Catalyst, SO2 oxidation

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Chapter 7 also shows that V, K, Na, Cs, S, O, Si02 catalyst is a key ingredient in ensuring rapid, efficient SO2 oxidation. Without catalyst, SO2 oxidation is slow at temperatures where the oxidation is thermodynamically efficient. 

Effect of gas recycle on first catalyst SO2 oxidation efficiency... 

These catalysts contained promoters to minimise SO2 oxidation. Second-generation systems are based on a combined oxidation catalyst and particulate trap to remove HC and CO, and to alleviate particulate emissions on a continuous basis. The next phase will be the development of advanced catalysts for NO removal under oxidising conditions. Low or 2ero sulfur diesel fuel will be an advantage in overall system development. 

The oxidation catalyst (OC) operates according to the same principles described for a TWO catalyst except that the catalyst only oxides HC, CO, and H2. It does not reduce NO emissions because it operates in excess O2 environments. One concern regarding oxidation catalysts was the abiUty to oxidize sulfur dioxide to sulfur trioxide, because the latter then reacts with water to form a sulfuric acid mist which is emitted from the tailpipe. The SO2 emitted has the same ultimate fate in that SO2 is oxidized in the atmosphere to SO which then dissolves in water droplets as sulfuric acid. 

Performance criteria for SCR are analogous to those for other catalytic oxidation systems NO conversion, pressure drop, catalyst/system life, cost, and minimum SO2 oxidations to SO. An optimum SCR catalyst is one that meets both the pressure drop and NO conversion targets with the minimum catalyst volume. Because of the interrelationship between cell density, pressure drop, and catalyst volume, a wide range of optional catalyst cell densities are needed for optimizing SCR system performance. 

A related approach is to interface an industrial promoted catalyst with a solid electrolyte (Fig. 12.2). In this case the bulk of the commercial catalyst must be conductive. This concept has been already demonstrated for the case of NH3 synthesis on Fe-based promoted commercial catalysts (BASF S6-10 RED)16 and for the case of SO2 oxidation on V2O5-K2S2O7 based catalysts (Haldor-Topsoe VK-58).17... 

The vanadium content of some fuels presents an interesting problem. When the vanadium leaves the burner it may condense on the surface of the heat exchanger in the power plant. As vanadia is a good catalyst for oxidizing SO2 this reaction may occur prior to the SCR reactor. This is clearly seen in Fig. 10.13, which shows SO2 conversion by wall deposits in a power plant that has used vanadium-containing Orimulsion as a fuel. The presence of potassium actually increases this premature oxidation of SO2. The problem arises when ammonia is added, since SO3 and NH3 react to form ammonium sulfate, which condenses and gives rise to deposits that block the monoliths. Note that ammonium sulfate formation also becomes a problem when ammonia slips through the SCR reactor and reacts downstream with SO3. 

Catalysts include oxides, mixed oxides (perovskites) and zeolites [3]. The latter, transition metal ion-exchanged systems, have been shown to exhibit high activities for the decomposition reaction [4-9]. Most studies deal with Fe-zeolites [5-8,10,11], but also Co- and Cu-systems exhibit high activities [4,5]. Especially ZSM-5 catalysts are quite active [3]. Detailed kinetic studies, and those accounting for the influence of other components that may be present, like O2, H2O, NO and SO2, have hardly been reported. For Fe-zeolites mainly a first order in N2O and a zero order in O2 is reported [7,8], although also a positive influence of O2 has been found [11]. Mechanistic studies mainly concern Fe-systems, too [5,7,8,10]. Generally, the reaction can be described by an oxidation of active sites, followed by a removal of the deposited oxygen, either by N2O itself or by recombination, eqs. (2)-(4). 

The evaluation of carriers and catalyst compositions showed that significantly higher SO2 oxidation activity could be achieved with Cs as a promoter under the operating conditions downstream the intermediate absorption tower as demonstrated by the results in Table 1, where the activity compared to the standard product is increased by more than a factor 2. This was clearly sufficient for the introduction of VK69 to the market as a new sulphuric acid catalyst. The activity results for different melt compositions were used to optimise the vanadium content and the molar ratios of K/V, Na/V. and Cs/V. However, the choice of Cs/V was not only a question of maximum activity, because of the significant influence of the Cs content on the raw material costs (the price of caesium is 50-100 times the price of potassium on a molar basis). Here, the economic benefits obtained by the sulphuric acid producer by the marginal activity improvement at high Cs content also had to be taken into account. 

Figure 13.2 Dependence of the intrinsic kinetic constant kc ofde-NO, and SO2 oxidation reactions (full squares and circles, respectively) on the V content of the catalyst. T = 350 °C, fede-NO, (Nmh ) fesOi-SOi (s )- Adapted from ref. [28]...

The catalyst must be designed to handle the abrasive environment where catalyst hnes are always present in the flue gas yet still perform with a low pressure drop typically below 5 inches of water column. It must also maintain activity continuously for a 5 year cycle, yet be selective enough to limit undesirable reactions like SO2 oxidation. The catalyst must also be able to withstand periodic blasts of steam or pressurized air coming from the soot blower system found in many of the newer FCCU SCR units. 

An important feature of a reactor operating with reversing flows is a gradual decrease of temperature of the packed bed outlet that allows for higher conversion in an adiabatic catalyst bed than for steady-state performance of an exothermic reversible reaction such as SO2 oxidation or ammonia synthesis. Conventional operation can provide only the temperature rise along the adiabatic catalyst bed. 

The role of water in SO2 oxidation over activated carbon is to react with the S03 formed to yield sulfuric acid. This removes SO3 from the catalyst... 

The electrochemical reaction proceeds most effectively in the presence of a catalyst, and the nature of the catalyst can have a significant effect upon the electrode overpotentials. As a matter of convenience, all of the early work in the electrolyzer development used platinum as both the anode (SO2 oxidation electrode) and cathode (H2 generation electrode) catalyst. It was recognized, however, that although platinum might be a technically satisfactory catalyst for the cathode, it was only marginally suitable as the anodic catalyst. 

Fig. 7.5. Heatup path for gas descending the Fig. 7.1 catalyst bed. It begins at the feed gas s input temperature and 0% SO2 oxidized. Its temperature rises as S02 oxidizes. Maximum attainable S02 oxidation is predicted by the heatup path-equilibrium curve intercept, 69% oxidized at 893 K in this case. This low % SO> oxidized confirms that efficient SO-> oxidation cannot be obtained in a single catalyst bed. Multiple catalyst beds with gas cooling between must be used.

Fig. 7.8. Heatup paths, intercepts and cooldown paths for Fig. 7.6 converter. They are described in Section 7.5. Final % SO2 oxidation after Fig. 7.6 s three catalyst beds is -98%.

Fig. 10.2 shows a typical equilibrium % SO2 oxidized vs. temperature curve for the Fig. 10.1 catalyst bed. This chapter and Appendix D show how it is prepared. 

Fig. 11.4. Segment of catalyst bed showing level L for calculating % SO2 oxidized equivalent to 850 K.

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