ANNEXURE I DETAILS OF PRODUCTS AND BYPRODUCTS (EXISTING AS WELL AS PROPOSED)

Transcription

1 ANNEXURE I DETAILS OF PRODUCTS AND BYPRODUCTS (EXISTING AS WELL AS PROPOSED) Sr. No. Products/By Products Units Existing Capacity 1 Soda Ash Plant Proposed Capacity Total Capacity after Expansion A Light Soda Ash TPD B Dense Soda Ash TPD C Vacuum Salt TPD Caustic Soda Plant A Product Caustic Soda (100%) TPD Hydrochloric Acid (100%) TPD B By Products Chlorine Gas (100%) TPD Hydrogen (100%) TPD Sodium Hypo Chlorite (100%) TPD Captive Power Plant Power MW Chlorine & Hydrogen Derivatives A Hydrogen Peroxide (100%) TPD B Epichlorohydrine (ECH) TPD C Glycerin TPD D Mono Chloro Acetic Acid (MCAA) By Products TPD Hydrochloric Acid (100%) TPD Mother Liquor of MCAA TPD Sodium Hypo Chlorite (100%) TPD Product E Trichloro Acetyl Chloride (TCAC) By Product TPD

2 Hydrochloric Acid (100%) TPD 9 9 Sodium Hypo Chlorite (100%) TPD 1 1 Sodium Bisulfite Solution (100%) 5 Toilet Soap Plant TPD 3 3 Toilet Soap TPD Detergent Powder TPD Detergent Cake TPD Fatty Acid TPD Glycerin TPD Bromine Plant Bromine TPD

3 ANNEXURE II BRIEF PROCESS DESCRIPTION 1. SODA ASH: Process Description The global theoretical equation for the production of soda ash, involving sodium chloride and calcium carbonate is as follows; 2 NaCl + CaCO 3 Na 2 CO 3 + CaCl 2 In practice the reaction is not possible and needs the participation of other substances and many different process steps to get the final product. The first reaction involves absorption of ammonia in salt solution, followed by reaction of ammoniated brine with carbon dioxide to obtain ammonium carbonate followed by ammonium carbonate. The continuous introduction of carbon dioxide injection and cooling the solution, precipitation of sodium bicarbonate is achieved and ammonium chloride is formed. The chemical reactions of the process are given below: NaCl + H 2 O + NH 3 NaCl + NH 4 OH 2 NH 4 OH + CO 2 (NH 4 ) 2 CO 3 + H 2 O (NH 4 )2CO 3 + CO 2 + H2O 2 NH 4 HCO 3 2 NH 4 HCO NaCl 2 NaHCO NH 4 Cl Sodium Bicarbonate crystals are separated from the mother liquor by filtration, followed by thermal decomposition to obtain sodium carbonate, water and carbon dioxide. Sodium carbonate, thus formed is called light soda ash because its bulk density is approximately 0.5 t/m 3. 2 NaHCO 3 Na 2 CO 3 + H 2 O + CO 2 CO 2 is recovered in the carbonation step. The mother liquor is treated to recover ammonia, by reacting with dry lime followed by steam stripping to recover free gaseous ammonia, which is recycled to absorption step. 2 NH 4 Cl + H 2 O+CaO CaCl NH H 2 O Carbon dioxide and Calcium oxide originate from limestone calcinations CaCO 3 CaO + CO 2 Calcium and magnesium which are impurities in the brine are removed by reacting with alkali and carbon dioxide to produce insoluble salts. Brine purification reactions are described in the following equations: Ca CO 3 CaCO 3 3

4 Mg OH Mg (OH) 2 The difference between Light and Dense Soda ash is bulk density & the size of particles. Dense Soda ash is produced via the monohydrate process. The hot light soda ash discharge from Calciner is transported via chain conveyors and bucket elevator to Hydrator. In hydrator Light Soda ash is mixed with water to form monohydrate according to the exothermic reaction: Na 2 CO 3 + H 2 O Na 2 CO 3.H 2 O The next step is dehydration and drying of the monohydrate in Fluid Bed Dryer according to endothermic reaction: Na 2 CO 3.H 2 O Na 2 CO 3 + H 2 O The Dense Soda Ash is cooled and transported to storage to packing plant. The block diagram of the Soda Ash Manufacturing unit is given in the Figure shown below. CO 2 gas MT NH 3 gas 0.32 MT Reuse in next operation Salt 2 MT Lime Stone 1.75 MT Ammonia 0.32MT Soda ash 1 MT Coke MT Process Sodium Sulphide MT Water 6 m 3 CaCl MT Waste water 6.5 m 3 4

