CN107081148A - Prepare the method for material for air purification and by material for air purification made from this method - Google Patents
Prepare the method for material for air purification and by material for air purification made from this method Download PDFInfo
- Publication number
- CN107081148A CN107081148A CN201710414079.6A CN201710414079A CN107081148A CN 107081148 A CN107081148 A CN 107081148A CN 201710414079 A CN201710414079 A CN 201710414079A CN 107081148 A CN107081148 A CN 107081148A
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- Prior art keywords
- weight
- air
- titanium oxide
- semi
- nano titanium
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- 238000004887 air purification Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 37
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000004065 semiconductor Substances 0.000 claims abstract description 48
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 36
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- 235000020234 walnut Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical class [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- B01J23/16—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
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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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
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
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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
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- B01J35/40—
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- B01J35/51—
Abstract
The present invention relates to a kind of method for preparing material for air purification, including using the solid mixture comprising following component water be used as adhesive in the presence of be well mixed, granulation, dry and be calcined：1) nano titanium oxide of 40 56 weight % semi-conducting material doping, 2) 42 50 weight % clay containing pyrolusite powder, and 3) 2 10 weight % activated carbon.The invention further relates to pass through material for air purification made from the inventive method.The material for air purification can effectively shorten the TVOC volatilization times and can potent purification air, this effect even can also carry out under conditions of no illumination, and the scavenging material is also with enough intensity in addition, so as to greatly prolong the air cleaning time.
Description
Technical field
The present invention relates to a kind of method for preparing material for air purification, and pass through air cleaning material made from this method
Material.
Background technology
Due to in-car, indoor decorating and refurnishing materials are lasting, muchly discharge toxic and harmful gas, and engine combustion has
Evil gas, air-conditioning system introduces the reasons such as in-car, indoor pernicious gas, and breed bacteria mould, in-car, indoor, especially
It is that in new car, the pernicious gases such as strong volatile organic compounds, peculiar smell can be diffused.Preferably, air is to dirt for the airtight performance of automobile
The dilution capacity for contaminating thing is very limited, and in-car pollutant concentration can remain high, it is often the case that automobile has used the several years,
In-car dusty gas still severe overweight, so as to cause greatly harm to health.In addition, newly-decorated room also can
There are these to a certain degree.
The amount of the volatile organic compounds carried in various materials is more, space volatilize concentration it is higher, volatilization when
Between it is longer, reach dynamic equilibrium by certain condition, now in-car people can breathe the dusty gas of high concentration.If
The process of strong degradation of contaminant is present, then the dynamic equilibrium of pollutant volatilization release will be broken, the pollutant in material
Just accelerated catalysis volatilization is discharged, and the volatile organic compounds for effectively making to carry in material are accelerated to consume by this process,
So that consumption is net.If vehicle or room air self-circulation system can also have strong purification function in dark condition, then can be with
Told newly by its respiration, i.e. soil pick-up, make the volatile organic compounds in material constantly accelerate volatilization to discharge, and it is constantly strong
Catalytic degradation is imitated, so as to reach the purpose of purification treatment.
Traditional nano titanium oxide, only under action of ultraviolet light, competence exertion light catalytic purifying effect, for automobile
With indoor lasting high density pollution gas, it appears low effort, air is purified to up to standard, it is clear that helpless, so right
Vehicle and room air self-circulation system will produce the high request of catharsis, incompatible.
Also some popular chemical reagent cover up the technology that in automobile or foreign flavor indoors are stimulated in the market, but these
Cure the symptoms, not the disease, simply temporarily mask smell, pollutant is not removed, and can increase some new pollutions on the contrary, this is to vapour
In-car or indoor air quality safety and improvement purification is at all unhelpful.
The content of the invention
For the above-mentioned problems in the prior art, the present inventor is in material for air purification, especially interior
Carry out deeply and widely studying with automobile inner air scavenging material field, as a result found, glued if pyrolusite powder will be contained
Native (being commonly called as high viscosity clay) obtains as the manganese source and be combined activated carbon as carrier and nano titanium oxide of bivalent manganese
Composite particles through dry and reducing condition under be calcined after, can effectively shorten the TVOC volatilization times and can potent purification it is empty
Gas, this effect even can also be carried out under conditions of no ultraviolet light and visible ray illumination.The present invention is based on foregoing hair
Now it is achieved.
Therefore, it is an object of the present invention to provide a kind of method for preparing material for air purification.By this method not only
It can easily be made material for air purification, and the material for air purification that obtains of this method is when can effectively shorten TVOC volatilizations
Between and can potent purification air, this effect even can also carry out under conditions of no ultraviolet light and visible ray illumination, in addition
The scavenging material also has enough intensity and long-term effect, so as to greatly prolong the air cleaning time.
It is a further object to provide pass through material for air purification made from preparation method of the present invention.The air is net
Change material can effectively shorten the TVOC volatilization times and can potent purification air, this effect is even in no ultraviolet light and visible
It can also be carried out under conditions of light illumination, the scavenging material also has enough intensity and long-term effect in addition, so as to greatly prolong sky
The gas clarification time.
Realizing the technical scheme of above-mentioned purpose of the present invention can be summarized as follows：
1st, a kind of method for preparing material for air purification, including using the solid mixture comprising following component in water as viscous
It is well mixed, granulate, dry and is calcined in the presence of mixture：
1) nano titanium oxide of 40-56 weight % semi-conducting material doping,
2) 42-50 weight % clay containing pyrolusite powder (rich 100,000,000,000,000 Industrial Co., Ltd.s purchase can be grown from Shandong), and
3) 2-10 weight % activated carbon (can be bought from Beijing Ke Cheng brilliance Technew SA), wherein above-mentioned each hundred
Point content is based on the gross weight of the solid mixture, and the percentage composition sum of all components of the solid mixture is
100 weight %.
2. according to the method for the 1st, wherein the solid mixture is included
1) nano titanium oxide of 45-50 weight % semi-conducting material doping,
2) 44-47 weight % clay containing pyrolusite powder (rich 100,000,000,000,000 Industrial Co., Ltd.s purchase can be grown from Shandong), and
3) 6-8 weight % activated carbon (can be bought from Beijing Ke Cheng brilliance Technew SA), wherein above-mentioned each hundred
Point content is based on the gross weight of the solid mixture, and the percentage composition sum of all components of the solid mixture is
100 weight %.
