CN107308983B - Room temperature removes the catalyst and preparation method thereof of interior VOC - Google Patents
Room temperature removes the catalyst and preparation method thereof of interior VOC Download PDFInfo
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- CN107308983B CN107308983B CN201710524253.2A CN201710524253A CN107308983B CN 107308983 B CN107308983 B CN 107308983B CN 201710524253 A CN201710524253 A CN 201710524253A CN 107308983 B CN107308983 B CN 107308983B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002808 molecular sieve Substances 0.000 claims abstract description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 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
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 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 74
- 238000003756 stirring Methods 0.000 claims description 62
- 239000000243 solution Substances 0.000 claims description 53
- 235000019441 ethanol Nutrition 0.000 claims description 37
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 32
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 26
- 238000010992 reflux Methods 0.000 claims description 21
- 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
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 11
- 239000008246 gaseous mixture Substances 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 238000010926 purge Methods 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 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 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- -1 myristyl-lutidines ammonium bromide Chemical class 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 2
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 239000005416 organic matter Substances 0.000 abstract description 3
- 238000004887 air purification Methods 0.000 abstract description 2
- 239000000470 constituent Substances 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
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 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
- 238000000746 purification Methods 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 101150013917 CAT8 gene Proteins 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 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
- 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 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
- 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
- NXGRFXYFVBQEHE-UHFFFAOYSA-N 2,6-dimethyl-3-tetradecylpyridine Chemical class C(CCCCCCCCCCCCC)C=1C(=NC(=CC=1)C)C NXGRFXYFVBQEHE-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000003213 activating effect 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
- 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
- 229910052799 carbon 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
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000003111 delayed effect Effects 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
- 238000011156 evaluation Methods 0.000 description 1
- 230000036541 health Effects 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
- 238000000643 oven drying Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 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
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
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- 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 fields, and in particular to a kind of room temperature removes the catalyst and preparation method thereof of interior VOC.The room temperature is except the titanium-silicon molecular sieve TS-1 that the carrier of the catalyst of interior VOC is multistage pore canal；Active constituent is the noble metal silicon dioxide composite material of core-shell structure, and the content of the active component accounts for the 0.1%-2% of catalyst gross mass.Catalyst of the invention is applicable at room temperature to the catalytic oxidative desulfurization of VOC in air.The TS-1 of multistage pore canal has bigger surface area and better mass transfer ability, stronger to organic matter adsorption capacity different types of in air；Simultaneously because containing Ti without Al in the TS-1 of multistage pore canal, therefore can effectively improve the water resistance of carrier, hydrone is reduced in the absorption of carrier surface, improves the service life of catalyst.
Description
Technical field
The invention belongs to air purification fields, and in particular to a kind of room temperature removes the catalyst and preparation method thereof of interior VOC.
Background technique
Since interior decoration causes room air to be contaminated, every year all can there are many due to interior decoration cause disease
Case, VOC is volatile organic matter, if too high levels, will cause to seriously affect to health, therefore is polluted to indoor VOC
The control of object is particularly important.
The method of VOC has following several in currently used clean room: (1) VOC remover utilizes microporous substances and surface
Activating agent generates the substance of difficult volatilization, forms thin film in body surface to inhibit the volatilization of VOC, the method is only delayed
The release of harmful substance is not eliminated really, and the substance that remover and pollutant generate be easy to cause secondary pollution；(2)
Absorption method, using the harmful components in some materials with adsorptivity such as active carbon absorption air, but this method is main
It is physical absorption, handles not in time, harmful substance can releases pollution air again；(3) photocatalytic method mainly utilizes dioxy
Change the photochemical catalysts such as titanium under the irradiation of light, generates the free radical with oxidability, so that the organic pollutants such as VOC are decomposed,
But such catalyst higher catalytic activity of competence exertion only under ultraviolet irradiation, and the release of VOC is a slow
Slow process, therefore discomposing effect is not satisfactory；(4) catalytic oxidation in the presence of a catalyst has the VOC etc. in air
Evil substance is converted to carbon dioxide and water, and the method high catalytic efficiency, purification are a kind of very promising purification sides completely
Method.
