STRUCTURAL CHARACTERIZATION OF ARABIAN HEAVY CRUDE OIL RESIDUE

The residue (370°C+) from Arabian Heavy Crude Oil was separated into four fractions, asphaltenes, resins, aromatcis and saturates. The four fractions were found to be free of artifacts and analytically significant in themselves. Each fraction was further characterized by elemental analysis, infrared spectroscopy, n.m.r. spectroscopy and mass spectroscopy. The aromatics are the major constituent of the residue and the ratio of asphaltenes, resins, aromatics and saturates is about 2:3:8:3. The strucutral characterization study led to the conclusion that asphaltene fraction is maximum hydrogen deficient followed by resins, aromatics and saturates thus suggesting larger degree of ring condensation in the structure of asphaltenes than resins and aromatics.     

STRUCTURAL CHARACTERIZATION OF ARABIAN HEAVY CRUDE OIL RESIDUE

ABSTRACT

The residue (370°C+) from Arabian Heavy Crude Oil was separated into four fractions, asphaltenes, resins, aromatcis and saturates. The four fractions were found to be free of artifacts and analytically significant in themselves. Each fraction was further characterized by elemental analysis, infrared spectroscopy, n.m.r. spectroscopy and mass spectroscopy. The aromatics are the major constituent of the residue and the ratio of asphaltenes, resins, aromatics and saturates is about 2:3:8:3. The strucutral characterization study led to the conclusion that asphaltene fraction is maximum hydrogen deficient followed by resins, aromatics and saturates thus suggesting larger degree of ring condensation in the structure of asphaltenes than resins and aromatics.     

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.     

固定床渣油加氢处理装置催化剂积炭分析与表征

利用扫描电镜（SEM）、程序升温氧化（TPO-MS）、CHO元素分析仪等手段,对固定床渣油加氢处理装置催化剂上的积炭进行分析与表征。结果表明,沿着物料方向,渣油加氢催化剂上的积炭量呈先减少后增加的趋势,积炭的H/C原子比逐渐降低,芳香性越来越强,氧化温度逐渐增高。积炭的生成和油品中的氮化物存在着一定关系,含氮原子的沥青质更容易吸附在催化剂酸性点上并形成焦炭。     

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.     

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.     

FZC系列渣油加氢处理催化剂的开发

抚顺石油化工研究院研制开发了FZC系列渣油加氢处理催化剂，并将它成功地用于茂名石油化工公司2．0Mt／a的含硫渣油加氢处理装置。工业实践表明，该系列催化剂活性高，对渣油转化能力强，对渣油中的硫、氮、残炭和重金属有很好的脱除效果，可推广应用。     

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。     

FZC系列常压渣油加氢处理催化剂的工业应用

大连西太平洋石油化工有限公司常压渣油加氢脱硫装置自第二生产周期以来 ,采用抚顺石油化工研究院研制的FZC系列催化剂 ,经实际运行证明其活性和稳定性良好 ,总体性能与国外同类系列催化剂水平相当 ,完全可以满足装置平稳运行的要求 ,具有良好的经济效益和社会效益。     

重质油大分子在模型催化剂中扩散行为的研究

采用F127为模板剂、正硅酸四乙酯为硅源,经水热法合成了FDU-12介孔分子筛, 将其作为模型孔道催化剂用于沥青质的扩散研究。通过N2吸附-脱附、XRD、TEM、SEM等对FDU-12进行表征。结果表明：升高晶化温度能够增大催化剂孔道的入口孔径,而笼孔径不变;降低组装温度能够增大分子筛的笼孔径,而入口孔径不变。运用吸附扩散法测定了沥青质在模型孔道催化剂中的有效扩散系数,结果表明：增加模型催化剂的入口孔径和笼孔径在一定范围内能够提高有效扩散系数,但是孔径过大会导致载体的比表面积下降,使有效扩散系数降低。     

重油纳米化助燃效果研究与表征

将复配的分散剂加入重油中制备得到重油纳米颗粒，采用氧弹热值对比法对所研制的纳米化重油进行实验室评价。研究结果表明，纳米化后的重油燃烧性能得到了改善，在掺水量为3％～12％时，重油的燃烧效率提高了2．5％～6．1％。通过TEM观察，纳米化后的重油呈水包油（O／W）型乳液结构，油水界面清晰，界面膜较厚，乳化油粒径约为20～50nm，油水分散均匀，并且分散后的重油粘度增幅小，掺水量在15％以内，粘度增幅不超过20％，并且随着掺水量的增加，乳化重油的粘度逐渐减少。另外，乳化重油稳定性好，室温下至少可保存6个月，在80℃下存放3天未发生破乳现象。     

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。     

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.     

