轻质油藏注空气低温高压氧化实验研究

空气驱是颇具发展前景的清洁、高效的提高采收率新技术。针对某轻质油藏流体特性开展了轻质原油与空气低温高压氧化实验研究。研究结果表明,氧化反应能大幅度降低空气中的氧气含量,使含氧量下降到安全范围内;氧化反应中有CO2和醛类等新物质生成,同时发生中间烃裂解现象。在实验条件下,裂解轻烃、自生CO2和空气中的N2对原油表现出较强的抽提能力。     

Effect of low-temperature oxidation of light oil on oil recovery during high pressure air injection

In this research, the low-temperature oxidation (LTO) behavior of light oil was evaluated via isothermal oxidation tube experiments. Also, the core model together with nuclear magnetic resonance (NMR) analyzer was implemented to explore the effect of LTO of light oil on oil recovery during high pressure air injection (HPAI). The results indicated that the polycondensation reaction of light components (C₅-C₆) and intermediate ones (C₇-C₁₇) for light oil was the preferred reaction path during LTO process. The oxygen addition was the primary oxidation reaction in LTO, but the LTO reaction presented a more favorable trend for the bond scission with the oxidation degree. Because of the gas flow steering resulting from property variation of light oil and heat release determined by LTO, the total oil recovery yielded by air flooding was 8.82% higher than nitrogen flooding.     

利用高压注空气技术开发低渗透轻质油油藏

本文主要介绍了利用高压注空气技术提高低渗透轻质油油藏采收率的原理，及其与稠油火烧油层工艺的主要区别，综合国外现场及实验室的研究资料，指出：油藏在空气过程中自燃、烟道气与轻质油油藏条件下发生混相，是低渗透轻质油油藏注空气成功开发的2个主要条件。并列举了国外注空气开发低渗透轻质油油藏的几个成功实例。     

Thermal investigation on crude oil oxidation kinetics through TG/DTG and DTA tests

In this nonisothermal research, the thermal behavior and oxidation kinetics of crude oils were investigated through TG/DTG and DTA tests at three heating rates. The resulting curves exhibit three integrated reactions of distinct oxidation mechanisms (LTO, FD, and HTO) sequentially in overlapped temperature intervals as reaction progresses, the behaviors of that are affected greatly by heating rate. Because of the larger amounts of heavy components and higher availability of deposited fuel, heavy oil exhibits more excellent heat release capability but higher kinetic parameters than light oil, especially in HTO region. Due to the insufficient parameters calculation based on a single kinetic method, other formulated models would be introduced for comparative analysis in the next work to upgrade kinetic research.     

The influence factors analysis of the light crude oil oxidation reaction process

During the high pressure air injection process, there are different types of oxidation reactions, which do not exist, and the predominant reaction type of is dependent on the specific conditions. In this study the influences of formation temperature, pressure, and oxidation time on light crude oxidation have been studied via oxidation experiments. And it is shown that the reaction types could be effectively improved by the temperature increment, which decreases the oil viscosity. As well, the pressure and oxidation time have obvious effects that were mainly present in oxygen addition reactions and the viscosity increase.     

The mechanism of the oxidation of light oil

High pressure air injection (HPAI) has been proven as an enhanced oil recovery process in many fields. The reactions associated with crude oil and oxygen are the main difference between HPAI and other gas injection processes. In order to study the reaction schemes, different experiments, such as the combustion tube, kinetic cell, accelerating rate calorimeter, and thermogravimetry analysis, are conducted. In this paper, a reaction scheme is build that includes three classes of reactions: low-temperature oxidation, cracking, and combustion. We then use simulation models with the proposed reaction scheme included to history match the data from a combustion tube experiment and a kinetic cell experiment. It is demonstrated that the reaction scheme is valid. Based on this study, lumping the crude oil into four pseudocomponents brings a good matching result, and the kinetic parameters are obtained through matching the experimental results.     

压力对轻质原油氧化动力学参数的影响

利用高压差示扫描量热仪(PDSC)研究了不同压力下轻质原油的氧化放热特性,并结合Friedman方法计算了反应体系的活化能,分析了不同反应阶段压力对氧化动力学参数的影响。结果表明:随着压力升高,放热起始温度、峰值温度和反应结束温度均趋向低温,放热量也随之增大,尤其低温氧化放热速度大幅提高,氧化反应明显加强,说明压力增大导致原油在低温下更容易发生氧化反应;活化能在低温氧化前期迅速上升再下降,进入低温氧化后期趋于稳定,到高温氧化阶段再次上升,活化能随反应进程的波动,说明原油反应行为或反应速度发生了变化;对比不同压力下各反应阶段的活化能发现,活化能均随压力升高而降低,说明压力对氧化反应有促进作用,压力越大,反应越容易进行。     

