原油及渣油色谱模拟蒸馏馏程测定的影响因素分析

采用色谱模拟蒸馏测定原油及渣油的馏程,研究了进样稀释比（CS2与油样的质量比）与内标量对模拟蒸馏馏程测定结果准确率的影响,并探讨了模拟蒸馏与实沸点蒸馏馏程测定偏差的规律。结果表明,原油、较重原油或渣油进样稀释比为3：2时,模拟蒸馏数据的准确性最高;增量内标法测定原油模拟蒸馏馏程时,随着样品重质组分含量的增加,适当减少内标物质量,可以减小模拟蒸馏和实沸点蒸馏数据的偏差;相同温度下,实沸点蒸馏收率较色谱模拟蒸馏低;温度低于400℃时模拟蒸馏与实沸点蒸馏曲线基本重合,最大质量收率偏差小于4％;高于400℃后,随着温度的升高,模拟蒸馏与实沸点蒸馏数据偏差增大,但最大偏差不大于10％。     

原油蒸馏装置实现推理技术在线闭环控制

美国炼制公司 3 2 5Ｍｔ/ａＷａｒｒｅｎ炼油厂采用的在线闭环控制系统大大改进了产品质量 ,并且改进了回流系统的控制 ,大大减少了原油切换时间 ,也减轻了操作人员的劳动强度。新的在线系统采用了两个控制软件实现了推理技术控制 :ＧＣＣ(综合的切割点控制器 )和ＣＰＰＭ (原油蒸馏装置性能监控器 )。该系统用以控制产品质量和初馏塔及常压塔内回流。使用推理技术的新控制系统包括 :采用两座塔的温度分布、压力、产品流量和其他过程测量参数建立进装置原油的实沸点 (ＴＢＰ) ;基于原油的ＴＢＰ和热量平衡预测产品质量和气液 (Ｖ Ｌ)分布 ;…     

分子蒸馏技术及其在渣油分离中的应用

综述了分子蒸馏技术的基本原理、主要特点、主要设备、在国内外的发展概况及应用现状。重点评述了分子蒸馏技术在延长实沸点蒸馏曲线和渣油深拔方面的应用进展。指出了分子蒸馏技术在原油评价领域应用的难点。     

原油蒸馏曲线单调递增指数函数样条插值方法研究

针对以虚拟组分法表征原油及其馏分油复杂组成时,常因蒸馏数据不足而导致蒸馏曲线不连续、不光滑,结果可靠性差,而传统二次、三次样条插值方法存在难以保证蒸馏曲线单调递增的问题,设计了一种包含3个参数的指数函数插值方法,从理论上保证了蒸馏曲线单调递增。进而,对52种原油的实沸点蒸馏数据进行插值验证,结果表明：指数函数插值法能够保证插值后的原油蒸馏曲线单调递增;在52种原油的插值结果中,指数函数插值与校验值拟合决定系数(R²)大于0.99的有37种,占比71.2%,三次样条插值结果R²大于0.99的仅有21种,占比40.4%;而指数函数插值结果的准确度高于三次样条插值结果的有50种,说明指数函数插值方法效果明显优于三次样条插值方法。因此,基于指数函数插值方法,采用虚拟组分法模拟计算原油加工过程的精确度明显提高。     

进口原油加工过程中的问题和对策

以工业数据为基础，介绍茂名石化公司２０多年来加工进口原油过程中遇到的问题和解决这些问题的对策。内容涉及原油蒸馏、减压蜡油加工、渣油加工、三废治理、设备腐蚀与防腐蚀措施等。     

重质常压渣油裂化中原料油化学性质与转化率,生焦率的关系

催化裂化原料转化率因子对原料油的评价有流化催化裂化装置的优化是一个很有用的途径。沸点在３２０℃～３５０℃范围内的原料油,其转化率因子的计算方法可在文献中查到,ＰＥＴＲＯＢＲＡＳ渣油裂化器,要掺炼相当大比例、终馏点比减压蜡油高的原料油,在其开工时,需要采用新的渣油性质分析方法,并能对极重原料油预见其转化率和生焦选择性因素。ＰＥＴＲＯＢＲＡＳ炼油厂曾加工过的原油,共为１５批常渣,分别用先进和传统的方法     

由石油馏分油的恩氏蒸馏曲线预测实沸点蒸馏曲线数学模型的初探

在大庆和胜利原油常压直馏馏分油48组实测数据的基础上,提出通过恩氏蒸馏曲线和密度数据直接计算实沸点蒸馏曲线的数学模型,其平均误差为1.31%,明显地优于常用的曲线换算方法(其相应误差为2.36%)。可供炼油及石油化工设计、生产、科研中计算机计算之用。     

