石蜡基减压渣油生产光亮油技术研究

对石蜡基减压渣油的性质进行了分析并进行了丙烷脱沥青试验,以样品C为原料,在石蜡基润滑油工业装置催化剂体系和主要工艺条件下进行了加氢处理试验并对样品G的产品分布和产品性质进行了分析,并对其≥480℃的馏分进行了酮苯脱蜡试验。结果表明:石蜡基减压渣油蜡含量8.8%,残炭、硫含量和氮含量相对适中,金属含量较低;随着抽提温度的升高,轻脱油的收率逐渐降低,残炭逐渐减小;随着加氢处理温度的降低,产品的密度、运动黏度和硫含量逐渐降低;酮苯脱蜡所得样品基本满足150BS指标要求,但硫含量偏高,可对石蜡基润滑油装置现有催化剂体系进行相应调整。     

委内瑞拉减压渣油的热解特性及其动力学研究

采用热重-质谱(TG-MS)联用对委内瑞拉减压渣油在不同升温速率下进行热解实验,研究其热解反应特性,并采用3种等转化率法和分布活化能模型(DEAM)求取减压渣油热解反应的动力学参数。实验结果表明,委内瑞拉减压渣油的热解主要反应温度区间为179～490℃,总质量损失率为77.54%,质量损失峰值在446℃达到最大,最大质量损失速率为317.38μg/min。Flynn-Wall-Ozawa(FWO)法比其他2种等转化率法能更好地描述减压渣油的热解过程,由其计算得到的热解活化能为56.77～178.91 kJ/mol。进一步采用DEAM模型将减压渣油分为4个假定组分,对升温速率为10℃/min条件下的热重分析(TG-DTG)数据进行分峰拟合,求得饱和分、芳香分、胶质和沥青质四组分动力学参数,并据此获得减压渣油总活化能分布曲线。结果表明,委内瑞拉减压渣油活化能主要集中在100～250 kJ/mol范围内,通过加权求和获得平均活化能为190.11 kJ/mol。     

石蜡基减渣C_3溶剂脱沥青工艺研究

中国石油克拉玛依石化公司石蜡基减渣饱和烃含量高,沥青质含量少,可通过溶剂脱沥青工艺生产石蜡基轻脱油,为30万t/a润滑油高压加氢装置提供优质原料,用以生产高粘度指数Bs光亮油.文章通过C3溶剂脱沥青试验,考查了抽提温度、溶剂比等工艺条件对脱沥青油性质及收率的影响.实验证明,通过脱沥青工艺,在压力4.2 MPa,溶剂比7:1,抽提温度为70℃条件下可以得到收率42%的、满足高压加氢进料要求的石蜡基轻脱油原料.     

减压渣油生产环保橡胶油与重交沥青的研究

以环烷基减压渣油为原料,通过丙烷脱沥青、糠醛精制与沥青调合工艺生产环保橡胶油与重交沥青。研究结果表明:以环烷基减压渣油为原料,通过丙烷脱沥青可以得到品质较好的轻脱沥青油及脱油沥青;以轻脱沥青油为原料,通过单塔糠醛精制可以生产CA值13%以上的环保橡胶油,通过双塔糠醛精制可以生产CA值23%以上的高芳环保橡胶油;以脱油沥青为原料,通过沥青调合工艺,可得到满足交通部A级道路石油沥青指标要求的50号和70号重交沥青。     

超声辐照法原油破乳脱水的室内研究

用一台功率1kW的超声波发生器，在声强0．65W／cm^2，频率20kHz，脉冲宽度97ms，间歇比3：1条件下，在55℃将江苏真武含水原油（800mL)辐照10min，静置沉降脱水，同时与自然沉降，化学破乳（破乳剂加量100mg/kg)，化学破乳＋超声辐照破乳等方法作了对比，超声辐照法的初期脱水速率高于化学破乳法，最终（360min)脱水率略高（60．8％对59．4％），化学破乳＋超声辐照法的初期脱水率高于化学破乳法但低于超声辐照法，最终脱水率提高至71．3％，超声辐照法脱出水含量量（17．67mg/L)比自然沉降法（56．32mg/L)，化学破乳法（42．58mg/L)和超声辐照＋化学破乳法（33.97mg/L)均有大幅度降低，与自然沉降法脱出水相比，超声辐照法脱出水中TGB，SRB，铁细菌数分别降低62．0％，52．6％，36．7％，讨论了超声辐照对含水原油破乳 脱水过程的影响。     

减压渣油热转化集总动力学的建模研究

以洛阳减压渣油为例,研究了减压渣油热转化集总动力学模型.对洛阳减压渣油分别在410、420、430和440℃下进行的热转化反应,通过数学分析建立了6集总动力学反应模型.减压渣油热转化反应生成裂化气、汽油、轻瓦斯油、重瓦斯油与焦炭,其反应均为2级反应;轻、重瓦斯油将继续发生2次反应,生成焦炭;动力学参数中缩合反应的活化能大于裂化生成馏分油的活化能,表明缩合反应对反应温度的变化更为敏感.计算结果表明,所建模型可以用来预测减压渣油热转化反应产物分布,预测值与实验值吻合较好.     

