Co-B/γ-Al2O3非晶态催化剂的制备及其催化乳酸乙酯液相加氢性能

doi:10.3866/PKU.WHXB201501052

物理化学学报 >> 2015, Vol. 31 >> Issue (3): 527-532.doi: 10.3866/PKU.WHXB201501052

Co-B/γ-Al₂O₃非晶态催化剂的制备及其催化乳酸乙酯液相加氢性能

赵凤伟, 沈美玉, 王琳, 杜长海

长春工业大学化学工程学院, 长春 130012

收稿日期:2014-11-05 修回日期:2015-01-02 发布日期:2015-03-06
通讯作者: 杜长海 E-mail:du661123@163.com
基金资助:
吉林省科技厅自然科学基金(201215117)资助项目

Preparation of Amorphous Co-B/γ-Al₂O₃ Catalyst and Its Performance in Catalytic Liquid Phase Hydrogenation of Ethyl Lactate

ZHAO Feng-Wei, SHEN Mei-Yu, WANG Lin, DU Chang-Hai

School of Chemical Engineering, Changchun University of Technology, Changchun 130012, P. R. China

Received:2014-11-05 Revised:2015-01-02 Published:2015-03-06
Contact: DU Chang-Hai E-mail:du661123@163.com
Supported by:
The project was supported by the Natural Science Foundation of Jilin Provincial Science &Technology Department, China (201215117).

摘要/Abstract

摘要：

采用浸渍-还原法制备了负载型Co-B/γ-Al₂O₃非晶态合金催化剂, 并将其应用于乳酸乙酯液相加氢制备1,2-丙二醇(1,2-PDO)反应中, 研究了其催化加氢性能. 采用电感耦合等离子体(ICP)发射光谱仪、X射线衍射(XRD)仪、透射电子显微镜(TEM)、差示扫描量热(DSC)、X射线光电子能谱(XPS)等手段对催化剂的性能进行了表征, 考察了制备条件对催化剂性能的影响. 结果表明, 新鲜的Co-B/γ-Al₂O₃催化剂具有非晶态结构, Co-B均匀地分散在载体γ-Al₂O₃上. 随着Co负载量的增加, 催化剂的热稳定性提高, 催化剂表面Co/B原子比增加. 当金属Co理论负载量为30%(质量分数, w)时, Co-B/γ-Al₂O₃催化剂表现出最高的加氢催化性能, 在160 ℃, 氢气压力为6.0 MPa条件下反应9 h, 乳酸乙酯的转化频率(TOF)为1.41 h^-1, 转化率达到93.63%, 1,2-丙二醇的选择性达到96.10%. 催化剂的加氢性能取决于其分散均匀的Co-B纳米粒子、较高的表面Co/B原子比及Co和B之间的电子转移效应.

关键词: 非晶态催化剂, Co-B/γ-Al₂O₃, 乳酸乙酯, 1,2-丙二醇, 催化加氢

Abstract:

Supported cobalt amorphous catalysts Co-B/γ-Al₂O₃ were prepared using an impregnation-chemical reduction method for liquid phase hydrogenation of ethyl lactate to 1,2-propanediol (1,2-PDO). The Co-B/γ-Al₂O₃ catalysts were characterized using inductively coupled plasma (ICP) optical emission spectrometry, X-ray diffraction (XRD), transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and X-ray photoelectron spectroscopy (XPS). The effects of the catalyst preparation conditions on the hydrogenation of ethyl lactate were investigated. All the fresh catalysts showed an amorphous structure and Co-B particles were dispersed uniformly on the γ-Al₂O₃ support. The thermal stability of the amorphous catalyst and the Co/B atomic ratio of surface composition increased with increasing the Co content. The Co-B/γ-Al₂O₃ amorphous catalyst showed the highest catalytic activity when the theoretical loading of metal Co was 30% (mass fraction, w). The ethyl lactate turnover frequency (TOF), conversion, and selectivity to 1,2-PDO reached 1.41 h^-1, 93.63%, and 96.10%, respectively at a reaction temperature of 160 ℃ and hydrogen pressure of 6.0 MPa for 9 h. The higher catalytic performance of the 30%(w) Co-B/γ-Al₂O₃ supported amorphous catalyst is attributed to its highly dispersing Co-B particles, higher Co/B atomic ratio of surface composition, and electron transfer effect between Co and B.

Key words: Amorphous catalyst, Co-B/γ-Al₂O₃, Ethyl lactate, 1,2-Propanediol, Catalytic hydrogenation

赵凤伟, 沈美玉, 王琳, 杜长海. Co-B/γ-Al₂O₃非晶态催化剂的制备及其催化乳酸乙酯液相加氢性能[J]. 物理化学学报, 2015, 31(3): 527-532.

ZHAO Feng-Wei, SHEN Mei-Yu, WANG Lin, DU Chang-Hai. Preparation of Amorphous Co-B/γ-Al₂O₃ Catalyst and Its Performance in Catalytic Liquid Phase Hydrogenation of Ethyl Lactate[J]. Acta Phys. -Chim. Sin., 2015, 31(3): 527-532.

