Methods and compositions for the prodution of aminated compounds from renewable feedstock

Abstract

A method for the production of higher value chemicals comprising pyrolyzing one or more sugar oxidation products in the absence of oxygen under conditions suitable for the formation of a reaction mixture comprising from about 1 wt.% to equal to or greater than about 50 wt.% glycolaldehyde based on the total weight of the reaction mixture; and recovering at least a portion of the glycolaldehyde. A method for the production of higher value chemicals comprising; pyrolyzing reactants comprising glucodialdose, 2-keto-D-glucose or both in the absence of oxygen under conditions suitable for the formation of a reaction mixture comprising from about 1 wt.% to equal to or greater than about 50 wt.% glycolaldehyde; recovering at least a portion of the glycolaldehyde to obtain recovered glycolaldehyde; and purifying the recovered glycolaldehyde to obtain a purity of from about 70% to about 85% to obtain purified glycolaldehyde.

Description

METHODS AND COMPOSITIONS FOR THE PRODUTION OF AMINATED COMPOUNDS FROM RENEWABLE FEEDSTOCKCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims benefit of and priority to U.S. provisional patent application Serial No 63 / 653,243 filed May 30, 2024, and entitled “METHODS AND COMPOSITIONS FOR THE PRODUCTION OF AMINATED COMPOUNDS FROM RENEWABLE FEEDSTOCK,” which is hereby incorporated herein by reference in its entirety for all purposes.STATEMENT REGARDING FEDERALLY SPONSOREDRESEARCH OR DEVELOPMENT

[0002] Not applicable.REFERENCE TO SEQUENCE LISTING

[0003] The instant application contains a Sequence Listing which has been submitted electronically in XML file format and is hereby incorporated by reference in its entirety. Said XML file, created on April 28,2025 is named “23PRC004-PCT_3416-15502.xml” and is 26,934 bytes in size.TECHNICAL FIELD

[0004] The present disclosure relates generally to producing aminated compounds from sugars. More particularly, the present disclosure relates to methods and pathways to produce aldehydes. More particularly, the present disclosure relates to the production of high value chemicals from platform molecules.BACKGROUND

[0005] With sustainability being a desired goal, tremendous progress in bio-based production routes from renewable raw materials to commercial goods continues to occur. Of particular interest is the formation of higher value chemicals from what are termed “platform molecules.” Herein platform molecules refer to bio-based or bioderived chemicals whose constituting elements totally originated from biomass and could be used as building blocks for the generation of commodity and refined chemicals.

[0006] Ethylene glycol (EG) (molecular formula C2H6O2) and propylene glycol (PG) (molecular formula C3H8O2) are organic compounds belonging to the class of alcohol derivatives known as glycols. At a fundamental level, they share a functional group that includes two hydroxyl (-OH) groups, enabling them to form strong hydrogen bonds with water and other substances. This characteristic is key to their excellent temperature stabilization and solvent capabilities. EG is well-known for its use in antifreeze, but in aerospace, it shines due to its ability to operate in a broad temperature range, resistance to freeze-thaw cycles, and compatibility with other specialized chemical additives. PG finds wide use in cosmetics, foods, pharmaceuticals, and even advanced life support systems for spacecraft, where any accidental leaks must pose minimal harm to astronauts.

[0007] Commercially, ethylene glycol is predominantly produced via the catalytic oxidation of ethylene (a hydrocarbon derived from petroleum or natural gas). Propylene glycol is commonly synthesized from propylene oxide, another petroleum by-product. A hydration process converts propylene oxide into PG in the presence of acidic or basic catalysts.

[0008] Other routes to create such glycols have been found, such as the Monosaccharide Industrial cracker (MOSAIK) process which can use monosaccharides (e.g., glucose) from first or second generation biomass or their mixtures as feedstock. The MOSAIK process is essentially sugar cracking to form an intermediate which is a glycolaldehyde-rich mixture of C1-C3 oxygenates. These intermediates can then be converted into chemicals ranging from commodities to specialties using heterogeneous catalysis. An ongoing need exists for novel methods utilizing platform molecules in the production of commodity and refined chemicals.BRIEF SUMMARY OF THE DISCLOSURE

[0009] Disclosed herein is a method for the production of higher value chemicals comprising pyrolyzing one or more sugar oxidation products in the absence of oxygen under conditions suitable for the formation of a reaction mixture comprising from about 1 wt.% to equal to or greater than about 50 wt.% glycolaldehyde based on the total weight of the reaction mixture; and recovering at least a portion of the glycolaldehyde.