Kinetic Study on the Hydrocracking Reaction of Vacuum Residue Using a Lumping Model

Abstract

Based on the experimental hydrocracking of vacuum residue, a kinetic study using a lumping model was carried out to gain insight into the characteristics of catalytic reactions. The lumped species were the saturates, aromatics, resins, and asphaltenes (SARA) constituents in the residue (798 K⁺) fraction and gas, naphtha, kerosene, gas oil, vacuum gas oil, and coke in the products. The pyrite reaction favoring hydrocracking to lighter products was more temperature-dependent than that using a mixture of pyrite and active carbon. The kinetic study showed that the addition of active carbon to pyrite limited the transformation of resins to asphaltenes.     

大庆减压渣油加氢裂化水溶性催化剂分散性研究

采用不同的分散方式及分散方法，考察了大庆减压渣油加氢裂化水溶性催化剂的分散效果。建立了分散性能参数来评价水溶性催化剂在渣油中分散效果的优劣。实验结果表明：水溶性催化剂的催化活性随其分散度的增加而增大，分散度增加，颗粒度减小，比表面积增大，因此活性增加。分散方式和分散方法对加氢裂化的影响很大，而分散时间和速度超过一定的值后对催化剂的分散效果影响不大。研究发现，分散性能参数与渣油加氢裂化结果存在相关性。     

减压渣油胶体稳定性的分子模拟研究

分子结构特性决定分子间相互作用,进而决定其溶解性能。通过分子模拟研究减压渣油不同结构分子的分子间相互作用、互溶性及由此导致的渣油胶体稳定性。研究表明,芳环数目越多、烷基侧链越短的分子结构内聚能密度越大,溶解度参数越大。在渣油体系中,沥青质、重胶质分子聚集形成胶核,饱和烃、芳香烃、轻胶质分子形成连续相。胶质分子结构影响其胶溶性能,侧链长度适中的胶质分子,其与沥青质、芳香分互溶性好,胶溶性能优异;沥青质的聚集程度随胶质分子含量的增加而降低。芳香分、胶质分子的协同作用使沥青质、饱和烃分子稳定存在于同一体系中,因此渣油胶体稳定性取决于不同分子结构的连续性和配伍性。     

Kinetic Study on the Hydrocracking Reaction of Vacuum Residue Using a Lumping Model

Based on the experimental hydrocracking of vacuum residue, a kinetic study using a lumping model was carried out to gain insight into the characteristics of catalytic reactions. The lumped species were the saturates, aromatics, resins, and asphaltenes (SARA) constituents in the residue (798 K⁺) fraction and gas, naphtha, kerosene, gas oil, vacuum gas oil, and coke in the products. The pyrite reaction favoring hydrocracking to lighter products was more temperature-dependent than that using a mixture of pyrite and active carbon. The kinetic study showed that the addition of active carbon to pyrite limited the transformation of resins to asphaltenes.     

减压渣油微观相结构特性的分子模拟

选用4种模型化合物代表减压渣油四组分(SARA),采用分子动力学模拟了减压渣油微观相结构,发现不同结构分子间相互作用的差异是减压渣油微观非均匀分布的本质原因,并通过电子分布特性分析了不同结构分子间相互作用差异的本质原因。沥青质分子间强相互作用使得沥青质分子自缔合形成聚集体;而多个胶质分子与沥青质分子的强相互作用封闭了沥青质分子自身进一步发生相互作用的活性位;同时,与胶质分子、饱和烃分子具有强相互作用的芳香烃分子将沥青质 胶质分子形成的聚集体分散在由芳香烃 饱和烃分子构成的连续相内,其中芳香烃分子更靠近胶质分子。因此,增加沥青质、饱和烃分子的含量会促进沥青质聚集,降低减压渣油稳定性;增加胶质、芳香烃分子的含量会阻碍沥青质聚集,提高减压渣油稳定性。     

超声波处理对渣油物性的影响

以四种不同来源和属性的渣油为原料,研究了超声波处理前后渣油基本物性和结构参数的变化,并对超声波处理前后渣油的加氢效果进行了对比研究 。结果表明：经超声处理后渣油的平均相对分子质量减小,粘度降低,密度基本不变;SARA四组分中,饱和分、芳香分和沥青质含量均减小,胶质的含量增加,胶质和沥青质的总含量增加;沥青质含量越高,经超声处理后胶质增加量越多,饱和分减少量越小,芳香分减少越大。超声波处理使渣油的平均分子总碳数C、芳环上的碳数CA、总环数RT、芳环数RA、环烷环数RN均减小,重油特征化参数KH增大,超声波处理改变了渣油的平均结构。沥青质含量和结构的变化是超声波处理引起渣油物性变化的最主要原因。     