3. according to the method for the 1st or 2, wherein in the nano titanium oxide that the semi-conducting material adulterates, titanium dioxide
The weight ratio that titanium and semi-conducting material are counted using metal oxide is 60：40-96:4, preferably 65:35-90:10.
4. according to the method for any one of 1-3, wherein the semi-conducting material is selected from：Tungsten, niobium, chromium, indium, tin, strontium,
Iron, vanadium, gallium, the oxide of germanium and zinc, are preferably selected from：The oxide of iron, zinc, vanadium, tin etc..
5. according to the particle chi of the method for any one of 1-4, the wherein nano titanium oxide of semi-conducting material doping
Very little is 1-100nm, particularly preferably more preferably 20-80nm, 1-30nm.
6. according to the method for any one of 1-5, wherein being calcined at 400-600 DEG C, preferably enter at 480-550 DEG C
OK.
7. according to the method for any one of 1-5, wherein after drying, desciccate is warming up to 1-3 DEG C of speed
400-600 DEG C, 480-550 DEG C is preferably warming up to, and be incubated 0.5-1 hours at such a temperature.
8. pass through the material for air purification obtained according to the method for any one of 1-7.
These and other purposes, features and advantages of the present invention are readily able to be common after the hereafter consideration present invention is combined
Technical staff understands.
Brief description of the drawings
Fig. 1 is the UV-vis DRS absorption of the composite particulate material comprising clay and titanium dioxide and pure titinium dioxide
Comparison diagram.
Fig. 2 is the schematic diagram of the air circulation system comprising material for air purification of the present invention.
Fig. 3 is the filtering screen with honeycomb.
Fig. 4 is the XRD of composite particles prepared by embodiment 1.
The electron spin resonance (ESR) that Fig. 5 is composite particles A1 and nano titanium oxide A raw materials prepared by embodiment 1 is examined
Survey hydroxyl radical free radical intensity contrast figure.
Embodiment
According to an aspect of the invention, there is provided a kind of method for preparing material for air purification, including will include as follows
The solid mixture of component is well mixed in the presence of water is as adhesive, granulates, dries and is calcined：
1) nano titanium oxide of 40-56 weight % semi-conducting material doping,
2) 42-50 weight % clay containing pyrolusite powder (rich 100,000,000,000,000 Industrial Co., Ltd.s purchase can be grown from Shandong), and
3) 2-10 weight % activated carbon (can be bought from Beijing Ke Cheng brilliance Technew SA), wherein above-mentioned each hundred
Point content is based on the gross weight of the solid mixture, and the percentage composition sum of all components of the solid mixture is
100 weight %.
Pure nano titanium oxide generally has to want exciting for ultraviolet light, could occur light-catalyzed reaction.However, the present invention is adopted
Nano titanium oxide is doped with semi-conducting material, the material in the case where being excited by ultraviolet light, visible ray, near infrared light,
Light-catalyzed reaction can be produced.The nano titanium oxide adulterated on the semi-conducting material, is incorporated to Chinese patent herein
" ZL02103829.5 " is used as reference in full, wherein the nano titanium oxide of the present invention corresponds to the conduct addressed in the patent
The nano titanium oxide of the semi-conducting material doping of matrix.
In order to prepare material for air purification of the present invention, it is necessary to the nano titanium oxide adulterated using semi-conducting material.At this
Can be ability as the semi-conducting material of dopant material in the nano titanium oxide for inventing the semi-conducting material doping used
Field technique personnel it is well-known those, the oxide such as niobium, tungsten, chromium, indium, tin, strontium, iron, vanadium, gallium, germanium and zinc, preferably
The oxide of iron, zinc, vanadium, tin etc..In the nano titanium oxide that the semi-conducting material adulterates, titanium dioxide and semiconductor material
Expect the weight (in terms of metal oxide) than usually 60:40-96:4, preferably 65:35-90:10.The semi-conducting material of the present invention
The particle size of the nano titanium oxide of doping is nanoscale, and preferably average grain diameter is 1-100nm, more preferably 20-80nm, spy
You Xuanwei not 1-30nm.
Nano titanium oxide used of the invention can be prepared by known methods, and preferably be produced by metastable state chloridising.Tool
For body, the metastable state chloridising comprises the following steps：
1) hydrolysis：Titanium tetrachloride raw water solution is obtained into the mixing liquid containing white precipitate；
2) sol gel reaction：In step 1) add alone or in combination in gained mixing liquid with oxidation susceptibility and/or
The compound of reducing property, dissolves white precipitate, forms uniform reaction solution, is then heated at a temperature of 50-150 DEG C
Make liquid slow evaporation, form sol-gel；
3) filtration washing：Filter and use water cyclic washing step 2) products therefrom, until pH is 6-8；
4) dry：By step 3) products therefrom drying at -30 DEG C to 30 DEG C of temperature and 5-15mmHg vacuum, obtain
To certainly into the metastable state TiO 2 precursor of microparticle system；With
5) high-temperature calcination：By step 4) gained presoma calcined at a temperature of 200-1000 DEG C 0.5-6 hours, wherein
Step 1) hydrolysis, in step 2) sol gel reaction or in step 1) and step 2) semiconductor material is added in the two
The precursor of material.
In above-mentioned metastable state chloridising, step 1) it is related to the hydrolysis of raw material titanium tetrachloride.Raw material used in the step
Can be technical grade titanium tetrachloride or the pure titanium tetrachloride of reagent.From a cost perspective, the preferably chlorination of technical grade four
Titanium.The concentration of titanium tetrachloride is had no it is specifically limited, but preferably by the control of its molar concentration in 0.01-30mol/L, preferably
In the range of 0.05-10mol/L, more preferably 0.09-5mol/L.Step 1) hydrolysis can be carried out under any pH value,
Such as pH value can be about 0-11, most preferably preferably 0-8, more preferably 0-5,1-3.It is preferred that being entered in the hydrolysing step using alkali
Row is a certain degree of to be neutralized, wherein the alkali that can be used is included such as ammonium hydroxide, sodium hydroxide, potassium hydroxide, preferred hydrogen
Amine-oxides.Consumption also no any limitation to the alkali, it can be 0.1-10 that for example its consumption, which is based on every mole of titanium tetrachloride,
Mole, preferably 0.5-5 moles, more preferably 1-3 moles.The temperature that hydrolysis is carried out is not particularly limited, can be in room
Carry out, but preferably carry out at room temperature under temperature or low temperature.Due to the hydrolysis very exothermic of titanium tetrachloride, it is therefore desirable to use
Conventional chilling method such as liquid nitrogen cooling, refrigerated bath etc. are cooled down.After the completion of hydrolysis, obtain mixed containing white precipitate
Close liquid.
