KH 150 BS加氢基础油中絮状物的分子类型分析

为了研究中国石油克拉玛依石化分公司150 BS加氢基础油(KH 150 BS)在低温下产生絮状物的原因,首先在低温下采用溶剂稀释和抽滤的方法分离出絮状物,然后用尿素提取出絮状物中的正构烷烃,并用气相色谱分析了其碳数分布,最后用气相色谱-质谱和红外光谱分析了絮状物和滤出油的组成,并且测定了絮状物和滤出油的相对分子质量。结果表明,KH 150 BS基础油中的絮状物是一些相对分子质量较大(617~819)和凝点较高的烃类化合物。这些烃类化合物主要由较长碳链、较低支化度(0.138 3~0.343 6)的链烷烃和大量的环数较低、带长侧链的环烷烃组成。在静止和冷却的条件下,这些碳氢化合物形成一个胶状的网络,将油包在其中,最后扩散到整个油中形成絮状物。     

APPLICATION OF MULTICOLUMN VALVE SWITCHING GAS CHROMATOGRAPHY FOR THE ANALYSIS OF NAPHTHA AND KEROSENE FRACTIONS OF SAUDI ARABIAN LIGHT CRUDE OIL

Abstract

The straight run naphtha and kerosene fractions of Saudi Arabian Light crude oil were analyzed for paraffins, olefins, naphthenes and aromatics (PONA) using a gas chromatographic technique. This method is based upon group type separation according to carbon numbers using a programmed multiple valve switching sequence and employing multicolumn approach. The chromatographic operating conditions and carrier gas flow rates were selected to determine PONA contents of naphtha and kerosene fractions. These straight run fractions were produced by an automatic true boiling point (TBP) apparatus. Boiling range distributions of these fractions were determined using a standard ASTM method of simulated distillation. PONA results were compared with the literature. Total paraffins, naphthenes and aromatics agreed with each other.     

STRUCTURAL CHARACTERIZATION OF SOLID n-PARAFFIN COMPONENTS DERIVED FROM MUKTA CRUDE OIL

ABSTRACT

The total solid paraffins (boiling 270°C+) separated from Mukta crude by urea adduction and its narrow fractions were analysed for their structural composition by proton NMR, infrared spectroscopy and gas chromatography. It has been observed that CH2/CH3 ratio in these samples varies from 7·9 to 13·8 while their average carbon number ranges from 17 to 29·6. The CH₂/CH₃ ratio and chain length of paraffins increases with increase in boiling range of the fractions.     

加氢裂化尾油窄馏分的催化裂化转化规律研究

将中东减压蜡油的加氢裂化尾油分为4个沸程范围不同的窄馏分,在固定流化床装置上考察了其催化裂化反应性能,采用GC/MS等方法对原料和裂化产物的烃类组成进行了分析。结果表明,4个窄馏分中饱和烃的质量分数均高于98.0%,随着馏分变重,窄馏分中的链烷烃含量增大,环烷烃含量减小,并且链烷烃和各族环烷烃均向高碳数方向移动。4个窄馏分均易于裂化,干气和焦炭产率低,液化气和汽油收率高。在相同的催化裂化条件下,随着馏分变重,其可裂化性能增强,干气和焦炭产率降低,液化气收率增加,汽油收率增加但辛烷值略有降低,柴油和重油收率均降低。     

APPLICATION OF MULTICOLUMN VALVE SWITCHING GAS CHROMATOGRAPHY FOR THE ANALYSIS OF NAPHTHA AND KEROSENE FRACTIONS OF SAUDI ARABIAN LIGHT CRUDE OIL

The straight run naphtha and kerosene fractions of Saudi Arabian Light crude oil were analyzed for paraffins, olefins, naphthenes and aromatics (PONA) using a gas chromatographic technique. This method is based upon group type separation according to carbon numbers using a programmed multiple valve switching sequence and employing multicolumn approach. The chromatographic operating conditions and carrier gas flow rates were selected to determine PONA contents of naphtha and kerosene fractions. These straight run fractions were produced by an automatic true boiling point (TBP) apparatus. Boiling range distributions of these fractions were determined using a standard ASTM method of simulated distillation. PONA results were compared with the literature. Total paraffins, naphthenes and aromatics agreed with each other.     

