In situ catalytic upgrading of heavy crude oil through low-temperature oxidation

The low-temperature catalytic oxidation of heavy crude oil (Xinjiang Oilfield, China) was studied using three types of catalysts including oil-soluble, watersoluble, and dispersed catalysts. According to primary screening, oil-soluble catalysts, copper naphthenate and manganese naphthenate, are more attractive, and were selected to further investigate their catalytic performance in in situ upgrading of heavy oil. The heavy oil compositions and molecular structures were characterized by column chromatography, elemental analysis, and Fourier transform infrared spectrometry before and after reaction. An Arrhenius kinetics model was introduced to calculate the rheological activation energy of heavy oil from the viscosity– temperature characteristics. Results show that the two oil-soluble catalysts can crack part of heavy components into light components, decrease the heteroatom content, and achieve the transition of reaction mode from oxygen addition to bond scission. The calculated rheological activation energy of heavy oil from the fitted Arrhenius model is consistent with physical properties of heavy oil (oil viscosity and contents of heavy fractions). It is found that the temperature, oil composition, and internal molecular structures are the main factors affecting its flow ability. Oil-soluble catalyst-assisted air injection or air huff-n-puff injection is a promising in situ catalytic upgrading method for improving heavy oil recovery.     

冷1块稠油低温空气氧化物模研究

为了进一步发展注气提高采收率技术,提高超稠油油藏的开发效果,采用低温空气氧化驱油物理模型实验,研究建立了二组线型物理模型,开展了冷1块稠油注空气驱油实验。实验研究了冷1块稠油与空气发生低温氧化的温度、产出含氧量,并对其原油低温氧化采油的可行性进行了分析。实验结果表明：随着温度的升高,冷1块稠油低温氧化的采出程度增大;将空气中的氧消耗到安全值以内,浸泡的时间随温度升高不断减少;冷1块进行注空气吞吐可以采出6．86％-10．24％的原油,技术上是可行的。     

稠油火驱过渡金属钴盐催化氧化实验

针对新疆红浅火驱工业化试验区稠油二次点火难的问题,开展过渡金属盐催化氧化稠油实验研究,评价过渡金属盐促进重质油火驱前缘稳定推进的效果.利用一维燃烧管开展火驱物理模拟实验,分析钴盐对稠油火驱前缘峰值温度和前缘推进的影响;采用同步热分析仪(TG-DTA)测定稠油氧化反应过程,建立稠油催化氧化动力学方程,计算稠油燃烧过程中低...     

非硫、磷有机钼添加剂在发动机油中的应用

从提高内燃机油的抗氧、抗磨、减摩性能出发,介绍了3种类型的非硫、磷有机钼添加剂在发动机油中的应用.有机钼胺络合物在基础油中不仅具有较好的抗腐蚀性能,而且与多种含硫添加剂具有较好的抗磨和减摩协同性能,环烷酸钼、异辛酸钼与烷基二苯胺在加压差热扫描量热实验(PDSC)和热油氧化实验(HOOT)中均体现出了较好的协同抗氧效果,钼酸酯化合物不仅与丁辛基二硫代磷酸锌和二戊基二硫代氨基甲酸锌表现出了突出的抗磨协同作用,而且与苯胺抗氧剂也表现出了很好的协同抗氧和沉积物抑制能力.     

Effect of oil-solubility catalysts on the low-temperature oxidation of heavy crude oil

Due to low oil recovery factor in heavy oil reservoir, air injection with catalyst becomes a competitive technology to effectively reduce viscosity of crude oil as a result of the low cost and small environment pollution. This paper determined the feasibility of air injection with catalyst in a heavy oil reservoir through static and dynamic experiments. The results indicated that under the effect of catalyst, oxidation between heavy oil and air could significantly reduce the viscosity of crude oil. The optimal catalyst contained 0.7?wt. % oil-solubility organic acid copper and 0.5?wt. % sodium hydroxide. With the oxidation time increasing, viscosity of crude oil decreased and oil recovery factor increased. With temperature increasing, viscosity of crude oil decreased sharply and oil recovery factor increased. The oil recovery factor of air huff-n-puff process was 30.2%. Air injection with catalyst in the reservoir is a promising technology.     

