Top Catal (2009) 52:18211825 DOI 10.

1007/s11244-009-9356-4

ORIGINAL PAPER

Two Reaction Pathways in the Selective Catalytic Reduction of NOx by C6H14 Over AgAl2O3 with H2 Co-Feeding
A. Yu. Stakheev P. V. Pributkov S. Dahl I. Gekas G. N. Baeva G. O. Bragina N. S. Telegina

Published online: 15 July 2009 Springer Science+Business Media, LLC 2009

Abstract The NOx reduction with n-C6H14 was studied over a 3% Ag/Al2O3 catalyst in the presence of hydrogen. The catalyst performance was evaluated by varying the H2 concentration from 0 to 1600 ppm and by comparing the results with blank runs in which an empty reactor with no catalyst was used. Two distinct reaction pathways were revealed: one at low-temperature (Treact \ 370 C) and another one at high-temperature (Treact [ 370390 C). Co-feeding of H2 promotes the reaction within the 150360 C interval. The high-temperature pathway (Treact [ 370390 C) seems to be almost independent of hydrogen co-feeding. The homogeneous gas-phase NOx oxidation initiated by NO presumably plays an important role in this high-temperature pathway. Keywords H2 effect SCR NOx deNOx Ag/Al2O3 Reaction mechanism Gas-phase reaction

1 Introduction Selective catalytic reduction of NOx by hydrocarbons (HC-SCR) is one of the most promising and straightforward method for the removal of NOx emissions from the exhaust gas of diesel powered vehicles. Among a large number of different materials that have been proposed and
A. Yu. Stakheev (&) P. V. Pributkov G. N. Baeva G. O. Bragina N. S. Telegina Zelinsky Institute of Organic Chemistry, Leninsky Pr. 47, 119991 Moscow, Russia e-mail: st@ioc.ac.ru S. Dahl I. Gekas Haldor Topsoe A/S, Nymllevej 55, P.O. Box 213, 2800 Lyngby, Denmark

tested for HC-SCR, Ag/Al2O3 has shown high activity both in laboratory and in full-scale tests. The discovery that adding small amounts of H2 could dramatically improve the performance of Ag/Al2O3 catalysts in the HC-SCR reaction has resulted in a renewed interest in these catalysts [1, 2]. However, in most investigations of the hydrogen effect, relatively high H2 concentrations have been used (e.g., H2 concentration of 10004000 ppm [3], 5000 ppm [4], 500 7200 ppm [5, 6], 5000 ppm: 1% [7], 1% [8, 9]). Therefore, experimental data on Ag/Al2O3 performance and a possible reaction mechanism within a practical range of H2 concentrations are scarce. In this study particular attention has been paid to the hydrogen role in hydrocarbon activation. In order to reveal NOx and H2 functions, we compared C6H14 conversion using feed mix of various compositions (300 ppm NOx and 0 ppm H2, 300 ppm NOx and 1000 ppm H2, NOx over Ag/Al2O3 and in empty reactor (gas-phase activation). Additional information was obtained by analysis of SCR selectivity in terms of number of NOx molecule reduced/ number of C6H14 molecules consumed within wide range of temperature (200500 C) and hydrogen partial pressure (01600 ppm).

2 Experimental 2.1 Catalyst Preparation An Ag/Al2O3 catalyst containing 2.3 wt% Ag was prepared by the solgel method according to a procedure similar to that described in the literature [10]. Aluminum isopropoxide (11.56 g) was dissolved in 100 ml of distilled water at 9095 C. The mixture was continuously stirred for 1 h. Then, 3.9 ml of 1 M HNO3 was added, and the mixture

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was stirred for 30 min. For Ag loading, the corresponding amount of AgNO3 was added dropwise to stirred alumina sol for 1 h. After that, water was removed on a rotary evaporator, and the product was dried overnight at 120 C and calcined at 600 C. The catalyst thus prepared was characterized by XPS, BET, and atomic absorption spectroscopy (AAS). BET surface area was 240 m2/g. Surface Ag/Al atomic ratio was found to be c.a. 0.013, which is approximately 1.2 times higher compared to that expected from AAS results. 2.2 Catalytic Tests The catalyst activity was tested in a xed-bed ow reactor using the feed gas containing 300 ppm NOx, 170 and 280 ppm C6H14, 01600 ppm H2, 7% O2, 9% H2O, 10% CO2. Catalytic tests were carried out at GHSV = 70 000 h-1 using the catalyst pellets of 0.40.8 mm in size. Reaction products were analyzed by an Eco Physics CLD 822 chemiluminescent NOx analyzer and a FTIR gas analyzer Gasmet (Temet Instruments Dx-4000n).

