Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Natural gas upgrading using a fluorinated MOF with tuned H2S and CO2 adsorption selectivity

An Author Correction to this article was published on 19 November 2018

This article has been updated

Abstract

The process used to upgrade natural gas, biogas and refinery-off-gas directly influences the cost of producing the fuel and often requires complex separation strategies and operational systems to remove contaminants such as hydrogen sulfide (H2S) and carbon dioxide (CO2). Here we report a fluorinated metal–organic framework (MOF), AlFFIVE-1-Ni, that allows simultaneous and equally selective removal of CO2 and H2S from CH4-rich streams in a single adsorption step. The simultaneous removal is possible for a wide range of H2S and CO2 compositions and concentrations of the gas feed. Pure component and mixed gas adsorption, single-crystal X-ray diffraction and molecular simulation studies were carried out to elucidate the mechanism governing the simultaneous adsorption of H2S and CO2. The results suggest that concurrent removal of CO2 and H2S is achieved via the integrated favourable sites for H2S and CO2 adsorption in a confined pore system. This approach offers the prospect of simplifying the complex schemes for removal of acid gases.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Correlation between pore volume and H2S/CO2 selectivity of fluorinated MOFs.
Fig. 2: H2S/CO2 removal performance of NbOFFIVE-1-Ni.
Fig. 3: H2S/CO2 removal performance of AlFFIVE-1-Ni.
Fig. 4: DFT-geometry optimized pure and binary gas loaded structures.

Similar content being viewed by others

Data availability

The X-ray crystallographic data for NbOFFIVE-1-Ni (H2S), AlFFIVE-1-Ni (H2S) and AlFFIVE-1-Ni (CO2) have been deposited at the Cambridge Crystallographic Data Centre (CCDC), under deposition numbers 1843109, 1843110 and 1859923, respectively. These data can be obtained free of charge from the CCDC via www.ccdc.cam.ac.uk. Crystallographic information for NbOFFIVE-1-Ni (H2S), AlFFIVE-1-Ni (H2S) and AlFFIVE-1-Ni (CO2) can also be found in Supplementary Data 13. All other relevant data supporting the findings of this study are available from the corresponding authors upon request.

Change history

  • 19 November 2018

    In the version of this Article originally published, the name of author Gongping Liu was mistakenly written with the names in reverse order. This has now been corrected.

References

  1. Nylund, N.-O., Laurikko, J. & Ikonen, M. Pathways for Natural Gas into Advanced Vehicles. Edited Draft Report 2002; Version 30.8.2002 (International Association for Natural Gas Vehicle (IANGV), 2002).

  2. Maricq, M. M., Chase, R. E., Xu, N. & Podsiadlik, D. H. The effects of the catalytic converter and fuel sulfur level on motor vehicle particulate matter emissions: gasoline vehicles. Environ. Sci. Technol. 36, 276–282 (2002).

    Article  Google Scholar 

  3. Abdel-Aal, H., Aggour, M. & Fahim, M. Petroleum and Gas Field Processing (CRC Press, Boca Raton, 2015).

    Book  Google Scholar 

  4. Belmabkhout, Y., Heymans, N., De Weireld, G. & Sayari, A. Simultaneous adsorption of H2S and CO2 on triamine-grafted pore-expanded mesoporous MCM-41 silica. Energy Fuels 25, 1310–1315 (2011).

    Article  Google Scholar 

  5. Zhao, S. et al. The hydrolysis of carbonyl sulfide at low temperature: a review. Sci. World J. 739501 (2013).

  6. Kadijani, J. & Narimani, E. Adsorptive desulfurization of liquefied petroleum gas for carbonyl sulfide removal. Open J. Chem. Eng. Sci. 1, 79–86 (2014).

    Article  Google Scholar 

  7. Tsai, J.-H., Jeng, F.-T. & Chiang, H.-L. Removal of H2S from exhaust gas by use of alkaline activated carbon. Adsorption 7, 357–366 (2001).

    Article  Google Scholar 

  8. Bhatt, P. M. et al. A fine-tuned fluorinated MOF addresses the needs for trace CO2 removal and air capture using physisorption. J. Am. Chem. Soc. 138, 9301–9307 (2016).

