Iqbal, UMP

Membrane Science & Technology

Iqbal Ahmed, PhD Sr. Consultant Research Fellow

Iqbal, UMP

Membrane Science & Technology

What is membrane History of Synthetic Membrane Fundamental aspects of membranes and membrane processes Membrane Separation Processes Relative to Contaminant Size Membrane Processes Phenomenon Fundamentals The Mass Transport Through Membranes

Membrane Potential Materials and structures of various synthetic membranes Synthetic Membrane Groundwork-Past Present & Future
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What is Membrane
Membrane is a thin sheet or layer of barrier which selectively separates (fractionates) materials from liquid/solid, liquid/ions, liquid/liquid, and gas mixtures via pores and/or minute gaps in the molecular arrangement of a continuous structure for example the animal glades. The popularity of membrane due to the gentle nature of the separation because high temperature, high energy and phase change are not required in membranes process, and the often low capital and operation costs easily installed and mobile able and 100% recycle

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Sources: Sep. and Purif. Tech. 74 (2010) 119129

History of Synthetic Membrane

Abbe Noilett Matteucci Graham Fick Traube Pfeffer Gibbs van Hoff Donnan Abel
Michaels, Manegold, McBain

1748 1845 1866 1865 1867 1877 1877 1911 1926 1934 1957 1960 1962
1963

Discovering of osmosis phenomenon in natural membranes Research on anisothropy of natural membranes Research on dialysis & gas separation on Rubber Membranes The first synthetic membrane from Nitrocellulosis Research on osmosis on synthetic membranes Research on osmosis on ceramic membranes Theory of osmosis phenomena (Noble prize) Distribution law (Noble prize) Research on dialysis (artificial Kidney) Research on electrodialysis
Gas separation on silicone rubber & Pervaporation of azeotropic mixtures

1926- 31 Research on reverse osmosis

Elder i in. Kammermeyer Londsdale Loeb &Surirayan

Mahon

Research on composite membranes

Preparation of Asymmetric membranes & Pore size controlling in membranes

Capillary membranes (hollow fiber membrane)

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Membrane Separation Processes Relative to Contaminant Size

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Adopted: Vortex Hydropore Filtration Spectrum

Contd

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Fundamental Aspects of Membranes & Membrane Processes

During the last 46 years membranes have evolved from a laboratory tool to industrial products with significant technical and commercial impact. Membranes and membrane processes are used in four main areas, which are Separation of molecular and particulate mixtures The controlled release of active agents Membrane reactors and artificial organs Energy storage and conversion systems
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AIChE Journal, May 2001 Vol. 47, No. 5

Classification of Membranes & Membrane Processes

Process Structure Symmetric, Asymmetric microporous Asymmetric microporous Thin film Asymmetric Asymmetric composite skintype thin MWCO kDa 106 Macrospores 103 -106 Mesopores 102 -103 Microspores filmnon-porous non-porous 106 Mesopores Dialysis Symmetric & Asymmetric Asymmetric, homogenous Polymer PV ED* LM Cations and anions exchange double emulsion < 200 non-porous 0.0005 Pore Size
(m)

Driving Force, Transport bar Mode P~ 0-1 P~ 0-10 P ~ 10-25 P ~ 10-100 P~ 10-100
Conc. difference

0.1-10 0.001-0.1 0.0001-0.001 0.001 0.0005 0.001-0.1

Sieving Sieving Solution diffusion Solution diffusion diffusion Sieving + diffusivity

MF UF NF RO GS

Asymmetric, composite, homogeneous polymer

Partial pressure Solution diffusion Electrical potential Ion migration

Concentration & pH Solution gradient

diffusion

The Mass Transport Through Membranes

Phase A Phase A A

Mathematical relations applicable to any membrane

Phenomenological equation that connects the fluxes of; o the electrical charges, o volume, that is, viscous flow,

XA

XA Driving force Mass transport

XA>XA

o individual components with the corresponding driving forces by a linear Relation:

Here J is a flux per unit area and X is a generalized driving force; the subscripts i and k refer to individual components, volume, and electrical charges; and L is a phenomenological coefficient relating the fluxes to the driving forces

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Here X is the driving force, C is the concentration, is the linear velocity, f is the friction coefficient, and D is the Maxwell-Stefan diffusion coefficient. The subscripts i and k refer to individual components.

