Water of Conversion

8/11/2019 Water of Conversion

1/28

Water-Gas Shift

Membrane Reactor Studies

Richard Killmeyer, Kurt Rothenberger, and Bret Howard

US DOE, NETL

Michael Ciocco and Bryan MorrealeNETL Site Support Contractors,

Parsons Project Services

Prof. Robert Enick and Felipe BustamanteNETL Research Associates

University of Pittsburgh

National Energy Technology Laboratory

Office of Science Technology

Fuels and Process Chemistry Division


2/28

NETLs Hydrogen Program

VisionFossil fuel resources are the transition feedstocks for the

production of hydrogen for broad-based applications in

the Hydrogen Economy Mission

Develop and demonstrate technology to produce and to

separate hydrogen for downstream uses, both inadvanced energy plant applications and in off-site

applications

Program Directions

Clean hydrogen for downstream processes

Transition to the Hydrogen Economy

CO2

capture and sequestration


3/28

Coal Gasification Technology Options

Coal,

Petroleum coke,Biomass,

Waste, etc.

Gasifier

ParticulateRemoval

Air Separator

Oxygen

Air

Steam

Particulates

Steam

Solid Waste

GasCleanup

Sulfur Byproduct

CompressedAir

Synthesis GasConversion

ShiftReactor

Fuels andChemicals

Generator

Steam Turbine

CombustionTurbine

Heat RecoverySteam Generator

Combustor

Air

Generator

Stack

Electric

Power

ElectricPower

ElectricPower

Hydrogen

H2Separation

Fuel Cells

GaseousConstituents

Solids

HYDROGEN

SHIFT REACTOR

H2 SEPARATION


4/28

H2 Membrane Reactor Concept

H2

SynthesisSynthesis

Gas...Gas...(H2, CO2, CO,

plus H2O,)

HighHigh

Pressure COPressure CO22

PurePure

HydrogenHydrogen

*WGS Reaction: CO + H2O CO2 + H2*High-T for favorable kinetics

*Membrane removes H2 to shift unfavorable

equilibrium to produce more H2


5/28

Equilibrium Conversion for theWater Gas Shift Reaction

[CO]0=[H2O]0, [CO2]0=[H2]0=0

0

10

20

30

40

50

60

70

80

90

100

200 300 400 500 600 700 800 900 1000

Temperature (o

C)

Reactantconversion(%)


6/28

Project Rationale

Designing WGS Membrane Reactors Requiresthe Consideration of Reaction Kinetics and

Mass Transport PhenomenaForward Water-Gas Shift Kinetics

Reverse Water-Gas Shift Kinetics

Catalytic Effect of Reactor Materials, MembraneMaterials & Heterogeneous Catalyst Particles

Heterogeneous Catalysis May Not Be Needed

Hydrogen Flux Through MembraneHydrogen Selectivity of Membrane

Durability of Membrane in Extreme Environments


7/28

Relevance to EE H2 Production R&D Plan

Project falls within the Technical Objective todevelop technology to produce pure H2 from coal

using a 600C membrane system at a cost of$0.79/kg by 2015

Related Technical Targets are based on use of a

membrane water-gas shift reactor in the system Project addresses Technical Task 4 on

Alternative and Improvements to Conventional

Water-Gas Shift and related technical barriers


8/28

FY03 Approach

Goal: evaluate WGS kinetics and membrane flux usingindustrial gas mixtures and conditions

complete reverse kinetics and CFD modeling to optimize

reactor geometry for forward reaction

measure forward kinetics in quartz & Inconel reactors to

determine reactor wall catalysis

measure forward kinetics in reactor lined with membranematerial to determine catalytic activity

measure membrane H2 permeability in presence of clean

syngas components (CO2, H2O, CO)conduct forward WGS using a membrane reactor at favorable

conditions


9/28

Project Timeline


10/28

FY02 & FY03 Accomplishments

High-T water-gas-shift (WGS) reaction concept: conducted first-ever hi-T and hi-P reverse WGS reaction kinetics study

reverse WGS significantly catalyzed by Inconel reactor wall

conducted CFD simulations for effect of reactor geometry on kinetics

completed intrinsic kinetics testing of forward WGS reaction

Designed & constructed HMT3 unit with enhanced featuresfor membrane reactor testing

