CN108455932A - A kind of surface whitewashing catalysis material enrichment method based on Magnetic force tracting - Google Patents
A kind of surface whitewashing catalysis material enrichment method based on Magnetic force tracting Download PDFInfo
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- CN108455932A CN108455932A CN201810157111.1A CN201810157111A CN108455932A CN 108455932 A CN108455932 A CN 108455932A CN 201810157111 A CN201810157111 A CN 201810157111A CN 108455932 A CN108455932 A CN 108455932A
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- 239000000463 material Substances 0.000 title claims abstract description 46
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 32
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- 239000011941 photocatalyst Substances 0.000 claims abstract description 38
- 239000007921 spray Substances 0.000 claims abstract description 36
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- 238000005507 spraying Methods 0.000 claims abstract description 22
- 230000001699 photocatalysis Effects 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000007146 photocatalysis Methods 0.000 claims abstract description 15
- 230000015556 catabolic process Effects 0.000 claims abstract description 12
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- 238000006731 degradation reaction Methods 0.000 claims abstract description 12
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- 230000008569 process Effects 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 38
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 22
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 239000004021 humic acid Substances 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
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- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 239000011398 Portland cement Substances 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000004566 building material Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
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- 239000012535 impurity Substances 0.000 claims description 3
- 230000006698 induction Effects 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 230000005415 magnetization Effects 0.000 claims description 3
- 230000003020 moisturizing effect Effects 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 238000007581 slurry coating method Methods 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 238000007306 functionalization reaction Methods 0.000 claims description 2
- 239000002159 nanocrystal Substances 0.000 claims description 2
- DGVVJWXRCWCCOD-UHFFFAOYSA-N naphthalene;hydrate Chemical compound O.C1=CC=CC2=CC=CC=C21 DGVVJWXRCWCCOD-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims 1
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- 239000000356 contaminant Substances 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 5
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- 231100001234 toxic pollutant Toxicity 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 description 9
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- 238000005516 engineering process Methods 0.000 description 5
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- 239000000203 mixture Substances 0.000 description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 4
- 230000006872 improvement Effects 0.000 description 3
- 230000005389 magnetism Effects 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5024—Silicates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- Catalysts (AREA)
Abstract
Proposed by the present invention is a kind of surface whitewashing catalysis material enrichment method based on Magnetic force tracting, and this method comprises the following steps：（1）Prepare the hydrophilic magnetic compound nanometer photocatalyst with high efficiency photocatalysis degradation property；（2）Prepare the building surface whitewashing liquid containing magnetic composite nano photochemical catalyst；（3）Building surface pre-processes；（4）Building surface slurries spray；（5）The Magnetic force tracting enrichment of catalysis material in surface spraying slurries；（6）It sprays grout curing.Hydrophilic magnetic compound nanometer photocatalyst is enriched with outside plus under magnetic field magnetic power draw in coating surface, it is formed with high density, the photocatalytic surfaces of high abundance, high exposed area, there is strong absorption and Photocatalytic Degradation Property, efficient low-consume to remove environmental contaminants toxic pollutant.
Description
Technical field
The surface that the present invention relates to a kind of based on Magnetic force tracting is whitewashed catalysis material enrichment method, and net dirty material is belonged to
Expect preparing technical field.
Background technology
With the fast development of economic society, the hazardous contaminant generated in industrial and agricultural production seriously threatens
The health of environment and the mankind seeks a kind of new and effective environmental improvement technology and is of great significance；Photocatalysis technology has because of it
Have the advantages that efficient, safe, energy saving, environmental-friendly, contaminant degradation is thorough, natural light can induce, it has also become one kind has
The emerging environmental improvement technology of important application foreground.
During at present prepared by photocatalysis construction material usually using it is interior mix, mix outside, the methods of surface coating；Inner blending method is in mix
A large amount of nano materials are put into water（Usual concentration 2%-8%）, addition is pre-mixed in uniform sand and cement admixture, due to big
Depositing nano-materials are measured inside construction material, it is difficult to touch illumination, only minute quantity nano material is attached to construction material
Surface participates in light-catalyzed reaction, and nano material loss is big, and reaction efficiency is low.Outer doping directly coats nano material to Building wood
Expect surface, nano material, which is easy to run off, to fall off, and the nano material being lost in environment will generate environment potential impact, photocatalysis drop
Solution performance is also significantly affected；Although nano material can be adhesively secured to material surface by surface coating method, there is plating
Film thickness is difficult to control, coating is easy to crack falls off, difficult repairs a series of technical barriers such as self-healing, difficult close fixation；Nano combined
During material preparation, how to improve nano particle material surface exposure density, concentration and bond strength, and then improve with
The contact area of illumination, enhancing photocatalytic degradation efficiency are current research hotspot problem and key technology bottleneck.