    Article  Google Scholar 

  9. Belmabkhout, Y., Guillerm, V. & Eddaoudi, M. Low concentration CO2 capture using physical adsorbents: Are metal–organic frameworks becoming the new benchmark materials? Chem. Eng. J. 296, 386–397 (2016).

    Article  Google Scholar 

  10. Bagreev, A. & Bandosz, T. J. A role of sodium hydroxide in the process of hydrogen sulfide adsorption/oxidation on caustic-impregnated activated carbons. Ind. Eng. Chem. Res. 41, 672–679 (2002).

    Article  Google Scholar 

  11. Adib, F., Bagreev, A. & Bandosz, T. J. Analysis of the relationship between H2S removal capacity and surface properties of unimpregnated activated carbons. Environ. Sci. Technol. 34, 686–692 (2000).

    Article  Google Scholar 

  12. Qian, Z., Xu, L.-B., Li, Z.-H., Li, H. & Guo, K. Selective absorption of H2S from a gas mixture with CO2 by aqueous N-methyldiethanolamine in a rotating packed bed. Ind. Eng. Chem. Res. 49, 6196–6203 (2010).

    Article  Google Scholar 

  13. Zhang, J.-P., Zhang, Y.-B., Lin, J.-B. & Chen, X.-M. Metal azolate frameworks: from crystal engineering to functional materials. Chem. Rev. 112, 1001–1033 (2012).

    Article  Google Scholar 

  14. Xue, D.-X. et al. Tunable rare-earth fcu-MOFs: a platform for systematic enhancement of CO2 adsorption energetics and uptake. J. Am. Chem. Soc. 135, 7660–7667 (2013).

    Article  Google Scholar 

  15. Xue, D.-X. et al. Tunable rare earth fcu-MOF platform: access to adsorption kinetics driven gas/vapor separations via pore size contraction. J. Am. Chem. Soc. 137, 5034–5040 (2015).

    Article  Google Scholar 

  16. Shekhah, O. Made-to-order metal–organic frameworks for trace carbon dioxide removal and air capture. Nat. Commun. 5, 4228 (2014).

    Article  Google Scholar 

  17. Schneemann, A. et al. Flexible metal–organic frameworks. Chem. Soc. Rev. 43, 6062–6096 (2014).

    Article  Google Scholar 

  18. Padial, N. M. et al. Highly hydrophobic isoreticular porous metal–organic frameworks for the capture of harmful volatile organic compounds. Angew. Chem. Int. Ed. 52, 8290–8294 (2013).

    Article  Google Scholar 

  19. Moulton, B. & Zaworotko, M. J. From molecules to crystal engineering: supramolecular isomerism and polymorphism in network solids. Chem. Rev. 101, 1629–1658 (2001).

    Article  Google Scholar 

  20. McDonald, T. M. et al. Cooperative insertion of CO2 in diamine-appended metal–organic frameworks. Nature 519, 303–308 (2015).

    Article  Google Scholar 

  21. Li, P. et al. Bottom-up construction of a superstructure in a porous uranium–organic crystal. Science 356, 624–627 (2017).

    Article  Google Scholar 

  22. Li, J.-R. et al. Porous materials with pre-designed single-molecule traps for CO2 selective adsorption. Nat. Commun. 4, 1538 (2013).

    Article  Google Scholar 

  23. Lammert, M. et al. Cerium-based metal organic frameworks with UiO-66 architecture: synthesis, properties and redox catalytic activity. Chem Commun. 51, 12578–12581 (2015).

    Article  Google Scholar 

  24. Kumar, A. et al. Direct air capture of CO2 by physisorbent materials. Angew. Chem. Int. Ed. 54, 14372–14377 (2015).

    Article  Google Scholar 

  25. Krause, S. et al. A pressure-amplifying framework material with negative gas adsorption transitions. Nature 532, 348–352 (2016).

    Article  Google Scholar 

  26. He, Y., Zhou, W., Qian, G. & Chen, B. Methane storage in metal–organic frameworks. Chem. Soc. Rev. 43, 5657–5678 (2014).

    Article  Google Scholar 

  27. Guillerm, V. et al. Discovery and introduction of a (3,18)-connected net as an ideal blueprint for the design of metal–organic frameworks. Nat. Chem. 6, 673–680 (2014).