原油调合法生产高等级道路沥青的研究

对三种原油生产重交通道路沥青的方法进行了研究，发现单种原油蒸馏法生产重交通道路沥青存在较大困难。而利用原油调合然后蒸馏的方法可将原先不能生产重交通道路沥青的某些原油来生产重交通道路沥青。这样不但能够生产质量符合国家现行标准及交通部行业标准的AH-70或AH-90重交通道路沥青，还可生产质量符合中海36-1技术要求的重交通道路沥青。原油调合法可弥补单种原油生产沥青的缺陷，起到性能互补的作用。     

亚太地区第一套渣油加氢裂化装置投产

日本ＴＯＮＥＮ公司第一套渣油田加氢裂化装置于１９９７年６月开工,该装置采用烃研究公司（现为ＩＦＰ北美公司）的Ｈ－ｏｉ工艺。本文论述的即是该项目从技术选型到开工的过程。加工能力为２５,０００ＢＰＳＤ（３９７５ｍ＾３／开工日）的该装置现场不到１３个月即告完成,创造了施工周期最短的纪录。由于ＴＯＮＥＮ公司优越的质量保证体系和操作培训,装置投产顺利。本文还将讨论该装置近期的运行及性能。设计Ｈ－ｏｉｌ装置是     

典型原油深拔蜡油及渣油性质研究--大庆原油深拔蜡油及渣油性质研究

对大庆原油进行了深度蒸馏试验，并对深度蒸馏所得的深拔蜡油和深拔渣油进行了详细的研究。结果表明：该原油各深拔蜡油窄馏分均是较好的催化裂化原料，当蜡油的切割点提高到570～640℃时，蜡油收率可比常规蜡油增加7．17％～14．12％，深拔的经济效益十分显著。各不同深度渣油均属较易加工的渣油。     

Extending the true boiling point curve of a heavy crude oil by means of molecular distillation and characterization of the products obtained

Petroleum is evaluated by means of the true boiling point (TBP) curve, making possible to investigate the yields of the products that will be obtained in refineries, as well as establishing operating strategies and process optimization. Refineries determine TBP curves until 838 K. With molecular distillation the TBP can reach values up to 973 K. Molecular distillation shows potential in the separation, purification, and concentration of products. Eta residue is fractioned and the TBP of the whole crude oil is extended. Products of the distillation were characterized by density, SimDis (simulated distillation), and molar mass. Results showed that density and molar mass of the cuts obtained increase as the process temperature increases. These analyses confirm the efficiency of the separation method by molecular distillation.     

石油馏分三种蒸馏曲线换算软件的设计与开发

以石油馏分的恩式蒸馏曲线作为基础,根据文献中提供的模型进行其他蒸馏曲线的关联和换算。以VB6．0作为开发用户操作界面为平台,设计了一个能分别对石油馏分恩式蒸馏曲线与实沸点蒸馏曲线、恩式蒸馏曲线与平衡汽化曲线和不同压力下平衡汽化曲线换算的软件,大大提高了蒸馏数据换算的效率和准确性。通过对文献提供的实例进行测试表明,该软件针对3种蒸馏曲线的换算均有很好的准确性和吻合性。     

True Boiling Point Extended Curve of Vacuum Residue Through Molecular Distillation

Molecular distillation is a separation process that explores high vacuum, operation at reduced temperatures, and low exposition of the material at the operating temperature. The term vacuum residue (heavy petroleum fractions) refers to the bottom of the vacuum distillation, which has an atmospheric equivalent temperature (AET) above 540°C. For the assay of the properties of petroleum and petroleum products, the use of the true boiling point (TBP) distillation analysis is accepted as a common practice; however, for heavy petroleum fractions, some difficulties appear for determination of TBP of these petroleum fractions. The objective of this work is to develop a new and a more appropriated method to extend the TBP curve to use it for characterizing vacuum residue of heavy petroleum. The falling film molecular distillator was used. The results showed that it is possible to extend the TBP curve through molecular distillation process with very good precision.     

Development of correlation for extension of the true boiling point (TBP) and molar mass

The true boiling point curve (TBP) is an important tool for the petroleum industry; it is used to obtain the behavior of petroleum during distillation. This work developed a correlation for the extension of the TBP curve by means of molecular distillation. TBP curve is well established for a temperature of 565°C in a conventional distillation. With the correlation developed, it is possible to reach values near 1,000°C. A second correlation was also developed for predicting the values of molar mass of waste petroleum. Both correlations demonstrated to be valid and represent a great advancement for the petroleum industry.     

