大庆外围稠油水热裂解地质协同催化降黏研究

为更好地实现稠油就地水热裂解降黏,以油藏矿物、催化剂和供氢剂为催化体系,检测其对大庆外围稠油水热裂解反应的催化作用.实验结果表明,油藏矿物可以催化稠油水热裂解反应,并可与催化剂协同催化稠油水热裂解,矿物与油溶性催化剂的协同催化效果好于水溶性催化剂;供氢剂的加入可进一步强化稠油水热裂解反应,与不添加供氢剂相比,反应后胶质...     

辽河稠油水热裂解催化及化学强化降黏研究

为确保稠油就地水热裂解降黏技术更好地实施,选取辽河油田齐40、齐108和杜32区块为研究目标,以油藏矿物、硫酸镍、环烷酸镍和甲酸供氢剂为催化体系,开展了对油藏矿物地质催化性能及其与外加化学剂协同催化作用的实验研究。实验结果表明,油藏矿物可催化稠油水热裂解反应,并可与催化剂协同催化稠油水热裂解。矿物组成不同,其协同效果不同。油砂矿物存在时,环烷酸镍与硫酸镍结合使用后的催化效果更强,并可节省环烷酸镍用量。甲酸供氢剂的加入可进一步强化稠油水热裂解反应。     

注蒸汽条件下稠油催化改质降黏实验研究

以自制的油溶性有机镍盐作为催化剂进行稠油水热裂解反应.考察了催化剂加量、反应温度、反应时间和加水量对催化水热裂解反应前后稠油黏度、族组成的影响.催化水热裂解反应的最佳条件为:反应温度240℃,反应时问24 h,加水量30％,催化剂质量分数0.1％.对反应前后稠油的元素分析结果表明,与水热裂解反应相比,加入催化剂后的稠油黏度由11000 mPa·s降至3414 mPa·s,沥青质、胶质含量分别降低1.7％、1.6％,芳香分、饱和分含量分别增加0.8％、2.5％,稠油中C含量降低,H含量增加,H、C原子数比提高,而杂原子与C的原子数比降低.图4表6参8     

地质催化稠油水热裂解反应可行性研究

基于油藏矿物的地质催化概念引入到稠油水热裂解开采技术中，开展了地质催化稠油水热裂解室内实验。结果表明，油藏矿物的加入使油样降粘率从10．6％增加到23．4％，降粘率增加了1倍以上。通过对矿物催化机理进行分析，指出以油藏矿物为催化剂的地质催化稠油水热裂解反应具有可行性。     

水热裂解开采稠油技术

水热裂解降粘开采稠油技术，是在注入蒸汽的条件下，借助于稠油与蒸汽之间发生的化学反应，降低稠油的粘度。从而达到井下降粘开采稠油的目的。从水热裂解反应、催化水热裂解反应、水热裂解反应影响因素、开采技术的可行性以及催化水热裂解反应机理等方面介绍了稠油水热裂解开采技术的研究进展，发现反应时间、反应温度、催化剂、催化剂加量、油层矿物等都影响稠油水热裂解反应；稠油水热裂解开采技术在理论上、油层催化裂化和催化剂选择的广泛性上都是可行的。对该技术的发展进行了探讨，认为水热裂解开采稠油技术具有广泛的发展前景，是未来开采稠油油藏的主要技术之一，指出当前水热裂解开采稠油技术的主要研究方向是研究高温水的特性及其作用以及合适的催化剂．并且设计合理的现场实施技术和工艺。     

注蒸汽条件下稠油催化改质降黏实验

利用高温高压反应釜研究了自制油溶性有机镍盐作为催化剂的稠油水热裂解反应,考察了催化剂的加入量、反应温度、反应时间和加水量对催化水热裂解反应前后稠油黏度、族组成的影响,优选出最佳改质降黏反应条件,在此条件基础上,对改质降黏反应前后稠油元素进行分析。结果表明,与未添加催化剂的相比,在反应温度为240℃、加水量30%的体系中,添加0.1%的过渡金属有机酸镍催化剂,反应24 h 后稠油的黏度下降明显,沥青质含量下降1.4%,胶质含量下降5.0%,芳香分含量增加3.5%,饱和分含量增加2.9%.     

