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CHAPTER – I BRIEF DESCRIPTION OF NATURE, SIZE, LOCATION OF THE PROJECT AND ITS IMPORTANCE TO THE COUNTRY, REGION, SCOPE OF THE STUDY -

2

INTRODUCTION

BASIC INFORMATION M/s. Nagarjuna Agrichem Limited (NACL) has established a pesticide manufacturing

unit at Arinama Akkivalasa village, Etcherta mandal (longitude and latitude of 830 47’

30” (E) and 180 16’ 40” (N) ), 16 KM away from Srikakulam town in Srikakulam district

in Andhra Pradesh. The plant area is spread over 119 acres of land. The Survey of

India Topo sheet bearing no. 65 N/15 includes the site.

LOCATION DETAILS

M/s. Nagarjuna Agrichem Limited Plot No.177, P.O, Allinagaram Arinama Akkivalasa (V), Etcherla (M), Srikakulam District 08942-281170, 281172 & 281174 Fax No.08942-281171 Longitude : 830 47’ 30’’ Latitude : 180 16’ 40’’

Kesavadasupuram (V) is at about 500 Mts. Arinama Akkivalasa (V) is at a distance of

1.0 Km. and Chilakapalem (V) is at about 1.5 Km. Pattusalipeta (V), Allinagaram (V),

Bhagavandasu peta (V) and Seshupeta (V) are in the radius of 3 Km.

Yerra cheruvu is at a distance of 400 Mts. and Akkivalasa tank is at about 800 Mts.

Budumuru Tank is at about 3 to 4 Km. Nagavali River is at about 12–15 Km.

North: Road; East: Hill; West: Plantation; South: Dry lands & Mango garden.

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Compliance with regard to Public Liability Insurance Policy

Policy No. 2007/01

Valid Upto : 16/06/2007

Amount : 150 lakhs

HWM Authorisation No. & Date

Common order No. APPCB/VSP/VZN/HO/W&A/2006, dated. 19/07/2006.

Taking in to cognizence of the requirement detailed by the market forces and the

continued growth of the organization in the field of pesticide production, Nagarjuna

Agrichem has arrived at a plan of action wherein some of the products of the existing

profile are discarded a new products are introduced as well as in the production

capacity.

IMPORTANCE OF THE PROJECT

Majority of the population in our country are dependent on agriculture and agricultural

out put has significant impact on our economy. We have to feed 16 % of the world

population with less than of 2% of landmass. Though we have achieved food security

after the green revolution, yields of crops are much lower that of the world standard.

Quality of agricultural products of our country is also not up to the mark because of

usage of out dated and substandard crop protection chemicals.

There is a need for supply of high quality and safe pesticides, fungicides and

herbicides (crop protection chemicals) to the former to enhance the crop yield to the

global level. Crop protection chemicals that we are manufacturing and proposed to

make king are safe with low toxicity and shelf life of less than 7 to 14 days after filed

application. After mixing with water, these chemicals gets hydrolyzed to the basic

nutrients Nitrogen, Phosphorous, Sulfur etc . As a result, crops are free from

pesticide residues and quality of agricultural commodities meet the international

standards.

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The products that we propose to make are currently supplied by leading multinational

companies and are very expensive . We are planning to manufacture these products

with indigenous technology developed in our R& D and supply to formers at

affordable prices.

Usage of crop protection chemicals manufactured by us by our formers will

effectively control pest attack, fungus and weeds and enhance the crop yield . This

will help us to make quality food available to public and ensure the food security .

Quality of the agricultural commodities will also meet the international standards and

foreign exchange can be earned by exports.

AGRO CHEMICALS MARKET

The size of the Indian agrochemicals market is Rs 4000 Crores and that of world is --

----- billion USD ( Rs ------- )

Global pesticide market is growing at a rate of 5 to 8 % annually. China is playing a

significant role in the manufacture of agrochemicals at low prices and dumping in the

world market including India. Quality of agrochemicals manufactured by China are

substandard and Indian agrochemicals companies are struggling to compete with

Chinese companies. We would like to face this challenge by manufacturing

agrochemicals with efficient process , which are developed in our R&D and tested in

our pilot plant. Production volumes also play a significant role in reduction of fixed

costs and to compete globally. The proposed expansion will help us to compete in

the global market and to supply safe crop protection chemicals to formers at

affordable prices.

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CHAPTER - II CONDENSED DESCRIPTION OF THOSE ASPECTS OF THE PROJECT (BASED ON PROJECT FEASIBILITY STUDY), LIKELY TO CAUSE ENVIRONMENTAL EFFECTS.

Location (maps showing general location, specific location, project boundary & project site layout)

Size or magnitude of operation (incl. Associated activities required by or

for the project

Proposed schedule for approval and implementation

Technology and process description

Project description. Including drawings showing project layout, components of project etc. Schematic representations of the feasibility drawings which give information important of EIA purpose

Description of mitigation measures incorporated into the project to

meet environmental standards, environmental operating conditions, or other EIA requirements

Assessment of New & untested technology for the risk of

technological failure

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THE PROJECT PROPOSAL

Nagarjuna Agrichem Limited have established the pesticide manufacture unit at

Arinama Akkivalasa village in Etcherla mandal of Srikakulam District, Andhra

Pradesh. The existing product profile and the production capacities were duly cleared

by the concerned authorities at the state level (AP Pollution Control Board) and at the

central level (Ministry of Environment and Forest, Govt. of India).

