工业原料制备大孔拟薄水铝石及在异佛尔酮选择性加氢中的应用

以废催化裂化催化剂处理生产的工业级硫酸铝与偏铝酸钠为原料制备拟薄水铝石，探究制备工艺、扩孔和改性等对拟薄水铝石晶型、孔结构、表面酸性以及形貌的影响。用自制的拟薄水铝石经过挤条、焙烧等过程制备相应的催化剂载体，负载Pd活性组分，研究改性Al2O3载体以及PdCl2和Pd(acac)2前驱体制备的Pd/Al₂O₃催化剂对异佛尔酮C==C选择性加氢反应的活性与选择性。通过优化反应条件得到了比表面积为413 m²/g，孔容为0.84 cm3/g，孔径为6.84 nm的拟薄水铝石。加入扩孔剂碳酸铵和硅酸钠后，拟薄水铝石的孔容分别增大至0.98和1.53 cm³/g，平均孔径分别增至7.70和12.34 nm。以碳酸铵扩孔得到的Al₂O₃为载体和以PdCl₂为前驱体制备得到的Pd/Al2O3催化剂对异佛尔酮C==C选择性加氢活性高，达到98.69%,3,3,5-三甲基环己酮选择性>99%，活性稳定性高。

Preparation of Pseudo-boehamite from Industrial Materials and Its Application in Selective Hydrogenation of Isophorone

Pseudo-boehmite is prepared from industrial grade aluminum sulfate and sodium meta-aluminate coming from waste FCC catalysts. The effects of preparation technology， conditions and modification on crystal type， pore structure， surface acidity and morphology of pseudo-boehmites are investigated. The activity and selectivity of Pd/Al₂O₃ catalyst prepared by modified Al₂O₃ carrier and PdCl₂ and Pd（acac）₂ precursors for the selective hydrogenation of isoporone CC are studied. The pseudo-boehmite with specific surface area of 413 m²/g， pore volume of 0.84 cm³/g and pore size of 6.84 nm is obtained at the optimized preparation conditions. After the addition of ammonium carbonate and sodium silicate， the pore volume of pseudo-boehmite increases to 0.98 cm³/g and 1.53 cm³/g， and the average pore size increases to 7.70 nm and 12.34 nm， respectively. The Pd/Al₂O₃ catalyst that is prepared using Al₂O₃ obtained by ammonium carbonate modifier as the carrier and PdCl₂ as the precursor shows an activity of 98.69% for the selective hydrogenation of isophorone CC， more than 99% selectivity of 3，3，5-trimethyl-cycloheeanon （TMCH）， and high activity stability.