水相生物油原位汽化-催化重整制氢工艺优化

Optimization of in-situ gasification&catalytic reforming process for hydrogen production from aqueous bio-oil

为了“碳达峰,碳中和”的目标,开发以可再生能源为主体的绿色制氢技术势在必行。基于原位汽化策略,本文在自主研发的固定床/流化床催化重整一体式反应装置上开展水相生物油催化重整制氢对比实验。结果发现,在经原位汽化改进后的催化重整制氢工艺中,流化床内水相生物油转化效率(95%左右)明显高于固定床(80%左右),两种反应体系中的H_(2)选择性均能100%保持较长时间稳定,但在反应进行到100min左右时,固定床反应体系中出现了明显的催化剂积炭失活现象,而流化床体系中催化剂始终保持较高活性,未发现积炭生成。从反应后液相产物分析可以发现,流化床反应体系中水相生物油各组分接近完全转化,而固定床反应体系中除有少量乙酸和苯酚残留外,还有少量酮类物质产生(丙酮等)。因此,原位汽化策略可以有效促进水相生物油催化重整制氢过程,结合流化床中催化剂的流化效果,将极大促进生物质-生物油-氢气的产业链推广进程。

Due to the component diversity of aqueous bio-oil,it faces the problems of uneven component gasification and low conversion efficiency of raw materials in the process of catalytic reforming for hydrogen production.In this study,the feeding system was optimized to make the aqueous bio-oil instantaneously vaporized in the reaction tube.On this basis,a set of catalytic reforming hydrogen production device integrating fixed bed and fluidized bed was designed and processed.A series of experiments were carried out to explore the conversion efficiency and hydrogen production effect of aqueous bio-oil in two reactors by in-situ gasification strategy.The results showed that the conversion efficiency of aqueous bio-oil in fluidized bed(about 95%)was significantly higher than that in fixed bed(about 80%),and the H_(2) selectivity in both reaction systems could remain stable at 100%for a long time The obvious deactivation of catalyst by carbon deposition occurred in the later stage(about 100min)of the fixed bed reaction system,while in the fluidized bed,the catalysts always maintained high activity without carbon deposition.Their liquid products were analyzed,and all the components of aqueous bio-oil were nearly completely transformed in fluidized bed,while a small amount of acetic acid and phenol remained for fixed bed and some ketones(acetone,etc.)were generated at the same time.These results prove that the in-situ gasification strategy greatly promotes the total component transformation of aqueous bio-oil.Combined with the fluidization effect of catalyst in fluidized bed,which can greatly enhance the catalytic conversion efficiency and stability,it will greatly promote the industrial chain process from biomass to bio-oil to hydrogen.