56

SELECTIVE CATALYTIC REDUCTION OF NO AND NO2 AT LOW TEMPERATURES

M. Koebel, G. Madia, M. Elsener A feed gas containing both NO and NO2 can react with NH3 according to two different reaction pathways at low temperatures: The fast SCR reaction has a positive and the ammonium nitrate reaction has a negative temperature coefficient. The deposition of ammonium nitrate in the pores of the catalyst may lead to its temporary deactivation.

INTRODUCTION

2 NH3 + 2 NO2

NH4NO3+ N2 + H2O

(4)

Forthcoming European legislation pertaining to heavy duty diesel engines calls for the simultaneous reduction of both particles and NOx emissions. It is now generally assumed, that the EURO 4 emission standards proposed for the year 2005 will be no longer feasible by primary measures alone but will require additional aftertreatment techniques. A possible technique to reduce NOx in lean exhaust is SCR (selective catalytic reduction). Due to toxicological and safety considerations urea is preferred over ammonia as a selective reducing agent. Urea may be regarded as a solid storage compound for ammonia, which is the active agent in both cases. Urea SCR has been investigated by us and others in the last years as the most promising technique to reduce NOx in the exhaust of mobile diesel engines [1, 2]. The main effort is directed to heavy duty engines used in trucks, but attempts are also made to develop a suitable technique for diesel passenger cars. The main reaction of SCR with ammonia is: 4 NH3 + 4 NO + O2
4 N2 + 6 H2O

In the following we report some basic experiments of this highly interesting chemistry. The practical issue of these experiments is to find the lowest possible temperature limit of the fast SCR reaction for the practical application of the process.

EXPERIMENTAL

The experiments were performed in a flow-trough reactor (gas flow 300 lN/h). The base feed gas used was adapted to a typical diesel exhaust gas, containing 10 % O2 and 5 % H2O with balance N2. NO and NO2 were added at various proportions to compose NOx and NH3 was used as reducing agent. The gases at the reactor outlet were analysed by means of an FTIR spectrometer. A ternary catalyst composed of TiO2, V2O5, WO3 was used as a powder and as a monolithic sample. Further details have been given in [5].

RESULTS

(1)

3.1 Standard and fast SCR at T>200C

Fig. 1 shows typical results for a monolithic sample obtained at 200C by varying the ratio of NO2/NOx. The performance plot is obtained by varying the addition of NH3 for the fixed concentration of 1000 ppm NOx and measuring the resulting slip (efflux) of NH3 at the reactor outlet.
100 90 80 70 NH3 [ppm] 60 50 40 30 20 10 0 0 10 20 30 40 50 60 70 80 90 100 DeNOx [%] 0% NO2 10% NO2 20% NO2 30% NO2 40% NO2 50% NO2

On the typical SCR catalysts based on TiO2-WO3V2O5 the "standard SCR" reaction has a useful rate in the temperature range 250-450C. However, at lower temperatures, the kinetics of this reaction are too slow for the practical application in a mobile SCR system. In a mobile system, only limited catalyst volumes are acceptable and this calls for a higher rate of the reaction. In order to increase the rate of NOx conversion it has been proposed to utilise the fact that the reaction rate of an equimolar mixture of NO and NO2 is much higher [1] ("fast SCR"): 4 NH3 + 2 NO + 2 NO2
4 N2 + 6 H2O

(2)

In a practical system the additional NO2 is produced by an oxidation precatalyst (Pt-based) upstream of the SCR catalyst. NO2 fractions above 50 % of total NOx should be avoided because excess NO2 can only react in a third slower reaction: 4 NH3 + 3 NO2
3.5 N2 + 6 H2O

(3)

It is also well known from the manufacturing process of nitric acid that NO2 and NH3 may form solid ammonium nitrate at low temperatures [3,4]. The reaction mechanism involves the dimerization of NO2 and the overall equation is:

Fig. 1: Performance of monolithic catalyst sample at T = 200C for various ratios of NO2/NOx at GHSV = -1 52000 h . Base feed + 1000 ppm NOx.

