Methanol synthesis from carbon dioxide and hydrogen using a ceramic memebrane reactor

Methanol was synthesized from CO₂ and H₂ using a silica/alumina composite membrane reactor, which improved methanol conversion to 150% of the value in conventional reactor, by in situ removal of water formed in catalytic reaction. This revised version was published online in June 2006 with corrections to the Cover Date.     

Two-temperature modeling of an arc plasma reactor

In this paper a two-temperature plasma model is established and applied to the injection of cold gases into an atmospheric-pressure, high-intensity argon arc. The required nonequilibrium plasma composition and the non-equilibrium transport properties are also calculated. The results show that the arc becomes constricted at the location of gas injection due to thermal and fluid dynamic effects of the injected cold flow. Enhanced Joule heating in the constricted arc path raises the electron as well as the heavy-particle temperatures. This temperature increase resists, via secondary effects, the penetration of the cold gas into the hot arc core which behaves more or less as a solid body as far as the injected flow is concerned. The temperature discrepancy between electrons and heavy particles is most severe at the location of cold flow injection, a finding which may have important consequences on chemical reactions in an arc plasma reactor.     

Study of the reduction of silicon monoxide in arc plasma

The results of study aimed to reveal the existence of kinetic limitations on the reduction of silicon monoxide with methane carbon in arc plasma in relation to the potential use of this process in the proposed advanced technology for manufacturing pure silicon are reported. It was concluded that the amount of silicon monoxide should be two times its stoichiometric amount required for the complete consumption of the methane carbon and there are no kinetic constraints on the process of silicon monoxide reduction over a time of τ = 4–5 ms at atmospheric pressure and a temperature of T = 2240–2350 K.     

Vibration—vibration energy exchange between carbon monoxide and carbon dioxide

Measurements have been made on the vibration—vibration (V—V) energy exchange rate between carbon monoxide and carbon dioxide in the temperature range 180 to 345 K. A steady-state vibrational fluorecence quenching technique was used in conjunction with an open flow gas system. Vibrational excitation of the carbon monoxide was accomplished by absorption of infrared radiation from prospane—oxygen flames. The measured rate constant for the process CO* (υ = 1) + CO₂ → CO + CO^*₂(001) increased linearly with temperature, and after correction for the V—V exchange rate fo the back reaction, the rate constant has a value of (2.2 ± 0.3) × 10³ torr^?1 s^?1 at 296 K. The data are compared to results at highest temperatures and to available theoretical calculations.     

Pyrolysis of nuclear reactor circulator oil in carbon dioxide

The ingress of circulator oil into the carbon dioxide coolant of a nuclear reactor can cause problems such as the deposition of carbon on the fuel elements.This paper describes the first stage of degradation when oil is pyrolysed, in carbon dioxide at temperatures between 600 and 900°C, and in helium at 900°C, for 20s. The degradation products were determined using gas chromatography with either a selective carbon monoxide monitor or a flame ionization detector. The chromatograph was combined with a mass spectrometer for the identification of the degradation produces.Hydrogen, carbon monoxide and a wide range of hydrocarbons are the initial degradation products. The amounts of individual reaction product, and the total amount formed (P) increased with pyrolysis temperature, T, according and the total amount = 1/T. The sensitivity to temperature of product formation varied from one product to another. Formation of carbon monoxide was least sensitive to temperature.It is clear that a chemical reaction takes place between the oil and carbon dioxide since the total amounl of product produced is much greater in carbon dioxide than in helium and the relative amounts of product produced in carbon dioxide differ considerably from those produced by pyrolysis in helium: for example, no carbon monoxide is detected when the oil is pyrolysed in helium.     

Influence of carbon dioxide and carbon monoxide on the kinetics of propylene polymerization

Retardation effect of the carbon oxides on propylene polymerization, catalyzed by the TiCl₃/AlEt₂Cl system, can be described in terms of a Langmuir type equation as selective adsorption of the carbon oxides on the polymerization sites.

---

, TiCl₃/AlEt₂Cl, , .

     

Reduction of NO by carbon monoxide on tin dioxide

The reduction of NO by carbon monoxide on SnO₂ has been studied in the temperature range from 90 to 450°C. The complicated temperature dependence of the reaction rate is due to the interaction of CO an CO₂ with the catalyst.

---

NO SnO₂ 90–450°C. , CO CO₂ .

