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Combustion and Flame 153 (2008) 119129 www.elsevier.com/locate/combustame

Use of multi-transition-metal-ion-exchanged zeolite 13X catalysts in methane emissions abatement


K.S. Hui, C.Y.H. Chao , C.W. Kwong, M.P. Wan
Department of Mechanical Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China Received 16 April 2007; received in revised form 10 December 2007; accepted 19 December 2007 Available online 6 February 2008

Abstract Methane is a potent greenhouse gas. It has a global warming potential (GWP) 23 times greater than carbon dioxide. Reducing methane emissions would lead to substantial economic and environmental benets. This study investigated the performance of multi-transition-metal-(Cu, Cr, Ni, and Co)-ion-exchanged zeolite 13X catalysts in methane emissions abatement. The catalytic activity in methane combustion using multi-ion-exchanged catalysts was studied with different parameters including the molar percentage of metal loading, the space velocity, and the inlet methane concentration under atmospheric pressure and at a relatively low reaction temperature of 500 C. The performance of the catalysts was determined in terms of the apparent activation energy, the number of active sites of the catalyst, and the BET surface area of the catalyst. This study showed that multi-ion-exchanged catalysts outperformed single-ion-exchanged and acidied 13X catalysts and that lengthening the residence time led to a higher methane conversion percentage. The enhanced catalytic activity in the multi-ion-exchanged catalysts was attributed to the presence of exchanged transition ions instead of acid sites in the catalyst. The catalytic activity of the catalysts was inuenced by the metal loading amount, which played an important role in affecting the apparent activation energy for methane combustion, the active sites, and the BET surface area of the catalyst. Increasing the amount of metal loading in the catalyst decreased the apparent activation energy for methane combustion and also the BET surface area of the catalyst. An optimized metal loading amount at which the highest catalytic activity was observed due to the combined effects of the various factors was determined. 2008 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
Keywords: Natural gas; Methane; Catalytic combustion; Zeolite 13X; Transition metal ions

1. Introduction Natural gas, composed primarily of methane, is known to be the cleanest-burning fossil fuel because of its low carbon content and negligible sulfur diox* Corresponding author. Fax: +852 2358 1543.

E-mail address: meyhchao@ust.hk (C.Y.H. Chao).

ide emissions. This makes it a very attractive energy source. The use of natural gas is expected to increase in the utility, transportation, and industrial sectors in the near future. On the other hand, when released to the atmosphere, methane is a potent greenhouse gas. It has a global warming potential (GWP) 23 times greater than carbon dioxide. Methane is emitted from a variety of anthropogenic activities, such as fossil fuel production, gas-powered biomass com-

0010-2180/$ see front matter 2008 The Combustion Institute. Published by Elsevier Inc. All rights reserved. doi:10.1016/j.combustame.2007.12.003

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bustion, operation of natural gas vehicles (NGVs), and waste management [1]. For example, in mine ventilation air, the methane concentration is 0.11 vol% [2]. In natural-gas-fueled vehicles, which are increasingly popular in some countries because of their low emissions of NOx and particulates [35], the unburned methane concentration in the exhaust is around 0.3 vol% [6]. It is estimated that 60% of global methane emissions are related to human-related activities [7]. Reducing methane emissions will lead to substantial economic and environmental benets. Catalytic combustion is considered to be an effective approach to methane emissions abatement [8]. Higher combustion efciency can be achieved at temperatures and concentrations much lower than those required for a stable homogeneous gas phase reaction to proceed without a catalyst [9]. The principle, difculties, and general developments in the eld of catalytic methane combustion have been described in review articles [10,11]. Among various catalysts, palladium-based catalysts are the most successful in catalytic methane combustion under lean fuel conditions [1215]. However, they suffer from such disadvantages as high volatility, poor availability, and high cost [11]. The search for alternative catalysts has increased in the past decades. It has been shown that metal oxides such as Cr2 O3 , CuO, NiO, and Co3 O4 are effective in methane combustion [1618]. Studies have also shown that the catalytic activity of multicomponent catalysts is superior to that of singlecomponent catalysts [1921]. There has been increasing interest in using metalion-exchanged zeolite (zeolite-X and -Y, mordenite, and ZSM-5, -11, and -48) catalysts in methane combustion [9,2225]. The presence of exchanged metal ions in a zeolite matrix as an isolated species can prevent metal agglomeration and sintering of catalysts. Rudham and Sanders showed that the kinetics of oxidation of methane by transition-metal-ionexchanged zeolite 13X was faster than that by corresponding bulk oxides [22]. The earlier studies [9, 2225] focused only on single-metal-ion-exchanged zeolites as catalysts in methane combustion; however, there has been no published report on the performance of multi-transition-metal-ion-exchanged zeolite catalysts in methane combustion. Performance information is important for the design of alternative and cheaper systems to abate methane emissions, especially considering the increasingly high cost and limited supply of precious metals. This work is motivated by the nding that a multitransition-metal-ion-exchanged zeolite 4A catalyst achieved a higher methane conversion percentage than the corresponding single-transition-metal-ionexchanged catalyst under the same total wt% of metal loading [26]. Compared with zeolite 4A (with a pore

