Mechanism of methanol decomposition by non-thermal plasma

In this investigation available experimental data in the literature were used to propose a reaction mechanism for the destruction of methanol using non-thermal plasma technology. In a recent study [M. Derakhshesh, J. Abedi, M. Omidyeganeh, Modeling of hazardous air pollutant removal in the pulsed corona discharge, Phys. Lett. A 373 (2009) 1051–1057.] the reactor performance equation for destruction of pollutants was developed. The order of reaction for methanol decomposition is estimated using a recently developed performance model and the available experimental data. It is found that that methanol decomposition reaction follows order one. In addition, using the experimental data available in the literature the rate constant for methanol decomposition is obtained and the overall rate was compared with our previous study.     

Decomposition of methylene chloride by electron beam and pulsed corona processing

Experiments on the plasma-assisted decomposition of dilute concentrations of methylene chloride in atmospheric-pressure N₂ and dry air streams by electron beam and pulsed corona processing are presented. This paper presents the first experimental evidence showing that the decomposition of methylene chloride in a non-thermal plasma at ambient gas temperature proceeds via reaction with nitrogen atoms. The decompositions is more efficient with energy deposition in electron beam generated plasmas because of the higher rate for electron-impact dissociation of N₂. In dry air mixture, the decomposition of methylene chloride is degraded substantially because the nitrogen atoms are consumed in the production of nitrogen oxides. At higher gas temperatures (300°C), the decomposition of methylene chloride in dry air is shown to proceed via reaction with oxygen atoms. The main products of methylene chloride decomposition in dry air mixtures are CO, CO₂, HCl, and probably Cl₂.     

A DFT-based microkinetic theory for Fe2O3 reduction by CO in chemical looping

Redox kinetics of oxygen carrier in chemical looping is an important component for material preparation, reactor design and process demonstration. How to bridge the gap between the microscale density functional theory (DFT) and the macroscale redox kinetics and develop a first-principle-based theoretical model is still a challenge in the field of chemical looping. This study addresses this challenge and proposes a DFT-based microkinetic rate equation theory to calculate the heterogeneous kinetics of Fe₂O₃ reduction by CO in chemical looping. Firstly, the DFT calculation is adopted to search the reaction pathways and to obtain the energy barriers of elementary reactions. Secondly, the DFT results are introduced into the transition state theory (TST) to calculate the reaction rate constants and build the rate equations of elementary surface reactions. Finally, by considering the bulk diffusion, a rate equation is developed to bridge the gap between the elementary surface reactions and the grain conversion. In the theory, the reaction mechanism obtained from DFT and kinetic rate constants obtained from TST are directly implemented into the rate equation to predict the reduction kinetics of oxygen carriers without fitting experimental data. The accuracy of the developed theory is validated by experimental data of two Fe₂O₃ oxygen carriers obtained from the thermogravimetric analyzer (TGA). The microkinetic rate equation theory is based on the first principles calculation and can predict directly the redox kinetics of oxygen carriers without depending on the experimental kinetic data, therefore, it provides a powerful theoretical tool to screen the oxygen carrier materials and optimize the microstructure of oxygen carriers.     

Modeling of the electrostatic corona discharge reactor

A model is presented for the electrostatic corona discharge reactor (ECDR) in a pin-plate configuration. The main objective is to describe the fundamental chemistry and physics governing the discharge behavior and to predict the ECDR performance under various operating conditions. The electric field strength is estimated assuming a space-charge-free field. A two-term spherical harmonic expansion is used to solve the Boltzmann equation for the electron energy distribution function (EEDF) and calculate the electron-molecule reaction rates using collision cross-section data. Species continuity equations are solved for the dry and wet air systems to predict ozone and NO_x at various feed flow rates (1630, 4890, 14, 670 cm/s) and an applied voltage of 10 kV. Among the various results reported, it is noted that the calculations indicate the Maxwell EEDF cannot be used because it overpredicts the electron-molecule rate coefficients by several orders of magnitude     

Influence of temperature and humidity on NO x removal by corona discharge

The object of this experimental investigation was the influence of temperature and humidity on the efficiency of removal of NO _x by a pulsed corona discharge from a mixture N₂ : O₂ : CO₂ : H₂O : NO simulating a combustion flue gas. The pulsed corona discharge was generated in a wire-to-cylinder reactor. It was found that removal of NO _x was most efficient when H₂O concentration corresponded with the saturated vapour pressure. In the case of the operating gas containing constant H₂O concentration removal of NO _x decreased with increasing temperature of the operating gas. Dedicated to Prof. Jan Janča on the occasion of his 60^th birthday. This work is devoted to the 60^th birthday of Professor Jan Janca, our good colleague, merited teacher, researcher and famous physicist, discussion with whom stimulated this and other our work during years.     

