Membrane Types and Factors Affecting Membrane Performance
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1 Advanced Membrane Technologies Stanford University, May 07, 2008 Membrane Types and Factors Affecting Membrane Performance Mark Wilf, Ph.D. Tetra Tech
2 Outline Membrane filtration (low pressure applications) Membrane materials and modules configuration Modes of operation Relevant R&R directions Reverse osmosis and NF membranes (high pressure applications) Membrane materials and modules configuration Modes of operation Relevant R&D directions
3 Membrane filtration
4 THE FILTRATION SPECTRUM um A MOLECULAR WEIGHT ,000 20, , ,000 Aqueous salts Carbon black Paint pigment RELATIVE SIZE OF COMMON MATERIALS Metal ions Pyrogens Virus Colloidal silica Bacteria Yeast cells Pollens Beach sand Sugars Albumin protein Milled flour FILTRATION TECHNO- LOGY Reverse Osmosis and NF Ultrafiltration Microfiltration Particle filtration
5 UF/MF terms TMP trans membrane pressure TMP = (P f + P c )/2 P p P f = feed pressure P c = concentrate pressure P p = permeate pressure SP specific permeability SP = Q/(A m * TMP) Q filtrate flow rate A m membrane area
6 MWCO Determination. Feed Pressure 1 bar (15 psi) R ejection [% ] 90% rejection for 200,000 MW E+03 1.E+04 1.E+05 1.E+06 1.E+07 Molecular weight, Daltons
![] 90% rejection for 200,000 MW 100 80 60](/docs-images/40/11405212/images/page_6.jpg "40 20 0 1.E+03 1.E+04 1.E+05 1.E+06 1.")
7 Commercial MF/UF membrane material CA Cellulose acetate PS polysulfone PES Polyether sulfone PAN Polyacrilonitrile PVDF Polyvinylidiene flouride PP Polypropylene PE Polyethylene PVC Polyvinyl chloride
8 Important membrane material property High porosity Narrow pore distribution or sharp MWCO High polymer strength: elongation, high burst and collapse pressure Good polymer flexibility Permanent hydrophilic character Wide range of ph stability Good chlorine tolerance Low cost
9 Preferred UF/MF membrane materials High mechanical strength & durability PVDF Polyvinylidiene flouride PS polysulfone PES Polyether sulfone PAN Polyacrilonitrile Low polymer cost PE Polyethylene
10 Membrane manufacturing and configuration Spinning capillary Casting flat sheet Extrusion and stretching capillary, flat sheet Thermally induced phase separation (TIPS) Supported, unsupported membranes Hollow fibers modules, spiral modules, plate and frame modules, other configurations
11 Polymer dope Bore liquid Polymer dope reservoir Spinneret detail Gear pump Spinneret Pump Bore liquid reservoir collection drum Coagulation bath Rinse bath Capillary membrane manufacturing process
12
13 PRESSURE DRIVEN CAPILLARY TECHNOLOGY
14 Pressure driven membrane cross section inside out operation Filtration Flow Path Outside Separating Layer Lumen (Feed)
15 Pressure driven membrane cross section outside in operation Outside (Feed) Separating Layer Filtration flow direction Lumen (Filtrate)
16 Configuration of pressure driven, capillary membrane module Feed Concentrate Filtrate Quick release end cap Filtrate Core Tube Maximize membrane area 100% Hydraulic sealing Potting Resin End Cap Integral connection with filtrate core tube Light weight & streamlined design
17 Example of pressure driven membrane module 0.8 mm fibre 1.2 mm fibre HYDRAcap 40: 30 m 2 (320 ft 2 ) 19 m 2 (200 ft 2 ) HYDRAcap 60: 46 m 2 (500 ft 2 ) 30 m 2 (320 ft 2 )
