Porous shaped metal-carbon product

Abstract

The invention relates to a method of making a porous shaped metal-carbon product, the method comprising: mixing a carbonaceous material with water, a water-soluble organic binder, and a (first) metal precursor to form a metal-carbon mixture, wherein the metal precursor is a compound selected from the group consisting of a metal carbonate, a metal oxide, a metal hydroxide, a salt of a metal acid, a heteropoly acid, a metal carboxylate, a metal carbide, a metal chloride, a compound containing a metal amine complex, a hydrate thereof, and a mixture of any two or more thereof; shaping the metal-carbon mixture to form a green shaped metal-carbon product; and heating the green shaped metal-carbon product to a carbonization temperature to produce a carbonized shaped metal-carbon product comprising a plurality of pores.

Description

[0001] This application is a divisional application of the invention patent application with application number 201680076800.9, the original application being filed on October 28, 2016, and entitled "Porous Molded Metal-Carbon Product". Technical Field

[0002] This invention provides novel porous metal-containing carbon-based materials and related methods and compositions. These materials are particularly suitable for use as catalysts. Background Technology

[0003] Renewable raw materials, such as sugars and their derivatives, are attractive sources of feedstock for the production of general-purpose chemicals due to their relative abundance and low cost. Most of these materials are water-soluble and can be processed in aqueous solutions. These natural materials contain significant amounts of oxygen that need to be removed during processing. This is typically achieved through catalytic hydrogenation, which removes excess oxygen in the form of water. Long-term catalyst stability is essential for the production of general-purpose chemicals, meaning that the catalyst must be stable, efficient, and selective under commercial reaction conditions for extended periods.

[0004] One of the cheapest and most readily available catalysts for this process is a metal supported on a mineral support, which can be used in fixed-bed applications. However, catalysts supported on mineral supports exhibit low stability in aqueous media due to the slow dissolution of the support. Therefore, there is a need for new materials that can be commercially produced and are stable in applications requiring use in aqueous environments. Such materials are useful in catalytic applications as well as other applications requiring long-term use under aqueous conditions. Summary of the Invention

[0005] In one aspect, the present invention provides a method for preparing porous shaped metal-carbon products, the method comprising:

[0006] The carbonaceous material is mixed with water, a water-soluble organic binder, and (first) a metal precursor to form a metal-carbon mixture, wherein the metal precursor is a compound selected from the group consisting of: metal carbonates, metal oxides, metal hydroxides, salts of metal acids, heteropoly acids, metal carboxylates, metal carbides, metal chlorides, compounds containing metal amine complexes, their hydrates, and mixtures of any two or more thereof.

[0007] The metal-carbon mixture is shaped to form a green-molded metal-carbon product; and

[0008] The green metal-carbon product is heated to a carbonization temperature to produce a carbonized metal-carbon product containing many pores.

[0009] In another aspect, the present invention provides porous shaped metal-carbon products made by the methods described herein.

[0010] In another aspect, the present invention provides a method for producing bis-hydroxymethyltetrahydrofuran (BHMTHF) from 2,5-bis-hydroxymethylfuran (BHMF), the method comprising:

[0011] BHMF is contacted with hydrogen in the presence of a hydrogenation catalyst containing the porous shaped metal-carbon product of the present invention to produce BHMTHF.

[0012] In another aspect, the present invention provides a method for producing a corresponding C3-C6 diol from a C3-C6 polyol, the method comprising:

[0013] C3-C6 polyols are contacted with hydrogen in the presence of a hydrodeoxygenation catalyst comprising the porous shaped metal-carbon product of the present invention to produce the corresponding C3-C6 diols.

[0014] In another aspect, the present invention provides a method for producing 1,6-hexanediamine (HMDA) from 1,6-hexanediol (HDO), the method comprising:

[0015] HDO is contacted with an amine in the presence of an amination catalyst containing the porous shaped metal-carbon product of the present invention to form HMDA.

[0016] In another aspect, the present invention provides a method for producing gluconic acid from glucose, the method comprising:

[0017] Glucose is contacted with oxygen in the presence of an oxidizing catalyst comprising the porous shaped metal-carbon product of the present invention to form gluconic acid.

[0018] In another aspect, the present invention provides a method for producing dicarboxylic acids from aldonic acid or its salts, esters or lactones, the method comprising:

[0019] Aldonic acid or its salts, esters or lactones are contacted with hydrogen in the presence of a halogenated compound and a hydroxygenation catalyst containing the porous shaped metal-carbon product of the present invention to form a dicarboxylic acid.

[0020] In another aspect, the present invention provides a method for producing 2,5-bis-hydroxymethylfuran (BHMF) from 5-hydroxymethylfurfural (HMF), the method comprising:

[0021] HMF is contacted with hydrogen in the presence of a hydrogenation catalyst containing the porous shaped metal-carbon product of the present invention to form BHMF.

[0022] In particular, the present invention relates to the following technical solutions:

[0023] 1. A method for preparing porous shaped metal-carbon products, the method comprising:

[0024] The carbonaceous material is mixed with water, a water-soluble organic binder, and (first) a metal precursor to form a metal-carbon mixture, wherein the metal precursor is a compound selected from the group consisting of: metal carbonates, metal oxides, metal hydroxides, salts of metal acids, heteropoly acids, metal carboxylates, metal carbides, metal chlorides, compounds containing metal amine complexes, their hydrates, and mixtures of any two or more thereof.

[0025] The metal-carbon mixture is shaped to form a green-molded metal-carbon product; and

[0026] The green metal-carbon product is heated to a carbonization temperature to produce a carbonized metal-carbon product containing many pores.

[0027] 2. The method according to technical solution 1, wherein the metal precursor comprises a metal as a base metal.

[0028] 3. The method according to technical solution 1 or 2, wherein the metal precursor comprises a metal selected from Cu, Pb, Ni, Zn, Fe, Mo, Al, Sn, W, Ta, Co, Bi, Cd, Ti, Zr, Sb, Mn, Be, Cr, Ge, V, Ga, Hf, In, Nb, Rh, Tl, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and combinations thereof.

[0029] 4. The method according to any one of technical solutions 1-3, wherein the metal precursor can decompose and be reduced to a metal at a temperature of about 250°C to about 1,000°C.

[0030] 5. The method according to any one of technical solutions 1-4, wherein the metal precursor is nickel carbonate or its hydrate.

[0031] 6. The method according to any one of technical solutions 1-5, wherein the metal precursor is hydrated ammonium metatungstate.

[0032] 7. The method according to any one of technical claims 1-6, wherein the metal precursor is present in the metal-carbon mixture in an amount of about 0.1 wt% to about 90 wt%, about 5 wt% to about 70 wt%, about 10 wt% to about 70 wt%, about 5 wt% to about 60 wt%, about 10 wt% to about 60 wt%, about 15 wt% to about 70 wt%, about 25 wt% to about 60 wt%, about 0.1 wt% to about 10 wt%, about 0.1 wt% to about 5 wt%, or about 0.5 wt% to about 5 wt%.

[0033] 8. The method according to any one of technical claims 1-7, wherein the carbonaceous material is present in the metal-carbon mixture in an amount of about 15% to about 80% by weight, about 20% to about 60% by weight, or about 15% to about 35% by weight.

[0034] 9. The method according to any one of technical solutions 1-8, wherein the water-soluble organic binder and the carbonaceous material are present in the metal-carbon mixture at a weight ratio of at least about 1:4, at least about 1:3, at least about 1:2, at least about 1:1, or at least about 1.5:1 water-soluble organic binder: carbonaceous material.

[0035] 10. The method according to any one of claims 1-9, wherein the adhesive is present in the metal-carbon mixture in an amount of about 10% by weight to about 50% by weight.

[0036] 11. The method according to any one of technical solutions 1-10, wherein water is present in the metal-carbon mixture in an amount not exceeding about 80% by weight of the metal-carbon mixture.

[0037] 12. The method according to any one of technical solutions 1-11, wherein the water-soluble organic adhesive is a water-soluble polymer.

[0038] 13. The method according to technical solution 12, wherein the water-soluble polymer is a carbohydrate.

[0039] 14. The method according to technical solution 13, wherein the carbohydrate is cellulose.

[0040] 15. The method according to any one of technical solutions 1-14, wherein the water-soluble organic binder is sugar.

[0041] 16. The method according to any one of claims 1-15, wherein the water-soluble organic adhesive comprises a mixture of a water-soluble polymer and sugar.

[0042] 17. The method according to any one of technical solutions 1-16, wherein the organic water-soluble binder is a mixture of cellulose and sugar.

[0043] 18. The method according to any one of technical solutions 1-17, further comprising premixing a subset of components selected from water, water-soluble organic binders, carbonaceous materials and metal precursors.

[0044] 19. The method according to any one of technical solutions 1-18, further comprising drying the metal-carbon mixture to remove at least a portion of the water before heating the green metal-carbon product to a carbonization temperature.

[0045] 20. The method according to technical claim 19, wherein the drying is carried out at a temperature of about 20°C to about 175°C, about 20°C to about 150°C, about 40°C to about 120°C, about 60°C to about 120°C, about 90°C to about 175°C, about 90°C to about 150°C, about 100°C to about 150°C, or about 100°C to about 140°C.

[0046] 21. The method according to any one of technical claims 1-20, wherein the carbonization temperature is in the range of about 250°C to about 1000°C, or about 300°C to about 950°C, or about 300°C to about 900°C, or about 350°C to about 900°C, or about 350°C to about 850°C or about 350°C to about 800°C.

[0047] 22. The method according to any one of technical solutions 1-21, further comprising contacting the carbonized metal-carbon product with a reducing agent at a temperature of about 100°C to about 600°C.

[0048] 23. The method according to any one of technical solutions 1-22, further comprising forming particles of the carbonized metal-carbon product.

[0049] 24. The method according to any one of technical claims 1-23, wherein the carbonized metal-carbon product comprises an amount of metal from about 0.1% by weight to about 70% by weight.

[0050] 25. The method according to any one of technical solutions 1-24, wherein the carbonized metal-carbon product is conductive.

[0051] 26. The method according to any one of technical solutions 1-25, wherein the carbonaceous material is carbon black.

[0052] 27. The method according to any one of technical solutions 1-26, wherein the carbonaceous material is activated carbon.

[0053] 28. The method according to any one of technical solutions 1-27, wherein the carbonaceous material is graphite.

[0054] 29. The method according to any one of technical solutions 1-28, wherein the carbonaceous material is a mixture of any two or more materials selected from carbon black, activated carbon, graphite and carbon nanotubes.

[0055] 30. The method according to any one of technical solutions 1-29, wherein the carbonaceous material has at least about 20m 2 / g, or approximately 20m 2 / g to approximately 500m 2 / g or approximately 550mg 2 / g to approximately 3500m 2 / g BET specific surface area.

[0056] 31. The method according to any one of technical claims 1-30, wherein the carbide-formed metal-carbon product has an associated pore volume, wherein approximately 50% to approximately 95% of the pore volume, as measured by the BJH method based on pores having a diameter of 1.7 nm to 100 nm, comes from pores having a pore diameter of approximately 5 nm to approximately 100 nm.

[0057] 32. The method according to technical solutions 1-31, wherein no more than about 10% of the pore volume comes from pores with a pore size of less than about 10 nm.

[0058] 33. The method according to any one of technical solutions 1-32, wherein the carbonized metal-carbon product has an associated thickness of approximately 0.1 cm. 3 / g to approximately 1.5cm 3 / g is the specific pore volume, as measured by the BJH method based on pores with diameters ranging from 1.7 nm to 100 nm.

[0059] 34. The method according to any one of claims 1-33, wherein the carbonized metal-carbon product exhibits a radial sheet crushing strength greater than about 4.4 N / mm (1 lb / mm).

[0060] 35. The method according to any one of technical solutions 1-34, further comprising depositing a second metal precursor on the surface of the carbonized metal-carbon product.

[0061] 36. A carbonized metal-carbon product according to any one of technical solutions 1-35.

[0062] 37. A porous shaped metal-carbon product comprising a porous carbon matrix and a metal component, wherein the metal component of the porous shaped metal-carbon product is present in a metal loading of at least about 10 wt%, at least about 11 wt%, at least about 12 wt%, at least about 13 wt%, at least about 14 wt%, at least about 15 wt%, at least about 16 wt%, at least about 17 wt%, at least about 18 wt%, at least about 19 wt%, or at least about 20 wt%.

[0063] 38. The product according to technical solution 37, wherein the metal component of the porous shaped metal-carbon product is a base metal.

[0064] 39. The product according to technical solution 38, wherein the metal component of the porous shaped metal-carbon product is selected from Cu, Pb, Ni, Zn, Fe, Mo, Al, Sn, W, Ta, Co, Bi, Cd, Ti, Zr, Sb, Mn, Be, Cr, Ge, V, Ga, Hf, In, Nb, Rh, Tl, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and combinations thereof.

[0065] 40. The product according to any one of technical solutions 37-39 further comprises a second metal deposited on the surface of the porous shaped metal-carbon product.

[0066] 41. A method for producing bis-hydroxymethyltetrahydrofuran (BHMTHF) from 2,5-bis-hydroxymethylfuran (BHMF), the method comprising:

[0067] BHMF is contacted with hydrogen in the presence of a multiphase hydrogenation catalyst containing a porous shaped metal-carbon product to form BHMTHF, wherein the metal component of the metal-carbon product is selected from Ni, Co, Cu, Ag, Pd, Pt, Ru, and combinations thereof.

[0068] 42. A method for producing the corresponding C3-C6 diol from a C3-C6 polyol, the method comprising:

[0069] C3-C6 polyols are contacted with hydrogen in the presence of a hydrodeoxygenation catalyst containing a porous shaped metal-carbon product to form the corresponding C3-C6 diol, wherein the metal component of the metal-carbon product is selected from Pd, Pt, Ir, Mo, W, V, Mn, Re, Zr, Ni, Cu, La, Sm, Y, Zn, Cr, Ge, Sn, Ti, Au, Rh, Co, and combinations thereof.

[0070] 43. The method according to technical solution 42, wherein the C3-C6 polyol is selected from 1,2,6-hexanetriol, 1,2,5-pentanetriol, 2H-tetrahydropyran-2-methanol, tetrahydrofuran-2,5-diethanol, furan-2,5-diethanol, 2,5-dihydrofuran-2,5-diethanol, L-glucan, L-glucan, levoglucosenol, 1,6-dehydro-3,4- -Dideoxy-pD-pyranose-2-one, isosorbide, hydroxymethylfurfural, sorbitol, glucose, fructose, xylitol, 3,4-dihydro-2H-pyran-2-carboxaldehyde, 1,2,5,6-hexanetetrol, 1,2,3,5,6-hexanepentol, 1,5-dehydro-3,4-dideoxyhexitol, 5-hydroxy-2H-tetrahydropyran-2-methanol, furfural, furfuryl alcohol, tetrahydrofurfural alcohol, pentoses and hexoses.

[0071] 44. The method according to technical solution 42 or 43, wherein the C3-C6 diol is selected from 1,5-pentanediol and 1,6-hexanediol.

[0072] 45. A method for producing 1,6-hexanediamine (HMDA) from 1,6-hexanediol (HDO), the method comprising:

[0073] 1,6-hexanediol and amine are contacted in the presence of an amination catalyst containing a porous shaped metal-carbon product to form HMDA, wherein the metal component of the porous shaped metal-carbon product is a metal selected from Ni, Ru and Rh.

[0074] 46. ​​A method for producing gluconic acid from glucose, the method comprising:

[0075] Glucose is contacted with oxygen in the presence of an oxidation catalyst containing a porous shaped metal-carbon product to form gluconic acid, wherein the metal component of the porous shaped metal-carbon product is a base metal.

[0076] 47. The method according to technical solution 46, wherein the porous shaped metal-carbon product further comprises a noble metal deposited thereon.

[0077] 48. A method for producing dicarboxylic acids from aldonic acid or its salts, esters, or lactones, the method comprising:

[0078] Aldonic acid or its salt, ester or lactone is contacted with hydrogen in the presence of a halogenated compound and a hydrodeoxygenation catalyst comprising the porous shaped metal-carbon product of the present invention to form a dicarboxylic acid, wherein the metal component of the porous shaped metal-carbon product is a base metal.

[0079] 49. The method according to claim 48, wherein the porous shaped metal-carbon product further comprises a noble metal deposited thereon.

