硅藻土对本体型催化剂水热/机械稳定性的影响
|
摘要
以炭黑为扩孔剂,采用溶胶-凝胶法制备了Ni-Mo复合氧化物粉体,以硅藻土与氢氧化铝干胶的混合物为黏合剂制备了本体型Ni-Mo复合氧化物催化剂,通过XRD,BET,Py-IR,NH_3-TPD等技术对催化剂进行表征,并以含小桐子油(体积分数为20%)的正辛烷溶液为原料,考察硅藻土对本体型加氢脱氧催化剂水热/机械稳定性的影响。结果表明,催化剂制备过程中加入硅藻土未明显影响催化剂的晶相,但是显著增大了催化剂的孔径,并且加入的硅藻土覆盖住部分暴露于催化剂表面及孔道内的Al~(3+),有效地抑制了Al_2O_3的水合反应及由此引起的催化剂孔结构的坍塌及金属颗粒的聚集,显著提高了催化剂的水热/机械稳定性。
Ni-Mo oxide powders were prepared by sol-gel method using carbon black as pore-enlarging agent.Ni-Mo composite oxide bulk catalysts were prepared by using a mixture of diatomaceous earth and alumina gel as binder.The catalysts were characterized by XRD,BET,Py-IR,NH_3-TPD.The effect of diatomaceous earth addition on hydrothermal/mechanical stability of bulk hydrodeoxygenation catalyst was examined.The hydrodeoxygenation performance was evaluated using n-octane solution containing 20% jatropha oil as the raw material.The results showed that the addition of diatomaceous earth during the preparation of the catalyst did not significantly affect the crystal phase of the catalyst,but significantly increased the pore size of the catalyst;the added diatomaceous earth covered part of the Al~(3+) exposed on the surface of the catalyst and in the pores,which can effectively inhibits the collapse of the pore structure of the catalyst and the aggregation of the metal particles caused by the hydration reaction of the Al_2O_3.As a result,the hydrothermal/mechanical stability of the catalyst are significantly improved.
Ni-Mo oxide powders were prepared by sol-gel method using carbon black as pore-enlarging agent.Ni-Mo composite oxide bulk catalysts were prepared by using a mixture of diatomaceous earth and alumina gel as binder.The catalysts were characterized by XRD,BET,Py-IR,NH_3-TPD.The effect of diatomaceous earth addition on hydrothermal/mechanical stability of bulk hydrodeoxygenation catalyst was examined.The hydrodeoxygenation performance was evaluated using n-octane solution containing 20% jatropha oil as the raw material.The results showed that the addition of diatomaceous earth during the preparation of the catalyst did not significantly affect the crystal phase of the catalyst,but significantly increased the pore size of the catalyst;the added diatomaceous earth covered part of the Al~(3+) exposed on the surface of the catalyst and in the pores,which can effectively inhibits the collapse of the pore structure of the catalyst and the aggregation of the metal particles caused by the hydration reaction of the Al_2O_3.As a result,the hydrothermal/mechanical stability of the catalyst are significantly improved.
引文
[1] Wakil M A,Kalam M A,Masjuki H H,et al.Influence of biodiesel blending on physicochemical properties and importance of mathematical model for predicting the properties of biodiesel blend[J].Energy Conversion & Management,2015,94:51-67
[2] Huber G W,Iborra S,Corma A.Synthesis of transportation fuels from biomass:Chemistry,catalysts and engineering[J].Chemical Reviews,2006,106(9):4044-4409
[3] Geuens J,Kremsner J M,Nebel B A.Microwave-assisted catalyst-free transesterification of triglycerides with 1-butanol under supercritical conditions[J].Energy Fuels,2008,22(1):643-645
[4] Furimsky E.Catalytic hydrodeoxygenation [J].Applied Catalysis A:General,2000,199(2):147-190
[5] 王威燕.生物油中含氧化合物加氢脱氧新型催化剂的制备、表征及性能研究[D].湘潭:湘潭大学,2011
[6] Holm M S,Saravanamurugan S,Taarning E.Conversion of sugars to lactic acid derivatives using heterogeneous zeotype catalysts[J].Science,2010,328(5978):602-605
[7] Zhang Fuqiang,Yan Yan,Yang Haifeng et al.Understanding effect of wall structure on the hydrothermal stability of mesostructured silica SBA-15[J].Journal of Physical Chemistry:B,2005,109(18):8723-8732
[8] Han Yu,Li Defeng,Zhao Lan.High-temperature generalized synthesis of stable ordered mesoporous silica-based materials by using fluorocarbon-hydrocarbon surfactant mixtures[J].Ange-Wandte Chemie International Edition,2003,42(31):3633-3637
[9] Doukkali M E,Iriondo A,Miletic N,et al.Hydrothermal stability improvement of NiPt-containing γ-Al2O3,catalysts tested in aqueous phase reforming of glycerol/water mixture for H2 production[J].International Journal of Hydrogen Energy,2017,22:13-15
[10] Sallem F,Chassagnon R,Megriche A,et al.Effect of mechanical stirring and temperature on dynamic hydrothermal synthesis of titanate nanotubes[J].Journal of Alloys & Compounds,2017,722:785-796
