Hankyong National University

March 21, 2019 (Thu)

Chapter 1. Overview of Membrane Science and Technology

Chang-Han Yun / Ph.D.

Contents

1.1 Introduction

1.2 Historical Development of Membranes

Contents
Contents
1.3 Types of Membranes

1.4 Membrane Process

Chapter 1. Overview of Membrane Science and Technology 2

1.1 Introduction
❖ Ability of a membrane = control the permeation rate of species through the membrane
<Example>
✓ Goal of the controlled drug delivery
Moderate the permeation rate of a drug from a reservoir to the body
✓ Goal of separation applications
Separate mixture to species by species by permeating some species through membrane
❖ Chapters 2 to 4 : Membrane science Transport mechanisms
✓ Basic topics to all membrane processes Membrane preparation
Boundary layer effects
❖ Chapter 5 to 10 : Industrial membrane separation processes
❖ Chapter 11 : Carrier facilitated transport
❖ Chapter 12 : Reviewing the medical applications of membranes
Membrane reactors
❖ Chapter 13 : Other membrane processes Membrane contactors
Piezodialysis.
Chapter 1. Overview of Membrane Science and Technology 3
 1.2 Historical Development of Membranes
❖ At 18th century
✓ Abbé Nolet(1748) : Used the word ‘osmosis’ to describe permeation of water through a
diaphragm
❖ 19th ∼ early 20th centuries
✓ Membranes had no industrial or commercial uses
✓ Used as laboratory tools to develop physical/chemical theories
<Example>
• Ideal dilute solution (van’t Hoff) by measuring solution osmotic pressure at 1887
• Kinetic theory of gases (Maxwell and others) from selective semipermeable membrane
✓ Early membrane : Bladders of pigs, cattle or fish and sausage casings made of animal gut
✓ Later membrane : Collodion (nitrocellulose) membranes
✓ Bechhold(1907) : Prepared nitrocellulose membranes of graded pore size by bubble test
✓ Elford, Zsigmondy and Bachmann, and Ferry : Improved on Bechhold’s technique

Chapter 1. Overview of Membrane Science and Technology 4

 1.2 Historical Development of Membranes
❖ Early 1930s : Commercial microporous collodion membranes(MF)
❖ 1940 ∼ 1960
Industrial Application Medical Application
✓ Expanded to other polymers as like CA memb. 1945 : Artificial kidney by W.J. Kolf
✓ Produce drinking water at 1945 1960’s : Membrane oxygenator
• Germany, EU, US Army 1966 : Controlled drug delivery systems(Alza)
• Millipore Corporation

❖ 1960 ∼ 2003
✓ Developed elements of modern membrane
(But used for only a few laboratory and small, specialized industrial applications)
✓ Total annual sales for all industrial applications < 20 million USD in 2003
• Reasons : too unreliable, too slow, too unselective, and too expensive

Chapter 1. Overview of Membrane Science and Technology 5

1.2 Historical Development of Membranes

❖ Early 1960s
✓ Loeb–Sourirajan : develop defect-free, high-flux, anisotropic RO
✓ Flux : early Loeb–Sourirajan RO = 10 × previous RO membrane
✓ Office of Saline Water (OSW) : funding to industrialize RO, UF, MF, ED
❖ 1960 ∼ 1980 : significant change in the status of membrane technology
✓ Other membrane formation processes, including interfacial polymerization
✓ Multi-layer composite casting and coating
❖ 1980’s
✓ Monsanto Prism® membrane for H2 separation(1980)
✓ Separation of N2 from air(DOW)
✓ Cynara and Separex to to separate CO2 from natural gas
✓ GFT for dehydration of alcohol

Chapter 1. Overview of Membrane Science and Technology 6

1.3 Types of Membranes

<Figure 1.1> Schematics of the principal types of membranes)

Chapter 1. Overview of Membrane Science and Technology 7
 1.3.1
1.3 Types of Membranes Isotropic Membranes
1.3.1.1 Microporous Membranes
❖ Structure and fuction of a microporous membrane = very similar to a conventional filter
❖ Pore size = 0.01 to 10 μm in diameter
❖ Separation of solutes = mainly by molecular size and pore size distribution
<Example> UF, MF, Membrane contactor
1.3.1.2 Non-porous Dense Membranes
❖ Diffusivity and solubility in the membrane ⇨ Determine separation of various components
❖ Usually use anisotropic structure to improve the flux
<Example> Gas separation, Pervaporation, RO membranes
1.3.1.3 Electrically Charged Membranes
❖ Membrane : dense or microporous (most commonly very finely microporous)
✓ Fixed positively charged ions ⇨ anion-exchange membrane
❖ Material
✓ Fixed negatively charged ions ⇨ cation-exchange membrane
✓ Fixed ions of membranes (much lesser extent by the pore size)
❖ Separation
✓ Charge and concentration of the ions in solution
<Example> Electrodialysis membranes
Chapter 1. Overview of Membrane Science and Technology 8
 1.3 Types of Membranes
1.3.2 Anisotropic Membranes
❖ Isotropic membrane < 20 μm ⇨ Mechanical strength = weak
Solution = Anisotropic
Transport rate ∝(membrane thickness)－1
❖ Top-layer(extremely thin) ⇨ active layer ⇨ determine separation properties
❖ Sub-layer(much thicker and porous) ⇨ mechanical supporter
❖ Most of commercial membrane = use an anisotropic membranes

1.3.3 Metal and Liquid Membranes

❖ Ceramic membranes
✓ Special class of microporous membranes ⇨ used in UF and MF applications
✓ Solvent resistance and thermal stability
❖ Dense metal membranes
✓ Particularly Pd membranes
✓ Considered for separation of H2 from gas mixtures
❖ Supported Liquid Membrane(SLM) : being developed for carrier facilitated transport processes
Chapter 1. Overview of Membrane Science and Technology 9
1.4 Membrane Process

