Hydrodynamics and heat and mass transfer at chemical conversions in slot reactors

In this paper, experimental and numerical investigations of the hydrodynamics and heat transfer in a disk slot heat exchanger-reactor for a radial flow of a gas mixture reacting on the channel walls are described. Data for the coefficients of heat transfer from the wall being heated to the gas flowing inside the reactor are presented. The temperature field of a catalytically active reactor plate at heat release on it has been investigated experimentally. Calculations of the flow and heat transfer in a slot reactor element for a catalytic reaction with heat release have been performed. Partial oxidation of methane in an oxygen medium with the formation of a hydrogen-containing synthesis gas in a two-dimensional microchannel has been investigated numerically. Data for the extent of the chemical conversion of methane versus the initial mixture consumption and reaction temperature are presented.     

Partial oxidation of methane in a rapid compression machine with internal heat recovery

A new method for the partial oxidation of methane in a rapid compression machine with internal heat recovery was proposed and examined. A rapid compression machine on the basis of an internal combustion engine with a cylinder divided by a partition with a crossflow orifice into two chambers was considered. Internal heat recovery was implemented using a thermal activator installed in the smaller (auxiliary) chamber. Calculations demonstrated that this method makes it possible to convert methane in methane-air mixtures with a hydrocarbon content of up to 24% at degrees of compression of 10 to 20 and peak pressures below 200 atm. A region (determined by the crossflow orifice diameter and degree of compression) within which a heat recovery cycle exists was revealed. It was demonstrated that, for mixtures containing 22% methane or less, the extent of conversion exceeds 93%, a value that makes it possible to generate useful energy at degrees of compression above 10.     

Efficiency of an electron-beam-pumped chemical laser with an SF6-H2 working mixture

Results are presented from a study of HF lasers pumped by non-chain chemical reactions initiated by a radially convergent and by a planar electron beam. The main channels of formation of vibrationally excited HF molecules are analyzed. The distribution of the energy density of the radiation in the output beam of a wide-aperture laser is measured. In 30 liters of a mixture of SF₆:H₂=8:1 at a pressure of 1.1 atm an output energy of ∼200 J is obtained at an ∼11% efficiency with respect to the energy deposition. It is shown that the admixture of a buffer gas of neon or argon improves the uniformity of the radiation energy distribution in the output beam of an HF laser pumped by a non-chain chemical reaction and initiated by an electron beam, and it also increases the output energy. Zh. Tekh. Fiz. 69, 76–81 (January 1999)     

Electric generators of singlet delta oxygen for an oxygen-iodine laser

Experimental and theoretical research into electric generators of singlet delta oxygen (SDO) for an oxygen-iodine laser made at the Lebedev Physics Institute and TRINITI is discussed. Breakdown and current-voltage characteristics of self-sustained electric discharge in SDO were studied both experimentally and theoretically, indicating that SDO and pure oxygen have quite different electric features. The electric properties and spectroscopy of an e-beam sustained discharge (EBSD) in oxygen and oxygen gas mixtures were experimentally studied. A comprehensive numerical model describing SDO kinetics in different kinds of discharge was developed. The pulsed EBSD in pure oxygen and its mixtures with noble gases was shown to be very unstable and characterized by low input energy. When adding small amounts of carbon monoxide or hydrogen, the electric stability of the EBSD increases, the specific input energy (SIE) per molecular component being more than order of magnitude higher and coming to 6.5 kJ/(l atm(O₂ + CO)) for the gas mixture O₂: Ar: CO = 1: 1: 0.1. Theoretical calculations demonstrated that, for an SIE of 6.5 kJ/(l atm), the SDO yield may reach ∼20%, exceeding its threshold value needed for oxygen-iodine laser operation at room temperature. The calibration of the optical scheme for measuring the SDO absolute concentration and yield using the detection of luminescence of the SDO going from a chemical SDO generator was performed. The measurement of the SDO yield demonstrated that it was ∼10.5% for an SIE of ∼3.0 kJ/(l atm(O2 + CO)), which is about 1.5 times less than the results of theoretical calculations for such an SIE. SDO production in RF slab discharge ignited in oxygen gas mixtures was experimentally studied, experimental SDO yield being about 10%. The choice of electrode material was demonstrated to be very important. Original Text ? Astro, Ltd., 2006.     

Investigation of SRS conversion of XeCl laser emission in lead vapor,methane, and hydrogen

We have thus optimized the conditions for SRS conversion of XeCl-laser emission in lead vapor, methane, and hydrogen. The greatest influence on the conversion efficiency is exerted for an SRS cell with lead by the divergence of the pump radiation, the focusing geometry, and the type of buffer gas. The maximum efficiency with respect to absorbed UV energy was ∼57% when xenon gas was used as the buffer, corresponding to 85% of the photon efficiency. The converted radiation could be continuously tuned in the 457.6–459.3 nm band. Addition of a light gas such as helium or hydrogen to methane raised the efficiency of conversion into Stokes components in methane to ∼24 %.     

