超声波辅助稠油层内催化水热裂解实验研究

将超声波应用到稠油催化水热裂解实验中,研究了超声波辅助催化水热裂解对胜利油田孤东稠油物化性质的影响。结果表明,超声波辅助作用下稠油的降黏率达到86.2%,与催化水热裂解相比,稠油的平均相对分子质量进一步减小,饱和烃和芳香烃组分含量增加,胶质和沥青质组分含量减少,稠油组分的氢碳原子比增加,杂原子含量减小。动态模拟实验中超声波辅助层内催化水热裂解效果显著,稠油采收率达到53.91%,降黏率达到80.5%。由此表明,超声波辅助催化水热裂解具有可行性,超声波与催化剂协同作用促进了水热裂解反应,一定程度上改善了稠油的品质。     

油藏矿物和化学剂强化稠油水热裂解降黏研究

采用大庆、辽河两种稠油,研究了油藏矿物、硫酸镍催化剂以及四氢萘供氢剂对其水热裂解反应的影响。结果表明,与单纯水热裂解相比,油藏矿物的加入能使两种稠油的平均相对分子质量减小,饱和烃和芳香烃组分含量增加,胶质和沥青质组分含量减少,稠油的降黏率分别从7.41%和12.95%增加到16.05%和25.29%,油藏矿物对稠油水热裂解反应具有催化作用;将硫酸镍和四氢萘加入反应体系后,稠油平均相对分子质量进一步降低,族组分中饱和烃和芳香烃进一步增加,胶质和沥青质组分进一步减少,稠油黏度明显降低,降黏率可高达84.39%。     

双亲催化剂作用超稠油水热裂解降黏机理研究

合成双亲催化剂,200℃与超稠油反应后,降黏率达96.26%。通过气相色谱仪、元素分析仪、分子量测定仪、红外光谱仪及核磁共振波谱仪对反应前后稠油的物化性质进行分析。结果表明,反应后稠油胶质与沥青质含量减小,稠油分子量下降,沥青质分子量降低幅度最大;稠油及其重质组分的氢碳原子比增加,硫的含量减小。稠油发生水热裂解反应的同时,存在沥青质的聚合反应,沥青质的裂解在降黏反应中起到了关键的作用;双亲催化剂促进了水热裂解反应,同时抑制了聚合反应;双亲型催化降黏剂携带的具有活性催化功能的离子协同高温水作用于分子中的C-S、C-N、C-O、C-C及C=S、C=O、C=N、C=S等键,使其发生系列链的断裂、加氢、开环、成环、脱硫等反应,促进了稠油黏度的降低,稠油及其重质组分的氢碳原子比增加,稠油的品质得到一定程度的改善。     

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。     

超稠油供氢水热裂解改质降黏研究

通过超稠油水热裂解反应前后黏度、沥青质、硫质量分数等性质的变化，研究了超稠油进行水热裂解的主要影响因素及规律。结果表明，超稠油中含有一定量的硫是地层注蒸汽温度下进行水热裂解反应的前提。温度和时间对反应有很大影响。供氢剂中四氢萘对超稠油水热裂解影响最大。四氢萘供氢剂与硫酸镍催化剂复配使用对超稠油水热裂解有协同效应。水热裂解物理模拟实验表明,胜利单家寺油田超稠油通过供氢催化水热裂解降黏率可达70%以上。胶质、沥青质、硫质量分数降低，H/C原子比提高，超稠油得到一定程度的改善。     

水溶性有机钴(Ⅱ)盐催化的稠油低温清洁水热裂解

为了开发新型稠油低温清洁水热裂解催化体系,合成了系列钴盐催化剂,用于低温下催化稠油热裂解,利用高温高压反应釜模拟井下热采条件,在反应温度为180℃、反应时间为24h、催化剂Co-3加量为0.5%,稠油降黏率可达到84.5%.稠油组分分析表明:水热裂解催化反应后,胶质、沥青质等重质组分含量减少;TGA和GC显示稠油经水热催化裂解反应后,轻质组分含量明显增加.     

