生物质甲醇中直接降解制取乙酰丙酸甲酯的研究
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摘要
生物质是唯一可替代化石资源获取液态燃料和化学品的可再生资源，其中碳水化合物是生物质资源中含量最丰富的组分，可通过生物或化学转化合成多种能源化学品，是目前生物质能开发利用研究的热点和重点。近年来由生物质转化合成乙酰丙酸酯引起了研究者们越来越广泛的关注，乙酰丙酸酯是一类重要的化学中间体和新能源化学品，具有高的反应特性和广泛的工业应用价值。目前开发的从生物质资源出发转化合成乙酰丙酸酯的潜在合成途径可概括为以下四种：直接醇解法、经乙酰丙酸酯化、经5-氯甲基糠醛醇解和经糠醇醇解。其中，生物质直接醇解法被认为是合成乙酰丙酸酯最具发展前景的转化途径，但是转化效率低、副反应严重、后处理麻烦等导致的高转化分离成本是目前制约该技术发展和规模化应用的主要障碍。
本论文针对目前生物质直接醇解转化合成乙酰丙酸酯的反应过程中存在的主要科学问题及其研究现状，开展了系列创新性研究，包括：价格低廉、绿色高效催化体系的开发；生物质醇解反应机理及反应动力学的探索；造纸污泥转化成乙酰丙酸酯的资源化利用技术途径；产物乙酰丙酸酯的分离纯化与表征。具体研究主要选择以纤维素和葡萄糖作为反应底物在甲醇体系中反应合成乙酰丙酸甲酯为代表性反应进行详细探讨。
论文选择和制备了多种不同类型的固体酸催化剂，用于在甲醇体系中催化转化碳水化合物合成乙酰丙酸甲酯。结果发现硫酸根促进的金属氧化物固体酸(如SO42–/TiO2)表现出良好的催化活性，乙酰丙酸甲酯收率较高，而甲醇自身缩合脱水生成二甲醚的副反应少，反应后容易与产物分离，回收经高温焙烧后可多次重复使用。对于复合固体酸SO_4~(2–)/ZrO_2–TiO_2，不同Zr/Ti摩尔比和不同焙烧温度的催化剂的表面性质和对葡萄糖醇解的效果明显不同，发现固体酸中存在的强酸位对乙酰丙酸甲酯的生成至关重要，葡萄糖转化成乙酰丙酸甲酯的反应活性与固体酸的酸密度呈良好线性关系。
另外，超低硫酸(≤0.01mol/L)是应用于在甲醇体系中催化转化碳水化合物合成乙酰丙酸甲酯。结果发现超低硫酸能提供足够的酸性位用于催化乙酰丙酸甲酯的生成，根据产物组分，提出了纤维素和葡萄糖在甲醇体系中转化合成乙酰丙酸甲酯的合理反应机理。与前面固体酸催化相比，超低硫酸催化活性更强，乙酰丙酸甲酯收率更高，原料适用范围更广。与传统稀硫酸催化相比，乙酰丙酸甲酯收率增加，甲醇自身缩合脱水成二甲醚副反应明显减少，同时对设备腐蚀明显减弱，反应后酸处理变得简单，产生废渣少。可见，超低硫酸催化在多方面表现出明显的优势，生产成本低，极具工业应用前景。
论文进一步考察了超低硫酸在甲醇体系中催化转化纤维素合成乙酰丙酸甲酯的反应动力学。实验发现，一种主要的、稳定的中间产物甲基葡萄糖苷是形成，据此建立了纤维素经甲基葡萄糖苷醇解生成乙酰丙酸甲酯的一级反应动力学模型，从而获得了相关的醇解反应活化能和对H+的反应级数，可为新工艺的开发和改进提供理论依据。
研究中另选择以卫生纸厂造纸污泥作为生物质原料，在甲醇体系中酸催化转化合成乙酰丙酸甲酯，采用响应面分析法对醇解工艺条件进行了优化。发现造纸污泥中约70%的组分能被液化，液体产物主要包括有乙酰丙酸甲酯、甲酸甲酯、2-二甲氧基甲基呋喃和甲基葡萄糖苷。乙酰丙酸甲酯最高收率可达理论值的60%以上，即每克造纸污泥大约可以得到0.29g乙酰丙酸甲酯，该转化技术可为造纸污泥的资源化利用提供新参考。
最后初步探索了产物乙酰丙酰甲酯的分离纯化。醇解反应后，根据体系中物质沸点的不同，采用常压蒸馏结合添加正十二烷作为助蒸剂的减压蒸馏法对反应产物进行分离，实现了多组分的分离及纯化，乙酰丙酸甲酯的分离效率达95%以上，纯度约为95%。利用红外光谱、核磁共振氢谱及碳谱表征对分离产物乙酰丙酸甲酯的化学结构进行了证实，物理性质与标准品一致。
综上所述，本论文开发了两种清洁有效的直接转化碳水化合物合成乙酰丙酸酯的新途径，尤其是超低硫酸催化，能有效地克服先前技术存在的诸多缺点，生成成本低，并提出了生物质醇解的合理反应机理和发展了其反应动力学，最后还探索了造纸污泥转化成乙酰丙酸酯的高效资源化利用以及产物的分离纯化。研究结果可为生物质基化学品乙酰丙酸酯的后续深入研究以及规模化生产提供理论指导和技术参考。
Biomass is the only renewable resources on the earth that can derive liquid fuel and finechemicals to replace the petroleum-based chemicals. Carbohydrate, is the most plentifulelement in biomass resources, can be converted into a variety of interesting bulk chemicalsvia biological or chemical pathways, which is one of the focuses in the field of biomassenergy today. Recently, the development of bioenergy concerning the synthesis of levulinateester from biomass has attracted more and more concerns. Levulinate ester is a kind ofimportant intermediates and energy chemicals having high reactivity and widespreadapplication in many fields. Up to now, there are four developed potential pathways for thesynthesis of levulinate esters from biomass conversion, including the direct acid-catalyzedalcoholysis of biomass, the esterification of levulinic acid that from hydrolysis of biomass, thealcoholysis of5-(chloromethyl)furfural derived from biomass, and the alcoholysis of furfurylalcohol that from hydrogenation of furfural. Among these, the direct acid-catalyzedalcoholysis of biomass is considered the most promising pathway for the synthesis oflevulinate ester, however, high cost production caused from low conversion efficiency, seriousside reaction and trouble post-treatment is the obstacle that restricts progress and large-scaleapplication of this technology.
