Preparation of Nitrogen Doped Mesoporous Carbon Supported Cobalt Catalyst and Its Performance for Removal of CO in Hydrogen-Rich Gas

doi:10.12096/j.2096-4528.pgt.22142

Abstract

Abstract:

In order to effectively remove CO from hydrogen-rich gas, cobalt-based nano-particle catalyst supported on nitrogen-doped ordered mesoporous carbon was prepared and characterized by X-ray diffraction (XRD), Raman spectrum, X-ray photoelectron spectroscopy (XPS) and thermogravimetry-mass spectrometry (TG-MS). The effects of nitrogen doping on the self-reduction behavior of the catalyst and CO methanation reaction performance were studied. The characterization results show that the nitrogen atoms introduced into the mesoporous carbon skeleton are mainly used as the nucleation sites of cobalt oxide, which have a strong interaction with the oxide carrier, and greatly improve the dispersion of cobalt species. Thus, small nano-cobalt particles with uniform particle size are formed, which significantly promote self-reduction reaction and thereby improve the reduction degree of the catalyst. The catalyst evaluation results show that, compared with the mesoporous carbon carrier without doping, the CO removal efficiency of the catalyst doped by nitrogen is much higher.

Key words: fuel cell, nitrogen doping, mesoporous carbon, self-reduction, methanation, CO removal

CLC Number:

TK 09

Haiguang WANG, Yongfeng LIU, Jun ZHANG. Preparation of Nitrogen Doped Mesoporous Carbon Supported Cobalt Catalyst and Its Performance for Removal of CO in Hydrogen-Rich Gas[J]. Power Generation Technology, 2023, 44(3): 373-381.

Figures/Tables 10

Fig. 1 Thermogravimetry curve of cyanamide annealed in the argon atmosphere

Tab. 1 Results of nitrogen physisorption, elemental analysis and Raman analysis

样品	氮气物理吸附			元素质量分数/%				Raman分析
样品	S_BET/(m²/g)	V_t/(cm³/g)	D_pore/nm	N	C	H	其他	I_D/I_G
OMC	580.7	0.65	4.2	0	92.6	2.6	4.8	0.98
NMC	540.2	0.63	4.1	10.5	87.3	1.1	1.1	1.13

Fig. 2 Raman spectra and small-angle XRD patterns of as-calcined samples

Fig. 3 Nitrogen physical adsorption isothermal curve of catalyst

Tab. 2 Texture properties and cobalt particle size of catalysts

样品	氮气物理吸附			STEM		H₂化学吸附
样品	S_BET/(m²/g)	V_t/(cm³/g)	D_pore/nm	d(Co⁰)/nm	S²	分散度/%	d(Co⁰)/nm
15Co/OMC	494.3	0.58	4.1	19.4	3.24	5.9	16.4
15Co/NMC	460.2	0.55	4.0	6.7	0.21	16.0	6.0

Fig. 4 Co 2p XPS spectra of catalyst

Fig. 5 HAADF-STEM images of autoreduced samples

Fig. 6 Changes of TG, DTG curves and mass spectrometry CO signals of heat treatment

Fig. 7 Structural transformation of samples by in-situ XRD detection during annealing treatment