5 Mass Balance: SALT RO / RAIN WATER COKE LIME STONE BRINE PREPARATION AIR LIME KILNS WASTE TREATMENT SETTLING OF SOLID PURIFIED BRINE CaCl2 Waste AMMONIA GAS ABSORPTION LIME DISTILLATION STEAM 38-40% CO2 ZERO DISCHARGE CLEAR LIQ. TO SALT WORKS AMMONIA MAKE UP CARBONATION COMPRESSION STEAM DENSIFICATION LSA CRUDE BICARBONATE FILTERATION 80-90% CO2 DSA STORAGE LSA STEAM CALCINATION CO2 + H2O MOTHER LIQUOR NH4Cl GAS CONDENSATION LSA & DSA PACKING FINAL PRODUCTS 2. CAUSTIC SODA: Process Description: The Caustic soda manufacturing technology being used i.e. membrane technology is completely environment friendly. The by products are hydrogen, chlorine & sodium hypo chlorite. Hydrochloric acid is manufactured using H 2 and Cl 2 (produced from cell house). Manufacturing process of Caustic Soda involves the following key steps: Brine Saturation: Desirable circulating rate of brine in saturator is attained by dissolving salt from solar salt works and depleted brine from the process. The water loss by membrane is compensated by supply of demineralized water. Chemical Preparation: In precipitation tanks saturated brine is treated to remove Ca, Mg & Sulphates by adding Na 2 CO 3, NaOH and Barium Chloride. Clarification: Flocculants are added to enhance the settling. Impurities are removed in clarifier. Main impurities are solids which are pumped to sludge filtration unit. Filtrate is recycled to clarifier. Filtration: Anthracite filters are used to remove suspended solids. Secondary Brine Purification: Polishing candle filters and ion exchange system is used for this process. The objective of producing ultra pure brine required for membrane cell 5

6 operation is achieved. Polished brine after heating through brine heater is passed through two ion exchange columns connected in series. The columns have cation exchange resin, which provides active sites for adsorption of residual calcium and magnesium salts still present in brine. Brine is passed through heat exchanger for achieving the temperature required at cell inlet. Electrolysis: Brine flows into the anode chamber. Cl 2 is liberated at the anode surface with depleted brine left behind. C l2 and depleted brine overflows from the anode chambers into the anolyte header. Weak caustic flows into the cathode chamber. H 2 is generated at the cathode surface and OH ions combine with the Na + ions diffusing through the membrane. A two phase mixture of 32% NaOH and hydrogen overflows into the catholyte header. Anode Reaction: 2NaCl 2Na + + Cl e Cathode Reaction: 2H 2 O + 2 e 2OH +H 2 Overall Reaction: 2NaCl + 2H 2 O 2NaOH + Cl 2 + H 2 Catholyte System: In the catholyte header the two phase mixture of NaOH and Hydrogen gets separated. This catholyte stream is tapped as Product and fed to the caustic evaporation unit. Whole stream is not tapped and some part is sent for internal consumption. Anolyte Dechlorination: Depleted brine containing dissolved chlorine (called anolyte) is dechlorinated in two stages: Vacuum dechlorination and chemical dechlorination. A part stream of chemically dechlorinated brine is be purged out of the system to keep the sulphate within the desired levels. Caustic Evaporation Unit: Here the incoming 32% Caustic is concentrated to 50%. The 50% caustic coming from this unit can be stored in 50% storage tank. Chlorine Treatment: The water vapor is removed, from the saturated chlorine, using series of coolers. The gas is then passed through the moist chlorine filter to remove the entrained brine aerosol. In drying towers 98% H 2 SO 4 is used to dry moist chlorine. The dried chlorine gas is compressed to the required pressure and then liquefied. Liquid chlorine from the liquefiers is sent to liquid chlorine storage tanks. Sniff gas from the liquefier containing inlets and chlorine gas is sent to the HCl synthesis unit. Excess sniff gas, is diverted to the waste air system. Hydrogen Treatment: Hydrogen gas leaving the cells saturated with water vapor is cooled. The cooled gas is passed through filters to remove the NaOH aerosols. Some amount of 6

7 hydrogen is required for HCl synthesis and a part of the gas is sent to caustic flaking unit to be used as fuel and a part is sent to hydrogen bottling through hydrogen compressors as per requirement and the balance hydrogen is vented through with flame arrestor. HCl Synthesis Unit Hydrogen is burnt in Chlorine atmosphere and the combustion gases are absorbed in water to yield a 32% HCl solution. HCl produced is pumped to HCl head tank from HCl receiver for internal consumption within plant. The Block diagram showing the Caustic Soda Manufacturing Process is shown in below figure; Cl2 Gas MT H2 Gas 7.65 MT Water MT Drift loss MT Evp. Loss MT Salt MT Salt MT Water NaOH 48% 546.1MT Water MT Na2CO MT Na2CO3 H2SO4 98% 5.51 MT H2SO MT Water HCL 32% 728.9MT Water MT A.cellulose 0.10 MT Flocculant 0.01 MT NaHSO MT Process water MT Hypo 59.2 MT Water MT 53.3 MT H2SO4 78% 6.9 MT Water 1.46 MT Sludge MT Liq. Effluent Water MT 270 MT CT Blow Down MT Purge Brine MT Water 270 MT 7

