CN108714418A - A kind of photocatalyst overlay film carrier material and preparation method thereof, application - Google Patents

A kind of photocatalyst overlay film carrier material and preparation method thereof, application Download PDF

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Publication number
CN108714418A
CN108714418A CN201810673113.6A CN201810673113A CN108714418A CN 108714418 A CN108714418 A CN 108714418A CN 201810673113 A CN201810673113 A CN 201810673113A CN 108714418 A CN108714418 A CN 108714418A
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photocatalyst
overlay film
carrier
particle
preparation
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于峰
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Beijing Sheng Rui New Mstar Technology Ltd
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Beijing Sheng Rui New Mstar Technology Ltd
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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    • B01J20/18—Synthetic zeolitic molecular sieves
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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    • B01J21/08—Silica
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    • B01J35/39—Photocatalytic properties
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
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    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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Abstract

The present invention provides a kind of photocatalyst overlay film carrier materials, are mainly prepared by the following raw material：The photocatalyst solution that carrier granular and mass percent concentration are 20% or more, preparation method include：(A) carrier granular is impregnated in photocatalyst solution more than for 24 hours, the carrier granular after immersion is leached, natural air drying；(B) 100 DEG C or more drying to get.The photocatalyst overlay film carrier material of the embodiment of the present invention by by photocatalyst overlay film on the carrier particles; in this way the Environmental Hormones class such as PARA FORMALDEHYDE PRILLS(91,95), benzene, bisphenol-A noxious substance on the carrier particles after; by ultraviolet light to the further photocatalysis of photocatalyst; harmful substance can be resolved into harmless water and carbon dioxide; to achieve the purpose that environmental protection, degradation of contaminant; avoid the drawbacks of carrier mass such as conventionally employed single activated carbon can only simply reach absorption, cannot implement detoxication completely.

