Research progress of selective CO methanation

doi:10.16085/j.issn.1000-6613.2021-0114

Abstract

Abstract:

Selective CO methanation is considered as the most promising deep CO removal technology for the low-temperature fuel cells. Furthermore, the key to its wide applications is the development of high-performance supported catalysts. The research progress of selective CO methanation in recent years is reviewed in this article. Starting with the selection and evaluation criteria of catalysts, this article focuse on the reaction mechanism of CO and CO₂ methanation, the effects of particle size, supports and promoters on the catalytic activity and selectivity. Finally, the research on selective CO methanation is summarized and future research direction is also prospected. It is concluded that selecting appropriate loading of active components, supports and promoters can significantly improve the activity of the catalyst. However, the metal-support interface can be controlled by the chloride ion modification and the preparation of Ru-Ni bimetal, which plays a vital role in the improvement of the selectivity. The research on the methanation reaction mechanism and the development of long-term stable catalysts will be the focus of future researches.

Key words: selective CO methanation, catalyst, reaction mechanism, reactivity, particle size effects, support

摘要：

CO选择性甲烷化被认为是适用于低温燃料电池的、最具发展潜力的CO深度去除技术，而该技术大规模应用的关键在于高性能负载型催化剂的开发。本文综述了近些年来CO选择性甲烷化的研究进展，以催化剂的选取和评判标准为起点，着重论述了CO和CO₂甲烷化的反应机理、粒径效应以及载体和助剂对催化剂活性和选择性的影响，最后总结了CO选择性甲烷化的研究并对未来的研究方向进行了展望。分析表明，选取合适的活性组分负载量以及载体和助剂可以大幅度提高催化剂的CO甲烷化活性，而通过氯离子改性以及Ru-Ni双金属的制备来控制金属-载体作用界面则是提高催化剂CO甲烷化选择性的关键。指出对甲烷化反应机理的研究和具有长期稳定性催化剂的开发是未来CO选择性甲烷化研究的重点。

关键词: CO选择性甲烷化, 催化剂, 反应机理, 活性, 粒径效应, 载体

CLC Number:

TQ426

JI Zike, BAO Cheng. Research progress of selective CO methanation[J]. Chemical Industry and Engineering Progress, 2022, 41(1): 120-132.

纪子柯, 包成. CO选择性甲烷化的研究进展[J]. 化工进展, 2022, 41(1): 120-132.

Figures/Tables 17

催化剂	反应气体体积分数/%				质量空速	体积空速	T_min	S_min（CO）	T_max	S_max（CO）	参考文献
催化剂	CO	CO₂	H₂	H₂O	/cm³·h^-1·g^-1	/h^-1	/℃	/%	/℃	/%	参考文献
5%Ru/Al₂O₃	0.56	21.7	42.2	He	19800		210	100	244	50	［5］
Ni/ZrO₂	1	20	79	0		8500	215	100	350	50	［6］
3%Ru/50%NiAlO_x/NF	1	20	79	0		250	180	100	280	50	［7］
RuNi/Al₂O₃-CNTs/NF	1	20	79	0		1400	190	100	250	50	［8］
MS/Ni/AlVO_x	0.43	17.1	67.9	14.53		2400	170	100	200	50	［9］
0.22TMS/0.039V/Ni	0.43	17.1	67.9	14.53		4800	164	100	198	50	［10］
Ni/CeO₂（Cl*）	1	20	65	10	29000		240	90	285	50	［11］
Ni（Cl_0.1）/ZrO₂	1	18	70	N₂	15000		215	100	295	50	［12］
Ru-Ni/TiO₂-Al₂O₃	1	20	50	He		2400	210	95	220	80	［13］
1%Ru/MA-40Ni	0.87	17.4	68.73	13		2400	190	100	260	50	［14］

CO直接解离	歧化反应
$C O + * → C O *$	$C O + * → C O *$
$H 2 + 2 * → H * + H *$	$H 2 + 2 * → H * + H *$
$C O * + * → C * + O * (R D S)$	$C O * + C O * → C O 2 + C * + * (R D S)$
$C * + 4 H * → C H 4 + 5 *$	$C * + 4 H * → C H 4 + 5 *$

