水热裂解反应对稠油粘度影响的实验研究

蒸汽吞吐是目前开采稠油的主要方法,在吞吐过程中蒸汽与稠油在高温下发生的水热裂解反应能够达到使稠油就地改质的目的。通过对辽河稠油样品进行实验,考察了在不同反应条件下,水裂解反应对稠油粘度的影响。结果表明:当无催化剂存在时,辽河稠油发生水热裂解反应的条件是:加入水量30%、反应温度大于等于200℃、反应时间大于等于36小时,经水热裂解反应,稠油的粘度可以降低28%以上;当有催化剂存在时,加入水量30%、催化剂加量0.05%、反应温度大于180℃、反应时间大于等于24小时,稠油的粘度可以降低82.4%以上。上述结果说明催化剂的存在,加速了稠油的水热裂解反应,从而大幅度降低了稠油粘度。     

超稠油乳化降粘剂SHVR-02的研制

用荧光法测得辽河油田杜84块杜54 30井超稠油(室温粘度54.8Pa·s)乳化剂的最佳HLB值为10.8。根据这一HLB值,由主剂脂肪醇聚氧乙烯醚、一种生物表面活性剂及辅剂快速渗透剂JFC配成了超稠油乳化降粘剂SHVR 02。当油水体积比为1.0∶0.7、水相中SHVR 02浓度为1g/L时,超稠油乳状液的粘度为492mPa·s,水相浓度增大至5g/L时乳状液粘度降至268mPa·s。在油水体积比1.0∶0.7、水相SHVR 02浓度3g/L、混合温度50℃条件下,粘度在6.2～20.9Pa·s的8种辽河稠油形成的乳状液,粘度在53～148mPa·s之间。乳状液在40～80℃放置10h后,粘度随放置温度升高略有下降(378→248mPa·s),放置温度为90℃时乳状液发生反相,粘度升至26.1Pa·s。SHVR 02的乳化降粘效果优于3种对比乳化剂。SHVR 02形成的超稠油乳状液易破乳,与联合站现用破乳剂配伍。表6参14。     

油层矿物对蒸汽作用下稠油组成与粘度变化的影响

实验考察了辽河田曙光采油厂的两种稠油在有和无油层岩心存在时水热裂解反应产物的差别,裂解反应温度240℃,反应时间24小时,油层岩心岩石矿和粘土矿物组成已知,作为对照,还考察了相同条件下的热裂解反应产物。实验结果表明该油层矿物对低含硫稠油的水热裂解有催化作用,与单纯水热裂解结果相比,有油层矿物参与的水热裂解使两种稠油的饱和烃芳香烃组分含量增加,胶质,沥青质组分含量减少,稠油平均相对分子质量略有下降,沥青质组分的平均相对分子质量有较大幅度下降,气体（H2,C1－C3烷烃,CO2及H2S）生成量增加,两种稠油的粘度（初始值88．5和124．3Pa.s)在水热裂解后分别下降13．4％和10．6％,在油层矿物参与下水热裂解后则分别下降25．6％和23．4％,这一实验研究结果有助于研制高效的稠油水热裂解催化剂。     

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     

胜利含盐特超稠油水热改质降粘研究

针对胜利油田特超稠油因黏度过高而难以集输的问题,研究水热处理对其改质降黏效果,探讨水热处理在稠油集输过程中应用的可行性。通过水热反应工艺参数的调变及黏度、元素组成、四组分组成、馏分分布、盐含量等分析,发现水热处理能有效降低胜利油田特超稠油的黏度,水热处理后稠油的黏度主要由裂化转化率决定;通过添加催化剂,改变水热处理温度和水热处理时间,可以有效控制稠油的裂化转化率。加入合适的催化剂,提高水热反应温度,延长反应时间,皆利于提高稠油的裂化转化率。加入催化剂,可降低水热反应温度和缩短反应时间。多孔炭质催化剂A存在下,反应温度330 ℃,反应时间60 min时,胜利特超稠油的裂化转化率高达30.11%,黏度由水热反应前的52 410 mPa·s降低至水热反应后的1 536 mPa·s,降黏率高达97.07%。水热改质后油品的流动性较好,可作为普通原油进行集输,表明水热处理在稠油集输过程中具有良好的应用前景。     

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。     

蒸汽和金属盐作用下稠油黏度的变化

在高温高压反应釜中实验考察了50℃黏度88.3 Pa.s、平均分子量654的辽河曙光稠油的水热裂解降黏条件及6种金属盐的催化效能。在裂解温度240℃下,当加水量≥30 mL/100 g稠油或裂解时间≥36小时时,裂解后稠油黏度的降幅变得很小;随裂解温度(160~280℃)升高,裂解后稠油的黏度降低。在裂解温度240℃、裂解时间48小时、加水量30 mL/100 g稠油、金属盐在水中的质量分数为0.02%的条件下,NiSO4.6H2O对稠油水热裂解的催化效能最好,其次是VOSO4和CuSO4.5H2O,Al2(SO4)3最差,裂解后稠油的黏度分别为32.4、36.7、42.6、52.4Pa.s,而空白值为62.4 Pa.s。图3表1参15。     

孤岛稠油水热裂解硫化氢产生速率模拟实验

文章针对稠油热采过程中产生的H₂S对生产环境造成不利影响的现状,在高压反应釜中模拟孤岛地下稠油热采条件,研究了反应时间、反应温度、岩心用量、水油比等因素对稠油水热裂解生成气体量及气体中H₂S浓度的影响规律,并进行了水热裂解前后稠油中总硫含量和硫分布的对比。结果表明,反应前期(24 h前)反应剧烈,H₂S生成量随时间迅速增加,稠油黏度快速下降,30 h后反应基本结束;较低温度(220℃和240℃)下水热裂解反应进行缓慢,H₂S生成量少,稠油黏度变化不大;较高温度下(280℃和300℃)下反应迅速,H₂S生成量大,稠油降黏率大幅增加;在体系中添加同一地层的岩心可增加水热裂解反应的程度;水油质量比对反应有较大影响,无水时基本无气体生成,当水油质量比达到0.2,继续增大比例时H₂S生成量变化不再明显。     

超稠油掺稀释剂脱水试验研究

方法根据辽河油区曙光油田曙一区超稠油密度大、粘度高、油水密度差小，胶质、沥青质含量高的特点，采用超稠油掺不同比例稀释剂进行不同条件下热化学沉降脱水。目的选择适合于超稠油脱水的工艺条件，解决超稠油脱水的难题。结果超稠油掺入一定比例（8：2，7：3）的稀释剂，加入一定量的（200～300mg／L）破乳剂LH－2或RS－2，在沉降12h和8h时，超稠油脱水可达到油净水清。结论曙一区超稠油掺不同比例的稀释剂进行脱水，能够满足脱水生产的需要。     

胜利稠油地下催化水热裂解改质研究及应用

针对胜利油样开展催化水热裂解改质研究,240℃-350℃范围内改质催化剂可提高水热裂解反应效率最高达52.63%、降低反应温度50℃,降粘效果30d无明显变化。初步形成改质效率表征方法。现场应用取得增油效果。     

超稠油水热催化裂解反应前后性质变化

为了更好地应用水热催化裂解技术对稠油进行开采,明确稠油性质变化的本质,对胜利油田超稠油进行微乳液纳米镍催化降黏剂水热催化裂解实验研究。实验结果表明,水热催化裂解反应后,稠油黏度大幅度降低,稠油中胶质、沥青质的含量下降,硫含量大幅降低,氮含量略减少。稠油氢碳原子比增加,平均分子质量减小。族组分中沥青质的平均分子质量减小幅度最大,说明沥青质裂解对稠油黏度的降低和平均分子质量的减小起到了关键作用。该研究为日后稠油水热催化裂解降黏技术的推广提供了技术参考。     

Ni~(2+)和Sn~(2+)改性的SO_4~(2-)/ZrO_2固体超强酸催化剂对稠油的降黏性能

稠油黏度高的特性使其开采难度较大。为降低胜利油田稠油的黏度,制备了金属离子(Ni2+和Sn2+)改性的SO42-/ZrO2固体超强酸催化剂,考察了这两种催化剂对稠油的降黏性能。实验结果表明,Ni2+和Sn2+改性的SO24-/ZrO2固体超强酸催化剂能在较低的温度下催化稠油降黏,在反应温度240℃、压力3~4MPa、反应时间24h、稠油与催化剂质量比100∶0.05的条件下,稠油的黏度由0.319Pa.s分别降至0.135Pa.s和0.163Pa.s,降黏率达57.7%和48.9%。反应后,稠油中的饱和烃含量增加,芳烃、胶质和沥青质含量减少,杂原子S和N的含量降低。同时发现,水的存在对稠油降黏不利。     

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.     

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...     

Influences on the Aquathermolysis of Heavy Oil Catalyzed by Two Catalysts With Different Ligands

The dodecyl benzene sulfonic iron and p-toluenesulfonic iron were prepared and used in catalytic aquathermolysis of Xinjiang extra-heavy oil (8.5 × 10⁴ mPa·s at 50°C). The same and different influences on the aquathermolysis of heavy oil catalyzed by them were studied in depth and compared. The compositions and structure of oil sample before and after reaction were analyzed by element analysis instrument, ¹H nuclear magnetic resonance and gas chromatography-mass spectrometry. The results showed that the p-toluenesulfonic iron exhibit better viscosity reduction effect and more significant changes for the oil sample than the dodecyl benzene sulfonic iron.     

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.     

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。     

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.     

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.