Glycerol Hydrogenolysis Process

Abstract

A process for catalytic hydrogenolysis of glycerol to produce propylene glycol and / or ethylene glycol is described.

Description

[Technical Field]

[0001] The present invention generally relates to a process for catalytic hydrogenolysis of glycerol to produce propylene glycol and / or ethylene glycol. [Background technology]

[0002] Carbon is a material that can be effectively utilized as a catalyst support or adsorbent. The most commonly used carbon-based supports for chemical catalysis have a high specific surface area (e.g., 500 m 2 Activated carbons are activated carbons that exhibit a porosity of 0.1 / 0.25 or greater. The production of activated carbons requires the activation of carbonaceous materials, such as charcoal, wood, coconut shell, or petroleum-derived carbon black, either by chemical activation, such as contacting the material with acid at elevated temperatures, or by steam activation. Both activation methods produce a high concentration of micropores and a resulting higher surface area. Depending on the source of the carbonaceous material, the resulting activated carbon may have a high content of residual inorganic ash and sulfur, as well as oxygen- or nitrogen-containing functional groups on the surface. Activated carbons are considered to have the optimal support structure for catalytic applications because they allow for good dispersion of catalytically active components and effective adsorption of chemical reagents onto the catalyst surface.

[0003] In recent years, there has been growing interest in the use of biorenewable materials as feedstocks to replace or supplement crude oil. See, for example, Klass, Biomass for Renewable Energy, Fuels, and Chemicals, Academic Press, 1998. These publications and all other cited publications are incorporated herein by reference. One of the major challenges in converting biorenewable resources, such as carbohydrates (e.g., glucose derived from starch, cellulose, or sucrose), into current commodities and specialty chemicals is the selective removal of oxygen atoms from the carbohydrates. Methods for converting carbon-oxygen single bonds into carbon-hydrogen bonds are known. See, for example, U.S. Pat. No. 8,669,397, which describes a process for converting glucose to adipic acid via the intermediate glucaric acid. One challenging aspect associated with the catalytic conversion of highly functionalized biorenewably derived molecules and intermediates is achieving the high levels of catalytic activity, selectivity, and stability required for commercial applications. Regarding catalytic activity and selectivity, highly functionalized, biorenewably derived molecules and intermediates derived from carbohydrates (e.g., glucose and glucaric acid) are non-volatile and therefore must be processed as solutions in the liquid phase. Compared to gas-phase catalytic processes, liquid-phase catalytic processes are known to have lower productivity due to slower diffusion rates from liquid to solid (and from gas phase to liquid to solid) than from gas phase to solid.

[0004] Another challenging aspect associated with the catalytic conversion of highly functionalized biorenewably derived molecules and intermediates is the use of chemically aggressive reaction conditions. For example, U.S. Patent No. 8,669,397 describes a catalytic conversion step carried out at high temperatures in the presence of polar solvents such as water and acetic acid. Polar solvents are typically required to dissolve nonvolatile, highly functionalized molecules such as glucose and glucaric acid, and high temperatures are necessary for a productive and affordable catalytic conversion step for commodity chemical applications. Therefore, a key challenge associated with the catalytic conversion of highly functionalized biorenewably derived molecules and intermediates is catalyst stability. Long-term catalyst stability is necessary for commodity chemical production, which means that the catalyst must be stable, productive, and selective under the reaction conditions for extended periods of time.

[0005] The challenges associated with the development of industrial shaped catalysts, particularly those for the conversion of biorenewably derived molecules and intermediates, are a) high productivity and selectivity compatible with catalysts that are economically feasible on an industrial scale, b) mechanical and chemical stability of the shaped catalyst support, and c) retention of catalytically active components by the support and avoidance of leaching of the catalytically active components into the polar solvent reaction medium. There remains a need for industrially scalable, highly active, selective, and stable catalyst supports and catalyst compositions that can meet these challenges. Summary of the Invention

[0006] Briefly, in various aspects, the present invention relates to processes for the hydrocracking of glycerol. Some processes involve supplying a feed composition comprising glycerol to a reaction zone and reacting the glycerol with hydrogen in the presence of a catalyst composition described herein (e.g., a catalyst composition comprising a shaped porous carbon product) to form a reaction product comprising propylene glycol and / or ethylene glycol. Other processes for hydrocracking glycerol involve supplying a feed composition comprising glycerol to a reaction zone and reacting the glycerol with hydrogen in the presence of a catalyst composition described herein to form a reaction product comprising propylene glycol and / or ethylene glycol, the catalyst composition comprising a catalytically active component comprising a metal selected from the group consisting of chromium, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, gold, and any combination thereof, and a catalyst support comprising a shaped porous carbon product comprising carbon black.

[0007] Other objects and features will be in part apparent and in part pointed out hereinafter. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a scanning electron microscope image of a cross section of a catalyst extrudate sample made with Monarch 700 carbon black. [Figure 2] FIG. 2 is an enlarged cross-section of one catalyst extrudate of FIG. 1. [Figure 3] FIG. 1 is a plot of cumulative pore volume (%) as a function of average pore size for raw Monarch 700 carbon black material. [Figure 4] 1 is a plot of cumulative pore volume (%) as a function of average pore size for virgin catalyst extrudates containing Monarch 700 carbon black material. [Figure 5] 1 is a plot of cumulative pore volume (%) as a function of average pore size for catalyst extrudates containing Monarch 700 carbon black material after 350 hours of use. [Figure 6] 1 is a plot of cumulative pore volume (%) as a function of average pore size for extrudates using Monarch 700 carbon black and a glucose / hydroxyethyl cellulose binder. [Figure 7] 1 is a plot of cumulative pore volume (%) as a function of average pore size for extrudates using Sid Richardson SC159 carbon black and glucose / hydroxyethyl cellulose binder. [Figure 8] 1 is a plot of cumulative pore volume (%) as a function of average pore size for extrudates using Sid Richardson SC159 carbon black and a glucose / hydroxyethyl cellulose binder exposed to oxygen at 300° C. for 3 hours. [Figure 9] 1 is a plot of cumulative pore volume (%) as a function of average pore size for extrudates using Asbury 5368 carbon black and glucose / hydroxyethyl cellulose binder. [Figure 10] 1 is a plot of cumulative pore volume (%) as a function of average pore size for Sud Chemie G32H-N-75 activated carbon extrudates. [Figure 11] 1 is a plot of cumulative pore volume (%) as a function of average pore size for Donau Supersorbon K4-35 activated carbon extrudates. [Figure 12] 1 is a pore size distribution of extrudates using Sid Richardson SC159 carbon black and glucose / hydroxyethyl cellulose binder as measured by mercury porosimetry. [Figure 13] 1 is a plot of pore size versus pore volume for carbon black extrudates. [Figure 14] 1 is an SEM image of Ni-Re on carbon black extrudate catalyst (catalyst without added nitric acid). [Figure 15] FIG. 15 is an EDX analysis of Ni—Re on carbon black extrudate catalyst shown in FIG. [Figure 16]1 is an SEM image of Ni-Re on carbon black extrudate catalyst (catalyst with added nitric acid). [Figure 17] FIG. 17 is an EDX analysis of Ni—Re on carbon black extrudate catalyst shown in FIG. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention generally relates to shaped porous carbon articles and processes for making these articles. The shaped porous carbon articles can be used, for example, as catalyst supports, chromatographic support materials, filter media, and adsorbents. The present invention also relates to catalyst compositions comprising these shaped porous carbon articles, processes for making the catalyst compositions, and various processes using the shaped porous carbon articles and catalyst compositions.

[0010] The present invention provides shaped porous carbon articles that exhibit high mechanical strength and resist crushing and abrasion during use. Furthermore, the shaped porous carbon articles have excellent chemical stability to reactive solvents, such as acids and other polar solvents, even at elevated temperatures. The shaped porous carbon articles are highly compatible with liquid-phase catalytic reactions, providing efficient mass transfer of relatively large molar volume compounds to and from the support surface.

[0011] The present invention also provides processes for making shaped porous carbon articles. The shaped porous carbon articles can be made from inexpensive and readily available materials, which is advantageous for improving process economics. Furthermore, the disclosed processes are suitable for making robust and mechanically strong shaped porous carbon articles through the use of water-soluble organic binders. These processes avoid the use of organic solvents, which require specialized handling and storage.

[0012] The present invention further provides catalyst compositions comprising the shaped porous carbon articles as catalyst supports and processes for making these catalyst compositions. The shaped porous carbon articles advantageously exhibit a high degree of retention of the catalytically active component(s) of the catalyst composition, thereby preventing or reducing the amount of catalytically active material leaching into the liquid-phase reaction medium. Furthermore, the catalyst compositions have a high degree of stability, which is necessary for the production of commodity chemicals.

[0013] Additionally, the present invention provides processes utilizing shaped porous carbon articles and catalyst compositions, such as processes for the conversion of biorenewably derived molecules and intermediates for general-purpose applications (e.g., the selective oxidation of glucose to glucaric acid), or for applications requiring the adsorption of relatively large molar volumes of compounds. Surprisingly, it has been discovered that the shaped porous carbon articles exhibit superior mechanical strength (e.g., mechanical piece crush strength and / or radial crushing strength), and that the use of catalyst compositions comprising the shaped porous carbon articles of the present invention results in unexpectedly higher productivity, selectivity, and / or yield in certain reactions compared to similar catalyst compositions comprising different catalyst supports.

[0014] Molded porous carbon products and methods of making them The shaped porous carbon products of the present invention can be made using carbon black. Carbon black materials include various subtypes, such as acetylene black, conductive black, channel black, furnace black, lamp black, and thermal black. The primary processes for carbon black production are furnace and thermal processes. Generally, carbon black is produced by the deposition of solid carbon particles formed in the gas phase by the combustion or pyrolysis of petroleum products. Carbon black materials are characterized by particles with diameters in the nanometer range, typically about 5 to about 500 nm. These materials also have a much smaller surface area, a higher concentration of mesopores, and lower ash and sulfur content than activated carbon. Carbon black materials can be effectively utilized commercially in many applications, such as fillers, pigments, reinforcing materials, and viscosity modifiers. However, due to their very small surface area, carbon black materials are not typically used as supports for chemical catalysts or adsorbents. Low surface area carbon black materials can be considered suboptimal as support structures for catalytic applications because the low surface area is believed to be detrimental to the effective dispersion of catalytically active components, leading to low catalytic activity.

[0015] As mentioned above, activated carbons are considered to have the optimal support structure for catalytic applications because they allow good dispersion of catalytically active components and effective adsorption and reaction of chemical reagents on the catalyst surface. In contrast, the use of carbon black as a catalyst support has been limited. To utilize carbon black as a support for chemical catalysts, several groups have reported methods for modifying carbon black materials. The reported modifications have focused on methods for increasing the surface area of ​​the carbon black material. U.S. Patent No. 6,337,302 describes a process for converting "virtually useless" carbon black into activated carbon for general-purpose applications. U.S. Patent No. 3,329,626 describes a method for converting carbon black with a surface area of ​​40-150 m². 2 / g carbon black material with a surface area of ​​approximately 1200 m2 after steam activation. 2 / g of activated carbon.

[0016] Despite these teachings, it has been surprisingly discovered that certain carbon black materials exhibiting unique combinations of properties, such as surface area, pore volume, and pore size, are highly effective for use as shaped porous carbon catalyst supports for catalytic reactions involving liquid-phase and mixed-phase reaction media. The shaped porous carbon articles of the present invention can be formed into robust, mechanically strong, and chemically stable shapes that reduce resistance to liquid and gas flow, withstand the process conditions of interest, and allow for stable catalytic operation over long periods of time. These shaped porous carbon articles provide high productivity and selectivity during long-term continuous-flow operation under demanding reaction conditions, including liquid-phase reactions in which the catalyst composition is exposed to reactive solvents such as acids and water at high temperatures.

[0017] Carbon black constitutes a major portion of the shaped porous carbon products of the present invention. Accordingly, the carbon black content of the shaped porous carbon products is at least about 35% by weight or more, e.g., 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, the carbon black content of the shaped porous carbon products 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.

[0018] Typically, the carbon black material used to make the molded porous carbon articles of the present invention has a BET specific surface area of ​​about 20 m 2 / g~about 500m 2 In various embodiments, the BET specific surface area of ​​the carbon black is about 20 m 2 / g ~ approx. 350m 2 / g, about 20m 2 / g ~ approx. 250m 2 / g, about 20m 2 / g ~ approx. 225m 2 / g, about 20m 2 / g~about 200m 2 / g, about 20m 2 / g~approx. 175m 2 / g, about 20m2 / g~approximately 150m 2 / g, approximately 20m 2 / g~approximately 125m 2 / g、またはabout 20m 2 / g~approximately 100m 2 / g, approximately 25m 2 / g~approximately 500m 2 / g, approximately 25m 2 / g~approximately 350m 2 / g, approximately 25m 2 / g~approximately 250m 2 / g, approximately 25m 2 / g~approximately 225m 2 / g, approximately 25m 2 / g~approximately 200m 2 / g, approximately 25m 2 / g~approximately 175m 2 / g, approximately 25m 2 / g~approximately 150m 2 / g, approximately 25m 2 / g~approximately 125m 2 / g, approximately 25m 2 / g~approximately 100m 2 / g, approximately 30m 2 / g~approximately 500m 2 / g, approximately 30m 2 / g~approximately 350m 2 / g, approximately 30m 2 / g~approximately 250m 2 / g, approximately 30m 2 / g~approximately 225m 2 / g, approximately 30m 2 / g~approximately 200m 2 / g, approximately 30m 2 / g~approximately 175m 2 / g, approximately 30m 2 / g~approximately 150m 2 / g, approximately 30m 2 / g~approximately 125m 2 / g、またはabout 30m 2 / g~approximately 100m 2 / g. The specific surface area of ​​a carbon black material is determined from nitrogen adsorption data using the Brunauer, Emmett and Teller (BET) theory. See J. Am. Chem. Soc. 1938, 60, 309-331 and ASTM Test Methods ASTM 3663, D6556, or D4567, which are standard test methods for measuring total and external surface areas by nitrogen adsorption and are incorporated herein by reference.

[0019] Carbon black materials typically have an average pore size greater than about 5 nm, greater than about 10 nm, greater than about 12 nm, or greater than about 14 nm. In some embodiments, the average pore size of the carbon black material used to make the shaped porous carbon products ranges from about 5 nm to about 100 nm, from about 5 nm to greater than about 70 nm, from 5 nm to about 50 nm, from about 5 nm to about 25 nm, from about 10 nm to about 100 nm, from about 10 nm to greater than about 70 nm, from 10 nm to about 50 nm, or from about 10 nm to about 25 nm. Such pore sizes allow for efficient transport of large molar volume reactant molecules (e.g., biorenewably derived molecules having a six-carbon atom framework) into and out of the pore structure of the catalytically active surface, thereby enhancing activity.

[0020] The carbon black material used to make the shaped porous carbon articles of the present invention also typically has a specific pore volume of about 0.1 cm 3 / g, approx. 0.2cm 3 / g or about 0.3 cm 3 The specific pore volume of carbon black material is about 0.1 cm 3 / g ~ approx. 1cm 3 / g, approx. 0.1cm 3 / g ~ approx. 0.9cm 3 / g, approx. 0.1cm 3 / g ~ approx. 0.8cm 3 / g, approx. 0.1cm 3 / g ~ approx. 0.7cm 3 / g, approx. 0.1cm 3 / g ~ approx. 0.6cm 3 / g, approx. 0.1cm 3 / g ~ approx. 0.5cm 3 / g, approx. 0.2cm 3 / g ~ approx. 1cm 3 / g, approx. 0.2cm 3 / g ~ approx. 0.9cm 3 / g, approx. 0.2cm 3 / g ~ approx. 0.8cm 3 / g, approx. 0.2cm 3 / g ~ approx. 0.7cm 3 / g, approx. 0.2cm 3 / g ~ approx. 0.6cm 3 / g, approx. 0.2cm 3 / g ~ approx. 0.5cm 3 / g, approx. 0.3cm 3 / g ~ approx. 1cm 3 / g, approx. 0.3cm 3 / g ~ approx. 0.9cm 3 / g, approx. 0.3cm 3 / g ~ approx. 0.8cm 3 / g, approx. 0.3cm 3 / g ~ approx. 0.7cm 3 / g, approx. 0.3cm 3 / g ~ approx. 0.6cm 3 / g, or approximately 0.3 cm 3 / g ~ approx. 0.5cm 3 / g. Carbon black materials with these specific pore volumes provide sufficient volume to allow uniform wetting and good dispersion of the catalytically active components, while at the same time allowing sufficient contact between the reactant molecules and the catalytically active surface. The average pore diameter and pore volume are measured according to the procedures described in EP Barrett, LG Joyner, PP Halenda, J. Am. Chem. Soc. 1951, 73, 373-380 (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. These documents are incorporated herein by reference.

[0021] Certain carbon black materials are known to be electrically conductive. Thus, in various embodiments, the shaped porous carbon product comprises conductive carbon black, and in some embodiments, the shaped porous carbon product is electrically conductive. In other embodiments, the shaped porous carbon product comprises non-conductive carbon black. In further embodiments, the shaped porous carbon product comprises non-conductive carbon black, and the shaped porous carbon product does not exhibit electrical conductivity suitable for use as a conductive electrode. In certain embodiments, the shaped porous carbon product comprises non-conductive carbon black and less than about 50%, less than about 40%, less than about 30%, less than about 20%, less than about 10%, less than about 5%, or less than about 1% conductive carbon black, based on the total weight of carbon black in the shaped porous carbon product and / or the total weight of carbon black used to make the shaped porous carbon product. In some embodiments, the shaped porous carbon product comprises carbon black that consists of, or essentially consists of, non-conductive carbon black.

[0022] In some embodiments, the carbon black comprises silica-bonded or alumina-bonded carbon black. In certain embodiments, the shaped porous carbon article further comprises graphite and / or a metal oxide (e.g., alumina, silica, titania, etc.).

[0023] Molded porous carbon products containing carbon black can be made by a variety of methods, including dry powder pressing, drip casting, injection molding, 3D printing, and other pelleting and granulation methods. For example, dry powder pressing involves compressing carbon black particles in a press, such as a hot or cold isostatic press or a calendar press. Other pelletizing and granulation methods include tumbling carbon black particles and contacting the particles with a spray liquid containing a binder.

[0024] Various methods for preparing shaped porous carbon products include mixing water, carbon black, and a binder to form a carbon black mixture, molding the carbon black mixture to form a shaped carbon black composite, and heating the shaped carbon black composite to carbonize the binder to a water-insoluble state to form a shaped porous carbon product. In various methods for preparing shaped porous carbon products, a binder solution can be prepared by mixing water and a binder before mixing with the carbon black. Typically, the binder solution and carbon black mixture is relatively concentrated. For example, the water content of the carbon black mixture is typically about 80% by weight or less, about 55% by weight or less, about 40% by weight or less, or about 25% by weight or less. In various embodiments, the water content of the carbon black mixture can be about 5% by weight to about 70% by weight, about 5% by weight to about 55% by weight, about 5% by weight to about 40% by weight, or about 5% by weight to about 25% by weight. The viscosity of the binder solution may vary, for example, depending on the binder content, and can be easily adjusted to suit a particular molding process by changing the relative amounts of the solid and liquid components. For example, the viscosity of an aqueous solution can be varied by adjusting the binder and type of binder used. Additionally, water and binder can be mixed and heated in various ways to form the binder solution. In some cases, heating can increase the amount of binder that can be incorporated into the binder solution and / or carbon black mixture (e.g., by increasing the solubility of the binder). For example, the water and binder can be heated to at least about 50°C, at least about 60°C, or at least about 70°C. In various embodiments, the water and binder can 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.

[0025] After mixing and heating to form the binder solution, the binder solution may be cooled, if desired, prior to mixing with the carbon black or prior to forming a shaped carbon black composite.

[0026] One method of making the shaped porous carbon article of the present invention includes mixing carbon black particles with a solution containing a binder to form a slurry, forming the slurry (e.g., by extrusion) to form a shaped carbon black composite, and heating or pyrolyzing the shaped carbon black composite to carbonize the binder and form the shaped porous carbon article.

[0027] In the methods for making the various inventive shaped porous carbon products described herein, a binder solution or binder and water is thoroughly mixed and blended with carbon black to form a carbon black mixture (e.g., a slurry or paste). The weight ratio of binder to carbon black in the carbon black 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 of binder to carbon black in the carbon black mixture 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, the carbon black content of the carbon black mixture is at least about 35% by weight or more, e.g., at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, or at least about 70% by weight, on a dry weight basis. In various embodiments, the carbon black mixture has a carbon black content of about 35% to about 80%, about 35% to about 75%, about 40% to about 80%, or about 40% to about 75% by weight on a dry weight basis. The binder content of the carbon black mixture is typically at least about 10% by weight or more, e.g., at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, or at least about 45% by weight on a dry weight basis. As described herein, in various methods for making shaped porous carbon articles of the present invention, the binder content of the carbon black mixture is about 10% to about 50%, about 10% to about 45%, about 15% to about 50%, about 20% to about 50%, or about 20% to about 45% by weight on a dry weight basis.

[0028] Various methods for producing shaped porous carbon products can further include pressing or kneading the carbon black mixture. Pressing or kneading the carbon black mixture can compress the mixture and reduce the water content of the mixture. Pressing or kneading the water, carbon black, and binder (carbon black mixture) can simultaneously mix the water, carbon black, and binder. For example, one method for simultaneously mixing the water, carbon black, and binder and pressing the resulting carbon black mixture can be performed using a Mueller mixer.

[0029] After mixing the carbon black and binder, the resulting carbon black mixture is formed into a shaped carbon black composite structure of the desired shape and dimensions by a forming technique such as extrusion, pelleting, pilling, tableting, cold or hot isostatic pressing, calendaring, injection molding, 3D printing, drip casting, or other known methods for producing shaped structures. Forming methods such as cold or hot isostatic pressing and 3D printing may or may not require a binder.

