Applied Catalysis B: Environmental 48 (2004) 95100

Continuous lean NOx reduction with hydrocarbons over dual pore system catalysts
Thomas Holma a,b , Anders Palmqvist a,b,c, , Magnus Skoglundh a,b , Edward Jobson a,c
b a Competence Centre for Catalysis, Chalmers University of Technology, SE-412 96 Gteborg, Sweden Department of Applied Surface Chemistry, Chalmers University of Technology, Kemivgen 10, SE-412 96 Gteborg, Sweden c Volvo Technology Corp., Chalmers Teknikpark, SE-412 88 Gteborg, Sweden

Received 7 October 2002; received in revised form 18 August 2003; accepted 21 September 2003

Abstract In order to reduce CO2 emissions there is a trend towards an increased use of more fuel-efcient lean burn combustion engines and thus an increased need for deNOx catalysts for such engines. In this study a mechanical mixture of CoFER and HZSM-5 zeolites was studied as a dual pore system catalyst for the continuous lean reduction of NOx with isobutane as reducing agent. The degree of NOx conversion was found to be strongly dependent on the oxygen concentration in the gas mixture, and the highest degree of reduction was achieved with 10% O2 . This optimum is explained by the need for NO2 as an intermediate for the catalyst to work efciently, and that above a certain oxygen concentration O2 oxidises the hydrocarbon resulting in a lower reduction potential for NOx . At an operating temperature of 350 C the conversion of NOx to N2 was 52% under steady-state conditions, but the efciency can be improved further by optimisation of the oxidising zeolite and of the mixing ratio of the two zeolites. 2003 Elsevier B.V. All rights reserved.
Keywords: HC-SCR; Zeolites; NOx reduction; Lean burn; Dual pore system catalyst

1. Introduction The increasing awareness of climate changes and the connection between accumulated CO2 in the atmosphere and global warming [1,2] emphasize the need to reduce anthropogenic emissions of CO2 . Power sources equipped with combustion engines, such as trucks and cars, contribute signicantly to the consumption of fuel and consequently to the CO2 emissions. It is therefore of high importance to develop more fuel-efcient combustion engines. In this context diesel and lean-burn engines are interesting and have up to 30% lower fuel consumption compared to conventional stoichiometric engines [3]. However, with a lean exhaust, i.e. oxygen excess, the conventional three-way catalyst is not able to efciently reduce nitrogen oxides (NOx ). This requires the development of new catalytic techniques for lean reduction of NOx from internal combustion engines.

Corresponding author. Tel.: +46-31-7722961; fax: +46-31-160062. E-mail address: anders.palmqvist@surfchem.chalmers.se (A. Palmqvist). 0926-3373/$ see front matter 2003 Elsevier B.V. All rights reserved. doi:10.1016/j.apcatb.2003.09.021

Some promising NOx abatement systems have been explored for this purpose. The NOx storage and reduction concept [4,5] has been thoroughly studied the last couple of years, but has been shown to be very sensitive to sulphur, present even in trace amounts [6]. An alternative approach is based on selective catalytic reduction using ammonia (NH3 -SCR). This method requires ammonia supply, which is one of the important drawbacks of that technique. A more preferable alternative is continuous catalytic reduction of NOx using unburned hydrocarbons from the combustion or post injection of fuel (HC-SCR). For acid zeolite HC-SCR catalysts, efcient NOx reduction is achieved by oxidising NO to NO2 , which quite easily can activate the hydrocarbons [7,8]. Precious metals have in general high activity for NO oxidation but in this connection, unfortunately also for oxidation of hydrocarbons by oxygen [9]. The consequence of a high HC oxidation activity is obviously consumption of the valuable reducing agent with less reduction of NO2 in the exhaust gas. A solution to this problem could be a catalyst with high activity for NO oxidation to NO2 and high activity for NO2 reduction to N2 with hydrocarbons but with low activity for oxidation of hydrocarbons with oxygen.

