助剂对球形Cu/SiO<sub>2</sub>催化剂甲醇脱氢制甲酸甲酯反应性能的影响

靳钰婷; 郭宇伟; 权燕红; 赵金仙; 任军

doi:10.12434/j.issn.2097-2547.20230188

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助剂对球形Cu/SiO₂催化剂甲醇脱氢制甲酸甲酯反应性能的影响

C1化学与催化转化

- 助剂对球形Cu/SiO₂催化剂甲醇脱氢制甲酸甲酯反应性能的影响
- Influence of additives on catalytic performance of spherical Cu/SiO₂ catalyst for dehydrogenation of methanol to methyl formate
- 低碳化学与化工 2024, 49(2): 17-25.
- 作者机构：
  
  1.太原理工大学省部共建煤基能源清洁高效利用国家重点实验室，山西太原 030024
  2.太原理工大学化学工程与技术学院，山西太原 030024
  3.山西潞安碳一化工有限公司，山西长治 046100
- 作者简介：
  
  靳钰婷（1995—），硕士研究生，研究方向为碳一化学与化工，E-mail：1948616770@qq.com。
  权燕红（1981—），博士，副教授，研究方向为碳一化学与化工，E-mail：quanyanhong@tyut.edu.cn；
  任　军（1974—），博士，教授，研究方向为碳一化学与化工，E-mail：renjun@tyut.edu.cn。
- 基金信息：
  
  国家自然科学基金(22108191;22179091);中国博士后科学基金(2022M712335)
- DOI：10.12434/j.issn.2097-2547.20230188
  中图分类号： TQ426.98
- 纸质出版日期：2024-02-25，
  
  收稿日期：2023-05-20，
  
  修回日期：2023-06-01，
- 稿件说明：
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靳钰婷,郭宇伟,权燕红等.助剂对球形Cu/SiO₂催化剂甲醇脱氢制甲酸甲酯反应性能的影响[J].低碳化学与化工,2024,49(02):17-25.

JIN Yuting,GUO Yuwei,QUAN Yanhong,et al.Influence of additives on catalytic performance of spherical Cu/SiO₂ catalyst for dehydrogenation of methanol to methyl formate[J].Low-carbon Chemistry and Chemical Engineering,2024,49(02):17-25.
靳钰婷,郭宇伟,权燕红等.助剂对球形Cu/SiO₂催化剂甲醇脱氢制甲酸甲酯反应性能的影响[J].低碳化学与化工,2024,49(02):17-25. DOI： 10.12434/j.issn.2097-2547.20230188.

JIN Yuting,GUO Yuwei,QUAN Yanhong,et al.Influence of additives on catalytic performance of spherical Cu/SiO₂ catalyst for dehydrogenation of methanol to methyl formate[J].Low-carbon Chemistry and Chemical Engineering,2024,49(02):17-25. DOI： 10.12434/j.issn.2097-2547.20230188.

摘要

甲醇脱氢制甲酸甲酯是实现甲醇下游产品多元化利用的绿色高效途径，使用助剂对SiO

催化剂进行改性已成为提高目标产物甲酸甲酯收率的有效策略。首先通过溶胶-凝胶法制备了球形SiO

负载Cu催化剂（Cu/SiO

），然后采用旋蒸法引入助剂制得CuM/SiO

（M = Ce或Al）催化剂，借助N

吸/脱附、扫描电子显微镜（SEM）、H

-N

O滴定和X射线衍射（XRD）等手段对催化剂进行了表征，并将催化剂用于甲醇脱氢制甲酸甲酯反应评价了其催化性能。结果表明，助剂可改变催化剂中活性Cu

物种的含量和表面酸碱性。与Cu/SiO

催化剂相比，CuCe/SiO

催化剂表面Cu颗粒的分散度提高，这促进了活性物种Cu

的形成，同时表面碱性位点减少，抑制了副反应发生，因而CuCe/SiO

催化剂表现出最高的活性。在300 ℃、0.2 MPa的反应条件下，CuCe/SiO

催化剂的甲醇转化率、甲酸甲酯选择性分别为29.2%、86.3%，甲酸甲酯收率为25.2%，均明显优于文献报道的Cu基催化剂。

Abstract

Methanol dehydrogenation to methyl formate is a green and efficient way to diversify methanol downstream products. The modification of Cu/SiO

catalyst with additive has become an effective strategy to increase the yield of the target product methyl formate. Firstly

spherical SiO

supported Cu catalyst (Cu/SiO

) was prepared by the sol-gel method

and then a series of CuM/SiO

(M = Ce or Al) catalysts were obtained through the introduction of additive to Cu/SiO

via the rotary evaporation method. The catalysts were characterized by N

absorption/desorption

scanning electron microscopy (SEM)

-N

O titration

X-ray diffraction (XRD) and so on

and their catalytic performances were evaluated for the reaction of methanol dehydrogenation to methyl formate. The results show that the additive can change the content of active Cu

species and the surface acidity of the catalysts. Compared with the Cu/SiO

catalyst

the

dispersion of Cu particles on the surface of CuCe/SiO

catalyst is increased

which promotes the formation of the active species Cu

while the surface alkaline site is reduced

which inhibits the occurrence of side reactions

and thus exhibits the highest activity. Under the reaction conditions of 300 °C and 0.2 MPa

the methanol conversion rate and the selectivity of methyl formate of CuCe/SiO

catalyst are 29.2% and 86.3%

respectively

and the yield of methyl formate is 25.2%

which are obviously better than that of Cu-based catalysts reported in the literature.

关键词

甲醇脱氢Cu基催化剂球形SiO2甲酸甲酯助剂

Keywords

methanol dehydrogenationcopper-based catalystspherical SiO2methyl formateadditive

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助剂对球形Cu/SiO2催化剂甲醇脱氢制甲酸甲酯反应性能的影响

Influence of additives on catalytic performance of spherical Cu/SiO2 catalyst for dehydrogenation of methanol to methyl formate

DOI：10.12434/j.issn.2097-2547.20230188

摘要

Abstract

关键词

Keywords

references

助剂对球形Cu/SiO₂催化剂甲醇脱氢制甲酸甲酯反应性能的影响

Influence of additives on catalytic performance of spherical Cu/SiO₂ catalyst for dehydrogenation of methanol to methyl formate