Mechanisms for formation of inorganic byproducts in plasma chemicalprocessing of hazardous air pollutants

Plasma chemical behavior of hazardous air pollutants (HAPs) (Cl ₂C=CCl₂, Cl₂C=CHCl, Cl₃C-CH ₃, Cl₂CH-CH₂Cl, CH₃Cl, CH ₃Br and benzene), their molecular probes (CH₄, CH ₃-CH₃, and CH₂=CH₂), and carbon oxides (CO_x) was investigated with a ferroelectric packed-bed plasma reactor to obtain information on the formation of CO _x and N₂O. It has been shown that the oxidation of CO to CO₂ is a slow reaction in plasma, and that CO and CO ₂ mainly result from different precursors. Simultaneous achievement of complete oxidative decomposition of HAPs in plasma and recovery of CO as a chemical feedstock could be favorable. The process of N₂O formation is affected by HAP structures and oxygen concentration. In the decomposition of olefinic HAPs, such as Cl₂ C=CCl₂ and Cl₂C=CHCl, high-power short-residence-time operations are effective in suppressing N₂ O formation. In the cases of CH₃Cl and CH₃Br, low specific energy density operations could be necessary to reduce N₂O concentrations. The yields and selectivities of CO, CO₂ and N₂O change drastically by adding only 2% of oxygen to N₂, and oxygen concentration is not a good factor to control these inorganic oxides     

Effects of Temperature, Voltage Properties, and Initial Gas Composition on the Plasma Reforming of Aliphatic Hydrocarbons With $hbox{CO}_{{bf 2}}$

CO₂ reforming of methane, propane, and neopentane was investigated with a ferroelectric packed-bed and silent discharge plasma reactors in N₂ at temperature from 303 to 433 K. The conversions of the substrate hydrocarbons and CO₂, and the yields of H₂ and CO were expressed as functions of reactor energy density irrespective of voltage waveform. The positive temperature effect on the hydrocarbon conversions and the product yields can be ascribed to the promotion of secondary decomposition of the hydrocarbons induced by radicals formed in situ because reactor power consumption was not affected by reaction temperature at the same frequencies and peak-to-peak voltages. At 303 K, the reactivity of the hydrocarbon decreased in the following order: neopentane > propane > methane. At 433 K, propane and neopentane showed the same reactivities. The molar ratio of H₂ to CO was affected by hydrocarbon structure and the initial concentration ratio of CO₂ to the carbon atom in hydrocarbon, but not by reaction temperature. Better carbon balances were obtained for all the hydrocarbons at 433 K than at 303 K, suggesting higher reaction efficiencies at 433 K. Carbon balance was also affected by initial gas composition, and the carbon atoms in reacted neopentane were quantitatively recovered as CO, CO₂ and lighter hydrocarbons at 10 of [CO₂]/[neopentane].     

The effect of residence time on the CO2 reduction fromcombustion flue gases by an AC ferroelectric packed bed reactor

An experimental investigation was conducted to reduce CO₂ from combustion gases using an AC ferroelectric packed bed reactor. This ferroelectric packed bed reactor consists of two mesh electrodes packed with ferroelectric particles between them. An AC voltage is applied to the reactor to generate partial or spark discharges. The results show the following: the CO₂ gas reduction rate increases with increasing flue gas residence time and primary applied power; the CO₂ gas reduction rate increases with decreasing gas flow rate and dielectric constant of packed ferroelectric particles; and the CO₂ concentration is reduced by up to 18000 ppm, and 108 g of CO₂ are removed by 1 kWh of primary applied energy used in the packed-bed reactor     

Decomposition of benzene using alumina-hybrid and catalyst-hybridplasma reactors

In order to investigate the effects of alumina and metal ions in plasma discharge, plasma reactors packed with a mixture of BaTiO₃ pellets and porous Al₂O₃ pellets (alumina-hybrid reactor), and with a-mixture of BaTiO₃ pellets and metal-supported Al₂O₃ pellets (catalyst-hybrid reactor) were examined for oxidation of dilute benzene in air. It was found that the oxidative decomposition of benzene was enhanced by concentrating benzene on the Al₂O₃ pellets and the catalyst pellets. Furthermore, the selectivities to CO ₂ in the alumina-hybrid reactor and the catalyst-hybrid reactors were higher than those in the plasma reactor packed with BaTiO ₃ pellets alone. In particular, the selectivities to CO₂ in the catalyst-hybrid reactors using Ag, Co, Cu and Ni/Al₂ O₃ were higher than those from the alumina-hybrid reactor. In addition, the presence of the alumina and catalysts suppressed the formation of N₂O     

