CN106975352A - A kind of visible-light photocatalyst WO3 and WO3 composite coatings are with preparing and applying - Google Patents

A kind of visible-light photocatalyst WO3 and WO3 composite coatings are with preparing and applying Download PDF

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Publication number
CN106975352A
CN106975352A CN201710305286.8A CN201710305286A CN106975352A CN 106975352 A CN106975352 A CN 106975352A CN 201710305286 A CN201710305286 A CN 201710305286A CN 106975352 A CN106975352 A CN 106975352A
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composite coating
coating
visible
base
prepared
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马保军
贠红娟
林克英
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Ningxia University
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Ningxia University
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • 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
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/45—Magnetic mixers; Mixers with magnetically driven stirrers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20776—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
    • B01D2259/802—Visible light
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
    • B01D2259/81—X-rays
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • B01J35/39—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2258—Oxides; Hydroxides of metals of tungsten

Abstract

The present invention relates to a kind of WO3The preparation of composite coating, and the Photocatalytic Performance Study for indoor and outdoor formaldehyde of degrading.A kind of WO3Preparation method, i.e. H2WO4Calcined through different temperatures.What is prepared concretely comprises the following steps：(1) a certain amount of H is weighed2WO4.(2) H that will be weighed in step (1)2WO4In different temperatures calcining, the 8h of calcination time 5, you can WO is made3Visible-light photocatalyst.(3) WO prepared by3It is dispersed through mixing with coating after body polyacrylamide is scattered, then mechanical agitation, sonic oscillation.(4) by the WO prepared by (3)3Composite coating is uniformly applied to the stromal surfaces such as glass or metope.PARA FORMALDEHYDE PRILLS(91,95) gas is degraded under the irradiation of 8w fluorescent lamps, after 8h, the degradation rate about 8% of its composite coating PARA FORMALDEHYDE PRILLS(91,95).Therefore, it is seen that WO is utilized under light3Composite coating degradation of formaldehyde has significant practical significance to improve the health of air quality and the mankind.

