溶液燃烧法制备Ni-Al2O3催化剂用于CO2-CH4重整研究

doi:10.15541/jim20150530

无机材料学报 ›› 2016, Vol. 31 ›› Issue (5): 485-491.DOI: 10.15541/jim20150530

溶液燃烧法制备Ni-Al₂O₃催化剂用于CO₂-CH₄重整研究

莫文龙, 马凤云, 刘月娥, 刘景梅, 钟梅, 艾沙·努拉洪

(煤炭清洁转化与化工过程新疆维吾尔自治区重点实验室, 新疆大学化学化工学院, 乌鲁木齐830046)

收稿日期:2016-10-29 修回日期:2015-12-20 出版日期:2016-05-20 网络出版日期:2016-04-25
作者简介:莫文龙(1987–), 男, 博士研究生. E-mail: 657232193@qq.com
基金资助:
国家高技术研究发展计划(863 计划)(2015AA050502).新疆大学博士研究生创新项目(XJUBSCX-2013008)

Preparation of Ni-Al₂O₃Catalysts by Solution Combustion Method for CO₂ Reforming of CH₄

MO Wen-Long, MA Feng-Yun, LIU Yue-E, LIU Jing-Mei, ZHONG Mei, Aisha·Nulahong

(Key Laboratory of Coal Clean Conversion & Chemical Engineering Process (Xinjiang Uyghur Autonomous Region), College of Chemistry and Chemical Engineering, Xinjiang University, Urumqi 830046, China)

Received:2016-10-29 Revised:2015-12-20 Published:2016-05-20 Online:2016-04-25
About author:MO Wen-Long. E-mail: 657232193@qq.com

摘要/Abstract

摘要：

采用溶液燃烧法制备了Ni含量为2wt%、4wt%、6wt%、8wt%和10wt%系列催化剂, 并对反应前后催化剂进行N₂吸附-脱附、XRD、H₂-TPR、TPH、Raman、TEM和TG-DTG等表征。与等体积浸渍法(以溶液燃烧法制备的Al₂O₃为载体)制备的催化剂相比, 溶液燃烧法制备的催化剂具有较大的比表面积, 孔径分布可分为2~4.5 nm和4.5~10 nm两段, 属典型的多级孔结构; NiO高度分散在载体上, 与载体具有较强的相互作用, 这种相互作用有利于提高催化剂的稳定性。催化剂210 h稳定性试验表明, 溶液燃烧法制备的Ni含量为8wt%试样的CH₄转化率维持在90%左右, 失活速率仅为0.035%/h, 优于浸渍法制备的相同Ni含量催化剂。

关键词: CO2-CH4重整, Ni-Al2O3催化剂, 合成气, 溶液燃烧法

Abstract:

Ni-Al₂O₃ catalysts with Ni loading of 2wt%, 4wt%, 6wt%, 8wt%, and 10wt% were prepared by solution combustion method for carbon dioxide reforming of methane to produce syngas, and characterized by N₂ adsorption-desorption method, XRD, H₂-TPR, TPH, Raman, TEM, and TG-DTG techniques. Results showed that all the catalysts preserved large specific surface areas and hierarchical pore size distributions (2-4.5 nm as one part and 4.5-10 nm as another part) as compared to 8IMNi-Al catalyst prepared by impregnation method (Al₂O₃ as support prepared by solution combustion method). NiO was highly dispersed in the Ni-Al₂O₃ catalysts, which combined with support with strong metal-support interaction (SMSI), improving the stability performance. The 210 h stability test of 8Ni-Al catalyst showed that conversion rate of CH₄ was around 90% with the deactivation rate of only 0.035%/h, lower than that of 8IMNi-Al catalyst within the 182 h endurance test. TG-DTG result demonstrated that carbon deposition rate of 8Ni-Al catalyst was only 0.34 mg/(h·g_cat), which was lower than that of 8IMNi-Al catalyst (0.80 mg/(h·g_cat)). Therefore, the Ni-Al₂O₃ catalyst prepared by solution combustion method presented well stability.

Key words: CO2 reforming of CH4, Ni-Al2O3 catalyst, syngas, solution combustion method

中图分类号:

O643

莫文龙, 马凤云, 刘月娥, 刘景梅, 钟梅, 艾沙·努拉洪. 溶液燃烧法制备Ni-Al₂O₃催化剂用于CO₂-CH₄重整研究[J]. 无机材料学报, 2016, 31(5): 485-491.

MO Wen-Long, MA Feng-Yun, LIU Yue-E, LIU Jing-Mei, ZHONG Mei, Aisha·Nulahong. Preparation of Ni-Al₂O₃Catalysts by Solution Combustion Method for CO₂ Reforming of CH₄[J]. Journal of Inorganic Materials, 2016, 31(5): 485-491.

