煤焦油加氢过程中NiWP/Al_2O_3催化剂失活研究
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摘要
在固定床加氢微型反应器上进行NiWP/Al_2O_3催化剂的煤焦油模化物加氢实验,分析了催化剂初期快速失活的原因。本实验采用N_2吸附-脱附、XRD、元素分析、SEM、TPO-MS、TG、FTIR和XPS等方法分析催化剂反应前后的性质变化及表面积碳情况,结果表明:随着反应进行,催化剂的加氢脱硫活性和加氢脱氧活性变化不大,而加氢脱氮活性快速下降;催化剂快速失活的主要原因是表面生成积碳,覆盖其表面的反应活性中心,使加氢反应活性下降;表面积碳的主要成分是芳香烃,还有少量脂肪烃。
The coal tar model compounds hydrogenation experiment on NiWP/Al_2O_3 catalyst was carried out in a fixed bed micro-reactor to analyze the reasons for the initial rapid deactivation of the catalyst.The properties of the catalyst before and after the reaction and the carbon on surface area were analyzed by N_2 adsorption-desorption,XRD,ultimate analysis,SEM,TPOMS,TG,FTIR and XPS.The results show that hydrodesulfurization and hydrodeoxygenation activity of the catalyst do not change much as the reaction progressed,while hydrodenitrogenation activity decreases rapidly.The main reason for the rapid deactivation of the catalyst is the formation of carbon on the surface,which coveres the active reaction centers on the surface and reduces the active sites of the hydrogenation reaction.The surface carbon deposition is mainly composed of aromatic hydrocarbons and a small amount of aliphatic hydrocarbons.
The coal tar model compounds hydrogenation experiment on NiWP/Al_2O_3 catalyst was carried out in a fixed bed micro-reactor to analyze the reasons for the initial rapid deactivation of the catalyst.The properties of the catalyst before and after the reaction and the carbon on surface area were analyzed by N_2 adsorption-desorption,XRD,ultimate analysis,SEM,TPOMS,TG,FTIR and XPS.The results show that hydrodesulfurization and hydrodeoxygenation activity of the catalyst do not change much as the reaction progressed,while hydrodenitrogenation activity decreases rapidly.The main reason for the rapid deactivation of the catalyst is the formation of carbon on the surface,which coveres the active reaction centers on the surface and reduces the active sites of the hydrogenation reaction.The surface carbon deposition is mainly composed of aromatic hydrocarbons and a small amount of aliphatic hydrocarbons.
引文
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[2]LEI Z,HU D N,PAN H T,et al.Research Progress of Coal Tar Catalytic Hydrogenation[J].Modern Chemical Industry,2014,34(1):30-33.
[3]GRANGE P,VANHAEREN X.Hydrotreating Catalysts,an Old Story with New Challenges[J].Catalysis Today,1997,36(4):375-391.
[4]佟瑞利,王永刚,张旭,等.P改性NiW/γ-Al2O3的低温焦油芳烃组分加氢性能研究[J].燃料化学学报,2015,43(12):1461-1469.TONG Ruili,WANG Yonggang,ZHANG Xu,et al.Effect of Phosphorous Modification on the Catalytic Properties of NiW/γ-Al2O3in the Hydrogenation of Aromatics from Coal Tar[J].Journal of Chemistry and Technology,2015,43(12):1461-1469.
[5]唐巍.煤低温热解焦油加氢实验研究及工艺流程模拟[D].杭州:浙江大学,2014.TANG Wei.Experiment Study on the Hydrogenation of Low Temperature Coal Tar and System Simulation[D].Hangzhou:Zhejiang University,2014.
[6]张明伟,宋纪蓉,马海霞,等.磷改性NiW/γ-Al2O3催化剂加氢处理低温煤焦油[J].石油化工,2017,46(9):1132-1137.ZHANG Mingwei,SONG Jirong,MA Haixia,et al.Application of Phosphorus Modified NiW/γ-Al2O3Sulfide Catalyst in the Hydrogenation of Low Temperature Coal Tar[J].Petrochemical Technology,2017,46(9):1132-1137.