     

A review of non-gravimetric methods of determining carbon dioxide and monoxide

The titrimetric and instrumental methods of measuring amounts of carbon dioxide and instrumental methods for carbon monoxide are reviewed.     

Biomass pyrolysis in a heated-grid reactor: Visualization of carbon monoxide and formaldehyde using Laser-Induced Fluorescence

The development of improved biomass pyrolysis models is vital for more accurate modelling and design of biomass conversion equipment. Such improved models must be based on reliable experimental data: biomass should be pyrolyzed at high heating rates and the reaction products should be measured using an on-line, non-intrusive method. Therefore, a heated grid reactor with heating rate of 300-600 K/s was used to study pyrolysis of biomass at temperatures in the range of 500-700 °C. The formation of formaldehyde and carbon monoxide from wood at high heating rates was successfully visualized using Laser-Induced Fluorescence (LIF). A thin vertical laser line or sheet was present directly above the biomass lying on the heated grid. Two-photon excitation at 230 nm was applied to induce fluorescence of carbon monoxide present in the volatiles, whereas excitation of formaldehyde was done at 355 nm. Visualization of these compounds shows that the release rises strongly with temperature; this typically happens on a timescale in the order of seconds. In principle, the method described allows for the determination of truly primary products. Future research is recommended, aimed at quantifying the concentrations measured by LIF. Care must be taken to calibrate for quenching of the fluorescence signal. Avoiding secondary reactions taking place in the gas phase is another experimental challenge.     

Trapping adsorption of carbon monoxide located between carbon dioxide adsorbed on magnesium oxide

Carbon monoxide adsorbed on MgO is strongly trapped by the adsorbed carbon dioxide, increasing the heat of adsorption from 85.4 to 184.1 kJ/mol. The trapped CO is thought to be captured by two or three adsorbed CO₂ and becomes less active to react with oxygen.

---

, MgO, , 85,4 184,1 /. , CO CO₂ .

     

The photochemically induced reaction of sulfur dioxide with alkanes and carbon monoxide

Abstract— The gas phase photochemical reactions of SO₂ induced by 3130 Å radiation have been studied in the presence of added alkanes or added CO. The quantum yields obtained in the reactions with the low molecular weight alkanes employed are lower than those obtained by previous workers. The quantum yields were found to be pressure dependent increasing slowly with increasing pressure. A stoichiometric ratio of one SO₂ removed per molecule of hydrocarbon consumed was observed only under experimental conditions of [SO₂] < [RH]. For reaction mixtures where [SO₂] < [RH] the ratio of [SO₂]/[RH] reacted always exceeded unity. The quantum yields decreased slightly with increasing temperature. In all the alkane reaction systems studied, the deposition of viscous, nonvolatile reaction products was observed. In the experiments with added CO, the quantum yields were computed with respect to the rate of CO₂ formation. At 25°C and equal pressures of SO₂ and CO, φco₂ was observed to be 0.005 and it decreased slightly with increasing temperature. The results obtained are interpreted in terms of the sulfoxidation of the alkanes and the oxidation of CO proceeding by way of a ³SO₂ reaction intermediate.     

Production of a highly dispersed carbon material and hydrogen from natural gas in a microwave reactor with metallic catalysts

Effect of a microwave field on metallic catalysts was studied in the reaction of decomposition of methane into hydrogen and highly dispersed carbon. The dependence of the conversion of methane, yield of carbon, and its composition on the chemical nature of a catalysts and reaction conditions was examined.     

State of the copper ions in the catalysts for oxidation of carbon monoxide to carbon dioxide

The state of the copper ions in the catalysts for the oxidation of carbon monoxide to carbon dioxide, prepared by dissolving an activated copper-containing aluminum alloy in water followed by calcination (method A) and by impregnation of the support produced by dissolving activated aluminum in water with copper nitrate solution (method B), was investigated by diffuse reflection electronic spectroscopy. It was established that the catalysts contain Cu ²⁺ ions stabilized in fields of octahedral symmetry. The concentration of these ions depends on the method of synthesis of the catalyst, its copper content, and the pretreatment temperature. It is higher in the samples produced by impregnation than in the samples produced by fusion; increase in the amount of copper leads to a decrease while increase in the calcination temperature leads to an increase in the concentration of the above-mentioned ions. Treatment of the oxide systems with the reaction mixture does not affect the state and concentration of Cu ²⁺. The catalytic activity of the samples depends on the method of preparation and increases with decrease in the amount of Cu ²⁺ (O_h) and with increase in the content of the CuO phase in the system.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 786–790, April, 1992.     

