Al助剂含量对CoMn催化剂结构及其合成气制高碳醇催化性能的影响

葛浩; 孙燕; 孙启文

doi:10.12434/j.issn.2097-2547.20240465

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Al助剂含量对CoMn催化剂结构及其合成气制高碳醇催化性能的影响

C1化学与催化转化 | 更新时间：2025-07-30

- Al助剂含量对CoMn催化剂结构及其合成气制高碳醇催化性能的影响
- Effect of Al additive contents on structure of CoMn catalysts and their catalytic performance in synthesis of higher alcohols from syngas
- 低碳化学与化工 2025, 50(7): 10-19.
- 作者机构：
  
  上海兖矿能源科技研发有限公司煤液化气化及高效低碳利用全国重点实验室，上海 201203
- 作者简介：
  
  葛浩（1991—），博士，工程师，研究方向为C1化学，E-mail：haoge_1122@163.com。
  孙启文（1958—），博士，研究员，研究方向为煤液化及新型煤化工，E-mail：yetech@ye-tech.com。
- 基金信息：
  
  国家重点研发计划(2023YFB4103200)
- DOI：10.12434/j.issn.2097-2547.20240465
  中图分类号： TQ016.1
- 收稿日期：2024-11-22，
  
  修回日期：2025-02-25，
  
  纸质出版日期：2025-07-25
- 稿件说明：
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葛浩,孙燕,孙启文.Al助剂含量对CoMn催化剂结构及其合成气制高碳醇催化性能的影响[J].低碳化学与化工,2025,50(07):10-19.

GE Hao,SUN Yan,SUN Qiwen.Effect of Al additive contents on structure of CoMn catalysts and their catalytic performance in synthesis of higher alcohols from syngas[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(07):10-19.
葛浩,孙燕,孙启文.Al助剂含量对CoMn催化剂结构及其合成气制高碳醇催化性能的影响[J].低碳化学与化工,2025,50(07):10-19. DOI： 10.12434/j.issn.2097-2547.20240465.

GE Hao,SUN Yan,SUN Qiwen.Effect of Al additive contents on structure of CoMn catalysts and their catalytic performance in synthesis of higher alcohols from syngas[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(07):10-19. DOI： 10.12434/j.issn.2097-2547.20240465.

摘要

通过设计高效的无机金属催化剂提升合成气制醇效率及高碳醇（C

醇）选择性对可持续化学和能源开发具有重要意义。为研究Al助剂对CoMn催化剂结构和合成气制高碳醇催化性能的影响，采用共沉淀法制备了不同 Al掺杂量的CoMnAl催化剂，利用XRD、SEM、EDX、N

吸/脱附、ICP、XPS和CO/H

/NH

-TPD等表征技术对比了Al助剂掺杂后对CoMn催化剂的结构、组成、形貌、化合价态以及表面化学性质等的影响，并在260 °C、3.0 MPa、

(CO):

(Ar) = 80:40:30及反应空速3000 h

-1

条件下对CoMnAl催化剂的催化性能进行了测试。结果表明，作为结构助剂时，适量的Al掺杂会与其他金属产生不同程度的金属间相互作用，从而影响催化剂的比表面积和颗粒尺寸；作为电子助剂时，Al与Co发生电子转移并形成Co-Al-O 活性相，进而影响催化剂的还原性能和氧缺陷形成，有效提高了催化剂的催化性能。原位FT-IR表征揭示了Al助剂掺杂后CoMnAl(0.3)催化剂的反应路径为醛基插入过程，有效抑制了反应中甲烷的生成，提高了总醇选择性，其总醇选择性达到42%，高碳醇在总醇中占比（物质的量分数）高达48.8%。通过精确调控Al助剂的掺杂量，可以有效调控催化剂的结构和表面氧缺陷，从而提高合成气制醇过程的高碳醇选择性。

Abstract

Designing effective inorganic metal catalysts to improve the efficiency of syngas-to-alcohol conversion and the selectivity of higher alcohols (C

alcohols) is critical for the development of sustainable chemistry and energy. To investigate the effect of Al additions on the structure and catalytic performance of CoMn catalysts in synthesis of higher alcohols from syngas

CoMnAl catalysts with varying Al addition quantities were produced by co-precipitation. The effects of Al doped on the structure

composition

morphology

valence state and surface chemical properties of CoMn catalysts were compared using characterization techniques such as XRD

SEM

EDX

adsorption/desorption

ICP

XPS and CO/H

/NH

-TPD. The c

atalytic performance of CoMnAl catalysts was tested under conditions of 260 ℃

3.0 MPa

(CO):

(Ar) = 80:40:30 and space velocity of 3000 h

-1

. The results show that when Al is doped in appropriate amounts as a structural promoter

it interacts with other metals to variable degrees

influencing the specific surface area and particle size of catalyst. As an electronic promoter

Al facilitates electron transfer with Co to form a Co-Al-O active phase

which in turn affects the reducibility and formation of oxygen defects of the catalyst

significantly enhancing its catalytic performance. In situ FT-IR characterization reveals that the reaction pathway of the CoMnAl(0.3) catalyst doped with Al additives is an aldehyde insertion process

which effectively inhibits the formation of methane in the reaction and improves the total alcohol selectivity to 42%. The percentage of higher alcohols in the total alcohols reaches 48.8% (mole fraction). By precisely controlling the Al doping amount

it is possible to effectively regulate the structure and surface oxygen defects of the catalyst

thereby enhancing the selectivity for higher alcohols in the syngas-to-alcohol process.

