CH4和CO2共转化反应机理研究进展

doi:10.16085/j.issn.1000-6613.2023-1069

摘要/Abstract

摘要：

综述了CH₄和CO₂共转化生成合成气、乙酸和C₂烃3种反应路径的反应步骤、关键中间体及反应产物选择性的影响因素。当生成合成气时，CH₄与CO₂的活化解离是关键步骤，催化剂载体表面为酸性或中性时反应遵循单功能机理，CH₄和CO₂在同一活性中心被活化，当载体为表面碱性时，CH₄和CO₂遵循双功能机理，在不同活性中心被活化，通常双功能机理的催化效率更高。当生成乙酸时，C-C耦合过程应被重点关注，该过程中气相CO₂可能直接插入M—CH₃键（Eley-Rideal机理）或先被吸附活化后再插入（Langmuir-Hinshelwood机理），后者反应能垒更低。当生成C₂烃时，活性氧物种被认为是反应过程中的关键中间体，其可能来源于催化剂中的晶格氧或CO₂的活化与解离。因此，在催化剂表面构建多个独立活性位点，以分别对CH₄和CO₂进行多位点协同催化被认为是良好的催化剂改性策略。另外，先进的模拟计算方法和原位表征手段能够深入揭示反应过程中催化剂和反应中间体的动态演变过程及机理，从而为真实CH₄和CO₂共转化反应过程中催化剂的设计提供理论指导。

关键词: 甲烷, 二氧化碳, 反应机理, 合成气, 乙酸, C₂烃

Abstract:

This review provides a comprehensive overview of the reaction pathways involved in the co-conversion of CH₄ and CO₂to produce syngas, acetic acid, and C₂ hydrocarbons. The focus is on elucidating the key reaction steps, intermediates, and the influencing factors on reaction selectivity. For the production of syngas, the activation and dissociation of CO₂ and CH₄ are identified as key steps. The mechanism depends on the acidity of the catalyst support. Acidic or neutral support follow a mono-functional mechanism, where both CH₄ and CO₂ are activated at the same active center. In contrast, a basic support leads to a bi-functional mechanism, involving the activation of CH₄ and CO₂ at different active centers. For acetic acid production, the C-C coupling process assumes to be significant. Two mechanisms are considered: the direct insertion of gas-phase CO₂ into the M—CH₃ bond (Eley-Rideal mechanism), and the prior adsorption of CO₂ followed by insertion (Langmuir-Hinshelwood mechanism), with a lower reaction energy barrier for the latter. For producing C₂ hydrocarbons, reactive oxygen species are considered to be key intermediates in the reaction, which may be derived from the activation and dissociation of lattice oxygen or CO₂ in the catalyst. To enhance the catalytic performance, constructing multiple active sites on the catalyst surface for the co-catalysis of CH₄ and CO₂ is regarded as a promising catalyst modification strategy. Furthermore, advanced simulation calculation methods and in-situ characterization techniques can help to reveal the dynamic evolution of reaction process and the catalytic mechanism, thus providing the theoretical guidance for the design of catalysts in the CH₄ and CO₂co-conversion reaction.

Key words: methane, carbon dioxide, reaction mechanism, syngas, acetic acid, C₂ hydrocarbons

中图分类号:

O643.3

成昊霖, 年瑶, 韩优. CH₄和CO₂共转化反应机理研究进展[J]. 化工进展, 2024, 43(1): 60-75.

CHENG Haolin, NIAN Yao, HAN You. Progress in the mechanism of CH₄ and CO₂co-conversion reactions[J]. Chemical Industry and Engineering Progress, 2024, 43(1): 60-75.

图/表 15

表1 CH4和CO2共转化相关反应的焓变和自由能变[6]

反应式	$Δ$ H_r^⊖/kJ·mol^-1	$Δ$ G_r^⊖/kJ·mol^-1
CH₄(g)+3CO₂(g) $→$ 4CO(g)+2H₂O(l)	+235.1	+209.2
CH₄(g)+CO₂(g) $→$ 2CO(g)+2H₂(g)	+247.5	+170.8
CH₄(g)+CO₂(g) $→$ CH₃COOH(l)	+36.4	+71.1
2CH₄(g)+CO₂(g) $→$ C₂H₆(g)+CO(g)+H₂O(l)	+58.8	+88.0
2CH₄(g)+2CO₂(g) $→$ C₂H₄(g)+2CO(g)+2H₂O(l)	+189.7	+208.3
2CH₄(g)+CO₂(g) $→$ CH₃COCH₃(l)+H₂O(l)	+8.5	+115.0

表1 CH4和CO2共转化相关反应的焓变和自由能变[6]

反应式	$Δ$ H_r^⊖/kJ·mol^-1	$Δ$ G_r^⊖/kJ·mol^-1
CH₄(g)+3CO₂(g) $→$ 4CO(g)+2H₂O(l)	+235.1	+209.2
CH₄(g)+CO₂(g) $→$ 2CO(g)+2H₂(g)	+247.5	+170.8
CH₄(g)+CO₂(g) $→$ CH₃COOH(l)	+36.4	+71.1
2CH₄(g)+CO₂(g) $→$ C₂H₆(g)+CO(g)+H₂O(l)	+58.8	+88.0
2CH₄(g)+2CO₂(g) $→$ C₂H₄(g)+2CO(g)+2H₂O(l)	+189.7	+208.3
2CH₄(g)+CO₂(g) $→$ CH₃COCH₃(l)+H₂O(l)	+8.5	+115.0

图1 CO2与CH4的共转化反应网络

图2 Ni x Al1O2-δ 催化剂上的DRM反应机理[13]

图3 催化剂改性前后进行甲烷干重整催化的单功能和双功能反应机理对比[14]

图4 Cu-CNN位点与Pd-BDCNN位点上的DRM反应机理[16]

图5 Ni纳米颗粒直径对DRM反应各基元步骤速率的影响[22]（括号中表示直径减小时各步骤速率常数的增减情况）

图6 在Ni9.6-V@HSS催化剂上进行DRM反应的反应机理[29]

图7 甲烷和二氧化碳在双功能Zn/H-ZSM-5沸石上共转化为乙酸的反应机理[35]

图8 CO2与CH4分子C-C耦合的E-R机理与L-H机理

表2 CH x 在Ru、Rh和Pd上的吸附能[41] (单位：eV)

解离物种	Ru	Rh	Pd
CH₃	-2.70	-2.58	-2.20
CH₂	-4.07	-3.77	-2.93
CH	-5.64	-5.45	-4.46

图9 不同催化剂下CH4-CO2合成乙酸的反应路径势能面[44]

图10 CeO2催化剂的金属元素掺杂对C-C耦合势垒的影响[45]

图11 Ca-Na-O-Cl催化剂上CH4和CO2生成C2烃的反应机理[60]

图12 操作条件对CO2-OCM反应CH4转化率的影响及其反应机理[62]

表3 CO2和CH4生成C2烃反应中二元金属氧化物催化剂的催化性能

催化剂	温度/K	V(CO₂)/V(CH₄)	C₂烃选择性/%	C₂烃产率/%
CaO-ZnO	1123	2.3	80.0	4.3
La₂O₃-ZnO	1123	2.0	90.6	2.8
Cr₂O₃-CaO	850	2.3	63.0	4.0
CeO₂-CaO	850	1.0	62.0	3.2
MnO₂-SrCO₃	875	2.3	51.0	4.5
Na₂WO₄-Mn/SiO₂	1093.15	2.0	94.0	4.5

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CH₄和CO₂共转化反应机理研究进展

Progress in the mechanism of CH₄ and CO₂co-conversion reactions

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