甲醛制备季戊四醇反应研究进展
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摘要
介绍了甲醛乙醛制备季戊四醇的反应机理和生产工艺。分析了现有工艺"钙法"、"钠法"、"钾法"、"缩合加氢法"的特点和存在的问题,比较得出以有机叔胺为催化剂催化甲醛与乙醛合成季戊四醇的"缩合加氢法"能够有效解决"钠法"腐蚀严重、三废污染严重的问题,成为工业化、绿色化制备季戊四醇的重点研究方向。
The reaction mechanism and production process of preparing pentaerythritol from formaldehyde acetaldehyde are introduced.The characteristics and existing problems of the existing processes such as "calcium method","sodium method","potassium method" and "condensation hydrogenation method" are analyzed.It is concluded that the "condensation hydrogenation" which the synthesis of pentaerythritol from formaldehyde and acetaldehyde was catalyzed by organic tertiary amine can effectively solve the problems of serious corrosion and waste pollution caused by "sodium method" and it becomes the key research direction of industrialization and green preparation of pentaerythritol.
The reaction mechanism and production process of preparing pentaerythritol from formaldehyde acetaldehyde are introduced.The characteristics and existing problems of the existing processes such as "calcium method","sodium method","potassium method" and "condensation hydrogenation method" are analyzed.It is concluded that the "condensation hydrogenation" which the synthesis of pentaerythritol from formaldehyde and acetaldehyde was catalyzed by organic tertiary amine can effectively solve the problems of serious corrosion and waste pollution caused by "sodium method" and it becomes the key research direction of industrialization and green preparation of pentaerythritol.
引文
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[2] 李峰.我国甲醛行业的发展动态[J].乙醛醋酸化工,2015(3):17-26.
[3] 乔晓辉,方奕文,黄晓昌.甲醛合成催化剂的研究进展[J].石油化工,2007,36(8):846-852.
[4] 傅向升.破解产能过剩优化供给结构-化解石化行业结构性产能过剩矛盾的思考[J].中国石油和化工,2016(9):4-11.
[5] 谭露璐.甲醛、乙醛气相羟醛缩合催化剂及反应工艺研究[D].上海:同济大学,2006.
[6] Markert M,Scheffler U,Mahrwald R.Asymmetric histidine-catalyzed cross-aldol reactions of enolizable aldehydes:access to defined configured quaternary stereogenic centers[J].J Am Chem Soc,2009,131(46):16642-16643.
[7] Rao Q Q,Luo S W,Gong L Z.Water as dual functional cocatalyst:A theoretical study on the mechanism of direct aldol reaction on water catalyzed by a leucine derivative[J].Chinese Science Bulletin,2010,55(17):1742-1752.
[8] Garroa R,Navarroa M T,Primo J.Lewis acid-containing mesoporous molecular sieves as solid efficient catalysts for solvent-free mukaiyama-type aldol condensation[J].Journal of Catalysis,2005,233(2):342-350.
[9] Torii H,Nakadai M,Ishihara K,et al.Symmetric direct aldol reaction assisted by water and a proline-derived tetrazole catalyst[J].Angew Chem Int Ed,2004,43(15):1983-1986.
[10] Serra-Holm V,Salmi T,Maki-Arvela P,et al.Comparison of activity and selectivity of weakly basic anion-exchange catalysts for the aldolization of butyraldehyde with formaldehyde[J].Organic Process Research and Development,2001,5:368-375.
[11] Salek J S,Pugach J,Elias C L,et al.Manufacture of trimethylolpropane:US,5763690[P].1998-06-09.
[12] 埃克L.制备季戊四醇的方法:CN,1165804A[P].1997-11-26.
[13] 扈士海.季戊四醇的生产应用及市场分析[J].河北工业科技,2009,26(1):58-60.
[14] 唐培堃,冯亚青.精细有机合成化学与工艺学[M].2版.北京:化学工业出版社,2006:324-328.
[15] 李峰.甲醛及其衍生物[M].北京:化学工业出版社,2010:223-262.
[16] 岳宏君.双季戊四醇的合成工艺研究[D].上海:华东理工大学,2000.
[17] 李正星.工业季戊四醇脱色除杂方法的研究[D].合肥:合肥工业大学,2015.
[18] Teruyuki N,Toshio W,Akira M,et al.Process for producing polyhydric alcohol:EP,0708073B1[P].1996-04-24.
[19] 王强,李玉普,张洁.低灰分钙法季戊四醇的制备方法:CN,104672060A[P].2014-12-24.
[20] 刘启东,朱建文,彭枝忠,等.一种单季戊四醇、双季戊四醇和三季戊四醇的生产方法:CN,101265166A[P].2008-09-17.
[21] 王春华,陈辉,唐勇,等.提高单季戊四醇产率的方法:CN,102432431A[P].2011-11-07.
[22] 陶长文,翁自飞.一种99级季戊四醇的生产方法:CN,105111047A[P].2015-08-28.
[23] 刘启东,李远喜,李万忠.一种钾法季戊四醇的生产方法:CN,104447202A[P].2014-11-14.
[24] Kelly G J.Aldol condensation:US,6586636B2[P].2003-07-01.
[25] 揭元萍,张传好,杨旭石,等.一种羟醛中间体的合成方法:CN,102285873A[P].2011-07-05.
[26] 徐成娟.季戊四醇绿色合成工艺研究[D].青岛:中国石油大学(华东),2014.
[27] 田家明,施以军.一种季戊四醇的合成方法:CN,105085188A[P].2015-11-25.