水溶性配合物催化的稠油低温热裂解研究

在一种新型稠油低温裂解催化体系中合成了两个系列10个过渡金属配合物催化剂。该反应体系中水对原油热降解反应有一定的影响,合适的用量水/油(质量比)为0.3。部分合成水溶性催化剂180℃下对稠油热裂解具有明显的催化作用,催化剂N5的降凝作用效果最好,经催化水热降解改质反应后原油的凝点降低11.4℃;催化剂N2和N5的催化降黏效果较好,降黏率可达70%以上,催化剂N5的最佳用量为0.5%;热重分析和气相色谱分析显示原油热催化降解反应后轻质组分明显增加。     

纳米Ni催化剂在超稠油水热裂解降黏中的应用研究

采用甲基环己烷水正辛醇AEO9形成的微乳液体系制备纳米金属Ni催化剂，并利用该催化剂催化辽河超稠油的水热裂解反应。研究结果表明， 280℃时纳米金属Ni能够促进超稠油的水热裂解反应。与原超稠油相比，反应后样品的硫质量分数由0.45%降到0.23%，胶质、沥青质质量分数分别降低了15.83%、15.33%；GC-MS分析结果表明，甲基环己烷在改质过程中能够脱氢生成甲苯；C、H元素分析结果表明，反应后样品中胶质、沥青质的H/C原子比增加，说明从甲基环己烷上脱下的氢能够转移到超稠油中。表面活性剂AEO9、水和油，在改质结束后的降温过程中，形成了稳定的油包水型乳液，起到乳化降黏作用；而添加的甲基环己烷、正辛醇均能起到稀释降黏作用；在上述降黏作用的协同影响下，反应后样品50℃时的黏度由原来的139800mPa·s降至2400mPa·s，由此表明，纳米Ni催化剂对辽河超稠油水热裂解降黏的催化效果显著。     

稠油催化降黏技术开发研究进展

随着常规油气资源的过量开发和快速消耗,稠油等低品位油气资源的高效开采越来越受到人们的重视.稠油由于其黏度大和流动性差导致开采效率低下、开发困难.因此,降低稠油黏度并提高其流动性是稠油高效开采的技术关键.1982年HYNE首次报道了金属催化剂在稠油水热降黏中的结果,Ni、Cu等金属催化剂的加入可以有效降低稠油黏度.此后,水热催化降黏的方法得到了长足的发展,目前催化剂的类型主要包括矿物质催化剂、水溶性催化剂、油溶性催化剂、分散性催化剂、超强酸催化剂等.在水热催化反应中稠油的4个组分(沥青、胶质、烷烃、芳香烃)会发生变化,特别是S、N等杂原子含量的变化对稠油的黏度和品质有着重要的影响.本文作者针对稠油的开采工艺、水热催化降黏剂的种类和特点、水热反应的机理等进行了评述,并对今后的研究方向进行了展望.     

自由基引发剂强化稠油催化水热裂解降黏行为

本文考察了自由基引发剂对胜利油田单56区块稠油样品催化水热裂解反应过程的协同强化作用.在反应温度为220℃,添加0.2 wt%的引发剂——过氧化二叔丁基,使水热裂解后的降黏率由不加引发剂时的61.4%升高到72.7%.此外,在引发剂存在、150℃条件下,降黏率可达到69.0%,表明引发剂的加入可显著提高较低反应温度下的水热裂解效果.对反应前后油样进一步分析发现,反应样品中饱和分、芳香分、胶质和沥青质平均分子量均下降;饱和分、芳香分含量增加,而胶质、沥青质含量下降;胶质、沥青质中氢碳原子比增加,含硫量减少,含氮量变化不大;表明重质组分在水热裂解过程中发生了裂解反应、尤其是含硫官能团在水热裂解中发生了反应;反应样品沥青质及胶质芳香环系的缩合程度降低.实验结果表明,反应过程中稠油重质组分发生了裂解,而且胶质的裂解程度更大,轻质组分含量增加,导致稠油黏度降低、流动性提高,在一定程度上改善了稠油的品质;引发剂可以在较低温度下产生自由基,从而使水热裂解反应在较低反应温度下有效进行.     

蒸气开采过程中金属盐对稠油粘度及平均分子量的影响

探讨了在注蒸气条件下，稠油的粘度和平均分子量随蒸气温度、反应时间的变化规律，研究了金属盐、油层矿物对稠油水热裂解反应的影响。实验结果表明，在注蒸气的条件下，辽河稠油可以发生水热裂解反应。金属盐的存在，可以加速稠油的水热裂解反应，从而导致粘度和平均分子量的进一步降低，使稠油的粘度由原始的124.5 Pa·s下降到32.4 Pa·s，下降了74.0%，平均分子量由反应前的654下降到398。高温下油层矿物对水热裂解反应有促进作用，在反应体系中，在有水时加入质量分数为10%的油层矿物时，稠油的粘度由原始的124.5 Pa·s下降到82.5 Pa·s，下降了33.7%。在蒸气条件下，在金属盐和油层矿物共存时，稠油粘度由124.5 Pa·s下降到26.8 Pa·s，下降了78.5%。这为实现井下催化降粘开采稠油提供了理论依据。     