In above-mentioned metastable state chloridising, step 2) it is related to the formation of sol-gel.Specifically, 10-180 DEG C, it is excellent
Select at a temperature of 30-100 DEG C and the compound with oxidation susceptibility and/or reducing property added into step 1 alone or in combination) gained
In hydrolysate, white precipitate dissolves, and uniform reaction solution is formed, then at 50-150 DEG C, preferably 70-100 DEG C
At a temperature of heating response solution 1-10 hours, make liquid slow evaporation, form sol-gel.For the oxidisability in the step
And/or reproducibility compound includes such as hydrochloric acid, ammonium sulfide, sulfuric acid, nitric acid, perchloric acid, sulfurous acid, stannous chloride, protochloride
Iron, natrium nitrosum, sodium dithionate etc..In this step, the consumption of oxidisability and/or reproducibility compound is based on every mole four
Titanium chloride is 0.01-10 moles, more preferably preferably 0.05-5 moles, 0.1-3 moles.Terms used herein " oxidation susceptibility " and
" reducing property " is a relative concept, i.e., when the element oxide number of compound used therefor is minimum, it is easy to lose electronics and quilt
It is defined as reducing agent；And when the element oxide number of compound used therefor is maximum, its readily available electronics is simultaneously defined as oxidant.
In above-mentioned metastable state chloridising, step 3) it is related to step 2) filtering and washing of gained sol-gel.Washing
Purpose is to remove acid group and other impurity.Washing should be repeated, until the pH value of sol-gel is about 6-8, preferably
6.5-7.5。
In above-mentioned metastable state chloridising, step 4) it is related to step 3) gained washed the drying of sol-gel.The step
It is preferably carried out：Sol-gel will have been washed and be placed under -30 DEG C to 30 DEG C of temperature and 5-15mmHg vacuum dry 3-
6 hours, the moisture and possible solvent in colloidal sol are thus removed, is obtained from the metastable state titanium dioxide forerunner into microparticle system
Body.
In above-mentioned metastable state chloridising, step 5) it is related to step 4) high temperature of gained metastable state TiO 2 precursor forges
Burn.The step is entered preferably at 200-1000 DEG C at a temperature of more preferably 500-980 DEG C in calciner commonly used in the art
OK.There is no any limitation to the atmosphere of calcining, calcining can be carried out under oxygen or oxygen containing air atmosphere, can also be in inertia
Carried out in the presence of gas such as nitrogen, ammonia, argon gas.Although calcining is optimal under oxygen atmosphere, production is considered
Security, production cost and production satisfaction property, the calcining step are carried out using air atmosphere.Calcination time can be small for 0.5-6
When.
In addition, the nano titanium oxide in order to obtain the semi-conducting material doping that the present invention needs, can be in step 1)
Hydrolysis, step 2) sol gel reaction or step 1) and step 2) precursor of semi-conducting material is added in the two, such as
The inorganic acid salt or acylate of niobium, tungsten, chromium, indium, tin, strontium, iron, vanadium, gallium, germanium and zinc etc., such as chloride, bromide, sulphur
Hydrochlorate, nitrate, phosphate, acetate etc..Its consumption should make after calcining titanium dioxide and semi-conducting material in gained matrix (with
Metal oxide meter) weight ratio be 60:40-96:4, preferably 65:35-90:10.
Present invention wording used in term " metastable state chloridising " and " metastable state TiO 2 precursor " is " metastable
State " refers in the sol-gel preparation process of the inventive method, gel shape from heterogeneous non-equilibrium, non-stability system
Into, by filtering, washing, vacuum drying, formed it is thermodynamically unstable, from into before the metastable state titanium dioxide of microparticle system
Drive body.The phase transition temperature that the presoma changes from Detitanium-ore-type to rutile-type is less than 1000 DEG C, hence it is evident that less than conventional stationarity two
The phase transition temperature (the rutile-type transition temperature range of conventional stationarity titanium dioxide is about 1100-1400 DEG C) of titanium oxide, this is
Metastable physical property characteristic.In addition, diffraction peaks broadening phenomenon, the large percentage of surface atom, table is presented in its X-ray diffraction spectra
Face unsaturated bond rich in etc., these all illustrate the present invention nano-TiO 2 precursor belong to metastable state material.Therefore, exist
" metastable state chloridising " term is used in this specification, conventional chloridising is different from.
In one embodiment of the invention, the nano titanium oxide of the semi-conducting material doping used can also be further
Surface is modified, and in order to open the reunion of nano titanium oxide, improves the stability of nano titanium oxide.Therefore, in semiconductor
Upper conjugated system organic matter is coated on the surface of material doped titanium dioxide nanoparticle (can now be referred to as matrix).As institute
Conjugated system organic matter is stated, it can be mentioned that maleic acid and its salt, fumaric acid and its salt, alkene sulfonic acid (such as vinyl sulfonic acid, propylene
Base sulfonic acid, allyl sulphonic acid etc.) and its salt, DBSA and its salt, optionally substituted acrylic acid and its salt etc..It is described
The weight for the nano titanium oxide (matrix) that the content of conjugated system organic matter is adulterated based on the semi-conducting material is usually
0.01-20 weight %, preferably 0.05-15 weight %, more preferably 0.1-10 weight %.
In order to coat conjugated system organic matter on the nano titanium oxide surface that semi-conducting material adulterates, by will be by Asia
Stable state chloridising production semi-conducting material doping nm TiO 2-base body and conjugated system organic matter in water in proportion
Fully mix, be aged and dry and carry out conjugated system Coated with Organic Matter.The ratio of described matrix and the organic matter in water
The nano titanium dioxide photocatalyst obtained after drying should be made to contain 0.01-20 weight %, preferably 0.05-15 weight %, it is more excellent
Select 0.1-10 weight % conjugated system organic matter.Ageing and drying can be at 80-150 DEG C, at a temperature of preferably 95-120 DEG C
Carry out 3-20 hours, preferably 5-15 hours.
