Stangland Eric E, Taylor Bradley, Andres Ronald P, Delgass W Nicholas
Forney Hall of Chemical Engineering, Purdue University, 480 Stadium Mall Drive, West Lafayette, Indiana 47907-2100, USA.
J Phys Chem B. 2005 Feb 17;109(6):2321-30. doi: 10.1021/jp048869h.
The effects of titanium connectivity, deposition solution neutralizing agent, and catalyst pretreatment were examined for a series of Au-on-titanium-containing supports for the direct gas-phase epoxidation of propylene using hydrogen and oxygen. The degree of titanium isolation was examined using pure titania, monolayer-titania on silica, submonolayer-titania on silica, and titanium silicalite-1 (TS-1) supports. Activity and selectivity were shown to increase as the degree of titanium isolation increased, with TS-1 and submonolayer-titania supports providing the best stability and yield. Isolation of the titanium was found to significantly reduce the cracking of propylene to ethanal and carbon dioxide. Sodium carbonate was found to be the best neutralizing agent for catalysts prepared using deposition-precipitation (DP). DP with ammonium hydroxide gave catalysts with reduced selectivity and activity. Titania-modified silica was found to produce better catalysts when the support was not calcined prior to gold deposition. Similarly, calcination was detrimental to catalysts prepared via deposition of a 2 nm gold colloid onto titania-modified supports even though the gold did not sinter. The beneficial effects of Ti site isolation and support acid/base control are best seen at higher temperatures, where only a few catalysts can maintain selectivity.
对于一系列用于氢气和氧气直接气相环氧化丙烯的负载型金-钛催化剂,研究了钛的连通性、沉积溶液中和剂和催化剂预处理的影响。使用纯二氧化钛、二氧化硅上的单层二氧化钛、二氧化硅上的亚单层二氧化钛以及钛硅分子筛-1(TS-1)载体来考察钛的隔离程度。结果表明,随着钛隔离程度的增加,活性和选择性提高,TS-1和亚单层二氧化钛载体表现出最佳的稳定性和产率。发现钛的隔离显著减少了丙烯裂解为乙醛和二氧化碳的反应。对于采用沉积沉淀法(DP)制备的催化剂,碳酸钠被发现是最佳的中和剂。用氢氧化铵进行沉积沉淀法得到的催化剂选择性和活性降低。当在金沉积之前不对载体进行煅烧时,发现二氧化钛改性的二氧化硅能制备出更好的催化剂。同样,煅烧对通过将2 nm金胶体沉积到二氧化钛改性载体上制备的催化剂不利,即使金没有烧结。钛位点隔离和载体酸碱控制的有益效果在较高温度下最为明显,此时只有少数催化剂能够保持选择性。