CN101167451A - Zeolite base composite antibiotic material and its preparation method - Google Patents
Zeolite base composite antibiotic material and its preparation method Download PDFInfo
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Abstract
The invention relates to zeolite-based composite antibiotic material and a process for preparation, the material of which is low-silicon-aluminum-ratio zeolite molecular sieve which is used as the base and carrier, the outer surface of the invention is covered with nanometer titanium dioxide particles, and the pore passages or cages of the invention are provided with metallic ions which have antibiotic effect. The process for preparing the material is that low-silicon-aluminum-ratio zeolite molecular sieve absorbs organic amine to saturation and then is dipped into soluble titanates for roasting to generate nanometer titanium dioxide on the outer surface of zeolite, and metallic ions such as silver ions, copper ions and the like which have antibiotic effect are exchanged to zeolite by the ion exchange process to form the novel composite antibiotic material. The composite antibiotic material not only has the antibiotic effect of metallic ions but also has the antibiotic effect of nanometer titanium dioxide, and thereby the antibiotic effect is strengthened. The composite antibiotic material is easy to prepare, low in price and suitable for industrial production.
Description
Technical field
The present invention relates to functional field of new, be specifically related to a kind of Zeolite base composite antibiotic material and preparation method thereof.The present invention is that substrate generates nano titanium oxide at outer surface of zeolite with the zeolite molecular sieve, thereby constitute a kind of new material with photocatalysis and ion exchanging function, pass through ion-exchange process again, silver, copper etc. had the metal ion exchanged of antibacterial action in zeolite, thereby form a kind of novel composite antibacterial material, make this material not only have the antibacterial action of metal ion, also there is the antibacterial action of nano titanium oxide the while, has strengthened antibacterial effect.
Background technology
Along with improving constantly of people's living standard, people begin to develop the functional article that can suppress microbial reproduction or killing bacteria.Wherein inorganic antiseptic with to human body safety, lasting, microorganism is difficult for developing immunity to drugs etc. is that characteristics receive much concern, comparatively ripe at present inorganic antibacterial material mainly contains two classes: the one, and to contain the metal ion bactericide that the antibacterial metal ions zeolite is representative (as Chinese invention patent ZL 02129700.2), this class material, good endurance safe and harmless to human body.The 2nd, be the metal oxide antibacterial agent (as Chinese invention patent ZL03117960.6) of representative with titanium dioxide, this class material non-toxic is harmless, to human body safety, the problem that can not exist organic antibacterial agent to flow out, but titanium dioxide anti-bacterial agent need could be realized the sterilization purpose under ultraviolet excitation.Above-mentioned anti-biotic material have many advantages can, but have some defectives: in case metal ion zeolite kill microorganisms, microorganism can be adsorbed on the surface of zeolite, can make the zeolite of metal ion lose the ability of killing germ again; What titanium dioxide anti-bacterial agent needed ultraviolet light excites the competence exertion antibacterial ability.
In order to improve the performance of anti-biotic material, the researcher has developed compound anti-biotic material, a kind of preparation method of composite inorganic antibacterial agent is disclosed as Chinese invention patent ZL 200410052644.1, to there be the titanium dioxide granule surface portion of photocatalytic activity to support loose structure calcium hydroxy phosphate clad, the loose structure of this clad supports the antibiotic property silver ion, therefore the existing photocatalysis of this antibacterial agent has the metal ion antibacterial functions again.The nano titanium dioxide anti-bacterial agent of loaded metal ion can effectively solve the problem that metal ion easily loses the ability of killing germ again, because nano titanium oxide itself has photocatalytic degradation bacterium, virus, organic effect, in antibiotic, the kill virus effect that do not have to utilize under the light source its metal ion, it can kill bacteria, virus, can utilize photocatalysis thoroughly to decompose the residue of elimination bacterium, virus again, can be widely used in many aspects such as dress ornament, toy, commodity, chemical fibre, coating, paint, pottery, plastics, hospital, public place.But a little less than the active force of nano titanium oxide and metal ion, be difficult to silver is loaded on the nano titanium oxide, and As time goes on, metal can ooze out slowly, lose, and loses original function; Also there is the preparation difficulty in the nano titanium dioxide anti-bacterial agent of same load silver, and problem such as cost an arm and a leg.
