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Pesticides and Fertilizer Industry
Submitted By: Akhil Krishnan R: 0001 Asith K.A:0009 Kimi Garg:0017 Sandeep Samisheety:0028
Submitted To: Pavan Kumar Mandapaka Dept of HSE UPES
INTRODUCTION A pesticide is any substance or mixture of substances intended for:
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preventing, destroying, repelling, or Mitigating any pest. Though often misunderstood to refer only to insecticides, the term pesticide also applies to herbicides, fungicides, rodenticides, molluscicides and various other substances used to control pests. Under United States law, a pesticide is also any substance or mixture of substances intended for use as a plant regulator, defoliant, or desiccant. Man employs pesticides as powerful environmental contaminants in order to improve environmental quality for himself and his domesticated animals and plants. In agriculture, pesticides are used to increase the cost/benefit ratio in favor of the farmers.In developing countries where food supplies are marginal, pesticide use may represent the margin between survival and starvation. In surveying the role of pesticides in environmental quality it must be considered that pests themselves generally affect adversely the quality of the environment. The spectrum ranges from a mosquito in the bedroom or a cockroach in the pantry to a plague of locusts or the tsetse flies. Therefore it must be recognized that the purposeful environmental contamination by pesticides generally provides environmental benefits substantially greater than the risk of environmental pollution. Presently, India has about 675 pesticides industries manufacturing about 75000 tonnes of pesticides. The pesticides industry has been identified as one of the highly polluting industries needing pollution control on priority. Many household products are pesticides. All of these common products are considered pesticides:
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Cockroach sprays and baits; Insect repellents for personal use; Rat and other rodent poisons; Flea and tick sprays, powders, and pet collars; Kitchen, laundry, and bath disinfectants and sanitizers; Products that kill mold and mildew; Some lawn and garden products, such as weed killers; and Some swimming pool chemicals.
Pyrethroid Pesticides were developed as a synthetic version of the naturally occurring pesticide pyrethrin. Carbamate Pesticides affect the nervous system by disupting an enzyme that regulates acetylcholine. Some are very poisonous (they were used in World War II as nerve agents). and pest control devices.These pesticides affect the nervous system by disrupting the enzyme that regulates acetylcholine. they usually are not persistent in the environment. Another way to think about pesticides is to consider those that are chemical pesticides or are derived from a common source or production method. There are several subgroups within the carbamates. y y y Pesticides Manufacture Pesticides include insecticides. Most organophosphates are insecticides. weedicides. y Organophosphate Pesticides . lavigated clay and hydrated calcium silicate (called inert).g. They have been modified to increase their stability in the environment. They were developed during the early 19th century. a neurotransmitter. The enzyme effects are usually reversible. However. Some synthetic pyrethroids are toxic to the nervous system. antimicrobials. rodenticides and plant growth regulants. There are many formulations used in manufacturing of pesticides. Other categories include biopesticides. Organochlorine Insecticides were commonly used in the past. which is found in chrysanthemums. but many have been removed from the market due to their health and environmental effects and their persistence (e. such as soapstone. Other examples are available in sources such as Recognition and Management of Pesticide Poisonings. They are: Dusting Powders (DP): The basic pesticides are mixed with a mineral base. Chemical Pesticides Some examples of chemically-related pesticides follow. were discovered in 1932.TYPES OF PESTICIDES Pesticides are often referred to according to the type of pest they control. 3 . which are similar to their effects on humans. fungicides. a neurotransmitter. DDT and chlordane). but their effects on insects.
