Synthesis of 2-ethyl-2-hexenal via n-butanal self-condensation catalyzed by La-Al2O3

doi:10.11949/j.issn.0438-1157.20151260

Abstract

Abstract:

2-Ethylhexanol is a kind of important plasticizer alcohols. n-Butanal self-condensation to 2-ethyl-2-hexenal is one of the important processes for industrial production of 2-ethylhexanol. In order to overcome the shortcomings such as equipment corrosion, environmental pollution and high production cost in the present industrial n-butanal self-condensation reaction using alkali aqueous catalyst, the La-modified γ-Al₂O₃ catalyst (La-Al₂O₃) was adopted to catalyze n-butanal self-condensation reaction. Firstly, the influence of different preparation methods and conditions on the La-Al₂O₃ catalytic activity was studied. The results showed that the catalytic activity of La-Al₂O₃ prepared by colloidal chemical method and calcined at 700℃ for 4 h was better. The existing acidic centers and basic centers matching with each other were the key to present better catalytic activity. The influence of reaction conditions on n-butanal self-condensation reaction was studied using the La-Al₂O₃ catalyst. The suitable reaction conditions were obtained as follows: mass ratio of catalyst to n-butanal 0.15:1, reaction temperature of 180℃ and reaction time of 8 h. Under the above conditions, the conversion of n-butanal was 90.6% and the selectivity of 2-ethyl-2-hexenal was 91.7%. La-Al₂O₃ could be reused for 4 recycles without losing its activity significantly. In addition, the by-products existing in the reaction system were identified by GC-MS analysis and then a possible reaction network for n-butanal self-condensation to 2-ethyl-2-hexenal catalyzed by La-Al₂O₃ was established.

Key words: n-butanal, La-Al₂O₃catalyst, catalysis, aldol self-condensation, multiphase reaction, synthesis, 2-ethyl-2-hexenal

摘要：

辛醇(2-乙基己醇)是一种重要的增塑剂醇。正丁醛自缩合合成辛烯醛是工业生产辛醇的重要步骤之一。为克服工业正丁醛自缩合反应因使用强碱水溶液催化剂所带来的设备腐蚀、污染环境、生产成本高等缺点,采用La改性γ-Al₂O₃催化剂(La-Al₂O₃)催化正丁醛自缩合反应。首先研究了制备方法和制备条件对La-Al₂O₃催化性能的影响,发现采用胶溶法、于700℃下焙烧4 h得到的La-Al₂O₃催化性能较好,具有相互匹配的酸碱中心是催化性能较好的关键。以适宜条件下制备的La-Al₂O₃为催化剂,研究了反应条件对正丁醛自缩合反应的影响,得到适宜的反应条件为:催化剂与正丁醛质量比为0.15、反应温度180℃、反应时间8 h。在此条件下,正丁醛的转化率最高达到90.6%,辛烯醛的选择性为91.7%。该催化剂重复使用4次,催化活性无明显下降。通过对反应液进行GC-MS分析,确定了正丁醛自缩合反应体系中的副产物,进而推测了可能的副反应,建立了La-Al₂O₃催化正丁醛自缩合合成辛烯醛的反应网络。

关键词: 正丁醛, La-Al₂O₃催化剂, 催化, 羟醛缩合, 多相反应, 合成, 辛烯醛

CLC Number:

TQ032

LIU Xiaohong, WANG Yi, AN Hualiang, ZHAO Xinqiang, WANG Yanji. Synthesis of 2-ethyl-2-hexenal via n-butanal self-condensation catalyzed by La-Al₂O₃[J]. CIESC Journal, 2016, 67(5): 1884-1891.

刘肖红, 王毅, 安华良, 赵新强, 王延吉. La-Al₂O₃催化正丁醛自缩合合成辛烯醛反应[J]. 化工学报, 2016, 67(5): 1884-1891.