Summary of the invention
The invention provides a kind of Zeolite base composite antibiotic material and preparation method thereof, its objective is and to obtain a kind of photocatalysis antibacterial effect that both had, have the metal ion antibacterial action again, and to human body safety, lasting, NEW TYPE OF COMPOSITE anti-biotic material that microorganism is difficult for characteristics such as developing immunity to drugs.
For achieving the above object, the technical scheme that Zeolite base composite antibiotic material of the present invention adopts is: a kind of Zeolite base composite antibiotic material, with the zeolite molecular sieve is carrier, described zeolite molecular sieve carrier is selected 8 oxygen membered ring channel structures or 10 oxygen membered ring channel structures or 12 oxygen membered ring channel structures, and silica alumina ratio is less than or equal to 19 natural or synthesis zeolite, the silver that contains antibacterial action in the duct of this zeolite molecular sieve or the cage, copper, zinc, nickel, bismuth, the above combination of one of mercury metal ion or its both and both, and the outer surface load of zeolite molecular sieve has nano-titania particle.
Related content in the technique scheme is explained as follows:
1, in the such scheme, described zeolite molecular sieve is the inorganic poromerics of a class that is widely used in fields such as absorption, heterocatalysis, gas separation and ion exchange, has only the low silica-alumina ratio zeolite molecular sieve that ion exchanging function is just arranged again.In order to improve ion-exchange effect, the silica alumina ratio of described zeolite molecular sieve≤15, the best is≤10.So-called silica alumina ratio is meant the ratio of silicon and aluminium atomicity in the zeolite molecular sieve, and it is an index of zeolite molecular sieve character, and what the present invention adopted is the zeolite molecular sieve of low silica-alumina ratio.
2, in the such scheme, the zeolite molecular sieve of described 8 oxygen membered ring channel structures adopts A type zeolite.
The zeolite molecular sieve of described 10 oxygen membered ring channel structures adopts a kind of in the following zeolite:
International code name commercial disignation source;
MFI ZSM-5 is synthetic;
TON ZSM-22 is synthetic;
FER ZSM-35 is synthetic;
The STI foresite is natural.
The zeolite molecular sieve of described 12 oxygen membered ring channel structures adopts a kind of in the following zeolite:
International code name commercial disignation source;
FAU Y type, the X type is synthetic;
LAL L type is synthetic;
MTN ZSM-12 is synthetic;
BEA β type is synthetic;
The MOR modenite is natural or synthetic.
3, in the such scheme, described " contain the above combination of one of the silver, copper, zinc, nickel, bismuth, mercury metal ion of antibacterial action or its both and both in the duct of zeolite molecular sieve or the cage; and the outer surface load of zeolite molecular sieve has nano-titania particle " be meant that nano-titania particle only loads on the outer surface of zeolite molecular sieve, and in the zeolite molecular sieve duct or not load in the cage, zeolite molecular sieve is again by the ion-exchange capacity of self, and the metal ion exchanged that will have an antibacterial action is in self duct or in the cage.