[0080] 50. A method for producing 2,5-bis-hydroxymethylfuran (BHMF) from 5-hydroxymethylfurfural (HMF), the method comprising:

[0081] HMF is contacted with hydrogen in the presence of a hydrogenation catalyst containing the porous shaped metal-carbon product of the present invention to form BHMF, wherein the metal component of the porous shaped metal-carbon product is selected from Ni, Zn, Co, Cu, Ag, Pt, Pd, Fe, Ru, Au, W, Sb, Bi, Pb and combinations thereof. Detailed Implementation

[0082] This invention provides novel porous metal-containing carbon-based materials (i.e., products) with desirable properties. These materials exhibit certain properties of the metal components used to prepare them. These durable porous materials are particularly suitable for use as catalysts, and for other applications requiring high mechanical strength.

[0083] In one embodiment, the present invention provides a method for preparing carbonized metal-carbon products, the method comprising:

[0084] Carbonaceous materials are mixed with water, a water-soluble organic binder, and a metal precursor to form a metal-carbon mixture, wherein the metal precursor is a compound selected from the group consisting of: metal carbonates, metal oxides, metal hydroxides, salts of metal acids, heteropoly acids, metal carboxylates, metal carbides, metal chlorides, compounds containing metal amine complexes, their hydrates, and mixtures of any two or more thereof.

[0085] The metal-carbon mixture is molded to form a green-molded metal-carbon product and

[0086] The green metal-carbon product is heated to a carbonization temperature to produce a carbonized metal-carbon product containing many pores (i.e., the "carbonization step").

[0087] The applicant has discovered that, despite the metal precursor being mixed with and subsequently carbonized with the other components of the metal-carbon mixture, the porous, carbonized, shaped metal-carbon product prepared by the methods described herein exhibits certain metallic properties. This effect is particularly pronounced when the product is used as a catalyst. As demonstrated in Example 5 below, its performance as a catalytic material is, if not better, than that of catalysts prepared by impregnating a mineral oxide-based support with a metal (and thus depositing the metal onto the surface of the mineral oxide-based support).

[0088] The examples also demonstrate that the metal precursors used in this invention do not necessarily have to be water-soluble to achieve this effect. They can be water-insoluble. One significance of the method for producing porous, metal-containing, carbon-based products exhibiting certain properties of the metal, which can be prepared not only from water-soluble metal precursors but also from water-insoluble metal precursors, is that it can achieve much higher metal loadings than those achieved using standard methods, such as impregnation. This is because higher metal loadings can be achieved in a single step without altering the functional form of the carrier material, which might otherwise affect the accessibility of the pores.

[0089] The method of this invention can incorporate a wide variety of metal types into / on carbon, which is challenging when using more commonly used metal precursors such as metal nitrates. Although metal nitrates, as strong oxidizing agents, can be heated together with mineral oxide materials to impregnate them without consequences, attempting to impregnate carbon on a large scale using the same method could be a potentially dangerous endeavor.

[0090] For certain metal precursors, in-situ reduction to the metal during the carbonization step is another advantage of this method, as it eliminates the need for a subsequent reduction process. While not wishing to be bound by theory, it is believed that during the carbonization step, the metal precursor may decompose and, in some cases, be reduced to the metal. Studies as described in the examples confirm that the resulting carbonization products exhibit catalytic activity. This indicates that the metal decomposition products are not only in a catalytically active form, but are also accessible to the reactants (i.e., located on the surface (external / internal)).

[0091] Another advantage of the method of the present invention is that the product is relatively "clean" in terms of the absence of potential contaminants, for example (when metal halides are not used as metal precursors) there are no halides, otherwise contaminants may need to be washed off before being used for certain purposes.

[0092] The metal precursor used in embodiments of this invention may comprise various metals. These metals may be base metals or noble metals. As used herein, the term "base metal" refers to a metal that is not a noble metal. The term "noble metal" herein refers to Ru, Rh, Pd, Ag, Os, Ir, Pt, or Au.

[0093] In some embodiments, the metal is selected from groups IV, V, VI, VII, VIII, IX, X, XI, XII, and XIII. In various embodiments, the metal is a d-block metal. Exemplary d-block metals include, for example, Ni, Co, W, Cu, Zn, Fe, Mo, Ni, Rh, Pd, Ag, Os, Ir, Pt, Au, etc.

[0094] In other embodiments, the metal precursor comprises a metal selected from Cu, Pb, Ni, Zn, Fe, Mo, Al, Sn, W, Ta, Co, Bi, Cd, Ti, Zr, Sb, Mn, Be, Cr, Ge, V, Ga, Hf, In, Nb, Rh, Tl, Ru, Rh, Pd, Ag, Os, Ir, Pt, or Au. Typically, the metal precursor comprises a base metal. In specific embodiments, the metal precursor comprises a metal selected from Cu, Pb, Ni, Zn, Fe, Mo, Al, Sn, W, Ta, Co, Bi, Cd, Ti, Zr, Sb, Mn, Be, Cr, Ge, V, Ga, Hf, In, Nb, Rh, and Tl. In some embodiments, the metal precursor comprises a metal selected from Ni, Co, Mo, Nb, and W. The metal precursor typically comprises a metal selected from Ni and W.

[0095] The method of the present invention can use various types of metal precursors, including metal carbonates, metal oxides, metal hydroxides, salts of metal acids, heteropolyacids, metal carboxylates, metal carbides, metal chlorides, compounds containing metal amine complexes, and their hydrates and mixtures of any two or more thereof. As explained above, the metal precursor can be water-soluble or water-insoluble. The term "water-insoluble" as used herein, when used in conjunction with a metal precursor, refers to a metal precursor with a solubility in water of less than 0.1% by weight. The term "water-soluble" when used in conjunction with a metal precursor refers to a metal precursor with a solubility in water of 0.1% by weight or greater.

[0096] Metal carbonates suitable for use in this invention include NiCO3, metal hydroxy carbonates such as NiCO3 2Ni(OH)2xH2O, etc. Metal amine complexes, such as nickel tetraamine carbonate (Ni(NH3)4(CO3)) and cobalt tetraamine carbonate (Co(NH3)4CO3), are also suitable. Suitable metal oxides include, for example, NiO, WO3, CoO, Co3O4, and Co2O3. Metal hydroxides suitable for use in this invention include, for example, Ni(OH)2, Co(OH)2, and W(OH)2. Exemplary metal salts suitable for the methods used in this invention include, for example, tungstates (e.g., hydrogen tungstate, polymeric W2O7). 2- Paratungstate A([W7O) 24 ] 6- ), paratungstate B([H2W) 12 O 42 ] 10- ), metatungstate (α-[H2W) 12 O 40 ] 6- ), tungstate Y([W 10 O 32 ]4- ), tungstate X(β-[H2W) 12 O 40 ] 6- (etc.), and their hydrates). Salts of metal acids can be formed first by premixing a metal acid or metal oxide (e.g., H₂WO₄, WO₃, etc.) with a base (e.g., NH₃, diamine (e.g., ethylenediamine), KOH, NaOH, etc.) to form the corresponding metal salt in aqueous solution (which can be introduced into a subsequent metal-carbon mixture). Exemplary metal salts that can be formed in this way include, for example, (NH₃)₂WO₄, K₂WO₄, (C₂H₈N₂)₂WO₄, etc. Heteropolyacids suitable for implementation of this invention include tungstic acid hydrate (H₄[Si(W₃O₄)₂WO₄]₂WO₄, etc. 10 )4]·xH2O), phosphotungstic acid hydrate (H3[P(W3O) 10 [4]xH2O), silicomolybdic acid (H4SiO4 12MoO3). Exemplary metal carboxylates suitable as metal precursors in this invention include metal formates, metal acetates, metal citrates, metal succinates, metal oxalates, metal lactates, etc. Specific examples include cobalt(III) 2-ethylhexanoate, cobalt(II) 2-ethylhexanoate ([CH3(CH2)3CH(C2H5)CO2]2Co), nickel(II) 2-ethylhexanoate ([CH3(CH2)3CH(C2H5)CO2]2Ni, nickel(II) acetate tetrahydrate (Ni(OCOCH3)24H2O), nickel(III) oxalate dihydrate (NiC2O4 2H2O), cobalt(III) oxalate dihydrate (CoC2O4·2H2O), etc. Exemplary metal carbides suitable for implementation of this invention include, for example, tungsten carbide (WC). Metal chlorides suitable for implementation of this invention include nickel chloride (NiCl2), etc. The term "compound containing a metal amine complex" herein refers to a metal complex having at least one ammonia (NH3) ligand complexed with a metal ion, and typically contains a counterion. Typical counterions include, for example, carbonate (including, for example, bicarbonate), halide, hydroxide, carboxylate, etc. In some embodiments, the metal precursor comprises a metal with a melting temperature greater than its carbonization temperature.

[0097] Preferred nickel-based precursors are nickel carbonate and its hydrates. Preferred tungsten-based precursors include salts of tungstate (i.e., in which tungsten exists as a tungstate anion), such as ammonium paratungstate, ammonium metatungstate, etc., and their hydrates, as well as solutions of tungsten trioxide (WO3) or tungstate (H2WO4) in alkali (e.g., ammonia (NH3), ammonium hydroxide, etc.).

[0098] The amount of metal precursor used in the metal-carbon mixture varies depending on the amount of metal required in the carbide-formed metal-carbon product. Those skilled in the art can readily calculate the amount of metal precursor required to achieve the desired target weight percentage of metal in the carbide-formed metal-carbon product. In some embodiments, the amount of metal precursor used in the metal-carbon mixture is from about 1 wt% to about 90 wt%, more typically from about 1 wt% to about 85 wt%, from about 1 wt% to about 80 wt%, from about 1 wt% to about 75 wt%, from about 1 wt% to about 70 wt%, from about 1 wt% to about 65 wt%, from about 1 wt% to about 60 wt%, from about 1 wt% to about 55 wt%, from about 1 wt% to about 50 wt%, from about 1 wt% to about 45 wt%, from about 1 wt% to about 40 wt%, from about 1 wt% to about 35 wt%, from about 1 wt% to about 30 wt%, from about 1 wt% to about 25 wt%, or from about 1 wt% to about 20 wt%. In other embodiments, the amount of the metal precursor in the metal-carbon mixture is about 5 wt% to about 70 wt%, about 10 wt% to about 70 wt%, about 15 wt% to about 70 wt%, about 5 wt% to about 60 wt%, about 10 wt% to about 60 wt%, about 15 wt% to about 60 wt%, about 20 wt% to about 60 wt%, or about 25 wt% to about 60 wt%. Typically, the amount of the metal precursor in the metal-carbon mixture is about 1 wt% to about 25 wt%, about 2 wt% to about 25 wt%, about 3 wt% to about 25 wt%, about 4 wt% to about 25 wt%, about 5 wt% to about 25 wt%, or about 5 wt% to about 20 wt%. In some embodiments, for example when the metal is a co-catalyst, the amount of the corresponding metal precursor in the metal-carbon mixture is from about 0.1 wt% to about 10 wt%, from about 0.1 wt% to about 5 wt%, or from about 0.5 wt% to about 5 wt%.

[0099] The water-soluble organic adhesive suitable for use in embodiments of the present invention is a water-soluble organic compound that can be carbonized at a temperature of about 250°C to about 1000°C and exhibits a solubility of at least about 1% by weight in water at a temperature of 50°C. In some embodiments, the water-soluble adhesive exhibits a solubility of at least about 2% by weight in water at a temperature of 50°C.

[0100] The water-soluble organic binder used in embodiments of the present invention is typically a water-soluble organic compound containing only carbon, oxygen, and hydrogen atoms. However, in some embodiments, the water-soluble organic binder may contain other types of atoms. Suitable water-soluble organic binders are carbohydrates or derivatives thereof, or non-carbohydrate compounds. Carbohydrates used in embodiments of the present invention can be monosaccharides, disaccharides, oligosaccharides, polysaccharides, or derivatives thereof. Suitable monosaccharides include, for example, glucose, fructose, galactose, ribose, etc. Suitable disaccharides include, for example, sucrose, lactose, maltose, trehalose, etc. Typically, the water-soluble organic binder contains sugars (i.e., monosaccharides and / or disaccharides) alone or with the water-soluble polymer. Exemplary oligosaccharides suitable for embodiments of the present invention include fructooligosaccharides, galactooligosaccharides, mannosaccharides, etc.

[0101] Exemplary polysaccharides include, for example, cellulose (e.g., methylcellulose, ethylcellulose, ethylmethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylhydroxyethylcellulose, ethylhydroxyethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, etc., and mixtures thereof), alginic acid, pectin, aldonic acid, etc., and mixtures thereof.

[0102] Suitable carbohydrate derivatives include, for example, polyols (such as sugar alcohols, such as sorbitol, glycerol, erythritol, threitol, aritol, xylitol, ribitol, mannitol, galactitol, fucitol, idutol, inositol, heptacapol, isomalt, maltitol, lactitol, maltotriol, maltotetratitol, polyglycitol, etc.); sugar acids (such as gluconic acid, glucuronic acid, etc.), amino sugars (such as glucosamine, etc.), sialic acid, etc.

[0103] Suitable water-soluble non-carbohydrate compounds for use in this invention include, for example, water-soluble non-carbohydrate polymers, water-soluble fatty acids or their salts, water-soluble fatty alcohols or their esters. Water-soluble non-carbohydrate polymers that can be used as adhesives in this invention include homopolymers, copolymers (or other polymers based on multiple monomers, such as peptides, polynucleotides, collagen, gelatin, etc.), and polymers that form hydrogels. Suitable non-carbohydrate polymers include, for example, polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetate, polyacrylate, polyethers (e.g., polyethylene glycol), polyols (e.g., glycerol), polyethylene oxide, polyoxymethylene, poly(oxymethylene), poly(ethylene phthalate), gum arabic, phenolic resin solutions, polyacrylamide, polylactic acid, and mixtures and copolymers thereof. Suitable copolymers include, for example, polylactic acid-co-glycolic acid.

[0104] In some embodiments, the water-soluble organic adhesive comprises a water-soluble polymer having a relatively low number-average molecular weight and / or capable of producing a solution with a relatively low viscosity. Accordingly, in various embodiments, the adhesive comprises a water-soluble polymer, wherein a 2% by weight aqueous solution or a 5% by weight aqueous solution of the water-soluble polymer has a viscosity at 25°C of not more than about 500 mPa⁻², or not more than about 400 mPa⁻², or not more than about 300 mPa⁻², or not more than about 200 mPa⁻², or not more than about 100 mPa⁻², or not more than about 75 mPa⁻², or not more than about 50 mPa⁻², and / or the water-soluble polymer has a number-average molecular weight (Mn) of not more than about 50,000 g / mol, or not more than about 40,000 g / mol, or not more than about 30,000 g / mol, or not more than about 25,000 g / mol, or not more than about 20,000 g / mol. In some embodiments, the adhesive comprises a water-soluble polymer, wherein a 2% by weight aqueous solution or a 5% by weight aqueous solution of the water-soluble polymer has a viscosity of about 2 to about 500 mPa-s, about 2 to about 400 mPa-s, about 2 to about 100 mPa-s, about 2 to about 75 mPa-s, or about 2 to about 50 mPa-s at 25°C. In these and other embodiments, the water-soluble polymer may have a number-average molecular weight (Mn) of about 2,000 to about 50,000 g / mol, about 5,000 to about 40,000 g / mol, about 5,000 to about 30,000 g / mol, about 5,000 to about 25,000 g / mol, about 5,000 to about 20,000 g / mol, about 20,000 to about 50,000 g / mol, about 10,000 to about 40,000 g / mol, about 10,000 to about 30,000 g / mol, about 10,000 to about 25,000 g / mol, or about 10,000 to about 20,000 g / mol. The water-soluble organic adhesives applicable to the implementation of this invention include those described in published PCT application WO 2015 / 168327 and US applications USSN62 / 247,721 and USSN15 / 131,829, each of which is hereby incorporated herein by reference.

[0105] The amount of binder used in this metal-carbon mixture is typically from about 10% to about 50% by weight. In some embodiments, the amount of binder is from about 10% to about 45% by weight, from about 15% to about 40% by weight, from about 20% to about 35% by weight, or from about 25% to about 35% by weight.

[0106] Those skilled in the art will recognize that the adhesive can be a mixture of the aforementioned compounds. For example, in some embodiments, the adhesive comprises at least one monosaccharide or disaccharide and at least one polysaccharide. In these embodiments, the weight ratio of the monosaccharide or disaccharide to the polysaccharide is typically from about 2:1 to about 30:1. More typically, this weight ratio is from about 3:1 to about 25:1, 3:1 to about 20:1, about 5:1 to about 20:1, or about 10:1 to about 20:1. In a preferred embodiment, the adhesive comprises a mixture of glucose and cellulose, such as hydroxyethyl cellulose.

