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    公开号:BR112012031494B1
    申请号:R112012031494
    申请日:2010-12-13
    公开日:2018-09-25
    发明作者:L Dias Eric；Frederick Salem George；Zhu Guang；Shoemaker James；Archer Raymond；J Murphy Vicent
    申请人:Rennovia Inc；
    IPC主号:
    专利说明:

    (54) Title: CATALYST COMPOSITION, AND, PROCESS FOR THE PREPARATION OF GLUCARIC ACID OR DERIVATIVES OF THE SAME (51) Int.CI .: B01J 21/06; B01J 21/08; B01J 23/52; B01J 21/16; B01J 21/18; B01J 35/00; B01J 37/02 (30) Unionist Priority: 11/06/2010 US 12/814188 (73) Holder (s): RENNOVIA, INC.
    (72) Inventor (s): VICENT J. MURPHY; JAMES SHOEMAKER; GUANG ZHU; RAYMOND ARCHER; GEORGE FREDERICK SALEM; ERIC L. DIAS (85) National Phase Start Date: 10/12/2012 “CATALYST COMPOSITION, AND, PROCESS FOR THE PREPARATION OF GLUCARIC ACID OR DERIVATIVES FROM THE SAME”
    FIELD OF THE INVENTION
    The present invention generally relates to catalysts composed of platinum and gold. The catalysts of the present invention are useful for the selective oxidation of compositions comprised of a primary alcohol and at least one secondary alcohol for carboxylic acids or derivatives thereof. The catalysts of the present invention are particularly useful for the selective oxidative chemocatalytic conversion of carbohydrates to carboxylic acids. More particularly, the catalysts of the present invention are useful for the selective oxidation of glucose to gluconic acid or derivatives thereof. The present invention is also directed to processes for the manufacture of such catalysts. The present invention is further directed to processes for converting glucose to glucaric acid and / or derivative thereof using such catalysts.
    BACKGROUND OF THE INVENTION
    Crude oil is currently the source of most consumer goods and organic chemical specialties. Many of these chemicals are used in the manufacture of polymers and other materials. Examples include ethylene, propylene, styrene, bisphenol A, terephthalic acid, adipic acid, caprolactam, hexamethylenediamine, adiponitrile, caprolactone, acrylic acid, acrylonitrile, 1,6-hexanediol, 1,3-propanediol and others. Crude oil is first refined into intermediate hydrocarbons, such as ethylene, propylene, benzene and cyclohexane. These intermediate hydrocarbons are then typically selectively oxidized using various processes to produce the desired chemicals. For example, crude oil is refined to cyclohexane which is then selectively oxidized to "KA oil" which is then further oxidized to produce adipic acid, an important industrial monomer used for the production of nylon 6,6. Many known processes are used industrially to produce these precursor petrochemicals found in crude oil. For example, see Ullmanrís Encyclopedia of Industrial Chemistry, Wiley 2009 (7th edition), which is incorporated herein by reference.
    For many years there has been an interest in using bio-renewable materials as a raw material to replace or complement crude oil. See, for example, Klass, Biomass for Renewable Energy, Fuels, and Chemicals, Academic Press, 1998, which is incorporated herein by reference. In addition, efforts have been made to produce carboxylic acids from renewable resources using processes that involve a combination of biocatalytic and chemocatalytic processes. See, for example, "Benzene-Free Synthesis of Adipic Acid", Frost et al. Biotechnol. Prog. 2002, Vol. 18, pp. 201-211, and US Patents 4,400,468, and 5,487,987.
    One of the biggest challenges for the conversion of bio-renewable resources such as carbohydrates (eg, glucose derived from cellulose, starch or sucrose), for consumer goods and specialty chemicals is the selective conversion of the primary alcohol group (hydroxyl) to a carboxyl group (COOH) in the presence of at least one secondary alcohol group.
    Glucose can be obtained from various sources containing carbohydrates, including conventional bio-renewable sources such as corn (more) grains, wheat, potatoes, cassava and rice, as well as alternative sources such as energy crops, plant biomass, agricultural residues, forest residues , sugar processing residues and household waste derived from vegetables. More generally, bio-renewable sources include any renewable organic matter that includes a source of carbohydrates, such as, for example, residues of yellow paint (Panicum virgatum), miscanthus, trees (hard and soft wood), vegetation and crops (for example, bagasse and corn straw). Other sources may include, for example, waste materials (for example, spent paper, green waste, municipal waste, etc.).
    Carbohydrates, like glucose, can be isolated from bio-renewable materials using methods that are known in the art. See, for example, Centi and van Santen, Catalysis for Renewables, Wiley-VCH, Weinheim 2007; Kamm, Gruber and Kamm, BiorefineriesIndustrial Processes and Products, Wiley-VCH, Weinheim 2006; Shang-Tian Yang, Bioprocessingfor Value-Added Products from Renewable Resources New Technologies and Applications, Elsevier BV 2007; Furia, Starch in the Food Industry, Chapter 8, CRC Handbook of Food Additives 2nd Edition CRC Press, 1973. See also chapters devoted to starch, sugar, and syrups in Kirk-Othmer Encyclopedia of Chemical Technology 5th Edition, John Wiley and Sons 2001 In addition, processes for converting starch to glucose are known in the art, see, for example, Schenck, “Glucose and Glucosecontaining Syrups” in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH 2009. In addition, methods for converting 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, Bioprocessingfor Value-Added Products from Renewable Resources New Technologies and Applications, Elsevier BV 2007.
    The selective oxidation of glucose to glucaric acid has been carried out using oxidation methods that employ platinum catalysts. See, for example, US Patent 2,472,168, which illustrates a method for the preparation of glucaric acid from glucose using a platinum catalyst in the presence of oxygen and a base. Other examples of preparing glucaric acid from glucose using a platinum catalyst in the presence of oxygen and a base are illustrated in the Journal of Catalysis Vol. 67, p. 1-13, and p. 14-20 (1981). Other oxidation methods have also been used, see, for example, US Patent 6,049,004,
    5,599,977, and 6,498,269, WO 2008/021054 and J. Chem. Technol. Biotechnol.
    76, p. 186-190 (2001), J. Agr. Food Chem. Vol. 1, p.779-783 (1953); J. Carbohydrate Chem. Vol. 21, p. 65-77 (2002); Carbohydrate Res. Vol. 337, p. 1059-1063 (2002); Carbohydrate Res. 336, p. 75-78 (2001), and Carbohydrate Res. Vol. 330, p. 21-29 (2001). However, these processes suffer from economic deficiencies due, among other issues, to process yield limitations, low conversion rates and limited selectivity due to deficiencies in the performance of existing catalysts. None of these catalysts or processes that employ them are used industrially for the selective oxidation of carbohydrates containing glucose, for the manufacture of specialty or industrial carboxylic acids or derivatives thereof.
    Thus, there remains a need for new, industrially scalable catalysts for the selective and commercially significant conversion of a primary hydroxyl group with a carboxyl group of compositions comprising a primary hydroxyl group and at least one secondary hydroxyl group. Desirably, there is a need to convert bio-renewable materials such as, for example, carbohydrates or polyols, to specialty or industrial carboxylic acids and derivatives thereof, and more particularly, for example, to convert glucose (derived from starch, cellulose, or sucrose), for important chemicals, such as glucaric acid and derivatives thereof.
    SUMMARY OF THE INVENTION
    The present invention is generally directed to catalyst compositions comprising gold and discrete platinum particles on a support where the ratio of platinum to gold on the support is in the range of about 100: 1 to about 1: 4 and the platinum is substantially present in the support as Pt (O).
    The present invention is also directed to catalyst compositions useful for the selective conversion of a primary hydroxyl group of compositions comprising a primary hydroxyl group and at least one secondary hydroxyl group to a carboxyl group, wherein the catalyst compositions comprise platinum and gold.
    The present invention is further directed to catalyst compositions comprising gold and discrete platinum particles on a support, where (a) the ratio of platinum to gold on the support is in the range of about 100: 1 to about 1: 4 , (b) the platinum is substantially present in the support as Pt (O), and (c) the particle sizes of the platinum particles are substantially in the range of about 2 to about 50 nanometers.
    In addition, the present invention is directed to catalyst compositions comprising particles comprising gold and particles of platinum on a support, where (a) the ratio of platinum to gold on the support is in the range of about 100: 1 to about 1: 4, (b) the platinum is substantially present in the support as Pt (O), (c) the particle sizes of the platinum particles are substantially in the range from about 2 to about 50 nanometers, and (d) the particle sizes of the gold-containing particles are substantially in the range of about 2 to about 20 nanometers.
    In addition, the present invention is directed to catalyst compositions produced by processes comprising the steps of a) providing a solid support, b) contacting the support with at least one compound containing gold, c) contacting the support and at least one gold-containing compound with a base, d) contacting the support with at least one platinum-containing compound, and e) treating the support and at least one platinum-containing compound under sufficient conditions to create particles containing gold and particles comprising platinum on the support, in that the platinum to gold ratio on the support is in the range of about 100: 1 to about 1: 4, the platinum is substantially present in the support as Pt (O), and the particle sizes of the platinum particles are substantially in the range of about 2 to about 50 nanometers.
    The present invention is further directed to processes for the preparation of glucaric acid or derivatives thereof, reacting glucose with an oxygen source in the presence of a catalyst comprising platinum and gold, and in the substantial absence of added base.
    Other objectives and characteristics will become apparent and / or will be pointed out below.
    BRIEF DESCRIPTION OF THE DRAWINGS
    Fig. 1 is a TEM photograph of the fresh catalyst prepared according to Example 2 (entry 21) composed of 4% by weight of platinum and 4% by weight of gold over 150-250 pm Saint Gobain Norpro Titania particles with a magnification of 88k.
    Fig. 2 is a TEM photograph of fresh catalyst of the present invention, as described with reference to Fig. 1 at a magnification of 53Ok.
    Fig. 3 is a TEM photograph of fresh catalyst of the present invention, as described with reference to Fig. 1 with a magnification of 53 Ok.
    Fig. 4 is a TEM photograph of fresh catalyst of the present invention, as described with reference to Fig. 1 at a magnification of 530k.
    DESCRIPTION OF THE PREFERRED EMBODIMENTS
    In accordance with the present invention, applicants disclose catalyst compositions composed of platinum and gold.
    The catalyst compositions of the present invention are particularly useful for the selective oxidation of a primary alcohol to a carboxyl in compositions comprising the primary hydroxyl group (alcohol) and at least one secondary hydroxyl group (alcohol). High selectivity and conversion in conjunction with unexpectedly high yield is a result of using the catalysts of the present invention. The conversion of carbohydrates and, more particularly, of glucose and derivatives thereof to oxidation products, such as glucaric acid and derivatives thereof, is especially effective employing the catalysts of the present invention.
    The catalyst compositions of the present invention comprise platinum and gold. These catalysts are heterogeneous, solid phase catalysts. In various modalities, metals are present on a support surface (that is, on one or more surfaces, internal or external). Suitable catalyst supports include carbon, surface treated with aluminas (such as passivated aluminas or coated aluminas), silicas, titanias, zirconias, zeolites, montmorillonites, and modifications, mixtures or combinations thereof. Preferred support materials include titanium, zirconia, silica and montmorillonite. Preferred support materials can be modified using methods known in the art, such as heat treatment, acid treatment, steam treatment or by introducing a dopant (for example, metal-doped titanias or metal-doped zirconias such as tungstate zirconia) . The catalyst support can be treated to promote preferential deposition of metals on the external surface of the support, in order to create a shell-type catalyst. The supports can be in a variety of shapes, such as powders, pellets, spheres, extrudates and xerogels.
    The performance of the catalyst, in general, is in part significantly dependent on the degree of uniformity of dispersion of the metals on the support. The platinum and gold-containing catalysts of the present invention can be produced by deposition processes known in the art, including, but not limited to, incipient moisture, ion exchange, and deposition-precipitation. In various embodiments, uniform dispersion can be achieved by forming a heterogeneous paste of the support, in combination with solubilized metal complexes. In certain embodiments, the supports can initially be dispersed in a liquid such as water. After that, in such embodiments, the solubilized metal complexes can be added to the paste containing the support. The heterogeneous mixture of solids and liquids can then be agitated, mixed and / or agitated to enhance the uniformity of the dispersion of the catalyst, which, in turn, allows for more uniform deposition of metals on the support surface after removal of liquids and additional treatments that may be needed and more fully described below.
    The gold component of the catalysts of the present invention is typically added to the support as a solubilized constituent to allow the formation of a uniform suspension. The base is then added to the suspension to create an insoluble gold complex that can be more evenly deposited on the support. For example, in various embodiments, the solubilized gold constituent is supplied to the suspension, for example, HAuCfi. After creating a well-dispersed, heterogeneous mixture, a base is added to the paste in order to form an insoluble gold complex that is then deposited on the surface of the support. Although any base that can effect the formation of an insoluble gold complex is usable, in various modalities, bases containing nitrogen, such as ammonia or urea are employed. It may be desirable, although not necessary, to collect the support on which the insoluble gold complex has been deposited prior to the addition of the platinum-containing constituent, that the collection can be readily achieved by any of a variety of means known in the art, such as , for example, centrifugation. The collected solids can optionally be washed and then heated to dryness. Heating can also be employed in order to reduce the gold complex on the Au support (0). Heating can be carried out at temperatures ranging from about 60 ° C (dry) to about 500 ° C (temperature at which gold can be effectively reduced). In several modalities, the heating step can be carried out in the presence of an atmosphere of reduction or oxidation in order to promote the reduction of the complex to deposit the gold on the support as Au (0). The heating times vary depending, for example, on the purpose of the heating step, and on the rate of decomposition of the base added to form the insoluble complex, and the heating times can vary from a few minutes to a few days. More typically, the heating time for the purpose of drying varies from about 2 to about 24 hours and for the reduction of the gold complex it is on the order of about 1 to 4 hours.