[0010] Also disclosed herein is a method for the production of higher value chemicals comprising; pyrolyzing reactants comprising glucodialdose, 2-keto-D-glucose or both in the absence of oxygen under conditions suitable for the formation of a reaction mixturecomprising from about 1 wt.% to equal to or greater than about 50 wt.% glycolaldehyde; recovering at least a portion of the glycolaldehyde to obtain recovered glycolaldehyde; and purifying the recovered glycolaldehyde to obtain a purity of from about 70% to about 85% to obtain purified glycolaldehyde.

[0011] Aspects described herein comprise a combination of features and characteristics intended to address various shortcomings associated with certain prior devices, systems, and methods. The foregoing has outlined rather broadly the features and technical characteristics of the disclosed aspects in order that the detailed description that follows may be better understood. The various characteristics and features described above, as well as others, will be readily apparent to those skilled in the art upon reading the following detailed description, and by referring to the accompanying drawings. It should be appreciated that the conception and the specific aspects disclosed may be readily utilized as a basis for modifying or designing other structures for carrying out the same purposes as the disclosed aspects. It should also be realized that such equivalent constructions do not depart from the spirit and scope of the principles disclosed herein.BRIEF DESCRIPTION OF THE DRAWINGS

[0012] For a detailed description of various exemplary aspects, reference will now be made to the accompanying drawings in which:

[0013] Figure 1A schematically depicts the reaction of 2-keto-D-glucose or glucodialdose to form glycolaldehyde followed by subsequent reactions to form higher value chemicals.

[0014] Figure 1 B schematically depicts the formation of a purified glycolaldehyde which is subsequently reductively aminated to form an amine.DETAILED DESCRIPTION

[0015] The following discussion is directed to various exemplary aspects. However, one of ordinary skill in the art will understand that the examples disclosed herein have broad application, and that the discussion of any aspect is meant only to be exemplary of that aspect, and not intended to suggest that the scope of the disclosure, including the claims, is limited to that aspect.

[0016] The figures are not necessarily to scale. Certain features and components herein may be shown exaggerated in scale or in somewhat schematic form and some details of conventional elements may not be shown in interest of clarity and conciseness.

[0017] In the following discussion and in the claims, the terms “including” and “comprising” are used in an open-ended fashion, and thus should be interpreted to mean “including, but not limited to... .” As used herein, the terms “approximately,” “about,” “substantially,” and the like mean within 10% (i.e., plus or minus 10%) of the recited value. Thus, for example, a recited angle of “about 80 degrees” refers to an angle ranging from 72 degrees to 88 degrees

[0018] Disclosed herein are methods and compositions for production of chemicals through a green and cost-efficient pathway. More particularly, disclosed herein are methods for the production of EG and PG, collectively termed herein “the glycols.” More particularly, disclosed herein are methods for the production of aminated compounds. The present disclosure of methods and compositions that provide even more green routes and pathways to replace compounds sourced from petrochemicals.

[0019] In an aspect, one or more reaction products of the present disclosure are characterized by equal to or greater than about 70% of the carbon atoms in the molecule originating from a renewable resource; additionally or alternatively equal to or greater than about 75%; additionally or alternatively equal to or greater than about 80%; additionally or alternatively equal to or greater than about 85%; additionally or alternatively equal to or greater than about 90%. Herein a renewable resource refers to a natural resource which will replenish to replace the portion depleted by usage and consumption, either through natural reproduction or other recurring processes in a finite amount of time on a human time scale. In one or more aspects, the renewable resource is a sugar. In one or more aspects, the renewable resource is glucose.

[0020] In an aspect, a method of the present disclosure comprises the production of the glycols via the pyrolysis of a sugar oxidation product. In one or more aspects, the sugar oxidation product comprises glucodialdose (GDA, also known as hydroxyacetaldehyde), 2-keto-D-glucose (2KG), or both. GDA, 2KG or both suitable for use in production of the glycols can be obtained from any source. In the alternative, GDA, 2KG or both is a biobased product obtained by the oxidation of glucose. For example, the GDA may be obtained from a chemoenzymatic process where glucose is converted to GDA using an oxidase catalyst system.

[0021] Specifically, glucose may be contacted with an oxidase catalyst system under conditions suitable for the formation of GDA. In one or more aspects, the oxidase catalyst system comprises (a) one or more oxidases; (b) one or more small molecule activators (SMA); and (c) one or more single electron oxidizers (SEO); each of which are described in further detail herein.

