Production Aspects of Membranes used in Medical and Industrial ...
Production Aspects of Membranes used in Medical and Industrial ...
Production Aspects of Membranes used in Medical and Industrial ...
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<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong> <strong>used</strong> <strong>in</strong><br />
<strong>Medical</strong> <strong>and</strong> <strong>Industrial</strong> Applications<br />
Kassel, DGMT Meet<strong>in</strong>g<br />
December 6 <strong>and</strong> 7th, 2006<br />
Dr. Wolfgang Ansorge<br />
MEMBRANA GmbH<br />
Wuppertal Germany<br />
www.membrana.com
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Content <strong>of</strong> Presentation / Outl<strong>in</strong>e<br />
� Goal <strong>of</strong> Presentation<br />
�Historical Background<br />
�Markets<br />
�Polymers <strong>and</strong> Solvents for <strong>Membranes</strong><br />
�Membrane Formation (SIPS <strong>and</strong> TIPS)<br />
�Poduction Processes<br />
�Typical Applications<br />
�Required Membrane Properties <strong>and</strong> Influence <strong>of</strong> <strong>Production</strong><br />
Parameters<br />
�Modules<br />
� Summary
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Goal <strong>of</strong> Presentation<br />
� Give a short historical overview <strong>and</strong> describe the market<br />
situation.<br />
� Provide an overview <strong>in</strong>sight <strong>of</strong> membrane formation<br />
mechanisms <strong>and</strong> subsequent consequences for materials<br />
<strong>used</strong> <strong>in</strong> membrane production <strong>and</strong> <strong>in</strong> the respective<br />
production processes.<br />
� Discuss some examples <strong>of</strong> membranes for medical <strong>and</strong><br />
<strong>in</strong>dustrial applications <strong>and</strong> the <strong>in</strong>fluence <strong>of</strong> the production<br />
processes on performance parameters.<br />
� Make a short side step to module manufactur<strong>in</strong>g.
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Historical Background <strong>and</strong><br />
Markets
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Membrana´s History<br />
start <strong>of</strong> CUPROPHAN ® capillary membrane<br />
start <strong>of</strong> dialysis membrane production<br />
start <strong>of</strong> CUPROPHAN ® production<br />
1920-40 major manufacturer <strong>of</strong><br />
“artificial silk”, worldwide<br />
famous artificial<br />
“Bemberg silk”<br />
”turkish red”<br />
dye<strong>in</strong>g company<br />
1792<br />
start <strong>of</strong> <strong>in</strong>dustrial membrane production<br />
(ACCUREL ® )<br />
1917<br />
<strong>in</strong>troduction <strong>of</strong> DIAPES ® <strong>and</strong> OXYPLUS ®<br />
start <strong>of</strong> SMC ® - <strong>and</strong> MicroPES ® membrane production 1995<br />
<strong>in</strong>troduction <strong>of</strong> HEMOPHAN ® <strong>and</strong> OXYPHAN ®<br />
1920<br />
1945<br />
1965<br />
1974<br />
1980<br />
Enka AG 1977<br />
Enka Glanzst<strong>of</strong>f AG 1972<br />
1988<br />
1999/2000<br />
Glanzst<strong>of</strong>f AG merged withVere<strong>in</strong>igten Glanzst<strong>of</strong>f Fabriken 1971<br />
J. P. Bemberg (major shareholder Vere<strong>in</strong>igte Glanzst<strong>of</strong>f Fabriken) 1925<br />
J.P. Bemberg 1792, ab 1900 J. P. Bemberg AG<br />
Forward <strong>in</strong>tegration module manufactur<strong>in</strong>g<br />
<strong>in</strong>troduction <strong>of</strong> PUREMA ®<br />
<strong>in</strong>troduction <strong>of</strong> DURAPES<br />
2004<br />
® <strong>and</strong> MicrolonTM <strong>in</strong>troduction <strong>of</strong> Liqui-Flux ®<br />
2006<br />
2005<br />
<strong>in</strong>troduction <strong>of</strong> HEXPET ® 2000<br />
Enka AG / Akzo 1988<br />
Acordis 1999<br />
Akzo Nobel Faser AG 1994<br />
Akzo Faser AG 1991<br />
Membrana GmbH,<br />
Polypore 2002