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Recently, Martens et al. presented a new concept for continuous reduction of NO with hydrocarbons under lean conditions [10]. They used a dual zeolite system consisting of mixtures of (Pt,H)FER and (Ag,H)MOR and achieved high reduction of NO with isooctane in synthetic lean exhausts. The authors found a synergetic effect when the separate zeolites were mechanically mixed and concluded the synergism to be due to selective NO oxidation in the small pore zeolite (Pt,H)FER and NO2 reduction to N2 in the large pore zeolite (Ag,H)MOR. In this work another zeolite combination has been evaluated for reduction of NO with hydrocarbons under lean conditions. The aim of the study was to illuminate the individual roles of the two zeolites, CoFER and HZSM-5, in a dual pore system type catalyst, and possible synergetic effects of mixing the two. Special emphasis was put on the effect of oxygen concentration on the reduction of NO using isobutane.

2. Materials and methods Zeolite HZSM-5 (CBV 3020) with a SiO2 /Al2 O3 molar ratio of 33 (and an impurity of 0.09 wt.% Fe2 O3 ) was supplied by Eka Chemicals as extrudates with a specic surface area of 347 m2 /g. Extrudated acidic ferrierite (HSZ-720HOD1S) with an initial SiO2 /Al2 O3 molar ratio of 16.3 and a specic surface area of the extrudates of 290 m2 /g was supplied by Tosoh. The extrudated catalyst particles were 1.5 mm 4 mm in size. The zeolite particles were 510 m in diameter for ZSM-5 and <1 m for the ferrierite. Specic surface areas were measured with nitrogen adsorption at 196 C using an ASAP 2010 instrument from Micromeritics. Ten grams of extrudated acidic ferrierite was ion exchanged to the sodium form at 80 C using an ion exchange column and slowly passing 2 dm3 of 0.125 M NaNO3 solution at pH = 7 through the bed. The same procedure was repeated, using a 20 mM Co(NO3 )2 solution at pH = 5. The extrudates were dried overnight and calcined at 550 C for 2 h. This procedure gave a Co/Al molar ratio of 0.025. Evaluation of the catalytic activity was performed in a continuous ow reactor system, which is described in detail elsewhere [11]. 2.5 g of extrudated CoFER was mixed with an equal amount of extrudated HZSM-5 and placed in a horizontally mounted reactor. The bed volume was 10.8 cm3 with a porosity of 70% and the temperature was measured 11 mm before the catalyst bed. The reactant gas mixture was obtained using gases of N2 (99.999%), O2 (99.95%), NO (10% in N2 ), isobutane (2% in Ar) and Bronkhorst Hitech mass-ow controllers. The gas was fed into the reactor with a total gas ow of 1350 ml/min, which corresponds to a space velocity of 25 000 h1 when taking the porosity of the bed into account. All gas concentrations given in this article are expressed on volume basis.

Before each experiment the catalyst bed was pre-treated in a stream consisting of 11% oxygen in nitrogen at 500 C for 20 min. Temperature ramps were performed from 500 to 100 C using a ramp speed of 5 C/min. The dependence of oxygen on the NOx reduction was investigated using gas mixtures composed of 1000 ppm NO, 800 ppm isobutane and O2 ranging from 0 to 12%, where N2 was used as balance. The catalysts in the steady-state experiments were pre-treated according to the same procedure as in the temperature ramps. The temperature was decreased stepwise by 50 C steps from 500 to 100 C and data was collected when the system had reached steady state. The time to get to steady state varied from about 10 min at high temperatures to about 2 h at lower temperatures. Reactant and product gases were analysed on-line using a chemiluminiscence detector (Eco Physics CLD 700 EL ht) for NO and NO2 and non-dispersive IR instruments (Maihak, Unor 610) for N2 O and Unor 6N for CO and CO2 . The conversion of NO to N2 was calculated from the concentrations of detected nitrogen compounds according to the following equation: ([NO]in [NO]out [NO2 ]out 2 [N2 O]out )/([NO]in [NO]out ) 100, where the subscripts denotes the concentrations at the reactor inlet and outlet, respectively. The hydrocarbon conversion was calculated from the formation of CO and CO2 using the following equation: (([CO]out + [CO2 ]out )/[C4 H10 ]in 400. To investigate if other products were formed, a gas phase FT-IR (Excalibur Series, Bio-Rad, FTS3000MX with liquid nitrogen cooled MC2 detector and Specac gascell with 2 m pathlength) was used during the steady-state experiments.

