稀土元素改性SO42-/TiO2及其催化合成乙酸松油酯的研究

赵黔榕1, 吴春华2, 毕韵梅1, 张 涛1, 龚 叶1, 佟艳秀1

（1. 云南师范大学化学化工学院，云南昆明650092；2. 西南林学院木质科学与装饰工程学院，云南昆明650224）

摘 要： 用几种稀土元素对单一型固体超强酸SO42-/TiO2进行改性。结果表明，用Ce4+改性效果较好,且当Ce4+质量分数为7.5％、经500℃焙烧3h后催化剂SO42-/TiO2-Ce4+的催化活性最佳，并用TEM、 XRD和IR对其结构进行了表征。该改性催化剂属于纳米级材料，粒径为32nm, 粒度均匀。并以该固体超强酸SO42-/TiO2-Ce4+为催化剂，松油醇和乙酸酐为原料合成乙酸松油酯。利用正交试验得到适宜的合成条件为：反应温度70℃、催化剂用量3％、松油醇与乙酸酐物质的量之比为1∶1.5、反应时间6h。在此条件下，松油醇转化率达99％，产物中乙酸松油酯含量达90％。与普通型固体超强酸进行比较，SO42-/TiO2-Ce4+具有更高的催化活性和选择性。
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关键词： 固体超强酸；稀土元素；乙酸松油酯；催化合成

中图分类号：TQ352.71; TQ462    文献标识码：A    文章编号：0253-2417(2006)04-0073-05

Studies on  Solid Superacid SO42-/TiO2 Modified  by Rare Earth Element and Its  Catalysis for Synthesis of Terpinyl Acetate

ZHAO Qian­rong1， WU Chun­hua2，BI Yun­mei1， ZHANG Tao1，GONG Ye1，TONG Yan­xiu1

（1.College of Chemistry and Chemical Engineering,Yunnan Normal University, Kunming 650092, China；2.Faculty of Wood Science and Decoration Engineering,Southwest Forestry College, Kunming 650224, China）

Abstract: Common solid superacid SO42-/TiO2 was modified by several rare earth elements. The results showed that Ce4+ was the best modifying agent among these rare earth substances. Ce4+­modified solid surperacid SO42-/TiO2­Ce4+ displayed excellent activity when superacid SO42-/TiO2 was impregnated by 7.5 % Ce4+ and then calcined at 500 ℃ for 3 h. The structure of SO42-/TiO2­Ce4+ was characterized by TEM, XRD and IR methods. The catalyst was a nanomaterial with  uniform granularity of 32 nm. Synthesis of terpinyl acetate from terpineol and acetic anhydride with solid superacid SO42-/TiO2­Ce4+as catalyst had been studied for the first time. By orthogonal test, the optimum condition was obtained as follows: reaction temperature 70 ℃, reaction time 6 h, catalyst dosage 3 %,ratio of terpineol to acetic anhydride 1∶1.5. Under this condition, the conversion of terpineol was over 99 %, and the content of terpinyl acetate in the product was 90 %. Compared with common superacid SO42-/TiO2, the modified SO42-/TiO2­Ce4+ had higher catalytic activity and selectivity.

Key words: solid superacid;rare earth element;terpinyl acetate;catalytic synthesis