By semi-conducting material, for example the impurity energy level such as zinc, tin, iron is adulterated and the surface energy level of a large amount of dangling bonds in surface is mixed
Miscellaneous, the effect of doping, which makes to produce close to the top of valence band in Nano semiconductor, connects nucleophobic doped energy-band, under conduction band
Side produces the doped energy-band for giving electronics, when the nano titanium oxide semiconductor of semi-conducting material doping is by more relatively low than ultraviolet light
Luminous energy when, for example during the energy of visible ray or near infrared light, it is possible to which photocatalysis produces electronics and excited, produced in valence band
The hole of positively charged, produces electronegative electronics on conduction band, forms electronics and the conducting carriers in hole, and with less than 10-6
The time of number of seconds magnitude, instantaneous migration to material surface plays due light-catalyzed reaction.Therefore, conventional pure nanometer titanium dioxide
Titanium generally has to want exciting for ultraviolet light, could occur light-catalyzed reaction, but the nano titanium oxide that the present invention is used is because mixing
Miscellaneous semi-conducting material, the material can produce light-catalyzed reaction when being excited by ultraviolet light, visible ray, near infrared light,
So as to organic contamination of degrading longer, antibacterial anti-mildew, no light can be used and shone.
Based on the gross weight for the solid mixture addressed in preparation method of the present invention, the nano-silica of semi-conducting material doping
The consumption for changing titanium is usually 40-56% weight %, preferably 45-50 weight %.
In order to prepare material for air purification of the present invention, it is necessary to use the combination of clay containing pyrolusite powder and activated carbon.Contain
Contain more rich multivalence manganese ion in pyrolusite powder clay, it is used as bivalent manganese source.Although in many mineral all containing manganese with
And many manganese compounds can be used as bivalent manganese source, but the present inventor has found first, makees when using clay containing pyrolusite powder
For manganese source, when providing reduction reaction conditionses by activated carbon, enough bivalent manganeses can be produced, so as to promote hydrogen peroxide to hydroxyl
The conversion of free radical.However, during using such as pure manganese dioxide, tetravalent manganese therein can not play promotion hydrogen peroxide to hydroxyl
The effect of radical conversion, actually using can not all promote hydrogen peroxide during the manganese compound of non-divalence to hydroxyl radical free radical
Transformation.
Clay containing pyrolusite powder is also referred to as high viscosity clay, really the clay containing pyrolusite powder.Pyrolusite powder is powder
The pyrolusite of shape.Pyrolusite be easy to be weathered into it is powdered, it is processed to have as grey black and steel grey pigment, main component
Manganese dioxide, the ground such as originating in Hunan, Yunnan, Hebei.Clay is a kind of matt toughness of widely distributed colloidal state in itself
Soil, be plastic when moist, be hard after roasting.Clay is the basic material of Production of Ceramics, is distributed in nature wide
General, reserves are big, and species is various, is a kind of valuable natural resources.Clay containing pyrolusite powder both can be prepared voluntarily, can also be purchased
Buy, for example growing rich 100,000,000,000,000 Industrial Co., Ltd.s purchase from Shandong obtains.
Clay containing pyrolusite powder and activated carbon also constitute carrier material together, support and company due to clay network skeleton
Connect so that the block with larger mechanical strength can be formed after roasting, while the also combination just because of clay and activated carbon
Effect, generates microcellular structure, adds suction-operated of the composite particulate material to contaminant molecule, so as to strengthen its photocatalysis
Effect.
Based on the gross weight for the solid mixture addressed in preparation method of the present invention, the consumption of the clay containing pyrolusite powder is usual
For 42-50 weight %, preferably 44-47 weight %.
In the present invention, the effect of activated carbon is to provide reproducibility effect and loose structure.Do not have as the type of activated carbon
There is special limitation, cocoanut active charcoal, active fruit shell carbon (including apricot shell activated carbon, fruit stone shell activated carbon, walnut shell can be used
Activated carbon), wood activated charcoal and coal mass active carbon.As the shape of activated carbon, powdered activated carbon, seed activity can be used
Charcoal, indefinite form material activated carbon, cylindrical activated carbon, spherical activated charcoal and other shapes of activated carbon.For example, can be from Beijing
The activated carbon that the purchase of Ke Cheng brilliance Technew SA is obtained.
Based on the gross weight for the solid mixture addressed in preparation method of the present invention, the consumption of activated carbon is usually 2-10 weights
Measure %, preferably 6-8 weight %.
In order to prepare material for air purification of the present invention, first by the nano titanium oxide adulterated comprising semi-conducting material, contain
The solid mixture of pyrolusite powder clay and activated carbon is well mixed in the presence of water, is then granulated.Due to the semiconductor material
Nano titanium oxide, clay containing pyrolusite powder and the activated carbon of material doping can not effectively be bonded together in itself to be suitable for then
Shaping or granulation, therefore usually require addition water the semi-conducting material is adulterated as adhesive nano titanium oxide,
Clay containing pyrolusite powder and activated carbon are uniformly bonded together, and then granulate, dry and are calcined.As water, it can use such as
Running water, distilled water, deionized water etc..The addition of water is usually 30-50 weight %, preferably 35-45 weight %, based on this
The gross weight for the solid mixture addressed in invention preparation method.In order to granulate, generally by the solid mixture in addition water
In the case of stirred in mixer, be for example stirred with about 200r/min rotating speed, then artificial granulation, can also be
Mix, granulate in comminutor.Comminutor can be single screw extrusion machine, double screw extruder.As needed, circle can be a granulated into
Post, spheroid, spheroid, pill, sheet etc..After granulation, dry.The drying is generally carried out at 90-110 DEG C, preferably in 95-
Carried out at 105 DEG C.Drying time is usually 30-120 minutes, preferably 60-80 minutes.After drying, heating roasting.Roasting
Purpose is the composite particles of the nano titanium oxide, clay containing pyrolusite powder and activated carbon in order to be adulterated comprising semi-conducting material
Sintering, forms firm particle, and the manganese in clay containing pyrolusite powder is reduced into bivalent manganese.Therefore, after generally drying
Particle be calcined at 400-600 DEG C, preferably at 480-550 DEG C be calcined.Advantageously, first by dried particle with 1-3
DEG C speed be warming up to 400-600 DEG C, be preferably warming up to 480-550 DEG C, and be incubated 0.5-1 hours at such a temperature.It is calcined gas
Atmosphere can be with nitrogen, air, preferably air.The material for air purification of the present invention is can obtain by roasting.
There is provided the material for air purification obtained by the inventive method according to another aspect of the present invention.Obviously, this hair
Bright material for air purification is the hole adsorbed gas contaminant molecule in porous material, material, so that the photocatalysis of reinforcing material
Effect.The each feature described above for the method for preparing material for air purification is accordingly adapted to air cleaning material of the present invention
Material.
