农业废弃物固体碱预处理过程中木素的结构表征及其脱除机理研究
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摘要
由于能源短缺和资源匮乏，利用木质纤维素等可再生资源代替石油等化石燃料来生产高附加值的化学品受到人们越来越多的关注。在众多的纤维素资源中，农业废弃物是一类来源丰富的纤维素资源，应用于生物质精炼工业具有很大的前景，因此研究它们的高效利用具有重要的现实意义。
固体碱活性氧蒸煮是由本实验室开发的一种环保、高效的生物质预处理工艺。其中，采用的固体碱主要是氧化镁，活性氧是氧气和过氧化氢。在固体碱活性氧蒸煮中，Mg~(2+)作为唯一的无机离子被引入到蒸煮系统，它不仅与O~(2-)结合作为碱源，同时也作为碳水化合物的保护剂。基于这个理论，本论文对固体碱活性氧蒸煮的脱木素机制进行了深入研究。
对玉米秸秆和蔗渣的木素进行3D HSQC-TOCSY NMR等分析发现，水溶性MWL与MWL中主要存在有紫丁香基（S）、愈创木基（G）和对羟基苯基（H）三种基本结构单元，β-O-4′（A/A′/A′′）、β-β′（B）和β-5′（C）等侧链连接形式，以及少量的酯化阿魏酸结构，蔗渣的MWL中没有发现紫丁香基的变形结构（S′/S′′）。水溶性MWL的分子量均比相同原料的MWL的小。此外，四种木素中均有大量的脂肪族羟基，和少量的愈创木基酚羟基与缩合的酚羟基。蔗渣的水溶性MWL中不存在对羟基苯基酚羟基、紫丁香基酚羟基和羧基。
固体碱活性氧蒸煮具有很高的脱木素率，能脱除玉米秸秆中85.5%的木素和蔗渣中95.4%的木素，同时对碳水化合物特别是纤维素有很好的保护作用。在蒸煮中，紫丁香基单元（S/S′/S′′）的反应活性很高，愈创木基（G）可以被氧化并生成新型的G′结构；而对羟基苯基（H）在蒸煮中是稳定的。对于木素中的侧链连接形式，酚型的β-O-4′（A/A′/A′′）结构可以发生碱性自氧化反应，而非酚型的β-O-4′（A/A′/A′′）结构具有不同的反应活性。非酚型的β-β′（B）和β-5′（C）结构在蒸煮中是稳定的，而β-1′（D）结构已被完全破坏。另外，脱除的酯化阿魏酸结构（FE）已被完全破坏，而对乙酰氧基苯甲酸结构（P）是稳定的。
目前发现，只有MgO和Mg(OH)_2两种固体碱用于蒸煮具有高脱木素率而又不发生碳化现象。固体碱可以为蒸煮提供一个弱碱性环境，防止原料的碳化，同时保护碳水化合物。氧气会与酚型木素结构反应，并将木素中的卞醇结构氧化成羰基，同时还会与环共轭结构反应。而过氧化氢会与木素侧链的羰基和双键反应，进一步提高了脱木素率。
在固体碱活性氧蒸煮中，不同蒸煮时间下脱除的木素结构单元不同，酸溶木素主要是在100℃前的升温阶段脱除的，而酸不溶木素的脱除和碳水化合物的降解主要发生在100℃后的升温阶段。对木素模型物的分析发现，愈创木酚和部分对羟基苯甲酸在蒸煮中是稳定的，而阿魏酸、4-香豆酸、尼泊金乙酯、丁香酚、肉桂酸和苯甲酸乙酯在蒸煮中均被完全破坏。此外，固体碱活性氧蒸煮中水溶性MWL的分子量变化较小，但MWL的分子量降低非常明显，即固体碱活性氧蒸煮对MWL的破坏更严重。同时发现蒸煮中会生成P结构。
几种固体碱活性氧蒸煮黄液的pH均较低，属于弱碱性环境，同时黄液中存在大量的甲酸和乙酸。黄液中存在的主要是碱析木素，且木素中均含有一定的Mg(OH)_2。对MgO/O_2、MgO/H_2O_2、MgO/H_2O_2/O_2三种蒸煮黄液分析发现，黄液中的酸碱抽提组分主要是邻苯二甲酸单(2-乙基己基)酯。
The use of lignocellulosic resources instead of petroleum and other fossil fuels asrenewable materials for the production of high value-added chemical products is concerenmore and more by the human because of energy shortages and resource scarcity. Among thelignocellulosic resources, agricultural residues are a type of cellulose resources with richreserves for the potential utilization in biomass refinery industry. Therefore, how to efficientlymake use of them is of great significance
Solid alkali and active oxygen cooking is an environmentally friendly and efficienttechnology that developed by our laboratory, where MgO is used as a solid alkali, oxygen andhydrogen peroxide are used as active oxygen. In the cooking process, Mg~(2+)is the onlyinorganic ion brought into the cooking system, not only as an alkali factor reacting with O~(2-),but also as a protective agent for carbohydrate. Based on this theory, the delignificationmechanism of the solid alkali and active oxygen cooking is researched in the present work.
