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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
BHARAT RASAYAN LIMITED – MOKHRA
BHARAT RASAYAN LTD. 3
Annexure: Site Location Map
Figure 1: Site Location Map in Haryana
Annexure - 2
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BHARAT RASAYAN LTD. 4
Annexure – 3 ( Site Lay out )
BHARAT RASAYAN LTD. FORM 1
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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
1 Bifenthrin Alcohol 0.57
2 SOCl2 0.34
3 Ethylene dichlride(Fresh + Recovered) 1.0
4 Lambda Cyhalothric Acid 0.63
5 Caustic Soda lye 47% 0.486
6 Potassium Carbonate 0.36
7 Dimethyl Formamide (DMF) (Fresh + Recovered) 1.13
8 Hexane (Fresh + Recovered) 1.170
9 Water 3.657
Total (Ton) 9.34
S. No.
Output in Ton /Ton of Product Disposals / ETP
Offsite Recycling Item Liquid
Effluent
Air
Emission Recovery
Solid
Waste
1 Bifenthrin - - 1.000 - Product
2 Sodium Sulfite
(19%) - - 2.11 - Byproduct
3 Hydrochloric
Acid (30%) - - 0.348 - Byproduct
4
Potassium
Chloride
solution
- 2.405 - Byproduct
5
Recovered
Ethylene dichloride
- - 0.960 - Recovered for Reuse
6 Recovered DMF - - 1.09 - Recovered for Reuse
7 Recovered
Hexane - - 1.12 -
Recovered for Reuse
8 Uncondensed
vapor - 0.192 - - Loss
9 Water - - - - To ETP
10 Residue - - - 0.12 To incinerator
Total
(Ton)
0 0.192 9.03 0.12
9.34
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3. Clodinafop Propargyl Technical
Process Description
Stage-1
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.
Process Flow Diagram of Clodinafop
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CHEMICAL REACTION - CLODINAFOP PROPARGYL
CH C – CH2OH + SOCl2 CH C - CH2Cl + HCl + SO2
Propargyl alcohol Thionyl Propargyl Chloride Hydrochloric Sulpherdioxide
56 Chloride 74.5 Acid [36.5] [64]
Stage-2 119
CH3 CH3
a)
C COOH C COOK
H
H + K2 CO3
+ KHCO3
+ DMF
OH OH
2-( 4-Hydroxy phenoxy Pot.Salt of HPPA - 220
Propionic acid ) -182 ( HPPA )
CH3
b) C -- COOK
H
Cl F
Pot.Salt of HPPA
+ K2CO3 +
N
F Pot. Carbonate OH
[138] MW=220
5-chloro-2,3-difloropyridine
[ 149.5]
Cl F
[100]
CH3 Pot.bicarbonate
N O C – COOK + KF + KHCO3
H
2 -[4-(5chloro-3-floro pyridin-2 oxy)phenoxy] Pot.Propionate +Pot.Floride
[349.5] [ 58]
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Remaining part of Clodinafop Propargyl reaction.
( C )
Cl F
CH3
N O C – COOK +CH C-CH2Cl
H
2 -[4-(5chloro-3-floropyridin-2 oxy)phenoxy ] Pot.propionate +Propargyl chloride
[349.5] [74.5]
Cl F
CH3
N C COO CH2 C CH + KCl
H Pot. Chloride
[ 74.5 ]
Clodinafop Propargyl
[ 349.5 ]
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Material Balance of Clodinafop Propargyl
S. No.
Input/Ton of Product Total Consumption to produce 1KG. of Clodinafop Technical Raw Materials
1 Propargyl Alcohol 0.300
2 Thionyl chloride 0.642
3 Dimethyl Formamide (DMF) (Fresh + Recovered) 2.74
4 Caustic Soda Lye 0.918
5 2-(4-hydroxy phenoxy propionic Acid) (HPPA) 0.61
6 5-Chloro 2,3 difluoro pyridine (CDFP) 0.52
7 Potassium carbonate 0.97
8 Methanol (Fresh + Recovered) 0.54
9 Toluene (Fresh + Recovered) 0.54
10 Water 6.86
Total (Ton) 14.64
S. No.
Output in Ton /Ton of Product Disposals / ETP
Offsite Recycling Item Liquid
Effluent
Air
Emission Recovery
Solid
Waste
1 Clodinafop - - 1 - Product
2 HCl (30%) - - 0.656 - Byproduct
3 Sodium
Sulfite(24%) - - 2.527 - Byproduct
4 Recovered
DMF - - 2.628 - Recovered for Reuse
5 Recovered
Methanol - - 0.516 - Recovered for Reuse
6 Recovered
Toluene - - 0.52 - Recovered for Reuse
7 DMF - 0.108 - - Loss
8 Methanol - 0.024 - - Loss
9 Toluene - 0.02 - - Loss
10 Salt + Water - - 6.366 - To ETP
11 Residue - - - 0.275 To Incinerator
Total (Ton) - 0.152 14.213 0.275
14.64
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4. 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.
