Fabrication of Polymer Membranes - Volker Abetz - Macro18
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Fabrication of Polymer Membranes
Volker Abetz
University of Hamburg, Institute of Physical Chemistry
Martin-Luther-King-Platz 6, 20146 Hamburg, Germany
Helmholtz-Zentrum Geesthacht, Institute of Polymer Research
Max-Planck-Straße 1, 21502 Geesthacht, Germany
Acknowledgement: Torsten Brinkmann, Md. Mushfequr Rahman, Ulrich A. Handge
Copyright © 2018 by Volker Abetz
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Content
1. Introduction
2. Membrane Geometries and Membrane Production
3. Membrane Modules
4. Development of a Membrane Process
Copyright © 2018 by Volker Abetz
2
Membranes for
Liquid and Gas Phase Separations
H2O CO2 / N2 O2 / N 2
CH4 / CO2
Copyright © 2018 by Volker Abetz
Largest Market for Membranes: Hemodialysis
Dialysis - Application:
Hemodialysis
Commercial dialyzer
Fresenius FMC-Magazin 2013
Scheme of hemodialysis
Copyright © 2018 by Volker Abetz http://www.fmc-ag.com
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Biogas Production
Decentralised
Co-fermentation media energy
Feed vessel production
Heat supply
Agriculture
GP conditioning
Conditioning unit unit CH4 enriched
CH enriched gas4
Manure Gas permeation gas
H2S Removal
Adsorption
Animal
feed Post condit-
Hygienisation 70°C Post condit-
Compres- ioning
ioning
sion Connection
Bio reactors Post
Cooling Cooling to Connection
gas grid
37-39°C fermentation
Decentralised to gas grid
Com- Com- Vacuum
energy
pump
Cond- pres- pres-
production
Condensate
ensate sion sion Off-gas
Gas
stations
Gas grid
Manure Manure storage Industry and decentralised Households
energy production
Copyright © 2018 by Volker Abetz
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Source: http://www.ewe-biogas.de/
Membrane Markets
HD = Hemodialysis
RO = Reverse Osmosis
UF = Ultrafiltration
MF = Microfiltration
ED = Electrodialysis
PV = Pervaporation
GS = Gas Separation
To give an impression where the big membrane business is located !!
Copyright © 2018 by Volker Abetz
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Membrane Process (Gas Permeation)
Heat exchanger:
Compressor: Process Retained
Driving force temperature Module Component
Feed Retentate
Membrane
Permeate
Permeating
Component
Vacuum pump:
Driving force
Copyright © 2018 by Volker Abetz
Membrane Process:
Principle of Separation
Module rejected component
Feed Retentate
Membrane
Permeate
permeating component
Copyright © 2018 by Volker Abetz
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Membranes for Separation Processes
Porous membrane Solution-diffusion membrane
Ultra- and microfiltration Gas and vapour permeation
Gas separation Pervaporation
Reverse osmosis
Nanofiltration
Copyright © 2018 by Volker Abetz
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Membrane Processes - Classification
Driving force Separation Physical Permeating particle / molecular size
mechanism State
Pressure difference Sieving mech. Microfiltration
(top layer filtrat.) Liquid /
Ultrafiltration
Difference in Liquid
Nanofiltration
chemical potential Sorption+Diffusion
Rev osmosis
Partial pressure/ Sorption+Diffusion Liquid / Gas Pervaporation
Difference in +Volatility
fugacity Gas / Gas Vapor perm.
Sorption+Diffusion Gas /Gas Gas perm.
Difference in Sorption+Diffusion Liquid / Dialysis
concentration / Liquid Diffusion dial.
activity difference
Electric potential Electrophoretic Liquid / Electrodial.
