US20060229476A1 - Activated carbon monolith catalyst, methods for making same, and uses thereof - Google Patents

Activated carbon monolith catalyst, methods for making same, and uses thereof Download PDF

Info

Publication number
US20060229476A1
US20060229476A1 US11/102,452 US10245205A US2006229476A1 US 20060229476 A1 US20060229476 A1 US 20060229476A1 US 10245205 A US10245205 A US 10245205A US 2006229476 A1 US2006229476 A1 US 2006229476A1
Authority
US
United States
Prior art keywords
activated carbon
monolith
catalyst
supporting
carbon monolith
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US11/102,452
Other languages
English (en)
Inventor
Robert Mitchell
Lee Mitchell
Joseph Keller
Jack L' Amoreaux
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
APPLIED TECHNOLOGY LP
Original Assignee
REALIST TECHNOLOGY LP
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by REALIST TECHNOLOGY LP filed Critical REALIST TECHNOLOGY LP
Priority to US11/102,452 priority Critical patent/US20060229476A1/en
Assigned to REALIST TECHNOLOGY LIMITED PARTNERSHIP reassignment REALIST TECHNOLOGY LIMITED PARTNERSHIP ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MITCHELL, ROBERT L. SR., KELLER, JOSEPH H., L'AMOREAUX, JACK H., MITCHELL, LEE M.
Priority to EP19181513.3A priority patent/EP3564209A1/de
Priority to PCT/US2006/012135 priority patent/WO2006110353A1/en
Priority to ES06749097T priority patent/ES2747901T3/es
Priority to PT67490979T priority patent/PT1877180T/pt
Priority to BRPI0609737A priority patent/BRPI0609737B1/pt
Priority to EP06749097.9A priority patent/EP1877180B1/de
Priority to CNA2006800174365A priority patent/CN101180122A/zh
Publication of US20060229476A1 publication Critical patent/US20060229476A1/en
Assigned to APPLIED TECHNOLOGY LIMITED PARTNERSHIP reassignment APPLIED TECHNOLOGY LIMITED PARTNERSHIP CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: REALIST TECHNOLOGY LIMITED PARTNERSHIP
Priority to US12/507,940 priority patent/US9637389B2/en
Priority to US15/498,643 priority patent/US10265681B2/en
Priority to US16/296,318 priority patent/US10478804B2/en
Priority to US16/663,438 priority patent/US10596549B2/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/354—After-treatment
    • C01B32/382—Making shaped products, e.g. fibres, spheres, membranes or foam
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B43/00—Formation or introduction of functional groups containing nitrogen
    • C07B43/04—Formation or introduction of functional groups containing nitrogen of amino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst

Definitions

  • the present invention relates generally to catalytic structures, methods for making same, and uses thereof.
  • this invention relates to activated carbon monolith catalysts and methods for making and using them.
  • Carbon catalysts play an important role in various chemical processes from industrial to pharmaceutical settings. Carbon catalysts enable chemical reactions to occur much faster, or at lower temperatures, because of changes that they induce in the reactants. Carbon catalysts may lower the energy of the transition state of chemical reactions, thus lowering the activation energy. Therefore, molecules that would not have had the energy to react, or that have such low energies that it is likely that they would take a long time to do so, are able to react in the presence of a carbon catalyst by reducing the energy required for the reaction to occur. Not only do carbon catalysts increase the rate of reaction, but they may also drive a reaction towards the desired product.
  • catalysts are applied to a substrate before introduction to a chemical process.
  • the substrate holds the catalyst while presenting the catalyst to reactants in the chemical process.
  • catalyst substrates, or supports include carbon or ceramic granules arranged in a bed, and ceramic monoliths.
  • carbons utilized as catalyst supports are either granules or powders.
  • carbons used for catalyst supports would be chosen only for their activity and selectivity.
  • the more common features that are important factors in determining activity and selectivity are surface area, pore volume, pore size, ash content, friability, availability, and/or other elements contained in the carbon matrix. The foregoing are not the only desirable features; rather, they are ones that are known to be obtainable within the art.
  • carbon catalyst supports are chosen more for properties that meet parameters of the chemical process, than for features that would make purely the best catalyst, for highest activity and selectivity. While a particular carbon substrate might have the best features for activity and selectivity, it may not be the best choice considering the chemical process parameters.
  • carbon granules suffer from attrition making exact pressure drop determinations difficult, and they scale up poorly in chemical processes.
  • the catalyst When chemical reactants trickle through a bed of granular carbon catalyst, the catalyst must be as attrition resistant as possible, less the bed collapse and flow cease or the catalyst metals be lost. Attrition is a particularly aggravating issue, because it alters the physical parameters of the chemical process as it proceeds, and causes financial loss, particularly when the catalyst is a precious metal.
  • carbons of choice are typically nutshell carbons, which are durable, but which have very small pores that can harshly limit activity and selectivity.
  • the carbon catalyst When a powder carbon catalyst is stirred violently in a batch reactor with chemical reactants, the carbon catalyst must be non-friable to some degree to allow it to be economically separated from the reaction at termination in order to prevent loss of the catalyst. Thus, perhaps one must exclude carbons with better catalytic properties, but which are too friable.
  • Ceramic catalytic monoliths have been used in the art for advantages they provide over fixed bed supports, such as predictable pressure drop through the catalyst bed, scalability based on a model that predicts performance through incremental increases in volume of catalyst with respect to the same reactant volume flow, separation of the catalysts from the reaction and from the product stream, practical continuous operation and ease of replacement of the catalyst, and layering of the catalyst or the catalysts either on the monoliths' wall depth or wall length, or both.
  • the low pressure drop of catalytic monoliths' allows them to operate at higher gas and liquid velocities. These higher velocities of gas and liquids promote high mass transfer and mixing.
  • Catalytic monolith development has been an ongoing process in an effort to enhance catalytic activity, catalytic selectivity, and catalyst life.
  • monoliths have advantages over fixed bed supports, there are still problems associated with traditional ceramic monoliths. Exposure of the catalytic metal in the catalytic monolith to the reactants is necessary to achieve good reaction rates, but efforts to enhance exposure of the catalytic metal often have been at odds with efforts to enhance adhesion of the metal to the monolith substrate. Thus, catalytic ceramic monoliths have fallen short of providing optimal catalytic selectivity and activity.
  • ceramic carbon catalyst monoliths developed to date may provide good selectivity and activity, but on the other hand may not be suitable for process parameters such as durability and inertness. Conversely, ceramic carbon catalyst monoliths suitable for such process parameters may have diminished selectivity and activity. Thus, it would be ideal to take a carbon with the best features for a catalyst based on its activity and selectivity, and then form a carbon monolith catalyst to fit the process parameters of choice.
  • the binding of carbons gives some degree of choice of carbon precursor, but the result is a carbon support with the binder as a new element.
  • These binders can vary from organic glues to pitches. In most cases, the binders are susceptible to attack by the reaction media in application. Some cause side reactions, or poison the catalyst. Furthermore, the result is a random binding of granules, or the creation of a new granule—a chopped extrudate of powdered carbon and binder. In either case, the parameters of flow are not predictable by simple, understandable models.
  • the carbons selected have generally been in use as unbound catalyst supports, and unbound activity and selectivity information on the carbon can sometimes be used, still the binder is not inert, and therefore binder influence is always an issue.
  • Carbonization of an organic material forms a support with little hope of prior carbon activity or selectivity information. Because the carbon is formed each time the support is prepared, and is limited to those precursor and organic materials that can be coated or formed and carbonized, commercially available carbons, known in the art to produce excellent catalyst, are excluded from consideration. Furthermore, the carbons normally used in preparation of catalyst supports are prepared from naturally occurring materials such as wood, peat, nutshell, and coal, and not from refined or organic chemicals. Carbon produced from naturally occurring material is known to retain some of the beneficial structural characteristics as well chemical nature of the precursor material. These characteristics are known to be important to the final activity and selectivity of the catalyst. While carbonization may be a way of producing a carbon coating or structure, it extends marginally the catalyst art, and does not produce a catalyst utilizing the known carbon methods of choice in the art.
  • a carbon monolith catalyst and a process for making the same, having attrition resistance, predictable pressure drop, high selectivity, high activity, and scalability for commercial economy and efficiency. More particularly, there is a need in the art to provide an activated carbon monolith catalyst which allows the manufacture of the catalyst of choice to fit the process parameters, while increasing the utility of the catalyst with predictable pressure drop through the catalyst bed, scalability based on a model that predicts performance through incremental increases in volume of catalyst with respect to the same reactant volume flow, separation of the catalysts from the reaction and from the product stream, practical continuous operation and ease of replacement of the catalyst, and layering of the catalyst or the catalysts either on the monolith's wall depth or wall length, or both, and while providing high selectivity and activity.
  • an activated carbon monolith catalyst comprising a finished self-supporting activated carbon monolith having at least one passage therethrough, and comprising a supporting matrix and substantially discontinuous activated carbon particles dispersed throughout the supporting matrix, and at least one catalyst precursor supported on the finished self-supporting activated carbon monolith.
  • the supporting matrix holds the activated carbon particles in a monolithic form.
  • the supporting matrix comprises a ceramic or another substantially inert material such as carbon.
  • the activated carbon monolith catalyst of this invention is not limited to use of precursor materials that must be carbonized to form a carbon catalyst support. It can include any activated carbon particles from any source. Thus, the activated carbon monolith catalyst of this invention can be made with activated carbon particles chosen for their superior activity and selectivity for a given application. The activated carbon monolith catalyst can then be expected to have a predictable activity and selectivity based on the knowledge available regarding the particular activated carbon particles used. In addition, the activated carbon particles in the activated carbon monolith catalyst of this invention are dispersed throughout the structure of the catalyst, giving depth to the catalyst activity and selectivity. The activated carbon particles are bound by a supporting matrix, which desirably is an inert binder and is not susceptible to attack by reaction media.
  • the activated carbon monolith catalyst of this invention exhibits the desirable features of a ceramic monolith, while also presenting the advantage of a choice of a wide variety of particulate carbon substrates. Such desirable features include ease of separation of the catalyst from a product in a chemical reaction, and predictable fluid flow, among others. Because the activated carbon particles are fixed in a monolithic form, regions of the monolith, in particular embodiments, can include different catalysts as desired. Such regions would not migrate in monolithic form as they would with loose activated carbon particles.
  • the catalyst can be chosen based on its superior activity and selectivity, while pressure drop through the monolith is predictable, processes using the activated carbon monolith catalyst are scalable based on a model that predicts performance through incremental increases in volume of catalyst with respect to the same volume flow, and the catalyst is separable from the reaction and product streams.
  • the activated carbon monolith catalyst is useful in continuous operations which were formerly practical only in batch processes; the activated carbon monolith catalyst is easy to replace, and the catalyst precursor can be layered either on the carbon monolith catalyst wall depth or wall length, or both.
  • the activated carbon monolith catalyst of this invention can be used in continuous processes because a process stream can flow through it. Due to the low pressure drop through the activated carbon monolith catalyst of this invention, continuous processes can operate at high velocities.
  • a method for making an activated carbon monolith catalyst comprising providing a finished self-supporting activated carbon monolith having at least one passage therethrough and comprising a supporting matrix and substantially discontinuous activated carbon particles dispersed throughout the supporting matrix and applying at least one catalyst precursor to said finished extruded activated carbon monolith.
  • a method for catalytic chemical reaction comprising contacting at least one reactant with an activated carbon monolith catalyst comprising (a) a finished self-supporting extruded activated carbon monolith having at least one passage therethrough and comprising a supporting matrix and substantially discontinuous activated carbon particles dispersed throughout the supporting matrix, and (b) at least one catalyst precursor on said finished extruded activated carbon monolith.
  • FIG. 1 is a perspective view of an activated carbon monolith catalyst made in accordance with an embodiment of the invention.
  • FIG. 2 is a partial side elevation of an activated carbon monolith catalyst of FIG. 1 with a portion of the skin removed to illustrate the flow of fluid through the honeycomb passages of the monolith.
  • this invention encompasses an activated carbon monolith catalyst comprising a finished self-supporting activated carbon monolith having at least one passage therethrough, and comprising a supporting matrix and substantially discontinuous activated carbon particles dispersed throughout the supporting matrix, and at least one catalyst precursor on the finished self-supporting activated carbon monolith.
  • a method for making an activated carbon monolith catalyst, and application of the activated carbon monolith catalyst in chemical processes, are also disclosed. Embodiments of this invention are described below, beginning with the structure and components of the activated carbon monolith catalyst, followed by methods of making and using the activated carbon monolith catalyst.
  • the term “activated carbon monolith catalyst” refers to a combination of an activated carbon monolith substrate and at least one catalyst precursor.
  • catalyst means a material that is present in a reaction, adjusts the activation energy of the reaction and provides some reaction selectivity, but is not consumed in the reaction.
  • catalyst precursor means a material that is capable of creating a catalytically active site on a substrate material. A catalyst precursor may or may not undergo a change in becoming catalytically active.
  • Suitable catalyst precursors are selected from precious metal, base metal, or a combination thereof.
  • precious metals include, but are not limited to, palladium, platinum, rhodium, ruthenium, iridium, osmium, silver, and gold.
  • the precious metal may also be reduced precious metal, precious metal oxide, precious metal sulfide, precious metal with modifiers, or a combination thereof.
  • modifiers include, but are not limited to, potassium, calcium, magnesium, sodium hydrated oxides, and sodium hydroxides.
  • Non-limiting examples of base metal include, but are not limited to, zinc, nickel, copper, manganese, iron, chromium, vanadium, molybdenum, and combinations thereof.
  • Base metal may also be present as oxides, hydrated oxides, carbonates, sulfides, or a combination thereof.
  • An illustrative example of the combination of catalyst precursors may be a solution of palladium chloride and sodium carbonate, to be combined with an activated carbon monolith to form an activated carbon monolith catalyst.
  • FIG. 1 illustrates an activated carbon monolith catalyst 10 made according to an embodiment of the present invention.
  • the activated carbon monolith catalyst 10 comprises a finished self-supporting activated carbon monolith and at least one catalyst precursor applied to the monolith.
  • finished self-supporting activated carbon monolith refers to a solid-phase material comprising activated carbon without any catalyst precursor yet added to the monolith.
  • the activated carbon monolith catalyst 10 shown in FIG. 1 comprises an activated carbon monolith having a honeycomb shape and comprising activated carbon particles, ceramic forming material, flux material, and water, to which at least one catalyst precursor has been applied.
  • the activated carbon monolith catalyst has a plurality of passages 12 extending through the monolith from a frontal end 14 to a rearward end 16 .
  • the passages 12 are substantially square in cross section, linear along their length, and formed by surrounding walls 18 , however, the passages can have other cross-sectional shapes such as rectangular, round, triangular, hexagonal, oval, elliptical, and the like.
  • the passages 12 are encased by an outer skin 20 of the monolith.
  • the activated carbon particles in the activated carbon monolith catalyst 10 are dispersed throughout the supporting matrix, giving depth to the catalyst activity and selectivity.
  • the activated carbon particles are bound by the supporting matrix, which desirably is an inert binder and is not susceptible to attack by reaction media.
  • the supporting catalyst is a ceramic, but other materials can be used as the supporting matrix.
  • a mixture of activated carbon particles and a polymer resin, such as a thermoplastic polymer can be formed into a monolith and pyrolyzed to convert the resin into a carbon matrix.
  • the activated carbon monolith catalyst 10 comprises a total catalyst precursor on the finished activated carbon monolith in an amount from about 0.01 percent to about 5.0 percent by weight of the activated carbon monolith catalyst.
  • the preferred range depends on the application of the metal of choice.
  • the total catalyst precursor on the finished extruded activated carbon monolith may be in an amount from about 0.01 percent to about 1.0 percent by weight of activated carbon monolith catalyst.
  • the total catalyst precursor on the finished extruded activated carbon monolith may be in an amount from about 1.0 percent to about 5.0 percent by weight of activated carbon monolith catalyst.
  • the activated carbon monolith catalyst is porous, with pores extending into the depths of the monolith walls. Because the activated carbon particles are substantially discontinuous and are dispersed throughout the ceramic matrix, it is possible, depending on the catalyst precursor and the conditions under which the catalyst precursor is applied to the monolith, for the catalyst precursor to be present on the exterior surface of the monolith walls, and into the depths of the monolith walls via passageways between the discontinuous activated carbon particles, via passageways between the ceramic matrix and the carbon particles, and via pores in the carbon particles themselves. Placement of the catalyst precursor within the monolith structure can be controlled by selection of catalyst precursor, and variation in parameters of catalyst precursor application such as temperature, ionic strength of catalyst precursor solution, duration of catalyst precursor application, pH of the catalyst precursor solution, and the like.
  • the catalyst precursor therefor is desirably disposed on the surface of the finished self-supporting activated carbon monolith, such surface including area on the exterior walls of the monolith as well as area within passageways and pores in the depth of the monolith walls.
  • FIG. 2 illustrates the flow of fluid through the passages 12 in the activated carbon monolith catalyst 10 .
  • a catalyst precursor applied on and within the walls of the monolith structure becomes catalytically active, and catalyzes a chemical reaction as reactants flow through the monolith.
  • the activated carbon monolith catalyst 10 is made by providing a finished self-supporting activated carbon monolith and applying at least one catalyst precursor to the finished activated carbon monolith.
  • the finished activated carbon monolith is formed by mixing together activated carbon, ceramic forming material, flux material, and water to make an extrudable mixture, wherein binder is optionally added.
  • the extrudable mixture is extruded through an extrusion die to form the monolith having a honeycomb structure.
  • the finished extruded activated carbon monolith may be a honeycombed structure, or any other structure which is capable of being made by the extrusion process.
  • the extruded honeycomb monolith After extrusion, the extruded honeycomb monolith retains its shape while it is dried and then fired at a temperature and for a time period sufficient to react or fuse the ceramic forming material together and form a ceramic matrix, having activated carbon particles dispersed throughout the ceramic matrix or structure, and exhibiting sufficient strength for its intended end use. At least one catalyst precursor is thereafter applied to the finished extruded activated carbon monolith.
  • such monoliths can be formed by pressing a suitable activated carbon and binder mixture with a die or press, or by drawing a suitable mixture through a die with a suitable drawing force.
  • a mixture of activated carbon particles and a polymer resin, such as a thermoplastic polymer can be pressed or drawn to form a monolith and pyrolyzed to convert the resin into a carbon matrix.
  • catalyst precursor solution is contacted with a solution comprising at least one catalyst precursor, such as for example, a palladium chloride solution.
  • the solution comprising at least one catalyst precursor hereinafter is referred to as “catalyst precursor solution”
  • Catalyst precursor solution is contacted with the finished activated carbon monolith at a controlled or timed rate.
  • Controlled or “timed rate” refers to the addition of the catalyst precursor solution, or other components of the coating process, at a defined rate which achieves the desired contact of the catalyst precursor to the finished activated carbon monolith.
  • Defined rate refers to any rate which is capable of being reproduced or recorded.
  • the “controlled” or “timed rate” may be defined as a rate of catalyst precursor solution or other coating component addition at about 0.5cc/second/gram of finished activated carbon monolith to about 50cc/second/gram of finished activated carbon monolith.
  • the timed rate may be 0.5cc/minute/gram of finished activated carbon monolith to about 100 cc/minute/gram of finished activated carbon monolith.
  • the catalyst precursor solution may be added to the finished activated carbon monolith at a timed rate of 15.0 cc every 6.0 seconds for a 6.0 gram finished activated carbon monolith.
  • the catalyst precursor solution is added for a period of time which will achieve an activated carbon monolith catalyst comprising a total weight of the catalyst precursor in the amount of about 0.01% to about 5.0% by weight to the total weight of the activated carbon monolith catalyst.
  • the time period will depend on the concentration of the catalyst precursor solution, and the controlled rate of addition of the catalyst precursor solution.
  • the addition of the catalyst precursor solution may last from about 10.0 minutes to about 1.0 hour.
  • the catalyst precursor application process also comprises other components such as water, buffering agent, optional reducing agent, and optional hydrogen peroxide, optional base, and optional acid.
  • the water preferably is deionized.
  • buffering agent refers to any compound which resists changes in pH upon the addition of small amounts of either acid or base.
  • a buffering agent comprises a weak acid or base and its salt.
  • Non-limiting examples of a buffering agent include, but are not limited to, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and sodium bicarbonate.
  • reducing agent refers any substance that can donate electrons to another substance or decrease the oxidation numbers in another substance.