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)
Stage –2 MW=151.5
CH3 CH3
a) CH
CH2CN CH3 HC—CN
+ CH3 CH – Br + NaOH + Cat-III TEBA
+ NaBr+H2O
Sod.bromide [103]
Cl Cl
ParachloroBenzyl cyanide + Isopropylbromide + Sodium hydroxide 4 -chloro phenyl isovaleryl nitril
MW=123 MW=40 MW=193.5
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Remaining part of Fenvalerate reaction
b)
CH3 CH3 CH3 CH3
CH CH
HC –CN HC COCl
+ SO2
+ H2SO4 + H2O + Cat-IV DMF+ SOCl2 + Hexane +HCl+H2O
Sulphuric Thionyl
Cl Acid Chloride Cl
MW=98 MW=119
4-chlorophenyl Isovaleryl Nitirile
c)
CH3 CH3
CH
HC – COCl
+ NaCN (Aq.) + OHC + Catalyst-V TEBA
Sodiumcyanide MPB
Cl
Para chlorophenyl Isovaleryl chloride
MW=231.5
CH3 CH3
CH H
HC COO C
+ Spent sodium cyanide for detoxification +NaCl
CN
Fenvalerate Technical
Cl MW=419
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Material Balance of Fenvalerate
S. No. Input/Ton of Product Total Consumption to produce
1KG. of Fenvalerate Technical Raw Materials
1 Para chloro Toluene 0.415
2 Chlorine 0.237
3 Catalyst I (Fresh + Recovered) ( AZDN) 0.002
4 Catalyst -II(TEA) 0.011
5 Sodium Cyanide 0.300
6 Isopropyl Bromide (Fresh + Recovered) 0.345
7 Caustic Soda Lye 0.762
8 Caustic Soda flakes 0.15
9 Catalyst III & V ( TEBA) 0.019
10 Sulphuric Acid 0.811
11 Sulphuric Acid 70% Wash 0.05
12 Dimethyl Formamide (DMF) 0.005
13 Thionyl chloride 0.356
14 Hexane (Fresh + Recovered) 1.160
15 Ethylene Dichloride (Fresh + Recovered) 0.03
16 Metaphenoxy Benzaldehyde 0.500
17 Soda Ash 0.01
18 Sodium hypo chlorite 0.05
19 Water 7.577
Total (Ton) 12.79
S. No.
Output in Ton /Ton of Product Disposals / ETP
Offsite Recycling Item Liquid
Effluent
Air
Emission Recovery
Solid
Waste
1 Fenvalerate - - 1 - Product
2 HCl 30% - - 0.765 - Byproduct
3 Spent acid - 1.251 - Byproduct
4 Sod. Sulphite Soln. (22%)
- - 1.693 - Byproduct
5 Catalyst - - 0.00184 - Recovered for Reuse
6 Isopropyl
bromide - - 0.01 - Recovered for Reuse
7 Hexane - - 1.12 - Recovered for Reuse
8 Ethylene Dichloride
- - 0.028 - Recovered for Reuse
9 Hexane - 0.040 - - Loss
10 Ethylene Dichloride
- 0.002 - - Loss
11 Uncondensed
Vapour 0.0656 - - Loss
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12 Spent Sod. Cyanide aq.
Soln.
1.9944 - - - To ETP through
detoxification unit
13 NaBr. Soln. 1.054 - - - To ETP through bromine recovery
15 Water 3.677 - - - To ETP
16 Residue - - - 0.04 To Incineration
17 Spent sod
hypochlorite 0.05 - -
-
TO ETP
Total (Ton)
6.78 0.108 5.87 0.04
12.79
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6. Fipronil Technical
Process Description
Trifluoromethane Sulfinyl chloride is reacted with 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoro methyl
phenyl)-1H-pyrazole to form Fipronil.Ethylene dischloride is used as solvent, which is recovered & reused.
Process Flow Diagram of Fipronil
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CHEMICAL REACTION OF FIPRONIL
CF3
S CN
CN
N
N + F3C S Cl Cat-B NH2 N + HCl
H2N N Sulfinyle chloride Cat –C MW=36.5
Cl Cl [152.5] Cl Cl
CF3 CF3
5-amino-3-cyano-2,6 – dichloro 4-trifluoromethyle Fipronil [ 437 ]
Phenyl pyrazole [ 321 ]
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Material Balance of Fipronil
S. No. Input/Ton of Product Total Consumption to
produce 1kg of Fipronil Technical Raw Materials
1 5-amino-3-cyno-1-(2,6-dichloro-4-trifluoro methyl phenyl)-1H-pyrazole
0.93
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
catalyst to form Lambda Cyhalothrin Tech.
Process Flow Diagram of Lamda Cyhalothrin
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CHEMICAL REACTION OF LAMBDA CYHALOTHRIN
CF3 + SOCl2 C F3
C = CH COOH C = HC COCl + HCl+SO2
Cl Cl
Lambda Acid Lambda Acid Chloride + Hydrochloric acid
MW=242.5 MW=261
CHO
CF3
C = CH COCl +
Cl O + NaCN + H2O
Lambda Acid chloride + MPB Sodium Cyanide Water
198
O +NaCN +NaCl
CF3
C = CH COO + CH -
Cl CN
Cyhalothrin Technical
MW=450
+ DIPA + IPA
Diisopropyl amine Isopropryl alcohol
O
CF3
C = CH COO CH + DIPA + IPA
Cl CN Di Isopropyl amine+ Isopropyl Alcohol
Lambda Cyhalothrin Technical
MW=450
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Material Balance of Lambda Cyhalothrin
S.
No.
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
glycol is recycle in next batch.
Process Flow Diagram of Metaphenoxy Benzaldehyde
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 32
CHEMICAL REACTION OF METAPHENOXY BENZALDEHYDE
Stage – 1
CHO CHO-- AlCl3
a) + AlCl3 + Br2 + Cl2 + EDC at + HCl
Br. Benzaldehyde + Aluminium Chloro +bromine + Chlorine - Complex + hydrochloric acid
MW=106
CHO – AlCl3 CHO
b) + H2O + HCl + ( Al2O3 + H2O + HCl ) (Alum)
Br. Br.
Stage – 2 Meta bromo benzaldehyde MW=185 O--CH2
CHO CH
O--CH2 CH2OH Cat-D PTSA
a) + CH2OH + H2O
Br. Br.
Meta bromo Benzaldehyde Mono ethylene glycol Meta bromo benzal acetal (MBBA)
MW=185 MW=62 MW=229 O—CH2 O—CH2
CH CH O— CH2 O—CH2
OH
b) + KOH + + Tol. CuCl + KBr.
