Research progress in the synthesis of isophorone by acetone self-condensation

doi:10.16085/j.issn.1000-6613.2016.04.036

Abstract

Abstract: In recent years, the acetone production keeps growing, resulting in excess production capacity in China. On the other hand, high value-added applications of acetone are relatively limited. The process of making acetone self-condensation into isophorone, and subsequently into isophorone diamine, isophorone diisocyanate, can greatly enhance the added value of acetone. The paper reviewed the production routes of isophorone by acetone self-condensation and the research progress of the catalysts. We emphasized to introduce the representative industrial production processes and catalysts, such as acetone liquid phase condensation with alkaline hydroxide as catalyst and acetone gas condensation with hydrotalcite as catalyst. Then, we further discussed the factors influencing the catalytic performance of Mg-Al solid base, and compared the advantages and disadvantages of the production routes of isophorone. Finally, the prospects of isophorone is forecasted.

Key words: acetone, isophorone, gas phase condensation, hydrotalcite, solid base

摘要： 近年来我国丙酮产量持续增长,丙酮产能逐渐过剩,与此同时,丙酮的高附加值利用相对较少;丙酮缩合制异佛尔酮,随后生产异佛尔酮二胺、异佛尔酮异氰酸酯等能够大大提高丙酮利用的附加值.本文对目前丙酮缩合制异佛尔酮的生产路线及催化剂研究进展进行了总结,重点介绍了有工业化应用的代表性工艺及催化剂,如以碱性氢氧化物为催化剂的丙酮液相缩合法以及以镁铝水滑石为催化剂的气相缩合法;在此基础上,进一步介绍了镁铝固体碱催化剂催化效果的影响因素,并对现有异佛尔酮合成工艺方法进行了分析、比较.最后对异佛尔酮的发展前景进行了展望.

关键词: 丙酮, 异佛尔酮, 气相缩合, 水滑石, 固体碱

CLC Number:

O643.32

LI Yunlong, LÜ Jiangang, JIN Zhaosheng. Research progress in the synthesis of isophorone by acetone self-condensation[J]. Chemical Industry and Engineering Progree, 2016, 35(04): 1190-1196.

李云龙, 吕建刚, 金照生. 丙酮缩合制异佛尔酮研究进展[J]. 化工进展, 2016, 35(04): 1190-1196.

