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ENVIRONMENTAL MANAGEMENT IN INDIAN CHLORALKALI INDUSTRIES

Dr.K.Subramanian, Scientist, Chlor-Alkali Division, Central Electrochemical Research Institute, Karaikudi-630006

Chlor-Alkali process is one of the chemical industry's leading workhorses and consists in the production of chlorine, sodium hydroxide (caustic soda) and hydrogen as a by-product. The chlorine and caustic soda are produced from the electrolysis of an aqueous solution of common salt or cooking salt. 2NaCl + 2H2 O Cl2 + H2+ 2NaOH This industry is the second largest consumer of electricity next to Aluminum. The term Chlor-Alkali is derived from the two products produced: chlor from chlorine and alkali from sodium hydroxide, which is part of a group of chemicals called alkalis. For one ton of Caustic soda produced, 0.88 ton of chlorine and 0.12 ton of Hydrogen are also produced. The caustic soda and chlorine industry is one of the largest chemical industry in the world as well as in India. Chlorine and Caustic soda have wide spread usage. Chlorine is mainly used for the production of PVC, Inorganics, pharmaceuticals(health sectors), automobiles, fire safety cloths, bleaching, water disinfection and purification. Caustic soda is used for the production of organics, soaps, paper, bleach and mineral oils. Hydrogen is used as a fuel, in fuel cells , for making hydrochloric acid and in hydrogenation of fatty acids to make refined food products

At present there are three processes available. Until 1980, there were only two conventional production processes for Chlor-Alkali Production 1) Diaphragm cell and 2) Mercury (amalgam) cell processes. Environmental and energy constraints lead to the development of modern membrane cell Process.

The worlds production of caustic soda comes around 700 lakh tonnes during 2003-2004 and in India, it is about 17 lakh tonnes (23 lakh tonnes-installed capacity). Indian chlor- alkali industry is 60 years old. Electrolytic caustic production started in India in 1940. First cell was a Diaphragm cell at installed at Mettur Chemicals, Mettur, Tamil Nadu in 1940. First mercury cell plant was also at the same place in 1951. First demonstration membrane cell plant was also set up in the same factory. All first in the Industry occurred in Tamilnadu only. The two conventional technologies for chlorine and caustic soda production: Mercury cell process and Diaphragm (asbestos) processes lead to environmental pollution as they use hazardous materials (asbestos and mercury) as hardware and prone to emission of pollutants. The pollutant Hg comes from Hg cell process, the asbestos from diaphragm cell process. In this lecture the role played by CECRI in containing the environmental hazards from this industry is discussed .Though the residual chlorine from liquefaction affects the environment to a great extent, contribution made in the electrochemistry angle only is discussed. Let us see the each process in detail and how far it adds up the pollutant to the environment. Chlorine is produced by electrolysis when an electric current is passed through a solution of brine (common salt dissolved in water). Co-products are caustic soda (sodium hydroxide) and hydrogen. All three are highly reactive, and technology has been developed to separate them and keep them separate 2.1.DIAPHRAGM CELLS

Cathode separates the cell into two compartments one containing the anode and the other containing the cathode. Diaphragm is deposited on the cathode screen. Brine enters the anode compartment and completely covers the anode and cathode fingers.

Chlorine leaves the cell through an outlet in the cell hood. Anolyte and sodium ions flow to through the diaphragm into the cathode compartment because of the difference in liquid level between the two compartments. Catholyte is 12 wt% NaOH and 16 18 wt % NaCl. Hydrogen is produced at the cathode and leaves through an outlet on the cathode. Cell liquor flows out through a level control pipe on the cathode chamber. The cell liquor can be fed to a triple effect evaporator operating on backward feed mode to get 50 wt% caustic which contains 1 wt% NaCl. The diaphragm with all cell hardware is shown in Fig.2.1 and with specific details of asbestos with cathode and anode is shown in cross sectional view in Fig.2.3.

