SO_3H-MCM-41对丙烯酸和异丁烯加成反应的催化性能  

Catalytic Performance of SO_3H-MCM-41 on Addition Reaction of Acrylic Acid and i-Butene

作　　者：周峰[1] 汤吉海[1] 陈献[1] 费兆阳[1,2] 崔咪芬[1] 乔旭[1,2] 

机构地区：[1]南京工业大学化学化工学院,江苏南京210009 [2]南京工业大学材料化学工程国家重点实验室,江苏南京210009

出　　处：《石油学报（石油加工）》2014年第4期629-637,共9页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：江苏省高校自然科学研究重点项目(09KJA530004);江苏省产学研前瞻性联合研究项目(BY2011105)资助

摘　　要：采用一步水热共缩合法制备了表面磺酸嫁接的介孔分子筛SO3H-MCM-41,采用XRD、N2吸附-脱附、红外吸收光谱、吡啶吸附红外光谱、酸碱滴定等手段对其物理化学性质进行了表征,考察了SO3H-MCM-41对丙烯酸与异丁烯直接加成反应合成丙烯酸叔丁酯的催化性能,在n(i-Butene)/n(Acrylic acid)=1时,探讨了催化剂制备条件n(Sulfonic acid)/n(Silica),丙烯酸与异丁烯加成反应条件m(t-Butanol)/m(Acrylic acid)、m(Catalyst)/m(Acrylic acid)和反应温度对反应转化率及产物选择性的影响。结果表明,SO3H-MCM-41表面成功嫁接了磺酸基团,嫁接后的分子筛具有纯硅MCM-41分子筛的晶体结构。提高n(i-Butene)/n(Acrylic acid)可以显著提高丙烯酸转化率,而丙烯酸叔丁酯选择性基本保持不变;采用n(Sulfonic acid)/n(Silica)=0.3制备的SO3H-MCM-41催化剂,在反应时间6h、、反应温度50℃、n(i-Butene)/n(Acrylic acid)=2、m(Catalyst)/m(Acrylic acid)=0.01和m(t-Butanol)/m(Acrylic acid)=0.04的条件下,丙烯酸转化率为90.0%,丙烯酸叔丁酯选择性为92.8%,二异丁烯选择性为4.8%。SO3H-MCM-41催化剂重复使用5次其催化活性保持稳定。在工业生产过程中,提高丙烯酸转化率有利于降低丙烯酸与丙烯酸叔丁酯的分离能耗。Mesoporous SOa H-MCM-41 was prepared by direct hydrothermal condensation method, and characterized by using XRD, Ne adsorption-desorption, FT-IR, Py-IR and acid-base titration. The catalytic performance of SOa H-MCM-41 on synthesis of t-butyl acrylate by the direct addition of acrylic acid with isobutene was studied. With n（i-Butene）/n（Acrylic acid） of 1, the effects of the preparation condition of n （Sulfonic aeid）/n （Silica） and the direct addition reaction conditions of reaction temperature, rn （ t-Butanol）/n （ Acrylic acid） and rn （ Catalyst）/n （ Acrylic acid） on conversion of acrylic acid and selectivity of t-butyl acrylate were investigated. It was shown that the sulfonic acid functional group was successfully grafted onto the surface of MCM-41 and the typical mesoporous structure of MCM-41 was generally remained. With the increase of n （i-Butene）/n（Acrylic acid） the conversion ofacrylic acid could be increased, while t-butyl acrylate selectivity was unchanged. With the SO3H-MCM-41 as catalyst prepared at n（Sulfonic acid）/n（Silica）=0.3 and under the conditions of reaction time 6 h, reaction temperature 50℃, n（i-Butene）/n（Acrylic acid） = 2, m （t-Butanol）/m （ Acrylic acid） = 0.01 and m （Catalyst）/m （ Acrylic acid） = 0.04 in the addition reaction, the conversion of acrylic acid could reach 90%, selectivity of t-butyl acrylate and diisobutylene were 92.8% and 4.8%, respectively. Moreover, the catalyst could be reused for 5 times with its catalytic activity essentially unchanged. High conversion of acrylic acid was benefit to reduce energy consumption of separation in industrial process.

关 键 词：SO3H-MCM-41 丙烯酸 异丁烯 丙烯酸叔丁酯 加成反应 

分 类 号：O624.5[理学—有机化学]