CN107308983A - Room temperature is except interior VOC catalyst and preparation method thereof - Google Patents
Room temperature is except interior VOC catalyst and preparation method thereof Download PDFInfo
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- CN107308983A CN107308983A CN201710524253.2A CN201710524253A CN107308983A CN 107308983 A CN107308983 A CN 107308983A CN 201710524253 A CN201710524253 A CN 201710524253A CN 107308983 A CN107308983 A CN 107308983A
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- room temperature
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- multistage pore
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001868 water Inorganic materials 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 3
- 239000011258 core-shell material Substances 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 65
- 238000003756 stirring Methods 0.000 claims description 64
- 239000000243 solution Substances 0.000 claims description 51
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 26
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 18
- 239000000969 carrier Substances 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000008246 gaseous mixture Substances 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 239000002808 molecular sieve Substances 0.000 claims description 8
- 238000010926 purge Methods 0.000 claims description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 7
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 3
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- -1 myristyl-lutidines ammonium bromide Chemical class 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims 2
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 239000005416 organic matter Substances 0.000 abstract description 3
- 238000004887 air purification Methods 0.000 abstract description 2
- 238000006477 desulfuration reaction Methods 0.000 abstract description 2
- 230000023556 desulfurization Effects 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000003643 water by type Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 101150013917 CAT8 gene Proteins 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 102100029272 5-demethoxyubiquinone hydroxylase, mitochondrial Human genes 0.000 description 2
- 101100219344 Arabidopsis thaliana CAT7 gene Proteins 0.000 description 2
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 2
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 2
- 102100021392 Cationic amino acid transporter 4 Human genes 0.000 description 2
- 101710195194 Cationic amino acid transporter 4 Proteins 0.000 description 2
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 2
- 101000770593 Homo sapiens 5-demethoxyubiquinone hydroxylase, mitochondrial Proteins 0.000 description 2
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 2
- 108091006231 SLC7A2 Proteins 0.000 description 2
- 108091006230 SLC7A3 Proteins 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- VFYUVMGJOFRPRT-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-dimethyl-nonylazanium Chemical compound CCCCCCCCC[N+](C)(C)C1CC(C)(C)N([O])C(C)(C)C1 VFYUVMGJOFRPRT-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 101100494447 Arabidopsis thaliana CAT9 gene Proteins 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J35/396—Distribution of the active metal ingredient
- B01J35/398—Egg yolk like
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to air purification field, and in particular to a kind of room temperature is except interior VOC catalyst and preparation method thereof.Described room temperature is except the HTS TS 1 that the carrier of interior VOC catalyst is multistage pore canal；Active component is the noble metal silicon dioxide composite material of core shell structure, and the content of described active component accounts for 0.1% the 2% of catalyst gross mass.The catalyst of the present invention is applicable catalytic oxidative desulfurization at room temperature to VOC in air.The TS 1 of multistage pore canal has bigger surface area and more preferable mass transfer ability, stronger to different types of organic matter adsorption capacity in air；Simultaneously because containing Ti without Al in the TS 1 of multistage pore canal, therefore the water resistance of carrier can be effectively improved, reduction hydrone improves the life-span of catalyst in the absorption of carrier surface.
Description
Technical field
The invention belongs to air purification field, and in particular to a kind of room temperature is except interior VOC catalyst and preparation method thereof.
Background technology
Because interior decoration causes room air to be contaminated, can all there is many because interior decoration triggers disease every year
Case, VOC is volatile organic matter, if too high levels, will cause to have a strong impact on to healthy, therefore indoor VOC is polluted
The control of thing is particularly important.
VOC method has following several in conventional clean room at present：(1) VOC removers, utilize microporous substances and surface
The material of the difficult volatilization of activating agent generation, in body surface formation thin film so as to suppress VOC volatilization, the method is to delay
The release of harmful substance, it is inreal to eliminate, and also the material that remover is generated with pollutant easily causes secondary pollution；(2)
Absorption method, using some there is the material such as activated carbon of adsorptivity to adsorb the harmful components in air, but this method is main
It is physical absorption, handles not in time, harmful substance can discharges pollution air again；(3) photocatalytic method, mainly utilizes dioxy
Change the photochemical catalysts such as titanium under the irradiation of light, produce the free radical with oxidability, so that the organic pollutions such as VOC are decomposed,
But such catalyst higher catalytic activity of competence exertion only under ultraviolet irradiation, and VOC release is individual slow
Slow process, therefore discomposing effect is not satisfactory；(4) catalytic oxidation, in the presence of a catalyst, VOC in air etc. is had
Evil material changes into carbon dioxide and water, and the method high catalytic efficiency, purification are complete, are a kind of very promising purification sides
Method.
Patent 200910211847.3, which discloses a kind of mixed oxide catalyst, is used for the noxious airs such as catalysis oxidation VOC
Composition, it is oxide carried on inertia porous inorganic oxide, it is characterised in that mixed oxide catalyst includes Mn, Cu and dilute
The mixed oxide of earth metal.Patent 201210066841.3 discloses a kind of modification purified for indoor air pollutants
X-type small crystal grain molecular sieve and preparation method thereof, comprises the following steps：X-type small crystal grain molecular sieve is used for raw material, by crushing,
Screening, attrition process are into irregular granular, and working process is into required size particles shape, oven for drying, then passes through microwave method
It is modified processing.The invention discloses the purification method of VOC in air a kind of for patent 201510236586.6.Palladium charcoal is catalyzed
Agent, alcohol are mixed according to a certain percentage with certain density alkaline aqueous solution, and the gas containing VOC is at 20-50 DEG C of temperature by mixed
Close after liquid, be purified air.But there is the low defect of catalytic efficiency in existing technology.
The content of the invention
It is an object of the invention to overcome the defect of prior art there is provided a kind of room temperature except interior VOC catalyst and its
Preparation method.
To realize the purpose of the present invention, the technical scheme used for：
A kind of room temperature removes interior VOC catalyst, and carrier is the titanium-silicon molecular sieve TS-1 of multistage pore canal；Active component is core
The noble metal silicon dioxide composite material of shell structure, the content of described active component accounts for the 0.1%-2% of catalyst gross mass.
Described noble metal is one kind in Ag, Au or pt.
Described room temperature is prepared except the method for interior VOC catalyst present invention additionally comprises a kind of, it is characterised in that including
Following step：
1) titanium-silicon molecular sieve TS-1 of multistage pore canal is prepared using following manner：
The aqueous solution of surfactant and tetraethyl orthosilicate TEOS solution are thoroughly mixed 0.5-1h, 4 third are added
The base ammonium hydroxide TPAOH aqueous solution continues to stir 0.5-1h, then adds butyl titanate TBOT aqueous isopropanol, continues to stir
Mix mixing 1-2h；By above-mentioned mixed solution heating stirring backflow 1-3h in 75-85 DEG C of water bath with thermostatic control, the alcohol in solution is removed,
Numerical value before the quality polishing of the solution obtained after backflow to heating stirring is flowed back with deionized water afterwards；
Above-mentioned solution moves into 150-160 DEG C of crystallization 18-36h in autoclave, take out sample be washed with deionized to
Neutrality, dry after in Muffle furnace 500-550 DEG C roasting 4-6h, that is, obtain the TS-1 carriers of multistage pore canal；
The mol ratio of wherein each material is TEOS:TBOT:Surfactant:TPAOH:Isopropanol:H2O=1:0.01-
0.02:0.1-0.2:0.1-0.4:0.1-0.5:20-100；
2) active component is uploaded：0.2ml-1ml noble metal colloidal sols are taken in beaker, ethanol solution is added, stirs
Ammonia spirit regulation pH to 9 or so is added afterwards, under conditions of stirring, 1 μ l tetraethyl orthosilicate is added dropwise every 30min, altogether drop
Plus three times, continue to stir at least 12h after completion of dropping, then sample is centrifuged, is cleaned with ethanol 3 times, is distributed to ethanol
In solution；Solution is added in the titanium-silicon molecular sieve TS-1 of 10g multistage pore canals obtained above afterwards, at least 2h is stirred, will be mixed
Compound 80-90 DEG C of drying in Rotary Evaporators, with volume ratio is that 1%O2/N2 gaseous mixtures purging at least 2 is small after near room temperature
When, that is, obtain required catalyst.
Described surfactant is cetyl trimethylammonium bromide, myristyl-lutidines ammonium bromide, 12
Alkyl trimethyl ammonium bromide, one kind in trialkyl methyl ammonium chloride, dimethyl diallyl ammonium chloride.
Compared with prior art, the beneficial effects of the invention are as follows：
The catalyst of the present invention is applicable catalytic oxidative desulfurization at room temperature to VOC in air.The TS-1 tools of multistage pore canal
There are bigger surface area and more preferable mass transfer ability, it is stronger to different types of organic matter adsorption capacity in air；Simultaneously because
Containing Ti without Al in the TS-1 of multistage pore canal, therefore the water resistance of carrier can be effectively improved, reduction hydrone is in carrier
The absorption on surface, improves the life-span of catalyst.Noble metal (Ag, Au, Pt) is coated as work by shell of silica in the present invention
Property composition, on the one hand can make that on the other hand metal dispersion is more uniform to protect metal, make metal more stable, preferably performance is urged
Change activity.
Embodiment
In order that those skilled in the art more fully understand technical scheme, in conjunction with the embodiments to this hair
It is bright to be described further.
Embodiment 1：
(1) preparation method of HTS (TS-1) carrier of multistage pore canal：By 2g myristyls-lutidines bromine
Change ammonium, which is added in 40g deionized waters and adds 12g tetraethyl orthosilicates (TEOS), is sufficiently stirred for 1h, adds 11g tetrapropyl hydrogen
Amine-oxides (TPAOH) aqueous solution continues to stir 1h；Then 0.2g butyl titanates (TBOT) are added in 0.4g isopropanols, will
The TBOT of formation aqueous isopropanol is added in above-mentioned solution, continues to stir mixing 1.5h；Will be upper in 80 DEG C of waters bath with thermostatic control
Mixed solution heating stirring backflow 2h is stated, the alcohol in solution is removed, afterwards with deionized water by the matter of the solution obtained after backflow
Measure the numerical value before polishing flows back to heating stirring；Above-mentioned solution moves into 160 DEG C of crystallization 25h in autoclave, takes out sample and uses
Deionized water is washed to neutrality, after drying in Muffle furnace 500 DEG C of roasting 5h, that is, obtain the TS-1 carriers of multistage pore canal；
(2) active component is uploaded：1ml silver sol is taken in beaker, 15ml ethanol is added, is stirring evenly and then adding into ammonia
The aqueous solution adjusts pH to 9, under conditions of stirring, and 1 μ l tetraethyl orthosilicate is added dropwise every 30min, is added dropwise three times, drips altogether
Continue to stir 12h after finishing, then sample is centrifuged, is cleaned 3 times, is distributed in ethanol solution with ethanol；Afterwards by solution
On the TS-1 carriers for being added to 10g multistage pore canals obtained above, 2h is stirred, 90 DEG C of bakings in Rotary Evaporators by mixture
It is dry, it is 1%O2/N2 gaseous mixtures purging 2 hours with volume ratio after near room temperature, that is, obtains required catalyst, numbering is CAT1.
Embodiment 2
(1) preparation method of HTS (TS-1) carrier of multistage pore canal：By 4g cetyl trimethylammonium bromides
It is added in 40g deionized waters and adds 12g tetraethyl orthosilicates (TEOS) and be sufficiently stirred for 1h, adds 11g tetrapropyl hydroxides
Ammonium (TPAOH) aqueous solution continues to stir 1h；Then 0.2g butyl titanates (TBOT) are added in 0.4g isopropanols, will be formed
TBOT aqueous isopropanol be added in above-mentioned solution, continue to stir mixing 1.5h；Will be above-mentioned mixed in 80 DEG C of waters bath with thermostatic control
Solution heating stirring backflow 2h is closed, the alcohol in solution is removed, is afterwards mended the quality of the solution obtained after backflow with deionized water
Numerical value before the neat backflow to heating stirring；Above-mentioned solution moves into 160 DEG C of crystallization 25h in autoclave, take out sample spend from
Sub- water washing to neutrality, after drying in Muffle furnace 500 DEG C of roasting 5h, that is, obtain the TS-1 carriers of multistage pore canal；
(2) active component is uploaded：0.5ml aurosol is taken in beaker, 15ml ethanol is added, is stirring evenly and then adding into
Ammonia spirit adjusts pH to 9, under conditions of stirring, and 1 μ l tetraethyl orthosilicate is added dropwise every 30min, is added dropwise three times altogether, is added dropwise
Continue to stir 12h after finishing, then sample is centrifuged, is cleaned 3 times, is distributed in ethanol solution with ethanol；Afterwards will be molten
Liquid is added on the TS-1 carriers of 10g multistage pore canals obtained above, stirs 2h, 90 DEG C of bakings in Rotary Evaporators by mixture
It is dry, it is 1%O2/N2 gaseous mixtures purging 2 hours with volume ratio after near room temperature, that is, obtains required catalyst, numbering is CAT2.
Embodiment 3
(1) preparation method of HTS (TS-1) carrier of multistage pore canal：By 2g DTABs
It is added in 40g deionized waters and adds 12g tetraethyl orthosilicates (TEOS) and be sufficiently stirred for 1h, adds 11g tetrapropyl hydroxides
Ammonium (TPAOH) aqueous solution continues to stir 1h；Then 0.3g butyl titanates (TBOT) are added in 0.6g isopropanols, will be formed
TBOT aqueous isopropanol be added in above-mentioned solution, continue to stir mixing 1.5h；Will be above-mentioned mixed in 80 DEG C of waters bath with thermostatic control
Solution heating stirring backflow 2h is closed, the alcohol in solution is removed, is afterwards mended the quality of the solution obtained after backflow with deionized water
Numerical value before the neat backflow to heating stirring；Above-mentioned solution moves into 160 DEG C of crystallization 25h in autoclave, take out sample spend from
Sub- water washing to neutrality, after drying in Muffle furnace 500 DEG C of roasting 5h, that is, obtain the TS-1 carriers of multistage pore canal；
(2) active component is uploaded：0.2ml platinum colloidal sol is taken in beaker, 15ml ethanol is added, is stirring evenly and then adding into
Ammonia spirit adjusts pH to 9, under conditions of stirring, and 1 μ l tetraethyl orthosilicate is added dropwise every 30min, is added dropwise three times altogether, is added dropwise
Continue to stir 12h after finishing, then sample is centrifuged, is cleaned 3 times, is distributed in ethanol solution with ethanol；Afterwards will be molten
Liquid is added on the TS-1 carriers of 10g multistage pore canals obtained above, stirs 2h, 90 DEG C of bakings in Rotary Evaporators by mixture
It is dry, it is 1%O2/N2 gaseous mixtures purging 2 hours with volume ratio after near room temperature, that is, obtains required catalyst, numbering is CAT3.
Embodiment 4
(1) preparation method of HTS (TS-1) carrier of multistage pore canal：By 4g dimethyl diallyl ammonium chlorides
It is added in 100g deionized waters and adds 24g tetraethyl orthosilicates (TEOS) and be sufficiently stirred for 1h, adds 11g tetrapropyl hydroxides
Ammonium (TPAOH) aqueous solution continues to stir 1h；Then 0.3g butyl titanates (TBOT) are added in 0.6g isopropanols, will be formed
TBOT aqueous isopropanol be added in above-mentioned solution, continue to stir mixing 1.5h；Will be above-mentioned mixed in 80 DEG C of waters bath with thermostatic control
Solution heating stirring backflow 2h is closed, the alcohol in solution is removed, is afterwards mended the quality of the solution obtained after backflow with deionized water
Numerical value before the neat backflow to heating stirring；Above-mentioned solution moves into 160 DEG C of crystallization 25h in autoclave, take out sample spend from
Sub- water washing to neutrality, after drying in Muffle furnace 500 DEG C of roasting 5h, that is, obtain the TS-1 carriers of multistage pore canal；
(2) active component is uploaded：1ml silver sol is taken in beaker, 15ml ethanol is added, is stirring evenly and then adding into ammonia
The aqueous solution adjusts pH to 9, under conditions of stirring, and 1 μ l tetraethyl orthosilicate is added dropwise every 30min, is added dropwise three times, drips altogether
Continue to stir 12h after finishing, then sample is centrifuged, is cleaned 3 times, is distributed in ethanol solution with ethanol；Afterwards by solution
On the TS-1 carriers for being added to 10g multistage pore canals obtained above, 2h is stirred, 90 DEG C of bakings in Rotary Evaporators by mixture
It is dry, it is 1%O2/N2 gaseous mixtures purging 2 hours with volume ratio after near room temperature, that is, obtains required catalyst, numbering is CAT4.
Embodiment 5
(1) preparation method of HTS (TS-1) carrier of multistage pore canal：2g trialkyl methyl ammonium chlorides are added
Into 40g deionized waters and add 12g tetraethyl orthosilicates (TEOS) and be sufficiently stirred for 1h, add 11g TPAOHs
(TPAOH) aqueous solution continues to stir 1h；Then 0.4g butyl titanates (TBOT) are added in 2.0g isopropanols, by formation
TBOT aqueous isopropanol is added in above-mentioned solution, continues to stir mixing 1.5h；By above-mentioned mixing in 80 DEG C of waters bath with thermostatic control
Solution heating stirring flows back 2h, the alcohol in solution is removed, afterwards with deionized water by the quality polishing of the solution obtained after backflow
Numerical value before being flowed back to heating stirring；Above-mentioned solution moves into 160 DEG C of crystallization 25h in autoclave, takes out sample deionization
Water washing to neutrality, after drying in Muffle furnace 500 DEG C of roasting 5h, that is, obtain the TS-1 carriers of multistage pore canal；
(2) active component is uploaded：0.5ml aurosol is taken in beaker, 15ml ethanol is added, is stirring evenly and then adding into
Ammonia spirit adjusts pH to 9, under conditions of stirring, and 1 μ l tetraethyl orthosilicate is added dropwise every 30min, is added dropwise three times altogether, is added dropwise
Continue to stir 12h after finishing, then sample is centrifuged, is cleaned 3 times, is distributed in ethanol solution with ethanol；Afterwards will be molten
Liquid is added on the TS-1 carriers of 10g multistage pore canals obtained above, stirs 2h, 90 DEG C of bakings in Rotary Evaporators by mixture
It is dry, it is 1%O2/N2 gaseous mixtures purging 2 hours with volume ratio after near room temperature, that is, obtains required catalyst, numbering is CAT5.
Embodiment 6
(1) preparation method of HTS (TS-1) carrier of multistage pore canal：By 4g cetyl trimethylammonium bromides
It is added in 40g deionized waters and adds 12g tetraethyl orthosilicates (TEOS) and be sufficiently stirred for 1h, adds 11g tetrapropyl hydroxides
Ammonium (TPAOH) aqueous solution continues to stir 1h；Then 0.4g butyl titanates (TBOT) are added in 0.8g isopropanols, will be formed
TBOT aqueous isopropanol be added in above-mentioned solution, continue to stir mixing 1.5h；Will be above-mentioned mixed in 80 DEG C of waters bath with thermostatic control
Solution heating stirring backflow 2h is closed, the alcohol in solution is removed, is afterwards mended the quality of the solution obtained after backflow with deionized water
Numerical value before the neat backflow to heating stirring；Above-mentioned solution moves into 160 DEG C of crystallization 25h in autoclave, take out sample spend from
Sub- water washing to neutrality, after drying in Muffle furnace 500 DEG C of roasting 5h, that is, obtain the TS-1 carriers of multistage pore canal；
(2) active component is uploaded：0.2ml platinum colloidal sol is taken in beaker, 15ml ethanol is added, is stirring evenly and then adding into
Ammonia spirit adjusts pH to 9, under conditions of stirring, and 1 μ l tetraethyl orthosilicate is added dropwise every 30min, is added dropwise three times altogether, is added dropwise
Continue to stir 12h after finishing, then sample is centrifuged, is cleaned 3 times, is distributed in ethanol solution with ethanol；Afterwards will be molten
Liquid is added on the TS-1 carriers of 10g multistage pore canals obtained above, stirs 2h, 90 DEG C of bakings in Rotary Evaporators by mixture
It is dry, it is 1%O2/N2 gaseous mixtures purging 2 hours with volume ratio after near room temperature, that is, obtains required catalyst, numbering is CAT6.
Comparative example 1
Prepare conventional Ag/ one channel TS-1 catalyst, it is therefore an objective to contrast with embodiment 1.TS-1 single holes in the present invention
Road carrier is commercially available.
1ml silver sol is taken in beaker, 15ml ethanol is added, is stirring evenly and then adding into the TS-1 in the single ducts of 10g
On carrier, 2h is stirred, mixture is dried, that is, obtains required catalyst, numbering is CAT7.
Comparative example 2
Prepare conventional Au/ one channel TS-1TS-1 catalyst, it is therefore an objective to contrast with embodiment 2.
1ml aurosol is taken in beaker, 15ml ethanol is added, is stirring evenly and then adding into 10g one channel TS-1 carriers
On, 2h is stirred, mixture is dried, that is, obtains required catalyst, numbering is CAT8.
Comparative example 3
Prepare conventional Pt/ one channel TS-1 catalyst, it is therefore an objective to contrast with embodiment 3.
1ml platinum colloidal sol is taken in beaker, 15ml ethanol is added, is stirring evenly and then adding into 10g one channel TS-1 carriers
On, 2h is stirred, mixture is dried, that is, obtains required catalyst, numbering is CAT9.
Comparative example 4
Prepare conventional Ag/ activated-carbon catalysts, it is therefore an objective to contrast with embodiment 1.1ml silver sol is taken in beaker,
15ml ethanol is added, is stirring evenly and then adding on 10g absorbent charcoal carriers, 2h is stirred, mixture is dried, that is, is urged needed for obtaining
Agent, numbering is CAT8.
The appreciation condition reacted except VOC：Raw material is 100ppm VOC/ high pure air gaseous mixtures, 30 DEG C of reaction temperature, gas
Body volume space velocity 400min-1, catalyst particle size 40-80 mesh negates point when answering 1h and carries out sampling analysis, pair of different catalysts
Than data, it is as shown in the table：
Table 1
| Catalyst is numbered | CAT1 | CAT2 | CAT3 | CAT4 | CAT5 | CAT6 |
| VOC removal efficiencies (%) | 78.5 | 82.6 | 82.1 | 79.4 | 80.9 | 81.2 |
| Catalyst is numbered | CAT7 | CAT8 | CAT9 | CAT8 | ||
| VOC removal efficiencies (%) | 40.3 | 41.6 | 42.5 | 30.5 |
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (4)
1. a kind of room temperature removes interior VOC catalyst, it is characterised in that carrier is the titanium-silicon molecular sieve TS-1 of multistage pore canal；It is living
Property composition be core shell structure noble metal silicon dioxide composite material, the content of described active component accounts for catalyst gross mass
0.1%-2%.
2. room temperature according to claim 1 removes interior VOC catalyst, it is characterised in that described noble metal is Ag, Au
Or one kind in pt.
3. prepare the catalyst that the room temperature described in claims 1-2 removes interior VOC, it is characterised in that comprise the steps：
1) titanium-silicon molecular sieve TS-1 of multistage pore canal is prepared using following manner：
The aqueous solution of surfactant and tetraethyl orthosilicate TEOS solution are thoroughly mixed 0.5-1h, tetrapropyl hydrogen is added
The amine-oxides TPAOH aqueous solution continues to stir 0.5-1h, then adds butyl titanate TBOT aqueous isopropanol, continues to stir mixed
Close 1-2h；By above-mentioned mixed solution heating stirring backflow 1-3h in 75-85 DEG C of water bath with thermostatic control, the alcohol in solution is removed, afterwards
Numerical value before the quality polishing of the solution obtained after backflow to heating stirring is flowed back with deionized water；
Above-mentioned solution moves into 150-160 DEG C of crystallization 18-36h in autoclave, takes out sample and is washed with deionized to neutrality,
After drying in Muffle furnace 500-550 DEG C roasting 4-6h, that is, obtain the TS-1 carriers of multistage pore canal；
The mol ratio of wherein each material is TEOS:TBOT:Surfactant:TPAOH:Isopropanol:H2O=1:0.01-0.02:
0.1-0.2:0.1-0.4:0.1-0.5:20-100；
2) active component is uploaded：0.2ml-1ml noble metal colloidal sols are taken in beaker, ethanol solution is added, added after stirring
Enter ammonia spirit regulation pH to 9 or so, under conditions of stirring, the tetraethyl orthosilicate that 1 μ l are added dropwise every 30min is added dropwise three altogether
It is secondary, continue to stir at least 12h after completion of dropping, then sample is centrifuged, is cleaned with ethanol 3 times, is distributed to ethanol solution
In；Solution is added in the titanium-silicon molecular sieve TS-1 of 10g multistage pore canals obtained above afterwards, at least 2h is stirred, by mixture
It is 1%O2/N2 gaseous mixtures purging at least 2 hours with volume ratio after 80-90 DEG C of drying, near room temperature in Rotary Evaporators, i.e.,
Obtain required catalyst.
4. according to claim 3 prepare the catalyst method that room temperature removes interior VOC, it is characterised in that described surface
Activating agent be cetyl trimethylammonium bromide, myristyl-lutidines ammonium bromide, DTAB,
One kind in trialkyl methyl ammonium chloride, dimethyl diallyl ammonium chloride.
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| CN108077308A (en) * | 2017-12-11 | 2018-05-29 | 合众（佛山）化工有限公司 | A kind of antimicrobial nano titania-silica aqueous dispersion of nucleocapsid |
| CN108246361A (en) * | 2018-01-08 | 2018-07-06 | 沈阳理工大学 | A kind of method for preparing molecular sieve type titanium cerium oxide catalysis material |
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| CN108246361B (en) * | 2018-01-08 | 2020-10-30 | 沈阳理工大学 | Method for preparing molecular sieve type titanium cerium oxide photocatalytic material |
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| CN109603897B (en) * | 2018-12-29 | 2021-09-17 | 霍宜康(上海)科技有限公司 | Composite material for purifying formaldehyde in airflow |
| CN109603897A (en) * | 2018-12-29 | 2019-04-12 | 韩旭霞 | A kind of composite material for purifying formaldehyde in air-flow |
| CN110026246A (en) * | 2019-04-12 | 2019-07-19 | 天津大学 | It can be used for the preparation method of the porous organic framework atom level catalyst of the carried noble metal of constant temperature catalyzing degradation VOCs |
| WO2020206976A1 (en) * | 2019-04-12 | 2020-10-15 | 天津大学 | Preparation method for noble metal-loaded porous organic framework atomic-scale catalyst for catalytic degradation of vocs at room temperature |
| CN111974156A (en) * | 2019-05-24 | 2020-11-24 | 宁夏大学 | Preparation method of scavenger for efficiently degrading gaseous pollutants |
| CN111420699A (en) * | 2020-05-27 | 2020-07-17 | 浙江大学 | Preparation method of molecular sieve surface organic base etching and Pt-loaded catalyst |
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