Solid-Phase Synthesis of Calcium Carbide in a Plasma Reactor

A laboratory-scale spout-fluid bed reactor with a dc plasma torch was used to study the solid-phase synthesis of calcium carbide. Calcium oxide powder with a mean particle size of 170 m was reacted with graphite powder (130 m). Argon was used to initiate the plasma and hydrogen gas was then added to increase power and raise the plasma jet enthalpy. Experimental results showed that the reaction took place in the vicinity of the plasma jet and that conversion to calcium carbide increased linearly with reaction time. The rate of conversion increased exponentially with plasma jet temperature, indicating that chemical reaction was the controlling mechanism. Microscopic analysis of the solid product showed that calcium carbide was formed around both reactants, and that the reaction followed a shrinking core model. Although melting and agglomeration of partially reacted particles occurred at high temperature, resulting in instability of the bed and impeding the reaction progress, high conversions are expected in a continuous process with optimized reactor design.     

Tungsten Carbide and Vanadium Carbide Nanopowders Synthesis in DC Plasma Reactor

Air–methane and nitrogen–hydrogen DC thermal plasma confined flows were used to synthesize tungsten carbide and vanadium carbide nanopowders. The influence of input process parameters such as C/W and C/V molar ratio, plasma jet chemical composition, plasma jet enthalpy, and reactants flow rates on the average nanoparticle size, chemical and crystallographic phase compositions were investigated. During post heat treatment, the synthesized MeC_1?x nanopowders were fully carburized to monocarbides WC and VC with particles size less than 80 and 40 nm correspondently.     

Nano-Particle Sizing in a Thermal Plasma Synthesis Reactor

The radio frequency inductively coupled thermal plasma synthesis process, based on the use of solution precursors as the process feedstock, has been employed for the production of ceria (CeO₂) nano-powders. A sampling probe has been developed to continuously withdraw synthesized nano-powders from all desired positions within the plasma chamber for subsequent analysis. Using this probe, it was possible to study the 3D mapping of the plasma synthesis process. A flow of helium was introduced into the sampling probe to quench sampled particles and to prevent further particle growth within the sampling probe. Numerical simulations of the plasma flow were performed to study the influence of the probe tip geometry on the plasma flow. The reactor wall product collection method was also applied for sampling probe performance verification. The effects of selected plasma power and reactor pressure on the synthesized nano-powders size were investigated with this sampling probe. The results indicated that size distribution of the synthesized nano-powders is locally monomodal, with particles sizes as small as 4 nm being synthesized.     

钛铁矿中钛的测定

利用钛铁矿能显著吸收微波的介电特性,采用家用微波炉,在微波辐照下,用浓磷酸消解矿样,并用氧化还原滴定法测定钛的含量,试验结果表明,该方法能快速分解矿样,测定结果准确,与传统分析方法比较,该法具有简便、快速、低耗、适应大批量样品分析等优点。还对钛铁矿的结构作了X-射线衍射分析。     

Optical Emission Spectroscopic Study of the Synthesis of Titanium Boride Nanoparticles in RF Thermal Plasma Reactor

Thermal plasma processes have been investigated by optical emission spectroscopy during the synthesis of TiB_x nanoparticles from TiO₂, B and C precursors using argon and helium both as plasma and sheath gases. Line-rich emission spectra were observed both in Ar–He–TiO₂–B and Ar–He–TiO₂–B–C cases. Emissions detected in the spectral region of 300–1000 nm were attributed to the electronic relaxation of excited Ti(I) and ionic fragments Ti(II), as well as the molecular species of TiO. The plasma temperature was calculated from the vibration–rotation temperature of the A–X electronic transition of TiO molecule by the least-squares fitting of experimental data to theoretical spectra. The temperatures at 100 mm downstream the torch outlet were found to be between 3800 and 2700 K for the Ar–He–TiO₂–B system, and between 5100 and 4300 K for the Ar–He–TiO₂–B–C system, respectively. The morphology of as-formed nanoparticles was characterized by transmission electron microscopy. Measurements of specific surface area, evaluated on the basis of Brunauer, Emmett and Teller equation, revealed that in all experimental setups titanium boride nanoparticles were formed with a mean particle size of 17–85 nm. On the basis of X-ray diffraction patterns, the solid reaction products were composed of TiB₂, boron doped titanium indicated as Ti(B), Ti₂O₃, H₃BO₃ and TiC. The actual composition of products depended on the synthesis conditions.     