Carbon dioxide reduction and carbon monoxide activation employing a reactive uranium(III) complex

The highly reactive, six-coordinate tris-aryloxide U(III) species, [((t-BuArO)3tacn)U] (1) reacts with CO2 in a 2e- reduction to produce CO and a dinuclear U(IV/IV) mu-oxygen bridged complex [{((t-BuArO)3tacn)U}2(mu-O)] (2). This reaction proceeds via a dinuclear CO2-bridged intermediate 3. Also, mononuclear 1 was treated with 1 atm of CO to yield dinuclear [{((t-BuArO)3tacn)U}2(mu-CO)] (4) with a CO ligand bridging two uranium ions in an unprecedented mu:eta1,eta1 fashion. The mixed-valent azido-bridged U(III/IV) complex 5 was synthesized from trivalent 1 and tetravalent [((t-BuArO)3tacn)U(N3)] and serves as an isostructural analogue of triatomic-bridged intermediate 3 as well as an electronic model for mixed-valent 4.     

Determination of carbon monoxide,methane and carbon dioxide in refinery hydrogen gases and air by gas chromatography

This paper illustrates a method for determining trace amounts of CO, CH4 and CO2 with the detection limit of 0.15, 0.15 and 0.20 microg/l, respectively, in refinery hydrogen gases or in air. A simple modification of a gas chromatograph equipped with a flame-ionization detector is presented. A Porapak Q column, additionally connected with a short molecular sieve 5A packed column and a catalytic hydrogenation reactor on the Ni catalyst have been applied. The principle of the analytical method proposed is the separation of CO from O2 before the introduction of CO to the methanizer. The analytical procedure and examples of the results obtained have been presented. The modification applied makes it possible to use the GC instrument for other determinations, requiring utilization of the Porapak Q column and the flame-ionization detector. In such cases, the short molecular sieve 5A column and the methanizer can be by-passed.     

Aminorhenium carbon dioxide complexes: formal oxidation of a carbon monoxide ligand with peroxy-acids or bromine/hydroxide

The electron-rich aminorhenium complexes η⁵:η¹-C₅H₄CH₂CH₂NR(CH₃)Re(CO)₂ (3a-d; R=methyl, benzyl, n-butyl, n-butyl-OH) are easily oxidized with peroxy-acids to give the corresponding η²-CO₂ complexes η⁵: η¹- C₅H₄CH₂CH₂NR(CH₃)Re(CO)(η²-CO₂) (4a-d) in excellent yield. The resultant η²-CO₂ complex is predominantly the anti-isomer. The structures of η²-CO₂ complex η⁵:η¹-C₅H₄CH₂CH₂N(CH₃)(n- C₄H₈OH)Re(CO)(η²-CO₂) (4d-anti) and the corresponding CO complex 3d have been confirmed by X-ray crystallography. The η²-CO₂ complexes 4a-4d are stable at ambient temperature under air. In addition to peroxy-acid oxidation, bromination of the aminorhenium dicarbonyl complexes followed by base treatment also provided the corresponding η²-CO₂ complexes. The reaction mechanism for the formation of CO₂ complex from the corresponding dicarbonyl is discussed briefly.     

Production of hydrogen peroxide from carbon monoxide, water and oxygen over alumina-supported Ni catalysts

Novel amorphous Ni–B catalysts supported on alumina have been developed for the production of hydrogen peroxide from carbon monoxide, water and oxygen. The experimental investigation confirmed that the promoter/Ni ratio and the preparation conditions have a significant effect on the activity and lifetime of the catalyst. Among all the catalysts tested, the Ni–La–B/γ-Al₂O₃ catalyst with a 1:15 atomic ratio of La/Ni, dried at 120 °C, shows the best activity and lifetime for the production of hydrogen peroxide. The deactivation of the alumina-supported Ni–B amorphous catalyst was also studied. According to the characterizations of the fresh and used catalysts by SEM, XRD and XPS, no sintering of the active component and crystallization of the amorphous species were observed. However, it is water poisoning that leads to the deactivation of the catalyst. The catalyst characterization demonstrated that the active component had changed (i.e., amorphous NiO to amorphous Ni(OH)₂) and then salt was formed in the reaction conditions. Water promoted the deactivation because the surface transformation of the active Ni species was accelerated by forming Ni(OH)₂ in the presence of water. The formed Ni(OH)₂ would partially change to Ni₃(PO₄)₂.