  • Non-limiting examples of reducing agent include, but are not limited to, sodium formate, potassium formate, hydrogen, sodium borohydride, sodium hypophosphite, hydrazine, and hydrazine hydrochloride. It is appreciate to those of ordinary skill in the art that not all metals such as base metals require a reducing agent.
  • the chlorides of some metals are soluble alone in water.
  • Others such as platinum or palladium, require hydrochloric acid, or being part of a potassium or sodium chloride compound for improved solubility.
  • palladium chloride may be dissolved in hydrochloric acid.
  • sodium chloropalladite is formed by adding sodium hydroxide to palladium chloride dissolved in hydrochloric acid.
  • Other chemical combinations to improve the solubility of the catalyst precursor are known in the art.
  • the temperature of the catalyst precursor solution may be from about 30.0° C. to about 75.0° C. In another example, the temperature may be from about 50.0° C. to about 65.0° C. Preferably the temperature is at 65.0° C.
  • the catalyst precursor solution is usually acidic.
  • the pH of the catalyst precursor solution may range from about 1.0 to about 6.9.
  • the pH of the catalyst precursor solution may range from about 4.0 to about 6.5.
  • the catalyst precursor application process may be carried out in an environment wherein the pH may range from about 1.0 to about 13.0 depending on the equipment and reagents utilized. It is appreciated that equipment such as stainless steel equipment (i.e. acid reactive equipment) requires a coating process environment wherein the pH is basic to avoid deterioration of the equipment. Alternatively, glass or glass-lined equipment may be suitable when using an acidic environment for the catalyst precursor application.
  • the method for making the activated carbon monolith catalyst 10 includes first mixing the dry ingredients of the extrudable mixture and then adding the liquid ingredients to the dry mixture; however, the order in which the ingredients are added to the extrudable mixture can be varied by alternating mixing of dry and liquid ingredients as long as the proper amount of moisture is added to make an extrudable mixture which holds its shape during and after extrusion.
  • a suitable finished activated carbon monolith is disclosed in U.S. Pat. No. 5,914,294, the disclosure of which is expressly incorporated herein by reference.
  • the activated carbon is desirably present in the extrudable mixture in an amount from about 20 to about 70 parts, by weight, and more desirably, in an amount from about 30 to about 50 parts, by weight.
  • a variety of activated carbons can be used in this invention.
  • the activated carbon surfaces adsorb volatile organic compounds and other chemical agents. The most suitable activated carbon will depend on the intended application, particularly the nature of the material to be adsorbed. Thus, the physical properties of the activated carbon, such as the surface area and the pore structure, may be varied depending on the intended application. Desirably, the activated carbon has a nitrogen B.E.T. surface from about 600 to about 2000 m 2 /g. More desirably, the activated carbon has a nitrogen B.E.T.
  • Suitable activated carbon can also be characterized by having a particle size such that more than 40% by weight of the activated carbon passes through a 200 mesh screen, and more desirably, by having a particle size such that more than 65% by weight of the activated carbon passes through a 200 mesh screen.
  • Activated carbon suitable for use in the present invention may be made from a variety of precursors including bituminous coal, lignite, peat, synthetic polymers, petroleum pitch, petroleum coke, coal tar pitch, and lignocellulosic materials.
  • Suitable lignocellulosic materials include wood, wood dust, wood flour, sawdust, coconut shell, fruit pits, nut shell, and fruit stones.
  • Suitable commercially available activated carbons include Nuchar® activated carbon available from Westvaco Corporation of New York, N.Y., Acticarbone® carbon available from Ceca SA of Paris, France, and Darco® carbon and Norit® carbon available from Norit-Americas of Marshall, Tex.
  • the ceramic forming material is present in the extrudable mixture in an amount from about 20 to about 60 parts, by weight, and more desirably, in an amount from about 30 to about 50 parts, by weight.
  • the term ceramic forming material means alumina/silicate-based material which, upon firing, is capable of reacting together with other ingredients to form a high strength, crystal/glass mixed-phase ceramic matrix.
  • the reacted ceramic material provides a matrix for supporting the activated carbon, and has sufficient strength to withstand handling and use of the monolith in the intended application and maintain its intended shape without cracking or otherwise disintegrating.
  • the ceramic forming material desirably includes a substantial portion of moldable material which is plastic in nature and thus, when mixed with liquid, can be molded or extruded into a shape and will maintain that shape through drying and firing.
  • a suitable plastic or moldable material is ball clay.
  • a particularly suitable commercially available ball clay is OLD MINE #4 ball clay available from Kentucky-Tennessee Clay Company of Mayfield, Ky.
  • Other suitable plastic-like ceramic forming materials include, but are not limited to, plastic kaolins, smectite clay minerals, bentonite, and combinations thereof. Bentonite and smectites are desirably used in combination with ball clay or kaolin.
  • the ceramic forming material also desirably includes a filler material which is non-plastic and reduces shrinkage of the monolith during the steps of drying and firing.
  • a suitable ceramic filler is calcined kaolin clay.
  • a particularly suitable commercially available calcined kaolin clay is Glomax LL available from Georgia Kaolin Company, Inc. of Union, N.J.
  • the filler desirably is present in the extrudable mixture in an amount up to about 15 parts, by weight, and more desirably, from about 1 to about 15 parts, by weight, and even more desirably, from about 3 to about 10 parts, by weight.
  • Other suitable filler materials include, but are not limited to, calcined kyanite, mullite, cordierite, clay grog, silica, alumina, and other calcined or non-plastic refractory ceramic materials and combinations thereof.
  • the flux material is present in the extrudable mixture in an amount from about 4 to about 20 parts, by weight, and aids in forming the ceramic bond between the ceramic forming materials by causing the ceramic forming material particles to react together and form a ceramic matrix at a lower firing temperature than if the flux material were not present. More desirably, the flux material is present in the extrudable mixture in an amount from about 4 to about 10 parts, by weight.
  • Suitable flux materials include, but are not limited to, feldspathic materials, particularly nepheline syenite and feldspar, spodumene, soda, potash, sodium silicate, glass frits, other ceramic fluxes, and combinations thereof.
  • a particularly desirable commercially available flux material is MINEX®7 nepheline syenite available from Unimin Specialty Materials, Inc. of Elco, Ill.
  • the binder is present in the extruded mixture in an amount from about 0.5 to about 9 percent, by weight, based on the solids content of the binder, and enhances the strength of the monolith after extrusion so that the extruded monolith maintains its shape and integrity after extrusion and through drying and firing.
  • the binder is desirably present in the extruded mixture in an amount from about 2 to about 7 percent, by weight, based on the solids content of the binder.
  • a particularly suitable binder is methylcellulose, and a suitable commercially available methylcellulose is METHOCEL A4M methylcellulose available from Dow Chemical Company of Midland, Mich.
  • methylcellulose is present in the extrudable mixture in an amount from about 0.5 to about 9 parts, by weight, of the extrudable mixture, and more desirably, from about 2 to about 7 parts, by weight.
  • Another suitable binder, used in combination with methylcellulose is an acrylic binder. Examples of such polymers are JONREZ D-2106 and JONREZ D-2104 available from Westvaco Corporation of New York, N.Y., and Duramax acrylic binder which is available from Rohm & Haas of Montgomeryville, Pa.
  • the acrylic polymer, having a medium to high glass transition temperature is desirably present in an amount from zero up to about 4 parts, by weight, of the extrudable mixture, based on the solids content of the acrylic binder.
  • Other suitable binders include hydroxypropyl methylcellulose polymers, CMC, polyvinyl alcohol, and other temporary binder/plasticizer additives.
  • sodium silicate which increases the strength of both the dry, but unfired monolith and the fired monolith, and is a flux material.
  • the sodium silicate is thus both a binder when the monolith is in the dry state and a flux material, and is added to the extrudable mixture as a solution.
  • the sodium silicate is desirably present in the extrudable mixture in an amount up to about 7 parts, by weight, based on the solids content of the sodium silicate, and more desirably in an amount from about 0.0 to about 7 parts, by weight, based on the solids content of the sodium silicate.
  • a suitable commercially available sodium silicate solution is a 40% solids, Type N solution, available from PQ Corporation, Industrial Chemicals Division, Valley Forge, Pa.
  • Other suitable binders for the dried monolith include silica sol and alumina sol.
  • the extrudable mixture includes water in an amount sufficient to make an extrudable mixture and desirably includes from about 60 to about 130 parts water, by weight of dry ingredients.
  • the water is chilled before it is added to the mixture and more preferably is added to the system at or near 0° C. This low temperature helps keep the ingredients cool during mixing, and helps to overcome any exotherm which may occur as a result of mixing the ingredients, or as a result of heating of the mixture, which occurs as a result of the mechanical action of mixing.
  • the extrudable mixture is formed into a shape, which will be the shape of the finished self-supporting activated carbon monolith, by passing the extrudable mixture through an extrusion die.
  • the finished self-supporting activated carbon monolith usually has a block or cylindrical shape, and includes at least one passageway along its length and desirably includes a plurality of passageways extending along the length of the finished self-supporting activated carbon monolith.
  • the activated carbon monolith catalyst is designed to be placed in a stream of a fluid containing one or more chemical reactants, such that the fluid is forced through the passages in the monolith. Ideally, the amount of internal surface area of the activated carbon monolith catalyst exposed to the fluid is designed to maximize the efficiency of the catalytic reaction.
  • a honeycomb-shaped structure is preferred for the finished self-supporting activated carbon monolith. Honeycomb extruders are known in the art of ceramics and have been used to produce ceramic monoliths.
  • the honeycomb structure of the finished self-supporting activated carbon monolith has an open frontal area greater than 50 percent and up to about 85 percent, and desirably about 74 percent, after drying and firing.
  • the open frontal area of the monolith is the percentage of open area of the monolith taken across a plane substantially perpendicular to the passageway length of the monolith.
  • the finished self-supporting activated carbon monolith desirably has a honeycomb pattern with square cells and about 540 cells per square inch.
  • the honeycomb structure desirably has a cell-to-cell pitch of about 0.043 inches, a cell wall thickness of about 6 mils, and an open frontal area of about 0.0014 square inches per cell.
  • the cell density may vary from 1 to 900 cells per square inch or higher, with the cell wall thickness ranging from about 150 mils to about 4 mils, and the cell-to-cell pitch varying from about 1 to about 0.033 inches.
  • the extruded activated carbon honeycomb monolith is dried in a manner so as to prevent cracking of the structure.
  • the extruded carbon honeycomb monolith is dried so that water is removed at substantially the same rate throughout the carbon honeycomb monolith.
  • Suitable drying methods include dielectric drying, microwave drying, warm air drying with the monolith wrapped in plastic or wet cloths, vacuum drying, freeze drying, and humidity control drying.
  • the dried extruded activated carbon honeycomb monolith is fired at a temperature from about 1600 to about 1950° F. and desirably from about 1850 to about 1950° F., in a nitrogen or other non-oxidizing or slightly reducing atmosphere.
  • the activated carbon honeycomb monolith should be fired at a temperature sufficient to react the ceramic forming materials together to create a matrix for holding the activated carbon and maintaining the honeycomb shape of the extrusion.
  • the bonds created by the firing should be sufficient to create a matrix having a strength able to withstand handling and use of the carbon monolith catalyst in intended applications.
  • the relatively high surface area of the material forming the finished self-supporting activated carbon monolith makes it desirable as a catalyst support.
  • the finished self-supporting activated carbon monolith is porous, and catalyst precursor can be applied on the exterior of the monolith and through the depth of the monolith via pores and passages in the monolith walls.
  • the finished self-supporting activated carbon monolith is made by extruding a mixture comprising: 30 parts, by weight, activated carbon; 50 parts, by weight, ball clay; 10 parts, by weight, calcined kaolin clay; 10 parts, by weight, nepheline syenite; 2.5 parts, by weight, methylcellulose; 2.8 parts, by weight, sodium silicate solids; and 75 parts, by weight, water.
  • the resulting finished self-supporting activated carbon monolith has a high structural integrity, exhibiting axial crushing strength of about 1500 psi and a modulus of rupture (MOR) of about 150 psi in the axial direction.
  • MOR modulus of rupture
  • the activated carbon monolith catalyst of this invention could be used in a variety of applications owing to the wide range of carbon content which the carbon monolith catalysts can contain.
  • crushing strengths of the finished self-supporting activated carbon monolith will vary depending on the relative amounts of carbon and ceramic forming material, the firing temperature, and the particle size of the ingredients.
  • the finished self-supporting activated carbon monolith may include activated carbon particles in an amount from about 20 to about 95% by weight of the finished self-supporting activated carbon monolith, preferably in an amount from about 20 to about 80% by weight of the finished self-supporting activated carbon monolith, and more preferably in an amount from about 30 to about 50% by weight of the finished self-supporting activated carbon monolith.
  • the higher loading of carbon greater then 80% by weight
  • the axial crushing strength of the finished self-supporting activated carbon monolith desirably ranges from 500 to 1600 psi.
  • a method for catalytic chemical reaction comprising contacting at least one reactant with an activated carbon monolith catalyst comprising (a) a finished self-supporting activated carbon monolith having at least one passage therethrough, and comprising a supporting matrix and substantially discontinuous activated carbon particles dispersed throughout the supporting matrix, and (b) at least one catalyst precursor on the finished activated carbon monolith.
  • reactant refers to any chemical compound in which a catalyst can affect a chemical reaction by increasing the reaction rate, and/or lowering the activation energy, and/or create a transition state of lower energy when the chemical compound is alone, in combination with another chemical compound, or in combination with at least two chemical compounds of the same species.
  • the carbon monolith catalyst of the present invention is suitable for various catalytic reactions.
  • Catalytic reaction or “reaction” as used herein refers to heterogeneous and homogeneous catalytic reaction.
  • Heterogeneous catalytic reaction involves the use of a catalyst in a different phase from the reactants. Typical examples involve a solid catalyst with the reactants as either liquids or gases, wherein one or more of the reactants is adsorbed onto the surface of the catalyst at active sites. Homogeneous catalytic reaction, on the other hand, involves the use of a catalyst in the same phase as the reactants.
  • nitrobenzene is passed through the activated carbon monolith catalyst comprising palladium, and under hydrogen pressure. The result is the production of aniline.
  • phenol is passed through the activated carbon monolith catalyst comprising palladium doped with sodium, and under hydrogen pressure.
  • the result is the production of cyclohexanone.
  • crude terephthalic acid containing such color bodies as 4-carboxybenzaldehyde is passed through the activated carbon monolith catalyst comprising palladium, and under hydrogen pressure.
  • the result is the production of purified terephthalic acid with very few color bodies present.
  • hydrogen and nitrogen are passed through the activated carbon monolith catalyst comprising ruthenium, and under pressure and heat. The result is the production of ammonia.
  • carbon monoxide or carbon dioxide is passed through the activated carbon monolith catalyst comprising ruthenium, and under hydrogen pressure and heat.
  • the result is a hydrocarbon, Fisher-Tropsch Synthesis.
  • hydrocarbon and water are passed through the activated carbon monolith catalyst comprising ruthenium.
  • This process is also known as steam cracking.
  • the result is hydrogen and carbon monoxide, wherein the hydrogen may be used in a fuel cell.
  • Nitrobenzene is passed through the activated carbon monolith catalyst comprising platinum, and under hydrogen pressure. The result is the production of aniline.
  • hydrogen and oxygen are passed through the activated carbon monolith catalyst comprising platinum, in a fuel cell.
  • the result is electricity.
  • amine and aldehyde or ketone are passed through the activated carbon monolith catalyst comprising sulfided platinum, and under hydrogen pressure.
  • the result is a reductive alkylation product.
  • nitrobenzene is passed through the activated carbon monolith catalyst comprising sulfided platinum, and under hydrogen pressure.
  • the result is a hydroxyl amine.
  • aniline is passed through the activated carbon monolith catalyst comprising rhodium, and under hydrogen pressure.
  • the result is the cyclohexylamine.
  • phenol is passed through the activated carbon monolith catalyst comprising rhodium and under hydrogen pressure.
  • the result is cyclohexanol.
  • gas phase catalytic reaction may also be achieved with the activated carbon monolith catalyst of the present invention.
  • Non-limiting examples include: Cyclic-condensation and Dehydrogenation, Heterocyclic Compounds Synthesis wherein R represent any chemical functional group which does not alter the chemical compounds.
  • a finished self-supporting activated carbon monolith made in accordance with U.S. Pat. No. 5,914,294 was placed in the reactor so as to have the sodium carbonate aqueous solution pass evenly through the cells of the monolith as the solution was agitated.
  • a solution of palladium chloride was prepared so as to have a palladium metal loading by weight of the carbon monolith of 0.1%.
  • the pH of this solution was adjusted to a pH of 4.0 using sodium bicarbonate. This solution was metered into the reactor.
  • the reactor was heated via an electronic temperature controlled device, so as to ramp to 65° C. in 30 minutes.
  • Example 2 In the same manner of Example 1, a finished self-supporting activated carbon monolith made in accordance with U.S. Pat. No. 5,914,294 was used to prepare a catalyst with a palladium metal loading of 5% by weight of the activated carbon monolith catalyst.
  • the activated carbon monolith catalyst of Example 2 was tested for its catalytic activity using nitrobenzene as a test reactant.
  • the activated carbon monolith catalyst was placed in the 500 ml glass bottle of a Rocking Parr Bomb. A quantity of 2 ml of pure nitrobenzene was added to the glass bottle along with 50 ml of methanol to act as a solvent. The bottle was inserted into the Rocking Parr Bomb at ambient temperature, which was 22° C. at the time of the test.
  • the bottle was pressurized to 60 psig with pure hydrogen. When agitation of the bottle commenced, time and hydrogen pressure in the bottle were recorded. Hydrogen pressure was seen to fall from 60 psig to 43.5 psig in 255 seconds. The temperature of the contents of the bottle were seen to rise from 22° C. to 31° C. in the same time period.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
US11/102,452 2005-04-08 2005-04-08 Activated carbon monolith catalyst, methods for making same, and uses thereof Abandoned US20060229476A1 (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
US11/102,452 US20060229476A1 (en) 2005-04-08 2005-04-08 Activated carbon monolith catalyst, methods for making same, and uses thereof
CNA2006800174365A CN101180122A (zh) 2005-04-08 2006-04-03 活性碳单块催化剂及其制备方法和用途
EP06749097.9A EP1877180B1 (de) 2005-04-08 2006-04-03 Verfahren zum hindurchleiten von nitrobenzol durch einen aktivkohle-monolith-katalysator, um anilin zu bilden
PCT/US2006/012135 WO2006110353A1 (en) 2005-04-08 2006-04-03 Activated carbon monolith catalyst, methods for making same, and uses thereof
ES06749097T ES2747901T3 (es) 2005-04-08 2006-04-03 Método para pasar nitrobenceno a través de un catalizador monolítico de carbón activado para formar anilina
PT67490979T PT1877180T (pt) 2005-04-08 2006-04-03 Método para passar nitrobenzeno através de um catalisador monólito de carvão ativado para formar anilina
BRPI0609737A BRPI0609737B1 (pt) 2005-04-08 2006-04-03 catalisador monolítico de carbono ativado, e, métodos para fabricar um catalisador monolítico de carbono ativado e para reação química catalítica
EP19181513.3A EP3564209A1 (de) 2005-04-08 2006-04-03 Hydrierung von nitrobenzol mit einem aktivkohlemonolithkatalysator
US12/507,940 US9637389B2 (en) 2005-04-08 2009-07-23 Activated carbon monolith catalyst, methods for making same, and uses thereof
US15/498,643 US10265681B2 (en) 2005-04-08 2017-04-27 Activated carbon monolith catalyst, methods for making same, and uses thereof
US16/296,318 US10478804B2 (en) 2005-04-08 2019-03-08 Activated carbon monolith catalyst, methods for making same, and uses thereof
US16/663,438 US10596549B2 (en) 2005-04-08 2019-10-25 Activated carbon monolith catalyst, methods for making same, and uses thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US11/102,452 US20060229476A1 (en) 2005-04-08 2005-04-08 Activated carbon monolith catalyst, methods for making same, and uses thereof

