Amination of Cyclohexane by Dielectric Barrier Discharge Processing in a Continuous Flow Microreactor: Experimental and Simulation Studies

A miniaturized flow device has been developed to combine microfluidics technology and plasma process. In this microreactor, atmospheric pressure dielectric barrier discharges are generated in a gas in contact with a liquid phase. This study was conducted with plasma generated in ammonia in contact with a flow of liquid cyclohexane. Cyclohexylamine was synthesized with a good selectivity, and the process can be implemented to improve conversion and effectiveness. Numerical simulations confirmed that NH₂ radicals are generated in the plasma and react with cyclohexyls radicals to achieve the reaction, giving a selectivity of 50% and a total molar conversion of 20% of cyclohexane. The effects of voltage and frequency on the selectivity and the experimental conversion rate were studied and discussed.

     

Simulation of the Kinetics of Cyclohexane Oxidation in a Barrier Discharge Reactor

The kinetics of cyclohexane oxidation in a barrier discharge reactor was simulated for a single voltage pulse. A significant difference between the yields of O₃ obtained experimentally (not detected) and theoretically (15.5 wt %) suggests that O₃ was absent from the reaction mixture because of a fast reaction between O(³ P) and an excited cyclohexane molecule. This hypothesis was indirectly supported by experimental data on the oxidation of a mixture of n-hexane and cyclohexene (50 : 50 wt %). The integrated rate constant of the reaction of O(³ P) with n-hexane was 1.4 × 10^–12 cm³/s, which is an order of magnitude higher than the published value 1.2 × 10^–13 cm³/s.     

气相色谱法分离正己烷和环己烷的实验设计与教学探索

The experiment of separating low toxic n-hexane and cyclohexane by traditional gas chromatography was improved with orthogonal experimental design. The effect of sample quantity, vaporization chamber temperature, detector temperature, column temperature, line velocity and separability of the split ratio were examined. Through the experiment, students could understand the use and maintenance of gas chromatography instruments. At the same time, they could understand separability and column efficiency of chromatography.     

添加气对非平衡等离子体转化低碳烷烃的影响

在常压下, 研究了添加气的种类(N₂, He, Ar, H₂, NH₃, CO和CO₂)对介质阻挡放电低碳烷烃(甲烷、 乙烷和丙烷)转化制低碳烯烃的影响. 结果表明, 以甲烷或乙烷为原料时, N₂, He, Ar和CO的引入有利于提高原料的转化率和总烯烃的选择性; 而CO₂, H₂和NH₃的引入对甲烷、 乙烷的转化率无明显影响, 但H₂和NH₃的引入会使总烯烃的选择性显著降低. 以丙烷为原料时, 所研究的添加气均可提高丙烷的转化率, 而只有CO的引入可提高总烯烃选择性. 综上所述, 80%(摩尔分数) CO添加量最有利于低碳烷烃转化成低碳烯烃, 对应的甲烷、 乙烷和丙烷的转化率分别提高了14.4%, 17.6%和42.8%, 总烯烃的选择性分别提高了19.9%, 25.0%和11.9%. 以CH₄为例, 通过对放电电流波形和等离子体区物种的发射光谱(OES)研究发现, 引入CO能显著增加等离子体的电子密度, 并且体系中出现激发态O^*物种(777.5和844.7 nm), 这种O^*物种能够促进C-H键的断裂, 有利于烯烃的生成. 因此, 等离子体区电子密度的增加和激发态O^*物种的出现可能是CH₄-CO体系中CH₄有效转化的主要原因.     

The Processing of Pyrolysis Fuel Oil by Dielectric Barrier Discharge Plasma Torch

In present paper, an atmospheric-pressure low-temperature plasma treatment of pyrolysis fuel oil (PFO) was investigated in dielectric barrier discharge plasma torch reactor. The effect of the applied voltage and the volume of feedstock, as the main parameters, on the cracking of PFO were studied. By increasing the applied voltage from 10 to 16 kV, the production rate of hydrocarbons containing methane, ethylene, acetylene, propane, propylene, and C₄ rise 18 times. In this case, the production rate of hydrogen increases by approximately 14 times and reaches 7.27 × 10^?3 mol/min for 16 kV. In the feedstock volume investigation, based on limitation of reactor volume, the production rate of hydrocarbons decreased from 0.44 × 10^?3 to 0.15 × 10^?3 mol/min by increasing volume of feedstock from 1 to 5 cc.     

Separation of Inert Gases by Means of the Diffusion Chromatography

Abstract

A mixture of inert gases, He, Ne, Ar, Kr and Xe can be separated into their respective components by applying the technique of diffusion chromatography, in which a special apparatus is not required. Only neccessary is the properly distributed micropores in the column. It can be operated above room temperature. The resultant chromatogram shows sufficient peak resolution except between He and Ne.     