Calcium silicate is used as adsorbent. butanol. Emulsified Concentrates (EC): The Emulsified Concentrates have three components consisting of basic pesticide. Emulsifiers used are polyoxyethylene. alkyl aryl sulphonate. including nontarget species. thereby reducing hazards to the operators. solvent and emulsifier. the pesticides industries may realize that there is wide scope in reducing the quantities of water usage and wastewater generation which may effect in reduction in cost of treatment. The unit operations. These concentrates give emulsions when diluted with water. Hence it is difficult to summarize a specific limit for water use and wastewater generation as done for other industries. stabilizer (3rd stage) Solvent (1st stage) Vessel Filter Packaging Basic pesticide (2nd stage) Wastewater Generation in Pesticide Industry: The entire manufacturing process for a particular product is a combination of various unit operations. triethanolamine and urea. air. ether. water. bottom sediments. Sometimes a stabilizer is also used. and food.Granules: The granule formulation consists of absorptive granular carrier (clay) containing solution of basic pesticide adsorbed on the surface. Environmental effects of pesticides Over 98% of sprayed insecticides and 95% of herbicides reach a destination other than their target species. Stabilizers used are epichlorohydine. Emulsifier. However. In view of the wide variety of process technology options. cyclohexane and xylene. 4 . the quantity of water used and waste water generation are widely varying from product to product and industry to industry. are to be identified so as to accurately identify the characteristics of wastewater generated. The granules need no further dilution and have easier application. where water is used and wastewater is generated. Solvents used are aromex.
Pesticide contaminates land and water when it escapes from production sites and storage tanks.Factors that affect a pesticide's ability to contaminate water include its water solubility. Some pesticides contribute to global warming and the depletion of the ozone layer. its vapor pressure. methyl parathion. The use of pesticides decreases the general biodiversity in the soil. Plants Nitrogen fixation. Pesticides that are applied to crops can volatilize and may be blown by winds into nearby areas. sometimes killing all the fish in a particular stream. weather. when it runs off from fields. Soil Many of the chemicals used in pesticides are persistent soil contaminants. and the method used to apply the chemical. its water solubility. the distance from an application site to a body of water. soil type. is hindered by pesticides in soil. The insecticides DDT. or leach. Pesticide surface runoff into rivers and streams can be highly lethal to aquatic life. because organic matter binds to and helps break down pesticides. Water There are four major routes through which pesticides reach the water: it may drift outside of the intended area when it is sprayed. when it is sprayed aerially. A smaller content of organic matter in the soil increases the amount of pesticide that will leave the area of application. and especially pentachlorophenol have been shown to interfere with legume-rhizobium chemical signaling. it may be carried to the water as runoff. and its resistance to being broken down over time. whose impact may endure for decades and adversely affect soil conservation. which can react with other chemicals and form a pollutant called ozone. Droplets of sprayed pesticides or particles from pesticides applied as dusts may travel on the wind to other areas or pesticides may adhere to particles that blow in the wind. Air Pesticides can contribute to air pollution. or it may be spilled. They may also be carried to water by eroding soil. through the soil. Pesticides that are sprayed onto fields and used to fumigate soil can give off chemicals called volatile organic compounds. Aquatic life Fish and other aquatic biota may be harmed by pesticide-contaminated water. which is required for the growth of higher plants. presence of a growing crop. 5 . and when it is sprayed into water to kill algae. it may percolate. Not using the chemicals results in higher soil quality. such as dust particles. The amount of pesticide that migrates from the intended application area is influenced by the particular chemical's properties: its propensity for binding to soil. when it is discarded. potentially posing a threat to wildlife.
Exposure to pesticides can range from mild skin irritation to birth defects. Insecticides are more toxic to aquatic life than herbicides and fungicides. Humans Pesticides can enter the human body through inhalation of aerosols. genetic changes. causing the fish to travel farther in search of food and exposing them to greater risk from predators. tumors. especially fruits and vegetables. But every human contains a percentage of pesticides found in fat samples in their body. Repeated exposure to sublethal doses of some pesticides can cause physiological and behavioral changes in fish that reduce populations. The effects of pesticides on human health are more harmful based on the toxicity of the chemical and the length and magnitude of exposure. suffocating the fish. Pesticides can accumulate in bodies of water to levels that kill off zooplankton.Application of herbicides to bodies of water can cause fish kills when the dead plants rot and use up the water's oxygen. decreased immunity to disease. and increased failure to avoid predators. such as abandonment of nests and broods. and through dermal exposure by direct contact of pesticides with skin. Children are most susceptible and sensitive to pesticides due to their small size and underdevelopment. through oral exposure by consuming food and water. the main source of food for young fish. The chemicals can bioaccumulate in the body over time. Farm workers and their families experience the greatest exposure to agricultural pesticides through direct contact with the chemicals. that are applied to water to kill plants are toxic to fish and other water animals at concentrations similar to those used to kill the plants. such as copper sulfite. endocrine disruption. they secrete into soils and groundwater which can end up in drinking water and pesticide spray can drift and pollute the air. Pesticides are sprayed onto food. The faster a given pesticide breaks down in the environment. Some herbicides. 6 . Application of herbicides to bodies of water can kill off plants on which fish depend for their habitat. blood and nerve disorders. and even coma or death. the less threat it poses to aquatic life. Pesticides can kill off the insects on which some fish feed. dust and vapor that contain pesticides.
