eia final -1st - nacl industries limited
TRANSCRIPT
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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 -
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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 ,
19
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.
25
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.