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The effect of ceria content on the performance of Pt/CeO2/Al2O3 catalysts in the autothermal reforming of methane

A.C.S.F. Santos1, B. A. Riguetto2, S. Damyanova3, F.B. Noronha4, F. B. Passos5, C.M.P.Marques2, J.M.C. Bueno1*

DEQ, Universidade Federal de So Carlos, C.P. 676, 13565-905, So Carlos, SP, Brazil. DQ, Universidade Federal de So Carlos, C.P. 676, 13565-905, So Carlos, SP, Brazil Institute of Catalysis, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria. Instituto Nacional de Tecnologia - INT, Av. Venezuela 82, CEP 20081-310, Rio de Janeiro, RJ,

Brazil.
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Universidade Federal Fluminense, Rua Passos da Ptria, 56, 24210-240 Niteri, Brazil. e-mail: jmcb@power.ufscar.br.

Abstract
Keywords: Pt catalysts, CeO2-Al2O3 carriers, XRD, TPR, OSC, partial oxidation of methane

1. Introduction

2.Experimental

2.1. Catalyst preparation The CeO2-Al2O3 carriers with various CeO2 loading were prepared by impregnation of alumina (Engelhard, SBET=205 m2/g) with an aqueous solution of diammonium hexanitrate cerate (NH4)2[Ce(NO3)6] (99.99% pure product from Aldrich) as described previously in [17]. CeO 2 carrier was obtained by calcination of (NH4)2[Ce(NO3)6] at 923 K in a flow of synthetic air for 2 h. Pt/Al2O3, Pt/CeO2 and Pt/CeO2-Al2O3 samples were prepared by impregnation of the corresponding carrier with a solution of H 2PtCl6.6H2O (Degussa) in ethanol. The appropriate amount of chloroplatinic acid was dissolved in ethanol and the support material was then added. After stirring for 2 h at room temperature ethanol was removed by Rotavapor at 343 K. The samples were dried at 333 K overnight and calcined at 773 or 1173 K for 2 h in air. For all samples the amount of Pt was about 1 wt%. The prepared samples were referred to as Pt/Al 2O3, Pt/CeO2, Pt/(x)CeO2-Al2O3, where x is the theoretical CeO2 content (1, 3, 6, 12 and 20 wt%).

2.2. Characterization Chemical analysis was obtained by inductively coupled plasma-atomic emission spectroscopy (ICP). The composition of the samples is summarized in Table 1. Surface areas (SBET) and pore volumes (Vp) were measured by N2 adsorption at liquid nitrogen temperature using Micromeritics ASAP 2000 apparatus. The results of nitrogen adsorption measurements are given in Table 1.

X-ray diffraction spectra of the samples were collected with a Rigaku DMAX 2500 PC diffractometer, using Cu-K radiation. The step-scans were taken over the range of 2 from 10 to 75o in steps of 0.020 o and the intensity data for each one were collected for 10 s. The size of the crystallites (DXRD) of ceria was determined using Scherrer equation [18]. TPR profiles were recorded on a Micromeritics Pulse Chemisorb 2705 fitted with a thermo conductivity detector (TCD) and controlled by a computer. In order to remove surface contaminants, the sample (0.100 g) loaded in a quartz reactor was pretreated at 423 K in a He stream for 1 h. After cooling to room temperature, a flow of 10 % H2/Ar (30 ml/min) was passing through the sample and the temperature was raised at a rate of 10 K/min up to 1373 K while the TCD signal was recorded. Oxygen storage capacity measurements were carried out in a micro-reactor coupled to a quadrupole mass spectrometer (Omnistar, Balzers). Prior to OSC analysis, the samples were reduced under H2 at 773 K for 1 h and heated to 1073 K in a flow of He. Then, the samples were cooled to 723 K and remained at this temperature during the analysis. The mass spectrometer was used to measure the composition of the reactor effluent as a function of the time while a 5% O2/He mixture was passed through the catalyst. Oxygen consumption was calculated from the curve corresponding to m/e = 32 taking into account a previous calibration of the equipment. The Pt dispersion was determined from the data of cyclohexane dehydrogenation rate and compared with a standard sample. The reaction of cyclohexane dehydrogenation was performed in a fixed-bed reactor at atmospheric pressure. The catalysts were reduced at 773 K for 1 h and the reaction was carried out at 543 K and WHSV = 170 h -1. The reactants were feed to the reactor by bubbling H2 through a saturator containing cyclohexane at 285 K (H2/HC =13.6). The exit gases were analyzed using a gas chromatograph (HP5890) equipped with a HP-INNOWAX capillary column.

2.3. Test reaction Catalytic reaction runs of partial oxidation of CH4 were conducted in a fixed bed quartz reactor at atmospheric pressure. The catalyst (20 mg) was diluted with SiC (36 mg) in order to minimize heat effects. The length of the catalytic bed was such that there was no temperature gradient along the catalytic bed. Prior to reaction, the samples were reduced in situ at 773 K for 1h in 10%H2/N2 flow (50 ml/min) and then heated up to 1073 K under N 2. The catalytic activity of different catalysts were carried out at 773 K and WHSV = 260 h -1. A reactant mixture with CH4:O2 ratio of 2:1 and a flow rate of 100 cm3/min was used. The stability test of the catalysts was carried out at 1073 K in the conditions like the catalytic activity measurements. The exit gases were analyzed using a gas chromatograph (Agilent 6890) equipped with a thermal conductivity detector and a CP-carboplot column (Chrompack).

3. Results 3.1. Characterization of the supports and catalysts Acknowledgments. The authors are grateful for the financial support of FAPESP (Fundao para o Amparo a Pesquisa do Estado de So Paulo), CNPq (Conselho Nacional de Desenvolvimento Cientifico e Tecnolgico) and Petrobras.

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