PRE-FEASIBILITY REPORT · 2019-04-11 · PRE-FEASIBILITY REPORT . FOR . Greenfield Multi-Purpose Plant for Manufacturing of Various Technical Grade Pesticides and Intermediates

PRE-FEASIBILITY REPORT FOR

Greenfield Multi-Purpose Plant for Manufacturing of Various Technical Grade Pesticides and Intermediates

AT

Plot No. D-3/5/3 GIDC Dahej Phase III, Tal Vagara, Dist. Bharuch, Gujarat

Total Production Capacity Pesticides Technical :26700 MTPA

Intermediate :4400 MTPA Plot Area: 100272.418 sqm (10.02 Ha)

Cost of the Project: 170 Cr [Schedule 5 (b), Category–A as per EIA Notification 2006,

amended till date]

April – 2019

Doc. No: 2018_ECSS_EIAI2_1800019

APPLICANT

CONSULTANTS

Shreeji Pesticides Pvt. Ltd. (Subsidiary of Willowood Chemicals Pvt. Ltd.)

Plot no 69/P Village manjusar Tal Savli Vadodara

PIN: 391775, State: Gujarat E-mail:

[email protected] Tel No: +91 2641-256315

Eco Chem Sales & Services Office floor, Ashoka Pavilion ’A’ New Civil Road, Surat, 395001

(NABET Accredited-NABET/EIA/1720/RA 051)

E-mail: [email protected] Tel No: +912612236223

mailto:[email protected]

Prefeasibility Report SHREEJI PESTICIDES PVT. LTD.

Eco Chem Sales & Services, Surat Greenfield Technical Grade Pesticides and Intermediates Manufacturing Plant 1

CONTENTS 1 EXECUTIVE SUMMARY ............................................................................................... 5

(i) Introduction ............................................................................................................. 5

(ii) Project Description .............................................................................................. 5

(iii) Environment ........................................................................................................ 6

(iv) Environment sensitivity ........................................................................................ 6

(v) Conclusion .......................................................................................................... 6

2 INTRODUCTION OF THE PROJECT/ BACKGROUND INFORMATION ...................... 7

(vi) Identification of Project and project Proponent .................................................... 7

(vii) Brief description of Nature of the Project ............................................................. 7

(viii) Need for the Project and its Importance to the Country and or Region ................ 8

(ix) Demand Supply Gap ........................................................................................... 8

(x) Import vs Indigenous production .......................................................................... 8

(xi) Export Possibility ................................................................................................. 8

(xii) Domestic/Export Markets .................................................................................... 8

(xiii) Employment Generation (Direct and Indirect) due to the project .......................... 8

3 PROJECT DESCRIPTION ............................................................................................. 9

(i) Type of project including interlinked and interdependent project, if any ................... 9

(ii) Location with co-ordinates ................................................................................... 9

(iii) Details of Alternate Sites Considered ................................................................ 10

(iv) Size or Magnitude of the Operations ................................................................. 11

(v) Project Description with Process Details............................................................ 13

(vi) Raw Materials & Final Products ....................................................................... 130

(vii) Storage and Transportation Details of Raw Materials ...................................... 138

(viii) Resource optimization/recycling and reuse envisaged in the project ............... 142

(ix) Availability of water its source, Energy/power requirement and source ............ 142

(x) Quantity of wastes (Liquid, gas & Solid) to be generated and scheme for their Management / disposal .............................................................................................. 144

(xi) Schematic representations of the feasibility drawing which give information of EIA purpose ...................................................................................................................... 150

4 SITE ANALYSIS ........................................................................................................ 152

(i) Connectivity ........................................................................................................ 152



(ii) Land Form, Land Use and Land ownership ..................................................... 152

(iii) Topography (along with map) .......................................................................... 152

(iv) Existing land use pattern ................................................................................. 152

(v) Existing Infrastructure ...................................................................................... 152

(vi) Soil Classification ............................................................................................ 152

(vii) Climatic Data from Secondary Sources ........................................................... 153

(viii) Social Infrastructure ........................................................................................ 153

5 PLANNING BRIEF .................................................................................................... 154

(i) Planning concept ................................................................................................ 154

(ii) Population Projection....................................................................................... 154

(iii) Landuse Planning ............................................................................................ 154

(iv) Assessment of Infrastructure Demand ............................................................. 155

(v) Amenities/ Facilities ......................................................................................... 155

6 PROPOSED INFRASTRUCTURE ............................................................................. 156

(i) Industrial Area (Processing Area) ....................................................................... 156

(ii) Residential Area (Non Processing Area) ......................................................... 156

(iii) Green Belt ....................................................................................................... 156

(iv) Social Infrastructure ........................................................................................ 156

(v) Connectivity (Traffic and Transportation Road/ Rail/ Metro/ Water ways etc) .. 156

(vi) Drinking Water Management ........................................................................... 156

(vii) Industrial Waste Management ......................................................................... 156

(viii) Power Requirement & Supply/ Source ............................................................ 156

7 REHABLITATION & RESETTLEMENT (R & R) PLAN ............................................. 157

(i) Policy to be adapted (Central /State) in respect of the project affected persons including home outsee, Land outsee and Landless labourers .................................... 157

8 PROJECT SCHEDULE AND COST ESTIMATE ....................................................... 158

(i) Likely date of start of construction and likely data of completion ......................... 158

(ii) Estimates project cost along with analysis in terms of economic viability of the project ........................................................................................................................ 158

9 ANALYSIS OF THE PROPOSAL (FINAL RECOMMENDATIONS) .......................... 159

(i) Financial and social benefits with special emphasis on the befit to the local people including tribal population, if any, in the area .............................................................. 159



LIST OF TABLES

Table 1-1: Environmental Sensitivity ..................................................................................... 6

Table 2-1: Project Description ............................................................................................... 7

Table 2-2: Manpower Details ................................................................................................ 8

Table 3-1: Co-ordinates of the project ................................................................................. 10

Table 3-2: Details of Proposed Production Capacity ........................................................... 11

Table 3-3: Raw Material details ......................................................................................... 130

Table 3-4: Storage and Transportation Details of Raw Materials ....................................... 138

Table 3-5: Details of Water Consumption .......................................................................... 142

Table 3-6: Power Requirements and Its Source ................................................................ 144

Table 3-7: Fuel details ....................................................................................................... 144

Table 3-8: Waterwater generation details .......................................................................... 144

Table 3-9:ETP details........................................................................................................ 145

Table 3-10: Process gas emission details ......................................................................... 149

Table 3-11: Flue gas emission details ............................................................................... 149

Table 3-12: Details of Solid & Hazardous Waste and its Management .............................. 150

Table 4-1: Site Connectivity .............................................................................................. 152

Table 5-1: Area Statement ................................................................................................ 154

Table 8-1: Capital Cost Projection ..................................................................................... 158

Table 8-2:Recurring/Operating Cost Per Annum ............................................................... 158



LIST OF FIGURES Figure 3-1: Water Balance Diagram .................................................................................. 143

Figure 3-2: Effluent Treatment Scheme ............................................................................ 147

Figure 3-3 Schematic diagram of Sewage Treatment plant ............................................... 148

Figure 3-4: EIA Purpose .................................................................................................... 151

Figure 5-1: Plant layout ..................................................................................................... 155

LIST OF MAPS

Map 3-1: General and Specific Location Map ........................................................................ 9

Map 3-2: Google Earth Image ............................................................................................. 10

LIST OF ANNEXURES

Annexure 1: Plot allotment letter ....................................................................................... 161

Annexure 2: Toposheet of the Region ............................................................................... 162

Annexure 3: PCPIR Document .......................................................................................... 163



1 EXECUTIVE SUMMARY

(i) Introduction

Shreeji Pesticides Pvt. Ltd. intends to set up a plant for manufacturing pesticides technical grade and intermediate products at Dahej GIDC, Bharuch, Gujarat. The total plot area is 100272.418 sqm (10.02 Ha). The cost of the proposed project is 170 Crores. The proponent proposes to manufacture 26700 MTPA of Pesticides Technical (Fungicides, Herbicides and Insecticides) and 4400 MTPA Intermediate.

Applicability of EIA notification – 2006

The project falls under following Schedule:

“Pesticide Industry and Pesticide Specific Intermediates (excluding formulation)”, Project or Activity 5(b), Category “A” as per MoEF&CC, EIA notification, 2006 and amended till date and it will be appraised at Central level. As the proposed project site falls under PCPIR, Dahej Industrial Estate Zone III, Public hearing will be exempted. PCPIR document is enclosed as Annexure 3.

Justification for the Project

Presently, India is leading in the manufacturing of agrochemicals and is likely to become a world leader very soon. India is having very good engineering & research scientist pool and long proven expertise of producing quality pesticides, insecticides and herbicides. To fulfill the demand supply gap, it is decided by Shreeji Pesticides Pvt. Ltd. to setup a new plant with the state of art technology. For this the company will be adopting modern machineries and equipment and process technologies, with emphasis on waste minimization techniques wherever required. The proposed project for manufacturing of various products is based on the market surveys and in house captive consumption.

(ii) Project Description

Land: The total plot area for the proposed project is 100272.418 sq.m (10.02 Ha) which has been procured from Dahej GIDC, Bharuch.

Power: The power requirement for proposed expansion will be 4550 KWH which will be sourced from DGVCL.

Water: Total water requirement will be 1445 KLD. 1183.4 KLD fresh water will be sourced from GIDC, Dahej, 240 KLD boiler condensate will be recycled back in process and 21.6 KLD will be recycled from Sewage Treatment Plant.

D.G Set: Four D.G Sets of 750 KWH will be used as emergency power back up only in case of power failure.

Fuel: FO/NG/Coal will be used as primary fuel in proposed project. FO (25 KLD) will be sourced from HPCL. Natural Gas (33000 SCM) will be sourced from GAIL. Coal (62 TPD) will be sourced from Indian supplier or Imported. HSD (25 KLD) will be used in D.G.Set and will be sourced from local supplier.



Manpower: During construction phase, the manpower requirement will be of 30 permanent and 400 temporary. During operational phase, manpower employed will be 150 permanent basis and 400 on temporary basis.

(iii) Environment

Wastewater Generation: Total effluent generation will be 521 KLD and Sewage generation will be 24 KLD. An Effluent Treatment Plant of 625 KLD will be provided to treat the effluent generated and STP of 25 KLD will be provided to treat the sewage. 5 KLD from group company will be treated in proposed Effluent treatment Plant.

Solid Waste / Hazardous Generation: Hazardous/ Solid Waste/ Municipal solid waste for Collection, storage and disposal will be carried out as per Hazardous & Other Wastes (Management and Trans boundary Movement) Rules, 2016. Generated landfilling waste will be sent to BEIL, Ankleshwar/Dahej (common TSDF).

Greenbelt Development: About 8345 Plants will be planted for Greenbelt Development on area of 33379 sqm which will be 33.33 % of plot area.

Air Environment: There will be 5 process stacks, 3 boiler stacks, 1 D.G.Stack and 1 Thermic Fluid Heater. Standard Air Pollution Control Measures will be provided to control emissions.

(iv) Environment sensitivity There is no agricultural, forestry, National parks, Wild life sanctuary, Eco sensitive areas within 15 km.

Table 1-1: Environmental Sensitivity Particular Details Distance with direction

Areas which are important or sensitive for ecological reasons - Wetlands, watercourses or other

water bodies, coastal zone, biospheres, mountains, forests

Narmada Estuary 10.26 kms towards S Water

Bodies/Watercourses 0.55 km towards NE

Coastal Zone Coastal area is located at an

aerial distance of 7.7 km towards W

Reserve Forests Dahej Reserve Forest at 8.6 kms towards SW

Areas used by protected, important or sensitive species of flora or fauna for breeding,

nesting, foraging, resting, over wintering, migration

Afforested Mangroves 8.6 kms towards SW

Nearest habitation Padariya Village 800m in NNE Densely populated or built-up

area Dahej 7.78 km in SW

(v) Conclusion

There is no adverse impact anticipated on environment due to proposed project.



2 INTRODUCTION OF THE PROJECT/ BACKGROUND INFORMATION

(vi) Identification of Project and project Proponent

Project

Shreeji Pesticides Pvt. Ltd. intends to set up a plant for manufacturing agrochemical technical grade and intermediates products. The proposed plants are meant for Multipurpose products. The plant will be supported with adequate utilities, tank-forms, warehouses etc.

The proponent proposes to establish a pesticide manufacturing unit at Plot No. D-3/5/3 GIDC Dahej Phase III, Tal Vagara, Dist. Bharuch, Gujarat having total plot area of 100272.418 sqm (10.02 Ha) & total investment is ~170 Cr. As the proposed project site falls under PCPIR, Dahej Industrial Estate Zone III, Public hearing will be exempted. PCPIR document is enclosed as Annexure 3.

Project Proponent

Shreeji Pesticides Pvt. Ltd. was established in the year 1989, acquired by Willowood Chemicals (Pvt) Limited in the year 2010, the plant is engaged in research and development, production, application and sales of agrochemicals. The pesticide unit plant is located in the Economic and Technical Development Zone in the city of Baroda, Gujarat, India and its employees includes doctorate and master’s degree holders as well as other experienced workers. The pesticide plant has also received accreditations of ISO9001:2008.

The pesticide plant mainly specializes in the contract manufacturing (Toll formulation) & development of agrochemicals for multinationals companies, and after years of relentless efforts has made great strides in the research, development, production and application of agrochemicals.

(vii) Brief description of Nature of the Project

The proposed project involves manufacturing of various Technical Grade Pesticides and Intermediates. Brief description of the project is given in Table 2-1.

Table 2-1: Project Description

S. No. Details Description

1. Nature Pesticides Manufacturing

2. Product Pesticides Technical (Fungicides,

Herbicides and Insecticides) 26700 MTPA

Intermediates 4400 MTPA

.3 Location Plot No. D-3/5/3 GIDC Dahej Phase III, Tal Vagara, Dist. Bharuch, Gujarat

4. Cost of the project 170 Crores



(viii) Need for the Project and its Importance to the Country and or Region

Need for the proposed products is based on the demand and supply gap in the current market. With increasing utilization of the current products, in future, to carter the requirement of all the products, it is essential to have the proposed manufacturing unit.

(ix) Demand Supply Gap

Indian Pesticides is one of the rapidly growing markets and has emerged a strong export oriented business. About 6000 MT/Year of Agro Chemical Product are manufactured in INDIA and 5000 Tons/Year sold in India and in others Countries 1000 MT/Year.

(x) Import vs Indigenous production

At present 400 Cr technical grade product is imported from Taiwan,Korea,China. After the proposed project this dependancy will be reduce and it will be boost to MAKE IN INDA campaign.

(xi) Export Possibility

Company may export the products as per reqiurements

(xii) Domestic/Export Markets

Company has both domestic and export market. As per the requirments the producers are introduced in the market

(xiii) Employment Generation (Direct and Indirect) due to the project

The proposed project will generate employment during the construction and operation phase. Local skilled and semi-skilled workers will be hired during construction phase as well as operation phase. During the operation phase, technical staff, general staff for administrative work and other ancillary services i.e. O&M contractor and maintenance services will be required on a temporary basis. Details of manpower is given in Table 2-2.

Table 2-2: Manpower Details S.No. Particular Number of Workers

1 Permanent Employment-During Construction 30

2 Temporary Employment-During Construction 400

3 Permanent Employment-During Operation 150

4 Temporary Employment-During Operation 400



3 PROJECT DESCRIPTION

(i) Type of project including interlinked and interdependent project, if any

The proposed project is not interlinked and interdependent project of the company

(ii) Location with co-ordinates

The project is proposed in Notified Industrial Estate at Plot No. D-3/5/3 GIDC Dahej Phase III, Tal Vagara, Dist. Bharuch, Gujarat. The area for Proposed plant is 100272.418 sqm (10.02 Ha). General & Specific location of project site is shown in Map 3-1 and Plant Boundary is shown in Map 3-2. Coordinates of project site are given in Table 3-1.

Map 3-1: General and Specific Location Map



Map 3-2: Google Earth Image

Table 3-1: Co-ordinates of the project

Point Latitude Longitude 1 21.774334° 72.632066° 2 21.773791° 72.631352° 3 21.772032° 72.630724° 4 21.771479° 72.630521° 5 21.770919° 72.633800° 6 21.773952° 72.634568° 7 21.773840° 72.634080° 8 21.773758° 72.634025° 9 21.773744° 72.632819°

10 21.773941° 72.632799° 11 21.773974° 72.632085° 12 21.774234° 72.632121°

(iii) Details of Alternate Sites Considered

The site was selected based on following considerations:

1. Proximity to Centrally located Delhi-Mumbai (DMIC) Industrial Corridor that is easily approachable from all parts of India

2. Readily available world class infrastructure water, CETP, gas, power, raw material supplier

3. Proximity to Gujarat Chemical Port Terminal Company Limited (GCPTCL)



4. Proximity to our R & D and pilot plant approx..150 km away from Dahej-III site. 5. Proximity to our formulation plant 140 km away from Dahej-III site

(iv) Size or Magnitude of the Operations The proponent proposes to manufacture 26700 MTPA of pesticides and 4400 MTPA of Intermediates. Details of Proposed Production Capacity are provided in Table 3-2.

Table 3-2: Details of Proposed Production Capacity S. No. Name Of Product Cas No. Ld50 Capacity

A Fungicides

11400 MTPA

1 Azoxystrobin Technical 131860-33-8 >5000 mg/kg 2 Boscalid Technical 188425-85-6 >5000 mg/kg 3 Carboxin Technical 5234-68-4 >3800 mg/kg 4 Chlorothalonil Technical 1897-45-6 >5000 mg/kg 5 Difenoconazole Technical 119446-68-3 >1450 mg/kg 6 Epoxiconazole Technical 106325-08-0 >5000 mg/kg 7 Hexaconazole Technical 79983-71-4 >2180 mg/kg 8 Kresoxim-Methyl Technical 143390-89-0 >5000 mg/kg 9 Penconazole Technical 66246-88-6 >2125 mg/kg 10 Picoxystrobin Technical 117428-22-5 >5000 mg/kg 11 Propiconazole Technical 60207-90-1 >1500 mg/kg 12 Prothioconazole Technical 178928-70-6 >6000 mg/kg 13 Pyraclostrobin Technical 175013-18-0 >5000 mg/kg 14 Tebuconazole Technical 107534-96-3 >3000 mg/kg 15 Thifluzamide Technical 130000-40-7 >5000 mg/kg 16 Trifloxystrobin Technical 141517-21-7 >5000 mg/kg B Insecticide

3300 MTPA

1 Chlorantraniliprole Technical 500008-45-7 >5000 mg/kg

2 Cyantraniliprole Technical 736994-63-1 >5000 mg/kg 3 Flubendiamide Technical 272451-65-7 >2000 mg/kg 4 Nitenpyram 150824-47-8 >1500 mg/kg 5 Pymetrozine Technical 123312-89-0 >5000 mg/kg 6 Spirodiclofen 148477-71-8 >2500 mg/kg 7 Spirotetramet 203313-25-1 >2000 mg/kg 8 Thiamethoxam Techncial 153719-23-4 >1563 mg/kg C Herbicides

12000 MTPA

1 Carfentrazone-Ethyl Technical 128639-02-1 >5100 mg/kg

2 Clethodim Technical 99129-21-2 >1600 mg/kg

3 Clodinafop-Propargyl Technical 105512-06-9 >1800 mg/kg

4 Clomazone Technical 81777-89-1 >2000 mg/kg 5 Chloransulam Technical 147150-35-4 >5000 mg/kg 6 Diclosulam Technical 145701-21-9 >5000 mg/kg

7 Fenoxaprop-P-Ethyl Technical 71283-80-2 >3500 mg/kg



S. No. Name Of Product Cas No. Ld50 Capacity 8 Flufenacet Technical 142459-58-3 >1500 mg/kg 9 Fomesafen Technical 72178-02-0 >1250 mg/kg

10 Glufosinate-Ammonium Technical 77182-82-2 >2000 mg/kg

11 Glyphosate 1071-83-6 12 Mesotrione Techncial 104206-82-8 >5000 mg/kg 13 Penoxsulam Technical 219714-96-2 >5000 mg/kg 14 Pretilachlor Technical 51218-49-6 >6000 mg/kg 15 Propanil Technical 709-98-8 >2500 mg/kg 16 Propaquizafop Technical 111479-05-1 >5000 mg/kg 17 Sulfentrazone Technical 122836-35-5 >2500 mg/kg

Total 26700 MTPA D Intermediate

4400 MTPA 1 1,2,4-Triazole 288-88-0 >1350 mg/kg 2 Ccmt 105827-91-6 DNA 3 Mnio 153719-38-1 3914 mg/kg



(v) Project Description with Process Details

FUNGICIDE

Azoxystrobin Step-I Phthalide is reacted with methyl formate in presence of Di methyl Carbonate and Sodium Hydride as well as Solvent -Toluene to form 3- Methoxy Methylidene -1- Benzofuran -2-(3-H) – One

OO

134.13Phthalide

+ CO

OCH3H

methyl formate

60.05

+ (CH3)2CO3

90.08

NaOH OO

COCH3

3-acetyl-1-benzofuran-2(3H)-one

+ Na2CO3

106+ CH3 OH

64.08

175.16

+ OH2

18.01

80 22

Step-II 3- Methoxy Methylidene -1- Benzofuran -2-(3-H) – One reacted with Sodium Methoxide in presence of Solvent – EDC to form Sodium -2- [1,3 Dimethoxy -3- Oxoprop -1- en -2- yl] Phenolate.

EDCOO

COCH3

3-acetyl-1-benzofuran-2(3H)-one

175.16

+ Na O CH3

sodium methanolate

ONa

COCH3

OCH3

O

sodium 2-(1-methoxy-1,3-dioxobutan-2-yl)phenolate229.18

Step-III Sodium -2- [1,3 Dimethoxy -3- Oxoprop -1- en -2- yl] Phenolate is reacted with 4,6 –Dichloro Pyrimidine in presence of Solvent – Toluene to give Methyl -2- [ 2- { ( 6- Chloro Pyrimidine -4 –yl)} Oxy Phenyl ] -3-methoxyprop -2- Ethanoate.

Toluene

ONa

COCH3

OCH3

O

sodium 2-(1-methoxy-1,3-dioxobutan-2-yl)phenolate

229.18

+NN

ClCl4,6-dichloropyrimidine

149

O

COCH3

OCH3

O

NN

Cl

methyl 2-{2-[(6-chloropyrimidin-4-yl)oxy]phenyl}-3-oxobutanoate

319.72

+ NaCl

58.44



Step-IV Methyl -2- [ 2- { ( 6- Chloro Pyrimidine -4 –yl)} Oxy Phenyl ] -3- methoxyprop -2- Ethanoate O- Cyano Phenol in presence of Potassium Hydroxide and Solvent – Di Methyl Formamide to give the Final product as AZOXYSTORBIN

O

COCH3

OCH3

O

NN

Cl

methyl 2-{2-[(6-chloropyrimidin-4-yl)oxy]phenyl}-3-oxobutanoate

319.72

+

CN

OH

2-hydroxybenzonitrile119.12

DMFO

COCH3

OCH3

O

NN

O

CNKOH

+ + OH2

74.55 18.01

KCl

Azoxystrobin402.38

Process Flow Diagram



Mass Balance

S. No.

Input(kg)/MT of Product

S. No.

Output/(kg) of Product

Raw Materials Quantity

Output Material Name

Product / By

Product Waste Water

Air Emission Recovery Loss Solid/Hazardous

Waste (kg)

1 Phthalate 320 1 Sodium carbonate- 258

2 Methyl Formate 142 2 Methanol 58

3 Di Methyl Carbonate 216 3 NaCl 140

4 Sodium Hydroxide 58 Toluene Loss 75

5 Toluene 2600 4 Toluene Recovery 2525

6 Sodium Methoxide 128 EDC loss 50

7 EDC 1200 5 EDC Recovery 1150

8 4,6 – Di Chloro

Pyrimidine 352 6 Azoxystrobin 1000

9 Ortho Cyano Phenol

283 7 KCl 180

10 Potassium Hydroxide 133 DMF Loss 40

11 DMF 1200 8 DMF Recovery 1160

12 Water 880 9 Aq. to ETP 857

10 Distillate residue 19

1636 857 0 4835 165 19

Total 7512 Total 7512

Boscalid Stage I: Preparation of 4-CPBA 1. Charge in a reactor THF and Mg, heat upto reflux, 2. Add slowly dichlorobenzene with toluene in 2 – 3 hours. 3. After complete addition cool mass to 15 ˚C 4. Add slowly trimethyl borate. 5. After complete addition reaction mass quenched in solution of HCl + water at low

temperature. 6. Layer separation 7. Recover solvent from organic layer and crude take to next step.



Chemical reaction

Cl

Cl

+ Mg2+ THF, Toluene

MgCl

Cl

1,4-dichlorobenzene147

171.3

MgCl

Cl171.3

+ B OCH3

OCH3

OCH3

103.9Trimethoxy borate

B

Cl

OH

OH

156.37Intermediate - I

Stage II: Preparation of Intermediate-II

1. Charge in a reactor Intermediate-I and Toluene, add catalyst. 2. Add 1-chloro-2-nitrobenzene and heat the mass to reflux and maintain till reaction

complete. 3. Filter the mass and remove catalyst. 4. Recover solvent from organic mass. 5. Take crude to next step

Chemical reaction

B

Cl

OH

OH

156.37Intermediate - I

+

NO2

Cl

1-chloro-2-nitrobenzene157.55

catalystToluene

NO2Cl4'-chloro-2-nitrobiphenyl

233.65Intermediate - II

Stage III: Preparation of Intermediate-III 1. In pressure reactor charge Intermediate-II of stage-II. 2. Add methanol and catalyst and take pressure of hydrogen and heat up to 60 ˚C. 3. Maintain reaction till completion. 4. Filter to recover catalyst and recover methanol. 5. Take crude to next step

Chemical reaction

H2/Pd - CMethanol

NO2Cl4'-chloro-2-nitrobiphenyl

233.65Intermediate - II

NH2Cl4'-chlorobiphenyl-2-amine

203.66Intermediate - III

Stage IV: Preparation of 2-chloropyridine-3-carbonyl chloride (Intermediate-IV)



1. Charge in a reactor Acetonitrile and CPCA 2. Add slowly PCl3 in 2 – 3 hours and maintain reaction up to completion. 3. After reaction completion add NaOH solution and stir for some time. 4. Separate layer. 5. Organic layer (Intermediate-III) to next step

Chemical reaction

Acetonitrile+ PCl3

N Cl

OH

O

2-chloropyridine-3-carboxylic acid157.55

N Cl

Cl

O

2-chloropyridine-3-carbonyl chloride176

Stage V: Preparation of Boscalid 1. Charge in a reactor Intermediate-III of stage –III and organic layer (intermediate-IV)

of stage-IV. 2. Add catalyst, and maintain reaction up to completion. 3. Filter the reaction mass and recover solvent. 4. In crude organic add XP-50, and reflux for 2 hours. 5. Cool to 10 ˚C, filter solid mass and dry Boscalid.