    In various embodiments, the concentration of the support in the paste can be in the range of about 1 to about 100 g of a solid / liter of paste, and in other embodiments the concentration can be in the range of about 5 to about 25 g of paste. solid / liter of paste.
    The mixture of paste containing the compound containing soluble gold is continued for a time sufficient to form at least a reasonably uniform suspension. The appropriate times can vary from minutes to a few hours. After adding the base to convert the gold-containing compound to an insoluble gold-containing complex, the uniformity of the slurry must be maintained long enough to allow the insoluble complex to form and deposit on the support. In various modalities, the time can vary from a few minutes to several hours.
    The gold deposited on the surfaces of the support forms particles that comprise gold. More typically, gold in the fresh catalyst exists as Au (0) particles and / or as gold-containing alloys, such as gold-platinum alloys. The particle size will vary, but the particles are substantially of a size generally less than or equal to about 20 nanometers (nm). "Size" means the largest, straight-line dimension of the particle, and "substantially" means at least about 50%. More typically, the particles are substantially of a size in the range of about 2 to about 15 nm and, more preferably, in the range of about 5 to about 12 nm.
    Platinum is typically added to the support or paste containing support after the deposition of gold on the support and, more preferably, after the decomposition of the base. Alternatively, the platinum can be added to the support or paste containing support prior to the addition of the solubilized gold compound as long as the platinum present on the support is in a form that will not redissolve by adding base used to promote gold deposition. about support. Platinum is usually added as a solution to a soluble precursor, or as a colloid. Platinum can be added as a compound selected from the group of platinum (II) nitrate, platinum (II) acetylacetonate (acac), tetra-aminoplatin nitrate (II), tetra-aminoplatin hydrogen phosphate (II) and tetra hydroxide -aminoplatin (II). The most preferred compounds include platinum (II) nitrate, platinum (II) acetylacetonate (acac), and platinum (II) tetraamine nitrate.
    After adding the platinum compound, the backing paste and platinum-containing compound is dried. Drying can be carried out at room temperature or at a temperature up to about 120 ° C. Most preferably, drying is carried out at a temperature in the range of about 40 ° C to about 80 ° C and even more preferably at about 60 ° C. The drying step can be carried out for a period of time ranging from about a few minutes to a few hours. Typically, the drying time is in the range of about 6 hours to about 24 hours.
    After drying the support having the platinum compound deposited on it, it is subjected to at least one heat treatment in order to reduce the platinum deposited as Pt (II) or Pt (IV) from Pt (O). The heat treatment (s) can be carried out in air or in any reducing or oxidizing atmosphere. In various modalities the heat treatment (s) is (are) carried out under an atmosphere of forming gas. Alternatively, a liquid reducing agent can be used to reduce platinum, for example, hydrazine or formaldehyde can be used to effect the necessary reduction of platinum. The atmosphere in which the heat treatment is performed depends on the platinum compound employed, with the objective being substantially the conversion of the platinum to the Pt (O) support.
    The temperatures at which the heat treatment (s) is (are) carried out generally range from about 200 ° C to about 600 ° C. More typically, the temperatures of the heat treatment (s) range from about 200 ° C to about 500 ° C and, preferably, range from about 200 ° C to about 400 ° C. Heat treatment is usually carried out over a period of time ranging from about 1 hour to about 5 hours. More typically, treatment is carried out over a period of time ranging from about 1 hour to about 3 hours. For example, at a heat treatment temperature of about 350 ° C, the treatment time is about 3 hours.
    The platinum deposited on the surfaces of the support forms particles. Generally, the platinum in the fresh catalyst exists substantially as particles of essentially Pt (O) and / or as alloys containing platinum, such as gold-platinum alloys. In various embodiments, the catalysts will comprise discrete platinum particles, particles comprising platinum and gold, and possibly gold particles. In certain preferred embodiments, essentially all particles consisting essentially of platinum exist as Pt (O). The particle size will vary, but the particles are substantially of a size generally less than or equal to about 50 nanometers (nm). By "size" is meant the largest dimension in a straight line of the particle. By "substantially" is meant at least about 50%. More typically, the particles are substantially of a size in the range of about 2 to about 50 nm and, preferably, in the range of about to about 30 nm. More preferably, the particles are at least substantially in the range of about 5 to about 20 nm and, more preferably, in the range of about 8 to about 12 nm.
    The molar ratio of platinum: gold can range, for example, from about 100: 1 to about 1: 4, from about 50: 1 to about 1: 4, from about 10: 1 to about 1: 4, or more preferably from about 3: 1 to about 1: 4. Most preferably, the platinum: gold molar ratio can vary, for example, from about 3: 1 to about 1: 2. Even more preferably, the platinum: gold molar ratio is in the range of about 2: 1 to about 1: 1.
    Figure 1 shows a TEM photograph taken at an 88k magnification of a 4 wt% Au catalyst - 4 wt% Pt of the present invention prepared according to Example 2 (entry 21). As shown, the metal particles (dark) in the support (light) are less than about 50 nm, at least about 50% are less than about 20 nm, and at least about 50% are less than about 15 nm but are generally equal to or greater than about 2 nm. Figures 2, 3 and 4 are photographs of the same fresh catalyst taken at 530k magnifications, clearly showing the presence of metallic particles of about 10 nm and nm, and as small as about 2 nm.
    In several other embodiments, a third metal (M3) can be added to produce a Pt / Au / M3 catalyst in which the M3 metal is not platinum or gold. In still other embodiments, a fourth metal (M4) can be added to produce a Pt / Au / M3 / M4 catalyst in which the M4 metal is not platinum or gold and are also not the same metals as the M3 metal. The M3 metal and the M4 metal can each be selected from the group 6 or group 10 metals, with palladium being the most preferred group 10 metal and tungsten being the most preferred group 6 metal.
    The total metal charge on the final catalyst (i.e., excluding any metal that is on the support) is generally less than or equal to about 10% by weight relative to the total weight of the catalyst. Generally, the total metal charge is in the range of about 1% to about 10%. More typically, the total weight percentage ranges from about 1% to about 8%, and more preferably, from about 1% to about 4%.
    Glucose is effectively converted to glucaric acid with a high yield by glucose reaction with oxygen (as used herein, oxygen can be supplied for the reaction as air, oxygen-enriched air, individually oxygen, or oxygen with other substantially inert constituents reaction) in the presence of catalyst compositions of the present invention, and in the absence of base added according to the following reaction:
    Glucose
    Carrying out the oxidation reaction in the absence of added base and in the presence of the catalyst compositions of the present invention does not lead to significant catalyst poisoning effects and the selectivity of the oxidation catalyst is maintained. In fact, catalytic selectivity can be maintained to achieve a yield of glucaric acid in excess of 60%, even 65% and, in some modalities, achieve yields in excess of 70% or higher. The absence of added base advantageously facilitates the separation and isolation of glucaric acid, thus providing a process that is more amenable to industrial application, and improves the overall economy of the process by eliminating a reaction component. The "absence of added base" as used herein, means that the base, if present (for example, as a constituent of a raw material), is present in a concentration that has essentially no effect on the effectiveness of the reaction ( that is, the oxidation reaction is being conducted essentially free of added base). It has also been found that this oxidation reaction can also be carried out in the presence of a weak carboxylic acid, such as acetic acid, in which glucose is soluble. The term "weak carboxylic acid", as used herein, means any substituted or unsubstituted carboxylic acid having a pKa of at least about 3.5, more preferably, at least about 4.5 and, more particularly, is selected from among unsubstituted acids, such as acetic acid, propionic acid or butyric acid, or mixtures thereof.
    The initial pH of the reaction mixture is not more than about 7, and is typically less than 7, such as, for example, 6 or less (for example, when a weak carboxylic acid is used to solubilize at least a portion of the glucose) . The initial pH of the reaction mixture is the pH of the reaction mixture before contact with oxygen in the presence of an oxidation catalyst. The pH of the reaction mixture after oxygen contact is expected to vary as the reaction proceeds. It is believed that as the concentration of glucaric acid increases (as the reaction proceeds), the pH will decrease from the initial pH.
    The process of producing glucaric acid or derivatives thereof from carbohydrates, such as glucose, can be carried out with the catalysts of the present invention in the essential absence of nitrogen as an active reaction constituent. Typically, nitrogen is used in processes known as an oxidizer, such as in the form of nitrate, in many cases, such as nitric acid. The use of nitrogen in a form in which it is an active reaction constituent, such as nitrate or nitric acid, results in the need for NOx reduction technology and acid regeneration technology, both of which increase the significant cost for the production of glucaric acid from these known processes, as well as providing a corrosive environment, which can adversely affect the equipment used to carry out the process. In contrast, for example, if air or oxygen-enriched air is used in the oxidation reaction of the present invention as an oxygen source, nitrogen is essentially an inactive or inert component. Thus, for example, an oxidation reaction that uses air or oxygen-enriched air is a reaction conducted essentially free of nitrogen in a form in which it would be an active reaction constituent.
    In general, the temperature of the oxidation reaction mixture is at least about 40 ° C, more typically 60 ° C, or higher. In various embodiments, the temperature of the oxidation reaction mixture is from about 40 ° C to about 150 ° C, from about 60 ° C to about 150 ° C, from about 70 ° C to about 150 ° C , from about 70 ° C to about 140 ° C, or from about 80 ° C to about 140 ° C.
    Typically, the partial pressure of oxygen is at least about 15 pounds per absolute square inch (psia) (104 kPa), at least about 25 psia (172 kPa), at least about 40 psia (276 kPa), or at least about 60 psia (414 kPa). In various embodiments, the partial pressure of oxygen is up to about 1000 psi (6895 kPa), or more typically in the range of about 15 psia (104 kPa) to about 500 psia (3447 kPa).
    The oxidation reaction is typically conducted in the presence of a solvent for glucose. Suitable solvents for the oxidation reaction include water and weak carboxylic acids such as acetic acid. The use of weak carboxylic acid as a solvent increases the cost of the process, the cost of which as a practical matter, must be balanced against any benefits derived from its use. Thus, solvents suitable for the present invention include water, mixtures of water and weak carboxylic acid, or weak carboxylic acid. The catalyst compositions of the present invention remain stable in the presence of the solvent.
    In general, the oxidation reaction can be conducted in a batch, semi-stacked or continuous reactor model using fixed bed reactors, drip bed reactors, paste phase reactors, moving bed reactors or any other model that allows heterogeneous catalytic reactions. Examples of reactors can be seen in Chemical Process Equipment - Selection and Design, Couper et al., Elsevier 1990, which is incorporated herein by reference. It should be understood that oxygen, glucose, any solvent, and the oxidation catalyst can be introduced into a suitable reactor separately or in various combinations.
    The reaction product of the oxidation step, as described above, will contain glucaric acid in the unexpected and considerable fraction, but it may also contain derivatives thereof, such as glucarolactones. These glucarolactones, like glucaric acid, constitute a hydrodeoxygenation substrate that is particularly susceptible to the production of adipic acid product as described below. The glucarolactones that may be present in the reaction mixture resulting from the oxidation step include mono- and di-lactones, such as D-glucaro-1,4, 4-lactone, D-glucaro-6,3-lactone, and Dglucaro-1,4: 6,3-dilactone. An advantage of higher concentrations of glucarolactones is to further improve the economy of a downstream hydrodeoxygenation step for the production of adipic acid, resulting from a reduction in the amount of water produced.
    The glucaric acid produced according to the above can be converted into several other glucaric acid derivatives, such as salts, esters, ketones, and lactones. Methods for converting carboxylic acids to such derivatives are known in the art, see, for example, Wade, Organic Chemistry 3rd ed, Prentice Hall 1995.
    Adipic acid is an example of an important industrial product that can be prepared by chemocatalytic conversion of a glucose source through intermediates, such as glucaric acid or derivatives thereof, whose intermediates are attainable from the use of the catalyst compositions of present invention. In this process, a hydrodeoxygenation substrate comprising glucaric acid or derivatives thereof can be converted to an adipic acid product.
    The hydrodeoxygenation substrate comprises a compound from Formulai:
    where X is independently hydroxyl, oxo, halo, acyloxy, or hydrogen, provided that at least one X is not hydrogen, R 1 is independently a salt-forming, hydrogen, hydrocarbyl, hydrocarbyl or hydrocarbyl ion, or a mono- or di-lactone of the same.
