含氮化合物对柴油超深度加氢脱硫催化剂运行稳定性的影响
|
摘要
采用中型固定床加氢装置考察了含氮化合物对柴油超深度加氢脱硫Ni-Mo-W型催化剂运行稳定性的影响。通过元素分析、N_2吸附-脱附、热重-质谱(TG-MS)联用、X射线光电子能谱(XPS)、高分辨透射电镜(TEM)等表征手段研究了催化剂失活的主要原因。实验结果表明:原料添加含氮化合物后,主要影响了催化剂的初活性,运转初期反应温度提高了7～10℃,但对催化剂的稳定性影响不大。根据催化剂失活原因的分析发现,原料添加含氮化合物前后,催化剂失活的主要原因均与其表面积炭的形成、孔体积的损失和边缘W比例的下降密切相关。
With using Ni-Mo-W/γ-Al_2O_3 catalyst,effect of nitrogen compounds on the running stability of ultra-deep hydro-desulfurization diesel catalyst was studied on a pilot plant unit.The reasons of catalyst deactivation were investigated by different characterization techniques which included elemental analysis,nitrogen adsorption-desorption,thermal gravity-mass spectrometry(TG-MS),X-ray photoelectron spectroscopy(XPS)and high resolution transmission electron microscopy(TEM).Experimental results suggest that nitrogen compounds mainly impact on catalyst initial activity,and lead to initial reaction temperature 7 to 10 ℃ higher.However,nitrogen compounds have little impact on catalyst stability.With/without nitrogen compounds adding into the feedstocks,the main reasons of catalyst deactivation are all mainly related to the surface coking,loss of pore volume and decrease of edge tungsten.
With using Ni-Mo-W/γ-Al_2O_3 catalyst,effect of nitrogen compounds on the running stability of ultra-deep hydro-desulfurization diesel catalyst was studied on a pilot plant unit.The reasons of catalyst deactivation were investigated by different characterization techniques which included elemental analysis,nitrogen adsorption-desorption,thermal gravity-mass spectrometry(TG-MS),X-ray photoelectron spectroscopy(XPS)and high resolution transmission electron microscopy(TEM).Experimental results suggest that nitrogen compounds mainly impact on catalyst initial activity,and lead to initial reaction temperature 7 to 10 ℃ higher.However,nitrogen compounds have little impact on catalyst stability.With/without nitrogen compounds adding into the feedstocks,the main reasons of catalyst deactivation are all mainly related to the surface coking,loss of pore volume and decrease of edge tungsten.
引文
[1]LANDAU M V.Deep hydrotreating of middle distillates from crude and shale oils[J].Catalysis Today,1997,36(4):393-429.
[2]TORRISI S,DICAMILLO D,STREET R,et al.Proven best practices for ULSD production[C]//San Antonio:National Petrochemical&Refiners Association,2002.
[3]王丹,宋金鹤,韩志波,等.柴油加氢精制催化剂的开发及工业应用[J].石油化工,2017,46(2):241-247.(WANG Dan,SONG Jinhe,HAN Zhibo,et al.Development and commercial application of diesel hydrotreating catalyst[J].Petrochemical Technology,2017,46(2):241-247.)
[4]FURIMSKY E,MASSOTH F E.Deactivation of hydroprocessing catalysts[J].Catalysis Today,1999,52(4):381-495.
[5]FURIMSKY E,MASSOTH F E.Hydrodenitrogenation of petroleum[J].Catalysis Reviews,2005,47(3):297-489.
[6]BREYSSE M,FURIMSKY E,KASZTELAN S,et al.Hydrogen activation by transition metal sulfides[J].Catalysis Reviews,2002,44(4):651-735.
[7]魏计春,齐邦峰,张会成.催化柴油中含氮化合物的研究[J].化工科技,2010,18(1):60-63.(WEI Jichun,QI Bangfeng,ZHANG Huicheng.The research of nitrogen compounds in diesel oil[J].Science&Technology in Chemical Industry,2010,18(1):60-63.)