Patent 200910211847.3 discloses a kind of mixed oxide catalyst for noxious airs such as catalysis oxidation VOC
Ingredient, 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 for indoor air pollutants purification
X-type small crystal grain molecular sieve and preparation method thereof, comprising the following steps: use X-type small crystal grain molecular sieve for raw material, by being crushed,
At irregular granular, working process is at required size particles shape, baking oven drying, then passes through microwave method for screening, attrition process
It is modified processing.The invention discloses the purification methods of VOC in air a kind of for patent 201510236586.6.Palladium charcoal is catalyzed
Agent, alcohol mix 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
After closing liquid, it is purified air.But have the defects that catalytic efficiency is low in existing technology.
Summary of the invention
It is an object of the invention to overcome the deficiencies of existing technologies, provide a kind of room temperature except the catalyst of interior VOC and its
Preparation method.
To achieve the purpose of the present invention, used technical solution are as follows:
A kind of room temperature removes the catalyst of interior VOC, and carrier is the titanium-silicon molecular sieve TS-1 of multistage pore canal；Active constituent is core
The noble metal silicon dioxide composite material of shell structure, the content of the active component account for the 0.1%-2% of catalyst gross mass.
The noble metal is one of Ag, Au or pt.
The invention also includes a kind of methods for preparing the room temperature and removing the catalyst of interior VOC, which is characterized 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 ethyl orthosilicate TEOS solution are thoroughly mixed 0.5-1h, add 4 third
Base ammonium hydroxide TPAOH aqueous solution continues to stir 0.5-1h, and the aqueous isopropanol of butyl titanate TBOT is then added, continues to stir
Mix mixing 1-2h；By above-mentioned mixed solution heating stirring reflux 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 reflux to heating stirring is flowed back with deionized water later；
Above-mentioned solution moves into 150-160 DEG C of crystallization 18-36h in autoclave, take out sample be washed with deionized to
Neutrality, it is dry after in Muffle furnace 500-550 DEG C of roasting 4-6h to get the TS-1 carrier for arriving multistage pore canal；
Wherein the molar ratio of 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: taking the 0.2ml-1ml noble metal colloidal sol in beaker, ethanol solution is added, stirs evenly
Ammonia spirit is added afterwards and adjusts pH to 9 or so, under stirring conditions, the ethyl orthosilicate of 1 μ l is added dropwise every 30min, drips altogether
Add three times, continues to stir at least 12h after being added dropwise, then sample is centrifugated, is cleaned 3 times with ethyl alcohol, is distributed to ethyl alcohol
In solution；Solution is added later in the titanium-silicon molecular sieve TS-1 of 10g multistage pore canal obtained above, stirs at least 2h, will mix
Object 80-90 DEG C of drying in Rotary Evaporators is closed, with volume ratio is that 1%O2/N2 gaseous mixture purging at least 2 is small after near room temperature
When to get arrive required catalyst.
The surfactant is cetyl trimethylammonium bromide, myristyl-lutidines ammonium bromide, 12
Alkyl trimethyl ammonium bromide, one of trialkyl methyl ammonium chloride, dimethyl diallyl ammonium chloride.
Compared with prior art, the beneficial effects of the present invention are:
Catalyst of the invention is applicable at room temperature to the catalytic oxidative desulfurization of VOC in air.The TS-1 of multistage pore canal has
There are bigger surface area and better mass transfer ability, it is stronger to organic matter adsorption capacity different types of in air；Simultaneously because
It containing Ti without Al in the TS-1 of multistage pore canal, therefore can effectively improve the water resistance of carrier, reduce hydrone in carrier
The absorption on surface improves the service life of catalyst.Noble metal (Ag, Au, Pt) is coated as work by shell of silica in the present invention
Property ingredient, on the one hand can make metal dispersion it is more uniform on the other hand protect metal, keep metal more stable, preferably play urge
Change activity.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, in conjunction with the embodiments to this hair
It is bright to be described further.
