Analysis of the critical active species for methylene blue decoloration in a dielectric barrier discharge plasma system

In the paper, a hybrid gas–liquid dielectric barrier discharge (DBD) plasma system was set up to treat a methylene blue (MB) solution. The effects of the change of the carrier gas, the gas bubbling rate and different kinds of scavenger addition, including sodium carbonate (Na₂CO₃), para benzoquinone (p-BQ), triethylenediamine and sodium dihydrogen phosphate (NaH₂PO₄), on the MB decoloration were reviewed to clarify the critical active species for the dye decoloration in the DBD plasma system. The obtained results show that higher decoloration of the MB solution could be achieved when O₂ was used as the carrier gas, which could be 100% after 20 min discharge treatment, and the result confirmed the crucial effect of O₃ in the MB decoloration. Based on the experiments of the scavenger addition, it could be concluded that O₂⁻ and ¹O₂ were two other important reactive oxygen species (ROS) for the MB decoloration. The results of the higher chemical oxygen demand removal and faster disappearance of the characteristic peak of the MB from the UV–vis analysis under O₂ bubbling conditions also proved the critical effect of the ROS formed by O₂ on the MB decoloration.     

Enhancing toluene removal in a plasma photocatalytic system through a black TiO_2 photocatalyst

An efficient toluene removal in air using a plasma photocatalytic system(PPS) not only needs favorable surface reactions over photocatalysts under the action of plasma,but also requires the photocatalysts to efficiently absorb light emitted from the discharge for driving the photocatalytic reactions. We report here that the PPS constructed by integrating a black titania(B-TiO_2)photocatalyst with a dielectric barrier discharge(DBD) can effectively remove toluene with above 70% CO_2 selectivity and remarkably reduced the concentration of secondary pollutants of ozone and nitrogen oxides at a specific energy input of 1500 J·l~(-1),while exhibiting good stability. Photocatalyst characterizations suggest that the B-TiO_2 provides a high concentration of oxygen vacancies for the surface oxidation of toluene in DBD,and efficiently absorbs ultraviolet–visible light emitted from the discharge to induce plasma photocatalytic oxidation of toluene. The presence of B-TiO_2 in the plasma region also results in a high discharge efficiency,facilitating the generation of large numbers of reactive species and thus the oxidation of toluene towards CO_2. The greatly enhanced performance of the PPS integrated with B-TiO_2 in toluene removal offers a promising approach to efficiently remove refractory volatile organic compounds from air at low temperatures.     

Plasma-catalytic degradation of tetracycline hydrochloride over Mn/γ-Al2O3 catalysts in a dielectric barrier discharge reactor

A coaxial dielectric barrier discharge (DBD) reactor was used for plasma-catalytic degradation of tetracycline hydrochloride over a series ofMn/γ-Al₂O₃ catalysts prepared by the incipient wetness impregnation method. The combination of plasma and theMn/γ-Al₂O₃ catalysts significantly enhanced the degradation efficiency of tetracycline hydrochloride compared to the plasma process alone, with the 10%Mn/γ-Al₂O₃ catalyst exhibiting the best tetracycline hydrochloride degradation efficiency. A maximum degradation efficiency of 99.3% can be achieved after 5 min oxidation and a discharge power of 1.3 W, with only 69.7% by a single plasma process. The highest energy yield of the plasma-catalytic process is 91.7 gkWh⁻¹. Probable reaction mechanisms of the plasma-catalytic removal of tetracycline hydrochloride were also proposed.     

Enhanced removal of ultrafine particles from kerosene combustion using a dielectric barrier discharge reactor packed with porous alumina balls

Ultrafine particles(UFPs) are harmful to human beings, and their effective removal from the environment is an urgent necessity. In this study, a dielectric barrier discharge(DBD) reactor packed with porous alumina(PA) balls driven by a pulse power supply was developed to remove the UFPs(ranging from 20 to 100 nm) from the exhaust gases of kerosene combustion. Five types of DBD reactors were established to evaluate the effect of plasma catalysis on the removal efficiency of UFPs. The influences of gas flow rate, peak voltage and pulse frequency of different reactors on UFPs removal were investigated. It was found that a high total UFP removal of91.4% can be achieved in the DBD reactor entirely packed with PA balls. The results can be attributed to the enhanced charge effect of the UFPs with PA balls in the discharge space. The UFP removals by diffusion deposition and electrostatic attraction were further calculated,indicating that particle charging is vital to achieve high removal efficiency for UFPs.     

