Forward Osmosis Principles, Trends, and Applications

Transcription

1 Forward Osmosis Principles, Trends, and Applications Tzahi Y. Cath Department of Civil and Environmental Engineering Colorado School of Mines Golden, Colorado DesalTech 215 San Diego, CA August 28, 215

2 Overview Osmosis and engineered osmosis Principles The three pillars of forward osmosis Membranes Draw solutions Systems and applications The path forward and requirements for successful adoption of the technology

3 Everything should be made as simple as possible, but not simpler. Albert Einstein

4 Is forward osmosis simple?

5

6 The Forward Osmosis Process

7 Osmosis and Engineered Osmosis ΔP=Δπ Brine Reconcentration Draw Solution Feed Brine Feed Osmosis (Osmotic Dilution) Engineered osmosis (Forward Osmosis (FO))

8 Draw Solutions NaCl Other inorganic salts (MgCl 2, MgSO 4, NH 4 HCO 3, etc.) Mixed salts Seawater and other natural brines (GSL, Dead Sea) Magnetic nanoparticles Organic molecules (sucrose, sodium acetate, polymethylamines, ethylenediamine tetraacetate, etc.) Fertilizers

9 Draw Solution Replenishment Processes Reverse osmosis Column distillation Membrane distillation Chemicals (switchable polarity (SPS): CO 2, etc.)

10 Membranes Early days RO membranes Cellulose triacetate blends (Osmotec/HTI) New Thin film composite polyamide Carbon nanotube Multi-wall carbon nanotubes Electrospun nanofibers Hollow fibers Aquaporin

11 Applications Early days Domestic wastewater treatment Food and beverage concentration Medical devices New Industrial wastewater Oil and gas wastewater Anaerobic digesters Osmotic dilution Fertigation Energy and material recovery

12 Capabilities (the promises ) Glorified pretreatment for desalination Simultaneous rejection of dissolved and suspended matter Desalination (brackish water, seawater, hypersaline brines) Concentration of streams Beverages and food Dilute streams Osmotic dilution of seawater Fertigation Controlled release (drugs, other chemicals) Dual-barrier systems Rejection of emerging trace organic contaminates Direct potable reuse

13 Back to membranes

14 Membranes for Forward Osmosis: The Needs RO-like performance High flux High rejection of dissolved species Low structural parameter (S) is critical S = tτ ε Active layer Water flux Salt flux Porous support π DS,b π DS,A Δπ π Feed,i π Feed,b

15 Membranes for Forward Osmosis: The Comparison Standard methods for evaluation of FO membranes call for testing with deionized water feed and 1 M NaCl DS Cath, T.Y., Elimelech, M, McCutcheon, J.R., McGinnis, R.L., Achilli, A., Childress, A.E., Nghiem, L.D., et al., Standard methodology for evaluating membrane performance in osmotically driven membrane processes, Desalination 312 (213)

16 Membranes for Forward Osmosis: The Comparison Standard methods for evaluation of FO membranes call for testing with deionized water feed and 1 M NaCl DS Active side facing DS Active side facing feed Water flux, L/m 2 -hr DS concentration, g/l But is it really the way to compare membranes? and can it determine which FO membrane is better? Cath, T.Y., Elimelech, M, McCutcheon, J.R., et al., Standard methodology for evaluating membrane performance in osmotically driven membrane processes, Desalination 312 (213)

17 Membranes for Forward Osmosis: The Practice Operation of an osmotic MBR (UFO-MBR) for more than 4 months with the HTI CTA membrane FO UF RO Holloway, R.W., Wait, A.S., Fernandes-da-Silva, A., Herron, J., Schutter, M., Lampi, K., Cath, T.Y., Long-term pilot scale investigation of novel hybrid ultrafiltration-osmotic membrane bioreactors, Desalination, 363 (215)