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通过对松辽盆地北部天然气的烃类和非烃类组成、甲烷碳同位素、分子量、重烃气浓度、甲烷系数、重烃系数等资料的分析，研究了盆地北部不同地区天然气化学组成特征和物理性质。同时根据天然气地化特征，对盆地北部天然气的成因类型进行了划分，并探讨了生物甲烷气、成熟—高成熟油型气、高成熟煤型气和过成熟煤型气的化学组成及分布规律。研究结果表明：生物甲烷气埋深浅、碳同位素轻、气组分甲烷含量高、氮气含量高；油型气主要分布于盆地中部含油组合（萨、葡、高油层），甲烷碳同位素重于生物气，轻于煤型气，烃气成分变化较大，受各种因素的影响，表现出不同的干湿性；高成熟和过成熟煤型气主要分布于深部含油气组合（扶余油层以下），碳同位素重，气组分甲烷含量高，天然气分子量低     

A COMPARATIVE STUDY OF HYDROCARBONS PRESENT IN NARROW BOILING RANGE NAPHTHA FRACTIONS OF SAUDI ARABIAN CRUDE OILS

Four Saudi crudes were distilled to produce four narrow boiling range naphtha fractions by true boiling point (TBP') distillation method. These fractions were analyzed for paraffins, olefins, naphthenes and aromatics using a multicolumn valve switching gas chromatographic technique in which hydrocarbons were separated and analyzed according to their types and carbon numbers. It was observed that with increasing average boiling points of the fractions, the paraffins decrease while aromatics have an increasing trend.     

十三集总催化重整反应动力学模型研究

根据集总理论 ,从催化重整反应规律出发 ,提出了包含十三个集总组分的催化重整反应模型。该模型将重整物料按分子大小集总为C6 ,C7,C8和C+ 9组分 ,每一个碳数的化合物又划分为烷烃、环烷烃和芳烃三个集总 ,裂化产物C- 5组分作为一个集总。集总组分之间主要发生烷烃脱氢环化、环烷烃脱氢芳构化和加氢裂化反应。根据重整反应特点建立了相应的动力学模型 ,并编制了工业重整反应器的模拟计算软件 ,可预测催化重整产物组成、产品产率和重整反应器温降 ,计算结果与生产数据基本吻合。     

A STUDY OF AROMATIC HYDROCARBONS IN QAIYARAH NAPTHA FRACTION 50-165° C USING GAS CHROMATOGRAPHY/MASS SPECTROSCOPY

ABSTRACT

Qaiyarah crude oil, which is one of the heaviest crude oil in the world and mainly aromatic to asphaltic in nature, was the subject of this investigation. Analysis of the aromatics is obtained by employing various methods of extraction, purification, gas chromatography and gas chromatography/mass spectroscopy (GC/MS). The study reveals the presence of mono, di and tri-aromatic hydrocarbons with their alkyl and aryl substituents. Moreover, the detected naphthenes are mainly cyclahexane, and deckaline with their aliphatic derivatives     

USE OF MASS SPECTROMETRY TO STUDY THE EFFECT OF HYDROCRACKING ON THE COMPOSITION OF BASE STOCKS

ABSTRACT

Mass spectrometry (MS) was used to study the compositional changes taking place during the hydrocracking process and the effect of composition on viscosity index (VI) of base stocks. The determination of compound types by MS required a separation of the petroleum samples into aromatic and nonaromatic fractions. After the hydrotreating of the feed, an increase in 1–ring naphthenes was observed. The value of an average ring number per mole did not change indicating the absence of ring–opening reactions. After the hydrocracking step, the MS analysis of the nonaromatic fraction showed a significant decrease in 1–6 ring naphthenes. A decrease in average ring number from 0.4 to 0.2 per mole indicated that the ring-opening reactions were taking place. The MS analysis of different hydrocracked base stocks, having a VI in the range from 143 to 148, showed no significant effect of paraffins/isoparaffins, 1-ring naphthenes and the condensed naphthenes on VI. The hydrocracked base stocks, having a VI of 143–144, were found to have an average ring number of 0.3 per mole. The hydrocracked base stocks, having a higher VI of 146–148, were found to have a lower average ring number of 0.2 per mole. The MS results indicated that the severity of hydrocracking and the extension of the ring-opening reactions were better described by an average ring number per mole rather than the contents of different chemistry hydrocarbons.     

