醋酸钯和四氯对苯醌催化氧化低浓度煤矿瓦斯制甲醇

XU Feng; LICh uang; JIA Shao-yang; WU Yang; ZHU Li-hua

醋酸钯和四氯对苯醌催化氧化低浓度煤矿瓦斯制甲醇

黑龙江科技大学安全工程学院, 黑龙江哈尔滨 150022

基金项目:

The project was supported by the National Natural Science Foundation of China 51374098

Scientific Research Foundation for Innovation Talents of Harbin City, China 2013RFQXJ085

Financial Assistance from Postdoctoral Scientific Research Developmental Fund of Heilongjiang Province LBH-Q14143

Training Program of the Major Research Plan of the Heilongjiang University of Science and Technology aq2013-2

详细信息

中图分类号: O643.32
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- 被引次数: 0
出版历程
- 收稿日期: 2015-09-18
- 修回日期: 2015-11-26
- 网络出版日期: 2022-03-23
- 刊出日期: 2016-06-01

Pd(OAc)₂ and chloranil-catalyzed oxidation of low-concentration coal mine gases to methanol

College of Safety Engineering, Heilongjiang University of Science and Technology, Harbin 150022, China

Funds:

The project was supported by the National Natural Science Foundation of China 51374098

Scientific Research Foundation for Innovation Talents of Harbin City, China 2013RFQXJ085

Financial Assistance from Postdoctoral Scientific Research Developmental Fund of Heilongjiang Province LBH-Q14143

Training Program of the Major Research Plan of the Heilongjiang University of Science and Technology aq2013-2

More Information

Corresponding author: E-mail: xufeng79_79@163.com

摘要

摘要: 利用自制的实验系统进行了醋酸溶液中低浓度瓦斯催化氧化制甲醇研究。实验结果表明, 以Pd(OAc)₂为催化剂, 反应体系中添加对苯醌或四氯对苯醌可改善甲烷活化环境, 四氯对苯醌对瓦斯催化氧化过程的作用效果好于对苯醌。四氯对苯醌用量、反应压力和反应温度对瓦斯催化氧化具有重要影响。甲醇生成量随四氯对苯醌用量、反应压力和反应温度升高而增加。CH₃OH是通过反应过程中产生的H₂O₂与CH₄相互作用形成的。CH₃COOCH₃一部分是由Pd²⁺直接氧化CH₄得到的;另一部分是由CH₃OH与反应溶剂CH₃COOH通过酯化反应形成的。
- 醋酸钯 /
- 四氯对苯醌 /
- 瓦斯 /
- 甲醇
Abstract: A self-made experimental system was used to study the catalytic oxidation of low-concentration coal mine gases to methanol in acetic acid solution.With Pd(OAc)₂ as catalyst, addition of p-benzoquinone or chloranil in the reaction system provides a beneficial environment for activation of methane, and chloranil shows a more positive effect.Chloranil amount and reaction temperature and pressure are the key factors influencing the catalytic properties.The target product yield has a positive relationship with these three factors.CH₃OH is formed from the reaction of generated H₂O₂ and CH₄.CH₃COOCH₃ is generated via two routes;one is direct oxidation of Pd²⁺ and CH₄, the other is esterification of CH₃OH and CH₃COOH.
- palladium acetate /
- chloranil /
- mine gases /
- methanol

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Figure 1 Schematic diagram of experimental apparatus

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Figure 2 Catalytic results obtained in the Pd(OAc)₂-chloranil-CO reaction system containing different amounts of chloranil (reaction conditions: 100μmol of Pd(OAc)₂, 140℃, 4MPa of mine gases)

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Figure 3 Catalytic results for oxidation of mine gases at different gas pressure (reaction conditions: 100μmol of Pd(OAc)₂, 140℃, 1500μmol of chloranil)

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Figure 4 Catalytic results for oxidation of mine gases at different temperature (1500μmol of chloranil, 100μmol of Pd(OAc)₂, gas pressure of 5MPa )

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Table 1 CH₃OH yield obtained over the Pd(OAc)₂ and 3%Pd/C in the oxidation of mine gases

Entry	Reaction system	CH₃OH yield m/μmol
1	3%Pd/C-p-benzoquinone -CO	105
2	3%Pd/C- chloranil -CO	120
3	Pd(OAc)₂-p-benzoquinone -CO	352
4	Pd(OAc)₂- chloranil -CO	385

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Table 2 O₂ conversions at different experimental conditions

Entry	Temperature t/℃	Pressure p/MPa	Amount of chloranil m/μmol	Conversion of O₂ x/%
1	140	4	0	1.8
2	140	4	500	4.2
3	140	4	1000	4.6
4	140	4	1500	7.5
5	140	2	1500	9.1
6	140	3	1500	7.7
7	140	5	1500	6.9
8	130	5	1500	2.3
9	150	5	1500	6.8
10	160	5	1500	6.5

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