Zurich2012_Presentation2 Minimised
- 1. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners Vladimir M. Sedivy MSc (Hons) Chem Eng, IMD President Salt Partners Ltd, Zurich, Switzerland Economy of Ultrapure Salt Feedstock in Membrane Cell Chloralkali Plants Watch the video record of this presentation: www.youtube.com/watch?v=ELZ3SYrDgJE (25’:44”)
- 2. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners Salt type World production Solar salt 90’000’000 t/y Rock salt 80’000’000 t/y Brines 80’000’000 t/y Total 250’000’000 t/y Salt production world-wide VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland
- 3. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners Salt user Salt consumption Chemical industry 150’000’000 t/y Food 60’000’000 t/y Other 40’000’000 t/y Salt consumption world-wide VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland
- 4. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland Salt Purities NaCl Purity (%) Rock salt 90 - 97 Crude sea salt 97 - 99 Washed sea salt 99 – 99.6 Purified sea salt 99.6 – 99.8 Refined salt 99.8 – 99.9 Vacuum refined salt 99.9 – 99.97 Ultrapure salt 99.97 – 99.997
- 5. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners Salt Prices Depend on Salt Purity VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland Industrial salt prices vary between USD 10.-/t and USD 100.-/t depending on salt purity 0 20 40 60 80 100 120 88 90 92 94 96 98 100 102 Salt Purity (% NaCl) SaltPrice(USD/t)
- 6. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners Important Impurities in Salt in 1996 VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland Rock salt Sea salt Lake salt Brines CaSO4 0.5 – 2% 0.5 – 1% 0.5 – 2% Saturated MgSO4 Traces 0.2 – 0.6% Traces Traces MgCl2 0.3 – 1% Traces CaCl2 Traces Na2SO4 Traces KCl Traces NaBr Traces Insolubles 1 – 30% 0.1 – 1% 1 – 10%
- 7. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners Important Impurities in Salt in 2012 VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland Ag, Al, As, Ba, Br, Ca, Cd, Cr, Cu, F, Fe, Hg, I, K, Li, Mg, Mn, Mo, N (as NH3 and as NO2), Ni, P, Pb, S (as SO4), Si (soluble), Si (total), Sr, Ti, V, Zn, TOC (Total Organic Carbon), Moisture, NORM (Naturally Occurring Radioactive Substances), Insolubles in 10% neutral brine, Insolubles in 2% neutral brine, Insolubles in alkaline brine, etc.
- 8. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland Max. Membrane Licensor A Membrane Licensor B Ca + Mg ppb 20 20 SO4 g/l 5 4 - 8 I ppm 0.1 0.2 Ba ppm 0.1 0.5 Sr ppm 0.4 0.1 Al ppm 0.1 0.1 SiO2 ppm 5 5 Fe ppm 0.05 0.1 Hg ppm 0.1 0.1 Ni ppm 0.01 0.01 Mn ppm - 0.01 F ppm - 0.5 TOC ppm 10 10 Important Impurities in Brine for Membrane Cells
- 9. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners The Basic Chloralkali Equation Caustic and Chlorine from Salt VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland 2 NaCl + 2 H2O + Electrical Energy = 2 NaOH + Cl2 + H2 119 36 82 71 2 1.45 1 1.68 1
- 10. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland 2 NaCl + CaCO3 = Na2CO3 + CaCl2 119 110 111 120 1.1 0.93 1 The Basic Chloralkali Equation Soda Ash from Salt and Lime
- 11. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners Why must brine for chloralkali manufacture be pure? VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland • Membrane damage in membrane cells • Hydrogen evolution in Hg-cells • Incrustations in soda ash production • Contaminated effluents • Bromine in chlorine for organic synthesis • etc. Brine for chloralkali manufacture must be purified.