57 In the practical application only values of DeNOx at low NH3-slip are of interest. It can be seen that the DeNOx for an NH3 slip of 10 ppm increases from 20 % for pure NO to 95 % with a 1:1 mixture NO + NO2. Expressed in terms of a first order rate law this corresponds to an increase by a factor of 13. The beneficial effect of NO2 may also be observed at higher temperatures, although in a less sensational manner due to the increasing rate of the standard SCR reaction. On the other hand, NO2 fractions above 50 % lead to a decrease of the catalyst performance.

3.3 Behaviour between 150 and 200C

Figure 3 shows the behaviour of both powder and monolithic catalyst samples with a 1:1 NO-NO2 mixture in the base feed gas in the temperature range 150-200C. Due to the fact that the fast SCR reaction (2) consumes equimolar amounts of NO and NO2, but the ammonium nitrate reaction NO2 only, the contributions of both reactions may be calculated. It can be seen that the ammonium nitrate reaction contributes increasingly with decreasing temperature to the total DeNOx. The fast SCR reaction follows an opposite trend.

3.2 Experiment at T=150C

Below about 200C the formation of ammonium nitrate (solid or liquid) according to reaction (4) must be considered. On a powder sample at 150C this is practically the exclusive reaction. Fig. 2 shows the result of a typical experiment with a monolithic sample which is first subjected 30 minutes to a base feed with 1000 ppm each of NO2 and NH3. It may be seen that during this time a considerable drop of the NH3 concentration occurs over the catalyst, the drop of NO2 being practically equal (not shown). Ammonia and NO2 are consumed according to the ammonium nitrate reaction (4).
1000
NH3 consumed in the reaction = 0.002925 mol NH3 desorbed = 0.001636 mol HNO3 desorbed = 0.00109 mol blank NH3 = 0.00031 mol

100 Total DeNOx and contributions [%] 90 80 70 60 50 40 30 20 10 0 140 150 160 170 T [C] 180 190 200 Monolith, total Monolith, fast SCR Monolith, NH4NO3 Powder, total Powder, fast SCR Powder, NH4NO3

500

800 Concentration [ppm]

NH3

stop feed

400

600

300 T [C]

400 NH3 200 NH3 blank 0 0 20 40 60 time [min] 80 100 HNO3

200

Fig. 3: NO2 converted due to the fast SCR reaction (2) and ammonium nitrate reaction (4) and resulting total DeNOx 4
[1]

100

REFERENCES
E. Jacob et al., NOx-Verminderung fr Nutzfahrzeugmotoren mit Harnstoff-SCR-Kompaktsystemen (GD-KAT), 19. Intern. Wiener Motorensymposium. 07.-08.05.1998, FortschrittBerichte VDI, Reihe 12, Nr. 348, Bd. 1, 366-86. M. Koebel, M. Elsener, M. Kleemann, UreaSCR: A promising technique to reduce NOx emissions from automotive diesel engines, Catal. Today 2031, 1-11 (2000). A. Mearns, K. Ofosu-Asiedu, Ammonium nitrate formation at low concentration mixtures of oxides of nitrogen, ammonia and water vapour, J. Chem. Biotechnol. 34A, 350, (1984). A. Mearns, K. Ofosu-Asiedu, Kinetics of reaction of low concentration mixtures of oxides of Nitrogen and ammonia J. Chem. Biotechnol. 34A, 341. (1984). M. Koebel, M. Elsener, G. Madia, Reaction Pathways in the SCR Process with NO and NO2 at Low Temperatures, Ind. Eng. Chem. Res., in print. Gmelin, Handbuch der anorganischen Chemie, Ammonium, 8. Ed., Lieferung 1, 109 (1936).

0 120

Fig. 2: Efflux of NH3 and HNO3 behind monolithic catalyst sample. For details see text.
An important issue is the decomposition products resulting from a subsequent heat-up of the ammonium nitrate formed. The subsequent thermal decomposition experiment shows that the decomposition yields only ammonia and nitric acid. Within the experimental error and considering the blank adsorption of NH3, half the amount of each NH3 and NO2 adsorbed are released in the thermal decomposition experiment according to: NH4NO3
NH3 + HNO3

[2]

[3]

(5)

[4]

It is well known from the literature [6] that pure ammonium nitrate can also decompose into N2O and water according to: NH4NO3
N2O + 2 H2O

(6)

[5]

In the above experiment no N2O could be detected. Only if the experiment is performed without water in the feed, some N2O ( 10 %) is formed in the subse quent thermal decompostion experiment.

[6]