【摘要】：隨著原油的不斷開采,常規(guī)原油資源開采量已經不能滿足世界石油資源需求的增長,能源的巨大缺口將由稠油、油砂瀝青等非常規(guī)原油資源來彌補。然而非常規(guī)原油粘度高、密度大、雜原子以及金屬含量高等特點給其開發(fā)、運輸及加工帶來了重大挑戰(zhàn)。如何高效改質劣質重油已經成為相應技術研究開發(fā)的熱點。本論文針對委內瑞拉超重油的減壓渣油開展了常規(guī)減粘改質及水熱減粘改質的研究,來探索高效的重油改質方法。論文分析了反應條件對生成油性質的影響,并建立了相應的反應動力學模型;通過分析熱改質反應前后氣體組成變化以及生成油瀝青質結構的變化揭示了水蒸汽及過渡金屬催化劑對減壓渣油降粘改質過程的作用機理。水熱降粘改質過程中,水蒸汽存在能夠抑制體系生焦,改善生成油安定性。在催化劑存在下,水蒸汽與重油大分子發(fā)生水蒸汽重整反應,將更多的氫從水蒸汽轉移到重油分子中,改善了重油品質。在相同生焦率(0.1w%)的前提下,三種改質工藝的理想渣油轉化率大小為催化改質CHVB水熱改質HVB常規(guī)改質VB。動力學研究結果表明,水熱減粘改質反應生成輕組分產物的反應速率要低于常規(guī)減粘,而表觀活化能要高,進一步闡釋了熱改質過程中水蒸汽存在能夠釋放活潑氫自由基緩和渣油熱轉化過程。催化劑的存在改變了渣油熱反應途徑,降低了表觀反應活化能,進而大幅度提高了反應速率。對熱改質生成油進行調合試驗,評價了改質油粘度及安定性,并篩選出了符合油品船運條件的熱改質工藝條件;試驗確定的最佳反應工藝條件為:410℃,20min,加水量6w%,環(huán)烷酸鎳催化劑加入量0.1w%。氣體組成分析數據表明水蒸汽參與了渣油熱改質化學反應。水蒸汽與渣油化合物發(fā)生水蒸汽重整反應,產生氫氣并在催化劑作用下進行加氫脫硫、大分子自由基奪氫等耗氫反應。渣油重組分中的雜原子化合物是參與渣油水熱裂解反應的重要組成部分,在催化劑的作用下雜原子化合物能夠與水蒸汽發(fā)生系列鏈的斷裂、加氫、開環(huán)、脫硫等脫雜原子反應,降低生成油粘度,提高了油品質量
[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.
【學位授予單位】：中國石油大學(華東)
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：TE624

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