CN109999797A - A kind of more effect high dispersive structure catalysts and preparation method for indoor purifying - Google Patents
A kind of more effect high dispersive structure catalysts and preparation method for indoor purifying Download PDFInfo
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- CN109999797A CN109999797A CN201910343887.7A CN201910343887A CN109999797A CN 109999797 A CN109999797 A CN 109999797A CN 201910343887 A CN201910343887 A CN 201910343887A CN 109999797 A CN109999797 A CN 109999797A
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- high dispersive
- formaldehyde
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- indoor purifying
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 230000000694 effects Effects 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 124
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 29
- 230000003647 oxidation Effects 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 7
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 238000012545 processing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 14
- 238000012986 modification Methods 0.000 claims description 14
- 238000006555 catalytic reaction Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 5
- 230000036571 hydration Effects 0.000 claims description 5
- 238000006703 hydration reaction Methods 0.000 claims description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 claims description 2
- HHDOORYZQSEMGM-UHFFFAOYSA-L potassium;oxalate;titanium(4+) Chemical compound [K+].[Ti+4].[O-]C(=O)C([O-])=O HHDOORYZQSEMGM-UHFFFAOYSA-L 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 239000012629 purifying agent Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- 239000006185 dispersion Substances 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 229930040373 Paraformaldehyde Natural products 0.000 abstract 1
- 239000012876 carrier material Substances 0.000 abstract 1
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 229920002866 paraformaldehyde Polymers 0.000 abstract 1
- 235000019256 formaldehyde Nutrition 0.000 description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
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- 238000006243 chemical reaction Methods 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- -1 salts sodium carbonate Chemical class 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- 208000014085 Chronic respiratory disease Diseases 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 208000024207 chronic leukemia Diseases 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 239000003317 industrial substance Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0225—Coating of metal substrates
- B01J37/0226—Oxidation of the substrate, e.g. anodisation
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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Abstract
The present invention discloses a kind of more effect high dispersive structure catalysts and preparation method thereof for indoor purifying, it will be by the self-growing one layer of ordered porous alumina of Metal Substrate as carrier, it is modified processing to it using alkali metal inorganic salts, metal oxide, improves the specific surface area of carrier material；Any one in modified carried noble metal platinum, palladium or two kinds of mixtures obtain more effect high dispersive structure catalysts of coupling photocatalysis and the indoor purifying without photocatalytic system.Due to the interaction between modified component metal oxide and noble metal active component, the dispersion degree of active component can be improved, so as to improve the catalytic activity of catalyst.Formaldehyde catalytically active assessment is carried out with catalyst prepared by the present invention, catalyst PARA FORMALDEHYDE PRILLS(91,95) has good attached ability, formaldehyde through catalytic oxidation can be efficiently carried out at room temperature, under the conditions of 0 DEG C of low temperature, removing formaldehyde still has good catalytic effect, and there is good tolerance, it can be good at carrying out industrial applications.
Description
Technical field
The present invention relates to catalytic oxidations to handle indoor air pollutants field, is used for indoor purifying more particularly to one kind
More effect high dispersive structure catalysts and preparation method thereof.
Background technique
Main source of the volatile organic compounds (VOCs) as atmosphere pollution, the indoor most common VOCs have benzene homologues
(benzene,toluene,xylene etc.) and formaldehyde carry out very big threat for human body health care belt.Wherein formaldehyde stands in the breach, and is indoor most typically
One of pollutant.Formaldehyde is mainly used in synthetic resin, rubber, leather industry, doctor as widely applied industrial chemicals
Medicine, dyestuff, construction material etc..China's national Specification, the concentration of Formaldehyde Pollution of Indoor Air object is no more than 0.08mg/m3.And
Formaldehyde is caused indoor formaldehyde concentration constantly to be accumulated and is increased final exceeded complaint and report by successively releasing in finishing material
Road is commonplace.People's Long Term Contact low dosage formaldehyde can cause chronic respiratory disease, leukaemia or even cancer etc., to human body
Health causes to plant threat.Therefore effectively purifying indoor formaldehyde pollution problem is extremely urgent.
