连续性气相催化转化低浓度生物燃气制甲醇

陆志恒; 谢玄兰; 李文志

doi:doi:10.19912/j.0254-0096.tynxb.2025-0142

English Version Journal Login

您当前的位置：

首页 >

文章列表页 >

连续性气相催化转化低浓度生物燃气制甲醇

更新时间：2026-07-22

- 连续性气相催化转化低浓度生物燃气制甲醇
- Vol. 47, Issue 4, Pages: 467-477(2026)
- 作者机构：
- 作者简介：
- 基金信息：
- DOI：doi:10.19912/j.0254-0096.tynxb.2025-0142
  CLC： TQ223
- Online First：08 May 2026，
  
  Published：2026
- 稿件说明：
移动端阅览
陆志恒, 谢玄兰, 李文志. 连续性气相催化转化低浓度生物燃气制甲醇[J]. 2026, 47(4): 467-477.
DOI：

陆志恒, 谢玄兰, 李文志. 连续性气相催化转化低浓度生物燃气制甲醇[J]. 2026, 47(4): 467-477. DOI： doi:10.19912/j.0254-0096.tynxb.2025-0142.

摘要

采用浸渍法制备一系列铜基沸石催化剂（xCu/MOR）

并在以水为氧化剂的连续性气相条件下开展催化生物燃气部分氧化制甲醇性能研究。结果表明

350 ℃条件下

甲醇产率随着铜负载量的增加呈火山型趋势

其中2Cu/MOR催化剂可实现67.3 μmol/（g·h）的高甲醇产率;进一步优化反应温度

2Cu/MOR催化剂在400 ℃反应条件下甲醇产率高达142.5 μmol/（g·h）。此外

使用X射线衍射、高分辨透射电子显微镜、X射线光电子能谱、紫外-漫反射可见光谱、甲烷程序升温脱附及傅里叶变换红外光谱技术进行催化剂表征分析

结果表明铜基沸石催化剂中铜元素分散均匀

表现出优异活性的2Cu/MOR催化剂有更多的孤立二价铜活性位点

反应过程中甲烷在孤立二价铜位点上吸附活化

形成的甲氧基中间体与水解离产生的羟基反应生成甲醇。

Abstract

A series of copper-based zeolite catalysts （Cu/MOR） were prepared by impregnation method

and the performance of catalytic partial oxidation of biogas to methanol was investigated under continuous gas-phase conditions with water as oxidant. The results show that the methanol yield at 350 ℃ shows a volcano trend with the increase of copper loading

in which the 2Cu/MOR catalyst can achieve a high methanol yield of 67.3 μmol/（g·h）; further optimization of the reaction temperature results in a high methanol yield of up to 142.5 μmol/（g·h） for the 2Cu/MOR catalyst at 400 ℃. In addition

catalyst characterization using X-ray diffraction

high-resolution transmission electron microscopy

X-ray photoelectron spectroscopy

UV-diffuse reflectance visible spectroscopy

methane programmed warming desorption

and Fourier transform infrared spectroscopy show that the copper element in the copper-based zeolite catalysts is uniformly dispersed

and the 2Cu/MOR catalysts that demonstrated excellent activity have more isolated divalent copper active species. During the reaction process

methane is adsorbed and activated on the isolated divalent copper sites

and the formed methoxy intermediate reactes with the hydroxyl group produced by hydrolysis to form methanol.

关键词

Keywords

references

李洪深, 楚洁璞, 徐伟涛, 等. 干法生物天然气BECCS工程碳负排效益分析[J]. 太阳能学报, 2024, 45(5): 158-164.

李天沛, 丁为民, 柴喜存, 等. 酸、碱、氧化试剂与低温冻融联合预处理对高粱秸秆厌氧发酵产甲烷的影响[J]. 太阳能学报, 2022, 43(3): 492-500.

李东, 叶景清, 王世光, 等. 稻草与猪粪连续混合厌氧消化制备生物燃气研究[J]. 太阳能学报, 2014, 35(10): 1850-1856.

