Operating parameters influencing Ultrafiltration of organic model solutions

Verónica García Molina Technical Service and Development Dow Water Solutions 27-28th November, Aachen
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Aquabase Workshop on Mitigation Technologies

STRUCTURE OF THE TALK • Overview Ultrafiltration • Experimental Results • Conclusions

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Verónica García Molina, Aachen 27-28th November

and ultimately lower turbidity. ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow Verónica García Molina. dissolved organics.Aquabase Workshop on Mitigation Technologies PRINCIPLES OF ULTRAFILTRATION What is Ultrafiltration? Ultrafiltration is a size exclusion membrane process that reject particles. taste & odor. high molecular weight species. pathogens. etc. Aachen 27-28th November . UF does not reject any dissolved salts. However. or other species like true color.

Aachen 27-28th November .Aquabase Workshop on Mitigation Technologies PRINCIPLES OF ULTRAFILTRATION What is Ultrafiltration? ionogen aqueous salts synthetic dye metal ion endotoxin sugar atomic radius gelatin latex / emulsion asbestos milled flour molecular macro molecular micro particle macro particle human hair beach sand carbon black albumin protein paint pigment tobacco smoke viruses bacteria indigo blue yeast cells activated carbon red blood cells Pollen 0.01 Relative size of common materials dP [µm] 0.0001 0.1 1 10 100 1000 UF ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow Verónica García Molina.001 0.

P.S. Pathogens Rotavirus [bar = 100 nm) F.D. U. Aachen 27-28th November . U. Coli Microcolony average cell is ~ 4 µm long James Shapiro and Clara Hsu.Aquabase Workshop on Mitigation Technologies PRINCIPLES OF ULTRAFILTRATION Why UF? Ultrafiltration membrane development has been accelerated due to more stringent drinking water rules around the world to remove pathogens from drinking water coupled with its potential of easy integrity validation. EPA [bar = 10 µm] E. University of Chicago ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow Verónica García Molina. Williams.A Lindquist.S. EPA Cryptospridium and Giardia H.

higher feed spacer required Verónica García Molina. Aachen 27-28th November ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow .Aquabase Workshop on Mitigation Technologies PRINCIPLES OF ULTRAFILTRATION Operation mode: Dead-end vs Cross-Flow Feed Feed Concentrate membrane membrane Permeate Dead-End Module Application Operation Cleaning Drawbacks Hollow fiber (submerged and pressurized) Feed ↓ TDS Discontinuous operation Back wash feasible Flux decline or feed pressure increase with time Permeate Cross-Flow Spiral wound Feed ↑ TDS Continuous operation Back wash not possible With high TDS.

Aquabase Workshop on Mitigation Technologies PRINCIPLES OF ULTRAFILTRATION While working in Dead-End modus: • Backwash (Reverse Filtration) o Often dosed with 15 ppm of NaClO (fouling control) o Flowrate is 200% of design flux (minimum 100 lmh) • Air Scrub o Air pressure is <1 bar delivered at the module o Frequency is typically every 6 hours when necessary ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow Verónica García Molina. Aachen 27-28th November .

Aachen 27-28th November .pH 2 • Alkali: NaOH 1000 ppm or NaClO 2000 ppm.Aquabase Workshop on Mitigation Technologies PRINCIPLES OF ULTRAFILTRATION While working in Dead-End modus: Chemically Enhanced Back-wash (approx. pH12 ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow Verónica García Molina. Every 72 hours) • Acid: HCl 1000 ppm ◦ Removes colloids and inorganic salt • Alkali: NaOH 500 ppm or NaClO 1000 ppm ◦ Removes organics or biofoulants from membrane Clean in Place (every 1 to 3 months) • Acid: HCl 2000 ppm .

Aachen 27-28th November .Aquabase Workshop on Mitigation Technologies PRINCIPLES OF ULTRAFILTRATION Main fields of applications of Ultrafiltration? • Municipal and industrial wastewater treatment and reuse ◦ Membrane Bioreactors ◦ Hygienization of WWTP ◦ Pre-filter before NF/RO • Drinking water processing ◦ Pre-treatment for NF/RO • Surface water treatment for industrial use ◦ Food industry ◦ Pharmaceutical industry ◦ Metal processing industry • Seawater pretreatment ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow Verónica García Molina.

