重质油在加工过程中结构基团转化规律的实验验证

按照结构基团理论,将石油馏分的化学组成划分为芳烃、环烷烃、烯烃和非烃元素等结构基因,其中芳烃和环烷烃还按照其环分布划分为若干个亚族基因。在重质油加工过程进行的化学反应都视为基团间或基因本身发生的反应。在大量的工业装置和实验室中试研究数据的基础上,对催化裂化、延迟焦化和加氢裂化工艺过程中原料油和产品之间的化学结构变化规律进行了研究,验证了结构基团理论的可行性,剖析了３个主要的重质油加工过程的化学本质和工艺特征,有利于炼油厂在进行重质油加工时选择合理的技术路线。     

NMR Fingerprinting of Chemical Changes in Asphalt Fractions on Oxidation

Abstract

The composition of asphalt has been the subject of much study because such data are required in determining its performance-related properties. A problem inherent in studying asphalt composition is its chemical complexity; however, the characterization of asphalt can be better achieved by separating into fractions. In this work, the chemical property of commercial-grade asphalt obtained from BAPCO refinery, Bahrain (BH), was carried out. The rolling thin-film oven (RTFO), used for short-term aging, and pressurized aging vessel (PAV), used for long-term aging, ASTM D4124 (1991) method was used to separate fresh and aged asphalt into four generic fractions such as asphaltenes, polar aromatics, naphthene aromatics, and saturates. The Corbett fractionation procedure was used to separate fresh and aged asphalt into four generic fractions such as asphaltenes, polar aromatics, naphthene aromatics, and saturates. Nuclear magnetic resonance (NMR) was employed to fingerprint the chemical changes that occurred in asphalt during the aging processes. NMR measurements of asphalt fractions showed that during aging, isomerization and dehydrogenation types of reactions took place. Significant differences were observed between the structure and composition of fresh and aged fractions of asphalt. Results from NMR spectrometry provided significant information concerning the chemical transformations that occurred during the aging processes.     

NAP10环保轮胎橡胶油

环保轮胎橡胶油通常是指IP346方法测定的DMSO抽出物——稠环芳烃PCA小于3%的橡胶操作油或者填充油,是无毒、绿色轮胎制品的重要原材料。中国石油克拉玛依石化公司率先应用重质环烷基馏分油经溶剂精制或者加氢精制、有效选择性脱除稠环芳烃PCA的工艺制备,开发出NAP10环保轮胎橡胶油产品,具有环烷烃含量高,与稀土顺丁橡胶、天然橡胶配合良好,有较好的耐曲挠、降压缩生热的能力,能显著降低滚动阻力等特点;可应用于轮胎制品部件及顺丁橡胶、溶聚丁苯橡胶的充油胶产品制造。该产品在国内首次实现了环烷基的轮胎油在轮胎橡胶行业的应用,并率先在国内获得欧盟环保检测认证。     

重油蒸馏过程中物料黏度变化的应用

考察了多种原油的渣油在不同蒸馏过程中运动黏度的变化,提出了收率等效黏度（Recovery equivalent viscosity,REV)、黏衰率（Viscosity reduce rate,θ）的概念,为重质油品馏程测定和深拔研究提供了新的研究手段。结果表明,大庆渣油的各种蒸馏过程皆具有典型的石蜡基裂解型特征;非典型石蜡基及多数中质中间基常压渣油减压蒸馏过程后产物体系总黏度下降,构成了中间基裂聚型特征。环烷基及偏环烷基常压渣油减压蒸馏过程后产物体系总黏度下降,构成了环烷基裂解型特征。重质中间基及个别环烷基常压渣油减压蒸馏过程后产物体系总黏度上升,构成了重质中间基或环烷基缩聚型特征。     

直馏柴油催化裂化生产轻质芳烃的研究

采用小型固定流化床催化裂化装置,考察了分子筛类型和反应条件对直馏柴油催化裂化反应的影响以及不同烃类组成的直馏柴油催化裂化产物分布特点。结果表明:选用富含环烷烃和单环芳烃的直馏柴油有利于提高轻质芳烃收率;在Y型分子筛催化剂作用下的直馏柴油催化裂化转化率最高,轻质芳烃收率可达13.22%;反应温度对轻质芳烃收率影响显著,反应温度由510℃提高到610℃时,转化率增加12.95百分点,轻质芳烃收率增加7.16百分点,提高原料的转化深度有利于增加轻质芳烃收率,但是汽油收率降低;剂油比对轻质芳烃收率影响较小,剂油比过高时,汽油收率下降。与直馏柴油相比,其催化裂化产物烃类组成中环烷烃质量分数减少26.4百分点,环烷烃参与反应的比例高达80.49%,环烷烃环数越多,参与反应的比例越高。     

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.     

