Promoting propane dehydrogenation with CO2 over Ga2O3/SiO2 by eliminating Ga-hydrides

doi:10.1016/S1872-2067(21)63900-1

Abstract

Abstract:

Due to the shortage supply of propylene and the development of shale gas, there is increased interest in on-purpose propane dehydrogenation (PDH) technology for propylene production. Ga-based catalysts have great potential in PDH, due to the high activity, low carbon deposit and deactivation. Ga-hydrides formed during PDH reduce the rate, selectivity and yield of propylene. In this contribution, CO₂ is introduced into PDH as a soft oxidant to eliminate the unfavorable intermediate species Ga^δ⁺-H_x re-generating Ga³⁺-O pairs, and also minimize coke deposition thereby improving the catalytic performance. In situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy experiments show that CO₂ can effectively eliminate Ga^δ⁺-H_x. At different temperatures, co-feeding CO₂ during PDH over Ga₂O₃/SiO₂ catalysts with different loadings significantly improves the stability of the conversion and selectivity, especially the latter, and provide a new dimension for improving the performance of PDH process.

Key words: Ga-hydrides, Ga₂O₃, CO₂, Propane dehydrogenation, In situ DRIFT

Yi Liu, Guanghui Zhang, Jianyang Wang, Jie Zhu, Xinbao Zhang, Jeffrey T. Miller, Chunshan Song, Xinwen Guo. Promoting propane dehydrogenation with CO₂ over Ga₂O₃/SiO₂ by eliminating Ga-hydrides[J]. Chinese Journal of Catalysis, 2021, 42(12): 2225-2233.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63900-1

https://www.cjcatal.com/EN/Y2021/V42/I12/2225

Figures/Tables 12

Fig. 1. XRD patterns and propane dehydrogenation performance of Ga2O3/SiO2 with different Ga loadings. (a) XRD patterns; (b) Propane conversion; (c) Propylene selectivity. Reaction conditions: 600 °C, P = 0.05 MPa, GHSV (gas hourly space velocity) = 3900 mL/g/h.

Fig. 2. (a) The amount of carbon deposition on 3Ga2O3/SiO2 and (b) C3H6 yield vs. TOS. Reaction conditions: 600 °C, 0.05 MPa, GHSV = 3900 mL/g/h.

Fig. 3. (a) The rate of C3H6 formation over 8Ga2O3/SiO2. Reaction conditions: 550 °C, 0.05 MPa, GHSV = 19500 mL/g/h, pre-treated in H2 at 650 °C for 1 h. (The C3H8 conversion ranges from 4% to 6%, below the equilibrium conversion of 32% at 550 °C [29].) (b) In situ DRIFT spectra during PDH at 550 °C after 50% H2/N2 pretreatment at 650 °C for 1 h. (c) Peak area of Ga-H (2035 cm?1) vs. time on stream. (d) MS profile obtained during propane dehydrogenation at 550 °C after 50% H2/N2 pretreatment at 650 °C for 1 h.

Fig. 4. In situ DRIFT spectra on Ga2O3. (a) During the treatment of H2; (b) during the treatment of N2 followed by CO2. Conditions: T = 600 °C, ambient pressure.

Fig. 5. In situ DRIFT spectra on 8Ga2O3/SiO2. H2 treatment for 1 h (black), H2 treatment followed by N2 treatment for 20 min (blue), H2 treatment followed by 5%CO2/N2 treatment for 20 min (red), H2 treatment followed by 20%CO2/N2 treatment for 20 min (pink). T = 600 °C, ambient pressure.

Fig. 6. (a) TPSR profiles of 8Ga2O3/SiO2; (b) In situ DRIFT spectra of 8Ga2O3/SiO2. H2 treatment for 1 h (black), H2 treatment followed by 5%CO2/Ar treatment for 20 min (red). T = 600 °C, ambient pressure.

Fig. 7. PDH performance of Ga2O3/SiO2 with different Ga loadings in the presence of CO2. (a) Propane conversion; (b) Propylene selectivity. Reaction conditions: 600 °C, 0.05 MPa, GHSV = 3900 mL/g/h, CO2:C3H8 = 1:1.

Fig. 8. HRTEM images of different samples. (a) Fresh 8Ga2O3/SiO2; (b) 8Ga2O3/SiO2 after PDH without CO2 for 4 h; (c) 8Ga2O3/SiO2 after PDH with CO2 for 4 h.