Invention content
Proposed by the present invention is a kind of surface whitewashing catalysis material enrichment method based on Magnetic force tracting, and purpose is intended to
The surface exposed area and density for promoting catalysis material in gunite coating improve the photocatalysis of coating by naturally photo-induced
High efficiency, stability, update property and the durability of degradation of contaminant.
Technical solution of the invention：A kind of surface whitewashing catalysis material enrichment method based on Magnetic force tracting, should
Method includes the following steps：
（1）Prepare the hydrophilic magnetic compound nanometer photocatalyst with high efficiency photocatalysis degradation property；
（2）Prepare the building surface whitewashing liquid containing magnetic composite nano photochemical catalyst；
（3）Building surface pre-processes；
（4）Building surface slurries spray；
（5）The Magnetic force tracting enrichment of catalysis material in surface spraying slurries；
（6）It sprays grout curing.
Advantages of the present invention：
（1）The magnetic composite nano photochemical catalyst of preparation have high efficiency of additive capability, high-hydrophilic, strong photocatalysis performance and preferably
Magneto separate performance；
（2）Distribution density, the number of construction material gunite coating surface photocatalytic nanometer particle are effectively increased using Magnetic force tracting
Amount, enhances the high efficiency of nano particle photocatalytic pollutant degradation, stability and durability in coating；
（3）Slurries spray and Magnetic force tracting is carried out continuously, and grout curing rear nano-photocatalyst is closely entrenched in coating surface, no
Loss easy to fall off；
（4）By natural light radiation, can thoroughly degrade the hazardous contaminant difficult to degrade of low concentration in environment removal, energy-saving ring
It protects, non-secondary pollution；
（5）It is simple for process, it is cheap, it large-scale promotion can be used in the net dirt of building surface.
Specific implementation mode
A kind of surface whitewashing catalysis material enrichment method based on Magnetic force tracting, specifically comprises the following steps：
（1）Prepare the hydrophilic magnetic compound nanometer photocatalyst with high efficiency photocatalysis degradation property；
（2）Prepare the building surface whitewashing liquid containing magnetic composite nano photochemical catalyst；
（3）Building surface pre-processes；
（4）Building surface slurries spray；
（5）The Magnetic force tracting enrichment of catalysis material in surface spraying slurries；
（6）It sprays grout curing.
The step（1）Prepare the hydrophilic magnetic compound nanometer photocatalyst with high efficiency photocatalysis degradation property, tool
Body method is as follows：
1）Using magnetic nano-particle as functionalization base core, magnetic ferroferric oxide nano-particles are surface modified or are modified；
2）Catalysis material is combined with magnetic nano-particle and prepares magnetic composite nano photochemical catalyst；
3）Hydrophilic magnetic composite Nano light is made by carrying out Hydrophilic modification to magnetic composite nano photochemical catalyst to urge
Agent；Make it while with high absorption property, highlight catalytic active again with certain magnetism, ensures to make in externally-applied magnetic field
With lower realization surface migration.
The magnetic nano-particle is preferably magnetic ferroferric oxide（Fe3O4）Nano-particle, magnetic ferroferric oxide
（Fe3O4）The preparation method of nano-particle preferably uses hydro-thermal method；The catalysis material is preferably nano-titanium dioxide（TiO2）
Colloidal sol, nano-titanium dioxide（TiO2）The preparation method of colloidal sol preferably uses sol-gel method；The hydrophilic magnetic is compound to be received
The synthesis preparation method of rice photochemical catalyst preferably uses hydro-thermal method.
It is described that magnetic ferroferric oxide is prepared using hydro-thermal method（Fe3O4）Nano-particle：By FeCl3·6H2O and ethylene glycol
With mass volume ratio 1:55 mix to solution clarification, then the anhydrous of final concentration of 0.05 g/ml is added in above-mentioned solution
Acetic acid is received, and after room temperature magnetic agitation 1h, 5 min of ultrasonic vibration is then transferred in polytetrafluoroethylene (PTFE) autoclave, will react
Kettle is put into 200 DEG C of reaction 8h of baking oven, is cooled to room temperature magnetic ferroferric oxide is made after reaction（Fe3O4）Nano-particle.