关键词

Keywords

references

LUK H T , MONDELLI C , FERRÉ D C , et al . Status and prospects in higher alcohol synthesis from syngas [J ] . Chemical Society Reviews , 2017 , 46 : 1358 - 1426 .

田园 , 娄舒洁 , 孟闪茹 , 等 . 合成气制高碳醇钴基催化剂研究进展 [J ] . 化工进展 , 2023 , 42 ( 4 ): 1869 - 1876 .

TIAN Y , LOU S J , MENG S R , et al . Recent progress of Co-based catalysts for higher alcohols synthesis form syngas [J ] . Chemical Industry and Engineering Progress , 2023 , 42 ( 4 ): 1869 - 1876 .

ZUO Y Y , LV J F , WEI N , et al . Effect of anions and cations on the self-assembly of ionic liquid surfactants in aqueous solution [J ] . Journal of Molecular Liquids , 2023 , 375 : 121342 .

GAO Z X , ZHAO H , LI Z M , et al . Photosynthetic production of ethanol from carbon dioxide in genetically engineered cyanobacteria [J ] . Energy & Environmental Science , 2012 , 5 ( 12 ): 9857 - 9865 .

WANG L , WANG J G , LITTLEWOOD J , et al . Co-production of biorefinery products from kraft paper sludge and agricultural residues: Opportunities and challenges [J ] . Green Chemistry , 2014 , 16 ( 3 ): 1527 - 1533 .

WANG C Q , LIN T J , QI X Z , et al . Direct conversion of syngas to higher alcohols over multifunctional catalyst: The role of copper-based component and catalytic mechanism [J ] . The Journal of Physical Chemistry C , 2021 , 125 ( 11 ): 6137 - 6146 .

杨展董 , 马恩娟 , 张乾 , 等 . 氮掺杂碳纳米管担载CuCoCe对合成气制低碳醇的催化性能 [J ] . 燃料化学学报 , 2020 , 48 ( 7 ): 804 - 812 .

YANG Z D , MA E J , ZHANG Q , et al . Catalytic performance of CuCoCe supported on nitrogen-doped carbon nanotubes for the synthesis of higher alcohols from syngas [J ] . Journal of Fuel Chemistry and Technology , 2020 , 48 ( 7 ): 804 - 812 .

ZENG F , XI X Y , CAO H T , et al . Synthesis of mixed alcohols with enhanced C 3+ alcohol production by CO hydrogenation over potassium promoted molybdenum sulfide [J ] . Applied Catalysis B: Environmental , 2019 , 246 ( 5 ): 232 - 241 .

徐浩浩 , 穆晓亮 , 房克功 . 氧空穴ZrO 2 复合CuFe催化剂合成气制高级醇反应性能研究 [J ] . 低碳化学与化工 , 2024 , 49 ( 10 ): 11 - 19 .

XU H H , MU X L , FANG K G . Study on reaction performances of oxygen-vacancies ZrO 2 composite CuFe catalysts for syngas to higher alcohols [J ] . Low-Carbon Chemistry and Chemical Engineering , 2024 , 49 ( 10 ): 11 - 19 .

WU D F , LIU S X , ZHONG M Q , et al . Nature and dynamic evolution of Rh single atoms trapped by CeO 2 in CO hydrogenation [J ] . ACS Catalysis , 2022 , 12 ( 19 ): 12253 - 12267 .

LI Y H , ZHAO Z , LU W , et al . Highly selective conversion of syngas to higher oxygenates over tandem catalysts [J ] . ACS Catalysis , 2021 , 11 ( 24 ): 14791 - 14802 .

NATHAN S S , ASUNDI A S , HOFFMAN A S , et al . Surface Fe clusters promote syngas reaction to oxygenates on Rh catalysts modified by atomic layer deposition [J ] . Journal of Catalysis , 2022 , 414 : 125 - 136 .

SUBRAMANIAN N D , GAO J , MO X H , et al . La and/or V oxide promoted Rh/SiO 2 catalysts: Effect of temperature, H 2 /CO ratio, space velocity, and pressure on ethanol selectivity from syngas [J ] . Journal of Catalysis , 2010 , 272 ( 2 ): 204 - 209 .

WON B D , JEONG M H , KIM M H , et al . Rh-Mn/Tungsten carbides for direct synthesis of mixed alcohols from syngas: Effects of tungsten carbide phases [J ] . Microporous and Mesoporous Materials , 2018 , 225 : 44 - 52 .

QI X Z , LIN T J , GONG K , et al . Direct synthesis of higher oxygenates via syngas over zinc oxide modified CoMn-based catalysts [J ] . Applied Catalysis A: General , 2022 , 648 : 118925 .

