CN100450366C - Method for preparing NaA nano molecular sieve/copperion/benzene carbonic acid composite bactericidal material - Google Patents
Method for preparing NaA nano molecular sieve/copperion/benzene carbonic acid composite bactericidal material Download PDFInfo
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- CN100450366C CN100450366C CNB2006101163092A CN200610116309A CN100450366C CN 100450366 C CN100450366 C CN 100450366C CN B2006101163092 A CNB2006101163092 A CN B2006101163092A CN 200610116309 A CN200610116309 A CN 200610116309A CN 100450366 C CN100450366 C CN 100450366C
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Abstract
The present invention relates to a preparation method of NaA nano molecular sieve/copper ion/benzoic acid composite germicidal material. Said method includes the following steps: utilizing oil bath reflux and synthesizing NaA nano zeolite molecular sieve at 60 deg.C; preparation of copper carried NaA nano zeolite (NaA-Cu2+) molecular sieve: utilizing electrostatic attraction force action between ions to make Cu2+ be fixed on the surface of NaA nano zeolite material so as to introduce Cu2+ active site; preparation of NaA nano zeolite molecular sieve/benzocopper ion/benzoic acid composite functional germicidal material: making the obtained copper carried NaA nano zeolite molecular sieve and sodium benzoate aqueous solution produce reaction so as to form the invented NaA nano molecular sieve/copper ion/benzoic acid composite germicidal material.
Description
Technical field
That the present invention relates to is the preparation method in a kind of modified Nano material technology field, the preparation method of particularly a kind of copper ion and the composite modified NaA nano molecular sieve of benzoic acid sterilization material.
Background technology
Because typical microorganism harmful substance in human settlement's systems (comprising water body, soil etc.) such as staphylococcus glucose coccus may be by the link of multiple complexity such as food chain circulation, directly influence threatens human beings'health.Therefore, along with modern's habitat environment awareness of safety improve constantly, how to develop provides highly effective and safe, function sterilization material with low cost, easy and simple to handle, particularly environment friendly, becomes the hot research problem that people pay close attention to gradually.The develop rapidly of modern molecular sieve of Nano zeolite synthetic technology has effectively promoted the continuous progress of environmentally friendly nano functional sterilization material.As everyone knows; after zeolite molecular sieve material enters nanoscale; its corresponding external surface area significantly improves; has good physical and chemical stability simultaneously; enrich the nano-pore of homogeneous; good ion-exchange performance and enrich adjustable surface nature is good catalyzer, adsorbent, ion-exchanger and functional material, is widely used in petrochemical industry, fine chemistry industry and environmental protection etc. and relates to micromolecular key areas.Although utilize zeolite structured in abundant alumina negative potential, the zeolite with carrying silver material of formation is to the existing report of the bactericidal action of oral cavity bacterium.But, influence product appearance because silver ion instability in the zeolite with carrying silver can cause the blackening of sterilization material.
Find by prior art documents, once reported in " Water Research (Britain " research of drinking water "), 2004,38,713 " and adopt nano titanium oxide, effectively remove the bacterial components that exists in the drinking water as a kind of catalysis material.But because requirement for experiment condition relative complex, particularly nano titanium oxide " inactivating effect " under certain condition of its sterilization process limited its further application to a certain extent.Simultaneously, Nano Silver and nano metal oxide materials also as a kind of effective sterilization material, constantly cause correlative study person's attention.There is report to utilize the result of study of metal oxide in " Langmuir (U.S. " Langmuir "), 2002,18,6679 " as sterilization material.But it is pointed out that the synthetic cost problem that metal oxide is higher relatively, become the key link of its development of restriction.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, the preparation method of a kind of NaA nano molecular sieve/copper ion/benzoic acid composite bactericidal material is provided.Make its low cost, syntheticly quickly and easily obtain that physico chemical property are stable, safe, nontoxic, a series of Different Silicon aluminum ratios of environmental type, the preparation method of the composite modified NaA nano molecular sieve of the copper ion of various grain sizes and benzoic acid sterilization material.