Numerical Modelling of Wood Gasification in Thermal Plasma Reactor

Biomass gasification for synthesis gas production represents a promising source of energy based on plasma treatment of renewable fuel resources. Gasification/pyrolysis of crushed wood as a model substance of biomass has been experimentally carried out in the plasma-chemical reactor equipped with gas–water stabilized torch which offer advantage of low plasma mass-flow, high enthalpy and temperature making it possible to attain an optimal conversion ratio with respect to synthesis gas production in comparison with other types of plasma torches. To investigate this process of gasification in detail with possible impact on performance, a numerical model has been created using ANSYS FLUENT program package. The aim of the work presented is to create a parametric study of biomass gasification based on various diameters of wooden particles. Results for molar fractions of CO for three different particles diameters obtained by the modeling (0.55, 0.52 and 0.48) at the exit are relatively good approximation to the corresponding experimental value (0.60). The numerical results reveal that the efficiency of gasification and syngas production slightly decreases with increasing diameter of the particles. Computed temperature inhomogeneities in the volume of the reactor are strongest for the largest particle diameter and decrease with decreasing size of the particles.     

Diamond Deposition on Substrates with Different Geometries in a Thermal Plasma Reactor

The effects of process parameters on diamond film deposition have been considered in an atmospheric-pressure dc thermal plasma jet reactor. Two different precursor injection systems have been evaluated, counterflow and side injection. The precursor flow rate using ethanol has been found to strongly affect crystal size as well as orientation of crystal growth planes. Further, crystal size on sharp edges has been found to be up to five times larger than on planar surfaces. The effects of substrate geometry on the morphology and area of deposited diamond have been investigated as well. The results of this study show that dc thermal plasma jets can provide high diamond deposition rates, for example on wires and drills, although crystal size and film thickness show substantial variation.     

Reduction of Metallurgical Wastes in an RF Thermal Plasma Reactor

Recovery of metals from iron and zinc oxides, as well as from zinc-containing metallurgical wastes, such as flue dust from the Siemens–Martin process and sludge from hot galvanizing, has been studied in an rf thermal plasma reactor under reducing conditions. The product composition was estimated by thermodynamic calculations based on the minimization of the Gibbs free enthalpy. Effects of the plate power of rf generator and the feed rate of powder on the chemical and phase composition of products have been investigated in detail. It has been proved that the rf thermal plasma treatment makes possible to produce unstable species in thermodynamic terms: metallic zinc was gained in the reaction of ZnO and hydrogen. The gradient cooling along the plasma reactor led to the segregation of the iron and zinc compounds. Valuable products were made from the particular wastes by a single step thermal plasma processing.     

Synthesis of Nanosized Silicon Carbide Through Non-Transferred Arc Thermal Plasma

A thermal plasma system was used for the preparation of nanosized SiC powder. First SiC was synthesized by solid-state reaction using waste silicon and activated carbon powders and then plasma processing was carried out to form nanosized SiC. Phase and structural analysis was carried out by X-ray diffraction which confirmed the formation of SiC in both cases. Plasma treatment did not show any kind of change in structure and phase of SiC; except little free silicon. Morphological investigation showed the formation of 20–30 nm spherical SiC particles after plasma treatment which was initially 1–5 μm. It was found that DC current played an important role in the reduction of particle size. It was proposed that nanosized SiC was formed due to the dissociation of grains from their grain boundary due to strong plasma gas stream.     

