【作者】 佟立成；

【导师】 常建民；

【作者基本信息】 北京林业大学 ， 木材科学与技术， 2012， 博士

【摘要】 能源和材料是人类社会可持续发展的基础和重要保障。利用可再生的生物质资源热裂解液化制备人造板用生物基树脂材料具有重要的科学意义和实际应用价值。本论文针对生物质热裂解液化制备酚醛树脂的关键科学技术问题展开系统研究和分析,主要进行了年处理1000t生物质热裂解液化中试生产线设计、生物质热裂解液化影响因素分析与工艺优化、生物质热裂解液化产物分析、以制备刨花板为去向的生物油酚醛树脂合成优化以及生物油酚醛树脂结构表征与固化机理研究。本论文将生物油的上游高效制备与下游的树脂合成应用有机地融合起来,从工业化应用的角度对生物质热裂解液化制备酚醛树脂产业链条中的关键科学问题进行技术攻关、熟化与创新研究,具有较强工程实践意义。本论文所得主要结论与创新点如下：(1)完成了年处理量为1000t的生物质热裂解液化中试生产线的工艺设计,对热解气流程、生物油流程、燃气供热流程以及冷却循环流程进行了理论分析和设计,将热解产生的不凝结气体循环用作流化载气和反应器的热源燃料,实现了生物质热裂解液化反应过程的自热化。(2)对生物质热裂解液化生产线的热力和动力进行了计算,求得单位时间木质原料热解反应需要的总热量为56kj,系统所需的总功率为76kW,甲烷的补给量为1.86kg/h；对生产线中的流化床反应器、旋风分离器、管壳式换热器、冷凝系统、水汽分离器、缓冲罐、暂存罐等进行了设计、选型和布局,运行表明所设计的各关键系统结构紧凑、性能优良,中试生产线整体运行稳定,达到了设计要求。(3)以杨木树皮为原料,以产油率、酚类物质含量、所合成生物油酚醛树脂胶黏剂粘剂的胶合强度为目标,快速热解优化工艺为：热解温度823K(550℃)、杨木树皮颗粒粒径0.3-0.45mm、螺旋进料器转速20r/min(对应的进料量为26kg/h),流化气体流量25m3/h。(4)杨木生物油主要有机成分为酚类、醛类、酸类、酮类和烃类物质,其在有机相中相对百分含量分别约为33.55%、32%、14%、8.75%、8.53%和2.91%；生物油的pH值约为3.33,粘度39.7mPa.s,含水率31.856%,密度1.146g/cm3,高位热值约为14.6MJ/kg,存储过程不稳定,pH和粘度会发生较明显变化；生物油的重均分子量为572,数均分子量为211,其分子量主要分布在小于560的区段(约占74%)。(5)杨木热解炭粒径主要集中于10-200μm之间,以40-100μm居多,其具有一定的碳含量和热值,可以直接用来作为一种燃料；碘吸附值、亚甲基蓝吸附值和比表面积均较低,作为吸附用活性炭使用前需进一步活化；不凝结气体主要包括CO、 C02、 H2、 CH4和H2O,相对百分含量分别约为40.16%、40.10%、7.95%、0.96%以及10.84%。(6)随F/P摩尔比升高,生物油酚醛树脂的粘度呈上升趋势,游离酚含量降低,静曲强度、内结合强度呈先增加后减小的趋势,甲醛释放量显著升高；随生物油替代率增加,生物油酚醛树脂的粘度、游离苯酚含量,胶接刨花板的静曲强度和内结合强度均下降,而甲醛释放量升高；随NaOH/P摩尔比升高,粘度升高趋势逐渐下降,游离苯酚含量,甲醛释放量下降,胶接刨花板的静曲强度和内结合强度先升高后小幅下降；随反应时间延长,树脂粘度升高趋势逐渐增大,游离苯酚含量、甲醛释放量均下降,静曲强度、内结合强度先升高后小幅下降。(7)综合考虑树脂各项性能与生产成本之间的关系,生物油酚醛树脂的较佳合成工艺条件为：F/P摩尔比为2.0,生物油替代率为35%, NaOH/P摩尔比为0.45,反应时间为50min；该优化合成工艺下BPF树脂胶接刨花板的静曲强度(MOR)为36MPa、内结合强度(IB)为0.79MPa均大幅超过刨花板国家标准(MOR≥18MPa, IB≥0.45MPa),甲醛释放量为0.56mg/100g远低于现行刨花板最低行业标准(≤5mg/100g)要求。(8)对生物油酚醛树脂和普通酚醛树脂进行了FTIR、13C-CP/MAS NMR和GPC测试,发现生物油酚醛树脂在固化过程中生物油中多元酚类结构上的羟甲基与苯酚结构单元上的羟甲基发生了共缩聚反应,生物油的引入提高了整个树脂体系的聚合度,生物油组分最终可较好地嵌入到整个树脂的固化体系。(9)对生物油酚醛树脂和酚醛树脂进行了DSC分析,发现生物油酚醛树脂的固化温度略高于酚醛树脂,说明酚醛树脂体系中生物油的引入需要更多的固化热量；采用Kissinger方法求出30%替代率生物油酚醛树脂的相关动力学参数,包括活化能105.3kJ/mol,频率因子8.32×1012s-1,反应级数为0.94。更多还原