Form the analysis of the cornstalk and bagasse lignins by3D HSQC-TOCSY NMR andother technologies, it was found that the water-soluble milled wood lignin (MWL) and MWLwere contained three types of basic structure units syringyl (S), guaiacyl (G) andp-hydroxyphenyl (H), main side-chain linkages β-O-4′(A/A′/A′′), β-β′(B) and β-5′(C)structures, and esterified ferulic acid structure (FE) with a little content. The transformationstructures of syringyl (S′/S′′) were not found in the water-soluble MWL of bagasse.Comparing to the MWL, the molecular weight of the water-soluble MWL from the same rawmaterial was smaller. In addition, a great amount of the aliphatic hydroxyl group, and smallamounts of phenolic hydroxyl group in guaiacyl and condensed phenolic hydroxyl group werefound in the four types of lignins. The phenolic hydroxyl groups in syringyl andp-hydroxyphenyl, and carboxyl group were not found in the MWL of bagasse.
The solid alkali and active oxygen cooking had a high delignification rate, which couldremove85.5%of lignin in cornstalk and95.4%of lignin in bagasse, and had a protectiveeffect for the carbohydrate especially for the cellulose. In the cooking process, the syringyl(S/S′/S′′) units had a high reactivity. A novel G′structure was formed byan oxidizing reactionof the guaiacyl (G) unit. However, the p-hydroxyphenyl unit was stable in the cooking. For the sid-chain linkages, the phenolic β-O-4′(A/A′/A′′) structures could be changed by analkaline autoxidation reaction, and their non-phenolic structures had different reactivities. Thenon-phenolic β-β′(B) and β-5′(C) structures were stable in the cooking process, but the β-1′(D) structure was completely destroyed in the cooking. Moreover, the removed esterifiedferulic acid structure (FE) was also broken in the cooking, while the esterifiedp-acetoxy-benzoic acid structure (P) was stable.
In our research, it was found that only the MgO and Mg(OH)_2used in solid alkali andactive oxygen cooking had a high delignification rate and not occurred carbonizationphenomena. The solid alkali effectively could provide a weakly alkaline environment fordelignification, prevent the raw material carbonizing, and also have a protective effect for thecarbohydrate. The oxygen affected changes in the phenolic structure, leading to the oxidationof a benzylic alcohol group into a carbonyl group, and the facile attack of the ring-conjugatedstructure. The hydrogen peroxide could react with the carbonyl groups and double bonds onlignin side-chains, and further increasing the delignification rate.
In the solid alkali and active oxygen cooking, the lignin structure units could be removedin different cooking time. The acid soluble lignin was mainly removed in the heating stage,with the temperature under100℃, the removal of the acid-insoluble lignin and thedegradation of the carbohydrate were occurred in the heating stage also, but with thetemperature above100℃. In the analysises of the lignin models, it was found that theguaiacol and partial p-hydroxybenzoic acid were stable in the solid alkali and active oxygencooking process. While ferulic acid, p-coumaric acid, ethyl4-hydroxybenzoate, eugenol,trans-cinnamic acid and ethyl benzoate were thoroughly broken. In addition, the molecularweight of the water-soluble MWL changed smaller compared to the MWL in the cooking,namely the MWL was destroyed more seriously in the solid alkali and active oxygen cooking.And the P structure could be formed in the cooking process.
The pH value of the yellow liquors from the solid alkali and active oxygen cooking waslow, which was a weak alkaline environment, and a large amount of the formic acid and aceticacid were found in the yellow liquors. The yellow liquors mainly contained alkali lignin, withcertain Mg(OH)_2precipitate in them. Form the analysis of the yellow liquors in the cookingwith MgO/O_2, MgO/H_2O_2and MgO/H_2O_2/O_2, the main components in alkali and acid extracts were phthalic acid, mono (2-ethylhexyl) ester.