Br. 56 Phenol Catalyst-E
94 +Pot. MBBA + Pot.Hydroxide Metaphenoxy Benzal Acetal (MPBA) bromide
c)
O — CH2 CHO CH
O— CH2 CH2OH +
+ H2O + H2SO4 CH2OH + H2SO4
Sulphuric acid MEG
MPBA 242 Metaphenoxybenzaldehyde
MW=198
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 33
Material Balance of Metaphenoxy Benzaldehyde
S. No. Input/Ton of Product Total Consumption to produce
1KG. of Metaphenoxy
Benzaldehyde Raw Materials
1 Ethylene dichloride 2.726
2 Benzaldehyde 0.7130
3 Alluminium chloride 1.1760
4 Bromine 0.590
5 Chlorine 0.250
6 Formic acid 0.025
7 Thiosulphate 0.0142
8 Hydrochloric Acid (HCl) 0.428
9 PTSA ( Cat-D) 0.001
10 Caustic Soda lye 0.159
11 Mono Ethyl Glycol 0.800
12 Catalyst-E ( CuCl) 0.00310
13 Toluene (Fresh + Recovered) 1.726
14 Potassium Hydroxide (KOH) 0.390
15 Phenol 0.590
16 Sulphuric Acid 0.032
17 Water 6.296
Total (Ton) 15..919
Output in Ton /Ton of Product Disposals / ETP
Offsite Recycling Item Liquid
Effluent
Air
Emission Recovery Solid Waste
1 Metaphenoxy Benzaldehyde
- - 1 - Product
2 Aq. Alum - - 5.298 - Byproduct
3 HCL 30% - - 0.818 - Byproduct
4 Rec. EDC - - 2.591 - Recovered for
Reuse
5 Catalyst ( PTSA)
- - 0.001 - Recovered for Reuse
6 Rec. MEG - - 0.76 - Recovered for
Reuse
7 Rec. Toluene - - 1.657 - Recovered for
Reuse
8
Water
recovered from MBBA
reaction
- - 0.1085 - Reused
9
Water recovered
from MPBA reaction
- - 0.1085 - Reused
10 Water from
KOH 0.039 - Reused
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 34
11
Water
recovered from spent
MEG
-- - 0.476 - Recovered & reused
12 EDC - 0.14 - - Loss
13 MEG - 0.04 - - Loss
14 Toluene - 0.07 - - Loss
15 Water 0.380 - - - To ETP
16 Effluent for
ventury 0.243 - - - To ETP
17 KBr. Soln.
- 1.928 - To ETP through bromine recovery
18 Residue - - - 0.167 To incineration
19 Sod. Sulphate 0.058 - - -
To incineration
Total
(Ton)
0.717 0.25 14.785 0.167
15.919
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 35
9. Permethrin Technical
Process Description
DV acid chloride reacted with Meta-phenoxybezyl alcohol & produced Permethrin tech. which is washed
with water & water is flushed under vacuum. Hydrogen chloride gas evolve is scrubbed in water.
Process Flow Diagram of Permethrin
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 36
CHEMICAL REACTION OF PERMETHRIN
H3C CH3
CH2OH
Cl
+ C HC COCl
Cl
Metaphenoxy Benzyl alcohol + DV Acid Chloride
MW=200 MW=227.5
H3C CH3
H
Cl H
C C COO C + HCl
Cl
H
Hydrochloric Acid
Permethrin Technical
MW=391
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 37
Material Balance of Permethrin
S. No. Input/Ton of Product Total Consumption to produce
1 KG. of Permenthrin Technical Raw Materials
1 Cypermethric Acid chloride 0.60
2 Metaphenoxy Benzyl alcohol 0.52
3 Caustic Soda Lye 0.03
4 Soda Ash 0.02
5 Acetic Acid 0.01
6 Water 1.31
Total (Ton) 2.49
S. No.
Output in Ton /Ton of Product Disposals / ETP
Offsite Recycling Item Liquid
Effluent Air
Emission Recovery
Solid Waste
1 Permethrin
Tech. - - 1 - Product
2 HCl Soln.
(31%) - - 0.32 - Byproduct
3 Ventury
Soln. 0.152 - - - To ETP
4 Water 1.014 - - - To ETP
Total
(Ton)
1.166 - 1.32 -
2.49
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 38
10. Safener (Cloquintocet Mexyl)
Process Description
Stage – 1
Monochloro acetic acid reacted with 2-heptanol and produced -2-chloroheptyl acetate. Toluene is used as
solvent. Recovered Toluene is reused in process.water formed in reaction is removed azeotropically.
Stage – 2
2-choro heptyl acetate reacted with 8-hydroxy 5-chloroquinoline and pot. Carbonate and produced
cloquintocet mexyl. N – methyl pyrolidone(NMP) is used as solvent.Recoverd NMP is reused.
Process Flow Diagram
MCA
2- HEPTANOL Recovered Toluene
Toluene Water
Residue for
Inceneration
Potassium Carbonate
Toluene Recovered NMP
NMP Recovered Toluene
Water Effluent Water 5-Chloro 8- Hydroxy
quinolene
DRYING
Safener Packaging
PREPARATION OF 2-
CHLOROHEPTYL
ACETATE
CONDENSATION
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 39
CHEMICAL REACTION OF SAFENER
Stage -1
Cl- CH2 - COOH + HO - CH2 – CH – CH2CH2 - CH3CH3 + Toluene
MCA
94.5 CH3 2-heptanol MW=116
Cl – CH2 – COO – CH2 – CH- CH2 – CH3 – CH2 – CH3 + H2O
2-Chloro heptyl acetate [192.5]
CH3
Stage-2
2)
Cl 5 chloro -8-hydroxy quinoline
2 chloro-heptyl acetate
+ Cl – CH2 – COO - CH2-CH-CH2-CH2-CH2 + ½ K2CO3 + Tol.+NMP
Pot.carbonate
N CH3 CH3 138
H
179.5
Cl
CH3
N
CH2 - COOCH2 – CH - CH2 - CH2 - CH2 CH3
+ KCl + H2O + CO2
Potassium Chloride
Cloquintocet Mexyl 74.5
(Safener)
335.5
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 40
Material Balance of Safener
S. No.
Input/Ton of Product Total Consumption to
produce 1 KG. of Safener (Cloquintocet Methyl)