Description

A kind of visible-light photocatalyst WO3And WO3Composite coating is with preparing and applying
Technical field
The present invention relates to a kind of WO3Photochemical catalyst and its technology of preparing with composite coating.By degradation of formaldehyde gas, Prove organic pollution in degradable environment in the sunlight.
Background technology
In recent years, with the continuous improvement of people's living standard, people to indoor and outdoor surroundingses it is attractive in appearance, comfortably also have Higher requirement, but used in interior decoration various finishing materials and furniture have become the main pollution of indoor and outdoor surroundingses Volatile organic compound can be all discharged in source, coating, paint, ornament and commodity as used in interior decoration. And by WO3Visible-light photocatalyst is mutually combined with coating and prepares the degraded that light catalyzed coating carries out formaldehyde gas, to reach fully Using the photocatalysis effect of sunshine and fluorescent lamp come the purpose of degradation of formaldehyde, with certain practical value.
Photocatalytic Oxidation With Semiconductors technology has turned into current most promising environmental improvement method, and such as indoor and outdoor air is net Very big positive role is all played in terms of change, waste water control and pollutant control：(1) semiconductor is in photocatalysis oxidation technique Field has the advantages that simple to operate, reaction condition is gentle, energy consumption is low and secondary pollution is few, thus pollutes field in processing environment Receive much concern；(2)WO3It is a kind of energy gap about 2.5-2.8eV n-type semiconductor, main absorb is less than 443nm wavelength Light, stability is good；(3)WO3The organic pollutions such as energy efficient degradation formaldehyde, environmental pollution is small, cheap.And with regard to ring For the purification of border, also there is very big application value for the interior without ultraviolet light.
Main component is visible ray in sunshine, and ultraviolet light composition only accounts for 5% or so.Therefore, degrade under visible light room Inside and outside organic pollution has significant practical significance to improve the health of environmental quality and the mankind.
The content of the invention
An object of the present invention is to provide a kind of WO3Visible-light photocatalyst.
The second object of the present invention is to provide a kind of above-mentioned WO3Visible-light photocatalyst, and it is combined with coating Method, this method is simple and easy to apply, it is not necessary to the equipment of complex and expensive.
Technical scheme
A kind of WO3Visible-light photocatalyst, i.e., through H2WO4Calcine and be made under (300-700 DEG C), calcination time is (5- 8h).Then by above-mentioned gained WO3It is compound with coating.
A kind of above-mentioned WO3The preparation method that visible-light photocatalyst and coating are combined is：
First by WO3Photochemical catalyst is dispersed through adding in U.S. color coating material of getting home after body polyacrylamide solution is scattered, wherein WO3 Addition be 1%-20%, the addition of dispersion polyacrylamide is WO32%, PH=7 of quality, magnetic agitation half is small When, then ultrasonic disperse 1h is uniformly applied to the glass surface with dry cloth wiped clean by mechanical agitation, sonic oscillation, is painted with One layer applies next layer again when coating is impregnated into glass surface, and smear makes it certainly altogether in 3 layers, the casing for being finally putting into black lucifuge So air-dry.
Beneficial effects of the present invention：
A kind of WO of the present invention3Visible-light photocatalyst, and it is combined with coating, this method is simple and easy to apply, it is not necessary to The equipment of complex and expensive.Due to WO3Band-gap energy it is smaller, be 2.5-2.8eV, under visible light can efficient degradation organic contamination Thing, environmental pollution is small, cheap.Also there is very big application value for the interior without ultraviolet light.
Prepared WO3Composite coating is uniformly applied to the stromal surfaces such as glass or metope.It is right under the irradiation of 8w fluorescent lamps Formaldehyde gas is degraded, after 8h, the degradation rate about 8% of its composite coating PARA FORMALDEHYDE PRILLS(91,95).Therefore, it is seen that WO is utilized under light3It is compound Coating degradation of formaldehyde has significant practical significance to improve the health of air quality and the mankind.
Brief description of the drawings
Fig. 1 .WO3XRD；
WO under Fig. 2 visible rays3The degradation effect figure of composite coating PARA FORMALDEHYDE PRILLS(91,95) gas；
The influence of Fig. 3 difference coating PARA FORMALDEHYDE PRILLS(91,95) gas degradation rates.
Embodiment
Invention will be further elaborated by specific embodiment below.
Embodiment 1
Take H2WO45h is calcined with 3 DEG C/min at 300 DEG C, 400 DEG C, 500 DEG C, 600 DEG C, 700 DEG C respectively, WO is produced3。
It can be seen that H from Fig. 1 XRD2WO4Gained WO is calcined through different temperatures3。
WO3The preparation of composite coating and the degraded of PARA FORMALDEHYDE PRILLS(91,95) gas：From calcining H under the conditions of 300 DEG C2WO4Time, 5h was made Standby WO3,
By WO3Photochemical catalyst is distributed to dispersion polyacrylamide solution, and polyacrylamide solution mass concentration is 10%, PH is adjusted using 1mol sodium hydroxides, base-material is then added to.
WO3Addition be 11%, the coating of selection is the U.S. color high-grade inner wall latex paint of family, dispersion polyacrylamide Addition is 2%, adds the distilled water of coating quality 10%, and PH=7, mechanical agitation half an hour, ultrasonic disperse 1h, formaldehyde is initial Concentration is 0.20mg/m3, temperature is room temperature.
The glass surface with dry cloth wiped clean is then uniformly applied to by mechanical agitation, sonic oscillation, one layer is painted with and treats Coating applies next layer again when being impregnated into glass surface, and smearing altogether in 3 layers, the casing for being finally putting into black lucifuge makes its natural wind It is dry.
WO under visible ray as can be seen from Figure 23The degradation effect figure of composite coating PARA FORMALDEHYDE PRILLS(91,95) gas.
From Fig. 2 it can be found that after 8w visible ray shines 8h, H2WO4The WO prepared under 300 DEG C of calcining heats3It is answered Close the degradation rate about 8% of coating PARA FORMALDEHYDE PRILLS(91,95).
Embodiment 2
Be the same as Example 1, difference from Example 1 is, from calcining H under the conditions of 300 DEG C2WO4Prepared by time 8h WO3。
After 8w visible ray shines 8h, prepared WO3The degradation rate of its composite coating PARA FORMALDEHYDE PRILLS(91,95) about 6.5%.
Embodiment 3
Be the same as Example 1, difference from Example 1 is, WO3Addition 20%.
After 8w visible ray shines 8h, prepared WO3The degradation rate of its composite coating PARA FORMALDEHYDE PRILLS(91,95) about 5.2%.
Embodiment 4
Be the same as Example 1, difference from Example 1 is, WO3It is molten that photochemical catalyst is distributed to dispersion polyacrylamide Liquid, adjusts PH=6.5 using 0.05mol sodium hydroxides, is then added to base-material.
After 8w visible ray shines 8h, prepared WO3The degradation rate of its composite coating PARA FORMALDEHYDE PRILLS(91,95) about 4.8%.
Embodiment 5
Be the same as Example 1, difference from Example 1 is, initial initial concentration of formaldehyde is concentration 0.80mg/m3。
After 8w visible ray shines 8h, prepared WO3The degradation rate of its composite coating PARA FORMALDEHYDE PRILLS(91,95) about 5.1%.
It is can be seen that from embodiment 1-5 under identical calcining heat, be 5h, WO in calcination time3Addition be 11%, initial initial concentration of formaldehyde is concentration 0.20mg/m3, WO3Photochemical catalyst is distributed to dispersion polyacrylamide solution, adopts When adjusting its PH with 1mol sodium hydroxides, the degradation rate highest of its composite coating PARA FORMALDEHYDE PRILLS(91,95), about 8%.
Embodiment 6
Be the same as Example 1, difference from Example 1 is, from calcining H under the conditions of 400 DEG C2WO4Prepared by time 5h WO3, WO3Addition be 11%.
WO under visible ray as can be seen from Figure 23The degradation effect figure of composite coating PARA FORMALDEHYDE PRILLS(91,95) gas.
Embodiment 7
Be the same as Example 1, difference from Example 1 is, from calcining H under the conditions of 500 DEG C2WO4Prepared by time 5h WO3, WO3Addition be 11%.
WO under visible ray as can be seen from Figure 23The degradation effect figure of composite coating PARA FORMALDEHYDE PRILLS(91,95) gas.
Embodiment 8
Be the same as Example 1, difference from Example 1 is, from calcining H under the conditions of 600 DEG C2WO4Prepared by time 5h WO3, WO3Addition be 11%.
WO under visible ray as can be seen from Figure 23The degradation effect figure of composite coating PARA FORMALDEHYDE PRILLS(91,95) gas.
Embodiment 9
Be the same as Example 1, difference from Example 1 is, from calcining H under the conditions of 700 DEG C2WO4Prepared by time 5h WO3, WO3Addition be 11%.
WO under visible ray as can be seen from Figure 23The degradation effect figure of composite coating PARA FORMALDEHYDE PRILLS(91,95) gas.
Embodiment 10
Be the same as Example 1, difference from Example 1 is, from calcining H under the conditions of 300 DEG C2WO4Prepared by time 5h WO3, WO3Addition be 11%, by its respectively with family U.S. color high-grade inner wall latex paint, one hundred when clean senior exterior wall paint, a new generation it is many Happy scholar, Artline be clean etc., and coating is combined.
The influence of different coating PARA FORMALDEHYDE PRILLS(91,95) gas degradation rates as can be seen from Figure 3
From Fig. 2 it can be found that after 8w visible ray shines 8h, H2WO4The WO prepared under different calcining heats3Its light Catalytic activity is variant, the WO prepared under 300 DEG C of calcining heats3The degradation rate highest of PARA FORMALDEHYDE PRILLS(91,95), about 8%, illustrate identical Light application time in the WO for preparing under 300 DEG C of calcining heats3Photocatalytic activity highest.
In Fig. 3, Paint#1 is the U.S. color high-grade inner wall latex paint of family, and clean senior exterior wall paint during Paint#2 one hundred, Paint#3 is new Generation Duo Leshi, Paint#4 Artline is clean.It can be seen that the degradation rate change of four kinds of coating is little, four kinds of coating after 8h Degradation rate reach 8% or so.

