CN108464302A - A kind of slow-release chlorine dioxide of solid carrier Zeolite support and preparation method thereof - Google Patents
A kind of slow-release chlorine dioxide of solid carrier Zeolite support and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of slow-release chlorine dioxide of solid carrier Zeolite support and preparation method thereof, includes the following steps：Surfactant is added in acid solution, and zeolite is soaked in the acid solution by step S1, then obtains modified zeolite by being separated by solid-liquid separation；The modified zeolite is immersed in transition metal salt solution by step S2, then by being separated by solid-liquid separation, roasting, obtains carrying transition metal zeolite, the carrying transition metal zeolite is used as the carrier of chlorine dioxide of solid carrier.The beneficial effects of the present invention are：A kind of slow-release chlorine dioxide of solid carrier Zeolite support prepared so that chlorine dioxide release is gentle, and rate of release is stablized；The activation energy and overpotential of sodium chlorite automatic oxidation reaction under acidic environment are reduced, realizes the purpose of slowly activation sodium chlorite release chlorine dioxide.
Description
Technical field
The present invention relates to disinfection agent carrier preparation fields, and in particular to a kind of slow-release chlorine dioxide of solid carrier Zeolite support and
Preparation method.
Background technology
Chlorine dioxide is a kind of nontoxic, harmless, efficient Strong oxdiative type disinfection sanitizer, has anti-corrosion, deodorization, fresh-keeping etc. concurrently
Function.Without cause a disease, without teratogenesis, without carcinogenic, food drug office of the U.S. (FDA), beautiful has just been obtained early in eighties of last century the eighties
The approval of Environmental Protection Agency of state (EPA) and United States Department of Agriculture (USDA).It is the A1 class disinfectant preparations to rank the first in safe disinfection method.
Under the same terms, sterilizing power is 2.63 times of chlorine, with bactericidal range is wide, effect is good, action time is short, dosage
The features such as few.
Since chlorine dioxide physical property is more special, when sterilizing, what is in most cases used is all titanium dioxide
The aqueous solution of chlorine.But since ClO 2 solution is there are use concentration when sterilizing is higher, deenergized period is shorter, transport and
Storage is very inconvenient, the shortcomings of needing matching while using, and it is excellent to be unable to give full play that gaseous chlorine dioxide range of scatter is wide, effect is strong
Point.And chlorine dioxide of solid carrier finished product has then well solved the above problem.Commonly using immobilized body has silica gel, calcium silicates, diatomite, cunning
Mountain flour, molecular sieve, activated carbon, high-hydroscopicity polyacrylic resin, agar, superpower absorption resin and carboxymethyl cellulose etc..It is more
The shortcomings of immobilized body adsorption capacity of number is low, and service life is not short, easy to maintain after chlorine dioxide of solid carrier, and effect is poor.
In view of drawbacks described above, creator of the present invention obtains the present invention finally by prolonged research and practice.
Invention content
To solve above-mentioned technological deficiency, the technical solution adopted by the present invention is, provides a kind of immobilized titanium dioxide of slow-release
The preparation method of chlorine Zeolite support, includes the following steps：
Surfactant is added in acid solution, and zeolite is soaked in the acid solution by step S1, then passes through solid-liquid
Isolated modified zeolite；
The modified zeolite is immersed in transition metal salt solution by step S2, then by being separated by solid-liquid separation, roasting, is obtained
Carrying transition metal zeolite, the carrying transition metal zeolite are used as the carrier of chlorine dioxide of solid carrier.
Preferably, the zeolite is powdered or graininess.
Preferably, the zeolite be clinoptilolite, modenite, erionite, heulandite, one kind in phillipsite or
Several mixtures.
Preferably, the acid solution is the mixture of one or more of hydrochloric acid, sulfuric acid, nitric acid, the acid solution
Concentration range is 0.5~5mol/L.
Preferably, the solid and liquid weight volume ratio range of the zeolite and the acid solution is 1:10~1:20g/mL.
Preferably, the surfactant is nona oxy benzene sulfonic acid sodium salt of perfluoro, neopelex, dodecyl sulphur
The mixture of one or more of sour sodium, Cocoamidopropyl betaine, the additive amount of the surfactant is ranging from
1000~5000mg/L.
