Chloro Alkalis
Chloro Alkalis
Chloro Alkalis
Chloro-Alkalis
Prabhdeep SinghVirdi
4/26/2010
Roll no 215
This Report contains the various details of Chloro-alkalies, their properties , manufacturing processes, top manufacturers and the economic scenario of the indutry
Chlor-Alkalies Contents
Introduction.................................................................................................................................................. 2 Properties of Causitic Soda and Chlorine...................................................................................................... 2 Caustic soda .............................................................................................................................................. 2 Chlorine ..................................................................................................................................................... 3 Top Manufacturers and their details ............................................................................................................ 4 REACTIONS ............................................................................................................................................. 5 Comparison of cell technologies ........................................................................................................... 6 Manufacturing process .............................................................................................................................. 7 Mercury cells ................................................................................................................................. 8 Diaphragm cells ................................................................................................................................... 9 Membrane cells ............................................................................................................................. 9 Chlorine processing..................................................................................................................... 10 Hydrogen processing ................................................................................................................... 11 Caustic soda processing ..................................................................................................................... 11 Brine processing ................................................................................................................................. 12 Environmental issues within the chlor/alkali industry ................................................................................ 13 Chlorine bleaching of wood pulp and dioxin emissions to the environment ................................... 13 Ozone layer depletion ......................................................................................................................... 14 Polyvinyl chloride plastic ................................................................................................................... 14 Mercury emissions ............................................................................................................................. 15 Asbestos .............................................................................................................................................. 15 Economic Overview of chloroalkal industry ............................................................................... 16 Major Chemicals .................................................................................................................... 16
Introduction Salt is one of the oldest and most popular condiments. What is relatively unknown, however, is that salt is also the raw material for one of the most potentially profitable chemical industries in the country chlor alkali. This is possibly one of the few industries where supply far exceeds demand, making it a promising candidate for export. So it seems almost surreal that the chlor alkali industry faces a threat from the imported product. The chlor alkali industry in India is around 60 years old. It began with a modest capacity of a few thousand tonnes per annum and has since grown into a 2.24 million tonnes per annum capacity industry
Caustic soda
Specific gravity Odour Melting point (calcination) Boiling point Hygroscopicity Solubility in water
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Chlorine
Colour Odour Boiling (liquefying) point Freezing (melting) point Density - liquid - dry gas Vapour Pressure Latent heat of vaporisation Liquid - Gas volume relationship Solubility in water
Gas-Greenish Yellow Liquidclear Amber Characteristic, suffocating -34C (1 atm) -101C (1 atm) 1.468 gms/cc at 0C and 3.617 atm 3.209 g/L (0C, 1 atm) 3.617 atm (at 0C) 68.7 cal/gm at -34C One volume of liquid chlorine weighs as much as 457.6 volumes of gas at 0C and 1 atm Slightly soluble
Chemical properties
I - Flammability 1. Neither liquid nor gaseous chlorine is explosive or flammable. II Reactivity than 5% of either component,
REACTIONS Electrochemical and chemical reactions occurring in mercury cells [1] 2Cl- ==> Cl2 + 2e[2] 2Na+ + 2Hg + 2e- ==> 2Na (in Hg) 2Cl- + 2Na+ + 2Hg ==> Cl2 + 2Na (in [3] Hg) [4] 2Na (in Hg) + 2H2O ==> H2 +2NaOH + Hg (anodic reaction) (cathodic reaction) (overall cell reaction) (decomposer reaction) (overall process reaction) (anodic reaction) (cathodic reaction) (overall ionic reaction) Electroche mical and chemical reactions occurring in diaphrag m and membran e cells Reaction [9] will contaminat e the caustic product with chlorate.
[5] 2NaCl + 2H2O ==> Cl2 +2NaOH + H2 [1] 2Cl ==> Cl2 + 2e
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[6] 2H2O + 2e- ==> 2OH- + H2 [7] 2Cl- + 2H2O ==> Cl2 + H2 + 2OH-
[5] 2NaCl + 2H2O ==> Cl2 +2NaOH + H2 (overall reaction) [8] Cl2 + 2NaOH ==> NaOCl + NaCl + H2O (side reaction) (side reaction)
Chemical reactions occurring in brine processing [10] CaSO4 + Na2CO3 ==> CaCO3 +NaSO4 (CaCO3 precipitates) (Mg(OH)2 precipitates)
Comparison of cell technologies Mercury Operating current density ( kA/m2) Cell voltage (V) NaOH strength (wt%) Energy consumption ( kWh/MT Cl2) at a current density of (kA/m2) Steam consumption (kWh/MT Cl2) for concentration to 50% NaOH 8 - 13 3.9 - 4.2 50 3360 (10) 0 Diaphragm Membrane 0.9 - 2.6 2.9 - 3.5 12 2720 (1.7) 610 3-5 3.0 - 3.6 33-35 2650 (5) 180
Saturated brine fed from the end box is electrolyzed at the anode to produce the chlorine gas, which flows from the top portion of the trough and then exits. The sodium ion generated reacts with the mercury to form sodium amalgam (an alloy of mercury and sodium), which flows out of the end box to a vertical cylindrical tank. About 0.25% to 0.5% sodium amalgam is produced in the cell. The sodium amalgam reacts with water in the decomposer, packed with graphite particles and produces caustic soda and hydrogen. Hydrogen, saturated with water vapor, exits from the top along with the mercury vapors. The caustic soda then flows out of the decomposer as 50% caustic. The unreacted brine flows out of the exit end box. Some cells are designed with chlorine and anolyte outlets from the end box, which are separated in the depleted brine tank. The mercury from the decomposer is pumped back to the cell.