To develop green chemistry for the purpose, aiming at present research situation andmain existing scientific problems for the direct alcoholysis of biomass to levulinate ester, aseries of innovation studies were performed in this dissertation. For example, development oflow cost and green efficient catalyst system, exploration of biomass alcoholysis mechanismand kinetics, resource utilization of paper sludge for levulinate ester synthesis, separation andcharacterization of the products. Specifically, conversion of cellulose and glucose into methyllevulinate in methanol medium was selected as the representative route for detailed study.
Firstly, some different types of solid acid catalysts were obtained from company and ownsynthesis, which were employed for the catalytic conversion of carbohydrate to methyllevulinate in methanol medium. Among these catalysts used, sulfated metal oxides (especiallySO_4~(2–)/TiO_2) were found to be a type of potential catalysts for prospective utilization, whichshowed remarkably high yield of methyl levulinate and had negligible undesired dimethyl ether formation from the dehydration of methanol. After reaction, the catalyst is recoverablefrom the resulting product mixture and reused multiple times after calcination. In the case ofSO_4~(2–)/ZrO_2–TiO_2, Zr/Ti molar ratio and calcinations temperature are two factors that stronglyaffected its surface properties and glucose reactivity in methanol medium. The resultssuggested that the moderate acid sites were responsible for the formation of methyl levulinateand the catalytic activity for methyl levulinate production from glucose almost increaseslinearly with the catalyst acid site density.
Secondly, extremely low sulfuric acid (≤0.01mol/L) was selected as acid catalyst for theconversion of carbohydrate to methyl levulinate in methanol medium. It found that extremelylow sulfuric acid offer enough acid site for the completion of reaction. Based on the detectedcompounds, a plausible reaction pathway for the acid-catalyzed conversion of cellulose andglucose to methyl levulinate in methanol medium was proposed. Compared with the first solidacid, extremely low sulfuric acid exhibited more catalytic activity with high methyl levulinateyield and good material adaptability. Compared to the conventional dilute sulfuric acidcatalysis, an advantage of extremely low sulfuric acid catalyst system is that methyl levulinateyield is high, negligible undesired dimethyl ether formed from the side reaction for thedehydration of methanol, the equipment corrosion was slight, and less spent acid need to beaddressed after reaction. In summary, this technology can provide a great help to acceleratethe development of the industrial production of levulinate ester from carbohydrate.