    As used herein, the term "hydrocarbyl" refers to hydrocarbyl fractions, preferably containing 1 to about 50 carbon atoms, preferably 1 to about 30 carbon atoms, and even more preferably 1 to about 18 carbon atoms, including branched or unbranched, and saturated or unsaturated species. The preferred hydrocarbil can be selected from the group consisting of alkyl, alkylene, alkoxy, alkylamino, thioalkyl, haloalkyl, cycloalkyl, cycloalkylalkyl, heterocyclyl, TV-heterocyclyl, heterocyclylalkyl, aryl, aralkyl, heteroaryl, A-heteroaryl, heteroaryl, heteroaryl, alkyl and similar. The hydrocarbyl may optionally be substituted hydrocarbyl. Thus, several hydrocarbyl groups can be further selected from substituted alkyl, substituted cycloalkyl and the like.
    Salt-forming ions include, without limitation, for example, ammonium ions and metal ions (for example, alkaline earth and alkaline metals). When R 1 is an ion-forming salt (ie, a cation), the carboxyl group can be considered to be an anion (ie, the carboxylate anion).
    In various embodiments, the hydrodeoxygenation substrate comprises a compound of Formula I, where X is hydroxyl and R 1 is independently a salt-forming, hydrogen, hydrocarbyl or substituted hydrocarbyl ion.
    As shown in Formula I, the hydrodeoxygenation substrate contains a six-carbon chain comprising four chiral centers. As a result, several stereoisomers are possible.
    The hydrodeoxygenation substrate can also contain several ketones. For example, and not wishing to be bound by theory, when gluconic acid is oxidized, ketones, such as 2-keto-glucaric acid (2,3,4-trihydroxy-5-oxohexanedioic acid) and 3-keto acid -glucárico (2,3,5-trihydroxy-4-oxohexanedioic acid) can be formed.
    The hydrodeoxygenation substrate may comprise several lactones derived from glucaric acid. For example, and not wishing to be bound by theory, it is believed that the various mono- and di-lactones are present in equilibrium with glucaric acid in aqueous solution, including, for example, D-glucaro-1,4-lactone, D -glucaro-6,3-lactone, and D-glucarol, 4: 6,3-dilactone. On the other hand, the processes were developed to quantitatively convert glucaric acid or a salt thereof in solution to one or more lactones and recover a stream of substantially pure lactone. For example, see "Convenient Large-Scale Synthesis of D-Glucaro-1,4,4,3,3-dilactone" Gehret et al., J. Org. Chem., 74 (21), pp. 8373-8376 (2009). In addition, lactones, such as L-ether-4-deoxy-hex-4enaro-6,3-lactone and L-erz7ro-4-deoxy-hex-4-enaro-6,3-lactone, can form from of thermal decomposition of D-Glucaro-1,4: 6,3-dilactone.
    Therefore, in various embodiments, the hydrodeoxygenation substrate comprises D-glucaro-1,4-lactone. In these and other embodiments, the hydrodeoxygenation substrate comprises D-Glucaro-6,3lactone. In addition, in these and other embodiments, the hydrodeoxygenation substrate comprises D-Glucaro-1,4,4,3-dilactone. In these and other embodiments, the hydrodeoxygenation substrate comprises L-ether-4desoxy-hex-4-enaro-6,3-lactone. In addition, in these and other embodiments, the hydrodeoxygenation substrate comprises and L-er / Zro-4desoxy-hex-4-enaro-6,3-lactone.
    When introducing elements of the present invention or the preferred modalities thereof, the articles "one", "one", "o", "a" and the term "referred to" are intended to mean that there are one or more of elements. The terms "comprising", "including" and "having" are intended to be inclusive and mean that there may be additional elements other than those listed.
    In view of the above, it will be seen that the various objects of the invention are achieved and other advantageous results achieved.
    As several changes can be made to the above compositions and processes without departing from the scope of the invention, it is intended that all the material contained in the description above be interpreted as illustrative and not in a limiting sense.
    Having described the invention in detail, it will be evident that modifications and variations are possible without departing from the scope of the invention defined in the appended claims.
    EXAMPLES
    The following non-limiting examples are provided to further illustrate the present invention.
    Catalyst Test Protocol 1
    The catalyst (approximately 8 mg) was weighed in a glass vial insert followed by the addition of an aqueous glucose solution (250 μΐ of 10% by weight). The glass bottle insert was loaded into a reactor and the reactor was closed. The atmosphere in the reactor was replaced with oxygen and pressurized to 75 psig at room temperature. The reactor was heated to 90 ° C and maintained at 90 ° C for 5 hours while the flasks were shaken. After 5 hours, stirring was stopped and the reactor was cooled to 40 ° C. The pressure in the reactor was then released slowly. The glass bottle insert was removed from the reactor and centrifuged. The clear solution was diluted with deionized water and analyzed by ion chromatography (IC), with conductivity and detection by Corona CAD (IC-conductivityCAD). Samples for CI analysis were prepared by adding 750 μΐ of water to the reaction flask, followed by a 25-fold dilution. Product yields were determined using a Dionex ICS-3000 chromatography system equipped with a Corona CAD detector (ESA Biosciences). The products were first separated on an Ionpac® AS11-HC column and then quantified by conductivity and detection by Corona CAD by comparison with calibration standards.
    Catalyst Test Protocol 2
    The catalyst (approximately 75 mg) was weighed in a glass vial insert followed by the addition of an aqueous glucose solution (2.3 ml of 10% by weight). The glass bottle insert was loaded into a reactor and the reactor was closed with a disposable stirring paddle mounted on the reaction vessel. The atmosphere in the reactor was replaced with oxygen and pressurized to 50 psig at room temperature. The reactor was heated to a pre-defined temperature in the range of 90 to 133 ° C. After the temperature stabilized, the pressure in the reactor was increased to 400 psig using oxygen at high pressure. The agitation was switched on at 1100 rpm. The 400 psig pressure and the pre-set temperature in the reactor were maintained for an extended period of time, through computer control. When a designated reaction time was reached, oxygen supply was interrupted, stirring was discontinued and the reactor was cooled to 40 ° C. The pressure in the reactor was then released slowly. The glass bottle insert was removed from the reactor and centrifuged. The clear solution was diluted with deionized water and analyzed by IC-conductivity-CAD as previously described.
    Example 1
    Approximately 88 μΐ of an aqueous solution of HAuCfi (containing 0.2254% by weight of gold) was added to a 10 mg suspension of Titania P25 (Acros Organics) in deionized water (450 μΐ) during stirring. The suspension was stirred at room temperature for 30 min. 250 μΐ of an aqueous NH4OH solution (4.0 M) was added to the above suspension and the resulting suspension was stirred at room temperature for 2 hours. The resulting suspension was then centrifuged and the supernatant was decanted. After the residual liquid was removed using filter paper, the light yellow solid was dried in an oven at 60 ° C overnight under a dry air purge.
    2.1 μΐ of an aqueous solution of Pt (NO 3 ) 2 (containing 7.7% by weight of platinum) was added to the above solid and the mixture was stirred to impregnate the support containing gold. The sample was dried in an oven at 60 ° C overnight under a dry air purge. The sample was then reduced to 350 ° C under a gas-forming atmosphere (¾ at 5% and N 2 at 95%) for 3 hours at a temperature ramp rate of 2 ° C / min. The final catalyst contained about 2.0% by weight of gold and 2.0% by weight of platinum.
    By adjusting the volume and concentration of the HAuCU, NH4OH, and Pt (O 3 ) 2 solutions , a series of other catalysts with various fillers of gold (0 to 8% by weight) and platinum (0 to 8% by weight) ) was prepared. Similar methods are also used to prepare catalysts based on other supports, including Titânia ST 31119 (Saint-Gobain Norpro), Zirconia Z-1628 (Daiichi Kigenso Kagaku Kogyo), Zirconia Z-1044 (Daiichi Kigenso Kagaku Kogyo), Silica- Titânia Cariact (Fuji Silysia), Silica Cariact Q-10 (Fuji Silysia), Davisil 635 (Sigma-Aldrich), and Zeolite CP 811C-300 (Zeolyst). These catalysts were tested for glucose oxidation using the Catalyst test protocol 1 and the results are summarized in Table 1.
    Entries 4 to 6, 9, 13, 22, 23, 28, 29, 38, 39, 45, 49 to 51, 61, 62, 67, 68, 79 and 80 are comparative entries for compositions outside the scope of the present invention . Except for entry 51, these entries illustrate, when compared to the other entries shown in Table 1, the conversion and other benefits achievable from the compositions of the present invention. Inlet 51, while exhibiting a higher conversion, causes the production of undesirable products of superoxidation at a given yield of glucaric acid which makes it impractical for commercial use, when compared to the catalysts of the present invention. In addition, many industrial processes employ recycling of unreacted substrate in order to improve overall conversion and a high concentration of undesirable products reduces yields, ultimately achievable from raw material.
    Table 1: Conditions and results of glucose oxidation in gold / platinum catalysts of Example 1
    Input Catalyst p. (mg) Support Au% p. Pt% p. Glucose conversion (%) Glucaric Acid Yield (%) 1 8.3 Silica Cariact Q-10 0.8 7.2 98 51 2 8.0 Silica Cariact Q-10 2.8 1.2 100 36 3 8.1 Silica Cariact Q-10 3.2 0.8 100 28 4 7.7 Silica Cariact Q-10 4.0 0.0 99 4
    Catalyst p. (mg) Support Au% p. Pt% p. Glucose conversion (%) Glucaric Acid Yield (%) 8.4 Silica CariactQ-10 8.0 0.0 100 6 8.3 Davisil silica 635 0.0 8.0 96 44 8.2 Davisil silica 635 1.6 6.4 100 53 8.4 Davisil silica 635 2.4 1.6 100 46 8.5 Davisil silica 635 8.0 0.0 100 6 8.5 Silica-Titania Cariact 2.8 1.2 100 29 8.5 Silica-Titania Cariact 5.6 2.4 100 40 8.5 Silica-Titania Cariact 7.2 0.8 100 20 8.2 Titania P25 0.0 8.0 86 33 8.4 Titania P25 0.4 3.6 97 33 8.2 Titania P25 1.2 2.8 100 39 7.8 Titania P25 1.6 2.4 100 45 8.4 Titania P25 1.6 6.4 100 62 8.3 Titania P25 2.0 2.0 100 33 8.5 Titania P25 2.4 5.6 100 64 8.3 Titania P25 3.2 0.8 100 11 7.7 Titania P25 3.2 4.8 100 57 8.3 Titania P25 3.6 0.4 100 5 8.0 Titania P25 4.0 0.0 100 1 7.8 Titania P25 4.0 4.0 100 46 7.8 Titania P25 4.8 3.2 100 21 8.0 Titania P25 5.6 2.4 100 18 8.2 Titania P25 6.4 1.6 100 14 7.6 Titania P25 7.2 0.8 100 8 7.8 Titania P25 8.0 0.0 100 1 8.1 Titania ST 31119 0.8 3.2 100 40 8.5 Titania ST 31119 1.2 2.8 100 49 7.7 Titania ST 31119 1.6 2.4 100 42 7.9 Titania ST 31119 2.0 2.0 100 43 8.0 Titania ST 31119 2.4 1.6 100 25 7.6 Titania ST 31119 2.8 1.2 100 22 8.5 Titania ST 31119 3.2 0.8 100 21 7.9 Titania ST 31119 3.6 0.4 100 13 8.1 Titania ST 31119 4.0 0.0 100 2 8.4 Titania ST 31119 8.0 0.0 96 1 8.0 Zeolite CP 811C-300 0.8 3.2 93 22 8.1 Zeolite CP 811C-300 1.2 2.8 100 29 8.2 Zeolite CP 811C-300 2.4 1.6 100 28 7.9 Zeolite CP 811C-300 2.8 1.2 100 20 7.7 Zeolite CP 811C-300 3.2 0.8 100 14 8.3 Zeolite CP 811C-300 3.6 0.4 99 6 8.0 Zeolite CP 811C-300 4.8 3.2 100 41 8.4 Zeolite CP 811C-300 5.6 2.4 100 31 7.7 Zeolite CP 811C-300 6.4 1.6 100 20 7.9 Zeolite CP 811C-300 8.0 0.0 100 7 7.9 Zirconia 1628 0.0 4.0 84 23 8.2 Zirconia 1628 0.0 8.0 98 50 8.1 Zirconia 1628 0.4 3.6 85 22 8.3 Zirconia 1628 0.8 3.2 97 22 8.3 Zirconia 1628 0.8 7.2 98 45 8.0 Zirconia 1628 1.2 2.8 100 25 7.8 Zirconia 1628 1.6 2.4 100 22 8.2 Zirconia 1628 2.4 1.6 100 16 7.9 Zirconia 1628 2.8 1.2 100 17 8.4 Zirconia 1628 3.2 0.8 100 14 8.5 Zirconia 1628 3.2 4.8 100 40 7.8 Zirconia 1628 3.6 0.4 100 7 7.8 Zirconia 1628 4.0 0.0 99 0 7.9 Zirconia 1628 4.0 4.0 100 33 8.3 Zirconia 1628 4.8 3.2 100 24 8.0 Zirconia 1628 5.6 2.4 100 16 8.0 Zirconia 1628 6.4 1.6 100 9 8.2 Zirconia 1628 8.0 0.0 71 0 7.6 Zirconia Z-1044 0.0 4.0 72 19 7.9 Zirconia Z-1044 0.4 3.6 88 29 7.8 Zirconia Z-1044 0.8 3.2 100 40 8.1 Zirconia Z-1044 1.2 2.8 100 44
    Input Catalyst p. (mg) Support Au% p. Pt% p. Glucose conversion (%) Glucaric Acid Yield (%) 72 7.8 Zirconia Ζ-1044 1.6 2.4 100 36 73 8.2 Zirconia Z-1044 2.0 2.0 100 36 74 8.0 Zirconia Z-1044 2.4 1.6 100 32 75 7.5 Zirconia Z-1044 2.4 5.6 100 58 76 8.1 Zirconia Z-1044 2.8 1.2 100 26 77 7.9 Zirconia Z-1044 3.2 0.8 100 19 78 7.9 Zirconia Z-1044 3.2 4.8 100 58 79 8.0 Zirconia Z-1044 3.6 0.4 100 7 80 8.5 Zirconia Z-1044 4.0 0.0 100 3 81 8.0 Zirconia Z-1044 4.0 4.0 100 57 82 8.0 Zirconia Z-1044 4.8 3.2 100 47 83 7.6 Zirconia Z-1044 5.6 2.4 100 31 84 7.7 Zirconia Z-1044 6.4 1.6 100 16
    Example 2 μΐ of an aqueous solution of HAuCl 4 (containing 0.2254% by weight of gold) was added to a suspension of 10 mg of titania (P25, Acros Organics) in deionized water (550 μΐ) with stirring. The suspension was stirred at room temperature for 30 min. 250 μΐ of an aqueous NH4OH solution (4.0 M) was added to the above suspension and the resulting suspension was stirred at room temperature for 2 hours. The suspension was then centrifuged and the supernatant was decanted. After the residual liquid was removed using filter paper, the light yellow solid was dried in an oven at 60 ° C overnight under a dry air purge.
