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LECTURE 6 Chlor Alkali Industries – Soda Ash, Caustic Soda, Chlorine

LECTURE 6 Chlor Alkali Industries – Soda Ash, Caustic Soda, Chlorine. Chapter 13 in Shreve’s Chemical Process Industies. Caustic soda, soda ash and chlorine Rank close to H 2 SO 4 and NH 3 in magnitude of $ value of use Lot of consumption in making other chemicals.

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LECTURE 6 Chlor Alkali Industries – Soda Ash, Caustic Soda, Chlorine

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  1. LECTURE 6ChlorAlkali Industries – Soda Ash, Caustic Soda, Chlorine Chapter 13 in Shreve’s Chemical Process Industies

  2. Caustic soda, soda ash and chlorine • Rank close to H2SO4 and NH3 in magnitude of $ value of use • Lot of consumption in making other chemicals. • Uses – Soaps, detergents, fibers and plastics, glass, petrochemicals, pulp n paper, fertilizer, explosives, solvents and other chemicals Chlor Alkali Industries

  3. Previously made by Causticization of soda ash with lime Na2CO3 + Ca(OH)2→ 2 NaOH + CaCO3 • Only 10% NaOH solution obtained • Electrolysis of Brine – Most popular method adopted nowadays. Caustic Soda – NaOH

  4. Brittle white solid • Readily absorbs moisture and CO2 from air • Sold on basis of Na2O content • 76% Na2O equivalent to 98% NaOH • Uses – Soaps, textiles, chemicals, petroleum refining, etc. Caustic Soda – NaOH

  5. Uses of Caustic Soda

  6. Electrolysis of Brine • Chlorine at Anode; Hydrogen along with alkali hydroxide at cathode • Three types of cell exist: • Mercury Cell • Diaphragm Cell • Membrane Cell • Raw Materials 1. Brine (NaCl) 2. Electricity Manufacture of NaOH

  7. Energy consumed in electrolysis is product of current flowing and potential of cell • Gibbs Helmholz equation represents the relation between electric energy and heat of reaction: Energy Changes-- Gibbs equation

  8. Found from heats of formation of the components of the overall reaction: • This reaction is broken down into following reactions for formation: Net ∆H for the overall reaction results from Heat of Reaction (∆H)

  9. ∆H is computed in Gibbs Helmholz equation to get E = 2.31 V • Voltage Efficiency = Epractical÷ETheoretical×100 • Generally range from 60 – 75 %. • Faraday’s Law: 96,500C of electricity passing through a cell produce 1 gm.eq. of chemical reactions at each electrode • Actually higher – Side reactions Voltage Efficiency

  10. Ratio of theoretical to actual current consumed is current efficiency (≈ 95-97%) • Current divided by area on which current acts is current density – high value desirable • Product of voltage efficiency and current efficiency is energy efficiency of cell Current efficiency and Energy efficiency

  11. Ratio of equivalents produced in the cell to equivalents charged • Usually about 60 – 65 %. • Diaphragm cells have very high decomposition efficiencies • But encounter difficulties with migration of hydroxyl ions back to anode  formation of hypochlorite ion • At anode, OH- ions give • Oxygen formed reacts with graphite anode, decreasing its life • In Metal anodes, oxygen does not react. Decomposition Efficiency

  12. Previously mercury was most widely used • Health and environmental problems with mercury discharge in nearby waters • Improved designs of membrane cells and cheaper purification techniques have reduced cost and improved efficiencies • Dominate the field nowadays Cell type

  13. Diaphragm Cells • Contain a diaphragm made of asbestos fibers to separate anode from cathode • Allows ions to pass through by migration • Graphite anode and cast iron cathode

  14. Asbestos Diaphragm

  15. Diaphragm Permits the construction of compact cells of lowered resistance as the electrodes can be placed close together • Diaphragms become clogged with use and should be replaced regularly • Diaphragm permits flow of brine from anode to cathode and thus greatly lessens side reactions • Cells with metal cathodes rarely get clogged diaphragms and operate for 1-2 years without requiring diaphragm replacements. Diaphragm Cells

