>

Francis Lau and Shain Doong

Gas Technology Institute
Des Plaines IL
francis.lau@gastechnology.org
GCEP Energy Workshops
April 26-27, 2004
Francis C. Arrillaga Alumni Center, Stanford University
Coal t o Hydr ogen: A Novel Membr ane
Reac t or f or Di r ec t Ex t r ac t i on
Combustion Fuel Cells Distributed Generation
GAS TECHNOLOGY
I NSTI TUTE
> Independent Not-for-Profit
R&D and Training Organization
18-acre campus
350,000 ft
2
facility
Labs, test facilities, library,
classrooms, offices
> Energy & Environmental Topics
> Fossil and Renewable Energy Focus
Pipeline Materials
Exploration & Production
Gasification
Pr oj ec t Goal
Develop a novel membrane gasification
reactor for low cost production of
hydrogen from coal
Pr oj ec t Team
> Gas Technology Institute
> University of Cincinnati (Dr. Jerry Lin)
> University of Florida (Dr. Eric Wachsman)
Pr oj ec t Sponsor s
> DOE/NETL
> DCEO/ICCI
> AEP
I ndust r i al Advi sor s
American Electric Power, utility
Wah Chang (Allegheny), metals, palladium
membrane
Schott Glass, sealant, hydrogen membrane
ProTek: high temperature membrane
manufacturing
Hydr ogen f r om Coal vi a Gasi f i c at i on
Conventional gasifier
Gasifier
Gas
cleaning
Shift
reaction
H
2
separation
coal
Oxygen/
steam
hydrogen
Membrane gasification reactor
Gasifier
membrane
hydrogen
coal
Oxygen/
steam
Gas
cleaning
CO
2
removal
CO
2
Power
generation
Pot ent i al Benef i t s of Membr ane Reac t or f or
Hydr ogen Pr oduc t i on f r om Coal
> High H
2
production efficiency:
Preliminary thermodynamic analysis indicates over 30 -
50% improvement in H
2
production efficiency over the
current gasification technologies
> Low cost:
reduce/eliminate downstream processing steps
> Clean product:
no further conditioning needed, pure hydrogen
> CO
2
sequestration ready:
simplify CO
2
capture process
> Power co-generation:
utilization of non-permeable coal syngas
Compar i son of Pr oc ess Opt i ons f or
Hydr ogen f r om Coal
Gasifier
Gas
cleaning
Conventional coal to hydrogen
Shift
reaction
H
2
separation 100 100 coal
Gasifier
Gas
cleaning
Membrane shift reactor
Membrane shift
reaction
coal
Membrane in gasifier
Membrane gasification reactor w/o shift reactor
coal
Membrane in gasifier
Gas
cleaning
Membrane gasification reactor w. membrane shift
Membrane shift
reaction
coal
H
2
H
2
H
2
H
2
H
2
For same coal feed
H
2
To gas
product cleaning
129 100
130 60
150 60
Gas cleaning
To power generation
Mass Bal anc e f or Pr oc ess Opt i ons f or
Hydr ogen f r om Coal
Process 1 2 3 4
Hydrogen product, mole 100 129 130 150
H
2
25 1 4 2
CH
4
5 5 0 0
CO 6 0 18 0
CO
2
90 96 83 101
H
2
O 26 21 27 10
Residual gas, mole
1. Conventional coal to hydrogen
2. Membrane shift reactor
3. Membrane gasification reactor w/o shift reactor
4. Membrane gasification reactor w. membrane shift
Membrane reactor increases hydrogen production by
Eliminate loss in PSA (Pressure Swing Adsorption) tail gas
More CO shift H
2
O+CO = CO
2
+H
2
Reform CH
4
CH
4
+H
2
O = CO+3H
2
Typi c al Capi t al Cost Br eak dow n f or Hydr ogen
Pr oduc t i on f r om Convent i onal Coal Gasi f i c at i on
20%
14%
16%
15%
20%
15%
Coal handling and
gasification
Gas cleanup
Shift and H2 separation
Air separation unit
Heat recovery and power
generation
Balance of plant
Membrane
gasification
reactor
reduces these
portions of
capital
Cost of hydrogen from coal: 75% capital, 25% coal and O&M
Membr ane Gasi f i c at i on Reac t or Of f er s a
Low Cost Opt i on f or Hydr ogen f r om Coal
3
4
5
6
7
8
n
a
t
u
r
a
l g
a
s
to
H
2
c
o
n
v
e
n
t
io
n
a
l c
o
a
l t
o
H
2
*
c
o
n
v
e
n
t
io
n
a
l c
o
a
l t
o
H
2
*
*
m
e
m
b
r
a
n
e
s
h
if
t
m
e
m
b
r
a
n
e
g
a
s
ifie
r
F
u
t
u
r
e
G
e
n
ta
r
g
e
t
h
y
d
r
o
g
e
n