18 TMP = (P f + P c )/2 P p SP = Q/(A m * TMP) Example of permeability results Test parameter P f, bar (psi) P c, bar (psi) P p, bar (psi) TMP, bar (psi) Q, l/hr (gpd) A m, m 2 (ft2) SP, l/m 2 -hr (gfd/psi) New membrane 0.25 (3.6) 0.15 (2.2) 0.10 (1.5) 0.10 (1.5) 3,500 (22,000) 46.5 (500) 750 (29) Field conditions 0.70 (10.1) 0.60 (8.5) 0.15 (2.2) 0.50 (7.2) 5,100 (32,300) 46.5 (500) 219 (8.9)
19 Integrity test procedure (ASTM D ) Off line tests Bubble point test Pressure hold test Diffusive air flow test Vacuum hold test Continuous (on line) tests Particle passage counting/monitoring Marked particles passage Turbidity measurements Acoustic sensing
20 Integrity test procedure pressure or vacuum hold Pressure decay rate (PDR) PDR = (Pi-Pf)/t Pi initial pressure Pf final pressure t time interval PDR = PDR (measured) rate of diffusion Vacuum decay rate (VDR) VDR = VDR (measured) rate of diffusion
21 Integrity test sequence HYDRABLOC Pressure Decay Rates with One Broken Fiber P ressure, psi Pressure, bar Pressure Decay T ime, minutes 0 10xHYDRAcap60 20xHYDRAcap60 Diffusion Only (No Breaks) 24xHYDRAcap60 48xHYDRAcap60 Single Module
22 Schematics of pressure driven capillary unit
23 PRESSURE DRIVEN CAPILLARY SYSTEM Process step Objective Duration Frequency Forward flow Permeate production min Continuous Backwash Foulants removals sec Every min Chemicals enhanced backwash (CEB) Foulanlts removal 1 15 min Once twice a day Cleaning in place Foulants removal 2 4 hr Every 1 6 months Integrity test Verification of membrane integrity 20 min Every 1 7 days
24 Isometric GA of HYDRAbloc 2D1288 Pressurized UF train ~ 2MGD filtrate flow
25 Vacuum driven membrane cross section outside in operation Outside (Feed) Separating Layer Filtration flow direction Lumen (Filtrate)
26 Schematics of vacuum driven capillary unit Air blower Strainer 100 m Vacuum pump Filtrate storage & backwash tank Backwas h pump Filtrate pump CIP1 CIP2 CEB1 CEB2 CEB3 Cleaning chemicals Backwash chemicals
27 VACUUM DRIVEN CAPILLARY SYSTEM Process step Objective Duration Frequency Permeation Permeate production min Continuous Backwash & tank deconcentration Foulants removals sec Every min Chemicals enhanced backwash (CEB) Foulanlts removal 1 15 min Twice a day once per week Cleaning in place Foulants removal 2 5 hr Every 1 6 months Integrity test Verification of membrane integrity 20 min Every 1 7 days
28 ZeeWeed 1000 Cassette for lower solids applications Cassette capacity 1,500-2,000 m 3 /d
29 Submersible membrane train configuration
30 ZeeWeed 500 Cassette for High Solids Applications Cassette capacity 750-1,000 m 3 /d in MBR 2,500-3,500 m 3 /d in water filtration
31 Application Potable water Tertiary filtration Seawater filtration Flux rate range, l/m2-hr (gfd) (35 75) (20 50) (25 40) Recovery rate range, %
32 Membrane filtration commercial products
33 Aquasource Membrane materials CA High hydrophilic, very wettable Pore size 0.01 µm 35 to100kd Fibre id 0.93 mm Cl 2 resistance quite high ph tolerance Modified PS Moderately hydrophilic, wettable Pore size 0.01 µm 35 to100kd Fibre id 0.96 mm Cl 2 resistance quite high ph tolerance 1 13
34
35 Inge Membrane Modified PES Moderately hydrophilic, easily wettable Pore size; UF nm Fibre id, 0.9 mm; od 4.3 mm Cl 2 resistance moderately high ph tolerance
36 Membrane Multibore Membrane 7 single capillaries combined into one fiber PES blended with a strong, hydrophilic polymer asymmetric membrane formed from polymer blend regular foam structure as active layer support burst pressure > 13 bar (190 psi)
