Research progress on catalytic methane reforming process

doi:10.11949/0438-1157.20240625

Abstract

Abstract:

Natural gas is abundant, and methane is the main ingredient, which is usually used through reforming to produce high-quality clean energy. However, the catalyst deactivation caused by carbon deposition and sintering in the reforming process is a key factor hindering the large-scale industrial development of this process. Based on iron-based catalysts, the research progress on the performance of methane cracking reforming catalysts was reviewed from the perspectives of catalyst active components, supports, additives and preparation methods. Based on Ni-Fe bimetallic catalysts, the research progress on the performance of methane steam reforming and carbon dioxide reforming catalysts was reviewed. The causes of catalyst deactivation and the methods to improve the performance of reforming catalysts are described. In order to promote the industrial application of the reforming process, the carbon deposition mechanism of iron-based catalysts should be deeply explored in the future, and appropriate carriers and additives should be selected to optimize the performance of iron-based catalysts.

Key words: methane reforming, catalyst, iron-based catalysis, activity, deactivation

摘要：

天然气储量丰富，是优质的清洁能源，甲烷作为其主要成分，通常经由重整工艺来制备。而重整过程中由积炭烧结等引起的催化剂失活问题是阻碍该工艺大规模工业化发展的关键因素。基于铁基催化剂，从催化剂活性组分、载体、助剂以及制备方法等角度综述了甲烷裂解重整催化剂性能的研究进展。基于Ni-Fe双金属催化剂综述了甲烷蒸汽重整及二氧化碳重整催化剂性能的研究进展。阐述了催化剂的失活原因以及提高重整催化剂性能的方法。为了促进重整工艺的工业应用，未来应深度探讨铁基催化剂的积炭机理，选取合适的载体及助剂来优化铁基催化剂的性能。

关键词: 甲烷重整, 催化剂, 铁基催化, 活性, 失活

CLC Number:

TF 554

Meilin SHI, Lianda ZHAO, Xingjian DENG, Jingsong WANG, Haibin ZUO, Qingguo XUE. Research progress on catalytic methane reforming process[J]. CIESC Journal, 2024, 75(S1): 25-39.

石美琳, 赵连达, 邓行健, 王静松, 左海滨, 薛庆国. 催化甲烷重整工艺的研究进展[J]. 化工学报, 2024, 75(S1): 25-39.

Figures/Tables 16

Fig.1 Conversion mode and use of methane

Table 1 Methane reforming process

甲烷重整工艺	反应方程式	H₂/CO	优点	缺点
裂解重整	CH₄ $\overset{}{̿}$ C+2H₂	—	不产生污染气体CO₂的同时产生高附加值的碳产品，绿色经济	碳的形成和沉积造成催化剂失活
蒸汽重整	CH₄+H₂O $\overset{}{̿}$ 3H₂+CO	3∶1	可以产生更高浓度的氢，运行效率高，产业成熟度高	外部热交换装置的额外费用高
干重整	CH₄+CO₂ $\overset{}{̿}$ 2CO+2H₂	1∶1	同时使用了两种温室气体	高温条件下催化剂易积炭烧结
部分氧化重整	CH₄+1/2O₂ $\overset{}{̿}$ CO+2H₂	2∶1	对硫杂质有更高的耐受性，能耗少，经济	纯氧成本高，气体混合物可能会发生爆炸

Table 1 Methane reforming process

甲烷重整工艺	反应方程式	H₂/CO	优点	缺点
裂解重整	CH₄ $\overset{}{̿}$ C+2H₂	—	不产生污染气体CO₂的同时产生高附加值的碳产品，绿色经济	碳的形成和沉积造成催化剂失活
蒸汽重整	CH₄+H₂O $\overset{}{̿}$ 3H₂+CO	3∶1	可以产生更高浓度的氢，运行效率高，产业成熟度高	外部热交换装置的额外费用高
干重整	CH₄+CO₂ $\overset{}{̿}$ 2CO+2H₂	1∶1	同时使用了两种温室气体	高温条件下催化剂易积炭烧结
部分氧化重整	CH₄+1/2O₂ $\overset{}{̿}$ CO+2H₂	2∶1	对硫杂质有更高的耐受性，能耗少，经济	纯氧成本高，气体混合物可能会发生爆炸

