Applied Catalysis A: General 296 (2005) 6369 www.elsevier.

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Oxidative dehydrogenation of isobutane to isobutene III Reaction mechanism over CePO4 catalyst
Yusaku Takita a,*, Xia Qing b, Akihide Takami a, Hiroyasu Nishiguchi a, Katsutoshi Nagaoka a
a

Department of Applied Chemistry, Faculty of Engineering, Oita University, Dannoharu, Oita 870-1192, Japan b School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China Received 16 March 2005; received in revised form 20 June 2005; accepted 29 July 2005 Available online 12 October 2005

Abstract Among rare earth phosphates, only CePO4 and LaPO4 exhibit very high activity for oxidative dehydrogenation (ODH) of isobutane. This phenomenon was studied in comparison with the corresponding oxides. Isobutene was formed over NdPO4, which was used as a representative of inactive phosphate catalysts, by simple dehydrogenation with 3032% selectivity, C3H6 and CO2 were formed with a selectivity of 2533% and 2030%, respectively. Isobutene was obtained at a higher selectivity of 7986% over CePO4 and LaPO4. No H2 formation suggests that the essential reaction was the ODH of isobutane. In the oxidation over metal oxides, isobutene selectivity was relatively high: 6070% over CeO2; however, the essential reaction was considered to be a simple dehydrogenation. Isobutene was formed at 4047% selectivity, but simple dehydrogenation of isobutane would proceed over Nd2O3 and La2O3. La2O3, Nd2O3, and NdPO4 have only weak acidic sites. CeO2 has weak acidic sites and those with intermediate strength; LaPO4 and CePO4 have relatively strong acidic sites in addition to the weak acidic sites and those of intermediate strength. Oxidative dehydrogenation activity was correlated with strong acidic sites. ODH of isobutane occurred in the reaction between lattice oxygen of CePO4 and isobutane. Introduction of NH3 into the reaction system reduced both ODH of isobutane and CO2 formation; and stopping the NH3 supply led to a resumption of the activity, which suggests the participation of acidic sites. CePO4 catalyst contained 2% excess Ce to P; in the prepared CePO4 sample, Ce4+ was detected by XPS. We conclude that acidic sites and redox between Ce4+ and Ce3+ play important roles in the ODH of isobutane. # 2005 Elsevier B.V. All rights reserved.
Keywords: Oxidative dehydrogenation of isobutane; Acidic sites; Reaction mechanism; CePO4; Lattice oxygen

1. Introduction Selective oxidation of saturated lower alkanes is an interesting subject from the viewpoint of the utilization of economical feedstock in the petrochemical industry. It is one of the most challenging subjects because it is quite difcult to achieve the selective oxidation of such compounds with no reactive functional groups. Oxidative dehydrogenation (ODH) of isobutane cannot be achieved over metal oxides, such as MoO3 and V2O5 on which selective oxidation of olens can proceed [16]. Metal phosphates have negative
* Corresponding author. Tel.: +81 97 554 7894; fax: +81 97 554 7979. E-mail address: takita@cc.oita-u.ac.jp (Y. Takita). 0926-860X/$ see front matter # 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.apcata.2005.07.049

large free energies of formation, in other words, they have very stabilized lattice oxygen ions which are strongly bonded with phosphorous ions. We have reported that isobutane was oxidatively dehydrogenated into isobutene selectively over the metal phosphate catalysts [714]. For example, when an isobutane-rich reactant gas mixture composed of 75 mol% isobutane, 5 mol% O2, and 20 mol% N2, was introduced as a feed gas, isobutane was oxidatively dehydrogenated into isobutene over Ni2P2O7, CePO4, and LaPO4 catalysts with approximately 80% selectivity at 500 550 8C, in contrast to the low selectivity of 2540% over other phosphates. The optimum oxygen concentration for isobutene formation was approximately 510 mol% and the oxygen fed was completely consumed during the oxidation.