Technical Raw Materials
1 Toluene (Fresh + Recovered) 1.48
2 2-Heptanol 0.38
3 Mono chloro Acetic Acid 0.31
4 5-chloro-8-hydroxy quinolone 0.56
5 n- methyl pyrolidone (NMP) 1.48
6 Potassium carbonate 0.49
7 Water 3.8
Total (Ton) 8.50
S. No.
Output in Ton /Ton of Product Disposals / ETP
Offsite Recycling Item Liquid
Effluent
Air
Emission Recovery
Solid
Waste
1 Safener - - 1 - Product
2
Pot. Chloride
K2CO3+KHCO3 +water
- - 3.4 - By-product
3 Rec. Toluene - - 1.42 - Recovered for Reuse
4 Rec. NMP - - 1.41 - Recovered for Reuse
5 NMP - 0.07 - - Loss
6 Toluene 0.06 Loss
7 Uncondensed
Vapor - 0.04 - - Loss
8 Water 1.062 - - - To ETP
9 Impurities - - - - To Incineration
10 Residue - - - 0.038 To Incineration
Total (Ton)
1.062 0.17 7.23 0.038
8.50
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 41
11. Thiomethoxam Technical
Process Description
3-methyl-4-nitro perhydro-1,3,5-oxadiazine is reacted with 2-chloro-5-chloromethyl-1,3-thiazole in
presence of suitable solvent and base to form Thiamethoxam.
Process Flow Diagram Thiomethoxam
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 42
CHEMICAL REACTION OF THIOMETHOXAM
N NO2
Cl S C
CH2Cl
+ NaOH + HN N CH3
N
O
2-chloro-5-chloromethyl thiazole 3-methyl-4-nitroperhydro,1,2,5 oxadiazene
MW=168 Sod.hydroxide MW=160
MW=40
N NO2
Cl S
CH2
N N CH3 + NaCl + H2O
N Sod.chloride
MW= 58.5
Thiomethoxam
MW=291.5
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 43
Material Balance of Thiomethoxam
S. No. Input/Ton of Product Total Consumption to
produce 1 KG. of
Thiomethoxam Technical Raw Materials
1 2-Chloro-5 –chloromethyl thiazole (CCMT) 0.70
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
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 44
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
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 45
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 ]
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 46
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
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 47
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
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 48
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
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 49
Material Balance of Difenconazole
1 2-(4-(4 chloro phenoxy )2-chloro phenyl )-2 bromo methyl 4 methyl -1 ,3dioxalone
1.29
2 1,2,4 triazole 0.25
3 Dimethyl formamide 4.00
4 Potassium carbonate 0.64
5 Methanol 2.500
6 Water 4.000
Total (Ton) 12.68
S. No.
Output in Ton /Ton of Product Disposals / ETP
Offsite Recycling Item Liquid
Effluent Air
Emission Recovery
Solid Waste
1 Difenconazole
Technical - - 1.00 - Product
2 Recovered DMF
- - 3.80 - Recovered & reused
3 Recovered Methanol
- 2.40 - Recovered & reused
4 Carbon dioixide - 0.068 - - Loss
5 Uncondensed vapor
0.30
6 Potassium Bromide
- 4.791 - For Bromine Recovery
7 Unreacted Potassium
Carbonate
- - - - To ETP
8 Water - - - - To ETP
9 Unreacted
1,2.4 -triazole 0.04 - - - To ETP
10 Water formed in reaction
0.03 - - - To ETP
Residue 0.25 Incineration
Total
(Ton)
0.07 0.37 11.99 0.25
12.68
BHARAT RASAYAN LTD. FORM 1
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14. Propanil Technical
Process Description
3,4-dichloro aniline is refluxed with excess propionic acid to form Propanil.
Excess propionic acid is recovered under reduced pressure and crude propanil is flushed
under reduced pressure to remove traces of propionic acid.
Process Flow Diagram of Propanil
Propionic Acid
3,4 dichloro aniline
Catalyst-H
Propionic acid recd. & reuse
Propanil Packing
Condensation
Distillation
Flushing
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 51
CHEMICAL REACTION OF PROPANIL
NH2 NH – C – CH2CH3
Cat-H
+ CH3CH2COOH + H2O + Propionic
Cl Cl Acid
Cl Cl
Propionic Acid Propanil MW=74 MW=218 3,4-Dichloro aniline MW=162
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 52
Material balance of Propanil
1 3,4- Dichloro aniline 0.752
2 Propionic acid 1.030
3 Catalyst 0.01
Total (Ton) 1.79
S. No.
Output in Ton /Ton of Product Disposals / ETP
Offsite Recycling Item Liquid
Effluent Air
Emission Recovery
Solid Waste
1 Propanil - - 1 - Product
2 Recovered
Propionic acid - - 0.66 - Recovered & reused
3 Propionic acid - 0.04 - - Loss
4 - - - -
5 Water to ETP+
catalyst 0.09 - - - ETP
6 Residue - - - -
Total (Ton)
0.09 0.04 1.66 -
1.79
BHARAT RASAYAN LTD. FORM 1
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15. Pyrazolsulfuron Tech.
Process Description
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
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 54
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
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 55
Materia Balance Pyrazolsufuron
1 Ethyl-1-methyl -5-sulphanamide isocyanide- 1-H pyrazole-
4-carboxylate 0.80
2 2- amino -4,6-dimethoxy pyrimidine 0.490
3 Toluene 3.00
4 Methanol 2.00
Total (Ton) 6.29
S. No.
Output in Ton /Ton of Product Disposals / ETP
Offsite Recycling Item Liquid
Effluent Air
Emission Recovery
Solid Waste
1 Pyrazosulfuron
Tech. - - 1.00 - Product
2 Toluene - - 2.90 - Recovered & reused
3 Methanol - - 1.93 - Recovered & reused
4 Uncondensed vapor
(Toluene)
- 0.17 - - Loss
5 Uncondensed vapor
(Methanol)
- - - - Loss
6 Residue 0.292 Incinerator
Total (Ton)
00 0.17 5.83 0.292
6.29
BHARAT RASAYAN LTD. FORM 1
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16. Parachlorophenyl alpha isopropyl acetic acid (PCA)
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 then dissolve in hexane crystalysed &
fiter.Materail dried & packed.