In material for air purification of the present invention, the nano titanium oxide of semi-conducting material doping can be produced in light-catalyzed reaction
Raw hydrogen peroxide (H2O2), the presence of bivalent manganese can promote hydrogen peroxide to be converted to hydroxyl radical free radical, so that hydrogen peroxide turns
Change and produce more hydroxyl radical free radicals, make the effect of catalytic degradation more notable.The nano titanium oxide adulterated by energy level is very
OH, O can be extremely produced in dark condition2 -、·HO2Deng free group and H2O2Deng peroxide.Therefore, will partly it lead
The material doped nano titanium oxide of body and bivalent manganese are combined, and can make composite catalyzing, the degraded catharsis in dark condition
It is stronger, be conducive to removing multiple types, the pollutant of high concentration in indoor and automobile.
Pure titinium dioxide belongs to wide band gap semiconducter.Have between the light absorption wavelength threshold value (λ g) and band-gap energy (Eg) of semiconductor
Following relation λ g (nm)=1240/ [Eg (eV)].Understand, absorbing wavelength threshold value is in ultra-violet (UV) band.Because ultraviolet light is only accounted for up to ground
The very small part of the sunshine in face so that the utilization rate of solar energy is very low, therefore as the key factor for limiting its application.
Fig. 1 is the composite particulate material (" clay-TiO comprising clay and titanium dioxide2- AC " is represented) and pure titinium dioxide
(“TiO2" represent) and UV-vis DRS absorb contrast.In composite particulate material due to content of titanium dioxide reduction and
UV absorption intensity decreases, are shown as a small absworption peak, but composite particulate material in whole visible ray and infrared part all
There is absorption.Because the energy gap of anatase is 3.2eV, greater band gap will could show that catalysis is lived under the exciting of ultraviolet light
Property.But UV energy only accounts for 5% in sunshine, and visible light energy accounts for 43%.Therefore composite particulate material is to sunshine
The middle overwhelming majority is all can absorb, and this will greatly improve the photocatalytic activity of titanium dioxide.Therefore, material for air purification of the invention
Utilization to sunshine will be much higher than pure nano titanium oxide.
In material for air purification of the present invention, hydrogen peroxide can promote it towards generation hydroxyl due to the presence of bivalent manganese
The direction of free radical is carried out.The embryonic stem-like cells formula equation that bivalent manganese is participated in is expressed as：
Mn2++H2O2-Mn3++·OH+OH-
Hydroxyl radical free radical (OH) has very high electronegativity or electrophilicity, and its electron affinity energy power is up to 569.3kJ, hydroxyl
Base free radical OH oxidation susceptibility is especially strong, and the oxidisability than potassium permanganate and potassium bichromate is also strong, can aoxidize many biographies
The inoxidizable organic substance of system method.Hydroxyl radical free radical can participate in taking out hydrogen plus and and the reaction of three classes, energy such as electro transfer
By capturing the hydrogen atom in organic pollutant molecule, filling the reaction paths such as unsaturated C-C keys, make various pollutants rapid
Degraded.
The organic volatile such as hydroxyl radical free radical and formaldehyde, toluene reacts, and is degraded to nontoxic or low toxicity small molecule.For example,
Hydroxyl radical free radical and toluene or the reaction of toluene intermediate product ultimately generate CO2And H2O, hydroxyl radical free radical OH and toluene molecule
Reaction is as follows：
The hydrogen peroxide H that bivalent manganese is produced in being reacted using optically catalytic TiO 22O2, produce more hydroxyl frees
Base OH, so as to increase OH generation, and then enhances the effect of photocatalytic pollutant degradation.In addition, bivalent manganese makes nanometer
The electronics and hole that titanium dioxide is produced in light-catalyzed reaction are easier separation, so as to improve its photocatalysis efficiency.Therefore, will
The nano titanium oxide and bivalent manganese of semi-conducting material doping are organically combined, and can be made the composite catalyzing in dark condition, be degraded
Catharsis is stronger, is conducive to removing multiple types, the pollutant of high concentration in automobile.
The porous nano titanium dioxide of the present invention and the composite particles of manganous compound, the stronger hydroxyl of composite catalyzing is certainly
By base OH signals, so as to substantially increase the photocatalysis of titanium dioxide.
Therefore, material for air purification of the present invention can be used for purifying air, in particular for purifying the air of a room or automobile
Interior air.The material is in the presence of moving air, especially circulation air, it might even be possible to degraded is played in dark condition net
Change is acted on, and the effect is stronger, so as to be conducive to removing multiple types, the pollutant of high concentration in indoor, automobile.
Therefore, material for air purification of the present invention can be used for producing air cleaning unit, in particular for production clean room
Interior air or the air cleaning unit for purifying automobile inner air.The purifier generally includes return air inlet, air outlet and air
Purification assembly, the clean air package is comprising material for air purification of the present invention and positioned at lower column position：Return air inlet, air outlet
And/or between return air inlet and air outlet.As clean air package, can for example be made as shown in Figure 3 has honeycomb
Purification web form, material for air purification of the present invention is filled into net in granular form.When producing air cleaning unit, by sky
Gas purification assembly is assembled into wherein so that the air from return air inlet suction after the purifying net from air outlet by sending out.Due to this
Invention material for air purification in air volatile contaminant (formaldehyde, benzene,toluene,xylene, ethylbenzene, styrene, germ,
Peculiar smell etc.) it is subject to potent degraded, it is translated into harmless CO2And H2O, so as to play significant net to automobile or room air
Change is acted on.
For example, a kind of vehicle air self-circulation system, the circulatory system can be made using material for air purification of the present invention
Including one or more clean air packages for including material for air purification of the present invention, the gas of suction passes through net after the component
Change, be then sent.
Fig. 2 is the schematic diagram of an embodiment of the air circulation system for automobile.The air circulation system is bag
Include the vehicle air self-circulation system of air return port system, air-out port system, cleaning system and interactive system.
Air return port system includes return air hole 12, return air valve 11 and outer return air inlet 13.Return air hole 12 is arranged on apparatus casing
The first side surface and extend inwardly to return air valve 11, be connected with return air valve 11, return air valve 11 and cleaning system phase
Connection.Outer return air inlet 13 is arranged on the lower surface of apparatus casing and extends inwardly to return air valve 11, is connected with return air valve 11
Connect.Return air valve 11 is double-direction control valve.