difference mobility Liquid Bipolar
electrodialysis
1 nm 0,1 µm 10 µm
Copyright © 2018 by Volker Abetz
10Membrane Processes - Classification
porous membrane
Pressure driving force
Microfiltration/ Retention of drops and particles, such as extraction of
Ultrafiltration: proteins from whey
Nanofiltration: Retention of components with M>300 kg/mol
Reverse osmosis: Retention of dissolved substances in water, eg sea
dense membrane
water desalination
Dialysis: Difference in concentration-driven permeation,
e.g. hemodialysis
Electrodialysis: Separation of ions by alternation of anion and cation selective
membranes, the driving force is the electric potential
Pervaporation: Liquid feed, evaporation of the passing material stream in
the permeate, theAbetz
Copyright © 2018 by Volker driving force is the difference in activity 11Membrane Processes - Classification
membrane
dense
Gas permeation/ Separation of gas and vapor mixtures, the driving force
Vapor permeation: is the difference of pressure or fugacity
membrane
porous
Contactors: The porous membrane is the mass transfer area for absorption,
extraction desorption or distillation processes
Membrane reactors: Combination of reaction and separation in a basic operation,
depending on the reaction conditions using porous or dense
membranes
Copyright © 2018 by Volker Abetz
12Gas Separation Membranes
State-of-the-art membrane materials
CO2 separation VOC recovery
Poly(ether-block-ester) PolyActive™ Poly(dimethyl siloxane) PDMS
Poly(ether-block-amide) PEBAX® Poly(octyl methyl siloxane) POMS
Cellulose acetate / triacetate Polymers of Intrinsic Microporosity PIM
Ethyl cellulose Polyacetylenes: Si; Ge; C
PDMS Teflon AF ® : 2400; 1600
Polymers of Intrinsic Microporosity PIM
H2 separation O2/N2 Separation Dehydration
Polyimides Cellulose Acetate Poly(vinyl alcohol)
PIM PDMS TYLOSE ®
PPO PIM Cellulose acetate / triacetate
PEI PPO
Catalytic membranes
Food storage PDMS
Nanofiltration
Ethyl cellulose PIM Modified PDMS
PEBAX PIM
TORLON®
Active and inactive additives to matrix materials
SiO2, TiO2, Pd nanoclusters, carbon (active and nano), PEG, amino compounds, active carriers etc.
Copyright © 2018 by Volker Abetz
13UF/MF membranes
State-of-the-art membrane materials
UF MF
Cellulose, regenerated Cellulose acetate Cellulose nitrate
Polyacrylonitrile Polysulfone/ Polyethylene
Polyethersulfone
Ceramic membranes Polytetrafluoroethylene
(Al2O3, TiO2, ZrO2, SiO2, SiC) Polyvinylidenfluoride
Polypropylene
Polyamide
Polycarbonate Track-etched Polyethylene terephthalate
Polyester Polycarbonate
Polyimide
Mesoporous Macroporous
mainly anisotropic isotropic
Copyright © 2018 by Volker Abetz
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M. Ulbricht, Polymer 2006, 47, 2217.Content
1. Introduction
2. Membrane Geometries and Membrane Production
3. Membrane Modules
4. Development of a Membrane Process
Copyright © 2018 by Volker Abetz
15Molecular Weight Cut-off
Rejection
Log MW
Copyright © 2018 by Volker Abetz
16UF / MF
State-of-the-art membrane preparation metohds
Symmetric MF Membranes
Track-etching Casting + leaching / evaporation Film-stretching
Anodising process
Asymmetric MF Membranes
Phase inversion Sintering /
Slip casting
Copyright © 2018 by Volker Abetz
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K. Scott, Handbook of Industrial Membranes, 2. ed., Ed. 2, Elsevier Science & Technology Books, Oxon (UK) 1999, 118.Membrane Preparation
Processing Via Sintering
Ia Ib
II III IV
I: Filling of mould III: Sintering under pressure
II: Precompression IV: Pressureless sintering EP 2 982 492
Copyright © 2018 by Volker Abetz
18Sintered Membranes
• Commercial Examples
• Ultra-high molecular weight polyethylene (UHMWPE) membranes
• UHMWPE: Excellent mechanical properties
• Processing requires special techniques
SEPRODYN®
• Poly(tetrafluoroethylene) (PTFE) membranes
• PTFE: High chemical and thermal stability
• High hydrophobicity
• Applications: Filter membranes, dust filters,
• pressure compensation units
Screw-in filter
Copyright © 2018 by Volker Abetz
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Figure sources: MICRODYN-NADIR GmbH (Wiesbaden); Berghof Products (Eningen)Uniaxial Stretching Method
Paste extrusion Rolling Uniaxial stretching at RT
Fine powder 5 mm 1 mm Direction of stretching
with lubricant
Paste extrusion
(10-20 cm/ min)
Thin sheet Multiple rolling to reduce the thickness Direction of rolling
Making microporous membranes by this uniaxial stretching method include three different stages:
1) Extrusion: To melt and extrude the polymer into uniaxially oriented films. It is crucial to achieve the
stacked lamellar morphology after extrusion and rolling process because only stacked lamellae are able
to form open pores during the process of streching.