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This suggests that the rate of donation of the lattice oxygen ions of the catalysts into the surface intermediate derived from isobutane was limited. These reaction conditions will be an important factor in achieving the selective oxidation of isobutane. As for the active oxygen species on the catalysts, we claried using the temperature programmed reduction (TPR) method and oxygen isotope exchange reactions that only the lattice oxygen located in the surface monolayer participated in the ODH of isobutane over the CePO4 and LaPO4 catalysts. Another important point raised by ongoing studies is that the catalysts that are effective for selective oxidation always possess acidic sites. We claried from the isobutane oxidation over rare earth phosphate catalysts that only two catalysts, CePO4 and LaPO4, are effective for the selective ODH of isobutane. Each metal phosphate has acidic sites with an intrinsic distribution of strength; however, only these two phosphates possess large amounts of acidic sites with an intermediate strength that corresponds to the NH3 desorption at 200400 8C in temperatureprogrammed desorption (TPD) spectra [13]. These results clearly show that ODH of alkanes requires the acidity of the catalysts. In this paper, the active sites and the reaction mechanism of the ODH of isobutane over the CePO4 catalyst are discussed.

mixture, which was composed of 75 mol% isobutane, 5 mol% oxygen, and 20 mol% nitrogen as an internal standard, was fed into the reactor. The reactant gas and efuent gas were analyzed by gas chromatography with columns of molecular sieves, silica gel, activated alumina, thermon 1000, and PEG 1000. Products were identied using a GCMS, JEOL Automass system. 2.3. TPD measurement TPD measurements were performed using an ordinary ow-type apparatus. The sample, 0.50 g, was evacuated at 550 8C for 1 h and then cooled to ambient temperature. NH3 was then introduced and equilibrated at 100 Torr at the same temperature. After 30 min of exposure, any gaseous NH3 that remained was replaced by He. The temperature of the samples was raised to 550 8C in a He stream of 30 cm3/min at a rate of 10 8C/min. Desorbed gas was recorded using a TCD detector and was analyzed by GCMS. 2.4. TPR measurement N2 gas containing 2 mol% of hydrogen was used as the carrier gas in the TPR measurements. The pretreatment of the samples is the same as in NH3 TPD measurements. 2.5. Circulated reaction system

2. Experimental 2.1. Catalyst preparation Metal phosphates and pyrophosphates were prepared by the following procedure. An aqueous solution of sodium pyrophosphate was added to an aqueous solution of each metal nitrate or chloride with stirring, and the precipitate that formed was separated by ltration. Each precipitate was adequately washed with pure water and then dried overnight at 130 8C. The catalyst powder calcined at 600 8C for 5 h in air was pressed into pellets and then crushed into 14 32 mesh granules. X-ray diffraction analysis (XRD) revealed that the catalysts calcined at 600 8C were phosphates. Oxides were prepared by the following procedure. An aqueous solution of ammonia was added to an aqueous solution of each metal nitrate until a pH of 7.0 was achieved. The next procedures followed were the same as those described for the preparation of phosphates. 2.2. Experimental procedure Each catalytic reaction was carried out using an ordinary ow-type reaction system with a xed catalyst bed, which is mentioned in reference [12]. The 1432 mesh SiC granules were charged in the upper and the lower part of the catalyst bed to avoid a homogeneous reaction, which may occur in the pre- and post-catalytic volumes. The reactant gas

The apparatus was composed of a reactor (cm3), circulation pump (cm3), sampling port (4.5 cm3), and Hg manometer (cm3). Here, 2.00 g of the CePO4 catalyst was oxidized by 100 Torr oxygen for 1 h at 550 8C and then evacuated at 550 8C for 30 min. After cooling to 500 8C, 1624 mmol of isobutane was introduced and circulated, and the composition of the gas phase was monitored by GCMS.

3. Results and discussion 3.1. Comparison of the catalytic activity of rare earth oxides and rare earth phosphates As noted in a previous paper [13], only the CePO4 and LaPO4 catalysts among the rare earth phosphates were highly effective for selective ODH of isobutane; therefore, the catalytic activities of the corresponding oxides, CeO2 and La2O3, and that of Nd2O3, which is representative of an oxide corresponding to a poor selectivity phosphate, were studied. The results are shown in Table 1. Some experimental results of phosphates are also shown in Table 1 to aid in comparison. As is evident from the table, isobutane conversion over Nd2O3, 6.0% at 550 8C, was much higher than that over NdPO4, 2.9%. High isobutene selectivity, 77.5%, was observed at 450 8C and the selectivity of C3H6, 15.1%, was

