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Received October 17, 2023
Accepted December 2, 2023
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Modifi ed Cu–ZnO Catalysts Supported on the Mixture of ZnO and Zn–Al Oxide for Methanol Production via Hydrogenation of CO and CO 2 Gas Mixture
Hyun-tae Song1
Hyun Dong Kim2
Yu-jeong Yang2
Jeong Min Seo2
Ye-na Choi2
Kwan-Young Lee2
Dong Ju Moon1 2†
Clean Energy Research Center, Korea Institute of Science and Technology (KIST) 1Division of Energy and Environment Technology, KIST School , Korea University of Science and Technology (UST) 2Department of Chemical & Biological Engineering , Korea University
djmoon@kist.re.kr
Korean Journal of Chemical Engineering, May 2024, 41(5), 1375-1389(15), https://doi.org/10.1007/s11814-024-00022-7
Abstract
Cu-based catalysts were created using a two-step co-precipitation method, which can produce methanol from synthesis gases
(H 2 and CO) that also contain CO 2 . The catalysts were manufactured by a two-step co-precipitation method and compared
with catalysts manufactured by a one-step co-precipitation method. The supports with Zn/Al = 1 (10ZA) and Zn/Al = 2
(20ZA) showed higher ZnAl 2 O 4 ratios than the other catalysts, and the catalysts using these supports showed a similar trend
to the ZnAl 2 O 4 ratio. Cu–ZnO/mixture ZnO and ZnAl 2 O 4 catalysts with more ZnAl 2 O 4 (C10Z/20ZA and C20Z/10ZA)
showed lower carbon and CO conversion losses and lower sintering of Cu (200) particles at the reaction temperatures (250,
300, and 350 °C) than the Cu–ZnO-ZnAl 2 O 4 (C30ZA) catalyst. Cu–ZnO/mixture ZnO and ZnAl 2 O 4 using support with Zn/
Al = 2 (C10Z/20ZA) achieved dispersion of Cu (44.2%) and a methanol yield (409.0 g MeOH /kg cat. /h) at a reaction temperature
of 250 °C, GHSV of 4,444 h −1 , and 40 bar.
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(2016)
2. A.R. Richard, M. Fan, Fuel 222 , 513 (2018)
3. M. Behrens, Angew. Chem. Int. Ed. 55 , 14906 (2016)
4. S.A. Kondrat, P.J. Smith, L. Lu, J.K. Bartley, S.H. Taylor, M.S.
Spencer, G.J. Kelly, C.W. Park, C.J. Kiely, G.J. Hutchings, Catal.
Today 317 , 12 (2018)
5. Y.M. Liu, J.T. Liu, S.Z. Liu, J. Li, Z.H. Gao, Z.J. Zuo, W. Huang,
J. CO2 Util. 20 , 59 (2017)
6. M. Bowker, ChemCatChem 11 , 4238 (2019)
7. L. Wang, L. Yang, Y. Zhang, W. Ding, S. Chen, W. Fang, Y. Yang,
Fuel Process Techonol. 91 , 723 (2010)
8. H. Jung, D.-R. Yang, O.-S. Joo, K.-D. Jung, Bull. Korean Chem.
Soc. 31 , 1241 (2010)
9. X.-M. Liu, G. Lu, Z.-F. Yan, J. Beltramini, Ind. Eng. Chem. Res.
42 , 6518 (2003)
10. J. Nakamura, T. Uchijima, Y. Kanai, T. Fujitani, Catal. Today 28 ,
223 (1996)
11. T. Fujitani, J. Nakamura, Catal. Lett. 56 , 119 (1998)
12. J. Bart, R. Sneeden, Catal. Today 2 , 1 (1987)
13. D. Sheldon, Johns. Matthey Technol. Rev. 61 , 172 (2017)
14. S. Ren, W.R. Shoemaker, X. Wang, Z. Shang, N. Klinghoff er, S.
Li, M. Yu, X. He, T.A. White, X. Liang, Fuel 239 , 1125 (2019)
15. M.N. Barroso, M.F. Gomez, J.A. Gamboa, L.A. Arrúa, M.C.
Abello, J. Phys. Chem. Solids 67 , 1583 (2006)
16. X. Zhang, G. Zhang, W. Liu, F. Yuan, J. Wang, J. Zhu, X. Jiang,
A. Zhang, F. Ding, C. Song, Appl. Catal. B 284 , 119700 (2021)
17. H.-T. Song, A. Fazeli, H.D. Kim, A.A. Eslami, Y.S. Noh, N.G.
Saeidabad, D.J. Moon, Fuel 283 , 118987 (2021)
18. P. Mierczynski, T.P. Maniecki, K. Chalupka, W. Maniukiewicz,
W.K. Jozwiak, Catal. Today 176 , 21 (2011)
19. L. Song, H. Wang, S. Wang, Z. Qu, Appl. Catal. B Environ. 322 ,
122137 (2023)
20. S. Wang, L. Song, Z. Qu, Chem. Eng. J. 8 , 144008 (2023)
21. S. Radha, J. Mani, R. Rajkumar, M. Arivanandhan, R. Jayavel, G.
Anbalagan, Mater. Res. Express 10 , 025501 (2023)
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P. Chaumette, P. Courty, Appl. Catal. 59 , 165 (1990)
23. W.S. Kim, D.R. Yang, D.J. Moon, B.S. Ahn, Chem. Eng. Res.
Des. 92 , 931 (2014)
24. H. Jung, D.R. Yang, K.D. Jung, Bull. Korean Chem. Soc. 36 , 2875
(2015)
25. A. Fazeli, A.A. Khodadadi, Y. Mortazavi, H. Manafi , Iran. J.
Chem. Chem. Eng. 32 , 45 (2013)
26. S. Sato, R. Takahashi, T. Sodesawa, K.-I. Yuma, Y. Obata, J.
Catal. 196 , 195 (2000)
27. J.R. Jensen, T. Johannessen, H. Livbjerg, Appl. Catal. A: Gen.
266 , 117 (2004)
28. Z. Chen, X. Zhao, S. Wei, D. Wang, X. Zhang, J. Shan, Korean J.
Chem. Eng. 39 , 2983 (2022)
29. B. Sundquist, Acta Metall. 12 , 67 (1964)
30. E. Giamello, B. Fubini, P. Lauro, A. Bossi, J. Catal. 87 , 443 (1984)
31. T. Wang, X. Wang, Y. Gao, Y. Su, Z. Miao, C. Wang, L. Lu, L.
Chou, X. Gao, J. Energy Chem. 24 , 503 (2015)
32. K. Sonobe, M. Tanabe, T. Imaoka, W.J. Chun, K. Yamamoto,
Chem. Eur. J. 27 , 8452 (2021)
33. C. Zhong, X. Guo, D. Mao, S. Wang, G. Wu, G. Lu, RSC Adv. 5 ,
52958 (2015)
34. C.R. Second, E. Edition, G. Ertl, H. Knözinger, F. Schüth, J. Weitkamp,
W.V.V.G. KGaA, Co, Handbook of heterogeneous catalysis,
2008.
35. P. Gao, F. Li, F. Xiao, N. Zhao, W. Wei, L. Zhong, Y. Sun, Catal.
Today 194 , 9 (2012)
36. Y. Zhang, L. Zhong, H. Wang, P. Gao, X. Li, S. Xiao, G. Ding, W.
Wei, Y. Sun, J. CO2 Util. 15 , 72 (2016)
37. V.D. Dasireddy, N.S. Štefančič, M. Huš, B. Likozar, Fuel 233 , 103
(2018)
38. N. Chotigkrai, P. Tannititam, S. Piticharoenphun, N. Triamnak,
S. Praserthdam, P. Praserthdam, Korean J. Chem. Eng. 39 , 920
(2022)
39. Y. Alajlani, F. Placido, A. Barlow, H.O. Chu, S. Song, S.U. Rahman,
R. De Bold, D. Gibson, Vacuum 144 , 217 (2017)
40. H. Tan, M.N. Hedhill, Y. Wang, J. Zhang, K. Li, S. Sioud, Z.A.
Al-Talla, M.H. Amad, T. Zhan, O.E. Tall, Catal. Sci. Technol. 3 ,
3360 (2013)
41. X. Fang, Y. Men, F. Wu, Q. Zhao, R. Singh, P. Xiao, L. Liu, T.
Du, P.A. Webley, Korean J. Chem. Eng. 38 , 747 (2021)
42. L. Grabow, M. Mavrikakis, ACS Catal. 1 , 365 (2011)
43. Z. Azizi, M. Rezaeimanesh, T. Tohidian, M.R. Rahimpour, Chem.
Eng. Process. 82 , 150 (2014)