Embodiment 1:
(1) preparation method of Titanium Sieve Molecular Sieve (TS-1) carrier of multistage pore canal: by 2g myristyl-lutidines bromine
Change ammonium, which is added in 40g deionized water and 12g ethyl orthosilicate (TEOS) is added, is sufficiently stirred 1h, adds 11g tetrapropyl hydrogen
Amine-oxides (TPAOH) aqueous solution continues to stir 1h；Then 0.2g butyl titanate (TBOT) is added in 0.4g isopropanol, it will
The aqueous isopropanol of the TBOT of formation is added in above-mentioned solution, continues to be stirred 1.5h；It will be upper in 80 DEG C of waters bath with thermostatic control
Mixed solution heating stirring reflux 2h is stated, the alcohol in solution is removed, later with deionized water by the matter of the solution obtained after reflux
Numerical value before measuring polishing to heating stirring reflux；Above-mentioned solution moves into 160 DEG C of crystallization 25h in autoclave, takes out sample and uses
Deionized water is washed to neutrality, it is dry after in Muffle furnace 500 DEG C of roasting 5h to get the TS-1 carrier for arriving multistage pore canal；
(2) active component is uploaded: taking the silver sol of 1ml in beaker, 15ml ethyl alcohol is added, is stirring evenly and then adding into ammonia
Aqueous solution adjusts pH to 9, under stirring conditions, the ethyl orthosilicate of 1 μ l is added dropwise every 30min, is added dropwise three times, drips altogether
Continue to stir 12h after finishing, then sample is centrifugated, is cleaned 3 times, is distributed in ethanol solution with ethyl alcohol；Later by solution
It is added on the TS-1 carrier of 10g multistage pore canal obtained above, stirs 2h, 90 DEG C of bakings in Rotary Evaporators by mixture
It is dry, it is 1%O2/N2 gaseous mixture purging 2 hours to get required catalyst, number CAT1 is arrived with volume ratio after near room temperature.
Embodiment 2
(1) preparation method of Titanium Sieve Molecular Sieve (TS-1) carrier of multistage pore canal: by 4g cetyl trimethylammonium bromide
It is added in 40g deionized water and 12g ethyl orthosilicate (TEOS) is added and 1h is sufficiently stirred, add 11g tetrapropyl hydroxide
Ammonium (TPAOH) aqueous solution continues to stir 1h；Then 0.2g butyl titanate (TBOT) is added in 0.4g isopropanol, will be formed
The aqueous isopropanol of TBOT be added in above-mentioned solution, continue to be stirred 1.5h；It will be above-mentioned mixed in 80 DEG C of waters bath with thermostatic control
Solution heating stirring reflux 2h is closed, the alcohol in solution is removed, is later mended the quality of the solution obtained after reflux with deionized water
Numerical value before the neat reflux 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, it is dry after in Muffle furnace 500 DEG C of roasting 5h to get the TS-1 carrier for arriving multistage pore canal；
(2) active component is uploaded: taking the aurosol of 0.5ml in beaker, 15ml ethyl alcohol is added, is stirring evenly and then adding into
Ammonia spirit adjusts pH to 9, under stirring conditions, the ethyl orthosilicate of 1 μ l is added dropwise every 30min, is added dropwise three times, is added dropwise altogether
After continue stir 12h, then sample is centrifugated, is cleaned 3 times, is distributed in ethanol solution with ethyl alcohol；It later will be molten
Liquid is added on the TS-1 carrier of 10g multistage pore canal obtained above, stirs 2h, 90 DEG C of bakings in Rotary Evaporators by mixture
It is dry, it is 1%O2/N2 gaseous mixture purging 2 hours to get required catalyst, number CAT2 is arrived with volume ratio after near room temperature.
