History of methanol synthesis
Supp (1990) and Olah et al. (2006) present good overviews on the characteristics of methanol and its production methods. This section is largely based on these reference books. Another source may be found at wikipedia.
Methanol has a history extending back to about 1661, when Boyle succeeded for the first time in recovering methanol from crude wood vinegar. The component was re-discovered in 1822 by Taylor, after which in 1835 Von Liebig succeeded in clarifying the chemical structure of methanol. In the hundred years following this, methanol was recovered to an increasing degree as wood alcohol by distilling wood.
In 1923, Mittasch and his staff succeeded in first producing methanol from carbon monoxide and hydrogen (‘synthesis gas’ or ‘syngas’) using a catalyst. Methanol was recovered together with a whole series of other components containing oxygen, and the catalyst only had very short cycle times. Patart then described a methanol synthesis process using hydrogenation active metals, and metal oxides stated to be the catalyst. This led to a first commercial plant. This process required vigorous conditions—pressures ranging from 300–1000 atm, and temperatures of about 400 °C. Modern methanol production has been made more efficient through use of catalysts (commonly containing copper) capable of operating at lower pressures.
At the beginning of the thirties, a series of commercial plants went into operation in the USA, with capacities per plant of 100 to 500 tons/day, using chromic acid activated zinc oxide catalyst. As early as 1935, it was recognised that copper-based catalysts provided considerable advantages for methanol synthesis, permitting considerably lower pressures and, above all, lower temperatures. But these catalists were extremely sensitive to sulphur components. After development of suitable syngas purification systems, mainly to remove sulphur, the first Low-Pressure Methanol process was brought onto the market by Imperial Chemical Industries Ltd (ICI), Great Britain. At that time, Lurgi Gesellschaft für Wärme und Chemoteknik from Germany also developed a low-pressure methanol process, which, contrary to the ICI quench reactor, applied a tubular reactor cooled with boiling water. Most of the methanol plants in the last 20 years operate according to the ICI or Lurgi processes, while numerous high-pressure units have been converted to the low-pressure system in the second half of the last century.
Literature References (RSW Chapter)
Supp E., 1990, How to produce methanol from coal, Springer-Verlag, ISBN 3-540-51923-8
Olah G.A., Goeppert A., Prakash G.K., 2006, Beyond Oil and Gas: the Methanol Economy, Wiley-VCH Verlag GmbH & Co., ISBN 3-527-31275-7
Patent no. 1,569,775 filed 12 January 1926
Spath P.L., Dayton D.C., 2003, Preliminary Screening – Technical and economic assessment of synthesis gas to fuels and chemicals with emphasis on the potential for Biomass-derived syngas, NREL/TP-510-34929
History of methanol synthesis