[0107] As used herein, the term "carbonaceous material" refers to elemental carbon in graphite form or amorphous carbon. When the carbonaceous material used in the embodiments of this invention is amorphous carbon, it is typically carbon black or activated carbon. The choice of carbonaceous material depends on the desired properties of the metal-containing carbon composite material. It has been found that the porous properties of the basic carbonaceous material substantially correspond to the corresponding properties in (carbonized) metal-containing carbon composite materials.

[0108] Accordingly, carbon black is typically used when a composite material with relatively low porosity and low specific surface area is required. Activated carbon is typically used when a composite material with relatively high porosity and high specific surface area is required. In some embodiments, carbon nanotubes may be desired as the carbonaceous material. In some applications, such as when a highly conductive material is required, graphite may be desired as the carbonaceous material. The aforementioned carbonaceous materials are readily available from commercial suppliers. Specific carbon blacks suitable for the methods of this invention include those described in published PCT application WO 2015 / 168327 and US applications USSN 62 / 247,721 and USSN 15 / 131,829, each of which is hereby incorporated by reference.

[0109] The weight ratio of binder to carbonaceous material in the metal-carbon mixture is typically at least about 1:4, at least about 1:3, at least about 1:2, at least about 1:1, or at least 1.5:1. The weight ratio can also be from about 1:4 to about 3:1, from about 1:4 to about 1:1, from about 1:3 to about 2:1, from about 1:3 to about 1:1, or about 1:1. Typically, on a dry weight basis, the amount of carbonaceous material in the metal-carbon mixture is at least about 35% by weight or greater, such as at least about 40% by weight, at least about 45% by weight, at least about 50% by weight, at least about 55% by weight, at least about 60% by weight, at least about 65% by weight, or at least about 70% by weight. In various embodiments, on a dry weight basis, the amount of carbonaceous material in the metal-carbon mixture is about 35% to about 80% by weight, about 35% to about 75% by weight, about 40% to about 80% by weight, or about 40% to about 75% by weight.

[0110] The metal-carbon mixture typically contains approximately 10% to approximately 80% by weight, more typically approximately 15% to approximately 75% by weight, approximately 15% to approximately 70% by weight, approximately 15% to approximately 65% ​​by weight, approximately 15% to approximately 60% by weight, approximately 15% to approximately 55% by weight, approximately 15% to approximately 50% by weight, approximately 15% to approximately 45% by weight, approximately 15% to approximately 40% by weight, approximately 15% to approximately 35% by weight, approximately 20% to approximately 70% by weight, approximately 20% to approximately 65% ​​by weight, approximately 20% to approximately 60% by weight, approximately 20% to approximately 55% by weight, approximately 20% to approximately 50% by weight, approximately 20% to approximately 45% by weight, approximately 20% to approximately 40% by weight, approximately 20% to approximately 35% by weight, or approximately 25% to approximately 35% by weight of carbonaceous material.

[0111] When carbon black is used, it can be either non-conductive or conductive. The carbon black material used to prepare the molded porous metal-carbon products of this invention also typically has a density greater than approximately 0.1 cm. 3 / g, greater than approximately 0.2cm 3 / g or greater than approximately 0.3cm 3 The specific pore volume is approximately 0.1 cm³ / g. 3 / g to approximately 1cm 3 / g, approximately 0.1cm 3 / g to approximately 0.9cm 3 / g, approximately 0.1cm 3 / g to approximately 0.8cm 3 / g, approximately 0.1cm 3 / g to approximately 0.7cm 3 / g, approximately 0.1cm 3 / g to approximately 0.6cm 3 / g, approximately 0.1cm 3 / g to approximately 0.5cm 3 / g, approximately 0.2cm 3 / g to approximately 1cm 3 / g, approximately 0.2cm 3 / g to approximately 0.9cm 3 / g, approximately 0.2cm 3 / g to approximately 0.8cm 3 / g, approximately 0.2cm 3 / g to approximately 0.7cm 3 / g, approximately 0.2cm 3 / g to approximately 0.6cm 3 / g, approximately 0.2cm 3 / g to approximately 0.5cm 3 / g, approximately 0.3cm 3 / g to approximately 1cm 3 / g, approximately 0.3cm 3 / g to approximately 0.9cm 3 / g, approximately 0.3cm 3 / g to approximately 0.8cm 3 / g, approximately 0.3cm 3 / g to approximately 0.7cm 3 / g, approximately 0.3cm 3 / g to approximately 0.6cm 3 / g, or approximately 0.3cm 3 / g to approximately 0.5cm 3 / g. Carbon black materials with these specific pore volumes provide sufficient volume to provide uniform wetting and good dispersion of the catalytically active components, while ensuring adequate contact between reactant molecules and the catalytically active surface. The average pore size and pore volume were determined according to the procedures described in EP Barrett, LG Joyner, PP Halenda, J. Am. Chem. Soc. 1951, 73, 373-380 (referred to herein as the "BJH method") and ASTM D4222-03 (2008) Standard Test Method for Determination of Nitrogen Adsorption and Desorption Isotherms of Catalysts and Catalyst Carriers by Static Volumetric Measurements (incorporated herein).

[0112] Typically, this carbon black has a density of approximately 20 μm. 2 / g to approximately 500m 2 / g BET specific surface area. In some embodiments, the BET specific surface area is approximately 20m². 2 / g to approximately 350m 2 / g, approximately 20m 2 / g to approximately 250m 2 / g, approximately 20m 2 / g to approximately 225m 2 / g, approximately 20m 2 / g to approximately 200m 2 / g, approximately 20m 2 / g to approximately 175m 2 / g, approximately 20m 2 / g to approximately 150m 2 / g, approximately 20m 2 / g to approximately 125m 2 / g, or approximately 20m 2 / g to approximately 100m 2 / g, approximately 25m 2 / g to approximately 500m 2 / g, approximately 25m 2 / g to approximately 350m 2 / g, approximately 25m 2 / g to approximately 250m 2 / g, approximately 25m 2 / g to approximately 225m 2 / g to approximately 150m 2 / g, approximately 25m 2 / g to approximately 125m 2 / g, approximately 25m 2 / g to approximately 100m 2 / g, approximately 30m 2 / g to approximately 500m 2 / g, approximately 30m 2 / g to approximately 350m 2 / g, approximately 30m 2 / g to approximately 250m 2 / g, approximately 30m 2 / g to approximately 225m 2 / g, approximately 30m 2 / g to approximately 200m 2 / g, approximately 30m 2 / g to approximately 175m 2 / g, approximately 30m 2 / g to approximately 150m 2 / g, approximately 30m 2 / g to approximately 125m 2 / g, or approximately 30m 2 / g to approximately 100m 2 / g. As used herein, the term “BET surface area” refers to the surface area determined by nitrogen adsorption data according to the Brunauer, Emmet, and Teller methods as described in J. Am. Chem. Soc. (1938) 60:309-331 and ASTM Test Methods D3663, D6556, or D4567 (Standard Test Methods for Surface Area Measurements by Nitrogen Adsorption) (which is incorporated herein by reference).

[0113] In some embodiments, such as when a high surface area metal-carbon product is required, the carbonaceous material is activated carbon. Activated carbon suitable for embodiments of the present invention typically exhibits a surface area greater than 500 m². 2 / g BET specific surface area. In some embodiments, the BET specific surface area of ​​the activated carbon is approximately 550m². 2 / g to approximately 3500m 2 / g. In some embodiments, the activated carbon has a BET specific surface area of ​​approximately 600 m². 2 / g to approximately 2500m 2 / g, approximately 600m 2 / g to approximately 2250m 2 / g, approximately 600m 2 / g to approximately 2000m 2 / g, or approximately 700m 2 / g to approximately 2000m 2 / g. In other embodiments, the activated carbon has a BET specific surface area of ​​approximately 800 m². 2 / g to approximately 2500m 2 / g, approximately 800m 2 / g to approximately 2000m 2 / g, or approximately 1000m 2 / g to approximately 2000m 2 / g.

[0114] In other embodiments, the carbonaceous material is graphite. The graphite can be natural or synthetic in fine-grained, medium-grained, or coarse-grained grades. Typically, the graphite is synthetic graphite. Graphite suitable for use in conjunction with this invention is in powder form and has a particle size greater than 1 g / cm³. 3 The bulk density is more typically greater than approximately 1.1 g / cm³. 3 In some implementations, it is greater than approximately 1.2 g / cm³. 3 The graphite used in embodiments of the present invention is typically porous, with a porosity of about 0.5 vol% to about 60 vol%, more typically about 0.5 vol% to about 55 vol%.

[0115] In some embodiments, the carbonaceous material is a mixture of any two or more forms of carbon selected from carbon black, activated carbon, and graphite. The use of such mixtures enables properties that are moderate in relation to the individual carbon forms. For example, although graphite typically has a molecular weight of less than 20 μm... 2 The use of appropriate relative amounts of graphite and carbon black or activated carbon blends can produce a BET surface area greater than 20 m² / g. 2 A mixture of / g.

[0116] The amount of water used in this metal-carbon mixture is typically from about 15% to about 70% by weight. More typically, it is from about 15% to about 65% by weight, from about 15% to about 60% by weight, from about 15% to about 55% by weight, from about 15% to about 50% by weight, from about 15% to about 45% by weight, from about 20% to about 40% by weight, or from about 25% to about 40% by weight.

[0117] In some embodiments, the metal-carbon mixture comprises: about 0.1 wt% to about 50 wt% of a metal precursor; about 20 wt% to about 35 wt% of carbonaceous material; about 20 wt% to about 35 wt% of a monosaccharide or disaccharide; about 0.5 wt% to about 5 wt% of a polysaccharide; and about 25 wt% to about 45 wt% of water.

[0118] The metal-carbon mixture may contain additives such as molding aids (e.g., lubricants, waxes such as stearic acid and its salts); wetting agents (e.g., surfactants); pore-forming agents; adhesives; organic solvents; etc., and combinations of two or more of these.

[0119] During the mixing step, the order in which the components are added is not important. However, for ease of mixing, it may be desirable to premix some components before mixing all the components together. For example, when the metal precursor is water-soluble, it can be premixed with water and optionally a water-soluble organic binder before adding the carbonaceous material to the mixture. Typically, water and the water-soluble organic binder are premixed together to form a binder solution. In embodiments where the metal precursor is insoluble in water, it may be desirable to premix the metal precursor with the carbonaceous material, and then mix the resulting combined dry mixture with the binder solution.

[0120] The metal-carbon mixture may be heated during the mixing process to promote the dissolution of soluble components, such as any water-soluble polymer. For example, in some embodiments, the metal-carbon mixture, or the premix of water and binder and optionally a water-soluble metal precursor, is heated to a temperature of at least about 50°C, at least about 60°C, or at least about 70°C during the mixing step. In various embodiments, the water and binder may be heated to a temperature of about 50°C to about 95°C, about 50°C to about 90°C, or about 60°C to about 85°C. Industrial mixers, such as milling machines, planetary mixers, drum mixers, disc mixers, twin-shaft mixers, cement mixers, or other types of mixers suitable for mixing highly viscous materials, can be used for mixing.

[0121] Following the mixing step, the metal-carbon mixture is pliable and readily processed into the desired shape or form during the molding step to form a green-molded metal-carbon product. As used herein, the term "green-molded metal-carbon product" refers to a metal-carbon mixture shaped to the desired shape but not yet carbonized, or a mixture thereof that is partially or completely dehydrated. During the molding step, the metal-carbon mixture is transformed into the desired shape using methods such as pressing, casting, injection molding, extrusion, as a paste coating, shot granulation, calendering, or 3D printing, optionally followed by breaking such shapes into smaller fragments (i.e., smaller molding fragments). This molding step can be carried out at elevated temperatures to reduce the viscosity of the mixture and the corresponding forces required to process the material into the desired shape. In some embodiments, the molding step is carried out at a temperature of at least about 50°C, at least about 60°C, or at least about 70°C. In various embodiments, the molding step is carried out at temperatures from about 50°C to about 95°C, from about 50°C to about 90°C, or from about 60°C to about 85°C. Suitable forming methods for the metal-carbon mixture include those methods for forming or shaping carbon black mixtures described in PCT application WO 2015 / 168327 and US applications USSN62 / 247,721 and USSN15 / 131,829, each of which is incorporated herein by reference.

[0122] In some embodiments, it may be desirable to remove all or part of the water from the green-formed metal-carbon product in a drying step prior to the carbonization step. Typically, this drying step is performed at ambient temperature (e.g., about 20°C) and pressure, or at temperatures ranging from about 20°C to about 175°C, about 20°C to about 150°C, about 40°C to about 120°C, about 60°C to about 120°C, about 90°C to about 175°C, about 90°C to about 150°C, about 100°C to about 150°C, or about 100°C to about 140°C. This drying step can be performed under vacuum or at pressure reduced relative to ambient pressure. Methods for drying green-formed carbon products suitable for the methods of the present invention include those for drying formed carbon composite materials described in PCT application WO2015 / 168327 and US applications USSN62 / 247,721 and USSN15 / 131,829, each of which is hereby incorporated by reference.

[0123] Carbonization is typically performed by heating the green-formed metal-carbon product to temperatures of approximately 250°C to approximately 1,000°C, approximately 300°C to approximately 900°C, approximately 300°C to approximately 850°C, approximately 300°C to approximately 800°C, approximately 350°C to approximately 850°C, approximately 350°C to approximately 800°C, approximately 350°C to approximately 700°C, approximately 400°C to approximately 850°C, or approximately 400°C to approximately 800°C. Suitable methods for carbonizing green-formed metal-carbon products include those methods for carbonizing molded carbon composites described in published PCT application WO2015 / 168327 and US applications USSN62 / 247,721 and USSN15 / 131,829, each of which is hereby incorporated herein by reference. The carbonization step, in particular, renders water-soluble organic binders insoluble in water.

[0124] The methods described herein advantageously incorporate a wide variety of metals into porous but durable carbon-based materials. Exemplary porous shaped metal-carbon products include, for example, porous shaped Ni-carbon products; porous shaped W-carbon products; porous shaped Co-carbon products; and so on, as well as such products having other metals deposited thereon (on the inner and outer surfaces). As used herein, when a particular metal is listed as a “metal” or “metal component” of the metal-carbon product, it refers to the metal corresponding to the metal precursor compound, wherein such metal remains on and / or in the porous shaped metal-carbon product after the carbonization step. While not wishing to be bound by any theory, it is believed that in-situ carbonization of the metal precursor within the metal-carbon mixture can affect the metal distribution in / on the porous shaped metal-carbon product compared to the metal distribution in / on a corresponding control product. The “corresponding control product” in this case is made from a green shaped carbon product in which the metal is not incorporated but added after carbonization (e.g., by impregnation). The distinction may be more pronounced when using water-insoluble metal precursors in the methods of the invention.

[0125] While not wishing to be bound by theory, it is believed that the carbonization of this metal-carbon mixture can alter the textural properties (e.g., surface area and porosity) of the carbonized product compared to a carbonized product without incorporated metal. When preparing porous shaped tungsten (W)-carbon products, a higher BET surface area was observed compared to the corresponding shaped carbon products prepared without tungsten. Similarly, the BJH specific pore volume in the W-carbon products of the present invention is lower than that in the tungsten-free products. Furthermore, the average pore size in the W-carbon products of the present invention is relatively larger than that in the corresponding shaped carbon products prepared without tungsten.

[0126] The method of the present invention offers further advantages. For example, when the metal precursor can be decomposed and reduced to the metal at the carbonization temperature (i.e., in-situ reduction), further reduction steps can be avoided. Such a method is economically attractive. However, in various embodiments, it may be desirable to reduce the metal in the shaped metal-carbon product by contacting the product with a reducing agent, such as hydrogen (e.g., by flowing 5% H2 / N2 at 350°C for 3 hours). The reduction of the shaped metal-carbon product is illustrated in the examples.

[0127] The metal component of the porous shaped metal-carbon product is typically present at a metal loading of approximately 0.1 wt% to approximately 50 wt%, approximately 0.1 wt% to approximately 45 wt%, 0.1 wt% to approximately 40 wt%, approximately 0.1 wt% to approximately 35 wt%, approximately 0.1 wt% to approximately 30 wt%, or approximately 0.1 wt% to approximately 25 wt% of the total weight of the porous shaped metal-carbon product. In some embodiments, the metal loading is approximately 0.5 wt% to approximately 50 wt%, approximately 1 wt% to approximately 50 wt%, approximately 1 wt% to approximately 45 wt%, approximately 1 wt% to approximately 40 wt%, approximately 1 wt% to approximately 35 wt%, approximately 1 wt% to approximately 30 wt%, approximately 1 wt% to approximately 25 wt%, or approximately 1 wt% to approximately 20 wt% of the total weight of the porous shaped metal-carbon product.

