SBA-15负载硫酸化氧化锆固体酸材料的设计合成及其酯交换反应催化性能研究  

Designed Synthesis of SBA-15 Supported Sulfated Zirconia Solid Acid Materials and Their Catalytic Performance for Transesterification Reaction

作　　者：段晓宣 王恒燕 潘大海[2] 陈树伟[2] 于峰[1] 闫晓亮[1] 李瑞丰[1] Duan Xiaoxuan;Wang Hengyana;Pan Dahai;Chen Shuwei;Yu Feng;Yan Xiaoliang;Li Ruifeng(College of Chemical Engineering and Technology,Taiyuan University of Technology,Taiyuan 030024,China;College of Chemistry,Taiyuan University of Technology,Taiyuan 030024,China)

机构地区：[1]太原理工大学化学工程与技术学院,太原030024 [2]太原理工大学化学学院,太原030024

出　　处：《化学学报》2024年第7期755-762,共8页Acta Chimica Sinica

基　　金：国家自然科学基金面上项目(21975174和22378286)资助.

摘　　要：借助硝酸锆水解所产生的弱酸性环境,结合高温水热处理,一步合成了具有规整有序孔道结构且孔壁表面富含锆氧物种的Zr-SBA-15介孔材料,并将其用于硫酸基团的高效稳定负载.介孔骨架中大量锆原子的高度均匀掺杂及孔壁表面Zr—O—Si键的形成不仅有利于负载更多量的硫酸基团,且能在诱使超强酸性中心产生的同时,有效抑制硫酸化锆氧活性组分在反应过程中流失,致使固体酸材料SO_(4)^(2)/Zr-SBA-15显示出较传统负载型硫酸化氧化锆固体酸更高的酸量和酸强度,继而在大豆油合成生物柴油酯交换反应中显示出明显提升的催化活性和稳定性,其在经三次重复使用过程中,均可实现将91%以上的大豆油近完全转化为生物柴油.Ordered mesoporous Zr-SBA-15 material with a highly homogenous distribution of Zr within mesoporous walls was synthesized by a facile one-step high temperature hydrothermal treatment approach.In the proposed approach,the coop-erative self-assembly between amphiphilic triblock copolymer P123 and silicon hydroxyl(Si-OH)species from the hydroly-sis of tetraethyl orthosilicate(TEOS)was carried out to form an organic-inorganic composite with an ordered mesostructure(as-synthesized SBA-15,silica matrices with an embeddedness of P123 micelles)under a weak acidic medium originated from the hydrolysis of zirconium tetranitrate;during the followed high temperature hydrothermal treatment process,the fur-ther hydrolysis of zirconium precursor promotes more Zr4+transferring to zirconium hydroxyl(Zr-OH)species,and the condensation between the Zr-OH species and Si-OH species,which exist in the synthesis solution and within the mesoporous walls of as-synthesized SBA-15,respectively,leads to a large amount of Zr atoms being highly homogenously grafted into the mesoporous walls of as-synthesized SBA-15 and the formation of framework Zr—O—Si bonds.After calcination to re-move the organic P123 micelles,the ordered mesoporous Zr-SBA-15 material was obtained and used as a support for the immobilization of sulfuric acid by a traditional impregnation method.The characterization results confirmed that compared to supports SBA-15 and SBA-15-supported zirconia(Zr/SBA-15,prepared by the impregnation of SBA-15 with zirconium tetranitrate aqueous soliton followed drying and calcination treatments),the use of support Zr-SBA-15 can realize a stable immobilization of much more sulfuric acid groups,due to the highly homogenous dispersions of ZrOx species on the meso-porous surface of Zr-SBA-15.In addition,the double attracting electron role from supported sulfuric acid group and Si ele-ment with higher electronegativity than that of Zr element can further induce an decrease in the electron cloud density of Zr4+existing in the surface Zr—O�

关 键 词：介孔材料 固体酸 硫酸化氧化锆 Zr-SBA-15 酯交换反应 

分 类 号：TE667[石油与天然气工程—油气加工工程] O643.36[理学—物理化学]