模拟乏燃料的氧化挥发首端工艺研究

通过实验室制备的UO₂模拟芯块,分别研究了氧化与还原气氛下,温度、气体组成和保温时间对粉化与转化过程的影响,结果显示,氧化条件为空气/450℃/4 h、还原条件为4%(体积分数)H₂-Ar/700℃/4 h的三次氧化还原循环流程,对UO₂模拟芯块和真实天然铀芯块均有良好的粉化效果。针对制成的包含有多种裂变元素的模拟乏燃料,在经过三次氧化还原循环流程处理的基础上,进一步结合1 200℃/4 h的更高温挥发技术,形成国内首个模拟后处理氧化挥发首端工艺。该工艺能够使Mo、Te、Se和Ru等半挥发性裂变元素以氧化物的形态被有效去除,去除率均达到85%以上。     

Effects of O2 addition on the plasma uniformity and reactivity of Ar DBD excited by ns pulsed and AC power supplies

Dielectric barrier discharges (DBDs) have been widely used in ozone synthesis, materials surface treatment, and plasma medicine for their advantages of uniform discharge and high plasma-chemical reactivity. To improve the reactivity of DBDs, in this work, the O₂ is added into Ar nanosecond (ns) pulsed and AC DBDs. The uniformity and discharge characteristics of Ar ns pulsed and AC DBDs with different O₂ contents are investigated with optical and electrical diagnosis methods. The DBD uniformity is quantitatively analyzed by gray value standard deviation method. The electrical parameters are extracted from voltage and current waveforms separation to characterize the discharge processes and calculate electron density n_e. The optical emission spectroscopy is measured to show the plasma reactivity and calculate the trend of electron temperature T_e with the ratio of two emission lines. It is found that the ns pulsed DBD has a much better uniformity than AC DBD for the fast rising and falling time. With the addition of O₂, the uniformity of ns pulsed DBD gets worse for the space electric field distortion by O₂⁻, which promotes the filamentary formation. While, in AC DBD, the added O₂ can reduce the intensity of filaments, which enhances the discharge uniformity. The ns pulsed DBD has a much higher instantaneous power and energy efficiency than AC DBD. The ratio of Ar emission intensities indicates that the T_e drops quickly with the addition of O₂ both ns pulsed and AC DBDs and the ns pulsed DBD has an obvious higher T_e and n_e than AC DBD. The results are helpful for the realization of the reactive and uniform low temperature plasma sources.     

Plasma propagation in single-particle packed dielectric barrier discharges: joint effects of particle shape and discharge gap

In this work, a single Al₂O₃ particle packed dielectric barrier discharge (DBD) reactor with adjustable discharge gap is built, and the influences of the particle shape (ball and column) and the residual gap between the top electrode and particle on the electrical and optical characteristics of plasma are studied. Our research confirms that streamer discharge and surface discharge are the two main discharge patterns in the single-particle packed DBD reactor. The strong electric field distortion at the top of the ball or column caused by the dielectric polarization effect is an important reason for the formation of streamer discharge. The length of streamer discharge is proportional to the size of the residual gap, but the number of discharge times of a single voltage cycle shows an opposite trend. Compared to the column, a smooth spherical surface is more conducive to the formation of large and uniform surface discharges. The surface discharge area and the discharge intensity reach a maximum when the gap is equal to the diameter of the ball. All in all, the results of this study will provide important theoretical support for the establishment of the synergistic characteristics of discharge and catalysis in plasma catalysis.     

Enhanced removal of benzene in nonthermal plasma with ozonation,flow recycling,and flow recirculation

A double stage AC/DC sequential high voltage reactor has been developed to study the decomposition of benzene in the air stream at atmospheric pressure. The removal efficiency was measured as a function of ozonation, flow recycling, and flow recirculation. Ozonation in the inlet, and recycling of the exhaust stream increased the removal of benzene, also with increasing of specific input energy (J l⁻¹) the effect of inlet flow ozonation on benzene decomposition was enhanced. The highest removal efficiency was obtained up to >99% in recirculation six times, while CO₂ selectivity reached 99.9% and energy efficiency was 0.59 g kWh⁻¹. O₃ production/ decomposition > production of OH radicals > electronic and ionic collisions were indicated as the main mechanisms influencing benzene abatement in this research.     