The present invention is achieved by the following technical solutions, and method concrete steps of the present invention are as follows:
(1) reflux by oil bath, under 60 ℃, synthetic NaA molecular sieve of Nano zeolite;
(2) copper-loaded NaA nano zeolite (NaA-Cu
2+) preparation of molecular sieve: make Cu by the effect of interionic electrostatic attraction
2+Be fixed in NaA nanosized zeolitic material surface, thereby introduce Cu
2+Avtive spot;
(3) preparation copper ion and the composite modified NaA nano molecular sieve of benzoic acid sterilization material: the copper-loaded NaA molecular sieve of Nano zeolite that will obtain, react with the Sodium Benzoate aqueous solution, form copper ion and the composite modified NaA nano molecular sieve of benzoic acid sterilization material.
Described Cu
2+Avtive spot is the alumina negative potential that utilizes in the NaA inorganic nano zeolite molecules sieve structure, by the fixing bivalent cupric ion of ion exchange process Electrostatic Absorption.
Described ion exchange by ion-exchange method, is introduced Cu in relevant nanometer zeolite molecular sieve skeleton structure
2+The operating process of avtive spot, utilize one of following dual mode to finish:
A: make the molecular sieve of Nano zeolite material place the 0.1mol/L copper nitrate solution, 60 ℃ of heating 3 hours that reflux under oil bath are so that Cu
2+Be fixed in NaA nanosized zeolitic material surface negative potential by the effect of interionic electrostatic attraction;
B: the molecular sieve of Nano zeolite material is fully mixed with the 0.1mol/L copper nitrate solution, be placed on and have in the teflon-lined stainless steel autoclave, 333 Kelvin's static reactions 3-4 hour are so that Cu
2+Be fixed in NaA nanosized zeolitic material surface negative potential by the effect of interionic electrostatic attraction.
Described copper-loaded NaA molecular sieve of Nano zeolite reacts with the Sodium Benzoate aqueous solution, is to utilize Cu
2+And the specificity chelation between benzoic acid molecule forms copper ion and the composite modified NaA nano molecular sieve of benzoic acid sterilization material.
The NaA molecular sieve of Nano zeolite that the present invention is synthetic according to idiomorphism, structure is formed controlled, can effectively avoid the introducing of exogenous impurity.Simultaneously, after NaA zeolite size entered nanoscale, corresponding external surface area significantly improved, and the alumina negative potential that enriches in the structure can be used as the ion exchange site, makes by interionic electrostatic attraction process, the fixing transition metal ions Cu that introduces
2+As the functional sterilizing group.Follow-up, further utilize Cu
2+And the specificity chelation between benzoic acid molecule, formation copper ion and the composite modified NaA nano molecular sieve of benzoic acid sterilization material.The selected NaA nanosized zeolitic material of the present invention, it is easy, synthetic with low cost to have building-up process, advantages such as regeneration are stablized, are easy to safe, nontoxic, environmental protection, physico chemical property, satisfies the sterilization needs of extensive representative microbial pollutant among the human settlement from now on.He Cheng NaA nanosized zeolitic material voluntarily, silica alumina ratio is 1: 1, through ion exchange process, can make transition metal ions Cu
2+By interionic electrostatic attraction process, be fixed in material surface.Utilize metal ion Cu simultaneously
2+And the specificity complexing between the benzoate anion obtains the composite modified NaA nano molecular sieve of copper ion and benzoic acid sterilization material.Relevant biological experiment result shows, in 5 hours, for the staphylococcus glucose coccus in the aqueous solution, can reach the germicidal efficiency more than 99%.
Description of drawings
Fig. 1 is the ESEM schematic diagram of synthetic NaA molecular sieve of Nano zeolite voluntarily.
Show among the figure: the corresponding synthetic voluntarily NaA molecular sieve of Nano zeolite that obtains, the crystal grain epigranular, regular shape does not have colloidal state or amorphous substance to exist, and shows that product is a pure phase, and degree of crystallinity is fine, and particle diameter is about 500 nanometers.
Fig. 2 is the XRD result schematic diagram of synthetic NaA molecular sieve of Nano zeolite voluntarily.
Show the synthetic voluntarily NaA molecular sieve of Nano zeolite that obtains among the figure, have whole characteristic diffraction peak signals of A type zeolite molecular sieve.
Fig. 3: the present invention is through the sterilization experiment result schematic diagram of difference after times of contact.
