TW400308B - Method of making mesoporous carbon - Google Patents

Abstract

Mesoporous carbon and method of making involves forming a mixture of a high carbon-yielding carbon precusor that when carbonized yields greater than about 40% carbon on a cured basis, and an additive that can be catalyst metal and/or low carbon-yielding carbon precusor that when carbonized yields no greater than about 40% by weight carbon on a cured basis. When a catalyst metal is used, the amount of catalyst metal after the subsequent carbonization step is no greater than about 1 wt. % based on the carbon. The mixture is cured, and the carbon precusors are carbonized and activated to produce mesoporous activated carbon.

Description

A7 B7 Printed by the Central Bureau of Standards of the Ministry of Economic Affairs-Industrial and Consumer Cooperatives 31 V. Description of the Invention (/) The application for this invention is based on the provisional US patent application No. 60/074241 filed on February 10, 1998 by Kishor P. Gadkaree. The name of the patent invention is " Mesoporous Carbon Bodies "and Gadkaree et al., On July 20, 1998, filed a provisional application for US Patent No. 60/093396. The name of the patent invention is · Method of Making Carbon Hav i ng Pore Size Distribution In the Mesopore Range " ° The present invention relates to the production of carbon with different pore sizes from carbon precursor products. The pore size is usually greater than 30 angstroms. It uses a low-yield carbon precursor product and / or a suitable metal catalyst compound. It has The ability to form a specific pore size / distribution, this characteristic is particularly important for purification and catalyst applications. BACKGROUND OF THE INVENTION Activated carbon has been found to be useful in many applications such as air and water purification, carbon in automotive gaseous emissions control Hydrogen adsorption and hydrocarbon adsorption in the cold start-up phase, etc. However, the fine pore structure of carbon (pores Gap diameter is less than 20 Angstroms and BET surface area is 1000-300 m 2 / g) suitable for many applications such as adsorbing gases such as light hydrocarbons and hydrogen sulfide, some applications require larger pore carbon for optimal adsorption and / Or catalyst applications. For example, removing larger molecular size pollutants such as liquid proteins, and traditional gaseous pollutants such as hydrocarbons or certain types of pesticides, which require specific surface characteristics and pore size distribution. When the catalyst or chemical reaction is limited by mass and thermal transfer, carbon with larger pores and gaps is preferred. At the same time, due to the consideration of catalyst loading and dispersion, medium-pore carbon is sometimes required. Whether in the form of coating film or substrate Activated carbon monomer, or the shape of the paper, the size of the paper is suitable for China National Standards (CNS) Regulation 8 (2 丨 〇χ 297mm) noon-. ·. # 11 i— nn-nn IV ▲ _____I I Order ......... (Please read the precautions on the back before filling out this page) V. Description of the invention (α) Activated carbon emission from printed products of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Can be used in many applications, especially those that require durability and low pressure drop, such as chemical reactions of several vessels or solvents or other corrosive media. Metal catalysts have been used to make support activity Carbon catalysts, such as disclosed in US Patent No. 5,480,823. However, there is no method to produce ie activated carbon, which has specially designed characteristics, such as porosity as some gaseous and liquid and catalysts Its application. Summary of the invention: One aspect of the present invention is to provide mesoporous carbon and a method for manufacturing mesoporous carbon, which include forming a mixture of high carbon generation rate carbon precursor product and additives, and the carbon precursor product of high carbon generation rate is carbonized. Generates more than 40% carbon. The ratio is calculated based on curing. The additive is a catalyst metal and / or a carbon precursor with a low carbon production rate. When carbonized, carbonized objects produce less than 40% carbon. The ratio is calculated based on curing. Benchmark. When a catalyst metal is used, the content of the catalyst metal after carbonization f · step is not more than 1% by weight, which is based on carbon. The mixture is cured to carbonize and activate the carbon precursor product to produce a mesoporous activated carbon. Detailed description; The present invention relates to the manufacture of activated carbon, by mixing a carbon precursor product with a high carbon generation rate, an additive with a low carbon generation rate, and / or a catalyst metal compound, followed by curing, carbonization, and finally carbon It is activated by heat treatment in an active chemical agent such as steaming, flying, and rolling carbon. When a catalyst metal compound is used, the amount of the catalyst metal after the carbonization step is not more than 1% by weight, which is calculated based on carbon. ‘The paper size is applicable to China; ^ Standard (CNS) Λ4 specification (2 丨 0X297 mm)

,, -------- dι · vv., 'f Please read the precautions on the back before filling in this page) | Order __— _ B7 V. Description of the invention (1) Medium porosity carbon system of the present invention Means the total pore volume is at least 50%, the total pore volume is between 60% and 90% of the volume in the range of 20 to 500 Angstroms and the gap volume of less than 25% is in the range of larger pores (greater than 500 Angstroms of carbon precursor product) Synthetic polymerizable carbonaceous material, which is transformed into carbon of continuous structure by heating. The carbon precursor product is preferred to particles that are more active and hinder, because carbon atoms are arranged in irregular three-dimensional graphite due to curing, carbonization, and activation. The structure of small plate continuity is not disturbed. 