[0022] The oxidase of the oxidase catalyst system may comprise any suitable oxidase enzyme. In some aspects, the oxidase of the oxidase catalyst system comprises a copper radical oxidase (CRO). CROs have been categorized as ‘green’ small-molecule oxidation catalysts as they lack dependence on an organic cofactor and require only molecular oxygen as a cosubstrate. CROs are non-flavoprotein alcohol oxidoreductases that employ molecular oxygen as a terminal electron acceptor to generate hydrogen peroxide. CROs include glyoxal oxidases (EC 1.1.3.-, GLOX) and galactose 6-oxidases (EC 1.1.3.9, GAO). GLOXes typically function on aldehydes such as methylglyoxal to produce acids. One GLOX from Phanerochaete chrysosporium primarily accepts alphadicarbonyl and alpha-hydroxycarbonyls. Pycnoporus cinnabarinus expresses three GLOXes, one of which has been found to function on methylglyoxal while the other two of which show high catalytic efficiency for glyoxylic acid. GAOs typically function on the Ce or similar alcohols of galactose or other sugars to produce aldehydes. By far, the most characterized CRO is GAO from Fusarium graminearum. Two additional CROs capable of oxidizing aliphatic alcohols were discovered in Colletotrichum graminicola and C. gloeosporioides (CgrAlcOx and CglAlcOx). An aryl-alcohol oxidase (CgrAAO) was also discovered in C. graminicola. In one or more aspects, a CRO for use in the present disclosure is a wildtype enzyme. In one or more aspects, a CRO for use in the present disclosure is a mutated enzyme. In one or more other aspects, a CRO suitable for use in the present disclosure comprises a mutated GAO. In one or more aspects, the CRO has any of SEQ ID NO:1 through SEQ ID NO:11.

[0023] In one or more aspects, the oxidase catalyst system disclosed comprises a SMA. Nonlimiting examples of SMAs suitable for use in the present disclosure include L- tryptophan, 2-mercaptobenzothiazole, L-histidine, methylchloroisothiazolinone, o- dianisidine, 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid (ABTS), 4- aminoantipyrine, L-tyrosine, (2,2,6,6-tetramethylpiperidin-1-yl)oxyl, chloromethylisothiazolinone, 4-thiazolecarboxylic acid, Sunset yellow FCF, tartrazine, p-benzoquinone, dicoumarol, phthalimide, saccharin, phthalic anhydride, erythrosine B,2-aminobenzothiazole, thiabendazole, 2-hydroxybenzothiazole, phenothiazine, 6- aminobenzothiazole, indigo carmine, naphthalimide, 2-aminothiazole, thiazole, 2H-1 ,4- benzothiazin-3(4H)-one, 2-oxindole, beta-lapachone, menaquinone, thiamine, 4- methyl-5-thiazoleethanol, Allura Red AC, menadione, p-cresol, Fast green FCF, Brilliant Blue FCF, methylisothiazolinone, caffeine, veratryl alcohol, fluorescein, and combinations thereof

[0024] In one or more aspects, the oxidase catalyst system disclosed herein comprises an SEO. In one or more aspects, the SEO is an enzyme such as a laccase, horseradish peroxidase, Dyp-type peroxidase, lactoperoxidase, chloroperoxidase, manganese peroxidase 1 , ascorbate peroxidase, dye-decolorizing peroxidase, unspecific peroxygenase, dehaloperoxidase, catalase-peroxidase, lignin peroxidase, soybean seed coat peroxidase, isoforms thereof or combinations thereof. In one or more aspects, the SEO has SEQ ID NO:18.

[0025] Exemplary reaction conditions for conversion of glucose to GDA may comprise one or more of the following parameters: an amount of glucose of from about 0.1 weight per volume percent (w / v%) to about 60 w / v%; additionally or alternatively, from about 5 w / v% to about 50 w / v%; additionally or alternatively, from about 10 w / v% to about 40 w / v% and an amount of oxidase (e.g., CRO) of from about 0.1 mg / L to about 30,000 mg / L; additionally or alternatively, from about 5 mg / L to about 500 mg / L; additionally or alternatively, from about 10 mg / L about 100 mg / L based on desired throughput of the reaction; and an oxygen pressure of from about 10 psi to about 400 psi; additionally or alternatively from about 25 psi to 300 psi; additionally or alternatively from about 50 psi to about 200 psi. Further reaction conditions may include a temperature ranging from about 1 °C to about 70 °C, additionally or alternatively from about 5 °C to about 30 °C; additionally or alternatively from about 10 °C to about 25 °C and an aqueous media such as a phosphate buffer at a pH of from about 5 to about 10; additionally or alternatively from about 6 to about 9; additionally or alternatively from about 7 to about 8.5.