[0030] Generally, shaped porous carbon products can be formed into shapes and dimensions suitable for use in known industrial reactor types, such as batch slurry systems, continuous slurry systems, stirred tank reactors, fixed beds, ebullated beds, and other known industrial reactor types. Shaped porous carbon products may be formed into a variety of shapes, including spheres, beads, cylinders, pellets, multilobed shapes, rings, stars, segmented cylinders, triholes, alpha shapes, and wheels. Shaped porous carbon products may also be formed into amorphous, non-geometric, and random shapes, as well as asymmetric shapes, such as hiflow rings and cones and alpha rings. The average diameter of the shaped porous carbon products is typically at least about 50 μm (0.05 mm), at least about 500 μm (0.5 mm), at least about 1,000 μm (1 mm), at least about 10,000 μm (10 mm), or greater, to meet process requirements.

[0031] Extrusion typically applies a pressure of at least about 100 kPa (1 bar), or from about 100 kPa (1 bar) to about 10,000 kPa (100 bar), 500 kPa (5 bar) to 5,000 kPa (50 bar), or 1,000 kPa (10 bar) to 3,000 kPa (30 bar) to the carbon black mixture.

[0032] In the drip casting method, a carbon black mixture containing carbon black particles and a binder is introduced as droplets into a casting bath to form a molded carbon black composite, which is then separated from the casting bath. Droplets of the carbon black mixture of controlled diameter can be dispensed through a nozzle of a certain size and dropped into the bath to produce solidified spherical carbon black composites of various diameters. In various embodiments of this method, the binder comprises alginate (or alginate in combination with another carbohydrate binder as described herein), which can be introduced into a bath containing a coagulation agent, such as an ionic salt (e.g., a calcium salt), as described in U.S. Pat. No. 5,472,648, which is incorporated herein by reference in its entirety. The droplets are then left substantially free in the ionic solution until the desired degree of coagulation and solidification is achieved. Alternatively, the drip casting bath used can be, for example, an oil bath or a bath used for freeze-drying. If an oil bath is used, the oil temperature is high enough to thermoset the binder (e.g., convert the binder into a three-dimensional gel). If a freeze-drying bath is used, the resulting beads are typically dried by vacuum treatment. The shaped carbon black composite from the casting process is then pyrolyzed.

[0033] As described in more detail below, other components can be added to the carbon black mixture to facilitate the molding process (e.g., lubricants, compatibilizers, etc.) or to provide other benefits. In various embodiments, the carbon black mixture further comprises a molding aid. For example, the molding aid can include a lubricant. Suitable molding aids include, for example, lignin or a lignin derivative.

[0034] Additionally, porogens can be mixed with carbon black and binders to modify and achieve desired pore characteristics in shaped porous carbon products. Other methods for modifying the porosity of shaped porous carbon products include blending two or more different starting materials (e.g., carbon blacks having different shapes and / or dimensions that are irregularly compressed to produce a multimodal pore size distribution, or carbon black from different sources / suppliers) or blending carbon with carbon black powder. One method for modifying the porosity of shaped porous carbon products includes multi-stage heat treatment and / or multi-stage compounding (e.g., pyrolysis of a shaped carbon black composite consisting of carbon powder and binder, followed by blending of fresh carbon black powder and binder and further pyrolysis of the resulting composite).

[0035] In various methods for fabricating molded porous carbon products, after processing of the carbon black mixture (e.g., slurry or paste) into a molded carbon black composite, the composite can be dried and dehydrated. Drying can be achieved by heating the composite under atmospheric pressure, typically at temperatures between room temperature (e.g., about 20°C) and about 150°C, between about 40°C and about 120°C, or between about 60°C and about 120°C. Other drying methods, such as vacuum drying, freeze drying, and dehydration, can also be used. When using certain fabrication methods for shaping (e.g., tableting, pressing), a drying step may not be necessary.

[0036] In various methods for making shaped porous carbon articles, a shaped carbon black composite (e.g., obtained from extrusion, pelleting, pilling, tableting, cold or hot isostatic pressing, calendaring, injection molding, 3D printing, drip casting, and other molding methods) is heat-treated in an inert (e.g., inert nitrogen atmosphere), oxidizing, or reducing atmosphere to carbonize at least a portion of the binder to a water-insoluble state and produce the shaped porous carbon article. Heat treatment is typically carried out at temperatures between about 250°C and about 1,000°C, about 300°C and about 900°C, about 300°C and about 850°C, about 300°C and about 800°C, about 350°C and about 850°C, about 350°C and about 800°C, about 350°C and about 700°C, about 400°C and about 850°C, or about 400°C and about 800°C. In some cases, and depending on the binder used, it has been found that lower carbonization temperatures result in gradual leaching of binder residues from the shaped porous carbon article, thereby reducing its mechanical strength for long-term catalytic use. Generally, to ensure longer-term stability, the heat treatment is carried out at a higher carbonization temperature within the range specified above. Optionally, after heat treatment, the resulting shaped porous carbon article may be washed to remove impurities.

[0037] In various preparation methods, the shaped porous carbon products of the present invention contain a binder or its carbonized product in addition to carbon black. Various documents, such as U.S. Patent No. 3,978,000, describe the use of acetone-soluble organic polymers and thermosetting resins as binders for shaped carbon supports. However, the use of flammable organic solvents and expensive thermosetting resins is not desirable or economical for the production of large quantities of shaped porous carbon products.

[0038] The mechanically strong, shaped porous carbon articles of the present invention can be produced by using an effective binder. The use of an effective binder results in a robust shaped porous carbon article that can withstand typical conditions in a continuous liquid-phase flow environment, where the liquid phase can include water or an acidic solvent, such as the environment in the transformation of biorenewably derived molecules or intermediates. In such cases, the shaped porous carbon article is mechanically and chemically stable, allowing for long-term operation without significant degradation of catalytic performance. Furthermore, the use of an effective binder results in a robust shaped porous carbon article that can withstand high temperatures.

[0039] Applicants have discovered that readily available water-soluble organic compounds are suitable as binders for producing mechanically strong molded porous carbon products. As used herein, a binder is considered water-soluble if it has a solubility of at least about 1% by weight, preferably at least about 2% by weight, at 50°C. Aqueous solutions of organic binders are well suited to commercial manufacturing processes. Organic binders that dissolve in aqueous solutions allow for good mixing and dispersion upon contact with carbon black materials. These binders also avoid safety and processing issues associated with the use of large amounts of organic solvents, which can be flammable and therefore require special storage and handling. These binders are also relatively inexpensive compared to expensive polymer-based binders. Thus, in various embodiments, the carbon black mixture does not contain water-immiscible solvents.

[0040] In various embodiments, the water-soluble organic binder comprises a carbohydrate or its derivative, which may be a monomeric, oligomeric, or polymeric carbohydrate (these are known as sugars, oligosaccharides, and polysaccharides). Carbohydrate derivatives (in monomeric, oligomeric, or polymeric form) are also included, in which the functional group or groups attached to the carbohydrate may be exchanged or derivatized. Such derivatives may be acidic or charged carbohydrates, such as alginic acid or alginates, or pectin, or aldonic, aldaric, uronic, xylonic, or xylaric acids (or oligomers, or polymers or salts thereof). Other derivatives include sugar alcohols and their polymeric forms (e.g., sorbitol, mannitol, xylitol, or carbohydrate-derived polyols). The carbohydrate binder may be used in the form of a syrup, such as molasses or corn syrup, or soluble starch, or soluble gum, or modifications thereof.

[0041] In various embodiments, the water-soluble organic binder comprises a saccharide selected from the group consisting of monosaccharides, disaccharides, oligosaccharides, derivatives thereof, and any combination thereof. In these and other embodiments, the water-soluble organic binder comprises (i) a saccharide selected from the group consisting of monosaccharides, disaccharides, oligosaccharides, derivatives thereof, and any combination thereof; (ii) a polymeric carbohydrate, a polymeric carbohydrate derivative, or a non-carbohydrate synthetic polymer, or any combination thereof. The weight ratio of (i) the saccharide to (ii) the polymeric carbohydrate, the polymeric carbohydrate derivative, or the non-carbohydrate synthetic polymer, or any combination thereof, can be from about 5:1 to about 50:1, from about 10:1 to about 25:1, or from about 10:1 to about 20:1.

[0042] In various embodiments, the water-soluble organic binder comprises a monosaccharide. For example, the monosaccharide is selected from the group consisting of glucose, fructose, hydrates thereof, syrups thereof (e.g., corn syrup, molasses, etc.), and combinations thereof. In further embodiments, the water-soluble organic binder comprises a disaccharide. Disaccharides include, for example, maltose, sucrose, syrups thereof, and combinations thereof.

[0043] As noted above, the binder can comprise a polymeric carbohydrate, a derivative of a polymeric carbohydrate, or a non-carbohydrate synthetic polymer, or any combination thereof.

[0044] In various embodiments, the binder comprises a polymeric carbohydrate, a polymeric carbohydrate derivative, or any combination thereof. The polymeric carbohydrate or polymeric carbohydrate derivative can comprise a cellulosic compound. Cellulosic compounds include, for example, methyl cellulose, ethyl cellulose, ethyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, and mixtures thereof.

[0045] Furthermore, the polymeric carbohydrate or polymeric carbohydrate derivative is selected from the group consisting of alginic acid, pectin, aldonic acid, aldaric acid, uronic acid, sugar alcohols, and salts, oligomers, and polymers thereof. The polymeric carbohydrate or polymeric carbohydrate derivative can also include starch or soluble gums.

[0046] In various embodiments, the water-soluble organic binder comprises a cellulose-based compound. In another embodiment, the binder comprises an acidic polysaccharide, such as alginic acid, pectin, or a salt thereof. In other embodiments, the binder comprises a soluble cellulose, such as an alkyl cellulose (e.g., hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, and carboxymethyl cellulose).

[0047] In various embodiments, the binder comprises a non-carbohydrate synthetic polymer. Water-soluble polymers or copolymers can be used as binders. For example, polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetate, polyacrylate, polyether (e.g., polyethylene glycol), and copolymers derived therefrom (which may be block copolymers comprising a water-insoluble block monomer and a water-soluble block monomer), as well as blends thereof, can be used. In some cases, the water-soluble copolymer may be a block copolymer comprising a water-soluble polymer block and a hydrophobic, carbonizable second polymer block (e.g., polystyrene). In another embodiment, a polymer dispersion in water, i.e., a water-insoluble polymer dispersed in water (using a surfactant), such as commercially available polyvinyl alcohol, polyacrylonitrile, polyacrylonitrile-butadiene-styrene, phenolic polymer, or lignin polymer dispersion, is used as the binder. Copolymers consisting of water-soluble branches (e.g., polyacrylic acid) and hydrophobic branches (e.g., polymaleic anhydride, polystyrene) can also be dissolved in water, allowing the hydrophobic branches to be carbonized without depolymerization during pyrolysis. Carbohydrates or their derivatives, water-soluble polymers, and dispersions of polymers in water can be used together in various combinations.

[0048] As mentioned above, water-soluble organic binders that can be used in combination with the sugar binder include water-soluble celluloses and starches (e.g., hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose), water-soluble alcohols (e.g., sorbitol, xylitol, polyvinyl alcohol), water-soluble acetals (e.g., polyvinyl butyral), water-soluble acids (e.g., stearic acid, citric acid, alginic acid, aldonic acid, aldaric acid, uronic acid, xylonic acid, or xylaric acid (or oligomers, polymers, or salts or esters thereof), polyvinyl acrylic acid (or salts or esters thereof)). In some embodiments, the water-soluble organic binder combination includes a cellulosic compound and a monosaccharide. In particular embodiments, the cellulosic compound includes hydroxyethyl cellulose or methyl cellulose, and the monosaccharide includes glucose, fructose, or hydrates thereof (e.g., glucose). In particular, one combination includes glucose and hydroxyethyl cellulose, which provides a shaped porous carbon product with improved mechanical strength, especially when processed at high carbonization temperatures. In other embodiments, the water-soluble organic binder combination includes a monosaccharide and a water-soluble alcohol, such as sorbitol, mannitol, xylitol, or polyvinyl alcohol. In other embodiments, the water-soluble organic binder combination includes a monosaccharide and a water-soluble acid, such as stearic acid, pectin, alginic acid, or polyacrylic acid (or a salt thereof). In further embodiments, the water-soluble organic binder combination includes a monosaccharide and a water-soluble ester, such as polyacrylate or polyacetate. In still other embodiments, the water-soluble organic binder combination includes a monosaccharide and a water-soluble acetal, such as polyacetal (e.g., polyvinyl butyral).

[0049] Other water-soluble compounds can be used in combination with carbohydrate or polymer binders. The combination of carbohydrate or other binders with selected water-soluble organic compounds can provide advantages in the fabrication and properties of the resulting molded porous carbon product. For example, water-soluble organic compounds such as stearic acid or stearates, e.g., Zr stearate or NH4, can provide lubrication during the molding process. Wetting agents (e.g., the GLYDOL series available from Zschimmer and Schwarz) can also be added.

[0050] The porogen may be added in combination with a binder (or binders). The porogen is typically added to occupy a certain molar volume in the formulation, such that after molding and heat treatment, the porogen thermally decomposes, leaving pores of a certain volume and diameter in the molded product. The presence of such pores can be beneficial for performance. For example, when used as a catalyst support, the presence of such pores can lead to more effective diffusion (of reactants and products) to and from the catalytically active surface. More efficient ingress and egress of reactants and products can lead to improved catalyst productivity and selectivity. Porogens are typically oligomeric (e.g., higher oligomeric dimers, trimers) or polymeric in nature. Water-soluble organic compounds, such as water-soluble linear and branched polymers and crosslinked polymers, are suitable for use as porogens. Polyacrylates (e.g., weakly crosslinked polyacrylates known as superabsorbents), polyvinyl alcohol, polyvinyl acetate, polyesters, polyethers, or copolymers thereof (which may be block copolymers) can be used as porogens. In some cases, the water-soluble copolymer may be a block copolymer comprising a water-soluble polymer block and a hydrophobic, carbonizable second polymer (e.g., polystyrene). In another embodiment, a polymer dispersion in water, i.e., a water-insoluble polymer dispersed in water (using a surfactant), such as commercially available polyvinyl alcohol, polyacrylonitrile, polyacrylonitrile-butadiene-styrene, or a phenolic polymer dispersion, is used as the binder. Copolymers consisting of a water-soluble branch (e.g., polyacrylic acid) and a hydrophobic branch (e.g., polymaleic anhydride, polystyrene) can also be used to dissolve the copolymer in water, allowing the hydrophobic branch to be carbonized without depolymerization during pyrolysis. Carbohydrates or their derivatives, (disaccharides, oligosaccharides, polysaccharides, e.g., sucrose, maltose, trihalose, starch, cellobiose, cellulose), water-soluble polymers, and polymer dispersions in water can be used together in any combination as porogens to obtain shaped porous carbon black products having the desired pore size and pore volume characteristics described herein.

[0051] Porogens can also be added as gels (e.g., pregel superabsorbents) or as water-insoluble, incompressible solids (e.g., polystyrene microbeads, lignin, phenolic polymers) or as expandable porogens, such as EXPANSEL microparticles available from Akzo Nobel Pulp and Performance (Sundsvall, Sweden). The molecular weight of the oligomer or polymer can also be selected to engineer the desired pore size and volumetric properties of the shaped carbon products of the present invention. For example, the desired shaped carbon products can have a unimodal, bimodal, or multimodal pore size distribution as a result of the addition of porogen. For example, a bimodal or multimodal pore size distribution can consist of a high percentage of pores between 10 and 100 nm, with additional pores greater than 100 nm. Such pore structures can confer performance advantages. For example, the presence of such a pore size distribution can lead to more effective diffusion (of reactants and products) through larger pores (transport pores) to and from catalytically active surfaces present in pores of 10-100 nm size. More efficient ingress and egress of reactants and products can lead to improved catalyst productivity and selectivity and / or yield.

[0052] After heat treatment of the molded carbon black composite, the resulting molded porous carbon article comprises carbon black and a carbonized binder. More generally, the molded porous carbon article may comprise carbon agglomerates. Without being bound by any particular theory, it is believed that the carbon agglomerates comprise carbon aggregates or particles that are at least partially physically bound or entangled by the carbonized binder. Additionally, and without being bound by any particular theory, the resulting agglomerates may comprise chemical bonds of the carbonized binder with the agglomerates or particles.

[0053] The carbonized binder comprises the carbonized product of the water-soluble organic binder described herein. Carbonization of the binder during fabrication of the shaped porous carbon article can reduce the weight of the original shaped carbon black composite. Thus, in various embodiments, the carbonized binder content of the shaped porous carbon article is about 10% to about 50% by weight, about 20% to about 50% by weight, about 25% to about 40% by weight, or about 25% to about 35% by weight (e.g., 30% by weight).

[0054] The specific surface area (BET surface area), average pore size, and specific pore volume of a formed porous carbon product are typically comparable to those exhibited by the carbon black material used to make the product. However, the fabrication process may decrease or increase these properties of the product relative to the carbon black material (e.g., about a 10-50% or 10-30% decrease or increase). In various embodiments, the formed porous carbon product has a specific surface area of ​​about 20 m 2 / g~about 500m 2 / g, about 20m 2 / g ~ approx. 350m 2 / g, about 20m 2 / g ~ approx. 250m 2 / g, about 20m 2 / g ~ approx. 225m 2 / g, about 20m 2 / g~about 200m 2 / g, about 20m 2 / g~approx. 175m 2 / g, about 20m 2 / g~about 150m 2 / g, about 20m 2 / g ~ approx. 125m 2 / g, or approximately 20m 2 / g~about 100m 2 / g, approx. 25m 2 / g~about 500m 2 / g, approx. 25m 2 / g ~ approx. 350m 2 / g, approx. 25m 2 / g ~ approx. 250m 2 / g, approx. 25m 2 / g ~ approx. 225m 2 / g, approx. 25m 2 / g~about 200m2 / g, approx. 25m 2 / g~approx. 175m 2 / g, approx. 25m 2 / g~about 150m 2 / g, approx. 25m 2 / g ~ approx. 125m 2 / g, approx. 25m 2 / g~about 100m 2 / g, approx. 30m 2 / g~about 500m 2 / g, approx. 30m 2 / g ~ approx. 350m 2 / g, approx. 30m 2 / g ~ approx. 250m 2 / g, approx. 30m 2 / g ~ approx. 225m 2 / g, approx. 30m 2 / g~about 200m 2 / g, approx. 30m 2 / g~approx. 175m 2 / g, approx. 30m 2 / g~about 150m 2 / g, approx. 30m 2 / g ~ approx. 125m 2 / g, or approximately 30m 2 / g~about 100m 2 / g. The specific surface area of ​​a shaped porous carbon product is determined from nitrogen adsorption data using Brunauer, Emmett and Teller. See J. Am. Chem. Soc. 1938, 60, 309-331 and the methods described in ASTM Test Methods ASTM D3663, D6556, or D4567. These are standard test methods for measuring surface area by nitrogen adsorption.

[0055] The shaped porous carbon products typically have an average pore size greater than about 5 nm, greater than about 10 nm, greater than about 12 nm, or greater than about 14 nm. In some embodiments, the shaped porous carbon products have an average pore size of about 5 nm to about 100 nm, about 5 nm to about 70 nm, 5 nm to about 50 nm, about 5 nm to about 25 nm, about 10 nm to about 100 nm, about 10 nm to about 70 nm, 10 nm to about 50 nm, or about 10 nm to about 25 nm. The shaped porous carbon products of the present invention also typically have a specific pore volume of about 0.1 cm for pores with diameters of 1.7 nm to 100 nm, as measured by the BJH method. 3 / g, approx. 0.2cm 3 / g or about 0.3 cm 3 In various embodiments, the shaped porous carbon product has a specific pore volume of pores with diameters between 1.7 nm and 100 nm of greater than about 0.1 cm3 / g, as measured by the BJH method. 3 / g ~ approx. 1.5cm 3 / g, approx. 0.1cm 3 / g ~ approx. 0.9cm 3 / g, approx. 0.1cm 3 / g ~ approx. 0.8cm 3 / g, approx. 0.1cm 3 / g ~ approx. 0.7cm 3 / g, approx. 0.1cm 3 / g ~ approx. 0.6cm 3 / g, approx. 0.1cm 3 / g ~ approx. 0.5cm 3 / g, approx. 0.2cm 3 / g ~ approx. 1cm 3 / g, approx. 0.2cm 3 / g ~ approx. 0.9cm 3 / g, approx. 0.2cm 3 / g ~ approx. 0.8cm 3 / g, approx. 0.2cm 3 / g ~ approx. 0.7cm 3 / g, approx. 0.2cm 3 / g ~ approx. 0.6cm 3 / g, approx. 0.2cm 3 / g ~ approx. 0.5cm 3 / g, approx. 0.3cm 3 / g ~ approx. 1cm 3 / g, approx. 0.3cm 3 / g ~ approx. 0.9cm 3 / g, approx. 0.3cm3 / g ~ approx. 0.8cm 3 / g, approx. 0.3cm 3 / g ~ approx. 0.7cm 3 / g, approx. 0.3cm 3 / g ~ approx. 0.6cm 3 / g, or approximately 0.3 cm 3 / g ~ approx. 0.5cm 3 / g. The average pore size and specific pore volume are measured according to the procedures described in EP Barrett, LG Joyner, PP Halenda, J. Am. Chem. Soc. 1951, 73, 373-380 (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. These documents are incorporated herein by reference.

[0056] The specific surface area is generally proportional to the concentration of micropores in the formed porous carbon product. In particular, formed porous carbon products typically have a low concentration of pores with an average diameter of less than 1.7 nm. Typically, pores with an average diameter of less than 1.7 nm account for less than about 10%, less than about 5%, less than about 4%, less than about 3%, or less than about 2.5% of the pore volume of the formed porous carbon product. Similarly, in various embodiments, the pore size distribution of the formed porous carbon product does not exhibit a peak below about 10 nm or less than about 5 nm. For example, the formed porous carbon product can have a pore size distribution in which the distribution peaks at diameters 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 20 nm. The formed porous carbon product can also have a pore size distribution in which the distribution peaks at diameters less than about 100 nm, less than about 90 nm, less than about 80 nm, or less than about 70 nm.