'High-yield carbon precursor product means that the precursor product will be converted to carbon due to carbonization due to the curing of more than 40% of the cured resin. It is particularly useful as a carbon precursor with a south-generation rate for the purposes of the present invention. The product is a precursor product of synthetic polymerization hindrance, such as a solution or a low viscosity liquid at room temperature or a synthetic resin that can be liquefied by heating or other means. The synthetic polymerizable carbon precursor product includes any liquid or liquefiable Carbon precursor product. Some examples of available carbon precursor products include thermosetting resins and some thermoplastic resins. Low-viscosity carbon precursor products (such as thermosetting resins) are preferentially applied as coatings because of their low viscosity and can be used in large quantities. Penetrates into the matrix. The staff of the Central Standards Bureau of the Ministry of Economic Affairs, Xiaoxian Cooperative, printed 5i. Generally, the viscosity of resin ranges from 50 to 100 cp. Any wax with a high carbon production rate can be used. Hope and cassia resin are most suitable. Hope resin is preferred Because of its low viscosity, high carbon generation rate, it is highly interconnected with other predecessors when curing, and it is low in price. Suitable phenol resins are soluble miscible resins such as those produced by Occidental Chemical Corporation 43250 and 43290 polyophen resins, and Durite soluble phenolic resins produced by Borden Chemical Company. A particularly preferred suitable liquid resin for cassia is Furcab-LP produced by Q〇Chemical Inc. This paper standard applies Chinese National Standard (CNS) Λ4 said Grid (210X 297mm) A7 ------ 5. Description of the invention (卬) The carbon precursor product contains a single high carbon generation rate. Body product material, or a mixture of two or more of the precursor product materials. Optionally, the formed activated carbon can be added to the liquid carbon precursor product to adjust the viscosity of the precursor product to form or shape a structure. In order to obtain the required carbon, the carbon precursor product with a low carbon yield and the carbon precursor product with a low carbon generation rate is mixed with the carbon precursor product with a high carbon generation rate. The carbon generation rate of the carbon precursor product with a low carbon generation rate is not greater than 40% of the solidified body.-Some carbon precursor products that are particularly useful for low breakage are interconnecting additives, such as glycerol, melamine, epoxy resin, and / or polyvinyl alcohol. . The use of a carbon precursor product with a low carbon generation rate alone does not make the catalyst gold; the I-item advantage is that the step of removing the metal is omitted, and the catalyst metal is unnecessary in the final product. When a catalytic metal is present in the carbon matrix, the effects of surface etching, trench formation, and etch pits created by each individual metal additive during the activation process are determined by its physical and chemical properties, carbon structure, and Reaction conditions β In order to selectively produce the required mesoporous activated carbon, the three effects are coordinated to produce the required pore size. Trenching and pitting provide an opportunity to form pores, and surface etching provides an opportunity to enlarge the pores. ‘'Printed by the staff of the Central Standards Bureau of the Ministry of Economic Affairs. Cooperatives are suitable metal catalysts for testing metals, testing metals, transition metals, and / or precious metals. Beneficially, the catalyst metals are Pt, Pd, Rh, Ag, Au, Fe, Re, Sn, Nb, V, Zn, Pb, Ge, As, Se, Co, Cr, Ni, Mn, Cu, Li, Mg , Ba, Mo, Ru, Os, Ir, Ca, Y or combinations thereof. Preferential use of metal is pt, c0, Ni, and / or Fe, especially Fe in the +3 valence oxidation state; containing Co is a special priority. This paper size applies Chinese National Standard (CNS) Λ4 specification (210X 297 mm) 7 A7 _________B7 V. Description of Invention (f) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The metal catalysts are prepared in advance. For example, it is the organic or inorganic surface of the catalyst metal. The heating will decompose into the catalyst or the catalyst metal oxide, such as sulfate, nitrate, etc. Metal compounds are finely dispersed into elemental forms? For gold> 1 powders tend to form larger particles in the graphite region rather than the beneficial opposite effect. Some examples of compounds are oxides, vapors, (except for alkali or alkaline earth metals) salts, carbosulfates, and complexes. Appropriate forms of gold-like organometallic compounds can be added for use with or without a carbon precursor product with a low carbon production rate. For example, the acetic acid salt is, for example, cobalt acetate, and / or the acetone compound is, for example, acetamidine, and / or iron is particularly suitable. However, we do not want to be bound by theory. We believe that the overall organic structure added to the resin solidifies into a matrix after curing to help form more pores, and this structure is removed during the carbonization process. Therefore, more catalysts are exposed to the surface during the activation step as a further enlargement of the pore size. 01% 至 1% 范围 内。 The amount of metal catalyst used in the present invention depends on the form or activity of the metal catalyst, the porosity and pore size distribution required at the end of the dream, but not more than 1%, and usually in the range of 0.01% to 1% , And usually in the range of 0.001% to 0.2% by weight, which is calculated based on the carbon existing after carbonization. For highly active cobalt, its concentration can be as low as 50 to 100 ppm. The amount of metal added significantly affects the resulting pore structure. Adding too much metal will significantly increase the metal sintering ratio. Sintered metal particles tend to close the pores and form so-called narrow neck pores. At the same time, when sintering occurs, the catalyst activity will decrease and even lose its activity. In some cases, carbon containing catalyst metal and low carbon generation rate is required. The paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (2 丨 〇 X 297 mm).

