甲烷催化裂解制氢和碳纳米材料研究进展

doi:10.16085/j.issn.1000-6613.2018-0183

摘要/Abstract

摘要： 甲烷通过催化裂解反应可生成不含碳氧化合物（CO_x）的高纯氢和碳纳米材料（如碳纤维或碳纳米管等），对我国能源结构的调整及新材料的应用具有重要意义。与其他制氢工艺相比，甲烷催化裂解制氢工艺具有反应过程简单、产物清洁无污染、反应成本低等优点，因此该工艺具有重要的工业应用前景。本文重点阐述了催化剂（活性组分、催化剂载体、制备方法等）以及反应条件（催化剂还原条件、空速、反应温度等）对甲烷转化率、氢气产率和碳纳米材料（形貌和产量）的影响并对甲烷催化裂解反应机理、催化剂的失活与再生进行了概述。甲烷催化裂解反应目前仍处于实验室研究阶段，高效催化剂的研制以及流化床反应器的优化是该反应实现工业化应用的必要前提。

关键词: 甲烷, 催化裂解, 制氢, 催化剂, 反应机理, 碳纳米材料, 失活, 再生

Abstract: Methane catalytic decomposition (MCD) can be utilized to produce high-purity hydrogen without carbon oxygen compounds (CO_x) and carbon nanomaterials (such as carbon nanofibers or carbon nanotubes). The catalytic decomposition of methane is of great significance to the adjustment of energy structure and application of advanced materials in China. Compared with other hydrogen production process, MCD has advantages such as simple reaction conditions, products without pollution and low cost, etc. Hence, MCD has a considerable application prospect in industry. In this review, the effects of catalysts (active components, carriers, preparation methods, etc) and reaction parameters (reduction of catalyst, space velocity, reaction temperature, etc) on methane conversion, hydrogen yield and carbon nanomaterials (morphology and yield) are discussed in detail. Meanwhile, the mechanism of MCD and the deactivation and regeneration of catalyst were also summarized. At present, the MCD is still at the stage of lab research. The high-performance catalyst and optimize of fluidized bed reactor is the essential prerequisite for the industrial application of MCD.

Key words: methane, catalytic decomposition, hydrogen production, catalyst, reaction mechanism, carbon nanomaterials, deactivation, regeneration

中图分类号:

O643.32

王迪, 胡燕, 高卫民, 崔彦斌. 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, CUI Yanbin. Progress of methane catalytic decomposition for hydrogen and carbon nanomaterials production[J]. Chemical Industry and Engineering Progress, 2018, 37(S1): 80-93.

