CN111247097A - Activated carbon and preparation method thereof - Google Patents
Activated carbon and preparation method thereof Download PDFInfo
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- CN111247097A CN111247097A CN201880059679.8A CN201880059679A CN111247097A CN 111247097 A CN111247097 A CN 111247097A CN 201880059679 A CN201880059679 A CN 201880059679A CN 111247097 A CN111247097 A CN 111247097A
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- activated carbon
- chloroform
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 350
- 238000002360 preparation method Methods 0.000 title description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 92
- 238000001179 sorption measurement Methods 0.000 claims abstract description 86
- 239000011148 porous material Substances 0.000 claims abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000010998 test method Methods 0.000 claims abstract description 10
- 238000011282 treatment Methods 0.000 claims description 84
- 239000005011 phenolic resin Substances 0.000 claims description 74
- 230000004913 activation Effects 0.000 claims description 43
- 238000010438 heat treatment Methods 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 19
- 238000012360 testing method Methods 0.000 claims description 19
- 229920001568 phenolic resin Polymers 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 238000003763 carbonization Methods 0.000 claims description 15
- 238000010298 pulverizing process Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- FIMJSWFMQJGVAM-UHFFFAOYSA-N chloroform;hydrate Chemical compound O.ClC(Cl)Cl FIMJSWFMQJGVAM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 230000035515 penetration Effects 0.000 claims description 3
- 239000012085 test solution Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000000691 measurement method Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 17
- 239000003575 carbonaceous material Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 239000001569 carbon dioxide Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 238000003825 pressing Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000002156 adsorbate Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000010000 carbonizing Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- GATVIKZLVQHOMN-UHFFFAOYSA-N Chlorodibromomethane Chemical compound ClC(Br)Br GATVIKZLVQHOMN-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003988 headspace gas chromatography Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- FMWLUWPQPKEARP-UHFFFAOYSA-N bromodichloromethane Chemical compound ClC(Cl)Br FMWLUWPQPKEARP-UHFFFAOYSA-N 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical class [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- -1 sawdust Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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Classifications
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- 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
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
-
- 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
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides an activated carbon having excellent adsorption properties. The BET specific surface area of the activated carbon of the present invention is 650m2Over/g, 1250m2A total pore volume of 0.25 cm/g or less3(ii) a water flow rate of chloroform of 71L/g or more in the water flow test method, wherein the average pore diameter is 1.8nm or more and 4.0nm or less.
Description
Technical Field
The invention relates to activated carbon and a preparation method thereof.
Background
Activated carbon is used in a wide range of fields as an adsorbent, an electrode material for a capacitor, a catalyst, and the like. In addition, as the raw material of the activated carbon, there may be mentioned plant-based materials such as sawdust, wood chips, coconut shells and the like; high polymer materials such as phenol resins, polyacrylonitriles, polyimides, and composites thereof (paper phenol resins and the like); and mineral materials such as coal, petroleum, coke, and various asphalts.
The present inventors have focused on the fact that paper phenol resins can control mesopores and micropores formed by controlling activation conditions, and have proposed activated carbon having a pore structure suitable for an adsorbate (patent document 1). Specifically, as an activated carbon which exhibits excellent adsorption performance not only in equilibrium adsorption amount to an organic halide but also under water passing conditions, an activated carbon in which the pore volume ratio of pore diameter of 2nm or less and the pore volume ratio of more than 2nm and 10nm or less are controlled is disclosed.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2015/152391 pamphlet
Disclosure of Invention
The inventors of the present invention have made extensive studies with the object of further improving the adsorption performance of the activated carbon after developing the activated carbon disclosed in patent document 1.
The present invention has been made in view of the above circumstances, and an object thereof is to provide an activated carbon having excellent adsorption performance, and a method for producing the activated carbon.
[1] The activated carbon of the present invention which can solve the above problems,
BET specific surface area of 650m2Over/g, 1250m2A total pore volume of 0.25 cm/g or less3(ii)/g or more, and an average pore diameter of 1.8nm or more and 4.0nm or less, chloroform in the following water flow test methodThe amount of water to be passed is 71L/g or more.
The water passing test method comprises the following steps: the test water was passed through a column packed with 2.0g of activated carbon having a particle size of 53 to 180 μm, the chloroform concentration before and after passing through the column was measured, and the chloroform flow rate (L/g) per 1g of activated carbon was determined from the total amount of filtered water (L) up to the breakthrough point as the chloroform flow rate.
Test water: distilled water with chloroform concentration of 0.06mg/L
Space Velocity (SV): 500h-1
The chloroform concentration determination method comprises the following steps: head space gas chromatograph
Penetration point: when the water concentration of chloroform in the column effluent exceeds 20% with respect to the column effluent
[2] The activated carbon according to the above [1], wherein the activated carbon of the present invention preferably has a chloroform equilibrium adsorption amount of 4.5mg/g or more in the equilibrium test method described below.
The balance test method comprises the following steps: a100 mL Erlenmeyer flask to which a predetermined amount of activated carbon and a stirrer were added was filled with a chloroform solution, the flask was sealed, the flask was stirred at 20 ℃ for 14 hours, the content of the Erlenmeyer flask was filtered, and the equilibrium concentration (mg/L) of chloroform and the equilibrium adsorption amount (mg/g) of chloroform per 1g of activated carbon were determined by the above-mentioned chloroform concentration measurement method for the filtrate, and an adsorption isotherm was prepared as the equilibrium adsorption amount (mg/g) at an equilibrium concentration of 0.06 mg/L.