Preferably, the transition metal salt solution is ferric nitrate, manganese nitrate, copper nitrate, cerous nitrate, chromic nitrate, cadmium nitrate
One or more of mixture, the concentration range of the transition metal salt solution is 0.1~1mol/L.
Preferably, the solid and liquid weight volume ratio range of the modified zeolite and the transition metal nitrate solution is 1:10
~1:20g/mL, dip time of the modified zeolite in the transition metal nitrate solution are 12~24 hours.
Preferably, the calcination temperature is 200~800 DEG C, roasting time is 2~5 hours.
Preferably, a kind of slow-release chlorine dioxide of solid carrier Zeolite support prepared according to any of the above-described method, is used as two
Aoxidize the carrier of chlorhexidine-containing disinfectant.
Compared with the prior art the beneficial effects of the present invention are：
1, a kind of slow-release chlorine dioxide of solid carrier Zeolite support prepared by the present invention so that chlorine dioxide release is flat
Slow, rate of release is stablized；
2, a kind of slow-release chlorine dioxide of solid carrier Zeolite support prepared by the present invention so that load the finished product of chlorine dioxide
Validity period it is longer, under conditions of wet storage the finished product shelf-life significantly promoted；
3, a kind of slow-release chlorine dioxide of solid carrier Zeolite support prepared by the present invention, passes through acidic treatment zeolite so that
The aperture increases in zeolite interior duct increase the adsorption effect of zeolite；
4, a kind of slow-release chlorine dioxide of solid carrier Zeolite support prepared by the present invention passes through dipping, roasting technique, load
Upper transition metal oxide can reduce under acidic environment the activation energy of sodium chlorite automatic oxidation reaction and excessively electric as catalyst
The purpose of slowly activation sodium chlorite release chlorine dioxide is realized in position.
Specific implementation mode
Below in conjunction with the embodiment of the present invention, the technical characteristic above-mentioned and other to the present invention and advantage are made in more detail
Explanation.
Embodiment one
A kind of preparation method of slow-release chlorine dioxide of solid carrier Zeolite support of the present invention is as follows：
(1) inorganic acid solution containing surfactant is prepared.Surfactant be nona oxy benzene sulfonic acid sodium salt of perfluoro (OBS),
The mixture of one or more of neopelex, lauryl sodium sulfate, Cocoamidopropyl betaine, addition
Amount is 1000~5000mg/L of acid solution total weight；Inorganic acid is the mixing of one or more of hydrochloric acid, sulfuric acid, nitric acid
Object, a concentration of 0.5~5mol/L；The natural zeolite of 0.5~3mm is pressed into solid and liquid weight volume ratio 1:10~1:20 ratio is impregnated
In the acid solution that surfactant is added after 1~2 hour, suction filtration obtains sour modified zeolite particle.The crystal structure of natural zeolite
It makes and includes：Aluminosilicate skeleton, skeleton include the duct and cavity of exchangeable cations, three portions such as hydrone of potential phase
Point；This construction of natural zeolite makes it have the characteristics such as selection absorption, ion exchange, thermostabilization, acid and alkali-resistance.Acidified modified
Purpose is that certain amorphous substances in duct is made to dissolve, and is carried out at the same time H+It exchanges, modified natural zeolite not only becomes acid
Property, and the aperture in duct is increased, and the adsorption effect of natural zeolite, i.e. ion-exchange performance are increased.Surface is added to live
Property agent purpose be reduce inorganic acid solution surface tension, enhance the permeability of solution, ensure acidified modified effect；
(2) compound concentration is the nitrate composite solution of 0.1~1mol/L.Wherein nitrate is ferric nitrate, manganese nitrate, nitre
The mixture of one or more of sour copper, cerous nitrate, chromic nitrate, cadmium nitrate.By sour modified zeolite and nitrate solution by solid
Liquid w/v 1:10~1:After 20 ratio is impregnated 12~24 hours, after draining supernatant, 2 are roasted in 200~800 DEG C~
5 hours, obtain carrying transition metal zeolite granular；Natural zeolite is a kind of porous silicoaluminate mine of anionic rack-like structure
Substance is made of oxygen-octahedron and aluminum-oxygen tetrahedron, and tetrahedral structure can only be connected with vertex, share an oxygen atom,
Can not " side " or " face " be connected；Aluminum-oxygen tetrahedron can not be from being connected, and interval at least will be there are one oxygen-octahedron；And silica four
Face body can then be connected certainly；Silicon atom in oxygen-octahedron obtains aluminum-oxygen tetrahedron after being replaced by aluminium atom.Due to aluminium atom
