Outline • Introduction • Membrane Issues • Other Issues Outline • Introduction • Membrane Issues –General fouling –Impact of SRT or F/M –Impact of MLSS –Impact of wet weather • Other Issues What is membrane fouling? • Membrane fouling is the loss of permeability with time • In practice, this is observed as an increase in the TMP required to maintain flow through the MBR • For engineers, the increase in TMP needs to be related to the flux rate and normalized for temperature this is called a temperature corrected “Permeability” or “Specific Flux” Definition of terms Po J = Q/A = membrane flux (m/s) Membrane permeability = J/TMP Pe TMP = Po-Pe (Pa) A Membrane fouling: TMP time Permeability J LP = TMP Typical units in USA: gal/(ft2.d.lb/in2) or gfd/psi Europe and Asia: L/(m2.h.bar) or LMH/bar Strict SI Units: m2.s/kg Temperature corrected permeability o 20 C P L = J⋅e (-0.0239(T -20)) TMP The above equation corrects for temperature effects on the viscosity of water. This equation is accurate within 5% for a temperature range of 5 to 40oC. WHY DO WE DO THIS?? Because changes in the viscosity of water directly impact TMP Temperature correction 2.0 1.6 Absolute viscosity of water, mPa•s As water temperature decreases viscosity of water increases Need to use a different equation 1.8 1.4 1.2 1.0 0.8 0.6 0.4 0.2 Actual Calculated All other conditions equal this increases the TMP 0.0 0 5 10 15 20 25 Temperature, ºC 30 35 40 45 Key MBR Research Projects List of Key Research Projects • 1999-2000 WERF study in San Diego • 1999-2000 Bureau of Reclamation II Study in San Diego • 2000-2004 STOWA project in the Netherlands • 2002-2005 WERF study in San Francisco • 2001-present King County in Seattle • 2003-2004 Bureau of Reclamation III Study in San Diego • 2002-present On-going research by Anjou Recherche • 2006-present EU funded Amadeus initiative Understanding MBR Fouling MBR fouling theory • Basic fundamentals of membrane fouling in MBRs are the same regardless of the manufacturer or configuration (Pressure or Vacuum) • Membrane fouling results from the interaction between the mixed liquor and membrane material – Complex mixture of organics – Metabolic byproducts and possibly influent substrate or partially degraded influent substrate – Cells and microbes – Cellular and microbial debris – Inert suspended solids – Dissolved inorganics (possible precipitants) Resistance in-series model • Simplistic model • Widely used with low-pressure membranes (MF/UF/MBR) • Can be used to provide powerful insights to MBR fouling TMP J= µw ⋅ R T J = membrane flux, m/s TMP = trans-membrane pressure, Pa µw = absolute viscosity of water, kg/m.s RT = total resistance to filtration, m-1 Resistance in-series model • • • • • RT=RM+RF+RC RT = Total resistance RM = Membrane RC = Cake Layer RF = Foulants – – – Organic Adsorption Inorganic Precipitation Pore blocking Membrane resistance, RM Determining RM 90000 80000 70000 60000 TMP (Pa) • RM is the hydraulic resistance due to the membrane alone • RM can be determined by performing a clean water flux profile on a clean membrane • Record TMP and temperature for 3 different flux rates • Plot TMP vs. m*J, slope is RM 50000 RM = 3x1012 m-1 40000 30000 20000 y = 3E+12x + 21823 R2 = 0.9996 10000 0 5.E-09 6.E-09 7.E-09 8.E-09 9.E-09 Viscosity * Flux (kg/s 2 ) 1.E-08 Other resistance terms • RT is obtained during normal MBR operation R T = – – – TMP µw ⋅ J Increases with time or total volume filtered Influenced by resistance of the filtration cake, RC Influenced by the degree of foulant present on the membrane, RF • RF can be roughly estimated at any point in an operation cycle – Drain the