固载化AlCl_3催化合成金刚烷

以固载化AlCl3为催化剂催化桥式四氢双环戊二烯(endo-TCD)异构化合成金刚烷。采用N2吸附、原子吸收和化学分析方法对载体的比表面积、孔分布和催化剂中氯化物负载量进行了表征;考察了载体类型、催化剂颗粒大小、反应温度、单釜反应时间对催化剂性能的影响。实验结果表明,以γ-Al2O3为载体制备的固载化AlCl3催化剂具有较高的活性和较好的金刚烷选择性;升高反应温度、延长单釜反应时间及使用大颗粒催化剂有利于提高金刚烷选择性。在以20～40目γ-Al2O3为载体的固载化AlCl3催化剂7.5mL、endo-TCD0.5g、环己烷用量20mL、反应温度413K、H2压力2.5MPa、单釜反应时间4h的条件下,endo-TCD转化率为100.0%,金刚烷选择性达24.6%,反应12次后金刚烷选择性降至14.0%。该催化剂可重复使用,失活原因是生成的焦油覆盖了催化剂表面的强酸中心。

Synthesis of Adamantane over Supported AlCl3 Catalyst

Adamantane(ADH) was synthesized by isomerization of endo-tetrahydrodicyclopentadiene(endo-TCD) over supported AlCl_3 catalyst.Surface and pore properties of the supports were characterized by N_2 adsorption,and halide loadings in catalysts were analyzed by atomic absorption spectrometry and chemical method.Effects of support types,particle sizes of catalyst,reation temperature and reaction time on conversion of endo-TCD and selectivity to ADH were investigated.Supported AlCl_3/γ-Al_2O_3 catalyst exhibites high activity and selectivity to ADH.With increases of reaction temperature,reaction time and partical size of catalyst,support to ADH rises.Under optimal reaction conditions:AlCl_3/γ-Al_2O_3 as catalyst,support partical size 20-40 mesh,bulk volume 7.5 mL,endo-TCD dosage 0.5 g,cyclohexane 20 mL,reaction time 4 h,reation temperature 413 K and H_2 pressure 2.5 MPa,conversion of endo-TCD and selectivity to ADH are 100.0% and 24.6% respectively.After 12 time reuses of the catalyst,selectivity to ADH drops to 14.0%.Cause of its deactivition is that strong acid centers on catalyst surface are partially covered by some byproducts such as tar.