For trivalent structure, in aluminum-oxygen tetrahedron, there are one the electricity prices of oxygen atom not to be neutralized, charge unbalance, thus alumina
Tetrahedron is negatively charged, in order to keep neutral, it is necessary to there is positively charged ion to offset, generally can by alkali and alkaline earth metal ions from
Sub such as Na, Ca, Sr, Ba, K, Mg metal ion compensates.The present invention is by dipping, roasting technique, transition metal in load
Oxide can reduce the activation energy and overpotential of sodium chlorite automatic oxidation reaction under acidic environment as catalyst, realize
The purpose of sodium chlorite release chlorine dioxide is slowly activated under acidic environment；
(3) covering is prepared.By chlorous acid sodium powder, silica white and diatomite by weight 2:1:1, in V-Mixer
It is sufficiently mixed to obtain covering；Chlorous acid sodium powder used Central Asia sodium chlorate >=82%, granularity are 50~100 mesh；Silica white
For Type B silica gel, granularity is 100~200 mesh；Diatomite is SiO2The diatomite concentrate of content >=90%.Sodium chlorite is to occur
The precursor composition of chlorine dioxide, silica white, diatomite are absorption, dry ingredient.Silica white is white particle, main component
It is made of the colloidal particle of formation agglutinate structure for the colloid system with solid property for silica, colloidal particle aggregation
Body space can form the micro hole structure inside covering, therefore it is that a kind of have abundant microcellular structure, specific surface area high, pure
The high high-quality absorption of degree height, activity, drying material；Diatomite is a kind of biogenic siliceous sedimentary rock, the diatom after refining
Soil has the characteristics that porosity is big, absorbability is strong, chemical property is stablized, and porosity reaches 80-90%, can absorb 1.5~4 times of dead weight
Moisture content, be a kind of good sorbing material；The compound use of Type B silica white and terra silicea purificata that the present invention selects can play
Draw humectant and adsorbent during drying stabilizer and use during diluent and the finished product storage of chlorous acid sodium powder
Etc. a variety of effects；
(4) adhesive is prepared.Adhesive is in the sodium alginate, polyvinyl alcohol, carboxymethyl cellulose of concentration 0.5~5%
The aqueous solution of one or more of mixtures；The adhesive that the present invention uses is played during disk pelletizing by load transitions
Metal zeolite particles, covering are bonded to the important auxiliary material of spherical particle, and the adhesive that the present invention uses has excellent antioxygen
The property changed；
(5) it is 1 by weight by carrying transition metal zeolite granular and covering:1 ratio puts into disc-type granulating machine
In, while adhesive is sprayed into, it coated, pelletized, adhesive straying quatity is the 3~8% of total weight of solids, and it is 1 to obtain grain size
The wet grain of chlorine dioxide of solid carrier particle of~5mm；
(6) after drying the wet grain of chlorine dioxide of solid carrier particle 2~4 hours at 80~105 DEG C, chlorine dioxide of solid carrier is obtained
Particle；The chlorine dioxide of solid carrier particle of the present invention is to be made up of sodium chlorite, silica white and diatomite disc-type granulating machine
Formed by way of granulation spherical of stabilization of covering, carrying transition metal zeolite granular and adhesive three
Grain；When hydrone or reducing substances are slowly intervened, the rate which can stablize releases chlorine dioxide
Body；
(7) chlorine dioxide of solid carrier particle is loaded in venting bags made of the materials such as non-woven fabrics or plastics dialysis membrane, then used
Slow-release chlorine dioxide of solid carrier finished granule is made in the sealing of aluminium plastic composite packaging bag.When finished product is in dry closed environment (original
Beginning outer packing) in, silica white and diatomite in covering can absorb the free moisture in finished product and form the stable crystallization water, suppression
It has made sodium chlorite to react with what acid transition metal oxide may occur, that is, has inhibited the release of chlorine dioxide, protect
The shelf life and stability of finished product are demonstrate,proved so that the shelf life of this finished product is not shorter than 2 years.It is (former when finished product is in ventilative environment
After beginning outer packing is opened), silica white and diatomite then play the role of drawing humectant, promote finished product to Environmental Water or reduction
Property substance absorption, cause sodium chlorite release chlorine dioxide with water or reacting for reducing substances.