8 Schematic Diagram of Caustic Soda Manufacturing Process VENT HYPO FILLING HYPOCHLORITE STORAGE WASTE GAS DECHLORINATION CHLORINE COOLING & DRYING 78% H 2 SO4 VENT 98% H 2 SO 4 CHLORINE COMPRESSION CHLORINE LIQUEFICATION HCL FILLING HCL STORAGE HCL SYNTHESIS UNIT H 2 TO STACK HYDROGEN TREATMENT LIQUID CHLORINE STORAGE CHLORINE FILLING BRINE PURIFICATION (ION EXCHANGE) ANODE CATHODE + - DM WATER HYDROGEN BOTTLING BRINE FILTRATION CHLORATE DESTRUCTION ANOLYTE DECHLORINATION CATHOLYTE SYSTEM CAUSTIC EVAPORATION BRINE CLARIFICATION SLUDGE FILTRATION SLUDGE NaHSO 3, NaOH 32% SOLUTION 48.5 / 50%NaOH SOLUTION BRINE BRINE PRECIPITATION FLOCCULANT SALT SALT SATURATION DM WATER/ CONDENSATE CAUSTIC TO STORAGE AND FILLING FLAKING UNIT CHEMICALS Na 2 CO 3,NaOH SALT FLAKES STORAGEAND BAGGING 3. CAPTIVE POWER PLANT In the case of lignite/coal fired boilers, steam generation with any of following firing technology is technically feasible: Circulating fluidized bed combustion (CFBC) Pressurized Fluidized Bed Combustion (PFBC) Integrated Gasification Combined Cycle (IGCC) Pulverized Fuel Firing (PF) Circulating fluidized bed combustion (CFBC) technology is adopted for the proposed captive power plant. A 100 MW captive power plant turbo alternator and 350 TPH TPH (standby) lignite/coal/petcoke based CFBC Boilers, along with captive power plant machineries will be installed in order to meet internal steam and power requirement for the proposed expansion. The steam generator units proposed for the plant will be compact, semi outdoor, natural/assisted circulation, balanced draft, single drum, water tube type provided with Circulating Fluidized Bed Combustion system using pan leg furnace configuration. In a 8

9 typical Circulating Fluidized Bed furnace, the lignite fed on a bed of suitable inert material with addition of a sorbent material (such as lime stone) is burnt in suspension through the action of primary air distributed below the combustor floor. In addition, secondary air is introduced at suitable points in the combustion zone to ensure controlled and complete combustion of the fuel. Suitable lignite feeding and limestone feeding arrangements are provided in the typical Circulating Fluidized Bed Combustion systems and is commonly used as bed material for initial start up of the boiler. The steam generators will be designed for satisfactory continuous operation with the range of lignite/coal expected for this plant without any need for auxiliary fuel oil for fire stabilization etc. Lignite and Coal are used as fuel after mixing in appropriate ratio. Steam generating unit would be provided with electrostatic precipitator in the flue gas path. The overall efficiency of ESP will be around 99.70% with one field remaining as operational standby. The ESP would have adequate number of ash hoppers provided with electric heaters. The design of ESP will be such that the dust burden at the outlet of chimney with one field out of service doesn t exceed 150 mg/nm 3 at 100 % BMCR with worst fuel. Common chimney for boiler G and H will be constructed. The NO x emission from the steam generator is least in case of CFBC steam generator design in view of low combustion temperature maintained in the furnace. The steam generator and auxiliaries will perform continuously within noise limits as per relevant standard specification but not more than 85 db (A) at 1.0 meter from any equipment or sub equipment. The steam from the boiler will go to back pressure turbo generators. The extracted back pressure steam will be used in process. 4. HYDROGEN PEROXIDE : MANUFACTURING PROCESS: This process is based on a circulating working solution, known as the AO (autoxidation) process for hydrogen peroxide production. The steps, which the working solution passes through, are hydrogenation, oxidation, drying and regeneration. The working solution consists of organic solvents and quinones, 2 ethylanthraquinone and 2 ethyltetrahydroanthraquinone and their reduced derivatives. The quinones act as carriers of hydrogen between the hydrogenation and oxidation steps. 9

10 Hydrogenation: The working solution and hydrogen are fed to a hydrogenator and in the presence of catalyst, 2 ethyltetranthraquinone (H 4 EAQ or THEAQ) is partially converted to 2 ethyltetrahydroanthraquinone (H 4 EAQH 2 or THEAQH 2 ) (Reaction 1). The conversion ration is primarily controlled by the amount and activity of the catalyst present in the system, temperature and hydrogen concentration. An excess flow of hydrogen (recycle) to the hydrogenator is maintained to fluidize the catalyst. The hydrogen is taken out in the reactor top and returned to the hydrogenator via a recycle compressor. The working solution and catalyst flow to the primary filters. Here the forward flow of liquid is separated from catalyst and passes on to an oxidizer feed tank while the remaining working solution and catalyst are returned to the hydrogenator. Oxidation: The hydrogenated working solution combined with air (oxygen) in an oxidizer. It is in this step of the process that hydrogen peroxide (H 2 O 2 ) is actually produced. The HEAQH 2 in the working solution chemically reacts with oxygen to produce H 4 EAQ and H 2 O 2 (Reaction 2). Hydrogen peroxide at this point is dissolved in the working solution and the only visible indication that reaction has taken place is a colour change in the working solution. The hydrogenated solution is dark brown, during the oxidation the colour changes and becomes reddish brown. In the top of the reactor, the inert fraction of the air is separated from the working solution and discharges through a solvent recovery system. The working solution flows into a degasser, where any dissolved inert gas is separated from the liquid phase. 10

11 Extraction: Working solution form the oxidizer degasser is fed into the bottom and demineralized water into the top of an extraction column. Water is the continuous phase and working solution the discontinuous phase. Due to the different densities of the two phases the working solution flows upwards and discharges from the top of the extractor after being stripped of its hydrogen peroxide. The aqueous phase discharging from the bottom of the extractor contains normally 30 35% hydrogen peroxide. Product Treatment: Hydrogen peroxide is discharged from the bottom of the extractor into a purification system. The function of the purification system is to remove traces of working solution components into order to minimize losses and get a low total organic carbon content of the crude product, which improves the stability. Drying: The working solution leaving the extractor is saturated with water. The drier reduces the water content by heating the working solution and flashing it under vacuum. The benefits with less water in the working solution are better catalyst efficiency and a lower operating temperature in the hydrogenator, resulting in less side reactions. Regeneration: Due to the circulating working solution, undesirable compounds (principally different quinine derivatives) can accumulate in the system. In order to keep the concentration of the undesirable compounds into active quinones. This is carried out in columns with activated alumina, the process is known as regeneration. If oxidized working solution is fed to the alumina beds a reaction known as reversion will occur. The reversion reaction converts H4EAQ to EAQ, and can be used to control the ration between tetra and anthra in the working solution. 11

