生物质制取苯甲醛和苯甲酸以及合成航空煤油组分的研究
发布时间：2018-09-18 12:41
【摘要】：目前,随着化石资源的大量消耗和环保问题的高度关注,开发新的绿色碳资源已成为社会经济可持续发展的全球性问题,并成为热点课题之一。本论文包括两方面研究内容:(1)针对现有生物质转化途径中难以定向合成高值芳香化学品的难题,提出并实现了生物油定向合成苯甲醛和苯甲酸的新途径;(2)探索研究了基于植物油催化裂解-低碳芳烃烷基化-芳烃加氢制备航空煤油芳烃和环烷烃组分的新方法。主要创新成果如下:一、生物油定向合成苯甲醛和苯甲酸研究生物油定向催化转化合成苯甲醛和苯甲酸分为三个反应步骤:(1)生物油催化裂解制备芳烃混合物;(2)芳烃混合物脱甲基制备富甲苯芳烃;(3)富甲苯芳烃液相选择性催化氧化制备苯甲醛和苯甲酸。1、生物油催化裂解制备芳烃混合物研究。选用Ga/HZSM-5分子筛作为催化剂,以生物油为原料并添加甲醇助剂,研究了生物油催化裂解制备低碳芳香烃混合物过程。深入研究了在催化剂和不同热化学环境(如温度、甲醇助剂、空速等)作用下生物油催化裂解行为;在优化条件下(T=450℃、生物油:甲醇=1:1),混合芳烃产率达到33.1wt%。此外,发现在生物油中添加甲醇能有效抑制了催化剂表面焦炭的形成,降低催化剂的失活,从而提高了芳烃混合物产率。探讨了生物油催化裂解反应机理,包括生物油裂解-脱氧-芳构化、甲醇芳构化、芳烃甲基化、芳烃脱烷基化、芳烃聚合反应以及氢转移反应等多渠道竞争反应历程。2、芳烃混合物脱甲基制备甲苯研究。甲苯是合成苯甲醛和苯甲酸的关键中间体,利用生物油催化裂解获得的混合芳烃为原料,研究了混合芳烃催化脱烷基制甲苯过程。利用优选的Re/HY催化剂,在优化条件下(T=540℃、生物油:甲醇=7:3),富甲苯芳烃产率为51.1wt%,液体产物主要包括49.1wt%苯、42.7wt%甲苯和6.1wt%二甲苯。研究了催化剂结构与性能之间关系,发现催化剂的酸度是芳烃催化脱烷基制甲苯的关键控制因素。研究催化剂稳定性与积碳之间关联以及催化剂失活的规律,获得了催化剂再生循环方法。3、甲苯液相催化氧化制备苯甲醛和苯甲酸研究。生物油催化裂解-芳烃脱甲基形成的甲苯选择性活化氧化是定向合成苯甲醛和苯甲酸的关键步骤之一。利用空气为氧化剂,研究了生物油基富甲苯低温液相氧化过程。深入研究在不同催化剂、氧化剂和反应温度与反应时间等氧化反应条件下生物油基芳烃选择性氧化规律;利用优选的CoCl2/NHPI复合催化剂,在T=80℃、t=2h条件下,甲苯转化率为45.2 C-mol%,苯甲酸和苯甲醛的选择性分别为37.5%为42.8%。结合产物与中间物分析、催化剂表征和芳烃模型化合物的催化氧化规律研究,探究了芳烃中C-H键活化氧化规律和反应历程,甲苯一次氧化主要形成苯甲醇和苯甲醛,苯甲醇和苯甲醛进一步发生二次氧化生成苯甲酸。二、植物油催化裂解制备航空煤油芳香烃和环烷烃组分研究植物油合成航空煤油芳香烃组分和环烷烃组分分为三个步骤:(1)植物油催化裂解制备低碳芳烃;(2)低碳芳烃烷基化制备C8-C15芳烃;(3)C8-C15芳烃饱和加氢制备C8-C15环烷烃。主要创新成果如下:1、植物油催化裂解制备低碳芳烃的研究。植物油在分子筛催化剂上发生高温断键(如碳-碳键,碳-氢键,碳-氧键等)过程,生成链状不饱和脂肪酸,再进一步发生脱碳、脱羧、脱氧、芳构化过程生成芳烃混合物。利用优选的HZSM-5(80)催化剂在500℃时,芳烃产率为45.1C-mol%。研究发现,催化剂的酸度、孔径大小均对植物油催化裂解有重要影响。2、低碳芳烃烷基化制备C8-C15芳烃的研究。植物油催化裂解液体产物是以C6-C9为主的低碳芳香烃混合物,而航空煤油典型碳数范围为C8-C15,因此需要在低碳芳烃的基础上加长碳链。选取[bmim]Cl-2AlCl3离子液体作为催化剂,在优化条件下(T=25℃、t=0.5h),C8-C15 的选择性为 86.2C-mol%。通过1H-NMR发现离子液体上的氢具有质子酸性(B酸),能与轻烯烃形成碳正离子,从而促使反应进一步进行。3、C8-C15芳烃饱和加氢制备C8-C15环烷烃的研究。实验选取5%Pd/Ac为催化剂,研究了反应温度、反应时间和反应压力对芳烃饱和加氢的影响。当温度为200℃、压力为5MPa、反应时间为6h时,芳烃的转化率为99.2%,C8-C15环烷烃选择性为90.9C-mol%。制备的环烷烃生物燃料基本满足航煤的特性要求。
[Abstract]:At present, with the large consumption of fossil resources and the high concern of environmental protection, the development of new green carbon resources has become a global issue of sustainable social and economic development, and has become one of the hot topics. A new approach to the directional synthesis of benzaldehyde and benzoic acid from bio-oils was proposed and realized; (2) A new method for the preparation of aromatic and naphthenic components from aviation kerosene by catalytic cracking of vegetable oils, alkylation of low-carbon aromatic hydrocarbons and hydrogenation of aromatic hydrocarbons was explored and studied. The synthesis of benzaldehyde and benzoic acid by directional catalytic conversion of oil can be divided into three steps: (1) catalytic cracking of bio-oil to produce aromatic mixture; (2) demethylation of aromatic mixture to prepare toluene-rich aromatic hydrocarbons; (3) liquid-phase selective catalytic oxidation of toluene-rich aromatic hydrocarbons to prepare benzaldehyde and benzoic acid. 1) catalytic cracking of bio-oil to prepare aromatic hydrocarbon mixture. A/HZSM-5 zeolite was used as catalyst to prepare low-carbon aromatic hydrocarbon mixture by catalytic cracking of bio-oil with methanol as promoter. The catalytic cracking behavior of bio-oil under different thermochemical conditions (such as temperature, methanol promoter, space velocity, etc.) was studied in detail. In addition, it was found that the addition of methanol to bio-oil could effectively inhibit the formation of coke on the catalyst surface, reduce the deactivation of the catalyst, thus increasing the yield of aromatic hydrocarbon mixture. Methylation of aromatic hydrocarbons, dealkylation of aromatic hydrocarbons, polymerization of aromatic hydrocarbons, and hydrogen transfer reactions. 