Embodiment two
A kind of preparation method of slow-release chlorine dioxide of solid carrier Zeolite support is as follows：
(1) the molten of nona oxy benzene sulfonic acid sodium salt of perfluoro containing surfactant (OBS) 1000mg/L and hydrochloric acid 3mol/L is prepared
Liquid；The natural zeolite of 0.5~1mm is pressed into solid and liquid weight volume ratio 1:10 ratio is soaked in the acid solution that surfactant is added
In after 1~2 hour, suction filtration obtain sour modified zeolite particle；
(2) nitrate composite solution is prepared, wherein ferric nitrate containing 0.2mol/L, 0.2mol/L manganese nitrates, 0.1mol/L nitre
Sour copper.It is 1 that sour modified zeolite and nitrate solution, which are pressed solid and liquid weight volume ratio,:15 ratio is impregnated 12 hours, and supernatant is drained
After liquid, is roasted 4 hours in 500 DEG C, obtain carrying transition metal zeolite granular；
(3) covering is prepared.By chlorous acid sodium powder, silica white and diatomite by weight 2:1:1, in V-Mixer
It is sufficiently mixed to obtain covering；Chlorous acid sodium powder used Central Asia sodium chlorate >=82%, 50~100 mesh of granularity；Silica white is
Type B silica gel, 100~200 mesh of granularity；Diatomite is SiO2The diatomite concentrate of content >=90%；
(4) adhesive is prepared.Adhesive is the sodium alginate aqueous solution of concentration 2%；
(5) it is 1 by weight by carrying transition metal zeolite granular and covering:1 ratio puts into disc-type granulating machine
In, while spraying into adhesive, coated, pelletized, adhesive straying quatity is the 5% of total weight of solids, obtain grain size be 2~
The wet grain of chlorine dioxide of solid carrier particle of 4mm；
(6) after drying the wet grain of chlorine dioxide of solid carrier particle 4 hours at 80 DEG C, chlorine dioxide of solid carrier particle is obtained；
(7) chlorine dioxide of solid carrier particle is loaded in venting bags made of non-woven fabrics, then is sealed with aluminium plastic composite packaging bag.
Embodiment three
A kind of preparation method of slow-release chlorine dioxide of solid carrier Zeolite support is as follows：
(1) preparation base containing surfactant sodium dodecyl benzene sulfonic acid sodium salt, lauryl sodium sulfate, sulfuric acid, the mixing of nitric acid are molten
Liquid, a concentration of 2000mg/L of neopelex, a concentration of 1000mg/L of lauryl sodium sulfate, sulfuric acid it is dense
Degree is 0.5mol/L, a concentration of 0.5mol/L of nitric acid；2~3mm natural zeolites are pressed into solid and liquid weight volume ratio 1:15 ratio
It is soaked in mixed solution 2 hours, suction filtration obtains sour modified zeolite particle；
(2) nitrate solution of cerous nitrate containing 0.1mol/L, 0.2mol/L manganese nitrates, 0.2mol/L copper nitrates is prepared, it will
Sour modified zeolite presses solid and liquid weight volume ratio 1 with nitrate solution:After 15 ratio is impregnated 20 hours, after draining supernatant, in
800 DEG C roast 4 hours, obtain carrying transition metal zeolite granular；
(3) covering is prepared.By chlorous acid sodium powder, silica white and diatomite by weight 2:1:1, in V-Mixer
It is sufficiently mixed to obtain covering；Chlorous acid sodium powder used Central Asia sodium chlorate >=82%, 50~100 mesh of granularity；Silica white is
Type B silica gel, 100~200 mesh of granularity；Diatomite is SiO2The diatomite concentrate of content >=90%；
(4) aqueous solution for containing 2% polyvinyl alcohol, 0.5% carboxymethyl cellulose is prepared as adhesive；
(5) by carrying transition metal zeolite granular and covering by weight 1:In 0.8 input disc-type granulating machine, simultaneously
Adhesive is sprayed into, coated, pelletized；Adhesive straying quatity is the 3% of total weight of solids；It is the immobilized of 3~5mm to obtain grain size
The wet grain of chlorine dioxide particle；
(6) after drying the wet grain of chlorine dioxide of solid carrier particle 2 hours at 100 DEG C, chlorine dioxide of solid carrier particle is obtained；
(7) by chlorine dioxide of solid carrier particle loaded in venting bags made of plastics dialysis membrane material, then with plastic-aluminum combined packet
Pack sealing.
