Conversion of syngas into lower olefins over a hybrid catalyst system

Abstract

Lower olefins, produced from syngas through Fischer-Tropsch synthesis, has been gaining worldwide attention as a non-petroleum route. However, the process demonstrates limited selectivity for target products. Herein, a hybrid catalyst system utilizing Fe-based catalyst and SAPO-34 was shown to enhance the selectivity toward lower olefins. A comprehensive study was conducted to examine the impact of various operating conditions on catalytic performance, such as space velocity, pressure, and temperature, as well as catalyst combinations, including loading pattern, and mass ratio of metal and zeolite. The findings indicated that the addition of SAPO-34 was beneficial for enhancing catalytic activity. Furthermore, compared with AlPO-34 zeolite, the strong-acid site on SAPO-34 was identified to crack the long-chain hydrocarbons, thus contributing to the lower olefin formation. Nevertheless, an excess of strong-acid sites was found to detrimentally impact the selectivity of lower olefins, attributed to the increased aromatization and polymerization of lower olefins. The detailed analysis of a hybrid catalyst in Fischer-Tropsch synthesis provides a practical strategy for improving lower olefins selectivity, and has broader implications for the application of hybrid catalyst in diverse catalytic systems.

Key words： Fischer-Tropsch synthesis; lower olefins; SAPO-34; hybrid catalyst; Fe-based catalyst

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant Nos. 22108200, 22108311), and the Natural Science Foundation of Zhejiang Province (Grant No. LQ22B060013). The authors also thank the Haihe Laboratory of Sustainable Chemical Transformations for financial support.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-024-2467-4 and is accessible for authorized users.

References

1 Torres Galvis H M , de Jong K P . Catalysts for production of lower olefins from synthesis gas: a review. ACS Catalysis, 2013, 3(9): 2130–2149

2 Zhai P , Li Y , Wang M , Liu J , Cao Z , Zhang J , Xu Y , Liu X , Li Y W , Zhu Q . . Development of direct conversion of syngas to unsaturated hydrocarbons based on Fischer-Tropsch route. Chem, 2021, 7(11): 3027–3051

3 Torres Galvis H M , Bitter J H , Khare C B , Ruitenbeek M , Dugulan A I , de Jong K P . Supported iron nanoparticles as catalysts for sustainable production of lower olefins. Science, 2012, 335(6070): 835–838

4 Zhou J , Chu W , Zhang H , Xu H , Zhang T . Effect of Fe content on FeMn catalysts for light alkenes synthesis. Frontiers of Chemical Engineering in China, 2008, 2(3): 315–318

5 Zhou W , Cheng K , Kang J , Zhou C , Subramanian V , Zhang Q , Wang Y . New horizon in C1 chemistry: breaking the selectivity limitation in transformation of syngas and hydrogenation of CO₂ into hydrocarbon chemicals and fuels. Chemical Society Reviews, 2019, 48(12): 3193–3228

6 Zhang Q , Kang J , Wang Y . Development of novel catalysts for Fischer-Tropsch synthesis: tuning the product selectivity. ChemCatChem, 2010, 2(9): 1030–1058

7 Wan H J , Wu B S , Zhang C H , Xiang H W , Li Y W , Xu B F , Yi F . Study on Fe-Al₂O₃ interaction over precipitated iron catalyst for Fischer-Tropsch synthesis. Catalysis Communications, 2007, 8(10): 1538–1545

8 Torshizi H O , Nakhaei Pour A , Mohammadi A , Zamani Y , Kamali Shahri S M . Fischer-Tropsch synthesis by reduced graphene oxide nanosheets supported cobalt catalysts: role of support and metal nanoparticle size on catalyst activity and products selectivity. Frontiers of Chemical Science and Engineering, 2020, 15(2): 299–309

9 Yuan Y , Huang S , Wang H , Wang Y , Wang J , Lv J , Li Z , Ma X . Monodisperse nano-Fe₃O₄ on α-Al₂O₃ catalysts for Fischer-Tropsch synthesis to lower olefins: promoter and size effects. ChemCatChem, 2017, 9(16): 3144–3152

10 Yang X , Yang J , Wang Y , Zhao T , Ben H , Li X , Holmen A , Huang Y , Chen D . Promotional effects of sodium and sulfur on light olefins synthesis from syngas over iron-manganese catalyst. Applied Catalysis B: Environmental, 2022, 300: 120716–120723

11 Liu S , Zhao Q , Han X , Wei C , Liang H , Wang Y , Huang S , Ma X . Proximity effect of Fe-Zn bimetallic catalysts on CO₂ hydrogenation performance. Transactions of Tianjin University, 2023, 29(4): 293–303