0 ≤2 ≤1 ≤5 ≤1000 ≤240 High COD UF RO DI UF COD removal 37.PRINCIPLES OF ULTRAFILTRATION CASE 1 Petrochemical Water Reclamation Source: Petrochemical plant wastewater Capacity: 560 m3/h Location: Beijing.5% Verónica García Molina. China Running Time: From 2005 Process: UF Pretreatment UF Feed Water Quality Item CODcr(mg/L) Turbidity(NTU) Oil(mg/L) NH3-N(mg/L) TSS(mg/L) TDS(mg/L) Ca2+(mg/L) Amount ≤40 ≤5. Aachen 27-28th November ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow .

5 4847 1122 69.5℃) 82.9 91.1 (15.PRINCIPLES OF ULTRAFILTRATION CASE 2 Microelectronics Water Reclamation Source: Plant industrial wastewater [from cut and grind process] Capacity:90 m3/h Location: Shanghai. China Running Time: From 2006 Process: Coagulation→Sedimentation→Bag Filter→ UF Parameter pH Turbidity CODcr TDS Actived Silica Total Silica Oil NTU mg/L mg/L mg/L mg/L mg/L Unit 7.6 0.08 Verónica García Molina. Aachen 27-28th November Feed water High turbidity High COD value ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow .

PRINCIPLES OF ULTRAFILTRATION CASE 3 High TSS Surface Water Treatment Operational Performance Feed 2 ppm NaOCl before UF System Process: Raw Water Tank UF Feed Pump Heater Exchanger OMEXELLTM UF High TSS raw water feed to OMEXELLTM UF directly RO Turbidity is less than 0.5 bar (average) CIP is only once during 2 years operation ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow Verónica García Molina.2 NTU (90%) TMP is less than 0.4 NTU (100%) and less than 0. Aachen 27-28th November .

Aachen 27-28th November .000 m3/d UF Permeate and 28.4bar Without CEB BW Frequency: >30min CIP Frequency: Once/3~4months ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow Verónica García Molina.800 m3/d RO Water Location: HeBei.PRINCIPLES OF ULTRAFILTRATION CASE 3 Seawater Pretreatment Source: Seawater Capacity: 50. China Running Time: From 2005 Process: Disc-Filter + UF + RO TMP is less than 0.

Aachen 27-28th November .Aquabase Workshop on Mitigation Technologies STRUCTURE OF THE TALK • Overview of Ultrafiltration • Experimental Results • Objective • Experimental Device • Discussion of results • Conclusions ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow Verónica García Molina.

Aachen 27-28th November .Aquabase Workshop on Mitigation Technologies EXPERIMENTAL PART Objective: Study the influence of some operating parameters on the performance of an UF test unit • Concentration of solutes in the Feed • Pressure Applied • pH of the solution • Presence of Calcium ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow Verónica García Molina.

Alginic Acid 300 rpm 1 – 3 bar Ambient Until a certain amount of permeate is collected Verónica García Molina. 20 kDa and 5 kDa (polyethersulfone) Dextran. Fulvic Acid. Humic Acid. NOM.Aquabase Workshop on Mitigation Technologies EXPERIMENTAL PART Ultrafiltration Test Cell Stirrer Membrane Feed and concentrate Permeate Pressurized air conduction Volume Membranes Solution Agitation Pressure Temperature Duration 400 mL 30 kDa (cellulose). Aachen 27-28th November ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow . Cellulose powder.

Aachen 27-28th November .Aquabase Workshop on Mitigation Technologies EXPERIMENTAL PART Influence of the solute concentration in the feed solution 1 mg/L 3 mg/L 5 mg/L 8 mg/L 10 mg/L 80 75 70 65 60 55 50 45 40 35 30 25 10 20 30 40 50 60 70 80 90 100 65 Permeability (L/m hbar) Permeability (L/m hbar) 60 55 50 45 40 35 30 25 10 20 30 40 50 60 70 80 90 100 2 Permeate Volume (mL) 2 Permeate Volume (mL) 30 kDa Cellulose membrane 20 kDa Polyethersulfone membrane Permeability vs. Permeate volume. Dextran solutions containing from 1 to 10 mg/L High concentrations → higher membrane fouling/cake layer formation ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow Verónica García Molina.