[0128] The carbonized shaped metal-carbon product typically has a carbon content of approximately 50% to approximately 99.9% by weight. More typically, the carbon content is approximately 55% to approximately 99% by weight, approximately 60% to approximately 99% by weight, approximately 65% ​​to approximately 99% by weight, approximately 70% to approximately 99% by weight, or approximately 75% to approximately 99% by weight of the total weight of the porous shaped metal-carbon product. The carbon content of the shaped metal-carbon product is determined by the following formula: [(weight of carbonaceous material used to prepare the metal-carbon mixture) / (weight of the porous shaped metal-carbon product)] x 100%.

[0129] When carbon black is used in the preparation of carbonized metal-carbon products, the product is typically a mesopore-dense product with a high mesopore concentration, the mesopores having a diameter of about 10 nm to about 100 nm or about 10 nm to about 50 nm. In some embodiments, at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% of the pore volume of these shaped metal-carbon products can be attributed to pores having a pore size of about 10 nm to about 100 nm as measured by the BJH method (based on pores having a diameter of 1.7 nm to 100 nm). The term "mesopore-dense metal-carbon-based material" herein refers to a metal-carbon-based material prepared according to the methods described herein using carbon black as the carbonaceous material.

[0130] In certain mesoporous densely formed carbide metal-carbon products of the present invention, the contribution of pores having a pore size of about 10 nm to about 100 nm to the pore volume (based on pores having a diameter of 1.7 nm to 100 nm) is about 50% to about 95%, about 50% to about 90%, about 50% to about 80%, about 60% to about 95%, about 60% to about 90%, about 60% to about 80%, about 70% to about 95%, about 70% to about 90%, about 70% to about 80%, about 80% to about 95%, or about 80% to about 90%. In other embodiments, the contribution of pores having a diameter of about 10 nm to about 50 nm to the pore volume (based on pores having a diameter of 1.7 nm to 100 nm) is at least about 35%, at least about 40%, at least about 45%, or at least about 50% of the pore volume measured by the BJH method (based on pores having a diameter of 1.7 nm to 100 nm).

[0131] Typically, these mesoporous, densely formed carbide metal-carbon products have a relatively low concentration of pores with diameters less than 10 nm, less than 5 nm, or less than 3 nm. In some embodiments, as measured by the BJH method (based on pores with diameters from 1.7 nm to 100 nm), no more than about 10%, no more than about 5%, or no more than about 1% of the pore volume of these materials are less than 10 nm, less than 5 nm, or less than 3 nm. In other embodiments, as measured by the BJH method (based on pores with diameters from 1.7 nm to 100 nm), the contribution of pores with diameters less than 10 nm, less than 5, or less than 3 nm to the pore volume is about 0.1% to about 10%, about 0.1% to about 5%, about 0.1% to about 1%, about 1% to about 10%, about 0.1% to about 5%, about 0.1% to about 1%, about 1% to about 10%, or about 1% to about 5%.

[0132] In some embodiments, the mesoporous densely packed carbide-formed metal-carbon product of the present invention has a pore size distribution with no visible peaks below 10 nm, and in some embodiments, no visible peaks below 5 nm. In these and other embodiments, the mesoporous densely packed carbide-formed metal-carbon product has a pore size distribution with peak values ​​greater than about 5 nm, greater than about 7.5 nm, greater than about 10 nm, greater than about 12.5 nm, greater than about 15 nm, or greater than about 20 nm, and typically less than about 100 nm, less than about 90 nm, less than about 80 nm, or less than about 70 nm.

[0133] The mesoporous dense carbide-formed metal-carbon products of this invention typically have a porosity of approximately 20 μm. 2 / g to approximately 500m 2 / g BET specific surface area. In some embodiments, the BET specific surface area is approximately 20m². 2 / g to approximately 350m 2 / g, approximately 20m 2 / g to approximately 250m 2 / g, approximately 20m 2 / g to approximately 225m 2 / g, approximately 20m 2 / g to approximately 200m 2 / g, approximately 20m 2 / g to approximately 175m 2 / g, approximately 20m 2 / g to approximately 150m 2 / g, approximately 20m 2 / g to approximately 125m 2 / g, or approximately 20m 2 / g to approximately 100m 2 / g, approximately 25m 2 / g to approximately 500m 2 / g, approximately 25m 2 / g to approximately 350m 2 / g, approximately 25m 2 / g to approximately 250m 2 / g, approximately 25m 2 / g to approximately 225m 2 / g to approximately 150m 2 / g, approximately 25m 2 / g to approximately 125m 2 / g, approximately 25m 2 / g to approximately 100m 2 / g, approximately 30m 2 / g to approximately 500m 2 / g, approximately 30m 2 / g to approximately 350m 2 / g, approximately 30m 2 / g to approximately 250m 2 / g, approximately 30m 2 / g to approximately 225m 2 / g, approximately 30m 2 / g to approximately 200m 2 / g, approximately 30m 2 / g to approximately 175m 2 / g, approximately 30m 2 / g to approximately 150m 2 / g, approximately 30m 2 / g to approximately 125m 2 / g, or approximately 30m 2 / g to approximately 100m 2 / g.

[0134] As measured by the BJH method (based on pores with diameters ranging from 1.7 nm to 100 nm), the specific pore volume of mesoporous densely packed carbide-formed metal-carbon products prepared according to the methods described herein is typically greater than approximately 0.1 cm³. 3 / g. As measured by the BJH method (based on pores with diameters from 1.7 nm to 100 nm), the specific pore volume of this mesoporous densely shaped metal-carbon product is typically greater than approximately 0.2 cm³. 3 / g or greater than 0.3cm 3 / g. In some embodiments, the mesoporous densely packed carbide-formed metal-carbon product of the present invention has a density of approximately 0.1 cm. 3 / g to approximately 1.5cm 3 / g, approximately 0.1cm3 / g to approximately 0.9cm 3 / g, approximately 0.1cm 3 / g to approximately 0.8cm 3 / g, approximately 0.1cm 3 / g to approximately 0.7cm 3 / g, approximately 0.1cm 3 / g to approximately 0.6cm 3 / g, approximately 0.1cm 3 / g to approximately 0.5cm 3 / g, approximately 0.2cm 3 / g to approximately 0.8cm 3 / g, approximately 0.2cm 3 / g to approximately 0.7cm 3 / g, approximately 0.2cm 3 / g to approximately 0.6cm 3 / g, approximately 0.2cm 3 / g to approximately 0.5cm 3 / g, approximately 0.3cm 3 / g to approximately 1cm 3 / g, approximately 0.3cm 3 / g to approximately 0.9cm 3 / g, approximately 0.3cm 3 / g to approximately 0.8cm 3 / g to approximately 1cm 3 / g, approximately 0.3cm 3 / g to approximately 0.9cm 3 / g, approximately 0.3cm 3 / g to approximately 0.8cm 3 / g, approximately 0.3cm 3 / g to approximately 0.7cm 3 / g, approximately 0.3cm 3 / g to approximately 0.6cm 3 / g, or approximately 0.3cm 3 / g to approximately 0.5cm 3 / g is the specific pore volume of pores with diameters ranging from 1.7 nm to 100 nm, as measured by the BJH method.

[0135] The mesoporous densely packed carbide-formed metal-carbon products of the present invention typically exhibit relatively high mechanical strength and stability, particularly under aqueous conditions. In some embodiments, these materials contain a radial piece crush strength greater than about 4.4 N / mm (1 lb / mm). In other embodiments, the mesoporous densely packed carbide-formed metal-carbon product contains a radial piece crush strength greater than about 8.8 N / mm (2 lbs / mm) or greater than about 13.3 N / mm (3 lbs / mm). In some embodiments, the radial piece crush strength of the mesoporous densely packed carbide-formed metal-carbon product of the present invention is from about 4.4 N / mm (1 lb / mm) to about 88 N / mm (20 lbs / mm), from about 4.4 N / mm (1 lb / mm) to about 66 N / mm (15 lbs / mm), or from about 8.8 N / mm (1 lb / mm) to about 44 N / mm (10 lbs / mm). As used herein, the term “radial sheet crushing strength” refers to the sheet crushing strength test procedure described in ASTM D4179 or ASTM D6175, which is incorporated herein by reference. Although some test methods limit the particles to a specified range of sizes, geometries, or manufacturing methods, these and similar test methods are sufficient to measure the crushing strength of irregularly shaped particles and particles of various sizes and manufacturing methods.

[0136] In some embodiments, the mesoporous densely packed carbide-formed metal-carbon products prepared according to the methods described herein exhibit atrium resistance and abrasion resistance characteristics. In these embodiments, the mesoporous densely packed carbide-formed metal-carbon product (prepared in extrusion form for this test) typically exhibits a rotating drum attrition index, as measured according to ASTM D4058-96, where more than at least about 85 wt% remains on a 20-mesh sieve after continuous rotation at 55 RPMs for 35 minutes in a rotating test drum. In some embodiments, these materials exhibit a rotating drum attrition index where more than at least about 90 wt%, more than about 91 wt%, more than about 92 wt%, more than about 93 wt%, more than about 94 wt%, more than about 95 wt%, more than about 96 wt%, more than about 97 wt%, more than about 98 wt%, or more than about 99 wt% remains on a 20-mesh sieve in the aforementioned abrasion test method.

[0137] The mesoporous densely packed carbide-formed metal-carbon products of the present invention typically exhibit minimal abrasion loss after a period of intense horizontal agitation. The term “abrasion loss” as used herein refers to the tolerance of a material to abrasion attributable to intense horizontal agitation of particles, measured within the limits of a 30-mesh sieve. The material was tested as follows: (1) the test material was first dusted on a 20-mesh sieve by gently moving the sieve from side to side at least 20 times; (2) the dusted sample was weighed and then transferred to a clean 30-mesh sieve stacked on a clean sieve rack for collecting fine particles; (3) the completed sieve stack was then assembled onto a sieve shaker (e.g., a RO-Tap RX-29 sieve shaker from WSTyler Industrial Group, Mentor, OH), securely covered, and shaken for approximately 30 minutes; (4) the resulting fine particles were weighed; and (5) the percentage abrasion loss by weight was calculated by dividing the weight of the collected fine particles by the weight of the dusted sample. In some embodiments, the mesoporous dense carbonized metal-carbon products of the present invention exhibit horizontal agitator wear losses of less than about 5%, less than about 3%, less than about 2%, less than about 1%, less than about 0.5%, less than about 0.2%, less than about 0.1%, less than about 0.05%, or less than about 0.03%.

[0138] In some applications, shaped metal-carbon products with relatively high surface areas, i.e., those with a surface area greater than approximately 500m², may be desirable. 2 / g BET specific surface area. The term "high surface area molded metal-carbon product" is used herein to refer to a molded metal-carbon product prepared according to the method of the present invention, in which the carbonaceous material is activated carbon. The high surface area molded metal-carbon products of the present invention typically exhibit a BET specific surface area greater than 500 m² / g. 2 / g BET specific surface area. In some embodiments, the BET specific surface area of ​​these materials is approximately 550m². 2 / g to approximately 3500m 2 / g. In some embodiments, these high surface area materials have a BET specific surface area of ​​approximately 600 m². 2 / g to approximately 2500m 2 / g, approximately 600m 2 / g to approximately 2250m 2 / g, approximately 600m 2 / g to approximately 2000m 2 / g, or approximately 700m 2 / g to approximately 2000m 2 / g. In other embodiments, the BET specific surface area of ​​this high surface area carbide-formed metal-carbon product is approximately 800 m². 2 / g to approximately 2500m 2 / g, approximately 800m 2 / g to approximately 2000m 2 / g, or approximately 1000m 2 / g to approximately 2000m 2 / g.

[0139] The high surface area formed metal-carbon products of this invention typically have a higher pore concentration of less than 10 nm than the mesoporous dense formed metal-carbon products described herein. Typically, as measured by the BJH method (based on pores with diameters from 1.7 nm to 100 nm), pores with a diameter of less than 10 nm contribute more than 10%, more than about 20%, or more than about 25% to the pore volume.

[0140] In some embodiments, when, for example, improved conductivity is required, it may be desirable to use graphite as a carbonaceous material in the preparation of the product of the present invention. When graphite is used alone as a carbonaceous material, the molded metal-carbon product typically has a conductivity of less than 20 μm. 2 / g BET specific surface area. However, as mentioned above, the porosity can be adjusted for the desired application using a mixture of graphite with carbon black and / or activated carbon in the metal-carbon mixture.

[0141] The porous shaped metal-carbon products of the present invention can be thermally or chemically treated to alter their physical and / or chemical properties. For example, the product can be chemically treated with an oxidizing agent to produce a more hydrophilic surface. In some embodiments, the porous shaped metal-carbon product can be surface-treated using known methods to attach desired functional groups to the surface of the material. See, for example, WO 2002 / 018929, WO97 / 47691, WO99 / 23174 and WO99 / 31175, which are incorporated herein by reference.

[0142] In some embodiments, it may be desirable to deposit additional metals onto the surface of the porous shaped metal-carbon product of the present invention (including the inner pore surface and the outer surface of the material), such as for certain catalytic applications. In these embodiments, a second metal (or a precursor thereof) is deposited onto the surface of the porous shaped metal-carbon product of the present invention, wherein the second metal comprises the same or different metal as the metal in the first metal precursor (i.e., the metal precursor incorporated into the metal-carbon mixture).

[0143] For catalytic applications, the second metal and the metal precursor can be any metal / metal precursor known to be suitable for catalytic applications / catalyst fabrication. The second metal or its precursor may comprise a base metal or a noble metal. In some embodiments, the second metal or its precursor comprises a metal selected from groups IV, V, VI, VII, VIII, IX, X, XI, XII, and XIII. In various embodiments, the metal is a d-block metal. Exemplary d-block metals include, for example, Ni, Co, W, Cu, Zn, Fe, Mo, Ni, Rh, Pd, Ag, Os, Ir, Pt, Au, etc.

[0144] In other embodiments, the second metal or its precursor comprises a metal selected from Cu, Pb, Ni, Zn, Fe, Mo, Al, Sn, W, Ta, Co, Bi, Cd, Ti, Zr, Sb, Mn, Be, Cr, Ge, V, Ga, Hf, In, Nb, Rh, Tl, Ru, Rh, Pd, Ag, Os, Ir, Pt, or Au. The second metal is typically a noble metal. In a specific embodiment, the second metal or its precursor comprises a metal selected from Cu, Pb, Ni, Zn, Fe, Mo, Al, Sn, W, Ta, Co, Bi, Cd, Ti, Zr, Sb, Mn, Be, Cr, Ge, V, Ga, Hf, In, Nb, Rh, and Tl.

[0145] In this step, known methods such as initial wet impregnation, ion exchange, deposition-precipitation, coating, vacuum impregnation, etc., are typically used to contact the shaped metal-carbon product with a metal precursor dissolved in a liquid medium. In some embodiments, after the deposition of the second metal, the resulting material is optionally dried, for example at a temperature of at least about 50°C, more typically at least about 120°C, for a period of time, typically at least about 1 hour, more typically at least about 3 hours or longer. Alternatively, the drying can be carried out continuously or in stages, using independently controlled temperature zones (e.g., 60°C, 80°C, and 120°C). Typically, drying is initiated by raising the temperature of the wet material to a temperature initially below the boiling point of the liquid medium, and then increasing the temperature.

[0146] After deposition and optional drying, the resulting product is heated in the presence of a reducing agent, such as hydrogen (e.g., a synthesis gas of 5% H2 and 95% N2), to reduce the metal precursor to a metal. The heating temperature is typically from about 150°C to about 600°C, from about 200°C to about 500°C, or from about 100°C to about 400°C. Heating typically takes place for about 1 hour to about 5 hours or from about 2 hours to about 4 hours. Reduction can also be carried out in the liquid phase. For example, metal deposition on the porous shaped metal-carbon product can be carried out in a fixed bed by pumping a liquid containing a reducing agent through the static composite material. In some embodiments, the resulting catalyst material is calcined, for example, at a temperature of at least about 200°C for a period of time (e.g., at least about 1, 2, or 3 hours). Example 7 illustrates the deposition of a second metal onto the surface of the shaped metal-carbon product, followed by drying, reduction, and depleted air calcination.