2. Demethylation of aromatic hydrocarbons to toluene. Toluene is the key intermediate in the synthesis of benzaldehyde and benzoic acid. Catalytic dealkylation of mixed aromatic hydrocarbons was studied using mixed aromatic hydrocarbons obtained from catalytic cracking of bio oils. The yield of toluene-rich aromatic hydrocarbons was 51.1wt% under the optimum conditions (T=540 C, bio-oil: methanol = 7:3). The liquid products mainly consisted of 49.1wt% benzene, 42.7wt% toluene and 6.1wt% xylene. The relationship between the structure and performance of the catalyst was studied. It was found that the acidity of the catalyst was aromatic hydrocarbon catalytic dealkylation to toluene. The relationship between catalyst stability and carbon deposition and the law of catalyst deactivation were studied. The regeneration cycle method of catalyst was obtained. 3. Preparation of benzaldehyde and benzoic acid by liquid phase catalytic oxidation of toluene. One of the key steps of formic acid is to study the low-temperature liquid-phase oxidation of toluene-rich bio-oil using air as oxidant. The selective oxidation of aromatic hydrocarbons in bio-oil under different oxidation conditions, such as catalyst, oxidant, reaction temperature and reaction time, etc. was studied in depth. The conversion of toluene was 45.2 C-mol% and the selectivity of benzoic acid and benzaldehyde was 37.5% and 42.8%, respectively. Combining with the analysis of products and intermediates, the characterization of catalysts and the catalytic oxidation of aromatic model compounds, the activation and oxidation rules of C-H bond in aromatic hydrocarbons and the reaction mechanism were studied. Secondary oxidation of formaldehyde, benzyl alcohol and benzaldehyde to benzoic acid. 2. Catalytic cracking of vegetable oil to prepare aromatic hydrocarbons and naphthenes in aviation kerosene C8-C15 aromatic hydrocarbons; (3) C8-C15 aromatic hydrocarbons saturated hydrogenation to prepare C8-C15 cycloalkanes. The main innovations are as follows: 1. Catalytic cracking of vegetable oils to produce low-carbon aromatic hydrocarbons. The yield of aromatics is 45.1C-mol% at 500 C. The acidity and pore size of the catalyst have important influence on the catalytic cracking of vegetable oil. 2. The alkylation of low-carbon aromatics to produce C8-C15 aromatics. The liquid product of catalytic cracking of vegetable oil is C6-C9. The selectivity of C8-C15 is 86.2 C-mol% under the optimum conditions (T = 25 C, t = 0.5 h). It is found that hydrogen in ionic liquids has protons by 1H-NMR. Acidic acid (B acid), which can form carbon cations with light olefins, promotes the reaction to proceed further. 3, C8-C15 aromatics saturated hydrogenation to C8-C15 naphthenes. 5% Pd/Ac was selected as catalyst to study the effects of reaction temperature, reaction time and reaction pressure on saturated hydrogenation of aromatics. The conversion of aromatic hydrocarbons was 99.2% and the selectivity of C8-C15 naphthenes was 90.9 C-mol% at h. The naphthene biofuels basically met the characteristics of aviation coal.