mixed liquor from the membrane tank (air off) – Fill the membrane tank with membrane permeate and perform flux profile - this provides RM+RF (possibly some residual RC that’s why this is an estimate) • Subtract RM (this was obtained before run began) and you can approximate the amount of foulant, RF • Remainder of RT is attributed to RC Hydrodynamic force balance • Membrane flux controls the rate of material transported to the membrane surface, JSS • The lift force controls the rate at which rejected material is re-suspended to the bulk solution, VL • Normal MBR operation – Jss ≤ VL – i.e. Operating at subcritical flux Critical Flux Critical flux • Conventionally denotes flux below which fouling does not take place – Membrane permeability remains as it was in pure water • Strict critical flux definition does not apply to MBR • Field et al., 1995 first adapted this concept to low pressure membranes • Le-Clech et al., 2003 further developed the critical flux concept for MBRs Illustration of critical flux 20 MLSS = 8 g/L SCFM = 30 scfm gfd 8.7 18 gfd 10.9 gfd 13.1 gfd 15.3 gfd 17.5 Vacuum Pressure, in Hg 16 14 12 10 8 6 4 2 0 0 2 4 6 Time, minutes 8 10 Factors affecting critical flux • Specific MBR hydrodynamics – Hollow fiber versus flat sheet – Coarse aeration distribution – Pressure vs. Vacuum MBR systems • Mixed liquor properties – Degree of flocculation » More disperse flocs with higher colloidal material is different than a well-flocculated sludge – Viscosity » The mixed liquor viscosity impacts the efficiency of VL » Higher viscosity - lower scouring efficiency Importance of coarse bubble air Adapted from Bérubé et al., 2005 AWWA MTC Constant flux experiments Single Phase = Water alone Dual Phase = Air/Water Conclusion: Maintaining clean, well-functioning, and well-distributed coarse bubble air is critical Cross-flow velocity Sludge Properties Colloidal Material Filamentous Microorganisms Particle Size Extracellular Polymeric Substances (EPS) Critical Flux Illustration MLSS = 10-12 g/L Air = 30 scfm Adapted from Fan et al., 2006 Water Research V40 RM RF RC –Jss = to membrane –VL = away from membrane –Jss ≥ VL (rapid fouling) “Typical” MBR Fouling Mechanisms Photos adapted from Miura et al., 2007 “Typical” MBR fouling mechanisms • Organics are the most common foulant under normal operating conditions in MBRs – – – Conservative flux Well functioning/distributed coarse aeration Controlled MLSS • Organic fouling is primarily attributed to the soluble or colloidal organics present in the mixed liquor – Particles ≤ 6 µm – Not incorporate into larger floc – Not yet clear whether colloidal or soluble is culprit (likely both) » Research has highlighted the importance of soluble carbohydrate or polysaccharides, but there is also literature to the contrary • Increased soluble/colloidal organic content results in increased membrane fouling rates Extracellular Polymeric Substances (EPS) and Soluble Microbial Products (SMP) Hydrolysis EPS Active Cell SMP Diffusion/Shear Adsorption and flocculation Substrate Organic fouling Adapted from Lesjean et al., 2005 Water Science and Technology Organic fouling 70 Total SMP = 7.0x + 36.8 2 R = 0.77 SMP concentration, mg/L 60 50 40 30 20 SMP = soluble microbial products (soluble protein + soluble carbohydrate) 10 0 0.0 0.5 1.0 1.5 2.0 2.5 Steady-state fouling rate, LMH/bar • d Adapted from Trussell et al., 2006 3.0 3.5 4.0 Inorganic foulants • Less severe than organic fouling for most municipal MBR applications • Certain waters (e.g. hard waters) can slowly develop an inorganic fouling layer – Low pH clean (most common is citric acid) will control this – This clean