两类典型渣油原料加氢过程中脱金属催化剂运转初期失活研究
|
摘要
采用碳硫元素分析(CS)、催化剂氮含量分析(CAT-N)、热重-质谱联用分析(TG-MS)以及低温静态N_2物理吸附等技术手段,分别对在中型固定床渣油加氢实验装置上运转0(硫化后)、162、262、562 h后的卸出加氢脱金属催化剂进行表征,以研究高氮低硫类渣油加氢过程运转初期催化剂失活快的原因。结果表明:在相同催化剂级配体系和相同工艺条件下,与加工高硫低氮类沙特阿拉伯轻质原油的渣油原料(沙轻渣油)的脱金属催化剂相比,加工高氮低硫类仪长管输原油的渣油原料(仪长渣油)的脱金属催化剂上形成了更多的积炭,沉积的硫化物略少,而氮化物较多;加工仪长渣油的脱金属催化剂上形成了更多的高温型积炭,且相比加工沙轻渣油的脱金属催化剂上形成的高温型积炭更难氧化燃烧;积炭对加工仪长渣油的脱金属催化剂的孔结构性质影响更大,比表面积、孔体积均低于加工沙轻渣油的脱金属催化剂,大孔占比更低。
The properties and deactivation behavior of the discharged hydrodemetallization(HDM) catalysts, which was used for 0, 162, 262 and 562 h in the fixed bed residue hydrotreating pilot unit with Yichang atmospheric residue(Yichang AR) and Saudi Arabian atmospheric residue(Saudi Arabian AR) as feedstocks, were characterized by elemental analysis of carbon and sulfur(CS), catalyst elemental analysis of nitrogen(CAT-N), thermogravimetric mass spectrometry analysis(TG-MS), and low temperature N_2 physical adsorption. Results show that more coke, less sulfur compound and more nitrogen compound deposited were formed for Yichang AR than those of Saudi Arabian AR, under the same grading HDM catalysts system and the same process conditions. In addition, more high-temperature type coke is formed on the HDM catalyst for Yichang AR, which is more difficult to be oxidized by combustion in air, with lower specific surface area and pore volume remained.
The properties and deactivation behavior of the discharged hydrodemetallization(HDM) catalysts, which was used for 0, 162, 262 and 562 h in the fixed bed residue hydrotreating pilot unit with Yichang atmospheric residue(Yichang AR) and Saudi Arabian atmospheric residue(Saudi Arabian AR) as feedstocks, were characterized by elemental analysis of carbon and sulfur(CS), catalyst elemental analysis of nitrogen(CAT-N), thermogravimetric mass spectrometry analysis(TG-MS), and low temperature N_2 physical adsorption. Results show that more coke, less sulfur compound and more nitrogen compound deposited were formed for Yichang AR than those of Saudi Arabian AR, under the same grading HDM catalysts system and the same process conditions. In addition, more high-temperature type coke is formed on the HDM catalyst for Yichang AR, which is more difficult to be oxidized by combustion in air, with lower specific surface area and pore volume remained.
引文
[1]聂红,杨清河,戴立顺,等.重油高效转化关键技术的开发及应用[J].石油炼制与化工,2012,43(1):1-6.(NIE Hong,YANG Qinghe,DAI Lishun,et al.Development and commercial application of key technology for efficient conversion of heavy oil[J].Petroleum and Petrochemicals,2012,43(1):1-6.)
[2]邵志才,贾燕子,戴立顺,等.不同类型渣油原料加氢反应特性的差异[J].石油炼制与化工,2017,48(1):1-5.(SHAO Zhicai,JIA Yanzi,DAI Lishun,et al.Characteristics difference in hydrotreating reaction of different residue feedstocks[J].Petroleum Processing and Petrochemical,2017,48(1):1-5.)
[3]张龙刚,聂红,戴立顺,等.渣油加氢反应过程中芳香性化合物转化规律[J].石油学报(石油加工),2018,34(1):34-41.(ZHANG Longgang,NIE Hong,DAILishun,et al.Transformation of different compounds during fixed bed residue hydrotreating[J].Acta Petrolei Sinica(Petroleum Processing Section),2018,34(1):34-41.)