Chemical reaction

N Cl

Cl

O

2-chloropyridine-3-carbonyl chloride176

+ NH2Cl4'-chlorobiphenyl-2-amine

203.66

NHCl

Cl

N

O

2-chloro-N-(4'-chlorobiphenyl-2-yl)pyridine-3-carboxamide343.2

(BOSCALID)






Mass Balance

S. No.

Input/MT of Product Output/(MT) of Product

Raw Materials Quantity Output Material Name

Product / By

Product Wates Water


Waste (kg)

1 1,4-dichlorobenzene 1000 Rec. Toluene 1950 2 Mg 170 Rec. THF 2950 3 Toluene 5000 Aq. layer 8430 4 THF 3000 Rec. catalyst 40 5 Trimethoxy borate 710 Rec. Toluene 3610

6 HCl 500 Rec.

Methanol 2450

7 water 5000 Methanol loss 50

8 1-chloro-2-nitrobenzene 1060 Process loss 200

9 Catalyst 70 Intermediate-III 1300

10 Methanol 2500 Organic layer (Intermediate-

IV) 2400

11 Pd-C 20 Rec. Solvent 1508 12 CPCA 1000 Rec. catalyst 50 13 Acetonitrile 3000 ML 2192 14 PCl3 350 Boscalid 2000



S. No.

Input/MT of Product Output/(MT) of Product


Product / By

Product Wates Water


Waste (kg)

15 Sodium hydroxide 50 16 Intermediate-III 1300

17 Intermediate-IV 2400 18 XP-50 2000 16322 0 0 12558 250 0


Carboxin Step-I Process description:- Carboxin is manufactured by reacting acetoacetanilide (AA) with sulfuryl chloride (SO2Cl2) to

give 2‐chloro‐3‐oxo‐N‐phenylbutanamide intermediate (2‐CPB).

O

CH3

O

NH

3-oxo-N-phenylbutanamide

177.2

+ S

O

O

ClCl

sulfuryl dichloride134.97

O

CH3

O

NH

Cl

+ SO2

+ ClH

2-chloro-3-oxo-N-phenylbutanamide211.64

64.06

36.46

Step-II Process description:- This intermediate is further reacted with 2‐mercaptoethanol (2‐ME) in presence of triethyl amine (TEA) to give 2‐(2‐hydroxyethylthio)‐3‐oxo‐N‐phenylbutanamide (2‐HEPB).

O

CH3

O

NH

Cl

2-chloro-3-oxo-N-phenylbutanamide211.64

+ OHSH

2-sulfanylethanol

78.13

(2 - mercaproethanol)

TEA S

O

NH

CH3

O

OH

2-[(2-hydroxyethyl)sulfanyl]-3-oxo-N-phenylbutanamide

253.31

+ ClH36.46

Step-III Process description:- Finally it is cyclised using PTSA to give carboxin technical.

S

O

NH

CH3

O

OH

2-[(2-hydroxyethyl)sulfanyl]-3-oxo-N-phenylbutanamide

253.31

PTSA S

O

NH

CH3

O

2-methyl-N-phenyl-5,6-dihydro-1,4-oxathiine-3-carboxamide

235.3

+ OH218.01




Mass Balance

S. No.

Input/(kg) of Product S.

No.



Product / By

Product Wates Water


Waste (kg)

1 Acetoacetanilide 994 1 SO2 gas 370

2 SO2Cl2 781 2 HCl gas 211

3 TEA 521 3 TEA HCl 708

4 2‐ME 403 4 Carboxin 660



5 PTSA 231 5 PTSA 231

6 Benzene 5610 6 Water distilate 50

7 Acetone 2640 7 Benzene recovered 5346

8 Water 5280 8 Benzene loss 264

9 Acetone recovered 2520

10 Acetone loss 120

11 Water to ETP 5280

12 Organic impurity 700

1599 5330 581 7866 384 700


Chlorothalanil Process description Tetrachloroisophtalic acid on ammonylsis forms its ammonium salt, which on further reaction with phosphorous pentaoxide forms the product Chlorothalanil.

COOH

Cl

COOH

Cl

Cl

Cl

2,4,5,6-tetrachlorobenzene-1,3-dicarboxylic acid(Tetrachloro isophthalic acid)

303.91

2 NH3+34

CONH2

Cl

CONH2

Cl

Cl

Cl

2,4,5,6-tetrachlorobenzene-1,3-dicarboxamide301.94

+ 2 H2O36

P2O5

CN

Cl

CN

Cl

Cl

Cl

2,4,5,6-tetrachlorobenzene-1,3-dicarbonitrile(Chlorotalonil)

+

265.91

2 H2O36




Mass Balance

S. No.

Input/MT of Product S.

No.


Raw Materials Quantity


Product / By

Product Wates Water


Waste (kg)

1 Tetrachloro Isophthalate 1055 1 Chlorthalonil 1020

2 Toluene 2000 2 Water Distillate 120

3 Ammonia Solution 125 3 Toluene

recovered 1950

4 Catalyst 20 4 Toluene loss 50

5 Water 850 5 Aq. layer to ETP 910

1020 1030 0 1950 50 0




Difenconazole Step-I 1,3-Dichloro Benzene is reacted with Acetyl Chloride in presence of Aluminum Chloride and Solvent – Ethylene Di Chloride to get 2,4-Dichloro Acetophenone

Cl

Cl1,3-dichlorobenzene

147

+ CH3 C

O

Clacetyl chloride

78.49

AlCl3/EDCCl

Cl

CO CH3

+ ClH

1-(2,4-dichlorophenyl)ethanone189.03

36.46

Step-II 2,4-Dichloro Acetophenone further reacted with 4-Chloro Phenol in presence of Potassium Hydroxide and Solvent- DMF to get 2-Chloro-4-(4-Chlorophenoxy) Acetophenone.

DMFCl

Cl

CO CH3

+ ClH


36.46

+

OH

Cl4-chlorophenol

128.55

O

Cl

Cl

C

CH3

O

1-[2-chloro-4-(4-chlorophenoxy)phenyl]ethanone281.13

Step-III 2-Chloro-4-(4-Chlorophenoxy) Acetophenone further reacted with Bromine in presence of Catalyst and Solvent - Ethylene Di Chloride to get 2-Chloro-4-(4-Chlorophenoxy) Phenacyl Bromide.

EDC/PTSA+ BrH

80.9

O

Cl

Cl

C

CH3

O

1-[2-chloro-4-(4-chlorophenoxy)phenyl]ethanone281.13

+ Br Br

159.8

O

Cl

Cl

C

CH2

O

Br2-bromo-1-[2-chloro-4-(4-chlorophenoxy)phenyl]ethanone

360.03

Step-IV 2-Chloro-4-(4-Chlorophenoxy) Phenacyl Bromide reacted with Propylene Glycol in presence of Solvent -Toluene to get 3-Chloro-4-(2-Bromomethyl-4-methyl-1,3-Dioxolane-2-yl)-4’-Chloro Diphenyl Ether.



Toluene+ OH2

18.01

O

Cl

Cl

C

CH2

O

Br

2-bromo-1-[2-chloro-4-(4-chlorophenoxy)phenyl]ethanone

360.03

+ CH2 CH CH3

OH OH

propane-1,2-diol76.09

O

Cl

Cl

C

CH2

O

Br

CH2

CHCH3

O

2-(bromomethyl)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolane

418.1

Step-V 3-Chloro-4-(2-Bromomethyl-4-methyl-1,3-Dioxolane-2-yl)-4’-Chloro Diphenyl Ether further reacted with 1,2,4-Triazole in presence of Potassium Hydroxide and Solvent DMF to get final product DIFENOCONAZOLE.

KOH/DMFO

Cl

Cl

C

CH2

O

Br

CH2

CHCH3

O

2-(bromomethyl)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolane

418.1

+NH

N

N

1H-1,2,4-triazole69.06

O

Cl

Cl

C

CH2

O

N

CH2

CHCH3

O

N

N

1-({2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolan-2-yl}methyl)-1H-1,2,4-triazole

406.26

+ BrH80.91

DIFENCONAZOLE






Mass Balance

Sr.No

Input/MT of Product Output/(kg) of Product Raw

Material Name

Qty (kg)


Product / By

Product Wates Water


Waste (kg)

1 1,3 Di Chloro

Benzene 392 30% HCl 324

2 Acetyl Chloride 208 20% AlCl3 2448

3 Aluminium Chloride 490 EDC recovered 4720

4 EDC 4800 EDC loss 80 5 Water 3055 Potassium chloride 205

6 4- Chloro Phenol 340 DMF recovered 3840

7 Di Methyl Formamide 1900 DMF loss 60

8 KOH 473 20% HBr solution 775 9 Bromine 422 Catalyst recovered 10 10 Catalyst 10 Toluene recovered 1970

11 Propylene Glycol 198 Toluene loss 30

12 Toluene 2000 DIFENCONAZOLE 1000

13 1,2,4 – Triazole 180 Aq. layer to ETP 670

14 DMF 2000 Process loss 16 KBr 320

5072 670 16 10540 170 0


Epoxiconazole Step-I Fluorobenzene is reacted with Chloro Acetyl chloride in presence of Aluminum chloride and Solvent – Ethylene Di Chloride to get 4-Fluoro Phenacyl Chloride.

+ CH2 C

O

ClCl

AlCl3/EDC

F

CO CH2Cl

+ ClH36.46

chloroacetyl chloride112.94

F

fluorobenzene96.1

2-chloro-1-(4-fluorophenyl)ethanone172.58

Step-II 4-Fluoro Phenacyl Chloride reacted with 1,2,4-Triazole in presence of Potassium Hydroxide and Solvent DMF to give 2-(1H-1,2,4-Triazole-1-yl)-4-Fluoro Acetophenone.



KOH/DMF

F

CO CH2Cl

+ ClH36.46

2-chloro-1-(4-fluorophenyl)ethanone172.58

+NH

N

N

1H-1,2,4-triazoleF

CO CH2 N

N

N

1-(4-fluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethanone205.18

69.06

Step-III 2-(1H-1,2,4-Triazole-1-yl)-4-Fluoro Acetophenone reacted with 2-Chloro benzyl chloride and Dimethyl Sulphide in presence of Potassium Hydroxide and Solvent DMF to give the final product EPOXICONAZOLE.

KOH/MIBK

F

CO CH2 N

N

N

1-(4-fluorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethanone

205.18

+ CH3 S CH3

(methylsulfanyl)methane62.13

+

CH2

Cl

Cl

1-chloro-2-(chloromethyl)benzene161.02

F

CO CH2 NN

NCH

Cl

+ClH

1-{[3-(2-chlorophenyl)-2-(4-fluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole

329.75

36.46

EPOXICONAZOLE






Mass Balance

Sr.No

Input/MT of Product Sr.

No.


Raw Material Name

Qty (kg)


Product / By

Product

Wates

Water

Air Emissio

n Recover

y Los

s Solid/Hazardou

s Waste (kg)

1 Fluoro Benzene 320 1 30% HCl 406

2 Chloro Acetyl

Chloride 375 2 20% AlCl3 2033

3 Aluminum Chloride 400 3 Rec. EDC 1270

4 EDC 1300 4 EDC loss 30 5 Water 2440 5 KCl 502

6 KOH 555 6 Epoxiconazole 1000

7 1,2,4 – Triazole 228 7 DMF

recovered 1765 8 DMF 1800 8 DMF loss 35

9 2- Chloro Benzyl

Chloride 530 9 Potassium

bisulphate 238

10 Di Methyl Sulphide 202 10 Aq. to ETP 853

11 Process loss 18

4179 853 18 3035 65 0 Total 8150 Total 8150

Hexaconazole Step-I 1,3-Dichloro benzene reacted with Pentanoyl chloride in presence of Aluminum chloride and Solvent – Ethylene Di Chloride to get 2,4-Dichloro Valerophenone.

+ CH2 CO

ClCH2CH2CH3

AlCl3/EDC

Cl

C

O

CH2

Cl

CH2 CH2 CH3

+ ClH36.46

Cl

Cl


231.11

pentanoyl chloride120.57 1-(2,4-dichlorophenyl)pentan-1-one

Step-II 2,4-Dichloro Valerophenone further reacted with Methylene-Triphenylphosphorane in presence of Solvent -THF to get 2-(2,4-Dichloro Phenyl)-n-hex-1-ene.



THF

Cl

C

O

CH2

Cl

CH2 CH2 CH3

+

231.111-(2,4-dichlorophenyl)pentan-1-one

+ (H5C6)3 P CH2

Methylene-Triphenylphosphorane276.3 Cl

C

CH2

CH2

Cl

CH2 CH2 CH3

(H5C6)3 P O278

229.14

2,4-dichloro-1-(hex-1-en-2-yl)benzene

Step-III 2-(2,4-Dichloro Phenyl)-n-hex-1-ene reacted with Bromine and Hydrogen Peroxide in presence EDC to get 1-Bromo-2-(2,4-Dichlorophenyl)-hexane-2-ol.

+

Cl

C

CH2

CH2

Cl

CH2 CH2 CH3

229.14

2,4-dichloro-1-(hex-1-en-2-yl)benzene

+ Br2 + H2O2

159.8 34

EDC

Cl

C

CH2

CH2

Cl

CH2 CH2 CH3OH

Br

BrH + O21/280.91 16

326.05

1-bromo-2-(2,4-dichlorophenyl)hexan-2-ol

Step-IV 1-Bromo-2-(2,4-Dichlorophenyl)-hexane-2-ol further reacted with 1,2,4-Triazole in presence of Potassium hydroxide and Solvent DMF to get final product HEXACONAZOLE.

+KOH/DMF

Cl

C

CH2

CH2

Cl

CH2 CH2 CH3OH

Br

BrH80.91

326.051-bromo-2-(2,4-dichlorophenyl)hexan-2-ol

+NH

N

N

1H-1,2,4-triazole69.06 Cl

CCH2 CH2

Cl

CH2 CH2 CH3

OH

NN

N

2-(2,4-dichlorophenyl)-1-(1H-1,2,4-triazol-1-yl)hexan-2-ol

314.2




Mass Balance

Sr.No

Input/MT of Product Output/(kg) of Product

Raw Material Name

Qty (kg)


Product / By

Product Wates Water


Waste (kg)

1 1,3 Di Chloro Benzene 510 30% HCl 421

2 Pentanoyl Chloride 417 20% AlCl3 3160

3 Aluminium Chloride 632 EDC

recovered 2790 4 EDC 2850 EDC loss 60

5 Water 3943 Tri Phenyl phosphanone 966



Sr.No


Raw Material Name

Qty (kg)


Product / By

Product Wates Water


Waste (kg)

6 Methyl

Triphenyl Phosphorane

944 THF recovered

1150

7 THF 1200 THF loss 50 8 Bromine 540 28% HBr 1005

9 Hydrogen Peroxide 116 Oxygen 50

10 KOH 178 Hexaconazole 1000

11 1,2,4 – Triazole 220 DMF

recovered 1065 12 DMF 1100 DMF loss 35 KBr 410

Aq. to ETP 468

Process loss 20

6962 468 70 5005 145 0


Kresoxim Methyl Step-I Phthalide is reacted with O-cresol in presence of potassium Hydroxide and Solvent – Xylene to give 2-(2-Methyl Phenoxy methyl) Benzoic acid.

O

O

Phthalide134.13

OH

CH3

+ KOH/Xylene

CH3

O

COOH

2-methylphenol108.13

O-cresol

2-[(2-methylphenoxy)methyl]benzoic acid

242.27

Step-II 2-(2-Methyl Phenoxy methyl) Benzoic acid reacted with Thionyl Chloride in presence of Solvent - Xylene to give 2-(2-Methyl Phenoxy methyl) Benzoyl chloride.



CH3

O

COOH + S OCl

Clthionyl dichloride

118.97

CH3

O

COCl+ SO2

ClH+64.06

36.46

HCl + KOH KCl OH2+36.46 56.1 74.55 18.01

NaOH + SO2 NaHSO340 64.06 104.05

2-[(2-methylphenoxy)methyl]benzoic acid

242.27 2-[(2-methylphenoxy)methyl]benzoyl chloride260.71

Step-III 2-(2-Methyl Phenoxy methyl) Benzoyl Chloride reacted with Sodium cyanide to give 2-(2-Methyl Phenoxy methyl) Benzoyl Cyanide.

CH3

O

COCl + NaCN

CH3

O

COCN + NaCl

58.4449

2-[(2-methylphenoxy)methyl]benzoyl chloride

260.72

{2-[(2-methylphenoxy)methyl]phenyl}(oxo)acetonitrile251.28

Step-IV 2-(2-Methyl Phenoxy methyl) Benzoyl Cyanide (Nitrile) further reacted with Methoxy amine in presence of Hydrochloric Acid and Solvent - Methanol to give final product KRESOXIM-METHYL

CH3

O

COCN ++ NH2 O CH3

O-methylhydroxylamine47.05 x 2 = 94.1

Methanol

30% HCl2

CH3

O

CN OCH3

C

OCH3

O

NH2 NH2

hydrazine32.04

{2-[(2-methylphenoxy)methyl]phenyl}(oxo)acetonitrile251.28 methyl

(2E)-(methoxyimino){2-[(2-methylphenoxy)methyl]phenyl}ethanoate

313.34






Mass Balance

Sr.No

Input/(kg) of Product

Sr.No

Output/(kg) of Product Raw

Material Name

Qty (kg)


Product / By

Product Wates Water


Waste (kg)

1 Ortho Cresol 360 1 KCl 250

2 Phthalide 447 2 Sodium

bisulphite 413

3 Potassium Hydroxide 187 3

Water to ETP 402

4 Xylene 1800 4 NaCl 195

5 Thionyl Chloride 398 5

Xylene recovered 1760

6 Sodium Hydroxide 163 6

Xylene loss 40

7 NaCN 202 7 Kresoxim

Methyl 1000

8 30%

Hydrochloric Acid

131 8

Hydrazine 50

9 Methanol 1000 9 Mehanol

recovered 980

10 Methoxy Amine 156 10

Methanol loss 20

11 Water 3975 11 Aq. to ETP 3693

12 Distillation

residue 16

1908 4095 0 2740 60 16


Penconazole Step-I 2-(2,4-Dichlorophenyl) Pentyl Alcohol reacted with Methane Sulfonyl Chloride in presence of Sodium hydroxide and solvent- Toluene to give 2-(2,4-Dichloro Phenyl) Pentyl Methane Sulfonate.

Cl

Cl

CH CH2 CH2 CH3

CH2

OH

+NaOH/Toluene

+ ClH

36.46

2-(2,4-dichlorophenyl)pentan-1-ol233

CH3SO2Cl

Methanesulphonyl chloride114.55

Cl

Cl

CH CH2 CH2 CH3

CH2

O S

O

OCH3

2-(2,4-dichlorophenyl)pentyl methanesulfonate311.22

Step-II 2-(2,4-Dichloro Phenyl) Pentyl Methane Sulfonate further reacted with 1,2,4-Triazole in presence of Sodium Methoxide and Solvent DMF to give final product PENCONAZOLE.



+CH3 OH

32.04

Cl

Cl

CH CH2 CH2 CH3

CH2

O S

O

OCH3

2-(2,4-dichlorophenyl)pentyl methanesulfonate

311.22

+NH

N

N


CH3ONa

DMF

Cl

Cl

CH CH2 CH2 CH3

CH2N

N

N

CH3SO3Na

+118.08

1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole284.18




Mass Balance

Sr.No

Input/(kg) of Product Output/(kg) of Product

Raw Material Name

Qty (kg)


Product / By

Product Wates Water


Waste (kg)

1 2-(2,4 –

dichlorophenyl) Pentyl Alcohol

905 30% HCl 478

2 Methane Sulphonyl Chloride

445 Rec. Toluene

1160

3 Sodium Hydroxide 155 Loss toluene 40

4 Toluene 1200 Penconazole 1000

5 1,2,4 – Triazole 264 Methanol 124

6 Sodium Methoxide 208

Methane Sulphonic

Acid Sodium Salt 466

7 DMF 1200 DMF loss 25 8 Water 858 DMF recov. 1175

Aq. layer to ETP 750

Process loss 17

2068 750 17 2335 65 0


Picxystrobin Step-I 3-Isochromanone is reacted with Methyl formate in presence of Di methyl carbonate and sodium hydride as well as Solvent - Toluene to give 4-(α-methyl Methylene)-3-Isochromanone.

O

O1,4-dihydro-3H-isochromen-3-one

148.15

+ CH3 O C

O

H

methyl formate60.05

(CH3)2CO3/NaOHToluene

O

O

H3CO

+ OH2

190.2

(4E)-4-(methoxymethylidene)-1,4-dihydro-3H-isochromen-3-one

18.01

Step-II 4-(α-methyl Methylene)-3-Isochromanone further reacted with Hydrochloric acid gas in presence of Solvent –EDC to give Methyl-2-(Chloromethyl)-α-methoxy Methylene-Benzene Acetate.



O

O

CHH3CO

190.2

(4E)-4-(methoxymethylidene)-1,4-dihydro-3H-isochromen-3-one

+ ClHCl

O OCH3

OCH3

methyl (2E)-2-[2-(chloromethyl)phenyl]-3-methoxyprop-2-enoate

240.68

EDC

Step-III Methyl-2-(Chloromethyl)-α-Methoxy Methylene-Benzene acetate reacted with 2-Hydroxy-6-

Trifluoromethyl pyridine to give final product PICOXYSTORBIN.

XyleneCl

O OCH3

OCH3

methyl (2E)-2-[2-(chloromethyl)phenyl]-3-methoxyprop-2-enoate

240.68

+O

O OCH3

OCH3

NF3C

367.32

+ ClH36.46

NF3C OH

6-(trifluoromethyl)pyridin-2-ol163.09

methyl (2E)-3-methoxy-2-[2-({[6-(trifluoromethyl)pyridin-2-yl]oxy}methyl)phenyl]prop-2-enoate






.Mass Balance

Sr.No


Raw Material Name

Qty (kg)


Product / By

Product Wates Water


Waste (kg)

1 3 - Iso Chromanone 445 Toluene

recovered 1270

2 Methyl Formate 180 Toluene loss 30

3 Di Methyl Carbonate 270 Sodium

carbonate 650

4 Sodium Hydride 287 Methanol 96

5 Toluene 1300 EDC recovered 1365

6 HCl gas 110 EDC loss 35

7 EDC 1400 Picoxystrobin 1000

8 2-Chloro-6-

Trifluoro Methyl

Pyridine

483 KCl

223

9 Potassium Hydroxide 168 Aq. to ETP 627

10 Xylene 1000 Xylene recovered 980

11 Water 666 Xylene loss 20

Distillation

residue 13

1969 627 0 3615 85 13


Propiconazole Step-I 1,3-Dichloro benzene is reacted with Acetyl chloride in presence of Aluminum Chloride and Solvent – Ethylene Di Chloride to get 2,4-Dichloro Acetophenone.

+ CH3 CO

Cl

AlCl3/EDC

Cl

C

O

CH3

Cl

+ ClH36.46

Cl

Cl


acetyl chloride78.5


Step-II 2,4-Dichloro Acetophenone further reacted with bromine in presence of Solvent - Ethylene Di Chloride to get 2,4-Dichloro Phenacyl Bromide.



PTSA/EDC

Cl

C

O

CH3

Cl

+ BrH80.91


+ Br2159.81

Cl

C

O

CH2

Cl

Br

2-bromo-1-(2,4-dichlorophenyl)ethanone267.93

Step-III 2,4-Dichloro Phenacyl bromide reacted with 1,2-Pentanediol in presence of Toluene to get 4-(2-Bromomethyl- 4-Propyl-1,3-Dioxolane-2-yl)-1,3-Dichlorobenzene.

Toluene+ OH2

18.01

Cl

C

O

CH2

Cl

Br

2-bromo-1-(2,4-dichlorophenyl)ethanone267.93

+ CH2 CH CH2 CH2 CH3

OH OHpentane-1,2-diol

104.14 Cl

CO

CH2

Cl

Br

CH2 CH CH2 CH2 CH3

O

2-(bromomethyl)-2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolane

354.06 Step-IV 4-(2-Bromomethyl-4-Propyl-1,3-Dioxolane-2-yl)-1,3-Dichlorobenzene further reacted with 1,2,4-Triazole in presence of Potassium hydroxide and Solvent DMF to get final product PROPICONAZOLE.