18 Membranes for Forward Osmosis: The Practice Operation of an osmotic MBR for more than 4 months with HTI CTA membrane TC flux, L/m 2 /hr TC flux TC pure water flux UF system online Days of UFO-MBR operation FO tank PO4 conc., mg/l Measured concentra5on Modeled concentra5ons Days of UFO- MBR opera>on Total system removal, % Sucralose (397.6) Acesulfame (163.2) Sulfamethoxazole (253.4) Naproxen (23.3) Acetaminophen (151.2) TCEP (285.5) Diphenhydramine (255.4) Caffeine (194.2) TCPP (327.6) Fluoxetine (39.3) TDCP (43.9) Ibuprofen (26.3) DEET (191.3) Atenolol (266.3) Propylparaben (18.2) Bisphenol A (228.3) Oxybenzone (228.2) Diclofenac (296.2) Triclocarban (315.6) Trimethoprim (29.3) Holloway, R.W., Wait, A.S., Fernandes-da-Silva, A., Herron, J., Schutter, M., Lampi, K., Cath, T.Y., Long-term pilot scale investigation of novel hybrid ultrafiltration-osmotic membrane bioreactors, Desalination, 363 (215)

19 Membranes for Forward Osmosis: The Practice Operation of FO with produced water for 48 under different operating conditions with CTA & TFC membranes Cellulose Triacetate (CTA) Polyamide TFC (TFC1) Polyamide TFC + Proprietary surface coating (TFC2)

20 Membranes for Forward Osmosis: The Practice Results for HTI CTA Normalized water flux, % Standardized Testing Methods [A] Chevron Feed Spacer Spiral Wound Crossflow Velocities Increased Transmembrane Pressure Hr 6 Hr 12 Hr 18 Hr 24 Hr OB 3 Hr 36 Hr 42 Hr 48 Hr Hr 6 Hr 12 Hr 18 Hr 24 Hr OB 3 Hr 36 Hr 42 Hr 48 Hr Hr 6 Hr 12 Hr 18 Hr 24 Hr OB 3 Hr 36 Hr 42 Hr 48 Hr Hr 6 Hr 12 Hr 18 Hr 24 Hr OB 3 Hr 36 Hr 42 Hr 48 Hr Test Set A Test Set B Test Set C Test Set D Osmotic backwash Coday, B.D., Almaraz, N., Cath, T.Y., Forward osmosis desalination of oil and gas wastewater: Impacts of membrane selection and industrial operating conditions, Journal of Membrane Science, 488 (215) 4-55.

21 Membranes for Forward Osmosis: The Practice Results for polyamide TFC + Proprietary surface coating (TFC2) Normalized water flux, % Standardized Testing Methods [A] Chevron Feed Spacer Spiral Wound Crossflow Velocities Increased Transmembrane Pressure Hr 6 Hr 12 Hr 18 Hr 24 Hr OB 3 Hr 36 Hr 42 Hr 48 Hr Hr 6 Hr 12 Hr 18 Hr 24 Hr OB 3 Hr 36 Hr 42 Hr 48 Hr Hr 6 Hr 12 Hr 18 Hr 24 Hr OB 3 Hr 36 Hr 42 Hr 48 Hr Hr 6 Hr 12 Hr 18 Hr 24 Hr OB 3 Hr 36 Hr 42 Hr 48 Hr Test Set A Tast Set B Test Set C Test Set D Osmotic backwash Coday, B.D., Almaraz, N., Cath, T.Y., Forward osmosis desalination of oil and gas wastewater: Impacts of membrane selection and industrial operating conditions, Journal of Membrane Science, 488 (215) 4-55.

22 Membranes for Forward Osmosis: The Practice Results for polyamide TFC + Proprietary surface coating (TFC2) 1 Normalized water flux (J /J o ), % KL733 EDTA CC Permeate volume, L Membrane flux recovery TFC2 CTA TFC1 Coday, B.D., Almaraz, N., Cath, T.Y., Forward osmosis desalination of oil and gas wastewater: Impacts of membrane selection and industrial operating conditions, Journal of Membrane Science, 488 (215) 4-55.

23 Back to draw solutions

24 Draw Solutions for Forward Osmosis: The Spectrum When I was young Cath, T.Y., Childress, A.E., Elimelech, M., Forward osmosis: Principles, applications, and recent developments, Journal of Membrane Science, 281 (26) 7-87.

25 Draw Solutions for Forward Osmosis: The Actual Impact 14 Draw Solution Concentration, M.5 M NaCl J w : NaCl.5 M MgCl 2 1. M NaCl 75 Water Flux, L/m 2 -hr J w : MgCl 2 J S : NaCl J S : MgCl Reverse Salt Flux, mmol/m 2 -hr Osmotic Pressure, MPa Hancock, N.T. and Cath, T.Y., Solute coupled diffusion in osmotically driven membrane processes, Environmental Science & Technology, 43 (17) (29)

26 Draw Solutions for Forward Osmosis: The Alternatives The impacts of reverse diffusion of NH 4 HCO 3 The implications of using polymethylamines and other organic draw solutions Implications of using fertilizers Back to NaCl?

