杂多酸复合物的制备及其催化合成2-（1-环已烯基）环已酮
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摘要
本文研究了杂多酸复合物的制备以及将其用于催化环己酮的自缩合反应生成2-(1-环己烯基)环己酮。课题采用了两种典型方法即回流吸附法、浸渍法制备杂多酸复合物。通过X射线衍射、热分析、红外光谱等手段对制备的杂多酸复合物进行了表征。考察得到了这一催化反应过程中的最佳工艺条件及催化剂的寿命。
首先,选用活性炭为载体采用回流吸附法负载磷钨酸制备复合物(PW_(12)/C)。通过差热分析表明复合物中磷钨酸的分解逐步发生,红外谱图表明活性炭上Keggin结构的磷钨酸分解温度在600℃附近。PW_(12)/C用于催化合成2-(1-环己烯基)环己酮,实验得到最佳工艺条件:复合物中磷钨酸的负载量25%催化效果最佳,用量占反应物质量的3.0%,反应时间2.5h,反应温度150℃。
其次,SBA-15分子筛具有高的比表面积,长程有序的孔道等特点,是良好的催化剂载体。SBA-15分子筛本身不具有酸性,本文采用浸渍法在该分子筛上引入磷钨酸,使其具有一定的酸强度。
采用浸渍法将磷钨酸负载到SBA-15分子筛内制备复合物(PW_(12)/SBA-15)。磷钨酸均匀分散于SBA-15分子筛内,保持Keggin结构不变。复合物中SBA-15载体与磷钨酸有较强的相互作用,造成载体的水热稳定性下降及磷钨酸的热稳定性下降。最后,将磷钨酸、磷钼酸按一定比例进行复配,采用浸渍法制备成负载型催化剂,催化合成2-(1-环己烯基)环己酮催化效果好,转化率达到86.5%,具有很好的工业应用前景。
In this work, we studied preparation of 12-tungstophosphoric acid composites, and then composites were employed as catalysts to synthesize 2-(1-cyclohexenyl)cyclohexanone in this paper. A series of 12-tungstophosphoric acid composites were prepared by two typical methods, namely reflux adsorption method and impregnation method. The composites were characterized by XRD,TG-DTA, IR etc. The optimum reaction conditions and longevity of catalysts were investigate.
First of all, active carbons were selected as supports to prepare 12-tungstophosphoric acid composites (PW12/C) by reflux adsorption method. The results of TG-DTA and other different analysis indicated that 12-tungstophosphoric acids decomposed gradually through analysis of samples calcined composites under the different temperatures. From the infrared spectrometry, we known the Keggin structure of 12-tungstophosphoric acid decomposed at the 600℃. The PW_(12)/C were used as catalysts for the synthesis of 2-(1-cyclohexenyl)cyclohexanone. The optimum reaction conditions were as follows:amount of 12-tungstophosphoric acid supported on active carbon 25%, amount of the catalyst used in the reactants 3.0%, reaction time 2.5h, reaction temperature 150℃.
Secondly, The molecular sieve SBA-15 has more good characters, such as higher specific surface, uniform porous channels. It is regarded as an excellent support. The molecular sieve SBA-15 itself does not has acidity. In this paper 12-tungstophosphoric acids were introduced in the mesoporous molecular sieve by impregnation method. The 12-tungstophosphoric acids also highly dispersed in the molecular sieve and kept Keggin structure. In the composites there are strong mutual interaction between the support SBA-15 and 12-tungstophosphoric acid, the hydrothermal stability of support and acid all dropped.
Finally, Phosphotungstic acid and phosphomolybdic acid were mixed in 1:1 proportion, The Catalytic activity was good when it was supported by Impregnation method, During the synthesis of 2-(1-cyclohexenyl)cyclohexanone, Conversion of cyclohexanone could reach 86.5%,The catalyst had favorable Industrial prospect.