快速蒸馏法及其在原油酸值分布规律研究中的应用

原油和馏分的酸值(TAN)是反映其加工过程中腐蚀性的重要指标。传统的实沸点蒸馏(TBP)方法未考虑石油酸在原油蒸馏过程中的分解,得到的馏分酸值严重偏低,影响了对馏分腐蚀性的判断以及相应防腐措施的制订。为此开发了一种原油快速蒸馏(RD)仪,采用短分馏柱、高真空度、高蒸馏速率对原油进行分段蒸馏切割,有效避免了原油中石油酸的分解,使各馏分酸值的加权值达到了原油酸值的90%以上。在此基础上,研究了几种典型高酸原油酸值的分布规律,发现原油可馏出部分的酸值基本上都是随着沸点的升高而增高。另外,通过傅里叶变换离子回旋共振质谱(FT-ICR MS)分析表明,实沸点蒸馏过程中酸值降低的主要原因是大分子石油酸的分解,而与石油酸的类型相关性较小。     

用沙特阿拉伯中质原油经减压蒸馏研制70号高等级道路沥青

用沙特阿拉伯中质原油经常规实沸点蒸馏及燃料型减压分馏直接生产的70号沥青不能满足中国石化集团公司的1号高等级道路沥青AH－70标准。采用二次减压蒸馏工艺可以直馏生产70号高等级道路沥青,分析了残留低相对分子质量组分对高等级道路沥青性能的影响,沥青中蜡油残留得多,针入度比低。第一次减压蒸馏的深度不能过大,切割温度以不超过500℃为宜;第二次减压蒸馏需提高真空度,进料温度以不超过360℃为好。     

Recovery and Characterization of Petroleum Residues Through the Molecular Distillation Process

Molecular distillation process is an efficient way to separate complex residues to obtain improvement and a more complete characterization of crude oils. It presents advantages such as to generate distillation products that can be experimentally characterized, and the operation conditions of this process generate distillate cuts with an atmospheric equivalent boiling point (AEBP) above 650°C without risks of thermal degradation. The aim of this work is to carry out the separation of two vacuum residues (VR) within the process temperature range from 550 to 670°C, using the Brazilian Molecular Distillation equipment. As a result, five distillate cuts and five residues from molecular distillation processing were generated. The molecular distillation (MD) technique provided a gain in distillate yield of about 10% over the conventional methods. The efficiency of the technique was verified through the vapor pressure osmometry experiments and the extension of true boiling point (TBP) curves of petroleum. The extended TBP curves by the molecular distillation process demonstrated that this alternative method is appropriate to extend the TBP curves to temperatures above those of the conventional methods.     

实沸点蒸馏前后高酸重质原油的石油酸分布表征

The molecular transformations of carboxylic acids in heavy acidic SL crude before and after true boiling point distillation were examined by ultra-high resolution negative-ion electrospray ionization （ESI） Fourier transform ion cyclotron resonance mass spectrometry （FT-ICR MS）. The acid class （heteroatom number）, type （z numbers） and carbon number distributions were positively characterized. It was found out that the total acid number （TAN） of SL crude decreased after true boiling point distillation, and the abundance of O2 class in mass spectra was also found to be reduced from 67.6% to 34.5% in SL TBP mixed crude as measured by MS spectra, indicating to a potential carboxylic acid decomposition. However, it was interesting that the carboxylic acids type distribution in both oils was almost the same although their relative abundance in SL TBP mixed crude turned to be much lower, suggesting that various petroleum carboxylic acid types have the similar thermal decomposition reaction behavior. Furthermore, for each O2 type of acids in SL TBP mixed crude, the abundance of carboxylic acids with carbon number higher than 35 was reduced greatly, especially for those with carbon number higher than 60, the mass peaks of which were nearly totally removed, indicating that the large carboxylic acid molecules in heavy fractions decomposedmore significantly because of longer heating time during the true boiling point distillation process. As a result, the reduction ofTAN may be caused by the thermal decomposition of carboxylic acids especially those with high carbon number, suggesting that quick distillation or much lower pressure is required to avoid the thermal decomposition.     

ASTM D-5307 and ASTM D-7169 SIMDIS Standards: A Comparison and Correlation of Methods

TBP curves are essential in process simulators of the refining industry, particularly for the heaviest fractions of crude oils. ASTM D-7169 and ASTM D-5307 are standards used in simulated distillation analysis for fast characterization of these fractions. In this report, correlations to convert data from the first one to the second-mentioned standard are reported. These correlations were obtained from our analytical laboratory and pilot plant experimental data, gathered so far.     

燃料型减压蒸馏塔的模拟计算

提出了一种用正构烷烃切割实沸点（TBP）蒸馏曲线的新方法，即积分自动选择正构烷烃法（IAC法）。模拟计算的结果表明：该方法可以准确地预测减压蒸馏高沸点馏分的物性数据；由于把压力作为变量处理，进一步提高了模拟计算的准确程度。