27 Draw Solutions for Forward Osmosis: The Alternatives Mixed draw solutions Water flux, L/m2-hr NaCl 48 bar total osmotic pressuren of DS 23 bar total osmotic pressure of DS 16 5% MgCl2 1% MgCl2 5% MgSO4 1% MgSO4 5% NaACE 1% NaACE 5% NaCIT 1% NaCIT Water flux, L/m2-hr NaCl 5% MgCl2 1% MgCl2 1% MgCl2 5% MgSO4 1% MgSO4 1% MgSO4 5% NaACE 1% NaACE 1% NaACE 5% NaCIT 1% NaCIT 1% NaCIT Holloway, R.W., Maltos, R., Vanneste, J., Cath, T.Y., Mixed draw solutions for improved forward osmosis performance, Journal of Membrane Science, 491 (215)

28 Draw Solutions for Forward Osmosis: The Alternatives Mixed draw solutions 48 bar total osmotic pressure of DS 23 bar total osmotic pressure of DS RSF, mmol/m2-hr RSF, mmol/m2-hr NaCl 5% MgCl2 1% MgCl2 5% MgSO4 1% MgSO4 5% NaACE 1% NaACE 5% NaCIT 1% NaCIT 1 NaCl 5% MgCl2 1% MgCl2 1% MgCl2 5% MgSO4 1% MgSO4 1% MgSO4 5% NaACE 1% NaACE 1% NaACE 5% NaCIT 1% NaCIT 1% NaCIT Holloway, R.W., Maltos, R., Vanneste, J., Cath, T.Y., Mixed draw solutions for improved forward osmosis performance, Journal of Membrane Science, 491 (215)

29 Draw Solutions for Forward Osmosis: The System Context What reconcentration process do you use? Solubility, g/l Osmotic pressure, MPa Osmotic pressure PVP (b) PVP, kpa LiCl LiBr CaCl2 MgCl2 Na(C2H5COO) HCOONa NaCl KBr (NH4)2SO4 KCl C2H3NaO2 Na3C6H5O7 Na2SO4 Mg(CH3COO)2 MgSO4 NH4HCO3 KHCO3 NaHCO3 LiCl LiBr CaCl2 MgCl2 Na(C2H5COO) HCOONa NaCl KBr (NH4)2SO4 KCl C2H3NaO2 Na3C6H5O7 Na2SO4 Mg(CH3COO)2 MgSO4 NH4HCO3 KHCO3 NaHCO3 osmotic pressures of 17.4 MPa (~2,5 psi) Kerri L. Hickenbottom, Johan Vanneste, and Tzahi Y. Cath, Assessment of alternative draw solutions for enhanced performance of an osmotic heat engine, in preparation.

30 Draw Solutions for Forward Osmosis: The System Context What reconcentration process do you use? Water flux, LMH PRO HCOONa CaCl2 KBr NaCl LiBr MgCl2 Flux Diffusivity LiCl Na(C2H5COO) Diffusivity (1-9 ) m 2 /s Water flux, LMH MD LiCl CaCl2 NaCl MgCl2 KBr LiBr Flux Feed PVP Na(C2H5COO) HCOONa MD Feed water PVP, kpa Generation cost, $/kwh KBr LiBr NaCl HCOONa LiCl Na(C2H5 MgCl2 CaCl2 osmotic pressures of 17.4 MPa (~2,5 psi) Kerri L. Hickenbottom, Johan Vanneste, and Tzahi Y. Cath, Assessment of alternative draw solutions for enhanced performance of an osmotic heat engine, in preparation.

31 Draw Solutions for Forward Osmosis: The System Context And there are other important system aspects of draw solution selection: Reverse salt flux Solute replenishment Corrosivity ph Thermal efficiency

32 Forward Osmosis: Systems and Applications Where are we on the commercialization timeline?

33 Forward Osmosis: Systems and Applications Where are we on the commercialization timeline? What are the best applications for forward osmosis? Need to have economical advantage