cavity of 4 ), zeolite 13X has a larger pore cavity of 12 , where the access of methane (with a molecular dimension of around 3.9 ) to the active sites may be better. In addition, the promising results of the study on zeolite 4A [26] suggest that zeolite 13X can be a good catalyst support. However, no tests using multi-transition-metal-ion-exchanged zeolite 13X for methane combustion have yet been conducted. This paper presents a performance evaluation of multi-transition-metal-ion-exchanged zeolite 13X catalysts in the combustion of low-concentration methane (1.13.2 vol%). The results are useful in the control of methane emissions from some industries, such as biological waste, waste water treatment facilities, and coal mine ventilation systems, which contain methane up to a concentration of 1 vol%. Acidied zeolite 13X was used as a catalyst support and the multi-transition-metal-ion-exchanged (Cu, Cr, Ni, and Co) zeolites were prepared by the ion-exchange method. The catalytic activity in methane combustion using multi-ion-exchanged catalysts was studied under different parameters including the mol% of metal loading, the space velocity, and the inlet methane concentration under atmospheric pressure and at 500 C. Different mol%s of each exchanged ion on the samples led to different BET surface areas, different apparent activation energies (hereafter called the activation energy for simplicity), and different numbers of active sites. The performance of the catalysts was determined in terms of the activation energy, the number of active sites in the catalyst, and the BET surface area of the catalyst.

2. Experiments 2.1. Preparation of multi-transition-metal-ion-exchanged catalysts Acidied zeolite 13X in cylinder pellets (Nacalai Tesque, code: 233-36, diameter: 23 mm, length: 57 mm) was used as the catalyst support in this study. The description as acidied zeolite 13X (hereafter called 13X for simplicity) means that the sample contained acid sites. All the compounds used to prepare the solutions for the ion-exchange experiments were of analytic grade. The ion-exchange experiments, simultaneously performed in multi-transitionmetal-ion solutions, were based on information from our laboratory study that shows the selectivity sequence and also the metal-loading capacity of the ions in 13X. The selectivity sequence of the metal ions by the adsorbent was mainly dependent on the initial concentrations of the metal ions and the initial pH of the solution. A similar observation was reported earlier [27]. Briey, the selectivity sequence

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Fig. 1. A schematic diagram of the experimental setup.

was Cu2+ > Cr3+ > Ni2+ > Co2+ for 13X at pH 4. In the ion-exchange experiments, 7 g of 13X pellets was put in a net holder and mixed with 100 ml of deionized water by stirring for 1 h, and then the pH of the solution was adjusted to 4 by adding a few drops of 2% HNO3 . Second, 100 ml of multi-transitionmetal-ion solutions containing Cu2+ , Cr3+ , Ni2+ , and Co2+ ions of 0.10.3 M each were prepared by dissolving measured quantities of nitrate salts in deionized water. Third, the multi-transition-metal-ion solution was poured into the zeolite 13X solution and the mixture was mechanically stirred at 600 rpm at 25 C for 24 h. No signicant adsorption of metal ions was observed after 24 h of stirring. After the ion exchange, the 13X pellets were ltered and washed by stirring in 1 l deionized water for 30 min. After another ltration, the 13X pellets were dried at 110 C overnight in air. It should be noted that nitrate anions were considered to be inert and they did not form precipitates or complexes with the corresponding metal ions under the experimental conditions. In addition, no precipitation of metal hydroxides in the solution was observed during the ion-exchange process. The metal ions in the 13X catalysts were present in an isolated state [22, 28,29]. 2.2. Characterization The pH value was measured by a MettlerToledo meter (MP 120). The bulk elemental composition of the catalysts was determined by a JEOL X-ray reective uorescence spectrometer (XRF, JSX 3201Z). Nitrogen adsorption/desorption tests were carried out at 77 K using a Coulter SA3100 physical-adsorption apparatus. The volume of the adsorbed nitrogen was normalized to standard temperature and pressure (STP). Prior to the experiments, the samples were dehydrated at 150 C for 2 h. The BET surface area was determined from the linear part of the BET plot (p/p0 = 0.050.2). The acidity of the catalysts was determined by NH3 desorption in a thermogravimetric analyzer (TGA) [30]. The catalysts were degassed