Comparative Study of Light and Heavy Oils Oxidation Using Thermal Analysis Methods

In this work, the oxidation behavior of light and heavy oils was investigated by combining TG-DTA test and oxidation tube experiments, in the presence and absence of cuttings, respectively. Results show that high content heavy components benefit low-temperature oxidation (LTO) performance and heavy oil has better oxidation activity at low temperature and is more easily oxidized. All samples undergo an endothermic reaction during the LTO stage and the faster the LTO rate is, a larger amount of energy is absorbed by oil, and more heat is released in the high-temperature oxidation stage. An excellent consistency is found between thermokinetic analysis and oxidation tube experiment results.     

火驱高温与低温氧化转换界限研究

火驱存在原油低温氧化和高温氧化2种燃烧状态,针对低温氧化过程不稳定、热效率低、采出程度低等问题,以杜66块火驱为研究对象,开展了室内物理模拟和数值模拟实验,通过耗氧量及不同组分尾气数据的历史拟合,建立了火驱反应动力学模型,构建了基于火驱前缘初始温度、通风强度的高温与低温氧化转换界限图版。研究表明:高温氧化下,杜66块原油视H/C原子比为0.5～2.0,CO/CO₂体积比为0.13～0.40;低温氧化过程燃烧不稳定,易熄灭;杜66块火驱高温与低温氧化的临界前缘初始温度和通风强度分别为280 ℃、1.0 m³/(m²·h),低于或接近临界值将面临转入低温氧化甚至熄火风险;基于杜66块火驱提出了维持最低通风强度、分层火驱等开发对策。该研究为火驱油藏工程设计提供了理论依据。     

Low-temperature isothermal oxidation of crude oil

In this work, the low-temperature oxidation (LTO) characteristics of different API gravity crude oils, involving one light, one medium, and one heavy, are studied comprehensively from the aspects of effluent gas, oxidized oil, and pressure drop. The results reveal that heavy oil exhibits faster LTO reaction rate and stronger O₂ consumption capability compared with lighter ones. There are a certain amount of carbonaceous deposits in oxidized oils and the carbonation progress of heavy oil is brought to a deeper degree. The pressure drop rule of oil samples is speculated to be the consequence of “skin effect” and crude oil with more heavy species shows higher oxidation activity, which contributes to an improved understanding about the LTO mechanism from the molecular perspective and needs further research.     

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.     

稠油井下改质降粘技术的研究进展

综述了三种稠油井下改质降粘技术：水热裂解降粘技术、注空气低温氧化降粘技术和离子液体改质降粘技术。分析了三种稠油改质降粘技术的作用原理、研究成果和优缺点。着重介绍了已经应用的水热裂解降粘技术和注空气低温氧化降粘技术。笔者认为稠油注空气低温氧化降粘技术具有更大的优势,并指出了稠油井下改质降粘技术所面临的问题。     

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。     

Differential scanning calorimetric study of heavy oil catalytic oxidation in the presence of manganese tallates

Metal tallates are attracting increasing interest in thermal enhanced oil recovery. Biodegraded heavy oil catalytic oxidation was investigated in the presence of manganese tallates. Differential scanning calorimetry (DSC) was used to highlight the effect of manganese tallates on the oxidation of heavy oil. The obtained data have been performed using the Kissinger method based on the isoconversional principle. Strong evidence of manganese tallates effect on heavy oil oxidation was illustrated in the high temperature oxidation region (HTO). The obtained catalyst increased constant rate in this region almost three times more than when reactions occur in its absence. We believe that we have found an innovative and economical solution to enhance heavy oil via in-situ combustion.     

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.     

稠油水热裂解反应催化剂适应性研究

以辽河油田的稠油为原料,环烷酸钴、环烷酸镍、柠檬酸钴或柠檬酸镍为催化剂,研究了稠油水热裂解反应催化剂在地层中的适应性。结果表明,催化剂与地层水的配伍性良好,不会对地层造成伤害。以柠檬酸钴为催化剂,稠油催化改质的反应条件为:温度240℃,时间24 h,稠油100 g,地层水30 g,催化剂摩尔浓度9×10-3mol/L;在此条件下,稠油降黏率最高(达到66.82%)。外加催化剂与油藏矿物具有协同效应,催化剂的加入能够强化矿物催化的稠油水热裂解反应。     