Table 2 Classification of catalytic materials for methane cracking process

项目	分类	作用
活性组分	贵金属类：Pt、Ru、Rh等非贵金属类：Ni、Fe、Co等碳基：石墨、活性炭、金刚石等	催化甲烷裂解，能够解离活化甲烷分子，具有活化O—O、H—O键等的能力
载体	Al₂O₃、SiO₂、MgO、CeO、ZrO₂、钙钛矿、介孔材料等	起到骨架的作用，可与活性组分相互作用，负载活性组分
助剂	MgO、CaO、CeO₂、La₂O₃等	提高催化剂活性、抗积炭抗烧结等能力
制备方法	溶胶-凝胶法、共沉淀法、浸渍法等	制备合成催化剂

Table 3 Research results of Ermakova et al［10］

活性组分	载体	析碳量/g	氢体积/cm³
Fe	ZrO₂	13.5	50.4
Fe	Al₂O₃	14	52.3
Fe	TiO₂	17.4	64.9
Fe	SiO₂	45	168
Fe	—	16.5	61.6

Table 4 Influence of catalyst preparation method on catalytic performance of Fe catalyst tested in methane decomposition［18］

催化剂	制备方法	甲烷转化率%	催化剂寿命/h	析碳量/g
Fe-Al₂O₃	浸渍法[Fe(NO₃)₃]	—	2	1.1
Fe-SiO₂	浸渍法[Fe(NO₃)₃]	—	2	0.7
Fe-Al₂O₃	共沉淀法（NH₄OH）	4	23	26.5
Fe-Al₂O₃	共沉淀法（NaOH）	6	6	3.3
Fe-Al₂O₃	共沉淀法（Na₂CO₃）	4	6	2.3

Fig.2 Steam reforming process diagram[20]

Fig.3 Mechanism diagram of nickel-iron modified calcite[27]

Fig.4 Equilibrium components of the CO2/CH4 system at 1 atm (a) and 10 atm (b)[33]

Fig.5 TEM images of Fe-Ni catalyst[44]

Fig.6 Application of C-O-H2 ternary phase diagram in direct reduction process[53]

Table 5 Partial studies on catalyst deactivation

工艺	催化剂	失活原因	文献
催化裂解重整	Ni-SiO₂	活性中心组分Ni烧结、积炭	[54]
催化裂解重整	Fe-Al₂O₃	积炭	[18]
蒸汽重整	Fe	Fe氧化	[23]
蒸汽重整	Ni-Ce/Al	活性中心组分Ni烧结	[55]
蒸汽重整	Ni/Ni-Ru	活性中心组分Ni烧结	[56]
蒸汽重整	Ni-Ru/CeO₂-Al₂O₃	硫中毒	[57]
蒸汽重整	Pt/CeO₂-La₂O₃-Al₂O₃	活性中心组分Pt烧结	[58]
干重整	Fe-Al₂O₃	积炭	[36]
干重整	Ni-Fe	积炭	[59]
干重整	Ni-SiO₂/TiO₂/MgO	活性中心组分Ni烧结、积炭	[60]
干重整	Ni	活性中心组分Ni烧结	[37]
干重整	Ni/MgO	Ni氧化	[61]
干重整	Ni-Co/TiO₂	Co氧化	[62]
干重整	Co/γ-Al₂O₃	Co氧化	[63]

Fig.7 ∆G⊝ -T curve

Fig.8 C-H-O ternary phase diagram (1atm)

Fig.9 Schematic diagram of nucleation and growth stages of carbon filaments on iron carbide particles

Fig.10 Mechanism model of methane pyrolysis on iron catalyst[67]

