CuCoCe Catalysts Supported on Carbon Nanotubes for Higher Alcohol Synthesis from Syngas†

doi:10.7503/cjcu20160185

Abstract

Abstract:

A series of CuCoCe catalysts was prepared by co-impregnation method using different carbon nanotubes as support. In order to improve alcohol synthesis property, the effects of the length and carboxyl group of carbon nanotubes on CuCoCe catalysts were investigated. The catalysts were characterized by X-ray diffraction, N₂ adsorption-desorption, transmission electron microscopy and X-ray photoelectron spectroscopy. The results showed that the catalyst supported on carbon nanotubes of 0.5—2 μm with 2.0%(mass fraction) carboxyl group had highest space-time yield(783.72 mg· $g cat - 1$ ·h^-1) and the selectivity of C₂₊OH reached 82.71%. The study showed that the short nanotubes can promote more metal particles into the interior of carbon nanotubes and make activity components disperse uniformly, which can significantly improve the conversion of CO and the space-time yield of alcohols. Existence of carboxyl group on carbon nanotubes can enhance the interaction between active metal and support, which can remarkably increase the selectivity of C₂₊OH.

Key words: Carbon nanotubes, Carboxyl group, Syngas, Higher alcohol, CuCoCe catalyst

CLC Number:

O643

TrendMD:

YOU Xiangxuan, FAN Jinchuan, HUANG Wei, ZHOU Youzhi, WEI Junyi. CuCoCe Catalysts Supported on Carbon Nanotubes for Higher Alcohol Synthesis from Syngas^†[J]. Chem. J. Chinese Universities, 2016, 37(9): 1694.

Figures/Tables 8

Table 1 Catalytic performance of different catalysts for CO hydrogenation reaction*

Cat.	CO conv.(%)	Carbon selectivity(molar fraction, %)			STY_ROH/ (mg· $g cat - 1$ ·h^-1)	Alcohol distribution(molar fraction, %)
Cat.	CO conv.(%)	CO₂	ROH	HC	STY_ROH/ (mg· $g cat - 1$ ·h^-1)	MeOH	EtOH	PrOH	BuOH
CNT	26.15	5.10	49.18	45.72	411.16	25.01	39.53	19.66	15.79
CNTC	43.66	3.03	48.89	48.08	638.50	13.29	37.67	27.70	21.34
SCNT	46.04	4.89	47.25	47.86	717.75	23.34	31.93	27.87	16.86
SCNTC	60.11	5.37	42.46	52.17	783.72	17.29	38.97	27.59	16.15

Table 1 Catalytic performance of different catalysts for CO hydrogenation reaction*

Cat.	CO conv.(%)	Carbon selectivity(molar fraction, %)			STY_ROH/ (mg· $g cat - 1$ ·h^-1)	Alcohol distribution(molar fraction, %)
Cat.	CO conv.(%)	CO₂	ROH	HC	STY_ROH/ (mg· $g cat - 1$ ·h^-1)	MeOH	EtOH	PrOH	BuOH
CNT	26.15	5.10	49.18	45.72	411.16	25.01	39.53	19.66	15.79
CNTC	43.66	3.03	48.89	48.08	638.50	13.29	37.67	27.70	21.34
SCNT	46.04	4.89	47.25	47.86	717.75	23.34	31.93	27.87	16.86
SCNTC	60.11	5.37	42.46	52.17	783.72	17.29	38.97	27.59	16.15

Fig.1 XRD patterns of different catalysts before(A) and after(B) reaction a. CNT; b. CNTC; c. SCNT; d. SCNTC.

Fig.2 N2 adsorption-desorption isotherms(A) and pore size distributions(B) of carbon nanotubes a. TNM3; b. TNMC3; c. TNSM3; d. TNSMC3.

Fig.3 N2 adsorption-desorption isotherms(A) and pore size distributions(B) of different catalysts before reaction a. CNT; b. CNTC; c. SCNT; d. SCNTC.