    Article  Google Scholar 

  28. Guillerm, V. et al. A supermolecular building approach for the design and construction of metal–organic frameworks. Chem. Soc. Rev. 43, 6141–6172 (2014).

    Article  Google Scholar 

  29. Gándara, F., Furukawa, H., Lee, S. & Yaghi, O. M. High methane storage capacity in aluminum metal–organic frameworks. J. Am. Chem. Soc. 136, 5271–5274 (2014).

    Article  Google Scholar 

  30. Eddaoudi, M. et al. Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage. Science 295, 469–472 (2002).

    Article  Google Scholar 

  31. Devic, T. & Serre, C. High valence 3p and transition metal based MOFs. Chem. Soc. Rev. 43, 6097–6115 (2014).

    Article  Google Scholar 

  32. Chen, Z. et al. Applying the power of reticular chemistry to finding the missing alb-MOF platform based on the (6,12)-coordinated edge-transitive net. J. Am. Chem. Soc. 139, 3265–3274 (2017).

    Article  Google Scholar 

  33. Bonnefoy, J., Legrand, A., Quadrelli, E. A., Canivet, J. & Farrusseng, D. Enantiopure peptide-functionalized metal–organic frameworks. J. Am. Chem. Soc. 137, 9409–9416 (2015).

    Article  Google Scholar 

  34. Benoit, V. et al. MIL-91(Ti), a small pore metal–organic framework which fulfils several criteria: an upscaled green synthesis, excellent water stability, high CO2 selectivity and fast CO2 transport. J. Mater. Chem. A 4, 1383–1389 (2016).

    Article  Google Scholar 

  35. Assen, A. H. et al. Ultra-tuning of the rare-earth fcu-MOF aperture size for selective molecular exclusion of branched paraffins. Angew. Chem. Int. Ed. 54, 14353–14358 (2015).

    Article  Google Scholar 

  36. Hamon, L. et al. Comparative study of hydrogen sulfide adsorption in the MIL-53(Al, Cr, Fe), MIL-47(V), MIL-100(Cr), and MIL-101(Cr) metal−organic frameworks at room temperature. J. Am. Chem. Soc. 131, 8775–8777 (2009).

    Article  Google Scholar 

  37. Vaesen, S. et al. A robust amino-functionalized titanium (IV) based MOF for improved separation of acid gases. Chem. Commun. 49, 10082–10084 (2013).

    Article  Google Scholar 

  38. Yang, Q. Y. et al. Probing the adsorption performance of the hybrid porous MIL-68(Al), A synergic combination of experimental and modelling tools. J. Mater. Chem. 22, 10210–10220 (2012).

    Article  Google Scholar 

  39. Hamon, L. et al. Molecular insight into the adsorption of H2S in the flexible MIL-53(Cr) and rigid MIL-47(V) MOFs, infrared spectroscopy combined to molecular simulations. J. Phys. Chem. C 115, 2047–2056 (2011).

    Article  Google Scholar 

  40. Bhatt, P. M. et al. Isoreticular rare earth fcu-MOFs for the selective removal of H2S from CO2 containing gases. Chem. Eng. J. 324, 392–396 (2017).

    Article  Google Scholar 

  41. Belmabkhout, Y. et al. Metal–organic frameworks to satisfy gas upgrading demands: fine-tuning the soc-MOF platform for the operative removal of H2S. J. Mater. Chem. A 5, 3293–3303 (2017).

    Article  Google Scholar 

  42. Fernandez, C. A. et al. Gas-induced expansion and contraction of a fluorinated metal−organic framework. Cryst. Growth Des. 10, 1037–1039 (2010).

    Article  Google Scholar 

  43. Allan, P. K. et al. Metal-organic frameworks for the storage and delivery of biologically active hydrogen sulfide. Dalton. Trans. 41, 4060–4066 (2012).

    Article  Google Scholar 

  44. Liu, J., Wei, Y., Li, P., Zhao, Y. & Zou, R. H2S/CO2 separation by metal–organic frameworks based on chemical-physical adsorption. J. Phys. Chem. 121, 13249–13255 (2017).