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Markets / Development <strong>of</strong> Dialyzers by Regions<br />
Mill Pcs<br />
200<br />
150<br />
100<br />
50<br />
0<br />
ROW<br />
W-Europe<br />
Japan<br />
NA<br />
23<br />
24<br />
30<br />
15<br />
+ 9%/a<br />
38<br />
31<br />
38<br />
35<br />
+ 7%/a<br />
2000 2005 2010E<br />
60<br />
39<br />
46<br />
54
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Markets / Oxygenations – Procedures: Potential<br />
<strong>in</strong> 1,000<br />
1.400<br />
1.200<br />
1.000<br />
800<br />
600<br />
400<br />
200<br />
0<br />
1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009<br />
ROW<br />
Japan<br />
USA<br />
Europa
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Markets / US-Membrane Systems Dem<strong>and</strong> MF <strong>and</strong> UF<br />
Adapted from: The Freedonia Group, Membrane Sep. Technologies, market report, Dec. 2003
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Polymers <strong>and</strong> Solvents
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Polymers / What is the Desired Membrane Design?<br />
� Appearance (hollow fiber, tube, flat sheet)<br />
� Permeability <strong>and</strong> selectivity to the desired solutes<br />
� Adequate siev<strong>in</strong>g characteristics (cut <strong>of</strong>fs)<br />
� Adequate water (or solvent) permeability<br />
� Chemical <strong>and</strong> physical resistance (pH, peroxides, acids,<br />
caustics, blood)<br />
� Low amounts <strong>of</strong> extractables (TOC, toxicity)<br />
� Heat resistance (sterilizeability)<br />
� Impermeability <strong>of</strong> bacteria / viruses (pharmaceutical appl.)
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Polymers / How to choose the Membrane Material?<br />
� Membrane form<strong>in</strong>g properties (mol weight distribution)<br />
� Solubility <strong>in</strong> commonly <strong>used</strong> solvents<br />
� Storage stability <strong>of</strong> the sp<strong>in</strong>n<strong>in</strong>g solution<br />
� Costs<br />
� Chemical structure with respect to<br />
�chemical stability (solvents <strong>and</strong> solutes <strong>used</strong> <strong>in</strong> the application)<br />
�physical stability (tensile strength, elongation at break)<br />
�hydrophilicity / hydrophobicity (wettability)<br />
�adsorptive properties aga<strong>in</strong>st solutes (foul<strong>in</strong>g)<br />
�extractable monomers or oligomers (TOC, toxicity)<br />
�stability aga<strong>in</strong>st oxidation (discolouration, sterilization)<br />
�stability aga<strong>in</strong>st heat / steam (temp. <strong>in</strong> application, sterilization)<br />
�bio- / hemocompatibility (prote<strong>in</strong> adsorption, cell stimulation)<br />
�make-up (w<strong>in</strong>d<strong>in</strong>g, pott<strong>in</strong>g, cutt<strong>in</strong>g, module design)
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Polymers / Typical Raw Materials<br />
� Dialysis<br />
� Cellulose / Modified Cellulose (DEAE, Benzyl) (Semi synthetic)<br />
� Cellulose Acetate (CA or CTA)<br />
� Polycarbonate (PC)<br />
� Polyacrylonitrile (PAN)<br />
� Polyamide (PA)<br />
� Polysulfone (PSu)<br />
� Polyethersulfone (PES)<br />
� Oxygenation<br />
� Polypropylene (PP)<br />
� Polyethylene (PE)<br />
� Polymethylpentene (PMP)<br />
� Plasma Treatment<br />
� Polypropylene (PP)<br />
� Polyethersulfone (PES)<br />
� Poly-(ethylene-v<strong>in</strong>ylalcohol) (EVAL)<br />
� Others<br />
(<strong>Industrial</strong> applications or l<strong>in</strong>ked to Medic<strong>in</strong>e)<br />
� Polyolef<strong>in</strong>s (PP, PE, PMP)<br />
� Polyethersulfone (PES)<br />
� Polyamides (PA 6, PA 6.6)<br />
� Polysulfone (PSu)<br />
� Cellulose Acetate (CA)<br />
� Polyv<strong>in</strong>ylidenefluoride (PVDF)<br />
� Polytetrafuoroethylene (PTFE)<br />
� Polyimides (PI)<br />
� Polyetherimides (PEI)<br />
� Polyetheretherketones (PEEK)<br />
� Silicones
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Solvents / How to Choose the Right System?<br />