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。     

渣油加氢催化剂全蜡油硫化

首次采用全蜡油硫化工艺完成了渣油加氢催化剂的高低温硫化,避免了常规硫化工艺中柴油和蜡油之间的切换,简化了硫化过程工艺操作,并有效缩短开工时间超过20 h。通过与低温柴油硫化和高温蜡油硫化的常规硫化工艺对比,从催化剂润湿吸附温升、硫化过程反应器压差、径向温差和不均匀分布因子等方面剖析了全蜡油硫化工艺的物流分布,并分析了硫化后催化剂的加氢处理性能及反应活性。通过对比分析发现,全蜡油硫化工艺在硫化过程中物流分布均匀,硫化效果满足工艺生产要求。     

重负荷工业齿轮油的研制

对研制重负荷工业齿轮油的基础油进行了分析，着重考察了油品的极压抗磨性，抗氧化安定性，防锈抗腐性，指出了油品中保持恰当的硫、磷比值是平衡各种添加剂协合性的关键。使用大庆原油生产的高粘度指数基础油及台湾的高粘度指数１５０ＢＳ，再与添加剂进行恰当的复合而不加抗氧剂即能通过油品的抗氧化性试验。研制产品性能达到了指标要求，并且综合性能优于进口同类复合剂调制的油品，研制产品经过实际应用，用户反映良好。     

FZC-20Q系列渣油加氢脱金属催化剂的研制及工业放大

抚顺石油工研究院（FRIPP）开发的FZC－20系列渣油加氢脱金属催化剂已实现了工业化，取得良好的应用效果。为进一步提高催化剂水平，对该催化剂的外观及表面性质等进行了改进，改进后催化剂的活性评价及2000h稳定性试验结果表明，其活性及稳定性均有提高。工业放大催化剂性能重复了小试结果。     

重质费-托合成油在不同分子筛催化剂上的裂化反应性能研究

采用小型固定流化床实验装置,考察了活性组分分别为USY,Beta,ZRP分子筛的3种催化剂对重质费-托合成油裂化反应性能的影响,重点研究了不同分子筛催化剂对汽油产率及性质的影响。结果表明：USY催化剂作用下的汽油产率最高,汽油中异构烷烃质量分数高达39.87%;Beta和ZRP催化剂作用下的液化气产率分别高达52.44%和50.92%,且液化气中丙烯的浓度高。不同分子筛催化剂对重质费-托合成油催化裂化性能的差别在于其反应机理不同,重质费-托合成油在ZRP催化剂中主要发生单分子反应,而在USY催化剂中双分子反应很活跃;Beta催化剂中主要发生单分子反应,其双分子反应活性高于ZRP分子筛,但低于USY分子筛。     

常压渣油掺炼催化裂化油浆提高蒸馏拔出率的研究

考察了掺兑催化裂化油浆对常压渣油蒸馏的影响。研究结果表明,在常压渣油中掺兑一定比例的催化裂化油浆可以提高减压蒸馏拔出率,掺兑 ５％ 催化裂化油浆蒸馏,可以多获得 ３％ ～４％ 的馏分油,并使减压渣油的延度有一定程度的改善。工业试验结果重复了实验室研究结果。     

降烯烃催化剂在重油催化裂化装置上的工业应用

介绍了乌鲁木齐石化公司炼油厂 1.2Mt/a重油催化裂化装置使用LBO 12和LBO 16降烯烃催化剂的情况。工业应用结果表明 ,当前者及后者在系统藏量分别达到 78%和 10 0 %时 ,通过适当调整操作条件 ,汽油烯烃体积分数分别下降 8～ 12和 15～ 2 0个百分点 ,对比LBO 12降烯烃催化剂 ,LBO 16催化剂降烯烃能力较强 ,柴油收率增加 0 .81个百分点 ,汽油收率下降 0 .87个百分点 ,液化气收率增加 0 .90个百分点 ,汽油RON略有下降 ,诱导期延长 ,抗重金属污染能力相当。