It is described to use Study on Synthesis of Nanocrystal Titanium Dionide（TiO2）Colloidal sol：Magnetic stirring apparatus rotating speed is 1000
It is stirred under rpm stirring conditions, the aqueous isopropanol of presoma tetrabutyl titanate is added drop-wise to pH with the speed of 120 drops/minute is
In 2.5 diluted nitric acid aqueous solution, the molar ratio of nitric acid and tetrabutyl titanate is respectively 76：1.42,75 DEG C of constant temperature stirrings（300
rpm）, alcohols is removed with rotary evaporation after flowing back 24 hours, finally obtains nano-titanium dioxide（TiO2）Colloidal sol.
The preparation method of the hydrophilic magnetic compound nanometer photocatalyst：
1）By magnetic ferroferric oxide（Fe3O4）Nano-particle, nano-titanium dioxide（TiO2）Colloidal sol is with mass ratio 1:3 mixing, add
Heat is to 80 DEG C, with 300-400rmin-1Speed stirs 2h, due to electrostatic interaction, nano-TiO2To Fe3O4Magnetic nanoparticle has
There is good covered effect, after reaction after 80 DEG C of continuous drying 3d, grinding, calcination 3h, obtains in 400 DEG C of nitrogen atmospheres
To magnetic Fe3O4-TiO2Compound nanometer photocatalyst；
2）Hydrophilic radical is modified：Utilize humic acid（HA）Hydrophilic radical modification is carried out, is specially dissolved in 0.1g HA
In the NaOH solution of a concentration of 0.01mol/L of 200mL, by magnetic Fe3O4-TiO2Compound nanometer photocatalyst is with HA solution with matter
Measure volume ratio 1:200 g/ml are mixed evenly under 50 DEG C, 600rpm/min rotating speeds, and continuously stirring 3h makes HA and magnetism
Fe3O4-TiO2Compound nanometer photocatalyst is fully reacted, and with alternately cleaning 6 times of second alcohol and water, each 5min is to remove unreacted
Reagent and impurity, it is last it is freeze-dried after the hydrophilic magnetic Fe that can be prepared by3O4-TiO2Composite photo-catalyst, preparation
Hydrophilic magnetic Fe3O4-TiO2Composite photo-catalyst average grain diameter is about 86nm, saturation magnetization 3-4Am2·Kg-1,
Coercivity is 1600-1800Am-1, there is good absorption property, photocatalysis performance and Magneto separate performance.
The step（2）Prepare the building surface whitewashing liquid containing magnetic composite nano photochemical catalyst：The building
Surface whitewashing liquid includes solid constituent and water；The solid component includes cement, building sand, water-reducing agent, interface adhesive；Contain
The specific preparation method of the building surface whitewashing liquid for the compound nanometer photocatalyst that is magnetic is as follows：
1）Prepare whitewashing powder：Cement, building sand, water-reducing agent, interface adhesive are pressed into cement：Building sand：Water-reducing agent：Boundary
Face binder=（0.8-1.1）：（1-1.2）:（0.002-0.01）：（0.6-1.5）（Weight ratio）Ratio mixing, then will be close
Aqueous magnetic composite nano photochemical catalyst is added by the 1.5%-3.5% additional proportions of cement weight, and the above component is mixed in proportion
Whitewashing powder is formed after conjunction；
2）Water and whitewashing powder are pressed（0.8-1.3）:（1.0-1.8）Weight ratio mixing, be sufficiently stirred in blender
It is even.
The portland cement that the cement preferred intensity grade is 42.5；The grain size of the building sand is 0.2mm-
0.63mm, clay content<3%；The selection of the interface adhesive meets JC/T907-2002《Concrete interface treating agent》Specification is wanted
It asks, is preferably suitable for the I type binders of cement concrete interface processing；The naphthalene system that the preferred water-reducing rate of water-reducing agent is 20%
Water-reducing agent.
The step（3）Building surface pre-processes：Water spray pretreatment is carried out to building material surface before spraying, is washed away
The floating ash in surface simultaneously ensures that spray-coating surface moistens.
