委内瑞拉劣质重油水热降粘改质研究

发布时间：2018-07-20 20:52

【摘要】：随着原油的不断开采,常规原油资源开采量已经不能满足世界石油资源需求的增长,能源的巨大缺口将由稠油、油砂沥青等非常规原油资源来弥补。然而非常规原油粘度高、密度大、杂原子以及金属含量高等特点给其开发、运输及加工带来了重大挑战。如何高效改质劣质重油已经成为相应技术研究开发的热点。本论文针对委内瑞拉超重油的减压渣油开展了常规减粘改质及水热减粘改质的研究,来探索高效的重油改质方法。论文分析了反应条件对生成油性质的影响,并建立了相应的反应动力学模型;通过分析热改质反应前后气体组成变化以及生成油沥青质结构的变化揭示了水蒸汽及过渡金属催化剂对减压渣油降粘改质过程的作用机理。水热降粘改质过程中,水蒸汽存在能够抑制体系生焦,改善生成油安定性。在催化剂存在下,水蒸汽与重油大分子发生水蒸汽重整反应,将更多的氢从水蒸汽转移到重油分子中,改善了重油品质。在相同生焦率(0.1w%)的前提下,三种改质工艺的理想渣油转化率大小为催化改质CHVB水热改质HVB常规改质VB。动力学研究结果表明,水热减粘改质反应生成轻组分产物的反应速率要低于常规减粘,而表观活化能要高,进一步阐释了热改质过程中水蒸汽存在能够释放活泼氢自由基缓和渣油热转化过程。催化剂的存在改变了渣油热反应途径,降低了表观反应活化能,进而大幅度提高了反应速率。对热改质生成油进行调合试验,评价了改质油粘度及安定性,并筛选出了符合油品船运条件的热改质工艺条件;试验确定的最佳反应工艺条件为:410℃,20min,加水量6w%,环烷酸镍催化剂加入量0.1w%。气体组成分析数据表明水蒸汽参与了渣油热改质化学反应。水蒸汽与渣油化合物发生水蒸汽重整反应,产生氢气并在催化剂作用下进行加氢脱硫、大分子自由基夺氢等耗氢反应。渣油重组分中的杂原子化合物是参与渣油水热裂解反应的重要组成部分,在催化剂的作用下杂原子化合物能够与水蒸汽发生系列链的断裂、加氢、开环、脱硫等脱杂原子反应,降低生成油粘度,提高了油品质量
[Abstract]:With the continuous exploitation of crude oil, the production of conventional crude oil can not meet the growth of world oil resource demand. The huge gap in energy will be made up of unconventional crude oil, such as heavy oil and oil sands asphalt. However, unconventional crude oil has high viscosity, large density, high impurity atoms and high metal content. It has become a major challenge. How to improve the quality of poor quality heavy oil has become a hot spot in the research and development of the corresponding technology. The reaction kinetics model was established. By analyzing the change of gas composition before and after the heat modification and the change of oil asphaltene structure, the mechanism of water vapor and transition metal catalyst was revealed in the process of reducing viscosity and modification of vacuum residuum. During the process of water heat reducing and viscosity modification, the existence of water vapor can inhibit the coking of the system and improve the life. In the presence of the catalyst, the steam reforming reaction of water vapor and heavy oil molecules, more hydrogen is transferred from the steam to the heavy oil molecules, and the quality of heavy oil is improved. Under the same raw coke rate (0.1w%), the ideal residual oil conversion rate of the three modification processes is the conventional modification of the modified CHVB hydrothermally modified HVB The results of the VB. dynamics study show that the reaction rate of the reaction of the water and heat reducing reaction is lower than that of the conventional viscosity reduction, but the apparent activation energy is higher. It is further explained that the presence of water vapor in the process of heat modification can release the thermal conversion process of the reactive hydrogen free radical residing residue. The activation energy of the apparent reaction was lower, and the reaction rate was greatly improved. The heat modification oil was adjusted and the viscosity and stability of the modified oil were evaluated, and the thermal modification conditions were selected. The optimum reaction conditions were as follows: 410, 20min, 6w%, and nickel naphthenate. The analysis data of the composition of 0.1w%. gas shows that steam is involved in the residing chemical reaction of residual oil. Steam reforming reaction of steam and residuum, producing hydrogen, hydrodesulfurization, large molecule free radical hydrogen and other hydrogen consumption. The important component of the cracking reaction, under the action of the catalyst, the hetero atomic compound can break up the chain of the series of water vapor, the hydrogenation, the opening ring, the desulphurization and so on, which reduces the viscosity of the generated oil and improves the quality of the oil.
【学位授予单位】：中国石油大学(华东)
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TE624

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