Reaction Processes in Organic Droplet Spray Plasma Reactors

虽然许多有机化合物通常使用高温、高压和/或催化工艺合成，但是应用低温放电等离子体工艺进行有机合成具有通过等离子体的空间和时间控制来提高能量效率和影响化学选择性和产率的潜力。 为了在碳氢化合物中引入官能团，例如OH基团，该项目涉及在暴露于有机液体小液滴的低温等离子体中引发的反应。 这项工作将推进我们的理解，在放电等离子体中的有机气体-液体反应的液滴暴露于环境温度和压力条件下的等离子体环境，使他们不蒸发。 该研究涉及合成各种有机化合物，从饱和和不饱和碳氢化合物液体开始，以小液滴的形式喷入反应器。 纯有机液滴将流入低温和低功率等离子体中，在那里发生蒸汽和界面反应。 在饱和烃的情况下，将研究羟基化反应形成醇，重点是具有6至10个碳的烃。 羟基自由基将由添加到流动气流中的少量水和/或过氧化氢蒸气形成。 在不饱和烃的情况下，氢化反应将用混合在氩气载体中的氢气进行研究。 将研究具有6至10个碳的不饱和烃以及选定的油。 在这两种情况下，选择性和产率将被分析为各种反应器特性的函数，包括气体和液体流速和组成，脉冲输入功率和频率，以及电极几何形状。 将被测试和分析的一般工作假设是，可以通过改变等离子体和反应器操作条件来控制来自有机液滴的有机化合物的等离子体反应的反应选择性和产率。 预期可溶于有机液相的反应产物将通过先前发现的从液态水滴产生过氧化氢的机制而受到青睐，由此液体可溶性产物优先积聚在液相中，在液相中它们被保护免于在周围气体中的等离子体降解。 本课题的目的是通过对等离子体的时空控制，开发在液相中向有机化合物导入功能性的新方法。本课题的目的是开发气液环境中的等离子体如何生成各种合成有机化合物的基础知识。 了解这些反应是如何发生的对于化学反应器的设计和操作非常重要，这些反应器可以在实际应用中用于制造许多有用的化合物。 例如，在这样的系统中，各种醇可以由烃制成，并且这项工作将对材料和化学合成以及燃料处理中使用的等离子体工艺的一系列其他应用产生影响。 这项工作预计将导致我们对等离子体化学的理解和进一步发展的重大进展，并对有效地从各种液态烃源生产有价值的有机化合物产生潜在影响。

While many organic compounds are commonly synthesized using high temperature, high pressure, and/or catalytic processes, the application of low temperature electric discharge plasma processes to perform organic synthesis has the potential to improve energy efficiency and to affect chemical selectivity and yield through spatial and temporal control of the plasma. In order to introduce functionality into hydrocarbons, for example OH groups, this project deals with reactions initiated in low temperature plasma exposed to small droplets of organic liquids. This work will advance our understanding of organic gas-liquid reactions in electrical discharge plasma where the liquid droplets are exposed to the plasma environment under ambient temperature and pressure conditions such that they are not evaporated. The research involves the synthesis of a wide range of organic compounds starting with saturated and unsaturated hydrocarbon liquids that are sprayed into the reactor as small droplets. The pure organic droplets will flow into the low temperature and low power plasma where vapor and interfacial reactions occur. In the case of saturated hydrocarbons, hydroxylation reactions to form alcohols will be investigated with emphasis on hydrocarbons with 6 to 10 carbons. Hydroxyl radicals will be formed from small amounts of water and or hydrogen peroxide vapors added to the flowing gas stream. In the case of unsaturated hydrocarbons hydrogenation reactions will be investigated with hydrogen mixed in an argon carrier. Unsaturated hydrocarbons with 6 to 10 carbons as well as selected oils will be studied. In both cases selectivity and yields will be analyzed as functions of the various reactor properties including gas and liquid flow rates and composition, pulsed input power and frequency, and electrode geometry. The general working hypothesis that will be tested and analyzed is that reaction selectivity and yield for plasma reactions of organic compounds from organic liquid droplets can be controlled through variation of plasma and reactor operating conditions. It is anticipated that the reaction products that are soluble in the organic liquid phase will be favored through a mechanism found previously for hydrogen peroxide generation from liquid water droplets whereby liquid soluble products preferentially accumulate in the liquid phase where they are protected from plasma degradation in the surrounding gas. In general, the project seeks to develop a new way to introduce functionality into organic compounds in the liquid phase through spatial and temporal control of the plasma.This project will develop fundamental knowledge on how plasma in gas-liquid environments leads to the formation of various synthetic organic compounds. Understanding of how such reactions occur is important for the design and operation of chemical reactors that can be used in practical applications to make many useful compounds. For example various alcohols can be made from hydrocarbons in such systems, and this work will have impact on a range of other applications of plasma processes used in material and chemical synthesis and fuels processing. This work is expected to lead to significant advances in our understanding and further development of plasma chemistry with potential impact on the production of valuable organic compounds efficiently from various liquid hydrocarbon sources.