can be done as infrequently as annually at many facilities • Coagulants are typically used in municipal wastewater treatment facilities – High coagulant doses create hydroxide precipitants (e.g. Fe(OH)3), or coagulant carryover (e.g. colloids not bound up in mixed liquor) that will result in inorganic fouling – It appears that an occasional low dose of coagulant can help reduce soluble and colloidal organic fouling Coagulant Addition Adapted from Holbrook et al., 2004 Water Environment Research Polymer Addition • Benefits of specialized polymer addition or “flux enhancers” are currently being researched – Reduces mixed liquor organic content (SMP) – Allows for increase in membrane flux by reducing colloidal organics • Benefits have not been demonstrated on long-term basis – Short-term increase in mixed liquor filterability occurs – High doses required for longer run times – Long-term impacts on sludge properties (e.g. post-polymer addition) have not been demonstrated Polymer Addition Adapted from Yoon et al., 2005 Water Science & Technology Other Important Fouling Mechanisms Changes in MLSS concentration • Increases in the MLSS concentration are important – Increases the JSS to the membrane surface – Increases the mixed liquor viscosity – Combination can result in operation above the critical flux without changing the membrane flux • Different researchers have reached different conclusions on the “maximum” MLSS concentration for membrane fouling • This is because the “maximum” MLSS depends on – Membrane hydrodynamics (e.g. flat sheet, hollow fiber, pressure vs. vacuum, etc.) – Membrane flux rate – Re-suspending efficiency (e.g. air rate, no air? - cross flow velocity, “jet”, mixed liquor viscosity) Changes in mixed liquor properties • Mixed liquor viscosity can change dramatically without the MLSS concentration changing! – Mixed liquor viscosity has been > 2 times greater depending on properties (e.g. 200 vs. 400 mPa.s at 18 g/L) – Mixed liquor viscosity depends upon the degree of flocculation, extracellular polymeric substance (EPS) concentration, and filament concentration • Mixed liquor filterability can change without changing MLSS concentration – If de-flocculation occurs, a dramatic increase in the RC will occur » » » Increase in colloidal content Disperse flocs and single cells Dramatic changes can be quantified by time to filter (TTF) Mixed liquor viscosity Adapted from Cui et al., 2003 Other important mixed liquor properties for MBR fouling • Key foulants arise from biomass, termed extracellular polymeric substances (EPS) – unbound fraction often referred to as soluble microbial product (SMP) – bound fraction (EPS) • These can be further fractionated into chemical types, namely: – polysaccharide (or carbohydrate) – protein Chemical foulant studies • Difficult to ubiquitously identify key foulant • Generally, high concentrations of SMP are a significant concern – Membrane fouling will increase – New research is showing importance of molecular weight of soluble organic (e.g. >10 kDa and < 100 kDa) • High concentrations of EPS do not always result in increased fouling rates – High EPS can be a sign of good flocculation (e.g. low colloidal and soluble organic content) – “Sticky” EPS can result at low EPS concentrations and produce high RC Is Pore Size Important? MF vs UF • A much debated topic • Some believe that MF has a higher fouling tendenacy than UF membranes • Some believe the MF and UF membranes in MBRs will produce significantly different effluent water qualities, possibly impact reactor design by the retention of additional organics • Hermanowicz et. al (2006) clarified a