, Equipment-(Please read the precautions on the back before filling out this page) Order 7 V. Invention Description (6 Α7 Β7 Printed on the precursor product as an additive by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, such as #such as riding acid or acetic acid Wrong and / or iron compound, it is useful to add and subtract compounds to the two railways. It is particularly beneficial to mix acetic acid or acetazol and tris / silanol.-Item manufacture medium silk The carbon method is to coat a precursor of carbon and a catalytic metal compound to coat a floating silk domain. For example, a honeycomb body is freshly added with paper, paper, and bumps to form a continuous activity. For example, about 7 yuan _ The property is first dissolved in a small amount of water, and then placed in _ milliliters of low-viscosity phenolic soluble resin. Wei compound plus Ming ⑽ is converted into a homogeneous solution. The suspension of the solution is then coated in The base f is, for example, a monomeric substrate formed from cordierite. The HGOt test is performed at 15 cycles, and then carbonized and activated in an active agent such as carbon dioxide or water vapor. The substrate has an outer surface. The pores extend from the outer surface to the matrix. The membrane penetrates and disperses throughout the pores. In its most useful form, the monomer matrix has channels through which the fluid passes, such as a network of pores to communicate from the outside to the inside, and / or the flow channels extend from the early body-view to the other— The end serves as a channel for the fluid to enter from the end and leave at the other end. ≫ The substrate must have sufficient strength to allow it to glow in time and be able to withstand the heat treatment temperature at which the active film is formed. ^ The required porosity of the entire substrate is at least 1 〇%, county land is greater than 25%, and the highest priority is greater than ·. For most uses, the required porosity range is about 45% to 55%. Preferentially, the matrix material porosity generates interconnected pores

The paper size of the edition is subject to the Chinese Standard (CNS) Λ4 ^ 77ϊ〇729τ5 ¥ Τ A7 — B7 V. Description of the invention (Γ /) Its main characteristics are pure _ other bumps and / or more to produce a distorted pore network in Within the matrix. ---- ： ---- ν'ΛΪ 衣! (Please read the notes on the back before filling out this page.) Suitable porous matrix materials include ceramics, glass ceramics, glass, metal, clay, and their age. Touch the composition to treat or discern the composition, such as a mixture, compound, or complex. -Some particularly suitable for the implementation of the present invention: cordierite, mullite, clay, oxidized gold, and gold oxides, talc, talc, oxidized arsenite, alkalates, oxidized aragonite, magnesite Salt, spinel, cinnamon earth, shixi stone shixi acid salt, butterfly compound, bauxite shixi acid salt, for example, Jingtu, __ earth Shixi acid salt, rhodolite xixi stone, feldspar, titanium white, fused silica , Nitride, boride carbide, for example, selected from carbide carbide, nitride carbide, or a mixture thereof. Cordierite is preferred because its thermal expansion coefficient is comparable to that of carbon, which will increase the stability of activated carbon objects. Some ceramic substrates have been disclosed in U.S. Patent Nos. 4,127,691 and 3,885,977. These patents are incorporated herein by reference. Suitable metallic materials are any metal or alloy or intermetallic compound that provides durable structural functions and does not soften below 600 ° C. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. Particularly useful are alloys of the iron family metals (ie, Fe, Ni, and Co), which can contain carbon (for example, steel, especially stainless steel or high temperature steel) or no carbon. At present, the high temperature resistant gold is mainly composed of iron family metals and aluminum. It is preferred to use iron family metals as iron. Particularly preferred are Fe, A1, and Cr. For example, Fe5-20AP 40Cr and Fe7-10A110-20Cr powders are particularly suitable for containing other possible additives. Generally, the formation of blessings is described in U.S. Patent Nos. 4,992,233,4758272, and 5,427,601. U.S. Patent Nos. 4,992,233 and 47,58,272 are methods for manufacturing porous sintered objects. Fe and the paper size apply the Chinese National Standard (CNS) Λ4 specification (210X297 mm) ί〇 A7 --- B7 V. Description of the invention) It is composed of A1 metal powder composition, and is optionally added with Cu, for example. U.S. Patent No. 54276G1 relates to porous sintered objects, the composition of which is in weight percent, the wire contains 5 to 40 Cr, 2 to 3G Al, 0 to 5_ metal, 0 to 4 rare earth gold; | oxide addition ship He Wei is a secondary metal and an unavoidable impurity, and the iron group metal is preferably iron. When a rare earth metal oxide is present, the particular metal is at least one Y, lanthanoid metal, Zr, Hf, Ti, Si, alkaline earth metal, B, Cu, and Sn. When there is no oxidation of alkaline earth metals, the special metal is at least one Y, lanthanide metal, Zr, Hf, Ti, Si, β, and the optional addition of alkaline earth metals, Cu, and Sn. -The substrate is preferably a thin-walled plate substrate or a honeycomb body, which forms a set of multiple open-ended cells extending between the ends of the honeycomb body. Generally, the density of the cells of the honeycomb body is between 235 cells / cm 2 and 1 cell / cm 2. Examples of commonly used honeycomb bodies are 94 cells / cm2, 62 cells / cm2, or 47 cells / cm2, and 31 cells / cm2. The present invention is not limited to these examples. 15 面。 Generally g2 cell / square centimeter honeycomb body wall thickness is about 0.15 surface. The siding thickness is usually from 0.1 to 0.15. The external dimensions and shape of the object are controlled by the application. The cordierite honeycomb is printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs, and is particularly suitable as a substrate for medium-pore activated carbon. Contact is achieved by any method that brings the carbon precursor product and the metal catalyst into close contact with the inorganic substrate. Contact methods include immersing the substrate in a solution or slurry of a carbon precursor product (with or without a catalyst metal), or spraying a solution or slurry of a carbon precursor product (with or without a catalyst metal) on the substrate. Another method for manufacturing activated carbon with catalytic metals is to mix the precursors of carbon (with or without catalytic metals), binders and / or fillers, and this paper size applies the Chinese National Standard (CNS) Λ4 specification (210X297 mm) ) Π A7 —-___ B7 V. Description of the invention (q) Forming aid, the mixture is shaped by extrusion. Enough to use some binders as temporary plasticizing organic binders such as = cellulose vinegar. —General fiber—Methylcellulose, ethyl cellulose, butyl cellulose, methylnaphthalene, ethyllin, methyl cellulose, propyl cellulose, and propyl cellulose Base f-based cellulose, 0 ethyl methyl cellulose, naphthyl f-based cellulose, and mixtures thereof. Methylcellulose and / or methylcellulose are particularly preferred as the organic binder 'methylcellulose suitable for the implementation of the present invention, and propylrogyl cellulose, and mixtures thereof are particularly preferred. Some suitable fillers include natural and synthetic hydrophilic, and hydrophobic, fibrous and non-heterogeneous, carbonizable A Division carbonized fillers. -Some natural fillers are soft, such as pine, red pine, mahogany, etc., such as whitewood, beech, birch, oak, etc., eyebrows, shell fiber examples are almond shell, coconut shell, apricot core shell Peanut shell, big walnut shell, walnut shell, etc. Cotton fibers such as cotton batting, cotton fiber, cell membrane fiber, cotton seed fiber cut f plant fiber such as hemp fiber, coconut wood fiber, jute fiber, Qiongliang or other materials Shu for example, corn cob, citrus peel (dried), Huanglu, peat peach, corn, yam potato, rice, cassava flour, coal powder, active i 'printed by the Consumers ’Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Wait. . -Some synthetic materials are regenerated cellulose, rayon fiber, cellophane 1㈣ suitable for testing. Examples of cruciform materials are fibers, cottonized '' wood 'loam, and mixtures thereof, which are preferably in the form of fibers. Some of the inorganic fillers can be oxygen-containing minerals such as clay zeolites, talc, etc., carbonates such as carbonic acid office, and adolite oxalates, such as high paper size. Applicable ^ ύΓΓ210χ297 公 1—) 11 V. Invention Explanation (I ο Α7 Β7 Printed by the Central Bureau of Standards of the Ministry of Economic Affairs and Consumers Cooperatives, t (like clay donated by clay), fly ash (doped acid salt Γ), for example, lithium salt is _shi (Zhengweiji titanate , Acid salt, wrong, oxidized wrong spinel, magnesium Mingwei salt, mullite, bauxite, alum trihydrate =, spinel, attapuigite > α salt fiber, cordierite powder, etc. /, Some examples of particularly suitable inorganic fillers are cordierite powder, talc clay, and aluminosilicate fibers. Other filler structures are exposed to external branches and siding pores due to carbonization, because they usually leave very Low carbon residue. Some organic fillers such as fiber, fiber, nylon fiber, polypropylene fiber (fiber) or powder, acrylic fiber, polyvinyl alcohol, etc. Some particularly suitable binders And fillers have been stated on May 20, 1996 In U.S. Patent Application No. 08/650685, some forming extrusion aids are, for example, soaps, fatty acids are, for example, oleic acid, sub-acids, etc., polyoxyethylene stearates, etc., or mixtures thereof. Especially preferred It is sodium stearate. The optimal amount of extrusion aid depends on the composition and binder. The carbon precursor product and the metal catalyst (if present) are mixed with the corrected amounts previously mentioned. The ingredients are mixed and the mixture is heat treated. The carbon precursor product is converted into continuous carbon (carbonization). The generated carbon is heat-treated to activate the carbon and generate an activated carbon structure. ° When the carbon precursor product is a thermosetting resin, the carbon precursor product is activated before and preferentially Curing before carbonization. Curing is usually achieved by heating the precursor product to a temperature of 100 ° C to 200 ° C for 0.5 to 5 hours. Curing is usually applied to the Chinese national standard (CNS) A4 specification (210X297 mm) 13 Please read the precautions before / fill in the "poultry clothes book page order" V. Description of the invention (A7 B7 2 1 1 I 1 · HI. I II 1 ----- 11 —II; ^ II — (Please Read first For the precautions, please fill in this education.) It is performed in the air under atmospheric pressure. When using a specific precursor product (for example, succinic methyl alcohol), curing can be performed at room temperature by adding a curing catalyst such as This is achieved by acid catalysts. Curing also keeps the metal compound catalyst in the carbon uniformly dispersed. Carbonization is the thermal decomposition of carbonized materials and metal compound catalysts (if present), thus removing low molecular weight species from the carbon (for example, Carbon dioxide, moisture, gaseous hydrocarbons, etc.) and the production of fixed carbon bodies and underdeveloped pore structures. The curing hinders the carbonization or conversion of the precursor product usually by reducing or inert gas (such as gas, argon) Gas, helium, etc.) is heated to a temperature of 400 ° (3 to 800 °) for 1 to 10 hours. The Central Bureau of Standards, Ministry of Economic Affairs, Cooperative Cooperative Association, 11 solidifies and carbonizes the carbon precursor products to produce substantially undisturbed carbon in carbon objects with uniformly dispersed catalyst particles (if present). Catalysts are usually aggregated into larger particles, unlike solidified structures, where the catalyst is dispersed in the form of molecules. The size of the catalyst particles is determined by the amount of catalyst initially added to the resin. The more catalyst in the initial resin, the easier it is for the catalyst particles to aggregate. The size of the catalyst particles also depends on the carbonization and activation temperature. Higher carbonization and activation temperatures will cause significant metal sintering, even when the metal concentration is low. When carbon is in the form of a coating film, the carbon coating film is embedded in the pores of the matrix and has relatively high adhesion. The outer surface of the carbon coating film is an undisturbed layer of carbon and carbon bonds. If interconnected pores are present in the matrix, interconnected reticular carbon will be formed in the composition, which results in a more adhesive carbon coating film. The undisturbed carbon coating film extending on the outer surface of the formed substrate provides a structure with multiple advantages. The multiple advantages are the ability of good catalysts, even though its carbon content is quite low. Table paper dimensions are applicable to Chinese National Standards (CNS) 8-4. Specifications (2 丨 〇χ 297mm) V. Description of the invention (丨 A7 B7 13 Employees of the Central Standards Bureau of the Ministry of Economic Affairs of the Consumer Cooperatives printed