Example IV
A kind of preparation method of slow-release chlorine dioxide of solid carrier Zeolite support is as follows：
(1) mixing of Cocoamidopropyl betaine containing surfactant, lauryl sodium sulfate, sulfuric acid, hydrochloric acid is prepared
Solution, a concentration of 4000mg/L of Cocoamidopropyl betaine, a concentration of 500mg/L of lauryl sodium sulfate, sulfuric acid
A concentration of 0.5mol/L, a concentration of 0.5mol/L of hydrochloric acid；3~4mm natural zeolites are pressed into solid and liquid weight volume ratio 1:20 ratio
Example is soaked in mixed solution 2 hours, and suction filtration obtains sour modified zeolite particle；
(2) nitrate for preparing cerous nitrate containing 0.1mol/L, 0.3mol/L manganese nitrates and 0.3mol/L copper nitrates is compound molten
Sour modified zeolite particle and nitrate solution are pressed solid and liquid weight volume ratio 1 by liquid:After 15 ratio is impregnated 20 hours, drain
After clear liquid, is roasted 4 hours in 800 DEG C, obtain carrying transition metal zeolite granular；
(3) covering is prepared.By chlorous acid sodium powder, silica white and diatomite by weight 2:1:1, in V-Mixer
It is sufficiently mixed to obtain covering；Chlorous acid sodium powder used Central Asia sodium chlorate >=82%, 50~100 mesh of granularity；Silica white is
Type B silica gel, 100~200 mesh of granularity；Diatomite is SiO2The diatomite concentrate of content >=90%；
(4) polyvinyl alcohol of compound concentration 3% and 0.8% sodium alginate mixture aqueous solution as adhesive；
(5) it is 1 by weight by carrying transition metal zeolite granular and covering:1 ratio puts into disc-type granulating machine
In, while adhesive is sprayed into, it coated, pelletized.Adhesive straying quatity be total weight of solids 5%, obtain grain size be 4~
The chlorine dioxide of solid carrier wet granular of 6mm；
(6) after drying chlorine dioxide of solid carrier particle (wet grain) 2 hours at 100 DEG C, chlorine dioxide of solid carrier particle is obtained；
(7) by chlorine dioxide of solid carrier particle loaded in venting bags made of plastics dialysis membrane material, then with plastic-aluminum combined packet
Pack sealing.
Embodiment five
Finished product chlorine dioxide content detection of the present invention：
(1) detection method
In mortar, by chlorine dioxide of solid carrier particulate abrasive powdering, 2g is accurately weighed, 0.0002g is accurate to.Claim
Sample is placed in the 250mL iodine flasks for being previously added 2g potassium iodide, mixing；It is added 1:8 sulfuric acid solution 20mL, mixing set dark place
30 minutes.It is titrated with sodium thiosulfate standard solution, 1mL starch indicator solutions is added when nearly terminal, continue to be titrated to blue disappearance,
Record sodium thiosulfate standard solution consumption ml V1.And make blank test, record sodium thiosulfate standard solution consumption milli
Rise number V0.Chlorine dioxide content X is calculated as follows in sample：
△ V=V1-V2- are the difference of the volume and void volume of titration sodium thiosulfate, mL；
C- is sodium thiosulfate standard solution actual concentrations, mol/L；
M- is example weight, g；
13.49-conversion factors are equal to the weight for the chlorine dioxide that 1mol/L sodium thiosulfate standard solutions 1ml is consumed
Amount.
(2) in each embodiment finished product chlorine dioxide content：
Chlorine dioxide content in 1. slow-release chlorine dioxide of solid carrier particle of table
Embodiment six
Finished product stability detection experiment of the present invention：
(1) detection method
1. test method：The finished product for taking Packing Sound is set in 37 DEG C of insulating boxs 3 months.In placing forward and backward two are measured respectively
Aoxidize chlorinity.
2. evaluation of result：If sample is after 37 DEG C are stored 3 months, chlorine dioxide content rate of descent≤15%, effectively
Phase can be set to 2 years.