Novak publication that suggested whether an MBR is MF or UF would impact the biological design – Having either an MF or UF produced similar COD at the same conditions Dynamic Cake Layer (Lee et al. 2001) • Solids (microbial floc) protect the membrane from direct exposure to organics • Acts as a “secondary” membrane • Membrane fouling rate will increase with a less effective dynamic cake layer – Poor flocculation US Bureau of Rec. Report (2000) Rapid fouling attributed to MF module Impact of SRT or F/M on Membrane Fouling Rationale F So = M θ H ⋅ X MLVSS • The SMBR process is currently limited to an MLSS concentration of 10 g/L • The F/M ratio is a key parameter to optimize reactor tank design – Small tank (low HRT) – Small tank (high F:M) Rationale Present Worth, $ Capital O&M θH, time Equipment and Apparatus • Pilot-scale SMBR • Treating primary effluent from the City of San Francisco’s SEP – COD = 325 mg/L – TSS = 98 mg/L Membrane Operation and Characteristics Zenon 500C Module Nominal = 0.035 µm Flux = 30 L/m2.h Air = 14 L/s Intermittent aeration • 9 min operating cycle followed by 30 sec relax • • • • • Experimental Methods • Initial operating conditions: MCRT = 10 d (F/M = 0.34 gCOD/gVSS.d) • Dissolved oxygen > 2 mg/L • Constant MLSS = 8g/L • Steady-state data collection began after 3 MCRTs • 2 week steady-state data collection period • MCRT was steadily decreased (5, 4, 3, 2 d) – F/M (0.53, 0.73, 0.84, 1.4 gCOD/gVSS.d) Membrane Performance at 10-d MCRT (F/M=0.34 gCOD/gVSS.d) Flux Specific Flux 300 40 Start-up Chemical Clean Large Foam Event 35 30 200 o 25 Specific Flux @ 20 C, LMH/bar 250 20 150 15 100 10 50 5 0 50 70 90 110 130 Days of Operation 150 170 0 190 Membrane Performance at 5-d MCRT (F/M=0.53 gCOD/gVSS.d) Flux Specific Flux 40 300 35 30 200 25 150 20 15 100 10 50 5 0 180 190 200 210 220 230 240 Days of Operation 250 260 270 0 280 Specific Flux @ 20oC, LMH/bar 250 Membrane Performance at 4-d MCRT (F/M=0.73 gCOD/gVSS.d) Flux Specific Flux 40 300 Intermittent Coarse Air Failure Foam Event 35 30 200 25 150 20 15 100 10 50 5 0 270 280 290 300 Days of Operation 310 320 0 330 Specific Flux @ 20oC, LMH/bar 250 Membrane Performance at 3-d MCRT (F/M=0.84 gCOD/gVSS.d) Flux Specific Flux 300 40 Routine Feed Line Cleaning Routine Feed Line Cleaning Intermittent Coarse Air Failure 35 30 200 25 20 150 15 100 10 50 5 0 355 360 365 370 375 380 Days of Operation 385 390 0 395 Specific Flux @ 20oC, LMH/bar 250 Membrane Performance at 2-d MCRT (F/M=1.4 gCOD/gVSS.d) Flux Specific Flux 40 300 Foam Event 35 30 200 25 20 150 15 100 10 50 5 0 390 395 400 405 Days of Operation 410 0 415 Specific Flux @ 20oC, LMH/bar 250 Effect of F/M on Steady-State Fouling Rate MCRT, d 10 5 4 3 2 4.0 3.5 3.0 y = 1.661x2.1977 R2 = 0.9517 2.5 2.0 1.5 1.0 0.5 0.0 0.0 0.2 0.4 0.6 0.8 F/M, g COD/g VSS.d 1.0 1.2 1.4 1.6 Steady-state Fouling Rate vs sCOD Soluble COD COD Rejection 100 90 sCOD = 3.8x + 61.3 80 90 2 R = 0.30 70 60 60 50 COD Rejection = -1.5x + 63.0 50 R2 = 0.24 40 40 30 30 20 20 10 10 0 0 0.0 0.5 1.0 1.5 2.0 2.5 Steady-state fouling rate, LMH/bar.d 3.0 3.5 4.0 COD Membrane Rejection, % 80 70 Steady-state Fouling Rate vs SMP Protein Carbohydrate Total 70 Total SMP = 7.0x + 36.8 R2 = 0.77 60 50 40 30 SMPp = 2.8x + 20.5 R2 = 0.36 20 SMPc = 4.2x + 16.2 R2 = 0.72 10 0 0.0 0.5 1.0 1.5 2.0 2.5 Steady-state fouling rate, LMH/bar.d 3.0 3.5 4.0 Conclusions • High organic loading rates (F/M) increased membrane fouling rates • Biological foaming was controlled mechanically • Increased steady-state membrane fouling rates correlated with SMP, not sCOD • Understanding membrane fouling at high organic loading rates allows engineers