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Fused chemical reactions to remediate paraffin plugging in sub-sea pipelines.

机译:熔融化学反应,用于补救海底管道中的石蜡堵塞。

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In this work, a timed release scheme of the citric acid-catalyst was used to fuse the highly exothermic reaction between ammonium chloride and sodium nitrite in a fused chemical reaction (FCR) system. The timed release was obtained by encapsulating the acid-catalyst in gelatin capsules then coating the capsules with a water-soluble polymer. The highly exothermic FCR system is demonstrated to be a feasible solution for the billion-dollar problem of paraffin deposition during crude oil production and transportation operations in sub-sea pipelines.; Studies of the exothermic reaction in an isothermal reactor showed that hydrogen ions catalyze the reaction by changing the concentration of the reacting species, not by changing the reaction pathways. The rate-limiting step involves the SN2 reaction between aqueous molecular ammonia and nitrogen trioxide to form nitrosamine. The activation energy of the reaction was found to be about 65.7 kJ/mol experimentally which compares very favorably (within 11%) with the value found from molecular modeling.; The facilitated diffusion of hydrogen ions away from the polymer interface is the principal process that determines the rate limiting step as well as the overall rate of the polymer dissolution. The facilitated diffusion effect increases significantly with an initial increase in the carrier concentration, then approaches a limit at high carrier concentration. However, there are optimum values of the carrier's pKa and of the solution pH which give a maximum facilitation effect. A homogenous chemico-diffusion model can predict concentration profiles of all species across the diffusion boundary layer and polymer dissolution rates which agree well with experimental results.; Good agreement between simulation and experimental results for the FCR system in both batch and flow conditions was achieved. Batch experiments showed that the heat release is controlled by the thickness of the polymeric coating and can be delayed as long as 20 hours. Flow experiments demonstrated that the FCR system could be controlled to provide a substantial amount of effective heat in-situ. This large amount of effective heat is sufficient to soften and melt the wax deposit. The model for the FCR system in flow conditions was also extended to apply in a typical sub-sea pipeline.
机译:在这项工作中,柠檬酸催化剂的定时释放方案用于融合熔融化学反应(FCR)系统中氯化铵和亚硝酸钠之间的高放热反应。通过将酸催化剂包封在明胶胶囊中,然后用水溶性聚合物包被胶囊来获得定时释放。事实证明,高放热的FCR系统是解决海底管道中原油生产和运输作业中石蜡沉积数十亿美元问题的可行解决方案。在等温反应器中放热反应的研究表明,氢离子通过改变反应物种的浓度而不是通过改变反应路径来催化反应。限速步骤涉及分子氨水溶液和三氧化氮之间的SN2反应,以形成亚硝胺。实验上发现该反应的活化能约为65.7 kJ / mol,与分子模型发现的值相比非常有利(11%以内)。氢离子从聚合物界面扩散的促进是决定速率限制步骤以及聚合物溶解总速率的主要过程。随着载体浓度的初始增加,促进的扩散效果显着增加,然后在高载体浓度下达到极限。但是,载体的pKa和溶液的pH值存在最佳值,可以提供最大的促进作用。均匀的化学扩散模型可以预测所有物种在扩散边界层上的浓度分布以及聚合物的溶解速率,这与实验结果非常吻合。在批量和流动条件下,FCR系统的仿真结果与实验结果之间都取得了很好的一致性。分批实验表明,放热受聚合物涂层厚度的控制,可以延迟长达20小时。流动实验表明,可以控制FCR系统以提供大量的有效原位热。大量的有效热量足以软化和熔化蜡沉积物。 FCR系统在流动条件下的模型也得到了扩展,可应用于典型的海底管道。

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