Fig.11 Activation pathways of methane and carbon dioxide

References 88

1	张云, 胡浩权, 靳立军. 镍基催化剂的制备及催化甲烷裂解制氢研究[C]//第四届能源转化化学与技术研讨会.成都, 2021.
	Zhang Y, Hu H Q, Jin L J. Study on preparation of nickel-based catalysts and catalytic pyrolysis of methane for hydrogen production[C]//4th Symposium on Energy Conversion Chemistry and Technology. Chengdu, 2021.
2	Qian J X, Chen T W, Enakonda L R, et al. Methane decomposition to produce CO _x -free hydrogen and nano-carbon over metal catalysts: a review[J]. International Journal of Hydrogen Energy, 2020, 45(15): 7981-8001.
3	Ermakova M A, Ermakov D Y. Ni/SiO₂ and Fe/SiO₂ catalysts for production of hydrogen and filamentous carbon via methane decomposition[J]. Catalysis Today, 2002, 77(3): 225-235.
4	Jang H T, Cha W S. Hydrogen production by the thermocatalytic decomposition of methane in a fluidized bed reactor[J]. Korean Journal of Chemical Engineering, 2007, 24(2): 374-377.
5	Ibrahim A A, Fakeeha A H, Al-Fatesh A S, et al. Methane decomposition over iron catalyst for hydrogen production[J]. International Journal of Hydrogen Energy, 2015, 40(24): 7593-7600.
6	Jin L J, Si H H, Zhang J B, et al. Preparation of activated carbon supported Fe-Al₂O₃ catalyst and its application for hydrogen production by catalytic methane decomposition[J]. International Journal of Hydrogen Energy, 2013, 38(25): 10373-10380.
7	Pinilla J L, Utrilla R, Lázaro M J, et al. Ni- and Fe-based catalysts for hydrogen and carbon nanofilament production by catalytic decomposition of methane in a rotary bed reactor[J]. Fuel Processing Technology, 2011, 92(8): 1480-1488.
8	Shah N, Panjala D, Huffman G P. Hydrogen production by catalytic decomposition of methane[J]. Energy & Fuels, 2001, 15(6): 1528-1534.
9	Pudukudy M, Yaakob Z, Akmal Z S. Direct decomposition of methane over SBA-15 supported Ni, Co and Fe based bimetallic catalysts[J]. Applied Surface Science, 2015, 330: 418-430.
10	Ermakova M A, Ermakov D Y, Chuvilin A L, et al. Decomposition of methane over iron catalysts at the range of moderate temperatures: the influence of structure of the catalytic systems and the reaction conditions on the yield of carbon and morphology of carbon filaments[J]. Journal of Catalysis, 2001, 201(2): 183-197.
11	Karaismailoğlu M, Figen H E, Baykara S Z. Methane decomposition over Fe-based catalysts[J]. International Journal of Hydrogen Energy, 2020, 45(60): 34773-34782.
12	Al-Fatesh A S, Kasim S O, Ibrahim A A, et al. Catalytic methane decomposition over ZrO₂supported iron catalysts: effect of WO₃ and La₂O₃ addition on catalytic activity and stability[J]. Renewable Energy, 2020, 155: 969-978.
13	Pudukudy M, Yaakob Z, Jia Q M, et al. Catalytic decomposition of methane over rare earth metal (Ce and La) oxides supported iron catalysts[J]. Applied Surface Science, 2019, 467: 236-248.
14	Liu L, Zachariah M R. Enhanced performance of alkali metal doped Fe₂O₃ and Fe₂O₃/Al₂O₃ composites As oxygen carrier material in chemical looping combustion[J]. Energy & Fuels, 2013, 27(8): 4977-4983.
15	Al-Fatesh A S, Fakeeha A H, Ibrahim A A, et al. Iron oxide supported on Al₂O₃ catalyst for methane decomposition reaction: effect of MgO additive and calcination temperature[J]. Journal of the Chinese Chemical Society, 2016, 63(2): 205-212.
16	Al-Fatesh A S, Fakeeha A H, Ibrahim A A, et al. Decomposition of methane over alumina supported Fe and Ni-Fe bimetallic catalyst: effect of preparation procedure and calcination temperature[J]. Journal of Saudi Chemical Society, 2018, 22(2): 239-247.
