Salt Presentation2

Salt Partners
Economy of Ultrapure Salt Feedstock in Membrane Cell Chloralkali Plants
Vladimir M. Sedivy
MSc (Hons) Chem Eng, IMD
President Salt Partners Ltd, Zurich, Switzerland
Watch the video record of this presentation: www.youtube.com/watch?v=ELZ3SYrDgJE (25:44)

Second International Flemion Seminar, Zurich, Switzerland, 13. - 14. June 2012
Salt Partners
Salt production world-wide

Salt type Solar salt Rock salt Brines Total World production 90000000 t/y 80000000 t/y 80000000 t/y 250000000 t/y
Vladimir M. Sedivy Salt Partners Ltd, Zurich, Switzerland
Salt Partners
Salt consumption world-wide

Salt user Chemical industry Food Other Salt consumption 150000000 t/y 60000000 t/y 40000000 t/y
Salt Partners
Salt Purities
NaCl Purity (%)
Rock salt Crude sea salt Washed sea salt Purified sea salt Refined salt Vacuum refined salt Ultrapure salt
90 - 97 97 - 99 99 99.6 99.6 99.8 99.8 99.9 99.9 99.97 99.97 99.997
Salt Partners
Salt Prices Depend on Salt Purity
120
100
Salt Price (USD/t)
80
60
40
20
0 88 90 92 94 96 Salt Purity (% NaCl) 98 100 102
Industrial salt prices vary between USD 10.-/t and USD 100.-/t depending on salt purity
Salt Partners
Important Impurities in Salt in 1996
Rock salt CaSO4 0.5 2%
Sea salt 0.5 1%
Lake salt 0.5 2%
Brines Saturated
MgSO4
MgCl2
Traces
0.2 0.6%
0.3 1%
Traces
Traces Traces Traces Traces Traces
Traces
CaCl2 Na2SO4 KCl NaBr Insolubles 1 30% 0.1 1%
1 10%
Salt Partners
Important Impurities in Salt in 2012
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.
Salt Partners
Important Impurities in Brine for Membrane Cells
Max.
Ca + Mg SO4 I Ba Sr
Membrane Licensor A Membrane Licensor B

20 5 0.1 0.1 0.4 0.1 5 0.05 0.1 0.01 20 4-8 0.2 0.5 0.1 0.1 5 0.1 0.1 0.01 0.01
ppb g/l ppm ppm ppm ppm ppm ppm ppm ppm ppm
Al SiO2 Fe Hg Ni Mn
F
TOC
ppm
ppm
10
0.5
10
Salt Partners
The Basic Chloralkali Equation
Caustic and Chlorine from Salt
2 NaCl + 2 H2O + Electrical Energy = 2 NaOH + Cl2 + H2

119 1.45 1.68
36
82 1
71 1
Salt Partners
The Basic Chloralkali Equation
Soda Ash from Salt and Lime
2 NaCl + CaCO3 = Na2CO3 + CaCl2 119 1.1 110 0.93 111 1 120
Salt Partners
Why must brine for chloralkali manufacture be pure?

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.

Salt Partners
Brine Purification: Ca and Mg Precipitation

Calcium precipitation
Ca++ + Na2CO3 = CaCO3 + 2 Na+ 40 108 Mg++ + 2 NaOH = Mg(OH)2 + 2 Na+ 24 82
Magnesium precipitation
Salt Partners
Brine Purification: Overdosing of Reagents
For calcium precipitation

0.4 kg Na2CO3 per m3 of brine 0.15 kg NaOH per m3 of brine
For magnesium precipitation
Salt Partners
Brine Purification: Sulphate Removal

With BaCO3
SO4-- + BaCO3 = BaSO4+ CO3-96 197 233 SO4-- + BaCl2 = BaSO4+ 2 Cl96 208 233 SO4-- + CaCl2 = CaSO4+ 2 Cl96 111 136 From 4 8 g/l to 80 g/l in purge as Na2SO4
With BaCl2 With CaCl2 With Nanofiltration
Salt Partners
Nanofiltration Operating Point
Salt Partners
Salt Partners Cost Survey Contributors
SNEP, Morocco Proinsal, Argentina Solvay, Spain Modi, India
Enichem, Italy
Standard Alkali, India NRC, India
GACL, India
Bandar Imam, Iran Borregaard, Norway
Grasim, India
Chemfab, India GHCL, India
Saukem, India
Century, India Heilbronn, Germany
Safi Salt, Jordan