(2) Detection of Stability result
It is measured by Detection of Stability method, finished product is after 37 DEG C are stored 3 months in embodiment 2, active ingredient (two
Chlorine monoxid) content rate of descent be 7.65%, Pass Test design requirement, storage life, can be set to 2 years.
Embodiment seven
The bactericidal property of finished product of the present invention is tested：
(1) experiment prepares
Closed cabin：Volume is 1.0m3The confined space of (120cm × 85cm × 100cm), inside sets flow perturbation fan,
Out of my cabin away from setting gathering hole at bottom 30cm.
Strain and concentration：Experimental strain is staphylococcus albus.It presses《Disinfection technology standard》(2008) it provides, in closed cabin
Space bacterial concentration should be up to 5 × 104~5 × 106cfu/m3.Therefore before testing, staphylococcus albus bacterial suspension should be first determined
Extension rate, meet to the regulation of airborne bacterial concentration in closed cabin.
(2) microbiological contamination method
The staphylococcus albus bacterial suspension for being diluted to normal concentration is poured into atomizer, with micro- life in closed cabin
Object aerosol generator microbiological contamination 40min.Microbiological contamination rear fan continues to disturb 5min, later static 5min；
In closed cabin using liquid knockout decline bioaerosol sampler carry out bacterial sampling, wherein sample solution be
The 20ml phosphate buffer solutions of sterilizing add 2~3 drop olive oil (can prevent sample liquid splash), and sample solution is poured into liquid and is hit
It hits and samples 10min in bottle, sampling flow 11L/min is denoted as and samples for the first time, and after 2 hours, same procedure carries out second
Sampling；
The sample liquid that 1ml has been adopted is taken with liquid-transfering gun on a sterile work bench, is laid in aseptic flat board.Each sample liquid spreads 2
Tablet will ensure that sample is uniform, then pours into sterilized nutrient agar on tablet before sampling, after its cooling
Tablet is placed in 37 DEG C of constant incubators and is cultivated 48 hours.Count flat-plate bacterial colony number；4 blank cultures are done with batch sample
Tablet is carried out at the same time culture, as negative control with test sample.
(2) sterilization test
1. the slow-release chlorine dioxide of solid carrier particle 20g in embodiment 2 is hung on loaded in venting bags in closed cabin.
Interruption opens fan.The sample detection after 2,5,8,12,24 hours.
2. the phosphate buffer solution that 20mL has been added dropwise to 2~3 drop olive oil is poured into liquid knockout bottle, liquid knockout is used
The bioaerosol sampler that declines samples 10min, sampling flow 11L/min, the sample that will have been adopted respectively in two closed cabins
Liquid takes 1mL to be laid on sterilized tablet every time on a sterile work bench, with liquid-transfering gun, then with sterilized plus neutralizer
Nutrient agar pour into tablet, each sample liquid spreads 2 tablets, and tablet is placed in 37 DEG C of incubators after its cooling
After middle culture 48 hours, bacterial inactivation rate is calculated.
(3) test result
2. slow-release chlorine dioxide of solid carrier particle bactericidal effect of table
From table 2 it can be seen that chlorine dioxide of solid carrier particle prepared by the embodiment of the present invention two, 12 hours bacterial inactivation rates
Reach 99.92%, can quickly and effectively kill bacterium and virus in air.
Embodiment eight
The degradation property of finished product PARA FORMALDEHYDE PRILLS(91,95) of the present invention
(1) experiment prepares
Closed cabin：Volume is 1.0m3The confined space of (120cm × 85cm × 100cm), inside sets flow perturbation fan,
Out of my cabin away from setting gathering hole at bottom 30cm.
The preparation of formaldehyde gas：It measures a certain amount of formalin to be placed on evaporating dish, is placed in closed cabin and fumigates.Wait for first
Aldehyde solution evaporation subsequent continuous unlatching flow perturbation fan 5min completely.Concentration of formaldehyde is detected using one air detection instrument of the L2 six directions.
(2) test method
By the slow-release chlorine dioxide of solid carrier particle 20g in embodiment 3 loaded in venting bags, hang in closed cabin, wind
Fan is in intermittently starting state, detects concentration of formaldehyde using one air detection instrument of the L2 six directions in different time, and calculate this finished product
The removal rate of PARA FORMALDEHYDE PRILLS(91,95).
