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Alumina membranes final presentation Presentation Transcript

  • 1. Supervisors: AYRAL Andre; andre.ayral@iemm.univ-montp2.fr BACCHIN Patrice ; bacchin@chimie.ups-tlse.fr January 26, 2012
  • 2. 1. Introduction Ceramics: ‘’The art and science of making and using solid articles which have as their essential component, and are composed in large of inorganic nonmetallic materials.’’ Kingerly ‘’All high-temperature chemistry and physics of nonmetallic materials, and the techniques of forming products at high temperatures.’’ Mitchell 2 January 26, 2012
  • 3. 1. Introduction Aluminum is the most abundant metal in the earths crust and the third most element in the earths crust, after oxygen and silicon. Aluminum is too reactive to be found pure. Bauxite (mainly aluminum oxide) is the most important ore. 3 January 26, 2012
  • 4. 1. Introduction The following information has been gathered: occurrence in nature mineralogical characteristics mechanical, thermal, chemical and colloidal properties alumina membranes fabrication modules and industrial applications 4 January 26, 2012
  • 5. 2. NomenclatureFigure 1: Dehydration Sequence Of Alumina Hydrates In Air 5 January 26, 2012
  • 6. 3. Structure And Mineralogical Properties Crystal structure is the main factor controls the properties of alumina In general, the phases of alumina are produced by pseudomorphic dehydration Pseudomorphosis is of considerable importance because of its effect on surface area of the intermediate phase structures, and on crystal size and size distribution 6 January 26, 2012
  • 7. 3. Structure And Mineralogical Properties Alumina is widely used as a catalyst or catalyst support in many heterogeneous catalytic processes owing to its high surface area, superior chemical activity and low cost. Resistance to:  softening  swelling and disintegration when immersed in water or other liquids  thermal shock and corrosion The ability to return to the original highly adsorptive from by a suitable thermal regenerative treatment 7 January 26, 2012
  • 8. 4. Mechanical – Thermal Properties Alumina has remarkable mechanical properties in comparison with conventional porcelains and other single oxide ceramics The interest in mechanical – thermal properties lead to several applications such as possible substitution of alumina ceramics for refractory metal parts in air- bone equipment, or fabrication forms. 8 January 26, 2012
  • 9. 4. Mechanical – Thermal PropertiesMechanical propertiesTensile Strength (MPa) 173 117Bending Strenght Mpa 413 307Modulus of Elasticity (E) X 108 MPa 26.8 21.27Compressive Strenght Mpa 3733 1600Modulus of Ridity(G) X 108 MPa 11.3 8.67Hardness on the mohs scale 9Thermal properties 2051Melting point OC ±9.7 3530Boiling Point OC ± 200 9 January 26, 2012
  • 10. 5. Chemical Properties Chemical reactions of alumina of general ceramic interest include the resistance to attack of sintered alumina by various reagents, particularly at high temperatures. Finely divided alumina is rapidly dissolved by HF, hot concentrated H2SO4, mixtures of these acids, ammonium fluoride, molten alkali bisulfates or pyrosulfates, and by concentrated HCl, especially when under pressure. 10 January 26, 2012
  • 11. 6. Alumina Membranes Alumina membranes are constantly growing area. In the Figure 3, it can be seen that, the publication numbers are highly increasing parallel with the membrane research especially during recent years. 11 January 26, 2012
  • 12. 6. Alumina Membranes Excellent mechanical strength Tolerance to solvents, as well as pH, oxidation, Can be used at significantly higher temperatures Have better structural stability Can be backflushed Less cost 12 January 26, 2012
  • 13. 6. Alumina Membranes Highly selective Permeable / Selective ( based on pore size and dist.) Durable Hydrophilic to maximize flow and minimize fouling 13 January 26, 2012
  • 14. 6. Alumina MembranesTable 2 : Selected commercial Alumina Membranes 14 January 26, 2012
  • 15. 6.1. Macroporous Membranes Usage: Filtration , diffusion, dispersion rolls, inkpads for fingerprinting Anodizing of pure aluminum most common path  Anodizing well controlled process and provides homogenous pore distribution  The preparation of regular pore arrays typically involves electrolytic polishing and multiple anodising steps or even mechanical pre-texturing. 15 January 26, 2012
  • 16. 6.1. Macroporous Membranes Macroporous alumina membranes also can be made from particles or discontinuous fibers by the use of a binder or by sintering . Silica, vitreous glass and also phosphate are widely used binders in the refractory and ceramic industry This method is generally used to produce alumina microfiltration filters, which contain larger pores and supports for ultrafiltration membranes, which contain smaller pores 16 January 26, 2012
  • 17. 6.2. Mesoporous Membranes Figure 4: Preparation procedure of boehmite sol 17 January 26, 2012
  • 18. 6.2. Mesoporous Membranes Figure 5: Schematic drawing of the rapid gelation processing, 1 - nozzle, 2 - atomizing sol and 3 -substrate. 18 January 26, 2012
  • 19. 6.2. Mesoporous Membranes Mesoporous γ-alumina membranes are formed by dip- coating a porous substrate in a Boehmite (γ-AlOOH) precursor sol, will be treated by heat and sintering steps. The quality and properties of the membrane depend on the dispersion rheology and quality of the Boehmite sol and the dip-coating process as well 19 January 26, 2012