井下裂解提高稠油油藏蒸汽吞吐采收率

开展了井下裂解就地改质稠油,提高稠油油藏蒸汽吞吐采收率的室内模拟实验和矿场应用试验。研究表明,油藏矿物可催化稠油水热裂解反应,其中黏土矿物的催化效果优于其他矿物,可使稠油黏度降低30%以上,黏土矿物含量越高,越有利于水热裂解反应;注入催化剂硫酸镍和供氢剂四氢萘溶液段塞后,蒸汽吞吐最终采收率大幅度提高,比单纯蒸汽吞吐提高8.8%,产出油降黏率增加51.7%,饱和烃、芳香烃含量分别增加38.0 mg/g 和26.3 mg/g,胶质、沥青质含量分别降低41.9 mg/g 和41.1 mg/g. 矿场试验结果表明,井下裂解就地改质稠油技术可延长蒸汽吞吐周期生产时间、提高日产油量、提高油汽比和回采水率,较大程度地改善蒸汽吞吐开发效果。     

稠油沥青质水热裂解供氢催化及地质协同作用研究

探讨了辽河稠油中沥青质在注蒸汽热采条件下供氢催化水热裂解反应行为,以及油藏矿物对沥青质水热裂解的强化作用,结果表明,油藏矿物与硫酸镍、甲酸供氢剂可协同催化沥青质水热裂解反应,最终可使沥青质降解率达到49.2%;供氢催化反应前后稠油中沥青质红外谱图说明稠油中沥青质在供氢催化改质降粘反应时所发生的化学结构的变化,反映了沥青质在反应过程中经历了侧链断裂、环烷脱氢芳构化以及芳香结构进一步缩合等反应;对沥青质水热裂解反应产物中轻组分进行气相色谱全烃分析,证实了在注蒸汽热采条件下沥青质可以实现部分催化降解。     

稠油水热裂解中的金属纳米粒子催化剂研究进展

为了促进稠油开采用催化水热裂解技术的发展,从作用机理、制备与改性方法、性能评价等方面,综述了国内外稠油水热裂解中的金属纳米粒子催化剂,包括镍基纳米粒子、钼基纳米粒子和铁基纳米粒子以及纳米粒子催化剂表面改性的研究现状,并对今后金属纳米粒子催化剂在稠油水热裂解中的研究与应用提出了建议与展望。     

化学剂强化稠油水热裂解降黏研究进展

介绍了稠油水热裂解反应及其机理。基于反应机理讨论了化学剂对稠油水热裂解降黏的强化作用，并从催化剂、供氢体、助剂等方面综述了国内外关于用化学剂强化稠油水热裂解降黏的研究情况。指出了用化学剂强化稠油水热裂解降黏的研究方向:以具体油藏矿物和稠油为基础，研发价格低、活性高、选择性高、反应条件宽的稠油水热裂解反应催化剂；寻找供氢效果好、来源广、可工业化应用的供氢体；优选合适的助剂，如表面活性剂，发挥乳化降黏等协同作用；与油藏堵水调剖技术相结合，充分发挥外加化学剂的作用。     

稠油水热裂解催化剂的研制及效果测定

高温水环境条件下发生的稠油水热裂解反应可使稠油重质组分明显降解,改善油品并降低黏度。气溶、油溶、水溶型镍催化剂均可在高温下明显催化稠油的水热裂解反应,降低稠油黏度,与无催化剂时相比,生成气体量分别增加49%、41%和21%。气溶、油溶、水溶型镍催化剂复配后(最佳质量比1∶1∶2),可使稠油采收率增加至8.5%,并使多孔介质中油样的黏度和平均相对分子质量分别下降89.6%、23%,胶质沥青质含量明显降低。先导性现场试验表明:每口井的试验周期稠油产量比上周期增加了81.2～226.1 t(未考虑周期递减率);开井生产30 d后,胶质沥青质减少,饱和烃与芳香烃增加,采出稠油的250℃馏分中轻组分明显增加。     

稠油水热催化改质降黏催化剂研究进展

稠油水热催化改质降黏开采技术是一项极具潜力的稠油开采新技术。在介绍稠油水热催化改质降黏开采重要性和必要性的基础上,综述了稠油水热催化改质降黏催化剂的研究进展,并对稠油水热催化改质降黏方法和催化剂的发展趋势进行了分析。稠油水热催化改质降黏催化剂的发展方向是开发高活性的催化剂体系,使稠油在更为温和条件下即能发生水热催化改质反应;将水热催化剂与其它降黏方法配合使用,开发复合型、集成型降黏工艺,发挥多种降黏手段的协同作用。     