    Another batch of material was prepared by repeating the above preparation except that after the light yellow solid was collected, it was washed with deionized water (twice 500 μΐ each) before being dried in an oven at 60 ° C during night under a dry air purge.
    2.1 μΐ of an aqueous solution of Pt (NO 3 ) 2 (containing 7.7% by weight of platinum) was added to the above solids and the mixtures were stirred to impregnate the supports containing gold. The samples were dried in an oven at 60 ° C overnight under a dry air purge. The samples were then reduced to 350 ° C under a gas-forming atmosphere (H 2 at 5% and N 2 at 95%) for 3 hours at a temperature ramp rate of 2 ° C / min. The final catalysts contained approximately 2.0% by weight of gold and 2.0% by weight of platinum.
    With the adjustment of the volume and concentration of the
    HAuCU NH4OH, and Pt (NO 3 ) 2 , a series of other catalysts with various fillers of gold (2 or 4% by weight) and platinum (2 or 4% by weight) was prepared using Zirconia Z-1628 (Daiichi Kigenso Kagaku Kogyo), Silica-Titania Cariact (Fuji Silysia) and Silica Cariact Q-10 (Fuji Silysia).
    These catalysts were tested for glucose oxidation using Catalyst test protocol 1 and the results are summarized in Table 2.
    Table 2: Conditions and Results of Glucose Oxidation in the Gold / Platinum Catalysts of Example 2
    Input Amountincatalyst Support Au% p Pt% p Wash after Au deposition Glucose conversion (%) Acid YieldGlucárico (%) 4 7.0 Silica Cariact Q-10 2 2 Not 100 28 5 7.2 Silica Cariact Q-10 2 2 Yes 100 28 7 7.1 Silica Cariact Q-10 4 4 Yes 100 48 8 8.0 Silica Cariact Q-10 4 4 Not 100 44 21 7.1 Titania ST 31119 4 4 Not 100 62 23 7.4 Titania-Silica Cariact 4 4 Yes 100 39 24 7.4 Titania-Silica Cariact 4 4 Not 100 41 29 6.6 Zirconia 1628 2 2 Yes 100 26 30 6.6 Zirconia 1628 2 2 Not 100 22
    Example 3 μΐ of an aqueous solution of HAuCfi (containing 0.2254% by weight of gold) was added to a suspension of 10 mg of titania (P25, Acros Organics) in deionized water (1900 μΐ) with stirring. The suspension (at a concentration of 5 mg support / ml) was stirred at room temperature for 30 min. 400 μΐ of an aqueous solution of urea (20% by weight) was added to the above suspension and the resulting suspension was heated to 80 ° C for 2 hours with stirring. The suspension was then cooled to room temperature, centrifuged and the supernatant was decanted. After the residual liquid was removed using filter paper, the light yellow solid was dried in an oven at 60 ° C overnight under a dry air purge.
    Another batch of material was prepared by repeating the above preparation except that after the light yellow solid was collected, it was washed with deionized water (2 times 2000 μΐ each) before being dried in an oven at 60 ° C during night under a dry air purge.
    2.1 μΐ of an aqueous solution of Pt (NO 3 ) 2 (containing 7.7% by weight of platinum) was added to the above solid and the mixture was stirred to impregnate the support containing gold. The sample was dried in an oven at 60 ° C overnight under a dry air purge. The sample was then reduced to 350 ° C under a gas-forming atmosphere (H 2 at 5% and N 2 at 95%) for 3 hours at a temperature ramp rate of 2 ° C / min. The final catalyst contained approximately 2.0% by weight of gold and 2.0% by weight of platinum.
    The similar method was also used to prepare catalysts based on other supports, including Zirconia Z-1628 (Daiichi Kigenso Kagaku Kogyo), Zirconia Z-1044 (Daiichi Kigenso Kagaku Kogyo), Silica-Titânia Cariact (Fuji Silysia) and Silica Cariact Q-10 (Fuji Silysia).
    These catalysts were tested for glucose oxidation using Catalyst test protocol 1 and the results are summarized in Table 3.
    Table 3: Conditions and results of glucose oxidation in the gold / platinum catalysts of Example 3
    Input Support Wash after Au deposition Suspension Concentration (mg support / ml) Catalyst Quantity (mg) Glucose conversion (%) Glucaric Acid Yield (%) 1 Silica Cariact Q-10 Not 5 9.2 100 23 2 Silica Cariact Q-10 Yes 5 7.0 100 17 3 Silica-Titania Not 5 8.8 100 30 4 Silica-Titania Yes 5 8.4 100 34 5 Titania P25 Not 5 7.4 100 35 6 Titania P25 Yes 5 7.0 100 37 7 Zirconia 1628 Not 5 7.4 80 11 8 Zirconia 1628 Yes 5 7.7 100 22 9 Zirconia Z-1044 Not 5 7.8 100 22 10 Zirconia Z-1044 Yes 5 7.2 100 26
    Example 4 μΐ of an aqueous solution of HAuC1 4 (containing 22.54% by weight of gold) was added to a suspension of 187 mg Cariact Q-10 Silica (Fuji Silysia) in deionized water (38 ml) with stirring. The suspension was stirred at room temperature for 30 min. 100 μΐ of an aqueous solution of NEfiOH (15.85 M) was added to the above suspension and the resulting suspension was stirred at room temperature for 2 hours. The suspension was then centrifuged and the supernatant was decanted. The light yellow solid was washed with deionized water (twice 35 ml each) at 50 ° C, before being dried in an oven at 60 ° C overnight under a dry air purge. The sample was then reduced to 200 ° C under a gas-forming atmosphere (H 2 at 5% and N 2 at 95%) for 3 hours at a temperature ramp rate of 2 ° C / min.
    mg of dry material from the above preparation were used for the next synthesis.
    12.8 μΐ of an aqueous solution of Pt (O3) 2 (containing 1.5% by weight of platinum) was added to the above solid (10 mg) and the mixture was stirred to impregnate the support containing gold. The sample was dried in an oven at 60 ° C overnight under a dry air purge. The sample was then reduced to 350 ° C under a gas-forming atmosphere (H 2 at 5% and N 2 at 95%) for 3 hours at a temperature ramp rate of 2 ° C / min. The final catalyst contained approximately 2.0% by weight of gold and 2.0% by weight of platinum.
    The catalyst was tested for glucose oxidation using Catalyst test protocol 1 and the results are summarized in Table 4.
    Table 4: Conditions and results of glucose oxidation in the gold / platinum catalysts of Example 4
    Input Support Catalyst Quantity(mg) Glucose Conversion (%) Glucaric Acid Yield (%) 1 Silica Cariat Q-10 8.3 100 48
    Example 5 μΐ of an aqueous solution of HAUCI4 (containing 22.54% by weight of gold) was added to a suspension of 187 mg Cariact Q-10 Silica (Fuji Silysia) in deionized water (38 ml) with stirring. The suspension was stirred at room temperature for 30 min. 100 μΐ of an aqueous NH4OH solution (15.85 M) was added to the above suspension and the resulting suspension was stirred at room temperature for 2 hours. The suspension was then centrifuged and the supernatant was decanted. The light yellow solid was washed with deionized water (twice 35 ml each) at 50 ° C, before being dried in an oven at 60 ° C overnight under a dry air purge. The sample was then reduced to 200 ° C under a gas-forming atmosphere (H 2 at 5% and N 2 at 95%) for 3 hours at a temperature ramp rate of 2 ° C / min.
    mg of dry material from the above preparation were used for the next synthesis.
    12.8 μΐ of an aqueous solution of Pt (NO 3 ) 2 (containing 1.5% by weight of platinum) was added to the above solid (10 mg) and the mixture was stirred to impregnate the support containing gold. The sample was dried in an oven at 60 ° C overnight under a dry air purge. The sample was calcined at 350 ° C in air for 3 hours, with a temperature ramp rate of 5 ° C / min, then reduced to 350 ° C under an atmosphere of gas in formation (H 2 at 5% and N 2 95%) for 3 hours at a temperature ramp rate of 2 ° C / min. The final catalyst contained approximately 2.0% by weight of gold and 2.0% by weight of platinum.
    The catalyst was tested for glucose oxidation using Catalyst test protocol 1 and the results are summarized in Table 5
    Table 5: Conditions and results of glucose oxidation in the gold / platinum catalysts of Example 5
    Input Support Catalyst Quantity (mg) Glucose Conversion (%) Glucaric Acid Yield (%) 1 Silica CariatQ-10 8.7 100 43
    Example 6 μΐ of an aqueous solution of HAuCl 4 (containing 22.54% by weight of gold) was added to a suspension of 187 mg Cariact Q-10 Silica (Fuji Silysia) in deionized water (38 ml) with stirring. The suspension was stirred at room temperature for 30 min. 100 μΐ of an aqueous NH4OH solution (15.85 M) was added to the above suspension and the resulting suspension was stirred at room temperature for 2 hours. The suspension was then centrifuged and the supernatant was decanted. The light yellow solid was washed with deionized water (twice 35 ml each) at
    50 ° C, before being dried in an oven at 60 ° C overnight under a dry air purge. The sample was then calcined at 350 ° C in the air for 3 hours, with a temperature ramp rate of 5 ° C / min.
    mg of dry material from the above preparation were used for the next synthesis.
    12.8 μΐ of an aqueous solution of Pt (NO 3 ) 2 (containing 1.5% by weight of platinum) was added to the above solid (10 mg) and the mixture was stirred to impregnate the support containing gold. The sample was dried in an oven at 60 ° C overnight under a dry air purge. The sample was then reduced to 350 ° C under a forming gas atmosphere (H 2 at 5% and N 2 at
    95%) for 3 hours with a temperature ramp rate of 2 ° C / min. The final catalyst contained approximately 2.0% by weight of gold and 2.0% by weight of platinum.
    The catalyst was tested for glucose oxidation using Catalyst test protocol 1 and the results are summarized in
    Table 6.
    Table 6: Conditions and results of glucose oxidation in the gold / platinum catalysts of Example 6
    Input Support Catalyst Quantity (mg) Glucose Conversion (%) Glucaric Acid Yield (%) 1 Silica CariatQ-10 8.4 100 42
    Example 7
    625 μΐ of an aqueous solution of HAuCU (containing 22.54% by weight of gold) was added to a suspension of 5.0 g of titania (P25, Acros Organics) in deionized water (500 ml) with stirring. The suspension was stirred at room temperature for 30 min. 30 ml of an aqueous urea solution (20% by weight) was added to the above suspension and the resulting suspension was heated to 80 ° C overnight, with stirring. The suspension was then cooled to room temperature, centrifuged and the supernatant was decanted. The light yellow solid was washed with deionized water (3 times of 400 ml each) at 50 ° C, before being dried in an oven at 60 ° C overnight under a dry air purge. The sample was then reduced to 200 ° C under a gas-forming atmosphere (H 2 at 5% and N 2 at 95%) for 3 hours at a temperature ramp rate of 2 ° C / min to produce 4.90 g of a purple solid.
    1,225 ml of an aqueous solution of Pt (NO 3 ) 2 (containing 11.4 wt% platinum) was added to the above purple solid in 4 portions. After each addition, the mixture was stirred to impregnate the support containing gold. The sample was dried in an oven at 60 ° C overnight under a dry air purge. The sample was then reduced to 350 ° C under a gas-forming atmosphere (H 2 at 5% and N 2 at 95%) for 3 hours at a temperature ramp rate of 2 ° C / min. The final catalyst contained approximately 4.0 wt% gold and 4.0 wt% platinum.