Proposals for an improvement in transformer diagnosis usingdissolved gas analysis (DGA)

The diagnosis of oil-immersed transformers using the dissolved gas analysis (DGA) technique has been well accepted and widely used. IEC Publication 599 touches on the diagnosis of faults involving paper insulation based on the ratio of CO₂/CO. It states that a fault involving paper insulation is probable when the CO₂/CO ratio is 3 or lower; we would like to propose a figure of 10     

$hbox{CO}_{bf 2}$ Reforming of Aliphatic Hydrocarbons With Silent Discharge Plasma

CO₂ reforming of methane ( CH₄) and propane (C₃H₈) was performed with a silent discharge reactor (SDR). The reactor performance was evaluated in terms of energy efficiencies for the conversion of the substrates and formation of H₂ and CO. The reactivity of C₃H₈ was 2- to 3-fold higher than that of CH₄, and both of CH₄ and C₃H₈ were reformed in the order of 10¹⁶ molecules/J at 298 K. The energy efficiencies for the conversion of these substrates increased with their initial concentrations, but decreased with an increase in reactor energy density. On the other hand, the energy efficiencies for the conversion of CO₂, which were not affected by the hydrocarbon types, were lower than those for the hydrocarbon substrates. A positive temperature effect was observed in the conversion of the hydrocarbon substrates only at low reactor energy densities from 298 to 433 K.     

膜法二氧化碳分离技术研究进展及展望

二氧化碳的排放导致了严重的环境和生态问题,而碳捕集、利用和封存技术(carbon capture,utilization and storage,CCUS)是减缓CO2排放的有效途径.在众多的CCUS方法中,膜分离因其能效高、成本低、投资少、维护运行简单等优点引起了广泛关注.综述了燃烧前捕集、燃烧后捕集和天然气脱碳中的...     

Numerical Investigation for CF4 Decomposition Using RF Low-Pressure Plasma

Among perfluorocompounds, is considered to be one of the most stable and difficult-to-decompose gases. We investigated the decomposition of CF₄ using the inductively coupled plasma (ICP) reactor with radio frequency (RF) power supply, which was used for semiconductor cleaning process as well as decomposition. This technology was confirmed to achieve an extremely high efficiency and more economical system in comparison with the conventional system. The purpose of this paper is to perform numerical simulation of CF₄ decomposition using RF low-pressure plasma. The experimental investigation of CF₄ the decomposition was performed to validate the computed results, and the reaction products such as CO, CO₂, and COF₂ upon the CF₄ decomposition were measured CO₂ using a analyzer and a Fourier transform infrared spectrophotometer. Then, the numerical simulations of the CF₄ decomposition using commercially available code were performed to obtain the gas temperature, electron temperature, electron number density, gas velocity, and chemical species number density distribution to cope with CF₄ the decomposition in the ICP reactor.     

Preliminary pilot plant tests of a corona discharge-electron beamhybrid combustion flue gas cleaning system

Pilot power plant tests of a corona discharge-electron beam hybrid combustion flow gas cleaning system have been conducted. Gas flow rate of the test loop is a heavy oil fired boiler flue gas with 1200 Nm³ /h, and one electron beam generator (500 kV×30 mA) is used with a corona discharge ammonia radical injection system (60 kV×5 mA), SO₂, CO, CO₂, NH₃, NO, NO_x and O₂ gases are monitored. The results show that up to 85% of NO_x and 98% of SO_x in flue gases are removed under a corona discharge-electron beam hybrid operations with significant small amount of leaked ammonias from exhaust flue gases     

Breakdown Characteristics of N2O Gas Mixtures for Quasiuniform Electric Field under Lightning Impulse Voltage

From the viewpoint of mitigating global warming by SF₆ gas, this paper discusses breakdown (BD) characteristics of different electronegative gas mixtures with N₂O gas as SF₆ gas substitutes for quasi-uniform electric field under lightning impulse voltage applications. Experimental results revealed the positive synergism in breakdown strength of binary N₂O / CO₂ and ternary N₂O / CO₂ / O₂ gas mixtures, respectively. Furthermore, N₂ gas as a retardant gas was also mixed with the electronegative gas mixtures in order to reduce the electron energy into the effective levels of electron attachment ability by the electronegative gas mixtures. As the result, ternary N₂O / CO₂ / N₂ and quaternary N₂O / CO₂ / O₂ / N₂ gas mixtures could exhibit the significant synergistic effect in breakdown strength. The optimum mixture rate of quaternary N₂O / CO₂ / O₂ / N₂ gas mixtures was consistent with that estimated by assuming the independent contribution of component gases to the improvement of impulse BD characteristics.     