Cleaning system include purification assembly 21 (for example filtering screen with honeycomb), by Blast mechanism into drum
Wind apparatus 22 and high temperature facilitate device 23 (urging fast volatile organic matter to accelerate volatilization for high temperature).Material for air purification of the present invention
It is filled into the purification assembly 21 with honeycomb as shown in Figure 3.
Purification assembly 21 is connected with air return port system, and air-blast device 22 is connected with purification assembly 21 and is arranged on relative
In the opposite side of air return port system.High temperature is facilitated device 23 and is connected with air-blast device 22, positioned at opposite with purification assembly 21
Side.
Air-out port system includes exhaust vent 31 and optional chemical purifying device.Chemical purifying device is deposited including chemical reagent
Reservoir 32 and fluid filling pump 33.Exhaust vent 31 is arranged on the second side surface of apparatus casing and extends inwardly to cleaning system and net
Change system is connected, and chemical purifying device is arranged on the passage that exhaust vent extends internally.Fluid filling pump 33 stores chemical reagent
The chemical reagent of device 32 is delivered to exhaust vent 31.As chemical reagent, water, air freshener, plants essential oil etc. can be used.
Interactive system includes the display device 41, control button 42 and operation strong 43 being made up of display screen.Control is pressed
Key 42 is used for air volume control key, temperature adjusting key, air circulation shift key, and operation strong 43 is used for air-conditioning switch.
People are watched by the display device 41 of interactive system, and are set by control button 42 and the strong control of operation 43
It is standby, vapour harmful gas in vehicle is passed into cleaning system by air return port system and purified, finally by air-out port system
Discharge, so as to efficiently solve the problem of automobile inner air is purified.
There is vehicle air self-circulation system including material for air purification of the present invention active soil pick-up to tell new, potent urge
Change, volatilization, high speed degrade, effectively shorten the TVOC volatilization times and have potent purification feature, especially when for vehicle sky at a high speed
During gas self-circulation purifying system, automobile that can be serious to current air pollution carries out sufficiently effective purification treatment.
Continue permanent volatilization release high concentration pernicious gas for automobile interior trim finishing material, the wide air of the present invention of bag is net
Change the air purifier or air circulation system of material, it is possible to achieve catalysis release, shortening volatilization cycle, potent pollution degradation
Thing.I.e. by the vehicle self-circulation system with the purification techniques, ceaselessly by pollutant catalysis volatilization, quick " suction ", so
The strongly active group hydroxy free radical being catalyzed afterwards by dynamic complex, discharges for a long time to the inner facility and ornament of car room
Volatile contaminant (formaldehyde, benzene,toluene,xylene, ethylbenzene, styrene, germ, peculiar smell etc.) is subject to potent degraded, by its turn
Turn to harmless CO2And H2O, the pollution for making time script several years can't get rid of, by the improvement in a couple of days or a few weeks, reaches
Degraded is removed, and realizes the self-circulation purifying of vehicle interior, reaches the effect of potent degradation of contaminant, and keeps in-car air for a long time
Clean purpose.
Embodiment
Below with reference to specific embodiment, the invention will be further described, but should not be construed as to present invention protection
The limitation of scope.
Reference implementation example 1：The nano titanium oxide A of di-iron trioxide semiconductor doping preparation
49 grams of (0.3mol) ferric trichlorides (Beijing Raw Materials Company of Chemical Industry) are dissolved in 1000ml l5% (weights at room temperature
Amount/volume) NH4In the OH aqueous solution.Then refrigerated bath is used, 0.6mol technical grades titanium tetrachloride (Tianjin Chemical Plant) is slow
Slowly it is added drop-wise in the aqueous solution, it is uniform in the case where at the uniform velocity stirring to produce white precipitate.Then 0.15mol perchloric acid is added under agitation
(factory of Beijing chemical industry two), dissolves white precipitate, obtains transparent liquid.The liquid is heated at 95 DEG C makes it evaporate 2 hours,
Unnecessary moisture is removed, sol-gel is obtained.Filtering gained sol-gel and with 500ml water washings 4 times, it is 7 to make its pH.Will
Sol-gel after washing is dried 3 hours under 20 DEG C and 10mmHg, obtains white micro mist, i.e. metastable state titanium dioxide forerunner
Body.By the white micro mist in calcining furnace at 800 DEG C calcine 1 hour, obtain di-iron trioxide doping nano titanium oxide,
Nano titanium oxide A is designated as, the wherein weight ratio of di-iron trioxide and titanium dioxide is 24:48, and particle diameter is 30-60nm.
Reference implementation example 2：The nano titanium oxide B of tin ash semiconductor doping preparation
8.5 grams of (0.033mol) butters of tin (Beijing Raw Materials Company of Chemical Industry) are dissolved in 1000ml 5% at room temperature
The NH of (weight/volume)4In the OH aqueous solution.Then refrigerated bath is used, by 0.6mol technical grades titanium tetrachloride (Tianjin chemical industry
Factory) it is slowly dropped in the aqueous solution, it is uniform in the case where at the uniform velocity stirring to produce white precipitate.Then 0.15mol is added under agitation
Hydrochloric acid (factory of Beijing chemical industry two), dissolves white precipitate, obtains transparent liquid.The liquid is heated at 95 DEG C makes it evaporate 2
Hour, unnecessary moisture is removed, sol-gel is obtained.Filtering gained sol-gel and with 500ml water washings 4 times, makes its pH
For 7.Sol-gel after washing is dried 3 hours under 20 DEG C and 10mmHg, white micro mist, i.e. metastable state titanium dioxide is obtained
Titanium precursors.By the white micro mist in calcining furnace at 860 DEG C calcine 1 hour, obtain tin ash doping nano-silica
Change titanium, be designated as nano titanium oxide B, the wherein weight ratio of tin ash and titanium dioxide is 5:48, and particle diameter is 20-
50nm。
Reference implementation example 3：The nano titanium oxide C of zinc oxide semi-conductor doping preparation
At room temperature by 19 grams of (0.15mol) zinc nitrates (Beijing Raw Materials Company of Chemical Industry) be dissolved in 1000ml5% (weight/
Volume) NH4In the OH aqueous solution.Then refrigerated bath is used, 0.6mol technical grades titanium tetrachloride (Tianjin Chemical Plant) is slow
It is added drop-wise in the aqueous solution, it is uniform in the case where at the uniform velocity stirring to produce white precipitate.Then 0.15mol nitric acid (north is added under agitation
Capital Raw Materials Company of Chemical Industry), white precipitate is dissolved, transparent liquid is obtained.The liquid is heated at 95 DEG C makes its evaporation 2 small
When, unnecessary moisture is removed, sol-gel is obtained.Filtering gained sol-gel and with 500ml water washings 4 times, makes its pH be
7.Sol-gel after washing is dried 5 hours under 20 DEG C and 10mmHg, white micro mist, i.e. metastable state titanium dioxide is obtained
Presoma.By the white micro mist in calcining furnace at 900 DEG C calcine 2 hours, obtain Zinc oxide doped nano titanium oxide,
Nano titanium oxide C is designated as, the wherein weight ratio of zinc oxide and titanium dioxide is 12:48, and particle diameter is 50-80nm.
