Zeolite Membrane for Reverse Osmosis

8/4/2019 Zeolite Membrane for Reverse Osmosis

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Treating CoalTreating Coal --Bed MethaneBed Methane

Produced Water for Beneficial UseProduced Water for Beneficial Useby MFI Zeolite Membranesby MFI Zeolite Membranes

Junhang Dong and Robert Lee

Participants:Liangxiong Li, Hai Xiao, Colin Edwards, Benjamin Brooks,Nining Liu, Ashlee Ryan, Marlene Maxesse, Theo Hoseman

Petroleum Recovery Research CenterDepartment of Petroleum & Chemical Engineering

New Mexico Institute of Mining and Technology, Socorro, NM 87801

Phone: (505) 835-5293; Fax: (505) 835-5293; Email: [email protected]

DOE-PERF Water Program Review Meeting, Annapolis, MD, Nov. 2005.


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1. OVERVIEW

Grant: NETL/DOE (DE-FC26-04NT15548) DoE project manager: Jesse Garcia (Tulsa)

Timeline

Project start date: October 1, 2004 Project end date: September 30, 2007 Percent complete: ~32%

Budget/Total Project Funding DOE: $855,204 Contractor: $285,068

Project Goal Demonstrate a new technology of reverse osmosis through

molecular sieve zeolite membranes for efficiently treating theCBM produced brines for beneficial use.

Funding received in FY04: $354,075Funding for FY05: $365,283


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2. SCOPE & APPROACH

Fundamental study for development of chemicallystable zeolite membranes for reverse osmosis (RO)purification of coal-bed methane produced water forbeneficial use. Project includes three phases:

Phase 1 (FY05): Understand the mass transport behaviors ofwater and ions in zeolite membrane and the effects ofoperation parameters on the RO performance. ( COMPLETE )

Phase 2 (FY06): Optimize the RO operation conditions and

effectively improve membrane. ( ON-GOING ) Phase 3 (FY07): Long-term laboratory RO test using a 0.1-m 2

tubular membrane unit for technical evaluation.


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2.1 TECHNICAL APPROACH & BENEFITS

Residual

Disposal reducedvolume

+

H2O

Na +{H2O}n

Desalination by size-exclusionof hydrated ions

Organic-containing CBMproduced brine

Clean Water

SEPARATION

(Beneficial uses)

Molecular sieve zeolites: Crystal: excellent

chemical, mechanical,and thermal stabilities.

Sub-nanometer poressuitable for molecular/ionseparation.

Benefits: Mitigate environmental

liability and relievefinancial burden causedby produced water in oiland gas production.

Ease water shortage inNM and southwest aridregions.


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2.2 DESALINATION MECHANISM2.2 DESALINATION MECHANISM

MFIMFI--type zeolite used in this project: pore size 0.55 nmtype zeolite used in this project: pore size 0.55 nm

Free permeation of water: molecular

size of water much smaller thanzeolitic pores;Rejection of ions: hydrated ion sizemuch larger than zeolitic pores.

Effect of the nanoscale intercrystalline pores:

decreases ion rejection rate, especially for highTDS brines.


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3. CURRENT STATUS3.1 High quality zeolite membranes synthesized

NaY (FAU) membranePore size 0.74 nm

Hydrophilic

Tubular and disc membranesTubes: Pall Corp.

MFI membranePore size: 0.55nm

Hydrophobic


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3.2 EFFECTS OF OPERATINGTEMPERATURE AND PRESSURE

Effect of applied pressureEffect of temperature

0

5

10

15

20

25

30

35

40

0 20 40 60 80

T, oC

F w , m

o l / m

2 - h

50.0%

60.0%

70.0%

80.0%

90.0%

100.0%

110.0%

r i

Na+, Fw

Li+, FwNa+ rejection

Li+ rejection

0.000

10.000

20.000

30.000

40.000

50.000

0.00 1.00 2.00 3.00

Pressure, MPa

W a t e r

f l u x m o l

/ m 2 . h

0.000

0.010

0.020

0.030

0.040

I o n

f l u x , m o l

/ m 2

. hFlux (water)Flux (ion)

ADVANTAGES: Increasing temperature and pressure significantlyenhances water flux while maintaining high ion rejection.


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3.3 ION AND WATERTRANSPORT MODEL

f i

cii f iwici

C iiiion

C D

C

RT E

K RT

E D J J J ,,1,

, / ',0,2,1, expexp =

===

94

95

96

97

98

99

100

0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0

Crystallographic radius, Angstrom

r i

, %

Li+ Na+ K+ Rb + Cs +

1.0E-11

1.5E-11

2.0E-11

2.5E-11

3.0E-11

0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0

Crystallographic size of ion, Angstrom

W a t e r

d i f f u s

i v i t y

, m 2 / s

1.0E-13

3.0E-13

5.0E-13

7.0E-13

9.0E-13

I o n

d i f f u s

i v i t y , m

2 / s

Water

Ion

Li+ Na+ K+ Rb+ Cs+

][ == p f

www

p pK

d dp

K J

High rejection for alkali metal ions; multivalent ions are easier to be separatedby size exclusion due to higher charge density (hence larger hydrated ions).


