Reaction characteristics of low temperature oxidation of light crude oil with disoxidation air
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摘要:
塔河北区块轻质原油与减氧空气在温度和压力作用下，探究其组分变化情况和耗氧量规律。在室内使用高温高压反应釜开展原油静态氧化实验，较为系统地研究不同含氧量及不同注气量的减氧空气对原油的氧化作用；并利用色谱分析对烃类分析，收集反应气体进行气体分析，气体组分和原油组分都有不同程度的变化。研究结果表明：①原油样本与减氧空气发生低温氧化反应，重质组分C21以上的组分均下降，低于C13的轻质组分含量均上升；②原油氧化效果随着含氧量上升而增强，反应过程组分对应"拐点"靠前；③含氧量一定时，改变油气比，反应对应的"拐点"不变；含氧量为下降趋势后趋于平缓；④低温氧化过程生成的CO2含量为上升趋势后趋于平缓；⑤在油藏温度（160℃）下，原油主要涉及2个反应热裂解和加氧反应。热裂解反应与含氧量无关，和温度有关，主要反应温度是160~200℃。高碳组分沥青质等重质组分会分解成饱和烃。加氧反应主要是芳香烃，胶质加氧反应也会生成沥青质。当2种反应同时存在时，沥青质参与热裂解的含量大于加氧反应芳香烃等生成的沥青质量，会导致沥青质含量减少。
Abstract:With the temperature and pressure effect, the composition change and oxygen consumption law of light crude oil and discoxidation air in Tahei North Block were studied. The static oxidation experiment of crude oil was carried out in a high temperature and high pressure reactor indoors to systematically study the oxidation effect of crude oil by disoxidation air with different oxygen content and different gas injection volume; the hydrocarbon was analyzed by chromatographic analysis, and the reaction gas was collected for gas analysis. The results showed that: ① The low-temperature oxidation reaction between crude oil sample and disoxidation air decreased the components above C21 and increased the content of light components below C13; ② The oxidation effect of crude oil increased with the increase of oxygen content, and the components in the reaction process corresponded to the "inflection point" in the front; ③ When the oxygen content was constant, the "inflection point" corresponding to the reaction remained unchanged by changing the oil-gas ratio; In the overall reaction process, the oxygen content decreased and then tended to be flat; ④ CO2 was generated in the process of low-temperature oxidation, and the CO2 content tended to be flat after increasing; ⑤At reservoir temperature (160℃), crude oil mainly involves two reaction thermal cracking and oxygenation reactions. The thermal cracking reaction is not related to the oxygen content, but to the temperature. The main reaction temperature is 160-200℃. Heavy components such as high-carbon asphaltene will be decomposed into saturated hydrocarbons. The oxygenation reaction is mainly aromatic hydrocarbon, and the resin oxygenation reaction will also produce asphaltene. When the two reactions exist at the same time, the content of asphaltene participating in thermal cracking is greater than the quality of asphaltene generated by oxygenation reaction aromatic hydrocarbon, which will lead to the decrease of asphaltene content.
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Key words:
- disoxidation air /
- oxygen content /
- low temperature oxidation /
- light crude oil /
- composition change
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图 2 3种含氧量的减氧空气与原油低温氧化反应前后的组分变化图
Figure 2. Composition changes before and after low temperature oxidation reaction of three kinds of oxygen containing disoxidation air and crude oil
图 3 3种含氧量的减氧空气与原油低温氧化反应气体组分(O2, CO2)变化图
Figure 3. Changes in gas composition (O2, CO2) in low temperature oxidation reaction among three kinds of oxygen containing disoxidation air and crude oil
图 4 3种不同注气量的减氧空气与原油低温氧化反应前后的组分变化图
Figure 4. Composition changes before and after low-temperature oxidation reaction between disoxidation air with three different gas injection rates and crude oil
表 1 塔河北区块轻质原油组分分布
Table 1. Composition distribution of light crude oil in Tahe North Block
碳数烃的分布 体积分数φB/% C10 6.15 C11~C15 35.89 C16~C20 27.31 C21~C25 15.80 C26~C30 9.73 C31~C35 4.37 >C35 0.75 总计 100.00 
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表 2 塔河北区块轻质原油在21%、12%、6%含氧量下族组分变化
Table 2. Change in 21%, 12% and 6% group components of light crude oil in Tahe North Block
含氧量
φB/%芳香烃 饱和烃 胶质 沥青质 wB/% 原油 28.69 43.03 16.60 11.68 6 11.56 65.09 19.16 5.19 12 7.49 68.69 21.59 4.23 21 1.49 72.66 24.91 2.94
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