王丰园, 金海炎, 闫振丽, 等. 复合菌系预处理对玉米秸秆厌氧沼气发酵的影响[J]. 太阳能学报, 2023, 44(8): 535-541.

刘锋章, 程博, 秦宁, 等. 太阳能驱动甲烷重整泡沫反应器聚光特性研究及优化设计[J]. 太阳能学报, 2024, 45(7): 599-606.

WANG L Q, JIN J T, LI W Z, et al.Highly selective catalytic oxidation of methane to methanol using Cu-Pd/anatase[J]. Energy & environmental science, 2024, 17(23): 9122-9133.

雷宇, 袁熹, 王颖, 等. 基于太阳能的甲烷重整制氢技术研究进展[J]. 太阳能学报, 2022, 43(12): 154-160.

王集杰, 韩哲, 陈思宇, 等. 太阳燃料甲醇合成[J]. 化工进展, 2022, 41(3): 1309-1317.

周家辉, 张润之, 徐钢, 等. 基于Copula-Shuffle方法的风光互补制氢合成绿色甲醇系统两阶段随机优化[J]. 太阳能学报, 2024, 45(9): 70-79.

叶结旺, 蒋剑春, 马中青, 等. 超临界甲醇中复合金属氧化物催化木质纤维生物质转化为液体燃料: 反应温度的影响[J]. 太阳能学报, 2020, 41(1): 172-178.

宋国辉, 赵亮, 王金平, 等. 绿电耦合生物质制甲醇的储能-释能效率和碳排放[J]. 太阳能学报, 2024, 45(12): 478-484.

罗东晓, 王华. 生物燃气高效利用技术[J]. 煤气与热力, 2019, 39(2): 28-30, 44.

袁亮, 安胜欣, 薛生, 等. 煤层气直接催化氧化制甲醇研究进展[J]. 科技导报, 2024, 42(12): 125-142.

XIE X L, LI C, LU Z H, et al.Noble metal modified copper-exchanged mordenite zeolite(Cu-ex-MOR) catalysts for catalyzing the methane efficient gas-phase synthesis methanol[J]. Energy, 2024, 300: 131595.

JIN Z, WANG L, ZUIDEMA E, et al.Hydrophobic zeolite modification for in situ peroxide formation in methane oxidation to methanol[J]. Science, 2020, 367(6474): 193-197.

DUMMER N F, WILLOCK D J, HE Q, et al.Methane oxidation to methanol[J]. Chemical reviews, 2023, 123(9): 6359-6411.

SNYDER B E R, BOLS M L, SCHOONHEYDT R A, et al. Iron and copper active sites in zeolites and their correlation to metalloenzymes[J]. Chemical reviews, 2018, 118(5): 2718-2768.

HAMMOND C, FORDE M M, AB RAHIM M H, et al. Direct catalytic conversion of methane to methanol in an aqueous medium by using copper-promoted Fe-ZSM-5[J]. Angewandte chemie (international ed in English), 2012, 51(21): 5129-5133.

[J]. Nature catalysis, 2022, 5(1): 45-54.

ALAYON E M, NACHTEGAAL M, RANOCCHIARI M, et al.Catalytic conversion of methane to methanol over Cu-mordenite[J]. Chemical communications, 2012, 48(3): 404-406.

ALAYON E M C, NACHTEGAAL M, BODI A, et al. Bis(μ-oxo) versus mono(μ-oxo)dicopper cores in a zeolite for converting methane to methanol: an in situ XAS and DFT investigation[J]. Physical chemistry chemical physics, 2015, 17(12): 7681-7693.

ZHANG H L, LYU J H, ZHANG Z, et al.Oxidation of methane to methanol by water over Cu/SSZ-13: impact of Cu loading and formation of active sites[J]. ChemCatChem, 2022, 14(5): e202101609.

SOGUKKANLI S, MOTEKI T, OGURA M.Selective methanol formation via CO-assisted direct partial oxidation of methane over copper-containing CHA-type zeolites prepared by one-pot synthesis[J]. Green chemistry, 2021, 23(5): 2148-2154.