Tab. 3 CO methanation reaction performance of self-reduced samples

样品

初始CO

体积分数

CO转化率/%

残余CO

体积分数

References 30

1	杨馥源，田雪沁，徐彤，等．面向碳中和电力系统转型的电氢枢纽灵活性应用[J]．电力建设，2021，42(8)：110-117． doi:10.12204/j.issn.1000-7229.2021.08.013
	YANG F Y， TIAN X Q， XU T，et al ．Flexibility of electro-hydrogen hub for power system transformation under the goal of carbon neutrality[J]．Electric Power Construction，2021，42(8)：110-117． doi:10.12204/j.issn.1000-7229.2021.08.013
2	曹蕃，郭婷婷，殷爱鸣，等．风光氢混合发电系统设计与能量管理策略研究进展[J]．分布式能源，2021，26(4)：1-14．
	CAO F， GUO T T， YIN A M，et al ．Research progress on optimal sizing and energy management strategy of wind-solar-hydrogen hybrid energy systems[J]．Distributed Energy，2021，26(4)：1-14．
3	黄倬，屠海令，张冀强，等．质子交换膜燃料电池的开发与应用[M]．北京：冶金工业出版社，2000：5-29．
	HUANG Z， TU H L， ZHANG J Q，et al ．Development and application of proton exchange membrane fuel cells[M]．Beijing：Metallurgical Industry Press，2000：5-29．
4	黄莎华，刘之景，王支逸．燃料电池开发现状及其发展趋势[J]．化学通报，2004，67(7)：551-557． doi:10.3969/j.issn.0441-3776.2004.07.006
	HUANG S H， LIU Z J， WANG Z Y ．Survey of the present condition of fuel cell and its development tendency[J]．Chemistry，2004，67(7)：551-557． doi:10.3969/j.issn.0441-3776.2004.07.006
5	赵海贺，陈泽宇，覃承富，等．车用燃料电池氢气循环系统引射特性研究[J]．电力工程技术，2022，41(1)：173-179． doi:10.12158/j.2096-3203.2022.01.023
	ZHAO H H， CHEN Z Y， QIN C F，et al ．Ejection characteristics of hydrogen cycle system for vehicular fuel cell[J]．Electric Power Engineering Technology，2022，41(1)：173-179． doi:10.12158/j.2096-3203.2022.01.023
6	李林，刘彤宇，李爽，等．甲醇重整制氢燃料电池发电研究进展[J]．发电技术，2022，43(1)：44-53． doi:10.12096/j.2096-4528.pgt.21116
	LI L， LIU T Y， LI S，et al ．Research progress of hydrogen production by methanol reforming for fuel cell power generation[J]．Power Generation Technology，2022，43(1)：44-53． doi:10.12096/j.2096-4528.pgt.21116
7	陈清泉，孙立清．电动汽车的现状和发展趋势[J]．科技导报，2005，23(4)：24-28． doi:10.3321/j.issn:1000-7857.2005.04.008
	CHEN Q Q， SUN L Q ．Present status and future trends of electric vehicles[J]．Science and Technology Review，2005，23(4)：24-28． doi:10.3321/j.issn:1000-7857.2005.04.008
8	王海光，刘永峰，张军．富氢气体脱除CO催化剂的制备及性能研究[J]．发电技术，2022，43(6)：901-907． doi:10.12096/j.2096-4528.pgt.22014
	WANG H G， LIU Y F， ZHANG J ．Preparation and its performance of catalyst for CO removal from hydrogen rich gas mixture[J]．Power Generation Technology，2022，43(6)：901-907． doi:10.12096/j.2096-4528.pgt.22014
9	SONG S Q， TSIAKARAS P ．Recent progress indirect ethanol proton exchange membrane fuel cells (DE-PEMFC)[J]．Applied Catalysis B：Environmental，2006，63(3/4)：187-193． doi:10.1016/j.apcatb.2005.09.018
10	刘其海．富氢重整气中CO选择性甲烷化剂催化剂的研究[D]．广州：华南理工大学，2009．
	LIU Q H ．Study on selective CO mathanation catalysts in hydrogen-rich gases[D]．Guangzhou：South China University of Technology，2009．
11	严菁，马建新，万钢．用于燃料电池汽车重整器的CO脱除技术[J]．天然气化工，2002，27(5)：35-38. doi:10.3969/j.issn.1001-9219.2002.05.010
	YAN J， MA J X， WAN G ．Methods of CO clean-up for the reformer of fuel cell vehicles[J]．Natural Gas Chemical Industry，2002，27(5)：35-38． doi:10.3969/j.issn.1001-9219.2002.05.010
12	纪玉国，赵震，余长春，等．Fischer-Tropsch合成钴基催化剂研究进展[J]．化工进展，2007，26(7)：927-933． doi:10.3321/j.issn:1000-6613.2007.07.004
	JI Y G， ZHAO Z， YU C C，et al ．Progress of cobalt-based catalysts in Fischer-Tropsch synthesis[J]．Chemical Industry and Engineering Progress，2007，26(7)：927-933． doi:10.3321/j.issn:1000-6613.2007.07.004
13	IGLESIA E， SOLED S L， FIANTO R A ．Fischer-Tropsch synthesis on cobalt and ruthenium metal dispersion and support effects on reaction and selectivity[J]．Journal of Catalysis，1992，137(1)：212-224． doi:10.1016/0021-9517(92)90150-g
14	李晨，马向东，应为勇，等．Co-Ru/γ-Al₂O₃催化剂的F-T合成性能[J]．石油化工，2008，37(1)：34-38． doi:10.3321/j.issn:1000-8144.2008.01.007
