焙烧温度对Pd/LDH催化剂上CH<sub>4</sub>-CO<sub>2</sub>两步梯阶转化合成乙酸的影响

王小双; 吴怡枭; 王菲; 张凯玮; 刘勇军; 黄伟

doi:10.12434/j.issn.2097-2547.20250140

您当前的位置：

首页 >

文章列表页 >

焙烧温度对Pd/LDH催化剂上CH₄-CO₂两步梯阶转化合成乙酸的影响

碳基资源催化转化 | 更新时间：2025-08-25

- 焙烧温度对Pd/LDH催化剂上CH₄-CO₂两步梯阶转化合成乙酸的影响
- Effects of calcination temperatures on CH₄-CO₂ two stepwise conversion to acetic acid over Pd/LDH catalysts
- 低碳化学与化工 2025, 50(8): 123-132.
- 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.太原理工大学化学与化工学院，山西太原 030024
  3.新疆智能装备研究院，新疆阿克苏 831399
- 作者简介：
  
  王小双（1999—），硕士研究生，研究方向为C1化工与多相催化，E-mail：1418662780@qq.com。
  刘勇军（1987—），博士，副教授，研究方向为C1化工与多相催化，E-mail：liuyongjun@tyut.edu.cn。
- 基金信息：
  
  国家自然科学基金(22479105;21908157);新疆维吾尔自治区自然科学基金(2024D01A130);山西省基础研究计划(202403021221040);榆林学院-中国科学院洁净能源创新研究院联合基金(YLU-DNL 2023002)
- DOI：10.12434/j.issn.2097-2547.20250140
  中图分类号： TQ426;O643.36
- 收稿日期：2025-03-27，
  
  修回日期：2025-04-16，
  
  纸质出版日期：2025-08-25
- 稿件说明：
移动端阅览
王小双,吴怡枭,王菲等.焙烧温度对Pd/LDH催化剂上CH₄-CO₂两步梯阶转化合成乙酸的影响[J].低碳化学与化工,2025,50(8):123-132.

WANG Xiaoshuang,WU Yixiao,WANG Fei,et al.Effects of calcination temperatures on CH₄-CO₂ two stepwise conversion to acetic acid over Pd/LDH catalysts[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(8):123-132.
王小双,吴怡枭,王菲等.焙烧温度对Pd/LDH催化剂上CH₄-CO₂两步梯阶转化合成乙酸的影响[J].低碳化学与化工,2025,50(8):123-132. DOI： 10.12434/j.issn.2097-2547.20250140.

WANG Xiaoshuang,WU Yixiao,WANG Fei,et al.Effects of calcination temperatures on CH₄-CO₂ two stepwise conversion to acetic acid over Pd/LDH catalysts[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(8):123-132. DOI： 10.12434/j.issn.2097-2547.20250140.

摘要

和CO

直接转化为乙酸是一种100%原子经济性的反应，但其反应条件较苛刻。水滑石（LDH）因具有比表面积大、活性组分分散性好和酸碱性可调等优点，在CH

-CO

催化转化领域具有良好的应用前景。以

(Mg)/

(Al)为5的MgAl-LDH为载体，采用离子交换法负载质量分数为5%的钯（Pd）作为活性组分，将所得前驱体在不同温度下进行焙烧制得了一系列Pd/LDH-X催化剂（X代表焙烧温度）。采用XRD、FT-IR和SEM等对催化剂的结构进行了表征，并研究了催化剂在CH

-CO

两步梯阶转化合成乙酸过程中的催化性能。结果表明，在本研究设定的CH

-CO

两步梯阶转化反应条件下反应30 min，150 ℃下焙烧所得Pd/LDH-150的催化性能最优，其乙酸时空收率为61.8 μmol/(g·h)，明显优于CH

-CO

共进料条件下的乙酸时空收率（2.4 μmol/(g·h)），且乙酸是唯一的液体产物。LDH的结构完整性是影响催化剂催化性能的关键因素，催化剂表面存在较多的中强酸性位点和中强碱性位点有利于乙酸的合成。焙烧温度过高会导致LDH的层状结构坍塌，造成表面中强酸性位点和中强碱性位点数量减少，从而对催化剂的催化性能产生不利影响。

