Effect of radionuclide 32P incorporation on the catalytical activity of the BASF K-3-10 catalyst for the low-temperature conversion of carbon monoxide by water vapour

1989 ◽  
Vol 54 (8) ◽  
pp. 2083-2090
Author(s):  
Alois Motl

The catalytical activity of the BASF K-3-10 catalyst for the low-temperature conversion of carbon monoxide by water vapour has been studied in dependence on the activity of incorporated radionuclide 32P. Radioactivity of the catalytical bed ranged from 0 to 630 MBq of incorporated 32P. It has been observed that at first the catalytical activity increases with the increasing activity of 32P and finally it reaches a limit value that is by about 50 per cent higher than that of the same non-radioactive catalyst. The comparison of these results with those obtained in the studies of the catalytical activity of the same catalyst pre-irradiated by β radiation of the 90Sr-90Y source revealed that in the case of radioactive beds the observed positive radiation-catalytical effect can be ascribed to the pre-irradiation of the catalyst (during the period between the preparation of the radioactive catalytical bed and the catalytical reduction itself) and to the interactions of the ionizing radiation with the catalyst during the subsequent operations. The radiation-catalytical effects induced by the two processes mentioned above differ substantially by their time stability. The probable explanation of the nature of these two effects is proposed using the published mechanism of this reaction.

1986 ◽  
Vol 51 (2) ◽  
pp. 279-287 ◽  
Author(s):  
Alois Motl

The catalytic activity of the BASF K-3-10 catalyst with regard to the low-temperature conversion of carbon monoxide by water vapour and its changes after irradiation of the contact area by gamma or beta radiation or by fast neutrons has been investigated. The irradiated samples exhibit a moderately or even substantially higher catalytic activity in comparison with the non-irradiated catalyst, the change being dependent on the absorbed dose; moreover, the effective activation energy of the reaction increases, too. Important differences in the action of different types of the ionizing radiation used have been observed and their probable explanation is offered. In course of these experiments the catalysts were analyzed and the specific surface of the catalyst was measured at various stages of their history. It has been found that at all stages the specific surfaces of the irradiated catalyst are equal to the respective specific surfaces of the non-irradiated contacts.


Implicit solutions of the time-dependent flame equations have been used to calculate, for assumed reaction mechanisms, the expected structures and properties of a series of hydrogen-carbon monoxide-oxygen-nitrogen flames, some containing traces of added water vapour, at atmospheric and reduced pressures. Predicted burning velocities at atmospheric pressure have been compared with: ( a ) recent measurements, reported here, of the effect of addition of up to 10 % carbon monoxide on the burning velocity of a low temperature hydrogen-oxygennitrogen flame; ( b ) previous measurements by Scholte & Vaags (1959c) on dry hydrogen-carbon monoxide-air mixtures over the whole composition range on the fuel-rich side of stoichiometric; and ( c ) previously reported measurements by Jahn (1934), Badami & Egerton (1955), Scholte & Vaags (1959 b )and Wires et al . (1959) for moist carbon monoxide-air or carbon monoxide-oxygen mixtures, with or without traces of added hydrogen. Additionally, the following comparisons are made: ( d )The mole fraction profile for the decay of a trace of carbon dioxide added to the low temperature hydrogen-oxygen-nitrogen flame has been recalculated with the aid of the full reaction mechanism, for comparison with the previously reported measurements of Dixon-Lewis et al. (1965). ( e ) Computed structures of two hydrogen-carbon monoxide-oxygen-argon flames burning at reduced pressure have been compared with previous measurements by Fenimore & Jones (1959) and Vandooren et al . (1975). ( f ) The mole fraction ratio X co /X CO 2 in the burnt gas from a low temperature, fuel-rich hydrogen-carbon monoxide-oxygen-argon flame at atmospheric pressure was measured by using a mass spectrometer. The measured ratio agreed to within 1 % with that predicted by computation of the complete flame properties. Both the calculated and measured ratios were higher than would correspond with the establishment of the water gas equilibrium in the flame. The major part of the observed changes in burning velocity from those of hydrogen-air mixtures can be satisfactorily explained by the addition of the single reaction (xxi) , OH + CO ⇌ C O 2 + H , ( xxi ) to the mechanism already established for the hydrogen-oxygen-nitrogen flame system (Dixon-Lewis 1979). This applies particularly to fuel-lean flames and to fuel-rich mixtures not too far from stoichiometric. For fuel-rich flames further from stoichiometric, and particularly for the measurements in §(a), agreement between predicted and measured burning velocities is improved by adding to the mechanism a series of chain terminating steps involving the formation and subsequent reactions of the formyl radical. For reasonable values of its rate coefficient, reaction (xxii), O + CO + M ⇌ C O 2 + M , ( xxii ) never exerts more than a minor influence on the burning velocity. The major features of the structure of the flames are: ( a ) a preferential oxidation of hydrogen in the early stages of the reaction zones, leading to overshoot in the water concentration followed by a slow approach to the water gas equilibrium from the carbon monoxide-water side; and ( b ) marked enrichment of the oxygen atom concentration in the radical pool as the hydrogen content of the flames is decreased. In the flames containing only traces of hydrogen, the degree of enrichment is markedly influenced by reaction (xxii).


2018 ◽  
Vol 52 (4) ◽  
pp. 307-311
Author(s):  
E. Yu. Liberman ◽  
A. V. Naumkin ◽  
A. A. Revina ◽  
A. I. Mikhailichenko ◽  
M. V. Tsodikov ◽  
...  

1980 ◽  
Vol 45 (12) ◽  
pp. 3402-3407 ◽  
Author(s):  
Jaroslav Bartoň ◽  
Vladimír Pour

The course of the conversion of methanol with water vapour was followed on a low-temperature Cu-Zn-Cr-Al catalyst at pressures of 0.2 and 0.6 MPa. The kinetic data were evaluated together with those obtained at 0.1 MPa and the following equation for the reaction kinetics at the given conditions was derived: r = [p(CH3OH)p(H2O)]0.5[p(H2)]-1.3.


1996 ◽  
Vol 15 (12) ◽  
pp. 2829-2832 ◽  
Author(s):  
Matthew S. Sigman ◽  
Bruce E. Eaton ◽  
Jerald D. Heise ◽  
Clifford P. Kubiak

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Bing Nan ◽  
Qiang Fu ◽  
Jing Yu ◽  
Miao Shu ◽  
Lu-Lu Zhou ◽  
...  

AbstractAs the technology development, the future advanced combustion engines must be designed to perform at a low temperature. Thus, it is a great challenge to synthesize high active and stable catalysts to resolve exhaust below 100 °C. Here, we report that bismuth as a dopant is added to form platinum-bismuth cluster on silica for CO oxidation. The highly reducible oxygen species provided by surface metal-oxide (M-O) interface could be activated by CO at low temperature (~50 °C) with a high CO2 production rate of 487 μmolCO2·gPt−1·s−1 at 110 °C. Experiment data combined with density functional calculation (DFT) results demonstrate that Pt cluster with surface Pt−O−Bi structure is the active site for CO oxidation via providing moderate CO adsorption and activating CO molecules with electron transformation between platinum atom and carbon monoxide. These findings provide a unique and general approach towards design of potential excellent performance catalysts for redox reaction.


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