a-蒎烯制备紫苏葶的新型催化剂的研究

【作者】 钟莉；

【导师】 王亚明；

【作者基本信息】 昆明理工大学 ， 应用化学， 2006， 硕士

【摘要】 紫苏葶是一种具有高附加价值的高甜、低热、无毒的优质甜味剂和高档香料,广泛应用于糕点、饮料、烟草、牙膏、医药等行业。国内外关于制备紫苏葶的研究很多,其中以天然可再生资源松节油（主要含a-蒎烯,约75%～95%）为原料经“三步法”合成法成本最低,产品质量优异;但所采用的Cu-Zn催化剂需高温高真空条件下才能实现对桃金娘烯醛异构化反应的催化。因而,探寻新型的、有效的催化剂,如环境友好型高活性催化剂——固体超强酸纳米材料催化剂,或者采用微波化学等新的实验技术和手段,使反应沿着反应条件更温和、更高效、环保的绿色化学方向发展,意义重大。 本论文将先进的纳米技术——溶胶-凝胶法用于催化剂的制备中,开发出了具有较高催化活性的用于a-蒎烯催化合成紫苏葶反应工艺的非均相固体超强酸催化剂,并对催化剂的制备及催化性能、反应工艺、催化剂的性能表征等进行了研究,得到以下结论: （1） 催化剂的种类、制备条件及催化性能考察 对催化剂的类型和制备条件进行了考察,发现SO₄^2-/TiO₂固体超强酸催化剂的催化活性最高;单因素考察和正交实验法结果表明焙烧温度对催化剂的催化活性影响最大,且SO₄^2-/TiO₂-催化剂的最佳制备条件为:浸渍液硫酸浓度为A3mol/L、焙烧时间为B1h、焙烧温度为C1℃。 （2） 反应工艺条件的考察 通过单因素考察和正交实验法对桃金娘烯醛异构化反应的工艺条件进行了考察,结果表明反应温度对反应的影响最大,并得出较好工艺条件为:反应温度为T2℃,压力为P2KPa、空速为H2h^-1。 （3） 首次用自制的固体超强酸纳米材料催化剂SO₄^2-/TiO₂应用于紫苏葶的制备工艺中,成功催化了桃金娘烯醛的异构化反应。 （4） 催化剂性能的测试 采用TPD、IR、BET等分析手段对催化剂进行了表征。IR分析结果表明:更多还原

【Abstract】 Perillartine is fine sweetener and high-grade spicery with high sweetness, low caloric and innocuity, safety for eating. It has been widely applied in many kinds of industrial departments such as cake, drink, tobacco, toothpaste , medicine industry and so on. There have been a great many of researches with regard to producing perillartine at home and abroad, among which synthesizing perillartine by the three-process- methode by natural reproducible resource turpentine which mainly contains α-Pinene, about 75%-95%, is the best one with the lowest cost and high quality product. However, the ancient Cu-Zn catalyst was use by the researchers, makeing the condition of myrtenal isomizing reactionvery hard----high temperature and deeply vacuum. Therefore, developingnew kinds of catalyst which possesses high catalytic activity and is more friendly to environment such as sol id superacid nano-catalyst or introducing into new developed experimental methods such as microwave-assistant technology is very necessary.In this paper , advanced nano-technology sol-gel method has been applied to prepare the catalyst and nonhomogeneous solid superacid catalyst with high catalytic activity used in the synthesis of perillartine by -pinene has been developed. Furthermore, the preparation and property of the catalyst, the technologic parameters of the reaction and the structure of the catalyst have been researched . The conclusions in our experiment research are as follows:（1） The investigation of the catalytic kind, preparation and propertyIn this part of the research, the catalytic kind and the preparationcondition have been investigated, which comes to a conclusion that SO₄^2-/TiO₂ solid superacid catalyst prepared by sol-gel method has the highest catalytic activity. By single factor and orthogonal experiments, we have found that the baking temperature is the maximal influencing factor forcatalytic activity of the SO24^/T\02 and the best preparation condition of it is : the vitriol ic concentration A3 mol/L, the baking time B1h and the baking temperature C1°C.（2） The investigation of the reaction conditionIn this part of the research, the condition of myrtenal isomizing reaction has been investigated. By single factor and orthogonal experiments, we have found that the temperature is the maximal influencing parameters and the best reaction condition is: the temperature T2°C , the pressure P2 KPa and the airspeed H2 h"1.（3） By our research , we have successfully developed a new kind of valid catalyst —solid superacid nano-catalys for the myrtenal isoma-zing reaction for the very first time.（4） the investigation of property of the catalyst Catalytic physical properties have been investigated by some analytical methods, such as TPD, IR, BET and so on. It turns out that the acidcentre model of SO^/TiO^. is chelate structure. It also tel Is us that theratio acreage wiI I decreased continuously by prolonging the baking time from B1 h to B2 h and then to B3 h, the baking temperature C1 °C can yieldSO^’/TiOj catalyst with the biggest ratio acreage , the most catalystsurface sour content and the best catalytic activity, and that the baking temperature is the maximal influencing factor for catalytic activity ofthe SO4"/TiO2 catalyst, but the vitriol ic concentration is the minimal one.更多还原