Abstract

The direct conversion of CH

and CO

to acetic acid is a 100% atom-economical reaction

but its reaction conditions are harsh. The hydrotalcite (LDH) has good application prospects in the field of CH

-CO

catalytic conversion due to its advantages of large specific surface area

good dispersion for active components and adjustable acid-base properties. MgAl-LDH with

(Mg)/

(Al) of 5 was used as the support

and palladium (Pd) with mass fraction of 5% was loaded as the active component by ion-exchange method

and a series of Pd/LDH-X catalysts (X represents the calcinatio

n temperature) were prepared by calcinating the resultant precursors at different temperatures. The structures of catalysts were characterized by XRD

FT-IR

SEM

etc.

and the catalytic performances of the catalysts were investigated in two-step stepwise conversion of CH

-CO

to acetic acid. The results show that the catalytic performance of Pd/LDH-150 obtained under calcination temperature of 150 ℃ is the best under the CH

-CO

two-step stepwise conversion reaction conditions set in this study for 30 min

with acetic acid spatiotemporal yield of 61.8 μmol/(g·h)

which is significantly greater than acetic acid spatiotemporal yield (2.4 μmol/(g·h)) under the CH

-CO

cofeeding conditions

and acetic acid is the only liquid product. The structural integrity of LDH is a key factor affecting the catalytic performance of the catalyst

and the presence of more medium-strong acidic sites and medium-strong basic sites on the surface of catalyst is favorable for the synthesis of acetic acid. Excessively high calcination temperature can lead to the collapse of the layered structure of LDH

resulting in the decrease of the number of medium-strong acidic sites and medium-strong basic sites on the surface

which can adversely affect the catalytic performance of the catalyst.

关键词

Keywords

references

YULIATI L , YOSHIDA H . Photocatalytic conversion of methane [J ] . Chemical Society Reviews , 2008 , 37 : 1592 - 1602 .

DONG Y S , WANG J , BAI Y , et al . Carbon-confined Ni based catalyst by auto-reduction for low-temperature dry reforming of methane [J ] . Fuel , 2023 , 339 : 127409 .

MU B S , ZHANG Y G , PENG M , et al . Radiocatalytic synthesis of acetic acid from CH 4 and CO 2 [J ] . Angewandte Chemie-International Edition , 2024 , 63 : e202407443 .

KURIOKA M , NAKATA K , JINTOKU T , et al . Palladium-catalyzed acetic acid synthesis from methane and carbon monoxide or dioxide [J ] . Chemical Letters , 1995 , 24 : 244 .

SHAVI R , KO J , CHO A , et al . Mechanistic insight into the quantitative synthesis of acetic acid by direct conversion of CH 4 and CO 2 : An experimental and theoretical approach [J ] . Applied Catalysis B: Environmental , 2018 , 229 : 237 - 248 .

ZHAO Y T , CUI C N , HAN J Y , et al . Direct C—C coupling of CO 2 and the methyl group from CH 4 activation through facile insertion of CO 2 into Zn-CH 3 σ-bond [J ] . Journal of the American Chemical Society , 2016 , 138 : 10191 - 10198 .

ZHAO Y T , FONTILLAS N , WANG H , et al . Single Pd atom-In 2 O 3 catalyzes production of CH 3 CH 2 OH from atom-economic C—C coupling of HCHO and CH 4 [J ] . ACS Catalysis , 2024 , 14 : 1714 - 1724 .

NIE X W , REN X X , TU C Y , et al . Computational and experimental identification of strong synergy of the Fe/ZnO catalyst in promoting acetic acid synthesis from CH 4 and CO 2 [J ] . Chemical Communications , 2020 , 56 : 3983 - 3986 .

DING Y H , HUANG W , WANG Y G , et al . Direct synthesis of acetic acid from CH 4 and CO 2 by a step-wise route over Pd/SiO 2 and Rh/SiO 2 catalysts [J ] . Fuel Processing Technology , 2007 , 88 : 319 - 324 .

ZHANG X Y , BIAN S , TIAN H F , et al . Thermodynamic possibility analysis of CH 3 COOH synthesis from CH 4 and CO 2 [J ] . Molecular Catalysis , 2024 , 559 : 114090 .

