Cu含量对以水滑石为前驱体的Cu/Co/Mn/Al催化剂高级醇合成性能的影响

doi:10.3866/PKU.WHXB201704143

物理化学学报 >> 2017, Vol. 33 >> Issue (8): 1672-1680.doi: 10.3866/PKU.WHXB201704143

Cu含量对以水滑石为前驱体的Cu/Co/Mn/Al催化剂高级醇合成性能的影响

廖珮懿^1,²,张辰^1,²,张丽君¹,杨彦章²,钟良枢²,郭晓亚¹,王慧^2,*(),孙予罕^2,*()

¹ 上海大学环境与化学工程学院,上海200444
² 中国科学院上海高等研究院,上海201210

收稿日期:2016-12-28 发布日期:2017-06-14
通讯作者: 王慧,孙予罕 E-mail:wanghh@sari.ac.cn;yhsun@sari.ac.cn
基金资助:
国家自然科学基金(21403278);神华集团有限责任公司;山西潞安矿业（集团）有限责任公司;荷兰皇家壳牌集团

Influences of Cu Content on the Cu/Co/Mn/Al Catalysts Derived from Hydrotalcite-Like Precursors for Higher Alcohols Synthesis via Syngas

Pei-Yi LIAO^1,²,Chen ZHANG^1,²,Li-Jun ZHANG¹,Yan-Zhang YANG²,Liang-Shu ZHONG²,Xiao-Ya GUO¹,Hui WANG^2,*(),Yu-Han SUN^2,*()

¹ School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444, P. R. China
² Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, P. R. China

Received:2016-12-28 Published:2017-06-14
Contact: Hui WANG,Yu-Han SUN E-mail:wanghh@sari.ac.cn;yhsun@sari.ac.cn
Supported by:
The project was supported by the National Natural Science Foundation of China(21403278);China Shenhua Coal to Liquid;Chemical Company Limited, Shanxi Lu?an Coal Corporation Limited;Shell Global Solutions International B. V

摘要/Abstract

摘要：

采用共沉淀法制备了一系列不同铜钴摩尔比（0，0.1，0.5，1.0，2.0）的Cu/Co/Mn/Al层状结构催化剂并考察了其在合成气制混合醇反应中的催化性能，采用N₂物理吸脱附、电感耦合等离子体原子发射光谱法（ICP-AES）、X射线衍射（XRD）、扫描电子显微镜（SEM）、氢气程序升温还原（H₂-TPR），热重分析（TG）和高分辨透射电子显微镜（HRTEM）等对催化剂进行了表征分析。结果表明，适当的铜钴摩尔比可以增大催化剂的比表面积，提高催化剂的还原性能，并能形成较规整的层状结构从而提供更均一分散的合成醇活性位，从而提高催化活性和醇选择性。当铜钴摩尔比为0.5时，得到最高的醇时空产率（STY）和醇质量选择性，分别为0.071 g·g^-1·h^-1和35.9%。

关键词: 高级醇合成, 水滑石前驱体, Cu/Co/Mn/Al催化剂, 铜钴摩尔比, 合成气转化

Abstract:

A series of Cu/Co/Mn/Al catalysts derived from hydrotalcite precursors with different Cu/Co molar ratios (0, 0.1, 0.5, 1.0, and 2.0) were prepared and used for the synthesis of higher alcohols from syngas. N₂ physical adsorption desorption, inductively coupled plasma atomic emission spectrometry (ICP-AES), X-ray diffraction (XRD), scanning electron microscopy (SEM), hydrogen temperature-programmed reduction (H₂-TPR), thermogravimetry (TG), and high-resolution transmission electron microscopy (HRTEM) techniques were employed to investigate the physical and chemical properties of the Cu/Co/Mn/Al catalysts. The results show that the optimum Cu content can increase specific surface area, improve reducibility, and form regular layered structure to provide more uniform distribution of active sites, thereby enhancing catalytic activity and alcohol selectivity. When the Cu/Co molar ratio was 0.5, the yield of alcohol and the alcohol selectivity reached the maximum values of 0.071 g·g^-1·h^-1 and 35.9%, respectively.

