Synthesis Gas Production by Partial Oxidation of Methane on Pt/Ce-ZrO2 Catalysts by Using Ceramic Membranes.
Maria Conceio Greca1, Lisiane Veiga Mattos1, Elaine R. de Oliveira2, Fbio Barbosa Passos2, Fbio Bellot Noronha1*
1
Instituto Nacional de Tecnologia Laboratrio de Catlise, Av. Venezuela 82, sala 518, CEP 20081-310 Rio de Janeiro, Brasil; e-mail fabiobel@[Link]
Departamento de Engenharia Qumica e Programa de Ps-graduao de Qumica Orgnica Universidade Federal Fluminense, Rua Passos da Ptria 156, Niteri, Brasil.
Important catalytic process, such as synthesis of methanol, Fischer-Tropsch synthesis, hydrodesulfurization and ammonia production requires synthesis gas (mixture of H2 and CO) as raw material. The most important commercial process of synthesis gas production is the steam reforming of methane. Since the steam reforming process has a high capital and operating costs (steam reforming is highly endothermic), alternatives routes to synthesis gas production from methane have been examined. The partial oxidation of methane over supported transition metals is a promising alternative due to the H2/CO ratio obtained, which is appropriated to production of transport fuels such as gasoline and diesel (gas-to-liquid process - GTL) [1,2]. Recent studies showed that Pt/ZrO2 catalysts are more stable in the partial oxidation than Pt/Al2O3 catalysts [3]. Furthermore, the addition of promoters such as CeO2 to ZrO2 can increase the thermal stability of this material and the oxygen transfer capacity [3]. Then, the Ce-ZrO2 supported Pt are a potential catalyst for the partial oxidation of methane. The partial oxidation of methane uses pure oxygen since process like GTL can not contain nitrogen. Then, cryogenic separation is required to O2 production, increasing the cost associated to the partial oxidation. Dense ceramic membranes, that can transport oxygen ions and electrons back from the reactor side to the oxygen/reduction interface, eliminate the need of the plant to separate oxygen from air and of the external electrodes [4]. Therefore, these materials have the potential to reduce the costs of the partial oxidation of methane. Ceramic membranes, such as perovskites of the ABO3 type have been used in partial oxidation reactors. The flux rates of oxygen and the stability of these materials are affected by the reaction conditions. Some works about the performance of these materials in partial oxidation of methane detected problems associated with stability of them under reaction conditions and with fabrication of reactors [5]. Thus, the goal of this work is (i) the development of ceramic membranes to separate oxygen from air and the study of the stability of these materials in the partial oxidation of methane; (ii) the study of the performance of Pt/Ce-ZrO2 catalyst on the partial oxidation of methane. Two different synthesis process of perovskites SrCo0.5FeO3 were compared: 1. Combustion synthesis: This method was previously described in the literature [6]. The powder was prepared from a mixture of Sr(NO3)2; Co(NO3)2.6H2O, Fe(NO3)3.9H2O and CO(NH2)2, respectively. This mixture was heated until boiling and calcined at 873 K in a mufle. The powder obtained was placed on rollers and the contents ball-milled about 15 h with ethyl alcohol to homogenization. Then, the material was dried at 337 K and crushed to a powder, which passed through a # 200 mesh screen. This powder was denoted SCF-C. 2. Mixed oxides: The powder was obtained from a conventional method of mixed oxides, using SrO, CoO and Fe2O3. This mixture was treated following the same procedure used to the power prepared by combustion synthesis. After homogenization, the material was calcined in a muffle at 1223 K, for 2 h, and it was denoted SCF-O. The sintering of materials obtained from both combustion synthesis and mixed oxide were done at 1423 K/2 h (SCF-Cs) and at 1423 K/3 h (SCF-Os), respectively. The powders SCF-C, SCF-Cs, SCF-O and SCF-Os were characterized by x-ray diffraction.
ZrO2 and Ce-ZrO2 supported Pt catalysts were prepared and their performance on partial oxidation of methane was evaluated. ZrO2 support was prepared by calcination of zirconium hydroxide (MEL Chemicals) at 1073 K, for 1 h in a muffle. The Ce0.75Zr0.25O2 support was obtained by co-precipitation method [18]. An aqueous solution of cerium (IV) ammonium nitrate and zirconium nitrate (Aldrich) was prepared with 75 and 25 % (mol %) of CeO2 and ZrO2, respectively. Then, the ceria and zirconium hydroxides were coprecipitated by the addition of an excess of ammonium hydroxide. Finally, the precipitate was washed with distillated water and calcined at 1073 K for 1 h in a muffle. Then, the catalysts were prepared by incipient wetness impregnation of the supports with an aqueous solution of H2PtCl6 (Aldrich) and were dried at 393 K. The samples Pt/ZrO2 and Pt/Ce0.75Zr0.25O2 were calcined under air (50 cm3/min) at 673 K for 2 h. All samples contained 1.5 %wt of platinum. The reducibility and oxygen transfer capacity of these materials were evaluated by Temperature Programmed Reduction (TPR) and Oxygen Storage Capacity (OSC). The effect of the support on the cleaning mechanism of the catalyst surface was investigated by the sequence of CH4/O2 pulses. All materials (SCF-C, SCF-Cs, SCF-O, SCF-Os, Pt/ZrO2 and Pt/Ce0.75Zr0.25O2) were tested on the reaction of partial oxidation of methane at 1073 K, using a reactant mixture with CH4:O2 ratio of 2:1 and a flow rate of 100 cm3/min. The results obtained by XRD experiments showed that the perovskite phase was obtained for all powders (SCF-C, SCF-Cs, SCF-O and SCF-Os). However, the structure of the perovskite obtained by combustion synthesis presented the higher stability on partial oxidation of methane. Then, the powder SCF-Cs seems to be the best material to use as membrane on this reaction. For Ce0.75Zr0.25O2 support, the XRD results showed the formation of a Ce-ZrO2 solid solution. Furthermore, Pt/ Ce0.75Zr0.25O2 catalyst proved to be more active, stable and selective than Pt/ZrO2 catalyst. The results were explained by the higher reducibility and oxygen storage/release capacity of Pt/ Ce0.75Zr0.25O2 catalyst, which allowed a continuous removal of carbonaceous deposits from the surface, favoring the stability and activity of the catalysts, as revealed by the CH4/O2 pulses.
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