Test solutions: chloroform solution with concentration of 0.06mg/L
Quality of the erlenmeyer flask: quality of Erlenmeyer flask before and after filling with chloroform solution
The particle size of the activated carbon is as follows: particle size of 180 μm or less
Amount of activated carbon in each test: 0.013g, 0.026g, 0.065g, 0.130g, 0.260g
Adsorption isotherm: the equilibrium concentration and the equilibrium adsorption amount are measured for each predetermined amount of the activated carbon, and the adsorption isotherm is prepared based on the results.
[3]According to the above [1]Or [2]]The activated carbon according to (1), wherein the activated carbon has a para-density of 1.3g/cm3The following paper phenol resin laminate was carbonized and then subjected to gas activationAnd (4) processing to obtain the product.
[4]A preferred production method of the activated carbon of the present invention is characterized in that the density is 1.3g/cm3The following paper phenol resin laminate was carbonized and then subjected to gas activation treatment.
[5] The method of producing activated carbon according to the above [4], wherein at least one treatment selected from a cleaning treatment, a drying treatment, a pulverizing treatment and a heating treatment is performed after the gas activation treatment.
[6]According to the above [4]]Or [5]]The method for producing activated carbon according to (1), wherein the carbonized product of the paper phenol resin laminate obtained by the carbonization treatment has a pore volume of 0.15cm and a pore diameter of 1 to 10 μm3More than g.
[7] An activated carbon for water purifiers, which is obtained by the production method according to any one of the above [4] to [6 ].
The present invention provides an activated carbon having characteristics superior to those of the activated carbon of the prior art in terms of adsorption performance, and a method for producing the activated carbon.
Drawings
FIG. 1 is a graph showing the relationship between the mercury penetration amount of carbide and the pore diameter.
FIG. 2 is a graph showing the relationship between the volume of macropores of 1 to 10 μm and the density of a paper phenol resin laminate.
FIG. 3 is a graph showing the relationship between the specific surface area of activated carbon and the amount of chloroform introduced in a water introduction test.
FIG. 4 is a graph showing the relationship between the specific surface area of activated carbon and the equilibrium adsorption amount of chloroform in the equilibrium test.
Fig. 5 is an electron microscope (SEM) photograph of the activated carbon of the example.
FIG. 6 is a diagram showing a method based on N2Graph of pore size distribution analyzed by BJH method on adsorption isotherms of adsorption method.
Detailed Description
The present inventors have conducted extensive studies to improve the adsorption performance of conventional activated carbon and, as a result, have found that the above problems can be solved by improving a paper phenol resin laminate used as a carbon material. Conventionally, a carbon raw material of activated carbon is used as a scrap of a paper phenol resin laminate commonly used as a printed wiring board in electronic components and the like. The present inventors have unexpectedly found that adsorption performance can be improved by using activated carbon having a lower density than conventional paper phenolic resin laminates as a carbon raw material, and thus have completed the present invention. The present invention will be explained below.
The activated carbon of the present invention is a substance to be adsorbed, and various substances are adsorbed in the same manner as known activated carbons, and trihalomethanes such as chloroform, trifluoromethane, chlorodifluoromethane, bromodichloromethane, dibromochloromethane and tribromomethane, and organic halogen compounds such as trichloroethane and trichloroethylene are preferable, trihalomethanes are more preferable, and chloroform is more preferable to have excellent adsorption performance. In the present invention, the term "adsorption performance" means that the adsorbate preferably has excellent adsorption performance under water passage conditions (hereinafter, also referred to as water passage adsorption performance), and more preferably has more excellent equilibrium adsorption capacity (hereinafter, also referred to as equilibrium adsorption performance). Hereinafter, the adsorption performance means water passing adsorption performance, but preferably includes equilibrium adsorption performance.
The BET specific surface area of the activated carbon of the present invention is 650m2Over/g, 1250m2A pore volume of 0.25 cm/g or less3(ii)/g or more, and an average pore diameter of 1.8nm or more and 4.0nm or less, and the amount of chloroform flowing through the water test method described in the examples is 71L/g or more.
Water absorption performance
The activated carbon of the present invention has superior water adsorption performance as compared with conventional activated carbon. The excellent water passage adsorption performance of the present invention is derived from a novel carbon material different from the conventional one as described later, but it is difficult to specify the physical structure derived from the carbon material even when the activated carbon produced is studied. However, since the water adsorption performance is superior to that of conventional activated carbon, the physical structure is different, and it is obvious that activated carbon is novel, and therefore, the amount of chloroform water to be passed is defined as an index indicating a physical structure which is difficult to be clarified. Specifically, the activated carbon of the present invention is based on the water flow test of the examples described later, and the amount of water flow capable of maintaining the chloroform removal rate of 80% or more is 71L/g or more, preferably 75L/g or more, more preferably 78L/g or more, still more preferably 80L/g or more, still more preferably 85L/g or more, and most preferably 95L/g or more.
