - 0.3 - Byproduct
4
Recovered
Isopropyl Alchohol
- - 0.75 - Recovered for Reuse
5
Recovered Di
iso Propyl Amine
- - 0.03 - Recovered for Reuse
6 Recovered
Hexane - - 2.50 - Recovered for Reuse
7 Isopropyl Alcohol
- 0.039 - - Loss
8 Di iso Propyl
Amine - 0.012 - - Loss
9 Hexane - 0.10 - - Loss
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10 Spent Cyanide
Solution 0.79663 - - -
To ETP through
Detoxification
11 Caustic Solution
0.221 - - - To ETP
12 Water 5.81 To ETP
Total (Ton) 6.82 0.151 5.93 0.00
12.91
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8. Metaphenoxy Benzaldehyde
Process Description
Stage-1
Benzaldehyde reacted with bromine and chlorine in presence of Aluminum chloride, Ethylene di chloride is
used as a solvent in above reaction. The Brominated mass quenched in water and washed. After washing organic mass is distilled and recovered Ethylene di chloride is reused in bromination. Distilled meta bromo
benzaldehyde taken for second stage reaction.
Stage-2
Metabromo benzaldehyde reacted with Mono ethylene glycol and produced meta bromo Benzal acetal.
This meta bromo benzalacetal react with KOH and phenol in presence of Toluene solvent and produce
metaphenoxy benzalacetal which on hydrolysis with sulphuric acid and water give Meta phenoxy Benzaldehyde and MEG water is neutralized with caustic lye and recovered water and mono ethylene
2 3-methyl-4-nitro per hydro, 1,2,5 oxadiazene (MNPO) 0.70
3 Dimethyl Formamide (DMF) 3.69
4 Methanol 1.06
5 Caustic Flakes 0.18
6 Hydrochloric acid -30% 0.035
7 Sodium hypochlorite 0.150
8 Water 2.640
Total (Ton) 9.155
S. No.
Output in Ton /Ton of Product Disposals / ETP
Offsite Recycling Item
Liquid Effluent
Air Emission
Recovery Solid
Waste
1 Thiomethoxam - - 1 - Product
2 Recovered DMF - - 3.51 - Recovered for Reuse
3 Recovered Methanol
- - 1.01 - Recovered for Reuse
4 Uncondensed
vapour - 0.24 - - Loss
6 Sodium Chloride 0.26 - - - To ETP
7 Unreacted
Caustic (100%) 0.01 - - - To ETP
8 Unreacted MNPO 0.07 - - - To ETP
9 Water 2.90 - - - To ETP
10 Residue - - - 0.16 To incinerator
Total (Ton)
3.24 0.24 5.52 0.16
9.155
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12. Diafenthiuron
Process Description
1-(2,6-diisopropyl-4-phenoxy phenyl)-thiourea continuously reflux in presence of xylene as a solvent till
conversion into 1,2-diisopropyl-2-isothiocynato-5-phenoxybenzene which is an isothiocynate derivative.
Organic layer is separated. Organic layer having 1,3-diisopropyl-2-isothiocynato-5-phenoxybenzene
obtained in step-II is then condensed with tertiary butyl amine to form Diafenthiuron.
Process Flow Diagram Diafenthiuron
O-Xylene Water
Thio-urea O-Xylene
Catalyst - MR
Tertiary Butyl amine
IPA
Water Aqueous to ETP
IPA
Isomerization
Condensation
Layer separation
Filtration & Drying
Packing
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CHEMICAL REACTION OF DIFENTHIURON
CH3 CH3
CH3 + Xylene + Cat-MR + CH3 C NH2
S CH3
NH2-C-NH
CH3 CH3 Tertiary Butyl amine
[ 73]
1-(2,6-Diisopropyl-4-phenoxyphenyl Thiourea
MW=328.6
CH3
CH3 C
CH3
CH3 – C – N – C N
CH3 H S H C + NH3
CH3 CH3 AMMONIA (17)
Diafenthiuron
[ 384.6 ]
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Material Balance Difenthiuron
