Educational Workshop Fabrication of Polymer Membranes · Title: Microsoft PowerPoint - Educational...

Fabrication of Polymer Membranes

Volker Abetz

University of Hamburg, Institute of Physical ChemistryMartin-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

1Copyright © 2018 by Volker Abetz

Content

1. Introduction

2. Membrane Geometries and Membrane Production

3. Membrane Modules

4. Development of a Membrane Process


Membranes forLiquid and Gas Phase Separations

H2O CO2 / N2 O2 / N2

CH4 / CO2

Copyright © 2018 by Volker Abetz

Largest Market for Membranes: Hemodialysis

Scheme of hemodialysis

Dialysis - Application:

Hemodialysis

Commercial dialyzerFresenius FMC-Magazin 2013http://www.fmc-ag.com


Biogas Production

Source: http://www.ewe-biogas.de/

Co-fermentation mediaFeed vessel

Agriculture

Animalfeed

Manure

Hygienisation 70°C

Bio reactors37-39°C

Post fermentation Cooling CoolingH

2S R

em

ova

l

Ad

so

rpti

on

Conditioning unitCH4 enriched gas

Post condit-ioning

Connection to gas grid

Off-gasCondensateCond-

ensate

Com-pres-sion

Com-pres-sion

Gasstations

HouseholdsIndustry and decentralised energy production

Manure Manure storage

Gas grid

Decentralised energy production

Decentralised energy production

GP conditioning unit CH4 enriched gas

Post condit-ioning

Vacuumpump

Compres-sion Connection

to gas grid

Gas permeation

Heat supply


Membrane Markets

HD = HemodialysisRO = Reverse OsmosisUF = UltrafiltrationMF = MicrofiltrationED = ElectrodialysisPV = PervaporationGS = Gas Separation

To give an impression where the big membrane business is located !!


Membrane

ModuleRetainedComponent

PermeatingComponent

Feed Retentate

Permeate

Compressor:Driving force

Vacuum pump:Driving force

Heat exchanger:Processtemperature

Membrane Process (Gas Permeation)


Membrane

Module rejected component

permeating component

Feed Retentate

Permeate

Membrane Process:Principle of Separation


Porous membrane Ultra- and microfiltration Gas separation

Solution-diffusion membrane Gas and vapour permeation Pervaporation Reverse osmosis Nanofiltration

Membranes for Separation Processes


Membrane Processes - Classification

Driving force Separation mechanism

PhysicalState

Permeating particle / molecular size

Pressure difference

Difference in chemical potential

Sieving mech. (top layer filtrat.)

Sorption+Diffusion

Liquid / Liquid

Partial pressure/Difference in fugacity

Sorption+Diffusion+Volatility

Sorption+Diffusion

Liquid / Gas

Gas / Gas

Gas /Gas

Difference in concentration / activity difference

Sorption+Diffusion Liquid / Liquid

Electric potential difference

Electrophoreticmobility

Liquid / Liquid

Microfiltration

Ultrafiltration

Nanofiltration

Rev osmosis

Pervaporation

Vapor perm.

Gas perm.

Dialysis

Diffusion dial.

Bipolar electrodialysis

Electrodial.

1 nm 0,1 µm 10 µm


Membrane Processes - Classification

Microfiltration/Ultrafiltration:

Nanofiltration:

Reverse osmosis:

Dialysis:

Electrodialysis:

Pervaporation:

Retention of drops and particles, such as extraction ofproteins from whey

Retention of components with M>300 kg/mol

Retention of dissolved substances in water, eg seawater desalination

Difference in concentration-driven permeation,e.g. hemodialysis

Separation of ions by alternation of anion and cation selectivemembranes, the driving force is the electric potential

Liquid feed, evaporation of the passing material stream in the permeate, the driving force is the difference in activity

Pre

ssur

edr

ivin

gfo

rce

por

ous

me

mb

rane

den

sem

em

bra

ne


Gas permeation/Vapor permeation:

Contactors:

Membrane reactors:

Separation of gas and vapor mixtures, the driving forceis the difference of pressure or fugacity

The porous membrane is the mass transfer area for absorption, extraction desorption or distillation processes

Combination of reaction and separation in a basic operation, depending on the reaction conditions using porous or dense membranes

den

sem

em

bra

nep

orou

sm

em

bra

neMembrane Processes - Classification


VOC recoveryPoly(dimethyl siloxane) PDMS

Poly(octyl methyl siloxane) POMSPolymers of Intrinsic Microporosity PIM

Polyacetylenes: Si; Ge; C Teflon AF ® : 2400; 1600

CO2 separationPoly(ether-block-ester) PolyActive™Poly(ether-block-amide) PEBAX®

Cellulose acetate / triacetateEthyl cellulosePDMS Polymers of Intrinsic Microporosity PIM

DehydrationPoly(vinyl alcohol)

TYLOSE ®

Cellulose acetate / triacetate

H2 separationPolyimidesPIMPPOPEI

O2/N2 SeparationCellulose Acetate

PDMSPIMPPO

NanofiltrationModified PDMS

PIM

Food storageEthyl cellulose

Catalytic membranesPDMSPIM

PEBAXTORLON®

Active and inactive additives to matrix materialsSiO2, TiO2, Pd nanoclusters, carbon (active and nano), PEG, amino compounds, active carriers etc.

13

Gas Separation MembranesState-of-the-art membrane materials


M. Ulbricht, Polymer 2006, 47, 2217.

14

UF/MF membranesState-of-the-art membrane materials

Cellulose acetate

Polysulfone/ Polyethersulfone

Polyvinylidenfluoride

Polyamide

Track-etched

Cellulose nitrate

Polyethylene

Polytetrafluoroethylene

Polypropylene

Polyethylene terephthalatePolycarbonate

Cellulose, regenerated

Polyacrylonitrile

Ceramic membranes(Al2O3, TiO2, ZrO2, SiO2, SiC)

PolycarbonatePolyesterPolyimide

UF MF

Mesoporousmainly anisotropic

Macroporousisotropic


Content

1. Introduction


3. Membrane Modules



16

Molecular Weight Cut-off

Log MW

Rej

ectio

n


17

UF / MFState-of-the-art membrane preparation metohds

Symmetric MF Membranes

Casting + leaching / evaporation Film-stretching

Asymmetric MF Membranes

Sintering / Slip casting

Phase inversion

Track-etchingAnodising process

K. Scott, Handbook of Industrial Membranes, 2. ed., Ed. 2, Elsevier Science & Technology Books, Oxon (UK) 1999, 118.


Membrane Preparation

Processing Via Sintering

I: Filling of mould III: Sintering under pressure

II: Precompression IV: Pressureless sintering EP 2 982 492

Ia Ib

II III IV


Sintered Membranes

• Commercial Examples

• Ultra-high molecular weight polyethylene (UHMWPE) membranes

• UHMWPE: Excellent mechanical properties

• Processing requires special techniques

• Poly(tetrafluoroethylene) (PTFE) membranes

• PTFE: High chemical and thermal stability

• High hydrophobicity

• Applications: Filter membranes, dust filters,

• pressure compensation units

Figure sources: MICRODYN-NADIR GmbH (Wiesbaden); Berghof Products (Eningen)

SEPRODYN®

Screw-in filter


20

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 thestacked lamellar morphology after extrusion and rolling process because only stacked lamellae are ableto 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.