[0147] In some embodiments, the surface-deposited metal is present in the form of the porous carbide-formed metal-carbon product at a weight percentage of approximately 0.1% to approximately 50%, approximately 0.1% to approximately 25%, approximately 0.1% to approximately 10%, approximately 0.1% to approximately 5%, approximately 0.25% to approximately 50%, approximately 0.25% to approximately 25%, approximately 0.25% to approximately 10%, approximately 0.25% to approximately 5%, approximately 1% to approximately 50%, approximately 1% to approximately 25%, approximately 1% to approximately 10%, approximately 1% to approximately 5%, approximately 5% to approximately 50%, approximately 5% to approximately 25%, or approximately 5% to approximately 10%. When the surface-deposited metal is a precious metal, it is typically present in an amount of approximately 0.25% to approximately 10% by weight. When the surface-deposited metal is a non-precious metal, it is typically present in an amount of approximately 0.1% to approximately 50% by weight.

[0148] The porous molded metal-carbon product of this invention is particularly suitable for use as a catalyst. As demonstrated in the examples, the type of catalytic activity can be tailored to a specific reaction by changing the type of metal used in the metal precursor. In some embodiments, this catalytic activity is hydrogenation activity, deoxygenation activity, oxidation activity, reduction activity, dehydration activity, or other known catalytic activity using a known active metal that can be carried out in a gaseous or liquid medium. The porous molded metal-carbon product can be used as a catalyst in batch, semi-batch, or continuous reactor formats known in the art, such as fixed-bed reactors, trickle-bed reactors, slurry-phase reactors, moving-bed reactors, etc. The product is suitable for gas-phase or liquid-phase reactions. The porous molded metal-carbon product is compatible with a wide variety of solvents, including organic solvents, as well as water and combinations thereof. Suitable compatible solvents include, for example, alcohols such as ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, isobutanol, sec-butanol, etc.; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, etc.; ethers such as dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, etc.; water; and mixtures thereof.

[0149] In one embodiment, the present invention provides a method for producing 2,5-bis-hydroxymethylfuran (BHMF) from 5-hydroxymethylfurfural (HMF), the method comprising:

[0150] HMF is contacted with hydrogen in the presence of a hydrogenation catalyst comprising the porous shaped metal-carbon product of the present invention to form BHMF, wherein the metal component of the porous shaped metal-carbon product is selected from Ni, Zn, Co, Cu, Ag, Pt, Pd, Fe, Ru, Au, W, Sb, Bi, Pb, and combinations thereof. In some embodiments, the metal component of the porous shaped metal-carbon product is a metal combination selected from Co / Cu, Ni / Cu, Ag / Ni, Ag / Co, and Ag / Ru. Typically, the metal component of the porous shaped metal-carbon product of the present invention is a metal selected from Ni, Cu, and mixtures thereof.

[0151] The porous shaped metal-carbon product typically contains a loading of about 0.5 wt% to about 99 wt% of a metal component. In some embodiments, this loading is about 0.1 wt% to about 25 wt%, or about 0.1 wt% to about 20 wt%, or about 0.1 wt% to about 18 wt%. When the porous shaped metal-carbon product contains two different types of metal components M1 and M2, the molar ratio of metal 1 to metal 2 (M1:M2) is typically about 25:1 to about 1:25, or about 25:1 to about 2:1, or about 20:1 to about 5:1.

[0152] The contact step is typically performed at a temperature of approximately 50°C to approximately 150°C, or approximately 80°C to approximately 130°C. In one embodiment, the hydrogen pressure during the contact step is approximately 50 psig to approximately 2000 psig. In another embodiment, the hydrogen pressure is approximately 100 psig to approximately 1500 psig. In a further embodiment, the hydrogen pressure is approximately 200 psig to approximately 1000 psig.

[0153] This contact step is typically carried out in an organic solvent, such as an alcohol, ester, ether, or a mixture thereof. Exemplary alcohols include, for example, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, isobutanol, sec-butanol, etc. Exemplary esters include, for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, etc. Exemplary ethers include, for example, dioxane, dioxolane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether. In one embodiment, the organic solvent contains less than about 25% by weight of water. In another embodiment, the organic solvent contains less than about 10% by weight of water. In another embodiment, the organic solvent contains less than about 5% by weight of water. In yet another embodiment, the organic solvent is substantially water-free.

[0154] In one embodiment, BHMF is generated from HMF with at least approximately 90% selectivity. In another embodiment, BHMF is generated from HMF with at least 95% selectivity. In some embodiments, BHMF is generated from HMF with at least 99% selectivity.

[0155] In some embodiments, at least approximately 85% of HMF is converted to BHMF. In some embodiments, at least approximately 90% of HMF is converted to BHMF. In other embodiments, at least approximately 95% of HMF is converted to BHMF. In a further embodiment, at least approximately 99% of HMF is converted to BHMF.

[0156] In one embodiment, the present invention provides a method for producing bis-hydroxymethyltetrahydrofuran (BHMTHF) from 2,5-bis-hydroxymethylfuran (BHMF), the method comprising:

[0157] BHMF is contacted with hydrogen in the presence of a multiphase hydrogenation catalyst comprising the porous shaped metal-carbon product of the present invention to form BHMTHF, wherein the metal component of the metal-carbon product is selected from Ni, Co, Cu, Ag, Pd, Pt, Ru, and combinations thereof. In some embodiments, the metal component is selected from Ni, Co, Pd, Ru, and Pt. In some embodiments, the metal component is selected from Ni, Pd, Co, and Pt. In other embodiments, the metal component is a combination of metals, such as those selected from Co and Cu; Ni and Cu, Ru and Cu; Ag and Ni; Ag and Co; Ag and Ru; and combinations of Cu, Co, and Ni. The metal component is typically Ni.

[0158] This porous molded metal-carbon product typically contains a loading of metal component from about 0.5 wt% to about 99 wt%. In some embodiments, this loading is from about 0.01 wt% to about 25 wt%, or from about 0.1 wt% to about 20 wt%, or from about 0.1 wt% to about 18 wt%. When the composite material contains two different metal species M1 and M2, the molar ratio of metal 1 to metal 2 (M1:M2) is typically from about 25:1 to about 1:25, or from about 25:1 to about 2:1, or from about 20:1 to about 5:1.

[0159] The contact step is typically performed at a temperature of approximately 80°C to approximately 150°C, or approximately 80°C to approximately 130°C. In one embodiment, the hydrogen pressure during the contact step is approximately 50 psig to approximately 2000 psig. In another embodiment, the hydrogen pressure is approximately 100 psig to approximately 1500 psig. In a further embodiment, the hydrogen pressure is approximately 200 psig to approximately 1000 psig.

[0160] This contact step is typically carried out in an organic solvent, such as an alcohol, ester, ether, or a mixture thereof. Exemplary alcohols include, for example, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, isobutanol, sec-butanol, etc. Exemplary esters include, for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, etc. Exemplary ethers include, for example, dioxane, dioxolane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether. In one embodiment, the organic solvent contains less than about 25% by weight of water. In one embodiment, the organic solvent is a mixture of 90% organic solvent and 10% water (v / v). In another embodiment, the organic solvent contains less than about 10% by weight of water. In another embodiment, the organic solvent contains less than about 5% by weight of water. In yet another embodiment, the organic solvent is substantially water-free.

[0161] In one embodiment, BHMTHF is generated from BHMF with at least approximately 80% selectivity. In some embodiments, BHMTHF is generated from BHMF with at least approximately 85% or at least approximately 90% selectivity. In another embodiment, BHMTHF is generated from BHMF with at least approximately 95% selectivity. In some embodiments, BHMTHF is generated from BHMF with at least 99% selectivity.

[0162] In some embodiments, at least approximately 85% of BHMF is converted to BHMTHF. In some embodiments, at least approximately 90% of BHMF is converted to BHMTHF. In other embodiments, at least approximately 95% of BHMF is converted to BHMTHF. In a further embodiment, at least approximately 99% of BHMF is converted to BHMTHF. Example 5 illustrates the use of a porous shaped Ni-carbon product as a heterogeneous hydrogenation catalyst to convert BHMF to BHMTHF.

[0163] In another embodiment, the present invention provides a method for producing corresponding C3-C6 diols from C3-C6 polyols, the method comprising:

[0164] C3-C6 polyols are contacted with hydrogen in the presence of a hydrodeoxygenation catalyst comprising the porous shaped metal-carbon product of the present invention to form the corresponding C3-C6 diols, wherein the metal component of the porous shaped metal-carbon product is selected from Pd, Pt, Ir, Mo, W, V, Mn, Re, Zr, Ni, Cu, La, Sm, Y, Zn, Cr, Ge, Sn, Ti, Au, Rh, Co, and combinations thereof. In some embodiments, the metal component is selected from Pt, W, and Mo. In some embodiments, the metal is selected from Pt and W. In other embodiments, the metal is W.

[0165] The porous molded metal-carbon product typically contains a loading of about 0.5 wt% to about 10 wt% of metal components. In some embodiments, this loading is about 0.2 wt% to about 10 wt%, or about 0.2 wt% to about 8 wt%, or about 0.2 wt% to about 5 wt%. In some embodiments, the total weight of the metal components is less than about 4 wt% of the total weight of the porous molded metal-carbon product. When the product contains two different types of metal components M1 and M2, the molar ratio of metal 1 to metal 2 (M1:M2) is typically about 20:1 to about 1:10, or about 10:1 to about 1:5, or about 8:1 to about 1:2.

[0166] In some embodiments, the C3-C6 diol is selected from 1,5-pentanediol and 1,6-hexanediol. The C3-C6 diol may also be selected from 1,2,6-hexanetriol, 1,2,5-pentanetriol, 2H-tetrahydropyran-2-methanol, tetrahydrofuran-2,5-diethanol, furan-2,5-diethanol, 2,5-dihydrofuran-2,5-diethanol, L-glucanone, L-glucan, levoglucosenol, 1,6-dehydro-3,4-dideoxy-pD-pyranose-2-one, isosorbide, C3-C6 polyols, including hydroxymethylfurfural, sorbitol, glucose, fructose, xylitol, 3,4-dihydro-2H-pyran-2-carboxaldehyde, 1,2,5,6-hexanetetrol, 1,2,3,5,6-hexanepentol, 1,5-dehydro-3,4-dideoxyhexitol, 5-hydroxy-2H-tetrahydropyran-2-methanol, furfural, furfuryl alcohol, tetrahydrofurfuryl alcohol, pentoses, and hexoses, can be produced directly or indirectly via one or more intermediates. Indirect production of C3-C6 diols can occur via intermediates such as furan-diethanol, tetrahydrofuran-diethanol, tetrahydropyran-2-methanol, levoglucosanol, and furfuryl alcohol.

[0167] The conversion of C3-C6 polyols to the corresponding C3-C6 diols can be carried out in the presence of a solvent. Solvents suitable for converting C3-C6 polyols to the corresponding C3-C6 diols in the presence of the catalyst of this invention include, for example, esters, alcohols, esters, ethers, ketones, or mixtures thereof. In various embodiments, water is the preferred solvent.

[0168] In one exemplary method, the C3-C6 polyol is 1,2,6-hexanetriol (HTO) and the C3-C6 diol is 1,6-hexanediol (HDO). Typically, the metal component of this porous molded metal-carbon product is a metal selected from Mo, W, and mixtures thereof. More typically, the porous molded metal-carbon product has a second metal deposited thereon (on both the inner and outer surfaces). Typically, this molded metal-carbon product is a porous molded W-carbon product having platinum deposited thereon (on both the inner and outer surfaces).

[0169] In one embodiment, the contact step is performed at a temperature of approximately 80°C to approximately 200°C. In another embodiment, the contact step is performed at a temperature of approximately 100°C to approximately 180°C. Typically, the hydrogen pressure during the contact step is approximately 200 psig to approximately 5000 psig, approximately 200 psig to approximately 4000 psig, approximately 200 psig, or 500 psig to approximately 3000 psig. In still other embodiments, the hydrogen pressure is approximately 200 psig or 500 psig to approximately 2000 psig.

[0170] In one embodiment, the desired C3-C6 diol is selectively generated from C3-C6 diol with at least about 80% selectivity. In another embodiment, the desired C3-C6 diol is selectively generated from C3-C6 diol with at least about 81%, at least about 82%, at least about 83%, at least about 84%, at least about 85%, at least about 86%, at least about 87%, at least about 88%, at least about 89%, at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 96%, at least about 97%, at least about 98%, or at least about 99% selectivity. In some embodiments, at least about 25% of the C3-C6 polyol is converted to the desired C3-C6 diol. In some embodiments, at least about 30% of the C3-C6 polyol is converted to the desired C3-C6 diol. In other embodiments, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, or at least about 95% of the C3-C6 polyol is converted into the desired C3-C6 diol. In one specific embodiment, the C3-C6 polyol is 1,2,6-hexanetriol and the C3-C6 diol is 1,6-hexanediol.

[0171] In another embodiment, the present invention provides a method for selectively amination of 1,6-hexanediol (HDO) to 1,6-hexanediamine (HMDA), comprising contacting 1,6-hexanediol with an amine in the presence of an amination catalyst comprising a porous shaped metal-carbon product of the present invention, wherein the metal component of the porous shaped metal-carbon product is selected from Ni, Ru, and Rh. The metal component is typically Ni. In some embodiments of this method, Ru and / or Rh are deposited as a second metal (or a mixture of metals) on the porous shaped metal-carbon product. Typically, the total weight of the metals is from about 0.1% to about 10%, from about 1% to about 6%, or from about 1% to about 5% of the total weight of the catalyst composition.

[0172] In this method, the molar ratio of Ru to Rh is important when both Ru and Rh are used. A byproduct of the method for converting HDO to HMDA is pentyramine. Pentyramine is an off-path byproduct of the HDO to HMDA conversion and cannot be converted to HMDA or to an intermediate that can be converted to HMDA in further reactions in the presence of the catalyst of this invention. However, the presence of too much rhodium has an adverse effect on the HMDA yield per unit area time (often referred to as space-time yield or STY). Therefore, the Ru:Rh molar ratio should be maintained in the range of about 20:1 to about 4:1. In various embodiments, the Ru:Rh molar ratio is about 10:1 to about 4:1 or about 8:1 to about 4:1. In some embodiments, a Ru:Rh molar ratio of about 8:1 to about 4:1 produces HMDA in a yield of at least 25%, with an HMDA / pentylamine ratio of at least 20:1, at least 25:1, or at least 30:1.

[0173] According to the present invention, HDO is converted to HMDA by reacting with an amine, such as ammonia, in the presence of the porous shaped metal-carbon product of the present invention. Typically, in some embodiments, the amine may be added to the reaction in gaseous or liquid form. Typically, the molar ratio of ammonia to HDO is at least about 40:1, at least about 30:1, or at least about 20:1. In various embodiments, it ranges from about 40:1 to about 5:1, or from about 30:1 to about 10:1. The reaction of HDO with the amine in the presence of the catalyst of the present invention is carried out at a temperature less than or equal to about 200°C. In various embodiments, the catalyst is contacted with HDO and the amine at a temperature less than or equal to about 100°C. In some embodiments, the catalyst is contacted with HDO and the amine at a temperature of about 100°C to about 180°C or about 140°C to about 180°C.

[0174] Typically, according to the invention, the reaction is carried out at a pressure not exceeding about 1500 psig. In various embodiments, the reaction pressure is from about 200 psig to about 1500 psig. In other embodiments, the pressure is from about 400 psig to about 1200 psig. In some preferred embodiments, the pressure is from about 400 psig to about 1000 psig. In some embodiments, the disclosed pressure range includes the pressure of NH3 gas and an inert gas such as N2. In some embodiments, the pressure of NH3 gas is about 50-150 psig and the pressure of the inert gas such as N2 is from about 700 psig to about 1450 psig.

[0175] In some embodiments, the catalyst is contacted with HDO and ammonia at a temperature of about 100°C to about 180°C and a pressure of about 200 psig to about 1500 psig. In other embodiments, the catalyst is contacted with HDO and ammonia at a temperature of about 140°C to about 180°C and a pressure of about 400 psig to about 1200 psig. In some embodiments, the disclosed pressure range includes the pressure of NH3 gas and an inert gas such as N2. In some embodiments, the pressure of NH3 gas is about 50-150 psig and the pressure of the inert gas such as N2 is about 500 psig to about 1450 psig.

[0176] The method of the present invention can be carried out in the presence of hydrogen. Typically, in those embodiments in which HDO and amines are reacted in the presence of hydrogen and the catalyst of the present invention, the partial pressure of hydrogen is equal to or less than about 100 psig.