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US12/507,940 Division US9637389B2 (en) 2005-04-08 2009-07-23 Activated carbon monolith catalyst, methods for making same, and uses thereof

Publications (1)

Publication Number Publication Date
US20060229476A1 true US20060229476A1 (en) 2006-10-12

Family

ID=36764740

Family Applications (5)

Application Number Title Priority Date Filing Date
US11/102,452 Abandoned US20060229476A1 (en) 2005-04-08 2005-04-08 Activated carbon monolith catalyst, methods for making same, and uses thereof
US12/507,940 Active US9637389B2 (en) 2005-04-08 2009-07-23 Activated carbon monolith catalyst, methods for making same, and uses thereof
US15/498,643 Active 2025-05-26 US10265681B2 (en) 2005-04-08 2017-04-27 Activated carbon monolith catalyst, methods for making same, and uses thereof
US16/296,318 Active US10478804B2 (en) 2005-04-08 2019-03-08 Activated carbon monolith catalyst, methods for making same, and uses thereof
US16/663,438 Active US10596549B2 (en) 2005-04-08 2019-10-25 Activated carbon monolith catalyst, methods for making same, and uses thereof

Family Applications After (4)

Application Number Title Priority Date Filing Date
US12/507,940 Active US9637389B2 (en) 2005-04-08 2009-07-23 Activated carbon monolith catalyst, methods for making same, and uses thereof
US15/498,643 Active 2025-05-26 US10265681B2 (en) 2005-04-08 2017-04-27 Activated carbon monolith catalyst, methods for making same, and uses thereof
US16/296,318 Active US10478804B2 (en) 2005-04-08 2019-03-08 Activated carbon monolith catalyst, methods for making same, and uses thereof
US16/663,438 Active US10596549B2 (en) 2005-04-08 2019-10-25 Activated carbon monolith catalyst, methods for making same, and uses thereof

Country Status (7)

Country Link
US (5) US20060229476A1 (de)
EP (2) EP3564209A1 (de)
CN (1) CN101180122A (de)
BR (1) BRPI0609737B1 (de)
ES (1) ES2747901T3 (de)
PT (1) PT1877180T (de)
WO (1) WO2006110353A1 (de)