Currently, purifying indoor formaldehyde method is concentrated mainly on ventilation ventilation, absorption method, plant absorption method, photochemical catalytic oxidation
And catalytic oxidation.Contrastingly, loaded noble metal catalyst belongs to compared with low temperature catalytic combustion technology, specifically in catalyst
Under the action of, flameless combustion occurs at a lower temperature for pernicious gas, and oxygenolysis generates nontoxic CO2And H2O has effect
The features such as rate is high, energy consumption is small, without secondary pollution, which is used widely.The research of loaded noble metal catalyst at present
It concentrates on particle or fine catalyst, noble metal (Pt, Au, Pd, Rh etc.) is usually supported on molecular sieve or metal oxygen
On compound and carrier, when preparation because current catalyst there are pressure drops big, poor thermal conductivity, it is easily broken the disadvantages of (such as Chinese patent
CN20141042073), it is difficult for beaded catalyst to be applied in the polluted gas such as industrial treatment formaldehyde, and uses anodic oxidation
Integrated catalyst can effectively solve this problem.
Patent CN106040230A discloses a kind of preparation side of integrated catalyst for formaldehyde low-temperature catalytic oxidation
Method, this method utilize homemade anodic oxidation aluminium sheet, are prepared by the effect that hot water closes rich in the porous of surface-active hydroxyl
The Pt/AlOOH integration catalyst of nanometer material structure, the conversion ratio 70% or so of formaldehyde under room temperature；Patent
CN102941111A discloses a kind of catalyst of metal carrier load for room temperature purifying formaldehyde, and the catalyst is by metal
Carrier, float on on porous material auxiliary agent and noble metal active component form, the metallic carrier of the catalyst is ferro-aluminum chromium
Alloy, selection noble metal is platinum, man, any one in gold, and auxiliary agent is selected in alkaline-earth metal or alkaline earth oxide
Any one or two or more mixtures.Patent CN109289845A discloses a kind of titanium dioxide composite noble metal catalysis
The preparation of agent, the catalyst mix system with precious metal salt solution by the modifying titanium dioxide that also Primordial Qi reduction titanium dioxide obtains
The catalyst obtained, the noble metal that the catalyst is selected are any one or two or more combinations in platinum, gold, palladium or iridium.
But the catalyst of above-mentioned existing technology is golden for the Pt partial size, dispersion degree and alkali that improve noble metal catalyst using auxiliary agent
Belong to and transition metal combines the influence for catalyst surface active hydroxyl not investigate.
Summary of the invention
In order to solve the problems, such as that existing catalyst noble metal dispersion degree is not high, the object of the present invention is to provide one kind to be used for
More effect high dispersive structure catalysts of indoor purifying and preparation method thereof, the preparation process of the catalyst is simple, and structuring is urged
Agent has the characteristics that pressure drop is low, heat and mass transfer performance is excellent and easy plastotype, has good industrial application value.
To achieve the above object, the present invention provides following schemes:
The present invention provides a kind of more effect high dispersive structure catalysts for indoor purifying, comprising:
Metallic carrier；The modification ordered porous alumina being grown on metallic carrier；With
The noble metal active component being carried on the modified ordered porous alumina；The noble metal active component
Average grain diameter is 1-6.9nm.
Further, the metallic carrier can be aluminum monolayer carrier or aluminium/iron zinc chrome/aluminium multilayer carrier, and shape includes plate
Shape, netted, honeycomb.
The present invention also provides a kind of preparation methods of above-mentioned scattered structuring metal-based catalyst, which is to pass through metal
The self-growing one layer of ordered porous alumina of carrier；And the film is modified, appointing in modified carried noble metal platinum, palladium
One or two of anticipating mixtures；
Preparation method includes the following steps:
1) by anodic oxidation, electricity execution and rubbing method processing, the metal base load with ordered porous alumina is obtained
Body；The anodic oxidation, electricity execution and rubbing method processing are using conventional treatment method in field, and details are not described herein；
2) metallic-based support that step 1) obtains is modified；
3) the carried noble metal active component on the modified support that step 2) obtains；
4) reduction treatment is carried out to the catalyst that step 3) obtains, obtains more effect high dispersive structures for indoor purifying
Catalyst.
Further, in the step 1), the ordered porous alumina of generation, film thickness is 10-300 μm, aperture 2-
50nm。
Preferably, control film thickness is 60-120 μm, aperture 2-12nm.
Further, in the step 2), modifying agent used is alkali metal inorganic salts.
Further, the alkali metal inorganic salts selection sodium carbonate, 30-95 DEG C of modification temperature, time 1-5h, preferably
70-90 DEG C, 3-4h.
Further, it after modification of sodium carbonate, is modified again using transistion metal compound, to increase catalyst
Specific surface area；The transistion metal compound selection titanium potassium oxalate, 30-95 DEG C of modification temperature, time 1-8h, preferably 70-
90 DEG C, 4-8h；It is modified to dry roasting, so that it is converted into metal oxide, 500-550 DEG C of maturing temperature, calcining time 1-4h.