[8]YOSHIMURA Y,SATO T,SHIMADA H,et al.Oxidative regeneration of spent molybdate and tungstate hydrotreating catalysts[J].Energy&Fuels,1994,8(2):435-445.
[9]GURICHARD B,ROY-AUBERGER M,DEVERS E,et al.Characterization of aged hydrotreating catalysts Part I:Coke depositions,study on the chemical nature and environment[J].Applied Catalysis A:General,2009,367(1/2):1-8.
[10]邱丽美,齐和日玛,刘清河,等.X射线光电子能谱法研究加氢脱硫催化剂中活性元素的化学态[J].石油学报(石油加工),2011,27(4):638-642.(QIU Limei,QI Herima,LIU Qinghe,et al.Investigation of chemical states for hydrodesulfurization catalysts by using X-Ray photoelectron spectroscopy[J].Acta Petrolei Sinica(Petroleum Processing Section),2011,27(4):638-642.)
[11]QIU L,XU G.Peak overlaps and corresponding solutions in the X-ray photoelectron spectroscopic study of hydrodesulfurization catalysts[J].Applied Surface Science,2010,256(11):3413-3417.
[12]HAN W,YUAN P,FAN Y,et al.Preparation of supported hydrodesulfurization catalysts with enhanced performance using Mo-based inorganic-organic hybrid nanocrystals as a superior precursor[J].Journal of Materials Chemistry,2012,22(48):25340-25353.
[13]HENSEN E J M,KOOYMAN P J,van DER MEER Y,et al.The relation between morphology and hydrotreating activity for supported MoS2 particles[J].Journal of Catalysis,2001,199(2):224-235.
[14]张妍茹.加氢催化剂活性金属高效再分散的研究[D].北京:石油化工科学研究院,2016.
[15]邵志才,高晓冬,李皓光,等.氮化物对柴油深度和超深度加氢脱硫的影响Ⅰ氮化物含量的影响[J].石油学报(石油加工),2006,22(4):12-18.(SHAO Zhicai,GAO Xiaodong,LI Haoguang,et al.Effect of nitrogencontaining compounds on deep and ultra deep HDS for diesel oil I Effect of the content of nitrogen-containing compounds[J].Acta Petrolei Sinica(Petroleum Processing Section),2006,22(4):12-18.)
[16]刘法.柴油馏分超深度加氢脱硫动力学模型研究[D].北京:石油化工科学研究院,2006.
[17]ANCHEYTA J,ANGELES M J,MACIAS M J,et al.Changes in apparent reaction order and activation energy in the hydrodesulfurization of real feedstocks[J].Energy&Fuels,2002,16(1):189-193.
[18]葛泮珠,丁石,张乐,等.氮化物对Ni-Mo-W和Co-Mo型催化剂超深度加氢脱硫反应的影响[J].石油化工,2017,46(2):171-176.(GE Panzhu,DING Shi,ZHANG Le,et al.Effect of nitrogen-compounds on ultra-deep HDS for diesel oil on Ni-Mo-W/Al2O3 and Co-Mo/Al2O3catalysts[J].Petrochemical Technology,2017,46(2):171-176.)
[19]MARAFI A,STAINSLAUS A,HAUSER A,et al.An investigation of the deactivation behavior of industrial Mo/Al2O3and Ni-Mo/Al2O3 catalysts in hydrotreating Kuwait atmospheric residue[J].Petroleum Science and Technology,2005,23:385-408.
[20]MATSUSHITA K,HAUSER A,MARAFI A,et al.Initial coke deposition on hydrotreating catalysts Part 1Changes in coke properties as a function of time on stream[J].Fuel,2004,83(7/8):1031-1038.
[21]DONG D,JEONG S,MASSOTH F E.Effect of nitrogen compounds on deactivation of hydrotreating catalysts by coke[J].Catalysis Today,1997,37(3):267-275.
[22]陈士锋,陈海,杨朝合.渣油加氢转化过程结焦催化剂的表征[J].石油学报(石油加工),2002,18(3):8-13.(CHEN Shifeng,CHEN Hai,YANG Chaohe.Characterization of coked catalysts for residual hydroconversion process[J].Acta Petrolei Sinica(Petroleum Processing Section),2002,18(3):8-13.)