Paste extrusion Rolling Uniaxial stretching at RT

Fine powderwith lubricant

Paste extrusion(10-20 cm/ min)

Thin sheet Multiple rolling to reduce the thickness

5 mm 1 mm

Direction of rolling

Direction of stretching

Uniaxial Stretching Method

http://www.che.vt.edu/Faculty/Wilkes/GLW/jays_page/glw-webpage-jay.htm


21

MD = Machine direction TD= Transverse direction

TEM micrograph (a) shows a uniaxially oriented high density polyethylene (HDPE) film melt extruded andcrystallized under directional flow. A stacked lamellar morphology is observed with the lamellae orientedalong the transverse direction. After a further annealing treatment, the melt extruded HDPE film wasdeformed along the machine direction. During the deformation process, the stacked lamellae tend toseparate to form microporous membranes, as shown in TEM micrograph (b).

http://www.che.vt.edu/Faculty/Wilkes/GLW/jays_page/glw-webpage-jay.htm

Uniaxial Stretching Method


22

Free radical emulsion or suspension polymerization

Properties

• Tm (1. melting) = 342 °C

• Tm (2.,3… melting) = 327 °C

• below Tm insoluble in all organic solents

• enormous melt viscosity (1010 Pa·s @ 380 °C)

extended chain crystals

folded chain crystals

Biaxially Stretched MembranePoly(tetrafluoro ethylene) (PTFE)

Goretex® membrane

3 µm


23

Etching bath

Membrane withporous structure

Radiation source

Polymer film

Two basic irradiation methods

1. fragments from the fission of heavy nuclei ( e.g. Cf or U)

2. heavy ion beams from accelerators

E. Drioli, L. Giorno, Comprehensive Membrane Science and Engineering, 1. ed., Elsevier, UK 2010, 98.S.K. Chakarvarti, Radiation Measurements 2009, 44, 1085.P. Apel, Radiation Measurements 2001, 34, 559.

Etching

• alkali solution (e.g. NaOH, KOH)

Pore-size and pore-shape

• uniform cylindrical, conical, tunnel-like, or cigar-like

• controllable due to e.g.

• target material

• the nature and energy of incident particles

• etch conditions (T, etchant, pre-etch storage)

Track Etched Membranes

A polymer film is bombarded with heavy ions and the radiation damaged areas are removed using an etching bath.


24

• symmetric membranes

• very narrow pore size distribution

• pores diameter ranging from few nm to mm

• prevention of surface roughness effects

• various materials

• used in microbiology or particle analysis

• pore size < membrane thickness• pore blocking• cake layer formation

P. Apel, Radiation Measurements 2001, 34, 559.

Polyethylene terephthalatecigar-like pores

non-parallel pore channelsPolycarbonate Polypropylene

slightly conical parallel pores

Polyethylene terephthalate“bow-tie” pores

1 µm

1 µm1 µm

1 µm



25

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



26

10 µm

© Satorius

Most common: non-solvent induced

H. Matsuyama,K. Ohga,T. Maki, M. Tearamoto, S. Nakatsuka, Journal of Applied Polymer Science 2002, 89, 3951.

precipitation bath

Alternative: thermally induced

Phase Inversion Process

Cellulosic membrane


27

limited pH-stability

not autoclavable (dry)

lack of tolerance to free chlorine

to aggressive cleaning chemicals

to temperature above 30 °C

susceptibility to biological degradation

gradual decline in flux over lifetime due to compaction

most-hydrophilic industrial-grade membrane material

low unspecific adsorption

high flux

high service life

inexpensive

easy to manufacture

low impact on environment (waste)

Properties

Cellulosic Membrane

CelluloseCellulose Triacetate


HZG Membrane Casting Machine

30 cm

Coating knife

Immersion bath

Solvent Evaporation

Nonwoven

Polymer solution

Casting of the polymer solution onto a substrate, e.g. nonwoven, on rolls up to 30cm width

S. Rangou, K. Buhr et al., J. Membr. Sci. 2014, 451, 266-275.


M. Radjabian, et al., Polymer 2014, 55, 2986-2997. K. Sankhala, et al., Adv. Mat. Int. 2017, 4, 1600991

Outside-in Membranes Inside-out Membranes

Isoporous Hollow Fiber Membranes


HZG Membrane Production Facility


Asymmetric Membranes withFinger Pore Substructure from NIPS

12% cellulose acetate (CA)in dimethylacetamide (DMAc)

12% polyamide (PA) in dimethylsulfoxide (DMSO)

12% polysulfone (PSU) in dimethylformamide (DMF)

