固体超强酸在松节油水合反应中的应用

【作者】 刘天成；

【导师】 王亚明；

【作者基本信息】 昆明理工大学 ， 应用化学， 2003， 硕士

【摘要】 松油醇是松节油再加工的最大宗产品之一，主要用作冶金浮选的起泡剂、医药、印刷油墨、纺织、燃料工业的助剂；广泛应用于合成香料中，是香精工业中产量最大的产品。制备高收率的松油醇有着重要的意义。 本论文是以松节油为原材料，采用自制的固体超强酸作催化剂一步催化水合制备松油醇。分三个部分进行：一，催化剂的制备及其催化性能考察，考察了四种类型的催化剂、粒径、焙烧温度、焙烧时间、浸渍浓度，发现固体超强酸催化剂D2的活性最佳，粒径为E3以上、焙烧温度A2、焙烧时间B2、浸渍浓度为C2时催化效果最好。二，松油醇的制备及结果讨论，从反应温度、时间、物料配比、酯化剂的种类与用量、溶剂的选择、催化剂寿命等几个进行了考察，结果发现反应温度为T3、时间L5小时、酯化剂用F3、物料配比为H3％、溶剂用G等时，松节油的转化率为86.29％、松油醇的收率为68.89％、固体超强酸催化剂的选择性为79.84％。催化剂的重复使用率很高，寿命长。三，催化剂的物性测试，讨论制备方法对D2结构的影响、超强酸酸性的测试以及D2固体超强酸的结构特征，在此基础上提出其超强酸酸性模型。XRD、TEM、IAS的结果表明，制备方法对D2结构有决定性影响。钼酸铵浸渍仅经干燥的Zr（OH）₄再焙烧制得的固体超强酸MoO₃／ZrO₂（Ⅰ）与浸渍晶态ZrO₂制得的部分氧化催化剂MoO₃／ZrO₂（Ⅱ）的载体形态有明显不同。活性组分的存在形式明显不同，在MoO₃／ZrO₂（Ⅱ）中，MoO₃以二维聚钼酸根形式单层分散在ZrO₂上（其中单斜ZrO₂为主）。在MoO₃／ZrO₂（1）中，活性相以二维聚钼酸根和Mo-O-Zr表面物种两种表面态存在于介稳的四方ZrO₂上，MoO₃含量超过一定值时，多余的MoO₂在A3℃即与四方ZrO₂发生反应形成体相Zr（MoO₄）₂。Mo-O-Zr表面物种中，Mo（Ⅵ）是四配位的，与四方ZrO₂结合很强，它很可能与MoO₃／ZrO₂具有超强酸性有密切关系。更多还原

【Abstract】 Terpineol, as one of the fruitful productions of turpentine, is mostly used in metallurgic floatation, medicine, printing ink, spin, fuel, industrial assist; extensive used in synthetical flavor, is the maximal production of essence industry. It is very important to prepare the high-yield terpineol.This paper prepared terpineol used turpentine as raw material by one-stepcatalyze hydration using self-regulating solid superacid as catalyst. Firstta preparingcatalyst and seeing about its catalysis capability, includes four kinds catalyst, particle diameter, baking temperature, baking time, soakage concentration. It was found thatcatalyst ,solid superacid D2,had optimum activity and its optimal catalysis effect was revealed while the diameter of catalyst more than E3, baking temperature A2, baking time B2, soaking concentration C2. Secondly, preparing terpineol and discussion of its results. It was put up by reaction-temperature, reaction-time, the ratio of catalyst and raw material, the kinds of esterify and dosage, the choice of solvent, catalyst life-span and so on. It was discovered that turpentine transform ratio was 86.29%, the yield ratio of terpineol was 68.89%, the selectivity of solid superacid catalyst was 79.84%. The repetition usage-ratio catalyst was very high and being lasting to using . Thirdly, the testing of catalyst characters, included the influence of preparation methods on MoQ3/ZrO2 structure, testing of superacid acid-mount and its structure characters. After that, putting forward the model of solid superacid on the basis of former discussions. It has been demonstrated by means of XRD , TEM and IAS that the preparation method has a decisive effect on the Structure of D2. D2 prepared by inprefnating Zr(OH)4 with the solution ammonium molybdate and then calcinating it at high temperature is a solid superacid ,while D2 prepared by impregnating crystallized ZrO2 is a catalyst for partial oxidation. There are some obvious difference in morphology of the support and in the forms of the active component between them. ZrOa is dominantly monoclinic, and MoO3 exists in the state of monolayer dispersion. MoO3 in D2 exists on metastable tetragonal ZrO2 in two kinds of surface species. When MoO3 content is beyond a certain value, it reacts with ZrO2(t) and turn into bulk Zr(MoO4)2 at A3. The Mo in Mo-O-Zr surface species is responsible for thesuperacidity of D2.更多还原