Description

A kind of photocatalyst overlay film carrier material and preparation method thereof, application
Technical field
The present invention relates to novel environment friendly sorbing material manufacture fields, in particular to a kind of photocatalyst overlay film carrier material Material and preparation method thereof, application.
Background technology
So-called Environmental Hormone hormone refers to the exogen interference endocrine chemical substance of organism, these substances can simulate Internal natural hormone is combined with hormonal receptor, influences hormonal amount in original body, and makes body generation pair Internal hormonal accumulation over effect, makes internal system lack of proper care.And then the functions such as normal reproductive, development are hindered, or even have Cause the harm of malignant tumour and biological extinction.Why environmental hormone substance will appear, first, due to a large amount of in food, drinking-water There are environmental hormone substance, causing the oligozoospermia of man, male degenerate so that male sterility it is occurred frequently.Second is that leading Cause the teratogenesis of pregnancy fetus.Through scientist the study found that the women of child-bearing age are polluted by environmental hormone for a long time, the fetus that can make to become pregnant is abnormal The possibility of shape greatly increases, and makes the face of fetus, the part deformity of limbs or sexual organ.Therefore the environment around us, drink The development condition of the development condition of itself, especially infant can be all influenced with the situation of water, therefore Environmental Hormone is swashed The work of the Adsorption of element is extremely urgent.
Sorbing material generally has stronger absorption property, therefore purposes is wider, the activated carbon in sorbing material Purposes is the most extensive, and activated carbon itself is a kind of porous solid carbonaceous of black, passes through powder by timber, shell, bamboo, coal etc. It is broken, molding or with uniform particle through carbonizing, activating production.The specific surface area of normal activated carbon is in 500-1700m2/ g, has Very strong absorption property is a kind of extremely wide industrial adsorbents of purposes.For activated carbon in daily use adsorption process, it can be effective The liquids and gases such as ground formaldehyde adsorption, benzene, polyphenol volatile organic matter (VOC), to micro Environmental Hormone hormone (such as bisphenol-A) Etc. harmful substances also have certain capturing ability, but activated carbon can only ensure simply adsorb and capture, can not be to having Evil substance is effectively decomposed, and than relatively limited, when actual treatment needs to replace repeatedly processing capacity, and processing cost is high, handles Intensity is big.
In view of this, special propose the present invention.
Invention content
The purpose of the present invention is to provide a kind of photocatalyst overlay film carrier material, by by photocatalyst overlay film in carrier granular On, it is further to photocatalyst by ultraviolet light to harmful substances such as the formaldehyde, benzene, Environmental Hormone that are adsorbed on carrier granular Harmful substance is resolved into harmless water and carbon dioxide by photocatalysis, to reach the mesh of environmental protection, degradation of contaminant , it is especially splendid to micro, low concentration content contaminant water, the decomposition removal effect of pernicious gas.Environmentally friendly cost is reduced, is solved The problem of trace contaminant (formaldehyde in hormone, gas in such as water body) of having determined removal, avoids conventionally employed single work The drawbacks of property charcoal substance can only be adsorbed simply, cannot implement detoxication completely.
The second object of the present invention is to provide the specific preparation method that above-mentioned light touches overlay film carrier material, the preparation side Method operating procedure is simple, and operating condition is mild, whole environmentally protective, toxic reagent, no any three wastes need not be used to generate, system Standby obtained material has both absorption and decomposability, significant effect.
The third object of the present invention is to provide the further application of above-mentioned optical catalyst carrier material, be widely used, for The substances such as formaldehyde, benzene, Environmental Hormone all have good adsorption-decomposition function effect, reduce processing cost, protect human health, It is fully environmentally protective, build a more comfortable living environment.
In order to realize that the above-mentioned purpose of the present invention, spy use following technical scheme：
An embodiment of the present invention provides a kind of photocatalyst overlay film carrier materials, are mainly prepared by following raw material：Carrier The photocatalyst solution that particle and mass percent concentration are 20% or more, wherein carrier granular are absorbing material granules.
Preferably, the carrier granular includes active carbon particle, zeolite granular, silica gel particle, sieve particle, aluminium oxide One of which in particle.
The noxious substances such as the optical catalyst carrier material PARA FORMALDEHYDE PRILLS(91,95) of the embodiment of the present invention, benzene, Environmental Hormone are in carrier After on particle, by ultraviolet light to the further photocatalysis of photocatalyst, harmful substance can be resolved into harmless water and Carbon dioxide, to achieve the purpose that environmental protection, degradation of contaminant.
Photocatalyst is to have certain photocatalytic activity under the irradiation of ultraviolet light, has strong oxidation to generate Ultra-oxygen anion free radical and hydroxyl radical free radical, such as in degradation of formaldehyde gas, reactive hydroxyl radical and super oxygen, it is cloudy from Sub- free radical aoxidizes jointly, first oxidizes the formaldehyde into hydroxy acid, is finally degraded into and is appreciated that carbon dioxide and water,
Preferably, between 0.35-20nm, the particle radius of the photocatalyst is the particle radius of the active carbon particle Between 5-10nm.Synthetic activity charcoal adsorbs the effect of organic matter and inorganic matter, and 0.35- is preferably selected when selecting active carbon particle More preferably it is that the active carbon particle between selecting mesoporous granularity 2-50nm between micropore granularity 0.35-2nm carries out between 20nm It is used in mixed way.
The particle radius of photocatalyst is more preferably between 8-10nm, in order to pick out light-catalyzed reaction best results Photocatalyst (nano-titanium dioxide) completes the screening of high-quality photocatalyst by selective absorption, to improve later photocatalysis Functioning efficiency.
Preferably, a concentration of 25-40% of the photocatalyst solution preferably adds to improve the adsorption effect of photocatalyst The photocatalyst solution of high concentration.
The photocatalyst solution of the present invention includes nano-titanium dioxide, nano zine oxide, nano silicon dioxide, the oxidation of nanometer three The mixed solution that one or more of two iron are formed.
, can be based on nano-titanium dioxide when practical dispensing, nano zine oxide, nano silicon dioxide, nanometer three aoxidize Supplemented by two iron.
The present invention also provides a kind of preparation methods of photocatalyst overlay film carrier material, include the following steps：
(A) carrier granular is impregnated in photocatalyst solution more than for 24 hours, the carrier granular after immersion is dripped Go out, natural air drying；
(B) 100 DEG C or more drying to get.
It has to control in this method, when finally being dried at 100 DEG C or more, it so also can further excitation nano TiO2The chelating of photocatalyst acts on.
Preferably, in the step (A), during early period is impregnated, temperature is controlled at 15 DEG C or more.
More preferably, the temperature of immersion controls between 20-25 DEG C.