Fig. 9. (a) TGA profiles of Ga2O3/SiO2 after PDH with or without CO2 for 4 h. Dashed lines indicate the first derivatives of the weight loss curves of the same color; (b) Carbon balance during propane dehydrogenation. Reaction conditions: 600 °C, 0.05 MPa, GHSV = 3900 mL/g/h.

Table 1 Carbon balance during propane dehydrogenation of Ga2O3/SiO2.

CO₂ introduction	3Ga₂O₃/SiO₂	5Ga₂O₃/SiO₂	8Ga₂O₃/SiO₂	10Ga₂O₃/SiO₂
CO₂:C₃H₈= 0:1	97%	92%	87%	86%
CO₂:C₃H₈= 1:1	98%	94%	92%	89%

Fig. 10. PDH performance of 3Ga2O3/SiO2. (a,b) Reaction conditions: 600 °C, 0.05 MPa, GHSV = 3900 mL/g/h; (c,d) Reaction conditions: 627 °C, 0.05 MPa, GHSV = 3900 mL/g/h.

Fig. 11. (a) C3H8-IR spectra of 8Ga2O3/SiO2; (b) CO2-IR spectra of 8Ga2O3/SiO2.

References

[1]	J. J. H. B. Sattler, J. Ruiz-Martinez, E. Santillan-Jimenez, B. M. Weckhuysen, Chem. Rev., 2014, 114, 10613-10653.
[2]	B. V. Vora, Top. Catal., 2012, 55, 1297-1308.
[3]	Z.-P. Hu, D. Yang, Z. Wang, Z.-Y. Yuan, Chin. J. Catal., 2019, 40, 1233-1254.
[4]	J. J. H. B. Sattler, I. D Gonzalez-Jimenez, L. Luo, B. A. Stears, A. Malek, D. G. Barton, B. A. Kilos, M. P. Kaminsky, T. W. G. M. Verhoeven, E. J. Koers, M. Baldus, B. M. Weckhuysen, Angew. Chem. Int. Ed., 2014, 53, 9251-9256.
[5]	B. Zheng, W. Hua, Y. Yue, Z. Gao, J. Catal., 2005, 232, 143-151.
[6]	E. A. Pidko, E. J. M Hensen, R. A. V. Santen, J. Phys. Chem. C, 2007, 111, 13068-13075.
[7]	W.-G. Kim, J. So, S.-W. Choi, Y. Liu, R. S. Dixit, C. Sievers, D. S. Sholl, S. Nair, C. W. Jones, Chem. Mater., 2017, 29, 7213-7222.
[8]	K. C. Szeto, Z. R. Jones, N. Merle, C. S. Rios, A. Gallo, F. L. Quemener, L. Delevoye, R. g. M. Gauvin, S. L. Scott, M. Taoufik, ACS Catal., 2018, 8, 7566-7577.
[9]	B. Xu, B. Zheng, W. Hua, Y. Yue, Z. Gao, J. Catal., 2006, 239, 470-477.
[10]	N. Raman, S. Maisel, M. Grabau, N. Taccardi, J. Debuschewitz, M. Wolf, H. Wittkämper, T. Bauer, M. Wu, M. Haumann, C. Papp, A. Goerling, E. Spiecker, J. Libuda, H.-P. Steinrück, P. Wasserscheid, ACS Catal., 2019, 9, 9499-9507.
[11]	N. M. Schweitzer, B. Hu, U. Das, H. Kim, J. Greeley, L. A. Curtiss, P. C. Stair, J. T. Miller, A. S. Hock, ACS Catal., 2014, 4, 1091-1098.
[12]	L. Benco, T. Bucko, J. Hafner, J. Catal., 2011, 277, 104-116.
[13]	J. Camacho-Bunquin, P. Aich, M. Ferrandon, A. B. Getsoian, U. Das, F. Dogan, L. A. Curtiss, J. T. Miller, C. L. Marshall, A. S. Hock, P. C. Stair, J. Catal., 2017, 345, 170-182.
[14]	S. Sokolov, M. Stoyanova, U. Rodemerck, D. Linke, E. V. Kondratenko, Catal. Sci. Technol., 2014, 4, 1323-1332.
[15]	G. Liu, Z.-J. Zhao, T. Wu, L. Zeng, J. Gong, ACS Catal., 2016, 6, 5207-5214.
[16]	C. Chen, M. Sun, Z. Hu, Y. Liu, S. Zhang, Z.-Y. Yuan, Chin. J. Catal., 2020, 41, 276-285.
[17]	Z. F. Han, X. L. Xue, J. M. Wu, W. Z. Lang, Y. J. Guo, Chin. J. Catal., 2018, 39, 1099-1109.
