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Institut de recherche de Chimie Paris

Purification of phosphoric acid by liquid-liquid extraction Mariana Campos Assuncao 1,2 , Alexandre Chagnes 1 , Hubert Halleux 2 , Gérard Cote 1 1, PSL Research University, Chimie ParisTech - CNRS, Institut de Recherche de Chimie Paris, 11 rue Pierre et Marie Curie, 75005 Paris, France

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Institut de recherche de Chimie Paris

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  1. Purification of phosphoric acid by liquid-liquid extraction Mariana Campos Assuncao1,2, Alexandre Chagnes1, Hubert Halleux2, Gérard Cote1 1, PSL Research University, Chimie ParisTech - CNRS, Institut de Recherche de Chimie Paris, 11 rue Pierre et Marie Curie, 75005 Paris, France 2 Prayon, Gansbroekstraat 31, B2870 Ruisbroek, Belgium Institut de recherche de Chimie Paris 2nd International Conference on Separation Techniques (26-28 September 2016)

  2. Production and applications of Phosphoric Acid Ammonia Potassium Electricity Silica Coke Sulfuric Acid Phosphate Rock 95% Sulfur 5% Pyrometallurgical Hydrometallurgical Phosphoroussulfides Phosphorouschlorides LIQUID-LIQUID EXTRACTION Chlorine • Fertilizers • Direct application rock (DAR) • Single superphosphate • Triple superphosphate • Mono ammonium phosphate (MAP) • Di ammonium phosphate(DAP) • NPK fertilizers Thermal Phosphoric Acid PurifiedPhosphoric Acid • Phosphorousderivativeproducts • Agrochemicals • Flameretardants • Intermediates • Lubrificantaddititives • Pharmaceuticals • Phosphoricacidproducts • Food grade • Cola grade • Pharmaceutical grade • Semi grades • Pyrophosphoricacid • Polyphosphoricacid The choice of the purification route depends on the application of the purified product and the limiting factor is usually its cost. 2nd International Conference on Separation Techniques (26-28 September 2016)

  3. Stratégie du choix d’un système d’extraction • Speciationdiagram H3PO4-Eau Reference : PhD thesis. Adrien Dartilongue. ENSTA-ENSCP The neutralform of H3PO4isprevalentuntil 5M, thus the interest in employingsolvatingextractants

  4. Context Diisopropyl ether( DIPE) Tributyl phosphate (TBP) Prayon’s process based on the selective extraction of H3PO4(TBP - DIPE) is the most used worldwide for this end. This work introduces a new purification system, 10 wt% A336 in 90 wt% DIPEand : 1. Reviews its extraction performances 2. Discusses its physicochemistry , particularly 3Φ transitions 3. Concludes on its industrial applicability Alamine 336 (A336) *C8-C10 2nd International Conference on Separation Techniques (26-28 September 2016)

  5. Purification of phosphoric acid Particularities of the system: High acid content Important volume variation during extraction Extraction of H3PO4 Organic Organic Expansion Aqueous Aqueous Contraction 2nd International Conference on Separation Techniques (26-28 September 2016)

  6. Extraction yield and selectivity Feed solution [H3PO4]=14 M Great selectivity The new system have a better yield and an interesting selectivity towards Ti. 2nd International Conference on Separation Techniques (26-28 September 2016)

  7. Physicochemistry properties Prayon Third phase There is a risk of 3rd phase transition during the extraction process Why 3-phases transitions take place? Which parameters favors the transition? 2nd International Conference on Separation Techniques (26-28 September 2016)

  8. Why 3Φ transitions takes place? 3Φ results from the coalescence aggregates in the organic phase Aggregates are formed as a result of : • Hydrogenbounds (supported by H3PO4, H2O...) • Electrostatic forces • Attractive van der Waals forces 2nd International Conference on Separation Techniques (26-28 September 2016)

  9. Why 3Φ transitions takes place? Attraction forces (FA): • van der Waals (electrostatic interactions among multipoles : H2O, etc.) Leads to 3Φ when FA>2KBT Repulsion forces (FR): • Steric repulsion • Thermal energy Leads to 2Φ H2O H2O Third-phase transition has been associated to an increase in the attraction forcesbetween the micelles. Phosphoric acid could be extracted into the core of reversed micelles. Two types of forces exists in the organic phase: 2nd International Conference on Separation Techniques (26-28 September 2016)

