EVALUATION OF FEEDSTOCKS FOR DEVELOPMENT OF HYDROCRACKING CATALYSTS FOR HEAVY OIL

A number of feedstocks namely Arab Light atmospheric residue (ALAR), Arab Heavy atmospheric residue (AHAR), vacuum gas oil (VGO) and hydrotreated vacuum gas oil (HT-VGO), were evaluated for their physical and chemical characteristics. The characterization results of the feedstocks show the complex nature and composition of both residues and gas oils. The distillation results showed that about 50 weight percent of Arab Light crude consists of atmospheric residue. The elemental analysis of the ALAR showed that high amount of carbon, sulfur and nitrogen is present along with heavy metals such as nickel and vanadium. In case of Arab Heavy crude oil, the atmospheric residue is even higher, that is 57 percent and contains higher amount of metals along with more carbon, sulfur and nitrogen contents. The determination of hydrocarbon types by HPLC exhibited that ALAR contains higher amount of saturates compared to AHAR but less amount of aromatics, polars and asphaltenes. ALAR was found to have 55% saturates, 27% aromatics, 12% polars and 6% asphaltenes while AHAR has 30% saturates, 42% aromatics, 18% polars and 10% asphaltenes. Molecular weight determination indicated that the molecular weight of ALAR was determined to be 511 compared to 595 for AHAR. ALAR being lighter, showed 54% distillation at 547°C while AHAR exhibited 45% distillation at 543°C. VGO was found to have 13% saturates, 68% aromatics and 19% polars while HT-VGO had 29% saturates, 63% aromatics and 8% polars. VGO was found to have high IBP and FBP compared to HT-VGO. On the basis of the characterization data, VGO was selected to be use with catalysts containing high pore size supports such as alumina, silica alumina and clay while HT-VGO was selected as feedstock for performance evaluation of zeolite based catalysts. ALAR and AHAR will be utilized in the later stages of the catalysts development work.     

油溶性催化剂存在下委内瑞拉劣质重油悬浮床加氢活性评价

制备了一种油溶性加氢催化剂。紫外光谱（UV）和红外光谱（IR）分析结果表明,合成产物含有目标有机基团的特征吸收谱带;原子吸收光谱（AAS）分析结果表明,催化剂活性组分Mo质量分数为5.44%;油溶性试验结果显示,该催化剂不溶于水、具有良好的有机溶剂互溶性。在高压反应釜中考察了反应温度、反应压力及催化剂加入量对委内瑞拉重油悬浮床加氢活性的影响,结果表明：油溶性催化剂对委内瑞拉劣质重油的悬浮床加氢反应具有较高的催化活性;当催化剂加入量为200 μg/g、反应温度为430 ℃、反应压力为8.0 MPa时,单位生焦轻油收率达42.69%。     

重质油悬浮床加氢技术新进展

综述了重质油悬浮床加氢工艺的最新进展,并对分散型催化剂的开发进展进行了系统的总结.重质油悬浮床加氢催化剂经历了非均相固体粉末催化剂和均相分散型催化剂两个过程,均相分散型催化剂又分为水溶性分散型催化剂和油溶性分散型催化剂两类.非均相固体粉末催化剂催化活性较低,而且致使尾油中含有大量的固体颗粒,处理和利用困难较大.分散型催化剂分散度较高,比表面积大,催化活性高,性能优越,是一种较为理想的催化剂.简要介绍了中国石油天然气股份有限公司和中国石油大学联合开发的新型重油悬浮床加氢技术.     

FF-36加氢裂化预处理催化剂的研制

FF-36催化剂是抚顺石油化工研究院研制的新型加氢裂化预处理催化剂，采用改性氧化铝为载体，添加无机化合物S＋纳米级含硅化合物，具有孔体积和比表面积大、酸性适中、加氢脱氮活性高、稳定性好等特点。200mL加氢装置试验结果表明，以伊朗VGO为原料，在氢分压14．7MPa、氢油体积比1000：1、体积空速1．0h^-1的条件下，控制加氢精制油氮质量分数相近时，FF-36催化剂反应温度比FF-26催化剂低2℃。1600h的稳定性试验结果表明该催化剂的稳定性较好。     

催化裂化催化剂的配方设计及研究进展

简述了为满足新要求所做的催化剂改进技术.在催化剂配方设计过程中,炼油厂应与科研设计单位、催化剂生产单位密切合作,选择或开发适应本厂原料性质、产品方案和装置特性的催化裂化催化剂.     