LOCATION DETAILS

M/s. Nagarjuna Agrichem Limited Plot No.177, P.O, Allinagaram Arinama Akkivalasa (V), Etcherla (M), Srikakulam District 08942-281170, 281172 & 281174 Fax No.08942-281171 Longitude : 830 47’ 30’’ Latitude : 180 16’ 40’’

Charts showing the location and project site layout are enclosed. MAGNITUDE OF OPERATION

The proposed project is to marginally modify the existing product range and increase

the production capacity to 30 tonnes per day from 12.5 tonnes per day.

PRODUCTS PERMITTED (Existing operations)

(a) Technical Grade Pesticides: The industry shall manufacture the products mentioned in Option –I or Option –II or Option –III at any time only. S.No Products Option–I

MT/Day Option–II MT/Day

Option–III MT/Day

1. Monocrotophos** 3.0 3.0 3.0 2. Acephate 4.0 -- -- 3. Dichlorovos 3.0 -- -- 4. Atrazine 2.0 2.0 2.0 5. Profenofos** -- 3.0 -- 6. Trcyclozole or Propiconazole 0.5 0.5 0.5 7. Isoxaben -- -- 0.5 8. Pretilachlor -- -- 1.0 9. Myclobutanil -- -- 0.5

Total: 12.5 8.5 7.5

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Liquid Formulations (One Product at a time)

MCP (36% - 60% )

Dichlorovos (76%)

Profenofos (40% - 72%) 8 KLD

Butachlor (50%)

Powder Formulations (One product at a time)

Acephate (42.5% - 75%)

Carbendazim (50%)

Atrazine (50%) 3 TPD By Products in Present Generation Sl.No Product Name By Product Qty

Kgs/day 1

Monocrotophos Ammonium Chloride 756

2

Profenofos 30% HBr Solution 25% NaBr & Nacl Solution Triethyl Amine

2381 5835 765

3

Propiconazole 45% HBr Solution 30% Hcl Solution

328 221.5

4

Tricyclazole 45% HBr Solution 224

5 Isoxaben 20% Hcl Solution 542 6

Pretilachlor Sodium Chloride 24% Sodium Bromide Solution

183 1358

7 Miclobutanil 20% Sodium Bromide Solution 2632

Products mentioned under either of the option were to be produced at a time.

It is proposed to increase the production capacity to 30tpd. The new product profile

as follows.

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Proposed Capacity

Industry proposed to increase the production capacity to 30 TPD from the present

12.5 TPD. The new product profile and production capacities after expansion are as

follows:

S. No

Product After

Expansion (TPD)

Remarks

1. Acephate 3.5 Existing with decreasing capacity

2. DDVP 2.0 Existing with decreasing capacity

3. Propiconazole 3.0 Existing with increasing capacity

4. Trcyclozole 2.0 Existing with increasing capacity

5. Profenofos 7.0 Existing with increasing capacity

6. Pretilachlor 6.5 Existing with increasing capacity

7. Isoxaben 1.0 Existing with increasing capacity

8. DAAM 0.75 New Product

9. 4-HBAGE 0.5 New Product

10. Myclobutanil 1.5 Existing with increasing capacity

11. Thifluzomide 1.0 New Product

12. Femlaconazole 0.75 New Product

13. DMBCP 0.5 New Product

Total: 30.0

Power 4.0 MW Captive Power Plant is proposed.

PRODUCT MT/DAY Acephate 3.5 DDVP 2.0 Propiconazole 3.0 Tricyclozole 2.0 Profenofos 7.0 Pretilachlor 6.5 Isoxaben 1.0 DAAM 0.75 4HBAGE 0.5 Myclobutonil 1.5 Thifluzomide 1.0 Fenbuconazole 0.75 DMBCP 0.5 Total 30.0

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Monocrotophos and Attrizine products are to be deleted in proposed expansion. By Products after Expansion:

S. No.

Name of the By-Products

From the Product

Capacity Kg/Day

1 25% HBr Solution Profenofos 6661.2

2 25% NaBr and NaCl Solutions

Profenofos 13614.0

3 Para chloro phenol Profenofos 6000.0

4 HCl 25% Profenofos 13000.0

5 25% HBr Solution Propiconozole 3542.4

6 25% HCl Solution Tricylazole 1612.8

7 20% HCl Solution Isoxaben 1574.0

8 25% HCl Solution Pretilachlor 6063.2

9 25% NaBr Solution Myclobutanil 5264.2

10 25% KBr Solution DMBCP 2800.0

HBr, KBr and NaBr solutions will be treated in existing Bromine plant Bromine will be

recovered. HCl and Para chloro phenol are to be sold to authorized parties.

The proposed expansion is with in the plant site and no additional land is

acquired. There was no necessity for examining alternative sites as the

proposed expansion to 30 tonnes per day is being carried out within the

existing plant premises.

Project Cost (Rs. in Crores) Existing Proposed Total

i) Land 1.543 1.543

ii) Building 11.325 1.5 12.825

iii) Plant & Machinery 62.463 33.5 95.963

iv) Other Facilities 20.0 20.00

Total 75.331 55.0 130.331

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SCHEDULES OF APPROVAL AND IMPLEMENTATION In respect of schedule of implementation of the expansion programme as detailed

above. The following steps have been taken by the organization.

