ChE ELMT: Membrane Technology

Lecture 2: Membrane Materials Elements and Configuration

Prof. Philipina A. Marcelo, Ph. D.
Department of Chemical Engineering and The Research Center for the Natural Sciences University of Santo Tomas

TYPES OF MEMBRANES
A. Ceramic Membranes: Current status and prospects for applications
Actual ceramic membrane elements are composed of a macroporous inorganic material supporting a multilayer porous ceramic structure exhibiting a non-deformable porosity with pore sizes ranging from macropores to micropores.
Macroporous materials: with a flat, tubular, multichannel, or monolithic geometry

Ceramic elements are the basic units in which mass transfer and separation obey different transport mechanisms relating to: Membrane physical characteristics: pore size, porosity and membrane thickness Physicochemical interactions between feed liquid and membrane surfaces Hydrodynamics in the elements

Chapter 6 in Sastre, A. M., Pabby, A. K., & Rizvi, S. S. H. (2009). Handbook of Membrane Separations. CRC Press, Taylor and Francis Group.

TYPES OF MEMBRANES
A. Ceramic Membranes: Current status and prospects for applications
First generation of porous ceramic membranes
New generations of microporous or dense ceramic membranes Devoted to liquid filtration Being developed for gas and vapor separation or biological and chemical catalytic reactors

Some exhibit high oxygen or hydrogen separation selectivity useful in new technologies for power generation Transport mechanisms are based on ion conduction in the solid at high temperature.

Chapter 6 in Sastre, A. M., Pabby, A. K., & Rizvi, S. S. H. (2009). Handbook of Membrane Separations. CRC Press, Taylor and Francis Group.

A. Ceramic Membranes: Current status and prospects for applications

Description of ceramic membranes:
Currently available ceramic membranes: made of macroporous support, one or several macroporous intermediate layers, and a meso- or microporous top layer. Production of membrane elements: Ceramic paste extrusion for supports Slip-casting of powder suspensions for microfiltration layers Solgel processing of colloidal suspensions for ultra- or nanofiltration layers

Chapter 6 in Sastre, A. M., Pabby, A. K., & Rizvi, S. S. H. (2009). Handbook of Membrane Separations. CRC Press, Taylor and Francis Group.

A. Ceramic Membranes: Current status and prospects for applications

Membrane elements:
Flat geometry vs. cylindrical shape Cylindrical shape is preferred. Better mechanical properties. Easier sealing of elements. Original design properties: tube diam. = 6 15 mm; wall thickness = 2 mm.

Chapter 6 in Sastre, A. M., Pabby, A. K., & Rizvi, S. S. H. (2009). Handbook of Membrane Separations. CRC Press, Taylor and Francis Group.

A. Ceramic Membranes: Current status and prospects for applications

Membrane elements:
Flat geometry vs. cylindrical shape Cylindrical shape is preferred. Better mechanical properties. Easier sealing of elements. Original design properties: tube diam. = 6 15 mm; wall thickness = 2 mm. First manufacturers: France (Membralox, Kerasep) Engineering challenge in the tubular geometry: high element volume to membrane surface ratio; high liquid flow for module feeding.
Chapter 6 in Sastre, A. M., Pabby, A. K., & Rizvi, S. S. H. (2009). Handbook of Membrane Separations. CRC Press, Taylor and Francis Group.

A. Ceramic Membranes: Current status and prospects for applications

Membrane elements:
Evolution of multichannel geometries of ceramic membranes

(a) Conventional cylindrical-shaped channels

(b) flower-like designed channels

Minimized both the volume to membrane surface ratio and feed flow.

Optimized both space occupancy of the membrane and channel wall thickness in the element.

Chapter 6 in Sastre, A. M., Pabby, A. K., & Rizvi, S. S. H. (2009). Handbook of Membrane Separations. CRC Press, Taylor and Francis Group.