参考文献

[1] CHEN W H, CHIU I H. Modeling of transient hydrogen permeation process across a palladium membrane[J]. Applied Energy, 2010, 87(3):1023-1032.
[2] ASHIK U P M, DAUD W M A W, ABBAS H F. Production of greenhouse gas free hydrogen by thermocatalytic decomposition of methane-A review[J]. Renewable Sustainable Energy Reviews, 2015, 44:221-256.
[3] ACAR C, DINCER I. Comparative assessment of hydrogen production methods from renewable and non-renewable sources[J]. International Journal of Hydrogen Energy, 2014, 39(1):1-12.
[4] 乔春珍. 含碳能源直接制氢中CO₂吸收剂的研究[D]. 北京:中国科学院研究生院(工程热物理研究所), 2006.
[5] ROSTRUPNIELSEN J R. Catalysis and large-scale conversion of natural gas[J]. Catalysis Today, 1994, 21(2/3):257-267.
[6] NAVARRO R M, PENA M A, FIERRO J L G. Hydrogen production reactions from carbon feedstocks:fossils fuels and biomass[J]. Chemical Reviews, 2007, 107(10):3952-3991.
[7] CHEN W H, CHENG Y C, HUNG C I. Transient reaction and exergy analysis of catalytic partial oxidation of methane in a Swiss-roll reactor for hydrogen production[J]. International Journal of Hydrogen Energy, 2012, 37(8):6608-6619.
[8] LI C, SIVARAM P. Low temperature synthesis of metal doped perovskites catalyst for hydrogen production by autothermal reforming of methane[J]. International Journal of Hydrogen Energy, 2016, 41(33):14605-14614.
[9] MONDAL K C, CHANDRAN S R. Evaluation of the economic impact of hydrogen production by methane decomposition with steam reforming of methane process[J]. International Journal of Hydrogen Energy, 2014, 39(18):9670-9674.
[10] 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.
[11] PING D, WANG C, DONG X, et al. Co-production of hydrogen and carbon nanotubes on nickel foam via methane catalytic decomposition[J]. Applied Surface Science, 2016, 369:299-307.
[12] ERMAKOVA M A, ERMAKOV D Y, KUVSHINOV G G, et al. New nickel catalysts for the formation of filamentous carbon in the reaction of methane decomposition[J]. Journal of Catalysis, 1999, 187(1):77-84.
[13] 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.
[14] AVDEEVA L B, KOCHUBEY D I, SHAIKHUTDINOV S K. Cobalt catalysts of methane decomposition:accumulation of the filamentous carbon[J]. Applied Catalysis A:General, 1999, 177(1):43.
[15] RESHETENKO T V, AVDEEVA L B, USHAKOV V A, et al. Coprecipitated iron-containing catalysts (Fe-Al₂O₃, Fe-Co-Al₂O₃, Fe-Ni-Al₂O₃) for methane decomposition at moderate temperatures:Part Ⅱ. Evolution of the catalysts in reaction[J]. Applied Catalysis A:General, 2004, 270(1/2):87-99.
[16] MANEERUNG T K, HIDAJAT K, KAWI S. LaNiO₃ perovskite catalyst precursor for rapid decomposition of methane:influence of temperature and presence of H₂ in feed stream[J]. Catalysis Today, 2011, 171(1):24-35.
[17] PIAO L Y, LI Y D, CHEN R L, et al. Methane decomposition to carbon nanotubes and hydrogen on an alumina supported nickel aerogel catalyst[J]. Catalysis Today, 2002, 74(1/2):145-154.
[18] ECHEGOYEN Y, SUElLVES I, LAZARO M J, et al. Thermocatalytic decomposition of methane over Ni-Mg and Ni-Cu-Mg catalysts:effect of catalyst preparation method[J]. Applied Catalysis A:General, 2007, 333(2):229-237.
[19] KOERTS T, DEELEN M J A G, VANSANTEN R A. Hydrocarbon formation from methane by a low-temperature 2-step reaction sequence[J]. Journal of Catalysis, 1992, 138(1):101-114.
[20] BAYAT N, REZAEI M, MESHKANI F. Hydrogen and carbon nanofibers synthesis by methane decomposition over Ni-Pd/Al₂O₃ catalyst[J]. International Journal of Hydrogen Energy, 2016, 41(12):5494-5503.
[21] 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.
