低温氧化对原油组成的影响

通过空气与原油在油藏温度和一定压力下低温氧化过程的模拟实验,对反应前后气体与原油的组成进行分析.结果表明,实验条件下低温氧化反应后原油芳烃含量减少,胶质含量增加,饱和烃含量和沥青含量基本不变,正构烷烃轻重组分比增加;原油黏度有所增加.     

重度原油注空气低温氧化过程研究(英文)

低温氧化反应对现场燃烧(ISC)技术点火的成功有十分重要的影响.采用高压氧化管,研究了不同温度压力下,新疆克拉玛依重度原油的低温氧化过程.结果表明,温度和压力的变化对低温氧化反应的放热程度、持续时间以及气体产物有明显影响.适合油样低温氧化反应的温度和压力分别为150℃和10MPa.此外,采用纯组分替代原油族组分进行低温氧化实验,研究低温氧化反应对原油族组分(饱和烃、芳香烃、胶质、沥青质)含量的影响.结果表明,原油所含族组分中,芳香烃组分最易被氧化,其含量由氧化前的19.17%减少到12.38%(150℃)和9.51%(250℃).随着低温氧化过程的进行,结构复杂的族组分(胶质、沥青质)的含量明显增加.实验数据对油藏实施注空气技术,以及该技术现场实施条件的确定有十分重要的指导意义.     

原油组分低温氧化机理和反应活性实验研究

分析了原油和原油组分低温氧化的机理,通过实验进行了不同油品低温氧化反应,考察了氧化反应前后原油族组成的变化,并研究了单组分(正十六烷、蜡、蒽、沥青质)在不同温度下的低温氧化速率和反应活性,得出了不同原油组分的低温氧化反应的活化能。结果表明,稠油较轻质油有更好的氧化反应活性,在较低温度下稠油更容易被氧化,原油中不同组分及含量是影响氧化反应活性和氧化反应速率的重要因素,重组分的沥青质和长链烷烃在低温下(70~90℃)氧化活性较高,正十六烷和蒽反应活性较之重组分低。揭示了原油组分低温氧化反应机理以及不同组分氧化反应活性的区别,为油田注空气工艺方案设计提供基础。     

马瑞原油在空气和氮气中的热解-氧化性能

低温氧化是注空气采油及原位燃烧采油技术中的重要化学反应,为深入认识原油在有氧环境下复杂热反应过程中的低温氧化特性,我们采用热重/差热分析法(TG/DTA)研究了线性升温和等温条件下马瑞(Merey)原油的热反应行为。 结果表明,Merey原油在空气及线性升温条件下的受热过程分4个阶段:气化段、低温氧化段、热解段和高温氧化段;相邻阶段的物理、化学主导过程的重叠增加了分析原油热反应特征的难度。 升温速率提高,气化段和低温氧化段的终止温度不变;热解段和高温氧化段的终止温度以及热解段的峰温随升温速率的增加而升高。 N₂气与空气下Merey原油的热重/微分热重(TG/DTG)数据对比表明,升温速率越高,空气下的高温氧化段与热解段重叠程度越大,这有利于燃烧但会降低原油采收率。 空气下等温时的TG/DTA结果表明随升温速率增加,升温至300 ℃时的失重率降低,不利于原油轻组分的气化。 反应温度越高,气化过程时间越长,失重分数越大。 Merey原油在低于300℃时低温氧化反应不是主导反应。     

A new quick method of determining the group hydrocarbon composition of crude oils and oil heavy residues based on their oxidative distillation (cracking) as monitored by differential scanning calorimetry and thermogravimetry

A calorimetric-thermogravimetric method is described of determining mass percent contents of distillate fractions, paraffins, base oils, resins, asphaltenes and carbines in various crude oils. The method is based on recording DSC curves of a 10–15 mg sample heated in air in a calorimetric-cell at a rate of 40–50 °C/min. Additionally, weight loss of sample is found at temperatures before and after the reaction. At temperatures from 220 °C or higher distillation of the hydrocarbon mixture starts to be accompanied by its exothermic oxidation, thereby making possible monitoring the distillation (oxidation) of consecutive HC fractions by simple calorimetric-techniques. Differential scanning calorimeter “Thermodat” of high-calorimetric-resolution and sensitivity equipped with dedicated software was used for conducting the experiments and performing all the calculations. Percent contents of the main constituents in a number of heavy and light crude oils were determined and formulas for establishing paraffinic, base oil and coke-forming potentials of crude oils and oil residues derived. One full analysis of a sample takes no longer than 1.0–1.5 h. The method can be used for on-line quality control of various petroleum products, such as atmospheric and vacuum oil residues, cracking residues, lubricants, ceresins and paraffins.     

