降低汽油硫含量MIP工艺专用催化剂鉴定

由中国石化石油化工科学研究院和中国石化沧州分公司、中国石化催化剂齐鲁分公司共同完成的“降低汽油硫含量MIP工艺专用催化剂CGP-2的开发和工业应用”项目，通过了中国石化股份公司科技开发部组织的技术鉴定。CGP-2催化剂中添加了选择吸附硫化物的酸碱对，可使MIP-CGP工艺第二反应区积炭后的催化剂具备了较好的焦炭选择性和更高的水热稳定性，可满足MIP-CGP催化裂化工艺双反应区，尤其是第二反应区降低催化裂化汽油烯烃同时降低汽油硫含量的需求。     

降低催化汽油硫含量助剂MS012荆门工业应用

石油化工科学研究院在第一代降硫助剂MS011的基础上,进一步对助剂的降硫组分的复配,以及助剂中不同降硫组分对主催化剂的影响进行了研究,开发出新一代降低催化裂化汽油硫含量助剂MS012。在中石化荆门分公司的应用表明:在稳定汽油的干点从185℃增加到197℃的情况下,汽油硫质量分数从5、6月平均780(mg/kg)降低到8、9月平均620(mg/kg),催化汽油收率的提高明显增加了装置的经济效益。     

安庆石化60万t／a蜡油加氢脱硫装置工业运行总结

介绍了安庆石化分公司60万t/a蜡油加氧脱硫装置改造及生产运行情况.工业运行结果表明,催化裂化装置进料经过加氢脱硫后,降低了催化裂化汽油的硫含量,从而使全公司汽油硫含量能够满足汽油新标准的要求.     

LTAG技术在齐鲁分公司催化裂化装置的应用

中国石化齐鲁分公司胜利炼油厂采用石油化工科学研究院开发的LTAG技术,在齐鲁3~#催化裂化装置进行工业应用。结果表明:实施LTAG技术后,催化裂化装置汽油收率升高4.91%,柴油收率降低7.36%。加氢LCO转化率、LPG选择性和汽油选择性分别为57.45%、7.21%和66.65%。催化裂化装置所产的稳定汽油性质变好,柴油性质没有明显变化。LTAG技术达到了压减催化柴油、多产汽油、降低柴汽比的目的。     

脱除催化裂化汽油中硫含量的技术及其新进展

介绍国外在降低催化裂化汽油中硫含量的技术及其新进展。包括新的催化剂和助剂技术、膜分离、Unipure ASR汽油氧化法工艺及传统的选择性加氢工艺等。并指出加大新型高效催化剂及助剂的研制与开发,与膜分离技术、选择性加氢技术等相结合．将是解决汽油中硫含量的长期对策：根据不同技术的特点优化装置配置,确定最佳的方案进行汽油调和,是满足不同阶段的清洁汽油中硫含量标准的一条经济的、有效的途径。     

降低FCC柴汽比技术开发及应用

针对成品油市场需求及环保要求的变化,开发了降柴汽比裂化催化剂和(加氢)催化柴油回炼技术,满足降低催化裂化装置柴汽比目的。该技术应用于中国石油化工股份有限公司长岭分公司两套催化裂化装置,工业应用结果表明两套催化裂化装置催化柴油产率大幅降低,汽油及液态烃收率提高,有效降低了装置的柴汽比。     

OCT-M催化裂化汽油选择性加氢脱硫技术的工业应用

介绍了由中国石化抚顺石油化工研究院开发的OCT-M催化裂化汽油选择性加氢脱硫技术特点及其在中国石化武汉分公司400 kt·a^－1OCT-M装置进行工业应用试验的情况。标定结果表明,FCC汽油硫含量由727～794 μg·g^－1降低到80～90 μg·g^－1,研究法辛烷值损失0.4～0.5个单位,取得了较好结果。     