1 Xylene 0.99
2 2,6 Di-isopropyl phenoxy phenyl thio urea 0.97
3 Catalyst MR 0.003
4 Tertiary butyl Amine 0.23
5 Isopropyl alcohol (IPA) 1.58
6 Water 0.200
Total (Ton) 3.98
S. No.
Output in Ton /Ton of Product Disposals / ETP
Offsite Recycling Item Liquid
Effluent
Air
Emission Recovery
Solid
Waste
1 Difenthiuron - - 1 - Product
2 Xylene
recovered - - 0.95 - Recovered & reused
3 IPA recovered - - 1.51 - Recovered & reused
4 Xylene - 0.049 - - Recovered & reused
5 IPA - 0.078 - - Loss
6 Water + TBA 0.22 - - - To ETP
7 Residue - - - 0.19 For incineration
Total (Ton)
0.22 0.13 3.45 0.19
3.98
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13. Difenconazole
Process Description
2-(4-(4-chlorophenoxy)-2-chlorophenyl)-2-bromomethyl-4-methyl-1,3-dioxolone is reacted with 1,2,4-triazole in presence of potassium carbonate as acid scavenger. DMF is used as a solvent in the reaction. Crude Difenconazole is purified by methanol to get pure Difenconazole (T)
Process Flow Diagram of Difenconazole
Pot.Carobonate
Bromo OxolaneDerivative KBr.soln.as by product
DMF
Water
1,2,4-Triazole DMF Recovered
Methanol
Recd.Methanol for recycling
Reactor
Filtration
Purification
Drying and Packing
Diafenconazole
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CHEMICAL REACTION OF DIFENCONAZOLE
N N + + 1 K2CO3 N 2 Pot.carbonate N C H CH2Br [ 69 ] [ 138l/2 69 ] [ 418 ] 2-(4-(4-chlorophenoxy)-2-chlorophenyl) 1,2,4 triazole -2-bromomethyle-4-methyl-1,3-dioxolone
N Carbondioxide + KBr + 1 CO2 + 1 H2O (water) Pot.bromide 2 2 N CH2 N [ 119 ] [ 44/2 22 ] [18 /2 9 ] [ 406 ] N Difenconazole
Ethyl-1-methyl-5-Sulfenamideisocyanate-1H-pyrazole-4-carboxylate is reacted with 2-amino-4,6-dimethoxy pyrimidine in presence of Toluene. Crude Pyrazosulfuron is purified by methanol to get pure Pyrazosulfuron (T)
Process Flow diagram of Pyrazolsulfuron
Ethyl-1-methyl-5-sulfenamide
isocyanate-1H-
Pyrazole 4-carboxylate
2-amino-4,6 dimethoxy
Pyrimidine
Toluene
Recd.Tolune
Methanol Recd. Methanol
Pyrazosulfuron
Reactor
Filtration
Purification
Drying & Packing
Packing
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CHEMICAL REACTION PYRAZOLSULFURON
CH3 NH2 N S - N = C= N N Toluene N + C– – CH2CH3 CH3O OCH3 2-amino-4,6-dimethoxy pyrimidine [ 155 ] Ethyl-1-methyl-5-sulfenamide isocyanate-1H-pyrazole-4-carboxylate MW=259 CH3 N OCH3 N N N S – NH – C – NH - N OCH3 C – 0 – CH2CH3 Pyrazosulfuron MW=414
