CLEANER PR PESTICIDE M Gujarat (Establish ENVIS Ce Supporte Governm Block No Phone: + Mail: gcp WebsiteRODUCTION GUIDELINE MANUFACTURING SECT t Cleaner Production Centre hed by Industries & Mines Department, GoG) entre on: Cleaner Production/Technology ed by: Ministry of Environment, Forest & Climate Change ment of India o: 11-12, 3 rd Floor, Udhyog Bhavan, Gandhinagar + 91 (079) 232 44 147 [email protected]; [email protected]; : www.gcpcgujarat.org.in, www.gcpcenvis.nic.in ES IN TOR e,
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CLEANER PRODUCTION GUIDELINES IN
PESTICIDE MANUFACTURING SECTOR
Gujarat Cleaner Production Centre(Established by Industries & Mines Department,ENVIS Centre on: Cleaner Production/TechnologySupported byGovernment of IndiaBlock NoPhone: + 91 (079) 232 44 147Mail: [email protected]: www.gcpcgujarat.org.in, www.gcpcenvis.nic.in
CLEANER PRODUCTION GUIDELINES IN
PESTICIDE MANUFACTURING SECTOR
Gujarat Cleaner Production Centre(Established by Industries & Mines Department, GoG)ENVIS Centre on: Cleaner Production/TechnologySupported by: Ministry of Environment, Forest & Climate Change, Government of IndiaBlock No: 11-12, 3rd Floor, Udhyog Bhavan, Gandhinagar
General Cleaner Production Options During Manufacturing of Pesticide
Meter and control the quantities of active ingredients to minimize wastage.
Reuse by-products from the process as raw materials or as raw material substitutes in
other processes.
• Use automated filling to minimize spillage.
• Use “closed” feed systems for batch reactors.
Use nitrogen blanketing where appropriate on pumps, storage tanks, and other
equipment to minimize the release of toxic organics.
Give preference to nonhalogenated and nonaromatic solvents where feasible.
Use high-pressure hoses for equipment cleaning to reduce wastewater.
Use equipment washdown waters and other process waters (such as leakages from pump
seals) as makeup solutions for subsequent batches.
Use dedicated dust collectors to recycle recovered materials.
• Vent equipment through a recovery system.
Maintain losses from vacuum pumps (such as water ring and dry) at low levels.
Return toxic materials packaging to the supplier for reuse or incinerate/destroy in an
environmentally acceptable manner.
Minimize storage time of off-specification products through regular reprocessing.
Find productive uses for off-specification products to avoid disposal problems.
Minimize raw material and product inventory to avoid degradation and wastage that
could lead to the formation of inactive but toxic isomers or by-products.
Label and store toxic and hazardous materials in secure, bunded areas.
In case of formulation industries, the levels of wastewater generation are either
considerably lower than in the ‘technical’ production or sometimes non-existent. It is
observed that most of these industries do not generate any process wastewater.
Best Available Waste Minimization Methods For Manufacturing Aspects
Waste Stream Waste Minimization Method
EquipmentCleaning Wastes
Maximize production runs. Store and reuse cleaning wastes. Use of wiper blades and squeegees. Use of low-volume, high-efficiency cleaning. Use of plastic or foam “pigs.”
Spills and AreaWash downs
Use of dedicated vacuum system. Use of dry cleaning methods. Use of recycled water for initial cleanup. Actively
involved supervision.
Off-SpecificationProducts
Strict quality control and automation. may be reprocessed at appropriate stage, to recover the product.
Containers
Return containers to supplier and or reuse as directed.
Triple rinse containers. Drums with liners versus plastic drums or bags.
Segregating solid waste.
Air Emissions
Control bulk storage air emissions. Dedicate dust collection systems. Use automatic enclosed cut-in hoppers. Eliminate emissions of ammonia from reaction of
anhydrous ammonia and phosphoric acid. Miscellaneous Wastewater
Streams Pave high spillage areas.
Process washwater
Where multiple washings in a reaction are involved, each cycle wash water to be stored and used in subsequent batches.
Steam condensatefrom ejectors
Many places this water can be used as wash water, without affecting the process.
Steam condensate can also be explored for boiler feed .
Vacuum pumpseal water
Use double stage pumps and recycle seal water rather than using as once flow system.
Process changes Improvements possible by changing reaction
conditions, solvents elimination, reduction in processing steps, etc.