� Availability<br />
� Polymer solubility properties (solution stability)<br />
� Toxicity (safe h<strong>and</strong>l<strong>in</strong>g � workers, extractables � patient <strong>and</strong> TOC)<br />
� Costs (price <strong>of</strong> f<strong>in</strong>al product)<br />
� Recovery (ability, procedure � costs)<br />
� Environmental aspects (waste water)<br />
� Chemical structure with respect to<br />
�thermal stability<br />
�oxidative stability<br />
�explosion safeness<br />
�melt<strong>in</strong>g <strong>and</strong> boil<strong>in</strong>g po<strong>in</strong>ts<br />
�vapour pressure<br />
�<strong>in</strong>ertness (no reaction with polymer or other igredients <strong>of</strong> sp<strong>in</strong>n<strong>in</strong>g solution)<br />
�miscibility with e.g. water or alcohols (extraction media)<br />
Remark: Not all properties may be fulfilled by a solvent (system)
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Solvents / Typical Systems<br />
� Solvents<br />
�Cuoxam (ammonia, caustic copper sulfate, sodium hydroxide)<br />
�Aprotic liquids (DMSO, DMF, DMAc, NMP)<br />
�Alcohols (methanol, ethanol, IPA or others)<br />
�Lactones, Lactams<br />
�Chlor<strong>in</strong>ated hydrocarbons (methylene-chloride etc.)<br />
�Oils (soy bean oil, castor oil, others)<br />
�Ethers (THF, others)<br />
� Additives<br />
�PVP, PEGs (poreformers, hydrophiliz<strong>in</strong>g agents, <strong>in</strong>creased viscosity)<br />
�Glycerol (pore conservation)<br />
�Other polymers (blend<strong>in</strong>g)<br />
�Stabilizers (antioxidants, protection aga<strong>in</strong>st discolouration, heat protection)
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Membrane Formation
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Membrane Formation / Mechanism <strong>of</strong> Phase<br />
Separation (SIPS)<br />
Path A<br />
metastable condition<br />
NG (nucleation growth)<br />
100<br />
0<br />
solvent<br />
A<br />
Polymer<br />
0<br />
100<br />
B<br />
0<br />
100<br />
non-solvent<br />
Path B<br />
unstable condition<br />
SD (sp<strong>in</strong>odal decomposition)<br />
Slow (controlled) precipitation Quick (uncontrolled) precipitation<br />
Adapted from: Membranen: Grundlagen, Verfahren und <strong>in</strong>d. Anwendung, K. Ohlrogge und K. Ebert, Wiley 2006
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Membrane Formation / Solvent Induced Phase<br />
Separation (SIPS)<br />
Pr<strong>in</strong>ciple<br />
Melted<br />
mass<br />
Capillary<br />
membrane<br />
Core liquid<br />
Polymer<br />
Sp<strong>in</strong>n<strong>in</strong>g / Cast<strong>in</strong>g Solution<br />
Sp<strong>in</strong>n<strong>in</strong>g<br />
Filtration<br />
Phase separation<br />
(formation <strong>of</strong> membrane)<br />
Wash<strong>in</strong>g/Extraction<br />
Dry<strong>in</strong>g<br />
Process<strong>in</strong>g for shipment<br />
Solvent /<br />
Additives<br />
Cast<strong>in</strong>g<br />
(flat sheet)<br />
Melted mass<br />
Flat<br />
membrane
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Membrane Formation / Mechanism <strong>of</strong> TIPS Process<br />
Nucleation <strong>and</strong> Growth<br />
At low cool<strong>in</strong>g rates<br />
Temperature<br />
Cool<strong>in</strong>g<br />
Polymer concentration<br />
Sp<strong>in</strong>odal Decomposition<br />
At high cool<strong>in</strong>g rates
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
<strong>Production</strong> Processes
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
<strong>Production</strong> Processes / PES Sp<strong>in</strong>n<strong>in</strong>g Process (SIPS)<br />
Modular concept for DIAPES ® , PUREMA ® , MicroPES ® <strong>and</strong> UltraPES<br />
Polymer<br />
solution<br />
Bore<br />
liquid<br />
Sp<strong>in</strong>neret<br />
coagulation pre-extraction<br />
Cross-section view<br />
Polymer sp<strong>in</strong>n<strong>in</strong>g<br />
solution<br />
make-up<br />
• dry<strong>in</strong>g<br />
• w<strong>in</strong>d<strong>in</strong>g<br />