ZHOU C X, LI S S, HE S, et al.Temperature-dependant active sites for methane continuous conversion to methanol over Cu-zeolite catalysts using water as the oxidant[J]. Fuel, 2022, 329: 125483.

BRINDLE J, NIGRA M M.The role of water and copper oxide in methane oxidation using AuPd nanoparticle catalysts[J]. Chemical engineering journal, 2022, 446: 136979.

CAO J X, QI G D, YAO B Q, et al.Partially bonded aluminum site on the external surface of post-treated Au/ZSM-5 enhances methane oxidation to oxygenates[J]. ACS catalysis, 2024, 14(3): 1797-1807.

DINH K T, SULLIVAN M M, NARSIMHAN K, et al.Continuous partial oxidation of methane to methanol catalyzed by diffusion-paired copper dimers in copper-exchanged zeolites[J]. Journal of the American Chemical Society, 2019, 141(29): 11641-11650.

POKHREL J, SHANTZ D F.Continuous partial oxidation of methane to methanol over Cu-SSZ-39 catalysts[J]. Journal of catalysis, 2023, 421: 300-308.

NARSIMHAN K, IYOKI K, DINH K, et al.Catalytic oxidation of methane into methanol over copper-exchanged zeolites with oxygen at low temperature[J]. ACS central science, 2016, 2(6): 424-429.

FU Y, LI C S, AN S X, et al.Cu and Zn bimetallic co-modified H-MOR catalyst for direct oxidation of low-concentration methane to methanol[J]. ACS omega, 2023, 8(30): 27179-27189.

LU Z H, WANG Y S, CHEN M Q, et al.Direct partial oxidation of low-concentration methane to methanol with copper-based clay catalysts[J]. International journal of hydrogen energy, 2024, 81: 535-547.

HONG Z, LI J H, XIONG C F, et al.Creation of cross directing intergrowth MOR/ZSM-5 with high catalytic activity: insights into the role of crystallization time[J]. Microporous and mesoporous materials, 2021, 320: 111102.

SUSHKEVICH V L, VAN BOKHOVEN J A. Methane-to-methanol: activity descriptors in copper-exchanged zeolites for the rational design of materials[J]. ACS catalysis, 2019, 9(7): 6293-6304.

GIORDANINO F, VENNESTRØM P N R, LUNDEGAARD L F, et al. Characterization of Cu-exchanged SSZ-13: a comparative FTIR, UV-Vis, and EPR study with Cu-ZSM-5 and Cu-β with similar Si/Al and Cu/Al ratios[J]. Dalton transactions, 2013, 42(35): 12741-12761.

WANG Y S, QIN B L, CHEN M Q, et al.Preparation of Cu-based spherical micromesoporous material by using sepiolite toward methanol production from catalytic oxidation of low-concentration coalbed methane[J]. Industrial & engineering chemistry research, 2024, 63(16): 6934-6950.

Views

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

EFFECT OF CATALYST AND TORREFACTION COUPLING ON PYROLYSIS CHARACTERISTICS OF ELM

CONTINUOUS CATALYTIC HYDROLYSIS OF CELLULOSE

COMPARISON OF THREE BIOMASS-DERIVED SYNGAS ON CATALYSTIC SYNTHESIS

REVIEW ON HYDROGEN-RICH GAS PRODUCTION FROM BIOMASS

基于双绕组异步电机的并网逆变系统及其多工况控制策略

Related Author

宋国辉

赵亮

王金平

王红艳

肖军

Mei Yanyang

Hou Jingfan

Li Wenqi

Related Institution

School of Mechanical and Power Engineering, Henan Polytechnic University

华东理工大学能源系

Guangzhou Institute of Energy Comersion, Chinese Academy of Sciences

中国科学院广州能源研究所广州510640

Section of Bioenergy and Environment,Faculty of Environmental Science and Engineering/State Key Labof Internal Combustion Engine,Tianjin University

AI问答

⁰