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.     

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-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。     

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。     

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。     

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.     

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。     

多产柴油重油裂化助剂的研究开发

采用添加孔改进剂的方法。开发了具有适当的酸中心分布，稳定的中孔分布的多产柴油重油裂化助剂。该助剂对不同催化剂具有很好的适应性。固定流化床评价结果表明，在多产柴油催化剂MLC-500中加入助剂，可以在保证重油裂化能力和轻质油收率的同时，提高柴油产率。     

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。     

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.     

加氢裂化防垢剂的开发

针对加氢裂化装置进料换热器结垢比较突出的情况，在对结垢机理进行研究的基础上，开发了防垢剂ＳＦＨ－１和ＳＦＨ－Ｂ。在３７５℃和３９０℃下实验室评价的防垢率，前者分别为８９．４％和６８．１％，后者为９２．７％和７０．４％。工业应用表明，当ＳＦＨ－Ｂ加入量在１００μｇ／ｇ时，原料换热器出口温度可维持开工初期水平，防垢剂的防垢效果良好，且对加氢催化剂无不良影响。     

浅议重油催化裂化技术的进步

回顾了国内外重油催化裂化技术的重要发展情况,包括重油催化裂化工艺发展初期装置的操作情况,重油催化裂化装置反应系统构件如进料雾化喷嘴、待生催化剂汽提设备、带预汽提的旋风分离器、油气快速分离器等的改进,催化剂的发展,催化剂再生温度的控制等;同时对这些技术进步进行了分析.     

加氢裂化尾油研制25~#变压器油

加氢裂化尾油粘度指数高,低硫、低氮、杂质含量少,倾点和粘度偏高。将加氢裂化尾油切割、精制得到合适粘度的7号白油,其倾点高、光稳定不好,仍不能直接用于生产25#变压器油。实验结果表明:降凝剂PL1401、T803可使7#白油的倾点降到-25℃,对界面张力影响不大;光稳剂UV-327可以明显地改善变压器油的光稳定性,其有效添加量为0.3%~0.4%。经复合实验表明,加氢裂化尾油经切割、精制后得到的7#白油,配以抗氧剂T501、金属钝化剂T553、光稳定剂UV-327、降凝剂T803B等添加剂可以生产符合GB 2536-90要求的25#变压器油。     

DEVELOPMENT AND PERFORMANCE EVALUATION OF SURFACE-ACTIVITY POLYMER FOR OIL FLOODING

从分子结构与性能关系入手,设计了具有降低油水界面张力能力强、空间位阻较小等特点的可聚合表面活性单体.采用低温引发体系,控制聚合温度,将可聚合表面活性单体与丙烯酰胺合成了一种新型驱油用表面活性聚合物,并利用红外光谱、原子力显微镜、冷冻刻蚀电镜,对其进行了结构表征.研究表明:表面活性聚合物在不同水质中具有良好的增黏性、表面活性、热稳定性;解决了色谱分离效应,又具有降低油水界面张力的能力,界面张力可达10-1mN/m;与普通聚丙烯酰胺相比,表面活性聚合物具有较高的采收率,能在一定程度上洗掉孔道中的残余油,克服了现有调驱剂波及效率和洗油效率不能兼顾的问题.     

加氢裂化尾油研制25#变压器油

加氢裂化尾油粘度指数高,低硫、低氮、杂质含量少,倾点和粘度偏高。将加氢裂化尾油切割、精制得到合适粘度的7号白油,其倾点高、光稳定不好,仍不能直接用于生产25#变压器油。实验结果表明：降凝剂PL1401、T803可使7#白油的倾点降到-25℃,对界面张力影响不大;光稳剂UV-327可以明显地改善变压器油的光稳定性,其有效添加量为0．3％-0．4％。经复合实验表明,加氢裂化尾油经切割、精制后得到的70白油,配以抗氧剂T501、金属钝化剂T553、光稳定剂UV-327、降凝剂T803B等添加剂可以生产符合GB2536—90要求的25#变压器油。     

中东常压渣油加氢脱硫反应催化剂初期失活模型

通过试验研究了三种在加氢脱硫反应中不问性质的中东常压渣油对渣油加氢催化剂初期失活速率的影响。结果表明,原料油的芳香烃、胶质和沥青质含量及粘度是影响渣油加氢脱硫反应催化剂初期失活速率的主要因素,在此基础上建立的中东常压渣油加氢脱硫反应催化剂初期失活模型,经试验验证该模型具有可靠性,可以用于实际预测。