[7]HUGHES R,HUTCHINGS G J,KOON C L,et al.Deactivation of FCC Catalysts Using N-hexadecane Feed with Various Additives[J].Applied Catalysis A:General,1996,144(1/2):269-279.
[8]魏亦明,赵基钢,孙进,等.柴油加氢脱硫Mo-Co/Al2O3催化剂初期快速失活原因分析[J].现代化工,2016,36(2):141-144.WEI Yiming,ZHAO Jigang,SUN Jin,et al.Early Stage Deactivation of Mo-Co/Al2O3Catalyst for HDS[J].Modern Chemical Industry,2016,36(2):141-144.
[9]ANCHEYTA J,BETANCOURT G,CENTENO G,et al.Catalyst Deactivation During Hydroprocessing of Maya Heavy Crude Oil(PartⅡ):Effect of Temperature During Time-on-stream[J].Energy and Fuels,2003,17(2):462-467.
[10]KOHLI K,PRAJAPATI R,MAITY S K,et al.Deactivation of Hydrotreating Catalyst by Metals in Resin and Asphaltene Parts of Heavy Oil and Residues[J].Fuel,2016,175:264-273.
[11]RODRIGUEZ E,FELIX G,ANCHEYTA J,et al.Modeling of Hydrotreating Catalyst Deactivation for Heavy Oil Hydrocarbons[J].Fuel,2018,225:118-133.
[12]YAN Yuxin,SHI Lei,LIU Qingya,et al.Coke and Radicals Formation on a Sulfided NiMo/γ-Al2O3Catalyst During Hydroprocessing of an Atmospheric Residue in Hydrogen Donor Media[J].Fuel Processing Technology,2017,159:404-411.
[13]BUTT J B,PETERSON E E.Activation,Deactivation and Poisoning of Catalysts[M].New York:Academic Press,1988.
[14]LIANG X C,WANG J F,LIAN P Y,et al.Investigation on the Causes of Hydrotreating Catalyst Deactivation[J].Journal of Petrochemical Universities,2001,14(2):50-53.
[15]陈晓珍,崔波,石文平,等.催化剂的失活原因分析[J].工业催化,2001,9(5):9-16.CHEN Xiaozhen,CUI Bo,SHI Wenping,et al.The Causes for Catalyst Deactivation[J].IndustrialCatalysis,2001,9(5):9-16.
[16]YOSHIMURA Y,MATSUBAYASHI N,YOKOKAWA H,et al.Temperature-programmed Oxidation of Sulfided Cobaltmolybdate/Alumina Catalysts[J].Industrial and Engineering Chemistry Research,1991,30(6):1092-1099.
[17]苏继新,肖天存,王海涛,等.重油加氢脱硫NiMo/γ-Al2O3催化剂的失活研究[J].分子催化,1999,13(4):297-303.SU Jixin,XIAO Tiancun,WANG Haitao,et al.Deactivation of NiMo/γ-Al2O3Catalyst for Heavy Oil Hydrodesulfurization[J].Journal of Molecular Catalysis(China),1999,13(4):297-303.
[18]罗陨飞.煤的大分子结构研究---煤中惰质组结构及煤中氧的赋存形态[D].北京:煤炭科学研究总院,2002.LUO Yunfei.Study on the Macromolecular Structure of Coal:Inertial Structure in Coal and the Occurrence Form of Oxygen in Coal[D].Beijing:Coal Science Research Institute,2002.
[19]王雪.工业固定床渣油加氢装置废催化剂上焦炭结构和组成研究[D].青岛:中国石油大学(华东),2014.WANG Xue.Study on Structure and Composition of Coke on Spent Catalysts of Commercial Fixed-bed Residue Hydrotreating Unit[D].Qingdao:China University of Petroleum(East China),2014.
[20]徐秀峰,张蓬洲.高分辨固体13C-NMR和XPS技术表征碳的骨架结构[J].煤炭转化,1995,18(4):57-62.XU Xiufeng,ZHANG Pengzhou.The Study of Carbon Structure by Solid 13C-NMR and XPS[J].Coal Conversion,1995,18(4):57-62.