17	Avdeeva L B, Goncharova O V, Kochubey D I, et al. Coprecipitated Ni-alumina and Ni-Cu-alumina catalysts of methane decomposition and carbon deposition(Ⅱ): Evolution of the catalysts in reaction[J]. Applied Catalysis A: General, 1996, 141(1/2): 117-129.
18	Avdeeva L B, Reshetenko T V, Ismagilov Z R, et al. Iron-containing catalysts of methane decomposition: accumulation of filamentous carbon[J]. Applied Catalysis A: General, 2002, 228(1/2): 53-63.
19	孙杰, 孙春文, 李吉刚, 等. 甲烷水蒸气重整反应研究进展[J]. 中国工程科学, 2013, 15(2): 98-106.
	Sun J, Sun C W, Li J G, et al. Research development of steam methane reforming reactions[J]. Engineering Sciences, 2013, 15(2): 98-106.
20	Yusuf B O, Umar M, Kotob E, et al. Recent advances in bimetallic catalysts for methane steam reforming in hydrogen production: current trends, challenges, and future prospects[J]. Chemistry, an Asian Journal, 2023: e202300641.
21	陈曦. 镍基催化剂制备及在甲烷水蒸气重整反应中的应用[D]. 大连: 大连理工大学, 2014.
	Chen X. Preparation of Ni-based catalyst and application in steam reforming of methane[D]. Dalian: Dalian University of Technology, 2014.
22	Meloni E, Martino M, Palma V. A short review on Ni based catalysts and related engineering issues for methane steam reforming[J]. Catalysts, 2020, 10(3): 352.
23	Jones G, Jakobsen J G, Shim S S, et al. First principles calculations and experimental insight into methane steam reforming over transition metal catalysts[J]. Journal of Catalysis, 2008, 259(1): 147-160.
24	Sharma R, Kumar A, Upadhyay R K. Bimetallic Fe‐promoted catalyst for CO‐free hydrogen production in high‐temperature‐methanol steam reforming[J]. ChemCatChem, 2019, 11(18): 4568-4580.
25	Wei Z H, Sun J M, Li Y, et al. Bimetallic catalysts for hydrogen generation[J]. Chemical Society Reviews, 2012, 41(24): 7994-8008.
26	Garai M H S, Khosravi-Nikou M R, Shariati A. Chemical looping steam methane reforming via Ni‐ferrite supported on cerium and zirconium oxides[J]. Chemical Engineering & Technology, 2020, 43(9): 1813-1822.
27	Hu Z F, Miao Z W, Wu J W, et al. Nickel-iron modified natural ore oxygen carriers for chemical looping steam methane reforming to produce hydrogen[J]. International Journal of Hydrogen Energy, 2021, 46(80): 39700-39718.
28	Tsodikov M V, Kurdymov S S, Konstantinov G I, et al. Core-shell bifunctional catalyst for steam methane reforming resistant to H₂S: activity and structure evolution[J]. International Journal of Hydrogen Energy, 2015, 40(7): 2963-2670.
29	Konstantinov G I, Kurdyumov S S, Maksimov Y V, et al. Hydrogen sulfide-resistant bifunctional catalysts for the steam reforming of methane: activity and structural evolution[J]. Catalysis in Industry, 2018, 10(1): 1-8.
30	Djaidja A, Messaoudi H, Kaddeche D, et al. Study of Ni-M/MgO and Ni-M-Mg/Al (M=Fe or Cu) catalysts in the CH₄-CO₂ and CH₄-H₂O reforming[J]. International Journal of Hydrogen Energy, 2015, 40(14): 4989-4995.
31	Braga A, Armengol-Profitós M, Pascua-Solé L, et al. Bimetallic NiFe nanoparticles supported on CeO₂as catalysts for methane steam reforming[J]. ACS Applied Nano Materials, 2023, 6(9): 7173-7185.
32	Arandiyan H, Li J H, Ma L, et al. Methane reforming to syngas over LaNi _x Fe_1- _x O₃(0≤x≤1) mixed-oxide perovskites in the presence of CO₂ and O₂ [J]. Journal of Industrial and Engineering Chemistry, 2012, 18(6): 2103-2114.
33	Wang S B, Lu G Q, Millar G J. Carbon dioxide reforming of methane to produce synthesis gas over metal-supported catalysts: state of the art[J]. Energy & Fuels, 1996, 10(4): 896-904.
34	李肖晓. 甲烷二氧化碳重整镍基催化剂的研究[D]. 青岛:青岛科技大学, 2016.
	Li X X. Carbon dioxide reforming of methane over Ni-based catalysts[D]. Qingdao: Qingdao University of Science & Technology, 2016.
35	吴兴亮, 吕凌辉, 马清祥,等. 甲烷二氧化碳重整镍基催化剂的研究进展[J]. 洁净煤技术, 2021, 27(3): 129-137.
