Methane decomposition to produce pure hydrogen and carbon nano materials over FeM catalysts

doi:10.16085/j.issn.1000-6613.2020-2226

Abstract

Abstract:

A series of Fe_xM_y (M=Mo, Cu, W) bimetallic catalysts were prepared by the fusion method using iron, molybdenum, copper and tungsten nitrate as raw materials. Fe₁₅M₁ (M=Mo, Cu, W) bimetallic catalysts were synthesized to investigate their catalytic decomposition of methane (CDM) activity. Results indicated that the catalytic activity of Fe₁₅Mo₁ was much higher than that of Fe₁₅Cu₁ and Fe₁₅W₁. The physical characteristics, structural composition, reduction characteristics and the graphitization of by-product carbon nano materials (CNMs) were characterized by means of specific surface area (BET), X?ray powder diffraction (XRD), H₂ temperature programmed reduction (H₂-TPR) and Raman spectra, respectively. Then, the effects of Mo doping and calcination temperature on the methane conversion and carbon yield over the Fe_xMo_y catalysts for CDM were further investigated. It was found that, the Fe₁Mo₁ catalyst had the best catalytic activity and stability, and its carbon yield (6g_C/g_cat) was higher than that of pure Fe (4.35g_C/g_cat). XRD and X-ray photoelectron spectroscopy (XPS) results showed that Fe₂(MoO₄)₃ phase was formed in Fe₁Mo₁, which increased the catalytic activity and stability. Transmission electron microscope (TEM) results indicated that the deposited CNMs over the spent Fe₁Mo₁ catalyst were bamboo-like carbon nano tubes.

Key words: methane, decomposition, catalyst, hydrogen production, carbon nano materials

摘要：

采用熔融法以铁、钼、铜和钨硝酸盐为原料，制备出一系列的Fe_xM_y（M=Mo、Cu、W）双金属催化剂。首先考察了一系列的Fe₁₅M₁（M=Mo、Cu、W）双金属催化剂的甲烷催化裂解（CDM）活性，Fe₁₅Mo₁的催化活性远高于Fe₁₅Cu₁和Fe₁₅W₁。通过比表面积测试（BET）、X射线衍射（XRD）、H₂程序升温还原（H₂-TPR）和拉曼光谱（Raman）等分析方法对Fe₁₅M₁的物理特性、结构组成、还原特性和副产物碳纳米材料（CNMs）的石墨化度等进行表征。进一步考察了金属Mo的掺杂量和焙烧温度对Fe_xMo_y双金属催化剂的甲烷转化率和碳产率的影响。Fe₁Mo₁表现出优异的催化性能，其碳产率（6g_C/g_cat）高于纯Fe的碳产率（4.35g_C/g_cat）。XRD和X射线光电子能谱（XPS）分析表明，Fe₁Mo₁双金属形成Fe₂(MoO₄)₃相，提高了其催化活性和稳定性；透射电镜（TEM）结果表明，Fe₁Mo₁催化剂CDM反应后的CNMs为竹节状的碳纳米管。

关键词: 甲烷, 裂解, 催化剂, 制氢, 碳纳米材料

CLC Number:

O611.65

QIAN Jingxia, CHEN Tianwen, LIU Dabin, ZHOU Lyu. Methane decomposition to produce pure hydrogen and carbon nano materials over FeM catalysts[J]. Chemical Industry and Engineering Progress, 2021, 40(11): 6102-6112.

钱敬侠, 陈天文, 刘大斌, 周吕. FeM双金属用于甲烷催化裂解制纯氢气和碳纳米材料[J]. 化工进展, 2021, 40(11): 6102-6112.