3 Results and Discussion Temperature dependencies of NOx conversion in the presence of different H2 concentrations are displayed in Fig. 1. NOx conversion in the absence of hydrogen is also given for comparison. As it can be seen, in the absence of hydrogen detectable NO reduction starts at temperatures between 350 and 370 C and demonstrates a conventional sigma-shaped light-off prole as the temperature is raised. Maximal NOx reduction is approached at *420450 C. Below 350 C NOx conversion is negligible without hydrogen added. Addition of 290 ppm H2 results in a
100%

signicant improvement of NOx conversion within the temperature range between 120 and 370 C. Accordingly, NOx conversion progressively improves with increasing H2 content from 290 to 1600 ppm. At 250 C the reaction order in H2 is approximately 0.35 and increases to *0.45 when the C6H14 concentration increases to 280 ppm. These results are in a good agreement with the data reported by Arve [9]. Above 370390 C the hydrogen effect seems to be minor and the temperature dependences of NOx conversion in the course of SCR with and without H2-cofeeding are essentially identical (Fig. 1). Analysis of the temperature dependence of the C6H14 conversion (Fig. 2) revealed a similar trend. In the absence of hydrogen we do not observe a detectable conversion below *350 C. Above this temperature conversion rapidly starts at the same temperature as NOx conversion and increases in parallel with NOx conversion. Upon addition of H2 (even as small as 290 ppm) C6H14 conversion is signicantly enhanced at a reaction temperature below 350 C. This H2-induced enhancement increases along with increasing H2 concentration. Evidently oxidation of C6H14 is associated with the NO reduction in both, H2-assisted and H2-free HC-SCR. These data are in a good agreement with the reaction mechanism proposed by Meunier and Arve [11, 12]. It is noteworthy that above 370390 C the hydrogen effect appears to vanish and C6H14 conversion follows the same temperature dependence as that in the absence of hydrogen. This tendency is particularly evident at low hydrogen content (290650 ppm). Tentatively, we can ascribe this effect to a depletion of reaction mixture in hydrogen along the catalyst bed, which should be more pronounced at low H2 concentration. As mentioned above, an analogous tendency can be noted for NOx conversion (Fig. 1).
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Fig. 1 Effect of H2 concentration on the temperature dependence of NOx conversion. Conditions: GHSV = 70 000 h-1, 300 ppm NOx, 170 ppm C6H14, 7% O2, 9% H2O, 10% CO2. H2 concentration = 01600 ppm

Fig. 2 Effect of H2 concentration on the temperature dependence of C6H14 conversion. Conditions: GHSV = 70 000 h-1, 300 ppm NOx, 170 ppm C6H14, 7% O2, 9% H2O, 10% CO2. H2 concentration = 01600 ppm

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300ppm NO, 1000ppm H 2 300ppm NO, 0ppm H2 1000ppm H2, 0ppm NO 0ppmNO, 0ppm H2
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Fig. 3 Effect of reaction mix composition on homogeneous gasphase C6H14 oxidation (without catalyst, in empty quartz reactor). Reaction conditions: Feed gas composition: 300/0 ppm NO, 7% O2, 9% H2O, 280 ppm C6H14, 1000/0 ppm H2, 10% CO2, balance with N2