Decomposition of volatile organic compounds by a novel electrode system integrating ceramic filter and SPCP method

We developed a new efficient apparatus for gas treatment in which a ceramic filter and SPCP (surface corona discharge induced plasma chemical process) were integrated. In this study, the feasibility of the reactor to decompose volatile organic compounds (VOCs) and performance were evaluated. The efficiency was examined against various conditions of initial concentration of VOCs, as trichloroethylene (TCE), toluene and benzene, and by using variable flow rates of carrier gases (air, nitrogen, and mixture of nitrogen and oxygen or water vapor). TCE was decomposed effectively within the reactor system, especially when the carrier gas contains oxygen or water as an oxygen source, whilst the decomposition efficiency was low with the nitrogen carrier. With a sufficient oxygen source, no organic by-products were detected in the treated gas, and TCE was oxidized to inorganic substances. Toluene and benzene were efficiently decomposed as well.For performance evaluation of such non-thermal plasma reactors for VOC treatment, we proposed a new parameter which is derived with substance based energy density, mSED (J/mol). The new parameter has merit to express the performance with a single parameter for a range of discharge power, flow rates, and initial concentrations of the gas to be treated. With the parameter proposed, the evaluation resulted in a new reactor in this study that has as high a performance as a conventional packed-bed reactor, and their performances are higher than pulse corona (PC), and dielectric barrier discharge reactors.     

New insights into the oxidation chemistry of pyrrole,an N-containing biomass tar component

Pyrrole, the smallest molecule with a nitrogen atom in the heterocycle ring, is an important tar component from coal and nitrogen-rich biomass devolatilization. Understanding the combustion chemistry of pyrrole can help to elucidate the pollutant formation chemistry from fuel nitrogen, thus enabling cleaner biomass energy utilization technologies. Experimental measurements were performed in a jet stirred reactor coupled with time of flight molecular beam mass spectrometry using synchrotron vacuum ultraviolet beam as photon ionization source, and gas chromatography-mass spectrometry to provide comprehensive measurements of 31 species including nine C₄ and C₅ N-containing compounds. Based on the evidence from the experiments and aiming to improve the kinetic model performance, possible formation routes are proposed with OH addition as the entrance reaction. Reaction rate coefficients for the OH addition channel as well as those for key H-atom abstraction reactions (H, OH, CH_3, and HO₂) were calculated by quantum chemical methods and updated in the model. The updated model can qualitatively predict the identified C₄ N-containing species and perform reasonably well for a large set of experimental data considered for validation, overall improving the performance of the previous model. The influence of the investigated reactions on the predictions of fuel reactivity and pollutant formation motivates further investigations of N-containing fuel chemistry.     

Mass transport characteristics in a pulsed plasma enhanced chemicalvapor deposition reactor for thin polymer film deposition

A pulsed plasma enhanced chemical vapor deposition (PECVD) reactor is used for the preparation of thin polyacetylene films. A theoretical model based on the mass transport characteristics of the reactor is developed in order to correlate with experimentally obtained spatial deposition profiles for the acetylene plasma polymer film deposited within the cylindrical reactor. Utilizing a free radical mechanism with gas phase initiation of the polymerization reaction as the rate controlling step, a system parametric study is performed to predict the Peclet number range of operation for the pulsed PECVD reactor. This parametric study indicates radical decay by diffusion to the reactor walls to be the significant physical phenomenon in the system. It is concluded that a quasi-steady-state model is a good tool for predicting the important mass transfer phenomena occurring in the pulsed plasma reactor     

Two-dimensional atomic hydrogen concentration maps in hot-filament diamond-deposition environment