[23]SAHOO S K,RAY S S,SINGH I D.Structural characterization of coke on spent hydroprocessing catalysts used for processing of vacuum gas oil[J].Applied Catalysis A:General,2004,278(1):83-91.
[24]CALLEJAS M A,INEZ M T M,BLASCO T,et al.Coke characterisation in aged residue hydrotreating catalysts by solid-state 13 C-NMR spectroscopy and temperature-programmed oxidation[J].Applied Catalysis A:General,2001,218:181-188.
[25]GE P,ZHANG L,DING S,et al.Correlation of deactivation of Ni-Mo-W/Al2O3 during ultra-low-sulfur diesel production with surface carbon species[J].China Petroleum Processing&Petrochemical Technology,2017,19(2):1-7.
[26]van DOOM J,MOULIJN J A,DJEGA-MARIADASSOU G.High-resolution electron microscopy of spent Ni-Mo/Al2O3 hydrotreating catalysts[J].Applied Catalysis,1990,63(1):77-90.
[27]DIEZ F,GATES B C,MILLER J T,et al.Deactivation of a Ni-Mo/γ-Al2O3 catalyst:Influence of coke on the hydroprocessing activity[J].Industrial&Engineering Chemistry Research,1990,29(10):1999-2004.
[2]TORRISI S,DICAMILLO D,STREET R,et al.Proven best practices for ULSD production[C]//San Antonio:National Petrochemical&Refiners Association,2002.
[3]王丹,宋金鹤,韩志波,等.柴油加氢精制催化剂的开发及工业应用[J].石油化工,2017,46(2):241-247.(WANG Dan,SONG Jinhe,HAN Zhibo,et al.Development and commercial application of diesel hydrotreating catalyst[J].Petrochemical Technology,2017,46(2):241-247.)
[4]FURIMSKY E,MASSOTH F E.Deactivation of hydroprocessing catalysts[J].Catalysis Today,1999,52(4):381-495.
[5]FURIMSKY E,MASSOTH F E.Hydrodenitrogenation of petroleum[J].Catalysis Reviews,2005,47(3):297-489.
[6]BREYSSE M,FURIMSKY E,KASZTELAN S,et al.Hydrogen activation by transition metal sulfides[J].Catalysis Reviews,2002,44(4):651-735.
[7]魏计春,齐邦峰,张会成.催化柴油中含氮化合物的研究[J].化工科技,2010,18(1):60-63.(WEI Jichun,QI Bangfeng,ZHANG Huicheng.The research of nitrogen compounds in diesel oil[J].Science&Technology in Chemical Industry,2010,18(1):60-63.)
[8]YOSHIMURA Y,SATO T,SHIMADA H,et al.Oxidative regeneration of spent molybdate and tungstate hydrotreating catalysts[J].Energy&Fuels,1994,8(2):435-445.
[9]GURICHARD B,ROY-AUBERGER M,DEVERS E,et al.Characterization of aged hydrotreating catalysts Part I:Coke depositions,study on the chemical nature and environment[J].Applied Catalysis A:General,2009,367(1/2):1-8.
[10]邱丽美,齐和日玛,刘清河,等.X射线光电子能谱法研究加氢脱硫催化剂中活性元素的化学态[J].石油学报(石油加工),2011,27(4):638-642.(QIU Limei,QI Herima,LIU Qinghe,et al.Investigation of chemical states for hydrodesulfurization catalysts by using X-Ray photoelectron spectroscopy[J].Acta Petrolei Sinica(Petroleum Processing Section),2011,27(4):638-642.)
[11]QIU L,XU G.Peak overlaps and corresponding solutions in the X-ray photoelectron spectroscopic study of hydrodesulfurization catalysts[J].Applied Surface Science,2010,256(11):3413-3417.
[12]HAN W,YUAN P,FAN Y,et al.Preparation of supported hydrodesulfurization catalysts with enhanced performance using Mo-based inorganic-organic hybrid nanocrystals as a superior precursor[J].Journal of Materials Chemistry,2012,22(48):25340-25353.