34 Forward Osmosis: Systems and Applications Contribution to impact category 1% 9% 8% 7% 6% 5% 4% 3% 2% 1% % Engineered Osmosis Transport & Disposal NF Energy NF Membranes NF Infrastructure NF Membrane CC RO Energy RO Membranes RO Infrastructure RO Membrane CC FO Energy FO Membranes FO Infrastructure FO Membrane CC Treatment Cost, $/bbl Fixed Capital Labor & Spares Energy Cleaning Chemicals OD GW SM AP EP CP NCP RE EcP FFD NF Membrane Replacement RO Membrane Replacement FO Membrane Replacement TRACI 2.1 impact category RO < 4 kwh/m 3 FO 1-15 kwh/m 3 Coday, B.D., Miller-Robbie, L., Beaudry, E.G., Munakata-Marr, J., Cath, T.Y., Life cycle and economic assessments of engineered osmosis and osmotic dilution for desalination of Haynesville shale pit water, Desalination, 369 (215),

35 Forward Osmosis: Systems and Applications Where are we on the commercialization timeline? What are the best applications for forward osmosis? Need to have economical advantage Need to have lower environmental footprint Hancock, N.T., Black, N., Cath, T.Y., Life cycle assessment of hybrid osmotically driven membrane processes for seawater desalination and wastewater reclamation, Water Research, 46 (4) (212)

36 Forward Osmosis: Systems and Applications Where are we on the commercialization timeline? What are the best applications for forward osmosis? Need to have economical advantage Need to have lower environmental footprint Hancock, N.T., Black, N., Cath, T.Y., Life cycle assessment of hybrid osmotically driven membrane processes for seawater desalination and wastewater reclamation, Water Research, 46 (4) (212)

37 Forward Osmosis: Systems and Applications Where are we on the commercialization timeline? What are the best applications for forward osmosis? Need to have economical advantage Need to have lower environmental footprint 3 25 Operation Materials OCWD 3 25 Operation Materials UFO-MBR Energy, kj/m Energy, kj/m bar 17 bar 34 bar 52 bar 69 bar 2 g/l 3 g/l 4 g/l 5 g/l R.W. Holloway, L. Miller-Robbie, M. Patel, J.R. Stokes, T.Y. Cath, Life-cycle assessment of two water reuse technologies: MF/RO/UV-AOP treatment and hybrid osmotic membrane bioreactors, Desalination, submitted.

38 Forward Osmosis: Systems and Applications Where are we on the commercialization timeline? What are the best applications for forward osmosis? Need to have economical advantage Need to have lower environmental footprint CO 2 equivalents, kg/m OCWD Operation Materials bar 17 bar 34 bar 52 bar 69 bar CO 2 equivalents, kg/m UFO-MBR Operation Materials 2 g/l 3 g/l 4 g/l 5 g/l R.W. Holloway, L. Miller-Robbie, M. Patel, J.R. Stokes, T.Y. Cath, Life-cycle assessment of two water reuse technologies: MF/RO/UV-AOP treatment and hybrid osmotic membrane bioreactors, Desalination, submitted.

39 Forward Osmosis: Systems and Applications Where are we on the commercialization timeline? What are the best applications for forward osmosis? Need to have economical advantage Need to have lower environmental footprint Need to be simple

40 Forward Osmosis: The Future Find the right applications Conduct techno-economic analysis and life cycle assessment Collaboration is a key! Academia academia Academia industry

41 Impacts of Exposure to Produced Water Shifts in Membrane Performance Change in SRSF, % CTA TFC2 KL EDTA Post chemical cleaning Specific Reverse Salt Flux (SRSF) = Js Jw B A J s Reverse solute flux J w Water flux B Solute perm. coef. A Water perm. coef.

42 Impacts of Exposure to Produced Water Water Flux and Reverse Salt Flux Post Exposure Water flux, L/m 2 -hr Pre exposure Post exposure CTA Draw solution conc., M Reverse salt flux, mmol/m 2 -hr Water flux, L/m 2 -hr Pre exposure Post exposure TFC Draw solution conc., M Reverse salt flux, mmol/m 2 -hr SRSF =.65 g/l SRSF 1 =.61 g/l SRSF =.24 g/l SRSF 1 =.13 g/l SRSF = J s J w

43 Academia-Industry Collaboration (Betamax vs. VHS)

44 Acknowledgements Membrane manufacturer Hydration Technology Innovations Membrane manufacturer Oasys Water NGL Energy Partners (formerly High Sierra) test site support Financial support US Department of Energy/RPSEA US Department of Energy/ARPA-e NSF/ERC ReNUWIt NSF/SRN AWG

45 Thank You