disaster, strong, high temperature. The carbon content of the structure formed is less than the matrix and the total weight of carbon 50%, usually less than 30%. The solidification and carbonization of the catalyst metal compound in the predecessor product will cause the catalyst to have a uniform and tight chemical bond with the undisturbed carbon structure. The size of the catalyst particles produced is supported by the catalyst and processed. Controlled by parameters and catalyst characteristics, the particle size is the main factor determining the pore size in activated carbon. Good dispersion and uniform catalyst particle size help to form intermediate pores in activated carbon in the subsequent activation step. Catalyst The way to achieve activation will essentially form new pores in the medium pore size range, and expand the straight path of the fine pores formed Increase pore volume. Fine pores formed without the use of the metal catalyst of the present invention or carbon precursors with low carbon production rates are usually unavoidable. In general, activation can be achieved by standard methods at 400-90 (TC carbon dioxide or water Steam implementation. If activation is carried out in water vapor, the temperature is preferably from 40.0 to 800. (:. For the carbonization and activation of catalyst resins, lower decomposition and activation temperatures are preferred. In the carbonization stage, low temperature not only helps to form larger metal particles with less sintering, but also produces a relatively less dense carbon structure. Two factors are very important for the subsequent pore formation in the activation step Scenery> For this reason, it is preferred to use a lower activation temperature. From this point of view, water vapor activation is preferred over carbon dioxide activation because lower temperatures are needed due to the higher reaction rate of water vapor. Exist The catalyst provides new catalytically active sites to encourage pores to begin to form during the activation process rather than only at the carbon site in the absence of catalyst activation. Carbon activation reaction is faster than that of non-catalyst carbon activation. Due to the catalytic and non-contact recording rule CNS, M specifications (plus millimeters (please read the precautions on the back before filling this page). A 7 _____B7_ V. Description of the invention () The difference in reaction rate between catalyst modes, under some activation conditions, the catalyst activation becomes more significant than that without catalyst activation. In addition, the presence of catalyst will be in the catalyst The activation process has different effects on the removal of pores. It depends on the characteristics of the catalyst on the carbon surface and the reaction conditions. It can generate pores larger than 30 angstroms. In one embodiment of the present invention, the catalyst metal is Pt. For example, in the form of gas platinum dihydrogen and activation temperature is about 650 ° C to 750 ° C and carried out in water vapor. This condition produces 60% to 95% of the total porosity of activated carbon in the medium pore range, and 80% to 90% of the medium pore volume is a pore size in the range of 40 to 300 Angstroms. In another embodiment of the present invention, the catalyst metal is Co, for example, in the form of cobalt nitrate and the activation temperature is about 65 ° C. to 75 ° C. and is performed in water vapor. Under this condition, 60% of the total porosity of activated carbon is generated. % To 85% is in the range of medium pores, and 60% to 90% of the volume of medium pores is in the range of 40 to 300 angstroms. Employees of the Central Standards Bureau of the Ministry of Economic Affairs, the Consumer Cooperatives, printed disasters in another embodiment of the present invention The catalyst metal is Fe, preferably in the +3 oxidation state, such as in the form of ferric nitrate hexahydrate, with an activation temperature of about 650 ° to 800 ° C and carried out in water vapor. This condition produces total activated carbon 80% to 95% of the porosity is in the medium pore range, and 85% to 95% of the medium pore volume is in the range of 30 to 60 angstroms. Synthetic polymer-based carbon precursor products, similar to phenol resins are usually in Inert gas _ carbonized to form a fine carbon hard carbon with a small range of graphite (also known as coke). The coke formed is carbon-rich and has a small amount of pores formed during the removal of volatile products. We believe that the pore size in carbon The increase is due to the application of the Chinese National Standard (CNS) for this paper size. Λ4 is now (210X297 mm). 15 V. Description of the invention (leaf) Α7 Β7 Consumers' cooperation with the Central Standards Bureau of the Ministry of Economic Affairs. Metal compounds and the use of water vapor or carbon dioxide to activate coke are caused by: 1) the characteristics of the coke vortex layer produced are improved, even before activation. In other words, the finely dispersed metal compounds are more carbonized than other processes in the carbonization process. Can promote the formation of disordered structure. 2) After carbonization, the metal compound is reduced to a metal state. It is highly active and promotes activity in its vicinity. Larger pores are thus created around the catalyst. The catalyst activation using metal additives significantly increases the activation rate. In addition, activation is preferentially performed near the middle of the metal particles. When the catalyst particles form cavities, trenching and surface etching on the entire carbon object, the pore size (grooves and cavities) formed is equal to or larger than the catalyst particle size. By adjusting the size of the catalyst particles, it is possible to selectively generate medium pores and even larger pores. I 3) Activation in water vapor preferentially activates carbon dioxide, and β water vapor produces a more porous structure, more carbon with medium porosity, and lower temperature than carbon dioxide. If a catalyst metal is present, it can be removed from the formed mesoporous activated carbon body, or if it is required in the catalyst operation, it can be retained. Removal is achieved by extracting the metal into the solution and washing the metal out of the activated carbon object using a liquid chemical treatment. The chemical is an acid and for example a bowl acid, which will extract most of the metal. For many metals, the replacement of nitric acid with hydrochloric acid will effectively perform a glowing function, which forms a complex compound with, for example, a chloride. For specific species, acetic acid can be used, which immediately forms acetate. If the carbon surface is oxidized, for example, if nitric acid is used or another

