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Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization Paula Moon and Seth Snyder Argonne National Laboratory Thomas Hayes, Gas Technology Institute Presentation at the 13 th International Petroleum Environmental Conference Oct 17-20, 2006

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Page 1: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced

Water Demineralization

Paula Moon and Seth Snyder Argonne National LaboratoryThomas Hayes, Gas Technology Institute

Presentation at the 13th International Petroleum Environmental ConferenceOct 17-20, 2006

Page 2: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

2

Overall Objective

Develop Electrodialysis for a cost-effective and reliable demineralization of produced waters for beneficial use purposes.Beneficial Use Examples:

IrrigationLivestockGroundwater Aquifer RechargeHabitat Maintenance/Surface Discharge

Page 3: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

3

Laboratory Evaluation Phase

1. Pretreatment to Remove Membrane Fouling factors (e.g. suspended solids)

2. Compare CBM Produced Water Electrodialysis Process Performance Using Selective (CMX-S) and non Selective (CMX) Cation Membranes to Minimize Fouling Factors

3. Evaluate Electrodialysis Membranes Back Diffusion Effect of a Dilute CBM Produced Water Feed and a large Salt Solution Concentration

4. Post Demineralization Treatment to adjust the Sodium Adsorption Ratio (SAR) to Levels Suited to Beneficial Use

5. Perform Long Term Membrane Stability Test with non Selective Membranes and a large Sodium Bicarbonate Solution in the Concentrate

Page 4: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

4

Electrodialysis Technology

Feed

Page 5: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

5

Schematic of Electrodialysis Stack

Page 6: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

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Performance Characteristics of EDStrengths

Applicable to low to moderate TDS

Energy costs excessive at TDS above 20,000 mg/l

Does not remove BTEX or PAH’s like naphthalene

High water recoveries > 92%Low pressure operation < 25 psiReduced precipitate formation in processResistant to fouling– ED Reversal (EDR)– CIP approaches

Also removes volatile acids

Limitations

Page 7: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

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ED Experiments Conducted

Wyoming CBM Produced Water– Constant Current Density and non selective cation

(CMX) membranes– Constant Current Density and selective cation

(CMX-S) membranes– Constant Current Density, non selective cation

membrane and concentrate with a high salt concentration of approximate 300 g/L sodium chloride

– Constant Current Density, non selective cation membrane and 50 g/L sodium bicarbonate

Page 8: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

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Process Flow Diagram- Produced Water Lab-Scale ED System

Page 9: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

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Produced Water Laboratory Scale Electrodialysis System

ED Membrane

Page 10: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

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Key Conditions for ED Lab Pilot in This Effort

Stack: 10 cell pairs

Membranes: AMX/CMX and AMX/CMX-S

ED Unit: Batch configuration Constant CurrentAverage Voltage Drop per cell <1.5 volts

Page 11: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

11

Wyoming CBM Produced Water Concentration

CBM Produced Water Conditions pH = 8.4Conductivity = 1783 uS/cmVolume = 10 L

Concentrate Solutions5 g/L, 300 g/L sodium chloride and 50 g/L sodium bicarbonate

Parameter Units InfluentSodium mg/L 670Calcium mg/L 6.7Magnesium mg/L 2.3Chloride mg/L 7Alkalinity mg/L as CaCO3 1300

Page 12: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

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Cation Membranes Characteristics

CMX CMX-SNon Selective Membrane Allow transport of monovalent and divalent cations

Good Mechanical Strength Good Mechanical Strength$500/m2 for laboratory scale $500/m2 for laboratory scale

2 yrs membrane lifetime

Selective Membrane (monoselective)Reject >90% Calcium

Reject >90% Magnesium

2 yrs membrane lifetime

Page 13: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

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Variation of pH and Effuent Conductivity with non Selective CMX Cation Membranes

0

500

1000

1500

2000

2500

3000

3500

0 10 20 30 40 50 60 70

Time (min)

Con

duct

ivity

(us/

cm)

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

9.0

pH

ConductivitypH

CD = 4 mAmps/cm2

Page 14: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

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Wyoming CBM Produced Water Divalent Ion Concentration Changes and % Desalting with non Selective CMX Membranes

0

1

2

3

4

5

6

7

Ion

Con

cent

ratio

n, m

g/L

0 52 57 65

Time, min

CalciumMagnesium

CD = 4 mAmps/cm2

92% 92% 87%87% 87%87%

Page 15: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

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Variation of pH and Effluent Conductivity with Selective CMX-S Cation Membranes

0

500

1000

1500

2000

2500

3000

0 10 20 30 40 50 60

Time (min)

Con

duct

ivity

(us/

cm)

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

9.0

pH

Conductivity CMX-SpH CMX-S

CD = 4 mAmps/cm2

Page 16: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

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Wyoming CBM Produced Water Divalent Ion Concentration Changes and % Desalting with Selective CMX-S Membranes

CD = 4 mAmps/cm2

0

1

2

3

4

5

6

7

Ion

Con

cent

ratio

n, m

g/L

0 40 50 55Time, sec

CalciumMagnesium37%

22%

52%

72%63%

62%

Page 17: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

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Power Consumption as a function of % Desalting, Cation Membrane Type and SAR

0.00

0.05

0.10

0.15

0.20

0.25

Pow

er C

onsu

mpt

ion,

kW

hr/lb

NaC

l equ

iv.