Equilibrium adsorption performance
In addition, the activated carbon of the present invention has an excellent balance adsorption performance as compared with conventional activated carbons. The excellent equilibrium adsorption performance of the present invention is also derived from a novel carbon material, and is defined by the equilibrium adsorption amount of chloroform as another index indicating a physical structure which is difficult to clarify, as in the case of the water passage adsorption performance. Specifically, the activated carbon of the present invention preferably has a chloroform adsorbing amount of 4.5mg/g or more, more preferably 5.0mg/g or more, further preferably 5.5mg/g or more, and further preferably 6.0mg/g or more per 1g of the activated carbon, based on the equilibrium test in examples to be described later. The activated carbon of the present invention may satisfy only the above water passage adsorption performance, but preferably satisfies both of the water passage adsorption performance and the equilibrium adsorption performance.
BET specific surface area of activated carbon
To ensure a sufficient adsorption amount, the BET specific surface area of the activated carbon was 650m2A ratio of 700m or more, preferably 700m2(ii) at least g, more preferably 750m2A total of 800m or more, preferably 800m2A total of 850m or more2More than g, most preferably 900m2More than g. On the other hand, if the balance between the volume ratio of micropores contributing to an increase in adsorption amount and the volume ratio of mesopores contributing to an increase in diffusion rate is sought, and the packing density of the activated carbon is taken into consideration, the BET specific surface area is 1250m2(ii) less than g, more preferably 1200m2A total of 1150m or less per gram2A total of 1100m or less, more preferably 1100m2(ii) less than g, most preferably 1050m2The ratio of the carbon atoms to the carbon atoms is less than g.
Total pore volume of activated carbon
The total pore volume of the activated carbon of the present invention means finenessPore volume of pore diameter of 30nm or less. In order to secure a sufficient adsorption amount, the total pore volume was 0.25cm3A volume of 0.30cm or more3A value of at least one gram, more preferably 0.35cm3A value of at least one gram, more preferably 0.40cm3A value of at least one gram, more preferably 0.45cm3More than g. The upper limit of the total pore volume is preferably 0.80cm3A value of less than or equal to g, more preferably 0.75cm3A value of 0.70cm or less in terms of/g or less3A concentration of 0.60cm or less in terms of/g3The ratio of the carbon atoms to the carbon atoms is less than g.
Average pore diameter of activated carbon
From the viewpoint of improving the efficiency of introducing an adsorbate into the activated carbon, the average pore diameter of the activated carbon is 1.80nm or more, more preferably 1.82nm or more, still more preferably 1.85nm or more, still more preferably 1.87nm or more, and most preferably 1.90nm or more. On the other hand, if the average pore diameter is too large, the packing density may be lowered, and therefore, the average pore diameter is 4.0nm or less, preferably 3.5nm or less, and more preferably 3.0nm or less.
Average particle diameter of activated carbon
The activated carbon of the present invention can be made into a shape and a size corresponding to the use. When activated carbon is used for water purifier applications or the like, it is preferably in the form of powder, granules, or granules thereof in view of contact efficiency. In view of the above contact efficiency, the average particle diameter of the activated carbon (i.e., the average particle diameter of the powder, granule or granulated product thereof) is preferably 10 μm or more, more preferably 20 μm or more, still more preferably 30 μm or more, preferably 500 μm or less, more preferably 300 μm or less, and still more preferably 200 μm or less.
The excellent water passing adsorption performance and equilibrium adsorption performance of the present invention are derived from the carbon raw material specified in the present invention. Therefore, even when different carbon materials having BET specific surface areas, total pore volumes, and average pore diameters falling within the above ranges are used, the carbon materials have different physical structures from the activated carbon derived from the predetermined carbon material of the present invention, and therefore, the water passage adsorption performance and the equilibrium adsorption performance of the present invention cannot be achieved.
The density of the active carbon is 1.3g/cm3The following paper phenol resin laminate (hereinafter also referred to as low-density paper phenol resin laminate) is used as the activated carbon as the carbon material. Specifically, the activated carbon of the present invention is preferably an activated carbon obtained by carbonizing a low-density paper phenol resin laminate and then performing a gas activation treatment. Activated carbon derived from a low-density paper phenolic resin laminate, having a density exceeding 1.3g/cm as compared with conventional activated carbon derived from a conventional paper phenolic resin laminate3The paper phenol resin laminate (hereinafter also referred to as a high-density paper phenol resin laminate) of (a) has more excellent adsorption performance than the activated carbon. Therefore, it is considered that the activated carbon derived from the low-density paper phenol resin laminate has a specific physical structure different from that of the activated carbon derived from the high-density paper phenol resin laminate, but for example, from electron microscope (SEM) photographs of example 4 and comparative example 2 shown in fig. 5, it is difficult to specify the physical structure of the activated carbon of the inventive example to such an extent that it can be distinguished from that of the comparative example, and even if the cross-sectional shape of the activated carbon is investigated, it is difficult to specify the activated carbon by each activated carbon. In addition, as shown in fig. 6, it is difficult to distinguish the activated carbon of the invention example from the activated carbon of the comparative example in the pore size distribution of the activated carbon, and it is difficult to specify the characteristics of the activated carbon of the present invention even when the activated carbon is examined by using other various analytical apparatuses. Therefore, one of the characteristics of the activated carbon of the present invention is that the activated carbon is preferably derived from a specific carbon raw material. In addition, since the excellent adsorption performance of the present invention cannot be obtained with conventional activated carbon derived from a high-density paper phenolic resin laminate, the degree of the effect obtained can be determined to be distinguishable from conventional activated carbon.