2) Annealing: The extruded films are annealed for to the perfection of the crystalline phase.
3) Stretching: In the last stage, the films are deformed along the machine direction to generate pores.
Copyright © 2018 by Volker Abetz
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http://www.che.vt.edu/Faculty/Wilkes/GLW/jays_page/glw-webpage-jay.htmUniaxial Stretching Method
MD = Machine direction TD= Transverse direction
TEM micrograph (a) shows a uniaxially oriented high density polyethylene (HDPE) film melt extruded and
crystallized under directional flow. A stacked lamellar morphology is observed with the lamellae oriented
along the transverse direction. After a further annealing treatment, the melt extruded HDPE film was
deformed along the machine direction. During the deformation process, the stacked lamellae tend to
separate to form microporous membranes, as shown in TEM micrograph (b).
Copyright © 2018 by Volker Abetz
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http://www.che.vt.edu/Faculty/Wilkes/GLW/jays_page/glw-webpage-jay.htmBiaxially Stretched Membrane
Poly(tetrafluoro ethylene) (PTFE)
Goretex® membrane
Free radical emulsion or suspension polymerization
3 µm
Properties
• Tm (1. melting) = 342 °C extended chain crystals
• Tm (2.,3… melting) = 327 °C folded chain crystals
• below Tm insoluble in all organic solents
• enormous melt viscosity (1010 Pa·s @ 380 °C)
Copyright © 2018 by Volker Abetz
22Track Etched Membranes
A polymer film is bombarded with heavy ions and the radiation damaged areas are removed using an etching bath.
Two basic irradiation methods
1. fragments from the fission of heavy nuclei ( e.g. Cf or U)
2. heavy ion beams from accelerators
Radiation Etching
source Membrane with
porous structure • alkali solution (e.g. NaOH, KOH)
Polymer film
Pore-size and pore-shape
• uniform cylindrical, conical, tunnel-like, or cigar-like
Etching bath • controllable due to e.g.
• target material
• the nature and energy of incident particles
• etch conditions (T, etchant, pre-etch storage)
E. Drioli, L. Giorno, Comprehensive Membrane Science and Engineering, 1. ed., Elsevier, UK 2010, 98.
Copyright © 2018 by Volker Abetz
S.K. Chakarvarti, Radiation Measurements 2009, 44, 1085. 23
P. Apel, Radiation Measurements 2001, 34, 559.Track Etched Membranes
Polycarbonate Polypropylene
non-parallel pore channels slightly conical parallel pores
• symmetric membranes
• very narrow pore size distribution
• pores diameter ranging from few nm to mm
• prevention of surface roughness effects 1 µm 1 µm
• various materials
• used in microbiology or particle analysis
• pore size < membrane thickness
• pore blocking
• cake layer formation 1 µm 1 µm
cigar-like pores “bow-tie” pores
Polyethylene terephthalate Polyethylene terephthalate
Copyright © 2018 by Volker Abetz
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P. Apel, Radiation Measurements 2001, 34, 559.Track Etched Membranes
Common materials
Polyethylene terephthalate
• good stability in acids and organic solvents
• biologically inert
• mechanically strong
• high etch rate achievable (UV-sensibilisation)
• wide range of pore sizes
• relatively hydrophilic
Polycarbonate
• higher sensitivity smaller pore sizes (10 nm)
• lower resistance to organic solvents
• lower wettability
Copyright © 2018 by Volker Abetz
25Phase Inversion Process
Most common: non-solvent induced Alternative: thermally induced
precipitation bath
© Satorius
10 µm
Cellulosic membrane
Copyright © 2018 by Volker Abetz