S. No. Input/Ton of Product Total Consumption to produce
1 KG.Of parachloro phenyl alpha isopropyl acetic acid Raw Materials
1 Para chloro Toluene 0.810
2 Chlorine 0.463
3 Catalyst –I ( AZDN) 0.004
4 Sodium Cyanide 0.318
5 TEA – II Catalyst 0.017
6 Caustic Lye for ventury + Alkyl 0.521
7 Isopropyle bromide 0.673
8 TEBA Catalyst – III 0.018
9 Caustic Soda Flakes 0.287
10 Sulphuric Acid 1.588
11 Hexane 1.76
12 Water 6.464
Total (Ton) 12.92
S. No.
Output in Ton /Ton of Product Disposals / ETP
Offsite Recycling Item Liquid
Effluent
Air
Emission Recovery
Solid
Waste
1 CPIA - - 1 - Product
2 HCl 30% - - 0.781 - Byproduct
3 Spent acid - - 2.25 - Byproduct
4 Isopropyl bromide
- - 0.02635 - Recovered for Reuse
5 Hexane - - 1.677 - Recovered for Reuse
6 Hexane - 0.083 - - Loss
7 Uncondensed
Vapor - 0.08 - - Loss
8
Spent Sod.
Cyanide aq. Soln.
1.54 - - - To ETP through
detoxification unit
9 NaBr. Soln. 2.014 - - - To ETP through
bromine recovery
10 NaCl+C.S Lye 0.129 - - - To ETP
11 Water 3.173 - - - To ETP
12 Impurities - - - To Incineration
13 Residue - - - 0.165 To Incineration
Total
(Ton)
6.855 0.163 5.732 0.165
12.92
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17. Para chloro benzyl cyanide (PCBCN)
Process Description
Stage – 1
Parachloro Toluene reacted with Chlorine in presence of a catalyst and produced para chlorobenzylchloride. This para chlorobenzyl chloride reacted with Aqueous sodium cyanide and produced
para chlorobenzyl cyanide. A catalyst is used in this reaction.
Process Flow Diagram of PCBCN
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CHEMICAL REACTION OF PCBCN
Stage – 1
CH3 CH2Cl
i
a) + Cl2 + Catalyst-I AZDN + HCl
Chlorine
Cl Cl
Parachloro Toluene Para chlorobenzylchloride
MW=126.5 MW=161
CH2 – Cl CH2CN
b) + H2O + NaCN + Catalyst-II TEA + NaCl
Cl Cl Para chlorobenzyl
Cyanide
Para chloroBenzylchloride + Sodium Cyanide (PCBCN)
[161] [49] [151.5]
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Material Balance of PCBCN
S. No. Input/Ton of Product Total Consumption to produce
1 KG. Of PCBCN Raw Materials
1 Para chloro Toluene 1.022
2 Chlorine 0.584
3 Catalyst (AZDN)- I 0.005
4 Sodium Cyanide 0.401
5 Catalyst (TEA) – II 0.014
6 Caustic for ventury 47% 0.037
7 Water 3.57
Total (Ton) 5.632
S. No.
Output in Ton /Ton of Product Disposals / ETP
Offsite Recycling Item Liquid
Effluent
Air
Emission Recovery
Solid
Waste
1 PCBCN - - 1 - Product
2 HCl 30% - - 0.985 - Byproduct
3 Catalyst -I 0.005 Reused
4 Uncondese
vapour - 0.1037 - Loss
5 Spent Sod. Cyanide aq.
Soln.
1.938 -
- -
To ETP through
detoxification unit
6 NaCl+C.S
Lye+water 0.16 -
- To ETP
7 Water 1.37168 - - - To ETP
8 Residue - - - 0.06896 To Incineration
Total (Ton)
3.47 0.1037 1.99 0.069
5.632
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18. Myclobutanil
Process Description
Parachloro benzyl cyanide is reacted with butyl bromide in presence of base to form 2-(4-chlorophenyl)hexane nitrile.
2-(4-chlorophenyl)hexane nitrile is then reacted with excess dichloro methane in presence of base to form 1-chloro-2-(4-chlorophenyl)-2-cyanohexane.
1-chloro-2-(4-chlorophenyl_-2-cyanohexane is reacted with 1-Sodium-1,2,4-H triazole in presence of base to form Myclobutanil.
