CN105536825B - Air sterilizing catalyst for clarifying and preparation method thereof - Google Patents

Air sterilizing catalyst for clarifying and preparation method thereof Download PDF

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Publication number
CN105536825B
CN105536825B CN201610010790.0A CN201610010790A CN105536825B CN 105536825 B CN105536825 B CN 105536825B CN 201610010790 A CN201610010790 A CN 201610010790A CN 105536825 B CN105536825 B CN 105536825B
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catalyst
inorganic porous
carrier
porous property
air
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CN105536825A (en
Inventor
李国培
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Shenzhen Kfair Environmental Technology Development Co Ltd
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Shenzhen Kfair Environmental Technology Development Co Ltd
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Priority to CN201610010790.0A priority Critical patent/CN105536825B/en
Priority to US15/554,020 priority patent/US10183187B2/en
Priority to PCT/CN2016/075854 priority patent/WO2017117861A1/en
Publication of CN105536825A publication Critical patent/CN105536825A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06Halogens; Compounds thereof
    • B01J27/08Halides
    • B01J27/10Chlorides
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/10Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
    • A62D3/17Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
    • A62D3/176Ultraviolet radiations, i.e. radiation having a wavelength of about 3nm to 400nm
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08Silica
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16Clays or other mineral silicates
    • B01J35/39
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20Organic substances
    • A62D2101/28Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/80Type of catalytic reaction
    • B01D2255/802Photocatalytic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/91Bacteria; Microorganisms

Abstract

The present invention provides a kind of catalyst for room air sterilization sterilizing and purifying.The carrier of the catalyst is by the inorganic porous materials such as silica, zeolite, diatomite, sepiolite, montmorillonite and aluminum oxide or cordierite, mullite ceramic honey comb as carrier, impregnate sodium chlorite stabilizing solution or Stable chlorine dioxide solution, drying forms, the material irradiates (tri- wave band of A, B, C is effective) through ultraviolet radiator, generates gaseous phase free radical OH, CIO2、·HO2, O isoreactivity particle and induce chain reaction, kill the microbes pollutants such as virus, bacterium and mould, the contaminants of chemical origins such as removal formaldehyde rapidly.It compared with the prior art, purification efficiency is high, without secondary pollution, long service life, it is simple and reliable, can be with man-computer symbiosis.Make air disinfection purifier made of filtering material with the catalyst, the third-party institution approved through CNAS and CMA is detected, in 30M3In experimental cabin, 15 minutes degerming rates 99.68%, 30 minutes degerming rates 99.99%.Reach 99.1% within formaldehyde removal rate 1 hour.