by heating them at 300 C for 2 h. The degassed catalysts were then subjected to NH3 adsorption at 25 C for 24 h. The adsorbed NH3 was then desorbed and quantied in the TGA analysis. In the NH3 desorption, the catalysts were rst equilibrated at 100 C for 60 min to remove any physisorbed NH3 , and then the rest of NH3 was desorbed using a 10 C/min temperature ramp to heat the catalysts from 100 to 550 C. The NH3 desorbed above 100 C was considered as chemisorbed NH3 and used in the acidity determination. 2.3. Catalytic methane combustion Fig. 1 shows a schematic diagram of the experimental setup for catalyst testing. The setup consisted of a pressurized methane gas cylinder (CH4 , 99.99%) with a pressure regulator, a pressurized synthetic air gas cylinder (22% O2 and 78% N2 ) with a pressure regulator, mass ow controllers (AALBORG, Model DFC26, methane: 010 ml/min, air: 050 ml/min, accuracy: 1% full scale; Model GFC17, air: 0500 ml/min, accuracy: 1.5% full scale), a mixer, a pressure gauge (Cecomp Electronics, range: 030 psi, accuracy: 0.25% full scale), a temperature-controlled chamber, a quartz tube reactor (inner diameter 6 mm, outer diameter 8 mm), and a nondispersive infrared (NDIR) gas analyzer (Q-Trak Plus, Model 8554) for the measurement of CO2 concentration. Measurement of the CO gas was achieved with the electrochemical sensor in the gas analyzer (range of detection: 0500 ppm, resolution: 1 ppm). Before the experiments, the NDIR gas analyzer was calibrated according to the manufacturers manual. The catalytic activity was evaluated in a 6-mminner-diameter and 600-mm-long cylindrical quartz tube reactor heated by a temperature-controlled chamber. The temperature-controlled chamber (internal volume 24.5 10.5 6 mm (L W H)) was built of high-temperature Kaowool ceramic ber (25 mm thick), which was further supported by hightemperature bricks. The temperature of the cham-

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Table 1 Elemental composition of the prepared catalysts and their BET surface area Sample M0 M1 M2 M3 M4 M5 M6 13X mol% Si 41.1 41.6 43.2 46.5 45.7 43.3 45.5 43.9 Al 28.4 29.8 30.7 28.5 28.9 31.6 32.1 32.7 Na 7.5 9.7 9.2 7.7 9.3 10.9 15.4 23.5 Cu 10 8 8 7 7 5 2 0 Cr 8 6 6 7 5 7 2 0 Ni 4 4 2 2 3 2 2 0 Co 1 1 1 1 1 1 1 0 Total metala 23 19 17 17 16 15 7 0 BET area (m2 /g) 40 51 58 62 70 101 412 532

a Cu, Cr, Ni, and Co elements.

ber was controlled by a temperature controller (Barnant Company, Model 689-0015) connected to two infrared heaters (600 W each) and a K-type (RS 219-444) thermocouple with a response time of 2 s. Catalysts, in pellet form (outer diameter 23 mm, length 12 mm), were placed in the middle of the tube, which was plugged with quartz wool at the two ends. The tube was heated by infrared heaters placed above and under the tube. A K-type thermocouple was xed to the middle of the catalyst bed to measure the reaction temperature and to maintain the reaction temperature at the set-point temperature. In order to ensure that the premixed gases could reach the same temperature as the temperature-controlled section of the tube, heating wire was also used to heat up the premixed gases before they entered the section. Comparing the heat release by combustion of methane on the catalysts under the current experimental conditions (0.31.1 J/s) with the heat supply (720 J/s) to maintain the operating temperature of the chamber at 500 C, the heat release due to combustion was too small to have a signicant impact on the temperature of the reaction chamber. A fairly constant reaction temperature of 500 3 C in the catalytic system was achieved. The reaction temperature of 500 C was used in this study because it is a practical operating temperature that can be easily achieved in the catalytic combustion systems. In all our tests, the relative humidity in the reactant stream was around 10%. Before the catalyst activity test, all catalysts were pretreated in the following way to ensure that the obtained catalytic activities were representative and not due to the freshness of the catalysts. First, all catalysts were treated in a 200 ml/min air stream at 500 C for 1 h. The temperature was increased from room temperature to 500 C at a rate of 10 C/min. Then, the catalysts were operated in a 200 ml/min stream of methane of 1 vol% for 6 h at 500 C. The performance of the catalyst was assessed on the basis of the percentage of methane conversion determined at different space velocities calculated at 500 C un-

der various methane concentrations. Space velocity is dened as the total volumetric ow rate of the gas at 500 C divided by the volume of the catalytic bed. The methane conversion % refers to the yield of CO2 from the combustion based on the equation (CH4 + 2O2 CO2 + 2H2 O). The methane conversion % was calculated 20 min after the start of each test to determine the methane conversion under stable conditions. The reported values are averages of two sets of independent experiments. New and pretreated catalysts were used in each set of independent experiments. In the current study, no reducing treatment was done on the catalysts before the experiments. The catalysts were treated in an oxidizing environment before the tests because a prereducing treatment would have a short-term effect on the activity of the catalyst, which would not capture performance capabilities under long-term operations.