12 FLOW DIAGRAM: Oxygen depleted air to atm Working Solution Inert & H2 Purge Activated carbon Solvent recovery Spent carbon Demineralized water H 2 Oxygen Depleted air H 3 PO 4 Oxidized W.S Hydrogenati on Catalyst Oxidized W.S Catalyst + Reduced W.S Catalyst + Reduced W.S Filtration Activated Alumina Reduced W.S Regeneration Oxidation Air Spent Alumina Ox. W.S Extraction H 2 O wt.% Organic return Product Cleaning Stabilizer H 2 O wt.% Concentrati on H 2 O 2 50 wt.% Day tanks and Product storage Vapour( water,solvent,inerts) Drying Water recovery (used as makeup water) Extracted W.S H 2 O 2 50 wt.% Packing & Loading 25

13 MATERIAL BALANCE : Inert & H 2 Purge 26 Nm 3 Solvent 2 g/m 3 Oxygen depleted air to atm 4000 Nm 3 Solvent 12.5 g/m 3 H Nm 3 Air 4100 Nm 3 Working Solution 3.1 Kg Catalyst 0.04 Kg Phosphoric Acid 0.3 Kg Stabilizer 1.3 Kg DM Water 2 m 3 Activated Alumina 10 Kg NaOH (100%) 1 Kg HNO 3 (100%) 1 Kg Activated carbon 1.01 Kg Inert N 2 25 Nm 3 H 2 O 2 (50 wt.%) 1.0 MT Catalyst 0.04 Kg Spent Alumina 10 Kg Spent Carbon 1.01 Kg Wastewater to ETP m 3 5. GLYCERIN & EPICHLOROHYDRINE (ECH) : The plant is designed to produce Epichlorohydrin from crude glycerin and HCl gas. The plant consists of I. Glycerin Purification Plant II. ECH Production Plant I. Glycerin Purification Plant The liquid raw materials like Crude Glycerin, Methanol and NaOH are stored in the storage tanks. Crude Glycerin and NaOH are pumped from the storage tanks into the neutralization vessel. Neutralization and Drying of Crude Glycerin: The Crude Glycerin is neutralized in the Vessel with approx. 30 % concentrated NaOH and preheated up to 120 C. In the first drying column, the main content of water is evaporated under atmospheric pressure and in the second drying column, the water content is reduced below 1 wt. % under 26

14 Vacuum. In the first drying column, the Methanol content is also removed together with the water. In the second drying column, the Glycerin content in the vapor is removed in the partial condenser. Rectification: After the dryer section, the crude Glycerin comes into the column bottom and is evaporated in a forced circulation evaporator and rectified in 3 packing sections. Refined glycerin is taken out from middle packing section. The by product is impure Glycerin collected from top packing section which is recycled into the column and only in case of bad Crude Glycerin quality approx. 5% of the total produced Glycerin has to be recycled into the Vessel. Purification of bottom product: Depending of the salt concentration in the crude Glycerin, a certain quantity of bottom product has to be pumped into the heavies separation decanter centrifuge where crude Glycerin stream is recycled to the bottom of column and another part is fed into the thin film evaporators where the main part of the Glycerin is separated and the remaining part goes into the lock hopper vessels. The bottom product consisting of 82 wt % MONG / Glycerin and 18 wt% heavies/polymers is removed from the lock hopper and sent to disposal pit. After natural cooling and solidification, product is dispatched outside plant. Salt purification (not required if crude glycerin is free of salt): The removed salt is mixed and purified with Methanol before the stream goes into Separator to separate the salt and into the dryer where the remaining Methanol is removed from the salt. The purified salt can be used for brine make up while the recovered Methanol goes into the neutralization Vessel. Methanol Distillation: The Methanol Water mixture from the top of the dryer column is purified in the methanol distillation column. The cleaned Methanol will be pumped back to the Methanol storage tank. II. ECH Production Plant The liquid raw materials like refined Glycerin and NaOH are stored in the storage tanks. HCl gas is delivered by pipeline from the HCl synthesis unit with pressure. Oxalic acid is delivered as a powder in bags. Glycerin and NaOH are pumped from the storage tanks into the reaction vessels. The Oxalic acid catalyst is dissolved in water once per day and then continuously pumped in the Chlorination reactor. 27