- 12. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland Brine Purification: Ca and Mg Precipitation Calcium precipitation Ca++ + Na2CO3 = CaCO3 + 2 Na+ 40 108 Magnesium precipitation Mg++ + 2 NaOH = Mg(OH)2 + 2 Na+ 24 82
- 13. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland Brine Purification: Overdosing of Reagents For calcium precipitation 0.4 kg Na2CO3 per m3 of brine For magnesium precipitation 0.15 kg NaOH per m3 of brine
- 14. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland Brine Purification: Sulphate Removal With BaCO3 SO4-- + BaCO3 = BaSO4+ CO3 -- 96 197 233 With BaCl2 SO4-- + BaCl2 = BaSO4+ 2 Cl- 96 208 233 With CaCl2 SO4-- + CaCl2 = CaSO4+ 2 Cl- 96 111 136 With Nanofiltration From 4 – 8 g/l to 80 g/l in purge as Na2SO4
- 15. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners Nanofiltration Operating Point VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland
- 16. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland SNEP, Morocco Proinsal, Argentina Solvay, Spain Modi, India Enichem, Italy GACL, India Grasim, India Saukem, India Standard Alkali, India Bandar Imam, Iran Chemfab, India Century, India NRC, India Borregaard, Norway GHCL, India Heilbronn, Germany Safi Salt, Jordan Arab Potash, Jordan Da Qing He, China EPETCO, Egypt Atul, India MISR, Egypt Quimpac, Peru Azraq, Jordan Dwory, Poland Petkim, Turkey TCC, India Tata, India Hellenic, Greece Borsodchem, Hungary Sind Alkalies, Pakistan Frutarom, Israel Nirou Clor, Iran Kothari, India Uniteca, Portugal Ittehad, Pakistan Aragonesas, Spain Ercros, Spain Shriram, India Sitara, Pakistan Saboo, India Solvay, Argentina Ballarpur, India Salexpor, Portugal Atanor, Argentina Jayshree, India Fine Salt, India Tokuyama, Japan Andhra Sugars, India Emisal, Egypt Sales Monzon, Spain Reliance, India Punta de Lobos, Chile DCW, India Tekel, Turkey Salgema, Brazil SPIC, India Formosa Plastic Rio Doce, Brazil El Nasr, Egypt Mabuhay Vinyl, Philippines Arabian Chlorine, Saudi Arabia Abadan Petrochemical, Iran DSW, Israel Salt Partners Cost Survey Contributors
- 17. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland Cost of Salt and Brine Treatment Cost of brine treatment and disposal Cost of salt, brine treatment and disposal (USD / t salt) (USD / t salt) Minimum 1.50 10 Average 10 25 Maximum 30 50
- 18. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland Relative Brine Treatment Cost Cost of brine treatment as percentage of salt cost Percentage of chloralkali production cost (%) (%) Minimum 100 3 Average 170 15 Maximum 300 40
- 19. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners Centrifuge separates salt and brine Conventional washing with water in the centrifuge VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland HYDROSAL Process CH-8053 Zurich Tel.: +41 (44) 422 26 82 Fax: +41 (44) 422 26 83 www.salt-partners.com Salt Centrifuge Purified Salt Water
- 20. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners Dissolve salt fines in water and use this pure brine to remove impurities from salt in the hydroextractor VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland HYDROSAL Process CH-8053 Zurich Tel.: +41 (44) 422 26 82 Fax: +41 (44) 422 26 83 www.salt-partners.com Salt Hydroextractor Centrifuge Filtrate Vessel Filtrate Pump Water Purified Salt
- 21. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners Hydraulically transport salt to the hydroextractor and return the transport brine to the elutriator VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland HYDROSAL Process CH-8053 Zurich Tel.: +41 (44) 422 26 82 Fax: +41 (44) 422 26 83 www.salt-partners.com Salt Slurry Pump Hydroextractor Centrifuge Filtrate Vessel Filtrate Pump Water Purified Salt
- 22. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners Circulate impure brine to control hydroclassification and elutriation efficiency VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland HYDROSAL Process CH-8053 Zurich Tel.: +41 (44) 422 26 82 Fax: +41 (44) 422 26 83 www.salt-partners.com Salt Slurry Pump Hydroextractor Centrifuge Filtrate Vessel Filtrate Pump Brine Pump Water Purified Salt