Description

Air sterilizing catalyst for clarifying and preparation method thereof
Technical field
The invention belongs to Green Chemistry high-level oxidation technology and environmental project application field, it is related in gaseous condition, scale Prepare gaseous phase free radical OH, ClO2、·HO2, O isoreactivity particle, and induce chain reaction.
Background technique
Microbes pollutant and contaminants of chemical origin in air pollution, generally use absorption, photocatalysis, anion, The methods of plasma, ozone are purified.In these methods, with high-concentrated ozone purification side
Method is most effective, 2.07 volts of the standard electrode potential of ozone, chemical reaction rate constant 101~102L/ (mols), Ozone kills mould (one kind of more difficult killing in microbes pollution) in the gas phase, and the time needs 100min, and ozone purification still has Shortcoming, and ozone is harmful to the human body, and air sterilizing purification indoors is unable to man-computer symbiosis.However OH have it is stronger Oxidability (2.80 volts of standard electrode potential), it is almost suitable with the oxidability of simple substance fluoride (2.87 volts), is a kind of strong Oxidation material.The reaction of OH belongs to radical reaction simultaneously, has very high chemical reaction rate 107~109L/(mol· S), 7 orders of magnitude higher than ozone.Its chemical time is less than 1s, 1~10s of biochemical reaction time.But due to the service life pole OH Short (10ns or so) is controlled so OH preparation and pollution control need to be carried out in the same time while generating OH Reason, that is must realize in-situ regeneration high concentration gaseous phase free radical, or scale prepare gaseous phase free radical OH, ClO2、·HO2, O isoreactivity particle.
Silicon dioxide meter has extremely strong affinity in face of water, and hydrone can irreversibly or reversibly be adsorbed on surface On, so silica surface is usually to be covered with by one layer of OH (hydroxyl) and absorption water.The former is bonded to surface Si original Hydroxyl on son, that is, chemical absorbed water;The latter is the water for being adsorbed on surface molecular, that is, the water of physical absorption.Big On the basis of measuring experimental fact, by us, observation and deep Theory Thinking, this characteristic of silica help us real for a long time The dream that scale prepares the gaseous phase free radicals such as hydroxyl radical free radical is showed.When silicon dioxide carried Stable chlorine dioxide solution, and pass through After 85 DEG C or less dryings, under no light, without heating state, ClO2Silica surface mechanical water (a small amount of) is set to have ionization water Solve H2O → H++OH-, to there is ClO2+H2O→HClO2+HClO3Slow hydrolysis it is outer, there is also the nonionics of chemical absorbed water Hydrolysis:
To there is ClO2+·H→HClO2
Overall reaction is ClO2+H2O→HClO2+·OH
In addition, there are also 2OH → H2O2
And OH+H2O2→·HO2+H2O
Above-mentioned non-ionic hydrolysis (free radical pattern) is not significant under normal circumstances, but is having substrate to react or have It can be greatly accelerated when being physically or chemically catalyzed, to there is a large amount of OH to generate.
·O+H2O→2·OH
·ClO+H2O+O2→HClO2+·HO2
3·O→O3
O2+·HO2→·OH+2O2
O3+H20→2·OH+O2
Since also there is the surface hydroxyl generated because adsorbing water on active aluminum oxide surface, so also there is above-mentioned titanium dioxide The characteristic of silicon.
It is mark that high-level oxidation technology, which is to generate OH, however the method that gaseous state generates OH at present, such as patent 201010567135.8 requiring huge optional equipment and at high cost with 201310700249.9, it is difficult large-scale industry and answers With.
Summary of the invention
Present invention aim to address high-level oxidation technologies to apply under gaseous condition, prior art in terms of pollutant control Deficiency, provide it is a kind of can scale prepare gaseous phase free radical OH, ClO2、·HO2, O air pollution treatment new method, Improve removal efficiency, without secondary pollution, long service life, it is simple and reliable, can be achieved in practice with man-computer symbiosis and Using.
The present invention provides sterilization and purification catalyst in a kind of air, and the catalyst includes the catalysis of inorganic porous property Agent carrier, the inorganic porous property catalyst carrier immersion stability ClO 2 solution or stability chlorite solution, warp 85 DEG C of following temperature are dry to be formed to moisture content≤8%, and the catalyst can produce gaseous phase free radical through ultraviolet radiator irradiation OH、·ClO2、·HO2, O active particle, adsorb and aoxidize kill air in microorganism, simultaneous oxidation remove air in Formaldehyde.
Feature of the invention:1. catalyst carrier can be silica, zeolite, sepiolite, diatomite, montmorillonite, three Al 2 O inorganic porous material (granularity >=100 mesh), preferably 2-3mm, 3-5mm, can be any of them, are also possible to A variety of mixtures or compound, immersion stability ClO 2 solution or stability chlorite solution, 85 DEG C or less dryings, It is formed to moisture content≤8%.The inorganic porous property catalyst carrier has 10 meters squared per grams or bigger specific surface area.It is more excellent Selection of land, the inorganic porous property catalyst carrier have the specific surface area of 100 meters squared per grams or more.
Feature of the invention:2. catalyst carrier can also pass through regular carrier, cordierite honeycomb ceramic or mullite bee Nest ceramics (- 900 mesh of 50 mesh of hole density), preferably 400 mesh, 150 × 150mm of specification, thickness can according to need any setting, excellent Select 25mm, 50mm, 100mm, 150mm.Immersion stability ClO 2 solution or stabilized sodium chlorite solution, 85 DEG C or less dry It is dry, until moisture content≤8% forms.
There are two types of application methods for the material:
1. irradiating through ultraviolet radiator, OH, ClO are generated2、·HO2, O isoreactivity particle, induce chain reaction, rapidly Virus, bacterium, mould and degradation chemical pollutant are killed, carbon dioxide, water and micro rock salt are eventually become.
2. can be irradiated without ultraviolet radiator, according to the difference of Environment control and improvement object directly as catalysis oxidation material Material, can equally degrade the microorganisms such as chemical pollutant and killing virus, bacterium, mould, and only purification efficiency is slightly poorer than first Kind of method, will reach same clean-up effect, increase by 30% or so when used catalyst amount with ultraviolet radiator when being irradiated.
There are two types of schemes for dipping solution of the present invention
First scheme:Stable ClO 2 solution is prepared, obtains purity >=98% with high purity chlorine dioxide generator Chlorine dioxide, with sodium carbonate peroxyhydrate (chemical general formula Na2CO3·mH2O2·nH2O it) is used as stabilizer, is made into one The absorbing liquid of certainty ratio is finally prepared to the solution that chlorine dioxide content is 2%-5%.
