铜钼组分对γ-Al2O3负载镍催化剂脂肪酸甲酯加氢脱氧性能的影响  

Influence of Cu and Mo components ofγ-Al2O3 supported nickel catalysts on hydrodeoxygenation of fatty acid methyl esters to fuel-like hydrocarbons

作　　者：JING Zhong-yu ZHANG Tao-qi SHANG Jiang-wei ZHAI Ming-lu YANG Hao QIAO Cong-zhen MA Xin-qi 景仲雨 张韬奇 商江伟 翟明路 杨浩[1] 乔聪震[1] 马新起[1] JING Zhong-yu;ZHANG Tao-qi;SHANG Jiang-wei;ZHAI Ming-lu;YANG Hao;QIAO Cong-zhen;MA Xin-qi(College of Chemistry and Chemical Engineering,Henan Province Engineering Research Center of Resource&Energy Recovery from Waste,Henan University,Kaifeng475004,China;Department of Automotive,City University of Zhengzhou,Zhengzhou　450000,China)

机构地区：[1]河南大学化学化工学院,废弃物资源能源化河南省工程技术研究中心,河南开封475004 [2]郑州城市职业学院,汽车工程系,河南郑州450000

出　　处：《燃料化学学报》2018年第4期427-440,共14页Journal of Fuel Chemistry and Technology

基　　金：The project was supported by National Science and Technology Supporting Program(2013BAB11B02)and Science and Technology Development Project of Henan Province(152102210258).

摘　　要：制备一系列包含或不包含铜、钼组分的Ni/γ-Al2O3催化剂，并对其进行表征和性能测试。考察了铜、钼负载量，浸渍顺序（包括连续浸渍和共浸渍），反应条件对脂肪酸甲酯加氢脱氧反应性能的影响。根据TG数据，使用过的20Ni-6Cu/γ-Al2O3催化剂其热失重小于20Ni/γ-Al2O3催化剂，这表明,铜的引入能够有效抑制反应过程中催化剂表面的积炭行为。对于20Ni-6Cu/γ-Al2O3和20Ni-6Cu-nMo/γ-Al2O3(n=2、5、8和12)催化剂，NH3-TPD分析结果显示，钼物相的引入对载体γ-Al2O3的酸性位有着显著影响，当钼负载量达到5%时，可以观察到一个新的酸位对应于中强酸位。铜和钼修饰过的催化剂其催化性能要高于Ni/γ-Al2O3催化剂。从XPS的分析可以看出，催化剂中的铜主要以正二价形式存在，钼主要以正四价和正六价形式存在，而且不同的浸渍顺序会影响催化剂表面活性组分的实际含量。此外，脂肪酸甲酯的转化率和烷烃产品的收率也和所制备出来的催化剂的浸渍顺序有关。在所有的催化剂中，使用连续浸渍（先浸渍镍铜组分、浸渍钼组分）所制备的三金属20Ni-6Cu-5Mo/γ-Al2O3催化剂展现了优异的催化性能。在适宜的反应条件下（350℃,2.5MPa,WSHV=2.0h-1,H2/oilratio=1250mL/mL），脂肪酸甲酯的转化率和烷烃产品的收率分别达到98.4%和94.2%。In this work,series of Ni/γ-Al 2O 3catalysts with or without Cu and Mo components were prepared,characterized and tested for the hydrodeoxygenation of fatty acid methyl esters(FAME)to hydrocarbons.The effects of Cu and Mo loading,impregnation sequence with sequential impregnation and co-impregnation involved and reaction conditions on catalytic performance were investigated.According to the TG data,the spent 20Ni-6Cu/γ-Al 2O 3catalyst gives less weight loss than the spent 20Ni/γ-Al 2O 3 catalyst,which indicates that the addition of copper inhibits the carbon deposits behavior on catalyst surface during reaction.For 20Ni-6Cu/γ-Al 2O 3and 20Ni-6Cu-n Mo/γ-Al 2O 3(n=2,5,8 and 12)catalysts,NH 3-TPD analysis shows that the addition of molybdenum phase has significant impact on the acid sites ofγ-Al 2O 3.When the loading of molybdenum is 5%,a new acid site is observed corresponding to the medium strength acid site.The Cu and Mo modified catalysts demonstrate better catalytic performance than Ni/γ-Al 2O 3catalysts.Based on XPS results,Cu in the catalysts exists in the Cu 2+and Mo in the catalysts has two states:Mo 4+and Mo 6+,and different impregnation sequences may influence the actual element composition of active phase on the surface of catalysts.In addition,the conversion of FAME and yield of alkane are related to the catalysts prepared with different impregnation sequence.Among all the catalysts,the trimetallic 20Ni-6Cu-5Mo/γ-Al 2O 3prepared by sequential impregnation(the former Ni and Cu impregnation,the latter Mo impregnation)exhibits optimal catalytic performance.Under appropriate reaction conditions 350℃,2.5 MPa,WSHV=2.0 h-1,H 2/oil ratio=1250 mL/mL,the conversion of FAME and yield of alkane are 98.4%and 94.2%.

关 键 词：加氢脱氧 脂肪酸甲酯 镍基催化剂 Γ-AL2O3 

分 类 号：TQ517.2[化学工程]