  • 20. 6.3. Microporous Membranes A conventional path to synthesis microporous membranes is slipcasting. In the slipcasting method, a porous support is usually made first by conventional ceramic processing techniques to provide rigid structure with relatively large pore size for slip deposition. The ability to consistently produce high quality alumina membranes on a commercial scale has been the key to wider acceptance of ceramic membranes as a separation tool. 20 January 26, 2012
  • 21. 21 January 26, 2012
  • 22. 7. Membrane Modules Tubular mode / Multichannel / Monolithic Cross-section of a monolithic multi-channel membrane element [Hsieh et al., 1998]Schematic side-view of membranemodule consisting of multi-channel elements [Remigy, 2007] 22 12/5/2012
  • 23. 7. Membrane Modules Composite or anisotropic / Multilayer Schematic representation of Polypeptide films formed insidepore walls of a thin anodic alumina membrane [Duran H. et al., 2004] 12/5/2012
  • 24. 7. Membrane Modules Honeycomb mode (a) AnoporeTM alumina membrane with honeycomb pore size distribution(b) Commercial version of honeycomb alumina membrane by Lianyungang Highborn Technology Co., Ltd 12/5/2012
  • 25. 7. Membrane Modules•Alumina/Titaniumoxide layers•7-84 channels•Pore size>0.8μm•Compact•d<1178mm•P>80bar•Θ>80oC•pH 0-14 Kerasep® alumina membrane module Bulk fermentation / Milk and dairy products / Beverages (beer, wine, water, fruit juice) 25 12/5/2012
  • 26. 8. Applications Adsorption layer of alumina Microfiltration – Ultrafiltration Crossflow filtration – High Crossflow velocity Transmembrane pressure : driving force of operation Concentration of soluble molecules and suspended solids & Clarification by removing suspended solids Pretreatment process
  • 27. 8.1 Liquid phase separation (LPS)1. Environmental Ions removal from wastewater (Cr, F, Ar)Eg. Microporous Alumina membrane for Heavy metals removal in petrochemical industry Oil Recovery2. Food/Beverage Clarification of juicesEg. Pretreatment prior ion exchange/chromatography of clarified juice Filtration of sugar cane juice Alcoholic beverages ECN industry demonstration of inorganic membrane module for3. Pharmaceutical liquid phase separation [ecn.nl] Fermentation broths clarification Eg. Recovery of antibiotics Fungal cells ultrafiltrationEg. microfiltration of biological media, such as human red blood cells Lysozyme ultrafiltration, Penicillin recovery
  • 28. 8.1 LPS / As (V) – Cr (III) Removal In a wide range of wastewaters, alumina membranes assumed to be suitable for Ar(V) and Cr (III) removal γ-Al2O3/α-Al2O3, mesoporous alumina / Calcium doped alumina / Composite membranes Concentration of arsenic ions decreased from 1ppm  in 5ppb Flocculation was used as a pretreatment / for the treatment of the stone cutting wastewaterExample: Pagana et al., 2008 : Composite γ-Al2O3 membranes made by sol–gel methodPilot system for Cr(III) and Ar(V) removalAr(V) 2 stages adsorption – ultrafiltration process in seriesCr(III)  1 adsorption-ultrafiltration parallel process
  • 29. 8.1 LPS / As(V) – Cr (III) Removal Flow diagram of the Cr (III) removal process [Pagana et al., 2008]Conclusion: Adsorption-ultrafiltration ion process using ceramic membranes may offer a low costeffective alternative arsenic and chromium purification technology basically in terms of membranestability, applied pressure and product flux with the additional advantage of being suitable forsmall local units
  • 30. 8.2 Gas Phase Separation (GPS)1. Carbon Dioxide Capture CO2/N2 separation H2/CO2 separation2. Hydrocarbons separation Acetone recovery Propane separation Alcoholic beverages INSIDE Céram membrane by TAMI industry [tami-industries.com]3. Catalytic reactors VOCs oxidation Methane to ethane reaction
  • 31. 8.2 GPS /VOCs removal Alumina membrane are used in combination with catalysts or used for catalyst recovery in a wide range of applicationsExample: Saraco et al., 1999 / University of Saragoza Chem. Eng.Lab. Pt/Al2O3 and perovskite-containing membranes Using hydrogenation reactions over Pt/Al2O3 catalysts in membrane module Purification (by catalytic combustion) of air streams containing volatile organic compounds (VOCs) in low concentrations Membrane would be expected to give high contact efficiency in the reaction of diluted streamsConclusion: The membrane performed very efficiently in the combustion of VOCs at lowtemperatures, although at the expense of a significant pressure drop. 31 12/5/201212/5/2012
  • 32. 8.2 GPS /VOCs removal Applications of membrane reactors [Coronas et al., 1999] Schematic of a multi tube membrane module for H2 and CO2 separation [Diriz et al., 2007]12/5/2012 32 12/5/2012 12/5/2012
  • 33. 9. Perspectives Nanotechnology / Composite structures Modifications Sensitive active layers Alumina Catalysts/ Surface Adsorption Nanofiltration Gas separation Lower Cost (10 times > Polymeric, Remigy, 2004) Lower Fragility / Fouling/ Cracking Application of ceramic membranes in fields “traditionally” dominated by polymeric membranes! 12/5/2012 33
  • 34. AcknowledgementsWe would like to express our sincere thanks to EM3E for its supportProf.A.Ayral, Prof.P.Bacchin and A.Julbe for their advices EM3E GROUP FOR THIS FIRST… HARD SEMESTER! 34 12/5/2012
  • 35. Goodbye France! 35 12/5/2012