CN112218711B - Adsorption sheet, method for producing adsorption sheet, and adsorption element - Google Patents
Adsorption sheet, method for producing adsorption sheet, and adsorption element Download PDFInfo
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- CN112218711B CN112218711B CN201980037618.6A CN201980037618A CN112218711B CN 112218711 B CN112218711 B CN 112218711B CN 201980037618 A CN201980037618 A CN 201980037618A CN 112218711 B CN112218711 B CN 112218711B
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 147
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 239000003463 adsorbent Substances 0.000 claims abstract description 264
- 239000002245 particle Substances 0.000 claims abstract description 162
- 239000000463 material Substances 0.000 claims abstract description 131
- 239000011230 binding agent Substances 0.000 claims description 71
- 239000010457 zeolite Substances 0.000 claims description 66
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 65
- 229910021536 Zeolite Inorganic materials 0.000 claims description 64
- 239000000835 fiber Substances 0.000 claims description 58
- 238000000197 pyrolysis Methods 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 33
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 30
- 229920006231 aramid fiber Polymers 0.000 claims description 28
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000004760 aramid Substances 0.000 claims description 21
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- 238000000354 decomposition reaction Methods 0.000 claims description 11
- 239000002250 absorbent Substances 0.000 claims description 8
- 230000002745 absorbent Effects 0.000 claims description 8
- 239000004693 Polybenzimidazole Substances 0.000 claims description 7
- 239000004642 Polyimide Substances 0.000 claims description 7
- 229920002480 polybenzimidazole Polymers 0.000 claims description 7
- 229920002577 polybenzoxazole Polymers 0.000 claims description 7
- 229920001721 polyimide Polymers 0.000 claims description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 6
- 239000004962 Polyamide-imide Substances 0.000 claims description 5
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 5
- 229920002312 polyamide-imide Polymers 0.000 claims description 5
- 229920003235 aromatic polyamide Polymers 0.000 claims description 4
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 claims description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 38
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 38
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 38
- 239000002243 precursor Substances 0.000 description 36
- 238000004458 analytical method Methods 0.000 description 31
- 238000000465 moulding Methods 0.000 description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 26
- 239000007864 aqueous solution Substances 0.000 description 19
- 239000000843 powder Substances 0.000 description 19
- 238000001878 scanning electron micrograph Methods 0.000 description 19
- 239000013078 crystal Substances 0.000 description 16
- 238000005245 sintering Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000005259 measurement Methods 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 13
- 239000008187 granular material Substances 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000012784 inorganic fiber Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 7
- 229920002689 polyvinyl acetate Polymers 0.000 description 7
- 239000011118 polyvinyl acetate Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000002612 dispersion medium Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 230000001133 acceleration Effects 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910001657 ferrierite group Inorganic materials 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000005192 partition Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000012798 spherical particle Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
-
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- 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
-
- 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
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
Abstract
An adsorption sheet comprising at least 1 or more kinds of adsorption materials (Ax: x=1, 2,3 … n), wherein the tap density of the adsorption materials (Ax) is Axa, the sphere volume calculated from the average particle diameter of the adsorption material particles when the adsorption material particles are assumed to be spherical is Axb, and the weight ratio (%) of the adsorption materials contained in the adsorption sheet is Axc, and the average particle number Axd per 1g of the adsorption sheet is represented by the following formula1 is represented by formula (Axd) = (1/Axa) × (1/Axb) × (Axc/100) (number/g) …, and the total average particle number of at least 1 or more adsorbent materials (Ax) contained in each 1g of the adsorbent sheet is represented by formula (2), and the specific strength of the adsorbent sheet is 2n·m/g or more.
Description
Technical Field
The present invention relates to an adsorption sheet for adsorbing and removing an organic solvent contained in air by an adsorbent, and a method for producing the adsorption sheet.
The present invention relates to an adsorption element for use in, for example, an exhaust gas treatment device for adsorbing and removing malodorous components such as organic solvents contained in air.
Background
As the adsorption sheet, known are: an adsorbent sheet produced by mixing an organic binder such as PVA (polyvinyl alcohol (polyvinyl alcohol)) with an organic fiber or an inorganic fiber and an adsorbent material (for example, refer to japanese patent application laid-open No. 9-94422 (patent document 1)).
Further, as the adsorbing element, there are known: an adsorption sheet containing an adsorption material, an organic fiber, an organic binder, an inorganic binder, and the like is molded into a honeycomb-shaped adsorption element by a honeycomb molding machine using a binder for honeycomb molding (for example, refer to japanese patent application laid-open No. 10-352 (patent document 2)).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 9-94422
Patent document 2: japanese patent laid-open No. 10-352
Disclosure of Invention
Problems to be solved by the invention
The adsorption sheet described in patent document 1 contains a zeolite adsorbent. Organic fibers and inorganic fibers as a framework material play a role in the flexibility and mechanical strength of the adsorption sheet. As the adsorption sheet, it is effective to increase the content ratio of the adsorption material in order to exhibit high performance. However, in contrast, the content ratio of the organic fibers and the inorganic fibers as the matrix material decreases, and as a result, there is a problem that the flexibility and strength of the adsorbent sheet decrease.
Patent document 2 also describes that zeolite is contained in the adsorption element as an adsorbent. The zeolite may be in the form of powder, granule or granule. Organic fibers and the like as a framework material play a role in the flexibility and mechanical strength of the adsorbent element. In order to exhibit high performance, it is effective to increase the content ratio of the adsorbent, but on the contrary, the content ratio of the organic fiber and the inorganic fiber as the framework material decreases, and as a result, there is a problem that the flexibility and strength of the adsorbent decrease.
The adsorbent sheet and the adsorbent material in the adsorbent element have specific apparent densities (bulk density) and tap density) which are closely related to the chemical species (activated carbon, zeolite, silica gel, etc.) and the bulk shape (particle diameter, fiber diameter, etc.) of the adsorbent material. Even if the content of the adsorbent contained in the adsorbent sheet is the same, the number of particles calculated from the apparent density and the particle diameter is different, and the number of particles is too large, so that the entanglement of the framework material becomes small, and the practical strength cannot be obtained.
In view of the above problems, an object of the present invention is to provide an adsorption sheet having excellent mechanical strength and adsorption performance as an adsorption sheet, and a method for producing the same.
In view of the above problems, an object of the present invention is to provide an adsorbent element having sufficient flexibility and strength as an adsorbent element and a high adsorbent material content ratio.
Means for solving the problems
The present inventors have made intensive studies to solve the above problems, and have finally completed the present invention. Namely, the present invention is as follows.
An adsorption sheet comprising at least 1 or more kinds of adsorption materials (Ax: x=1, 2,3 … n), wherein the tap density of the adsorption material (Ax) is Axa, the sphere volume calculated from the average particle diameter of the adsorption material particles when the adsorption material particles are assumed to be spherical is Axb, and the weight ratio (%) of the adsorption material contained in the adsorption sheet is Axc, and the average particle number Axd per 1g of the adsorption sheet is represented by the following formula 1.
[ number 1]
Axd = (1/Axa) × (1/Axb) × (Axc/100) (g) … type 1
The total average particle number of at least 1 or more adsorbent materials (Ax) contained per 1g of the adsorbent sheet is represented by the following formula 2. The specific strength of the adsorption sheet is more than 2 N.m/g.
[ number 2]
(Is the total average particle number of at least 1 or more kinds of adsorbing materials (Ax) contained in each 1g of the adsorbing sheet
In another embodiment, the total ratio of at least 1 or more of the adsorbing materials (Ax) contained in the adsorbing sheet is 40 wt% or more of the adsorbing sheet.
In other modes, the tap density of the adsorption material (Ax) is 0.1g/cm 3 The above.
In other aspects, the adsorbent material (Ax) is a zeolite.
A method for producing an adsorption sheet, which comprises at least 1 or more adsorption materials (Ax: x=1, 2,3 … n), wherein the tap density of the adsorption material (Ax) is Axa, the sphere volume calculated from the average particle diameter of the adsorption material particles when the adsorption material particles are assumed to be spherical is Axb, and the weight ratio (%) of the adsorption material contained in the adsorption sheet is Axc, and the average particle number Axd per 1g of the adsorption sheet is represented by the following formula 1.
[ number 3]
Axd = (1/Axa) × (1/Axb) × (Axc/100) (g) … type 1
The total average particle number of at least 1 or more adsorbent materials (Ax) contained per 1g of the adsorbent sheet is represented by the following formula 2. The specific strength of the adsorption sheet is more than 2 N.m/g.
[ number 4]
(Is the total average particle number of at least 1 or more kinds of adsorbing materials (Ax) contained in each 1g of the adsorbing sheet
In another embodiment, the adsorbent (Ax) further comprises an organic fiber (B-1) having a melting point or pyrolysis temperature of 300 ℃ or higher and an organic component (B-2) having a pyrolysis temperature of less than 300 ℃.
In other embodiments, the organic fiber is at least one polymer selected from the group consisting of an aramid polymer, a benzimidazole polymer, a benzoxazole polymer, and a polyimide polymer.
In other embodiments, the organic component is at least one selected from the group consisting of polyvinyl alcohol polymers, polyacrylonitrile polymers, and polyvinylpyrrolidone polymers.
An adsorbent element having a honeycomb structure comprising at least 1 or more adsorbent materials (Ax: x=1, 2,3 … n) and adsorbent sheets (adsorbent element precursors) having a plurality of air channels, wherein the average particle number Axd per 1g of the adsorbent sheets is represented by the following formula 1, wherein the tap density of the adsorbent materials (Ax) is Axa, the spherical volume calculated from the average particle diameter of the adsorbent particles when the adsorbent particles are spherical is Axb, and the weight ratio (%) of the adsorbent materials (Ax) contained in the adsorbent sheets is Axc.