Y. Takita et al. / Applied Catalysis A: General 296 (2005) 6369 Table 1 Oxidation of isobutane over rare earth oxides Catalyst (SSA, m2/g) Nd2O3 (11.5) Temperature (K) 723 773 823 723 773 793 823 723 773 798 823 773 823 773 823 773 823 Conversion (%) C4H10 1.5 3.4 6.0 1.1 1.8 3.0 6.2 1.8 2.4 2.9 3.8 2.1 2.9 4.11 10.2 2.46 8.18 97.0 98.9 46.1 99.4 O2 98.6 100 100 98.1 98.2 98.2 99.1 98.2 98.5 98.7 98.8 1/4CH4 4.5 5.3 9.7 0.4 1.6 3.3 5.3 2.2 3.9 5.3 6.6 5.0 8.1 0.4 1.3 0.5 0.9 1/2C2H6 0.5 0.4 0.6 Selectivity (%) 3/4C3H6 15.1 20.9 32.9 7.9 9.2 10.1 11.0 8.6 17.9 23.8 28.5 24.7 33.2 4.6 6.7 7.4 7.8 i-C4H8 77.5 46.4 44.0 44.5 62.1 69.0 69.8 46.9 44.5 42.3 41.8 30.8 32.3 78.7 86.4 86.2 84.2 1/4CO 3.5 3.2 2.7 5.5 8.7 16.2 14.9 11.6 8.4 9.7 6.1 8.5 3.0 4.0 3.1 1/4CO2 2.4 23.5 12.9 44.0 24.3 12.1 5.1 26.0 18.6 16.8 14.4 29.3 19.8 6.6 2.0 0.7 3.1 Rate of H2 evolution, Aa (mmol/min) 6.71 9.33 10.8 6.98 16.2 34.5 77.5 7.82 12.4 16.0 22.3 20.7 21.6 0.09 0 0 0 Rate of H2 formation, Bb (mmol/min) 8.63 14.4 27.1 7.1 17.0 37.2 86.6 8.93 15.0 20.3 29.3 23.7 23.9 0.54 3.72 0.34 2.01

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A/Bb (%) 59.1 55.4 46.3 132 136 152 158 87.3 106 93 93 174 122 2.7 4.1 1.4 2.8

CeO2 (30.0)

0.1 0.1 0.2 0.2 0.3 0.5d 0.6d 0 0.1d 0.1d

La2O3 (7.0)

NdPO4c (15.9) CePO4c (16.8) LaPO4c (30.8)

Feed gas composition (mol%): isobutane 74.2, O2 5.5, N2 20.2; catalyst 5.5 cm3 (5.11 g); feed rate: 30 cm3/min. a Analyzed by GC. b A + 3(rate of CH4 formation) + (rate of C2H6 formation). c From [2]. d C2H4.

also relatively high. With an increase in the reaction temperature, the selectivity of isobutene reduced to 44% and, conversely, the selectivity of C3H6 was increased over Nd2O3. The formation of CO2 increased once at 500 8C and then decreased to 12.9%. The isobutene selectivity over Nd2O3, 4446% at 500550 8C, was slightly higher than that over NdPO4. Complete oxidation to CO and CO2 was more pronounced over NdPO4 than over Nd2O3. With respect to the formation of hydrogen, the formation rate over NdPO4 was larger than that over Nd2O3. The formation of hydrogen suggests that the simple dehydrogenation of isobutane also proceeds. Since the formation of C3H6 and C4H8 accompanies the formation of equivalent amounts of H2 and since the formations of CH4 and C2H6 consume thrice and equimolar amounts of H2, C4 H10 3H2 ! 4CH4 C4 H10 H2 ! 2C2 H6 C4 H10 ! 4=3C3 H6 H2 C4 H10 ! C4 H8 H2 (1) (2) (3) (4)

The contribution of the simple dehydrogenation was estimated from the stoichiometry of these reactions. The ratio of the sum of the rate of actual H2 formation and that required for the CH4 and C2H6 formation against the sum of the calculated rates for the formation of actual C1C4 hydrocarbon production is shown in Table 1. According to this calculation, the ratio for Nd2O3 is 46.359.1%, sug-

