In-Cu/SiO_2催化剂用于醋酸甲酯加氢反应制乙醇（英文）
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摘要
工业上常用玉米生产乙醇,从而造成粮食和燃料的选择两难局面.随着页岩气研究的不断深入以及全球可观的煤炭存量,用醋酸甲酯加氢制乙醇已引起广泛关注.铜基催化剂对酯加氢生成醇有高的转化率和选择性,其中铜铬催化剂性能较高,但铬对人体和环境的潜在危害限制了其广泛应用.Cu/SiO_2催化剂价格低廉,环境友好,但其稳定性较差,容易失活不利于工业上应用.因此人们对Cu/SiO_2催化剂进行改性.本文采用氨蒸法制备了一系列掺杂不同量氧化铟(In_2O_3)的Cu催化剂(In-Cu/SiO_2).采用X射线衍射(XRD)、氮气吸脱附、氢气程序升温脱附(H_2-TPD)、傅里叶变换红外光谱(FT-IR)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)以及电感耦合等离子体发射光谱(ICP-OES)等手段对催化剂进行了表征,同时评价了催化剂的活性和稳定性.结果发现,In_2O_3的改性提高了Cu/SiO_2催化剂在醋酸甲酯加氢制乙醇反应中的活性和稳定性;其中当添加1%In_2O_3时,醋酸甲酯转化率从-83.7%提高至97.8%(反应温度523 K,反应压力3 MPa,氢酯摩尔比15,液时空速2 h1),且对液时空速的变化耐受性比较强.当液时空速大于-3 h1时,随着液时空速的增加,Cu/SiO_2催化剂的活性和选择性急剧下降,而1In-Cu/SiO_2催化剂变化相对较小.TEM和XRD结果表明,适量In_2O_3的掺入改善了Cu/SiO_2催化剂活性组分的分散性,铜粒径变小;FT-IR和N_2O化学吸附结果显示,In_2O_3的加入使得页硅酸铜含量增加,从而有效地抑制了催化剂还原过程中铜的聚合,因此催化剂性能提高.XPS结果表明,表面Cu~0和Cu~+活性位点之间的协同作用有助于改善催化剂性能.Cu/SiO_2和1In-Cu/SiO_2催化剂100 h的稳定性测试发现,Cu/SiO_2催化剂的失活主要是由于活性组分颗粒尺寸聚集变大和表面Cu~0和Cu~+分布的破坏所致;而1In-Cu/SiO_2催化剂物化性质几乎保持不变,表明适量的In_2O_3可稳定Cu/SiO_2催化剂,延长其使用寿命.由此推断,In_2O_3可能作为一种隔离剂以抑制铜纳米粒子的热迁移和聚集,从而有效地提高Cu/SiO_2催化剂活性和稳定性.
A series of indium oxide-modified Cu/SiO_2 catalysts were synthesized and used to produce ethanol via methyl acetate hydrogenation. In-Cu/SiO_2 catalyst containing 1.0 wt% In_2O_3 exhibited the best catalytic activity and stability. The physicochemical properties of the synthesized catalysts were investigated using several characterization methods and the results showed that introducing suitable indium to Cu/SiO_2 increased the copper dispersion, diminished the copper crystallite size, and enriched the surface Cu~+ concentration. Furthermore, the Cu/SiO_2 catalyst gradually deactivated during the stability test, which was mainly attributed to copper sintering and the valence change in surface copper species. In contrast, indium addition can inhibit the thermal transmigration and accumulation of copper nanoparticles to stabilize the catalyst.
A series of indium oxide-modified Cu/SiO_2 catalysts were synthesized and used to produce ethanol via methyl acetate hydrogenation. In-Cu/SiO_2 catalyst containing 1.0 wt% In_2O_3 exhibited the best catalytic activity and stability. The physicochemical properties of the synthesized catalysts were investigated using several characterization methods and the results showed that introducing suitable indium to Cu/SiO_2 increased the copper dispersion, diminished the copper crystallite size, and enriched the surface Cu~+ concentration. Furthermore, the Cu/SiO_2 catalyst gradually deactivated during the stability test, which was mainly attributed to copper sintering and the valence change in surface copper species. In contrast, indium addition can inhibit the thermal transmigration and accumulation of copper nanoparticles to stabilize the catalyst.
引文
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