固体碱活性氧蒸煮是由本实验室开发的一种环保、高效的生物质预处理工艺。其中，采用的固体碱主要是氧化镁，活性氧是氧气和过氧化氢。在固体碱活性氧蒸煮中，Mg~(2+)作为唯一的无机离子被引入到蒸煮系统，它不仅与O~(2-)结合作为碱源，同时也作为碳水化合物的保护剂。基于这个理论，本论文对固体碱活性氧蒸煮的脱木素机制进行了深入研究。
对玉米秸秆和蔗渣的木素进行3D HSQC-TOCSY NMR等分析发现，水溶性MWL与MWL中主要存在有紫丁香基（S）、愈创木基（G）和对羟基苯基（H）三种基本结构单元，β-O-4′（A/A′/A′′）、β-β′（B）和β-5′（C）等侧链连接形式，以及少量的酯化阿魏酸结构，蔗渣的MWL中没有发现紫丁香基的变形结构（S′/S′′）。水溶性MWL的分子量均比相同原料的MWL的小。此外，四种木素中均有大量的脂肪族羟基，和少量的愈创木基酚羟基与缩合的酚羟基。蔗渣的水溶性MWL中不存在对羟基苯基酚羟基、紫丁香基酚羟基和羧基。
固体碱活性氧蒸煮具有很高的脱木素率，能脱除玉米秸秆中85.5%的木素和蔗渣中95.4%的木素，同时对碳水化合物特别是纤维素有很好的保护作用。在蒸煮中，紫丁香基单元（S/S′/S′′）的反应活性很高，愈创木基（G）可以被氧化并生成新型的G′结构；而对羟基苯基（H）在蒸煮中是稳定的。对于木素中的侧链连接形式，酚型的β-O-4′（A/A′/A′′）结构可以发生碱性自氧化反应，而非酚型的β-O-4′（A/A′/A′′）结构具有不同的反应活性。非酚型的β-β′（B）和β-5′（C）结构在蒸煮中是稳定的，而β-1′（D）结构已被完全破坏。另外，脱除的酯化阿魏酸结构（FE）已被完全破坏，而对乙酰氧基苯甲酸结构（P）是稳定的。
目前发现，只有MgO和Mg(OH)_2两种固体碱用于蒸煮具有高脱木素率而又不发生碳化现象。固体碱可以为蒸煮提供一个弱碱性环境，防止原料的碳化，同时保护碳水化合物。氧气会与酚型木素结构反应，并将木素中的卞醇结构氧化成羰基，同时还会与环共轭结构反应。而过氧化氢会与木素侧链的羰基和双键反应，进一步提高了脱木素率。
在固体碱活性氧蒸煮中，不同蒸煮时间下脱除的木素结构单元不同，酸溶木素主要是在100℃前的升温阶段脱除的，而酸不溶木素的脱除和碳水化合物的降解主要发生在100℃后的升温阶段。对木素模型物的分析发现，愈创木酚和部分对羟基苯甲酸在蒸煮中是稳定的，而阿魏酸、4-香豆酸、尼泊金乙酯、丁香酚、肉桂酸和苯甲酸乙酯在蒸煮中均被完全破坏。此外，固体碱活性氧蒸煮中水溶性MWL的分子量变化较小，但MWL的分子量降低非常明显，即固体碱活性氧蒸煮对MWL的破坏更严重。同时发现蒸煮中会生成P结构。
几种固体碱活性氧蒸煮黄液的pH均较低，属于弱碱性环境，同时黄液中存在大量的甲酸和乙酸。黄液中存在的主要是碱析木素，且木素中均含有一定的Mg(OH)_2。对MgO/O_2、MgO/H_2O_2、MgO/H_2O_2/O_2三种蒸煮黄液分析发现，黄液中的酸碱抽提组分主要是邻苯二甲酸单(2-乙基己基)酯。
The use of lignocellulosic resources instead of petroleum and other fossil fuels asrenewable materials for the production of high value-added chemical products is concerenmore and more by the human because of energy shortages and resource scarcity. Among thelignocellulosic resources, agricultural residues are a type of cellulose resources with richreserves for the potential utilization in biomass refinery industry. Therefore, how to efficientlymake use of them is of great significance
Solid alkali and active oxygen cooking is an environmentally friendly and efficienttechnology that developed by our laboratory, where MgO is used as a solid alkali, oxygen andhydrogen peroxide are used as active oxygen. In the cooking process, Mg~(2+)is the onlyinorganic ion brought into the cooking system, not only as an alkali factor reacting with O~(2-),but also as a protective agent for carbohydrate. Based on this theory, the delignificationmechanism of the solid alkali and active oxygen cooking is researched in the present work.
