生物質(zhì)制取苯甲醛和苯甲酸以及合成航空煤油組分的研究
發(fā)布時間：2018-09-18 12:41
【摘要】：目前,隨著化石資源的大量消耗和環(huán)保問題的高度關(guān)注,開發(fā)新的綠色碳資源已成為社會經(jīng)濟(jì)可持續(xù)發(fā)展的全球性問題,并成為熱點(diǎn)課題之一。本論文包括兩方面研究內(nèi)容:(1)針對現(xiàn)有生物質(zhì)轉(zhuǎn)化途徑中難以定向合成高值芳香化學(xué)品的難題,提出并實(shí)現(xiàn)了生物油定向合成苯甲醛和苯甲酸的新途徑;(2)探索研究了基于植物油催化裂解-低碳芳烴烷基化-芳烴加氫制備航空煤油芳烴和環(huán)烷烴組分的新方法。主要創(chuàng)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轉(zhuǎn)化合成苯甲醛和苯甲酸分為三個反應(yīng)步驟:(1)生物油催化裂解制備芳烴混合物;(2)芳烴混合物脫甲基制備富甲苯芳烴;(3)富甲苯芳烴液相選擇性催化氧化制備苯甲醛和苯甲酸。1、生物油催化裂解制備芳烴混合物研究。選用Ga/HZSM-5分子篩作為催化劑,以生物油為原料并添加甲醇助劑,研究了生物油催化裂解制備低碳芳香烴混合物過程。深入研究了在催化劑和不同熱化學(xué)環(huán)境(如溫度、甲醇助劑、空速等)作用下生物油催化裂解行為;在優(yōu)化條件下(T=450℃、生物油:甲醇=1:1),混合芳烴產(chǎn)率達(dá)到33.1wt%。此外,發(fā)現(xiàn)在生物油中添加甲醇能有效抑制了催化劑表面焦炭的形成,降低催化劑的失活,從而提高了芳烴混合物產(chǎn)率。探討了生物油催化裂解反應(yīng)機(jī)理,包括生物油裂解-脫氧-芳構(gòu)化、甲醇芳構(gòu)化、芳烴甲基化、芳烴脫烷基化、芳烴聚合反應(yīng)以及氫轉(zhuǎn)移反應(yīng)等多渠道競爭反應(yīng)歷程。2、芳烴混合物脫甲基制備甲苯研究。甲苯是合成苯甲醛和苯甲酸的關(guān)鍵中間體,利用生物油催化裂解獲得的混合芳烴為原料,研究了混合芳烴催化脫烷基制甲苯過程。利用優(yōu)選的Re/HY催化劑,在優(yōu)化條件下(T=540℃、生物油:甲醇=7:3),富甲苯芳烴產(chǎn)率為51.1wt%,液體產(chǎn)物主要包括49.1wt%苯、42.7wt%甲苯和6.1wt%二甲苯。研究了催化劑結(jié)構(gòu)與性能之間關(guān)系,發(fā)現(xiàn)催化劑的酸度是芳烴催化脫烷基制甲苯的關(guān)鍵控制因素。研究催化劑穩(wěn)定性與積碳之間關(guān)聯(lián)以及催化劑失活的規(guī)律,獲得了催化劑再生循環(huán)方法。3、甲苯液相催化氧化制備苯甲醛和苯甲酸研究。生物油催化裂解-芳烴脫甲基形成的甲苯選擇性活化氧化是定向合成苯甲醛和苯甲酸的關(guān)鍵步驟之一。利用空氣為氧化劑,研究了生物油基富甲苯低溫液相氧化過程。深入研究在不同催化劑、氧化劑和反應(yīng)溫度與反應(yīng)時間等氧化反應(yīng)條件下生物油基芳烴選擇性氧化規(guī)律;利用優(yōu)選的CoCl2/NHPI復(fù)合催化劑,在T=80℃、t=2h條件下,甲苯轉(zhuǎn)化率為45.2 C-mol%,苯甲酸和苯甲醛的選擇性分別為37.5%為42.8%。結(jié)合產(chǎn)物與中間物分析、催化劑表征和芳烴模型化合物的催化氧化規(guī)律研究,探究了芳烴中C-H鍵活化氧化規(guī)律和反應(yīng)歷程,甲苯一次氧化主要形成苯甲醇和苯甲醛,苯甲醇和苯甲醛進(jìn)一步發(fā)生二次氧化生成苯甲酸。二、植物油催化裂解制備航空煤油芳香烴和環(huán)烷烴組分研究植物油合成航空煤油芳香烴組分和環(huán)烷烴組分分為三個步驟:(1)植物油催化裂解制備低碳芳烴;(2)低碳芳烴烷基化制備C8-C15芳烴;(3)C8-C15芳烴飽和加氫制備C8-C15環(huán)烷烴。主要創(chuàng)新成果如下:1、植物油催化裂解制備低碳芳烴的研究。植物油在分子篩催化劑上發(fā)生高溫?cái)噫I(如碳-碳鍵,碳-氫鍵,碳-氧鍵等)過程,生成鏈狀不飽和脂肪酸,再進(jìn)一步發(fā)生脫碳、脫羧、脫氧、芳構(gòu)化過程生成芳烴混合物。利用優(yōu)選的HZSM-5(80)催化劑在500℃時,芳烴產(chǎn)率為45.1C-mol%。研究發(fā)現(xiàn),催化劑的酸度、孔徑大小均對植物油催化裂解有重要影響。2、低碳芳烴烷基化制備C8-C15芳烴的研究。植物油催化裂解液體產(chǎn)物是以C6-C9為主的低碳芳香烴混合物,而航空煤油典型碳數(shù)范圍為C8-C15,因此需要在低碳芳烴的基礎(chǔ)上加長碳鏈。選取[bmim]Cl-2AlCl3離子液體作為催化劑,在優(yōu)化條件下(T=25℃、t=0.5h),C8-C15 的選擇性為 86.2C-mol%。通過1H-NMR發(fā)現(xiàn)離子液體上的氫具有質(zhì)子酸性(B酸),能與輕烯烴形成碳正離子,從而促使反應(yīng)進(jìn)一步進(jìn)行。3、C8-C15芳烴飽和加氫制備C8-C15環(huán)烷烴的研究。實(shí)驗(yàn)選取5%Pd/Ac為催化劑,研究了反應(yīng)溫度、反應(yīng)時間和反應(yīng)壓力對芳烴飽和加氫的影響。當(dāng)溫度為200℃、壓力為5MPa、反應(yīng)時間為6h時,芳烴的轉(zhuǎn)化率為99.2%,C8-C15環(huán)烷烴選擇性為90.9C-mol%。制備的環(huán)烷烴生物燃料基本滿足航煤的特性要求。
[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.
【學(xué)位授予單位】：中國科學(xué)技術(shù)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：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.
【學(xué)位授予單位】：中國科學(xué)技術(shù)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：V312;O625
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