酸催化在化学工业尤其是石油化工中有着广泛的用途。与传统的浓硫酸催化剂相比，固体超强酸催化剂具有高活性、高选择性、低腐蚀、低污染以及容易与反应物分离、可重复利用、热稳定性好等特点，符合绿色催化的要求，因而对固体超强酸的研究成为当前的热点之一。 本文以ZrO2为载体负载SO42-，用沉淀-浸渍法制备出固体超强酸SO42-/ZrO2。分别通过水热方法改性；添加其他金属氧化物对载体复合改性；最后在复合载体ZrO2-Al2O3上负载SO42-和MoO3制备了固体超强酸MoO3/ SO42-/ ZrO2-Al2O3。用固体超强酸MoO3/ SO42-/ ZrO2-Al2O3催化合成乙酸丁酯并对其合成工艺进行了优化。 首先通过实验以催化合成乙酸丁酯为探针反应对催化剂SO42-/ZrO2的制备工艺条件进行了优化，得到的最佳制备条件是：陈化pH值等于8；陈化时间为24h；硫酸浸渍液浓度为0.5mol/L；浸渍时间为16h；焙烧温度为550℃。 对在最佳条件下制备的催化剂SO42-/ZrO2与水热改性后的催化剂的催化活性进行了比较，发现水热改性可以提高催化活性；通过添加其它金属氧化物对载体进行了改性，选择了合适的复合金属氧化物Al2O3，确定了合适的Zr/Al原子比为3/2，确定了制备复合载体催化剂的硫酸浸渍液浓度为1.0mol/L，确定了制备复合载体催化剂的焙烧温度为600℃；在复合载体ZrO2- Al2O3的基础上，通过同时负载SO42-和MoO3制备了固体超强酸MoO3/ SO42-/ ZrO2-Al2O3，确定了MoO3的最佳负载量为8wt.%，最佳焙烧温度为650℃，对硫元素的分析发现适当的硫含量有利于提高催化活性，硫含量过高催化活性会降低。 对固体超强酸催化剂分别进行了XRD和FT-IR表征，验证了催化活性与结构变化之间的关系，XRD分析表明改性后的固体超强酸MoO3/ SO42-/ ZrO2-Al2O3中ZrO2和Al2O3以无定形态存在，FT-IR分析表明SO42-与催化剂载体之间的结合属于螯合双配位。通过TG分析表明催化剂MoO3/ SO42-/ ZrO2-Al2O3具有很好的热稳定性，在600℃以前没有硫的分解，用Hammett指示剂法对酸强度进行了表征，表明是固体超强酸。 最后用制备的固体超强酸催化剂MoO3/ SO42-/ ZrO2-Al2O3催化合成乙酸丁酯，对合成的工艺条件进行了优化，并对催化剂的使用寿命进行了考察。得到的最佳合成条件是：催化剂用量0.8g，占反应物总质量的4%；带水剂环己烷的用量为4mL；正丁醇和乙酸的比例为1.6；反应时间为120min。催化剂重复使用5次后对乙酸的转化率仍在80%以上。对合成产物进行了红外光谱分析，从红外图谱与标准图谱对比确认合成产物确实是乙酸丁酯。

Acid catalysts are found numerous applications in many areas of the chemical industry especially in the petroleum industry. Compared with the traditional catalyst H2SO4, solid superacid has many advantages such as high activity, well selectivity, no corrosiveness, no pollution, and liability to be separated from the reaction material. It is a green industrial catalyst that is helpful to recycling and possesses wide prospect of application. Thus, research on solid superacid has drawn more and more attention in industrial catalyst field. In this paper, superacid catalysts SO42-/ZrO2 were prepared by precipitation and impregnation method. The catalysts were modified seperately by hydrothermally, by prepare ZrO2-Al2O3 mixed oxide carrier, and by prepare MoO3 promoted SO42-/ ZrO2-Al2O3 superacid catalysts.Then the catalysts MoO3/ SO42-/ ZrO2-Al2O3 were used in the esterification of acetic acid and n-butanol. The result showed that the solid superacid behaved well in the esterification. First, the preparation conditions of the catalyst SO42-/ZrO2 were made sure by experiment. The preparing conditions were optimized and discussed according to different yields through which the activity of the catalyst in esterification of acetic acid and n-butanol was measured. The best preparing conditions were as following: pH=8;the depositing time equal to 24h; the concentration of H2SO4 equal to 0.5mo1/L;the impregnated time equal to 16h;and the burning temperature equal to 550℃. Second, the solid superacid SO42-/ZrO2 was modified.The results show that the catalysts modified by hydrothermally have better activity in esterification.The appropriate mixed metal oxide Al2O3 were selected,and the suitable Zr/Al atom ratio were 3/2 in the mixed oxide carrier.In preparing the catalysts SO42-/ ZrO2-Al2O3 , the concentration of H2SO4 equal to 1.0mo1/L, the calcinated temperature equal to 600℃. The catalysts MoO3/ SO42-/ ZrO2-Al2O3 were prepared by impregnating mixed oxide carrier ZrO2-Al2O3 into appropriate solution of H2SO4 and ammonium molybdate. The esterification results show that the catalytic activity disagree with the contents of sulphur. It indicate that appropriate amount sulphur were help to increase the catalytic activity ,and there were the best catalytic activity when added 8.0wt.%MoO3 and calcinated at 650℃. Third, the solid superacids were analyzed and characterized by XRD, FT-IR and TG. The relationships between properties and structures were also investigated. By the FT-IR analyzed, we found that SO42- is combined with metal oxide in a chelating bidentate mode;by XRD we found that the ZrO2 and Al2O3 were amorphous;by TG analyzed, we found that the catalysts have high thermal decomposition temperature,it is stability when the temperature were 600℃.The acid strength were investigated by Hammett indicators method,which show the catalysts were superacid. Finally, the solid superacid MoO3/ SO42-/ ZrO2-Al2O3 was used to catalyze the esterification of acetic acid and n-butanol.The synthesis conditions had been optimized and discussed by the yield of esterification. The best conditions were as following: reaction for 120min;molar ratio of acid and ethanol 1:1.6;the water-carrying agent 4mL;the content of catalyst 4%. The best yield was 88.9% The solid superacid can be reused for five times and the yield no less 80%.At last, the result of esterification was analyzed by FT-IR and the result showed it was n-butyl acetate.