• cutt<strong>in</strong>g<br />
Bore liquid<br />
wrapp<strong>in</strong>g<br />
pipel<strong>in</strong>e<br />
air<br />
water<br />
extraction<br />
&<br />
dry<strong>in</strong>g
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
<strong>Production</strong> Processes / PES<br />
Partial view <strong>of</strong> the plant
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
<strong>Production</strong> Processes / DIAPES ® Membrane Structure<br />
Scann<strong>in</strong>g Electron Microscopy<br />
= 5 nm<br />
= 100 nm<br />
30 µm<br />
= 10 nm
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
<strong>Production</strong> Processes / UltraPES Membrane Structure<br />
Scann<strong>in</strong>g Electron Microscopy<br />
Function:<br />
Poresize<br />
about:<br />
Separation<br />
Layer<br />
220 µm<br />
Support Layer Protection<br />
Layer<br />
6 – 7 nm Up to 500 nm 20 - 100 nm
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
<strong>Production</strong> Processes / Flat Membrane Cast<strong>in</strong>g<br />
(SIPS)<br />
Polymer<br />
solution<br />
Climate box<br />
Cast<strong>in</strong>g unit<br />
Chill roll<br />
Precipitation Wash<strong>in</strong>g<br />
stretch<strong>in</strong>g<br />
relaxation<br />
post<br />
treatment<br />
control <strong>of</strong><br />
<strong>in</strong>tegrity <strong>and</strong><br />
dimensions<br />
optional<br />
Roll<br />
•Dry<strong>in</strong>g<br />
•W<strong>in</strong>d<strong>in</strong>g<br />
•Cutt<strong>in</strong>g
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
<strong>Production</strong> Processes / PES Flat-Membrane Structures<br />
Scann<strong>in</strong>g Electron Microscopy<br />
MicroPES ® 2F<br />
DuraPES ® 200<br />
Asymmetrical structure<br />
Very asymmetrical structure<br />
Chill Roll Side Air Side Cross Section
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
<strong>Production</strong> Processes / Flux Comparison<br />
<strong>Membranes</strong> out <strong>of</strong> SIPS Process<br />
Nom<strong>in</strong>al pore size (µm)<br />
1,6<br />
1,4<br />
1,2<br />
1<br />
0,8<br />
0,6<br />
0,4<br />
0,2<br />
For DuraPES ® fluxes are higher than for comparable MicroPES ® types<br />
UltraPES ®<br />
DIAPES ® HF<br />
FractioPES ®<br />
MicroPES ® 1F PH<br />
MicroPES ® MicroPES<br />
2F<br />
® MicroPES<br />
4F<br />
® MicroPES 6F<br />
® 0.3/2<br />
DuraPES ® DuraPES<br />
200<br />
® DuraPES<br />
450<br />
® 600<br />
0<br />
102 103 105 104 > 500<br />
MicroPES ® 12F<br />
log hydraulic permeability - water [ml / (h x m² x mmHg)]<br />
> 500 ml / h m² mmHg = > 0,65 ml / m<strong>in</strong> cm² bar<br />
= Technical Products („F“ represents Flat <strong>Membranes</strong>)<br />
= <strong>Medical</strong> Products (for comparison)<br />
10 6
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
<strong>Production</strong> Processes / Process Scheme (TIPS)<br />
Polymer Solvent<br />
Heat<br />
Temperature<br />
controlled air gap<br />
Gas N 2<br />
Heated<br />
extruder<br />
Or sp<strong>in</strong>n<strong>in</strong>g bar <strong>and</strong> chill roll<br />
<strong>in</strong>stead <strong>of</strong> sp<strong>in</strong>neret<br />
No gas needed<br />
Sp<strong>in</strong>neret<br />
Gas Melted polymer<br />
<strong>and</strong> high<br />
temperature<br />
solvent<br />
1. sp<strong>in</strong>n<strong>in</strong>g 2. extraction 3. dry<strong>in</strong>g <strong>and</strong> w<strong>in</strong>d<strong>in</strong>g
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
<strong>Production</strong> Processes / SEM <strong>of</strong> OXYPHAN ® (PP)<br />
Inner surface Cross section Outer surface
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
<strong>Production</strong> Processes / Flat Membrane Cast<strong>in</strong>g<br />
(Mixed TIPS <strong>and</strong> SIPS)<br />
Polymer<br />
Dosage<br />
Heated<br />
extruder<br />
Solvent<br />
Mixer<br />
Precipitation Wash<strong>in</strong>g<br />
So called „solution mach<strong>in</strong>e“<br />