KOH/DMF

+ BrH80.91

Cl

CO

CH2

Cl

Br

CH2 CH CH2 CH2 CH3

O

2-(bromomethyl)-2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolane

354.06

+NH

N

N

1H-1,2,4-triazole69.06 Cl

CO

CH2

Cl

N

CH2 CH CH2 CH2 CH3

ON

N

1-{[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]methyl}-1H-1,2,4-triazole

342.22






Mass Balance

Sr.no


Raw Material Name

Qty (kg)


Product/By-Product

(kg) Wates Water

Air Emission

(kg) Recovery

(kg) Solvent

Loss (kg)

Solid/Hazardous Waste (kg)

1 1,3 Di Chloro

Benzene 452 30% HCl 375

2 Acetyl Chloride 238 20% AlCl3 2786

3 Aluminium Chloride 558 28% HBr

solution 890

4 EDC 1600 EDC recovered 1570

5 Water 3715 EDC loss 30

6 Bromine 553 Toluene recovered 980

7 Catalyst 10 Toluene loss 20

8 1,2 – Butanediol 320 Water

recovered 55

9 Toluene 1000 Propiconazole 1000

10 Potassium Hydroxide 166 DMF

recovered 975

11 1,2,4 – Triazole 210 DMF loss 25

12 DMF 1000 KBr 390

Aq. to ETP 712

Process loss 14

5441 712 14 3580 75 0


Prothioconazole

Step-I 1,2 Dichloro Benzene reacts with 1-Chloro Cyclo Propane & 2-Hydroxy Propanyl Chloride in presence of Solvent Xylene and Catalyst to give Intermediate (A) 1-Chlorocyclopropyl-3-(2-Chlorobenzyl)-2-Hydroxy Chloro Propane.

CH2 CH CH3

OH

Cl

1-chloropropan-2-ol

94.54

+Cl

chlorocyclopropane76.52

+

Cl

Cl

1,2-dichlorobenzene

147

catalystxylene

Cl

CH2 CH2C

OH

ClCl

+ ClH

1-chloro-2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)propan-2-ol

279.59

36.46+ H2

2.01

Step-II Intermediate (A) when reacts with 1,2 Dihydro 3H – 1,2,4 Triazole 3-Thione in presence of Solvent & Catalyst to give the final product Prothioconazole.



catalystCl

CH2 CH2C

OH

ClCl

+ ClH

1-chloro-2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)propan-2-ol

279.59

36.46+

NH

N

NHS

1,2-dihydro-3H-1,2,4-triazole-3-thione101.13

Cl

CH2 CH2C

OH

Cl

N

N

NH

S2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione

344.26




Mass Balance

Pyraclostrobin Step-I 1, 4 Dichloro Benzene reacts with 3-Chloro Pyrazole in presence of catalyst & solvent Xylene to form Intermediate (A) as 3-Chloro 4-Chloro Phenyl Pyrazole.

Cl

Cl1,4-dichlorobenzene

147

+N

NH

Cl

N

Cl

N

Cl

3-chloro-1H-pyrazole102.52

+ ClH

3-chloro-1-(4-chlorophenyl)-1H-pyrazole213.06

36.46

Step-II 2-Chloro Benzyl Alcohol reacts with N-Methoxy Carbamate to form second Intermediate (B) N-methoxy, N-(2-Oxymethyl Phenol) Carbamate.

Sr.No


Raw Material Name

Qty (kg)


Product / By

Product Wates Water

Air Emission Recovery Loss Solid/Hazardo

us Waste (kg)

1 1,2 Dichloro Benzene 455 30% HCl 750

2 Chloro Cyclopropane 236 Catalyst 20

3 2 – Hydroxy

Propanyl Chloride

295 Hydrogen 6

4 Xylene 2000 Prothioconazole 1015 5 Catalyst 20 Aq. to ETP 1059 6 Water 1543 Xylene recovered 1960

7 2,4 Dihydro

1,2,4 Triazole 5 –Thione

315 Xylene loss

40

Process loss 14

1765 1059 20 1960 40 20




CH2

Cl

OH

2-chloro benzyl alcohol142.58

+ COCH3NH

O

H3CO

methyl methoxycarbamate105.09

CH2

N

OH CH3CO

O

OCH3 + ClH

methyl [2-(hydroxymethyl)phenyl]methoxycarbamate211.2

36.46

Step-III (A) & (B) then undergoes Condensation reaction in presence of Catalyst & Solvent Xylene gives the final product Pyraclostrobin.

CH2

N

OH CH3CO

O

OCH3

methyl [2-(hydroxymethyl)phenyl]methoxycarbamate

211.2

+N

N

Cl

Cl

N

N

Cl

OCH2

N

CH3CO

O

OCH3

+ ClH

Pyraclostrobin

387.82

36.46

3-chloro-1-(4-chlorophenyl)-1H-pyrazole213.06






Mass Balance

Sr.No


Raw Material Name

Qty (kg)


Product / By

Product Wates Water


Waste (kg)

1 1,4 Dichloro Benzene 422 Catalyst 10

2 3 – Chloropyrazole 275 30% HCl 840

3 Xylene 4000 Pyraclostrobin 1000

4 Catalyst 10 Aq. To ETP 955

5 2 –

Chlorobenzyl Alcohol

350 Xylene recovery 3950

6 N – Methoxy Carbamate 270 Xylene loss 50

7 Water 1500 Distillation residue 22

Total 1840 955 0 3950 50 32


Tebuconazole Step-I 1-(4-Chlorophenyl)-4,4-Dimethyl-3-Pentanone reacted with Sodium Methoxide & Dimethyl Sulfide in presence of Toluene to get 2- [ 2-( 4- Chlorophenyl)ethyl ]-2-(1,1 – Di methyl ethyl ) Oxirane.

CH2

Cl

CH2 C

O

C

CH3

CH3

CH3

1-(4-chlorophenyl)-4,4-dimethylpentan-3-one

224.72

+ CH3 O Na

sodium methanolate

54.02

+ CH3 S CH3

(methylsulfanyl)methane

62.13

Toluene

CH2

Cl

CH2 C

CH2

C

CH3

CH3

CH3O

2-tert-butyl-2-[2-(4-chlorophenyl)ethyl]oxirane

+

238.75

CH3OH32.04

+ CH3 S Na

70.09sodium methanethiolate

Step-II 2- [ 2-( 4- Chlorophenyl)ethyl ]-2-(1,1 – Di methyl ethyl ) Oxirane. is reacted with 1,2,4-Triazole in presence of DMF to give final product TEBUCONAZOLE

DMF

CH2

Cl

CH2 C

CH2

C

CH3

CH3

CH3O

2-tert-butyl-2-[2-(4-chlorophenyl)ethyl]oxirane

238.75

+NH

N

N

69.061H-1,2,4-triazole

CH2

Cl

CH2 C C

CH3

CH3

CH3OH

CH2

N

N

N

1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol

307.81




Mass Balance

Sr.No

Input/(kg) of Product Sr.

No.


Raw Material Name

Qty (kg)


Product / By

Product

Wates

Water

Air Emissio

n Recover

y Los

s Solid/Hazardou

s Waste (kg)

1

1-(4 – Chloropheny

l) 4-4-Dimethyl -3- Pentanoate

675 1 Methanol 95

2 Sodium Methoxide 152 2 Rec. Toluene 1360

3 Di Methyl Sulphide 186 3 Loss toluene 40



Sr.No

Input/(kg) of Product Sr.

No.


Raw Material Name

Qty (kg)


Product / By

Product

Wates

Water

Air Emissio

n Recover

y Los

s Solid/Hazardou

s Waste (kg)

4 Toluene 1400 4 20% Sodium

Methyl Sulphide

1048

5 Water 1706 5 Tebuconazole 1000

6 1,2,4 – Triazole 206 6 DMF loss 30

7 DMF 1100 7 DMF recov. 1070

8 Aq. layer to ETP 768

9 Process loss 14

2143 768 14 2430 70 0


Thifluzamide In the first step, Ethyl trifluoroacetate (ETFFA) is chlorinated at low temperature and the chlorinated compound is thioacetamide in presence of solvent and finally reacted NaOH and acidified to get thiazole acid. The acid is chlorinated by Thionyl chloride in toluene. Finally the thiazole acid chloride is reacted with 2,6‐dibromo‐4‐trifluoromethoxyaniline in presence of solvent. The product is isolated by filtration and washing and drying.

Step-I: Preparation of Ethyl - 4, 4, 4- Tri-fluoro -2 - Chloro Acetoacetate. Chemical reaction

O

F3C

O

OC2H5

Ethy l - 4, 4, 4 - trif luoro acetoacetate

184.11

+ Cl Clchlorine

70.9

O

F3C

O

OC2H5Cl

+ ClH

Ethy l 2 chloro - 4, 4, 4 - trif luoro acetoacetate218.55

36.45

ClH + Na OH +Na Cl OH2

36.46 39.99 58.44 18.01

Step-II: Preparation of 2 - Methyl -4 - trifluoromethyl -5 - thiazole carboxylic acid ethyl ester. Chemical reaction



O

F3C

O

OC2H5Cl

Ethy l 2 Chloro - 4, 4, 4 - trif luoro acetoacetate

218.55

+

ClH + Na OH +Na Cl OH2

36.46 39.99 58.44 18.01

S

NH2CH3

ethanethioamide

75.13

ET3N / AcCS

N

CH3

CF3

O

OC2H5 + ClH

239.21

36.45

+ OH2

18.012- Methyl - 4 - trifluoromethyl - 5 -thiazole carboxylic acid ester

Step-III: Preparation of 2- Methyl- 4- trifluoromethyl -5 - thiazole carboxylic acid. Chemical reaction

NaOH/HClS

N

CH3

CF3

O

OC2H5

2 - Methy l - 4 - trif luoromethy l - 5 -thiazole carboxy lic acid ester

239.21

S

N

CH3

CF3

O

OH+

2 - Methy l - 4 - trif luoromethy l - 5 -thiazole carboxy lic acid

H5C2 OHethanol

211.1646.06

Step-IV: Preparation of 2- Methyl- 4- trifluoromethyl- 5- thiazole carboxylic acid chloride. Chemical reaction

S

N

CH3

CF3

O

OH

2 - Methy l - 4 - trif luoromethy l - 5 -thiazole carboxy lic acid

211.16

TolueneS

O

ClClthionyl dichloride

+

118.97

S

N

CH3

CF3

O

Cl+ ClH

SO2

36.45

64.06+

2-methyl-4-(trifluoromethyl)-1,3-thiazole-5-carbonyl chloride229.6

SO2 + 2 NaOH Na2SO4 + H2

64.06 80 142.04 2

Step-V: Preparation of N - (2, 6- dibromo -4 - (trifluoromethoxy) phenyl)-2-methyl-4- trifluoromethyl -5 - thiazolecarboxamide. Chemical reaction



Acetonitri leS

N

CH3

CF3

O

Cl

2-methyl-4-(trifluoromethyl)-1,3-thiazole-5-carbonyl chloride

229.6

+

NH2

Br Br

OCF3

2,6-dibromo-4-(trifluoromethoxy)aniline

334.92

S

N

CH3

CF3

O

NH

Br

Br

OCF3

N-[2,6-dibromo-4-(trifluoromethoxy)phenyl]-2-methyl-4-(trifluoromethyl)-1,3-thiazole-5-carboxamide

528.06

+ ClH36.45




Mass Balance

Sr.No


Raw Material Name

Qty (kg)


Product / By

Product Wates Water


Waste (kg)

1 Ethyl trifluoroacetate 598 NaCl 293

2 Chlorine gas 198 Water to ETP 1308

3 Sodium Hydroxide 131 AcC

recovered 950

4 Water 3241 AcC loss 50 5 Ethanethiomide 196 Process loss 59

6 Triethyl amine (ET3N) 15 Ethanol

recovred 115

7 Acetonitrile 1000 Aq. layer 1282 8 NaOH 475 30% HCl 565

9 HCl 30% 315 Toluene recovered 1920

10 Thionyl chloride 276 Toluene loss 80 11 Toluene 2000 Na2SO4 328 12 DBTFMA 705 H2 gas 4

Water to ME 1196

Thifluzamide 1000

2186 3786 63 2985 130 0


Trifloxystrobin Step-I 2-Methyl Aniline is reacted with Sodium Nitrite and Hydrochloric acid to give 2-Methyl benzene Diazonium salt by diazotization.

NH2

CH3

2-methylaniline107.15

N+

CH3

N

+ OH2NaNO2 ClH

72.9269

Cl-

OH2

Na Cl58.44

+ +

154.6

22

36.02+

Step-II 2-Methyl Benzene Diazonium salt further reacted with Glyoxylic Acid methyl ester Oxime to give 2-Methyl phenyl glyoxalin acid methyl ester Oxime.



N+

CH3

N Cl-

OH2

154.6

+H

OCH3 N

O

OH

methyl (2E)-(hydroxyimino)ethanoate

103.07

C

CH3

C

NOH

O

OCH3

methyl (2Z)-(hydroxyimino)(2-methylphenyl)ethanoate

193.2

N2 HCl+ +28 36.46

Step-III 2-Methyl Phenyl Glyoxylic Acid methyl ester Oxime reacted with Dimethyl sulfate in presence of Sodium Hydroxide to give 2-Methyl Phenyl Glyoxylate-o-methyl Oxime.

C

CH3

C

NOH

O

OCH3

methyl (2Z)-(hydroxyimino)(2-methylphenyl)ethanoate

193.2

+(CH3)2SO4

SO

O O

OCH3CH3

126.13

Methy lation/NaOHC

CH3

C

NO

O

OCH3

CH3

SO

O O

OCH3H

Methy l bisuphate2-Methyl Phenyl Glyoxylate-o-methyl Oxime

207.22

+

112.1

Step-IV 2-Methyl Phenyl Glyoxylate-o-methyl Oxime further on chlorination with chlorine gas in presence of Solvent –EDC gives 2-Methyl chloride phenyl Glyoxylate-o-methyl Oxime.

Chlorination/EDCC

CH3

C

NO

O

OCH3

CH3

2-Methyl Phenyl Glyoxylate-o-methyl Oxime

207.22

++ Cl Cl

70.91

C

CH2

C

NO

O

OCH3

CH3

Cl

ClH

methyl (2Z)-[2-(chloromethyl)phenyl](methoxyimino)ethanoate241.67

36.46

Step-V 2-Methyl chloride Phenyl Glyoxylate-o-methyl Oxime reacted with Sodium [-1- [3- ( Trifluoromethyl) Phenyl ] Ethylidene ] Amine ] Oxidanide in presence of Solvent – DMF to give final product TRIFLOXYSTORBIN.

DMF

+

C

CH2

C

NO

O

OCH3

CH3

Cl

NaCl

methyl (2Z)-[2-(chloromethyl)phenyl](methoxyimino)ethanoate

241.67

58.44

+F3C

CH3

N ONa

sodium ({(1E)-1-[3-(trifluoromethyl)phenyl]ethylidene}amino)oxidanide

225.14

C

CH2

C

NO

O

OCH 3

CH3

OC CF3

CH3

N

methyl (2Z)-(methoxyimino)(2-{[({(1E)-1-[3-(trifluoromethyl)phenyl]ethylidene}amino)oxy]methyl}phenyl)ethanoate

408.37






Mass Balance

Sr.No

Input/MT of Product Output/(kg) of Product Input

Material Name

Qty (kg)


Product/By-Product

(kg) Wates Water

Air Emission

(kg) Recovery

(kg) Solvent

Loss (kg)


1 2 – Methyl

Aniline 275 NaCl 580

2 Sodium Nitrite 177 N2 71

3

30% Hydrochloric

Acid 338 Water to ETP

303

4

Glyoxylic Acid Methyl Ester Oxime

259 Methyl bisulphate 151

5 Sodium

Hydroxide 306 30% HCl 310

6 Di Methyl Sulphate 160 EDC

recovered 1160

7 Chlorine

Gas 190 EDC loss 40

8 EDC 1200 Trifloxystrobin 1000

9

Sodium [1-{(3-Trifluoro

Methyl) Phenyl}

Ethylidene Amino]

Oxidanide

518 DMF recovered

1360

10 DMF 1400 DMF loss 40

11 Water 3792 Aq. to ETP 3582

Distillation

residue 18

2041 3885 71 2520 80 18


HERBICIDE Carfentrazone

Stage I: Intermediate – I Sodium sulfite solution was charged to a mixture of 2-fluoroaniline, sodium nitrite solution & hydrochloric acid at 40 – 45°C. The subsequent mass was basified with caustic lye solution & the resultant product of this step (Intermediate – I) was obtained by filtration.

NH2

F2-fluoroaniline

111.11

+ ClH + NaNO2Na2SO3NaOH

NH

F

NH2

126.13Intermediate

-I

(2-fluorophenyl)hydrazine

Stage II: Intermediate – II A mixture of Intermediate - II, acetaldehyde, sodium cyanate and acetic acid in solvent methanol was chlorinated using chlorine gas at 50 – 55 °C for 6 – 8 hours. Product of this step (Intermediate II) was filtered after recovery of methanol under reduced pressure.



F

NH NH2

126.13Intermediate

-I

+ CH3CHO + NaOCN + CH3COOHCH3OH/Cl2

(2-fluorophenyl)hydrazine

F

NN

NH

O

CH3

2-(2-fluorophenyl)-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one

193.17Intermediate

-II

Stage III: Intermediate – III A mixture of intermediate - II in solvent dimethyl formamide and potassium carbonate was heated to 175 – 180°C. Freon 22 gas was purged for 3 – 4 hours. The mass was cooled to 50 – 60°C and resultant solid was filtered. Chlorine gas was purged to the filtrate for 2 – 3 hours at 65 – 75°C. Dimethyl formamide was distilled off, residue quenched in water and the product of this step (Intermediate III) was obtained by filtration.

F

NN

NH

O

CH3

2-(2-fluorophenyl)-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one

193.17Intermediate

-II

+ CHF2Cl

Freon gas

K2CO3+ DMF/Cl2

F

NN

N

O

CH3

Cl

CHF2

2-(4-chloro-2-fluorophenyl)-4-(difluoromethyl)-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one

277.63

Intermediate-III

86.46

Stage IV: Intermediate – IV Nitric acid was charged to a mixture containing Intermediate – III in solvent dichloroethane and oleum at room temperature. The reaction mass was quenched in water and the resultant product (Intermediate – IV) was obtained by filtration. Solvent dichloroethane recovered during the process was recycled.

F

NN

N

O

CH3

Cl

CHF2

2-(4-chloro-2-fluorophenyl)-4-(difluoromethyl)-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one

277.63

Intermediate-III

H2SO4/HNO3

F

NN

N

O

CH3

Cl

CHO2N F

F

2-(4-chloro-2-fluoro-5-nitrophenyl)-4-(difluoromethyl)-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one

322.62Intermediate

-IV

Stage V: Intermediate – V A solution containing intermediate – IV in solvent isopropyl alcohol (IPA) and Pd/C catalyst was pressurized using hydrogen at 70 – 80°C for a period of 11 – 12 hours. The mass was



cooled to 50 – 60°C & Pd/C Catalyst was filtered off & recycled. Solvent IPA was distilled, residue was quenched in water and the product (Intermediate-IV) was obtained by filtration.

F

NN

N

O

CH3

Cl

CHO2N F

F

2-(4-chloro-2-fluoro-5-nitrophenyl)-4-(difluoromethyl)-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one

322.62Intermediate

-IV

5% Pd/C

IPA, H2

F

NN

N

O

CH3

Cl

CHNH2

F

F

2-(5-amino-4-chloro-2-fluorophenyl)-4-(difluoromethyl)-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one

292.64

Intermediate-V

Stage VI: Carfentrazone A mixture of Intermediate – V, ethyl acrylate and acetonitrile was charged to the reactor. Mixture was heated to 50 – 60°C and chlorine gas was purged. Acetonitrile was distilled off and the residue was quenched in water & the product was isolated by filtration. Recovered acetonitrile was recycled in subsequent batches.

F

NN

N

O

CH3

Cl

CHNH2

F

F

2-(5-amino-4-chloro-2-fluorophenyl)-4-(difluoromethyl)-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one

292.64

Intermediate-V

O

CH2

O

CH3

+

ethyl prop-2-enoate

100.11

F

NN

N

O

CH3

Cl

CHF

F

Cl

O

OCH3

ethyl 2-chloro-3-{2-chloro-5-[4-(difluoromethyl)-3-methyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl]-4-fluorophenyl}propanoate

412.19Carfentrazone




Mass Balance

Sr.no

Input(kg)/MT of Product Output/(kg) of Product


Product/ By-Product (kg)

Waste Water

Air Emission (kg)

Recovery (kg)

Solvent

Loss (kg)

Solid/Hazardous Waste

(kg)

1 2-fluoroaniline 730 Aqueous effluent

45546.25

2 Sodium nitrite 460 Sodium sulphite 1352

3 Hydrochloric acid 4210 Water Vapour 5408

4 Sodium sulphite 2710 Methanol recovered 3843

5 Water 42906 Methanol loss 321



Sr.no



Product/ By-Product (kg)

Waste Water

Air Emission (kg)

Recovery (kg)

Solvent

Loss (kg)


(kg)

6 20% NaOH solution 4275

Scrubbed sodium

hydroxide solution

(containing sodium hypochlori

te)

2592

7 Caustic lye solution 2644 Drying

loss 734.25

8 Acetaldehyde 382 Dimethyl formamid

e 6141

9 Chlorine 1085 Dimethyl formamid

e loss 147.5

10 Acetic acid 500 Dichloroet

hane recovered 3074

11 Methanol 4000 Dichloroethane loss 176

12 10% sodium

hydroxide Solution

1500 Spent acid

14793.4

13 Potassium carbonate 924

Isopropyl alcohol

recovered 5700

14 Dimethyl formamide 7500

Isopropyl alcohol

loss 625

15 Dichlorodifluoromethane 665

Catalyst Pd/C

recovered 59.5

16 Freon gas 895 Carfentrazone 1000

17 Oleum 5565.2 Acetonitril

e recovered 4825

18 Nitric acid 502.2 Acetonitrile loss 475

19 Dichloroethane 3250 20 Isopropyl alcohol 6325 21 Catalyst Pd / C 59.5 22 Ethyl acrylate 425 23 Acetonitrile 5300

2352 62931.65 6142.25 23642.5 1744.

5 0

Total 96812.9 Total 96812.9 Clethodim Step-I 5 – (Propyl 2 thio Ethyl) Cyclohexane 1:3 Dione is reacted with propionyl chloride to form the intermediate as – I



CHS CH3CH2CH3

CH2

OO

5-[2-(ethylsulfanyl)propyl]cyclohexane-1,3-dione214.32

+ CH2 CO

ClCH3

propanoyl chloride92.52

CHS CH3CH2CH3

CH2

OO CH2C

O

CH3

5-[2-(ethylsulfanyl)propyl]-3-oxocyclohex-1-en-1-yl propanoate270.38

Intermediate - 1Step-II Intermediate - I on isomerisation in presence of Aluminium Chloride gives the intermediate - II

CHS CH3CH2CH3

CH2

OO CH2C

O

CH3

5-[2-(ethylsulfanyl)propyl]-3-oxocyclohex-1-en-1-yl propanoate

270.38

Intermediate - 1

+ AlCl3133.34

CH2 C

O

CH3

CHS CH3CH2CH3

CH2

O OH

270.38Intermediate - 2

5-[2-(ethylsulfanyl)propyl]-3-hydroxy-2-propanoylcyclohex-2-en-1-one

Step-III Intermediate -II on reaction with 1 Chloro 3 - allyl Oxy amine in presence of Solvent gives the final product Clethodim

+

CH2 C

O

CH3

CHS CH3CH2CH3

CH2

O OH

270.38Intermediate - 2

NH2 O CH2 CH CH Cl

O-(3-chloroprop-2-en-1-yl)hydroxylamine107.53

Toluene

CH2C

NHCH3

CH

S

CH3

CH2

CH3

CH2

O

OCH2

CHCCl

H

O

2-[1-({[(2E)-3-chloroprop-2-en-1-yl]oxy}amino)propylidene]-5-[2-(ethylsulfanyl)propyl]cyclohexane-1,3-dione

359.91Clethodim

5-[2-(ethylsulfanyl)propyl]-3-hydroxy-2-propanoylcyclohex-2-en-1-one




Mass Balance

Sr.no


Input Material Name

Qty (kg)


Product / By-

Product (kg)

Waste Water

Air Emission

(kg) Recovery

(kg) Solvent

Loss (kg)


1

5-Propyl 2-Thio Ethyl

Cyclohexane 1,3 dione

625 Clethodim 1020

2 Propionyl Chloride 285 Recovered

Toluene 2450 3 AlCl3 450 Toluene loss 50

4 1-Chloro 3-Allyl Oxy Amine

330 20% NH3 solution 2250

5 Toluene 2500 Aq. layer to ETP 1220 6 water 2800

3270 1220 0 2450 50 0




Clodinafop Propargyl Step-I 2,3 – Di Fluoro -5 - Chloro Pyridine is reacted with 2 - ( 4- Hydroxy Phenoxy) Propionic Acid in presence of Solvent - Di Methyl Formamide ( DMF) and Sodium Hydroxide to form 2- [ -4 – {( 5 Chloro -3- Fluoro -2-Pyridinyl ) Oxy} Phenoxy ] Propionic Acid.

FH + NaOH NaF + OH220 18.0140 41.99

N F

FCl

+

OH

O CH

CH3

C

OH

O

DMF

N O

FCl

O CH CH3

COHO

182.172-(4-hydroxyphenoxy)propanoic acid

+ FH205-chloro-2,3-difluoropyridine

149.52

2-{4-[(5-chloro-3-fluoropyridin-2-yl)oxy]phenoxy}propanoic acid

311.69

Step-II 2- [ -4 – {( 5 Chloro -3- Fluoro -2- Pyridinyl ) Oxy} Phenoxy ] Propionic Acid is reacted with Propargyl chloride in Presence of Sodium Hydroxide as well as Solvent -Toluene to form final product as CLODINAFOP PROPARGYL

DMF

N O

FCl

O CH CH3

COHO

+ ClH36.46

+ CH2 C CHCl

Propargyl chloride74.5

N O

FCl

O CH CH3

COO CH2 C CH

NaOH + ClH NaCl + OH240 36.46 18.0158.44

2-{4-[(5-chloro-3-fluoropyridin-2-yl)oxy]phenoxy}propanoic acid

311.69

prop-2-yn-1-yl 2-{4-[(5-chloro-3-fluoropyridin-2-yl)oxy]phenoxy}propanoate349.74

The starting material, the sodium salt of 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)-phenoxy]-propionate is obtained as follows:



(a) 3-amino-2,3-dichloropyridine

To a solution of 129.2 g (0.69 mol) of 2,5-dichloro-3-nitropyridine in 1300 ml of dioxane is added 26.0 g of Raney-nickel, that has previously been washed with ethanol. This mixture is then hydrogenated with hydrogen under normal pressure at 20°-35° C. After uptake of 20% of the theoretical amount of hydrogen, another 30 g of washed Raney-nickel catalyst are added. After hydrogenating for 22 hours, the catalyst is filtered off, the solvent is evaporated and the residue is crystallized from hexane/ethyl acetate. Thus, 84.9 g of 3-amino-2,5-dichloropyridine (78% of the theory) are obtained, which melts at 129°-132° C.

