La_2O_3含量对La-Ni/ZrO_2-Al_2O_3催化剂甲烷化性能的影响
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摘要
采用浸渍法制备了复合氧化物ZrO_2-Al_2O_3,在此基础上采用共浸渍法制备了La-Ni/ZrO_2-Al_2O_3催化剂,考察了催化剂中La2O3含量对催化剂CO甲烷化活性的影响,并利用BET、XRD和TPR对催化剂的物化性能进行了分析。结果表明当La2O3含量为2%~6%(质量分数,下同)时,其在低温和高温时的催化活性均比Ni/ZrO_2-Al_2O_3有一定的提升。另外比较了催化剂4La-Ni/ZrO_2-Al_2O_3和Ni/ZrO_2-Al_2O_3在500℃下连续反应100 h的活性和积碳,结果显示催化剂4La-Ni/ZrO_2-Al_2O_3具有很好的稳定性和优良的抗积碳性能。
ZrO_2-Al_2O_3 composite oxides were prepared by impregnation method,and La-Ni/ZrO_2-Al_2O_3 catalysts with different La2 O3 contents were prepared by co-impregnation method. The effect of La_2O_3 contents was test for CO methanation and analyzed by BET,XRD and TPR. The results showed that introducing a small amount of La_2O_3( 2% —6%) into Ni/ZrO_2-Al_2O_3 catalyst could increase its methanation activity,especially at low temperature range and high temperature range. Furthermore,the continuous reactions of 100 h under 500 ℃ were performed to investigate the stability performance and carbon deposition of the 4 La-Ni/ZrO_2-Al_2O_3 and Ni/ZrO_2-Al_2O_3. The 4 La-Ni/ZrO_2-Al_2O_3 catalyst displayed superior stability and excellent anti-carbon deposition property than Ni/ZrO_2-Al_2O_3.
ZrO_2-Al_2O_3 composite oxides were prepared by impregnation method,and La-Ni/ZrO_2-Al_2O_3 catalysts with different La2 O3 contents were prepared by co-impregnation method. The effect of La_2O_3 contents was test for CO methanation and analyzed by BET,XRD and TPR. The results showed that introducing a small amount of La_2O_3( 2% —6%) into Ni/ZrO_2-Al_2O_3 catalyst could increase its methanation activity,especially at low temperature range and high temperature range. Furthermore,the continuous reactions of 100 h under 500 ℃ were performed to investigate the stability performance and carbon deposition of the 4 La-Ni/ZrO_2-Al_2O_3 and Ni/ZrO_2-Al_2O_3. The 4 La-Ni/ZrO_2-Al_2O_3 catalyst displayed superior stability and excellent anti-carbon deposition property than Ni/ZrO_2-Al_2O_3.
引文
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[19]Bradford M C J,Vannice M A.Catalytic reforming of methane with carbon dioxide over nickel catalysts I.Catalyst characterization and activity[J].Applied Catalysis A:General,1996,142(1):73-96
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[2]Mok Y S,Kang H C,Lee H J,et al.Effect of nonthermal plasma on the methanation of carbon monoxide over nickel catalyst[J].Plasma Chemistry and Plasma Processing,2010,30(4):437-447
[3]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):2 432-2 438
[4]Shalabi M A,Zaidi S A,Ai-Salen M A.Effect of reduction conditions on the activity of Ni/γ-Al2O3catalyst for methanation reaction[J].Chemical Engineering Communications,1997,157(1):23-33
[5]罗来涛,王敏炜,李凤仪,等.La2O3对Ni-Mo/γ-Al2O3催化剂CO和CO2甲烷化的影响[J].中国稀土学报,1999,17(2):120-124Luo Laitao,Wang Minwei,Li Fengyi,et al.Effect of La2O3on Methanation of CO and CO2over Ni-Mo/γ-Al2O3Catalyst[J].Journal Of The Chinese Rare Earth Society,1999,17(2):120-124(in Chinese)
[6]刘新华,苗茵,李晓丽,等.La2O3对Ni/γ-Al2O3甲烷化催化剂的助催化作用[J].物理化学学报,1995,11(8):746-750Liu Xinhua,Miao Yin,Li Xiaoli.Promoting effect of La2O3methanation catalyst[J].ACTA Physico chimica sinica,1995,11(8):746-750(in Chinese)
[7]Yang R,Xing C,Lv C,et al.Promotional effect of La2O3and Ce O2on Ni/γ-Al2O3catalysts for CO2reforming of CH4[J].Applied Catalysis A:General,2010,385(1):92-100
[8]Guo C,Wu Y,Qin H,et al.CO methanation over Zr O2/Al2O3supported Ni catalysts:A comprehensive study[J].Fuel Processing Technology,2014,124:61-69
[9]Wei J,Iglesia E.Isotopic and kinetic assessment of the mechanism of reactions of CH4with CO2or H2O to form synthesis gas and carbon on nickel catalysts[J].Journal of Catalysis,2004,224(2):370-383
[10]Hwang S,Lee J,Hong U G,et al.Hydrogenation of carbon monoxide to methane over mesoporous nickel-Malumina(M=Fe,Ni,Co,Ce,and La)xerogel catalysts[J].Journal of Industrial and Engineering Chemistry,2012,18(1):243-248
[11]Derekaya F B,Ya爧ar G.The CO methanation over Na Yzeolite supported Ni/Co3O4,Ni/Zr O2,Co3O4/Zr O2and Ni/Co3O4/Zr O2catalysts[J].Catalysis Communications,2011,13(1):73-77
[12]Guo J,Lou H,Zhao H,et al.Dry reforming of methane over nickel catalysts supported on magnesium aluminate spinels[J].Applied Catalysis A:General,2004,273(1):75-82
[13]Martnez R,Romero E,Guimon C,et al.CO2reforming of methane over coprecipitated Ni-Al catalysts modified with lanthanum[J].Applied Catalysis A:General,2004,274(1):139-149
[14]Sun H,Ding Y,Duan J,et al.Transesterification of sunflower oil to biodiesel on Zr O2supported La2O3catalyst[J].Bioresource Technology,2010,101(3):953-958
[15]Zhang J,Xin Z,Meng X,et al.Effect of Mo O3on the heat resistant performances of nickel based MCM-41methanation catalysts[J].Fuel,2014,116:25-33
[16]Zhao A,Ying W,Zhang H,et al.Ni-Al2O3catalysts prepared by solution combustion method for syngas methanation[J].Catalysis Communications,2012,17:34-38
[17]Hu D,Gao J,Ping Y,et al.Enhanced investigation of CO methanation over Ni/Al2O3catalysts for synthetic natural gas production[J].Industrial&Engineering Chemistry Research,2012,51(13):4 875-4 886
[18]Zou X,Wang X,Li L,et al.Development of highly effective supported nickel catalysts for pre-reforming of liquefied petroleum gas under low steam to carbon molar ratios[J].International Journal of Hydrogen Energy,2010,35(22):12 191-12 200
[19]Bradford M C J,Vannice M A.Catalytic reforming of methane with carbon dioxide over nickel catalysts I.Catalyst characterization and activity[J].Applied Catalysis A:General,1996,142(1):73-96
[20]Wang S,Lu G.A comprehensive study on carbon dioxide reforming of methane over Ni/γ-Al2O3catalysts[J].Industrial&Engineering Chemistry Research,1999,38(7):2 615-2 625