Another approach to describe the mass transport in membrane processes is based on a relation developed by Maxwell and Stefan:

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AIChE Journal, May 2001 Vol. 47, No. 5

Membrane Potential
Global sales of membranes Total sales are forecast to grow from US$8 billion in 2003 to US$12.4 billion by 2008, reaching the US$10 billion total in 2006. The water industry (water and waste water treatment) of Asia is expanding from 23 billion US$ 2003 to 31 billion US$ in 3 years with a growth rate of nearly 10% per annum and the market is set to further double to 64 billion US$ by 2010 and reach 118 billion US$ by 2015.

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Contd
Unfortunately this growth is slow in market because of its production cost and the limited number of appropriate polymers Value growth will be promoted by the use of efficient manufacturing/fabrication techniques, hence high performance membranes Generally polymeric membranes production is a complicated process since it involves many steps. These steps are illustrated in Figure 1 on the next slide.
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Commercial Available Hydrophilic & Hydrophobic Polymers (Iqbal, 2008/2009) Hydrophilic Polymers PVAL Cellulose and its derivative PVC Cellulose acetate PA Cellulose acetate butyrate PAA Cellulose acetate propionate PEOX Cellulose nitrate PAN Cellulose propionate PVAC Ethyl cellulose PVB Carboxymethyl cellulose PHS Hydrophobic Polymers PSf Poly tetrafluoro ethylene PES PVDF PC PP PMMA Polyethylene Silicone Polyphenylene oxide Polyphenylene sulfide Polystyrene PPO PPS PS Iqbal, UMP

Poly(viny1 alcohol) Poly(viny1 chloride) Polyamide Poly(acry1ic acid) Poly(ethy1ene oxide) Polyacrylonitrile Poly(viny1 acetate) Poly(viny1 butyral) Poly (p-hydroxystyrene) Polysulfone Polyethersulfone Poly (vinylidene fluoride) Polycarbonate Polypropylene poly(methyl methacrylate)

CA CAB CAP CN CP EC CMC

PTFE PE

Membranes Groundwork

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M. Ulbricht / Polymer 47 (2006) 22172262

Polymeric Membranes Groundwork

Solvents: NMP, DMAc, DMF, DMSO, Acetone, alcohol, acetic acid, formic acid Material selection & drying Process Dry for 1 day to 1 Week at 60 150 oC Preparation of homogeneous dope solution (Dissolution may take 4hr24hr at 55oC-110 oC Membranes casting or Spinning Module; HF, SW, FS and Tubular Potting Process at least 24 hrs Organic and Inorganic additives CA, CR, CN, PA, PSf, PES, PVDF, PEEK, PI, PVA, PAN, PC, PFSA,

Dry/wet Phase Inversion Process Post Treatment

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Materials and structures of various synthetic membranes

Normally, membrane material is manufactured from following materials;

Polymer (Commodities & Engineered polymers) Ceramic, Glass, Metals, Liquid Polymeric Membrane Structure Symmetric Structure Asymmetric Structure Integral Asymmetric Cylindrical Sponge type Porous skin layer
Homogeneous skin layer

Homogeneous
Composite Structure

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Contd

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Polymers as Materials for Industrially Established Separation Membranes