Properties and Chemical Composition of Typical Coker Gas Oil

Abstract

The coker gas oil from Daqing, Shengli, and Liaohe, which are three famous oil fields in China, are studied. The properties, chemical composition, and structural composition of coker gas oil from Daqing, Shengli, and Liaohe saturated hydrocarbon are analyzed. The results show that nitrogen and sulfur content in Daqing coker gas oil is the lowest, and saturated hydrocarbon content is the highest, and Daqing coker gas oil is the most easily processed raw material, and Liaohe coker gas oil mediates between two raw materials, but Shengli coker gas oil is the most difficult to process. By comparing with vacuum gas oil and nitrogen, sulfur content and carbon residue in the coker gas oils is higher and saturated hydrocarbon content is lower. Shengli coker gas oil is a somewhat inferior raw material. The factor of effecting on the processing and use of coker gas oil are analyzed, and the processing ways of coker gas oil are put forward.     

Study of individual hydrocarbon's composition of gasoline fraction of Tamsagbulag oil, Mongolia

In order to conduct complex research in oil that originated in Mongolia for further application of petroleum not only as fuel but also as raw material for organic synthesis, we need to study the physical and chemical characteristics, individual and group hydrocarbon's composition of main petroleum fractions. A number of studies and surveys on the physical and chemical characteristics, group hydrocarbon's composition of petroleum deposits in Zuun-Bayan, Sukhaibulag, Tsagaan Elst, Tamsagbulag have been carried out earlier through n-g-M, aniline point, dispersimetric methods successfully. Yet a detailed chromatographical and NMR spectroscopic study for individual hydrocarbon's composition of Tamsagbulag oil main fractions has not been conducted. In the present study, the results of GC analyses of gasoline fractions of wells 19-3, 19-13 and 19-10, Tamsagbulag, Eastern Mongolia were presented. The gasoline fractions of given wells are characterized by high concentration of paraffins and presence of trace amount of olefins. A total of 69 paraffins, 45 naphthenes, 41 aromatics and 3 olefins were identified, totalling 158 individual hydrocarbons from each samples of gasoline fraction. The first attempts to classify Tamsagbulag oil under individual hydrocarbon composition data were successfully conducted and the hypothesis (supposition) of a genetic classification of given oil as “sapropelic” type was made.     

COMPOSITIONAL ANALYSIS OF PETROLEUM WAXES BY ZEOLITE MOLECULAR SIEVE-GCMS

ABSTRACT

To investigate the composition of petroleum waxes, studies were carried out on the extraction of normal paraffins from petroleum waxes by zeolite molecular sieve type 5A. Time required for adsorption of different molecular weight n-paraffins from standard mixture and petroleum waxes has been ascertained. Un-adsorbed part of the waxes has been investigated by GC-MS technique. Recovery of adsorbed hydrocarbon from molecular sieve was done by supercritical fluid extraction.     

Isomerization of Gas Condensate C5—C6 Paraffins on Pd—Catalysts

The prohibition on use of tetraethyllead and the requirement of significantly reducing the aromatic hydrocarbon content make it necessary to incorporate large quantities of branched C₅—C₆ paraffins in gasolines. These compounds can be obtained by isomerization of the corresponding linear paraffins, components of the stable condensate manufactured at gas processing plants (GPP). The skilled use and improvement of the properties of gas condensate are an important practical problem.     