overflow and evaporation of toxic volatile matter into the atmosphere 7 .Wastewater Treatment: Existing Treatment Facilities: The flow diagrams of wastewater treatment adopted in some of the industries are shown below Observations on Existing Treatment Systems: The problems associated with the present wastewater treatment options adopted by the industries are as follows: A. Solar Evaporation System The solar evaporation system has limitations based on quantity of effluent and climatic condition at the site. The effluent in the evaporation tanks if not a leachate-proof holding arrangement. may cause pollution by virtue of precolation.
it is required to manage the wastewater very effectively such that he waste is minimized. unless properly segregated. bear high dissolved solids thus affecting the biological treatment. Disposal of Wastewater: From the point of wastewater discharge various industries it is observed that wastewater is disposed to y On land for irrigation y Public drain/sewer/nullah y River/creek y Sea y Solar evaporation tanks(within factories limit) Choosing the mode of disposal for treated effluent is very important in view of the toxic nature of effluent. cost in treatment and risk due to pollution are lowered and the environment is protected. Wastewater Management: The conventionally adopted end-of-the-pipe treatment technology is not only ineffective but is also costly. The level of treatment required is to be decided based on the actual quality of the receiving body. daily. whereas the ASP(Activated Sludge Plant) type of biological treatment system needs a relatively uniform rate of organic loading and without shock loads due to toxicity. non-uniform flows etc.B. in view of the effluent and the complexity of the pollution problem from the pesticides industries. Under extreme climatic conditions. Biological Treatment System The characteristics and the quantity of wastewater in a pesticides industry are varying from products to products and also seasonally. and hourly. Also. The wastewaters. biological treatment does not work efficiently as the microbes find difficulty in surviving. Various aspects for an effective wastewater management are: y Location of the plant y Plant layout y Waste minimization y Reduction of Raw Material Losses y Recycling and Reuse of Wastewater y In-plant Control y Treatment Control y Waste Segregation and Pretreatment 9 .
Most solids can be removed using simple sedimentation techniques with the solids recovered as slurry or sludge. Equalized and steady flows are very important for improved efficiency. The common physical methods are flow equalization. sedimentation with or without coagulation. filtration and adsorption. Oils and grease removal Many oils can be recovered from open water surfaces by skimming devices. flocculation may be used. skimming is also a cost-efficient method to remove most of the oil before using membrane filters and 10 . oil and grease removal. grease and other hydrocarbons from water. and biological methods. using alum salts or the addition of polyelectrolytes. sludge removal. Considered a dependable and cheap way to remove oil.Effluent treatment Plant: The treatment of liquid wastes can be achieved by employing physical. At other times. chemical. In such case filtration or ultrafiltration may be required. Although. oil skimmers can sometimes achieve the desired level of water purity. reliability and control of treatment plant. Very fine solids and solids with densities close to the density of water pose special problems.
y Protection of micro-organisms in biological treatment system. Eg: DDT y Aliphatic compounds are in general more degradable than aromatic. y Halogen substitution to an aromatic compound renders it less degradable. producing a waste sludge (or floc) containing the oxidized material. y Protection of system organisms. These are: y Compounds in emulsified form are not readily available to micro-organisms.chemical processes. Hydraulic oils and the majority of oils that have degraded to any extent will also have a soluble or emulsified component that will require further treatment to eliminate. producing wastewater that is more difficult to treat. Stabilization ponds. oxidation. Dissolving or emulsifying oil using surfactants or solvents usually exacerbates the problem rather than solving it. The biological methods used for pesticide containing wastewater include: y y y y Trickling filters. Skimmers will prevent filters from blinding prematurely and keep chemical costs down because there is less oil to process. Activated sludge process: Activated sludge is a biochemical process for treating sewage and industrial wastewater that uses air (or oxygen) and microorganisms to biologically oxidize organic pollutants. Biological treatment: It includes aerobic treatment and anaerobic treatment. y Reaction control on many chemical treatment processes.It is required for: y Corrosion control.5.5-8. In general. detoxification etc. an activated sludge process includes: y An aeration tank where air (or oxygen) is injected and thoroughly mixed into the wastewater. 11 . Activated sludge process. The chemical treatment includes neutralization. if direct discharge is employed. Some of the factors affect the biodegradability. Neutralization is required to maintain a pH of 6. Aerated lagoons.