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In order to gain better insight into the impact of hydrogen on C6H14 activation two sets of experiments were carried out. In the rst set we studied C6H14 conversion in the gas-phase using an empty reactor without catalyst load. The overall ow rate and composition of the reaction mixture were kept identical to that used for measuring the SCR activity. Additionally we measured C6H14 conversion upon removing hydrogen, NO, and both components out of reaction mix. In the absence of H2 and NO in the reaction mixture the C6H14 oxidation is essentially negligible within the temperature range of C6H14-SCR (Fig. 3). When H2 is switched to the reaction feed, we observe a minor improvement of the C6H14 conversion, though it does not exceed *17% at 500 C. However C6H14 conversion increases sharply when NO was switched into the feed gas. Addition of hydrogen to the NO-containing reaction mixture seems to slightly enhance C6H14 conversion. However this effect is minor. The data obtained clearly indicates that NOx promotes C6H14 conversion within the temperature range of C6H14-SCR. It is important that nitric oxide promotes C6H14 oxidation via a catalytic mechanism, since no NOx conversion was observed in the empty reactor. It is conceivable that gasphase hexane oxidation, which is initiated by NO, involves free-radical steps as suggested by several authors [13, 14]. On the other hand, the effect of hydrogen on gas-phase homogeneous hexane oxidation is found to be minor. In the second set of experiments we revealed the effect of switching 300 ppm NO and 1000 ppm H2 into and out of the SCR feed stream over AgAl2O3 catalyst (Fig. 4). In the absence of H2 and NO the temperature curve of C6H14 conversion is shifted toward higher temperature by *200 C as compared to that observed in the course of the SCR process. Switching 1000 ppm H2 into the feed stream

Fig. 4 C6H14 conversion over Ag/Al2O3 catalyst under different reaction conditions within a broad temperature range of 100700 C. Reaction conditions: GHSV = 70 000 h-1, feed gas composition: 300/0 ppm NO, 7% O2, 9% H2O, 280 ppm C6H14, 1000/0 ppm H2, 10% CO2, balance with N2

results in a minor improvement of C6H14 conversion, though the effect of hydrogen is not pronounced. When 300 ppm NOx is switched into the feed stream (conventional C6H14-SCR without H2-cofeeding), the C6H14 conversion is drastically enhanced. It is noteworthy that the light-off temperature of C6H14 conversion is essentially identical to that observed in gas-phase C6H14 oxidation upon addition of NO (see Fig. 3). The corresponding dependence is shown in Fig. 4 for comparison. This coincidence presumably indicates that gas-phase C6H14 oxidation initiated by NO plays an important role in conventional C6H14-SCR without H2-cofeeding. On the other hand, C6H14 conversion was notably enhanced over AgAl2O3 as compared to gas-phase C6H14 oxidation (by *20%). When 1000 ppm H2 is switched into feed stream in addition to 300 ppm NOx (H2-assisted C6H14-SCR) the C6H14 conversion is drastically improved within the low-temperature range (Treact. \ 370390 C). Above *380 C one can observe a bending of the temperature dependence of hexane conversion and the further temperature dependence of C6H14 conversion follows that observed in the conventional C6H14-SCR (without H2-cofeeding). Only a minor improvement of the C6H14 conversion upon H2-cofeeding can be discerned. It is informative to analyze the temperature dependence of the selectivity of C6H14-SCR in terms of number of NOx molecules reduced/number of C6H14 molecules consumed (Fig. 5). Evidently at Treact [ 400 C the temperature dependence of the SCR selectivity with H2 co-feeding follows the same trend as traditional SCR (without H2 addition). However with decreasing reaction

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1600 ppm H2 2

ppm NOx conv./ ppm C 6H14 conv.

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Fig. 5 Temperature dependence of C6H14-De-NOx selectivity at concentrations. Reaction conditions: different H2 GHSV = 70,000 h-1, feed gas composition: 300 ppm NO, 7% O2, 9% H2O, 170 ppm C6H14, 01600 ppm H2, 10% CO2, balance with N2

temperature below *400 C the selectivity of H2-assisted HC-SCR increases sharply in contrast to traditional SCR. The data obtained allow us to reveal several observations important for clarifying overall reaction mechanism of H2-assisted HC-SCR. (1) In the absence of NOx the hexane oxidation is negligible within a temperature range of effective C6H14-SCR (Fig. 4) and becomes signicant only at Treact. [ 500 C. The silver catalyst demonstrates very low activity in C6H14 oxidation, since the temperature dependencies over AgAl2O3 (Fig. 4) and upon homogeneous gas-phase oxidation in the empty reactor (Fig. 3) are similar. (2) Addition of 1000 ppm hydrogen into feed stream (in the absence of NOx) results in a minor improvement of the C6H14 oxidation (Fig. 4). However this process seems to be negligible within the temperature range of H2-assisted HCSCR (150500 C). Apparently, activation of C6H14 through direct partial oxidation over reduced Ag(0), as proposed by Brosius [15], is minor at least at low H2 concentration (1000 ppm). (3) Upon switching 300 ppm NO into the reaction mixture (without H2 co-feeding) C6H14 conversion is signicantly enhanced in both homogeneous gas-phase C6H14-oxidation (Fig. 3) and C6H14-SCR (Fig. 4). Very similar light-off temperatures in both processes indicate that a homogeneous gas-phase C6H14-oxidation may play an important role in C6H14-SCR at Treact. [ 370390 C, as it was suggested by several authors [13, 14, 16]. It is noteworthy that the homogeneous gas-phase oxidation of