	Wu X L, Lyu L H, Ma Q X, et al. Research progress of nickel-based catalysts for carbon dioxide reforming of methane[J]. Clean Coal Technology, 2021, 27(3): 129-137.
36	Tokunaga O, Osada Y, Ogasawara S. Reaction of CO₂-CH₄ as a high-level heat transport system[J]. Fuel, 1989, 68(8): 990-994.
37	Gadalla A M, Bower B. The role of catalyst support on the activity of nickel for reforming methane with CO₂ [J]. Chemical Engineering Science, 1988, 43(11): 3049-3062.
38	Benrabaa R, Boukhlouf H, Bordes-Richard E, et al. Nanosized nickel ferrite catalysts for CO₂ reforming of methane at low temperature: effect of preparation method and acid-base properties[C]//Scientific Bases for the Preparation of Heterogeneous Catalysts - Proceedings of the 10th International Symposium. Amsterdam: Elsevier, 2010: 301-304.
39	郑幼松, 邹宗鹏, 吕莉, 等. 甲烷干重整抗失活镍基催化剂研究进展[J]. 天然气化工—C₁化学与化工, 2021, 46(6): 1-8, 16.
	Zheng Y S, Zou Z P, Lv L, et al. Research progress of anti-deactivation nickel based catalysts for dry reforming of methane[J]. Natural Gas Chemical Industry, 2021, 46(6): 1-8, 16.
40	Theofanidis S A, Galvita V V, Konstantopoulos C, et al. Fe-based nano-materials in catalysis[J]. Materials, 2018, 11(5): 831.
41	Buelens L C, Galvita V V, Poelman H, et al. Super-dry reforming of methane intensifies CO₂ utilization via Le Chatelier's principle[J]. Science, 2016, 354(6311): 449-452.
42	Margossian T, Larmier K, Kim S M, et al. Supported bimetallic NiFe nanoparticles through colloid synthesis for improved dry reforming performance[J]. ACS Catalysis, 2017, 7(10): 6942-6948.
43	Tomishige K, Li D L, Tamura M, et al. Nickel-iron alloy catalysts for reforming of hydrocarbons: preparation, structure, and catalytic properties[J]. Catalysis Science & Technology, 2017, 7(18): 3952-3979.
44	Theofanidis S A, Batchu R, Galvita V V, et al. Carbon gasification from Fe-Ni catalysts after methane dry reforming[J]. Applied Catalysis B: Environmental, 2016, 185: 42-55.
45	Theofanidis S A, Galvita V V, Poelman H, et al. Enhanced carbon-resistant dry reforming Fe-Ni catalyst: role of Fe[J]. ACS Catalysis, 2015, 5(5): 3028-3039.
46	Hwang S, Hong U G, Lee J, et al. Methanation of carbon dioxide over mesoporous Ni-Fe-Al₂O₃ catalysts prepared by a coprecipitation method: effect of precipitation agent[J]. Journal of Industrial and Engineering Chemistry, 2013, 19(6): 2016-2021.
47	Kim S M, Abdala P M, Margossian T, et al. Cooperativity and dynamics increase the performance of NiFe dry reforming catalysts[J]. Journal of the American Chemical Society, 2017, 139(5): 1937-1949.
48	Zhang T, Liu Z X, Zhu Y A, et al. Dry reforming of methane on Ni-Fe-MgO catalysts: influence of Fe on carbon-resistant property and kinetics[J]. Applied Catalysis B: Environmental, 2020, 264: 118497.
49	Wang H, Srinath N V, Poelman H, et al. Hierarchical Fe-modified MgAl₂O₄ as a Ni-catalyst support for methane dry reforming[J]. Catalysis Science & Technology, 2020, 10(20): 6987-7001.
50	Kim C, Kim Y. Promotional effect of iron on nickel-based catalyst for combined steam-carbon dioxide reformation of methane[J]. Journal of Nanoscience and Nanotechnology, 2020, 20(9): 5506-5509.
51	Yang E, Noh Y, Lim S, et al. The effect of Fe in perovskite catalysts for steam CO₂ reforming of methane[J]. Journal of Nanoscience and Nanotechnology, 2017, 16(2): 1938-1941.
52	Song X, Dong X L, Yin S L, et al. Effects of Fe partial substitution of La₂NiO₄/LaNiO₃catalyst precursors prepared by wet impregnation method for the dry reforming of methane[J]. Applied Catalysis A: General, 2016, 526: 132-138.
