Starch-Enhanced Synthesis of Oxygenates from Methane and Carbon Dioxide Using Dielectric-Barrier Discharges

In this work, starch has been used to enhance the oxygenate formation directly from methane and carbon dioxide using dielectric-barrier discharges (DBDs). The use of starch inhibits the formation of liquid hydrocarbons and significantly increases the selectivity of oxygenates. Oxygenates produced include primarily formaldehyde, methanol, ethanol, formic acid, and acetic acid. The total selectivity is about 10–40% with conversion of methane and carbon dioxide of about 20%. Lower methane feed concentration favors the production of oxygenates, and higher feed flow rate leads to higher selectivity of oxygenates in the presence of starch.     

电解二氧化锰的掺钛研究

在硫酸锰和氯化锰体系中加入浓度相同的钛(Ⅲ)盐，可制得掺钛量不同的电解二氧化锰(EMD)。BET比表面积测定、X光电子能谱、红外光谱分析、阴极电位扫描和恒电流放电实验表明：掺钛EMD的空腔内表面积变大，钛离子在EMD颗粒表层被大大富集。掺进的TiO₂进入EMD的晶格，钛使得Mn-O键强度下降。含钛量为0.25～0.4%的EMD(化学式为MnO_x)在碱液中放电时，当x>1.80，钛对MnO_x放电无明显的影响；当x>1.75，且放电深度为放电的第一步时，钛使EMD的放电极化变小。     

Light paraffin oxidative conversion in a silent electric discharge

Methane, ethane, and their mixtures with oxygen have been passed through the silent electric discharge at various operating conditions Beside.carbon oxides and water, formaldehyde and methane, and acetaldehyde and ethanol from ethane were the other major products. The effect of temperature, pressure, discharge voltage, contact time, and oxygen concentration have been examined. The rate of oxygen consumption is almost independent of oxygen concentration and depends mainly on the discharge voltage. The selectivities of methanol formation from methane and ethanol/formation from ethane were 20 and 15%, respectively.     

The Role of Dielectric Barrier Discharge Atmosphere and Physics on Polypropylene Surface Treatment

Dielectric barrier discharge (DBD) is the discharge involved in corona treatment, widely used in industry to increase the wettability or the adhesion of polymer films or fibers. Usually DBD's are filamentary discharges but recently a homogeneous glow DBD has been obtained. The aim of this paper is to compare polypropylene surface transformations realized with filamentary and glow DBD in different atmospheres (He, N₂, N₂ + O₂ mixtures) and to determine the relative influence of both the discharge regime and the gas nature, on the polypropylene surface transformations. From wettability and XPS results it is shown that the discharge regime can have a significant effect on the surface transformations, because it changes both the ratio of electrons to gas metastables, and the space distribution of the plasma active species. This last parameter is important at atmospheric pressure because the mean free paths are short (m). These two points explain why in He, polypropylene wettability increase is greater by a glow DBD than by a filamentary DBD. In N₂, no significant effect of the discharge regime is observed because electrons and metastables lead to the same active species throughout the gas bulk. The specificity of a DBD in N₂ atmosphere compared to an atmosphere containing oxygen is that it allows very extensive surface transformations and a greater increase of the polypropylene surface wettability. Indeed, even in low concentration and independently of the discharge regime, when O₂ is present in the plasma gas, it controls the surface chemistry and degradation occurs.     

The instability of the planar structure of carbanion ⊖:CH2-CN

Ab initio SCF calculations using uniform quality extended basis set supplemented with polarization functions predict a slightly pyramidal carbanion centre in :CH₂-CN. This finding is in contrast to the usual finding of planar geometry of carbanion centres generated next to other conjugative groups. Although the predicted barrier to pyramidal inversion is very small (0.1 kcal/mole) it is estimated that correlation energy contributions, neglected in any SCF calculations, may be too small to remove the barrier. The present results confirm earlier experimental findings that counter-ion and solvent effects can have a dominant role in determining the geometry of this unusual ion in actual chemical systems.     

Studies on Gas Purification by a Pulsed Microwave Discharge at 2.46 GHz in Mixtures of N2/NO/O2 at Atmospheric Pressure

Pulsed microwave discharges operated at atmospheric pressure in gas mixtures containing N₂, O₂, and NO are investigated experimentally and theoretically for various gas mixture constituents and operating conditions with respect to the ability of exhaust gas purification. The rotational gas temperature and the vibrational temperature of N₂ are derived from CARS measurements. The composition of the exhaust gas after treatment is monitored using FTIR spectroscopy. The processes of the chemical, electronic, and vibrational kinetics are described by a model that has been developed to calculate the species densities. The results obtained show that in N₂/NO gas mixtures an overall reduction of NO_x takes place. In the case of N₂/O₂/NO gas mixtures, no net reduction of NO_x is achieved for a pulsed microwave power below 3600 W, a pulse length of 50 s, and a typical repetition frequency of 2 kHz.     

