Water-Gas Shift

Membrane Reactor Studies

Richard Killmeyer, Kurt Rothenberger, and Bret Howard
US DOE, NETL
Michael Ciocco and Bryan Morreale
NETL Site Support Contractors,
Parsons Project Services
Prof. Robert Enick and Felipe Bustamante
NETL Research Associates
University of Pittsburgh
National Energy Technology Laboratory
Office of Science & Technology
Fuels and Process Chemistry Division
NETLs Hydrogen Program
Vision
Fossil 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 in
advanced energy plant applications and in off-site
applications
Program Directions
Clean hydrogen for downstream processes
Transition to the Hydrogen Economy
CO
2
capture and sequestration
Coal Gasification Technology Options
Coal,
Petroleum coke,
Biomass,
Waste, etc.
Gasifier
Particulate
Removal
Air Separator
Oxygen
Air
Steam
Particulates
Steam
Solid Waste
Gas
Cleanup
Sulfur Byproduct
Compressed
Air
Synthesis Gas
Conversion
Shift
Reactor
Fuels and
Chemicals
Generator
Steam Turbine
Combustion
Turbine
Heat Recovery
Steam Generator
Combustor
Air
Generator
Stack
Electric
Power
Electric
Power
Electric
Power
Hydrogen
H
2
Separation
Fuel Cells
Gaseous
Constituents
Solids
HYDROGEN
SHIFT REACTOR
H2 SEPARATION
H
2
Membrane Reactor Concept
H
2
Synthesis
Synthesis
Gas...
Gas...
(H
2
, CO
2
, CO,
plus H
2
O,)
High
High
Pressure CO
Pressure CO
2 2
Pure
Pure
Hydrogen
Hydrogen
*WGS Reaction: CO + H
2
O CO
2
+ H
2
*High-T for favorable kinetics
*Membrane removes H
2
to shift unfavorable
equilibrium to produce more H
2
Equilibrium Conversion for the
Water Gas Shift Reaction
[CO]
0
=[H
2
O]
0
, [CO
2
]
0
=[H
2
]
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)
R
e
a
c
t
a
n
t

c
o
n
v
e
r
s
i
o
n

(
%
)
Project Rationale
Designing WGS Membrane Reactors Requires
the Consideration of Reaction Kinetics and
Mass Transport Phenomena
Forward Water-Gas Shift Kinetics
Reverse Water-Gas Shift Kinetics
Catalytic Effect of Reactor Materials, Membrane
Materials & Heterogeneous Catalyst Particles
Heterogeneous Catalysis May Not Be Needed
Hydrogen Flux Through Membrane
Hydrogen Selectivity of Membrane
Durability of Membrane in Extreme Environments
Relevance to EE H2 Production R&D Plan
Project falls within the Technical Objective to
develop technology to produce pure H
2
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
FY03 Approach
Goal: evaluate WGS kinetics and membrane flux using
industrial 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 membrane
material to determine catalytic activity
measure membrane H
2
permeability in presence of clean
syngas components (CO
2
, H
2
O, CO)
conduct forward WGS using a membrane reactor at favorable
conditions
Project Timeline
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 features
for membrane reactor testing
F. Bustamante et al., Very High-T, High-P Homogeneous
WGS 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 H
2
Symp., Boston MA, 08/02
F. Bustamante et al., Kinetics of the Homogeneous WGS
Reverse Reaction at Elevated Temp., AIChEJ (in press, 2003)
NETL Hydrogen Separation Facilities
3 H
2
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
Experimental Setup
CO
2
H
2
FCV
FCV
GC
Vent
TI
PCV
Heated Line
PI
Quartz Reactor
Premixed H
2
&CO
2
Feed
Overburden CO2
Reactor Effluent
Inconel Alloy 600
Thermocouple
Heating Element
Quartz
Heating Element
High-T, Low-P Reverse WGS Kinetics
CFD Modeling of Flow Patterns in Reactor
Reactor
Effluent
Reactor
Feed
Graven & Long, 1954
NETL, 2002
Simulations performed by S. Shi (Fluent) and B. Rodgers (NETL)
Kinetic Expression for the Reverse WGS
Reaction Based on the Bradford Mechanism
Reverse Reaction
CO
2
+ H
2
H
2
O + CO
r = - k
r
[H
2
]
0.5
[CO]
1
k
r
= k
ro
exp(-E
a
/RT)
High-Temperature (>850
o
C), 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
)
l
n

k

Graven & Long, 1954 Kaskan, 1964 (cited by Tingey)
Tingey, 1966 Kochubei & Moin, 1969
Karim & Mohindra, 1974 NETL Low-P, Quartz & Nipple
947
o
C 917
o
C 932
o
C 903
o
C 890
o
C 876
o
C 863
o
C 851
o
C
Ea, NETL, Low-P = 47.3 Kcal/mol
Ea, G&L = 56 Kcal/mol
High-Temperature (>850
o
C), 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
)
l
n