For reaching above-mentioned purpose, the technical scheme that composite antibacterial material preparation method of the present invention adopts is: a kind of preparation method of Zeolite base composite antibiotic material, and it thes contents are as follows:
(1), raw material
1., zeolite molecular sieve selects 8 oxygen membered ring channel structures or 10 oxygen membered ring channel structures or 12 oxygen membered ring channel structures, and silica alumina ratio is less than or equal to 19 natural or synthesis zeolite;
2., solubility titanium salt;
3., organic amine selects a kind of in primary amine, secondary amine, the tertiary amine, wherein:
Primary amine chemical general formula: R
1-NH
2
R
1=C
1-C
12Alkyl;
The secondary amine chemical general formula:
R
2=C
1-C
12Alkyl; R
3=CH
3
The tertiary amine chemical general formula:
R
4=C
1-C
12Alkyl; R
5=CH
3R
6=CH
3
4., the solubility salt of the metal ion of antibacterial action is arranged, select following one or both and two or more combinations: silver, copper, zinc, nickel, bismuth, mercury;
(2), technology
1., the solubility titanium salt is dissolved in the corresponding solvent, be made into the titanium salt solution of concentration at 1～5mol/L;
2., the zeolite molecular sieve pre-burning is made wherein water evaporates, fully dehydration is cooled to room temperature, and the zeolite molecular sieve absorption organic amine after will dewater again carries out preliminary treatment to saturation state with this duct, inside with organic amine obstruction zeolite molecular sieve;
3., pretreated zeolite molecular sieve is immersed in the titanium salt solution, the mass ratio that the solubility titanium salt combines with zeolite molecular sieve is 0.1～1, the oven dry of dipping back, 300～600 ℃ of following roastings 1～10 hour, when waiting to reduce to room temperature, it is taken out, the organic amine in the zeolite molecular sieve duct is resolved into H with this
2O, CO
2And the nitride gas volatilization, make the duct recover ortho states, the titanium salt superficial growth outside that loads on zeolite molecular sieve outer surface simultaneously becomes titanium dioxide nano-particle;
4., the zeolite molecular sieve that will reduce to room temperature is put in the solubility salt solution that concentration is 0.1～1mol/L antibacterial metal ions, by ion exchange antibacterial metal ions is incorporated in the zeolite molecular sieve duct, oven for drying is put in centrifugation then, get final product goods.
Related content in the technique scheme is explained as follows:
1, in the such scheme, described solubility titanium salt is selected a kind of in the pure salt, butyl titanate of halide, the titanium of titanium.The pure salt of described titanium comprises titanium tetraethoxide, four titanium propanolates, four butanols titaniums, four amylalcohol titaniums etc.Aspect result of use, the pure salt and the butyl titanate of titanium are better.
2, in the such scheme, it is better that described sintering temperature is controlled at 500 ℃ ± 50 scopes.Because it is relevant that sintering temperature and the crystalline phase of nano titanium oxide are organized, the too high nano titanium oxide of temperature changes the rutile phase into, and temperature then is the anatase phase in 500 ℃ ± 50 scopes, and the photocatalysis performance of anatase phase is better.
3, in the such scheme, it is better that described calcined temperature is controlled at 500 ℃ ± 50 scopes.Because the internal microcellular structure more complicated of zeolite molecular sieve is fully dewatered for making it, and consider that the such temperature range of production efficiency is proper.
4, in the such scheme, the described ion-exchange time that antibacterial metal ions is incorporated in the zeolite molecular sieve duct is 24～60 hours.
5, in the such scheme, described preparation technology the is 4. in the step, when select two kinds and two or more combinations the metal ion of antibacterial action is arranged the time, carry out ion exchange sequentially.
