高分散、大孔径硫化铁/SiO<sub>2</sub>催化剂的沉淀沉积法制备及其对减压渣油的高效转化

摘要针对重质油浆态床铁基催化剂活性低,反应压力较高的问题。设计了沉淀沉积的溶胶-凝胶法制备催化剂前驱体,经预硫化处理得到SiO₂担载的高分散硫化铁催化剂。考察了催化剂在较低压力下(5 MPa)对模型化合物萘、Merey减压渣油的催化性能,以氮气吸附-脱附、ICP、XRD、Mössbauer(MES)、SEM-EDS和TEM等手段对催化剂及前驱体进行了表征。在催化剂较低的w(铁) [w(Fe₂O₃)/ w(SiO₂)中Fe₂O₃为20%]下,减压渣油转化反应的轻质油产率可达54.9%,焦炭产率低至1.6%。催化剂的优越性能归因于催化剂前驱体中Fe₂O₃及催化剂中硫化铁的高分散与平均孔径约为20 nm的大孔径。催化剂通过简单易行的方法制备:通过调节溶胶的pH值,使得氢氧化铁胶粒带正电,氧化硅微粒带负电;利用静电吸引实现氢氧化铁的高分散和"限域"(以抑制其团聚),由颗粒堆积获得大孔径。

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	蔺聪福
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	冯富祥
	刘源

关键词：硫化铁催化剂高分散浆态床反应器溶胶-凝胶

Abstract： Aiming at the problem of low activity and high reaction pressure of heavy oil slurry bed iron-based catalysts, the precursor was prepared by the precipitated sol-gel method, and the highly dispersed iron sulfide catalyst supported by SiO₂ was obtained by pre-sulfidation. The catalytic performance of the catalyst at a low pressure (5 MPa) on the model compounds naphthalene and Merey vacuum residue was investigated, and the catalyst and precursor were characterized by nitrogen adsorption-desorption, ICP, XRD, Mössbauer (MES), SEM-EDS, TEM and other methods. At the low iron content of the catalyst (Fe₂O₃ in Fe₂O₃/SiO₂ is 20%), the yield of light oil can reach 54.9%, and the coke yield can be as low as 1.6%. The good performance of the catalyst is attributed to the high dispersion of Fe₂O₃ in the catalyst precursor and iron sulfide in the catalyst and the large pore size with an average pore size of about 20 nm. The catalyst is prepared by a simple and easy method: by adjusting the pH value of the sol, the iron hydroxide colloids are positively charged and the silica particles are negatively charged, and the electrostatic attraction is used to achieve high dispersion and "confinement" of iron hydroxide (to inhibit its agglomeration), and the large pore size is obtained by particle packing.

Keywords： iron sulfide catalyst highly dispersed slurry-bed reactor sol-gel

Received 2022-05-05;

Fund:国家自然科学基金面上项目(22178368)。

Corresponding Authors: 刘源,教授,E-mail:yuanliu@tju.edu.cn。 Email: yuanliu@tju.edu.cn

About author: 蔺聪福(1996-),男,硕士研究生,现从事重质油转化方面的研究。

引用本文:

蔺聪福, 白杨, 田磊, 郭强, 杨勇, 冯富祥, 刘源.高分散、大孔径硫化铁/SiO₂催化剂的沉淀沉积法制备及其对减压渣油的高效转化[J]. 化学工业与工程, 2024,41(4): 65-75

LIN Congfu, BAI Yang, TIAN Lei, GUO Qiang, YANG Yong, FENG Fuxiang, LIU Yuan.Preparation of highly dispersed and large pore size iron sulfide/SiO₂ catalyst by precipitation deposition method and its efficient conversion of vacuum residue[J]. Chemcial Industry and Engineering, 2024,41(4): 65-75

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