CO直接解离	歧化反应
$C O + * → C O *$	$C O + * → C O *$
$H 2 + 2 * → H * + H *$	$H 2 + 2 * → H * + H *$
$C O * + * → C * + O * (R D S)$	$C O * + C O * → C O 2 + C * + * (R D S)$
$C * + 4 H * → C H 4 + 5 *$	$C * + 4 H * → C H 4 + 5 *$

HCO路径		COH路径
	$C O + * → C O *$		$C O + * → C O *$
$C O + * → C O *$	$H 2 + 2 * → H * + H *$	$C O + * → C O *$	$H 2 + 2 * → H * + H *$
$H 2 + 2 * → H * + H *$	$C O * + H * → H C O * + * (R D S)$	$H 2 + 2 * → H * + H *$	$C O * + H * → C O H * + * (R D S)$
$C O * + H * → H C O * + * (R D S)$	$H C O * + H * → H C O H * + *$	$C O * + H * → C O H * + * (R D S)$	$C O H * + H * → H C O H * + *$
$H C O * + * → H C * + O *$	$H C O H * + * → H C * + O H *$	$C O H * + * → C * + O H *$	$H C O H * + H * → C H 2 O H * + *$
$C H * + 3 H * → C H 4 + 4 *$	$C H * + 3 H * → C H 4 + 4 *$	$C * + 4 H * → C H 4 + 5 *$	$C H 2 O H * + * → C H 2 * + O H *$
			$C H 2 * + 2 H * → C H 4 + 3 *$

HCO路径		COH路径
	$C O + * → C O *$		$C O + * → C O *$
$C O + * → C O *$	$H 2 + 2 * → H * + H *$	$C O + * → C O *$	$H 2 + 2 * → H * + H *$
$H 2 + 2 * → H * + H *$	$C O * + H * → H C O * + * (R D S)$	$H 2 + 2 * → H * + H *$	$C O * + H * → C O H * + * (R D S)$
$C O * + H * → H C O * + * (R D S)$	$H C O * + H * → H C O H * + *$	$C O * + H * → C O H * + * (R D S)$	$C O H * + H * → H C O H * + *$
$H C O * + * → H C * + O *$	$H C O H * + * → H C * + O H *$	$C O H * + * → C * + O H *$	$H C O H * + H * → C H 2 O H * + *$
$C H * + 3 H * → C H 4 + 4 *$	$C H * + 3 H * → C H 4 + 4 *$	$C * + 4 H * → C H 4 + 5 *$	$C H 2 O H * + * → C H 2 * + O H *$
			$C H 2 * + 2 H * → C H 4 + 3 *$

反应类型	反应方式	反应方式判定	活性位点位置	主要中间体	限速步骤	影响因素
CO甲烷化	解离	C－O键断裂是否有H协助	活性金属	C_ad	C_ad的加氢	温度、表面结构
	缔合			HCO_ad	HCO_ad的生成
				COH_ad	COH_ad的生成
CO₂甲烷化	解离	是否生成CO_ad中间体	活性金属	CO_ad	CO_ad的解离	反应气体组成、制备方法、活性组分负载量
	缔合		金属-载体作用界面	CO_ad	CO_ad的生成
			金属-载体作用界面	HCOO_ad	HCOO_ad的加氢

