朱园园,何茜,安华良,耿艳楼,赵新强,王延吉

• 1:河北工业大学化工学院绿色化工与高效节能河北省重点实验室

摘要(Abstract)：

在单因素试验的基础上,采用响应曲面法对TiO_2催化正丁醛气相自缩合反应条件进行了优化。结果表明,在空时8 g·min?m L~(-1)、反应温度180℃、反应压力2.0 MPa的条件下,辛烯醛收率为81.2%,选择性为96.6%。在此基础上考察了TiO_2催化剂的稳定性,发现运行300 h后正丁醛的转化率、辛烯醛的收率和选择性基本保持不变,说明TiO_2具有良好的催化稳定性。

关键词(KeyWords)： TiO_2;响应曲面法;正丁醛;羟醛缩合

Abstract:

Keywords:

基金项目(Foundation): 国家自然科学基金(21476058,21506046);; 天津市自然科学青年基金(16JCQNJC06100)

作者(Author): 朱园园,何茜,安华良,耿艳楼,赵新强,王延吉

参考文献(References)：

• [1]Hanna D G,Shylesh S,Li Y P,et al.Experimental and theoretical study of n-butanal self-condensation over Ti species supported on silica[J].ACS Catalysis,2014,4(9):2908-2916.
• [2]Zhang X L,An H L,Zhang H Q,et al.n-Butyraldehyde self-condensation catalyzed by sulfonic acid functionalized ionic liquids[J].Industrial and Engineering Chemistry Research,2014,53(43):16707-16714.
• [3]LOU Hui(楼辉),SUN Hui(孙辉),DUAN Jin-zhao(段谨钊),et al.A method for n-butyraldehyde aldol self-condencsation catalyzed by magnesium oxide and its preparation(氧化镁催化剂催化正丁醛缩合反应的方法及其制备):CN,102070419[P].2011-5-25.
• [4]CUI Long(崔龙),LüHong-qiu(吕红秋),WANG Zhen-fan(王振凡),et al.A solid base catalyst of aldol condensation and its application(一种羟醛缩合反应固体碱催化剂及应用):CN,102019177A[P].2011-4-20.
• [5]King F,Kelly G J.Combined solid base/hydrogenation catalysts for industrial condensation reactions[J].Catalysis Today,2002,73(1-2):75-81.
• [6]SU Bo(苏博),LANG Wan-zhong(郎万中),ZENG Qun-ying(曾群英),et al.Preparation of organic functionalized mesoporous catalysts and their applications to the self-condensation reaction of n-butanal to 2-ethylhexenal(有机官能化介孔催化剂制备及其在正丁醛自缩合制辛烯醛反应中的应用)[J].The Chinese Journal of Process Engineering(过程工程学报),2010,10(2):361-366.
• [7]Watanabe Y,Sawada K,Hayashi M.A green method for the self-aldol condensation of aldehydes using lysine[J].Green Chemistry,2010,12(3):384-386.
• [8]Jose T,Sudheesh N,Shukla R S.Amino functionalized chitosan as a catalyst for selective solvent-free self-condensation of linear aldehydes[J].Journal of Molecular Catalysis A:Chemical,2010,333(1-2):158-166.
• [9]ZHAO Yue-chang(赵月昌),LIANG Xue-zheng(梁学正),GAO Shan(高珊),et al.Study on the catalytic aldol condensation by superacid and its solvent effection(固体超强酸催化下的醛酮自身缩合及其溶剂效应的研究)[J].Journal of Molecular Catalysis(China)(分子催化),2007,21(4):315-318.
• [10]CHEN Cui-na(陈翠娜),LIU Xiao-hong(刘肖红),AN Hua-liang(安华良),et al.n-Butyraldehyde aldol self-condensation catalyzed by H4SiW12O40/SiO2(H4SiW12O40/SiO2催化正丁醛自缩合反应)[J].CIESC Journal(化工学报),2014,65(6):2106-2112.
• [11]LIU Xiao-hong(刘肖红),WANG Yi(王毅),AN Hua-liang(安华良),et al.Synthesis of 2-ethyl-2-hexenal via n-butanal self-condensation catalyzed by La-Al2O3(La-Al2O3催化正丁醛自缩合合成辛烯醛反应)[J].CIESC Journal(化工学报),2016,67(5):1884-1891.
• [12]Xiong C,Liang N,An H L,et al.n-Butyraldehyde self-condensation catalyzed by Ce-modifiedγ-Al2O3[J].RSC Advances,2015,5(125):103523-103533.
• [13]XIONG Chao(熊超).Reaction kinetics of n-butanal aldol condensation over Ce-Al2O3 catalyst and its catalytic stability(Ce-Al2O3催化正丁醛自缩合反应动力学及催化稳定性研究)[D].Tianjin(天津):Hebei University of Technology(河北工业大学),2016.
• [14]Sun D,Moriya S,Yamada Y,et al.Vapor-phase self-aldol condensation of butanal over Ag-modified TiO2[J].Applied Catalysis A:General,2016,524:8-16.
• [15]Zhao L,An H,Zhao X,et al.TiO2-catalyzed n-valeraldehyde self-condensation to 2-propyl-2-heptenal:acid catalysis or base catalysis?[J].Industrial and Engineering Chemistry Research,2016,55(48):12326-12333.
• [16]HE Xi(何茜),AN Hua-liang(安华良),ZHAO Xin-qiang(赵新强),et al.Effects of crystal forms of TiO2 on n-butanal self-condensation(TiO2晶型对催化正丁醛自缩合反应性能的影响)[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2017,31(5):1103-1112.
• [17]SUN Xiao-xue(孙晓雪),LIU Zhong-neng(刘仲能),GU Song-yuan(顾松园),et al.Acid leaching of spent Co-Mo hydroprocessing catalyst(钴钼基加氢处理催化剂酸浸过程研究)[J].Industrial Catalysis(工业催化),2017,25(7):51-56.
• [18]YANG Liang-ru(杨亮茹),WANG Hai-tao(王海涛),KANG Yan-long(康彦龙),et al.Green oxidation of(methylthio)pyrimidine-5-carboxylate derivatives(甲硫基嘧啶-5-羧酸乙酯衍生物的绿色氧化)[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2016,30(5):1158-1163.
• [19]GU Zhi-qi(顾执奇),ZHANG Shi-han(张士汉),XU Dan-hua(徐丹华),et al.Nitrogen and phosphorus Co-doped TiO2 for photocatalytic removal of gaseous chlorobenzene under high humidity condition:preparation,characterization and performance(氮磷共掺杂TiO2的制备、结构表征及高湿度下光催化净化氯苯废气的研究)[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2017,31(5):1201-1209.
• [20]Kim S M,Lee M E,Choi J W,et al.Conversion of biomass-derived butanal into gasoline-range branched hydrocarbon over Pd-supported catalysts[J].Catalysis Communications,2011,16(1):108-113.
• [21]HE Xi(何茜).Catalytic performance of TiO2 for n-butanal self-condensation(TiO2催化正丁醛自缩合反应性能研究)[D].Tianjin(天津):Hebei University of Technology(河北工业大学),2017.