[0026] In one or more aspects, the oxidase catalyst systems disclosed herein comprise GAO or a mutated GAO which is present in an amount ranging from about 0.01 g / L to about 1 g / L; additionally or alternatively, from about 0.1 g / L to about 1 g / L; additionally or alternatively, from about 0.2 g / L to about 1 g / L; additionally or alternatively, from about 0.4 g / L to about 1 g / L; additionally or alternatively, from about 0.6 g / L to about 1 g / L; additionally or alternatively, from about 0.75 g / L to 1 g / L; additionally or alternatively,about 0.01 g / L, about 0.05 g / L, about 0.1 g / L, about 0.2 g / L, about 0.3 g / L, about 0.4 g / L, about 0.5 g / L, about 0.6 g / L, about 0.7 g / L, about 0.8 g / L, about 0.9 g / L or, additionally or alternatively, about 1 g / L. The catalytic composition may comprise an SEO in an amount ranging from about 1 mg / L to about 250 mg / L; additionally or alternatively, from about 5 mg / L to about 250 mg / L, additionally or alternatively, from about 10 mg / L to about 250 mg / L; additionally or alternatively, from about 25 mg / L to about 250 mg / L; additionally or alternatively, from about 50 mg / L to find 250 mg / L; additionally or alternatively, from about 75 mg / L to 250 mg / L; additionally or alternatively, from about 100 mg / L to 250 mg / L; additionally or alternatively, from about 150 mg / L to 250 mg / L; additionally or alternatively, about 1 mg / L, about 5 mg / L, about 10 mg / L, about 15 mg / L, about 20 mg / L, about 25 mg / L, about 30 mg / L, about 35 mg / L, about 40 mg / L, about 45 mg / L, about 50 mg / L, about 55 mg / L, about 60 mg / L, about 65 mg / L, about 70 mg / L, about 75 mg / L, about 80 mg / L, about 85 mg / L, about 90 mg / L, about 95 mg / L, about 100 mg / L, about 105 mg / L, about 110 mg / L, about 115 mg / L, about 120 mg / L, about 125 mg / L, about 130 mg / L, about 135 mg / L, about 140 mg / L, about 145 mg / L, about 150 mg / L, about 155 mg / L, about 160 mg / L, about 165 mg / L, about 170 mg / L, about 175 mg / L, about 180 mg / L, about 185 mg / L, about 190 mg / L, about 195 mg / L, about 200 mg / L, about 205 mg / L, about 210 mg / L, about 215 mg / L, about 220 mg / L, about 225 mg / L, about 230 mg / L, about 235 mg / L, about 240 mg / L, about 245 mg / L or, additionally or alternatively, about 250 mg / L.

[0027] The oxidase catalyst may comprise an SMA in an amount ranging from about 1 ppm to about 500 ppm on a weight basis; additionally or alternatively, from about 5 ppm to about 500 ppm; additionally or alternatively, from about 10 ppm to about 500 ppm; additionally or alternatively, from about 20 ppm to about 500 ppm; additionally or alternatively; additionally or alternatively, from about 40 ppm to about 400 ppm; additionally or alternatively, from about 50 ppm to about 350 ppm; additionally or alternatively, from about 75 ppm to about 200 ppm; additionally or alternatively, about 1 ppm, about 5 ppm, about 10 ppm, about 15 ppm, about 20 ppm, about 25 ppm, about 30 ppm, about 35 ppm, about 40 ppm, about 45 ppm, about 50 ppm, about 55 ppm, about 60 ppm, about 65 ppm, about 70 ppm, about 75 ppm, about 80 ppm, about 85 ppm, about 90 ppm, about 95 ppm, about 100 ppm, about 105 ppm, about 110 ppm, about 115 ppm, about 120 ppm, about 125 ppm, about 130 ppm, about 135 ppm, about 140 ppm, about 145 ppm, about 150 ppm, about 155 ppm, about 160 ppm, about 165ppm, about 170 ppm, about 175 ppm, about 180 ppm, about 185 ppm, about 190 ppm, about 195 ppm, about 200 ppm, about 205 ppm, about 210 ppm, about 215 ppm, about 220 ppm, about 225 ppm, about 230 ppm, about 235 ppm, about 240 ppm, about 245 ppm, about 250 ppm, about 255 ppm, about 260 ppm, about 265 ppm, about 270 ppm, about 275 ppm, about 280 ppm, about 285 ppm, about 290 ppm, about 295 ppm, about 300 ppm, about 305 ppm, about 310 ppm, about 315 ppm, about 320 ppm, about 325 ppm, about 330 ppm, about 335 ppm, about 340 ppm, about 345 ppm, about 350 ppm, about 355 ppm, about 360 ppm, about 365 ppm, about 370 ppm, about 375 ppm, about 380 ppm, about 385 ppm, about 390 ppm, about 395 ppm, about 400 ppm, about 405 ppm, about 410 ppm, about 415 ppm, about 420 ppm, about 425 ppm, about 430 ppm, about 435 ppm, about 440 ppm, about 445 ppm, about 450 ppm, about 455 ppm, about 460 ppm, about 465 ppm, about 470 ppm, about 475 ppm, about 480 ppm, about 485 ppm, about 490 ppm, about 495 ppm; additionally or alternatively, about 500 ppm.