References

[1] 李平. 异佛尔酮的合成及应用[J]. 四川化工与腐蚀控制,1999,2(1):54-55.
[2] 樊森. 赢创上海异佛尔酮生产基地投产:完成全球战略性布局[J]. 中国涂料,2014,29(8):92-94.
[3] TDI替代品原料国产化迈出一大步异佛尔酮将自主规模化生产[J]. 江苏氯碱,2012(3):32.
[4] 吕咏梅. 异佛尔酮合成技术进展与应用开发[J]. 杭州化工,2005,35(2):6-8.
[5] 李贵贤,任若飞,强光明,等. 异佛尔酮合成研究进展[J]. 甘肃科技,2011,27(5):26-29.
[6] Ballard S A,Haury V E. Production of isophorone:US2334226[P]. 1944.
[7] Ballard S A,Haury V E. Production of isophorone and related products:US2399976[P]. 1946.
[8] 毛丽秋,李谦和. 丙酮液相一步法合成异佛尔酮[J]. 湖南师范大学自然科学学报,2000,23(3):67-71.
[9] 董宇航,陈文强,宋琦,等. 液相法合成异佛尔酮反应研究[J]. 广州化工,2011,39(15):89-91.
[10] 何岩,员玫,李浩,等. 一种丙酮在碱性催化剂下液相缩合制备异佛尔酮的方法:中国,201110325843.5[P]. 2011-10-18.
[11] 何岩,员玫,李浩,等. 一种异佛尔酮的合成方法:中国,201110325830.8[P]. 2011-10-18.
[12] Teissier R,Kervennal J. Process for obtaining isophorone:US5849985[P]. 1998.
[13] 刘勤. 异佛尔酮的合成路线及其影响因素分析[J]. 精细化工中间体,2012,42(3):6-12.
[14] 马春香,刘钢,朱万春,等. 共沉淀法制备的镁铝氧化物催化剂上丙酮气相缩合反应[J]. 高等学校化学学报,2009,30(12):2429-2433.
[15] 马春香. 固体碱催化剂上丙酮气相缩合制异佛尔酮反应性能研究[D]. 长春:吉林大学,2009.
[16] Ordóñez S,Díaz E,León M,et al. Hydrotalcite-derived mixed oxides as catalysts for different C-C bond formation reactions from bioorganic materials[J]. Catalysis Today,2011,167(1):71-76.
[17] 党明岩,左继成. 镁铝复合氧化物催化剂气相法合成异佛尔酮[J]. 辽宁化工,2002,31(9):373-375.
[18] 高鹏程. 丙酮气固多相法合成异佛尔酮的催化剂及工艺研究[D]. 北京:中国石油大学,2008.
[19] 谢丽莎,陈霄榕,刘然,等. 丙酮气固相催化合成异佛尔酮固体催化剂的研究[J]. 河北工业大学学报,2011,40(1):64-67.
[20] 王琼,于海斌,南军. 镁铝复合氧化物制备及其丙酮缩聚制异佛尔酮反应研究[J]. 无机盐工业,2014,46(5):69-72.
[21] 邓晓丰. 镁铝氧化物固体催化剂制备异佛尔酮的研究[J]. 浙江化工,2014,45(7):16-19.
[22] 刘自力,刘艳,陆柏楼. 水滑石的合成及其对催化丙酮合成异佛尔酮的影响[J]. 广州大学学报:自然科学版,2011,10(4):14-19.
[23] 梁东. 固体碱催化剂的制备及其催化合成异佛尔酮的反应性能研究[D]. 大连:大连理工大学,2011.
[24] 张夏丽. 合成异佛尔酮的固体碱催化剂研究[D]. 北京:中国石油大学,2009.
[25] 刘然. 固体催化剂上丙酮缩合制备异佛尔酮的研究[D]. 天津:河北工业大学,2008.
[26] 吴亚娟,谭涓,梁东,等. 复合氧化物固体碱催化丙酮制备异佛尔酮[J]. 石化技术,2012,19(4):7-11.
[27] Ma C,Liu G,Wang Z,et al. Aldol condensation of acetone over Mg-Al mixed oxides catalyst prepared by a citric acid route[J]. Reaction Kinetics and Catalysis Letters,2009,98(1):149-156.
[28] Zhang J J,Liu Z L,Qin Z Z,et al. Preparation of MgAlY-LDO solid base catalysts and their catalytic performance on the synthesis of isophorone via acetone condensation[J]. Advanced Materials Research,2012,550-553:424-428.
[29] Liu Y,Sun K,Ma H,et al. Cr,Zr-incorporated hydrotalcites and their application in the synthesis of isophorone[J]. Catalysis Communications,2010,11(10):880-883.
[30] 李志新. 铝镁锆类水滑石催化合成异佛尔酮[D]. 齐齐哈尔:齐齐哈尔大学,2012.
[31] Kelkar C,Schutz A. Efficient hydrotalcite-based catalyst for acetone condensation to α-isophorone——scale up aspects and process development[J]. Applied Clay Science,1998,13(5):417-432.
[32] 周玮,宋丕双,马中义,等. 镁铝催化剂在丙酮缩合制备异佛尔酮反应中的失活研究[J]. 化工科技,2011,19(2):21-24.
[33] 李凯荣,陈宵榕,周玮,等. 一种丙酮合成异佛尔酮的多相催化方法:200910083130.5[P]. 2009-04-30.
[34] 赵坚强,张玉善,李春伟. 一种用于丙酮多相法合成异佛尔酮的催化剂的制备方法:201110130003.3[P]. 2011-05-19.
[35] 赵坚强,张玉善,李春伟. 一种合成异佛尔酮的固体碱催化剂及其应用:201110158175.1[P]. 2011-06-14.
[36] 谢丽莎,陈霄榕. 固体酸碱性质对丙酮缩合生成异佛尔酮反应的影响[J]. 化工进展,2010,29(7):1230-1234.
[37] 王玉环,王国甲. 丙酮在固体碱催化剂上的缩合反应[J]. 高等学校化学学报,1993,14(10):1448-1450.
[38] Krivtsov I,Faba L,Díaz E,et al. A new peroxo-route for the synthesis of Mg-Zr mixed oxides catalysts:application in the gas phase acetone self-condensation[J]. Applied Catalysis A:General,2014,477:26-33.
[39] Faba L,Díaz E,Ordóñez S. Gas phase acetone self-condensation over unsupported and supported Mg-Zr mixed-oxides catalysts[J]. Applied Catalysis B:Environmental,2013,142-143:387-395.
[40] Canning A,Jackson S,McLeod E,et al. Aldol condensation of acetone over CsOH/SiO₂:a mechanistic insight using isotopic labeling[J]. Applied Catalysis A:General,2005,289(1):59-65.
[41] Di Cosimo J,Diez V,Apesteguia C. Base catalysis for the synthesis of α,β-unsaturated ketones from the vapor-phase aldol condensation of acetone[J]. Applied Catalysis A:General,1996,137(1):149-166.
[42] Di Cosimo J,Apesteguía C R. Study of the catalyst deactivation in the base-catalyzed oligomerization of acetone[J]. Journal of Molecular Catalysis A:Chemical,1998,130(1):177-185.
[43] 郑平,阮济之. 丙酮在沸石催化剂上的缩合反应[J]. 精细化工,1993:10(1):32-35.
[44] 易旺成. 异佛尔酮的合成工艺研究[D]. 杭州:浙江大学,2006.
[45] Isao F,Katsuhiko M. Production of acetone dehydrative condensation product:JP 09-151152[P]. 1997.
[46] Zamora M,López T,Gómez R,et al. Acetone gas phase condensation on alkaline metals doped TiO₂ sol-gel catalysts[J]. Applied Surface Science,2005,252(3):828-832.
[47] Zamora M,López T,Asomoza M,et al. Alkaline doped TiO₂ sol-gel catalysts:effect of sintering on catalyst activity and selectivity for acetone condensation[J]. Catalysis Today,2006,116(2):234-238.
[48] Zamora M,Lopez T,Gomez R,et al. Oligomerization of acetone over titania-doped catalysts (Li,Na,K and Cs):effect of the alkaline metal in activity and selectivity[J]. Catalysis Today,2005,107-108:289-293.
[49] Stevens M,Foley H. Oxidized caesium/nanoporous carbon materials:solid-base catalysts with highly-dispersed active sites[J]. Chemical Communications,1999,(3):275-276.
[50] Thomas L,Tanner R,Gill P,et al. Aldol condensation reactions of acetone over alkali-modified vanadium phosphate catalysts[J]. Physical Chemistry Chemical Physics,2002,4(18):4555-60.
[51] 刘自力,李辉. 一种用于丙酮缩合法制备异佛尔酮的催化剂:200910193252.X[P]. 2009-10-23.
[52] 陈健明,崔迎祥,姚震,等. 一种异佛尔酮的制备方法:201310419951.8[P]. 2013-09-13.