生物质快速热解油气接力式碱性催化提质的应用基础研究

Fast pyrolysis of biomass and upgraded products by relay catalysis is one of the most promising approaches for the industrialization of fast pyrolysis oil delicate modification. Fast pyrolysis of biomass and upgraded products by relay catalysis avoids the difficulties of liquid feed and the condensation during the second heating of bio-oil when using the traditional method. Moreover, the yield and quality of light oil can be improved. The recycle and regeneration of catalysts are easier than the traditional method. However, there is relatively little foundational research about this method. This project will use the new built fast pyrolysis-catalysis-gas chromatograph and mass spectrometer to investigate the relationship between catalyst components-preparation-structure and selectively upgrading products. The preparation of catalyst will be optimized. The pilot plant equipment of double reaction tubes (5 L/h) with high temperature millisecond pyrolysis and upgraded products by relay catalysis will be used to reveal the thermal shock effect on the cracking of heavy oil macromolecule during the instant contact between high temperature catalyst and pyrolysis vapor. The relationship between fast pyrolysis reaction conditions-catalytic upgrading reaction conditions-products yield will be established. The theory of high temperature millisecond pyrolysis of biomass and catalytic upgrading of pyrolysis vapor will be provided. This project will lay the foundation for the in-depth development and applications of the large scale pyrolysis oil vapor of biomass. Furthermore, this project will provide the indication for improving the yield and quality of light oil.

生物质快速裂解油气接力式催化提质充分利用了热解油气的热量，避免了传统方法中生物油二次加热的缩合缩聚和液相进料困难，轻质油收率和品质提高，催化剂回收与再生相对容易，是目前最有可能实现生物质热解油品精制改性技术工业化的途径之一，但相关基础研究极少。本项目拟采用新建的快速热解-催化-气质联用仪和实验方法，探明催化剂组成-制备-结构与热解油气选择性提质的关联耦合机制，优选最佳催化剂制备方法；采用5L/h双反应管高温毫秒热解与油气接力式催化提质耦合热态中试装置，揭示高温催化剂与生物油气接触瞬间对重油大分子裂化形成的“热冲击”作用，阐明快速热解反应条件-催化改质反应条件-目标产物液收率的关联耦合机制，提出生物质高温毫秒热解和热解油气催化改质耦合的调控转化理论。该研究将为大规模生物热解油气下行循环流化床接力式催化提质工艺新技术的深度开发及推广应用奠定基础，也为下一步提高生物轻质油收率和品质指明了方向。

生物质快速裂解油气接力式催化提质能够充分利用了热解油气热量，避免传统方法中生物油二次加热的缩合缩聚，提高轻质油收率和品质，催化剂回收与再生容易，是目前最有可能实现生物质热解油品精制改性工业化的途径之一。.（1）利用快速热解-催化改质-气质联用仪，揭示了生物质快速热解油气碱性催化裂解机理，阐明了铝酸钙催化剂与产物构效关系，筛选出催化剂的最优合成工艺及条件。结果表明选用炭黑作为模板剂、n(CaO)/n(Al2O3)=1.7，煅烧温度1350℃制备的催化剂性能最优。铝酸钙催化剂主要通过CO的路径脱氧并降低反应的活化能，催化裂解活性：半纤维素>淀粉类>油酯类>纤维素类≈蛋白质类>木质素类；木质素以缩合生焦反应为主，纤维素、半纤维素以裂解为主，是液收的主要来源；油脂族的挥发分达100%，热解后固体残留几乎为0，产物富含烯烃。.（2）利用下行床-固定床串行中试装置，揭示了快速热解条件-催化条件-目标产物的关联耦合机制，结果表明，松木525℃时热解液收最高达到60%、玉米秸秆425℃时热解液收最高达到45.51%。随着催化温度升高，焦油产率下降，裂解气产率上升，其中H2、CH4以及C2、C3烃含量上升，CO2含量下降；催化热解油的pH有所提高；碱性催化剂能够降低生物油分子量，使生物油向低碳数分布；碱性催化对纤维素和半纤维素在C5-C6上具有较高选择性。木质素热解经催化后，酚类物质变少，醇类和C=O化合物变多，C9-C10含量提高；松木屑热解油气催化后所得焦油主要为醛类、酮类、酚类、烃类、呋喃类以及其它类，随着催化停留时间延长，醛类产物降低，酮类、呋喃类产物先上升后下降，烃类产物上升；催化停留时间越长，铝酸钙裂解活性越强，脱氧效果越强。.（3）发表论文16篇，其中SCI一区论文7篇，二区8篇。授权美国发明专利6项，实审美国发明1项；申请中国发明5项、实用新型2项；获中国石化联合会科技进步一等奖1项、二等奖1项，青岛市技术发明一等奖1项；项目负责人获泰山学者青年专家人才项目，培养研究生8名。其中，校级优秀博士毕业论文和优秀硕士毕业论文各1个，学生获中国“互联网+”大赛全国铜奖、山东省“互联网+”大赛金奖、 “未来杯”青创赛特等奖各1项。圆满完成了项目目标要求。.该研究将为大规模生物热解油气下行床接力式催化提质工艺新技术的深度开发奠定基础，为提高生物轻质油收率和品质指明方向。