镍系催化剂的制备、表征及其甲烷化性能的研究
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摘要
采用混合法在球磨机内制备了高温合成气制甲烷的催化剂载体,并添加不同质量二氧化钛和氧化镧助剂对其做了改性,经焙烧成型和负载后进行甲烷化催化反应。表征了成型催化剂的机械强度、BET、氢气程序升温还原(H2-TPR)、TPD、TG、X射线衍射(XRD)等,并在固定床反应器中评价其甲烷化催化反应性能。结果表明,所制备的催化剂在600℃以上,2 MPa条件下可稳定使用,且具有较高的催化活性、抗烧结及抗积炭特性。TiO_2助剂的添加提高了催化剂的机械性能和耐高温性能,而La_2O_3助剂的添加有利于镍在载体表面的分散,增加催化剂的活性,降低了载体的表面酸性,抑制了积炭的产生,因此可以延长催化剂的使用寿命。
The catalyst carrier for methane production from syngas at high temperature was prepared in a ball mill by mixing method.The catalyst carrier was modified by adding additives TiO_2 and La_2O_3 with different quality.After calcination and loading,methanation reaction was carried out.The mechanical strength and BET of the catalyst was tested,and the catalyst was also characterized by hydrogen temperature-programmed reduction(H_2-TPR),TPD,TG and XRD etc.,and its methanation catalytic performance was evaluated in a fixed-bed reactor.The results showed that the prepared catalyst could be used stably under the condition of above 600 ℃ and 2 MPa,and had higher catalytic activity,anti-sintering and anti-carbon properties.The addition of TiO_2 could improve the mechanical properties and high temperature resistance of the catalyst,while the addition of La_2O_3 helped to disperse nickel on the surface of the support,increase the activity of the catalyst,reduce the surface acidity of the support,and inhibit the formation of carbon.Thus,the service life of the catalyst could be prolonged.
The catalyst carrier for methane production from syngas at high temperature was prepared in a ball mill by mixing method.The catalyst carrier was modified by adding additives TiO_2 and La_2O_3 with different quality.After calcination and loading,methanation reaction was carried out.The mechanical strength and BET of the catalyst was tested,and the catalyst was also characterized by hydrogen temperature-programmed reduction(H_2-TPR),TPD,TG and XRD etc.,and its methanation catalytic performance was evaluated in a fixed-bed reactor.The results showed that the prepared catalyst could be used stably under the condition of above 600 ℃ and 2 MPa,and had higher catalytic activity,anti-sintering and anti-carbon properties.The addition of TiO_2 could improve the mechanical properties and high temperature resistance of the catalyst,while the addition of La_2O_3 helped to disperse nickel on the surface of the support,increase the activity of the catalyst,reduce the surface acidity of the support,and inhibit the formation of carbon.Thus,the service life of the catalyst could be prolonged.
引文
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[2]Vannice M.The catalytic synthesis of hydrocarbons from H2/CO mixtures over the GroupⅧmetalsⅤ.The catalytic behavior of silicasupported metals[J].J.Catal.,1975,37(488):1-8.
[3]Takenaka S,Shimizu T,Otsuka K.Complete removal of carbon monoxide in hydrogen-rich gas stream through methanation over supported metal catalysts[J].International Journal of Hydrogen Energy,2004,29(10):1065-1073.
[4]Gao J J,Jia C M,Li J,et al.Ni/Al2O3,catalysts for CO methanation:Effect of Al2O3,supports calcined at different tempera-tures[J].Journal of Energy Chemistry,2013,22(6):919-927.
[5]Aziz M A A,Jalil A A,Triwahyono S,et al.Highly active Ni-promoted mesostruc-tured silica nanoparticles for CO2metha-nation[J].Applied Catalysis B:Environ-mental,2014,147(7):359-368.
[6]Yu Y,Jin G Q,Wang Y Y,et al.Synthetic natural gas from CO hydrogenation over silicon carbide supported nickel catalysts[J].Fuel Processing Technology,2011,92(12):2293-2298.
[7]葛鑫,李碧静,胡静,等.焙烧温度对二氧化钛催化性能的影响[J].化学工程,2011,39(11):61-65.
[8]王欣,王佩玲,程一兵.TiO2和MgO微量添加剂对Al2O3陶瓷烧结致密化的影响[J].无机材料学报,2001,16(5):979-984.
[9]Bing J S,Hu C,Zhang L L.Enhanced mineralization of pharmaceuticals by surface oxidation over mesoporousγ-Ti-Al2O3suspension with ozone[J].Applied Catalysis B:Environmental,2017,202:118-126.
[10]胡泽善,张量渠.La2O3对天然气蒸汽转化Ni/α-Al2O3催化剂性能的影响[J].催化学报,1992,13(2):83-89.
[11]周吉萍,李春义,张兆斌,等.Ni/Al2O3催化剂上甲烷的分解温度和时间对积碳的影响[J].催化学报,1999,20(4):391-392.
[12]许峥,李玉敏,张继炎,等.甲烷二氧化碳重整制合成气的镍基催化剂性能Ⅱ.碱性助剂的作用[J].催化学报,1997,18(5):364-367.
[13]沈平生,李大东,闵恩泽,等.二氧化钛载体强度和孔结构的关系[J].催化学报,1984,5(4):320-325.