3. Results and discussion 3.1. Characterization of the prepared catalysts Table 1 shows the elemental composition of the 13X and the multi-transition-metal-ion-exchanged 13X catalysts (codes M0 to M6). Compared to the 13X, the slight decrease of element content such as Si and Al in the ion-exchanged catalysts was due to partial dissolution of the zeolite under the preparation conditions [27]. The decrease in Na was due to an ion exchange between the multi-ions and the Na+ ions. The BET surface areas of the catalysts are listed in Table 1. The tests showed that the BET surface area generally decreased with increasing mol% of metal loading. It is expected that more pore cavities in the zeolite were blocked by adding more transition metal ions, leading to the reduction of the accessibility of nitrogen as observed from the lower BET surface area. M3 and M2 had the same total mol% of metal loading but showed a slight difference in the BET surface area. This indicates that the difference in the specied

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Fig. 2. Acidity of the prepared catalysts.

Fig. 3. The inuence of reaction temperature on methane conversion percentage. Experimental conditions: inlet methane concentration of 1.1 vol%, space velocity of 1500 h1 , and catalyst mass of 2.8 g.

mol% of each element caused a slight difference in the BET surface area. The acidic strength of the sample was quantied by the temperature used to desorb chemically adsorbed NH3 . The higher the temperature used to desorb chemically adsorbed NH3 , the stronger the acid sites are. The area under the temperature-programmed desorption (TPD) curve represents the number of acid sites in the sample. Fig. 2 shows the acidity (the acidic strength and the number of acid sites) of the catalysts. The acidic strengths of all catalysts were similar, as indicated by their desorption peaks at the same temperature. The 13X catalyst had the largest number of

acid sites because it had the largest area under the TPD curve. The multi-ion-exchanged catalysts had relatively smaller numbers of acid sites. The number of acid sites of the multi-ion-exchanged catalysts decreased with increasing mol% of metal loading. This was because the H+ ions, leading to the acidity of the catalyst, were replaced by the metal ions. 3.2. Catalytic activity and methane combustion Fig. 3 shows that greater methane conversion was achieved with increasing reaction temperature from 350 to 500 C under the tested conditions. Be-

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Fig. 4. Methane conversion percentages of the multi-ion- and the single-ion-exchanged catalysts. Experimental conditions: inlet methane concentration of 0.3, 0.6, and 1.2 vol%, space velocity of 86,000 h1 , reaction temperature of 500 C, and catalyst mass of 0.2 g.

low a reaction temperature of 350 C, no methane combustion on the catalysts was observed. The results showed that a reaction temperature of 500 C is the most effective in methane combustion within our tested range of reaction temperatures. In terms of thermal management of the system and material properties of the zeolite-based catalysts, it is not suggested that such catalytic combustion systems be operated at reaction temperatures higher than 500 C. Similar ndings were obtained in our previous study [26]. Therefore, in the current study, reaction temperature was xed at 500 C in further experiments investigating the inuence of other parameters such as inlet methane concentrations and space velocities on the performance of the catalysts. 3.2.1. The effect of the multi-ion-exchanged catalyst compared with a single-ion-exchanged catalyst Rudham and Sanders showed that, under the same experimental conditions, an activity sequence in methane combustion is Cu(19)-13X > Cr(19)13X > Ni(19)-13X > Co(18)-13X = H(22)-13X > 13X, where the number inside each parentheses corresponds to the wt% of the exchanged ions [22]. That is, Cu is the most active element among Cu, Cr, Ni, and Co in methane combustion. There is less study of multi-ion-exchanged zeolites versus single-ion-exchanged zeolites in methane combustion in the literature. We tested the hypothesis that multi-ion-exchanged catalysts outperform singleion-exchanged catalysts. Two catalysts with the same total mol% of metal loading, Cu-13X and M4, were tested under varying conditions. Fig. 4 shows the

methane conversion percentages of these two catalysts. The methane conversion percentage indicates the amount of methane reacted within a specic time frame (the space velocity or the residence time). The gure shows that the multi-ion-exchanged catalyst outperformed the single-ion-exchanged catalyst, even though Cu ions are the most active element among the tested elements in the methane combustion. The good activity of the multi-ion-exchanged catalyst in methane combustion may be due to synergistic effects, which seem to be a general phenomenon in a number of catalytic reactions for mixtures of many different catalytic metals and metal oxides [20]. 3.2.2. The inuence of the space velocity on methane conversion percentage with different multi-ion-exchanged catalysts Fig. 5 shows the methane conversion percentages of different catalysts at various space velocities. The tests were carried out at an inlet methane concentration of 1.1 vol% with 2.8 g of catalyst and a reaction temperature of 500 C. No CO was detected in any test. The results show that the methane conversion percentage decreased with increasing space velocity. A higher methane conversion percentage was achieved with a lower space velocity. This was due to the increase in the residence time for reactant molecules to diffuse into the active sites of the zeolite pore structure for reaction or diffusion of desorbed carbon dioxide and water from the active sites. Under the test conditions, the zeolite catalysts were in the pore diffusion control regime, as Ryoo et al. reported

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Fig. 5. The inuence of space velocity on methane conversion percentage. Experimental conditions: inlet methane concentration of 1.1 vol%, space velocity of 150013,100 h1 , reaction temperature of 500 C, and catalyst mass of 2.8 g.

