Treating Coal-Bed Methane Produced Water for Beneficial Use by MFI Zeolite Membranes

Contract #: DE-FC26-04NT15548Project term: 10/01/04 ~ 09/30/07

Principal Investigator: Junhang DongProject Manager: Robert Lee

Petroleum Recovery Research CenterPetroleum and Chemical Engineering Department

New Mexico Tech, Socorro, NM 87801Ph: (505) 835-5293; Fax: (505) 835-5210; Email: jhdong@nmt.edu

Program Manager: Jesse Garcia

NETL/DOE, TulsaApril 17, 2004

THE RESEARCH GROUP

Justin Monroe, Ben Brooks, Marlene Axness, Alex Bourandas, Junhang Dong, Rich Zhang, Theo Hosemann Xuehong Gu, Liangxiong Li, Colin Edwards, Ani Kulkarni, Chunkai Shi

Spring 2005

1% PW, 1,800ppm

100% PW, 180,000ppm

10% PW, 18,000ppm

0% PW

0% PW 1% PW, 1,800ppm

100% PW, 180,000ppm

10% PW, 18,000ppm

Grass Alfalfa

From Brittni Romero (Socorro middle school), NM State Science Fair 2005

Hobbs oilfield PW 180,000ppm; Farmington CBM PW 18,000ppm.

(Hobbs) (~CBM)

Gas-field & OilfieldProduced Water Clean Water

ConcentratedProd. Water

CBM Produced Water Management Challenge and Our Strategy

Disposal, e.g. deep well injection (costly) …

SEPARATION

(Beneficial uses)

Challenge: Lacking of technology for efficient SEPARATION

Goal of this project:Reverse osmosis purification of CBM produced water by molecular sieve zeolite membranes

Comparison With Benchmark Polymeric RO Membranes

Properties Polymer Membrane Zeolite membrane

Organic resistance Poor Excellent

Organic rejection Incapable of Very good

Ion rejection Good Good

Applicable TDS levelLow (<4%) High (to saturation)

Membrane regeneration Difficult Simple

Lifetime Short (< 3 mon) Long (> 5yr)

Chemical stability Unstable in low pH Stable: acidic to basic

Operating pressure >800 Psi < 450 Psi

Thermal stability Poor Outstanding

Water flux >5 kg/h.m2 ~0.5 kg/h.m2

Membrane cost Low High

PROJECT OBJECTIVES

PHASE 1: Mechanisms of the reverse osmosis process on zeolite membranes and factors determining the membrane performance (10/04 ~09/05)

PHASE 2: Membrane improvement and operating condition optimization to enhance water flux and ion rejection (10/05~09/06)

PHASE 3: Long-term reverse osmosis operation, data generation, and evaluations of technical and

economic feasibilities (10/06~09/07)

GO/NO GO point

GO/NO GO point

SCHEDULE

TaskYEAR 1 YEAR 2 YEAR 3

Q1

Q2

Q3

Q4

Q1

Q2

Q3

Q4

Q1

Q2

Q3

Q4

Subtask 1.1. Synthesize and improve zeolite membranes ● ● ● ● ● ● ● ● ● ●

Subtask 1.2. Water and ion transport mechanisms ● ● ●

Subtask 1.3. Effects of operating conditions ● ● ●

Subtask 2.1. Membrane modification in simple solutions ● ● ●

Subtask 2.2. Membrane modification in produced water ● ● ●

Subtask 2.3. Stability of modified membrane ● ●

Subtask 3.1. Build 0.1-m2 membrane unit ●

Subtask 3.2. Long-term operation test ● ● ● ●

Subtask 3.3. Technical and economic evaluations ? ? ? ? ●

Subtask 3.4. Final report ●

Research Progress (PHASE 1)SUBTASK 1.1 Synthesize and improve zeolite membranes• In-situ growth is better than seed-secondary growth for MFI type (pd = 0.55nm)• Seed-secondary growth is better than in-situ for FAU type (pd = 0.74 nm)• Synthesis of high quality MFI membranes on commercial tube substrates (Pall Co.)

NaY (FAU) membrane Substrates and DESAL unitMFI membrane

Characterization & broader applications

0 10 20 30 40 50Vapor partial pressure, kPa

0

2E-8

4E-8

6E-8

8E-8

Gas

per

mea

nces

, molm

-2S

-1P

a-1

0

1

2

3

4

5

CO

2/N2 S

epar

atio

n fa

ctor

C O 2 perm eanceN 2 perm eanceC O 2/N2 separation factor

NaY for CO2/N2/H2O separation at 200oC. (Ind. Eng. Chem. Res., 2005)

Zeolite framework

Pt-Co cluster

CH

4 feed

H2 sw

eep

CH4

CHx

H2

C2+

H+

Zeolite pore

r

N

nn

N

nnnn

CcatCoPtN

nn HHnHCCHn

o

2

2222

300~,4

2

)]1([)()(

Pt-Co/NaY for CH4 conversion to H2 and C2+. (Catalysis Letters, 2005)