特高压配套外送电源碳排放水平研究

随着国家清洁低碳、安全高效的现代电力工业体系的构建,远距离、大容量配套新能源电力外送已成为转变能源资源配置的一项重要途径.如何评估此类项目CO2排放水平及节能减排效益,已受到各界关注.以陕北某特高压直流输电工程为例,对其配套外送电源的CO2排放水平进行研究.结果表明:该工程实施火电与新能源打捆外送,不仅扩大送端省份的新...     

富氧燃烧气氛石灰石溶解特性研究

在实验室小型试验台上研究富氧燃烧气氛下湿法脱硫用石灰石溶解特性,研究结果表明：较高的CO₂浓度对石灰石的溶解有促进作用,CO₂体积分数在80%时,石灰石的溶解速率明显增大;在相同的pH值情况下,CO₂浓度越高,石灰石的溶解速率越快。在pH=4.5时,低浓度CO₂气氛比高浓度CO₂气氛下溶解时间增加70 min,CO₂浓度对溶解速率的影响比较明显。     

Comparison of SF6/N2 and SF6/CO2 gas mixtures as alternatives to SF6 gas

The interest in SF₆ gas mixtures has been re-ignited in recent years by the issue of the greenhouse effect of the SF₆ gas, and most research work is now focused on a SF₆/N₂ gas mixture, which is suitable for application in electrical apparatus with slightly non-uniform fields. This paper presents a comparison of SF₆/N₂ and SF₆/CO₂ gas mixtures with a viewpoint of their possible applications to gas-insulated transformers, where both highly non-uniform field problems and partial discharges in gas/film insulation are inevitable. It is shown that in this case the dielectric strength of SF₆/CO₂ is superior to that of SF₆/N ₂ with a minor disadvantage related to the gas decomposition in SF₆/CO₂. However, this may not be a problem for the SF₆/CO₂ gas mixture to be used in gas-insulated transformers, where internal breakdown is not allowed     

Factors and intermediates governing byproduct distribution fordecomposition of butane in nonthermal plasma

Plasma chemical decomposition of butane was investigated with a ferroelectric parked-bed plasma reactor to obtain the information on the fundamental chemical processes occurring in nonthermal plasma. It has been shown that butane decomposition efficiencies are higher in nitrogen rather than in air. This fact suggests that energy transfer from hot electrons to butane is mainly responsible for the initial decomposition of butane. Nitrogen incorporation was observed for acetonitrile only in dry nitrogen and for nitromethane in air. Barium titanate and water have been shown to act as monooxygen transfer agents in nitrogen. Lattice oxygen atoms in barium titanate can be consumed in the formation of N ₂O and CO, depending on reaction conditions. Water is much more reactive than barium titanate as an oxidant in nonthermal plasma, and it can oxygenate butane to butanols, epoxidize 1- and 2-butenes, and oxidize CO to CO₂. Water, which has a dichotomic nature regarding oxygenation/hydrogenation in plasma, can act as a hydrogen source toward alkyl radicals formed in the initial decomposition of butane. In air, triplet oxygen molecules are the most reactive oxygen source in the presence or absence of water and carbon balance can be improved with suppression of byproducts due to promoted autoxidation processes     

Catalysis-assisted plasma technology for carbon tetrachloridedestruction

Single-stage, catalysis-assisted plasma technology is a new concept developed to decompose carbon tetrachloride (CCl₄), one of the greenhouse gases, and to reduce the reaction by-products at the same time. A laboratory-scale plasma reactor used a packed-bed reactor with 1-mm spherical BaTiO₃ pellets. The configuration employed a unique one-stage catalysis/plasma process in which the BaTiO ₃ pellets were coated or impregnated by active catalysts such as Co, Cu, Cr, Ni, and V. The power supply used for these experiments was either a 50-Hz neon transformer or an 18-kHz inverter neon transformer. Enhancement of the CCl₄ destruction and the conversion of by-product CO to CO₂ were demonstrated using Ni catalyst in the one-stage plasma reactor     