Fig. 6. The inuence of inlet methane concentration on methane conversion percentage. Experimental conditions: inlet methane concentration of 1.1, 2.1, and 3.2 vol%, space velocity of 1500 h1 , reaction temperature of 500 C, and catalyst mass of 2.8 g.

that diffusion limitation is predominant in zeolite pore structures in catalytic methane combustion [31]. 3.2.3. The inuence of the inlet methane concentration on methane conversion % with different multi-ion-exchanged catalysts Fig. 6 shows the methane conversion percentages of different catalysts at various inlet methane concentrations. The tests were carried out at inlet methane concentrations from 1.1 to 3.2 vol%, a space velocity of 1500 h1 , with 2.8 g catalyst and a reaction temperature of 500 C. No CO was detected in any of the tests. The results show that the methane conver-

sion percentage decreased with increasing methane concentration. However, the actual amount of converted methane increased with the methane inlet concentration, as shown in Table 2. This indicates that the turnover frequencies (TOF, mole methane converted/gram catalyst second) was enhanced by the higher methane inlet concentration despite the apparent decrease in the methane conversion percentage. Since the same amount of catalyst was used in different experiments, the number of active sites for methane combustion remained unchanged. When the inlet methane concentration kept increasing, there would eventually not be enough active sites available

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Table 2 Rates of methane conversion by the catalysts expressed as mmole methane converted/(gram catalyst s) (the data were obtained under the same experimental conditions as in Fig. 6) Catalyst M0 M1 M2 M3 M4 M5 M6 13X Inlet methane concentration (vol%) 1.1 5.43E05 6.77E05 7.22E05 1.39E04 1.39E04 1.22E04 2.78E05 5.83E06 2.1 9.62E05 1.20E04 1.29E04 2.48E04 2.61E04 2.14E04 4.08E05 8.45E06 3.2 1.29E04 1.57E04 1.73E04 3.31E04 3.52E04 2.86E04 4.00E05 1.07E05

1.39E04 2.91E04 4.44E04 Control (100%)a Heat release (100%)b 1.11E01 2.34E01 3.56E01 (J/(gram catalyst s))
a Assumes a catalyst achieves 100% methane conversion. b Heat of combustion of methane is 802 kJ/mol.

for the reactions. Thus, methane conversion percentage decreased with increasing methane concentration. However, in our tested cases, it was not clear if all the active sites had been used or not. Compared to 13X, the multi-ion-exchanged catalysts were more active in methane combustion, as shown in Figs. 5 and 6. The multi-ion-exchanged catalysts were around 434 times more active than the 13X catalyst. According to Fig. 2, all samples had the same acidic strength, but 13X had the largest number of acid sites. The results, depicted in Fig. 6, show that the effect of the metal ions was more prominent than the effect of the number of acid sites available in the catalysts in methane combustion. According to other studies [23,32], the reaction mechanism can be briey described in a few steps. The reactants are rst adsorbed on the exchanged ions sites. These ions can be alkali ions, alkaline earth metal ions, transition metal ions, or H+ ions. Dissociations of the adsorbed oxygen to form atomic oxygen then occur. Finally, reactions between the adsorbed reactants and the atomic oxygen proceed to form carbon dioxide and water. The reactions in all tested samples (13X and the M series) generally followed these steps. However, the activity of the zeolitetype catalyst in methane combustion is mainly inuenced by the type of exchanged ions existing in the zeolite [22]. Different types of exchanged ions in the catalyst can lead to different activation energies in the reaction. In Fig. 6, the difference in the methane conversion percentages of all samples is related to the nature of the exchanged ions. Exchanged ions are responsible for the activation of oxygen and methane molecules.