37 Norit Membrane PES/PVP Hydrophilic, easily wettable Pore size; UF nm Fibre id, 0.8 mm (1.5 mm); od 1.3 mm (2.5 mm) Cl 2 resistance moderately high ph tolerance Module diameter 200 mm Membrane area 40 m 2
38 Norit UF train 7000m3/day (1.9 mgd)
39 Memcor (Siemens) submersible CMF S
40 Memcor (Siemens) pressurized CP
41 Membrane Fouling in Wastewater Reclamation Fouling Processes Organic Adsorption Colloidal Material Biogrowth Scaling
42 Effect of pretreatment on operating parameters in wastewater reclamation systems 400 Energy 5 F eed p ressu re, p si Pressure Conventional pretreatment Membrane pretreatment Energy Pressure E n erg y u se kw h r/kg allo n 100 0
43 Cl 2 FeCl 3 CO 2 Wastewater treatment plant Acid and/or SI Secondary effluent Cl 2 RO wastewater reclamation with membrane pretreatment
44 Orange County, CA GWR System Secondary Effluent MF Backwash/ Waste to Head of Plant 86 MGD MF System 70 MGD RO System 70 MGD UV System RO Concentrate Ocean Outfall AOP Barrier Recharge Basins MF System Recovery: 90% 0.2 micron pore RO System Recovery: 80% - 85% 5 mgd per train Flux rate: 12 gfd UV System Low Pressure/High Output 8 trains with 3 vessels per train Hydrogen peroxide
45 Nitrogen and phosphorus reduction process (three stages) Iron/Alum for P reduction Filtrate Raw sewage Denitrification Aerated anoxic Nitrification DO < < DO < 0.8 DO > 2.0 Recirculation Sludge disposal
46 A Basic MBR Production Train Biological reactor 2.Membranes 3.Permeate pump & air blower 4. Control panel 5. Permeate & air piping 2 3 4
47 R&D directions membrane filtration Lower cost of membrane products Reduction of energy requirement Permanent hydrophilic membranes Reduction of fouling tendency Easy identification of integrity breach Simplified system configuration Replacement of chemical membrane cleaning with biological processes
48 Desalination
49 Energy usage in desalination processes Energy, kwhr/m Evaporation Reverse Osmosis MSF MED VC SWRO BWRO WW RECL MSF Multistage flash, MED Multieffect distillation, VC Vapor compression, SWRO Sea water RO, BWRO Brackish water RO, WWRECL- Wastewater reclamation
50 COMMERCIAL MEMBRANES AND MEMBRANE MODULE CONFIGURATIONS
51 N HC O C O H N C O H N O O O O O O C C C C C C C O O O H H H H H H H Chemical structure of cellulose triacetate (A) and polyamide (B) membrane material A B H H
52 Support fabric Trough with polymer solution Finished polysulfone UF membrane Manufacturing process of polysulfone membrane support
53 Amine solution Polysulfone membrane Oven TMC solution Amine rinse bath PA membrane Manufacturing process of polyamide membrane barrier on polysulfone support
54 Semipermeable membrane layer ~2000 Angstrom Microporous polymeric support Fabric backing 0.2 mm 0.008"
55 PA membrane surface Polymeric support Fabric backing
56 Evolution of performance of brackish membranes S p e c. f lu x, l/m 2 - h r- b a r & s a lt p a s s a g e, % Cellulose acetate Polyamide Spec flux Salt Pass
57 Evolution of performance of seawater membranes S p e c. f lu x, l/m 2 - h r- b a r & s a lt p a s s a g e, % CA PA Spec flux Salt Pass
58 Feed Brine Spacer Concentrate Product Membrane Permeate Carrier
59 Feed channel 0.7 mm (0.031 ) Feed spacer configuration Configurations of feed channel and feed spacer net
60 Osmotic pressure is function of concentration and temperature Salinity, ppm TDS 5,000 20,000 35,000 70,000 80,000 30C (86 F) 3.3 bar (48 psi) 13.9 bar (201 psi) 25.7 bar (372 psi) 51.3 bar (744 psi) 59.0 bar (856 psi) 15C (59 F) 3.2 bar (46 psi) 13.2 bar (191 psi) 24.5 bar (355 psi) 48.8 bar (708 psi) 56.1 bar (813 psi)