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H. Matsuyama,K. Ohga,T. Maki, M. Tearamoto, S. Nakatsuka, Journal of Applied Polymer Science 2002, 89, 3951.Cellulosic Membrane
Cellulose
Cellulose Triacetate
Properties
most-hydrophilic industrial-grade membrane material limited pH-stability
low unspecific adsorption not autoclavable (dry)
high flux lack of tolerance to free chlorine
high service life to aggressive cleaning chemicals
inexpensive to temperature above 30 °C
easy to manufacture susceptibility to biological degradation
low impact on environment (waste) gradual decline in flux over lifetime due to compaction
Copyright © 2018 by Volker Abetz
27HZG Membrane Casting Machine
Casting of the polymer
solution onto a substrate,
30 cm
e.g. nonwoven, on rolls
up to 30cm width
Coating
Polymer Solvent
knife
solution Evaporation
Nonwoven
Immersion bath
Copyright © 2018 by Volker Abetz
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S. Rangou, K. Buhr et al., J. Membr. Sci. 2014, 451, 266-275.Isoporous Hollow Fiber Membranes
Outside-in Membranes Inside-out Membranes
Copyright © 2018 by Volker Abetz
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M. Radjabian, et al., Polymer 2014, 55, 2986-2997. K. Sankhala, et al., Adv. Mat. Int. 2017, 4, 1600991HZG Membrane Production Facility
Copyright © 2018 by Volker Abetz
30Asymmetric Membranes with
Finger Pore Substructure from NIPS
12% cellulose acetate (CA) 12% polyamide (PA) in 12% polysulfone (PSU) in
in dimethylacetamide (DMAc) dimethylsulfoxide (DMSO) dimethylformamide (DMF)
Filtration rate Retention Retention Porosity (%)
(m/s) g-globulin bovin serum
albumin (BSA)
12% CA in 3.5 x 10-5 99 98 80
DMAc
12% PA in 2.1 x 10-5 97 72 82
DMSO
12% PSU in 1.9 x 10-5 96 80 83
DMF Copyright © 2018 by Volker Abetz
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H. Strathmann, Introduction to Membrane Science and Technology, Wiley-VCH, Weinheim 2011Commercial Polymer Membranes
Made by Phase Inversion
Membrane Material Membrane Structure Membrane Process
Cellulose Acetate (CA) Asymmetric EP, MF, UF, RO
Cellulose mixed esters Asymmetric and symmetric MF, D
Polyacrylonitrile (PAN) Asymmetric UF
Polyamide (aromatic and Symmetric and asymmetric MF, UF, RO, MC
aliphatic) (PA)
Polyimidie (PI) Symmetric and asymmetric UF, RO, GS
Polypropylene (PP) Symmetric MF, MD, MC
Polyethersulfone (PESU) Symmetric and asymmetric UF, MF, GS, D
Polysulfone (PSU) Symmetric and asymmetric UF, MF, GS, D
Sulfonated polysulfone Symmetric and asymmetric UF, RO, NF
(SPSU)
Polyvinylidenefluiride Symmetric and asymmetric UF
(PVDF)
D: dialysis MF: microfiltration
EP: electrophoresis NF: nanofiltration
GS: gas separation RO: reverse osmosis
MC: membrane contactor UF: ultrafiltration
MD:
Copyright © 2018 membrane
by Volker Abetz distillation 32
H. Strathmann, Introduction to Membrane Science and Technology, Wiley-VCH, Weinheim 2011Membrane Formation by
„Phase Inversion“
Copyright © 2018 by Volker Abetz
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V. Abetz, Macromol. Rapid Commun. 2015, 36, 10.Composite Membranes with
Block Copolymers
Alignment of cylindrical structure of PS-b-PLA at the surface
selective non-selective
solvent
Copyright © 2018 by Volker Abetz
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W.A. Philipp, M. A. Hillmyer, E. Cussler, Macromolecules, 2010, 43, 7763.Membrane Formation by
„Phase Inversion“
N
N
Copyright © 2018 by Volker Abetz
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A. Jung, S. Rangou, C. Abetz, V. Filiz, V. Abetz, Macromol. Mater. Eng. 2012, 729(8), 790-798.Upscaling of Integral Asymmetric