  16. Major Advantage – Can run on dilute (20%), fairly impure brine • Dilute brine produces NaOH 11% (NaCl 15%) • Consumes lot of energy for evaporation • For 1 ton of 50% caustic need 2600 kg of water to be evaporated. • Some amount of Chloride ion remains and is highly objectionable to some industries (Rayon) Diaphragm Cells– Advantages & Disadvantages

  17. Membrane Cells • Use semipermeable membrane to separate anode and cathode compartments. • Separate compartments by porous chemically active plastic sheets; that allows sodium ions to pass but reject hydroxyl ions.

  18. Membrane Cell

  19. Membrane Cell

  20. Purpose of membrane is to exclude OH- and Cl- ions from anode chamber • Thus making the product far lower in salt than that from a diaphragm cell • Membrane cells operate using more concentrated brine and produce purer, more concentrated product • (30-35% NaOH containing 50 ppm of NaCl) • Requires only 715 kg of water to be evaporated to produce 1 M ton of 50% NaOH Advantages of Membrane Cell

  21. Because of difficulty and expense of concentration and purification, only large diaphragm cells are feasible • Membrane cells produce concNaOH • considerable saving in energy (Evaporation) • and saving in freight (operate to the point of caustic use) • Small, efficient units may cause a revolution in the distribution of the chlor-alkali industry, particularly if efficiencies remain high Advantages of Membrane Cell

  22. Membranes are more readily clogged than diaphragms, so some of savings are lost, bcos of necessity to pretreat the brine fed in order to remove Ca and Mg before electrolysis Disadvantage of Membrane Cells

  23. Operate differently than the other two • Cathode is a flowing pool of mercury; graphite anode • Electrolysis produces a mercury-sodium alloy (amalgam) • Amalgams is decomposed in a separate vessel as: 2Na.Hg + 2H2O → 2 NaOH + H2 + Hg Mercury Cells

  24. 50% NaOH is produced with very low salt content (30 ppm) • No evaporation needed • Small loss of mercury to environment poses severe problems. Advantages and Disadvantages of Mercury

  25. Mercury Cell

  26. MERCURY CELL

  27. Brine Purification • Brine Electrolysis • Evaporation and Salt Separation • Final Evaporation • Finishing of Caustic • Special Purification of Caustic Unit Operations and Chemical Conversions

  28. Ca, Fe and Mg compounds plug the diaphragm • Precipitation with NaOH is commonly used to remove them • Addditional treatment with phosphates is required for membrane cells • Sulphates may be removed by BaCl2. • Brine is preheated with other streams to reduce energy requirement. Brine Purification

  29. 3.0 – 4.5 V per cell is used; whichever method is adopted • Monopolar – Cells connected in parallel and low voltage applied to each cell • Bipolar – Cells are connected in series and high voltage applied Brine Electrolysis

  30. 11 % NaOH (Diaphragm cells); 35% (Membrane Cells) are concentrated to 50% NaOH in multiple effect nickel tubed evaporators • Salt crystallizes out and recycled • Concentrated to 73% reduces shipping cost but greatly increases the shipping and unloading problems • High m.p of conc material makes steam-heated lines and steam heating of tank cars necessary. • Mp for 50% caustic 12°C; for 73%, 65°C. Evaporation and Salt Separation

  31. Membrane cells produce more concentrated caustic than diaphragm cells • Less Evaporation or treatment needed (Membrane cell) • Mercury cells produce 50% solution, so no evaporation is needed Evaporation and Salt Separation

  32. Cooled and settled 50% caustic may be concentrated in a single-effect evaporator to 70 – 75% NaOH using steam at 500-600 kPa. • Strong caustic must be handled in steam-traced pipes to prevent solidification • It is run to finishing pots • Another method – Treating 50% Caustic solution with Ammonia • Countercurrent system in pressure vessels • Anhydrous crystals separate from resulting aq. ammonia Final Evaporation