15 Chlorination of Glycerin: The Glycerin is heated in the circulation loop of the storage tank up to 80 C and is absorbing the excess of HCl Gas in the scrubber, preheated up to 120 C in heat exchanger and is reacted with the excess of HCl from the Chlorination reactor. The main Chlorination step is taking place in the reactor, where on the bottom is the feed of the preheated Glycerin, the HCl gas and the catalyst oxalic acid together with the bottom product from the vacuum distillation. The reaction happens in two steps: Step one: C 3 H 8 O 3 + HCl = C 3 H 7 ClO 2 + H 2 O Step two: C 3 H 7 ClO 2 + HCl = C 3 H 6 Cl 2 O + H 2 O Step one is much faster than step two. Separation of Reaction Products: Dichlorhydrin and Water: The overflows of the reactor are collected in the vessel and pumped into the vacuum distillation columns where water and Dichlorhydrin is separated from the Glycerin and Monochlorhydrin as a bottom product. Separation of Waste Products A small purge is continuously separated from the reactor circuit and distilled in the thin film evaporator to separate the Dichlorhydrine & Monochlorhydrin to reduce the product losses in the waste. The liquid waste stream is then sent to incinerator. Saponification into Epichlorohydrin: The saponification works according the reaction: C 3 H 6 Cl 2 O + NaOH = C 3 H 5 ClO + H 2 O + NaCl To avoid polymerization as side reaction the NaOH is fed as a 20 wt% solution, which is prepared inside the plant. Separation of Epichlorohydrin from Brine: After saponification step, the brine is treated in the stripper column and nearly azeotropic mixture of water and Epichlorohydrin is recovered on the top of the stripper. After condensing the vapors, water rich phase and an Epichlorohydrin rich phase is obtained. The water rich phase is recycled into the stripper and the Epichlorohydrin rich phase is the feed for the Epichlorohydrin purification unit. Purification of Epichlorohydrin (99.8 wt.%): To obtain high quality Epichlorohydrin a two column rectification is necessary. In the first column, the water content is separated and in the second column, the Epichlorohydrin is recovered as a top product and as bottom product some polymers and equilibrium products are separated. 28

16 Effluent Brine Stream: Effluent brine from ECH distillation columns shall be sent to the separate crystallizers/pond for solar evaporation of this stream so as to recover the salt. FLOW DIAGRAM : Crude Glycerin NaOH Methanol +Water Glycerin Purification Plant Salt MONG/Glycerin Foot Oxalic Acid Refined Glycerin D.M.Water Waste gas from glycerin purification plant HCl gas Dichlorohydrin + Water Chlorination Waste gas Purge (Residues) Waste Incinerator Flue gas to ATM NaOH Saponification Steam Effluent Brine Recycle Stripper Column Water rich phase Recycle Epichlorohydrin purification unit Epichlorohydrin Epichlorohydrin 29

17 MATERIAL BALANCE : Waste gas to Incinerator 0.6 Ton Methanol/Water 0.08 Ton Crude Glycerin 8.2 Ton Oxalic Acid 4 Kg NaOH (100 wt. %) 4.46 Ton Cl 2 gas 7.2 Ton H 2 gas 0.30 Ton DM Water 14 m 3 Refined Glycerin 6.6 Ton to ECH Plant ECH 6.25 Ton Brine 20 m 3 Waste water from GPP 4.1 m 3 Waste gas & Purge (Residues) To Waste Incinerator 0.34 Ton 32 wt.% HCl 1.4 Ton Salt 0.4 Ton Glycerin Foot/MONG 0.6 Ton 6. MONO CHLORO ACETIC ACID (MCAA): Manufacturing Process: Mono Chloro Acetic Acid (MCAA) is produced by continuous chlorination of acetic acid in presence of catalyst. After reaction is over, the Crude MCAA is fed to the crystallizers where it is cooled. The slurry containing crude MCAA crystals is fed to the pusher centrifuge continuously. Pusher Centrifuge continuously separates ML and MCAA powder. Powder is packed using auto filling system. Gases containing HCl & Chlorine is passed through the scrubbers wherein these are scrubbed with water and caustic soda solution respectively to get 32% HCl solution and Hypo. Mother liquor from the centrifuge is collected separately and taken for further chlorination to get second crop of Mono Chloro acetic acid. The MCAA powder collected from centrifuge is packed in HDPE 50 kg capacity bags. The MCAA powder is white free flowing needle crystal and hygroscopic in nature. 30

18 Chemical Reaction: CH 3 COOH + Cl 2 > ClCH 2 COOH Acetic Acid Chlorine + HCl Monochloro acetic Acid Hydrochloric Acid FLOW DIAGRAM: Chlorine Gas SMC/Acetic Anhydride Catalyst Water Dilute Caustic Acetic Acid Continuous Chlorination HCL+Cl 2 gas Acidic Scrubber 32% HCL solution Chlorine gas Alkali Scrubber Crude MCAA HCL+Cl 2 gas Chlorine gas Hypo Crystalizer Batch Reactor MCAA Slurry ML for processing Crude MCAA Filtration Crystalizer Hydrogen MCAA Powder for Packing MCAA Slurry Catalyst Unreacted Hydrogen Filtration ML Hydrogenation MCAA Powder for Packing MCAA + Catalyst Slurry Filtration ML MCAA powder Wet catalyst 31