Paper phenolic resin laminate
In the present invention, a low-density paper phenolic resin laminate is used as the carbon raw material. The paper phenol resin laminate is a composite of a paper base material (hereinafter referred to as a mesoporous material) which is likely to form relatively large pores and a phenol resin (hereinafter referred to as a microporous material) which is likely to form relatively small pores. Further, if the carbide of the low-density paper phenol resin laminate is subjected to a gas activation treatment, an activated carbon having a pore structure contributing to improvement of water passage adsorption performance or balance adsorption performance can be obtained. The paper phenol resin laminate specified in the present invention has a density lower than that of known paper phenol resin laminates, and is a novel material. Then, the carbide of the novel paper phenolic resin laminate is activated to obtain activated carbon having a physical structure different from that of a conventional high-density paper phenolic resin laminate.
In the present invention, the low-density paper phenol resin laminate is carbonized, but as shown in fig. 1, the carbide derived from the low-density paper phenol resin laminate has a significantly higher pore volume with a pore diameter of 1 to 10 μm than the carbide derived from the high-density paper phenol resin laminate. It is considered that such carbide derived from a low-density paper phenol resin laminate having a specific pore structure is different from carbide derived from a high-density paper phenol resin laminate in the gas diffusion state in the carbide at the time of gas activation treatment. That is, it is considered that the density of carbide derived from the low-density paper phenol resin laminate is low, and the gas diffusion property inside is high when the gas activation treatment is performed, thereby affecting the formed pores and pore structure. It is considered that, due to the difference in the formation process of the fine pores and the fine pore structure, the physical structure of the activated carbon derived from the low-density paper phenol resin laminate differs from that of the activated carbon derived from the high-density paper phenol resin laminate subjected to the carbonization treatment and the activation treatment under the same conditions, and the difference appears as a difference in adsorption performance. The paper phenolic resin laminate of the present invention exhibiting such a difference had a density of 1.30g/cm3Hereinafter, it is preferably 1.25g/cm3Hereinafter, more preferably 1.20g/cm3Hereinafter, more preferably 1.15g/cm3The following. The lower limit of the density of the paper phenolic resin laminate is preferably 0.70g/cm3Above, more preferably 0.80g/cm3Above, more preferably 0.90g/cm3Above, most preferably 1.00g/cm3The above.
As a raw material constituting the low-density paper phenol resin laminate of the present invention, paper and phenol resin similar to those of paper phenol resin laminates used in conventional printed wiring boards and the like can be used, and other additives and compositions are not limited. In addition, the production method of the low-density paper phenol resin laminate can be carried out according to the conventional production method, but the production conditions need to be adjusted to achieve the above density. For example, the density of the paper phenol resin laminate can be adjusted to a desired low density by adjusting the pressing pressure at the time of molding and pressing the laminate of paper phenol resin (prepreg) obtained by impregnating a paper base with a phenol resin. In addition, the paper phenol resin laminate is molded under high-pressure molding pressure in order to impart strength and durability suitable for printed wiring boards for electronic parts and the like. Therefore, the known paper phenol resin molded products have been densified to exceed the density specified in the present invention. On the other hand, the low-density phenol resin laminate of the present invention can be obtained by reducing the pressing pressure, but is not suitable for printed wiring board use because of its low density and low strength and durability, but has strength and durability required as an adsorbent for water purifier use and the like.
Grinding Process 1
In the present invention, the low-density paper phenol resin laminate may be subjected to a pulverization treatment before the carbonization treatment. For example, by miniaturizing the low-density paper phenol resin laminate, uniform carbonization treatment or activation treatment can be performed in a short time, and thus, the paper can be appropriately pulverized according to the size of the carbonization furnace. For example, the low-density paper phenolic resin laminate after grinding is preferably 70% or more, more preferably 75% or more, and even more preferably 80% or more, and the particle size is preferably 5.0mm or less, more preferably 4.0mm or less, and even more preferably 3.35mm or less. The lower limit may be appropriately determined in consideration of operability and the like.
Carbonization treatment Process
The carbonization treatment step is a step of carbonizing the low-density paper phenol resin laminate to obtain a carbide. Carbides obtained by carbonizing a low-density phenolic resin laminate (hereinafter also referred to as low-density carbides) have a pore volume (hereinafter also referred to as large pore volume) of 1 to 10 μm in pore diameter, which is significantly developed. When a low-density carbide having a large pore volume is subjected to a gas activation treatment, the gas diffusivity during the gas activation is improved, and the obtained activated carbon has a pore structure contributing to the improvement of the adsorption performance. Large pore volume of low density carbide exerting the above effectsThe product is preferably 0.13cm3A value of at least g, more preferably 0.15cm3A value of at least one gram, more preferably 0.20cm3More than g.
The ratio of the low-density carbide to the total macropore volume of 1 to 10 μm is preferably 40% or more, more preferably 45% or more, still more preferably 50% or more, and still more preferably 55% or more. The higher the macropore volume ratio, the higher the gas diffusivity during the activation treatment, and the more the pore structure contributing to the improvement of the adsorption performance of the obtained activated carbon can be obtained, which is preferable.
Preferably, the carbonization treatment conditions are appropriately adjusted to obtain low-density carbides having the above-described large pore volume. The atmosphere during the carbonization treatment is preferably an inert gas atmosphere such as nitrogen, helium, or argon. The heat treatment is preferably performed at a temperature and for a time at which the low-density paper phenol resin laminate does not burn, and the temperature of the carbonization treatment (furnace temperature) is preferably 500 ℃ or higher, more preferably 550 ℃ or higher, preferably 1000 ℃ or lower, and more preferably 950 ℃ or lower. The holding time at the carbonization temperature is preferably 1 minute or more, more preferably 5 minutes or more, further preferably 10 minutes or more, preferably 10 hours or less, more preferably 8 hours or less, further preferably 6 hours or less.