H – C – C N Cl – CH2- C - CN + Cl – CH2 -Cl + NaOH + NaCl + H2O dichloromethane MW=85 Cl Cl 2-(4-chlorophenyl)hexane nitrile 1-chloro-2-(4-chlorophenyl)-2-cyano hexane MW = 207.5 MW= 256 CH2CH2CH2CH3 CN N
Cl-CH2-C-CN CH3CH2CH2CH2- C –CH2-N N N + N + NaOH + NaCl + H2O N H Cl Cl 1,2,4-Triazole Myclobutanil MW = 256 MW=69 MW=288.5
1-chloro-2-(4-chlorophenyl)-2-cyano hexane
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Material Balance of Myclobutanil
S. No.
Input/Ton of Product Total Consumption to
produce 1 kg Of parachloro
pheny alpha isopropyl acetic acid
Raw Materials
1 Parachloro benzyl cyanide 0.68
2 Butyl Bromide 0.61
3 Dichloro Methane 1.10
4 1,2,4- triazole 0.29
5 Dimethyl formamide 3.00
6 Sodium hydroxide 0.51
7 Water 6.20
Total (Ton) 12.40
S. No.
Output in Ton /Ton of Product Disposals / ETP
Offsite Recycling Item Liquid
Effluent Air
Emission Recovery
Solid Waste
1 Mucobutanly Tech. - - 1.00 - Product
2 Sodium Bromide Soln.
2.64 - - - Byproduct
3 Recovered Dicloro
Methane - - 0.72 - Recovered & reuse
4 Uncondensed vapour
of dichlor methane - 0.04 - - Loss
5 Recovered DMF - 2.85 - Recovered for
Reuse
6 Uncondensed vapor
of DMF - 0.15 - Loss
7 Sodium chloride - - 0.20 To landfill site
8 Water wash –I 1.64 - - - To ETP
9 Water wash-II 3.16 - - - To ETP
Total (Ton)
7.44 0.19 4.57 0.20
12.40
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19. Tebuconazole Tech.
Process Description
2-[2[(4-chlorophenyl)ethyl]-2-(1,1-dimethyl-ethyl)oxirane is reacted with 1,2,4-Triazole in presence of base using Dimethyl formamide as a solvent to form Tebuconazole.
Dimethyl formamide is recovered and crude product is formed slurry with water and filtered.
Diethyl – 5 ethyl pridine -2,3-dicarboxylate and 2-amino-2,3-dimethyl butyramide is reacted with in presence of sodium methoxide. Product is obtained as sodium salt of Imazethapyr then acidified with
S. No. Input/Ton of Product Total Consumption to produce
1KG. Of PCBCN Raw Materials
1 Diethyl-5-ethyl pyridine-2,3-dicarboxylate 1.09
2 2-amino-2,3-dimethyl butyramide 0.59
3 Sodium Methoxide 0.58
4 Toluene 3.50
5 HCl (28%) 1.39
Total (Ton) 7.15
S. No.
Output in Ton /Ton of Product Disposals / ETP
Offsite Recycling Item Liquid
Effluent Air
Emission Recovery
Solid Waste
1 Imazethapyre
Tech. - - 1.00 - Product
2 Toluene - - 3.40 - To ETP
3 Uncondensed vapour
(Toluene)
- 0.100 - - To ETP
4 Ethanol 0.4 - - - To ETP
5 Methanol 0.343 - - - To ETP
6
Unreacted
2-amino-2,3-dimethyl
butyramide
0.030 - - - To ETP
7 Water 1.01 - - - To ETP
8 Sodium
Chloride 0.63 - - - To ETP
9 Residue - 0.25 Incinerator
Total (Ton)
2.40 0.100 4.40 0.25
7.15
Bromine Recovery
Potassium or sodium bromide solution obtained from different products are acidified with hydrochloric acid or sulphuric acid as per requirement & acidified aqueous is taken for bromine recovery by passing chlorine
at higher temperature.
