KEMIRA Project Objective 1

1. Compare the effect of coagulation conditions (e.g. dose, pH) for conventional coagulation (coagulation/ flocculation/ sedimentation/ filtration) on RO feed water quality in terms of TEP and biopolymers removal and RO fouling potential (MFI-UF) reduction.

2.

Understand and propose mechanisms for the interaction between TEPs, biopolymers and coagulant using analytical techniques such as FTIR, Laser Raman Microscopy, etc.
Simulate the fouling rate and CIP frequency in SWRO using a model equation in combination with MFI-UF values obtained from different coagulation conditions.

3.

Research Approach

Compare effect of coagulation conditions on RO feed quality

Understand mechanisms between coagulant and TEPs

Simulate CIP frequency in RO membranes

Experimental Conditions

Compare effect of coagulation conditions on RO feed quality

Coagulation Conditions PIX-111 FeCl3 RM G = 1,100s-1 RM t = 20s Flocculation G = 45s-1 Flocculation t = 15min Settling t = 20min Filtration Conditions

Cellulose acetate

0.45m

Experimental Matrix

pH
8 5 0

Coagulant dose (mgFe/L)

0.5 1 5 10 20

Settled

Filtered

Analytical Parameters
Settled
Biopolymers MFI-UF10kDa TEP10kDa TEP0.4 Fe

Filtered

Volume [mL] 40 60 1000 100

x x x x

x x x x x

UV254
Turbidity

x
x

100
100

Sample Preparation
Maximum volume that can be withdrawn from each jar = 500mL Volume required per experimental condition (dose, pH) = 1.5L, hence 3 jars are coagulated per experiment

Jar 1 Settled/Filtered LC-OCD (biopolymers) Fe, UV254, Turbidity TEP10kDa MFI-UF10kDa Jar 2 TEP0.4 Settled Jar 3 TEP0.4 Filtered

Feed Water
Chaetoceros affinis (marine diatom)
rel. Signal Response

LC-OCD Analysis (harvest day 15)

2.0 1.5 1.0 0.5 0.0 0 20 40 60 Time [min] 80 100

20kDa < Biopolymers < 2m

Biopolymers Conc. 2.3mgC/L

Feed solution concentration for experiments = 0.5mgC/L as biopolymers Total feed water volume required for all experiments = 36L Ideally all experiments within this matrix should be done with the same batch of TEP Experiments were performed with 2 distinct batches of TEP
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Results

Effect of Coagulation on MFI-UF10kDa

MFI-UF10kDa measurements performed with 10kDa regenerated cellulose (RC) filters at 60L/m2h
Settled (pH=8) 30000 25000 MFI-UF10kDa [s/L2] MFI-UF10kDa [s/L2] 20000 15000 10000 5000 bdl 0 SSW Feed 0 0.5 1 5 10 20 Coagulant Dose [mg Fe/L] 0 SSW Feed 0 0.5 1 5 10 20 Coagulant Dose [mg Fe/L] Filtered (pH=8) 30000 25000 20000 15000 10000 5000 Settled (pH=5) Filtered (pH=5)

MFI-UF10kDa decreases consistently with increase in coagulant dose for settled and filtered water samples at pH 8 At pH 5, MFI-UF10kDa values do not decrease significantly for settled samples for coagulant dose > 5mgFe/L Filtration through 0.45m significantly reduces MFI-UF10kDa for both pH values 9

Normalized MFI-UF10kDa
Settled (pH=8) 120% Settled (pH=5) Filtered (pH=8) Filtered (pH=5)

100% Normalized MFI-UF10kDa

80%

60%

40%

20% bdl

0%

SSW

Feed

0.5

10

20

Coagulant dose (mg Fe/L)

10

Fe Residual
Settled (pH 8) 2.4 2.0 1.6 1.2 0.8 0.4 0.0
bdl bdl bdl

Filtered (pH 8) 2.4 2.0 1.6 1.2 0.8 0.4 0.0

Settled (pH 5)

Filtered (pH 5)

Fe Residual [mgFe/L]

SSW

Feed

0.5

10

20

Fe Residual [mgFe/L]

Feed

0.5

10

20

Coagulant dose [mg Fe/L]

Coagulant Dose [mg Fe/L]

