生物质脱氧降解行为主要产物的定性定量分析及应用研究
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摘要
随着人类社会的发展,世界能源的消耗逐年提高。然而,化石能源的不可再生性及其使用给环境带来的问题,使得开发可再生性和环境友好性的新型能源成为科研人员工作的重点之一。本项研究的核心在于研究高效的生物质能源转化技术,并开发实用性生物质能源工艺。本研究首先由木质纤维素高效湿式脱氧降解技术展开。针对生物质高压水降解过程中,木质纤维素湿式脱氧降解转化率较低、渣产量较大、以及水的超临界状态需要较高的操作温度和操作压力等问题,本研究将互补溶剂概念引入生物质湿式脱氧降解研究。研究结果发现,采用典型互补溶剂1,4-二氧六环-水混合溶剂能够降低稻草湿式脱氧降解渣相产物的产率。在1,4-二氧六环和水混合湿式脱氧降解体系中,水发挥着亲核剂的作用。水会与稻草中原木素的一些活性中心发生反应,而1,4-二氧六环溶解纤维素和半纤维素,并注入生物质组织内部,与原木素结合。1,4-二氧六环将木质素碎片由木质纤维素组织溶入反应试剂,并引发随后的一系列降解反应。
在生物质湿式脱氧降解转化过程中,生物质降解的中间产物和自由基等会发生一系列聚合和再聚合反应。在较低的降解温度下,反应产物中以固相产物,即残渣相居多。当湿式脱氧降解反应温度升高时,木质素的降解效率大幅提高。木质素降解生成的苯氧基自由基与纤维素和半纤维素降解所产生的自由基、产物以及产物二次降解所形成的中间产物结合,形成各相湿式脱氧降解产物。当反应体系进入超临界状态时,混合溶剂的溶解能力和传质特性得到明显的提高。混合溶剂良好的溶解性能和传质特性使稻草湿式脱氧降解反应更加激烈的进行,促进轻组分的生成。
供氢溶剂能够为木质纤维素湿式脱氧降解体系提供氢,改善降解产物的相关性质。为了考察供氢溶剂对木质纤维素湿式脱氧降解转化率的影响,本研究将供氢溶剂-水混合溶剂引入反应体系,考察木质纤维素在乙醇-水混合溶剂和异丙醇-水混合溶剂中的湿式脱氧降解行为。湿式脱氧降解温度、降解停留时间和混合溶剂混合比例对稻草降解行为的影响得到研究。在供氢过程中,木质纤维素本身的氢和供氢溶剂提供的α-氢能够与反应体系中的氧结合生成水的过程,以及反应体系中的碳和氧相结合,生成稳定的气态产物CO2和较稳定的气态产物CO的过程是生物质湿式脱氧降解过程中两种主要的脱氧过程。脱氧过程促进了液相产物的热值随着温度的升高而提高。水的亲核性与醇溶剂的供氢性共同作用使得醇与水混合溶剂成为木质纤维素湿式脱氧降解过程中的互补溶剂,能够促进木质纤维素的湿式脱氧降解。在稻草乙醇-水和异丙醇-水混合溶剂湿式脱氧降解反应体系中,脱氧作用促进了轻组分产率随着温度的升高而增加,即氧与反应体系中的碳结合生成C02/CO和氧与反应体系中的氢结合生成水。较高的降解温度也会促进湿式脱氧降解中间产物进一步的降解,生成更小的小分子和挥发分物质,进而提高轻组分的产率。乙醇和异丙醇的供氢作用能够与木质纤维素降解过程中的自由基和活性碎片结合,生成较稳定的产物成分。这一过程也促进了小分子和挥发分物质的生成。
随着人类社会的发展,人类日常生活产生的废物种类也日益增多。在新能源开发过程中,最理想的发展模式应当是利用当地或短运输距离地区所产生的废物以开发新能源。污水处理厂数量和规模的发展对社会如何高效率地、高附加值地处理污水厂污泥提出了更高的要求。与生物质比较,污水厂污泥不具有难降解的木质纤维素结构,其更加容易降解转化有用的高附加值原料。在污泥湿式脱氧降解过程中,脱羰基脱氧作用仍然是污泥湿式脱氧降解过程中的主要作用之一。溶剂填充率对污泥的湿式脱氧降解行为影响较大。在溶剂填充率过高的情况下,反应体系中的重聚合作用得到促进。反应体系的重聚合反应促进聚合产物的生成。这些聚合产物最终进入液相和固相,增加油相和渣相的产率；并将氧带入液相产物,降低液相产物的热值。在污泥原料中的某些金属(Ni、Ca、Cr、Cu、Fe、Zn和碱土金属)本身也能够对污泥的湿式脱氧降解过程产生催化作用。因而,在污泥湿式脱氧降解过程中,催化剂的加入对污泥过程的影响不大。通过对污泥湿式脱氧降解液相产物的GC-MS和FTIR分析,酯类物质是液相产物中的主要成分。污泥湿式脱氧降解工艺可能是生产生物柴油类燃料的有效途径之一。但是,湿式脱氧降解过程不能降低液相产物中的含氮物质和金属成分。含氮物质和金属成分提高了液相产物的潜在危害,限制了液相产物的用途。
生物质湿式脱氧降解过程不要求原料进行干燥处理。因此,在原料准备阶段,生物质湿式脱氧降解工艺具有自身的经济优势。但是,相对较高的系统压力仍然是限制生物质湿式脱氧降解工艺向连续式工艺发展的主要障碍。在本项研究中,生物质干式脱氧降解工艺的新技术——生物质流化床烘焙和颗粒化联用技术得到研究和开发。流化床因其优良的传质和传热性能,以及便于连续式操作的优点,为生物质工业化应用的发展提供了便利。在本项研究中,通过对流化床结构的改进,木屑这种非典型性流化颗粒可以在没有流化介质存在的情况下,稳定地在流化床中流化。在改装流化床中,木屑的烘焙过程在不同影响因素(烘焙温度和烘焙停留时间)作用下的行为得到研究,主要表征内容有烘焙木屑失重、热值、能量转化率、能量密度、粒径分布、堆积密度和吸水性等。试验结果表明,随着烘焙温度和烘焙停留时间的提高,烘焙木屑的失重和热值提高,而烘焙木屑的能量转化率和吸水性降低。提高烘焙停留时间能够提高烘焙木屑的能量密度。在较高的反应温度、较低的烘焙停留时间下,烘焙木屑的堆积密度最小。木质纤维素的两种主要成分半纤维素和木质素的降解行为是大部分表征内容变化的主要原因。在烘焙过程中,半纤维素是最容易发生降解的成分。大部分半纤维素在烘焙前期完成降解。而木质素是一种缓慢降解的成分。木质素的降解是烘焙反应后期,烘焙木屑失重和热值继续提高的主要原因。
