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Volumn 125, Issue 11, 2003, Pages 3384-3396

Catalytic gas phase oxidation of methanol to formaldehyde

Author keywords

[No Author keywords available]

Indexed keywords

GAS PHASE OXIDATION;

EID: 0037454325     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja028839x     Document Type: Article
Times cited : (226)

References (103)
  • 5
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    • In Metal-Oxo and Metal-Peroxo Species in Catalytic Oxidations; Meunier, B., Ed.; Springer: Berlin
    • (b) Schröder, D.; Schwarz, H.; Shaik, S. In Metal-Oxo and Metal-Peroxo Species in Catalytic Oxidations; Meunier, B., Ed.; Springer: Berlin, 2000; Struct. Bond.; Vol. 97, p 91.
    • (2000) Struct. Bond. , pp. 91
    • Schröder, D.1    Schwarz, H.2    Shaik, S.3
  • 8
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    • (a) For a selection of other studies on the gas-phase chemistry of molybdenum oxo species, see: Cassady, C. J.; McElvany, S. W. Organometallics, 1992, 11, 2367.
    • (1992) Organometallics , vol.11 , pp. 2367
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  • 17
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    • (a) A number of gas-phase catalytic cycles have been established using mass spectrometry. See for example: oxidation of CO Kappes, M. M.; Staley, R. H. J Am. Chem. Soc. 1981, 103, 1286.
    • (1981) J. Am. Chem. Soc. , vol.103 , pp. 1286
    • Kappes, M.M.1    Staley, R.H.2
  • 19
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    • oxidation of methane
    • (c) Shi, Y.; Ervin, K. M. J. Chem. Phys. 1998, 108, 1757; oxidation of methane.
    • (1998) J. Chem. Phys. , vol.108 , pp. 1757
    • Shi, Y.1    Ervin, K.M.2
  • 23
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    • Howe-Grant, M., Ed.; John Wiley and Sons: New York
    • The huge demand for formaldehyde-based resins for particleboard wood products makes formaldehyde one of the top 25 chemicals produced in industrial countries, with approximately 15 million metric tons of formaldehyde (37% aqueous solution) produced annually. See for example: Gerberich, H. R.; Seaman, G. C. Formaldehyde in Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed.; Howe-Grant, M., Ed.; John Wiley and Sons: New York, 1994: vol. 11, p 929-950.
    • (1994) Formaldehyde in Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed. , vol.11 , pp. 929-950
    • Gerberich, H.R.1    Seaman, G.C.2
  • 24
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    • note
    • A molybdenum(VI) trioxide-based catalyst or a metallic silver catalyst is used. About 70% of newly installed production capacity uses the former. The heterogeneous catalysis is typically carried out at atmospheric pressure and 300-400°C with atmospheric dioxygen as the oxidant. High methanol conversion (>99%) and selectivity for formaldehyde (>95%) can be achieved. ibid.
  • 31
    • 0000442667 scopus 로고
    • (a) See for example: Groff, R. P. J. Catal. 1984. 86, 215.
    • (1984) J. Catal. , vol.86 , pp. 215
    • Groff, R.P.1
  • 42
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    • Ginsberg, A. P. Ed.; John Wiley & Sons; New York
    • Hur, N. H.; Klemperer, W. G.; Wang, R.-C. In Inorganic Synthesis; Ginsberg, A. P. Ed.; John Wiley & Sons; New York, 1990; Vol. 27, p 79-80.
    • (1990) Inorganic Synthesis , vol.27 , pp. 79-80
    • Hur, N.H.1    Klemperer, W.G.2    Wang, R.-C.3
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    • Bowers, M. T. Ed.; Academic Press: New York
    • Su, T.; Bowers, M. T. In Gas-Phase Ion Chemistry; Bowers, M. T. Ed.; Academic Press: New York, 1979: p. 83.
    • (1979) Gas-Phase Ion Chemistry , pp. 83
    • Su, T.1    Bowers, M.T.2
  • 71
    • 0242559509 scopus 로고    scopus 로고
    • Alcohol acidities are from: http://webbook.nist.gov/chemistry/.
  • 72
    • 0242475748 scopus 로고    scopus 로고
    • note
    • Alcohol is present in the ion trap during all stages of a multistage experiment. If alcohol is used in initial reactions of the catalytic cycle (e.g., reaction 1) it remains present during later reactions.
  • 76
    • 0242644170 scopus 로고    scopus 로고
    • note
    • A very small amount of alkene loss is also observed from dimolybdate centres with straight chain alkoxo ligands. This typically represents less than 2% of the amount of aldehyde loss.
  • 77
    • 0039479067 scopus 로고
    • We adopt the notation whereby the first carbon of the alkoxo ligand is denoted as the α-carbon
    • Westheimer, F. H. Chem. Rev. 1949, 45, 419. We adopt the notation whereby the first carbon of the alkoxo ligand is denoted as the α-carbon.
    • (1949) Chem. Rev. , vol.45 , pp. 419
    • Westheimer, F.H.1
  • 78
    • 0242559508 scopus 로고    scopus 로고
    • note
    • -, suggesting a crude estimate for the KIE of this reaction of 6.
  • 79
  • 80
    • 0037080141 scopus 로고    scopus 로고
    • -. This ion could not be mass selected in the ion trap instrument, presumably due to its 'fragile' nature (consistent with the observation of 'peak fronting' for this species, see: McClellan, J. E.; Murphy, J. P., III.; Mulholland, J. J.; Yost, R. A. Anal. Chem. 2002, 74, 402).
    • (2002) Anal. Chem. , vol.74 , pp. 402
    • McClellan, J.E.1    Murphy J.P. III2    Mulholland, J.J.3    Yost, R.A.4
  • 81
    • 0242475747 scopus 로고    scopus 로고
    • note
    • -1 s-1.
  • 82
    • 0242559506 scopus 로고    scopus 로고
    • note
    • - (Figure 6).
  • 83
    • 0242644169 scopus 로고    scopus 로고
    • note
    • - sample that is unreactive towards methanol and nitromethane represents a 'sink' in the catalytic cycles of Figure 1.
  • 84
    • 0242475746 scopus 로고    scopus 로고
    • note
    • - ions. To test this proposition, the rate of reaction was measured over a 10-fold range of methanol pressure, effectively varying the average number of collisions with helium before collision with methanol. Reaction rate was found to be independent of methanol pressure.
  • 85
    • 0242559507 scopus 로고    scopus 로고
    • note
    • - and the degree of collisional activation used, but no attempts have been made to quantify the influence of these factors.
  • 88
    • 0242475745 scopus 로고    scopus 로고
    • note
    • -. Given that these species are generated via collisional activation, kinetic considerations are also likely to be important in determining the relative populations of these isomers.
  • 91
    • 0242559505 scopus 로고    scopus 로고
    • note
    • - described earlier may in fact be an average isotope effect for these two processes.
  • 94
    • 0242559504 scopus 로고    scopus 로고
    • note
    • Ditungstate species have been observed before using electrospray: see refs 6b,d.
  • 98
    • 0242559502 scopus 로고    scopus 로고
    • note
    • 3l.
  • 99
    • 0242644167 scopus 로고    scopus 로고
    • note
    • - were also observed (M = Mo, W).
  • 103
    • 0003595639 scopus 로고
    • and references therein
    • Iwasawa, Y. In Tailored Metal Catalysts; Iwasawa, Y. Eds.; D. Reidel Publishing Company: Holland, 1986, p 54-60 and references therein.
    • (1986) Tailored Metal Catalysts , pp. 54-60
    • Iwasawa, Y.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.