Block Copolymer Membranes
Porosity: 8%
Track etching membrane
Copyright © 2018 by Volker Abetz
36Self-Assembly in Solvents of Different
Quality
Copyright © 2018 by Volker Abetz
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M. Radjabian et al., ACS Applied Materials & Interfaces 2017, 9, 31224.PS-b-P4VP Membranes with Different
Pore Sizes (ca. 15 -100 nm)
Molecular weight and composition control pore size
≈ 55 nm
Pore Sizes (ca. 15 -100 nm)
≈ 45 nm
4-Vinyl pyridin content
Pore size ≈ 25 nm ≈ 35 nm ≈ 40 nm
:
: molecular weight
Molecular weight (PS-b-P4VP)
Copyright © 2018 by Volker Abetz
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S. Rangou et al., J. Membr. Sci. 2014, 451, 266-275.Tailoring Pore Size by Blending
60 PS83.7P4VP16.3100 / PS75P4VP25100
Mean pore diameter (nm)
50
40
30
29 nm
20 25 nm
21 nm
10
0.0 0.2 0.4 0.6 0.8 1.0
XPS75P4VP25100
Copyright © 2018 by Volker Abetz
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M. Radjabian, V. Abetz, Advanced Materials 2015, 27, 352-355.Double Stimuli Responsive
Membranes
Modification of pH-responsive PS-b-P4VP
membranes with a temperature sensitive
polymer (pNIPAM-NH2)
=> Double stimuli-responsive membrane
0.4 µm 0.4 µm
polydopamine
coating pNIPAM-NH2
T > LCST pH <
T < LCST pH >
Copyright © 2018 by Volker Abetz
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J. I. Clodt , V. Filiz et al., Adv. Funct. Mater. 2013, 23, 731-738.Double Stimuli Responsive
Membranes
Temperature- and pH dependent water flux
Membrane after polydopamine coating and further reaction with pNIPAM-NH2
1400
Water flux [Lh m bar ]
-1
1200 T=45°C
1000
-2
T=40°C
800
-1
T=35°C
600
400 T=30°C
200
T=25°C
0
3.2 3.4 3.6 3.8 4 4.2 4.4 4.6 4.8 5 5.2
pH
Copyright © 2018 by Volker Abetz
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J. I. Clodt , V. Filiz et al., Adv. Funct. Mater. 2013, 23, 731-738.Multilayer Thin Film Composite
Membrane
Protection layer Composite separation δ 300 nm (3 layers)
Separation layer layers (d 0.3 µm)
Gutter layer
Porous support layer
(d 50 µm)
Non-woven
(d 100 µm)
Copyright © 2018 by Volker Abetz
42Thin Film Composite Membrane
Preparation
Composite
membrane
Porous supporting
membrane
Casting solution
Copyright © 2018 by Volker Abetz
43Production of Thin Film Composite
Membrane
Oven (100°C)
PAN porous membrane
Composite membrane
Casting Solution
Copyright © 2018 by Volker Abetz
44Gas Phase Separation Membrane Material Toolbox
Selective Layer Polymers
Polyimides PEG containing polymers
Thermally rearranged polymers Polymers of intrinsic microporosity
Polyacetylenes Perfluorinated amorphous polymers
45 Copyright © 2018 by Volker Abetz
A. Tena et al., Sci. Adv., 2016, 2, e1501859.; A. Tena et al., Macromolecules 2017, 50, 5839.Semicrystalline Polymeric Membrane
Polyether based block copolymers
PEBAX®
Polyamide Polyether
PolyActive™
A
B
Poly(ethylene glycol) terephthalate (PEGT) Polybutylene terephthalate (PBT)
A - Amorphous soft segments
B - Crystalline hard segments
Copyright © 2018 by Volker Abetz
46Polymers for Gas Separation Membranes
Polymer P(CO2)* CO2/N2 CO2/CH4 CO2/H2
Polysulphone 4.92 24.6 23.4 -
Cellulose Acetate 5.96 25.8 29.1 0.4
Polycarbonate 7.5 25 23.4 0.62
Matrimid 8.9 35.6 40.5 0.37
Ethyl Cellulose 14.7 22.4 10.4 1.9
Polyimide 44 35.2 30.3 -
Poly(phenylene oxide) 56.8 19.9 25.8 0.67
Poly(4-methyl pentene-1) 69.5 11.8 - 0.68
Poly(phenylene oxide) brominated 78 30 15.6 -
PEBAX 82.1 55.5 15.6 9.9