Yield of singlet oxygen from optically pumped CCl<Subscript>4</Subscript> solution of fullerenes

Boiling occurs in a solution of oxygen and fullerenes in CCl₄ upon optical pumping of C₆₀ upon the fast appearance of incandescent fullerenes in cold solvent. Upon single-photon absorption, a spherical zone of the critical state of CCl₄ is formed within 5 ns (with a diameter of 22–25 nm, P _cr ∼ 45 atm, and T _cr ∼ 556 K). This spherical zone (gas-bubble nucleus) expands to a diameter of ∼100–400 nm for 2–5 ns. If the external pressure (natural or artificial) is rapidly released, the bubble accelerates and emerges into a vacuum chamber within 0.7–25 μs (the length of the passage is 0.1–5 cm depending on the construction of the singlet oxygen generator). We note that singlet oxygen appears 50 ns after the absorption of a photon by fullerene (i.e., inside of the almost formed gas bubble that only begins to emerge from the liquid to a low-pressure gas region).     

Hydrogen production by methanol steam reforming in an annular microchannel on a Cu-ZnO catalyst

Steam reforming of methanol into a hydrogen-containing gas under activated methanol conversion on annular microchannel walls was experimentally investigated. The methanol conversion was carried out on a copper-zinc catalyst deposited on the channel internal wall. The concentrations of the chemical conversion products in the output gas mixture were determined at different reactor temperatures and residence times. The channel wall temperature range within which the methanol steam reforming is intensified was also determined. It was shown that the CO content in the reaction products is determined by the CO₂ partial pressure rather than by the reactor temperature. A kinetic model of methanol steam reforming on a copper-zinc catalyst was developed.     

On the mechanism of the deflagration-to-detonation transition in a hydrogen-oxygen mixture

The flame acceleration and the physical mechanism underlying the deflagration-to-detonation transition (DDT) have been studied experimentally, theoretically, and using a two-dimensional gasdynamic model for a hydrogen-oxygen gas mixture by taking into account the chain chemical reaction kinetics for eight components. A flame accelerating in a tube is shown to generate shock waves that are formed directly at the flame front just before DDT occurred, producing a layer of compressed gas adjacent to the flame front. A mixture with a density higher than that of the initial gas enters the flame front, is heated, and enters into reaction. As a result, a high-amplitude pressure peak is formed at the flame front. An increase in pressure and density at the leading edge of the flame front accelerates the chemical reaction, causing amplification of the compression wave and an exponentially rapid growth of the pressure peak, which “drags” the flame behind. A high-amplitude compression wave produces a strong shock immediately ahead of the reaction zone, generating a detonation wave. The theory and numerical simulations of the flame acceleration and the new physical mechanism of DDT are in complete agreement with the experimentally observed flame acceleration, shock formation, and DDT in a hydrogen-oxygen gas mixture.     

Filling boron nitride nanotubes with metals

The authors’ endeavors over the last few years with respect to boron nitride (BN) nanotube metal filling are reviewed. Mo clusters of 1–2 nm in size and FeNi Invar alloy (Fe ∼60 at. %; Ni ∼40 at. %) or Co nanorods of 20–70 nm in diameter were embedded into BN nanotube channels via a newly developed two-stage process, in which multi-walled C nanotubes served as templates for the BN multi-walled nanotube synthesis. During cluster filling, low-surface-tension and melting-point Mo oxide first filled a C nanotube through the open tube ends, followed by fragmentation of this filling into discrete clusters via O₂ outflow and C→BN conversion within tubular shells at high temperature. During nanorod filling, C nanotubes containing FeNi or Co nanoparticles at the tube tips were first synthesized by plasma-assisted chemical vapor deposition on FeNi Invar alloy or Co substrates, respectively, and, then, the nanomaterial was heated to the melting points of the corresponding metals in a flow of B₂O₃ and N₂ gases. During this second stage, simultaneous filling of nanotubes with a FeNi or Co melt through capillarity and chemical modification of C tubular shells to form BN nanotubes occurred. The synthesized nanocomposites were analyzed by scanning and high-resolution transmission electron microscopy, electron diffraction, electron-energy-loss spectroscopy and energy-dispersive X-ray spectroscopy. The nanostructures are presumed to function as ‘nanocables’ having conducting metallic cores (FeNi, Co, Mo) and insulating nanotubular shields (BN) with the additional benefit of excellent environmental stability. Received: 10 October 2002 / Accepted: 25 October 2002 / Published online: 10 March 2003 RID="*" ID="*"Corresponding author. Fax: +81-298/51-6280, E-mail: golberg.dmitri@nims.go.jp     