DBD coupled with MnOx/γ-Al2O3 catalysts for the degradation of chlorobenzene

This paper investigates the degradation of chlorobenzene by dielectric barrier discharge(DBD)coupled with MnOx/γ-Al2O3 catalysts.MnOx/γ-Al2O3 catalysts were prepared using the impregnation method and were characterized in detail by N2 adsorption/desorption,x-ray diffraction and x-ray photoelectron spectroscopy.Compared with the single DBD reactor,the coupled reactor has a better performance on the removal rate of chlorobenzene,the selectivity of COx,and the inhibition of ozone production,especially at low discharge voltages.The degradation rate of chlorobenzene and selectivity of COx can reach 96.3%and 53.0%,respectively,at the specific energy density of 1350 J l-1.Moreover,the ozone concentration produced by the discharge is significantly reduced because the MnOx/Al2O3 catalysts contribute to the decomposition of ozone to form oxygen atoms for the oxidation of chlorobenzene.In addition,based on analysis of the byproducts,the decomposition mechanism of chlorobenzene in the coupled reactor is also discussed.     

Inactivation of Staphylococcus aureus by the synergistic action of charged and reactive plasma particles

In this paper, a low-pressure capacitively coupled plasma discharge sustained in an argonoxygen mixture was studied in order to evaluate its properties in terms of inactivation of Staphylococcus aureus. The plasma parameters as electron temperature and plasma density were measured by the Langmuir probe (N_e ≈ 10¹⁵ m⁻³, T_e ≈ 1.5 eV), while the neutral atom density was in the range of 10²¹ m⁻³. In the plasma phase, oxygen radicals were taken as reference of the reactive species with antimicrobial activity, and oxygen spectral lines, over a range of plasma process parameters, were investigated by the optical emission spectroscopy. Optimal plasma conditions were found, and a count reduction of 4 log in a few minutes of the bacterium proves the potentiality of an industrial grade plasma reactor as a sterilization agent.     

Naphthalene oxidation by different non-thermal electrical discharges at atmospheric pressure

Gaseous naphthalene has been removed by air plasma generated by pulsed corona discharges at 100°C (LSPM) and dielectric barrier discharges (DBD) up to 250 °C (LPGP) in different reactors geometries. Naphthalene has been chosen as one of unburned hydrocarbon present in exhaust gas engine during the cold start of vehicles. The comparison between the different discharge geometries has been possible using the specific input energy (SIE) as relevant parameter for pollutant removal process control considering the differences in the electrical characteristics and the differences of gas flow. The best naphthalene degradation is obtained in the wire-to cylinder (WTC) corona discharge and the stem-to-cylinder DBD with an energy cost β respectively of 10 and 20 J L ^-1. The main by-products issues of the naphthalene oxidation are CO₂ and CO reaching 45% in Multi-Pin-to-Plan corona discharge. We detected polyaromatic hydrocarbons in the gas phase (few ppm) and in the solid phase deposited in the reactors. The introduction of water in the discharges promotes the naphthalene degradation by OH-atom, which has better oxidising power than O-atom in dry air.     

热压烧结UN陶瓷芯块的性能

UN燃料具有铀密度高、熔点高、热导率高、热膨胀系数低、辐照稳定性好等优点,是未来空间核电源、核火箭、快堆和ADS的重要候选燃料。本文采用金属铀粉与氮气在300～400℃直接发生化合反应,制得单相U₂N₃粉末。粒度为38.3 μm的U₂N₃粉末在1 600 ℃真空热压烧结,制得相对密度为93.5%、存在少量金属铀相的UN陶瓷;而18.1 μm的U₂N₃粉末在1 550 ℃真空热压烧结,制得相对密度为96.1%、不残留金属铀相的UN陶瓷,U与N的总质量分数为99.57%,每个金属杂质含量均低于50 μg/g,氧含量为1 048 μg/g,碳含量为502 μg/g。U₂N₃在1 027 ℃以上将会完全分解成UN,UN在1 627 ℃以上也会发生分解。     

A method of removing helium ash and impurities from fusion reactors

By injecting streams of small pellets through the edge of a reactor plasma, helium ash and other impurities can be captured and removed from the reactor. Calculations show that sufficient pumping capacity is available to remove 10²¹ He/s and that the equilibrium density of pellet material in the plasma is probably tolerable. If successful, this method of ash removal and impurity control simplifies reactor design considerably.     