[0057] Additionally, the shaped porous carbon product advantageously exhibits a high concentration of mesopores having diameters of about 10 nm to about 100 nm, about 20 nm to about 100 nm, or about 10 nm to about 50 nm. Thus, in various embodiments, at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90%, or at least about 95% of the pore volume of the shaped porous carbon product is attributable to pores having an average pore diameter of about 10 nm to about 100 nm, as measured by the BJH method, based on pores having diameters of 1.7 nm to 100 nm. For example, when measured by the BJH method using pores with diameters of 1.7 nm to 100 nm as a standard, about 50% to about 99%, about 50% to about 95%, about 50% to about 90%, about 50% to about 80%, about 60% to about 99%, about 60% to about 95%, about 60% to about 90%, about 60% to about 80%, about 70% to about 99%, about 70% to about 95%, about 70% to about 90%, about 70% to about 80%, about 80% to about 99%, about 80% to about 95%, about 80% to about 90%, or about 90% to about 99% of the pore volume of the molded porous carbon product is attributable to pores with an average pore diameter of about 10 nm to about 100 nm. In various embodiments, at least about 35%, at least about 40%, at least about 45%, or at least about 50% of the pore volume of the formed porous carbon product is attributable to pores having an average pore size of about 20 to about 90 nm or about 10 to about 50 nm, as measured by the BJH method, based on pores having a diameter of 1.7 to 100 nm. For example, at least about 35% to about 80%, about 35% to about 75%, about 35% to about 65%, about 40% to about 80%, about 40% to about 75%, or about 40% to about 70% of the pore volume of the formed porous carbon product is attributable to pores having an average pore size of about 20 to about 90 nm or about 10 to about 50 nm, as measured by the BJH method, based on pores having a diameter of 1.7 to 100 nm.

[0058] Typically, the formed porous carbon product exhibits a relatively low concentration of pores less than 10 nm, less than 5 nm, or less than 3 nm. For example, based on pores with diameters between 1.7 nm and 100 nm, about 10% or less, about 5% or less, or about 1% or less of the pore volume of the formed porous carbon product is attributable to pores with an average pore diameter of less than 10 nm, less than 5 nm, or less than 3 nm, as measured by the BJH method. In various embodiments, based on pores with diameters between 1.7 nm and 100 nm, about 0.1% 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% of the pore volume of the formed porous carbon product is attributable to pores with an average pore diameter of less than 10 nm, less than 5 nm, or less than 3 nm, as measured by the BJH method.

[0059] The shaped porous carbon products described herein are mechanically strong and stable. Crushing strength refers to the resistance of a solid to compression and is an important property in industrial applications of shaped porous carbon products such as those described herein. Devices for measuring the crushing strength of individual solid particles typically include a dynamometer, which measures the incremental force applied to the solid during the advancement of a piston. The applied force increases until the solid breaks, is crushed into small pieces, and ultimately becomes a powder. The corresponding value of the crushing force is defined as the crushing strength and is typically averaged over multiple samples. Standard protocols for measuring crushing strength are known in the art. For example, the mechanical strength of shaped porous carbon products can be measured by the crushing strength test protocols described by ASTM D4179 or ASTM D6175. These ASTMs are incorporated herein by reference. Some of these test methods are reportedly limited to particles of a certain size range, shape, or manufacturing method. However, the crush strength of irregularly shaped particles and particles of various sizes and manufacturing methods can nevertheless be adequately measured by these and similar test methods.

[0060] In various embodiments, shaped porous carbon articles made according to the present invention have a radial crushing strength greater than 1 lb / mm (4.4 N / mm), greater than 2 lb / mm (8.8 N / mm), or greater than 3 lb / mm (13.3 N / mm). In particular embodiments, the radial crushing strength of the shaped porous carbon article is from about 1 lb / mm (4.4 N / mm) to about 20 lb / mm (88 N / mm), from about 1 lb / mm (4.4 N / mm) to about 15 lb / mm (66 N / mm), or from about 2 lb / mm (8.8 N / mm) to about 10 lb / mm (44 N / mm). In measuring radial crushing strength, the force measured is relative to the dimension of the solid article perpendicular to the applied load, which may typically range from about 0.5 mm to about 20 mm, from about 1 mm to about 10 mm, or from about 1.5 mm to 5 mm. For irregularly shaped porous carbon products, radial crushing strength is measured by applying a load perpendicular to the longest dimension of the solid.

[0061] Mechanical crush strength can also be reported on a unitless basis with respect to the dimensions of the shaped porous carbon product (e.g., for a generally spherical solid or solid having approximately equal cross-sectional dimensions). Shaped porous carbon products made according to the present invention typically have a crush strength of greater than about 5 lb (22 N), greater than about 8 lb (36 N), or greater than 10 lb (44 N). In various embodiments, the shaped porous carbon products can have a crush strength of from about 5 lb (22 N) to about 20 lb (88 N), from about 5 lb (22 N) to about 15 lb (66 N), or from about 7.5 lb (33 N) to about 15 lb (66 N).

[0062] In addition to crush strength, the shaped porous carbon articles also exhibit desirable abrasion and attrition resistance. Several test methods exist that are suitable for measuring the abrasion and attrition resistance of shaped porous carbon articles and catalysts made according to the present disclosure. These methods are a measure of the propensity of a material to generate fines during handling, handling, and use during operation.

[0063] One such method is the abrasion index, measured by ASTM D4058-96 (Standard Test Method for Attrition and Abrasion of Catalysts and Catalyst Carriers), which is a measure of a material's (e.g., extrudate or catalyst particle) resistance to abrasive wear by repeatedly impacting the particle against a hard surface in a specified rotating test drum. This method is incorporated herein by reference. This test method is generally applicable to tablets, extrudates, spheres, granules, pellets, and irregularly shaped particles, typically having at least one dimension greater than about 1 / 16 inch (1.6 mm) or about 3 / 4 inch (19 mm), although abrasion measurements can also be performed on larger sized materials. Variable and fixed speed rotating cylinder abrasimeters designed according to ASTM D4058-96 are readily available. Typically, the material to be tested is placed in the drum of the rotating test cylinder and rotated at about 55 to about 65 RPM for 35 minutes. The material is then removed from the test cylinder and sieved through a 20-mesh sieve. The percentage (by weight) of the original material sample retained on the 20-mesh sieve is referred to as the "retention percentage." Formed porous carbon products (e.g., extrudates) and catalysts made therefrom typically exhibit a rotary drum wear index such that the retention percentage is greater than about 85%, greater than about 90%, greater than about 92%, greater than about 95%, greater than about 97%, or greater than about 99% by weight, as measured by ASTM D4058-96 or a similar method. A retention percentage of greater than about 97% indicates a material with exceptional mechanical stability and robust structure, particularly desirable for industrial applications.

[0064] The attrition rate (ABL) is another measure of the durability of shaped porous carbon products (e.g., extrudates) and catalysts made therefrom. Similar to the attrition index, the results of this test can be used as a measure of the material's resistance to abrasive wear due to vigorous horizontal shaking of particles within the confines of a 30-mesh sieve. Typically, the material to be tested is first dedusted on a 20-mesh sieve by gently moving the sieve sideways at least about 20 times. The dedusted sample is then weighed and transferred into a clean 30-mesh sieve stacked on top of a clean sieve pan for fines collection. The entire sieve stack is then assembled on a sieve shaker (e.g., a RO-Tap RX-29 sieve shaker manufactured by Industrial Group, Mentor, Ohio), securely capped, and shaken for about 30 minutes. The collected product fines are weighed and divided by the weight of the dedusted sample to calculate the attrition rate of the sample as a weight percent. Formed porous carbon products (e.g., extrudates) and catalysts therefrom typically have horizontal shaking in-sieve attrition rates of less than about 5 wt.%, less than about 3 wt.%, less than about 2 wt.%, less than about 1 wt.%, less than about 0.5 wt.%, less than about 0.2 wt.%, less than about 0.1 wt.%, less than about 0.05 wt.%, or less than about 0.03 wt.%. Attrition rates of less than 2% are particularly desirable for industrial applications.

[0065] The shaped porous carbon articles and methods of making the shaped porous carbon articles of the present invention include various combinations of the features described herein. For example, in various embodiments, the shaped porous carbon article comprises a carbonized binder comprising the carbonized product of (a) carbon black and (b) a water-soluble organic binder, wherein the shaped porous carbon article has a BET specific surface area of ​​about 20 m 2 / g~about 500m 2 / g or approximately 25m 2 / g ~ approx. 250m 2 / g, with an average pore diameter of greater than about 10 nm and a specific pore volume of about 0.1 cm 3 / g, a radial crushing strength greater than about 4.4 N / mm (1 lb / mm), and a carbon black content of at least about 35 wt.%. In other embodiments, the shaped porous carbon product comprises carbon agglomerates, and the shaped porous carbon product has an average diameter of at least about 50 μm and a BET specific surface area of ​​about 20 m 2 / g~about 500m 2 / g or approximately 25m 2 / g ~ approx. 250m 2 / g, with an average pore diameter of greater than about 10 nm and a specific pore volume of about 0.1 cm 3 / g and a radial crushing strength of greater than about 4.4 N / mm (1 lb / mm).

[0066] The formed porous carbon products of the present invention can also have a low sulfur content. For example, the formed porous carbon products can have a sulfur content of about 1% by weight or about 0.1% by weight or less.

[0067] Characteristics and properties such as carbon black type, binder, specific surface area, specific pore volume, average pore size, crush strength, abrasion and wear resistance, and carbon black content can be independently adjusted or varied within the ranges described herein, and the shaped porous carbon products can be further defined by the properties described herein.

[0068] For example, the formed porous carbon product includes (a) carbon black and (b) a carbonized binder including the carbonized product of a water-soluble organic binder, and the formed porous carbon product has a BET specific surface area of ​​about 20 m 2 / g~about 500m 2 / g, with an average pore diameter of greater than about 5 nm and a specific pore volume of about 0.1 cm 3 / g, a radial crushing strength greater than about 4.4 N / mm (1 lb / mm), a carbon black content of at least about 35% by weight, and a carbonized binder content of about 20% to about 50% by weight.

[0069] In another embodiment, the shaped porous carbon article of the present invention comprises a carbonized binder comprising the carbonization product of (a) carbon black and (b) a water-soluble organic binder, wherein the shaped porous carbon article has a BET specific surface area of ​​about 20 m 2 / g~about 500m 2 / g or approximately 25m 2 / g ~ approx. 250m 2 / g, with an average pore diameter of greater than about 10 nm and a specific pore volume of about 0.1 cm 3 / g, a radial crushing strength of greater than about 4.4 N / mm (1 lb / mm), and a carbon black content of at least about 35 wt.%, wherein the shaped porous carbon product has at least about 35% of its pore volume attributable to pores having an average pore diameter of about 10 nm to about 50 nm, when the pore volume is measured based on pores having a diameter of 1.7 nm to 100 nm.

[0070] Yet another shaped porous carbon product of the present invention comprises carbon agglomerates, the shaped porous carbon product having an average diameter of at least about 50 μm and a BET specific surface area of ​​at least about 20 m 2 / g~about 500m 2 / g or approximately 25m 2 / g ~ approx. 250m 2 / g, with an average pore diameter of greater than about 10 nm and a specific pore volume of about 0.1 cm 3 / g, a radial crushing strength of greater than about 4.4 N / mm (1 lb / mm), and the shaped porous carbon product has at least about 35% of its pore volume attributable to pores having an average pore diameter of about 10 nm to about 50 nm, when the pore volume is measured based on pores having a diameter of 1.7 nm to 100 nm.

[0071] Methods of the present invention include various combinations of the features, characteristics, and method steps described herein. For example, various methods of making a shaped porous carbon product include combining and heating water and a water-soluble organic binder to form a binder solution; combining carbon black particles with the binder solution to form a carbon black mixture; shaping the carbon black mixture to form a shaped carbon black composite; and heating the shaped carbon black composite to carbonize the binder to a water-insoluble state and form the shaped porous carbon product, wherein the water and binder are heated to a temperature of at least about 50° C., and the binder comprises (i) a saccharide selected from the group consisting of monosaccharides, disaccharides, oligosaccharides, derivatives thereof, and any combination thereof, and (ii) a polymeric carbohydrate, a derivative of a polymeric carbohydrate, or a non-carbohydrate synthetic polymer, or any combination thereof.

[0072] Another method of making a shaped porous carbon product includes mixing water, carbon black, and a water-soluble organic binder to form a carbon black mixture; shaping the carbon black mixture to form a shaped carbon black composite; and heating the shaped carbon black composite to carbonize the binder to a water-insoluble state to form a shaped porous carbon product, wherein the binder comprises (i) a saccharide selected from the group consisting of monosaccharides, disaccharides, oligosaccharides, derivatives thereof, and any combination thereof, and (ii) a polymeric carbohydrate, a derivative of a polymeric carbohydrate, or a non-carbohydrate synthetic polymer, or any combination thereof.

[0073] Further methods include combining water, carbon black, and a binder to form a carbon black mixture; shaping the carbon black mixture to form a shaped carbon black composite; and heating the shaped carbon black composite to carbonize the binder to a water-insoluble state to form a shaped porous carbon product, wherein the binder comprises a saccharide selected from the group consisting of monosaccharides, disaccharides, oligosaccharides, derivatives thereof, or any combination thereof, and wherein the weight ratio of binder to carbon black in the carbon black mixture is 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.

[0074] Yet another method includes combining water, carbon black, and a binder to form a carbon black mixture; shaping the carbon black mixture to form a shaped carbon black composite; and heating the shaped carbon black composite to carbonize the binder to a water-insoluble state to form a shaped porous carbon product, wherein the binder comprises a saccharide selected from the group consisting of monosaccharides, disaccharides, oligosaccharides, derivatives thereof, or any combination thereof, and wherein the water content of the carbon black mixture is about 80% by weight or less, about 55% by weight or less, about 40% by weight or less, or about 25% by weight or less.

[0075] Another method for making a shaped porous carbon product by extrusion preferably includes mixing carbon black particles with an aqueous solution containing a water-soluble organic binder compound selected from the group consisting of monosaccharides, disaccharides, oligosaccharides, polysaccharides, and combinations thereof to form a carbon black mixture; molding the carbon black mixture under a pressure of at least 500 kPa (5 bar) to form a shaped carbon black composite; drying the shaped carbon black material at a temperature of from about room temperature (e.g., about 20°C) to about 150°C; and heating the dried shaped carbon black composite to a temperature of from about 250°C to about 800°C in an oxidizing, inert, or reducing atmosphere (e.g., an inert N2 atmosphere) to carbonize the binder to a water-insoluble state and form a shaped porous carbon product, the carbon black mixture comprising at least about 40% by weight carbon black and at least about 40% by weight binder on a dry basis, the shaped porous carbon product having an average diameter of at least about 50 μm and a BET specific surface area of ​​at least about 20 m. 2 / g~about 500m 2 / g or approximately 25m 2 / g ~ approx. 250m 2 / g, with an average pore diameter of greater than about 10 nm and a specific pore volume of about 0.1 cm 3 The carbon black content of the shaped porous carbon product may be at least about 35% by weight or as described herein. In some embodiments, the shaped porous carbon product has at least about 35% of its pore volume attributable to pores having an average pore size of about 10 nm to about 50 nm, when the pore volume is measured based on pores having a diameter of 1.7 nm to 100 nm. The carbon black may optionally be heated during the shaping step (e.g., extrusion, pelleting, pilling, tableting, cold or hot isostatic pressing, calendaring, injection molding, 3D printing, drip casting, or other methods) to facilitate shaping of the carbon black mixture into the desired shape.

[0076] Further shaped porous carbon articles and methods of making of the present invention include any combination of the features described herein, where said features are independently substituted for or added to the above-described embodiments.

[0077] The shaped porous carbon black products may also be wash-coated or dip-coated onto other materials to create structured composites. The shaped porous carbon black products (at least micron-sized) may be heterogeneous, isolated composite domains (e.g., carbon domains primarily in carbon-ZrO composites or large pore (mm-sized) ceramic foams) as well as layered or structured materials (e.g., carbon black wash-coatings on inert supports such as steatite, plastic, or glass balls).

[0078] The shaped porous carbon black products of the present invention can be further subjected to thermal or chemical treatments to alter the physical and chemical properties of the shaped porous carbon black product. For example, chemical treatments such as oxidation can create a more hydrophilic surface, which can provide advantages (improved wetting and dispersion) for catalyst fabrication. Oxidation methods are known in the art. See, for example, U.S. Pat. Nos. 7,922,2805 and 6,471,763. In other embodiments, the shaped porous carbon black products have been surface treated using known methods for introducing functional groups into carbon-based substrates. See, for example, WO 2002 / 018929, WO 97 / 47691, WO 99 / 23174, WO 99 / 31175, WO 99 / 51690, WO 2000 / 022051, and WO 99 / 63007. All of these patents are incorporated herein by reference. The functional groups may be ionizable groups such that they contain anionic or cationic moieties when the shaped porous carbon black article is exposed to ionizing conditions. This embodiment is useful when the shaped porous carbon black article is used as a separation medium in chromatography columns and other separation devices.

[0079] Catalyst composition and method of preparation Various aspects of the present invention also relate to catalyst compositions and methods of making catalyst compositions comprising the shaped porous carbon articles as catalyst supports. The shaped porous carbon articles of the present invention allow for effective dispersion and immobilization of catalytically active components or precursors thereof on the surface of the carbon article. The catalyst compositions of the present invention are suitable for use in long-term continuous-flow operation step reactions under demanding reaction conditions, such as liquid-phase reactions in which the shaped porous carbon articles are exposed to reactive solvents such as acids and water at high temperatures. Catalyst compositions comprising the shaped porous carbon articles of the present invention exhibit the operational stability required for general-purpose applications.

[0080] Generally, the catalyst compositions of the present invention comprise a shaped porous carbon article as a catalyst support and a catalytically active component or precursor thereof on the surface (external and / or internal surface) of the support. In various catalyst compositions of the present invention, the catalytically active component or precursor thereof comprises a metal on the surface of the shaped porous carbon article. In these and other embodiments, the metal comprises at least one metal selected from Groups IV, V, VI, VII, VIII, IX, X, XI, XII, and XIII. Some preferred metals include cobalt, nickel, copper, zinc, iron, vanadium, molybdenum, manganese, barium, ruthenium, rhodium, rhenium, palladium, silver, osmium, iridium, platinum, gold, and combinations thereof. In various embodiments, the metal comprises at least one d-block metal. Some preferred d-block metals include cobalt, nickel, copper, zinc, iron, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, gold, and combinations thereof. Typically, the metal(s) on the surface of the catalyst support constitute from about 0.1% to about 50%, from about 0.1% to about 25%, from about 0.1% to about 10%, from about 0.1% to about 5%, from about 0.25% to about 50%, from about 0.25% to about 25%, from about 0.25% to about 10%, from about 0.25% to about 5%, from about 1% to about 50%, from about 1% to about 25%, from about 1% to about 10%, from about 1% to about 5%, from about 5% to about 50%, from about 5% to about 25%, or from about 5% to about 10% of the total weight of the catalyst.

[0081] Generally, the metal may be present in various forms (e.g., elemental, metal oxide, metal hydroxide, metal ion, metalate, polyanion, oligomer, or colloid, etc.), but typically the metal is reduced to its elemental form during preparation of the catalyst composition or in situ in the reactor under reaction conditions.

[0082] The metal(s) can be deposited on the surface of the shaped porous carbon article by methods known in the art, including, but not limited to, incipient wetness impregnation, ion exchange, deposition precipitation, coating, and vacuum impregnation. When two or more metals are deposited on the same support, they can be deposited sequentially or simultaneously. Multiple impregnation steps are also possible (e.g., dual impregnation of the same metal under different conditions to increase overall metal loading or tailor metal distribution throughout the shell). In various embodiments, the metal(s) for the oxidation catalyst deposited on the shaped porous carbon article forms a shell that at least partially covers the surface of the carbon article.

[0083] In other words, the metal deposited on the shaped porous carbon article coats the exterior surface of the carbon article. In various embodiments, the metal penetrates the surface pores of the shaped porous carbon article, forming a shell layer ("eggshell") of about 10 μm to about 400 μm, or about 50 μm to about 150 μm (e.g., about 100 μm). In certain embodiments, the shell can form the lower surface, producing a lower surface zone ("yolk") of 10 μm to about 400 μm that contains the catalytically active metal. Structured shells, characterized by different metal distributions throughout the shell for various metals, are also possible.

[0084] In other embodiments, a metal or metals may be deposited on the carbon black particles prior to the formation of the shaped porous carbon product. Accordingly, in these embodiments, the carbon black mixture further comprises a metal, such as a d-block metal. Some preferred d-block metals include cobalt, nickel, copper, zinc, iron, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, gold, and combinations thereof. In various embodiments, the metal comprises at least one metal selected from Groups IV, V, VI, VII, VIII, IX, X, XI, XII, and XIII. Preferred metals include cobalt, nickel, copper, zinc, iron, vanadium, molybdenum, manganese, barium, ruthenium, rhodium, rhenium, palladium, silver, osmium, iridium, platinum, gold, and combinations thereof. Typically, the metal(s) can comprise about 0.1% to about 50%, about 0.1% to about 25%, about 0.1% to about 10%, about 0.1% to about 5%, about 0.25% to about 50%, about 0.25% to about 25%, about 0.25% to about 10%, about 0.25% to about 5%, about 1% to about 50%, about 1% to about 25%, about 1% to about 10%, about 1% to about 5%, about 5% to about 50%, about 5% to about 25%, or about 5% to about 10%. For example, if the metal used is a precious metal, the metal content can be about 0.25% to about 10% of the total weight of the shaped porous carbon product. Alternatively, if the metal used is a non-precious metal, the metal content can be about 0.1% to about 50% of the total weight of the shaped porous carbon product.

[0085] In various embodiments, after metal deposition, the catalyst composition is optionally dried, for example, for at least about 1 hour, more typically 3 hours or more, at a temperature of at least about 50° C., more typically at least about 120° C. Alternatively, drying can be carried out in a multi-stage manner with sequential or independently controlled temperature zones (e.g., 60° C., 80° C., and 120° C.).

