趙黔榕1, 吳春華2, 畢韻梅1, 張 濤1, 龔 葉1, 佟艷秀1

（1. 云南師范大學(xué)化學(xué)化工學(xué)院，云南昆明650092；2. 西南林學(xué)院木質(zhì)科學(xué)與裝飾工程學(xué)院，云南昆明650224）

摘 要： 用幾種稀土元素對(duì)單一型固體超強(qiáng)酸SO42-/TiO2進(jìn)行改性。結(jié)果表明，用Ce4+改性效果較好,且當(dāng)Ce4+質(zhì)量分?jǐn)?shù)為7.5％、經(jīng)500℃焙燒3h后催化劑SO42-/TiO2-Ce4+的催化活性最佳，并用TEM、 XRD和IR對(duì)其結(jié)構(gòu)進(jìn)行了表征。該改性催化劑屬于納米級(jí)材料，粒徑為32nm, 粒度均勻。并以該固體超強(qiáng)酸SO42-/TiO2-Ce4+為催化劑，松油醇和乙酸酐為原料合成乙酸松油酯。利用正交試驗(yàn)得到適宜的合成條件為：反應(yīng)溫度70℃、催化劑用量3％、松油醇與乙酸酐物質(zhì)的量之比為1∶1.5、反應(yīng)時(shí)間6h。在此條件下，松油醇轉(zhuǎn)化率達(dá)99％，產(chǎn)物中乙酸松油酯含量達(dá)90％。與普通型固體超強(qiáng)酸進(jìn)行比較，SO42-/TiO2-Ce4+具有更高的催化活性和選擇性。

關(guān)鍵詞： 固體超強(qiáng)酸；稀土元素；乙酸松油酯；催化合成

中圖分類號(hào)：TQ352.71; TQ462    文獻(xiàn)標(biāo)識(shí)碼：A    文章編號(hào)：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