Effects of promoter Na and Zn on catalytic performances of Fe based catalysts for CO<sub>2</sub> hydrogenation to light olefins

LIU Wei; ZU Haonan; WU Huashuai; WANG Mingyi; DING Chuanmin; WANG Junwen

doi:10.12434/j.issn.2097-2547.20240019

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Effects of promoter Na and Zn on catalytic performances of Fe based catalysts for CO₂ hydrogenation to light olefins

- Effects of promoter Na and Zn on catalytic performances of Fe based catalysts for CO₂ hydrogenation to light olefins
- Vol. 49, Issue 8, Pages: 107-114(2024)
- 作者机构：
  
  太原理工大学化学工程与技术学院，山西太原 030024
- 作者简介：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20240019
  CLC： TQ426;TK91
- Published：25 August 2024，
  
  Received：15 January 2024，
  
  Revised：21 February 2024，
- 稿件说明：
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刘伟,俎浩楠,吴华帅等.助剂Na和Zn对Fe基催化剂催化CO₂加氢制低碳烯烃反应性能的影响[J].低碳化学与化工,2024,49(08):107-114.

LIU Wei,ZU Haonan,WU Huashuai,et al.Effects of promoter Na and Zn on catalytic performances of Fe based catalysts for CO₂ hydrogenation to light olefins[J].Low-carbon Chemistry and Chemical Engineering,2024,49(08):107-114.
刘伟,俎浩楠,吴华帅等.助剂Na和Zn对Fe基催化剂催化CO₂加氢制低碳烯烃反应性能的影响[J].低碳化学与化工,2024,49(08):107-114. DOI： 10.12434/j.issn.2097-2547.20240019.

LIU Wei,ZU Haonan,WU Huashuai,et al.Effects of promoter Na and Zn on catalytic performances of Fe based catalysts for CO₂ hydrogenation to light olefins[J].Low-carbon Chemistry and Chemical Engineering,2024,49(08):107-114. DOI： 10.12434/j.issn.2097-2547.20240019.

摘要

通过Fe基催化剂催化CO

加氢直接合成低碳烯烃是实现CO

资源化利用的重要途径之一。目前Fe基催化剂的CO

加氢反应催化活性和低碳烯烃选择性仍然较低。通过模板剂-等体积浸渍两步法制备了一系列Fe基催化剂，研究了碱金属助剂Na和过渡金属助剂Zn对Fe基催化剂催化CO

加氢制低碳烯烃反应性能的影响及其作用机制。结果表明，在CO

加氢反应中（反应条件：

= 320 ℃，

= 2.0 MPa，

(CO

) = 3:1，空速为8000 mL/(g·h)），经助剂Zn和Na改性的Fe2Zn1-Na催化剂（

(Fe):

(Zn) = 2:1，Na的负载量（质量分数）为2%）显示出最优的催化性能（CO

转化率为36.5%，CO选择性为13.6%，C

烯烷比为6.5）。并且在线反应80 h后，

该催化剂的催化活性和产物选择性仍保持相对稳定。采用N

吸/脱附、XRD、H

-TPR、CO-TPR、CO

-TPD和XPS等对反应前后的催化剂进行了表征。表征结果显示，助剂Na可以促进Fe基催化剂在反应过程中Fe

相的形成和稳定存在；助剂Zn的引入使Fe基催化剂上形成了ZnFe

物相，同时在Na的作用下，大大提高了Fe2Zn1-Na催化剂的稳定性。与Fe-Na催化剂相比，Fe2Zn1-Na催化剂中Fe物种周围的电子云密度更强，低碳烯烃选择性更高，但诱导期略微变长。Na和Zn的添加不仅能够促进Fe基催化剂的碳化过程，还能增强催化剂的表面碱性，促进CO

在其表面的吸附，从而提高CO

转化率。

Abstract

The direct synthesis of light olefins through CO

hydrogenation catalyzed by Fe based catalysts is one of the important ways to achieve the resource utilization of CO

. At present

the catalytic activity and light olefin selectivity of Fe based catalysts for CO

hydrogenation reaction are still relatively low. A series of Fe based catalysts were prepared by a two-step method of template-equal volume impregnation. The catalytic performance and mechanism of alkali metal promoter Na and transition metal promoter Zn on Fe based catalysts for CO

hydrogenation to light olefins were studied. The results show that in the CO

hydrogenation reaction (reaction conditions:

= 320 ℃

= 2.0 MPa

(CO

) = 3:1

space velocity of

8000 mL/(g·h))

the Fe2Zn1-Na catalyst modified with Zn and Na additives (

(Fe):

(Zn) = 2:1

Na loading (mass fraction) of 2%) shows the optimal catalytic performance (CO

conversion rate of 36.5%

CO selectivity of 13.6% and C

olefin and alkane ratio of 6.5). Moreover

after 80 h of online reaction

the catalytic activity and product selectivity of the catalyst remaineds relatively stable. The catalysts before and after the reaction were characterized by N

adsorption/desorption

XRD

-TPR

CO-TPR

-TPD and XPS. The characterization results show that the additiv

e Na can promote the formation and stable existence of Fe

phase in Fe based catalysts during the reaction process. The introduction of Zn as an auxiliary agent resulteds in the formation of ZnFe

phase on Fe based catalysts

which greatly improveds the stability of Fe2Zn-Na catalyst under the simultaneous action of Na. Compared with Fe-Na catalyst

the electron cloud density around Fe species in Fe2Zn1-Na catalyst is stronger

and the light olefin selectivity is higher

but the induction period is slightly longer. The addition of Na and Zn can not only promote the carbonization process of Fe based catalysts

but also enhance the surface alkalinity of the catalysts and promote the adsorption of CO

on its surface

thereby increasing the conversion rate of CO

关键词

CO2加氢低碳烯烃ZnFe2O4助剂稳定性

Keywords

CO2 hydrogenationlight olefinsZnFe2O4promotersstability

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Effects of promoter Na and Zn on catalytic performances of Fe based catalysts for CO2 hydrogenation to light olefins

DOI：10.12434/j.issn.2097-2547.20240019

摘要

Abstract

关键词

Keywords

references

Effects of promoter Na and Zn on catalytic performances of Fe based catalysts for CO₂ hydrogenation to light olefins