    The catalyst was tested for glucose oxidation using Catalyst test protocol 2 and the results are summarized in Table 7.
    Table 7: Conditions and results of glucose oxidation in the gold / platinum catalyst of Example 7
    Input Temperature (° C) Reaction Time (h) Glucose conversion (%) Glucaric Acid Yield (%) 1 91 3.0 100 42 2 91 5.0 100 50 3 98 3.0 100 49 4 98 5.0 100 59 5 105 3.0 100 59 6 105 5.0 100 67 7 112 3.0 100 67 8 112 5.0 100 70 9 119 2.0 100 66 10 133 1.0 100 65
    Example 8
    The method similar to that of Example 7 was used to prepare titania-based catalysts (ST 31119, Saint-Gobain Norpro).
    This catalyst was tested for glucose oxidation using the Catalyst test protocol 2 and the results are summarized in Table 8.
    Table 8: Conditions and results of glucose oxidation in the gold / platinum catalyst of Example 8
    Input Temperature (° C) Reaction Time (h) Glucose conversion (%) Glucaric Acid Yield (%) 1 91 5.0 100 51 2 98 3.0 100 52 3 98 5.0 100 59 4 105 3.0 100 58 5 112 3.0 100 68 6 119 2.0 100 69 7 119 3.0 100 71 8 126 2.0 100 70
    Example 9
    312 μΐ of an aqueous solution of HAuC1 4 (containing 22.54% by weight of gold) was added to a suspension of 5.0 g of titania (P25, Acros Organics) in deionized water (500 ml) with stirring. The suspension was stirred at room temperature for 30 min. 15 ml of an aqueous urea solution (20% by weight) was added to the above suspension and the resulting suspension was heated to 80 ° C overnight, with stirring. The suspension was then cooled to room temperature, centrifuged and the supernatant was decanted. The light yellow solid was washed with deionized water (3 times of 400 ml each) at 50 ° C, before being dried in an oven at 60 ° C overnight under a dry air purge. The sample was then reduced to 200 ° C under a gas-forming atmosphere (H 2 at 5% and N 2 at 95%) for 3 hours at a temperature ramp rate of 2 ° C / min to produce 4.90 g of a purple solid.
    612 μΐ of an aqueous solution of Pt (NO 3 ) 2 (containing 11.4 wt% platinum) was added to the above purple solid in 4 portions. After each addition, the mixture was stirred to impregnate the support containing gold. The sample was dried in an oven at 60 ° C overnight under a dry air purge. The sample was then reduced to 350 ° C under a gas-forming atmosphere (H 2 at 5% and N 2 at 95%) for 3 hours at a temperature ramp rate of 2 ° C / min. The final catalyst contained approximately 2.0% by weight of gold and 2.0% by weight of platinum.
    This catalyst was tested for glucose oxidation using Catalyst test protocol 2 and the results are summarized in Table 9.
    Table 9: Conditions and results of glucose oxidation in the gold / platinum catalyst of Example 9
    Input Temperature(° C) Reaction time (h) Glucose substrate% p Glucose conversion (%) Glucaric Acid Yield (%) 1 90 5.0 10 100 32 2 90 3.0 10 100 26 3 90 5.0 20 100 21
    Example 10 μΐ of an aqueous solution of HAuC1 4 (containing 0.2254% by weight of gold) was added to a 10 mg suspension of titania (ST 31119, Saint-Gobain Norpro) in deionized water (450 μΐ), with stirring . The suspension was stirred at room temperature for 30 min. 250 μΐ of an aqueous NHjOH solution (4.0 M) was added to the above suspension and the resulting suspension was stirred at room temperature for 2 hours. The suspension was then centrifuged and the supernatant was decanted. After the residual liquid was removed using filter paper, the light yellow solid was dried in an oven at 60 ° C overnight under a dry air purge.
    2.1 μΐ of an aqueous solution of (NH 3 ) 4Pt (NO 3 ) 2 (containing 7.7% by weight of platinum) was added to the above solid and the mixture was stirred to impregnate the support containing gold. The sample was dried in an oven at 60 ° C overnight under a dry air purge. The sample was then reduced to 350 ° C under a gas-forming atmosphere (H 2 at 5% and N 2 at 95%) for 3 hours at a temperature ramp rate of 2 ° C / min. The final catalyst contained approximately 2.0% by weight of gold and 2.0% by weight of platinum.
    With the adjustment of the volume and concentration of the HAuC1 4 , NH4OH, and (NH 3 ) 4 Pt (NO 3 ) 2 solutions , a series of other catalysts with various fillers of gold (0 to 2% by weight) and platinum ( 0 to 2% by weight) was prepared. A similar method was also used to prepare catalysts based on Z-1044 Zirconia (Daiichi Kigenso Kagaku Kogyo). These catalysts were tested for glucose oxidation using Catalyst test protocol 1 and the results are summarized in Table 10.
    Table 10: Conditions and results of glucose oxidation in the gold / platinum catalyst of Example 10
    Input Catalyst quantity (mg) Support Au% p Pt% p Glucose conversion (%) Glucaric Acid Yield (%) 1 8.8 Titania ST 31119 1.4 2.6 100 28 2 8.6 Titania ST31119 2.0 2.0 100 30 3 9 Zirconia Z-1044 1.4 2.6 100 35 4 8.6 Zirconia Z-1044 2.0 2.0 100 17
    Example 11
    2.1 μΐ of an aqueous solution of Pt (NO 3 ) 2 (containing 7.7% by weight of platinum) was added to 10 mg of titania (ST 31119, SaintGobain Norpro) and the mixture was stirred to impregnate the support. The sample was dried in an oven at 60 ° C overnight under a dry air purge. The sample was then reduced to 350 ° C under a gas-forming atmosphere (H 2 at 5% and N 2 at 95%) for 3 hours at a temperature ramp rate of 2 ° C / min.
    μΐ of an aqueous solution of HAuC1 4 (containing 0.2254% by weight of gold) was added to a suspension of the above solid in deionized water (550 μΐ), with stirring. The suspension was stirred at room temperature for 30 min. 250 μΐ of an aqueous NH4OH solution (4.0 M) was added to the above suspension and the resulting suspension was stirred at room temperature for 2 hours. The suspension was then centrifuged and the supernatant was decanted. After the residual liquid was removed using filter paper, the solid was collected and dried in an oven at 60 ° C overnight under a dry air purge. The sample was then reduced to 350 ° C under a gas-forming atmosphere (H 2 at 5% and N 2 at 95%) for 3 hours at a temperature ramp rate of 2 ° C / min. The final catalyst contained approximately 2.0% by weight of gold and 2.0% by weight of platinum.
    By adjusting the volume and concentration of the HAuC1 4 , NH4OH, and Pt (NO 3 ) 2 solutions, a series of other catalysts with various fillers of gold (0.4 to 2% by weight) and platinum (1, 0 to 3.2% by weight) was prepared. A similar method was also used to prepare catalysts based on Z-1044 Zirconia (Daiichi Kigenso Kagaku Kogyo). These catalysts were tested for glucose oxidation using Catalyst test protocol 1 and the results are summarized in Table
    11.
    Table 11: Conditions and results of glucose oxidation in the gold / platinum catalyst of Example 11
    Input Catalyst quantity (mg) Support Au% p Pt% p Glucose conversion (%) Glucaric Acid Yield (%) 1 8.2 Titania ST 31119 0.4 1.6 72 15 2 8.7 Titania ST 31119 0.7 1.3 100 25 3 8.2 Titania ST 31119 0.8 3.2 93 30 4 7.9 Titania ST 31119 1.0 1.0 100 21 5 8.9 Titania ST 31119 1.4 2.6 100 43 6 8.8 Titania ST 31119 2.0 2.0 100 43 7 7.9 Zirconia Z-1044 0.4 1.6 72 11 8 7.9 Zirconia Z-1044 0.7 1.3 100 27 9 8.4 Zirconia Z-1044 0.8 3.2 97 33 10 7.3 Zirconia Z-1044 1.0 1.0 100 27 11 8 Zirconia Z-1044 1.4 2.6 100 47 12 8.3 Zirconia Z-1044 2.0 2.0 100 42
    Example 12
    2.1 μΐ of an aqueous solution of Pt (NO 3 ) 2 (containing 7.7% by weight of platinum) was added to 10 mg of titania (ST 31119, SaintGobain Norpro) and the mixture was stirred to impregnate the support. The sample was dried in an oven at 60 ° C overnight under a dry air purge. The sample was then calcined at 500 ° C in air for 3 hours, with a temperature ramp rate of 5 ° C / min.
    88 μΐ of an aqueous solution of HAuCl 4 (containing 0.2254 wt.% Gold) was added to a suspension of the above solid in deionized water (550 μΐ), with stirring. The suspension was stirred at room temperature for 30 min. 250 μΐ of an aqueous solution of
    NHtOH (4.0 M) was added to the above suspension and the resulting suspension was stirred at room temperature for 2 hours. The suspension was then centrifuged and the supernatant was decanted. After the residual liquid was removed using filter paper, the solid was dried and an oven at 60 ° C overnight under a dry air purge. The sample was then reduced to 350 ° C under a gas-forming atmosphere (H 2 at 5% and N 2 at 95%) for 3 hours at a temperature ramp rate of 2 ° C / min. The final catalyst contained approximately 2.0% by weight of gold and 2.0% by weight of platinum.
    By adjusting the volume and concentration of the HAuCfi, NH4OH, and Pt (NO 3 ) 2 solutions , a series of other catalysts with various fillers of gold (0 to 2% by weight) and platinum (0 to 2% in weight) was prepared. A similar method was also used to prepare catalysts based on Z-1044 Zirconia (Daiichi Kigenso Kagaku Kogyo). These catalysts were tested for glucose oxidation using Catalyst test protocol 1 and the results are summarized in Table 12.
    Table 12: Conditions and results of glucose oxidation in the gold / platinum catalyst of Example 12
    Input Catalyst Quantity (mg) Support Au% p Pt% p Glucose conversion (%) Glucaric Acid Yield (%) 1 7.9 Titania ST 31119 0.4 1.6 85 17 2 8.1 Titania ST 31119 0.7 1.3 100 28 3 7.9 Titania ST 31119 0.8 3.2 100 44 4 8.2 Titania ST 31119 1.0 1.0 100 21 5 7.7 Titania ST 31119 1.4 2.6 100 49 6 8.2 Titania ST 31119 2.0 2.0 100 43 7 7.8 Zirconia Z-1044 0.4 1.6 99 23 8 8.2 Zirconia Z-1044 0.7 1.3 100 30 9 7.7 Zirconia Z-1044 0.8 3.2 100 46 10 7.9 Zirconia Z-1044 1.0 1.0 100 27 11 9.2 Zirconia Z-1044 1.4 2.6 100 51 12 8.5 Zirconia Z-1044 2.0 2.0 100 40
    Example 13
    Preparation of platinum / gold catalyst from Au / TiO2 [Sud Chemie 02-10]
    Pt (NO 3 ) 2 solution was added to a 1.5% dry sample of commercial gold / titania catalyst [Süd Chemie 02-10] (where the total volume of the Pt (NO 3 ) 2 volume was combined to equal the pore volume of the catalyst), with stirring, after which the material was dried in an oven at 120 ° C for 1 hour, followed by reduction under flow of 5% by volume of H 2 in N 2 at 350 ° C for 3 hours. The results are presented as an entry in Table 13.
    Preparation of 4% by weight platinum / gold catalyst
    4% by weight
    The Pt (NO3) 2 solution and the AuC1 2 solution were added to a dry sample of Titânia Norpro ST 61120 (Saint Gobain Norpro) with stirring, after which the material was dried in an oven at 120 ° C for 16 hours . A solution of Pt (NO3) 2 was subsequently added to the dry sample of Au / Titânia NorPro ST 61120 with stirring, after which the material was dried in an oven at 120 ° C for 16 hours followed by a reduction at 350 ° C under a current of 5% by volume of H 2 in N 2 for 3 hours. The results are presented as Entry 2 of Table 13.
    Table 13
    Input Support PrecursorMl PrecursorM2 Temp(° C) Time(H) AmountinCatalyst(mg) YieldinAcidglecárico(%) 1 1.5% Pt 1.5% Au / Titania [Süd Chemie 02-10] - Pt (NO 3 ) 2 100 5 8 55 2 4% Pt 4% Au / Titânia NorPro ST 61120 HAuC1 2100 5 8 32
    权利要求:
    Claims (17)
    [1]
    1. Catalyst composition, characterized by the fact that it comprises particles of gold-platinum alloy and particles of platinum (0) on a support, where (a) the molar ratio of platinum to gold on the support is
    5 from 4: 1 to 1: 1, and (b) the particle sizes of the platinum particles (0) are substantially in the range of 5 to 30 nanometers, and (c) the goldplatin alloy is formed at a temperature between 200 ° C and 350 ° C.
    [2]
    2. Catalyst composition according to claim 1, characterized by the fact that the support is selected from the group consisting of
    10 in titania, zirconia, silica, zeolite, carbon and montmorillonite.
    [3]
    3. Catalyst composition according to claim 1 or 2, characterized by the fact that it still comprises a metal selected from the group 6 metals.