19 MATERIAL BALANCE: Unreacted Hydrogen 0.36 Ton Chlorine Gas 100 Ton Acetic acid 79 Ton Acetic Anhydride/SMC 4 Ton MCAA powder 120 Ton Hydrogen gas 0.72 Ton Catalyst 0.15 Ton Dilute caustic soda 53.7 Ton Water Ton 32% HCl Solution Ton Hypo Ton ML Ton Wet catalyst 0.19 Ton 7. TRI CHLORO ACETYL CHLORIDE: Manufacturing Process: ML collected from centrifuge is having 50% MCAA and 50% DCAA (Di Chloro Acetic Acid). It is charged to the hydrogenation reactor in batch mode. DCAA is converted back to MCAA and is filtered to get the additional crop of MCAA crystals. The ML coming out after this process is taken to another reactor where it is reacted with chlorine gas in presence of catalysts. Chloro Acetyl Chloride (CAC) and Di Chloro Acetyl Chloride (DCAC) are in crude form and are distilled and pure mixture of CAC and DCAC is collected. It is further reacted with pyridine at high temp. Tri Chloro Acetyl Chloride (TCAC) is produced in crude form. It is distilled and purified to get 99.5% TCAC liquid. Final discharge of ML contains 50% MCAA and 50% DCAA. It is collected separately. It is a by product in the process. HCl and unreacted chlorine gases from reactors are taken to the water and alkali scrubbers respectively. Here we get 32% HCl solution and Hypo 15% solution as by products. Gases from the reacted are scrubbed in soda ash tower, water scrubbers and dilute caustic scrubbers. Sodium bi sulfite dilute solution, 32% HCl solution and dilute hypo 32

20 solution we received as by products. Final vent is from caustic ventury in which free chlorine gas will be 30 to 40 ppm. There is no air emission and no liquid pollution. It is a completely closed system there is no environmental pollutions from the system. Chemical Reaction: 4CH 3 COOH + 15Cl 2 + S 2 Cl 2 > 4CCl 3 COCl + 16HCl + SO 2 Acetic Acid FLOW DIAGRAM: Liquid Chlorine Sulphur mono Chloride Tri Chloro Acetyl Chloride Hydrochloric Acid Sulphur Dioxide ML Water + Unreacted Acetic Acid Distillation Chlorine + HCl + SO 2 Dilute soda solution Distilled ML Chlorine Water Scrubber Dilute NaHSO 3 solution SMC + catalyst Chlorination Chlorine + HCl Water Dilute Caustic Solution Fore cut/inter cut/end cut Crude TCAC Distillation Acid Scrubber Chlorine Alkali Scrubber TCAC TAR 32% HCl Solution Dilute Hypo Solution 33

21 MATERIAL BALANCE: Water + Unreacted Acetic Acid Ton ML Ton Chlorine Ton SMC + Catalyst 3.35 Ton Dilute Soda solution Ton Dilute Caustic Solution Ton Water 19 Ton TCAC 8.8 Ton 32 % HCl Solution Ton Dilute Hypo Solution Ton Fore cut/inter cut/end cut 3.98 Ton TAR 1.52 Ton Dilute NaHSO 3 Solution Ton 34

22 Sr. No. Soda Ash Plant Source ANNEXURE III DETAILS OF WATER CONSUMPTION Water Consumption (m 3 /day) Existing Proposed Total 1. Domestic Process Boiler Cooling Others Total (I) Toilet soap plant 1. Domestic Process Washing Cooling Total (II) Caustic Soda Plant & Captive Power Plant 1. Domestic Process Boiler Cooling Salt works Total (III) Salt works Bromine Plant Total (IV) Process Cooling Total (V) Chlorine & Hydrogen Derivatives 1. Domestic Process + DM Cooling + Chilling Boiler Washing/Others Total (VI) Grand Total (I to VI)

23 Sr. No. Soda Ash plant DETAILS OF WASTEWATER GENERATION Source Wastewater Generation (m 3 /day) Existing Proposed Total 1. Domestic Process Boiler Cooling Others Toilet Soap plant Total Domestic Process Washing Cooling Total Caustic Soda Plant & CPP 1. Domestic Process Boiler Cooling Salt works Total Salt works Total Bromine plant 1. Cooling tower Process Chlorine & Hydrogen Derivatives Total Domestic Process + DM Cooling + Chilling Boiler Washing/Others Total (VI) Grand Total (I to VI)

24 ANNEXURE III WASTEWATER TREATMENT PROCESS 1. Soda Ash Plant Effluent Treatment System: The effluent from the Soda Ash plant mainly consists of suspended solids. The effluent is pumped into the Primary Settling Ponds through pipelines. The Settling Ponds having trapezoidal settling facility where the effluent is retained for settling of solids. The overflow of the Primary Settling Ponds is taken into one of the two large impervious Clear Liquor Collection Ponds. The Clear liquor from the Clear liquor pond is utilized in the existing Salt works to recover additional Salt and Gypsum. Effluent from Soda Ash Plant Clear Liquor Tank (100 acres) Settler Tank (200 acres) Sump Utilization in Existing Salt Works for Recovery of Salt & Gypsum 37

25 2. Caustic Soda Plant Effluent Treatment System: The process effluents and floor washing from the caustic soda & Captive Power plant needs ph correction. The two streams are pumped to neutralization tank through pipelines and treated with HCl/NaOH to ensure complete neutralization. The neutralized effluent is settled and the supernatant is sent to Salt work. The blow downs from the cooling towers of caustic soda plant from both the once through cooling system, and fresh water cooling towers are sent to salt works. Cooling water from caustic soda plant, captive power plant (once through cooling water) and boiler are sent to salt works. ETP 1 (Existing) Floor Washings Process Effluent Neutralization Tank (2 Nos.) 10 m X 5 m X 2m Treated Water Tank (1 Nos.) 10 m X 5 m X 2m Treated Effluent used for Green belt development Or Dust Suppression purpose ETP 2 (Proposed) Floor Washings Process Effluent Neutralization Tank Treated Water Tank Treated Effluent used for Green belt development Or Dust Suppression purpose 38