GUO S X , LI Z S , YIN R , et al . Oxygen vacancy over CoMnO x catalysts boosts selective ethanol production in the higher alcohol synthesis from syngas [J ] . ACS Catalysis , 2023 , 13 ( 21 ): 14404 - 14414 .

SUN K , TAN M H , BAI Y X , et al . Design and synthesis of spherical-platelike ternary copper-cobalt-manganese catalysts for direct conversion of syngas to ethanol and higher alcohols [J ] . Journal of Catalysis , 2019 , 378 : 1 - 16 .

YANG R O , XIA Z M , ZHAO Z , et al . Characterization of CoMn catalyst by in situ X-ray absorption spectroscopy and wavelet analysis for Fischer-Tropsch to olefins reaction [J ] . Journal of Energy Chemistry , 2019 , 32 : 118 - 123 .

DELARIVA A T A , HANSEN T W , CHALLA S R , et al . In situ transmission electron microscopy of catalyst sintering [J ] . Journal of Catalysis , 2013 , 308 : 291 - 305 .

XU J , WEI J , ZHANG J X , et al . Precisely synergistic synthesis of higher alcohols from syngas over iron carbides [J ] . Chemical Catalysis , 2023 , 3 ( 4 ): 100584 .

DU X , ZHANG M W , FANG K G . Preparation of silicon foam supported CoMn catalysts and their catalytic performances in higher alcohol synthesis via syngas [J ] . Journal of Fuel Chemistry and Technology , 2024 , 52 ( 9 ): 1224 - 1234 .

YIN P , HU S L , QIAN K , et al . Quantification of critical particle distance for mitigating catalyst sintering [J ] . Nature Communications , 2021 , 12 : 4865 .

YANG Y Z , LIN T J , QI X Z , et al . Direct synthesis of long-chain alcohols from syngas over CoMn catalysts [J ] . Applied Catalysis A: General , 2018 , 549 : 179 - 187 .

LIN T J , QI X Z , WANG X X , et al . Direct production of higher oxygenates by syngas conversion over a multifunctional catalyst [J ] . Angewandte Chemie International Edition , 2019 , 58 ( 14 ): 4627 - 4631 .

DAMMA D , SMIRNIOTIS P G . Recent advances in the direct conversion of syngas to oxygenates [J ] . Catalysis Science & Technology , 2021 , 11 : 5412 - 5431 .

LI Z J , YAO N , CEN J , et al . Effects of alkali metal promoters on the structure-performance relationship of CoMn catalysts for Fischer-Tropsch synthesis [J ] . Catalysis Science & Technology , 2020 , 10 : 1816 - 1826 .

REN Y W , LEI X , WANG H , et al . Enhanced catalytic performance of La-doped CoMn 2 O 4 catalysts by regulating oxygen species activity for VOCs oxidation [J ] . ACS Catalysis , 2023 , 13 ( 12 ): 8293 - 8306 .

SHI Z S , TAN Q Q , TIAN C , et al . CO 2 hydrogenation to methanol over Cu-In intermetallic catalysts: Effect of reduction temperature [J ] . Journal of Catalysis , 2017 , 379 : 78 - 89 .

ZHAO N , CHEN Y , LI X , et al . Preparation of high performance Co 3 O 4 /Al 2 O 3 catalysts by doping Al into ZIF-67: Effect of Al sources on Fischer-Tropsch synthesis [J ] . Applied Surface Science , 2021 , 570 : 151127 .

HU J T , WEI Z Y , ZHANG Y L , et al . Edge-rich molybdenum disulfide tailors carbon-chain growth for selective hydrogenation of carbon monoxide to higher alcohols [J ] . Nature Communications , 2023 , 14 : 6808 .

LOCUS R , VERBOEKEND D , ZHONG R Y , et al . Enhanced acidity and accessibility in Al-MCM-41 through aluminum activation [J ] . Chemical Material , 2016 , 28 ( 21 ): 7731 - 7743 .

TONG Y , ZHANG L , MA H , et al . Understanding the structural and catalytic properties of Al(IV)-2 acidic sites of ZSM-5 [J ] . Materials , 2024 , 17 : 2824 .

GONG K , WEI Y , LIN T J , et al . Maximizing the interface of dual active sites to enhance higher oxygenate synthesis from syngas with high activity [J ] . ACS Catalysis , 2023 , 13 ( 7 ): 4533 - 4543 .

QI X Z , LIN T J , AN Y L , et al . Regulating oxygen vacancies for enhanced higher oxygenate synthesis via syngas [J ] . ACS Catalysis , 2023 , 13 ( 17 ): 11566 - 11579 .

DAI X X , JIANG W Y , WANG W L , et al . Supercritical water syntheses of transition metal-doped CeO 2 nano-catalysts for selective catalytic reduction of NO by CO: An in situ diffuse reflectance Fourier transform infrared spectroscopy study [J ] . Chinese Journal of Catalysis , 2018 , 39 ( 4 ): 728 - 735 .

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