[18]	T. Davies, S. H. Taylor, J. Mol. Catal. A, 2004, 220, 77-84.
[19]	K. Searles, G. Siddiqi, O. V. Safonovab, C. Copéret, Chem. Sci., 2017, 8, 2661-2666.
[20]	B. Hu, N. M. Schweitzer, G. Zhang, S. J. Kraft, D. J. Childers, M. P. Lanci, J. T. Miller, A. S. Hock, ACS Catal., 2015, 5, 3494-3503.
[21]	D. P. Estes, G. Siddiqi, F. Allouche, K. V. Kovtunov, O. V. Safonova, A. L. Trigub, I. V. Koptyug, C. Copéret, J. Am. Chem. Soc., 2016, 138, 14987-14997.
[22]	B. Hu, A. B. Getsoian, N. M. Schweitzer, U. Das, H. Kim, J. Niklas, O. Poluektov, L. A. Curtiss, P. C. Stair, J. T. Miller, A. S. Hock, J. Catal., 2015, 322, 24-37.
[23]	A. B. Getsoian, U. Das, J. Camacho-Bunquin, G. Zhang, J. R. Gallagher, B. Hu, S. Cheah, J. A. Schaidle, D. A. Ruddy, J. E. Hensley, T. R. Krause, L. A. Curtiss, J. T. Miller, A. S. Hock, Catal. Sci. Technol., 2016, 6, 6339-6353.
[24]	V. J. Cybulskis, S. U. Pradhan, J. J Lovón-Quintana, A. S. Hock, B. Hu, G. Zhang, W. N. Delgass, F. H. Ribeiro, J. T. Miller, Catal. Lett., 2017, 147, 1252-1262.
[25]	N. Rane, A. R. Overweg, V. B. Kazansky, R. A. v. Santen, E. J. M. Hensen, J. Catal., 2006, 239, 478-485.
[26]	N. M. Phadke, E. Mansoor, M. Bondil, M. Head-Gordon, A. T. Bell, J. Am. Chem. Soc., 2019, 141, 1614-1627.
[27]	M. B. Ansari, S.-E. Park, Energy Environ. Sci., 2012, 5, 9419-9437.
[28]	M. Chen, J. Xu, F.-Z. Su, Y.-M. Liu, Y. Cao, H.-Y. He, K.-N. Fan, J. Catal., 2008, 256, 293-300.
[29]	S. Gómez-Quero, T. Tsoufis, P. Rudolf, M. Makkee, F. Kapteijnc, G. Rothenberg, Catal. Sci. Technol., 2013, 3, 962-971.
[30]	G. D. Meitzner, E. Iglesia, J. E. Baumgartner, E. S. Huang, J. Catal., 1993, 140, 209-225.
[31]	E. J. M Hensena, M. Garcia-Sanchez, N. Ranea, P. C. M. M. Magusina, P.-H. Liub, K.-J. Chaob, R. A. Sante, Catal. Lett., 2005, 101, 79-85.
[32]	S. E. Collins, M. A. Baltanás, J. L. G Fierro, A. L. Bonivardi, J. Catal., 2002, 211, 252-264.
[33]	V. B. Kazansky, I. R. Subbotina, R. A. van Santen, E. J. M. Hensen, J. Catal., 2005, 233, 351-358.
[34]	V. B. Kazansky, I. R. Subbotina, R. A. van Santen, E. J. M. Hensen, J. Catal., 2004, 227, 263-269.
[35]	S. E. Collins, M. A. Baltanás, A. L. Bonivardi, Langmuir, 2005, 21, 962-970.
[36]	J. Vecchietti, M. A. Baltanás, C. Gervais, S. E. Collins, G. Blanco, O. Matz, M. Calatayud, A. Bonivardi, J. Catal., 2017, 345, 258-269.
[37]	Y. Liu, Z. H. Li, J. Lu, K.-N. Fan, J. Phys. Chem. C, 2008, 112, 20382-20392.
[38]	Z. Xie, Y. Ren, J. Li, Z. Zhao, X. Fan, B. Liu, W. Song, L. Kong, X. Xiao, J. Liu, G. Jiang, J. Catal., 2019, 372, 206-216.
[39]	S. E. Collins, M. A. Baltanás, A. L. Bonivardi, J. Phys. Chem. B, 2006, 110, 5498-5507.

Promoting propane dehydrogenation with CO₂ over Ga₂O₃/SiO₂ by eliminating Ga-hydrides

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