to design a compact SMBR without: – excessive maintenance costs or – failing to meet the design capacity Why does high F/M cause membrane fouling Effect of F/M on Steady-State Fouling Rate MCRT, d 10 5 4 3 2 4.0 3.5 3.0 y = 1.661x2.1977 R2 = 0.9517 2.5 2.0 1.5 1.0 0.5 0.0 0.0 0.2 0.4 0.6 0.8 F/M, g COD/g VSS.d 1.0 1.2 1.4 1.6 Equipment and Apparatus • Bench-scale SMBR • Treating primary effluent from the City of San Francisco’s SEP – COD = 325 mg/L – TSS = 98 mg/L Membrane Operation and Characteristics • Mitsubishi Sterapore® • Nominal pore size = 0.4 µm • Membrane flux = 18 L/m2.h • Coarse bubble air = 0.4 L/s • 9 min operating cycle followed by 30 sec relax Experimental Methods • Operating conditions: MCRT = 10 d (F/M = 0.50 gCOD/gVSS.d) MCRT = 2 d (F/M = 2.34 gCOD/gVSS.d) • Dissolved oxygen > 2 mg/L • Constant MLSS = 1.4 g/L • Steady-state data collection began after 3 MCRTs • 2 week steady-state data collection period Tools Used to Understand Membrane Fouling • Steady-state membrane fouling rate during operation • Molecular weight distribution of influent, SMP and effluent • FTIR of clean and fouled membranes • Batch filtration experiments expressed as Modified Fouling Index (MFI) – Stir cell filtration of steady state mixed liquor with UF (NMWCO = 300 kDa, PES) – Data presented as MFI at 20oC and 210 kPa • Fouled membrane resistances Fouled Membrane Resistance Terms • R=RM+RF+RC • R = Total resistance • RM = Membrane • RC = Cake Layer • RF = Foulants – Organics Adsorption – Inorganic Precipitation Membrane Performance at 10-d MCRT (F/M=0.50 gCOD/gVSS.d) Flux Specific Flux 600 40 Start up 66 Days at 10-d MCRT (F/M = 0.50 gCOD/gVSS.d) 35 30 400 25 20 300 15 200 10 Steady-state fouling rate 100 Chemical Cleaning 5 0 0 0 10 20 30 40 Days of Operation 50 60 70 80 Specific Flux @ 20oC, LMH/bar 500 Membrane Performance at 2-d MCRT (F/M=2.34 gCOD/gVSS.d) Flux Specific Flux 40 600 25 Days at 2-d MCRT (F/M = 2.34 gCOD/gVSS.d) 35 30 Chemical Cleaning Chemical Cleaning Chemical Cleaning 400 25 20 300 15 200 Steadystate 10 100 5 Improper Wasting Volumes 0 75 80 85 90 Days of Operation 95 100 0 105 Specific Flux @ 20oC, LMH/bar 500 Steady-State Membrane Fouling Rates F/M MCRT gCOD/gVSS.d d 10 2 0.50 2.34 Steady-state Fouling Rate @ 20oC LMH/bar.d 2.60 59.0 SMPc SMPp Total SMP mg/L 24 10 mg/L 14 49 mg/L 38 59 • Membrane fouling rates increased with F/M • Total SMP concentration increased with F/M • Unlike pilot-scale work, SMPc did not increase with increasing F/M Carbohydrate Molecular Weight Increased at Low MCRT (High F/M) > 10 kDa 10 kDa - 1 kDa < 1 kDa Carbohydrate concentration, mg/L 25 20 15 10 5 0 Influent SMP - 10 d SMP - 2 d Sample Effluent - 10 d Effluent - 2 d Protein Molecular Weight Increased at Low MCRT (High F/M) > 10 kDa 10 kDa - 1 kDa < 1 kDa Protein Concentration, mg/L 70 60 50 40 30 20 10 0 Influent SMP - 10 d SMP - 2 d Sample EFF - 10 d EFF - 2 d Fouled Membrane FTIR Results 100 10-d MCRT (Green) Virgin (Blue) 80 60 2-d MCRT %T 40 20 10 4000 3000 2000 W a v e n u m b e r[c m -1 ] 3380 - indicates OH stretching 1660 and 1540 - indicates NH and COO- (protein) 1060 - indicates CO stretching of polysaccharides 1000 650 Fouled Membrane Resistance 10-d MCRT Fouling Resistance During 10 days MCRT Operation 25 Before cleaning 20 y = 4.2319x R2 = 0.9979 y = 0.4014x R2 = 0.5914 Physical y = 4.0956x 15 Chemical R2 = 0.9757 10 5 0 0 5 10 15 20 25 Viscosity * Flux (µ µg/s2) After 66 d of operation without a chemical clean 30 35 40 Fouled Membrane Resistance 2-d MCRT Fouling Resistance During 2 days MCRT Operation 25 Before cleaning y = 2.0627x R2 = 0.9919 20 15 y = 1.7468x Physical R2 = 