为了便于烘焙木屑的运输、储存和应用,经过流化床烘焙处理的木屑通过加热压制过程制成颗粒。制作颗粒过程中的能量消耗、颗粒吸水性及颗粒强度等因素是评价流化床烘焙-颗粒化联用工艺性能的主要指标。
在颗粒压制过程中,压制能量消耗量随着木质素降解程度的增加而增加。木质素是木屑中的粘结剂。木质素在烘焙过程中部分降解生成焦炭。同时,随着烘焙温度和烘焙停留时间的提高,颗粒密度也逐渐降低。颗粒密度的降低从一个方面说明,在同样的压力下,深度烘焙的木屑更加难以塑化,变得比较脆硬。因此,烘焙过程本身对于颗粒制作过程是不利的。
然而,通过对烘焙木屑制得颗粒的吸水性能研究发现,由烘焙木屑制得颗粒的吸水性要远低于由木屑原料制得颗粒的吸水性。提高烘焙温度和烘焙停留时间能够降低颗粒的吸水性。具有吸水性的半纤维素在较高烘焙温度和较高烘焙停留时间降解程度更高。木质纤维素天然结构也随之破坏,并降低对水分的吸收能力。与烘焙木屑的吸水性相比,烘焙木屑的吸水性要高于由同一条件下烘焙木屑制得的颗粒的吸水性。样品的结构也会对吸水性产生影响。烘焙颗粒的紧密结构能够对吸水过程产生抵制作用。因此,烘焙颗粒的吸水性较低。
在烘焙过程,木屑的木质素降解生成焦炭,使得烘焙颗粒的Meyer强度值低于由木屑原料制成的颗粒强度。同时,由在高烘焙温度、低烘焙停留时间得到的烘焙木屑制成的颗粒强度要低于由在低烘焙温度、高烘焙停留时间得到的烘焙木屑制成的颗粒强度的结果说明,相对于烘焙停留时间,烘焙温度对于木屑中木质素的降解程度影响更大。
本项研究揭示了生物质类物质在湿式与干式环境下的降解行为,研究了主要过程参数,特别是降解温度,对降解过程的影响机理。通过对主要表征指标的比较和考核,考察不同互补溶剂和供氢溶剂对生物质降解过程的作用机制。研究结果揭示,针对不同的生物质原料,可以通过选用不同功能的湿式脱氧降解溶剂,得到不同类型的湿式脱氧降解产物。为未来生物质应用工业的发展提供了参考依据。本研究将流化床工艺引入生物质固体产物加工工艺,避免了流化辅料对固体产物纯洁度的影响。流化床工艺的引入扩大了生物质烘焙技术的发展范围,为工业化利用的进一步发展提供了基础。
The energy consumption in the world has been increased in these years, as the development of this world. However, the fossil resource is limited, whose amount is decreasing as the increasing requirement of human. Several researchers have been working on the sustainable and renewable bio-energy with high efficiency. In this study, most of jobs were operated on the bio-energy with high efficiency and technology on the bio-energy in the industry.
The wet-decomposition of lignocellulose with high efficience was carried out in the first section of the present study. During the decomposition of biomass, the main problems were focused on the low conversion, the higher residue yield and the higher requirement of operation temperature and pressure, respectively. Therefore, the synergistic solvent was introduced into the wet-decomposition system. It was shown by the results that the residue yield was reduced in the1,4-dioxane-water mixture. In that mixture, water played as a nucleophile and reacts with some active centers in the protolignin. Meanwhile, The1,4-dioxane solvent solubilizes the cellulose and semi-cellulose, and impregnates the plant tissue, carrying the reagents to the protolignin and the resulting lignin fragments from the inner part of the cell to the solution. After then, several reactions were improved.