12 . peat moss. The process involves adsorption of organic compounds in the wastewater by the microbial slime layer. Marine coastal water. gravel. trickling biofilter. As the slime layer thickens. Trickling filter process: A trickling filter consists of a bed of rocks. diffusion of air into the slime layer to provide the oxygen required for the biochemical oxidation of the organic compounds. Firm should incorporate the Monitoring system to evaluate the performance of the pollution control systems. slag. gardening/irrigation purpose or disposed. the treated wastewater should confirm to the CPCB. For any of these disposals. water and other products of the oxidation. biological filter or biological trickling filter. it becomes difficult for the air to penetrate the layer and an inner anaerobic layer is formed. or plastic media over which wastewater flows downward and contacts a layer (or film) of microbial slime covering the bed media. Inland surface water. The treated wastewater may be disposed to: y y y Public sewer. Disposal of Treated Wastewater: The treated wastewater may be for floor wash. An enclosure or a container which houses the bed of filter medium. Aerobic conditions are maintained by forced air flowing through the bed or by natural convection of air. A system for distributing the flow of wastewater over the filter medium. Part of the waste sludge is recycled to the aeration tank and the remaining waste sludge is removed for further treatment and ultimate disposal. A system for removing and disposing of any sludge from the treated effluent. The treatment of sewage or other wastewater with trickling filters is among the oldest and most well characterized treatment technologies. The components of a complete trickling filter system are: fundamental components: y y y y A bed of filter medium upon which a layer of microbial slime is promoted and developed. A trickling filter is also often called a trickle filter. The end products include carbon dioxide gas.y A settling tank (usually referred to as a "clarifier" or "settler") to allow the waste sludge to settle. It must also evaluate the impact of the disposed wastewater on the receiving environment.
and the scarcity of heath care facilities especially in the rural areas where most of the agricultural activities occur. 13 .Strategies for reducing agricultural pesticide contamination Several strategies that have been suggested to reduce agricultural pesticide contamination and its effects include comprehensive risk communication and education programs. While the need exists to prevent or reduce agricultural pesticide contamination and its effects world-wide. Pests can be prevented by removing pest breeding sites. 2. 9. and the adoption of Integrated Pesticide Management (IPM). 1. crop rotation that may disrupt the life cycle of pests. and use biocontrol agents such as birds and other pest eating organisms. and biological control such as the use of insect predators. There are a variety of alternative pesticides such as manually removing weeds and pests from plants. special attention needs to be paid to developing countries for several reasons. the adverse human health effects of pesticide poisoning are particularly high in many of these countries because of the low nutritional status. Eliminating Pesticides Due to the toxic effect caused by the pesticides upon the environment some of them are banned from normal use in India. 5. 3.No. 8. applying heat. They are as follows: PESTICIDES RESTRICTED FOR USE IN INDIA S. Name of Pesticides Aluminium Phosphide DDT Methyl Bromide Methyl Parathion Sodium Cyanide Methoxy Ethyl Mercuric Chloride (MEMC) Monocrotophos Endosulfan Fenitrothion Diazinon Many alternatives are available to reduce the effects pesticides have on the environment. Also. 6. 4. the discontinuation of calendar spraying. selection of disease-resistant hybrids. maintaining healthy soils which breed healthy plants that are resistant to pests. 7. planting native species that are naturally more resistant to native pests. 10. IPM emphasizes non-chemical and cultural cultivation pest control strategies such as removal of diseased plant parts. the use of appropriate personal protective clothing. covering weeds with plastic and placing traps and lures to catch or move pests.