- 23. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners Elutriation VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland Elutriation in upwards flowing brineSettling velocities in brine NaCl Gypsum 100-150µ
- 24. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners Hydroclassification VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland Salt bed with buried impurities Hydroclassification of impurities in partially fluidised salt bed
- 25. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners Hydroextraction VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland 25% NaCl NaCl is recrystallised on crystal surface Impurities are extracted from cavities by diffusion Hydroextraction / Displacement crystallisation 15% NaCl4%6% MgSO4MgCl2
- 26. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners Hydroextraction does not work in all vessels VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland In this vessel salt flows out mainly through the centre So called rat hole develops in the centre of the vessel
- 27. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners Hydroextraction works only with plug flow of salt VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland Picture 1: Injection of black ink into brine flowing upwards through salt flowing downwards in plug flow Picture 2: Black ink flows upwards with brine in counter- current flow Picture 3: Second black ink injection. There are no traces of black colour in the salt flowing downwards in plug flow
- 28. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners Solution mining for natural gas storage, co-generation, brine purification, salt crystallisation and refining plant in Portugal VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland
- 29. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners 40 t/h salt purification plant in Portugal producing purest industrial salt in Europe VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland Performance test Ca ppm 0.6 Mg ppm 0.2 SO4 ppm 53
- 30. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners High quality European vacuum salt “A” before and after HYDROSAL purification VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland Commercial vacuum salt product HYDROSAL purified Ca ppm < 1 < 1 Mg ppm 0.12 0.07 SO4 ppm 118 29 K ppm 87 72 Br ppm 35 34 I ppm < 0.1 < 0.1 Ba ppm < 0.02 < 0.02 Sr ppm < 0.1 < 0.1 Al ppm < 0.05 < 0.05 SiO2 ppm 0.58 0.23
- 31. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners High quality European vacuum salt “E” before and after HYDROSAL purification VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland Commercial vacuum salt product HYDROSAL purified Ca ppm 6.5 5.8 Mg ppm 3.1 2.9 SO4 ppm 191 33 K ppm 36 29 Br ppm 29 28 I ppm < 0.1 < 0.1 Ba ppm < 0.02 < 0.02 Sr ppm 0.1 < 0.1 Al ppm < 0.05 0.05 SiO2 ppm 0.81 0.47
- 32. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners High quality European vacuum salt “N” before and after HYDROSAL purification VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland Commercial vacuum salt product HYDROSAL purified Ca ppm 211 66 Mg ppm 6.8 1.2 SO4 ppm 820 229 K ppm 225 185 Br ppm 43 36 I ppm 0.4 < 0.1 Ba ppm 0.04 < 0.02 Sr ppm 6.3 2.2 Al ppm 1.0 0.1 SiO2 ppm < 0.1 < 0.1
- 33. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland Costs Related to Salt Use in Membrane Chloralkali Manufacture • Salt Storage and Handling • Salt Dissolution and Brine Purification • Contaminated Sludge Handling and Disposal • Purge Decontamination, Disposal and Salt Loss • Ferrocyanide, Silica, Bromine and Iodine Removal • Power Consumption • Hydrochloric Acid Consumption • Membrane Life • Production Loss or Extra Production Capacity
- 34. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland Comparative Study on Differential Costs in a Membrane Cell Plant having Following Parameters: • Plant Capacity: 300’000 t/y of Chlorine • Conversion from Mercury to Membranes • Sulphate Removal with Nanofiltration • Washed Salt with Bromine, Iodine and Ferrocyanide • Ultrapure Salt without Bromine, Iodine and Ferrocyanide • Ultrapure Salt in Silos, no Contamination • Primary Brine Purification Plant Redundant • Membrane Cells with Acidification • Production Loss or Extra Production Capacity