Fig.4 TEM images of the CNT(A), CNTC(B), SCNT(C) and SCNTC(D) catalysts

Table 2 Textural properties of different catalysts

Sample	Outside diameter/nm	Length/μm	Content of —COOH (mass fraction, %)	Specific surface area/(m²·g^-1)	V/(cm³·g^-1)	Average pore size/nm
TNM3	10—20	10—30	0.0	156.0	1.76	45.1
TNMC3	10—20	10—30	2.0	171.5	1.75	40.8
TNSM3	10—20	0.5—2	0.0	177.5	1.16	26.1
TNSMC3	10—20	0.5—2	2.0	179.4	0.65	25.5
CNT				143.9	0.98	27.3
CNTC				147.6	0.94	25.4
SCNT				137.5	0.78	22.8
SCNTC				155.1	0.80	20.6

Fig.5 Cu2p XPS spectra of different catalysts before(A) and after(B) reaction a. CNT; b. CNTC; c. SCNT; d. SCNTC.

Fig.6 Co2p XPS spectra of the different catalysts before(A) and after reaction(B) a. CNT; b. CNTC; c. SCNT; d. SCNTC.

References 29

[1]	Fang K. G., Li D. B., Lin M. G., Xiang M. L., Wei W., Sun Y. H., Catalysis Today,2009, 147(2), 133—138
[2]	Xiao K., Bao Z. H., Qi X. Z., Wang X. X., Zhong L. S., Fang K. G., Lin M. G., Sun Y. H., Chin. J. Catal., 2013, 34(1), 116—129
	(肖康, 鲍正洪, 齐行振, 王新星, 钟良枢, 房克功, 林明桂, 孙予罕. 催化学报, 2013, 34(1), 116—129)
[3]	Xu H. Y., Chu W., Deng S. Y., Acta Phys.-Chim. Sin., 2010, 24(2), 345—349
	(徐慧远, 储伟, 邓思玉. 物理化学学报, 2010, 24(2), 345—349)
[4]	Jiao G. P., Ding Y. J., Zhu H. J., Li X. M., Li J.W., Dong W. D., Pei Y. P., Chin. J. Catal., 2009, 30(8), 825—829
	(焦桂萍, 丁云杰, 朱何俊, 李显明, 李经伟, 董文达, 裴彦鹏. 催化学报, 2009, 30(8), 825—829)
[5]	Mao D. S., Guo Q. S., Yu J. Han L. P., Lu G. Z., Acta Phys.-Chim. Sin., 2012, 27(11), 2639—2645
	(毛东森, 郭强胜, 俞俊, 韩璐蓬, 卢冠忠. 物理化学学报, 2012, 27(11), 2639—2645)
[6]	Liu J. G., Ding M. Y., Wang T. J., Ma L. L., Acta Phys.-Chim. Sin., 2012, 28(8), 1964—1970
	(刘建国, 定明月, 王铁军, 马隆龙. 物理化学学报, 2012, 28(8), 1964—1970)
[7]	Lin M. G., Fang K. G., Li D. B., Sun Y. H., Chin. J. Catal., 2008, 29(6), 559—565
	(林明桂, 房克功, 李德宝, 孙予罕. 催化学报, 2008, 29(6), 559—565 )
[8]	Wang N., Fang K. G., Lin M. G., Jiang D., Sun Y. H., Natural Gas Chemical Industry,2010, 35(2), 6—9
	(王宁, 房克功, 林明桂, 姜东, 孙予罕. 天然气化工,2010, 35(2), 6—9)
[9]	Niu L. L., Huang L., Du J. J., Wei Y., Hu C. F., Ye J. Y., Chen W. Y., Chem. J. Chinese Universities,2015, 36(10), 1873—1879
	(牛璐璐, 黄棣, 杜晶晶, 魏延, 胡超凡, 叶家业, 陈维毅. 高等学校化学学报,2015, 36(10), 1873—1879)
[10]	Liang X. L., Dong X., Li H. Y., Lin G. D., Zhang H. B., Journal of Xiamen University(Natural Science), 2005, 44(4), 445—449
	(梁雪莲, 董鑫, 李海燕, 林国栋, 张鸿斌. 厦门大学学报:自然科学版, 2005, 44(4), 445—449)