Conversion ofwastes into useful
products
Absorption of HCl gases with chilled water to get HCL acid
Spent H2SO4 from Nitrations to be used for SSP
production. Absorb NH3 in chilled water to get aqueous
Ammonia. Emulsions and rag
formation inreactions
Use of de-emulsifiers and resins for proper separation of organic and aqueous layers and reduce the carryover of organics and rag in aqueous layers.
SolventExtraction
Extraction of aqueous waste layers by suitable solvents to recover
Clean Technologies and Methods for Recovery of Pollutants
SR. No.
Identified Priority
PollutantsControl System
ExpectedEfficiency
TechnicallyAchievable
average Conc.
(mg/Nm3)
CostRs/Lacs
1. HCl � Water Scrubber� Caustic Scrubber� Water/Caustic Scrubber
90 %99 %99%
8.6517.57.0
9.3713.404.11
2. Cl2 � Caustic Scrubber� Water/Caustic Scrubber
99 %99 %
0.150.01
3.164.06
3. CH3Cl � Liquification & Recovery System� Incineration after distillation
99 %
99 %
Ni
-
107.5
-
4. H2S � Scrubber with NaOCL media� Scrubber with NaOH media� Charcoal Scrubber
96 %
99 %
97 %
8.5
0.43
5.6
57.7
11.3
11.3
5. SO2 � Water Scrubber� Water Scrubber (Ring jet scrubber) + Mist Eliminator + Demister� Mist Eliminator
96 %98 %
99 %
-12.64
1.1
7.720.0
0.8
6. NH3 � Two Stage Water Scrubber� Recovery System
98 %
99 %
26.2
-
23.4
79.4
7. HBr � Caustic Scrubber 98 % 11.7 5.84
8. CH3OH Channelised Emission was not observed
Product wise Cleaner Production Options
Product Cleaner Production Options
Monocrotophos In the manufacturing process of Monocrotophos, chlorination efficiency can be improved by providing multiple entries of chlorine in the reactor. Process conditions are to be optimized to minimize formation of dichlorides of Monocrotophos Aceto Acetamide (MMA), which are, resulting in formation of other products going in the waste. Purer Trimethyl Phosphite (TMP) is to be used to minimize input of impurities coming along with TMP leading to waste.
Profenophos In the manufacturing process of Prefenophos, efficiency of bromination needs to be improved by adopting stagewise bromination and optimizing the process parameters. This will minimize formation of other bromides and impurities, which form waste. Recovery of Trimethyl Ethyl Amine Bromide (TMEABr) from aqueous layer will reduce the load on ETP and presence of organic impurities in ETP sludge.
Acephate In the manufacturing process of Acephate, lower overall efficiency of the process and lower recovery efficiencies for solvent are leading to waste. There is a scope to optimize process efficiency and improve solvent recovery system and thereby reduce the waste.
Chloropyrophos In Chlorpyriphos manufacturing process, lower extraction efficiency isresulting in loss of Chlorpyriphos in the waste. Use of centrifugal extractors with optimized process conditions will improve extraction of Chlorpyriphos and thereby reduce the waste.
Ethion In the manufacturing processof Ethion, direct controlled addition of P2S5 in alcohol and elimination of solvent may result in total elimination of process waste.
Zinc/Aluminiumphosphide
In the manufacturing process of phosphides of zinc and aluminium part of the phosphorous is burnt for generating high temperature. This in turn results in generation of waste. Developing an electric arc furnace will solve this problem. Dusting of the product also needs to be minimized.
Endosulfan In the manufacturing process of Endosulfan, recovery of Endosulfan needs to be improved by improving centrifugation and thereby reducing Endosulfan in the waste
Cypermetharin In Cypermethrin manufacturing process, there is a scope to reduce thequantity of sodium cyanide used and thereby reduce the load ondetoxification and generation of detoxification sludge.
Fenvalerate In the manufacturing process of Fenvalerate, better heat transfer andtemperature control will reduce the loss of alkyl in alkyl distillation. Use of acidic ion exchange resin can minimize requirement of acid and thereby generation of waste.
Malathion In the manufacturing process of Malathion and Dimethoate, minimizing water content of methanol, P2S5 and equipment will minimize generation of phosphoric acid, which results in formation of waste.
Dimethoate Drying of Malathion and Dimethoate at lower temperature, using higher vacuum will reduce thermal degradation of the product.