  33. Dowtherm heated evaporators – removal of water • Product is pumped by a C.P that discharges the molten material into thin steel drums or into a flaking machine Finishing of Caustic

  34. Troublesome impurities in 50% caustic are Fe, NaCl and NaClO3. • Fe removed by treating caustic with 1% CaCO3 and filtration • NaCl and NaClO3 may be removed using aq. NH3 • To further reduce salt content for some uses; caustic is cooled to 20°C as shown in following diagram Special Purification of Caustic

  35. Purification of Caustic soda

  36. Dried Chlorine is compressed to 240 or 550 kPa • Lower pressure – rotary compressor • Larger capacities and Pressures – Centrifugal and non-lubricated reciprocating compressors • Heat of compression is removed and gas condensed • Liquid Cl is stored in small cylinders • Hydrogen used in making other compounds • With Cl HCl • Hydrogenation of fatty acids (Soap manufacture) • Ammonia Chlorine and Hydrogen

  37. Soda Ash Manufacture Sodium Carbonate

  38. Physical • Odourless/hygroscopic; alkaline in nature • Mp. 851 °C; M.wt = 106, Density @ 20 °C = 2.53 g/cm3; • Chemical • Thermal Decomposition at 1000 °C/200 Pa • Na2CO3 Na2O + CO2 • Lethal dose = 4g/kg (rat); 15g/kg human Soda Ash

  39. Glass Industry • Water softening agent • Baking soda manufacture • Paper making • In Power generation to remove SO2 from flue gas Uses of Soda Ash

  40. Manufacturing processes Le Blanc Process Solvay Process

  41. 2 NaCl + H2SO4 Na2SO4 + 2 HCl • Na2SO4 + 2C  Na2S + 2 CO2 • Na2S + CaCO3 Na2CO3 + CaS • Disadvantages • Solid Phase • Amount of energy • CaS pollutant Le Blanc Process

  42. LeBlanc Process Reaction Scheme

  43. LeBlanc Process Diagram

  44. Continuous process using limestone, ammonia and NaCl to produce Na2CO3 Solvay Process

  45. Solvay Process

  46. Brine (NaCl) Ammoniated Brine Ammonia NaCl H2O NH3 Limestone CaCO3 NH3 CO2 Lime in Kiln Carbonating Tower NH4Cl Ammonia Recovery Filter CaO H2O Ca(OH)2 Lime Slaker NaHCO3 Waste by product CaCl2 300 °C Product Na2CO3 • Food additive • 2. Electrolyte • 3. Dehydrating agent

  47. Solvay Tower • 2 NH3 + CO2 + H2O  (NH4)2CO3 (exothermic) • (NH4)2CO3 + CO2 + H2O  2 NH4HCO3 • NH4HCO3 + NaCl  NaHCO3 + NH4Cl2 Middle of Carbonator • Lime Kiln • CaCO3  CaO + CO2 • CaO + H2O  Ca(OH)2 • Calciner • 2 NaHCO3  Na2CO3 + CO2 + H2O • Ammonia Recovery • 2 NH4Cl + Ca(OH)2  CaCl2 + 2 NH3 + 2 H2O Reactions

  48. Brine Preparation • Ammonia Absorption • Precipitation of bicarbonate • Filtration of bicarbonate • Calcination of bicarbonate • Recovery of Ammonia Manufacturing Steps

  49. Solvay Process • NH3 Absorber • Counter current flow; Baffles tray • Cooler to remove heat of solution • Slightly less than atm pressure • Made of Cast iron • At exit; NaCl = 260 g/l; NH3 = 80-90 kg/m3; CO2 = 40-50 kg/m3 • Carbonator • 6 -9 in number; 20-30 m in height • Exothermic reaction 60 °C • To reduce solubility of NaHCO3 use cooler at bottom @ 30 °C • Vacuum Rotary filter at bottom

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