Invented by Vincent J. Murphy, James Shoemaker, Guang Zhu, Raymond Archer, George Frederick Salem, Eric L. Dias, Archer Daniels Midland Co
The Archer Daniels Midland Co invention works as follows
Disclosed is a catalyst made of platinum and gold. The catalysts can be used to selectively oxidize compositions that contain a primary and secondary alcohol groups, where at least one of the alcohol groups is converted into a carboxyl. The catalysts include particles of gold and platinum in a supported catalyst, where the platinum and gold molar ratio is between 100:1 and 1:4, and the particles of platinum are sized from 2 to 50 nm. Methods for the oxidative, chemocatalytic transformation of carbohydrates into carboxylic acid or derivatives are also disclosed. Also disclosed are methods for selectively oxidizing glucose into glucaric acids or derivatives of the same using platinum and gold catalysts. “Furthermore, methods for producing such catalysts are also disclosed.Background for Oxidation catalysts
Crude oil is the current source of many commodity and specialty organic chemical products. These chemicals are used to make polymers and other materials. Some examples include ethylene propylene styrene bisphenol A, caprolactam hexamethylenediamine adiponitrile caprolactone acrylonitrile acrylic acid 1,6-hexanediol 1,3-propanediol and others. First, crude oil is refined into hydrocarbons intermediates, such as ethylene propylene benzene and cyclohexane. The hydrocarbon intermediates produced are typically selectively converted to the desired chemical using various processes. As an example, crude oils are refined to cyclohexane and then selectively oxidized into ‘KA oil’. This is further oxidized to produce adipic acids, which are used in the manufacture of nylon 6,6. Industrially, many known processes are used to produce these petrochemicals using crude oil as a precursor. Ullmann’s Encyclopedia of Industrial Chemistry Wiley 2009 (7th Edition), for example, is incorporated by reference.
Since many years, there has been an interest in using biorenewable material as a feedstock that can replace or complement crude oil. Klass, Biomass For Renewable Energy, Fuels, and Chemicals, Academic Press, 1997, is a good example. There have also been attempts to produce carboxylic acid from renewable resources by combining biocatalytical and chemocatalytical processes. Frost et. al., Benzene-Free Reaction of Adipic Acid. Biotechnol. Prog. 2002, Vol. 18, pp. U.S. Pat. Nos. Nos. Nos.
One of the biggest challenges in converting biorenewable materials such as carbohydrates, (e.g. glucose derived from starch or cellulose, or sucrose), into current commodity and speciality chemicals is the conversion of the primary alcohol group (hydroxyl) to a carboxyl (COOH) group when there is at least a second alcohol group.
Glucose can be obtained from various carbohydrate-containing sources including conventional biorenewable sources such as corn grain (maize), wheat, potato, cassava and rice as well as alternative sources such as energy crops, plant biomass, agricultural wastes, forestry residues, sugar processing residues and plant-derived household wastes. Biorenewable sources are any organic material that is renewable and contains carbohydrates. Examples include switch grass, miscanthus trees (hardwoods and softwoods), vegetation and crop residues such as bagasse, corn stover, etc. Other sources include wastes (e.g. spent paper, municipal wastes, green wastes, etc .).
The art allows for the isolation of carbohydrates such as glucose from biorenewables. See, for example, Centi and van Santen, Catalysis for Renewables, Wiley-VCH, Weinheim 2007; Kamm, Gruber and Kamm, Biorefineries-Industrial Processes and Products, Wiley-VCH, Weinheim 2006; Shang-Tian Yang, Bioprocessing for Value Added Products from Renewable Resources New Technologies and Applications, Elsevier B. V. 2007; Furia, Starch in the Food Industry, Chapter 8, CRC Handbook of Food Additives 2nd Edition CRC Press, 1973. Kirk-Othmer Encyclopedia of Chemical Technology, 5th Edition (John Wiley and Sons, 2001) contains chapters on Starch, Syrups, and Sugar. The art also includes processes for converting starch into glucose. See, for instance, Schenck’s?Glucose & Glucose-containing syrups? Ullmann’s Encyclopedia of Industrial Chemistry Wiley-VCH 2009 Furthermore, methods to convert cellulose to glucose are known in the art, see, for example, Centi and van Santen, Catalysis for Renewables, Wiley-VCH, Weinheim 2007; Kamm, Gruber and Kamm, Biorefineries-Industrial Processes and Products, Wiley-VCH, Weinheim 2006; Shang-Tian Yang, Bioprocessing for Value-Added Products from Renewable Resources New Technologies and Applications, Elsevier B. V. 2007.
The selective oxidation from glucose to glucaric acids has been attempted using platinum catalysts. U.S. Patent No. No. No. Journal of Catalysis Vol. 67, pages 1-13 and 14-20 (1981). There are also other oxidation techniques; for example, U.S. Pat. Nos. Nos. Technol. Biotechnol. Vol. 76, p. 186-190 (2001); J. Agr. Food Chem. Vol. Vol. Vol. Vol. Vol. Carbohydrate Res. Carbohydrate Res. Vol. 330, p. 21-29 (2001). These processes are however plagued by economic problems due to, amongst other things, limitations in process yield, low conversion rates and limited selectivity because of shortcomings in the performance existing catalysts. These catalysts and the processes that employ them are not used in industrial applications for the selective oxidation glucose-containing carbohydrates, to produce industrial carboxylic acid or derivatives of those acids.
Thus, there remains a need for new, industrially scalable catalysts for the selective and commercially-meaningful conversion of a primary hydroxyl group to a carboxyl group of compositions comprising a primary hydroxyl group and at least a secondary hydroxyl group. There is a desire to convert biorenewables such as carbohydrates or polyols into specialty or industrial carboxylic acid and derivatives of these acids. More specifically, it would be desirable to convert glucose (derived either from starch or cellulose) to important chemicals like glucaric and derivatives.
The present invention is directed to catalyst compositions containing gold and discrete platinum particles on a support, where the ratio of gold to platinum on the support ranges from approximately 100:1 up to approximately 1:4, and the platinum is essentially present on the supporting as Pt(0).
The present invention also relates to catalyst compositions that are useful for selectively converting a primary group hydroxyl of compositions containing a primary group hydroxyl and at least one secondary hydroxyl to a carboxyl, wherein the compositions of catalysts include platinum and gold.
The present invention further relates to catalyst compositions containing gold and discrete platinum particles on a support, wherein: (a) the proportion of gold to platinum on the support ranges from approximately 100:1 up to about 1 to 4, (b) platinum is largely present on the substrate as Pt(0) and (c), the particle size of the platinum particles is substantially between 2 and 50 nanometers.
The present invention also relates to catalyst compositions that contain particles of gold and platinum on a substrate, where (a) there is a ratio of gold to platinum in the range from 100:1 to 1:4, (b), the platinum is largely present on the substrate as Pt(0) and (c) particle sizes for the platinum are in the vicinity of 2 to 50 nanometers and (d) particle sizes for the gold-containing particle are in the vicinity of 2 to 20 nanometers.
The present invention also relates to catalyst compositions that are produced by processes including the following: a) providing solid support; b) contacting support with gold-containing compounds; c) contacting support and gold-containing compounds with a base; d) contact the support with platinum-containing compounds, and e). treating the support together with the atleast one platinum-containing substance under conditions sufficient to produce on the supported particles comprising both gold and platinum.
The present invention also relates to processes for the preparation of glucaric acids or derivatives thereof, which include reacting glucose with an oxygen source in the presence of gold and platinum catalysts and without adding any base.
Other objects and features are revealed and/or pointed out in the following paragraphs.
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