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

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.

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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.

Additional information

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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.

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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

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.

Competing interests

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

Correspondence to Youssef Belmabkhout or Mohamed Eddaoudi.

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)

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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.