林木剩余物快速热解与热解油制备酚醛树脂技术及应用

针对林木剩余物资源利用率不高、人造板用胶黏剂依赖化石资源、环保性不理想等难题，本项目在国家科技支撑、自然基金、国家林业局“948”、科技部农转金等6项课题支持下，历时10余年，在林木剩余物热裂解炼制装备、富酚热解油制备技术、热解油酚醛树脂合成技术等三方面取得突破性进展，研制出林木剩余物快速热解装备，创制出环境友好、高附加值的热解油酚醛树脂胶黏剂产品，创建了富酚热解油炼制及热解油制胶工业化生产模式。主要科技创新如下： 1. 创制林木剩余物快速热解装备。累计研发出自热式林木剩余物快速热解实验设备4台、工业化中试生产线2条，实现了热解油的连续、稳定化生产，集成了热解尾气循环利用、分级可控冷凝等多项创新功能。所创制的新型流化床式热解反应器、生物质进料器、复合冷凝器等关键功能组件，解决了多年来困扰生物质热解炼制转化效率低、生物质颗粒连续进料困难和热解油难以高效收集的技术难题。热裂解设备连续稳定生产30天以上，热解尾气自供热比例达到75%以上，热解油产率稳定在50%-60%。 2. 构建生物质热裂解炼制酚类物质的基础理论体系，创立富酚热解油生产技术。阐明了热裂解炼制富酚热解油过程中原料响应特性及成分富集机制，揭示了金属盐催化剂对生物质木质素热裂解过程中酚类物质转化路径的影响，解明了木质素高效解聚生成酚类物质规律，形成了富酚热解油炼制的基础理论，提出了富酚热解油调控方法。研发出集原料预处理、热裂解过程定向调控于一体的富酚热解油生产工艺技术，热解油得率平均达到50wt%以上，酚类物质富集程度达到15wt%以上，附加值提高20%-30%。 3. 发明热解油全油利用制备酚醛树脂胶黏剂工艺技术。研发出多元同步聚合、逐级连续反应及协同催化技术，解决了热解油加入比例有限、合成反应过程不稳定、树脂固化能耗高等难点，实现了热解油全油直接利用。研发出高性能、环境友好型热解油酚醛树脂胶黏剂产品，热解油替代苯酚、甲醛等石化原料比例高达50%，成本降低10%-25%，甲醛释放量低于日本JIS F☆☆☆☆级标准限量值。本项目获授权发明专利19件、实用新型专利4件 出版专著1部，发表期刊论文101篇（SCI 21篇、EI 10篇） 曾获高等学校科学研究优秀成果奖技术发明二等奖1项，培养研究生23人，其中获全国百篇优博提名1人。

Facing the challenges of low utilization rate of forest residues, heavy dependence on fossil-based raw materials for wood-based panel adhesives, and unsatisfactory environmental performance, this project, supported by 6 research projects including the National Key Technology R&D Program, National Natural Science Foundation of China, State Forestry Administration "948" Program, and Ministry of Science and Technology Agricultural Science and Technology Achievement Transformation Fund, has achieved breakthroughs in three aspects after over a decade of research: forest residue fast pyrolysis refining equipment, phenol-rich pyrolysis oil preparation technology, and pyrolysis oil-based phenolic resin synthesis technology. We have developed a fast pyrolysis equipment for forest residues, created an environmentally friendly and high-value-added pyrolysis oil-based phenolic resin adhesive product, and established an industrial production mode for phenol-rich pyrolysis oil refining and adhesive production from pyrolysis oil. The main technological innovations are as follows:
1. Development of forest residue fast pyrolysis equipment. We have developed 4 self-heating experimental fast pyrolysis devices for forest residues and 2 industrial pilot production lines, realizing continuous and stable production of pyrolysis oil, and integrating multiple innovative functions such as pyrolysis tail gas recycling and graded controllable condensation. The newly developed key functional components including a fluidized bed pyrolysis reactor, biomass feeder, and composite condenser have solved the long-standing technical problems of low conversion efficiency in biomass pyrolysis refining, difficulty in continuous feeding of biomass particles, and inefficient collection of pyrolysis oil. The pyrolysis equipment can operate continuously and stably for more than 30 days, with a self-heating supply ratio of pyrolysis tail gas reaching over 75%, and a stable pyrolysis oil yield of 50%-60%.
2. Establishment of the basic theoretical system for biomass pyrolysis refining to produce phenolic compounds, and creation of phenol-rich pyrolysis oil production technology. We have clarified the feedstock response characteristics and component enrichment mechanism during the pyrolysis refining of phenol-rich pyrolysis oil, revealed the influence of metal salt catalysts on the conversion pathway of phenolic substances during the pyrolysis of biomass lignin, elucidated the law of efficient depolymerization of lignin to produce phenolic substances, formed the basic theory of phenol-rich pyrolysis oil refining, and proposed a regulation method for phenol-rich pyrolysis oil. We have developed a production technology for phenol-rich pyrolysis oil integrating feedstock pretreatment and directional regulation of the pyrolysis process, with an average pyrolysis oil yield of over 50 wt%, a phenolic substance enrichment degree of over 15 wt%, and an increase in added value of 20%-30%.
3. Invention of a process technology for preparing phenolic resin adhesives using full pyrolysis oil. We have developed multi-component synchronous polymerization, stepwise continuous reaction and synergistic catalysis technologies, solving the difficulties of limited addition ratio of pyrolysis oil, unstable synthesis reaction process, and high resin curing energy consumption, and realizing direct full-oil utilization of pyrolysis oil. We have developed a high-performance, environmentally friendly pyrolysis oil-based phenolic resin adhesive product, with the substitution ratio of pyrolysis oil for petrochemical raw materials such as phenol and formaldehyde reaching up to 50%, a cost reduction of 10%-25%, and formaldehyde emission lower than the limit value of Japan's JIS F☆☆☆☆ standard. This project has obtained 19 authorized invention patents and 4 utility model patents, published 1 monograph and 101 journal papers (21 SCI-indexed papers, 10 EI-indexed papers), won the Second Prize of Technical Invention, Outstanding Scientific Research Achievements Award of Colleges and Universities, and trained 23 graduate students, including 1 recipient of the National 100 Excellent Doctoral Dissertations Nomination.