- 35. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland Washed Salt A Ultrapure Salt B Ca (%) 0.1 0.00005 Mg (%) 0.01 0.00001 SO4 (%) 0.4 0.003 Insolubles (%) 0.5 0 Moisture (%) 7 0.02 NaCl (dry basis) (%) 98.9 99.996 Membrane Plant Operation with Salt A and B
- 36. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland Washed Salt A Ultrapure Salt B Salt cost (EUR/y) 14’820’000 23’010’000 Salt handling labour (EUR/y) 330’000 300’000 Fuel (EUR/y) 40’000 0 Salt handling maintenance (EUR/y) 80’000 120’000 Process water (EUR/y) 20’000 330’000 Brine purification chemicals (EUR/y) 1’170’000 50’000 Primary brine purification power (EUR/y) 330’000 0 Primary brine purification labour (EUR/y) 330’000 0 Primary brine purif. maintenance (EUR/y) 300’000 0 Solids disposal (EUR/y) 770’000 0 Membrane Plant Operation with Salt A and B
- 37. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland Washed Salt A Ultrapure Salt B Nanofiltration plant cost (EUR/y) 800’000 0 Nanofiltration power (EUR/y) 120’000 0 Nanofiltration refrigeration water (EUR/y) 20’000 0 Nanofiltration treated water (EUR/y) 40’000 0 Nanofiltration reactants (EUR/y) 50’000 0 Nanofiltration membrane replacement (EUR/y) 40’000 0 Nanofiltration plant maintenance (EUR/y) 60’000 0 Bromine removal (EUR/y) 1’500’000 0 Ferrocyanide removal (EUR/y) 0 0 Iodine removal (EUR/y) 0 0 Membrane Plant Operation with Salt A and B
- 38. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland Washed Salt A Ultrapure Salt B Power consumption differential (EUR/y) 0 - 830’000 Hydrochloric acid differential (EUR/y) 0 - 980’000 Membrane life differential (EUR/y) 0 - 220’000 Plant depreciation differential (EUR/y) 0 - 720’000 Total (EUR/y) 21’060’000 21’060’000 Salt delivered cost (EUR/t) 27.25 46.58 Salt price differential (EUR/t) - + 20.33 Salt price differential (%) - +74.6% Membrane Plant Operation with Salt A and B
- 39. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland Conclusions: • Ultrapure salt makes primary brine purification redundant • With ultrapure salt ,anion removal systems are not required • With ultrapure salt, membrane life of up to 8 years is possible • With ultrapure salt, plant operating cost is reduced • With ultrapure salt, plant extra capacity is not required • With ultrapure salt, loss of production is avoided • Ultrapure salt can be EUR 20.33 / t or 74.6% more expensive than washed salt for the same chlorine production economy calculated in the example • Each case must be examined considering specific costs
- 40. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Salt Partners VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland SNEP, Morocco Proinsal, Argentina Solvay, Spain Modi, India Enichem, Italy GACL, India Grasim, India Saukem, India Standard Alkali, India Bandar Imam, Iran Chemfab, India Century, India NRC, India Borregaard, Norway GHCL, India Heilbronn, Germany Safi Salt, Jordan Arab Potash, Jordan Da Qing He, China EPETCO, Egypt Atul, India MISR, Egypt Quimpac, Peru Azraq, Jordan Dwory, Poland Petkim, Turkey TCC, India Tata, India Hellenic, Greece Borsodchem, Hungary Sind Alkalies, Pakistan Frutarom, Israel Nirou Clor, Iran Kothari, India Uniteca, Portugal Ittehad, Pakistan Aragonesas, Spain Ercros, Spain Shriram, India Sitara, Pakistan Saboo, India Solvay, Argentina Ballarpur, India Salexpor, Portugal Atanor, Argentina Jayshree, India Fine Salt, India Tokuyama, Japan Andhra Sugars, India Emisal, Egypt Sales Monzon, Spain Reliance, India Punta de Lobos, Chile DCW, India Tekel, Turkey Salgema, Brazil SPIC, India Formosa Plastic Rio Doce, Brazil El Nasr, Egypt Mabuhay Vinyl, Philippines Arabian Chlorine, Saudi Arabia Abadan Petrochemical, Iran DSW, Israel Thanks to Salt Partners Cost Survey Contributors
- 41. Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012 Why not turn your salt into gold? VladimirM.Sedivy SaltPartnersLtd,Zurich,Switzerland