[11]	Shi L. M., Chu W., Deng S. Y., Journal of Natural Gas Chemistry,2011, 20(1), 48—52
[12]	Bao X. H., Sci. Sin. Chim., 2012, 42(4), 355—362
	(包信和. 中国科学化学, 2012, 42(4), 355—362)
[13]	Abbaslou R. M. M., Tavassoli A., Soltan J., Dalaia A. K., Applied Catalysis A: General,2009, 367(1), 47—52
[14]	Han T., Huang W., Wang X. D., Tang Y., Liu S. Q., You X. X., Acta Phys.-Chim. Sin., 2014, 30(11), 2127—2133
	(韩涛, 黄伟, 王晓东, 唐钰, 刘双强, 游向轩. 物理化学学报, 2014, 30(11), 2127—2133)
[15]	Wang P., Bai Y. X., Xiao H., Tian S. P., Zhang Z. Z., Wu Y. Q., Xie H. J., Yang G. H., Han Y. Z., Tan Y. S., Catalysis Communications,2015, 75, 92—97
[16]	Guo Q. S., Mao D. S., Yu J., Hang L. P., Journal of Fuel Chemistry and Technology,2012, 40(9), 1103—1109
[17]	Tang D. H., Zhang W. R., Wang Y. F., Miao J., Qiao Z. A., Huo Q. S., Zhang L. R., Chem. Res. Chinese Universities,2014, 30(4), 531—537
[18]	Zhao X. L., Sun H. J., Peng T. J., Chem. J. Chinese Universities,2016, 37(4), 728—735
	(赵小龙, 孙红娟, 彭同江. 高等学校化学学报,2016, 37(4), 728—735)
[19]	Huang W., Li W. H., Sun J. X., Yin L. H., Chin. J. Catal., 2010, 31(11), 1393—1398
	(黄伟, 李文辉, 孙景晓, 阴丽华. 催化学报, 2010, 31(11), 1393—1398)
[20]	Yin D. H., Li W. H., Yang W. S., Zhong B., Peng S. Y., Progress in Chemistry,2001, 13(2), 118—127
	(银董红, 李文怀, 杨文书, 钟炳, 彭少逸. 化学进展,2001, 13(2), 118—127)
[21]	Jiang Q., Chen J. K., Chen Z., He L. M., Lu X. Y., Hu A. L., Chem. J. Chinese Universities,2016, 37(1), 73—78
	(江奇, 陈建康, 陈姿, 和腊梅, 卢晓英, 胡爱琳, 高等学校化学学报,2016, 37(1), 73—78)
[22]	Peng F., Huang W., Han T., Chem. J. Chinese Universities,2013, 34(11), 87—2593
	(彭芬, 黄伟, 韩涛. 高等学校化学学报,2013, 34(11), 2587—2593)
[23]	Bao X. H., Sci. Sin. Chim., 2009, 39(10), 23—1133
	(包信和. 中国科学, 2009, 39(10), 23—1133)
[24]	Li Z. H., Huang W., Zuo Z. J., Song Y. J., Xie K. C., Chin. J. Catal., 2009, 30(2), 171—177
	(李志红, 黄伟, 左志军, 宋雅君, 谢克昌. 催化学报, 2009, 30(2), 171—177)
[25]	Xu B. L., Yang R. Q., Meng F. Z., Reubroycharoen P., Vitidsant T., Zhang Y., Yoneyama Y., Tsubaki N., Catalysis Surveys from Asia,2001, 13(3), 147—163
[26]	Li F., Sakaiya Y., Fujimoto K., Applied Catalysis A: General,1999, 180(s1/2), L11—L13
[27]	Wang J. J., Chernavskii Petr A., Wang Y., Khodakov Andrei Y., Fuel,2013, 103(1), 1111—1122
[28]	Fang Y. Z., Liu Y., Zhang L. H., Applied Catalysis A: General,2011, 397(1), 183—191
[29]	Wang F. Y., Lu D. X., Peng S. Y., Dai L. Z., Journal of Molecular Catalysis,1995, 9(1), 44—52
	(王峰云, 陆大勋, 彭少逸, 戴立珍. 分子催化,1995, 9(1), 44—52)