The first commercial route to BDO was based on Reppe process which involved the reaction of formaldehyde with acetylene and subsequent stages of hydrogenation to produce BDO. However, it required careful handling of acetylene. BDO made in this way provided one of the chemical routes to butadiene developed during World War II to support synthetic rubber production.
Therefore, it is ironic that Mitsubishi developed a butadiene process to make BDO when BDO was originally made to make butadiene. This was the first non-acetylene process to be commercialised and proceeds via acetoxylation followed by hydrogenation and hydrolysis. The process can be designed to make BDO, THF or both.
Lyondell (formerly Arco Chemical), using technology originally developed by Kuraray, produces 1,4 butanediol using propylene oxide as a feedstock. The first step in the Lyondell process is the isomerisation of propylene oxide to allyl alcohol. The second step is the hydroformylation of allyl alcohol to 4-hydroxy-butyraldehyde. The third and final step is the hydrogenation of the 4-hydroxy-butyraldehyde to BDO.
Analogous to this process is the Dairen process operated in Taiwan. However, in this case, allyl alcohol is derived from propylene via allyl acetate. The chemistry is similar to vinyl acetate production using propylene acetoxylation. Allyl acetate is converted to allyl alcohol via dehydration, with the recovered co-product acetic acid recycled.
During the 1990s, a number of butane-based processes were commercialised proceeding via maleic anhydride and maleic ester, maleic acid and such. The first units built used the Davy (ex-Kvaerner) process concept where maleic anhydride is converted to the ester which then undergoes fixed-bed hydrogenolysis to make a mixture of BDO, THF and GBL. The first licences used ethanol, but later generations use methanol.
Davy continues to simplify its esterification/hydrogenolysis process reducing complexity, equipment items and capital costs. It is now possible to manufacture large amounts of THF in the Davy process.
The Davy process can, in principle, be integrated with any commercial maleic anhydride process. In recent projects, for example BASF/Petronas in Kuantan, Malaysia, the Davy process has been integrated with Huntsman Mars V/VI maleic anhydride technology.
The BP/Lurgi Geminox process, however, uses a fluidised n-butane oxidation process to manufacture maleic acid. Hydrogenolysis of maleic acid produces a mixture of BDO, THF and GBL.
The DuPont transport bed concept has been used to make THF from n-butane in Gijon, Spain. Rather than reacting n-butane with free oxygen in air, the transport bed catalyst 'fixes' oxygen in a regeneration system and becomes an oxygen carrier/catalyst for the conversion of n-butane to maleic acid.
Several companies have recently developed a biotransformation process for BDO. In North America, a consortium involving Argonne National Laboratory, Oak Ridge National Laboratory, Pacific Northwest National Laboratory and the National Renewable Energy Laboratory, has been supported by the US Department of Energy's (US DoE) Alternative Feedstocks Programme. The consortium aims to commercialise the process with Applied Carbochemicals and Arkenol, respectively.
(Source: The evolution continues, by Mark Morgan, Nexant ChemSystems, ECN 23 July 2004)
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Butanediol
Uses and Outlook
Butanediol (BDO) is a valuable chemical intermediate used in the production of high performance polymers, solvents and fine chemicals. The BDO chain has three main branches – polymers, tetrahydrofuran (THF) derivatives and gamma-butyrolactone (GBL) derivatives. When converted to THF, its highest volume derivative, BDO is used to produce polytetramethylene ether glycol (PTMEG) which is used mainly in the production of spandex fibres.
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