k

Graven & Long, 1954 Tingey, 1966
Karim & Mohindra, 1974 NETL Low-P, Quartz & Nipple
NETL High-P, Quartz & Nipple
947
o
C 917
o
C 932
o
C 903
o
C 890
o
C 876
o
C 863
o
C 851
o
C
Ea, NETL, Low-P = 47.3 Kcal/mol
Ea, NETL, High-P = 53.1 Kcal/mol
Inconel Reactor
Premixed H
2
&
CO
2
Reactor Effluent
Thermocouple
Heating Element
Inconel Alloy 600
Heating Element
WGS Reverse Reaction Test Data (Inconel
reactor, 900
o
C, 101.3 kPa, Equimolar H
2
and CO
2
feed)
0.01
0.1
1
10
100
0.0 0.1 0.2 0.3 0.4 0.5
Residence time, s
C
O
2

c
o
n
v
e
r
s
i
o
n
,

%
Inconel reactor
Inconel reactor, Inconel-packing
Inconel reactor, quartz-packing
Quartz reactor
Equilibrium conversion
High-Pressure (16 atm), High-Temperature
Reverse WGS in an Inconel Reactor
1
10
100
500 550 600 650 700 750 800 850 900
Temperature (
o
C)
C
O
2

c
o
n
v
e
r
s
i
o
n

(
%
)
Inconel Reactor
Equilibrium conversion
Quartz Reactor
Kinetic Expression for the Forward WGS
Reaction Based on the Bradford Mechanism
Forward Reaction
H
2
O + CO CO
2
+ H
2
r = -k
f
[H
2
O]
1
[CO]
0.5
k
f
= k
fo
exp(-E
a
/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 O
2
purge to
produce CO
2
High-Temperature (>850
o
C), High-Pressure
(16 atm) Forward WGS in a Quartz Reactor
-5.5
-5
-4.5
-4
-3.5
-3
-2.5
-2
-1.5
-1
0.00083 0.000835 0.00084 0.000845 0.00085 0.000855 0.00086 0.000865 0.00087 0.000875
1/T (K
-1
)
l
n

(
k
)
NETL, High Pressure GRI prediction, using G&L rate expression
GRI prediction (numerical solution of Bradford mechanism) G&L, experimental data
Ea, NETL = 69.7 Kcal/mol
Ea, G&L = 65. 6 Kcal/mol
Ea, GRI = 71. 6 Kcal/mol
925
o
C 900
o
C 875
o
C
Ambient-P, Forward WGS
Inconel Reactor Wall Effects
0.01
0.1
1
10
100
300 400 500 600 700 800 900 1000
Temperature (
o
C)
H
2
O

c
o
n
v
e
r
s
i
o
n

(
%
)
Inconel Reactor
Equilibrium Conversion
Quartz Reactor
(x
CO
)
0
= 0.72, (x
H2O
)
0
= 0.28, (x
CO2
)
0
= (x
H2
)
0
, ~ 0.5 1 s
Related Project Activities Funded by DOE-FE
Development of membrane reactors requires
knowledge of both reaction kinetics and
membrane performance
Membranes will be evaluated over a wide
range of T (up to 900
o
C) and P (up to 400 psia)
The H
2
permeance and selectivity of dense
membranes and porous membranes will be
investigated
The effect of CO
2
, H
2
O and CO on permeance
and selectivity will be determined
The effect of gaseous contaminants (e.g. H
2
S)
on membrane performance will be evaluated
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
]
P
e
r
m
e
a
n
c
e
,

k
'

[
m
o
l

/

m
2

/

s

/

P
a
0
.
5
]
1000-Micron, Unsupported
Pd
100-Micron Pd / Has
25-Micron Pd / Has
22-Micron Pd / Has (Ma)
1000-Micron, Unsupported
Ta
1.2-Micron Pd / Ta
0.04-Micron Pd / Ta
25-Micron PdCu / Has
25-Micron PdCu (60/40) /
Has
977
o
C
560
o
C 352
o
C
60%Pd-40%Cu Alloy Permeance Through
Phase Transition
fcc + bcc fcc
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
]
P
e
r
m
e
a
n
c
e

[
m
o
l

/

m
2

/

s

/

P
a
0
.
5
]
977C 727C 560C 441C 352C 283C
40 60 80
300
600
900
Pd wt%
T
e
m
p

(
C
)
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 0.00180
1/T [K
-1
]
H
y
d
r
o
g
e
n

P
e
r
m
e
a
n
c
e

[
m
o
l

/

m
2

/

s

/

P
a
0
.
5
]
Hydrogen Exposure
Hydrogen Sulfide
Exposure
977
o
C 283
o
C 352
o
C 441
o
C 560
o
C 727
o
C
Pure Palladium
fcc Phase
bcc Phase
Mixed
Phase
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, or
heterogeneous catalyst particles
Construction of a sulfur-resistant membrane
reactor for the forward water-gas shift reaction
Incorporation of all reaction kinetics results
and permeability results into a high T, high P
WGS membrane reactor model