61 RO TERMS NDP - net driving pressure Driving force of the water transport (flux) through the membrane. NDP = P f - P os - P p P d (+ Perm os ) P f - feed pressure P os average feed osmotic pressure P p P d - permeate pressure - pressure drop across RO element Perm os - permeate osmotic pressure
62 Seawater system: 40,000 ppm TDS, 50% recovery 70 P ressure, bar Feed pressure Net driving pressure Osmotic pressure Concentrate pressure Element position
63 Concentration factor in RO system Concentration factor CF = 1/(1-R) CF = 0.5*(1+1/(1-R)) CF = ln(1/(1-r))/r Concentrate Arithmetic average Logarithmic average Recovery rate, %
64 Concentration polarization Membrane ions concentration level in feed
65 RO TERMS TCF - temperature correction factor Temperature affects water and salt transport across the membrane, approximately at the same magnitude. The transport rate changes at about 3% per degree C. TCF = 1/exp(2700 (1/(273+t)-1/298)) t temperature C
66 RO TERMS Water transport, Qw : Qw = Kw A NDP TCF Kw water transport coefficient A - membrane area Salt transport, Qs : Qs = Ks A C TCF Ks salt transport coefficient C - salt concentration gradient
67 RO TERMS Permeate salinity Cp Qs/Qw = Ks A C TCF/ Kw A NDP TCF = Ks C / Kw NDP C recovery rate NDP feed pressure
68 8 and 16 diameter elements 8 element Membrane area 40m2 (430 ft2) Nominal flow 45 m3/day (12,000 gpd) Avg. field flow 19 m3/day (5,000 gpd) 16 element Membrane area 140 m2 (1,500 ft2) Nominal flow 155 m3/day (41,000 gpd) Avg. field flow 68 m3/day (18,000 gpd)
69 Permeate flow per vessel at an average permeate flux rate of 20.4 l/m2-hr (12 GFD) Elements per vessel 8 37 m2/el. (400 ft2/el.) 8 40 m2/el. (430 ft2/el.) m2/el. (1,500 ft2/el.) m3/day (72,000 GPD) m3/day (90,000 GPD) m3/day (28,800 GPD) 117 m3/day (31,000 GPD) 408 m3/day (108,000 GPD) m3/day (33,600 GPD) 136 m3/day (36,000 GPD) 477 m3/day (126,000 GPD) m3/day (38,400 GPD) 156 m3/day (41,300 GPD) 545 m3/day (144,000 GPD)
70 Water flow in a pressure vessel assembly 10 m3/hr (44 gpm) feed 5 m3/hr (22 gpm) permeate 5 m3/hr (22 gpm) concentrate
71 PG Pressure vessel, 1st stage Permeate FI Pressure vessel, 1st stage Feed Pressure vessel, 1st stage Pressure vessel, 1st stage Pressure vessel, 2nd stage PG Pressure vessel, 2nd stage FI Concentrate Two Stage RO System
72 Concentrate manifold Permeate manifold Permeate sampling panel Local display panel Two-stage brackish unit, 32:14 (7M) array 4.0 X 2.9 X 8 m, 8000 m3/d 13.1 X 9.5 X 26, 2.1 mgd Feed manifold
73 RO membrane categories Nanofiltration for color removal Nanofiltration for sulfate reduction Nanofiltration for hardness reduction Low pressure brackish RO High rejection brackish RO Low pressure seawater RO High rejection seawater RO
74 Commercial offering of nanofiltration RO membrane modules Element model Hydracore ESNA-LF SU620F NF-90 NF-270 Membrane area, m2 (ft2) 37.1 (400) 37.1 (400) 37.1 (400) 37.1 (400) 37.1 (400) Permeate flow, m3/d (gpd) 31.0 (8,200) 29.5 (7,800) 21.9 (5,800) 37.9 (10,000) 47.3 (12,500) Salt rejection, Test flux rate, l/m2-hr (gfd) 34.8 (20.5) 33.2 (19.5) 24.7 (14.5) 42.5 (25.0) 55.9 (32.9) Permeability, l/m2-hrbar (gfd/psi) 7.7 (0.31) 7.2 (0.29) 8.7 (0.35) 11.9 (0.48) 15.7 (0.63) Relative salt transport: salt passage flux rate 17.4 (10.2) 6.6 (3.9) 11.1 (6.5) 1.3 (0.8) 1.7 (1.0)