The step（4）Building surface slurries spray：By step（2）Middle preparation contains magnetic composite nano photocatalysis
The box for feeding odd of refractory gunning equipment, flush coater operating pressure preferred 6MPa-when slurries spray is added in the building surface whitewashing liquid of agent
8MPa, the preferred 0.1cm -0.3cm of nozzle diameter, spray gun preferred 20cm -50cm, coating layer thickness at a distance from coated article face are preferred
0.2cm -0.5cm；The preferred cement throwing jet of the refractory gunning equipment, spraying machine for external wall or similar product.
The step（5）The Magnetic force tracting enrichment of catalysis material in surface spraying slurries：Step（4）After slurries spraying,
Immediately（Interval time<5min）The magnetic composite nano catalysis material in spraying slurries is carried out using additional high-intensity magnetic field device
Magnetic force tracting is enriched with；It is preferable to use ndfeb magnets in the additional high-intensity magnetic field device, to improve the surface of magnetic Nano material
Migration effect, magnetic induction intensity >=4000GS of ndfeb magnet, magnet is 3cm away from slurry coating surface distance when Magnetic force tracting
- 10cm, Magnetic force tracting time 2min -5min.
The step（6）It sprays grout curing：To ensure the adhesion strength of gunite coating and building material, coating is improved
Stability and persistence, in step（5）It is to be coated that drying is fully cured in spray slurry surface water spray moisturizing after terminating 8h and 16h
It completes afterwards.
Magnetic composite nano photochemical catalyst in slurries is sprayed to be enriched in coating surface outside plus under magnetic field magnetic power draw,
The nano-photo catalytic surface with high density, high abundance, high exposed area is formed after solidification, to hazardous contaminant in environment
With strong suction-operated, and photocatalytic degradation reaction is carried out under natural lighting effect, efficient low-consume removes environmental contaminants.
The present invention is modified by nano-photocatalyst material, it is made to have strongly hydrophilic, magnetism, high absorption and degradation property,
Surface whitewashing processing is carried out to building by blending cement mortar, outside plus under magnetic field magnetic power draw, increases photocatalysis
Material promotes the surface exposure of catalysis material in gunite coating in the distribution density and solidification rate of setting on gunite coating surface
Area and density, by naturally photo-induced, improve the high efficiency of the photocatalytic pollutant degradation of coating, stability, update property and
Durability.
Below by way of specific embodiment be described in detail invention implementation steps, it is therefore intended that make those skilled in the art into
One step understands the present invention, but the invention is not limited in any way；It should be pointed out that coming to those skilled in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Range.
Embodiment 1
Magnetic Fe in a kind of river concrete side slope gunite coating3O4-TiO2The surface enrichment method of composite photocatalyst material, tool
Body includes the following steps：
（1）Prepare hydrophilic magnetic Fe3O4-TiO2Composite photocatalyst material；
（2）Preparation contains magnetic Fe3O4-TiO2The river concrete side slope surface whitewashing liquid of composite photocatalyst material；
（3）River concrete side slope surface preparation；
（4）River concrete slope table starch adhesive liquid sprays；
（5）The Magnetic force tracting enrichment of catalysis material in the slurries of surface；
（6）It sprays grout curing.