Effect of formation factors on light crude oil oxidation via TG-FTIR

This research aimed at the investigation of the effect of formation factors on the light crude oil during the high temperature air injection process. For this purpose, thermogravimetric and Fourier Transform Infrared Spectroscopy techniques were combined to investigate the light crude oil and oil mixed with formation water and sand at 58, 250, and 450 °C, respectively. The results showed that at different temperature range, the mass drop rate presented different trend and the formation water and sand increased the activation energy of the oxidation reaction. The formation sand exhibited the excellent catalytic effect at relative low temperature. The oxygen addition reaction massively was trigged at 250 °C, and the bond scission reaction dominated at 450 °C. With different additives at different temperature range, the type, concentration, and produced timing of the products presented different tendency.     

原油空气氧化前后多环芳烃组分的气相色谱-质谱分析

采用柱层析法对空气氧化前后的原油进行族组分分离,利用气相色谱-质谱(GC-MS)分离测定其芳香烃组分,分析多环芳烃组分的变化.结果表明,随着氧化过程的进行,烷基化多环芳烃占多环芳烃的含量从氧化前的71.5%增加到92.0%(175℃)和90.2%(225℃).轻质组分萘和菲的优势逐渐被重质组分艹屈取代.侧链少的多环芳烃比侧链多的更易氧化.氧化后,其他稠环化合物蒽、萤蒽、芘、苯并蒽含量降低,苯并萤蒽含量增加;苯并芘在175℃氧化后含量降低,而在225℃氧化后含量增加.与此同时,175℃氧化后生成了原油所不含有的三芳甾烃、联苯和苯并呋喃.     

压力对塔里木原油四组分热解性能的影响

压力对深层油藏原油热化学过程的影响尚存在较大争议,为研究其在油藏原油热解成气过程中的作用机理,我们在450℃、5~40 MPa压力下对塔里木原油四组分(饱和分、芳香分、胶质和沥青质)进行了封闭体系的热解实验,通过气相色谱(GC)和气相色谱/质谱(GC/MS)分别对原油四组分热解反应的气体产物及饱和分热解过程的液态产物进行了分析。结果表明,在450℃、24 h及不同压力下,沥青质热解产气率高于胶质、芳香分和饱和分;四组分的气相热解产物中,C1的产率明显高于C2~C5组分。增大压力抑制沥青质、胶质及芳香分的热解产气过程而促进饱和分的热解产气过程。随压力的增大,饱和分热解的液态产物的主峰组分碳数先减小,再增大。压力低于20 MPa时,饱和分热解过程中以裂解反应为主;高于30 MPa时,增大压力有利于缩合反应。研究结果可为认识深层油藏原油的稳定程度及天然气的成因提供一定的理论参考。     

Multidimensional gas chromatographic determination of paraffins, olefins and aromatics in naphthas

In order to cope with the increasing demand for gasoline and the need to reduce environmental impact for sustainable development, refineries have installed refining technology by introducing cracking, reforming, isomerization and alkylation. The standard EN 228: 2004 outlines the specification that gasoline, deriving from the blend of several fractions, must have for use in modem piston engines. Naphtha is one of the products from distilling crude oil that can be used as starting material in the reforming process whose derivatives, which are a fraction of gasoline, depend on the composition of the naphtha. Knowledge of the naphtha composition thus enables to provide the final composition of the products of reforming, the efficiency of the plant and also provides information about the crude oil used. In this paper some naphtha samples were analysed by multidimensional gas chromatography. This technique allows in a single analysis a good separation of the hydrocarbon types and within each hydrocarbon type a good carbon number separation.     

色谱-质谱法定性分析柴油浸洗泥浆气的组成

在钻井开采地下石油的过程中,需要加入一定量的柴油作为清洗润滑剂,因此在采出的原油泥浆中会存在混入的柴油组分,在一定温度下,其中的可挥发成分会释放出来,对环境和人身健康造成一定的影响。为了确定原油泥浆中可挥发组分,我们采用色谱-质谱联用技术[1],利用高效毛细管柱的分     

Fractional and component analysis of crude oils by the method of dynamic microdistillation—Differential scanning calorimetry coupled with thermogravimetry

High-resolution differential scanning calorimetry was used to accurately establish the temperature intervals of oxidation/distillation of the major components of crude oils. Some theoretical aspects of the method of dynamic microdistillation, enabling consecutive distillation (oxidation) of the main components of hydrocarbon mixtures, are discussed. The experimental TG-DSC curves show that the temperature scan of the run can be divided into six regions, of which the first belongs to simple distillation of the sample's liquid constituent (the distillate) and the others to oxidative cracking distillation of the solid (heavy) residue. The latter occur in the order paraffins + light oils, middle base oils, heavy base oils, condensed aromatics (resins) and asphaltenes. The probable oxidation mechanisms of different classes of petroleum hydrocarbons operating in different temperature regions are discussed. Full quantitative fractional and group component analysis of a number of crude oils of different chemical classes and geological age was carried out by the combined TG-DSC techniques under specially chosen experimental conditions (those of dynamic microdistillation).     