Show among the figure that behind 24 hours reaction contact time, the composite modified NaA nano molecular sieve of 0.02g copper ion and benzoic acid sterilization material can make that concentration is about 10 in the system
6The light grey glucose coccus of/ml is removed substantially fully.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described in further detail.
Example 1
1., by the oil bath reaction unit, synthetic voluntarily NaA molecular sieve of Nano zeolite
A. take by weighing aluminic acid and receive and be dissolved in the deionized water, stir it is fully dissolved.
B. take by weighing sodium hydroxid and silica gel, mix and stir.
C. the solution of aluminic acid being received adds in sodium hydroxid-silica gel mixed liquor, stir 1 hour even to solution.
D. the reaction mixture thing is poured in the reactor, placed 333 Kelvins' oil bath reaction unit, stirring and refluxing added thermal response 6 hours.
E. after reaction finishes, take out reactor, use deionized water cyclic washing reactant liquor to pH neutrality.
F. the product after will cleaning is put into drying baker, and the oven dry product is 2 hours under 373 Kelvins, gets the Na-A molecular sieve.
2., add in the thermal reaction apparatus in oil bath, selecting the centrifuge tube of the polyvinyl chloride material of 150ml volume is heating container, the 0.1mol/L copper nitrate solution that built-in 100ml prepares voluntarily, after accurately take by weighing 0.5g NaA nanosized zeolitic material, under the magnetic stirring apparatus effect, keep the abundant oscillatory regime of the inner aaerosol solution of corresponding heating container, under 60 ℃, add hot reflux, kept about three hours, so that Cu
2+Be fixed in NaA nanosized zeolitic material surface negative potential by the effect of interionic electrostatic attraction.Treat above-mentioned add copper-loaded NaA molecular sieve of Nano zeolite aaerosol solution that hot reflux obtains and be cooled to room temperature after, clean with the deionized water vibration repeatedly, to remove the bivalent cupric ion of the non-specific binding that may exist in the corresponding molecular screen material, the ammonia spirit of selecting 0.1mol/L concentration in the process does not occur Cu as indicator in the outflow solution behind wash-out
2+Same NH
4 +Between the blue complex that may form.I.e. expression is non-specifically bound in the Cu in the material
2+, by complete wash-out.To prepare copper-loaded NaA molecular sieve of Nano zeolite.
3., with the above-mentioned copper-loaded NaA molecular sieve of Nano zeolite that obtains, and concentration is that the benzoic acid of 0.1mol/L-0.5mol/L is received between the aqueous solution, at room temperature, under the magnetic stirring apparatus effect, fully vibration mixes, and utilizes Cu
2+With the specificity chelation between the benzoate anion, form copper ion and the composite modified NaA molecular sieve of Nano zeolite of benzoic acid sterilization material.Copper ion and the composite modified NaA molecular sieve of Nano zeolite of benzoic acid sterilization material with preparing clean repeatedly with deionized water, remove may be residual the benzoic acid composition, after be positioned in the baking oven, the moisture content that may exist in the material is removed in 80 ℃ of heating.In order to stand-by.
Example 2
1., by the oil bath reaction unit, synthetic voluntarily NaA molecular sieve of Nano zeolite
A takes by weighing aluminic acid and receives and be dissolved in the deionized water, stirs it is fully dissolved.
B takes by weighing sodium hydroxid and silica gel, mixes and stirs.
C receives solution with aluminic acid and adds in sodium hydroxid-silica gel mixed liquor, stir 1 hour even to solution.
D pours the reaction mixture thing in the reactor into, places 333 Kelvins' baking oven, reacts 6 hours.
After the e reaction finishes, take out reactor, use deionized water cyclic washing reactant liquor to pH neutrality.
Product after f will clean is put into drying baker, and the oven dry product is 2 hours under 373 Kelvins, removes the moisture content in the corresponding aaerosol solution, gets the Na-A molecular sieve.