    Google Scholar 

  45. Mohideen, M. I. H. et al. A fine-tuned MOF for gas and vapor separation: A multipurpose adsorbent for acid gas removal, dehydration, and BTX sieving. Chem 3, 822–833 (2017).

    Article  Google Scholar 

  46. Cadiau, A., Adil, K., Bhatt, P. M., Belmabkhout, Y. & Eddaoudi, M. A metal–organic framework–based splitter for separating propylene from propane. Science 353, 137–140 (2016).

    Article  Google Scholar 

  47. Cadiau, A. et al. Hydrolytically stable fluorinated metal–organic frameworks for energy-efficient dehydration. Science 356, 731–735 (2017).

    Article  Google Scholar 

  48. Adil, K. et al. Valuing metal–organic frameworks for postcombustion carbon capture: a benchmark study for evaluating physical adsorbents. Adv. Mater. 29, 1702953 (2017).

    Article  Google Scholar 

  49. Nugent, P. et al. Porous materials with optimal adsorption thermodynamics and kinetics for CO2 separation. Nature 495, 80–84 (2013).

    Article  Google Scholar 

  50. Shekhah, O. et al. A facile solvent-free synthesis route for the assembly of a highly CO2 selective and H2S tolerant NiSIFSIX metal–organic framework. Chem. Commun. 51, 13595–13598 (2015).

    Article  Google Scholar 

  51. APEX2 Ver. 2014.11-0 (Bruker AXS Inc., 2014).

  52. SAINT Ver.8.34A (Bruker AXS Inc., 2014).

  53. SADABS Ver. 2014/15 (Bruker AXS Inc., 2014).

  54. SHELXS-97, Program for Crystal Structure Solution. (Univ. of Göttingen, 1997).

  55. Sheldrick, G. M. Crystal structure refinement with SHELXL. Acta Crystallogr. C 71, 3–8 (2015).

    Article  Google Scholar 

  56. Farrugia, L. J. WinGX and ORTEP for Windows: an update. J. Appl. Cryst. 45, 849–854 (2012).

    Article  Google Scholar 

  57. Koros, W. J. & Paul, D. R. Design considerations for measurement of gas sorption in polymers by pressure decay. J. Polym. Sci. Polym. Phys. Ed. 14, 1903–1907 (1976).

    Article  Google Scholar 

Download references

Acknowledgements

Y.B., P.M.B., A.C. and M.E. thank the Aramco sponsored research fund (contract 66600024505). M.E., Y.B., G.L. and W.J.K acknowledge support from KAUST CRG Research Grant URF/1/2222-01. G.M. and M.E. acknowledge the KAUST Center Partnership Fund Program (CPF-2910). We also acknowledge support by King Abdullah University of Science and Technology. We thank S.R. Tavares for fruitful discussions on the computation work.

Author information

Authors and Affiliations

Authors

Contributions

Y.B., P.B., K.A. and M.E. conceived and designed the research. A.C., K.A. and P.B. designed and synthesized materials. A.S., P.B. and K.A. carried out crystallographic experiments. Y.B. and P.B. carried out adsorption experiments and breakthrough measurements. G.L. and W.J.K. collected H2S adsorption isotherms. R.P. and G.M. performed computational studies. M.E., Y.B., P.B., K.A., R.P. and G.M. wrote the manuscript. M.E. and Y.B. supervised the project.

Corresponding authors

Correspondence to Youssef Belmabkhout or Mohamed Eddaoudi.

Ethics declarations

Competing interests

The results of this publication have been submitted for a patent filing application US2018/0093218 A1.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary figures 1–21, Supplementary tables 1–4, Supplementary notes 1–2, Supplementary references

Supplementary Data 1

Crystal structure data for NbOFFIVE-1-Ni (H2S)

Supplementary Data 2

Crystal structure data for AlFFIVE-1-Ni (H2S)

Supplementary Data 3

Crystal structure data for AlFFIVE-1-Ni (CO2)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Belmabkhout, Y., Bhatt, P.M., Adil, K. et al. Natural gas upgrading using a fluorinated MOF with tuned H2S and CO2 adsorption selectivity. Nat Energy 3, 1059–1066 (2018). https://doi.org/10.1038/s41560-018-0267-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41560-018-0267-0

This article is cited by

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing