The use of a tartaric–Co(II) complex in the catalytic aquathermolysis of heavy oil

A tartaric–Co(II) complex was synthesized and then used in aquathermolysis of heavy oil as a catalyst at relatively low temperature, 180°C. The effects of water amount and catalyst concentration 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 present of water and the tartaric–Co(II) complex at low temperature. Besides, the catalytic aquathermolysis could not only decrease the viscosity of heavy oil, but also remove some heteroatoms, finally making the flow properties better and the quality upgraded.     

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.     

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.     

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。     

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.     

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。     

The aquathermolysis of heavy oil from Riphean-Vendian complex with iron-based catalyst: FT-IR spectroscopy data

In this paper, we investigated the influence of steam treatment on structural group composition of resins and asphaltenes of heavy oil. The object of investigation was oil-saturated rocks from Riphean-Vendian complex. The extracted crude oil was determined as a high-viscous fluid. The resins and asphaltenes destructed in a small extent due to thermal treatment. The oil-soluble iron-based catalyst intensified the destructive processes. The content of sulfur compounds (-SO) in resins and asphaltenes drastically decreased due to reduction reaction of sulfoxide to sulfide and hydrogen sulfide. The results showed that catalytic aquathermolysis, even at low temperature ranges, promoted the cracking reaction of most macromolecular components and increased the content of light fractions of heavy oil. Consequently, it reduced its viscosity.     

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。     

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。     

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。     

油酸改性Fe2(MoO4)3用于稠油水热催化降黏的研究

利用自制油酸改性Fe2(MoO4)3催化剂，将其用于新疆克拉玛依稠油水热催化降黏的研究，考察了催化剂加入量、反应温度、反应时间对稠油水热催化改质降黏的影响，得到最佳工艺条件为：催化剂添加量（w）0.4%，反应温度240 ℃，反应时间36 h，此时降黏率为61.21 %。稠油族组成分析结果表明有13.2%（w）的稠油重组分裂解成轻组分，这是稠油黏度降低的主要原因。通过进一步对反应前后稠油重组分进行元素分析、FT-IR、1H NMR谱图分析，发现稠油重组分在反应过程中存在脱硫、脱氮、加氢开环、支链断裂等反应。     

Aquathermolysis of conventional heavy oil with superheated steam

This paper presents a new aquathermolysis study of conventional heavy oil in superheated steam. A new high temperature autoclave was designed, where volume and pressure could be adjusted. Aquathermolysis was studied on two different conventional heavy oil samples under different reaction times and temperatures. Experimental results show that aquathermolysis does take place for conventional heavy oil. As reaction time increases, the oil viscosity reduces. However, the reaction will reach equilibrium after a certain period of time and won＇t be sensitive to any further reaction time any more. Analysis shows that, while resin and asphaltenes decrease, saturated hydrocarbons and the H/C ratio increase after reaction. The main mechanism of aquathermolysis includes hydrogenization, desulfuration reaction of resin and asphaltenes, etc.     

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...     

Study of catalytic aquathermolysis of heavy oil in the presence of a hydrogen donor

We have studied the effect of catalytic aquathermolysis of heavy oil in the presence of a hydrogen donor (formic acid) on the viscosity of Liaohe extra-heavy oil. The paraffinic/naphthenic and aromatic hydrocarbon content of the oil as well as the H:C ratio of the oil increase after aquathermolysis in the presence of a hydrogen donor, while the sulfur, resin, and asphaltene content decreases dramatically. We use the thermogravimetric method to show that with aquathermolysis in the presence of formic acid, a substantial portion of the asphaltenes in the heavy oil is converted to paraffins. Accelerating the aquathermolysis reaction results in a synergistic effect between the catalyst and the hydrogen donor.     

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.     

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%.     

The mechanism of H2S generation in the recovery of heavy oil by steam drive

Laboratory experimental simulation reactions between heavy oil and water at different temperatures are conducted. The large amount of H₂S gas in the steam drive recovery in the Shengli oilfield is mainly formed during the aquathermolysis of sulfocompounds in heavy oil. Temperature is a controlling factor influencing the aquathermolysis of heavy oil. The higher the temperature is, the more H₂S gas is generated. Furthermore, the release of H₂S dissolved in formation water at high temperature and the catalytic effect of mineral ions on the aquathermolysis reduces the temperature of the reaction between heavy oil and formation water in the generation of H₂S gas.     

渣油加氢装置反应温度操作初探

介绍渣油加氢处理装置在催化剂床层平均反应温度相同时，各催化剂床层反应温度的不同组合对产品质量和装置运转周期的影响。试验结果表明，在渣油加氢催化剂的级配装填系统中，催化剂床层平均反应温度相同时各催化剂床层反应温度的不同组合对加氢常压渣油产品性质影响较小。为了保持加氢装置的长周期运转，各催化剂床层反应温度不应随意调整，脱金属催化剂的反应温度应有一低限值。     

Changes in the subfractional composition of heavy oil asphaltenes under aquathermolysis with oil-soluble CO-based catalyst

The asphaltenes extracted from the heavy oil sample and products of non-catalytic and catalytic aquathermolysis in the presence of cobalt-based catalyst precursors and hydrogen donor were investigated. Five fractions of asphaltenes and carbene-carboid were obtained by solvent extraction method. In the products of catalytic aquathermolysis processes, the content of resins and asphaltenes decreased, while the content of light hydrocarbon fractions (saturates and aromatics) slightly increased in contrast with non-catalytic processes. This result is due to intensification of destructive hydrogenation reactions, mostly on the weak –C–S–C– bonds of resins and asphaltenes. This study revealed redistribution phenomenon between the asphaltene fractions and decrease in average molecular mass of all asphaltene fractions under catalyst influence.     

低硫超稠油水热裂解反应的研究

研究了反应温度、反应时间、加水量对辽河曙一区超稠油水热裂解反应的影响。结果表明，随反应温度、反应时间和添加物料中水油比的增加，水热裂解反应后油样的饱和份、芳香份的含量逐渐增大，沥青质、胶质含量逐渐减小；在反应温度为240℃、反应时间24小时、添加的水油质量比为0.5时，超稠油水热裂解反应基本完成，50℃粘度由超稠油原样的147.5Pa·s降低到115.4Pa·s，平均相对分子量由超稠油原样的674降低到550。由此可知，含硫量仅为0.45m%的辽河曙一区超稠油能够通过水热裂解反应降低其粘度，实现降粘开采。