Alternative plan:Stabilized sodium chlorite solution is prepared, each component content is as follows in the solution:Chlorite 0.1- 10, stabilizer 0.1-5, buffer 0.05-15, absorbent 0.1-75.
Chlorite refers to ClO containing chlorition2 Salt, such as:Sodium chlorite, potassium chlorite, lithium chlorite, such as Sodium chlorite, potassium chlorite, lithium chlorite.
Stabilizer is also strong oxidizer, such as:Potassium permanganate, H2O2, perchlorate, nitrate etc..
Buffer, which refers to, can make solution ph maintain substantially invariable substance, usually salt in a certain range, at this In can only use the salt of strong base weak acid, such as sodium carbonate or borate, citrate.
Absorbent refers to chemical absorbent, there is chemical reaction between solute, the solubility of solute not only with vapor liquid equilibrium Rule is related and related with chemical balance rule.Chemical absorbent is the solution of certain active component, such as carbonic acid mostly Potassium, sodium carbonate, sodium hydroxide, aqueous solution of potassium hydroxide etc..
It is a kind of in above two scheme to be used as maceration extract, the above-mentioned inorganic porous carrier of any one is impregnated, through 85 DEG C or less Temperature is dry until moisture content≤8%, obtains catalysis material required for us.
The present invention also provides a kind of sterilizing and purifying method, this method uses above-mentioned catalyst, which can be according to not Any shape is pre-machined into same requirement, is placed in microenvironment air filtration system or portable air sterilizing and purifying is set It is standby upper, the irradiation of catalyst process >=30 microwatts/square centimeter intensity ultraviolet light, can remove microbes pollutant and Chemical pollutant.
In one embodiment, the ultraviolet light is provided by mercury ultraviolet radiator or LED ultraviolet radiator.A, B, C in ultraviolet radiator The irradiation of three wave bands (wavelength 400-180nm) can excite the catalysis material scale generate gaseous phase free radical OH, ClO2、·HO2, O isoreactivity particle, as long as exposure intensity is identical, LED light or mercury ultraviolet lamp effect are essentially identical.Central air supply Filtration system, C-band (185nm) ultraviolet radiator of catalyst (windage is small) through there is ozone to generate using peak nest ceramics as carrier Irradiation, clean-up effect it is further preferred that.And sterilizing and purifying device is moved, it is most handy not produce ozoniferous A or B band ultraviolet;Such as LED Lamp can use A band ultraviolet light to reduce cost.
When air humidity is big (such as larger than 80%), existing photocatalysis oxidation technique or room temperature heterogeneous catalytic oxidation technology pair Pollutant-degrading gene, all can sharp fall, and catalyst of the present invention, without because humidity it is big and impacted, in life This meteorological condition can often occur;When gas is very dry, when water volume concentration is lower than 4%, the chemical contamination of this catalyst Purification removal rate has larger impact, and still, this extreme drying regime is without appearance in air.
Detailed description of the invention
The beaded catalyst installation test model machine KF-501A of the present invention of attached drawing 1.
Bacteria-eliminating efficacy figure of the above-mentioned model machine of attached drawing 2 to staphylococcus aureus.
The above-mentioned model machine of attached drawing 3 is compared except formaldehyde curve and famous brand name clarifier and high-concentrated ozone.
The above-mentioned model machine of attached drawing 4 is except formaldehyde curve minimum power except formaldehyde curve and Switzerland's famous brand name I maximum power compare.
Specific embodiment
Embodiment 1
Example produces stabilized sodium chlorite stablizing solution first, measures 5000ml pure water, weighs 400g content 80% Sodium chlorite, in water dissolve after, weigh sodium chloride 100g continue in water stirring dissolve, then be added tetra- Heshui boron of 20g Sour sodium finally plus 30% hydrogen peroxide of 20ml content filters after stirring, finally between sodium carbonate adjustment pH value 8.0-9.5.So The silica that 3000g granularity is 3~5mm is added afterwards all to impregnate in a liquid, keeps stirring, after 1~2 hour, drips remaining to the greatest extent Liquid, fan dries up and to be placed on 65 DEG C of vacuum furnaces dry, until moisture content≤8% can come out and cool down it is spare.With this material system It is assemblied in a double-faced ventilated home disinfecting clarifier KF-501A (Fig. 1) at two strainers, which does not fill UV Lamp, the HEPA net cooperation with H13 purify room air.
Embodiment 2
By third party testing agency, disinfection purifier degerming rate described in embodiment 1 is detected, test is It is carried out in 30 cubic metres of Laboratory Module, detection data is recorded in following table.
Figure it is seen that work 20 minutes, disinfection purifier of the invention is high to the degerming rate of staphylococcus aureus Up to 99.68%.
Embodiment 3
By third party testing agency, disinfection purifier described in embodiment 1 carries out gaseous pollutant removal rate Detection, test is carried out in 30 cubic metres of Laboratory Module, environment temperature (25 ± -2) DEG C, ambient humidity (50 ± 10) % RH。
Testing procedure is as follows:
(1) to-be-detected machine is put by GB/T 18801-2008 requirement to experimental cabin center, air purifier is adjusted to work Make state, detection closes air purifier after working well;
(2) start temperature and humidity control device, make temperature control within the scope of 23 to 27 DEG C, relative humidity control 40 to Within the scope of 60%RH;
(3) a certain amount of gaseous pollutant gas is added in experimental cabin, makes it by using gas pollutant generator Initial concentration reaches 8 to 12 times of the corresponding limit value of GB/T 18883-2002, closes generator;
(4) gaseous pollutant is involved in vortex by the fan opened in experimental cabin, is stirred 10min, is closed wind after mixing Fan;
(5) after fan is static, initial concentration sample is acquired;
(6) start to test after the completion of the acquisition of initial concentration sample, acquisition 1 hour sample of test;
(7) it is not turned on air purifier, condition same as sample test does blank control, tests Natural Attenuation.
Calculation method and testing result see the table below
(C0' it is control group initial concentration, Ct' be control group final concentration)
(C0For test group initial concentration, CtFor test group final concentration)
Testing result:
Fig. 3 is shown as 10 cubic metres of experimental cabin KF-501A except formaldehyde curve graph and high-concentrated ozone machine and famous foreign product Board clarifier removes formaldehyde curve graph.
Fig. 4 is shown as 10 cubic metres of experimental cabin KF-501A minimum powers except formaldehyde curve and Switzerland's famous brand name I maximum work Rate removes formaldehyde curve graph.