[0177] The conversion of HDO to HMDA can also be carried out in the presence of a solvent. Suitable solvents for the conversion of HDO to HMDA in the presence of the catalyst of this invention may include, for example, water, alcohols, esters, ethers, ketones, or mixtures thereof. In various embodiments, water is the preferred solvent.

[0178] The chemicatalytic conversion of HDO to HMDA may produce one or more byproducts, such as pentylamine and hexylamine. Byproducts subsequently converted to HMDA through further reactions in the presence of the catalyst of the present invention are considered on-path byproducts. Other byproducts, such as pentylamine and hexylamine, are considered off-path byproducts for the reasons discussed above. According to the present invention, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, or at least 70% of the product mixture from a single-pass reaction of HDO with an amine (e.g., ammonia) in the presence of the catalyst of the present invention are HMDA.

[0179] The resulting product mixture can be separated into one or more products by any suitable method known in the art. In some embodiments, the product mixture can be separated by fractionation at pressures below atmospheric pressure. For example, in some embodiments, HMDA can be separated from the product mixture at temperatures of approximately 180°C and approximately 220°C. HDO can be recovered from any remaining other products of the reaction mixture by one or more conventional methods known in the art, including, for example, solvent extraction, crystallization, or evaporation. On-path byproducts can be recycled to the reactor used to produce the product mixture, or, for example, fed to a second reactor where the on-path byproducts are further reacted with ammonia in the presence of the catalyst of the present invention to produce additional HMDA.

[0180] One series of catalytic applications for the porous molded metal-carbon product of the present invention is the selective oxidation of hydroxyl groups to carboxyl groups in a liquid or gaseous reaction medium. An exemplary reaction is the selective oxidation of aldoses to aldonic diacids. Aldoses include, for example, pentoses and hexoses (i.e., C-5 and C-6 monosaccharides). Pentoses include ribose, arabinose, xylose, and lythose, while hexoses include glucose, allose, arbutin, mannose, gulose, idole, galactose, and tarose. Accordingly, in various embodiments, the present invention also relates to a method for the selective oxidation of aldoses to aldonic diacids, comprising reacting the aldose with oxygen in the presence of an oxidizing catalyst comprising the porous molded metal-carbon product of the present invention to form aldonic diacids. Typically, the porous molded metal-carbon product is a base metal-carbon product having a noble metal, such as platinum, deposited thereon (i.e., on both the outer and inner surfaces). More typically, the noble metal is a mixture of platinum and gold. The base metal component of the base metal-carbon product is typically tungsten.

[0181] In one specific embodiment, the present invention provides a method for the selective oxidation of glucose to gluconic acid, comprising contacting glucose with oxygen in the presence of an oxidation catalyst comprising a porous shaped metal-carbon product as described herein to form gluconic acid. Typically, the porous shaped metal-carbon product is a base metal-carbon product having a noble metal, such as platinum, deposited thereon (i.e., on both the outer and inner surfaces). More typically, the noble metal is a mixture of platinum and gold. The base metal component of the base metal-carbon product is typically tungsten. Example 14 describes the conversion of glucose to gluconic acid using Au-Pt on a porous shaped W-carbon product.

[0182] U.S. Patent No. 8,669,397 (the entire contents of which are incorporated herein by reference) discloses various catalytic methods for the oxidation of glucose to gluconic acid. Generally, glucose can be converted to gluconic acid in high yield by reacting glucose with oxygen (e.g., air, oxygen-enriched air, oxygen alone, or oxygen containing other components substantially inert to the reaction) in the presence of an oxidation catalyst according to the following reaction:

[0183]

[0184] The oxidation can be carried out without the addition of an external base (e.g., KOH) or with the initial pH of the reaction medium and / or the pH of the reaction medium at any point in the reaction being no greater than about 7, 7.0, 6.5, or 6. 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. In practice, catalytic selectivity can be maintained to achieve gluconic acid yields of more than about 30%, 40%, 50%, and 60%, and in some cases, yields of more than 65% or higher. The absence of an external base advantageously facilitates the separation and segregation of gluconic acid, thereby providing a method more suitable for industrial applications and improving overall process economy by eliminating reaction components. As used herein, "without an external base" means that if a base is present (e.g., as a component of the feedstock), it is present at a concentration that does not substantially affect the reaction efficacy; that is, the oxidation reaction is carried out with substantially no external base. The oxidation reaction can also be carried out in the presence of weak carboxylic acids, such as acetic acid (in which glucose is soluble). As used herein, the term “weak carboxylic acid” means any unsubstituted or substituted carboxylic acid having a pKa of at least about 3.5, more preferably at least about 4.5, and is more particularly selected from unsubstituted acids such as acetic acid, propionic acid, or butyric acid, or mixtures thereof.

[0185] The oxidation reaction can be carried out at increased oxygen partial pressure and / or higher oxidation reaction mixture temperature, which tends to increase the gluconic acid yield when the reaction is carried out without the addition of an external base or at a pH below approximately 7. Typically, the oxygen partial pressure is at least approximately 15 psia (104 kPa), at least approximately 25 psia (172 kPa), at least approximately 40 psia (276 kPa), or at least approximately 60 psia (414 kPa). In various embodiments, the partial pressure of oxygen is at most about 1,000 psia (6895 kPa), and more typically from about 15 psia (104 kPa) to about 500 psia (3447 kPa), about 75 psia (517 kPa) to about 500 psia (3447 kPa), about 100 psia (689 kPa) to about 500 psia (3447 kPa), or about 150 psia (1034 kPa) to about 500 psia (3447 kPa). Typically, the temperature of the oxidation reaction mixture is at least about 40°C, at least about 60°C, at least about 70°C, at least about 80°C, at least about 90°C, at least about 100°C, or higher. In various embodiments, the temperature of the oxidation reaction mixture is about 40°C to about 200°C, about 60°C to about 200°C, about 70°C to about 200°C, about 80°C to about 200°C, about 80°C to about 180°C, about 80°C to about 150°C, about 90°C to about 180°C, or about 90°C to about 150°C.

[0186] The oxidation of glucose to gluconic acid can also be carried out without nitrogen as the active reactant. Some methods use nitrogen compounds such as nitric acid as the oxidant. The use of nitrogen as an active reactant, such as nitrates or nitric acid, necessitates the use of NO. x Both emission reduction and acid regeneration technologies significantly increase the cost of producing gluconic acid by these known methods and provide a corrosive environment that can harmfully affect the equipment used to implement the methods. Conversely, in the case of using air or oxygen-enriched air as the oxygen source in the oxidation reaction of the present invention, nitrogen is essentially an inactive or inert component. Therefore, the oxidation reaction using air or oxygen-enriched air is a reaction carried out in the absence of nitrogen in essentially no reactive reactive form.

[0187] A method suitable for depositing platinum and gold, including the identification of suitable precursors, is described in U.S. Patent Application Publication 2011 / 0306790, which is incorporated herein by reference. This disclosure describes various oxidation catalysts comprising catalytically active components containing platinum and gold, which can be used for the selective oxidation of compositions consisting of primary alcohols. When platinum is used, the mass ratio of glucose to platinum is typically from about 10:1 to about 1000:1, from about 10:1 to about 500:1, from about 10:1 to about 200:1, or from about 10:1 to about 100:1.

[0188] In another series of chemical transformations, this porous shaped metal-carbon product is suitable as a hydrodeoxygenation catalyst for the hydrodeoxygenation of carbon-hydroxyl groups in liquid or gaseous reaction media to form carbon-hydrogen groups. For example, a series of chemical transformations in which the catalyst compositions of the present invention are particularly suitable is the selective halide-promoted hydrodeoxygenation of aldonic acid or its salts, esters or lactones to dicarboxylic acids. Accordingly, the porous shaped metal-carbon product of the present invention as described herein can be used as a hydrodeoxygenation catalyst. Therefore, the present invention also relates to a selective halide-promoted hydrodeoxygenation method of aldonic acid, comprising contacting aldonic acid or its salts, esters or lactones with hydrogen in the presence of a halogenated compound and a hydrodeoxygenation catalyst comprising the porous shaped metal-carbon product of the present invention to form a dicarboxylic acid. Typically, this porous shaped metal-carbon product is a porous shaped base metal-carbon product having at least one noble metal deposited thereon (on the outer and inner surfaces). Typically, the precious metal is selected from Ru, Rh, Pd, Pt, Au, Ag, Os, Ir, and combinations thereof. The metal composition of the porous shaped metal-carbon product is typically selected from Co, Ni, Ti, V, Cr, Mn, Fe, Cu, Mo, W, and combinations thereof.

[0189] The hydrodeoxygenation catalyst of the present invention can be used for the selective halide-promoted hydrodeoxygenation of gluconic acid or its salts, esters or lactones to adipic acid. U.S. Patent No. 8,669,397, mentioned above and incorporated herein by reference, describes a chemical catalytic method for the hydrodeoxygenation of gluconic acid to adipic acid.

[0190] Adipic acid or its salts and esters can be prepared by reacting gluconic acid or its salts, esters or lactones with hydrogen in the presence of a hydrodeoxygenation catalyst and a halogen source according to the following reactions:

[0191]

[0192] In the above reaction, gluconic acid or its salts, esters, or lactones are converted to adipic acid products via catalytic hydrodeoxygenation, wherein a carbon-hydroxyl group is converted to a carbon-hydrogen group. In various embodiments, the catalytic hydrodeoxygenation is hydroxyl-selective, wherein the reaction is carried out with substantially no conversion of the one or more other non-hydroxyl functional groups of the substrate.

[0193] The halogen source can be selected from ionic, molecular, and mixtures thereof. Halogen sources include hydrohalic acids (e.g., HCl, HBr, HI, and mixtures thereof; preferably HBr and / or HI), halide salts, (substituted or unsubstituted) alkyl halogens, or molecular (diatomic) halogens (e.g., chlorine, bromine, iodine, or mixtures thereof; preferably bromine and / or iodine). In various embodiments, the halogen source is in a diatomic form, a hydrohalic acid, or a halide salt, more preferably in a diatomic form or a hydrohalic acid. In some embodiments, the halogen source is a hydrohalic acid, particularly hydrogen bromide.

[0194] Typically, the molar ratio of halogen to gluconic acid or its salt, ester, or lactone is approximately equal to or less than about 1. In various embodiments, the molar ratio of halogen to gluconic acid or its salt, ester, or lactone is typically from about 1:1 to about 0.1:1, more typically from about 0.7:1 to about 0.3:1, and even more typically from about 0.5:1.

[0195] Typically, this reaction makes it possible to recover halogen sources and to use halogens in catalytic amounts (where the molar ratio of halogen to gluconic acid or its salt, ester or lactone is less than about 1) to recover and recycle them for continued use as halogen sources.

[0196] Typically, the temperature of the hydrodeoxygenation reaction mixture is at least about 20°C, typically at least about 80°C, and more typically at least about 100°C. In various embodiments, the temperature of the hydrodeoxygenation reaction is in the range of about 20°C to about 250°C, about 80°C to about 200°C, about 120°C to about 180°C, or about 140°C to 180°C. Typically, the partial pressure of hydrogen is at least about 25 psia (172 kPa), more typically at least about 200 psia (1379 kPa) or at least about 400 psia (2758 kPa). In various embodiments, the partial pressure of hydrogen is from about 25 psia (172 kPa) to about 2500 psia (17237 kPa), from about 200 psia (1379 kPa) to about 2000 psia (13790 kPa), or from about 400 psia (2758 kPa) to about 1500 psia (10343 kPa).

[0197] This hydrodeoxygenation reaction can be carried out in the presence of a solvent. Suitable solvents for this selective hydrodeoxygenation reaction include water and carboxylic acids, amides, esters, lactones, sulfoxides, sulfones, and mixtures thereof. Preferred solvents include water, mixtures of water and weak carboxylic acids, and weak carboxylic acids. A preferred weak carboxylic acid is acetic acid.

[0198] The embodiments of the present invention include the following:

[0199] 1. A method for preparing porous shaped metal-carbon products, the method comprising:

[0200] The carbonaceous material is mixed with water, a water-soluble organic binder and (first) a metal precursor to form a metal-carbon mixture, wherein the metal precursor is a compound selected from the group consisting of: metal carbonates, metal oxides, metal hydroxides, salts of metal acids, heteropoly acids, metal carboxylates, their hydrates and mixtures thereof.

[0201] The metal-carbon mixture is shaped to form a green-molded metal-carbon product; and

[0202] The green metal-carbon product is heated to a carbonization temperature to produce a carbonized metal-carbon product containing many pores.

[0203] 2. The method of implementation scheme 1, wherein the metal precursor is a metal carbonate or its hydrate.

[0204] 3. The method of implementation scheme 1, wherein the metal precursor is a metal oxide or its hydrate.

[0205] 4. The method of implementation scheme 1, wherein the metal precursor is a metal hydroxide or its hydrate.

[0206] 5. The method of implementation scheme 1, wherein the metal precursor is a salt of a metal acid or a hydrate thereof.

[0207] 6. The method of implementation scheme 1, wherein the metal precursor is a heteropolyacid or its hydrate.

[0208] 7. The method of implementation scheme 1, wherein the metal precursor is a carboxylate of a metal acid or its hydrate.

[0209] 8. The method of any one of embodiments 1-7, wherein the metal precursor comprises a metal as a base metal.

[0210] 9. The method according to any one of embodiments 1-7, wherein the metal precursor comprises a metal selected from Cu, Pb, Ni, Zn, Fe, Mo, Al, Sn, W, Ta, Co, Bi, Cd, Ti, Zr, Sb, Mn, Be, Cr, Ge, V, Ga, Hf, In, Nb, Rh, Tl, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and combinations thereof.

[0211] 10. The method of embodiment 9, wherein the metal precursor comprises a metal selected from Cu, Pb, Ni, Zn, Fe, Mo, Al, Sn, W, Ta, Co, Bi, Cd, Ti, Zr, Sb, Mn, Be, Cr, Ge, V, Ga, Hf, In, Nb, Rh, Tl, and combinations thereof.

[0212] 11. The method of embodiment 10, wherein the metal precursor comprises a metal selected from Ni, Co, W, Nb, Mo, and combinations thereof.

[0213] 12. The method of any one of embodiments 1-7, wherein the metal precursor is decomposed and reduced to a metal at a temperature of about 250°C to about 1,000°C.

[0214] 13. The method of any one of embodiments 1-2 and 8-11, wherein the metal precursor is nickel carbonate or its hydrate.

[0215] 14. The method of any one of embodiments 1, 5 and 8-11, wherein the metal precursor is hydrated ammonium metatungstate.

[0216] 15. The method of any one of embodiments 1-12, wherein the metal precursor is water-insoluble.

[0217] 16. The method of any one of embodiments 1-12, wherein the metal precursor is water-soluble.

[0218] 17. The method of any one of embodiments 1-16, wherein the metal precursor is present in the metal-carbon mixture in an amount from about 0.1% by weight to about 90% by weight.

[0219] 18. The method of embodiment 17, wherein the metal precursor is present in the metal-carbon mixture in an amount of about 5% to about 70% by weight.

[0220] 19. The method of embodiment 18, wherein the metal precursor is present in the metal-carbon mixture in an amount of about 10% to about 70% by weight.

[0221] 20. The method of embodiment 18, wherein the metal precursor is present in the metal-carbon mixture in an amount of about 5% to about 60% by weight.

[0222] 21. The method of embodiment 18, wherein the metal precursor is present in the metal-carbon mixture in an amount of about 10% to about 60% by weight.

[0223] 22. The method of embodiment 18, wherein the metal precursor is present in the metal-carbon mixture in an amount of about 15% to about 70% by weight.

[0224] 23. The method of embodiment 22, wherein the metal precursor is present in the metal-carbon mixture in an amount of about 25% to about 60% by weight.

[0225] 24. The method of embodiment 17, wherein the metal precursor is present in the metal-carbon mixture in an amount of about 0.1% by weight to about 10% by weight.

[0226] 25. The method of embodiment 24, wherein the metal precursor is present in the metal-carbon mixture in an amount of about 0.1% by weight to about 5% by weight.

[0227] 26. The method of embodiment 25, wherein the metal precursor is present in the metal-carbon mixture in an amount of about 0.5% by weight to about 5% by weight.

[0228] 27. The method of any one of embodiments 1-26, wherein the carbonaceous material is present in the metal-carbon mixture in an amount of about 15% by weight to about 80% by weight.

[0229] 28. The method of embodiment 27, wherein the carbonaceous material is present in the metal-carbon mixture in an amount of about 20% to about 60% by weight.