The step（1）Prepare hydrophilic magnetic Fe3O4-TiO2The step of composite photocatalyst material, is as follows：
1）Fe is prepared using hydro-thermal method3O4Magnetic nanoparticle：By FeCl3·6H2O and ethylene glycol are with mass volume ratio 1:55 is mixed
It closes stirring to solution to clarify, then the anhydrous acetic acid of final concentration of 0.05 g/ml is added in above-mentioned solution and receives, room temperature magnetic agitation
After 1h, 5 min of ultrasonic vibration is then transferred in polytetrafluoroethylene (PTFE) autoclave, and reaction kettle is put into 200 DEG C of reactions of baking oven
8h is cooled to room temperature Fe is made after reaction3O4Magnetic nanoparticle；
2）Nano-TiO is prepared using sol-gel method2Colloidal sol：Magnetic stirring apparatus rotating speed is to be stirred under 1000 rpm stirring conditions,
The aqueous isopropanol of presoma tetrabutyl titanate is added drop-wise to the diluted nitric acid aqueous solution that pH is 2.5 with the speed of 120 drops/minute
In, the molar ratio of nitric acid and tetrabutyl titanate is respectively 76：1.42,75 DEG C of constant temperature stirrings（300 rpm）, used after flowing back 24 hours
Rotary evaporation removes alcohols, finally obtains nano-TiO2Colloidal sol；
3）Prepare magnetic Fe3O4-TiO2Composite photo-catalyst：By Fe3O4Magnetic nanoparticle, nano-TiO2Colloidal sol is with mass ratio 1:
3 mixing, are heated to 80 DEG C, with 300-400rmin-1Speed stirs 2h, due to electrostatic interaction, nano-TiO2To Fe3O4Magnetism is received
Rice grain has good covered effect, after reaction after 80 DEG C of continuous drying 3d, grinding, in 400 DEG C of nitrogen atmospheres
Calcination 3h, obtains magnetic Fe3O4-TiO2Composite photo-catalyst；
4）Hydrophilic radical is modified：Utilize humic acid（HA）Hydrophilic radical modification is carried out, is specially dissolved in 0.1g HA
In the NaOH solution of a concentration of 0.01mol/L of 200mL, by step 3）The magnetic Fe of acquisition3O4-TiO2Composite photo-catalyst and HA
Solution is with mass volume ratio 1:200 g/ml are mixed evenly under 50 DEG C, 600rpm/min rotating speeds, and continuously stirring 3h makes HA
With Fe3O4-TiO2Composite photo-catalyst fully reacts, and with alternately cleaning 6 times of second alcohol and water, each 5min is unreacted to remove
Reagent and impurity, the hydrophilic magnetic Fe that can be prepared by after finally freeze-dried3O4-TiO2Composite photo-catalyst, the parent of preparation
Aqueous magnetic Fe3O4-TiO2Composite photo-catalyst average grain diameter is about 86nm, saturation magnetization 3-4Am2·Kg-1, rectify
Stupid power is 1600-1800Am-1, there is good absorption property, photocatalysis performance and Magneto separate performance.
The step（2）Preparation contains magnetic Fe3O4-TiO2It sprays on the river concrete side slope surface of composite photocatalyst material
Slurries：Liquid solid constituent of whitewashing selects cement, building sand, water-reducing agent and interface adhesive, the wherein intensity of portland cement
Grade is 42.5, and building sand grain size is 0.2mm, clay content<3%, the selection of interface adhesive is suitable for coagulating cement Soil Interface
The I type binders of processing, water-reducing agent are the naphthalene water reducer that water-reducing rate is about 20%, spray cement in slurry configurations：Building sand：
Water-reducing agent：The ratio of interface adhesive is 0.9:1:0.005：0.8（Weight ratio）, magnetic composite nano photochemical catalyst additional proportion
It is the 2% of cement weight；Whitewashing powder is formed after the above component is mixed in proportion, and water and whitewashing powder are pressed 1:1.2 ratio
Mixing, stirs in blender.
The step（3）River concrete side slope surface preparation：River concrete side slope surface is sprayed before spraying
Water pretreatment washes away the floating ash in surface and ensures that spray-coating surface moistens.
The step（4）River concrete slope table starch adhesive liquid sprays：By step（2）Middle preparation contains Fe3O4-TiO2
The box for feeding odd of refractory gunning equipment is added in the whitewashing liquid of composite photocatalyst material, and refractory gunning equipment is spraying machine for external wall, and slurries spray when spraying
Painting machine operating pressure is 8MPa, and nozzle diameter 0.2cm, spray gun is 40 cm at a distance from coated article face, and coating layer thickness is
0.5cm, the range of Channel slope contact water body when coating coverage area is located at river water body highest and lowest water level.
The step（5）The Magnetic force tracting enrichment of catalysis material in the slurries of surface：Step（4）After slurries spraying, immediately
（Interval time<5min）Using additional high-intensity magnetic field device to the magnetic Fe in spraying slurries3O4-TiO2Composite photocatalyst material into
Row Magnetic force tracting is enriched with, and ndfeb magnet is used in additional high-intensity magnetic field device, and the magnetic induction intensity of ndfeb magnet is 5000GS,
Magnet is 3.5 cm, Magnetic force tracting time 3min away from slurry coating surface distance when Magnetic force tracting.