Concentration Feed Feed + Concentration Feed membrane membrane membrane Permeate Permeate Permeate High concentrations → higher membrane fouling→ lower flow ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow Verónica García Molina. Aachen 27-28th November .Aquabase Workshop on Mitigation Technologies EXPERIMENTAL PART Influence of the solute concentration in the feed solution .

6 0.Aquabase Workshop on Mitigation Technologies EXPERIMENTAL PART Influence of the solute concentration in the feed solution 1 0.Concentration + Concentration 30 kDa membrane Cake layer model: ↑ Concentration ↓ Passage 20 kDa membrane Difussion Model: ↑ concentration difference ↑ Passage ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow Verónica García Molina.9 0.7 0. Aachen 27-28th November .Concentration + Concentration Retention 0.8 30 kDa 20 kDa 30 kDa Membrane .5 0.4 1 3 5 7 9 11 . Re tention = 1 − CODpermeate COD feed Dextran Concentration (mg/mL) 20 kDa Membrane .

Aachen 27-28th November .29 0.25 Flux vs.27 Permeate Volume (mL) 0.57 3 bar 0. 5 kDa Polyethersulfone membrane Higher transmembrane pressure results in faster accumulation of solutes → higher passage Re tention = 1− CODpermeate CODfeed ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow Verónica García Molina.Aquabase Workshop on Mitigation Technologies EXPERIMENTAL PART Influence of the transmembrane pressure 33 30 27 1 bar 2 bar 3 bar Higher transmembrane pressure results in higher permeate production Retention values after UF of solutions containing NOMs and Dextran 1 bar NOM 1R101N (10 mg/mL) 5 kDa 0.62 0.45 Flux (mL/m h) 24 21 18 15 12 9 0 3 6 9 12 15 18 21 24 2 NOM 1R108N (10 mg/L) 5 kDa Dextran (3 mg/mL) 30 kDa 0. Permeate volume.65 2 bar 0. 10 mg/L of Fulvic Acids solutions.48 0.44 0.

7 64 62 60 58 56 54 52 50 48 Zeta Potential [mV] 0 -1 -2 -3 -4 -5 2 3 4 5 Measured Values Average Flux (mL/m h) 2 0 10 20 30 40 50 60 70 80 90 100 Permeate Volume (mL) Flux vs. 30 kDa Cellulose membrane pH 6 7 8 9 10 The higher the pH: -The membrane is more negatively charged . 3 mg/L of Dextran solutions at different pH conditions.Dextran more negatively charged due to deprotonation ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow Verónica García Molina. Permeate volume. Aachen 27-28th November .8 pH 6 pH 8 pH 9.Aquabase Workshop on Mitigation Technologies EXPERIMENTAL PART Influence of the pH of the feed solutions 1 pH 4.

Higher resistance for the water ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow Verónica García Molina. 5 kDa Polyethersulfone membrane Fastest formation of a fouling layer on the surface of the membrane. Permeate volume.2 mg/L CaCl2. Aachen 27-28th November .Membrane Flux (L/m h) 2 Permeate Volume (mL) Flux vs.Aquabase Workshop on Mitigation Technologies EXPERIMENTAL PART Influence of the presence of Ca2+ in the feed solution 160 140 120 100 80 60 40 20 0 10 20 30 40 50 60 70 80 90 100 3 g/L Alginic Acid 3 g/L Alginic Acid + 218.2H2O Bridging characteristics of Ca2+ between: -Solute – Solute -Solute .

Aachen 27-28th November .Aquabase Workshop on Mitigation Technologies STRUCTURE OF THE TALK • Overview of Ultrafiltration • Experimental Results • Conclusions ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow Verónica García Molina.

pH and presence of divalent cations have been proved to have a direct influence on the process • Membrane selection plays a crucial role for the success of the process ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow Verónica García Molina.Aquabase Workshop on Mitigation Technologies CONCLUSIONS •Conclusions • Flux decline during UF operation still remains an issue for its further development • Concentration in feed. Aachen 27-28th November . applied pressure.

Aachen 27-28th November .Aquabase Workshop on Mitigation Technologies THANK YOU VERY MUCH FOR YOUR ATTENTION ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow Verónica García Molina.