Diammonium phosphate etc Phosphatic fertilizers like single super phosphates and triple super phosphates These fertilizers need a variety of raw materials and intermediates like natural gas . 6% use imported ammonia an 1% use other sources. 4%use coal. feedstock used.FERTILISER MANUFACTURING INDUSTRY INTRODUCTION India is one of the largest Nirtogen fertilizer producer in the world. Lime sludge. The major air emissions are SO2. fuel oil etc. Major liquid effluents are nitrogen and urea nitrogen. However there are some old industries which follows old and outdated methods and machine which does not help in optimization of emissions 14 . Fluorides and phosphates. Gypsum. Fly-ash. Natural gas. The industry faces a problem of utilization/disposal of waste generated in fertilizer production namely Phospho-gypsum. Fertilizers can be divided into three categories: I. Electrolysis of water. which needs a variety of feedstocks like Lignite. hard coke. Associated gas. fertilizer industry too produces some gaseous/liquid/solid effluents depending upon the technology adopted. technology and methods used by industries are becoming more and more sophisticated which will help to decrease the emissions and improve the fuel consumption which will result in good environmental conditions. Oil and grease. and Fluorine. nitric acid. Today about 52% of the fertilizer plants use natural gas as a raw material. Naphtha. waste catalyst etc. Chemical sludge from nitro ETP. sulphuric acids etc. Suspended solids. Calcium carbonate. 24% use Naphtha. The disposal of wastes creates damages to underground water and endanger ecosystem.fuel oils. Inerts generated in nitrophosphate plant. Nitrogenous fertilizers Complex fertilizers like Nitrophosphates. So there is a need for developing a suitable and acceptable technology or recycling/utilization of waste and for recovery of useful/ valuable material from waste. II. III. Chromates. Coal. Environment management has been organized to focus attention on the efforts made by the fertilizer industry in this direction. NOx. Solid wastes Generated are mainly Carbon sludge. EMISSIONS FROM FERTILIZER INDUSTRY Like any other chemical industry. Coke oven gas. location of the industry etc. CONTROL OF GASEOUS EMISSIONS Over the years. carbon dioxide. 13% use fuel oil. Considering the diversity of the resources the plants are located mostly at the point nearest to the feed stocks. Hydrofluosilicic acid chromium sludge.
7% conversion efficiency will give out an emission of 197 ppm.7%. when its efficiency decreases to 97% its concentration increases to nearly 2000 ppm. Acid mist consist of liquid droplets of sulphuric acids ranging from 10 . II. Mist is formed when water vapor in the air combines with SO3 in the convertor. The liquid droplets acts as a spherical collector for the urea dust which ranges from 2..and its standards.5%-99. A sulphuric acid plant with 6% SO2 feed working at 99. All plants use Vanadium catalyst to convert SO2 to SO3 according to contact process most of the new plants are having a conversion capacity of 99. along with fuel consumption. Air is drawn from this annular duct by a ring of liquid jets consisting of nozzles arranged in annular space which provides the energy required to overcome the pressure drop in the system. In a typical 1000 tpd plant around 200 ± 500 mg/nm3 of urea dust will be formed in the process which has to be controlled else it would cause air pollution to a devasting extent. which is ten times of the earlier concentration so special control measures have to be made to reduce it during start up and shutdown So sulphuric acid plants are equipped with either a start up heater to increase catalyst bed temperature to the required level or a start up scrubber ± which is packed with towers of caustic soda to absorb the SO2 ± in this case Sodium Sulphate or Sodium Bisulphate is formed depending on the PH of the scrubbing solution. During this prilling process particulate matter is emitted solid urea is obtained in a prilling tower by cooling the solution with air to expel its water content. As said above major gaseous emissions are sulphates. which is further converted to solid form by prilling techniques. It causes a visible and persistent plume in the stack but also results in equipment corrosion. During start up and shutdown catalysts beds will become cold which results in poor conversion factors and causes high emissions of SO2 which causes a threat to environment. Urea solution is taken out when its concentration reaches 15 .07 microns.200 microns. nitrates and d fluorides CONTROL OF SULPHUR DIOXIDE EMISSION & SULPHURIC ACID MIST: Sulphuric acis is produced by oxidation of sulphur to SO2 and then to SO3. Mostly wet scrubbers are used for particulate matter removal dust laden air rising through the prilling tower enters the annular duct. which is absorbed to produce sulphuric acid. To prevent this problem from happening different types of mist eliminators are used I. Impaction type fibre bed mist eliminator Mesh pad type mist eliminator CONTROL OF PARTICULATE MATTER UREA DUST: Urea is produced by reacting NH3 and CO2 at elevated temperatures and pressure.