gesting that 50% of the hydrocarbons are formed by simple dehydrogenation and cracking of isobutane. In the case of CeO2, the ratio exceeded 100%. This suggests that hydrocarbons are formed by simple dehydrogenation and that other reactions, perhaps steam reforming of isobutane or the formed hydrocarbons, would proceed. Since the ratio for La2O3 takes a value close to 100%, experimental results can be explained only in terms of simple dehydrogenation and cracking of isobutane. The results of phosphates can be clearly classied into two categories. The ratios for NdPO4 were 174% and 122% at 500 and 550 8C, respectively. This indicates that the simple dehydrogenation and cracking of isobutane are the major reactions over NdPO4. On the contrary, although only a small amount of H2 formation was observed over CePO4, the contribution of simple dehydrogenation was estimated to be less than 2.7%. No hydrogen was obtained in the reaction over LaPO4. The selectivity values for isobutene over CePO4 and LaPO4 were appreciably higher than that over NdPO4. These results suggest that the essential reaction is the ODH of isobutane over these two catalysts. The selectivity for isobutene over CeO2 is signicantly high at approximately 70%; however, the essential reaction would be a simple dehydrogenation of isobutane. Propene is a very important feedstock in petrochemistry. Therefore, these two phosphates are of interest from the viewpoint of practical applications because the sum of the selectivity values for C3H6 and C4H8 is extremely high, i.e. 9293%.

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3.2. Participation of the acidic character of the catalysts in the ODH of isobutane In the previous section, it has been claried that the catalytic properties of rare earth oxides and the corresponding phosphates are not uniform. It has been reported that acidic sites promote the ODH of hydrocarbons; propane oxidation over V2O5/Nb2O3 [15], AlNbO4 [16], Mo/gAl2O3 [17], VMgO [18], and Co0.95MoOx [19]. Therefore, the participation of the acidic character of oxides and phosphates in the ODH of isobutane was studied by means of TPD of ammonia. The TPD spectra of NH3 adsorbed on these catalysts are shown in Fig. 1. The spectra of the LaPO4 and CePO4 catalysts were similar to each other; they were composed of two large desorption peaks with peak tops at 100150 8C and 250300 8C, respectively. In the cases of LaPO4 and CePO4, the second peak has a tailing at higher temperatures of 550 8C. In contrast to these spectra, the spectrum of

NdPO4 was composed of one desorption peak at 50220 8C with a peak top at 150 8C. Differences in these phosphate catalysts are very clear; LaPO4 and CePO4 catalysts have weak acidic sites, those of intermediate strength, and strong acidic sites, while the NdPO4 catalyst has only weak acidic sites. As for the TPD of NH3 of the metal oxides, La2O3 exhibited only a small peak at 160270 8C and Nd2O3 also exhibited a very small desorption peak at 135200 8C. In contrast to these spectra, CeO2 exhibited a large desorption peak at 40380 8C and a very small peak at 420475 8C. In other words, Nd2O3 has no acidic sites, La2O3 has a small amount of weak acidic sites, and CeO2 has weak acidic sites as well as those of intermediate strength. The catalysts are thus classied into three groups: La2O3Nd2O3, and NdPO4 belong to the rst group, which have no acidic sites or has only weak acidic sites. The second group contains CeO2, which has acidic sites of weak and of intermediate strength. The third one consists of CePO4 and LaPO4, which have weak acidic sites, those of intermediate strength, and strong acidic sites. This classication appears to be reected in the selectivity of the catalysts for oxidation of isobutane; the catalysts of group 1 show the high selectivity for CO and CO2. The group 2 catalyst shows relatively high selectivity for isobutene and the catalysts of the third group show the high isobutene selectivity. It can be concluded from these facts that the strong acidic sites promote the oxidative dehydrogenation of isobutane. The acidic sites with intermediate strength promote the simple dehydrogenation of isobutane. In the case of CeO2, which has acidic sites of intermediate strength and where the selectivity of isobutene is relatively high; however, isobutene would be formed via simple dehydrogenation of isobutane. 3.3. The effect of NH3 addition on the ODH of isobutane over the CePO4 catalyst The authors have reported in a previous paper that, among the various rare earth phosphates, the selective ODH proceeds only over CePO4 and LaPO4 catalysts [7]. In the previous section, it was claried that the strong acidic sites of both the catalysts are related to the oxidative dehydrogenation of isobutane. To examine the participation of acidic sites, we studied the effect of coexistence of NH3 in the reaction system on the ODH of isobutane using the CePO4 catalyst. The results are shown in Fig. 2. After a steady reaction was achieved at 550 8C, 4.76 mol% of NH3 was introduced in the reactor. When NH3 was introduced, the rate of isobutene formation declined to 72% of the value before NH3 introduction within approximately 300 min and then it achieved a steady state. The rate of CO2 formation immediately decreased to 20% of the value before NH3 introduction. The rate of oxygen consumption, which was at as high a level as approximately 95% in the absence of NH3, is slightly increased to 97% by NH3 addition. No exact analysis of NH3 concentration was carried out, but a part of

Fig. 1. TPD spectra of NH3 of some phosphates and their corresponding oxides. Catalyst: 0.50 g; pre-evacuated at 550 8C for 1 h; NH3 adsorption: 100 Torr at RT for 30 min; carrier gas: He, 30 cm3/min; rate: 10 8C/min.

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Fig. 2. Effect of NH3 on the ODH of isobutane. Catalyst: CePO4, 5.11 g; feed gas composition (mol%): 75 isobutane, 5 O2, 20 N2, or 75 isobutane, 5 O2, 15 N2, 5 NH3; feed rate: 30 cm3/min; reaction temperature: 500 8C; *: isobutene, &: CO2.

NH3 was oxidized and unreacted NH3 was detected in the eluted gas. If the entire added 4.76 mol% NH3 is to be completely oxidized, 3.57 mol% O2 is required, as given by the following equation: NH3 + 3/4O2 ! 1/2N2 + 3/2H2O. An increase in oxygen consumption may reect the progress of oxidation of NH3. NH3 should preferably adsorb on the strong acidic sites, so that the sharp reduction of CO2 formation may reect the situation. Further, the reduction of isobutene formation by the introduction of NH3 shows that oxidative dehydrogenation of isobutane would be competitive with the adsorption of NH3. Perhaps abstraction of H from isobutane molecules by Ce4+ may compete with the adsorption of NH3 molecules onto Ce4+. Since the concentration of NH3 was as low as 4.76%, isobutene formation would not stop completely. After 2600 min, introduction of NH3 was halted. Subsequently, the rate of isobutene formation recovered rapidly to the initial level. On the other hand, the CO2 formation also increased by stopping NH3 introduction, but it exceeded the initial rate. It is of interest to observe the rebound of CO2 formation; it may be due to the effect of concentration of surface hydroxyls that accumulated during the combustion of NH3. It can be concluded from these results that the acidic sites will participate in the ODH of isobutane. 3.4. Participation of lattice oxygen on the surface of CePO4 In the previous paper [7], the authors have reported that only a limited amount of lattice oxygen ions on the CePO4 surface participated in the oxygen isotopic exchange reaction. This suggests that lattice oxygen can play a role in the catalytic oxidation of isobutane. To conrm the participation of surface lattice oxygen, we carried out the reaction between isobutane and lattice oxygen of the CePO4

Fig. 3. Oxidation of isobutane in the absence of gaseous oxygen. Catalyst: CePO4, 2.00 g; feed gas composition (mol%): 75 isobutane, 25 N2; feed rate: 30 cm3/min; reaction temperature: 500 8C; *: isobutene, &: CH4, C2H6, and C3H6, ~: CO2.

catalyst in the absence of gaseous oxygen using a closed circulation system (130 cm3). Fig. 3 shows the time course of the formation of the products at 500 8C. Hydrocarbons such as CH4, C2H6, C3H6, isobutene and CO2 were obtained from the reaction until 300 min. No CO was formed. CO2 formation was observed until 50 min. The total selectivity of isobutene was approximately 81.3%, which is similar to the 78.7% in the reaction by ow-type reactor (see Table 1). Selectivity of CO2 was only 2.9%; this is much lower than 8.5% CO and 6.6% CO2 in the reactions by ow-type reactor. The rates (slopes of both curves) of isobutene and C1C3 hydrocarbon formation increased with reaction time. This suggests that strong acidic sites, perhaps Lewis acid sites, were generated by the oxygen removal from the catalyst surface. No hydrogen was detected in the gas phase throughout the experiment. The weight of the catalyst used was 2.00 g and the specic surface area of the catalyst was 16.8 m2/g. The amount of surface oxygen ions was calculated to be 16.8 2.00 1019/2 6.02 1023 or 279 mmol O2 for oxygen ions having an exposure of approximately 1019 atm./m2 to the surface. The amount of the oxygen consumed by the TPR measurement up to 550 8C was approximately 30% of surface oxygen, as reported in Ref. [7]. Based on these results, the amount of surface oxygen that is available for use in the reaction is estimated to be 83.7 mmol O2. The amount of the oxygen required to form the actual products at 300 min as shown in Fig. 3 is calculated to be 44.4 mmol O2, which is approximately 53% of the available surface oxygen and 15.9% of surface oxygen. Therefore, the results shown in Fig. 3 were estimated to be the products of the reaction between the surface lattice oxygen ions and isobutane. This experiment shows that only the lattice oxygen ions of CePO4 surface participated in the ODH of isobutane.