Gas activation treatment step
The gas activation treatment step is a step of obtaining activated carbon by subjecting the low-density carbide to a gas activation treatment. The activated carbon obtained by gas activation of low-density carbide has a specific pore structure which is excellent in water adsorption performance and equilibrium adsorption performance, although the specific pore structure is not clear.
The conditions of the gas activation treatment step may be appropriately adjusted so as to obtain the activated carbon. The gas activation treatment refers to a method of heating carbide to a predetermined temperature and then supplying an activation gas to perform the activation treatment. The temperature (furnace temperature) at the time of gas activation treatment is preferably 400 ℃ or more, more preferably 500 ℃ or more, further preferably 600 ℃ or more, preferably 1500 ℃ or less, more preferably 1300 ℃ or less, further preferably 1100 ℃ or less. The temperature increase rate at this time is preferably 1 ℃/min or more, more preferably 2 ℃/min or more, further preferably 6 ℃/min or more, preferably 100 ℃/min or less, more preferably 50 ℃/min or less, further preferably 25 ℃/min or less. The heating holding time is preferably 0.1 hour or more, more preferably 0.25 hour or more, preferably 10 hours or less, and more preferably 7.5 hours or less.
As the activating gas, water vapor, air, carbon dioxide, oxygen, combustion gas, and a mixed gas thereof can be used. Hereinafter, steam will be described as an example, but the present invention can be applied to other activated gases such as carbon dioxide. When the water vapor is supplied, the concentration of the water vapor supplied in the activation treatment is preferably 40 Vol% or more, more preferably 50 Vol% or more, further preferably 60 Vol% or more, preferably 100 Vol% or less, more preferably 90 Vol% or less, and further preferably 85 Vol% or less. If the concentration of the supplied water vapor is within the above range, the formation of fine pores by the activation reaction becomes better, and the activation reaction proceeds more efficiently, whereby the productivity can be improved.
The steam may be supplied without diluting the steam or diluted with an inert gas and supplied, but in order to efficiently perform the activation reaction, it is preferable to supply the steam diluted with an inert gas. When the water vapor is diluted with the inert gas and supplied, the partial pressure of the water vapor in the mixed gas (total pressure 101.3kPa) is preferably 40kPa or more, more preferably 50kPa or more, and still more preferably 70kPa or more.
Treatment after gas activation treatment
The activated carbon after steam activation may be subjected to at least one treatment selected from (a) a washing treatment, (b) a drying treatment, (c) a pulverizing treatment 2, and (d) a heating treatment. (a) The activated carbon after steam activation is washed with a known solvent such as water, an acid solution, or an alkali solution. By washing the activated carbon, impurities such as ash can be removed. (b) The drying treatment is a step of removing water and the like contained in the activated carbon after the steam activation or after the washing. The drying treatment may be carried out by exposing the activated carbon to a predetermined temperature or under heating for a predetermined period of time. (c) The pulverization treatment 2 is a step of adjusting the particle size of the activated carbon to a size according to the application. The pulverization treatment 2 may be carried out using a disk mill, a ball mill, a bead mill, or the like, and may be adjusted to a predetermined particle size by classification or the like as necessary. (d) The heat treatment is a step of subjecting the activated carbon to a high-temperature heat treatment in an inert atmosphere. The amount of acidic functional groups of the activated carbon can be reduced or even removed by heat treatment. The activated carbon derived from the low-density paper phenolic resin laminate of the present invention can improve adsorption performance if the amount of acidic functional groups is reduced, and therefore, it is preferable to perform (d) heat treatment. The inert atmosphere in the heat treatment is the same as that in the carbonization step. The heat treatment may be carried out at a temperature and for a time sufficient to reduce the acidic functional group, and is preferably 400 ℃ or more, more preferably 600 ℃ or more, preferably 1300 ℃ or less, and more preferably 1200 ℃ or less. The heating holding time is preferably 0.5 hour or more, more preferably 1 hour or more, further preferably 1.5 hours or more, preferably 10 hours or less, and more preferably 8 hours or less.
The treatment after the gas activation treatment may be performed alone, or 2 or more kinds of treatment may be performed in any combination. In the case of combining the washing treatment and the other treatment, the washing treatment may be performed at any time before and after the pulverization treatment, but the washing treatment is preferably performed before the drying treatment or the heating treatment. A preferable combination of the plurality of treatments is (i) a pulverization treatment-cleaning treatment, (ii) a cleaning treatment-pulverization treatment, more preferably a combination of (iii) a pulverization treatment-cleaning treatment-drying treatment, (iv) a cleaning treatment-pulverization treatment-drying treatment, and still more preferably a combination of (v) a pulverization treatment-cleaning treatment-heating treatment, (vi) a cleaning treatment-pulverization treatment-heating treatment. Further, the heating treatment may be performed after the drying treatment, but since the activated carbon can be dried by the heating treatment, the drying treatment may be omitted in consideration of the treatment efficiency. In the above-mentioned preferred combinations (iii) to (vi), if particle size adjustment or the like is not required, the pulverization treatment may be omitted. In addition, in order to adjust the particle size, classification treatment may be performed by a sieve or the like as necessary, or classification treatment may be performed as a final step after the above treatment.