纳米Fe_3O_4催化剂在稠油水热裂解降黏中的应用

通过高温热解法和低温双相回流法制备了四种不同尺寸的纳米Fe_3O_4催化剂,并将其应用于辽河油田稠油水热裂解降黏实验中。结果表明,制备过程中加入重烷基苯磺酸钠(HABS)表面活性剂能够有效提高Fe_3O_4催化剂在稠油水热裂解体系中的分散性,以高温热解法制备出的HABS修饰的9 nm Fe_3O_4催化剂降黏效果最佳。当稠油量为250 g时,按m(稠油)∶m(催化剂)∶m(油层水)质量比为100∶0.3∶30加入催化剂和油层水,加入0.75 g正作为己烷供氢体,在240℃下反应24 h,辽河油田稠油黏度从86200 mPa·s下降到2065 mPa·s,降黏率高达到97.6%。反应机理分析显示,纳米Fe_3O_4催化剂攻击稠油长链上键能最低C-S键,使其断键,重组分转化为轻组分。     

New view on the oxidation mechanisms of crude oil through combined thermal analysis methods

In the previous study, the oxidation behavior of four Chinese crude oils (Oil 1 to 4) in the presence and absence of rock cuttings was investigated by thermogravimetry/derivative thermogravimetry (TG/DTG) techniques and oxidation tube experiments. The present work investigates the thermal behavior of these oils by combining DTG–DTA method. First, we conducted comparative analysis about mass loss rate from DTG curves and endothermic/exothermic phenomenon from DTA curves attempting to clarify the endothermic or exothermic mechanism in crude oil low-temperature oxidation. Finally, we combined the thermal analysis method with low-temperature oil oxidation tube experiment in porous media to ascertain, whether the two methods are consistent in the aspect of low-temperature oxidation mechanism of crude oil by O₂ consumption rate and CO₂ generating rate (carbon bond stripping reaction rate). Results show that crude oils undergo an endothermic oxidation behavior during low-temperature oxidation stage, suggesting the decomposition of hydrocarbon components. Clay can play a catalytic effect on low-temperature oil oxidation. The results of DTG–DTA tests can also better reflect oil oxidation mechanism under real conditions.     

Thermal kinetics study of light oil oxidation using TG/DTG techniques

In this study, the oxidation behavior of crude oils in the presence and absence of rock cuttings was investigated by thermogravimetry/derivative thermogravimetry (TG/DTG) techniques. Prior to these tests, the composition of cuttings and properties of crude oils were analyzed. Three obvious reaction regions were observed from the TG/DTG curves which are recognized as low-temperature oxidation (LTO), fuel deposition (FD), and high-temperature oxidation. The effects of light components (C_7–15), heavy fractions (asphaltene, paraffin, resin), and cutting on oil oxidation behavior were analyzed. Kinetic analysis of crude oils and oil + cutting mixtures was performed by Arrhenius method, and the data were analyzed at last. Results show that high content C_7–15 hydrocarbons can provide negative effect on the LTO behavior of crude oil. On the contrary, the high content unsaturated heavy hydrocarbons including asphaltene, paraffin, and resin are benefit for the oxidation performance. In addition, a shortened FD stage and higher peak temperature in LTO region are observed by addition of cutting. Cutting especially clay in it plays an active role of catalyzing in oil oxidation reaction.     

Colloidal catalysts based on iron(III) oxides. 2. Peculiarities of catalyzed oxidation of palm oil

The catalytic activity of an iron(III)-oxide-based colloidal catalyst with respect to oxidation of palm oil with atmospheric oxygen at 60°C is investigated. In a microheterogeneous system of palm oil containing phospholipids and large amounts of ??-tocopherol and ??-carotene, oxidation in the presence of the catalyst proceeds by a latent radical mechanism. This mechanism manifests itself as oxygen uptake against a background of almost constant concentrations of natural antioxidants, i.e., ??-tocopherol and ??-carotene. Using a model reaction of oxidation of an individual natural olefin, limonene, it is shown that, in the presence of the catalyst and trace amounts of hydroperoxide, oxidation of the hydrocarbon occurs through the chain free-radical mechanism. The presence of a phospholipid (egg lecithin) dramatically decelerates the catalytic oxidation of limonene and makes the process proceed through the latent radical mechanism, the rate of which is unaffected by oil-soluble inhibitors.     