首先,选用活性炭为载体采用回流吸附法负载磷钨酸制备复合物(PW_(12)/C)。通过差热分析表明复合物中磷钨酸的分解逐步发生,红外谱图表明活性炭上Keggin结构的磷钨酸分解温度在600℃附近。PW_(12)/C用于催化合成2-(1-环己烯基)环己酮,实验得到最佳工艺条件:复合物中磷钨酸的负载量25%催化效果最佳,用量占反应物质量的3.0%,反应时间2.5h,反应温度150℃。
其次,SBA-15分子筛具有高的比表面积,长程有序的孔道等特点,是良好的催化剂载体。SBA-15分子筛本身不具有酸性,本文采用浸渍法在该分子筛上引入磷钨酸,使其具有一定的酸强度。
采用浸渍法将磷钨酸负载到SBA-15分子筛内制备复合物(PW_(12)/SBA-15)。磷钨酸均匀分散于SBA-15分子筛内,保持Keggin结构不变。复合物中SBA-15载体与磷钨酸有较强的相互作用,造成载体的水热稳定性下降及磷钨酸的热稳定性下降。最后,将磷钨酸、磷钼酸按一定比例进行复配,采用浸渍法制备成负载型催化剂,催化合成2-(1-环己烯基)环己酮催化效果好,转化率达到86.5%,具有很好的工业应用前景。
In this work, we studied preparation of 12-tungstophosphoric acid composites, and then composites were employed as catalysts to synthesize 2-(1-cyclohexenyl)cyclohexanone in this paper. A series of 12-tungstophosphoric acid composites were prepared by two typical methods, namely reflux adsorption method and impregnation method. The composites were characterized by XRD,TG-DTA, IR etc. The optimum reaction conditions and longevity of catalysts were investigate.
First of all, active carbons were selected as supports to prepare 12-tungstophosphoric acid composites (PW12/C) by reflux adsorption method. The results of TG-DTA and other different analysis indicated that 12-tungstophosphoric acids decomposed gradually through analysis of samples calcined composites under the different temperatures. From the infrared spectrometry, we known the Keggin structure of 12-tungstophosphoric acid decomposed at the 600℃. The PW_(12)/C were used as catalysts for the synthesis of 2-(1-cyclohexenyl)cyclohexanone. The optimum reaction conditions were as follows:amount of 12-tungstophosphoric acid supported on active carbon 25%, amount of the catalyst used in the reactants 3.0%, reaction time 2.5h, reaction temperature 150℃.
Secondly, The molecular sieve SBA-15 has more good characters, such as higher specific surface, uniform porous channels. It is regarded as an excellent support. The molecular sieve SBA-15 itself does not has acidity. In this paper 12-tungstophosphoric acids were introduced in the mesoporous molecular sieve by impregnation method. The 12-tungstophosphoric acids also highly dispersed in the molecular sieve and kept Keggin structure. In the composites there are strong mutual interaction between the support SBA-15 and 12-tungstophosphoric acid, the hydrothermal stability of support and acid all dropped.
Finally, Phosphotungstic acid and phosphomolybdic acid were mixed in 1:1 proportion, The Catalytic activity was good when it was supported by Impregnation method, During the synthesis of 2-(1-cyclohexenyl)cyclohexanone, Conversion of cyclohexanone could reach 86.5%,The catalyst had favorable Industrial prospect.
引文
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[1]王新平,叶兴凯,吴越.杂多酸在活性炭表面含氧基团上的化学键合作用.物理化学学报.1995,12(11):1105-1108
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[1]陈瑶,曾崇余。2-(1-环己烯基)环己酮合成反应的动力学。南京工业大学学报。2005,27(4)
[2]郑汝骊,王恩波.钼磷的多酸化学[J].化学通报,1984,(9)12-16.
[3]a)王恩波,赵世良,郑汝骊.石油化工.1985,14(10):615
b)王恩波.应用化学.1992,9(1):56
[4]Keggin J F.Proceedings of the Royal Society of London,Series A:Mathematical and Physical Sciences[J].Proc.R.Soc,1934,144:75.
[5]Keggin J F.Structure of the Molecule of 12-Phosphotungstic Acid[J].Nature,1933,131:908.
[6]王恩波,胡长文,许林.多酸化学导论[M],北京:化学工业出版社,1998,14-16.
[7]Timofeeva M N.Review Acid Catalysis by heteropoly acids[J].Appl Catal A:General,2003,256:19-35.
[8]Dimitris E,Katsoulis,Michael T.New Chemistry for Heteropolyanions in Anhydrous Nonpolar Solvents.Coordinative Unsaturation of Surface Atoms.Polyanion Oxygen Carriers[J].J.Am.Chem.Soc,1984,106(9):2737-2738.
[9]Altenau S L,P ope M T.Models for Heteropoly Blues.Degress of Valence Trapping in Vanadium and Molybenumtitated keggin Anions[J].Inorg chem,1975,2:417.