FF-20加氢裂化预处理催化剂的研制

FF-20催化剂是FRIPP研制的新型高活性加氢裂化预处理催化剂。该催化剂以改性氧化铝为载体,采用一次浸渍法担载W、Mo、Ni金属组分,具有孔容大、比表面积大、孔分布集中、金属分布均匀等特点。催化剂性能评价试验结果表明：该催化剂用于加工处理国内外典型高硫蜡油,具有加氢脱硫脱氮活性高、芳烃加氢饱和能力强、稳定性好等特点,是一种性价比较高的馏分油加氢处理催化剂。     

FF-26加氢裂化预处理催化剂的研制及工业放大

考察了添加含硅、磷等元素的助剂对氧化铝孔结构和表面化学性质的影响，并采用该改性氧化铝制备出一种孔结构合理、金属分布均匀、酸性适宜的重油加氢处理催化剂FF-26。小型加氢试验装置的评价结果显示，在相同的工艺条件下，以高硫的伊朗VGO为原料，该催化剂反应温度比3936催化剂低13℃；以劣质高氮的胜利VGO为原料，该催化剂反应温度比FF-16催化剂低2℃。1700h寿命试验表明，FF-26催化剂具有良好的加氢脱氮活性和稳定性。     

FF-46加氢裂化预处理催化剂的开发与应用

为了满足加氢裂化装置加工硫、氮等杂质含量高的原料的需要,中国石化抚顺石油化工研究院采用Mo、Ni为活性金属组分,通过合适的助剂降低载体表面的强酸量,使用络合技术负载活性金属,研制出新一代具有高加氢脱氮活性的加氢裂化预处理催化剂FF-46,并在中国石化镇海炼化分公司等单位的加氢裂化装置上实现工业应用。实验室小型装置评价结果表明,FF-46催化剂活性明显优于其它技术制备的催化剂,同时也优于工业参比剂;工业应用结果表明,FF-46催化剂的脱硫、脱氮活性高, 能够满足装置长周期运转的要求。     

系列新型重油催化裂化催化剂的工业开发与应用

采用特定方法对催化剂载体和活性分子筛进行改性，制得了一系列性能良好的载体和改性分子筛，并将其应用于重油催化剂上，针对不同炼油厂原料油的实际情况及市场的需求，研制开发出了系列重油催化裂化催化剂，改变了催化剂的活性，选择性，稳定性，并在工业装置上运转，取得了较好的效果。     

石蜡基原料油加氢异构脱蜡制润滑油基础油催化剂的研制

以AEL分子筛为载体,制备出一种贵金属异构脱蜡催化剂;以n-C12为模型物,以大庆炼化加氢预精制后的650SN糠醛精制油为实际原料考察该催化剂的加氢异构化催化性能。试验结果表明,所制备的异构脱蜡催化剂对n-C12以及650SN糠醛精制油均具有良好的异构化活性和选择性,其性能优于国外同类参比剂,加工650SN糠醛精制油时,可高收率地生产出优质API Ⅲ类润滑油基础油,目标产品倾点为－21 ℃,比采用参比剂时低6 ℃,重质基础油收率为62.79%,比采用参比剂时高5.55百分点。     

重油加氢分散型催化剂的研究现状与进展

综述了重油加氢裂化分散型催化剂的研究现状与进展.重油加氢裂化分散型催化剂主要分为3大类:固体粉末添加剂、有机金属化合物及无机化合物.非均相固体粉末催化剂价格低廉,但存在活性低、加入量大,对设备磨损严重等不足,并给尾油的处理带来难度.而均相催化剂包括有机金属化合物及无机化合物,主要分为油溶性催化剂和水溶性催化剂2大类,均相催化剂可以均匀地分散在原料油中,具有较高的加氢活性.     

重油加氢裂化四集总反应动力学模型的研究

以800 kt/a重油加氢裂化装置为背景,根据加氢裂化反应机理,建立了四集总模型作为加氢裂化反应动力学模型。采用高斯-牛顿法对模型的参数进行了估计和四阶龙格-库塔法计算有初始值的常微分方程,并用现场实测数据进行了验证。结果表明:模型的计算值与实测值平均相对误差小于5%,因此该集总模型具有较高的模拟精度。     

加氢裂化尾油临氢降凝催化剂及工艺研究

以ZSM-5分子筛为载体制备了Ni/Ca/ZSM-5临氢降凝催化剂,研究了催化剂中Ni、Ca改性对润滑油基础油凝点、收率和黏度指数的影响。结果表明,Ni、Ca改性后,催化剂的裂化活性降低,润滑油基础油的收率和黏度指数升高。以加氢裂化尾油为原料,对Ni-Ca/ZSM-5催化剂进行加氢工艺考察,最佳反应条件为：反应温度310 ℃、体积空速3.0 h-1、反应压力15 MPa、氢油体积比500,在此条件下,润滑油基础油凝点为－17 ℃,黏度指数为93,收率为72%。     

超稠油氧化催化剂的制备及性能

以金属Ni、Cu、Fe的硫酸盐分别和乙酰丙酮为原料合成了3种金属盐催化剂CT1、CT2和CT3,CT1和CT2催化剂在330℃均具有很好的热稳定性。考察了在地层温度150℃下含水量、空气压力以及反应时间对稠油氧化后的酸值、吸氧量、族组成和黏度的影响。实验结果表明:氧化催化反应产物的饱和分增加、胶质降低。提高空气压力、延长反应时间以及降低含水率有助于催化氧化过程中酸性物质的生成和氧气的消耗,含水率降低容易导致稠油过度氧化而缩合生成沥青质,进而形成焦炭。CT1的催化降黏效果优于CT2和CT3。CT1注空气催化氧化稠油的适宜反应条件为:油水质量比7/3,反应压力1.0 MPa,反应时间24～36 h,在此条件下稠油降黏率大于76%。     