    [4]
    Catalyst composition according to any one of the claims 1 to 3, characterized by the fact that the sizes of the gold particles are substantially in the range of 2 to 20 nanometers.
    [5]
    Catalyst composition according to any one of claims 1 to 4, characterized by the fact that at least 50% of the platinum particles have a size in the range of 8 to 12 nanometers.
    20
    [6]
    Catalyst composition according to any one of claims 1 to 5, characterized in that at least 50% of the gold particles have a size in the range of 5 to 12 nanometers.
    [7]
    Catalyst composition according to any one of claims 1 to 6, characterized in that the support is selected from the
    25 group consisting of titania, zirconia and silica.
    [8]
    Catalyst composition according to any one of claims 1 to 7, characterized in that the support comprises titania.
    [9]
    9. Catalyst composition according to any of the
    Petition 870180051560, of 6/15/2018, p. 13/20 claims 1 to 8, characterized by the fact that the catalyst has the ability to catalyze the conversion of glucose into glucaric acid with a yield greater than 60%.
    [10]
    Catalyst composition according to any one of claims 1 to 9, characterized in that the molar ratio of platinum to gold is in the range of 3: 1 to 1: 1.
    [11]
    Catalyst composition according to any one of claims 1 to 10, characterized in that the molar ratio of platinum to gold is in the range of 2: 1 to 1: 1.
    10
    [12]
    Catalyst composition according to any one of claims 1 to 11, characterized in that the total metal charge of the catalyst is 10% by weight or less.
    [13]
    Catalyst composition according to any one of claims 1 to 12, characterized in that the total metal charge
    15 of the catalyst is 1 to 8% by weight.
    [14]
    Catalyst composition according to any one of claims 1 to 13, characterized in that the total metal charge of the catalyst is 2 to 4% by weight.
    [15]
    15. Process for the preparation of glucaric acid or lactones 20 thereof, characterized in that it comprises reacting glucose with an oxygen source in the presence of a catalyst composition as defined in any one of claims 1 to 14, and in the substantial absence base added
    [16]
    Catalyst composition according to any one of claims 1 to 14, characterized by the fact that it still comprises a metal selected from the metals in Group 10.
    [17]
    Catalyst composition according to any one of claims 1 to 14, characterized in that the support comprises zirconia.
    Petition 870180051560, of 6/15/2018, p. 14/20
    1/2
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    同族专利:
    公开号 | 公开日
    CN102971074A|2013-03-13|
    JP2013533798A|2013-08-29|
    WO2011155964A1|2011-12-15|
    US20170158593A1|2017-06-08|
    SG186205A1|2013-01-30|
    JP5882309B2|2016-03-09|
    US20160075676A1|2016-03-17|
    US20140256982A1|2014-09-11|
    CN102971074B|2019-01-04|
    US9156766B2|2015-10-13|
    US20100317823A1|2010-12-16|
    AU2010355259B2|2016-05-26|
    BR112012031494A2|2016-11-01|
    US9434709B2|2016-09-06|
    AU2010355259A1|2013-01-10|
    EP2579981A1|2013-04-17|
    US8669397B2|2014-03-11|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB600871A|1945-10-17|1948-04-21|Walter Norman Haworth|Improvements relating to the manufacture of 5-hydroxymethyl 2-furfural|
    GB591858A|1944-05-30|1947-09-01|Walter Norman Haworth|Improvements relating to the manufacture of 5-hydroxy-methyl furfural or levulinic acid|
    US2472168A|1948-10-12|1949-06-07|Charles L Mehltretter|Process for the preparation of d-glucosaccharic acid|
    US2750394A|1952-05-22|1956-06-12|Food Chemical And Res Lab Inc|Manufacture of 5-hydroxymethyl 2-furfural|
    US2851468A|1953-06-10|1958-09-09|Dendrol Inc|Preparation of hydroxymethylfurfural from cellulosic materials|
    US2929823A|1956-11-26|1960-03-22|Merck & Co Inc|Production of 5-hydroxymethylfurfural|
    US2917520A|1957-09-11|1959-12-15|Arthur C Cope|Production and recovery of furans|
    US3083236A|1958-09-10|1963-03-26|Merck & Co Inc|Hydrogenation of 5-hydroxy-methyl furfural|
    US3070633A|1958-09-10|1962-12-25|Merck & Co Inc|Process for producing 1, 6-hexanediol|
    GB876463A|1959-02-25|1961-09-06|Atlas Powder Co|Process for preparing hydroxymethyl furfural|
    US3118912A|1960-04-18|1964-01-21|Rayonier Inc|Preparation of hydroxymethylfurfural|
    US3189651A|1962-01-16|1965-06-15|Merck & Co Inc|Process for preparing hexamethylenediamine compounds from 5-aminomethyl-2-furfurylamine compounds|
    US3225066A|1963-04-18|1965-12-21|Atlas Chem Ind|Process for the preparation of tetrahydrofuran-cis, 2,5-dicarboxylic acid and salts thereof|
    US3326944A|1964-03-09|1967-06-20|Atlas Chem Ind|Method of producing dehydromucic acid|
    GB1044883A|1964-03-12|1966-10-05|British Petroleum Co|Alkaryl esters of aliphatic dicarboxylic acids|
    GB1208101A|1966-10-13|1970-10-07|Johnson Matthey Co Ltd|Improvements in and relating to the catalytic oxidation of glucose|
    US3483228A|1966-10-18|1969-12-09|Merck & Co Inc|Method for producing 5-hydroxymethyl furfural|
    US3860626A|1967-07-26|1975-01-14|Inst Neorganicheskoi Khim|Methods for the preparation of borotrihydroxyglutarate|
    US4060547A|1968-08-15|1977-11-29|Monsanto Company|Production of dicarboxylic acids|
    DE1916601C3|1969-04-01|1975-01-09|Basf Ag, 6700 Ludwigshafen|Process for the production of adipic acid dinitrile|
    CH569790A5|1970-12-14|1975-11-28|Procter & Gamble|
    DE2233977A1|1971-07-14|1973-02-01|Unilever Nv|PROCESS FOR PREPARING OXYDED CARBOHYDRATES|
    US3761579A|1971-09-01|1973-09-25|Monsanto Co|Hydrogen iodide|
    JPS5513243Y2|1973-06-25|1980-03-25|
    US3917707A|1974-07-31|1975-11-04|Du Pont|Suppression of 1,2-diaminocyclohexane formation during production of hexamethylenediamine|
    US4363815A|1975-07-23|1982-12-14|Yu Ruey J|Alpha hydroxyacids, alpha ketoacids and their use in treating skin conditions|
    US4078139A|1975-07-31|1978-03-07|Schering Corporation|Process for deoxygenating secondary alcohols|
    US4067900A|1975-08-25|1978-01-10|Monsanto Company|Hydrogenolysis of alcohols, ketones, aldehydes, esters and ethers|
    JPS53144506U|1977-04-20|1978-11-14|
    FR2464260B1|1979-09-05|1983-01-21|Roquette Freres|
    US4302432A|1980-11-21|1981-11-24|Eastman Kodak Company|Preparation of hydrogen iodide, lithium iodide and methyl iodide|
    US4337202A|1981-04-16|1982-06-29|Boise Cascade Corporation|Process of making L-gulono gamma lactone|
    US4401823A|1981-05-18|1983-08-30|Uop Inc.|Hydrogenolysis of polyhydroxylated compounds|
    US4400468A|1981-10-05|1983-08-23|Hydrocarbon Research Inc.|Process for producing adipic acid from biomass|
    FR2528842B1|1982-06-16|1985-09-06|Agrifurane Sa|IMPROVED DECARBONYLATION PROCESS FOR FURFURAL IN ORDER TO OBTAIN FURANNE AND DECARBONYLATION CATALYST FOR ITS IMPLEMENTATION|
    US4439551A|1983-03-18|1984-03-27|Texaco, Inc.|Packaging foam polyurethane composition employing novel polyol blend|
    JPH0130637Y2|1983-06-03|1989-09-19|
    FR2551754B1|1983-09-14|1988-04-08|Roquette Freres|PROCESS FOR THE MANUFACTURE OF 5-HYDROXYMETHYLFURFURAL|
    JPH0419985B2|1983-10-24|1992-03-31|Kawaken Fuainkemikaru Kk|
    FR2556344A1|1983-12-12|1985-06-14|British Petroleum Co|Process for production of furfural and 5-furfural and corresponding hydrogenated derivatives|
    US4533743A|1983-12-16|1985-08-06|Atlantic Richfield Company|Furfural process|
    DK165008C|1984-01-23|1993-02-22|Akzo Nv|PROCEDURE FOR THE PREPARATION OF 2-KETOALDONIC ACIDS|
    US4605790A|1985-05-21|1986-08-12|E. I. Du Pont De Nemours And Company|Phenol from coal and biomass|
    US4722997A|1985-05-31|1988-02-02|Stamicarbon, B.V.|Process for the preparation of nylon 4,6|
    JPH0532477B2|1985-10-03|1993-05-17|Yamasa Shoyu Kk|
    DE3601281C2|1986-01-17|1988-08-04|Sueddeutsche Zucker Ag, 6800 Mannheim, De|
    FR2597474B1|1986-01-30|1988-09-23|Roquette Freres|PROCESS FOR THE OXIDATION OF ALDOSES, CATALYST IMPLEMENTED AND PRODUCTS THUS OBTAINED.|
    DE3643011A1|1986-12-17|1988-06-30|Basf Ag|METHOD FOR PRODUCING CAPROLACTAM FROM 6-AMINOCAPRONIC ACID, THEIR ESTERS AND AMIDES|
    US5149680A|1987-03-31|1992-09-22|The British Petroleum Company P.L.C.|Platinum group metal alloy catalysts for hydrogenation of carboxylic acids and their anhydrides to alcohols and/or esters|
    AT387247B|1987-05-12|1988-12-27|Voest Alpine Ind Anlagen|COMBINED PROCESS FOR THE THERMAL AND CHEMICAL TREATMENT OF BIOMASS CONTAINING LIGNOCELLULOSE AND FOR THE EXTRACTION OF FURFURAL|
    US4820880A|1987-05-18|1989-04-11|Michigan Biotechnology Institute|Process for the production of 3,4-dideoxyhexitol|
    DE3842825C2|1988-01-08|1991-01-24|Fried. Krupp Gmbh, 4300 Essen, De|
    US4833230A|1988-06-21|1989-05-23|Research Corporation Technologies, Inc.|Polyhydroxypolyamides and process for making same|
    DE3823301C1|1988-07-09|1989-11-02|Degussa Ag, 6000 Frankfurt, De|
    DE3826073A1|1988-07-30|1990-02-01|Hoechst Ag|METHOD FOR THE OXIDATION OF 5-HYDROXYMETHYLFURFURAL|
    US5359137A|1989-04-26|1994-10-25|E. I. Du Pont De Nemours And Company|Preparation of adipic acid from lactones|
    US5247012A|1989-12-08|1993-09-21|The Geon Company|Glutaric acid based polyester internally plasticized PVC|
    US5071754A|1990-01-23|1991-12-10|Battelle Memorial Institute|Production of esters of lactic acid, esters of acrylic acid, lactic acid, and acrylic acid|
    US5252473A|1990-01-23|1993-10-12|Battelle Memorial Institute|Production of esters of lactic acid, esters of acrylic acid, lactic acid, and acrylic acid|
    FR2664273B1|1990-06-27|1994-04-29|Beghin Say Sa|NEW PROCESS FOR THE PREPARATION OF 5-HYDROXYMETHYLFURFURAL FROM SACCHARIDES.|
    FR2663933B1|1990-06-27|1994-06-17|Beghin Say Sa|NEW PROCESS FOR THE PREPARATION OF 5-HYDROXYMETHYLFURFURAL FROM SACCHARIDES.|
    FR2669635B1|1990-11-22|1994-06-10|Furchim|PROCESS FOR THE MANUFACTURE OF HIGH PURITY HYDROXYMETHYLFURFURAL .|
    FR2670209B1|1990-12-07|1995-04-28|Commissariat Energie Atomique|PROCESS FOR THE PREPARATION OF FURFURAL HYDROXYMETHYL-5 BY HETEROGENEOUS CATALYSIS.|
    DE4106937A1|1991-03-05|1992-09-10|Bayer Ag|METHOD FOR RECOVERY OF ADIPINIC ACID|
    US5132456A|1991-05-07|1992-07-21|The Regents Of The University Of California|Sorption of carboxylic acid from carboxylic salt solutions at PHS close to or above the pKa of the acid, with regeneration with an aqueous solution of ammonia or low-molecular-weight alkylamine|
    US5276240A|1991-10-18|1994-01-04|Board Of Regents, The University Of Texas System|Catalytic hydrodehalogenation of polyhalogenated hydrocarbons|
    EP0548399B1|1991-12-23|1996-09-25|Cerestar Holding B.V.|Process for the production of oxyacids from carbohydrates|
    US5196617A|1992-01-14|1993-03-23|Engelhard Corporation|Method of hydrodehalogenating halogenated organic compounds in aqueous environmental sources|
    US5434233A|1992-08-12|1995-07-18|Kiely; Donald E.|Polyaldaramide polymers useful for films and adhesives|
    US5430214A|1992-10-01|1995-07-04|The Dow Chemical Company|Hydrodehalogenation process and catalyst for use therein|
    US5281647A|1992-11-10|1994-01-25|Miles Inc.|Polymeric plasticizers and a process for preparing the same|
