Abstract: A series of sulphated Al2O3-TiO2 mixed oxides were prepared by sol-gel and dipping process and used as catalysts in synthesis of borneol. The structure and properties of SO42-/TiO2-Al2O3 solid superacid catalysts were characterized by XRD, NH3-TPD, FT-IR, Py-FTIR, XPS, SEM techniques, and relationship between the catalytic performance and the structure was explored. The optimal condition for the preparation of the catalyst was obtained as follows: n(TiO2)/n(Al2O3)=1∶2, concentration of impregnation 1 mol/L, calcination temperature of the catalysts 500 ℃. Meanwhile, the effects of the dosage of level of catalyst, molar ratio of α-pinene to oxalic acid, reaction time on borneol synthesis reaction was investigated. The results showed that when the dosage of level of catalyst was 6% and molar ratio of α-pinene to oxalic acid was 1∶0.4, by using the program temperature heating method (65 ℃-1 h, 75 ℃-4 h, 90 ℃-1 h), i.e. the optimized condition, the resultant solid superacid SO42-/TiO2-Al2O3 catalyst performed the best catalytic effect to borneol synthesis reaction, as α-pinene was completely converted and high selectivity of borneol (58.63% yield) was achieved. After 6 times reuse, the catalyst still maintained good performance—α-pinene conversion rate unchanged, yield of borneol decreased by 2.99%.
王鹤林,蒋丽红,王亚明,焦星星,潘登. 固体超强酸SO42-/TiO2-Al2O3的制备及其催化合成冰片*[J]. 材料导报编辑部, 2017, 31(22): 43-49.
WANG Helin, JIANG Lihong, WANG Yaming, JIAO Xingxing, PAN Deng. Preparation of SO42-/TiO2-Al2O3 Soild Superacid Catalyst and Its Catalytic Activity for Borneol Synthesis. Materials Reports, 2017, 31(22): 43-49.
1 Yin Q, Shi X, Ding H, et al. Interactions of borneol with DPPC phospholipid membranes: A molecular dynamics simulation Study[J]. Int J Mol Sci, 2014,15(11):20365. 2 Ehrnh?ferressler M M, Fricke K, Pignitter M, et al. Identification of 1,8-cineole, borneol, camphor, and thujone as anti-inflammatory compounds in a salvia officinalis L. infusion using human gingival fibroblasts[J]. J Agric Food Chem, 2013,61(14):3451. 3 Li Y H, Sun X P, Zhang Y Q, et al. The antithrombotic effect of borneol related to its anticoagulant property[J]. Am J Chin Med, 2008,36(4):719. 4 Liu R, Zhang L, Lan X, et al. Protection by borneol on cortical neurons against oxygen-glucose deprivation/reperfusion: Involvement of anti-oxidation and anti-inflammation through nuclear transcription factor κappaB signaling pathway[J]. Neurosci, 2011,176:408. 5 Imanshahidi M, Hosseinzadeh H. The pharmacological effects of salvia, species on the central nervous system[J]. Phytother Res, 2006,20(6):427. 6 Kong Q X, Wu Z Y, Chu X, et al. Study on the anti-cerebral ischemia effect of borneol and its mechanism[J]. Afr J Tradit, Complementary Altern Med, 2014,11(1):161. 7 Almeida J R G D S, Souza G R, Silva J C, et al. Borneol, a bicyclic monoterpene alcohol, reduces nociceptive behavior and inflammatory response in mice[J]. Sci World J, 2013,2013(4):808460. 8 Bhatia S P, Letizia C S, Api A M. Fragrance material review on borneol[J]. Food Chem Toxicol, 2008,46(11):S77. 9 Zhao J Y, Yang L, Du S Y, et al. Comparative pharmacokinetic studies of borneol in mouse plasma and brain by different administrations[J]. J Zhejiang Uni, Sci B, 2012,13(12):990. 