Evaluation on a double-chamber gas-liquid phase discharge reactor for benzene degradation

A double-chamber gas-liquid phase DBD reactor (GLDR), consisting of a gas-phase discharge chamber and a gas-liquid discharge chamber in series, was designed to enhance the degradation of benzene and the emission of NOx. The performance of the GLDR on discharge characteristics, reactive species production and benzene degradation was compared to that of the single-chamber gas phase DBD reactor (GPDR). The effects of discharge gap, applied voltage, initial benzene concentration, gas flow rate and solution conductivity on the degradation and energy yield of benzene in the GLDR were investigated. The GLDR presents a higher discharge power, higher benzene degradation and higher energy yield than that of the GPDR. NO₂ emission was remarkably inhibited in the GLDR, possibly due to the dissolution of NO₂ in water. The benzene degradation efficiency increased with the applied voltage, but decreased with the initial concentration, gas flow rate, and gas discharge gap, while the solution conductivity presented less influence on benzene degradation. The benzene degradation efficiency and the energy yield reached 61.11% and 1.45 g kWh^–1 at 4 mm total gas discharge gap, 15 kV applied voltage, 200 ppm benzene concentration, 0.2 L min⁻¹ gas flow rate and 721 μS cm⁻¹ water conductivity. The intermediates and byproducts during benzene degradation were detected by FT-IR, GC-MS and LC-MS primarily, and phenols, CO_x, and other aromatic substitutes, O₃, NO_x, etc, were determined as the main intermediates. According to these detected byproducts, a possible benzene degradation mechanism was proposed.     

Development of low power non-thermal plasma jet and optimization of operational parameters for treating dyes and emerging contaminants

Non-thermal plasma has emerged as an effective treatment system against the latest class of highly recalcitrant and toxic environmental pollutants termed emerging contaminants (ECs). In the present work, a detailed experimental study is carried out to evaluate the efficacy of a non-thermal plasma jet with two dyes, Rd. B and Met. Blue, as model contaminants. The plasma jet provided a complete dye decoloration in 30 min with an applied voltage of 6.5 kV_p−p. ·OH, having the highest oxidation potential, acts as the main reactive species, which with direct action on contaminants also acts indirectly by getting converted into H2O2 and O3. Further, the effect of critical operational parameters viz, sample pH, applied voltage (4.5‒6.5 kV_p−p), conductivity (5‒20 mS cm⁻¹), and sample distance on plasma treatment efficacy was also examined. Out of all the assessed parameters, the applied voltage and sample conductivity was found to be the most significant operating parameters. A high voltage and low conductivity favored the dye decoloration, while the pH effect was not that significant. To understand the influence of plasma discharge gas on treatment efficacy, all the experiments are conducted with argon and helium gases under the fixed geometrical configuration. Both the gases provided a similar dye decoloration efficiency. The DBD plasma system with complete dye removal also rendered maximum mineralization of 73% for Rd. B, and 60% for Met. Blue. Finally, the system's efficiency against the actual ECs (four pharmaceutical compounds, viz, metformin, atenolol, acetaminophen, and ranitidine) and microbial contaminant (E. coli) was also tested. The system showed effectivity in the complete removal of targeted pharmaceuticals and a log2.5 E. coli reduction. The present systematic characterization of dye degradation could be of interest to large communities working towards commercializing plasma treatment systems.     