The remaining NO is converted in to N2 with the help of oxygen in tail gas ant fuel gas at temperature between 650700C.in this method reduction of NOx in the gas system is done with slight excess of stochiometric quantities of ammonia over a mixed catalyst.almost 10-15% for further processing. III. content in the tail gas varies from 1000-3000 ppm of which approximately 60% is NO2 and the rest is NO. The NOx. Selective: . IV. The extended absorption is made possible by provision of large absorption columns. The unabsorbed part of oxides of nitrogen and inerts are emitted to atmosphere which generally contains . Two catalysts are used in this reaction the first is based on precious metals mixed metallic oxides. The exit gas is decolorized by mixing with a fuel gas like natural gas and the mixture is passed over a catalyst bed which converts the NO2 into NO rendering exit gas colorless. Tail gas produced are mainly nitrogen.2.e 2000-3000 ppm NOx. Four types of processes which can be used to reduce or control emissions are I. 16 .4% of NOx and 2-3% free oxygen. water vapor. Outlet concentration of urea will get reduced to 30-50% mg/nm3 CONTROL OF OXIDES OF NITROGEN: Nitric acid is commercially produced by reducing ammonia with air to produce nitrogen oxides which are then absorbed in water to yield the acid. Catalytic reduction (selective and non-selective) Extended absorption Chemical absorption Absorption CATALYTIC COMBUSTION Non ± Selective: . noble or iron group or V2O5 on alumina which promotes NOx reduction and the second is platinum based which destroys or converts any ammonia fed to the system into harmless nitrogen. which is used to power the plant¶s compressor.. II. and oxides of nitrogen is normaly preheated and expanded through a tuebine to recover energy.The oxides of nitrogen formed during the combustion of ammonia are absorbed in water to form nitric acid. EXTENDED ABSORPTION The extended absorption process aims to continuing the process of absorption of the NOx in water beyond the level at which it normally ends .i.
CHEMICAL ABSORPTION The tail gas should be scrubbed with a liquid containing caustic soda or urea. The fluorine emissions are controlled by scrubbing these gases in either Venturi scrubbers. After cleaning the tail gas substantially in additional absorber. The condensate produced from the shift conversion. This leads to choking of scrubber nozzles. triple superphosphates or converted to wet phosphoric acid and there on to other fertilizers. CO2 absorption and methanation sections of a typical ammonia plant contains high concentration of ammonia.the condensate first flows to a CO2 flash vessel where most of the dissolved CO2 flashes away. The effluents generated in various sections of the plants are conveyed to the effluent treatment plant through segregated sewers as some of the effluents needs separate specific treatments before common treatment. LIQUID EFFLUENTS Liquid effluents generated in a fertilizer plant vary in nature. From there this is ent to condensate stripper where mainly 17 . In case of caustic . One of the commomly encountered problems is deposition of silica when concentration of phosphoric acid less than 50%. Water is used as the scrubbing liquor which converts the HF and SiF4 to H2 SiF4. it results in the formation of NaNO2 and NaNO3. packed towers. ABSORPTION The absorption of NOx on a fixed bed of solids has not been extensively commercialized as other processes. A typical quantity of condensate for a plant producing 900tpd ammonia is around 50m3/hr. liquid scrubbing could be adopted to reduce the pollution levels. There should be provision to reuse and recover the NaNO2/NaNO3 from the solution otherwise it could act as a source of pollution. quality and quantity depending upon various factors. crossflow scrubbers or a spray chamber. CONTROL OF FLUORINE EMISSIONS Fluoropatite ores are used for the production of fertilizers such as single superphosphates. Liquid scrubbing system is best adopted in combination with extended absorption. methanol and CO2. Hence nozzles have to be periodically cleaned and specially designed for this service. Efficient scrubbing system can operate upto 25% H2SiF4 but above this point the SiF4 vapour pressure rises steeply. Normal absorption on activated carbon or molecular sieves is very efficient but the absorbers must be regenerated either by thermal desorption or by pressure reduction.fluorine content may differ in rocks according to its source from 1-5% and is released as Silicon tetrafluoride (SiF4) and Hydrogen Fluoride (HF). Some common treatment and control measures are PROCESS CONDENSATE STRIPPERS:These are generally used in ammonia plants.
Here principle dissociation of ammonium ions to free ammonia at PH of 10-11. Effluent than goes to the denitrification tank where nitrates are anaerobicaly converted to nitrogen in the presence of carbon source like methanol or molasses.5 ± 8 50+ 4 100 10 0.2 0. the stripped condensate leaving the bottom of thr tower contains only 10 ppm of ammonia and is used back in the plant completely. Aerators are provided in the nitrification tank for oxidation of ammonical nitrogen to nitrates.2 0. PARAMETER pH Ammonical nitrogen Free ammonia Total Kjeldahl Nitrogen (TKN) Nitrate nitrogen Cyanide (CN) Vanadium Arsenic Hexavalent chromium Total chromium Suspended solids Oil and grease CONCENTRATION mg/l(except PH) 6. AIR STRIPPING WITH RECOVERY: Air stripping invariably leads to contamination of the environment with the ammonia.1 2 100 10 NOT TO EXCEED Liquid effluent standard for nitrogenous and complex fertilizer industries AIR STRIPPING FOLLOWED BY NITRIFICATION AND DENITRIFICATION: It is used to remove ammonical nitrogen in fertilizer industry.ammonia and methanol are stripped off in a distillation tower by means of stream at 4 kg/cm2 and at 180®C.2 0. Use of (NH4)2SO4 and NH4NO3 has to be 18 . The process destroys alkanity and lowers the PH which has to be adjusted by addition of Mg CO3. In this process.denitrification. Sludge removal is done in the final clarifier where polyelectrolyte is added to improve the setting characteristics. effluent is sent to the nitrification tank where residual ammonical nitrogen is converted to nitrates. The pH of the effluent is raised by the addition of alkali usually lime and the free ammonia is then stripped with air in a counter current stripping tower. This is followed by biological treatment by nitrification . For plant generating 100m3/hr of air /hr for stripping the ammonia and 14 tonnes per day of nitric acid or 11 tonnes per day of sulphuric acid for recovery.
1. while the solution returns to the lower part of the tower where the remaining ammonia is stripped out by means of vapour produced in the reboiler which is fed by 4.5-1% urea. As diposal of Cr(OH)3 is problematic due to some regulation some more alternatives are currently used for the safed diposal of the material. A typical composition of effluent is 4-5% ammonia. This blowdown contains 15-20mg/l of chromates in hexavalent form.5-2% CO2 and . arounf 450 ± 480 kg of effluent is generated for each metric tone of urea produced. this results in precipitation of fluoride as calcium fluoride and phosphates as mono and dicalcium phosphate/calcium hydroxylapatite. it is more focused to use these waste in such a way that new value product can be made out of it.5 kg/cm2.5 kg/cm2 saturated steam.the vapors produced in the hydrolyser are sent to an overhead condenser. SOLID WASTES Waste is an unavoidable factor of an industry. this not only help to dispose waste but also helps to generate profit for the company. The liquid effluent containing residual ammonical nitrogen (normally less than 250 mg/litre) can now be spent for biological treatment through nitrification. CONTROL REDUCTION OF CHROMATES Chromates in the form of sodium chromate or dichromate are added as a corrosion inhibitor in circular cooling waters for heat exchange equipment. CONTROL OF FLUORIDES AND PHOSPHATES Fluorides and phosphates are normally removed by adding lime.this is then precipitated using lime and caustic soda as Cr(OH)3. Since water contains urea after stripping of ammonia in the upper part of the tower.found within theplant or has to be marketed. HYDROLYSER STRIPPER Urea production in all plants is accompanied with a large amount of water . To maintain a certain level of total dissolved solids in the cooling water. The nitrates can then be denitrified as explained. a small quantity has to be discharged termed as blowdown. Some methods to utilize these watses are 19 . The feed is preheated before it enters the tower. Removal of this is achieved by lowering pH of the effluent to 2-3 and then reducing the hexavalent chromate to its trivalent form. This water is pumped to a distillation tower operating at 2. it is pumped into the hydrolyser where urea is decomposed into ammonia and carbon dioxide by means of saturated steam ata pressure of around 26 kg/cm2g.
