An efficient way to use CO2 as chemical feedstock by coupling with alkanes

doi:10.1016/S1872-2067(23)64416-X

Abstract

Abstract:

The most promising method to eliminate CO₂ is to find large-scale and value-added applications of CO₂as a carbon resource. However, the utilization of CO₂ as feedstock for basic chemicals has long been a great challenge owing to its high thermodynamic stability. Herein, we report the coupling conversion of CO₂ with light alkanes over the HZSM-5 zeolite with much higher aromatic selectivity than light alkanes as the only reactant. A CO₂ conversion of 17.5% and n-butane conversion of 100% with aromatic selectivity of 80% could be achieved by the coupling reaction at the CO₂ to n-butane ratio of 0.475, in which CO₂ not only acted as an agent for balancing hydrogen in the reaction but also partly (~25%) incorporated into the aromatic products. Methyl-substituted lactones (MLTOs) and methyl-substituted cycloalkenones (MCEOs) were identified as key intermediates during the coupling reaction. ¹³C isotope labeling experiments, ¹³C solid-state NMR, in-situ diffuse reflectance infrared Fourier transform spectroscopy, and density functional theory (DFT)calculations revealed that CO₂could react with carbonium ions generated from alkane cracking to form MLTOs, which could further get converted into MCEOs, thus generating aromatic compounds. This coupling reaction provides guidance for the direct utilization of CO₂ to produce value-added chemicals with the simultaneous transformation of light alkanes.

Key words: CO₂ utilization, Light alkanes, Aromatics, Catalysis, Zeolite

Changcheng Wei, Wenna Zhang, Kuo Yang, Xiu Bai, Shutao Xu, Jinzhe Li, Zhongmin Liu. An efficient way to use CO₂ as chemical feedstock by coupling with alkanes[J]. Chinese Journal of Catalysis, 2023, 47: 138-149.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64416-X

https://www.cjcatal.com/EN/Y2023/V47/I4/138

Figures/Tables 9

Fig. 1. Catalytic performance of light alkanes conversion in CO2 or He. (a) Comparison of alkane conversion and the product distribution for the conversion of n-butane, n-pentane, and n-hexane in He or CO2. Reaction conditions: 0.4 g HZSM-5(17), T = 500 °C, Pn-alkane = 21 kPa, in CO2 (PCO2 = 2355 kPa and PAr = 124 kPa) or He (PHe = 2479 kPa), total flow = 30 mL/min at standard temperature and pressure (STP), time on stream (TOS) = 2.4 h. (b) Catalytic performance of n-butane conversion in CO2 or He plotted as a function of TOS. Detailed comparison of aromatics (c) and C1?C3 alkanes (d) selectivity. Others are mainly composed of C4+ alkanes, and A9+ aromatics includes ethylbenzene and the aromatics with more than eight carbon atoms. The amount of hydrogen in the products was very small (< 0.5 wt%) and the carbon balance was calculated about 97% for the reactions.

Fig. 2. Effects of reaction conditions on the coupling reaction of n-butane with CO2 over HZSM-5. Effects of CO2 partial pressure on the coupling reaction: (a) n-butane conversion and products selectivity; (b) C1?C3 alkane selectivity, the molar ratio of converted CO2 to converted n-butane and (H/C)hydrocarbons ratios. Reaction conditions: 0.4 g HZSM-5(17), T = 450 °C, Pn-butane = 13 kPa, PCO2 = 454?2355 kPa and PAr = 33?124 kPa, total flow = 10-48 mL/min at STP, TOS = 2.4 h. (c) Effects of reaction temperature on the coupling reaction. Reaction conditions: 0.4 g HZSM-5(17), Pn-butane = 31 kPa, PCO2 = 2346 kPa and PAr = 123 kPa, total flow = 20 mL/min at STP, TOS = 2.4 h. (d) Effects of contact time on the coupling reaction. Reaction conditions: 0.02-0.8 g HZSM-5(17), T = 500 °C, Pn-butane = 31 kPa, PCO2 = 2346 kPa and PAr = 123 kPa, total flow = 20 mL/min at STP, TOS = 2.4 h. (e) Catalytic performance of coupling reaction at relative low ratio of CO2 to n-butane. Reaction conditions: 1.2 g HZSM-5(17), T = 550 °C, P = 2500 kPa, PCO2/Pn-butane/PAr = 1.9/0.4/0.1, 1.9/1/0.1, 1.9/2/0.1 and 1.9/4/0.1, total flow = 30 mL/min at STP, TOS = 2.1 h. (f) Optimization of CO2 conversion plotted as a function of TOS. Reaction conditions: 1.2 g HZSM-5(17), T = 550 °C, Pn-butane = 1667 kPa, PCO2 = 792 kPa and PAr = 42 kPa, total flow = 30 mL/min at STP. Others are mainly composed of C4+ alkanes, and A9+ aromatics includes ethylbenzene and the aromatic products with more than eight carbon atoms.