During the wet-decomposition of biomass, intermediate products and free radicals were reacted as polymerization and repolymerization. The solid products, named as residue, were the main products, when the runs were operated at low temperature. The decomposition of lignin was enhanced with increasing the reaction temperature. The phenoxy radicals were produced from the decomposition of lignin, while other kinds of radicals were produced from the the decomposition of cellulose and hemicellulose. They always polymerized with the intermediate products from the redecomposition of decomposition products. After then, the final products were produced. The solubility and mass transfer ability of mixture were significantly improved, and consequently enhanced the wet-decomposition of rice straw, which improved the formation of light fractions.
The wet-decomposition system of lignocellulose was received hydrogen from hydrogen-donor. Several properties of final products could be improved by the hydrogen-transfer process. The effects of hydrogen-donor on the wet-decomposition of lignocellulose were investigated in this study. The wet-decompositions of lignocellulose in the ethanol-water mixture and2-proponal-water mixture were carried out, in order to identify the properties of hydrogen-donor during the wet-decomposition process. Several parameters were involved in this study, such as temperature, holding time and mixture ratio.
The hydrogen in biomass and α-hydrogen from hydrogen-donor were combined with the oxygen in the system, and then produced water during the hydrogenation. Meanwhile, the carbon in the system was combined with oxygen, and then produced carbon monoxide and carbon dioxide. Those two processes are the main oxygen removal routes during the wet-decomposition. The higher heating values of liquid products were enhanced by the removal of oxygen. The mixture of alcohol and water could play as synergistic solvent as the nucleophilicity of water and hydrogenation of alcohol. The wet-decomposition of biomass could be improved by the synergistic solvent.
The formation of light fraction was improved with temperature increasing as removal of oxygen. The removal of oxygen was due to the formation of carbon dioxide/carbon monoxide and water during the wet-decomposition of rice straw in mixture of ethanol-water or2-proponal-water mixture. The intermediate products were further decomposed, which produced smaller compounds and volatiles. Therefore, the yield of light fraction was increased. The hydrogen from ethanol and2-proponal could stabilize the free radicals and fragments from decomposition of lignocellulose via the polymerization. Therefore, the formations of smaller compounds and volatiles were enhanced.