Reduction of CO2 from combustion gases by DC coronatorches

An experimental investigation has been conducted to reduce CO₂ from combustion gases by using DC corona torches. This plasma device, the corona torch, consists of two small-diameter hollow electrodes. The gas flow enters the upstream cylindrical hollow electrode and exits at a downstream cylindrical hollow electrode. Therefore, all the reactive gas passes through the active corona-induced plasma zone. High-speed gas flow near the exit of the electrode cools the electrodes; hence, the chemical reactions and the stability of discharge are enhanced. Various amounts of argon gas were added to the model combustion gas (N₂:O₂:CO₂=0.745:0.15:0.105). The results show that the CO₂ gas reduction rate increases with increasing corona current when the model gas is seeded with argon. The CO₂ gas reduction rate increases when the percentage of argon gas in the mixture increases up to 20%, and decreases when the percentage of argon gas in the mixture increases above 20%     

CO2活化氮掺杂炭气凝胶的制备及其性能研究

以间苯二酚、甲醛、氧化石墨烯和三聚氰胺为原料,通过溶胶-凝胶法制备氮掺杂炭气凝胶,再对其进行CO₂活化。用X射线衍射光谱法（XRD）、扫描电子显微镜法（SEM）、X射线光电子光谱法（XPS）和N₂吸附等进行物理性能分析,用交流阻抗谱、恒流充放电测试等进行电化学性能测试。随着活化温度的提高,材料表面形成了密集的具有大量孔的内部相互交联的网络结构。当活化温度为900℃时,所制备的样品比表面积最高,由NCAG-4的1 194 m²/g增大到CO₂-900-NCAG-4的1 849 m²/g。在经过活化以后,CO₂-900-NCAG-4表现出了最佳的电化学性能,将其组装成超级电容器,充放电循环2 000次后电容保持率达94.31%。     

CO2体积分数对燃煤细颗粒物在水汽环境中凝结长大的影响

为研究燃煤烟气中CO₂体积分数对细颗粒物在水汽环境中凝结长大效果的影响,建立了计算模型并搭建了实验平台,分别从理论计算和实验研究两方面探讨了CO₂体积分数对细颗粒物凝结长大效果的影响。结果表明:随着CO₂体积分数升高,混合烟气的热、质扩散系数均降低,生长管内平均过饱和度增加,细颗粒物长大效果明显;管壁温度越高,随着CO₂体积分数的提高,细颗粒物粒径越大。     

Interruption capability of CF/sub 3/I Gas as a substitution candidate for SF/sub 6/ gas

We studied the interruption performance of CF₃I gas because its environmental effect is smaller than that of SF₆ gas with a model arc-extinguishing chamber. First, we measured the arc time constant and arc power loss coefficient using Mayr's equation. Comparing CF₃I with other gases, the arc time constants are SF₆3I2< H₂2. The arc power loss coefficient is H₂>SF₆ >CO₂>Air>N₂ >CF₃I. Next, we evaluated the short line fault (SLF) interruption capability by measuring the di/dt-dv/dt characteristic. Consequently, the SLF interruption performance of pure CF₃I was about 0.9 times that of SF₆. However, CF₃I application to gas insulated switchgear (GIS) and gas circuit breakers (GCB) is difficult because the liquefying temperature of the gas is high. Therefore, we adopted a countermeasure to obtain a lower liquefying temperature mixing CF₃I with CO₂. The result showed that the SLF interruption performance of the mixture approximated that of pure CF₃I when the ratio of CF₃ I exceeds 20%     

微富氧燃烧技术下氨法脱碳试验研究

针对微富氧燃烧下烟气组分（CO₂体积分数约30%~40% ）,利用填料塔进行了氨法脱碳试验研究,考察了烟气CO₂浓度、氨水浓度、吸收液pH值、氨水流量、烟气温度、烟气流量等因素对CO₂脱除率的影响。试验结果表明：① 随氨水浓度、吸收液pH值、氨水流量增加以及填料增多,CO₂脱除率升高,但在pH值=10.5时出现一定波动;② 烟气温度为50 ℃时,CO₂脱除率最高;③ 当氨水中NH₃质量分数大于4%时,烟气中CO₂脱除率达90%以上,微富氧燃烧条件下,单位质量氨（1 kg NH₃）对烟气中CO₂吸收质量为0.32 kg,脱碳效率是常规燃烧条件下的2倍多,因此采用微富氧燃烧有利于缩小吸收塔和再生塔的体积、降低能耗。