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Switching Between Oxidation Types Using Molybdenum Phosphate Catalysts for Paraffin Activation Using Doped Fe as Surface Acidity Modifier and MoOx as an Oxygen Insertion Tool

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Abstract

A comparative study of the activation of n-hexane over 12-molybdophopshoric acid (H3PMo12O40 or HPA), Fe3+ doped HPA (Fe0.69H0.93PMo12O40) and an iron phosphate catalyst (P/Fe = 1.22) was carried out. The Fe doped HPA catalyst is thermally more stable and less acidic than the unmodified HPA catalyst. The HPA and the Fe doped HPA catalysts both catalytically produced 2,5-dimethyltetrahydrofuran and 2,5-hexadione (oxygenates), with the Fe doped HPA catalyst selectively producing more oxygenates than the HPA catalyst. The iron phosphate catalyst produced cis-2-hexene and 1-hexene but no oxygenates, which implies that the iron phosphate catalyst promotes dehydrogenation, but not oxygen insertion. At 360 °C, the HPA catalyst initiated benzene formation reactions. At isoconversion of ca. 8% under isothermal conditions, the iron phosphate catalyst gave the highest selectivity (72%) towards benzene, which may have formed through both catalytic and non-catalytic reactions. In contrast, the Fe doped HPA catalyst showed a lower benzene selectivity than the HPA catalyst with a corresponding increase in cyclic oxygenates.

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References

  1. Friedrich HB, Govender N, Mathebula MR (2006) The effect of voids and dilution on n-hexane oxidation over a VMgO catalyst. Appl Catal A 297:81–89

    Article  CAS  Google Scholar 

  2. Fadlalla MI, Friedrich HB (2014) The effect of the oxidation environment on the activity and selectivity to aromatics and octenes over cobalt molybdate in the oxidative dehydrogenation of n-octane. Catal Sci Techol 4:4378–4385

    Article  CAS  Google Scholar 

  3. Adams DL, Dyson PJ, Tavener SJ (2004) Chemistry in alternative reaction media. Wiley, Chichester

    Google Scholar 

  4. Krishna SH, Huang KF, Barnett KJ et al (2018) Oxygenated commodity chemicals from chemo-catalytic conversion of biomass derived heterocycles. AlChE J 64:1910–1922

    Article  CAS  Google Scholar 

  5. Carrillo P, Shi R, Teeluck K et al (2018) In situ formation of FeRh nanoalloys for oxygenate synthesis. ACS Catal 8:7279–7286

    Article  CAS  Google Scholar 

  6. Resasco DE, Wang B, Crossley S (2016) Zeolite-catalysed C–C bond forming reactions for biomass conversion to fuels and chemicals. Catal Sci Techol 6:2543–2559

    Article  CAS  Google Scholar 

  7. Pradhan S, Bartley JK, Bethell D et al (2012) Non-lattice surface oxygen species implicated in the catalytic partial oxidation of decane to oxygenated aromatics. Nat Chem 4:134–139

    Article  CAS  Google Scholar 

  8. Guo Z, Liu B, Zhang QH et al (2014) Recent advances in heterogeneous selective oxidation catalysis for sustainable chemistry. Chem Soc Rev 43:3480–3524

    Article  CAS  Google Scholar 

  9. Wang XX, Wang Y, Tang QH et al (2003) MCM-41-supported iron phosphate catalyst for partial oxidation of methane to oxygenates with oxygen and nitrous oxide. J Catal 217:457–467

    Article  CAS  Google Scholar 

  10. Mestl G, Ilkenhans T, Spielbauer D et al (2001) Thermally and chemically induced structural transformations of Keggin-type heteropoly acid catalysts. Appl Catal A 210:13–34

    Article  CAS  Google Scholar 

  11. Pope MT (1983) Heteropoly and isopoly oxometalates, inorganic chemistry concepts 8. Springer, Berlin

    Book  Google Scholar 

  12. Millet J-MM (1998) FePO catalysts for the selective oxidative dehydrogenation of isobutyric acid into methacrylic acid. Catal Rev Sci Eng 40:1–38

    Article  CAS  Google Scholar 

  13. Ai M (1996) Comparison of catalytic properties for partial oxidation between heteropolyacids and phosphates of vanadium and iron. J Mol Catal A 114:3–13

    Article  CAS  Google Scholar 

  14. Cavani F (1998) Heteropolycompound-based catalysts: a blend of acid and oxidizing properties. Catal Today 41:73–86

    Article  CAS  Google Scholar 

  15. Ai M (1999) Characteristics of iron phosphate as a catalyst for partial oxidation. Catal Today 52:65–69

    Article  CAS  Google Scholar 

  16. Harilal A, Dasireddy VDBC, Friedrich HB (2016) An oxidative route for the production of methyl methacrylate: a study over iron phosphate catalysts. Catal Lett 146:1169–1181

    Article  CAS  Google Scholar 

  17. Harilal A, Dasireddy VDBC, Friedrich HB (2018) Effect of water and methanol in the production of methyl methacrylate over iron phosphate catalysts. React Kinet Mech Cat 124:265–277

    Article  CAS  Google Scholar 

  18. Rocchiccioli-Deltcheff C, Fournier M, Franck R et al (1983) Vibrational investigations of polyoxometalates. 2. Evidence for anion-anion interactions in molybdenum(VI) and tungsten(VI) compounds related to the Keggin structure. Inorg Chem 22:207–216

    Article  CAS  Google Scholar 

  19. Langpape M, Millet J-MM (2000) Effect of iron counter-ions on the redox properties of the Keggin-type molybdophosphoric heteropolyacid: part I. An experimental study on isobutane oxidation catalysts. Appl Catal A 200:89–101

