节点文献
超稠油水热裂解反应催化剂及其载体的研制
Studies on Aquathermolysis Catalyst and Its Carrier for Super Heavy Oil
【作者】 赵晓非;
【导师】 刘永建;
【作者基本信息】 大庆石油学院 , 油气田开发工程, 2006, 博士
【摘要】 常规原油的产量在上个世纪的最后二十年达到最高峰以后,预计将进入持续的下降阶段,并且这种下降是大势所趋。在这种条件下,一方面随着人口的增长以及人们对能源需求量的增加,另一方面由于能源的短缺以及原油价格的不断攀升,迫切要求提高非常规原油的开采量,使得稠油、超稠油在国民经济中承担着越加重要的任务。超稠油以其丰富的资源,促使着人们为开采技术的不断发展作着不懈的努力。普遍采用的蒸汽吞吐技术具有较高的采油速度、投资较少、工艺较简单的优点,但是原油采收率不高。因此有必要研究出一种低成本、高收率的稠油开采新技术,以指导现场实验。本文针对辽河油田超稠油开采实际,特别是根据采油时注入井中的蒸汽与地下超稠油之间发生的水热裂解反应,开发一种油层中能就地、不可逆降粘的采油新工艺及其应用中涉及的新型化学剂。本文重点研究内容是研制和筛选实用的催化剂及其载体,依此强化井下超稠油就地水热裂解达到提高采收率的目的。在研究超稠油水热裂解反应机理方面,以噻吩、四氢噻吩为模型化合物,研究了模型化合物的水热裂解反应,较全面地完善了超稠油水热裂解反应的机理。研究结果表明,在反应体系中加入适当的催化剂,可以加速辽河超稠油的水热裂解反应,缩短水热裂解反应的时间,使超稠油的粘度大大下降。同时,超稠油的族组成、平均分子量和结构都发生了较大的变化。研制出了适合于辽河超稠油的水热裂解催化剂体系:主催化剂为 Fe2+(Ni2+)。加入过渡金属活性组分后,其降粘效果存在着明显的不同,降粘效果最明显的应属 Fe2+、Ni2+,降粘率分别为:50.3%和 54.7%。自制了脂肪醇聚氧乙烯醚类乳化剂,确定可用该乳化剂作为催化剂体系的外部载体,这样保证了超稠油降粘重复性好。助催化剂为四氢化萘。将作为供氢剂的四氢化萘加入到“稠油+水+催化剂”体系后,降粘率由超稠油水热裂解的 57.1%提高到 72.6%,说明供氢剂具有抑制超稠油的粘度增加的作用。确定了适用的 pH 范围。当 pH 达到 6 左右时(酸浓度=3×10-4wt%),降粘率为92%,表明酸起到了裂化的作用。确定了超稠油最佳工艺条件:反应温度:180℃、反应时间:24hr、催化剂浓度:0.02wt%、加水量:20~30wt%、供氢剂加量:0.06wt%、pH:6、超稠油降粘率达到 92.4%。通过对反应后的稠油为期 60 天的稳定性考察:粘度反弹率不到 5%,说明采用水热裂解法能够达到不可逆降粘的目的。本文的研究工作对辽河油田稠油、超稠油的有效开采具有重要的指导意义。
【Abstract】 The world’s conventional crude oil production is expected to reach its peak in the second decade ofthe coming century and enter a permanent decline phase. Unconventional oil from heavy oil resources willstart making significant contributions to the world’s growing population. The peaking of conventional oilcombined with physical shortages and crude price escalation, will mark the beginning of commercialproduction from the world’s huge deposits of tar sands and super heavy oil. Super heavy oil is an importantportion of the global petroleum resource. Thermal methods particularly stem injection are the mostsuccessful enhanced oil recovery processes. It has the advantages of higher oil recovery speed, fewerinvestment and simple technology method, yet its crude oil recovery ratio is not high. Therefore, it isnecessary to study and development a new kind of technology which has low cost and higher oil recoveryto instruct the field experiments.According to heavy oil and super heavy oil’ properties of Liaohe oil field reality, especially aim atoccurring aquthermolysis reaction between super heavy oil and stem when stem inject in the oil well, anew chemical agent and its technology which has been developed for the purpose irreversible reducingviscosity in situ. The important content of the article is to develop and select a kind of suitable catalyst andits carrier to enhance aquthermolysis reaction so as to achieve irreversible reducing viscosity.In order to investigate the reaction mechanism of heavy oils, the model compounds were determinedbased on the heavy oil’s properties. Thiophene and tetrahydrothiophene are the suitable candidates formodel compounds for investigate the mechanisms of aquathermolysis. The studing on mechanisms ofaquathermolysis for super heavy oils shows that:The aquathermolysis reaction of heavy oil can bepromoted after adding suitable catalyst in the system with water at high temperature, the reaction timedecreased and the viscosity of super heavy oil droped obviously. At the same time, the super heavy oilgroup composing, the mean molecular weight and the structure changed greatly.The catalyst system has been developed for Liaohe oil field. The main catalysts for aquathermolysisare made from nickel, iron and so on. After joined the transition metal active components, the effects ofdecreasing viscosity of super heavy oil were obvious. The degree of decreasing viscosity of Fe2+ and Ni2+reached to 50.3% and 54.7% respectively. Self-made a kind of emulsification viscosity reducer preparedfrom a fatty alcohol polyoxyethylene ether,aim at being catalyst external carrier insure the repetition ofreducing viscosity is better. Tetrahydric naphthalin, being the auxiliary catalyst, is added in catalyst system,the reducing viscosity rate increase to 72.6% from 57.1%, which indicate tetrahydric naphthalin has thefunction of restraining super heavy oil increasing viscosity. When pH achieves to 6 (acid concentration =3×10-4wt%)around , the reducing viscosity rate of super heavy oil increase to 92%, indicated the acidplayed as the cracking role.Under the optimum processing conditions of reaction temperature:180℃、reaction time:24hrs;catalyst concentration :0.20wt%、water adding:20~30wt%、hydrogen donor:0.06 wt %、pH:6、the viscosity of heavy oil from 183.8 Pa.s decrease 14.4 Pa.s,reducing viscosity ratio reach to 92.4%,andwithin 60d observed these viscosities were re-increased no more than 5%,shows that :Being a new superoil recovery method, aquthermolysis is able to achieve irreversible reducing viscosity goal.This research work has an important guiding sense to heavy oil and super heavy oil of Liaohe oil fieldfor effective developing.
【Key words】 Super Heavy Oil; Aquathermolysis; Catalyst; Active Component; Hydrogen Donor; Tetrahydrothiophene;