Change of asphaltene and resin properties after catalytic aquathermolysis

Resin and asphaltene were separated from Liaohe heavy oil. Catalytic aquathermolysis of asphaltene and resin was investigated by using water soluble catalysts （NiSO4 and FeSO4） and oil soluble catalysts （nickel naphthenate and iron naphthenate）. Before and after aquathermolysis, the properties of the resin and asphaltene was compared by means of ultimate analysis, vapor pressure osmometer （VPO） average molecular weight, X-ray diffraction （XRD）,^13C and ^1H nuclear magnetic resonance （NMR）. The conversion sequence was as follows： No-catalyst〈NiSO4〈FeSO4〈nickel naphthenate〈iron naphthenate. In the presence of catalysts, the amount of H2 and CO increased significantly, while H2S in the gas product decreased. The molecular weight of asphaltene and resin increased after reaction without catalyst. But the catalysts restrained this trend. The H/C ratio of asphaltene and resin decreased after reaction. From the results of average structural parameters and molecular weight, it was found that asphaltene and resin were partly aggregated after aquathermolysis.     

Clean aquathermolysis of heavy oil catalyzed by Fe(III) complex at relatively low temperature

In order to develop a clean catalyst for aquathermolysis of heavy oil at relatively low temperature, a series of water-soluble Fe(III) complexes were prepared as the catalysts for the catalytic aquathermolysis of heavy oil. Under the optimized condition, the adding amount of Fe-3 (a complex of Fe(III) and citrate) is 0.1%, the reaction temperature is 180°C, and the reaction time is 24 h, the heavy oil viscosity reduction ratio reaches to 80.1% (40°C). Results of the composition analysis show that the contents of resin and asphaltene decrease and the saturated hydrocarbon and aromatic increase. GC analysis shows that the light components increase remarkably after the aquathermolysis.     

Zn(II) Complex Catalyzed Coupling Aquathermolysis of Water-Heavy Oil-Methanol at Low Temperature

A Zn(II) coordination complex was synthesized, characterized, and used for catalytic aquathermolysis of heavy oil at low temperatures for the first time. The effects of water content and catalyst concentration on aquathermolysis were investigated. And then a tri-component coupling aquathermolysis of waterheavy oil-methanol was designed and the reaction conditions were investigated. With the catalyst and methanol, the reaction occurred at temperatures as low as 180°C. The viscosity of the product was also substantially reduced from around 24 400 to 6420 mPa s by the decomposition of the large hydrocarbon molecules.     

Ethanol enhanced aquathermolysis of heavy oil catalyzed by a simple Co(II) complex at low temperature

Co(II) 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, ethanol amount on aquathermolysis were investigated in this work. The crude oil before and after aquathermolysis was fully characterized, and the mechanism of viscosity reduction was discussed at last. The results show that heavy oil can undergo aquathermolysis in the presence of water and the Co(II) complex at low temperature. Furthermore, it was found that ethanol can enhance the catalytic aquathermolysis. 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. The experimental results prove that the combination of catalyst and ethanol has a synergetic effect, which contributes to the great reduction of viscosity and improvement of heavy oil quality.     

Aquathermolysis of heavy crude oil with ferric oleate catalyst

Oil-soluble catalysts could be of special significance for reducing the viscosity of heavy crude oil, because of their good dispersion in crude oil and high catalytic efficiency toward aquathermolysis. Ferric oleate was synthesized and applied as catalyst in the aquathermolysis reaction of Shengli heavy oil. It was found that ferric oleate was more efficient for heavy oil cracking than Co and Ni oleates. Besides, it was superior to oleic acid and inorganic ferric nitrate and achieved the highest viscosity reduction rate of up to 86.1%. In addition, the changes in the components of Shengli heavy oil before and after aquathermolysis were investigated by elemental analysis, Fourier transform infrared spectrometry, and ¹H nuclear magnetic resonance spectroscopy. Results indicated that ferric oleate contributed to a significant increase in the content of light components and decrease in the content of resin, N and S. The as-prepared ferric oleate showed good activity for reducing the viscosity and improving the quality of the heavy crude oil, showing promising application potential in aquathermolysis of heavy crude oil.