In a word, principle of the present invention is: as substrate and carrier, only at its outer surface carried titanium dioxide nano particle, the metal ion that will have antibacterial action again is incorporated in the zeolite cavity that keeps ortho states or in the cage with the zeolite molecular sieve of low silica-alumina ratio.Because titanium dioxide nano-particle has the photocatalysis antibacterial effect, metal ion has antibacterial action, has therefore obtained a kind of composite antibacterial material that had not only had photocatalysis antibacterial but also had the metal ion antibacterial action.The mechanism of photocatalysis antibacterial is: when shining light wavelength less than 400nm, and TiO
2It is right that the separation of charge of nanocrystal produces electronics-hole, and the hole that is positioned at valence band has strong oxidability, can be the rapid oxidation Decomposition of most organic matter H
2O, CO
2Deng innocuous substance.The antibiotic mechanism of metal ion: when bacterium contacts with metal ion, can destroy the bacterium agent structure, metal ion enters in the bacterial cell and the enzyme combination of bacterial multiplication in other words, makes enzyme deactivation, reaches fungi-proofing antibiotic purpose.As metal ions such as silver, copper, zinc bacterium is had the contact killing action, they can enter in the cell by the penetration cell wall, and react with sulfenyl-SH, make protein coagulating, and the activity of destroying the cell synzyme makes cell forfeiture division growth ability and death; Metal ion can also destroy microorganisms electric transmission system, respiratory system and substance delivery system; And metal ion is a haptoreaction to bacterium, and the haptoreaction sterilization is a light requirement photograph not.
In order to obtain this material, in preparation technology, want earlier zeolite molecular sieve to be adsorbed organic amine to saturation state, be organic amine (stopping up the duct) abrim in the pore passage structure of zeolite molecular sieve, be immersed in then in the solubility titanium salt that the organic amine when roasting in the duct resolves into H with organic amine
2O, CO
2And nitride gas volatilization, make duct keep intact (having ion exchanging function), the titanium salt superficial growth outside that loads on zeolite molecular sieve outer surface simultaneously becomes nano-titania particle, by ion exchange metal ion is incorporated in the zeolite cavity again, thereby has obtained the composite antibacterial material of above-mentioned feature.
Because the technique scheme utilization, the present invention compared with prior art has following advantage and effect:
1, the invention provides a kind of low cost, oversimplify, the method of nontoxic pollution-free is used for the outer surface growth of nano titanium dioxide particle at the low silica-alumina ratio zeolite molecular sieve, and metal ion is incorporated in the zeolite cavity by the mode of ion exchange, make a kind of both had photocatalysis antibacterial and the antibiotic composite antibacterial material of metal ion, because this composite antibacterial material adopts zeolite molecular sieve to do substrate and carrier, strengthened the active force of nano titanium oxide and metal ion, and can stop slowly oozing out of metal ion, more increase their synergistic enhancing effect; This composite has Heat stability is good, is easy to reclaim, and is fit to characteristics such as large-scale production, is the very promising novel materials of a class.
2, composite antibiosis material feature provided by the invention can be tested with the following method:
(1) X-ray diffraction.Material of the present invention is the composite that zeolite molecular sieve and nano titanium oxide are formed, and can provide the strong diffraction maximum of zeolite molecular sieve and the broadening characteristic diffraction peak of titanium dioxide in the x-ray diffraction pattern, judges with this whether nano titanium oxide forms.
(2) transmission electron microscope.Can be clear that existence and the size of nano titanium oxide by transmission electron microscope at the zeolite molecular sieve grain surface.
(3) adsorption experiment.Take by weighing 1.00g Zeolite based nano-titanium dioxide composite, adding 50mL concentration is the CuSO of 250mg/L
4Solution stirs, and certain hour pipettes the solution about (the preceding short back of rule blanking time is long) 3mL at interval, and the centrifuging and taking supernatant liquor is with atomic emissions spectrophotometer measurement Cu
2+The variation of concentration.
(4) antibacterial experiment.Choose Escherichia coli and be anti-microbial property test bacterial classification, choosing LB agar is the culture of strains base, under 37 ℃ temperature, cultivated 12 hours, with culture with distilled water by centrifugation and washing, make 10
3ML
-1The bacterium liquid of magnitude is stand-by.Take by weighing the antibacterial agent of the preparation of 2.5mg, add the colibacillary bacterium liquid of 100mL, under 37 ℃, shake, it is fully reacted, at 0,2,4,6,12 and 24 hour, the above-mentioned reactant liquor of measuring 0.1ml was measured the anti-microbial property of antibacterial agent by viable bacteria counting method respectively.
