1. Catalytic WGS Multi-Function Membrane Reactor
P. Bossard Ph.D., J. Mettes Ph.D.
Power & Energy Inc.
106 Railroad drive,
Ivyland, PA, USA
Power+Energy, Inc.

2. P+E acknowledges support for this project under a BAA contract from the Office of Naval Research, Ships and Engineering Systems Division, Code 331 Arlington VA and guidance from NAVSEA, Energy Conversion Section, Code 9823, Philadelphia
Power+Energy, Inc.

3. Topics Integrated Fuel Processor
Wall Catalyzed Micro-Channel Water-Gas Shift Membrane Reactor
Sulfur immunity
Wall Catalyzed Micro-Channel Reformer
Manufacturability
Power+Energy, Inc.

4. Fuel Processing
Power+Energy, Inc.

5. Conventional and New Fuel Processing Schemes*
REFORMER
WGS
REACTOR H2
SEPARATOR H2
PURIFIER
FUEL
CELL
FUEL &
WATER
ELECTRICITY
Conventional
REFORMER
MEMBRANE
REACTOR
FUEL
CELL
FUEL &
WATER
ELECTRICITY
New
* Z. Dardas, UTC, On-Board Vehicle, Cost Effective Hydrogen Enhancement Technology for Transportation PEM Fuel Cells, FY 2003 Progress Report on DOE website.
Power+Energy, Inc.

6. Quotation*: “The best possible solution for H2 separation in fuel processing would be a membrane reactor combining shift and separation, realizing a significant leap forward in efficiency and lowered cost”
* Kurt S. Rothenberger et al., Palladium-copper Alloy Membrane Performance under Continuous H2S Exposure, Report, available at NETL/DOE website.
Power+Energy, Inc.

7. Experimental setup for integrated fuel processor and WGS membrane reactor test
Power+Energy, Inc.

8. Reformer and Membrane Reactor
multifunctional membrane reactor
Power+Energy, Inc.

9. Ethanol Conversion to Hydrogen with Integrated Fuel Processor
Power+Energy, Inc.

10. WGS Reaction in Micro-channel Wall-catalyzed Membrane Reactor
Operating conditions membrane reactor:
Temperature 650 °C, pressure 100 psia,
NO ADDED Catalyst, micro-channel with hastelloy wall,
High (10:1) steam to carbon ratio to drive the reformer cracking reaction close to completion and minimize coking (no coke deposition was detected after the experiment)
residence time in the micro channel 0.24 sec.
Power+Energy, Inc.

11. Results WGS in Micro-channel Wall-catalyzed Membrane Reactor
CO2/CO concentration ratios:
5 at inlet membrane reactor (0.5% of total carbon as CH4)
9 at outlet membrane reactor (1.7% of total carbon as CH4)
Corresponding to 40 % WGS conversion.
Good agreement with DOE data with inconel reactor, see next two slides.
Same measurements on a similar membrane reactor with a micro-channel with stainless steel wall operating at 500 °C showed little measurable CO conversion.
Power+Energy, Inc.

12. Reversed WGS, DOE results*
* R. Killmeyer et al., Water-Gas Shift Membrane Reactor Studies, NETL FY 2003 Progress Report, available on the DOE/NETL website.
Power+Energy, Inc.

13. WGS Conversion versus Residence Time*
* R. Killmeyer et al., Water-Gas Shift Membrane Reactor Studies, NETL FY Progress Report, available on the DOE/NETL website.
Power+Energy, Inc.

14. Sulfur immunity Extreme H2S exposure of micro-channel membrane module;
well over 10x the levels reforming 3000 ppmww diesel fuel
The membrane’s hydrogen separation remained unchanged
Sulfur contribution on alloy composition within the noise level of about 0.5%.
Power+Energy, Inc.

15. Unaffected membrane (left) next to FeS slab (right) from micro-channel
SEM Picture
Unaffected membrane (left) next to FeS slab (right) from micro-channel
Power+Energy, Inc.

16. EDAX spectrum of unaffected membrane next to FeS slab
Power+Energy, Inc.

17. Wall-Catalyzed Micro-Channel Reformer Test Setup
Power+Energy, Inc.

18. Wall-Catalyzed Micro-channel Reformer Test Conditions
Ethanol/water mixture with a steam to carbon ratio of 10
950 and 750 °C wall-catalyzed reactor temperature
Feedrate mixture 0.25 cc/min corresponding to a maximum extractable H2 flowrate of 85.6 cc/min
90 microliter reactor volume,
Geometric surface area per reactor volume 300 cm2/cm3,
50 milliseconds residence time, 0.5 m/sec. gas speed.
Power+Energy, Inc.

19. Wall-Catalyzed Micro-channel Reformer Results
110 ± 20 cc/min. dry gas mixture at 950 °C reactor temperature
Mixture composition:
66% H2, 13% CO, 6% CH4 and 15% CO2 at 950 °C,
58% H2, 18% CO, 12% CH4 and 12% CO2 at 750 °C
Corresponding H2 flow rate: 73 ± 15 cc/min at 950 °C reactor temperature
Power+Energy, Inc.

20. Wall-Catalyzed Micro-channel Reformer Advantages
Addresses dominant limiting poor heat transfer between the reactor wall and the inside of the traditional catalyst bed*.
No conventional catalyst, no hot spots, no dead volume.
Good outlook for sulfur immunity.
Highly scalable and manufacturable micro channel design.
Potential for a fuel neutral device.
* H. Chul Yoon et al., Reactor design limitations for the steam reforming of methanol, Applied Catalysis B: Environmental, 26 Sept. 2007, pp
Power+Energy, Inc.

21. Same basic manufacturing techniques as for hydrogen purifier.
Manufacturability
Same basic manufacturing techniques as for hydrogen purifier.
Purifiers consistently used in semiconductor manufacturing with 24/7 reliability with single digit ppb impurity levels*.
High level of automation in place:
- HSMA unit contains 2700 membranes
- automated welding
- each membrane individually leak checked, after installation into manifold
- various inspection and diagnostic tests per individual membrane.
* H. Funke et al., Optimization of palladium cell for reliable purification of hydrogen in MOCVD, Journal of crystal growth  (J. cryst. growth), vol. 248, Feb. 2003, pp 72-76(5),  ISSN     CODEN JCRGAE.
Power+Energy, Inc.

22. HSMA H2 Separator for the Navy, delivered Jan
HSMA H2 Separator for the Navy, delivered Jan. 08, with up to 200 kW(e) Capacity*
* Reformate: 265 psia, 65% H2 (steam reforming)
H2 delivery at 20 psia, 450 °C operating temp.
Power+Energy, Inc.

23. 2700 Membranes HSMA, width 22”, height 26” and 24” deep
Power+Energy, Inc.

24. HSMA final assembly
Power+Energy, Inc.

25. Conclusion
Demonstration of integrated ethanol reforming setup with up to 85% yield producing slpm flow of pure hydrogen consistently over a 2 months period.
Wall-catalyzed Water-Gas Shift membrane reactor with Palladium alloy membrane and Hastalloy micro-channel configuration demonstrated to perform 40 % WGS conversion at high temperature operation 650 °C.
High sulfur tolerance and chemical inertness was illustrated by SEM and EDAX analysis of a membrane alloy under “unrealistically” high exposure.
Wall-catalyzed micro channel reformer concept addresses dominant heat transfer steam reformer bottleneck and traditional catalyst issues.
Manufacturing automation discussed and real world 200 kWe HSMA performance spec. and assembly pictures shown.
Power+Energy, Inc.