More and more kinds of waste were produced as human activities. The ideal situation is that most of the waste can be converted into energy or other useful products. The feedstock should be picked up around local area or somewhere with low transportation cost. As the development of maniple waste water plants, the treatment of sludge is one of the importants fields for scientists. The conversion of sludge into energy or other useful products with high efficiency is one of the hot fields. As there are few lignocelluloses in sludge, the decomposition process is much easier compared with typical biomass. Compared with typical biomass, similar situation can be indicated that the deoxygenation and decarboxylation was still one of the main reactions in the wet-decomposition of sludge. Solvent filling ratio affected the wet-decomposition of sludge significantly. The repolymerization reaction was improved with higher solvent filling ratio. Polymerized products were extracted into the liquid and solid fraction, resulting in the increment of oil and residue yields. The oxygen was introduced into those products with repolymerization. Therefore, the higher heating values of oil fractions were decreased.
The wet-decomposition process can be catalyzed by several metals involved in the sludge, such as Ni, Ca, Cr, Cu, Fe, Zn, and alkaline-earth metal, etc. The addition of catalysts didn't improve the wet-decomposition process significantly. The liquid products were analyzed by the GC-MS and FTIR, which indicated that the esters were the main compounds. It was shown by those results that the wet-decomposition of sludge could be a promising route for the production of bio-diesel. Howver, it should be noted that nitrogenous and metal compounds must be removed before wet-decomposition, which could limit the application of that technology.
The economic advantage of biomass wet-decomposition is that the raw material doesn't need be dried before operation. However, presently, that process cann't be operated continuously as the high pressure inside. A continue procedure was required by the industrial application. In this study, a new technology was investigated for industrial research, including torrefaction in fluidized bed and torrefied sawdust pelletization. The advantage of that technology is that the fluidized bed is a potential reactor which can be operated continuously with great mass and heat transfer ability. The typical batch fluidized bed was modified in this study. The sawdust could be fluidized in that reactor. The properties of torrefied sawdust were investigated under different torrefaction temperature and residence time, including weight loss, heating value, energy yield, energy density, particle size distribution, bulk density, and moisture absorption, etc. It was shown by the results that the weight loss and heating values of torrefied sawdust could be increased with increasing temperature and residence time, while energy yield and moisture absorption had the opposite trend. The energy density was enhanced with increasing residence time. The lowest bulk density was obtained at the condision with higher temperature and shorter residence time. The reasons for most results were focused on the decomposition of hemicellulose and lignin during the torrefaction. Hemicellulose is the active compound in sawdust. Most of hemicellulose was decomposed in the first30minutes of the torrefaction. However, lignin is a less active compound compared with hemicellulose. The slow decomposition of lignin was operated in the whole process of torrefaction.
The torrefied sawdust should be compressed into small pellets, which can be transported, reserved and application more easily. The pelletization energy consumption, moisture absorption and hardness of pellets were investigated in this studv.
During the pelletization, the compression energy consumption was increased with increasing the decomposition of lignin. Lignin is the natural stiffener in sawdust. Lignin was decomposed into char in the torrefaction. Meanwhile, the densities of pellets were reduced with increasing the torrefaction temperature and residence time. It was shown by those results that the further torrefied sawdust became more brittle and less plastic.
However, according to the further results, the moisture absorptions of pellets from torrefied sawdust were significantly lower that those of raw sawdust pellets. The moisture absorptions of pellets from torrefied sawdust were decreased with increasing torrefaction temperature and torrefaction residence time. Hemicellulose with high moisture absorption ability was decomposed further at higher torrefaction temperature with longer torrefaction residence time. The natural structure of lignocellulose was destroyed, resulting in the decrement of moisture absorption.
Meanwhile, compared with the moisture absorption of torredied sawdust, the moisture absorptions of pellets made of torredied sawdust with same torrefaction condition were lower. It was indicated that the structure of sample affected the moisture absorption. The moisture absorption was reduced during the compression.
The Meyer hardnesses of pellets of torrefied sawdust were lower than those of raw sawdust pellets, as the decrement of lignin amount during the torrefaction. The Meyer hardnesses of pellets, which made of torrefied sawdust at higher torrefaction temperature and shorter residence time, were lower than those made of torrefied sawdust at lower torrefaction temperature and longer residence time. It can be due to that torrefaction temperature is the primary parameter compared with residence time.