This paper size is suitable for t Siljia County (C1 ^ J Λ4 size (210x297mm) I1! ^^ 1 * mm — ^ ϋ I mm ^ i K ^ _ 士 I i I-/---I 一 ^ _ (Please read the precautions on the back before filling this page) A7 ______ _____B7 V. Description of the invention ([7] An additional oxidant that requires further treatment in nitrogen or oxygen at elevated temperature to produce a reducing surface. Metal removal It can also be achieved by treating the carbon body with heat or gaseous chemical agents, which will form volatile metal compounds and release volatile compounds into gas by heating. The chemical agents are carbon monoxide, hydrogen, and chlorine, etc. The nature of the catalyst is determined by the properties of the catalysts. Due to the high volatility, the test metal can be removed directly from carbon objects by heat treatment. Examples of metals such as wNi, Fe, co can be removed by using volatile carboxyl compounds formed by carbon monoxide. For more details To illustrate the invention, the following non-limiting examples are presented. All ingredients, proportions and percentages are calculated on a weight basis unless otherwise stated. Examples of catalyst metals: Example 1: (Comparative Printed by the Consumers' Cooperatives of the Prospective Bureau of the Ministry of Economic Affairs ¾ > -II II!-I In--8 I Μ5 "---- -i 1 ..... I -I--m 丁 _ 、- β (Please read the notes on the back before filling out this page) Low-viscosity phenol resin of about 100 to 150 cp is impregnated and coated on the ceramic cordierite honeycomb body, which has a porosity of about 50%. At 95 ° C Dry, dry at 150 ° C: solidify, carbonize at 750 ° C in nitrogen and activate at 90 ° C carbon dioxide for different periods of time. The percentage of pores in the three phases was determined using nitrogen absorption in volume ratio. The pore volume percentage of the fine pore range is determined using the standard t method. The medium pore volume percentage is determined using the BJH method. The characteristics of the activated carbon formed are mainly the characteristics of fine pore carbon. Larger than 80% of the pore volume is within the micro pore range. The surface area is at least more than 1000m2 / g carbon. Although the percentage of medium pores has only slightly increased due to the increase in the degree of activated combustion, the increase of the radius compared with the degree of carbon combustion. The paper dimensions are subject to Chinese national standards ( CNS > Λ4 Grid (210X297 Mm > V. Description of the invention (A) A7 B7 17 Bei Gongxiao, Central Bureau of Standards, Ministry of Economic Affairs? ≫ Zuoshe Seal ¾ is quite small. Traditional activated carbon manufacturing will tend to produce rich no matter how high it burns. Carbon in the pores. The surface area is significantly improved with the degree of combustion. The pore size distribution does not change significantly with increasing the degree of combustion. Within the scope of the example, the carbon is activated to stabilize the carbon removal. Reaction: Example 2: The present invention uses iron osmate as a catalyst metal. About 7 grams of ferric acid was added to a small amount of water. After it was completely dissolved, it was mixed with 1000 ml of a soluble phenol resin (resole) (the same resin as above) and vigorously stirred to ensure that the catalyst precursor product was uniformly dispersed. The metal-containing mixture was impregnated and coated on a cordierite honeycomb body having a porosity of about 50%, and dried at 95 t: and at 150 °. (: Under curing, and under 750. (: 1 hour completion in nitrogen, and activation in water vapor and nitrogen gas mixture at 700 ° C for 1 to 4 hours. The activated carbon sample produced was adsorbed using nitrogen Isothermal analysis of the pore size distribution. The activated carbon formed is mainly medium pores with a medium pore content of about 80-90% of the total pores. Carbon has approximately 10% fine pores and larger pores. Porosity is about 30 to 60 Angstroms (85% of medium pores) with a peak of 38 Angstroms. The surface area of medium pore carbon is 500 to 650 m2 / g carbon. The total surface area is significantly reduced in the case of catalyst-assisted activation, which indicates the presence of Larger pores. The number of fine pores decreases significantly with increasing catalyst content. The number of medium pores tends to increase with the degree of burning off. Iron-containing carbon produces medium pore carbon, with a peak at 38 Angstroms in the medium pore range. Example 3: The present invention uses cobalt nitrate as the catalyst metal. Approximately 7.0 grams are used, the rest is too much (please read the precautions on the back before filling this page)

This paper size applies to the Chinese National Standard (CNS) Λ4 specification (2 丨 0X297 mm). 18 V. Description of the invention () A7 B7 The printing process and ㈣2 side of the κΠζ industrial and consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The resulting activity, which contains large to large feet, and 20 to 25% larger pores. The surface area is within the range of 45 to 100% carbon. Chain-containing carbon produces a bimodal distribution in the medium pore range, with peaks at 38 and 250 Angstroms. 'Eighth Example 4: The present invention is implemented in accordance with the procedure of Example 2, except that the addition of a metal compound is reduced to 2.8 grams, and the activation is at 700. (: Water vapor and nitrogen mixed gas. The formed activated carbon has 60% medium pores and 25% larger pores, and its surface area is about 600 m2 / g. The carbon has a single peak at 25 Angstroms in the medium range. The size of the spikes will make 75% of the medium pore volume pores in the range of 100 to 400 Angstroms. Example 5: The gas starter acid lice (CPA) of the present invention is used as a catalyst metal. Add about 5 grams of CPA and the rest It is the same as Examples 2 and 3. The produced activated carbon contains about 70% of medium pores and 10¾ large pores, and its surface area is close to 550 m2 / g. The main peak value of the carbon in the range of medium pores is 100 Angstroms. The size of the spikes will make 80% of the medium pore volume pores in the range of 40 to 300 Angstroms. Example 6: The soluble phenolic resin produced by Occidental Chemical Co., Niagara Falls, NY, is coated on cordierite honeycombs. And dried in gOtT, cured at 125-150 ° C, and carbonized at 90 ° C in nitrogen and activated in carbon dioxide at 900 ° C, the pore size distribution of the carbon formed was [cro-metric (norcross, Ga) ASAP 2000 instrument by measurement It is measured by nitrogen adsorption isotherm. All carbon is mainly fine pores, and the pores are within 10 angstroms.

Please ▲ Read the remarks again. Fill in the paper. I The size of the paper is applicable to the Chinese National Standard (CNS) M (210 x 297 mm) A7 B7 V. Within the scope of the description of the invention (丨 9) or less . Example 7: The invention Example 6 was repeated, except that 1% acetopropyl iron was added to the resin before coating. The coated honeycomb body is cured, carbonized, and activated in carbon dioxide. The average pore size of about 60% of the intermediate pores is about 90 Angstroms. Example 8: Comparison of extruded resin honeycomb bodies by mixing 55.6% to produce soluble phenolic resins such as inc., 14.7% cordierite slag, 22.2% cellulose fiber, 2% phosphoric acid, 4.6 % Methocel, 0.9% sodium stearate. The extruded mixture and the formed honeycomb bodies were dried, cured, carbonized at 90 ° C, and activated in carbon dioxide at 100 ° C. The pore size distribution shows that all fine pore carbons have an average pore size of about 5 Angstroms and there are very few or no intermediate pores. Example 9: The invention The experiment of Example 8 was repeated, except that 1% acetic acid was added to the resin before mixing. The samples were processed using the procedure of Example 8. The pore size distribution shows that 70% by volume is about 400 Angstroms. Example 7: The invention The process of Example 6 was repeated, except that glycerol and acetic acid were added to the resin and printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. The percentage calculation basis was the total coating liquid. Similar to the coating and treatment process of Example 6, the average pore size of the pore volume such as the% pore volume as shown in Figure 5 is about 500 angstroms. Only 20% of the volume is within the range of fine pores. Example 11: The present invention performs a test similar to Example 10, and about 20% of polyvinyl alcohol is added to the phenolic table paper. The Chinese National Standard (CNS) 297 '£ y Μ' 40030 ^ A7 -------- -B7 V. Description of invention (Η) 20 · Consumption cooperation between employees of the Central Bureau of Standards of the Ministry of Economic Affairs, Du printed resins, and added 1% cool acid diamonds before coating. The samples were processed using the example 6 process, and the pore size distribution showed that 69% of the volume was within the range of medium pores and 33% was within the range of fine pores. The above examples 6-12 show that the addition of iron or cobalt salts or cross-linking additives such as glycerol, melamine, or polyvinyl alcohol, the pore size distribution can be changed to larger pores, such as greater than 50. Ah, it is not formed during the conversion of soluble phenol resin. Example 13: Comparatively contains 55.5% Borden Inc. produced Durite liquid hope resin, 22.2% BH40 cellulose fiber, 14.7% cordierite slag, 4.7% Methocel, 0.9% sodium stearate, And 2% acid-filled raw materials are mixed in a grinder and re-extruded into a honeycomb body with 400 cells per square inch and the wall thickness is about 12 mil. The samples were dried at 90 ° C and at 125-150. (: Lower curing. Carbonization in 90Q ° C nitrogen for 6 hours and activation in carbon dioxide at 85 ° C for 4 hours. The pore size distribution of the formed honeycomb body is in the range of 2-20 angstroms. Does not exist Porosity greater than 20 Angstroms. Example 14: (Invention) Approximately .1% acetic acid was added to the raw material of Example 13. The sample was cured, carbonized, and activated in 75 (Tc carbon dioxide for 4 hours. Activation temperature Decreased because cobalt promotes carbon vaporization and highly uncontrolled combustion occurs at 850 ° C. The presence of larger volumes of pores in the 50-no Angstrom range confirms that mesopores can be produced using catalysts. The object is, for example, a honeycomb body, which is used as a catalyst support in a chemical or petrochemical reactor, or as an application for adsorption or water purification. T 〔: installation 丨 (please read the precautions on the back before filling / ¾ page) Paper size applies to Chinese National Standards (CNS> A4 specification (2 丨 0x297)) 21 21 A7 B7 400308 V. Description of the invention (> 〇) Example 15: Comparative approximately 16. 59 grams of nickel nitrate is first dissolved in 5 Milliliter of water and then mixed in 1000 milliliters of soluble phenolic resin. Using this high metal content resin as a dip coating, a carbon-coated honeycomb body was produced according to a similar process to Example 2. The metal content in the final carbon Above. The final porous carbon has a pore size distribution of 37% fine pores, 28% medium pores, and 35% larger pores. Significantly larger pores are produced due to the high content of catalyst metal. People It is understood that the present invention has been described in detail for some enumerated and specific embodiments, but the present invention is not limited to these embodiments, which can be used in other ways without departing from the spirit of the present invention and the scope of the following patent applications. I-- -I —n I —I! -11 _ < Buckle II ..... n -II— n, π seif (Please read the notes on the back before filling this page) Central Standards of the Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperatives ¾ One at ... Gu Jun I 懔 Family

Claims (1)