Description of drawings
Accompanying drawing 3 is in the presence of composite (Zeolite based nano-titanium dioxide double function composite), Cu
2+The figure of concentration changes with time.As can be seen from Figure 3 TiO
2The composite that forms with the NaY zeolite molecular sieve has ion exchanging function, along with the increase of swap time, Cu
2+Concentration progressively descends.
Accompanying drawing 4 is Zeolite base composite antibiotic material antibacterial experiment figure.Ordinate is a coliform count, and abscissa is the time, and along with the growth in reaction time, active coliform count progressively reduces.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one:
Adopt silica alumina ratio (Si/Al) be 2.3 NaY (FAU) zeolite molecular sieve 500 ℃ of pre-burnings 3 hours, fully dehydration is cooled to room temperature, the zeolite molecular sieve after will dewater again adsorbs triethylamine (organic amine) to saturation state and carries out preliminary treatment.
Take by weighing the TiCl of 0.5g
3Be positioned in the magnetic boat, the deionized water that adds 3ml, 1g has been adsorbed organic amine to saturated NaY zeolite molecular sieve flooded wherein, stirred, 100 ℃ of heating, evaporating water, the magnetic boat is put into Muffle furnace, 500 ℃ of roastings 2 hours, when treating that sample is reduced to room temperature, sample is taken out, and putting into concentration is 0.1mol/L CuSO
4Exchange 48 hours, centrifugation, the solid sample that separation is obtained with distilled water is washed till does not have copper ion in the eluate, put into oven for drying, promptly gets product, is designated as TiO
2-CuY.This product characterizes proof through X-ray diffraction, transmission electron microscope: nano titanium oxide crystal grain forms at the NaY zeolite surface, and it is of a size of the 5-8 nanometer.Through anti-microbial property test proof, this material has kill activity to germs such as Escherichia coli.
If need to introduce two or more antibacterial metal ions in the duct of zeolite molecular sieve or the cage, can carry out ion exchange sequentially and can realize by ion-exchange process.
Embodiment two:
Adopt silica alumina ratio (Si/Al) be 7 EFR zeolite molecular sieve 500 ℃ of pre-burnings 3 hours, fully dehydration is cooled to room temperature, the zeolite molecular sieve after will dewater again adsorbs n-butylamine (organic amine) to saturation state and carries out preliminary treatment.
Take by weighing the TiCl of 0.4g
3Be positioned in the magnetic boat, the deionized water that adds 2ml, 1g has been adsorbed organic amine to saturated EFR zeolite molecular sieve flooded wherein, stirred, 100 ℃ of heating, evaporating water, the magnetic boat is put into Muffle furnace, 500 ℃ of roastings 2 hours, when treating that sample is reduced to room temperature, sample is taken out, and putting into concentration is 0.1mol/LAgNO
3Exchange 48 hours, centrifugation, the solid sample that separation is obtained with distilled water is washed till does not have silver ion in the eluate, put into oven for drying, promptly gets product, is designated as TiO
2-AgEFR.Show with X-ray diffraction, transmissioning electric mirror test: the size at the nano-titania particle of EFR zeolite surface production is about 10 nanometers.Through anti-microbial property test proof, this material has kill activity to germs such as Escherichia coli.
Embodiment three:
Adopt silica alumina ratio (Si/Al) be 10 TON zeolite molecular sieve 500 ℃ of pre-burnings 3 hours, fully dehydration is cooled to room temperature, the zeolite molecular sieve after will dewater again adsorbs propylamine (organic amine) to saturation state and carries out preliminary treatment.