In this study, the wet-decomposition and dry-decomposition of biomass were investigated, in order to identify the effects of key parameters and mechanism in the decomposition process. The roles of synergistic solvents and hydrogen-donor were shown with the comparisons of the effects of key parameters. Different wet-decomposition products can be obtained from different feedstocks with different wet-decomposition solvents. In this study, several basic results were provided for the future industrial application. The fluidized bed was introduced into the production of biomass solid products without procedure of solid products separation. The scope of torrefaction was expanded for the industrial application in the near future.
在生物质湿式脱氧降解转化过程中,生物质降解的中间产物和自由基等会发生一系列聚合和再聚合反应。在较低的降解温度下,反应产物中以固相产物,即残渣相居多。当湿式脱氧降解反应温度升高时,木质素的降解效率大幅提高。木质素降解生成的苯氧基自由基与纤维素和半纤维素降解所产生的自由基、产物以及产物二次降解所形成的中间产物结合,形成各相湿式脱氧降解产物。当反应体系进入超临界状态时,混合溶剂的溶解能力和传质特性得到明显的提高。混合溶剂良好的溶解性能和传质特性使稻草湿式脱氧降解反应更加激烈的进行,促进轻组分的生成。
供氢溶剂能够为木质纤维素湿式脱氧降解体系提供氢,改善降解产物的相关性质。为了考察供氢溶剂对木质纤维素湿式脱氧降解转化率的影响,本研究将供氢溶剂-水混合溶剂引入反应体系,考察木质纤维素在乙醇-水混合溶剂和异丙醇-水混合溶剂中的湿式脱氧降解行为。湿式脱氧降解温度、降解停留时间和混合溶剂混合比例对稻草降解行为的影响得到研究。在供氢过程中,木质纤维素本身的氢和供氢溶剂提供的α-氢能够与反应体系中的氧结合生成水的过程,以及反应体系中的碳和氧相结合,生成稳定的气态产物CO2和较稳定的气态产物CO的过程是生物质湿式脱氧降解过程中两种主要的脱氧过程。脱氧过程促进了液相产物的热值随着温度的升高而提高。水的亲核性与醇溶剂的供氢性共同作用使得醇与水混合溶剂成为木质纤维素湿式脱氧降解过程中的互补溶剂,能够促进木质纤维素的湿式脱氧降解。在稻草乙醇-水和异丙醇-水混合溶剂湿式脱氧降解反应体系中,脱氧作用促进了轻组分产率随着温度的升高而增加,即氧与反应体系中的碳结合生成C02/CO和氧与反应体系中的氢结合生成水。较高的降解温度也会促进湿式脱氧降解中间产物进一步的降解,生成更小的小分子和挥发分物质,进而提高轻组分的产率。乙醇和异丙醇的供氢作用能够与木质纤维素降解过程中的自由基和活性碎片结合,生成较稳定的产物成分。这一过程也促进了小分子和挥发分物质的生成。
随着人类社会的发展,人类日常生活产生的废物种类也日益增多。在新能源开发过程中,最理想的发展模式应当是利用当地或短运输距离地区所产生的废物以开发新能源。污水处理厂数量和规模的发展对社会如何高效率地、高附加值地处理污水厂污泥提出了更高的要求。与生物质比较,污水厂污泥不具有难降解的木质纤维素结构,其更加容易降解转化有用的高附加值原料。在污泥湿式脱氧降解过程中,脱羰基脱氧作用仍然是污泥湿式脱氧降解过程中的主要作用之一。溶剂填充率对污泥的湿式脱氧降解行为影响较大。在溶剂填充率过高的情况下,反应体系中的重聚合作用得到促进。反应体系的重聚合反应促进聚合产物的生成。这些聚合产物最终进入液相和固相,增加油相和渣相的产率；并将氧带入液相产物,降低液相产物的热值。在污泥原料中的某些金属(Ni、Ca、Cr、Cu、Fe、Zn和碱土金属)本身也能够对污泥的湿式脱氧降解过程产生催化作用。因而,在污泥湿式脱氧降解过程中,催化剂的加入对污泥过程的影响不大。通过对污泥湿式脱氧降解液相产物的GC-MS和FTIR分析,酯类物质是液相产物中的主要成分。污泥湿式脱氧降解工艺可能是生产生物柴油类燃料的有效途径之一。但是,湿式脱氧降解过程不能降低液相产物中的含氮物质和金属成分。含氮物质和金属成分提高了液相产物的潜在危害,限制了液相产物的用途。
