固體超強(qiáng)酸催化劑的制備及催化α-蒎烯合成龍腦
發(fā)布時(shí)間：2019-06-05 01:47
【摘要】：龍腦是一種重要的醫(yī)藥工業(yè)及香料原料,具有開竅醒神、消腫止痛、清熱解毒之功效,主要用于治療心血管疾和腦血管病。在香料上是名貴的定香劑和配置高級(jí)香水重要原料。廣泛應(yīng)用于醫(yī)藥及香料工業(yè)。龍腦可由α-蒎烯經(jīng)酯化-皂化反應(yīng)制得,而松節(jié)油中含有大量的α-蒎烯。我國(guó)松節(jié)油資源極其豐富,價(jià)格低廉,因此,催化α-蒎烯合成龍腦在我國(guó)松脂深加工行業(yè)中具有重要現(xiàn)實(shí)意義。本論文制備了 3種固體超強(qiáng)酸SO_4~(2-)/TiO_2-SiO_2、SO_4~(2-)/TiO_2-Al203、S04--/TiO_2-La~(3+)催化劑,首次應(yīng)用于α-蒎烯酯化-皂化合成龍腦反應(yīng)。具體研究?jī)?nèi)容和結(jié)果如下:(1)固體超強(qiáng)酸SO_4~(2-)/TiO_2-SiO_2催化α-蒎烯合成龍腦采用溶膠凝膠法制備了固體超強(qiáng)酸SO_4~(2-)/TiO_2-SiO_2催化劑,以α-蒎烯的酯化-皂化反應(yīng)為探針反應(yīng)。采用TEM和XPS等表征手段對(duì)催化劑的結(jié)構(gòu)和形貌進(jìn)行了分析,簡(jiǎn)單研究XRD、Py-1R和NH3-TPD與制備條件n(Ti)/n(Si)和硫酸浸漬濃度之間的關(guān)系,通過單因素實(shí)驗(yàn)考察反應(yīng)溫度、反應(yīng)時(shí)間、催化劑用量、物料摩爾比等工藝條件對(duì)催化α-蒎烯合成龍腦的影響。在此基礎(chǔ)上通過正交實(shí)驗(yàn)優(yōu)化合成龍腦的工藝條件,得到適宜的工藝條件反應(yīng)時(shí)間7h,反應(yīng)溫度70℃,催化劑用量為α-蒎烯的7%,n(α-蒎烯):n(草酸)=1:0.4時(shí),SO_4~(2-)/TiO_2-SiO_2固體超強(qiáng)酸酸顯示出良好的催化活性和穩(wěn)定性,α-蒎烯的轉(zhuǎn)化率達(dá)到100%,龍腦的收率可達(dá)58.14%,重復(fù)使用5次后,α-蒎烯的轉(zhuǎn)化率均為100%,龍腦的收率為53.60%以上。(2)固體超強(qiáng)酸SO_4~(2-)/TiO_2-Al203的制備及其催化合成龍腦用溶膠-凝膠法和浸漬法制備了系列SO_4~(2-)/TiO_2-Al203固體超強(qiáng)酸催化劑,運(yùn)用XRD,NH3-TPD,FT-IR,Py-IR,XPS,SEM等技術(shù)手段,研究了復(fù)合催化劑材料的結(jié)構(gòu)與性質(zhì),初步探討了固體超強(qiáng)酸SO_4~(2-)/TiO_2-A1203催化劑的構(gòu)效關(guān)系。得到適宜的催化劑制備條件:n(TiO_2):(Al203)=1:2、硫酸浸漬濃度1mol/L、催化劑焙燒溫度500℃,同時(shí)考察物料摩爾比、催化劑用量、反應(yīng)時(shí)間等對(duì)催化合成冰片的影響。結(jié)果表明在物料摩爾比為1:0.4,催化劑用量為α-蒎烯質(zhì)量的7%,采用程序升溫方式(65℃ 1 h,75℃ 4 h,90℃ 1 h)進(jìn)行加熱的條件下,SO_4~(2-)/TiO_2-Al2O3固體超強(qiáng)酸催化劑催化活性最高,α-蒎烯的轉(zhuǎn)化率高達(dá)100%,龍腦的收率高達(dá)59.74%,SO_4~(2-)/TiO_2-Al2O3固體超強(qiáng)酸催化劑在重復(fù)使用6次的情況下,α-蒎烯的轉(zhuǎn)化率均不變,龍腦的收率下降2.99%,催化劑的重復(fù)使用性良好。(3)納米稀土固體超強(qiáng)酸SO_4~(2-)/TiO_2-La~(3+)的制備及其催化α-蒎烯合成龍腦采用浸漬法制備了稀土固體超強(qiáng)酸SO_4~(2-)/TiO_2-La~(3+)催化劑。通過TEM、XRD、XPS、NH3-TPD、Py-IR和TG表征對(duì)催化劑的結(jié)構(gòu)形貌、酸強(qiáng)度、酸性質(zhì)和重復(fù)使用性進(jìn)行了分析。結(jié)果顯示,稀土元素La改性后的催化劑的Bronsted酸位點(diǎn)明顯增加,且S04--/TiO_2-La~(3+)催化劑為固體超強(qiáng)酸,催化劑的平均粒徑在50nm以內(nèi)。以催化α-蒎烯酯化皂化合成龍腦為探針反應(yīng),評(píng)價(jià)該催化劑的活性及穩(wěn)定性。實(shí)驗(yàn)結(jié)果顯示,在最適條件下,α-蒎烯的轉(zhuǎn)化率為100%,龍腦的收率為6 2.60%,并且催化劑重復(fù)使用5次后活性基本保持不變,具有較好的活性及穩(wěn)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.
【學(xué)位授予單位】：昆明理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O643.36
本文編號(hào)：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.
【學(xué)位授予單位】：昆明理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O643.36
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