冷却通道表面处理对超临界烃热裂解结焦的抑制作用-化学工艺专业论文.docxVIP

PAGE PAGE 3 摘 要 实现高超音速飞行需要解决推动力和热障两大难题。吸热燃料既可通过燃烧 提供动力，又可作为冷却剂满足冷却要求，具有巨大的应用前景。但燃料裂解过 程中不可避免发生结焦，成为制约其应用的一个主要因素，是实现飞行器高超音 速飞行急需解决的问题。 本文采用预氧化、制备 MOCVD 涂层等方法对 321# 不锈钢管(?3 mm×0.5 mm) 进行表面处理，并对预处理管的性质进行了系统研究，利用超临界 RP-3 的热裂 解反应为探针，研究表面处理的裂解结焦行为。 预氧化反应管表面性质不同，结焦行为有异。600~800 oC 预氧化管 Cr 氧化 物不断向金属表面迁移， Fe、Ni 氧化物向金属内部迁移，降低结焦，但同时产 生大量空缺位提供渗碳通道，最终导致结焦量虽依次降低仍高于空管，只有 900 oC 预氧化管表面形成一层致密的 Cr2O3 膜才得以抑制，几乎不生成纤维碳。 以仲丁醇铝为原料，采用 MOCVD 法，在不锈钢管内壁制备了厚度 为 318-1280 nm 的 Al2O3 涂层。XRD 结果显示 Al2O3 涂层本质上为无定形态。随着 涂层厚度从 318 nm 增加到 1280 nm，涂层的结焦抑制率从 37% 提高到 69%。 TPO 和 SEM 的分析结果表明 Al2O3 涂层不仅抑制金属催化焦的形成，也抑制芳 烃聚合焦的生成。 对比MOCVD 法制备的1 μm 厚的Al2O3、TiO2 和ZrO2 三种涂层，结焦抑制 率分别为64%、60% 和23%。ZrO2 涂层由于抗热冲击性能较差，高温下从金属 表面剥落，抑制结焦效果较差。 涂层同时抑制催化焦炭和裂解焦炭形成的机制在于：涂层能够覆盖金属表面 活性位点，在烃类小分子和金属表面之间创建一层障碍物，抑制催化焦炭形成， 而裂解结焦通常生成于催化焦活性位点周围，随后一并得到抑制。 关键词： 预氧化 MOCVD 涂层（Al2O3、TiO2、ZrO2） 厚度 超临界热裂解 纤 维碳 芳烃碳 ABSTRACT For future hypersonic aircrafts, hydrocarbon fuels not only serve as a conventional role of the propellant but also an ideal coolant to resolve the problem of thermal management by removing the waste heat from aircrafts. However, a byproduct of carbonaceous deposits is inevitably generated accompanied with the cracking of jet fuel, which is taken as one of uncertain issues in utilizing hydrocarbon fuels as the heat sink for advanced cooling. In this work, the stainless steel tube (?3 mm×0.5 mm) was pretreated by means of pre-oxidation and MOCVD coating. We characterized the pretreated tubes, and studied the thermal cracking/coking of supercritical RP-3 over pretreated tubes. The amount of carbon deposition was decreased as pre-oxidation temperature increased. However, the surfaces of tubes pre-oxidated at 600~800 oC were very rough, even though the coking amounts gradually decreased but still exceeding the amouts in bare tube. Only when the tube surface pre-oxidated at 900 oC formed a compact film, the cokes were inhibited. Increasing pre-oxidation temperature, Cr was migrated to the surface and Fe, Ni was migra