Hookers Cell

Hookers Diaphragm Cell Plant

ENVIRONMENTAL HAZARDS OF ASBESTOS: Most vital component of the Diaphragm cell is the diaphragm, which allows percolation of the brine from the anode side to the cathode side. Widely used Diaphragm material has been asbestos in the form of fiber. Asbestos was chosen because of its good chemical stability and its ion exchange properties. Asbestos is relatively inexpensive. It is a homogenous mixture of Al2O3, SiO2, CaO, MgO and other acid insoluble salts mostly oxides. Asbestos is coated on to the cathode surface to a thickness of 3 to 4 mm by vacuum deposition. The permeability of the membrane is a very vital process parameter. In the case of diaphragm cells, when graphite anodes are used, graphite particles clog the diaphragm and impair the percolation of brine through it. When the permeability of the diaphragm becomes very poor it has to be removed and re deposited. As asbestos is carcinogenic, the frequency of its deposition is an environmental hazard.

Hazards of Hg pollution:

Hg in water and air is a silent hazard. Hg , entering the environment through industrial effluent discharges, enters human body either by inhalation of air containing Hg vapours or through food chain i.e., grass to cattle milk, thro, the soil to vegetables and thro, the tiny organisms in the river to fish. Hg accumulated in human body affects the central nevous system thro brain damage, leads to convulsions and mental retardation and often death. [ Hg vapour present in atmosphere is inhaled by human beings of which 75-80% is absorbed and accumulated in brain after diffusion across the membranes. Subsequent Hg exeretion from brain is very slow. Some metallic Hg oxidizes in blood and the Hg ions thus formed is bound to plasma proteins or haemoglobin. Hg Pollution: There are 25 Hg cell plants in our country having a production capacity of 9.63LTA. A conservative estimate of 0.25 kg of Hg loss per tonne of NaOH makes the environment richer by 200T of Hg. Every year around 80-85% of our annual import of about 250T is consumed by this industry. A major fraction of this Hg consumed (apart from carry our with products) is released into the environment through cell room ventilation, brine sludge and waste streams ASBESTOS IS CARCINOGENIC: Handling of asbestos powder and its slurry in caustic solution cause cancer. Caustic will soften the skin of humans while handling asbestos slurry to make asbestos diaphragm over cathode for diaphragm cell and asbestos will get into touch with flush easily and dry powder or asbestos in air goes to respiratory system and causes cancer.

Mercury Cell Process: The electrolytic cell has titanium anodes located above a mercury cathode, which flows along the bottom of the cell. Under the action of a direct current on brine, chlorine is released at the anode and sodium dissolves in the mercury cathode to give an amalgam. The sodium amalgam passes out of the electrolytic cell into a separate reactor, away from the chlorine. Here, it reacts with water to give hydrogen and 50% caustic soda . This regenerates the mercury, which is then returned to the electrolytic cell. Salt is added to the brine leaving the cell and the brine is recirculated. The mercury process produces extremely pure, high quality caustic soda, suitable for use in textile applications. The Principle of mercury cell process is shown below

Electrochemical Reactions: Primary Cell: ANODE: Cl- Cl2 + e ; Cathode: Na+ + e + Hg Hg-Na(0.25wt%) Secondary Cell (Denuder or decomposer): Hg-Na(0.25%) + H2O NaOH (50wt%) + H2 + Hg

A view down the middle aisle of 70,000-tonnes/year mercury process chlorine plant in The Netherlands. The circular vessels are amalgam decomposers

Additional industrial sources of mercury emissions include:


Iron and steel sectors Cement industry Municipal and hospital waste incinerators Coal-burning for power generation and industrial uses Gold mining and refining Thermometers Dental amalgam. Due to the complexity of identifying anthropogenic sources and possible emission rates, the OECD considers estimates of global emissions are extremely difficult to make. Global anthro-pogenic emissions of mercury to air were estimated at 3,560 tonnes in 1983, and to water and soil at 4,600-8,300 tonnes, respectively (including atmospheric fall-out, but excluding disposal of mine tailings, smelter slags and waste). Natural sources Most natural mercury deposits are at fairly shallow depths (a few metres to about 700 metres). Mercury is extracted by underground and opencast mining of cinnabar ore. Heating the ore, followed by condensation of the vapour produces liquid mercury. Global mercury production has fallen steadily from 6,500 tonnes in 1986 to 3,260 tonnes in 1996. Some 1,350 tonnes of mercury were mined in the EU in 1996, according to the report prepared for EU Commission DG III. In addition to primary extraction, there is significant secondary production of mercury, including recycling, recovery and industrial reprocessing. In 1982, the OECD estimated it to be up to 40% of primary production. OECD estimates of natural emissions of mercury to air, water and land range from 2,50015,000 tonnes/year. These originate from soil, vegetation, forest fires, water surfaces and geological sources: Degassing from geological mineral deposits Emissions from volcanic activities Photoreduction of divalent mercury in natural waters Biological formation of elemental mercury (or possibly dimethylmercury) from methylmercury Volatilisation from soil Seismic activities such as earthquakes Geothermal sources - including the oceanic crust - related to submarine volcanoes. Substantial improvements have been made, with mercury emissions reduced by over 95% from 1997 to 1999. This compares with estimated global total man-made and natural emissions of 20,000 tonnes per year Duration Production by Years Hg 1975-80 1981-85 1986-90 1991-95 1996-97 Hg consumed Production by Diaphragm cells 100000 x 5 90000 x 5 70000 40000 0 Asbestos consumed

1997-98 1998-99 1999-00 2000-01 2001-02 2002-03

2.3. GRAPHITE ANODES Carbon was the first anode material used for the electrolytic production of caustic soda and chlorine. While using carbon, the products were contaminated with carbon particles. This drawback was eliminated with the discovery of artificial graphite at the beginning of the century. Though graphite possessed better physical and chemical properties than carbon, it also has its own disadvantages.

1.During operation, Graphite is consumed due to electrochemical attack of O2, resulting from a side reaction. 2H2O_ 2H2 + O2 and chemical attack by HClO present in the electrolyte due to the dissolution of Cl2. Cl2 + H2O HClO + HCl C+ HClO CO + HCl

These reactions weaken intercrystalline bonds and graphite begins to spall off as result of mechanical erosion. Graphite consumption is of the order of 2 to 4 kg per tonne of caustic produced. Entire graphite anode set has to be replaced once in 10 to 12 months. 2.Gradual oxidation of graphite to CO and CO2 results in the widening of the anode cathode gap, thereby increasing the cell voltage and hence power consumption for the production of caustic. 3. The graphite particles are plugged into the pores of asbestos diaphragm and rendering the diaphragm offering higher resistance and ineffective 4.Periodic adjustment for maintaining the fixed (3-4mm) interelectrode gap between Hg and graphite/ replacement of graphite anodes increases operating cost and leads to substantial emissions and spillages of mercury to the environment in the case of mercury cells. 4.Products are contaminated. Cl2 contained CO2 and NaOH has graphite particles.

4. POLLUTION ABATEMENT AND ROLE OF CECRI FOR THAT:


Abatement of pollution from chlor-alkali industry can be done by (i) (ii) (iii) treatment of effluent before discharging to air or waterways . adopting technology which can lessen pollution. adopting technology which does not involve pollutants.

Among the above, CECRI has developed (i) an alternate anode which keeps its dimensions constant thereby frequent cell openings are not required, which lessen pollution to a considerable extent and (ii) developed components for a technology which does not involve pollutants.