Polyactive 115 45.6 17 10.2
Poly(vinyl trimethyl silane) 190 23.8 14.6 0.95
Poly(dimethyl siloxane) 3489 9.9 3.5 4.9
Teflon AF 3900 5 6.5 1.2
Highlighted polymers are used in CO2/x separation processes
* Permeability in Barrer: 1Barrer = 1*10-10Copyright
cm3(STP) cm-2 s-1 cmHg-1
cmAbetz
© 2018 by Volker
47CO2 Supply to Algae Bioreactors
Co-operation between SSC Strategic Science Consult GmbH and HZG
Photo synthesis: algae fassade house
CO2 from heating flue gas: Increase of content from 9 to 40% required
Gas permeation unit equipped with CO2 selective membrane
Fluegas
Fluegas
CO2 rich
permeate
CO2 lean
Retentate Membrane
module
Copyright © 2018 by Volker Abetz
48
T. Wolff et al., Greenhouse Gas Sci. Technol. 2015, 15, 505.Content
1. Introduction
2. Membrane Geometries and Membrane Production
3. Membrane Modules
4. Development of a Membrane Process
Copyright © 2018 by Volker Abetz
49Requirements for Membrane Modules
• high packing density(AM/VM)
• low polarization effects, especially in RO, PV, VP, GP
• low pressure losses
• good cleaning possibilities (flushability, removal of solids), especially in UF / MF
• uniform flow over (no dead spots)
• high solids loading (UF / MF)
• mechanical, thermal and chemical stability
• cost-effective membrane change
• cost-effective manufacturing
Copyright © 2018 by Volker Abetz
50Basic Types of Membrane Modules
3-End Module 2-End Module
Feed
Feed Retentate
(liquid)
(Concentrate)
all systems Permeate
Permeate
(here shown for GP / VP) UF/MF temporary (liquid)
4-End Module, internal flushing 4-End Module, external flushing
Feed Retentate Feed Retentate
Sweep Sweep gas
gas
GP/VP Permeate GP/VP Permeate
Copyright © 2018 by Volker Abetz
51Classification of Membrane Modules
Flat sheet membranes Tubular membranes
Disk module Tubular module
Envelope type Capillary module
/Cushion module
Hollow fiber module
Spiral wound module
Packing density Modul flushability
cost-effective manufacturing Solids loading capacity
Copyright © 2018 by Volker Abetz
52amafilter Ultrafiltration Plant
Envelope membrane modules
Copyright © 2018 by Volker Abetz
53Reverse Osmosis
Seawater desalination
plant in Ashkelon, Israel
Copyright © 2018 by Volker Abetz
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R. Borsani, S. Rebagliati, Desalination 2005, 182, 29-37.Content
1. Introduction
2. Membrane Geometries and Membrane Production
3. Membrane Modules
4. Development of a Membrane Process
Copyright © 2018 by Volker Abetz
55Levels of Membrane Process
Membrane: mass and heat transport locally taking place
Module: change of concentration, pressure and temperature profiles
along the process line
Module interconnection: arrangement of membrane modules in series and parallel
circuits, required additional equipment such as heat exchangers, condensers,
compressors and pumps
Overall process: optimal transfer concentrations in relation to the total process,
determination of returns, total optimization with respect to
energy consumption and economy
Copyright © 2018 by Volker Abetz
56Membrane Process Development
Lab. scale investigations Pilot scale membrane Pilot plants
Permeation behaviour production
Module design Process simulation/design Comp. pilot plant/simulation
0.07
29.05 m3
VF (STP) h
0.06
n-C4H10 Mole fraction yR,C4 [-]
VF 34.20 m(STP)
3
h
44.46 m3
V
0.05 F (STP) h
0.04 Lines: Simulation
Symbols: Experiment
0.03
0.02
0.01
0
0 0.4 0.8 1.2 1.6 2 2.4 2.8 3.2
2
Copyright © 2018 by Volker Abetz Membrane area Az [m ]
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