26 3. H 2 O 2 Plant Effluent Treatment System: Process Effluent Treatment Scheme From Process plant Process Effluent 10% NaOH Equipment Description: 1 10% NaOH Dosing Tank 2 10% NaOH Dosing Pump 3 10% NaOH Dosing Pump 4 Neutralization Reactor 5 Agitator 6 Treated Effluent Transfer Pump To Utility ETP 4 Compartment I Compartment II 6 Treated Effluent 39

27 Utility Effluent Treatment Scheme Alum NaOCL 1 2 Equipment Description: 1 Alum dosing Tank 2 Alum dosing pump 3 NaOCL Dosing Tank 4 NaOCL Dosing Pump 5 Effluent Transfer Pump 6 Utility Effluent Pit 7 ph Adjustment Pit 8 Transfer Pump 9 Filtered Water Transfer Pump 10 Filtered Water Pit 11 Sand Filter 3 From Utility Area Utility Effluent 4 11 From Process ETP Treated Effluent To RO Treatment Treated Effluent

28 1. MCAA & TCAC PLANT EFFLUENT TREATMENT SYSTEM: Process Description of the Effluent Treatment Plant EFFLUENT COLLECTION AND EQUALIZATION: All the effluent streams coming from plant and utilities are collected in a collection sump. Where it is directed to ETP as per the hydraulic flow diagram mentioned on the attached drawing for further treatment. PRIMARY TREATMENT: All the equalized effluent taken for neutralization tank. Where hydrated lime will be used as neutralizing agent. Than it is to be pumped in a batch wise manner to flash mixture where organic matter is remove by coagulation, flocculation and precipitation with the help of Ferric Alum/ Ploy aluminum Chloride/Lime and polyelectrolyte. After completion of precipitation, treated effluent is passed through primary clarifier to separate out solid sludge. Clear effluent from primary clarifier is allowed to overflow in bioreactor for secondary biological treatment. Sludge from the bottom of primary clarifier is taken into sludge sump. Filter press will be used as dewatering equipment. Effluent emerging out from primary treatment will be reduced COD and TDS as organic dissolved solids also get precipitated out. SECONDARY TREATMENT /AERATION For secondary biological treatment, Industry will be provided aeration tank having three partitions having volumetric capacity of 600 KL each so total volume of aeration tank will be 1800 kl with 24 hrs retention time to considering 50% recycle of sludge water. For desired reduction of COD and BOD, the suitable bacterial culture will be nourished and desired level of MLSS and MLVSS will always be maintained in the aerator by adding cow dung or other nutrients like Urea/DAP as and when required. For providing required amount of air for biological degradation, twin lob blower of 25 HP x 3 will be provided. Such large bio reactor will ensure long residence time and result into desired COD reduction in bioreactor on the daily basis. The overflow of aeration tank will be directed to final clarifier having mechanical scrapper to efficient sludge settling. The settled sludge will be taken to sludge sump from where it will be fed to above referred filter press for further compaction. Clear treated effluent from final clarifier will overflow to final treated effluent collection well from where after due analysis treated effluent will be reuse in gardening/plantation with in plant premises. 41

29 UNIT OF EFFLUENT TREATMENT PLANT Sr. No. Description 1 Oil & Grease Trap 2 Collection Tank 3 Neutralization Tank 4 Chemical Dosing Tank 5 Flash Mixer 6 Flocculation Chamber 7 Primary Clarifier 8 Aeration Tank 9 Secondary Clarifier 10 Filter press (Dewatering Unit) 11 Sludge Sump 12 Treated Effluent Sump 42

30 Sr. No. ANNEXURE IV DETAILS OF SOLID WASTE AND HAZARDOUS WASTE SOLID WASTE GENERATION AND DISPOSAL: Solid Waste Quantity (TPD) Mode of Disposal 1 Settling Pond Sludge Existing Proposed After Expansion Shall be used in road construction, salt works bund preparation Shall be used in boilers for desulphurization in boilers 2 Lime stone rejects /under size 3 Brine Sludge Nonhazardous; Shall be used dumped in identified area 4 Fly ash/ Bottom ash Brick manufacturing, bund preparation, road making etc 5 Incineration Ash Brick manufacturing, bund preparation, road making etc HAZARDOUS WASTE GENERATION & DISPOSAL Sr. No. Hazardous Waste 1 Soda Ash Plant Waste Oil/ Lub. Oil from Spent ion exchange resins Discarded bags/drums/con tainers etc Category Quantity (MTPA) Mode of Disposal Existing Proposed Total After Expansion Collection, Storage, Transportation & disposal by selling to Registered Recyclers L cation & L anion Collection, Storage, (once in 10 years) Transportation, Disposal by selling to authorized recyclers or sent to NECL Nandesari for Incineration Collection, Storage, Transportation, Disposal by selling to authorized recyclers 43

31 2. Caustic Soda Plant Waste Oil/ Lub. Oil from Spent ion exchange resins Residue/ Sludge & Filter sludge Collection, Storage, Transportation & disposal by selling to Registered Recyclers Collection, Storage, Transportation, Disposal by selling to authorized recyclers or sent to NECL Nandesari for Incineration Collection, Storage, Transportation, Disposal at TSDF ETP sludge Collection, Storage, Transportation, Disposal at TSDF Spent Sulphuric Acid (80%) 3. Toilet Soap Plant D Collection, Storage, Transportation, reuse as raw material for Nirma Ltd. Moraiya and other end users. Waste Oil/ Lub Collection, Storage, Oil from Transportation & disposal by selling to Registered Recyclers ETP sludge Collection, Storage, Transportation, Disposal at TSDF Glycerin foot D6 II Collection, Storage, Transportation & disposal by selling to M/s. Ultratech Cement for Co incineration in cement kiln/necl for Incineration. Spent Sulphuric Acid (80%) D Collection, Storage, Transportation, reuse as raw material for Nirma Ltd. Moraiya and other end users. 44