[ number 5]
Axd = (1/Axa) × (1/Axb) × (Axc/100) (g) … type 1
The total average particle number of at least 1 or more of the adsorbent materials (Ax) contained per 1g of the adsorbent sheet is represented by the following formula 5. The planar compression strength of the adsorption element is more than 3 kPa.
[ number 6]
(Is the total average particle number of at least 1 or more kinds of adsorbing materials (Ax) contained in each 1g of the adsorbing sheet
The adsorbent element of claim 9, wherein the adsorbent sheet has fibers as a skeletal material.
In other embodiments, the thickness of the adsorption sheet is 0.16mm to 0.25mm.
In other aspects, the honeycomb structure has a honeycomb count of 30/cm 2 ～70/cm 2 。
In another aspect, the absorbent element according to any one of claims 9 to 12, wherein a total ratio of at least 1 or more of the absorbent materials (Ax) included in the absorbent element is 40% by weight or more of the absorbent element.
In other modes, the tap density of the adsorption material (Ax) is 0.1g/cm 3 The above.
In other aspects, the adsorbent material (Ax) is a zeolite.
Effects of the invention
According to the adsorption sheet and the manufacturing method thereof, the adsorption sheet having excellent mechanical strength and adsorption performance and the manufacturing method thereof are made possible.
According to this adsorbing element, it is possible to provide an adsorbing element having both sufficient flexibility and strength and a high adsorbing material content ratio.
Drawings
Fig. 1 is a graph showing various characteristics of each example and each comparative example of the adsorption sheet in embodiment 1.
FIG. 2 is a graph showing the relationship between the sintered sheet strength (N.m/g) and the total number of adsorbent particles (in/g) contained in the adsorbent sheet in each example and each comparative example of the adsorbent sheet in embodiment 1.
Fig. 3 is a diagram showing the shape of the adsorbing element in embodiment 2, that is, the honeycomb shape.
Fig. 4 shows an enlarged view of a portion of the adsorbing material having the shape of the adsorbing element in embodiment 2, that is, a honeycomb shape.
Fig. 5 is a graph showing various characteristics of each example of the adsorption sheet and each comparative example in embodiment 2.
Symbol description
2a groove portions, 2b pad portions.
Detailed Description
(embodiment 1)
Hereinafter, an adsorption sheet according to embodiment 1 of the present invention and a method for producing the same will be described with reference to the drawings. In the embodiments described below, numbers, amounts, and the like are mentioned, and the scope of the present invention is not necessarily limited to the numbers, amounts, and the like unless otherwise specified. The same reference numerals are given to the same components and corresponding components, and the description may not be repeated. Structures in the appropriate combination embodiments are included in the present invention.
[ Wet method Mixed papermaking (papermaking with adsorption material added therein) ]
When the adsorption material and the framework materials such as organic fibers/inorganic fibers are mixed and manufactured to obtain the adsorption sheet, the adsorption material reduces winding points among the framework materials. Therefore, from the viewpoint of the bulk density and particle diameter of the adsorbent, it is preferable that the smaller the specific volume representing the volume occupied by the unit mass, the smaller the occupied volume of the adsorbent, and the less the entanglement points between the framework materials. In practice, this is synonymous with the reciprocal of the preferred specific volume, i.e. the dense adsorbent material.
The shape of the adsorbent is powder, granule, fiber, etc., and in view of the content in the adsorbent sheet, it is general that not 1 powder, 1 granule, 1 fiber, but a large amount of powder, granule, fiber is carried. Therefore, bulk density and tap density (also referred to as compact bulk density) are examples of the packing density of the powder, particles, and fiber aggregate, but in order to consider an adsorption sheet in which an adsorption material is packed at a high content ratio, tap density representing a compact packed state is particularly important.
When the mixed paper is made into a wet paper, the adsorbent is preferably in the form of powder or granule, and particularly preferably in the form of powder. The tap density of the powder is preferably 0.1g/cm 3 ～2.0g/cm 3 Further preferably at 0.2g/cm 3 ～1.0g/cm 3 Within a range of (2).
[ relation with particle size ]
The particle diameter of the adsorbent (Ax) can be evaluated by laser diffraction or the like, and is preferably in the range of 0.001 μm to 30.0 μm, more preferably in the range of 0.01 μm to 20 μm. The particle size of the adsorbent is easily dependent on the type of adsorbent, and particularly zeolite is easily different in crystal size depending on the type of crystal. Depending on the type of zeolite crystals, the crystal size may be 3 μm or less, and in this case, it is difficult to obtain a completely dispersed state, and the laser diffraction may result in a larger particle size (secondary particle size) than the actual particle size. In this case, the average value of the crystal size of the minimum unit confirmed by image analysis such as SEM is regarded as the average particle diameter.
The adsorbent material in an embodiment is activated carbon or zeolite. Activated carbon and zeolite are excellent in adsorbing and desorbing low concentration organic compounds.
In the case of activated carbon, the form is a powder having an average particle diameter of 10 μm or more and 50 μm or less, or a fiber having an average fiber diameter of 10 μm or more and 30 μm or less. The raw materials of the activated carbon are not particularly specified, and include coconut shell, coal, pitch, phenol resin, polyacrylonitrile, cellulose, and the like.
The adsorbent material in an embodiment is preferably a zeolite. The zeolite has a high heat resistance temperature and lower reactivity with an organic solvent or the like at the time of adsorption than activated carbon, and therefore has excellent heat resistance and low risk of heat generation. Further, since zeolite has a pore structure clearer than that of activated carbon, adsorption performance to organic solvents and the like is excellent. In the case of zeolite, the zeolite is in the form of powder having an average particle diameter of 1 μm or more and 20 μm or less. The zeolite is a naturally occurring zeolite, but synthetic zeolite is preferred. Specifically, the beta-type, ZSM-5-type, ferrierite (ferrierite) type, mordenite (morbenite) type, L-type, Y-type, A-type and the like are included.
The adsorbent in the embodiment is more preferably a high silica zeolite having a high silica/alumina ratio. This is because the high-silicon zeolite is less susceptible to moisture and humidity in the gas to be treated, for example, by adsorbing an organic solvent from the gas to be treated. The silica/alumina ratio is preferably 15 or more, more preferably 50 or more.
The adsorbent element of an embodiment comprises at least one adsorbent material. One or more of the various activated carbons and zeolites described above may be selected. In the case of selecting a plurality of adsorbent materials, the ratio thereof is not particularly limited. The adsorbent may be appropriately selected according to the treatment conditions of the gas to be treated.
When the tap density of the adsorbent (Ax) is [ Axa ] and the sphere volume calculated from the average particle diameter of the adsorbent particles assuming a spherical shape is [ Axb ] and the weight ratio of the adsorbent contained in the adsorbent sheet is [ Axc ], the average particle number [ Axd ] contained in each 1g of the adsorbent sheet is represented by the following [ formula 1].
[ number 7]
Axd = (1/Axa) × (1/Axb) × (Axc/100) (g) … type 1
As described above, when the adsorbent is produced by mixing the adsorbent with the framework material such as the organic fiber and the inorganic fiber, the strength of the adsorbent tends to be lowered because the adsorbent reduces the entanglement points between the framework materials. Therefore, in order to obtain practical strength, it is preferable to suppress the total number of particles to a certain amount or less, and the total average particle number of at least 1 or more kinds of the adsorbent Ax contained in each 1g of the adsorbent sheet is represented by the following [ formula 2 ]]Preferably 8.0X10 12 The following is given.
[ number 8]
(Is the total average particle number of at least 1 or more kinds of adsorbing materials (Ax) contained in each 1g of the adsorbing sheet
[ organic fiber B-1]
The organic component (B) in the present embodiment is a component that acts as a carrier for the adsorbent (Ax) when the adsorbent is produced and also acts as a carrier after the adsorbent is molded, and is an organic fiber that is a pulp or a short fiber having a fiber length of about 10mm or less, in particular, a fiber that has an excellent heat resistance at 300 ℃ or higher, and has a melting point or a pyrolysis temperature. When the pyrolysis temperature is less than 300 ℃, a significant decrease in strength is inevitably generated at the high temperatures encountered in the adsorption and desorption operations. Specifically, the fiber is prepared from aramid fiber, meta-aramid fiber, polybenzimidazole (PBI), polybenzoxazole (PBO), polyimide, polyamide imide, polyether ketone and the like.
[ organic Adhesives B-2]
The organic component (B) preferably contains, in addition to the heat-resistant organic component (B-1), a substance having a pyrolysis temperature of less than 300 ℃. The low-temperature decomposable organic component (B-2) has a function of a binder for causing the adsorbent (Ax) to be attached to the adsorbent at a high ratio in the production of the adsorbent. The organic component having low-temperature decomposability may be PVA (polyvinyl alcohol (polyvinyl alcohol)), starch, polyacrylonitrile, or the like, but PVA is preferable.
When the low-temperature decomposable organic component (B-2) causes a large coverage of the adsorbent (Ax) and the adsorption performance is significantly low, the coverage of the adsorbent (Ax) can be reduced by subjecting the adsorbent sheet to a high-temperature heat treatment to cause the low-temperature decomposable organic component (B-2) to become carbide or decompose and disappear.
[ inorganic Binder C ]
In the present embodiment, the inorganic binder (C) may be added so that the adsorbent (Ax) and the framework material of the adsorbent sheet at high temperature remain fixed. For example, it may be dissolved in water, the adhesive is uniformly dispersed on the sheet, cured by reaction, gelation, or the like at the time of heat treatment, and the adsorbent material and the framework material are firmly fixed at the time of curing. The pyrolysis temperature is preferably 300 ℃ or higher, and the reaction heat is generated by the organic solvent having high reactivity, but the catalytic performance is low due to ignition and combustion of the sheet, and the adsorption performance of the adsorbent (Ax) is hardly lowered due to the coverage. For example, phosphate-based binders such as sodium hexametaphosphate and silicate-based binders such as sodium silicate are preferable.
[ content of adsorbent Ax ]
The amount of the adsorbent (Ax) contained in the heat-resistant adsorbent sheet of the present embodiment is preferably 40% by weight or more. In view of the adsorption performance, productivity, and falling of the adsorbent, 50 wt% or more is preferable. When the content of the adsorbent (Ax) is less than 40%, sufficient adsorption performance cannot be obtained. The upper limit of the weight of the adsorbent (Ax) is not limited, but the limit is 80% by weight in order to maintain sufficient sheet strength. When it exceeds 80% by weight, the softness of the adsorption sheet becomes insufficient and difficult to process. The amount of the organic component (B) contained in the heat-resistant adsorbent sheet of the present embodiment is 5 to 60% by weight based on the total amount of the organic component and the thermal oxide thereof used in the production of the adsorbent sheet.
When the content of the organic component (B) is less than 5%, the loading capacity of the adsorbent is insufficient, and when the content is 60% or more, there arises an inconvenience that the amount of the adsorbent to be used must be reduced. When the inorganic binder component (C) is contained in the adsorption sheet of the present embodiment, the inorganic binder component (C) is preferably 5 to 30% by weight. If the amount is less than 5% by weight, the fixation between the adsorbent (Ax) and the matrix material is poor, and if it is 30% or more, the flexibility is poor, which is not preferable.
[ method for producing adsorption sheet ]
The absorbent sheet of the present embodiment can be produced by, for example, a wet papermaking method using the absorbent material (Ax), the organic component (B), the inorganic binder (C), and, if necessary, glass fibers and a polymer binder.
[ considerations of B-1 and B-2 in the manufacturing method ]
The organic component (B) used in the method for producing an adsorption sheet of the present embodiment is preferably a low-temperature decomposable organic component (B-2) which is pyrolyzed at 150 to 300℃in addition to the heat-resistant organic fiber (B-1) such as the above-mentioned aramid fiber. The low-temperature decomposable organic component (B-2) functions as a binder for binding the (Ax) component to the (B-1) component and the (B-1) component during wet papermaking.
Since the component (B-2) covers the sheet-like material and the adsorbing material of the final adsorbing element (adsorbing element of the present embodiment) after the honeycomb molding, the component (B-2) can be subjected to a high-temperature heat treatment to change it into carbide or decompose it to disappear, and the covering of the adsorbing material on the final adsorbing element (adsorbing element of the present embodiment) can be reduced.
When the sheet and the honeycomb are heat-treated, the heat treatment is preferably performed in an air atmosphere using a heating oven or the like. The heat treatment temperature is lower than the melting point or decomposition temperature (T1 ℃) of the heat-resistant organic component (B-1), preferably 5 to 20 ℃ (T1-5 to T1-20 ℃) and higher than the decomposition temperature (T2 ℃) of the low-temperature decomposition component (B-2), preferably 100 to 200 ℃ (T2+100 to T2+200 ℃) and the treatment time at this temperature is 1 to 60 minutes, preferably 1 to 30 minutes. Typically from 350℃to 450℃for 1 to 10 minutes.
The specific strength of the adsorbent sheet is preferably 2N/m.g or more. At a strength of less than 2N/m.g, the adsorption sheet is liable to fracture or crack, and is not practical.
Gram weight (basis weight) (g/m) of adsorption sheet 2 ) There are no particular restrictions, but it is preferably 10g/m 2 ～200g/m 2 . When the particle size is less than 10g/m 2 In this case, the mechanical strength of the sheet is weakened, and the mechanical strength of the honeycomb structure cannot be maintained. If it exceeds 200g/m 2 The thickness of the sheet becomes too thick, so that the sheet loses flexibility and the sheet cracks and the adsorbing material falls off easily.
Example (example)
The method for measuring the properties of the adsorption sheet according to the present embodiment is as follows. Various characteristics of each example and each comparative example are shown in fig. 1 and 2.
(1) Method for measuring tap density of adsorption material
About 40g of the adsorbent material was placed in a constant volume container and dried in vacuo at 180℃for 15 hours or more. After cooling in the dryer for 20 minutes, the dry mass was measured to a number of bits of 0.1 mg. The mass of the dried sample was S (g). The whole dry sample was placed in a 200mL measuring cylinder, and the bottom surface of the measuring cylinder was tapped (the bottom surface of the measuring cylinder was tapped) for 3 minutes. The number of bits from volume (mL) to 1mL after 3 minutes was read. If this is used as the filling volume A (mL), the tap density L (g/mL) is determined by the following formula 3. In addition, since 1mL is 1cm 3 Thus the unit g/mL and g/cm of tap density L 3 Synonymous.
[ number 9]
L (g/mL) =S (g)/(A (mL) … type 3)
(2) Method for measuring average particle diameter of adsorbent and method for calculating sphere volume when spherical particles are assumed
The average particle diameter of the adsorbent is calculated by observing the crystal particle diameter of the adsorbent by SEM image in advance, and measuring the average particle diameter by a laser diffraction scattering particle size distribution measuring device when the crystal particle diameter is 3 μm or more, and measuring the average particle diameter by SEM image analysis when the crystal particle diameter is less than 3 μm.
< method for measuring average particle diameter by laser diffraction/scattering particle size distribution measuring apparatus >
The measuring apparatus used was LA-950V2 manufactured by horiba, inc., the measuring cell used was a wet circulation cell (flow rate measuring cell), sodium hexametaphosphate (0.1 mass% aqueous solution) was used as a dispersion medium, and an aluminum silicate-water system (refractive index: 1.66-1.33) was used as a refractive index setting of the object to be measured.
[ measurement procedure ]
1. A predetermined amount of dispersion medium was injected into the measuring cell, and initial adjustment of the optical system and blank measurement were performed.
2. After the blank measurement, an adsorption material was added to the cell so that the transmittance of the dispersion medium was in the range of about 90% to 70%.
3. After ultrasonic waves (frequency 20 kHz) were applied for several seconds for defoaming, 1 measurement was performed.
4. After the measurement, ultrasonic waves were applied for a predetermined time (5 minutes) to disperse the sample, and the measurement was performed again.
5. The data measured again after applying the ultrasonic wave for a prescribed time (5 minutes) was analyzed, and the median particle diameter (particle diameter with a cumulative frequency of 50%) was taken as the average particle diameter.
< method for measuring average particle diameter by SEM image analysis >
The measuring device used a Hitachi scanning electron microscope (SU 1510) with an acceleration voltage of 15.0kV.
[ measurement procedure ]
1. Double faced adhesive tape was attached to the SEM observation table, and the adsorbent material was spread on the double faced adhesive tape, and excess adsorbent material was removed.
2. Platinization was performed on an SEM observation stage coated with the adsorbent material.
3. The observation stage of 2 was set to the SEM image observation apparatus.
4. At the above acceleration voltage, 3000 times of pictures were taken at 3 different positions.
5. Photographs taken 3000 times were blanket printed with A4 paper.
6. 2 diagonal lines were drawn on the printed photograph with a pencil, 20 particles with well-defined boundaries on the diagonal lines were selected, and 2 points of the short diameter and the long diameter were measured with a ruler. The length of the scale (μm) of the SEM photograph was measured with a scale, and the short diameter and the long diameter of the particles measured with the scale were converted into μm.
7. A photograph was taken of 3 pieces of the particles at a magnification of 3000 times during the operation of 6. The short diameter and the long diameter of the total of 60 particles were calculated, and the average value of all the values was regarded as the average particle diameter (. Mu.m) obtained by SEM observation.
< method for calculating sphere volume assuming spherical particle >
Assuming that the average particle diameter calculated by laser diffraction or SEM image analysis is R (μm), the sphere volume Q (cm) of each particle is given when the particle is spherical 3 And/or) is obtained from the following equation 4.
[ number 10]
Q(cm 3 /number) = [4/3]×(R×10 -4 /2) 3 X 3.14 … type 4
(3) Specific strength measuring method
Measured according to JIS-P-8113 "test method of paper and paperboard-stretching characteristics". The test width was 15mm and the length was 50mm.
The adsorption sheet of the present invention is described in detail based on the following examples and comparative examples.
Example 1 ]
As the adsorbent A1, 37.5% by weight of a tap density of 0.54g/cm was used 3 As the adsorbent A2, a ZSM-5 (MFI) zeolite having an average particle diameter of 3.3 μm as measured by laser diffraction and a tap density of 0.36g/cm of 37.5% by weight was used 3 Y-type (FAU) zeolite having an average particle diameter of 1.2 μm as calculated by SEM image analysis, 17 wt% of pulp-like and staple-fiber-like aramid fibers (heat-resistant organic component: B-1) as heat-resistant organic components, 8 wt% of PVA (low-temperature pyrolysis organic component: B-2) as pyrolysis organic binder, and a wet papermaking apparatus were used to prepare a sheet having a grammage of 100g/m 2 Is a weight of (c).
Next, the sheet was immersed in a 20 wt% aqueous solution of sodium hexametaphosphate as an inorganic binder, and dried in air at 100 ℃, and sodium hexametaphosphate was fixed in a 5 wt% sheet to obtain a precursor sheet. Thereafter, the adsorbent sheet was obtained by heat-treating in a sintering furnace at 400℃for about 3 minutes in air.
Example 2 ]
As the adsorbent A1, 37.5% by weight of a tap density of 0.39g/cm was used 3 A ZSM-5 (MFI) zeolite having an average particle diameter of 9.9 μm obtained by laser analysis was used as the adsorbent A2, and a tap density of 0.34g/cm was 37.5% by weight 3 Y-type (FAU) zeolite having an average particle diameter of 0.7 μm as calculated by SEM photograph analysis, 17 wt% of pulp-like and staple-fiber-like aramid fibers (heat-resistant organic component: B-1) as heat-resistant organic components, 8 wt% of PVA (low-temperature pyrolysis organic component: B-2) as pyrolysis organic binder, and a wet papermaking apparatus were used to prepare a sheet having a grammage of 100g/m 2 Is a weight of (c).
Next, the sheet was immersed in a 20 wt% aqueous solution of sodium hexametaphosphate as an inorganic binder, and dried in air at 100 ℃, and sodium hexametaphosphate was fixed in a 5 wt% sheet to obtain a precursor sheet. Thereafter, the adsorbent sheet was obtained by heat-treating in a sintering furnace at 400℃for about 3 minutes in air.
Example 3 ]
As the adsorbent A1, 37.5% by weight of a tap density of 0.58g/cm was used 3 ZSM-5 (MFI) zeolite having an average particle diameter of 4.8 μm obtained by laser analysis, and tap density of 0.34g/cm was used as the adsorbent A2 at 37.5% by weight 3 Y-type (FAU) zeolite having an average particle diameter of 0.7 μm as calculated by SEM photograph analysis, 17 wt% of pulp-like and staple-fiber-like aramid fibers (heat-resistant organic component: B-1) as heat-resistant organic components, 8 wt% of PVA (low-temperature pyrolysis organic component: B-2) as pyrolysis organic binder, and a wet papermaking apparatus were used to prepare a sheet having a grammage of 100g/m 2 Is a weight of (c).
Next, the sheet was immersed in a 20 wt% aqueous solution of sodium hexametaphosphate as an inorganic binder, and dried in air at 100 ℃, and sodium hexametaphosphate was fixed in a 5 wt% sheet to obtain a precursor sheet. Thereafter, the adsorbent sheet was obtained by heat-treating in a sintering furnace at 400℃for about 3 minutes in air.
Example 4 ]
As the adsorbent A1, 60% by weight of a catalyst having a tap density of 0.54g/cm was used 3 ZSM-5 (MFI) zeolite (MFI) having an average particle diameter of 3.2 μm obtained by laser analysis, and a tap density of 0.36g/cm was used as the adsorbent A2 at 37.5% by weight 3 Y-type (FAU) zeolite having an average particle diameter of 1.2 μm as calculated by SEM photograph analysis, 17 wt% of pulp-like and staple-fiber-like aramid fibers (heat-resistant organic component: B-1) as heat-resistant organic components, 8 wt% of PVA (low-temperature pyrolysis organic component: B-2) as pyrolysis organic binder, and a wet papermaking apparatus were used to prepare a sheet having a grammage of 100g/m 2 Is a weight of (c).
Next, the sheet was immersed in a 20 wt% aqueous solution of sodium hexametaphosphate as an inorganic binder, and dried in air at 100 ℃, and sodium hexametaphosphate was fixed in a 5 wt% sheet to obtain a precursor sheet. Thereafter, the adsorbent sheet was obtained by heat-treating in a sintering furnace at 400℃for about 3 minutes in air.
Example 5 ]
As the adsorbent A1, 75% by weight of a catalyst having a tap density of 0.39g/cm was used 3 ZSM-5 (MFI) zeolite having an average particle diameter of 9.9 μm obtained by laser analysis, 17% by weight of pulp-like and staple-like aramid fibers (heat-resistant organic component: B-1) as heat-resistant organic component, 8% by weight of PVA (low-temperature pyrolysis organic component: B-2) as pyrolysis organic binder, and a wet paper machine was used to prepare a sheet having a grammage of 100g/m 2 Is a weight of (c).
Next, the sheet was immersed in a 20 wt% aqueous solution of sodium hexametaphosphate as an inorganic binder, and dried in air at 100 ℃, and sodium hexametaphosphate was fixed in a 5 wt% sheet to obtain a precursor sheet. Thereafter, the adsorbent sheet was obtained by heat-treating in a sintering furnace at 400℃for about 3 minutes in air.
Example 6 ]
As the adsorbent A1, 75% by weight of a catalyst having a tap density of 0.58g/cm was used 3 ZSM-5 (MFI) zeolite having an average particle diameter of 4.8 μm obtained by laser analysis, 17% by weight of pulp-like and staple-like aramid fibers (heat-resistant organic component: B-1) as heat-resistant organic component, 8% by weight of PVA (low-temperature pyrolysis organic component: B-2) as pyrolysis organic binder, and a wet paper machine was used to prepare a sheet having a grammage of 100g/m 2 Is a weight of (c).
Next, the sheet was immersed in a 20 wt% aqueous solution of sodium hexametaphosphate as an inorganic binder, and dried in air at 100 ℃, and sodium hexametaphosphate was fixed in a 5 wt% sheet to obtain a precursor sheet. Thereafter, the adsorbent sheet was obtained by heat-treating in a sintering furnace at 400℃for about 3 minutes in air.
Example 7 ]
As the adsorbent A1, 75% by weight of a catalyst having a tap density of 0.54g/cm was used 3 ZSM-5 (MFI) zeolite having an average particle diameter of 3.2 μm obtained by laser analysis, 17% by weight of pulp-like and staple-like aramid fibers (heat-resistant organic component: B-1) as heat-resistant organic component, 8% by weight of PVA (low-temperature pyrolysis organic component: B-2) as pyrolysis organic binder, and a wet paper machine was used to prepare a sheet having a grammage of 100g/m 2 Is a weight of (c).
Next, the sheet was immersed in a 20 wt% aqueous solution of sodium hexametaphosphate as an inorganic binder, and dried in air at 100 ℃, and sodium hexametaphosphate was fixed in a 5 wt% sheet to obtain a precursor sheet. Thereafter, the adsorbent sheet was obtained by heat-treating in a sintering furnace at 400℃for about 3 minutes in air.
Example 8 ]
As the adsorbent A1, 75% by weight of a catalyst having a tap density of 0.59g/cm was used 3 Beta zeolite with an average particle size of 0.8 μm (BEA) calculated by SEM image analysis, 17 wt% pulp-like and short-fiber-like aramid fiber (heat-resistant organic component: B-1) was used as the heat-resistant organic component, 8 wt% PVA (low-temperature pyrolysis organic component: B-2) was used as the pyrolysis organic binder, and a sheet was produced by a wet paper machine to have a grammage of 100g/m 2 Is a weight of (c).
Next, the sheet was immersed in a 20 wt% aqueous solution of sodium hexametaphosphate as an inorganic binder, and dried in air at 100 ℃, and sodium hexametaphosphate was fixed in a 5 wt% sheet to obtain a precursor sheet. Thereafter, the adsorbent sheet was obtained by heat-treating in a sintering furnace at 400℃for about 3 minutes in air.
Comparative example 1 ]
As the adsorbent A1, 15% by weight of a catalyst having a tap density of 0.39g/cm was used 3 ZSM-5 (MFI) zeolite having an average particle diameter of 10.7 μm obtained by laser analysis was used as the adsorbent A2, and 60% by weight of a tap density of 0.34g/cm was used 3 Y-type (FAU) boiling point with average particle diameter of 0.7 μm calculated by SEM image analysisStone, 17 wt% of pulp-like and short-fiber-like aramid fibers (heat-resistant organic component: B-1) were used as heat-resistant organic components, 8 wt% of PVA (low-temperature pyrolysis organic component: B-2) was used as a pyrolysis-type organic binder, and a sheet was produced by using a wet paper machine to give a sheet having a grammage of 100g/m 2 Is a weight of (c).
Next, the sheet was immersed in a 20 wt% aqueous solution of sodium hexametaphosphate as an inorganic binder, and dried in air at 100 ℃, and sodium hexametaphosphate was fixed in a 5 wt% sheet to obtain a precursor sheet. Thereafter, the adsorbent sheet was obtained by heat-treating in a sintering furnace at 400℃for about 3 minutes in air.
Comparative example 2 ]
As the adsorbent A1, 15% by weight of a catalyst having a tap density of 0.54g/cm was used 3 ZSM-5 (MFI) zeolite having an average particle diameter of 3.2 μm obtained by laser analysis, 60 wt% of tap density of 0.36g/cm was used as the adsorbent A2 3 Y-type (FAU) zeolite having an average particle diameter of 1.3 μm as calculated by SEM image analysis, 17 wt% of pulp-like and short-fiber-like aramid fibers (heat-resistant organic component: B-1) as heat-resistant organic components, 8 wt% of PVA (low-temperature pyrolysis organic component: B-2) as pyrolysis organic binder, and a wet papermaking apparatus were used to prepare a sheet having a grammage of 100g/m 2 Is a weight of (c).
Next, the sheet was immersed in a 20 wt% aqueous solution of sodium hexametaphosphate as an inorganic binder, and dried in air at 100 ℃, and sodium hexametaphosphate was fixed in a 5 wt% sheet to obtain a precursor sheet. Thereafter, the adsorbent sheet was obtained by heat-treating in a sintering furnace at 400℃for about 3 minutes in air.
Comparative example 3 ]
As the adsorbent A1, 75% by weight of a catalyst having a tap density of 0.34g/cm was used 3 Y-type (FAU) zeolite having an average particle diameter of 0.7 μm as calculated by SEM image analysis, 17 wt% of pulp-like and short-fiber-like aramid fibers (heat-resistant organic component: B-1) were used as heat-resistant organic components, and 8 wt% of P was used as a pyrolyzable organic binder VA (low temperature pyrolysis organic component: B-2), and sheet-like material was produced by using a wet papermaking apparatus so as to have a grammage of 100g/m 2 Is a weight of (c).
Next, the sheet was immersed in a 20 wt% aqueous solution of sodium hexametaphosphate as an inorganic binder, and dried in air at 100 ℃, and sodium hexametaphosphate was fixed in a 5 wt% sheet to obtain a precursor sheet. Thereafter, the adsorbent sheet was obtained by heat-treating in a sintering furnace at 400℃for about 3 minutes in air.
The adsorption sheet of the present embodiment is an adsorption sheet produced by a wet papermaking method and having at least 1 type of adsorbent, and in order to achieve coexistence of the strength of the adsorption sheet and a high content ratio of the adsorbent, the total particle number contained in the sheet calculated from the bulk density and the particle diameter of the adsorbent is appropriately set, and the obtained adsorption sheet is excellent in flexibility and strength by using, as a framework raw material, an organic component having a melting point or pyrolysis temperature of 300 ℃ or more and an organic component and an inorganic binder having a pyrolysis temperature of less than 300 ℃, and also excellent in adsorption performance because the content ratio of the adsorbent is extremely high.
As shown in the above examples and comparative examples, the strength of the adsorption sheet was significantly different depending on the total number of the adsorption material particles contained in the adsorption sheet by making the total number of the particles 8.0X10 12 In the following, a suction element sheet having sufficient practical strength can be obtained.
(embodiment 2)
An adsorption element according to embodiment 2 of the present invention is described below with reference to the drawings. In the embodiments described below, numbers, amounts, and the like are mentioned, and the scope of the present invention is not necessarily limited to the numbers, amounts, and the like unless otherwise specified. The same reference numerals are given to the same components and corresponding components, and the description may not be repeated. It has been proposed from the beginning to use the structures in the embodiments in appropriate combinations.
[ Wet method Mixed papermaking (papermaking with adsorption material added therein) ]
The adsorption sheet is obtained by mixing and manufacturing the adsorption material and the framework materials such as organic fibers or inorganic fibers, and when the adsorption element formed into a honeycomb shape is obtained by using the binder for honeycomb molding through a honeycomb molding machine, the adsorption material reduces winding points among the framework materials. Therefore, from the viewpoint of the bulk density and particle diameter of the adsorbent, it is preferable that the smaller the specific volume representing the volume occupied by the unit mass, the smaller the occupied volume of the adsorbent, and the less the entanglement points between the framework materials.
In practice, this is synonymous with the reciprocal of the preferred specific volume, i.e. the dense adsorbent material. The shape of the adsorbent is powder, granule, fiber, etc., and in view of the content in the adsorbent element, it is general that not 1 powder, 1 granule, 1 fiber, but a large amount of powder, granule, fiber is carried. Therefore, bulk density or tap density (also referred to as compact bulk density) is known as the packing density of the powder, particle, or fiber aggregate, but tap density representing a compact packed state is particularly important as an adsorbent element in order to have a high content ratio of the adsorbent material.
When the mixed paper is made into a wet paper, the adsorbent is preferably in the form of powder or granule, and particularly preferably in the form of powder. The tap density of the powder is preferably 0.1g/cm 3 ～2.0g/cm 3 Further preferably at 0.2g/cm 3 ～1.0g/cm 3 Within a range of (2).
[ relation with particle size ]
The particle diameter of the adsorbent (Ax) can be evaluated by laser diffraction or the like, and is preferably in the range of 0.001 μm to 30.0 μm, more preferably in the range of 0.01 μm to 20 μm. The particle size of the adsorbent is easily dependent on the type of adsorbent, and particularly zeolite is easily different in crystal size depending on the type of crystal. Depending on the type of zeolite crystals, the crystal size may be 3 μm or less, and in this case, it is difficult to obtain a completely dispersed state, and the laser diffraction may result in a larger particle size (secondary particle size) than the actual particle size. In this case, the average value of the crystal size of the minimum unit confirmed by image analysis such as SEM (scanning electron microscope: scanning Electron Microscope) is regarded as the average particle diameter.
The adsorbent material in an embodiment is activated carbon or zeolite. Activated carbon and zeolite are excellent in adsorbing and desorbing low concentration organic compounds.
In the case of activated carbon, the form is a powder having an average particle diameter of 10 μm or more and 50 μm or less, or a fiber having an average fiber diameter of 10 μm or more and 30 μm or less. The raw materials of the activated carbon are not particularly specified, and include coconut shell, coal, pitch, phenol resin, polyacrylonitrile, cellulose, and the like.
The adsorbent material in an embodiment is preferably a zeolite. The zeolite has a high heat resistance temperature and lower reactivity with an organic solvent or the like at the time of adsorption than activated carbon, and therefore has excellent heat resistance and low risk of heat generation. Further, since zeolite has a pore structure clearer than that of activated carbon, adsorption performance to organic solvents and the like is excellent. In the case of zeolite, the zeolite is in the form of powder having an average particle diameter of 1 μm or more and 20 μm or less. The zeolite is a naturally occurring zeolite, but is suitable for artificially synthesizing zeolite. Specifically, the beta-type, ZSM-5-type, ferrierite (ferrierite) type, mordenite (morbenite) type, L-type, Y-type, A-type and the like are included.
The adsorbent in the embodiment is more preferably a high silica zeolite having a high silica/alumina ratio. This is because the high-silicon zeolite is less susceptible to moisture and humidity in the gas to be treated, for example, by adsorbing an organic solvent from the gas to be treated. The silica/alumina ratio is preferably 15 or more, more preferably 50 or more.
The adsorbent element of an embodiment comprises at least one adsorbent material. One or more of the various activated carbons and zeolites described above may be selected. In the case of selecting a plurality of adsorbent materials, the ratio thereof is not particularly limited. The adsorbent may be appropriately selected according to the treatment conditions of the gas to be treated.
When the tap density of the adsorbent (Ax) is [ Axa ], the sphere volume calculated from the average particle diameter of the adsorbent particles assuming a spherical shape is [ Axb ], and the weight ratio of the adsorbent contained in the adsorbent sheet is [ Axc ], the average particle number [ Axd ] contained in each 1g of adsorbent element is represented by the following [ formula 1].
[ number 11]
Axd = (1/Axa) × (1/Axb) × (Axc/100) (g) … type 1
As described above, when the adsorbent is produced by mixing the adsorbent with the framework material such as the organic fiber and the inorganic fiber, the strength of the adsorbent tends to be lowered because the adsorbent reduces the entanglement points between the framework materials. Therefore, in order to obtain practical strength, it is preferable to suppress the total number of particles to a certain amount or less, and the total average particle number of at least 1 or more kinds of the adsorbent Ax contained in each 1g of the adsorbent sheet is represented by the following [ formula 2]]Preferably 8.0X10 12 The following is given.
[ number 12]
(Is the total average particle number of at least 1 or more kinds of adsorbing materials (Ax) contained in each 1g of the adsorbing sheet
[ organic fiber B-1]
The organic component (B) in the present embodiment is a component that acts as a carrier for the adsorbent (Ax) when the adsorbent is produced and also acts as a carrier after the adsorbent is molded, and is an organic fiber that is a pulp or a short fiber having a fiber length of about 10mm or less, in particular, a fiber that has an excellent heat resistance at 300 ℃ or higher, and has a melting point or a pyrolysis temperature. When the pyrolysis temperature is less than 300 ℃, a significant decrease in strength is inevitably generated at the high temperatures encountered in the adsorption and desorption operations. Specifically, the fiber is prepared from aramid fiber, meta-aramid fiber, polybenzimidazole (PBI), polybenzoxazole (PBO), polyimide, polyamide-imide, polyether ketone and the like.
[ organic Adhesives B-2]
The organic component (B) preferably contains, in addition to the heat-resistant organic component (B-1), a substance having a pyrolysis temperature of less than 300 ℃. The low-temperature decomposable organic component (B-2) has a function of a binder for causing the adsorbent (Ax) to be attached to the adsorbent at a high ratio in the production of the adsorbent. The organic component having low-temperature decomposability may be PVA (polyvinyl alcohol (polyvinyl alcohol)), starch, polyacrylonitrile, or the like, but PVA is preferable.
When the low-temperature decomposable organic component (B-2) causes a large coverage of the adsorbent (Ax) and the adsorption performance is significantly low, the coverage of the adsorbent (Ax) can be reduced by subjecting the adsorbent sheet to a high-temperature heat treatment to cause the low-temperature decomposable organic component (B-2) to become carbide or decompose and disappear.
[ inorganic Binder C ]
In the present embodiment, the inorganic binder (C) may be added to maintain the fixation of the adsorbing material (Ax) and the framework material of the adsorbing sheet at high temperature, and the groove portions 2a and the pad portions 2b constituting the honeycomb may be maintained fixed in the adsorbing sheet having a plurality of air passages as shown in fig. 3 and 4.
For example, it may be dissolved in water, the adhesive is uniformly dispersed on the sheet, cured by reaction, gelation, or the like at the time of heat treatment, and the adsorbent material and the framework material are firmly fixed at the time of curing. Further, it is preferable that the pyrolysis temperature is 300 ℃ or higher, and the reaction heat is generated by an organic solvent having high reactivity, but the catalytic performance is low due to ignition and combustion of the sheet, and it is difficult to cause a decrease in the adsorption performance of the adsorbent (Ax) due to the coating. For example, phosphate-based binders such as sodium hexametaphosphate and silicate-based binders such as sodium silicate are preferable.
An inorganic adhesive (C-1) for maintaining the fixation of the adsorbing material (Ax) and the fibrous component member and an inorganic adhesive (C-2) for maintaining the fixation of the groove portion 2a and the pad portion 2b constituting the honeycomb are not required to use the same kind of adhesive, and it is desirable to use an adhesive more advantageous in productivity.
[ Ax content of adsorbent ]
The amount of the adsorbent (Ax) contained in the adsorbent element of the present embodiment is preferably 40 wt% or more. In view of the adsorption performance, productivity, and falling of the adsorbent, 50 wt% or more is preferable. When the content of the adsorbent (Ax) is less than 40%, sufficient adsorption performance cannot be obtained. The upper limit of the weight of the adsorbent is not limited, but the limit is 80 wt% or less to maintain the shape of the adsorbent element. When it exceeds 80% by weight, the softness of the adsorption sheet becomes insufficient and difficult to process. The amount of the organic component (B) included in the adsorbing element of the present embodiment is 5 to 60% by weight of the total amount of the organic component used in the production of the precursor of the adsorbing element (precursor element) and the thermal oxide used in the heat treatment.
When the content of the organic component (B) is less than 5%, the loading capacity of the adsorbent is insufficient, and when the content is 60% or more, the inconvenience arises that the amount of the adsorbent to be used must be reduced. The amount of the inorganic binder component (C) contained in the adsorption element of the present embodiment is 5 to 30% by weight. If the amount is less than 5% by weight, the fixation between the adsorbent (Ax) and the matrix material is poor, and if it is 30% by weight or more, the flexibility is poor, which is not preferable.
[ Honeycomb Structure ]
In the structure of the adsorbing element of the present embodiment, the honeycomb structure is preferable from the viewpoints of mechanical strength and manufacturing cost, and the number of cells is 30 cells/cm 2 About 70/cm 2 Is good. Further preferably, the number of cells is 50 to 70 cells/cm 2 . When the number of cells is less than 30/cm 2 When the adsorption performance is reduced, the adsorption capacity exceeds 70 pieces/cm 2 In this case, the thickness of the sheet constituting the partition walls of the honeycomb structure needs to be reduced, and the mechanical strength of the sheet becomes weak, so that the sheet cannot be produced. The honeycomb structure has a honeycomb shape, as shown in FIG. 1, of 1 to 3mm in wave height and 2 to 4mm in wavelength, although the honeycomb shape is not particularly limited. Further preferably, the wave height is 1mm to 1.6mm and the wavelength is 2mm to 2.6mm. Here, the honeycomb structure refers to a three-dimensional structure composed of a plurality of small spaces (honeycomb shape) surrounded by side walls.
In the present embodiment, the thickness of the partition walls of the honeycomb structure constituting the adsorbing element is preferably 0.16mm to 0.25 mm. If the thickness is less than 0.16mm, the thickness of the sheet constituting the partition wall needs to be thinner, and the mechanical strength of the sheet becomes weak, so that the sheet cannot be produced. If the thickness exceeds 0.25mm, the separator becomes thick, and the above-mentioned number of cells cannot be obtained.
In the present embodiment, the grammage of the sheet constituting the adsorbing element is 65g/m 2 ～90g/m 2 Preferably, it is. When the particle size is less than 65g/m 2 In this case, the mechanical strength of the sheet becomes weak, and the mechanical strength of the honeycomb structure after heat treatment cannot be maintained. Over 90g/m 2 In this case, the partition wall becomes thick, and the number of cells cannot be obtained.
[ method for producing adsorption element ]
The adsorption element of the present embodiment can be manufactured as follows: the method comprises the steps of preparing an adsorbent (Ax), an organic component (B) and an inorganic binder (C) into a honeycomb-shaped honeycomb (precursor element) by using a honeycomb molding binder, and then subjecting the precursor element to a heat treatment at a temperature equal to or lower than the melting point of the heat-resistant organic component of the organic component (B) and equal to or higher than the decomposition temperature of the low-temperature decomposable organic component for 1 to 60 minutes to thermally oxidize and decompose the low-temperature decomposable organic component, thereby causing most of the low-temperature decomposable organic component to become carbide or to decompose and disappear.
[ considerations of B-1 and B-2 in the manufacturing method ]
The organic component (B) used for producing the adsorption element of the present embodiment preferably uses a low-temperature decomposable organic component (B-2) which is pyrolyzed at 150 to 300℃in addition to the heat-resistant organic fiber (B-1) such as the above-mentioned aramid fiber. The low-temperature decomposable organic component (B-2) functions as a binder for binding the (Ax) component to the (B-1) component and the (B-1) component during wet papermaking. Since the component (B-2) covers the sheet-like material and the adsorbing material of the final adsorbing element (adsorbing element of the present embodiment) after the honeycomb molding, when the adsorbing performance is significantly impaired, the component (B-2) can be subjected to a high-temperature heat treatment to change it into carbide or decompose it to disappear, and the covering of the adsorbing material on the final adsorbing element (adsorbing element of the present embodiment) can be reduced.
When the sheet and the honeycomb are heat-treated, the heat treatment is preferably performed in an air atmosphere using a heating oven or the like. The heat treatment temperature is lower than the melting point or decomposition temperature (T1 ℃) of the heat-resistant organic component (B-1), preferably 5 to 20 ℃ (T1-5 to T1-20 ℃) and higher than the decomposition temperature (T2 ℃) of the low-temperature decomposition component (B-2), preferably 100 to 200 ℃ (T2+100 to T2+200 ℃) and the treatment time at this temperature is 1 to 60 minutes, preferably 1 to 30 minutes. Typically from 350℃to 450℃for 1 to 10 minutes.
The planar compressive strength of the adsorbing element is preferably 3kPa or more. At an intensity of less than 3kPa, the adsorbing element is easily crushed, and a large number of air passages are crushed to disappear, so that the performance as the adsorbing element cannot be exerted, and thus it is not practical.
Gram weight (g/m) of adsorbent sheet 2 ) There are no particular restrictions, but it is preferably 10g/m 2 ～200g/m 2 . When the particle size is less than 10g/m 2 In this case, the mechanical strength of the sheet is weakened, and the mechanical strength of the honeycomb structure cannot be maintained. If it exceeds 200g/m 2 The thickness of the sheet becomes too thick, so that the sheet loses flexibility and the sheet cracks and the adsorbing material falls off easily.
Example (example)
The method for measuring the properties of the adsorption sheet according to the present embodiment is as follows. Various characteristics of each example and each comparative example are shown in fig. 5.
(1) Method for measuring tap density of adsorption material
About 40g of the adsorbent material was placed in a constant volume container and dried in vacuo at 180℃for 15 hours or more. After cooling in the dryer for 20 minutes, the dry mass was measured to a number of bits of 0.1 mg. The mass of the dried sample was S (g). The whole dry sample was placed in a 200mL measuring cylinder, and the bottom surface of the measuring cylinder was tapped (the bottom surface of the measuring cylinder was tapped) for 3 minutes. The number of bits from volume (mL) to 1mL after 3 minutes was read. If this is used as the filling volume A (mL), the tap density L (g/mL) is determined by the following formula. In addition, since 1mL is 1cm 3 Thus the unit g/mL and g/cm of tap density L 3 Synonymous.
[ number 13]
L (g/mL) =S (g)/(A (mL) … type 3)
(2) Method for measuring average particle diameter of adsorbent and method for calculating sphere volume when spherical particles are assumed
The average particle diameter of the adsorbent is calculated by observing the crystal particle diameter of the adsorbent by SEM image in advance, and measuring the average particle diameter by a laser diffraction scattering particle size distribution measuring device when the crystal particle diameter is 3 μm or more, and measuring the average particle diameter by SEM image analysis when the crystal particle diameter is less than 3 μm.
< method for measuring average particle diameter by laser diffraction/scattering particle size distribution measuring apparatus >
The measuring apparatus used was LA-950V2 manufactured by horiba, inc., the measuring cell used was a wet circulation cell (flow rate measuring cell), sodium hexametaphosphate (0.1 mass% aqueous solution) was used as a dispersion medium, and an aluminum silicate-water system (refractive index: 1.66-1.33) was used as a refractive index setting of the object to be measured.
[ measurement procedure ]
1. A predetermined amount of dispersion medium was injected into the measuring cell, and initial adjustment of the optical system and blank measurement were performed.
2. After the blank measurement, an adsorption material was added to the cell so that the transmittance of the dispersion medium was in the range of about 90% to 70%.
3. After ultrasonic waves (frequency 20 kHz) were applied for several seconds for defoaming, 1 measurement was performed.
4. After the measurement, ultrasonic waves were applied for a predetermined time (5 minutes) to disperse the sample, and the measurement was performed again.
5. The data measured again after applying the ultrasonic wave for a prescribed time (5 minutes) was analyzed, and the median particle diameter (particle diameter with a cumulative frequency of 50%) was taken as the average particle diameter.
< method for measuring average particle diameter by SEM image analysis >
The measuring device used a Hitachi scanning electron microscope (SU 1510) with an acceleration voltage of 15.0kV.
[ measurement procedure ]
1. Double faced adhesive tape was attached to the SEM observation table, and the adsorbent material was spread on the double faced adhesive tape, and excess adsorbent material was removed.
2. Platinization was performed on an SEM observation stage coated with the adsorbent material.
3. The observation stage of 2 was set to the SEM image observation apparatus.
4. At the above acceleration voltage, 3000 times of pictures were taken at 3 different positions.
5. Photographs taken 3000 times were blanket printed with A4 paper.
6. 2 diagonal lines were drawn on the printed photograph with a pencil, 20 particles with well-defined boundaries on the diagonal lines were selected, and 2 points of the short diameter and the long diameter were measured with a ruler. The length of the scale (μm) of the SEM photograph was measured with a scale, and the short diameter and the long diameter of the particles measured with the scale were converted into μm. .
7. A photograph was taken of 3 pieces of the particles at a magnification of 3000 times during the operation of 6. The short diameter and the long diameter of the total of 60 particles were calculated, and the average value of all the values was regarded as the average particle diameter (. Mu.m) obtained by SEM observation.
< method for calculating sphere volume assuming spherical particle >
Assuming that the average particle diameter calculated by laser diffraction or SEM image analysis is R (μm), the sphere volume Q (cm) of each particle is given when the particle is spherical 3 And/or) is obtained from the following equation 4.
[ number 14]
Q(cm 3 /number) = [4/3]×(R×10 -4 /2) 3 X 3.14 … type 4
(3) Specific strength measuring method
Measured according to JIS-P-8113 "test method of paper and paperboard-stretching characteristics". The test width was 15mm and the length was 50mm.
(4) Method for measuring plane compression strength
Corrugated board according to JIS-Z-0403-1' part 1: planar compressive Strength test method. The test width was 30mm and the length was 30mm.
The adsorption element of the present invention is described in detail based on the following examples and comparative examples.
Example 11 ]
As the adsorbent A1, 37.5% by weight of a tap density of 0.54g/cm was used 3 As the adsorbent A2, a ZSM-5 (MFI) zeolite having an average particle diameter of 3.3 μm as measured by laser diffraction and a tap density of 0.36g/cm of 37.5% by weight was used 3 As the heat-resistant organic component, 17 wt% of slurry-like or short-fiber-like aramid fibers (heat-resistant) were used, which were Y-type (FAU) zeolite having an average particle diameter of 1.2 μm as calculated by SEM image analysisThe machine comprises the following components: b-1) as the pyrolyzed organic binder, 8 wt% PVA (low temperature pyrolyzable organic component: b-2) producing a sheet-like article by using a wet papermaking apparatus to have a grammage of 75g/m 2 Is a weight of (c).
Next, the sheet was immersed in a 7 wt% aqueous solution of sodium hexametaphosphate as an inorganic binder, and dried in air at 100 ℃, and sodium hexametaphosphate was fixed in a 5 wt% sheet to obtain a precursor sheet.
Then, using a honeycomb molding machine, the precursor sheet was molded into a honeycomb number of 15 pieces/cm using a polyvinyl acetate emulsion having a solid content of 50% of the binder for honeycomb molding 2 Is a honeycomb (adsorbent element precursor). The amount of the binder for honeycomb molding used at this time was about 3% by weight based on the weight of the sheet after impregnation. The honeycomb was then heat treated in a sintering furnace at 400 c for about 3 minutes in air to obtain an adsorption element.
Example 12 ]
As the adsorbent A1, 37.5% by weight of a tap density of 0.39g/cm was used 3 A ZSM-5 (MFI) zeolite having an average particle diameter of 9.9 μm obtained by laser analysis was used as the adsorbent A2, and a tap density of 0.34g/cm was 37.5% by weight 3 Y-type (FAU) zeolite having an average particle diameter of 0.7 μm as calculated by SEM photograph analysis, 17 wt% of pulp-like and short-fiber-like aramid fibers (heat-resistant organic component: B-1) as heat-resistant organic components, 8 wt% of PVA (low-temperature pyrolysis organic component: B-2) as pyrolysis organic binder, and a wet papermaking apparatus were used to prepare a sheet having a grammage of 100g/m 2 Is a weight of (c).
Next, the sheet was immersed in a 7 wt% aqueous solution of sodium hexametaphosphate as an inorganic binder, and dried in air at 100 ℃, and sodium hexametaphosphate was fixed to a 5 wt% sheet to obtain a precursor sheet.
Then, using a honeycomb molding machine, the precursor sheet was molded into a honeycomb number of 15 pieces/cm using a polyvinyl acetate emulsion having a solid content of 50% of the binder for honeycomb molding 2 Is a honeycomb (adsorbent element)A precursor). The amount of the binder for honeycomb molding used at this time was about 3% by weight based on the weight of the sheet after impregnation. The honeycomb was then heat treated in a sintering furnace at 400 c for about 3 minutes in air to obtain an adsorption element.
Example 13 ]
As the adsorbent A1, 60% by weight of a catalyst having a tap density of 0.54g/cm was used 3 ZSM-5 (MFI) zeolite having an average particle diameter of 3.2 μm obtained by laser analysis, and tap density of 0.36g/cm was used as the adsorbent A2 at 37.5% by weight 3 Y-type (FAU) zeolite having an average particle diameter of 1.2 μm as calculated by SEM photograph analysis, 17 wt% of pulp-like and short-fiber-like aramid fibers (heat-resistant organic component: B-1) as heat-resistant organic components, 8 wt% of PVA (low-temperature pyrolysis organic component: B-2) as pyrolysis organic binder, and a wet papermaking apparatus were used to prepare a sheet having a grammage of 75g/m 2 Is a weight of (c).
Next, the sheet was immersed in a 7 wt% aqueous solution of sodium hexametaphosphate as an inorganic binder, and dried in air at 100 ℃, and sodium hexametaphosphate was fixed to a 5 wt% sheet to obtain a precursor sheet.
Then, using a honeycomb molding machine, the precursor sheet was molded into a honeycomb number of 15 pieces/cm using a polyvinyl acetate emulsion having a solid content of 50% of the binder for honeycomb molding 2 Is a honeycomb (adsorbent element precursor). The amount of the binder for honeycomb molding used at this time was about 3% by weight based on the weight of the sheet after impregnation. The honeycomb was then heat treated in a sintering furnace at 400 c for about 3 minutes in air to obtain an adsorption element.
Example 14 ]
As the adsorbent A1, 75% by weight of a catalyst having a tap density of 0.39g/cm was used 3 ZSM-5 (MFI) zeolite having an average particle diameter of 9.9 μm obtained by laser analysis, 17% by weight of pulp-like and short-fiber-like aramid fibers (heat-resistant organic component: B-1) as heat-resistant organic component, and 8% by weight of PVA (low-temperature pyrolysis organic component: B-2) as pyrolysis-type organic binderA sheet was produced by using a wet papermaking apparatus so that the grammage was 75g/m 2 Is a weight of (c).
Next, the sheet was immersed in a 20 wt% aqueous solution of sodium hexametaphosphate as an inorganic binder, and dried in air at 100 ℃, and sodium hexametaphosphate was fixed to a 5 wt% sheet to obtain a precursor sheet.
Then, using a honeycomb molding machine, the precursor sheet was molded into a honeycomb number of 15 pieces/cm using a polyvinyl acetate emulsion having a solid content of 50% of the binder for honeycomb molding 2 Is a honeycomb (adsorbent element precursor). The amount of the binder for honeycomb molding used at this time was about 3% by weight based on the weight of the sheet after impregnation.
Comparative example 11 ]
As the adsorbent A1, 15% by weight of a catalyst having a tap density of 0.39g/cm was used 3 ZSM-5 (MFI) zeolite having an average particle diameter of 10.7 μm obtained by laser analysis was used as the adsorbent A2, and 60% by weight of a tap density of 0.34g/cm was used 3 Y-type (FAU) zeolite having an average particle diameter of 0.7 μm as calculated by SEM image analysis, 17 wt% of pulp-like and short-fiber-like aramid fibers (heat-resistant organic component: B-1) as heat-resistant organic components, 8 wt% of PVA (low-temperature pyrolysis organic component: B-2) as pyrolysis organic binder, and a wet papermaking apparatus were used to prepare a sheet having a grammage of 75g/m 2 Is a weight of (c).
Next, the sheet was immersed in a 20 wt% aqueous solution of sodium hexametaphosphate as an inorganic binder, and dried in air at 100 ℃, and sodium hexametaphosphate was fixed to a 5 wt% sheet to obtain a precursor sheet.
Then, using a honeycomb molding machine, the precursor sheet was molded into a honeycomb number of 15 pieces/cm using a polyvinyl acetate emulsion having a solid content of 50% of the binder for honeycomb molding 2 Is a honeycomb (adsorbent element precursor). However, since the strength of the sheet is weak, cracks and breaks of the sheet are remarkable at the time of honeycomb molding, and proper honeycomb molding cannot be performed.
Comparative example 12 ]
As the adsorbent A1, 15% by weight of a catalyst having a tap density of 0.54g/cm was used 3 ZSM-5 (MFI) zeolite having an average particle diameter of 3.2 μm obtained by laser analysis, 60 wt% of tap density of 0.36g/cm was used as the adsorbent A2 3 Y-type (FAU) zeolite having an average particle diameter of 1.3 μm as calculated by SEM image analysis, 17 wt% of pulp-like and staple-fiber-like aramid fibers (heat-resistant organic component: B-1) as heat-resistant organic components, 8 wt% of PVA (low-temperature pyrolysis organic component: B-2) as pyrolysis organic binder, and a wet papermaking apparatus were used to prepare a sheet having a grammage of 75g/m 2 Is a weight of (c).
Then, using a honeycomb molding machine, the precursor sheet was molded into a honeycomb number of 15 pieces/cm using a polyvinyl acetate emulsion having a solid content of 50% of the binder for honeycomb molding 2 Is a honeycomb (adsorbent element precursor). However, since the strength of the sheet is weak, cracks and breaks of the sheet are remarkable at the time of honeycomb molding, and proper honeycomb molding cannot be performed.
Comparative example 13 ]
As the adsorbent A1, 75% by weight of a catalyst having a tap density of 0.34g/cm was used 3 Y-type (FAU) zeolite having an average particle diameter of 0.7 μm as calculated by SEM image analysis, 17 wt% of pulp-like and short-fiber-like aramid fibers (heat-resistant organic component: B-1) as heat-resistant organic components, 8 wt% of PVA (low-temperature pyrolysis organic component: B-2) as pyrolysis organic binder, and a wet paper machine was used to prepare a sheet having a grammage of 75g/m 2 Is a weight of (c).
Next, the sheet was immersed in a 20 wt% aqueous solution of sodium hexametaphosphate as an inorganic binder, and dried in air at 100 ℃, and sodium hexametaphosphate was fixed to a 5 wt% sheet to obtain a precursor sheet. Thereafter, the adsorbent sheet was obtained by heat-treating in a sintering furnace at 400℃for about 3 minutes in air.
Then, using a honeycomb molding machine, the precursor sheet is molded into a honeycomb number by using a polyvinyl acetate emulsion having a solid content of 50% of the binder for honeycomb molding 15 pieces/cm 2 Is a honeycomb (adsorbent element precursor). However, since the strength of the sheet is weak, cracks and breaks of the sheet are remarkable at the time of honeycomb molding, and proper honeycomb molding cannot be performed.
The adsorbent element of the present embodiment has at least 1 or more adsorbent materials, and in order to achieve both the strength of the adsorbent element and the high content ratio of the adsorbent materials, the total particle count included in the adsorbent element calculated from the bulk density and the particle diameter of the adsorbent materials is appropriately set, and organic components having a melting point or pyrolysis temperature of 300 ℃ or more and organic components having a pyrolysis temperature of less than 300 ℃ and inorganic binders are used as framework raw materials, whereby the obtained adsorbent element is excellent in flexibility and strength, and further, since the content ratio of the adsorbent materials is extremely high, the adsorbent performance is excellent.
As described above, there is a significant difference in the strength of the adsorbent element depending on the total number of adsorbent material particles contained in the adsorbent element, by setting the total number of particles to 8.0X10 12 Hereinafter, an adsorption element having a sufficient practical strength was obtained.
The presently disclosed embodiments are considered in all respects to be illustrative and not restrictive. The scope of the invention is indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are intended to be embraced therein.
Claims (13)
1. An adsorption sheet comprising at least 1 or more adsorption materials Ax, an organic component B, and an inorganic binder C, wherein the adsorption materials Ax are as follows: x=1, 2,3 … n,
the organic component B comprises an organic fiber B-1 and an organic component B-2, wherein the organic fiber B-1 is a fiber made of aramid, meta-aramid, polybenzimidazole, polybenzoxazole, polyimide, polyamide imide and polyether ketone,
the melting point or pyrolysis temperature of the organic fiber B-1 is above 300 ℃, the organic component B-2 has low-temperature decomposability for pyrolysis at 150-300 ℃,
the amount of the adsorbent Ax contained in the adsorbent sheet is 40 to 80 wt% of the adsorbent sheet, the amount of the organic component B contained in the adsorbent sheet is 5 to 60 wt% of the total amount of the organic component and the thermal oxide thereof used in producing the adsorbent sheet,
the tap density of the adsorbent Ax was Axa,
When the adsorbent particles are spherical, the sphere volume calculated from the average particle diameter of the adsorbent particles is Axb,
The weight ratio of the adsorbent contained in the adsorbent sheet was Axc%,
the average particle number Axd contained in each 1g of the adsorbent sheet is represented by the following formula 1,
axd = (1/Axa) × (1/Axb) × (Axc/100) (g) … type 1
The total average particle number of at least 1 or more of the adsorbent materials Ax contained per 1g of the adsorbent sheet is represented by the following formula 2,
is the total average particle number of at least 1 or more kinds of the adsorbing materials Ax contained in each 1g of the adsorbing sheet,
the specific strength of the adsorption sheet is more than 2 N.m/g.
2. The absorbent sheet according to claim 1, wherein the absorbent material Ax has a tap density of 0.1g/cm 3 The above.
3. An adsorption sheet according to claim 1, wherein the adsorption material Ax is a zeolite.
4. A method for producing an adsorption sheet comprising at least 1 or more adsorption materials Ax, an organic component B, and an inorganic binder C, wherein the adsorption materials Ax are as follows: x=1, 2,3 … n,
the method optionally comprises heat treatment after forming the sheet-like material by wet method, wherein the heat treatment temperature is lower than the melting point or decomposition temperature of the heat-resistant organic fiber and B-1, and higher than the decomposition temperature of the organic component B-2,
the method comprises that when the heat treatment is carried out, the organic component B comprises organic fibers B-1, and when the heat treatment is not carried out, the organic component B comprises organic fibers B-1 and organic components B-2,
the organic fiber B-1 is a fiber made of aramid fiber, meta-aramid fiber, polybenzimidazole, polybenzoxazole, polyimide, polyamide imide and polyether ketone,
The melting point or pyrolysis temperature of the organic fiber B-1 is above 300 ℃, the organic component B-2 has low-temperature decomposability for pyrolysis at 150-300 ℃,
the amount of the adsorbent Ax contained in the adsorbent sheet is 40 to 80 wt% of the adsorbent sheet, the amount of the organic component B contained in the adsorbent sheet is 5 to 60 wt% of the total amount of the organic component and the thermal oxide thereof used in producing the adsorbent sheet,
the tap density of the adsorbent Ax was Axa,
When the adsorbent particles are spherical, the sphere volume calculated from the average particle diameter of the adsorbent particles is Axb,
The weight ratio of the adsorbent contained in the adsorbent sheet was set to Axc%,
the average particle number Axd contained in each 1g of the adsorbent sheet is represented by the following formula 1,
axd = (1/Axa) × (1/Axb) × (Axc/100) (g) … type 1
The total average particle number of at least 1 or more of the adsorbent materials Ax contained per 1g of the adsorbent sheet is represented by the following formula 2,
is obtained by 1g of the adsorption sheetThe total average particle number of at least 1 or more kinds of the adsorbing materials Ax contained,
the specific strength of the adsorption sheet is more than 2 N.m/g.
5. The method for producing an adsorption sheet according to claim 4, wherein the adsorption sheet further comprises an organic fiber B-1 having a melting point or pyrolysis temperature of 300 ℃ or higher and an organic component B-2 having a pyrolysis temperature of less than 300 ℃ in addition to the adsorption material Ax.
6. The method for producing an adsorption sheet according to claim 5, wherein the organic fiber is at least one polymer selected from the group consisting of an aramid polymer, a benzimidazole polymer, a benzoxazole polymer and a polyimide polymer.
7. The method for producing an adsorption sheet according to claim 5 or claim 6, wherein the organic component is at least one selected from the group consisting of polyvinyl alcohol-based polymers, polyacrylonitrile-based polymers and polyvinylpyrrolidone-based polymers.
8. An adsorption element having a honeycomb structure using an adsorption sheet having a plurality of air channels, wherein the adsorption sheet contains at least 1 or more adsorption materials Ax, an organic component B, and an inorganic binder C, and the adsorption materials Ax are as follows: x=1, 2,3 … n,
optionally comprising performing a heat treatment at a temperature which is lower than the melting point or the decomposition temperature of the heat-resistant organic fiber B-1 and higher than the decomposition temperature of the organic component B-2 after the honeycomb is formed,
the method comprising the step of performing the heat treatment while the organic component B comprises the organic fiber B-1, the method comprising the step of performing the heat treatment while the organic component B comprises the organic component B-1 and the organic component B-2,
The organic fiber B-1 is a fiber made of aramid fiber, meta-aramid fiber, polybenzimidazole, polybenzoxazole, polyimide, polyamide imide and polyether ketone,
the melting point or pyrolysis temperature of the organic fiber B-1 is above 300 ℃, the organic component B-2 has low-temperature decomposability for pyrolysis at 150-300 ℃,
the amount of the adsorbent Ax contained in the adsorbent sheet is 40 to 80 wt% of the adsorbent sheet, the amount of the organic component B contained in the adsorbent sheet is 5 to 60 wt% of the total amount of the organic component and the thermal oxide thereof used in producing the adsorbent sheet,
the tap density of the adsorption material Ax was Axa,
When the adsorbent particles are spherical, the sphere volume calculated from the average particle diameter of the adsorbent particles is Axb,
The weight ratio of the adsorbing material Ax contained in the adsorbing sheet was Axc%,
the average particle number Axd contained per 1g of the adsorption sheet is represented by the following formula 1,
axd = (1/Axa) × (1/Axb) × (Axc/100) (g) … type 1
The total average particle number of at least 1 or more of the adsorbent materials Ax contained per 1g of the adsorbent sheet is represented by the following formula 5,
the average particle number of at least 1 kind of the adsorption material Ax contained in each 1g of the adsorption sheet is equal to or more than 3 kPa.
9. The adsorbent element of claim 8, wherein the adsorbent sheet has fibers as a skeletal material.
10. An adsorption element according to claim 8 or claim 9, wherein the thickness of the adsorption sheet is 0.16-0.25 mm.
11. According to claim8 or 9, wherein the honeycomb structure has a honeycomb number of 30/cm 2 ～70/cm 2 。
12. An adsorption element according to claim 8 or claim 9, wherein the adsorption material Ax has a tap density of 0.1g/cm 3 The above.
13. An adsorption element according to claim 8 or claim 9, wherein the adsorption material Ax is a zeolite.
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| JP2018-108047 | 2018-06-05 | ||
| JP2018108048A JP6516047B1 (en) | 2018-06-05 | 2018-06-05 | Adsorption element |
| JP2018-108048 | 2018-06-05 | ||
| JP2018108047A JP7183578B2 (en) | 2018-06-05 | 2018-06-05 | Adsorption sheet and manufacturing method thereof |
| PCT/JP2019/022003 WO2019235429A1 (en) | 2018-06-05 | 2019-06-03 | Adsorbing sheet, adsorbing sheet production method, and adsorbing element |
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| TWI818996B (en) | 2023-10-21 |
| KR20210015932A (en) | 2021-02-10 |
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| TW202003103A (en) | 2020-01-16 |
| CN112218711A (en) | 2021-01-12 |
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