2., add in the thermal reaction apparatus in oil bath, selecting the centrifuge tube of the polyvinyl chloride material of 150ml volume is heating container, the 0.1mol/L copper nitrate solution that built-in 100ml prepares voluntarily, after accurately take by weighing 0.5g NaA nanosized zeolitic material, under the magnetic stirring apparatus effect, keep the abundant oscillatory regime of the inner aaerosol solution of corresponding heating container, under 60 ℃, add hot reflux, kept about three hours, so that Cu
2+Be fixed in NaA nanosized zeolitic material surface negative potential by the effect of interionic electrostatic attraction.Treat above-mentioned add copper-loaded NaA molecular sieve of Nano zeolite aaerosol solution that hot reflux obtains and be cooled to room temperature after, clean with the deionized water vibration repeatedly, to remove the bivalent cupric ion of the non-specific binding that may exist in the corresponding molecular screen material, the ammonia spirit of selecting 0.1mol/L concentration in the process does not occur Cu as indicator in the outflow solution behind wash-out
2+Same NH
4 +Between the blue complex that may form.I.e. expression is non-specifically bound in the Cu in the material
2+, by complete wash-out.To prepare copper-loaded NaA molecular sieve of Nano zeolite.
3., with the above-mentioned copper-loaded NaA molecular sieve of Nano zeolite that obtains, and concentration is that the benzoic acid of 0.1mol/L-0.5mol/L is received between the aqueous solution, at room temperature, under the magnetic stirring apparatus effect, fully vibration mixes, and utilizes Cu
2+With the specificity chelation between the benzoate anion, form copper ion and the composite modified NaA molecular sieve of Nano zeolite of benzoic acid sterilization material.With copper ion and the composite modified NaA molecular sieve of Nano zeolite of the benzoic acid sterilization material for preparing.Clean repeatedly with deionized water, remove may be residual the benzoic acid composition, after be positioned in the baking oven, the moisture content that may exist in the material is removed in 80 ℃ of heating.In order to stand-by.
Example 3
1., by the oil bath reaction unit, synthetic voluntarily NaA molecular sieve of Nano zeolite
A takes by weighing aluminic acid and receives and be dissolved in the deionized water, stirs it is fully dissolved.
B takes by weighing sodium hydroxid and silica gel, mixes and stirs.
C receives solution with aluminic acid and adds in sodium hydroxid-silica gel mixed liquor, stir 1 hour even to solution.
D pours the reaction mixture thing in the reactor into, places 333 Kelvins' baking oven, reacts 6 hours.
After the e reaction finishes, take out reactor, use deionized water cyclic washing reactant liquor to pH neutrality.
Product after f will clean is put into drying baker, and the oven dry product is 2 hours under 373 Kelvins, removes the moisture content in the corresponding aaerosol solution, gets the Na-A molecular sieve.
2., accurately take by weighing 0.5g NaA nanosized zeolitic material, place the 0.1mol/L copper nitrate solution that 100ml prepares voluntarily after, fully mix vibration, transfer in the stainless steel cauldron of inner liner polytetrafluoroethylene, in baking oven, 333 Kelvin's static reactions 3-4 hour are so that Cu
2+Be fixed in NaA nanosized zeolitic material surface negative potential by the effect of interionic electrostatic attraction.Treat above-mentioned add copper-loaded NaA molecular sieve of Nano zeolite aaerosol solution that hot reflux obtains and be cooled to room temperature after, clean with the deionized water vibration repeatedly, to remove the bivalent cupric ion of the non-specific binding that may exist in the corresponding molecular screen material, the ammonia spirit of selecting 0.1mol/L concentration in the process does not occur Gu as indicator in the outflow solution behind wash-out
2+Same NH
4 +Between the blue complex that may form.I.e. expression is non-specifically bound in the Cu in the material
2+, by complete wash-out.To prepare copper-loaded NaA molecular sieve of Nano zeolite.
3., with the above-mentioned copper-loaded NaA molecular sieve of Nano zeolite that obtains, and concentration is that the benzoic acid of 0.1mol/L-0.5mol/L is received between the aqueous solution, at room temperature, under the magnetic stirring apparatus effect, fully vibration mixes, and utilizes Cu
2+With the specificity chelation between the benzoate anion, form copper ion and the composite modified NaA molecular sieve of Nano zeolite of benzoic acid sterilization material.Copper ion and the composite modified NaA molecular sieve of Nano zeolite of benzoic acid sterilization material with preparing clean repeatedly with deionized water, remove may be residual the benzoic acid composition, after be positioned in the baking oven, the moisture content that may exist in the material is removed in 80 ℃ of heating.In order to stand-by.