32 4 Chlorine & Hydrogen Derivatives Waste Oil/ Lub. Oil Discarded containers/ Barrels/empty drums/empty bags Collection, Storage, Transportation & disposal by selling to Registered Recyclers Collection, Storage and disposal by selling to authorized recyclers. ETP sludge Collection, Storage, Transportation, Disposal at TSDF Glycerin foot D6 II Collection, Storage & incineration in plant incinerator. Catalyst from regeneration Spent Carbon from solvent recovery Spent Carbon from ETP Distillation Residue Collection, Storage, Transportation, Disposal at Common Haz. Waste incineration facility Collection, Storage, Transportation, Disposal at Common Haz. Waste incineration facility Collection, Storage, Transportation, Disposal at TSDF Collection, Storage, Transportation, Disposal at Common Haz. Waste incineration facility 45

33 ANNEXURE V DETAILS OF STACKS AND PROCESS VENTS DETAILS OF STACK EMISSIONS Sr. Stack Attached to Stack Height Stack Air Pollution Pollutant No. (m) Dia. (m) Control System 1 Soda Ash Plant Boiler A, B, C & D (100 TPH each) 100 (Common stack) 5.04 ESP to Each boilers PM SO2 NOx DG Sets (2 nos.) 24 (each) Caustic Soda & CPP Boiler E & F (200 TPH each) 121 (Common Stack) 4.5 ESP PM SO2 NOx Boiler G & H (350 TPH TPH standby) 121 (Common Stack) 4.5 ESP PM SO2 NOx (Proposed) DG Set (1000 KVA) PM DG Set (1500 KVA) SO2 Proposed NOx DG Set (1500 KVA) Proposed 3 Toilet Soap Thermic Fluid PM Heater SO2 NOx 46

34 DETAILS OF PROCESS EMISSIONS Sr. Vent Attached to Stack Stack Air Pollution Pollutant No. Height (m) Dia. (m) Control System 1 Soda Ash Plant Lime Kilns (A to F) 6 nos. 68 (Common Stack) scrubbers and two ESP in Series PM, SO2, NOx Ammonia Recovery Brine Scrubbers Ammonia System (Common Stack) (3 nos.) Lime Grinding System Bag Filter PM (3 nos.) Calcinations Vessel 29 each 0.7 Water Scrubber PM (2 nos.) Densification Water Scrubber PM Densification Water Scrubber PM Lime Kilns (G & H) 2 nos. (Proposed) 68 (Common Stack) 0.8 One scrubbers and one ESP in Series PM, SO2, NOx Ammonia Recovery Brine Scrubbers Ammonia System (D & E) 2 nos. (Proposed) (Common Stack) (2 nos.) Lime Grinding System Bag Filter PM (2 nos.) (Proposed) Calcinations Vessel (2 nos.) (Proposed) 29 (Common vent) 0.7 Water Scrubber PM Densification Water Scrubber PM (Proposed) 47

35 2 Caustic Soda and CPP HCl Synthesis Unit Water Scrubbers HCl & Cl2 HCl Synthesis Unit Water Scrubbers HCl & Cl2 Waste Dechlorination System 1 Waste Dechlorination System 2 Gas Gas HCl Synthesis Unit 3 (Proposed) HCl Synthesis Unit 4 (Proposed) Waste Dechlorination Gas System 3 (Proposed) 3. Bromine Plant Debromination System 4. Chlorine & Hydrogen Derivatives Solvent (Proposed) Hydrogenation (purge (Proposed) Recovery Plant gas) Incinerator & its scrubber (Proposed) HCl Synthesis Unit (Proposed) Chlorination (Proposed) Plant % NaOH Scrubber % NaOH Scrubber Cl2 Cl Water Scrubbers HCl & Cl Water Scrubbers HCl & Cl % NaOH Scrubber Cl Alkali Scrubber Bromine Ceramic + Activated Carbon Filter Ceramic + Activated Carbon Filter Aromatic Solvent H2 + Aromatic Solvent Water Scrubber PM, SO2, CO, NOx, HCl, TOC Water Scrubbers HCl Acidic/Water Scrubber (3 nos.) SO2, HCl, Cl2 Chlorination Plant Alkali Scrubber Cl2 48

36 (Proposed) Chlorination (Proposed) Hydrogenation (purge (Proposed) Plant gas) (3 nos.) Water Scrubber SO2, HCl, Cl H2 49

37 Annexure VI Noise level, at existing plant Sr. No. Location Noise level in db(a) 1 Near Security Main Gate No Near Guest House Near Security Gate No Near Safety office Near Canteen Near Laboratory Near Work Shop area Toilet soap packing area Near Toilet soap ETP Near CCR Electrical Near DG Room Near Boiler operator office Near Boiler Stack area PWP Station area Calcination and Filtration Area Near Brine Purification Grinding mill area Lime kiln area Near Bricks Manufacturing area Near RO Plant area Near Thermic Fluid Heater Near Salt works office Near Diesel Pumping station