[0028] As will be understood by one of ordinary skill in the art with the benefit of the present disclosure, reactions of the type disclosed herein may result in the production of byproducts (e.g., hydrogen peroxide, etc.) that can detrimentally impact other components of the reaction mixture. For example, hydrogen peroxide may degrade the enzyme resulting in a loss of catalytic activity. In such aspects, mitigation of the detrimental effects of hydrogen peroxide may be carried out such as by the introduction of a catalase (E.C. 1.11.1.61 ), the use of a hydrogen peroxide-resistant enzyme or combinations thereof. In one or more aspects, the oxidase catalyst system further comprises a catalase which may have any of SEQ ID NO: 12 to SEQ ID NO: 17.

[0029] The reaction product, GDA (or 2KG) may be used without further purification. Additionally or alternatively at least a portion of the reaction product is further processed using any suitable methodologies to purify the reaction product in order to meet some user and / or process desired purity level.

[0030] In one or more aspects, GDA, 2-KG, or both are subjected to pyrolysis under conditions suitable for the production of glycolaldehyde. Pyrolysis is a general term for the thermal decomposition of any organic material including wood, plants, and fossil fuels. Thermal decomposition may occur either with the combustion of the reactant or without the combustion of the reactant.

[0031] Pyrolysis of GDA, 2KG or both may be carried under suitable conventional pyrolysis conditions or using fast pyrolysis. For example, a conventional pyrolysisprocess is described in U.S. Pat. No. 3,106,473 while fast pyrolysis techniques are described in U.S. Pat. No. 4,876,108, where the relevant portions of each are incorporated herein. In one or more aspects, pyrolysis reaction conditions comprise one or more of the following: reaction temperatures of equal to or greater than about 200 °C; additionally or alternatively from about 200 °C to about 1000 °C; additionally or alternatively from about 400 °C to about 800 °C; additionally or alternatively from about 600°C to about 800°; and a reaction time of from about 1 minute to about 24 hours; additionally or alternatively from about 10 minutes to about 12 hours; additionally or alternatively from about 1 hour to about 8 hours.

[0032] The pyrolysis reaction product of GDA, 2-KG or both may be used as prepared or could be further processed for example by concentration (e.g., evaporation procedures) and / or distillation before being used in subsequent processes of the present disclosure. The pyrolysis reaction product may contain glycolaldehyde, glyoxal, pyruvaldehyde, formaldehyde, acetol orcombinations thereof. In one or more aspects, the pyrolysis reaction product comprises glycolaldehyde in amounts ranging from about 1 wt.% to equal to or greater than about 50 wt.% based on the total weight of the condensate; additionally or alternatively from about 5 wt.% to equal to or greater than about 45 wt.%; additionally or alternatively from about 10 wt.% to equal to or greater than about 40 wt.%; additionally or alternatively from about 15 wt.% to equal to or greater than about 35 wt.%; additionally or alternatively about 1 wt.%, about 2 wt.%, about 4 wt.%, about 6 wt.%, about 8 wt.%, about 10 wt.%, about 12 wt.%, about 14 wt.%, about 16 wt.%, about 18 wt.%, about 20 wt.%, about 22 wt.%, about 24 wt.%, about 26 wt.%, about 28 wt.%, about 30 wt.%, about 32 wt.%, about 34 wt.%, about 36 wt.%, about 38 wt.%, about 40 wt.%, about 42 wt.%, about 44 wt.%, about 46 wt.%, about 48 wt.%, or about 50 wt.%.

