1.

COPPER SMELTER PROJECT DESCRIPTION The objective of this chapter is to discuss various processes of the Copper Smelter Project, with particular reference to their pollution generating potential. The latter is important for environmental impact analysis of and the development of environmental management plan for the project. The integrated copper smelter project will comprise a copper smelter plant, sulfuric acid plant, phosphoric acid plant, precious metal recovery plant and captive power plant. The copper smelter plant will be based on Outokumpu Flash Smelting Technology. The sulfuric acid plant will use technology from Monsanto Enviro-Chem, USA. The electrolytic refining process for copper extraction is based on the ISA electro refining process and MIM, Australia, designed by Outokumpu. The precious metal plant will use the technology from Outokumpu, Finland. The lignite based captive power plant and phosphoric acid plant with fluorine recovery system will utilize technology from Prayon, Belgium. The operation of each of these plants is discussed in the following paragraphs. The pollution potential of each plant with respect to the generation of air pollutants, water pollutants and solid waste is also discussed. However, quantitative details related to the discharge of potential pollutants are provided in Chapter 6, which discusses the environmental impact assessment.

1.1

Copper Smelter Plant The copper smelter plant operation will involve i) ii) iii) iv) v) Receiving, storage and processing of raw material, i.e., copper concentrate, silica flux and coke. Extraction of copper from the copper concentrate using Flash Smelting Furnace (FSF) and Peirce Smith Converter. Fire refining of the blister copper to produce 99.5% Cu as anodes. Electrolytic refining to produce 99.99% Cu as copper cathods, and Recovery of Grade B copper anodes from the spent electrolyte.

Flash Smelting area process block diagram and Refinery area block diagram are shown in Figure 3.1 and Figure 3.2, respectively. Various processes of the plant are discussed in detail in the following paragraphs. 1.1.1 Storage and processing of raw material The copper concentrate, silica flux and coke will be transported to the plant premises using a belt conveyor system from the jetty, and stored in storage bays.
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The concentrate will be stored in a covered building with a capacity to hold 2 months supply. The concentrate from the storage bays will be blended with silica flux and coke in proper proportion and the blend will be transferred to day bins, which will be made of concrete with stainless steel inside lining. The concentrate mixture will be fed into a concurrent flow multicoil steam dryer to reduce the moisture content to less than 0.2% to meet the requirement of the feed for a flash furnace. This mixture will be stored in dry bins. The mixture from the dry bins will be conveyed into the charge drag conveyor to feed the mixture into the furnace. There is potential for dust emissions from the dryer. Bag filters will be provided to clean the off gases from the dryer before these are discharged into the atmosphere through the dryer stack. 1.1.2 Flash smelting furnace operation The dried concentrate mixture will be smelted in a flash smelting furnace, which will be preheated to 1300C. The fuel oil fired burners will be used for preheating the furnace. Preheated oxygen enriched air will be fed during the smelting operation to control the process temperature, the latter depending on the degree of oxygen enrichment. In case, the concentrate reaction heat (reactions are exothermic) is low, some fuel will have to be introduced into the reaction shaft. Smelting of the concentrate will result in the formation of two layers viz., bottom layer comprising the matte the top layer will be the flash smelting slag. The matte (65% copper) from the smelter will periodically be poured through launders to the matte ladles and carried to a Peirce Smith converter, whereas the slag will be transmitted to the electric slag cleaning furnace. The flash smelting furnace off gases will be treated for particulate dust recovery using an electrostatic precipitator which will be transferred to the flue dust bin of the flash smelting furnace. The dust free and sulfur dioxide rich flue gas stream will be treated for the recovery of sulfur dioxide. 1.1.3 Pierce smith converter operation In the converter, copper matte from the flash smelter will be subjected to two stage process i.e., slag blow and copper blow. In the slag blow process, air will be blown through the molten matte to remove sulfur and iron to produce white metal. The latter would mix with silica to produce molten slag, which will be transmitted to the electric slag cleaning furnace. Silica flux will be fed to the converter from silica flux bins. During the copper blow stage, sulfur in white metal will be blown to sulfur dioxide producing blister copper. The blister copper produced in the converter is expected to contain about 98.5% copper. Blister copper produced in the Pierce Smith converter is likely to contain various impurities e.g., sulfur, oxygen, nickel, iron, zinc, lead, cobalt, selenium, arsenic, antimony, bismuth, gold and silver. These impurities will be removed by fire