c
o
s
t
,

$
/
M
M
B
t
u
*With CO
2
Capture. ** Without CO
2
Capture.
Data based on a study by Parsons Infrastructure and Technology Group, Inc. Hydrogen Production
Facilities Plant Performance and Cost Comparisons, Final Report DOE Contract DE-AM26-99FT40465,
March 2002 (Natural gas: $3.15/MMBtu, Coal: $1.00/MMBtu)
H
2
cost of membrane gasifier case is based on the 50% increase in hydrogen production with 20%
increase in capital for membrane module.
Advanc ed Cer ami c s I dent i f i ed as
Candi dat e Membr ane Mat er i al s
> Certain perovskite-based oxides possess both proton and electron
conductivities at high temperatures (500~ 1200
o
C).
Hydrogen at high pressure
e
-
e
-
H
+
Mixed proton/electron
conducting membrane
H
2
2H
+
+2e
-
2H
+
+2e
-
H
2
H
+
Hydrogen at low pressure
Cer ami c Mat er i al of Per ovsk i t e Type I dent i f i ed as a
Leadi ng Candi dat e Membr ane f or H
2
Separ at i on
> ABO
3-
( oxygen deficiency)
> Conduct both ions (proton or oxide) and electrons
> Proton forms an OH group
> For use in H
2
separation
A : Ba or Sr
B : Ce
B-site dopants :
Y, Yb, Nd, Gd, Eu, .
> Adding a metal phase to the ceramic matrix cermet
To improve electronic conductivity
Li t er at ur e Revi ew on Hi gh Temper at ur e
Hydr ogen Separ at i on Membr ane - Mi x ed I oni c -
El ec t r oni c Conduc t or
Team
Flux, cc/min/cm
2
thickness, mm T, C membrane
U. of Cincinnati
0.04 1.6
900 SrCe
0.95
Tm
0.05
O
3-
Nagoya U. (Japan) 0.056 1 900 SrCe
0.95
Yb
0.05
O
3-
Wachsman (US patent) 0.05 2 600 BaCe
0.95
Gd
0.15
O
3-
Wachsman (US patent) 0.42 2 600 BaCe
0.95
Eu
0.15
O
3-
Argonne 0.072 1 800 SrCe
0.95
Y
0.05
O
3-
UC Berkeley 1.3 0.002 680 SrCe
0.95
Yb
0.05
O
3-
Argonne 20 0.4 900 cermet
Eltron 4 0.2 950 cermet
Hi gh Temper at ur e H
2
Membr ane Mat er i al
Devel opment
> Target flux performance: 50 cc/cm
2
/min
> Current approach:
Operating at higher pressure, higher temperature with
thinner membranes
Addressing chemical stability and durability of membrane
materials
> Test membranes prepared in-house and by others (U. of
Florida and U. of Cincinnati)
> Ceramic membrane development program
GTIs capability to make solid oxide fuel cell membrane
funded by Illinois Clean Coal Institute (ICCI)
> Membrane testing for permeation
Existing unit, low pressure, < 950
o
C
New high pressure unit, 1100
o
C and 1000 psi
I ni t i al Membr ane Mat er i al s t o be Test ed
> BaCe
0.8
Y
0.2
O
3-
(BCY)
25 m, supported on a porous BCY layer (400 m total)
> SrCe
x
Tm
1-x
O
3-
(SCTm)
2 mm
> SrCe
x
Eu
1-x
O
3-
(SCEu)
10-25 m
> Ni/Pd/BCY dual phase membrane
Thi n Membr anes Pr epar ed by Tape-
Cast i ng Tec hni que
Suppor t ed Thi n Fi l m Cer ami c Membr anes
GTI s Suppor t ed Thi n Cer ami c Membr ane
- SEM Pi c t ur e
GTI s Membr ane Per meat i on Appar at us
- ambi ent pr essur e and 1000
o
C
T. C.
1
4
3
2
Membrane
Heated zone T. C.
1
4
3
2
Membrane
Heated zone
1
4
3
2
Membrane Membrane
Heated zone Heated zone
Feed
inlet
Feed
outlet
Sweep
inlet Sweep
outlet
Desi gn of Hi gh Temper at ur e/Hi gh Pr essur e
Hydr ogen Per meat i on Uni t
Membrane diameter:1.25
Max Temp: 1100
o
C
Max Pressure:1000 psi
hydrogen
Inert
sweeping
gas
membrane
Cylindrical
heater
non-permeate
permeate
Inner tube
Outer tube
GTI Hi gh t emper at ur e/Hi gh Pr essur e
Per meat i on Uni t
Hi gh Pr essur e Benc h-sc al e Reac t or
Membr ane Gasi f i c at i on Model i ng -Mat c hi ng
r eac t i on k i net i c s and hydr ogen per meat i on r at e
coal synthesis gas
hydrogen
H
2
H
2
p
H2
f
noncatalytic gas phase rxn
H
2
O+CO = CO
2
+H
2
CH
4
+H
2
O = CO+3H
2
(CH
4
+CO
2
= 2CO+2H
2
)
700-400
o
F approach to equilibrium
for reforming reactions
non-permeate
J
H2
(hydrogen flux) =
RT/F
2

H
[(p
H2
f
)
n
(p
H2
p
)
n
]A/L
p
H2
p
n: 0.25-0.5

H
: proton conductivity
A: membrane area
L: thickness
Membrane tube
Pot ent i al Tec hni c al I ssues and Bar r i er s
> Chemical stability under CO
2
environments for Ba and Sr
cerate perovskites
> Tolerance to other contaminants, sulfur, chlorine, carbon
deposit, etc.
> Steam may increase oxygen conductivity and reduce proton
conductivity
> Higher temperature (>1000C) favors oxygen (oxide)
transport than proton transport
> Interfacial polarization for very thin membrane, may need
catalyst layer to facilitate hydrogen dissociation
GTI Fl ex -Fuel Test Fac i l i t y
Capac i t y: 10 20 t pd c oal , 20 t o 40 t pd bi omass
Pl ug and Pl ay: Feed and gas c ondi t i oni ng syst ems
GTI Fl ex Fuel Test Fac i l i t y
Gasifier Primary Cyclone
0 2 4 6 8 10 year
Material synthesis
Membrane screening & testing
Contaminant issues
Stability & durability
Membrane Module Development
Roadmap of Membr ane Gasi f i c at i on
Reac t or Devel opment
Module configuration design
Large scale membrane
manufacturing
Membrane Gasifier Scale-up
Engineering design
Bench scale testing
Pilot unit testing
Prototype demonstration
Membrane Material
Development