24 2013

FC-6
Hydrogen production from high temperature shift reaction of the simulated waste-derived syngas
over metal oxide incorporated Fe/Al catalysts
Hak-Min Kim1), Dae-Woon Jeong1), Won-Bi Han1), Hyun-Suk Na1), Jae-Oh Shim1), Yeol-Lim Lee1),
Hyun-Seog Roh1),*, Yong-Chil Seo1), Yong Taek Lim2), Jae Hoi Gu2)
1)
Department of Environmental Engineering, Yonsei University, Wonju, Gangwon 220-710, S. Korea
2)
Plant Engineering Center, Institute for Advanced Engineering (IAE), Suwon, Gyeonggi 443-749, S. Korea
1.

Introduction

Due to the increasing environmentally friendly energy concerns, H2 attracts significant research interest because it
is a clean energy carrier [1]. In general, hydrogen production from syngas obtained from the reforming of natural gas
can be achieved through the water gas shift reaction (WGS). However, due to the high cost and limited availability of
natural gas, there is a need to develop different processes for hydrogen production from renewable resources [2].
Especially, using waste as an energy source reduces the CO2 emission and exploits an otherwise unused product [3].
Moreover, the production of hydrogen from waste is a management option that has not received recent attention.
WGS is an important process in waste gasification plant for clean hydrogen production from waste-derived
syngas. In general, WGS is carried out at two different temperature regions: high temperature shift (HTS; 350 ~ 500
o
C) using Fe2O3-Cr2O3 catalyst and low temperature shift (LTS; 190 ~ 250 oC) using CuO-ZnO-Al2O3 catalyst [4]. By
the way, the exit temperature of waste-derived syngas is relatively high. Therefore, it is economical to employ HTS of
waste-derived syngas for hydrogen production. The commercial catalyst for HTS is a Fe2O3-Cr2O3 catalyst. However,
the environmental problems related to hexavalent chromium (Cr6+) should be addressed [5]. Thus, many attempts have
been made to develop advanced chromium-free HTS catalysts. Therefore, the objective of the present study is to
compare the catalytic performance of metal oxide (Ni and Cu) incorporated Fe/Al catalysts (chromiumfree) for HTS
over simulated waste-derived syngas under severe conditions.
2.

Experimental

2.1. Catalyst preparation

A solution of Fe (III) nitrate was prepared by dissolving 0.050 M Fe(NO3)39H2O (98%, Aldrich) in distilled
water. Potassium carbonate solution was used as a precipitating agent prepared by dissolving 0.135 M K2CO3 (99%,
Aldrich) in distilled water. In a typical synthesis, precipitation reaction was carried out by the addition of both
solutions to well stirred distilled water kept at 70 oC. The precipitate was then allowed to digest for 6 h under the same
condition. Then, the precipitate was washed with distilled water to remove K+ ion impurity before drying in the oven
at 100 oC for 12 h. The catalyst with aluminum and metal oxide (copper or nickel) was prepared by dissolving a
required quantity of aluminum nitrate (98%, Aldrich) and metal oxide precursor (copper nitrate (99%, Aldrich) or
nickel nitrate (99%, Aldrich)) in the minimum amount of water and the required wt.% of Fe2O3 powder under stirring
condition. The weight ratio was 93/7 for Fe/Al, 83/7/10 for Fe/Al/Cu, and 83/7/10 for Fe/Al/Ni. After stirring for 12 h,
the aluminum and metal oxide incorporated Fe2O3 was kept in the oven at 100 oC for 5 h to remove the water. The
prepared samples were calcined at 400 oC for 3 h in air.
2.2. Catalytic reaction
Activity tests were carried out from 350 to 550 oC under atmospheric pressure in a fixed-bed micro-tubular quartz
reactor with an inner diameter of 4 mm. The catalyst charge was 90 mg. T-union was employed at the exit of quartz
reactor to install a thermocouple. A thermocouple was inserted into the catalyst bed to measure the reaction
temperature. Prior to each catalytic measurement, the catalyst was reduced in 2% H2/N2 from room temperature to 400
o
C at a heating rate of 4.6 oC/min and then the temperature was maintained for 1 h. Afterwards, the temperature was
decreased to 350 oC. The simulated waste-derived syngas consisted of 38.2vol.% CO, 21.5vol.% CO2, 2.3vol.% CH4,
29.2vol.% H2, and 8.8vol.% N2 which represents a typical syngas from waste gasifier that might enter the WGS reactor
in a waste gasification system. The feed H2O/(CH4 + CO + CO2) ratio was intentionally fixed at 2.0 to avoid coke