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refining and electrorefining to obtain copper with specific physical and chemical properties. The process gases from the converter hoods will be treated for dust removal. Dust so collected will be transferred back to the dust bin of the flash smelting furnace and the gases will be further cleaned in the gas cleaning section of the sulfuric acid plant. Heat carried by flue gases will be recovered by using a waste heat boiler. A small amount of gas leaking outside the primary gas hood will be captured by the secondary gas hood and then led through the secondary gas scrubbers to the main stack. 1.1.4 Refining and anode casting operation Blister copper from the converter will be charged to an anode furnace for fire refining to increase the copper content to 99.5%. The furnace will be heated by using fuel oil to keep copper in the molten state during charging. After charging, oxidation will be carried out by blowing air through the tuyeres in molten copper. Impurities such as iron will be transformed to the slag and sulfur will be transferred to the gaseous phase. The off-gases from the anode furnace will be incinerated. The slag will be skimmed with utmost care to avoid remixing of impurities with copper during deoxidation. The oxidation phase will be followed by deoxidation phase, where only the excess oxygen will be removed from the copper by using LPG as the reducing agent. The refined copper will be caste into copper anodes on a rotating anode casting wheel. The anode cooling waters will be circulated through the water cooling area where copper scales will be settled in a settling tank and the water will be cooled using cooling towers. These anodes will be dispatched to a tank house for electrorefining. During deoxidation stage and idling, the anode furnace off-gases are led through a ventilation gas bag house to the anode casting area stack. 1.1.5 Electro-refining operation The electrorefining cell will be used for further refining of the extracted copper. The cell will contain permanent stainless steel cathodes and copper anodes casted from the blister copper in an electrolytic solution i.e. an acidic copper sulfate solution. DC current will be passed through cells, which would result in the movement of copper ions from the copper anode to the stainless steel cathode resulting in 99.99% of copper deposition on the cathodes. The product cathode is transported to the storage. During the electrorefining process, the copper anode will be dissolved except for those impurities, which include precious metals e.g., selenium, tellurium and lead. Other metals such as copper, nickel, arsenic, antimony and bismuth will dissolve
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partially. The impurities will deposit as slime at the bottom of the electrolytic cells. The slime will also contain finely divided copper powder from the chemical degradation of cuprous oxide contained in the anodes. The slime will be removed from the cells at the anode replacement time and will be pumped to the slime treatment thickener for settling. The thickened slime will then be leached batchwise in an atmospheric leaching reactor. In the reactor, the anode slime, electrolyte and added acid will be mixed by introducing oxygen. The mixture will be filtered. The copper containing filtrate will be treated in the decopperising system after possible cementation of tellurium to avoid contamination. The copper free leached slime will be transported to the precious metal plant for further processing. Other impurities will partially leach out into the electrolyte. A small portion of the electrolyte will be bled off in the process to restrict the level of impurities in the electrolyte. The cathodes and anode scrap from the commercial cells will be washed free of electrolyte and anode slime. Anode scrap will be recycled to the smelter. The electrolyte bleed and scrap wash water will be treated in the effluent treatment plant. 1.1.6 Treatment of spent electrolyte The bleed from the electrolytic cells will be treated to recover copper sulfate, grade B copper cathodes and copper/arsenic precipitate. An evaporative copper sulfate crystallizer will be used for the recovery of copper, which will be returned to the main circuit for keeping the copper concentration at a constant level. The spent electrolyte from the crystallizer will be led to the liberator cells for further treatment. The process will involve three stage electrowinning to produce Grade B cathodes, impure cathodes and As/Cu powder. The first stage solid cathodes will be sold in the market, whereas the second stage impure cathodes will be sent back to the smelter. The latter will be washed using high-pressure water jets in the scrap washing machine. Cu/As powder will be packed in PVC drums for storage. This powder will contain antimony, bismuth and tellurium in addition to copper and arsenic. The decopperised bleed will be sent to the neutralization unit of the ETP for further treatment. Water from anode scrap washing will also be led to the ETP. 1.1.7 Slag cleaning furnace In the slag cleaning furnace, the flash smelting furnace slag (2% copper content) and Pierce Smith converter slag (10% copper) will be treated by adding coke, which will reduce copper and other metal oxides present in the slag. Coke and reverts will be fed through the furnace roof. Electric power will be needed for
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reduction reactions, heat losses and smelting of reverts. At temperatures higher than, gases containing SO2 and dust will have to be discharged, and these gases will be led to the atmosphere through the electric furnace stack. Slag from the electric furnace will be tapped into a slag granulation unit. The granulation launders will be fitted with nozzles through which water will be sprayed on the molten slag to form slag granules. Granulation water will be circulated through a settling pond, cooling pond and cooling towers. A part of granulation water will be bled off to maintain its quality. The size of granules would typically vary from 0.17 mm to 6 mm. Granulated slag will be transported to the slag storage area. The matte from the slag cleaning furnace will be taken back to the Pierce Smith converter. The granulation water bleed will be led to the ETP for treatment. 1.1.8 Cooling water circuit The cooling water is first pumped to the head tank of the jacket cooling system. Water flows from the head tank to the copper cooling elements of the flash smelting, slag cleaning and anode furnaces. Warm water from the cooling elements is led through plate heat exchangers and then returned to the jacket water tank. A small bleed is led out, which can be used for general cooling or as process water, and the corresponding amount of make up water is added. 1.1.9 Pollution generation potential of the smelter plant Gaseous emissions Dust will be generated during the drying of the copper concentrate mixture in the drying area. The dust will be collected in bag filters, and the uncaptured portion of the dust will be discharged into the atmosphere through the dryer stack. Dust emissions will also be generated at the converter feed system and these will be led to the atmosphere the converter area stack. During smelting operation, gas leakages from matte slag tapping, slag cleaning furnace, secondary gas hoods will be collected and passed through the secondary gas scrubber, and the unabsorbed gases will be discharged into the atmosphere through the main stack. The anode furnace off-gases generated during deoxidation stage and idling will be led through a ventilation gas bag house to capture dust. The small amount of dust which escapes the filter will be discharged into the atmosphere through the anode casting area stack.

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Dust and sulfur dioxide containing gases will also be discharged into the atmosphere from the slag cleaning electric furnace when the temperature of incineration gases is higher than 180C. Liquid effluents Various liquid effluent streams generated in the copper smelter plant operation are: Bleed from the liberator cell or spent electrolyte containing mainly sulfuric acid and heavy metals; Bleed from slag granulation unit; Bleed from cooling water circuit; and Scrubber water from the secondary gas scrubber.

The secondary gas scrubber will receive gases from other plants. Both process waters and cooling water will be recycled to the maximum extent possible to minimize the generation of wastewater. Only the bleed from a process stream will be discharged to maintain the quality of the stream. The above identified waste streams are treated in the Effluent Treatment Plant. Solid wastes Slag generated from FSF and PS converter after cleaning and granulation will have to be either disposed off as a solid waste or reutilised. Liquid effluent streams that will be treated in the Effluent Treatment Plant (ETP) will contribute to the generation of the ETP sludge, which needs to be disposed off. Copper / Arsenic powder separated from the Grade B copper cathodes in the third stage of the electrowining process need to be adequately packed and disposed off. 1.2 Cakes and Billets Plant Copper cathodes from electrorefining process will be stored in buckets in the storage area of the cakes and billets plant, ready for discharging these into the charging wagon. These cathodes will be fed into the induction furnace by tilting the charge wagon at the front opening of the induction furnace. The latter will be a channel type induction furnace which completely operates on electricity. During melting, the furnace will be in a horizontal position and during casting it will be tilted to allow the melt to flow into a casting mold along a refractory lined launder till the desired length of cast is reached. These molds will be oscillating and the melt in these molds will be covered by graphite powder to prevent oxidation. The mold will be surrounded by a special copper jacket which will be water cooled. Upon leaving the bottom of the mold, the already solidified cast
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will further cooled by direct cooling water spray. The cast will be sawn from both ends and the edge cuttings will be recycled to the furnace. The sawn casts will be transported out of the building by means of roller conveyors. Gas burners will be provided for preheating the launder prior to casting to control the flow of molten metal. The fumes will be collected by a fume hood and exhausted to atmosphere via the anode casting stack. Gaseous emissions Fume from the anode casting unit will be led to the anode casting stack for discharging these into the atmosphere. 1.3 Precious Metal Plant The leached slime from the refinery area will be further treated in the precious metal plant, which would involve the recovery of the following precious metals. Selenium recovery Silver recovery Gold and platinum recovery