Key words: Higher alcohols synthesis, Layered-double hydroxide, Cu/Co/Mn/Al catalyst, Cu/Co molar ratio, Syngas conversion

廖珮懿,张辰,张丽君,杨彦章,钟良枢,郭晓亚,王慧,孙予罕. Cu含量对以水滑石为前驱体的Cu/Co/Mn/Al催化剂高级醇合成性能的影响[J]. 物理化学学报, 2017, 33(8), 1672-1680. doi: 10.3866/PKU.WHXB201704143

Pei-Yi LIAO,Chen ZHANG,Li-Jun ZHANG,Yan-Zhang YANG,Liang-Shu ZHONG,Xiao-Ya GUO,Hui WANG,Yu-Han SUN. Influences of Cu Content on the Cu/Co/Mn/Al Catalysts Derived from Hydrotalcite-Like Precursors for Higher Alcohols Synthesis via Syngas[J]. Acta Phys. -Chim. Sin. 2017, 33(8), 1672-1680. doi: 10.3866/PKU.WHXB201704143

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201704143

https://www.whxb.pku.edu.cn/CN/Y2017/V33/I8/1672

参考文献

1	Pan X. L. ; Fan Z. L. ; Chen W. Nat. Mater. 2007, 6, 507.
2	Spivey J. J. ; Egbebi A. Chem. Soc. Rev. 2007, 36, 1514.
3	Subramani V. ; Gangwal S. K. Energy Fuels. 2008, 22, 814.
4	Gupta M. ; Smith M. L. ACS Catal. 2011, 1, 641.
5	Fang K. G. ; Li D. B. ; Lin M. G. Catal. Today. 2009, 147, 133.
6	Choi Y. M. ; Liu P. J. Am. Chem. Soc. 2009, 131, 13054.
7	Prieto G. ; Concepción P. J. Catal. 2011, 280, 274.
8	Yang N. Y. ; Medford A. J. ; Liu X.Y. J. Am. Chem. Soc. 2016, 138, 3705.
9	Sun J. ; Wan S. L. ; Wang F. Ind. Eng. Chem. Res. 2015, 54, 7841.
10	Epling W. S. ; Minahan D. M. J. Catal. 1998, 175, 175.
11	Xu M. T. ; Gines M. J. L. ; Hilmen A. M. J. Catal. 1997, 171, 130.
12	Xiang M. L. ; Li D. B. ; Li W. H. Catal. Commun. 2007, 8, 503.
13	Shou H. ; Ferrari D. ACS Catal. 2012, 2, 1408.
14	Thao N. T. ; Niaki M. H. Z. J. Catal. 2007, 245, 348.
15	Subramanian N. D. ; Balaji G. Catal. Today. 2009, 147, 100.
16	Xu H. Y. ; Chu W. ; Deng S. Y. Acta Phys. -Chim. Sin. 2010, 26, 345.
16	徐慧远; 储伟; 邓思玉. 物理化学学报, 2010, 26, 345.
17	Xiao K. ; Qi X. Z. Catal. Sci. Technol. 2013, 3, 1591.
18	Wang J. J. ; Chernavskii P. A. J. Catal. 2012, 286, 51.
19	Yang Y. Z. ; Qi X. Z. ; Wang X. X. Catal. Today. 2016, 270, 101.
20	Prieto G. Z. ; Beijer S. Angew. Chem. Int. Ed. 2014, 53, 6397.
21	Liu Y. J. ; Zuo Z. J. Fuel. Process. Technol. 2016, 144, 186.
22	Xiang Y. Z. ; Chitry V. J. Am. Chem. Soc. 2013, 135, 7114.
23	Duan X. Chem. Soc. Rev. 2014, 43, 7040.
24	Gao W. ; Zhao Y. F. ; Liu J. M. Catal. Sci. Technol. 2013, 31, 324.
25	Grey C. P. Science 2008, 321, 113.
26	Ma K. Y. ; Cheng J. P. J. Alloy. Compd. 2016, 679, 277.
27	Yuan Z. ; Wang L. ; Wang J. Appl. Catal. B: Environ. 2011, 101, 431.
28	Xia S. ; Nie R. ; Lu X. J. Catal. 2012, 296, 1.
29	Anton J. ; Nebel J. Appl. Catal. A: Gen. 2015, 505, 326.
30	Su J. J. ; Zhang Z. P. J. Catal. 2016, 336, 94.
31	Gao P. ; Li F. ; Zhan H. J. J. Catal. 2013, 298, 51.
32	Wang J. J. ; Chernavskii P. A. J. Catal. 2012, 286, 51.
33	Deng S. Y. ; Chu W. ; Chu W. J. Nat. Gas. Chem. 2008, 17, 369.
34	Alejandre. A. ; Medina F. ; Salagre P. Chem. Mater. 1999, 11, 939.
35	Smith M. L. ; Campos. A. ; Spivey J. J. Catal. Today. 2012, 182, 60.
36	Frantisek K. ; Tomas R. ; Jana D. J. Solid State Chem. 2006, 179, 812.
37	Pei Y. ; Jian S. ; Chen Y. RSC Adv. 2015, 5, 76330.
38	Byoung K. K. ; Dae S. P. ; Yang S. Y. Catal. Commu. 2012, 24, 90.
39	Ning X. ; An Z. ; He J. J. Catal. 2016, 340, 236.
40	Xu Z. P. ; Zeng H. C. J. Phys. Chem. B. 2000, 104, 10206.
41	Cheng. J. ; Yu. J.J. ; Wang. X. P. Energy Fuels 2008, 22, 2131.
42	Velu S. ; Sabde D. P. Chem. Mater. 1998, 10, 3451.
43	Trujillano R. ; Holgado M. J. Phys. B 2006, 373, 267.
44	Behrens. M. ; Kasatkin. I. Chem. Mater. 2010, 22, 386.
45	Gao P. ; Yang H. J. CO 2Util. 2016, 16, 32.
46	Cheng X. F. ; Wu B. S. J. Mol. Catal. A: Chem. 2010, 329, 103.
47	Laan G. P. V. Catal. Rev. 1999, 41, 255.
48	Matsuzaki T. ; Takeuchi K. ; Hanaoka T. Catal. Today 1996, 28, 251.