催化汽油选择性加氢脱硫技术OCT-MD的工业应用

介绍了抚顺石油化工研究院开发的OCT-MD催化裂化汽油选择性加氢脱硫技术的特点及其在中国石化镇海炼化分公司0.7 Mt/a OCT-MD装置进行工业应用的情况,标定结果表明,FCC汽油的硫含量由308～483μg/g降低到50μg/g左右,辛烷值(RON)损失0.4～0.8个单位,工业应用取得了较好的效果。     

洛阳石化工程公司研制出新型脱硫助剂

日前，一种用于降低催化裂化汽油硫含量的新产品LDS-S1脱硫助剂，在河南洛阳石化工程公司成功问世。催化裂化汽油生产采用该助剂后，在保持系统藏量8％至10％比例时，催化汽油硫含量可有效降低25％至30％。     

分子筛催化剂在中国台湾省桃园炼油厂的工业应用

中国石化石油化工科学研究院和中国石化催化剂长岭分公司合作开发的以PSRY和REUSY分子筛为主要活性组元的CC 20D型催化裂化催化剂在中国台湾省中油公司（CPC）桃园炼油厂催化装置应用成功。结果表明,和国外催化剂相比,轻油加液化气收率提高1.05个百分点,丙烯产率提高1.38个百分点,转化率提高4.93个百分点,研究法汽油辛烷值达94.0。     

MAC催化剂在玉门催化装置上的应用

中石油玉门炼油厂催化装置采用两段提升管设计,装置长期存在剂耗高,催化剂自然跑损量大,烟机入口粉尘浓度高的问题,严重影响装置长周期运行。2019年5月开始应用由中石化催化剂长岭分公司采用新型粘结剂及载体技术设计的MAC专用剂,结果表明,当新剂藏量达到70%时,汽油及液化气收率提高,总液收增加,催化剂跑损量减少,油浆固含量及烟机入口浓度降低,催化剂单耗降低,有利于装置安全长周期运行。     

催化裂化原料加氢预处理催化剂的研制

为满足FCC原料预处理的要求,开发了一种高脱硫、脱氮活性的FCC原料预加氢处理催化剂。该催化剂以氟改性氧化铝为载体,Ni Mo为活性组分,比表面积为169 m2·g-1,孔容为0.31 m L·g-1,平均孔径为6.5 nm,最可几孔径为3.35 nm和8.00 nm,孔径(4~10)nm占71%,具有大孔容、高比表面积和活性金属组分分散性好等特点。在100 m L固定床加氢试验装置上,以中国石化青岛炼化公司的高硫低氮混合蜡油和江苏新海石化有限公司的高硫高氮焦化蜡油为原料进行加氢活性评价。结果表明,在反应温度370℃、反应压力10.0 MPa、空速1.0 h-1和氢油体积比700∶1条件下,高硫低氮混合蜡油的脱硫、脱氮率分别为98.0%和96.5%,对高硫高氮焦化蜡油的脱硫、脱氮率分别为93.2%和90.0%。催化剂表现出原料适应性强,能有效脱除原料中的硫氮化合物,具有较高的加氢活性。     

YD-CADS汽油超深度催化吸附脱硫技术中试研究

陕西延长石油（集团）有限责任公司炼化公司和中国科学院大连化学物理研究所共同开发的YD-CADS汽油固定床超深度催化吸附脱硫组合技术,以全馏分FCC汽油为原料生产超低硫清洁汽油,采用脱二烯烃和催化吸附脱硫串联固定床工艺,具有流程短、投资低、占地少和操作简单等优点。中试结果表明,处理硫含量约100 μg·g^-1的FCC汽油时,汽油产品硫含量小于10 μg·g^-1,烯烃饱和小于2%,研究法辛烷值损失小于0.8个单位,目的产品汽油收率大于99%,化学氢耗小于0.2%。     

Behavior of sulfur species present in atmospheric residue in fluid catalytic cracking