[4]董凯,邵志才,刘涛,等.仪长渣油加氢处理反应规律的研究Ⅰ.仪长渣油性质特点及加氢反应特性[J].石油炼制与化工,2015,46(1):1-5.(DONG Kai,SHAOZhicai,LIU Tao,et al.Study on hydrotreating reactivity of Yichang residueⅠCharacterization and hydrotreating reactivity of Yichang residue[J].Petroleum Processing and Petrochemical,2015,46(1):1-5.)
[5]崔瑞利,赵愉生,于双林,等.渣油加氢脱残炭催化剂的失活研究[J].石油化工,2013,42(4):411-414.(CUI Ruili,ZHAO Yusheng,YU Shuanglin,et al.Deactivation of catalyst for removing residue carbon in hydrotreating residue oil[J].Petrochemical Technology,2013,42(4):411-414.)
[6]邹亢,徐广通,盖金祥,等.高温原位XRD和TG-MS法研究S Zorb工业吸附剂热解行为[J].石油学报(石油加工),2015,31(3):732-740.(ZOU Kang,XUGuangtong,GAI Jinxiang,et al.Study on thermal decomposition processing of commercial S Zorb sorbent by using in Situ HT-XRD and TG-MS[J].Acta Petrolei Sinica(Petroleum Processing Section),2015,31(3):732-740.)
[7]HAUSER A,STANISLAUS A,MARAFI A,et al.Initial coke deposition hydrotreating catalysts PartⅡStructure elucidation of initial coke on hydrodematallation catalysts[J].Fuel,2005,84(2/3):259-269.
[8]van DOORN J,MOULIJN J A,DJEGA-MARIADSSOU G.High-resolution electron microscopy of spent Ni-Mo/Al2O3hydrotreating catalysts[J].Applied Catalysis,1990,63(1):77-90.
[2]邵志才,贾燕子,戴立顺,等.不同类型渣油原料加氢反应特性的差异[J].石油炼制与化工,2017,48(1):1-5.(SHAO Zhicai,JIA Yanzi,DAI Lishun,et al.Characteristics difference in hydrotreating reaction of different residue feedstocks[J].Petroleum Processing and Petrochemical,2017,48(1):1-5.)
[3]张龙刚,聂红,戴立顺,等.渣油加氢反应过程中芳香性化合物转化规律[J].石油学报(石油加工),2018,34(1):34-41.(ZHANG Longgang,NIE Hong,DAILishun,et al.Transformation of different compounds during fixed bed residue hydrotreating[J].Acta Petrolei Sinica(Petroleum Processing Section),2018,34(1):34-41.)
[4]董凯,邵志才,刘涛,等.仪长渣油加氢处理反应规律的研究Ⅰ.仪长渣油性质特点及加氢反应特性[J].石油炼制与化工,2015,46(1):1-5.(DONG Kai,SHAOZhicai,LIU Tao,et al.Study on hydrotreating reactivity of Yichang residueⅠCharacterization and hydrotreating reactivity of Yichang residue[J].Petroleum Processing and Petrochemical,2015,46(1):1-5.)
[5]崔瑞利,赵愉生,于双林,等.渣油加氢脱残炭催化剂的失活研究[J].石油化工,2013,42(4):411-414.(CUI Ruili,ZHAO Yusheng,YU Shuanglin,et al.Deactivation of catalyst for removing residue carbon in hydrotreating residue oil[J].Petrochemical Technology,2013,42(4):411-414.)
[6]邹亢,徐广通,盖金祥,等.高温原位XRD和TG-MS法研究S Zorb工业吸附剂热解行为[J].石油学报(石油加工),2015,31(3):732-740.(ZOU Kang,XUGuangtong,GAI Jinxiang,et al.Study on thermal decomposition processing of commercial S Zorb sorbent by using in Situ HT-XRD and TG-MS[J].Acta Petrolei Sinica(Petroleum Processing Section),2015,31(3):732-740.)
[7]HAUSER A,STANISLAUS A,MARAFI A,et al.Initial coke deposition hydrotreating catalysts PartⅡStructure elucidation of initial coke on hydrodematallation catalysts[J].Fuel,2005,84(2/3):259-269.
[8]van DOORN J,MOULIJN J A,DJEGA-MARIADSSOU G.High-resolution electron microscopy of spent Ni-Mo/Al2O3hydrotreating catalysts[J].Applied Catalysis,1990,63(1):77-90.