AMX/CMX, 95% AMX/CMX, 96% AMX/CMX-S, 88% AMX/CMX-S, 92%

SAR 10.2

SAR 9.3

SAR 10.9

SAR 8.3

CD= 4 mAmps/cm2

Page 18: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

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Effect of Amount of Sodium in the Soil

USDA Agriculture Handbook # 60, Diagnosis and Improvement of Saline and Alkali Soils, page 80, 1954

Irrigation water with excess amount of sodium can adversely impact soil structure and plant growth.

Page 19: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

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Wyoming CBM Produced Water with AMX/CMX-S Membranes at CD = 4 mAmps/cm2 and Post Demineralization Treatment

Parameter Units Influent Effluent Adjusted SAR Adjusted SAR Adjusted SAR

w/limestone w/CaCO3 w/CaSO4

Sodium mg/L 670 56 55 56 57

Calcium mg/L 6.7 1.9 18 17 690

Magnesium mg/L 2.3 0.9 1.6 2.7 1.0

Alkalinity mg/L CaCO3 1300 350 180 210 140

Chloride mg/L 140 7 11 13 11

Conductivity us/cm 2650 331 333 324 2820

SAR 56.2 8.3 3.3 3.3 0.6

pH 8.3 7.0 8.3 8.3 7.9

Level Suited to Beneficial Use

Page 20: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

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Back Diffusion observed at the beginning of the ED run with a salt concentration greater than 300 g/L NaCl

0

500

1000

1500

2000

2500

3000

0 20 40 60 80 100 120 140 160 180

Time (min)

Effl

uent

Con

duct

ivity

(us/

cm)

0.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

9.0

pH

ConductivitypH

AMX/CMX membranes and CD= 4 mAmps/cm2

0.53 kWh/lb NaCl equiv.and 92 % desalting

Page 21: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

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Wyoming CBM Produced Water Concentration

CBM Produced Water ConditionspH = 8.6Conductivity = 2780 uS/cmVolume = 10 L

Concentrate Solution50 g/L sodium bicarbonate

Parameter Units InfluentSodium mg/L 840Calcium mg/L 6.7Magnesium mg/L 2.7Chloride mg/L 39Alkalinity mg/L as CaCO3 1400

Page 22: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

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Effuent Conductivity and Cell Voltage Profiles for Long Term Membrane Stability Test with AMX/CMX Membranes and CD= 3 mAmps/cm2

0

500

1000

1500

2000

2500

3000

3500

0 2 4 6 8 10 12 14 16 18 20

Time ( hr)

Effl

uent

Con

duct

ivity

(us/

cm)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

Cel

l Vol

tage

(vol

ts)

ConductivityCell Voltage

Page 23: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

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Effluent and Concentrate pH Profiles for Long Term Membrane Stability Test with AMX/CMX membranes and CD= 3 mAmps/cm2

5.0

5.5

6.0

6.5

7.0

7.5

8.0

8.5

9.0

9.5

0 2 4 6 8 10 12 14 16 18 20Time (hr)

pH

Effluent pHConcentrate pH

Page 24: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

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Concentrate Solution @ 20 hrs of Membrane Stability Test with AMX/CMX Membranes

Parameter Units ConcentrateSodium mg/L 16000Calcium mg/L 14Magnesium mg/L 49Chloride mg/L 440Alkalinity mg/L as CaCO3 36000

Page 25: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

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ConclusionsProduced water recovery efficiency >90 %

Modest energy input: 0.14 – 0.20 kWh/lb NaCl equiv. removed

Achieves 92% removal of dissolved solids

New selective membrane CMX-S reduces scaling potential

Back diffusion observed for concentrate solutions greater than 300 g/L NaCl

Non selective membrane with a sodium bicarbonate solution in theconcentrate perform well in long term membrane test

Page 26: Integrated Electrodialysis Membrane Stability Results for Cost-Effective CBM Produced Water Demineralization

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Acknowledgments

This Work was Supported with Funding from DOE/NETL-NPTO

Thanks to Brian A. Hodgson from Marathon Oil Company for supplying the CBM Produced Water to run these experiments