4.1. DEVELOPMENT OF TITANIUM SUBSTRATE INSOLUBLE ANODE - (TSIA) The disadvantages of the usage of graphite anodes in the production of Caustic soda and chlorine have been discussed earlier. Further Graphite, itself is being produced by an electrolytic process consuming 9000 Kwh per tonne. Further the cost of electrical energy was also increasing at a steady and constant rate. All these necessitated a concerted search, international in scope to find an alternate anode material, which could keep constant, dimensions with time. Central electrochemical research institute, Karaikudi has developed a novel type of dimensionally stable anodes known as Titanium substrate insoluble anode (TSIA) by depositing a combination of mixed oxides of platinum group metals such as Ruthenium, Iridium, Platinum etc with oxides of valve metals such as Titanium, Tantalum , Zirconium etc over a corrosion resistant substrate like Titanium, Tantalum ,Zirconium or their alloys. In simple terms, TSIA has a titanium base which is activated a catalytic coating consisting of a mixture of oxides of platinum group metals and oxides of valve metals. The coating is imparted by thermal decomposition. The process was patented in 1972. Industrial TSIA and Graphite anodes are shown in Fig.4.1.

Fig.4.1

The advantages of TSIA are numerous. Though the initial cost of such anodes is four times higher than that of conventional graphite anodes, it has been established that they are highly economical in the long run due the following advantages: 1.Dimensional stability. 2.Longer life. 3.Ability to function effectively at higher current densities. 4.Purer products. 5.Lesser cell interruptions and 6.10 15 % power saving (350 Kwh / tonne of caustic) due to a).Lower chlorine overvoltage . b).Lesser bubble effect resulting from higher free surface for the escape of chlorine gas. c).Higher electrical conductivity. d).Lower and constant cell voltage and e).Operation at lower and constant inter electrode gap. In addition to chlorine production, TSIA can be used for 1.Manufacture of chlorates, bromates and iodates. 2.Electrowinnig of metals. 3.Insitu generation of hypochlorite by the electrolysis of sea water. 4.Cathodic protection by impressed current. 5.Electro - organic syntheses.

All raw materials for the production of TSIA are at present available indigenously. The effective life of the electrocatalytic coating ranges from 18 36 months depending upon the current density and the operating / cell working conditions in mercury cell and over 60 months in diaphragm cells. The TSIA structures can be recoated with the electrocatalyst as and when the coating wears out and reinstalled. The life cycle of the structure varies with the operating and cell conditions : but usually last for four to five recoatings. The cost of the raw materials especially titanium and precious metal compounds are showing an upward trend always. So the cost of TSIA per m2 geometrical area mainly depends on the design of structure, current density of the cell, type of cell and prevailing electrocatalyst cost. Approximately it varies from Rs 30000 70000 per m2deponding on the current density and type of cell. To prove the technical viability of the invention field trials were conducted in various commercial chlor - alkali plants in the country. The first field trial was conducted in a diaphragm cell at DCM chemical works, New Delhi in 1972. Favourable results in this plant encouraged other units to follow suit. Field trials were then successfully conducted in low current density mercury cells and high current density mercury cells. By 1976, Indian chloralkali industry was convinced of the technical feasibility, commercial viability and the energy conservation aspects of TSIA developed by CECRI.. The process know - how was released for commercial production to three industrial establishments namely : 1.Titanium Equipment and Anode Manufacturing Company Limited, Madras. (1976). 2.Bharat Heavy Plates and Vessels Limited, Visakapatnam. (1981). 3.Titanor Components Limited, Goa. (Formerly WIMCO, Bombay.) (1983).

The first commercial caustic soda unit with the TSIA supplied by the first licensee was commissioned in 1978. The plant recorded a power saving of 12 %. Orders started pouring in from other units as well. Hence the process was released to two more parties. By 1982, the entire caustic production was based on TSIA.

TOTAL POWER SAVED UPTO 31.03.2004 : 5500 MILLION Kwh COST OF POWER SAVED : RS 9500 MILLION

When graphite anodes are used, frequent opening of the cells are needed for the removal of graphite pieces fallen down, for the adjustment of inter electrode gap, when graphite anodes wears and also for the regular cleaning of the cell. In all these cases, mercury vapours escape from the mercury cells into the atmosphere. When TSIA is used in the cells, as the electrodes maintain their dimensions constant through out their life time, Periodical opening of the cell are not required. This itself has been estimated to reduce mercury emissions by over 50%. When TSIA is used in the place of graphite anodes in the case of Diaphragm cells, the permeability of the diaphragm is preserved for longer time. The life of the diaphragm has been found to be increased by over 40%. Advantages of Graphite in Diaphragm cell: For every ton of NaOH produced, about 800 gm of asbestos is consumed or let to the environment. But with TSIAnodes life of diaphragm is about 12 months, i.e hazard to environment is halved For one ton per day caustic plant with graphite anode, 200 kg of asbestos is required for every 6 months, afterwards, it should be renewed. (hence for 180 ton of caustic produced using graphite anode, about 200 kg of asbestos is lost or buried to environment The graphite fitted as well as TSIA fitted diaphragm cells are shown here:

4.2. ENVIRONMENTAL FRIENDLY MEMBRANE CELLS The two conventional technologies for the chlor alkali production are not environmentally acceptable as the Diaphragm cell technology involve carcinogenic asbestos as separator and the Mercury amalgam process use the hazardous pollutant mercury as cathode. Further these processes consume 3200 kWh electrical energy per tonne of caustic produced. As an environmental friendly and energy conserving alternate, Membrane cell technology for chloralkali production has been developed in India (CECRI) as well all over world. In this technology, neither Asbestos nor Mercury is used. The only imported component involved is CATION EXCHANGE MEMBRANE (CEM), which separates the anode compartment and the cathode compartment. The anode compartment is made of Titanium and in it activated Titanium expanded mesh acts as anode. The cathode compartment is made of Nickel and in it activated perforated Nickel sheet acts as cathode. Ultra pure saturated brine is fed to the anode compartment and depleted brine is discharged. 30% Caustic is fed to the cathode compartment. Chlorine gas is evolved at the anode and Hydrogen gas and Hydroxide ions are generated at the cathode by the reduction of water molecules. CEM permits only Sodium ions to pass through to the cathode compartment where it combines with hydroxide ions to form sodium hydroxide. 33% caustic flows out of the cathode compartment. As CEM prevents the migration of chloride ions to the cathode compartment, the caustic produced is highly pure. The Principle of membrane cell is shown in Fig.4.2

The first membrane cell plant in India was established at M/s Chemfab Alkalis, Pondicherry in 1985. Depending on the manner in which electrical connections are made between the cell units, electrolysers are classified as mono polar or bipolar. In the mono polar cells all anode and all cathode elements are arranged in parallel, forming an electrolyser having high amperage and low voltage. In the bipolar cells the cathode of a cell is connected to the anode of the

subsequent cell so that cells are connected is series forming an electrolyser with low amperage and high voltage. 4.2.1. CECRI has developed mopolar as well as bipolar membrane cell technologies with anodes and cathode indigenously developed at CECRI. 4.2.2.Dimensionally stable anodes and its coatings and catalytic cathodes are vital components of this technology. CECRI has developed ANODE and CATHODE (with innovative catalytic coatings) for these types of cells. The Developmental process in CECRI is shown here:

Further in Membrane cells the higher % conversion per pass (33 %) is allowed, while in the conventional technologies, 5 conversions per pass are 15 % only. Volume of electrolyte required in Membrane cells is 10 m3 per tonne of caustic while in the conventional technologies it is four times this value. This also helps indirectly to reduce the volume of effluent from the process considerably. 4.2.1. Catalytic anodes for membrane cells: To fulfill the stringent conditions of membrane cell operation suitable anode electrocatalysts have been developed. The advantages of newly developed anode for use in membrane cells are as follows 1). Oxygen evolution is suppressed and product chlorine purity is high 2). High current efficiency of 94-95 3). Membrane damage due to improper electrolyte circulation has been avoided and bubble effect has been eliminated 4). Service life of anode coating has been improved (5 years) 5). The performance of the newly developed TSIA for use in membrane cells was evaluated in 6000-Ampere prototype membrane cell. 4.2.2. Catalytic Cathodes for Membrane Cells: Conventional cathodes namely MS, SS or Nickel used in the electrolysis of aqueous alkali metal halide solutions exhibit very high