Due to the proposal to increase the production capacity by way of expansion, the

pollution loads at the points of generation are likely to increase. M/s Nagarjuna

Agrichem Limited is conscious of its responsibility towards the society in

minimizing the pollution load due to the proposed expansion and accordingly

decided to carry out the Environmental impact Assessment to identify the

negative and positive impacts and to delineate effective measures to control the

pollution and to mitigate the environmental pollution.

The organization also proposes to have a sea outfall, so that the impacts are

minimized on the lands around the plant. The outfall location off Peddagedda has

also been identified, based on technical evaluation.

The Nagarjuna Agrichem has given the assignment to the Institute of

Development and Planning Studies (IDPS), Visakhapatnam to undertake the

required studies in regard to environmental concerns and prepare the necessary

documentation. The IDPS is an institution supported by the State Government

with core grant support.

Adopting the new gazette notification issued by the Ministry of Environment and

Forest, Govt. of India in respect of Environmental Impact Assessment Form – 1

has been duly filled and Supporting Documentation and charts are enclosed.

The Nagarjuna Agrichem has been issued the consent for operation and they

have complied with all the stipulations and provisions detailed in the CFO issued

by the APPCB to the existing product profile.

Public hearing for expansion of the product profile and capacity has been

successfully completed.

The implementation period is estimated at six months from date of approval and

sanction by the Ministry of Environment and Forests, Govt. of India.

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TECHNOLOGY AND PROCESS DESCRIPTION

The process description of the above mentioned products in described in brief along

with material balance. The utilities and the pollution control equipment that are in

existence and the new facilities proposed are presented.

PROCESS DESCRIPTIONS WITH MATERIAL BALANCE

1. ACEPHATE Process Description

The process for acephate consists of four steps: Structural Rearrangement,

Acetylation, Purification of Acephate and Solvent Recovery. The process flow

diagram is given in figure-II.1

Structural Rearrangement and Acetylation

Dimethyl Phosphyril Amido Thioate (DMPAT) is isomerized in a reactor using

dimethyl sulphate. Dimethyl Sulphate (DMS) is added at a controlled rate and at a

steady temperature. DMPAT gets converted to Methamidophos during the reaction

as indicated below:

DMPAT DMS Methamidophos DMS M.W 141 M.W 126 M.W 141 M.W 126

Acetic anhydride is added to the above reaction mass at a controlled rate by

maintaining steady temperature. Acetic anhydride reacts with methamidophos and

forms acephate and acetic acid as given below:

Methamidophos Acetic Anhydride Acephate Acetic Acid M.W 141 M.W 102 M.W 183 M.W 60

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Neutralization

The material from the rector is pumped to a neutralizer and adequate quantity

of ammonia is added slowly in the reactor to neutralize acetic acid. After

completion of neutralization, water is charged to neutralizer to dissolve

ammonia acetate. The above mass is pumped to separators where organic

layer is separated. Dichloromethane wash is given to aqueous layer to extract

dissolved acetate and to minimize organic matter in it and the aqueous layer is

separated and pumped to a bulk storage tank in ETP (The aqueous layer

incinerated in a dedicated incinerator).

Concentration

The organic layer is concentrated by vacuum distillation and recovered

dichloromethane is recycled. The concentration mass is charged in crystallizer and

crystallized in ethyl acetate solvent media.

Filtration and Drying Acephate slurry from crystallizer is filtered. The cake from the filter is transferred to

dryer. After drying, acephate is collected in 50 kg capacity drums. The mother liquor

is pumped to distillation vessel for recovery. Ethyl acetate is recovered by vacuum

distillation. Residue is collected in drums and sent for incineration. The material

balance for this product (3.5MT/day) is presented in Table-II.1

Table- II-1: Material Balance for Acephate Technical (3.5 MT/day)

Input Output

Sno Raw

Material M. Wt. Quantity / Ton

(kgs) Quantity /

Day Raw Material M. Wt. Quantity / Ton (kgs)

Quantity / Day

1 DMTPAT 141.1 1260 4410 Acephate 183.2 1000 3500

2 DMS 126 116 406 Aq. Waste 0 1502 5257

3 A.A. 102 787 2754.5 Organic Waste 0 419 1466.5

4 CH2Cl2 0 112.5 393.75 DCM Loss 112.5 393.75

5 E.A. 0 62.5 218.75 EA loss 62.5 218.75

6 Ammonia 17 157.5 551.25 0 0

7 Water 18 600.5 2101.75 0 0

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Total 3095.5 10836 Total 3096 10836 DMTPAT:Diemthyl Thiophosphyril amide; Thioate;DMS: Diemthyl Sulphate; CH2Cl2= Methylene Chloride; E.A. = Ethyl acetate;A.A. = Acetic Anhydride.

Figure-II.1 : Flow Diagram for the production of Acephate

Acetic Anhydride Ammonia Water DCM

DMPAT Aqueous watse

DMS sent to ETP

DCMSteam condensate(ejector)

Sent to ETP

EA for recycle

EN Dryer-1

Steam condensate(ejector)

Crystalizer Sent to ETP

DCM for

Recyle EA for recycle

Dryer-2

Steam condensate(ejector)

Sent to ETP

EA solvent for

extraction

Neutralisation Extraction

Organic residue

sent to Incinarator

Concentration

Solvent Recovery

Filter

Acephate (Tech)

Acephate (Tech)

Isomerisation Acetylation

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2. Dichlorovos (DDVP)

Process Description

The Process flow diagram for Manufacturing of DDVP is given in Figure –II.2. Raw

materials used for the manufacture of DDVP are Chloral and Trimethyl Phosphite.