[0230] 29. The method of embodiment 27, wherein the carbonaceous material is present in the metal-carbon mixture in an amount of about 15% to about 35% by weight.

[0231] 30. The method of any one of embodiments 1-29, wherein the water-soluble organic binder and the carbonaceous material are present in the metal-carbon mixture in a weight ratio of at least about 1:4, at least about 1:3, at least about 1:2, at least about 1:1 or at least about 1.5:1.

[0232] 31. The method of any one of embodiments 1-30, wherein the adhesive is present in the metal-carbon mixture in an amount of about 10% by weight to about 50% by weight.

[0233] 32. The method of any one of embodiments 1-31, wherein water is present in the metal-carbon mixture in an amount not exceeding about 80% by weight of the metal-carbon mixture.

[0234] 33. The method of any one of embodiments 1-32, wherein the water-soluble organic adhesive is a water-soluble polymer.

[0235] 34. The method of embodiment 33, wherein the water-soluble polymer is a carbohydrate.

[0236] 35. The method of embodiment 34, wherein the carbohydrate is cellulose.

[0237] 36. The method of any one of embodiments 1-22, wherein the water-soluble organic binder is sugar.

[0238] 37. The method of any one of embodiments 1-32, wherein the organic water-soluble binder is a mixture of cellulose and sugar.

[0239] 38. The method of any one of embodiments 1-37, wherein the mixing step is carried out in a mixer selected from a grinding mill, a planetary mixer, a drum mixer, a disc mixer, a twin-shaft mixer, and a cement mixer.

[0240] 39. The method according to any one of embodiments 1-38, further comprising premixing a subset of components selected from water, water-soluble organic binders, carbonaceous materials and metal precursors.

[0241] 40. The method of embodiment 39, which includes premixing water and a water-soluble organic adhesive together to form an adhesive solution.

[0242] 41. The method of implementation scheme 39, which includes premixing water, water-soluble organic binder and metal precursor together.

[0243] 42. The method of implementation scheme 39, further comprising premixing the carbonaceous material and the metal precursor together.

[0244] 43. The method of any one of embodiments 1-42, wherein the molding step comprises a process selected from pressing, casting, injection molding, extrusion, coating, pelletizing, granulation, calendering and 3D printing.

[0245] 44. The method of embodiment 43, wherein the molding step further comprises breaking down the product selected from processes such as pressing, casting, injection molding, extrusion, coating, pelletizing, granulation, calendering, and 3D printing into smaller fragments.

[0246] 45. The method of any one of embodiments 1-44, further comprising drying the metal-carbon mixture to remove at least a portion of the water before heating the green metal-carbon product to a carbonization temperature.

[0247] 46. ​​The method of embodiment 45, wherein the drying is performed at a temperature of about 20°C to about 150°C, or about 40°C to about 120°C, or about 60°C to about 120°C.

[0248] 47. The method of any one of embodiments 1-46, wherein the carbonization temperature is about 250°C to about 1000°C, or about 300°C to about 950°C, or about 300°C to about 900°C, or about 350°C to about 900°C, or about 350°C to about 850°C or about 350°C to about 800°C.

[0249] 48. The method of any one of embodiments 1-47, further comprising contacting the carbonized metal-carbon product with a reducing agent at a temperature of about 100°C to about 600°C.

[0250] 49. The method of any one of embodiments 1-48, further comprising forming particles of the carbonized metal-carbon product.

[0251] 50. The method of any one of embodiments 1-49, wherein the carbonized metal-carbon product comprises an amount of metal from about 0.1% by weight to about 70% by weight.

[0252] 51. The method of any one of embodiments 1-50, wherein the carbonized metal-carbon product exhibits catalytic activity.

[0253] 52. The method of any one of embodiments 1-51, wherein the carbonized metal-carbon product is conductive.

[0254] 53. The method of any one of embodiments 1-52, wherein the carbonaceous material is carbon black.

[0255] 54. The method of any one of embodiments 1-52, wherein the carbonaceous material is activated carbon.

[0256] 55. The method of any one of embodiments 1-52, wherein the carbonaceous material is graphite.

[0257] 56. The method of any one of embodiments 1-52, wherein the carbonaceous material is a mixture of any two or more materials selected from carbon black, activated carbon and graphite.

[0258] 57. The method according to any one of embodiments 1-54 and 56, wherein the carbonaceous material has at least about 20m 2 / g BET specific surface area.

[0259] 58. The method of embodiment 57, wherein the carbonaceous material has approximately 20m 2 / g to approximately 500m 2 / g BET specific surface area.

[0260] 59. The method of any one of embodiments 1-53 and 57-58, wherein the carbonized metal-carbon product comprises a pore volume, wherein approximately 50% to approximately 95% of the pore volume, as measured by the BJH method based on pores having a diameter of 1.7 nm to 100 nm, comes from pores having a pore size of approximately 5 nm to approximately 100 nm.

[0261] 60. The methods of embodiments 1-53 and 57-59, wherein no more than about 10% of the pore volume comes from pores with a pore size of less than about 10 nm.

[0262] 61. The method according to any one of embodiments 1-53 and 57-60, wherein the carbonized metal-carbon product comprises approximately 0.1 cm 3 / g to approximately 1.5cm 3 / g of specific pore volume with diameters ranging from 1.7 nm to 100 nm, as measured by the BJH method.

[0263] 62. The method of any one of embodiments 1-53 and 57-61, wherein the carbonized metal-carbon product exhibits a radial sheet crushing strength greater than about 4.4 N / mm (1 lb / mm).

[0264] 63. The method according to any one of embodiments 1-52 and 54, wherein the carbonaceous material has a thickness of approximately 550m. 2 / g to approximately 3500m 2 / g BET specific surface area.

[0265] 64. The method of any one of embodiments 1-63, further comprising depositing a second metal precursor on the surface of the carbonized metal-carbon product.

[0266] 65. The method of implementation 64, wherein the second metal precursor comprises a metal different from the metal in the first metal precursor.

[0267] 66. The method of implementation scheme 65, wherein the second metal precursor comprises a metal as a precious metal.

[0268] 67. Carbonized metal-carbon products according to any one of implementation schemes 1-66.

[0269] 68. A porous shaped metal-carbon product comprising a porous carbon matrix and a metal component, wherein the metal component of the porous shaped metal-carbon product is present at a metal loading of at least about 10% by weight.

[0270] 69. The porous molded metal-carbon product of embodiment 68, wherein the metal loading is at least about 11 wt%, at least about 12 wt%, at least about 13 wt%, at least about 14 wt%, at least about 15 wt%, at least about 16 wt%, at least about 17 wt%, at least about 18 wt%, at least about 19 wt%, or at least about 20 wt%.

[0271] 70. The product of any one of embodiments 66-67, wherein the metal component of the porous shaped metal-carbon product is a base metal.

[0272] 71. The product of any one of embodiments 68-70, wherein the metal component of the porous shaped metal-carbon product is selected from Cu, Pb, Ni, Zn, Fe, Mo, Al, Sn, W, Ta, Co, Bi, Cd, Ti, Zr, Sb, Mn, Be, Cr, Ge, V, Ga, Hf, In, Nb, Rh, Tl, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and combinations thereof.

[0273] 72. The product of embodiment 71, wherein the metal component of the metal-carbon product is selected from Cu, Pb, Ni, Zn, Fe, Mo, Al, Sn, W, Ta, Co, Bi, Cd, Ti, Zr, Sb, Mn, Be, Cr, Ge, V, Ga, Hf, In, Nb, Rh, Tl, and combinations thereof.

[0274] 73. The product of embodiment 72, wherein the metal component of the metal-carbon product is selected from Ni, Co, W, Nb, Mo, and combinations thereof.

[0275] 74. The product of embodiment 73, wherein the metal component of the metal-carbon product is selected from Ni, W, and combinations thereof.

[0276] 75. The product of any one of embodiments 67-74, further comprising a second metal deposited on the surface of the porous shaped metal-carbon product.

[0277] 76. The product of embodiment 75, wherein the second metal is different from the metal component of the metal-carbon product.

[0278] 77. A porous shaped metal-carbon product according to implementation scheme 76, wherein the second metal is a precious metal.

[0279] 78. The porous molded metal-carbon product of embodiment 77, wherein the precious metal is selected from Pt and Au.

[0280] 79. The porous shaped metal-carbon product of any one of embodiments 67-78, wherein the product is catalytically active.

[0281] 80. A method for producing bis-hydroxymethyltetrahydrofuran (BHMTHF) from 2,5-bis-hydroxymethylfuran (BHMF), the method comprising:

[0282] BHMF is contacted with hydrogen in the presence of a multiphase hydrogenation catalyst containing a porous shaped metal-carbon product to form BHMTHF, wherein the metal component of the metal-carbon product is selected from Ni, Co, Cu, Ag, Pd, Pt, Ru, and combinations thereof.

[0283] 81. The method of any one of embodiments 80, wherein the metal component is Ni.

[0284] 82. The method of any one of embodiments 80-81, wherein the metal component is present at a metal loading of about 0.5% by weight to about 99% by weight.

[0285] 83. The method of any one of embodiments 80-82, wherein the contact step is performed at a temperature of about 80°C to about 150°C.

[0286] 84. The method of any one of embodiments 80-83, wherein hydrogen is present at a pressure of about 50 psig to about 2000 psig.

[0287] 85. The method of any one of embodiments 80-84, wherein BHMTHF is prepared with at least about 90% selectivity.

[0288] 86. The method of any one of implementations 80-85, wherein at least approximately 85% of BHMF is converted into BHMTHF.

[0289] 87. A method for producing the corresponding C3-C6 diol from a C3-C6 polyol, the method comprising:

[0290] C3-C6 polyols are contacted with hydrogen in the presence of a hydrodeoxygenation catalyst containing a porous shaped metal-carbon product to form the corresponding C3-C6 diol, wherein the metal component of the metal-carbon product is selected from Pd, Pt, Ir, Mo, W, V, Mn, Re, Zr, Ni, Cu, La, Sm, Y, Zn, Cr, Ge, Sn, Ti, Au, Rh, Co, and combinations thereof.

[0291] 88. The method of any one of embodiments 87, wherein the metal component is Ni.

[0292] 89. The method of any one of embodiments 87-88, wherein the metal component is present at a metal loading of about 0.5% by weight to about 10% by weight.

[0293] 90. The method of any one of embodiments 87-89, wherein the C3-C6 polyol is selected from 1,2,6-hexanetriol, 1,2,5-pentanetriol, 2H-tetrahydropyran-2-methanol, tetrahydrofuran-2,5-diethanol, furan-2,5-diethanol, 2,5-dihydrofuran-2,5-diethanol, L-glucan, L-glucan, levoglucosenol, 1,6-dehydro-3- ,4-Dideoxy-pD-pyranose-2-one, isosorbide, hydroxymethylfurfural, sorbitol, glucose, fructose, xylitol, 3,4-dihydro-2H-pyran-2-carboxaldehyde, 1,2,5,6-hexanetetraol, 1,2,3,5,6-hexanepentol, 1,5-dehydro-3,4-dideoxyhexitol, 5-hydroxy-2H-tetrahydropyran-2-methanol, furfural, furfuryl alcohol, tetrahydrofurfural, pentose, and hexose.

[0294] 91. The method of any one of embodiments 87-90, wherein the C3-C6 diol is selected from 1,5-pentanediol and 1,6-hexanediol.

[0295] 92. The method of any one of embodiments 87-91, wherein the porous shaped metal-carbon product further comprises Pt deposited on the surface of the porous shaped metal-carbon product.

[0296] 93. The method according to any one of embodiments 87-92, wherein the C3-C6 polyol is 1,2,6-hexanetriol and the C3-C6 diol is 1,6-hexanediol.

[0297] 94. The method of any one of embodiments 87-93, wherein the contact step is performed at a temperature of about 80°C to about 200°C.

[0298] 95. The method of any one of embodiments 87-94, wherein hydrogen is present at a pressure of about 200 psig to about 3000 psig.

[0299] 96. The method of any one of embodiments 87-95, wherein the C3-C6 diol is obtained with at least about 80% selectivity.

[0300] 97. A method for producing 1,6-hexanediamine (HMDA) from 1,6-hexanediol (HDO), the method comprising:

[0301] 1,6-hexanediol and amine are contacted in the presence of an amination catalyst containing a porous shaped metal-carbon product to form HMDA, wherein the metal component of the porous shaped metal-carbon product is a metal selected from Ni, Ru and Rh.

[0302] 98. A method for producing gluconic acid from glucose, the method comprising:

[0303] Glucose is contacted with oxygen in the presence of an oxidation catalyst containing a porous shaped metal-carbon product to form gluconic acid, wherein the metal component of the porous shaped metal-carbon product is a base metal.

[0304] 99. The method of embodiment 98, wherein the porous shaped metal-carbon product further comprises a noble metal deposited thereon.

[0305] 100. A method for producing dicarboxylic acids from aldonic acid or its salts, esters, or lactones, the method comprising:

[0306] Aldonic acid or its salt, ester or lactone is contacted with hydrogen in the presence of a halogenated compound and a hydroxygenation catalyst comprising the porous shaped metal-carbon product of the present invention to form a dicarboxylic acid, wherein the metal component of the porous shaped metal-carbon product is a base metal.

[0307] 101. The method of embodiment 100, wherein the porous shaped metal-carbon product further comprises a noble metal deposited thereon.

[0308] 102. A method for producing 2,5-bis-hydroxymethylfuran (BHMF) from 5-hydroxymethylfurfural (HMF), the method comprising:

[0309] HMF is contacted with hydrogen in the presence of a hydrogenation catalyst containing the porous shaped metal-carbon product of the present invention to form BHMF, wherein the metal component of the porous shaped metal-carbon product is selected from Ni, Zn, Co, Cu, Ag, Pt, Pd, Fe, Ru, Au, W, Sb, Bi, Pb and combinations thereof.

[0310] The above and other aspects of the invention can be better understood by referring to the following non-limiting embodiments.

[0311] Example

[0312] Example 1

[0313] Preparation of 10% Ni-carbon catalyst

[0314] 33.80 g of basic nickel carbonate hydrate NiCO3·2Ni(OH)2·xH2O (Mw 358.12x=3) (SKU 544183) from Sigma-Aldrich was added to an aqueous solution (250 g) containing 42.0 wt% glucose (ADM Corn Processing, dextrose monohydrate 99.7DE, with a glucose content of 91.2255 wt%) and 3.0 wt% hydroxyethyl cellulose (SKU 54290, viscosity 80-125 cP, 2% in H2O, at 20°C) from Sigma-Aldrich to form a suspension under stirring. Then 100 g of carbon black powder (Timcal Ensaco 250 g, 65m) was added. 2 / g) was added to the suspension above. The mixture was blended in a laboratory mill and run for 2 hours to ensure good mixing and kneading of the material. The material was then loaded into a 1” Bonnot BB Gun extruder and extruded into spaghetti-shaped strips with a cross-sectional diameter of approximately 1.5 mm. These strips were dried overnight in a 120°C oven under dry air purging. They were then treated for 2 hours at 800°C with a heating rate of 30°C / min under a continuous N2 stream to produce carbon black extrudate. Finally, the catalyst was reduced at 430°C for 6 hours in a synthesis gas stream (5% H2, 95% N2) and passivated for 2 hours at room temperature with a gas mixture of 0.1% O2 / N2.

[0315] Example 2

[0316] Preparation of 15% Ni-carbon catalyst

[0317] 54.65 g of basic nickel carbonate hydrate NiCO3·2Ni(OH)2·xH2O (Mw 358.12x=3) (SKU 544183) from Sigma-Aldrich was added to an aqueous solution (250 g) containing 42.0 wt% glucose (ADM Corn Processing, dextrose monohydrate 99.7DE, with a glucose content of 91.2255 wt%) and 3.0 wt% hydroxyethyl cellulose (SKU 54290, viscosity 80-125 cP, 2% in H2O, at 20°C) from Sigma-Aldrich to form a suspension under stirring. Then 100 g of carbon black powder (Timcal Ensaco 250 g, 65m) was added. 2 / g) was added to the above suspension and the mixture was blended in a laboratory mill for 2 hours to ensure good mixing and kneading of the material. The material was then loaded into a 1” Bonnot BB Gun extruder and extruded into spaghetti-shaped strips with a cross-sectional diameter of approximately 1.5 mm. These strips were dried overnight in a 120°C oven under dry air purging. They were then treated at 800°C for 2 hours under a continuous N2 stream at a heating rate of 30°C / min to produce carbon black extrudate. Finally, the catalyst was reduced at 430°C for 6 hours in a synthesis gas stream (5% H2, 95% N2) and passivated at room temperature with a gas mixture of 0.1% O2 / N2 for 2 hours.