Soil Microbial Degradation of Vacuum Residue

Abstract

The effect of microbial consortia on the alteration of petroleum residual structure and portions was studied, which can propose an alternative or complementary method for stringent upgrading heavy crude oil methods, which consist of heavy and complex hydrocarbons. Biological processing of petroleum heavy fractions and residua may provide an alternative or complementary process in refining heavy crudes—the dominant refinery feed in the future—with less severe process conditions and higher selectivity to upgrade heavy fractions of crude oil. The primary objective was to observe the ability of an indigenous bacterial consortium taken from a soil bellow the vacuum column contaminated with vacuum residue (VR) for several decades from the Tehran refinery distillation unit, in degradation of residua components. Enrichment with VR, as sole source of carbon and energy, is the selected biosurfactant-producing microbial consortium. The biodegradation of net VR using indigenous consortia from this specific ecosystem was studied. The considered period of biodegradation of these heavy hydrocarbons was remarkably shorter than usual studies. Bacterial growth and VR biodegradation ability of this consortium analyzed with SARA test in 20 days. Studying the inoculum size and aeration effect revealed the significance of oxygen for this consortia activity and the similarity of 7% and 5% inoculation on alteration percentage of alkane, aromatic, and asphaltene and resin in VR. Results study revealed a 30.4%, 6.9%, and 9.4% decrease in the asphaltene, aromatics, and saturated aliphatic contents of VR, respectively, in only 20 days in 30°C at 150 rpm.     

减压渣油热反应行为的实验研究

在氢气气氛下用非等温方法考察了沈北、孤岛、南阳、草桥和辽河减压渣油的热反应行为,研究发现：在渣油热转化的两个温度区间内,采用分段一级动力学模型较好地拟合了实验数据,确定了渣油在两个温区内的动力学参数;本实验条件下,氢气气氛基本上不影响渣油的热转化。     

Determination by PIXE of the Metallic Content in Vacuum Residue,Asphaltenes and Maltenes

Abstract

Asphaltenes from Mexican Maya crude oil were precipitated during one agitation hour using n-C₅, n-C₆, n-C₇, and n-C₈ at room temperature. Later the asphaltenes were washed with a soxhlet extraction system during 24 hr to remove the maltenes. The characterization of the vacuum residue, asphaltenes, and maltenes was realized using proton induced x-ray emission (PIXE) for the direct determination of the distributions and abundances of metals in the vacuum residue and their respective fractions. The analysis revealed that vacuum residue contains Fe, Al, V, and Ni, while the asphaltenes and maltenes mainly contain V and Ni.     

Determination by PIXE of the Metallic Content in Vacuum Residue, Asphaltenes and Maltenes

Asphaltenes from Mexican Maya crude oil were precipitated during one agitation hour using n-C₅, n-C₆, n-C₇, and n-C₈ at room temperature. Later the asphaltenes were washed with a soxhlet extraction system during 24 hr to remove the maltenes. The characterization of the vacuum residue, asphaltenes, and maltenes was realized using proton induced x-ray emission (PIXE) for the direct determination of the distributions and abundances of metals in the vacuum residue and their respective fractions. The analysis revealed that vacuum residue contains Fe, Al, V, and Ni, while the asphaltenes and maltenes mainly contain V and Ni.     

大港减渣超临界萃取物的FTIR分析

通过大量的溶剂选择性实验,选取对大港减渣的16个超临界萃取物都具有优异溶解性能的环己烷为良性溶剂,并对每个萃取物分别进行KTIR分析,探索大港减渣所含基团的规律性。分析结果表明,不同大港减渣超临界萃取物的红外光谱图有一定的类似性,说明其含有的基团接近;大港减渣超临界萃取物含有10余种官能团,其中烷烃的含量最大;不同萃取物中同一种基团的含量不同。     

Thermal Hydrocracking Kinetics of Chinese Gudao Vacuum Residue

Abstract

The thermal hydrocracking kinetics of Chinese Gudao vacuum residue was studied in a batch autoclave reactor. The temperature ranged in 390–435°C and the initial hydrogen pressure was 7.0 MPa at 20°C. Ammonium phosphomolybdate (APM) in its dispersed phase was the catalyst. The reaction products, gas, naphtha, atmospheric gas oil (AGO), vacuum gas oil (VGO) and coke, were separated during and after experiments, and their yields vs. reaction time were obtained, for four reaction temperatures: 390, 405, 420, and 435°C. The activation energy was calculated from a traditional kinetic model to be 218.6 kJ/mol. A new kinetic model was proposed in this work that allows for the calculation of activation energy with a minimum number of three tests, each at a different temperature. This is comparable to the traditional model which requires a minimum of 12 tests; a minimum of four tests for one temperature and a minimum of three temperatures. The activation energy calculated from the new model with four tests is 229.6 kJ/mol, only 5% greater than that obtained from the traditional model. The reaction rate constants obtained from this model are also consistent with those from the traditional model.