The formation of bonds between the exchanged ions and the oxygen or methane molecules is controlled by the nature of the exchanged ions. Compared to the ions in 13X, transition metal ions in the M series are known to have higher available oxidation states and lower ionization potentials, which make them more active in the adsorption of molecules where bond formation is easier [30]. Because of the properties of the transition metal ions, the M series samples had higher methane combustion activities than did 13X. Among the M series catalysts, Fig. 6 shows a trend for the methane conversion percentage to increase from sample M6 to M4 and then decreased afterward. This observation may suggest that samples with too low (M6) or too high (M0 and M1) mol% of metal loading were not active in methane combustion. There was an optimized mol% of metal loading with which the catalyst achieved the highest methane conversion percentage. Apparently, M4 offered the peak performance due to its high total metal loading and not too low BET surface area. The methane conversion percentage depends on the reaction rate, which is related to the activation energy, the number of active sites, and the BET surface area of the catalyst. In order to explain the trend in Fig. 6, experiments were conducted to determine the activation energy and the active sites of the catalysts. A similar approach that was used by Hoyos et al. [33] and Neyestanaki et al. [34] was adopted. Experiments were conducted under conditions (inlet methane concentration of 0.6 vol%, space velocity of 86,000 h1 , reaction temperature of 420500 C, and catalyst mass of 0.2 g) to limit methane conversion to be smaller than 10% in order to minimize the inuence of pore diffusion and the bulk mass transfer resistances on the calculation of activation energy. Under the tested conditions, the reactor was considered as an integral ow reactor system and the reaction was assumed to be a rst-order reaction with respect to methane and a zero-order reaction with respect to oxygen [22,34]. The methane conversion percentage in relation to the temperature is given by the equation [33,34] ln ln(1 x) = E/RT + ln(K0 m/F ), (1)

where x , E , R , K0 , m, and F are the fractional methane conversion, the activation energy, the gas constant, the reaction rate constant, the mass of the catalyst, and the volumetric feed ow rate, respectively. Fig. 7a shows the Arrhenius plots for the methane conversion by the catalysts. The activation energy, E , and the K0 m/F values were calculated from the linear part of the Arrhenius plot in Fig. 7a. The K0 m/F value is a dimensionless constant that is proportional to the number of active sites present in the catalyst, as suggested by Hoyos et al. [33] and

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(a)

(b) Fig. 7. (a) Arrhenius plots for methane conversion by the catalysts. Experimental conditions: inlet methane concentration of 0.6 vol%, space velocity of 86,000 h1 , reaction temperature of 420500 C, and catalyst mass of 0.2 g. Lines are the results of linear tting to the experimental data. (b) The calculated activation energy in the combustion of methane and the active sites of the catalysts. The values were calculated based on the data in (a).

Neyestanaki et al. [34]. The K0 m/F value was determined at a temperature of 500 C. Fig. 7b shows the calculated values of E and K0 m/F of different catalysts. Compared to the M series samples, the observed low activation energy of 13X may be due to the presence of greater numbers of acid sites in the sample. The values of the activation energy of the M series showed that increasing the mol% of metal loading decreased the activation energy in the methane combustion. Catalysts having relatively low activation energies carry out reaction rates higher than those having higher activation energies. It is important to note that both the transition

ions and the H+ ions can be active sites for methane combustion. As reported by Rudham and Sanders, the H+ ions were not as active as the transition ions in 13X in methane combustion [22]. Although 13X had a greater number of acid sites than the M series samples had, it had the lowest K0 m/F value. The K0 m/F value does not just reect the number of active sites of the catalyst. It implies a combined effect of the number of active sites and the strength of the active sites in methane combustion. As the mol% of the total metal loading increased from M6 to M0, the K0 m/F value (which was also inuenced by the BET surface area) increased from M6 to M4 and then de-

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creased from M4 to M0. The differences in the E and K0 m/F values among different catalysts were due to different active metal species, the mol% of the metal loading, and the BET surface area. It should be noted that the results in Fig. 7 were obtained under a kinetically controlled regime where the methane conversion was limited to be smaller than 10%. The results in Fig. 7b lead to the idea that the M5 catalyst should achieve a lower methane conversion percentage than the M0 and M1 catalysts in Fig. 6, since the M5 catalyst had the highest activation energy and the lowest K0 m/F value among the three catalysts. However, this was not the case, as shown in Fig. 6, where both kinetic and mass transfer resistances may play a role in the tested conditions. According to Table 1, the higher mol% of metals in M0 and M1 blocked the pore cavities of the catalysts, which reduced the BET surface area of the catalysts. The results in Figs. 6 and 7b implied that both kinetic and mass transfer resistances play a role in the tested conditions in Fig. 6, where the BET surface area played a role in the mass transfer resistance of the catalysts. The enhanced catalytic activity of multi-ion-exchanged catalysts was inuenced by the amount of metal loading, which plays important roles in the activation energy for methane combustion, the number of active sites, and the BET surface area of the catalyst. These three effects are coupled together and their respective effects can be different depending on whether the combustion reactions are carried out in the mass-diffusion-controlled zone or the kinetically controlled zone. There existed an optimized mol% of metal loading where the highest catalytic activity was observed under our experimental conditions. A previous study [22] reported the following activity sequence in methane combustion: Cu-13X > Cr-13X > Ni-13X > Co-13X. The current study extends the previous work and may provide information about the inuence of different metal ions in the multi-ion-exchanged catalysts on the measured activities in methane combustion. The inuence of the fourth metal ions on the activity of methane conversion was revealed by xing the contents of the other metal ions under similar total metal content. In this way, catalysts M3 and M5 compare the inuence of Cu ions on the measured activity of methane conversion; catalysts M1 and M2 compare the inuence of Ni ions on the activity of methane conversion; catalysts M3 and M4 compare the inuence of Cr ions on the activity of methane conversion. From Table 1 and Fig. 6, comparing M3 with M5, the lower activity of M5 could be due to the lower Cu-content in the catalyst. Comparing M1 with M2, the lower activity of M1 could be due to the higher Ni-content in the catalyst. Comparing M3 with M4, the lower activity of M3 could be due to the higher Cr-content in

the catalyst. However, the inuence of the BET surface area of the catalysts on the measured activities could not be neglected in the present comparisons. Increasing loading of the metal content in the catalyst reduces its BET surface area, which reduces the access of the reactants to the active sites for reactions. This is because more windows of the pore cavities of the catalysts were blocked by adding more metal ions. Even if M3 and M2 had the same total mol% of metal loading, they showed a slight difference in the BET surface area of the samples. It is extremely difcult, if not impossible, to achieve high or constant loading of the metal content in the catalyst without reduction of its BET surface area, as shown in Table 1. An extra set of experiments was conducted in order to compare the methane combustion efciency of the M series catalysts with the methane combustion efciency of the Pd ion-exchanged zeolite-type catalysts (Fig. 7 of [31]) reported in the literature. Experimental conditions (inlet methane concentration of 1 vol%, space velocity of 60,000 h1 , reaction temperature of 500 C, and catalyst powder of 0.05 g, which is mixed with 1.3 g quartz powder), similar to the work of Seo and co-workers [31], were applied to the M3 and M4 catalysts. In the work of Seo and co-workers, methane conversion of 72, 70, 50, and 40 was achieved by the Pd(0.8)/KIT, Pd(0.8)/MOR, Pd(0.8)/FAU, and Pd(0.7)/MCM, respectively. In the current study, methane conversion of 8 and 7.5% was achieved by the M3 and the M4 catalysts, respectively, at such a high space velocity condition. This result was not surprising because Pd ions are known to be the most active ions in methane combustion. In the work of Rudham and Sanders [22], under the same experimental conditions, the activity of methane conversion by the Pd ions in zeolite 13X was the highest compared to other transition metal ions (Cu, Cr, Ni, and Co ions) in zeolite 13X. Methane conversion of 5% can be achieved by the Pd-13X at reaction temperature of 271 C; however, a reaction temperature of 463 C was required by the Cu-13X. On the other hand, at lower space velocity (such as 1500 h1 ), our zeolite 13X catalytic system demonstrated very high catalytic performance (close to 100% in some cases). Taking into account the lower cost of zeolite 13X compared to Pd-based catalysts, applications under low space velocity conditions seem to be promising.

4. Conclusions This study investigated the performance of multitransition-metal-ion-exchanged zeolite 13X as a catalyst on catalytic methane combustion at a relatively low temperature of 500 C. The results showed that the multi-ion-exchanged catalysts outperformed the

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single-ion-exchanged and the 13X catalysts. Zeolitebased catalysts were more active at low inlet velocities, where higher methane conversion percentages were achieved. The enhanced catalytic activity was mainly related to the presence of the transition ions instead of the presence of acid sites in the sample. The enhanced catalytic activity of the sample was inuenced by the mol% of the metal loading, which played important roles in affecting the activation energy for methane combustion, the number of active sites, and the BET surface area of the catalysts. With the M series samples, an increasing mol% of metal loading reduced both the activation energy of methane combustion and the BET surface area of the sample. Compared to that for 13X, the K0 m/F values (proportional to the number of active sites) of the M series samples were larger, due to the addition of transition metal ions. Among the M series samples, there was an optimized amount of metal loading that had the best catalytic performance based on the combined effect of the K0 m/F value, the catalytic activity, and the BET surface area. Further addition of metal loading led to blockage of the pore cavities (as shown by the reduction of the BET surface area), resulting in a reduction in the catalytic activity. Based on these promising results, more effort should be made in exploring the origin of the synergistic effect or any suppression effect of multiple transition-metal species on methane combustion using zeolite 13X-based catalysts. The possible limitations of using zeolite-based catalysts in catalytic combustion of methane also need to be studied in detail. Acknowledgments The authors thank the Materials Characterization & Preparation Facility and the Advanced Engineering Materials Facility of the Hong Kong University of Science and Technology for technical support. Funding for this research was provided by RGC Grant HKUST 6188/03E. References
[1] D. Blaha, K. Bartlett, P. Czepiel, R. Harriss, P. Crill, Atmos. Environ. 33 (2) (1999) 243255. [2] S. Su, A. Beath, H. Guo, C. Mallett, Prog. Energy Combust. Sci. 31 (2) (2005) 123170. [3] H. Kunimi, S. Ishizawa, Y. Yoshikawa, Atmos. Environ. 31 (2) (1997) 145158. [4] T. Beer, T. Grant, D. Williams, H. Watson, Atmos. Environ. 36 (4) (2002) 753763. [5] P. Goyal, Sidhartha, Atmos. Environ. 37 (38) (2003) 54235431. [6] M. Gambino, S. Iannaccone, M.F. Pidria, G. Miletto, M. Rollero, in: World Automotive Congress, 2004, F264-279.