N Cl

Cl N+

O

O-

2,5-dichloro-3-nitropyridine192.98

+ H2

6

Raney-Nickel

DioxaneN Cl

Cl NH2

2,5-dichloropyridin-3-amine163

+ OH22336.02

(b) 2,5-dichloro-3-fluoropyridine

To 450 ml (22.5 mol) of hydrogen fluoride in a stainless steel reaction vessel are added at a temperature of -5° to -1°, 163 g (1.0 mol) of 3-amino-2,5-dichloropyridine. Then there are added while stirring at the same temperature 82.8 g (1.2 mol) of sodium nitrite into the solution. The reaction mixture is stirred for 1.5 hours at -5° to -1°, then the temperature is slowly raised to +60° C. After the evolution of gas has ceased, the hydrogen fluoride is distilled off and the residue is taken up in methylene chloride. Ice/water is then added thereto and the cold mixture is neutralized with concentrated ammonium hydroxide solution. The organic phase separated and the water phase is extracted three times with methylene chloride. The organic phases are washed with water, dried over magnesium sulfate, filtered through silicagel and evaporated. Thus, 141.5 g (85% of the theory) of 2,5-dichloro-3-fluoropyridine are obtained.

N Cl

Cl NH2

2,5-dichloropyridin-3-amine163

+ FHhydrogen fluoride

20

Sodium nitrite solution

N Cl

Cl F

2,5-dichloro-3-fluoropyridine165.98

+ NH3

ammonia17.03

(c) 5-chloro-2,3-difluoropyridine

A suspension of 64.6 g (1.1 mol) of potassium fluoride and 11.25 g (0.075 mol) of cesium-fluoride in 240 ml of sulfolane (1,1-dioxo-tetrahydrothiophene) is heated to 140° C. By



reducing the pressure 50 ml of sulfolane are distilled off. To the suspension a solution of 61.4 g (0.37 mol) of 2,5-dichloro-3-fluoropyridine in 20 ml of sulfolane is added. The reaction-mixture is then stirred for 35 hours at a temperature of 140°, cooled and poured into ice/water. The organic material is extracted with ether. The ethereal layer is washed with water dried over magnesium sulfate, filtered and evaporated to yield 48.7 g of a colourless oil (88% of the theory) which boils at 65°-66° at 133 mbar.

N Cl

Cl F

2,5-dichloro-3-fluoropyridine165.98

SO O

tetrahydrothiophene 1,1-dioxide120.17

+ KF58.09

+ CsF151.9

+N F

Cl F

5-chloro-2,3-difluoropyridine149.52

(d) 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)-phenoxy]-propionic acid methyl ester

To a stirred mixture of 21.6 g (0.11 mol) of 2-(4-hydroxyphenoxy)-propionic acid methyl ester, 15.2 g (0.11 mol) of potassium carbonate, 1.45 g (0.0055 mol) of 18-Crown-6 ether and 100 ml of acetonitrile is added dropwise a solution of 14.95 g (0.10 mol) of 5-chloro-2,3-difluoropyridine in 30 ml of acetonitrile and the mixture is heated at a temperature of 50° to 60° C. during 40 hours. The mixture is then poured into ice/water. The organic material is extracted with ethyl acetate, washed with a saturated salt solution, dried over magnesium sulfate, filtered and evaporated. The oily residue is purified by chromatography over a silica gel column with a hexane/ethyl acetate 3:1 solvent. After evaporation of the solvent one obtain 20.4 g of the above ester (63% of the theory) is obtained in crystalline form. The melting point is 63°-64° C.

N F

Cl F

5-chloro-2,3-difluoropyridine

149.52

OH

O

CH3

O

OCH3

methyl (2R)-2-(4-hydroxyphenoxy)propanoate196.2

+K2CO3

Acetonitrile O

O

CH3

O

OCH3

N

Cl

F

methyl (2R)-2-{4-[(5-chloro-3-fluoropyridin-2-yl)oxy]phenoxy}propanoate

325.72

(e) 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)-phenoxy]-propionic acid sodium salt

To a solution of 13.0 g (0.04 mol) 2-[4-(5-chloro-3-fluoropyridin-2-yloxy)]-propionic acid methyl ester in 65 ml of dioxane is added 42 ml of 1N sodium hydroxide. Then it is stirred for



21/2 hours at a temperature of 35° C. The mixture is then concentrated to dryness at room temperature in a rotatory evaporator. The remaining salt 13.2 g is used without further purification.

O

O

CH3

O

OCH3

N

Cl

F

methyl (2R)-2-{4-[(5-chloro-3-fluoropyridin-2-yl)oxy]phenoxy}propanoate

325.72

1N NaOH

DioxaneO

O

CH3

O

ONa

N

Cl

F

sodium (2R)-2-{4-[(5-chloro-3-fluoropyridin-2-yl)oxy]phenoxy}propanoate333.67

O

O

CH3

O

ONa

N

Cl

FHCl

DioxaneO

O

CH3

O

OH

N

Cl

F

sodium (2R)-2-{4-[(5-chloro-3-fluoropyridin-2-yl)oxy]phenoxy}propanoate

333.67

(2R)-2-{4-[(5-chloro-3-fluoropyridin-2-yl)oxy]phenoxy}propanoic acid311.69




Mass Balance

Sr.no


Input Material Name

Qty (kg)


Product/By-Product

(kg) Waste Water

Air Emission

(kg) Recovery

(kg) Solvent

Loss (kg)


1

2, 3–Di Fluoro–5–

Chloro Pyridine

448 NaF 127

2

2–(4–Hydroxy

Phenoxy) Propionic

548 Rec.DMF

1170



Sr.no


Input Material Name

Qty (kg)


Product/By-Product

(kg) Waste Water

Air Emission

(kg) Recovery

(kg) Solvent

Loss (kg)


Acid

3 NaOH 240 DMSO loss 30 4 DMF 1200 Water rec. 55

5 Propargyl Chloride 180 Clodinafop

Propargyl 1000 6 Toluene 1000 Toluene loss 980 7 Water 450 Toluene rec. 20

Residue 5

NaCl 175

Water to ETP 504

1302 504 0 2205 50 5


Clomazone Step-I Synthesis of 3-chloro-N-hydroxy-2, 2-dimethylpropanamide (CNHP)

CH2 C CO

ClCH3

CH3

Cl

3-chloro-2,2-dimethylpropanoyl chloride

Mol Wt. 155.02

+ N+

OH

HH

HClH

NaOHCH2 C C

O

NHCH3

CH3

ClOH

3-chloro-N-hydroxy-2,2-dimethylpropanamide Mol Wt. 151.59

+Mol Wt. 72.9

Cl-

hydroxylamine hydrochloride

Mol Wt. 69.46

2

ClH + NaOH NaCl + OH22 2 2 272.9 80 116.9 36.02

Step-II Synthesis of 4, 4-dimethyl-3-isoxazolidinone (DIO)

CH2 C CO

NHCH3

CH3

ClOH

3-chloro-N-hydroxy-2,2-dimethylpropanamide

Mol Wt. 151.59

NH

O

OCH3

CH3

4,4-dimethyl-1,2-oxazolidin-3-one

Mol Wt. 115.13

NaOH

+ ClHMol Wt. 36.46

Step-III Synthesis of Clomazone



.

NH

O

OCH3

CH3

4,4-dimethyl-1,2-oxazolidin-3-one

Mol Wt. 115.13

+

Cl

CH2 ClNa2CO3

Cl

CH2 NC

O CH2

C

OCH3

CH3

2-(2-chlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one

(Clomazone)

Mol Wt. 239.7

+ ClH

Mol Wt. 36.46

1-chloro-2-(chloromethyl)benzene

Mol Wt. 161.02




Mass Balance

Sr.no


Input Material Name

Qty (kg)


Product/By-Product

(kg) Waste Water

Air Emission

(kg) Recovery

(kg) Solvent

Loss (kg)


1

3-chloro-2, 2-dimethylpropanoyl

chloride 713 NaCl 1850

2 hydroxylamine hydrochloride 318 Water to ETP 3869

3 50% NaOH

solution 1048 Clomazone 815

4 Water 3400 Dichloromethane recovered 2360

5

Sodium Carbonate or

NaOH 383 Dichloromethane

loss 40

6 2-chlorobenzyl

chloride 672 Hexane recovered 1950

7 Dichloromethane 2400 Hexane loss 50

8 Hexane 2000

2665 3869 0 4310 90 0 Total 10934 Total 10934

Cloransulam Step-I Hydrazine reaction 2-Ethoxy-4,6-difluoropyrimidine react with hydrazine in presence of Methanol to produce 2-Ethoxy-4-hydrazino-6-fluoropyrimidine

NN

OC2H5

FF2-ethoxy-4,6-difluoropyrimidine

160.12

+ NH2 NH2

hydrazine32.04

Methanol NN

OC2H5

NHF NH2

+ FH

2-ethoxy-4-fluoro-6-hydrazinylpyrimidine172.16

hydrogen fluoride20

Step-II Cyclization and isomerization reaction 2-Ethoxy-4-hydrazino-6-fluoropyrimidine react with CS2 in the presence of ET3N to get 5-ethoxy-7-fluoro-[1,2,4]triazolo[4,3-c]pyrimidine-3(2H)-thione approx.

ET3NNN

OC2H5

NHF NH2

2-ethoxy-4-fluoro-6-hydrazinylpyrimidine172.16

+ CS2

76.14

NN

OC2H5

F

N

N

SH

5-ethoxy-7-fluoro[1,2,4]triazolo[4,3-c]pyrimidine-3(2H)-thione

214.22

+ SH2

34.08

Isomerisation From 5-ethoxy-7-fluoro-[1,2,4] triazolo[4,3-c]pyrimidine-3(2H)-thione to form 5-ethoxy-7-fluoro-[1,2,4]triazolo[1,5-c]pyrimidine-3-thiol



NN

OC2H5

F

N

N

SH

5-ethoxy-7-fluoro[1,2,4]triazolo[4,3-c]pyrimidine-3(2H)-thione

214.22

NN

OC2H5

F

N

NSH

5-ethoxy-7-fluoro[1,2,4]triazolo[1,5-c]pyrimidine-2-thiol214.22

Step-III chlorosulfonylation 5-ethoxy-7-fluoro-[1,2,4]triazolo[1,5-c]pyrimidine-3-thiol to 5-ethoxy-7-fluoro-[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonyl chloride

.

NN

OC2H5

F

N

NSH

5-ethoxy-7-fluoro[1,2,4]triazolo[1,5-c]pyrimidine-2-thiol

214.22

NaClO4

ClH

NN

OC2H5

F

N

NSO2Cl

5-ethoxy-7-fluoro[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonyl chloride

280.66

Step-IV Amidation 5-ethoxy-7-fluoro-[1,2,4] triazolo[1,5-c]pyrimidine-2-sulfonyl chloride in Dichloromethane react with 2-AMINO-3-CHLORO-BENZOIC ACID METHYL ESTER to get Cloransulam.

NN

OC2H5

F

N

NSO2Cl

5-ethoxy-7-fluoro[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonyl chloride

280.66

+ NH2

Cl

C OCH3

O

methyl 2-amino-3-chlorobenzoate185.6

NN

OC2H5

F

N

NS

O

O

NH

Cl

C OCH3

O

methyl 3-chloro-2-{[(5-ethoxy-7-fluoro[1,2,4]triazolo[1,5-c]pyrimidin-2-yl)sulfonyl]amino}benzoate

429.81

+ ClH

36.46






Mass Balance

Sr.no


Input Material Name

Qty (kg)


Product/By-Product

(kg) Waste Water

Air Emission (kg)

Recovery (kg)

Solvent Loss (kg)


(kg)

1

2-Ethoxy-4,6-difluoropyrimidi

ne 627 Methanol

recovered 2630

2 hydrazine 80 % 255 Methanol loss 120

3 Methanol 2750 30% HF 262

4 Water 184 Drying loss 327

5 Triethyl amine 560 H2S 130

6 Carbon

disulphide 314 Filtrate to ETP 6461

7 Hydrogen

peroxide 30% 628 Cloransulam 1000 8 30% HCl 25 30% HCl 330

9

30% Sodium methylate- methanol solution

745 Dichloromethane recovered

550

10 Conc. HCl 422 Dichloromethane loss 40

11

Dichloromethane Hydrochloric

acid 980

12 Sodium

perchlorate 490 13 Water 278



Sr.no


Input Material Name

Qty (kg)


Product/By-Product

(kg) Waste Water

Air Emission (kg)

Recovery (kg)

Solvent Loss (kg)


(kg) 0

14 Dichloromethan

e 590

15

2-Amino-3-Chlorobenzoic

acid methyl ester

500

1592 6461 457 3180 160 0

Diclosulam Process Description It is prepared from 5-ethoxy-)-7-fluoro-[1,2,4]-triazolo[1,5-c]pyrimidine-2-sulfonyl Chloride and 2,6-Dichloroaniline through a condensation reaction in an organic solvent in the presence of 3,5-Dimetylpyridine as catalyst. Reaction mass stir at 48 ° C for 24 hrs. After completion of the reaction, filter the reaction mass and dry the wet cake of product.


N NN S

Cl

NF

O O

O+

Cl

NH2

Cl

N NN S

NHN

F

O OO

Cl

Cl

5-Ethoxy-7-Fluoro[1,2,4]Triazolo[1,5-]Pyrimidine-2-Sulfonyl Chloride

2,6-Dichloro Aniline -(2,6-Dichlorophenyl)-5-Ethoxy-7-Fluoro[1,2,4]Triazolo[1,5- ]Pyrimidine-2-Sulfonamide

N

Mol. Wt.: 406.22Mol. Wt.: 162.02Mol. Wt.: 280.66

C C

N

CH3H3C

N

CH3H3C

+ + HCl

3,5-Dimethyl Pyridine

Mol. Wt.: 107.15

Hydrochloric Acid3,5-Dimethyl Pyridine

Mol. Wt.: 107.15 Mol. Wt.: 36.5



Mass Balance

Sr.no


Input Material Name

Qty (kg)


Product/By-Product

(kg) Waste Water

Air Emission

(kg) Recovery

(kg) Solvent

Loss (kg)


1

5-ethoxy-)-7-fluoro-[1,2,4]-triazolo[1,5-

c]pyrimidine-2-sulfonyl Chloride

749 Product (Diclosulam) 1000

2 2,6-Dichloroaniline 642 3,5-

Dimetylpyridine 823

3 3,5-Dimetylpyridine 866 Hydrochloric

Acid 97 4 Acetonitrile 22942 Solvent 21801

5 Dimethyl Sulfoxide (DMSO)

8 Process Loss

1486

23721 0 0 0 1486 0


Fenoxaprop P Ethyl Step-I 2,6 - Dichloro Benzoxazole is reacted with 2- ( 4- Hydroxy Phenoxy ) Propionic Acid in presence of Sodium Hydroxide as well as Solvent – Di Methyl Sulfoxide ( DMSO) to form 2 – [ 4 - ( 6 –

Chloro -2- Benzoxazole ) Phenoxy ] Propionic Acid .

Chemical reaction

O

NCl

Cl

2,6-dichloro-1,3-benzoxazole188.01

+

O CH

CH3

CO

OH

OH

2-(4-hydroxyphenoxy)propanoic acid182.17

DMF/NaOHO

NO

Cl

O CH

CH3

CO

OH

2-{4-[(6-chloro-1,3-benzoxazol-2-yl)oxy]phenoxy}propanoic acid

333.72

+ NaCl58.44

Step-II 2 – [ 4 - ( 6 – Chloro -2- Benzoxazole ) Phenoxy ] Propionic Acid undergoes chlorination by Thionyl Chloride in presence of Solvent – Toluene to form 2-[ 4 - ( 6 – Chloro -2- Benzoxazole ) Phenoxy ] Propionic Acid Chloride .

Chemical reaction

O

NO

Cl

O CH

CH3

CO

OH

2-{4-[(6-chloro-1,3-benzoxazol-2-yl)oxy]phenoxy}propanoic acid

333.72

+ SCl

ClO

thionyl dichloride118.97

TolueneO

NO

Cl

O CH

CH3

CO

Cl2-{4-[(6-chloro-1,3-benzoxazol-2-yl)oxy]phenoxy}propanoyl chloride

352.16

+ ClH + SO264.0636.46



SO2

64.06 + NaOH Na2SO42

40 x 2 = 80 142.04+ H2

2 Step-III 2 – [ 4 - ( 6 – Chloro -2- Benzoxazole ) Phenoxy ] Propionic Acid Chloride is finally reacted with Sodium Ethoxide in presence of Solvent – Toluene to form the Final Product as FENOXYPROP P ETHYL.

Chemical reaction O

NO

Cl

O CH

CH3

CO

Cl+ CH2

CH3ONa

Toluene

2-{4-[(6-chloro-1,3-benzoxazol-2-yl)oxy]phenoxy}propanoyl chloride

352.16

sodium ethanolate

68.05

O

NO

Cl

O CH

CH3

CO

O CH2 CH3

ethyl 2-{4-[(6-chloro-1,3-benzoxazol-2-yl)oxy]phenoxy}propanoate

361.77 + NaCl

58.44 Process Flow Diagram



Mass Balance

Sr.no


Input Material Name

Qty (kg)


Product/By-Product

(kg) Waste Water

Air Emission

(kg) Recovery

(kg) Solvent

Loss (kg)


1 3, 6 – Di Chloro

Benzoxazole 610 NaCl 586

2

2 – (4 – Hydroxy

Phenoxy) Propionic

Acid

590 DMF recovered

1360

3 NaOH 121 Xylene loss 40 4 DMF 1400 30% HCl 398

5 Thionyl Chloride 384 Toluene

recovered 2420 6 Toluene 2500 Toluene loss 80

7 20% NaOH solution 1125 Na2SO4 400

8 Sodium Ethoxide 222 Water to ETP 905

9 water 1200 Fenoxaprop P Ethyl 1000

Aq. layer 963

2384 1868 0 3780 120 0


Flufenacet Process description 2-(methylsulfonyl)-5-(trifluoromethyl)-1,3,4-thiadiazole, catalyst & EDC are added in to the reactor under stirring to get uniform slurry. The solution of N-(4-fluorophenyl)-2-hydroxy-N-isopropylacetamide in Ethylene dichloride is added in the reaction mass to maintaining the desired temperature. 25% aqueous Sodium hydroxide solution is also added. Reaction mass is stirred at desired temperature, until the reaction is over. There after Layers are separated, Aqueous layer is further extracted and Acidified. Excess solvent is recovered for recycling. The mass is filtered to get crude product and washed by Methanol to get desired quality of final product. Solvents are recovered & recycled.

Chemical Reaction

CH3N

CH3O

F

OH

N-(4-fluorophenyl)-2-hydroxy-N-(propan-2-yl)acetamide

211.23

+N N

SS

O

O

CH3F

FF

2-(methylsulfonyl)-5-(trifluoromethyl)-1,3,4-thiadiazole

232.2

25% NaOH

EDC N N

SF

FF

CH3N

CH3O

F

O

N-(4-fluorophenyl)-N-(propan-2-yl)-2-{[5-(trifluoromethyl)-1,3,4-thiadiazol-2-yl]oxy}acetamide

363.33(FLUFENACET)




Mass Balance

Sr.no


Input Material Name

Qty (kg)


Product/By-Product

(kg) Waste Water

Air Emission

(kg) Recovery

(kg) Solvent

Loss (kg)


1 N-(4-fluorophenyl)-2-

hydroxy-Nisopropylacetamide

520 Flufenacet 1000

2 2-(Methylsulfonyl)-5-

(trifluoromethyl)-1,3,4-thiadiazole

635 EDC recovered

2328

3 PTSA 6 EDC loss 122

4 25% Sodium hydroxide 708 Methanol

recovered 1330

5 5% Hydrochloric acid 575 Methanol

loss 70

6 Methanol 1400 Aq. to ETP 1289

7 Ethylene dichloride 2450 Drying loss 155

1000 1289 155 3658 192 0




Fomesafen Step-I 3 - Hydroxy -6- Nitro Benzoic Acid is reacted with 3,4 – Chloro Benzotrifluoride in presence of Solvent –Di Methyl Sulfoxide ( DMSO) and Sodium Hydroxide to form 2- Nitro -5- ( 2- Chloro -4- Trifluoro methyl Phenoxy) Benzoic Acid.

Cl

Cl

F

F

F+ NO2OH

COOH

O

Cl

F

F

F

NO2

COOH

1,2-dichloro-4-(trifluoromethyl)benzene215

DMSO NaOH

+ NaCl58.44

+ OH218.01

5-hydroxy-2-nitrobenzoic acid183.11

5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid

361.65(Intermediate - I)

Step-II 2- Nitro -5- ( 2- Chloro -4- Trifluoromethyl Phenoxy) Benzoic Acid (Intermediate – I) undergoes Chlorination by Thionyl Chloride in Presence of Solvent – Toluene to form Acid Chloride which on further reaction with Ammonium Hydroxide to form 2- Nitro -5- ( 2- Chloro -4- Trifluoromethyl Phenoxy) Benzamide.



O

Cl

F

F

F

NO2

COOH

5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid

361.65(Intermediate - I)

+ S Cl

Cl

Othionyl dichloride

118.97

Toluene

NH4OH

O

Cl

F

F

F

NO2

COCl

35.04

NH4Cl53.49

64.06

2

2 + ClH

+ SO2

36.46

5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoyl chloride380.1

O

Cl

F

F

F

NO2

CONH2

5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzamide360.67

+ + OH218.01

NaOH40

+ SO264.06

Na2SO3 + OH2126.04

218.01

Step-III 2- Nitro -5- (2- Chloro -4- Trifluoromethyl Phenoxy) Benzamide is further reacted with Methane Sulfonyl Chloride (MSC) in presence of Solvent – Toluene to form the final product Fomesafen.

O

Cl

F

F

F

NO2

CONH2

5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzamide360.67

+ CH3 SO2 Cl

114.55Methane sulphonyl chloride

Toluene

O

Cl

F

F

F

NO2

NHO

S O

CH3

O

5-[2-chloro-4-(trifluoromethyl)phenoxy]-N-(methylsulfonyl)-2-nitrobenzamide

438.76(Fomesafen)

+ClH36.46






Mass Balance

Sr.no


Input Material Name

Qty (kg)


Product/By-Product

(kg) Waste Water

Air Emission

(kg) Recovery

(kg) Solvent

Loss (kg)


1 3-Hydroxy-6-Nitro Benzoic

Acid 485 Rec. DMSO

2060

2 3,4-Di Chloro Benzotrifluoride 567 DMSO loss 40

3 DMSO 2100 Salt NaCl 154

4 NaOH 277 Rec. Toluene 1180

5 20% NH4OH solution 458 Toluene

loss 20

6 Toluene 2400 Salt NH4Cl 142 7 Water 910 30% HCl 342

8 Methane Sulfonyl Chloride

300 Sodium sulphite 270

Aq. layer 775

Rec. Toluene 1180

Toluene loss 24

30% HCl 300

Fomesafen 1000

Residue 10

2208 775 0 4420 84 10


Glufosinate Ammonium Process description

Charge water, HCl and n-Butyl (3-cyano-3-hydroxypropyl) methyl propionate in the reactor.

The mass is subjected to acidolysis at 45 – 50°C.

After the acidolysis reaction cool the mass to 20°C and purge ammonia gas at 20 – 25°C,

centrifuge and dry the cake to get Glufosinate Ammonium Technical. Send aqueous ML to

ETP.

Step-I

P

O

OHCH3 CH2 CH2 CH CN

NH2

(3-amino-3-cyanopropyl)methylphosphinic acid

162.12

+ ClH + OH2236.46 36.02

P

O

OHCH3 CH2 CH2 CH COOH

NH2

2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid(Glufosinate)

181.12

+ NH4Cl53.49

Step-II



P

O

OHCH3 CH2 CH2 CH COOH

NH2

2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid(Glufosinate)

181.12

+ NH3 + OH217.03 18.01

P

O

OHCH3 CH2 CH2 CH C

NH2

ONH4

O

[3-amino-4-(aminooxy)-4-oxobutyl]methylphosphinic acid

(Glufosinate Ammonium)196.14

+ OH218.01


Mass Balance

Sr.no


Input Material Name

Qty (kg)


Product/By-Product

(kg) Waste Water

Air Emission

(kg) Recovery

(kg) Solvent

Loss (kg)


1 WATER 3718 Glyphosate tech 1000

2 SODIUM TUNGSTATE 5 CO2 247

3 PMIDA 1621 Aq. later to ETP 4722.8

4 SODIUM METABISULFITE 21

5 VANADIUM SULPHATE 0.4

6 H2O2 604

1000 4722.8 247 0 0 0

Total 5969.4 Total 5969.8



Glyphosate Process description

Phosphono Methyl Imino Diacetic Acid (PMIDA) is charged in water in a reactor under stirring. Catalyst Sodium Tungstate is charged and the temperature is raised to 65 – 70°C while stirring.

Hydrogen peroxide is then added to the mass at the same temperature. A clear solution is formed. Cool to 30°C and add catalyst Vanadium sulphate to form Glyphosate.