Production of gas mixtures with regulated ratios between ethylene and carbon monoxide by the gas-phase oxidative cracking of light alkanes

It was found that, in the gas-phase oxidative cracking of C₂-C₅ light alkanes, the ratio between ethylene and CO in the products depends on both the residence time in a reactor and the process temperature. This is due to a change in the contributions of product formation and/or consumption channels with increasing the conversion of the reactants. However, the hydrocarbon/oxygen ratio is the main parameter responsible for the limiting ratio between these products reached in the region of deep conversions of both of the reactants. The channels of formation and, correspondingly, the composition of the main products of oxidative cracking change on going from ethane to n-pentane. In this case, the ethylene: CO ratio increases due to an increase in the concentration of ethylene in the products as the number of carbon atoms in the initial alkane molecule is increased at a constant alkane: oxygen ratio. In the oxidative cracking of the C₂₊ alkane constituents of natural gases, it is necessary to consider the influence of methane, which inhibits the oxidative conversion of heavier alkanes in comparison with their oxidation in an inert gas atmosphere. This leads to a significant decrease in the conversion of oxygen and an increase in the ethylene: CO ratio in the reaction products.     

Characterization of liquid products of automobile tire pyrolysis

The liquid product of automobile tire pyrolysis and its fractions were studied. The amount of the liquid hydrocarbon fraction is 40–45% of the total weight of pyrolysis products. The hydrocarbon fraction is similar in its characteristics to low-sulfur heavy crude oil. Fractionation of the hydrocarbon fuel was performed. The maximal yield of the light distillation fraction is 39% (temperature interval 180–340°C). The extent to which the characteristics of the light fraction obtained meet the regulations was evaluated. The light fraction of hydrocarbon fuel produced by pyrolysis is recommended for use as a component of diesel motor fuel after additional purification.     

Characterization of a heavy oil–propane system in the presence or absence of asphaltene precipitation

When a light hydrocarbon solvent is injected into a heavy oil reservoir under a sufficiently high reservoir pressure, asphaltene precipitation occurs so that the heavy oil is in situ deasphalted during a hydrocarbon solvent-based heavy oil recovery process. The physicochemical properties of this in situ deasphalted heavy oil are rather different from those of the original crude oil in the heavy oil reservoir. In this paper, a heavy oil sample is saturated with a typical light hydrocarbon solvent (i.e., propane) under different saturation pressures in a see-through windowed high-pressure saturation cell. The heavy oil–propane system is characterized by measuring and comparing several important physicochemical properties of the propane-saturated heavy oil samples under different saturation pressures and the flashed-off heavy oil samples, such as the solubility, oil-swelling factor, density, viscosity, asphaltene content, hydrogen and carbon aromaticities. When the heavy oil is saturated with propane at P ≤ 780 kPa and T = 20.8 °C, there is no observable asphaltene precipitation and deposition under a microscope camera. The respective properties of the propane-saturated heavy oil samples taken from the upper and lower parts of the saturation cell are measured and found to be essentially the same within the experimental errors so that the entire system is considered to be almost homogeneous. If the saturation pressure is increased to P = 850 kPa, strong asphaltene precipitation occurs and some large asphaltene particles are deposited onto the bottom of the saturation cell. In this case, the heavy oil is deasphalted and the flashed-off heavy oil has lower density, viscosity, asphaltene content, hydrogen and carbon aromaticities than those of the original heavy crude oil.     

DMC聚醚的降解研究

研究DMC聚醚 (双金属催化剂的聚环氧丙烷 )的降解现象 .讨论了各种因素对降解的影响 ,以及降解中不饱和度的变化情况 .实验表明 ,DMC聚醚的降解与自由基有关 ,降解在常温下 1 5天后开始发生 ,在抗氧剂存在下受到抑制 .加入抗氧剂 1 0 1 0和 61 8可使聚醚得以稳定储存     

Effect of different clay concentrations on crude oil combustion kinetics by thermogravimetry

The objective of this research was to investigate the effect of different clay composition and concentrations on the thermal behaviour and kinetics of heavy crude oil in limestone matrix by thermogravimetry (TG/DTG). In TG/DTG experiments, three distinct reaction regions were identified in all of the crude oil + limestone mixture known as low temperature oxidation (LTO), fuel deposition (FD) and high temperature oxidation (HTO) respectively. Addition of clay to porous matrix significantly affected the reaction regions. Significant reduction of activation energy due to addition of clay to crude oil indicates the catalytic effect of clay on crude oil combustion.