【学位授予单位】：中国科学技术大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：V312;O625
[Abstract]:At present, with the large consumption of fossil resources and the high concern of environmental protection, the development of new green carbon resources has become a global issue of sustainable social and economic development, and has become one of the hot topics. A new approach to the directional synthesis of benzaldehyde and benzoic acid from bio-oils was proposed and realized; (2) A new method for the preparation of aromatic and naphthenic components from aviation kerosene by catalytic cracking of vegetable oils, alkylation of low-carbon aromatic hydrocarbons and hydrogenation of aromatic hydrocarbons was explored and studied. The synthesis of benzaldehyde and benzoic acid by directional catalytic conversion of oil can be divided into three steps: (1) catalytic cracking of bio-oil to produce aromatic mixture; (2) demethylation of aromatic mixture to prepare toluene-rich aromatic hydrocarbons; (3) liquid-phase selective catalytic oxidation of toluene-rich aromatic hydrocarbons to prepare benzaldehyde and benzoic acid. 1) catalytic cracking of bio-oil to prepare aromatic hydrocarbon mixture. A/HZSM-5 zeolite was used as catalyst to prepare low-carbon aromatic hydrocarbon mixture by catalytic cracking of bio-oil with methanol as promoter. The catalytic cracking behavior of bio-oil under different thermochemical conditions (such as temperature, methanol promoter, space velocity, etc.) was studied in detail. In addition, it was found that the addition of methanol to bio-oil could effectively inhibit the formation of coke on the catalyst surface, reduce the deactivation of the catalyst, thus increasing the yield of aromatic hydrocarbon mixture. Methylation of aromatic hydrocarbons, dealkylation of aromatic hydrocarbons, polymerization of aromatic hydrocarbons, and hydrogen transfer reactions. 2. Demethylation of aromatic hydrocarbons to toluene. Toluene is the key intermediate in the synthesis of benzaldehyde and benzoic acid. Catalytic dealkylation of mixed aromatic hydrocarbons was studied using mixed aromatic hydrocarbons obtained from catalytic cracking of bio oils. The yield of toluene-rich aromatic hydrocarbons was 51.1wt% under the optimum conditions (T=540 C, bio-oil: methanol = 7:3). The liquid products mainly consisted of 49.1wt% benzene, 42.7wt% toluene and 6.1wt% xylene. The relationship between the structure and performance of the catalyst was studied. It was found that the acidity of the catalyst was aromatic hydrocarbon catalytic dealkylation to toluene. The relationship between catalyst stability and carbon deposition and the law of catalyst deactivation were studied. The regeneration cycle method of catalyst was obtained. 3. Preparation of benzaldehyde and benzoic acid by liquid phase catalytic oxidation of toluene. One of the key steps of formic acid is to study the low-temperature liquid-phase oxidation of toluene-rich bio-oil using air as oxidant. The selective oxidation of aromatic hydrocarbons in bio-oil under different oxidation conditions, such as catalyst, oxidant, reaction temperature and reaction time, etc. was studied in depth. The conversion of toluene was 45.2 C-mol% and the selectivity of benzoic acid and benzaldehyde was 37.5% and 42.8%, respectively. Combining with the analysis of products and intermediates, the characterization of catalysts and the catalytic oxidation of aromatic model compounds, the activation and oxidation rules of C-H bond in aromatic hydrocarbons and the reaction mechanism were studied. Secondary oxidation of formaldehyde, benzyl alcohol and benzaldehyde to benzoic acid. 2. Catalytic cracking of vegetable oil to prepare aromatic hydrocarbons and naphthenes in aviation kerosene C8-C15 aromatic hydrocarbons; (3) C8-C15 aromatic hydrocarbons saturated hydrogenation to prepare C8-C15 cycloalkanes. The main innovations are as follows: 1. Catalytic cracking of vegetable oils to produce low-carbon aromatic hydrocarbons. The yield of aromatics is 45.1C-mol% at 500 C. The acidity and pore size of the catalyst have important influence on the catalytic cracking of vegetable oil. 2. The alkylation of low-carbon aromatics to produce C8-C15 aromatics. The liquid product of catalytic cracking of vegetable oil is C6-C9. The selectivity of C8-C15 is 86.2 C-mol% under the optimum conditions (T = 25 C, t = 0.5 h). It is found that hydrogen in ionic liquids has protons by 1H-NMR. Acidic acid (B acid), which can form carbon cations with light olefins, promotes the reaction to proceed further. 3, C8-C15 aromatics saturated hydrogenation to C8-C15 naphthenes. 5% Pd/Ac was selected as catalyst to study the effects of reaction temperature, reaction time and reaction pressure on saturated hydrogenation of aromatics. The conversion of aromatic hydrocarbons was 99.2% and the selectivity of C8-C15 naphthenes was 90.9 C-mol% at h. The naphthene biofuels basically met the characteristics of aviation coal.
【学位授予单位】：中国科学技术大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：V312;O625
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