Ru修饰负载型Co基费托合成催化剂性能研究

闫敬如; 娄舒洁; 孟闪茹; 肖海成

doi:10.12434/j.issn.2097-2547.20220372

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Ru修饰负载型Co基费托合成催化剂性能研究

碳一分子资源化利用

- Ru修饰负载型Co基费托合成催化剂性能研究
- Study on performance of supported Co-based Fischer Tropsch catalysts modified by Ru
- 低碳化学与化工 2023, 48(5): 46-54.
- 作者机构：
  
  1.中国石油天然气股份有限公司石油化工研究院,北京 102206
  2.中国石油大学(北京) 化学工程与环境学院,北京 102249
- 作者简介：
  
  闫敬如（1996—），硕士研究生，研究方向为碳一化工，E-mail：2982464162@qq.com。
  娄舒洁（1989—），博士，高级工程师，硕士生导师，研究方向为碳一化工与精细化学品合成，E-mail：loushujie@petrochina.com.cn。
- 基金信息：
  
  国家自然科学基金(2017YFA0700100);中国石油科学研究与金属开发项目(2019A-2409-02;2019E-25;2020-CB-02-15-02)
- DOI：10.12434/j.issn.2097-2547.20220372
  中图分类号：
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闫敬如, 娄舒洁, 孟闪茹, 等. Ru修饰负载型Co基费托合成催化剂性能研究[J]. 低碳化学与化工, 2023,48(5):46-54.

YAN Jingru, LOU Shujie, MENG Shanru, et al. Study on performance of supported Co-based Fischer Tropsch catalysts modified by Ru[J]. Low-carbon Chemistry and Chemical Engineering, 2023,48(5):46-54.
闫敬如, 娄舒洁, 孟闪茹, 等. Ru修饰负载型Co基费托合成催化剂性能研究[J]. 低碳化学与化工, 2023,48(5):46-54. DOI： 10.12434/j.issn.2097-2547.20220372.

YAN Jingru, LOU Shujie, MENG Shanru, et al. Study on performance of supported Co-based Fischer Tropsch catalysts modified by Ru[J]. Low-carbon Chemistry and Chemical Engineering, 2023,48(5):46-54. DOI： 10.12434/j.issn.2097-2547.20220372.

摘要

Ru助剂可以提高Co物种的分散度和还原度，抑制烧结和积炭，进而起到改善Co基催化剂的结构和费托反应催化性能的作用。采用共沉淀法分别制备了不同载体负载的Co基催化剂（Co/MgO、Co/MnO,2,、Co/NaY、Co/SiO,2,和Co/ZnO，Co负载量（质量分数，下同）均为30%）；再以RuCl,3,•,x,H,2,O为Ru助剂修饰以上Co基催化剂，采用等体积浸渍法分别制得了Ru负载量为0.5%和1.0%的Ru修饰负载型Co基费托合成催化剂。采用N,2,吸附、XRD和H,2,-TPR等对催化剂的结构进行了表征，采用固定床反应器评价了催化剂的费托合成催化性能。结果表明，不同负载量的Ru助剂对不同载体负载的Co基催化剂的影响不同。浸渍Ru助剂后，所有催化剂的比表面积和孔容均下降；H,2,-TPR表征表明Ru助剂能够促进Co物种的还原、降低还原温度，并抑制Co与载体之间难还原物种的生成。Co/MnO,2,系列催化剂在270 ℃下才能体现出活性，其中0.5%Ru-Co/MnO,2,具有最低甲烷选择性（5.45%）和最高C,5+,选择性（72.83%）。

Abstract

Ru promoter can improve the dispersion and reduction of Co species, inhibit sintering and carbon deposition, thus improve the structure of Co-based catalyst and its catalytic performance in Fischer Tropsch reaction. Co-based catalysts (Co/MgO, Co/MnO,2, Co/NaY, Co/SiO,2, and Co/ZnO, the loading amount (mass fraction, the same below) of Co is 30%) supported on different supports were prepared by coprecipitation method. Then RuCl,3,•,x,H,2,O was used as Ru promoter to modify the above Co-based catalysts and supported Co-based Fischer Tropsch catalysts modified by Ru were obtained by equal volume impregnation method with the loading amount of Ru is 0.5% and 1.0%, respctively. The structure of the catalysts were characterized by N,2, adsorption, XRD and H,2,-TPR, and the catalytic performance of the catalyst in Fischer Tropsch synthesis were evaluated in a fixed bed reactor. The results show that different loading amounts of Ru promoter have different effects on Co-based catalysts on various supports. For all the catalysts, the specific surface area and pore volume decrease after impregnation with Ru promoter. H,2,-TPR characterization shows that Ru promoter can promote the reduction of Co species, lower the reduction temperature and inhibit the formation of refractory species between Co and the support. Co/MnO,2, series catalysts show their activities at the temperature as high as 270 ℃, and 0.5%Ru-Co/MnO,2, has the lowest methane selectivity (5.45%) and the highest C,5+, selectivity (72.83%).

关键词

费托合成Co基催化剂氧化物载体Ru助剂

Keywords

Fischer Tropsch synthesisCo based catalystoxide supportRu promoter

references

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