[0086] Typically, drying begins below the boiling point of the solvent (e.g., 60°C) and is then increased in temperature. In these and other embodiments, the catalyst is dried under subatmospheric or atmospheric conditions. In various embodiments, the catalyst is reduced after drying (e.g., by flowing 5% H in N at 350°C for 3 hours). Still further, in these and other embodiments, the catalyst is calcined, for example, at at least about 200°C for a period of time (e.g., at least about 3 hours).

[0087] In some embodiments, the catalyst composition of the present invention is prepared by depositing a catalytically active component or precursor thereof after the shaped porous carbon article has been formed (i.e., by depositing directly on the surface of the shaped porous carbon article). The catalyst composition of the present invention can be prepared by contacting the shaped porous carbon article with a solubilized metal complex or a combination of solubilized metal complexes. The heterogeneous mixture of solid and liquid is then stirred, mixed, and / or shaken to enhance uniformity of catalyst dispersion, which in turn allows for more uniform deposition of the metal(s) on the support surface upon liquid removal. After deposition, the metal complex(es) on the shaped porous carbon article are heated and reduced under a reducing agent, such as a hydrogen-containing gas (e.g., forming gas: 5% H2 and 95% N2). The temperature at which heating is performed typically ranges 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 is typically performed for a time period ranging from about 1 hour to about 5 hours, or from about 2 hours to about 4 hours. The reduction can also be carried out in the liquid phase, for example, the catalyst composition can be treated in a fixed bed with a liquid containing the reducing agent pumped through the static catalyst.

[0088] In another embodiment, the catalyst composition of the present invention is prepared by depositing a catalytically active component or precursor thereof onto carbon black prior to forming the shaped porous carbon article. In one such method, a slurry of carbon black and solubilized metal complex(es) is prepared. The carbon black may be first dispersed in a liquid, such as water. The solubilized metal complex(es) can then be added to the carbon black-containing slurry. The heterogeneous mixture of solids and liquid is then stirred, mixed, and / or shaken to increase the uniformity of the catalyst dispersion, which in turn allows for more uniform deposition of the metal(s) on the carbon black surface upon removal of the liquid. After deposition, the metal complex(es) on the carbon black are heated and reduced with a reducing agent as described above. The metal-loaded carbon black particles can then be formed by methods described for forming porous carbon articles. The slurry can also be wash-coated onto an inert support rather than formed into bulk catalyst pellets.

[0089] The catalyst composition comprising the shaped porous carbon product as a catalyst support can be effectively utilized in a variety of reactor types, particularly reactors adapted for liquid phase media, such as batch slurry, continuous slurry stirred tank reactors, cascade stirred tank reactors, bubble slurry reactors, fixed beds, ebullated beds, and other known industrial reactor types. Thus, in various aspects, the present invention further relates to a method of preparing a reactor for liquid phase catalytic reactions. In other aspects, the present invention further relates to a method of preparing a reactor for gas phase catalytic reactions. The method comprises charging the reactor with a catalyst composition comprising the shaped porous carbon product described herein as a catalyst support. In some embodiments, the reactor is a fixed bed reactor.

[0090] Various methods for making catalyst compositions according to the present invention include mixing and heating water and a water-soluble organic binder to form a binder solution; mixing carbon black particles with the binder solution to form a carbon black mixture; molding the carbon black mixture to form a molded carbon black composite; heating the molded carbon black composite to carbonize the binder to a water-insoluble state and form a molded porous carbon product; and depositing a catalytically active component, or a precursor thereof, on the molded porous carbon product to form the catalyst composition, wherein the water and binder are heated to a temperature of at least about 50° C., and the binder comprises (i) a saccharide selected from the group consisting of monosaccharides, disaccharides, oligosaccharides, derivatives thereof, and any combination thereof, and (ii) a polymeric carbohydrate, a derivative of a polymeric carbohydrate, or a non-carbohydrate synthetic polymer, or any combination thereof.

[0091] Another method includes mixing water, carbon black, and a water-soluble organic binder to form a carbon black mixture; shaping the carbon black mixture to form a shaped carbon black composite; heating the shaped carbon black composite to carbonize the binder to a water-insoluble state to form a shaped porous carbon product; and depositing a catalytically active component, or a precursor thereof, on the shaped porous carbon product to form a catalyst composition; the binder comprises (i) a saccharide selected from the group consisting of monosaccharides, disaccharides, oligosaccharides, derivatives thereof, and any combination thereof, and (ii) a polymeric carbohydrate, a derivative of a polymeric carbohydrate, or a non-carbohydrate synthetic polymer, or any combination thereof.

[0092] A further method of making a catalyst composition according to the present invention comprises mixing water, carbon black, and a binder to form a carbon black mixture; shaping the carbon black mixture to form a shaped carbon black composite; heating the shaped carbon black composite to carbonize the binder to a water-insoluble state and form a shaped porous carbon product; and depositing a catalytically active component, or a precursor thereof, on the shaped porous carbon product to form the catalyst composition, wherein the binder comprises a saccharide selected from the group consisting of monosaccharides, disaccharides, oligosaccharides, derivatives thereof, or any combination thereof, and wherein the weight ratio of binder to carbon black in the carbon black mixture is 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.

[0093] Another method includes mixing water, carbon black, and a binder to form a carbon black mixture; molding the carbon black mixture to form a molded carbon black composite; heating the molded carbon black composite to carbonize the binder to a water-insoluble state and form a molded porous carbon product; and depositing a catalytically active component, or a precursor thereof, on the molded porous carbon product to form a catalyst composition, wherein the binder comprises a saccharide selected from the group consisting of monosaccharides, disaccharides, oligosaccharides, derivatives thereof, or any combination thereof, and the water content of the carbon black mixture is about 80% by weight or less, about 55% by weight or less, about 40% by weight or less, or about 25% by weight or less.

[0094] A still further method includes depositing a catalytically active component or a precursor thereof onto a shaped porous carbon article to form a catalyst composition, the shaped porous carbon article comprising (a) carbon black and (b) a carbonized binder comprising the carbonized product of a water-soluble organic binder, the shaped porous carbon article having a BET specific surface area of ​​about 20 m 2 / g~about 500m 2 / g, with an average pore diameter of greater than about 5 nm and a specific pore volume of about 0.1 cm 3 / g, a radial crushing strength greater than about 4.4 N / mm (1 lb / mm), a carbon black content of at least about 35% by weight, and a carbonized binder content of about 20% to about 50% by weight.

[0095] Catalytic Process Catalyst compositions comprising the shaped porous carbon products of the present invention are useful for a variety of catalytic transformations, such as oxidation, reduction, dehydration, hydrogenation, and other known transformations, with appropriate active metal loadings, and which can be carried out in gaseous or liquid media. Thus, in a further aspect, the present invention relates to processes for the catalytic transformation of reactants.

[0096] The process of the present invention involves contacting a liquid medium containing reactants with a catalyst composition comprising a shaped porous carbon product as a catalyst support. In various embodiments, the shaped porous carbon product comprises a carbonized binder comprising the carbonized product of (a) carbon black and (b) a water-soluble organic binder, the shaped porous carbon product having a BET specific surface area of ​​about 20 m 2 / g~about 500m 2 / g or approximately 25m 2 / g ~ approx. 250m 2 / g, with an average pore diameter of greater than about 10 nm and a specific pore volume of about 0.1 cm 3 / g, a radial crushing strength greater than about 4.4 N / mm (1 lb / mm), and a carbon black content of at least about 35 wt.%. In other embodiments, the shaped porous carbon product comprises carbon agglomerates, and the shaped porous carbon product has an average diameter of at least about 50 μm and a BET specific surface area of ​​about 20 m 2 / g~about 500m 2 / g or approximately 25m 2 / g ~ approx. 250m 2 / g, with an average pore diameter of greater than about 10 nm and a specific pore volume of about 0.1 cm 3 / g and a radial crushing strength of greater than about 4.4 N / mm (1 lb / mm). Typically, the catalyst composition has excellent mechanical strength (e.g., mechanical crushing strength and / or radial crushing strength) and is stable to continuous flow of the liquid medium and reaction conditions for at least about 500 hours or about 1,000 hours without a substantial loss in catalyst productivity, selectivity, and / or yield.

[0097] Furthermore, it has been unexpectedly discovered that catalyst compositions comprising the shaped porous carbon products of the present invention are highly productive and selective catalysts for certain chemical transformations, such as, but not limited to, the transformation of highly functionalized and / or non-volatile molecules, including bio-renewably derived molecules and intermediates for general-purpose applications.

[0098] catalytic oxidation One set of chemical transformations for which the catalyst compositions of the present invention are suitable is the selective oxidation of hydroxyl groups to carboxyl groups in a liquid or gaseous reaction medium. For example, one set of chemical transformations for which the catalyst compositions of the present invention are particularly suitable is the selective oxidation of aldoses to aldaric acids. Thus, as described herein, the catalyst compositions of the present invention can be used as oxidation catalysts. Aldoses include, for example, pentoses and hexoses (i.e., C-5 and C-6 monosaccharides). Pentoses include ribose, arabinose, xylose, and lyxose, while hexoses include glucose, allose, altrose, mannose, gulose, idose, galactose, and talose. Thus, in various embodiments, the present invention also relates to a process for the selective oxidation of aldoses to aldaric acids, comprising reacting the aldose with oxygen in the presence of a catalyst composition as described herein to form the aldaric acid. Typically, the catalyst composition comprises at least platinum as a catalytically active component.

[0099] The catalytic compositions of the present invention have been found to be particularly selective for the oxidation of glucose to glucaric acid. Accordingly, the present invention relates to a process for the selective oxidation of glucose to glucaric acid, comprising reacting an aldose with oxygen in the presence of a catalytic composition as described herein to form glucaric acid. U.S. Pat. No. 8,669,397 (incorporated herein by reference in its entirety) discloses various catalytic processes for the oxidation of glucose to glucaric acid. Generally, glucose can be converted to glucaric 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: [ka] The oxidation can be carried out in the absence of added base (e.g., KOH), or when the initial pH of the reaction medium and / or the pH of the reaction medium at any time during the reaction is about 7 or less, 7.0 or less, about 6.5 or less, or about 6 or less. The initial pH of the reaction mixture is the pH of the reaction mixture prior to contact with oxygen in the presence of an oxidation catalyst. Indeed, catalyst selectivity can be maintained to achieve glucaric acid yields of greater than about 30%, about 40%, about 50%, or about 60%, and in some cases, glucaric acid yields of 65% or greater. The presence of an added base advantageously facilitates separation and isolation of glucaric acid, thereby providing a process more suitable for industrial application and improving overall process economics by removing reaction components. As used herein, "in the absence of added base" means that a base, if present (e.g., as a component of the feedstock), is present at a concentration that does not substantially affect the activity of the reaction, i.e., the oxidation reaction is carried out substantially in the absence of added base. The oxidation reaction can also be carried out in the presence of a weak carboxylic acid, such as acetic acid, in which glucose is soluble. As used herein, the term "weak carboxylic acid" refers to any unsubstituted or substituted carboxylic acid having a pKa of at least about 3.5, more preferably at least about 4.5, and more specifically selected from unsubstituted acids such as acetic acid, propionic acid, or butyric acid, or mixtures thereof.

[0100] The oxidation reaction can be carried out under elevated oxygen partial pressure and / or higher oxidation reaction mixture temperatures, which conditions tend to increase the yield of glucaric acid when the reaction is carried out in the absence of added base or at a pH below about 7. Typically, the partial pressure of oxygen is at least about 15 pounds per square inch absolute (psia) (104 kPa), at least about 25 psia (172 kPa), at least about 40 psia (276 kPa), or at least about 60 psia (414 kPa). In various embodiments, the partial pressure of oxygen ranges up to about 1,000 psia (6895 kPa), more typically from about 15 psia (104 kPa) to about 500 psia (3447 kPa), from about 75 psia (517 kPa) to about 500 psia (3447 kPa), from about 100 psia (689 kPa) to about 500 psia (3447 kPa), or from about 150 psia (1034 kPa) to about 500 psia (3447 kPa). Generally, 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 greater. 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. Surprisingly, catalyst compositions comprising shaped porous carbon products as catalyst supports enable oxidation of glucose at high temperatures (e.g., about 100°C to about 160°C or about 125°C to about 150°C) without thermal degradation of the catalyst. In particular, it has been discovered that reactor formats capable of providing relatively high liquid throughput, such as fixed-bed reactors, in combination with catalyst compositions comprising shaped porous carbon products containing carbon black, enable oxidation at temperatures greater than 140°C (e.g., 140°C to 150°C).

[0101] The oxidation of glucose to glucaric acid can also be carried out in the absence of nitrogen as an active reactant. Some processes employ nitrogen compounds, such as nitric acid, as the oxidizing agent. The use of forms of nitrogen that are active reactants, such as nitrate or nitric acid, results in NO xThis creates the need for reduction and acid regeneration techniques, both of which add significant costs to the production of glucaric acid from these known processes and, in addition, result in a corrosive environment that can adversely affect the equipment used to carry out the process. In contrast, for example, in the oxidation reaction of the present invention, when air or oxygen-enriched air is used as the oxygen source, nitrogen is a substantially inactive or inert component. Thus, the oxidation reaction using air or oxygen-enriched air is an essentially nitrogen-free reaction in a form in which nitrogen would otherwise be an active reactant.

[0102] In various embodiments, glucose is oxidized to glucaric acid in the presence of a catalyst composition comprising a shaped porous carbon article described herein as a catalyst support and a catalytically active component on the support. In certain embodiments, the catalytically active component comprises platinum. In some embodiments, the catalytically active component comprises platinum and gold.

[0103] Applicants have unexpectedly discovered that an oxidation catalyst composition comprising the shaped porous carbon product of the present invention provides greater selectivity and yield for the production of glucaric acid from glucose than a similar catalyst comprising a similar support material, such as activated carbon. In particular, Applicants have unexpectedly discovered that improved selectivity and yield for glucaric acid can be achieved by using an oxidation catalyst composition comprising a shaped porous carbon product as a catalyst support and a catalytically active component comprising platinum and gold on the surface of the shaped porous carbon product (i.e., on the surface of the catalyst support).

[0104] The oxidation catalyst can include any of the shaped porous carbon articles described herein. For example, in various embodiments, the shaped porous carbon article includes a carbonized binder comprising the carbonized product of (a) carbon black and (b) a water-soluble organic binder, wherein the shaped porous carbon article has a BET specific surface area of ​​about 20 m 2 / g~about 500m 2 / g or approximately 25m 2 / g ~ approx. 250m 2 / g, with an average pore diameter of greater than about 10 nm and a specific pore volume of about 0.1 cm 3 / g, a radial crushing strength greater than about 4.4 N / mm (1 lb / mm), and a carbon black content of at least about 35 wt.%. In other embodiments, the shaped porous carbon product comprises carbon agglomerates, and the shaped porous carbon product has an average diameter of at least about 50 μm and a BET specific surface area of ​​about 20 m 2 / g~about 500m 2 / g or approximately 25m 2 / g ~ approx. 250m 2 / g, with an average pore diameter of greater than about 10 nm and a specific pore volume of about 0.1 cm 3 / g and a radial crushing strength of greater than about 4.4 N / mm (1 lb / mm). Another shaped porous carbon product according to the present invention also has at least about 35% of its pore volume attributable to pores having an average pore diameter of about 10 nm to about 50 nm, when the pore volume is measured based on pores having a diameter of 1.7 nm to 100 nm.

[0105] The improved glucaric acid yield is typically at least about 30%, at least about 35%, at least about 40%, at least about 45%, or at least about 50% (e.g., about 35% to about 65%, about 40% to about 65%, or about 45% to about 65%). Furthermore, the improved glucaric acid selectivity is typically at least about 70%, at least about 75%, or at least about 80%.

[0106] In various embodiments, the catalytically active component comprising platinum and gold, or a precursor thereof, is in the form described in U.S. Patent Application Publication No. 2011 / 0306790, which is incorporated herein by reference in its entirety. This publication describes various oxidation catalysts comprising catalytically active components comprising platinum and gold that are useful for the selective oxidation of compositions comprising a primary alcohol group and at least one secondary alcohol group (e.g., glucose).

[0107] In various embodiments, an oxidation catalyst composition according to the present invention comprises a shaped porous carbon article as a catalyst support, as described herein, containing gold particles in the form of a gold-containing alloy and particles consisting essentially of platinum(0) as catalytically active components on the surface of the catalyst support. Typically, the total metal loading of the catalyst composition is about 10 wt.% or less, about 1 wt.% to about 8 wt.%, about 1 wt.% to about 5 wt.%, or about 2 wt.% to about 4 wt.%.

[0108] To oxidize glucose to glucaric acid, a sufficient amount of catalytically active component relative to the amount of reactant (i.e., glucose) must be present. Thus, in the inventive processes for the oxidation of glucose to glucaric acid described herein, in which the catalytically active component comprises platinum, the weight 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.

[0109] In various embodiments, the oxidation catalyst of the present invention can be prepared according to the following method. The gold component of the catalyst is typically added to the shaped porous carbon article as a solubilized component, allowing for the formation of a uniform suspension. A base is then added to form an insoluble gold complex that can be more uniformly deposited on the support. For example, the solubilized gold component is added to the slurry as a gold salt, such as HAuCl. Once a well-dispersed, heterogeneous mixture is produced, a base is added to the slurry to form an insoluble gold complex, which is deposited on the surface of the shaped porous carbon article. While any base capable of affecting the insoluble gold complex can be used, bases such as KOH and NaOH are typically used. Although not required, it may be desirable to collect the shaped porous carbon article with the insoluble gold complex deposited thereon before adding the platinum-containing component. This collection can be easily accomplished by any of a variety of means known in the art, such as centrifugation. The collected solid can optionally be washed and then heated to dry. Heating can also be performed to reduce the gold complex to gold(0) on the support. Heating can be carried out at temperatures ranging from about 60°C (for drying) to about 500°C (at which gold can be effectively reduced). In various embodiments, the heating step can be carried out in the presence of a reducing or oxidizing atmosphere to facilitate the reduction of the complex and deposit the gold on the support as gold(0). The heating time will vary depending, for example, on the purpose of the heating step and the decomposition rate of the added base to form the insoluble complex; heating times can range from several minutes to several hours. More typically, heating times for drying are on the order of about 2 to about 24 hours, and for reduction of the gold complex, heating times are on the order of about 1 to about 4 hours.

[0110] In various embodiments, the concentration of the shaped porous carbon product in the slurry may range from about 1 to about 100 g solids / liter of slurry, and in other embodiments, from about 5 to about 25 g solids / liter of slurry.

[0111] Mixing of the slurry containing the soluble gold-containing compound is continued for a time sufficient to form at least a fairly uniform suspension. Suitable times can range from several minutes to several hours. After the addition of the base to convert the gold-containing compound to an insoluble gold-containing complex, the uniformity of the slurry must be maintained for a time sufficient to allow the insoluble complex to form and deposit on the shaped porous carbon article. In various embodiments, the time can range from several minutes to several hours.

[0112] Platinum can be added to the shaped porous carbon article or its slurry after deposition of gold on the shaped porous carbon article or after heat treatment to reduce the gold complex on the support to gold(0). Alternatively, platinum can be added to the shaped porous carbon article or its slurry before the addition of the solubilized gold compound, provided that the platinum present on the support is in a form that will not redissolve upon addition of the base used to promote deposition of gold onto the support. Platinum is typically added as a solution of a soluble precursor or as a colloid. Platinum is available in the following forms: platinum(II) nitrate, platinum(IV) nitrate, platinum oxynitrate, platinum(II) acetylacetonate (acac), tetraammineplatinum(II) nitrate, tetraammineplatinum(II) hydrogen phosphate, tetraammineplatinum(II) hydrogen carbonate, tetraammineplatinum(II) hydroxide, H2PtCl6, PtCl4, Na2PtCl4, K2PtCl4, (NH4)2PtCl4, Pt(NH3)4Cl2, and mixed Pt(NH3). x Cl y , K2Pt(OH)6, Na2Pt(OH)6, (NMe4)2Pt(OH)6, and (EA)2Pt(OH)6 (where EA = ethanolamine). More preferred compounds include platinum(II) nitrate, platinum(IV) nitrate, platinum(II) acetylacetonate (acac), tetraammineplatinum(II) hydroxide, K2PtCl4, and K2Pt(OH)6.

[0113] After addition of the platinum compound, the support slurry and platinum-containing compound are dried. Drying can be carried out at room temperature or at temperatures up to 120°C. More preferably, drying is carried out at a temperature ranging from about 40°C to about 80°C, more preferably at about 60°C. The drying step can be carried out for a time ranging from about several minutes to several hours. Typically, drying times range from about 6 to about 24 hours. Drying can also be carried out using a band calciner or belt dryer (preferred for commercial applications) in a continuous or multi-stage temperature ramp from about 60°C to about 120°C.

[0114] After drying the support with the deposited platinum compound, the support is subjected to at least one heat treatment to reduce the platinum deposited as platinum(II) or platinum(IV) to platinum(0). The heat treatment(s) can be carried out in air or any reducing or oxidizing atmosphere. In various embodiments, the heat treatment(s) is carried out under a forming gas atmosphere. Alternatively, the platinum can be reduced using a liquid reducing agent. For example, hydrazine, formaldehyde, formic acid, or salts thereof (e.g., sodium formate), or NaH2PO2 can be used to effect the required platinum reduction. The atmosphere in which the heat treatment is carried out depends on the platinum compound employed, and the objective is to substantially convert the platinum on the support to platinum(0).

[0115] The temperature at which the heat treatment(s) is / are carried out is typically in the range of about 150°C to about 600°C. More typically, the temperature at which the heat treatment(s) is / are carried out is in the range of about 200°C to about 500°C, preferably in the range of about 200°C to about 400°C. The heat treatment is typically carried out for a time period ranging from about 1 hour to about 8 hours, or from about 1 hour to about 3 hours.