Activated persulfate by DBD plasma and activated carbon for the degradation of acid orange Ⅱ

In this study, the effect of activated peroxydisulfate(PDS) by dielectric barrier discharge(DBD) plasma and activated carbon(HGAC) on the removal of acid orange Ⅱ(AOⅡ) was investigated. The effects of applied voltage, PDS dosage, HGAC dosage, initial pH value, and inorganic anions on the removal rate of AOⅡ were discussed. The main free radicals degrading azo dyes during the experiment were also studied. Experimental results show that the removal rate of AOⅡ in DBD/HGAC/PDS synergistic system is much higher than that in the single system. With the applied voltage of 16 kV, HGAC dosage of 1 g l-1, PDS and AOⅡ molar ratio of 200:1, initial pH value of 5.4 and concentration of AOⅡ solution of 20 mg l-1, the removal rate of AOⅡ reached 97.6% in DBD/HGAC/PDS process after 28 min of reaction.Acidic and neutral conditions are beneficial for AOⅡ removal. Sulfate and hydroxyl radicals play an important role in the removal of AOⅡ. Inorganic anions are not conducive to the removal of AOⅡ.     

Numerical modelling of a low power non-transferred arc plasma reactor for methane conversion

Thermal flow characteristics and the methane conversion reaction in a low power arc plasma reactor for efficient storage and transport of methane, which is the main component of shale gas, were simulated. The temperature and velocity distributions were calculated according to the type of discharge gases and arc current level by a self-developed magnetohydrodynamics (MHD) code and a commercial ANSYS-FLUENT code; the transport of chemical species was analyzed as including the chemical reactions of methane conversion. The simulated results were verified by the comparison of calculated and measured arc voltages with permissible low error as under 4%. Three C₂ hydrocarbon gases with ethane (C₂H₆), ethylene (C₂H₄), and acetylene (C₂H₂) were selected as the converted species of methane from experimental data. The mass fraction of C₂ hydrocarbons and hydrogen as the product of the conversion reaction at the reactor was also calculated. Those values show good agreement with the actual experimental results in that the major conversion reaction occurred in C₂H₂ and hydrogen, and the conversions to C₂H₆, C₂H₄, and hydrogen were minor reactions of methane pyrolysis conversion.     

Design of a MT-DBD reactor for H_2S control

This study aimed to discuss the removal of hydrogen sulfide(H_2S)with non-thermal plasma produced by a multilayer tubular dielectric barrier discharge reactor,which is useful in the field of plasma environmental applications.We explored the influence of various factors upon H_2S removal efficiency(η_(H_2S))and energy yield(Ey),such as specific energy density(SED),initial concentration,gas flow velocity and the reactor configuration.The study showed that we can achieveη_(H_2S)of 91%and the best Ey of 3100 mg kWh~(-1)when we set the SED,gas flow velocity,initial H_2S concentration and layers of quartz tubes at 33.2 J 1~(-1),8.0 m s~(-1),30 mg m~(-3)and five layers,correspondingly.The average rate constant for the decomposition of hydrogen sulfide was 0.206 gm~(-3)s~(-1).In addition,we also presented the optimized working conditions,byproduct analysis and decomposition mechanism.     

改装元素分析—稳定同位素比值质谱联用仪测定固体样品硫同位素

本文对元素分析—稳定同位素比值质谱联用仪(EA-IRM S)进行改装,并利用其测定不同形态硫同位素标准物质和样品.结果表明,在色谱柱后加装SO2气体捕集管,可捕集氧化还原产生的SO2气体,并重复调用作为参考气使用,无需外部引入高纯SO2气体,减小了其对仪器管路腐蚀和实验室环境危害;硫酸钡进样量约400μg时,捕集管中的...     

Numerical analysis of thermal plasma scrubber for CF4 decomposition

CF₄ gas emitted in the semiconductor and display manufacturing process is a very harmful greenhouse gas. It must be removed or converted safely due to its extreme toxicity. Although a CF₄ decomposition system using a thermal plasma scrubber was commercialized, its removal efficiency is limited. In this work, a numerical analysis of CF₄ decomposition in the thermal plasma scrubber was carried out in order to propose an efficient decomposition environment. The decomposition and recombination temperatures of CF₄ were analyzed using thermodynamic equilibrium calculations. The chemical reaction of CF₄ decomposition into carbon and fluorine gas was considered in this numerical analysis. The injection position and angle of the CF₄ were controlled in order to enhance the decomposition rate. The vertical injection of CF₄ near the torch exit improved the mixing of the CF₄ with the thermal plasma flame. In addition, it was confirmed that the high temperature region expanded due to a vortex generated by strong turbulence in the bottleneck-shaped reactor. As a result, it is revealed that the CF₄ injection location and the reactor configuration are the most important factors in improving the decomposition rate.