Abstract: The conversion of mine gas as the feedstock to produce highly valuable chemicals and liquid fuel(methanol) has become a research hot spot. Catalytic oxidation, an effective technique for activating mine gas, has received considerable attention in recent years. The research on highly efficient and cheap catalysts is critically important for catalytic oxidation of mine gas into methanol.Using ferric nitrate, copper nitrate and ZSM-5 molecular sieve as raw materials, Fe₂O₃/ZSM-5, CuO/ZSM-5 and Fe₂O₃-CuO/ZSM-5 catalysts were prepared by the ion exchange method, and their selective oxidation of low concentration mine gas to methanol were investigated in acetic acid. Results showed that Fe₂O₃/ZSM-5, CuO/ZSM-5 and Fe₂O₃-CuO/ZSM-5 all had catalytic activity for the selective oxidation of mine gas to methanol, and Fe₂O₃-CuO/ZSM-5 exhibited the most evident catalytic effect. Meanwhile, the active metal loading had significant effect on the catalytic activity of the catalyst, and theoretically the best loadings of Fe and Cu were 4.21% and 3.22%, respectively. When the addition of Fe₂O₃-CuO/ZSM-5 (x_Fe=4.21%, x_Cu=3.22%) was 0.1g and the amount of acetic acid was 30mL, the optimum reaction conditions of oxidation of mine gas (with the volume fraction of methane being 20%) to methanol catalyzed by Fe₂O₃-CuO/ZSM-5 were: initial reaction pressure 4.0 MPa, reaction temperature 200℃ and reaction time 3h.

Key words: Fe₂O₃-CuO/ZSM-5, catalyst, partial oxidation, mine gas, methanol

摘要： 采用催化氧化的方法,将煤矿抽采瓦斯制成高价值的化学品或液体燃料甲醇是其综合利用的一个发展方向。寻找对瓦斯转化具有较好的催化效果,且能替代贵金属催化剂的普通催化剂是瓦斯催化氧化制甲醇的研究重点。本文以硝酸铁、硝酸铜和ZSM-5分子筛为原料,采用离子交换法制备了Fe₂O₃/ZSM-5、CuO/ZSM-5和Fe₂O₃-CuO/ZSM-5催化剂,并在乙酸溶剂中考察了3种催化剂催化低浓度瓦斯部分氧化合成甲醇的性能。结果表明,Fe₂O₃/ZSM-5、CuO/ZSM-5和Fe₂O₃-CuO/ZSM-5对瓦斯部分氧化制甲醇反应均有催化活性,但Fe₂O₃-CuO/ZSM-5的催化效果最明显,且Fe、Cu负载量对催化剂的催化活性影响较为显著,Fe和Cu的最佳理论负载量分别为4.21%和3.22%。在Fe₂O₃-CuO/ZSM-5(x_Fe=4.21%,x_Cu=3.22%)添加量为0.1g、乙酸溶剂用量30mL的条件下,Fe₂O₃-CuO/ZSM-5催化甲烷体积分数为20%配制瓦斯制甲醇的最佳反应条件为初始反应压力4.0MPa、反应温度200℃、反应时间3h。

关键词: Fe₂O₃-CuO/ZSM-5, 催化剂, 部分氧化, 瓦斯, 甲醇