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070265161A1 (en) * 2006-05-11 2007-11-15 Gadkaree Kishor P Activated carbon honeycomb catalyst beds and methods for the manufacture of same
US20080132408A1 (en) * 2006-10-11 2008-06-05 Applied Technology Limited Partnership Carbon black monolith, carbon black monolith catalyst, methods for making same, and uses thereof
US20080207443A1 (en) * 2007-02-28 2008-08-28 Kishor Purushottam Gadkaree Sorbent comprising activated carbon, process for making same and use thereof
US20080289213A1 (en) * 2007-05-22 2008-11-27 Hee Ja Lee Garbage dryer
US20090252663A1 (en) * 2008-04-02 2009-10-08 Todd Marshall Wetherill Method and system for the removal of an elemental trace contaminant from a fluid stream
US20090297762A1 (en) * 2008-05-30 2009-12-03 Kishor Purushottam Gadkaree Flow-Through Sorbent Comprising A Metal Sulfide
US20090297885A1 (en) * 2008-05-30 2009-12-03 Kishor Purushottam Gadkaree Composite Comprising An Inorganic Substrate With A Coating Comprising Activated Carbon And Metal Sulfide
US20090308793A1 (en) * 2006-07-26 2009-12-17 NANOTECH INVESTMENT 2 (PTY) LTD Suite 8, Panorama Office Estate Activation, refining, and use of oil shale
US20100004119A1 (en) * 2008-07-03 2010-01-07 Kishor Purushottam Gadkaree Sorbent Comprising Activated Carbon Particles, Sulfur And Metal Catalyst
US20100127421A1 (en) * 2008-11-25 2010-05-27 Dabich Ii Leonard Charles Bi-directional flow for processing shaped bodies
US20100130352A1 (en) * 2008-11-25 2010-05-27 Dabich Ii Leonard Charles Methods For Processing Shaped Bodies
US20100127418A1 (en) * 2008-11-25 2010-05-27 Ronald Alan Davidson Methods For Continuous Firing Of Shaped Bodies And Roller Hearth Furnaces Therefor
US20100150814A1 (en) * 2008-12-15 2010-06-17 Kishor Purushottam Gadkaree Methods For Forming Activated Carbon Material For High Energy Density Ultracapacitors
US7998898B2 (en) 2007-10-26 2011-08-16 Corning Incorporated Sorbent comprising activated carbon, process for making same and use thereof
WO2013009600A3 (en) * 2011-07-08 2013-03-07 University Of Florida Research Foundation, Inc. Porous stabilized beds, methods of manufacture thereof and articles comprising the same
WO2012118656A3 (en) * 2011-02-28 2013-03-14 Corning Incorporated Method of coating a catalyst on a substrate
US8741243B2 (en) 2007-05-14 2014-06-03 Corning Incorporated Sorbent bodies comprising activated carbon, processes for making them, and their use
WO2014138397A1 (en) * 2013-03-08 2014-09-12 Basf Corporaton Base metal catalyst and method of using same
WO2014185957A1 (en) * 2013-05-14 2014-11-20 Ciris Energy, Inc. Treatment of carbonaceous feedstocks
US20160367963A1 (en) * 2014-01-29 2016-12-22 Ford Global Technologies, Llc Hydrocarbon trap with increased zeolite loading and improved adsorption capacity
US9669379B2 (en) 2011-12-22 2017-06-06 University Of Florida Research Foundation, Inc Solar thermochemical reactor, methods of manufacture and use thereof and thermogravimeter
FR3045415A1 (fr) * 2015-12-18 2017-06-23 Air Liquide Procede de fabrication d'un adsorbant structure monolithique autosupporte
US9776154B2 (en) 2012-12-21 2017-10-03 University Of Florida Research Foundation, Inc. Material comprising two different non-metallic parrticles having different particle sizes for use in solar reactor
WO2017174592A1 (en) * 2016-04-04 2017-10-12 Ajo Industrie S.À R.L. Catalyst mixture for the treatment of waste gas
US10239036B2 (en) 2011-12-22 2019-03-26 University Of Florida Research Foundation Solar thermochemical reactor, methods of manufacture and use thereof and thermogravimeter
US10471388B2 (en) 2016-04-04 2019-11-12 Cppe Carbon Process & Plant Engineering S.A. Sulfur dioxide removal from waste gas
US10478776B2 (en) 2016-04-04 2019-11-19 Cppe Carbon Process & Plant Engineering S.A. Process for the removal of heavy metals from fluids
CN110711605A (zh) * 2019-10-13 2020-01-21 西安凯立新材料股份有限公司 活性炭载体处理方法、钯炭催化剂的制备方法及应用
US10906017B2 (en) 2013-06-11 2021-02-02 University Of Florida Research Foundation, Inc. Solar thermochemical reactor and methods of manufacture and use thereof
CN113058627A (zh) * 2021-03-30 2021-07-02 中建三局绿色产业投资有限公司 Al/Si-C基多孔核壳分离球体及其负载型催化剂和应用
WO2022039739A1 (en) * 2020-08-19 2022-02-24 SM Intellectual Technologies LLC Trinuclear basic iron (iii) acetate solid absorbent compositions and methods for the removal or sweetening of mercaptan sulfur compounds from hydrocarbon streams

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060229476A1 (en) 2005-04-08 2006-10-12 Mitchell Robert L Sr Activated carbon monolith catalyst, methods for making same, and uses thereof
KR101362894B1 (ko) * 2009-12-09 2014-02-14 한국세라믹기술원 전사 방법을 이용한 고체산화물 연료전지용 셀 제조방법
WO2016149129A1 (en) 2015-03-13 2016-09-22 Donaldson Company, Inc. Activated carbon and catalyst filter
CN104994461B (zh) * 2015-07-03 2019-07-05 歌尔股份有限公司 吸音颗粒及其加工方法和扬声器模组及其封装方法
CN109574853A (zh) * 2017-09-29 2019-04-05 普济生物科技（台州）有限公司 用于合成苯胺类化合物的方法、催化剂及其应用
CA3092887C (en) * 2018-06-21 2023-08-01 Heraeus Deutschland GmbH & Co. KG Precious metal catalyst briquettes, process for the manufacture and for the incineration thereof
US11840670B2 (en) * 2020-12-22 2023-12-12 Applied Technology Limited Partnership Hydrogenation of oleochemical derivatives and systems
CN112547052A (zh) * 2020-12-25 2021-03-26 陕西科技大学 一种锰氧化物甲醛降解材料及其制备方法和催化剂