Effects of Precursors and Plasma Parameters on Fullerene Synthesis in RF Thermal Plasma Reactor

Synthesis of fullerenes from graphite powders of different grade was studied in a radiofrequency (RF) plasma reactor. Dependence of fullerene yield on the properties and feed rate of precursors and on the helium content of plasma gas was studied in details. The fullerene yield was influenced by the mean size and the thermal conductivity of graphite particles on the one hand, and the helium content of the gas phase on the other. Soot containing fullerene mixture of 5.9% was produced in best conditions found in this work. The main component of the fullerene mixture was C₆₀. In addition, it contained about 30% of C₇₀ (corresponding to a C₆₀/C₇₀ mass ratio of 2.64). Higher fullerenes such as C₈₄ were also detected by mass spectroscopy (MS) and high performance liquid chromatography (HPLC).     

Analytical Model of a Plasma Reactor

This paper presents a simple analytical model to estimate the effect of theboundary layer on the performance of a dc plasma reactor. A graphite linerwas inserted inside the reactor to raise the wall temperature. The model wasused to predict the Destruction and Removal Efficiency (DRE) of the reactorwith and without the graphite liner. The DRE of the device was measured forboth conditions and was found to be in close agreement with the predictedvalues. The model has shown that the DRE is a strong function of the walltemperature of the flight tube and is insensitive to the change in thetube's diameter.     

Formation of NO from N2/O2 Mixtures in a Flow Reactor: Toward an Accurate Prediction of Thermal NO

We have conducted flow reactor experiments for NO formation from N₂/O₂ mixtures at high temperatures and atmospheric pressure, controlling accurately temperature and reaction time. Under these conditions, atomic oxygen equilibrates rapidly with O₂. The experimental results were interpreted by a detailed chemical model to determine the rate constant for the reaction N₂ + O ? NO + N (R1). We obtain k₁ = 1.4 × 10¹⁴ exp(?38,300/T) cm³ mol^?1 s^?1 at 1700–1800 K, with an error limit of ±30%. This value is 25% below the recommendation of Baulch et al. for k₁, while it corresponds to a value k_1b of the reverse reaction 25% above the Baulch et al. evaluation. Combination of our results with literature values leads to a recommended rate constant for k_1b of 9.4 × 10¹² T^0.14 cm³ mol^?1 s^?1 over 250–3000 K. This value, which reconciles the differences between the forward and reverse rate constant, is recommended for use in kinetic modeling.     

Graphitization of Carbon Particles in a Non-thermal Plasma Reactor

The production of nanomaterials using non-thermal plasmas remains the focus of ongoing investigations due to advantageous properties of this class of processes, most notably the intense plasma-induced heating arising from energetic recombination events occurring at the surface of nanoparticles, which allows for the tailored synthesis of crystalline nanoparticles. In this work, the authors discuss an in situ, in-flight Fourier Transform Infrared absorption spectroscopy technique to investigate the temperature variation of carbon nanoparticles during their synthesis in an acetylene–argon–hydrogen non-thermal RF plasma. Based on the FTIR measurements, decreasing hydrogenation levels and the progressive onset of an incandescence signal were observed at increasing RF input power. In the high RF power region, the carbon particle temperature, derived by fitting the corresponding FTIR spectra with a modified Planck’s law, shows values above 2000 K. The corresponding ex situ characterization of the synthesized materials by Transmission Electron Microscopy and Raman Spectroscopy displays the production of highly graphitic particles and loss of bonded hydrogen from the material, hence supporting the substantial nanoparticle heating derived from the FTIR measurements.     

Estimation of Kinetic Parameters of Thermal Oxidation of Ilmenite

The aim of the presented work was the investigation of thermal oxidation of ilmenite in static air atmosphere. The investigations were carried out by use of a derivatograph (MOM, Hungary). The changes of crystallographic structure of investigated samples were identified by X-ray diffractometry on Philips PW-1710 diffractometer. In temperature above 500°C appears structure of hematite Fe₂O₃. On the basis of the thermogravimetric measurements, the contracting area and contracting volume models were found as the best fitting experimental data. This revised version was published online in August 2006 with corrections to the Cover Date.     

Nitrogen Functionalization of Carbon Black in a Thermo-Convective Plasma Reactor

We have developed a simple plasma reactor for functionalizing powders. The reactor uses thermo-convective cells to mix the powder during the treatment and to ensure high homogeneity. The reactor has been used to treat batches of 50–150 mg of carbon black in a gas mixture of He/N₂ at 40 Torr. By using repetitive treatments on fractions of carbon black recovered from the cap of the treatment vessel (due to its fluidization during the treatment), we were able to fix a concentration of nitrogen functionalities of 13% at. N/C (as measured by XPS). We report the working conditions of the reactor and the results obtained.     

