From the early 1800s until the mid-1920s, the distillation of wood to make 'wood alcohol' was the major source of methanol. According to some statistics, methanol production reached 30,000 tonnes in 1923, consuming some 3m tonnes of wood feedstock. However, this inefficient method of methanol production was quickly replaced by large scale processes based on hydrogen-carbon oxide mixtures introduced in the 1920s.
A major breakthrough came in the early 1970s with the development of low pressure processes replacing the high pressure route. Today, nearly all production is based on these processes consuming natural gas, naphtha or refinery light gas with a shift in production to those countries with low cost natural gas.
Synthesis gas, a mixture of carbon monoxide, carbon dioxide and hydrogen, is first produced in a reformer. This is carried out by passing a mixture of the hydrocarbon feedstock and steam through a heated tubular reformer. The ratio of hydrogen and carbon in the syngas may need to be adjusted by purging excess hydrogen or adding carbon dioxide. Developments here include the use of autothermal reforming, either alone or in combination with a primary reformer, in which oxygen is mixed with the steam.
The syngas is cooled and then compressed before being fed to the methanol converter. The methanol synthesis takes place in the presence of copper-based catalysts at 250-260oC. The crude methanol is recovered and purified by distillation.
Air Products has developed a liquid phase methanol converter which uses a slurry of copper catalyst in an inert paraffinic liquid. A demonstration plant has been integrated into Eastman Chemical's coal gasification facility at Kingsport, Tennessee, where it obtains its syngas feedstock.
Plant designers are developing very large capacity plants in the 5000-10,000 tonnes/day range that could produce low-cost methanol for fuel uses and light olefins production when based on inexpensive natural gas. Two approaches are being taken: some are pursuing pure oxygen addition resulting in total autothermal reforming; others are taking the non-oxygen route with compact reforming and low pressure methanol synthesis.
The Dutch-based biomethanol producer BioMCN has developed a process to make biomethanol from glycerine, a by-product in biodiesel production. It plans to start large scale production in Delfzijl in 2009 with production capacity reaching 800,000 tonne/year within five years.
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Methanol
Uses and Outlook
The three largest derivatives of methanol are formaldehyde, methyl tertiary butyl ether (MTBE) and acetic acid. However, methanol is seeing growing demand in fuel applications such dimethyl ether (DME), biodiesel and the direct blending into gasoline.
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