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 57
Process Flow Diagram PCA
BHARAT RASAYAN LTD. FORM 1
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CHEMICAL REACTION OF PCA
Stage – 1
CH3 CH2Cl
i
a) + Cl2 + Catalyst-AZDN + HCl
Chlorine
Cl Cl
Parachloro Toluene Para chlorobenzylchloride
MW=126.5 MW=161
CH2 – Cl CH2CN
b) + H2O + NaCN + Catalyst-TEA + NaCl
Sod.chloride [58.5]
Cl Cl Para chlorobenzyl
Cyanide
Para chloroBenzylchloride + Sodium Cyanide (PCBCN)
Stage –2 MW=151.5
CH3 CH3
a) CH
CH2CN CH3 HC—CN
+ CH3 CH – Br + NaOH
+ NaBr+H2O
Sod.bromide
Cl Cl [103]
ParachloroBenzyl cyanide + Isopropylbromide + Sodium hydroxide 4 -chloro phenyl isovaleryl nitril
MW=123 MW=40 MW=193.5
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 59
Remaining part of PCA reaction
b)
CH3 CH3 CH3 CH3
CH CH
HC –CN H C COOH
+ H2SO4 + H2O + Hexane + H2SO4+H2O
Sulphuric +(NH4)2SO4
Cl Acid Cl Amm.sulphate
MW=98 Parachlorophenyl [132]
4-chlorophenyl Isovaleryl nitrile Isopropyle acetic acid
[ 193.5] [ 212.5]
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BHARAT RASAYAN LTD. 60
Material Balance of PCA
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
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 62
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
BHARAT RASAYAN LTD. FORM 1
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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.
Process flow diagram of Myclobutanil
Butyl Bromide
PCBCN Sod. Bromide Soln.
Caustic Soda Soln.
Dichloromethane
Caustic Soda Soln. Sodium Chloride Soln.
1,2,4-Triazole
DMF Sodium Chloride
Caustic Soda Flakes
Water Recd. DMF
Water as Effluent
Myclobutanil
Condensation
Condensation
Condensation
Recovery & Washing
Drying & Packing
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 65
CHEMICAL REACTION OF MYCLOBUTANIL
CH2CH2CH2CH3
CH2CN H – C - CN + CH3CH2CH2CH2Br + NaOH + NaBr + H2O Sod.hydroxide [40] Sod.bromide [103] Cl Cl PCBCN Butyl bromide 2-(4-chloropheny)hexane nitrile MW=151.5 MW = 137 MW = 207.5 CH2CH2CH2CH3 CH2CH2CH2CH3
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
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 66
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
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 67
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.
Wet cake is dried and packed in suitable packing.
Process flow diagram Tebuconazole
2-[2[(4-chlorophenyl)
Ethyl]-2-(1,1dimethyle-ethyle)Oxirane
1,2,4-Triazole
Sod. Hydroxide
DMF
Recovered DMF
Water
Waste Water to Effluent
Condensation
Filtration & Drying
Washing
Recovery
Tebuconazole
Packing
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 68
CHEMICAL REACTION OF TEBUCONAZOLE
H
N
+ N + NaOH
Cl C N Sod.hydroxide [40 ]
C CH3 1,2,4-Triazole [69]
CH3
CH3
2-[2[(4-chlorophenyl) ethyl]-2-(1,1-dimethyl-ethyl)
Oxirane [ 238 ]
OH CH3
Cl CH CH2 C C CH3 + NaOH
CH2 CH3
N
N
N
Tebuconazole
MW = 307.5
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 69
Material Balance of Tebuconazole
S. No. Input/Ton of Product Total Consumption to produce
1 KG.Of parachloro pheny
alpha isopropyl acetic acid Raw Materials
1 2-[2[(4-chlorophenyl)ethyl]-2-(1,1 dimethyl-ethyl)oxirane 0.86
2 1,2,4-Triazole 0.30
3 Sodium Hydroxide 0.17
4 DMF 4.00
5 Water 3.00
Total (Ton) 8.33
S. No.
Output in Ton /Ton of Product Disposals / ETP
Offsite Recycling Item Liquid
Effluent
Air
Emission Recovery
Solid
Waste
1 Tebuconazole
Tech. - - 1.00 - Product
2 Recovered DMF - - 3.80 - Recovered and
reuse
3
Unreacted
Sodium
Hydroxide
0.144 - - - To ETP
4 1,2,4-Triazole
Sodium Salt 0.07 - - - To ETP
5 Water formed 0.01 - - - To ETP
6 Impurities 0.11 - - - To ETP
7 Uncondensed
DMF - 0.200 - - Loss
8 Water 3.00 - - - To ETP
Total (Ton)
3.33 0.200 4.80 00
8.33
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 70
20. Imiazethapyre Tech.
Process Description
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
HCl to get IMAZETHAPYR (T)
Process Flow diagram Imiazethapyre
Diethyl 5-ethyle
Pyridine-2,3 dicarboxylate
2-amoni-2,3 dimethyl Effluent
Butyramide
Toluene
HCl
Reactor
Filtration & Drying
Imiazethapyre
Packing
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 71
CHEMICAL REACTION OF IMIAZETHAPYRE
NH2 CH3 CH3 COOC2H 5 Sod.methoxide [108] + C – C – CH + 2CH3ONa + 2 HCl Hydrochloric acid N NH2 CH3 (36.5×2) COOC2H5 Diethyl -5-ethyl pyridine – 2 2-amino-2,3-dimethyl -3-dicarboxylate butyramide [ 251] [130] COOH N CH3 N + 2C2H5OH + 2 CH3OH + 2 NaCl Ethanol Methanol Sod.chloride
HN [46 x 2 ] [32x2] [58.5 x 2]
[92] [64] [117]
[289 ]
Imiazethapyr
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 72
Material Balance
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
3 1,2,4-triazole Solid 31.85 - Fiber Drum Ambient Ambient 400 50 Kg. 20
4 5-amino-3-cyno-1-(2,6-dichloro-4-trifluoro methyl
Pheny)-1H-pyrazole
Solid 9.30 Lachrymator Fiber Drum Ambient Ambient 280 25 Kg. 7
5 2-amino-4,6-dimethoxy
pyrimidine Solid 9.82 - Fiber Drum Ambient Ambient 160 50 Kg. 8
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 74
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)
6 3,4-dichloroaniline Solid 37.50 - Poly Bag Ambient Ambient 800 25 Kg. 20
7 Dichloromethane Liquid 16.50 Flammable MS storage
tank Ambient Ambient 1 10 KL 10
8 Diethyl-5-ethyl pyridine-2,3-
decarboxylate Solid 27.25 Non-Hazard Fiber Drum Ambient Ambient 400 50 Kg. 20
9 Ethyle-1-Methyl-5-sulfinamide isocyanate-
H,pyrazole-4-carboxylate
Solid 16.00 Toxic Fiber Drum Ambient Ambient 240 50 Kg. 12
10 2-amino-2,3-dimethyl
butyamide Solid 14.75 Non-Hazard Fiber Drum Ambient Ambient 200 50 Kg. 10
11 2-Heptanol Liquid 11.40 Toxic MS Drum Ambient Ambient 58 170 Kg. 9.86
12 5-chloro-8-hydroxy
quinolone Solid 16.8 Non-Hazard HDPE bags Ambient Ambient 416 30 kg. 12.48
13 2-chloro-5-chloromethyl thiazole (CCMT)
Liquid 210.00 Lachrymator HDPE drum Ambient Ambient 80 250 Kg. 20
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 75
Sr.