Product slurry is cooled to 20°C, centrifuged and dried to get Glyphosate technical.

Step-I

N

O O

OH

P

OH

OH

OH O

2,2'-[(phosphonomethyl)imino]diacetic acid227.1

+ OH OHhydrogen peroxide

34.01

NH

O

OH

P

OH

OH O+ CH2 O

[(phosphonomethyl)amino]acetic acid169.07

formaldehyde30.02

+44 18.01

+ OH2CO2




Mass Balance

Sr.no


Input Material Name

Qty (kg)


Product/By-Product

(kg) Waste Water

Air Emission

(kg) Recovery

(kg) Solvent

Loss (kg)


1 WATER 2385 Glyphosate tech 1000

2 SODIUM TUNGSTATE 5 CO2 247

3 PMIDA 1621 Aq. later to ETP 4722.8

4 SODIUM METABISULFITE 21

5 VANADIUM SULPHATE 0.4

1 H2O2 604

2 Water for washing 1333

1000 4722.8 247 0 0 0

Total 5969.4 Total 5969.8

Mesotrione Step-I The desired quantities of 1,3-cyclohexadione, EDC, acetone cyanohydrin, Triethyl amine and 2-nitro-4-methylsulfonyl benzoyl chloride under a nitrogen blanket are added in to the reactor. Heated the mass up to desired temperature until reaction is completed.

After the completion of the reaction, cool the reaction mass and water is added. pH is adjusted by sulfuric acid then layers are separated. Organic layer is washed by sodium hydroxide solution and layers are separated. Solvent is recovered from organic layer and recycled. Aqueous layer pH is adjusted by sulfuric acid, Cooled & filtered to get product. Wet cake is then dried as a finished product.

NO2

Cl

O

SO

OCH3

methyl 4-(chlorocarbonyl)-3-nitrobenzenesulfinate

263.65

+O O

cyclohexane-1,3-dione112.12

1,2 Dichloroethane

ET3N. Acetonecynohydrine

NO2 O

SO

OCH3

O

O

methyl 4-[(2,6-dioxocyclohexyl)carbonyl]-3-nitrobenzenesulfinate

339.32

+ ClH36.46




Mass Balance

Sr.no


Input Material Name

Qty (kg)


Product/By-Product

(kg)

Waste

Water

Air Emission (kg)

Recovery (kg)

Solvent Loss (kg)


1 1,3-

cyclohexadione

387 30% HCl 430

2 Ethylene Dichloride 9000 Mesotrion

e 1000

3 Acetone Cyanohydrin 107 EDC

recovered 8940 4 Triethylamine 100 EDC loss 60

5

2-nitro-4-methylsulfonyl

benzoyl chloride

914 Aq. layer

4935

6 Water 3300 Drying loss 182

7 Sulfuric acid sol. 835 Organic

residue 96

8 10% Sodium hudroxide sol. 1000

1430 4935 182 8940 60 96




Penoxsulam Process description

To the mixture of trizolopyrimidine amine, DMSO and pyridine was added substituted benzene sulphonyl chloride and reaction mixture was stirred for 8h. After completion of reaction DMSO is distilled out completely. To the crude mixture water was added, stirred and filtered. Filtrate was dried completely to afford desired product as penoxsulam.

NN

N

N

OCH3

OCH3

NH2

5,8-dimethoxy[1,2,4]triazolo[1,5-c]pyrimidin-2-amine195.18

+

S

OF

F

F

FFO

O

Cl

+N

2-(2,2-difluoroethoxy)-6-(trifluoromethyl)benzenesulfonyl chloride324.65

pyridine70.1

DMSO

NN

N

N

OCH3

OCH3

NH S

O

F

F

FFF

O

O

2-(2,2-difluoroethoxy)-N-(5,8-dimethoxy[1,2,4]triazolo[1,5-c]pyrimidin-2-yl)-6-(trifluoromethyl)benzenesulfonamide

483.37

+N

ClH

pyridine hydrochloride

115.56




Mass Balance

Sr.no


Input Material Name

Qty (kg)


Product/By-Product

(kg) Waste Water

Air Emission

(kg) Recovery

(kg) Solvent

Loss (kg)


1 Trizolopyrimidine amine 404 Penoxsulam 1000

2 Sulphonyl chloride 672 Water to

ETP 1160

3 Pyridine 164 DMSO recovery 1930

4 DMSO 2020 DMSO loss 90 5 Water 1000 Drying loss 80

1000 1160 80 1930 90 0 Total 4260 Total 4260

Pretilachlor Step-I In the first step, 2,6‐Diethylanilie ( DEA ) is taken excess in a reactor and is reacted with

Propoxychloroethane at reflux temperature for 20 hours. After completion of the reaction, the mass is neutralized by caustic and the aqueous is separated. The organic is taken for the recovery of the excess DEA and the product N‐Propoxyethyl‐2,6‐diethylaniline (PEDA) is vacuum distilled.



CH3CH3

NH2

2,6-diethylaniline

149.23

+CH3

OBr

1-(2-bromoethoxy)propane167.04

Na2CO3/water CH3CH3

NH CH3

O

+ BrH

2,6-diethyl-N-(2-propoxyethyl)aniline235.36

80.91

BrH80.91 x 2 = 161.82

+ Na2CO3106

NaBr + CO2 H2O22

102.89 x 2 = 205.78 44+

18.01

Step-II In the second step, the step 1 product PEDA is reacted with chloroacetylchloride in presence of solvent N-hexane at room temperature. After the reaction, the acid HCl is neutralized and the product is washed with water and the solvent is distilled and the product is packed as technical Pretilachlor.

CH3CH3

NH CH3

O

2,6-diethyl-N-(2-propoxyethyl)aniline235.36

+ ClCl

O

chloroacetyl chloride112.94

TolueneCH3CH3

N CH3

OCl

O

+ ClH

2-chloro-N-(2,6-diethylphenyl)-N-(2-propoxyethyl)acetamide

(PRETILACHLOR)311.84

36.45






Mass Balance

Sr.no


Input Material Name

Qty (kg)


Product/By-Product

(kg) Waste Water

Air Emission

(kg) Recovery

(kg) Solvent

Loss (kg)


1 2,6-

diethyl aniline

1699 NaBr 222

2

1-Bromo-2-

Propoxy Ethane

466 CO2

60

3 Sodium carbonate 403 Water

distillate 25

4 Water 5300 2,6-diethyl

aniline recov

1130

5 CAC 387 2,6-diethyl aniline loss 5

6 Triethyl amine 363 Aq. to ETP 5720

7 Toluene 1500 Pretilachlor 1000

Toluene recovery 1425

Toluene loss 75

30% HCl 416

Organic residue 40

1638 5745 60 2555 80 40 Total 10118 Total 10118

Propanil Process description

Propanil tech manufacture is a single step process. It involves reaction of 3, 4‐Dichloroaniline (DCA) with propionic acid at 140‐150°C. Water is formed during the course of reaction.

Excess propionic acid and azeotropic water are removed. The residual mass thus obtained in molten state is Propanil technical. Chemical

NH2

Cl

Cl

3,4-dichloroaniline162

+O

CCH2

CH3OH

propanoic acid74.07

NH

Cl

Cl C

O

CH2 CH3

+ OH2

N-(3,4-dichlorophenyl)propanamide(PROPANIL)

218.07

18.01




Mass Balance

Sr.no


Input Material Name

Qty (kg)


Product (kg)

Waste Water

Air Emission

(kg) Recovery

(kg) Solvent

Loss (kg)


1 3,4‐DCA 747 Propanil 1000

2 Propionic acid 404 Water distillate 80

Process loss 71

1000 80 71 0 0 0


Propaquizafop

Process description Thionyl chloride was added to the stirred solution of (R)-2-(4-((6-chloroquinoxalin-2-yl)oxy) phenoxy)propanoic acid in toluene and stirred for few hours. After completion of reaction toluene was distilled out. Into this DMF and propan-2-one O-(2-hydroxyethyl) oxime was charged, pyridine was added slowly into this reaction and stirred for 6h. After completion of reaction DMF was distilled completely and crude mixture was treated with water. White solid was filtered and dried to get desired product.



N

N O

OCH3

OOH

CH3

344

+

OH

O

CH3

N

CH3

2-[(propan-2-ylideneamino)oxy]ethanol117.14

(R)

N

N

OCH3

OO N

OCH3

Cl

O CH3

(R)+ SO2 + C5H5N.HCl

443

64 115




Mass Balance

Sr.no


Input Material Name

Qty (kg)


Product (kg)

Waste Water

Air Emission

(kg) Recovery

(kg) Solvent

Loss (kg)


1 Carboxylic acid 777 Propaquizafop 1000

2 Alcohol 265 Toluene recovered 2960

3 Thionyl chloride 269 Toluene loss 148

4 Pyridine 178 DMF recovery 3690 5 DMF 3885 DMF loss 195 6 Toluene 3108 Water to ETP 2300 7 Water 2000 Drying loss 189

1000 2300 189 6650 343 0 Total 10482 Total 10482

Sulfentrazone

STEP I: Intermediate – I A mixture of phenyl hydrazine, acetaldehyde, sodium cyanate and acetic acid in solvent methanol was chlorinated using chlorine gas over a period of 6 – 8 hours at 50 – 55 °C. Product of this step (Intermediate I) was filtered after recovery of methanol under reduced pressure.

NH NH2

+ CH3CHO +

phenylhydrazine108.14

NaOCN + CH3COOHMethanol/Cl2

N

NNH

O

CH35-methyl-2-phenyl-2,4-dihydro-3H-1,2,4-triazol-3-one

175.18Intermediate-I

STEP II : Intermediate – II A mixture of intermediate - I in solvent dimethyl formamide and potassium carbonate was heated to 175 – 180°C. Freon 22 gas was purged for 3 – 4 hours. The mass was cooled to 50 – 60°C and the resultant solid was filtered. Chlorine gas was purged to the filtrate over a period of 4 – 5 hours maintaining the temperature of the mass at 65 – 75°C. Solvent dimethyl formamide was distilled off under reduced pressure, residue quenched in water and filtered to give Intermediate – II.



DMF/Cl2N

NNH

O

CH3

5-methyl-2-phenyl-2,4-dihydro-3H-1,2,4-triazol-3-one

175.18Intermediate-I

+ CHF2ClFreon gas

K2CO3+ N

NN

O

CH3

ClCl

CHF2

294.08Intermediate-II

2-(2,4-dichlorophenyl)-4-(difluoromethyl)-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one

STEP III : Intermediate – III Nitric acid was charged to a mixture containing Intermediate – II in solvent dichloroethane and oleum at ambient temperature. The mass was quenched in water & the resultant product (Intermediate – III) was obtained by filtration. Solvent dichloroethane recovered during the process was recycled.

N

NN

O

CH3

ClCl

CHF2

294.08Intermediate-II

+ H2SO4 + HNO3 N

NN

O

CH3

ClCl

O2NCHF2

339.08Intermediate-III

2-(2,4-dichlorophenyl)-4-(difluoromethyl)-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one

2-(2,4-dichloro-5-nitrophenyl)-4-(difluoromethyl)-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one

STEP IV: Intermediate – IV A solution containing intermediate – III in solvent isopropyl alcohol (IPA) and Pd/C catalyst was pressurized using hydrogen at 70 – 80°C for a period of 10 – 11 hours. The mass was cooled to 50 – 60°C & Pd/C Catalyst was filtered off and recycled. Solvent IPA was distilled, residue was quenched in water and the product (Intermediate-IV) was obtained by filtration.

N

NN

O

CH3

ClCl

O2NCHF2

339.08Intermediate-III

5% Pd/CIPA, H2 N

NN

O

CH3

ClCl

NH2 CHF2

309.1Intermediate-IV

2-(2,4-dichloro-5-nitrophenyl)-4-(difluoromethyl)-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one

2-(5-amino-2,4-dichlorophenyl)-4-(difluoromethyl)-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one



STEP V: Sulfentrazone A mixture of Intermediate – IV, toluene and pyridine was charged to the reactor. Mixture was heated to 50 - 60°C and methane sulfonyl chloride was charged. Reaction was subjected to a series of extractions. Pyridine was recovered by extraction with dichloromethane. Toluene was distilled and the residue was quenched in water and filtered to yield Sulfentrazone technical. Recovered toluene was recycled in subsequent batches.

N

NN

O

CH3

ClCl

NH2 CHF2

Intermediate-IV

CH3SO2Cl+Pyridine

Toluene N

NN

O

CH3

ClCl

NH

SO2CH3

CHF2

309.1 SULFENTRAZONE387.19

2-(5-amino-2,4-dichlorophenyl)-4-(difluoromethyl)-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one

N-{2,4-dichloro-5-[4-(difluoromethyl)-3-methyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl]phenyl}methanesulfonamide




Mass Balance

Sr.no


Input Material Name

Qty (kg)


Product/By-

Product (kg)

Waste Water

Air Emission (kg)

Recovery (kg)

Solvent

Loss (kg)


(kg)

1 Phenyl hydrazine 765 Methanol recovered 3788

2 Acetaldehyde 376 Methanol loss 344.5

3 Sodium cyanate 530 Aqueous effluent

38815.2

4 Chlorine 530

Scrubbed NaOH

solution (containing

sodium hypochlorite

)

2472

5 Acetic acid 500 Drying loss 805.3

6 20% NaOH solution 500 DMF recovered 6578.5

7 Methanol 4000 DMF loss 132.5

8 Water 36685 Dichloroeth

ane recovered

4352.85

9 Potassium carbonate 900 Dichloroeth

ane loss 580.7 10 Dimethyl formamide 7550 Spent acid 10291.6

11 Dichlorodifluoromethane 650 IPA

recovered 2566.75 12 Chlorine gas 1778 IPA loss 606.1

13 10% sodium hydroxide 1000 Catalyst Pd

/ C 63.2

14 Oleum 4450 Sulfentrazone 1000

15 Nitric acid 385.5 Toluene recovered 4599.9

16 Dichloroethane 2620 Toluene loss 498.4

17 Isopropyl alcohol 6415 Pyridine recovered 441.5

18 Catalyst Pd / C 63.2 Pyridine loss 49.1

19 Methane sulfonyl chloride 689

20 Pyridine 490.6

21 Toluene 4983.8

22 Dichloromethane 2125

11291.6 41287.2 805.3 22327.5 2211.

3 63.2

Total 77986.1 Total 77986.1

INSECTICIDE Chlorantraniliprole

Process description The desired quantities of 2-amino-5-chloro-N,3-dimethylbenzamide, Toluene, 3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carbonyl chloride and Triethyl amine are charged in to the reactor and stirred at desired temperature until reaction is over.

Once the reaction is completed, water is added in to the reaction mass, Heat the mass up to desired temperature then layers are separated, Organic layer is cooled and the product is isolated by filtration and Solvent is recovered from ML for recycle.

Chemical Reaction



NH2

CH3Cl

ONHCH3

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

198.65

+N

NN

Cl

Br

Cl

O

3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carbonyl chloride

320.95

NH

CH3Cl

ONHCH3

N

NN

Cl

Br

O

3-bromo-N-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamide

483.14

+ ClH

36.46




Mass Balance

S. No.


Input Material Name

Qty (kg)


Product/By-Product

(kg) Waste Water

Air Emission

(kg) Recovery

(kg) Solvent

Loss (kg)


1

2-amino-5-chloro-N,3-

dimethyl benzamide

440 Chlorantraniliprole 1000

2

3-bromo-1-(3-

chloropyridin-2-yl)-1H-

pyrazole-5-carbonyl chloride


3 Triethyl amine 225 Toluene

recovered 2990

4 Toluene 3150 Toluene loss 160

5 Water 2300 30% HCl 270

Drying loss 146

1270 2255 146 2990 160 0


Cyantraniliprole Process description

The desired quantities of Xylene, 2-amino-5-cyano-N,3-dimethylbenzamide, 3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carbonyl chloride and Triethyl amine are charged in to the reactor. The reaction mass is stirred at the desired temperature until reaction is over. Once the reaction is completed, water is added in to the reaction mass and heated up to desired temp., then layers are separated, Organic layer is cooled to isolate the product by filtration and dried the product. solvent is recovered from Organic ML and reused.

Chemical Reaction

CH3

ONHCH3

NH2

N

+N

NN

Cl

Br

Cl

O

3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carbonyl chloride

320.95

+ ClH

36.46

2-amino-5-cyano-N,3-dimethylbenzamide

189.21

CH3

ONHCH3

NH

N

N

NN

Cl

Br

O

3-bromo-1-(3-chloropyridin-2-yl)-N-[4-cyano-2-methyl-6-(methylcarbamoyl)phenyl]-1H-pyrazole-5-carboxamide

473.71




Mass Balance

Sr.no


Input Material Name

Qty (kg)


Product/By-Product

(kg) Waste Water

Air Emission

(kg) Recovery

(kg) Solvent

Loss (kg)


1

2-amino-5-cyano-N, 3-

dimethyl benzamide

430 Cyantraniliprole 1000

2

3-bromo-1-(3-

chloropyridin-2-yl)-1H-

pyrazole-5-carbonyl chloride


3 Triethyl amine 230 Xylene

recovered 3150

4 Xylene 3320 Toluene loss 170

5 Water 2500 30% HCl 275

Drying loss 155

1275 2455 155 3150 170 0


Flubendiamide

Step-1: Preparation of N-(1, 1-Dimethyl-3-Methylthioethyl)-3-Iodo-Phthalamic Acid

It is prepare from 3- Iodophthalic Anhydride and 1, 1-Dimethyl-2-Methylthioethylamine using Dimethylacetamide (DMA) as solvent in presence of Triethylamine. The reaction mixture is stir for 1.0 hr at room temperature. After completion of reaction, the solvent is remove under reduced pressure.



Step-2: Preparation of 3-(1, 1-Dimethyl-2-Methylthioethylimino)-4-Iodo-3H-Isobenzofuran-1-one It is prepare from N-(1, 1-Dimethyl-3-Methylthioethyl)-3-Iodo-Phthalamic Acid and Trifluoroacetic Anhydride using Toluene as solvent. The reaction mixture is stir for 30 min at room temperature. The solvent is remove under reduced pressure to obtain the product.

Step-3: Preparation of N2-[1, 1-Dimethyl-2-(Methylthio) ethyl]-3-Iodo-N1-[2- Methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl) ethyl] Phenyl]-1,2-Benzenedicarboxamide It is prepare by reacting of 3-(1, 1-Dimethyl-2-Methylthioethylimino)-4-Iodo-3H-Isobenzofuran- 1-one and 4- Heptafluoroisopropyl-2-Methylaniline using Acetonitrile as solvent in presence of Trifluoroacetic Acid as a catalyst. The reaction mixture is stir for 3.0 hrs. The precipitate is collect by filtration and dry the product.

OR

O

O

O

I

H2NS

OR

Et3N

I

NH S

O

COOH

OR

Mol. Wt.: 393.24

+

Mol. Wt.: 274.01

4-Iodo-2-Benzofuran-1,3-Dione 3-Iodo-2-{[2-Methyl-1-(Methylsulfanyl)Propan-2-yl]Carbamoyl}Benzoic Acid

Mol. Wt.: 119.23

2-Methyl-1-(Methylsulfanyl)Propan-2-Amine

1,1-Dimethyl-2-Methylthioethylamine3-Iodopthalic Anhydride N-(1,1-Dimethyl-3-Methylthiomethyl)-3-Iodo-pthalamic Acid

I

NH S

O

COOH

(CF3CO)2O

Mol. Wt.: 393.24

OR OR

Mol. Wt.: 375.23

O

N

O

I

S2CF3COOH

3-Iodo-2-{[2-Methyl-1-(Methylsulfanyl)Propan-2-yl]Carbamoyl}Benzoic Acid

+

(3Z)-4-Iodo-3-{[2-Methyl-1-(Methylsulfanyl)Propan-2-yl]Imino}-2-Benzofuran-1(3H)-One

Mol. Wt.: 210.03

Trifluoroacetic Anhydride

N-(1,1-Dimethyl-3-Methylthiomethyl)-3-Iodo-pthalamic Acid

3-(1,1-DImethyl-2-Methylthioethylamino-4-Iodo-3H-Isobenzofuran-1-One

+

Mol. Wt.: 228.04

Trifluoroacetic Acid



Step-4: Preparation of N2-[1, 1-Dimethyl-2-(methylsulfonyl) ethyl]-3-iodo-N1-[2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl) ethyl]phenyl]-1,2-benzenedicarboxamide (Flubendiamide) It is prepared by oxidation of N2-[1, 1-Dimethyl-2-(Methylthio) ethyl]-3-Iodo-N1-[2- Methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl) ethyl] Phenyl]-1,2-Benzenedicarboxamide with M-Chloroperbenzoic Acid (MCPBA) using Dichloromethane (DCM) as solvent. The reaction mixture is then stir for 3.0 hrs at room temperature. The solvent is remove under reduced pressure.

O

N

O

IS H3C

H2N

CF3

CF3

FCF3COOH

OR

Mol. Wt.: 375.23

OR

I

S

CF3

F3CF

HN

NH

O

O

Mol. Wt.: 650.39

CF3COOH

N2-[1,1-Dimethyl-2-(Methylthio)Ethyl]-3-Iodo-N1-[2-Methyl-4-[1,2,2,2-Tetrafluoro-1-(Trifluoromethyl)Ethyl]Phenyl]-1,2-Benzenedicarboxamide

(3Z)-4-Iodo-3-{[2-Methyl-1-(Methylsulfanyl)Propan-2-yl]Imino}-2-Benzofuran-1(3H)-One

4-[1,1,1,2,3,3,3-Heptafluoropropane-2-yl]-2-Methylaniline

Mol. Wt.: 275.17 Mol. Wt.: 114.02

+ +

(Catalyst)

4-Heptafluoropropyl]-2-Methylaniline3-(1,1-DImethyl-2-Methylthioethylamino-4-Iodo-3H-Isobenzofuran-1-One


Mol. Wt.: 114.02

+


I

S

CF3

F3CF

HN

NH

O

O

COOOH

Cl

Mol. Wt.: 650.39 Mol. Wt.: 345.14 Mol. Wt.: 682.39

O

O

CF3

OI

HN

NH

S

F3CF

O COOH

Cl

Mol. Wt.: 313.14

+

N2-[1,1-Dimethyl-2-(Methylthio)Ethyl]-3-Iodo-N1-[2-Methyl-4-[1,2,2,2-Tetrafluoro-1-(Trifluoromethyl)Ethyl]Phenyl]-1,2-Benzenedicarboxamide

N2-[1,1-Dimethyl-2-(Methylsulfonyl)Ethyl]-3-Iodo-N1-[2-Methyl-4-[1,2,2,2-Tetrafluoro-1-(Trifluoromethyl)Ethyl]Phenyl]-1,2-Benzenedicarboxamide

Flubendiamide

2.

M-Chloroperbenzoic Acid

2.