[11] Mokaya R,Jones W,Davies M E,et al.The mechanism of chlorophyll adsorption on acid-activated clays [J].Journal of Solid State Chemistry,1994,111(1):157-163
[12] Mokaya R.The effect of particle size on aluminosilicate MCM-41 catalysts prepared via grafting routes [J].Journal of Catalysis,1999,186(2):470-477
[13] 亢丽娜,郭江渊,张鸿喜,等.Ni/SiO2-Al2O3催化剂在水相加氢体系中的活性及稳定性研究[J].分子催化,2014,28(2):119-125
[14] 赵永祥,李海涛,孙自瑾,等.一种SiO2-C Al2O3载体及制备方法和应用:中国,CN106902800A[P].2017-06-30
[15] 赵永祥,李海涛,宋美婷,等.一种Ni-SiO2/Al2O3催化剂的制备方法:中国,CN102145286B[P].2011-08-10
[16] 中华人民共和国国家标准.GB/T 5534—2008 动植物油脂皂化值的测[S].2009
[17] Wang Qiang,Cheng Haiyang,Liu Ruixia,et al.Influence of metal particle size on the hydrogenation of malefic anhydride over Pd/C catalysts in ScCO2[J].Catal Today,2009,148(1):368-372
[18] Taniike T,Chammingkwan P,Thang V Q,et al.Validation of BET specific surface area for heterogeneous Ziegler-Natta catalysts based on αs-plot [J].Applied Catalysis A:General,2012,437/438:24-27
[19] 耿国龙,任亮亮,王炜,等.扩孔对本体型Ni-Mo复合氧化物催化剂加氢脱氧性能的影响[J].高校化学工程学报,2015,29(4):837-842
[20] Guo Xinwen,Shen Jianping,Song Chunshan,et al.Effects of SiO2/Al2O3,MgO modification and hydrothermal treatment on shape-selectvity methylation of 4-methylbiphenyl with methanol over HZSM-5 zeolite catalysts[J].Studies in Surface Science & Catalysis,2004,154:2247-2254
[21] 徐冬梅,纪道玉,孟凡禹,等.生物油含氧化合物加氢脱氧反应机理研究进展[J].生物质化学工程,2017(3):23-34
[2] Huber G W,Iborra S,Corma A.Synthesis of transportation fuels from biomass:Chemistry,catalysts and engineering[J].Chemical Reviews,2006,106(9):4044-4409
[3] Geuens J,Kremsner J M,Nebel B A.Microwave-assisted catalyst-free transesterification of triglycerides with 1-butanol under supercritical conditions[J].Energy Fuels,2008,22(1):643-645
[4] Furimsky E.Catalytic hydrodeoxygenation [J].Applied Catalysis A:General,2000,199(2):147-190
[5] 王威燕.生物油中含氧化合物加氢脱氧新型催化剂的制备、表征及性能研究[D].湘潭:湘潭大学,2011
[6] Holm M S,Saravanamurugan S,Taarning E.Conversion of sugars to lactic acid derivatives using heterogeneous zeotype catalysts[J].Science,2010,328(5978):602-605
[7] Zhang Fuqiang,Yan Yan,Yang Haifeng et al.Understanding effect of wall structure on the hydrothermal stability of mesostructured silica SBA-15[J].Journal of Physical Chemistry:B,2005,109(18):8723-8732
[8] Han Yu,Li Defeng,Zhao Lan.High-temperature generalized synthesis of stable ordered mesoporous silica-based materials by using fluorocarbon-hydrocarbon surfactant mixtures[J].Ange-Wandte Chemie International Edition,2003,42(31):3633-3637
[9] Doukkali M E,Iriondo A,Miletic N,et al.Hydrothermal stability improvement of NiPt-containing γ-Al2O3,catalysts tested in aqueous phase reforming of glycerol/water mixture for H2 production[J].International Journal of Hydrogen Energy,2017,22:13-15
[10] Sallem F,Chassagnon R,Megriche A,et al.Effect of mechanical stirring and temperature on dynamic hydrothermal synthesis of titanate nanotubes[J].Journal of Alloys & Compounds,2017,722:785-796
[11] Mokaya R,Jones W,Davies M E,et al.The mechanism of chlorophyll adsorption on acid-activated clays [J].Journal of Solid State Chemistry,1994,111(1):157-163
[12] Mokaya R.The effect of particle size on aluminosilicate MCM-41 catalysts prepared via grafting routes [J].Journal of Catalysis,1999,186(2):470-477
[13] 亢丽娜,郭江渊,张鸿喜,等.Ni/SiO2-Al2O3催化剂在水相加氢体系中的活性及稳定性研究[J].分子催化,2014,28(2):119-125
[14] 赵永祥,李海涛,孙自瑾,等.一种SiO2-C Al2O3载体及制备方法和应用:中国,CN106902800A[P].2017-06-30
[15] 赵永祥,李海涛,宋美婷,等.一种Ni-SiO2/Al2O3催化剂的制备方法:中国,CN102145286B[P].2011-08-10
[16] 中华人民共和国国家标准.GB/T 5534—2008 动植物油脂皂化值的测[S].2009
[17] Wang Qiang,Cheng Haiyang,Liu Ruixia,et al.Influence of metal particle size on the hydrogenation of malefic anhydride over Pd/C catalysts in ScCO2[J].Catal Today,2009,148(1):368-372
[18] Taniike T,Chammingkwan P,Thang V Q,et al.Validation of BET specific surface area for heterogeneous Ziegler-Natta catalysts based on αs-plot [J].Applied Catalysis A:General,2012,437/438:24-27
[19] 耿国龙,任亮亮,王炜,等.扩孔对本体型Ni-Mo复合氧化物催化剂加氢脱氧性能的影响[J].高校化学工程学报,2015,29(4):837-842
[20] Guo Xinwen,Shen Jianping,Song Chunshan,et al.Effects of SiO2/Al2O3,MgO modification and hydrothermal treatment on shape-selectvity methylation of 4-methylbiphenyl with methanol over HZSM-5 zeolite catalysts[J].Studies in Surface Science & Catalysis,2004,154:2247-2254
[21] 徐冬梅,纪道玉,孟凡禹,等.生物油含氧化合物加氢脱氧反应机理研究进展[J].生物质化学工程,2017(3):23-34