辽河超稠原油加工方案的初步研究

为合理充分利用辽河油田曙－区超稠原油对其性质做了综合评价。结果表明,此原油蜡含量低,胶质和沥青含量高,属低硫环烷基原油,是生产道路沥青的优质原料。根据原油性能,提出了利用此原油的加工方案,指出用它作原料生产高等级道路沥青是最佳的加工方案,选取炼油厂贫蜡富芳废油作改性剂,可调合出符合GB50092－96标准的高等级道路沥青。     

减压渣油及其四组分在接触剂上的裂化反应规律

以减压渣油为原料,采用热解色谱和热重-质谱,考察了减压渣油及其四组分(饱和分、芳香分、胶质和沥青质)在惰性接触剂L HBK和酸性接触剂C上的裂化反应.结果表明:四组分在有孔无酸剂L HBK上裂化程度由强到弱的顺序为胶质、沥青质、芳香分、饱和分,在有孔有酸剂C上裂化程度由强到弱的顺序为饱和分、芳香分、胶质≈沥青质.四组分...     

油煤共炼的理论基础及工艺过程优选

从原料油和煤的主要物化特征入手,描述了其热解和加氢热解的化学过程,在此基础上提出了采用两个反应器的新的工艺流程。油、煤热解过程有大量小分子烃类产生,从过程机理出发,选择合适的煤种,采取适当的措施便可以得到一定产率的轻质燃料油。油和煤的物化结构特征有差别,它们加氢热解生成的轻质燃油的组成不同,油加氢裂化生成的轻质燃油主要是大分子侧链及部分烷烃裂解产物;而来自煤的轻质燃油主要是单环、双环、三环芳烃,链烷烃量较少。油煤加氢共炼需要妥善应对原料油中胶质、沥青质热裂解带来的影响,避免其对煤热解造成负面影响。     

高氮高酸重质原油加工工艺的开发

针对辽河原油为代表的高氮、高酸重质原油的特点 ,提出了以溶剂脱氮工艺为核心的延迟焦化 溶剂脱氮 催化裂化 (或加氢裂化 )组合加工工艺 ,开发了用高氮减压渣油为催化裂化 ,尤其是加氢裂化装置提供优质原料的新工艺。溶剂脱氮工艺 ,可将焦化馏分油中绝大部分裂化性能优良的饱和烃保留在脱氮油中 ,氮脱除率达 85%以上 ,脱氮油质量优于直馏馏分油 ;富含芳烃的抽出油 ,既可返回焦化装置加工提高焦炭质量 ,亦可用来生产高附加值化工产品。与传统加工工艺相比 ,该组合工艺装置投资少、流程简单、加工费用低 ,有效解决了高氮、高酸重质原油加工过程中所遇到的难题。该工艺已实现工业化。渣油预处理工艺具有很强的脱氮、脱重金属和脱残炭能力 ,与催化裂化工艺组合也是加工高氮、高酸重质原油行之有效的工艺路线之一。     

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.     

一个反映重油平均分子结构的特征因数

构造了一个简单的粘重函数KL。考察了不同油品和纯烃的KL值，认为几值对于油品平均分子结构的反映是准确的，随重油的平均相对分子质量增大而降低。对于相对分子质量近似的烃，烷烃KL值＞环烷烃KL值＞芳烃KL值；重油的平均相对分子质量和环化程度越高，KL值越小；普通原油KL值＞重质原油KL值；对于同一种原油，常压馆分KL值＞减压憎分KL值＞原油KL＞常压渣油KL值＞减压渣油KL值；随拔出深度增大，渣油见值减小。     

催化裂化重芳烃作橡胶软化剂的应用研究

介绍了催化裂化回炼油和／或油浆经抽提所得到的催化裂化重芳烃的性质，考察了把它作橡胶软化剂时，对橡胶的加工性能及物理性能的影响。综合评价认为，催化裂化重芳烃是一种性能优良的橡胶软化剂。     

Transformations of oil cut hydrocarbons in catalytic modification with α-olefins

The change in the structural and group composition of paraffins and naphthenes and aromatics in the oil cut before and after alkylation with a-olefins was investigated. Oligoalkylation of these hydrocarbons and rupture of naphthene rings in hybrid structures and isomerization of alkyl fragments are reflected in the quality of the products obtained. __________ Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 2, pp. 32–34, March–April, 2007.     