M-Chlorobenzoic Acid

+






Mass Balance

Sr.no


Input Material Name Qty (kg)


Product (kg)

Waste

Water

Air Emissio

n (kg) Recover

y (kg) Solvent Loss

(kg)

Solid/Hazardous

Waste (kg)

1

N2-[1, 1-Dimethyl-2-(Methylthio) ethyl]-3-Iodo-N1-[2- Methyl-4-[1,2,2,2- tetrafluoro-1-(trifluoromethyl) ethyl]

Phenyl]-1,2-Benzenedicarboxamid

e

1415

3-(1, 1-Dimethyl-2-Methylthioethylimino)-

4-Iodo-3H-Isobenzofuran-1-one

1357

2 1,1-Dimethyl-2-Methylthioethylamine 768 Flubendiamide 1000

3 3- Iodophthalic Anhydride 1768 M-Chlorobenzoic Acid

(MCBA) 510

4

3-(1, 1-Dimethyl-2-Methylthioethylimino)-

4-Iodo-3H-Isobenzofuran-1-one

1357 N-(1, 1-Dimethyl-3-Methylthioethyl)-3-

Iodo-Phthalamic Acid 2032

5 4-

Heptafluoroisopropyl-2-Methylaniline

503

N2-[1, 1-Dimethyl-2-(Methylthio) ethyl]-3-Iodo-N1-[2- Methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl) ethyl]

Phenyl]-1,2-Benzenedicarboxamid

e

1415

6 Acetonitrile 4605 Process Losses 2687 7 Dichloromethane

(DCM) 8581 Recovered Acetonitrile 4500

8 Dimethylacetamide (DMA) 6647 Recovered DCM

(Dichloromethane) 8405

9 M-Chloroperbenzoic Acid (MCPBA) 548 Recovered DMA

(Dimethylacetamide) 6315

10 N-(1, 1-Dimethyl-3-Methylthioethyl)-3-

Iodo-Phthalamic Acid 2032 Recovered

Triethylamine 123

11 Toluene 5587 Removed Toluene 5510 12 Triethylamine 129 Trifluoroacetic Acid 1178 13 Trifluoroacetic Acid 7 14 Trifluoroacetic

Anhydride 1085 15 13002 0 0 19343 2687 0

Total 35032 35032



Nitenpyram Step-I Synthesis of Vinylidene Chloride

Elimination reaction to 1,1,2-trichloroethane as a starting material, hydrogen sodium hydroxide solution the reaction was carried out at -15 ° C~100 ° C elimination reaction, to give vinylidene chloride, the reaction equation:

CH CH2 ClCl

ClNaOH

1,1,2-trichloroethane133.4

C CH2Cl

Cl

1,1-dichloroethene96.94

+ OH2 Na Cl+58.4418.01

Step-2 Synthesis of 1,1,1- trichloro-2-nitroethane the nitration reaction, the vinylidene chloride in the presence of a catalyst Al, nitrification reaction with nitric acid and hydrochloric acid, to give 1,1,1- trichloro-2-nitroethane was isolated and purified after the reaction, reaction equation:

C CH2Cl

Cl

1,1-dichloroethene96.94

HNO3

C CH2Cl

Cl

Cl

NO2

1,1,1-trichloro-2-nitroethane178.4

+ OH2

18.01HCl

63.01

36.46

Step-3 Synthesis of Intermediate N-ethyl-2-chloro-5-pyridyl methyl amine N- alkylation reaction with 2-chloro-5-chloromethyl pyridine starting materials, water as solvent, at -10~50 ° C, and triethylamine phase transfer catalyst under reaction A2, the reaction product was desolventized, alkali washing, distillation of the intermediate N - ethyl-2-chloro-5-pyridyl methyl amine, reaction equation:

NCl

CH2Cl

2-chloro-5-(chloromethyl)pyridine162.01

+ CH3 CH2 NH2

ethanamine45.08

NCl

CH2 NH CH3CH2

N-[(6-chloropyridin-3-yl)methyl]ethanamine

170.64

+ ClH36.46

Step-4 Synthesis of Intermediate I- chloro -N- {(6 - pyridin-3-chloro) methyl} -N- ethyl-2-nitroethylene-amine condensation reaction of the ethyl-2-chloro-5-pyridin-N- methylamine with said I, I, I- trichloro-2-nitroethane in a methylene chloride solvent, acid binding agent is added, in the A3 phase transfer catalyst, at -10~50 ° C, the reaction to give a condensate I- chloro -N- {(6 - pyridin-3-chloro) methyl} -N- ethyl-2-nitroethylene-amine, reaction equation:



NCl

CH2 NH CH3CH2

N-[(6-chloropyridin-3-yl)methyl]ethanamine

170.64

+ C CH2Cl NO2

Cl

Cl

1,1,1-trichloro-2-nitroethane

178.4

NCl

CH2 N CHC

C2H5

Cl

NO2

1-chloro-N-[(6-chloropyridin-3-yl)methyl]-N-ethyl-2-nitroethenamine

276.11

+ 2 HCl72.92

Step-5 Synthesis of Nitenpyram

methylamino reaction, the a group of reaction with said condensation reaction is carried out in the same reaction pot, after completion of the condensation reaction to give a condensate I- chloro -N - {(6- chloro-Jie ratio given -3- Jie) methyl } -N_ ethyl-2-nitro-vinylamine, then at -10~50 ° C, aqueous methylamine was added dropwise, the reaction product was extracted, desolventized, recrystallized nitenpyram, reaction equation :

NCl

CH2 N CHC

C2H5

Cl

NO2

1-chloro-N-[(6-chloropyridin-3-yl)methyl]-N-ethyl-2-nitroethenamine

276.11

NCl

CH2 N CHC

C2H5

NH

NO2

CH3CH3 NH2+methanamine

31.05

+ ClH36.46

N-[(6-chloropyridin-3-yl)methyl]-N-ethyl-N'-methyl-2-nitroethene-1,1-diamine

270.7






Mass Balance

Sr.No


Input Material Name Qty(kg)


Product/By-Product

(kg) Waste Water

Air Emission

(kg) Recovery

(kg) Solvent

Loss (kg)


1 1,1,2- trichloroethane 940 NaCl

recovered 421

2 NaOH 282 Water to ETP 5532

3 water 5340 30% HCl 2879

4 HCl 30% 764 Methylene chloride

recovered 1160

5 HNO3 396 Methylene chloride

loss 40

6 2-chloro-5-

chloromethyl pyridine

950 nitenpyram 1000

7 Ethyl amine 265 Process loss 63

8 20% NaOH 800

9 Methylene chloride 1200

10 methane amine 158 3879 5532 63 1581 40 0


Pymetrozine Process description

Charge 3-Pyridine carboxaldehyde, 1,2,4-Triazine-3(4H)-1,4-Amino-5,6-dihydro-6-methyl

and toluene in a reactor under stirring. Raise the temperature to 65°C and maintain for 6 hrs.

Once the reaction completes, distil half of the toluene and cool to crystallize the mass.

Centrifuge and dry the crude mass to get technical grade Pymetrozine. Recover the toluene

from the ML by distillation.

N

H

O

pyridine-3-carbaldehyde107.11

+N

NH

N

NH2

O

CH3

4-amino-6-methyl-4,5-dihydro-1,2,4-triazin-3(2H)-one

128.13

Toluene N

NH

N

N

O

CH3N

H

+ OH2

6-methyl-4-[(pyridin-3-ylmethylidene)amino]-4,5-dihydro-1,2,4-triazin-3(2H)-one

217.22

18.01




Mass Balance

Sr.no


Input Material Name

Qty (kg)


Product (kg)

Waste

Water

Air Emissio

n (kg) Recover

y (kg) Solvent Loss (kg)


1 3 Pyridine

Carboxaldehyde

519 Pymetrozone 519

2

1,2,4 Triazine-3 (4H) 1,4 -

Aamino-5,6 -(Dihydro-6-

Methyl)

639 Water recovered 639

3 Toluene 2000

Toluene recovered 2000

4 Water for washing

1500 Toluene loss 1500

519 0 0 2639 1500 0


Spirodiclofen

Step I: 1-cyano-cyclohexanol

Preparation of 1-cyano-cyclohexanol Under mechanical stirring, was added 748 kg of cyclohexanone in 500ml three-necked flask, 296 holding temperature of sodium cyanide, in 1000 lit of water, ice bath at 5-10 ° C, was slowly added dropwise 40% sulfuric acid solution, addition time holding tank, after the completion of the dropwise addition stirring was continued for 30min, the product was extracted with ethyl acetate, the combined ethyl acetate layer was washed with water, dried over anhydrous over sodium sulfate, and concentrated to give 820 kg of liquid product, 86.0% yield, was used without purification in the next reaction.



O

98.14

NaCNOH CN

125.16cyclohexanone 1-hydroxycyclohexanecarbonitrile

Step II: Intermediate – II ( 2,4- dichloro phenylacetyl chloride) added to the reaction flask 1926 kg 2,4- dichloro-phenylacetic acid and thionyl chloride 2300 kg heated 75-100 C The reaction was stirred at reflux for 4h, thionyl chloride was distilled off under reduced pressure to give a yellow liquid 2074 kg, 98. 8% yield.

Cl

Cl

COOH

(2,4-dichlorophenyl)acetic acid205.03

S

O

ClCl

thionyl dichloride

118.97

Cl

Cl

O

Cl

(2,4-dichlorophenyl)acetyl chloride223.48

+ ClH + SO2

36.46 64.06

Step III: Intermediate – III (2,4-dichloro-1-cyano-acid cyclohexyl ester) A reaction flask was added dropwise 2074 kg 2,4 dichlorophenylacetyl chloride (Intermediate-II) and 4148 kg dichloromethane under 820 kg crude cyclohexanol cyano (Intermediate-I), pyridin-1442 kg of, 6222 kg dichloromethane, ambient conditions mixture was left Ih addition was complete, the reaction and stirring was continued for 12h, 10370 3% hydrochloric acid solution was added and extracted 3 times with ethyl acetate, the ethyl acetate layer was washed with 5% sodium carbonate solution twice, and finally washed with water, then dried over anhydrous sodium sulfate, and concentrated to give a brown paste 2406 kg, it was used directly without purification in the next step.

OH CN

1-hydroxycyclohexanecarbonitrile

125.16

+O

Cl

Cl

Cl

(2,4-dichlorophenyl)acetyl chloride223.48

O

O

Cl

Cl CN

1-cyanocyclohexyl (2,4-dichlorophenyl)acetate

312.19

+ ClH

36.46

Step IV: Intermediate – IV

Add 2,4-dichloro acid 1-cyano-cyclohexyl ester 2406 reaction flask crude sulfuric acid and methanol 16043 kg (1003 kg sulfuric acid, methanol 15040 kg ), was heated to reflux and stirred for 60-80 ° C, the reaction 2¾ so, after most of the methanol was distilled off, wait a cooled 40 ° C was added 50ml of water, the product was extracted three times with ethyl acetate, ethyl acetate layers were combined, washed with 5% sodium bicarbonate solution



three times and then washed with water, dried over anhydrous sodium sulfate, and concentrated to give crude product 1772 kg, it can be used in the next reaction without purification.

O

O

Cl

Cl CN

1-cyanocyclohexyl (2,4-dichlorophenyl)acetate

312.19

+ CH3 OH

methanol32.04

O

O

Cl

Cl CH3COOH

INTERMEDIATE-IV

346.52

1-[2 [(2,4-dichloro-phenyl)-2-acetoxy]-1-cyclohexane carboxylic acid methyl ester

Step V: Intermediate – V 3- (2,4-dichlorophenyl) -2-oxo-1-oxa-spiro W. 5] - Preparation of decyl alcohol _3_ alkenyl _4_ ， [0019] 1772 kg- reaction flask was added [2_ (2,4-dichloro - phenyl) - acetoxy] - cyclohexanecarboxylic acid methyl ester group and 399 kg of magnesium ethoxide in 4000 kg ethanol, -5 to 10 ° C reaction 14h. 45. 3%。 After most of the solvent was distilled off, 11075 kg of 5% hydrochloric acid was added, extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and concentrated to give solid crude product 1220 kg, 95% after recrystallization from ethanol to give product 1174 The above 3 steps 45.3% overall yield.

O

O

Cl

Cl CH3COOH

INTERMEDIATE-IV

346.52

1-[2 [(2,4-dichloro-phenyl)-2-acetoxy]-1-cyclohexane carboxylic acid methyl ester

O

OHCl

ClO

3-(2,4-dichlorophenyl)-4-hydroxy-1-oxaspiro[4.5]dec-3-en-2-one

313.17

base

Step VI: Spirodiclofen A reaction flask at room temperature was added 927 kg 3- (2,4_ dichlorophenyl) _2_ oxo-oxa-spiro [4.5] - dec-3-ene-4- ol), 1000 kg triethylamine, 2000 kg dichloromethane, 663 kg 2,2- dimethylbutyryl chloride was added dropwise, with stirring at room temperature the reaction cell. The reaction solution was washed 3 times with hydrochloric acid, then twice with saturated sodium bicarbonate solution, and finally washed twice with water, dried over anhydrous sodium sulfate, and concentrated to give a solid product 5. Sg, after recrystallization from 95% ethanol to give 1000 kg product, yield 94.0%, content of 98. 4%

O

OHCl

ClO

3-(2,4-dichlorophenyl)-4-hydroxy-1-oxaspiro[4.5]dec-3-en-2-one

313.17

+ CH3

Cl

O

2,2-dimethylbutanoyl chloride134.6

O

OCl

ClO

411.36

Spirodiclofen

+ ClH

36.46










Mass Balance

Sr.no


Input Material Name

Qty (kg)


Product/By-Product

(kg)

Waste

Water

Air Emissio

n (kg) Recover

y (kg)

Solvent

Loss (kg)


1 2,2-

dimethylbutyryl chloride

400 Aq to ETP

15052

2 2,4- dichloro-phenylacetic

acid 565 Dichloroethane

loss 60

3 3%

hydrochloric acid solution

1500 Dichloroethane recovered

3020

4 5%

hydrochloric acid

1000 dichloromethane loss

50

5 5% sodium bicarbonate 1000 Dichlorometha

ne recovered 1950

6 5% sodium carbonate solution

1800 Ethanol loss

150

7 Cyclohexanone 340 ethanol

recovered 3350

8 Dichloromethane 5080 Ethyl acetate 1440

9 Ethanol 3500 Ethyl acetate loss 150

10 Ethyl acetate 5240 Ethyl acetate recovered 2910

11 hydrochloric acid 1000 HCl gas 308

12 magnesium ethoxide 232 Methanol

recovered 2400 13 Methanol 2500 Process loss 9 14 Pyridine 762 SO2 176

15 sodium

bicarbonate solution

2000 Spirodiclofen 1000

16 sodium cyanide 170

Thionyl chloride recovery

340

17 Sulphuric acid 450

18 Thionyl chloride 676

19 Triethylamine 1000 20 Water 3150

2440 1505

2 484 13970 419 0




Spirotetramet

Step I: 1-Intermediate-I

1,4-dioxaspiro[4,5]decan-8-one reacts with Potassium cyanide and ammonium carbonate in presence of Methanol and water at 60 C and then neutralize with HCl at 0 C to get Intermediate-I

O O

O1,4-dioxaspiro[4.5]decan-8-one

156.18

+ Na C NSodium cyanide

49

+ (NH4)2CO3

Ammonium carbonate96

MeOH/water

HCl

O O

NHO

NH O

9,12-dioxa-1,3-diazadispiro[4.2.4.2]tetradecane-2,4-dione226.23

+ NaCl + NH4Cl58.44 53.49

Step II: Intermediate – II Intermediate-I under hydrolysis with 3N NaOH gives Intermediate-II

3 N NaOH to pH 6

O O

NHO

NH O

9,12-dioxa-1,3-diazadispiro[4.2.4.2]tetradecane-2,4-dione

226.23

reflux

O O

NH2

O

OH

8-amino-1,4-dioxaspiro[4.5]decane-8-carboxylic acid201.2

Step III: Intermediate – III Intermediate-II react with methanol in acidic condition to geies Intermediate-III

Dry HCl

reflux

O O

NH2

O

OH

8-amino-1,4-dioxaspiro[4.5]decane-8-carboxylic acid

201.2

O O

NH2

O

OCH3

+ CH3 OH

methanol32.04

methyl 8-amino-1,4-dioxaspiro[4.5]decane-8-carboxylate215.24

+ OH2

18

Step IV: Intermediate – IV



Intermediate-III react with (2,5-dimehtlphenyl)acetyl chloride using solvent Acetonitrile to give Intermediate-IV

Acetonitrile

K2CO3

O O

NH2

O

OCH3

methyl 8-amino-1,4-dioxaspiro[4.5]decane-8-carboxylate

215.24

+ CH3 CH3

O

Cl

(2,5-dimethylphenyl)acetyl chloride182.64

CH3

CH3

NHO

O

O OCH3O

Intermediate IV361.43

138.2

+ ClH36.46

k2CO3 + 2 HCl 2 KCl + CO2 + OH2

138.2 72.92 149.1 44 18.01

Step V: Intermediate – V Intermediate-IV undergo rearrangement in the presence of DMF and Potassium t-Butoxide to produce Intermediate-V

DMF

CH3

CH3

NHO

O

O OCH3O

Intermediate IV361.43

CH3

CH3

NH

O

O

O

OH

329.39

CH3 OH

32.04

t-BuOK+

11-(2,5-dimethylphenyl)-12-hydroxy-1,4-dioxa-9-azadispiro[4.2.4.2]tetradec-11-en-10-one

methanol

Step VI: Intermediate-VI Intermediate-V under go refulux in presence of 4N HCl, to produce Intermediate-VI

Reflux

CH3

CH3

NH

O

O

O

OH

329.39

4N HCl

11-(2,5-dimethylphenyl)-12-hydroxy-1,4-dioxa-9-azadispiro[4.2.4.2]tetradec-11-en-10-one

CH3

CH3

NH

O

O

OH +

O

oxirane

44.05

3-(2,5-dimethylphenyl)-4-hydroxy-1-azaspiro[4.5]dec-3-ene-2,8-dione

285.33Step VII: Spirotetramet



Intermediate-V under go refulux in presence of 4N HCl, to produce Intermediate-VI

CH3

CH3

NH

O

O

OH

285.33

CH3

O

Cl

78.5

CH3

CH3

NH

O

O

O

OCH3

ClH

327.37

(SPIROTETRAMET)

36.46

HCl NaOH NaCl OH2

36.46 40 58.44 18.01

3-(2,5-dimethylphenyl)-4-hydroxy-1-azaspiro[4.5]dec-3-ene-2,8-dione

+

acetyl chloride

+

3-(2,5-dimethylphenyl)-2,8-dioxo-1-azaspiro[4.5]dec-3-en-4-yl acetate

DCM, TEA

4-DMAP

+ +




Mass Balance

Sr.no




Product (kg)

Waste Water

Air Emission

(kg) Recover

y (kg)

Solvent

Loss (kg)


1 (2,5-

dimehtlphenyl)acetyl chloride

676 Acetonitrile recovered

2200

2 1,4-

dioxaspiro[4,5]decan-8-one

628 Ammonium chloride 204

3 20% NaOH in scrubber 680 Aq to ETP 2415

4 3N NaOH 1500 CO2 128

5 4-dimethylaminopyridine 20 DCM

recovered 3000 6 4N HCl 1500 DMF loss 50

7 Acetonitrile 2200 DMF recovered 2450

8 Acetyl chloride 272 Filtrate to ETP 3432

9 Ammonium carbonate 284 KCl 524

10 Dichloromethane 3000 Methanol loss 110

11 DMF 2500 Methanol recovered 3910

12 Dry HCl 140 ML to ETP 664 13 HCl gas 488 NaCl 664

14 K2CO3 510 Oxirane recovered 140



Sr.no




Product (kg)

Waste Water

Air Emission

(kg) Recover

y (kg)

Solvent

Loss (kg)


15 Methanol 3900 Process loss 137

16 NaOH solution in scrubber 160 Spirotetramet 1000

17 Potassium t-Butoxide 100 Water recovered 66

18 Sodium Cyanide 196 19 TEA 200 20 Water 2140 2392 6511 128 11766 297 0


Thiamethoxam The desired quantities of DMC (solvent), 2-chloro-5-chloromethyltriazole, 3-Methyl 1-1-Nitroimino-perahydrooxadiazine and Catalyst are charged along with K2CO3 into the reactor. The stirred mixture is heated to reaction temp till the whole reactants reached to desired level.

Once the reaction is over, the reaction mass pH is adjusted with HCl & Water. The excess solvent from organic layer is recovered for re-cycling & the product is cooled, filtered & dried.

Chemical reaction

S

NCl

Cl

2-chloro-5-(chloromethyl)-1,3-thiazole

168.04

+N

O

NHCH3

NNO2

(4Z)-3-methyl-N-nitro-1,3,5-oxadiazinan-4-imine160.13

S

NCl

N N

O

CH3

NNO2

(4E)-3-[(2-chloro-1,3-thiazol-5-yl)methyl]-5-methyl-N-nitro-1,3,5-oxadiazinan-4-imine

291.71

+ ClH36.46




Mass Balance

Sr.no




Product (kg)

Waste

Water

Air Emission (kg)

Recovery (kg)

Solvent

Loss (kg)


(kg)

1 N,N Dimethyl Carbonate 4774

Thiamethoxam 1000

2 2-chloro-5- chloromethyltriazole 764 Aq. layer 5297

3 3-Methyl 1-1-

Nitroiminoperahydrooxadiazine

836 DMC recovered 4536

4 Methyl ammonium hydroxide penta hydrate 18 Residue 135

5 K2CO3 1100 Drying loss 431

6 Water 2725

7 HCl 1182

1000 5297 431 4536 0 135




INTERMEDIATE 1,2,4 – Triazole:

Step -I: Formic Acid is reacted with dry Ammonia to form Formamide which on reaction with Hydrazine hydrate gives the final Product 1,2,4 Triazole. During the reaction ammonia & water molecules are formed in stichiometric quantities.

Chemical Reaction:

CHO

OHformic acid

46.02

+ NH3

17.03

CHO

NH2

+ OH2

formamide45.04

18.01

CHO

NH2

formamide45.04 x 2 = 90.08

+ NH2 NH2 OH2

hydrazine hydrate50.06

NH

N

N


+ OH2 + NH3

18.01 x 3 = 54.03 17.032 3




Mass Balance

Sr.no


Input Material Name

Qty (kg)


Product (kg)

Waste Water

Air Emission

(kg) Recovery

(kg) Solvent

Loss (kg)


1 Formic Acid 85% 2000 1,2,4

Triazole 1032

2 Ammonia Gas 900 Distilled

water 983

3 Hydrazine Hydrate

80% 1000

Recovered Formic Acid

366

4 water 2315 Recovered Hydrazine Hydrate

75

Recovered Liquid

Ammonia 3759

1032 983 0 4200 0 0


2-Chloro-5-Chloromethylthiazole

Step-1: Preparation of 1, 2, 3-Trichloroprapane

It is prepare by Chlorine gas bubbled continuously into Allyl Chloride at a rate of about 5-

10 gm/hrs. under constant stir at 450C – 500C for 3-4 hrs.

Chemical Reaction:

ClCl2

Cl

Cl

Cl

Allyl Chloride 1,2,3-trichloropropane

Mol. Wt.: 76.52 Mol. Wt.: 147.43

+

Chlorine

Mol. Wt.: 2 x 35.5

45-50 0C

3-4 hrs

Step-2: Preparation of 2, 3-Dichloroprop-1-ene

2, 3-Dichloroprop-1-ene is prepared from 1, 2, 3-trichloropropane by adding slowly 25%

aqueous NaOH solution at room temperature in presence of phase transfer catalyst. The

pH is kept at about 14 and stirring is continue to overnight. The reaction progress is

monitored by GC. After completion of reaction, adding water to separate the layer and

the organic layer as well as crude is distilled the product at 69-72°C under 30 mmHg

vacuum.

Chemical reaction:



Cl

Cl

Cl

NaOH

H2O

TEBA

Cl

Cl

NaCl H2O

2,3-dichloroprop-1-ene

Mol. Wt.: 110.97

+

1,2,3-trichloropropane

Mol. Wt.: 147.43

+

Mol. Wt.: 40

Sodium Hydroxide

+

Mol. Wt.: 58.44

Sodium Chloride

Step-3: Preparation of 2-Dichloro-3-Isothiocyanato prop-1-ene

It is prepare by reacting of 2, 3-dichloropropene with sodium thiocyanate in presence of

TEBA (Triethyl benzyl ammonium chloride as phase transfer catalyst using toluene as

solvent. The mixture is heat under reflux (about 100 ℃ to 105 ℃) for 1.5 to 2.0 hours

and then cooled to room temperature. Add water under stirring and stir for 15 min. The

reaction mixture is allow to stand for layer separation. Toluene from the organic layer is

distil under vacuum and also the residue was distilled under high vacuum. The distillate

of 2-Dichloro-3-Isothiocyanato prop-1-ene (Product) is recover as a yellow oil liquid.

Chemical reaction:

Cl

Cl

NaSCN

H2O

N C SCl

NaCl

2-chloro-3-isothiocyanato prop-1-ene

Mol. Wt.: 133.60

2,3-dichloroprop-1-ene

Mol. Wt.: 110.97

+ +

Mol. Wt.: 81.07

TEBA

100-105 0C & 1.5 to 2 hrs

[58.44]

Step-4: Preparation of 2-Chloro-5-Chloromethylthiazole (CCMT)

It is prepared by reacting of 2-Dichloro-3-Isothiocyanato prop-1-ene with Sulfuryl Chloride and toluene. The reaction mixture is warm to 45 °C and add dropwise sulfuryl chloride in 2.0 hrs at 45 ° C. and thereafter 1.0 hr the mixture was further stir at 80 °C. The toluene is distil under reduced pressure and finally product is also distil under high vacuum.

N C SCl

SO2Cl2

S

N

Cl

Cl SO2 HCl

2-chloro-5-chloromethylthiazole

Mol. Wt.: 168.04

2-chloro-3-isothiocyanato prop-1-ene

Mol. Wt.: 133.60

+

Sulfuryl Chloride

Mol. Wt.: 134.97

+ +Toluene

[64.06] [36.46]






Mass Balance

Sr.no


Input Material Name

Qty (kg)


Product/By-Product

(kg) Waste Water

Air Emissio

n (kg) Recover

y (kg) Solvent Loss

(kg)

Solid/ Hazardous Waste (kg)

1 Allyl Chloride 760.78 Process Loss 871.1

2 Chlorine gas 684.69 Sodium

Chloride 1018.98

3 Sodium

Hydroxide, (Flakes)

358.13 Water 2037.6

1

4 TEBA (Catalyst) 20.33 Recovered

Toluene 2034.02

5 Total Water

2126.87 Toluene Loss 239.1

6 Sodium

Thiocyanate

700.39 2-Chloro-5-

Chloromethylthiazole

1000

7 Toluene 3478.27

Sulphur Dioxide 493.86

8 Sulfuryl Chloride

1052.01

Hydrochloric Acid 281.65

Recovered

Toluene 1205.15

Total 2018.98 2319.26 1364.96 3239.17 239.1 0

Total 9181.47 Total 9181.47

3-Methyl-N-Nitroimino-Perhydro-l, 3, 5-Oxadiazine

Step-1: Preparation of N-Methyl-N’-Nitroguanidine

It is prepare by reacting of N-Nitroguanidine with aqueous Methyl Amine in aqueous

medium at 60 0C and evolved of Ammonia gas during the reaction.

NHNH2

NH

N+

O

O-

CH3NH2

Mol. Wt.: 104.07

NH NH

NH

N+

O

O-

N-Nitroguanidine

+

Methyl Amine

Mol. Wt.: 31.06

N-Methyl-N'-Nitroguanidine

Mol. Wt.: 118.09

+ NH3

Ammonia Gas

Mol. Wt.: 17

Step-2: Preparation of 3-Methyl-N-Nitroimino-Perhydro-l, 3, 5-Oxadiazine (MNIO)

3-Methyl-N-Nitroimino-Perhydro-l, 3, 5-Oxadiazine (MNIO) from N-Methyl-N’-

Nitroguanidine and Paraformaldehyde at room temperature using Formic acid (98-100%)

The reaction is carried out by refluxing the reaction mixture at 105°C -107°C for 5-6 hrs

and separate out Water with Formic acid azeotropically. Distilled out formic acid under

vacuum, add DM water and agitate for 15.0 minute at room temperature. Filter and dry

the cake at 80-90°C. Formic acid can be recycled.