[22] AWADALLAH A E, ABOUL-ENEIN A A, ABOUL-GHEIT A K. Various nickel doping in commercial Ni-Mo/Al₂O₃ as catalysts for natural gas decomposition to CO_x-free hydrogen production[J]. Renewable Energy, 2013, 57:671-678.
[23] LI J M, DONG L, XIONG L P, et al. High-loaded Ni-Cu-SiO₂ catalysts for methane decomposition to prepare hydrogen and carbon filaments[J]. International Journal of Hydrogen Energy, 2016, 41(28):12038-12048.
[24] SARASWAT S K, PANT K K. Ni-Cu-Zn/MCM-22 catalysts for simultaneous production of hydrogen and multiwall carbon nanotubes via thermo-catalytic decomposition of methane[J]. International Journal of Hydrogen Energy, 2011, 36(21):13352-13360.
[25] BAYAT N, MESHKANI F, REZAEI M. Thermocatalytic decomposition of methane to CO_x-free hydrogen and carbon over Ni-Fe-Cu/Al₂O₃ catalysts[J]. International Journal of Hydrogen Energy, 2016, 41(30):13039-13049.
[26] CHEN J, HE M, WANG G W, et al. Production of hydrogen from methane decomposition using nanosized carbon black as catalyst in a fluidized-bed reactor[J]. International Journal of Hydrogen Energy, 2009, 34(24):9730-9736.
[27] SZYMANSKA M, MALAIKA A, RECHNIA P, et al. Metal/activated carbon systems as catalysts of methane decomposition reaction[J]. Catalysis Today, 2015, 249:94-102.
[28] FAKEEHA A H, KHAN W U, AL-FATESH A S, et al. Production of hydrogen from methane over lanthanum supported bimetallic catalysts[J]. International Journal of Hydrogen Energy, 2016, 41(19):8193-8198.
[29] UDDIN M N, DAUD, W M A W, ABBAS H F. Co-production of hydrogen and carbon nanofibers from methane decomposition over zeolite Y supported Ni catalysts[J]. Energy Conversion and management, 2015, 90:218-229.
[30] AWADALLAH A E, Aboul-Enein A A. Catalytic decomposition of methane to CO_x-free hydrogen and carbon nanotubes over Co-W/MgO catalysts[J]. Egyptian Journal of petroleum, 2015, 24:299-306.
[31] AWADALLAH A E, EL-DESOUKI D S, ABOUL-ENEIN A A, et al. Catalytic thermal decomposition of methane to CO_x-free hydrogen and carbon nanotubes over MgO supported bimetallic group VⅢ catalysts[J]. Applied Surface Science, 2014, 296:100-107.
[32] LI J, KEVIN J S. Methane decomposition and catalyst regeneration in a cyclic mode over supported Co and Ni catalysts[J]. Applied Catalysis A:General, 2008, 349(1/2):116.
[33] 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.
[34] TAKENAKA S, KOBAVASHI S, OGIHARA H, et al. Ni/SiO₂ catalyst effective for methane decomposition into hydrogen and carbon nanofibers[J]. Journal of Catalysis, 2003, 217(1):79-81.
[35] LI J Z, LU G X, LI K, et al. Active Nb₂O₅-supported nickel and nickel-copper catalysts for methane decomposition to hydrogen and filamentous carbon[J]. Journal of Molecular Catalysis A:Chemical, 2004, 221(1/2):105-112.
[36] HITOSHI O, SAKAE T, ICHIRO Y, et al. Formation of highly concentrated hydrogen through methane decomposition over Pd-based alloy catalysts[J]. Journal of Catalysis, 2006, 238(2):353-360.
[37] TAKENAKA S, SHIGETA Y, TANABE E, et al. Methane decomposition into hydrogen and carbon nanofibers over supported Pd-Ni catalysts[J]. Journal of Catalysis, 2003, 220(2):468-477.
[38] OTSUKA K, SEINO T, KOBAYASHI S, et al. Production of hydrogen through decomposition of methane with Ni-supported catalysts[J]. Chemistry Letters, 1999(11):1179-1180.
[39] AWADALLAH A E, EL-DESOUKI D S, ABOUL-GHEITET N A K, et al. Effect of crystalline structure and pore geometry of silica based supported materials on the catalytic behavior of metallic nickel particles during methane decomposition to CO_x-free hydrogen and carbon nanomaterials[J]. International Journal of Hydrogen Energy, 2016, 41(38):16890-16902.