3. Results and discussion A mixture of the two zeolites CoFER and HZSM-5 was evaluated as a dual pore system catalyst for continuous lean NOx reduction using isobutane as hydrocarbon. The respective roles of the two zeolites were initially evaluated. The idea of using a mixture of two zeolites was to exploit their differences in catalytic selectivity for the reactions involved to achieve a high deNOx activity. By combining the two zeolites in one catalyst a mixture of NO, O2 and hydrocarbon would thus yield a reduction of NO via an intermediate oxidation of NO to the more reactive NO2 [10,12]. The individual zeolites would not be expected to work as well as catalysts for the two desired main reactions, i.e. the deNOx reaction and the total oxidation of the hydrocarbon. Fig. 1a shows the concentration of NOx at the reactor outlet during three ow reactor experiments (cooling ramps) with an inlet gas mixture containing 1000 ppm NO, 8% O2 and 800 ppm isobutane over a 50:50 wt.% mixture of CoFER and HZSM-5, compared with the two individual zeolites HZSM-5 and CoFER. The CoFER showed a low conversion and/or adsorption in the entire interval studied, whereas the mixture exhibited a much higher NOx conversion and/or adsorption. The HZSM-5 did also show good conversion

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Fig. 1. (a) NOx concentration at the reactor outlet over a 50:50 wt.% physical mixture of CoFER and HZSM-5, compared to the individual CoFER and HZSM-5 samples. Inlet gas composition: 1000 ppm NO, 800 ppm isobutane, 8% O2 , and N2 as balance; SV = 25 000 h1 . (b) Formation of CO () and CO2 (- - -) over a 50:50 wt.% physical mixture of CoFER and HZSM-5 (a), compared with the individual CoFER (b) and HZSM-5 (c) samples. Inlet gas composition: 1000 ppm NO, 800 ppm isobutane, 8% O2 , and N2 as balance; SV = 25 000 h1 .

Fig. 2. (a) Concentration of NO, NO2 and NOx at the reactor outlet for a reaction between 1000 ppm NO and 8% O2 over HZSM-5. (b) Concentration of NO, NO2 and NOx at the reactor outlet for a reaction between 1000 ppm NO and 8% O2 over CoFER.

of NO, and above 220 C even to a larger extent than the mixture of CoFER and HZSM-5. The peak activity for NO reduction was found at slightly below 350 C for the both active catalysts. In Fig. 1b the formation of CO and CO2 for the three ow reactor experiments are shown as a function of temperature, and it is obvious that the HZSM-5 and the mixture both activate the hydrocarbon more efciently than the CoFER catalyst. The oxidation of the hydrocarbon was more efcient over the mixture of the zeolites than over the HZSM-5 catalyst alone since the mixture gave more CO2 and less CO compared to the HZSM-5 alone. The key to the high deNOx activity of the HZSM-5 catalyst can be found in its high NO oxidation activity shown in Fig. 2a. HZSM-5 has previously been reported to be able to oxidise NO to NO2 with O2 [12], and it is obvious from the present data that this activity is sufciently high to convert also a large fraction of the NO to NO2 . Most probably it is this ability together with the acidic properties of

the HZSM-5 zeolite that results in the high deNOx activity found in this study. In Fig. 2b the explanation for the better low-temperature activity of the mixed catalyst can be found in its higher activity for NO oxidation below 230 C compared to the HZSM-5 catalyst. Under these conditions the empty reactor did not produce any detectable amount of NO2 . To conclude the study this far the results show that a dual pore system catalyst based on CoFER and HZSM-5 is active for selective reduction of NOx with isobutane under lean conditions. A more optimal oxidation catalyst (larger amount of Co in the ferrierite or another oxidising metal) and a more optimal mixing ratio of the two zeolites can be expected to give even higher reduction of NOx . Since the production of NO2 is a crucial step in the dual pore system catalyst the inuence of O2 concentration in the reactant gas was investigated. Fig. 3a shows the catalytic activity of a 50:50 wt.% mixture of CoFER and HZSM-5 as the concentration of NOx at the reactor outlet versus reactor temperature for a series of gas mixtures containing 760 ppm NOx , 800 ppm iso-C4 H10 , and between 0 and 12% O2 .