hydrogen over voltage of the order of 350 mV at a current density of 300 mA per square cm. In order to save energy, we have developed Catalytic cathodes. Catalytic cathodes consist of Nickel or Nickel-plated SS activated by a coating of Nickel stabilised by a mixture of precious metals or their oxides. The coating is imparted by the Thermal Decomposition Technique developed by the group already for the production of titanium Substrate Insoluble Anodes. The hydrogen over voltage of these cathodes is only 70 mV at a current density of 300 mA per square cm. The life of the active coating has been evaluated in 30-wt% NaOH solutions at a current density of 3 kA per square meter at 80 0C to be over Three Years. Energy saving due to these cathodes is 200 kWh per tonne of caustic. The process for the manufacture of these cathodes was patented in India. (INDIAN PATENT: 179959 of 1990). Further improvements have been made and the present activated cathode is superior the previous one in terms of performance namely improved coating life and enhanced tolerance towards metallic impurities present in the electrolyte. The activated cathodes were patented in USA. ( US PATENT: 5855751 of 1999 ) Advantages of the Catalytic Cathodes for membrane cells: Low hydrogen overvoltage of the order of 70 80 mV at 3 kA / m 2 . Energy saving of the order of 250 kWh per tonne of caustic. Enhanced tolerance towards metallic impurities in the electrolyte. Easier method of processing of the electrodes.

Recently Technological know how for the coating / recoating of membrane cell (1).Anodes and (2).Cathodes have been licensed to M/S. GRASIM INDUSTRIES ( CHEMICAL DIVISION) OF ADITYA BIRLA GROUP. They are using our technology for recoating the anodes and cathodes of their Membrane cells. The performance of our electrodes is on par with the imported ones.

5. SUMMARY:

In Indian as well as in the world scenario, the environmental management of chlor-alkali industries has been done to a great extent by the invention and adoption of metal anodes (TSIA) in the place of graphite anodes and replacement of conventional mercury and diaphragm cell processes by the modern membrane Cell technology. The scientific innovations in this field saved not only the earth but also the energy to a great extent.

. MERCURY CELLS Mercury cells contain no diaphragm. Here separation of anode and cathode products is achieved by the use of an Hg cathode. The mercury (sodium amalgam) cell (Fig.2.2) process actually involves two cells an electrolyser and a decomposer. In the electrolyser, flowing mercury is the cathode and graphite or TSIA-(Titanium substrate insoluble anode) as anode. Purified aqueous NaCl solution is electrolysed between anodes and flowing mercury cathodes. While chlorine is liberated at the anode, sodium ions are reduced at the Hg cathode forming sodium amalgam(0.20-0.25 wt%).The amalgam flows over to the decomposer where it reacts with water to form caustic solution, hydrogen gas and pure Hg. Hg is recycled to the electrolyser. Concentration of NaOH produced in the process can be maintained at

any level between 40 and 50 wt% by regulating the water fed to the decomposer. Caustic from this process contains only 50 ppm of NaCl. For every tonne of caustic produced, 0.25 kg of Hg is lost by means of spillage and evaporation. But Hg pollution is not as alarming as in developed countries, as the plants are well scattered.

The electrolyser consists of a long shallow inclined (5 10 mm per m) trough provided with a cover containing hole at regular intervals for holding the anodes. Cell cover and the sides of the cell trough are rubber lined. Bottom of the trough is rubber lined in the case of low current density cells and are bare in the case of high current density cells. In the case of rubber-lined bottom, bare MS discs are provided at regular intervals for current connection. Denuder or decomposer may be vertical or horizontal design and made of cast iron filled with treated graphite blocks. If the denuder is vertical, it is positioned at the outlet end of the electrolyser. If it is horizontal, it is kept beneath the electrolyser.

Anode: Cl- Cl2 + e ; Cathode(Hg): Na+ + e Na(Hg) Na+ + Cl- Cl2 + Na(Hg) ; Decomposer reaction: H2O + Na(Hg) H2+NaOH- + Hg

Eo : 1.36 V Eo : -1.77 V Eo : 3.13 V Eo : -1.08V