F. Bustamante et al., Very High-T, High-P HomogeneousWGS Reaction Kinetics, AIChE Mtg., Reno NV, 11/01

F. Bustamante et al., Kinetic Study of the Reverse WGSR in

Hi-T, Hi-P Systems, ACS H2 Symp., Boston MA, 08/02 F. Bustamante et al., Kinetics of the Homogeneous WGS

Reverse Reaction at Elevated Temp., AIChEJ (in press, 2003)


11/28

NETL Hydrogen Separation Facilities

3 H2 Membrane Test Units

Constructed FY99 to FY02

Temperatures to 900C

Pressures to 400 psi Disk & tubular membranes

1/4 to 1/2 membranes

Feed gas flexibility Membrane separation &

reactor configurations

Clean and sulfur-laden

gas feedstocks Online analysis of

products by GC


12/28

Experimental Setup

CO2

H2

FCV

FCV GC

Vent

TI

PCV

Heated Line

PI


13/28

Quartz Reactor

Premixed H2& CO2 Feed

Overburden CO2

Reactor Effluent

Inconel Alloy 600

Thermocouple

Heating Element

Quartz

Heating Element


14/28

High-T, Low-P Reverse WGS Kinetics

CFD Modeling of Flow Patterns in Reactor

Reactor

Effluent

Reactor

Feed

Graven & Long, 1954NETL, 2002

Simulations performed by S. Shi (Fluent) and B. Rodgers (NETL)


15/28

Kinetic Expression for the Reverse WGSReaction Based on the Bradford Mechanism

Reverse Reaction

CO2 + H2 H2O + CO

r = - kr[H2]0.5[CO]1

kr= kro exp(-Ea/RT)


16/28

High-Temperature (>850oC), Low-Pressure(1 atm) Reverse WGS Quartz Reactor

-6

-5

-4

-3

-2

-1

0.00081 0.00082 0.00083 0.00084 0.00085 0.00086 0.00087 0.00088 0.00089 0.0009

1/T (K-1

)

lnk

Graven & Long, 1954 Kaskan, 1964 (cited by Tingey)

Tingey, 1966 Kochubei & Moin, 1969

Karim & Mohindra, 1974 NETL Low-P, Quartz & Nipple

947oC 917oC932oC 903oC 890oC 876oC 863oC 851oC

Ea, NETL, Low-P = 47.3 Kcal/mol

Ea, G&L = 56 Kcal/mol


17/28

High-Temperature (>850oC), High-Pressure(16 atm) Reverse WGS in a Quartz Reactor

-6

-5

-4

-3

-2

-1

0.00081 0.00082 0.00083 0.00084 0.00085 0.00086 0.00087 0.00088 0.00089 0.0009

1/T (K-1

)

lnk

Graven & Long, 1954 Tingey, 1966

Karim & Mohindra, 1974 NETL Low-P, Quartz & Nipple

NETL High-P, Quartz & Nipple

947oC 917oC932oC 903oC 890oC 876oC 863oC 851oC

Ea, NETL, Low-P = 47.3 Kcal/mol

Ea, NETL, High-P = 53.1 Kcal/mol


18/28

Inconel Reactor

Premixed H2 &CO2

Reactor Effluent

Thermocouple

Heating Element

Inconel Alloy 600

Heating Element


19/28

WGS Reverse Reaction Test Data (Inconelreactor, 900oC, 101.3 kPa, Equimolar H2 and CO2 feed)