[10]Misono M.Heterogeneous catalysis by heteropoly compounds of Molybdenum and Tungsten[J].Catal Rev,1987,29(2-3):269-321.
[11]Misono M,Okuhara T,Ichiki T,et al.Pseudoliquid behavior of heteropoly compound catalysts.Unusual pressure dependences of the rate and selectivity for ethanol dehydration[J].J Am Chem Soc,1987,109(18):5535-5536.
[12]吴越,叶兴凯,杨向光等.杂多酸的固载化--关于制备负载型酸催化剂的一般原理[J].分子催化,1996,10(4):299-313.
[13]Baba T,Ono Y.Heteropolyacids and their salts supported on acdic Ion-exchange resin as highly active sold-acid catalysts[J].Appl Catal,1986,22(2):321-324.
[14]李颜,顾树玲.用改性离子交换树脂催化合成乙酸乙酯的研究[J].石油化工,1996,35(2):50-54.
[15]廖安平,童张法.强酸型阳离子交换树脂催化合成醋酸正丁酯[J].化学反应工程与工艺,1995,11(4):406-408.
[16]Caliman E,Dias J A,Dias S C.Solvent effect on the preparation of H_3PW_(12)O_(40)supported on alumina[J].Catal Today,2005,107-108:816-825.
[17]华瑞年,龚剑,王东仁等.γ-Al_2O_3负载杂多酸催化合成二甲醚[J].东北师范大学报(自然科学版),1997,(4):37-39.
[18]Yoon M,Chang J A,Kim Y.Heteropoly acid-incorporated TiO_2 colloids as novel photocatalytic systems resembling the photosynthetic reaction center[J].J Phys Chem B,2001,105(13):2539-2545.
[19]王新平,叶新凯,吴越.活性炭表面杂多酸的稳定性和酸性[J].催化学,1994,15(4):314-317.
[20]欧国勇,杨辉荣,方岩雄等.负载型杂多酸催化剂研究进展.化工进展,2001,(8):18
[21]Luis R P,Carmen V C,Mirta N B.Adsorption of Tungstophosphoric or Tungstosilicic Acids from Ethanol-Water Solutions on Carbon.Joural of colloid and interface science.1997,190,318-326
[22]Timofeeva M N,Matrosova M M,Reshetenko T V.etal.Filamentous carbons as a support for heteropoly acid.J.Mol.Catal.A Chem.2004,211(1-2):131-137
[23]Timofeeva M N,Matrosova M M,Ilinich G N.et al.Esterification of n-Butanol with Acetic Acid in the Presence of H_3PW_(12)O_(40)Supported on Mesoporous Carbon Materials.Kinetics and Catalysis.2003,44(6):778-787
[24]Vazquez P G,Blanco M N,Caceres C V.et al.Catalysts based on supported 12-molybdophosphoric acid.Catal Lett.1999,60(4):205-215
[25]Pizzio L R.Caceres C V.Blanco M N.Acid catalysts prepared by impregnation of tungstophosphoric acid solutions on different supports.Appl Catal A:General.1998,167:283-294
[26]ChuWen-ling,Yang Xiang-guang,Ye Xing-kai.et al.Adsorption of dodecatungstosilicic acid on to activated carbons from aqueous and acidic media.Adsorpt Sci Technol.1997,15(1):1-14
[27]楚文玲,叶兴凯,吴越.杂多酸在活性炭上的固载化Ⅳ.活性炭在酸性介质中对硅钼和磷钼酸杂多酸的吸附.离子交换与吸附.1995,11(6):518-523
[28]王新平,叶兴凯,吴越.活性炭表面杂多酸的稳定性和酸性.催化化学.1994,15(4):314-317
[29]刘文彬,邱琪浩,王军等.固载杂多酸催化合成双酚芴.精细化工.2007,24(12):1153-1158
[30]楚文玲,杨向光,叶兴凯等.活性炭固载杂多酸催化合成乙酸丁酯的研究.工业催化.1995,(4):28-34
[31]吴茂祥,高冬寿,李定.活性炭固载杂多酸催化合成柠檬酸三丁酯.精细化工.1999,16(4):24-27
[32]吴茂祥,高冬寿,李定.活性炭固载杂多酸催化合成柠檬酸三丁酯.现代化工.1999,19(3):29-31
[33]张龙,王树江,杨文龙.固载杂多酸催化剂PW_(12)/C催化合成二甘醇二苯甲酸酯.石油化工.1998,27(8):564-566。
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