Shape-selective synthesis of para-xylene through tandem CO2 hydrogenation and toluene methylation over ZnCeZrOx/MCM-22 catalyst

doi:10.1016/S1872-2067(25)64668-7

Abstract

Abstract:

Selective synthesis of value-added xylenes and para-xylene (PX) by CO₂ hydrogenation reduces the dependence on fossil resource and relieves the environment burden derived from the greenhouse gas CO₂. Herein, modified MCM-22 zeolite combined with ZnCeZrO_x solid solution is reported to catalyze the tandem CO₂ hydrogenation and toluene methylation reaction at a relatively low temperature (< 603 K), showing xylene selectivity of 92.4% and PX selectivity of 62% (PX/X, 67%) in total aromatics at a CO₂ conversion of 7.7%, toluene conversion of 23.6% and low CO selectivity of 11.6%, as well as giving high STY of xylene (302.0 mg·h^-1·g_cat^-1) and PX (201.6 mg·h^-1·g_cat^-1). The outstanding catalytic performances are closely related to decreased pore sizes and eliminated external surface acid sites in modified MCM-22, which promoted zeolite shape-selectivity and suppressed secondary reactions.

Key words: MCM-22 zeolite, CO₂ hydrogenation, Toluene methylation, Tandem reaction, Para-xylene

Jie Tuo, Zhenteng Sheng, Xianchen Gong, Qi Yang, Peng Wu, Hao Xu. Shape-selective synthesis of para-xylene through tandem CO₂ hydrogenation and toluene methylation over ZnCeZrO_x/MCM-22 catalyst[J]. Chinese Journal of Catalysis, 2025, 73: 174-185.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64668-7

https://www.cjcatal.com/EN/Y2025/V73/I6/174

Figures/Tables 7

Fig. 1. XRD pattern (a), SEM image (b) and TEM images (c,d) of ZnCeZrOx solid solution.

Fig. 2. (a) Catalytic performances for the tandem CO2 hydrogenation and toluene methylation reaction over ZnCeZrOx/MCM-22 catalysts after the modification of MCM-22. (b) The xylenes distribution over different catalysts. (c) The CO2 carbon usage over different catalysts. Reaction conditions: catalyst mass 0.25 g, ZnCeZrOx/zeolite mass ratio 1:1, reduction temperature 673 K, reaction temperature 603 K, pressure 3 MPa, the gas flow rate (H2/CO2 volume ratio = 3:1) 50 mL·min-1, WHSV of toluene 1.2 h-1, reaction time 15 h. (d) Toluene and CO2 conversion, as well as xylenes selectivity, PX selectivity in xylenes, and PX productivity with TOS over the physical mixed composite catalyst of ZnCeZrOx/MS13-2. Reaction conditions: catalyst mass 0.25 g, ZnCeZrOx/MS13-2 mass ratio 1:1, reduction temperature 673 K, reaction temperature 603 K, pressure 3 MPa, the gas flow rate (H2/CO2 volume ratio = 3:1) 50 mL·min-1, WHSV of toluene 1.2 h-1.

Fig. 3. (a) XRD patterns of MCM-22 and MS13-2. TEM images of MCM-22 (b) and MS13-2 (c).

Fig. 4. Ar sorption isotherms and corresponding pore width distribution (insert) of different MCM-22 zeolites.

Fig. 5. (a) p-, m-, o-Xylene desorption FTIR spectra over the MS13-2 zeolite. (b) The residual percentage of xylene isomers according to the peak-intensity changes (signal at 2929 cm?1) over the MS13-2 zeolite at different desorption times (data calculated from Table S7). (c) m-Xylene desorption FTIR spectra over different MCM-22 zeolites. (d) The residual percentage of m-xylene according to the peak-intensity changes (signal at 2929 cm?1) over different MCM-22 zeolites at different desorption time (data calculated from Table S8).

Fig. 6. 2,6-Ditertbutylpyridine-adsorbed IR spectra of MCM-22 and the modified zeolites.

Fig. 7. (a) STY of xylenes (green) and PX (red) at different temperatures over modified MCM-22 (pentagram symbols) and ZSM-5 zeolites in tandem toluene methylation and CO2 hydrogenation, where the data of ZSM-5 are adopted from the representative literatures from the reference as shown in Table S4. (b) Proposed PX synthesis strategy over modified MCM-22. (c) In-situ DRIFTS with the TOS for CO2 hydrogenation reaction over ZnCeZrOx solid solution under the CO2/H2 flow (50 mL·min-1) at 603 K and 0.1 Mpa. (d) In-situ DRIFTS with TOS over the composite catalyst of ZnCeZrOx/MS13-2 in CO2/H2 flow (50 mL·min-1) at 603 K and 0.1 Mpa. The spectra were recorded at intervals of 1 min from 0 to 30 min after reduction of the sample with H2 (30 mL·min-1) for 2 h at 673 K and purged with He (30 mL·min-1) for 0.5 h at 603 K. (e) In-situ DRIFTS with the TOS for toluene methylation in the presence of CO2/H2 (50 mL·min-1) over ZnCeZrOx/MS13-2 at 603 K and 0.1 Mpa. The spectra were recorded at intervals of 1 minute from 0 to 30 min after reduction of the sample with H2 (30 mL·min-1) for 2 h at 673 K and purged with He (30 mL·min-1) for 0.5 h at 603 K. Then toluene was continuously introduced into in-situ chamber in CO2/H2 flow at 603 K.

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Shape-selective synthesis of para-xylene through tandem CO₂ hydrogenation and toluene methylation over ZnCeZrO_x/MCM-22 catalyst

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