Sound waves generated due to the absorption of a pulsed electron beam in gas

The results of an experimental investigation of acoustic vibrations (their frequency, amplitude, and attenuation coefficient) generated in a gas mixture as a result of the injection of a high-current pulsed electron beam into a closed reactor are presented. It is shown that the change in the phase composition of the initial mixture under the action of the electron beam leads to a change in the frequency of the sound waves and to an increase in the attenuation coefficient. By measuring the change in frequency, it is possible to evaluate with sufficient accuracy (about 2%) the degree of conversion of the initial products in the plasmochemical process. Relations describing the dependence of the sound energy attenuation coefficient on the size of the reactor and on the thermal and physical properties of the gases under study are derived. It is shown that a simple experimental setup measuring the parameters of acoustic waves can be used for monitoring the plasmochemical processes initiated by a pulsed excitation of a gas mixture.     

Laser gain measurements at 193 nm in a small discharge cell containing ArF excimer laser gas mixtures

Spatial and temporal gain profiles as well as the peak net gain at 193 nm have been measured in X-ray preionized discharges excited by a single pulse electrical system working in the charge transfer mode. Ar- and F₂-containing laser gas mixtures with He or Ne as a buffer gas have been used. With a pumping pulse duration of ∼ 100 ns (FWHM) and a specific peak power deposition of ∼ 1 MW cm^-3 bar^-1 in a gas mixture containing F₂ : Ar : He (0.1%:5%:94.9%), at 2 bar total pressure, a very high peak net gain coefficient of ∼ 30% cm^-1 was measured in the gas discharge. The FWHM of the gain waveform was ∼ 60 ns. PACS 42.55.Lt; 42.60.Lh; 52.80.-s     

Conversion of coals with various degree of metamorphism in supercritical water with formic acid

Conversion of coals with various degrees of metamorphism in supercritical water (SCW) was studied under the isochoric conditions at the temperatures of 380–800 °C. At conversion, formic acid, increasing the hydrogenating properties of the medium, was added into SCW. The results of conversion are comparable with the results of pyrolysis under the same temperatures. It was found that the degree of conversion in SCW is 10–15 % higher than that at pyrolysis. An addition of formic acid increases the conversion degree. After processing, there are almost no liquid organic substances escaped into SCW. However, some agglomerates, whose strength is comparable with the strength of lump coal, are formed because of dissolution of the organic matter in the mixture of SCW and formic acid.     

Equation of state of fluid helium at high temperatures and densities

Hugoniot curves and shock temperatures of gas helium with initial temperature 293 K and three initial pressures 0.6, 1.2, and 5.0 MPa were measured up to 15000 K using a two-stage light-gas gun and transient radiation pyrometer. It was found that the calculated Hugoniot EOS of gas helium at the same initial pressure using Saha equation with Debye-Hückel correction was in good agreement with the experimental data. The curve of the calculated shock wave velocity with the particle velocity of gas helium which is shocked from the initial pressure 5 MPa and temperature 293 K, i.e., theD ≈u relation,D=C ₀+λu (u<10 km/s, λ=1.32) in a low pressure region, is approximately parallel with the fittedD ≈u (λ=1.36) of liquid helium from the experimental data of Nellis et al. Our calculations show that the Hugoniot parameter λ is independent of the initial density p{in0}. TheD≈u curves of gas helium will transfer to another one and approach a limiting value of compression when their temperature elevates to about 18000 K and the ionization degree of the shocked gas helium reaches 10⁻³.     

First-sound rarefaction and compression waves in superfluid He-II

The evolution of the form of first-sound waves, excited in superfluid He-II by a pulsed heater, with increasing power Q of the perturbing heat pulse is investigated. In liquid compressed to 13.3 atm, a first-sound rarefaction wave (wave of heating) is observed, which transforms into a compression wave and then into a compression shock wave as Q increases, i.e., the change in the conditions of heat transfer at a solid-He-II interface can be judged according to the change in the form of the sound wave. It follows from our measurements that in He-II compression waves are excited at pressures P⩾1 atm primarily as a result of the thermal expansion of a normal He-I liquid layer arising at the He-II-heater interface for power Q above a critical level. Pis’ma Zh. éksp. Teor. Fiz. 69, No. 10, 716–720 (25 May 1999)     

Kinetic investigation of the ozone-assisted partial oxidation of fuel-rich natural gas mixtures at elevated pressure

