Supervisors: AYRAL Andre; andre.ayral@iemm.univ-montp2.fr BACCHIN Patrice ; bacchin@chimie.ups-tlse.

fr
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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
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1. Introduction
Aluminum is the most abundant metal in the earth's crust and the third most element in the earth's crust, after oxygen and silicon.

Aluminum is too reactive to be found pure. Bauxite (mainly aluminum oxide) is the most important ore.

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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

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2. Nomenclature
Figure 1: Dehydration Sequence Of Alumina Hydrates In Air

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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
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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

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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 airbone equipment, or fabrication forms.

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4. Mechanical Thermal Properties

Mechanical properties
Tensile Strength (MPa) Bending Strenght Mpa Modulus of Elasticity (E) X 108 MPa Compressive Strenght Mpa Modulus of Ridity(G) X 108 MPa Hardness on the mohs scale Thermal properties Melting point OC Boiling Point OC
9

173 413 26.8 3733 11.3

117 307 21.27 1600 8.67

9
2051 9.7 3530 200
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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.
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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.
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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
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6. Alumina Membranes
Highly selective Permeable / Selective ( based on pore size and dist.) Durable Hydrophilic to maximize flow and minimize fouling

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6. Alumina Membranes
Table 2 : Selected commercial Alumina Membranes

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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.

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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
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6.2. Mesoporous Membranes

Figure 4: Preparation procedure of boehmite sol

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6.2. Mesoporous Membranes

Figure 5: Schematic drawing of the rapid gelation processing, 1 nozzle, 2 - atomizing sol and 3 -substrate.

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6.2. Mesoporous Membranes

Mesoporous -alumina membranes are formed by dipcoating a porous substrate in a Boehmite (-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

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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.

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7. Membrane Modules
Tubular mode / Multichannel / Monolithic

Cross-section of a monolithic multi-channel membrane element [Hsieh et al., 1998]

Schematic side-view of membrane module consisting of multi-channel 22 elements [Remigy, 2007]

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7. Membrane Modules
Composite or anisotropic / Multilayer

Schematic representation of Polypeptide films formed inside pore walls of a thin anodic alumina membrane [Duran H. et al., 2004]
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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
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7. Membrane Modules

Alumina/Titanium oxide layers 7-84 channels Pore size>0.8m Compact d<1178mm P>80bar >80oC pH 0-14
Kerasep alumina membrane module

Bulk fermentation / Milk and dairy products / Beverages (beer, wine, water, fruit juice)
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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

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 Recovery

2. Food/Beverage

Clarification of juices

Eg. Pretreatment prior ion exchange/chromatography of clarified juice

Filtration of sugar cane juice Alcoholic beverages

ECN industry demonstration of inorganic membrane module for liquid phase separation [ecn.nl]

3. Pharmaceutical
Fermentation broths clarification Eg. Recovery of antibiotics Fungal cells ultrafiltration

Eg. microfiltration of biological media, such as human red blood cells

Lysozyme ultrafiltration, Penicillin recovery

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
-Al2O3/-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 wastewater

Example:
Pagana et al., 2008 : Composite -Al2O3 membranes made by solgel method

Pilot system for Cr(III) and Ar(V) removal Ar(V) 2 stages adsorption ultrafiltration process in series Cr(III) 1 adsorption-ultrafiltration parallel process

8.1 LPS / As(V) Cr (III) Removal

Flow diagram of the Cr (III) removal process [Pagana et al., 2008]

Conclusion: Adsorption-ultraltration ion process using ceramic membranes may oer a low cost eective alternative arsenic and chromium purication technology basically in terms of membrane stability, applied pressure and product ux with the additional advantage of being suitable for small local units

8.2 Gas Phase Separation (GPS)

1. Carbon Dioxide Capture

CO2/N2 separation H2/CO2 separation

2. Hydrocarbons separation
Acetone recovery Propane separation Alcoholic beverages
INSIDE Cram membrane by TAMI industry [tami-industries.com]

3. Catalytic reactors VOCs oxidation Methane to ethane reaction

8.2 GPS /VOCs removal

Alumina membrane are used in combination with catalysts or used for catalyst recovery in a wide range of applications
Example: 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 streams

Conclusion: The membrane performed very efficiently in the combustion of VOCs at low temperatures, although at the expense of a significant pressure drop.

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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]
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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

Acknowledgements
We would like to express our sincere thanks to

EM3E for its support

Prof.A.Ayral, Prof.P.Bacchin and A.Julbe for their advices

EM3E GROUP FOR THIS FIRST HARD SEMESTER!
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Goodbye France!
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