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201501052

https://www.whxb.pku.edu.cn/CN/Y2015/V31/I3/527

参考文献

(1) Fan, Y. X.; Zhou, C. H.; Zhu, X. H. Catal. Rev. 2009, 51, 293. doi: 10.1080/01614940903048513
(2) Chaminand, J.; Djakovitch, L. A.; Gallezot, P.; Marion, P.; Pinel, C.; Rosier, C. Green Chem. 2004, 6, 359. doi: 10.1039/b407378a
(3) Dusselier, M.; VanWouwe, P.; Dewaele, A.; Makshina, E.; Sels, B. F. Energy & Environmental Science 2013, 6, 1415. doi: 10.1039/c3ee00069a
(4) Corma, A.; Iborra, S.; Velty, A. Cat. Rev. 2007, 107, 2411.
(5) Zhang, Z. G.; Jackson, J. E.; Miller, D. J. Appl. Catal. A 2001, 219, 89. doi: 10.1016/S0926-860X(01)00669-X
(6) Luo, G.; Yan, S. R.; Qiao, M. H.; Zhuang, J. H.; Fan, K. N. Appl. Catal. A 2004, 275, 95. doi: 10.1016/j.apcata.2004.07.024
(7) Yang, Q.; Zhang, J.; Zhang, L.; Fu, H. Y.; Zheng, X. L.; Yuan, M. L.; Chen, H.; Li, R. X. Catal. Commun. 2013, 40, 37. doi: 10.1016/j.catcom.2013.05.023
(8) Fan, G. Y.; Zhang, Y.; Zhou, Y. F.; Li, R. X.; Chen, H.; Li, X. J. Chem. Lett. 2008, 37, 852. doi: 10.1246/cl.2008.852
(9) Simonov, M. N.; Zaikin, P. A.; Simakova, I. L. Appl. Catal. B 2012, 119, 340.
(10) Kasinathan, P.; Yoon, J.W.; Hwang, D.W.; Lee, U.; Hwang, J. S.; Hwang, Y. K.; Chang, J. S. Appl. Catal. A 2013, 451, 236. doi: 10.1016/j.apcata.2012.10.027
(11) Xue, J. J.; Cui, F.; Huang, Z.W.; Zuo, J. L.; Chen, J.; Xia, C. G. Chin. J. Chem. 2011, 29, 1319. doi: 10.1002/cjoc.v29.7
(12) Huang, L.; Zhu, Y. L.; Zheng, H. Y.; Du, M. X.; Li, Y.W. Appl. Catal. A 2008, 349, 204. doi: 10.1016/j.apcata.2008.07.031
(13) Ji,W. R.; Tan, Y. B.; Zeng, Y. L.; Ying, H. J.; Hu, L. B. Journal of Zhejiang University of Technology 2013, 41, 183. [计伟荣, 谭冶斌, 曾玉龙, 应惠娟, 胡凌波. 浙江工业大学学报, 2013, 41, 183.]
(14) Chen, Y. Catal. Today 1998, 44, 3. doi: 10.1016/S0920-5861(98)00169-2
(15) Molnáar, Á.; Smith, G. V.; Bartók, M. Adv. Catal. 1989, 36, 329.
(16) Wang,W. Y.; Zhang, X. Z.; Yang, Y. Q.; Yang, Y. S.; Peng, H. Z.; Luo, H. A. Acta Phys. -Chim. Sin. 2012, 28, 1243. [王威燕, 张小哲, 杨运泉, 杨彦松, 彭会左, 罗和安. 物理化学学报, 2012, 28, 1243.] doi: 10.3866/PKU.WHXB201203081
(17) Li, H.; Liu, J.; Xie, S. H.; Qiao, M. H.; Dai,W. L.; Li, H. X. J. Catal. 2008, 259, 104. doi: 10.1016/j.jcat.2008.07.015
(18) Chen, Y. Z.; Liaw, B. J.; Chiang, S. J. Appl. Catal. A 2005, 284, 97. doi: 10.1016/j.apcata.2005.01.023
(19) Ma, X. Y.; Zhao, F.W.; Sun, D.; Du, C. H. Fine Chemicals 2014, 31, 452. [马晓雨, 赵凤伟, 孙德, 杜长海. 精细化工, 2014, 31, 452.]
(20) Li, H. X.; Li, H.;Wang, M. H. Appl. Catal. A 2001, 207, 129. doi: 10.1016/S0926-860X(00)00662-1
(21) Chiang, S. J.; Yang, C. H.; Chen, Y. Z.; Liaw, B. J. Appl. Catal. A 2007, 326, 180. doi: 10.1016/j.apcata.2007.04.019
(22) Xu, D. Y.; Zhao, L.; Dai, P.; Ji, S. F. J. Nat. Gas Chem. 2012, 21, 488. doi: 10.1016/S1003-9953(11)60395-2
(23) Wang, L. J.; Li,W.; Zhang, M. H.; Tao, K. Y. Appl. Catal. A 2004, 259, 185. doi: 10.1016/j.apcata.2003.09.037
(24) Yamashita, H.; Funabiki, T.; Yoshida, S. J. Chem. Soc. Chem. Commun. 1984, 868.
(25) Zhang, R. B.; Li, F. Y.; Shi, Q. J.; Luo, L. T. Appl. Catal. A 2001, 205, 279. doi: 10.1016/S0926-860X(00)00574-3
(26) Yang, C. C.; Chen, M. S.; Chen, Y.W. Int. J. Hydrog. Energy 2011, 36, 1418. doi: 10.1016/j.ijhydene.2010.11.006
(27) Li, H. X.; Li, H.; Zhang, J.; Dai,W. L.; Qiao, M. H. J. Catal. 2007, 246, 301. doi: 10.1016/j.jcat.2006.12.014
(28) Li, H.; Li, H, X.; Deng, J. F. Catal. Today 2002, 74, 53. doi: 10.1016/S0920-5861(01)00530-2
(29) Long, J. Y.; Ma, L.; He, D. H. Acta Phys. -Chim. Sin. 2010, 26, 2719. [龙俊英, 马兰, 贺德华. 物理化学学报, 2010, 26, 2719.] doi: 10.3866/PKU.WHXB20101022

