固体超强酸SO_4~(2-)/ZrO_2/La_2O_3-HZSM-5的制备和性能
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摘要
引入稀土元素镧并以HZSM-5分子筛担载,制备得固体超强酸催化剂SO_4~(2-)/ZrO_2/La_2O_3-HZSM-5(SZLH),利用FTIR、TEM、SEM、BET等分析测试对催化剂结构进行表征,以癸二酸二丁酯合成反应为模型反应,考察催化剂组成及制备条件对催化性能影响。结果表明,引入镧元素和HZSM-5分子筛可增强SO_4~(2-)/ZrO_2固体超强酸催化剂稳定性和使用寿命,提高催化活性。La~(3+)浸渍浓度为0.07 mol/L,500℃焙烧3h所得催化剂活性最好,在催化癸二酸二丁酯的反应中酯化率可达96.5%,具有良好的重复使用和再生能力。
The solid superacid SO_4~(2-)/ZrO_2/La_2 O_3-HZSM-5(SZLH) was prepared by adding rare earth element La and molecular sieve HZSM-5 to SO_4~(2-)/ZrO_2. The effects of composition and preparation conditions on the structure and activity of catalysts were studied by FT-IR, TEM, SEM and BET. The results showed that the existence of La and HZSM-5 can enhance the acid strength and exhibit better stability and catalytic activity than the catalyst SO_4~(2-)/ZrO_2. The catalysis of the catalyst SZLH was evaluated by esterification of sebacic acid and n-butanol, and the 96.5% yield of dibutyl sebacate was obtained under the optimal reaction conditions using the catalyst impregnated 0.07 mol/L La~(3+) and calcinated at 500℃ for 3 h, which can be availably reused and regenerated.
The solid superacid SO_4~(2-)/ZrO_2/La_2 O_3-HZSM-5(SZLH) was prepared by adding rare earth element La and molecular sieve HZSM-5 to SO_4~(2-)/ZrO_2. The effects of composition and preparation conditions on the structure and activity of catalysts were studied by FT-IR, TEM, SEM and BET. The results showed that the existence of La and HZSM-5 can enhance the acid strength and exhibit better stability and catalytic activity than the catalyst SO_4~(2-)/ZrO_2. The catalysis of the catalyst SZLH was evaluated by esterification of sebacic acid and n-butanol, and the 96.5% yield of dibutyl sebacate was obtained under the optimal reaction conditions using the catalyst impregnated 0.07 mol/L La~(3+) and calcinated at 500℃ for 3 h, which can be availably reused and regenerated.
引文
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[13]赵璧英,马华容,唐有祺.制备方法对MoO_3/ZrO_2结构的影响及MoO_3/ZrO_2固体超强酸的结构特征[J].催化学报,1995,16(3):171-176.
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[2]熊道陵,汪杨,李洋,等.固体酸SO_4~(2-)/C-TiO_2-La_2O_3的制备及其催化性能的研究[J].稀土,2018,39(4):1-9.
[3]廖洋,李洋,马骏,等.SO_4~(2-)/ZrO_2-Nd_2O_3固体酸的制备及其催化活性[J].电子科技大学学报,2015,44(1):140-146.
[4]Arata K,Matsuhashi H,Hino M,Nakamura H.Synthesis of solid superacids and their activities for reactions of alkanes[J].Catalysis Today,2003,81(1):17-20.
[5]Reddy B M,Sreekanth P M,Lakshmanan P,Khan A.Synthesis,characterization and activity study of SO_4~(2-)/Cex Zr1-xO2 solid superacid catalyst[J].Journal of Molecular Catalysis A:Chemica,2006,244(1-2):1-3.
[6]Sohn J R,Lee S H,Lim J S.New solid superacid catalyst prepared by doping ZrO2 with Ce and modifying with sulfate and its catalytic activity f or acid catalysis[J].Catalysis Today,2006,116(2):143-145.
[7]陈淑芬,甘黎明,史文权,等.SO_4~(2-)/La_2O_3-TiO_2催化合成尼泊金酯[J].兰州石化职业技术学院学报,2007,7(3):1-3.
[8]陈淑芬,甘黎明,史文权.SO_4~(2-)/La_2O_3-TiO_2-HZSM-5催化合成癸二酸二丁酯[J].精细石油化工,2005,25(4):7-10
[9]陈淑芬,甘黎明,史文权.SO_4~(2-)/La_2O_3-ZrO_2催化合成亚油酸乙酯[J].应用化工,2006,35(11):822-824.
[10]陈淑芬,甘黎明,尚秀丽,张春兰.SO_4~(2-)/La_2O_3-ZrO_2-HZSM-5催化合成柠檬酸酯[J].兰州石化职业技术学院学报,2013,13(4):12-15.
[11]Furuta S,Mat suhashi H,Arata K.Catalytic action of sulfuted tin oxide for etherification and esterification in comparison with sulphated zirconia[J].Applied Catalysis A:General.2004,269(1-2):187-190.
[12]陈君华,丁志杰,郭雨,等.铁改性HMS分子筛的制备及表征[J].硅酸盐通报,2010,29(4):804-809.
[13]赵璧英,马华容,唐有祺.制备方法对MoO_3/ZrO_2结构的影响及MoO_3/ZrO_2固体超强酸的结构特征[J].催化学报,1995,16(3):171-176.
[14]田部浩三,野依良治.崔圣范,译.超强酸和超强碱[M].北京:化学工业出版社,1986∶106-112.