渣油固定床加氢系列催化剂的研制和工业应用

介绍了FZC系列渣油加氢催化剂包括保护剂、脱金属剂、脱硫剂和脱氮剂等的特点,以及催化剂制备过程中使用的新技术。实验室评价结果表明该系列催化剂活性高、稳定性好、容金属杂质能力强,工业应用结果显示该系列催化剂具有良好的低温活性,能满足工业生产的需要。     

RUF渣油加氢脱金属催化剂载体制备

通过第一次工业试生产,较好地掌握了RUF催化剂载体滚球成型工艺.总结了各种控制因素对成型的影响,并对其原理作了透彻的剖析.生产实践表明,催化剂载体滚球成型过程中各种因素都对最后成球品质有着重要的影响,其中水量的控制、滚球转速和鼓风量是最关键的因素.滚球成型制备工艺提供了一种新的催化剂(载体)成型技术.     

PHR系列固定床渣油加氢催化剂的研制开发与工业应用

中国石油石油化工研究院通过深入研究渣油原料的结构组成与加氢转化行为特征,成功开发出包括保护剂、脱金属剂、脱硫剂和脱残炭剂4大类共12个牌号的PHR系列固定床渣油加氢催化剂。在保护剂中构建了"毫米-微米-纳米"多级孔体系,其微米级孔（PHR-402、PHR-403催化剂）与纳米级孔（PHR-404催化剂）均为双峰分布,微米级孔（PHR-402、PHR-403催化剂）主要分布在1μm附近区域和30~200μm的较宽泛区域,纳米级孔（PHR-404催化剂）的集中孔径则分别约为13nm和250nm,纳米级孔中大于100nm的孔比例达到35%。脱金属剂具有双峰分布的孔结构及内高外低的活性金属含量分布,其"扩散孔"孔径达到微米级（2300nm）,大于100nm的孔比例超过20%。工业应用结果表明,PHR系列渣油加氢催化剂具有高而稳定的脱硫、脱氮、脱残炭等活性,催化剂内部孔结构的利用率高,且床层压降更低,有利于延长装置运转周期。     

FZC-24A渣油加氢脱金属催化剂的开发

进行了FZC-24A渣油加氢脱金属催化剂开发及工业放大。以沙中常渣为原料在小型固定床加氢装置上进行了催化剂稳定性试验。结果表明,FZC-24A渣油加氢脱金属催化剂活性和稳定性优于参比剂。工业放大催化剂性能重复了小试结果。     

渣油加氢脱残炭催化剂的研制

本文介绍了渣油加氢脱残炭催化剂的开发概况。实验室和工业放大催化剂评价试验结果表明,新催化剂具有良好的加氢脱残炭能力及较高的活性稳定性。     

S-RHT渣油加氢脱金属催化剂的研制及工业应用

本文论述了渣油加氢脱金属催化剂的基本设计思路,介绍了抚顺石油化工研究院开发的FZC-20系列渣油加氢脱金属催化剂的性能及其配套催化剂在茂名S-RHT渣油加氢处理装置上工业应用标定结果。工业应用的标定结果表明,FZC-20系列渣油加氢脱金属催化剂及其配套催化剂具有良好的活性及稳定性,装置运行平稳,产品质量好,完全能满足炼厂长期生产要求。     

S-RHT新型渣油加氢保护剂和脱金属催化剂的开发

根据我国加工中东进口原油的发展需要，开发出比第一代国产保护剂和脱金属催化剂以及同类进口剂综合性能更好的S-RHT新型保护剂和脱金属催化剂。其物化性能有显著改进，脱杂质活性和稳定性明显提高。     

渣油加氢处理系列催化剂性能和工业应用

介绍了中石化抚顺石油化工研究院开发成功的第一代减压渣油和常压渣油两大系列加氢处理催化剂的性能和在工业装置上的应用情况。介绍了近几年来在该领域所取得的最新进展。     

ＦＺＣ系列常压渣油加氢处理催化剂的开发及工业应用

为提高我国的渣油加氢处理技术,抚顺石油化工研究院（ＦＲＩＰＰ）开发了ＦＺＣ系列常压渣油加氢处理配套催化剂,可用于含硫常压渣油加氢处理。工业应用结果表明,催化剂活性高、稳定性好,装置运行平稳,产品质量好,满足了用户生产使用的要求。     

Studies on recycling and utilization of spent catalysts: Preparation of active hydrodemetallization catalyst compositions from spent residue hydroprocessing catalysts