生物质湿式脱氧降解过程不要求原料进行干燥处理。因此,在原料准备阶段,生物质湿式脱氧降解工艺具有自身的经济优势。但是,相对较高的系统压力仍然是限制生物质湿式脱氧降解工艺向连续式工艺发展的主要障碍。在本项研究中,生物质干式脱氧降解工艺的新技术——生物质流化床烘焙和颗粒化联用技术得到研究和开发。流化床因其优良的传质和传热性能,以及便于连续式操作的优点,为生物质工业化应用的发展提供了便利。在本项研究中,通过对流化床结构的改进,木屑这种非典型性流化颗粒可以在没有流化介质存在的情况下,稳定地在流化床中流化。在改装流化床中,木屑的烘焙过程在不同影响因素(烘焙温度和烘焙停留时间)作用下的行为得到研究,主要表征内容有烘焙木屑失重、热值、能量转化率、能量密度、粒径分布、堆积密度和吸水性等。试验结果表明,随着烘焙温度和烘焙停留时间的提高,烘焙木屑的失重和热值提高,而烘焙木屑的能量转化率和吸水性降低。提高烘焙停留时间能够提高烘焙木屑的能量密度。在较高的反应温度、较低的烘焙停留时间下,烘焙木屑的堆积密度最小。木质纤维素的两种主要成分半纤维素和木质素的降解行为是大部分表征内容变化的主要原因。在烘焙过程中,半纤维素是最容易发生降解的成分。大部分半纤维素在烘焙前期完成降解。而木质素是一种缓慢降解的成分。木质素的降解是烘焙反应后期,烘焙木屑失重和热值继续提高的主要原因。
为了便于烘焙木屑的运输、储存和应用,经过流化床烘焙处理的木屑通过加热压制过程制成颗粒。制作颗粒过程中的能量消耗、颗粒吸水性及颗粒强度等因素是评价流化床烘焙-颗粒化联用工艺性能的主要指标。
在颗粒压制过程中,压制能量消耗量随着木质素降解程度的增加而增加。木质素是木屑中的粘结剂。木质素在烘焙过程中部分降解生成焦炭。同时,随着烘焙温度和烘焙停留时间的提高,颗粒密度也逐渐降低。颗粒密度的降低从一个方面说明,在同样的压力下,深度烘焙的木屑更加难以塑化,变得比较脆硬。因此,烘焙过程本身对于颗粒制作过程是不利的。
然而,通过对烘焙木屑制得颗粒的吸水性能研究发现,由烘焙木屑制得颗粒的吸水性要远低于由木屑原料制得颗粒的吸水性。提高烘焙温度和烘焙停留时间能够降低颗粒的吸水性。具有吸水性的半纤维素在较高烘焙温度和较高烘焙停留时间降解程度更高。木质纤维素天然结构也随之破坏,并降低对水分的吸收能力。与烘焙木屑的吸水性相比,烘焙木屑的吸水性要高于由同一条件下烘焙木屑制得的颗粒的吸水性。样品的结构也会对吸水性产生影响。烘焙颗粒的紧密结构能够对吸水过程产生抵制作用。因此,烘焙颗粒的吸水性较低。
在烘焙过程,木屑的木质素降解生成焦炭,使得烘焙颗粒的Meyer强度值低于由木屑原料制成的颗粒强度。同时,由在高烘焙温度、低烘焙停留时间得到的烘焙木屑制成的颗粒强度要低于由在低烘焙温度、高烘焙停留时间得到的烘焙木屑制成的颗粒强度的结果说明,相对于烘焙停留时间,烘焙温度对于木屑中木质素的降解程度影响更大。
本项研究揭示了生物质类物质在湿式与干式环境下的降解行为,研究了主要过程参数,特别是降解温度,对降解过程的影响机理。通过对主要表征指标的比较和考核,考察不同互补溶剂和供氢溶剂对生物质降解过程的作用机制。研究结果揭示,针对不同的生物质原料,可以通过选用不同功能的湿式脱氧降解溶剂,得到不同类型的湿式脱氧降解产物。为未来生物质应用工业的发展提供了参考依据。本研究将流化床工艺引入生物质固体产物加工工艺,避免了流化辅料对固体产物纯洁度的影响。流化床工艺的引入扩大了生物质烘焙技术的发展范围,为工业化利用的进一步发展提供了基础。
The energy consumption in the world has been increased in these years, as the development of this world. However, the fossil resource is limited, whose amount is decreasing as the increasing requirement of human. Several researchers have been working on the sustainable and renewable bio-energy with high efficiency. In this study, most of jobs were operated on the bio-energy with high efficiency and technology on the bio-energy in the industry.
