Study on catalytic performances of activated carbon loaded bimetallic catalysts for ethanol gas phase carbonylation reaction

LIU Peng; WANG Xiaobin; DING Chuanmin; MENG Yuanyuan; WANG Mingyi; WU Huashuai; WU Ailian; WANG Junwen

doi:10.12434/j.issn.2097-2547.20240161

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Study on catalytic performances of activated carbon loaded bimetallic catalysts for ethanol gas phase carbonylation reaction

- Study on catalytic performances of activated carbon loaded bimetallic catalysts for ethanol gas phase carbonylation reaction
- Vol. 50, Issue 1, Pages: 47-53(2025)
- 作者机构：
  
  1.太原理工大学化学与化工学院，山西太原 030024
  2.上海电气集团国控环球工程有限公司，山西太原 030000
- 作者简介：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20240161
  CLC： TQ523
- Published：25 January 2025，
  
  Received：16 April 2024，
  
  Revised：14 May 2024，
- 稿件说明：
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LIU PENG, WANG XIAOBIN, DING CHUANMIN, et al. Study on catalytic performances of activated carbon loaded bimetallic catalysts for ethanol gas phase carbonylation reaction. [J]. Low-carbon chemistry and chemical engineering, 2025, 50(1): 47-53.
DOI：

LIU PENG, WANG XIAOBIN, DING CHUANMIN, et al. Study on catalytic performances of activated carbon loaded bimetallic catalysts for ethanol gas phase carbonylation reaction. [J]. Low-carbon chemistry and chemical engineering, 2025, 50(1): 47-53. DOI： 10.12434/j.issn.2097-2547.20240161.

摘要

乙醇气相羰基化法是一种非石油途径生产丙酸的方法，以活性炭为载体的Ni基催化剂广泛应用于该反应。为了提高该催化剂催化活性，在Ni基催化剂的基础上进一步分别掺杂铁、铜和铈元素，制备了一系列Ni-X（X = Fe、Cu或Ce）双金属催化剂，通过N

物理吸/脱附、XRD和XPS等探究了金属分散性与Ni

相对含量（

(Ni

+ Ni

)）对反应性能的影响。在250 ℃、0.1 MPa和原料（

(CO):

OH):

I) = 40:20:1）体积空速为1.2 h

-1

条件下，对Ni-X双金属催化剂进行了乙醇气相羰基化反应催化性能评价。结果表明，在Ni-Ce双金属催化剂表面存在Ni物种与CeO

之间的协同作用，该协同作用促进Ni

还原为Ni

，使催化剂表面出现更多活性位点，同时抑制了Ni金属表面堆积，促进了Ni金属分散。相比于Ni-Fe和Ni-Cu双金属催化剂，Ni-Ce双金属催化剂具有最高催化活性，反应6 h时该催化剂的乙醇转化率、丙酸与丙酸乙酯联合选择性以及丙酸与丙酸乙酯联合时空收率分别为70.9%、28.0%以及220.4 mg/(g·h)。

Abstract

Ethanol gas phase carbonylation is a non-petroleum route for the production of propionic acid

and Ni-based catalysts supported on activated carbon are widely used in this reaction. In order to enhance the catalytic activity

a series of Ni-X (X = Fe

Cu or Ce) bimetallic catalysts were prepared by further doping Fe

Cu or Ce on the basis of Ni-based catalysts. The effects of metal dispersion and Ni

relative content

(Ni

+ Ni

) on the reaction performances were investigated by N

physical adsorption/desorption

XRD

XPS

etc. The activity of Ni-X bimetallic catalysts for ethanol gas phase carbonylation was evaluated under the conditions of 250 ℃

0.1 MPa and the feedstock (

(CO):

OH):

I) = 40:20:1) space velocity of 1.2 h

-1

. The results show that there exists a synergistic interaction between Ni species and CeO

on the surface of the Ni-Ce bimetallic catalyst

which promotes the reduction of Ni

to Ni

and the appearance of more active sites on the catalyst surface

as well as inhibits the surface accumulation of Ni metal and promotes the dispersion of Ni metal. Compared with Ni-Fe and Ni-Cu bimetallic catalysts

the Ni-Ce bimetallic catalysts have the highest catalytic activity

and the ethanol conversion rate

combined selectivity of propionic acid and ethyl propionate and combined space-time yield of the catalyst at 6 h are 70.9%

28.0% and 220.4 mg/(g·h)

respectively.

关键词

双金属催化剂乙醇气相羰基化分散性活性位点活性炭

Keywords

bimetallic catalystsethanolgas-phase carbonylationdispersibilityactive siteactivated carbon

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