Chloral is charged in a glass-lined reactor. Trimethyl phosphite is added at a

controlled rate over a period of 12 hrs. Maintaining around 50oC temperature in the

reactor. Hot water is used to maintain the temperature. Methyl Chloride gas

generated during the reaction is sent to incinerator through a Caustic trap and Flame

arrestor. After ensuring that the reaction is completed, the material is transferred to

another glass-lined vessel. Degasification is done in this vessel under vacuum to

remove residual methyl chloride gas traces of chloral derivatives and Trimethyl

phosphite. The vent of the ejector is connected to incinerator through a Caustic trap

and flame arrestor. After Degasification, DDVP of 97% purity is packed in HDPE lined

drums of 200 kgs capacity. The material balance for this product (2.0MT/day) is

presented in Table-II.2.

METHYLCHLORIDE-GAS TO INCINERATOR - 1

Figure- II.2: Process Flow Diagram for Dichlorovos (DDVP)

CONDENSATE

TMP

CHLORAL

DDVP (Tech)

REACTOR

EJECTOR

EVAPORATOR

SENT TO ETP

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Table-II.2: Material Balance for Dichlorovos Technical (2.0 MT/day)

Input Output

Sno Raw

Material M. Wt. Quantity / Ton (kgs)

Quantity / Day Raw Material M. Wt.

Quantity / Ton (kgs)

Quantity / Day

1 Chloral 147.5 700 1400 Dichlorovos 221 1000 2000 2 TMP 124 600 1200 Methyl chloride 50.5 226 452 3 Chloral + TMP 74 148 Total 1300 2600 Total 1300 2600

TMP = Trimethyl Phosphite

3.Profenofos

Process Description

The process flow block diagram for Manufacturing of Profenofos is given in Figure II-

3 Various stages of the process i.e. Bromination, EPT formation, Ammonium salt of

EPT formation, Profenofos reaction and Purification of profenofos are described

below.

OCP formation

Chlorine will be purged in phenol and off gases (HCl) will be scrubbed sold as by

product. The organic mass will be distilled in fractionation tower to collect purified

Ortho- chloro phenol and as a by product purified Para- chloro phenol will be

collected and same will be sold. Still residue will be incinerated.

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Bromination

After charging chlorobenzene initially, ortho-chloro phenol is taken into a glass-lined

Reactor and bromine is added at a controlled rate from a batch tank. A temperature

range of 25-43oC is maintained. During addition, bromine reacts with ortho-chloro

phenol and forms hydrogen bromide and 4-bromo-2-chloro-phenol in the solvent

media of chlorobenzene.

Hydrogen bromide gas generated during the reaction is scrubbed with water and the

resultant 24%-26% of HBr solution in water from the scrubber is sent for the bromine

recovery section or for drumming. The equipment is maintained leak proof during the

reaction and maintenance time. The duration for this stage is

about13hours

T

he brominated mass is transferred to the reactor for neutralizing the free HBr 20%

aqueous sodium bicarbonate solution and 20% aqueous solution of sodium

hydroxide. After neutralization, chlorobenzene is distilled off under vacuum.

EPT Reaction

4-Bromo-2-Chlorophenol (BCP) is condensed with diethyl

thiophosphoroamidochloride (DETC) in the presence of trimethylaminesulphate and

other catalysts. During the reaction, BCP reacts with DETC and forms 4-Bromo-2-

Chlorophenyl diethyl phosphorotheiate (EPT) and hydrochloric acid, which reacts

instantaneously with caustic and forms sodium chloride. After completion of the

reaction, settle the mass for 1hour at 15oC and then, a fore-cut of aqueous

trimethylamine is distilled and is recycled. The organic and aqueous layers are

separated. The time for this stage is about 12.5hours.

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TMA-EPT Reaction

The EPT formed is reacted with 30% TMA under controlled conditions to obtain

Ammonium salt of EPT. The temperature is maintained at 70oC for 6 hours. The

excess TMA is distilled off and the water and organic layers are separated. The

aqueous layer is sent to ETP and the organic layer, which consists of the Ammonium

salt of EPT, is transferred to another reactor for profenofos reaction. The time

needed for this stage is about 14 hours.

Profenofos Reaction & Purification:

The n-propyl bromide is added into the reactor where it reacts with the concentrated

ammonium salt of EPT and forms profenofos and n-propyl-ethyl ammonium bromide.

After completion of the reaction, the reaction mass is maintained at 60oC for 4 hours.

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The material is concentrated under vacuum and the excess n-propyl bromide is

recovered after concentration, Profenofos (Tech) is collected in drums. The final

purification including distillation requires 20 hours. The material balance for this

product (7.0MT/day) is presented in Table-II.3

Table-II.3: Material Balance for Profenofos Technical (7.0 MT/day)

Input Output

Sno Raw Material M. Wt.

