SCR process

Fig. 7. NO reduction using selective catalytic recovery (SCR) (a) basic principles of the SCR process where represent gas particles and (b) effect of...

Reactions. The SCR process is termed selective because the ammonia reacts selectively with NO at temperatures >232° C in the presence of excess oxygen (44). The optimum temperature range for the SCR catalyst is determined by balancing the needs of the redox reactions. 

In the SCR process, ammonia, usually diluted with air or steam, is injected through a grid system into the flue/exhaust stream upstream of a catalyst bed (37). The effectiveness of the SCR process is also dependent on the NH to NO ratio. The ammonia injection rate and distribution must be controlled to yield an approximately 1 1 molar ratio. At a given temperature and space velocity, as the molar ratio increases to approximately 1 1, the NO reduction increases. At operations above 1 1, however, the amount of ammonia passing through the system increases (38). This ammonia sHp can be caused by catalyst deterioration, by poor velocity distribution, or inhomogeneous ammonia distribution in the bed. 

Selective catalytic reduction (SCR) is cmrently the most developed and widely applied FGT technology. In the SCR process, ammonia is used as a reducing agent to convert NO, to nitrogen in the presence of a catalyst in a converter upstream of the air heater. The catalyst is usually a mixture of titanium dioxide, vanadium pentoxide, and hmgsten trioxide. SCR can remove 60-90% of NO, from flue gases. Unfortunately, the process is very expensive (US 40- 80/kilowatt), and the associated ammonia injection results in an ammonia slip stream in the exhaust. In addition, there are safety and environmental concerns associated with anhydrous ammonia storage. 

When a 1 1 mixture of NO and NO2 (i.e., NO2/NOx=0,5) is fed to the SCR reactor at low temperature (200 °C) where the thermodynamic equilibrium between NO and NO2 is severely constrained by kinetics, the NO2 conversion is much greater than (or nearly twice) the NO conversion for all three catalysts. This observation is consistent with the following parallel reactions of the SCR process [6] Reaction (2) is the dominant reaction due to its reaction rate much faster than the others, resulting in an equal conversion of NO and NO2. On the other hand, Reaction (3) is more favorable than Reaction (1), which leads to a greater additional NO2 conversion by Reaction (3) compared with the NO conversion by Reaction... 

Understanding the kinetics of the SCR process helps greatly in developing new and better catalysts. For efficient operation, one important issue is to maximize NO con-... 

Figure 10.15. Catalytic cycle for the SCR process over acidic V -OH sites and redox V=0 sites. [Adapted from N.-Y. Topsoe, Science 26S (1994) 1217.]...

The SCR process would be even more attractive if ammonia could be avoided. Numerous investigations have been performed using more easily handled hydrocarbons, but no process has yet been found that can compete with the ammonia (or... 

Describe the SCR-process for the removal of NOx from stationary power plants. Which reactants are usually used for the SCR process ... 

From the results discussed above as well as from the literature data [5-10,12-14] it follows that an important role of O2 in the SCR process is to convert NO into NOj. The latter then initiates methane oxidation into CO, and is itself reduced into NO and N2. Both NO, and O2 may participate in CH4 oxidation (Fig. 1B) and the ratio between the rates of these competitive oxidation reactions will be critical for the selectivity of the SCR process. Hence, the absolute rates of CH4 oxidation by Oj were compared with those occurring in the SCR process. The rates of these reactions were determined under different reaction conditions (using the... 

Fig. IB shows that at all temperatures the rate of CH4 oxidation by O2 alone is lower than the rate of CH4 oxidation during the SCR reaction, e.g., at 400 C with CoZSM-5 catalyst the difference between these rates is about 10 times. With increasing temperature this difference diminishes due to the different activation energies of these reactions (Fig. 2). At high temperatures these rates become comparable (in considering Figs. IB and 2 recall that the rate of CH4 oxidation during the SCR process includes a contribution from the rate of CH4 oxidation by O2 alone). These data suggest that below 500 C O2 does not compete effectively with NO, for CH4, but that at high temperatures such a competition must exist. The data of Table I support this view. At ADO C an increase in 62 concentration results in an increase in conversions of both NO into N2 and CH4 into CO2. At the same time, variation of Oj concentration by a factor of 13 has practically no effect on the...