The activated carbon of the present invention can be used as an adsorbent for an adsorbate present in water in the atmosphere. The adsorbent is particularly suitable for removing the following adsorbates contained in tap water or industrial wastewater, and is more preferably used as activated carbon for water purifiers. The mode of the water purifier using the activated carbon of the present invention is not particularly limited, and the activated carbon can be applied to various known water purifiers.
[ examples ] A method for producing a compound
The present invention will be described more specifically below with reference to examples, but the present invention is not limited to the following examples, and can be modified and implemented as appropriate within the scope conforming to the gist of the present invention described above and below, and all of them are included in the technical scope of the present invention.
Example 1
Carbon raw material: the pressing pressure at the time of molding and pressing a laminate of paper phenolic resin (prepreg) was adjusted so that the used density was 1.1g/cm3The paper phenol resin laminate of (3) is used as a carbon material.
A pulverization step 1: the carbon material was charged into a pulverizer (DAS-20 manufactured by Daiko Seiko Co., Ltd.) to pulverize the carbon material. At this time, the carbon material is pulverized by a sieve in the pulverizer so that the proportion of 3.35mm or less is 80% or more at a diameter of 8 mm.
A carbonization treatment procedure: 200g of the pulverized carbon material was charged into a muffle furnace (manufactured by Toyo thermal Co., Ltd.), the temperature in the furnace was raised to 700 ℃ under a nitrogen flow (2L/min) (temperature raising rate: 10 ℃/min), and the resultant mixture was held for 2 hours to obtain a carbide of the carbon material.
An activation treatment process: 50g of the carbide was charged into a rotary kiln (manufactured by tanacach), the temperature in the kiln was raised to 910 ℃ (10 ℃/min), and then steam was circulated in the kiln together with nitrogen gas (1L/min) while maintaining the temperature (steam concentration: 70 Vol%), and steam activation was carried out for 20 minutes to obtain activated carbon.
A grinding step 2: the particle size of the obtained activated carbon was pulverized to 180 μm or less with a mortar.
A cleaning procedure: the pulverized activated carbon was washed with 5.0% hydrochloric acid (60 ℃ C.) and then with warm water (60 ℃ C.) to prepare activated carbon 1.
Example 2
Activated carbon 2 was produced by subjecting the activated carbon obtained in the same manner as in example 1 to the following treatment, except that the steam activation time was changed to 9 minutes.
A heat treatment process: the washed activated carbon was charged into a muffle furnace (manufactured by Toyo Seisaku-Sho Co., Ltd.), heated to 900 ℃ under a nitrogen flow (2L/min) (heating rate: 10 ℃/min), and then held for 2 hours to prepare activated carbon 2.
Example 3
Activated carbon 3 was produced in the same manner as in example 2, except that the steam activation time was changed to 15 minutes.
Example 4
Activated carbon 4 was prepared by subjecting activated carbon 1 of example 1 to the following treatment.
A heat treatment process: the washed activated carbon was put into a muffle furnace, heated to 900 ℃ under nitrogen flow (2L/min) (heating rate: 10 ℃/min), and then held for 2 hours to prepare activated carbon 4.
Example 5
Activated carbon 5 was produced in the same manner as in example 2, except that the steam activation time was changed to 30 minutes.
Example 6
50g of the carbonized carbon material of example 1 was charged into a rotary kiln, the temperature in the kiln was raised to 910 ℃ under nitrogen flow (1L/min), and then carbon dioxide (2.3L/min) was passed through the kiln together with nitrogen (1.0L/min) (carbon dioxide concentration 70 Vol%) while maintaining the temperature (1.0L/min), thereby obtaining activated carbon, which was activated for 32 minutes.
A grinding step 2: the particle size of the obtained activated carbon was pulverized to 180 μm or less with a mortar to obtain activated carbon.
The pulverized activated carbon was subjected to a cleaning step and a heat treatment step under the same conditions as in example 2, to prepare activated carbon 6.
Comparative example 1
Carbon raw material: the same carbon raw material as that of the activated carbon No.1 used in the examples of patent document 1 was used. Specifically, the pressing pressure at the time of molding and pressing a laminate of paper phenol resin (prepreg) was adjusted so that the density used was 1.44g/cm3The paper phenol resin laminate of (3) is used as a carbon material. Activated carbon was obtained by performing the grinding step 1, the carbonization step, the activation step, and the grinding step 2 in the same manner as in example 1. The obtained activated carbon was subjected to a cleaning step and a heat treatment step in the same manner as in example 2, to prepare activated carbon 7. In addition, comparative examples 1 to 3 are activated carbons simulating the invention examples of patent document 1.
Comparative example 2
Activated carbon 8 was produced in the same manner as in comparative example 1, except that the steam activation time was changed to 30 minutes.
Comparative example 3
Activated carbon 9 was produced in the same manner as in comparative example 1, except that the steam activation time was changed to 45 minutes.
Comparative example 4
The measurement conditions for the various properties in this example are as follows. The measurement results are shown in Table 1.
[ Density of paper phenolic resin laminate ]
The density of the phenolic resin laminate was calculated based on the following formula.