【Abstract】 Energy and materials are the basis for sustainable development of human society. It has great scientific importance and practical value to use fast pyrolysis technology of renewable biomass resources for preparing woody bio-resin materials. This paper intended for key technologies of wood fast pyrolysis and bio-oil phenolic resins synthesis. It mainly includes the design of pilot production line of biomass pyrolysis liquefaction with processing1000tonnes biomass a year, analysis and process optimization of influence factors of biomass pyrolysis liquefaction, analysis on products of biomass pyrolysis liquefaction, synthesis optimization of bio-oil phenolic resin for preparation of particle board, study on the curing mechanism and structural characterization of bio-oil phenolic resin. This paper organically combined upstream preparation of bio-oil efficiently with its downstream synthesis application. And then, much effort had been put on the key technologies of wood fast pyrolysis and bio-oil phenolic resins synthesis by technology research, improvement and innovation from the perspective of industrial application, which has important engineering practice significance. The main conclusions and innovations derived from this paper are as follows.(1) The design of pilot production line of biomass pyrolysis liquefaction with processing1000tonnes biomass a year has been finished. The pyrolysis vapor process, bio-oil process, gas heating process and cooling cycles process have been analysed theoretically and designed. The self-heating process of biomass pyrolysis liquefaction has been realized when using non-condensation of gases for circulating as a flow of carrier gas and heat source of fluidized-bed reactor.(2) Heat and power on the pilot production line of biomass pyrolysis has been calculated. The total calories in woody raw materials for pyrolysis is56kJ; The system required total power is76kW; The increment of methane is1.86kg/h. Fluidized bed reactor, cyclone separator, shell-and-tube heat exchanger, condensation system, moisture separators, buffer tank, staging, tank were designed and selected. Expermental running indicated that the key systems were compact and had excellent performance and the pilot production line ran stability and met the design requirements. (3) In order to improve the yield and content of phenols of bio-oil and bonding strength of phenol-formaldehyde resin adhesive, poplar bark was taken as raw materials for the optimum technologies of fast pyrolysis, which are:pyrolysis temperature of823K(550℃), particle size of0.3-0.45mm, Screw-feeder speed of20r/min(feeding rate of26kg/h), Streams of gas flow of25m3/h.(4) The main organic components of Poplar bio-oil are phenols, aldehydes, acids, and ketones and hydrocarbons and the relative percentage contents are33.55%,32%,14%,8.75%,8.53%and2.91%separately. The pH value of bio-oil was about3.33; The viscosity was39.7mPa-s; The water content was31.856%; The relative density was1.146g/cm3; The high calorific value was14.6MJ/kg. The PH and viscosity would change obviously. The weight-average molecular weight was572; The number-average molecular weight was211. The molecular weight of bio-oil was main distributed less than560.(5) The particle size of bio-char of Poplar was mainly in10-200μm and mostly in40-100μm. The bio-char has a certain amount of carbon content and caloric value and can be used for a kind of fuels directly. It should be further activation before using of adsorption of activated carbon because of the low methylene blue adsorption value and specific surface area. Non-condensing gas components analysis showed that it was included CO, CO2, H2, CH4and H2O and the relative percentage contents are40.16%,40.10%,7.95%,0.96%and10.84%.(6) As the increase of F/P molar ratio, the viscosity of bio-oil-phenolic resin gone up, free phenol content reduced, MOR and IB increased firstly and then reduced and formaldehyde increased significantly. As the increase of substitution rate of bio-oil, the viscosity of bio-oil-phenolic resin, free phenol content and MOR and IB reduced and formaldehyde emission increased. As the increase of NaOH/P molar ratio, the increasing trend of viscosity declined gradually, free phenol content reduced, formaldehyde emission reduced and MOR and bond strength increased firstly and then reduced. As the increase of reaction time, the viscosity of bio-oil-phenolic resin gone up, free phenol content reduced, formaldehyde emission reduced and MOR and IB increased firstly and then reduced in small scale.(7) Comprehensive consideration of the relationship between resin performance and production costs, the better technological conditions for synthesis of bio-oil-phenolic resin were F/P molar ratio of2.0, bio-oil substitution rate of35%, NaOH/P molar ratio of0.45, reaction time of50min. The optimization of synthesis technology was that the MOR and IB of BPF resin was36MPa and0.79MPa, which exceeds national standards substantially for Particle board (MOR>18MPa, IB>0.45MPa) and formaldehyde emission was0.56mg/100g, which well below the current minimum of Particle board industry standards (≤5mg/100g).(8) Analysis of bio-oil-phenolic resin and common phenolic resin using FTIR,13C-CP/MAS and GPC. It is found that the hydroxymethyl on the class structure of polyphenols of bio-oil and hydroxymethyl on structural units of phenol occurred copolycondensation reaction during the curing process. The degree of polymerization improved with the addition of bio-oil. Bio-oil components can be better embedded in the resin curing system eventually.(9) Analysis of bio-oil-phenolic resin and common phenolic resin using DSC found that the curing temperature of bio-oil-phenolic resin slightly higher than that of common phenolic resin, so more of the curing heat was needed with the addition of bio-oil. Dynamic parameters of bio-oil-phenolic resin with bio-oil substitution rate of30%has been calculated using the method of Kissinger, included activation energy of105.3kJ/mol, frequency factor of8.32×1012s-1, reaction series of0.94.更多还原