C6H14 is initiated by NO, but no NOx reduction is observed. AgAl2O3 is required for accomplishment of the reaction by NO reduction. (4) Addition of 1000 ppm H2 into feed stream containing 300 ppm NO signicantly improves C6H14 conversion at 150380 C (Fig. 4). It is important that the improvement is observed only when NO is present in the feeding mixture. This nding implies that upon H2-cofeeding C6H14 conversion at 150380 C does not proceed independently, but appears to be a part of the overall C6H14DeNOx process, which is in general agreement with a reaction mechanism originally proposed by Meunier et al. and more recently modied by Eranen et al. and Breen et al. [6, 11, 17]. In the absence of NO, the hydrogen effect on C6H14 conversion was found to be minor. (5) The selectivity of the SCR process with H2-cofeeding is similar to that in the absence of H2 within temperature range above 380400 C (Fig. 5). This may imply a similar reaction mechanism above the light-off temperature where gas-phase homogeneous oxidation occurs. However below 380400 C the selectivity of the H2-assisted SCR is increased with decreasing reaction temperature unlike in contrast to that observed for conventional SCR without H2cofeeding. Presumably this is indicative of a different reaction mechanism in the H2-assisted HC-SCR, which became predominant below 380400 C. Since the reaction selectivity depends only slightly on the H2 concentration (within 2901600 ppm range), one can suggest that hydrogen is not directly involved as a reductant in SCR. Rather the role of hydrogen may consist in the removal of strongly bound silver nitrates and cyanide species, and the formation of nitrite and nitro species, which are much more reactive than nitrato species and more readily able to activate the hydrocarbon [5, 15, 18, 19].

4 Conclusion The data obtained are in accordance of two distinct reaction pathways: one at low-temperature (Treact \ 370 C) and another one at high-temperature (Treact [ 370 390 C). Co-feeding of H2 promotes the reaction within the 150360 C interval. The low-temperature pathway proceeds with high efciency in terms of C6H14 consumption: the efciency of the reaction is *25 mol NOx,conv/ mol C6H14,conv and increases with increasing reaction temperature. The high-temperature pathway (Treact [ 370 390 C) seems to be almost independent of hydrogen co-feeding and NOx conversion remains essentially identical to that in conventional NOx SCR (in the absence of hydrogen co-feeding). The selectivity of the high-temperature pathway is signicantly lower and the efciency of the reaction decreases to *10.8 mol NOx,conv/

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1825 7. Richter M, Bentrup U, Eckelt R, Schneider M, Pohl M-M, Fricke R (2004) Appl Catal B 51:261 8. Eranen K, Klingstedt F, Arve K, Lindfords L-E, Murzin DYu (2004) J Catal 227:327 9. Arve K, Backman H, Klingstedt F, Eranen K, Murzin DYu (2007) Appl Catal B 70:65 10. Yoldas BE (1975) Am Ceram Soc Bull 54:286 11. Meunier FC, Breen JP, Zuzaniek V, Olsson M, Ross JRH (1999) J Catal 187:493 12. Arve K, Backman H, Klingstedt F, Eranen K, Murzin DYu (2006) Appl Catal A Gen 303:96 13. Lukyanov DB et al (1996) J Catal 163:447 14. Cheung CC, Kung MC (1999) Catal Lett 61:131 15. Brosius R, Arve K, Groothaert MH, Martens JA (2005) J Catal 231:344 16. Smits RHH, Iwasawa Y (1995) Appl Catal B 6:L201 17. Eranen K, Klingstedt F, Arve K, Lindfords L-E, Murzin DYu (2004) J Catal 227:328343 18. Shimizu K, Shibata J, Satsuma A (2006) J Catal 239:402 19. Bentrup U, Richter M, Fricke R (2005) Appl Catal B 55:213

mol C6H14,conv when the reaction temperature increases to above 380400 C. Homogeneous gas-phase NOx oxidation initiated by NO presumably plays an important role in the mechanism at high temperature (Treact [ 370390 C).

References
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