Density (g/cm) of paper phenolic resin laminate3) Mass (g) of paper phenol resin laminate/volume (length cm. times. width cm. times. thickness cm) of paper phenol resin laminate
[ macroporous volume of carbide ]
Samples (carbide) having a particle diameter of 0.5mm or more in the range of mercury intrusion pressure of 0.152 to 414MPa were measured by a mercury porosimeter (Auto Pore IV9520, manufactured by Micrometrics). In the analysis of the large pore volume, the large pore volume was determined using the integrated value of the mercury intrusion amount with a pore diameter of 0.05 μm to 107 μm.
Further, the total value of the mercury intrusion amount in the pore diameter of 1 to 10 μm of the sample was used to determine the pore volume up to the pore diameter of 1 to 10 μm.
The pore size distribution based on the measurement results is shown in fig. 1.
[ pore distribution of activated carbon ]
For each of the obtained activated carbons, 0.2g of the activated carbon was vacuum-dried at 200 ℃ and then subjected to N-based drying using ASAP2400 (manufactured by Shimadzu corporation)2The adsorption isotherm of the adsorption method was analyzed by the BJH method to determine the pore size distribution. The results are shown in FIG. 6.
[ specific surface area of activated carbon ]
After 0.2g of a sample (activated carbon) was heated in vacuum at 250 ℃, an adsorption isotherm was obtained using a nitrogen adsorption apparatus (ASAP-2400 manufactured by Micromeritics), and a specific surface area (m) was calculated by the BET method2/g)。
[ Total pore volume of activated carbon ]
The nitrogen adsorption amount at a relative pressure (p/p0) of 0.93 from the nitrogen adsorption isotherm was defined as the total pore volume (cm)3/g)。
[ average pore diameter of activated carbon ]
The average pore diameter is calculated based on the following equation assuming that the shape of the pores formed in the activated carbon is cylindrical.
Average pore diameter (nm) (4 × total pore volume (cm))3In terms of/g))/specific surface area (m)2/g)×1000
[ Water passage test ]
In order to reduce the pressure loss due to the fine powder, a column (diameter: 15mm) was packed with 2.0g of activated carbon having a particle size of 53 to 180 μm, and a water flow test was carried out in accordance with JIS S3201 (2010: test method for household water purifier). Specifically, raw water with a chloroform concentration adjusted to 0.06mg/L was supplied at a Space Velocity (SV) for 500h-1Through the column. The chloroform concentration before and after passing through the column was quantitatively determined by headspace gas chromatography. The breakthrough point was set to the chloroform concentration of the effluent water 20 relative to the influent water to the column% of chloroform was added to the solution at the point of breakthrough, and the amount of chloroform introduced at the point of breakthrough (total amount of filtered water (L)/mass of activated carbon (g)) was calculated]) As filtration performance. Incidentally, TurboMatrix HS manufactured by Perkinelmer was used as a headspace gas chromatograph sample injector, and QP2010 manufactured by Shimadzu corporation was used as a gas chromatograph mass spectrometer.
[ balance test ]
Chloroform (CHCl)3)0.5g was diluted with 50mL of methanol, and then diluted 10-fold with methanol to prepare a test stock solution. The test solution (2 mL) was diluted with pure water to prepare a chloroform solution having a concentration of 2 mg/L. After a stirrer was placed in a brown conical flask having a capacity of 100mL and a predetermined amount of activated carbon having a particle size of 180 μm or less (the amount of activated carbon in each test was 0.013 g: 0.026 g: 0.065 g: 0.130 g: 0.260g), the flask was filled with a chloroform solution, sealed with a glass plug coated with Teflon (registered trademark) grease, and fixed with a clip. Further, the mass of the flask before and after the water injection was measured, and the mass of the chloroform solution in the flask was calculated. Then, the flask was placed in a constant temperature bath maintained at 20 ℃ and stirred for 14 hours using a magnetic stirrer. After the stirring, the activated carbon and the solution in the flask were filtered by a syringe filter, and the obtained filtrate was subjected to headspace gas chromatography in the same manner as in the above water test to determine the equilibrium concentration (mg/L) of chloroform and the equilibrium adsorption amount (mg/g) per 1g of activated carbon obtained by dividing the mass of the activated carbon used, to prepare an adsorption isotherm, and the equilibrium adsorption amount at the equilibrium concentration of 0.06mg/L was calculated as the adsorption amount to chloroform. The results are shown in the column "equilibrium adsorption amount (mg/g)" in the table. The adsorption isotherm is an equilibrium adsorption amount at the time of measuring the equilibrium concentration and the equilibrium adsorption amount of the above-mentioned predetermined amount of the activated carbon, creating an adsorption isotherm from the results of the measurement, and then calculating the equilibrium adsorption amount.
[ TABLE 1]
As shown in fig. 1 and 2, it is understood that the volume of large pores of 1 to 10 μm of low-density carbide derived from the low-density paper phenol resin laminate (examples 1 to 6) is significantly larger than that of high-density carbide derived from the high-density paper phenol resin laminate (comparative examples 1 to 4). Furthermore, as shown in table 1, when the activated carbons of examples 1 to 6 and comparative examples 1 to 4 were compared with each other in each group, no clear difference was observed in terms of physical structures such as specific surface area, pore volume, and average pore diameter, but significant effects were obtained in the water passage test results shown in fig. 3 and the equilibrium test results shown in fig. 4. Therefore, from the results, it is also understood that the difference in physical structure of the activated carbon occurs due to the density of the paper phenol resin laminate as the carbon material, and this effectively acts to improve the water passage adsorption performance and the equilibrium adsorption performance.
