正丁烷氧化制马来酸酐VPO催化剂的合成及性能研究

O. Diyuk
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摘要

采用传统法和气压热法合成了载体型和负载型钒磷氧化物VPO催化剂。结果表明,使用气溶胶作为VPO相的支撑,取决于其引入反应混合物的时间。它可以形成磷酸钒基氢VOHPO4 0.5H2O的催化剂前驱体,或者形成焦磷酸钒基(VO)2P2O7相,作为正丁烷选择性氧化成马来酸酐的催化活性相。使用由热原气溶胶形成的改性气凝胶作为VPO相的支撑,导致VOHPO4∙0.5H2O相的形成。研究发现,载体的性质影响VOHPO4∙0.5H2O相的形成特征,特别是影响所得VPO相的结晶面比。在应用的VPO相中,使用气泥土作为支撑物导致基面相对含量降低,而使用气泥土凝胶导致基面相对含量增加。研究了散装和负载型VPO样品在标准(1.7 vol.%)和富集(3.4 vol.%)正丁烷混合物中选择性氧化正丁烷制马来酸酐的催化性能。研究发现,在散装样品中富集正丁烷的混合物中,正丁烷的转化率和马来酸酐的选择性急剧降低。与散装样品相比,负载型VPO样品具有更高的正丁烷氧化率和更高的生产率。结果表明,使用气压热合成和气溶胶凝胶作为载体可以提高马来酸酐的选择性,这与VPO相基面相对含量的增加有关。气溶胶凝胶负载的VPO催化剂的催化性能得到了改善,使回收技术具有广阔的发展前景。这可以使马来酸酐的生产更加经济。
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Synthesis and properties of VPO catalysts for oxidation of n-butane to maleic anhydride
Bulk and supported vanadium-phosphorus oxide VPO catalysts were synthesized by traditional and barothermal methods. It was shown that the use of aerosil as a support for the VPO phase, depending on the time of its introduction into the reaction mixture. It can lead to the formation of catalyst precursor of vanadyl hydrogen phosphate VOHPO4 0.5H2O, or a phase of vanadyl pyrophosphate (VO)2P2O7 as already the catalytically active phase for selective oxidation of n-butane to maleic anhydride. The use of a modified aerosil gel formed from pyrogenic aerosol, as a support for the VPO phase, leads to the formation of VOHPO4∙0.5H2O phase. It has been found that the nature of support affects the features of formation of VOHPO4∙0.5H2O phase, in particular, the ratio of crystallographic planes in resulting VPO phase. The use of aerosil as a support leads to a decrease in the relative content of the basal plane, while use of aerosil gel leads to an increase in the relative content of the basal plane in applied VPO phase. The catalytic properties of bulk and supported VPO samples were studied in the selective oxidation of n-butane to maleic anhydride in standard (1.7 vol.%) and enriched (3.4 vol.%) n-butane mixtures. It has been found that in an enriched n-butane mixture for bulk samples, the n-butane conversion and selectivity for maleic anhydride are sharply reduced. It has been found that supported VPO samples have a higher specific rate of n-butane oxidation and higher productivity compared to bulk samples. It was shown that use of barothermal synthesis and aerosol gel as a support made it possible to increase the selectivity of maleic anhydride, which is associated with an increase in the relative content of the basal plane of VPO phase. The achieved improved catalytic properties of VPO catalysts supported with aerosol gel make recycling technology promising. This can make the production of maleic anhydride more economical.
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