Plasma polymerization anda-C:H film ablation in microwave discharges in methane diluted with argon and hydrogen

Neutral hydrocarbons are observed from a microwave discharge in a fast flow of (A) 0.5–6% methane in argon, (B) 0.5–6% methane in hydrogen, and (C) hydrogen over a previously depositeda-C:H film. System (A) produces polyacetylenic and other hydrocarbons through C₈ by predominantly gas-phase reactions and deposits ana-C: H film. Reactions under conditions (B) and (C) produce hydrocarbon radicals and molecules with masses through 300 that in case (B) arise from both gas-phase reactions and film ablation, and in case (C) from film ablation alone. Proposals are made for the mechanisms of gas-phase polymerization, film deposition, and ablation. Hydrocarbon ions observed downstream from these discharges appear to arise from ionization of neutral species with a distribution determined by subsequent ion-molecule reactions and selective diffusion losses.Work supported by NSF Grant CHE-87-21744.     

Gas-phase reactions in plasmas of SF6 with O2 in He

Processes which occur in microwave discharges of dilute mixtures of SF₆ and O₂ in He have been examined using a flow reactor sampled by a mass spectrometer. Two classes of experiments were performed. In the first set of experiments, mixtures containing 6×10¹¹ cm^–3 SF₆, 6×10¹⁶ cm^–3 He, and O₂ in the range (0–3.6)×10¹³ cm^–3 were passed through a 20-W 2450-MHz microwave discharge. The gas mixtures arriving at a sample point downstream from the discharge were examined for SF₆, SF₄, SOF₂, SOF₄, SO₂F₂, SO₂, F, and O. In the second class of experiments, rate coefficients were measured for the reactions of SF₄ with O and O₂ and for the reaction of SF with O. The rate coefficient for the reaction of SF with O was found to be (4.2±1.5)×10^–11 cm^–3 s^–1. SF₄ was found to react so slowly with both oxygen atoms and oxygen molecules that only upper limits could be placed on the rate coefficients for these reactions. These values were 2×10^–14 cm³ s^–1 and 5×10^–15 cm³ s^–1 for reactions with O and O₂ respectively. The observed distribution of products from the discharged mixtures is discussed in terms of the measured rate coefficients.     

Plasma etching of refractory metals (W,Mo, Ta) and silicon in SF6 and SF6-O2. An analysis of the reaction products

The etching rates and reaction products of refractory metals (W, Mo, and Ta) and silicon have been studied in a SF₆-O₂ r.f. plasma at 0.2 torr. The relative concentrations of WF₆ and WOF₄ and the intensities of the WF _n ⁺ (n=3–5), WOF _m ⁺ (m=1–3), MoF _n ⁺ , and MoF _m ⁺ ions have been measured by mass spectroscopy. An analysis of the neutral composition of the plasma during etching of these metals and a comparison with the results obtained for silicon show that at least two species are involved for W and Mo etching: fluorine and oxygen atoms. A reaction scheme is proposed.     

Reforming of CO<Subscript>2</Subscript>-Containing Natural Gas Using an AC Gliding Arc System: Effect of Gas Components in Natural Gas

The objective of the present work was to study the reforming of simulated natural gas via the nonthermal plasma process with the focus on the production of hydrogen and higher hydrocarbons. The reforming of simulated natural gas was conducted in an alternating current (AC) gliding arc reactor under ambient conditions. The feed composition of the simulated natural gas contained a CH₄:C₂H₆:C₃H₈:CO₂ molar ratio of 70:5:5:20. To investigate the effects of all gaseous hydrocarbons and CO₂ present in the natural gas, the plasma reactor was operated with different feed compositions: pure CH₄, CH₄/He, CH₄/C₂H₆/He, CH₄/C₂H₆/C₃H₈/He and CH₄/C₂H₆/C₃H₈/CO₂. The results showed that the addition of gas components to the feed strongly influenced the reaction performance and the plasma stability. In comparisons among all the studied feed systems, both hydrogen and C₂ hydrocarbon yields were found to depend on the feed gas composition in the following order: CH₄/C₂H₆/C₃H₈/CO₂ > CH₄/C₂H₆/C₃H₈/He > CH₄/C₂H₆/He > CH₄/He > CH₄. The maximum yields of hydrogen and C₂ products of approximately 35% and 42%, respectively, were achieved in the CH₄/C₂H₆/C₃H₈/CO₂ feed system. In terms of energy consumption for producing hydrogen, the feed system of the CH₄/C₂H₆/C₃H₈/CO₂ mixture required the lowest input energy, in the range of 3.58 × 10⁻¹⁸–4.14 × 10⁻¹⁸ W s (22.35–25.82 eV) per molecule of produced hydrogen.