Quantity / Ton (kgs)

Quantity / Day

Raw Material

M. Wt.

Quantity / Ton (kgs)

Quantity / Day

1 Phenol 93 857.14 6000 Profenofos 373.4 1000.0 7000 2 Bromine 179.9 485.00 3395 HBr (30%) 36.5 793.0 5551

3 DETPC 188.5 567.00 3969 NaBr(25%) 102.9 1945.0 13615 4 NaOH(48%) 40 506.00 3542 TMA 59 255.0 1785

5 NPB 123 350.00 2450 PCP 128.5 857.1 6000

6 TMA Sulfate - 25.00 175 Organic

res. 45.7 320 7 TMA 59 220.00 1540 HCl 25% 36.5 1857.1 13000

8 Water 18 2842.86 19900 0

9 Chlorine 71 900.00 6300

TOTAL 6753.00 47271 TOTAL 6753 47271

TMASulfate = Trimethyl Amine Sulfate; TMA = Tri methyl amine; DETPC = Diethyl Thyophosphoryl chloride; PCP = Para- Chloro Phenol ,

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Figure II.3 : Process flow diagram for Profenofos

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4.Propiconazole

Process Description:

The process involves 5 steps. i. Acetal formation. ii. Formation of bromoketal

compound iii. Neutralization of bromoketal mass iv. Propiconazole reaction v.

Purification of propiconazole. The process flow diagram is given in figure-II.4

2,4- Dichloroacetophenone (DiCAP) is reacted with pentane 1,2 diol (1,2PDL) to form

acetal compound in the presence of 1,2 - dichloroethane. Para toluene Sulphonic

Acid (PTSA) is used as a catalyst. Water, which is formed during the reaction, is

removed and PTSA remains in the aqueous layer.

The acetal compound is reacted with bromine to form bromoketal. A batch tank is

used to add bromine slowly to the acetal compound in 1,2-dichloroethane. The

required quantity of bromine is pumped from the bulk storage tank to the batch tank.

Hydrogen bromide gas evolves during the reaction and it is scrubbed with water to

obtain 30% HBr solution, which is sent to bromine recovery unit. The bromoketal

mass is neutralized with aqueous NaOH and the unreacted bromine reacts with

NaOH to form NaBr and NaBrO3. Then, the layers are separated. The aqueous layer

is sent to ETP for treatment. 1,2 dichloroethane is distilled off from the organic layer.

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The

solvent DMSO is added to bromoketal mass to accomplish reaction with triazole..

The bromoketal mass, which contains the impurities of acetal, is reacted with the

potassium salt of triazole. The potassium salt of triazole is obtained by reacting 1,2,4

triazole with potassium hydroxide. Water is formed along potassium triazole. After

completing the reaction to form propiconazole, DMSO along with water is distilled off

as a fore-cut. The crude propiconazole is extracted with hexane. Finally,

propiconazole is concentrated to the desired purity by distilling of n-hexane. As the

solubility of propiconazole in hexane is very low, large quantities of hexane are

required in purification step. The material balance for this product (3.0MT/day) is

presented in Table-II.4

Table-II.4: Material Balance for Propiconozole (PCZ) Technical (3.0 MT/day)

Input Output

Sno Raw Material M. Wt. Quantity / Ton (kgs)

Quantity / Day Raw Material M. Wt.

Quantity / Ton (kgs)

Quantity / Day

1 Di CAP 189 684.18 2052.5 PCZ 342 1137 3411

2 1,2 PDL 104 376.48 1129.4 HBr 81 287 861

3 Bromine 160 578 1734.0 Aqueous - I - 1945 5835

4 NaOH (48%) 40 140 420.0 Aqueous - II - 342 1026

5 1,2,4- Triazole 69 370 1110.0 Still Residue - 457.5 1372.5

6 Water 18 2020 6060.0 DMSO Loss 78 25 75

7 DMSO 78 25 75.0 Hexane loss 84 250 750

8 Hexane loss 84 250 750.0 Benzene loss 78 15 45

9 Benzene 78 15 45.0 0

Total 4458.66 13376.0 4458.5 13376

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Figure – II. 4 : Process flow drawing for Propiconazole

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5.Tricyclazole Process Description :

Tricyclazole, a systematic fungicide, controls the rice blast in transplanted and direct

seeded rice. It is safer and stable solid compound. The process flow diagram is given

in figure-II.5. The following are the process steps:

Formation of Aminobenzothiazole:

Orthotoludine is dissolved in chlorobenzene and is reacted with

ammoniumthiocyanate under reflux to form ortho toulyl urea. The liberated ammonia

reacts with sulfuric acid and ammonium sulfate is formed. The reaction mass is

reacted with chlorine 2-amino-4-methyl benzo thiozole. The off gas, HCl, is scrubbed

with water and is sold out as dilute hydrochloric acid. The product is filtered and the

solid product is taken for tricyclazole reaction. The chlorobenzene in the filtrate is

separated and recovered by distillation and aqueous salts are disposed as fertilizer.

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Tricyclazole reaction

Aminobenzothiozole is reacted with hydrazine hydrate in xylene solvent and then with

formic acid. The Unreacted formic acid is distilled out and is reused. The ammonia

liberated is scrubbed in water and is sent to the acephate production. After

completion of reaction, the product is filtered and washed with water. The washed

water is sent to MEE. The material balance for this product (2.0MT/day) is presented

in Table-II.5.

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Figure-II.5: Process Flow Diagram of Tricyclzole

Table-II.5: Material Balance for Tricyclozole Technical (2.0 MT/day)

Input Output

S.No Raw Material M. Wt.

Quantity / Ton (kgs)

Quantity / Day Raw Material M. Wt.