[1]	韩波,程寒松. 镍族金属团簇在催化加氢过程中的应用[J]. 物理化学学报, 2017, 33(7): 1310 -1323 .
[2]	仇松柏,翁育靖,刘琪英,马隆龙,张琦,王铁军. 乙二醇促进制备高分散的Co/SiO₂催化剂及其催化乳酸乙酯转化为1,2-丙二醇的气相加氢活性[J]. 物理化学学报, 2016, 32(6): 1511 -1518 .
[3]	高爽, 颜见标, 丛德全, 随强盛, 夏延洋, 程东东, 包强, 王振旅, 王力彦. Sn改性的Ru/H-CMK-3催化剂的制备及其肉桂醛选择性加氢性能的研究[J]. 物理化学学报, 2015, 31(7): 1391 -1398 .
[4]	王威燕, 张小哲, 杨运泉, 杨彦松, 彭会左, 罗和安. La-Ni-Mo-B非晶态催化剂的制备及其苯酚加氢脱氧催化性能[J]. 物理化学学报, 2012, 28(05): 1243 -1251 .
[5]	毛东森, 郭强胜, 俞俊, 韩璐蓬, 卢冠忠. Ce添加对Cu-Fe/SiO₂催化合成气制低碳醇性能的影响[J]. 物理化学学报, 2011, 27(11): 2639 -2645 .
[6]	龙俊英, 马兰, 贺德华. 负载型非晶态Co-B催化剂在1-辛烯氢甲酰化中的应用[J]. 物理化学学报, 2010, 26(10): 2719 -2725 .
[7]	郑小娟, 周娅芬, 付海燕, 陈华, 李贤均, 李瑞祥. 酯加氢反应中影响羧基活化的因素[J]. 物理化学学报, 2010, 26(10): 2699 -2704 .
[8]	许兴中;杨建锋;李小年;严新焕. 激光溅射法制备Pt/CNTs催化剂用于邻氯硝基苯的液相加氢反应[J]. 物理化学学报, 2008, 24(01): 121 -126 .
[9]	赵永祥;秦晓琴;侯希才;徐贤伦;刘滇生. 镍基催化剂的制备、表征及选择加氢性能[J]. 物理化学学报, 2003, 19(05): 450 -454 .
[10]	金亚旭;刘宗健;陈卫祥;徐铸德. 纳米碳管负载金属镍催化叶绿素加氢反应[J]. 物理化学学报, 2002, 18(05): 459 -462 .
[11]	范荫恒;廖世健;李伟娜;徐杰;王复东. 纳米KH颗粒的热稳定性及其化学反应活性[J]. 物理化学学报, 2002, 18(01): 55 -58 .
[12]	张晓昕, 马爱增, 慕旭宏, 闵恩泽, 黄晓茜, 王蓉. 负载型Ni-B非晶态合金催化剂的表征[J]. 物理化学学报, 2000, 16(02): 180 -183 .
[13]	范荫恒, 廖世健, 余道容. 纳米氢化钠的热稳定性和化学反应活性[J]. 物理化学学报, 1998, 14(12): 1057 -1060 .
[14]	盛春, 周诗瑶, 李和兴, 邓景发. Ni-P/SiO₂催化剂晶化过程及其加氢活性研究[J]. 物理化学学报, 1998, 14(02): 164 -168 .

Co-B/γ-Al₂O₃非晶态催化剂的制备及其催化乳酸乙酯液相加氢性能

Preparation of Amorphous Co-B/γ-Al₂O₃ Catalyst and Its Performance in Catalytic Liquid Phase Hydrogenation of Ethyl Lactate

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 14

Metrics

推荐阅读 0