Zr-SBA-15催化肉桂醛的MPV转移加氢性能
|
摘要
以正硅酸乙酯和硝酸氧锆为原料,采用一锅法制备了不同Zr/Si物质的量比的Zr-SBA-15催化剂,借助N_2物理吸附、XRD、NH_3-TPD、吡啶-原位红外光谱考察了Zr/Si物质的量比对Zr-SBA-15结构、织构、表面酸性质及催化肉桂醛Meerwein-Ponndorf-Verley(MPV)转移加氢性能的影响;探讨了Zr-SBA-15结构、织构及表面酸性质对其催化肉桂醛MPV转移加氢性能的影响机制。结果表明,Zr-SBA-15催化剂均呈现规整的介孔结构特征,表面酸中心以L酸为主。随Zr/Si物质的量比增加,Zr-SBA-15催化剂的最可几孔径逐渐减小,L酸量持续增加,B酸量变化不大,肉桂醛转化率呈现先增加后趋于稳定的趋势,目标产物肉桂醇选择性增加,副产物1-苯丙烯-2-丙基醚选择性下降。在Zr/Si物质的量比为0.10时,Zr-SBA-15催化剂显示最优的催化性能,肉桂醛转化率为96.2%,目标产物肉桂醇选择性达到95.2%,经7次循环后催化剂仍保持90%以上的肉桂醛转化率和95%以上的肉桂醇选择性。
A series of Zr-SBA-15 catalysts with different Zr/Si molar ratio were prepared by one-pot method using tetraethyl orthosilicate and zirconium dinitrate oxide as raw matrials.The effects of Zr/S molar ratio on the structure,texture,surface acidity and catalytic performance of Zr-SBA-15 catalysts for the(Meerwein-Ponndorf-Verley)MPV transfer hydrogenation of cinnamaldehyde were investigated by means of N_2 physical adsorption,X-ray powder diffraction,NH_3 temperature-programmed desorption and pyridine in situ infrared spectroscopy.The results showed that all prepared Zr-SBA-15 catalysts exhibited regular hexagonal mesoporous structure with L acid as main surface acid center.With the increase of Zr/Si molar ratio,the most probable pore size of Zr-SBA-15 catalyst decreased gradually,the amount of L acid kept increasing,while the amount of B acid changed lightly.The conversion of cinnamaldehyde initially increased and then tended to be stable.The selectivity of the target product cinnamyl alcohol increased However,the selectivity of the by-product 1-benzene propylene-2-propyl ether decreased.When the Zr/S molar ratio was 0.1,the prepared Zr-SBA-15 catalyst showed the optimal catalytic performance.The conversion of cinnamaldehyde reached 96.2%,and the selectivity of cinnamyl alcohol was 95.2%.After the Zr-SBA-15 catalyst being recycled for 7 times,the conversion of cinnamaldehyde was still kept above 90%and the selectivity of cinnamyl alcohol was over 95%.
A series of Zr-SBA-15 catalysts with different Zr/Si molar ratio were prepared by one-pot method using tetraethyl orthosilicate and zirconium dinitrate oxide as raw matrials.The effects of Zr/S molar ratio on the structure,texture,surface acidity and catalytic performance of Zr-SBA-15 catalysts for the(Meerwein-Ponndorf-Verley)MPV transfer hydrogenation of cinnamaldehyde were investigated by means of N_2 physical adsorption,X-ray powder diffraction,NH_3 temperature-programmed desorption and pyridine in situ infrared spectroscopy.The results showed that all prepared Zr-SBA-15 catalysts exhibited regular hexagonal mesoporous structure with L acid as main surface acid center.With the increase of Zr/Si molar ratio,the most probable pore size of Zr-SBA-15 catalyst decreased gradually,the amount of L acid kept increasing,while the amount of B acid changed lightly.The conversion of cinnamaldehyde initially increased and then tended to be stable.The selectivity of the target product cinnamyl alcohol increased However,the selectivity of the by-product 1-benzene propylene-2-propyl ether decreased.When the Zr/S molar ratio was 0.1,the prepared Zr-SBA-15 catalyst showed the optimal catalytic performance.The conversion of cinnamaldehyde reached 96.2%,and the selectivity of cinnamyl alcohol was 95.2%.After the Zr-SBA-15 catalyst being recycled for 7 times,the conversion of cinnamaldehyde was still kept above 90%and the selectivity of cinnamyl alcohol was over 95%.
引文
[1]Wu Wentao(武文涛),Jia Yingping(贾颖萍),Yin Jingmei(尹静梅),et al.Research progress on selective hydrogenation of cinnamaldehyde to cinnamyl alcohol[J].Chemical Intermediates(化工中间体),2009,5(4):1-5.
[2]Cao Genting(曹根庭),Xue Jilong(薛继龙),Xiao Xuechun(肖雪春),et al.Mechanism analysis of surface hydrogenation of cinnamaldehyde on M13(M=Au,Pt)Clusters[J].CIESC Journal(化工学报),2016,67(4):1333-1339.
[3]Ma H F,Yu T,Pan X L,et al.Confinement effect of carbon nanotubes on the product distribution of selective hydrogenation of cinnamaldehyde[J].Chinese Journal of Catalysis,2017,38(8):1315-1321.
[4]Xu Liyong(许莉勇),Zhang Xinbo(张新波),Zhang Bin(张斌),et al.Recent progress in heterogeneous catalytic selective hydrogenation of cinnamaldehyde to cinnamylalcohol[J].Chinese Journal of Modern Applied Pharmacy(中国现代应用药学),2010,27(7):599-603.
[5]Evans D A,Nelson S G,Gagne M R,et al.A chiral samarium-based catalyst for the asymmetric Meerwe-in-Ponndorf-Verley reduction[J].Journal of the American Ceramic Society,1993,115(2):9800-9801.
[6]Campbell E J,Zhou H Y,Nguyen S T.Catalytic MeerweinPondorf-Verley reduction by simple aluminum complexes[J].Organic Letters,2001,3(15):2391-2393.
[7]Boukha Z,Fitian L,Haro M L.Influence of the calcintion temperature on the nano-structural properties,surface basicity,and catalytic behavior of alumina-supported lanthana samples[J].Journal of Catalysis,2010,272(1):121-130.
[8]Komanoya T,Nakajima K,KitanoM,et al.Synergistic catalysis by Lewis acid and base Sites on ZrO2 for Meerwein-Ponndorf-Verley reduction[J].Journal of Physical Chemistry C,2015,119(47):26540-26546.
[9]Cai W M,Yang J,Sun H F,et al.Surface titanium oxide loaded on a special alumina as high-performance catalyst for reduction of cinnamaldehyde by isopropanol[J].Chinese Journal of Catalysis,2017,38(8):1330-1337.
[10]Gao Z K,Hong Y C,Hu Z,et al.Transfer hydrogenation of cinnamaldehyde with 2-propanol on Al2O3 and SiO2-Al2O3 catalysts:role of Lewis and Br?nsted acidic sites[J].Catalysis Science and Technology,2017,7(19):4511-4519.
[11]Liu S H,Jaenicke S,Chuah G K.Hydrous zirconia as a selective catalyst for the Meerwe in Ponndorf Verley reduction of cinnamaldehyde[J].Journal of Catalysis,2002,206(2):321-330.
[12]Jin Bin(金滨),Zhang Bo(张波),Liao Jiangfen(廖江芬),et al.Progress on MPV reduction catalysts ofα,β-unsaturated aldehydes/ketones[J].Chemical Production and Technology(化工生产与技术),2006,13(2):38-41.
[13]Zhu Y Z,Jaenicke S,Chuah G K.Supported zirconium propoxideaversatile heterogeneous catalyst for the Meerwein Ponndorf Verley reduction[J].Journal of Catalysis,2003,218(2):396-404.
[14]Zhu Y Z,Chuah G K,Jaenicke S.Chemo-andregios elective Meerwein-ponndorf-verley and Oppenauer reactions catalyzed by Al-free Zr-zeolite beta[J].Journal of Catalysis,2004,227(1):1-10.
[15]Lou Xinyue(娄馨月),Chen Xihui(陈希慧),Ren Lifeng(任利锋).Catalyzing activity of ZrO2/SiO2 samples in Meerwein-PonndorfVerley reduction of citral[J].Journal of Guangxi University:Natural Science Edition(广西大学学报:自然科学版),2009,34(6):740-743.
[16]Zhao D,Feng J,Huo Q,et al.Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores[J].Science,1998,279(5350):548-552.
[17]Melero J A,Bautista L F,Iglesias J,et al.Zr-SBA-15 acid catalyst:optimization of the synthesis and reaction conditions for biodiesel production from low-grade oils and fats[J].Catalysis Today,2012,195(1):44-53.
[18]Yang L,Yang X,Tian E,et al.Mechanistic insights into the production of methyl lactate by catalytic conversion of carbohydrates on mesoporous Zr-SBA-15[J].Journal of Catalysis,2016,333:207-216.
[19]Tan Ying(谈瑛),Li Yongfei(李勇飞),Wei Yuanfeng(魏元峰),et al.High selective synthesis of orthoisomer of bisphenol F catalyzed by Zr-SBA-15[J].CIESC Journal(化工学报),2016,67(5):1900-1906.
[20]Maria D G,Alina M B,Juan M C,et al.Evidences of the in situ generation of highly active Lewis acid species on Zr-SBA-15[J].Applied Catalysis A:General,2009,371:85-91.
[21]Yang Xiyao(杨锡尧).Research methods of solid catalysts.Chapter13 temperature-programming analysis techniques(below)[J].Petrochemical(石油化工),2002,31(1):63-73.
[22]Tabe Hiromi,Misonoo Cheng,Ono Kami,et al.New solid acid and bases:their catalytic properties,Second Edition[M].Beijing:Chemical Industry Press(化学工业出版社),1992:89.
[2]Cao Genting(曹根庭),Xue Jilong(薛继龙),Xiao Xuechun(肖雪春),et al.Mechanism analysis of surface hydrogenation of cinnamaldehyde on M13(M=Au,Pt)Clusters[J].CIESC Journal(化工学报),2016,67(4):1333-1339.
[3]Ma H F,Yu T,Pan X L,et al.Confinement effect of carbon nanotubes on the product distribution of selective hydrogenation of cinnamaldehyde[J].Chinese Journal of Catalysis,2017,38(8):1315-1321.
[4]Xu Liyong(许莉勇),Zhang Xinbo(张新波),Zhang Bin(张斌),et al.Recent progress in heterogeneous catalytic selective hydrogenation of cinnamaldehyde to cinnamylalcohol[J].Chinese Journal of Modern Applied Pharmacy(中国现代应用药学),2010,27(7):599-603.
[5]Evans D A,Nelson S G,Gagne M R,et al.A chiral samarium-based catalyst for the asymmetric Meerwe-in-Ponndorf-Verley reduction[J].Journal of the American Ceramic Society,1993,115(2):9800-9801.
[6]Campbell E J,Zhou H Y,Nguyen S T.Catalytic MeerweinPondorf-Verley reduction by simple aluminum complexes[J].Organic Letters,2001,3(15):2391-2393.
[7]Boukha Z,Fitian L,Haro M L.Influence of the calcintion temperature on the nano-structural properties,surface basicity,and catalytic behavior of alumina-supported lanthana samples[J].Journal of Catalysis,2010,272(1):121-130.
[8]Komanoya T,Nakajima K,KitanoM,et al.Synergistic catalysis by Lewis acid and base Sites on ZrO2 for Meerwein-Ponndorf-Verley reduction[J].Journal of Physical Chemistry C,2015,119(47):26540-26546.
[9]Cai W M,Yang J,Sun H F,et al.Surface titanium oxide loaded on a special alumina as high-performance catalyst for reduction of cinnamaldehyde by isopropanol[J].Chinese Journal of Catalysis,2017,38(8):1330-1337.
[10]Gao Z K,Hong Y C,Hu Z,et al.Transfer hydrogenation of cinnamaldehyde with 2-propanol on Al2O3 and SiO2-Al2O3 catalysts:role of Lewis and Br?nsted acidic sites[J].Catalysis Science and Technology,2017,7(19):4511-4519.
[11]Liu S H,Jaenicke S,Chuah G K.Hydrous zirconia as a selective catalyst for the Meerwe in Ponndorf Verley reduction of cinnamaldehyde[J].Journal of Catalysis,2002,206(2):321-330.
[12]Jin Bin(金滨),Zhang Bo(张波),Liao Jiangfen(廖江芬),et al.Progress on MPV reduction catalysts ofα,β-unsaturated aldehydes/ketones[J].Chemical Production and Technology(化工生产与技术),2006,13(2):38-41.
[13]Zhu Y Z,Jaenicke S,Chuah G K.Supported zirconium propoxideaversatile heterogeneous catalyst for the Meerwein Ponndorf Verley reduction[J].Journal of Catalysis,2003,218(2):396-404.
[14]Zhu Y Z,Chuah G K,Jaenicke S.Chemo-andregios elective Meerwein-ponndorf-verley and Oppenauer reactions catalyzed by Al-free Zr-zeolite beta[J].Journal of Catalysis,2004,227(1):1-10.
[15]Lou Xinyue(娄馨月),Chen Xihui(陈希慧),Ren Lifeng(任利锋).Catalyzing activity of ZrO2/SiO2 samples in Meerwein-PonndorfVerley reduction of citral[J].Journal of Guangxi University:Natural Science Edition(广西大学学报:自然科学版),2009,34(6):740-743.
[16]Zhao D,Feng J,Huo Q,et al.Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores[J].Science,1998,279(5350):548-552.
[17]Melero J A,Bautista L F,Iglesias J,et al.Zr-SBA-15 acid catalyst:optimization of the synthesis and reaction conditions for biodiesel production from low-grade oils and fats[J].Catalysis Today,2012,195(1):44-53.
[18]Yang L,Yang X,Tian E,et al.Mechanistic insights into the production of methyl lactate by catalytic conversion of carbohydrates on mesoporous Zr-SBA-15[J].Journal of Catalysis,2016,333:207-216.
[19]Tan Ying(谈瑛),Li Yongfei(李勇飞),Wei Yuanfeng(魏元峰),et al.High selective synthesis of orthoisomer of bisphenol F catalyzed by Zr-SBA-15[J].CIESC Journal(化工学报),2016,67(5):1900-1906.
[20]Maria D G,Alina M B,Juan M C,et al.Evidences of the in situ generation of highly active Lewis acid species on Zr-SBA-15[J].Applied Catalysis A:General,2009,371:85-91.
[21]Yang Xiyao(杨锡尧).Research methods of solid catalysts.Chapter13 temperature-programming analysis techniques(below)[J].Petrochemical(石油化工),2002,31(1):63-73.
[22]Tabe Hiromi,Misonoo Cheng,Ono Kami,et al.New solid acid and bases:their catalytic properties,Second Edition[M].Beijing:Chemical Industry Press(化学工业出版社),1992:89.