This lime sludge is also used for flooring. The ash is conveyed to slurry dump and is converted into slurry and transported to ash pond through pipeline. Higher cost compared to conventional bricks 2. It is used as filler material to manufacture 20:20:0 grades ANP. tiles and building materials. where settling of carbon takes place and overflow is treated for removal of ammonical nitrogen. UTILIZATION OF SPEND HARD COKE IN BOILERS: The effluent coming from ammonia plant is expected to contain 200ppm of oil. Process involved firing in kiln which in turn involved use of fuel like coal 4. REUSE OF SOLID WASTES FLY-ASH-CLAY BRICKS TECHNOLOGY: Developed by CBRI roorkee for manufacture of Fly ash bricks. The carbon which gets accumulated will get drained of which can be used as a fuel for boiler and has a calorific value of 8547 Kcal/kg. size and colour. which can be stored in brick lined pond from where it is supplied to customers which is ultimately used for manufacturing of sagol and neutralization. Clay available in our area is coarser than fly-ash and has lumps which requires grinding of clay 5. The oil soaked coke removed from effluent treatment plant is utilized in boiler which results in saving equivalent quantity of coal. UTILIZATION OF INERTS GENERATED IN AMMONIUM NITRO PHOSPHATE: During digestion of rock phosphate some portion of rock phosphate remains as inert which is an unavoidable by product in ammonium nitro phosphate plant. Vast area of land required for obtaining earth 20 . Ash consumption 1. During the reaction lime sludge is generated. UTILIZATION OF FLY-ASH: Ash is produced as a result of burning of pulverized coal in fired boilers. gravity separation is followed by hard coke adsorption facility. To remove this oil from effluent.UTILIZATION OF CARBON SLUDGE IN BOILER AS FUEL: The carbon slurry formed during the start up and shutdown is stored ina slurry pond. Process involved mixing of black cotton soil with flt-ash and was resulting usage of top layer of fertile agriculture land 3. Fly-ash is mixed with black cotton soil 34% and burnt in bricks in kilns with same compressive strength of 80 kg/cm2 and of uniform shape. UTILIZATION OF LIME SLUDGE: Lime sludge is generated while treating effluent for removal of ammonical nitrogen.
byproduct of gypsum is used in manufacture of cements. Number of plants required to be established Other building materials with fly-ash: a) Activated pozzolona: it is fy ash only in which lime reactivity index is increased by increasing its surface area and removal of unburnt carbon. The thus treated and after satisfying the MINAS limits may join the effluents of other product plants. All the industries shall meet MINAS irrespective of the mode and place of discharge of treated effluent. It is applicable to all waste waters of the fertilizer plant. Gypsum is mainly used by sulphuric acid manufacturing industry in the form of phosphogypsum. insulation boards and plater of paris.6. paints. textile.lime.sand and other additives. WASTE GYPSUM Gypsum. the effluents of fertilser plants should be adequately treated to meet the stipulations of MINAS. CaSO4. The MINAS is based on the pollution control technology already practiced by some or other industries in the country. partition blocks. 21 .plater and flooring mass. d) Fly-ash bricks: of all the other uses fly ash bricks are the most demanding material and it consumes almost 80% of fly-ash and rest are binding agent. MINIMAL NATIONAL STANDARD (MINAS) It will cover all the fertilizer plant. Besides these industries pharmaceuticals. is a major solid waste disposed from chemical and fertilizer industries. c) Lime pozzolona: this is prepared by mixing 1 part of hydrated lime and 2 parts of flyash and can be used as masonary mortar. and tiles. It can be grinded with Portland cement clinker or blended uniformly with Portland cement to make Portland pozzolona cement b) Portland pozzolona cement (PPC): it is prepared by either grinding cement clinker and fly-ash in the cement mill or by uniformly blending with Portland cement in blenders the percentage of fly ash shall not exceed 25. asbestos products. While evaluating MINAS the present status of presently operating industries and also the industries which are likely to come in near future are considered with special stress on the aspects of pollutions and control measures. etc also use gypsum byproducts. This ensures practicability of implementation and achievability of the MINAS limits. sheets.
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