Based on the above findings, kinetic investigation on the conversion of cellulose tomethyl levulinate in methanol medium catalyzed by extremely low sulfuric acid wasperformed. During the methanolysis of cellulose, a key and stable intermediate product ofmethyl glucoside was produced, so a simplified kinetic model of first-order reaction for thegeneration of methyl levulinate from cellulose via methyl glucoside was developed, and thecorresponding activation energy and reaction order of H+were evaluated using the method ofnon-linear least squares regression analyses. The kinetic results can provide theoretic basis forthe development and improvement of novel process.
Primary sludge from a toilet paper mill was used as biomass material to produce methyllevulinate in methanol medium, technical conditions for the acid-catalyzed methanolysis ofpaper sludge were optimized by response surface analysis (RSA). The results indicated that about seventy percent of the paper sludge was liquefied, the major liquid phase productsincluded methyl glucoside, methyl levulinate, methyl formate and2-(dimethoxymethyl)furan.Under the optimum conditions, the yield of methyl levulinate is around60%of the availablecarbohydrate on the initial substrate, corresponding to methyl levulinate yield of290g/kg ofdry paper sludge. This conversion technology can provide new reference for the resourceutilization of paper sludge.
After the methanolysis of glucose, the products were isolated and purified by adistillation technique that combines an atmospheric distillation with a vacuum distillationwhere n-dodecane was added to help distil the heavy products. The chemical structure ofmethyl levulinate was confirmed using FTIR,1H-NMR and13C-NMR, respectively. Thepurity of isolated methyl levulinate was about95%and the separation efficiency of methyllevulinate reached95%with this method.
In conclusion, the present study developed two novel, green and efficient strategies forthe conversion of carbohydrate to levulinate ester, especially extremely low sulfuric acidcatalyst system, which can effectively overcome many disadvantages of the conventionaltechnology with low production cost. A plausible reaction pathway for the alcoholysis ofcarbohydrate was proposed and a convictive kinetic model was developed. Efficient resourceutilization of paper sludge for the synthesis of levulinate ester and the multi-componentsseparation of products were realized. The findings of this dissertation can provide theoreticalguidance and technical reference for further research and industrial scale production ofbiomass-based levulinate ester.
本论文针对目前生物质直接醇解转化合成乙酰丙酸酯的反应过程中存在的主要科学问题及其研究现状，开展了系列创新性研究，包括：价格低廉、绿色高效催化体系的开发；生物质醇解反应机理及反应动力学的探索；造纸污泥转化成乙酰丙酸酯的资源化利用技术途径；产物乙酰丙酸酯的分离纯化与表征。具体研究主要选择以纤维素和葡萄糖作为反应底物在甲醇体系中反应合成乙酰丙酸甲酯为代表性反应进行详细探讨。
论文选择和制备了多种不同类型的固体酸催化剂，用于在甲醇体系中催化转化碳水化合物合成乙酰丙酸甲酯。结果发现硫酸根促进的金属氧化物固体酸(如SO42–/TiO2)表现出良好的催化活性，乙酰丙酸甲酯收率较高，而甲醇自身缩合脱水生成二甲醚的副反应少，反应后容易与产物分离，回收经高温焙烧后可多次重复使用。对于复合固体酸SO_4~(2–)/ZrO_2–TiO_2，不同Zr/Ti摩尔比和不同焙烧温度的催化剂的表面性质和对葡萄糖醇解的效果明显不同，发现固体酸中存在的强酸位对乙酰丙酸甲酯的生成至关重要，葡萄糖转化成乙酰丙酸甲酯的反应活性与固体酸的酸密度呈良好线性关系。