In conclusion, although at present time we cannot unambiguously define the reaction steps leading to Nj formation, we have attempted to suggest steps that seem to be reasonable and hope that our proposals will be useful for further investigation of the detailed mechanism of the SCR process. 

For similar motivations, there are limited incentives to develop an alternative SCR process for stationary sources based on methane (CH4-SCR) or other HCs, or based on NTP technologies, if not for specific, better applications. The situation is instead quite different for mobile sources, and in particular for diesel engine emissions. The catalytic removal of NO under lean conditions, e.g. when 02 during the combustion is in excess with respect to the stoichiometric one (diesel and lean-burn engines, natural gas or LPG-powered engines), is still a relevant target in catalysis research and an open problem to meet future exhaust emission regulations. 

Figure 1.2. Schematic flow diagram of SCR process and of the trays and monoliths of the SCR reactor.

Catalyst cost constitutes 15-20% of the capital cost of an SCR unit therefore, it is essential to operate at temperatures as high as possible to maximize space velocity and thus minimize catalyst volume. At the same time, it is necessary to minimize the rate of oxidation of S02 to S03, which is more temperature sensitive than the SCR reaction. The optimum operating temperature for the SCR process using titanium and vanadium oxide catalysts is about 38CM180oC. Most installations use an economizer bypass to provide flue gas to the reactors at the desired temperature during periods when flue gas temperatures are low, such as low-load operation. 

Low-temperature activity promotion is an issue in mobile (diesel) applications, but may not be a critical issue in several stationary applications, apart from those where the temperature of the emissions to be treated is below 200°C (for example, when a retrofitting SCR process must be located downstream from secondary exchangers, or in the tail gas of expanders in a nitric acid plant). In the latter cases, a plasmacatalytic process [91] could be interesting. In the other cases, the use of NTP together with the SCR catalyst is not economically viable. However, the synergetic combination of plasma and catalysts has been shown to significantly promote the conversion of hazardous chemicals such as dioxins [92], Although this field has not yet been explored, it may be considered as a new plasmacatalytic SCR process for the combined elimination of NO, CO and dioxins in the emissions from incinerators. 

Montanari el al., for example, studied a Co—H-MFI sample through FT-IR spectroscopy of in situ adsorption and coadsorption of probe molecules [o-toluonitrile (oTN), CO and NO] and CH4-SCR process tests under IR operando conditions. The oTN adsorption and the oTN and NO coadsorption showed that both Co2+ and Co3+ species are present on the catalyst surface. Co3+ species are located inside the zeolitic channels while Co2+ ions are distributed both at the external and at the internal surfaces. The operando study showed the activity of Co3+ sites in the reaction. The existence of three parallel reactions, CH4-SCR, CH4 total oxidation and NO to NOz oxidation, was also confirmed. Isocyanate species and nitrate-like species appear to be intermediates of CH4-SCR and NO oxidation, respectively. A mechanism for CH4-SCR has been proposed. On the contrary, Co2+ substitutional sites, very evident and predominant in the catalyst, which are very hardly reducible, seemed not to play a key role in the SCR process [173],... 

Madia, G., Elsener, M., Koebel, M. et al. (2002) Thermal stability of vanadia-tungsta-titania catalysts in the SCR process, Appl. Catal. B, 39, 181. 

SCR systems at stationary diesel engines profit from the high exhaust gas temperatures of about 350-400 C, caused by the usually constant high load operation conditions of the diesel engine. In this temperature window nearly all known SCR catalysts are very active. Moreover, weight and size of the exhaust gas catalyst are usually not strictly limited, which results in a good NO, reduction efficiency (DeNOJ. However, DeNO, is not the only criterion for an SCR catalyst. Further requirements are excellent selectivities regarding NO and urea/ammonia as well as low ammonia slip, which is an undesired secondary emission of the SCR process. Therefore, all SCR catalysts exhibit surface acidity, which is necessary to store ammonia on the catalyst surface and, thus, to prevent ammonia slip. 

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