No. Chemical State
Consumption,(MT/An
num
Hazard
Involved
Means of
Storage
Operating
Condition
(Storage)
No of
Drum
or Vessel
Packing size
Max.
Storage
Capacity (MT)
Press (Kg/Cm2)
Temp (0C)
14
3-methyl-4-nitro per
hydro,1,2,5
oxadiazene(MNPO)
Solid 210.00 - Fiber Drum Ambient Ambient 800 25 Kg. 20
15 2(4-hydroxy phenoxy
propionic Acid)HPPA) Solid 61.00 Fiber Drum Ambient Ambient 400 50 Kg. 20
16 5-Chloro 2,3 difluro pyridine (CDFP)
Liquid 52.00 - M.S. Drum Ambient Ambient 100 200 20
17 Copouros chlorite Solid 5.58 - HDPE bags Ambient Ambient 100 20 2
18 4-dimethyl amino pyridine Solid 3.000 Lachrymator Fiber Drum Ambient Ambient 80 25 Kg. 2
19 Methanol Liquid 537.00 MS storage
tank Ambient Ambient 1 30 KL 30
20 Acetic Acid Liquid 144.50 - HDPE drum Ambient Ambient 25 200 Kg. 5
21 Ammonia ( solution 20% ) Liquid 0.30 - HDPE drum Ambient Ambient 4 50 Kg. 0.2
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 76
Sr.
No. Chemical State
Consumption,(
MT/Annum
Hazard
Involved
Means of
Storage
Operating Condition
(Storage) No of
Drum or Vessel
Packing size
Max. Storage
Capacit
y (MT) Press
(Kg/Cm2) Temp (0C)
22 Aluminium Chloride Liquid 2116.80 Evalution of
HCl gas bags Ambient Ambient 1000 25 Kg. 25
23 Benzaldehyde Liquid 1283.40 HDPE drum Ambient Ambient 200 200 Kg. 40
24 Bifenthrin Alcohol Solid 68.40 bags Ambient Ambient 800 25 Kg. 20
25 Bromine Liquid 1062.00 Toxic Glass Bottle Ambient Ambient 6666 3 kg. 19.98
26 Butyl Bromide Liquid 9.15 Inflammable MS Drum Ambient Ambient 30 250 kg. 7.5
27 Catalyst MR liquid 0.45 - HDPE drum Ambient Ambient 5 50 Kg. 0.25
28 Catalyst –H Liquid 0.15 - HDPE drum Ambient Ambient 1 100 kg. 0.1
29 Caustic Soda Flakes Solid 462.85 Corrosive HDPE bags Ambient Ambient 200 50 kg. 10
30 Caustic Lye ( 47%) Liquid 709.02 Corrosive MS storage
tank Ambient Ambient 2 20 KL 36
31 Chlorine Gas 671.50 Toxic Cylinder Ambient Ambient 22 900 kg. 19.8
32 Azobis Isobutaronitrile
Solid 1.90 Fiber Drum Ambient Ambient 50 20 kg. 1
33 Cypermethrin Acid
Chloride Liquid 347.750 -
Plstic coated
MS. Drums Ambient Ambient 72 250 kg. 18
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 77
Sr.
No. Chemical State
Consumption,(MT/A
nnum
Hazard
Involved
Means of
Storage
Operating Condition
(Storage) No of Drum
or Vessel
Packing size
Max. Storage
Capacity (MT)
Press (Kg/Cm2)
Temp (0C)
34 Di isopropyl Amine Liquid 12.00 - MS Drum Ambient Ambient 35 140 kg. 4.9
35 Di isopropyl phenoxy
phenyl thio urea Solid 145.50 - HDPE bags Ambient Ambient 400 50 Kg. 20
36 Dimethyl Formamide (DMF) Liquid 1963.70 - MS Drum Ambient Ambient 150 200 kg. 30
37 Ethylene Dichloride (EDC) Liquid 5386.80 Toxic MS storage tank Ambient Ambient 1 40 KL 30
38 Hexane Liquid 2656.20 Fire hazard MS storage tank Ambient Ambient 2 20 KL 25
39 Formic Acid Liquid 45.00 - HDPE drum Ambient Ambient 142 35 kg. 4.97
40 Hydrochloric Acid (30%) Liquid 780.90 Corrosive HDPE storage
Tank Ambient Ambient 2 20 KL 20
41 Isoprypyl Alcohol Liquid 237.00 Fire hazard MS storage tank Ambient Ambient 1 30 KL 25
42 Isoprypyl Bromide Liquid 237.50 Toxic HDPE drum Ambient Ambient 80 250 Kg. 20
43 Lambda Acid Solid 240.60 Toxic HDPE bags Ambient Ambient 1200 25 kg. 30
44 Lambda Powder (seeding) Solid 6.00 irritated hdpe drum Ambient Ambient 125 40 kg. 5
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 78
Sr.