Further, in the step 3), the noble metal active component of selection is that platinum, any one or two kinds in palladium are mixed
Close object.
Further, in the step 3), by adjusting solution pH value, hydration is carried out under high temperature and is supported on metal-based catalyzed
In agent；30-95 DEG C of hydration temperature, time 1-5h, preferably 70-90 DEG C, 3-4h.
Further, in the step 4), reduction treatment is carried out using sodium borohydride or hydrogen.
The step 2) and step 3) sequence are interchangeable or synchronous can carry out.
By the weight of catalyst be 100% in terms of, based on metal element wt, the weight hundred of metal oxide in the modification
Divide ratio for 0.5-15%, such as 0.5%, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 15%, preferably 2%-10%；It is expensive
The weight percent of metal active constituent is 0.1%-3%, such as 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%,
It is preferred that 1.5%-2.0%.
The activity rating condition of catalyst are as follows: the catalyst is applied to formaldehyde through catalytic oxidation activation evaluating system -3m3Ring
In the test chamber of border, catalyst area 30cm*28cm=0.084m2, the initial concentration 1.0ppm of formaldehyde, room temperature environment (temperature:
25 ± 3 DEG C, relative humidity RH:60 ± 10%), recycle wind speed 1.80m/s.
The present invention also provides a kind of catalysis oxidation first of above-mentioned more effect high dispersive structure catalysts for indoor purifying
The method of aldehyde,
When concentration of formaldehyde is greater than 0.1ppm, the catalysis oxidation of formaldehyde is carried out under the conditions of ultraviolet light；
When concentration of formaldehyde is less than 0.1ppm, the catalysis oxidation of formaldehyde is carried out under the conditions of no ultraviolet light；
When initial concentration of formaldehyde is greater than 0.1ppm, the catalysis oxidation of formaldehyde is first carried out under the conditions of ultraviolet light, works as first
When aldehyde concentration is less than 0.1ppm, formaldehyde treating technology is carried out under the conditions of no ultraviolet light.
The invention discloses following technical effects:
1, for the present invention using the metallic-based support with ordered porous alumina, which can be spontaneous by Metal Substrate
Pellumina is grown, film thickness is controllable, and aperture is controllable；And the type carried catalyst has low pressure drop, mass-and heat-transfer good, Yi Jiyi
The advantages that plastotype, can have and be applied in air purifier well, carry out miniature set in evolution device in the market, be conducive to work
Industry；
2, the modification provided by the invention to metallic-based support, Na2CO3Solution alkaline, under suitable alkaline condition, meeting
Its specific surface area is improved in corrosion vector duct；And in two groups of modifications, modified solution temperature is higher, and dipping can improve for a long time
Carrier specific surface area, and since the interaction between modified component and noble metal active component, carrier specific surface area increase, it inhales
Attached position is increased, and hydroxyl increases, and the absorption of Pt is promoted to disperse；Part Pt can be supported on TiO2Surface, TiO2Electricity can be provided for it
Son makes Pt be enriched with electronics, so that the dispersion degree of noble metal active component is improved, to further improve urging for catalyst
Change activity；
3, more effect high dispersive structure catalysts prepared by the present invention for indoor purifying can be in room temperature normal temperature environment
CO efficiently is converted by formaldehyde through catalytic oxidation down2And H2O is suitable for indoor air purification, and has good tolerance, answers
When for air purifier, good catalytic activity can be still kept after the operation that works long hours.
Detailed description of the invention
It in order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below will be to institute in embodiment
Attached drawing to be used is needed to be briefly described, it should be apparent that, the accompanying drawings in the following description is only some implementations of the invention
Example, for those of ordinary skill in the art, without creative efforts, can also obtain according to these attached drawings
Obtain other attached drawings.
Fig. 1 is catalytically active assessment of the embodiment 1-6 preparation for more effect high dispersive structure catalysts of indoor purifying
As a result, it shows influence of the modifying agent Different adding amount to the catalytic activity of catalyst.
Fig. 2 is the tolerance test chart of more effect high dispersive structure catalysts for indoor purifying prepared by embodiment 6,
It is indicated the time required to being down to standard value 0.08ppm with HCHO concentration.
Fig. 3 is more effect high dispersive structure catalysts for indoor purifying of the preparation of embodiment 6 in condition of different temperatures
Under conversion ratio.