[13]HENSEN E J M,KOOYMAN P J,van DER MEER Y,et al.The relation between morphology and hydrotreating activity for supported MoS2 particles[J].Journal of Catalysis,2001,199(2):224-235.
[14]张妍茹.加氢催化剂活性金属高效再分散的研究[D].北京:石油化工科学研究院,2016.
[15]邵志才,高晓冬,李皓光,等.氮化物对柴油深度和超深度加氢脱硫的影响Ⅰ氮化物含量的影响[J].石油学报(石油加工),2006,22(4):12-18.(SHAO Zhicai,GAO Xiaodong,LI Haoguang,et al.Effect of nitrogencontaining compounds on deep and ultra deep HDS for diesel oil I Effect of the content of nitrogen-containing compounds[J].Acta Petrolei Sinica(Petroleum Processing Section),2006,22(4):12-18.)
[16]刘法.柴油馏分超深度加氢脱硫动力学模型研究[D].北京:石油化工科学研究院,2006.
[17]ANCHEYTA J,ANGELES M J,MACIAS M J,et al.Changes in apparent reaction order and activation energy in the hydrodesulfurization of real feedstocks[J].Energy&Fuels,2002,16(1):189-193.
[18]葛泮珠,丁石,张乐,等.氮化物对Ni-Mo-W和Co-Mo型催化剂超深度加氢脱硫反应的影响[J].石油化工,2017,46(2):171-176.(GE Panzhu,DING Shi,ZHANG Le,et al.Effect of nitrogen-compounds on ultra-deep HDS for diesel oil on Ni-Mo-W/Al2O3 and Co-Mo/Al2O3catalysts[J].Petrochemical Technology,2017,46(2):171-176.)
[19]MARAFI A,STAINSLAUS A,HAUSER A,et al.An investigation of the deactivation behavior of industrial Mo/Al2O3and Ni-Mo/Al2O3 catalysts in hydrotreating Kuwait atmospheric residue[J].Petroleum Science and Technology,2005,23:385-408.
[20]MATSUSHITA K,HAUSER A,MARAFI A,et al.Initial coke deposition on hydrotreating catalysts Part 1Changes in coke properties as a function of time on stream[J].Fuel,2004,83(7/8):1031-1038.
[21]DONG D,JEONG S,MASSOTH F E.Effect of nitrogen compounds on deactivation of hydrotreating catalysts by coke[J].Catalysis Today,1997,37(3):267-275.
[22]陈士锋,陈海,杨朝合.渣油加氢转化过程结焦催化剂的表征[J].石油学报(石油加工),2002,18(3):8-13.(CHEN Shifeng,CHEN Hai,YANG Chaohe.Characterization of coked catalysts for residual hydroconversion process[J].Acta Petrolei Sinica(Petroleum Processing Section),2002,18(3):8-13.)
[23]SAHOO S K,RAY S S,SINGH I D.Structural characterization of coke on spent hydroprocessing catalysts used for processing of vacuum gas oil[J].Applied Catalysis A:General,2004,278(1):83-91.
[24]CALLEJAS M A,INEZ M T M,BLASCO T,et al.Coke characterisation in aged residue hydrotreating catalysts by solid-state 13 C-NMR spectroscopy and temperature-programmed oxidation[J].Applied Catalysis A:General,2001,218:181-188.
[25]GE P,ZHANG L,DING S,et al.Correlation of deactivation of Ni-Mo-W/Al2O3 during ultra-low-sulfur diesel production with surface carbon species[J].China Petroleum Processing&Petrochemical Technology,2017,19(2):1-7.
[26]van DOOM J,MOULIJN J A,DJEGA-MARIADASSOU G.High-resolution electron microscopy of spent Ni-Mo/Al2O3 hydrotreating catalysts[J].Applied Catalysis,1990,63(1):77-90.
[27]DIEZ F,GATES B C,MILLER J T,et al.Deactivation of a Ni-Mo/γ-Al2O3 catalyst:Influence of coke on the hydroprocessing activity[J].Industrial&Engineering Chemistry Research,1990,29(10):1999-2004.