Detoxification of Spent Sodium Cyanide Aqueous
Caustic soda lye & spent sodium cyanide is charged in vessel, then chlorine is passed at low temperature,
sodium hypo chlorite is formed in citu which reacts with sodium cyanide &destroy to nitrogen ,sod
chloride & sodium carbonate.
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Annexure 1: Raw Material & Products Storage Details
Table 1: Details of Raw Material & Product
Sr. No
Chemical State Consumption, (MT/Annum
Hazard Involved Means of Storage
Operating Condition (Storage)
No of Drum
or Vessel
Packing size
Max. Storage Capacity
(MT) Press
(Kg/Cm2) Temp (0C)
Raw Materials
1
2(4(chlorophenyl )-2-chlorophenyl) 2-
bromomethyl-4methyl -1,3 dioxolone
Liquid 64.50 Non-Hazard M.S. Drum Ambient Ambient 100 200 kg. 20
2
2-[2[(4-chlorophenyl)ethyl]-2-(1,1-
dimethyl-ethyl)oxirane Liquid 43.00 Non-Hazard M.S. Drum Ambient Ambient 100 200 kg. 20
6 Potassium bromide (soln) Liquid 3726.7 Corrosive MS storage
tank Ambient Ambient 1 40 KL 40 KL
7 Sodium Bromide (soln) Liquid 758.6 Corrosive MS storage
tank Ambient Ambient 2 20 KL 40 KL
23499.26 14 300 KL
FORM 1
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Annexure 2: Waste Water Generation Details
S.
No. Area
Effluent Generation in KLD
Disposal Mode Existing
After Product Mix
1 Domestic 30 35 To STP & used for
Gardening
2 Industrial Process 34.43 35.62 To Pretreatment & MEE. Condensate of MEE to
ETP Washing 2.0 3.0
Cooling 4 5 Condensate of MEE and
outlet of Utilities will be treated in ETP and
finally reused in plant Boiler 5 6
Total (Industrial) 45.43 49.62
Total Waste Water
Generation KL/Day 75.43 84.62
FORM 1
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Annexure 3: Waste Water Treatment Plant Details
Details of Existing Effluent Treatment Plant
M/s. Bharat Rasayan Limited have an Effluent Treatment Plant consisting of primary, secondary and tertiary treatment units. The effluent confirming the SPCB standards shall be collected in the tank
before it is reused.
Process Description: ETP
For the proposed pesticide manufacturing unit, the raw water will be utilized for Processing, Cooling,
Washing, Boiler, Scrubber and domestic purpose. The effluent generated from the same sources will be sent to Proposed Evaporation System. Water will be evaporated, condensed and recycled to
process/scrubber/sent to proposed ETP. After recovery of solvent from mother liquor, water will be
sent to ETP. The biodegradable effluent will be sent to ETP.
Primary Treatment:
The biodegradable effluent is first passed through the Oil & Grease tank to remove oil & grease content from the effluent. The effluent is equalized & neutralized by addition of either acid or caustic.
The pH will be adjusted to 6.5 (range 6.5 to 9.5). the mixing is provided by air diffusion. There will is a one no. of equalization tanks, then mass from equialsation tank is taken to neutralization reactor for
pH maintaining. Once pH is achieved, then the neutralized wastewater is collected into settling cum
clarifier and then transferred to sludge drying bed &water to holding tank. From holding tank water is taken to MEE for distilling water.
Secondary Treatment:
Condensed Water from MEE is taken to storage tank for it. From storage tank water is taken to
charging overhead tank. From overhead tank it is taken to aeration tank for aeration for biological
treatment. For biological treatment two no of tanks are provided. Each tanks is fitted with fine bubble diffuser & air is provided by blower. From biological tank partial mass is taken in clarifier for
decanting clarifier water in holding tank. Sludge from bottom of clarifier is recycle & partial sludge is filtered by filter bed. Sludge is send to TSDF site .