Polymer Barrier type Morphology Cross-section Anisotropic Anisotropic Isotropic Isotropic Anisotropic Isotropic Anisotropic Anisotropic Anisotropic Isotropic Isotropic track-etched Anisotropic Isotropic Isotropic Thickness (m) 0.1 0.1 50300 100500 0.1 50500 0.1 0.1 0.1 100500 635 0.1 100500 50500 0.1 100500 0.1 0.05 0.1 635 0.05 50500 0.1 50500 0.1<110 0.1 0.1 GS, RO UF MF MF UF, D ED, fuel cell UF UF UF MF MF GS ED MF GS MF UF RO, NF GS MF RO, NF MF GS, NF MF GS PV, NF (organophilic) GS UF, Dialysis Membrane process

Cellulose acetates (CA)

Cellulose nitrate (CN) Cellulose, regenerated (CR) Perfluorosulfonic acid polymer (PFSA) Polyacrylonitrile (PAN) Polyetherimides (PEI) Polyethersulfones (PES) Polyethylene terephthalate (PET) Polyphenylene oxide Poly(styrene-co-divinylbenzene), sulfonated or aminated Polytetrafluoroethylene , Teflon (PTFE)

Nonporous Mesoporous Microporous Macroporous Mesoporous Nonporous Mesoporous Mesoporous Mesoporous Macroporous Macroporous Nonporous Nonporous Macroporous Nonporous Macroporous Mesoporous Nonporous Nonporous Macroporous Nonporous Macroporous Nonporous Macroporous Nonporous Nonporous Mesoporous

Polyamide, aliphatic (PA) Polyamide, aromatic Polyamide, aromatic, in situ synthesized Polycarbonates, aromatic (PC) Polyether, aliphatic crosslinked, in situ synthesized Polyethylene (PE) Polyimides (PI) Polypropylene (PP) Polysiloxanes (PDMS) Polysulfones (PSf) PolyvinylUMP alcohol, crosslinked (PVC) Iqbal,

Isotropic Anisotropic Anisotropic/composite Anisotropic Isotropic track-etched Anisotropic/composite Isotropic Anisotropic Isotropic Anisotropic/composite Anisotropic Anisotropic Anisotropic/composite

Nonporous

<110 PV (hydrophilic) M. Ulbricht / Polymer 47 (2006) 22172262

Contd

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Commercially available membranes

Manufacturer ami (DOW/FILMTEC ami (DOW/ FILMTEC) AMC USA/China Aquious AsahiKasei Dainippon KOCH KOCH KOCH Luxx Ultra-Tech Inc (USA) Millipore Millipore membrane elements Nitto Denko PALL Polymem Sterlitech Synder TriSep Brand Name M-U4040 PES MU2540 PAN AC 120 R01 UltraBar UF AP series PF004D HFK-131 HFK-328 L Series Ultracel Biomax PB Amicon M-series Hydracap BTS polymem Sterl UF PES 100 UE10 Material Module PES (SW) Hydrophilic PAN.(SW) Modified PES (HF) PES (HF) Hydrophilic PAN (HF) PMP (HF) SMP. PES (SW) SMP. PES (SW) 10 5 100 MWCO kDa 10 20 15 100-150 69 Flux L.m-2.h-1 4.5-18.2 at 3.2 bar 50 at 3.5 bar 112 at 4.1 bar 27 16 36 24-53 24-53 32 27-45 35-45 at 1 bar 97.2 at 1 bar at 9.3 bar 51-128 187.2 at 3 bar 313.2 at 1 bar 9.2-210 51 2.1 Application Pharmaceutical & food industry Waste-water Pharmaceutical & food ndustry Surface-water treatment Pharmaceutical and food ndustry Surfactant solved water Waste water Waste water PVC separation Waste-water Food industry Protein Purification Protein Purification Oil-water separation Waste water Pharmaceutical & food industry Protein purification pharmaceutical & food industry Gelation separation Dairy and Food industry

*HF 8H-72-35-PMPW SMP. PSf (HF)

PVDF, PES PS (Tubular) 5 PES (HF) CA (HF) Mod. Hydro. PAN (HF) Hydro.PES (HF) Asym.PES Casseette PSf HF PES -HF PES (SW) PES (SW) 5 10 0.03-1 m 150 0.5-10 6 0.04 - 23 70 10

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