A. Ceramic Membranes: Current status and prospects for applications

Membrane elements:
Evolution of multichannel geometries of ceramic membranes
Produced by TAMI Industries in France. Cross section diam = 10 25 mm # of channels = 3 to 39 Filtration area = up tp 0.5 m2 Increase in membrane surface compared with cylindrical-shaped channels 30%
Ceramic membranes with flower-like geometry

Chapter 6 in Sastre, A. M., Pabby, A. K., & Rizvi, S. S. H. (2009). Handbook of Membrane Separations. CRC Press, Taylor and Francis Group.

A. Ceramic Membranes: Current status and prospects for applications

Membrane elements:
Evolution of multichannel geometries of ceramic membranes

(a) Conventional cylindricalshaped channels

(b) flower-like designed channels

(c) honey-combed type structure

Minimized both the volume to membrane surface ratio and feed flow. 30 250 m2/m3.

High density of cells and Optimized both space thin walls larger occupancy of the hydraulic section and membrane and channel high membrane surface. wall thickness in the element. Up to 800 m2/m3. 130 400 m2/m3.

Chapter 6 in Sastre, A. M., Pabby, A. K., & Rizvi, S. S. H. (2009). Handbook of Membrane Separations. CRC Press, Taylor and Francis Group.

A. Ceramic Membranes: Current status and prospects for applications

Membrane elements:
Evolution of multichannel geometries of ceramic membranes
Significant increase in surface to element volume ratio compared to previous geometries. Tight arrangements of cells with small cross section area efficient turbulent flow, reduced pumping energy for feed flow, high filtration surface per element.
Chapter 6 in Sastre, A. M., Pabby, A. K., & Rizvi, S. S. H. (2009). Handbook of Membrane Separations. CRC Press, Taylor and Francis Group.

A. Ceramic Membranes: Current status and prospects for applications

Membrane elements:
Hollow fiber and capillary ceramic membranes Compact and low-cost HF outer diam < 0.5 mm Capillary outer diam > 0.5 mm Filter area = 0.05 to 1 m2; suitable for micro-, ultra- and nanofiltration. Can be specially designed for gas separation and hightemperature applications of up to 700 C.

Chapter 6 in Sastre, A. M., Pabby, A. K., & Rizvi, S. S. H. (2009). Handbook of Membrane Separations. CRC Press, Taylor and Francis Group.

A. Ceramic Membranes: Current status and prospects for applications

Porous Membrane Structure
Most ceramic membrane elements are constructed from supported multiple ceramic layers constituting an asymmetric porous structure. Alumina, titania and zirconia: commonly used for ceramic membranes and support materials. Cordierite, silicon carbide, and silicon nitride: recently developed and usually used for monolith. Glass: can be used being a homogeneous material. Metallic or macroporous carbon materials: can be used as support.

Asymmetric alumina structure

Asymmetric carbon structure

homogeneous alumina structure

homogeneous glass structure

Chapter 6 in Sastre, A. M., Pabby, A. K., & Rizvi, S. S. H. (2009). Handbook of Membrane Separations. CRC Press, Taylor and Francis Group.

A. Ceramic Membranes: Current status and prospects for applications

Porous Membrane Structure
Most ceramic membrane elements are constructed from supported multiple ceramic layers constituting an asymmetric porous structure. Microfilters: macroporous ceramic membranes (pore diam > 50 nm) deposited on ceramic, carbon or metallic porous supports. Obtained by two successive processing techniques: (1) extrusion of ceramic pastes to produce cylindrically shaped macroporous support, (2) slip-casting of ceramic powder slurries to obtain the supported MF layer.

Asymmetric alumina structure

Asymmetric carbon structure

homogeneous alumina structure

homogeneous glass structure

Chapter 6 in Sastre, A. M., Pabby, A. K., & Rizvi, S. S. H. (2009). Handbook of Membrane Separations. CRC Press, Taylor and Francis Group.

A. Ceramic Membranes: Current status and prospects for applications

Porous Membrane Structure
Most ceramic membrane elements are constructed from supported multiple ceramic layers constituting an asymmetric porous structure. Ultrafilters: an additional mesoporous ceramic layer (2 nm < pore diam < 50 nm) is deposited, most often by solgel process. Ultrafiltration with ceramic membranes are based on mesoporous top layers

Asymmetric alumina structure

Asymmetric carbon structure

homogeneous alumina structure

homogeneous glass structure

Chapter 6 in Sastre, A. M., Pabby, A. K., & Rizvi, S. S. H. (2009). Handbook of Membrane Separations. CRC Press, Taylor and Francis Group.