No. Chemical State
Consumption,(MT/A
nnum
Hazard
Involved
Means of
Storage
Operating Condition
(Storage) No of Drum
or
Vessel
Packing size
Max. Storage
Capacity
(MT) Press
(Kg/Cm2)
Temp
(0C)
45 Metaphenoxy Benzaldehyde Liquid 529.050 Toxic HDPE drum Ambient Ambient 180 200 kg. 36
46 Metaphenoxy benzalalcohol Liquid 52.00 Toxic hdpe drum Ambient Ambient 88 225 kg. 19.8
47 Monochloro Acetic Acid Solid 9.30 Toxic HDPE bags Ambient Ambient 160 50 kg. 8
48 Mono Ethyl Glycol Liquid 1440.00 Toxic MS storage
tank Ambient Ambient 1 30 KL 30
49 n-methyl pyrolidine (NMP) Liquid 44.40 Toxic HDPE drum Ambient Ambient 100 200 kg. 20
50 Orthoxylene Liquid 34.85 Fire hazard MS storage
tank Ambient Ambient 1 30 KL 10
51 Parachloro Benxyl cyanide Liquid 10.20 lachrymator HDPE drum Ambient Ambient 40 200 kg. 8
52 Parachloro Toluene Liquid 88.70 Fire hazard M.S. Drum Ambient Ambient 150 200 kg. 30
53 Paratolune sulphonic acid
(PTSA) Solid 1.80 - HDPE bags Ambient Ambient 24 50 1.2
54 Phenol Solid 1062.00 Corrosive MS storage
tank Ambient Ambient 1 30 KL 30
55 Potassium Carbonate Solid 186.90 Fire hazard HDPE bags Ambient Ambient 800 25 kg. 20
56 Potassium Hydroxide (KOH) Solid 702.00 - HDPE bags Ambient Ambient 800 50 Kg. 40
57 Propargyl alcohol Liquid 30.00 - MS Drum Ambient Ambient 111 180 kg. 19.98
58 Propionic Acid Liquid 51.50 - HDPE drum Ambient Ambient 100 200 kg. 20
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 79
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)
59 Sodium methoxide Solid 14.5 corrosive HDPE drum Ambient Ambient 80 50 kg. 4
60 Soda Ash Solid 86.00 Toxic HDPE bags Ambient Ambient 200 50 kg. 10
61 Sodium bicarbonate
(NaHCO3) Solid 3.00 - HDPE bags Ambient Ambient 40 50 kg. 2
62 Sodium Thiosulfite Solid 25.56 Highly toxic HDPE bags Ambient Ambient 100 50 kg. 5
63 Sodium Cyanide Solid 302.00 Highly toxic MS Drum Ambient Ambient 400 50 kg. 20
64 Sodium Hypo Chlorite Liquid 242.80 - HDPE storage
Tank Ambient Ambient 1 15 KL 20
65 Sulphuric Acid 70% wash Liquid 15.00 Corrosive HDPE drum Ambient Ambient 16 250 Kg. 4
66 Sulphuric Acid Liquid 618.50 Corrosive MS storage tank Ambient Ambient 1 30 KL 30
67 Tertiary butyl amine Liquid 34.50 corrosive M.S. Drum Ambient Ambient 75 200 15
68 Thionyl chloride Liquid 286.60 Corrosive/tox
ic MS drum Ambient Ambient 100 300 kg. 30
69 Toluene Liquid 3352.70 Fire hazard MS storage tank Ambient Ambient 2 20 KL 30
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 80
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)
70 Triethylamine (TEA) Liquid 19.70 - MS Drum Ambient Ambient 66 150 kg. 9.9
71 Trifloromethan sulfinyl chloride
Liquid 49.00 - Coated MS
drum Ambient Ambient 400 50 kg. 20
72 Trimethyle amine hydrochloride
Solid 49.00 Toxic HDPE bags Ambient Ambient 400 25 kg. 10
73 Triethyl benzyl ammonium chloride
Solid 20.60 Lachrymator HDPE drum Ambient Ambient 25 200 kg. 5
TOTAL 29255.98 20515 1236.94
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 81
Sr. No.
Chemical State Production , (MT/Annum
Hazard Involved
Means of Storage
Operating Condition
(Storage) No of
Drum or
Vessel
Storage Capacity
Max.
Storage Capacity
(MT) Press
(Kg/Cm2) Temp (0C)
PRODUCTS
1 Alpha Cypermethrin Solid 100 Toxic Fiber Drum Ambient Ambient 100 50 Kg. 5
2 Bifenthrin Technical Solid 120 Toxic MS drum Ambient Ambient 50 200 kg. 10
3 Clodinafop Technical Solid 100 Toxic Fiber Drum Ambient Ambient 500 40 kg. 20
4 Cypermethrin Technical Liquid 350 Toxic MS Drum Ambient Ambient 180 200 Kg. 36
5 Difenthiuron Technical Solid 150 Toxic Fiber Drum Ambient Ambient 400 40 kg. 16
6 Difenconoazole Solid 50 Toxic Fiber Drum Ambient Ambient 200 50 kg. 10
7 Fipronil Technical Solid 100 Toxic Fiber Drum Ambient Ambient 125 40 kg. 5
8 Fenvalerate Technical Liquid 300 Toxic MS Drum Ambient Ambient 100 200 kg 20
9 Imiazethapyre Technical Solid 25 Toxic Fiber Drum Ambient Ambient 100 50 kg. 5
10 Lambda Cyhalothrin
Technical Liquid 300 Toxic M.S. Drum Ambient Ambient 100 200 kg.
20
11 Metaphenoxy Benzaldehyde Liquid 1800 Toxic HDPE drum Ambient Ambient 160 225 kg. 36
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 82
Sr. No.
Chemical State Consumption, (MT/Annum
Hazard Involved
Means of Storage
Operating Condition
(Storage) No of
Drum or
Vessel
Storage Capacity
Max.