In example 1 and example 4, the activated carbon was different in the presence or absence of heat treatment after the activation treatment. The specific surface area, pore volume and average pore diameter of both activated carbons were approximately the same, and no difference was found in the physical structure based on these. However, the activated carbon of example 4 subjected to the heat treatment showed more excellent water passing adsorption performance and equilibrium adsorption performance, and it is understood that the reduction of the amount of the acidic functional group by the heat treatment contributes to the improvement of the adsorption performance.
Although the same activation conditions were applied to example 4 and comparative example 1, and to example 5 and comparative example 2, the activated carbon derived from the low-density paper phenol resin laminate (examples 4 and 5) showed a tendency to increase in specific surface area, pore volume, and average pore diameter, and further, water-passing adsorption performance and equilibrium adsorption performance were significantly improved, as compared to the activated carbon derived from the high-density paper phenol resin laminate (comparative examples 1 and 2). From these results, it is understood that the activated carbon derived from the low-density paper phenol resin laminate has a physical structure effective for improving adsorption performance even when the activation treatment is performed under the same conditions.
Claims (7)
1. An activated carbon having a BET specific surface area of 650m2Over/g, 1250m2A total pore volume of 0.25 cm/g or less3(ii)/g or more, an average pore diameter of 1.8nm or more and 4.0nm or less, and a water flow amount of chloroform in the following water flow test method of 71L/g or more,
the water passing test method comprises the following steps: passing test water through a column packed with 2.0g of activated carbon having a particle size of 53 to 180 μm, measuring the chloroform concentration before and after passing through the column, and determining the chloroform water flow (L/g) per 1g of activated carbon from the total amount of filtered water (L) up to the breakthrough point as the chloroform water flow,
test water: distilled water with chloroform concentration of 0.06mg/L
Space Velocity (SV): 500h-1
The chloroform concentration determination method comprises the following steps: head space gas chromatograph
Penetration point: the point when the water concentration of chloroform in the column effluent water exceeds 20% with respect to the column influent water.
2. The activated carbon according to claim 1, wherein the equilibrium adsorption amount of chloroform in the equilibrium test method is 4.5mg/g or more,
the balance test method comprises the following steps: a100 mL Erlenmeyer flask containing a predetermined amount of activated carbon and a stirrer was filled with a chloroform solution, the flask was sealed, the flask was stirred at 20 ℃ for 14 hours, the content of the Erlenmeyer flask was filtered, the equilibrium concentration (mg/L) of chloroform and the equilibrium adsorption amount (mg/g) of chloroform per 1g of activated carbon were determined by the above-mentioned chloroform concentration measurement method for the filtrate, and an adsorption isotherm was prepared as the equilibrium adsorption amount (mg/g) at an equilibrium concentration of 0.06mg/L,
test solutions: chloroform solution with concentration of 0.06mg/L
Quality of the erlenmeyer flask: quality of Erlenmeyer flask before and after filling with chloroform solution
The particle size of the activated carbon is as follows: particle size of 180 μm or less
Amount of activated carbon in each test: 0.013g, 0.026g, 0.065g, 0.130g, 0.260g
Adsorption isotherm: the equilibrium concentration and the equilibrium adsorption amount are measured for each predetermined amount of the activated carbon, and the adsorption isotherm is prepared based on the results.
3. The activated carbon according to claim 1 or 2, wherein the activated carbon is of a para-density of 1.3g/cm3The following paper phenol resin laminates were carbonized and then gas-activatedAnd (4) carbon.
4. A method for preparing activated carbon is characterized in that the para-density is 1.3g/cm3The following paper phenol resin laminate was carbonized and then subjected to gas activation treatment.
5. The method for producing activated carbon according to claim 4, wherein at least one treatment selected from a cleaning treatment, a drying treatment, a pulverizing treatment, and a heating treatment is performed after the gas activation treatment.
6. The method for producing activated carbon according to claim 4 or 5, wherein the volume of pores having a pore diameter of 1 to 10 μm of the carbide of the paper-phenolic resin laminate obtained by the carbonization treatment is 0.15cm3More than g.
7. An activated carbon for water purifiers, which is obtained by the production method according to any one of claims 4 to 6.
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| JP6144655B2 (en) * | 2014-09-12 | 2017-06-07 | 株式会社タカギ | Molded adsorbent and water purifier using the same |
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2018
- 2018-09-28 WO PCT/JP2018/036346 patent/WO2020065930A1/en active Application Filing
- 2018-09-28 CN CN201880059679.8A patent/CN111247097B/en active Active
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| JP2002161439A (en) * | 2000-09-12 | 2002-06-04 | Toyobo Co Ltd | Low-pressure loss and nonwoven fabric-style activated carbon fiber and method for producing the same |
| CN105555714A (en) * | 2014-04-03 | 2016-05-04 | 关西热化学株式会社 | Activated carbon for water purifier |
| CN106573781A (en) * | 2014-07-25 | 2017-04-19 | 关西热化学株式会社 | Activated carbon with excellent adsorption performance and process for producing same |
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| CN112892481A (en) * | 2021-01-21 | 2021-06-04 | 北京再益生物科技有限公司 | Modified activated carbon, modification method thereof and application thereof |
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| Publication number | Publication date |
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| CN111247097B (en) | 2024-03-05 |
| WO2020065930A1 (en) | 2020-04-02 |
| KR102576958B1 (en) | 2023-09-11 |
| KR20210058742A (en) | 2021-05-24 |
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