Sulfur dioxide oxidation rate

E. HamUton, personal communication), Calvert estimated sulfur dioxide oxidation rates by hydroperoxy, methylperoxy, hydroxyl, and methoxy radicals to be 0.85, 0.16, 0.23-1.4, and 0.48%/h, respectively. 

Stockwell, W. R., The Effect of Gas-Phase Chemistry on Aqueous-Phase Sulfur Dioxide Oxidation Rates, J. Atmos. Chem., 19, 317-329 (1994). 

Table IV. Observed Sulfur Dioxide Oxidation Rates (Continued)...

It is partly the fault of statistics that experimenters have misconstrued the value of the number and precision of data points relative to the value of the location of the points. The importance of the location of the data in the model specification stage can be seen from Fig. 1, which represents literature data (M3) on sulfur dioxide oxidation. The dashed and solid lines represent the predicted rates of two rival models, and the points are the results of two series of experimental runs. It can be seen that neither a greater number of experimental points nor data of greater precision will be of major assistance in discriminating between the two rival models, if data are restricted to the total pressure range from 2 to 10 atm. These data simply do not place the models in jeopardy, as would data below 2 atm and greater than 10 atm total pressure. This is presumably the problem in the water-gas shift reaction, which is classical in terms of the number of models proposed, each of which adequately represent given sets of data. 

Yamamoto, K., M. Seki, and K. Kawazoe. Effect of sulfuric acid accumulation on the rate of sulfur dioxide oxidation on activated carbon surface. Nippon Kaguku Kaiski 7 1268-2179, 1973. (in Japanese, summary in English)... 

Several other reports have also shown the importance of effective catalyst wetting on the performance of a bench-scale trickle-bed reactor. Hartman and Coughlin37 concluded that for sulfur dioxide oxidation in qojjntercurrejQt trickle-bed reactor packed with carbon particles, the catalyst was not completely wet at low liquid flow rates (of the order of 5 x 10 4 cm s-1). Sedricks and Kenney86 found that, during catalytic hydrogenation of crotonaldehyde in a cocurrent trickle-bed reactor, liquid seeped. into dry palladium-on-alumina... 

The entropy production of a sulfur dioxide oxidation (exothermic) reactor with heat exchangers was minimised in two different cases.Case 1 was a four-bed reactor with intermediate heat exchangers of a given total area, see Figure 8. The entropy production rate was calculated from the entropy balance over the system. All inlet and outlet flow conditions were kept constant, except the pressure at the outlet. Tlie... 

To date, there have been several unsuccessful attempts to fit these results to a simple model—for example, one based on a shrinking unreacted core or on reaction of a porous solid. The apparent role of water in the mechanism suggests that sulfur dioxide may be oxidized to sulfur trioxide on the surface and that sulfur trioxide diffuses through a product layer to react with calcium carbonate. This concept would be consistent with the similar kinetics observed for half- and fully calcined stone since the rate-determining step would presumably be the same in either case. This view is supported by the observation that reactivity in a fluidized bed decreases somewhat above about 850 °C because the thermodynamics of sulfur dioxide oxidation become less favorable. On the other hand, Borgwardt s observations with fully calcined stone (1) suggest that the decreased reactivity is caused by hard-burning of the stone. 

It is necessary to create vacancies on the inner surface to allow continued adsorption. Vacancies, however, are created by sulfur dioxide oxidation and the subsequent transport of the generated sulfuric acid to readily accessible inner pores. Therefore, the adsorption rate is now controlled by the rate of oxidation and transport. This interdependent relationship is characteristic of this phase of adsorption. 

Catalysts may therefore be designed for nse in specific duties. For power plant, the design must balance the reaction rates of NOX reduction and sulfur dioxide oxidation in the restricted range of temperature of flue gas leaving the boiler, or at the dust and sulfur dioxide removal stages. A low activity catalyst that reaches maximum NOX reduction between, say 380°-400°C, can be more efficient than a catalyst that is more active between 300°-350°C because, overall, it produces less sulfur trioxide at the fixed operating temperature. ... 

High Temperature Corrosion. The rate of oxidation of magnesium adoys increases with time and temperature. Additions of berydium, cerium [7440-45-17, lanthanum [7439-91-0] or yttrium as adoying elements reduce the oxidation rate at elevated temperatures. Sulfur dioxide, ammonium fluoroborate [13826-83-0] as wed as sulfur hexafluoride inhibit oxidation at elevated temperatures. 

Metals and alloys, the principal industrial metalhc catalysts, are found in periodic group TII, which are transition elements with almost-completed 3d, 4d, and 5d electronic orbits. According to theory, electrons from adsorbed molecules can fill the vacancies in the incomplete shells and thus make a chemical bond. What happens subsequently depends on the operating conditions. Platinum, palladium, and nickel form both hydrides and oxides they are effective in hydrogenation (vegetable oils) and oxidation (ammonia or sulfur dioxide). Alloys do not always have catalytic properties intermediate between those of the component metals, since the surface condition may be different from the bulk and catalysis is a function of the surface condition. Addition of some rhenium to Pt/AlgO permits the use of lower temperatures and slows the deactivation rate. The mechanism of catalysis by alloys is still controversial in many instances. 

The remaining. SO percent or less ot supply must have an average emission rate below the system average for fossil-fuel-emitted sulfur dioxide, nitrogen oxide, and carbon dioxide. 

Sufur rapidly oxidizes to sulfur dioxide in the combustion chamber, Some of this sulfur dioxide undergoes further oxidation to produce the very corrosive gas sulfur trioxide. The conversion rate is fairly low and is dependent on several factors, including ... 

The promotor effect of SO2 increases with the amount added to the reaction medium (Fig.3). An effect of the addition of sulfur dioxide has also been observed on the oxidation of decane with an increase of the activation energy expected for such a poisoning. This addition leads to a noticeable decrease of the rate of oxidation at low temperature, where Cu sulfate is stable, but the effect becomes negligible at about 600 K. At this temperature, the conversion of decane estimated by the evolution of the peak e/m = 57, characteristic of the hydrocarbon, is close to 100% with CufTi02 catalysts in presence or not of SO2 (Figure 4). With Cu/Zr02 SO2 inhibits decane oxidation below 640 K. At 640 K a conversion of about 60% is observed in both the presence or absence of additive and an acceleration of oxidation is noticed at higher temperatures. 

Hydrogen sulfide in the air is oxidized at a relatively slow rate by molecular oxygen (02) but at a much faster rate by hydroxide (OH) radicals, forming the sulfhydryl radical and ultimately sulfur dioxide or sulfate compounds (Hill 1973 NSF 1976). Sulfur dioxide and sulfates are eventually removed from the atmosphere through absorption by plants and soils or through precipitation (Hill 1973). 

Mathur and Thodos Chem. Eng. Sci., 21 (1191), 1966] used the initial rate approach to analyze the kinetics of the catalytic oxidation of sulfur dioxide. They summarized the most plausible rate controlling steps for the reaction as ... 

Eklund, R.B. (1956), The Rate of Oxidation of Sulfur Dioxide with a Commercial Vanadium Catalyst, Almgvist and Wik-sell, Stockholm. 

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