The wet-decomposition of lignocellulose with high efficience was carried out in the first section of the present study. During the decomposition of biomass, the main problems were focused on the low conversion, the higher residue yield and the higher requirement of operation temperature and pressure, respectively. Therefore, the synergistic solvent was introduced into the wet-decomposition system. It was shown by the results that the residue yield was reduced in the1,4-dioxane-water mixture. In that mixture, water played as a nucleophile and reacts with some active centers in the protolignin. Meanwhile, The1,4-dioxane solvent solubilizes the cellulose and semi-cellulose, and impregnates the plant tissue, carrying the reagents to the protolignin and the resulting lignin fragments from the inner part of the cell to the solution. After then, several reactions were improved.
During the wet-decomposition of biomass, intermediate products and free radicals were reacted as polymerization and repolymerization. The solid products, named as residue, were the main products, when the runs were operated at low temperature. The decomposition of lignin was enhanced with increasing the reaction temperature. The phenoxy radicals were produced from the decomposition of lignin, while other kinds of radicals were produced from the the decomposition of cellulose and hemicellulose. They always polymerized with the intermediate products from the redecomposition of decomposition products. After then, the final products were produced. The solubility and mass transfer ability of mixture were significantly improved, and consequently enhanced the wet-decomposition of rice straw, which improved the formation of light fractions.
The wet-decomposition system of lignocellulose was received hydrogen from hydrogen-donor. Several properties of final products could be improved by the hydrogen-transfer process. The effects of hydrogen-donor on the wet-decomposition of lignocellulose were investigated in this study. The wet-decompositions of lignocellulose in the ethanol-water mixture and2-proponal-water mixture were carried out, in order to identify the properties of hydrogen-donor during the wet-decomposition process. Several parameters were involved in this study, such as temperature, holding time and mixture ratio.
The hydrogen in biomass and α-hydrogen from hydrogen-donor were combined with the oxygen in the system, and then produced water during the hydrogenation. Meanwhile, the carbon in the system was combined with oxygen, and then produced carbon monoxide and carbon dioxide. Those two processes are the main oxygen removal routes during the wet-decomposition. The higher heating values of liquid products were enhanced by the removal of oxygen. The mixture of alcohol and water could play as synergistic solvent as the nucleophilicity of water and hydrogenation of alcohol. The wet-decomposition of biomass could be improved by the synergistic solvent.
The formation of light fraction was improved with temperature increasing as removal of oxygen. The removal of oxygen was due to the formation of carbon dioxide/carbon monoxide and water during the wet-decomposition of rice straw in mixture of ethanol-water or2-proponal-water mixture. The intermediate products were further decomposed, which produced smaller compounds and volatiles. Therefore, the yield of light fraction was increased. The hydrogen from ethanol and2-proponal could stabilize the free radicals and fragments from decomposition of lignocellulose via the polymerization. Therefore, the formations of smaller compounds and volatiles were enhanced.
More and more kinds of waste were produced as human activities. The ideal situation is that most of the waste can be converted into energy or other useful products. The feedstock should be picked up around local area or somewhere with low transportation cost. As the development of maniple waste water plants, the treatment of sludge is one of the importants fields for scientists. The conversion of sludge into energy or other useful products with high efficiency is one of the hot fields. As there are few lignocelluloses in sludge, the decomposition process is much easier compared with typical biomass. Compared with typical biomass, similar situation can be indicated that the deoxygenation and decarboxylation was still one of the main reactions in the wet-decomposition of sludge. Solvent filling ratio affected the wet-decomposition of sludge significantly. The repolymerization reaction was improved with higher solvent filling ratio. Polymerized products were extracted into the liquid and solid fraction, resulting in the increment of oil and residue yields. The oxygen was introduced into those products with repolymerization. Therefore, the higher heating values of oil fractions were decreased.