FAU (NaY) Membranes

MFI for separations of xylene isomers. (AIChE J. 2005. In preparation)

MFI-fiber integrated sensor for water monitoring. (Optics Letters, 2005)

MFI Type Membranes

-46.0

-45.0

-44.0

-43.0

-42.0

-41.0

-40.0

0 10 20 30 40 50 60 70 80

Concentration (ppm)

Opt

ical

Pow

er (d

Bm

)0

5

10

15

20

25

30

0 20 40 60 80 100

P-xylene molar ratio, %

Sepa

ratio

n fa

ctor

, p/o

300 oC250 oC200 oC

Surface

Cross-sectionPore dia. ~ 0.55 nm

Film of inter-grown crystals

Undesirable intercrystal pore

Zeolitic pore

SUBTASK 1.2 Water and ion transport mechanisms

RO permeation mechanism:1. Rejection size exclusion (high)2. Lower rejection at intercrystal pores3. Flux: water and ion diffusivities

Ion and Water Transport Through the Zeolite MembraneIon and Water Transport Through the Zeolite Membrane— — Separation MechanismSeparation Mechanism

0.0

0.5

1.0

1.5

2.0

2.5

2.9 3.0 3.1 3.2 3.3 3.4 3.5 3.6

1000/T, 1/K

ln(F

W)

-12.0

-10.0

-8.0

-6.0

-4.0

-2.0

0.0

2.0

ln(F

i)

Water (LiCl)Water (NaCl)Li+Na+

RO desalination for LiCl and NaCl solutions of 2.75MPa.

T, oC0.1 M LiCl 0.1 M NaCl

ri, % Fi, mol·m-2·h-1 FW, mol·m-2·h-1 ri, % Fi, mol·m-2·h-1 FW, mol·m-2·h-1

10 99.3 0.52104 3.57 97.2 1.26104 3.91

30 99.0 0.79104 3.83 98.0 2.11104 5.66

50 98.8 1.39104 5.92 98.7 12.52104 6.44

60 98.7 1.89104 7.17

1.3 Effects of operating conditions

94

96

98

100

0.6 0.8 1 1.2 1.4 1.6 1.8 2Crystallographic radius, Angstrom

Li+ Na+ K+ Rb+ Cs+

0.0

2.0

4.0

6.0

8.0

10.0

0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0Crystallographic radius ion, Angstrom

0.0E+00

3.0E-04

6.0E-04

9.0E-04

1.2E-03

1.5E-03water

solute ion

Li+ Na+ K+ Rb+ Cs+

Mechanism: Theoretical model for ion transport & RO process

RTECK

RTEECK

RTE

RTECKnn fififiii

3,

'1

210,1

20

1,1

0 expexp)(expexp

RTE

CKn ww4'

2 exp

RT

EEC

KK

CnnCnn

nxC fiwwiw

iw

isolfi

43,'

2

'1

1', exp)/(/

Fick’s Law equation: pifiDa

ii

ii

CCRTE

DddC

DJ ,,0 exp

RT

EEKK

i43

'2

'1

1, exp

',

',,

0,

'

,, exp pifiDii

iciDi

CCRTE

DddC

DJ

fiici

fiDiiDi

CD

CRT

EEKK

RTE

DJ ,1,,

,43'2

'1,

0,, expexp

][,

pf

wwDw

ppK

ddpKJ

RTE

RTKVRTvKD Dw

ww

wWw,0 exp)(

wi

DwDii nn

JJxx

xxxx

//

)1/()1/( ,,

1

2

11

222,

wfi

DwDiiimi CC

JJ/

/)()(

,

,,2,1,,

Modified Diffusion Model (Steps 1+2):

Ions entering zeolitic pores:

Water entering zeolitic pores:

Ion con. Inside pore on feed side:

Step 1 selectivity:

Ion flow rate:

Step 2 selectivity:

Overall selectivity:

Water flow rate:

Effect of inter-crystal pores and membrane modifications(PHASE 2, SUBTASK 2.1)

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)Sa

lute

reje

ctio

n (%

)

Before

After

Difference

0.37 0.09 0.04 0.010.0150.02

Feed Concentration (M)

Minor adjustment1. Economic evaluation (via simulation) earlier ?

Received many inquiries about the economic feasibility. 2. Start building the demon unit earlier ?

Program status

Slightly ahead the schedule

Sensor Program at NMTSensor Program at NMTHai Xiao (PRRC/EE, NMT)Hai Xiao (PRRC/EE, NMT)

Junhang Dong (PRRC/ChE, NMT)Junhang Dong (PRRC/ChE, NMT)

• Strategy: Strategy: Nanomaterial-enabled optical chemical sensors by interdisciplinary

approaches.

