Petroleum Recovery Research Center, A Division of the New Mexico Institute of Mining and

TechnologyPRRC

Desalination

Using Zeolite Membranes

Robert L. LeePetroleum Recovery Research Center (PRRC)

New Mexico Tech, Socorro

Petroleum Recovery Research Center, A Division of the New Mexico Institute of Mining and

TechnologyPRRC

PRRC/NM Tech:• A research arm of New Mexico oil and gas industry, only for oil

and gas industry, dedicated to industry’s interests alone.

• PRRC/NM Tech research directions are governed by its advisory board members including:(1) New Mexico Oil & Gas Association (NMOGA)(2) Independent Producers Association (IPANM) (3) New Mexico Oil Conservation Division (NMOCD)(4) New Mexico State Land Office (NMSLO)

• NMOGA, IPANM, NMOCD, and SLO are policy-making organizations but PRRC/NM Tech is for research only.

Petroleum Recovery Research Center, A Division of the New Mexico Institute of Mining and

TechnologyPRRC

PRRC Produced Water Research • Water Shutoff and Conformance Improvement

(Seright, PRRC/NM Tech)• Optimal Process Identification

(Hightower, Sattler, Sandia)• Produced Water Quality Data/Mapping

(Cather, PRRC/NM Tech)• Brine Treatment Innovations, WaterDog

(Dong, PRRC/NM Tech)

Petroleum Recovery Research Center, A Division of the New Mexico Institute of Mining and

TechnologyPRRC

Funding & Acknowledgements• Funding:

– 1/3 of PRRC/NM Tech’s resources are devoted to produced water projects.

– Current contracted budget: ~ $3.6M

• Acknowledgements:

– NPTO/NETL/DOE ~ $2.0M

– State of New Mexico ~ $1.4M

– NM Tech President Office ~ $0.2M

– Endorsements from NMOGA, IPANM, NMOCD, and SLO

Petroleum Recovery Research Center, A Division of the New Mexico Institute of Mining and

TechnologyPRRC

1) In 1998, PRRC/NM Tech started its desalination research effort.

2) Research focused on high-salinity produced water:- >> 50,000 ppm in San Juan basin- >> 100,000 ppm in Permian basin

3) 1999-2002 (Whitworth), studied compacted bentonite clay membranes. Unfortunately, the charged layers are destroyed in highly concentrated brines.

WaterDog Phase I, 1998-2002

Petroleum Recovery Research Center, A Division of the New Mexico Institute of Mining and

TechnologyPRRC

WaterDog Phase II, 2003 --

• The new synthetic Zeolite membrane was successfully tested by Dr. Dong’s group at PRRC/NM Tech.

• The Zeolite membrane has ~ 90% salt rejection rate of an 80,000 ppm produced water.

• It is an inorganic membrane.

• It should be easy to manufacture, is promising to be commercialized…………………..

• The patent application was filed in May 2003.

Liangxiong, Li a,b; Junhang, Dong a; Robert L. Lee b

a Department of Petroleum & Chemical Engineering b Petroleum Recovery Research Center (PRRC)

New Mexico Tech, Socorro

Polycrystalline Zeolite Membranes for produced water treatment

Introduction

• Produced water treatment

– High salt concentration (as high as 20 wt%, 200,000 ppm)

– Dissolvable hydrocarbon

– High cost of treatment ($1.7/barrel)

• Polymeric membrane

– Serious hydrolysis at produced water condition

– Sensitive to pH changes

• Inorganic membrane– High flux ($$)

– High thermal and chemical stability ($$)

– Regeneration capability ($$)

– Perhaps, low pretreatment cost ($$$$$$)

Zeolite Membrane Synthesis

Film formation

Nucleation Crystal growth

Synthesis methods used:

• In-situ crystallization• Second growth• Vapor phase conversion

Continuous zeolite layer

Porous -alumina support

Water bottle to prevent sample evaporation

Sample collector

Feed outlet

Feed tank

Sample analysis

Membrane cell

Feed pressure control and pressure gaugeHigh pressure N2

from cylinder

Flow control valve

Feed solution

Salt Removal Experiment

Mechanisms of Ion Removal by Zeolite Membrane

Mechanism A Size exclusion

Pore size5.6Å

(0.56 nano)