Claims (7)

1. a kind of visible-light photocatalyst WO3, it is characterised in that:It is by H2WO4Calcine and be made at 300-700 DEG C, during calcining Between be 5-8h.
2. a kind of WO3Composite coating, it is characterised in that：Applied as the interiro wall latex paint of base-material, exterior wall paint, interior wall coating or exterior wall WO is added in material3With dispersant polyacrylamide, wherein WO3Addition be that (more excellent is 10%- by the 1%-20% of base-material quality 12%), the addition of dispersant polyacrylamide is WO3The 0.5%-3% (being more preferably 1%-2%) of quality；
Described visible-light photocatalyst WO3It is by H2WO4Calcine and be made under 300-700 DEG C (more excellent is 300-500 DEG C), forge The burning time is 5-8h (more excellent is 5-6h).
3. WO as claimed in claim 23Composite coating, it is characterised in that：When base-material is the U.S. color high-grade inner wall latex paint of family, one hundred Clean senior exterior wall paint, the how happy scholar's coating of a new generation or the clean coating of Artline.
4. the WO described in a kind of Claims 2 or 33The preparation method of composite coating, it is characterised in that：Specifically include following steps:
First by WO3Photochemical catalyst is dispersed through being added in base-material after body polyacrylamide solution is scattered, polyacrylamide solution quality Concentration is 8%-12% (more excellent is 8%-10%), and magnetic agitation is more than half an hour, more than ultrasonic disperse 1h.
5. preparation method as claimed in claim 4, it is characterised in that：
By WO3Photochemical catalyst is distributed to dispersion polyacrylamide solution, uses 0.05-2mol (more excellent for 1-2mol) hydroxide Sodium adjusts PH=6.5-7.5 (more excellent is PH=7), is then added to base-material.
6. the WO described in a kind of Claims 2 or 33The application of composite coating, it is characterised in that：The composite coating can be applied or It is added to body surface, it can stop to thing has formaldehyde gas progress photocatalytic degradation in local environment atmosphere.
7. WO as claimed in claim 63The application of composite coating, it is characterised in that：Initial concentration of formaldehyde in ambiance 0.20-1.0mg/m3, temperature is room temperature.
CN201710305286.8A 2017-05-03 2017-05-03 A kind of visible-light photocatalyst WO3 and WO3 composite coatings are with preparing and applying Pending CN106975352A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107913717A (en) * 2017-11-27 2018-04-17 大连理工大学 A kind of preparation method and application of catalysis electrode for contamination control
CN107913717B (en) * 2017-11-27 2020-08-25 大连理工大学 Preparation method and application of catalytic electrode for pollution control

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Application publication date: 20170725