Example 4
1., by the oil bath reaction unit, synthetic voluntarily NaA molecular sieve of Nano zeolite
A takes by weighing aluminic acid and receives and be dissolved in the deionized water, stirs it is fully dissolved.
B takes by weighing sodium hydroxid and silica gel, mixes and stirs.
C receives solution with aluminic acid and adds in sodium hydroxid-silica gel mixed liquor, stir 1 hour even to solution.
D pours the reaction mixture thing in the reactor into, places 333 Kelvins' oil bath reaction unit, and stirring and refluxing added thermal response 6 hours.
After the e reaction finishes, take out reactor, use deionized water cyclic washing reactant liquor to pH neutrality.
Product after f will clean is put into drying baker, and the oven dry product is 2 hours under 373 Kelvins, gets the Na-A molecular sieve.
2., accurately take by weighing 0.5g NaA nanosized zeolitic material, after placing the 0.1mol/L copper nitrate solution that 100ml prepares voluntarily, fully mix vibration, transfer in the stainless steel cauldron of inner liner polytetrafluoroethylene, in baking oven, 333 Kelvin's static reactions 3-4 hour are so that Cu2+ is fixed in NaA nanosized zeolitic material surface negative potential by the effect of interionic electrostatic attraction.Treat above-mentioned add copper-loaded NaA molecular sieve of Nano zeolite aaerosol solution that hot reflux obtains and be cooled to room temperature after, clean with the deionized water vibration repeatedly, to remove the bivalent cupric ion of the non-specific binding that may exist in the corresponding molecular screen material, the ammonia spirit of selecting 0.1mol/L concentration in the process Cu2+ do not occur with the blue complex that may form between NH4+ as indicator in the outflow solution behind wash-out.I.e. expression is non-specifically bound in the Cu2+ in the material, by complete wash-out.To prepare copper-loaded NaA molecular sieve of Nano zeolite.
3., with the above-mentioned copper-loaded NaA molecular sieve of Nano zeolite that obtains, and concentration is that the benzoic acid of 0.1mol/L-0.5mol/L is received between the aqueous solution, at room temperature, under the magnetic stirring apparatus effect, fully vibration mixes, utilize Cu2+ with the specificity chelation between the benzoate anion, form copper ion and the composite modified NaA molecular sieve of Nano zeolite of benzoic acid sterilization material.Copper ion and the composite modified NaA molecular sieve of Nano zeolite of benzoic acid sterilization material with preparing clean repeatedly with deionized water, remove may be residual the benzoic acid composition, after be positioned in the baking oven, the moisture content that may exist in the material is removed in 80 ℃ of heating.In order to stand-by.
Example 5
1., by the oil bath reaction unit, synthetic voluntarily NaA molecular sieve of Nano zeolite
A takes by weighing aluminic acid and receives and be dissolved in the deionized water, stirs it is fully dissolved.
B takes by weighing sodium hydroxid and silica gel, mixes and stirs.
C receives solution with aluminic acid and adds in sodium hydroxid-silica gel mixed liquor, stir 1 hour even to solution.
D pours the reaction mixture thing in the reactor into, places 333 Kelvins' oil bath reaction unit, and stirring and refluxing added thermal response 6 hours.
After the e reaction finishes, take out reactor, use deionized water cyclic washing reactant liquor to pH neutrality.
Product after f will clean is put into drying baker, and the oven dry product is 2 hours under 373 Kelvins, gets the Na-A molecular sieve.
2., add in the thermal reaction apparatus in oil bath, selecting the centrifuge tube of the polyvinyl chloride material of 150ml volume is heating container, the 0.1mol/L copper nitrate solution that built-in 100ml prepares voluntarily, after accurately take by weighing 0.5g NaA nanosized zeolitic material, under the magnetic stirring apparatus effect, keep the abundant oscillatory regime of the inner aaerosol solution of corresponding heating container, under 60 ℃, add hot reflux, keep about three hours, so that Cu2+ is fixed in NaA nanosized zeolitic material surface negative potential by the effect of interionic electrostatic attraction.Treat above-mentioned add copper-loaded NaA molecular sieve of Nano zeolite aaerosol solution that hot reflux obtains and be cooled to room temperature after, clean with the deionized water vibration repeatedly, to remove the bivalent cupric ion of the non-specific binding that may exist in the corresponding molecular screen material, the ammonia spirit of selecting 0.1mol/L concentration in the process Cu2+ do not occur with the blue complex that may form between NH4+ as indicator in the outflow solution behind wash-out.I.e. expression is non-specifically bound in the Cu2+ in the material, by complete wash-out.To prepare copper-loaded NaA molecular sieve of Nano zeolite.
