From Glycerol to Value‐Added Products
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Hunt J. A., 1999, Pharm. J., 263, 985
See the recent report from Frost & Sullivan: “R&D Creating New Avenues for Glycerol” (August 4 2006) available online athttps://www.frost.com/prod/servlet/market‐insight‐top.pag?docid=77264824.
The US agribusiness company Archer Daniels Midland recently announced plans to make propylene glycol from glycerol instead of propylene oxide. Dow Chemical closed its glycerol plant in Texas early this year when Procter & Gamble Chemicals shut down a natural glycerol refinery in England. See:
McCoy M., 2006, Chem. Eng. News, 84, 6
As of July 2006 pure glycerol was sold at 600–800 €/ton while crude glycerol of high quality obtained by biodiesel production was sold at 600–700 €/ton with glycerol currently priced at around 850 USD/ton. At prices approaching 770 USD/ton glycerol becomes a significant platform chemical. If as anticipated biodiesel production grows to 3.23 million tons worldwide an extra 323 000 tons of glycerol would reach the market thus rendering glycerol a readily available commodity.
Crude glycerol from biodiesel production is an excellent additive for concrete enhancing its resistance to compression and grinding and lowering its setting time. Mechanical tests carried out on “clinker” (the cement precursor which is mixed with gypsum to yield the concrete) samples doped with crude glycerol show in all cases that raw glycerol imparts better mechanical and chemical properties compared to those samples doped with commercial additives including pure glycerol. Tests on an industrial scale using trucks of crude glycerol confirmed the results on the laboratory scale and commercialization of cement added with biodiesel glycerol started in late 2006.M.Rossi M.Pagliaro R.Ciriminna C.Della Pina W.Kesber WO2006051574 2004.
Under basic conditions:
H.Kimura Jpn. Pat. Application 95253 1993; under acidic conditions:
H.Kimura Jpn. Pat. Application 253062 1994;
H.Kimura Jpn. Pat. Application 315624 1994.
Kimura H., 1999, Recent Res. Dev. Polym. Sci., 3, 327
F. J.Liotta Jr. L. J.Karas H.Kesling US Patent 5308365 1994.
V. P.Gupta US Patent 5476971 1995.
H. Noureddini W. R. Dailey B. A. Hunt “Production of Ethers of Glycerol from Crude Glycerol”1998. Paper posted at DigitalCommons at the University of Nebraska‐Lincoln:http://digitalcommons.unl.edu/chemeng_biomaterials/18/.
By the Netherlands‐based consortium Procedé Group bv with the involvement of industrial partners. According to an EU directive by the year 2010 5.75 % of the total amount of fuel consumed in the EU should originate from renewable sources. In Germany alone this would mean 30 million tons equivalent to 3 million tons of glycerol or to 10 millions tons of GTBE (a likely antidetonant). If realized it could be easily absorbed by the market as large amounts of TBE are already available on the market as it used as the starting material of MTBE still in the EU (but it is banned in California and 19 other US states).
J. Spooner‐Wyman D. B. Appleby “Heavy‐Duty Diesel Emissions Characteristics of Glycerol Ethers” 25th Symposium on Biotechnology for Fuels and Chemicals Breckenridge Colorado2003:http://www.nrel.gov/biotechsymp25/session5_pp.html.
For instance NOF Corporation in Japan recently developed a new antifreeze (Camag) composed of glycerol and potassium acetate to prevent freezing of roads in the cold northern district of Japan.
For this achievement Professor G. J. Suppes was awarded the 2006 Presidential Green Chemistry Challenge Awards:http://www.epa.gov/greenchemistry/pubs/pgcc/winners/aa06.html. Polyol Partners can also hydrocrack glycerol and form propylene glycol: C. Boswell Chemical Marketing Reporter January 24 2005.
W.Girke H.Klenk D.Arntz T.Haas A.Neher US Patent 5387720 1995.
Biebl H., 1999, Appl. Mech. Rev., 52, 289
H. Petitdemange H. Biebl “Production of 1 3‐Propanediol From Glycerol Surpluses. Yield Optimisation by Technological Development and by Genetic Strain Improvement” http://www.biomatnet.org/secure/Air/S233.htm.
D. Liu “Integrated Production for Biodiesel and 1 3‐Propanediol with Lipase‐Catalyzed Transesterification and Fermentation”. Presentation at the Japanese Institute of Energy 2006:http://www.jie.or.jp/pdf/21%5B1%5D.Prof.DehuaLIU.pdf#search=%22Liu%2Bpropanediol%22.
Small‐scale production of these highly branched glycidol polymers has been commercialized in Europe by Hyperpolymers (Germany).
Solvay is building a facility utilizing this new process which should be operative in the first half of 2007 with the required glycerol supplied from the biodiesel producer Diester Industrie.