[0116] In various embodiments, the oxidation catalytic metal(s) deposited on the shaped porous carbon article form a shell that at least partially covers the surface of the carbon article. In other words, the metal deposited on the shaped porous carbon article coats the exterior surface of the carbon article. In various embodiments, the metal penetrates the surface pores of the shaped porous carbon article, forming a shell layer ("eggshell") of about 10 μm to about 400 μm, or about 50 μm to about 150 μm (e.g., about 100 μm). In certain embodiments, the shell can form a lower surface, producing a lower surface zone ("yolk") of 10 μm to about 400 μm that contains the catalytically active metal.

[0117] Catalytic Hydrodeoxygenation The catalyst composition of the present invention is particularly suitable for the hydrodeoxygenation of carbon-hydroxyl groups to carbon-hydrogen groups in a liquid or gaseous reaction medium. For example, the catalyst composition of the present invention is particularly suitable for the selective halide-promoted hydrodeoxygenation of aldaric acids, or their salts, esters, or lactones, to dicarboxylic acids. Therefore, as described herein, the catalyst composition of the present invention can be used as a hydrodeoxygenation catalyst. Accordingly, the present invention also relates to a process for the selective halide-promoted hydrodeoxygenation of aldaric acids, comprising reacting an aldaric acid, or its salts, esters, or lactones, with hydrogen to form dicarboxylic acids in the presence of a halogen-containing compound and the catalyst composition as described herein. Typically, the catalyst composition contains at least one noble metal as a catalytically active component.

[0118] The catalyst compositions of the present invention have been found to be particularly selective for the halide-promoted hydrodeoxygenation of glucaric acid or its salts, esters, or lactones to adipic acid. U.S. Patent No. 8,669,397, referenced above and incorporated herein by reference, describes a chemical catalytic process for the hydrodeoxygenation of glucaric acid to adipic acid.

[0119] Adipic acid or salts and esters thereof can be prepared by reacting glucaric acid or its salts, esters, or lactones with hydrogen in the presence of a hydrodeoxygenation catalyst and a halogen source according to the following reaction: [ka]

[0120] In the above reaction, glucaric acid or its salt, ester, or lactone is converted to the adipic acid product by catalytic hydrodeoxygenation, in which a carbon-hydroxyl group is converted to a carbon-hydrogen group. In various embodiments, the catalytic hydrodeoxygenation is hydroxyl-selective, and the reaction proceeds to completion without substantial conversion of one or more other non-hydroxyl functional groups of the substrate.

[0121] The halogen source may be in a form selected from the group consisting of ions, molecules, 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 halides, or molecular (diatomic) halogens (e.g., chlorine, bromine, iodine, or mixtures thereof; preferably bromine and / or iodine). In various embodiments, the halogen source is a diatomic form, a hydrohalic acid, or a halide salt, and more preferably a diatomic form or a hydrohalic acid. In certain embodiments, the halogen source is a hydrohalic acid, particularly hydrobromic acid.

[0122] Generally, the molar ratio of halogen to glycerol, or a salt, ester, or lactone thereof, is about 1 or less than about 1. In various embodiments, the molar ratio of halogen to glycerol, or a salt, ester, or lactone thereof, is usually about 1:1 to about 0.1:1, more typically about 0.7:1 to about 0.3:1, and even more typically about 0.5:1.

[0123] Generally, the reaction allows for the recovery of the halogen source, and a catalytic amount of halogen (the molar ratio of halogen to glucaric acid or its salt, ester, or lactone is less than about 1) can be used, recovered, and recycled for continuous use as the halogen source.

[0124] Generally, 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 hydrodeoxygenation reaction temperature ranges from about 20° C. to about 250° C., from about 80° C. to about 200° C., from about 120° C. to about 180° C., or from about 140° C. to about 180° C. Typically, the partial pressure of hydrogen is at least about 25 psia (172 kPa), more typically about 200 psia (1379 kPa) or at least about 400 psia (2758 kPa). In various embodiments, the hydrogen partial pressure 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).

[0125] The hydrodeoxygenation reaction can be carried out in the presence of a solvent. Suitable solvents for the selective hydrodeoxygenation reaction include water and carboxylic acids, amides, esters, lactones, sulfoxides, sulfones, and mixtures thereof. Preferred solvents include water, water and a weak carboxylic acid, and a weak carboxylic acid. A preferred weak carboxylic acid is acetic acid.

[0126] Applicants have discovered that a hydrodeoxygenation catalyst composition comprising the shaped porous carbon product of the present invention provides improved selectivity and yield for the production of adipic acid. In particular, Applicants have unexpectedly discovered that improved selectivity and yield for adipic acid can be achieved by using the shaped porous carbon product of the present invention as a catalyst support and an oxidation catalyst composition comprising a catalytically active component on the surface of the shaped porous carbon product (i.e., on the surface of the catalyst support).

[0127] The catalyst can include any of the shaped porous carbon products described herein. For example, in various embodiments, the shaped porous carbon product includes a carbonized binder comprising (a) carbon black and (b) a carbonized product of a water-soluble organic binder, wherein the shaped porous carbon product has a BET specific surface area of ​​about 20 m 2 / g~about 500m 2 / g or approximately 25m 2 / g ~ approx. 250m 2 / g, with an average pore diameter of greater than about 5 nm and a specific pore volume of about 0.1 cm 3 / g, a radial crushing strength greater than about 4.4 N / mm (1 lb / mm), and a carbon black content of at least about 35 wt.%. In other embodiments, the shaped porous carbon product comprises carbon agglomerates, and the shaped porous carbon product has an average diameter of at least about 50 μm and a BET specific surface area of ​​about 20 m 2 / g~about 500m 2 / g or approximately 25m 2 / g ~ approx. 250m 2 / g, with an average pore diameter of greater than about 5 nm and a specific pore volume of about 0.1 cm 3 / g and a radial crushing strength of greater than about 4.4 N / mm (1 lb / mm). Another shaped porous carbon product according to the present invention also has at least about 35% of its pore volume attributable to pores having an average pore diameter of about 10 nm to about 50 nm, when the pore volume is measured based on pores having a diameter of 1.7 nm to 100 nm.

[0128] The catalytically active component or precursor thereof can comprise a precious metal selected from the group consisting of ruthenium, rhodium, palladium, platinum, and combinations thereof. In various embodiments, the hydrodeoxygenation catalyst comprises two or more metals. For example, in some embodiments, a first metal is selected from the group consisting of cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum (or more specifically, ruthenium, rhodium, palladium, and platinum), and a second metal is selected from the group consisting of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, rhodium, palladium, silver, tungsten, iridium, platinum, and gold (or more specifically, molybdenum, ruthenium, rhodium, palladium, iridium, platinum, and gold). In select embodiments, the first metal is selected from the group consisting of platinum, rhodium, and palladium, and the second metal is selected from the group consisting of ruthenium, rhodium, palladium, platinum, and gold. In particular embodiments, the first metal is platinum and the second metal is rhodium. In these and other embodiments, the molar ratio of platinum to rhodium in the catalyst compositions of the present invention ranges from about 3:1 to about 1:2, or from about 3:1 to about 1:1.

[0129] In various embodiments, the metal(s) deposited on the shaped porous carbon article for hydrodeoxygenation catalysis form a shell that at least partially covers the surface of the carbon article. In other words, the metal deposited on the shaped porous carbon article coats the exterior surface of the carbon article. In various embodiments, the metal penetrates the surface pores of the shaped porous carbon article, forming a shell layer ("eggshell") of about 10 μm to about 400 μm, or about 50 μm to about 150 μm (e.g., about 100 μm). In certain embodiments, the shell can form a lower surface, producing a lower surface zone ("yolk") of 10 μm to about 400 μm that contains the catalytically active metal.

[0130] Hydrodeoxygenation of 1,2,6-hexanetriol Another chemical conversion for which the catalyst composition of the present invention is advantageous is the selective hydrodeoxygenation of 1,2,6-hexanetriol to 1,6-hexanediol (HDO) and 1,2,5,6-hexanetetraol to 1,6-HDO. Accordingly, one process of the present invention relates to the selective hydrodeoxygenation of 1,2,6-hexanetriol, comprising reacting 1,2,6-hexanetriol with hydrogen to form HDO in the presence of the catalyst composition disclosed herein. In embodiments of this process, the catalytically active component of the catalyst composition comprises platinum. In some embodiments, the catalytically active component of the catalyst composition comprises platinum and at least one metal (M2) selected from the group consisting of molybdenum, lanthanum, samarium, yttrium, tungsten, and rhenium. In certain embodiments, the catalytically active component of the catalyst composition comprises platinum and tungsten.

[0131] Typically, the total weight of the metal(s) is about 0.1% to about 10%, 0.2% to 10%, about 0.2% to about 8%, or about 0.2% to about 5% of the total weight of the catalyst. In more preferred embodiments, the total weight of the metals in the catalyst is less than about 4%. The molar ratio of platinum to (M2) can vary, for example, from about 20:1 to about 1:10. In various embodiments, the molar ratio of M1:M2 ranges from about 10:1 to about 1:5. In even more preferred embodiments, the ratio of M1:M2 ranges from about 8:1 to about 1:2.

[0132] Typically, the conversion of 1,2,6-hexanetriol to HDO is carried out at a temperature ranging from about 60°C to about 200°C or from about 120°C to about 180°C, and under a hydrogen partial pressure ranging from about 200 psig to about 2000 psig or from about 500 psig to about 2000 psig.

[0133] Catalytic amination of 1,6-hexanediol Additionally, the catalyst composition of the present invention is also useful for the selective amination of 1,6-hexanediol (HDO) to 1,6-hexamethylenediamine (HMDA). Accordingly, another process of the present invention relates to the selective amination of 1,6-hexanediol to 1,6-hexamethylenediamine, comprising reacting HDO with an amine in the presence of the catalyst composition disclosed herein. In various embodiments of this process, the catalytically active component of the catalyst composition comprises ruthenium.

[0134] In some embodiments of this process, the catalytically active component of the catalyst composition comprises ruthenium and, optionally, a second metal such as rhenium or nickel. One or more other d-block metals, one or more rare earth metals (e.g., lanthanides), and / or one or more main group metals (e.g., Al) may be present along with the ruthenium and combinations of ruthenium and rhenium. In select embodiments, the catalytically active phase consists essentially of ruthenium and rhenium. Typically, the combined weight of the metal(s) is about 0.1% to about 10%, 1% to 6%, or about 1% to about 5% of the total weight of the catalyst composition.

[0135] When the catalyst of the present invention contains a combination of ruthenium and rhenium, the molar ratio of ruthenium to rhenium is important. A by-product of the process of converting HDO to HMDA is pentylamine. Pentylamine is an off-pathway by-product of the conversion of HDO to HMDA that cannot be converted to HMDA or to an intermediate that can be converted to HMDA upon further reaction in the presence of the catalyst of the present invention. However, the presence of excessive rhenium can adversely affect the yield of HMDA per unit area per hour (commonly known as space-time yield, or STY). Therefore, the ruthenium:rhenium molar ratio should be maintained in the range of about 20:1 to about 4:1. In various embodiments, the ruthenium:rhenium molar ratio is in the range of about 10:1 to about 4:1 or about 8:1 to about 4:1. In some embodiments, a molar ratio of ruthenium:rhenium of about 8:1 to about 4:1 produces HMDA in at least 25% yield, with an HMDA / pentylamine ratio of at least 20:1, at least 25:1, or at least 30:1.

[0136] In the present invention, HDO is converted to HMDA by reacting HDO with an amine, such as ammonia, in the presence of a catalyst of the present invention. Generally, in some embodiments, the amine can be added to the reaction system 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, the molar ratio of ammonia to HDO 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 composition of the present invention is carried out at a temperature of 200°C or less. In various embodiments, the catalyst composition is contacted with the HDO and the amine at a temperature of about 100°C or less. In some embodiments, the catalyst is contacted with the HDO and the amine at a temperature ranging from about 100°C to about 180°C or from about 140°C to about 180°C.

[0137] Generally, in the present invention, the reaction is carried out at a pressure not exceeding 1500 psig. In various embodiments, the reaction pressure ranges from about 200 psig to about 1500 psig. In other embodiments, the pressure ranges from about 400 psig to about 1200 psig. In certain preferred embodiments, the pressure ranges from about 400 psig to about 1000 psig. In some embodiments, the disclosed pressure ranges include the pressure of NH3 gas and an inert gas such as N2. In some embodiments, the pressure of NH3 gas ranges from about 50 to 150 psig, and the pressure of the inert gas such as N2 ranges from about 700 psig to about 1450 psig.

[0138] In some embodiments, the catalyst is contacted with the HDO and amine at a temperature ranging from about 100°C to about 180°C and a pressure ranging from about 200 psig to about 1500 psig. In other embodiments, the catalyst is contacted with the HDO and amine at a temperature ranging from about 140°C to about 180°C and a pressure ranging from about 400 psig to about 1200 psig. In some embodiments, the disclosed pressure ranges include the pressure of NH3 gas and an inert gas such as N2. In some embodiments, the pressure of the NH3 gas is in the range of about 50-150 psig, and the pressure of the inert gas such as N2 is in the range of about 500 psig to about 1450 psig.

[0139] The process of the present invention can be carried out in the presence of hydrogen. Typically, in embodiments where HDO and amines are reacted in the presence of hydrogen and the catalyst of the present invention, the hydrogen partial pressure is about 100 psig or less.

[0140] The conversion of HDO to HMDA can also be carried out in the presence of a solvent. Suitable solvents for use with the conversion of HDO to HMDA in the presence of the catalyst of the present invention can include, for example, water, alcohols, esters, ethers, ketones, or mixtures thereof. In various embodiments, the preferred solvent is water.

[0141] The chemically catalyzed conversion of HDO to HMDA may produce one or more by-products, such as, for example, pentylamine and hexylamine. By-products that can subsequently be converted to HMDA by further reaction in the presence of a catalyst of the invention are considered on-path by-products. Other by-products, such as pentylamine and hexylamine, are considered off-pathway by-products for the reasons discussed above. In 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 resulting from a single-pass reaction of HDO with an amine (e.g., ammonia) in the presence of a catalyst of the invention is HMDA.

[0142] The 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 fractional distillation under subatmospheric pressure. For example, in some embodiments, HMDA can be separated from the product mixture at a temperature of about 180°C to about 220°C. HDO can be recovered from any other remaining products of the reaction mixture by one or more conventional methods known in the art, including, for example, solvent extraction, crystallization, or evaporation processes. The pathway byproducts can be recycled to the reactor in which they are used to produce a product mixture, or can be fed to a second reactor where, for example, they are further reacted with ammonia in the presence of a catalyst of the invention to produce additional HMDA.

[0143] Glycerol hydrogenolysis Another chemical conversion for which the catalyst supports and catalyst compositions of the present invention are useful is the hydrocracking of glycerol to various diols, particularly propylene glycol (1,2-propanediol) and / or ethylene glycol (1,2-ethanediol). For example, glycerol hydrocracking processes are described in U.S. Pat. Nos. 6,479,713 and 7,928,148, and U.S. Patent Application Publication No. 2018 / 0201559, the contents of which are incorporated herein by reference. Thus, in various embodiments, a glycerol hydrocracking process includes supplying a feed composition comprising glycerol to a reaction zone, and reacting the glycerol with hydrogen in the presence of a catalyst composition described herein to form a reaction product comprising propylene glycol and / or ethylene glycol.

[0144] In some embodiments, a process for hydrocracking glycerol includes supplying a feed composition containing glycerol to a reaction zone and reacting the glycerol with hydrogen in the presence of a catalyst composition in the reaction zone to form a reaction product containing propylene glycol and / or ethylene glycol. The catalyst composition includes a catalytically active component including a metal selected from the group consisting of chromium, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, gold, and any combination thereof, and a catalyst support including a shaped porous carbon product containing carbon black. The shaped porous carbon product can include one or more characteristics described herein (e.g., specific surface area, average pore size, specific pore volume, mesoporosity, pore size distribution, radial and mechanical crush strengths, average diameter, abrasion index, attrition rate, etc.). The shaped porous carbon product can also include a carbonized product of the binder described herein (e.g., carbonized sugars, cellulosic compounds, etc.).

[0145] For example, catalysts comprising shaped porous carbon products as catalyst supports exhibiting a high level of mesoporosity have been found to be particularly effective catalysts for this reaction. The shaped porous carbon products advantageously exhibit a high concentration of mesopores ranging from about 10 nm to about 100 nm, from about 20 nm to about 100 nm, or from about 10 nm to about 50 nm. Thus, in various embodiments, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, or at least about 95% of the pore volume of the shaped porous carbon products is attributable to pores having an average 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. For example, when measured by the BJH method using pores with diameters of 1.7 nm to 100 nm as a standard, about 50% to about 99%, about 50% to about 95%, about 50% to about 90%, about 50% to about 80%, about 60% to about 99%, about 60% to about 95%, about 60% to about 90%, about 60% to about 80%, about 70% to about 99%, about 70% to about 95%, about 70% to about 90%, about 70% to about 80%, about 80% to about 99%, about 80% to about 95%, about 80% to about 90%, or about 90% to about 99% of the pore volume of the molded porous carbon product is attributable to pores with an average pore diameter of about 10 nm to about 100 nm. In various embodiments, at least about 35%, at least about 40%, at least about 45%, or at least about 50% of the pore volume of the formed porous carbon product is attributable to pores having an average pore size of about 20 nm to about 90 nm or about 10 nm to about 50 nm, as measured by the BJH method, based on pores having a diameter of 1.7 nm to 100 nm. For example, at least about 35% to about 80%, about 35% to about 75%, about 35% to about 65%, about 40% to about 80%, about 40% to about 75%, or about 40% to about 70% of the pore volume of the formed porous carbon product is attributable to pores having an average pore size of about 20 nm to about 90 nm or about 10 nm to about 50 nm, as measured by the BJH method, based on pores having a diameter of 1.7 nm to 100 nm.

[0146] Additionally, in various embodiments, the formed porous carbon product has a relatively low concentration of macropores. For example, in some embodiments, about 10% or less, at least about 5% or less, or about 3% or less of the pore volume of the formed porous carbon product is attributable to pores with an average pore diameter of about 100 nm or greater, as measured by mercury porosimetry. In particular embodiments, about 0.1% to about 10%, about 0.1% to about 5%, about 0.1% to about 3%, about 1% to about 10%, about 1% to about 5%, or about 1% to about 3% of the pore volume of the formed porous carbon product is attributable to pores with an average pore diameter of about 100 nm or greater, as measured by mercury porosimetry. Further details regarding mercury porosimetry analysis are provided in the Examples.

[0147] The present process for hydrogenolysis of glycerol has been shown to advantageously result in high yields of propylene glycol, for example, various processes result in yields of propylene glycol that are at least about 50%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, or at least about 80%.

[0148] As discussed above, these hydrocracking processes involve reacting glycerol with hydrogen. In various embodiments, the partial pressure of hydrogen in the reaction zone is at least about 300 psi, at least about 1000 psi, at least about 1800 psi, or at least about 2000 psi. In some embodiments, the partial pressure of hydrogen in the reaction zone is from about 300 psi to about 2000 psi, from about 1000 psi to about 2000 psi, or from about 1800 psi to about 2000 psi. In some cases, increasing the flow rate of hydrogen relative to the flow rate of glycerol in the reaction zone has been found to increase the yield of propylene glycol.

[0149] As discussed above, the catalyst composition typically includes at least one catalytically active component comprising a metal selected from the group consisting of chromium, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, gold, and any combination thereof. In some embodiments, the catalytically active component includes rhenium. In various embodiments, the catalytically active component includes nickel. In further embodiments, the catalytically active component includes copper. In various embodiments, the catalytically active component includes a combination of metals. For example, the combination of metals can be selected from the group consisting of nickel and rhenium, copper and rhenium, and cobalt and rhenium. In certain embodiments, the catalyst composition further includes manganese, molybdenum, and / or zinc.

[0150] The catalyst composition can be doped with a catalytically active component as described herein. In some embodiments, the catalyst composition has a loading of the catalytically active component of about 0.1 wt. % or more, about 1 wt. % or more, about 2 wt. % or more, about 3 wt. % or more, about 4 wt. % or more, or about 5 wt. % or more. In various embodiments, the catalyst composition has a loading of the catalytically active component of about 0.1 wt. % to about 10 wt. %, about 0.1 wt. % to about 7.5 wt. %, about 0.1 wt. % to about 5 wt. %, about 0.5 wt. % to about 10 wt. %, about 0.5 wt. % to about 7.5 wt. %, about 0.5 wt. % to about 5 wt. %, about 1 wt. % to about 10 wt. %, about 1 wt. % to about 7.5 wt. %, or about 1 wt. % to about 5 wt. %.

[0151] A catalyst composition for the hydrocracking of glycerol can have a catalyst structure described herein. For example, the catalytically active component can form a shell layer that at least partially covers the surface of the shaped porous carbon article. In some embodiments, the catalytically active component is primarily present in the surface pores of the shaped porous carbon article to form a shell layer having a thickness of about 10 μm to about 400 μm, or about 50 μm to about 150 μm. In these and other embodiments, the catalyst composition includes an inner region (e.g., core) and an outer region (e.g., shell), the outer region having a higher concentration of catalytically active component than the inner region. See, e.g., Figures 14 and 16. In some embodiments, the concentration of catalytically active component in the outer region is at least 2-fold, 5-fold, 10-fold, or 100-fold higher than the concentration of catalytically active component in the inner region. In further embodiments, the catalyst composition has an average diameter, and the outer region comprises at least about 5%, at least about 10%, at least about 20%, about 5% to about 50%, or about 10% to about 40% of the average diameter. In some embodiments, the interior region comprises at least about 20%, at least about 30%, at least about 40%, about 20% to about 80%, or about 20% to about 70% of the average diameter.

[0152] The hydrocracking processes described herein can be carried out in the presence of a co-catalyst. One example of a co-catalyst is a base. Thus, in some embodiments, the reaction zone can further comprise a co-catalyst comprising a base. In various embodiments, the base comprises sodium hydroxide. The base (e.g., sodium hydroxide) can also be fed to the reaction zone together with the feed composition comprising glycerol, or, as described in U.S. Pat. No. 9,938,215, can be fed in a batch process to the inlet of a continuous flow tubular reactor and one or more additional points along the length of the reactor, or at the start and one or more subsequent times.

