亲油Meso-MxFe3-ηO4-δ重质油悬浮床加氢裂化催化剂的设计合成

Slurry-phase hydrocracking is an obviously efficient and economical technique for refining heavy oil, in which catalyst is the key. At present, the existing catalysts have such problems as low activity, high coke yield and high cost, which urgently need to be solved. This project intends to develop controllable synthesis method to prepare a new generation iron based catalyst for slurry phase hydrocracking of heavy oil. In essence: the Meso-Fe3O4 pore structure will be designed based on the relationship of heavy oil molecule diffusion-reaction performance with the catalyst pore size, accurate modulation of physicochemical property of Meso-MxFe3-ηO4-δ will be achieved through metal doping, oleophylic Meso-MxFe3-ηO4-δ catalyst will be obtained via organic surface modification, hence oleophylic Meso-MxFe3-ηO4-δ catalyst with high activity, high selectivity and low coking will be developed. The effects of catalyst composition and structure on the heavy oil conversion, liquid selectivity and coking yield will be systematically investigated, therefore the structure-activity relationship of catalyst will be established, as well as the mechanism of slurry-phase hydrocracking of heavy oil and the deactivation mechanism will be clarified, the regeneration method will be designed. The achievement of this project will provide the theoretical basis and technical support for the development of slurry-phase hydrocracking catalyst of heavy oil. It is greatly significant for the efficient conversion of heavy oil.

悬浮床加氢是一种高效、经济的重质油加工技术，催化剂是该技术的关键。目前现有催化剂存在活性低、生焦量高、生产成本高等的问题亟需解决。本项目拟发展可控合成策略创制出新一代重质油悬浮床加氢裂化铁基催化剂，其核心在于：基于重质油分子扩散-反应性能与催化剂孔道大小的关系设计Meso-Fe3O4孔道结构，通过金属原子掺杂实现Meso-MxFe3-ηO4-δ物理化学性质的精准调变，采用有机表面修饰获得亲油Meso-MxFe3-ηO4-δ催化剂，最终创制出活性高、选择性好、生焦量低的亲油Meso-MxFe3-ηO4-δ催化剂。系统考察催化剂组成和结构对重质油转化率、液体选择性、焦炭产率的影响规律，阐明重质油悬浮床加氢反应机制，建立催化剂的构-效关系，明确失活机理，并发展失活催化剂的再生方法。本项目的研究成果将为重质油悬浮床加氢裂化催化剂的开发提供理论基础和技术支撑，对重质油的高效转化具有重大深远的意义。

随着原油供应重质化、劣质化的趋势不断加剧，而轻质化、清洁化的石油产品需求日益增加，对炼油工业的可持续发展提出了严峻的挑战。悬浮床加氢技术因其原料适应性强、转化率高、工艺过程相对简单，被公认为最有前景的重质油高效转化路线，成本低廉、活性高的催化剂是该技术的核心。首先，本项目采用溶胶-凝胶法和沉淀法制备出不同介孔结构的氧化铁、系统考察不同合成条件对氧化铁晶型结构和孔道结构的影响，揭示重质油分子扩散-反应性能与催化剂孔道大小的关系，表明氧化铁催化剂的介孔孔道有助于提高重油分子扩散与金属活性中心位点接触，增加催化剂的加氢和裂化反应性能。其次，利用金属原子Ti掺杂调控催化剂Fe离子的电子结构，并是催化剂结构中产生大量的缺陷位，从而提高了Fe催化剂的加氢活性，在渣油加氢裂化反应中显著地抑制副产物气体和焦炭的产生。接着，构筑亲油型介孔Fe氧化物催化剂，该催化剂在油品中高度分散，与反应物分子充分接触，提高了催化剂的活性中心的利用率，从而可进一步提高催化剂的加氢裂化反应性能。最后，系统考察催化剂组成和结构对重质油转化率、液体收率、焦炭产率的影响规律，阐明重质油悬浮床加氢反应机制，建立催化剂的构-效关系，基于催化剂失活机理发展催化剂的再生方法。本项目的研究成果将为重质油悬浮床加氢裂化催化剂的开发提供理论基础和技术支撑，对重质油的高效转化具有重大深远的意义。