固体超强酸催化剂的制备及催化α-蒎烯合成龙脑
发布时间：2019-06-05 01:47
【摘要】：龙脑是一种重要的医药工业及香料原料,具有开窍醒神、消肿止痛、清热解毒之功效,主要用于治疗心血管疾和脑血管病。在香料上是名贵的定香剂和配置高级香水重要原料。广泛应用于医药及香料工业。龙脑可由α-蒎烯经酯化-皂化反应制得,而松节油中含有大量的α-蒎烯。我国松节油资源极其丰富,价格低廉,因此,催化α-蒎烯合成龙脑在我国松脂深加工行业中具有重要现实意义。本论文制备了 3种固体超强酸SO_4~(2-)/TiO_2-SiO_2、SO_4~(2-)/TiO_2-Al203、S04--/TiO_2-La~(3+)催化剂,首次应用于α-蒎烯酯化-皂化合成龙脑反应。具体研究内容和结果如下:(1)固体超强酸SO_4~(2-)/TiO_2-SiO_2催化α-蒎烯合成龙脑采用溶胶凝胶法制备了固体超强酸SO_4~(2-)/TiO_2-SiO_2催化剂,以α-蒎烯的酯化-皂化反应为探针反应。采用TEM和XPS等表征手段对催化剂的结构和形貌进行了分析,简单研究XRD、Py-1R和NH3-TPD与制备条件n(Ti)/n(Si)和硫酸浸渍浓度之间的关系,通过单因素实验考察反应温度、反应时间、催化剂用量、物料摩尔比等工艺条件对催化α-蒎烯合成龙脑的影响。在此基础上通过正交实验优化合成龙脑的工艺条件,得到适宜的工艺条件反应时间7h,反应温度70℃,催化剂用量为α-蒎烯的7%,n(α-蒎烯):n(草酸)=1:0.4时,SO_4~(2-)/TiO_2-SiO_2固体超强酸酸显示出良好的催化活性和稳定性,α-蒎烯的转化率达到100%,龙脑的收率可达58.14%,重复使用5次后,α-蒎烯的转化率均为100%,龙脑的收率为53.60%以上。(2)固体超强酸SO_4~(2-)/TiO_2-Al203的制备及其催化合成龙脑用溶胶-凝胶法和浸渍法制备了系列SO_4~(2-)/TiO_2-Al203固体超强酸催化剂,运用XRD,NH3-TPD,FT-IR,Py-IR,XPS,SEM等技术手段,研究了复合催化剂材料的结构与性质,初步探讨了固体超强酸SO_4~(2-)/TiO_2-A1203催化剂的构效关系。得到适宜的催化剂制备条件:n(TiO_2):(Al203)=1:2、硫酸浸渍浓度1mol/L、催化剂焙烧温度500℃,同时考察物料摩尔比、催化剂用量、反应时间等对催化合成冰片的影响。结果表明在物料摩尔比为1:0.4,催化剂用量为α-蒎烯质量的7%,采用程序升温方式(65℃ 1 h,75℃ 4 h,90℃ 1 h)进行加热的条件下,SO_4~(2-)/TiO_2-Al2O3固体超强酸催化剂催化活性最高,α-蒎烯的转化率高达100%,龙脑的收率高达59.74%,SO_4~(2-)/TiO_2-Al2O3固体超强酸催化剂在重复使用6次的情况下,α-蒎烯的转化率均不变,龙脑的收率下降2.99%,催化剂的重复使用性良好。(3)纳米稀土固体超强酸SO_4~(2-)/TiO_2-La~(3+)的制备及其催化α-蒎烯合成龙脑采用浸渍法制备了稀土固体超强酸SO_4~(2-)/TiO_2-La~(3+)催化剂。通过TEM、XRD、XPS、NH3-TPD、Py-IR和TG表征对催化剂的结构形貌、酸强度、酸性质和重复使用性进行了分析。结果显示,稀土元素La改性后的催化剂的Bronsted酸位点明显增加,且S04--/TiO_2-La~(3+)催化剂为固体超强酸,催化剂的平均粒径在50nm以内。以催化α-蒎烯酯化皂化合成龙脑为探针反应,评价该催化剂的活性及稳定性。实验结果显示,在最适条件下,α-蒎烯的转化率为100%,龙脑的收率为6 2.60%,并且催化剂重复使用5次后活性基本保持不变,具有较好的活性及稳定性。
[Abstract]:The borneol is an important pharmaceutical industry and a spice raw material, and has the effects of inducing resuscitation, relieving pain, and clearing away heat and toxic materials, and is mainly used for treating cardiovascular diseases and cerebrovascular diseases. It is a valuable flavoring agent and an important raw material for high-grade perfume. It is widely used in medicine and perfume industry. The borneol can be prepared by the esterification-saponification reaction of the sidecene and the turpentine, and the turpentine contains a large amount of n-ene. The oil resources of turpentine in our country are abundant, so the prices are low and factory-direct.We even have the best prices on turpentine in our country. Three solid superacid SO _ 4 ~ (2-)/ TiO _ 2-SiO _ 2, SO _ 4 ~ (2-)/ TiO _ 2-Al203, S04--/ TiO _ 2-La ~ (3 +) catalysts were prepared for the first time. The solid superacid SO _ 4 ~ (2-)/ TiO _ 2-SiO _ 2 catalyst was prepared by sol-gel method with solid superacid SO _ 4 ~ (2-)/ TiO _ 2-SiO _ 2, and the esterification-saponification of the solid superacid SO _ 4 ~ (2-)/ TiO _ 2-SiO _ 2 was prepared by sol-gel method. The structure and morphology of the catalyst were analyzed by means of TEM and XPS. The relationship between XRD, Py-1R and NH3-TPD and the preparation conditions n (Ti)/ n (Si) and the concentration of sulfuric acid was studied. The reaction temperature, the reaction time and the amount of the catalyst were investigated by single factor experiment. The effect of the process