Deposition of Gold Nanoparticles on Polypropylene Nonwoven Pretreated by Dielectric Barrier Discharge and Diffuse Coplanar Surface Barrier Discharge

The aim of this study was to examine and compare the potentials of two different ambient air plasma treatments: volume dielectric barrier discharge and diffuse coplanar surface barrier discharge, for the activation of polypropylene (PP) nonwovens surface. This was done in order to enhance the deposition of gold nanoparticles (AuNPs) onto PP surface. AuNPs were attached onto PP surface from colloidal solution prepared without stabilizers. Scanning electron microscopy, atomic force microscopy, attenuated total reflection-Fourier transform infrared spectroscopy, water absorption, and AuNPs uptake were used to assess the surface changes due to the plasma treatment, and to evaluate the durability of the achieved treatment effects. Finally, as a very important aspiration of the research, antibacterial activity of AuNPs loaded PP nonwovens against pathogens Staphylococcus aureus and Escherichia coli was evaluated in vitro. The plasma modified PP nonwovens have highly improved wetting and sorption properties. The PP nonwovens loaded with 17–62 mg/kg AuNPs exhibit antibacterial activity against tested pathogens. Surprisingly, this activity was enhanced by the first sample rinsing.     

Flue Gas Desulfurization by Dielectric Barrier Discharge

There are many problems with flue gas desulfurization by traditional gas ionization discharge, including the large size of the plasma source, high energy consumption, and the need for a traditional desulfurization method. This paper introduces oxidization of SO₂ to sulfuric acid (H₂SO₄) in a duct by reactive oxygen species (O₂ ⁺, O₃) produced by strong ionization dielectric barrier discharge. The entire plasma reaction process is completed within the duct without the use of absorbents, catalysts, or large plasma source. The reactive oxygen species O₂ ⁺ reacts with gaseous H₂O in the flue gas to generate ·OH radicals, which can oxidize trace amounts of SO₂ in large volumes of the flue gas to produce H₂SO₄. Sulfuric acid is also produced by O₃ oxidation of SO₂ to SO₃, and SO₃ reacting with gaseous H₂O in the flue gas. Experimental results showed that with a gas temperature of 22 °C and reactive oxygen species injection rate of 0.84 mg/L, the SO₂ removal rate was 81.4 %, and the SO₄ ^2? concentration in the recovered liquid H₂SO₄ reached 53.8 g/L.     

Transformations of Cyclohexane under the Action of in situ Generated Aluminum Halides

Transformations of inert cyclohexane into dimethyldecalins under mild conditions in the presence of a simple catalytic system consisting of aluminum metal and halomethanes were studied.     

Features of Propylene Oxidation by Carbon Dioxide in Dielectric Barrier Discharge

High Energy Chemistry - The study is a continuation of the research cycle concerning the oxidation of propylene in dielectric-barrier discharge plasma to propylene oxide and the corresponding...     

Characterization of RF Discharge in Liquid n-Hexane and its Application to Synthesize Carbon Nano-Particles

The RF plasma discharge in liquid n-hexane is used to synthesize carbon nanoparticles. The results show that amorphous carbon nanoparticles with size of 5?C25?nm are the main product in the plasma in liquid n-hexane. Carbon nano-tubes of average diameter of 19?nm and length of 500?nm are also observed. The energy efficiency for carbon nanoparticles production is 2.9?mg/kJ which is more than 10 times larger than that of typical arc discharge synthesis method. The high speed observation indicates that the RF plasma in liquid has an alternating behaviour and it does not continuously emit light. The OES results show that H and C₂ are the main observed species in the plasma. Based on the OES data, it is shown that plasma temperature is 4,030?K and the electron density is 2.54?×?10²²?m^?3. Our results suggest that this method can be considered as a new route for carbon nanostructures production.     

Point and Multipoint to Plane Barrier Discharge Process for Removal of NOx from Engine Exhaust Gases: Understanding of the Reactional Mechanism by Isotopic Labeling

An experimental study on the removal of NO_x in a simulated vehicle exhaust gas has been carried out using point to plane and multipoint to plane DBD corona reactors. Hydrocarbon (C₃H₆) and NO_x by-products were systematically investigated with a Gas Chromatography coupled to a Mass Spectrometry (GC/MS). NO_x (NO and NO₂) and CO output were also monitored with a gas analyzer in order to complete the mass balance. ¹⁸O tracer technique analyzes is applied to investigate the mechanism of propylene decomposition. From the plasma chemical reaction pathway proposed, it is apparent that the oxygen activation is one of the important steps for initiating the oxidation processes and the R-NO_x formation. We present data for the reaction of the (N₂/O₂/C₃H₆/CO₂NO/H₂O system in the corona discharge reactors mentioned above. This system has been shown to generate a significant amount of aldehyde. CH₃NO₂ and CH₃ONO₂ are the main R-NO_x compounds produced. Reactant composition and discharge energy densities (controlled by a numerical oscilloscope) were the operating parameters under study in wet and dry air mixture. Water vapors played an important role in NO_x removal (especially in NO₂ removal) via the reaction forming HNO₃. Therefore, in wet-gas mixture supplied reactors the highest removal rates of NO_x were as high as 30%, while in dry-gas only 15%. Different dielectric materials such as Al₂O₃/SiO₂ and TiO₂ on Al₂O₃/SiO₂ support have been used.     