Cast<strong>in</strong>g unit (heated)<br />
Chill roll (controlled cool<strong>in</strong>g)<br />
stretch<strong>in</strong>g<br />
relaxation<br />
post<br />
treatment<br />
control <strong>of</strong><br />
<strong>in</strong>tegrity <strong>and</strong><br />
dimensions<br />
optional<br />
Roll<br />
•Dry<strong>in</strong>g<br />
•W<strong>in</strong>d<strong>in</strong>g<br />
•Cutt<strong>in</strong>g
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
<strong>Production</strong> Processes / Typical SEM (PA)<br />
Chill roll side Air side<br />
Mag. 5000<br />
Smaller but<br />
more pores<br />
Cross section<br />
Mag. 5000<br />
Larger but<br />
less pores<br />
Mag. 500<br />
More or less symmetrical
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
<strong>Production</strong> Processes / Melt Extrusion <strong>and</strong> Stretch<strong>in</strong>g<br />
(CELGARD ® )<br />
Scheme Melt Extrusion<br />
Polymer<br />
Dosage<br />
Heated<br />
extruder<br />
Air Cool<strong>in</strong>g<br />
Die<br />
Filter<br />
Spool<br />
W<strong>in</strong>d<strong>in</strong>g <strong>of</strong> non porous<br />
capillary
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
<strong>Production</strong> Processes / Melt Extrusion <strong>and</strong> Stretch<strong>in</strong>g<br />
(CELGARD ® )<br />
Scheme Stretch<strong>in</strong>g<br />
Spool<br />
Anneal<br />
Non porous capillary<br />
Cold Stretch<br />
Hot Stretch<br />
Spool<br />
Porous capillary
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
<strong>Production</strong> Processes / CELGARD ® - Extruder<br />
“Precursor Precursor Spool” Spool
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
<strong>Production</strong> Processes / CELGARD ® X30-240 HFM<br />
Celgard X30-240<br />
typical values<br />
Thickness 28 µ<br />
Gurley 35 sec<br />
Porosity 40%<br />
Shr<strong>in</strong>kage 2.5 %<br />
Pore size 0.03 x 0.6 µm
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Typical <strong>Medical</strong> Applications
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Typical <strong>Medical</strong> Applications / Hemodialysis<br />
Blood<br />
>200ml/m<strong>in</strong><br />
Capillary<br />
membranes<br />
Dialysate Blood<br />
Dialyzer<br />
500ml/m<strong>in</strong><br />
Dialysate + ultrafiltrate<br />
>500ml/m<strong>in</strong><br />
Dialysate<br />
to waste
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Typical <strong>Medical</strong> Applications / Oxygenation<br />
dra<strong>in</strong><strong>in</strong>g l<strong>in</strong>es<br />
cardiotomy<br />
arterial<br />
filter<br />
blood (3-6l/m<strong>in</strong>)<br />
oxygenator<br />
O 2 + CO 2<br />
O 2
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Typical <strong>Medical</strong> Application / Plasmaseparation<br />
filtered<br />
plasma<br />
blood<br />
>200ml/m<strong>in</strong><br />
capillary<br />
membranes<br />
blood<br />
plasma<br />
filter<br />
about 40ml/m<strong>in</strong><br />
removed<br />
replacement by plasma plasma<br />
<strong>of</strong> healthy donors<br />
(therapeutic plasmapheresis)
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Required Membrane Properties
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Required Membrane Properties / Hemodialysis<br />
Blood UFR<br />
ml/hm²mmHg<br />
Flux <strong>and</strong> Siev<strong>in</strong>g Coefficients<br />
LF<br />
PUREMA ®<br />
L<br />
LF+<br />
DIAPES ®<br />
LF100<br />
HP<br />
DIAPES ®<br />
HP200<br />
DIAPES ®<br />
HF800XP<br />
Synthetic Dialysis <strong>Membranes</strong> (PES)<br />
HF<br />
6 10 - 12 15 - 20 > 30<br />
PUREMA ®<br />
H<br />
DIAPES ®<br />
HF800<br />
Remark: Increased siev<strong>in</strong>g coefficients also implement <strong>in</strong>creased ß2-M clearances / siev<strong>in</strong>g coefficient
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Required Membrane Properties / Hemodialysis<br />
S.E.T. – Siev<strong>in</strong>g Enhanc<strong>in</strong>g Technology<br />
%<br />
Vit. B12: 2,88 nm<br />