Embodiment 3
(1) preparation method of Titanium Sieve Molecular Sieve (TS-1) carrier of multistage pore canal: by 2g dodecyl trimethyl ammonium bromide
It is added in 40g deionized water and 12g ethyl orthosilicate (TEOS) is added and 1h is sufficiently stirred, add 11g tetrapropyl hydroxide
Ammonium (TPAOH) aqueous solution continues to stir 1h；Then 0.3g butyl titanate (TBOT) is added in 0.6g isopropanol, will be formed
The aqueous isopropanol of TBOT be added in above-mentioned solution, continue to be stirred 1.5h；It will be above-mentioned mixed in 80 DEG C of waters bath with thermostatic control
Solution heating stirring reflux 2h is closed, the alcohol in solution is removed, is later mended the quality of the solution obtained after reflux with deionized water
Numerical value before the neat reflux 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, it is dry after in Muffle furnace 500 DEG C of roasting 5h to get the TS-1 carrier for arriving multistage pore canal；
(2) active component is uploaded: taking the platinum colloidal sol of 0.2ml in beaker, 15ml ethyl alcohol is added, is stirring evenly and then adding into
Ammonia spirit adjusts pH to 9, under stirring conditions, the ethyl orthosilicate of 1 μ l is added dropwise every 30min, is added dropwise three times, is added dropwise altogether
After continue stir 12h, then sample is centrifugated, is cleaned 3 times, is distributed in ethanol solution with ethyl alcohol；It later will be molten
Liquid is added on the TS-1 carrier of 10g multistage pore canal obtained above, stirs 2h, 90 DEG C of bakings in Rotary Evaporators by mixture
It is dry, it is 1%O2/N2 gaseous mixture purging 2 hours to get required catalyst, number CAT3 is arrived with volume ratio after near room temperature.
Embodiment 4
(1) preparation method of Titanium Sieve Molecular Sieve (TS-1) carrier of multistage pore canal: by 4g dimethyl diallyl ammonium chloride
It is added in 100g deionized water and 24g ethyl orthosilicate (TEOS) is added and 1h is sufficiently stirred, add 11g tetrapropyl hydroxide
Ammonium (TPAOH) aqueous solution continues to stir 1h；Then 0.3g butyl titanate (TBOT) is added in 0.6g isopropanol, will be formed
The aqueous isopropanol of TBOT be added in above-mentioned solution, continue to be stirred 1.5h；It will be above-mentioned mixed in 80 DEG C of waters bath with thermostatic control
Solution heating stirring reflux 2h is closed, the alcohol in solution is removed, is later mended the quality of the solution obtained after reflux with deionized water
Numerical value before the neat reflux 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, it is dry after in Muffle furnace 500 DEG C of roasting 5h to get the TS-1 carrier for arriving multistage pore canal；
(2) active component is uploaded: taking the silver sol of 1ml in beaker, 15ml ethyl alcohol is added, is stirring evenly and then adding into ammonia
Aqueous solution adjusts pH to 9, under stirring conditions, the ethyl orthosilicate of 1 μ l is added dropwise every 30min, is added dropwise three times, drips altogether
Continue to stir 12h after finishing, then sample is centrifugated, is cleaned 3 times, is distributed in ethanol solution with ethyl alcohol；Later by solution
It is added on the TS-1 carrier of 10g multistage pore canal obtained above, stirs 2h, 90 DEG C of bakings in Rotary Evaporators by mixture
It is dry, it is 1%O2/N2 gaseous mixture purging 2 hours to get required catalyst, number CAT4 is arrived with volume ratio after near room temperature.
Embodiment 5
(1) preparation method of Titanium Sieve Molecular Sieve (TS-1) carrier of multistage pore canal: 2g trialkyl methyl ammonium chloride is added
Into 40g deionized water and 12g ethyl orthosilicate (TEOS) is added 1h is sufficiently stirred, adds 11g tetrapropylammonium hydroxide
(TPAOH) aqueous solution continues to stir 1h；Then 0.4g butyl titanate (TBOT) is added in 2.0g isopropanol, by formation
The aqueous isopropanol of TBOT is added in above-mentioned solution, continues to be stirred 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, later with deionized water by the quality polishing of the solution obtained after reflux
Numerical value to before heating stirring reflux；Above-mentioned solution moves into 160 DEG C of crystallization 25h in autoclave, takes out sample deionization
Water washing to neutrality, it is dry after in Muffle furnace 500 DEG C of roasting 5h to get the TS-1 carrier for arriving multistage pore canal；
(2) active component is uploaded: taking the aurosol of 0.5ml in beaker, 15ml ethyl alcohol is added, is stirring evenly and then adding into
Ammonia spirit adjusts pH to 9, under stirring conditions, the ethyl orthosilicate of 1 μ l is added dropwise every 30min, is added dropwise three times, is added dropwise altogether
After continue stir 12h, then sample is centrifugated, is cleaned 3 times, is distributed in ethanol solution with ethyl alcohol；It later will be molten
Liquid is added on the TS-1 carrier of 10g multistage pore canal obtained above, stirs 2h, 90 DEG C of bakings in Rotary Evaporators by mixture
It is dry, it is 1%O2/N2 gaseous mixture purging 2 hours to get required catalyst, number CAT5 is arrived with volume ratio after near room temperature.