[Table 1.1] Membrane technologies addressed in this book

Category Process Status

Developed ✓ Microfiltration(MF) ✓ Well-established unit operations
for industry ✓ Ultrafiltration(UF) ✓ No major breakthroughs seem imminent
✓ Reverse osmosis(RO)
✓ Electrodialysis(ED)
Developing ✓ Gas separation(GS) ✓ A number of plants have been installed.
for industry ✓ Pervaporation(PV) ✓ Market size and applications are expanding
To-be-developed ✓ Carrier facilitated transport ✓ Major problems remain to be solved before
for industry ✓ Membrane contactors large scale industrial application
✓ Piezodialysis, etc.
Medical ✓ Artificial kidneys ✓ Well-established processes
applications ✓ Artificial lungs ✓ Still the focus of research to improve
✓ Controlled drug delivery performance, for example, improving
biocompatibility

Chapter 1. Overview of Membrane Science and Technology 10

 1.4.1
1.4 Membrane Process Δp Driven Process
Δp Driven Process(RO, UF, MF )
❖ MF membrane : Filter colloidal particles bacteria from 0.1 to 10 μm by sieving mechanism
❖ UF membrane : Filter dissolved macromolecules (ex, proteins) by sieving mechanism
❖ RO membrane : ✓ Pores = 3 ∼ 5 Å ⇨ range of thermal motion of the polymer chain
✓ Mechanism : solution-diffusion

<Figure 1.2> Filtration spectrum

Chapter 1. Overview of Membrane Science and Technology 11
 1.4.1
1.4 Membrane Process Δp Driven Process

Simple model of Δp driven membrane process

✓ Series of cylindrical capillary pores of diameter(d) ⇨ Poiseuille’s law ⇨ Flux(q)

✓ Flux/pore : (1.1) where Δp = pressure difference

across pore
μ = liquid viscosity
✓ Flux/area : (1.2)
ℓ = pore length
N = Number of pore/area
✓ For equal area and porosity(ε), (1.3)

✓ By combining Eq(1.2) and Eq(1.3) ⇨ (1.4)

✓ Eq(1.4) ⇨ J ∝d2 ⇨ Big difference in Δp for same J among MF, UF and RO

Chapter 1. Overview of Membrane Science and Technology 12

 1.4.2
1.4 Membrane Process Electrodialysis(ED)
Electrodialysis(ED) membrane process
✓ Membrane = charged membranes ✓ Driving force = electrical potential difference
✓ Module configuration = stack style ✓ Pair of anion and cation exchange membranes in a cell
✓ Industrial application
• Desalination of
brackish water
• Deionization of
cheese whey
• Environmental

<Figure 1.3> Schematic of an electrodialysis process

Chapter 1. Overview of Membrane Science and Technology 13
 1.4.3
1.4 Membrane Process ΔC Driven Process
Gas separation membranes Pervaporation
❖ Serviced by more than 20 companies ❖ Serviced by a few companies
❖ Selectively permeable to one component ❖ Driving force = low vapor pressure on the
of the feed mixture(high pressure); permeate-side
permeate is enriched in this species.
❖ Major current applications
❖ Major current applications
✓ Dehydration of 90∼95% ethanol solutions
✓ H2 from N2 ✓ N2 from air (produce more than 99.9% ethanol)
✓ Ar and CH4 in ammonia plants ✓ Removal of dissolved organics from water
✓ CO2 from CH4 in natural gas Purified liquid

Feed(Liquid)

<Figure 1.5> Schematic of

Basic pervaporation process
<Figure 1.4> Schematic of basic gas separation process Condensed permeate liquid
Chapter 1. Overview of Membrane Science and Technology 14
 1.4.3
1.4 Membrane Process ΔC Driven Process
Facilitated transport membranes
❖ Driving force in gas separation = Δpi in gas
❖ Driving force in metal separation = flow of H+ or OH－ in the other direction
❖ Very high membrane selectivity(But no commercial application)
❖ principal problem ✓ Physical instability of liquid membrane
✓ Chemical instability of the carrier agent
Facilitated transport
(HEM = Hemoglobin)

Coupled transport

<Figure 1.6> Schematic examples of carrier

facilitated transport of gas and ions
Chapter 1. Overview of Membrane Science and Technology 15
 1.4.4
1.4 Membrane Process Medical Application
Artificial Dialyser ※ Artificial lung : very similar with artificial kidney dialyser
❖ The 1st successful artificial kidney = cellophane (regenerated cellulose) dialysis membranes(1945)
❖ Single largest application of membranes (in terms of membrane area and sales value)
❖ Hollow fiber membrane module for dialysis
• Blood = feeding into lumen-side and circulating
✓ Membrane area = 1 m2
• Dialysate = feeding into shell-side countercurrently
✓ Diffuse metabolites (Urea, creatinine, and other low MW species) to dialysate

<Figure 1.7> Schematic of a hollow fiber artificial kidney dialyser

Chapter 1. Overview of Membrane Science and Technology 16

 1.4.4
1.4 Membrane Process Medical Application
Controlled Drug Delivery ※ Total market = more than 3 billion USD per year
❖ Designed to deliver drugs through the skin
✓ Drug surrounded by membrane ✓ Release constantly
❖ Application using moderate delivery of drugs through skin
✓ Nnitroglycerine (for angina)
✓ Nicotine (for smoking cessation)
✓ Estradiol (for hormone replacement therapy)
❖ Application using implants and tablets by osmosis or biodegradation

<Figure 1.8> Schematic of transdermal patch in which the rate of delivery

of drug to the body is controlled by a polymer membrane.
Chapter 1. Overview of Membrane Science and Technology 17