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Reactivity and reusability of mesoporous alumina nanoparticles modified with sulfuric acid and niobic acid in the alkylation of resorcinol

机译:硫酸和铌酸修饰的间孔氧化铝纳米粒子在间苯二酚烷基化中的反应性和可重复使用性

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摘要

With the development of large molecule hydrocarbon processes, mesoporous alumina which possesses high surface area with narrow pore size distribution has received a great deal of attention. However, its acid properties lack Bronsted acidity and showed only Lewis acid sites, making it an inactive solid catalyst in the alkylation of resorcinol, a reaction which requires the usage of solid acid catalysts with both Bronsted and Lewis acidity. In this study, in order to introduce Bronsted acidity to mesoporous alumina, sulfuric acid (H2SO4) and niobic acid (Nb2O5.nH2O) are introduced to the alumina. The reactivity of mesoporous alumina nanoparticles (MAN), Nb2O5.nH2O/MAN and H2SO4/MAN were tested out on the alkylation of resorcinol with methyl tert-butyl ether. No product was obtained using pure MAN, while both H2SO4/MAN and Nb2O5.nH2O/MAN managed to produce butylated resorcinol. Mesoporous alumina nanoparticles incorporated with sulfuric acid produced a greater amount of dibutylated resorcinol, which theoretically is a better antioxidant compared to monobutylated resorcinol. The reusability of the H2SO4/MAN catalyst was also better as dibutylated product was still obtained even in the second use. This indicates that sulfuric acid has created a more stable and also higher strength of Bronsted acidity in alumina as compared to niobic acid
机译:随着大分子烃工艺的发展,具有高表面积,窄孔径分布的介孔氧化铝受到了广泛的关注。然而,其酸性质缺乏布朗斯台德酸度并且仅显示路易斯酸位点,使其成为间苯二酚烷基化中的惰性催化剂,该反应需要使用具有布朗斯台德和路易斯酸度的固体酸催化剂。在这项研究中,为了将布朗斯台德酸度引入介孔氧化铝中,将硫酸(H2SO4)和铌酸(Nb2O5.nH2O)引入氧化铝中。在间苯二酚与甲基叔丁基醚的烷基化反应中测试了介孔氧化铝纳米粒子(MAN),Nb2O5.nH2O / MAN和H2SO4 / MAN的反应性。使用纯MAN不能获得任何产品,而H2SO4 / MAN和Nb2O5.nH2O / MAN都可以生产丁基化间苯二酚。掺有硫酸的中孔氧化铝纳米颗粒产生了大量的二丁基间苯二酚,理论上比单丁基化间苯二酚是更好的抗氧化剂。 H2SO4 / MAN催化剂的可重复使用性也更好,因为即使在第二次使用中仍可获得二丁基化产物。这表明与铌酸相比,硫酸在氧化铝中产生了更稳定的布朗斯台德酸度,并且强度更高。

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