Chemical reaction:



HCHO

O N

NH

NN+

O

O-

Mol. Wt.: 160.13

OOH

N-Methyl-N'-Nitroguanidine

Mol. Wt.: 118.09

+ +

Mol. Wt.: 30.03

Formaldehyde Formic Acid

Mol. Wt.: 46.03

3-Methyl-4-Nitroimino-Perhydro 1, 3, 5-Oxadiazine

HCHO+

Mol. Wt.: 30.03

Formaldehyde

+ H2O

Mol. Wt.: 18

Water

NH NH

NH

N+

O

O-




Mass Balance

Sr.no


Input Material Name

Qty (kg)


Product/By-Product

(kg) Waste Water

Air Emission (kg)

Recovery (kg)

Solvent

Loss (kg)


1 N-Nitroguanidine 939.65 Water

2740.45

2 25% Aq .Methyl Amine

1358.05

Ammonia Gas 153.5

3 Water 1634.97

Process Loss 507.02

4 Paraformaldehyde 468.2

3-Methyl-N-

Nitroimino-

Perhydro-l, 3, 5-

Oxadiazine

1000

5 Formic Acid 4680.1 Recovered Formic

Acid 4586.5

Formic Acid Loss 93.5

1000 2740.45 660.52 4586.5 93.5 0

Total 9080.97 Total 9080.97



(vi) Raw Materials & Final Products

Proposed productwise raw material details are provided in Table 3-3.

Table 3-3: Raw Material details

S.No. Product Raw Materials Consumption for (Per MT) Indigenous/Imported Transportation

Fungicide

1 Azoxystrobin

Phthalide 320 Indigenous/Imported Road/Sea Methyl Formate 142 Indigenous/Imported Road/Sea

Di Methyl Carbonate 216 Indigenous/Imported Road/Sea Sodium Hydride 58 Indigenous Road

Toluene 1400 Indigenous Road Sodium Methoxide 128 Indigenous/Imported Road/Sea

EDC 1200 Indigenous Road 4,6 – Di Chloro

Pyrimidine 352 Indigenous/Imported Road/Sea

Ortho Cyano Phenol 283 Indigenous/Imported Road/Sea Potassium Hydroxide 133 Indigenous Road

DMF 1200 Indigenous Road Water 880 Indigenous Road

2 BOSCALID

1,4-dichlorobenzene 1000 Indigenous/Imported Road/Sea Mg 170 Indigenous Road

Toluene 5000 Indigenous Road THF 3000 Indigenous Road

Trimethyl borate 710 Indigenous/Imported Road/Sea HCl 500 Indigenous Road

Water 5000 Indigenous Road 1-chloro-2-nirobenzene 1060 Indigenous/Imported Road/Sea

Catalyst 20 Indigenous/Imported Road/Sea Methanol 2500 Indigenous Road

Pd/C 20 Indigenous/Imported Road/Sea Acetonitrile 3000 Indigenous Road

PCl3 350 Indigenous Road NaOH 50 Indigenous Road

Catalyst 50 Indigenous/Imported Road/Sea XP-50 2000 Imported Road/Sea

3 Carboxin

Acetoacetanilide 1506 Indigenous/Imported Road/Sea SO2Cl2 1183 Indigenous Road

TEA 789 Indigenous Road 2‐ME 611 Imported Road/Sea PTSA 350 Indigenous Road

Benzene 8500 Indigenous Road Acetone 4000 Indigenous Road Water 8000 Indigenous Road

4 Chlorothalanil

Tetrachloro Isophthalic acid 1055 Imported Sea/Road

Toluene 2000 Indigenous Road Ammonia Solution 125 Indigenous Road

Catalyst (phosphorous pentaoxide) 20 Indigenous/Imported Sea/Road

Water 850 Indigenous Road

5 Difenconazole

1,3 Di Chloro Benzene 392 Imported/Indigenous Sea/Road Acetyl Chloride 208 Imported/Indigenous Sea/Road

Aluminium Chloride 490 Imported/Indigenous Sea/Road EDC 4800 Indigenous Road KOH 473 Indigenous Road

4- Chloro Phenol 340 Imported/Indigenous Sea/Road Di Methyl Formamide 3900 Indigenous Road

Bromine 422 Imported/Indigenous Sea/Road Catalyst 10 Imported/Indigenous Sea/Road

Propylene Glycol 198 Imported/Indigenous Sea/Road 1,2,4 – Triazole 180 Imported/Indigenous Sea/Road

Toluene 2000 Indigenous Road





6 Epoxiconazole

Fluoro Benzene 320 Imported/Indigenous Sea/Road Chloro Acetyl Chloride 375 Imported/Indigenous Sea/Road

Aluminium Chloride 400 Imported/Indigenous Sea/Road EDC 1300 Indigenous Road KOH 555 Indigenous Road

1,2,4 – Triazole 228 Imported/Indigenous Sea/Road DMF 1800 Indigenous Road

2- Chloro Benzyl Chloride 530 Imported/Indigenous Sea/Road

Di Methyl Sulphide 202 Imported/Indigenous Sea/Road Water 2440 Indigenous Road

7 Hexaconazole

1,3 Di Chloro Benzene 510 Imported/Indigenous Sea/Road Pentanoyl Chloride 417 Imported/Indigenous Sea/Road Aluminium Chloride 632 Imported/Indigenous Sea/Road

EDC 2850 Indigenous Indigenous Methylene Triphenyl

Phosphorane 944 Imported/Indigenous Sea/Road

Bromine 540 Indigenous Indigenous THF 1200 Indigenous Indigenous

Hydrogen Peroxide 116 Indigenous Indigenous KOH 178 Indigenous Indigenous

1,2,4 – Triazole 220 Imported/Indigenous Sea/Road DMF 1100 Indigenous Indigenous Water 3943 Indigenous Indigenous

8 Kresoxim Methyl

Ortho Cresol 360 Imported/Indigenous Sea/Road Phthalide 447 Imported/Indigenous Sea/Road

Potassium Hydroxide 187 Indigenous Road Xylene 1800 Indigenous Road

Thionyl Chloride 398 Indigenous Road Sodium Hydroxide 163 Indigenous Road Sodium Cyanide 172 Indigenous Road

30% Hydrochloric Acid 131 Indigenous Road Methanol 1000 Indigenous Road

Methoxy Amine 156 Imported/Indigenous Sea/Road Water 3975 Indigenous Road

9 Penconazole

2-(2,4 – dichlorophenyl) Pentyl Alcohol 905 Imported Sea/Road

Methane Sulphonyl Chloride 445 Imported Sea/Road

Sodium Hydroxide 155 Indigenous Road Toluene 1200 Indigenous Road

1,2,4 – Triazole 264 Imported/Indigenous Sea/Road Sodium Methoxide 208 Indigenous Road


10 Picoxystrobin

3 - Iso Chromanone 445 Imported Sea/Road Methyl Formate 180 Imported/Indigenous Sea/Road

Di Methyl Carbonate 270 Imported/Indigenous Sea/Road Sodium Hydride 287 Imported/Indigenous Sea/Road

Toluene 1300 Indigenous Road HCl gas 110 Indigenous Road

EDC 1400 Indigenous Road 2-Chloro-6-Trifluoro

Methyl Pyridine 483 Imported Sea/Road

Potassium Hydroxide 168 Indigenous Road Xylene 1000 Indigenous Road Water 666 Indigenous Road

11 Propiconazole

1,3 Di Chloro Benzene 452 Imported Sea/Road Acetyl Chloride 238 Imported/Indigenous Sea/Road

Aluminium Chloride 558 Imported/Indigenous Sea/Road EDC 1600 Indigenous Road

Bromine 553 Indigenous Road Catalyst 10 Imported/Indigenous Sea/Road

1,2 – Butanediol 320 Imported/Indigenous Sea/Road Toluene 1000 Indigenous Road

Potassium Hydroxide 166 Indigenous Road 1,2,4 – Triazole 210 Imported/Indigenous Sea/Road





12 Prothioconazole

1,2,4 triazole 353 Imported/Indigenous Sea/Road paraformaldehyde 154 Imported/Indigenous Sea/Road

chloroform 2500 Indigenous Road Thionyl chloride 1200 Indigenous Road

Sulphur 169 Indigenous Road DMF 4500 Indigenous Road

Ethyl acetate 2600 Indigenous Road saturated sodium

bicarbonate 1000 Indigenous Road

magnesium turnings 125 Indigenous Road tetrahydrofuran 2500 Imported/Indigenous Sea/Road

I- (1- chloro-cyclopropyl) -2- (2-chlorophenyl)

ethanone 888 Imported Sea/Road

10% aqueous acetic acid 1000 Indigenous Road dichloromethane 1500 Indigenous Road

13 Pyraclostrobin

1,4 Dichloro Benzene 422 Imported/Indigenous Sea/Road 3 – Chloropyrazole 275 Imported Sea/Road

Xylene 4000 Indigenous Road Catalyst 10 Imported/Indigenous Sea/Road

2 – Chlorobenzyl Alcohol 350 Imported Sea/Road N – Methoxy Carbamate 270 Imported Sea/Road


14 Tebuconazole

1-(4 – Chlorophenyl) 4-4-Dimethyl -3-

Pentanoate 675 Imported Sea/Road

Sodium Methoxide 152 Imported/Indigenous Sea/Road Di Methyl Sulphide 186 Imported/Indigenous Sea/Road

Toluene 1400 Indigenous Road 1,2,4 – Triazole 206 Imported/Indigenous Sea/Road


15 Thifluzamide

Ethyl trifluoroacetate 598 Imported Sea/Road Chlorine gas 198 Indigenous Road

Ethanethiomide 196 Imported/Indigenous Sea/Road Triethyl amine (ET3N) 15 Indigenous Road

Acetonitrile 1000 Indigenous Road NaOH 606 Indigenous Road

HCl 30% 315 Indigenous Road Thionyl chloride 276 Indigenous Road

Toluene 2000 Indigenous Road Water 3241 Indigenous Road

2,6-dibromo-4-(trifluoromethoxy)aniline

(DBTFMA) 705 Imported Sea/Road

16 Trifloxystrobin

2 – Methyl Aniline 275 Imported/Indigenous Sea/Road Sodium Nitrite 177 Indigenous Road

30% Hydrochloric Acid 338 Indigenous Road Glyoxylic Acid Methyl

Ester Oxime 259 Imported Sea/Road

Sodium Hydroxide 306 Indigenous Road Di Methyl Sulphate 160 Imported/Indigenous Sea/Road

Chlorine Gas 190 Indigenous Road EDC 1200 Indigenous Road

Sodium [1-{(3-Trifluoro Methyl) Phenyl}

Ethylidene Amino] Oxidanide

517 Imported Sea/Road


Herbicide

1 Carfentrazone

2-fluoroaniline 730 Imported Sea/Road Sodium Nitrite 460 Indigenous Road

Hydrochloric Acid 4210 Indigenous Road Sodium Sulfite 2710 Indigenous Road




Caustic lye Solution 2644 Indigenous Road 20% Sodium Hydroxide 4275 Indigenous Road 10% Sodium Hydroxide 1500 Indigenous Road

Acetaldehyde 382 Indigenous Road Chlorine 1085 Indigenous Road

Acetic Acid 500 Indigenous Road Methanol 4000 Indigenous Road

Potassium Carbonate 924 Indigenous Road Dimethylformaide 7500 Indigenous Road

Dichlorofluoromethane 665 Indigenous/Imported Sea/Road Oleum 5565.2 Indigenous Road

Nitric Acid 502.2 Indigenous Road Dichloroethane 3250 Indigenous Road Catalyst Pd/C 59.5 Indigenous Road Ethyl Acrylate 425 Indigenous Road

Acetonitrile 5300 Indigenous Road IPA 6325 Indigenous Road

Water 42906 Indigenous Road Freon gas 895 Indigenous/Imported Road

2 Clethodim

5-Propyl 2-Thio Ethyl Cyclohexane 1,3 dione 625 Imported Sea/Road

Propionyl Chloride 285 Imported/Indigenous Sea/Road Aluminum Chloride 450 Imported/Indigenous Sea/Road 1-Chloro 3-Allyl Oxy

Amine 330 Imported/Indigenous Sea/Road


3 Clodinafop Propargyl

2, 3 – Di Fluoro–5–Chloro Pyridine 448 Imported Sea/Road

2–(4–Hydroxy Phenoxy) Propionic Acid 548 Imported Sea/Road

Sodium Hydroxide 240 Indigenous Road Di Methyl Formamide

(DMF) 1200 Indigenous Road

Propargyl Chloride 180 Imported/Indigenous Sea/Road Toluene 1000 Indigenous Road Water 450 Indigenous Road

4 Clomazone

3-chloro-2, 2-dimethylpropanoyl

chloride 875 Imported Sea/Road

hydroxylamine hydrochloride 390 Indigenous/Imported Sea/Road

50% NaOH solution 1286 Indigenous Road Water 4172 Indigenous Road

Sodium Carbonate or NaOH 470 Indigenous Road

2-chlorobenzyl chloride 825 Indigenous/Imported Sea/Road Dichloromethane 2945 Indigenous Road

Hexane 2454 Indigenous Road

5 Cloransulam

2-Ethoxy-4,6-difluoropyrimidine 627 Imported Sea/Road

hydrazine 80 % 255 Imported/Indigenous Sea/Road Carbon disulphide 314 Indigenous Road

methanol 2750 Indigenous Road Triethylamine 560 Indigenous Road

Hydrogen peroxide 30% 628 Indigenous Road Hydrochloric acid 30% 447 Indigenous Road

30% Sodium methylate- methanol solution 745 Indigenous Road

Dichloromethane Hydrochloric acid 980 Indigenous Road

Sodium perchlorate 490 Indigenous Road Dichloromethane 590 Indigenous Road

2-AMINO-3-CHLORO-BENZOIC ACID METHYL ESTER

500 Imported/Indigenous Sea/Road

water 2964 Indigenous Road 6 Diclosulam 5-ethoxy-)-7-fluoro- 749 Imported Sea/Road




[1,2,4]-triazolo[1,5-c]pyrimidine-2-sulfonyl

Chloride 2,6-Dichloroaniline 642 Imported/Indigenous Sea/Road 3,5-Dimetylpyridine 866 Imported/Indigenous Sea/Road

Acetonitrile 22942 Indigenous Road Dimethyl Sulfoxide

(DMSO) 8 Indigenous Road

7 Fenoxaprop P Ethyl

3, 6 – Di Chloro Benzoxazole 610 Imported Sea/Road

2 – (4 – Hydroxy Phenoxy) Propionic Acid 590 Imported Sea/Road

Sodium Hydroxide 121 Indigenous Road DMF 1400 Indigenous Road

Thionyl Chloride 384 Indigenous Road Toluene 2500 Indigenous Road

20% NaOH solution 1125 Indigenous Road Sodium Ethoxide 222 Imported Sea/Road


8 FLUFENACET

N-(4-fluorophenyl)-2-hydroxy-

Nisopropylacetamide 520 Imported Sea/Road

2-(Methylsulfonyl)-5-(trifluoromethyl)-1,3,4-

thiadiazole 635 Imported Sea/Road

PTSA 6 Indigenous Road 25% Sodium hydroxide 708 Indigenous Road 5% Hydrochloric acid 575 Indigenous Road

Methanol 1400 Indigenous Road Ethylene dichloride 2450 Indigenous Road

9 Fomesafen

5-Hydroxy-2-Nitro Benzoic Acid 485 Imported Sea/Road

3,4-Di Chloro Benzotrifluoride 567 Imported Sea/Road

Sodium Hydroxide 277 Indigenous Road Dimethyl sulphoxide 2100 Imported/Indigenous Sea/Road

20 % Ammonium Hydroxide Solution 458 Indigenous Road

Toluene 2400 Indigenous Road Methane Sulfonyl

Chloride 300 Imported/Indigenous Sea/Road


10 Glufosinate Ammonium

n-Butyl (3-cyano-3-hydroxypropyl) methyl

propionate 850 Imported Sea/Road

HCl 35% 549 Indigenous Road AMMONIA 100 Indigenous Road

WATER 1800 Indigenous Road

11 Glyphosate

SODIUM TUNGSTATE 5 Imported/Indigenous Sea/Road PMIDA 1621 Imported/Indigenous Sea/Road

SODIUM METABISULFITE 21 Indigenous Road

VANADIUM SULPHATE 0.4 Imported/Indigenous Sea/Road H2O2 604 Indigenous Road Water 3718 Indigenous Road

12 Mesotrione

1,3-cyclohexadione 387 Imported Sea/Road Ethylene dichloride 9000 Indigenous Road

Acetone cyanohydrins 107 Imported Sea/Road Triethylamine 100 Indigenous Road

2-nitro-4-methylsulfonyl benzoyl chloride 914 Imported Sea/Road

Sulfuric acid solution 835 Indigenous Road 10 %Sodium hydroxide 1000 Indigenous Road

water 3300 Indigenous Road

13 Penoxsulam

Trizolopyrimidine amine 404 Imported Sea/Road Sulphonyl chloride 672 Indigenous Road

Pyridine 164 Indigenous Road DMSO 2020 Indigenous Road





14 Pretilachlor

2,6-diethyl aniline 1699 Imported Sea/Road 1-Bromo-2-Propoxy

Ethane 466 Imported Sea/Road

Sodium carbonate 403 Indigenous Road CAC 387 Imported Sea/Road

Triethyl amine 363 Indigenous Road Toluene 1500 Indigenous Road Water 5300 Indigenous Road

15 PROPANIL 3,4‐DCA 747 Imported Sea/Road Propionic acid 404 Imported/Indigenous Sea/Road

16 PROPAQUIZAFOP

Carboxylic acid 777 Imported/Indigenous Sea/Road Alcohol 265 Indigenous Road

Thionyl chloride 269 Indigenous Road Pyridine 178 Indigenous Road

DMF 3885 Indigenous Road Toluene 3108 Indigenous Road Water 2000 Indigenous Road

17 Sulfentrazone

Phenyl Hydrazine 765 Imported/Indigenous Sea/Road Acetaldehyde 376 Imported/Indigenous Sea/Road

Sodium Cyanate 530 Imported/Indigenous Sea/Road Acetic acid 500 Indigenous Road Chlorine 2308 Indigenous Road Methanol 4000 Indigenous Road

20% Sodium Hydroxide 500 Indigenous Road Potassium Carbonate 900 Indigenous Road

Dimethylformaide 7550 Indigenous Road Dichlorofluoromethane 650 Imported/Indigenous Sea/Road

Oleum 4450 Indigenous Road Nitric Acid 385.5 Indigenous Road

Dichloroethane 2620 Imported/Indigenous Sea/Road Catalyst Pd/C 63.2 Imported/Indigenous Sea/Road

Methane Sulfonylchloride 689 Imported/Indigenous Sea/Road

Pyridine 490.6 Indigenous Road Toluene 4983.8 Indigenous Road

Dichloromethane 2125 Indigenous Road IPA 6415 Indigenous Road

Water 36685 Indigenous Road 10% Sodium Hydroxide 1000 Indigenous Road

Insecticide

1 Chlorantraniliprole

2-amino-5-chloro-N,3-dimethylbenzamide 440 Imported/Indigenous Sea/Road

3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carbonyl

chloride


Triethyl amine 225 Indigenous Road Toluene 3150 Indigenous Road Water 2300 Indigenous Road

2 CYANTRANILIPROLE

2-amino-5-cyano-N, 3-dimethyl benzamide 430 Imported Sea/Road

3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carbonyl

chloride

725 Imported Sea/Road

Triethyl amine 230 Indigenous Road Xylene 3320 Indigenous Road Water 2500 Indigenous Road

3 Flubendiamide

3- Iodophthalic Anhydride 1768 Imported Sea/Road

1,1-Dimethyl-2-Methylthioethylamine 768 Imported Sea/Road

Triethylamine 129 Indigenous Road Trifluoroacetic Anhydride 1085 Indigenous Road 4- Heptafluoroisopropyl-

2-Methylaniline 503 Imported/Indigenous Sea/Road




Trifluoroacetic Acid 7 Indigenous Road M-Chloroperbenzoic

Acid (MCPBA) 548 Imported/Indigenous Sea/Road

Dimethylacetamide (DMA) 6647 Imported/Indigenous Sea/Road

Toluene 5587 Indigenous Road Acetonitrile 4605 Indigenous Road

Dichloromethane (DCM) 8581 Indigenous Road

4 Nitenpyram

1,1,2- trichloroethane 940 Imported Sea/Road NaOH 282 Indigenous Road

30 % HCl 764 Indigenous Road HNO3 396 Indigenous Road

Ethyl amine 265 Indigenous Road 20% NaOH 800 Indigenous Road

Methylene chloride 1200 Indigenous Road Methane amine 158 Imported/Indigenous Sea/Road

Water 5340 Indigenous Road 1,1,1- trichloro-2-

nitroethane 1009 Imported Sea/Road

5 Pymetrozine

3 Pyridine Carboxaldehyde 519 Imported Sea/Road

1,2,4 Triazine-3 (4H) 1,4 -Aamino-5,6 -(Dihydro-6-

Methyl) 639 Imported Sea/Road


6 Spirodiclofen

Cyclohexanone 340 Indigenous Road sodium cyanide 170 Imported/Indigenous Sea/Road

Ethyl acetate 5240 Indigenous Road Water 3150 Indigenous Road

2,4- dichloro-phenylacetic acid 565 Imported Sea/Road

Thionyl chloride 676 Imported/Indigenous Sea/Road Dichloromethane 5080 Indigenous Road

Pyridine 762 Indigenous Road 3% hydrochloric acid

solution 1500 Indigenous Road

5% sodium carbonate solution 1800 Indigenous Road

Sulphuric acid 450 Indigenous Road Methanol 2500 Indigenous Road

5% sodium bicarbonate 1000 Indigenous Road magnesium ethoxide 232 Imported/Indigenous Sea/Road

Ethanol 3500 Indigenous Road HCl for 5% hydrochloric

acid 1000 Indigenous Road

Triethylamine 1000 Indigenous Road 2,2- dimethylbutyryl

chloride 400 Imported Sea/Road

hydrochloric acid 1000 Indigenous Road sodium bicarbonate

solution 2000 Indigenous Road

7 Thiamethoxam

N,N Dimethyl Carbonate 4774 Imported Sea/Road 2-chloro-5-

chloromethyltriazole 764 Imported Sea/Road

3-methyl-4-nitroimino-perahydro 1,3,5-

oxadiazine (Solid) 836 Imported Sea/Road

Tetramethylammonium hydroxide pantahydrate 18 Indigenous Road

Potassium carbonate (K2CO3) 1100 Indigenous Road

Hydrochloric acid (HCl) 1182 Indigenous Road Water 2725 Indigenous Road

8 Spirotetramet 1,4-

dioxaspiro[4,5]decan-8-one

628 Imported Road

Sodium Cyanide 196 Imported/Indigenous Sea/Road




Ammonium carbonate 284 Indigenous Road HCl gas 488 Indigenous Road

Methanol 3900 Indigenous Road 3N NaOH 1500 Indigenous Road Dry HCl 140 Indigenous Road NaOH 160 Indigenous Road (2,5-

dimehtlphenyl)acetyl chloride


Acetonitrile 2200 Indigenous Road K2CO3 510 Indigenous Road

Potassium t-Butoxide 100 Imported/Indigenous Sea/Road DMF 2500 Indigenous Road

4N HCl 1500 Indigenous Road Acetyl chloride 272 Indigenous Road

Dichloromethane 3000 Indigenous Road TEA 200 Indigenous Road

4-dimethylaminopyridine 20 Imported/Indigenous Sea/Road 20% NaOH in scrubber 680 Indigenous Road

water 2140 Indigenous Road

Intermediate

1 1,2,4 – Triazole

Formic Acid 85% 2000 Imported/Indigenous Sea/Road Ammonia Gas 900 Indigenous Road

Hydrazine Hydrate 80% 1000 Imported/Indigenous Sea/Road Water 2315 Indigenous Road

2 CCMT

Allyl Chloride 761 Imported/Indigenous Sea/Road Chlorine gas 685 Indigenous Road

Sodium Hydroxide, (Flakes) 358 Indigenous Road

TEBA (Catalyst) 20 Imported/Indigenous Sea/Road Sodium Thiocyanate 700 Indigenous Road

Sulfuryl Chloride 1052 Imported/Indigenous Sea/Road Toluene 3478 Indigenous Road Water 2127 Indigenous Road

3 MNIO

N-Nitroguanidine 940 Imported/Indigenous Sea/Road 25% Aqueous Methyl

Amine 1358 Indigenous road

Paraformaldehyde 468 Imported/Indigenous Sea/Road Formic Acid 4680 Imported/Indigenous Sea/Road

Water 1636 Indigenous road



(vii) Storage and Transportation Details of Raw Materials

Storage and transportation details of raw materials are provided in Table 3-4.

Table 3-4: Storage and Transportation Details of Raw Materials Sr. No.

Raw Material Max. Storage capacity (Qty. MT/)

Hazards Mode of Storage

No. of units

Physical state of Raw Material

Mode of Transportation

Safety measures to be provided

1 Conc. Sulphuric acid

10 Corrosive Storage tank, MS/PPFRP

1 Liquid By Tanker/ By road

Safety showers Dyke wall Caution note Level gauge Double drain valve Scrubber Required PPEs

2 Dimethyl Formamide

20 Flammable Storage tank, MS/CS


Double static earthing Dyke wall around solvent

storage area. Fire extinguisher and

hydrant point Tanker unloading

procedure Flame arrestor on vent line

of tank Jumper clips on flanges Fencing and No smoking

and prohibited area. Flame proof pumping

station

3 Acetonitrile 20 Flammable Storage tank, MS/CS


4 EDC 20 Flammable Storage tank, MS/CS


5 Toluene 20 Flammable Storage tank, MS/CS


6 Monochloro Benzene

10 Flammable Storage tank, MS/CS


7 Xylene 20 Flammable Storage tank, MS/CS


8 Methanol 15 Flammable Storage tank, 1 Liquid By Tanker/ By



Sr. No.



No. of units




MS/CS road 9 Hexane 15 Flammable Storage tank,

MS/CS 1 Liquid By Tanker/ By

road 10 Chlorine 10 Toxic/

Corrosive MS cylinder (900 kg)

11 Pressurized gas

By Road Exhaust hood connected with caustic scrubber over chlorine handling area.

Facility for eye wash station and quick drenching proximal to work area.

