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超声波协同金属催化剂裂解稠油降粘研究

作者:润色论文网  来源:www.runselw.com  发布时间:2019/10/24 10:21:41  

摘要:超声波作为一种能量传播形式,具有方向性强和穿透性强的特点,其中空化作用的形成可以引起局部高温和高压,进而可产生非常强烈的微反应环境中心。向稠油中加入催化剂,可降低反应所需要的活化能。两者结合使稠油发生催化超声反应有望通过改变稠油中各组分的含量分布从根本上不可逆地降低稠油粘度,改善稠油品质。

采用溶液法制备了两种油溶性的镍金属催化剂,硬脂酸镍和月桂酸镍,并将其 分别应用于稠油超声降粘实验中,得出最佳的超声波处理时间为16min,最佳的催化剂浓度为硬脂酸镍0.4wt%,月桂酸镍0.6wt%。通过对油样流变性、四组分含量、饱和烃气相,胶质、沥青质红外的分析也表明脂肪酸镍催化剂能对稠油实现较大程度的降粘,其中硬脂酸镍因具备较长链的有机配体,效果更佳。

制备了NiCl2与[bmim]Cl比值分别为0.25:0.75和0.35:0.65的两种不同镍含量的离子液体,并分别研究了超声功率,超声时间和加入稠油中的镍基离子液体的浓度三个条件对稠油超声改质降粘的效果。得出两种镍基离子液体均对稠油有较好的降粘效果,其中当设置参数为超声10min,功率150w×99%时,加入1.6wt%的0.25:0.75 镍基离子液体降粘效果较好。

对不同条件反应前后的油样分别进行了四组分含量及结构的分析,结果表明, 与原油相比,单独超声波作用确实可使稠油产生裂解降粘效果,而超声波与离子液体的结合使用则能产生协同效应加深裂解程度。各组分的含量呈现规律性变化,饱和烃含量增加,芳香烃、胶质含量降低。基于气相、红外和氢谱的分析表明超声催化过程中的作用方式为:作为重质组分的沥青质和胶质具有大分子芳香环状结构,经历烷基侧链的裂解反应,导致烷基链的缩短或去除,以及烷基链分支度的增加。

As a form of energy transmission,ultrasonic waves have the characteristics of strong directivity and strongpenetration. And the formation of cavitation during ultrasound process caninduce localized high-temperature and high-pressure, which is more intensecondition for the micro-environment of the reaction center. Adding a catalystto the heavy oil, the activation energy required for the reaction can belowered. The combination of the two makes the catalytic ultrasonic reaction ofheavy oil, and it is expected that the viscosity of the heavy oil can befundamentally irreversibly reduced by changing the content distribution of eachcomponent in the heavy oil to improve the quality of the heavy oil.

Two oil-soluble nickel metal catalysts,nickel stearate and nickel laurate, were prepared by solution method andapplied to the ultrasonic viscosity reduction test of heavy oil respectively.The best ultrasonic treatment time was 16 min. The best catalyst concentrationwas 0.4wt% of nickel stearate, 0.6wt% of nickel laurate. According to theanalysis of oil samples rheological, four component content, gas chromatographyof saturate, infrared spectrum of resin and asphaltene showed that the fattyacid nickel catalyst can achieve a greater degree of viscosity reduction forheavy oil, of which nickel stearate has better effect due to the longer chainorganic ligand.

Two kinds of ionic liquids with differentnickel chloride contents were prepared, and the ratio of NiCl2 to [bmim]Cl was0.25:0.75 and 0.35:0.65. The effects of ultrasonic power, ultrasonic time andconcentration of nickel-based ionic liquid on the viscosity reduction of heavyoil were studied separately.

It is concluded that both nickel-basedionic liquids have good viscosity-reducing effect. When the ultrasonicparameter is 10min and the power is 150w×99%, the viscosity reduction effect isbetter when the 0.25:0.75 nickel-based ionic liquids is added in an amount of1.6wt%.

The oil content of different conditionsbefore and after the reaction was analyzed by four components and structure.The results show that compared with crude oil, the ultrasonic effect alone canmake the cracking and viscosity reduction effect of heavy oil, and thecombination of ultrasonic and ionic liquid It can produce synergistic effectsand deepen the degree of cracking. The content of each component showed aregular change, the content of saturated hydrocarbons increased, and thecontent of aromatic hydrocarbons and resins decreased. Based on thecharacterization of gas chromatography, infrared spectroscopy and nuclearmagnetic resonance spectroscopy, it can be known that as heavy componentasphaltenes and resins have a macromolecular aromatic ring structure, both canundergo cleavage reaction of alkyl side chains, resulting the shorten orremoval of alkyl chain and the increase in the branching degree.

关键词:重油;超声波离子液体;胶质;沥青质

heavy oil; ultrasound; ionic liquids;resin; asphaltene

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