Preferably, in the step (A), the time control of natural air drying is more than for 24 hours.
Preferably, the time control of drying is between 8-10h.
The photocatalyst overlay film carrier material of the present invention has very wide in water, in air in terms of absorption, decomposing organic matter General application has very efficient processing capacity for many harmful substances in the presence of environment.
Compared with prior art, beneficial effects of the present invention are：
(1) harmful substance, can be resolved into harmless water and carbon dioxide by photocatalyst overlay film carrier material of the invention, To achieve the purpose that environmental protection, degradation of contaminant, reduce pollutant harmless treatment cost；
(2) the preparation method operating procedure of the above-mentioned sorbing material of the present invention is simple, and operating condition is mild, whole green ring It protects, toxic reagent, no any three wastes need not be used to generate, the material being prepared has both absorption and decomposability, effect Significantly.
Specific implementation mode
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is The conventional products that can be obtained by commercially available purchase.
Embodiment 1
The preparation method of photocatalyst overlay film absorbent charcoal material carries out in accordance with the following steps：
1) by particle radius be 2-20nm high grade activated carbon grain, nonpolarity ionized water photocatalyst solution (photocatalyst Particle radius is 8-10nm) in impregnate for 24 hours；
2) in soaking process, the temperature of solution controls between 15-20 DEG C, and the mass percent concentration of photocatalyst solution exists Between 20-30%, after impregnating for 24 hours, activated carbon is leached, natural air drying for 24 hours, carries out preliminary crystallization chelating；
3) it is then placed in drying box under 100 DEG C of constant temperature, dries 8-10h, further crystallization, chelating, solidification are for progress It can.
Embodiment 2
The preparation method of photocatalyst coated Natural Zeolite material carries out in accordance with the following steps：
1) by the high-quality zeolite grain that particle radius is 5-10nm, in nonpolarity ionized water nanometer titanium dioxide titanium solution (nanometer The particle radius of titanium dioxide be 5-6nm) in impregnate 26h；
2) in soaking process, the temperature of solution controls between 25-30 DEG C, the mass percent of nanometer titanium dioxide titanium solution Concentration after impregnating 26h, zeolite is leached, natural air drying 26h between 25-35%, carries out preliminary crystallization chelating；
3) it is then placed in drying box under 100 DEG C of constant temperature, dries 8-10h, carry out further crystallization, chelating, solidification, TiO is seen under microscope2Crystallization.
Embodiment 3
The preparation method of photocatalyst overlay film absorbent charcoal material carries out in accordance with the following steps：
1) the high grade activated carbon grain for being 40-50nm by high grade activated carbon grain that particle radius is 0.35-2nm, particle radius, In nonpolarity ionized water photocatalyst (nano-titanium dioxide 60wt%, nano zine oxide 40wt%) solution (particle of photocatalyst half Diameter is 9-10nm) in impregnate 26h；
2) in soaking process, the temperature of solution controls between 20-25 DEG C, and the mass percent concentration of photocatalyst solution exists Between 35-40%, 2h is mixed after all substances are added, after impregnating 26h, activated carbon is leached, natural air drying 25h carries out preliminary crystallization chelating；
3) it is then placed in drying box under 100 DEG C of constant temperature, dries 8-10h, further crystallization, chelating, solidification are for progress It can.
Embodiment 4
The preparation method of photocatalyst overlay film silica gel material carries out in accordance with the following steps：
1) the high-quality silicon particle for being 10-20nm by high-quality silicon particle, particle radius that particle radius is 0.35-2nm, in nothing Polar ion water photocatalyst (nano-titanium dioxide 70wt%, nano silicon dioxide 30wt%) solution (particle radius of photocatalyst For 4-5nm) in impregnate 27h；
2) in soaking process, the temperature of solution controls between 30-40 DEG C, and the mass percent concentration of photocatalyst solution exists Between 35-40%, 3h is mixed in 300rpm after all substances are added, and after impregnating 27h, silica gel is leached, natural wind Dry 27h, carries out preliminary crystallization chelating；
3) it is then placed in drying box under 110 DEG C of constant temperature, dries 8-10h, carry out further crystallization, chelating, solidification.
Embodiment 5
The preparation method of photocatalyst overlay film absorbent charcoal material carries out in accordance with the following steps：
1) the high grade activated carbon grain for being 10-20nm by high grade activated carbon grain that particle radius is 0.35-2nm, particle radius, 27h is impregnated in nonpolarity ionized water photocatalyst solution (particle radius of photocatalyst is 4-5nm)；
2) in soaking process, the temperature of solution controls between 25-30 DEG C, and the mass percent concentration of photocatalyst solution exists Between 35-40%, 3h is mixed in 200rpm after all substances are added, and after impregnating 27h, activated carbon is leached, natural 27h is air-dried, preliminary crystallization chelating is carried out；
3) it is then placed in drying box under 110 DEG C of constant temperature, dries 8-10h, carry out further crystallization, chelating, solidification, TiO is seen under microscope2Crystallization.
Experimental example 1
The photocatalyst overlay film carrier material that 1-5 of the embodiment of the present invention is prepared and commercially available active carbon particle (compared with Example 1) formaldehyde absorbing experiment measurement is carried out, specific experiment process is：Above-mentioned material, which is added separately to concentration of formaldehyde, is In 5.00% 50ml formalins, 20 DEG C of isothermal vibrations absorption 4h, 5h, for 24 hours, after 36h, 72h, in PARA FORMALDEHYDE PRILLS(91,95) aqueous solution Concentration of formaldehyde is redeterminated, 4h, 5h, for 24 hours, these time points of 36h, 72h be required to the formaldehyde in PARA FORMALDEHYDE PRILLS(91,95) aqueous solution Concentration is tested, and specific test result is as follows shown in table 1：It is commercially available same to carry out used active carbon particle when the experiment One product.
1 test result of table
Can be seen that from the result of above-mentioned table 1 typically only uses active carbon particle after testing for 24 hours, and adsorbance is Saturation is subsequently without any adsorption effect, but the sorbing material of the present invention not only has the effect of absorption, also further The effect of degradation, in this way during adsorbing progress synchronous with degradation so that treatment effect is more excellent, in addition to inhaling The stability of material after attached degradation treatment itself has also carried out further experiment, by the material after above-mentioned experiment in deionization In water after 5-10h, the content of formaldehyde in water is measured, specific test result is as follows：
2 test result of table
From the test result of above-mentioned table 2 it can also be seen that the present invention by being added to photocatalyst after, this stature can be improved The absorption stability of material, not only absorption, capacity of decomposition are promoted, and ensure that certain stability of material after adsorbing, will not Pernicious gas is parsed again.
Above-mentioned material tests the aqueous solution containing bisphenol-A and also has identical test result.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from the present invention's It, can be there are many other changes and modification in the case of spirit and scope.It is, therefore, intended that including in the following claims Belong to all such changes and modifications in the scope of the invention.