Claims (8)

1. sterilization and purification catalyst in a kind of air, which is characterized in that the catalyst is catalyzed comprising inorganic porous property Agent carrier, the inorganic porous property catalyst carrier immersion stability ClO 2 solution or stability chlorite solution, warp 85 DEG C of following temperature are dry to be formed to moisture content≤8%, and the catalyst is irradiated through ultraviolet radiator generates gaseous phase free radical OH、·ClO2、·HO2, O active particle, adsorb and aoxidize kill air in microorganism, simultaneous oxidation remove air in Formaldehyde.
2. catalyst according to claim 1, it is characterised in that, the inorganic porous property catalyst carrier is that hole density is The cordierite honeycomb ceramic or mullite ceramic honey comb of 50 mesh to 900 mesh, by the inorganic porous property catalyst carrier series connection and/ Or parallel combination uses.
3. catalyst according to claim 1, it is characterised in that, the inorganic porous property catalyst carrier be granularity >= Aluminum oxide, silica, zeolite, sepiolite, montmorillonite, the diatomite one or more of them mixture or multiple of 100 mesh Object is closed, the inorganic porous property catalyst carrier has 10 meters squared per grams or bigger specific surface area.
4. catalyst according to claim 3, which is characterized in that the inorganic porous property catalyst carrier is flat with 100 Square rice/gram or more specific surface area, granularity 2-3mm.
5. catalyst according to claim 1, it is characterised in that, with high purity chlorine dioxide generator obtain purity >= 98% chlorine dioxide is made into absorbing liquid using sodium carbonate peroxyhydrate as stabilizer, is finally prepared to chlorine dioxide and contains Amount is the solution of 2%-5%.
6. catalyst according to claim 1, it is characterised in that, each component content in the stability chlorite solution It is as follows:Chlorite 0.1-10, stabilizer 0.1-5, buffer 0.05-15, absorbent 0.1-75, chlorite are chlorous Alkali metal salt or chlorous alkali salt.
7. a kind of sterilizing and purifying method, which is characterized in that use catalyst described in claim 1, the catalyst is according to difference Requirement any shape is pre-machined into, be placed in microenvironment air filtration system or portable air sterilizing and purifying device On, the irradiation of catalyst process >=30 microwatts/square centimeter intensity ultraviolet light can remove microbes pollutant.
8. sterilizing and purifying method according to claim 7, it is characterised in that, the ultraviolet light by mercury ultraviolet radiator or LED ultraviolet radiator provides.
CN201610010790.0A 2016-01-09 2016-01-09 Air sterilizing catalyst for clarifying and preparation method thereof Active CN105536825B (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201610010790.0A CN105536825B (en) 2016-01-09 2016-01-09 Air sterilizing catalyst for clarifying and preparation method thereof
US15/554,020 US10183187B2 (en) 2016-01-09 2016-03-08 Catalyst for disinfection, sterilization and purification of air, and preparation method thereof
PCT/CN2016/075854 WO2017117861A1 (en) 2016-01-09 2016-03-08 Catalyzer for sterilizing, disinfecting and purifying air, and preparation method thereof

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