WO_3/ZrO_2固体酸催化剂上苯和1-十二烯的烷基化

Alkylation of Benzene With 1-Dodecene Over the WO_3/ZrO_2 Solid Acid

通过偏钨酸铵和氢氧化锆的润湿-浸渍法制备了WO3/ZrO2固体酸催化剂,对催化剂进行了表征,并在苯和1-十二烯的烷基化反应中进行了评价。考察了催化剂的焙烧温度、反应时间、WO3的质量分数、苯烯摩尔比、催化剂的质量分数等对烷基化反应的影响以及催化剂的再生性能。结果表明,焙烧温度在750~850℃,WO3的质量分数为5%~25%的WO3/ZrO2体系可以形成超强酸,其表面上同时存在L酸中心和B酸中心,并且可以相互转化。WO3/ZrO2固体超强酸催化剂在苯和1-十二烯的液相烷基化反应中表现出良好的催化性能和可再生性。反应的适宜条件为：反应时间为45 min,催化剂焙烧温度为750℃,WO3的质量分数为15%,苯与1-十二烯的摩尔比为10,催化剂的质量分数4%。在此条件下,1-十二烯的转化率为97.3%,LAB的选择性为93.7%,2-LAB的选择性为71.4%。

The liquid-phase alkylation of benzene with 1-dodecene was carried out over WO3/ZrO2 solid superacid catalysts, which was prepared by reaction of zirconium oxyhydroxide with ammonium metatungstate with wet impregnation method. All the catalysts were characterized. The effects of the calcination temperatures, WO3 loading, reaction times, the mole ratio of benzene and 1-dodocene, and mass fraction of catalyst as well as the regeneration of catalyst were studied. The results show that solid superacid sites can be formed in the WO3/ZrO2 system when calcination temperatures is 750 - 850 ℃ and mass fraction of WO3 is 5%- 25 % ; both Lewis and Bronsted acidic centers appear on their surfaces and can transform with each other. WO3/ZrO2 solid superacid catalyst shows high catalytic activities and good regeneration in the liquid-phase alkylation of benzene with 1-dodecene. The optimum reaction conditions are as follows., reaction time 45 min. , calcinations temperature 750℃, mass fraction of WO3 15 %, mole ratio of benzene and 1--dodecene 10, mass fraction of catalyst 4%. Under these conditions, conversion of 1-dodecene is 97.3 %, selectivity of linear chain alkyl benzene （LAB） is 93.7 % and selectivity of 2 -LAB is 71.4%.