Pyrolysis and Oxidation of Methane in a RF Plasma Reactor

The chemical kinetic effects of RF plasma on the pyrolysis and oxidation of methane were studied experimentally and computationally in a laminar flow reactor at 100 Torr and 373 K with and without oxygen addition into He/CH₄ mixtures. The formation of excited species as well as intermediate species and products in the RF plasma reactor was measured with optical emission spectrometer and Gas Chromatography and the data were used to validate the kinetic model. The kinetic analysis was performed to understand the key reaction pathways. The experimental results showed that H₂, C₂ and C₃ hydrocarbon formation was the major pathways for plasma assisted pyrolysis of methane. In contrast, with oxygen addition, C₂ and C₃ formation dramatically decreased, and syngas (H₂ and CO) became the major products. The above results revealed oxygen addition significantly modified the chemistry of plasma assisted fuel pyrolysis in a RF discharge. Moreover, an increase of E/n was found to be more beneficial for the formation of higher hydrocarbons while a small amount of oxygen was presented in a He/CH₄ mixture. A reaction path flux analysis showed that in a RF plasma, the formation of active species such as CH₃, CH₂, CH, H, O and O (¹D) via the electron impact dissociation reactions played a critical role in the subsequent processes of radical chain propagating and products formation. The results showed that the electronically excitation, ionization, and dissociation processes as well as the products formation were selective and strongly dependent on the reduced electric field.     

Effects of Carbide Formation in Graphene Growth

Besides carbon solubility, the carbide formation possibility is another important factor to differentiate various substrate materials in graphene growth. A recent experiment indicates that the formation of transition metal carbides (TMCs) can suppress carbon precipitation. In this study, Mo₂C, a representative of TMCs, is used to study the effects of carbide formation in graphene growth from first principles. Carbon diffusion in Mo₂C bulk turns out to be very difficult and it becomes much easier on the Mo₂C(001) surface. Therefore, carbon precipitation suppression and graphene growth can be realized simultaneously. A direction depended diffusion behavior is observed on the Mo₂C(101) surface, which makes it less favorable for graphene growth compared to the (001) surface.     

Hydrogen Production from Methane Decomposition Using a Mobile and Elongating Arc Plasma Reactor

Plasma Chemistry and Plasma Processing - Hydrogen and solid carbon were produced through methane decomposition in a plasma reactor with a parallel set of screw type helix and rod-like electrodes....     

Decomposition of Benzene in Air in a Plasma Reactor: Effect of Reactor Type and Operating Conditions

The decomposition of benzene was carried out in two types of plasma reactors packed with BaTiO₃ pellets: one reactor had two stainless steel electrodes (SUS reactor), and the other reactor had a glass layer between two concentric electrodes (GL reactor). The decomposition efficiency and the suppression of formation of N₂O and NO_x were greater in the GL reactor than in the SUS reactor. In contrast, the suppression of O₃ formation and the oxidation to CO_x in the SUS reactor were superior to those in the GL reactor. The effect of wa eform and frequency of applied ac power was in estigated for each reactor.     

Methane Decomposition in a Barium Titanate Packed-Bed Nonthermal Plasma Reactor

The behavior of lattice oxygen species of the ferroelectric material during methane oxidation was investigated using a nonthermal plasma reactor packed with BaTiO ₃ pellets. Lattice oxygen species in BaTiO ₃ play an important role in the formation of N ₂ O and the oxidation of CH ₄ . The oxidation products such as CO and CO ₂ were formed from independent reaction pathways. Lattice oxygen species were able to preferentially oxidize the carbon species deposited on the pellet surface into CO. Also, N ₂ O and NO _x were independently formed in the N ₂–O ₂ reaction, suggesting that different oxygen species give N ₂ O and NO _x. N ₂ O was produced by the oxidation of molecular nitrogen with lattice oxygen species.