Citations (86)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US455509A (en) * 1891-07-07 Back for metallic knobs
US617079A (en) * 1899-01-03 Bone-black substitute and method of manufacture
US1524843A (en) * 1921-01-08 1925-02-03 Charles C Ruprecht Process of preparing fuller's earth
US1589081A (en) * 1919-12-05 1926-06-15 Adler Rudolf Adsorptive charcoal for medicinal purposes
US1985840A (en) * 1927-11-26 1934-12-25 Samuel S Sadtler Smoking tobacco
US2108860A (en) * 1934-11-12 1938-02-22 Paul Bechtner Method of and substance for treating tobacco smoke
US2391312A (en) * 1943-02-01 1945-12-18 Filtrol Corp Catalyst and method for forming catalysts
US2439358A (en) * 1945-07-03 1948-04-06 Bendix Aviat Corp Attitude gyro
US2439538A (en) * 1948-04-13 Deodorizing composition of matter
US2951087A (en) * 1958-03-28 1960-08-30 Nat Lead Co Clay complexes with conjugated unsaturated aliphatic compounds of four to five carbon atoms
US3089502A (en) * 1960-07-18 1963-05-14 James P Davidson Density control apparatus
USRE25400E (en) * 1963-06-18 Adsorbent briquets for combined odor
US3592779A (en) * 1968-11-06 1971-07-13 Standard Oil Co Ohio Acid sludge as binder for the production of shaped carbonaceous articles and activation thereof
US3632385A (en) * 1970-03-17 1972-01-04 Atomic Energy Commission Carbon composite structures and method for making same
US3690634A (en) * 1969-09-11 1972-09-12 Ryosuke Enya Device for making molten metal for casting
US3825460A (en) * 1971-05-18 1974-07-23 Nippon Toki Kk Thin-walled carbonaceous honeycomb structures and process for making same
US3859421A (en) * 1969-12-05 1975-01-07 Edward E Hucke Methods of producing carbonaceous bodies and the products thereof
US3864277A (en) * 1970-05-15 1975-02-04 North American Carbon Hard granular activated carbon and preparation from a carbonaceous material a binder and an inorganic activating agent
US3891574A (en) * 1971-11-15 1975-06-24 Agency Ind Science Techn Hollow spheres of activated carbon and method for manufacture thereof
US3927186A (en) * 1973-02-28 1975-12-16 Chemotronics International Inc Method for the preparation of carbon structures
US3960761A (en) * 1973-05-05 1976-06-01 Bayer Aktiengesellschaft Production of strong active carbon moldings
US3960771A (en) * 1973-04-20 1976-06-01 Japan Synthetic Rubber Co., Ltd. Composite adsorbent
US4029600A (en) * 1975-03-19 1977-06-14 American Cyanamid Company Carbon particulates with controlled density
US4051098A (en) * 1970-04-02 1977-09-27 Sumitomo Durez Company, Ltd. Method of preparing shaped active carbon
US4058483A (en) * 1975-06-13 1977-11-15 Imperial Chemical Industries Limited Adsorbent material
US4124529A (en) * 1976-06-02 1978-11-07 Bergwerksverband Gmbh Carbonaceous adsorbents and process for making same
US4220553A (en) * 1978-11-20 1980-09-02 Parker-Hannifin Corporation Method of making filter block of an adsorbent and phenolic-polyurethane binder
US4225569A (en) * 1977-06-14 1980-09-30 Kanebo Ltd. Carbon-carbon composite material and method for its production
US4259299A (en) * 1978-09-29 1981-03-31 Osaka Oxygen Ind Ltd. Process for removing ozone from an ozone-containing gas
US4338106A (en) * 1979-11-09 1982-07-06 Nippon Soken, Inc. Canister for fuel evaporative emission control system
US4399052A (en) * 1980-12-22 1983-08-16 Kabushiki Kaisha Kobe Seiko Sho Activated carbonaceous honeycomb body and production method thereof
US4518704A (en) * 1980-12-08 1985-05-21 Kyoto Ceramic Kabushiki Kaisha Activated carbon formed body and method of producing the same
US4677086A (en) * 1984-05-18 1987-06-30 Westvaco Corporation Shaped wood-based active carbon
US4808559A (en) * 1987-03-21 1989-02-28 Huls Aktiengesellschaft Method of manufacturing a catalyst for hydration of olefins to alcohols
US4923843A (en) * 1986-09-25 1990-05-08 Aluminum Company Of America Peptized activated carbon/alumina composite
US4954469A (en) * 1988-08-01 1990-09-04 Robinson Ken K Granulated activated carbon for water treatment
US4968651A (en) * 1989-07-12 1990-11-06 Norton Company Inert ceramic catalyst bed supports
US4992319A (en) * 1988-05-18 1991-02-12 Nichias Corporation Activated carbon supporting honeycomb structure and process for fabricating the same
US4999330A (en) * 1988-03-22 1991-03-12 Universite Du Quebec A Trois-Rivieres High-density adsorbent and method of producing same
US5037791A (en) * 1988-07-28 1991-08-06 Hri, Inc. Porous metal oxide supported carbon-coated catalysts and method for producing same
US5043310A (en) * 1989-01-19 1991-08-27 Takeda Chemical Industries, Ltd. Moldable compositions of activated carbon and molded articles produced therefrom
US5194414A (en) * 1991-01-21 1993-03-16 Toshimi Kuma Method of manufacturing a gas absorbing element or a catalyst carrier having a honeycomb structure
US5215690A (en) * 1990-12-24 1993-06-01 Corning Incorporated Method of making activated carbon and graphite structures
US5306675A (en) * 1992-10-28 1994-04-26 Corning Incorporated Method of producing crack-free activated carbon structures
US5356852A (en) * 1990-12-24 1994-10-18 Corning Incorporated Activated carbon structures
US5376609A (en) * 1993-08-23 1994-12-27 Corning Incorporated Activated carbon bodies having bentonite and cellulose fibers
US5389325A (en) * 1993-09-24 1995-02-14 Corning Incorporated Activated carbon bodies having phenolic resin binder
US5403548A (en) * 1992-02-28 1995-04-04 Takeda Chemical Industries Ltd. Activated carbon adsorbent and applications thereof
US5403809A (en) * 1992-12-21 1995-04-04 W. R. Grace & Co.-Conn. Composite inorganic supports containing carbon for bioremediation
US5451554A (en) * 1993-08-12 1995-09-19 Corning, Inc. Activated carbon bodies having epoxy resin and bentonite binders
US5451444A (en) * 1993-01-29 1995-09-19 Deliso; Evelyn M. Carbon-coated inorganic substrates
US5482915A (en) * 1993-09-20 1996-01-09 Air Products And Chemicals, Inc. Transition metal salt impregnated carbon
US5488023A (en) * 1994-08-12 1996-01-30 Corning Incorporated Method of making activated carbon having dispersed catalyst
US5488021A (en) * 1993-12-17 1996-01-30 Corning Incorporated Activated carbon bodies having clay binder and method of making same
US5510063A (en) * 1994-04-15 1996-04-23 Corning Incorporated Method of making activated carbon honeycombs having varying adsorption capacities
US5543096A (en) * 1994-09-12 1996-08-06 Corning Incorporated Method for producing activated carbon bodies having silicone resin binder
US5658372A (en) * 1995-07-10 1997-08-19 Corning Incorporated System and method for adsorbing contaminants and regenerating the adsorber
US5750026A (en) * 1995-06-02 1998-05-12 Corning Incorporated Device for removal of contaminants from fluid streams
US5820967A (en) * 1995-02-27 1998-10-13 Corning Incorporated Extruded structures from thermosetting resins
US5914294A (en) * 1996-04-23 1999-06-22 Applied Ceramics, Inc. Adsorptive monolith including activated carbon and method for making said monlith
US5998328A (en) * 1997-10-08 1999-12-07 Corning Incorporated Method of making activated carbon-supported catalysts
US5997829A (en) * 1995-05-26 1999-12-07 Hitachi Chemical Company, Ltd. Environment purifying material
US6097011A (en) * 1994-05-26 2000-08-01 Corning Incorporated Electrically heatable activated carbon bodies for adsorption and desorption applications
US6129846A (en) * 1997-11-14 2000-10-10 Corning Incorporated Activated carbon composite with crystalline tin silicate
US6156697A (en) * 1997-11-04 2000-12-05 Corning Incorporated Method of producing high surface area carbon structures
US6171373B1 (en) * 1996-04-23 2001-01-09 Applied Ceramics, Inc. Adsorptive monolith including activated carbon, method for making said monolith, and method for adsorbing chemical agents from fluid streams
US6228803B1 (en) * 1998-02-10 2001-05-08 Corning Incorporated Method of making mesoporous carbon
US6251822B1 (en) * 1998-07-20 2001-06-26 Corning Incorporated Method of making activated carbon derived from pitches
US6372289B1 (en) * 1999-12-17 2002-04-16 Corning Incorporated Process for manufacturing activated carbon honeycomb structures
US20020082168A1 (en) * 2000-12-11 2002-06-27 Graham James Richard Activated carbon for odor control and method for making same
US20020103081A1 (en) * 2001-02-01 2002-08-01 Helsa-Werke Helmut Sandler Gmbh & Co. Kg. Activated carbon molded body and use thereof
US6455023B1 (en) * 2000-10-11 2002-09-24 Corning Incorporated Metallic catalysts for non-neutral liquid media
US20020155252A1 (en) * 2001-01-31 2002-10-24 Masanori Tsuji Molded product of activated carbon and a method for production thereof
US6479704B1 (en) * 2001-04-20 2002-11-12 Air Products And Chemicals, Inc. Hydrogenation with monolith reactor under conditions of immiscible liquid phases
US20020178706A1 (en) * 2000-02-04 2002-12-05 The Procter & Gamble Company Air filtering device
US20030022787A1 (en) * 2001-04-11 2003-01-30 Westvaco Corporation Method of making shaped activated carbon
US20030050510A1 (en) * 2001-08-30 2003-03-13 Welp Keith Allen Monolith catalytic reactor coupled to static mixer
US20030049185A1 (en) * 2001-08-30 2003-03-13 Welp Keith Allen Monolith catalytic reactor coupled to static mixer
US20030143370A1 (en) * 2002-01-21 2003-07-31 Ngk Insulators, Ltd. Porous honeycomb structure body, the use thereof and method for manufacturing the same
US20030157003A1 (en) * 2002-02-15 2003-08-21 Machado Reinaldo Mario Catalyst holder and agitation system for converting stirred tank reactor to fixed bed reactor
US20040045438A1 (en) * 2001-03-13 2004-03-11 Place Roger Nicholas Method and equipment for removing volatile compounds from air
US20040069147A1 (en) * 2000-02-04 2004-04-15 The Procter & Gamble Company Air deodorization device having a detachable cartridge member
US6737445B2 (en) * 1999-09-15 2004-05-18 Tda Research, Inc. Mesoporous carbons and polymers
US20040116279A1 (en) * 2002-12-16 2004-06-17 Addiego William P. Supported metal catalysts
US20040118747A1 (en) * 2002-12-18 2004-06-24 Cutler Willard A. Structured adsorbents for desulfurizing fuels
US20040259727A1 (en) * 2001-12-20 2004-12-23 Andrea Bartolini Catalytic composition for the dehydrogenation of alkylaromatic hydrocarbons

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB191502409A (en) 1915-02-15 1915-07-15 Ewald Hanus Improvements relating to Ball Grinding Machines.
GB191503078A (en) 1915-02-25 1915-12-16 Smith Nehemiah Lord Improvements in or connected with Notice Boards or Indicators.
GB341233A (de) 1928-12-13 1931-01-15 I.G. Farbenindustrie Aktiengesellschaft
US2455509A (en) 1943-05-26 1948-12-07 Chemical Developments Corp Method of extruding irregularly shaped carbon rods
US3089195A (en) 1957-12-18 1963-05-14 Amsted Ind Inc Process for producing a shaped graphite article
US3454502A (en) 1966-04-27 1969-07-08 Calgon Corp Activated carbon tablet
JPS5795817A (en) 1980-12-08 1982-06-14 Kyocera Corp Manufacture of molded body of activated carbon
JPS5969146A (ja) 1982-10-15 1984-04-19 Nakajima Kagaku Sangyo Kk 粉末活性炭素を原料としたフイルタ−状吸着材の製造法
JPH01192765A (ja) 1988-01-29 1989-08-02 Ibiden Co Ltd 炭化ケイ素質ハニカム構造体の製造方法
JP2612878B2 (ja) 1988-01-29 1997-05-21 イビデン株式会社 炭化ケイ素質ハニカム構造体の製造方法
US5066628A (en) * 1988-12-20 1991-11-19 Amoco Corporation Catalyst and process for high selectivity reforming with PT/RE on BA-K-L zeolite
JPH03271152A (ja) 1990-03-20 1991-12-03 Ibiden Co Ltd セラミック焼結体の製造方法
US5283365A (en) * 1990-05-15 1994-02-01 Mitsui Toatsu Chemicals, Incorporated Process for preparing high-purity aniline
JP2922980B2 (ja) 1990-05-23 1999-07-26 イビデン株式会社 ハニカム構造のセラミックス焼結体の製造方法
US5104540A (en) * 1990-06-22 1992-04-14 Corning Incorporated Coated molten metal filters
EP0648535B1 (de) * 1993-10-15 1999-05-26 Corning Incorporated Verfahren zur Herstellung von Körpern mit imprägnierten Poren
JPH07132233A (ja) 1993-11-09 1995-05-23 Babcock Hitachi Kk ハニカム触媒の製造法
DE69817942T2 (de) * 1997-07-28 2004-07-29 Corning Inc. Katalysator zum Entfernen von Quecksilber und Verfahren zu dessen Herstellung und Verwendung
EP1683575A3 (de) * 2001-04-20 2006-08-02 Air Products and Chemicals, Inc. Verfahren zur Hydrierung von organischen Verbindungen über einem monolithischen Katalysator
WO2003024892A1 (en) 2001-09-21 2003-03-27 Stobbe Tech Holding A/S Porous ceramic structures and a preparing method
WO2004071955A1 (en) * 2003-02-17 2004-08-26 Jong-Seob Shim Manufacturing method of activated carbon structure having a frame
KR100953545B1 (ko) * 2004-03-23 2010-04-21 삼성에스디아이 주식회사 담지촉매 및 그 제조 방법
US20060229476A1 (en) * 2005-04-08 2006-10-12 Mitchell Robert L Sr Activated carbon monolith catalyst, methods for making same, and uses thereof