Filtration rate (m/s)

Retention g-globulin

Retention bovin serum albumin (BSA)

Porosity (%)

12% CA in DMAc

3.5 x 10-5 99 98 80

12% PA in DMSO

2.1 x 10-5 97 72 82

12% PSU in DMF

1.9 x 10-5 96 80 83

H. Strathmann, Introduction to Membrane Science and Technology, Wiley-VCH, Weinheim 2011


Commercial Polymer MembranesMade by Phase Inversion

Membrane Material Membrane Structure Membrane ProcessCellulose Acetate (CA) Asymmetric EP, MF, UF, ROCellulose mixed esters Asymmetric and symmetric MF, DPolyacrylonitrile (PAN) Asymmetric UFPolyamide (aromatic and aliphatic) (PA)

Symmetric and asymmetric MF, UF, RO, MC

Polyimidie (PI) Symmetric and asymmetric UF, RO, GSPolypropylene (PP) Symmetric MF, MD, MCPolyethersulfone (PESU) Symmetric and asymmetric UF, MF, GS, DPolysulfone (PSU) Symmetric and asymmetric UF, MF, GS, DSulfonated polysulfone (SPSU)

Symmetric and asymmetric UF, RO, NF

Polyvinylidenefluiride (PVDF)

Symmetric and asymmetric UF

D: dialysisEP: electrophoresisGS: gas separationMC: membrane contactorMD: membrane distillation

MF: microfiltrationNF: nanofiltrationRO: reverse osmosisUF: ultrafiltration

H. Strathmann, Introduction to Membrane Science and Technology, Wiley-VCH, Weinheim 2011


Membrane Formation by„Phase Inversion“

V. Abetz, Macromol. Rapid Commun. 2015, 36, 10.


W.A. Philipp, M. A. Hillmyer, E. Cussler, Macromolecules, 2010, 43, 7763.

Composite Membranes with Block Copolymers

Alignment of cylindrical structure of PS-b-PLA at the surface

selective non-selectivesolvent


K.-V. Peinemann, V. Abetz, P.F.W. Simon, Nature Materials 2007, 6, 992-996.A. Jung, S. Rangou, C. Abetz, V. Filiz, V. Abetz, Macromol. Mater. Eng. 2012, 729(8), 790-798.

Membrane Formation by„Phase Inversion“

N

N


Upscaling of Integral AsymmetricBlock Copolymer Membranes

Porosity: 8%

Track etching membrane


Self-Assembly in Solvents of Different Quality

M. Radjabian et al., ACS Applied Materials & Interfaces 2017, 9, 31224.


Pore Sizes (ca. 15 -100 nm)

Pore size ≈ 25 nm

Molecular weight (PS-b-P4VP)

4-V

inyl

pyr

idin

con

ten

t

≈ 55 nm

≈ 40 nm

≈ 45 nm

≈ 35 nm

S. Rangou et al., J. Membr. Sci. 2014, 451, 266-275.

: : molecular weight

Molecular weight and composition control pore size

PS-b-P4VP Membranes with Different Pore Sizes (ca. 15 -100 nm)


0.0 0.2 0.4 0.6 0.8 1.010

20

30

40

50

60

29 nm25 nm

21 nm

XPS75P4VP25100

PS83.7P4VP16.3100 / PS75P4VP25

100

Me

an p

ore

dia

met

er (

nm)

Tailoring Pore Size by Blending

M. Radjabian, V. Abetz, Advanced Materials 2015, 27, 352-355.


Double Stimuli Responsive Membranes

polydopamine coating pNIPAM-NH2

T > LCST

T < LCST

pH <

0.4 µm 0.4 µm

Modification of pH-responsive PS-b-P4VP membranes with a temperature sensitive polymer (pNIPAM-NH2)=> Double stimuli-responsive membrane