The Precious Metal Plant block diagram is shown in Figure 3.3. 1.3.1 Selenium recovery Selenium roasting The leached slime from the refinery will be transferred to the roasting trays, and then carried to the roasting furnace. Roasting will be carried out at 600C in the presence of sulfur dioxide and oxygen, which will be fed as reagents. As a result of roasting, Selenium Dioxide (SeO2) will be generated in the furnace, which will be sucked out through an ejector and passed through aqueous solution containing sulfuric acid. Here, SeO2 will be reduced to elemental selenium by sulfur dioxide. In this process, SO2 will be oxidized to SO3, which will subsequently be absorbed in the aqueous solution containing sulfuric acid. A part of the sulfuric acid solution (bleed) will be used for slime leaching. The desalinized slime will be discharged into a feeding bin of the Dor'e Smelting Furnace. The reduced elemental raw selenium powder will be filtered, washed and dried or directly smelted to produce 99.5% commercial grade selenium. Exhaust gases from roasting will be led to secondary scrubbing area of the precious metal plant. Vapor gases generated during filtering will be collected by a hood and then led to the ventilation pipeline. Selenium distillation
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Dried crude selenium will be loaded into a distillation retort, and then placed into a distillation furnace. The furnace will be electrically heated to a temperature of about 700C at which the distillation of selenium will take place. Distilled selenium will be run down into flowing water so that selenium is granulated. The granulated selenium (99.95%) is dried and packed. The distillation residue is recycled to the selenium roasting furnace. The exhaust gases will be filtered through bag filters and led to the ventilation pipeline. The collected dust will be circulated to the selenium roasting trays. 1.3.2 Silver recovery Dor'e smelting The desalinized slime will be mixed with soda and borax and then smelted batchwise in a rotary type Dor'e furnace (TROF - converter) for the recovery of silver. The smelting process will be carried out in two stages. In the first stage, the materials will be smelted and primary slag separated out from metal. The primary slag will be sent to the copper smelter. In the second stge of smelting, oxygen refining will be carried out in the furnace. The refined metal will be cast into anodes and subsequently subjected to silver electrolysis. The silver rich slag produced during the refining stage will be recycled into the furnace along with the subsequent feed batches. The fule gases will be passed through a bat filter and vented out through a stck. The flue dust will be recycled to the Dor'e Smelting Furnace. Silver electrolysis Dor'e anodes will be subjected to electrolysis in Moebius cells to separate silver from gold and platinum metals. Silver will dissolve in the nitric electrolyte and on the passage of current will deposit as crystals on the cathodes. These silver crystals will be scrapped from the cathode surface, washed, dried, melted and cast into bars or granules. Gold, platinum and some silver left in the anodes will be collected in bags surrounding the anodes. After the electrolyte has been contaminated, it will be replaced by a new electrolyte (AgNO3). The spent electrolyte and washing waters will be treated in the desilverizing tank. Silver cementation In this process, all spent solutions, which may contain dissolved silver, will be desilverized. These solutions include the spent electrolyte from the silver electrolysis, washing waters of gold mud, and washing waters of crystal silver. The desilverizing will be carried out in a desilverisation tank by the cementation reaction with zinc or copper powder. The cement silver produced in this process
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will be filtered, washed and recycled to the Dor'e furnace. Waste liquid will either be partly or totally recirculated in the process. Any effluent wll be treated in the effluent treatment plant. 1.3.3 Gold and platinum recovery Gold treatment process The gold mud harvested from the Moebius cells will be washed and then boiled in concentrated sulfuric acid to remove residual silver to get gold sand containing typically 90-95% gold. The Ag2SO4 formed in the process will be decanted and led to the desilverizing tank. Gold sand will be leached with concentrated hydrochloric acid (30-35% HCl) using hydrogen peroxide (50% H 2O2) as a reagent. After leaching, the batch will be filtered and the residue mostly silver chloride (AgCl) will be recycled to the Dor'e smelting process. The leached product (AuCl3) will be subjected to the precipitation process where gold will be precipitated in two steps using sodium-meta-bisulfite (Na 2S2O5) as a reagent. The fine gold powder (Au > 99.99%) obtained after the reduction will be filtered, washed, dried and finally melted to form gold bars. The process is repeated several times till most of the gold is recovered. Platinum metal will be precipitated from the solution using metallic iron, where platinum metal chlorides will be reduced to form iron chlorides. The concentrate, which contains 85-95% platinum metal, will be washed, dried and sold. The bleed off will be transferred to the effluent treatment plant for further processing. Cement silver from the leaching of gold mud and spent electrolyte produced in Moebius system as well as residue from the gold treatment process are also recycled to the Dor'e furnace. 1.3.4 Pollution potential of the PM plant Air emissions Exhaust gases containing sulfur dioxide and dust from selenium roasting will be passed through secondary scrubber and then led to the scrubber gas stack of the main stack. Vapors from selenium filtering and distillation will be lead through ventilation bag filter and then discharged into the atmosphere through the precious metal stack. Flue gases from the silver recovery process will also be vented out to the atmosphere after passing through a bag house. Liquid effluents The following effluent streams will be generated from the precious metal plant:
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Bleed from the spent electrolyte; Waste liquid from the silver cementation process; and Wash waters

Solid waste Liquid effluent streams that will be treated in the Effluent Treatment Plant (ETP) will contribute to the generation of the ETP sludge, which needs to be disposed off. 1.4 Sulfuric Acid Plant The SO2 rich gases from the flash smelting furnace and the converter are used to produce sulfuric acid in the sulfuric acid plant. Various steps involved in the production are : Cleaning of the sulfur dioxide (SO2) gases from the smelter Drying of the sulfur dioxide gas Converting sulfur dioxide gas into sulfur trioxide (SO2) gas, and Absorbing sulfur trioxide gas in the dilute acid to form 96-98% sulfuric acid