LIU Y J , ZHANG C Y , WANG R J , et al . Low-temperature thermocatalytic coupling of CH 4 and CO 2 to ethanol over Zn-Ce/ZSM-5 by a stepwise technique [J ] . ACS Catalysis , 2024 , 14 : 8823 - 8835 .

张倩 , 温月丽 , 王斌 , 等 . 层状金属氧化物用于二氧化碳吸附及其催化加氢转化的研究进展 [J ] . 天然气化工—C1化学与化工 , 2021 , 46 ( 3 ): 7 - 14 .

ZHANG Q , WEN Y L , WANG B , et al . Research progress of layered metal oxide in adsorption and catalytic hydrogenation of carbon dioxide [J ] . Natural Gas Chemical Industry , 2021 , 46 ( 3 ): 7 - 14 .

MA J Y , ZHANG Q Q , CHEN Z Y , et al . Design of frustrated Lewis pair in defective TiO 2 for photocatalytic non-oxidative methane coupling [J ] . Chem Catalysis , 2022 , 2 : 1775 - 1792 .

DOU L G , LIU Y D , SHAO T , et al . Disentangling metallic cobalt sites and oxygen vacancy effects in synergistic plasma-catalytic CO 2 /CH 4 conversion into oxygenates [J ] . Applied Catalysis B: Environmental , 2022 , 318 : 121830 .

LI J W , DOU L G , SHAO T , et al . Revealing the active sites of the structured Ni-based catalysts for one-step CO 2 /CH 4 conversion into oxygenates by plasma-catalysis [J ] . Journal of CO 2 Utilization , 2021 , 52 : 101675 .

QI C X , AMPHLETT J C , PEPPLEY B A . Product composition as a function of temperature over NiAl-layered double hydroxide derived catalysts in steam reforming of methanol [J ] . Applied Catalysis A: General , 2006 , 302 : 237 - 243 .

AURNOB A K M K , DING K , KAUFFMAN D R , et al . Low temperature catalytic conversion of CH 4 , CO 2 , and C 2 H 4 to value-added C 3 oxygenates and olefins via C 1 —C 2 coupling on Pd-Au/CeO 2 [J ] . Applied Catalysis B: Environmental , 2023 , 322 : 122107 .

NKINAHAMIRA F , YANG R , ZHU R , et al . Current progress on methods and technologies for catalytic methane activation at low temperatures [J ] . Advanced Science , 2023 , 10 : 2204566 .

LI Y F , ZHENG K , SHEN Y , et al . Acetic acid production from CH 4 and CO 2 via synergistic catalysis between Pd particles and oxygen vacancies generated in ZrO 2 [J ] . The Journal of Physical Chemistry C , 2023 , 127 : 5841 - 5854 .

LI P , LIU W , DENNIS J S , et al . Ultrafine alloy nanoparticles converted from 2D intercalated coordination polymers for catalytic application [J ] . Advanced Functional Materials , 2016 , 26 : 5658 - 5668 .

LQBAL M A , FEDEL M . Ordering and disordering of in situ grown MgAl-layered double hydroxide and its effect on the structural and corrosion resistance properties [J ] . International Journal of Minerals, Metallurgy and Materials , 2019 , 26 : 1570 - 1577 .

PARK S J , KIM Y , JONES C W . NaNO 3 -promoted mesoporous MgO for high-capacity CO 2 capture from simulated flue gas with isothermal regeneration [J ] . ChemSusChem , 2020 , 13 : 2988 - 2995 .

BAR A , KUMAR S , SINGH R S . Efficient removal of Congo red from aqueous solutions using calcined and uncalcined MgZnFe ternary layered double hydroxide (LDH) [J ] . Surfaces and Interfaces , 2024 , 55 : 105341 .

JIN L , HUANG Q J , ZENG H Y , et al . Organic modification of Mo-decorated MgAl layered double hydroxide for polymer flame retardancy [J ] . Composites Part A: Applied Science and Manufacturing , 2020 , 129 : 105717 .

LIU J Q , SONG J Y , XIAO H D , et al . Synthesis and thermal properties of ZnAl layered double hydroxide by urea hydrolysis [J ] . Powder Technology , 2014 , 253 : 41 - 45 .