3., with the above-mentioned copper-loaded NaA molecular sieve of Nano zeolite that obtains, and concentration is that 0.1 benzoic acid is received between the aqueous solution, under the effect of water bath with thermostatic control shaker, under 30 ℃ of heating conditions, utilize Cu2+ with the specificity chelation between the benzoate anion, form copper ion and the composite modified NaA molecular sieve of Nano zeolite of benzoic acid sterilization material.Copper ion and the composite modified NaA molecular sieve of Nano zeolite of benzoic acid sterilization material with preparing clean repeatedly with deionized water, remove may be residual the benzoic acid composition, after be positioned in the baking oven, the moisture content that may exist in the material is removed in 80 ℃ of heating.In order to stand-by.
Example 6
1., by the oil bath reaction unit, synthetic voluntarily NaA molecular sieve of Nano zeolite
A takes by weighing aluminic acid and receives and be dissolved in the deionized water, stirs it is fully dissolved.
B takes by weighing sodium hydroxid and silica gel, mixes and stirs.
C receives solution with aluminic acid and adds in sodium hydroxid-silica gel mixed liquor, stir 1 hour even to solution.
D pours the reaction mixture thing in the reactor into, places 333 Kelvins' baking oven, reacts 6 hours.
After the e reaction finishes, take out reactor, use deionized water cyclic washing reactant liquor to pH neutrality.
Product after f will clean is put into drying baker, and the oven dry product is 2 hours under 373 Kelvins, removes the moisture content in the corresponding aaerosol solution, gets the Na-A molecular sieve.
2., add in the thermal reaction apparatus in oil bath, selecting the centrifuge tube of the polyvinyl chloride material of 150ml volume is heating container, the 0.1mol/L copper nitrate solution that built-in 100ml prepares voluntarily, after accurately take by weighing 0.5g NaA nanosized zeolitic material, under the magnetic stirring apparatus effect, keep the abundant oscillatory regime of the inner aaerosol solution of corresponding heating container, under 60 ℃, add hot reflux, keep about three hours, so that Cu2+ is fixed in NaA nanosized zeolitic material surface negative potential by the effect of interionic electrostatic attraction.Treat above-mentioned add copper-loaded NaA molecular sieve of Nano zeolite aaerosol solution that hot reflux obtains and be cooled to room temperature after, clean with the deionized water vibration repeatedly, to remove the bivalent cupric ion of the non-specific binding that may exist in the corresponding molecular screen material, the ammonia spirit of selecting 0.1mol/L concentration in the process Cu2+ do not occur with the blue complex that may form between NH4+ as indicator in the outflow solution behind wash-out.I.e. expression is non-specifically bound in the Cu2+ in the material, by complete wash-out.To prepare copper-loaded NaA molecular sieve of Nano zeolite.
3., with the above-mentioned copper-loaded NaA molecular sieve of Nano zeolite that obtains, and concentration is that 0.1 benzoic acid is received between the aqueous solution, under the effect of water bath with thermostatic control shaker, under 30 ℃ of heating conditions, utilize Cu2+ with the specificity chelation between the benzoate anion, form copper ion and the composite modified NaA molecular sieve of Nano zeolite of benzoic acid sterilization material.Copper ion and the composite modified NaA molecular sieve of Nano zeolite of benzoic acid sterilization material with preparing clean repeatedly with deionized water, remove may be residual the benzoic acid composition, after be positioned in the baking oven, the moisture content that may exist in the material is removed in 80 ℃ of heating.In order to stand-by.
Example 7
1., by the oil bath reaction unit, synthetic voluntarily NaA molecular sieve of Nano zeolite
A takes by weighing aluminic acid and receives and be dissolved in the deionized water, stirs it is fully dissolved.