注空气开发中地层原油氧化反应特征

通过分析中国不同类型油藏注空气开发的技术优势,依据室内实验和现场试验的研究成果,阐述了轻质油和稠油不同氧化阶段的氧化反应特征。研究认为,不同氧化阶段地层原油的氧化反应特征存在明显差异：在中低温氧化阶段,氧气直接与原油接触,温度越高氧化反应越强;无论轻质油还是稠油,高温氧化阶段氧化反应的主要对象是焦碳而不是原油。进一步提出了划分轻质油和稠油氧化反应4个阶段的温度区间,轻质油比稠油中温氧化反应的起始温度低,放热量大,轻质油比稠油更容易诱发氧化反应;轻质油高温放热峰值（8.06 mW/mg）略高于中温放热峰值（6.42 mW/mg）,而稠油高温放热峰值却是中温放热峰值的5倍,稠油注空气火驱开发应该以实现高温氧化为主要目标。因此,根据油藏温度和油品性质等关键指标可选择空气驱或火驱等注空气开发方式：当油藏温度小于120℃时,由于氧化放热不明显,为了避免注空气开发的爆炸风险,应以减氧空气驱有效补充地层能量的开发方式为主;当油藏温度大于120℃时,在油藏条件下原油就可发生明显的氧化反应,此时可实施不减氧空气驱,充分利用原油氧化反应放热提高采收率;对于油藏温度小于120℃的稠油油藏,可通过电加热器等人工手段实现高温点火,进行高温火驱开发。     

Catalytic effect of in-situ preparation of copper oxide nanoparticles on the heavy oil low-temperature oxidation process in air injection recovery

In situ prepared hydrophobic CuO nanoparticles, about 84.3 nm in mean diameter, was synthesized and used to catalyze heavy oil low-temperature oxidation (LTO) reaction. Experimental results showed the average oxygen consumption rate with CuO nanoparticles addition increased by 1.4 times, and the residue oxygen content in tail gas in autoclave was decreased from 8.76% to 3.9% compared to the blank experiment (without CuO nanoparticles). In addition, the CuO nanoparticles could facilitate the cleavage reaction during LTO. This study can provide guidelines to improve effectively the safety of air flooding technology in the heavy oil.     

Catalytic effect of zinc naphthenate on the heavy oil low-temperature oxidation in an air injection process

Air-assisted steam flooding is a new effective technique for enhanced oil recovery in heavy oil reservoirs. The authors prepared zinc naphthenate as the catalyst in the laboratory and the investigated effects on low-temperature oxidation of heavy oil through the isothermal reactor. The results indicated that zinc naphthenate could accelerate the oxygen consumption rate and facilitate the cleavage reaction in the low-temperature oxidation process. The data shed more light on the mechanisms of low-temperature oxidation reactions of heavy oil and can provide a new way to enhance the recovery of heavy oil reservoir.     

Influence of clay minerals on oxidation reaction of light crude oil

By means of the static oxidation test of crude oil, the influence of clay minerals on the light crude oil oxidation reaction under reservoir temperature and pressure was investigated by means of orthogonality analysis method. Based on the thermogravimetric analysis, the oxidation characteristics of clay minerals on crude oil during heating were analyzed. The results show that the clay minerals have different catalytic effects on light crude oil, of which montmorillonite has the best catalytic effect and kaolinite has the worst. And they have the positive effect to light crude oil on air injection, which could enhance oil recovery.     

吐哈盆地鄯善油田轻质油藏注空气开发机理研究

为了探讨轻质油藏注空气提高采收率的机理,在注空气室内实验研究的基础上,运用热采数值模拟技术．研究了鄯善油田不同开发阶段注空气后油藏内原油低温氧化反应过程、相态变化规律及分布特征、油藏能量的变化规律;同时研究了油藏温度、油藏压力和空气注入速度等因素对轻质油藏注空气开发效果的影响,阐明了注空气开发的主要驱油机理,即烟道气驱和附加的热效应,对轻质油藏注空气开发矿场试验具有一定的指导作用。     

稀油火烧油层物理模拟

注空气开发主要分为稀油注空气低温氧化以及稠油火烧油层2种技术。针对轻质原油火烧油层技术开展研究,采用热重/差示扫描量热同步热分析仪研究稀油高温氧化放热特性和反应动力学参数;在实验压力为5 MPa条件下采用高压燃烧管研究稀油高温火烧前缘传播稳定性以及稀油火烧油层基础参数。研究结果表明:测试稀油高温氧化活化能为148 kJ/mol,与文献中稠油高温燃烧反应活化能相近;人工点火后,稀油可以形成稳定的高温氧化前缘,实现稳定的高温燃烧驱替,前缘温度高达500℃;出口CO₂浓度和燃料的视H/C原子比进一步证明,燃烧前缘处的反应类型为高温氧化反应;稀油火烧油层驱油效率达92%,空气/油比为858 m³/t,具有较高的驱油效率和较低空气/油比。     

Sensitivity study on thermal behavior and kinetics of crude oil using thermal analysis techniques

In this study, the effect of heating rate, oil chemical composition, and clay mineral type on thermokinetic behaviors of oil oxidation was investigated by TG and DTA tests. The results show that temperature intervals of reactions are extended and peak and burnout temperatures are shifted to higher values when increasing the heating rate. Heavier oil with more heavy components exhibits faster reaction rate and higher energy requirement in the low-temperature oxidation stage, and releases more heat in the high-temperature oxidation stage. The catalytic properties and surface area effect of clays can positively influence the high-pressure air injection process through forming more carbonaceous deposits and lowering the activation energy of reactions.     