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As mentioned below, CePO4 contained approximately 2% of CeO2 as an impurity. If only CeO2 participates in the oxidation, the oxygen required to produce the actual products until 300 min is approximately 19.1% of oxygen ions of 0.04 g CeO2 or 232 mmol O2. In both the cases, it is possible to form the products from the reaction between lattice oxygen and isobutane. 3.5. The valence of Ce at the CePO4 surface In the previous section, we concluded that lattice oxygen at the catalyst surface participated in the oxidative dehydrogenation of isobutane. However, the formal valence of Ce ions in CePO4 is Ce3+. Next, we investigate the manner in which the oxidation of isobutane over the CePO4 catalyst proceeds. Two sets of redox pairs are considered in the redox mechanism: (Ce2+ and Ce3+) and (Ce3+ and Ce4+). Since Ce2+ is not stable under the reaction conditions, it is most probable that the redox occurs between Ce3+ and Ce4+. The valence of Ce ions in the CePO4 catalyst was examined by XPS from this viewpoint. The results are shown in Fig. 4. Fig. 4a is the spectrum of CeO2; this sample emitted signals at 916.8, 898.0, and 883.0 eV, which are characteristic of

Ce4+ [2023]. Fig. 4c is the spectrum of natural monazite (CePO4). This compound emitted signals at 904 and 886 eV, which are characteristic of Ce3+. The signals at 901 and 883 eV are the satellites of the peaks at 904 and 886 eV. The spectrum of natural monazite appears to emit no signal at around 917 eV, which is characteristic of Ce4+. Fig. 4b is the spectrum of the CePO4 sample which was used during the ODH of isobutane. This spectrum is composed of signals at 886, 904.6, and 917.4 eV; therefore, this sample contains Ce3+ and Ce4+. Chemical analysis of this sample shows that the ratio of Ce/P is 51/49. No CeO2 was detected by XRD; however, it is clear that this sample contains approximately 2 mol% of CeO2. Taking this result into consideration, we conclude that observation of Ce4+ in XPS is quite reasonable. To change the valence of Ce3+ in CePO4 is not so easy, but CeO2 has many redoxable lattice oxygen ions. Therefore, a small amount of CeO2 contained as an impurity in the prepared CePO4 catalyst would be responsible for the oxidation of isobutane and the reaction would proceed by redox between Ce3+ and Ce4+. In the case of LaPO4, similarly to CePO4, oxygen isotope equilibration occurs over LaPO4, suggesting that there are easily removable oxygen ions on the surface of LaPO4. A part of the La3+ ions located on the outermost layer may bind to oxygen ions instead of phosphate ions. This La ion may act as a redox catalyst. We tentatively propose a reaction mechanism for isobutane oxidation over CePO4, as shown in Fig. 5. Isobutane is adsorbed onto the lattice O2 and Ce4+ to form isobuthylcarbenium ion and H. Isobutene is released from

Fig. 4. XPS spectra of Ce compounds. (a) CeO2, (b) CePO4 prepared in this study, (c) natural monazite (CePO4).

Fig. 5. Suggested reaction mechanism on the CePO4 catalyst.

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buthylcarbenium and a proton remains. The electron of H migrates to Ce4+ to form Ce3+ and an H radical. The elimination of a water molecule from the surface results in the formation of OH and H radical to form a pair of Ce3+. Elimination of a water molecule forms a pair of Ce3+, which is then oxidized by molecular oxygen to Ce4+, i.e. its original state. The upper part of the gure shows the cracking of isobutane. If propylene is eliminated from an isobuthylcalbenium ion adsorbed on the strong acidic site, a methylcarbenium ion remains on the surface. Subsequently, the methylcarbenium ion recombines with H to from a methane molecule. In the cracking process, redox of Ce ions is not required.

4. Conclusions (1) Only CePO4 and LaPO4 have strong acidic sites which participate in the ODH of isobutane. (2) Lattice oxygen ions over CePO4 surface participate in the ODH of isobutane. (3) Ce4+ ions contained in the CePO4 sample play a role in the ODH of isobutane. (4) The ODH of isobutane will proceed via redox of Ce3+ and Ce4+.

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