镍基复合催化剂的制备及其在生物质气化气体净化中的应用
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摘要
采用共沉淀法制备了NiO/TiO_2复合催化剂,通过XRD、XPS和SEM等手段对催化剂的物质组成及形貌进行了表征。结果表明,NiO/TiO_2复合催化剂中含有锐钛矿型TiO_2和NiO两相,形貌为纳米花球,微球的大小在1μm左右;NiO以纳米颗粒的形式附着在TiO_2纳米花表面,这种结构有利于NiO/TiO_2复合催化剂比表面积的增大,以及催化活性的增强。以城市垃圾为生物质原料,NiO/TiO_2复合催化剂和ICI46-1型催化剂为催化剂,进行了催化生物质气化实验,比较了两种催化剂的催化活性和使用寿命。结果表明,NiO/TiO_2复合催化剂的催化活性明显优于ICI46-1型催化剂。当NiO/TiO_2复合催化剂的使用寿命为300 min时,城市生活垃圾气化的燃气产率为1.70 m~3/kg(MSW),而燃气中的焦油含量仅0.27 g/m~3,催化剂活性仍保持在98%以上。
In this paper, NiO/TiO_2 catalysts were prepared by coprecipitation, and their composition and morphology were characterized by means of XRD, XPS and SEM. Catalytic biomass gasification experiments were carried out using municipal solid waste as biomass raw material, NiO/titanium dioxide composite material and ICI46-1 catalyst as catalyst. The catalytic activity and service life of NiO/titanium dioxide catalyst and ICI46-1 catalyst were compared. The results show that the NiO/TiO_2 composite material contained two phases of anatase TiO_2 and NiO, whose morphology was nano-sphere, and the size of microsphere was about 1 μm. NiO was attached to the surface of TiO_2 nano-flower in the form of nano-particles. This structure was beneficial to the increase of specific surface area and catalytic activity of NiO/TiO_2 composites. The catalytic gasification test resulted show that the catalytic activity of NiO/TiO_2 was obviously better than that of ICI46-1 catalyst. When the service life was 300 min, the gas yield of municipal solid waste pine wood gasification was 1.70 m~3/kg(MSW), while the tar in gas was only 0.27 g/m~3. When the service life reached 300 min, the activity of the catalyst remained above 98%, prolonging the service life of the catalyst.
In this paper, NiO/TiO_2 catalysts were prepared by coprecipitation, and their composition and morphology were characterized by means of XRD, XPS and SEM. Catalytic biomass gasification experiments were carried out using municipal solid waste as biomass raw material, NiO/titanium dioxide composite material and ICI46-1 catalyst as catalyst. The catalytic activity and service life of NiO/titanium dioxide catalyst and ICI46-1 catalyst were compared. The results show that the NiO/TiO_2 composite material contained two phases of anatase TiO_2 and NiO, whose morphology was nano-sphere, and the size of microsphere was about 1 μm. NiO was attached to the surface of TiO_2 nano-flower in the form of nano-particles. This structure was beneficial to the increase of specific surface area and catalytic activity of NiO/TiO_2 composites. The catalytic gasification test resulted show that the catalytic activity of NiO/TiO_2 was obviously better than that of ICI46-1 catalyst. When the service life was 300 min, the gas yield of municipal solid waste pine wood gasification was 1.70 m~3/kg(MSW), while the tar in gas was only 0.27 g/m~3. When the service life reached 300 min, the activity of the catalyst remained above 98%, prolonging the service life of the catalyst.
引文
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[5] Gross R,Leach M,Bauen A.Progress in renewable energy[J].Environment International,2004,29(1):105-122.
[6] Hamelinck C N,André P C F.Future prospects for production of methanol and hydrogen from biomass[J].Journal of Power Sources,2002,111(1):1-22.
[7] Jasinskas A,Zaltauskas A,Kryzeviciene A.The investigation of growing and using of tall perennial grasses as energy crops[J].Biomass & Bioenergy,2008,32(11):981-987.
[8] Li W,Yan Y,Huang M,et al.Modification of dolomite for hydrogen production via catalytic gasification of residue derived from biomass hydrolysis[J].International Journal of Global Energy Issues,2007,28(4):419-429.
[9] Peng Dong,Xu Chenghua Feng Chao,et al.Preparation of Ni/TiO2-Al2O3 catalyst and its application in glycerin water steam reforming synthetic gas[J].Chinese Journal of Synthetic Chemistry,2014,22(1):40-45(in Chinese).彭东,徐成华,封超,等.Ni/TiO2-Al2O3催化剂的制备及其在甘油水蒸汽重整制合成气中的应用[J].合成化学,2014,22(1):40-45.
[10] Karthikeyan D,Shin G S,Moon D J,et al.Aqueous phase reforming of glycerol over the Pd loaded Ni/Al2O3 catalysts[J].J Nanosci Nanotechnol,2011,11(2):1443-1446.
[11] 李双明,于春令,刘章科,等.生物质气化焦油催化裂解研究[J].中国水运,2011,11(4):238-241.
[12] Lu Wen,Kong Meng,Yang Qi,et al.The effect of the carrier on the properties of nickel-based catalyst and toluene water vapor reforming[J].Chemical Reaction Engineering and Process,2012,28(3)238-243(in Chinese).卢雯,孔猛,杨琦,等.载体对镍基催化剂及其甲苯水蒸气重整性能的影响[J].化学反应工程与工艺,2012,28(3)238-243.
[13] Zhang Qiuyun,Li Hu,Qin Wenting,et al.Solid acid used as highly efficient catalyst for esterification of free fatty acids with alcohols[J].China Petroleum Processing & Petrochemical Technology,2013,15(1):19-24.
[14] Zhao Liang,Zhang Jun,Sheng Changdong,et al.Progress in catalysts for hydrogen production by biomass supercritical water gasification[J].Moderm Chemical Industry,2009,29(s2):65-68(in Chinese).赵亮,张军,盛昌栋,等.生物质超临界水气化制氢中催化剂的研究进展[J].现代化工,2009,29(s2):65-68.
[15] Zhang Y M,Sun G G,Gao S Q,et al.Characteristics and kinetics of steam-gasification regeneration for coked FCC catalyst in a micro-fluidized bed reactor[J].Acta Petrolei Sinica,2014,30(6):1043-1051.
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