[CONTACT] Head, Department of Environmental Engineering, Yonsei University, South Korea
Tel: +82-33-760-2834, Fax: +82-33-760-2571, E-mail: hsroh@yonsei.ac.kr
[KEY WORDS] Water-gas shift, High temperature shift, Waste-derived syngas, Metal oxide, Chromium-free

24 2013

formation. A gas hourly space velocity (GHSV) of 40,057 h1 was used to screen the catalysts in this study.
3.

Result and Discussion

Fig. 1 depicts the CO conversion with reaction temperature over Fe/Al, Fe/Al/Cu, and Fe/Al/Ni catalysts. The
Fe/Al/Ni catalyst showed relatively stable CO conversion with reaction temperature. However, CO conversion values
of Fe/Al/Ni are lower than those of Fe/Al/Cu catalyst. The CO conversion of Fe/Al was increased from 27.1% to
46.9% within the temperature range between 450 oC and 550 oC. As a consequence, the Fe/Al/Cu catalyst exhibited the
highest CO conversion within all of temperature range. Fig. 2 shows selectivity to CO2 and CH4 over Fe/Al, Fe/Al/Cu,
and Fe/Al/Ni catalysts at the reaction temperature of 350 oC. In the case of both Fe/Al and Fe/Al/Ni, the undesirable
methanation reaction took place slightly at 350 oC. However, 100% selectivity to CO2 was obtained over Fe/Al/Cu
catalyst. Above 400 oC, almost 100% CO2 selectivity was maintained for all the catalysts (not shown here). Thus, it is
also confirmed that Cu is effective in preventing the methanation reaction in HTS. Therefore, Fe/Al/Cu can be a
promising catalyst for HTS reaction in waste-gasification, because it has a relatively high WGS activity.
100
100
80

Selectivity (%)

CO conversion (%)

80

60

40
Equilibrium
Fe/Al/Cu
Fe/Al/Ni
Fe/Al

20

350

400

450

500

60
40
20

CH4
CO2

550

Fe/Al/Cu

Fe/Al/Ni

Fe/Al

Temperature ( C)

Fig. 1. CO conversion with reaction temperature over

Fe/Al, Fe/Al/Cu, and Fe/Al/Ni catalysts. (H2O/(CH4
+CO+CO2) = 2.0; GHSV = 40,057 h1).

4.

Fig. 2. Selectivity to CO2 and CH4 with reaction

temperature over Fe/Al, Fe/Al/Cu, and Fe/Al/Ni
catalysts. (H2O/(CH4+CO+CO2) = 2.0; T = 350 oC;
GHSV = 40,057 h1).

Conclusion

Fe/Al/Cu exhibited the highest CO conversion as well as 100% selectivity to CO2 using the simulated
waste-derived syngas with the high CO concentration. The remarkable catalytic performance of Fe/Al/Cu catalyst is
mainly ascribed to the synergy effect of Cu metal.
5.

Acknowledgements

This work was supported by the New & Renewable Energy Technology Development Program of the Korea
Institute of Energy Technology Evaluation and Planning (KETEP) grant funded by the Korea government Ministry of
Knowledge Economy (2011T100200273).
6. References
[1] H.-S. Roh, Y. Wang, D.L. King, Top. Catal. 49 (2008) 32-37.
[2] B.E Logan, Environ. Sci. Technol. 38 (2004) 160A-167A.
[3] D.-W. Jeong, V. Subramanian, J.-O. Shim, W.-J. Jang, Y.-C. Seo, H.-S. Roh, J.H. Gu, Y.T. Lim Catal. Lett. 143
(2013) 438-444.
[4] H.-S. Roh, D.-W. Jeong, K.-S. Kim, I.-H. Eum, K.Y. Koo, W.L. Yoon, Catal. Lett. 141 (2011) 95-99.
[5] Y. Sun, S.S. Hla, G.J. Duffy, A.J. Cousins, D. French, L.D. Morpeth, J.H. Edwards, D.G. Roberts, Int. J. Hydrogen
Energy 36 (2011) 79-86.