[0033] In one or more aspects, and with reference to Figure 1 B, glycolaldehyde obtained by pyrolysis as disclosed herein is subjected to any number of purification processes (e.g., chromatography, distillation, evaporation) to produce a purified glycolaldehyde that may be use in further reactions. Herein a purified glycolaldehyde is characterized by a purity of from about 70% to about 95%, additionally or alternatively from about 75% to about 90%, additionally or alternatively from about 80% to about 90%. With reference to Figure 1 B, the purified glycolaldehyde can be reductively aminated in the presence of a reducing agent. For example and as shown in Figure 1 B, the reductive aminationis carried out in the presence of hydrogen, a suitable hydrogenation catalyst and nitrogen-containing compound (e.g., ammonia) to form an amine. In one or more aspects, a hydrogenation catalyst for use in the present disclosure comprises (i) a transition-metal compound or transition-metal salt and (ii) a support material. For example, the hydrogenation catalyst may comprise iron (Fe), copper (Cu), rhodium (Rh), rhenium (Re), iridium (lr), cobalt (Co), nickel (Ni), platinum (Pt), palladium (Pd), gold (Au), ruthenium (Ru), oxides thereof, or combinations thereof. In one or more aspects, the support material comprises an inert or substantially inert material such as glass, titania, silica, alumina, zirconia, ceria, ceramic, or carbon.

[0034] With reference to Figure 1A, in one or more aspects, glycolaldehyde can serve as an intermediate for the production of any number of higher value chemicals. For example, glycolaldehyde can be contacted with a nitrogen source (e.g., ammonia) in the presence of a catalyst (e.g., Rainey nickel) and undergo reductive amination. Herein a Raney Nickel catalyst refers to a fine-grained nickel also known as spongy nickel that is derived from a nickel-aluminum alloy.

[0035] In an alternative aspect, glycolaldehyde may be subjected to a thermal cracking process (e.g., MOSAIK) to mixtures of C1-C3 oxygenates. In yet another aspect, glycolaldehyde may be hydrogenated in the presence of a hydrogenation catalyst, for example of the type previously disclosed herein, to form the glycols.

[0036] Disclosed herein are processes for the preparation of glycolaldehyde using GDA as a starting material. Pyrolysis of the GDA and / or 2KG results in improved methods of generating glycolaldehyde with increase conversion and improved selectivity. Glycolaldehyde may then be reductively aminated to form higher value nitrogencontaining compounds, thermally cracked to form oxygenates or hydrogenated to form glycols. The processes disclosed herein represent novel methodologies for producing value added chemicals without the disadvantages associated with conventional production methodologies.ADDITIONAL DISCLOSURE

[0037] The following are additional nonlimiting exemplary aspects of the presently disclosed subject matter

[0038] A first aspect which is a method for the production of higher value chemicals comprising; pyrolyzing one or more sugar oxidation products in the absence of oxygen under conditions suitable for the formation of a reaction mixture comprising from about1 wt.% to equal to or greater than about 50 wt.% glycolaldehyde based on the total weight of the reaction mixture; and recovering at least a portion of the glycolaldehyde.

[0039] A second aspect which is the method of the first apsect wherein the one or more sugar oxidation products comprise glucodialdose, 2-keto-D-glucose or combinations thereof.

[0040] A third aspect which is the method of any of the first through second aspects wherein conditions suitable for the formation of a reaction mixture comprise a temperature of equal to or greater than about 200 °C.

[0041] A fourth aspect which is the method of any of the first through third aspects wherein conditions suitable for the formation of a reaction mixture comprise reaction times of from about 1 minute to about 24 hours.

[0042] A fifth aspect which is the method of any of the first through fourth aspects wherein the sugar is glucose.

[0043] A sixth aspect which is the method of any of the first through fifth aspects further comprising: subjecting the reaction mixture to one or more means of purifying the reaction mixture to produce a product comprising glycolaldehyde having a purity of equal to or greater than about 70%.

[0044] A seventh aspect which is the method of any of the first through sixth aspects further comprising subjecting the glycolaldehyde to conditions suitable for reductive amination to form an amine product.