高频介质阻挡放电烟气脱硫研究

采用高频介质阻挡放电的方式产生低温等离子体,研究在不加入NH₃的情况下流动态SO₂的去除情况.实验表明,在输入电压为12 kV,SO₂浓度为5400 mg/m³,气体流量为0.36 m³/h,相对湿度为55%时,脱硫率可达到70%以上;水气的存在对SO₂的去除有较大的促进作用,升高电压和增加O₂量对脱硫率的促进作用有限.对实验结果进行了解释,并提出了反应机理.     

Blood Coagulation and Living Tissue Sterilization by Floating-Electrode Dielectric Barrier Discharge in Air

Thermal plasma discharges have been widely used in the past for treatment of living human and animal tissue. However, extensive thermal damage and tissue desiccation occurs due to extreme temperatures. Some solutions have been offered where the temperature is lowered by short current pulses, addition of noble gases, or significant decrease in the size of treatment electrodes. We propose a method of direct treatment of living tissue that occurs at room temperature and pressure without visible or microscopic tissue damage. The presented Floating-Electrode Dielectric Barrier Discharge plasma is proven electrically safe to human subjects and our results show no gross (visual) or histological (microscopic) damage to skin samples in minutes, complete tissue sterilization from skin flora in seconds, and blood clot formation in seconds of electric plasma treatment. We also observe significant hastening of blood clot formation via electric plasma induced catalysis of “natural” processes occurring in human blood. A model describing these processes is offered.An erratum to this article can be found at     

Plasma Activation of Wood Surface by Diffuse Coplanar Surface Barrier Discharge

Radial cuts of Pedunculate oak (Quercus robur L.) heartwood was activated by Diffuse Coplanar Surface Barrier Discharge (DCSBD) plasma. The plasma treatment resulted in a considerable increase of free surface energy and in the substantial reduction of 50 μl water droplet uptake time. FTIR analysis confirmed the formation of additional polar functional groups on the wood surface due to the plasma treatment. This is consistent with the shift of wood surface pH level towards more acidic values. The energy efficiency of the DCSBD plasma treatment is better comparing to the known volume dielectric barrier discharge treatment method.     

Destruction of Styrene in an Air Stream by Packed Dielectric Barrier Discharge Reactors

This study presents the decomposition rates of styrene vapors with non-packed and packed bed dielectric barrier discharge reactors. The concentrations of intermediate byproducts at various plasma operation conditions were evaluated. The results showed that although styrene vapors could be almost completely removed at low styrene inlet concentration of 132 ppm, the selectivity of CO₂ as the major product was rather low in a non-packed bed reactor. It was found that solid carbon containing compound was the major byproduct. An increase in the styrene inlet concentration tended to reduce the styrene removal efficiency, it also led to increase in the solid byproduct. The reactors that packed with glass, Al₂O₃ or Pt–Pd /Al₂O₃ pellets could improve the styrene decomposition efficiency and reduce the formation of intermediate products, of which the best oxidation of styrene to CO₂ could be achieved with a Pt–Pd /Al₂O₃ packed bed reactor. The carbon byproducts could also be reduced if the rector length was increased. The concentrations of ozone formed during the plasma process were also evaluated for the non-packed and packed bed reactors. The plasma reactor that packed with Pt–Pd /Al₂O₃ pellets was proved to have the lowest O₃ concentration.     

CARS Diagnostic and Modeling of a Dielectric Barrier Discharge

Dielectric barrier discharges (DBD) with planar- and knife-shaped electrodes are operated in N₂O₂NO mixtures under a pressure of 20 and 98 kPa. They are excited by means of consecutive unipolar or bipolar high-voltage pulse packages of 10 kV at a pulse repetition rate of 1 and 2 kHz. The rotational and vibrational excitation of N ₂ molecules and the reduction of nitric oxide (NO) in the discharge have been investigated using coherent anti-Stokes Raman scattering (CARS) technique. Rotational (gas) temperatures near the room temperature and vibrational temperatures of about 800 K at atmospheric pressure and 1400 K at a pressure of 20 kPa are observed. Therefore, chemical reactions of NO with vibrationally excited N ₂ are probably insignificant. One-dimensional kinetic models are developed that balance 35 chemical reactions between 10 species and deliver equations for the population density of excited vibrational levels of N ₂ together with a solution of the Boltzmann equation for the electrons. A good agreement between measured vibrational temperatures of N ₂ , the concentration of NO, and calculated data is achieved. Modeling of the plasma discharge verifies that a DBD operated with a N₂NO mixture reduces the NO content, the simultaneous presence of O ₂ , already 1%, is enough to prevent the NO reduction.