    Article  CAS  Google Scholar 

  20. Ai M, Muneyama E, Kunishige A et al (1993) Effects of methods of preparing iron phosphate and P/Fe compositions on the catalytic performance in oxidative dehydrogenation of isobutyric acid. J Catal 144:632–635

    Article  CAS  Google Scholar 

  21. Ai M, Muneyama E, Kunishige A et al (1994) Characteristics of iron phophate as a catalyst for partial oxidation. Bull Chem Soc Jpn 67:551–556

    Article  CAS  Google Scholar 

  22. Ai M, Ohdan K (1997) Effects of differences in the structures of iron phosphates on the catalytic action in the oxidative dehydrogenation of lactic acid to pyruvic acid. Appl Catal A 165:461–465

    Article  CAS  Google Scholar 

  23. Miller JE, Gonzales MM, Evans L et al (2002) Oxidative dehydrogenation of ethane over iron phosphate catalysts. Appl Catal A 231:281–292

    Article  CAS  Google Scholar 

  24. Rao KN, Lingaiah N, Suryanarayana I et al (2003) A comparison of structure and catalytic functionality of 12-molybdophosphoric acid and its ammonium salt in the ammoxidation of 2-methylpyrazine to 2-cyanopyrazine. Catal Lett 90:31–38

    Article  CAS  Google Scholar 

  25. Rocchiccioli-Deltcheff C, Aouissi A, Bettahar MM et al (1996) Catalysis by 12-molybdophosphates: 1. catalytic reactivity of 12-molybdophosphoric acid related to its thermal behavior investigated through IR, Raman, polarographic, and X-ray diffraction studies: a comparison with 12-molybdosilicic acid. J Catal 164:16–27

    Article  CAS  Google Scholar 

  26. Song K, Moon SH, Lee WY (1991) Catalytic properties of thermally decomposed 12-molybdophosphoric and l0-molybdo-2-vanadophosphoric acids. Korean J Chem Eng 8:33–38

    Article  CAS  Google Scholar 

  27. Fournier M, Feumi-Jantou C, Rabia C et al (1992) Polyoxometalates catalyst materials: X-ray thermal stability study of phosphorus-containing heteropolyacids H3 +xPM12 –xVxO40·13–14H2O (M = Mo, W; x = 0–1). J Mater Chem 2:971–978

    Article  CAS  Google Scholar 

  28. Marosi L, Platero EE, Cifre J et al (2000) Thermal dehydration of H3 + xPVxM12−xO40·yH2O Keggin type heteropolyacids; formation, thermal stability and structure of the anhydrous acids H3PM12O40, of the corresponding anhydrides PM12O38.5 and of a novel trihydrate H3PW12O40·3H2O. J Mater Chem 10:1949–1955

    Article  CAS  Google Scholar 

  29. Huynh Q, Millet J-MM (2005) Characterization of iron counter-ion environment in bulk and supported phosphomolybdic acid based catalysts. J Phys Chem Solids 66:887–894

    Article  CAS  Google Scholar 

  30. Huang F, Su Y, Long Z et al (2018) Enhanced formation of 5-hydroxymethylfurfural from glucose using a silica-supported phosphate and iron phosphate heterogeneous catalyst. Ind Eng Chem Res 57:10198–10205

    Article  CAS  Google Scholar 

  31. Ai M, Ohdan K (1999) Effects of the method of preparing iron orthophosphate catalyst on the structure and the catalytic activity. Appl Catal A 180:47–52

    Article  CAS  Google Scholar 

  32. Fadlalla MI, Farahani MD, Friedrich HB (2018) Three inter-linked active sites in the dehydrogenation of n-octane over magnesium molybdate based catalysts and their influences on coking and cracking side reactions. Mol Catal 461:86–96

    Article  CAS  Google Scholar 

  33. O’Connor RP, Schmidt LD (2001) Oxygenates and olefins from catalytic partial oxidation of cyclohexane and n-hexane in single-gauze chemical reactors. Stud Surf Sci Catal 133:289–296

    Article  Google Scholar 

  34. Busca G, Finocchio E, Ramis G et al (1996) On the role of acidity in catalytic oxidation. Catal Today 32:133–143

    Article  CAS  Google Scholar 

  35. Damoyi NE, Friedrich HB, Kruger HG et al (2017) Density functional theory studies of the uncatalysed gas-phase oxidative dehydrogenation conversion of n-hexane to hexenes. Comput Theor Chem 1114:153–164

    Article  CAS  Google Scholar 

  36. Pillay B, Mathebula MR, Friedrich HB (2009) The oxidative dehydrogenation of n-hexane over Ni–Mo–O catalysts. Appl Catal A 361:57–64

    Article  CAS  Google Scholar 

  37. Mizuno N, Misono M (1998) Heterogeneous catalysis. Chem Rev 98:199–217

    Article  CAS  Google Scholar 

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Acknowledgements

We thank Sasol and THRIP for financial assistance, Drs. F. Prinsloo, N. Govender and A. Harilal from Sasol for their input, and Mr. M. Mamo (University of Witwatersrand) for running TGA and DSC samples.

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Funding was provided by Sasol and THRIP (Grant No. TP1208035643).

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Correspondence to Holger B. Friedrich.

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Mncwabe, Z., Farahani, M.D. & Friedrich, H.B. Switching Between Oxidation Types Using Molybdenum Phosphate Catalysts for Paraffin Activation Using Doped Fe as Surface Acidity Modifier and MoOx as an Oxygen Insertion Tool. Catal Lett 150, 728–737 (2020). https://doi.org/10.1007/s10562-019-02943-z

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