Pd(OAc)2 and chloranil-catalyzed oxidation of low-concentration coal mine gases to methanol
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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。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.
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Key words:
- palladium acetate /
- chloranil /
- mine gases /
- methanol
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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)
Figure 3. Catalytic results for oxidation of mine gases at different gas pressure (reaction conditions: 100μmol of Pd(OAc)2, 140℃, 1500μmol of chloranil)
Figure 4. Catalytic results for oxidation of mine gases at different temperature (1500μmol of chloranil, 100μmol of Pd(OAc)2, gas pressure of 5MPa )
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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