References 81

1	PARK E D, LEE D, LEE H C. Recent progress in selective CO removal in a H₂-rich stream[J]. Catalysis Today, 2009, 139(4): 280-290.
2	SNYTNIKOV P V, ZYRYANOVA M M, SOBYANIN V A. CO-cleanup of hydrogen-rich stream for LT PEM FC feeding: catalysts and their performance in selective CO methanation[J]. Topics in Catalysis, 2016, 59(15): 1394-1412.
3	VANNICE M A. The catalytic synthesis of hydrocarbons from H₂/CO mixtures over the group Ⅴ‍‍Ⅲ metals[J]. Journal of Catalysis, 1975,37(3):449-461.
4	TAKENAKA S, SHIMIZU T, OTSUKA K. Complete removal of carbon monoxide in hydrogen-rich gas stream through methanation over supported metal catalysts[J]. International Journal of Hydrogen Energy, 2004, 29(10): 1065-1073.
5	DJINOVIĆ P, GALLETTI C, SPECCHIA S, et al. Ru-based catalysts for CO selective methanation reaction in H₂-rich gases[J]. Catalysis Today, 2011, 164(1): 282-287.
6	PING D, DONG X F, ZANG Y H, et al. Highly efficient MOF-templated Ni catalyst towards CO selective methanation in hydrogen-rich reformate gases[J]. International Journal of Hydrogen Energy, 2017, 42(23): 15551-15556.
7	WANG C X, PING D, DONG X F, et al. Construction of Ru/Ni-Al-oxide/Ni-foam monolithic catalyst for deep-removing CO in hydrogen-rich gas via selective methanation[J]. Fuel Processing Technology, 2016, 148: 367-371.
8	PING D, DONG C J, ZHAO H, et al. A novel hierarchical RuNi/Al₂O₃-carbon nanotubes/Ni foam catalyst for selective removal of CO in H₂-rich fuels[J]. Industrial & Engineering Chemistry Research, 2018, 57(16): 5558-5567.
9	MIYAO T, SAKURABAYASHI S, SHEN W H, et al. Preparation and catalytic activity of a mesoporous silica-coated Ni-alumina-based catalyst for selective CO methanation[J]. Catalysis Communications, 2015, 58: 93-96.
10	HAYASHI K, MIYAO T, HIGASHIYAMA K, et al. Catalytic performance of mesoporous silica-covered nickel core-shell particles for selective CO methanation[J]. Applied Catalysis A: General, 2015, 506: 143-150.
11	KONISHCHEVA M V, POTEMKIN D I, SNYTNIKOV P V, et al. The insights into chlorine doping effect on performance of ceria supported nickel catalysts for selective CO methanation[J]. Applied Catalysis B: Environmental, 2018, 221: 413-421.
12	GAO Z M, WANG L L, MA H W, et al. Durability of catalytic performance of the chlorine-doped catalyst Ni(Cl_x)/ZrO₂ for selective methanation of CO in H₂-rich gas[J]. Applied Catalysis A: General, 2017, 534: 78-84.
13	DAI X P, LIANG J, MA D, et al. Large-pore mesoporous RuNi-doped TiO₂-Al₂O₃nanocomposites for highly efficient selective CO methanation in hydrogen-rich reformate gases[J]. Applied Catalysis B: Environmental, 2015, 165: 752-762.
14	CHEN A H, MIYAO T, HIGASHIYAMA K, et al. High catalytic performance of ruthenium-doped mesoporous nickel-aluminum oxides for selective CO methanation[J]. Angewandte Chemie International Edition, 2010, 49(51): 9895-9898.
15	LEGRAS B, ORDOMSKY V V, DUJARDIN C, et al. Impact and detailed action of sulfur in syngas on methane synthesis on Ni/γ-Al₂O₃ catalyst[J]. ACS Catalysis, 2014, 4(8): 2785-2791.
16	PANAGIOTOPOULOU P, KONDARIDES D I, VERYKIOS X E. Mechanistic study of the selective methanation of CO over Ru/TiO₂ catalyst: identification of active surface species and reaction pathways[J]. The Journal of Physical Chemistry C, 2011, 115(4): 1220-1230.
17	SEHESTED J, DAHL S, JACOBSEN J, et al. Methanation of CO over nickel: mechanism and kinetics at high H₂/CO ratios[J]. The Journal of Physical Chemistry B, 2005, 109(6): 2432-2438.
18	ARAKI M, PONEC V. Methanation of carbon monoxide on nickel and nickel-copper alloys[J]. Journal of Catalysis, 1976, 44(3): 439-448.
19	TISON Y, NIELSEN K, MOWBRAY D J, et al. Scanning tunneling microscopy evidence for the dissociation of carbon monoxide on ruthenium steps[J]. The Journal of Physical Chemistry C, 2012, 116(27): 14350-14359.
20	CIOBICA I M, SANTEN R A VAN. Carbon monoxide dissociation on planar and stepped Ru(0001) surfaces[J]. The Journal of Physical Chemistry B, 2003, 107(16): 3808-3812.
21	FOPPA L, COPÉRET C, COMAS-VIVES A. Increased back-bonding explains step-edge reactivity and particle size effect for CO activation on Ru nanoparticles[J]. Journal of the American Chemical Society, 2016, 138(51): 16655-16668.
22	VENDELBO S B, JOHANSSON M, MOWBRAY D J, et al. Self blocking of CO dissociation on a stepped ruthenium surface[J]. Topics in Catalysis, 2010, 53(5/6): 357-364.
23	ECKLE S, ANFANG H G, BEHM R J. Reaction intermediates and side products in the methanation of CO and CO₂ over supported Ru catalysts in H₂-rich reformate gases[J]. The Journal of Physical Chemistry C, 2011, 115(4): 1361-1367.
24	WANG Y X, SU Y, ZHU M Y, et al. Mechanism of CO methanation on the Ni₄/γ‍-Al₂O₃ and Ni₃Fe/γ‍-Al₂O₃ catalysts: a density functional theory study[J]. International Journal of Hydrogen Energy, 2015, 40(29): 8864-8876.
25	ZHI C M, WANG Q, WANG B J, et al. Insight into the mechanism of methane synthesis from syngas on a Ni(111) surface: a theoretical study[J]. RSC Advances, 2015, 5(82): 66742-66756.
26	FAJÍN J L C, GOMES J R B, CORDEIRO M N D S. Mechanistic study of carbon monoxide methanation over pure and rhodium-or ruthenium-doped nickel catalysts[J]. The Journal of Physical Chemistry C, 2015, 119(29): 16537-16551.
27	ANDERSSON M P, ABILD-PEDERSEN F, REMEDIAKIS I N, et al. Structure sensitivity of the methanation reaction: H₂ induced CO dissociation on nickel surfaces[J]. Journal of Catalysis, 2008, 255(1): 6-19.
28	ZHI C M, ZHANG R G, WANG B J. Comparative studies about CO methanation over Ni(211) and Zr-modified Ni(211) surfaces: qualitative insight into the effect of surface structure and composition[J]. Molecular Catalysis, 2017, 438: 1-14.
29	FOPPA L, LANNUZZI M, COPÉRET C, et al. CO methanation on ruthenium flat and stepped surfaces: key role of H-transfers and entropy revealed by ab initio molecular dynamics[J]. Journal of Catalysis, 2019, 371: 270-275.
30	WANG X, HONG Y C, SHI H, et al. Kinetic modeling and transient DRIFTS-MS studies of CO₂ methanation over Ru/Al₂O₃ catalysts[J]. Journal of Catalysis, 2016, 343: 185-195.
31	FALBO L, VISCONTI C G, LIETTI L, et al. The effect of CO on CO₂ methanation over Ru/Al₂O₃ catalysts: a combined steady-state reactivity and transient DRIFT spectroscopy study[J]. Applied Catalysis B: Environmental, 2019, 256: 117791.
32	KESAVAN J K, LUISETTO I, TUTI S, et al. Nickel supported on YSZ: the effect of Ni particle size on the catalytic activity for CO₂ methanation[J]. Journal of CO₂ Utilization, 2018, 23: 200-211.
33	REN J, GUO H L, YANG J Z, et al. Insights into the mechanisms of CO₂ methanation on Ni(111) surfaces by density functional theory[J]. Applied Surface Science, 2015, 351: 504-516.
34	ALDANA P A U, OCAMPO F, KOBL K, et al. Catalytic CO₂ valorization into CH₄ on Ni-based ceria-zirconia. Reaction mechanism by operando IR spectroscopy[J]. Catalysis Today, 2013, 215: 201-207.
35	XU X L, TONG Y Y, HUANG J, et al. Insights into CO₂ methanation mechanism on cubic ZrO₂ supported Ni catalyst via a combination of experiments and DFT calculations[J]. Fuel, 2021, 283: 118867.
36	PAN Q S, PENG J X, WANG S, et al. In situ FTIR spectroscopic study of the CO₂ methanation mechanism on Ni/Ce_0.5Zr_0.5O₂[J]. Catalysis Science & Technology, 2014, 4(2): 502-509.
37	SOLIS-GARCIA A, LOUVIER-HERNANDEZ J F, ALMENDAREZ-CAMARILLO A, et al. Participation of surface bicarbonate, formate and methoxy species in the carbon dioxide methanation catalyzed by ZrO₂-supported Ni[J]. Applied Catalysis B: Environmental, 2017, 218: 611-620.
38	RUI Z, RUI N, FAN Z G, et al. Effect of the structure of Ni/TiO₂ catalyst on CO₂ methanation[J]. International Journal of Hydrogen Energy, 2016, 41(47): 22017-22025.
39	MIAO B, MA S S K, WANG X, et al. Catalysis mechanisms of CO₂ and CO methanation[J]. Catalysis Science & Technology, 2016, 6(12): 4048-4058.
40	JIA X Y, ZHANG X S, RUI N, et al. Structural effect of Ni/ZrO₂ catalyst on CO₂ methanation with enhanced activity[J]. Applied Catalysis B: Environmental, 2019, 244: 159-169.
41	ZHANG Z M, TIAN Y, ZHANG L J, et al. Impacts of nickel loading on properties, catalytic behaviors of Ni/γ-Al₂O₃ catalysts and the reaction intermediates formed in methanation of CO₂[J]. International Journal of Hydrogen Energy, 2019, 44(18): 9291-9306.
42	TADA S, KIKUCHI R, URASAKI K, et al. Effect of reduction pretreatment and support materials on selective CO methanation over supported Ru catalysts[J]. Applied Catalysis A: General, 2011, 404(1/2): 149-154.
43	TADA S, KIKUCHI R. Mechanistic study and catalyst development for selective carbon monoxide methanation[J]. Catalysis Science & Technology, 2015, 5(6): 3061-3070.
44	ECKLE S, AUGUSTIN M, ANFANG H G, et al. Influence of the catalyst loading on the activity and the CO selectivity of supported Ru catalysts in the selective methanation of CO in CO₂ containing feed gases[J]. Catalysis Today, 2012, 181(1): 40-51.
45	PANAGIOTOPOULOU P, KONDARIDES D I, VERYKIOS X E. Selective methanation of CO over supported Ru catalysts[J]. Applied Catalysis B: Environmental, 2009, 88(3/4): 470-478.
46	ABDEL-MAGEED A M, WIDMANN D, OLESEN S E, et al. Selective CO methanation on highly active Ru/TiO₂ catalysts: identifying the physical origin of the observed activation/deactivation and loss in selectivity [J]. ACS Catalysis, 2018, 8(6): 5399-5414.
47	NEMATOLLAHI B, REZAEI M, LAY E N. Preparation of highly active and stable NiO-CeO₂ nanocatalysts for CO selective methanation[J]. International Journal of Hydrogen Energy, 2015, 40(27): 8539-8547.
48	NEMATOLLAHI B, REZAEI M, AMINI E, et al. Preparation of high surface area Ni/MgAl₂O₄ nanocatalysts for CO selective methanation[J]. International Journal of Hydrogen Energy, 2017, 43(2): 772-780.
