CN106794456A - Photocatalyst Composite and its manufacture method - Google Patents
Photocatalyst Composite and its manufacture method Download PDFInfo
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- CN106794456A CN106794456A CN201580045815.4A CN201580045815A CN106794456A CN 106794456 A CN106794456 A CN 106794456A CN 201580045815 A CN201580045815 A CN 201580045815A CN 106794456 A CN106794456 A CN 106794456A
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- Prior art keywords
- photocatalyst
- mentioned
- photocatalyst composite
- granular
- composite
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 500
- 239000002131 composite material Substances 0.000 title claims abstract description 307
- 238000000034 method Methods 0.000 title claims description 157
- 238000004519 manufacturing process Methods 0.000 title claims description 61
- 239000002245 particle Substances 0.000 claims abstract description 186
- 239000002250 absorbent Substances 0.000 claims abstract description 146
- 230000002745 absorbent Effects 0.000 claims abstract description 146
- 239000003054 catalyst Substances 0.000 claims description 111
- 239000000203 mixture Substances 0.000 claims description 67
- 230000008569 process Effects 0.000 claims description 61
- 239000000853 adhesive Substances 0.000 claims description 59
- 230000001070 adhesive effect Effects 0.000 claims description 59
- 229910021536 Zeolite Inorganic materials 0.000 claims description 39
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 39
- 239000010457 zeolite Substances 0.000 claims description 39
- 238000000465 moulding Methods 0.000 claims description 32
- 239000006185 dispersion Substances 0.000 claims description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 16
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 16
- 238000009826 distribution Methods 0.000 claims description 15
- 230000004044 response Effects 0.000 claims description 11
- 230000008859 change Effects 0.000 claims description 10
- 238000001802 infusion Methods 0.000 claims description 10
- 238000003856 thermoforming Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 239000004113 Sepiolite Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052624 sepiolite Inorganic materials 0.000 claims description 7
- 235000019355 sepiolite Nutrition 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 5
- 230000008023 solidification Effects 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 238000013007 heat curing Methods 0.000 claims description 3
- 238000001723 curing Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 67
- 230000002045 lasting effect Effects 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 94
- 239000003463 adsorbent Substances 0.000 description 39
- 238000000354 decomposition reaction Methods 0.000 description 39
- 230000000694 effects Effects 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 24
- 239000003795 chemical substances by application Substances 0.000 description 23
- 238000011156 evaluation Methods 0.000 description 23
- 238000010586 diagram Methods 0.000 description 15
- 238000007493 shaping process Methods 0.000 description 15
- 238000001179 sorption measurement Methods 0.000 description 11
- 230000007774 longterm Effects 0.000 description 10
- 238000005469 granulation Methods 0.000 description 9
- 230000003179 granulation Effects 0.000 description 9
- HIHOEGPXVVKJPP-JTQLQIEISA-N 5-fluoro-2-[[(1s)-1-(5-fluoropyridin-2-yl)ethyl]amino]-6-[(5-methyl-1h-pyrazol-3-yl)amino]pyridine-3-carbonitrile Chemical compound N([C@@H](C)C=1N=CC(F)=CC=1)C(C(=CC=1F)C#N)=NC=1NC=1C=C(C)NN=1 HIHOEGPXVVKJPP-JTQLQIEISA-N 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 7
- 239000002781 deodorant agent Substances 0.000 description 7
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 230000002186 photoactivation Effects 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000012798 spherical particle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229940084030 carboxymethylcellulose calcium Drugs 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 230000035943 smell Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 101000905241 Mus musculus Heart- and neural crest derivatives-expressed protein 1 Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Offer can make absorption property and the lasting Photocatalyst Composite of decomposability.Photocatalyst Composite (1) of the invention is contained：Absorbent particles (2) with transmitance；And photocatalyst granular (3), absorbent particles (2) and photocatalyst granular (3) exist with dispersity.
Description
Technical field
The present invention relates to Photocatalyst Composite and its manufacture method, more particularly to absorbent particles and photocatalyst granular
The Photocatalyst Composite and its manufacture method of the solid-state existed with dispersity.
Background technology
It is in the past known to combine to make decomposing volatile organic compound (VOC by adsorbent and photochemical catalyst：Volatile
Organic Compounds), the method that improves of the performance of odorous substance etc..
For example, disclosing the deodorant or odor removal filter for combining zeolite and photochemical catalyst in patent document 1,2.
Specifically, Figure 15 is the sectional view of the deodorant for schematically showing the record of patent document 1.As shown in figure 15,
The deodorant 101 that patent document 1 is recorded is using the covering zeolite granular 102 of particulate 103 of the photochemical catalyst of visible-light response type
Surface composition.According to the deodorant 101, can have a sufficient gas removal rate, and indoors, it is ultraviolet in automobile etc.
The gas also under the considerably less situation of line with stabilization removes ability.
In addition, the odor removal filter that patent document 2 is recorded is on the surface of the cellular formed body containing hydrophobic zeolite
It is supported with the composition of photochemical catalyst.Hydrophobic zeolite adsorbs odor pollutant and is difficult adsorption moisture, therefore can be in higher concentrations
Trapping odor pollutant.In addition, efficiently decomposing what is trapped by the effect supported in the photochemical catalyst on hydrophobic zeolite surface
Odor pollutant.Thus, adsorbent reactivation, sustainable utilization absorption affinity can be made, therefore deodorant power is very outstanding.
Prior art literature
Patent document
Patent document 1：Japanese Laid-Open Patent Publication " JP 2007-167699 publications (on July 5th, 2007 is open) "
Patent document 2：Japanese Laid-Open Patent Publication " JP 2002-136811 publications (on May 14th, 2002 is open) "
The content of the invention
Problems to be solved by the invention
But, in the composition that patent document 1,2 is recorded, following problem can be produced：The absorption property of adsorbent is insufficient,
The decomposability of photochemical catalyst cannot continue.
Specifically, in the composition that patent document 1,2 is recorded, it is and is supported with photochemical catalyst on the surface of adsorbent
Constitute.Therefore, photochemical catalyst is also limited to the whole surface of adsorbent by photochemical catalyst relative to the loading maximum of adsorbent
Layer covering amount.But, the amount of exposing on the surface of the loading more at most adsorbent of photochemical catalyst is fewer, therefore adsorbent becomes
Must be not exposed to decompose object.The result is that, it is impossible to give full play to the absorption property of adsorbent.
And, when used over time, supporting the photochemical catalyst in the surface of adsorbent can peel off, therefore photochemical catalyst
Amount it is not enough.As a result, the decomposability of photochemical catalyst is possible to reduce over time.
The present invention is to complete in view of the above problems, and absorption property and decomposability can be made its object is to provide one kind
Lasting Photocatalyst Composite.In addition, absorption property and decomposability can be taken into account another object of the present invention is to provide one kind
The Photocatalyst Composite of energy.
The scheme for solving problem
In order to solve the above problems, the Photocatalyst Composite of an embodiment of the invention is the photochemical catalyst of solid-state
Composition, contains：Absorbent particles, it has at least one party in transmitance and light reflective；And photocatalyst granular,
Above-mentioned Photocatalyst Composite is characterised by that above-mentioned absorbent particles and photocatalyst granular exist with dispersity.
Invention effect
An implementation method of the invention, plays following effect：A kind of Photocatalyst Composite can be provided, it can make
The absorption property of adsorbent and the decomposability of photochemical catalyst continue.In addition, an implementation method of the invention, also functions to
Following effect：The decomposability of a kind of Photocatalyst Composite, its absorption property that can take into account adsorbent and photochemical catalyst can be provided
Energy.
Brief description of the drawings
Fig. 1 is the schematic diagram of the outward appearance of the Photocatalyst Composite for briefly showing embodiments of the present invention 1.
Fig. 2 is the general of the evaluating apparatus that use in the gas absorption decomposability evaluation for show above-mentioned Photocatalyst Composite
Sketch map.
Fig. 3 is the coordinate diagram of the evaluation result of the gas absorption decomposability for showing above-mentioned Photocatalyst Composite.
Fig. 4 is the figure for showing to above-mentioned Photocatalyst Composite shoot the SEM image for obtaining.
Fig. 5 is to show shoot the SEM image for obtaining to the existing Photocatalyst Composite as comparison other
Figure.
Fig. 6 is to show to carry out the gas absorption performance of above-mentioned Photocatalyst Composite and existing Photocatalyst Composite
The coordinate diagram for comparing.
Fig. 7 is to show to carry out the gas decomposability of above-mentioned Photocatalyst Composite and existing Photocatalyst Composite
The coordinate diagram for comparing.
Fig. 8 is the sectional view of the Photocatalyst Composite for schematically showing embodiments of the present invention 2.
Fig. 9 is the sectional view of the Photocatalyst Composite for schematically showing embodiments of the present invention 3.
Figure 10 is the sectional view of the Photocatalyst Composite for schematically showing embodiments of the present invention 4.
Figure 11 is the stereogram of the outward appearance of the Photocatalyst Composite for schematically showing embodiments of the present invention 5.
Figure 12 is the sectional view of the Photocatalyst Composite for schematically showing embodiments of the present invention 5.
Figure 13 is the per unit absorbent particles amount by above-mentioned Photocatalyst Composite and existing Photocatalyst Composite
The coordinate diagram that is compared of gas absorption performance.
Figure 14 is the per unit photocatalyst granular by above-mentioned Photocatalyst Composite and existing Photocatalyst Composite
The coordinate diagram that the gas absorption performance of amount is compared.
Figure 15 is the sectional view of the deodorant for schematically showing the record of patent document 1.
Specific embodiment
(implementation method 1)
Hereinafter, embodiments of the present invention are described in detail.Additionally, embodiments described below is an example of the invention
Son, does not limit the content of invention.
[composition of Photocatalyst Composite 1]
First, the composition of the Photocatalyst Composite of present embodiment is illustrated using Fig. 1.Fig. 1 is to briefly show the present invention
Implementation method 1 Photocatalyst Composite 1 outward appearance schematic diagram.As shown in figure 1, the photochemical catalyst combination of present embodiment
Thing 1 is solid-state (solid), forms the aggregate that absorbent particles 2 and photocatalyst granular 3 exist with dispersity.And,
Space 6 is formed with Photocatalyst Composite 1.
Absorbent particles 2 can adsorb and/or decompose the decomposition object of Photocatalyst Composite 1.Absorbent particles 2 have
At least one party in transmitance and light reflective.Specifically, absorbent particles 2 have is absorbed photocatalyst granular 3
Wavelength light at least a portion transmitted through or reflection property, or with the wavelength for being absorbed photocatalyst granular 3
Light at least a portion transmitted through and a part reflection property.For example, absorbent particles 2 can include zeolite, sepiolite, Jie
The mixture of various (at least 2 kinds) materials among hole silica, atlapulgite or these materials.
The mineral such as zeolite, sepiolite, mesoporous silicon oxide and atlapulgite have in the ripple from visible ray near ultraviolet
Region medium wavelength long then absorptivity more long is lower, light transmission and light reflectivity sum property higher.The configuration of zeolite does not have
Be particularly limited to, can using BEA, CHA, EMT, ERI, FAU, FER, GIS, HEU, LTA, LTL, MAZ, MEI, MEL, MFI, MOR,
The various configurations such as MTW, OFF or MCM41, MCM48.In addition, zeolite can use natural type, synthesis type is could be used that.
The size (average grain diameter) of absorbent particles 2 is not particularly limited, in general such as diameter (feelings of spherical particle
Condition) or maximum length (situation of non-spherical particle) be more than 0.1 μm, less than 1 μm of degree.Absorbent particles 2 have light
The reasons why at least one party in transmittance and light reflective, is explained below.Additionally, the size (average grain diameter) of absorbent particles 2
Show to be distributed the value that meter is measured and is observed with SEM/TEM and determined by optical grain size.
Photocatalyst granular 3 can adsorb by absorbing light and/or decompose the decomposition object of Photocatalyst Composite 1.
That is, photocatalyst granular 3 is to show photocatalyst activity by irradiating the light of the wavelength with band gap energy above to it.
The wavelength of the light that photocatalyst granular 3 absorbs is not particularly limited.For example, photocatalyst granular 3 can be absorb visible ray and
Show the photochemical catalyst of the visible-light response type of photocatalyst activity, or absorb ultraviolet and show photochemical catalyst
The photochemical catalyst of the ultraviolet-responsive type of activity, can also be the photochemical catalyst of visible-light response type and the light of ultraviolet-responsive type
The mixture of catalyst.However, it is preferred to photochemical catalyst of the photocatalyst granular 3 for visible-light response type.
It is preferred that the photochemical catalyst of visible-light response type is for for example including WO3、W25O73、W20O58、W24O68Or theirs is mixed
The tungsten oxide of compound.Alternatively, it is also possible to be modified into by importing specific metal ion or importing nitrogen to oxygen position
Titanium dioxide (the TiO also worked in visible region2) it is used as the photochemical catalyst of visible-light response type.Visible-light response type
Photochemical catalyst can also be tungsten oxide with so improve after titanium dioxide mixture.
On the other hand, the photochemical catalyst of ultraviolet-responsive type can enumerate such as titanium dioxide (TiO2：Also referred to as aoxidize
Titanium) etc..
The size of photocatalyst granular 3 is not particularly limited, it is preferred that smaller than absorbent particles 2.Thus, can urge light
Catalyst particles 3 are reliably dispersed to the inside of Photocatalyst Composite 1.The size (average grain diameter) of photocatalyst granular 3 is preferably
Such as diameter (situation of spherical particle) or maximum length (situation of non-spherical particle) are more than 1nm, the journey of below 10nm
Degree.Additionally, the size (average grain diameter) of photocatalyst granular 3 is represented and being measured by optical grain size distribution meter and being used SEM/
The value that TEM is observed and determined.
In Photocatalyst Composite 1, the containing ratio (weight ratio) of absorbent particles 2 and photocatalyst granular 3 is as long as root
Set according to the purposes of Photocatalyst Composite 1, be not particularly limited.In the situation of the effect for paying attention to absorbent particles 2
Under, it is set to the Photocatalyst Composite 1 more than photocatalyst granular 3 containing absorbent particles 2.On the other hand, paying attention to
In the case of the effect of photocatalyst granular 3, the photochemical catalyst group more than absorbent particles 2 containing photocatalyst granular 3 is set to
Compound 1.For example, it is preferable to the weight ratio of the photocatalyst granular 3 of absorbent particles 2/ is 1~9, more preferably 1.5~4.By
This, the effect (absorption property) as absorbent particles 2 obtains the light of balance with the effect (decomposability) of photocatalyst granular 3
Carbon monoxide-olefin polymeric 1.
The ratio (voidage) in the space 6 in Photocatalyst Composite 1 can be arbitrarily set, it is preferred that for example relative to light
The volume % of volume ratio 100 of carbon monoxide-olefin polymeric 1 is 30~50 volume %.Here, voidage represents Photocatalyst Composite 1
It is apparent on volume void 6 (space) shared by ratio.Thus, there is the wavelength zone of light reflective in absorbent particles 2
Also can be same with the wavelength region with transmitance in domain, light is reached the inside of Photocatalyst Composite 1.In addition, decomposing
Object can be impregnated with space 6, and can fully be adsorbed in the absorbent particles 2 of the inside of Photocatalyst Composite 1.
As long as the form solid-state of Photocatalyst Composite 1, is not particularly limited.As shown in figure 1, in this embodiment party
In formula, in Photocatalyst Composite 1, absorbent particles 2 and photocatalyst granular 3 include block aggregate.Photochemical catalyst
Composition 1 can also be each forms, preferably bullet form such as powder, particle, bullet (pellet), honeycomb, film.
Additionally, Photocatalyst Composite 1 can also include absorbent particles 2 and photocatalyst granular 3, it is also possible to comprising it
Its composition.For example, it is also possible to comprising various adhesives etc..
[manufacture method of Photocatalyst Composite 1]
Next, the manufacture method of explanation Photocatalyst Composite 1.The manufacture method of Photocatalyst Composite 1 is without spy
Do not limit, for example, following manufacture method is contemplated that, wherein including：Dispersion step, makes absorbent particles 2 and photocatalyst granular
3 from the surface of Photocatalyst Composite 1 towards inner dispersion.
Specifically, in above-mentioned dispersion step, by powdered absorbent particles 2 and powdered photocatalyst granular
3 mixing, the aggregate of these particles are fixed and are configured to bulk.That is, the manufacture method of Photocatalyst Composite 1 is included：To inhale
Attached dose of particle 2 and the mixed processes of the mixing of photocatalyst granular 3；And make the He of absorbent particles 2 mixed by mixed processes
The forming process of the shaping of photocatalyst granular 3.Thus, Photocatalyst Composite 1 can be manufactured.
In addition, the condition shaped according to the fixation, can form space 6 in Photocatalyst Composite 1.For example, by powder
The absorbent particles 2 of last shape and powdered photocatalyst granular 3 are mixed with certain ratio, and the aggregate of these particles is fixed
After shaping (inside of Photocatalyst Composite 1 fixed shaping) is the bulk with space, will be powdered around it
Absorbent particles 2 and powdered photocatalyst granular 3 are mixed in other ratios, and by same or other shaping sides
Method makes its with carrying space fixed shaping (the fixed shaping on the surface of Photocatalyst Composite 1), to form free thus, it is possible to manufacture
The Photocatalyst Composite 1 of gap 6.In addition, in the manufacture method, as long as the powdered adsorbent when making each fixed shaping
Grain 2 is identical with the ratio of powdered photocatalyst granular 3, can just manufacture the ratio of components of absorbent particles and photocatalyst granular
Uniform Photocatalyst Composite.
The manufacturing process of Photocatalyst Composite 1 is not particularly limited, and can be carried out by ring mould mode or flat-die mode
Granulation, or can also be granulated by cuber.Can apply to other prilling process of the manufacture of Photocatalyst Composite 1
Spray drying, extruding pelletization can be enumerated, granulation, thermoforming granulation etc. is rotated.
In addition, in the case of by granulating manufacture Photocatalyst Composite 1, except absorbent particles 2 and photochemical catalyst
Beyond particle 3, it is also possible to mix other compositions.The typical case of other compositions is adhesive.For example, it is also possible to will be used as adhesive
Clay, CMC (carboxymethylcellulose calcium), resinae etc. organic or inorganic adhesive and absorbent particles 2 and photocatalysis
Agent particle 3 is mixed together and shapes, and thus manufactures Photocatalyst Composite 1.
So manufacture Photocatalyst Composite 1 from process and decompose object impregnability from the viewpoint of, preferably into
Shape is approximately spherical.Be configured to it is approximately spherical in the case of particle diameter (diameter) be not particularly limited, preferably such as 0.5mm with
On, the degree of below 5mm.In other words, particle diameter (diameter) is preferably formed as more than 0.5mm, the bullet form of the degree of below 5mm
Photocatalyst Composite 1.If particle diameter is less than 0.5mm, it may happen that difficult in terms for the treatment of, if greater than 5mm, then
It is possible that problem in terms of the impregnability of object is decomposed.
[effect of Photocatalyst Composite 1]
Then, the effect of Photocatalyst Composite 1 is illustrated.As described above, Photocatalyst Composite 1 includes absorbent particles
2 and photocatalyst granular 3.Absorbent particles 2 and photocatalyst granular 3 can adsorb and/or decompose Photocatalyst Composite 1
Decompose object.Decompose the free position that object can be gas or liquid.Decomposing object can enumerate such as toluene, two
Odorous substances such as the volatile organic solvents such as toluene, acetaldehyde (VOC), acetic acid, hydrogen sulfide, methyl mercaptan etc..Photocatalyst Composite 1
With by adsorbing or decomposing this decomposition object so as to the effect being removed, the use such as smelly eliminating, deodorant is thus suitable for
On the way.
Absorbent particles 2 typically have following feature：Adsorption rate is fast, but cannot proceed to inhale if saturation
It is attached.On the other hand, photocatalyst granular 3 typically has following feature：Decomposition rate is slow, but will not saturation and can persistently divide
Solution.Therefore, if absorbent particles 2 and photocatalyst granular 3 combined, absorbent particles 2 can rapid adsorption decomposition object
Thing, and the decomposition object decomposition for being adsorbed absorbent particles 2 using photocatalyst granular 3.Therefore, absorbent particles 2 are not
Can saturation.On the other hand, the decomposition rate of photocatalyst granular 3 depends on the concentration for decomposing object.When photocatalyst granular 3
When decomposition object to being adsorbed in absorbent particles 2 with high concentration is decomposed, decomposition rate also accelerates.Therefore, photocatalysis
Agent composition 1 can obtain absorbent particles 2 will not saturation and photocatalyst granular 3 the fast synergy of decomposition rate.
In the Photocatalyst Composite 1 of present embodiment, absorbent particles 2 and photocatalyst granular 3 are with dispersity
In the presence of.Thus, for example Photocatalyst Composite 1 is arranged in the gaseous environment for wanting to be removed, thus, it is possible to utilize adsorbent
The effect of particle 2 is adsorbed to removing object gas, and then photocatalyst granular 3 absorbs light, thus, it is possible to utilize photochemical catalyst
The effect of particle 3 will remove object gas and decompose.
In addition, in Photocatalyst Composite 1, photocatalyst granular 3 not only disperses to be present in Photocatalyst Composite 1
Most surface, also dispersion are present in inside.But, absorbent particles 2 have at least one party in transmitance and light reflective.Cause
This, in the case where absorbent particles 2 have transmitance, light can directly reach the photocatalyst granular 3 of inside.In addition,
Space 6 is formed with Photocatalyst Composite 1, therefore in the case where absorbent particles 2 have transmitance and with light
In the case of reflexive, light can be transferred through the photocatalyst granular 3 that space 6 reliably reaches inside.Particularly, zeolite, Hai Pao
The mineral such as stone are lower in the then absorptivity more long of the wavelength region medium wavelength from visible ray near ultraviolet, and light transmission reflects with light
Rate sum is higher.Therefore, as long as making absorbent particles 2 include transmitance zeolite high, sepiolite or their mixture,
The photocatalyst granular 3 inside enough light arrival can just be made.
So, in the Photocatalyst Composite 1 of present embodiment, with transmitance and light reflective at least one
The absorbent particles 2 and photocatalyst granular 3 of side exist with dispersity.Thus, can easily be processed, absorption will not be hindered
The adsorption capacity of agent particle 2 and ensure the photocatalyst granular 3 of q.s.Decomposed accordingly, it is capable to provide and play gas absorption high
Performance, gas decomposability is not easy to the Photocatalyst Composite 1 for reducing during long-term use.So as to can provide can make adsorbent
The absorption property of particle 2 and the lasting Photocatalyst Composite 1 of the decomposability of photocatalyst granular 3.In addition, can provide can be simultaneous
Turn round and look at the Photocatalyst Composite 1 of the decomposability of the absorption property and photocatalyst granular 3 of absorbent particles 2.
In addition, being formed with space 6 in the Photocatalyst Composite 1 of present embodiment.Thus, have in absorbent particles 2
In having a wavelength region of light reflective, also can be same with the wavelength region with transmitance, pass light through space 6 and reach light and urge
The inside of agent composition 1.In addition, decomposing object can be impregnated with space 6, and can be in the absorption inside Photocatalyst Composite 1
Adsorbed in agent particle 2.In addition, relative to 100 volume % of Photocatalyst Composite 1, make space 6 with 30 volume % with
The upper, ratio of below 50 volume % is formed, thus, it is possible to more reliably make light reach the inside of Photocatalyst Composite 1, and energy
Decomposition object is set fully to be adsorbed in the absorbent particles 2 of the inside of Photocatalyst Composite 1.
[evaluation of Photocatalyst Composite 1]
(manufacture of the Photocatalyst Composite 1 of evaluation object)
Photochemical catalyst uses tungsten oxide, adsorbent to use the zeolite of ZSM-5 types, adhesive to use CMC.Make tungsten oxide：Boiling
Stone：The weight ratio of adhesive is 1：8.5：0.5, extruding pelletization and rotation granulation is applied in combination to manufacture the photocatalysis of bullet form
Agent composition 1.
(manufacture of the Photocatalyst Composite of comparison other (comparative example 1,2))
[comparative example 1] is supported with the Photocatalyst Composite of photochemical catalyst in ceramic surface
Photochemical catalyst uses tungsten oxide, ceramics to use the ceramic filter of porous (spongy).Make tungsten oxide：Ceramic filter
The weight ratio of device is 1：9, the Photocatalyst Composite that photochemical catalyst is supported with ceramic surface is manufactured by impregnating.
[comparative example 2] is supported with the Photocatalyst Composite of photochemical catalyst in zeolite surface
Photochemical catalyst uses tungsten oxide, adsorbent to use the zeolite bullet of β types.Make tungsten oxide：The weight ratio of zeolite is
1.5：8.5, the Photocatalyst Composite that photochemical catalyst is supported with zeolite surface is manufactured by impregnating.Additionally, right evaluating
As different from the configuration of the zeolite used in comparative example 2, but in the case of with the powder of each zeolite of Object Evaluation, separately really
Accept with equal ability (velocity of gas sorption=1.6 [h-1]).
(evaluation method)
Fig. 2 is to show that the measurement system evaluated for the gas absorption decomposability for carrying out Photocatalyst Composite 1 (is evaluated
Device 10) skeleton diagram.As shown in Fig. 2 evaluating apparatus 10 include shading case 11, light source 12, gas pouch 13 and culture dish 14.
Light source 12 is set by the direction shone on the ground from the internal roof center of shading case 11.Gas pouch 13 is arranged at the ground of shading case 11
Face center, culture dish 14 is accommodated in the inside of gas pouch 13.Shading case 11 be prevent light shading case 11 it is inside and outside it
Between transmitted through structure, the light beyond the light sent from light source 12 will not be irradiated to gas pouch 13.Light source 12 use wavelength for
The blue led of 450nm, is irradiated with the radiant illumination of about 7mW/cm2.Gas pouch 13 has the capacity of 5L, in wavelength 450nm
It is nearby transparent, is that can be confined to the structure that gas cannot come in and go out.Culture dish 14 is made up of quartz glass, herein place want into
The object (Photocatalyst Composite 1) of the measure of promoting the circulation of qi body adsorption-decomposition function speed.
Decompose object gas using aldehydes gas as VOC, as various smells the reason for gas representative.Determine gas
The time dependence of bulk concentration change, is taken as the logarithm of gas concentration, when transverse axis is taken as the time, by the size of slope in the longitudinal axis
[h-1] is defined as gas absorption decomposition rate.The time of the change in concentration that the decomposition of absorption and gas for gas brings according to
For bad property, because the logarithm is in line, therefore either which kind of initial concentration calculating all without influence slope, but herein
If the initial concentration of gas is for about 500ppm and is measured.That is, by the aldehydes gas of 500ppm be placed with measure
The culture dish 14 of object (Photocatalyst Composite 1) encloses gas pouch 13 together, from the irradiation light of light source 12, determines gas concentration
The temporal correlation of change.The measure of gas concentration uses the acetaldehyde detection pipe that gas technology (ガ ス テ ッ Network) is manufactured
No.92。
Additionally, now light irradiation can not also be carried out from light source 12, effect according to absorbent particles 2 is thus only determined
Velocity of gas sorption.
(evaluation result)
By above-mentioned evaluation method, the gas absorption decomposition rate of the Photocatalyst Composite 1 of evaluation object is determined.Figure
3 is the coordinate diagram of the evaluation result of the gas absorption decomposability for showing Photocatalyst Composite 1.Additionally, in the coordinate diagram of Fig. 3
In, the Photocatalyst Composite for being also shown for being supported with photocatalyst granular as the surface in ceramics of comparison other (compares
Example 1) measurement result.
As shown in figure 3, in comparative example (ceramics+photochemical catalyst (surface supports)), in the absence of absorbent particles 2, therefore
If not carrying out the adsorption-decomposition function that light irradiation is hardly visible gas.But, photochemical catalyst is occurred in that by carrying out light irradiation
The effect of grain, gas absorption decomposition rate is determined as 0.8 [h-1].
And in the Photocatalyst Composite 1 (zeolite+photochemical catalyst mixing bullet) of evaluation object, when not carrying out light irradiation
Gas adsorption rate be 1.5 [h-1], by carrying out light irradiation, gas decomposition rate rises to 2.8 [h-1].
It follows that not being that the effect of absorbent particles 2 and light are urged in the Photocatalyst Composite 1 of present embodiment
The simple addition of the effect of catalyst particles 3, and gas absorption decomposability higher has been played by synergy.
Next, illustrating the Photocatalyst Composite 1 of present embodiment and showing as comparison other using Fig. 4~Fig. 7
The ratio of some Photocatalyst Composites (being supported with the Photocatalyst Composite of photocatalyst granular on the surface of absorbent particles)
Relatively result.Fig. 4 is the figure for showing to shoot Photocatalyst Composite 1 SEM image for obtaining.Fig. 5 is shown to as relatively more right
As the existing Photocatalyst Composite of (comparative example 2) shoots the figure of the SEM image for obtaining.
In the past, as described in above-mentioned patent document 1,2, the hand of absorbent particles and the combined effect of photocatalyst granular is played
What section was taken is photocatalyst granular is supported in the method on the surface of absorbent particles.Its design is, in order that photochemical catalyst
Gas etc. is decomposed object decomposition and needs irradiation light by particle, and photochemical catalyst is configured into the absorbent particles in easy irradiation light
Surface.
And in the Photocatalyst Composite 1 of present embodiment, photocatalyst granular 3 not only disperses to be present in photochemical catalyst
The surface of composition 1, also dispersion is present in inside.
As described above, the Photocatalyst Composite (comparative example 2) of the Photocatalyst Composite 1 of evaluation object and comparison other
Zeolite is used as absorbent particles, the composition of proportions of degree of the photocatalyst granular 3 with weight than about 10~20%.
As shown in figure 4, on the surface of the Photocatalyst Composite 1 of evaluation object, particle diameter is for about the zeolite of 0.5 μm of degree
Particle (absorbent particles 2) largely exposes, and is found everywhere the particle of the photocatalyst granular 3 of the degree that particle diameter is for about 0.1 μm.
And it is as shown in Figure 5, it is known that in the Photocatalyst Composite of comparative example 2, the surface base of zeolite (absorbent particles)
This is covered by photocatalyst granular.In this composition, what is exposed on surface is photocatalyst granular, and zeolite does not reveal on surface
Go out, therefore gas absorption performance cannot be given full play to.
Next, illustrating that Photocatalyst Composite 1 and the actual gas of existing Photocatalyst Composite are inhaled based on Fig. 6
The measurement result of attached performance.Fig. 6 is by the gas of Photocatalyst Composite 1 and existing Photocatalyst Composite (comparative example 2)
The coordinate diagram that absorption property is compared.Additionally, in figure 6, as a comparison, being also shown for not being supported with photocatalyst granular
The measurement result of the velocity of gas sorption of the single bullet of zeolite.
As shown in fig. 6, the gas absorption of the Photocatalyst Composite 1 (zeolite+photochemical catalyst mixing bullet) of evaluation object
Speed is 1.5 roughly the same [h-1] with the bullet of only zeolite.
And the velocity of gas sorption of the Photocatalyst Composite (zeolite bullet+photochemical catalyst (surface supports)) of comparative example 2
It is 1.2 [h-1], it is known that compared with the Photocatalyst Composite 1 and single zeolite of evaluation object, gas absorption performance is relatively low.
Accounted for reference to the result of the SEM image of Fig. 5 and the result of Fig. 6, it is contemplated that because zeolite surface is urged by light
Catalyst particles are covered, therefore photocatalyst granular 3 brings negative effect to the gas absorption performance of absorbent particles 2.
Next, illustrating that Photocatalyst Composite 1 and the actual gas of existing Photocatalyst Composite are inhaled based on Fig. 7
The measurement result of attached performance.Fig. 7 is by the gas of Photocatalyst Composite 1 and existing Photocatalyst Composite (comparative example 2)
The coordinate diagram that decomposability is compared.
As shown in fig. 7, gas decomposition rate is 2.8 [h-1].The result shows, even such as Photocatalyst Composite 1
Such photocatalyst granular 3 is present in the composition of the inside of bullet, by using absorbent particles 2 with transmitance and can
See the photocatalyst granular 3 of photoresponse type, light can also sufficiently achieve the photocatalyst granular 3 of inside.It is thus identified that photocatalysis
Agent composition 1 has and the Photocatalyst Composite for making photocatalyst granular support the comparative example 2 in the surface of absorbent particles
(zeolite bullet+photochemical catalyst (surface supports)) is the gas decomposability of same degree.
On the other hand, in the Photocatalyst Composite of comparative example 2, photochemical catalyst is supported with zeolite bullet surface
Grain, thus by long-term use just in case in the case of occurring to come off chip etc. from bullet, can be preferential from being present in surface
Photocatalyst granular it is peeling-off.As a result, gas decomposability constantly declines, only absorbent particles are eventually become
Bullet.
And in Photocatalyst Composite 1, until inside all there is photocatalyst granular 3, even if therefore long-term use,
Gas decomposability can be made to continue without being wholly absent.Accordingly, it is capable to realize long-life Photocatalyst Composite 1.
Additionally, in Photocatalyst Composite 1, the ratio (ratio of components) of absorbent particles 2 and photocatalyst granular 3 is at it
Each internal position is uniform.Thus, even if there occurs that chip comes off, the ratio of absorbent particles 2 and photocatalyst granular 3
Example is also fixed.Therefore, in Photocatalyst Composite 1, total energy keeps absorption and the optimum balance for decomposing.In addition, inhaling
In the case that attached dose of particle 2 and photocatalyst granular 3 are extremely consumed, by additional supplement identical Photocatalyst Composite 1,
And the balance of absorption and decomposition can be kept and recover gas absorption decomposability.
As described above, in Photocatalyst Composite 1, absorbent particles 2 and photocatalyst granular 3 are deposited with dispersity
, therefore can continue absorption property and decomposability.
(implementation method 2)
Based on Fig. 8 another embodiment of the present invention as described below.Additionally, for convenience of description, to with above-mentioned
The component mark identical reference of the component identical function of being illustrated in implementation method, the description thereof will be omitted.
Fig. 8 is the sectional view of the Photocatalyst Composite 1a for schematically showing embodiments of the present invention 2.Such as Fig. 8 institutes
Show, the Photocatalyst Composite 1a of present embodiment approximately spherical bullet form.Additionally, although not shown, in photochemical catalyst
In composition 1a, absorbent particles 2 and photocatalyst granular 3 exist with dispersity.The inside of Photocatalyst Composite 1a is
The double-layer structure of outer layer (superficial layer) 4a and internal layer 5a.In Photocatalyst Composite 1a, the absorbent particles 2 in outer layer 4a
Ratio is higher than the ratio of photocatalyst granular 3, ratio of the ratio of photocatalyst granular 3 than absorbent particles 2 in internal layer 5a
It is high.That is, in Photocatalyst Composite 1a, absorbent particles 2 and photocatalyst granular 3 are outer layer 4a's and internal layer 5a
There is ratio uneven.Additionally, Photocatalyst Composite 1a is double-layer structure, but can also be more than three layers of multilayer knot
Structure.
According to Photocatalyst Composite 1a, absorbent particles 2 contains in the outer layer 4a of contact decomposition object is easier
The amount of having is high.Thus, can implement function such as：Object is decomposed using the rapid adsorption of absorbent particles 2 in the more presence of outer layer 4a
Thing, is carefully decomposed in the containing ratio of photocatalyst granular 3 internal layer 5a high using more photocatalyst granulars 3.
In addition, in Photocatalyst Composite 1a, from from the viewpoint of long-term, can be more than the ratio of absorbent particles 2
Outside consumes, therefore can realize short-term attention absorption, the bullet of the long-term Photocatalyst Composite 1a for paying attention to decomposing.
The preparation method of the Photocatalyst Composite 1a of this double-layer structure is for example contemplated that following method：By pressure
Block, using ring mould, the die forming of flat-die, be initially formed internal layer 5a, then change material proportion outer layer 4a is formed again.
Preparation method is not limited to these, it is also possible to many of two-layer or even more than three layers are made by being formed in order from internal layer 5a
The Photocatalyst Composite 1a of Rotating fields.
(implementation method 3)
Based on Fig. 9 another embodiment of the present invention as described below.Additionally, for convenience of description, to with above-mentioned
The component mark identical reference of the component identical function of being illustrated in implementation method, the description thereof will be omitted.
Fig. 9 is the sectional view of the Photocatalyst Composite 1b for schematically showing embodiments of the present invention 3.The light of Fig. 9
Carbon monoxide-olefin polymeric 1b is that the absorbent particles 2 in the outer layer 4a of the Photocatalyst Composite 1a of Fig. 8 and internal layer 5a are urged with light
The ratio of catalyst particles 3 is in turn.That is, the inside of Photocatalyst Composite 1b is also the two-layer of outer layer 4b and internal layer 5b
Structure.In Photocatalyst Composite 1b, the ratio of photocatalyst granular 3 is higher than the ratio of absorbent particles 2 in outer layer 4a,
The ratio of absorbent particles 2 is higher than the ratio of photocatalyst granular 3 in internal layer 5a.Additionally, Photocatalyst Composite 1b is two
Rotating fields, but can also be more than three layers of sandwich construction.
According to Photocatalyst Composite 1b, the function opposite with Photocatalyst Composite 1a can be realized.That is, according to
Photocatalyst Composite 1b, can realize that short-term attention is decomposed, the bullet of the long-term Photocatalyst Composite 1b for paying attention to absorption.Light is urged
The preparation method of agent composition 1b is likewise, therefore omitting the description with Photocatalyst Composite 1a.
(implementation method 4)
Based on Figure 10 another embodiment of the present invention as described below.Additionally, for convenience of description, to with above-mentioned
The component mark identical reference of the component identical function of being illustrated in implementation method, the description thereof will be omitted.
Figure 10 is the sectional view of the Photocatalyst Composite 1c for schematically showing embodiments of the present invention 4.Figure 10's
Photocatalyst Composite 1c is that the internal layer 5a of the Photocatalyst Composite 1a of Fig. 8 is formed as into sandwich construction.That is, light is urged
Agent composition 1c possesses outer layer (superficial layer) 4c and internal layer 5c, and internal layer 5c includes 12 layers 51~62.
And, in Photocatalyst Composite 1c, inside, absorbent particles 2 and photochemical catalyst are gone to from outer layer 4c
Ratio (ratio of components) consecutive variations of particle 3.That is, in Photocatalyst Composite 1c, in outer layer 4c and internal layer 5c (layers
51~62) in, the presence ratio of absorbent particles 2 and the sum of photocatalyst granular 3 is uneven.In the example of Figure 10, more go to
The center of Photocatalyst Composite 1c, the ratio of absorbent particles 2 is lower, and the ratio of photocatalyst granular 3 is higher.But also may be used
In turn, more to go to the center of Photocatalyst Composite 1c, the ratio of absorbent particles 2 is higher, the ratio of photocatalyst granular 3
Example is lower.
Photocatalyst Composite 1c is the composition same with Photocatalyst Composite 1a, thereby serves to be combined with photochemical catalyst
Thing 1b same effect.
In addition, in the Photocatalyst Composite 1a of implementation method 2,3, in 1b, between outer layer 4a, 4b and internal layer 5a, 5b,
Absorbent particles 2 drastically change with the ratio of components of photocatalyst granular 3, therefore in granulation, it some times happens that cracking or stripping
Deng.
And in the Photocatalyst Composite 1c of present embodiment, between outer layer 4c and internal layer 5c, absorbent particles 2 with
The ratio of components of photocatalyst granular 3 is consecutive variations, therefore the generation of cracking or stripping etc. can be reduced in granulation.
The preparation method of Photocatalyst Composite 1c is for example contemplated that following prilling process：Make as rotating granulation
In the prilling process that bullet grows in order from internal layer 5c (the most layer 62 of inner side), the group of the material of input is changed with growth
Into than.Preparation method not limited to this, by using the prilling process grown since internal layer 5c (the most layer 62 of inner side), and can root
According to the ratio for freely controlling with a distance from outer layer 4c (surface) absorbent particles 2 and photocatalyst granular 3.
(implementation method 5)
Based on Figure 11 and Figure 12 another embodiment of the present invention as described below.Additionally, for convenience of description, to with
The component mark identical reference of the component identical function of illustrating in the above-described embodiment, the description thereof will be omitted.
Figure 11 is the stereogram of the outward appearance of the Photocatalyst Composite 1d for schematically showing embodiments of the present invention 5.
Figure 12 is the sectional view of the Photocatalyst Composite 1d for schematically showing embodiments of the present invention 5.Such as Figure 11 and Figure 12 institutes
Show, it is solid-state (solid) that the Photocatalyst Composite 1d of present embodiment is same with the Photocatalyst Composite 1 of implementation method 1
, form the aggregate that absorbent particles 2 and photocatalyst granular 3 exist with dispersity.And, as shown in figure 12,
Space 6 is also formed with Photocatalyst Composite 1d.
Photocatalyst Composite 1d is with the maximum difference of Photocatalyst Composite 1, Photocatalyst Composite 1d
Surface photocatalyst granular 3 distribution density highest.For Photocatalyst Composite 1d, photocatalyst granular 3 point
Although cloth density be not particularly limited, but distribution density is high then more to be paid attention to decomposing, and distribution density is low then more to pay attention to absorption.Also
It is to say, the distribution density of photocatalyst granular 3 is higher, Photocatalyst Composite 1d will more pay attention to the effect of photocatalyst granular 3
Really (decomposability).
Specifically, as shown in figure 12, in Photocatalyst Composite 1d, the distribution density of photocatalyst granular 3 be
The surface of Photocatalyst Composite 1 is intensive, sparse internally.In other words, irradiated from certain direction to Photocatalyst Composite 1d
In the case of directional light, if not considering the reflected light of absorbent particles 2 by by the photocatalyst granular 3 of directional light direct irradiation
Area ratio with absorbent particles 2 is set to " A ", by not by the photocatalyst granular 3 of directional light direct irradiation and absorbent particles 2
Volume ratio be set to " B ", then in Photocatalyst Composite 1,1/A ≠ 0, B ≠ 0, and A ＞ B.
Above-mentioned " A " can photoactivation agent particle 3 Photocatalyst Composite 1d it is apparent on surface shared by area/suction
Attached dose of particle 2 Photocatalyst Composite 1d it is apparent on surface shared by area represent.Above-mentioned " B " can photoactivation agent
Particle 3 the volume/absorbent particles 2 shared by the inside of Photocatalyst Composite 1d Photocatalyst Composite 1d inside institute
The volume that accounts for is represented.Photocatalyst Composite 1d in above-mentioned " A " it is apparent on the area on surface for example can be according to electricity consumption
The photo of the shootings such as sub- microscope is calculated.Each volume energy in above-mentioned " B " is directly calculated by observation, the radioscopy in section
Go out, also can be by the density and voidage from Photocatalyst Composite 1d, the density of photocatalyst granular 3 and absorbent particles
2 density calculates weight ratio, and calculates volume ratio by calculating.
As long as additionally, the distribution density of photocatalyst granular 3 is maximum on the surface of Photocatalyst Composite 1d, also may be used
Being with going to composition that is internal and gradually decreasing.
In Photocatalyst Composite 1d, photocatalyst granular 3 plays effect by light, therefore stronger in light
The surface of Photocatalyst Composite 1d exists more at most more efficient.It is therefore preferable that the distribution density of photocatalyst granular 3 is urged in light
The surface highest of agent composition 1d.That is, preferably A ＞ B.On the other hand, as long as absorbent particles 2 are not contacted with decomposition object
Absorption property, therefore preferably 1/A ≠ 0 cannot just be played.Even in addition, the inside of Photocatalyst Composite 1d, adsorbent
Grain 2 reflected light and transmitted light can also reach, and light can directly be reached by space 6 inside photocatalyst granular 3.By
This, internal photocatalyst granular 3 can also play effect, therefore preferably B ≠ 0.
[manufacture method of Photocatalyst Composite 1d]
Next, the manufacture method of explanation Photocatalyst Composite 1d.The manufacture method of Photocatalyst Composite 1d does not have
It is particularly limited to, it is contemplated that for example following manufacture method.
For example, can be manufactured in the following way：By powdered absorbent particles 2 and powdered photochemical catalyst
Grain 3 mixes (the 1st mixed processes) in certain ratio, and the bulk for being shaped with space is fixed as the aggregate of these particles
(the fixed shaping inside Photocatalyst Composite 1d) (the 1st forming process), then, is compared around it by photocatalyst granular 3
Initially powdered absorbent particles 2 and powdered photocatalyst granular 3 are mixed (the 2nd mixing work by ratio many during shaping
Sequence), make both that shaping (photochemical catalyst is fixed with space with same with the 1st forming process or other manufacturing process
The fixed shaping on composition 1d surfaces) (the 2nd forming process).Additionally, the manufacturing process of the 1st forming process and the 2nd forming process
It is same with the manufacturing process illustrated in implementation method 1.
In addition, Photocatalyst Composite 1d can also be manufactured in the following way：Mixed processes and shaping in implementation method 1
After operation, also enter to exercise photocatalyst granular 3 and support in the supporting procedures on the surface of the molding obtained by forming process.
According to this manufacture method, Photocatalyst Composite 1d can be easily manufactured.
Additionally, space 6 can be formed when the Photocatalyst Composite 1d of present embodiment is manufactured, therefore in [light described later
The evaluation of carbon monoxide-olefin polymeric 1d] in manufacture method in, photocatalyst granular 3 can be made to impregnated in including absorbent particles 2
Photocatalyst granular 3 is set to impregnate to the inside of bullet with during the bullet of adhesive.
[effect of Photocatalyst Composite 1d]
So, in the Photocatalyst Composite 1d of present embodiment, photocatalyst granular 3 not only disperses to be present in light urges
The most surface of agent composition 1, also dispersion is present in inside.Also, the distribution density of photocatalyst granular is in photochemical catalyst group
The surface highest of compound 1d.That is, the distribution density of photocatalyst granular 3 is intensive on the surface of Photocatalyst Composite 1d, including
Portion is sparse.Therefore, in addition to the effect of the Photocatalyst Composite 1 of implementation method 1, moreover it is possible to make most photocatalyst granulars 3
Stronger light, can realize the raising of decomposability.
In addition, being formed with space 6 in Photocatalyst Composite 1d, therefore the energy of adsorption of absorbent particles 2 will not be hindered
Power, and can ensure that the photocatalyst granular 3 of q.s.
[evaluation of Photocatalyst Composite 1d]
(manufacture of the Photocatalyst Composite 1d of evaluation object)
Photochemical catalyst uses tungsten oxide, adsorbent to use the zeolite of ZSM-5 types, adhesive to use polyethylene.Make tungsten oxide：
Zeolite：The weight ratio of adhesive is 0.5：4.5：5, become by thermoforming be formed with space bullet form it
Afterwards, photocatalyst-supporting is made around bullet by dipping, finally produces the tungsten oxide of surrounding (surface)：Internal oxidation
Tungsten：Zeolite：The weight ratio of adhesive is 1.7：0.5：4.5：The Photocatalyst Composite 1d of 5 bullet form.
Additionally, according to optical surface observation, calculated Photocatalyst Composite 1d surface " photochemical catalyst area/
Adsorbent area ratio (A) " is for about 100.In addition, according to the calculating of photochemical catalyst and each density of adsorbent, having calculated light and having urged
The ratio between the photochemical catalyst volume/adsorbent volume of the inside of agent composition 1d B is for about 0.03, and has calculated photochemical catalyst combination
The voidage of thing 1d is for about 37%.
(manufacture of the Photocatalyst Composite of comparison other (comparative example 3))
Photochemical catalyst uses tungsten oxide, adsorbent to use the zeolite of ZSM-5 types, adhesive to use polyethylene.Make tungsten oxide：
Zeolite：The weight ratio of adhesive is 2.5：2.5：5, the Photocatalyst Composite of bullet form is manufactured by thermoforming.
Additionally, according to optical surface observation, estimating the journey of photochemical catalyst area/adsorbent area ratio A=0.005
Degree, according to the calculating of density, estimates the degree of the ratio between photochemical catalyst volume/adsorbent volume B=0.03.And calculated and compare
The voidage of the Photocatalyst Composite of example 3 is for about 37%.
(evaluation method)
Evaluation method with implementation method 1 is same, and the photochemical catalyst group of embodiment is evaluated using the evaluating apparatus shown in Fig. 2
The Photocatalyst Composite of compound 1d and comparative example.
Decompose object gas using aldehydes gas as VOC, as various smells the reason for gas representative.First,
Measure does not adsorb gas concentration change during aldehydes gas to the Photocatalyst Composite irradiation light of embodiment and comparative example 3,
To no longer see gas concentration change time point gas decrement divided by adsorbent amount and as the per unit amount of adsorbent
Limit adsorbance.Then, the decomposition of aldehydes gas is carried out to the Photocatalyst Composite irradiation light of embodiment and comparative example.
The decomposition amount of gas is calculated by determining by the change of the gas concentration lwevel of the decomposition generation of aldehydes gas, by the decomposition amount
Change slope divided by photochemical catalyst the result for measuring as photochemical catalyst per unit average decomposition rate.Second
The measure of aldehyde gas concentration uses the acetaldehyde detection pipe No.92 and carbon dioxide detection pipe of gas technology manufacture
No.2LC。
(evaluation result)
The limit adsorbance of the Photocatalyst Composite 1d of present embodiment and average is determined by above-mentioned evaluation method
Decomposition rate.Figure 13 is the coordinate diagram of the evaluation result of the limit adsorbance for showing Photocatalyst Composite 1d.Additionally, in Figure 13
Coordinate diagram in, as comparison other be also shown for surface be not supported with photocatalyst granular Photocatalyst Composite (ratio
Compared with example 3) measurement result.
As shown in figure 13, in the Photocatalyst Composite 1d and comparative example 3 of present embodiment, limit adsorbance it is identical or
The Photocatalyst Composite 1d of present embodiment is slightly excellent.It is contemplated that this is because, the photochemical catalyst in present embodiment is combined
The surface of thing 1d, it is different from the conventional example that above-mentioned patent document 1,2 is recorded, there is no photoactivation agent particle 3 to cover photochemical catalyst
The whole surface of composition 1, but absorbent particles 2 is exposed to surface, in addition, internally there is space, therefore gas energy
It is impregnated with and is fully adsorbed.
Next, illustrating the measure knot of the average decomposition rate in Photocatalyst Composite 1d and comparative example 3 based on Figure 14
Really.Figure 14 is the coordinate diagram for being compared the gas decomposability of Photocatalyst Composite 1d and comparative example 3.
As shown in figure 14, average decomposition rate is 21.8 [ppm@5L/h] in comparative example 3, and in photochemical catalyst combination
It is 26.3 [ppm@5L/h] in thing 1d.The result shows, even the photocatalyst granular as comparative example 3 is present in bullet
Inside composition, by using the absorbent particles with transmitance and light reflective as Photocatalyst Composite 1d
2 and the photocatalyst granular 3 of visible-light response type shaped in the way of with space 6, the light that light can also substantially arrive inside is urged
Catalyst particles 3 and carry out the decomposition of gas.And, in Photocatalyst Composite 1d, in the photocatalyst granular 3 that surface supports
Direct light, therefore decomposition efficiency is high.It is therefore intended that the Photocatalyst Composite 1d of present embodiment on the whole with comparative example
3 compare, and the gas decomposition efficiency of photocatalyst granular 3 is higher.It is thus identified that Photocatalyst Composite 1d is not chased after with surface
Plus supporting that the comparative example 3 of photocatalyst granular is higher compared to average decomposition rate, gas decomposition efficiency aspect is more excellent.
As described above, in Photocatalyst Composite 1d, photocatalyst granular 3 to be distributed in surface intensive, internally
It is sparse.Thus, the absorption property of adsorbent and the decomposability of photochemical catalyst can be taken into account and continues it, moreover it is possible to urge numerous light
Catalyst particles the last 3 light, can realize the raising of decomposability.
(implementation method 6)
Another embodiment of the present invention as described below.In the present embodiment, the photochemical catalyst group of implementation method 5 is illustrated
The manufacture method of compound 1d.Additionally, for convenience of description, to with the component identical work(for illustrating in the above-described embodiment
The component mark identical reference of energy, the description thereof will be omitted.
In the manufacture method of the Photocatalyst Composite 1d of present embodiment, make absorbent particles 2 and photochemical catalyst
3 dispersion step from the surface of Photocatalyst Composite 1d towards inner dispersion of grain is included：Forming process, uses absorbent particles
2 and thermoplasticity adhesive form molding, the molding is formed with space 6；And supporting procedures, make photocatalyst granular 3
Support in the surface of the molding for being formed with above-mentioned space 6.
For example, in above-mentioned forming process, powdered absorbent particles 2 to be used as the thermoplastic resin of adhesive
(thermoplasticity adhesive) fixation is shaped with the bulk in space 6.Then, after forming process, above-mentioned supporting procedures are carried out,
Thus, photocatalyst granular 3 is made to support in the surface of the molding obtained by forming process by infusion process.Thus, can letter
Just Photocatalyst Composite 1d is manufactured.
The thermoplasticity adhesive used in the above-mentioned forming process e.g. thermoplasticity tree such as polypropylene, polyethylene
Fat.In addition, as long as the manufacturing process of the manufacturing process heating of above-mentioned forming process, is not particularly limited.For example, shaping
Method can also be：The granulation carried out by thermoforming, makes the mixed particulate stream of absorbent particles 2 and thermoplasticity adhesive
Enter mould and heated and shaped.
On the other hand, the infusion process of the photocatalyst granular 3 in above-mentioned supporting procedures for example can be following method：Make light
Catalyst granules 3 is scattered in water, alcohol equal solvent, and penetrates into the molding obtained by above-mentioned forming process (with space 6
Block fixed molding), by heat or at normal temperatures dry it.
According to this method, in supporting procedures, the dispersion liquid of photocatalyst granular 3 can be not only impregnated with by forming process
The surface of the fixed molding for obtaining, also can be being impregnated with space 6 to a certain degree.Therefore, photochemical catalyst to a certain degree can also be made
Particle 3 is supported in the inside of fixed molding.As a result, photocatalyst granular 3 can be made reliably to be dispersed to photochemical catalyst group
The inside of compound 1d, makes photocatalyst granular 3 support in internal absorbent particles 2.
And, in the manufacture method of present embodiment, preferably after supporting procedures, also include：Fixed work order, passes through
After heating softens above-mentioned thermoplasticity adhesive, solidify the thermoplasticity adhesive of softening, thus by above-mentioned photochemical catalyst
Particle 3 is fixed on thermoplasticity adhesive.
So, when fixed work order is carried out after the supporting procedures that photocatalyst granular 3 is supported by infusion process, in fixation
Thermoplasticity adhesive can soften in operation, and be cooled to normal temperature.Thus, when thermoplasticity adhesive solidifies again, can be by
Photocatalyst granular 3 is fixed on thermoplasticity adhesive.As a result, photocatalyst granular 3 can be made to support in photochemical catalyst group
Thermoplasticity adhesive inside compound 1d.Accordingly, it is capable to make photocatalyst granular 3 reliably support in Photocatalyst Composite 1d
Inside.
(implementation method 7)
Another embodiment of the present invention as described below.In the present embodiment, the photochemical catalyst group of implementation method 5 is illustrated
Other manufacture methods of compound 1d.Additionally, for convenience of description, to with the component phase for illustrating in the above-described embodiment
The component mark identical reference of same function, the description thereof will be omitted.
In the manufacture method of the Photocatalyst Composite 1d of present embodiment, make absorbent particles 2 and photochemical catalyst
3 dispersion step from the surface of Photocatalyst Composite 1d towards inner dispersion of grain is included：Forming process, uses absorbent particles
2 and Thermocurable adhesive form molding, the molding is formed with space 6；And supporting procedures, make photocatalyst granular 3
Support in the surface of the molding for being formed with above-mentioned space 6.
For example, in above-mentioned forming process, the Thermocurable adhesive solidified with multiple conditions for being used as adhesive will
The powdered thermoforming of absorbent particles 2.For example, 2 stages thermosetting of the adhesive using the heat cure under conditions of 2 differences
The property changed adhesive.Also, in forming process, the bulk with space 6 is formed to fix by the solidification in the 1st stage.Then,
Above-mentioned supporting procedures are carried out after forming process, thus, photocatalyst granular 3 is supported in by forming process by infusion process
The surface of the molding for obtaining.Thus, Photocatalyst Composite 1d can easily be manufactured.
It is preferred that the Thermocurable adhesive used in above-mentioned forming process uses the Thermocurable solidified with multiple conditions
Adhesive.For example, the Thermocurable adhesive of this property can enumerate the 2 stages thermosetting of the heat cure under conditions of 2 differences
The property changed resin, more specifically, can enumerate silicone resinoid or epoxylite.
In addition, as long as the manufacturing process of the manufacturing process heating in above-mentioned forming process, is not particularly limited.Example
Such as, manufacturing process can also be：The granulation carried out by thermoforming, makes the mixed of absorbent particles 2 and Thermocurable adhesive
Particle is closed to flow into mould and heated and shaped.
On the other hand, the infusion process of the photocatalyst granular 3 in above-mentioned supporting procedures for example can be following method：Make light
Catalyst granules 3 is scattered in water, alcohol equal solvent, and penetrates into the molding obtained by above-mentioned forming process (with space 6
Block fixed molding), by heat or at normal temperatures dry it.
According to this method, in supporting procedures, the dispersion liquid of photocatalyst granular 3 can be not only impregnated with by forming process
The surface of the fixed molding for obtaining, also can be being impregnated with space 6 to a certain degree.Therefore, photochemical catalyst to a certain degree can also be made
Particle 3 is supported in the inside of fixed molding.As a result, photocatalyst granular 3 can be made reliably to be dispersed to photochemical catalyst group
The inside of compound 1d, makes photocatalyst granular 3 support in internal absorbent particles 2.
And, in the manufacture method of present embodiment, preferably also included after supporting procedures：Fixed work order, with it is upper
State and make under the different condition of cure of forming process Thermocurable adhesive and solidify, photocatalyst granular 3 is thus fixed on thermosetting
The property changed adhesive.
So, when operation is fixed after the supporting procedures that photocatalyst granular 3 is supported by infusion process, solid
Determine that the solidification in the 2nd stage occurs in operation, photocatalyst granular 3 can be fixed on Thermocurable adhesive.As a result, can make
Photocatalyst granular 3 supports the thermoplasticity adhesive in the inside of Photocatalyst Composite 1d.Accordingly, it is capable to make photochemical catalyst
Grain 3 is reliably supported in the inside of Photocatalyst Composite 1d.
(summary)
The Photocatalyst Composite 1,1a, 1b, 1c, 1d of mode of the invention 1 be solid-state Photocatalyst Composite 1,1a,
1b, 1c, contain：Absorbent particles 2, it has at least one party in transmitance and light reflective；And photocatalyst granular
3, above-mentioned absorbent particles 2 and photocatalyst granular 3 are the compositions existed with dispersity.
According to above-mentioned composition, absorbent particles and photocatalyst granular exist with dispersity.That is, photocatalyst granular is not
It is to exist only in the surface of absorbent particles the technology recorded such as patent document 1,2, but is also present in dispersity
The inside of Photocatalyst Composite.Thus, decomposing object will not be hindered to the absorption of absorbent particles by photocatalyst granular,
Therefore absorption property high can be played.
And, it is not photocatalyst granular is supported (covering) in the structure on the surface of absorbent particles according to above-mentioned composition
Into, therefore compared with this case, more photocatalyst granulars can be contained.In addition, will not also occur photocatalyst granular from
The problem that the surface of absorbent particles is peeled off.Also, absorbent particles have transmitance, therefore light can also substantially arrive at presence
In internal photocatalyst granular.Thus, can continue the decomposability of photochemical catalyst.
Accordingly, it is capable to providing, absorption property and the lasting Photocatalyst Composite of decomposability can be made.In addition, can provide can be simultaneous
Turn round and look at the Photocatalyst Composite of absorption property and decomposability.
The Photocatalyst Composite 1,1a, 1b, 1c, 1d of mode of the invention 2 is preferably formed with space in mode 1.This
The Photocatalyst Composite 1,1a, 1b, 1c, 1d of the mode 3 of invention is combined preferably in mode 2 relative to above-mentioned photochemical catalyst
The volume % of thing 100, the ratio shared by above-mentioned space is 30~50 volume %.
According to above-mentioned composition, in absorbent particles 2 have the wavelength region of light reflective, light can reach light by space
The inside of carbon monoxide-olefin polymeric.That is, in the wavelength region that absorbent particles have light reflective, also can with light
Radioparent wavelength region is same, light is reached the inside of Photocatalyst Composite.In addition, gas can be impregnated with space, urged in light
Also can fully be adsorbed in the absorbent particles of the inside of agent composition.
The Photocatalyst Composite 1,1a, 1b, 1c, 1d of mode of the invention 4 preferably in mode 1~3, above-mentioned photocatalysis
Agent particle 3 includes the photochemical catalyst of visible-light response type.The Photocatalyst Composite 1,1a, 1b, 1c, 1d of mode of the invention 5
Can also be, in mode 4, the titanium dioxide that above-mentioned photocatalyst granular 3 includes tungsten oxide, worked in visible region
Or their mixture.
According to above-mentioned composition, photocatalyst granular includes tungsten oxide, is modified into what is also worked in visible region
The photochemical catalyst of the visible-light response types such as titanium dioxide, therefore photocatalyst activity is shown by absorbing visible ray.Thus,
Can be decomposed to decomposing object in the wavelength long of the photochemical catalyst than ultraviolet-responsive type.Accordingly, it is capable to provide indoors,
Can also stablize the Photocatalyst Composite for playing absorption property and decomposability under the considerably less situation of grade ultraviolet in automobile.
The Photocatalyst Composite 1,1a, 1b, 1c, 1d of mode of the invention 6 preferably in mode 1~5, above-mentioned adsorbent
Particle 2 includes the mixture of many kinds of substance among zeolite, sepiolite, mesoporous silicon oxide, atlapulgite or these materials.
According to above-mentioned composition, absorbent particles include being particularly transmitance in the wavelength region from visible ray near ultraviolet
The mixture of many kinds of substance among zeolite high, sepiolite, mesoporous silicon oxide, atlapulgite or these materials.Thus,
Light can be made reliably to reach the photocatalyst granular that the inside of Photocatalyst Composite is present.Accordingly, it is capable to combine photochemical catalyst
The absorption property and decomposability of thing continue for a long time.
The Photocatalyst Composite 1,1a, 1b, 1c, 1d of mode of the invention 7 is bullet form preferably in mode 1~6.
According to above-mentioned composition, due to being the Photocatalyst Composite 1,1a, 1b, 1c, 1d of bullet form, therefore with powder
State situation about using compare, it is not necessary to other carrying body etc., can not make in the range of the reduction of gas absorption decomposability
Directly use the block with volume to a certain degree.Therefore, can easily be used in terms for the treatment of.
The Photocatalyst Composite 1,1a, 1b, 1c, 1d of mode of the invention 8 can also be, be substantially ball in mode 7
The bullet form of shape, its a diameter of more than 0.5mm, below 5mm.Thus, the simplicity in terms for the treatment of can be maintained, and makes decomposition
Object is reliably impregnated into Photocatalyst Composite.
The composition of the Photocatalyst Composite 1d of mode of the invention 9 can also be, in mode 1~8, photochemical catalyst
Surface highest of the distribution density of grain in above-mentioned Photocatalyst Composite 1d.
According to above-mentioned composition, photocatalyst granular 3 is densely distributed the surface of Photocatalyst Composite 1d, dilute internally
Dredge, therefore the direct light of meeting of photocatalyst granular 3 supported on surface, thus decomposition efficiency is high.
And, if being formed with space 6 in Photocatalyst Composite 1d, the surface of Photocatalyst Composite 1d will not
The all coverings of photoactivation agent particle 3, and absorbent particles 2 are exposed to surface.Thus, absorption can all be played in surface and inside
The absorption property of agent and the decomposability of photochemical catalyst.Accordingly, it is capable to make the decomposability of the absorption property of adsorbent and photochemical catalyst
Can more reliably continue, and can more reliably take into account the two.
The Photocatalyst Composite 1 of mode of the invention 10 can also be, in mode 1~8, above-mentioned absorbent particles 2
In the inside of Photocatalyst Composite 1 it is uniform with the ratio of components of photocatalyst granular 3.
According to above-mentioned composition, absorbent particles and photocatalyst granular are uniformly present in Photocatalyst Composite.Therefore,
The Photocatalyst Composite for being always to maintain absorption and the optimum balance for decomposing can be provided.
The Photocatalyst Composite 1 of mode of the invention 11 can also be, in mode 1~8, with going to photochemical catalyst
The ratio of components of the inside of composition, above-mentioned absorbent particles and photocatalyst granular increases or reduces.
According to above-mentioned composition, with the inside for going to Photocatalyst Composite, above-mentioned absorbent particles and photochemical catalyst
The ratio of components of grain changes, therefore absorbent particles and photocatalyst granular are unevenly present in Photocatalyst Composite
In.Thus, in the case of absorbent particles reduction, short-term attention absorption can be being realized, for a long time attention point with inside is gone to
The Photocatalyst Composite of solution.On the other hand, with go to it is internal and in the case of absorbent particles are increased, can realize in short term
Pay attention to decomposing, the long-term Photocatalyst Composite for paying attention to absorption.
The composition of the Photocatalyst Composite 1,1a, 1b, 1c, 1d of mode of the invention 12 can also be, in mode 1~11
In, also contain adhesive.Thus, the shaping of Photocatalyst Composite can be made to become easy, can easily manufactures photochemical catalyst combination
Thing.
The manufacture method of the Photocatalyst Composite 1,1a, 1b, 1c, 1d of mode of the invention 13 is that a kind of light of solid-state is urged
The manufacture method of agent composition, above-mentioned Photocatalyst Composite contains：Absorbent particles, there is transmitance and light to reflect for it
At least one party in property；And photocatalyst granular, above-mentioned manufacture method includes：Dispersion step, make above-mentioned absorbent particles and
Photocatalyst granular is from the surface of above-mentioned Photocatalyst Composite towards inner dispersion.
According to above-mentioned composition, can manufacture can make absorption property and the lasting Photocatalyst Composite of decomposability and energy simultaneous
Turn round and look at the Photocatalyst Composite of absorption property and decomposability.
The manufacture method of the Photocatalyst Composite 1,1a, 1b, 1c, 1d of mode of the invention 14 can also be, in mode
In 13, above-mentioned dispersion step is included：Mixed processes, by above-mentioned absorbent particles and photocatalyst granular；And forming process, make
Absorbent particles and the photocatalyst granular shaping mixed by above-mentioned mixed processes.Thus, photochemical catalyst can easily be manufactured
Composition.
The manufacture method of the Photocatalyst Composite 1d of mode of the invention 15 can also be, in mode 14, comprising：Load
Operation is carried, photocatalyst granular 3 is supported in the surface of the molding obtained by above-mentioned forming process.
According to above-mentioned composition, the distribution density of photocatalyst granular 3 can be easily manufactured Photocatalyst Composite 1d's
Surface highest Photocatalyst Composite 1d.
The manufacture method of the Photocatalyst Composite 1,1a, 1b, 1c, 1d of mode of the invention 16 can also be, in mode
In 13, above-mentioned dispersion step is included：Forming process, using above-mentioned absorbent particles and thermoplasticity adhesive or using above-mentioned
Absorbent particles and Thermocurable adhesive form molding, and the molding is formed with space；And supporting procedures, make above-mentioned light
Catalyst granules is supported in the surface of the molding for being formed with above-mentioned space.
According to above-mentioned composition, can easily manufacture can make absorption property and the lasting Photocatalyst Composite of decomposability with
And the Photocatalyst Composite of absorption property and decomposability can be taken into account.
The manufacture method of the Photocatalyst Composite 1d of mode of the invention 17 can also be, in mode 16, above-mentioned
Forming process carries out thermoforming with thermoplasticity adhesive, in above-mentioned supporting procedures, supports above-mentioned photocatalyst granular
In the surface of the molding that above-mentioned space is formed with by infusion process, after above-mentioned supporting procedures, comprising：Fixed work order,
After heating softens above-mentioned thermoplasticity adhesive, solidify the thermoplasticity adhesive of softening, thus urge above-mentioned light
Catalyst particles are fixed on thermoplasticity adhesive.
According to above-mentioned composition, in supporting procedures, making the dispersion liquid of photocatalyst granular be impregnated with space by dipping
Photocatalyst granular is supported after the inside of the molding in space is formed with, be fixed operation.Thus, by fixed work order
Heating, photocatalyst granular can be fixed on thermoplasticity adhesive.Accordingly, it is capable to easily manufacture photocatalyst granular 3
Surface highest Photocatalyst Composite 1d of the distribution density in Photocatalyst Composite 1d.
The manufacture method of the Photocatalyst Composite 1d of mode of the invention 18 can also be, in mode 16, above-mentioned
Thermoforming is carried out with the Thermocurable adhesive for solidifying under multiple conditions in forming process, in above-mentioned supporting procedures, is made
Above-mentioned photocatalyst granular is supported in the surface of the molding that above-mentioned space is formed with by infusion process, above-mentioned supporting procedures it
Afterwards, comprising：Fixed work order, solidifies above-mentioned Thermocurable adhesive under the condition of cure different from above-mentioned forming process, by
Above-mentioned photocatalyst granular is fixed on Thermocurable adhesive by this.
According to above-mentioned composition, formed by the solidification in the 1st stage of forming process：It is formed with the molding in space.So
Afterwards, in supporting procedures, the dispersion liquid of photocatalyst granular is impregnated with space and support photocatalyst granular by dipping
After the inside of the molding in space is formed with, operation is fixed.Thus, the solidification in the 2nd stage of fixed work order can be passed through
Photocatalyst granular 3 is fixed on 2 stage Thermocurable adhesives.Accordingly, it is capable to easily manufacture the distribution of photocatalyst granular 3
Surface highest Photocatalyst Composite 1d of the density in Photocatalyst Composite 1d.
It is by powdered adsorbent and powdered photochemical catalyst that the gas absorption of mode of the invention 21 decomposes bullet
Mixing, and the bullet for being configured to bulk is fixed as the aggregate of powder, adsorbent has transmitance, and photochemical catalyst is can
See photoresponse type.
According to above-mentioned composition, the photochemical catalyst of q.s is can ensure that, therefore with gas absorption decomposability high, can be real
Even if existing long-term use, the gas absorption that gas decomposability is not easy to reduce decomposes bullet.
The gas absorption of mode of the invention 22 decomposes bullet, and in mode 21, above-mentioned adsorbent includes boiling
Stone, sepiolite or their mixture.
According to above-mentioned composition, for the adsorbent particularly with transmitance, therefore luminous energy are substantially arrived inside bullet, energy
Realize gas decomposability high.
The gas absorption of mode of the invention 23 decomposes bullet.In mode 21 or 22, above-mentioned photocatalysis
Agent includes tungstic acid (WO3), be modified into can by importing specific metal ion or by importing nitrogen to oxygen position
See the titanium dioxide (TiO also worked in light region2) or their mixture.
According to above-mentioned composition, the photochemical catalyst particularly with the characteristic reacted with visible ray, therefore phase can be constituted
Than in the photochemical catalyst reacted to ultraviolet light, can with wavelength division gas more long, can use than general adsorbent
The longer light of transmitance wavelength higher, therefore gas decomposability high can be realized.
The gas absorption of mode of the invention 24 decompose bullet and can also be in mode 21~23 it is approximately spherical, its
The degree of a diameter of φ 0.5mm~φ 5mm.
According to above-mentioned composition, compared with situation about being used with the state of powder, it is not necessary to other carrying body etc., can not make
In the range of the reduction of gas absorption decomposability, the block with volume to a certain degree, therefore the energy in terms for the treatment of are directly used
Simplicity is used.
It can also be that in mode 21~24, adsorbent and light are urged that the gas absorption of mode of the invention 25 decomposes bullet
Each position of the presence ratio of agent inside bullet is uniform.
According to above-mentioned composition, even if in the case where for example there occurs that chip comes off etc. by long-term use, also can
Always the ratio of adsorbent and photochemical catalyst is kept to fix, one can be shown optimal proportion and acted, thus can reduce due to
The reduction of gas absorption decomposability caused by long-term use.
It can also be that in mode 21~25, adsorbent and light are urged that the gas absorption of mode of the invention 26 decomposes bullet
The presence ratio of agent can be showed with the function with a distance from bullet surface.
According to above-mentioned composition, as gas and light are impregnated with and concentration changes from bullet surface, but can freely set accordingly
The ratio of fixed optimal adsorbent and photochemical catalyst.
The invention is not restricted to the respective embodiments described above, various changes can be carried out in the scope shown in claim, will be
The appropriately combined implementation method for obtaining of disclosed technical scheme is also contained in technology of the invention respectively in different implementation methods
Scope.Can also be by by disclosed solution pool forms new technical characteristic respectively in each implementation method.
Industrial utilizability
Photocatalyst Composite of the invention can be suitable for air purifier, deodoriser, can be suitable for as utilization
Family, meeting room, shop, factory, medical office, automobile, electric car, ship, airborne vehicle of occasion etc..
Description of reference numerals
1、1a、1b、1c、1d：Photocatalyst Composite
2：Absorbent particles
3：Photocatalyst granular
6：Space.
Claims (18)
1. a kind of Photocatalyst Composite,
It is the Photocatalyst Composite of solid-state, contains：Absorbent particles, it has at least in transmitance and light reflective
Side；And photocatalyst granular, above-mentioned Photocatalyst Composite is characterised by,
Above-mentioned absorbent particles and photocatalyst granular exist with dispersity.
2. Photocatalyst Composite according to claim 1, it is characterised in that
It is formed with space.
3. Photocatalyst Composite according to claim 2, it is characterised in that
Relative to the volume % of above-mentioned Photocatalyst Composite 100, the ratio shared by above-mentioned space is 30~50 volume %.
4. the Photocatalyst Composite described in any one in claims 1 to 3, it is characterised in that
Above-mentioned photocatalyst granular includes the photochemical catalyst of visible-light response type.
5. Photocatalyst Composite according to claim 4, it is characterised in that
Above-mentioned photocatalyst granular includes tungsten oxide, the titanium dioxide worked in visible region or their mixing
Thing.
6. the Photocatalyst Composite described in any one in claim 1 to 5, it is characterised in that
Above-mentioned absorbent particles are including more among zeolite, sepiolite, mesoporous silicon oxide, atlapulgite or these materials
Plant the mixture of material.
7. the Photocatalyst Composite described in any one in claim 1 to 6, it is characterised in that
It is bullet form.
8. Photocatalyst Composite according to claim 7, it is characterised in that
It is approximately spherical bullet form, its a diameter of more than 0.5mm, below 5mm.
9. the Photocatalyst Composite described in any one in claim 1 to 8, it is characterised in that
Surface highest of the distribution density of photocatalyst granular in above-mentioned Photocatalyst Composite.
10. the Photocatalyst Composite described in any one in claim 1 to 8, it is characterised in that
The ratio of components of above-mentioned absorbent particles and photocatalyst granular is uniform in the inside of Photocatalyst Composite.
Photocatalyst Composite described in 11. any one in claim 1 to 8, it is characterised in that
With the inside for going to Photocatalyst Composite, the ratio of components of above-mentioned absorbent particles and photocatalyst granular increase or
Reduce.
Photocatalyst Composite described in 12. any one in claim 1 to 11, it is characterised in that
Also contain adhesive.
A kind of 13. manufacture methods of Photocatalyst Composite,
Above-mentioned Photocatalyst Composite is solid-state, is contained：Absorbent particles, it has in transmitance and light reflective at least
One side；And photocatalyst granular, above-mentioned manufacture method is characterised by,
Comprising：Dispersion step, makes the surface court of above-mentioned absorbent particles and photocatalyst granular from above-mentioned Photocatalyst Composite
Internally disperse.
The manufacture method of 14. Photocatalyst Composites according to claim 13, it is characterised in that
Above-mentioned dispersion step is included：
Mixed processes, above-mentioned absorbent particles and photocatalyst granular are mixed；And
Forming process, shapes the absorbent particles mixed by above-mentioned mixed processes and photocatalyst granular.
The manufacture method of 15. Photocatalyst Composites according to claim 14, it is characterised in that
Comprising：Supporting procedures, further make photocatalyst granular support in the table of the molding obtained by above-mentioned forming process
Face.
The manufacture method of 16. Photocatalyst Composites according to claim 13, it is characterised in that
Above-mentioned dispersion step is included：
Forming process, uses above-mentioned absorbent particles and thermoplasticity adhesive or use above-mentioned absorbent particles and heat cure
Property adhesive form molding, the molding is formed with space；And
Supporting procedures, make above-mentioned photocatalyst granular support in the surface of the molding for being formed with above-mentioned space.
The manufacture method of 17. Photocatalyst Composites according to claim 16, it is characterised in that
In above-mentioned forming process, thermoforming is carried out using thermoplasticity adhesive,
In above-mentioned supporting procedures, above-mentioned photocatalyst granular is set to support in the molding that above-mentioned space is formed with by infusion process
Surface,
After above-mentioned supporting procedures, comprising：Fixed work order, after heating softens above-mentioned thermoplasticity adhesive, makes soft
The thermoplasticity adhesive solidification of change, is thus fixed on thermoplasticity adhesive by above-mentioned photocatalyst granular.
The manufacture method of 18. Photocatalyst Composites according to claim 16, it is characterised in that
In above-mentioned forming process, thermoforming is carried out using the Thermocurable adhesive for solidifying under multiple conditions,
In above-mentioned supporting procedures, above-mentioned photocatalyst granular is set to support in the molding that above-mentioned space is formed with by infusion process
Surface,
After above-mentioned supporting procedures, comprising：Fixed work order, makes above-mentioned heat under the condition of cure different from above-mentioned forming process
Curing adhesive solidifies, and above-mentioned photocatalyst granular thus is fixed on into Thermocurable adhesive.
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| JP2014173265 | 2014-08-27 | ||
| JP2014-173265 | 2014-08-27 | ||
| JP2014-259410 | 2014-12-22 | ||
| JP2014259410A JP5851578B1 (en) | 2014-08-27 | 2014-12-22 | Photocatalyst composition and method for producing the same |
| PCT/JP2015/064592 WO2016031319A1 (en) | 2014-08-27 | 2015-05-21 | Photocatalyst composition and method for producing same |
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| CN106794456B CN106794456B (en) | 2020-03-06 |
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| JP (1) | JP5851578B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108097034A (en) * | 2017-11-10 | 2018-06-01 | 浙江裕文环保科技有限公司 | Can quickly, the environmentally protective nanometer sustained-release gel of high-efficient cleaning removal organic polluter |
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| CN106794456B (en) | 2020-03-06 |
| WO2016031319A1 (en) | 2016-03-03 |
| JP2016047516A (en) | 2016-04-07 |
| JP5851578B1 (en) | 2016-02-03 |
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