Patent Citations (94)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US455509A (en) * 1891-07-07 Back for metallic knobs
US617079A (en) * 1899-01-03 Bone-black substitute and method of manufacture
US2439538A (en) * 1948-04-13 Deodorizing composition of matter
USRE25400E (en) * 1963-06-18 Adsorbent briquets for combined odor
US1589081A (en) * 1919-12-05 1926-06-15 Adler Rudolf Adsorptive charcoal for medicinal purposes
US1524843A (en) * 1921-01-08 1925-02-03 Charles C Ruprecht Process of preparing fuller's earth
US1985840A (en) * 1927-11-26 1934-12-25 Samuel S Sadtler Smoking tobacco
US2108860A (en) * 1934-11-12 1938-02-22 Paul Bechtner Method of and substance for treating tobacco smoke
US2391312A (en) * 1943-02-01 1945-12-18 Filtrol Corp Catalyst and method for forming catalysts
US2439358A (en) * 1945-07-03 1948-04-06 Bendix Aviat Corp Attitude gyro
US2951087A (en) * 1958-03-28 1960-08-30 Nat Lead Co Clay complexes with conjugated unsaturated aliphatic compounds of four to five carbon atoms
US3089502A (en) * 1960-07-18 1963-05-14 James P Davidson Density control apparatus
US3592779A (en) * 1968-11-06 1971-07-13 Standard Oil Co Ohio Acid sludge as binder for the production of shaped carbonaceous articles and activation thereof
US3690634A (en) * 1969-09-11 1972-09-12 Ryosuke Enya Device for making molten metal for casting
US3859421A (en) * 1969-12-05 1975-01-07 Edward E Hucke Methods of producing carbonaceous bodies and the products thereof
US3632385A (en) * 1970-03-17 1972-01-04 Atomic Energy Commission Carbon composite structures and method for making same
US4051098A (en) * 1970-04-02 1977-09-27 Sumitomo Durez Company, Ltd. Method of preparing shaped active carbon
US3864277A (en) * 1970-05-15 1975-02-04 North American Carbon Hard granular activated carbon and preparation from a carbonaceous material a binder and an inorganic activating agent
US3825460A (en) * 1971-05-18 1974-07-23 Nippon Toki Kk Thin-walled carbonaceous honeycomb structures and process for making same
US3891574A (en) * 1971-11-15 1975-06-24 Agency Ind Science Techn Hollow spheres of activated carbon and method for manufacture thereof
US3927186A (en) * 1973-02-28 1975-12-16 Chemotronics International Inc Method for the preparation of carbon structures
US3960771A (en) * 1973-04-20 1976-06-01 Japan Synthetic Rubber Co., Ltd. Composite adsorbent
US3960761A (en) * 1973-05-05 1976-06-01 Bayer Aktiengesellschaft Production of strong active carbon moldings
US4029600A (en) * 1975-03-19 1977-06-14 American Cyanamid Company Carbon particulates with controlled density
US4058483A (en) * 1975-06-13 1977-11-15 Imperial Chemical Industries Limited Adsorbent material
US4124529A (en) * 1976-06-02 1978-11-07 Bergwerksverband Gmbh Carbonaceous adsorbents and process for making same
US4225569A (en) * 1977-06-14 1980-09-30 Kanebo Ltd. Carbon-carbon composite material and method for its production
US4259299A (en) * 1978-09-29 1981-03-31 Osaka Oxygen Ind Ltd. Process for removing ozone from an ozone-containing gas
US4220553A (en) * 1978-11-20 1980-09-02 Parker-Hannifin Corporation Method of making filter block of an adsorbent and phenolic-polyurethane binder
US4338106A (en) * 1979-11-09 1982-07-06 Nippon Soken, Inc. Canister for fuel evaporative emission control system
US4518704A (en) * 1980-12-08 1985-05-21 Kyoto Ceramic Kabushiki Kaisha Activated carbon formed body and method of producing the same
US4399052A (en) * 1980-12-22 1983-08-16 Kabushiki Kaisha Kobe Seiko Sho Activated carbonaceous honeycomb body and production method thereof
US4677086A (en) * 1984-05-18 1987-06-30 Westvaco Corporation Shaped wood-based active carbon
US4923843A (en) * 1986-09-25 1990-05-08 Aluminum Company Of America Peptized activated carbon/alumina composite
US4808559A (en) * 1987-03-21 1989-02-28 Huls Aktiengesellschaft Method of manufacturing a catalyst for hydration of olefins to alcohols
US4999330A (en) * 1988-03-22 1991-03-12 Universite Du Quebec A Trois-Rivieres High-density adsorbent and method of producing same
US4992319A (en) * 1988-05-18 1991-02-12 Nichias Corporation Activated carbon supporting honeycomb structure and process for fabricating the same
US5037791A (en) * 1988-07-28 1991-08-06 Hri, Inc. Porous metal oxide supported carbon-coated catalysts and method for producing same
US4954469A (en) * 1988-08-01 1990-09-04 Robinson Ken K Granulated activated carbon for water treatment
US5043310A (en) * 1989-01-19 1991-08-27 Takeda Chemical Industries, Ltd. Moldable compositions of activated carbon and molded articles produced therefrom
US4968651A (en) * 1989-07-12 1990-11-06 Norton Company Inert ceramic catalyst bed supports
US5215690A (en) * 1990-12-24 1993-06-01 Corning Incorporated Method of making activated carbon and graphite structures
US5356852A (en) * 1990-12-24 1994-10-18 Corning Incorporated Activated carbon structures
US5194414A (en) * 1991-01-21 1993-03-16 Toshimi Kuma Method of manufacturing a gas absorbing element or a catalyst carrier having a honeycomb structure
US5403548A (en) * 1992-02-28 1995-04-04 Takeda Chemical Industries Ltd. Activated carbon adsorbent and applications thereof
US5306675A (en) * 1992-10-28 1994-04-26 Corning Incorporated Method of producing crack-free activated carbon structures
US5403809A (en) * 1992-12-21 1995-04-04 W. R. Grace & Co.-Conn. Composite inorganic supports containing carbon for bioremediation
US5597617A (en) * 1993-01-29 1997-01-28 Corning Incorporated Carbon-coated inorganic substrates
US5451444A (en) * 1993-01-29 1995-09-19 Deliso; Evelyn M. Carbon-coated inorganic substrates
US5451554A (en) * 1993-08-12 1995-09-19 Corning, Inc. Activated carbon bodies having epoxy resin and bentonite binders
US5376609A (en) * 1993-08-23 1994-12-27 Corning Incorporated Activated carbon bodies having bentonite and cellulose fibers
US5482915A (en) * 1993-09-20 1996-01-09 Air Products And Chemicals, Inc. Transition metal salt impregnated carbon
US5389325A (en) * 1993-09-24 1995-02-14 Corning Incorporated Activated carbon bodies having phenolic resin binder
US5488021A (en) * 1993-12-17 1996-01-30 Corning Incorporated Activated carbon bodies having clay binder and method of making same
US5510063A (en) * 1994-04-15 1996-04-23 Corning Incorporated Method of making activated carbon honeycombs having varying adsorption capacities
US6097011A (en) * 1994-05-26 2000-08-01 Corning Incorporated Electrically heatable activated carbon bodies for adsorption and desorption applications
US5488023A (en) * 1994-08-12 1996-01-30 Corning Incorporated Method of making activated carbon having dispersed catalyst
US5543096A (en) * 1994-09-12 1996-08-06 Corning Incorporated Method for producing activated carbon bodies having silicone resin binder
US5820967A (en) * 1995-02-27 1998-10-13 Corning Incorporated Extruded structures from thermosetting resins
US5997829A (en) * 1995-05-26 1999-12-07 Hitachi Chemical Company, Ltd. Environment purifying material
US5750026A (en) * 1995-06-02 1998-05-12 Corning Incorporated Device for removal of contaminants from fluid streams
US5658372A (en) * 1995-07-10 1997-08-19 Corning Incorporated System and method for adsorbing contaminants and regenerating the adsorber
US6171373B1 (en) * 1996-04-23 2001-01-09 Applied Ceramics, Inc. Adsorptive monolith including activated carbon, method for making said monolith, and method for adsorbing chemical agents from fluid streams
US6284705B1 (en) * 1996-04-23 2001-09-04 Westvaco Corporation Adsorptive monolith including activated carbon, method for making said monolith, and method for adsorbing chemical agents from fluid streams
US5914294A (en) * 1996-04-23 1999-06-22 Applied Ceramics, Inc. Adsorptive monolith including activated carbon and method for making said monlith
US5998328A (en) * 1997-10-08 1999-12-07 Corning Incorporated Method of making activated carbon-supported catalysts
US6156697A (en) * 1997-11-04 2000-12-05 Corning Incorporated Method of producing high surface area carbon structures
US6129846A (en) * 1997-11-14 2000-10-10 Corning Incorporated Activated carbon composite with crystalline tin silicate
US6228803B1 (en) * 1998-02-10 2001-05-08 Corning Incorporated Method of making mesoporous carbon
US6248691B1 (en) * 1998-02-10 2001-06-19 Corning Incorporated Method of making mesoporous carbon
US6251822B1 (en) * 1998-07-20 2001-06-26 Corning Incorporated Method of making activated carbon derived from pitches
US6737445B2 (en) * 1999-09-15 2004-05-18 Tda Research, Inc. Mesoporous carbons and polymers
US6372289B1 (en) * 1999-12-17 2002-04-16 Corning Incorporated Process for manufacturing activated carbon honeycomb structures
US20020178706A1 (en) * 2000-02-04 2002-12-05 The Procter & Gamble Company Air filtering device
US20040069147A1 (en) * 2000-02-04 2004-04-15 The Procter & Gamble Company Air deodorization device having a detachable cartridge member
US6455023B1 (en) * 2000-10-11 2002-09-24 Corning Incorporated Metallic catalysts for non-neutral liquid media
US20020082168A1 (en) * 2000-12-11 2002-06-27 Graham James Richard Activated carbon for odor control and method for making same
US20020155252A1 (en) * 2001-01-31 2002-10-24 Masanori Tsuji Molded product of activated carbon and a method for production thereof
US6787494B2 (en) * 2001-01-31 2004-09-07 Japan Envirochemicals, Ltd. Molded product of activated carbon and a method for production thereof
US20020103081A1 (en) * 2001-02-01 2002-08-01 Helsa-Werke Helmut Sandler Gmbh & Co. Kg. Activated carbon molded body and use thereof
US20040045438A1 (en) * 2001-03-13 2004-03-11 Place Roger Nicholas Method and equipment for removing volatile compounds from air
US20030022787A1 (en) * 2001-04-11 2003-01-30 Westvaco Corporation Method of making shaped activated carbon
US6610628B2 (en) * 2001-04-20 2003-08-26 Air Products And Chemicals, Inc. Polymer network/carbon layer on monolith support and monolith catalytic reactor
US20030027718A1 (en) * 2001-04-20 2003-02-06 Nordquist Andrew Francis Polymer network/carbon layer on monolith support and monolith catalytic reactor
US6479704B1 (en) * 2001-04-20 2002-11-12 Air Products And Chemicals, Inc. Hydrogenation with monolith reactor under conditions of immiscible liquid phases
US20030049185A1 (en) * 2001-08-30 2003-03-13 Welp Keith Allen Monolith catalytic reactor coupled to static mixer
US20030050510A1 (en) * 2001-08-30 2003-03-13 Welp Keith Allen Monolith catalytic reactor coupled to static mixer
US20050129594A1 (en) * 2001-08-30 2005-06-16 Welp Keith A. Monolith catalytic reactor coupled to static mixer
US20040259727A1 (en) * 2001-12-20 2004-12-23 Andrea Bartolini Catalytic composition for the dehydrogenation of alkylaromatic hydrocarbons
US20030143370A1 (en) * 2002-01-21 2003-07-31 Ngk Insulators, Ltd. Porous honeycomb structure body, the use thereof and method for manufacturing the same
US20030157003A1 (en) * 2002-02-15 2003-08-21 Machado Reinaldo Mario Catalyst holder and agitation system for converting stirred tank reactor to fixed bed reactor
US20040116279A1 (en) * 2002-12-16 2004-06-17 Addiego William P. Supported metal catalysts
US6916943B2 (en) * 2002-12-16 2005-07-12 Corning Incorporated Supported metal catalysts
US20040118747A1 (en) * 2002-12-18 2004-06-24 Cutler Willard A. Structured adsorbents for desulfurizing fuels