The preparation of composite particles：
Embodiment 1
Example, weighs 47 weight % clay containing pyrolusite powder (purchased from the limited public affairs of rich 100,000,000,000,000 industry of Shandong taste in mass ratio
Department), 45 weight % nano titanium oxide A and 8 weight % activated carbon (being purchased from Beijing Ke Cheng brilliance Technew SA),
Under 200r/min speed stirring, adding the gross weight based on clay containing pyrolusite powder, nano titanium oxide A and activated carbon is
40 weight % deionized water, is well mixed, and granulating and forming is small spherical granules, is dried 70 minutes at 100 DEG C, then with 3
DEG C/min programming rates rise to 550 DEG C, and keep at such a temperature after 0.5h, sintering obtains composite particles A1.
The XRD spectrum of the composite particles is shown in Fig. 4, the ESR detection hydroxyls of composite particles A1 and nano titanium oxide A raw materials from
Fig. 5 is shown in by rheobase comparison diagram.
From fig. 4, it can be seen that the big diffraction maximum and obvious MnO that have obvious titanium dioxide phase in XRD diffracting spectrums are spread out
Penetrate peak.Wherein, TiO2As the key component in composite particles, photocatalysis main function, MnO are played2Due to the reduction of activated carbon
Property effect and be rendered as MnO.
Fig. 5 is composite particles A1 and the electron spin resonance of nano titanium oxide A under equal conditions prepared by embodiment 1
ESR detects hydroxyl radical free radical intensity contrast figure.From figure 5 it can be seen that under conditions of with the presence of bivalent manganese, hydroxyl radical free radical OH letters
Number intensity is high nearly 2 times.Bivalent manganese in this explanation manganese compound makes optically catalytic TiO 2 reaction be easier towards generation hydroxyl
Base free radical OH direction is carried out, and bivalent manganese is to hydroxyl radical free radical OH generation with very strong facilitation.
Embodiment 2
Example, weighs 45 weight % clay containing pyrolusite powder (purchased from the limited public affairs of rich 100,000,000,000,000 industry of Shandong taste in mass ratio
Department), 48 weight % nano titanium oxide B and 7 weight % activated carbon (being purchased from Beijing Ke Cheng brilliance Technew SA),
Under 200r/min speed stirring, adding the gross weight based on clay containing pyrolusite powder, nano titanium oxide B and activated carbon is
40 weight % deionized water, be well mixed, granulating and forming is ellipsoidal particle, at 95 DEG C dry 80 minutes, then with 2 DEG C/
Min programming rates rise to 520 DEG C, and keep at such a temperature after 0.75h, and sintering obtains composite particles A2.
Embodiment 3
Example, weighs 44 weight % clay containing pyrolusite powder (purchased from the limited public affairs of rich 100,000,000,000,000 industry of Shandong taste in mass ratio
Department), 50 weight % nano titanium oxide C and 6 weight % activated carbon (being purchased from Beijing Ke Cheng brilliance Technew SA),
Under 200r/min speed stirring, adding the gross weight based on clay containing pyrolusite powder, nano titanium oxide C and activated carbon is
40 weight % deionized water, is well mixed, and granulating and forming is small long particle shape particle, is dried 60 minutes at 105 DEG C, then with 1
DEG C/min programming rates rise to 480 DEG C, and keep at such a temperature after 1h, sintering obtains composite particles A3.
Comparative example 1
Example, weighs 50 weight % nano titanium oxide A and 50 weight % kaolinton (without manganese member in mass ratio
Element, Co., Ltd is processed purchased from Hebei Lingshou County illuminate into mineral products), under 200r/min speed stirring, add viscous based on kaolinite
Soil and nano titanium oxide A gross weight are 40% deionized water, are well mixed, and granulating and forming is small spherical granules,
Dried at 100 DEG C 60 minutes, then rise to 550 DEG C with 2 DEG C/min programming rates, and kept at such a temperature after 0.5h, sintered
To composite particles BA1, the particle is free of manganese element after testing.
Comparative example 2
Example, weighs 50 weight % nano titanium oxide B and 50 weight % kaolinton (without manganese member in mass ratio
Element, Co., Ltd is processed purchased from Hebei Lingshou County illuminate into mineral products), under 200r/min speed stirring, add viscous based on kaolinite
Soil and nano titanium oxide B gross weight are 40% deionized water, are well mixed, and granulating and forming is small spherical granules,
Dried at 100 DEG C 60 minutes, then rise to 550 DEG C with 2 DEG C/min programming rates, and kept at such a temperature after 0.5h, sintered
To composite particles BB1, the particle is free of manganese element after testing.
Comparative example 3
Example, weighs 50 weight % nano titanium oxide C and 50 weight % kaolinton (without manganese member in mass ratio
Element, Co., Ltd is processed purchased from Hebei Lingshou County illuminate into mineral products), under 200r/min speed stirring, add viscous based on kaolinite
Soil and nano titanium oxide C gross weight are 40% deionized water, are well mixed, and granulating and forming is small spherical granules,
Dried at 100 DEG C 60 minutes, then rise to 550 DEG C with 2 DEG C/min programming rates, and kept at such a temperature after 0.5h, sintered
To composite particles BC1, the particle is free of manganese element after testing.
Comparative example 4
Example, weighs 25 weight % MnO in mass ratio2Powder, 50 weight % nano titanium oxide A and 25 weight %
Kaolinton (is free of manganese element, Co., Ltd is processed into mineral products purchased from Hebei Lingshou County illuminate), is stirred in 200r/min speed
Under, add and be based on MnO2The gross weight of powder, kaolinton and nano titanium oxide A is 40% deionized water, is well mixed,
Granulating and forming is small spherical granules, is dried at 100 DEG C 60 minutes, then rises to 550 DEG C with 2 DEG C/min programming rates, and
0.5h is kept at this temperature, sintering obtains composite particles BA2, manganese of the particle without bivalent manganese but containing other chemical valences.