Ion Hydrated Diameter (Angstroms)

H2O 5.6

Li+ 7.6

Na+ 7.2

K+ 6.6

Mg++ 8.6

Ca++ 8.2

OH- 6.0

Cl- 6.6

NO3- 6.8

Mechanism B Double layerOverlapping

(inter crystals)

Zeolite Membrane--Image of Surface

• In situ crystallization

Zeolite Membrane--Image of Cross-Section

Zeolite

Alumina Support

XRD Pattern of Zeolite Layer

2

0 10 20 30 40 50

Rel

ativ

e In

ten

sity

alumina substrate

Zeolite Membrane

MFI type zeolite

Ion Removal Testing of Brine

Number Ions in feed solution

TDS

(104mg/l)

Pressure

(MPa)

Ion Rejection

(R, %)

Flux

(kg/m2.h)

AZA01 K+,Na+,Ca2+,Mg2+

, NH4+, and Cl-

3.92

(39K ppm)

2.41

(350 psi)

74.5% 0.112

AZS04 Na+, and Cl- 0.55 2.07 89.2% 0.135

BZA04 Mg2+, and Cl- 0.94 2.07 68.6% 0.081

BZA05 Ca2+, and Cl- 1.10 2.07 57.6% 0.096

BZA06 Na+, and SO42- 1.42 2.07 57.4% 0.097

EZA01 Na+, and Cl- 0.50 2.07 76.8% 0.240

tA

QF

m

w

%100

)(

)()(

feeds

permsfeeds

C

CCR

Ion Removal Testing of Brine

0 20 40 60 80 100Time, h

0.15

0.25

0.35

0.10

0.20

0.30

0.40

Flu

x, k

g m

h

-10

10

20

30

50

60

70

0

40

80

Rej

ection (R

), %

-2

-1

Flux

Rejection

0.00

0.20

0.40

0.60

0.80

1.00

1.20

0 20 40 60 80 100 120 140 160 180 200

Time (hours)

Flux

(kg/

(m2.

h))

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

Ion

reje

ctio

n (%

)

Flux

Rejection

Membrane-AZA01 Membrane-AZS04

TDS, 3.92104 mg/l

Ion rejection, 74.5%

Flux, 0.112 (kg/m2.h)

TDS (0.55104mg/l)

Ion rejection, 89.2%

Flux, 0.135 (kg/m2.h)

Temperature (oC)

0 20 40 60 80 100

Flu

x (K

g/(

m2 .

h))

Per

mea

nce

(K

g/(

Mp

a.m

2 .h

))

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Flux Permeance

Separation and Flux at Different Temperature

Temperature (C)

0 20 40 60 80 100

Sep

arat

ion

eff

icie

ncy

(%

)0

10

20

30

40

50

60

70

80

Na+

K+

Ca2+

NH4+

Mg2+

a. Flux vs. temperature b. Separation vs. temperature

Separation for Various Ions (Membrane BZA)

Ion

Sal

t re

ject

ion

(%

)

0

20

40

60

80

Na+ K+ Ca2+ Mg2+ SO42- Br- Cl-

• Zeolite membranes show promising properties for ion removal in

produced water.

• The preliminary ion removal cross-flow experiment revealed that:

- MFI Zeolite membrane shows salt rejection of 75% in 4104 mg/l brine

and 90% for 5500mg/l sodium chloride solution.

- Thin and defect-free Zeolite membranes may show high ion rejection

and high flux for application in produced water treatment.

Summary

• Future work:

- Optimize Zeolite synthesis to minimize the cost of membrane

preparation;

- Synthesize and test the desalination of A-type and Y-type

Zeolite membranes;

- Study the mechanism of ion rejection by various types of

Zeolite membrane.

Summary

Acknowledgement

NPTO/NETL/DOE (Dr. Lawson, John Ford)State of New Mexico (Governor, Senators, Representatives)NM Tech President Office (Dr. Lopez)NMOGA, IPANM, NMOCD, and SLO(Bob Gallagher, Deborah Seligman, Jeff Harvard,

Tucker Bayless, Lori Wrotenbery, and Jami Baily)

PRRC Separation group members:Dr. Junhang Dong (group leader)Ashlee RyanXuehong GuAditi MajumdarKatsuya SugimotoAmber WoodyattLiangxiong Li