Form the analysis of the cornstalk and bagasse lignins by3D HSQC-TOCSY NMR andother technologies, it was found that the water-soluble milled wood lignin (MWL) and MWLwere contained three types of basic structure units syringyl (S), guaiacyl (G) andp-hydroxyphenyl (H), main side-chain linkages β-O-4′(A/A′/A′′), β-β′(B) and β-5′(C)structures, and esterified ferulic acid structure (FE) with a little content. The transformationstructures of syringyl (S′/S′′) were not found in the water-soluble MWL of bagasse.Comparing to the MWL, the molecular weight of the water-soluble MWL from the same rawmaterial was smaller. In addition, a great amount of the aliphatic hydroxyl group, and smallamounts of phenolic hydroxyl group in guaiacyl and condensed phenolic hydroxyl group werefound in the four types of lignins. The phenolic hydroxyl groups in syringyl andp-hydroxyphenyl, and carboxyl group were not found in the MWL of bagasse.
The solid alkali and active oxygen cooking had a high delignification rate, which couldremove85.5%of lignin in cornstalk and95.4%of lignin in bagasse, and had a protectiveeffect for the carbohydrate especially for the cellulose. In the cooking process, the syringyl(S/S′/S′′) units had a high reactivity. A novel G′structure was formed byan oxidizing reactionof the guaiacyl (G) unit. However, the p-hydroxyphenyl unit was stable in the cooking. For the sid-chain linkages, the phenolic β-O-4′(A/A′/A′′) structures could be changed by analkaline autoxidation reaction, and their non-phenolic structures had different reactivities. Thenon-phenolic β-β′(B) and β-5′(C) structures were stable in the cooking process, but the β-1′(D) structure was completely destroyed in the cooking. Moreover, the removed esterifiedferulic acid structure (FE) was also broken in the cooking, while the esterifiedp-acetoxy-benzoic acid structure (P) was stable.
In our research, it was found that only the MgO and Mg(OH)_2used in solid alkali andactive oxygen cooking had a high delignification rate and not occurred carbonizationphenomena. The solid alkali effectively could provide a weakly alkaline environment fordelignification, prevent the raw material carbonizing, and also have a protective effect for thecarbohydrate. The oxygen affected changes in the phenolic structure, leading to the oxidationof a benzylic alcohol group into a carbonyl group, and the facile attack of the ring-conjugatedstructure. The hydrogen peroxide could react with the carbonyl groups and double bonds onlignin side-chains, and further increasing the delignification rate.
In the solid alkali and active oxygen cooking, the lignin structure units could be removedin different cooking time. The acid soluble lignin was mainly removed in the heating stage,with the temperature under100℃, the removal of the acid-insoluble lignin and thedegradation of the carbohydrate were occurred in the heating stage also, but with thetemperature above100℃. In the analysises of the lignin models, it was found that theguaiacol and partial p-hydroxybenzoic acid were stable in the solid alkali and active oxygencooking process. While ferulic acid, p-coumaric acid, ethyl4-hydroxybenzoate, eugenol,trans-cinnamic acid and ethyl benzoate were thoroughly broken. In addition, the molecularweight of the water-soluble MWL changed smaller compared to the MWL in the cooking,namely the MWL was destroyed more seriously in the solid alkali and active oxygen cooking.And the P structure could be formed in the cooking process.
The pH value of the yellow liquors from the solid alkali and active oxygen cooking waslow, which was a weak alkaline environment, and a large amount of the formic acid and aceticacid were found in the yellow liquors. The yellow liquors mainly contained alkali lignin, withcertain Mg(OH)_2precipitate in them. Form the analysis of the yellow liquors in the cookingwith MgO/O_2, MgO/H_2O_2and MgO/H_2O_2/O_2, the main components in alkali and acid extracts were phthalic acid, mono (2-ethylhexyl) ester.
引文
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