[0045] An eighth aspect which is the method of any of the first through seventh aspects wherein conditions suitable for reductive amination comprise the presence of a nitrogencontaining compound, a catalyst or both,

[0046] A ninth aspect which is the method of the eighth aspect wherein the nitrogencontaining compound comprises ammonia.

[0047] A tenth aspect which is the method of any of the eighth through ninth aspects wherein the catalyst comprises Rainey nickel.

[0048] An eleventh aspect which is the method of any of the eighth through tenth aspects wherein the amine comprises ethanolamine.

[0049] A twelfth aspect which is the method of any of the first through eleventh aspects further comprising subjecting the glycolaldehyde to conditions suitable for hydrogenation to form a glycol product.

[0050] A thirteenth aspect which is the method of the twelfth aspect wherein conditions suitable for hydrogenation comprise the presence of a hydrogen, a hydrogenation catalyst or both.

[0051] A fourteenth aspect which is the method of any of the twelfth through thirteenth aspects wherein the hydrogenation catalyst comprises (i) a transition-metal compound, a transition-metal salt or combinations thereof and (ii) a support material.

[0052] A fifteenth aspect which is the method of any of the twelfth through fourteenth aspects wherein (i) the transition-metal compound, the transition-metal salt or combinations thereof comprises iron (Fe), copper (Cu), rhodium (Rh), rhenium (Re), iridium (Ir), cobalt (Co), nickel (Ni), platinum (Pt), palladium (Pd), gold (Au), ruthenium (Ru), oxides thereof, or combinations thereof.

[0053] A sixteenth aspect which is the method of any of the twelfth through fifteenth aspects wherein the support material comprises s glass, titania, silica, alumina, zirconia, ceria, ceramic, carbon or combinations thereof.

[0054] A seventeenth aspect which is the method of any of the first through sixteenth aspects further comprising subjecting the glycolaldehyde to conditions suitable for thermal cracking and recovering a product mixture comprising C1-C3 oxygenates.

[0055] An eighteenth aspect which is a method for the production of higher value chemicals comprising; pyrolyzing reactants comprising glucodialdose, 2-keto-D-glucose or both in the absence of oxygen under conditions suitable for the formation of a reaction mixture comprising from about 1 wt.% to equal to or greater than about 50 wt.% glycolaldehyde; recovering at least a portion of the glycolaldehyde to obtain recovered glycolaldehyde; and purifying the recovered glycolaldehyde to obtain a purity of from about 70% to about 85% to obtain purified glycolaldehyde.

[0056] A nineteenth aspect which is the method of the eighteenth aspect further comprising contacting the purified glycolaldehyde with a hydrogenation catalyst under conditions suitable for the formation of a glycol.

[0057] A twentieth aspect which is the method of any of the eighteenth through nineteenth aspects further comprising contacting the purified glycolaldehyde with a Rainey nickel catalyst under conditions suitable for the formation of an amine.EXAMPLES

[0058] The subject matter having been generally described, the following examples are given as particular aspects of the disclosure and are included to demonstrate thepractice and advantages thereof, as well as aspects and features of the presently disclosed subject matter. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventors to function well in the practice of the present subject matter, and thus can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific aspects which are disclosed and still obtain a like or similar result without departing from the scope of the instant disclosure. It is understood that the examples are given by way of illustration and are not intended to limit the specification of the claims to follow in any manner.PROPHETIC EXAMPLE

[0059] A value added chemical is prepared from glucose using the methods disclosed herein. Particularly, GDA or 2KG is prepared by the oxidation of glucose catalyzed by a mutant GAO in the presence of a suitable SEO and SMA. A reactant comprising GDA, 2KG or both is pyrolyzed by exposing to a temperature of equal to or greater than about 200 °C for a time period suitable for formation of a reaction product comprising equal to or greater than about 20% glycolaldehyde. The reaction product or a purified portion thereof may be subjected to hydrogenation by the introduction of hydrogen at 90 bar and 80 °C in the presence of a suitable hydrogenation catalyst and nitrogen source for a reaction time of about 6 hours. The resulting reaction product may comprise an amine.