53	Ribeiro T R, Ferreira Neto J B, Takano C, et al. C-O-H₂ternary diagram for evaluation of carbon activity in CH₄-containing gas mixtures[J]. Journal of Materials Research and Technology, 2021, 13: 1576-1585.
54	Aiello R, Fiscus J E, Loye H C Z, et al. Hydrogen production via the direct cracking of methane over Ni/SiO₂: catalyst deactivation and regeneration[J]. Applied Catalysis A: General, 2000, 192(2): 227-234.
55	Yang X, Da J W, Yu H T, et al. Characterization and performance evaluation of Ni-based catalysts with Ce promoter for methane and hydrocarbons steam reforming process[J]. Fuel, 2016, 179: 353-361.
56	Luna E C, Becerra A M, Dimitrijewits M I. Methane steam reforming over rhodium promoted Ni/Al₂O₃catalysts[J]. 1999, 67(2): 247-252.
57	Xie C, Chen Y S, Li Y, et al. Sulfur poisoning of CeO₂-Al₂O₃-supported mono- and bi-metallic Ni and Rh catalysts in steam reforming of liquid hydrocarbons at low and high temperatures[J]. Applied Catalysis A: General, 2010, 390(1/2): 210-218.
58	Mortola V B, Damyanova S, Zanchet D, et al. Surface and structural features of Pt/CeO₂-La₂O₃-Al₂O₃ catalysts for partial oxidation and steam reforming of methane[J]. Applied Catalysis B: Environmental, 2011, 107(3/4): 221-236.
59	彭瑞峰. 镍铁体系构筑与促进甲烷干重整性能调控[D]. 徐州: 中国矿业大学, 2021.
	Peng R F. Construction of high-efficiency nickel-iron catalyst system and its methane dry reforming performance tailoring[D]. Xuzhou: China University of Mining and Technology, 2021.
60	Swaan H M, Kroll V C H, Martin G A, et al. Deactivation of supported nickel catalysts during the reforming of methane by carbon dioxide[J]. Catalysis Today, 1994, 21(2/3): 571-578.
61	李琳, 张露明, 张煜华, 等. 镍负载量对Ni/MgO(111)催化甲烷二氧化碳重整反应性能影响[J]. 燃料化学学报, 2015, 43(3): 315-322.
	Li Lin, Zhang L M, Zhang Y H, et al. Effect of Ni loadings on the catalytic properties of Ni/MgO(111) catalyst for the reforming of methane with carbon dioxide[J]. Journal of Fuel Chemistry and Technology, 2015, 43(3): 315-322.
62	Takanabe K, Nagaoka K, Aika K I. Improved resistance against coke deposition of titania supported cobalt and nickel bimetallic catalysts for carbon dioxide reforming of methane[J]. Catalysis Letters, 2005, 102(3): 153-157.
63	Ruckenstein E, Wang H Y. Carbon deposition and catalytic deactivation during CO₂ reforming of CH₄ over Co/γ-Al₂O₃ catalysts[J]. Journal of Catalysis, 2002, 205(2): 289-293.
64	万云云. 甲烷二氧化碳重整工艺研究[D]. 淮南: 安徽理工大学, 2016.
	Wan Y Y. Study on reforming process of methane with carbon dioxide[D]. Huainan: Anhui University of Science & Technology, 2016.
65	Sacco A, Geurts F W A H, Jablonski G A, et al. Carbon deposition and filament growth on Fe, Co, and Ni foils using CH₄-H₂-H₂O-CO-CO₂ gas mixtures[J]. Journal of Catalysis, 1989, 119(2): 322-341.
66	Tsipouriari V A, Efstathiou A M, Zhang Z L, et al. Reforming of methane with carbon dioxide to synthesis gas over supported Rh catalysts[J]. Catalysis Today, 1994, 21(2/3): 579-587.
67	Zhou L, Enakonda L R, Harb M, et al. Fe catalysts for methane decomposition to produce hydrogen and carbon nano materials[J]. Applied Catalysis B: Environmental, 2017, 208: 44-59.
68	Hasebe M, Ohtani H, Nishizawa T. Effect of magnetic transition on solubility of carbon in bcc Fe and fee Co-Ni alloys[J]. Metallurgical Transactions A, 1985, 16(5): 913-921.
69	Wirth C T, Bayer B C, Gamalski A D, et al. The phase of iron catalyst nanoparticles during carbon nanotube growth[J]. Chemistry of Materials, 2012, 24(24): 4633-4640.
70	Wrobel R J, Hełminiak A, Arabczyk W, et al. Studies on the kinetics of carbon deposit formation on nanocrystalline iron stabilized with structural promoters[J]. The Journal of Physical Chemistry C, 2014, 118(28): 15434-15439.