B takes by weighing sodium hydroxid and silica gel, mixes and stirs.
C receives solution with aluminic acid and adds in sodium hydroxid-silica gel mixed liquor, stir 1 hour even to solution.
D pours the reaction mixture thing in the reactor into, places 333 Kelvins' baking oven, reacts 6 hours.
After the e reaction finishes, take out reactor, use deionized water cyclic washing reactant liquor to pH neutrality.
Product after f will clean is put into drying baker, and the oven dry product is 2 hours under 373 Kelvins, removes the moisture content in the corresponding aaerosol solution, gets the Na-A molecular sieve.
2., accurately take by weighing 0.5g NaA nanosized zeolitic material, after placing the 0.1mol/L copper nitrate solution that 100ml prepares voluntarily, fully mix vibration, transfer in the stainless steel cauldron of inner liner polytetrafluoroethylene, in baking oven, 333 Kelvin's static reactions 3-4 hour are so that Cu2+ is fixed in NaA nanosized zeolitic material surface negative potential by the effect of interionic electrostatic attraction.Treat above-mentioned add copper-loaded NaA molecular sieve of Nano zeolite aaerosol solution that hot reflux obtains and be cooled to room temperature after, clean with the deionized water vibration repeatedly, to remove the bivalent cupric ion of the non-specific binding that may exist in the corresponding molecular screen material, the ammonia spirit of selecting 0.1mol/L concentration in the process Cu2+ do not occur with the blue complex that may form between NH4+ as indicator in the outflow solution behind wash-out.I.e. expression is non-specifically bound in the Cu2+ in the material, by complete wash-out.To prepare copper-loaded NaA molecular sieve of Nano zeolite.
3., with the above-mentioned copper-loaded NaA molecular sieve of Nano zeolite that obtains, and concentration is that 0.1 benzoic acid is received between the aqueous solution, under the effect of water bath with thermostatic control shaker, under 30 ℃ of heating conditions, utilize Cu2+ with the specificity chelation between the benzoate anion, form bivalent cupric ion and the composite modified NaA molecular sieve of Nano zeolite of benzoic acid sterilization material.Copper ion and the composite modified NaA molecular sieve of Nano zeolite of benzoic acid sterilization material with preparing clean repeatedly with deionized water, remove may be residual the benzoic acid composition, after be positioned in the baking oven, the moisture content that may exist in the material is removed in 80 ℃ of heating.In order to stand-by.
Example 8
1., by the oil bath reaction unit, synthetic voluntarily NaA molecular sieve of Nano zeolite
A takes by weighing aluminic acid and receives and be dissolved in the deionized water, stirs it is fully dissolved.
B takes by weighing sodium hydroxid and silica gel, mixes and stirs.
C receives solution with aluminic acid and adds in sodium hydroxid-silica gel mixed liquor, stir 1 hour even to solution.
D pours the reaction mixture thing in the reactor into, places 333 Kelvins' oil bath reaction unit, and stirring and refluxing added thermal response 6 hours.
After the e reaction finishes, take out reactor, use deionized water cyclic washing reactant liquor to pH neutrality.
Product after f will clean is put into drying baker, and the oven dry product is 2 hours under 373 Kelvins, gets the Na-A molecular sieve.
2., accurately take by weighing 0.5g NaA nanosized zeolitic material, after placing the 0.1mol/L copper nitrate solution that 100ml prepares voluntarily, fully mix vibration, transfer in the stainless steel cauldron of inner liner polytetrafluoroethylene, in baking oven, 333 Kelvin's static reactions 3-4 hour are so that Cu2+ is fixed in NaA nanosized zeolitic material surface negative potential by the effect of interionic electrostatic attraction.Treat above-mentioned add copper-loaded NaA molecular sieve of Nano zeolite aaerosol solution that hot reflux obtains and be cooled to room temperature after, clean with the deionized water vibration repeatedly, to remove the bivalent cupric ion of the non-specific binding that may exist in the corresponding molecular screen material, the ammonia spirit of selecting 0.1mol/L concentration in the process Cu2+ do not occur with the blue complex that may form between NH4+ as indicator in the outflow solution behind wash-out.I.e. expression is non-specifically bound in the Cu2+ in the material, by complete wash-out.To prepare copper-loaded NaA molecular sieve of Nano zeolite.