Figures/Tables 18

References 57

1	IBRAHIM A A, AL‐FATESH A S, KHAN W U, et al. Influence of support type and metal loading in methane decomposition over iron catalyst for hydrogen production[J]. Journal of the Chinese Chemical Society, 2015, 62(7): 592-599.
2	王迪, 胡燕, 高卫民, 等. 甲烷催化裂解制氢和碳纳米材料研究进展[J]. 化工进展, 2018, 37(S1): 80-93.
	WANG Di, HU Yan, GAO Weimin, et al. Progress of methane catalytic decomposition for hydrogen and carbon nanomaterials production[J]. Chemical Industry and Engineering Progress, 2018, 37(S1): 80-93.
3	彭乔. 甲烷裂解制氢催化剂的制备及其性能与模拟研究[D]. 武汉: 华中师范大学, 2016.
	PENG Qiao. The preparation of methane cracking catalyst for hydrogen production and its performance and simulation studies[D]. Wuhan: Central China Normal University, 2016.
4	AL-FATESH A S, IBRAHIM A A, ALSHAREKH A M, et al. Methane decomposition over strontium promoted iron catalyst: effect of different ratio of Al/Si support on hydrogen yield[J]. Chemical Engineering Communications, 2020, 207(8): 1148-1156.
5	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, 467/468: 236-248.
6	GENG S, HAN Z, HU Y, et al. Methane decomposition kinetics over Fe₂O₃ catalyst in micro fluidized bed reaction analyzer[J]. Industrial & Engineering Chemistry Research, 2018, 57(25): 8413-8423.
7	KARAISMAILOGLU M, FIGEN H E, BAYKARA S Z. Hydrogen production by catalytic methane decomposition over yttria doped nickel based catalysts[J]. International Journal of Hydrogen Energy, 2019, 44(20): 9922-9929.
8	UPHAM D C, AGARWAL V, KHECHFE A, et al. Catalytic molten metals for the direct conversion of methane to hydrogen and separable carbon[J]. Science, 2017, 358(6365): 917-921.
9	ASHIK U P M, WAN DAUD W M A, ABBAS H F. Production of greenhouse gas free hydrogen by thermocatalytic decomposition of methane—A review[J]. Renewable and Sustainable Energy Reviews, 2015, 44: 221-256.
10	QIAN J X, CHEN T W, ENAKONDA L R, et al. Methane decomposition to pure hydrogen and carbon nano materials: state-of-the-art and future perspectives[J]. International Journal of Hydrogen Energy, 2020, 45(32): 15721-15743.
11	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.
12	ALLAEDINI G, TASIRIN S M, AMINAYI P, et al. Bulk production of bamboo-shaped multi-walled carbon nanotubes via catalytic decomposition of methane over tri-metallic Ni-Co-Fe catalyst[J]. Reaction Kinetics, Mechanisms and Catalysis, 2015, 116(2): 385-396.
13	CALAFAT Á, SÁNCHEZ N. Production of carbon nanotubes through combination of catalyst reduction and methane decomposition over Fe-Ni/ZrO₂ catalysts prepared by the citrate method[J]. Applied Catalysis A: General, 2016, 528: 14-23.
14	OLIVEIRA P F, RIBEIRO L P, ROSMANINHO M G, et al. Effect of Sn on methane decomposition over Fe supported catalysts to produce carbon[J]. Hyperfine Interactions, 2011, 203(1/2/3): 67-74.
15	FAKEEHA A H, IBRAHIM A A, NAEEM M A, et al. Methane decomposition over Fe supported catalysts for hydrogen and nano carbon yield[J]. Catalysis for Sustainable Energy, 2015, 2(1): 71-82.
16	TORRES D, PINILLA J L, LÁZARO M J, et al. Hydrogen and multiwall carbon nanotubes production by catalytic decomposition of methane: thermogravimetric analysis and scaling-up of Fe-Mo catalysts[J]. International Journal of Hydrogen Energy, 2014, 39(8): 3698-3709.
17	ZHOU L, ENAKONDA L R, LI S, et al. Iron ore catalysts for methane decomposition to make CO_x free hydrogen and carbon nano material[J]. Journal of the Taiwan Institute of Chemical Engineers, 2018, 87: 54-63.
18	FAKEEHA A H, IBRAHIM A A, KHAN W U, et al. Hydrogen production via catalytic methane decomposition over alumina supported iron catalyst[J]. Arabian Journal of Chemistry, 2018, 11(3): 405-414.
19	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.
20	SIMON A, SEYRING M, KAMNITZ S, et al. Carbon nanotubes and carbon nanofibers fabricated on tubular porous Al₂O₃ substrates[J]. Carbon, 2015, 90: 25-33.
21	TORRES D, PINILLA J, SUELVES I. Co-, Cu- and Fe-doped Ni/Al₂O₃ catalysts for the catalytic decomposition of methane into hydrogen and carbon nanofibers[J]. Catalysts, 2018, 8(8): 300.
22	ZHANG C, ZHANG W, DREWETT N E, et al. Integrating catalysis of methane decomposition and electrocatalytic hydrogen evolution with Ni/CeO₂ for improved hydrogen production efficiency[J]. ChemSusChem, 2019, 12(5): 1000-1010.
23	CALGARO C O, PEREZ-LOPEZ O W. Graphene and carbon nanotubes by CH₄ decomposition over CoAl catalysts[J]. Materials Chemistry and Physics, 2019, 226: 6-19.
24	PUDUKUDY M, YAAKOB Z, AKMAL Z S. Direct decomposition of methane over Pd promoted Ni/SBA-15 catalysts[J]. Applied Surface Science, 2015, 353: 127-136.
25	WANG J, JIN L, LI Y, et al. Preparation of Fe-doped carbon catalyst for methane decomposition to hydrogen[J]. Industrial & Engineering Chemistry Research, 2017, 56(39): 11021-11027.
26	NISHII H, MIYAMOTO D, UMEDA Y, et al. Catalytic activity of several carbons with different structures for methane decomposition and by-produced carbons[J]. Applied Surface Science, 2019, 473: 291-297.
27	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.
28	TANG L, YAMAGUCHI D, BURKE N, et al. Methane decomposition over ceria modified iron catalysts[J]. Catalysis Communications, 2010, 11(15): 1215-1219.
29	PUDUKUDY M, KADIER A, YAAKOB Z, et al. Non-oxidative thermocatalytic decomposition of methane into CO_x free hydrogen and nanocarbon over unsupported porous NiO and Fe₂O₃ catalysts[J]. International Journal of Hydrogen Energy, 2016, 41(41): 18509-18521.
30	AWADALLAH A E, ABOUL-ENEIN A A, KANDIL U F, et al. Facile and large-scale synthesis of high quality few-layered graphene nano-platelets via methane decomposition over unsupported iron family catalysts[J]. Materials Chemistry and Physics, 2017, 191: 75-85.