0.9895 y = 0.4303x 10 R2 = 0.9315 Chemical 5 0 0 5 10 15 20 Viscosity * Flux (µ µg/s2) After 5 d of operation without a chemical clean 25 30 Fouled Membrane Resistance Terms B A RMembrane 9% RMembrane 21% RCake 3% RFoulant 64% RFoulant 88% R = 4.23x1012 m-1 R = 2.07x1012 m-1 Fouled membrane R distribution for SMBR: A) 10-d MCRT (0.5 gCOD/gVSS.d) B) 2-d MCRT (2.34 gCOD/gVSS.d) RCake 15% Batch Filtration Results • Operating membrane permeability was similar when analyzed 63 and 71 LMH/bar for the 2-d and 10-d MCRTs • Factor of 2 in total fouled resistance • Used a batch filtration test to better understand these differences and importance of various components to fouling • Stir cell filtration of steady state mixed liquor with UF (NMWCO = 300 kDa, PES) • Data presented as MFI at 20oC and 210 kPa Batch Filtration Results SRT, d 10 2 Modified Fouling Index, 10-3 s/L2 Mixed Liquor Soluble SS Mixture Effect 17 11 2 4 47 27 12 8 • Higher sludge resistance observed d MCRT • Reduction in sludge filterability observed as membrane fouling at 2was – Fouled resistances 4.23 (10-d) and 2.07 (2d) with measurement was made on membrane permeate – Fouled permeability 71 (10-d) and 63 (2-d) with measurement was made during operation Batch Filtration Results SRT, d 10 2 Modified Fouling Index, 10-3 s/L2 Mixed Liquor Soluble SS Mixture Effect 17 11 2 4 47 27 12 8 • MFI was higher for all fractions at MCRT = 2 d • Sludge was centrifuges at 12,000 g for 15 minutes – Soluble fraction was supernatant – Suspended solids (SS) fraction was pellet • SS was measured by resuspending pellet with batch stir cell permeate • Soluble MFI was almost 3 times higher at low MCRT • SS MFI increased 6 times at low MCRT (sticky cake) • Mixture effect was observed at both conditions SMBR Sludge- Low EPS/High Colloidal Material Activated Sludge- High EPS/Low Colloidal Material EPS Data Mean Concentration, mg/gVSS MCRT, d < 1 kDa 10 kDa - 1 kDa > 10 kDa Carbohydrate 10 4.3 17.6 7.8 2 5.5 6.8 18.3 Protein 10 30.6 46.2 14.4 2 48.5 11.3 60.9 Total 29.7 30.6 91.2 120.7 No difference in total carbohydrate concentration most commonly cited foulant More total protein at low MCRT More high molecular weight organics at low MCRT Carbohydrate EPS B A < 1 kDa 14% > 10 kDa 26% < 1 kDa 18% 10 kDa - 1 kDa 22% > 10 kDa 60% 10 kDa - 1 kDa 60% Carbohydrate Total Concentration: 29.7±1.7 mg/gVSS Carbohydrate Total Concentration: 30.6±1.5 mg/gVSS Dramatic shift between the >10kDa and 10-1 kDa range A) 10-d MCRT (0.5 gCOD/gVSS.d) B) 2-d MCRT (2.34 gCOD/gVSS.d) Protein EPS B A > 10 kDa 16% < 1 kDa 34% < 1 kDa 40% 10 kDa - 1 kDa 50% Protein Total Concentration: 91.2±6.6 mg/gVSS > 10 kDa 51% 10 kDa - 1 kDa 9% Protein Total Concentration: 120.7±20.3 mg/gVSS AGAIN - a dramatic shift between the >10kDa and 10-1 kDa range A) 10-d MCRT (0.5 gCOD/gVSS.d) B) 2-d MCRT (2.34 gCOD/gVSS.d) Conclusions • High organic loading rates (F/M) increased membrane fouling rates • Increased steady-state membrane fouling rates correlated with total SMP • MW of carbohydrate and protein SMP increased with F/M • Membrane rejected higher MW SMP • FTIR indicated protein and carbohydrate presence on fouled membranes with stronger adsorptions resulting from the 2-d MCRT condition Conclusions • Membrane fouling was primarily due to the adsorption of organics and RF was dominate resistance term of fouled membranes • RC increased with F/M and this was attributed to changes in floc properties that result in a “sticky” cake • Sludge filtration resistance (MFI) increased with F/M • MFI of suspended solids increased 6 times, supporting the increasing importance of the cake layer with increasing F/M