Viscosity reduction of citric-Fe(III) in catalytic aquathermolysis of heavy oil at low temperature

A Fe(III) coordination complex was synthesized, characterized, and then used in aquathermolysis of heavy oil as catalyst at relatively low temperature, 180°C. The effects of water amount, catalyst concentration on aquat hermolysis were investigated in this work. The crude oil before and after aquathermolysis was fully characterized, and the mechanism of viscosity reduction was discussed in detail. The results show that heavy oil can undergo aquathermolysis in the present of water and citric-F e(III) complex at low temperature. Besides, the catalytic aquathermolysis could not only decrease the viscosity of heavy oil, but also remove some heteroatoms, finally make the flow properties better and the quality upgraded.     

Methanol enhanced catalytic viscosity-reduction of heavy oil by transition metal-Mannich base complex under low temperature

A series of transition metal-Mannich base complex was synthesized and screened for catalytic aquathermolysis of heavy oil and the results showed that the Ni(II)-Mannich base complex is the most effective one. The structure of catalyst was characterized by Fourier transform infrared (FTIR), ultraviolet and visible spectrophotometer (UV), and the group compositions C/H/N elemental analysis (EL), and thermogravimetric analysis (TGA) of the heavy oil were also conducted. The viscosity of the heavy oil can be decreased by 82.6% using 1.0 wt % catalyst with 15 wt % methanol in a reaction under 180°С for 24 h, and the composition analysis shows that 9.0% asphaltene is converted to resin and saturated HC. The group composition and the element content of the heavy oil before and after the aquathermolysis reaction were tested and analyzed.     

Magnetite nanoparticle mediated catalytic aquathermolysis of Omani heavy crude oil

The worldwide demand for energy continues to grow and the production of heavy crude is escalating due to shortage of conventional light crude. The transportation of heavy crude oil from the head-well to the refinery is a challenging task due to its high viscosity and low API gravity. Catalytic aquathermolysis is one of the most significant and cost-effective viscosity reduction techniques employed in the up gradation of the crude oil at elevated temperatures and hence to enhance oil extraction process. In this study, catalytic aquathermolysis of Omani heavy crude oil was performed using magnetite nanoparticles (NPs). The NPs were synthesised by reverse co-precipitation method using iron salts in alkaline medium. The synthesised NPs were characterized using Scanning Electron Microscopy (SEM), X-Ray Powder Diffraction (XRD), Energy Dispersive X- Ray analysis (EDX) and Fourier Transform Infrared Spectroscopy (FTIR). The XRD results exhibited a characteristic peak confirming the high purity of iron oxide nanoparticles. The FTIR spectral analysis designated two well-defined peaks corresponding to wave numbers of 500 ?cm^?1 and 630 ?cm^?1, endorses the presence of Fe–O. The catalytic aquathermolysis experiments were carried out in a Parr high temperature-high pressure batch reactor at different experimental conditions. The processing parameters in temperature range of 250 ?°C - 300 ?°C, 0.1% to 0.3% catalyst loading, water to oil ratio of 1:7 to 3:7 with 24–72 ?h of reaction time. The initial pressure in the reactor was maintained at 32 ?bars and the optimization was performed using the Taguchi method to maximize the level of heavy oil. An orthogonal array was employed to analyse the effects of mean response and mean signal-to-noise ratio (S/N) to upgrade the heavy oil. The regression analysis was used to establish a relationship between the viscosity and experimental parameters. The experimental outcomes indicates that the maximum reduction in viscosity occurred at a processing temperature of 300 ?°C, 1:7 ?W/O ratio, 0.1 ?wt% of catalyst concentration and 48 ?h of reaction time. Similarly, the optimum conditions for the reduction in API gravity were obtained at 280 ?°C temperature, 3:7 ?W/O ratio, 0.2 ?wt% of catalyst concentration and a reaction time of 24 ?h.     

稠油在水蒸汽作用下组成变化研究

报道了在水蒸汽作用下辽河油田稠油发生的化学变化,研究结果表明,稠油在水蒸汽作用下,其组成中饱和烃`芳香烃含量增加,胶质沥青质含量减少,粘度下降28%以上.气相色谱分析结果表明,稠油经水蒸汽作用后,其累积炭原子数少于C25的已经达到50.97%,远远超过处理前的17.93%.这为进一步实现稠油井下催化降粘开采提供了依据.