conditions such as the molar ratio of the material on the synthesis of dragon brain by the catalysis of l-ene. on the basis of which, the process conditions of the synthetic borneol are optimized by the orthogonal experiment, the reaction time of the process is 7 hours, the reaction temperature is 70 DEG C, the amount of the catalyst is 7% of the 1-graphene, n (1-graphene): n (oxalic acid) is 1: 0.4, The solid superacid acid of SO _ 4 ~ (2-)/ TiO _ 2-SiO _ 2 shows good catalytic activity and stability. The conversion rate of 1-polyoxyalkylene can reach 100%, the yield of borneol is 58.14%, the conversion rate of L-graphene is 100%, and the yield of borneol is 53.60%. (2) The preparation of solid superacid SO _ 4 ~ (2-)/ TiO _ 2-Al203 and its catalytic synthesis of the solid superacid catalyst of SO _ 4 ~ (2-)/ TiO _ 2-Al203 were prepared by sol-gel method and impregnation method. The structure and properties of the composite catalyst were studied by means of XRD, NH3-TPD, FT-IR, Py-IR, XPS and SEM. The structure-effect relationship of solid superacid SO _ 4 ~ (2-)/ TiO _ 2-A203 catalyst was studied. The preparation conditions of the catalyst are as follows: n (TiO _ 2): (Al203) = 1:2, the concentration of the sulfuric acid is 1 mol/ L, the roasting temperature of the catalyst is 500 DEG C, and the influence of the molar ratio of the materials, the amount of the catalyst, the reaction time and the like on the synthesis of the borneol is also investigated. The results showed that the catalytic activity of SO _ 4 ~ (2-)/ TiO _ 2-Al _ 2O _ 2-Al _ 2O _ 2-Al _ 2O _ 2-Al _ 2O _ 2-Al _ 2O _ 2-Al _ 2O _ 2-Al _ 2O _ 2-Al _ 2O _ 2-Al _ 2O _ 2-Al _ 2O _ 2-Al _ 2O _ 2-Al _ 2O _ 2-Al _ 2O _ 2 _ 2-Al _ 2O _ 2 _ 2-Al _ 2O _ 2 _ 2-Al _ 2O _ 2 _ 2-Al _ 2O _ 2 _ 2-Al _ 2O _ 2 The conversion rate of the catalyst was as high as 100%, the yield of the borneol was 59.74%, the SO _ 4 ~ (2-)/ TiO _ 2-Al2O3 solid superacid catalyst was used for 6 times, the conversion rate of the L-graphene was unchanged, the yield of the borneol decreased by 2.99%, and the reusability of the catalyst was good. (3) The preparation of the nano-rare-earth solid superacid SO _ 4 ~ (2-)/ TiO _ 2-La ~ (3 +) and the synthesis of the catalyst of the solid superacid SO _ 4 ~ (2-)/ TiO _ 2-La ~ (3 +) by the impregnation method. The structural morphology, acid strength, acid property and reusability of the catalyst were analyzed by means of TEM, XRD, XPS, NH3-TPD, Py-IR and TG. The results show that the BRONsted acid site of the catalyst modified by the rare-earth element La is obviously increased, and the S04--/ TiO _ 2-La-(3 +) catalyst is a solid superacid, and the average particle diameter of the catalyst is within 50 nm. And the activity and the stability of the catalyst are evaluated by catalyzing the esterification and saponification of the Fischer-graphene to synthesize the borneol as a probe. The results showed that, under the optimum conditions, the conversion rate was 100%, the yield of the borneol was 62.60%, and the activity of the catalyst was kept unchanged after 5 times, and the activity and the stability were good.