另外，超低硫酸(≤0.01mol/L)是应用于在甲醇体系中催化转化碳水化合物合成乙酰丙酸甲酯。结果发现超低硫酸能提供足够的酸性位用于催化乙酰丙酸甲酯的生成，根据产物组分，提出了纤维素和葡萄糖在甲醇体系中转化合成乙酰丙酸甲酯的合理反应机理。与前面固体酸催化相比，超低硫酸催化活性更强，乙酰丙酸甲酯收率更高，原料适用范围更广。与传统稀硫酸催化相比，乙酰丙酸甲酯收率增加，甲醇自身缩合脱水成二甲醚副反应明显减少，同时对设备腐蚀明显减弱，反应后酸处理变得简单，产生废渣少。可见，超低硫酸催化在多方面表现出明显的优势，生产成本低，极具工业应用前景。
论文进一步考察了超低硫酸在甲醇体系中催化转化纤维素合成乙酰丙酸甲酯的反应动力学。实验发现，一种主要的、稳定的中间产物甲基葡萄糖苷是形成，据此建立了纤维素经甲基葡萄糖苷醇解生成乙酰丙酸甲酯的一级反应动力学模型，从而获得了相关的醇解反应活化能和对H+的反应级数，可为新工艺的开发和改进提供理论依据。
研究中另选择以卫生纸厂造纸污泥作为生物质原料，在甲醇体系中酸催化转化合成乙酰丙酸甲酯，采用响应面分析法对醇解工艺条件进行了优化。发现造纸污泥中约70%的组分能被液化，液体产物主要包括有乙酰丙酸甲酯、甲酸甲酯、2-二甲氧基甲基呋喃和甲基葡萄糖苷。乙酰丙酸甲酯最高收率可达理论值的60%以上，即每克造纸污泥大约可以得到0.29g乙酰丙酸甲酯，该转化技术可为造纸污泥的资源化利用提供新参考。
最后初步探索了产物乙酰丙酰甲酯的分离纯化。醇解反应后，根据体系中物质沸点的不同，采用常压蒸馏结合添加正十二烷作为助蒸剂的减压蒸馏法对反应产物进行分离，实现了多组分的分离及纯化，乙酰丙酸甲酯的分离效率达95%以上，纯度约为95%。利用红外光谱、核磁共振氢谱及碳谱表征对分离产物乙酰丙酸甲酯的化学结构进行了证实，物理性质与标准品一致。
综上所述，本论文开发了两种清洁有效的直接转化碳水化合物合成乙酰丙酸酯的新途径，尤其是超低硫酸催化，能有效地克服先前技术存在的诸多缺点，生成成本低，并提出了生物质醇解的合理反应机理和发展了其反应动力学，最后还探索了造纸污泥转化成乙酰丙酸酯的高效资源化利用以及产物的分离纯化。研究结果可为生物质基化学品乙酰丙酸酯的后续深入研究以及规模化生产提供理论指导和技术参考。
Biomass is the only renewable resources on the earth that can derive liquid fuel and finechemicals to replace the petroleum-based chemicals. Carbohydrate, is the most plentifulelement in biomass resources, can be converted into a variety of interesting bulk chemicalsvia biological or chemical pathways, which is one of the focuses in the field of biomassenergy today. Recently, the development of bioenergy concerning the synthesis of levulinateester from biomass has attracted more and more concerns. Levulinate ester is a kind ofimportant intermediates and energy chemicals having high reactivity and widespreadapplication in many fields. Up to now, there are four developed potential pathways for thesynthesis of levulinate esters from biomass conversion, including the direct acid-catalyzedalcoholysis of biomass, the esterification of levulinic acid that from hydrolysis of biomass, thealcoholysis of5-(chloromethyl)furfural derived from biomass, and the alcoholysis of furfurylalcohol that from hydrogenation of furfural. Among these, the direct acid-catalyzedalcoholysis of biomass is considered the most promising pathway for the synthesis oflevulinate ester, however, high cost production caused from low conversion efficiency, seriousside reaction and trouble post-treatment is the obstacle that restricts progress and large-scaleapplication of this technology.
To develop green chemistry for the purpose, aiming at present research situation andmain existing scientific problems for the direct alcoholysis of biomass to levulinate ester, aseries of innovation studies were performed in this dissertation. For example, development oflow cost and green efficient catalyst system, exploration of biomass alcoholysis mechanismand kinetics, resource utilization of paper sludge for levulinate ester synthesis, separation andcharacterization of the products. Specifically, conversion of cellulose and glucose into methyllevulinate in methanol medium was selected as the representative route for detailed study.