• Challenges:Challenges: Highly sensitive and selective for in-situ and continuous operation.

• ObjectiveObjective Robust sensors for in-situ detection/monitoring of various chemicals involved energy industryenergy industry and environment protectionenvironment protection.

Sensors for Produced Water Management

● Approach: Approach: Miniaturized sensors by integrating zeolites with optical fibers

● Objective Objective In-situ monitoring of various organics in produced water

-35.3

-35.1

-34.9

-34.7

0 100 200 300 400 500

Isop. concentration (ppmv)

Sen

sor o

utpu

t (dB

m)

-34.745

-34.735

-34.725

-34.715

-34.705

-34.695

0 20 40 60 80

Time (s)

Zeol

ite s

enso

r out

put (

dBm

)

10ppm

Silicalite sensor response to isopropanol concentration in water.

MFI (Si/Al=200) sensor response to pentanoic acid in water.

-46.0

-45.0

-44.0

-43.0

-42.0

-41.0

-40.0

0 10 20 30 40 50 60 70 80

Concentration (ppm)

Opt

ical

Pow

er (d

Bm)

34ppm

-49.5

-48.5

-47.5

5.8 6 6.2 6.4Time (hrs)

Out

put (

dBm

)

(a)

100m

(b)

10m

(d)

~4 m fiber

zeolite(c)

Optical fiber

Laser diode (1539.5nm)

3dB fiber coupler

Fiber sensor head

Antireflection angle-cleaved endface Optical

power meter

Zeolite coating

Optical fiber

Computer

Needle

Stirrer

Sensors for Coal-Firing Power PlantsSensors for Coal-Firing Power PlantsFunded by DOE/NETL (4/1/05 – 3/31/08)Funded by DOE/NETL (4/1/05 – 3/31/08)

● Objective: Objective: Develop low-cost, reliable, and miniaturized sensors for in-situ monitoring of gas composition in flue or host gas streams of coal-firing power plants.

● Challenge: Challenge: Harsh environment: high temperature, high pressure, and particulates

● Strategy:Strategy: Nanocrystalline doped-ceramic enabled optical fiber sensors

Drop of polymeric precursor

Optical fiber (a)

Precursor coating

(b)

YSZ coated fiber tipYSZ coated fiber tip

Typical LFPG transmission spectrum

Protection film

Whitelight source

Optical fiber

Gas sensor OSA

Chemsorber film

LPFG

Cladding

Core

Optical fiber

Photo of the Photo of the experimental experimental setupsetup

Sensor Sensor response to response to OO22 and N and N22 at at 500500CC

One of the One of the proposed proposed sensor sensor structuresstructures

Sensors for Environmental MonitoringSensors for Environmental Monitoring• Sensors for in-situ chemical vapor detectionSensors for in-situ chemical vapor detection

0 10 20 30 401.8

2.2

2.6

3

Time (s)

Sen

sor o

utpu

t (nW

)

100% N2

Isopropanol (1.3%) in N2

Sensor response to isopropanol concentration in N2. Inset: response to gas switching.

• Sensors for in-situ detection of heavy ions (e.g. Hg) Sensors for in-situ detection of heavy ions (e.g. Hg)

Optic fiber

Isopropanol saturator

Vent

N2 from cylinder

Triple-point water bath (0oC)

N2 from cylinder

Gas mass flow controllers Valve

Valve Mixer

1/32” ID SS tubular sensor chamber

Signal processing

Light source

Optical fiber

50:50 fiber coupler

Optical detections Zeolite coated sensor

Reference unit

Thermal diffusion region

Fiber core

Option 3: Thermal treatment

Cladding

Zeolite coating

Option 1: Etched fiber Option 2: Tapered fiber

Zeolite coating

Principle of zeolite-coated fiber mercury sensor

Sensors for Hydrogen InfrastructureSensors for Hydrogen InfrastructurePlanned WorkPlanned Work

• Fiber sensors for hydrogen production and fuel cellsFiber sensors for hydrogen production and fuel cells – Real time and in-situ monitoring the chemical compositions Real time and in-situ monitoring the chemical compositions

to achieve optimal fuel cell operations.to achieve optimal fuel cell operations.– Small size for easy deployment/integration.Small size for easy deployment/integration.– High temperature capability and material compatibility for High temperature capability and material compatibility for

solid oxide fuel cells. solid oxide fuel cells.

• Fiber sensors for hydrogen transportation and Fiber sensors for hydrogen transportation and storagestorage– Continuous monitoring of hydrogen flow and leakage. Continuous monitoring of hydrogen flow and leakage. – Remote and distributed operation to pin-point the problem. Remote and distributed operation to pin-point the problem. – Passiveness for maximum safety. Passiveness for maximum safety.

THANK YOU!THANK YOU!

SSOCORRO OCORRO NMNM WWILDLIFE ILDLIFE RREFUGEEFUGE