The step（6）It sprays grout curing：To ensure the adhesion strength of gunite coating and river concrete side slope, improves and apply
The stability and persistence of layer, in step（5）It is to be coated to be fully cured in spray slurry surface water spray moisturizing after terminating 8h and 16h
It completes after drying.
It sprays grout curing and river concrete side slope secret to bond, be formed with high density, high abundance, high exposed area
Magnetic Fe3O4-TiO2Composite photocatalyst surface has strong suction-operated to hazardous contaminant in environment, and in natural light
According to lower progress photocatalytic degradation reaction is induced, carrying out efficient, sustaining degradation to poisonous and harmful environmental contaminants in water body removes.
Claims (10)
- The catalysis material enrichment method 1. the surface based on Magnetic force tracting is whitewashed, it is characterized in that including the following steps：（1）Prepare the hydrophilic magnetic compound nanometer photocatalyst with high efficiency photocatalysis degradation property；（2）Prepare the building surface whitewashing liquid containing magnetic composite nano photochemical catalyst；（3）Building surface pre-processes；（4）Building surface slurries spray；（5）The Magnetic force tracting enrichment of catalysis material in surface spraying slurries；（6）It sprays grout curing.
- The catalysis material enrichment method 2. the surface according to claim 1 based on Magnetic force tracting is whitewashed, it is characterized in that institute State step（1）The hydrophilic magnetic compound nanometer photocatalyst with high efficiency photocatalysis degradation property is prepared, the specific method is as follows：1）Using magnetic nano-particle as functionalization base core, magnetic ferroferric oxide nano-particles are surface modified or are modified；2）Catalysis material is combined with magnetic nano-particle and prepares magnetic composite nano photochemical catalyst；3）Hydrophilic magnetic composite Nano light is made by carrying out Hydrophilic modification to magnetic composite nano photochemical catalyst to urge Agent.
- The catalysis material enrichment method 3. the surface according to claim 2 based on Magnetic force tracting is whitewashed, it is characterized in that institute It is magnetic ferroferric oxide nano-particles to state magnetic nano-particle, and the preparation method of magnetic ferroferric oxide nano-particles uses water Hot method；The catalysis material is nano titanic oxide sol, and the preparation method of nano titanic oxide sol uses sol-gel Method；The synthesis preparation method of the hydrophilic magnetic compound nanometer photocatalyst uses hydro-thermal method.
- The catalysis material enrichment method 4. the surface according to claim 3 based on Magnetic force tracting is whitewashed, it is characterized in that institute It states and magnetic ferroferric oxide nano-particles is prepared using hydro-thermal method：By FeCl3·6H2O and ethylene glycol are with mass volume ratio 1:55 is mixed It closes stirring to solution to clarify, then the anhydrous acetic acid of final concentration of 0.05 g/ml is added in above-mentioned solution and receives, room temperature magnetic agitation After 1h, 5 min of ultrasonic vibration is then transferred in polytetrafluoroethylene (PTFE) autoclave, and reaction kettle is put into 200 DEG C of reactions of baking oven 8h is cooled to room temperature magnetic ferroferric oxide nano-particles are made after reaction.
- The catalysis material enrichment method 5. the surface according to claim 3 based on Magnetic force tracting is whitewashed, it is characterized in that institute It states and uses Study on Synthesis of Nanocrystal Titanium Dionide colloidal sol：Magnetic stirring apparatus rotating speed is to be stirred under 1000 rpm stirring conditions, The aqueous isopropanol of presoma tetrabutyl titanate is added drop-wise to the diluted nitric acid aqueous solution that pH is 2.5 with the speed of 120 drops/minute In, the molar ratio of nitric acid and tetrabutyl titanate is respectively 76：1.42,75 DEG C, the stirring of 300 rpm constant temperature, reflux are used after 24 hours Rotary evaporation removes alcohols, finally obtains nano titanic oxide sol.