The selective removal of sulfur species in atmospheric residue (AR) is strongly wanted since the species of the hydrodesulfurized AR (HDS-AR) define the sulfur content of the product gasoline in the subsequent fluid catalytic cracking (FCC). Hence, the correlations between sulfur species in HDS-AR and FCC gasoline were explored in the present study. HDS-AR was fractionated into vacuum gas oil (VGO) and vacuum residue (VR) by distillation. Reactivities of HDS-AR (S = 3000 mass ppm) and its VGO (S = 900 mass ppm) were measured by micro activity test to clarify which fractions and sulfur compounds in HDS-AR were converted into gasoline and its sulfur species. The yields and sulfur contents of the product gasoline were 45.0 mass% and 52 mass ppm from HDS-AR and 47.7 mass% and 14 mass ppm from VGO, respectively. The sulfur content of the gasoline from HDS-AR was markedly higher than that from HDS-VGO. The saturate and aromatic fractions in HDS-AR are mainly converted to the gasoline in the FCC process, providing similar gasoline yields from HDS-VGO and HDS-AR. Thiophene, methylthiophenes, and benzothiophenes were major sulfur species in both gasolines from HDS-AR and HDS-VGO. Such sulfur species are concluded to be derived from benzothiophenes in VGO and dibenzothiophenes in VR fractions, respectively through hydrogen transferring ring opening and dealkylation during FCC. Sulfur compounds are also produced from H₂S and olefins in FCC, increasing the sulfur content in the product gasoline. The larger sulfur content in the gasoline from HDS-AR than that from HDS-VGO is ascribed to more H₂S being produced during the FCC process as well as dibenzothiophenes being present in the feed.     

催化裂化汽油降硫剂的制备与应用

为降低汽油硫含量,以锌和镧为有效元素合成了催化裂化汽油脱硫钝化剂,在催化裂化装置上进行了工业应用试验。结果表明,当加入量为300×10^-6时,汽油中总硫可以从204×10^-6降低到140×10^-6,脱硫率达36.37%;当加入量为（500～600）×10^-6时,脱硫率可达到50%以上。汽油中的噻吩硫主要以硫化氢形态转移至干气、液化气中。脱硫钝化剂对平衡催化剂的主要性质和FCC产品分布没有明显影响,亦有良好的金属钝化效果。     

新型催化裂化重油助剂ECA-100的开发与应用

以原位晶化技术与半合成加工工艺有机结合的ISCT技术为核心制备新型催化裂化重油助剂ECA-100,ECA-100具有分子筛含量高、活性高、重油转化能力强、焦炭选择性好、液收和轻质油收率高、汽油烯烃含量低和辛烷值高等特点,具有高抗磨损能力和良好抗重金属污染能力。在河北大港石化公司和广东天乙集团有限公司工业应用表明,ECA-100助剂是性能优良的高活性催化裂化重油助剂。     

INTEGRATING ALBEMARLE RESOLVE DESULFURIZATION TECHNOLOGY WITH NOVEL PETRO-CANADA PROCESS CONCEPTS IN COMMERCIAL FCCU OPERATIONS

The gasoline and distillate sulfur regulations promulgated throughout the world to reduce tail-pipe emissions are now strongly impacting refinery operations and investments. FCC gasoline is recognized as the principal contributor of sulfur to the gasoline pool and has become the focus for meeting the new specifications. The difficulty in removing sterically hindered sulfur species in the fluid catalytic cracking unit (FCCU) cycle oil drives up the hydrogen and investment costs for treating the distillates. Although installation of pre- and post-treatment facilities is planned by many refiners, other non-capital approaches such as undercutting are being evaluated to meet interim and future sulfur levels. Even when expensive treatment facilities are installed, operating costs can be lowered and the flexibility of the facility increased with improvements in the ability to remove sulfur in the FCCU. In this article, we detail Petro-Canada's experience in integrating Albemarle's RESOLVE sulfur reduction technology with a combination of innovative process ideas. These concepts include heavy naphtha recycle, coprocessing of hydrogen donor feeds, and recycle of light cycle oil (LCO) to a specially designed stripper reactor. Special attention is paid to the interaction of deep FCC feed hydrodesulfurization with the FCC performance. The results demonstrate that very low FCC gasoline sulfur levels can be achieved without significant capital investment through novel approaches to recycle, creative integration of cat feed hydrotreating unit (CFHTU)-FCCU designs and operations, and application of state-of-the-art sulfur reduction additive technology. An added benefit of the RESOLVE 950 sulfur reduction technology is the substantial elimination of sulfur oxides in the FCC flue gas. This has been observed in Petro-Canada operations and numerous other RESOLVE 950 applications around the world.     