The partial oxidation of natural gas in HCCI engines in terms of a polygeneration process could be a promising technology to flexibly produce useful chemicals, heat, and work, depending on demand. Because natural gas is relatively inert, high intake temperatures or compression ratios are required to initiate its conversion which can result in a lower lifetime of the engine. Alternatively, small amounts of more reactive species such as ozone can be added to the initial mixture to provide radicals at more moderate conditions and initiate the main ignition. In this study, plug-flow reactor experiments are performed to assess the influence of ozone on the fuel conversion and product formation during the partial oxidation of methane and natural gas. Experiments are performed in the temperature range of 373 K to 973 K at 4 bar and equivalence ratios of 2. Molecular-beam mass spectrometry coupled with electron ionization is used as analytical technique to detect the mixture composition at the outlet of the reactor. The results show that even very small amounts of ozone can help to shift the conversion onset to much lower temperatures and increase the yields of useful chemicals. The data can further be used to improve reaction mechanisms describing the conversion of hydrocarbons in the presence of ozone. A literature ozone reaction mechanism has been implemented in two recent hydrocarbon mechanisms and the results of simulations using these mechanisms are compared to the experimental data with respect to the low-temperature intermediates which influence ignition. Predictions differ substantially from the experimental results identifying starting points for further investigations. The speciation data provided in this work contribute to extending the reaction kinetics of ozone assisted fuel conversion to higher pressure.     

Equation of state of fluid helium at high temperatures and densities

Helium, hydrogen, and their isotopes are the simplest monoatomic and diatomic molecules. It is relatively easy to describe their properties using the basic principles of quantum mechanics. In condensed matter physics, hydrogen and helium serve as the models for the condensed matter properties at extreme conditions so that both experi- mental and theoretical physicists pay much attention to the study of their properties[1], especially the insulator-metal transition of hydrogen[2]. The aim to st…     

A study of the characteristics of the combustion of a Ti +0.5C granular mixture in an inert gas flow

The characteristics of the combustion of a Ti +0.5C granular mixture in a quartz tube under conditions of blowing with argon are studied. The gas flow (cocurrent filtration) is provided by a fixed pressure drop (<1 atm) across the feedstock bed. The dynamics of gas evolution during the combustion the Ti + 0.5C granular mixture, both in the presence and absence of blowing is investigated. The blowing is demonstrated to influence the chemical and phase composition of the condensed synthesis products. It is shown that blowing the Ti + 0.5C granular mixture with a cocurrent argon flow of increases the burning rate.     

Current progress on heat conduction in one-dimensional gas channels

We give a brief review of the past development of model studies on one-dimensional heat conduction. Particularly, we describe recent achievements on the study of heat conduction in one-dimensional gas models including the hard-point gas model and billiard gas channel. For a one-dimensional gas of elastically colliding particles of unequal masses, heat conduction is anomalous due to momentum conservation, and the divergence exponent of heat conductivity is estimated as α≈0.33 in k ∼ L ^α . Moreover, in billiard gas models, it is found that exponent instability is not necessary for normal heat conduction. The connection between heat conductivity and diffusion is investigated. Some new progress is reported. A recently proposed model with a quantized degree of freedom to study the heat transport in quasi-one dimensional systems is illustrated in which three distinct temperature regimes of heat conductivity are manifested. The establishment of local thermal equilibrium (LTE) in homogeneous and heterogeneous systems is also discussed. Finally, we give a summary with an outlook for further study about the problem of heat conduction.     

Enhancement of inner tube formation from peapods in de-pressurized inert gas environment

C₆₀ molecules encased in single-wall carbon nanotubes, so-called peapods, can be transformed into small-diameter tubes inside the host tubes after high-temperature heat treatment in vacuum at ∼1200 °C. Here, we report an experiment on high-temperature heat treatment of peapods in inert gas environment, and show the evidence of enhancing the formation rate of inner tubes, the rate being more than ∼6 times higher in Ar environment and ∼9 times higher in He than that in vacuum. This means that the inert gas atoms markedly accelerate the polymerization of C₆₀. In contrast to Ar and He, it is found that H₂ gas does not enhance the C₆₀ polymerization. PACS 61.46.Fg; 81.05.Tp; 82.60.Qr     

Adiabatic frequency conversion of ultrafast pulses

A new method for efficient, broadband sum and difference frequency generation of ultrafast pulses is demonstrated. The principles of the method follow from an analogy between frequency conversion and coherent optical excitation of a two-level system. For conversion of ultrafast pulses, the concepts of adiabatic conversion are developed further in order to account for dispersion and group velocity mismatch. The scheme was implemented using aperiodically poled nonlinear crystals and a single step nonlinear mixing process, leading to conversion of near-IR (∼790 nm) ultrafast pulses into the blue (∼450 nm) and mid-IR (∼3.15 μm) spectral regions. Conversion bandwidths up to 15 THz FWHM and efficiencies up to 50% are reported.