71	Sharma R, Moore E, Rez P, et al. Site-specific fabrication of Fe particles for carbon nanotube growth[J]. Nano Letters, 2009, 9(2): 689-694.
72	Arora S, Prasad R. An overview on dry reforming of methane: strategies to reduce carbonaceous deactivation of catalysts[J]. RSC Advances, 2016, 6(110): 108668-108688.
73	朱清江, 李德康, 班延鹏, 等. 甲烷二氧化碳联合水蒸气重整过程中镍基催化剂硫中毒与再生研究[J]. 天然气化工—C1化学与化工, 2022, 47(4): 83-91.
	Zhu Q J, Li D K, Ban Y P, et al. Sulfur poisoning and regeneration of nickel-based catalyst in process of combined steam and carbon dioxide reforming of methane[J]. Natural Gas Chemical Industry, 2022, 47(4): 83-91.
74	Olsson R G, Turkdogan E T. Catalytic effect of iron on decomposition of carbon monoxide( Ⅱ ): Effect of additions of H₂, H₂O, CO₂, SO₂ and H₂S[J]. Metallurgical Transactions, 1974, 5(1): 21-26.
75	Karcher W, Glaude P. Inhibition of carbon deposition on iron and steel surfaces[J]. Carbon, 1971, 9(5): 617-625.
76	Bartholomew C H. Carbon deposition in steam reforming and methanation[J]. Catalysis Reviews, 1982, 24(1): 67-112.
77	Lucrédio A F, Bellido J D A, Assaf E M. Effects of adding La and Ce to hydrotalcite-type Ni/Mg/Al catalyst precursors on ethanol steam reforming reactions[J]. Applied Catalysis A: General, 2010, 388(1/2): 77-85.
78	王锐, 刘雪斌, 陈燕馨, 等. 金属-载体相互作用对CH₄/CO₂重整反应中Rh基催化剂抗积炭性能的影响[J]. 催化学报, 2007, 28(10): 865-869.
	Wang R, Liu X B, Chen Y X, et al. Effect of metal-support interaction on coking resistance of Rh-based catalysts in CH₄/CO₂ reforming[J]. Chinese Journal of Catalysis, 2007, 28(10): 865-869.
79	Gallego G S, Batiot-Dupeyrat C, Barrault J, et al. Dry reforming of methane over LaNi_1- _y B _y O₃ (B = Mg, Co) perovskites used as catalyst precursor[J]. Applied Catalysis A: General, 2008, 334(1/2): 251-258.
80	Wang Z Y, Cao X M, Zhu J H, et al. Activity and coke formation of nickel and nickel carbide in dry reforming: a deactivation scheme from density functional theory[J]. Journal of Catalysis, 2014, 311: 469-480.
81	李彬. 基于提高甲烷重整活性的镍基催化剂的修饰及性能研究[D]. 广州: 华南理工大学, 2021.
	Li B. Modificationand catalytic performance study based on improving reactivity of nickel based catalysts for methane reforming[D]. Guangzhou: South China University of Technology, 2021.
82	高志博, 王晓波, 刘金明, 等. 甲烷水蒸气重整制合成气的研究进展[J]. 高师理科学刊, 2012, 32(2): 79-81, 89.
	Gao Z B, Wang X B, Liu J M, et al. The progress in study of Methane steam reforming to synthesis gas[J]. Journal of Science of Teachers' College and University, 2012, 32(2): 79-81, 89.
83	Borowiecki T, Denis A, Rawski M, et al. Studies of potassium-promoted nickel catalysts for methane steam reforming: effect of surface potassium location[J]. Applied Surface Science, 2014, 300: 191-200.
84	Parizotto N V, Rocha K O, Damyanova S, et al. Alumina-supported Ni catalysts modified with silver for the steam reforming of methane: effect of Ag on the control of coke formation[J]. Applied Catalysis A: General, 2007, 330: 12-22.
85	Wan H J, Li X J, Ji S F, et al. Effect of Ni loading and Ce _x Zr_1- _x O₂ promoter on Ni-based SBA-15 catalysts for steam reforming of methane[J]. Journal of Natural Gas Chemistry, 2007, 16(2): 139-147.
86	Shen J, Reule A A C, Semagina N. Ni/MgAl₂O₄ catalyst for low-temperature oxidative dry methane reforming with CO₂ [J]. International Journal of Hydrogen Energy, 2019, 44(10): 4616-4629.
87	Takenaka S, Ogihara H, Yamanaka I, et al. Decomposition of methane over supported-Ni catalysts: effects of the supports on the catalytic lifetime[J]. Applied Catalysis A: General, 2001, 217(1/2): 101-110.
88	Choudhary T V, Goodman D W. CO-free production of hydrogen via stepwise steam reforming of methane[J]. Journal of Catalysis, 2000, 192(2): 316-321.