Firstly, some different types of solid acid catalysts were obtained from company and ownsynthesis, which were employed for the catalytic conversion of carbohydrate to methyllevulinate in methanol medium. Among these catalysts used, sulfated metal oxides (especiallySO_4~(2–)/TiO_2) were found to be a type of potential catalysts for prospective utilization, whichshowed remarkably high yield of methyl levulinate and had negligible undesired dimethyl ether formation from the dehydration of methanol. After reaction, the catalyst is recoverablefrom the resulting product mixture and reused multiple times after calcination. In the case ofSO_4~(2–)/ZrO_2–TiO_2, Zr/Ti molar ratio and calcinations temperature are two factors that stronglyaffected its surface properties and glucose reactivity in methanol medium. The resultssuggested that the moderate acid sites were responsible for the formation of methyl levulinateand the catalytic activity for methyl levulinate production from glucose almost increaseslinearly with the catalyst acid site density.
Secondly, extremely low sulfuric acid (≤0.01mol/L) was selected as acid catalyst for theconversion of carbohydrate to methyl levulinate in methanol medium. It found that extremelylow sulfuric acid offer enough acid site for the completion of reaction. Based on the detectedcompounds, a plausible reaction pathway for the acid-catalyzed conversion of cellulose andglucose to methyl levulinate in methanol medium was proposed. Compared with the first solidacid, extremely low sulfuric acid exhibited more catalytic activity with high methyl levulinateyield and good material adaptability. Compared to the conventional dilute sulfuric acidcatalysis, an advantage of extremely low sulfuric acid catalyst system is that methyl levulinateyield is high, negligible undesired dimethyl ether formed from the side reaction for thedehydration of methanol, the equipment corrosion was slight, and less spent acid need to beaddressed after reaction. In summary, this technology can provide a great help to acceleratethe development of the industrial production of levulinate ester from carbohydrate.
Based on the above findings, kinetic investigation on the conversion of cellulose tomethyl levulinate in methanol medium catalyzed by extremely low sulfuric acid wasperformed. During the methanolysis of cellulose, a key and stable intermediate product ofmethyl glucoside was produced, so a simplified kinetic model of first-order reaction for thegeneration of methyl levulinate from cellulose via methyl glucoside was developed, and thecorresponding activation energy and reaction order of H+were evaluated using the method ofnon-linear least squares regression analyses. The kinetic results can provide theoretic basis forthe development and improvement of novel process.
Primary sludge from a toilet paper mill was used as biomass material to produce methyllevulinate in methanol medium, technical conditions for the acid-catalyzed methanolysis ofpaper sludge were optimized by response surface analysis (RSA). The results indicated that about seventy percent of the paper sludge was liquefied, the major liquid phase productsincluded methyl glucoside, methyl levulinate, methyl formate and2-(dimethoxymethyl)furan.Under the optimum conditions, the yield of methyl levulinate is around60%of the availablecarbohydrate on the initial substrate, corresponding to methyl levulinate yield of290g/kg ofdry paper sludge. This conversion technology can provide new reference for the resourceutilization of paper sludge.
After the methanolysis of glucose, the products were isolated and purified by adistillation technique that combines an atmospheric distillation with a vacuum distillationwhere n-dodecane was added to help distil the heavy products. The chemical structure ofmethyl levulinate was confirmed using FTIR,1H-NMR and13C-NMR, respectively. Thepurity of isolated methyl levulinate was about95%and the separation efficiency of methyllevulinate reached95%with this method.
In conclusion, the present study developed two novel, green and efficient strategies forthe conversion of carbohydrate to levulinate ester, especially extremely low sulfuric acidcatalyst system, which can effectively overcome many disadvantages of the conventionaltechnology with low production cost. A plausible reaction pathway for the alcoholysis ofcarbohydrate was proposed and a convictive kinetic model was developed. Efficient resourceutilization of paper sludge for the synthesis of levulinate ester and the multi-componentsseparation of products were realized. The findings of this dissertation can provide theoreticalguidance and technical reference for further research and industrial scale production ofbiomass-based levulinate ester.
引文
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