[7] B. Metz, Climate Change 2001: Mitigation: Contribution of Working Group III to the Third Assessment Report of the Intergovernmental Panel on Climate Change, Cambridge University Press, New York, 2001. [8] R.W. Sidwell, H. Zhu, R.J. Kee, D.T. Wickham, Combust. Flame 134 (12) (2003) 5566. [9] A.K. Neyestanaki, N. Kumar, L.E. Lindfors, Appl. Catal. B Environ. 7 (12) (1995) 95111. [10] J.H. Lee, D.L. Trimm, Fuel Process. Technol. 42 (23) (1995) 339359. [11] T.V. Choudhary, S. Banerjee, V.R. Choudhary, Appl. Catal. A Gen. 234 (12) (2002) 123. [12] T. Grifn, W. Weisenstein, V. Scherer, M. Fowles, Combust. Flame 101 (12) (1995) 8190. [13] A. Schlegel, P. Benz, T. Grifn, W. Weisenstein, H. Bockhorn, Combust. Flame 105 (3) (1996) 332340. [14] P. Gelin, M. Primet, Appl. Catal. B Environ. 39 (1) (2002) 137. [15] M. Lyubovsky, L.L. Smith, M. Castaldi, H. Karim, B. Nentwick, S. Etemad, R. LaPierre, W.C. Pfefferle, Catal. Today 83 (14) (2003) 7184. [16] R.B. Anderson, K.C. Stein, J.J. Feenan, L.J.E. Hofer, Ind. Eng. Chem. 53 (10) (1961) 809812. [17] G.K. Boreskov, Kinet. Catal. 14 (1) (1973) 724. [18] L.P. Davydova, V.V. Popovskii, N.N. Bulgakov, A.A. Davydov, A.A. Kazakova, N.M. Dobrynkin, Kinet. Catal. 29 (5) (1988) 11621168. [19] T. Rao, K.R. Krishnamurthy, J. Catal. 95 (1) (1985) 209219. [20] J. Haber, in: R.A. Sheldon, R.A. van Santen (Eds.), Catalytic Oxidation: Principles and Applications, World Scientic, Hong Kong, 1995, pp. 1751. [21] I. Wierzba, A. Depiak, Chem. Eng. J. 91 (23) (2003) 287294. [22] R. Rudham, M.K. Sanders, J. Catal. 27 (2) (1972) 287 292. [23] N.V. Nekrasov, A.A. Slinkin, A.V. Kucherov, G.O. Bragina, E.A. Katsman, S.L. Kiperman, Kinet. Catal. 38 (1) (1997) 7780. [24] C.M. deCorrea, A.L. Villa, Appl. Catal. B Environ. 10 (4) (1996) 313323. [25] M.S. Zina, A. Ghorbel, Solid State Sci. 6 (9) (2004) 973980. [26] K.S. Hui, C.Y.H. Chao, in: 8th APISCEU, 2006, FC106. [27] K.S. Hui, C.Y.H. Chao, S.C. Kot, J. Hazard. Mater. 127 (13) (2005) 89101. [28] K.I. Slovetskaya, Russ. Chem. Bull. 53 (10) (2004) 21682171. [29] C.Y.H. Chao, K.S. Hui, W. Kong, P. Cheng, J.H. Wang, Int. J. Heat Mass Transfer 50 (78) (2007) 13021313. [30] S. Chatterjee, H.L. Greene, Y.J. Park, J. Catal. 138 (1) (1992) 179194. [31] M.W. Ryoo, S.G. Chung, J.H. Kim, Y.S. Song, G. Seo, Catal. Today 83 (14) (2003) 131139. [32] L.M. Aparicio, J.A. Dumesic, J. Mol. Catal. 49 (2) (1989) 205221. [33] L.J. Hoyos, H. Praliaud, M. Primet, Appl. Catal. A Gen. 98 (2) (1993) 125138. [34] A.K. Neyestanaki, N. Kumar, L.E. Lindfors, Fuel 74 (5) (1995) 690696.

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