[0153] The hydrogenolysis processes described herein can be carried out under neutral or basic conditions (e.g., weakly basic to basic conditions). For example, the reaction can be carried out at a pH of about 7 to about 11, about 7.5 to about 10, about 8 to about 14, or about 10 to about 13.

[0154] The hydrocracking processes described herein can be carried out at temperatures of from about 150°C to about 300°C, from about 175°C to about 250°C, from about 190°C to about 250°C, or from about 190°C to about 225°C.

[0155] The feed composition may further comprise an aqueous glycerol solution. In some embodiments, the feed composition has a glycerol concentration of about 10% by weight or greater, about 20% by weight or greater, about 30% by weight or greater, about 40% by weight or greater, about 10% to about 50% by weight, or about 20% to about 40% by weight. In certain embodiments, the feed composition further comprises at least one other polyol selected from the group consisting of pentoses, hexoses, and sugar alcohols. [Example]

[0156] Surface areas were determined from nitrogen adsorption data using the BET method as described in S. Brunauer, P. E. Hammett, E. Teller, J. Am. Chem. Soc. 1938, 60, 309-331, and ASTM D3663-03(2008) Standard Test Method for Surface Area of ​​Catalysts and Catalyst Carriers. Average pore diameters and pore volumes were measured according to the procedures described in E. P. Barrett, L. G. Joyner, P. P. Halenda, J. Am. Chem. Soc. 1951, 73, 373-380, 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.

[0157] Mercury porosimetry measurements were performed using a Micromeritics Instrument Corporation AutoPore V Mercury Porosimeter. An appropriate amount of carbon extrudate was placed in a suitable penetrometer, and mercury intrusion was measured in two sequential stages: a reduced pressure analysis (0-50 psia), followed by a high pressure analysis (50-33,000 psia). A total of 712 data points were collected over the full pressure range at a contact angle of 154.0°.

[0158] Radial crush strength measurements were performed using a press equipped with a Dillon GS100 Digital Force Gauge in accordance with ASTM D6175-03(2013) Standard Test Method for Radial Crush Strength of Extruded Catalyst and Catalyst Carrier Particles. The average radial crush strength is the average of independent measurements made on at least 10 different extruded pellets.

[0159] Single Pellet Crush Strength was measured using a press equipped with a Dillon GS100 Digital Force Gauge in accordance with ASTM D4179-03(2013) Standard Test Method for Single Pellet Crush Strength of Formed Catalysts and Catalyst Carriers. Single Pellet Crush Strength is the average of measurements made on at least 10 different extruded pellets.

[0160] Example 1. Preparation of Carbon Black Extrudates 36.4 g of carbon black powder (Cabot Vulcan XC72, 224 m 2 1 / g) was added in portions to a heated (overnight at 80°C) aqueous solution (136.5 g) containing 24.3 wt% Cerelose Dextrose (Ingredion) and 4.7 wt% Hydroxyethylcellulose (Sigma-Aldrich) (SKU 54290, viscosity 80-125 cP, 2% in H2O at 20°C). The mixture was stirred well using a spatula to form a paste. This paste was then transferred to a syringe, and the material was extruded into spaghetti-like threads approximately 1.5 mm in diameter. After drying for 5 hours in a 70°C oven under a dry air purge, these threads were cut into pieces approximately 1.0 cm long. The binder was then carbonized to form carbon black extrudates by heating to 350°C at a rate of 10°C / min under a continuous N2 flow for 2 hours. The properties of the resulting extrudates are shown in Table 1. [Table 1]

[0161] Example 2. Characterization of the constituent carbon black powders Properties of various carbon black powders used in molded porous carbon black products.

[0162] A. Physical properties of carbon black powder Using the above methods, the BET specific surface area, specific average pore diameter, and specific pore volume of these carbon black powder starting materials were measured and are shown in Table 2. [Table 2]

[0163] B. Catalyst performance As described below, carbon black powder was evaluated as a catalyst support material in the oxidation reaction of glucose to glucaric acid.

[0164] (i) Oxidation of glucose to glucaric acid (Protocol 1) Appropriately concentrated aqueous solutions of Me4NAuO2 and PtO(NO3) were added together to carbon black powder by the incipient wetness impregnation method and stirred to impregnate the support. The sample was dried in an oven at 70 °C overnight, then heated to 350 °C at a rate of 2 °C / min under a forming gas (5% H2 and 95% N2) atmosphere and reduced for 4 hours to produce a catalyst with a composition of 2.0 wt% Au and 2.0 wt% Pt. Different catalysts with various Au and Pt loadings on particles from various commercial carbon black powders or extrudates were prepared in a similar manner by using other carbon black supports, Au and Pt precursors, and controlled amounts of Au and Pt in solution.

[0165] These catalysts were tested for glucose oxidation using the following test protocol. The catalyst (8 mg) was weighed into a glass vial insert, followed by the addition of 250 μL of 0.55 M aqueous glucose solution. The glass vial insert was placed in a reactor, and the reactor was closed. The atmosphere in the reactor was replaced with oxygen and pressurized to 75 psig at room temperature. The reactor was heated to 110°C and held at each temperature for 2 hours while the vial was shaken. The shaking was then stopped, and the reactor was cooled to 40°C. The pressure in the reactor was then slowly released. The glass vial insert was removed from the reactor and centrifuged. The solution was diluted with deionized water and analyzed by ion chromatography to determine the yield of glucaric acid. Selectivity was determined as 100% x (glucaric acid) / (the sum of glucaric acid and all off-pathway species). Off-pathway species that cannot be converted to glucaric acid include 2-ketogluconic acid, 3-ketogluconic acid, 4-ketogluconic acid, 5-ketogluconic acid, trihydroxyglutaric acid, tartaric acid, tartronic acid, and oxalic acid. On-pathway species include glucose, gluconic acid, guluronic acid, and glucuronic acid. On-pathway species are not used in the selectivity calculations because these intermediates can be partially converted to glucaric acid and are not considered off-pathway. The results are shown in Table 3. [Table 3]

[0166] (ii) Oxidation of glucose to glucaric acid (Protocol 2) Appropriately concentrated aqueous solutions of K2Pt(OH)6 and CsAuO2 were added together to carbon black powder by the incipient wetness impregnation method and stirred to impregnate the support. The sample was dried in an oven at 40 °C overnight and then reduced for 3 h at a rate of 5 °C / min to 250 °C under a forming gas (5% H2 and 95% N2) atmosphere. The final catalyst was washed with deionized water and finally dried at 40 °C to yield a catalyst with a composition of 2.44 wt% Pt and 2.38 wt% Au. Different catalysts with various Au and Pt loadings on particles from various commercial carbon black powders or extrudates were prepared in a similar manner by using other carbon black supports, Au and Pt precursors, and controlled amounts of Au and Pt in solution.

[0167] These catalysts were tested for glucose oxidation using the following test protocol: 10 mg of catalyst was weighed into a glass vial insert, followed by the addition of 250 μL of 0.55 M aqueous glucose solution. The glass vial insert was placed in a reactor, and the reactor was closed. The atmosphere in the reactor was purged with oxygen and pressurized to 75 psig at room temperature. The reactor was heated to 90°C and held at each temperature for 5 hours while the vial was shaken. The shaking was then stopped, and the reactor was cooled to 40°C. The pressure in the reactor was then slowly released. The glass vial insert was removed from the reactor and centrifuged. The solution was diluted with deionized water and analyzed by ion chromatography to determine the yield of glucaric acid and the selectivity, as defined herein. The results are shown in Table 4. [Table 4]

[0168] Example 3. Preparation of molded porous carbon black products using various carbon black powders and binders Different carbon black extrudates were made as described in Example 1 by using other carbon black powders and carbohydrate binders. Other carbon black powders include, but are not limited to, Orion carbon HI-BLACK 40B2, Orion HI-BLACK 50LB, Orion Hi-Black 50L, Orion HP-160, Orion Carbon HI-BLACK N330, Timcal Ensaco 150G, Timcal Ensaco 250G, Timcal Ensaco 260G, Timcal Ensaco 250P, Cabot Vulcan XC72R, Cabot Monarch 120, Cabot Monarch 280, Cabot Monarch 570, Cabot Monarch 700, Asbury 5365R, Asbury 5353R, Asbury 5345R, Asbury 5352, Asbury 5374, Asbury 5348R, Asbury 5358R, Sid Richardson SC159, and Sid Richardson SR155. Other carbohydrate binders include, but are not limited to, Cargill Clearbrew 60 / 44IX (80% carbohydrate), Casco Lab Fructose 90 (70% carbohydrate), and Molasses (80% carbohydrate). Formulations using these various carbon blacks and binders have provided illustrative examples of molded carbon products of the present invention. Properties of some of these embodiments are described in more detail below.

[0169] Example 4. Crush Testing of Carbon Black Extrudates Extruded pellets (numbered 1-8 below) approximately 1.5 mm in diameter were prepared according to the method described in Example 1, except that the pyrolysis time and temperature were varied as indicated in the Extrudate Description column of Table 5. After the pyrolysis step, the extrudates were cut into sizes ranging from 2-6 mm in length. The percentage of carbonized binder (after pyrolysis) present in the molded carbon product was determined by mass balance, i.e., [(wt 成形炭素製品 -weight カーボンブラック(配合物中) / weight 成形炭素製品) x 100]. The total binder content after pyrolysis (i.e., total carbonized binder) varied from 15 to 50 wt%.

[0170] Additional extruded pellets (numbered 9-11 below) were prepared according to the following procedure: Approximately 24.0 g of carbon black powder (Timcal Ensaco 250G, 65 ml) was added. 2 1 / g) was added in portions to an aqueous solution (100.0 g) containing 25.0 wt. % Cerelose Dextrose (obtained from Ingredion). The mixture was stirred well using a spatula to form a paste. This paste was then loaded into a syringe, and the material was extruded into spaghetti-like threads with a diameter of 1.5 mm. After drying in an oven at 100°C under a dry air purge for 3 hours, these threads were cut into small pieces (2-6 mm long). They were then processed under one of the following conditions to form carbon black extrudates: (1) 250°C for 3 hours (10°C / min heating rate) under continuous N2 flow; (2) 800°C for 4 hours (10°C / min heating rate) under continuous N2 flow; or (3) 200°C for 3 hours (10°C / min heating rate) in air. The binder content varied from 15 to 50 wt. Table 5 shows the crush strength data for the extrudates produced. [Table 5]

[0171] Example 5. Preparation of catalyst composition Cabot Vulcan XC72 carbon black extrudates prepared in Example 1 were further cut into pieces approximately 0.5 cm long. 21.5 g of these extrudates were mixed with 13 ml of an aqueous solution containing 0.17 g of Au in the form of Me4NAuO2 and 0.26 g of Pt in the form of PtO(NO3). The mixture was stirred to impregnate the carbon black support and dried overnight in an oven at 60°C under a dry air purge. The sample was then reduced for 4 hours at a rate of 2°C / min to 350°C under a forming gas (5% H2 and 95% N2) atmosphere. The final catalyst consisted of approximately 0.80 wt% Au and 1.2 wt% Pt.

[0172] Using other carbon black extrudates prepared by the above method, it was possible to prepare a series of Pt-Au extrudate catalysts spanning a range of Au and Pt loadings, Pt / Au ratios, and metal distributions (e.g., eggshell, uniform, lower surface zone).

[0173] Cross sections of catalyst extrudate samples made with Cabot Vulcan XC72 carbon black were analyzed by scanning electron microscopy. Figure 1 is an image of this analysis. The image shows that platinum and gold metals have deposited on the outer surface of the carbon black extrudate, forming a shell coating on the outer surface of the carbon black extrudate. Figure 2 shows a close-up of one catalyst extrudate cross section, including measurements of the diameter of the carbon black extrudate (i.e., 1.14 mm) and the thickness of the platinum and gold shell on the outer surface of the carbon black extrudate (average approximately 100 μm).

[0174] Example 6. Testing of Au / Pt carbon black extrudate catalyst (using Cabot Monarch 700) for the oxidation of glucose to glucaric acid in a fixed-bed reactor A catalyst containing 0.80 wt% Au and 1.20 wt% Pt was prepared by mixing extrudates based on Cabot Monarch 700 carbon black with glucose and hydroxyethyl cellulose binders. The catalyst was then prepared by mixing 42.0 g of Cabot Monarch 700 carbon black with 145.8 g of binder solution (prepared by heating a solution containing 3.4 wt% hydroxyethyl cellulose and 28.6 wt% glucose at 80°C overnight). The resulting paste was syringed and extruded into spaghetti-like threads with a diameter of 1.5 mm. After drying in an oven at 100°C under a dry air purge for 3 hours, the threads were cut into smaller pieces (2–6 mm long) and pyrolyzed at 350°C for 2 hours under a nitrogen atmosphere. The carbonized binder content in the final carbon extrudates was 31 wt%. Catalysts were then prepared using the method described in Example 5. Glucose oxidation reactions were carried out in a 12.7 mm (0.5 in) OD x 83 cm long 316 stainless steel tube using cocurrent downward flow of gas and liquid. The catalyst bed was vibration-packed with 1.0 mm glass beads to a depth of approximately 8 cm from the top, followed by a 67 cm bed containing 20.0 g of 0.80 wt % Au + 1.2 wt % Pt loaded Cabot Monarch 700 carbon black pellets (0.5 cm long and 1.5 mm diameter, prepared using the method described in Example 3), followed by 1.0 mm glass beads to a depth of approximately 8 cm from the bottom. A pad of quartz wool separated the glass beads from the catalyst bed.

[0175] The packed reactor tube was fixed in an aluminum block heater equipped with a PID controller. Gas (compressed dry air) and liquid flows were regulated by mass flow controllers and an HPLC pump, respectively. The reactor pressure was controlled by a backpressure regulator as shown in Table 6. The catalyst was tested for approximately 350 hours of time on stream (TOS). Table 6 shows the fixed-bed reactor conditions and the resulting extrudate catalyst performance. The catalyst productivity in Table 6 is 35 g (glucaric acid)·(g (Pt+Au)) -1 ·hr -1 or 0.70 g (glucaric acid)·(g (catalyst))-1 ·hr -1 is. [Table 6]

[0176] BET surface area measurements and BJM pore volume distribution measurements were performed on the following carbon black and extrudate samples: Sample 1: Monarch 700 carbon black material. Sample 2: Fresh Monarch 700 extrudate made according to this example. Sample 3: Monarch 700 extrudate of Example 4 after 350 hours of operation in a fixed bed reactor (described in Example 6). Sample 4: An aqueous solution (915.0 g) containing 4.0 wt% hydroxyethyl cellulose (Sigma-Aldrich, SKU 54290, viscosity 80-125 cP, 2% in HO at 20 °C) and 56.0 wt% glucose (ADM Corn Processing, Dextrose Monohydrate 99.7 DE; glucose content 91.2255 wt%) was prepared by stirring 36.6 g of hydroxyethyl cellulose and 561.7 g of Dextrose Monohydrate in 316.7 ml of deionized water at 80 °C for 16 hours. After cooling to ambient temperature, this viscous solution was added to 400.0 g of carbon black powder (Cabot Monarch 700) in a blender / kneader, and the materials were mixed / kneaded for 1 hour. The material was then added to a 1" Bonnot BB Gun Extruder and extruded into spaghetti-like strands of approximately 1.5 mm cross-sectional diameter. These strands were dried in an oven at 120°C under a dry air purge for 16 hours and then pyrolyzed under a nitrogen atmosphere at a rate of 5°C / min to 800°C for 2 hours. The final carbonized binder content was 36 wt%. Sample 5: Prepared as described in Example 9. Sample 6: Prepared as described in Example 12. Sample 7: An aqueous solution (166.0 g) containing 4.0 wt% hydroxyethylcellulose (Sigma-Aldrich, SKU 54290, viscosity 80-125 cP, 2% in HO at 20 °C) and 56.0 wt% glucose (ADM Corn Processing, Dextrose Monohydrate 99.7 DE; glucose content 91.2255 wt%) was prepared by stirring 6.64 g of hydroxyethylcellulose and 84.8 g of dextrose monohydrate in 74.6 ml of deionized water at 80 °C for 16 hours. After cooling to room temperature, this viscous solution was added to 60.0 g of carbon powder (Asbury 5368) in a blender / kneader, and the materials were mixed / kneaded for 1 hour. The material was then added to a 1" Bonnot BB Gun Extruder and extruded into spaghetti-like threads of approximately 1.5 mm cross-sectional diameter. These threads were dried in an oven at 120°C under a dry air purge for 16 hours and then pyrolyzed under a nitrogen atmosphere at a rate of 5°C / min to 800°C for 2 hours. The final carbonized binder content was 40 wt%. Sample 8: Commercially available activated carbon extrudate Sud Chemie G32H-N-75. Sample 9: Commercially available activated carbon extrudate Donau Supersorbon K4-35. The results are shown in Table 7. [Table 7]

[0177] Figure 3 shows a plot of cumulative pore volume (%) as a function of average pore size for raw Monarch 700 carbon black material. Figure 4 shows a plot of cumulative pore volume (%) as a function of average pore size for a fresh catalyst made from Monarch 700 carbon black and carbon black extrudates using a glucose / hydroxyethyl cellulose binder. Figure 5 shows a plot of cumulative pore volume (%) as a function of average pore size for the catalyst extrudates of Figure 2 after 350 hours of use in a fixed-bed reactor for the oxidation of glucose to glucaric acid. Figure 6 shows a plot of cumulative pore volume (%) as a function of average pore size for extrudates using Monarch 700 carbon black and a glucose / hydroxyethyl cellulose binder. Figure 7 shows a plot of cumulative pore volume (%) as a function of average pore size for extrudates using Sid Richardson SC159 carbon black and a glucose / hydroxyethyl cellulose binder. Figure 8 shows a plot of cumulative pore volume (%) as a function of average pore size for extrudates made according to Example 12 using Sid Richardson SC159 carbon black and a glucose / hydroxyethyl cellulose binder. Figure 9 shows a plot of cumulative pore volume (%) as a function of average pore size for extrudates using Asbury 5368 carbon black and a glucose / hydroxyethyl cellulose binder. Figure 10 shows a plot of cumulative pore volume (%) as a function of average pore size for Sud Chemie G32H-N-75 commercially available activated carbon extrudates. Figure 11 shows a plot of cumulative pore volume (%) as a function of average pore size for Donau Supersorbon K4-35 commercially available activated carbon extrudates.

[0178] Figure 12 shows the pore size distribution of extrudates using Sid Richardson SC159 carbon black and a glucose / hydroxyethyl cellulose binder, as measured by mercury porosimetry. These plots demonstrate that the contribution of micropores to the pore volume of carbon black extrudate catalysts (both fresh and used) is very small. In particular, the plots show that the contribution of micropores (pores less than 3 nm) is less than 10% of the BJH pore volume. In some cases, the contribution of micropores (pores less than 3 nm) is less than 6% of the BJH pore volume, and in other cases, the contribution of micropores (pores less than 3 nm) is less than 4% of the BJH pore volume. In contrast, the contribution of micropores to the pore volume of activated carbon extrudate catalysts is significantly higher, at 40%. The plots also show that the contribution of pore volume from pores with average diameters of approximately 10 nm to 50 nm for carbon black catalysts was greater than approximately 40%. On the other hand, the contribution to the pore volume from pores with an average diameter of about 10 nm to 50 nm for the activated carbon catalyst was less than about 15%. The plot shows that the contribution to the pore volume from pores with an average diameter of about 10 nm to 100 nm for the carbon black catalyst was greater than about 70%. On the other hand, the contribution to the pore volume from pores with an average diameter of about 10 nm to 100 nm for the activated carbon catalyst was less than about 15%.

[0179] Example 7. Testing of Au / Pt carbon black extrudate catalyst (using Cabot Vulcan XC72) in a fixed-bed reactor for the oxidation of glucose to glucaric acid A catalyst containing 0.80 wt. % Au and 1.20 wt. % Pt was prepared by mixing extrudates based on Cabot Vulcan XC72 carbon black with 36.4 g of Cabot Vulcan XC72 carbon black and 136.5 g of a binder solution (prepared by heating a solution containing 3.7 wt. % hydroxyethyl cellulose and 24.4 wt. % glucose at 80°C overnight). The resulting paste was placed in a syringe, and the material was extruded into 1.5 mm diameter spaghetti-like strands. The extrudates were subsequently dried in air at 120°C for 4 hours and pyrolyzed at 350°C for 2 hours under a nitrogen atmosphere. The binder content in the final pyrolytic carbon extrudates was 30 wt. %. The catalyst was prepared using the method described in Example 3. The catalyst was tested in the same 12.7 mm (0.5 inch) OD fixed-bed reactor as in Example 6. Table 8 shows the fixed-bed reactor conditions and the resulting extrudate catalyst performance. The catalyst productivity in Table 8 is 36 g (glucaric acid)·(g (Pt+Au)) -1 ·hr -1 or 0.72 g (glucaric acid)·(g (catalyst)) -1 ·hr -1 is. [Table 8]

[0180] Example 8. Oxidation of glucose to glucaric acid - high surface area activated carbon (comparative example) A Pt-Au catalyst supported on high surface area activated carbon was prepared using the same synthesis procedure as described in Example 6. The activated carbon extrudates were crushed and sieved to a size of less than 90 μm prior to catalyst preparation and screening. The catalyst was screened in the same reactor under the same conditions as described in Example 2(B)(ii). As shown in Table 9, the high surface area activated carbon support was found to exhibit lower activity and lower selectivity (as defined herein). [Table 9]

[0181] Example 9. Preparation of Carbon Black Extrudate Catalysts - Attrition and Wear Testing An aqueous solution (113 g) containing 4.0 wt% hydroxyethylcellulose (Sigma-Aldrich, SKU 54290, viscosity 80-125 cP, 2% in HO at 20 °C) and 56.0 wt% glucose (ADM Corn Processing, Dextrose Monohydrate 99.7 DE; glucose content 91.2255 wt%) was prepared by stirring 4.5 g of hydroxyethylcellulose and 69.4 g of Dextrose Monohydrate in 39.1 ml of deionized water at 80 °C overnight. After cooling to room temperature, this viscous solution was mixed with 50 g of carbon black powder (Sid Richardson SC159, 231 ml) in a blender / kneader. 2 / g) and the material was mixed / kneaded for 1 hour. The material was then added to a 1" Bonnot BB Gun Extruder and extruded into spaghetti-like threads of approximately 1.5 mm cross-sectional diameter. These threads were dried overnight in a 120°C oven under a dry air purge and then pyrolyzed under a nitrogen purge at a rate of 5°C / min to 800°C for 4 hours. The extruded and pyrolyzed samples were cut into approximately 0.5 cm long pieces for testing. The properties of the resulting extrudates are shown in Table 10. BET and crush strength measurements were performed as described in this disclosure. [Table 10]

[0182] The extrudates made according to this example were evaluated for wear index (ASTM D4058-96) and wear rate according to the following procedures.

[0183] Measurement of wear index. The ASTM Attrition Test (ATTR) is a measure of the resistance of catalyst or extrudate particles to abrasive wear by repeatedly impacting the particles against a hard surface in a specified test drum. The diameter and length of the drum are similar to those described in ASTM D4058 and equipped with a rotating device capable of imparting a rotation of 55-65 RPM to the test drum. The percentage of the original sample retained on the 20-mesh sieve is called the "retention" result of the test. The results of this test can be used, in relative comparison, as a measure of fines generation during handling, transfer, and use of the catalyst or extrudate material. For industrial applications, a retention result of greater than 97% is desirable.

[0184] Approximately 100 g of the extrudate material prepared in Example 9 above was transferred to a test drum, the drum secured, transferred to a rolling device, and rotated at 55-65 RPM for 35 minutes. After testing, the sieve retention weight percent was 99.7%.

[0185] Measurement of wear rate. The attrition rate (ABL) is another measure of the resistance of catalyst or extrudate particles to attrition due to vigorous horizontal shaking of the particles within the confines of a 30-mesh sieve. The results of this method can be used, in relative comparison, as a measure of fines generation during handling, transportation, and use of the catalyst or adsorbent material. For industrial applications, an attrition rate of less than 2 wt. % is desirable. Approximately 100 g of extrudate material prepared in Example 9 was first dedusted on a 20-mesh sieve by gently moving the sieve sideways at least about 20 times. The dedusted sample was then transferred to a clean 30-mesh sieve stacked on top of a clean sieve pan for fines collection. The entire sieve stack was then assembled on a RO-Tap RX-29 sieve shaker, securely capped, and shaken for about 30 minutes. The resulting fines were weighed, yielding a sample attrition rate of 0.016 wt. %.

[0186] Example 10. Testing of the Au / Pt carbon black extrudate catalyst of Example 9 in a fixed-bed reactor for the oxidation of glucose to glucaric acid Carbon black extrudates prepared as described in Example 9 were further cut into approximately 0.5 cm long pieces for testing. To 27.0 g of these extrudates was added 8.0 ml of an aqueous solution containing 0.16 g of Au in the form of Me4NAuO2 and 0.24 g of Pt in the form of PtO(NO3). The mixture was stirred to impregnate the carbon black support and dried in an oven at 70 °C for 1 hour under a dry air purge. The sample was then heated to 350 °C at a rate of 2 °C / min under a forming gas (5% H2 and 95% N2) atmosphere and reduced for 4 hours. The final catalyst consisted of approximately 0.60 wt% Au and 0.90 wt% Pt. Using other carbon black extrudates prepared by the methods described herein, a series of Pt-Au extrudate catalysts can be prepared, spanning a range of Au and Pt loadings, Pt / Au ratios, and metal distributions (e.g., eggshell, uniform, lower surface zone).

[0187] The oxidation of glucose to glucaric acid was carried out in a 1 / 2" OD x 83 cm long 316 stainless steel tube using cocurrent downward flow of gas and liquid. The catalyst bed was vibrated and packed to a depth of approximately 10 cm from the top with 1.0 mm glass beads, followed by a 63 cm bed containing 27.4 g of 0.60 wt % Au + 0.90 wt % Pt loaded Sid Richardson SC159 carbon black pellets (0.5 cm long and 1.4 mm diameter, prepared using the method described), followed by 1.0 mm glass beads packed to a depth of approximately 10 cm from the bottom. A pad of quartz wool separated the glass beads from the catalyst bed.

[0188] The packed reactor tube was fixed in an aluminum block heater equipped with a PID controller. Gas (compressed dry air) and liquid flows were regulated by mass flow controllers and an HPLC pump, respectively. The reactor pressure was controlled by a back pressure regulator, as shown in Table 11. The catalyst was tested for approximately 920 hours of run time and showed stable performance. Table 11 shows the fixed-bed reactor conditions and the resulting extrudate catalyst performance. The catalyst productivity in Table 11 was 23 grams (glucaric acid)·(grams (Pt+Au)) -1 ·hr -1 or 0.35 g (glucaric acid)·(g (catalyst)) -1 ·hr -1 is. [Table 11]

[0189] After 920 hours on stream, the catalyst extrudates were removed and reused for mechanical crush strength testing. The average single crush strength and average ring crush strength data were consistent with the data in Table 10 within experimental error, thereby indicating that the extrudate catalysts made by the described method are productive, selective, and stable under the described continuous flow conditions.

[0190] Example 11. Testing of Au / Pt carbon black extrudate catalysts (using Asbury 5368) in a fixed-bed reactor for the oxidation of glucose to glucaric acid The reaction was carried out in a 1 / 2" OD x 83 cm long 316 stainless steel tube using cocurrent downward flow of gas and liquid. The catalyst bed was vibration packed with 1.0 mm glass beads to a depth of approximately 8 cm from the top, followed by a 73 cm bed thickness containing 35.0 g of 0.50 wt % Au + 0.85 wt % Pt supported Asbury 5368 extruded pellets (0.5 cm long and 1.4 mm diameter, prepared using the method described in Example 9 above, as previously described for Sample 7 (Example 6) above), followed by the 1.0 mm glass beads to a depth of approximately 8 cm from the bottom. A pad of quartz wool separated the glass beads from the catalyst bed.

[0191] The packed reactor tube was fixed in an aluminum block heater equipped with a PID controller. Gas (compressed dry air) and liquid flows were regulated by mass flow controllers and an HPLC pump, respectively. The reactor pressure was controlled by a back pressure regulator, as shown in Table 12. The catalyst was tested at a TOS of approximately 240 hours and showed stable performance. Table 12 shows the fixed-bed reactor conditions and the resulting extrudate catalyst performance. The catalyst productivity in Table 12 is 20 grams (glucaric acid)·(grams (Pt+Au)) -1 ·hr -1 or 0.27 g (glucaric acid)·(g (catalyst)) -1 ·hr -1 is. [Table 12]

[0192] Example 12. Preparation of carbon black extrudate catalyst-loaded partial oxidation support Sid Richardson SC159 carbon black extrudates were oxidized in air at a rate of 5°C / min to 300°C for 3 hours to obtain partially oxidized pellets, as described in Example 9. To 36.0 g of these partially oxidized extrudates was added an aqueous solution (9.0 ml) containing 0.18 g of Au in the form of Me4NAuO2 and 0.31 g of Pt in the form of PtO(NO3). The mixture was stirred to impregnate the carbon black support and dried overnight in an oven at 60°C under a dry air purge. The sample was then reduced under a forming gas (5% H2 and 95% N2) atmosphere at a rate of 2°C / min to 350°C for 4 hours. The final catalyst consisted of approximately 0.50 wt% Au and 0.85 wt% Pt. Other carbon black extrudates prepared by the methods described herein can be used to prepare a series of Pt-Au extrudate catalysts spanning a range of Au and Pt loadings, Pt / Au ratios, and metal distributions (e.g., eggshell, uniform, lower surface zone). The oxidation of glucose to glucaric acid was carried out in a 1 / 2" OD x 83 cm long 316 stainless steel tube using cocurrent downward flow of gas and liquid. The catalyst bed was vibrated and packed to a depth of approximately 6 cm from the top with 1.0 mm glass beads, followed by a 70.4 cm bed containing 34.5 g of 0.50 wt. % Au + 0.85 wt. % Pt-loaded partially oxidized Sid Richardson SC159 carbon black pellets (0.5 cm long and 1.5 mm diameter, prepared using the method described in Example 2), followed by 1.0 mm glass beads packed to a depth of approximately 6 cm from the bottom. A pad of quartz wool separated the glass beads from the catalyst bed.

[0193] The packed reactor tube was fixed in an aluminum block heater equipped with a PID controller. Gas (compressed dry air) and liquid flows were regulated by mass flow controllers and an HPLC pump, respectively. The reactor pressure was controlled by a back pressure regulator, as shown in Table 13. The catalyst was tested at a TOS of about 230 hours and showed stable performance. Table 13 shows the fixed-bed reactor conditions and the resulting extrudate catalyst performance. The catalyst productivity in Table 13 was 26 grams (glucaric acid)·(grams (Pt+Au)) -1 ·hr -1or 0.36 g (glucaric acid)·(g (catalyst)) -1 ·hr -1 is. [Table 13]

[0194] Example 13. Preparation of carbon black extrudates using poly(vinyl alcohol) porogen An aqueous solution (490.0 g) containing 8.0 wt% Mowiol 8-88 poly(vinyl alcohol) (Mw 67k, Sigma-Aldrich 81383) and 36.0 wt% glucose (ADM Corn Processing, Dextrose Monohydrate 99.7 DE; % glucose content 91.2255 wt%) was prepared by stirring 39.2 g of Mowiol 8-88 poly(vinyl alcohol) and 193.4 g of Dextrose Monohydrate in 257.4 ml of deionized water overnight at 70° C. After cooling to room temperature, this solution was added to 230 g of carbon black powder (Sid Richardson SC159) in a blender / kneader, and the materials were mixed / kneaded for 1 hour. The material was then added to a 1" Bonnot BB Gun Extruder and extruded into spaghetti-like strands of approximately 1.5 mm cross-sectional diameter. These strands were further dried overnight in a 90°C oven under a dry air purge and then pyrolyzed under a nitrogen atmosphere at a rate of 5°C / min to 600°C for 4 hours. The final carbonized binder content was 24 wt%. The resulting extrudates (3-5 mm long) were collected in a 149 m² oven. 2 / g surface area, 0.35 cm 3 / g and an average pore size of 16 nm. The average ring crushing strength of these pellets was measured to be 11.5 N / mm. The single crushing strength was measured to be 42 N.

[0195] Example 14. Testing of Au / Pt activated carbon extrudate catalysts (using Clariant Donau Supersorbon K4-35 activated carbon extrudates) in a fixed-bed reactor for the oxidation of glucose to glucaric acid A catalyst based on activated carbon Clariant Supersorbon K4-35 was prepared using the same method as described in Example 7. The glucose oxidation reaction was carried out using the same method as described in Example 2(B)(ii). A 73 cm thick catalyst bed containing 27.0 g of 0.53 wt % Au + 0.90 wt % Pt supported Clariant Supersorbon K4-35 activated carbon pellets, 0.5 cm long and 1.4 mm in diameter, was tested for approximately 40 hours of time on stream (TOS). Table 14 shows the fixed-bed reactor conditions and the resulting extrudate catalyst performance. After 40 hours of operation, the glucaric acid yield and catalyst productivity were lower than those of the shaped carbon black catalyst of the present invention. [Table 14]

[0196] Example 15. Preparation of carbon black extrudates An aqueous solution (915 g) containing 4.0 wt% hydroxyethyl cellulose (HEC) (Sigma-Aldrich, SKU 54290, viscosity 80-125 cP, 2% in HO at 20 °C) and 56.0 wt% glucose (ADM Corn Processing, Dextrose Monohydrate 99.7 DE; glucose content 91.2 wt%) was prepared by stirring 36.6 g of hydroxyethyl cellulose and 561.7 g of Dextrose Monohydrate in 316.7 ml of deionized water at approximately 80 °C for 2 hours. This viscous solution was added to 400.1 g of Sid Richardson SC159 carbon black powder, and the mixture was then mixed for an additional 10 minutes. The material was then loaded into a 1" diameter Bonnot extruder equipped with a 1 / 4" spacer and a 1.6mm die with cylindrical holes and extruded into spaghetti-like strands. The extrudates were dried overnight in a 110°C oven and then pyrolyzed at 800°C for 4 hours (after increasing the temperature at a rate of 5°C / min until the target temperature was reached) in a stationary laboratory furnace under a nitrogen purge (Table 15). [Table 15]

[0197] Example 16. Preparation of carbon black extrudates An aqueous solution (3813 g) containing 4.0 wt% hydroxyethyl cellulose (HEC) (Sigma-Aldrich, SKU 54290, viscosity 80-125 cP, 2% in HO at 20 °C) and 56.0 wt% glucose (ADM Corn Processing, Dextrose Monohydrate 99.7 DE; glucose content 91.2 wt%) was prepared by stirring 153 g of hydroxyethyl cellulose and 2340 g of Dextrose Monohydrate in 1320 ml of deionized water at approximately 80 °C for 3 hours. This viscous solution was added to 1670 g of Sid Richardson SC159 carbon black powder in a Mueller mixer over 3.5 minutes, and the mixture was then mixed in the Mueller mixer for an additional 20 minutes. The material was then loaded into a 2" diameter Bonnot extruder equipped with five dies (JMP Industries, part number 0388P062) with 26 cylindrical holes each of 1 / 16" inside diameter, but no spacers, and extruded into spaghetti-like strands. 1515 g of extrudate was dried overnight in an oven at 110°C, yielding 1240 g of dried extrudate. The product was then pyrolyzed at 800°C for 4 hours in a stationary tube furnace under a nitrogen purge (Table 16). [Table 16]

[0198] Example 17. Preparation of carbon black extrudates using batch pyrolysis in a rotary tubular furnace An aqueous solution (3813 g) containing 4.0 wt. % Dow Cellosize HEC QP40 hydroxyethyl cellulose (viscosity 80-125 cP, 2% in HO at 20°C) and 56.0 wt. % glucose (ADM Corn Processing, Dextrose Monohydrate 99.7 DE; glucose content 91.2 wt. %) was prepared by stirring 153 g of hydroxyethyl cellulose and 2340 g of Dextrose Monohydrate in 1320 ml of deionized water at approximately 80°C for 3 hours. This viscous solution was added to 1670 g of Sid Richardson SC159 carbon black powder in a Mueller mixer over 3.5 minutes, after which the mixture was mixed in the Mueller mixer for an additional 20 minutes. The material was then loaded into a 2" diameter Bonnot extruder equipped with five dies (JMP Industries, part number 0388P062) with 26 cylindrical holes, each 1 / 16" inside diameter, but no spacers, and extruded into spaghetti-like strands. 3.9 kg of the extrudate was dried overnight in an oven at 110°C, producing 2.93 kg of dried extrudate. This dried extrudate was then sieved through an 18-mesh screen, and 2.91 kg of the sieved material was collected.

[0199] The above mixing, extruding, drying and sieving procedure was repeated three more times to produce a total of four batches of dried, sieved extrudate, which were combined as summarized in Table 17. [Table 17]

[0200] Next, 650 g batches of the combined dried and sieved extrudates were pyrolyzed in a rotary tube furnace under a nitrogen purge at 800°C for 2 hours, yielding approximately 350 g of pyrolysis product from each batch. For each batch, 650 g of carbon black extrudate (made from Sid Richardson Sc159 and a hydroxyethyl cellulose binder) was loaded into an MTI Corporation 5" Quartz Tube Three Zone Rotary Tube Furnace (OTF-1200X-5L-R-III-UL). The carbon black extrudates were pyrolyzed in a 5" quartz tube rotating at 4.0 rpm under a nitrogen atmosphere at 800°C for 2 hours using the following heating schedule: room temperature to 200°C: 10°C / min, 200°C to 600°C: 5°C / min, 600°C to 800°C: 10°C / min, and held at 800°C for 2 hours, after which the temperature was allowed to cool to room temperature while maintaining the nitrogen purge. 350 g of pyrolyzed carbon black extrudates were recovered for a mass yield of 51.5%. Properties of the batch pyrolyzed extrudates are shown in Table 18. Other carbon black extrudates can be pyrolyzed at various temperatures in a similar manner or using a continuously operated rotary kiln as described in the following examples. [Table 18]

[0201] Example 18. Preparation of carbon black extrudates using continuous pyrolysis in a rotary kiln The blending, extrusion, drying, and sieving procedure described in Example 17 was repeated 10 more times to produce an additional 33.4 kg of dried, sieved extrudate, which was combined. 25.7 kg of the combined dried and sieved extrudate was then pyrolyzed in a continuous rotary kiln using a continuous nitrogen purge (countercurrent to the extrudate) and a continuous feed of 0.5 kg / hr of dried extrudate, and the product was collected at several set points summarized in Table 19. The rotary kiln was electrically heated. The temperature set points for the external heaters are listed in Table 19, along with the calculated residence time of the material in the heating zone. The temperature and residence time were adjusted to affect the surface area of ​​the product. A total of 12.5 kg of pyrolysis product was collected. The overall mass yield was 48.5%. [Table 19]

[0202] Example 19. Hydrodeoxygenation of glucaric acid dilactone to adipic acid Appropriately concentrated aqueous solutions of rhodium nitrate and platinum nitrate were added together to carbon black powder (ground from carbon black pellets) by the incipient wetness impregnation method and stirred to impregnate the support. The sample was dried in an oven at 60°C overnight, then heated to 350°C at a rate of 2°C / min under a forming gas (5% H2 and 95% N2) atmosphere and reduced for 4 hours to produce a catalyst with a composition of 1.0 wt% Rh and 2.0 wt% Pt. Different catalysts with various Rh and Pt loadings on various extrudate-derived particles were prepared in a similar manner by using other carbon black supports, Rh and Pt precursors, and controlled amounts of Rh and Pt in solution.

[0203] These catalysts were tested for the hydrodeoxygenation of glucaric dilactone using the following test protocol: 16 mg of catalyst was weighed into a glass vial insert, followed by 125 μL of a solution containing 0.80 M glucaric dilactone, 0.80 M HBr, and 2.0 M water. The glass vial insert was placed in a reactor, and the reactor was closed. The atmosphere in the reactor was replaced with hydrogen and pressurized to 900 psig at room temperature. The reactor was heated to 120°C and held at 120°C for 1 hour while the vial was shaken. The reactor was then heated to 160°C and held at 160°C for 2 hours while the vial was shaken. The shaking was then stopped, and the reactor was cooled to 40°C. The pressure in the reactor was slowly released. The glass vial insert was removed from the reactor and centrifuged. The clear solution was hydrolyzed with NaOH, diluted with deionized water, and analyzed by ion chromatography to determine the yield of adipic acid. The properties of the carbon black starting material and the results of the reaction screen are shown in Table 20. [Table 20]

[0204] Example 20. Testing of Rh / Pt carbon black extrudate catalyst in a fixed-bed reactor for the hydrodeoxygenation of glucaric acid to adipic acid The Cabot Vulcan XC72 carbon black particles used in this experiment were 150-300 μm particles crushed and sieved from extruded pellets prepared by the method described in the previous example. The reaction was carried out in a 6.4 mm (0.25 in) OD x 38 cm long zirconium tube using cocurrent downward flow of gas and liquid. The catalyst bed was vibrated to a depth of approximately 5 cm from the top with 200-300 μm glass beads, followed by the catalyst (a 28 cm thick bed containing 19.0 g of 0.90 wt% Rh + 2.1 wt% Pt-loaded carbon black particles with a particle size of 150-300 μm), followed by the 200-300 μm glass beads to a depth of approximately 5 cm from the bottom. A pad of quartz wool separated the glass beads from the catalyst bed.

[0205] The packed reactor tube was fixed in an aluminum block heater equipped with a PID controller. Gas (compressed hydrogen) and liquid flows were regulated by mass flow controllers and an HPLC pump, respectively. The substrate solution contained 0.80 M D-glucaric acid-1,4:6,3-dilactone, 0.40 M HBr, and 2.0 M water in acetic acid. The reactor pressure was controlled by a backpressure regulator as shown in Table 21. The external temperatures of the upper and lower reactor halves were controlled at 110°C and 160°C, respectively. The catalyst was tested for approximately 350 hours of operation and showed stable performance. Table 21 shows the fixed-bed reactor conditions and the resulting catalyst performance. [Table 21]

[0206] Example 21. Hydrodeoxygenation of 1,2,6-Hexanetriol to 1,6-Hexanediol Pt(NO3) x and H4SiO4 * 12WO3 or PtONO3 and H4SiO4 * An appropriately concentrated aqueous solution of 12WO3 was added to approximately 50 mg of Ensaco 250G carbon and stirred to impregnate the support. The sample was dried overnight in an oven under static air at 40°C and then reduced for 3 hours at 350°C under a forming gas (5% H2 and 95% N2) atmosphere. The final catalyst had a metal content of approximately 4.09 wt% Pt and 3.42 wt% W.

[0207] These catalysts were tested for 1,2,6-hexanetriol hydrodeoxygenation using the following catalytic test protocol: The catalyst (approximately 10 mg) was weighed into a glass vial insert, followed by the addition of 200 μL of 0.8 M aqueous 1,2,6-hexanetriol solution. The glass vial insert was placed in a reactor, and the reactor was closed. 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 held at each temperature for 150 minutes while the vial was shaken. After 150 minutes, the shaking was stopped, and the reactor was cooled to 40°C. The pressure in the reactor was then slowly released. The glass vial insert was removed from the reactor and centrifuged. The solution was diluted with methanol and analyzed by gas chromatography equipped with a flame ionization detector. The results are shown in Table 22. [Table 22]

[0208] Example 22. Hydrodeoxygenation of 1,2,6-Hexanetriol to 1,6-Hexanediol Ammonium metatungstate and H 26 N6W 12 O 40 An appropriately concentrated aqueous solution of Pt(NMe4)2(OH)6 was added to approximately 500 mg of Ensaco 250G and stirred to impregnate the carbon black support. The sample was heated to 600°C at a rate of 5°C / min under a nitrogen atmosphere and heat-treated for 3 hours. An appropriately concentrated aqueous solution of Pt(NMe4)2(OH)6 was added to 50 mg of the above sample and stirred to impregnate the carbon support. The sample was dried overnight at 40°C in an oven under static air, then heated to 250°C at a rate of 5°C / min under a forming gas (5% H2 and 95% N2) atmosphere and reduced for 3 hours. The final catalyst had a metal content of approximately 4.5 wt% Pt and 2 wt% W.

[0209] These catalysts were tested for 1,2,6-hexanetriol hydrodeoxygenation using the following catalytic testing protocol: The catalyst (approximately 10 mg) was weighed into a glass vial insert, followed by the addition of 200 μL of 0.8 M aqueous 1,2,6-hexanetriol solution. The glass vial insert was placed in a reactor, and the reactor was closed. 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 held at each temperature for 150 minutes while the vial was shaken. After 150 minutes, the shaking was stopped, and the reactor was cooled to 40°C. The pressure in the reactor was then slowly released. The glass vial insert was removed from the reactor and centrifuged. The clear solution was diluted with methanol and analyzed by gas chromatography equipped with a flame ionization detector. The results are shown in Table 23. [Table 23]

[0210] Example 23. Hydrodeoxygenation of 1,2,6-Hexanetriol to 1,6-Hexanediol Ammonium metatungstate and H 26 N6W 12 O 40 An appropriately concentrated aqueous solution of Pt(NMe4)2(OH)6 was added to approximately 500 mg of carbon black material and stirred to impregnate the carbon black support. The sample was heat-treated under a nitrogen atmosphere at a rate of 5°C / min to 600°C for 3 hours. An appropriately concentrated aqueous solution of Pt(NMe4)2(OH)6 was added to approximately 50 mg of the above sample and stirred to impregnate the carbon support. The sample was dried overnight at 60°C in an oven under static air, then heated to 350°C at a rate of 5°C / min under a forming gas (5% H2 and 95% N2) atmosphere and reduced for 3 hours. The final catalyst had a metal content of approximately 5.7 wt% Pt and 1.8 wt% W.

[0211] These catalysts were tested for 1,2,6-hexanetriol hydrodeoxygenation using the following catalytic test protocol: The catalyst (approximately 10 mg) was weighed into a glass vial insert, followed by the addition of 200 μL of 0.8 M aqueous 1,2,6-hexanetriol solution. The glass vial insert was placed in a reactor, and the reactor was closed. 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 held at each temperature for 150 minutes while the vial was shaken. After 150 minutes, the shaking was stopped, and the reactor was cooled to 40°C. The pressure in the reactor was then slowly released. The glass vial insert was removed from the reactor and centrifuged. The clear solution was diluted with methanol and analyzed by gas chromatography equipped with a flame ionization detector. The results are shown in Table 24. [Table 24]

[0212] Example 24. Small-Scale Batch Reactor Experiments for the Amination of 1,6-Hexanediol to Form 1,6-Hexamethylenediamine Amination of 1,6-Hexanediol to Produce 1,6-Hexamethylenediamine - Analytical Details Product composition was determined by HPLC analysis using a Thermo Ultimate 3000 dual analytical chromatography system. Hexamethylenediamine (HMDA), hexamethyleneimine (HMI), and pentylamine were eluted with a mobile phase containing HO / MeCN / TFA and detected using a charged aerosol detector (CAD). 1,6-Hexanediol (HDO) was eluted with a mobile phase containing HO / MeCN / TFA and detected using a refractive index detector (RI). In certain examples, an internal standard, N-methyl-2-pyrrolidone (NMP), was used in the substrate feed to correct for variations in product effluent concentrations due to NH outgassing. NMP was eluted with a mobile phase containing HO / MeCN / TFA and detected by UV at 210 nm. Total products were quantified by comparison to calibration standards. Selectivity was reported as the yield of HMDA divided by the sum of HMDA and pentylamine.

[0213] Experiment 1 Preparation of Ru-supported catalysts An appropriately concentrated aqueous solution of Ru(NO)(NO3)3 was added to a 96-vialet array of carbon support vials, each containing 10 or 20 mg of carbon support. The volume of the ruthenium solution was adjusted to equal the pore volume of the support. Each sample was stirred and impregnated onto the support. The samples were dried in an oven at 60°C for 12 hours under a dry air purge. The catalyst was reduced under a forming gas (5% H2 and 95% N2) atmosphere at a rate of 2°C / min to 250°C for 3 hours. The final catalyst consisted of 2 weight percent ruthenium.

[0214] Catalyst screening procedure A substrate solution consisting of 0.7 M 1,6-hexanediol in concentrated aqueous NHOH was added to the catalyst series prepared above. The vials were covered with a Teflon pinhole sheet, a silicone pinhole mat, and a steel gas diffusion plate. The reactor insert was placed in a pressure vessel and purged twice with NH3 gas. The pressure vessel was charged with NH3 gas to 100 psi at ambient temperature and then increased to 680 psi with N2. The reactor was placed on a shaker and vortexed at 160 °C and 800 rpm. After 3 hours, the reactor was cooled to room temperature, evacuated, and purged with nitrogen before being unsealed. The sample was diluted with water and then centrifuged to separate the catalyst particles. An aliquot was removed from the supernatant and further diluted with dilute aqueous trifluoroacetic acid for analysis by HPLC. The results are summarized in Table 25. [Table 25]

[0215] Experiment 2 Preparation of Ru / Re supported catalysts Appropriately concentrated aqueous solutions of Ru(NO)(NO) containing various amounts of HReO were added to 0.15 g of support and stirred to impregnate the support. The volume of the metal solution was adjusted to equal the pore volume of the support. The samples were dried in an oven at 60 °C for 3 hours under a dry air purge. Catalyst amounts ranging from 10 to 20 mg were weighed into glass vials in a 96-vial array. The catalysts were reduced under a forming gas (5% H and 95% N) atmosphere at 60 °C for 3 hours, then heated to 250 °C at a rate of 2 °C / min and reduced for 3 hours. The final catalysts consisted of 4.04 weight percent ruthenium with various rhenium loadings of 0, 0.4, 0.7, and 1.9 wt%.

[0216] Catalyst screening procedure A substrate solution consisting of 1.549 M 1,6-hexanediol in concentrated aqueous NHOH was added to the catalyst series prepared above. The vials were covered with a Teflon pinhole sheet, a silicone pinhole mat, and a steel gas diffusion plate. The reactor insert was placed in a pressure vessel and purged twice with NH3 gas. The pressure vessel was charged with NH3 gas to 100 psi at ambient temperature and then increased to 680 psi with N2. The reactor was placed on a shaker and vortexed at 160 °C and 800 rpm. After 3 hours, the reactor was cooled to room temperature, evacuated, and purged with nitrogen before being unsealed. The sample was diluted with water and then centrifuged to separate the catalyst particles. An aliquot was removed from the supernatant and further diluted with dilute aqueous trifluoroacetic acid for analysis by HPLC. The results are summarized in Table 26 below. [Table 26]

[0217] Experiment 3 Preparation of Ni / Ru-loaded Ensaco250G Appropriately concentrated aqueous solutions containing Ni(NO3)2 and / or Ru(NO)(NO3)3 were added to approximately 0.4 g of carbon black support by incipient wetness impregnation and stirred to impregnate the support. The volume of the metal solution was adjusted to equal the pore volume of the support. Each catalyst was heat-treated in a tube furnace under N2 at 60 °C for 12 hours, then heated to 300 °C at a rate of 5 °C / min and reduced for 3 hours.

[0218] Catalyst amounts ranging from 15 to 25 mg were weighed into glass vials in a 96-vial array. The catalyst was reduced in a forming gas (5% H and 95% N) atmosphere at a rate of 2 °C / min to 450 °C for 3 h. Before removal from the tube furnace, the catalyst was passivated with 1% O in N at room temperature.

[0219] Catalyst Screening Procedure A A substrate solution consisting of 0.7 M 1,6-hexanediol in concentrated aqueous NHOH was added to the catalyst series prepared above. The vials were covered with a Teflon pinhole sheet, a silicone pinhole mat, and a steel gas diffusion plate. The reactor insert was placed in a pressure vessel and purged twice with NH3 gas. The pressure vessel was charged with NH3 gas to 100 psi at ambient temperature and then increased to 680 psi with N2. The reactor was placed on a shaker and vortexed at 160 °C and 800 rpm. After 3 hours, the reactor was cooled to room temperature, evacuated, and purged with nitrogen before being unsealed. The sample was diluted with water and then centrifuged to separate the catalyst particles. An aliquot was removed from the supernatant and further diluted with dilute aqueous trifluoroacetic acid for analysis by HPLC. The results are summarized in Table 27 below. [Table 27]

[0220] Catalyst Screening Procedure B The passivated catalysts were reactivated in water under H2 at 180°C for 3 hours. Most of the water was removed from each catalyst, leaving enough to act as a protective layer. The catalysts were then screened as described in Procedure A above. The results are summarized in Table 28 below. [Table 28]

[0221] Fixed-bed experiments Preparation of 2 wt% Ru-loaded carbon Ensaco 250G Carbon extrudates made from Ensaco 250G carbon black and a carbohydrate binder were crushed to a size of 150-300 μm. An appropriately concentrated aqueous solution of Ru(NO)(NO3)3 was added to 4.77 g of crushed extrudates and stirred to impregnate the support. The volume of the metal solution was adjusted to equal the pore volume of the support. The sample was dried in an oven at 60 °C under a dry air purge for 12 hours. The catalyst was then heated to 250 °C at a rate of 2 °C / min under a forming gas (5% H2 and 95% N2) atmosphere and reduced for 3 hours. The catalyst was washed with water and again crushed to a size of 106-300 μm to remove any fines that may have been generated during the metal impregnation step.

[0222] Preparation of 10.5 wt% Ni and 0.45 wt% Ru loaded carbon Ensaco 250G Carbon extrudates made from Ensaco 250G carbon black and a carbohydrate binder were crushed to a size range of 106–300 μm. An appropriately concentrated aqueous solution containing Ni(NO3)2·6H2O and Ru(NO)(NO3)3 was added to 10 g of crushed extrudates and stirred to impregnate the support. The volume of the metal solution was adjusted to equal the pore volume of the support. The catalyst was dried in an oven at 60 °C for 12 h under a dry air purge and then pyrolyzed at 300 °C for 3 h under N2. The catalyst was then heated to 450 °C at a rate of 2 °C / min under forming gas (5% H2 and 95% N2) and reduced for 3 h. After cooling to room temperature, the catalyst was passivated at room temperature using 1% O2 in N2 before removal from the tube furnace. The catalyst was washed with water and again crushed to a size range of 106–300 μm to remove any fines that may have been generated during the metal impregnation step.

[0223] 2 wt% Ru supported carbon catalyst The reaction was carried out in a 0.25-inch OD x 570 mm long 316 stainless steel tube with a 2 μm 316 stainless steel frit at the bottom of the catalyst bed. The reactor was vibratory packed with 1 g of SiC beads (90-120 μm), followed by 3 g of 2 wt. % ruthenium-on-carbon Ensaco 250G catalyst (100-300 μm), and finally 2.5 g of SiC beads on top. A 1 / 4 layer of glass wool was used between each layer. The packed reactor tube was mounted vertically in an aluminum block heater equipped with a PID controller. An HPLC pump delivered the liquid feed to the top of the reactor, and a backpressure regulator controlled the reactor pressure. The reaction was run at 160 °C. Product effluent was collected periodically for analysis by HPLC. No degradation in catalyst activity was observed after 1650 h.

[0224] Three different feed compositions were investigated using 160°C and reactor pressures ranging from 800 to 1000 psi. In all cases, N-methyl-2-pyrrolidone (NMP) was used as an internal standard. Feed 1: 0.7 M 1,6-hexanediol and 0.14 M NMP in concentrated NH4OH. Feedstock 2: 0.7 M 1,6-hexanediol, 0.14 M hexamethyleneimine, and 0.14 M NMP in concentrated NH4OH. Feedstock 3: 1.54 M 1,6-hexanediol, 0.308 M hexamethyleneimine, and 0.308 M NMP in concentrated NH4OH. The results are summarized in Table 29 below.

[0225] 10.5 wt% Ni / 0.45 wt% Ru supported carbon catalyst The reaction was carried out as described above for the Ru-only catalyst. A total of 3 g of Ni / Ru catalyst was placed in the reactor and reactivated at 180°C under H2 prior to the introduction of the feed solution. No loss in catalytic activity was observed after 650 hours. The results are summarized in Table 29 below. [Table 29]

[0226] Example 25. Preparation of carbon black extrudates Carbon black extrudates were prepared according to the following procedure: To prepare a binder solution, 552.67 grams of dextrose monohydrate (ADM Corn Processing, 91.22 wt% glucose content) was dissolved in 455.63 grams of DI water at 70° C. The solution was then cooled to 50° C. 20.51 grams of hydroxyethyl cellulose was added to the mixture and stirred overnight.

[0227] Then, 450 grams of the binder solution was mixed with 200.6 grams of carbon black powder using a Winkworth Mixer (Model 1Z) (mixing for approximately 1 hour) and extruded using a Diamond America 1-inch single screw extruder (Model TT100CS). This same mixing / extrusion procedure was repeated again the same day with another 450 gram portion of carbon. The strands were dried in a forced air oven at 120°C for approximately 2 hours and then hand-crushed. The extrudates were then allowed to dry overnight.

[0228] The carbon was divided into four approximately 250 gram portions and pyrolyzed in a rotary kiln. Each portion was processed separately in the rotary kiln. The temperature of the kiln was increased at a rate of 30°C / min until a maximum of 800°C was reached. This temperature was maintained for two hours and then cooled. The kiln was set to rotate at 6.6 rpm. During the temperature increase, a large amount of water vapor and other pyrolysis products were formed. Between approximately 350°C and 450°C, a large amount of gas was formed.

[0229] After pyrolysis and cooling, the extrudates were washed. The desired amount of DI water was heated to 60°C in a beaker. The extrudates were then added, and the slurry was stirred at 300-350 rpm for 4 hours while maintaining the water temperature at 60°C. The beaker was covered with a watch glass to prevent excessive evaporation. The initial water:carbon ratio was maintained at 10:1 (vol / wt). The extrudates were separated, rinsed with DI water, and dried overnight in an oven at 80°C.

[0230] A 0.31 gram sample of the extrudate (bulk volume 0.33 cm) 3 ) were analyzed for various physical properties by mercury porosimetry. Table 30 shows the complete analytical results. A plot of pore size versus pore volume is shown in Figure 13. [Table 30-1] [Table 30-2] [Table 30-3] [Table 30-4] [Table 30-5]

[0231] Extrudate samples were also analyzed for various physical properties by nitrogen adsorption (BJH method). The molded carbon black extrudates were added to a tared Tristar II sample holder and placed under vacuum at 120 °C overnight to remove all volatiles. The mass of the carbon support after this pretreatment was 154.7 mg. Nitrogen isotherm data were collected at 77.3 K. Data were collected using a Micromeritics TriStar II 3020 instrument and analyzed using vendor-supplied software (version 3.02). For BJH analysis of all desorption data between 1.7 and 300 nm pore sizes, a Faas correction was applied, using the Halsey thickness equation of t = 3.54 × [(-5.000 / ln(p / p0))^0.333] with default parameters. The BET specific surface area was determined to be 178.5 m. 2 / g. Table 31 shows the nitrogen isotherm data collected during the analysis. Table 32 shows the t-plot data. Table 33 shows the BJH desorption pore distribution. [Table 31-1] [Table 31-2] [Table 32] [Table 33]

[0232] Example 26. Preparation of nickel-rhenium catalyst Approximately 8.87 grams of nickel nitrate hexahydrate, 1.79 g of perrhenic acid, and nitric acid were added to water to bring the volume to 5.81 mL. The carbon extrudates prepared in Example 25 were poured into a small tumbler, and the solution containing the nickel and rhenium precursors was slowly sprayed onto the carbon using a Sonaer nozzle and syringe pump. The beaker and spray equipment were rinsed to capture any remaining metal solution, bringing the total volume to 9.96 mL. The catalyst was rolled under airflow for approximately 30 minutes and then vacuum dried in an oven overnight at 80°C and 75 Torr.

[0233] A second catalyst was prepared using the same method, except that no nitric acid was added during metal deposition.

[0234] Example 27. Hydrogenolysis of glycerol The first nickel-rhenium catalyst prepared in Example 26 (with nitric acid added during metal deposition) was evaluated for glycerol hydrogenolysis. The catalyst was loaded into a 30 cc reactor. The reactor was then purged with hydrogen at a flow rate of 100 ml / min. After purging, the reactor was pressurized to 1800 psi with hydrogen. Hydrogen and glycerol were then fed to the reactor as a 40 wt. % solution along with sodium hydroxide cocatalyst. The evaluation details are shown in Table 34. The catalyst was evaluated at various reaction temperatures, hydrogen flow rates, and cocatalyst concentrations. Periodic liquid samples were analyzed by HPLC and GC. The pH of all samples was between 7.5 and 9.9. This catalyst improved the yield and selectivity of propylene glycol and the conversion of glycerol. [Table 34]

[0235] Selected samples from the above evaluation were analyzed for various products (EG = ethylene glycol, PG = propylene glycol) and by-products (BDO = butanediol). The results of these analyses are shown in Table 35. These samples were also analyzed for catalyst metals, the presence of which would indicate leaching from the catalyst. The results show that no nickel or rhenium was detected at levels above the detection limit (0.5 mg / kg). Therefore, no leaching of catalyst metals was observed in this evaluation. [Table 35]

[0236] A second nickel-rhenium catalyst prepared in Example 26 was also evaluated for the hydrogenolysis of glycerol. Details of this evaluation are shown in Table 36. Periodic liquid samples were analyzed by HPLC and GC. Conversion increased significantly with increasing hydrogen flow rate. [Table 36]

[0237] Example 28. Analysis of Ni-Re on Carbon Black Extrudates The Ni-Re catalyst prepared in Example 26 was analyzed using energy dispersive X-ray spectroscopy (EDX) in conjunction with scanning electron microscopy (SEM).

[0238] Figure 14 shows an SEM image of the Ni-Re on carbon black extrudate catalyst. For this catalyst, no nitric acid was added during nickel deposition. Figure 15 shows the EDX analysis of this catalyst. The EDX results show that the nickel reaches the inner region of the extrudate support (see Sample 2).

[0239] Figure 16 shows an SEM image of a second Ni-Re on carbon black extrudate catalyst. For this catalyst, nitric acid was added during nickel deposition. Figure 17 shows the EDX analysis of this catalyst. The EDX results indicate that nickel did not deposit in the inner region of the extrudate support (see Samples 2 and 3). Instead, nickel was concentrated in the outer region of the catalyst as a shell.

[0240] When introducing elements of the invention or preferred embodiment(s) thereof, the articles "a," "an," "the," and "said" are intended to mean the presence of one or more elements. The terms "comprising," "including," and "having" are intended to be inclusive and mean that there may be additional elements other than the listed elements.

[0241] In view of the above, it will be seen that the several objects of the invention are achieved and other advantageous results attained.

[0242] It is intended that all matter contained in the above description and accompanying drawing(s) be interpreted as illustrative and not in a limiting sense, as various changes can be made in the compositions, methods, and processes described above without departing from the scope of the present invention.

[0243] Having described the invention in detail, it will be apparent that modifications and variations are possible without departing from the scope of the invention as defined in the appended claims.

Claims

1. 1. A process for the hydrocracking of glycerol, comprising: supplying a feed composition comprising glycerol to a reaction zone; and reacting within said reaction zone said glycerol with hydrogen in the presence of a catalyst composition to form a reaction product comprising propylene glycol and / or ethylene glycol, said catalyst composition comprising a shaped porous carbon article as a catalyst support and a catalytically active component or precursor thereof, said shaped porous carbon article comprising: (a) carbon black and (b) a carbonized binder comprising a carbonized product of a water-soluble organic binder comprising a sugar and a cellulose-based compound; Including, at least 35% of the pore volume of the shaped porous carbon product is attributable to pores having an average pore diameter of 20 nm to 90 nm as measured by the BJH method, based on pores having a diameter of 1.7 nm to 100 nm, and not more than 10% of the pore volume of the shaped porous carbon product is attributable to pores having an average pore diameter of 100 nm or more as measured by mercury porosimetry; The process wherein the catalytically active component or precursor thereof comprises a metal selected from the group consisting of chromium, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, gold, and any combination thereof.

2. 10. The process of claim 1, wherein no more than 5% of the pore volume of the shaped porous carbon product is attributable to pores having an average pore diameter of 100 nm or greater, as measured by mercury porosimetry.

3. 10. The process of claim 1, wherein 0.1% to 10% of the pore volume of the shaped porous carbon product is attributable to pores having an average pore diameter of 100 nm or greater, as measured by mercury porosimetry.

4. 4. The process of any one of claims 1 to 3, wherein the partial pressure of hydrogen in the reaction zone is at least 2.1 MPa (300 psi).

5. The process of any one of claims 1 to 4, wherein the catalytically active component comprises rhenium, nickel or copper.

6. The process of any one of claims 1 to 5, wherein the catalytically active component comprises a combination of metals selected from the group consisting of nickel and rhenium, copper and rhenium, and cobalt and rhenium.

7. The process according to any one of claims 1 to 6, wherein the loading of the catalytically active component in the catalyst composition is 0.1 wt% to 10 wt%.

8. The BET specific surface area of ​​the molded porous carbon product is 20 m ２ / g~500m ２ The process of any one of claims 1 to 7, wherein the hydroxyl group is 0.15 to 0.25g.

9. 9. The process of any one of claims 1 to 8, wherein at least 40% of the pore volume of the shaped porous carbon product is attributable to pores with an average pore size of 20 to 90 nm, as measured by the BJH method, based on pores having a diameter of 1.7 nm to 100 nm.

10. 10. The process of any one of claims 1 to 9, wherein at least 50% of the pore volume of the shaped porous carbon product is attributable to pores having an average pore size of 10 nm to 100 nm, as measured by the BJH method, based on pores having a diameter of 1.7 nm to 100 nm.

11. The process of any one of claims 1 to 10, wherein the shaped porous carbon product has a pore size distribution such that the peak of the pore size distribution is less than 100 nm in diameter.

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