J. I. Clodt , V. Filiz et al., Adv. Funct. Mater. 2013, 23, 731-738.

pH >


Temperature- and pH dependent water flux

Membrane after polydopamine coating and further reaction with pNIPAM-NH2

0

200

400

600

800

1000

1200

1400

3.2 3.4 3.6 3.8 4 4.2 4.4 4.6 4.8 5 5.2

pH

Wat

er f

lux

[Lh

-1m

-2b

ar-1

]

T=45°C

T=40°C

T=35°C

T=30°C

T=25°C

J. I. Clodt , V. Filiz et al., Adv. Funct. Mater. 2013, 23, 731-738.

Double Stimuli Responsive Membranes


Multilayer Thin Film Composite Membrane

Non-woven (d 100 µm)

Porous support layer (d 50 µm)

δ 300 nm (3 layers)Composite separation layers (d 0.3 µm)

Gutter layer

Protection layer

Separation layer


Thin Film Composite Membrane Preparation

Porous supporting membrane

Casting solution

Composite membrane


Casting Solution

Oven (100°C)

Composite membrane

PAN porous membrane

Production of Thin Film Composite Membrane


Polyimides PEG containing polymers

Thermally rearranged polymers Polymers of intrinsic microporosity

Polyacetylenes Perfluorinated amorphous polymers

Gas Phase Separation Membrane Material ToolboxSelective Layer Polymers

45

A. Tena et al., Sci. Adv., 2016, 2, e1501859.; A. Tena et al., Macromolecules 2017, 50, 5839.


Semicrystalline Polymeric Membrane

Polyether based block copolymers

A - Amorphous soft segmentsB - Crystalline hard segments

A

B

Polyamide Polyether

Poly(ethylene glycol) terephthalate (PEGT) Polybutylene terephthalate (PBT)

PolyActive™

PEBAX®


Polymers 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*10-10 cm3(STP) cm cm-2 s-1 cmHg-1


CO2 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 richpermeate

CO2 leanRetentate Membrane

module

T. Wolff et al., Greenhouse Gas Sci. Technol. 2015, 15, 505.


Content

1. Introduction


3. Membrane Modules



Requirements 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


Basic Types of Membrane Modules

3-End Module 2-End Module

4-End Module, external flushing4-End Module, internal flushing

Feed Retentate(Concentrate)

Permeate

Feed(liquid)

Permeate(liquid)

Feed

Permeate

Retentate Feed Retentate

Permeate

all systems(here shown for GP / VP) UF/MF temporary

Sweepgas

GP/VP

Sweep gas

GP/VP


Classification of Membrane Modules

Flat sheet membranes Tubular membranes

Disk module

Envelope type/Cushion module

Spiral wound module

Tubular module

Capillary module

Hollow fiber module

Packing densitycost-effective manufacturing

Modul flushabilitySolids loading capacity


amafilter Ultrafiltration Plant

Envelope membrane modules


Seawater desalinationplant in Ashkelon, Israel

R. Borsani, S. Rebagliati, Desalination 2005, 182, 29-37.

Reverse Osmosis


Content

1. Introduction


3. Membrane Modules



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 toenergy consumption and economy

Levels of Membrane Process


Membrane Process Development

Lab. scale investigations

Permeation behaviour

Pilot scale membraneproduction

Pilot plants

Module design Process simulation/design Comp. pilot plant/simulation

0

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0 0.4 0.8 1.2 1.6 2 2.4 2.8 3.2

Membrane area Az [m2]

n-C

4H

10 M

ole

fra

ctio

n y

R,C

4 [-

]

Lines: SimulationSymbols: Experiment

hm44.46V

hm34.20V

hm29.05V

3(STP)F

3(STP)F

3(STP)F

0

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0 0.4 0.8 1.2 1.6 2 2.4 2.8 3.2

Membrane area Az [m2]

n-C

4H

10 M

ole

fra

ctio

n y

R,C

4 [-

]

Lines: SimulationSymbols: Experiment

hm44.46V

hm34.20V

hm29.05V

3(STP)F

3(STP)F

3(STP)F


Educational Workshop Fabrication of Polymer Membranes · Title: Microsoft PowerPoint - Educational...

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