About 99.8% of SO2 present in smelter gases will be recovered during the production of sulfuric acid. After recovering SO 2 in the form of H2SO4, SO2 emissions in the flue gas stream are expected to be in the range of 150-500 ppm. Figure 3.4 shows the sulfuric acid plant area block diagram. 1.4.1 Gas cleaning section The smelter gas containing SO2 will be cleaned using Monsanto Enviro-Chem's state-of-the-art Dyna Wave gas cleaning system. in this system, gas will enter the top of a reverse jet scrubber and the circulating weak acid will be injected upward. A standing wave of highly turbulent flow will be created at the point where the liquid is reversed by the gas. In this region, also called as forth zone, the gas will be efficiently quenched; and dust, condensed fume and SO3/acid mist will be removed from the gas stream. Two reverse jet scrubbers will be used if the amount of contamination in the gas is high. The gas will then be led to the final reverse jet scrubber, where halogens will be removed and the gas will be cooled to meet acid plant water balance requirements by bringing it in contact with externally cooled weak acid. Make up water will be fed into the final reverse jet scrubber to adjust weak acid strength. The weak acid effluent will be led countercurrent from the final to first vessel, stripped of SO2 using air, and finally pumped to effluent treatment plant. The stripping air leaving from the first reverse jet scrubber will be led to a duct. The cooled gas leaving the Dyna Wave System will then be passed through a
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chevron vane demister located at the top of the final vessel to remove the remaining particles of acid mist and metallic fumes; and solids will be removed by using wet electrostatic precipitators. After leaving the wet electrostatic mist precipitators, the gas will enter the drying section of the acid plant. 1.4.2 Gas drying section The cleaned gas from Dynba Wave gas cleaning system and the final wet electrostatic precipitators will be diluted by air to adjust the O 2/SO2 ratio and then passed through the drying tower where strong sulfuric acid will be countercurrently sprayed. As a result, moisture present in the gas stream will be absorbed into the strong acid. Heat evolved during the absorption process will be dissipated by externally cooling the circulating acid by using cooling water. The latter will be recirculated through cooling towers. The acid circulated in the drying tower will get diluted due to water vapor removed from the SO2 gas. 1.4.3 Conversion and absorption of SO2 The dry and clean SO2 gas will be led to the contact converter for oxidizing it to SO3 using vanadium pentoxide (V2O5) catalyst at 420-650C. The oxidation reactions are exothermic and these will generate heat. This heat will be mainly utilized in preheating of incoming gases. The conversion of SO 2 to SO3 will be a two stage process. In the first stage, the gas will be passed through the vanadium pentoxide catalyst layer three times. After each pass, the oxidized hot gas will be cooled back to minimum ignition temperature (420C). the gas will be led through interpass absorption tower, where SO3 is absorbed into circulating acid. About 96% of the SO2 gas will be converted into SO3 during the first stage of conversion. The unabsorbed gas will be led back to the converter for the second stage of conversion where the gas passes over one more layer of catalyst. Finally, the gas will be led through the final absorption tower to the main stack for venting it into the atmosphere. The total conversion, after 3 + 1 passes is expected to be over 99.75%. In the absorption towers, sulfur trioxide will be absorbed into 98-99% sulfuric acid. The SO2 gas will react with the water content of the acid to further concentrate the sulfuric acid. There will be a total of three acid circulating systems with their own circulating pumps, pipings, acid cooling heat exchangers and pump tanks. One of these systems will be used for gas drying. The other two will be used for SO3 interpass absorption and final absorption towers. The three acid circulating systems will be interconnected to allow the control of the acid concentrations in each of the acid circulation systems. The drying acid will be concentrated with strong absorption acid, and the absorption acid will be diluted with drying acid. The concentration of absorption acid is kept constant by adjusting make-up water. Acid will be pumped from the final absorption pump
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tank to a product pump tank. The product concentration will be maintained at 9396% acid. The product acid will finally be pumped to the storage tank. 1.4.4 Heat recovery The reactions involved in the conversion of SO2 into SO3 and absorption of SO3 into dilute H2SO4 will be highly exothermic. The heat generated from SO 2 conversion and SO3 absorption will be recovered by closed hot water circulating systems. The generated hot waters will be utilized by hot water users and/or cooled with a heat exchanger connected to the secondary cooling system at the cooling water area. 1.4.5 Acid storage The role of the acid storage in the acid plant area will be to store the product sulfuric acid in the place from where the acid can be further pumped to acid storage near the harbor. 1.4.6 Pollution potential of the sulfuric acid plant Air emissions The unabsorbed gases from the conversion and absorption unit of the sulfuric acid plant will be vented into the atmosphere through the acid plant stack of the main stack. Liquid effluent A portion of the weak acid left after the stripping of sulfur dioxide gas from the concentrated sulfuric acid will be discharged into the ETP. Solid waste Liquid effluent streams, treated in the Effluent Treatment Plant (ETP) will contribute to the generation of the ETP sludge, which needs to be disposed off. 1.5 Phosphoric Acid Plant Phosphoric acid plant uses rock phosphate and sulfuric acid from the sulfuric acid plant as the raw materials. Rock Phosphate of mesh size 40% will be ground in an open circuit ball mill to obtain rock phosphate slurry with 68 to 70% solid content. The slurry will be pumped to multi-compartment reactor where it would react with 98% sulfuric acid to form phosphoric acid and phosphogypsum. Being exothermic, the reaction will generate heat. The temperature of the reactor will be maintained between 78 to 80C to facilitate the reaction to take dihydrate route

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and the formation of gypsum crystals. Due to exothermic nature of the reaction, fumes of HF and SiF4 will be generated in the reactor. The slurry from the reactor will be pumped to belt filter to a separate phosphogypsum crystals from the liquid phase phosphoric acid (29%). This dilute phosphoric acid will be concentrated up to 52% to meet the merchant grade standard in a rubber lined flash chamber. Vacuum in the chamber will be maintained by two stage steam ejectors. During acid concentration process, fluorine vapors will also be evolved. The HF and F carrying gases from the reactor, belt filter section and concentration chamber will be led to a gas scrubber involving three stage washings with cold water. The scrubbed gas will be vented to the atmosphere through a 60 meter tall stack. The phosphogypsum separated out by the belt filter from acid slurry will be dumped in a rectangular storage/dump yard. The storage / dump yard will be lined with a synthetic LDPE liner to prevent the contamination of subsoil with acid water. The liquid from the dump yard will be collected by a garland drain with a pit from where it will be pumped out of the yard. The plant will also have a continuous blowdown of acidic water at the rate of 45 m/hr from the cooling tower. The blowdown will be maintained by giving a purge from the fluorine absorber seal tank. The liquid effluents from the plant will be collected in an effluent buffer tank and pumped to liquid effluent neutralization unit for two stage neutralization with CaCO3 solution. The neutralized effluent will be routed to the treated effluent lagoon of the centralized effluent treatment plant. 1.5.1 Pollution potential of the phosphoric acid plant Air emissions The unabsorbed gases containing F from the scrubber unit of the phosphoric acid plant will be vented to the atmosphere through the Phosphoric acid plant stack. Liquid effluent The following liquid effluents will be generated by the plant: Scrubber water Phosphoric acid dump yard effluent Phosphoric acid plant blowdown

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These effluents will be subjected to two stage neutralization with CaCO 3 solution and the neutralized effluent discharged into the treated effluent lagoon. Solid waste Phosphogypsum produced as a byproduct will have to be disposed off adequately or used as a resource. 1.6 Captive Power Plant A 24.5 MW lignite based Captive Power Plant will be installed to supplement power supplied by the Gujarat Electricity Board and during emergency power sheeding or grid failure. The power plant will use 140 T/Hr Circulating Fludised Bed Combustion (CFBC) boiler with MCR rating at 66 Kg/cm steam pressure and 485C steam temperature at superheated outlet. In CFBC boilers, fuel particles in suspension escaping the combustion chamber of the furnace will be captured by a cyclone and circulated back to the combustion chamber. This would results in better combustion efficiency. A condensing type steam turbine with provision to extract steam for regenerative feed heating and process requirements will be used. The turbine will be complete with steam ejectors, deaerating heater and boiler feed pumps. The condensate from the condenser will be pumped to the condensate storage tank, where from it will be sent to the deaerator through a LP heater. The condensate is finally circulated back to boiler through a HP heater. The use of CFCB boiler will also result in low NOx emissions. Under usual operating conditions of the boiler, 90% of fuel nitrogen will be converted to N2. The thermal NOx, which is produced at temperatures of 1200 to 1300C, will not be formed as the optimum temperature in the fludised bed is about 850C. The SO2 emissions from the boiler furnace will be limited by injecting limestone on the furnace bed. The limestone injection will fix sulfur present in coal into ash and a very little quantity of SO2 will escape into the atmosphere. Since fly ash is recirculated into the combustion chamber, line stone reutilisation for sulfur fixation will be very high. An electrostatic precipitator will be used for collecting particulate matter, and only small portion of fly ash will be discharged into the atmosphere. 1.6.1 Pollution generating potential of the captive power plant Air emissions The combustion of lignite will generate fly ash, SO 2 and NOx. Even though circulating fludised bed combustion boiler with lime injection system will
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considerably reduce SO2 and NOx emissions, small quantities of these pollutants will have to discharged into the atmosphere. An electrostatic precipitator will be used for capturing fly ash, and only a very small percentage of it will be discharged into the air. Liquid effluent Boiler blowdown will constitute to liquid waste generated from the captive power plant. The quantity of this waste will be very small. Solid waste Solid waste will constitute fly ash collected by the electrostatic precipitator and bottom clinker i.e., bottom ash and gypsum (produced as a result of sulfur fixation of lime stone in the boiler furnace). In this chapter, potential sources of air pollution, liquid waste and solid waste have been identified for each plant of the Copper Smelter Project. As is obvious from the above discussion, various pollution control systems are already part of the various process units. These pollution control systems along with other mitigation measures planned for reducing adverse environmental implications of the project are discussed in the following chapter. 2.0 MITIGATION MEASURES The selection/identification of mitigation measures for reducing the adverse environmental impacts of the copper smelter project formed the integral part of the copper smelter project design. Thus, the selection of clean and efficient technologies, installation of the end-of-pipe air pollution control equipment and setting up of the effluent treatment plant were important elements of the project design. In addition to these, the solid waste management, greenbelt and community welfare plans were prepared to alleviate the other adverse impacts anticipated due to the project. This chapter highlights various design/technology related features of the copper smelter project and end-of-pipe pollution controls installed for protecting the air, water and land environment. The salient points of the greenbelt development, solid waste management and community welfare plans are also highlighted in this chapter. 2.1 Air Pollution Controls Air pollution sources of the project will be equipped with appropriate pollution control equipment to reduce emissions to levels which comply with the emission standards and / or do not cause violation of the ambient air quality standards. Table 4.1 depicts various air pollution sources of the copper smelter project and the control equipment that will be used for each of these sources.

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A short description on the operation of the equipments listed in Table 4.1 is presented in the following paragraphs. Cyclones Cyclones, because of their low cost, are commonly used for collecting dust. Since these can be constructed with refractory lining, dust bearing hot gases (up to 982C) can easily be treated by cyclones. The dust bearing gas stream is tangentially introduced into a cyclone to impart it a circular motion. Dust particles being heavier than gas molecules are thrown out against the wall by the centrifugal force. These dust particles slide down the walls and get collected in a hopper. Cyclones are typically effective for larger size particles (dust), and therefore, will be used for dust generated in dryer area. Electrostatic Precipitators (ESP) It is an extremely efficient air-pollution control device for capturing particulate matter (particularly small size particles which are generated in combustion processes) from a gas stream with efficiency more than 99 percent. In an ESP, a high voltage source is used to negatively charge corona to create a strong electric field. Due to this strong electric field, gas molecules get ionized and particles present in the gas stream become negatively charged. These negatively charged particles move towards the grounded collecting plates, from where these are periodically removed. The initial capital investment for an ESP is high, but it is off set by its low operating cost. ESPs will be used for collecting fly ash from the captive power plant. Table 2.1 Various sources of air pollution and the Controls to be adopted Plant Area Concentrate Drying Area Pollution Source Dryer Off Gases Smelter & Converter Off Gases Smelting Furnace & Converter Launders, tapholes and openings in smelter and electric furnace Converter Pollutant Dust (bearing Cu concentrate) SO2 Dust (bearing Cu, copper oxides and sulfides) Fugitive Fumes containing SO2 Control Facility Cyclone and Electrostatic Precipitator for recovery and recycle of dust. ESP for recovery and recycle of dust (dust free gas taken to acid plant for sulfuric acid production) To be exhausted outside building through hood, ducting, ID fan, stack. Axial fans to be installed at top floor for general exhaust. To be exhausted outside

