焙烧温度对酯加氢制醇Cu-Al-Ba催化剂性能的影响

doi:10.3866/PKU.WHXB20100642

摘要/Abstract

摘要：

通过共沉淀法在不同焙烧温度下制备了新型无铬Cu-Al-Ba催化剂. 测试了其在高压釜中将棕榈油甲酯加氢制备高碳醇的反应性能. 结果表明催化剂的焙烧温度对催化性能有较大影响. 在从150 ℃升至750 ℃的过程中, 高碳醇的收率显示了三个阶段的变化, 相应地, 催化剂前驱体的热重(TG-DTG)曲线也显示了三个阶段的失重. X射线衍射(XRD)、X射线荧光(XRF), 透射电镜-能谱分析-选区电子衍射(TEM-EDS-SAED)、N₂物理吸附和程序升温还原(TPR)表征表明, 催化剂是由一种孔雀石-勃?石-碳酸钡前驱体制得的. 在300或550 ℃焙烧后, 催化剂组成为晶态的CuO、BaCO₃和非晶态的Al₂O₃. 其中, 非晶态的Al₂O₃为CuO的高分散提供了大的比表面, 杆状的BaCO₃组分有利于提供微孔结构. 在更高的焙烧温度750 ℃，新物相BaAl₂O₄的形成破坏了催化剂中的非晶态结构, 导致其比表面积和孔容的急剧下降, 并引起CuO物种的聚结. 550 ℃焙烧的催化剂显示了最高的高碳醇收率, 达到92.3%，这归因于其大的比表面积、大孔容和较高的CuO分散性.

关键词: 加氢, 酯, 高碳醇, Cu-Al-Ba催化剂, 焙烧温度

Abstract:

Novel chromium-free Cu-Al-Ba catalysts were prepared by co-precipitation and were calcined at different temperatures. Their performance during the hydrogenation of palm oil esters to higher alcohols was evaluated in an autoclave. Results showed that the catalytic properties of the catalysts were greatly influenced by the calcination temperatures. The yield of higher alcohols showed three steps when the calcination temperature of the catalysts was raised from 150 to 750 ℃. The thermogravimetric (TG-DTG) curves of the precursor also exhibited three steps related to mass loss. X-ray power diffraction (XRD), X-ray fluorescence (XRF), transmission electron microscopy-energy dispersive spectrometry-selected area electron diffraction (TEM-EDS-SAED), N₂-physisorption, and temperature- programmed reduction (TPR) characterization revealed that the catalysts were obtained from a malachite-boehmite-BaCO₃ precursor. After calcination at 300 or 550 ℃, the catalysts were found to be composed of crystalline CuO and BaCO₃ as well as amorphous Al₂O₃. Amorphous Al₂O₃ has a large surface area which results in a high dispersion of CuO. Rod-like BaCO₃ helps in the provision of micropores. The formation of BaAl₂O₄ at a calcination temperature of 750 ℃ destroys the amorphous structure and causes a sharp decline in the surface area and pore volume of the catalyst and this causes CuO aggregation. An optimal higher alcohol yield of 92.3% was obtained over the Cu-Al-Ba catalyst that was calcined at 550 ℃ due to its larger surface area, larger pore volume, and higher degree of CuO dispersion.

Key words: Hydrogenation, Ester, Higher alcohol, Cu-Al-Ba catalyst, Calcination temperature

袁鹏, 刘仲毅, 孙海杰, 刘寿长. 焙烧温度对酯加氢制醇Cu-Al-Ba催化剂性能的影响[J]. 物理化学学报, 2010, 26(08), 2235-2241. doi: 10.3866/PKU.WHXB20100642

YUAN Peng, LIU Zhong-Yi, SUN Hai-Jie, LIU Shou-Chang. Influence of Calcination Temperature on the Performance of Cu-Al-Ba Catalyst for Hydrogenation of Esters to Alcohols[J]. Acta Phys. -Chim. Sin. 2010, 26(08), 2235-2241. doi: 10.3866/PKU.WHXB20100642

