Nitrogen oxides, catalytic reduction

Removal of NOx from stack gas presents some formidable problems. Possible approaches to NOx removal are catalytic decomposition of nitrogen oxides, catalytic reduction of nitrogen oxides, and sorption of NOx by liquids or solids. 

Process of selective catalytic reduction of nitrogen oxides by ammonia (SCR) involves injection of ammonia into a gas stream containing nitrogen oxides, then reduction of NOx by ammonia on the surface of a catalyst typically containing vanadium oxide on titania. The reactions involved are mildly exothermic (additional heat is required in most cases). Limits of the optimal process temperature, usually from 200 to 350°C, are dictated by catalyst activity at low temperatures and by the reaction selectivity at high temperatures. The NOj-containing gas flows often have low temperature and variable flow rates and concentrations. This combination of factors makes application of an RFR to NO reduction advantageous. One industrial unit for NO selective catalytic reduction was reported to operate in Russia [44], with ammonia water injection between two catalyst beds. 

TABLE 25-25 Advantages and Disadvantages of Selective Catalytic Reduction of Nitrogen Oxides... 

Selective Catalytic Reduction of Nitrogen Oxides The traditional approach to reducing ambient ozone concentrations has been to reduce VOC emissions, an ozone precurssor. In many areas, it has now been recognized that ehmination of persistent exceedances of the National Ambient Air Qnality Standard for ozone may reqnire more attention to reductions in the other ingredients in ozone formation, nitrogen oxides (NOJ. In such areas, ozone concentrations are controlled by NO rather than VOC emissions. 

Nitric Acid Plant - Nitrogen oxide levels should be controlled to a maximum of 1.6 kg/t of 100% nitric acid. Extended absorption and technologies such as nonselective catalytic reduction (NSCR) and selective catalytic reduction (SCR) are used to eontrol nitrogen oxides in tail gases. 

Reactions involving the catalytic reduction of nitrogen oxides are of major environmental importance for the removal of toxic emissions from both stationary and automotive sources. As shown in this section electrochemical promotion can affect dramatically the performance of Rh, Pd and Pt catalysts (commonly used as exhaust catalysts) interfaced with YSZ, an O2 ion conductor. The main feature is strong electrophilic behaviour, i.e. enhanced rate and N2 selectivity behaviour with decreasing Uwr and , due to enhanced NO dissociation. 

Emission control from heavy duty diesel engines in vehicles and stationary sources involves the use of ammonium to selectively reduce N O, from the exhaust gas. This NO removal system is called selective catalytic reduction by ammonium (NH3-SGR) and it is additionally used for the catalytic oxidation of GO and HGs.The ammonia primarily reacts in the SGR catalytic converter with NO2 to form nitrogen and water. Excess ammonia is converted to nitrogen and water on reaction with residual oxygen. As ammonia is a toxic substance, the actual reducing agent used in motor vehicle applications is urea. Urea is manufactured commercially and is both ground water compatible and chemically stable under ambient conditions [46]. 

It has been reported that titanium supported vanadium catalyst is active for ammonia oxidation at temperatures above 523 K [2,3]. Also, supported vanadium oxides are known to be efficient catalyst for the catalytic reduction of nitrogen oxides (NO ) in the presence of ammonia [4]. This work investigates the nanostructured vanadia/Ti02 for low temperature catalytic remediation of ammonia in air. 

Wet air pollution control (WAPC) devices are used to treat exhaust gases from stainless steel pickling operations, thereby generating wastewater, which are treated using the selective catalytic reduction (SCR) technology in which anhydrous ammonia is injected into the gas stream prior to a catalyst to reduce NO, to nitrogen and water. The most common types of catalysts are a metal oxide, a noble metal, or zeolite. 

These harmful effects of nitrogen oxides being known from several years, regulations in their emissions have been progressively introduced in most of the countries worldwide. Therefore, new technologies have been introduced to either limit their formation or convert them to N2. Among these technologies, the selective catalytic reduction (SCR) was the one which was most successfully developed. 

Abstract A review is provided on the contribution of modern surface-science studies to the understanding of the kinetics of DeNOx catalytic processes. A brief overview of the knowledge available on the adsorption of the nitrogen oxide reactants, with specific emphasis on NO, is provided first. A presentation of the measurements of NO, reduction kinetics carried out on well-characterized model system and on their implications on practical catalytic processes follows. Focus is placed on isothermal measurements using either molecular beams or atmospheric pressure environments. That discussion is then complemented with a review of the published research on the identification of the key reaction intermediates and on the determination of the nature of the active sites under realistic conditions. The link between surface-science studies and molecular computational modeling such as DFT calculations, and, more generally, the relevance of the studies performed under ultra-high vacuum to more realistic conditions, is also discussed. 

With the advance of three-way catalysis for pollution control, used mainly in automobile catalytic conversion but also for the purification of gas exhausts from stationary sources, a need has arisen to develop a basic understanding of the reactions associated with the reduction of nitrogen oxides on transition metal catalytic surfaces [1,2]. That conversion is typically carried out by using rhodium-based catalysts [3], which makes the process quite expensive. Consequently, extensive effort has been placed on trying to minimize the amount of the metal needed and/or to replace it with an alternatively cheaper and more durable active phase. However, there is still ample room for improvement in this direction. By building a molecular-level picture of theprocesses involved,... 

Less, but still significant, information is available on the surface chemistry of other nitrogen oxides. In terms of N20, that molecule has been shown to be quite reactive on most metals on Rh(110), for instance, it decomposes between 60 and 190 K, and results in N2 desorption [18]. N02 is also fairly reactive, but tends to convert into a mixed layer of adsorbed NO and atomic oxygen [19] on Pd(lll), this happens at 180 K, and is partially inhibited at high coverages. Ultimately, though the chemistry of the catalytic reduction of nitrogen oxide emissions is in most cases controlled by the conversion of NO. 

This review has highlighted the key contributions of modern surface science to the understanding of the kinetics and mechanism of nitrogen oxide reduction catalysis. As discussed above, the conversion of NO has been taken as the standard to represent other NOx, and CO has typically been used as the reducing agent in these studies. The bulk of the work has been carried out on rhodium and palladium surfaces, the most common transition metals used in three-way catalytic converters. 

Armor, J.N. (1995) Catalytic reduction of nitrogen oxides with methane in the presence of excess oxygen A review, Catal. Today, 26, 147. 

Matsumoto, S. (2000) Catalytic Reduction of Nitrogen Oxides in Automotive Exhaust Containing Excess Oxygen by NOx Storage-Reduction Catalyst, Cat. Tech., 4, 102. 

Devadas, M. (2006) Selective catalytic reduction (SCR) of nitrogen oxides with ammonia over Fe-ZSM5, PhD. Thesis No. 16524, ETH Zurich. 

Wichterlova, B., Sazama, P., Breen, J.P. et al. (2005) An in situ UV-vis and FTIR spectroscopy study of the effect of H2 and CO during the selective catalytic reduction of nitrogen oxides over a silver alumina catalyst, J. Catal. 235, 195. 

Martin, J.A., Yates, M., Avila, P. et al. (2007) Nitrous oxide formation in low temperature selective catalytic reduction of nitrogen oxides with V205/Ti02 catalysts, Appl. Catal. B... 

Broer, S. and Hammer, T. (2000) Selective catalytic reduction of nitrogen oxides by combining a non-thermal plasma and a V205-W03/Ti02 catalyst, Appl. Catal. B Env. 28, 101-11. 

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