This paper reports the two-dimensional mapping of atomic hydrogen concentration with two-photon excited laser induced fluorescence in a multi-wire grid hot-filament chemical vapor deposition reactor. The measurements were made in a diamond film deposition environment under different filament temperatures and wire configurations. The measurement was calibrated with a titration reaction using NO₂ as a titrant. The kinetic gas temperature in the reactor was measured from the Doppler broadening of the Lyman-β transition excited in the fluorescence. The filament temperature was found to have a significant effect on atomic hydrogen production and transfer to the substrate. The axial concentration distributions were compared to a one-dimensional kinetic gas–surface chemistry model with good agreement. The model produced a reasonable estimate for the bulk diamond film growth rate. Received: 25 June 2001 / Revised version: 15 February 2002 / Published online: 2 May 2002     

A compact high-voltage pulse generator using a rotary airhole sparkgap

A pulsed-corona-discharge nonthermal plasma technique offers the advantages of energy efficiency and capability for the simultaneous removal of coexisting pollutants. The key to success in a nonthermal plasma approach is to produce a corona discharge in which the bulk of the electrical energy goes into the production of energetic electrons, rather than into gas molecules heating. By driving the nonthermal plasma reactor with very short pulses of high-voltage, short-lived corona discharge plasmas are created that consist of energetic electrons, which in turn produce the radicals and ozone responsible for the decomposition of the toxic molecules. Because of the short lifetime of the pulsed corona discharge, little electrical power is dissipated in movement of heavy molecule ions in the processing region, thus avoiding heating the gas and providing good electrical energy efficiency.A high-voltage pulse generator with a rotary airhole sparkgap, instead of a conventional rotary ball sparkgap, has been proposed. Its rise and fall time characteristics to be used as a smart pulse generator for pulsed corona discharge-type nonthermal plasma reactor were investigated. Parametric studies showed that the proposed airhole sparkgap had a very fast rise time, very short fall time, very low-and-stable breakdown voltage, and reliable pulse repetition characteristics, compared with the conventional rotary ball sparkgap.     

Mathematical analysis of positive pulsed corona discharge processemployed for removal of nitrogen oxides

A mathematical model was proposed to describe the behaviour of the removal of nitrogen oxides (NO_x) in a positive pulsed corona discharge reactor. The proposed model takes into account radical production at each pulsing and subsequent radical utilization for NO_x removal. The production efficiencies of radicals such as O, OH, H, and N were derived by considering direct electron impact on dissociation of gaseous molecules, followed by excitation transfer reactions of excited oxygen atoms. The production efficiencies of those species were used for the model calculations. The proposed model could adequately predict the experimental data. Of the active species present, the ozone (O₃) produced by the reaction of O radical with oxygen was found to play the crucial role in oxidation of NO to NO₂ , both theoretically and experimentally     

Thermal decomposition of dichloroketene and its reaction with H atoms

The thermal unimolecular decomposition of dichloroketene CCl₂CO → CCl₂ + CO (reaction 1) was studied experimentally and computationally. Dichloroketene was produced by the pulsed laser photolysis of hexachloroacetone, and the kinetics of its decay due to reaction 1 was monitored using photoionization mass spectrometry. Rate constants of reaction 1 were determined in direct time-resolved experiments as a function of temperature (740–870 K) and bath gas density ([He] = (3–25) × 10¹⁶ atom cm⁻³, [N₂] = 12 × 10¹⁶ molecule cm⁻³). Reaction 1 is in the falloff region under these conditions. The potential energy surface (PES) of reaction 1 was studied using quantum chemical methods. The experimental k₁ (T, P) dependence was reproduced with an RRKM/master equation model based on quantum chemical calculations. Parameterized expressions for the rate constants of reaction 1 and the reverse reaction, that of CCl₂ with CO, were obtained over wide ranges of temperatures and pressures. The enthalpy of formation of CCl₂CO was determined in quantum chemical calculations. The kinetics of the reaction of dichloroketene with hydrogen atoms (reaction 2), an important channel of destruction of CCl₂CO in flames, was studied computationally. The PES of reaction 2 was studied using quantum chemical methods. Temperature and pressure dependences of the rate constants of the four dominant reaction channels were obtained in transition state theory and master equation calculations; the technique of isodesmic reactions for transition states was applied to the channel of Cl atom abstraction. Analysis of the experimental data and the computational models of reactions 1 and 2 demonstrates that thermal decomposition is a major pathway of destruction for dichloroketene in combustion systems.     