Take by weighing the TiCl of 0.4g
4Be positioned in the magnetic boat, add the absolute ethyl alcohol of 2ml, stirring and dissolving, add the 2ml deionized water again, 1g has been adsorbed organic amine to saturated TON zeolite molecular sieve flooded wherein, stirred, 100 ℃ of heating, evaporating water, the magnetic boat is put into Muffle furnace, 500 ℃ of roastings 5 hours, when treating that sample is reduced to room temperature, sample is taken out, and putting into concentration is 0.1mol/L ZnSO
4Exchange 48 hours, centrifugation, the solid sample that separation is obtained with distilled water is washed till does not have zinc ion in the eluate, put into oven for drying, promptly gets product, is designated as TiO
2-ZnTON.Characterize demonstration with X-ray diffraction, transmission electron microscope: the nano-titania particle size that generates on TON zeolite grain surface is about 10 nanometers.Through anti-microbial property test proof, this material has kill activity to germs such as Escherichia coli.
Embodiment four:
Adopt silica alumina ratio (Si/Al) be 4 STI zeolite molecular sieve 500 ℃ of pre-burnings 3 hours, fully dehydration is cooled to room temperature, the zeolite molecular sieve after will dewater again adsorbs Trimethylamine (organic amine) to saturation state and carries out preliminary treatment.
Take by weighing the TiCl of 0.5g
4Be positioned in the magnetic boat, add the absolute ethyl alcohol of 2ml, stirring and dissolving, add the 3ml deionized water again, 1g has been adsorbed organic amine to saturated STI zeolite molecular sieve flooded wherein, stirred, 100 ℃ of heating, evaporating water, the magnetic boat is put into Muffle furnace, 400 ℃ of roastings 5 hours, when treating that sample is reduced to room temperature, take out sample, putting into concentration is 0.2mol/L NiSO
4Exchange 48 hours, centrifugation, the solid sample that separation is obtained with distilled water is washed till non-nickle ion in the eluate, puts into oven for drying, promptly gets product, is designated as TiO
2-NiSTI, this product show that through X-ray diffraction, transmission electron microscope the size of the TiO 2 particles that generates on STI zeolite grain surface is about 10 nanometers.Through anti-microbial property test proof, this material has kill activity to germs such as Escherichia coli.
Embodiment five:
Adopt silica alumina ratio (Si/Al) be 10 ZSM-5 zeolite molecular sieve 500 ℃ of pre-burnings 3 hours, fully dehydration is cooled to room temperature, the zeolite molecular sieve after will dewater again adsorbs propylamine (organic amine) to saturation state and carries out preliminary treatment.
The butyl titanate that takes by weighing 1g is positioned in the magnetic boat, adds the deionized water of 3ml, stirring and dissolving, 1g has been adsorbed organic amine to saturated ZSM-5 zeolite molecular sieve to be flooded wherein, stir, in 100 ℃ of heating, evaporating water, the magnetic boat is put into Muffle furnace, 500 ℃ of roastings 5 hours, when treating that sample is reduced to room temperature, sample is taken out, sample is taken out, and putting into concentration is 0.1mol/L Bi (NO
3)
3Exchange 48 hours, centrifugation, the solid sample that separation is obtained with distilled water is washed till does not have bismuth ion in the eluate, put into oven for drying, promptly gets product, is designated as TIO
2-BiZSM-5, X-ray diffraction, transmission electron microscope characterize proof: the size of the TiO 2 particles that generates on ZSM-5 zeolite grain surface is about 15 nanometers.Through anti-microbial property test proof, this material has kill activity to germs such as Escherichia coli.
The foregoing description only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the personage who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalences that spirit essence is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (10)
1. Zeolite base composite antibiotic material, it is characterized in that: be carrier with the zeolite molecular sieve, described zeolite molecular sieve carrier is selected 8 oxygen membered ring channel structures or 10 oxygen membered ring channel structures or 12 oxygen membered ring channel structures, and silica alumina ratio is less than or equal to 19 natural or synthesis zeolite, contain the above combination of one of the silver, copper, zinc, nickel, bismuth, mercury metal ion of antibacterial action or its both and both in the duct of this zeolite molecular sieve or the cage, and the outer surface load of zeolite molecular sieve there is nano-titania particle.