The low temperature oxidation characteristics of SARA fractions in air flooding process

The Low Temperature Oxidation (LTO) characteristics of SARA fractions isolated from light crude oil were studied applying the static oxidation experiments. The results show that the LTO reaction of SARA fractions can occur when temperature is above 50°. Under reservoir conditions, the oxidation activities of the SARA fractions were resin > aromatics > saturate. The theoretical LTO reaction rate of crude oil calculated based on the SARA oxidation characteristics is in good agreement with the measured value. Therefore, it is an effective method to reveal the LTO mechanism of crude oil by studying the LTO mechanism of SARA fractions.     

注空气开采过程中稠油结焦量影响因素

通过建立油藏高温、高压反应模拟实验装置,物理模拟了稠油注空气开采过程中焦炭的生成过程,研究了反应气氛、温度、压力以及空气通风强度对稠油生焦量的影响。研究表明：在空气气氛下,原油低温氧化显著促进了焦炭生成,5 MPa反应压力下,每克稠油最高焦炭生成量为0.375 g,是氮气气氛下最高生焦量的2.5倍,焦炭初始生成温度受低温氧化影响比氮气条件降低了近200℃。随压力升高,加剧的低温氧化反应提高了焦炭生成量,但是5 MPa后压力影响不再显著。随空气通风强度增加,生焦量并非持续增加,而是在33.4 N·m³/（m²·h）附近存在极值。进一步对比分析了焦炭的高温氧化消耗与原油组分蒸馏失重对焦炭生成量的影响。其结果表明,焦炭氧化是空气气氛下温度自225℃升高至300℃过程中焦炭净生成量减少的主要原因。在氮气气氛下,随温度升高至450℃,加剧的原油热解缩聚反应增加了生焦量,但温度进一步升高引起焦炭自身热解失重,生焦量降低。另外,实验还发现,当温度超过200℃时,反应管内油砂中心温度超过外壁面加热控制温度。分析表明,超温现象由原油组分的低温氧化和部分活性较强的焦炭高温氧化引起,因此该稠油存在油层自燃点火的应用潜力。     

Research on oxidation kinetics of tight oil from Wolfcamp field

Thermogravimetry and differential scanning calorimetry were performed on a tight oil that was collected from the Wolfcamp shale reservoir, USA. The results indicate that although the oil has similar properties to those of a light oil, it shows similar thermal-oxidative behaviors to those of a heavy oil. Kinetic data of the tight oil as activation energy and frequency factor were estimated by the Arrhenius method. This kinetic analysis could provide us insight to characterize the reactivity of the tight oil, and establish parameter values for kinetic models used in the numerical simulation of the air injection process.     

轻质原油低温氧化催化技术

注空气采油技术由于气源和成本优势,具有广阔的发展潜力,但是安全问题一直是限制其应用的重要因素。为加快氧气消耗速率,降低生成烟道气中氧气的含量,提高注空气的安全性,进行了原油低温氧化催化技术研究。通过评价过渡金属元素对低温氧化反应的催化效果,筛选了催化剂及其用量;研究了温度、压力、含水率和岩石矿物等对催化性能的影响,并采用多管平行实验研究了不同反应阶段低温氧化反应的特征;在动力学参数计算和红外谱图分析的基础上研究了原油低温氧化催化反应的催化机理。实验结果表明:过渡金属元素Cu对原油低温氧化反应有很好的催化效果,优选的催化剂为CuCl₂,最佳用量为原油质量的0.88%,在油藏条件下可提高反应速率近2倍;温度和压力升高对低温氧化反应有促进作用,在所研究的温度、压力和反应阶段内,催化剂的低温氧化催化效果显著;催化剂对原油低温氧化反应的催化机理为配位催化,可显著降低反应的活化能,加快低温氧化反应速率,提高原油的耗氧能力。     

轻质油油藏蒸汽驱采油研究进展

调研了国内、国外轻质油油藏蒸汽驱采油研究的相关资料,综述了此项研究在驱油机理、驱油效率影响因素、油藏筛选标准等方面取得的新进展,总结了针对低渗透裂缝型及高孔隙度油藏蒸汽驱模拟研究的成果。蒸汽驱技术可以进一步提高聚合物驱后轻质油油藏的采收率。