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) 119 129

History of Synthetic Membrane

Abbe Noilett Matteucci Graham 1748 1845 1866 Discovering of osmosis phenomenon in natural membranes Research on anisothropy of natural membranes Research on dialysis & gas separation on Rubber Membranes

Fick Traube
Pfeffer Gibbs van Hoff Donnan Abel
Michaels, Manegold, McBain

1865 1867
1877 1877 1911 1926

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)

1926- 31 Research on reverse osmosis 1934 1957 1960 1962

1963

Elder i in. Kammermeyer Londsdale Loeb &Surirayan

Mahon

Research on electrodialysis
Gas separation on silicone rubber & Pervaporation of azeotropic mixtures

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 MF UF NF RO GS Dialysis Structure Symmetric, Asymmetric microporous Asymmetric microporous Thin film Asymmetric MWCO kDa 106 Macrospores 103 -106 Mesopores 102 -103 Microspores Pore Size
(m)

Driving Force, bar P~ 0-1 P~ 0-10 P ~ 10-25 P ~ 10-100 P~ 10-100

Transport Mode Sieving Sieving Solution diffusion Solution diffusion diffusion Sieving + diffusivity Solution diffusion Ion migration Solution diffusion

0.1-10 0.001-0.1 0.0001-0.001 0.001 0.0005

Asymmetric skin- type thin film non-porous composite Asymmetric, composite, homogeneous polymer Symmetric & Asymmetric non-porous 106 Mesopores

0.001-0.1

Conc. difference

PV

Asymmetric, homogenous Polymer

non-porous

0.0005

Partial pressure Electrical potential

Concentration & pH gradient

ED* LM

Cations and anions exchange double emulsion

< 200

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

XA>XA

Mass transport

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 Cellulose and its derivative PVAL Cellulose acetate PVC Cellulose acetate butyrate PA Cellulose acetate propionate PAA Cellulose nitrate PEOX Cellulose propionate PAN Ethyl cellulose PVAC Carboxymethyl cellulose PVB PHS Hydrophobic Polymers

Poly(viny1 alcohol) Poly(viny1 chloride) Polyamide Poly(acry1ic acid) Poly(ethy1ene oxide) Polyacrylonitrile Poly(viny1 acetate) Poly(viny1 butyral) Poly (p-hydroxystyrene)

CA CAB CAP CN CP EC CMC

Polysulfone
Polyethersulfone Poly (vinylidene fluoride) Polycarbonate Polypropylene poly(methyl methacrylate)

PSf
PES PVDF PC PP PMMA

Poly tetrafluoro ethylene

Polyethylene Silicone Polyphenylene oxide Polyphenylene sulfide Polystyrene

PTFE
PE

PPO PPS PS Iqbal, UMP

Membranes Groundwork

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M. Ulbricht / Polymer 47 (2006) 22172262

Polymeric Membranes Groundwork

Material selection & drying Process CA, CR, CN, PA, PSf, PES, PVDF, PEEK, PI, PVA, PAN, PC, PFSA,

Solvents: NMP, DMAc, DMF, DMSO, Acetone, alcohol, acetic acid, formic acid

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

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

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

Polyvinyl alcohol, crosslinked (PVC) Polyvinylidenefluoride (PVDF)

Nonporous
Mesoporous Macroporous

Anisotropic/composite
Anisotropic Isotropic

<110
0.1

PV (hydrophilic)
UF

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50300 MF 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 Brand Name M-U4040 PES MU2540 PAN AC 120 R01 UltraBar UF AP series PF004D HFK-131 HFK-328

Material Module
PES (SW) Hydrophilic PAN.(SW) Modified PES (HF) PES (HF) Hydrophilic PAN (HF) PMP (HF) SMP. PES (SW) SMP. PES (SW) SMP. PSf (HF) PVDF, PES PS (Tubular) PES (HF)

MWCO kDa
10 20 15 100-150 69 10 5 100 5 5

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

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

KOCH *HF 8H-72-35-PMPW Luxx Ultra-Tech L Series Inc (USA) Millipore Ultracel Biomax PB Millipore Amicon membrane M-series elements Nitto Denko Hydracap PALL Polymem Sterlitech Synder TriSep BTS polymem Sterl UF PES 100 UE10

CA (HF) Mod. Hydro. PAN (HF) Hydro.PES (HF)

Asym.PES Casseette PSf HF PES -HF PES (SW) PES (SW)

10
0.03-1 m 150 0.5-10 6 0.04 - 23 70 10

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

THANKS YOUR KIND ATTENTION & WILL BE APPRECIATE TO YOUR QUESTIONS