Tertiary Treatment:
For the finishing of the treated effluent getting from the overflow of the clarifier, tertiary treatment
will be introduced. The overflow of the clarifier tank is overflow by gravity to a collection tank from
where it is passed through pressure sand filter & activated carbon filter. The final treated effluent is collected in collection tank and is reused
Details of Units of ETP
Sr. No. Name of Unit Dimension No. of Units
1. Equalization Tank 8.7 x 8.7 X 2.13 1
2. Neutralization Tank with coarse diffuser
3.1 x 3.1 x 2.13 1
3. Lime Dosing Tank 5000 ltrs 1
4. Flocculation & reaction reactor 10000ltrs 1
5. Primary Clarifier – I 28000 ltrs 1
6. Intermediate Collection Tank 10.0 X6.5X2.3 1
7. Aeration Tank – I 10.0 X6.5X2.3 1
8. Aeration Tank – II 8 X 8 X 2.5 1
9. Secondary Settling tank – I 15000 ltrs 1
10. Intermediate tank 6000 ltrs 1
11. Dual Media Filter 5 m3 1
12. Carbon bed filter 2 m3 1
FORM 1
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Sr. No. Name of Unit Dimension No. of Units
13. Treated Water tank 20000 ltr 1
14. Sludge Sump 5.1 x 5.1 x (2.5 + 0.5) 1
15. Filter Press - 1
Evaporation System
Process Description:
The feed effluent is preheated by using hot condensate coming from the evaporator. The effluent is fed to continuous multiple effect evaporator and the effluent concentrated continuously by using
steam as heating medium to the first effect. The evaporated and condensed water is recycled to Scrubbers / ETP.
The evaporation is carried till the inorganic salts is start crystallizing in the evaporator and slurry is formed. The slurry of salts and effluent is withdrawn and fed to a Nutsche Filter for separating the
solids. Two Nutsche filters will be provided to sustain continuous operation. The solids coming from the Nutsche filter will be manually scooped and dumped to GEIPL , Pali (nearest TSDF site).
Details of Effluent Treatment PlantS
PRE-TREATMENT UNITS: 1. Screening Chamber: 1 No.
Effluent generated from various production areas will be collected into a screen chamber via gravity /
pumping. Screening Chamber will be made of RCC with internal acid proof brick lining since the pH of
incoming effluent is acidic in nature. The chamber will be provided with fine screens – MS FRP lined for arresting the floating matter and large size suspended matter. From this chamber the effluent will
flow under gravity to Oil & Grease Trap Unit.
2. Oil and Grease Trap: 1 No.
Effluents from screening chamber will overflow to an Oil & Grease Trap under gravity. Oil and Grease chamber is baffle walled tank. Oil and Grease collected is removed manually by scrapping and shall
be disposed off as Hazardous wastes (waste oils) which shall form a part of Hazardous solid wastes
along with ETP Sludge.
3. Equalization cum Neutralization Tanks: 1 Nos.
Overflow from Oil & Grease Trap will be taken to Equalization cum Neutralization Tanks under gravity. The prime purpose of these tanks is for collection and storage of effluents generated and to
have proper equalization of effluents in order to have constant load onto the further treatment units.
This is designed as PROCESS for operational ease. This equalized effluent will be further subjected to lime, alum & poly dosing for neutralization cum flocculation. A reactor is used for pH adjustment /
primary treatment of flocculation and precipitation.
Course Bubble Aeration grid with Twin lobe blower system is provided in this tank for mixing the
effluents for proper equalization and keeping the tank contents into suspension.
Dosing of Lime, Alum & poly shall be carried out in the reactor for neutralization and flocculation.
From this reactor, the flocculated effluent shall be further transferred to Primary Settling Tank for
settlement of chemical sludge.