Atul, India Dwory, Poland Vladimir M. Sedivy Salt Partners Ltd, Zurich, Switzerland
Arab Potash, Jordan

MISR, Egypt Petkim, Turkey
Da Qing He, China

Quimpac, Peru TCC, India
EPETCO, Egypt
Azraq, Jordan Tata, India
Hellenic, Greece
Nirou Clor, Iran Aragonesas, Spain
Borsodchem, Hungary
Kothari, India Ercros, Spain
Sind Alkalies, Pakistan

Uniteca, Portugal Shriram, India
Frutarom, Israel
Ittehad, Pakistan Sitara, Pakistan
Saboo, India
Atanor, Argentina Andhra Sugars, India
Solvay, Argentina
Jayshree, India Emisal, Egypt
Ballarpur, India
Fine Salt, India Sales Monzon, Spain
Salexpor, Portugal
Tokuyama, Japan Reliance, India
Punta de Lobos, Chile

SPIC, India Mabuhay Vinyl, Philippines
DCW, India
Formosa Plastic Arabian Chlorine, Saudi Arabia
Tekel, Turkey
Rio Doce, Brazil Abadan Petrochemical, Iran
Salgema, Brazil
El Nasr, Egypt DSW, Israel
Salt Partners
Cost of Salt and Brine Treatment
Cost of brine treatment Cost of salt, brine and disposal treatment and disposal (USD / t salt) Minimum Average Maximum 1.50 10 30 (USD / t salt) 10 25 50
Salt Partners
Relative Brine Treatment Cost
Cost of brine treatment as percentage of salt cost
Percentage of chloralkali production cost (%) 3 15 40
(%) Minimum Average Maximum 100 170 300
Salt Partners
HYDROSAL Process
CH-8053 Zurich Tel.: +41 (44) 422 26 82 Fax: +41 (44) 422 26 83 www.salt-partners.com
Salt Centrifuge Water Purified Salt
Centrifuge separates salt and brine

Conventional washing with water in the centrifuge
Salt Partners
HYDROSAL Process
Salt Hydroextractor
Centrifuge Purified Salt
Water
Filtrate Vessel
Dissolve salt fines in water and use this pure brine to remove impurities from salt in the hydroextractor
Filtrate Pump
Salt Partners
HYDROSAL Process
Hydroextractor
Salt
Water
Filtrate Vessel
Hydraulically transport salt to the hydroextractor and return the transport brine to the elutriator
Slurry Pump
Filtrate Pump
Salt Partners
HYDROSAL Process
Hydroextractor
Salt
Water
Filtrate Vessel
Circulate impure brine to control hydroclassification and elutriation efficiency

Slurry Pump Brine Pump
Filtrate Pump
Salt Partners
Elutriation
Settling velocities in brine

NaCl Gypsum 100-150
Elutriation in upwards flowing brine
Salt Partners
Hydroclassification
Salt bed with buried impurities
Hydroclassification of impurities in partially fluidised salt bed
Salt Partners
Hydroextraction
Hydroextraction / Displacement crystallisation
6% 4% 15% NaCl
MgCl2 MgSO4
Impurities are extracted from cavities by diffusion
NaCl is recrystallised on crystal surface
25% NaCl
Salt Partners
Hydroextraction does not work in all vessels
In this vessel salt flows out mainly through the centre
So called rat hole develops in the centre of the vessel
Salt Partners
Hydroextraction works only with plug flow of salt
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 countercurrent flow
Picture 3: Second black ink injection. There are no traces of black colour in the salt flowing downwards in plug flow
Salt Partners
Solution mining for natural gas storage, co-generation, brine purification, salt crystallisation and refining plant in Portugal
Salt Partners
40 t/h salt purification plant in Portugal producing purest industrial salt in Europe
Performance test Ca Mg SO4 ppm ppm ppm 0.6 0.2 53
Salt Partners
High quality European vacuum salt A before and after HYDROSAL purification
Commercial vacuum salt product

Ca Mg SO4
HYDROSAL purified
<1 0.07 29 72 34 < 0.1 < 0.02 < 0.1 < 0.05 0.23
ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm
<1 0.12 118 87 35 < 0.1 < 0.02 < 0.1 < 0.05 0.58
K Br I Ba Sr Al SiO2
Salt Partners
High quality European vacuum salt E before and after HYDROSAL purification