Notice 400 Dirty A8 B8 C8 D8 22 Six Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs printed a patent application for a patent park 1. A method for manufacturing a medium-pore activated carbon, the method includes: a) forming an exhibited compound, the compound It is composed of high-carbon-generation carbon precursor products and additives. The high-carbon-generation carbon precursor products generate more than 40% when carbonized. It is based on curing and the additives are made of catalytic metals. Carbon is selected as the type of the product and its composition. The carbon product that has a low production rate produces less than 40% carbon when carbonized. It is based on curing. The catalyst metal used is the catalyst metal after the carbonization step. The content is not greater than 1% by weight, which is based on calculation; b) curing the mixture; c) carbonizing the carbon precursor product in the mixture; and d) activating the carbon to produce a mesoporous activated carbon. 2. The method according to item 1 of the scope of patent application, wherein the carbon precursor product with high carbon generation rate is a thermosetting resin. 3. The method according to item 2 of the scope of patent application, wherein the carbon precursor product with high carbon generation rate is a phenol resin. 4. The method according to item 1 of the scope of patent application, wherein the additive is a catalyst metal. 5. The method according to item 4 of the scope of patent application, wherein the amount of catalyst metal is 0.01% to 0.2% by weight, which is calculated on the basis of carbon. 6. The method according to item 4 of the scope of patent application, wherein the catalyst metal is provided as a compound, and the metal is selected from alkali metals, alkaline earth metals, transition metals, precious metals, and combinations thereof. 7. The method according to claim 6 of the patent, wherein the catalyst metal is selected from co, Fe, Ni, Pt, and a combination thereof. 8. The method according to item 4 of the scope of the patent application, in which the catalytic metal is organic gold paper 1 and applicable to the Chinese National Standard (CNS) Ya 4 4 (210X297) mf — ^ — ^ 1 — ml > lfli fnn 1 · in ^ nn ti ^ n HI In— tn en ^ fK (Please read the notes on the back before filling in this card) i 6. The scope of patent application 400308 is provided in the form of compound. 9. The method according to item 8 of the scope of patent application, wherein the organic compound is selected from acetic acid, acetonitrile, iron, and a combination thereof. 10 'The method according to item 1 of the scope of patent application, wherein the additive is a carbon precursor product with a low carbon production rate. 11. The method according to item 10 of the patent application scope, wherein the carbon precursor product of low carbon generation rate is selected from propylene glycol, melamine formic acid, epoxy resin and / or polyvinyl alcohol, and a combination thereof. 12. The method according to the scope of patent application (1), wherein the additive is a carbon precursor product and a catalyst metal composition which are low in productivity. 13. According to the method of claim 12, the metal of the towel is provided as a gold layer compound, and the metal is selected from iron, cobalt, and a combination thereof. 14. According to the method of item 12 of Zhongshouwei, the cap precursor metal is provided by cobalt acetate and the carbon precursor product with low carbon generation rate is selected from glycerol, polyvinyl alcohol, and its composition. 15. The method according to item 1 of the patent application, wherein the carbon precursor product and the additive are coated on the substrate with a coating film. 16. According to the method of applying for patent encirclement and item 15, Ji Xia is jealous. 17. The oldest method according to the scope of the patent application, in which the carbon precursor product and additives are mixed with a binder and shaped into an object. 18. The method according to item 17 of the scope of patent application, wherein forming is achieved by extrusion. 19. The method according to item 18 of the patent application, wherein the carbon precursor product, the additive, and the binder are extruded into a honeycomb body. This paper size is applicable to China Standard (CNS) A4 specification (210X297). -Packing -------- Order -----, narrative 23 ___ (Please read the precautions on the back before filling this page) Printed by Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs, 400308________ --- VI. Patent Application ABCD 24 Zhongjialou, Ministry of Economic Affairs, is a printed bodywork cooperative. 20. The method according to item i of the scope of patent application, where The activation is carried out in a gas, which is selected from the type of water vapor and dioxin. 21. A method according to item 20 of the patent application, wherein the activation is performed in water vapor. '22. The method according to item 20 of the scope of patent application, wherein the activation temperature is 400t: to 80t. 23. The method according to item 20 of the scope of patent application, wherein a catalyst metal is used, the catalyst metal is platinum, and the activation temperature is 65 ° C to 750 ° C. 24. The method according to item 22 of the scope of patent application, wherein a catalyst metal is used, the catalyst metal is cobalt, and the activation temperature is 65 ° C to 750 ° C. 25. The method according to item 22 of the scope of patent application, wherein a catalyst metal is used, the catalyst metal is +3 valent iron, and the activation temperature is from 65 to 800 t. 26. An activated carbon manufactured according to method 23 of the scope of the patent application, which has a porosity characteristic that 60% to 95% of the total pores are in the medium pore range, and 80% to 90% of the pores have a medium pore volume. Sizes range from 40 to 300 Angstroms. 27. An activated carbon manufactured according to the 24th method of the patent application, which has a porosity characteristic that 60% to 85% of the total pores are in the range of medium pores, and 60% to 90% of pores of medium pore volume Sizes range from 100 to 400 Angstroms. 28. An activated carbon manufactured in accordance with method 25 of the scope of the patent application, which has a ceremonial clearance rate characterized by 8% to 95% of the total pore-gap in the middle pore range and 85% to 95% of the medium pore volume. Pore size in the range of 30 to 60 angstroms. 0 This paper size is applicable to Chinese National Standard (CNS) A4 grid (2Η) x 297 mm.) --- ^ ------ 1, -pack ---- --Order ------ 4 (Please read the notes on the back before filling this page)