References 20

[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]	朱燕. 丁辛醇加氢催化技术进展 [J]. 上海化工, 2008, 33(1): 25-30. ZHU Y. Process progress in hydrogenation of butanol and 2-ethylhexenol [J]. Shanghai Chemical Industry, 2008, 33(1): 25-30.
[3]	KING F, KELLY G J. Combined solid base/hydrogenation catalysts for industrial condensation reactions [J]. Catalysis Today, 2002, 73(1/2): 75-81.
[4]	KELLY G J, KING F, KETT M. Waste elimination in condensation reactions of industrial importance [J]. Green Chemistry, 2002, 4: 392-399.
[5]	SHEN W Q, TOMPSETT G A, XING R, et al. Vapor phase butanal self-condensation over unsupported and supported alkaline earth metal oxides [J]. Journal of Catalysis, 2012, 286: 248-259.
[6]	HATTORI H. Solid base catalysts: generation of basic site and application to organic synthesis [J]. Applied Catalysis, A: General, 2001, 222(1/2): 247-259.
[7]	YUTAKA W, KAZUE S, MINORU H. A green method for the self-aldol condensation of aldehydes using lysine [J]. Green Chemistry, 2010, 12: 384-386.
[8]	张媛媛. 正丁醛自缩合生成辛烯醛新型催化工艺研究[D]. 上海: 上海师范大学, 2010. ZHANG Y Y. The study of new catalytic technology of self-condensation of butanal to 2-ethylhexenal[D]. Shanghai: Shanghai Normal University, 2010.
[9]	张钟宪, 鲁晓明, 罗红, 等. 正二十面体十二钨多酸催化丙酮羟醛缩合的初探 [J].首都师范大学学报(自然科学版), 2002, 23(1): 46-51. ZHANG Z X, LU X M, LUO H, et al. Catalysis of dodecatungstic acid with icosahedron to aldol condensation of acetone [J]. Journal of Capital Normal University(Natural Science Edition), 2002, 23(1): 46-51.
[10]	MEDIAVILLA M, MELO L, DIAZ Y, et al. MIBK from acetone on Pd/H-[Ga]ZSM-5 catalysts: effect of metal loading [J]. Microporous and Mesoporous Materials, 2008, 116(1/2/3): 627-632.
[11]	PAULIS M, MARTIN M, SORIA D B, et al. Preparation and characterization of niobium oxide for the catalytic aldol condensation of acetone [J]. Applied Catalysis A: General, 1999, 180(1): 411-420.
[12]	IDRISS H, BARTEAU M A. Selectivity and mechanism shifts in the reaction of acetaldehyde on oxidized and reduced TiO2(001) surface [J]. Catalysis Letters, 1996, 40(3): 147-153.
[13]	MUSKO N E, GRUNWALDT J D. Heterogeneously catalysed aldol reactions in supercritical carbon dioxide as innovative and non-flammable reaction medium [J]. Topics in Catalysis, 2011, 54(16/17/18): 1115-1123.
[14]	SWIFT H E, BOZIK J E, MASSOTH F E. Vapor-phase aldol condensation of n-butyraldehyde using a reduced tin-silica catalyst [J]. Journal of Catalysis, 1969, 15(4): 407-416.
[15]	赵月昌, 梁学正, 高珊, 等. 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]. 分子催化, 2007, 21(4): 315-318. ZHAO Y C, LIANG X Z, GAO S, et al. Study on the catalytic aldol condensation by superacid and its solvent effection [J]. Journal of Molecular Catalysis (China), 2007, 21(4): 315-318.
[16]	陈翠娜,刘肖红,安华良,等. H4SiW12O40/SiO2催化正丁醛自缩合反应 [J]. 化工学报, 2014, 65(6): 2106-2112. CHEN C N, LIU X H, AN H L, et al. n-Butyraldehyde aldol self-condensation catalyzed by H4SiW12O40/SiO2 [J]. CIESC Journal, 2014, 65(6): 2106-2112.
[17]	梁宁. 正丁醛羟醛缩合反应及与加氢反应集成催化剂研究[D]. 天津: 河北工业大学, 2014. LIANG N. Research on catalysis for n-butanal aldol condensation and for n-butanal aldol condensation-hydrogenation reaction integration [D]. Tianjin: Hebei University of Technology, 2014.
[18]	XIONG C, LIANG N, AN H L, et al. n-Butyraldehyde self-condensation catalyzed by Ce-modified γ-Al2O3 [J]. RSC Advances, 2015, 5(125): 103523-103533.
[19]	ZHANG X L, AN H L, ZHANG H Q, et al. n-Butyraldehyde self-condensation catalyzed by sulfonic acid functionalized ionic liquids [J]. Industrial & Engineering Chemistry Research, 2014, 53(43): 16707-16714.
[20]	IDRISS H, KIM K S, BARTEAU M A. Carbon-carbon bond formation via aldolization of acetaldehyde on single crystal and polycrystalline TiO2 surfaces [J]. Journal of Catalysis, 1993, 139(1): 119-133.

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

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