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)
for industry ✓ Ultrafiltration(UF)
✓ Reverse osmosis(RO)
✓ Electrodialysis(ED)
Developing ✓ Gas separation(GS)
for industry ✓ Pervaporation(PV)
To-be-developed ✓ Carrier facilitated transport
for industry ✓ Membrane contactors
✓ Piezodialysis, etc.
Medical ✓ Artificial kidneys
applications ✓ Artificial lungs
✓ Controlled drug delivery
✓ Well-established unit operations
✓ No major breakthroughs seem imminent
✓ A number of plants have been installed.
✓ Market size and applications are expanding
✓ Major problems remain to be solved before
large scale industrial application
✓ Well-established processes
✓ Still the focus of research to improve
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 Membrane Process
Gas separation membranes
❖ Serviced by more than 20 companies
❖ Selectively permeable to one component
of the feed mixture(high pressure);
permeate is enriched in this species.
❖ Major current applications
✓ H2 from N2 ✓ N2 from air
✓ Ar and CH4 in ammonia plants
✓ CO2 from CH4 in natural gas
<Figure 1.4> Schematic of basic gas separation process
1.4.3
ΔC Driven Process
Pervaporation
❖ Serviced by a few companies
❖ Driving force = low vapor pressure on the
permeate-side
❖ Major current applications
✓ Dehydration of 90∼95% ethanol solutions
(produce more than 99.9% ethanol)
✓ Removal of dissolved organics from water
Purified liquid
Feed(Liquid)
<Figure 1.5> Schematic of
Basic pervaporation 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