[0318] Example 3

[0319] Preparation of 20% Ni-carbon catalyst

[0320] 79.10 g of basic nickel carbonate hydrate NiCO3·2Ni(OH)2·xH2O (Mw 358.12x=3) (SKU 544183) from Sigma-Aldrich was added to an aqueous solution (250 g) containing 42.0 wt% glucose (ADM Corn Processing, dextrose monohydrate 99.7DE, with a glucose content of 91.2255 wt%) and 3.0 wt% hydroxyethyl cellulose (SKU 54290, viscosity 80-125 cP, 2% in H2O, at 20°C) from Sigma-Aldrich to form a suspension under stirring. Then 100 g of carbon black powder (Timcal Ensaco 250 g, 65m) was added. 2 / g) was added to the above suspension and the mixture was blended in a laboratory mill for 2 hours to ensure good mixing and kneading of the material. The material was then loaded into a 1” Bonnot BB Gun extruder and extruded into spaghetti-shaped strips with a cross-sectional diameter of approximately 1.5 mm. These strips were dried overnight in a 120°C oven under dry air purging. They were then treated at 800°C for 2 hours under a continuous N2 stream at a heating rate of 30°C / min to produce carbon black extrudate. Finally, the catalyst was reduced at 430°C for 6 hours in a synthesis gas stream (5% H2, 95% N2) and passivated at room temperature with a gas mixture of 0.1% O2 / N2 for 2 hours.

[0321] Example 4

[0322] Comparison of Ni-alumina catalyst preparation

[0323] 25.6 g of Ni(NO3)2x6H2O (Alfa-Aesar) was dissolved in 15 mL of DI water. 6 mL of this solution was added to 6 g of alumina support (XA 31132, Saint-Gobain). The material was dried at 120 °C for 2 h and calcined at 350 °C for 3 h. The material was then reduced at 430 °C for 6 h in a synthesis gas (5% H2, 95% N2) and passivated for 2 h with a gas mixture of 0.1% O2 / N2. The calculated Ni loading was 15.3% by weight.

[0324] Example 5

[0325] Catalytic hydrogenation activity test

[0326] All catalysts, including comparatives, were tested in high-throughput mode in a HiP-HOSS reactor according to the following procedure (see "High-Throughput Heterogeneous Catalyst Research", Howard W. Turner, Anthony F. Volpe Jr. and WH Weinberg, Surface Science 603 (2009) 1763-1769, which are hereby cited and incorporated herein by reference). 20 mg of catalyst was placed in a 1 mL vial containing 0.2 mL of a 0.4 M solution of BHMF (2,5-dimethylfuran) in 90% i-PA + 10% H₂O (v / v). The experiment was conducted at 110 °C and a hydrogen pressure of 700 psi for 3 h. The observed products were 2,5BHMTHF (2,5-dimethyltetrahydrofuran) and 1,2,6HTO (1,2,6-hexanetriol). The results are presented in Table 1.

[0327] Table 1. Hydrogenation Activity

[0328]

[0329] The results show that the Ni-C catalyst prepared according to the procedure of the present invention has good hydrogenation activity and selectivity for double bond hydrogenation comparable to that of Ni / alumina catalysts with similar Ni loading.

[0330] Example 6

[0331] Tungsten-containing carbon black extrudates were prepared using carbon black powder and carbohydrate-based binders.

[0332] 200 grams of carbon black powder (Timcal Ensaco 250G, 65m) 2A mixture of 42.0 wt% glucose (ADM Corn Processing, dextrose monohydrate 99.7DE, with a glucose content of 91.2255 wt%), 3.0 wt% hydroxyethyl cellulose from Sigma-Aldrich (SKU 54290, viscosity 80-125 cP, 2% in H2O at 20°C), and 0.82 wt% ammonium metatungstate hydrate from Sigma-Aldrich (SKU 358975) was added to an aqueous solution (500 g) containing Sigma-Aldrich glucose (ADM Corn Processing, dextrose monohydrate 99.7DE, with a glucose content of 91.2255 wt%), hydroxyethyl cellulose from Sigma-Aldrich (SKU 54290, viscosity 80-125 cP, 2% in H2O at 20°C), and ammonium metatungstate hydrate from Sigma-Aldrich (SKU 358975). The mixture was blended in a laboratory grinder for 2 hours to ensure good mixing and kneading of the materials. The material was then loaded into a 1” Bonnot BB Gun extruder and extruded into spaghetti-shaped strips with a cross-sectional diameter of approximately 1.5 mm. These strips were dried overnight in a 120°C oven under dry air purging. They were then treated for 2 hours at 800°C with a heating rate of 30°C / min under a continuous flow of N2 to produce carbon black extrudates. Different carbon black extrudates were prepared in a similar manner using other carbon black powders and carbohydrate binders, as well as various amounts of other tungsten-containing compounds.

[0333] Example 7

[0334] Preparation of platinum-supported tungsten-containing carbon black extrudates

[0335] 15 g of the tungsten-containing carbon black extrudate from Example 6 was evenly distributed into 30 40 mL vials. An aqueous solution of Pt(NO3)2(Heraeus) of appropriate concentration (approximately 4.3 wt% Pt) was added to each of the 30 vials and stirred to impregnate the support. The samples were dried in an oven at 60 °C under static air for 3 hours; then calcined at 360 °C in air at a heating rate of 5 °C / min for 2 hours. Approximately 10% mass loss was recorded during the heat treatment to achieve a final catalyst metal content of approximately 5.9 wt% Pt and 1.2 wt% W.

[0336] Example 8

[0337] Catalytic hydrodeoxygenation activity test

[0338] The reaction was carried out in a 1 / 2” OD × 83cm long 316 stainless steel tube with a parallel downward flow of gas and liquid. The catalyst bed was vibrated and filled with 1.0 mm glass beads at the top to a depth of about 40 cm, followed by the addition of catalyst (28.5 cm bed depth, containing 10.0 g), and then SiC was filled at the bottom to a depth of about 8 cm. Quartz cotton plugs separated the catalyst bed from the SiC.

[0339] The packed reactor tubes were clamped in an aluminum block heater equipped with a PID controller at 120°C. The flow rates of the gas (hydrogen) and the 0.4 M 1,2,6-hexanetriol (Spectrum Chemical and TCI America) in water were adjusted using a mass flow controller and an HPLC pump, respectively. A back pressure regulator maintained the reactor pressure at 1000 psig. The catalyst was tested under these conditions for approximately 429 hours (ToS). The liquid effluent was diluted with methanol and analyzed by gas chromatography with flame ionization detection. Table 2 describes the fixed-bed reactor conditions and the performance of the resulting catalyst.

[0340] Table 2. 1,2,6-Hexanetriol to 1,6-Hexanediol

[0341]

[0342] Example 9

[0343] Tungsten-containing carbon black extrudates were prepared using carbon black powder and carbohydrate-based binders.

[0344] 200 grams of carbon black powder (Timcal Ensaco 250G, 65m) 2 A mixture of 275 g water, 210 g glucose (ADM Corn Processing, dextrose monohydrate 99.7DE, with a glucose content of 91.2255 wt%), 15 g hydroxyethyl cellulose from Sigma-Aldrich (SKU 54290, viscosity 80-125 cP, 2% in H2O (20°C)), and 8.35 g (carrier ID "b"), 19.95 g (carrier ID "c"), and 33.65 g (carrier ID "d") of ammonium metatungstate hydrate ("AMT") (SKU 358975) from Sigma-Aldrich were added. The mixture was blended in a laboratory grinder for 2 hours to ensure good mixing and kneading of the materials. The material was then loaded into a 1" Bonnot BB Gun extruder and extruded into spaghetti-shaped strips with a cross-sectional diameter of approximately 1.5 mm. These strips were dried overnight in a 120°C oven under dry air purging. They were then treated for 2 hours at 800°C with a heating rate of 30°C / min under a continuous flow of N2 to produce carbon black extrudate.

[0345] Different amounts of tungsten oxide (VI) (Lot 25575500) from Strem Chemicals were used: (carrier ID "e") 0.92 g; (carrier ID "f") 1.86 g; (carrier ID "g") 3.76 g and 100 g of carbon black powder (Timcal Ensaco 250G, 65m) 2A 1 / g (g) compound was added to an aqueous solution containing 135g water, 105g glucose (ADM Corn Processing, 99.7DE dextrose monohydrate with a glucose content of 91.2255% by weight), and 7.5g hydroxyethyl cellulose (SKU 54290, viscosity 80-125cP, 2% in H2O (20°C)) from Sigma-Aldrich. The mixture was blended in a laboratory mill for 2 hours to ensure good mixing and kneading of the material. The material was then loaded into a 1” Bonnot BB Gun extruder and extruded into spaghetti-shaped strips with a cross-sectional diameter of approximately 1.5 mm. These strips were dried overnight in a 120°C oven under dry air purging. They were then treated for 2 hours under a continuous N2 stream at 800°C with a heating rate of 30°C / min to produce a carbon black extrudate.

[0346] Example 10

[0347] Preparation of platinum-supported tungsten-containing carbon black extrudates

[0348] (Carrier ID b in Table 3)

[0349] 15 g of the tungsten-containing carbon black extrudate (2 wt% W) from Example 9 was evenly divided into 30 40 mL vials. An aqueous solution of Pt(NO3)2 (Heraeus) of appropriate concentration was added to each of the 30 vials and stirred to impregnate the support. The samples were dried in an oven at 60 °C under static air for 3 h; then calcined at 360 °C in air at a heating rate of 5 °C / min for 2 h. The contents of the 30 vials were combined. Approximately 5% mass loss was recorded during the heat treatment to achieve a final catalyst metal content of approximately 5.1 wt% Pt and 2 wt% W. A 0.25 g sample of the final catalyst was further heat-treated at 75 °C in a 5% hydrogen / 95% nitrogen atmosphere at a heating rate of 5 °C / min for 3 h.

[0350] Example 11

[0351] Preparation of platinum-supported tungsten-containing carbon black extrudates

[0352] (Carrier ID cg in Table 3)

[0353] 0.5 g of each tungsten-containing carbon black extrudate from Example 10 was evenly distributed into one of five 40 mL vials. An aqueous solution of Pt(NO3)2 (Heraeus) of appropriate concentration was added to each vial and stirred to impregnate the support. The samples were dried in an oven at 60 °C under static air for 3 hours; then calcined at 360 °C in air at a heating rate of 5 °C / min for 2 hours. 0.25 g of each of the above catalysts was further heat-treated at 75 °C under a 5% hydrogen / 95% nitrogen atmosphere at a heating rate of 5 °C / min for 3 hours.

[0354] Example 12

[0355] Testing of tungsten-containing carbon black extrusion in a batch reactor for the hydrodeoxidation of 1,2,6-hexanediol to 1,6-hexanediol The product contains platinum

[0356] The following catalyst testing procedure was used to test the 12 extrudate catalysts used for the reduction of 1,2,6-hexanetriol (Spectrum Chemical). The extrudate catalysts were crushed. Small samples (approximately 10 mg) of each catalyst were weighed into glass inserts, followed by the addition of 200 μl (0.8 M) of an aqueous solution of 1,2,6-hexanetriol. The glass inserts were loaded into the reactor and the reactor was shut off. The atmosphere in the reactor was purged with hydrogen and pressurized to 670 psig at room temperature. The reactor was heated to 160 °C and maintained at 160 °C for 2.5 h while the inserts were shaken. After 2.5 h, shaking was stopped and the reactor was cooled to 40 °C. The pressure in the reactor was then slowly released. The glass inserts were removed from the reactor. The solution was diluted with methanol and analyzed by gas chromatography with flame ionization detection. The results are summarized in Table 3.

[0357] Table 3. 1,2,6-Hexanetriol to 1,6-Hexanediol

[0358]

[0359] C – Calcination conditions

[0360] R – Reduction condition

[0361] Example 13

[0362] Preparation of gold-platinum loaded tungsten-containing crushed carbon black extrudate

[0363] 0.1 g of each tungsten-containing carbon black extrudate from Example 9 was placed in a 4 mL vial and crushed into powder. An aqueous solution of NMe4AuO2 and PtO(NO3) of appropriate concentration was added to each of the six vials and stirred to impregnate the support. The samples were dried in an oven at 60 °C under a 5% hydrogen / 95% nitrogen atmosphere for 3 h; then further treated at 350 °C at a heating rate of 5 °C / min for 3 h. The metal loading of each catalyst was approximately 0.51 wt% Au and 0.93 wt% Pt.

[0364] Example 14

[0365] Testing of gold-loaded tungsten-containing crushed carbon black extrudate in a batch reactor for glucose oxidation to gluconic acid. platinum

[0366] Six catalysts for the oxidation of glucose (ADM) were tested using the following catalyst test procedure. Approximately 16 mg of catalyst was weighed into a glass vial liner, followed by the addition of an aqueous glucose solution (250 μl, 20% by weight). The glass vial liner was loaded into the reactor and the reactor was shut off. The atmosphere in the reactor was purged with oxygen and pressurized to 150 psig at room temperature. The reactor was heated to 110 °C and maintained at 110 °C for 2 hours while the vial was shaken. After 2 hours, shaking was stopped and the reactor was cooled to 40 °C. The pressure in the reactor was then slowly released. The glass vial liner was removed from the reactor. The solution was diluted with water and analyzed by ion chromatography using CAD / connectivity detection. A summary of the results is provided in Table 4.

[0367] Table 4. Glucose to gluconic acid yield

[0368] b* 2.0 AMT 88％ 15％ c 4.6 AMT 81％ 12％ d 7.5 AMT 88％ 19％ e 0.5 <![CDATA[WO3]]> 82％ 13％ f 1.0 <![CDATA[WO3]]> 90％ 17％ g 2.0 <![CDATA[WO3]]> 94％ 21％

[0369] *Use 12 mg catalyst

[0370] Although preferred embodiments of the invention have been illustrated and described, it should be recognized that various modifications can be made thereto without departing from the spirit and scope of the invention.

Claims

1. A method for producing corresponding C3-C6 diols from C3-C6 polyols, the method comprising: C3-C6 polyols are contacted with hydrogen in the presence of a hydrodeoxygenation catalyst to form the corresponding C3-C6 diols, wherein the hydrodeoxygenation catalyst comprises a porous shaped tungsten-carbon product containing carbon black and platinum is deposited thereon. The porous shaped tungsten-carbon product is prepared by a method comprising the following steps: A carbonaceous material containing carbon black is mixed with water, a water-soluble organic binder, and a tungsten precursor to form a tungsten-carbon mixture, wherein the tungsten precursor is a salt of tungstate. The tungsten-carbon mixture is shaped to form a green tungsten-carbon product; and The green tungsten-carbon product is heated to the carbonization temperature to produce the porous tungsten-carbon product.

2. The method according to claim 1, wherein the C3-C6 polyol is selected from the group consisting of 1,2,6-hexanetriol, 1,2,5-pentanetriol, tetrahydrofuran-2,5-diethanol, furan-2,5-diethanol, 2,5-dihydrofuran-2,5-diethanol, L-glucan, isosorbide, sorbitol, xylitol, 1,2,5,6-hexanetetrol, 1,2,3,5,6-hexanepentol, 5-hydroxy-2H-tetrahydropyran-2-ethanol, pentoses, and hexoses.

3. The method according to claim 1, wherein the C3-C6 diol is selected from the group consisting of 1,5-pentanediol and 1,6-hexanediol.

4. The method of claim 1, wherein, based on the total weight of the porous shaped tungsten-carbon product, the tungsten in the porous shaped tungsten-carbon product is present with a metal loading of 0.1% to 25% by weight.

5. The method of claim 1, wherein the porous shaped tungsten-carbon product exhibits a radial sheet crushing strength greater than 4.4 N / mm.

6. The method according to any one of claims 1 to 5, wherein no more than 10% of the pore volume of the porous shaped tungsten-carbon product comes from pores with a diameter of less than 10 nm.

7. The method according to any one of claims 1 to 5, wherein the porous shaped tungsten-carbon product comprises a specific pore volume of 0.1 cm 3 / g to 1.5 cm 3 / g of pores having a diameter of 1.7 nm to 100 nm as measured by the BJH method.

8. The method according to any one of claims 1 to 5, wherein the carbonaceous material comprises having a 20 m 2 / g to 500m 2 / g BET specific surface area of ​​carbon black.

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