Dosing of chemicals is carried out by means of three HDPE open top dosing tanks each for lime,
alum & poly. 10% concentration of Lime, Alum & 2% Poly solution shall be prepared in these dosing tanks. The tanks are of made of HDPE / FRP
4. Primary Settling Tank - 1: 1 No.
FORM 1
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The flocculated effluents from Equalization cum neutralization reactor will be pumped directly into
Primary Settling tank for removal of the chemical sludge by settling.
This chemical sludge falls under the Hazardous Waste Category as per the Hazardous Waste
Management and Handling Rules. The sludge will be directly taken to Sludge Drying Beds and further temporarily stored in HDPE/LDPE bag packing in the Hazardous Waste Storage Shed provided in the
ETP area. The sludge will be finally disposed off into a secured landfill site. The supernatant from the
primary settling tank will be further conveyed under gravity to the Intermediate Collection Tank.
5. Intermediate Collection Tank - 1: 1 No
An Intermediate Collection Tank – 1 will be provided for collection of supernatant from Primary settling tank. From this Feed Tank, the equalized and primarily treated effluents shall be pumped to
the 1st Unit of MEE i.e. Solvent Stripper for stripping of solvents which will further pass through Multi Effect Evaporator.
MEE System: Multi Effect Evaporator with Solvent Stripper & Nutch Filter: 50 KL Capacity – Total 1
Solvent Stripper and MEE System are proposed to evaporate the neutralized effluents of process +
washings. The Solvent Stripper removal the low boiling point solvents and the MEE will generate residue and condensate. MEE system will be designed to cater for high TDS by selection of suitable
material for Calandria Tubes. The system will be designed with Thermo Vapour Compressor with
Three to four stage of Falling Film or Forced Circulation Evaporation System. The concentrate solids will be filtered out in a nutch filter whereas the filtrate will be recycled back into the system. MEE
Condensate will be collected into the Collection Tank of Post Treatment Units.
Solids from MEE will be collected and packed in bags for intermittent storage in Hazardous Waste
Storage area in ETP. They will be further dispose off into Secured Landfill site.
POST TREATMENT UNITS:
Condensate from MEE plant is taken in a storage tank,from storage tank it is taken in charging tank from charging tank condensate is charged in biological treatment tank. Biological treant tank is fitted
with fone bubble air diffuser. These diffuser are connected with root blower. After aeration treated mass is transferred to clarifier, overflow of clarifier is collected in a tank. Sludge is transferred back
to biological tank. Part of sludge is transferred to filter. Which collected & send to TSDF.
1. Pressure Sand Filter:
Pressure Sand Filter will be provided as a form of tertiary treatment for removal of residual suspended solids. The filter is consist of different gradations of gravel & sand bed. The filter is
provided with necessary valve arrangements for inflow and outflow and backwashing of the system.
The backwash water from the system will be taken to the Equalization cum Collection tank for re-treatment.
2. Activated Carbon Filter:
Activated Carbon Filter will be provided as a form of tertiary treatment for removal of residual
organics, odor, color & organic TDS by means of adsorption process. The filter will consist of
gradations of gravel & sand sub bed and over which is provided activated carbon of high iodine value. The filter will be provided with necessary valve arrangements for inflow and outflow and
backwashing of the system. The backwash water of the system shall be taken to the Equalization cum Collection Tank for re- treatment. The sand and activated carbon filters are provided as part of
tertiary polishing treatment for catering to residual pollution load in order to meet the specified disposal norms.
Outlet of PSF and ACF will be taken to Final Collection Tank (Guard Pond) for storage to be further
use in plant .
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3. Sludge Drying Beds:
The chemical sludge formed in physio-chemical treatment from primary settling tank will be directly
collected in Sludge Drying Beds.
The sludge drying beds will be divided into compartments to facilitate in easy sludge drying handling and disposal. The dried sludge falls under hazardous waste category and should be filled in
HDPE/LDPE bags and finally disposed to a secured landfill. Leachate from Sludge Drying Bed will be collected in leachate collection sump and pumped back to equalization cum collection tanks.