DEVELOPMENT OF DIRECT UPGRADING PROCESS FOR HEAVY CRUDE OIL

The direct upgrading process from heavy crude oil to sweet and light oil (IKC process) has been developed for about 10 years in Idemitsu Kosan. Compared with conventional refinery scheme consisting of YR-HDS, VGOHYC and so on, the new refinery scheme combined with IKC process and Topper was always economically feasible with lower cost and smaller energy consumption. In the existing refinery of no middle distillate HDS and residue HDS of HYC plants to supplement IKC process is expected to be one of the efficient methods to cope with the environmental regulations.     

稠油油溶性破乳剂的研制与性能评价

针对塔河稠油沥青质含量高,并含有机械杂质的特点,合成了聚丙烯酸聚醚油溶性破乳剂,考察了合成路线、丙烯酸加量、引发剂加量、滴加温度等合成条件对产品性能的影响,并与助剂复配研制了油溶性复合破乳剂RP-04。实验室动态模拟试验评价结果表明,RP-04与现场对比剂的三级脱后油的水含量分别为0.09%和0.70%,盐（NaCl）含量分别为7 mg/L和9 mg/L。破乳剂与脱盐助剂联合使用可使脱后油总氯含量从16 μg/g降低到4.9 μg/g。     

多产喷气燃料和优质尾油的国产加氢裂化催化剂工业应用

为应对市场需求变化,中国石油独山子石化分公司2.0 Mt/a加氢裂化装置于2019年换采用由中国石化石油化工科学研究院开发的国产精制剂RN-410B和RHC-133B.装置运行初期结果表明:在尾油收率为35.87％的情况下,喷气燃料收率为35.94％;与上周期相比,在相近转化深度下,喷气燃料收率增加13.05百分点,喷...     

DEVELOPMENT OF HIGH-PERFORMANCE HEAVY OIL HYDROCRACK1NG CATALYSTS: CHARACTERIZATION OF ATMOSPHERIC RESIDUE FEED

ABSTRACT

The characterization results of the atmospheric residue obtained from Saudi Arabian Light crude oil show the complex nature and composition of this material. The distillation results showed that about 50 percent of Arab Light crude is the atmospheric residue. The elemental analysis of the residue showed that high amount of carbon, sulfur and nitrogen is present along with heavy metals such as nickel and vanadium. The determination of hydrocarbon types by HPLC exhibited that 12% polars and 27% aromatics are present along with 6% asphaltenes. Nuclear magnetic resonance study conducted on the residue and its fraction provides a detailed composition in terms of aliphatic and aromatic nature of the residue and its fractions. The results showed that the residue contains 21% aromatic and 79% aliphatic carbon. The aliphatic carbon is present in saturates and as side chains of aromatic and polar molecules whereas the aromatic carbons are those in the ring structure. Asphaltenes separated from the residue were characterized for their different properties to understand its complexity. The use of electron spin resonance spectroscopy provides determination of the free radicals present in the residue. Asphaltenes were analyzed using the state-of-the-art high temperature high pressure electron spin resonance (ESR) technique in the temperature range 20 to 625 °C and at 30 and 50 bar hydrogen pressure. The ESR determination at 30 bar shows that me pressure was not enough to prevent the boiling of the asphaltene and thus a decrease in the spin concentration was observed beyond 350 °C temperature. The data at 50 bar pressure showed the adequacy of this pressure for ESR measurement. The PMRTA analysis of asphaltene showed a decrease in residual hydrogen with increasing temperature.     

延迟焦化加热炉重燃料油喷嘴的研制

基于先进的气泡雾化机理设计并试验研究了一种新型泡沫－气流多级雾化渣油喷嘴,显著地改善了雾化质量,其雾化粒度〈２０μｍ,实现了短火焰的要求,并成功解决了小流量喷嘴同易堵塞的问题,该喷嘴较好地满足了延迟焦化加热炉采用多嘴短焰,以降低炉管表面生的工艺要求。     

用油溶性双金属催化剂加氢裂化处理辽河减压渣油

用２００μｇ／ｇ（以渣油中的金属为基准）二烷基二硫代氨基甲酸钼、环烷酸镍、环烷酸铁等几种油溶性催化剂或其混合物在氢初压７．０ＭＰａ、温度４３０℃、反应时间１ｈ的操作条件下裂化处理辽河减压渣油，结果表明，双金属催化剂体系中存在着轻微的协同效应，当铁、钼（或镍）两种金属含量的质量比在２∶３附近时，协同效应最为显著，但在抑制生焦反应的同时，也降低了渣油的转化率。催化剂的活性形式是非化学计量的硫化物，在多组分体系条件下形成复合硫化物。