固体酸催化合成ε-己内酯的研究 Ⅰ.催化剂的表征及其催化性能  

Synthesis of ε-Caprolactone over Solid Acid Catalysts Ⅰ.Characterization and Activity of the Catalysts

作　　者：张光旭[1] 欧华强[1,2] 胡昌林[1] 徐文涛[1] 

机构地区：[1]武汉理工大学化学工程学院,湖北武汉430070 [2]中国天辰工程有限公司,天津300400

出　　处：《石油化工》2011年第5期486-491,共6页Petrochemical Technology

基　　金：武汉理工大学自主创新研究基金项目(2010-ZY-HG-004)

摘　　要：采用浸渍法和混烧法,以γ-Al2O3或Al-MCM-41为载体分别负载B2O3和WO3活性组分,制备了可用于环己酮催化氧化合成ε-己内酯的固体酸催化剂,通过XRD、N2吸附-脱附、SEM和TEM等技术对催化剂进行了表征,并利用ε-己内酯合成实验评价了催化剂的性能。实验结果表明,混烧法制备的B2O3/γ-Al2O3催化剂对环己酮氧化合成ε-己内酯具有较高的活性。在B2O3/γ-Al2O3催化剂用量为0.8 g,第一步反应中丙酸65.19 g、双氧水25.00 g、48.13 kPa、3 h,第二步反应中环己酮5.40 g、50℃、常压、2 h的条件下,ε-己内酯的选择性和收率分别达95.80%和85.97%。在该催化反应中,催化剂的比表面积、孔径及孔体积等结构参数对催化活性影响不大,而高温焙烧过程中B2O3进入γ-Al2O3晶相后产生的晶格缺陷是该催化剂高活性的关键。The supported B2O3 or WO3 catalysts with γ-Al2O3 or Al-MCM-41 as supports for catalytic oxidation of cyclohexanone to ε-caprolactone were prepared by impregnation and cocalcination methods separately. The catalysts were characterized by means of XRD, N2 adsorptiondesorption, SEM and TEM. Their catalytic performances in the synthesis of ε-caprolactone were investigated. The results showed that B2 O3/γ-Al2O3 catalyst prepared by co-calcination had better catalytic activity than the others. Under the conditions： in the first step reaction, catalyst dosage 0.8 g, propionic acid dosage 65.19 g, hydrogen peroxide dosage 25.00 g, pressure 48.13 kPa and time 3 h, and in the second step reaction, cyclohexanone dosage 5.40 g, temperature 50 ℃, normal pressure and time 2 h, the selectivity and the yield of ε-caprolactone could reach 95. 80% and 85. 97%, respectively. In the catalytic reaction, the effects of specific surface area, pore diameter and pore volume of the catalysts on its activity were little. The crystal defects in the B2 O3/γ-Al2O3 catalyst, which were formed due to introduction of B2O3 active constituent to γ-Al2O3 crystalline phase during the high temperature co-calcination process, were the key factor of high activity of the catalyst.

关 键 词：环己酮 Ε-己内酯 固体酸催化剂 浸渍法 混烧法 

分 类 号：TQ032.4[化学工程]