Methanol Ullman Encyclopedy

Methanol

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Methanol
Eckhard Fiedler, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany Georg Grossmann, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany D. Burkhard Kersebohm, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany ¨ Gunther Weiss, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany Claus Witte, BASFAktiengesellschaft, Ludwigshafen, Federal Republic of Germany Introduction . . . . . . . . . . . . . . . Physical Properties . . . . . . . . . . . Chemical Properties . . . . . . . . . . Production . . . . . . . . . . . . . . . . Principles . . . . . . . . . . . . . . . . . Thermodynamics . . . . . . . . . . . . . Kinetics and Mechanism . . . . . . . . Byproducts . . . . . . . . . . . . . . . . . Catalysts. . . . . . . . . . . . . . . . . . Catalysts for High-Pressure Synthesis Catalysts for Low-Pressure Synthesis Production of Low-Pressure Catalysts Catalyst Deactivation . . . . . . . . . . Other Catalyst Systems . . . . . . . . . Process Technology . . . . . . . . . . . Production of Synthesis Gas . . . . . Synthesis . . . . . . . . . . . . . . . . . . Reactor Design . . . . . . . . . . . . . .Distillation of Crude Methanol . . . Construction Materials . . . . . . . . Handling, Storage, and Transportation . . . . . . . . . . . . . . . . . . . . . Explosion and Fire Control . . . . . Storage and Transportation . . . . . Quality Specifications and Analysis Environmental Protection . . . . . . Uses . . . . . . . . . . . . . . . . . . . . . Use as Feedstock for Chemical Syntheses . . . . .. . . . . . . . . . . . . . . Use as Energy Source . . . . . . . . . Other Uses . . . . . . . . . . . . . . . . Economic Aspects . . . . . . . . . . . . Toxicology and Occupational Health Toxicology . . . . . . . . . . . . . . . . . Occupational Health . . . . . . . . . . References . . . . . . . . . . . . . . . . .

1. 2. 3. 4. 4.1. 4.1.1. 4.1.2. 4.1.3. 4.2. 4.2.1. 4.2.2. 4.2.3. 4.2.4. 4.2.5.5. 5.1. 5.2. 5.3.

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5.4. 5.5. 6. 6.1. 6.2. 7. 8. 9. 9.1. 9.2. 9.3. 10. 11. 11.1. 11.2. 12.

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1. Introduction
Methanol [67-56-1], CH3 OH, M r 32.042, also termed methyl alcohol or carbinol, is one of the most important chemical raw materials. Worldwide production capacity in 1989 was ca. 21×106 t/a.About 85 % of the methanol produced is used in the chemical industry as a starting material or solvent for synthesis. The remainder is used in the fuel and energy sector; this use is increasing. In 1993 world wide production capacity was 22.4×106 t/a. Historical Aspects. Methanol was first obtained in 1661 by Sir Robert Boyle through the rectification of crude wood vinegar over milk of lime. He namedthe new compound adiaphorus spiritus lignorum. Justus von Liebig (1803 – 1873) and J. B. A. Dumas (1800 – 1884) independently determined the composition of

methanol. The term “methyl” was introduced into chemistry in 1835 on the basis of their work. From ca. 1830 – 1923, “wood alcohol”, obtained by the dry distillation of wood, remained the only important source of methanol. As early as 1913,A. Mittasch and coworkers at BASF successfully produced organic compounds containing oxygen, including methanol, from carbon monoxide and hydrogen in the presence of iron oxide catalysts during developmental work on the synthesis of ammonia. The decisive step in the large-scale industrial production of methanol was made by M. Pier and coworkers in the early 1920s with the development of asulfurresistant zinc oxide – chromium oxide catalyst. By the end of 1923 the process had been converted from the developmental to the production stage at the BASF Leuna Works. Processes based on the above work were performed at high pressure (25 – 35 MPa) and 320 – 450 ◦ C. They dictated the industrial pro-

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a16 465

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Methanol...