(3) experimental result
The degradation property of 3. slow-release chlorine dioxide of solid carrier particle PARA FORMALDEHYDE PRILLS(91,95) of table
From table 3 it can be seen that slow-release chlorine dioxide of solid carrier particle can effective this harmful substance of degradation of formaldehyde.
The foregoing is merely presently preferred embodiments of the present invention, is merely illustrative for the purpose of the present invention, and not restrictive
's.Those skilled in the art understand that in the spirit and scope defined by the claims in the present invention many changes can be carried out to it,
It changes or even equivalent, but falls in protection scope of the present invention.
Claims (10)
1. a kind of preparation method of slow-release chlorine dioxide of solid carrier Zeolite support, which is characterized in that include the following steps：
Surfactant is added in acid solution, and zeolite is soaked in the acid solution by step S1, then passes through separation of solid and liquid
Obtain modified zeolite；
The modified zeolite is immersed in transition metal salt solution by step S2, then by being separated by solid-liquid separation, roasting, is loaded
Transition metal zeolite, the carrying transition metal zeolite are used as the carrier of chlorine dioxide of solid carrier.
2. the preparation method of slow-release chlorine dioxide of solid carrier Zeolite support as described in claim 1, which is characterized in that the boiling
Stone is powdered or graininess.
3. the preparation method of slow-release chlorine dioxide of solid carrier Zeolite support as claimed in claim 2, which is characterized in that the boiling
Stone is the mixture of one or more of clinoptilolite, modenite, erionite, heulandite, phillipsite.
4. the preparation method of slow-release chlorine dioxide of solid carrier Zeolite support as described in claim 1, which is characterized in that the acid
Solution is the mixture of one or more of hydrochloric acid, sulfuric acid, nitric acid, and the concentration range of the acid solution is 0.5~5mol/L.
5. the preparation method of the slow-release chlorine dioxide of solid carrier Zeolite support as described in claim 1-4 is any, which is characterized in that
The solid and liquid weight volume ratio range of the zeolite and the acid solution is 1:10~1:20g/mL.
6. the preparation method of slow-release chlorine dioxide of solid carrier Zeolite support as claimed in claim 5, which is characterized in that the table
Face activating agent is nona oxy benzene sulfonic acid sodium salt of perfluoro, neopelex, lauryl sodium sulfate, cocamidopropyl propyl amide beet
The mixture of one or more of alkali, additive amount ranging from 1000~5000mg/L of the surfactant.
7. the preparation method of slow-release chlorine dioxide of solid carrier Zeolite support as described in claim 1, which is characterized in that the mistake
Cross the mixing that metal salt solution is one or more of ferric nitrate, manganese nitrate, copper nitrate, cerous nitrate, chromic nitrate, cadmium nitrate
The concentration range of object, the transition metal salt solution is 0.1~1mol/L.
8. the preparation method of slow-release chlorine dioxide of solid carrier Zeolite support as claimed in claim 8, which is characterized in that described to change
Property zeolite and the transition metal nitrate solution solid and liquid weight volume ratio range be 1:10~1:20g/mL, the modified boiling
Dip time of the stone in the transition metal nitrate solution is 12~24 hours.
9. the preparation method of slow-release chlorine dioxide of solid carrier Zeolite support as described in claim 1, which is characterized in that the roasting
It is 200~800 DEG C to burn temperature, and roasting time is 2~5 hours.
10. prepared by a kind of preparation method according to any slow-release chlorine dioxide of solid carrier Zeolite supports of claim 1-9
The slow-release chlorine dioxide of solid carrier Zeolite support gone out is used as the carrier of disinfection agent of chlorine dioxide.
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| CN111743072A (en) * | 2020-07-30 | 2020-10-09 | 深圳赛利特瑞环保科技有限公司 | Chlorine dioxide immobilized molecular sieve for removing formaldehyde, disinfection and odor |
| CN112244038A (en) * | 2020-09-15 | 2021-01-22 | 东莞东阳光科研发有限公司 | Chlorine dioxide sustained release agent and preparation method thereof |
| CN112825863A (en) * | 2021-01-08 | 2021-05-25 | 山东观变生物科技有限公司 | Chlorine dioxide slow-release liquid and preparation method thereof |
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