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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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