PW/介孔Hβ沸石催化合成金刚烷的研究  

Preparation of Adamantane over PW/meso-Hβ Zeolite Catalyst

作　　者：周志伟[1] 秦娟 王巍[1] 武文良[1] 

机构地区：[1]南京工业大学化学化工学院,江苏南京210009 [2]江苏省科技金融服务中心,江苏南京210042

出　　处：《高校化学工程学报》2013年第4期615-621,共7页Journal of Chemical Engineering of Chinese Universities

基　　金：江苏省自然科学基金资助项目(BK2008376)

摘　　要：采用NaOH溶液对含有模板剂氢氧化四乙基铵(TEAOH)的Hβ沸石进行脱硅处理,制备了介孔Hβ沸石;采用过量液相浸渍法制备了一系列介孔Hβ沸石负载磷钨酸(PW)催化剂,考察了其在桥式四氢双环戊二烯(endo-TCD)异构化制备金刚烷反应中的催化性能;并采用XRD、液N2吸附和NH3-TPD对催化剂的物化性质进行了表征。表征结果表明,当PW酸负载量达到30%时,其仍能在介孔Hβ沸石表面高度分散,且对应的催化剂的酸量最大。采用30%PW/介孔Hβ沸石为催化剂,在反应温度240℃,w(catalyst)/w(endo-TCD)=0.6,反应时间为5 h时,endo-TCD的转化率达到99.4%;与PW/Hβ沸石相比,PW/介孔Hβ沸石由于其存在部分介孔,金刚烷的收率提高至原来的1.46倍,原来的22.4%提高至32.7%;且催化剂再生能力良好,重复使用6次后,金刚烷收率还高达28.7%。Desilicated mesoporous Hβ zeolite was prepared through treating Hβ zeolite including template tetraethylammonium hydroxide（TEAOH） with NaOH aqueous solution.12-Tungstophosphoric acid（PW） was immobilized on the desilicated mesoporous Hβ zeolite at room temperature to form the PW/meso-Hβ catalysts.The physical and chemical properties of the PW/meso-Hβ catalysts were characterized by X-ray diffraction（XRD）,liquid N2 adsorption-desorption and temperature programmed desorption of ammonia（NH3-TPD）,respectively;and the catalytic performances of the prepared PW/meso-Hβ catalysts were investigated by catalyzing the isomerization reaction of endo-tetrahydrodicyclotadiene（endo-TCD） to form adamantane（ADH） in a 100 mL batch stainless-steel autoclave with stirring.The results show that the loaded PW could still be highly dispersed on the surface of the desilicated mesoporous Hβ zeolite when the PW loading is 30%,and the 30%PW/meso-Hβ catalyst has the largest acid amount.When using 30%PW/meso-Hβ zeolite as catalyst,99.4% conversion of endo-TCD can be obtained under the following conditions： reaction temperature of 240℃,the catalyst to endo-TCD mass ratio of 0.6 and reaction time of 5 h.In comparison with PW/Hβ catalyst,the yield of ADH increases from 22.4% to 32.7% because of the presence of mesopores in the desilicated Hβ zeolite.The catalytic activity of used catalyst can be recovered and the yield of ADH can still reach 28.7% after 6 times reuse.

关 键 词：金刚烷 异构化 磷钨酸 介孔Hβ沸石 

分 类 号：O621.255.8[理学—有机化学] TQ032.41[理学—化学]