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB20100642

https://www.whxb.pku.edu.cn/CN/Y2010/V26/I08/2235

参考文献

[1]. Hark, S. V. D.; Harrod, M.; MΦller, P. JAOCS, 1999, 76(11): 1363
[2]. Peters, R. A. Economics of a world scale fatty alcohol business.// Applewhite, T. H. Proceedings World Conference on Oleochemicals into the 21st Century, Champaign: American Oil Chemists′ Society, 1991: 181-188
[3]. Echeverri, D. A.; Marín, J. M.; Restrepo, G. M.; Rios, L. A. Appl. Catal. A-Gen., 2009, 366: 342
[4]. Pérez-Cadenas, A. F.; Kapteijn, F.; Zieverink, M. M. P.; Moulijn, J. A. Catal. Today, 2007, 128: 13
[5]. Nikolaou, N.; Papadopoulos, C. E.; Lazaridou, A.; Koutsoumba, A.; Bouriazos, A.; Papadogianakis, G. Catal. Commun., 2009, 10: 451
[6]. Rieke, R. D.; Thakur, D. S.; Roberts, B. D.; White, G. T. JAOCS, 1997, 74(4): 333
[7]. Luo, G.; Yan, S.; Qiao, M.; Fan, K. Appl. Catal. A-Gen., 2007, 332: 79
[8]. Nomura, K.; Ogura, H.; Imanishi, Y. J. Mol. Catal. A-Chem., 2002, 178: 105
[9]. Figueiredo, F. C. A.; Jordao, E.; Carvalho, W. A. Appl. Catal. A- Gen., 2008, 351: 259
[10]. Miyake, T.; Makino, T.; Taniguchi, S.; Watanuki, H.; Niki, T.; Shimizu, S.; Kojima, Y.; Sano, M. Appl. Catal. A-Gen., 2009, 364: 108
[11]. Brands, D. S.; Poels, E. K.; Bliek, A. Appl. Catal. A-Gen., 1999, 184: 279
[12]. Corbos, E. C.; Courtois, X.; Bion, N.; Marecot, P.; Duprez, D. Appl. Catal. B-Environ., 2008, 80: 62
[13]. Xiao, J.; Li, X.; Deng, S.; Wang, F.; Wang, L. Catal. Commun., 2008, 9: 563
[14]. Lindholm, A.; Currier, N. W.; Dawody, J.; Hidayat, A.; Li, J.; Yezerets, A.; Olsson, L. Appl. Catal. B-Environ., 2009, 88: 240
[15]. Yuan, P.; Zhu, W.; Liu, S. Flav. Frag. Cosm., 2007, 4: 19
[16]. Paquot, C.; Hautfenne, A. Standard methods for the analysis of oils, fats and derivatives. 7th Revised and Enlarged Edition, Oxford: Blackwell Scientific Publications Ltd., 1987: 73-116
[17]. Szailer, T.; Kwak, J. H.; Kim, D. H.; Szanyi, J.; Wang, C.; Peden, C. H. F. Catal. Today, 2006, 114: 86
[18]. Li, J.; Pan, Y.; Xiang, C.; Ge, Q.; Guo, J. Ceram. Inter., 2006, 32: 587
[19]. Kumari, V. D.; Subrahmanyam, M.; Ratnamala, A.; Venugopal, D.; Srinivas, B.; Phanikrishna Sharma, M. V.; Madhavendra, S. S.; Bikshapathi, B.; Venkateswarlu, K.; Krishnudu, T.; Prasad, K. B. S.; Raghavan, K. V. Catal. Commun., 2002, 3: 417
[20]. Chen, L.; Shen, Y.; Xie, A.; Zhu, J.; Wu, Z.; Yang, L. Cryst. Res. Technol., 2007, 42(9): 886
[21]. Lefèvre, G.; Duc, M.; Lepeut, P.; Caplain, R.; Fédoroff, M. Langmuir, 2002, 18: 7530
[22]. Koga, N.; Fukagawa, T.; Tanaka, H. J. Therm. Anal. Calor., 2001, 64: 965
[23]. Huang, H.; Cao, G.; Fan, C.; Wang, S.; Wang, S. Korean J. Chem. Eng., 2009, 26(6): 1574
[24]. Waugh, K. C. Catal. Today, 1992, 15: 51
[25]. Rasmussen, P. B.; Kazuta, M.; Chorkendorff, I. Surf. Sci., 1994, 318: 267
[26]. Yoshihara, J.; Parker, S.; Schafer, A.; Campbell, C. T. Catal. Lett., 1995, 31: 313
[27]. Chinchen, G. C.; Denny, P. J.; Jennings, J. R.; Spencer, M. S.; Waugh, K. C. Appl. Catal., 1988, 36: 1
[28]. Busca, G.; Costantino, U.; Marmottini, F.; Montanari, T.; Patrono, P.; Pinzari, F.; Ramis, G. Appl. Catal. A-Gen., 2006, 310: 70
[29]. Porta, P.; Campa, M. C.; Fierro, G.; Lo Jacono, M.; Minelli, G.; Moretti, G.; Stoppa, L. J. Mater. Chem., 1993, 3: 505
[30]. Bart, J. C. J.; Sneeden, R. P. A. Catal. Today, 1987, 2: 1
[31]. Chinchen, G. C.; Mansfield, K.; Spencer, M. S. Chemtech, 1990, 20(11): 692
[32]. Guo, P. J.; Chen, L. F.; Yan, S. R.; Dai, W. L.; Qiao, M. H.; Xu, H. L.; Fan, K. N. J. Mol. Catal. A-Chem., 2006, 256: 164
[33]. Chen, L. F.; Guo, P. J.; Zhu, L. J.; Qiao, M. H.; Shen, W.; Xu, H. L.; Fan, K. N. Appl. Catal. A-Gen., 2009, 356: 129
[34]. Chen, L. F.; Guo, P. J.; Qiao, M. H.; Yan, S. R.; Li, H. X.; Shen, W.; Xu, H. L.; Fan, K. N. J. Catal., 2008, 257(1): 172