【作者】 张宇；

【导师】 郭洪臣；

【作者基本信息】 大连理工大学 ， 工业催化， 2016， 硕士

【摘要】 丙烯作为仅次于乙烯的世界第二大石油化工原料,其产能衡量着国家的国民经济水平。而丙烯氧化反应是得到重要三碳有机物的过程,可以得到包括环氧丙烷、丙烯醛、丙酮、丙醛等在内的许多高附加值丙烯衍生物。而其中环氧丙烷和丙烯醛作为丙烯氧化物中产量占比最大的两种物质,其生产过程和催化剂应用受到了广泛的关注和研究。本文分别以环氧丙烷（PO）和丙烯醛（An）为目标产物,以Ag/TS-1（μm）和 Mo-Bi-Fe-Co复合氧化物为丙烯氧化反应的催化剂开展研究。首先考察了制备方法、制备条件、Ag载量、TS-1载体、反应条件等因素对丙烯在Ag/TS-1（μm）上气相氧化制环氧丙烷反应性能的影响。通过XRD、UV-vis、TEM等手段来进一步研究影响催化剂的银颗粒尺寸、氧化态银物种等关键因素。在此基础上,尝试合成一系列Mo-Bi-O催化剂。考察了合成方法、催化剂组成、合成条件、沉淀剂加入等因素对丙烯在Mo-Bi-O催化剂上选择氧化制丙烯醛反应性能的影响。通过详细的表征手段来分析表征分析催化剂的活性相态、寻找最优催化剂结构形式。实验结果表明,在25℃、pH=7条件下采用沉积沉淀法制备得到的3.0wt%Ag/TS-1（μ m）催化剂上反应性能最佳。在空速2000ml·h-1·g-1cat、反应温度180℃、进料比V（C3H6）:V（O2）:V（H2）:V（Ar）=1:2:2:3条件下,得到了1.09%的丙烯转化率和85.6%的PO选择性。本文研究发现反应最佳Ag颗粒尺寸为8nm,氧化态银物种的出现有利于反应活性的提高。以钼酸铵和硝酸铋为前驱体,采用共沉淀法在60℃和pH=7下沉淀,400℃空气下焙烧1h条件下得到的Mo₂Bi₂Fe_0.2Co_0.02（1ml丙酸作为沉淀剂）催化剂的反应性能最佳。在空速1500 ml·h-1·g-1cat,反应温度360℃、进料比V（C3H6）:V（O2）:V（Ar）=1:2:8条件下,得到了66.24%的丙烯转化率和73.32%的丙烯醛选择性。通过表征发现：β-Bi2Mo2O9是该反应的活性相物种、Fe/Co元素和丙酸的加入有利于改进催化剂的性能。更多还原

【Abstract】 propylene is the second largest raw petrochemical materials in the world and its production measures a country’s national economy level. Propylene oxidation reaction is a process to acquire important C3 organics including propylene oxide, acrolein, acetone, propionaldehyde and so on. As propylene oxide and acrolein are the two most biggest products, their preparation process and catalystic application received wide attention and research.In this paper propylene oxide and acrolein were obtained as target products. Ag/TS-1 and Mo-Bi-Fe-Co were the catalysts in respective reactions. First, the influence of preparing method, preparing condition, Ag loadings, TS-1 supports and reaction condition on the performance of Ag/TS-1 for propylene epoxidation was investigated. Ag particles size, oxidized Ag species were found through XRD, UV-vis, TEM and so on. Then, a series of Mo-Bi-O catalysts were synthetized independently. The influence of synthetic methods, catalyst components, synthesis conditions and the addition of precipitators on the performance of Mo-Bi-O catalysts for propylene selective oxidation was investigated. The active phase in the catalysts and the optimal form of catalyst were found by detailed characterization means.The results shows that 3.0wt%Ag/TS-1（μm） catalysts acquired by DP method under aging temperature of 25℃, and pH value of 7 gave the best catalytic performance. Over this catalyst,0.96% propylene conversion and 81.18% selectivity to PO has been obtained under the reaction condition of 180℃,2000ml·h-1·g-1 cat and V（O2）:V（C3H6）:V（H2）:V（Ar）= 1:2:3:3. The characterizations found that the optimal Ag particles size is 8nm and the oxidized Ag species is favorable to propylene epoxidation.Mo₂Bi₂Fe_0.2Co_0.02 （1ml propionic acid as precipitator）catalysts acquired by CP method, under pH value of 7, caclined at 400℃ for 1h, gave the best catalytic performance. Over this catalyst,66.24% propylene conversion and 73.32% selectivity to An has been obtained under the reaction condition of 360℃, 1500ml·h-1·g-1·cat and V（O2）:V（C3H6）:V（Ar）= 1:2:8. The characterizations found that β-Bi2Mo2O9 is the active phase in the catalysts. The addition of Fe, Co and propionic acid is favorable to the performance of catalysts.更多还原