Ca Mg SO4
HYDROSAL purified
5.8 2.9 33 29 28 < 0.1 < 0.02 < 0.1 0.05 0.47
6.5 3.1 191 36 29 < 0.1 < 0.02 0.1 < 0.05 0.81
Salt Partners
High quality European vacuum salt N before and after HYDROSAL purification

Ca Mg SO4
HYDROSAL purified
66 1.2 229 185 36 < 0.1 < 0.02 2.2 0.1 < 0.1
211 6.8 820 225 43 0.4 0.04 6.3 1.0 < 0.1
Salt Partners
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
Salt Partners
Comparative Study on Differential Costs in a Membrane Cell Plant having Following Parameters:
Plant Capacity: 300000 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
Salt Partners
Membrane Plant Operation with Salt A and B
Washed Salt A
Ca Mg
Ultrapure Salt B
0.00005 0.00001 0.003 0 0.02 99.996
(%) (%) (%) (%) (%) (%)
0.1 0.01 0.4 0.5 7 98.9
SO4 Insolubles Moisture NaCl (dry basis)
Salt Partners
Washed Salt A Ultrapure Salt B

Salt cost Salt handling labour Fuel
(EUR/y) (EUR/y) (EUR/y)
14820000 330000 40000
23010000 300000 0
Salt handling maintenance

Process water Brine purification chemicals Primary brine purification power Primary brine purification labour Primary brine purif. maintenance Solids disposal
(EUR/y)
(EUR/y) (EUR/y) (EUR/y) (EUR/y) (EUR/y) (EUR/y)
80000
20000 1170000 330000 330000 300000 770000
120000
330000 50000 0 0 0 0
Salt Partners

Nanofiltration plant cost Nanofiltration power Nanofiltration refrigeration water
(EUR/y) (EUR/y) (EUR/y)
800000 120000 20000
0 0 0
Nanofiltration treated water

Nanofiltration reactants Nanofiltration membrane replacement Nanofiltration plant maintenance Bromine removal Ferrocyanide removal Iodine removal
(EUR/y)
(EUR/y) (EUR/y) (EUR/y) (EUR/y) (EUR/y) (EUR/y)
40000
50000 40000
0
0 0 0 0 0 0
60000
1500000 0
Salt Partners

Power consumption differential Hydrochloric acid differential (EUR/y) (EUR/y) 0 0 - 830000 - 980000
Membrane life differential

(EUR/y)
(EUR/y) (EUR/y) (EUR/t) (EUR/t) (%)
0
0 21060000 27.25 -
- 220000
- 720000 21060000 46.58 + 20.33 +74.6%
Plant depreciation differential Total Salt delivered cost Salt price differential Salt price differential
Salt Partners
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
Salt Partners
Thanks to Salt Partners Cost Survey Contributors
SNEP, Morocco Proinsal, Argentina Solvay, Spain Modi, India
Enichem, Italy
Standard Alkali, India NRC, India
GACL, India
Bandar Imam, Iran Borregaard, Norway
Grasim, India
Chemfab, India GHCL, India
Saukem, India
Century, India Heilbronn, Germany
Safi Salt, Jordan

Atul, India Dwory, Poland Vladimir M. Sedivy Salt Partners Ltd, Zurich, Switzerland
Arab Potash, Jordan

MISR, Egypt Petkim, Turkey
Da Qing He, China

Quimpac, Peru TCC, India
EPETCO, Egypt
Azraq, Jordan Tata, India
Hellenic, Greece
Nirou Clor, Iran Aragonesas, Spain
Borsodchem, Hungary
Kothari, India Ercros, Spain
Sind Alkalies, Pakistan

Uniteca, Portugal Shriram, India
Frutarom, Israel
Ittehad, Pakistan Sitara, Pakistan
Saboo, India
Atanor, Argentina Andhra Sugars, India
Solvay, Argentina
Jayshree, India Emisal, Egypt
Ballarpur, India
Fine Salt, India Sales Monzon, Spain
Salexpor, Portugal
Tokuyama, Japan Reliance, India
Punta de Lobos, Chile

SPIC, India Mabuhay Vinyl, Philippines
DCW, India
Formosa Plastic Arabian Chlorine, Saudi Arabia
Tekel, Turkey
Rio Doce, Brazil Abadan Petrochemical, Iran
Salgema, Brazil
El Nasr, Egypt DSW, Israel
Why not turn your salt into gold?