75 Commercial offering of brackish RO membrane modules Element model ESPA2+ ESPA4+ TMG BW30- XLE440 BW30 LE- 440 Membrane area, m2 (ft2) 40.0 (430) 40.0 (430) 40.0 (430) 40.9 (440) 40.9 (440) Permeate flow, m3/d (gpd) 41.6 (11,000) 49.2 (13,000) 41.6 (11,000) 48.1 (12,700) 48.1 (12,700) Salt rejection, Test flux rate, l/m2-hr (gfd) 43.5 (25.6) 51.3 (30.2) 43.5 (25.6) 49.1 (28.9) 49.1 (28.9) Permeability, l/m2-hr-bar (gfd/psi) 5.0(0.20) 8.2 (0.33) 6.2 (0.25) 7.7 (0.31) 6.0 (0.24) Relative salt transport: salt passage flux rate (0.153) (0.181) (0.128) (0.289) (0.202)
76 Commercial offering of seawater RO membrane modules Element model SWC4+ SWC5 TM SW30HR- LE SW30HR- XLE Membrane area, m2 (ft2) 37.1 (400) 37.1 (400) 37.1 (400) 37.1 (400) 37.1 (400) Permeate flow, m3/d (gpd) 24.6 (6,500) 34.1 (9,000) 24.6 (6,500) 26.5 (7,000) 34.1(9,000) Salt rejection, Test flux rate, l/m2-hr (gfd) 27.6 (16.3) 38.2 (22.5) 27.6 (16.3) 31.3 (18.4) 38.2 (22.5) Permeability, l/m2-hrbar (gfd/psi) 1.0 (0.04) 1.5 (0.06) 1.0 (0.04) 1.2 (0.05) 1.5 (0.06) Relative salt transport: salt passage flux rate (0.032) (0.045) (0.041) (0.046) (0.067)
77 SPECIAL NANOFILTRATION MEMBRANE (HYDRACORE)
78 HYDRACoRe Nanofiltration for color removal 1000 MWCO 50% salt rejection, minimizes product water instability and need for post treatment 8,200 gpd for a 365 sq ft element Chlorine tolerant
79 Surface of HydraCoRe at 4000 X magnification Typical Interfacial Polyamide RO Membrane HydraCoRe Membrane
80 HydraCoRe ion rejection Anion A - A 2- Cation Cl SO 4 Molecular Weight M + Na 23 50% 90% M 2+ Mg 24 20% 35% Ca 40 12% -
81 Orange County Groundwater Basin Cross-Section
82 Irvine Ranch Project membrane elements testing Parameter Feed HydraCoRe permeate Conventional Nanofiltration permeate Color, CU 200 <5 <5 Conductivity us/cm Calcium mg/l Specific flux 0.43 (10.7) 0.48 (11.9) gfd/psi (l/m3-hr-bar)
83 Irvine Ranch Plant hydraulics Permeate 28,000 m3/day (7.35 MGD), Concentrate 2400 m3/day (0.64 MGD), Recovery 92% 1,160 m3/hr (5,100 gpm) 102 m3/hr (450 gpm)
84 Irvine Ranch Plant concentrate flow reduction Permeate 30,000 m3/day (7.90 MGD), Concentrate 600 m3/day (0.16 MGD), Recovery 98% R = 92% 1,330 m3/hr (5,485 gpm) R = 85% 25 m3/hr (111 gpm)
85 Irvine Ranch NF Plant: Feed, Permeate and Concentrate Samples Feed Permeate Concentrate
86 High water ph shifts equilibrium to the right B(OH)3 (aq) + H2O H+(aq) +B(OH)4- (aq) Low water ph shifts equilibrium to the left
87 Seawater RO system. Recovery rate 50%. Boron concentration in feed 5.0 ppm Feed ph Boron rejection, % Boron passage, % Boron in permeate, ppm
88 Brackish RO system. Recovery rate 85%. Boron concentration in feed 2.0 ppm Feed ph Boron passage, % Boron in permeate, ppm Boron in passage, % Boron in permeate, ppm Brackish membranes Seawater membranes
89 Boron species distribution at 25 C Fraction of B(OH) Low salinity Seawater Concentrate ph of solution
90 Second pass RO system. Recovery rate 90%. Boron concentration in feed 1.4 ppm Feed ph Boron rejection, % Boron passage, % Boron in permeate, ppm
91 Seawater RO. Combined recovery rate 50% ph = B = 5.0 ppm ph = 10.4 B = < 1.0 ppm Rec. = 50% 100 Pass 1 50 Scale inhibitor NaOH 50 Single pass system with ph adjustment of the 1st pass feed
92 R&D directions reverse osmosis Selective rejection of dissolved species Higher boron rejection Increased water permeability without increasing solute transport Reduction of fouling tendency Control of biofouling in seawater systems Replacement of chemical membrane cleaning with biological processes Reduction of scaling tendency in brackish RO processes
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