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.     

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.     

南疆原油重组分适宜加工方向分析

对南疆原油350～520℃减压馏分进行综合分析,发现该原油减压馏分黏度指数较低(64～85),不适合生产高黏度指数润滑油,可考虑生产低凝点润滑油。该馏分平均分子中烷基侧链上的碳原子占总碳原子的百分数为59.30%,重金属镍+钒质量分数仅0.15μg/g,可直接作为重油催化裂化的原料。南疆原油520℃以上的渣油组分性质分析表明,该渣油属于第3类渣油,其密度在980.0 kg/m3以上,残炭值达24.80%,100℃运动黏度高达13 000 mm2/s,硫质量分数达1.98%,钒质量分数高达170.5μg/g。该渣油作为焦化原料硫含量较高,将对焦化产品的质量产生影响,可采用溶剂脱沥青工艺生产一定量的沥青。如果作为重油催化裂化原料的掺料,必须考虑调配比例,控制硫和金属钒含量,以防催化剂中毒。     

芳烃生产技术展望

通过对分离技术、反应生成技术、目的产品转移技术、甲基烷基化技术以及组合工艺最大程度增产芳烃技术等国内外芳烃生产技术进展进行分析,总结出近年来芳烃生产的技术进步与创新主要体现在催化剂和吸附剂性能的提高、新型反应及分离工艺的开发与应用、采用组合工艺最大化增产芳烃、单位产品物耗能耗的降低、装置规模的不断扩大等方面,而芳烃生产原料短缺是长期困扰芳烃生产的现实问题。归纳了紧紧围绕拓宽原料来源、开发新型高性能催化剂与吸附剂、应用组合生产工艺和装置大型化等芳烃生产技术发展趋势,提出了以建设国产化大型芳烃联合装置为契机,加快开发并形成原料多样化、产品结构调整灵活、物耗能耗更低并具有自主知识产权的芳烃成套生产技术的建议。提出应加快开发LPG、轻烯烃、芳烃抽余油等轻烃芳构化技术,使芳烃副产进一步增值;加强炼油-化工资源的一体化工作,充分利用催化裂化轻循环油、裂解重质汽油、炼厂重质芳烃以及煤焦油用以生产BTX;加大芳烃与煤化工结合的力度,尽快工业化实施甲苯甲基化生产二甲苯技术;进一步拓展生产芳烃的原料,开发并利用甲醇、纤维素等生物质生产芳烃新技术。     

减压渣油溶剂脱沥青-焦化总液体收率的研究

以减压渣油为原料采用溶剂脱沥青过程，得到了不同m（H）／m（C）的脱油沥青，利用重油热加工精确评价装置，对4种焦化原料进行焦化行为研究，研究不同W／（H）／m（C）的沥青的焦化行为和产品分布。结果表明：随着焦化原料W／（H）／m（C）的增加，瓦斯气收率变化不大，馏出油收率明显增加，残渣油收率明显降低，m（H）／m（C）每增加1个百分点，馏出油收率增加10个百分点，残渣油收率降低10个百分点；饱和分、芳香分、胶质含量能够显著影响液体油品的收率。对于溶剂脱沥青一焦化组合工艺，在溶剂脱沥青过程中，提高脱沥青油的抽出率，组合工艺的总液体油品收率就会增加，在可实现的范围内，脱沥青油抽出率每提高20个百分点左右，则总的液体油品收率增加5个百分点左右；对实验数据进行回归分析，得到了实验所用渣油焦化转化率的数学归纳式。     

孤岛VRDS渣油研制重质润滑油基础油制取重质基础油可行性探讨

孤岛减压渣油经加氢裂化后的尾油,化学组成和性质发生了很大变化,接近石蜡基的大庆减压渣油：色谱模拟脱沥青研究表明,在很高的脱沥青油收率下,脱沥青油的残炭值、氮含量仍保持较低水平,脱蜡油性能优越,孤岛ＶＲＤＳ渣油可以作为生产重质润滑油基础油的原料。