Operating parameters influencing Ultrafiltration of organic model solutions

Vernica Garca 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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Vernica Garca Molina, Aachen 27-28th November

Aquabase Workshop on Mitigation Technologies

PRINCIPLES OF ULTRAFILTRATION What is Ultrafiltration?

Ultrafiltration is a size exclusion membrane process that reject particles, pathogens, high molecular weight species, and ultimately lower turbidity. However, UF does not reject any dissolved salts, dissolved organics, or other species like true color, taste & odor, etc.

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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

0.0001

0.001

0.01

Relative size of common materials dP [m]

0.1

10

100

1000

UF

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Vernica Garca Molina, Aachen 27-28th November

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.
Pathogens

Rotavirus [bar = 100 nm) F.P. Williams, U.S. EPA

Cryptospridium and Giardia H.D.A Lindquist, U.S. EPA

[bar = 10 m]

E. Coli Microcolony average cell is ~ 4 m long James Shapiro and Clara Hsu, University of Chicago Trademark of The Dow Chemical Company (Dow) or an affiliated company of Dow Vernica Garca Molina, Aachen 27-28th November

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, higher feed spacer required
Vernica Garca Molina, Aachen 27-28th November

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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

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Vernica Garca Molina, Aachen 27-28th November

Aquabase Workshop on Mitigation Technologies

PRINCIPLES OF ULTRAFILTRATION While working in Dead-End modus:

Chemically Enhanced Back-wash (approx. 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 ;pH 2 Alkali: NaOH 1000 ppm or NaClO 2000 ppm; pH12

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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
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PRINCIPLES OF ULTRAFILTRATION
CASE 1 Petrochemical Water Reclamation
Source: Petrochemical plant wastewater Capacity: 560 m3/h Location: Beijing, China Running Time: From 2005 Process: UF Pretreatment UF Feed Water Quality
Item CODcrmg/L TurbidityNTU Oilmg/L NH3-Nmg/L TSSmg/L TDSmg/L Ca2+mg/L Amount 40 5.0 2 1 5 1000 240
High COD

UF RO

DI

UF COD removal 37.5%

Vernica Garca Molina, Aachen 27-28th November

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PRINCIPLES OF ULTRAFILTRATION
CASE 2 Microelectronics Water Reclamation
Source: Plant industrial wastewater [from cut and grind process] Capacity90 m3/h Location: Shanghai, China Running Time: From 2006 Process: CoagulationSedimentationBag Filter UF
Parameter pH Turbidity CODcr TDS Actived Silica Total Silica Oil NTU mg/L mg/L mg/L mg/L mg/L Unit 7.5 4847 1122 69.1 (15.5) 82.9 91.6 0.08
Vernica Garca Molina, Aachen 27-28th November

Feed water

High turbidity High COD value

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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 0.4 NTU (100%) and less than 0.2 NTU (90%)
TMP is less than 0.5 bar (average) CIP is only once during 2 years operation

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Vernica Garca Molina, Aachen 27-28th November

PRINCIPLES OF ULTRAFILTRATION
CASE 3 Seawater Pretreatment
Source: Seawater Capacity: 50,000 m3/d UF Permeate and 28,800 m3/d RO Water Location: HeBei, China Running Time: From 2005 Process: Disc-Filter + UF + RO

TMP is less than 0.4bar Without CEB BW Frequency: >30min CIP Frequency: Once/3~4months

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Aquabase Workshop on Mitigation Technologies

STRUCTURE OF THE TALK Overview of Ultrafiltration Experimental Results Objective Experimental Device Discussion of results Conclusions

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Vernica Garca 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

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Vernica Garca Molina, Aachen 27-28th November

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), 20 kDa and 5 kDa (polyethersulfone) Dextran, Humic Acid, Fulvic Acid, NOM, Cellulose powder, Alginic Acid 300 rpm 1 3 bar Ambient Until a certain amount of permeate is collected
Vernica Garca Molina, Aachen 27-28th November

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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

Permeate Volume (mL)

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
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Aquabase Workshop on Mitigation Technologies

EXPERIMENTAL PART
Influence of the solute concentration in the feed solution

- 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 Vernica Garca Molina, Aachen 27-28th November

Aquabase Workshop on Mitigation Technologies

EXPERIMENTAL PART
Influence of the solute concentration in the feed solution
1 0.9 0.8 30 kDa 20 kDa

30 kDa Membrane

- Concentration

+ Concentration

Retention

0.7 0.6 0.5 0.4 1 3 5 7 9 11 .

Re tention = 1

CODpermeate COD feed

Dextran Concentration (mg/mL)

20 kDa Membrane

- Concentration

+ Concentration

30 kDa membrane Cake layer model: Concentration Passage 20 kDa membrane Difussion Model: concentration difference Passage
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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 0.65 2 bar 0.57 3 bar 0.45

Flux (mL/m h)

24 21 18 15 12 9
0 3 6 9 12 15 18 21 24

NOM 1R108N (10 mg/L) 5 kDa Dextran (3 mg/mL) 30 kDa

0.62

0.44

0.27

Permeate Volume (mL)

0.48 0.29 0.25

Flux vs. Permeate volume. 10 mg/L of Fulvic Acids solutions. 5 kDa Polyethersulfone membrane

Higher transmembrane pressure results in faster accumulation of solutes higher passage

Re tention = 1 CODpermeate CODfeed

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Vernica Garca Molina, Aachen 27-28th November

Aquabase Workshop on Mitigation Technologies

EXPERIMENTAL PART
Influence of the pH of the feed solutions
1
pH 4.8
pH 6
pH 8
pH 9.7

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)

10 20 30 40 50 60 70 80 90 100

Permeate Volume (mL)

Flux vs. Permeate volume. 3 mg/L of Dextran solutions at different pH conditions. 30 kDa Cellulose membrane

pH

10

The higher the pH: -The membrane is more negatively charged - Dextran more negatively charged due to deprotonation

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Vernica Garca Molina, Aachen 27-28th November

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 + 218.2 mg/L CaCl2.2H2O

Bridging characteristics of Ca2+ between: -Solute Solute -Solute - Membrane

Flux (L/m h)

Permeate Volume (mL)

Flux vs. Permeate volume. 5 kDa Polyethersulfone membrane

Fastest formation of a fouling layer on the surface of the membrane; Higher resistance for the water

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Vernica Garca Molina, Aachen 27-28th November

Aquabase Workshop on Mitigation Technologies

STRUCTURE OF THE TALK Overview of Ultrafiltration Experimental Results Conclusions

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Vernica Garca Molina, Aachen 27-28th November

Aquabase Workshop on Mitigation Technologies

CONCLUSIONS

Conclusions Flux decline during UF operation still remains an issue for its further development Concentration in feed, applied pressure, 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

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Vernica Garca Molina, Aachen 27-28th November

Aquabase Workshop on Mitigation Technologies

THANK YOU VERY MUCH FOR YOUR ATTENTION

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Vernica Garca Molina, Aachen 27-28th November