- The catalysis material enrichment method 6. the surface according to claim 1 based on Magnetic force tracting is whitewashed, it is characterized in that institute State the preparation method of hydrophilic magnetic compound nanometer photocatalyst：1）By magnetic ferroferric oxide nano-particles, nano titanic oxide sol with mass ratio 1:3 mixing, are heated to 80 DEG C, with 300 -400r·min-1Speed stirs 2h, after reaction after 80 DEG C of continuous drying 3d, grinding, in 400 DEG C of nitrogen atmospheres Calcination 3h, obtains magnetic Fe3O4-TiO2Compound nanometer photocatalyst；2）Hydrophilic radical is modified：Hydrophilic radical modification is carried out using humic acid, is specially dissolved in 0.1g humic acid In the NaOH solution of a concentration of 0.01mol/L of 200mL, by magnetic Fe3O4-TiO2Compound nanometer photocatalyst and humic acid solution With mass volume ratio 1:200 g/ml are mixed evenly under 50 DEG C, 600rpm/min rotating speeds, and continuously stirring 3h makes humic acid With magnetic Fe3O4-TiO2Compound nanometer photocatalyst is fully reacted, and with alternately cleaning 6 times of second alcohol and water, each 5min is to remove Unreacted reagent and impurity, the hydrophilic magnetic Fe that can be prepared by after finally freeze-dried3O4-TiO2Composite photo-catalyst, The hydrophilic magnetic Fe of preparation3O4-TiO2Composite photo-catalyst average grain diameter is about 86nm, saturation magnetization 3-4A m2·Kg-1, coercivity 1600-1800Am-1。
- The catalysis material enrichment method 7. the surface according to claim 1 based on Magnetic force tracting is whitewashed, it is characterized in that institute State step（2）Prepare the building surface whitewashing liquid containing magnetic composite nano photochemical catalyst：The building surface whitewashing liquid Including solid constituent and water；The solid component includes cement, building sand, water-reducing agent, interface adhesive；Contain magnetic coupling The specific preparation method of the building surface whitewashing liquid of nano-photocatalyst is as follows：1）Prepare whitewashing powder：Cement, building sand, water-reducing agent, interface adhesive are pressed into cement：Building sand：Water-reducing agent：Boundary Face binder=（0.8-1.1）：（1-1.2）:（0.002-0.01）：（0.6-1.5）The ratio of weight ratio mixes, then will be hydrophilic Property magnetic composite nano photochemical catalyst by cement weight 1.5%-3.5% additional proportions be added, the above component is mixed in proportion Whitewashing powder is formed afterwards；2）Water and whitewashing powder are pressed（0.8-1.3）:（1.0-1.8）Weight ratio mixing, be sufficiently stirred in blender It is even.
- The catalysis material enrichment method 8. the surface according to claim 7 based on Magnetic force tracting is whitewashed, it is characterized in that institute It is portland cement to state cement；The grain size of the building sand is 0.2mm-0.63mm, clay content<3%；The interface adhesive Selection meet JC/T907-2002《Concrete interface treating agent》Code requirement is suitable for the I of cement concrete interface processing Type binder；The naphthalene water reducer that the water-reducing agent water-reducing rate is 20%.
- The catalysis material enrichment method 9. the surface according to claim 1 based on Magnetic force tracting is whitewashed, it is characterized in that institute State step（3）Building surface pre-processes：Water spray pretreatment is carried out to building material surface before spraying, washes away the floating ash in surface simultaneously Ensure spray-coating surface moistening；The step（4）Building surface slurries spray：By step（2）Middle preparation containing magnetic composite nano photochemical catalyst The box for feeding odd of refractory gunning equipment is added in building surface whitewashing liquid, and flush coater operating pressure is 6MPa -8MPa, spray when slurries spray Mouthpiece diameter is 0.1cm-0.3cm, and spray gun is 20-50cm, coating layer thickness 0.2-0.5cm at a distance from coated article face；The spray Sizing device is cement throwing jet or spraying machine for external wall.
- The catalysis material enrichment method 10. the surface according to claim 1 based on Magnetic force tracting is whitewashed, it is characterized in that institute State step（5）The Magnetic force tracting enrichment of catalysis material in surface spraying slurries：Step（4）It is used in 5 minutes after slurries spraying Additional high-intensity magnetic field device carries out Magnetic force tracting enrichment to the magnetic composite nano catalysis material in spraying slurries；The outer reinforcement Magnetic field device is ndfeb magnet, magnetic induction intensity >=4000GS of ndfeb magnet, and magnet is away from slurry coating when Magnetic force tracting Surface distance is 3cm -10cm, Magnetic force tracting time 2min -5min；The step（6）It sprays grout curing：In step（5）Knot After beam 8h and 16h, spray water moisturizing in spray slurry surface, it is to be coated be fully cured it is dry after complete.
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