Settled supernatant exceeds RO manufacturers recommendation for RO feed; 0.05mgFe/L At pH 5, filtration through 0.45m does not reduce iron residual below guideline value

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Effect of Coagulation on UV254 Absorbance

Filtered (pH=8) 0.045 Filtered (pH=5)

0.040
0.035

UV254 [abs/cm]

0.030 0.025 0.020 0.015 0.010 0.005 0.000 SSW Feed 0 0.5 1 5 10 20 Coagulant Dose [mg Fe/L]

UV254 absorbance increases with the presence of dissolved iron at pH 5 UV254 absorbance is reduced for coagulant dose 5mgFe/L at pH 8

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Effect of Coagulation on Turbidity

Settled (pH 8) 2.4 2.0 Turbidity [NTU] 1.6 1.2 0.8 Turbidity [NTU] Filtered (pH 8) 2.4 2.0 1.6 1.2 0.8 Settled (pH 5) Filtered (pH 5)

0.4
0.0 SSW Feed 0 0.5 1 5 Coagulant dose [mg Fe/L] 10 20

0.4
0.0 SSW Feed 0 0.5 1 5 Coagulant dose [mg Fe/L] 10 20

For settled water, turbidity decreases with increase in coagulant dose at pH 8. This trend is not observed at pH 5 Filtration reduces turbidity well below the RO feed recommended turbidity of 1.0 NTU for both pH values

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Biopolymers Concentration (LC-OCD)

BP (pH 8) 700 Biopolymer Concentration [g/L] 600 500 400 300 200 BP (pH 5) Removal (pH 8) Removal (pH 5) 0.8 0.7 Normalized Removal 0.6 0.5 0.4 0.3 0.2 0.1 0 SSW Feed 0 0.5 1 5 10 20 Coagulant dose [mg Fe/L]

100
0

Biopolymer reduction is relatively higher for pH 8 than pH 5 Maximum biopolymers removal is approximately 70% at 20mgFe/L and pH 8
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F-EEM Settled Samples at pH 8

SSW Blank

Feed

0mgFe/L

0.5mgFe/L

1mgFe/L

5mgFe/L

10mgFe/L

20mgFe/L

Protein-like peak observed for feed water, that decreases in intensity with increase in coagulant dose

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F-EEM Filtered Samples at pH 8

Feed

0mgFe/L

0.5mgFe/L

1mgFe/L

5mgFe/L

10mgFe/L

20mgFe/L

Filtration almost completely eliminates the protein-like peak Increase in coagulant dose does not significantly affect the intensities of the peaks
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F-EEM Settled Samples at pH 5

SSW Blank

Feed

0mgFe/L

0.5mgFe/L

1mgFe/L

5mgFe/L

10mgFe/L

20mgFe/L

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F-EEM Filtered Samples at pH 5

SSW Blank

Feed

0mgFe/L

0.5mgFe/L

5mgFe/L

10mgFe/L

20mgFe/L

Feed, Filtered

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Effect of Coagulation on TEP0.4

Settled pH 8 0.35 Filtered pH 8

0.30
TEP0.4um (mg Xeq/L) 0.25 0.20 0.15 0.10 0.05 0.00
LOD

Feed

0.5

10

20

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Effect of Coagulation on TEP10kDa

Settled (pH=8) 8 7 TEP10kDa (mg Xeq/L) Filtered (pH=8) 7 Settled (pH 5) Filtered (pH 5)

6
5 4 3 2 1 0 SSW Feed 0 0.5 1 5 10 20 Feed 0 Coagulant dose (mg Fe/L) 0.5 1 5 10 Coagulant Dose [mgFe/L] 20

6
TEP10kDA [mgXeq/L] 5 4 3 2 1 0

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Summary of Findings
MFI-UF10kDa is significantly lowered for coagulant doses >10mgFe/L and filtration through 0.45m Turbidity residual is strongly enhanced (to <1NTU) by filtration Fe residual is reduced to <0.05mgFe/L for coagulant concentrations 1-10mgFe/L with filtration for pH 8. Fe residual is significantly higher even at pH 5. Biopolymers removal of up to 70% can be achieved at high coagulant concentrations (i.e. 20mgFe/L) TEP10kDa measurements require further verification of blanks

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Plan of Experiments Complete TEP0.4 measurements for settled and filtered samples at pH 5

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Thank You!

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