Embodiment 6
(1) preparation method of Titanium Sieve Molecular Sieve (TS-1) carrier of multistage pore canal: by 4g cetyl trimethylammonium bromide
It is added in 40g deionized water and 12g ethyl orthosilicate (TEOS) is added and 1h is sufficiently stirred, add 11g tetrapropyl hydroxide
Ammonium (TPAOH) aqueous solution continues to stir 1h；Then 0.4g butyl titanate (TBOT) is added in 0.8g isopropanol, will be formed
The aqueous isopropanol of TBOT be added in above-mentioned solution, continue to be stirred 1.5h；It will be above-mentioned mixed in 80 DEG C of waters bath with thermostatic control
Solution heating stirring reflux 2h is closed, the alcohol in solution is removed, is later mended the quality of the solution obtained after reflux with deionized water
Numerical value before the neat reflux 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, it is dry after in Muffle furnace 500 DEG C of roasting 5h to get the TS-1 carrier for arriving multistage pore canal；
(2) active component is uploaded: taking the platinum colloidal sol of 0.2ml in beaker, 15ml ethyl alcohol is added, is stirring evenly and then adding into
Ammonia spirit adjusts pH to 9, under stirring conditions, the ethyl orthosilicate of 1 μ l is added dropwise every 30min, is added dropwise three times, is added dropwise altogether
After continue stir 12h, then sample is centrifugated, is cleaned 3 times, is distributed in ethanol solution with ethyl alcohol；It later will be molten
Liquid is added on the TS-1 carrier of 10g multistage pore canal obtained above, stirs 2h, 90 DEG C of bakings in Rotary Evaporators by mixture
It is dry, it is 1%O2/N2 gaseous mixture purging 2 hours to get required catalyst, number CAT6 is arrived with volume ratio after near room temperature.
Comparative example 1
Prepare conventional Ag/ one channel TS-1 catalyst, it is therefore an objective to compare with embodiment 1.TS-1 single hole in the present invention
Road carrier is commercially available.
It takes the silver sol of 1ml in beaker, 15ml ethyl alcohol is added, is stirring evenly and then adding into the TS-1 in the single duct 10g
On carrier, 2h is stirred, mixture is dried to get required catalyst, number CAT7 is arrived.
Comparative example 2
Prepare conventional Au/ one channel TS-1TS-1 catalyst, it is therefore an objective to compare with embodiment 2.
It takes the aurosol of 1ml in beaker, 15ml ethyl alcohol is added, is stirring evenly and then adding into 10g one channel TS-1 carrier
On, 2h is stirred, mixture is dried to get required catalyst, number CAT8 is arrived.
Comparative example 3
Prepare conventional Pt/ one channel TS-1 catalyst, it is therefore an objective to compare with embodiment 3.
It takes the platinum colloidal sol of 1ml in beaker, 15ml ethyl alcohol is added, is stirring evenly and then adding into 10g one channel TS-1 carrier
On, 2h is stirred, mixture is dried to get required catalyst, number CAT9 is arrived.
Comparative example 4
Prepare conventional Ag/ activated-carbon catalyst, it is therefore an objective to compare with embodiment 1.Take the silver sol of 1ml in beaker,
15ml ethyl alcohol is added, is stirring evenly and then adding on 10g absorbent charcoal carrier, stirs 2h, mixture is dried and is urged to get needed for
Agent, number CAT8.