图/表 8

表1 催化剂的比表面积、孔体积和平均孔径

Table 1 Specific surface area, pore volume and average pore diameter of catalysts

Catalysts	S_BET/(m²·g^-1)	V/(m³·g^-1)	D/nm
Al₂O₃	196	0.425	4.7
8IMNi-Al	147	0.215	4.3
2Ni-Al	183	0.283	4.0
4Ni-Al	179	0.258	4.3
6Ni-Al	173	0.237	4.3
8Ni-Al	165	0.227	4.3
10Ni-Al	155	0.203	4.4

图1 催化剂的XRD图谱

Fig. 1 XRD patterns of the catalysts

图2 催化剂的H2-TPR谱图

Fig. 2 H2-TPR profiles of the catalysts

图3 不同反应温度下CH4(a)和CO2(b)转化率及H2/CO(c)比随Ni含量的变化

Fig. 3 CH4 (a) and CO2 (b) conversions and H2/CO ratio (c) versus Ni content (GHSV=14400 mL/(gcat•h))

图4 不同反应空速下CH4 (a)和CO2 (b) 及H2/CO(c)比转化率随Ni含量的变化

Fig. 4 CH4 (a) and CO2 (b) conversions and H2/CO (c) versus Ni content at various GHSV (T=800 ℃)

图5 8IMNi-Al和8Ni-Al试样的稳定性测试

Fig. 5 Long term stability test for the catalysts 8IMNi-Al and 8Ni-Al

图6 寿命试验后试样的TG分析(a), XRD表征(b), Raman表征(c)和TPH表征(d)

Fig. 6 TG curves (a), XRD patterns (b), Raman spectra (c), and TPHspectra (d) of the endurance-tested catalysts

图7 8IMNi-Al (a, b)和8Ni-Al (c, d)催化剂实验前后TEM照片

Fig. 7 TEM images of the catalysts 8IMNi-Al before (a) and after (b) reaction, and 8Ni-Al before (c) and after reaction (d)

参考文献 17

[1]	ROH HYUN-SEOG, JUN KI-WON.Carbon dioxide reforming of methane over Ni catalyst supported on Al2O3 modified with La2O3, MgO and CaO.Catalyst Surveys from Asia, 2008, 12(4): 239-252.
[2]	YANG Y Y, DING S, JIN Y, et al.Milliseconds steam reforming of methane using Rh/MgO/γ-A12O3 catalyst.Journal of Chemical Industry and Engineering (China), 2009, 60(8): 1981-1987.
[3]	MO W L, MA F Y, LIU H X, et al.Influence of γ-Al2O3 prepared by template method on performance of Ni-based catalysts for CH4/CO2 reforming.Chemical Industry and Engineering Progress, 2014, 33(1): 187-193.
[4]	ZHANG J G, WANG H, DALAI A K.Development of stable bimetallic catalysts for carbon dioxide reforming of methane.Journal of Catalysis, 2007, 249(2): 300-310.
[5]	MESHKANI F, REZAEI M.Nanocrystalline MgO supported nickel-based bimetallic catalysts for carbon dioxide reforming of methane.International Journal of Hydrogen Energy, 2010, 35(19): 10295-10301.
[6]	MO W L, MA F Y, LIU H X, et al.Influence of precipitants on performance of NiO/γ-Al2O3 catalysts for CH4/CO2 reforming.Natural Gas Chemical Industry, 2014, 39(3): 42-47.
[7]	LI M F, MO W L, MA F Y, et al.Colloidmill circulating impregnation method for preparation of NiO/γ-Al2O3 catalyst for CO2-CH4 reforming.Natural Gas Chemical Industry, 2014, 39(3): 1-4.
[8]	SHARMA S, HU Z P, ZHANG P, et al.CO2 methanation on Ru-doped ceria.Journal of Catalysis, 2011, 278(2): 297-309.
[9]	HOU Z Y, CHEN P, FANG H L, et al.Production of synthesis gas via methane reforming with CO2 on noble metals and small amount of noble-(Rh) promoted Ni catalysts. International Journal of Hydrogen Energy, 2006, 31(5): 555-561.
[10]	ZHENG Y F, ZHONG S B, LV D Y, et al.Effect of calcination temperature of Cu-Mn/-Al2O3 catalysts on performance for catalytic oxidation of toluene.Journal of Inorganic Materials, 2015, 30(7): 694-698.
[11]	OZKARA-AYDINOGLU S, AKSOYLU A E.Carbon dioxide reforming of methane over Co-X/ZrO2 catalysts (X ¼ La, Ce, Mn, Mg, K).Catalysis communicatioins, 2010, 11(15): 1165-1170.
[12]	ZHANG S B, WANG J K, LIU H T, et al.One-pot synthesis of Ni-nanoparticle-embedded mesoporous titania/silica catalyst and its application for CO2 reforming of methane.Catalysis communicatioins, 2008, 9(6): 995-1000.
[13]	HU X, LU G X.Comparative study of alumina-supported transition metal catalysts for hydrogen generation by steam reforming of acetic acid.Applied Catalysis B: Environmental, 2010, 99(1/2): 289-297.
[14]	BARROSO-QUIROGA M M, CASTRO-LUNA A E. Catalytic activity and effect of modifiers on Ni-based catalysts for the dry reforming of methane.International Journal of Hydrogen Energy, 2010, 35(11): 6052-6056.
[15]	DAZA C E, MORENO S, MOLINA R.Co-precipitated Ni-Mg-Al catalysts containing Ce for CO2 reforming of methane.International Journal of Hydrogen Energy, 2011, 36(6): 3886-3894.
[16]	GUO J J, LOU H, ZHENG X M.The deposition of coke from methane on a Ni/MgAl2O4 catalyst.Carbon, 2007, 45(6): 1314-1321.
[17]	XU J K, ZHOU W, WANG J H, et al.Characterization and analysis of carbon deposited during the dry reforming of methane over Ni/La2O3/Al2O3catalysts. Chinese of Journal Catalysis, 2009, 30(11): 1076-1084.

溶液燃烧法制备Ni-Al₂O₃催化剂用于CO₂-CH₄重整研究

Preparation of Ni-Al₂O₃Catalysts by Solution Combustion Method for CO₂ Reforming of CH₄

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