3., with the above-mentioned copper-loaded NaA molecular sieve of Nano zeolite that obtains, and concentration is that 0.1 benzoic acid is received between the aqueous solution, under the effect of water bath with thermostatic control shaker, under 30 ℃ of heating conditions, utilize Cu2+ with the specificity chelation between the benzoate anion, form copper ion and the composite modified NaA molecular sieve of Nano zeolite of benzoic acid sterilization material.Copper ion and the composite modified NaA molecular sieve of Nano zeolite of benzoic acid sterilization material with preparing clean repeatedly with deionized water, remove may be residual the benzoic acid composition, after be positioned in the baking oven, the moisture content that may exist in the material is removed in 80 ℃ of heating.In order to stand-by.
Among the foregoing description 1-8, as shown in Figure 1, 2, 3:
Fig. 1 has shown: the corresponding synthetic voluntarily NaA molecular sieve of Nano zeolite that obtains, and the crystal grain epigranular, regular shape does not have colloidal state or amorphous substance to exist, and shows that product is a pure phase, and degree of crystallinity is fine, and particle diameter is about 500 nanometers; Shown among Fig. 2 figure: synthesize the NaA molecular sieve of Nano zeolite that obtains voluntarily, have whole characteristic diffraction peak signals of A type zeolite molecular sieve; Shown among Fig. 3 figure: behind 24 hours reaction contact time, the composite modified NaA molecular sieve of Nano zeolite of 0.02g bivalent cupric ion and benzoic acid functional sterilizing material can be about 10 with concentration in the system
6The light grey glucose coccus of/ml is removed substantially fully.
Claims (1)
1, the preparation method of the composite modified NaA nano molecular sieve of a kind of copper ion and benzoic acid sterilization material is characterized in that concrete steps are as follows:
(1) reflux by oil bath, under 60 ℃, synthetic NaA molecular sieve of Nano zeolite;
A takes by weighing sodium aluminate solution in deionized water, stirs it is fully dissolved,
B weighing sodium hydroxide and silica gel mix and stir,
C receives solution with aluminic acid and adds in sodium hydroxid-silica gel mixed liquor, stir 1 hour even to solution,
E pours the reaction mixture thing in the reactor into, places 333 Kelvins' oil bath reaction unit, and stirring and refluxing added thermal response 6 hours,
After the F reaction finishes, take out reactor, use deionized water cyclic washing reactant liquor to pH neutrality,
Product after G will clean is put into drying baker, and the oven dry product is 2 hours under 373 Kelvins, gets the Na-A molecular sieve;
(2) preparation of copper-loaded NaA molecular sieve of Nano zeolite: make Cu
2+Be fixed in NaA nanosized zeolitic material surface, by one of following two kinds of ion-exchange methods, in corresponding NaA nano molecular sieve structure, adsorb fixedly bivalent cupric ion, thereby introduce Cu
2+Avtive spot;
A: make the molecular sieve of Nano zeolite material place the 0.1mol/L copper nitrate solution, 60 ℃ of heating 3 hours that reflux under oil bath are so that Cu
2+Be fixed in NaA nanosized zeolitic material surface negative potential by the effect of interionic electrostatic attraction;
B: the molecular sieve of Nano zeolite material is fully mixed with the 0.1mol/L copper nitrate solution, be placed on and have in the teflon-lined stainless steel autoclave, 333 Kelvin's static reactions 3-4 hour are so that Cu
2+Be fixed in NaA nanosized zeolitic material surface negative potential by the effect of interionic electrostatic attraction;
(3) preparation copper ion and the composite modified NaA molecular sieve of Nano zeolite of benzoic acid function sterilization material: the copper-loaded NaA molecular sieve of Nano zeolite that will obtain, with concentration be that the Sodium Benzoate aqueous solution of 0.1mol/L-0.5mol/L reacts, at room temperature, by the magnetic stirring apparatus mixing of fully vibrating, clean repeatedly with deionized water, after be positioned in the baking oven heating and finish preparation and form copper ion and the composite modified NaA nano molecular sieve of benzoic acid sterilization material.
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