焦化液化气脱硫醇工艺技术改造

天津石化在炼制高硫原油时,焦化液化气胺脱后总硫高达16000mg／Nm3,导致原焦化液化气脱硫醇装置的产品不合格,产品总硫在1000mg／Nm3左右,在作为民用燃料销售时需要掺兑硫含量较低的催化液化气或降低价格,严重影响了天津石化的经济效益。为此,中石化炼油事业部组织SEI、天津石化和河北精致有限公司进行了长达2年的攻关和优化改造,采用液化气深度脱硫专利技术,成功解决了焦化液化气硫形态复杂、脱除难的问题,脱硫后焦化液化气总硫降低到100mg／Nm3以下,达到通过气体分馏装置生产合格丙烯的要求,成为中石化焦化液化气深度脱硫和利用的首个成功案例。     

INTEGRATING ALBEMARLE RESOLVE DESULFURIZATION TECHNOLOGY WITH NOVEL PETRO-CANADA PROCESS CONCEPTS IN COMMERCIAL FCCU OPERATIONS

The gasoline and distillate sulfur regulations promulgated throughout the world to reduce tail-pipe emissions are now strongly impacting refinery operations and investments. FCC gasoline is recognized as the principal contributor of sulfur to the gasoline pool and has become the focus for meeting the new specifications. The difficulty in removing sterically hindered sulfur species in the fluid catalytic cracking unit (FCCU) cycle oil drives up the hydrogen and investment costs for treating the distillates. Although installation of pre- and post-treatment facilities is planned by many refiners, other non-capital approaches such as undercutting are being evaluated to meet interim and future sulfur levels. Even when expensive treatment facilities are installed, operating costs can be lowered and the flexibility of the facility increased with improvements in the ability to remove sulfur in the FCCU. In this article, we detail Petro-Canada's experience in integrating Albemarle's RESOLVE sulfur reduction technology with a combination of innovative process ideas. These concepts include heavy naphtha recycle, coprocessing of hydrogen donor feeds, and recycle of light cycle oil (LCO) to a specially designed stripper reactor. Special attention is paid to the interaction of deep FCC feed hydrodesulfurization with the FCC performance. The results demonstrate that very low FCC gasoline sulfur levels can be achieved without significant capital investment through novel approaches to recycle, creative integration of cat feed hydrotreating unit (CFHTU)-FCCU designs and operations, and application of state-of-the-art sulfur reduction additive technology. An added benefit of the RESOLVE 950 sulfur reduction technology is the substantial elimination of sulfur oxides in the FCC flue gas. This has been observed in Petro-Canada operations and numerous other RESOLVE 950 applications around the world.     

OCT-ME技术生产“无硫汽油”工业应用

为了满足在辛烷值损失较小的情况下生产"无硫汽油",抚顺石油化工研究院开发出了OCT-ME催化汽油选择性加氢脱硫技术。2012年,首套OCT-ME装置在中国石化湛江东兴石油化工有限公司成功工业应用,标定结果表明OCT-ME技术将FCC汽油硫质量分数由平均466μg/g降低到9.7μg/g,RON损失1.8个单位,表明OCT-ME技术能够满足我国炼厂生产"无硫汽油"的需要。