31	PUDUKUDY M, YAAKOB Z, DAHANI N, et al. Production of CO_x free hydrogen and nanocarbon via methane decomposition over unsupported porous nickel and iron catalysts[J]. Journal of Cluster Science, 2017, 28(3): 1579-1594.
32	ASHIK U P M, DAUD W M A W. Stabilization of Ni, Fe, and Co nanoparticles through modified Stöber method to obtain excellent catalytic performance: preparation, characterization, and catalytic activity for methane decomposition[J]. Journal of the Taiwan Institute of Chemical Engineers, 2016, 61: 247-260.
33	WANG H Y, LUA A C. Methane decomposition using Ni-Cu alloy nano-particle catalysts and catalyst deactivation studies[J]. Chemical Engineering Journal, 2015, 262: 1077-1089.
34	PUDUKUDY M, YAAKOB Z, TAKRIFF M S. Methane decomposition over unsupported mesoporous nickel ferrites: effect of reaction temperature on the catalytic activity and properties of the produced nanocarbon[J]. RSC Advances, 2016, 6(72): 68081-68091.
35	QIAN J X, ENAKONDA L R, WANG W J, et al. Optimization of a fluidized bed reactor for methane decomposition over Fe/Al₂O₃ catalysts: activity and regeneration studies[J]. International Journal of Hydrogen Energy, 2019, 44(60): 31700-31711.
36	ZHOU L, ENAKONDA L R, SAIH Y, et al. Catalytic methane decomposition over Fe-Al₂O₃[J]. ChemSusChem, 2016, 9(11): 1243-1248.
37	REDDY ENAKONDA L, ZHOU L, SAIH Y, et al. Methane-induced activation mechanism of fused ferric oxide-alumina catalysts during methane decomposition[J]. ChemSusChem, 2016, 9(15): 1911-1915.
38	ZHANG X, NIU Y, LI Y, et al. Synthesis, optical and magnetic properties of α-Fe₂O₃ nanoparticles with various shapes[J]. Materials Letters, 2013, 99: 111-114.
39	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.
40	EBERT D Y, DOROFEEVA N V, SAVEL’EVA A S, et al. Silica-supported Fe-Mo-O catalysts for selective oxidation of propylene glycol[J]. Catalysis Today, 2019, 333: 133-139.
41	YUE Y, LIU B, LY N, et al. Direct synthesis of hierarchical FeCu‍‐ZSM-5 zeolite with wide temperature window in selective catalytic reduction of NO by NH₃[J]. ChemCatChem, 2019, 11(19): 4744-4754.
42	AL-FATESH A S, DE KASIM S O, IBRAHIM A A, et al. Catalytic methane decomposition over ZrO₂ supported iron catalysts: effect of WO₃ and La₂O₃ addition on catalytic activity and stability[J]. Renewable Energy, 2020, 155: 969-978.
43	DECK C P, VECCHIO K. Prediction of carbon nanotube growth success by the analysis of carbon-catalyst binary phase diagrams[J]. Carbon, 2006, 44(2): 267-275.
44	FAKEEHA A H, AL-FATESH A S, CHOWDHURY B, et al. Bi-metallic catalysts of mesoporous Al₂O₃ supported on Fe, Ni and Mn for methane decomposition: effect of activation temperature[J]. Chinese Journal of Chemical Engineering, 2018, 26(9): 1904-1911.
45	PINILLA J L, UTRILLA R, KARN R K, et al. High temperature iron-based catalysts for hydrogen and nanostructured carbon production by methane decomposition[J]. International Journal of Hydrogen Energy, 2011, 36(13): 7832-7843.
46	WROBEL R, HELMINIAK 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.
47	PUDUKUDY M, YAAKOB Z, KADIER A, et al. One-pot sol-gel synthesis of Ni/TiO₂ catalysts for methane decomposition into CO_x free hydrogen and multiwalled carbon nanotubes[J]. International Journal of Hydrogen Energy, 2017, 42(26): 16495-16513.
48	CHAI S P, LEE K Y, ICHIKAWA S, et al. Synthesis of carbon nanotubes by methane decomposition over Co-Mo/Al₂O₃: process study and optimization using response surface methodology[J]. Applied Catalysis A: General, 2011, 396(1/2): 52-58.
49	AWADALLAH A E, ABOUL-ENEIN A A, ABOUL-GHEIT A K. Effect of progressive Co loading on commercial Co-Mo/Al₂O₃ catalyst for natural gas decomposition to CO_x-free hydrogen production and carbon nanotubes[J]. Energy Conversion and Management, 2014, 77: 143-151.
50	AWADALLAH A E, ABOUL-ENEIN A A, AZAB M A, et al. Influence of Mo or Cu doping in Fe/MgO catalyst for synthesis of single-walled carbon nanotubes by catalytic chemical vapor deposition of methane[J]. Fullerenes, Nanotubes and Carbon Nanostructures, 2017, 25(4): 256-264.
51	DENG J L, LIU J X, SONG W Y, et al. Selective catalytic reduction of NO with NH₃ over Mo-Fe/beta catalysts: the effect of Mo loading amounts[J]. RSC Advances, 2017, 7(12): 7130-7139.
52	NOVOTNÝ P, YUSUF S, LI F, et al. Oxidative dehydrogenation of ethane using MoO₃/Fe₂O₃ catalysts in a cyclic redox mode[J]. Catalysis Today, 2018, 317: 50-55.
53	BAEK M, GUAN-WOO K, PARK T, et al. NiMoFe and NiMoFeP as complementary electrocatalysts for efficient overall water splitting and their application in PV-electrolysis with STH 12.3[J]. Small, 2019, 15(49): e1905501.
54	BOWKER M, BROOKES C, CARLEY A F, et al. Evolution of active catalysts for the selective oxidative dehydrogenation of methanol on Fe₂O₃ surface doped with Mo oxide[J]. Physical Chemistry Chemical Physics, 2013, 15(29): 12056.
55	LI Y K, ZHANG G, LU W T, et al. Amorphous Ni-Fe-Mo suboxides coupled with Ni network as porous nanoplate array on nickel foam: a highly efficient and durable bifunctional electrode for overall water splitting[J]. Advanced Science, 2020, 7(7): 1902034.
56	LU Y, ZHU Z P, SU D S, et al. Formation of bamboo-shape carbon nanotubes by controlled rapid decomposition of picric acid[J]. Carbon, 2004, 42(15): 3199-3207.
57	KUDUS M H A, AKIL H M, MOHAMAD H, et al. Effect of catalyst calcination temperature on the synthesis of MWCNT-alumina hybrid compound using methane decomposition method[J]. Journal of Alloys and Compounds, 2011, 509(6): 2784-2788.