JING F L , ZHANG Y Y , LUO S Z , et al . Nano-size MZnAl (M = Cu, Co, Ni) metal oxides obtained by combining hydrothermal synthesis with urea homogeneous precipitation procedures [J ] . Applied Clay Science , 2010 , 48 : 203 - 207 .

LEI F , ZHANG R X , YANG J L , et al . Highly Selective Conversion of CH 4 to high value-added C1 oxygenates over Pd loaded ZnTi-LDH [J ] . Advanced Energy Materials , 2023 , 13 : 2301118 .

WANG Y F , LIU X Y , MENG L W , et al . Promotion of catalytic performance of Pd/Al 2 O 3 for o -xylene oxidation by morphological control [J ] . Chemical Engineering Journal , 2023 , 472 : 145013 .

JANG E J , LEE J , OH DG , et al . CH 4 oxidation activity in Pd and Pt-Pd bimetallic catalysts: Correlation with surface PdO x quantified from the DRIFTS study [J ] . ACS Catalysis , 2021 , 11 : 5894 - 5905 .

KULJIRASETH J , WANGRIYA A , MALONES J M C , et al . Synthesis and characterization of AMO LDH-derived mixed oxides with various Mg/Al ratios as acid-basic catalysts for esterification of benzoic acid with 2-ethylhexanol [J ] . Applied Catalysis B: Environmental , 2019 , 243 : 415 - 427 .

GUO X P , PENG Z J , HU M X , et al . Highly active Ni-based catalyst derived from double hydroxides precursor for low temperature CO 2 methanation [J ] . Industrial & Engineering Chemistry Research , 2018 , 57 ( 28 ): 9102 - 9111 .

PRINETTO F , GHIOTTI G , DURAND R , et al . Investigation of acid-base properties of catalysts obtained from layered double hydroxides [J ] . The Journal of Physical Chemistry B , 2000 , 104 : 11117 - 11126 .

WU J F , YU S M , WANG W D , et al . Mechanistic insight into the formation of acetic acid from the direct conversion of methane and carbon dioxide on zinc-modified H-ZSM-5 zeolite [J ] . Journal of the American Chemical Society , 2013 , 135 : 13567 - 13573 .

LI Y F , LIU B , LIU J , et al . Tuning the lewis acidity of ZrO 2 for efficient conversion of CH 4 and CO 2 into acetic acid [J ] . New Journal Chemistry , 2021 , 45 : 8978 - 8985 .

MIAO C L , HUI T L , LIU Y N , et al . Pd/MgAl-LDH nanocatalyst with vacancy-rich sandwich structure: Insight into interfacial effect for selective hydrogenation [J ] . Journal of Catalysis , 2019 , 370 : 107 - 117 .

LIU Y J , WANG R J , RUSSELL C K , et al . Mechanisms for direct methane conversion to oxygenates at low temperature [J ] . Coordination Chemistry Reviews , 2022 , 470 : 214691 .

TOYAO T , KAYAMORI S , MAENO Z , et al . Heterogeneous Pt and MoO x Co-loaded TiO 2 catalysts for low-temperature CO 2 hydrogenation to form CH 3 OH [J ] . ACS Catalysis , 2019 , 9 : 8187 - 8196 .

浏览量

下载量

CNKI被引量

文章被引用时，请邮件提醒。

提交

工具集

关联资源

焙烧温度对MOF衍生Cu@C催化剂催化草酸二甲酯加氢制乙二醇性能的影响

合成气绿色合成乙酸研究进展

Mo助剂对Ni/C催化剂上甲醇羰基化性能的影响

焙烧温度对Pd/LDH催化剂上CH4-CO2两步梯阶转化合成乙酸的影响

Effects of calcination temperatures on CH4-CO2 two stepwise conversion to acetic acid over Pd/LDH catalysts

DOI：10.12434/j.issn.2097-2547.20250140

摘要

Abstract

关键词

Keywords

references

焙烧温度对Pd/LDH催化剂上CH₄-CO₂两步梯阶转化合成乙酸的影响

Effects of calcination temperatures on CH₄-CO₂ two stepwise conversion to acetic acid over Pd/LDH catalysts