Comparative example 5
Example, weighs 25 weight % MnO in mass ratio2Powder, 50 weight % nano titanium oxide B and 25 weight %
Kaolinton (is free of manganese element, Co., Ltd is processed into mineral products purchased from Hebei Lingshou County illuminate), is stirred in 200r/min speed
Under, add and be based on MnO2The gross weight of powder, kaolinton and nano titanium oxide B is 40% deionized water, is well mixed,
Granulating and forming is small spherical granules, is dried at 100 DEG C 60 minutes, then rises to 550 DEG C with 2 DEG C/min programming rates, and
0.5h is kept at this temperature, sintering obtains composite particles BB2, manganese of the particle without bivalent manganese but containing other chemical valences.
Comparative example 6
Example, weighs 25 weight % MnO in mass ratio2Powder, 50 weight % nano titanium oxide C and 25 weight %
Kaolinton (is free of manganese element, Co., Ltd is processed into mineral products purchased from Hebei Lingshou County illuminate), is stirred in 200r/min speed
Under, add and be based on MnO2The gross weight of powder, kaolinton and nano titanium oxide C is 40% deionized water, is well mixed,
Granulating and forming is small spherical granules, is dried at 100 DEG C 60 minutes, then rises to 550 DEG C with 2 DEG C/min programming rates, and
0.5h is kept at this temperature, sintering obtains composite particles BC2, manganese of the particle without bivalent manganese but containing other chemical valences.
Application implementation case
Composite particles prepared by each embodiment and comparative example respectively self-assemble to vehicle air self-loopa system as shown in Figure 2
In system, be specifically uniformly be filled into honeycomb filtering screen as shown in Figure 3, it is then packaged, consumption be 800 grams/
dm3, as the purification assembly in vehicle air self-circulation system.Reference standard QB/T 2761-2006 carry out going for organic gas
Except effect detection.Testing result is as shown in table 1 below.
Claims (8)
1. a kind of method for preparing material for air purification, including in water it regard the solid mixture comprising following component as adhesive
In the presence of be well mixed, granulation, dry and be calcined：
1) nano titanium oxide of 40-56 weight % semi-conducting material doping,
2) 42-50 weight % clay containing pyrolusite powder (rich 100,000,000,000,000 Industrial Co., Ltd.s purchase can be grown from Shandong), and
3) 2-10 weight % activated carbon (can be bought from Beijing Ke Cheng brilliance Technew SA), wherein above-mentioned each percentage contains
Amount is based on the gross weight of the solid mixture, and the percentage composition sum of all components of the solid mixture is 100
Weight %.
2. method according to claim 1, wherein the solid mixture is included
1) nano titanium oxide of 45-50 weight % semi-conducting material doping,
2) 44-47 weight % clay containing pyrolusite powder (rich 100,000,000,000,000 Industrial Co., Ltd.s purchase can be grown from Shandong), and
3) 6-8 weight % activated carbon (can be bought from Beijing Ke Cheng brilliance Technew SA), wherein above-mentioned each percentage contains
Amount is based on the gross weight of the solid mixture, and the percentage composition sum of all components of the solid mixture is 100
Weight %.
3. according to the method for claim 1 or 2, wherein in the nano titanium oxide that the semi-conducting material adulterates, titanium dioxide
The weight ratio that titanium and semi-conducting material are counted using metal oxide is 60：40-96:4, preferably 65:35-90:10.
4. method as claimed in one of claims 1-3, wherein the semi-conducting material is selected from：Tungsten, niobium, chromium, indium, tin, strontium,
Iron, vanadium, gallium, the oxide of germanium and zinc, are preferably selected from：The oxide of iron, zinc, vanadium, tin etc..
5. the particle chi of the nano titanium oxide of method as claimed in one of claims 1-4, wherein semi-conducting material doping
Very little is 1-100nm, particularly preferably more preferably 20-80nm, 1-30nm.
6. method as claimed in one of claims 1-5, wherein being calcined at 400-600 DEG C, preferably enters at 480-550 DEG C
OK.
7. method as claimed in one of claims 1-5, wherein after drying, desciccate is warming up to 1-3 DEG C of speed
400-600 DEG C, 480-550 DEG C is preferably warming up to, and be incubated 0.5-1 hours at such a temperature.
8. the material for air purification obtained by method as claimed in one of claims 1-7.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108187651A (en) * | 2017-12-28 | 2018-06-22 | 山东纳安环保科技有限公司 | A kind of preparation method and application for carrying zinc nano-titanium dioxide |
| CN111514883A (en) * | 2019-08-30 | 2020-08-11 | 南京林业大学 | Preparation method of carbon-based catalyst for indoor air purification |
| CN112246083A (en) * | 2020-09-04 | 2021-01-22 | 秦立新 | Negative oxygen ion air purifying agent, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1448214A (en) * | 2002-03-29 | 2003-10-15 | 徐瑞芬 | Nano titanium dioxide photocatalyst,prep. and use thereof |
| CN1805780A (en) * | 2003-06-19 | 2006-07-19 | 开利公司 | Air purification system comprising a catalyst and a light source |
| CN106732572A (en) * | 2016-11-16 | 2017-05-31 | 中山大学 | A kind of scavenging material of gaseous contaminant and its preparation method and application |
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2017
- 2017-06-05 CN CN201710414079.6A patent/CN107081148B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1448214A (en) * | 2002-03-29 | 2003-10-15 | 徐瑞芬 | Nano titanium dioxide photocatalyst,prep. and use thereof |
| CN1805780A (en) * | 2003-06-19 | 2006-07-19 | 开利公司 | Air purification system comprising a catalyst and a light source |
| CN106732572A (en) * | 2016-11-16 | 2017-05-31 | 中山大学 | A kind of scavenging material of gaseous contaminant and its preparation method and application |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108187651A (en) * | 2017-12-28 | 2018-06-22 | 山东纳安环保科技有限公司 | A kind of preparation method and application for carrying zinc nano-titanium dioxide |
| CN111514883A (en) * | 2019-08-30 | 2020-08-11 | 南京林业大学 | Preparation method of carbon-based catalyst for indoor air purification |
| CN112246083A (en) * | 2020-09-04 | 2021-01-22 | 秦立新 | Negative oxygen ion air purifying agent, and preparation method and application thereof |
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