49	DU J P, GAO J J, GU F N, et al. A strategy to regenerate coked and sintered Ni/Al₂O₃ catalyst for methanation reaction[J]. International Journal of Hydrogen Energy, 2018, 43(45): 20661-20670.
50	LIU Y J, GAO J J, LIU Q, et al. Preparation of high-surface-area Ni/α‍-Al₂O₃ catalysts for improved CO methanation[J]. RSC Advances, 2015, 5(10): 7539-7546.
51	ZENG Y, MA H F, ZHANG H T, et al. Highly efficient NiAl₂O₄-free Ni/γ-Al₂O₃ catalysts prepared by solution combustion method for CO methanation[J]. Fuel, 2014, 137: 155-163.
52	詹吉山, 郭翠梨, 张俊涛, 等. TiO₂对Ni/Al₂O₃催化剂CO甲烷化性能的影响[J]. 燃料化学学报, 2012, 40(5): 589-593.
	ZHAN J S, GUO C L, ZHANG J T, et al. Effects of TiO₂ promoter on the catalytic performance of Ni/Al₂O₃ in CO methanation[J]. Journal of Fuel Chemistry and Technology, 2012, 40(5): 589-593.
53	LE T A, KANG J K, PARK E D. CO and CO₂ methanation over Ni/SiC and Ni/SiO₂ catalysts[J]. Topics in Catalysis, 2018, 61(15/16/17): 1537-1544.
54	LE T A, KIM T W, LEE S H, et al. Effects of Na content in Na/Ni/SiO₂ and Na/Ni/CeO₂ catalysts for CO and CO₂ methanation[J]. Catalysis Today, 2017, 303: 159-167.
55	LAKSHMANAN P, KIM M S, PARK E D. A highly loaded Ni@SiO₂ core-shell catalyst for CO methanation[J]. Applied Catalysis A: General, 2016, 513: 98-105.
56	KOKKA A, RAMANTANI T, PETALA A, et al. Effect of the nature of the support, operating and pretreatment conditions on the catalytic performance of supported Ni catalysts for the selective methanation of CO[J]. Catalysis Today, 2020, 355: 832-843.
57	XU M, HE S, CHEN H, et al. TiO_2-_x-modified Ni nanocatalyst with tunable metal-support interaction for water-gas shift reaction[J]. ACS Catalysis, 2017, 7(11): 7600-7609.
58	CHEN S L, ABDEL-MAGEED A M, GAUCKLER C, et al. Selective CO methanation on isostructural Ru nanocatalysts: the role of support effects[J]. Journal of Catalysis, 2019, 373: 103-115.
59	ABDEL-MAGEED A M, WIDMANN D, OLESEN S E, et al. Selective CO methanation on Ru/TiO₂ catalysts: role and influence of metal-support interactions[J]. ACS Catalysis, 2015, 5(11): 6753-6763.
60	JIA X Y, RUI N, ZHANG X S, et al. Ni/ZrO₂ by dielectric barrier discharge plasma decomposition with improved activity and enhanced coke resistance for CO methanation[J]. Catalysis Today, 2019, 334: 215-222.
61	SILVA D C D DA, LETICHEVSKY S, BORGES L E P, et al. The Ni/ZrO₂ catalyst and the methanation of CO and CO₂[J]. International Journal of Hydrogen Energy, 2012, 37(11): 8923-8928.
62	LE T A, KIM M S, LEE S H, et al. CO and CO₂ methanation over supported Ni catalysts[J]. Catalysis Today, 2017, 293/294: 89-96.
63	KONISHCHEVA M V, POTEMKIN D I, BADMAEV S D, et al. On the mechanism of CO and CO₂ methanation over Ni/CeO₂ catalysts[J]. Topics in Catalysis, 2016, 59(15/16): 1424-1430.
64	LIU J, YU J, SU F B, et al. Intercorrelation of structure and performance of Ni-Mg/Al₂O₃ catalysts prepared with different methods for syngas methanation[J]. Catalysis Science & Technology, 2014, 4(2): 472-481.
65	文博, 朱明远, 代斌. Ca²⁺、Mg²⁺在MCM-41离子交换制备镍基催化剂对合成气甲烷化的性能分析[J]. 石河子大学学报(自然科学版), 2016, 34(3): 360-366.
	WEN B, ZHU M Y, DAI B. Preparation of nickel-based catalysts by Ca²⁺, Mg²⁺ exchange in MCM-41 for methanation of synthesis gas properties exploration[J]. Journal of Shihezi University (Natural Science), 2016, 34(3): 360-366.
66	HAN Y H, QUAN Y H, ZHAO J X, et al. Promotion effect by Mg on the catalytic behavior of MgNi/WO₃ in the CO methanation[J]. International Journal of Hydrogen Energy, 2020, 45(55): 29917-29928.
67	TADA S, KIKUCHI R, TAKAGAKI A, et al. Effect of metal addition to Ru/TiO₂ catalyst on selective CO methanation[J]. Catalysis Today, 2014, 232: 16-21.
68	GONG D D, LI S S, GUO S X, et al. Lanthanum and cerium co-modified Ni/SiO₂ catalyst for CO methanation from syngas[J]. Applied Surface Science, 2018, 434: 351-364.
69	张旭, 王子宗, 陈建峰. 助剂对煤基合成气甲烷化反应用镍基催化剂的促进作用[J]. 化工进展, 2015, 34(2): 389-396.
	ZHANG X, WANG Z Z, CHEN J F. Effects of promoters on supported nickel-based syngas methanation catalysts[J]. Chemical Industry and Engineering Progress, 2015, 34(2): 389-396.
70	MIYAO T, TANAKA J, SHEN W H, et al. Catalytic activity and durability of a mesoporous silica-coated Ni-alumina-based catalyst for selective CO methanation[J]. Catalysis Today, 2015, 251: 81-87.
71	李春启. 新型合成气甲烷化催化剂La₂O₃-ZrO₂-Ni/Al₂O₃的制备与性能[J]. 化工进展, 2019, 38(6): 2776-2783.
	LI Chunqi. Preparation of a noval catalyst of La₂O₃-ZrO₂-Ni/Al₂O₃ and its performance in syngas mechanation[J]. Chemical Industry and Engineering Progress, 2019, 38(6): 2776-2783.
72	MIYAO T, SHEN W H, CHEN A H, et al. Mechanistic study of the effect of chlorine on selective CO methanation over Ni alumina-based catalysts[J]. Applied Catalysis A: General, 2014, 486: 187-192.
73	高志明, 代倩子, 马宏伟. 添加氯离子对Ni/CeO₂催化剂CO选择甲烷化反应催化性能的促进[J]. 北京理工大学学报, 2016, 36(4): 429-434, 440.
	GAO Z M, DAI Q Z, MA H W. Effect of chlorine doped in Ni/CeO₂ catalyst on selective methanation of CO in H₂-rich gas[J]. Transactions of Beijing Institute of Technology, 2016, 36(4): 429-434, 440.
74	SHIMODA N, SHOJI D, TANI K, et al. Role of trace chlorine in Ni/TiO₂ catalyst for CO selective methanation in reformate gas[J]. Applied Catalysis B: Environmental, 2015, 174/175: 486-495.
75	SHIMODA N, FUJIWARA M, TANI K, et al. Durability of Ni/TiO₂ catalyst containing trace chlorine for CO selective methanation[J]. Applied Catalysis A: General, 2018, 557: 7-14.
76	ZYRYANOVA M M, SNYTNIKOV P V, GULYAEV R V, et al. Performance of Ni/CeO₂ catalysts for selective CO methanation in hydrogen-rich gas[J]. Chemical Engineering Journal, 2014, 238: 189-197.
77	LIU B, YAO N, LI S, et al. Methanation of CO in hydrogen-rich gas on Ni-Ru/SiO₂ catalyst: the type of active sites and Ni-Ru synergistic effect[J]. Chemical Engineering Journal, 2016, 304: 476-484.
78	吕晓阳, 孟凡会, 李忠. 双金属Ni-Ru催化剂在加氢及制氢反应中的研究进展[J]. 天然气化工（C1化学与化工）, 2017, 42(1): 108-113.
	LYU X Y, MENG F H, LI Z. Recent advance in bimetallic Ni-Ru catalyst for catalytic hydrogenation and hydrogen production reactions[J]. Natural Gas Chemical Industry, 2017, 42(1): 108-113.
79	TADA S, KIKUCHI R, TAKAGAKI A, et al. Study of Ru-Ni/TiO₂catalysts for selective CO methanation[J]. Applied Catalysis B: Environmental, 2013, 140/141: 258-264.
80	TADA S, MINORI D, OTSUKA F, et al. Effect of Ru and Ni ratio on selective CO methanation over Ru-Ni/TiO₂[J]. Fuel, 2014, 129: 219-224.
81	YANG K W, ZHANG M H, YU Y Z. Effect of transition metal-doped Ni(211) for CO dissociation: insights from DFT calculations[J]. Applied Surface Science, 2017, 399: 255-264.

[1]	ZHANG Mingyan, LIU Yan, ZHANG Xueting, LIU Yake, LI Congju, ZHANG Xiuling. Research progress of non-noble metal bifunctional catalysts in zinc-air batteries [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 276-286.
[2]	SHI Yongxing, LIN Gang, SUN Xiaohang, JIANG Weigeng, QIAO Dawei, YAN Binhang. Research progress on active sites in Cu-based catalysts for CO₂ hydrogenation to methanol [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 287-298.
[3]	XIE Luyao, CHEN Songzhe, WANG Laijun, ZHANG Ping. Platinum-based catalysts for SO₂ depolarized electrolysis [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 299-309.
[4]	YANG Xiazhen, PENG Yifan, LIU Huazhang, HUO Chao. Regulation of active phase of fused iron catalyst and its catalytic performance of Fischer-Tropsch synthesis [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 310-318.
[5]	WANG Lele, YANG Wanrong, YAO Yan, LIU Tao, HE Chuan, LIU Xiao, SU Sheng, KONG Fanhai, ZHU Canghai, XIANG Jun. Influence of spent SCR catalyst blending on the characteristics and deNO _x performance for new SCR catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 489-497.
[6]	DENG Liping, SHI Haoyu, LIU Xiaolong, CHEN Yaoji, YAN Jingying. Non-noble metal modified vanadium titanium-based catalyst for NH₃-SCR denitrification simultaneous control VOCs [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 542-548.
[7]	CHENG Tao, CUI Ruili, SONG Junnan, ZHANG Tianqi, ZHANG Yunhe, LIANG Shijie, PU Shi. Analysis of impurity deposition and pressure drop increase mechanisms in residue hydrotreating unit [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4616-4627.
[8]	WANG Peng, SHI Huibing, ZHAO Deming, FENG Baolin, CHEN Qian, YANG Da. Recent advances on transition metal catalyzed carbonylation of chlorinated compounds [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4649-4666.
[9]	GAO Yanjing. Analysis of international research trend of single-atom catalysis technology [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4667-4676.
[10]	ZHANG Qi, ZHAO Hong, RONG Junfeng. Research progress of anti-toxicity electrocatalysts for oxygen reduction reaction in PEMFC [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4677-4691.
[11]	GE Quanqian, XU Mai, LIANG Xian, WANG Fengwu. Research progress on the application of MOFs in photoelectrocatalysis [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4692-4705.
[12]	WANG Weitao, BAO Tingyu, JIANG Xulu, HE Zhenhong, WANG Kuan, YANG Yang, LIU Zhaotie. Oxidation of benzene to phenol over aldehyde-ketone resin based metal-free catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4706-4715.
[13]	GE Yafen, SUN Yu, XIAO Peng, LIU Qi, LIU Bo, SUN Chengying, GONG Yanjun. Research progress of zeolite for VOCs removal [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4716-4730.
[14]	WU Haibo, WANG Xilun, FANG Yanxiong, JI Hongbing. Progress of the development and application of 3D printing catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 3956-3964.
[15]	XIANG Yang, HUANG Xun, WEI Zidong. Recent progresses in the activity and selectivity improvement of electrocatalytic organic synthesis [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4005-4014.