Quantity / Ton (kgs)

Quantity / Day

1 Orthotoluidine 107 626 1205.0 Tricyclazole 189 1039 2000.0

2 Ammonthiocyanate 76 445 856.6 HBr 45% 81 444 854.7

3 Bromine 160 404 777.7 DCE( Rec) 97 1950 3753.6

4 Dichloroethane(DCE) 97 2000 3849.9 Xylene( Rec) 106 1950 3753.6

5 Xylene 106 2000 3849.9 DCE Loss 97 50 96.2

6 Formic Acid 46 301 579.4 Xylene Loss 106 50 96.2

7 Hydrazine Hydrate 50 278 535.1 Aq. Waste 1340 2579.4

8 Water 18 864 1663.1 Ammonia 17 95 182.9 TOTAL 6918 13316.7 TOTAL 6918 13316.7

6. ISOXABEN

Process Description:

The process flow diagram is given in figure-II.6. The first step in the synthesis of

isoxaben is the esterification of 2-ethyl-2-methyl butyric acid (EMBA) with Iso Butyl

Alcohol (IBA) in toluene using p-toluene sulfonic acid (p-TSA) as the catalyst. After

washing the crude product with water, the aqueous phase is removed and the

organic phase is dried by azeotropic distillation. The azeotropic water and the acidic

aqueous solutions are mixed together as Aqueous I.

26

In the second step, the organic phase is reacted with Aceto Nitrile (AN) and a slurry

of Sodium Hydride (NaH) in Tetra Hydro Furan (THF). After reaction the product

ketonitrile is dissolved in water and is taken for next step.

In the third step, hydroxylamine sulfate is added to convert the ketonitrile to 5-

isoxazolamine, which is recovered by a toluene extraction.

In the fourth step, the other part of the molecule 2,6-dimethoxy benzoyl chloride

(DMBCl) is prepared by reacting 2,6-dimethoxybenzoic acid (DMBA) with Thionyl

Chloride in toluene. The off gases HCl and SO2 are scrubbed in water and dilute

caustic soda solution.

27

In the fifth step, the final coupling of the 2,6-dimethoxybenzoyl chloride with 5-

isoxazolamine is also carried out in toluene.

Filtering and drying isolate the product Isoxaben. The material balance for this

product (1.0MT/day) is presented in Table-II.6.

Table-II.6 Material Balance for Isoxaban Technical (1.0 MT/day)

Input Output

Sno Raw Material M. Wt. Quantity / Ton (kgs)

Quantity / Day Raw Material M. Wt.

Quantity / Ton (kgs)

Quantity / Day

1 EMBA 130.19 390.57 390.57 Isoxaben 332.41 992.24 992.24

2 Iso Butanol 74.12 224.59 224.59 EMBAEster 186.3 2.80 2.80

3 PTSA 192.2 2.88 2.88 Iso Butanol 74.12 2.22 2.22

4 Water 18.02 2816.29 2816.29 2,6, MBA 182.18 2.73 2.73

5 Toluene 92.1 225.00 225.00 Aqueous –I 176.00 176.00

6 Acetonitrile 41.05 122.53 122.53 Aqueous –II 1717.00 1717.00

7 NaH 24 72.36 72.36 Aqueous –III 2252.00 2252.00 8 T H F 72.1 40.00 40.00 Tolune loss 92.1 225.00 225.00 9

HXAS 164.15 492.46 492.46 THF loss 72.1 40.00 40.00 10

2,6-MBA 182.18 546.54 546.54 11

SOCl2 118.98 356.94 356.94

12 NaOH 40 120.00 120.00

Total 5410.16 5410.16

5410.00 5410.00

EMBA: 2-Ethyl-2-Methyl Butyric Acid; PTSA: p-Toluene Sulphonic Acid; NaH: Sodium Hydride; THF: TetraHydroFuran; HXAS: Hydroxyl Amine Sulphate; 2,6-MBA: 2,6-Methoxy Benzoic Acid; SOCl2 : Thionyl Chloride

28

Figure II.6 : Process Flow Diagram for Isoxaben

29

7. MYCLOBUTANIL

Process Description: The process flow diagram is given in Figure-II.7. Step 1

Para Chloro phenyl acetonitrile (PCAN) is reacted with N Butyl Bromide (NBB) in

presence of sodium hydroxide 48 % solution in water media to produce 2-Butyl-2-(4-

chlorophenyl) acetonitrile - (BCPA) After reaction, extra water is added, stirred and

organic is separated out. The crude BCPA is taken for next step. Aqueous sodium

bromide solution is sold out for bromine recovery.

Step 2 BCPA is then reacted with Dibromo methane (DBM) in presence of sodium hydroxide

48% solution in water as solvent media; to produce 2-Butyl -2-chloromethyl-2-(4-

chlorophenyl) acetonitrile (BCAN) BCAN is worked up by addition of water and layers

separated. The aqueous layer is sold to outside parties for Bromine/Bromide

recovery. The organic layer containing BCAN is isolated and taken for final

Myclobutanil reaction.

Step 3 BCAN is reacted with sodium 1,2,4 Triazole in solvent media dimethyl formamide

(DMF) to produce final product Myclobutanil. DMF is distilled out from the reaction

mass, and water is added and mass filtered.

30

Table-II.7: Material Balance for Myclobutanil Technical (1.5 MT/day)

Input Output

S.No. Raw Material M. Wt. Quantity / Ton (kgs)

Quantity / Day Raw Material M. Wt.

Quantity / Ton (kgs)

Quantity / Day

1 PCAN 151.5 549.9 795.21 Miclobutanil 288.8 1000.0 1446

2 NBB 137

497.4 719.28 CCHB 300.5

15.9 22.95

3 NaOH 40

145.2 210 CCP – 207.5

11.1 16.08

4 Water 18

4416.3 6386 PCAN 151.5

8.3 11.94

5 PTC

4.0 5.79 Aqueous I

1848.0 2672.16

6 DBM 174

9.3 13.47 Aqueous II

1820.3 2632.2

7 NaOH 40

143.0 206.85 Aqueous III

1376.7 1990.74

8 PTC

3.9 5.7 DMF Loss

100.2 144.9

9

Na 1,2,4 Triazole

91

320.5 463.5

DBM Loss 174

9.3 13.47

10 DMF 100.2 144.9

Total 6190.0 8950.7 Total 6189.8 8950.44

PCAN : p-Chloro Phenyl Aceto Nitrile; NBB: n-Butyl Bromide; DBM=Dibromomethane; DMF:Dimethyl Formamide

31

Figure –II.7 : Process Flow Diagram for Myclobutanil The filtrate is sold to outside parties for Bromine/Bromide recovery and cake

containing final product MYCLOBUTANIL ( - butyl - - (4 chlorophenyl) - 1H -

1,2,4 - triazole - 1- propanenitrile) is dried and packed. The material balance for this

product (1.5MT/day) is presented in Table-II.7.

8. PRETILACHLOR Process Description: The process flow diagram is given in Figure-II.8 CPE Formation Propoxy ethanol will be reacted with SOCl2 to form chloropropoxy ethane. Off gases

SO2 and HCl will be scrubbed.

32

PEDA formation 2,6 Diethylaniline (DEA) is reacted with Chloro Propoxy Ethane (CPE) to give

intermediate N Propoxy Ethyl 2,6 Diethyl Aniline hydrochloride (PEDA.HCl) at 130

deg C. After the reaction, Reaction mass is neutralised with caustic at room

temperature upto pH 7.0. Aq.layer containing NaCl is separted out and organic layer

PEDA is washed with water and taken to the Pretilachlor reaction.

Pretilachlor Formation:

The crude PEDA is washed with water and caustic & NaCl solution is separated and

sold out. The organic layer (PEDA) is taken into solvent toluene and chloro acetyl

chloride is gradually added in presence of TEA to the form pretilachlor at 60 deg C.

After reaction, the mass is filtered and the product is concentrated.

33

The solid TEA.HCl is neutralized by NaOH and TEA is recovered. Aqueous waste

concentrated and the salt Nacl is sent for softener regeneration. Pretilachlor after

removal of toluene is packed. The material balance for this product (6.5MT/day) is

presented in Table-II.8.

Table-II.8: Material Balance for Pretilachlor Technical (6.5 MT/day)

Input Output

Sno Raw

Material M. Wt.

Quantity / Ton (kgs)

Quantity / Day Raw Material

M. Wt.

Quantity / Ton (kgs)

Quantity / Day

1 2,6DEA 149 476 3093 Pretilachlor 311.5 975.2 6338.6

2

Propoxy Ethanol

104

277 1800

PEDA 235

7.5 48.8

3 NaOH 40 253 1647 2,6 DEA 149 4.8 30.9

4 CAC 113 361 2344 CPE 122.5 5.3 34.7

5 Toluene 92 25 165 C A C 113 7.2 46.9

6 TEA 101 17 108 Aq.Waste 1033.0 6714.5

7 Water 18 1642 10672 Nacl 58.5 185.0 1202.5

8 SOCl2 119 381 2479 TEA Loss 101 16.7 108.3

9 Water 18 56.7 368.3

10 Nacl 58.5 183.1 1189.9

11 TolueneLoss - 25.4 165

12 HCl 36.5 735.4 4780

13 SO2 64 196.9 1280

Total 3432 22308 3432 22308

2,6 DEA: 2,6,Diethyl Aniline; CPE: ChloroPropoxy Ethane; CAC: ChloroAcetyl Chloride; PEDA: N Propoxy Ethyl 2,6 Diethyl Aniline

34

Figure-II. 8 : Process Flow Diagram for Pretilachlor

35

9. 4 H BAGE 4HBAGE is manufactured in two steps. The process flow diagram is given in Figure-

II.9. In the first step, 1,4-Butanediol is reacted with Epichlorohydrin in the presence

of sodium hydroxide.

The product 1,4-BDMGE is purified by fractional distillation under vacuum. This

product is reacted with monomethyl acrylate, isolated and distilled under vacuum to

get 4HBAGE. The material balance for this product (0.5MT/day) is presented in

Table-II.9.

Figure – II.9: Process Flow Diagram for 4HBAGE

36

Table-II.9: Material Balance for 4HBAGE Technical (0.5 MT/day)

Input Output

Sno Raw Material M. Wt. Quantity / Ton (kgs)

Quantity / Day Raw Material M. Wt.