Fig. 3. Effects of the Al/(Si+Al) ratio of HZSM-5 on the coupling reaction of n-butane with CO2. Products selectivity (a) and conversion and (H/C)hydrocarbons ratios (b). Reaction conditions: 0.4 g catalyst, T = 500 °C, Pn-butane = 31 kPa, PCO2 = 2346 kPa and PAr = 123 kPa, total flow = 20 mL/min at STP, TOS = 2.4 h. Others are mainly composed of C4+ alkanes.

Fig. 4. (a) 13C distribution of representative products in the effluent during the coupling reaction of n-butane with 13CO2. Contrast of MS spectra of toluene (b) and p-xylene (c) in the effluent during the coupling reaction of n-butane with 13CO2 (up) and 12CO2 (bottom) over HZSM-5. Reaction conditions: 0.2 g HZSM-5(17), T = 450 °C, Pn-butane = 4 kPa, PHe = 162 kPa, PCO2 = 333 kPa, total flow = 9 mL/min at STP.

Fig. 5. GC-MS analysis of retained species occluded in spent HZSM-5(17). (a) GC-MS results (retention times of up to 18 min) of the retained species occluded in spent zeolite after the coupling reaction at 250 °C. (b) Peak area of MCEOs relative to that of internal standard at different temperatures; (c) 13C distribution of oxygenated compounds occluded in spent zeolite after the coupling reaction of n-butane with 13CO2. Reaction conditions: 0.2 g HZSM-5(17), T = 200 and 450 °C, Pn-butane = 4 kPa, PHe = 162 kPa, PCO2 = 333 kPa, total flow = 9 mL/min at STP, and the catalyst was removed after the coupling reaction for 1 h.

Fig. 6. (a) GC-MS results for the retained species occluded in HZSM-5(17) after GVL conversion at different temperature. (b) In situ UV-vis spectra recorded during GVL conversion. (c,d) Gas chromatogram of products in the effluent during GVL conversion over HZSM-5(17) at different temperature: (c) chromatogram results detected by FID; (d) chromatogram results detected by TCD. Reaction conditions: 0.2 g HZSM-5(17), carrier gas (He) = 30 mL/min at STP, WHSV = 1 h?1, TOS = 0.8 h. (e) Peak area ratio of butadiene to CO (black) and butene to CO2 (red) in GC spectra of GVL conversion. Reaction conditions: 0.1 g HZSM-5(17), T = 400 °C, carrier gas (He) = 20 mL/min at STP, WHSV = 1.3 h?1.

Fig. 7. (a) GC-MS results of retained species occluded in spent HZSM-5(17) after the conversion of propene in CO2 or He atmosphere. Reaction conditions: 0.2 g HZSM-5(17), T = 200 °C, Ppropene = 1.8 kPa, PCO2 or PHe = 360 kPa, total flow = 22 mL/min at STP. The catalysts were removed after 5 min of reaction. 13C MAS NMR spectra of HZSM-5(17) on the co-reaction of propene with 13CO (b) or 12CO (c) at different temperatures.

Fig. 9. Proposed mechanism of the aromatic formation (Route A) and CO formation (Route B) for the coupling conversion of n-butane and CO2 over HZSM-5. The calculated free energy barriers of all the elementary reactions (at 450 °C) are given in kJ/mol.

Fig. 8. In situ DRIFT spectra recorded during n-butane conversion in CO2 (a) or Ar (b) atmosphere.

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An efficient way to use CO₂ as chemical feedstock by coupling with alkanes

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