Solution of Sodium Thiosulphate provided near Bromine handling area for neutralization.

11 Bromine 10 Toxic/ Corrosive

Storage tank MSGL


12 Thionyl Chloride 15 Toxic/ Corrosive

Storage tank MSGL


Exhaust hood connected with caustic scrubber over Thionyl chlorine handling area.

13 Hydrochloric acid 40 Corrosive PPFRP/Syntex tank


Safety showers Dyke wall Caution note Level gauge Double drain valve Scrubber Required PPEs

14 Nitric acid 40 Corrosive Storage tank, MS/PPFRP


15 Hydrogen gas 50 kg Flammable MS cylinder (0.5 kg)

100 Pressurized gas

By Road Fire extinguisher and hydrant point

16 Sodium cyanide 3 Toxic Drums (50 kg) 60 Solid By Road Adequate PPEs and safety



Sr. No.



No. of units




gears for all workers. Adequate ventilation

system in working area. Adequate antidote provision

for sodium cyanide leakage available in facility.

Ware house shall be made as per statutory requirement with restricted area.

17 PCl3 1 Toxic/ Corrosive

Drums (200 kg)

5 Liquid By Road Adequate PPEs and safety gears for all workers.

Adequate ventilation system in working area.

Adequate antidote provision for sodium cyanide leakage available in facility.

Ware house shall be made as per statutory requirement with restricted area.

Facility for Eye wash station and quick drenching proximal to all workers.

18 Hydrazine hydrate 10 Toxic HDPE Drums (200 kg)

50 Liquid By Road

19 Triethyl amine 10 Toxic Storage tank, MS

1 Liquid By tanker/ By road

20 Caustic lye 48% 15 Corrosive Storage tank, MS

2 Liquid By tanker/ By road

Dyke wall around the storage tank

21 Dichloro Benzene 10 Flammable Storage tank, 1 Liquid By Tanker/ By Double static earthing



Sr. No.



No. of units




MS/CS road Dyke wall around solvent storage area.

Fire extinguisher and hydrant point

Tanker unloading procedure

Flame arrestor on vent line of tank

Jumper clips on flanges Fencing and No smoking

and prohibited area. Flame proof pumping

station

22 Ethyl acetate 15 Flammable Storage tank, MS/CS


23 Isopropyl alcohol 15 Flammable Storage tank, MS/CS


24 Ethanol 10 Flammable Storage tank, MS/CS




(viii) Resource optimization/recycling and reuse envisaged in the project

Leakages and spillages will be avoided to minimize the product loss.

(ix) Availability of water its source, Energy/power requirement and source

Availability of water its source, Energy/power, Fuel required and its source are described in following sections:

Water

Total water requirement will be 1445KLD. 1183.4 KLD fresh water will be sourced from GIDC, Dahej, 240 KLD boiler condensate will be recycled in boilers and 21.6 KLD for gardening water will be sourced from proposed Sewage Treatment Plant. Details of water consumption is provided in Table 3-5. Water Balance is provided in Figure 3-1.Table 3-5

Table 3-5: Details of Water Consumption Water Consumption Source

Sr No Usages Types Quantity KLD

1 Domestic 30 GIDC

2 Industrial

a) Processing 435 GIDC

b) Cooling 460 GIDC

c) Boiler 480 [240 KLD recycled + 240 KLD fresh]

d) Washing 15 GIDC

e) Gardening 25 [21.6 KLD treated STP + 3.4 KLD Fresh]

Total 1445

Prefeasibility Report SHREEJI PESTICIDES


Figure 3-1: Water Balance Diagram



Energy/ Power

Details of Energy and Power requirement are tabulated in Table 3-6.

Table 3-6: Power Requirements and Its Source

Sr No Particulars Quantity Source/Remarks

1 Domestic Power 50 KWH DGVCL 2 Industrial Power 4500 KWH 1 D.G.Set 4 Back Up

Diesel Generator will be kept as power backup.

Fuel

Coal / Natural Gas / Furnace oil will be used as primary fuel. HSD will be used as fuel for D.G Set. Details of fuel used in provided in Table 3-7.

Table 3-7: Fuel details

Sr No Particulars Quantity Source/Remarks

1 FO, or 25000 Liters/day HPCL 2 NG, or 33000 SCM GAIL 3 Coal 62 TPD Indian/ Imported 4 HSD (D.G.Set) 25000 Liters/day Local

(x) Quantity of wastes (Liquid, gas & Solid) to be generated and scheme for their Management / disposal

Waste Water and its Management

ETP shall be design for 625 KLD. All required Equipment space and sizing shall also be

considered as per KLD. Details of wastewater generation is provided in Table 3-8.

Trade or process plant effluent This is expected from production plant and utilities typically from:

1. Process / Manufacturing operations

2. Utilities

a. Boiler Blow Down

b. Cooling Tower Blow Down

Domestic Effluent

a. Wastewater from washroom

b. Wastewater from canteen

Table 3-8: Waterwater generation details Waste water Generation Disposal

Sr No Usages Types Quantity KLD 1 Domestic 24 STP 2 Industrial



Waste water Generation Disposal a) Processing 174 ETP b) ATFD 245.52 ETP c) Boiler 86 ETP d) Washing 15 ETP e) Sub-Total 520.52 ETP f) Total 545

Treatment to meet discharge effluent standards

1. Domestic Wastewater.i.e sewage will be treated in separate STP of 25 KLD. 2. Effluent from Boiler Blow Down, Cooling Tower Blow Down and High TDS stream

from process will be treated in Multi Effect Evaporator 3. Effluent from washing, Low TDS stream from process and MEE condensate will be

treated in proposed Effluent Treatment Plant.

Recovery of water

1. Domestic wastewater treated in sewage treatment plant will be treated and used in gardening.

2. Boiler condensate will be recycled and reused in process.

Design Details of ETP

Design details of all civil units of the proposed ETP are given in Table 3-9. Effluent

treatment scheme is provided in Figure 3-2 and Sewage treatment scheme is provided

in Figure 3-3.

Table 3-9:ETP details Description Capacity Qty MoC Total Vol. (M³)

Screen Chamber 2000*1000*600 1 RCC 1.2

Oil & Grease Trap 2000*3500*3600 2 RCC 25.2

Oil & Grease Trap 2000*2650*3600 1 RCC 19.08

Equalisation Tank 5000*4700*3600 1 RCC 84.6



Settling Tank 5000*2500*3200 5 RCC 40

Collection Tank 8000*2600*4000 4 RCC 83.2

Bioreactor Tank 38000*7500*4000 2 RCC 1140

Supernatant Tank 3500*5500*3000 1 RCC 57.75

Treated Water Tank 11500*3000*3000 1 RCC 103.5

Sludge Tank 3500*5500*3000 1 RCC 57.75



Description Capacity Qty MoC Total Vol. (M³)

Lime Dosing Tank 2000*2500*2500 2 RCC 12.5

Alum Dosing Tank 2000*1600*2500 2 RCC 8

Poly Dosing Tank 710*700*1000 1 RCC 0.497

Urea Dosing Tank 780*700*1000 1 RCC 0.546

Dap Dosing Tank 710*700*1000 1 RCC 0.497

Floculation Tank 1000*2500*1200 3 RCC 3

Primary Treatment

Raw effluents will be collected in a tank at plant. Then it will be pumped to neutralization

tank, where alkali will be administered to achieve nearly 10 pH. Then effluent will be

pumped to a flash mixer & primary clarifier to undergo physico-chemical treatment.

Coagulant will be also added to aid settling / floatation of charged particulate matters if

any. The effluent leaving the flash mixer will gravitates to a primary settling tank wherein

polyelectrolyte will be added to aid in the settling of particulate matter by allowing them

to agglomerate into large easily settleable flocks.

Secondary Treatment

The clarified effluent from the primary clarifier will be taken to plain aeration tanks where

the pH will be adjusted to near neutral. This aerated effluent will be routed subsequently

to undergo two-stage aerobic biological treatment using the activated sludge process.

Herein the organic matter in the effluent undergoes biological oxidation in the Aeration

tank to produce carbon dioxide and water. There will be an increase in the population of

micro organisms within the Aeration tank which need to be removed by a secondary

clarifier. A major portion of the settled biomass will be re-circulated back to the Aeration

tank to maintain a viable population of micro-organisms to have an aerobic environment

due to which efficient oxidation of organic matter can occur. The remaining portion of the

biomass depending on the growth kinetics of the population of micro organisms within

the reactor will be generated / treated as sludge. This sludge will be separated by

decanter and then dried on beds and finally sent to BEIL for land disposal.

Multi Effect Evaporator (MEE)

We will be installing a forward feed four effect system to suit the requirement. The Feed

from the feed balance tank shall be pumped to a series of the shell & tube type heat

exchangers using the vapors of each effect as a heating media. Pre-heated feed from

feed preheaters is feed to Forced circulation calendria and then passed through the next

Forced circulation evaporator. The Vapors from the preceding effects are used as a



heating medium on the shell side of next calendria. The part of the solution is recycled

back to the same effect to maintain the flow characteristics. Sufficient areas have been

provided on each effect to ensure effective heat transfer. Vapor liquid separators

mounted at the Top part of Forced circulation calendria, with tangential entry are

provided to ensure the efficient separation of liquid and vapors. These shall be of

adequate capacity with sight glass/light glass and manholes.

For circulation specially designed highly efficient Axial Flow pump has been provided.

Product is extracted by means of a product pump. An efficient thermo compressor is

mounted on the vapors separator 1 which compresses the vapors from the same effect

and discharge to shell side of calendria – 1 as heating media. The dry saturated steam

at 3.5 kgs/cm2 (g) is used as motive. Vacuum Pump/ Steam jet ejedtor connected to a

barometric condenser to maintain the desired vacuum level.

Figure 3-2: Effluent Treatment SchemeSewage Treatment Plant

Domestic effluent will be treated in Sewage treatment plant (STP Capacity 25 KLD). The

various unit operations of STP consist of primary sedimentation tank, grit chamber,

aeration tank, sedimentation tank, chlorination tank and sludge drying bed.

First the raw sewage will be collected in primary sedimentation tank where suspended

solids and BOD will be removed to some extent.

The remaining BOD levels are proposed to be reduced in aeration tank followed by

secondary sedimentation tank. The purpose of an aeration tank is mainly to increase the



DO content of effluent and to convert biological dissolved solids to suspended solids.

The dissolved oxygen content can be increased by mechanical surface aerators. It also

provides vigorous agitation and mixing in the water to disperse the oxygen and keeps

the solids in suspension.

The effluent will be passed into the secondary sedimentation tank where the converted

suspended solids will settle and will be removed as sludge. In this system BOD levels

will be reduced to greater extent.

The treated effluent will be chlorinated and will be disposed on land for irrigation. The

sludge which will be collected from primary sedimentation tank and secondary

sedimentation tank will be disposed on drying beds which consist of well drained beds of

sand and gravel. The sludge cake, which will be formed on top of the sand beds, will be

used for manure.

The treated sewage will be further chlorinated and diluted and then used for green belt

development.

Figure 3-3 Schematic diagram of Sewage Treatment plant



Air Emissions Details

Details of process gas emission is provided in Table 3-10 and flue gas emission is provided in

Stack no.

Stack attached to

Stack height in meter

Air pollution control system Parameter Permissible

limit Stack Dia (mm)

1 Process plant -1 30 Water/Caustic Scrubber

PM 100 mg/ Nm3

1000

H2S 5 ppm NO2 50 ppm HCl 20 mg/ Nm3 Cl2 9 mg/ Nm3 HBr 5 mg/ Nm3


PM 100 mg/ Nm3

1000



PM 100 mg/ Nm3

1000

H2S 5 ppm NO2 50 ppm HCl 20 mg/ Nm3 Cl 9 mg/ Nm3

HBr 5 mg/ Nm3

4 Process plant - 4 30 Water/Caustic Scrubber

PM 100 mg/ Nm3

1000


HBr 5 mg/ Nm3


PM 100 mg/ Nm3

1000

H2S 5 ppm NO2 50 ppm H2S 20 mg/ Nm3 NO2 9 mg/ Nm3 HCl 5 mg/ Nm3 Cl 100 mg/ Nm3

HBr 5 ppm

Table 3-11.

Table 3-10: Process gas emission details Stack

no. Stack attached

to Stack height

in meter Air pollution

control system Parameter Permissible limit Stack Dia (mm)


PM 100 mg/ Nm3

1000



PM 100 mg/ Nm3

1000



PM 100 mg/ Nm3

1000


HBr 5 mg/ Nm3

4 Process plant - 4 30 Water/Caustic Scrubber

PM 100 mg/ Nm3

1000 H2S 5 ppm NO2 50 ppm HCl 20 mg/ Nm3 Cl 9 mg/ Nm3



Stack no.

Stack attached to

Stack height in meter

Air pollution control system Parameter Permissible

limit Stack Dia (mm)

HBr 5 mg/ Nm3


PM 100 mg/ Nm3

1000

H2S 5 ppm NO2 50 ppm H2S 20 mg/ Nm3 NO2 9 mg/ Nm3 HCl 5 mg/ Nm3 Cl 100 mg/ Nm3

HBr 5 ppm

Table 3-11: Flue gas emission details

S. No.

Source of emission Stack

Type of Fuel

Quantity of Fuel Type of

emissions i.e. Air Pollutants

Air Pollution Control Measures

With Capacity Height (meter) MT/Day (APCM)

1 DG Set (750 KvA) (4 Nos.) 20 HSD 15

PM – 150 mg/ Nm3; SOx – 100 ppm; NO2 – 50

ppm

DG will be used as stand by

2 Boiler – 15 Tonnes 45 NG/ HSD 10

PM – 150 mg/ Nm3; SOx – 100 ppm; NO2 – 50

ppm

For NG as fuel, APCM is not considered

In case of other feuls, standard APCM norms are considered

3 Boiler - 15 Tonnes 45 NG/ HSD 10

PM – 150 mg/ Nm3; SOx – 100 ppm; NO2 – 50

ppm



4 Boiler – 15 Tonnes 45 NG/ HSD 10

PM – 150 mg/ Nm3; SOx – 100 ppm; NO2 – 50

ppm



5 TFH - 1 30 Thermic oil 10

PM – 150 mg/ Nm3; SOx – 100 ppm; NO2 – 50

ppm



Solid and Hazardous Wastes and Management

Details of Solid and Hazardous generated along with its management is provided in Table 3-12.

Table 3-12: Details of Solid & Hazardous Waste and its Management

Sr No Type of Waste Waste

Quantity

Category (as per HWM Rules,

2016) Method of Disposal

1 Used Lube Oil 500 Lit./month 5.1 Given to CPCB Authorized reprocessors

2 Process /Distillation Residue

1102.68 MT/year 29.1 Incineration in Common

Incineration facility 3 ETP Sludge 150 kg/day 29.2 Disposal at BEIL

4 Date Expired /off

Specification Products

25 MT /year 29.3 Incineration in Common Incineration facility

5 Spent Solvent 150 MT/ month 29.4

Incineration in Common Incineration facility

6

Packing Materials

Empty Bags 2000 Bags/month 33.1

Given to GPCB

Barrel 1000 Barrel Authorized Vendor



/month

7 Spent Carbon from ETP 250 kg/ month 36.2

Incineration / Common Incineration facility of BEIL

Ankleshwar

8 Sludge from wet scrubber

1000 kg/ month 37.1

Incineration / Common Incineration facility

9

Production and /or industrial use of glues, organic

cements, adhesive and resins

1.0 MT / year 23.1 Given back to the supplier

(manufacturer) against new resins.

10 MEE Salt 10 MT/day 35.3 Disposal to BEIL

Contaminated PPE's, Insulation waste Batteries , E-Waste, Lead & lead compounds, Non –recyclable plastic waste/Gaskets/Insulations/ PPE’s will be generated and will be handled based on prevailing legislation. The domestic waste generated will be recycled as manure and used for green belt development

(xi) Schematic representations of the feasibility drawing which give information of EIA purpose

Schematic representation of the feasibility drawing which give information of EIA purpose: A Schematic representation of the feasibility drawing is provided in Figure 3-4.



Figure 3-4: EIA Purpose

Type of Industry

Pesticide & Pesticide Secific Intermediates

Type of category as per EIA notification (Catagery -5(b) -A)

Proposed Activity:

Pesticides Tecnical & intermediates manufacturing greenfield project

Submission of Form-1 and Pre-Feasibility

Report & Draft ToR

Resource requirments

Raw Material : Sourced from Manufacturer / Traders of the same.

Land: GIDC, Dahej

Water: Will be sourced from GIDC

Power: Power will be sourced through Madhya Gujarat Vij Co. Limited

Env. Mgt. Plan (EMP)

Air Pollution Control Measures: Adequate air pollution control system will be installed.

Water Pollution : STP and ETP provided. Treated effluent to be disposed in GIDC drain.

Greenbelt Area: Above 33% of the total area will be developed.

Health & Safety measures will be followed properly.

Domestic: Will be treated in STP.

Industrial:: High TDS will be treated in MEE and low TDS in ETP.

Gas emissions: Adequate APCM will be provided.

Hazardous waste: will be disposed off as per hazardous waste 2016

Fugitive emission: efficient control system

Presentation before the EAC for ToR/EC

Site location :

Plot No. D-3/5/3 GIDC Dahej Phase III, Tal

Vagara, Dist. Bharuch, Gujarat



4 SITE ANALYSIS

(i) Connectivity

The project will be located in Dahej GIDC, which is very well connected to State Highway. Details of site connectivity is provided in Table 4-1.

Table 4-1: Site Connectivity

Particular Details Distance with direction

Nearest Road SH-6 Adjacent in West direction

Nearest railway station Dahej 8.3 km towards SW Bharuch 38.3 km towards ESE

Nearest Airport Surat 73 km towards S

Vadodara 86.61 km towards NE

(ii) Land Form, Land Use and Land ownership The land is in the form of industrial shed owned by Gujarat Industrial Development Corporation. The Plot has been allotted by GIDC and documents of the same is enclosed as Annexure 1.

(iii) Topography (along with map) Dahej GIDC is located on west of Bharuch district at Gulf of Khambhat. Topographically, the area is almost flat with gentle slope toward south and southwest i.e. toward Gulf. Geologically, entire area is covered with recent age deposits of fluvial and marine origin. Major part of it is covered with dark gray to brown Stiff clayey soil. Toposheet of the region is attached as Annexure 2.

(iv) Existing land use pattern

Proposed project is the barren and un-developed land/plot which is located in Gujarat Industrial Development Corporation (GIDC), Phase III Dahej. The existing land is an undeveloped land and does not include agricultural, forestry, CRZ and there are no national parks, wild life sanctuary, eco sensitive areas within the study area

(v) Existing Infrastructure

GIDC Notified Industrial Estate of Dahej has available infrastructure like water, electricity, roads, rail, transportation, availability of raw material and drainage system.

(vi) Soil Classification The project area falls under South Gujarat Agro-Climatic Zone-II and AEZ-21(Bharuch District).The Zone is characterized by 70-80 cm rain fall, 1-3 % soil slope .The soil depth is >100 cm and predominantly soils are clayey but near port soils are sandy in texture. Majority soils of this area have developed from the trap and mostly having montmorrilonite predominant clay mineral. The soil salinity is < 2.0 dS/m but due to ingress of sea water soils are highly saline especially in Lakhigam. At and around project are soils are barren



and Prosopis julifera (Gandobaval) is seen. However, in the surrounding area sorghum, cotton, tur and fodder crops are grown.

(vii) Climatic Data from Secondary Sources

The general agro-climatic zone of the study area is Semi-arid.

Information presented in subsequent paragraphs is from the most recently published Long Term Climatological Tables for the nearest observatory, Bharuch by the Indian Meteorological Department (IMD).

Rainfall Data

The total rainfall in year is observed to be 924.8 mm. Distribution of rainfall by season is 2.3 mm in winter (December, January, February), 14.3 mm in summer (March, April, May), 869.3 mm in monsoons (June, July, August, September) and 38.9 mm in post-monsoon (October - November).

Temperature Data

Mean daily maximum temperature is recorded in the month of April at 40 °C.

From October to December, both day and night temperatures begin to decrease rapidly. January is generally the coldest month, with a minimum temperature of 11.9 °C.

During the post-monsoon months of October and November, day temperatures remain between 16.9-22.0 ºC. In winters, i.e. December, January and February, average day temperatures remain between 11.9-14.4 ºC.

Humidity

Most humid conditions are found in the monsoons, followed by post-monsoons, winter and summer in that order. Mornings are more humid than evenings and humidity ranges from a high of 80-90% in monsoon mornings to a low of 26-38% in summer evenings. During post-monsoon season, in morning humidity remains between 68-75% and in the evening it remains between 37-44%.

Cloud Cover

The area remains cloudy between June - September, which is the active period of the monsoon season. Cloud cover is 6-8 oktas during monsoon season, while it is 0-2 oktas in post monsoon, winter and summer season.

Seismic Zone: The general agro-climatic zone of the study area is Semi-arid.

(viii) Social Infrastructure

Key infrastructure such as hospitals, schools, bank, places of worship and social/ community facilities such as park, market, playground etc. education, health care, community development, income distribution, employment and social welfare are available in nearby area of Dahej Industrial Estate.



5 PLANNING BRIEF

(i) Planning concept

There is a cluster of numerous large-scale, medium-scale and small-scale industries which includes Agro Based, Soda Water, Cotton textiles, Leather, Chemical, Engineering units, Mineral based specialilty chemicals, pesticides and others in the Gujarat Industrial Development Corporation (GIDC) notified Estate of Dahej.

(ii) Population Projection Not applicable

(iii) Landuse Planning

Proposed project is located within the Notified Industrial Estate by Government of Gujarat and due to the proposed project there will not be any change in the land use pattern of the region.The area statement of the project area is provided in Table 5-1.

Table 5-1: Area Statement Sr No Particulars Area Sq mts

1 Plant 7200 2 ETP and WTP 2360 3 Storage 3930 4 Admin, Security, Canteen 1777 5 Greenbelt Area (33% of Total Plot Area) 33379 6 Utility, R&D, Solvent Recovery 2501 7 Parking 11371 8 Open Area 37007

9 Pump Room for Fire Tank, Toilet and Hydrogenation Area 748

Total 100272

Site layout plan is provided in Figure 5-1.



Figure 5-1: Plant layout

(iv) Assessment of Infrastructure Demand

There is no need for any infrastructure demand in terms of physical or social needs for the proposed expansion.

(v) Amenities/ Facilities

Basic Amenities like public transport, water supply, telecommunications, educational institutions, hospitals etc. are available in nearby area of Dahej Industrial Estate.



6 PROPOSED INFRASTRUCTURE

(i) Industrial Area (Processing Area)

Proposed infrastructure will be developed as per standard engineering design considering

all the relevant parameters related to environment, health and safety.

(ii) Residential Area (Non Processing Area)

No residential area is involved in the proposed project.

(iii) Green Belt

Green belt will be provided and maintained at the tune of 33% of the total land area.

(iv) Social Infrastructure

Availability of drinking water facilities, toilets, parking area etc.

(v) Connectivity (Traffic and Transportation Road/ Rail/ Metro/ Water ways etc)

The project site is very well connected by road network.

(vi) Drinking Water Management

The water will be supplied by Gujarat Industrial development Corporation (GIDC).

(vii) Industrial Waste Management

Details of Industrial Waste management are already provided in section above.

(viii) Power Requirement & Supply/ Source

The power requirement is 4550 KW which will be procured from Dakshin Gujarat Vij Company Ltd. For emergency and as back-up D.G set (4 Nos.) of 750 KVA will be installed.



7 REHABLITATION & RESETTLEMENT (R & R) PLAN

(i) Policy to be adapted (Central /State) in respect of the project affected persons including home outsee, Land outsee and Landless labourers

There will be no rehabilitation and resettlement undertaken as labors and workers from local & nearby areas for the proposed construction activity which will be minor as the proposed expansion activity is to be undertaken at the existing site.



8 PROJECT SCHEDULE AND COST ESTIMATE

(i) Likely date of start of construction and likely data of completion

After obtaining Environmental clearance and Consent to Establish from GPCB, the company shall start the proposed construction and commissioning of the project and complete the project within 20 months.

(ii) Estimates project cost along with analysis in terms of economic viability of the project

Estimated project capital cost along recurring cost is given in Table 8-1 and Table 8-2 respectively.

Table 8-1: Capital Cost Projection

Sr No. Description Cost Rs. In Lakh

1 Land 2153

2 Land / Site development 547

3 Building 5667

4 Plant & Machinery 7770

5 Misc. Assets 113

6 STP Cost 10

7 ETP Cost 650

8 APCM Cost 70

9 Greenbelt Development 20

Total 17000

Table 8-2:Recurring/Operating Cost Per Annum

Component Proposed (Rs. in Lacs/annum)

Environment & Safety Management System 530

Air 12

Water 24

Solid waste Disposal 62

Greenbelt Maintenance 5

Total 633



9 ANALYSIS OF THE PROPOSAL (FINAL RECOMMENDATIONS)

(i) Financial and social benefits with special emphasis on the befit to the local people including tribal population, if any, in the area Proposed project will provide benefits to the local people in terms of financial and social welfare. From the proposed project, there shall be increase to foreign exchange generated by

Exports. Reduce dependence on Imports hence reducing for risks. There shall be direct or indirectly increase in employment generation for the local

people and lead to ensure continued employment to existing workforce without affecting work conditions and hence supporting their families.

The company will allocate budget for CER activities, which can lead to improved social infrastructure, if planned properly.

The proposed expansion project shall not have any adverse environmental impacts because adequate protection measures will be provided to achieve permissible norms of GPCB.



ANNEXURE

S



Annexure 1: Plot allotment letter



Annexure 2: Toposheet of the Region



Annexure 3: PCPIR Document























Documents

PRE-FEASIBILITY REPORT · 2019-04-11 · PRE-FEASIBILITY REPORT . FOR . Greenfield Multi-Purpose Plant for Manufacturing of Various Technical Grade Pesticides and Intermediates