[40] 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.
[41] PUDUKUDY M, YAAKOB Z, TAKRIFF M S. Methane decomposition into CO_x free hydrogen and multiwalled carbon nanotubes over ceria, zirconia and lanthana supported nickel catalysts prepared via a facile solid state citrate fusion method[J]. Energy Conversion and Management, 2016, 126:302-315.
[42] MANEERUNG T, HIDAJAT K, KAWI S. Co-production of hydrogen and carbon nanofibers from catalytic decomposition of methane over LaNi_(1-x)M_xO_3-α perovskite (where M=Co, Fe and X=0, 0. 2, 0. 5, 0. 8, 1)[J]. International Journal of Hydrogen Energy, 2015, 40(39):13399-13411.
[43] LI Y, ZHANG B C, XIE X W, et al. Novel Ni catalysts for methane decomposition to hydrogen and carbon nanofibers[J]. Journal of Catalysis, 2006, 238(2):412-424.
[44] 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, 41:18509-18521.
[45] LUA A C, WANG H Y. Hydrogen production by catalytic decomposition of methane over Ni-Cu-Co alloy particles[J]. Applied Catalysis B:Environmental, 2014, 156:84-93.
[46] SUELVES I, LAZARO M J, MOLINER R, et al. Characterization of NiAl and NiCuAl catalysts prepared by different methods for hydrogen production by thermo catalytic decomposition of methane[J]. Catalysis Today, 2006, 116(3):271-280.
[47] SUELVES I, LAZARO M J, ECHEGOYEN Y, et al. Decomposition of methane over Ni-SiO₂ and Ni-Cu-SiO₂ catalysts:effect of catalyst preparation method[J]. Applied Catalysis A:General, 2007, 329:22-29.
[48] 曾群. 催化剂制备及反应条件对制备纳米碳管的影响[D]. 天津:天津大学, 2007.
[49] 梁威, 陈晨, 李腾, 等. 还原条件对甲烷催化裂解催化剂活性影响探究[J]. 天然气化工(C1化学与化工), 2016, 41(1):15-20, 74.
[50] SUELVES I, LAZARO M J, MOLINER R, et al. Hydrogen production by thermo catalytic decomposition of methane on Ni-based catalysts:influence of operating conditions on catalyst deactivation and carbon characteristics[J]. International Journal of Hydrogen Energy, 2005, 30(15):1555-1567.
[51] 潘智勇, 沈师孔. Ni/SiO₂催化剂上甲烷催化裂解制氢[J]. 燃料化学学报, 2003, 36(5):466-470.
[52] 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.
[53] OTSUKA K, KOBAYASHI S, TAKENAKA S. Hydrogen-deuterium exchange studies on the decomposition of methane over Ni/SiO₂[J]. Journal of Catalysis, 2001, 200(1):4-9.
[54] BAKER R T K, BARBER M A, HARRIS P S, et al. Nucleation and growth of carbon deposits from the nickel catalyzed decomposition of acetylene[J]. Journal of Catalysis, 1972, 26(1):51-62.
[55] NIELSEN J R, TRIMM D L. Mechanisms of carbon formation on nickel-containing catalysts[J]. Journal of Catalysis, 1977, 48(1/2/3):155-165.
[56] MARINAA E, DMITRY Y E, ANDREY 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 yeild of carbon and morphology of carbon filaments[J]. Journal of Catalysis, 2001, 201(2):183-197.
[57] 曹磊. 纳米镍基催化剂用于甲烷裂解反应的研究[D]. 天津:天津大学, 2003.
[58] ZAVARUKHIN S G, KUVSHINOV G G. The kinetic model of formation of nanofibrous carbon from CH₄-H₂ mixture over a high-loaded nickel catalyst with consideration for the catalyst deactivation[J]. Applied Catalysis A:General, 2004, 272(1/2):219-227.
[59] 张志, 唐涛, 陆光达. 甲烷催化裂解制氢技术研究进展[J]. 化学研究与应用, 2007, 19(1):1-9.
[60] AIELLO R, FISCUS J E, ZUR LOYE H C, 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.
[61] TAKENAKA S, KATO E, TOMIKUBO Y, et al. Structural change of Ni species during the methane decomposition and the subsequent gasification of deposited carbon with CO₂ over supported Ni catalysts[J]. Journal of Catalysis, 2003, 219(1):176-185.
[62] 李建中, 吕功煊, 李克. 甲烷在Ni/SiO₂催化剂上裂解制碳纳米管和氢气[J]. 石油与天然气化工, 2004, 33(4):222-225.
[63] 金鑫. 甲烷催化裂解制备氢气和碳纳米管[J]. 应用化工, 2011, 40(8):1390-1392.
[64] 张志, 唐涛, 陆光达, 等. 催化裂解甲烷制备氢气和碳纳米纤维[J]. 应用化学, 2008, 25(2):245-250.