Sol-gel derived Fe2O3-based , Al2O3 supported oxygen carriers for hydrogen production via a chemical looping cycleNur Sena Yüzbasi , Qasim Imtiaz , Christoph R. Müller*Laboratory of Energy Science and Engineering , ETH Zurich , Leonhardstrasse 27 , 8092Zurich , Switzerland*Corresponding author: firstname.lastname@example.orgKeywords: Hydrogen production , sol-gel , iron oxide , iron precursors. Current technologies for hydrogen production such as the steam methane reforming (SMR) process have high production capacities of ̴15 kte H2/year or greater. However , due to issues associated with the storage and distribution of H2 , processes that allow the distributed production of H2 on a small scale may be advantageous.1 For example , the distributed production of high purity hydrogen from biomass (with simultaneous CO2 capture) can be achieved by modifying the conventional thermo-chemical looping combustion process. Here , biomass is first gasified with steam to produce a synthesis gas i.e. a mixture of predominantly CO , H2 , CO2 and H2O. The synthesis gas subsequently reduces iron oxide to a lower oxidation state , thereby producing CO2 and H2O which can be separated via condensation. Subsequent re-oxidation of the reduced iron oxide with steam yields high purity H2. One of the key challenges of the above described looping process is the synthesis of iron oxide-based oxygen carriers that possess (i) a high reactivity , (ii) stable redox characteristics over many cycles and (iii) tolerance to typical synthesis gas impurities e.g. sulphurous components or tarry substances. Recent studies have demonstrated that pure iron oxide , i.e. unsupported iron oxide , deactivates after only a few cycles when reduced completely to Fe. 1 , 2A possibility to stabilize the redox characteristics of iron oxide based oxygen carriers is to stabilize Fe2O3 with a support material e.g. Al2O3 ,3 ZrO2 ,4 MgAl2O4.5 With regards to synthesis techniques , sol-gel methods have received some attention recently since they ensure a homogeneous mixing of the different components and allow the control of the pore structure and surface area of the material. However , there is only limited work on Fe-based oxygen carriers synthesized via sol-gel techniques.3 , 7 In this study , we prepared different Fe2O3-based , Al2O3 supported oxygen carriers (containing 60 wt. % Fe2O3) to assess critically the influence of the iron precursor , viz. iron nitrate (Fe(NO3)3·9H2O) , iron chloride (FeCl3) or iron acetylacetonate (Fe(C5H7O2)3) , on the yield of H2. In addition , the effect of the pH on the structure of the synthesized materials was studied. For comparison , pure iron oxide , i.e. unsupported iron oxide manufactured via mechanical mixing technique , was used. The oxygen carriers were characterized using (i) a thermogravimetric analyser (TGA) , (ii) a packed bed reactor , (iii) X-ray diffraction (XRD) , (iv) N2 adsorption , (v) high resolution scanning electron microscopy (HR-SEM) and (vi) Fourier transform infrared spectroscopy (FTIR). It was found that the oxygen carriers synthesized using iron chloride or iron acetylacetonate as the iron precursor possessed the highest surface areas and pore volumes. In addition , SEM images showed that the use of iron nitrate or iron acetylacetonate as the iron precursor resulted in oxygen carriers that possessed a homogenous and nano-structured morphology. The cyclic H2 production of the oxygen carriers was tested over 15 cycles in a fixed bed reactor. Pure Fe2O3 possessed a high initial H2 yield of i.e.~ 13 mmol/g oxygen carrier. However , after the first cycle the quantity of H2 produced decreased substantially. On the other hand , Al2O3-supported oxygen carriers showed stable redox characteristics over 15 cycles. Oxygen carriers synthesized using iron nitrate as the iron precursor showed the highest H2 yield , i.e. ~ 6 mmols/g oxygen carrier which is nonetheless less than the theoretically expected H2 yield. The lower H2 yield is linked to formation of hercynite , FeO·Al2O3 (as confirmed by the XRD) since its re-oxidation with steam is thermodynamically limited. 7References: C. D. Bohn , C. R. Müller , J. P. Cleeton , A. N. Hayhurst , J. F. Davidson , S. A. Scott , J. S. Dennis , Ind. Eng. Chem. Res. , 47 (2008) 7623-7630. C. D Bohn , J. P. Cleeton , C.R. Müller , S. Y. Chuang , S. A. Scott , J. S. Dennis , Energy Fuels , 24 (2010) 4025-4033. A. M. Kierzkowska et al. , Ind. Eng. Chem. Res. , 49 (2010) 5383-5391. W. Liu , J. S. Dennis , S.A. Scott , Ind. Eng. Chem. Res. , 51 (2012) 16597-16609. J. Adanez et al. , Progress in Energy and Combustion Science , 38 (2012) 215-282. F. Li , H. R. Kim , D. Sridhar , F. Wang , L. Zeng , J. Chen , L. S. Fan , Energy and Fuels , 23 (2009) 4182-4189. P. R. Kidambi , J. P. E. Cleeton , S. A. Scott , J. S. Dennis , C. D. Bohn , Energy and Fuels , 26 (2012) 603-617.
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