Fugitive fumes
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Secondary Fumes Anode Refining and Casting Plant Refinery Plant Gas from Anode Furnace Fumes generated in Cell house

containing SO2 and other minor constituents Dust

building through hood, ducting, ID fan and stack. To be exhausted outside the building through hood, ducting, ID fan and stack. Alternatively, this shall be used in rotary dryer. Building ventilation system for adequate air exchange. Also fume extraction systems for selected areas. Double Contact Double Absorption (DCDA) Plant Treated in scrubber before discharge into the atmosphere. Lime injection for SO2 capture and ESP for fly ash capture.

Acidic fumes

Sulfuric Acid Tail Gas Plant Phosphoric Tail Gas Acid Plant Captive Power Plant Dust and Gas

SO2/ SO3 and acid mist Acid Mist, Fluorides etc. SO2, NOx and Ash particles

Bag House Filters Bag houses find wide range of application as far as particulate matter collection is concerned. The dust particles present in a gas stream passed through a bag house filter are removed first by sieving action of the fabric of the bag and later by sieving action of pores of the dust layer collected on the surface of the bag. Mechanical shakers or high pressure air pulse introduced in the opposite direction are used to periodically dislodge dust from the fabric. The efficiency of fabric filters are normally above 98 percent and can go up to 99.9%. Ventilation gases from bin and conveyor local ventilations, anode furnace offgases during idle and deoxidation stages and ventilation gases from electric slag cleaning furnace will be cleaned in bag houses. The clean gases will then be led to the main stack. Secondary Gas Scrubber Scrubbers are efficient gas cleaning devices. In a scrubber, a gas stream is passed counter current to the liquid stream to allow the latter to capture undesirable gases or particles present in the gas stream. A scrubber will be used for cleaning secondary gases from the following sources: The connection between flash smelting furnace and waste heat boiler Converter secondary hoods Smelter furnace tap holes
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Launders Ladle spots Anode furnace gases during oxidation

The secondary gases will be treated by one stage wet scrubbing using calcium hydroxide {Ca(OH)2} as the reagent. The efficiency of desulfurization is expected to be about 99% and the level of SO 2 in the exhaust gases is expected to be 50 ppm. The treated gases will be led to the main stck for venting these into the atmosphere. Lime injection and Circulating Fludised - Combustion (CFBC) boiler To limit the generation of air pollutants from the .. based captive power plant, 140 T/Hr Circulating Fludised Bed Combustion (CFBC) boiler will be used. In CFBC boilers, fuel particles in suspension escaping the combustion chamber of the furnace will be captured by a cyclone and circulated back to the combustion chamber. This would results in better combustion efficiency and reduction in the particulate matter levels in the exhaust gases. The particulate matter or fly ash will further be captured by an electrostatic precipitator so that only a small portion of fly ash is discharged into the atmosphere. The use of CFCB boiler will also result in low NOx emissions. Under usual operating conditions of the boiler, 90% of fuel nitrogen will be converted to N2. The thermal NOx, which is produced at temperatures of 1200 to 1300C, will not be formed in this case, as the optimum temperature in the fluidised bed is about 850C. The SO2 emissions from the boiler furnace will be limited by injecting limestone on the furnace bed. The limestone injection will fix sulfur present in coal into ash and a very small quantity of SO2 will escape into the atmosphere. Since fly ash is recirculated into the combustion chamber, lime stone reutilisation for sulfur fixation will also be very high. 2.2 Liquid Waste Management The copper smelter and associated plants will generate a number of effluent streams, which need to be treated before discharging these into a surface water body or on land. A discussion on processes resulting in the generation of these effluent waste streams is provided in Chapter 3. Table 4.2 highlights important characteristics of these waste water streams. These waste water streams will be led to an Effluent Treatment Plant for removing pollutants and bringing the effluent quality in compliance with the effluent standards. The major focus of ETP is the conversion of dissolved arsenic and other heavy metals into the insoluble form and separate these solids from the effluent to be stored adequately. Table 2.2 : Characteristics of the influent to the Effluent Treatment Plant
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Impurity Sulfuric Acid Copper Lead Nickel Arsenic Cadmium Zinc Iron Mercury Fluorine Chlorine Solids/Inerts