    NL9300540A|1993-03-25|1994-10-17|Inst Voor Agrotech Onderzoek|Method for oxidizing carbohydrates.|
    US5597714A|1993-03-26|1997-01-28|Arkenol, Inc.|Strong acid hydrolysis of cellulosic and hemicellulosic materials|
    US5562777A|1993-03-26|1996-10-08|Arkenol, Inc.|Method of producing sugars using strong acid hydrolysis of cellulosic and hemicellulosic materials|
    US5426219A|1993-07-26|1995-06-20|A.E. Staley Manufacturing Co.|Process for recovering organic acids|
    DE69426907T2|1993-08-11|2001-09-27|Mitsubishi Gas Chemical Co|Titanosilicate catalyst particles|
    US5487987A|1993-09-16|1996-01-30|Purdue Research Foundation|Synthesis of adipic acid from biomass-derived carbon sources|
    US5426252A|1993-10-15|1995-06-20|Akzo Nobel Nv|Catalytic hydrodechlorination of a chloromethane|
    LV10857B|1993-12-28|1996-08-20|Univ Rigas Tehniska|Method for producing of glucaric acid |
    US5625110A|1994-07-26|1997-04-29|Leuna-Katalysatoren Gmbh|Hydrodehalogenation catalyst|
    US5811628A|1994-07-26|1998-09-22|Leuna-Katalysatoren Gmbh|Method for the complete hydrodechlorination of chlorinated hydrocarbons|
    US5516960A|1994-08-02|1996-05-14|Board Of Regents, The University Of Texas System|Process for producing hydrocarbon fuels|
    US5599977A|1995-06-02|1997-02-04|Kiely; Donald E.|Oxidation process|
    FR2736636B1|1995-07-11|1997-09-19|Roquette Freres|PROCESS FOR THE MANUFACTURE OF XYLARIC ACID AND USES THEREOF|
    DE19535395C1|1995-09-23|1997-03-06|Degussa|Process for the hydrogenolysis of C-O and C = O bonds in organic substances|
    FR2740707B1|1995-11-08|1997-12-26|Rhone Poulenc Chimie|PROCESS FOR THE PREPARATION OF A RUTHENIUM / TIN BI-METAL CATALYST|
    DE19542287A1|1995-11-14|1997-05-15|Suedzucker Ag|Process for the preparation of di- and higher-oxidized carboxylic acids of carbohydrates, carbohydrate derivatives or primary alcohols|
    US5919994A|1995-11-29|1999-07-06|E. I. Du Pont De Nemours And Company|Catalytic halogenated hydrocarbon processing and ruthenium catalysts for use therein|
    JP2001519708A|1995-11-29|2001-10-23|イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー|Halogenated hydrocarbon treatment catalysts, their precursors and their production and use|
    US5721189A|1995-12-07|1998-02-24|Akzo Nobel N.V.|Treatment to improve the durability of a hydrodechlorination catalyst and catalyst|
    DE19548289A1|1995-12-22|1997-06-26|Basf Ag|Process for the simultaneous production of caprolactam and hexamethylenediamine|
    ES2156363T3|1996-03-01|2001-06-16|Basf Ag|PROCEDURE FOR OBTAINING 1,6-HEXANODIOL WITH A PURITY GREATER THAN 99%.|
    DE19609069A1|1996-03-08|1997-09-11|Episucres Sa|Catalytic hydrolysis of complex sugar solutions|
    US5766439A|1996-10-10|1998-06-16|A. E. Staley Manufacturing Co.|Production and recovery of organic acids|
    US6028025A|1996-10-21|2000-02-22|Massachusetts Institute Of Technology|Metalloporphyrin oxidation catalyst covalently coupled to an inorganic surface and method making same|
    TW377306B|1996-12-16|1999-12-21|Asahi Chemical Ind|Noble metal support|
    JPH10216518A|1997-02-10|1998-08-18|Toyota Motor Corp|Gold alloy catalyst|
    JP4756719B2|1997-02-17|2011-08-24|ダイセル化学工業株式会社|Oxidation catalyst system, oxidation method and oxide production method|
    US5789333A|1997-03-05|1998-08-04|Iowa State University Research Foundation, Inc.|Catalyst system comprising a first catalyst system tethered to a supported catalyst|
    US5900511A|1997-03-28|1999-05-04|E. I. De Pont De Nemours And Company|Process for continuous hydrogenation of adiponitrile|
    AU7291598A|1997-05-07|1998-11-27|George A. Olah|Nanoscale solid superacid catalysts with pendant fluoroalkylsulfonic acid or fluoro, perfluoroalkylsulfonic acid groups|
    JP3903598B2|1997-09-24|2007-04-11|トヨタ自動車株式会社|Exhaust gas purification catalyst and method for producing the same|
    DE19743621C1|1997-10-02|1999-03-25|Rwe Dea Ag|Oxidation of primary alcohol to aldehyde and acid|
    US5998657A|1998-04-15|1999-12-07|Eastman Chemical Company|Process for the generation of α, β-unsaturated carboxylic acids and esters using niobium catalyst|
    JP2000070718A|1998-06-17|2000-03-07|Nippon Shokubai Co Ltd|Production of benzyl ester|
    US6232264B1|1998-06-18|2001-05-15|Vanderbilt University|Polymetallic precursors and compositions and methods for making supported polymetallic nanocomposites|
    DE19839338A1|1998-08-28|2000-03-02|Basf Ag|Improved process for the simultaneous production of 6-aminocapronitrile and hexamethylenediamine|
    FR2785608B1|1998-11-05|2000-12-29|Rhone Poulenc Fibres|PROCESS FOR HEMIHYDROGENATION OF DINITRILES|
    US6087296A|1998-11-05|2000-07-11|E. I. Du Pont De Nemours & Co.|Raney iron catalyst and a process for hydrogenating organic compounds using said catalyst|
    US6049004A|1998-12-11|2000-04-11|Kiely; Donald E.|Nitric acid removal from oxidation products|
    DE19905655A1|1999-02-11|2000-08-17|Karl Zeitsch|Process for the production of furfural by delayed relaxation|
    US5986127A|1999-03-15|1999-11-16|E. I. Du Pont De Nemours And Company|Aminonitrile production|
    DE19911504B4|1999-03-16|2006-02-23|Südzucker AG Mannheim/Ochsenfurt|Process for the industrial oxidation of alcohols, aldehydes or polyhydroxy compounds|
    US6436866B1|1999-05-26|2002-08-20|Asahi Kasei Kabushiki Kaisha|Lewis acid catalyst composition|
    US6399540B1|1999-08-12|2002-06-04|Sumitomo Chemical Co., Ltd.|Porous titania, catalyst comprising the porous titania|
    JP4555415B2|1999-09-01|2010-09-29|ダイセル化学工業株式会社|Catalyst comprising nitrogen-containing heterocyclic compound, and method for producing organic compound using the catalyst|
    KR100460371B1|1999-09-21|2004-12-08|아사히 가세이 가부시키가이샤|Catalysts for hydrogenation of carboxylic acid|
    US6569670B2|1999-09-30|2003-05-27|Cognis Corporation|Fermentation process|
    US6569802B1|1999-11-30|2003-05-27|E. I. Du Pont De Nemours And Company|Catalyst for selective hydrogenation of dinitriles|
    FR2801901B1|1999-12-07|2003-11-14|Roquette Freres|PROCESS FOR THE TRANSFORMATION OF ORGANIC MATERIALS, PARTICULARLY SACCHARIDES, COMPRISING AN ENZYMATIC OXIDATION STEP IN THE PRESENCE OF RUTHENIUM OR PALLADIUM|
    JP2001316311A|2000-03-03|2001-11-13|Asahi Kasei Corp|Highly pure 1,5-pentanediol|
    US6498269B1|2000-10-17|2002-12-24|The University Of Connecticut|Method for the oxidation of aldehydes, hemiacetals and primary alcohols|
    TWI294308B|2000-11-15|2008-03-11|Daicel Chem|
    BR0115877A|2000-11-20|2003-10-07|Cargill Inc|3-hydroxypropionic acid and other organic compounds|
    US6559275B2|2000-12-01|2003-05-06|Canon Kabushiki Kaisha|Method for producing aliphatic polyester|
    US20020111458A1|2000-12-01|2002-08-15|Masato Minami|Method for producing aliphatic polyester|
    US6692578B2|2001-02-23|2004-02-17|Battelle Memorial Institute|Hydrolysis of biomass material|
    US6518440B2|2001-03-05|2003-02-11|Gene E. Lightner|Hydroxymethylfurfural derived from cellulose contained in lignocellulose solids|
    US6716339B2|2001-03-30|2004-04-06|Corning Incorporated|Hydrotreating process with monolithic catalyst|
    JP2002308819A|2001-04-12|2002-10-23|Canon Inc|Method for producing caproic acid from cellulose and method for recycling cellulose as resources|
    MXPA03009905A|2001-04-30|2004-01-29|Ciba Specilaty Chemicals Holdi|Use of metal complex compounds as oxidation catalysts.|
    US7138035B2|2001-05-08|2006-11-21|National Starch And Chemical Investment Holding Corporation|Process for the selective modification of carbohydrates by peroxidase catalyzed oxidation|
    US6441202B1|2001-08-20|2002-08-27|Gene E. Lightner|Heterocyclic compounds extracted by a hydrocarbon|
    WO2003028884A1|2001-09-28|2003-04-10|Daicel Chemical Industries, Ltd.|Catalysts comprised of n-substituted cyclic imides and processes for preparing organic compounds with the catalysts|
    US6844447B2|2001-12-18|2005-01-18|Metabolix Inc.|Methods of making intermediates from polyhydroxyalkanoates|
    US6773512B2|2001-12-31|2004-08-10|Danisco Sweeteners Oy|Method for the recovery of sugars|
    BR0307300A|2002-02-01|2005-09-06|Cargill Inc|Integration of at least two processes to reuse acid|
    BRPI0309915B1|2002-05-10|2020-06-23|Wisconsin Alumni Research Foundation|METHOD OF PRODUCTION OF HYDROCARBONES FROM OXYGENED HYDROCARBONS|
    FR2843050B1|2002-08-01|2005-04-15|Inst Francais Du Petrole|METAL CATALYST OF GROUP VI AND GROUP VIII AT LEAST IN PART IN THE FORM OF HETEROPOLYANIONS IN THE OXIDE PRECURSOR|
    GB0218010D0|2002-08-05|2002-09-11|Ciba Spec Chem Water Treat Ltd|Production of a fermentation product|
    GB0218012D0|2002-08-05|2002-09-11|Ciba Spec Chem Water Treat Ltd|Production of a fermentation product|
    US6894135B2|2002-12-10|2005-05-17|The University Of Montana|Method for preparing high molecular weight random polyhydroxypolyamides|
    ES2217962B1|2003-02-14|2006-02-16|Universidad Politecnica De Valencia|CRYSTAL POROUS MATERIAL , ITS PREPARATION PROCEDURE AND ITS USE IN THE CATALITICAL CONVERSION OF ORGANIC COMPONENTS.|
    WO2005005033A2|2003-06-30|2005-01-20|New Jersey Institute Of Technology|Catalysts and methods for making same|
    US20070027341A1|2003-07-01|2007-02-01|Michele Rossi|Process and catalyst for the preparation of aldonic acids|
    JP2005060447A|2003-08-19|2005-03-10|Toray Ind Inc|Polyamide resin|
    JP2005154302A|2003-11-21|2005-06-16|Mitsubishi Gas Chem Co Inc|Method for oxidizing glucide|
    WO2005059152A1|2003-12-18|2005-06-30|Cerestar Holding B.V.|Oxidation of carbohydrates by means of peroxidases and nitroxy radicals|
    JP2005200321A|2004-01-14|2005-07-28|Canon Inc|Method for producing 5-hydroxymethylfurfural and furfural|
    ES2357037T3|2004-01-16|2011-04-15|Novozymes, Inc.|METHODS FOR DEGRADING LIGNOCELLULOSIC MATERIALS.|
    JP2005232116A|2004-02-23|2005-09-02|Canon Inc|Method for producing lactic acid, 5-hydroxymethylfurfural and furfural|
    CN100564330C|2004-02-27|2009-12-02|陶氏环球技术公司|From the aqueous stream that contains organic compound, reclaim the method for this organic compound|
    US6958405B2|2004-03-09|2005-10-25|Arco Chemical Technology, L.P.|Polymer-encapsulated titanium zeolites for oxidation reactions|
    US7413882B2|2004-03-25|2008-08-19|Novozymes, Inc.|Methods for degrading or converting plant cell wall polysaccharides|
    WO2005123669A1|2004-06-10|2005-12-29|Board Of Trustees Of Michigan State University|Synthesis of caprolactam from lysine|
    JP2008515769A|2004-06-30|2008-05-15|イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー|Synthesis of aldonolactone, aldarolactone, and aldodilactone using azeotropic distillation|
    CN1993365A|2004-06-30|2007-07-04|纳幕尔杜邦公司|Synthesis of aldonolactones, aldarolactones, and aldarodilactones using azeotrophic distillation|
    US20060084800A1|2004-06-30|2006-04-20|Chenault Henry K|Synthesis of aldonolactones, aldarolactones, and aldarodilactones using azeotropic distillation|
    JP2008511318A|2004-09-01|2008-04-17|アグロテクノロジーアンドフードイノベイションズビー．ブイ．|Fermentation method with improved substrate conversion efficiency|
    US7371894B2|2004-09-02|2008-05-13|Eastman Chemical Company|Optimized liquid-phase oxidation|
    US7393963B2|2004-12-10|2008-07-01|Archer-Daniels-Midland Company|Conversion of 2,5-furaldehyde to industrial derivatives, purification of the derivatives, and industrial uses therefor|
    US7317116B2|2004-12-10|2008-01-08|Archer-Daniels-Midland-Company|Processes for the preparation and purification of hydroxymethylfuraldehyde and derivatives|
    US20060182681A1|2004-12-28|2006-08-17|Fortum Oyj|Catalytic materials and method for the preparation thereof|
    BRPI0609771A2|2005-03-21|2011-10-18|Univ Ben Gurion|process for producing a liquid fuel composition, diesel fuel composition, and, mixed fuel composition|
    US7781191B2|2005-04-12|2010-08-24|E. I. Du Pont De Nemours And Company|Treatment of biomass to obtain a target chemical|
    EP1869197A2|2005-04-12|2007-12-26|E.I. Dupont De Nemours And Company|Treatment of biomass to obtain ethanol|
    US7985566B2|2005-04-22|2011-07-26|Mitsubishi Chemical Corporation|Biomass-resource-derived polyester and production process thereof|
    WO2006119357A2|2005-05-02|2006-11-09|University Of Utah Research Foundation|Processes for catalytic conversion of lignin to liquid bio-fuels|
    US20060264684A1|2005-05-19|2006-11-23|Petri John A|Production of diesel fuel from biorenewable feedstocks|
    EP1937821A4|2005-09-09|2009-11-11|Genomatica Inc|Methods and organisms for the growth-coupled production of succinate|
    US7608689B2|2005-09-30|2009-10-27|Novozymes, Inc.|Methods for enhancing the degradation or conversion of cellulosic material|
    JP2007145736A|2005-11-25|2007-06-14|Canon Inc|Manufacturing method of 5-hydroxymethylfurfural|
    US7459597B2|2005-12-13|2008-12-02|Neste Oil Oyj|Process for the manufacture of hydrocarbons|
    US7678950B2|2005-12-16|2010-03-16|Conocophillips Company|Process for converting carbohydrates to hydrocarbons|
    CN101346302B|2005-12-21|2013-07-10|维仁特公司|Catalysts and methods for reforming oxygenated compounds|
    US7829035B2|2006-01-19|2010-11-09|Massachusetts Institute Of Technology|Oxidation catalyst|
    EP1984514A4|2006-01-27|2010-09-01|Univ Massachusetts|Systems and methods for producing biofuels and related materials|
    KR100723394B1|2006-02-07|2007-05-30|삼성에스디아이 주식회사|Non-pyrophoric catalyst for water-gas shift reaction and method of producing the same|
    US20070215484A1|2006-03-15|2007-09-20|Peterson Otis G|Electrochemical conversion of polyalcohols to hydrocarbons|
    US20070219397A1|2006-03-15|2007-09-20|Battelle Memorial Institute|Method for conversion of beta-hydroxy carbonyl compounds|
    JP4804187B2|2006-03-28|2011-11-02|キヤノン株式会社|Method for producing furan-2,5-dicarboxylic acid|
    MY154790A|2007-03-08|2015-07-31|Virent Inc|Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons|
    EP2061860B1|2007-03-08|2013-12-18|Virent, Inc.|Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons|
    WO2007146636A1|2006-06-06|2007-12-21|Wisconsin Alumni Research Foundation|Catalytic process for producing furan derivatives from carbohydrates in a biphasic reactor|
    ES2895946T3|2006-06-09|2022-02-23|Albemarle Netherlands Bv|Catalytic hydrodeoxygenation of an oxygenated product feedstock|
    US7994347B2|2006-06-09|2011-08-09|Battelle Memorial Institute|Hydroxymethylfurfural reduction methods and methods of producing furandimethanol|
    US7692041B2|2006-08-07|2010-04-06|The University Of Montana|Method of oxidation using nitric acid|
    US7939681B2|2006-08-07|2011-05-10|Battelle Memorial Institute|Methods for conversion of carbohydrates in ionic liquids to value-added chemicals|
    US20090250653A1|2006-08-07|2009-10-08|Kiely Donald E|Hydroxycarboxylic Acids and Salts|
    UA92823C2|2006-08-18|2010-12-10|Айоджен Энерджи Корпорейшн|Process for obtaining salt or organic acid from an aqueous sugar stream|
    CN100537511C|2006-08-30|2009-09-09|中国石油天然气股份有限公司|Method and equipment for continuous esterification production of adipic acid dimethyl ester|
    US20080103340A1|2006-10-27|2008-05-01|Archer-Daniels-Midland Company|Applications of biobased glycol compositions|
    US7700788B2|2006-10-31|2010-04-20|Battelle Memorial Institute|Hydroxymethyl furfural oxidation methods|
    EP2087033B1|2006-10-31|2019-12-11|Bio-tec Environmental, LLC|Chemical additives to make polymeric materials biodegradable|
    US20080223519A1|2006-12-06|2008-09-18|Locko George A|Polyamide polyols and polyurethanes, methods for making and using, and products made therefrom|
    US20080206562A1|2007-01-12|2008-08-28|The Regents Of The University Of California|Methods of generating supported nanocatalysts and compositions thereof|
    WO2008144514A2|2007-05-17|2008-11-27|Massachusetts Institute Of Technology|Polyol-based polymers|
    US20090018300A1|2007-07-11|2009-01-15|Archer-Daniels-Midland Company|Monomers and polymers from bioderived carbon|
    US7947483B2|2007-08-10|2011-05-24|Genomatica, Inc.|Methods and organisms for the growth-coupled production of 1,4-butanediol|
    EP2033958A1|2007-09-07|2009-03-11|Furanix Technologies B.V|Hydroxymethylfurfural ethers from sugars and di- and triols|
    US7385081B1|2007-11-14|2008-06-10|Bp Corporation North America Inc.|Terephthalic acid composition and process for the production thereof|
    JP5775305B2|2007-11-15|2015-09-09|ザ ユニバーシティー オブ モンタナ|Hydroxy polyamide gel former|
    CN106119112B|2008-03-27|2021-07-13|基因组股份公司|Microorganisms for the production of adipic acid and other compounds|
    US8075642B2|2008-04-14|2011-12-13|Wisconsin Alumni Research Foundation|Single-reactor process for producing liquid-phase organic compounds from biomass|
    DE102008037065A1|2008-08-08|2010-02-11|Clariant International Ltd.|Process for the preparation of aryl polyglycolcarboxylic acids by direct oxidation|
    CN101486639B|2009-02-18|2012-01-04|南京林业大学|Novel method for synthesizing mixed glucose derivative|
    CN101695657B|2009-10-27|2012-10-10|北京大学|Method for producing lactic acid by using glycerin and special catalyst for production of lactic acid by using glycerin|ES2371839B1|2010-06-16|2012-11-19|Consejo Superior De Investigaciones Científicas |BIOMASS CONVERSION PROCESS IN LIQUID FUEL.|
    CA2807561A1|2010-08-06|2012-02-09|Mascoma Corporation|Production of malonyl-coa derived products via anaerobic pathways|
    EP2697202B1|2011-04-13|2015-07-22|Rennovia, Inc.|Production of caprolactam from carbohydrate-containing materials|
    WO2013029149A1|2011-08-26|2013-03-07|Polyvalor Societe En Commandite|Methods for the valorization of carbohydrates|
    CA2858815C|2011-12-14|2020-09-08|Rennovia, Inc.|Water concentration reduction process|
    EP2790806A1|2011-12-14|2014-10-22|Rennovia, Inc.|Process for the separation of mono-and di-carboxylic acid compounds|
    CN104169259B|2012-02-23|2016-09-21|莱诺维亚公司|Caprolactam is produced from adipic acid|
    EA028465B1|2012-05-15|2017-11-30|Ренновиа, Инк.|Reduction catalysts|
    EA201492252A1|2012-06-11|2015-05-29|Ренновиа, Инк.|METHOD FOR OBTAINING ADIPIC ACID FROM 1,6-HEXANDIOL|
    JP2016532704A|2013-08-23|2016-10-20|レノビア インコーポレイテッド|Formation of 1,6-hexanediol from adipic acid|
    US11253839B2|2014-04-29|2022-02-22|Archer-Daniels-Midland Company|Shaped porous carbon products|
    ES2877375T3|2014-04-29|2021-11-16|Archer Daniels Midland Co|Method for preparing shaped porous products based on carbon black|
    WO2021236586A1|2020-05-18|2021-11-25|Archer-Daniels-Midland Company|Processes for the hydrogenolysis of glycerol|
    EP3142966B1|2014-05-12|2020-01-29|Virdia, Inc.|Hydrogenation of oxygenated molecules from biomass refining|
    KR101679914B1|2014-08-18|2016-11-25|현대자동차주식회사|Synthesis method of glucaric acid|
    JP6290756B2|2014-09-17|2018-03-07|旭化成株式会社|Method for producing compound having two or more carboxyl groups from primary alcohol, and catalyst used therefor|
    EP3789097A1|2014-09-29|2021-03-10|Archer-Daniels-Midland Company|A concentrated glucaric acid product|
    CA2897454A1|2015-07-03|2017-01-03|Governing Council Of The University Of Toronto|Microorganisms and methods for biosynthesis of adipic acid|
    US10722867B2|2015-10-28|2020-07-28|Archer-Daniels-Midland Company|Porous shaped carbon products|
    US10464048B2|2015-10-28|2019-11-05|Archer-Daniels-Midland Company|Porous shaped metal-carbon products|
    US10821422B2|2015-11-17|2020-11-03|University Of Kansas|Methods of forming and using metal alloy oxidative catalysts|
    WO2017123763A1|2016-01-13|2017-07-20|Rennovia Inc.|Processes for the preparation of 2,5-furandicarboxylic acid and intermediates and derivatives thereof|
    EP3580206B1|2017-02-10|2021-03-03|Basf Se|Process for preparing d-glucaro-6,3-lactone|
    CN107188795A|2017-06-05|2017-09-22|中国石油大学|A kind of method that low-temperature catalytic oxidation method prepares saccharic acid|
    BR112020000611A2|2017-07-12|2020-07-14|Stora Enso Oyj|purified products via 2,5-furanedicarboxylic acid pathway|
    WO2019014393A1|2017-07-12|2019-01-17|Stora Enso Oyj|Novel processes for preparation of 2,5-furandicarboxylic acid|
    CN111132968A|2017-10-05|2020-05-08|巴斯夫欧洲公司|N-alkyl-D-glucaric acid-6-amide derivatives and alkylammonium salts thereof as intermediates for the preparation of D-glucaric acid-6, 3-lactone monoamide|
    EP3781551A1|2018-04-18|2021-02-24|Basf Se|D-glucaro-6,3-lactone monoester and a process for the preparation thereof|
    KR20200024577A|2018-08-28|2020-03-09|현대자동차주식회사|Method of manufacturing bio-adipic acid derived from glucose|
    KR20200024578A|2018-08-28|2020-03-09|현대자동차주식회사|Manufacturing method of adipamide which is an Intermediate for bio nylon composition|
    KR20200025040A|2018-08-29|2020-03-10|현대자동차주식회사|Method for manufacturing the Adipic acid|
    KR20200073635A|2018-12-14|2020-06-24|현대자동차주식회사|Regeneration control method for improving durability of exhaust gas purification system|
    EP3782976A1|2019-08-21|2021-02-24|Kemijski Institut|Sustainable process for producing muconic, hexenedioic and adipic acidfrom aldaric acids by heterogeneous catalysis|
    CN110568043B|2019-08-26|2022-02-01|宁德师范学院|Pt @ Au/C bimetallic nano material and method for detecting glucose by using same|
    EP3822247A1|2019-11-18|2021-05-19|Archer Daniels Midland Company|Processes for preparing aldaric, aldonic, and uronic acids|
    EP3822248A1|2019-11-18|2021-05-19|Archer Daniels Midland Company|Processes for preparing aldaric, aldonic, and uronic acids|
    CN113069545A|2021-03-29|2021-07-06|华南农业大学|Long-acting antibacterial material with underwater adhesion photo-thermal dual responsiveness and preparation and application thereof|
    法律状态:
    2018-03-20| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2018-07-31| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2018-09-25| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/12/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    2019-02-26| B25A| Requested transfer of rights approved|Owner name: ARCHER-DANIELS-MIDLAND COMPANY (US) |
    优先权:
    申请号 | 申请日 | 专利标题
    US12/814,188|US8669397B2|2009-06-13|2010-06-11|Production of adipic acid and derivatives from carbohydrate-containing materials|
    PCT/US2010/060143|WO2011155964A1|2010-06-11|2010-12-13|Catalyst comprising platinum and gold nano - particles and its use for oxidation of glucose and preparation method of such a catalyst|
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