12 Zhao Q , Huang S , Han X , Chen J , Wang J , Rykov A , Wang Y , Wang M , Lv J , Ma X . Highly active and controllable MOF-derived carbon nanosheets supported iron catalysts for Fischer-Tropsch synthesis. Carbon, 2021, 173: 364–375

13 Wang Y , Huang S , Teng X , Wang H , Wang J , Zhao Q , Wang Y , Ma X . Controllable Fe/HCS catalysts in the Fischer-Tropsch synthesis: effects of crystallization time. Frontiers of Chemical Science and Engineering, 2020, 14(5): 802–812

14 Ramirez A , Gong X , Caglayan M , Nastase S F , Abou-Hamad E , Gevers L , Cavallo L , Dutta Chowdhury A , Gascon J . Selectivity descriptors for the direct hydrogenation of CO₂ to hydrocarbons during zeolite-mediated bifunctional catalysis. Nature Communications, 2021, 12(1): 5914–5926

15 Sun Q , Wang N , Yu J . Advances in catalytic applications of zeolite-supported metal catalysts. Advanced Materials, 2021, 33(51): 2104442–2104478

16 Yang L , Wang C , Zhang L , Dai W , Chu Y , Xu J , Wu G , Gao M , Liu W , Xu Z . . Stabilizing the framework of SAPO-34 zeolite toward long-term methanol-to-olefins conversion. Nature Communications, 2021, 12(1): 4661–4671

17 Pan X , Jiao F , Miao D , Bao X . Oxide-zeolite-based composite catalyst concept that enables syngas chemistry beyond Fischer-Tropsch synthesis. Chemical Reviews, 2021, 121(11): 6588–6609

18 Qiu T , Wang L , Lv S , Sun B , Zhang Y , Liu Z , Yang W , Li J . SAPO-34 zeolite encapsulated Fe₃C nanoparticles as highly selective Fischer-Tropsch catalysts for the production of light olefins. Fuel, 2017, 203: 811–816

19 Přech J , Strossi Pedrolo D R , Marcilio N R , Gu B , Peregudova A S , Mazur M , Ordomsky V V , Valtchev V , Khodakov A Y . Core-shell metal zeolite composite catalysts for in situ processing of Fischer-Tropsch hydrocarbons to gasoline type fuels. ACS Catalysis, 2020, 10(4): 2544–2555

20 Dai W , Cao G , Yang L , Wu G , Dyballa M , Hunger M , Guan N , Li L . Insights into the catalytic cycle and activity of methanol-to-olefin conversion over low-silica AlPO-34 zeolites with controllable Brønsted acid density. Catalysis Science & Technology, 2017, 7(3): 607–618

21 Xu L , Du A , Wei Y , Wang Y , Yu Z , He Y , Zhang X , Liu Z . Synthesis of SAPO-34 with only Si(4Al) species: effect of Si contents on Si incorporation mechanism and Si coordination environment of SAPO-34. Microporous and Mesoporous Materials, 2008, 115(3): 332–337

22 Liu X , Zhou W , Yang Y , Cheng K , Kang J , Zhang L , Zhang G , Min X , Zhang Q , Wang Y . Design of efficient bifunctional catalysts for direct conversion of syngas into lower olefins via methanol/dimethyl ether intermediates. Chemical Science, 2018, 9(20): 4708–4718

23 Assen A H , Virdis T , De Moor W , Moussa A , Eddaoudi M , Baron G , Denayer J F M , Belmabkhout Y . Kinetic separation of C₄ olefins using Y-fum-fcu-MOF with ultra-fine-tuned aperture size. Chemical Engineering Journal, 2021, 413: 127388–127395

24 Nasser A H , Guo L , ELnaggar H , Wang Y , Guo X , AbdelMoneim A , Tsubaki N . Mn-Fe nanoparticles on a reduced graphene oxide catalyst for enhanced olefin production from syngas in a slurry reactor. RSC Advances, 2018, 8(27): 14854–14863

25 Xu Y , Liu D , Liu X . Conversion of syngas toward aromatics over hybrid Fe-based Fischer-Tropsch catalysts and HZSM-5 zeolites. Applied Catalysis A, General, 2018, 552: 168–183

26 Kim J H , Rhim G B , Choi N , Youn M H , Chun D H , Heo S . A hybrid modeling framework for efficient development of Fischer-Tropsch kinetic models. Journal of Industrial and Engineering Chemistry, 2023, 118: 318–329

27 Todic B , Nowicki L , Nikacevic N , Bukur D B . Fischer-Tropsch synthesis product selectivity over an industrial iron-based catalyst: effect of process conditions. Catalysis Today, 2016, 261: 28–39

28 Wu L , Liu Z , Xia L , Qiu M , Liu X , Zhu H , Sun Y . Effect of SAPO-34 molecular sieve morphology on methanol to olefins performance. Chinese Journal of Catalysis, 2013, 34(7): 1348–1356

29 Thiessen J , Rose A , Meyer J , Jess A , Curulla-Ferré D . Effects of manganese and reduction promoters on carbon nanotube supported cobalt catalysts in Fischer-Tropsch synthesis. Microporous and Mesoporous Materials, 2012, 164: 199–206

30 Zhang Q , Cheng K , Kang J , Deng W , Wang Y . Fischer-Tropsch catalysts for the production of hydrocarbon fuels with high selectivity. ChemSusChem, 2014, 7(5): 1251–1264

31 Wang Y N , Ma W P , Lu Y J , Yang J , Xu Y Y , Xiang H W , Li Y W , Zhao Y L , Zhang B J . Kinetics modelling of Fischer-Tropsch synthesis over an industrial Fe-Cu-K catalyst. Fuel, 2003, 82(2): 195–213

32 Li Y , Wang M , Liu S , Wu F , Zhang Q , Zhang S , Cheng K , Wang Y . Distance for communication between metal and acid sites for syngas conversion. ACS Catalysis, 2022, 12(15): 8793–8801

33 Amoo C C , Xing C , Tsubaki N , Sun J . Tandem reactions over zeolite-based catalysts in syngas conversion. ACS Central Science, 2022, 8(8): 1047–1062

34 Gao P , Dang S , Li S , Bu X , Liu Z , Qiu M , Yang C , Wang H , Zhong L , Han Y . . Direct production of lower olefins from CO₂ conversion via bifunctional catalysis. ACS Catalysis, 2017, 8(1): 571–578

35 Wei J , Yao R , Ge Q , Wen Z , Ji X , Fang C , Zhang J , Xu H , Sun J . Catalytic hydrogenation of CO₂ to isoparaffins over Fe-based multifunctional catalysts. ACS Catalysis, 2018, 8(11): 9958–9967

36 Zhu Y , Pan X , Jiao F , Li J , Yang J , Ding M , Han Y , Liu Z , Bao X . Role of manganese oxide in syngas conversion to light olefins. ACS Catalysis, 2017, 7(4): 2800–2804

37 Rahimi N , Karimzadeh R . Catalytic cracking of hydrocarbons over modified ZSM-5 zeolites to produce light olefins: a review. Applied Catalysis A, General, 2011, 398(1-2): 1–17

38 Huang Q , Tang Y , Wang S , Chi Y , Yan J . Effect of cellulose and polyvinyl chloride interactions on the catalytic cracking of tar contained in syngas. Energy & Fuels, 2016, 30(6): 4888–4894

39 Weber J L , Dugulan I , de Jongh P E , de Jong K P . Bifunctional catalysis for the conversion of synthesis gas to olefins and aromatics. ChemCatChem, 2018, 10(5): 1107–1112

40 Xu Y , Liu J , Ma G , Wang J , Wang Q , Lin J , Wang H , Zhang C , Ding M . Synthesis of aromatics from syngas over FeMnK/SiO₂ and HZSM-5 tandem catalysts. Molecular Catalysis, 2018, 454: 104–113

41 Wang T , Xu Y , Shi C , Jiang F , Liu B , Liu X . Direct production of aromatics from syngas over a hybrid FeMn Fischer-Tropsch catalyst and HZSM-5 zeolite: local environment effect and mechanism-directed tuning of the aromatic selectivity. Catalysis Science & Technology, 2019, 9(15): 3933–3946

42 Wu L , Liu Z , Qiu M , Yang C , Xia L , Liu X , Sun Y . Morphology control of SAPO-34 by microwave synthesis and their performance in the methanol to olefins reaction. Reaction Kinetics, Mechanisms and Catalysis, 2013, 111(1): 319–334

43 Sun C , Wang Y , Wang Z , Chen H , Wang X , Li H , Sun L , Fan C , Wang C , Zhang X . Fabrication of hierarchical ZnSAPO-34 by alkali treatment with improved catalytic performance in the methanol-to-olefin reaction. Comptes Rendus Chimie, 2018, 21(1): 61–70

44 KimH DSongH TFazeliAAlizadeh EslamiANohY SGhaffari SaeidabadNLeeK YMoonD J. CO/CO₂ hydrogenation for the production of lighter hydrocarbons over SAPO-34 modified hybrid FTS catalysts. Catalysis Today, 2022, 388–389: 410–416