Enhanced Performance for Mesoporous Beta Zeolites Supported Pd in the Methane Catalytic Combustion★

doi:10.6023/A23040175

Abstract

The environmental problems caused by the release of unburned methane from stationary and mobile combustion processes is becoming more serious in recent years. The catalytic combustion of methane has been regarded to be superior to the conventional combustion, and consequently efficient catalysts play important roles during the process. In this study, mesoporous Beta zeolites have been prepared in the presence of a kind of polymer polydiallyldimethylammonium chloride (PDADMAC) as the mesoscale template and been used for the catalytic combustion of methane after supporting Pd. The samples have been intensively characterized by a series of techniques including X-ray diffraction (XRD), N₂ adsorption, scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), temperature program reduction (H₂-TPR) etc. It was found that mesoporous volume of the samples could be controlled by altering the amount of mesoporous template (PDADMAC) and Pd nanoparticles supported on mesoporous Beta zeolites were smaller and more reducible than those supported on the conventional Beta zeolites. Furthermore, Pd(II) species were assigned to be the crucial active sites based on the results of XPS together with H₂-TPR, and the ratio of the Pd(II) determined the catalytic performance. The relatively strong interaction between Pd and the hydroxyl group (caused by the formation of mesopores) of mesoporous Beta zeolites benefit the high ratio of Pd(II) species. As a result, mesoporous Beta zeolites supported Pd showed better catalytic performance in the catalytic combustion of methane than the conventional Beta zeolites supported Pd. As a typical example, Pd/meso-Beta-H2 sample gave T₉₀ (90% conversion temperature) at only 342 ℃, which was much lower than that of Pd/Beta without mesopores (384 ℃) at the same condition. Additionally, catalytic life test exhibited that Pd/meso-Beta-H2 sample was stable and the conversion remained even after 50 h at high temperatures. Kinetics analysis revealed that the apparent activation energies for mesoporous Beta zeolites supported Pd (86~118 kJ/mol) were much lower than that of the conventional Beta zeolites supported Pd (140 kJ/mol). The excellent catalytic performance of mesoporous Beta zeolites supported Pd would be potentially important for the catalytic combustion of methane in the future.

Key words: zeolite, mesopores, Pd, methane, catalytic combustion

Cite this article

Xupan Xu, Kai Fan, Shengze Zhao, Jian Li, Shan Gao, Zhongbiao Wu, Xiangju Meng, Feng-Shou Xiao. Enhanced Performance for Mesoporous Beta Zeolites Supported Pd in the Methane Catalytic Combustion^★[J]. Acta Chimica Sinica, 2023, 81(9): 1108-1112.

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Fig. & Tab. 8

Figure 1. (A) XRD patterns and (B) nitrogen sorption isotherms of Pd/Beta (a), Pd/meso-Beta-H1 (b), Pd/meso-Beta-H2 (c), Pd/meso-Beta- H3 (d) and Pd/meso-Beta-H4 (e) samples

Sample	PDADMAC/SiO₂	S_BET/ (m²•g^–1)	V_micro/ (cm³•g^–1)	V_meso/ (cm³•g^–1)
Pd/Beta	0	484	0.22	0.06
Pd/meso-Beta-H1	0.067	501	0.20	0.17
Pd/meso-Beta-H2	0.133	474	0.19	0.20
Pd/meso-Beta-H3	0.155	427	0.14	0.33
Pd/meso-Beta-H4	0.200	485	0.12	0.95

Table 1. Structural parameters of Beta samples

Figure 2. (A) TEM images and (B) Pd particle size distribution of Pd/meso-Beta-H2 (a) and Pd/Beta samples (b)

Figure 3. (A) Pd3d XPS spectra and (B) H2-TPR profiles of Pd/Beta (a), Pd/meso-Beta-H1 (b), Pd/meso-Beta-H2 (c), Pd/meso-Beta-H3 (d) and Pd/meso-Beta-H4 (e) samples

Figure 4. (A) Light-off curves of Pd/Beta (a), Pd/meso-Beta-H1 (b), Pd/meso-Beta-H2 (c), Pd/meso-Beta-H3 (d) and Pd/meso-Beta-H4 (e) samples, and (B) catalytic stability testing of Pd/meso-Beta-H2 (a) and Pd/Beta (b) at 345 ℃

Figure 5. Arrhenius curves of (a) Pd/Beta, (b) Pd/meso-Beta-H1, (c) Pd/meso-Beta-H2, (d) Pd/meso-Beta-H3 and (e) Pd/meso-Beta-H4 at methane conversion below 15%

Catalyst	E_a/(kJ•mol^–1)	Reaction order of methane	Reaction order of oxygen
Pd/Beta	140	0.69	0.40
Pd/meso-Beta-H1	105	0.66	0.45
Pd/meso-Beta-H2	98	0.68	0.43
Pd/meso-Beta-H3	86	0.66	0.44
Pd/meso-Beta-H4	118	0.70	0.44

Table 2. Dynamic data of samples in the catalytic combustion of methane

Figure 6. (A) Estimation of methane and (B) oxygen orders from the dependence of rate on the reactant concentration in methane oxidation over the Pd/Beta (a), Pd/meso-Beta-H4 (b), Pd/meso-Beta-H1 (c), Pd/meso-Beta-H2 (d) and Pd/meso-Beta-H3 (e)

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