催化剂	比表面积/m²·g^-1	孔容/cm³·g^-1	孔径/nm
Fe	2.7	0.02	40.3
Fe₁₅Mo₁	11.1	0.07	40.5
Fe₁₅Cu₁	0.4	—	—
Fe₁₅W₁	16.4	0.09	29.1

催化剂	比表面积/m²·g^-1	孔容/cm³·g^-1	孔径/nm
Fe	2.7	0.02	40.3
Fe₁₅Mo₁	11.1	0.07	40.5
Fe₁₅Cu₁	0.4	—	—
Fe₁₅W₁	16.4	0.09	29.1

催化剂	比表面积/m²·g^-1	孔容/cm³·g^-1	孔径/nm
Fe	2.7	0.02	40.3
Fe₁₅Mo₁	11.1	0.07	40.5
Fe₅Mo₁	8.8	0.06	33.5
Fe₃Mo₁	7.8	0.06	38.7
Fe₁Mo₁	0.7	0.01	38.8
Fe₁Mo_1.5	0.07	—	—

催化剂	比表面积/m²·g^-1	孔容/cm³·g^-1	孔径/nm
Fe	2.7	0.02	40.3
Fe₁₅Mo₁	11.1	0.07	40.5
Fe₅Mo₁	8.8	0.06	33.5
Fe₃Mo₁	7.8	0.06	38.7
Fe₁Mo₁	0.7	0.01	38.8
Fe₁Mo_1.5	0.07	—	—

[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]	LAI Shini, JIANG Lixia, LI Jun, HUANG Hongyu, KOBAYASHI Noriyuki. Research progress of ammonia blended fossil fuel [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4603-4615.
[8]	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.
[9]	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.
[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]	BAI Zhihua, ZHANG Jun. Oxidative removal of NO in DTPMPA/Fenton system [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4967-4973.
[15]	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.