[0060] The subject matter having been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the subject matter. The aspects described herein are exemplary only and are not intended to be limiting. Many variations and modifications of the subject matter disclosed herein are possible and are within the scope of the disclosed subject matter. Where numerical ranges or limitations are expressly stated, such express ranges or limitations should be understood to include iterative ranges or limitations of like magnitude falling within the expressly stated ranges or limitations (e.g . , from about 1 to about 10 includes, 2, 3, 4, etc.; greater than 0.10 includes 0.11 , 0.12, 0.13, etc.). Use of the term "optionally" with respect to any element of a claim is intended to mean that the subject element is required, or alternatively, is not required. Both alternatives are intended to be within the scope of the claim. Use of broader terms such as comprises, includes, having, etc.should be understood to provide support for narrower terms such as consisting of, consisting essentially of, comprised substantially of, etc.

[0061] Accordingly, the scope of protection is not limited by the description set out above but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims. Each and every claim is incorporated into the specification as an aspect of the present disclosure. Thus, the claims are a further description and are an addition to the aspects of the present invention. The discussion of a reference herein is not an admission that it is prior art to the presently disclosed subject matter, especially any reference that may have a publication date after the priority date of this application. The disclosures of all patents, patent applications, and publications cited herein are hereby incorporated by reference, to the extent that they provide exemplary, procedural or other details supplementary to those set forth herein.

Claims

CLAIMSWhat is claimed is:1 . A method for the production of higher value chemicals, the method comprising; pyrolyzing one or more sugar oxidation products in the absence of oxygen under conditions suitable for the formation of a reaction mixture comprising from about 1 wt.% to equal to or greater than about 50 wt.% glycolaldehyde based on the total weight of the reaction mixture; and recovering at least a portion of the glycolaldehyde.

2. The method of claim 1 , wherein the one or more sugar oxidation products comprise glucodialdose, 2-keto-D-glucose or combinations thereof.

3. The method of claim 1 , wherein conditions suitable for the formation of a reaction mixture comprise a temperature of equal to or greater than about 200 °C.

4. The method of claim 1 , wherein conditions suitable for the formation of a reaction mixture comprise reaction times of from about 1 minute to about 24 hours.

5. The method of claim 1 , wherein the sugar is glucose.

6. The method of claim 1 , further comprising: subjecting the reaction mixture to one or more means of purifying the reaction mixture to produce a product comprising glycolaldehyde having a purity of equal to or greater than about 70%.

7. The method of claim 1 , further comprising subjecting the glycolaldehyde to conditions suitable for reductive amination to form an amine product.

8. The method of claim 1 , wherein conditions suitable for reductive amination comprise the presence of a nitrogen-containing compound, a catalyst or both,9. The method of claim 8, wherein the nitrogen-containing compound comprises ammonia.

10. The method of claim 8, wherein the catalyst comprises Rainey nickel.11 . The method of claim 8, wherein the amine comprises ethanolamine.

12. The method of claim 1 , further comprising subjecting the glycolaldehyde to conditions suitable for hydrogenation to form a glycol product.

13. The method of claim 12, wherein conditions suitable for hydrogenation comprise the presence of a hydrogen, a hydrogenation catalyst or both.

14. The method of claim 12, wherein the hydrogenation catalyst comprises (i) a transition-metal compound, a transition-metal salt or combinations thereof and (ii) a support material.

15. The method of claim 12, wherein (i) the transition-metal compound, the transitionmetal salt or combinations thereof comprises iron (Fe), copper (Cu), rhodium (Rh), rhenium (Re), iridium (lr), cobalt (Co), nickel (Ni), platinum (Pt), palladium (Pd), gold (Au), ruthenium (Ru), oxides thereof, or combinations thereof.

16. The method of claim 12, wherein the support material comprises s glass, titania, silica, alumina, zirconia, ceria, ceramic, carbon or combinations thereof.

17. The method of claim 1 , further comprising subjecting the glycolaldehyde to conditions suitable for thermal cracking and recovering a product mixture comprising C1-C3 oxygenates.

18. A method for the production of higher value chemicals, the method comprising; pyrolyzing reactants comprising glucodialdose, 2-keto-D-glucose or both in the absence of oxygen under conditions suitable for the formation of a reaction mixture comprising from about 1 wt.% to equal to or greater than about 50 wt.% glycolaldehyde;recovering at least a portion of the glycolaldehyde to obtain recovered glycolaldehyde; and purifying the recovered glycolaldehyde to obtain a purity of from about 70% to about 85% to obtain purified glycolaldehyde.

19. The method of claim 18, further comprising contacting the purified glycolaldehyde with a hydrogenation catalyst under conditions suitable for the formation of a glycol.

20. The method of claim 18, further comprising contacting the purified glycolaldehyde with a Rainey nickel catalyst under conditions suitable for the formation of an amine.

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