生物油模型物糠醛催化加氢试验研究
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摘要
选取糠醛作为生物油催化提质的模型物,以Al2O3分子筛为催化剂载体,制备的活性物质分别为NiFe、Ni-Cu和Ni-Ce3种双金属催化剂,研究了活性组分负载量、反应温度和氢醛摩尔比对糠醛常压下催化加氢效果的影响。结果表明:当催化剂为7.5%Ni-7.5%Cu/Al2O3、反应温度为200℃、氢醛摩尔比为5.0时,能达到最佳效果,糠醛的转化率为69.95%,糠醇的选择性达到了96.26%。催化剂表征结果表明:活性物质在载体上分散效果较好,用后催化剂表面积炭主要为未降解的有机物或者其聚合物。
Furfural was selected for bio-oil catalytic qualitative modelin this paper,used Al2O3 molecular sieve as catalyst carrier,preparation of active substances were Ni-Fe,Ni-Cu and Ni-Ce three kinds of double metal catalyst,to study the effects of active component loading,reaction temperature and hydrogen ratio on catalytic hydrogenation of furfural aldehyde effect. The results showed that the best results can be achieved when the Al2O3 was the carrier and the capacity of the active material of Ni-Cu was7. 5%,and the reaction temperature was 200℃ and hydrogen aldehyde molar ratio was5. The yield of the target product furfuryl alcohol was 67. 33% and the conversion rate was 69. 95% and the selectivity is 96. 26%. The results showed that: the active materials of the carrier were dispersed effectively. The main material of carbon deposit on the surface of catalysts are not degradation of organic matter or the polymer after reaction.
Furfural was selected for bio-oil catalytic qualitative modelin this paper,used Al2O3 molecular sieve as catalyst carrier,preparation of active substances were Ni-Fe,Ni-Cu and Ni-Ce three kinds of double metal catalyst,to study the effects of active component loading,reaction temperature and hydrogen ratio on catalytic hydrogenation of furfural aldehyde effect. The results showed that the best results can be achieved when the Al2O3 was the carrier and the capacity of the active material of Ni-Cu was7. 5%,and the reaction temperature was 200℃ and hydrogen aldehyde molar ratio was5. The yield of the target product furfuryl alcohol was 67. 33% and the conversion rate was 69. 95% and the selectivity is 96. 26%. The results showed that: the active materials of the carrier were dispersed effectively. The main material of carbon deposit on the surface of catalysts are not degradation of organic matter or the polymer after reaction.
引文
[1]刘荣厚.生物质能工程[M].北京:化学工业出版社,2009:1-35.
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[3]Mahfud F H,Ghijsen F,Heeres H J.Hydrogenation of fast pyrolyis oil and model compounds in a two-phaseaqueous organic system using homogeneous ruthenium catalysts[J].Journal of Molecular Catalysis A:Chemical,2007,264(1-2):227-236.
[4]Sepulveda C,Leiva K,Garcia R.Hydrodeoxygenation of 2-methoxyphenol over MO2N catalysts supported on activated carbons[J].Catalysis Today,2011,172:232-239.
[5]魁彦萍,曹晶,周赫,等.生物油的成分分析及物性测定[J].化工生产与技术,2010(5):52-54.
[6]李凭力,肖文平,常贺英,等.糠醛生产工艺的发展[J].林产工业,2006,33(2):13-16.
[7]Rao R,Dandekar A,Baker R T K,et al.Properties of Copper chromite catalysts in Hydrogenation Reactions[J].J Catal,1997,171(2):406-419.
[8]赵修波,蒋新,周红军.糠醛液相加氢催化剂的研制及工业应用[J].工业催化,2005,13(10):47-50.
[9]Li H,Luo H,Zhuang L,et al.Liquid phase hydrogenation of furfural to furfuryl alcohol over the Fe-promoted Ni-B amorphous alloy catalysts[J].Journal of Molecular Catalysis a:Chemical,2003,203(1):267-275.
[10]刘琪英,李勇,蔡伟杰,等.镍基催化剂上糠醛选择性加氢合成糠醇[J].分子催化,2007,21(4):294-299.
[11]Li H,Zhang S,Luo H.A Ce-promoted Ni–B amorphous alloy catalyst(Ni-Ce-B)for liquid-phase furfural hydrogenation to furfural alcohol[J].Materials Letters,2004,58(22):2741-2746.
[12]Li Y,Xu X,Zhang P,et al.Highly selective Pd@mpgC 3 N 4 catalyst for phenol hydrogenation in aqueous phase[J].RSC Advances,2013,27(3):10973-10982.
[2]Marquevich M,Czernik S,Chornet E,et al.Hydrogen from biomass:steam reforming of model compounds of fast-pyrolysis oil[J].Energy&Fuels,1999,13(6):1160-1166.
[3]Mahfud F H,Ghijsen F,Heeres H J.Hydrogenation of fast pyrolyis oil and model compounds in a two-phaseaqueous organic system using homogeneous ruthenium catalysts[J].Journal of Molecular Catalysis A:Chemical,2007,264(1-2):227-236.
[4]Sepulveda C,Leiva K,Garcia R.Hydrodeoxygenation of 2-methoxyphenol over MO2N catalysts supported on activated carbons[J].Catalysis Today,2011,172:232-239.
[5]魁彦萍,曹晶,周赫,等.生物油的成分分析及物性测定[J].化工生产与技术,2010(5):52-54.
[6]李凭力,肖文平,常贺英,等.糠醛生产工艺的发展[J].林产工业,2006,33(2):13-16.
[7]Rao R,Dandekar A,Baker R T K,et al.Properties of Copper chromite catalysts in Hydrogenation Reactions[J].J Catal,1997,171(2):406-419.
[8]赵修波,蒋新,周红军.糠醛液相加氢催化剂的研制及工业应用[J].工业催化,2005,13(10):47-50.
[9]Li H,Luo H,Zhuang L,et al.Liquid phase hydrogenation of furfural to furfuryl alcohol over the Fe-promoted Ni-B amorphous alloy catalysts[J].Journal of Molecular Catalysis a:Chemical,2003,203(1):267-275.
[10]刘琪英,李勇,蔡伟杰,等.镍基催化剂上糠醛选择性加氢合成糠醇[J].分子催化,2007,21(4):294-299.
[11]Li H,Zhang S,Luo H.A Ce-promoted Ni–B amorphous alloy catalyst(Ni-Ce-B)for liquid-phase furfural hydrogenation to furfural alcohol[J].Materials Letters,2004,58(22):2741-2746.
[12]Li Y,Xu X,Zhang P,et al.Highly selective Pd@mpgC 3 N 4 catalyst for phenol hydrogenation in aqueous phase[J].RSC Advances,2013,27(3):10973-10982.
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