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Fig. 3. (a) NOx concentration at reactor outlet over the physical mixture of CoFER and HZSM-5. Inlet gas composition: 760 ppm NO, 800 ppm isobutane, 0, 2, 4, 8, 10 and 12% O2 , and N2 as balance; SV = 25 000 h1 . (b) Formation of CO2 over the physical mixture of CoFER and HZSM-5. Inlet gas composition: 760 ppm NO, 800 ppm isobutane, 0, 2, 4, 8, 10 and 12% O2 , and N2 as balance; SV = 25 000 h1 . (c) Formation of CO over the physical mixture of CoFER and HZSM-5. Inlet gas composition: 760 ppm NO, 800 ppm isobutane, 0, 2, 4, 8, 10 and 12% O2 , and N2 as balance; SV = 25 000 h1 . (d) Conversion of isobutane to CO and CO2 over the physical mixture of CoFER and HZSM-5. Inlet gas composition: 760 ppm NO, 800 ppm isobutane, 0, 2, 4, 8, 10 and 12% O2 , and N2 as balance; SV = 25 000 h1 .

Fig. 3bd show the corresponding formation of CO2 and CO and the calculated conversion of isobutane, respectively. In absence of oxygen there was no signicant decrease in NOx concentration over the catalyst, except for a very small amount above 300 C (Fig. 3a). This indicates not only that there was very little reaction with NO taking place in the absence of oxygen, but also that there was no appreciable adsorption of NO in the two zeolites present. Fig. 3bd show a corresponding low conversion of isobutane when there was no O2 present, and the low conversion found above 300 C can be attributed to oxidation by NO. In presence of oxygen there was a decrease in the NOx concentration shown in Fig. 3a, and an increase in the conversion of isobutane as shown in Fig. 3d. The conversion of NOx was highest slightly above 300 C for all oxygen concentrations studied. The reduction of NOx was found to increase with increasing oxygen concentration up to an oxygen concentration of 10% where it was found to be the

highest and corresponded to a NOx conversion of 74% at 300 C. Interestingly, the conversion of NOx was slightly lower at 12% O2 than at 10% O2 , indicating that there was an optimum oxygen concentration for the reduction of NOx . Since very little adsorption or reaction of NO was observed in absence of O2 , the decrease in NOx observed in the presence of O2 should be due to formation of NO2 , which subsequently either adsorbs in the zeolites or reacts with isobutane. The NO2 was formed by the oxidation of NO with O2 in increasing amounts with increasing O2 concentration. An explanation for the higher conversion of NOx at 10% O2 than at 12% O2 might be that a too high oxygen level might lead to that the hydrocarbon also can be oxidised by oxygen, which would lead to a consumption of the hydrocarbon by the oxygen. Fig. 3b shows that the formation of CO2 increased with increasing O2 concentration (also for 12% O2 ) as expected. The formation of CO followed a more complicated trend

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Fig. 4. NOx and isobutane conversion over the physical mixture of CoFER and HZSM5 at steady-state conditions as a function of temperature. Inlet gas composition: 760 ppm NO, 800 ppm isobutane, 10% O2 , and N2 as balance; SV = 25 000 h1 .

Fig. 5. Selectivity of NO reacted over the physical mixture of CoFER and HZSM-5 at steady-state conditions. NO2 and N2 O are measured values, whereas N2 was calculated as N2 = (NOin NOout NO2out 2 N2 Oout )/(NOin NOout ) 100. Inlet gas composition: 760 ppm NO, 800 ppm isobutane, 10% O2 , and N2 as balance; SV = 25 000 h1 .