Concentration (g/l) 12.49 0.06 0.06 0.32 0.43 0.01 0.06 0.05 0.00 0.08 0.05 0.12

Quantity (t/yr.) 7923.3 38.9 34.9 204.2 274.4 6.2 40.6 34.0 1.1 50.2 33.3 75.5

Figure 2.1 shows the block diagram of the effluent treatment plant. The ETP consists of two storage tanks to receive various waste water streams from the Copper Smelter Project. Each of the two storage tanks will have a capacity of 400 m. Tank 1 will receive scrubber and slag granulation waters. Tank 2 will receive effluents from the anode casting unit, precious metal plant, refinery and sulfuric acid plants. The two tanks will be connected to accommodate overflow from each other. Miscellaneous effluent comprising rain and wash waters will be taken by both the tanks. The effluent with controlled concentration of dissolved arsenic (440 mg/l) and acid content of 12 g/l from the storage tanks will be led to three precipitation/neutralization tanks connected to each other is series so that outflow from one flows into the next. Each of these tanks will have an operational volume of 95 m and total volume of 134 m. each of the precipitation/neutralization tank will be provided with an air injection system which feeds in air and mixes it with the waste water with the help of an agitator. The latter will also keep the solids in suspended state. In the first reaction tank, aqueous ferrous sulfate (FeSO 4) will be added and the oxidation of ferrous to ferric state and As+3 to As+5 will be carried out. Excess iron, about three fold compared with the stoichiometric amount, will be required for the precipitation of ferric arsenate precipitate. The ferrous sulfate solution will be prepared by dissolving 23.6 tons of ferrous sulfate hexahydrate FeSO4 x 7H2O in 60 m of water and agitating the batch. The batch volume may be adjusted as per the requirement. In the second and third reaction tank, lime will be added. Sulfuric acid will be neutralized and excess iron precipitated as geothite. Lime milk will be prepared in a separate tank by mixing slacked lime Ca(OH)2 with water to produce suspension containing about 200 g/l. lime. As pH of the suspension will rise, dissolved heavy metals will be precipitated as hydroxides. The following reactions provide the basis for the treatment in neutralization/precipitation tanks.
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H3AsO4 + FeSO4 + Ca(OH)2 + 0.25 O2 FeAsO4 + CaSO4 + 2.5 H2O HAsO2 + FeSO4 + 1.75 O2 + Ca(OH)2 FeAsO4 + CaSO4 + 1.5 H2O H2SO4 + Ca(OH)2 CaSO4 + H2O FeSO4 + Ca(OH)2 + 0.25 O2 CaSO4 + FeOOH + 0.5 H2O The suspension from the third neutralization/precipitation tank will be fed to the thickener where flocculant is added to the mixture. In this tank, suspension will be thickened from 33 g solids/l to 200 g/l. Flocculant solution will be made in the flocculant. The overflow from the thickener, which contains very less amount of solids will flow to the circulation tank by gravity and will be used for the preparation of ferrous solution, lime suspension and flocculant solution. The excess water in the circulation tank will be pumped to the effluent lagoon and subsequently filtered by sand filters. Each sand filter will have circulating sand bed, which is continuously cleaned with the help of water and compressed air. The compressed air would lift the dirt from the sand bed. Six sand filters are envisaged for treating the whole effluent volume. After sand filtration, solids in the treated effluent are expected to contain less than 30 mg/l solids and comply with the effluent standards. Table 4.3 provides the expected quality of treated effluent, which will be led into the effluent pond. Table 2.3 : Expected quality of treated effluent to be stored in the effluent pond Characteristics Copper Lead Nickel Arsenic Cadmium Zinc Iron Mercury Fluorine Chlorine Solids Concentration (mg/l) 3.0 0.1 3.0 0.2 2.0 5.0 3.0 0.01 2.0 50 30

The underflow will be pumped to an automatic horizontal plate filter press, which would be provided with filtration, pressure drying, air drying and discharging stages. The filtrate will be collected in the filtrate tank. The filter cake will be taken to the ETP sludge storage place. Although the cake will appear to be dry, it will contain water about the same weight as solids.
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2.3

Solid Waste Management The following six types of solid wastes will be generated by the copper smelter project. Various methods that will be used to dispose off or reutilise these solid wastes are briefly discussed in this section. The detailed discussion is provided in 'Solid Waste Disposal Plan' and 'Phosphogypsum Reutilisation Plan' reports which are prepared as a part of this EIA and EMP study. Granulated slag Filter cake from the effluent treatment plant Copper/Arsenic precipitate from the refinery Spent catalyst from the sulfuric acid plant Fly ash and bottom ash from the captive power plant Phosphogypsum from the phosphoric acid plant

2.3.1

Granulated slag Granulated slag will be generated from the flash smelter furnace and Pierce Smith converter during the copper smelter operation. The amount of granulated slag produced for 100,000 tons of annual copper production is estimated to be between 82,500 and 115,500 tons. Taking into account the maximum production of 115,500 tons of slag with density of 3.6 tons per cubic meter, 1.98 hectares of area (200m x 90m) has been designated for storing slag up to 5 meter stack height. This storage space will accommodate the slag production for 2.6 years. Since, the slag has reuse potential, storage need not to be provided for the plant's life time production. Moreover, the stack height can be increased to accommodate more slag, if necessary. The storage site will not require any liner, as fajalites and other silicates comprising slag are inert. The granulated slag could have different uses depending the size of granules. Being hard and dense, these granules make ideal abrasives. The slag can be used as substitute for sand blasting, filler for saphalt shingles and black roofing granules. In addition to exploring market for the above uses, the slag my also be provided at subsidized rates for subsurface filling of the surrounding village roads.

2.3.2

Filter cake from the effluent treatment plant This waste type does not have any reutilisation potential, and hence provisions are made for safe on-site disposal of the waste produced for the entire life time of the plant. The latter is assumed to be 30 years. Considering an average annual production of 42,600 tons of ETP cake (wet weight), the total quantity of ETP cake generated in 30 years will be approximately 1.278 million tons. An area of 14.91 hectares (497m x 300m) will be reserved on-site for the disposal/storage of the ETP cake.
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The ETP cake would fall under the hazardous waste category as it will contain Arsenic, Cadmium, Lead and Mercury in quantities higher than limits specified the hazardous waste category of the Hazardous Waste (Management and Handling) Rules, 1989. To prevent percolation of these heavy metals and other impurities in the ground water and sub-soil systems, the storage/disposal site for ETP cake will have a double layer composite liner along with leachate collection and removal system (LCRS). Sumps will be provided for both primary and secondary LCRS for the periodic monitoring of the leachate quality. The leachate will be circulated back to the effluent treatment plant. The detailed description about the development of the site for storing the ETP cake is provided in 'the Solid Waste Disposal Plan' report. This site will be developed in stages, if necessary. 2.3.3 Copper/Arsenic precipitate from the refinery The amount of copper/arsenic precipitate or powder produced from the refinery is expected to be 327 tons per annum with arsenic content being about 96 tons per annum. This Cu / As precipitate will be stored in PVC drums. These drums will be stored on-site. Employees handling this waste will be trained for this purpose. The allocated area for storing these waste containing drums will have restricted access. 2.3.4 Spent catalyst Vanadium Pentoxide will be used as a catalyst during the production of sulfuric acid. The annual average change of catalyst is expected to be 51.4 tons. The spent catalyst will be smelted in the Flash Smelting Furnace in small quantities. The possibility of selling the spent catalyst back to vendor will be explored. 2.3.5 Ash from the Captive Power Plant Fly ash The amount of fly ash generated per year from the lignite based captive power plant, which needs to be disposed off, is estimated to be about 45,900 tons. The emphasis will be placed on exploring the market for the utilization of this fly ash in cement industry. However, on-site storage provision will be made to store the fly ash for over 2 years to allow for the development of market or accommodate ash when the market is sluggish. An area of 1.98 hectares (200m x 90m) will be reserved for the storage of fly ash produced for 2.18 years. Although fly ash, depending on its characteristics, can have several potential uses, focus has been placed on using fly ash in cement industry because of the following factors:

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Cement industry has the potential to utilize fly ash in bulk quantities. Cement industry is an organized sector, and doing business with an organized sector is easier than doing business with an unorganized sector such as construction industry or agricultural sector. Since phosphogypsum that will be produced from the phosphoric acid plant also has use potential in cement industry, marketing efforts for both fly ash and phosphogypsum can be combined.

Fly ash is already being used by several cement industries, and there may be more pressure from the government on the cement industry for using fly ash. Fly ash when mixed with Calcium Hydroxide (or burnt lime and water) chemically reacts with the latter to form the same types of binding agents as Portland cement. Fly ash may be added to Portland cement up to the replacement level of 20-30 percent. In fact, fly ash addition to cement could have a number of technological advantages, which include reduction in water demand, improved workability, reduction in water segregation, reduction in the heat of hydration, and therefore, less susceptibility to thermal cracking. Some disadvantages of mixing fly ash with cement include increase in the initial setting time and reduction in initial strength even though the ultimate strength after 28 days and 1 year will be the same as Portland cement. As mentioned above, fly ash characteristics will also determine its use potential in cement industry. These characteristics are determined by both nature of coal / lignite used in the captive power plant as well as the type of combustion technology used. Since the captive power plant will use Circulating Fludised-bed Boiler technology, which has high combustion efficiency, the carbon content of fly ash will be low. Also, the use of highly pulverized coal will be used in boiler furnace, which would result in fine particle size fly ash. Both the low carbon content in and fine particle size of the fly ash will enhance its reactivity, which is desirable for mixing fly ash with Portland cement. Moreover, for better quality control, the composition of fly ash will be regularly monitored to meet the specifications of the cement industry with which the agreement for selling the fly ash will be signed. Bottom ash / ash clinker The bottom ash or ash clinker along with gypsum (produced as a result of lime injection in the furnace to capture SO2) will be stored on-site. An area of 4.14 hectares (460m x 90m) of land will be kept aside for storing this waste. As this waste can not be reused, provision will be made to store this waste for the plant life, which is taken as 30 years.

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2.3.6

Phosphogypsum from the phosphoric acid plant The annual production of phosphogypsum from the phosphoric acid plant with the annual production capacity of 1,00,000 tons is expected to be 5,00,000 tons. This is a huge quantity of waste, which on inadequate disposal could have both quantitative and qualitative impacts on various environmental components depending on the mode of disposal. Fortunately, phosphogypsum has several potential uses, which include using it i) ii) iii) iv) As additive in the manufacture of cement for retarding setting time, In manufacturing of ammonium sulfate (fertilizer), As soil additive for alkaline agricultural soils, and In manufacturing of plaster and plaster boards.

To begin with, the focus will be on the use of phosphogypsum in cement industry, and the market for the same will be explored. Phosphogypsum could be added in place of gypsum to cement clinker obtained from the incineration of finely ground mixture of lime bearing material such as calcium carbonate with clay or laterite containing aluminium silicate. Phosphogypsum or gypsum is added to retard the setting time of cement for better workability. Typically, gypsum or phosphogypsum required to be added to the clinker as a retarder is about 4 percent of the cement produced. Using this as a basis, the demand for gypsum/phosphogypsum in the cement industry in Gujarat and adjacent states is estimated to be about 13.72 lakh tons, which could theoretically accommodate 5 lakh tons of phosphogypsum produced. Moreover, since phosphogypsum needs to be added at the grinding stage of the cement clinker, phosphpgypsum could be directly supplied to grinding plants. The replacement of natural (mineral) gypsum by phosphogypsum as a retarder could have limitations. Due to P2O5 content and fluoride impurities in phosphogypsum, hydration characteristics of cement could get affected. These impurities, particularly if soluble, delay setting time beyond desirable limits and also reduce early age compression strengths of cement. Hence, the desirable quality of phosphogypsum will be maintained so that it is acceptable to the cement industry. The recommended chemical composition of phosphogypsum for using it in the cement industry is shown in Table 2.4. The use of phosphogypsum to convert ammonium carbonate fertilizer to ammonium sulfate will also be explored in the long run. In this process, phosphochalk of equal quantity will be produced which would have to be disposed off either as a landfilling material or using it in the cement industry. Table 2.4 : Recommended chemical composition of Phosphogypsum Constituent
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Recommended Limit

Gypsum content (CaSO4 2H2O) Lime content (CaO) Sulfur trioxide content (SO3) Phosphorous Pentaoxide- P2O5 Total Water soluble Fluorides Total Water soluble Free Chloride Organic Matter Gypsum hemihydrate Free moisture

> 85% > 27.5% > 39.5% < 1.0% < 0.1% < 0.3% < 0.1% < 0.01% < 0.01% Nil < 2.0%

Even though, emphasis is placed on the use of phosphogypsum, about 11.65 hectares of land will be reserved for the on-site storage of phosphogypsum. About 5 meter high stack at this site can accommodate 2 years of phosphogypsum production. If necessary, the stack height could be as high as 18 meters. The site reserved for storing phosphogypsum will be lined with low density poly-ethylene (LDPE) sheets to prevent leachate (which may contain F) percolation in the ground water and subsoil system. 2.4 Greenbelt Development About 194,526 trees covering 758, 541 square meters of land area (which is about 35 percent of the project site area) will be planted to enhance the environmental quality. These trees will help in absorbing greenhouse gases and other air pollutants discharged from the copper smelter project to some extent. The tree cover will also improve the aesthetics of the site and act as wind breaker. The layout of the greenbelt is shown in Figure 4.2.

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