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3.4 PRELIMINARY RESULTS ON

MEMBRANE IMPROVEMENT(PHASE II)

0.0%

10.0%

20.0%

30.0%40.0%

50.0%

60.0%

70.0%

80.0%

90.0%100.0%

0 0.5 1 1.5 2 2.5 3 3.5

Debye length (nm)

S a l u

t e r e j e c

t i o n

( % )

Before

After

Difference

0.37 0.09 0.04 0.010.0150.02

Feed Concentration (M)

RO performance: before andafter modification.

Online healing: deposition of metalion oligomers in intercrystal pores.


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3.5 COMPARISON WITH TRADITIONALRO MEMBRANES

BASED ON RO RESULTS FOR CBM PRODUCED WATER FROM FARMINGTON, NM

Properties Polymer Membrane Zeolite membrane

Organic resistance Poor Excellent

Organic rejection Incapable of Good (>90% BETX)

Ion rejection Good (>95%) Good (>95%, 1%TDS)

Applicable TDS level Low (10%TDS)

Membrane regeneration NO YESLifetime Short (< 3 mon) Long (> 5yr ?)

Chemical stability Unstable in low pH Stable: acidic to basic

Operating pressure >800 Psi < 500 Psi

Thermal stability Poor Excellent

Water flux >5 kg/h.m 2 ~1.0 kg/h.m 2 ( r i>80%)

Membrane cost Low High{

A d v a n t a g e s

I s s u e s


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CONCLUSION/PLANS (Phase II)

Zeolite membranes are capable ofpurifying oil and gas field brines.

Enhance water flux and ion rejection:

optimize operating conditions andimprove membrane: Temperature and pressureTemperature and pressure Thinner membranesThinner membranes Intercrystal pore repairing/minimizationIntercrystal pore repairing/minimization


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TRANSFER OF KNOWLEDGE

PUBLICATIONS in leading journals L. Li, J. Dong, T.M. Nenoff, Transport of Alkali Metal Ions in MFI Zeolite Membranesduring Reverse Osmosis. Environmental Science & Technology , submitted (2005).

X. Gu, J. Dong, T. M. Nenoff , D. E. Ozokwelu, Separation of p -Xylene fromMulticomponent Vapor Mixtures Using Tubular MFI Zeolite Membranes. Journal of Membrane Science, revised after peer reviewed (2005).

J. Zhang, J. Dong, M. Luo, H. Xiao, S. Murad, R. A. Normann, Zeolite-Fiber IntegratedOptical Chemical Sensors for Detection of Dissolved Organics in Water. Langmuir , 21(2005), 8609.

H. Xiao, J. Zhang, J. Dong. M. Luo, R. Lee, V. Romero, Synthesis of MFI zeolite films onoptical fibers for detection of chemical vapors, Optics Letters , 30, 11(2005), 1270.

X. Gu, J. Zhang, J. Dong, T.M. Nenoff, A Platinum-Cobalt-Loaded NaY Zeolite Membranefor Nonoxidative Conversion of Methane to Higher Hydrocarbons and Hydrogen.Catalysis Letters , 102, 1-2 (2005), 9.

X. Gu, J. Dong, T.M. Nenoff, Synthesis of defect-free FAU-type zeolite membranes andseparation for dry and moist CO 2 /N2 mixtures. Ind. Eng. Chem. Res. , 44 (2005), 937.

* L. Li, J. Dong, T.M. Nenoff, R. Lee, Desalination by Reverse Osmosis Using MFI ZeoliteMembranes. Journal of Membrane Science , 243(2004) 401.

PRESENTATIONS in national conferences J. Dong, L. Li, H. Xiao, R. Lee, Treating Coal-Bed Methane Produced Water for

Beneficial Use By Reverse Osmosis through Zeolite Membranes, Ground WaterProtection Council (GWPC) Annual Meeting, Portland, OR, September 24 28, 2005.

* L. Li, A. Ryan, T.M. Nenoff, J. Dong, R. Lee, Purification of Coal-Bed Methane ProducedWater by Zeolite Membranes. SPE Annual Meeting (Paper # 89892) , Houston, TX, Sept.

27 29, 2004.


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RELATIONSHIPS

TO OTHER DOE PROJECTS Membrane/thin film synthesis technology developed

in this project has been used in the following DOEfunded projects:

Zeolite membranes for WGS membrane reactors for hydrogen

production (EERE/DOE) Catalytic membranes for conversion of biomass-derived stocks

to hydrogen (HNEI/DOE & EERE through Sandia) Zeolite-integrated chemical sensors for clean energy technology

and environmental monitoring (NETL/DOE & WERC) Zeolite membranes for xylene separation (OIT/DOE) Zeolite membranes for CO 2 separation (NETL/DOE)


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Zeolite Membrane for Reverse Osmosis