Quantity / Ton (kgs)

Quantity / Day

1 1,4 BDL 90.12 2181.8 1200 4HBAGE 200.2 1000.0 5502 EPCH 92.5 3636.4 2000 Tolune loss 92 363.6 2003 NaOH 48% 40 2181.8 1200 Hexane loss 86 545.5 3004 Water 18 7636.4 4200 Aqueous - I - 10009.1 55055 Toluene 92 363.6 200 Aqueous - II - 4552.7 25046 Hexane 86 545.5 300 NaOH 48% 40 2181.8 12007 Methylacrylate 86.1 2727.3 1500 Organic residue - 727.3 4008 TBT - 90.9 50 9 MEHQ(Catalyst) - 9.1 5 10CBC - 7.3 4

Total 19380.0 10659 19380.0 10659

1,4 BDL:1,4-Butanediol; EPCH : Epichlorohydrin; TBT: Tetra-N-Butoxy Titanium; MEHQ :

CBC : Copper Dibutyl-Dithiocarbamate ;

10. DAAM

Process description : The process flow diagram is given in Figure-II.10.

DAAM Reaction: Di Acetone Alcohol is reacted with Acrylonitrile in the presence of

H2SO4 (98%) will form DAAM crude. (Reaction Temp: 100C.)

DAAM Neutralization : H2SO4 reacts with Ammonium Hydroxide (NH4OH) will form

Ammonium Sulphate solution. Excess water will be removed by evaporation.

(Neutralization Temp: 250C to 300C)

37

DAAM Hydrolysis : Impurities of DAAM (AAM and TBAM) will hydrolyze at 700C

temp and separated into aqueous.

DAAM Extraction and Toluene Recovery : Crude DAAM washed with n-Hexane

and extracted by Toluene and aqueous will be separated. Toluene is distilled out to

get DAAM.(Temp 600C & Vacuum : 740 mm/Hg)

Product Distillation : DAAM will be purified by fractionation. Fore cut and last cut

shall be discarded. The temperature is maintained at 1020C under vacuum of: 758

mm/Hg.). The material balance for this product (0.75MT/day) is presented in Table-

10.

Table-II.10: Material Balance for DAAM Technical (0.75 MT/day)

Input Output

Sno Raw Material M. Wt. Quantity / Ton (kgs)

Quantity / Day Raw Material M. Wt.

Quantity / Ton (kgs)

Quantity / Day

1 DAA 116 975 731.25 Final product 169 900 675

2 ACN 53 623 467.25 Fore Cut - 50 37.5

3 H2SO4 (96%) 98 2100 1575 Last cut - 50 37.5

4 Water - 18 5150 3862.5 Aquous stream I - 7806 5854.5

5 Ammonia(25%) 17 2800 2100 Aquous stream II - 2654 1990.5

6 0 Tolune loss 92 200 150

7 Toluene 92 200 150 Organic residue 188 141

Total 11848 8886 11848 8886

DAA: Di Acetone Alcohol; ACN : Acrylonitrile

38

Figure –II.10: Process Flow Diagram for DAAM

11. FENBUCONAZOLE The process flow diagram is given in Figure-II.11.The first step in the synthesis is the

reaction of p-chlorostyrene (p-CS) with an excess of benzyl cyanide (BC) in dimethyl

sulfoxide (DMSO) .

The reaction is complete in a matter of minutes at 70-90oC. The DMSO is striped off.

The excess BC is removed by steam distillation and the residue Intermediate I

product is dissolved in dichloromethane (DCM). The organic phase is then washed

with water. The 53% solution of intermediate I in DCM is transferred to the next step.

39

The second step is the alkylation of intermediate I with DCM to make intermediate II

using phase transfer catalysis. The DCM solution of intermediate I from the first step

is slowly added to a mixture of DCM, and a phase transfer catalyst. The DMSO is

stripped off, the crude product is dissolved in xylene at 80oC.

The final purification step is crystallization form the xylene by cooling below 5oC. The

product is recovered by filtering washing first with xylene then isopropanol. The

normal purity of technical fenbuconazole is 97% coming out. The material balance for

this product (0.75MT/day) is presented in Table-II.11.

Table- II.11: Material Balance for Fenbucanazole Technical (0.75 MT/day)

Input Output

S no Raw Material M. Wt.

Quantity / Ton (kgs)

Quantity / Day Raw Material M. Wt.

Quantity / Ton (kgs)

Quantity / Day

1 BC 117 408.7 306.5 Fenbucanazole 336.54 1000.0 750.0 2 Chloro styrene 138.5 489.4 367.0 HCl (25%) 36.5 480.8 360.6 3 DCM 85 300.9 225.7 Aqueous - 6688.5 5016.3 4 Water 18 6666.7 5000.0 Xylene loss 106 160.0 120.0 5 Na.1,2,4Triazole 91 303.7 227.8 Organic residue - 240.0 180.0 6 Xylene 106 266.7 200.0 7 DMSO 133.3 100.0

Total 8569.3 6427.0 Total 8569.3 6427.0

40

Figure –II.11: Process Flow Diagram for Fenbucanazole 12. THIFLUZAMIDE The process flow diagram is given in Figure-II.12. The first step in the synthesis of thifluzamide is chlorination of freshly distilled ETFAA. The ETFAA needs to be distilled slowly before use because the molecule tens to form a dimmer upon standing.

The ETFAA is reacted with chlorine gas in the absence of any solvent. After warming to

ambient temperature and purging dissolved HCl with nitrogen, the CI-ETFAA is isolated

without further purification as a colorless oil.