Inul<strong>in</strong>:4,60 nm<br />
ß2-m: 5,94 nm<br />
pore size<br />
α1−m: 8,28 nm<br />
BSA:10,64 nm<br />
PUREMA H<br />
Fresenius FX<br />
Polyflux S<br />
PUREMA ®<br />
Conventional Polysulfone
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Required Membrane Properties / Hemodialysis<br />
PUREMA ® : Active Surface Management<br />
Red: hydrophobic surface (PES)<br />
Green: hydrophilic surface (PVP)<br />
Blue dots: active centers<br />
Blue circles: mediation <strong>of</strong> the<br />
<strong>in</strong>teractions <strong>of</strong> tox<strong>in</strong>s <strong>and</strong><br />
prote<strong>in</strong>s across the whole <strong>in</strong>ner<br />
surface
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Required Membrane Properties / Hemodialysis<br />
Pr<strong>in</strong>ciple <strong>of</strong> P.E.T. ® - Performence Enhanc<strong>in</strong>g Technology<br />
Membrane capillaries, specially comb<strong>in</strong>ed with<br />
multifilament yarn<br />
Remark: Improved low molecular weight clearance by<br />
optimized dialysate flow
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Required Membrane Properties / Hemodialysis<br />
Pr<strong>in</strong>ciple <strong>of</strong> P.E.T. ® : Clearance Improvement<br />
Clearance (ml/m<strong>in</strong>)<br />
350<br />
300<br />
250<br />
200<br />
150<br />
+ 7.1%<br />
+ 6.7%<br />
DIAPES (1.7m²) without P.E.T.<br />
DIAPES (1.7m²) with P.E.T.<br />
+ 7.4%<br />
Q B = 400ml/m<strong>in</strong><br />
Q D = 500ml/m<strong>in</strong><br />
Q F = 10 ml/m<strong>in</strong><br />
+ 6.6%<br />
Urea Creat<strong>in</strong><strong>in</strong>e Phosphate Vit B12
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Required Membrane Properties / Oxygenation<br />
� O 2 <strong>and</strong> CO 2 transfer rates <strong>in</strong>fluenced by pore structure<br />
(� TIPS – process)<br />
� Plasma breakthrough <strong>in</strong>fluenced by hydrophobicity <strong>of</strong><br />
polymer (PP or PMP) <strong>and</strong> membrane structure<br />
(sk<strong>in</strong> � PMP)<br />
� Hydrodynamics <strong>of</strong> blood flow <strong>in</strong>fluenced by membrane<br />
make-up<br />
(� mat formation)
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Required Membrane Properties / Oxygenation<br />
Mat formation to optimize hydrodynamics <strong>of</strong> blood flow<br />
Polyester warp thread<br />
100 % visual <strong>in</strong>spection<br />
Cross-wound mat
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Required Membrane Properties / Plasmatreatment<br />
� High plasma flux<br />
(� surface porosity <strong>and</strong> pore size)<br />
� Appropriate <strong>in</strong>ner diameter<br />
(� optimal hydrodynamics)<br />
� Smooth surface<br />
(� no damage <strong>of</strong> cells)
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
<strong>Industrial</strong> Applications
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Selection <strong>of</strong> Typical <strong>Industrial</strong> Applications<br />
<strong>Membranes</strong>: e.g. MicroPES ® , DuraPES ® , UltraPES, Celgard ®<br />
� Filtration <strong>of</strong> liquids<br />
� water, w<strong>in</strong>e, beer, milk, fruit juices<br />
�prefiltration or f<strong>in</strong>al filtration with different pore sizes<br />
� >1 µm down to 0.05 µm <strong>in</strong> Micr<strong>of</strong>iltration<br />
� cut-<strong>of</strong>f 50 – 150 kD <strong>in</strong> Ultrafiltration<br />
� cut-<strong>of</strong>f < 50 kD <strong>in</strong> Nan<strong>of</strong>iltration<br />
� Sterile filtration <strong>in</strong> pharmaceutical processes � ultraclean water<br />
� nom<strong>in</strong>al pore size 0,2 µm (Micr<strong>of</strong>iltration) � retention <strong>of</strong> pseudomonas dim<strong>in</strong>utas<br />
� mechanical stability � manufactur<strong>in</strong>g <strong>of</strong> pleated cartridges<br />
� high porosity � high water fluxes<br />
� low adsorption � high service life<br />