Claims (10)

1. a kind of photocatalyst overlay film carrier material, which is characterized in that be mainly prepared by the following raw material：Carrier granular and quality The photocatalyst solution that percent concentration is 20% or more；
The carrier granular is absorbing material granules；
Preferably, the carrier granular includes active carbon particle, zeolite granular, silica gel particle, sieve particle, alumina particle In one of which.
2. photocatalyst overlay film carrier material according to claim 1, which is characterized in that the carrier granular is activated carbon Grain.
3. photocatalyst overlay film carrier material according to claim 2, which is characterized in that the particle of the active carbon particle half Diameter is between 0.35-20nm, and the particle radius of the photocatalyst is between 5-10nm.
4. photocatalyst overlay film carrier material according to claim 1, which is characterized in that the photocatalyst solution it is a concentration of 25-40%；
The photocatalyst solution includes in nano-titanium dioxide, nano zine oxide, nano silicon dioxide, nanometer di-iron trioxide The mixed solution that one or more are formed.
5. the preparation method of claim 1-4 any one of them photocatalyst overlay film carrier materials, which is characterized in that including as follows Step：
(A) carrier granular is impregnated in photocatalyst solution more than for 24 hours, the carrier granular after immersion is leached, from So air-dry；
(B) 100 DEG C or more drying to get.
6. preparation method according to claim 5, which is characterized in that in the step (A), the temperature of immersion is controlled 15 DEG C or more.
7. preparation method according to claim 6, which is characterized in that the temperature of immersion controls between 20-25 DEG C.
8. preparation method according to claim 5, which is characterized in that in the step (A), the time control of natural air drying More than for 24 hours.
9. preparation method according to claim 5, which is characterized in that in the step (B), the time of drying is 8-10h, 100 DEG C of constant temperature.
10. claim 1-4 any one of them photocatalyst overlay films carrier material adsorbs in water, in air, decomposing organic matter The application of aspect.
CN201810673113.6A 2018-06-26 2018-06-26 A kind of photocatalyst overlay film carrier material and preparation method thereof, application Pending CN108714418A (en)

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CN113980416A (en) * 2021-11-17 2022-01-28 重庆科聚孚新材料有限责任公司 Plastic product containing composite catalyst and preparation method thereof

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CN113969035A (en) * 2021-11-17 2022-01-25 重庆科聚孚新材料有限责任公司 Plastic product for removing VOC and odor by adopting photocatalyst and preparation method thereof
CN113980416A (en) * 2021-11-17 2022-01-28 重庆科聚孚新材料有限责任公司 Plastic product containing composite catalyst and preparation method thereof

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