10 Zhao Zhendong, Liu Xianzhang. Fine chemical utilization of turpentine oil (Ⅱ)——perfumes derived from turpentine oil(A)[J]. Biomass Chem Eng, 2001,35(2):38(in Chinese). 赵振东,刘先章. 松节油的精细化学利用(Ⅱ)——松节油合成日化香料(上)[J].生物质化学工程, 2001,35(2):38. 11 Bai Yun. The general situation of flavor from turpentine oil[J]. China Food Addit, 2006(4):133(in Chinese). 白芸. 从松节油制得的食用香料概况[J].中国食品添加剂, 2006(4):133. 12 Liu S, Xie C, Yu S, et al. Esterification of α-pinene and acetic acid using acidic ionic liquids as catalysts[J]. Catal Commun, 2008, 9(7):1634. 13 Li Qun, Huang Shuyun. Study on catalytic synthesis of borneol with solid strong acid[J]. Chem Ind For Prod,1996(2):45(in Chinese). 黎群,黄淑云. 固体强酸催化合成冰片的研究[J].林产化学与工业,1996(2):45. 14 Yang Yiwen, Chen Huizong, Li Lei. Synthesis of borneol from α-Pinene catalyzed by solid superacid SO42-/ZrO2-NiO[J]. Adv Fine Petrochem,2009,10(9):36(in Chinese). 杨义文,陈慧宗,李蕾. 固体超强酸SO42-/ZrO2-NiO催化α-蒎烯合成龙脑[J].精细石油化工进展, 2009,10(9):36. 15 Wang Chunying, Wang Pan, Qi Xinhua, et al. Transformation of cellulose to levulinic acid over SO42-/Al2O3-TiO2 catalyst[J]. Chem Ind Eng Prog, 2009, 28(1):126(in Chinese). 王春英,王攀,漆新华,等. SO42-/Al2O3-TiO2转化纤维素生成乙酰丙酸[J].化工进展, 2009,28(1):126. 16 Han Huan, Jiang Lihong, Wang Yaming, et al. Preparation of Ni/TiO2-Al2O3 catalyst and its application in catalyzing hydrogrnation of turpentine[J]. Chem Ind For Prod,2016(1):92(in Chinese). 韩欢,蒋丽红,王亚明,等. Ni/TiO2-Al2O3催化剂的制备及其在松节油催化加氢反应中的应用[J]. 林产化学与工业,2016(1):92. 17 Jiang Y X, Chen X M, Mo Y F, et al. Preparation and properties of Al-PILC supported SO42-/TiO2, superacid catalyst[J]. J Mol Catal A: Chem, 2004,213(2):231. 18 Zhu Jianfei, Zhu Yiqing. The influence o preparation conditions of Al2O3/TiO2 upon acid sites properties[J]. Chin J Inorg Chem,1999,15(4):429(in Chinese). 朱建飞,朱毅青. Al2O3-TiO2二元氧化物的制备条件对酸性的影响[J].无机化学学报, 1999,15(4):429. 19 Schoonheydt R, Lunsford J. In infrared spectroscopic characterization of the adsorption and reactions of SO2 on MgO[J]. Asia-Pac Conf Commun Fourth Optoelectron Commun Conf, 1972(2):1446. 20 Yadav G D, Nair J J. Sulfated zirconia and its modified versions as promising catalysts for industrial processes[J]. Microp Mesop Mater, 1999,33(1-3): 1. 21 Zhai Long, Xu Lianchi, Liu xiguang, et al. Preparation and catalytic activity of mesoporous WO3-CeO2-ZrO2 solid superacid catalyst[J]. J Chin Silic Soc, 2016,44(7):1033(in Chinese). 翟龙,许连池,刘曦光,等. 介孔WO3-CeO2-ZrO2固体超强酸的制备与催化性能[J].硅酸盐学报,2016,44(7):1033. 22 Guan Guofeng, Tan Qiang, Wan Hui. Synthesis of tetraoctyl pyromellitate on solid superacid SO42-/TiO2- Al2O3[J]. Petrochem Technol, 2005,34(7):643(in Chinese). 管国锋,谭强,万辉. SO42- /TiO2-Al2O3固体酸催化剂的表征及其催化合成均苯四甲酸四异辛酯[J].石油化工,2005,34(7):643. 23 Xia Q H, Hidajat K, Kawi S. Effect of ZrO2 loading on the structure, acidity, and catalytic activity of the SO42-/ZrO2/MCM-41 acid catalyst[J]. J Catal, 2002,205(2):318. 24 Yu M S, Rubtsov V I, Vasilets V N, et al. EELS, XPS and IR study of C60·2S8 compound[J]. Synth Met, 1995,70(1):1381. 25 Dutta S N, Dowerah D, Frost D C. Study of sulphur in Assam coals by X-ray photoelectron spectroscopy[J]. Fuel, 1983,62(7): 840. 26 Wei F, Ni L, Cui P. Preparation and characterization of N-S-codoped TiO2 photocatalyst and its photocatalytic activity[J]. J Hazard Mater, 2008,156(1-3): 135.
渝公网安备50019002502923号 版权所有：《材料导报》编辑部
2017, Vol. 31 