分散型环烷酸钴催化剂的制备及其在重油悬浮床加氢裂化中的应用

采用皂化反应和复分解反应合成了适用于重油悬浮床加氢裂化反应的分散型环烷酸钴催化剂,并优化了合成条件;通过光学显微镜、激光粒度仪、XRD和SEM方法对硫化后的催化剂进行了表征;通过釜式反应评价了该催化剂在委内瑞拉380号燃料油悬浮床加氢裂化反应中的性能。实验结果表明,合成分散型环烷酸钴催化剂的优化条件为:在皂化反应中,NaOH质量分数15%,环烷酸与NaOH摩尔比1∶0.995,皂化温度95℃,皂化时间3 h;在复分解反应中,CoSO4溶液质量分数15%,以滴加方式加入CoSO4溶液,复分解反应温度90℃,复分解反应时间2 h。该催化剂硫化后颗粒分散度较大,团聚不明显,表面粗糙,有较大的比表面积,主要以立方晶系Co9S8晶型存在,并对重油悬浮床加氢裂化反应有较好的抑焦效果。     

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.     

Low-temperature oxidation and thermal kinetics analysis of light and medium crude oils

In this research, low-temperature oxidation (LTO) and thermal kinetics analysis of light and medium crude oils were analyzed by static isothermal experiments and thermogravimetry (TG). The results elucidated that, during LTO process, medium oil possessed stronger oxygen consumption capability than light oil and oxygen addition was the dominating reaction path for both light and medium oils; more heavy components contained in medium oil were oxidized to form higher molecular-weight material with lower H/C. In TG experiments, three main reaction zones were identified known as LTO, fuel deposition (FD) and high-temperature oxidation (HTO). Compared with light oil, LTO range and corresponding mass loss were lowered for medium oil with more oxygenated compounds left behind to be converted into coke materials. The activation energy for medium oil were higher than that for light oil in LTO stage while less in HTO stage owing to the difference of oil components.     

环烷酸丁酯增塑剂

研究了环烷酸中中性油的分布和酯化催化剂,使用铁系或铝系催化剂进行环烷酸和丁醇的酯化反应,反应物用蒸馏法分离,轻馏分可用作柴油掺和料,馏余物可用作重油燃料,主馏分是环烷酸丁酯。应用实验证明,环烷酸丁酯是性能良好的辅助增塑剂。此外,还讨论了产品的酸值、色泽和工业化生产的可能性。     

稠油油田空气辅助蒸汽驱现场试验

为考察稠油油田空气辅助蒸汽驱的开采效果,开展了稠油油田空气辅助蒸汽驱现场试验研究工作。在齐40块蒸汽驱试验区选择原油濒临枯竭的、油藏已经发生严重蒸汽窜流和超覆的、亟待改变开发方式的5个井组进行现场试验,结果表明:5个试验井组平均单井组日产油由14.8 t/d升至16.1 t/d,油汽比由0.14升至0.17;油层纵向动用程度明显提高,分析认为是注入的空气在纵向和平面上首先向蒸汽驱优势方向波及,与残余原油发生低温氧化反应使孔隙中沥青质沉积增加,降低油层渗透率,迫使蒸汽转向,扩大蒸汽波及范围。研究认为:空气辅助蒸汽驱宜采用连续式空气/蒸汽注入方式;汽气比接近1: 40可取得较高采收率;70 m井距注入的空气与地下原油发生低温氧化反应,油藏温度有所提高,产出氧气含量可降到安全范围内。现场试验取得成功,利用空气辅助蒸汽驱改善稠油油田蒸汽驱开发效果具有可行性。所选试验井组存在的问题在普通稠油蒸汽驱井组生产后期具有普遍性,因此本文试验方法和相关技术参数可为类似井组开展空气辅助蒸汽驱试验提供参考。     

满足国Ⅵ排放的重负荷燃气发动机油研制及应用

随着国Ⅵ排放法规的执行,发动机厂商纷纷推出满足国Ⅵ排放的重型燃气车,该车辆主要采用当量燃烧与三元催化后处理相结合的技术路线,对润滑油的磷含量、硫酸盐灰分以及高温氧化性能提出了苛刻要求,文章主要阐述了国Ⅵ重负荷燃气发动机油的性能要求,并对研制的重负荷燃气发动机油在国Ⅵ重型燃气发动机1000 h的应用进行了研究,结果表明,重负荷燃气发动机油具有优异的高温清净性和抗氧化和抗磨损能力,可满足国Ⅵ重型燃气发动机的用油要求。