� second filtration step: Ultrafiltration � modules with capillaries<br />
� last step: Reverse Osmosis<br />
� Endotox<strong>in</strong> filters � ultraclean dialysate <strong>in</strong> cl<strong>in</strong>ics<br />
� high porosity � high water fluxes<br />
� adsorption <strong>of</strong> endotox<strong>in</strong>s � safety, no breakthrough<br />
� Oil / water separation<br />
� Degass<strong>in</strong>g<br />
Typical polymers: PSu, PES, PP, CA, PVDF, PTFE<br />
Many other applications not mentioned
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Selection <strong>of</strong> Typical <strong>Industrial</strong> Applications<br />
Typical Pharmaceutical UPW system<br />
Multimedia<br />
filtration RO<br />
Po<strong>in</strong>ts<br />
<strong>of</strong> Use<br />
Reclaim<br />
Water<br />
Reclaim<br />
Tank<br />
Membrane<br />
Deaerator<br />
CO2<br />
Removal<br />
UV<br />
Micr<strong>of</strong>iltration<br />
Ultrafiltration<br />
Polish<strong>in</strong>g<br />
Bed<br />
Recycle<br />
UV<br />
UV<br />
Micr<strong>of</strong>iltration<br />
DI Beds<br />
Membrane<br />
Degasifier<br />
Dissolved O2 &<br />
N2 Removal<br />
UV<br />
Ultrafiltration<br />
Mixed<br />
Bed<br />
Storage<br />
Tank<br />
Ozonation
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Module Manufactur<strong>in</strong>g
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Module Manufactur<strong>in</strong>g / Requirements<br />
�Hous<strong>in</strong>g<br />
- stability aga<strong>in</strong>st mechanical stress, heat, pressure, chemicals <strong>and</strong><br />
low amount <strong>of</strong> extractables<br />
�Pott<strong>in</strong>g material<br />
- see above <strong>and</strong> additionally good adhesion properties � no leaks<br />
�General construction<br />
- high membrane surface area, flow distribution, exchangeability (complete <strong>and</strong> <strong>of</strong><br />
membrane elements), cleanability
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Module Manufactur<strong>in</strong>g / Examples<br />
Liqui-Cel ® Degasifier with Celgard ®<br />
215 m 2 membrane area<br />
Aqueous<br />
Stream<br />
Aqueous<br />
Stream<br />
Cartridge<br />
Vacuum <strong>and</strong>/or<br />
Strip Gas<br />
Distribution Tube<br />
Hollow fiber Membrane<br />
Baffle<br />
Collection Tube<br />
Hous<strong>in</strong>g<br />
Strip<br />
Gas
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Module Manufactur<strong>in</strong>g / Examples<br />
R<br />
Ultrafiltration module with UltraPES
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Module Manufactur<strong>in</strong>g / Examples<br />
Membrana Module Assortment
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Summary
<strong>Production</strong> <strong>Aspects</strong> <strong>of</strong> <strong>Membranes</strong><br />
Summary<br />
� Polymers <strong>and</strong> solvents have to be chosen accord<strong>in</strong>g to the production<br />
process, costs, environmental aspects <strong>and</strong> determ<strong>in</strong>ed application<br />
� All together these parameters / set-ups are determ<strong>in</strong><strong>in</strong>g the membrane<br />
structure<br />
� Special steps <strong>in</strong> the production like addition <strong>of</strong> additives, polymer<br />
functionalization or <strong>in</strong>telligent make-ups are aid<strong>in</strong>g to <strong>in</strong>crease the<br />
performance <strong>of</strong> membranes or membrane devices<br />
� The needs <strong>of</strong> membrane or membrane device performance are def<strong>in</strong>ed<br />
either by the application or by customer requirements<br />
� Therefore, the membrane manufacturer has to provide a variety <strong>of</strong> all the<br />
items mentioned above<br />
� Module design requires additional know how <strong>and</strong> has to fit to membrane<br />
properties<br />
� Comb<strong>in</strong>ation <strong>of</strong> both areas <strong>of</strong> knowledge <strong>in</strong> one company
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