	LI C， MA X D， YING W Y，et al ．Catalytic performance of Co-Ru/γ-Al₂O₃ catalyst for Ficher-Tropsch synthesis[J]．Petrochemical Technology，2008，37(1)：34-38． doi:10.3321/j.issn:1000-8144.2008.01.007
15	李剑锋，侯学锋，代小平，等．不同载体和前驱体对钴基催化剂浆相费托合成性能的影响[J]．石油大学学报(自然科学版)，2004，28(5)：94-98．
	LI J F， HOU X F， DAI X P，et al ．Effect of supports and precursors on Co-based fine particle catalyst for slurry phase Fischer-Tropsch synthesis[J]．Journal of China University of Petroleum (Natural Science Edition)，2004，28(5)：94-98．
16	HA K S， KWAK G， JUN K W，et al ．Ordered mesoporous carbon nanochannel reactors for high-performance Fischer-Tropsch synthesis[J]．Chemical Communications，2013，49(45)：5141-5143． doi:10.1039/c3cc00297g
17	FU T， JIANG Y， LV J，et al ．Effect of carbon support on Fischer-Tropsch synthesis activity and product distribution over Co-based catalysts[J]．Fuel Processing Technology，2013，110：141-149． doi:10.1016/j.fuproc.2012.12.006
18	RADKEVICH V Z， SENKO T L， WILSON K，et al ．The influence of surface functionalization of activated carbon on palladium dispersion and catalytic activity in hydrogen oxidation[J]．Applied Catalysis A：Genetal，2008，335(2)：241-251． doi:10.1016/j.apcata.2007.11.029
19	DEIFALLAH M， MCMILLAN P F， CORA F ．Electronic and structural properties of two-dimensional carbon nitride graphenes[J]．The Journal of Physical Chemistry C，2008，112(14)：5447-5453． doi:10.1021/jp711483t
20	LI X， WANG H， ROBINSON J T，et al ．Simultaneous nitrogen doping and reduction of graphene oxide[J]．Journal of the American Chemical Society，2009，131(43)：15939-15944． doi:10.1021/ja907098f
21	CHEN W， PAN X， WILLINGER M G，et al ．Facile autoreduction of iron oxide/carbon nanotube encapsulates[J]．Journal of the American Chemical Society，2006，128(10)：3136-3137． doi:10.1021/ja056721l
22	CHEN W， PAN X， BAO X ．Turing of redox properties of iron and iron oxides via encapsulation within carbon nanotubes[J]．Journal of the American Chemical Society，2007，129(23)：7421-7426． doi:10.1021/ja0713072
23	LU A H， LI W C， SCHMIDT W，et al ．Easy synthesis of an ordered mosoporous carbon with a hexagonally packed tubular structure[J]．Carbon，2004，42(14)：2939-2948． doi:10.1016/j.carbon.2004.07.006
24	JUN Y S， HONG W H， ANTONIETTI M，et al ．2D hexagonal carbon nitride and titanium nitride/carbon composites[J]．Advanced Materials，2009，21(42)：4270-4274． doi:10.1002/adma.200803500
25	ZHAO Y， LIU Z， CHU W，et al ．Large scale synthesis of nitrogen-rich carbon nitride microfibers by using graphitic carbon nitride as precursor[J]．Advanced Materials，2008，20(9)：1777-1781． doi:10.1002/adma.200702230
26	YAN S C， LI Z S， ZOU Z G ．Photodegradation performance of g-C₃N₄ fabricated by directly heating melamine[J]．Langmuir，2009，25(17)：10397-10401． doi:10.1021/la900923z
27	XU X， LI Y， GONG Y，et al ．Synthesis of palladium nanopaticles supported on mesoporous N-doped carbon and their catalytic ability for biofuel upgrade[J]．Journal of the American Chemical Society，2012，134(41)：16987-16990． doi:10.1021/ja308139s
28	ZHAO D， HUO Q， FENG J，et al ．Nonionic triblock and star diblock copolymer and oligomeric surfactant syntheses of highly ordered，hydrothermally stable， mesoporous silica structure[J]．Journal of the American Chemical Society，1998，120(24)：6024-6036． doi:10.1021/ja974025i
29	POON S W， PAN J S， TOK E S ．Nucleation and growth of cobalt nanostructures on highly oriented pyrolytic graphite[J]．Physical Chemistry Chemical Physics，2006，8(28)：3326-3334． doi:10.1039/b604627b
30	BEZEMER G L， BITTER J H， KUIPERS H P C E，et al ．Cobalt particle size effects in the Fischer-Tropsch reaction studied with carbon nanofiber supported catalysts[J]．Journal of the American Chemical Society，2006，128(12)：3956-3964． doi:10.1021/ja058282w

[1]	Bofei WANG, Haozhe XIAO, Guohao LI, Wenheng XIU, Yunhao MO, Mingjie ZHU, Zhen WU. A Review of Energy Management Strategy for Hydrogen-Electricity Hybrid Power System Based on Control Target [J]. Power Generation Technology, 2023, 44(4): 452-464.
[2]	Lei WU, Liju PENG, Shuang LI, Yixiang SHI, Ningsheng CAI. Simulation and Analysis of Steady State Characteristics of Hundred Kilowatt Proton Exchange Membrane Fuel Cell Combined Heat and Power System Based on Hydrogen Production From Natural Gas [J]. Power Generation Technology, 2023, 44(3): 350-360.
[3]	Yiwen CHEN, Jinbin ZHAO, Junzhou LI, Ling MAO, Keqing QU, Guoqing WEI. Challenges and Prospects of Hydrogen Energy Storage Under the Background of Low-carbon Transformation of Power Industry [J]. Power Generation Technology, 2023, 44(3): 296-304.
[4]	Jianlin LI, Chenxi SHAO, Zedong ZHANG, Zhonghao LIANG, Fei ZENG. Analysis of Hydrogen Industry Policy and Commercialization Model [J]. Power Generation Technology, 2023, 44(3): 287-295.
[5]	Zhenzhen YE, Xinqi CHEN, Shuting ZHANG, Jian WANG, Chaojie CUI, Gang ZHANG, Lei ZHANG, Luming QIAN, Ying JIN, Weizhong QIAN. Long Period Operation of Ionic Liquid Based Electrical Double Layer Capacitor at 45 ℃ and 3 V [J]. Power Generation Technology, 2023, 44(2): 213-220.
[6]	Quanbin ZHANG, Qiongfang ZHOU. Research on the Development Path of China’s Thermal Power Generation Technology Based on the Goal of “Carbon Peak and Carbon Neutralization” [J]. Power Generation Technology, 2023, 44(2): 143-154.
[7]	Haiguang WANG, Yongfeng LIU, Jun ZHANG. Preparation and Its Performance of Catalyst for CO Removal From Hydrogen Rich Gas Mixture [J]. Power Generation Technology, 2022, 43(6): 901-907.
[8]	Yakun HUANG, Jinyi LIU, Xiaosong ZHANG. Configuration Optimization of Off-Grid Energy System Based on HT-PEMFC and VRFB [J]. Power Generation Technology, 2022, 43(2): 305-312.
[9]	Lin LI, Tongyu LIU, Shuang LI, Yixiang SHI, Ningsheng CAI. Research Progress of Hydrogen Production by Methanol Reforming for Fuel Cell Power Generation [J]. Power Generation Technology, 2022, 43(1): 44-53.
[10]	Xinru GUO, Yumin GUO, Fang LUO, Jiangfeng WANG, Pan ZHAO. Analysis of Energy, Exergy and Ecology Characteristics of Phosphoric Acid Fuel Cell [J]. Power Generation Technology, 2022, 43(1): 73-82.
[11]	Ming ZHONG,Kexun LI,Gaosheng WEI. Research Progress of Air Cathode in Microbial Fuel Cell System [J]. Power Generation Technology, 2019, 40(6): 598-604.
[12]	Shengzhe ZHOU,Qiang CUI,Maoyuan ZHANG,Guoting XIA,Kai WANG. Study on the Management of Fuel Cell Vehicle Energy System Using Hybrid Fuzzy Logic Controller [J]. Power Generation Technology, 2018, 39(6): 554-560.
[13]	Hongyu ZENG,Yixiang SHI,Ningsheng CAI. Development and Prospect of Fuel Cell Technology for Distributed Power System [J]. Power Generation Technology, 2018, 39(2): 165-170.