为明确环烷基稠油在火驱过程中生成焦炭的规律和石油焦炭基本性质,应用动态气流氧化原油装置,开展了环烷基稠油注空气燃烧生成焦炭过程的研究,并对生成的石油焦炭进行了组成和结构表征。研究表明:环烷基稠油在250~300 ℃开始生成焦炭,随着反应温度升高,焦炭产率逐渐增加,温度达到450 ℃时,焦炭产率最高,为10.8%;温度为500~600 ℃时,焦炭的燃烧反应加剧,焦炭收率降至4.6%。电镜观察焦炭为0.05~1.00 μm碳层叠加的致密片层结构,以400 ℃为分界点可以将焦炭分为2类。300~350 ℃生成焦炭的H/C为0.78~0.82,为含有大量烷基链的氧化焦炭;400 ℃时裂解反应加剧,稠油成焦过程由加氧反应为主转变为裂解反应为主;400~600 ℃生成焦炭的H/C为0.33~0.47,为芳香度和石墨化程度更高的裂解焦炭。该研究对环烷基稠油火驱开发点火及火线控制具有一定指导意义。
The process of coke generation of naphthenic heavy oil during air injection combustion was studied to clarify the law of coke generation and the basic properties of petroleum coke in the fire flooding process of naphthenic heavy oil, and the composition and structure of generated petroleum coke were characterized through a dynamic airflow oxidation crude oil device. The study showed that the coke generation from naphthenic heavyoil starts at about 250-300 ℃, and the coke yield increases gradually with the rise of the reaction temperature and the highest coke yield of 10.8% is obtained when the temperature reaches 450 ℃; the combustion reaction of coke intensifies, and the yield decreases to 4.6% when the temperature is 500-600 ℃. The coke is observed as a dense lamellar structure with 0.05-1.00 μm carbon layers superimposed on each other by electron microscope, and it could be classified into two categories with 400 ℃ as the demarcation point. The H/C atomic ratio of coke generated is 0.78-0.82 at 300-350 ℃, which is oxidized coke containing many alkyl chains. The cracking reaction intensifies at 400 ℃, and the process of heavy oil coke formation transforms from the primary oxygenation reaction to that of cracking, and most cokes generate at 400 ℃. The H/C atomic ratio of the coke generated at 400-600 ℃ is 0.33-0.47, which was cracked coke with higher aromaticity and graphitization degree. This study is of some significance for the ignition and fireline control during fire flooding development of naphthenic heavy oil.
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