  10. Why 3Φ transitions takes place? Apolar Polar Third Phases transitions depends on : • Lipophilic barriers (length of alkyl chain) • Micelle’s core polarity • Temperature • Diluent In our case [H3PO4]organd [H2O]orgchange as [H3PO4]aq,initialis increased. 2nd International Conference on Separation Techniques (26-28 September 2016)

  11. Why 3Φ transitions takes place? Reverse micelles in the organic phase have strongintermolecular attraction whentheircoresincludeshigh H2O concentration H2O exists in reverse micelles as : • Free water • Bulky water • Anion bounded water • Cation bounded water The avarage radius of aggregationincreaseswhen the acid and/or H2O concentration increases. 2nd International Conference on Separation Techniques (26-28 September 2016)

  12. Composition of 3Φ system Heavy Transfer of diluent Light Water activity decreases The volume of the heavy phase increases 40% because the diluent is re-inserted between the micelles. 2nd International Conference on Separation Techniques (26-28 September 2016)

  13. Composition of 3Φ system Extracted H3PO4 in organic phase as equilibrium [H3PO4]aqincreases 2Φ 2Φ 3Φ [H3PO4] in heavy organic phase is only weakly modified as equilibrium [H3PO4]aq Increases H3PO4 has low effect on the variation of wdw forces 2nd International Conference on Separation Techniques (26-28 September 2016)

  14. Composition of 3Φ system Extracted H2O in organic phase as equilibrium [H3PO4]aqincreases Higher extracted water concentration, stronger wdw attractive forces : splitting of the organic phase 3Φ 2Φ 2Φ Water expelled from the cores of micelles as water activity decreases: decrease of wdw attractive forces Still low extracted water concentration: weak attractive wdw forces – single organic phase Again low extracted water concentration: weaker attractive wdw forces – again single organic phase H2O is a key component to control attractive wdw forces between micelles 2nd International Conference on Separation Techniques (26-28 September 2016)

  15. Most important findings 2Φ 3Φ 2Φ 1.71M 0.86 M 0.79 M 0.72 M [H3PO4] 2nd International Conference on Separation Techniques (26-28 September 2016)

  16. CONCLUSION 2nd International Conference on Separation Techniques (26-28 September 2016)

  17. Thank you for the attention Questions ? 2nd International Conference on Separation Techniques (26-28 September 2016)

  18. Comité de suivi de thèse(20/11/2015)

  19. The total of moles of acid increases consistently but total moles of water remains the same. As we move towards the border of 3Φ→ 2Φ

  20. Isothermes avec le DIPE 2nd International Conference on Separation Techniques (26-28 September 2016)

  21. Composition of 3Φ system 100 % DiPE 50% Transfer of diluent The volume of the heavy phase increases 538%because the diluent is re-inserted between the micelles. 2nd International Conference on Separation Techniques (26-28 September 2016)

  22. Composition of 3Φ system Extracted H3PO4 in organic phase as equilibrium [H3PO4]aqincreases [H3PO4] in heavy organic phase decreases as equilibrium [H3PO4]aq Increases 2nd International Conference on Separation Techniques (26-28 September 2016)

  23. Composition of 3Φ system 2nd International Conference on Separation Techniques (26-28 September 2016) 2nd International Conference on Separation Techniques (26-28 September 2016)

  24. Isothermes avec le DBE 2nd International Conference on Separation Techniques (26-28 September 2016)

  25. ACIDE Heavy Transfer of diluent Light Water activity decreases The volume of the heavy phase increases 37% because the diluent is re-inserted between the micelles. 2nd International Conference on Separation Techniques (26-28 September 2016)

  26. EAU 2nd International Conference on Separation Techniques (26-28 September 2016)

  27. 2nd International Conference on Separation Techniques (26-28 September 2016)

  28. As acidity increases the species ether-H+ are formed : Solvation of the hydronium ion and delocalisatio of the positive charge between the hydrogens that take part on the pyramidal structure Diamond, R. M. & Tuck, D. G. in Progress in Inorganic Chemistry2, 109 (F. Albert Cotton, 2009). 2nd International Conference on Separation Techniques (26-28 September 2016)

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