with increasing amounts of CO with increasing oxygen concentration until reaching a maximum for the 10% O2 concentration. In addition the temperature of maximum CO formation was shifted to lower values as the oxygen concentration was increased. The shape of the curves of CO and CO2 formation suggests that there were more than one mechanism active through which the isobutane was oxidised. In order to nd out to what extent the decrease in the outlet NOx signal could be attributed to adsorption and reaction, respectively, the mixture of the two zeolites was evaluated under the same conditions as the temperature ramp with 10% O2 but at steady-state conditions and constant temperatures. The temperature was decreased stepwise in 50 C steps from 500 C and the instrumental readings were collected when steady-state conditions had been reached. Fig. 4 shows the degree of NOx and HC conversion over the mixture of zeolites at steady-state conditions. At steady state, the outlet NOx concentration was higher than in the corresponding ramps, indicating that some adsorption of NO2 occurred in the catalyst. Considering that the molar ratio of NO:HC at the reactor inlet was relatively high (close to 1) the degree of NOx conversion achieved was still high. The maximum in NOx conversion seemed to be at a somewhat higher temperature than in the ramp experiment. This could be due to that in the ramp experiment there was adsorption occurring, which can result in an apparent lower temperature of the minimum in NOx concentration. The selectivity for the NO conversion is presented in Fig. 5 and a high tendency towards N2 was found. Above 300 C more than 80% of the converted NO was reduced to N2 . Although the expected nitrogen-containing end products from a reaction between NO2 and the hydrocarbon are N2 O or N2 , intermediate formation of, e.g. alkyl nitrates [13] and alkyl amines have also been reported [14]. For this reason gas phase FT-IR analysis of the reaction products was performed. The results from these measurements are shown in

Fig. 6 and the spectra taken at steady-state conditions showed the presence of NO, NO2 (1599 and 1629 cm1 for both), and N2 O (2238 cm1 ). Very small peaks at 922, 950 and 966 cm1 at 450 C could not be assigned to NH3 since the expected peak at 3338 cm1 for NH3 was not found [15]. A small peak at 833 cm1 between 150 and 250 C could not be unambiguously assigned to alkyl nitrates. The absorption of alkyl amines appears in the region 16601625 cm1 . In this region NO and NO2 also absorb strongly, making the assignment of alkyl amines in the gas outlet not possible [16]. A small peak at 712 cm1 could not be unambiguously assigned to HCN since the required peak at 3311 cm1 was ab-

Fig. 6. Gas phase FT-IR spectra showing absorbance at steady-state conditions over the physical mixture of CoFER and HZSM-5 as a function of reactor temperature. Inlet gas composition: 760 ppm NO, 800 ppm isobutane, 10% O2 , and N2 as balance; SV = 25 000 h1 .

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sent [15]. If, however, the 712 cm1 peak would be assigned to HCN, it would at the most correspond to a maximum concentration of 19 ppm in our experiments based on comparison between spectra from literature taking into account differences in optical path length. The amount of nitrogen in HCN would then correspond to less than 2.5% of the total NO concentration used in our study. The main remaining peaks in Fig. 6 can be assigned to isobutane (2966 cm1 ), CO2 (2358 and 670 cm1 ), CO (2100 and 2200 cm1 ), and water (1500 and 3800 cm1 ). 4. Conclusions Mechanichal mixtures of CoFER and HZSM-5 were found to be active in reducing NOx to N2 with isobutane. The degree of NOx conversion was found to be strongly dependent on the oxygen concentration in the gas mixture, and the highest degree of reduction was achieved at 10% O2 . This optimum can be explained by the need for NO2 for the catalyst to efciently reduce NOx . NO2 forms in increasing amounts as the oxygen concentration is increased, but above a certain oxygen concentration the hydrocarbon starts to become oxidised also by oxygen resulting in a lower reduction of NOx . Under steady-state conditions no nitrogen-containing molecules besides NO, NO2 and N2 O could unambiguously be detected by gas phase FT-IR. The conversion of NOx to N2 was 52% during steady-state conditions at the optimal temperature of 350 C. The results also indicate that improved results can be expected using a more suitable oxidation catalyst and an optimised mixing ratio of the two zeolites. Acknowledgements This work has been performed within the Competence Centre for Catalysis (KCK), which is nancially supported

by The Swedish Energy Agency and the member companies: AB Volvo, Saab Automobile AB, Johnson Matthey-CSD, Perstorp AB, AUL-MTC AB, EKA Chemicals/Akzo Nobel Catalysts, and the Swedish Space Agency. This work was also nancially supported by the KK-foundation. The companies Tosoh and EKA Chemicals are gratefully acknowledged for providing the ferrierite and ZSM-5 samples, respectively.

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