Mo-promoted Pd/NaY catalyst for indirect oxidative carbonylation of methanol to dimethyl carbonate

doi:10.1016/S1872-2067(24)60019-7

Abstract

Abstract:

A chlorine-free catalyst consisting of zeolite Y modified with Pd (Pd/NaY) catalyst has been prepared and used in the indirect oxidative carbonylation of methanol to dimethyl carbonate (DMC). The activity and stability of the catalyst were further improved by introducing molybdenum into Pd/NaY using a top-down approach (Pd-Mo/NaY catalyst). The Pd-Mo/NaY catalyst exhibited higher stability compared to the Pd/NaY. A high CO conversion of 97% and DMC selectivity of 80% during a 30-hour catalytic test for the Pd-Mo/NaY were obtained. Furthermore, the incorporation of Mo was found to partially heal the silanols and hinder the aggregation of Pd in the Pd-Mo/NaY catalyst. The interactions between Mo and Pd increased the amount of active Pd²⁺ species and enhanced the adsorption of CO reactant on the Pd-Mo/NaY catalyst. The key reaction intermediate of COOCH₃* was captured by in situ diffuse reflectance infrared Fourier transform spectroscopy. The stabilization of active Pd²⁺ species contributed to the enhanced catalytic activity of the Pd-Mo/NaY catalyst in the indirect oxidative carbonylation of methanol to DMC reaction.

Key words: Zeolite, NaY, Palladium, Carbonylation, Dimethyl carbonate

Ke Huang, Shicheng Yuan, Rongyan Mei, Ge Yang, Peng Bai, Hailing Guo, Chunzheng Wang, Svetlana Mintova. Mo-promoted Pd/NaY catalyst for indirect oxidative carbonylation of methanol to dimethyl carbonate[J]. Chinese Journal of Catalysis, 2024, 60: 327-336.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60019-7

https://www.cjcatal.com/EN/Y2024/V60/I5/327

Figures/Tables 14

Fig. 1. Conversion of CO and CH3ONO, selectivity of DMC, dimethoxymethane (DMM) and methyl formate (MF) over the catalysts Pd/NaY (A) and Pd-Mo/NaY (B) as a function of time on stream in the gas-solid phase indirect oxidation of methanol to DMC. Reaction conditions: 0.100 g catalyst, CO/CH3ONO/N2 = 1/6/33 (volume), GHSV = 8000 mL gcat.?1 h?1, 110 °C, 0.1 MPa.

Fig. 2. Effect of the CO/CH3ONO ratio on the CH3ONO conversion and DMC selectivity over the Pd-Mo/NaY catalyst in the gas-solid phase indirect oxidation of methanol to DMC. Reaction conditions: 0.100 g catalyst, CO/CH3ONO/N2 = 1, 1.2, 1.5, 2, 3/6/33 (volume), GHSV = 8000-12000 mL gcat.?1 h?1, 110 °C, 0.1 MPa.

Table 1 Physicochemical properties and catalytic performance of the Pd/NaY and Pd-Mo/NaY catalysts.

Catalyst	Status	S_BET^a (m² g⁻¹)	V_mic^a (cm³ g⁻¹)	TOF (s⁻¹)^b	E_a^c (kJ mol⁻¹)
Pd/NaY	fresh	887	0.33	0.005	72
Pd/NaY	after 30 h test	863	0.32	-	-
Pd-Mo/NaY	fresh	857	0.32	0.019	87
Pd-Mo/NaY	after 30 h test	794	0.30	-	-

Fig. 3. Arrhenius plot for the DMC synthesis on the Pd/NaY and Pd-Mo/NaY catalysts (Ea, apparent activation energy). Reaction conditions: mixture of 0.010 g catalyst and 0.090 g α-Al2O3 (diluent), CO/CH3ONO/N2 = 1/6/33 (volume), GHSV = 80,000 mL gcat.?1 h?1, 0.1 MPa.

Fig. 4. XRD patterns in the range of 3°-50°(A) and enlarged patterns (B) in the range of 30°-45°: fresh Pd/NaY (a), Pd/NaY after 30 h catalytic test (b), fresh Pd-Mo/NaY (c), Pd-Mo/NaY after 30 h catalytic test (d), and NaY zeolite (e).

Fig. 5. TEM images of used catalysts after 30 h catalytic test: Pd/NaY (a1,a2) and Pd-Mo/NaY (b1,b2). Insets: particle size distribution of Pd nanoparticles in samples Pd/NaY (a1) and Pd-Mo/NaY (b1) determined by measuring of about 200 nanoparticles.

Fig. 6. SEM images and EDS elemental mapping of Pd/NaY (a) and Pd-Mo/NaY (b) used catalysts after 30 h catalytic test.

Fig. 7. FT-IR spectra of NaY (a), Pd/NaY (b), Mo/NaY (c) and Pd-Mo/NaY (d) samples in the OH stretching vibration region (3400-3800 cm?1).

Fig. 8. FT-IR spectra of CO adsorbed at -140 °C on NaY (A), Mo/NaY (B), Pd/NaY (D) and Pd-Mo/NaY (E) samples. (C) The band areas at 2167 cm-1 versus the CO partial pressure. (F) The band areas at 2169 cm-1 versus the CO partial pressure. The spectra were collected at the equilibrium CO partial pressure of 132 Pa (a) -385 Pa (g).

Fig. 9. DRIFTS spectra of CO adsorbed on used Pd/NaY catalysts after 2 h (a) and 6 h (b) catalytic test, and on used Pd-Mo/NaY catalysts after 2 h (c) and 6 h (d) catalytic test recorded at 35 °C.

Fig. 10. H2-TPR profiles of fresh Pd/NaY (a) and Pd-Mo/NaY (b) catalysts.

Fig. 11. XPS spectra of Pd 3d (A) and Mo 3d (B) regions of used Pd/NaY (a) and Pd-Mo/NaY (b) catalysts.

Table 2 The peak areas of Pd0, Pd2+, and Pd2+/Pd0 area ratio of the used catalysts Pd/NaY and Pd-Mo/NaY determined by XPS a.

Catalyst	Area of Pd⁰		Area of Pd²⁺		Pd^2/Pd⁰ ratio
Pd/NaY	1367^a	1640^a		1.2
Pd-Mo/NaY	1524^a	2437^a		1.6

Fig. 12. In situ DRIFTS spectra of CO and CH3ONO reactants on Pd/NaY (A) and Pd-Mo/NaY (B) catalysts, and the corresponding surface species on the Pd/NaY (C) and Pd-Mo/NaY (D) catalysts after parching with N2 recorded at different temperatures: 30, 50, 70, 90, 110 and 125 °C.

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