[1]	刘影, 刘晓放, 夏林, 黄超杰, 吴兆萱, 王慧, 孙予罕. 以类水滑石为前驱体的Cu/ZnO/Al₂O₃催化剂用于CO_x加氢合成甲醇：CO在反应混合物中的作用[J]. 物理化学学报, 2022, 38(3): 2002017 - .
[2]	邵自龙, 刘晓放, 张书南, 王慧, 孙予罕. 负载型Rh基催化剂上的CO加氢制乙醇反应：载体效应[J]. 物理化学学报, 2021, 37(10): 1911053 - .
[3]	高鹏, 李枫, 赵宁, 王慧, 魏伟, 孙予罕. 以类水滑石为前驱体的Cu/Zn/Al/（Zr）/（Y）催化剂制备及其催化CO₂加氢合成甲醇的性能[J]. 物理化学学报, 2014, 30(6): 1155 -1162 .
[4]	汪海有;刘金波;傅锦坤;蔡启瑞. 合成气转化为乙醇的反应机理[J]. 物理化学学报, 1991, 7(06): 681 -687 .

Cu含量对以水滑石为前驱体的Cu/Co/Mn/Al催化剂高级醇合成性能的影响

Influences of Cu Content on the Cu/Co/Mn/Al Catalysts Derived from Hydrotalcite-Like Precursors for Higher Alcohols Synthesis via Syngas

RichHTML

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 4

Metrics

推荐阅读 0