[1]	Ran WANG, Huan WANG, Xiaoyun XIONG, Huimin GUAN, Yunfeng ZHENG, Cailin CHEN, Yucai QIN, Lijuan SONG. Visual analysis of mass transfer enhanced active site utilization efficiency of FCC catalyst [J]. CIESC Journal, 2024, 75(9): 3198-3209.
[2]	Shuzhen WANG, Yuting WANG, Mengxi MA, Wei ZHANG, Jiangnan XIANG, Haiying LU, Yan WANG, Binbin FAN, Jiajun ZHENG, Weijiong DAI, Ruifeng LI. Synthesis of ZSM-22 molecular sieve by two-step crystallization and its hydroisomerization performance [J]. CIESC Journal, 2024, 75(9): 3176-3187.
[3]	Yachao LIU, Xiaojie TAN, Xudong LI, Rui WANG, Hui WANG, Xuan HAN, Qingshan ZHAO. Synthesis of efficient cobalt carbonate nanosheets based on DES for oxygen evolution reaction [J]. CIESC Journal, 2024, 75(9): 3320-3328.
[4]	Mengting ZHANG, Shulin WANG, Xi SANG, Xinghao YUAN, Gang XU. Artificial Cu-TM1459 metalloenzyme catalyzes asymmetric Michael addition reaction [J]. CIESC Journal, 2024, 75(9): 3255-3265.
[5]	Shaojun DOU, Liang HAO. Mesoscale simulation of coupled gas charge transfer process in PEMFC catalyst layer [J]. CIESC Journal, 2024, 75(8): 3002-3010.
[6]	Yin WANG, Pengfei CHU, Hu LIU, Jing LYU, Shouying HUANG, Shengping WANG, Xinbin MA. Influence of aluminum sol with different pH on performance of shaped mordenite catalyst for dimethyl ether carbonylation [J]. CIESC Journal, 2024, 75(7): 2533-2543.
[7]	Lu YANG, Congcong LIU, Tongtong MENG, Boyuan ZHANG, Tengfei YANG, Wen’an DENG, Xiaobin WANG. Hydrogenation and coke-suppression performance of dispersed catalyst in coal/heavy oil co-processing reactions [J]. CIESC Journal, 2024, 75(7): 2556-2564.
[8]	Xusheng LIU, Zeyang LI, Yusen YANG, Min WEI. Research progress on electrocatalytic carbon dioxide reduction to gaseous products [J]. CIESC Journal, 2024, 75(7): 2385-2408.
[9]	Li LUO, Wenyao CHEN, Jing ZHANG, Gang QIAN, Xinggui ZHOU, Xuezhi DUAN. Alumina structure and surface property regulation for catalyzing methanol dehydration to dimethyl ether [J]. CIESC Journal, 2024, 75(7): 2522-2532.
[10]	Tianwen WANG, Su YAN, Mengyuan ZHAO, Tianrang YANG, Jianguo LIU. Mechanisms of chromium poisoning in solid oxide cell air electrodes and research advances in enhancing chromium-resistivity [J]. CIESC Journal, 2024, 75(6): 2091-2108.
[11]	Yu DING, Changze YANG, Jun LI, Huidong SUN, Hui SHANG. Research progress and prospects of atomic-scale molybdenum-based hydrodesulfurization catalysts [J]. CIESC Journal, 2024, 75(5): 1735-1749.
[12]	Tingting ZHAO, Lixiang YAN, Fuli TANG, Minzhi XIAO, Ye TAN, Liubin SONG, Zhongliang XIAO, Lingjun LI. Research progress on design strategies and reaction mechanisms of photo-assisted Li-CO₂ battery catalysts [J]. CIESC Journal, 2024, 75(5): 1750-1764.
[13]	Jinhong MO, Xue HAN, Yixiang ZHU, Jing LI, Xuyu WANG, Hongbing JI. Investigation of Pt-Ga/CeO₂-ZrO₂-Al₂O₃bifunctional catalyst for the catalytic conversion of n-butane into olefins [J]. CIESC Journal, 2024, 75(5): 1855-1869.
[14]	Yiwei FAN, Wei LIU, Yingying LI, Peixia WANG, Jisong ZHANG. Research progress on catalytic dehydrogenation of dodecahydro-N-ethylcarbazole as liquid organic hydrogen carrier [J]. CIESC Journal, 2024, 75(4): 1198-1208.
[15]	Xudong JIA, Bolong YANG, Qian CHENG, Xueli LI, Zhonghua XIANG. Preparation of high-efficiency iron-cobalt bimetallic site oxygen reduction electrocatalysts by step-by-step metal loading method [J]. CIESC Journal, 2024, 75(4): 1578-1593.