A. Ceramic Membranes: Current status and prospects for applications

Porous Membrane Structure
Most ceramic membrane elements are constructed from supported multiple ceramic layers constituting an asymmetric porous structure. Nanofilters: produced in the same way as ultrafilters by depositing a very thin microporous membrane (pore diam < 2 nm) on the ultrafiltration layer. Two categories of micropores: (1) supermicropores > 0.7 nm (2) ultramicropores < 0.7 nm
homogeneous alumina structure homogeneous glass structure

Asymmetric alumina structure

Asymmetric carbon structure

Chapter 6 in Sastre, A. M., Pabby, A. K., & Rizvi, S. S. H. (2009). Handbook of Membrane Separations. CRC Press, Taylor and Francis Group.

A. Ceramic Membranes: Current status and prospects for applications

Zeolite Membranes
A variety of crystalline, hydrated aluminosilicates with a framework structure, which have been used for a long time as detergent builders (in view of their ion-exchange properties), adsorbents, and catalysts.
Zeolite membranes: offer the advantage of uniform pore diameters in the size range of many interesting gas and liquid environment, and with high thermal stability.

Chapter 6 in Sastre, A. M., Pabby, A. K., & Rizvi, S. S. H. (2009). Handbook of Membrane Separations. CRC Press, Taylor and Francis Group.

Zeolite Membranes
Synthesis of zeolite (W. Schmidt)
Heating at autogenous pressure in an autoclave:

Thermodynamically meta-stable

Chapter 6 in Sastre, A. M., Pabby, A. K., & Rizvi, S. S. H. (2009). Handbook of Membrane Separations. CRC Press, Taylor and Francis Group.

Zeolite Membranes
Synthesis of zeolite (W. Schmidt)

* Random orientation in crystals.

1. In Situ hydrothermal synthesis One-step, direct membrane synthesis that involves the nucleation and growth of zeolite crystals on the support surface.
The as-received porous support is immersed in the liquid precursor gel, and the membrane is heated under autogenous pressure.
Chapter 6 in Sastre, A. M., Pabby, A. K., & Rizvi, S. S. H. (2009). Handbook of Membrane Separations. CRC Press, Taylor and Francis Group.

Zeolite Membranes
Synthesis of zeolite (W. Schmidt)

* The rate and direction of crystal growth can be controlled.

2. Ex Situ hydrothermal synthesis or secondary growth method First step: a closely packed layer of colloidal zeolite crystals (seeds), synthesized homogeneously, is deposited onto the surface of a support.
Second step: crystal growth with a secondary gel under hydrothermal synthesis conditions.
Chapter 6 in Sastre, A. M., Pabby, A. K., & Rizvi, S. S. H. (2009). Handbook of Membrane Separations. CRC Press, Taylor and Francis Group.

A. Ceramic Membranes: Current status and prospects for applications

Zeolite Membranes
Scanning electron micrograph of an H-ZSM5 membrane obtained using in situ crystallization.

Scanning electron micrograph of silicalite membranes over nonporous alumina substrates after 20 h of secondary growth synthesis conditions.
Chapter 6 in Sastre, A. M., Pabby, A. K., & Rizvi, S. S. H. (2009). Handbook of Membrane Separations. CRC Press, Taylor and Francis Group.

A. Ceramic Membranes: Current status and prospects for applications

Zeolite Membranes

Applications of catalytic membrane reactors as (a) contactors using opposing reactant mode, (b) interfacial contactors for triphasic reactions, and (c) efficient gas-solid contactors uisng forced flow mode.
Chapter 6 in Sastre, A. M., Pabby, A. K., & Rizvi, S. S. H. (2009). Handbook of Membrane Separations. CRC Press, Taylor and Francis Group.

Chapter 6 in Sastre, A. M., Pabby, A. K., & Rizvi, S. S. H. (2009). Handbook of Membrane Separations. CRC Press, Taylor and Francis Group.