The dehydrogenation of methanol to methyl formate Part I: Kinetic studies using copper-based catalysts

Chemical Engineering and Processing: Process Intensification

Volumn 44, Issue 3, 2005, Pages 393-402

  Huang, X ^a   Cant, N W ^a   Wainwright, M S ^a   Ma, L ^a  

^a UNIVERSITY OF NEW SOUTH WALES   (Australia)

Author keywords

Copper chromite catalyst; Kinetics; Methanol dehydrogenation; Methyl formate; Skeletal copper catalyst

Indexed keywords

ACTIVATION ENERGY; ADSORPTION; CATALYST ACTIVITY; COPPER COMPOUNDS; DEHYDROGENATION; DISSOCIATION; FORMALDEHYDE; MATHEMATICAL MODELS; REACTION KINETICS;

LANGMUIR-HINSELWOOD MODEL; METHYL FORMATE; REACTION ORDER;

METHANOL;

DEHYDROGENATION;

EID: 7244234313     PISSN: 02552701     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.cep.2004.05.012     Document Type: Article

References (25)

1. T. Abe, Y. Nishide, N. Muro, H. Higuchi, Process for producing carboxylic acid esters and formamide, J 91-345190, Mitsubishi Gas Chemical Co. Inc., Japan.
2. 1, Mol. Chem. 1 (1986) 491.
3. A. Guerrero-Ruiz, I. Rodriguez-Ramos, G. Fierro, Dehydrogenation of methanol to methyl formate over supported copper catalysts, Appl. Catal. 72 (1991) 119.
4. T.P. Minyukova, N.V. Shtertser, L.P. Davydova, I.I. Simentsova, A.V. Khasin, T.M. Yurieva, CO-free methyl formate from methanol: the control of the selectivity of the process on Cu-based catalysts, Khimiya v Interesakh Ustoichivogo Razvitiya 11 (2003) 189.
5. L. Ma, M.S. Wainwright, Development of skeletal copper-chromia catalysts. I. Structure and activity promotion of chromia on skeletal copper catalysts for methanol synthesis, Appl. Catal. A 187 (1999) 89.
6. S.P. Tonner, D.L. Trimm, M.S. Wainwright, N.W. Cant, Dehydrogenation of methanol to methyl formate over copper catalysts, Ind. Eng. Chem. Prod. Res. Dev. 23 (1984) 384.
7. S.P. Tonner; The copper-catalysed dehydrogenation of methanol, Ph.D. Thesis, University of New South Wales, 1984.
8. L. Ma, M.S. Wainwright, in: D. Morrell (Ed.), Catalysis of Organic Reactions-Chemical Industries, Marcel Dekker, New York, 2002, p. 225.
9. H.K. Hall, J.H. Baldt, Thermochemistry of strained-ring bridgehead nitriles and esters, J. Am. Chem. Soc. 93 (1971) 140.
10. J. Chao, K.R. Hall, K.N. Marsh, R.C. Wilholt, Thermodynamic properties of key organic oxygen compounds in the carbon range CI to C4. Part 2. Ideal gas properties, J. Phys. Chem. Ref. Data 15 (1986) 1369.
11. I. Barin, Thermochemical Data of Pure Substances, Part I, VCH Press, p. 640.
12. M. Ai, Dehydrogenation of methanol to methyl formate over copper-based catalysts, Appl. Catal. II (1984) 259.
13. G. Ertl, H. Knozinger, J. Weitkamp, Handbook of Heterogeneous Catalysis, VCH, Weinheim, Germany, 1997.
14. M.J. Chung, D.J. Moon, K.Y. Park, S.K. Ihm, Mechanism of methyl formate formation on Cu/ZnO catalyst, J. Catal. 136 (1992) 609.
15. E.J. Billo, Excel for Chemists, Wiley, New York, 2001.
16. J.W. Evans, Studies of the copper catalysed hydrogenolysis of alkyl esters, Ph.D. Thesis, The University of New South Wales, 1983.
17. N.W. Cant, S.P. Tonner, D.L. Trimm, M.S. Wainwright, Isotopic labeling studies of the mechanism of dehydrogenation of methanol to methyl formate over copper-based catalysts, J. Catal. 91 (1985) 197.
18. 2CO on a Cu(1 1 0) catalyst, J. Catal. 53 (1978) 208.
19. M. Bowker, R.J. Madix, XPS, UPS and thermal desorption studies of alcohol adsorption on copper(l 1 0): metnanol, Surf. Sci. 95 (1980) 190.
20. D.B. Clarke, D.K. Lee, M.J. Sandoval, A.T. Bell, Infrared studies of the mechanism of methanol decomposition on Cu/SiOz, J. Catal 150 (1994) 81.
21. G.J. Millar, C.H. Rochester, K.C. Waugh, Infrared study of the adsorption of methanol on oxidized and reduced copper/silica catalysts, J. Chem. Soc., Faraday Trans. 87 (1991) 2795.
22. 2, J. Catal. 184 (1999) 357.
23. E. Miyazaki, I. Yasumori, Kinetics of the catalytic decomposition of methanol, formaldehyde, and methyl formate over a copper-wire surface, Bull Chem. Soc. Jpn. 40 (1967) 2012.
24. K. Takahashi, K. Takezawa, H. Kobayashi, Mechanism of formation of methyl formate from formaldehyde over copper catalysts, Chem. Lett. (1983) 1061.
25. D.M. Monti, N.W. Cant, D.L. Trimm, M.S. Wainwright, Hydrogenolysis of methyl formate over copper on silica. I. Study of the mechanism using labeled compounds, J. Catal. 100 (1986) 17.