Except VOC reaction evaluation condition: raw material be 100ppm VOC/ high pure air gaseous mixture, 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 number | CAT1 | CAT2 | CAT3 | CAT4 | CAT5 | CAT6 |
| VOC removal efficiency (%) | 78.5 | 82.6 | 82.1 | 79.4 | 80.9 | 81.2 |
| Catalyst number | CAT7 | CAT8 | CAT9 | CAT8 | ||
| VOC removal efficiency (%) | 40.3 | 41.6 | 42.5 | 30.5 |
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (3)
1. the catalyst that a kind of room temperature removes interior VOC, which is characterized in that carrier is the titanium-silicon molecular sieve TS-1 of multistage pore canal；It is living
Property ingredient be core-shell structure noble metal silicon dioxide composite material, the content of the active component accounts for catalyst gross mass
0.1%-2%；
The preparation room temperature includes the following steps: the Titanium Sieve Molecular Sieve of 1) multistage pore canal except the method for the catalyst of interior VOC
TS-1 is prepared using following manner:
The aqueous solution of surfactant and ethyl orthosilicate TEOS solution are thoroughly mixed 0.5-1h, add tetrapropyl hydrogen
Amine-oxides TPAOH aqueous solution continues to stir 0.5-1h, and the aqueous isopropanol of butyl titanate TBOT is then added, and it is mixed to continue stirring
Close 1-2h；By above-mentioned mixed solution heating stirring reflux 1-3h in 75-85 DEG C of water bath with thermostatic control, the alcohol in solution is removed, later
Numerical value before the quality polishing of the solution obtained after reflux 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 to get arrive multistage pore canal TS-1 carrier；
Wherein the molar ratio of 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: take the 0.2ml-1ml noble metal colloidal sol in beaker, ethanol solution be added, after mixing evenly plus
Enter ammonia spirit and adjust pH to 9, under stirring conditions, the ethyl orthosilicate of 1 μ l is added dropwise every 30min, is added dropwise altogether three times, drop
It adds and continues to stir at least 12h after finishing, then sample is centrifugated, is cleaned 3 times, is distributed in ethanol solution with ethyl alcohol；It
Solution is added afterwards in the titanium-silicon molecular sieve TS-1 of 10g multistage pore canal obtained above, stirs at least 2h, mixture is being rotated
80-90 DEG C of drying in evaporimeter with volume ratio is that 1%O2/N2 gaseous mixture purges at least 2 hours to get to institute after near room temperature
Need catalyst.
2. the catalyst that room temperature according to claim 1 removes interior VOC, which is characterized in that the noble metal is Ag, Au
Or one of pt.
3. the catalyst that room temperature according to claim 1 removes interior VOC, which is characterized in that the surfactant is
Cetyl trimethylammonium bromide, myristyl-lutidines ammonium bromide, dodecyl trimethyl ammonium bromide, trialkyl first
One of ammonium chloride, dimethyl diallyl ammonium chloride.
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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 |
| CN109046446A (en) * | 2018-08-30 | 2018-12-21 | 河北科技大学 | A kind of metal oxide/HTS-1 titanium-silicon molecular sieve catalyst and its preparation method and application |
| CN111085205B (en) * | 2018-10-23 | 2022-12-06 | 华东理工大学 | Carbon Porous Metal Based Integral Modified TS-1 Catalyst, Preparation Method and Application |
| 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 |
| CN110026246B (en) * | 2019-04-12 | 2020-08-28 | 天津大学 | Preparation method of noble metal-supported 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 |
| CN111420699B (en) * | 2020-05-27 | 2021-07-13 | 浙江大学 | A kind of preparation method of molecular sieve surface organic alkali etching and supported Pt catalyst |
| CN111841625A (en) * | 2020-08-20 | 2020-10-30 | 江苏博霖环保科技有限公司 | Preparation method of catalyst for treating VOCs (volatile organic compounds) by using fiber composite molecular sieve membrane |
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