Cited By (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090233789A1 (en) * 2006-05-11 2009-09-17 Kishor Purushottam Gadkaree Activated Carbon Honeycomb Catalyst Beds and Methods For The Manufacture Of Same
US20070265161A1 (en) * 2006-05-11 2007-11-15 Gadkaree Kishor P Activated carbon honeycomb catalyst beds and methods for the manufacture of same
US20090308793A1 (en) * 2006-07-26 2009-12-17 NANOTECH INVESTMENT 2 (PTY) LTD Suite 8, Panorama Office Estate Activation, refining, and use of oil shale
US20080132408A1 (en) * 2006-10-11 2008-06-05 Applied Technology Limited Partnership Carbon black monolith, carbon black monolith catalyst, methods for making same, and uses thereof
US20080207443A1 (en) * 2007-02-28 2008-08-28 Kishor Purushottam Gadkaree Sorbent comprising activated carbon, process for making same and use thereof
US8741243B2 (en) 2007-05-14 2014-06-03 Corning Incorporated Sorbent bodies comprising activated carbon, processes for making them, and their use
US20080289213A1 (en) * 2007-05-22 2008-11-27 Hee Ja Lee Garbage dryer
US7998898B2 (en) 2007-10-26 2011-08-16 Corning Incorporated Sorbent comprising activated carbon, process for making same and use thereof
US20090252663A1 (en) * 2008-04-02 2009-10-08 Todd Marshall Wetherill Method and system for the removal of an elemental trace contaminant from a fluid stream
US20090297762A1 (en) * 2008-05-30 2009-12-03 Kishor Purushottam Gadkaree Flow-Through Sorbent Comprising A Metal Sulfide
US20090297885A1 (en) * 2008-05-30 2009-12-03 Kishor Purushottam Gadkaree Composite Comprising An Inorganic Substrate With A Coating Comprising Activated Carbon And Metal Sulfide
US8124213B2 (en) 2008-05-30 2012-02-28 Corning Incorporated Flow-through sorbent comprising a metal sulfide
US8691722B2 (en) 2008-07-03 2014-04-08 Corning Incorporated Sorbent comprising activated carbon particles, sulfur and metal catalyst
US20100004119A1 (en) * 2008-07-03 2010-01-07 Kishor Purushottam Gadkaree Sorbent Comprising Activated Carbon Particles, Sulfur And Metal Catalyst
US20100127418A1 (en) * 2008-11-25 2010-05-27 Ronald Alan Davidson Methods For Continuous Firing Of Shaped Bodies And Roller Hearth Furnaces Therefor
US20100130352A1 (en) * 2008-11-25 2010-05-27 Dabich Ii Leonard Charles Methods For Processing Shaped Bodies
US20100127421A1 (en) * 2008-11-25 2010-05-27 Dabich Ii Leonard Charles Bi-directional flow for processing shaped bodies
US20100150814A1 (en) * 2008-12-15 2010-06-17 Kishor Purushottam Gadkaree Methods For Forming Activated Carbon Material For High Energy Density Ultracapacitors
US8784764B2 (en) * 2008-12-15 2014-07-22 Corning Incorporated Methods for forming activated carbon material for high energy density ultracapacitors
WO2012118656A3 (en) * 2011-02-28 2013-03-14 Corning Incorporated Method of coating a catalyst on a substrate
WO2013009600A3 (en) * 2011-07-08 2013-03-07 University Of Florida Research Foundation, Inc. Porous stabilized beds, methods of manufacture thereof and articles comprising the same
US9966171B2 (en) 2011-07-08 2018-05-08 University Of Florida Research Foundation, Inc. Porous stabilized beds, methods of manufacture thereof and articles comprising the same
US12119148B2 (en) 2011-07-08 2024-10-15 University Of Florida Research Foundation, Inc. Porous stabilized beds, methods of manufacture thereof and articles comprising the same
US11705255B2 (en) 2011-07-08 2023-07-18 University Of Florida Research Foundation, Inc. Porous stabilized beds, methods of manufacture thereof and articles comprising the same
US10991490B2 (en) 2011-07-08 2021-04-27 University Of Florida Research Foundation, Inc. Porous stabilized beds, methods of manufacture thereof and articles comprising the same
US10239035B2 (en) 2011-12-22 2019-03-26 University Of Florida Research Foundation, Inc. Solar thermochemical reactor, methods of manufacture and use thereof and thermogravimeter
US10239036B2 (en) 2011-12-22 2019-03-26 University Of Florida Research Foundation Solar thermochemical reactor, methods of manufacture and use thereof and thermogravimeter
US9669379B2 (en) 2011-12-22 2017-06-06 University Of Florida Research Foundation, Inc Solar thermochemical reactor, methods of manufacture and use thereof and thermogravimeter
US9776154B2 (en) 2012-12-21 2017-10-03 University Of Florida Research Foundation, Inc. Material comprising two different non-metallic parrticles having different particle sizes for use in solar reactor
WO2014138397A1 (en) * 2013-03-08 2014-09-12 Basf Corporaton Base metal catalyst and method of using same
CN105026041A (zh) * 2013-03-08 2015-11-04 巴斯夫公司 贱金属催化剂及其使用方法
WO2014185957A1 (en) * 2013-05-14 2014-11-20 Ciris Energy, Inc. Treatment of carbonaceous feedstocks
CN105431403A (zh) * 2013-05-14 2016-03-23 克里斯能量有限公司 含碳原料的处理方法
US10906017B2 (en) 2013-06-11 2021-02-02 University Of Florida Research Foundation, Inc. Solar thermochemical reactor and methods of manufacture and use thereof
US20160367963A1 (en) * 2014-01-29 2016-12-22 Ford Global Technologies, Llc Hydrocarbon trap with increased zeolite loading and improved adsorption capacity
US10926240B2 (en) * 2014-01-29 2021-02-23 Ford Global Technologies, Llc Hydrocarbon trap with increased zeolite loading and improved adsorption capacity
FR3045415A1 (fr) * 2015-12-18 2017-06-23 Air Liquide Procede de fabrication d'un adsorbant structure monolithique autosupporte
US10478776B2 (en) 2016-04-04 2019-11-19 Cppe Carbon Process & Plant Engineering S.A. Process for the removal of heavy metals from fluids
US10471388B2 (en) 2016-04-04 2019-11-12 Cppe Carbon Process & Plant Engineering S.A. Sulfur dioxide removal from waste gas
US20190118139A1 (en) * 2016-04-04 2019-04-25 Ajo Industrie S.À R.L. Catalyst mixture for the treatment of waste gas
AU2017248029B2 (en) * 2016-04-04 2021-05-27 Cppe Carbon Process & Plant Engineering S.A. Catalyst mixture for the treatment of waste gas
US11369922B2 (en) * 2016-04-04 2022-06-28 Cppe Carbon Process & Plant Engineering S.A. Catalyst mixture for the treatment of waste gas
CN109070072A (zh) * 2016-04-04 2018-12-21 Ajo工业有限责任公司 用于废气处理的催化剂混合物
WO2017174592A1 (en) * 2016-04-04 2017-10-12 Ajo Industrie S.À R.L. Catalyst mixture for the treatment of waste gas
CN110711605A (zh) * 2019-10-13 2020-01-21 西安凯立新材料股份有限公司 活性炭载体处理方法、钯炭催化剂的制备方法及应用
WO2022039739A1 (en) * 2020-08-19 2022-02-24 SM Intellectual Technologies LLC Trinuclear basic iron (iii) acetate solid absorbent compositions and methods for the removal or sweetening of mercaptan sulfur compounds from hydrocarbon streams
CN113058627A (zh) * 2021-03-30 2021-07-02 中建三局绿色产业投资有限公司 Al/Si-C基多孔核壳分离球体及其负载型催化剂和应用

Also Published As

Publication number Publication date
US20190201871A1 (en) 2019-07-04
WO2006110353A1 (en) 2006-10-19
BRPI0609737A2 (pt) 2011-10-18
US10596549B2 (en) 2020-03-24
CN101180122A (zh) 2008-05-14
US20090326270A1 (en) 2009-12-31
PT1877180T (pt) 2019-10-11
EP1877180A1 (de) 2008-01-16
US10478804B2 (en) 2019-11-19
US20170225151A1 (en) 2017-08-10
EP1877180B1 (de) 2019-07-24
US10265681B2 (en) 2019-04-23
ES2747901T3 (es) 2020-03-12
BRPI0609737B1 (pt) 2016-10-04
US20200055027A1 (en) 2020-02-20
US9637389B2 (en) 2017-05-02
EP3564209A1 (de) 2019-11-06

Similar Documents

Publication Publication Date Title
US10596549B2 (en) Activated carbon monolith catalyst, methods for making same, and uses thereof
US20080132408A1 (en) Carbon black monolith, carbon black monolith catalyst, methods for making same, and uses thereof
CN1200769C (zh) 除汞催化剂及其制备和使用方法
US6696384B2 (en) Method of making shaped activated carbon
US6573212B2 (en) Method of making shaped activated carbon
CA2442241C (en) Shaped activated carbon
US6472343B1 (en) Shaped activated carbon
GB2026467A (en) Monolithic support for catalysts
JPS6231984B2 (de)
US7304013B2 (en) Metal oxide catalysts
CN100344583C (zh) 一种烧结微纤结构化微米尺度颗粒的多孔复合材料及制造方法
JPH0260602B2 (de)
CA1258450A (en) Process for the preparation of catalyst supports and materials produced thereby
CN115400579A (zh) 一种脱氯剂及其制备方法和应用
Gadkaree et al. High surface area carbon substrates for environmental applications
JP2006212527A (ja) 触媒、触媒担体及び触媒担体の製造方法
JPS6058186B2 (ja) 押出成形方法による高強度炭素質系構造体の製造方法
CN107335419A (zh) 一种叠层结构多孔催化炭膜的制备方法
JPS6058187B2 (ja) 押出成形方法による高強度炭素質系構造体の製造法
JPS6018214B2 (ja) ガス浄化用触媒体

Legal Events

Date Code Title Description
AS Assignment

Owner name: REALIST TECHNOLOGY LIMITED PARTNERSHIP, GEORGIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MITCHELL, ROBERT L. SR.;MITCHELL, LEE M.;KELLER, JOSEPH H.;AND OTHERS;REEL/FRAME:016560/0221;SIGNING DATES FROM 20050411 TO 20050412

AS Assignment

Owner name: APPLIED TECHNOLOGY LIMITED PARTNERSHIP, GEORGIA

Free format text: CHANGE OF NAME;ASSIGNOR:REALIST TECHNOLOGY LIMITED PARTNERSHIP;REEL/FRAME:020700/0936

Effective date: 20070612

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION