异丁烯与醋酸酯化合成醋酸叔丁酯
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摘要
以锆复合氧化物和大孔强酸性阳离子交换树脂为催化剂,催化异丁烯与醋酸合成了醋酸叔丁酯。采用正丁胺电位滴定法对催化剂的酸强度和酸量进行了表征。结果表明:对异丁烯与醋酸酯化反应而言,随着酸量增加,转化率增大,但酸强度增大会导致选择性下降。以异丁烯质量分数为10%的混合烃为原料,D008为催化剂,异丁烯单程转化率可达80%,醋酸叔丁酯的选择性为95.98%。
Esterification of acetic acid with isobutene to tert-butyl acetate catalyzed by zirconium composite oxides and macroporous strong acid cation exchange resin was investigated. The acid strength and the number of acid site of catalysts were measured by potentiometric titration with n-butylamine. The results showed that the conversion of isobutene increases with increasing the acid amount, but the selectivity of tert-butyl acetate decreases with increasing the acid strength. When the esterification was carried out using the mixed hydrocarbon containing 10% mass fraction of isobutylene as raw material and D008 as catalyst, the single conversion of isobutene reached 80% and the selectivity of tert-butyl acetate reached 95.98%.
Esterification of acetic acid with isobutene to tert-butyl acetate catalyzed by zirconium composite oxides and macroporous strong acid cation exchange resin was investigated. The acid strength and the number of acid site of catalysts were measured by potentiometric titration with n-butylamine. The results showed that the conversion of isobutene increases with increasing the acid amount, but the selectivity of tert-butyl acetate decreases with increasing the acid strength. When the esterification was carried out using the mixed hydrocarbon containing 10% mass fraction of isobutylene as raw material and D008 as catalyst, the single conversion of isobutene reached 80% and the selectivity of tert-butyl acetate reached 95.98%.
引文
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[3]Huang Yuxin(黄玉鑫),Tang Jihai(汤吉海),Chen Xian(陈献),et al.Process simulation of tert-butyl acetate production by distillation column integrated with side reactors under different temperatures[J].CIESC Journal(化工学报),2015,66(10):4045-4046.
[4]Harmer M A,Sun Q.Solid acid catalysis using ion-exchange resins[J].Applied Catalysis A,2001,221(1):45-62.
[5]Xu Bin(徐斌),Huang Hua(黄华),Xie Qiongyu(谢琼玉).Method for preparing and purifying tert-butyl acetate:CN1884248[P].2006-07-04.
[6]Ma Y D,Wang Q L,Hao Y,et al.Zeolite-catalyzed esterification I.Synthesis of acetates,benzoates and phthalates[J].Applied Catalysis A,1996,139(51):51-57.
[7]Kirumakki S R,Nagaraju A N,Chary K V R.Esterification of alcohols with acetic acid over zeolites Hβ,HY and HZSM5[J].Applied Catalysis A,2006,299(1):185-192.
[8]Gokulakrishnan N,Pandurangan A,Sinha P K.Esterification of acetic acid with propanol isomers under autogeneous pressure:Acatalytic activity study of Al-MCM-41 molecular sieves[J].Journal of Molecular Catalysis A,2007,263(55):55-61.
[9]Makoto M.Recent progress in the practical applications of heteropolyacid and perovskite catalysts:Catalytic technology for the sustainable society[J].Catalysis Today,2009,144(3):285-291.
[10],Suwannakarn K,Lotero E,Jr J G G,et al.A comparative study of gas phase esterification on solid acid catalysts[J].Catalysis Letters,2007,114(122):122-128
[11]López D E,Suwannakarn K,Bruce D A,et al.Esterification and transesterification on tungstated zirconia:Effect of calcination temperature[J].Journal of Catalysis,2007,247(1):43-50
[12]Hideshi H,Yoshi O.Solid acid catalysis[M].Gao Zi(高兹),Yue Yinghong(乐英红),Hua Weiming(华伟明),trans.Shanghai:Fudan University Press,2015:177.
[13]Liu Xuan(刘璇).Study on tert-butyl acetate synthesis[D].Shanghai:East China University of Science and Technology(华东理工大学),2010.
[14]Santiesteban J G,Vartuli J C,Han S,et al.Influence of the preparative method on the activity of highly acidic WOx/ZrO2 and the relative acid activity compared with zeolites[J].Journal of Catalysis,1997,168(2):431-441.
[15]Liu H Y,Ma Z,Chu Y,et al.Surfactant-assisted synthesis,characterization and catalytic properties of nanostructure porous WO3/ZrO2 solid acid[J].Colloids and Surfaces A,2006,287(1):10-15.
[16]Agustín M A,Gonzalo P,Maria A A,et al.Influence of the preparative route on the properties of WOx-ZrO2 catalysts:A detailed structural,spectroscopic,and catalytic study[J].Journal of Catalysis,2007,248(2):288-302.
[17]Zhou W,Nikolaos S,Xu H,et al.Nature of catalytically active sites in the supported WO3/ZrO2 solid acid system:A current perspective[J].ACS Catalysis,2017,7(3):2181-2198.
[18]Li Pengfei(李鹏飞),Pang Xianshen(庞先燊).A study on the solid superacid catalyst of AlCl3 supported resin-characterization of catalyst[J].Speciality Petrochemicals(精细石油化工),1993,(2):29-32.
[19]Cid R,Pecchi G.Potentiometric method for determining the number and relative strength of acid sites in colored catalysts[J].Applied Catalysis,1985,14(1):15-21.
[20]Kozo T.New solid and bases their catalytic properties[M].Zheng Lubin(郑禄彬)trans.Beijing:Chemical Industry Press,1992:193-194.
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