准噶尔盆地乌夏地区生物降解原油中饱和烃组成解析

运用全二维气相色谱/飞行时间质谱(GC×GC/TOFMS)结合全二维气相色谱/氢火焰离子检测(GC×GC/FID)实现了对准噶尔盆地乌夏地区不同生物降解程度原油饱和烃复杂混合物成分的分析研究,提升了对生物降解原油组成及成因机理认识。结果显示:①乌夏地区生物降解原油中不可识别混合物主要由烷基取代环状化合物及其同系物组成,这些环状化合物主要以六元环为基本单元,包括单环烷烃(类胡萝卜烷)、双环烷烃(十氢化萘,脱-A,B环-甾烷)、三环烷烃(菲满类、三环萜烷、断甾烷)和金刚烷类、四环烷烃(甾烷、断藿烷、四环萜烷)和五环烷烃(藿烷、25-降藿烷)等六大类化合物;②不同生物降解原油中饱和烃总量变化不大,饱和烃中不同族系化合物随着生物降解作用增强呈现此消彼长的变化规律,在重度生物降解阶段,双环烷烃存在大量同系物及同分异构体,可能是微生物作用新生成的化合物,并且由于自身较强的抗生物降解能力,使双环烷烃成为饱和烃的优势成分,占饱和烃总量的50%左右,而多环烃类化合物含量随着生物降解程度逐渐增加,主要是由抗降解能力相对较强的高环数化合物的逐渐富集形成。     

Characterization of Different Molecular Weight Fractions Separated from Utah Maltenes by Gel Permeation Chromatography

ABSTRACT

Maltenes derived from Utah bitumens were separated by gel permeation chromatography ( OPC) into fractions having number average molecular weights ( MW) in the range from 300 to 11985. The fractions were examined by vapor pressure osmometry, absorption spectrometry in the visible region as well as proton and carbon -13 NMR. The results are reported in comparison with those for the corresponding fractions separated from Athabasca maltenes. Utah fractions appeared to be more aliphatic with longer average aliphatic chains lengths. Branched and alicyciic types were more abundant in Utah samples, especially those with low MW, There was an apparent difference in the hydrocarbon structure of both Utah and Athabasca maltenes GPC     

An Algorithm for Pseudocompound Delumping and Lumping into Homologous Groups

An algorithm for pseudocompound delumping and lumping into homologous groups is developed. This algorithm is useful for modeling refineries when using commercial simulators and detailed reactor models. Generally, commercial simulators represent petroleum fractions using pseudocompounds; however, reactor models and their kinetics are based on known compounds. This algorithm delumps the pseudocompounds into homologous groups that are represented by model compounds, which are then used by a detailed reactor model. After the reaction, the outlet stream is lumped again to pseudocompounds that are used in the remaining operations of the commercial simulator. The lumping operations are based on mass balance principles and fundamental properties of the hydrocarbon mixture. This algorithm is applied to the modeling of a hydrotreatment unit that belongs to the Mexican System of Refineries which uses a detailed three phase trickle bed reactor. The problem is to delump and lump the pseudocompounds, which represent light gas oil, into paraffins, naphthenes, and mono and polyaromatics. Results show a good agreement with industrial data.     

润滑油基础油分子表征方法及其黏度性质预测

采用气相色谱/场电离飞行时间质谱(GC/FI TOF MS)对润滑油基础油进行分子表征。依据精确相对分子质量和质谱图平均丰度分别进行定性和定量分析,可简单快速地获得基础油中链烷烃及一环～六环环烷烃的碳数分布结果。基于基础油分子组成数据,采用Kennard-Stone方法将样品集分为校正集和验证集,依据偏最小二乘方法(PLS)建立预测黏度和黏度指数的模型,模型验正集及预测集预测值的标准偏差分别小于2.0 mm²/s和2.0,相关系数均大于0.99。所建模型对基础油黏度及黏度指数的预测适用性好、准确度高,具有一定的实用价值。     

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.     

分子水平重油表征技术开发及应用

重油是十分复杂的烃类、非烃类化合物的混合物,弄清其详细的分子组成不仅是分析测试工作者追求的目标,也是实现石油炼制技术跨越式发展的重要前提。近10年来,石油化工科学研究院以应用为导向,采用傅里叶变换离子回旋共振质谱仪(FI-ICR MS)、全二维气相色谱质谱联用仪(GC×GC/MS)、气相色谱串联质谱联用仪(GC/MS/MS)、气相色谱飞行时间质谱仪(GC/TOF MS)等多种高分辨质谱仪器,结合固相萃取分离技术、化学衍生技术、化学计量学以及其他仪器分析技术,开发出多种分析方法,不仅能够得到烃类、非烃类化合物按碳数分布或者按沸点分布的信息,而且还能得到重油中某些分子的定性定量数据。这些方法针对性强、重复性好、提供的信息丰富,已经在科研和生产中发挥重要作用,而且也为将来的分子水平石油炼制打下了很好的基础。