纳秒脉冲放电处理有机染料废水的实验研究

随着印染行业的快速发展,印染废水的排放与日俱增。由于废水中的有机物具有成分复杂、难以降解的特点,若未经有效处理直接排放,会对生态环境造成严重的污染和危害。试验设计了一种多针-网式反应器循环处理有机组分为酸性红73(AR73)的模拟废水,其采用自行设计的基于TLT(Transmission Line Transformer)的高压重频纳秒脉冲电源驱动。电源可以产生峰值电压为50 kV,脉宽40 ns,上升沿20 ns的纳秒脉冲信号,工作频率可达500 Hz。试验考察了峰值电压、放电频率、染料初始质量浓度及作用时间等因素对AR73降解效果的影响。为评价处理效果,采用紫外分光光度法分别测量了废水中剩余染料浓度、过氧化氢浓度等指标。结果表明,在初始浓度30 mg/L,循环流量3.4 L/min,放电间距30 mm,峰值电压44.26 kV,放电频率200 Hz条件下处理30 min,AR73降解率可以达到83.20%,单次脉冲注入能量为11.73 mJ,过氧化氢浓度为47.36μmol/L,反应器脱色能效(G50)可以达到31.07 g·kW^-1·h^-1。增大放电电压可以进一步提高AR73降解率,溶液中活性物质浓度提高,但是能量效率有所下降。     

Predictive model of decontamination efficiency of gaseous pollutant by non-equilibrium plasma

During non-equilibrium plasma (NEP) reactions, chemical bonds of pollutant compound are broken by energy generated in the reactor so that the pollutants are decontaminated. In this study, the energy conversion factor (E_f) is defined as the ratio of the dissociation energy of chemical bonds destroyed in NEP reaction system to the energy inputted in plasma reactor. The energy conversion factor of chemical bonds (E_f,i), S–H, C–Cl, C–S, C–H, C–C etc., were determined by decontamination experiments of H₂S and 2-CEES in plasma reactor. Based on the E_f,is, the predictive model of NEP decontamination efficiency of gaseous pollutant was developed and applied to predict decontamination efficiency of CH₃CH₂SH, in which all E_f,is of chemical bonds are known as described above. It was shown by the decontamination experiment of CH₃CH₂SH that the predictive value was well agreed to experimental data. Therefore, the model can be used to predict decontamination efficiency of those pollutants in which all E_f,is of chemical bonds have been determined. An improved model is also produced by the analysis of predictive error.     

Pulsed corona discharge driven by Marx generator: Diagnostics and optimization for NOx treatment

A compact, repetitive Marx generator with an external trigger is constructed and coupled with a wire-to-plate corona reactor for a positive pulsed corona discharge studies. The reactor resistance and capacitance behavior during the pulse was observed. It was found that the reactor's capacitance increases three times during the pulse due to the streamer propagation from anode to grounded electrode. Using the time development of the capacitance and resistance during the pulse and the reactor inter-electrode distance, the streamer velocity has been calculated to be 1 × 10⁶ m/s, for system arrangement presented in this work. As an indicator of chemical activity of pulsed corona, ozone production was measured. Emission spectroscopy measurements in the UV region were performed to detect species that appear in the discharge and to determine vibrational and rotational temperatures, which are found to be 3200 K and 340 K respectively. As a measure of pollution control potential of the constructed pulsed corona system, NO oxidation efficiency was investigated and compared with results presented in literature. It was shown that pulsed corona systems with significantly longer pulse durations are competitive with several times shorter pulse duration systems, which implies that chemical efficiency of secondary streamers is comparable with efficiency of primary streamers.     

Experimental Study of Nanofluid Convective Heat Transfer for Implementation of Dispersion Model Considering Non-Uniform Particle Distribution

Thermal dispersion model has been used here to simulate heat transfer of water–Al₂O₃ nanofluid. A new form for dispersion thermal conductivity has been introduced in which non-uniform concentration distribution is applied on the model. It was observed that the non-uniformity of concentration increases at greater Reynolds numbers and average concentrations. An experimental set-up was made, and an experimental study was conducted to find the empirical coefficient in the dispersion thermal conductivity. The obtained results show that the developed dispersion model is able to properly simulate heat transfer of the nanofluid and provides more accurate results in comparison with a homogenous model.     