Fig. 4 is the more effect high dispersive structure catalysts for indoor purifying that prepare of embodiment 6 whether there is or not ultraviolet lightings
Under the conditions of catalytically active assessment result.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to the accompanying drawing and specific real
Applying mode, the present invention is described in further detail.
Embodiment 1-6
A kind of more effect high dispersive structure catalysts for indoor purifying, comprising:
Metallic carrier；The modification ordered porous alumina being grown on metallic carrier；The modification is orderly with being carried on
Noble metal active component on multiaperture pellumina；
It is prepared according to the following steps:
1) by anodized, the metallic-based support with ordered porous alumina is obtained, and control film thickness and be
10-300 μm, aperture 2-50nm；
2) metallic-based support that step 1) obtains is modified using alkali metal inorganic salts sodium carbonate, modification temperature 30-
95 DEG C, time 1-5h, preferably 70-90 DEG C, 3-4h；It is modified, is changed again using transistion metal compound titanium potassium oxalate
Warm-natured 30-95 DEG C of degree, time 1-8h, preferably 70-90 DEG C, 4-8h；It is modified to dry roasting, so that it is converted into metal oxidation
Object, 500-550 DEG C of maturing temperature, calcining time 1-4h；
3) by adjusting solution pH value, carried noble metal active group is hydrated on the modified support that step 2) obtains under high temperature
Point；30-95 DEG C of hydration temperature, time 1-5h, preferably 70-90 DEG C, 3-4h；
4) reduction treatment is carried out using sodium borohydride to the catalyst that step 3) obtains, obtains more function for indoor purifying
Imitate high dispersive structure catalyst.
It wherein, is in terms of 100% by the weight of catalyst, sodium carbonate is based on sodium element weight, the weight percent of sodium carbonate
It is 2%；For titanium dioxide based on titanium elements weight, the weight percent of titanium dioxide is 0-10%；The weight percent of platinum is
2%.
The agent of embodiment 1-6 metal oxide modified, noble metal active component, noble metal active component dispersion degree and your gold
Belong to active component partial size and is shown in Table 1.
Table 1 indicates that different modifying agent usage amounts (are with the weight of catalyst on the influence of noble metal active component dispersion degree
100% meter)
The catalyst prepared in above-described embodiment is subjected to formaldehyde catalysis reaction under room temperature environment.Take 0.084m2Catalyst,
It is fitted into air purifier, tests in 3m3It (is prepared) and is carried out according to GB/T 18801-2008 in environmental test chamber, using GB/
The concentration of phenol reagent method measurement formaldehyde in T18204.26-2000.Initial concentration of formaldehyde is 0.8-1.0ppm, temperature
Degree is room temperature, recycles wind speed 1.80m/s, and every 5min sampling is primary.Fig. 1 is more function that embodiment 1-6 preparation is used for indoor purifying
Imitate the catalytically active assessment result of high dispersive structure catalyst.
It will be seen from figure 1 that more effect high dispersive structure catalysts for indoor purifying of embodiment 1-6 preparation can
The usage amount of the efficient catalysis oxidation formaldehyde under room temperature normal temperature environment, metal oxide modified agent influences noble metal active component
Dispersion degree, thus further influence formaldehyde catalytic degradation efficiency.On the other hand, prepared by the present invention for the more of indoor purifying
Effect high dispersive structure catalyst is easy to use, can change shape, size according to demand.
Fig. 2 is the tolerance test chart of more effect high dispersive structure catalysts for indoor purifying prepared by embodiment 6,
It is indicated the time required to being down to standard value 0.08ppm with HCHO concentration.To integrated catalyst in 3m when tolerance is tested3Ring
Border test chamber intermittent is tested formaldehyde through catalytic oxidation effect 18 times totally, after continuing working 2048 minutes (34h), catalyst activity
There is no significant changes, still there is good formaldehyde catalytic degradation effect.Illustrate that the stability of catalyst is preferable, there is good reality
Border application prospect.
The catalyst prepared in above-described embodiment 6 is applied in formaldehyde combustion system, reaction condition are as follows: catalyst
0.3g, concentration of formaldehyde 200ppm carry out the property of catalyst at different temperatures at air speed 3000-15,000L/ (gh)
It can evaluate, as a result as shown in Figure 3.Catalyst just has good catalytic activity at 0 DEG C of low temperature.