【学位授予单位】：昆明理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36
本文编号：2493161
[Abstract]:The borneol is an important pharmaceutical industry and a spice raw material, and has the effects of inducing resuscitation, relieving pain, and clearing away heat and toxic materials, and is mainly used for treating cardiovascular diseases and cerebrovascular diseases. It is a valuable flavoring agent and an important raw material for high-grade perfume. It is widely used in medicine and perfume industry. The borneol can be prepared by the esterification-saponification reaction of the sidecene and the turpentine, and the turpentine contains a large amount of n-ene. The oil resources of turpentine in our country are abundant, so the prices are low and factory-direct.We even have the best prices on turpentine in our country. Three solid superacid SO _ 4 ~ (2-)/ TiO _ 2-SiO _ 2, SO _ 4 ~ (2-)/ TiO _ 2-Al203, S04--/ TiO _ 2-La ~ (3 +) catalysts were prepared for the first time. The solid superacid SO _ 4 ~ (2-)/ TiO _ 2-SiO _ 2 catalyst was prepared by sol-gel method with solid superacid SO _ 4 ~ (2-)/ TiO _ 2-SiO _ 2, and the esterification-saponification of the solid superacid SO _ 4 ~ (2-)/ TiO _ 2-SiO _ 2 was prepared by sol-gel method. The structure and morphology of the catalyst were analyzed by means of TEM and XPS. The relationship between XRD, Py-1R and NH3-TPD and the preparation conditions n (Ti)/ n (Si) and the concentration of sulfuric acid was studied. The reaction temperature, the reaction time and the amount of the catalyst were investigated by single factor experiment. The effect of the process conditions such as the molar ratio of the material on the synthesis of dragon brain by the catalysis of l-ene. on the basis of which, the process conditions of the synthetic borneol are optimized by the orthogonal experiment, the reaction time of the process is 7 hours, the reaction temperature is 70 DEG C, the amount of the catalyst is 7% of the 1-graphene, n (1-graphene): n (oxalic acid) is 1: 0.4, The solid superacid acid of SO _ 4 ~ (2-)/ TiO _ 2-SiO _ 2 shows good catalytic activity and stability. The conversion rate of 1-polyoxyalkylene can reach 100%, the yield of borneol is 58.14%, the conversion rate of L-graphene is 100%, and the yield of borneol is 53.60%. (2) The preparation of solid superacid SO _ 4 ~ (2-)/ TiO _ 2-Al203 and its catalytic synthesis of the solid superacid catalyst of SO _ 4 ~ (2-)/ TiO _ 2-Al203 were prepared by sol-gel method and impregnation method. The structure and properties of the composite catalyst were studied by means of XRD, NH3-TPD, FT-IR, Py-IR, XPS and SEM. The structure-effect relationship of solid superacid SO _ 4 ~ (2-)/ TiO _ 2-A203 catalyst was studied. The preparation conditions of the catalyst are as follows: n (TiO _ 2): (Al203) = 1:2, the concentration of the sulfuric acid is 1 mol/ L, the roasting temperature of the catalyst is 500 DEG C, and the influence of the molar ratio of the materials, the amount of the catalyst, the reaction time and the like on the synthesis of the borneol is also investigated. The results showed that the catalytic activity of SO _ 4 ~ (2-)/ TiO _ 2-Al _ 2O _ 2-Al _ 2O _ 2-Al _ 2O _ 2-Al _ 2O _ 2-Al _ 2O _ 2-Al _ 2O _ 2-Al _ 2O _ 2-Al _ 2O _ 2-Al _ 2O _ 2-Al _ 2O _ 2-Al _ 2O _ 2-Al _ 2O _ 2-Al _ 2O _ 2 _ 2-Al _ 2O _ 2 _ 2-Al _ 2O _ 2 _ 2-Al _ 2O _ 2 _ 2-Al _ 2O _ 2 _ 2-Al _ 2O _ 2 The conversion rate of the catalyst was as high as 100%, the yield of the borneol was 59.74%, the SO _ 4 ~ (2-)/ TiO _ 2-Al2O3 solid superacid catalyst was used for 6 times, the conversion rate of the L-graphene was unchanged, the yield of the borneol decreased by 2.99%, and the reusability of the catalyst was good. (3) The preparation of the nano-rare-earth solid superacid SO _ 4 ~ (2-)/ TiO _ 2-La ~ (3 +) and the synthesis of the catalyst of the solid superacid SO _ 4 ~ (2-)/ TiO _ 2-La ~ (3 +) by the impregnation method. The structural morphology, acid strength, acid property and reusability of the catalyst were analyzed by means of TEM, XRD, XPS, NH3-TPD, Py-IR and TG. The results show that the BRONsted acid site of the catalyst modified by the rare-earth element La is obviously increased, and the S04--/ TiO _ 2-La-(3 +) catalyst is a solid superacid, and the average particle diameter of the catalyst is within 50 nm. And the activity and the stability of the catalyst are evaluated by catalyzing the esterification and saponification of the Fischer-graphene to synthesize the borneol as a probe. The results showed that, under the optimum conditions, the conversion rate was 100%, the yield of the borneol was 62.60%, and the activity of the catalyst was kept unchanged after 5 times, and the activity and the stability were good.
【学位授予单位】：昆明理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36
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