Diaphragm cells The diaphragm cell is a rectangular box with metal anodes supported from the bottom with copper-base plates, which carries a positive current. The cathodes are metal screens or punch plates connected from one end to the other end of the rectangular tank. Asbestos, dispersed as a slurry in a bath, is vacuum Fig. 6. Schematic of a diaphragm cell. deposited onto the cathodes, forming a diaphragm. Saturated brine enters the anode compartment and the chlorine gas liberated at the anode during electrolysis, exits from the anode compartment. It is saturated with water vapor at a partial pressure of water over the anolyte. The sodium ions are transported from the anode compartment to the cathode compartment, by the flow of the solution and by electromigration, where they combine with the hydroxyl ions generated at the cathode during the formation of the hydrogen from the water molecules. The diaphragm resists the back migration of the hydroxyl ions, which would otherwise react with the chlorine in the anode compartment. In the cathode compartment, the concentration of the sodium hydroxide is ~12%, and the salt concentration is ~14%. There is also some sodium chlorate formed in the anode compartment, dependent upon the pH of the anolyte. Membrane cells
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Caustic soda processing Caustic soda is marketed as 50%, 73%, or anhydrous (dry) beads or flakes. The mercury cell can produce 50% and 73% caustic directly. The caustic from the decomposer is cooled and passed once or twice through an activated carbon filter to reduce the mercury levels in the caustic. After filtration, the mercury concentration is lowered to the parts-per-million (ppm) levels. Even these low levels of mercury may be unacceptable to some customers, who then have to switch to using membrane grade caustic soda. The mercury cell caustic soda has a
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Environmental issues within the chlor/alkali industry There are several environmental concerns that have made a significant impact on the growth of the chlor-alkali industry over the past twenty years and will dictate the future growth as well. These issues are highly debated, and the associated "chemophobia" is likely to adversely affect the chlorine consumption profile in the future. Chlorine bleaching of wood pulp and dioxin emissions to the environment
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Rs. 9,600 crore industry (US $ 2.2 billion) Covers a wide spectrum of products - Soda ash, Caustic soda, Sulphuric acid, Chlorine Calcium Carbonate, Hydrogen Peroxide, Potassium Chlorate, Lead Phosphorus, Titanium Dioxide, Aluminium Fluoride, Carbon Blac Inorganic chemicals are used mainly in the manufacture of detergents, glass industry, soaps, fertilisers, alkalies, etc.
1552.1 1540 1545.8 1560 1243.1 1250 1309.2 1320 709 715 702.9 715 230
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Reasons for capacity additions - a surge in demand for chlorine (by product) There are four processes for making caustic soda diaphragm cell, mercury cell, membrane cell and chemical process technology Membrane cell the most energy efficient process and is being increasingly adopted. In all new plants, it is mandatory to use this technology
Industry
Capacity : 1964,500 tonnes; 98-99 production 1320,000 tonnes Industry characterised by 45 players with turnovers ranging from Rs. 15-20 crores (US $ 3.5 mn - US $ 4.5 mn) Average plant size - 42,000 tpa 5 - 6 large players having an annual turnover of Rs 80 crores (US $ 18 million) dominate the market NaCl, a major raw material, available in Gujarat (60 % of Indias salt production is from Gujarat) NaCl accounts for 15 - 20% of cost of production of caustic soda cost. Many companies have captive salt farms
Major Players
GACL, Bharuch Kanoria Chemicals, Ahmedabad DCM, Kota Tata Chemicals, Jamnagar SIEL, Kota Andhra Sugar, Kovvur
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Chlorine is generated as a co-product with caustic soda It is a toxic, hazardous chemical and is used in the manufacture of PVC, pulp and paper, bleaching powder, etc. Difficult to handle - has to be transported in heavy cylinders freight cost high. Hence sales are restricted to nearby locations. Chlorine consumption likely to improve with increase in production and consumption of PVC / Plastics
Industry
Installed capacity - 1031,000 tonnes 98-99 production - 715,000 tonnes Industry characterised by over 40 players Most manufacturers produce a wide range of chemicals. Chlorine often a co-product of caustic soda Companies located in the Gujarat belt
Major Players
Gujarat Alkalies & Chemicals - Vadodara DCM Sriram - Kota Kanoria Chemicals - Ahmedabad Andhra Sugar - Kovvur Punjab Alkalies - Jallandhar
References
http://en.wikipedia.org/wiki/Chlorine
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