0.01

0.1

1

10

100

0.0 0.1 0.2 0.3 0.4 0.5

Residence time, s

CO2conversion,

%

Inconel reactor

Inconel reactor, Inconel-packing

Inconel reactor, quartz-packingQuartz reactor

Equilibrium conversion


20/28

High-Pressure (16 atm), High-TemperatureReverse WGS in an Inconel Reactor

1

10

100

500 550 600 650 700 750 800 850 900

Temperature (oC)

CO2con

version(%)

Inconel Reactor

Equilibrium conversion

Quartz Reactor


21/28

Kinetic Expression for the Forward WGSReaction Based on the Bradford Mechanism

Forward Reaction

H2O + CO CO2 + H2 r = -kf[H2O]

1[CO]0.5

kf= kfo exp(-Ea/RT)

Exponents of 1 and 0.5 verified Boudouard reaction produces C

2CO = C + CO2

Suppress C deposits via short reaction runs Removal of C deposits via overnight O2 purge to

produce CO2


22/28


23/28

Ambient-P, ForwardWGS Inconel Reactor Wall Effects

0.01

0.1

1

10

100

300 400 500 600 700 800 900 1000

Temperature (oC)

H2Oc

onversion(%)

Inconel Reactor

Equilibrium ConversionQuartz Reactor

(xCO)0 = 0.72, (xH2O)0 = 0.28, (xCO2)0 = (xH2)0, ~ 0.5 1 s


24/28

Related Project Activities Funded by DOE-FE

Development of membrane reactors requiresknowledge of both reaction kinetics andmembrane performance

Membranes will be evaluated over a widerange of T (up to 900o C) and P (up to 400 psia)

The H2 permeance and selectivity of dense

membranes and porous membranes will beinvestigated

The effect of CO2, H2O and CO on permeanceand selectivity will be determined

The effect of gaseous contaminants (e.g. H2S)on membrane performance will be evaluated


25/28

Summary of Membrane Permeability Test Data

1.0E-07

1.0E-06

1.0E-05

1.0E-04

1.0E-03

0.0008 0.0010 0.0012 0.0014 0.0016 0.0018 0.0020 0.0022

1/T [K -1]

Pe

rmeance,

k'[m

ol/m

2/

s/Pa0.5]

1000-Micron, UnsupportedPd

100-Micron Pd / Has

25-Micron Pd / Has

22-Micron Pd / Has (Ma)

1000-Micron, UnsupportedTa

1.2-Micron Pd / Ta

0.04-Micron Pd / Ta

25-Micron PdCu / Has

25-Micron PdCu (60/40) /Has

977oC 560oC 352oC


26/28

60%Pd-40%Cu Alloy Permeance ThroughPhase Transition

fcc + bccfcc

1.0E-06

1.0E-05

1.0E-04

1.0E-03

0.0008 0.001 0.0012 0.0014 0.0016 0.0018

1/T [K-1

]

Permeance[mol/m

2/

s/Pa

0.5]

977C 727C 560C 441C 352C 283C

40 60 80300

600

900

Pd wt%

Temp(C)


27/28

Sulfur Tolerance of 60/40 Pd-Cu

1.0E-08

1.0E-07

1.0E-06

1.0E-05

1.0E-04

1.0E-03

0.00080 0.00100 0.00120 0.00140 0.00160 0.001801/T [K

-1]

HydrogenPermean

ce[mol/m

2/

s/P

a0.5]

Hydrogen Exposure

Hydrogen Sulfide

Exposure

977oC 283

oC352

oC441

oC560

oC727

oC

Pure Palladium

fcc Phase bcc PhaseMixed

Phase


28/28

Future Plans

Kinetics studies of the forward WGS reaction

Effect of membrane materials on reaction

kinetics, e.g. Pd, PdCu alloys Effect of sulfur poisoning on catalytic reactor

materials, membrane materials, orheterogeneous catalyst particles

Construction of a sulfur-resistant membranereactor for the forward water-gas shift reaction

Incorporation of all reaction kinetics results

and permeability results into a high T, high PWGS membrane reactor model

Documents

Water of Conversion