The wet-decomposition process can be catalyzed by several metals involved in the sludge, such as Ni, Ca, Cr, Cu, Fe, Zn, and alkaline-earth metal, etc. The addition of catalysts didn't improve the wet-decomposition process significantly. The liquid products were analyzed by the GC-MS and FTIR, which indicated that the esters were the main compounds. It was shown by those results that the wet-decomposition of sludge could be a promising route for the production of bio-diesel. Howver, it should be noted that nitrogenous and metal compounds must be removed before wet-decomposition, which could limit the application of that technology.
The economic advantage of biomass wet-decomposition is that the raw material doesn't need be dried before operation. However, presently, that process cann't be operated continuously as the high pressure inside. A continue procedure was required by the industrial application. In this study, a new technology was investigated for industrial research, including torrefaction in fluidized bed and torrefied sawdust pelletization. The advantage of that technology is that the fluidized bed is a potential reactor which can be operated continuously with great mass and heat transfer ability. The typical batch fluidized bed was modified in this study. The sawdust could be fluidized in that reactor. The properties of torrefied sawdust were investigated under different torrefaction temperature and residence time, including weight loss, heating value, energy yield, energy density, particle size distribution, bulk density, and moisture absorption, etc. It was shown by the results that the weight loss and heating values of torrefied sawdust could be increased with increasing temperature and residence time, while energy yield and moisture absorption had the opposite trend. The energy density was enhanced with increasing residence time. The lowest bulk density was obtained at the condision with higher temperature and shorter residence time. The reasons for most results were focused on the decomposition of hemicellulose and lignin during the torrefaction. Hemicellulose is the active compound in sawdust. Most of hemicellulose was decomposed in the first30minutes of the torrefaction. However, lignin is a less active compound compared with hemicellulose. The slow decomposition of lignin was operated in the whole process of torrefaction.
The torrefied sawdust should be compressed into small pellets, which can be transported, reserved and application more easily. The pelletization energy consumption, moisture absorption and hardness of pellets were investigated in this studv.
During the pelletization, the compression energy consumption was increased with increasing the decomposition of lignin. Lignin is the natural stiffener in sawdust. Lignin was decomposed into char in the torrefaction. Meanwhile, the densities of pellets were reduced with increasing the torrefaction temperature and residence time. It was shown by those results that the further torrefied sawdust became more brittle and less plastic.
However, according to the further results, the moisture absorptions of pellets from torrefied sawdust were significantly lower that those of raw sawdust pellets. The moisture absorptions of pellets from torrefied sawdust were decreased with increasing torrefaction temperature and torrefaction residence time. Hemicellulose with high moisture absorption ability was decomposed further at higher torrefaction temperature with longer torrefaction residence time. The natural structure of lignocellulose was destroyed, resulting in the decrement of moisture absorption.
Meanwhile, compared with the moisture absorption of torredied sawdust, the moisture absorptions of pellets made of torredied sawdust with same torrefaction condition were lower. It was indicated that the structure of sample affected the moisture absorption. The moisture absorption was reduced during the compression.
The Meyer hardnesses of pellets of torrefied sawdust were lower than those of raw sawdust pellets, as the decrement of lignin amount during the torrefaction. The Meyer hardnesses of pellets, which made of torrefied sawdust at higher torrefaction temperature and shorter residence time, were lower than those made of torrefied sawdust at lower torrefaction temperature and longer residence time. It can be due to that torrefaction temperature is the primary parameter compared with residence time.
In this study, the wet-decomposition and dry-decomposition of biomass were investigated, in order to identify the effects of key parameters and mechanism in the decomposition process. The roles of synergistic solvents and hydrogen-donor were shown with the comparisons of the effects of key parameters. Different wet-decomposition products can be obtained from different feedstocks with different wet-decomposition solvents. In this study, several basic results were provided for the future industrial application. The fluidized bed was introduced into the production of biomass solid products without procedure of solid products separation. The scope of torrefaction was expanded for the industrial application in the near future.
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