Spent catalysts form a major source of solid wastes in the petroleum refining industries. Due to environmental concerns, increasing emphasis has been placed on the development of recycling processes for the waste catalyst materials as much as possible. In the present study the potential reuse of spent catalysts in the preparation of active new catalysts for residual oil hydrotreating was examined. A series of catalysts were prepared by mixing and extruding spent residue hydroprocessing catalysts that contained C, V, Mo, Ni and Al₂O₃ with boehmite in different proportions. All prepared catalysts were characterized by chemical analysis and by surface area, pore volume, pore size and crushing strength measurements. The hydrodesulfurization (HDS) and hydrodemetallization (HDM) activities of the catalysts were evaluated by testing in a high pressure fixed-bed microreactor unit using Kuwait atmospheric residue as feed. A commercial HDM catalyst was also tested under similar operating conditions and their HDS and HDM activities were compared with that of the prepared catalysts. The results revealed that catalyst prepared with addition of up to 40 wt% spent catalyst to boehmite had fairly high surface area and pore volume together with large pores. The catalyst prepared by mixing and extruding about 40 wt% spent catalyst with boehmite was relatively more active for promoting HDM and HDS reactions than a reference commercial HDM catalyst. The formation of some kind of new active sites from the metals (V, Mo and Ni) present in the spent catalyst is suggested to be responsible for the high HDM activity of the prepared catalyst.     

渣油悬浮床加氢裂化催化剂研究

介绍了开发的水溶性和油性渣油悬浮床加氢裂化催化剂,并采用该催化剂进行加氢裂化实验。以常、减压渣油为原料,单程通过时<538　℃的馏分油收率为60％～90%,反应生成油的甲苯不溶物质量分数可以控制在1.0%以下。在催化剂开发的过程中,采用“均匀设计”软件进行实验方案的设计并对试验结果进行优化,所开发的催化剂具有较好的加氢和抑焦性能     

新一代FZC渣油加氢处理催化剂的工业应用

介绍新一代FZC系列渣油加氢处理催化剂的工业应用。新一代FZC系列渣油加氢处理催化剂性能显著提高,催化剂体系具有高的容金属能力和抗结焦能力,活性和稳定性好,能够有效保证装置长周期稳定运行,催化剂整体加氢性能显著提升。工业应用表明,新一代FZC系列渣油加氢处理催化剂能够很好满足用户要求。     

第二代常压渣油加氢脱硫催化剂的开发研制

随着市场对轻质油品的需求量上升和环保法规的日趋严格，全世界都更加关注渣油的轻质化技术。第二代常压渣油加氢脱硫催化剂采用挤条成型技术，活性组分以浸渍或完全混捏的方式加入，使催化剂成本大幅度降低，同时使最终催化剂具有高孔容、高比表面和适中堆密度，与第一代催化剂相比，活性和稳定性更好。     

补硫延长渣油加氢催化剂的寿命

在渣油加氢处理催化剂的稳态失活阶段,将含有硫化剂的馏份油送入催化剂床层,以提高循环氢中的硫含量。中试结果表明,每次补硫可大大延长催化剂的使用寿命。该工艺可应用于工业装置紧急停工后的重新开工过程中,能为炼油厂带来可观的经济效益。     

Preparation of heavy oil hydrotreating catalyst from spent residue hydroprocessing catalysts

In recent years, increasing emphasis has been placed on recycling spent hydroprocessing catalysts due to environmental regulations which list them as hazardous waste materials. In the present work, the recycling of spent residue hydroprocessing catalysts that contained high levels of vanadium was investigated by using them in the preparation of active new hydrotreating catalyst after subjecting them to different treatments such as decoking, acid-leaching and hydrothermal treatment. Catalyst extrudates containing different levels of V, Mo and Ni on Al₂O₃ were prepared by mixing the spent catalyst powder with boehmite in different proportions followed by peptization, kneading and extrusion. The prepared catalyst extrudates were characterized by chemical analysis and surface area and porosity measurements. The HDS and HDM activities of the catalysts were tested using Kuwait atmospheric residue as feed and compared with that of a reference HDM catalyst. Partial leaching of vanadium from the spent catalyst opened up the pores, and the catalyst prepared by mixing the metal-leached spent catalyst (MLSC) with boehmite had higher surface area and pore volume and showed higher hydrotreating activity than that prepared from unleached spent catalyst. Hydrothermal treatment of the spent catalyst increased its porosity and surface area. Catalysts prepared from hydrothermally treated spent catalyst (HTSC) had higher surface area and pore volume and showed higher HDM and HDS activities than that prepared from the spent catalyst without hydrothermal treatment. The catalysts prepared from the treated spent catalysts also exhibited substantially higher HDM and HDS activities than the reference commercial HDM catalyst. The results indicate that spent catalysts containing high levels of vanadium together with Mo and Ni on Al₂O₃ can be used in the preparation of active HDM/HDS catalysts, and thereby, their environmental problem can be reduced.