The catalyst prepared in above-described embodiment 6 is subjected to formaldehyde catalysis reaction under ultraviolet irradiation condition, takes 0.084m2It urges
Agent is fitted into air purifier, is tested in 3m3(being prepared according to GB/T18801-2008) carries out in environmental test chamber, uses
The concentration of phenol reagent method measurement formaldehyde in GB/T18204.26-2000.Initial concentration of formaldehyde is 0.8-1.0ppm,
Temperature is room temperature, recycles wind speed 1.80m/s, and every 5min sampling is primary, carries out catalyst whether there is or not the performances under ultraviolet lighting to comment
Valence, as a result as shown in figure 4, faster, catalytic effect is more preferable, illustrates, ultraviolet light for Degradation Formaldehyde rate under discovery ultraviolet irradiation condition
According under the conditions of, not only there is metal catalytic oxidation effect, there are also photocatalysis, the two synergistic effect, co-catalysis Degradation Formaldehydes.
Embodiment described above is only that preferred embodiment of the invention is described, and is not carried out to the scope of the present invention
It limits, without departing from the spirit of the design of the present invention, those of ordinary skill in the art make technical solution of the present invention
Various changes and improvements, should all fall into claims of the present invention determine protection scope in.
Claims (10)
1. a kind of more effect high dispersive structure catalysts for indoor purifying characterized by comprising
Metallic carrier；The modification ordered porous alumina being grown on metallic carrier；With
The noble metal active component being carried on the modified ordered porous alumina；The noble metal active component is averaged
Partial size is 1-6.9nm；
It is in terms of 100% by the weight of catalyst, the weight percent of noble metal active component is based on metal element wt
0.1%-3%.
2. a kind of more effect high dispersive structure catalysts for indoor purifying according to claim 1, which is characterized in that
The metallic carrier can be aluminum monolayer carrier or aluminium/iron zinc chrome/aluminium multilayer carrier, and shape includes plate, netted, honeycomb.
3. a kind of preparation side of the described in any item more effect high dispersive structure catalysts for indoor purifying of claim 1-2
Method, which is characterized in that preparation method includes the following steps:
1) by anodic oxidation, electricity execution and rubbing method processing, the metallic-based support with ordered porous alumina is obtained；
2) metallic-based support that step 1) obtains is modified；
3) the carried noble metal active component on the modified support that step 2) obtains；
4) reduction treatment is carried out to the catalyst that step 3) obtains, obtains more effect high dispersive structured catalysis for indoor purifying
Agent.
4. the preparation method of more effect high dispersive structure catalysts according to claim 3 for indoor purifying, special
Sign is, in the step 1), the ordered porous alumina of generation, film thickness is 10-300 μm, aperture 2-50nm.
5. the preparation method of more effect high dispersive structure catalysts according to claim 3 for indoor purifying, special
Sign is, in the step 2), modifying agent used is alkali metal inorganic salts.
6. the preparation method of more effect high dispersive structure catalysts according to claim 5 for indoor purifying, special
Sign is, the alkali metal inorganic salts select sodium carbonate, 30-95 DEG C of modification temperature, time 1-5h.
7. the preparation method of more effect high dispersive structure catalysts according to claim 6 for indoor purifying, special
Sign is, after modification of sodium carbonate, is modified again using transistion metal compound；The transistion metal compound is selected
Titanium potassium oxalate, 30-95 DEG C of modification temperature, time 1-8h；It is modified to dry roasting, so that it is converted into metal oxide, roasting temperature
500-550 DEG C of degree, calcining time 1-4h.
8. the preparation method of more effect high dispersive structure catalysts according to claim 3 for indoor purifying, special
Sign is, in the step 3), the noble metal active component of selection is platinum, any one or two kinds of mixtures in palladium, described
In step 4), reduction treatment is carried out using sodium borohydride or hydrogen.
9. the preparation method of more effect high dispersive structure catalysts according to claim 8 for indoor purifying, special
Sign is, in the step 3), by adjusting solution pH value, hydration is carried out under high temperature and is supported in metal-based catalyst；Hydration
30-95 DEG C of temperature, time 1-5h.
10. a kind of catalysis oxidation formaldehyde of more effect high dispersive structure catalysts described in claim 1 for indoor purifying
Method, which is characterized in that
When initial concentration of formaldehyde is greater than 0.1ppm, the catalysis oxidation of formaldehyde, concentration of formaldehyde are first carried out under the conditions of ultraviolet light
When less than 0.1ppm, formaldehyde treating technology is carried out under the conditions of no ultraviolet light.
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