Salt Presentation2

Enviado por

Dados do documento

Direitos autorais

Formatos disponíveis

Compartilhar este documento

Compartilhar ou incorporar documento

Opções de compartilhamento

Você considera este documento útil?

Este conteúdo é inapropriado?

Direitos autorais:

Formatos disponíveis

Salt Presentation2

Enviado por

Direitos autorais:

Formatos disponíveis

Salt Partners

Economy of Ultrapure Salt Feedstock in Membrane Cell Chloralkali Plants

MSc (Hons) Chem Eng, IMD

President Salt Partners Ltd, Zurich, Switzerland

Watch the video record of this presentation: www.youtube.com/watch?v=ELZ3SYrDgJE (25:44)

Salt production world-wide

Vladimir M. Sedivy Salt Partners Ltd, Zurich, Switzerland

Salt consumption world-wide

Vladimir M. Sedivy Salt Partners Ltd, Zurich, Switzerland

Vladimir M. Sedivy Salt Partners Ltd, Zurich, Switzerland

90 - 97 97 - 99 99 99.6 99.6 99.8 99.8 99.9 99.9 99.97 99.97 99.997

Salt Price (USD/t)

Vladimir M. Sedivy Salt Partners Ltd, Zurich, Switzerland

0 88 90 92 94 96 Salt Purity (% NaCl) 98 100 102

Rock salt CaSO4 0.5 2%

Sea salt 0.5 1%

Lake salt 0.5 2%

CaCl2 Na2SO4 KCl NaBr Insolubles 1 30% 0.1 1%

Vladimir M. Sedivy Salt Partners Ltd, Zurich, Switzerland

Membrane Licensor A Membrane Licensor B

2 NaCl + 2 H2O + Electrical Energy = 2 NaOH + Cl2 + H2

119 1.45 1.68

Vladimir M. Sedivy Salt Partners Ltd, Zurich, Switzerland

Why must brine for chloralkali manufacture be pure?

Vladimir M. Sedivy Salt Partners Ltd, Zurich, Switzerland

Brine for chloralkali manufacture must be purified.

Brine Purification: Ca and Mg Precipitation

Ca++ + Na2CO3 = CaCO3 + 2 Na+ 40 108 Mg++ + 2 NaOH = Mg(OH)2 + 2 Na+ 24 82

Brine Purification: Overdosing of Reagents

For calcium precipitation

0.4 kg Na2CO3 per m3 of brine 0.15 kg NaOH per m3 of brine

For magnesium precipitation

Brine Purification: Sulphate Removal

With BaCl2 With CaCl2 With Nanofiltration

Vladimir M. Sedivy Salt Partners Ltd, Zurich, Switzerland

Safi Salt, Jordan

Arab Potash, Jordan

Da Qing He, China

Sind Alkalies, Pakistan

Punta de Lobos, Chile

Vladimir M. Sedivy Salt Partners Ltd, Zurich, Switzerland

Percentage of chloralkali production cost (%) 3 15 40

(%) Minimum Average Maximum 100 170 300

Salt Centrifuge Water Purified Salt

Vladimir M. Sedivy Salt Partners Ltd, Zurich, Switzerland

Centrifuge separates salt and brine

Centrifuge Purified Salt

Vladimir M. Sedivy Salt Partners Ltd, Zurich, Switzerland

Centrifuge Purified Salt

Vladimir M. Sedivy Salt Partners Ltd, Zurich, Switzerland

Centrifuge Purified Salt

Vladimir M. Sedivy Salt Partners Ltd, Zurich, Switzerland

Circulate impure brine to control hydroclassification and elutriation efficiency

Slurry Pump Brine Pump

Settling velocities in brine

Elutriation in upwards flowing brine

Vladimir M. Sedivy Salt Partners Ltd, Zurich, Switzerland

Salt bed with buried impurities

Hydroclassification of impurities in partially fluidised salt bed

Vladimir M. Sedivy Salt Partners Ltd, Zurich, Switzerland

NaCl is recrystallised on crystal surface

Vladimir M. Sedivy Salt Partners Ltd, Zurich, Switzerland

In this vessel salt flows out mainly through the centre

So called rat hole develops in the centre of the vessel