2. Zeolite base composite antibiotic material according to claim 1 is characterized in that: the silica alumina ratio of described zeolite molecular sieve is less than or equal to 15.
3. Zeolite base composite antibiotic material according to claim 2 is characterized in that: the silica alumina ratio of described zeolite molecular sieve is less than or equal to 10.
4. Zeolite base composite antibiotic material according to claim 1 is characterized in that: the zeolite molecular sieve of described 8 oxygen membered ring channel structures adopts A type zeolite;
The zeolite molecular sieve of described 10 oxygen membered ring channel structures adopts a kind of in MFI, TON, FER, the STI zeolite;
The zeolite molecular sieve of described 12 oxygen membered ring channel structures adopts a kind of in FAU, LAL, MTN, BEA, the MOR zeolite.
5. the preparation method of a Zeolite base composite antibiotic material is characterized in that:
(1), raw material
1., zeolite molecular sieve selects 8 oxygen membered ring channel structures or 10 oxygen membered ring channel structures or 12 oxygen membered ring channel structures, and silica alumina ratio is less than or equal to 19 natural or synthesis zeolite;
2., solubility titanium salt;
3., organic amine selects a kind of in primary amine, secondary amine, the tertiary amine, wherein: primary amine chemical general formula: R
1-NH
2
R
1=C
1-C
12Alkyl;
The secondary amine chemical general formula:
R
2=C
1-C
12Alkyl; R
3=CH
3
The tertiary amine chemical general formula:
R
4=C
1-C
12Alkyl; R
5=CH
3R
6=CH
3
4., the solubility salt of the metal ion of antibacterial action is arranged, select following one or both and two or more combinations: silver, copper, zinc, nickel, bismuth, mercury;
(2), technology
1., the solubility titanium salt is dissolved in the corresponding solvent, be made into the titanium salt solution of concentration at 1～5mol/L;
2., the zeolite molecular sieve pre-burning is made wherein water evaporates, fully dehydration is cooled to room temperature, and the zeolite molecular sieve absorption organic amine after will dewater again carries out preliminary treatment to saturation state with this duct, inside with organic amine obstruction zeolite molecular sieve;
3., pretreated zeolite molecular sieve is immersed in the titanium salt solution, the mass ratio that the solubility titanium salt combines with zeolite molecular sieve is 0.1～1, the oven dry of dipping back, 300～600 ℃ of following roastings 1～10 hour, when waiting to reduce to room temperature, it is taken out, the organic amine in the zeolite molecular sieve duct is resolved into H with this
2O, CO
2And the nitride gas volatilization, make the duct recover ortho states, the titanium salt superficial growth outside that loads on zeolite molecular sieve outer surface simultaneously becomes titanium dioxide nano-particle;
4., the zeolite molecular sieve that will reduce to room temperature is put in the solubility salt solution that concentration is 0.1～1mol/L antibacterial metal ions, by ion exchange antibacterial metal ions is incorporated in the zeolite molecular sieve duct, oven for drying is put in centrifugation then, get final product goods.
6. preparation method according to claim 5 is characterized in that: described solubility titanium salt is selected a kind of in the pure salt, butyl titanate of halide, the titanium of titanium.
7. preparation method according to claim 5 is characterized in that: described sintering temperature is controlled at 500 ℃ ± 50 scopes.
8. preparation method according to claim 5 is characterized in that: described calcined temperature is controlled at 500 ℃ ± 50 scopes.
9. preparation method according to claim 5 is characterized in that: the described ion-exchange time that antibacterial metal ions is incorporated in the zeolite molecular sieve duct is 24～60 hours.
10. preparation method according to claim 5 is characterized in that: described preparation technology the is 4. in the step, when select two kinds and two or more combinations the metal ion of antibacterial action is arranged the time, carry out ion exchange sequentially.
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