Storage Capacity
(MT) Press
(Kg/Cm2)
Temp
(0C)
12 Myclobutanil Technical Solid 15 Toxic Fiber Drum Ambient Ambient 20 50 Kg. 1
13 Para Chlorophenyl isopropyl
acetic acid Solid 200 Toxic HDPE bags Ambient Ambient 40 500 kg. 20
14 Para Chloro benzyl cyanide Liquid 100 Toxic HDPE drum Ambient Ambient 90 200 kg. 18
15 Permethrin Technical Liquid 100 Toxic MS Drum Ambient Ambient 50 200 kg. 10
16 Propanil Technical Solid 50 Toxic MS Drum Ambient Ambient 50 200 kg. 10
17 Pyrizolesulfuron Technical Solid 20 Toxic Fiber Drum Ambient Ambient 40 50 2
18 Safener ( CloquintocetMexyl Solid 30 Toxic Fiber Drum Ambient Ambient 125 40 kg. 5
19 Thiamethoxam Technical Solid 300 Toxic Fiber Drum Ambient Ambient 625 40 kg. 25
20 Tebuconazole Solid 50 Toxic Fiber Drum Ambient Ambient 40 50 kg. 2
TOTAL 4260 3585 298
BHARAT RASAYAN LTD. FORM 1
BHARAT RASAYAN LTD. 83
Sr. No.
Chemical State Consumption, (MT/Annum
Hazard Involved
Means of Storage
Operating Condition
(Storage) No of
Drum or
Vessel
Storage Capacity
Max.
Storage Capacity
(MT) Press
(Kg/Cm2) Temp (0C)
LIST OF BYPRODUCTS
1 Alum Liquid 9536.4 Corrosive HDPE
storage Tank Ambient Ambient 3 20 KL 60 KL
2 Pot. Chloride Liquid 5036.5 Corrosive HDPE
storage Tank Ambient Ambient 2 20 KL 40 KL
3 Spent Acid Liquid 824.95 Corrosive HDPE
storage Tank Ambient Ambient 2 20 KL 40 KL
4 Hydrochloric Acid 28% Liquid 2236.2 Corrosive HDPE
storage Tank Ambient Ambient 2 20 KL 40 KL
5 Sodium Sulfite Liquid 1427.1 Corrosive HDPE
storage Tank Ambient Ambient 2 20 KL 40 KL
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
BHARAT RASAYAN LTD.
BHARAT RASAYAN LTD. 84
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
BHARAT RASAYAN LTD.
BHARAT RASAYAN LTD. 85
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
BHARAT RASAYAN LTD.
BHARAT RASAYAN LTD. 86
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.
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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.
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Block Diagram of ETP (100 KLD):
Polyelectrolyte
Lime
Plant –A+B
Plant - C
For Plant use
Oil Separator Retention Pond for treated cyanide
Skimmer
Lime sludge beds
Size: 4 x 3 x 1 m
8.6x8.6x1.7m ETP water collection Tank
MEE Plant
Pond No.2
8.6x8.6x1.7m Equalization Tank with Cost Diffuser
Neutralization R-702
Cap.10Kl
Primary settler Cap.28 KL
Pond No.3
Airation
10x6.5x1.7m
MEE distill
water 20 KL
Pond No.9
43.3x24x .4
Feed Tank
4 KL
Biological Airation
Pond No.1 – 150 KL
Biological Airation Pond No.2 (10x6.5x1.5m)
Carbon Filter Media Filter
Clear Water Holding
Tank Cap.20 KL
Pond No.10
24x3x1 Pond No.11
42x26.7x1.85
Pond No.12
42x25.5x2.85
Solid waste
Residue storage Shed (13x7x1.5)
Size:16x13x1.5
Lime Sludge Storage Shed
Size: 10 x 23 x 3
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Annexure 4: Water Consumption Details
S.
No. Area
Water Consumption in KLD
Existing After Product Mix
1 Domestic 30 35
2 Industrial Process
48.004 66.719
3 Washing 2.0 3.0
4 Cooling 20.0 30
5 Boiler 50.0 60
Total (Industrial) 150.004 194.719
Gardening 30.0 40
Total Water Consumption KL/day 180.004 234.719
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Annexure 5: Fuel Consumption
S. No.
Name of Fuel Consumption
Existing After Product Mix
1
Furnace Oil
5.5MT/Day 6.5 MT/Day
2 Coke 8.5MT /day 10 MT/Day
3 HSD* 0.85 MT/Day 1 MT/Day
*For emergency use only in DG Set
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Annexure 6: Hazardous Waste Generation
Sr. No. Type of Waste
Category
as per HW
TOTAL QUANTITY, MT/Year
Treatment / Disposal Method
Existing After
Product
Mix
1. Used Oil 5.1 0.726 1
Collection, Storage, Transportation & Disposal
by selling to registered reprocessor / reuse as
lubricant
2.
Process Waste / Waste Residue containing
Pesticides
29.1 229.42 529.22
Collection, Storage,
Incineration at common Incineration / Disposal of
Incinerable waste to Cement Industry
3. ETP Sludge 29.2 1236 1550.0
Collection, Storage, Transportation & Disposal
at nearest TSDF site (GEIPL, Pali) / Sludge from
Primary Treatment to Cement Industry
4. Date Expired / off specification
products
29.3 Nil 1.0 Collection, Storage,
Incineration at common
incineration
5. Discarded Container
33.3 3000 Nos. 5000 Nos. Collection, Storage, Decontamination,
Detoxification & sell to authorized vendor 6.
Discarded bag / liners
33.3 3 4
7.
Distillation
Residue from contaminated
organic solvents
36.4 0 0 Collection, Storage,
Incineration at common
incinerator
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Annexure 7: Stack Details
Flue Gas Stacks
Stack Attached to Sources Stack Height, m Stack Top Dia, m
Existing
Boiler 1 30 1M
DG Set–I (1250 KVA) 11 300mm
DG Set – II (275 KVA) 11 300mm
After Product Mix
Boiler 1 30 1M
DG Set–I (1250 KVA) 11 300mm
DG Set – II (275 KVA) 11 300mm
Thermic Fluid Heater 30
Process Vents
Stack Attached to Stack height in m
Existing
Process Vent – I 15
Process Vent – II 15
Process Vent- III 15
Process Vent- IV 15
After Product Mix
Process Vent – I 15
Process Vent – II 15
Process Vent- III 15
Process Vent –IV 15