非链式脉冲DF化学激光器反应动力学模型

依据非链式脉冲氟化氘(DF)激光器的反应机理, 采用速率方程理论, 综合考虑了基态DF分子、D₂分子、D原子、F原子对激发态DF分子的消激发作用, 建立了非链式脉冲DF激光器反应动力学模型. 运用Runge-Kutta法对该模型进行数值计算, 得到了增益区内各组分粒子数密度随时间的变化关系. 进而运用该模型研究了工作气体配比和输出镜反射率对DF激光器腔内光子数密度、 单脉冲能量、脉冲宽度和输出功率的影响, 得到了最佳气体配比和最佳输出镜反射率参数. 采用放电引发方式对非链式DF激光器进行了实验研究, 实验测得脉冲波形及单脉冲能量与速率方程理论模型计算结果基本一致. 本文的研究结果可为非链式脉冲DF激光器的优化设计提供理论参考. 关键词： 脉冲DF激光器 动力学模型 速率方程 数值计算     

A kinetic study on pyrolysis of iso-propylcyclohexane: Fuel structure effects of alkylcyclohexane isomers on reaction mechanisms

To reveal insights into the fuel decomposition and combustion mechanisms of alkylcycloalkanes, an intermediate-to-high-temperature pyrolysis investigation of iso-propylcyclohexane (i-PCH) was carried out in a flow reactor at low and atmospheric pressures. The quantitative measurements were accomplished with the aid of synchrotron vacuum ultraviolet photoionization mass spectrometry and the mole fraction profiles of over thirty species were evaluated. A new kinetic model for i-PCH was developed, and the model feasibility was validated by the measured data. Model analyses revealed that the CH₃-dissociation reaction is the most sensitive reaction for the destruction of the fuel, and this reaction together with the hydrogen abstractions on active carbon sites takes the dominance of the fuel decomposition. Due to the low bond dissociation energies (BDEs) of the C-C and C-H bonds in the isopropyl group, the primary decomposition temperatures of i-PCH are lower than those of n-propylcyclohexane (n-PCH). Besides, the isopropyl side-chain structure affects many aspects of combustion characteristics of the fuel involving the initial fuel consumption routes and formation of branched species pool, leading to the enhancement of some hexatomic species and inhibition of aromatics production.     

Removal of NOx from NO2∶NO∶N2 mixture by a pulsed and dc streamer corona in a needle-to-plate reactor

The results of laboratory experiments on reduction of NO _x in the oxygen free gas mixture NO₂NON₂ simulating exhaust gas, by means of pulsed and dc streamer corona discharges generated in a needle-to-plate reactor have been presented. The results show that the dc corona discharge is more efficient in De-NO _x process than the pulsed corona discharge. This is in contrast to the results obtained in the wire-to-cylinder reactors where the pulsed corona discharge removes NO _x more efficiently. The results also lead to the conclusion that in the dc streamer corona discharge the short pulses and long interelectrode distances are recommended in order to increase the NO _x conversion rate.Presented at 17^th Symposium Plasma Physics and Technology, Prague, June 13–16, 1995.This work was financially supported by the Polish Academy of Sciences (projects IMP 3.1 and 3.3) and by the Polish Committee for Scientific Research (KBN Grant No. P40103304).     

A novel linear transformation model for the analysis and optimisation of chemical kinetics

In this study, a novel model for the analysis and optimisation of numerical and experimental chemical kinetics is developed. Concentration–time profiles of non-diffusive chemical kinetic processes and flame speed profiles of fuel–oxidiser mixtures can be described by certain characteristic points, so that relations between the coordinates of these points and the input parameters of chemical kinetic models become almost linear. This linear transformation model simplifies the analysis of chemical kinetic models, hence creating a robust global sensitivity analysis and allowing quick optimisation and reduction of these models. Firstly, in this study the model is extensively validated by the optimisation of a syngas combustion model with a large data set of imitated ignition experiments. The optimisation with the linear transformation model is quick and accurate, revealing the potential for decreasing the numerical costs of the optimisation process by at least one order of magnitude compared to established methods. Additionally, the optimisation on this data set demonstrates the capability of predicting reaction rate coefficients more accurately than by currently known confidence intervals. In a first application, methane combustion models are optimised with a small experimental set consisting of OH(A) and CH(A) concentration profiles from shock tube ignition experiments, species profiles from flow reactor experiments and laminar flame speeds. With the optimised models, especially the predictability for the flame speeds of mixtures of hydrogen, carbon monoxide and methane can be increased compared to established models. With the analysis of the optimised models, new information on the low pressure reaction coefficient of the fall-off reaction H+CH₃(+M)?CH₄(+M) is determined. In addition, the optimised combustion model is quickly and efficiently reduced to validate a new rapid reduction scheme for chemical kinetic models.