CN102000832A - Preparation method and purification process of nano silver - Google Patents
Preparation method and purification process of nano silver Download PDFInfo
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- CN102000832A CN102000832A CN2010105665982A CN201010566598A CN102000832A CN 102000832 A CN102000832 A CN 102000832A CN 2010105665982 A CN2010105665982 A CN 2010105665982A CN 201010566598 A CN201010566598 A CN 201010566598A CN 102000832 A CN102000832 A CN 102000832A
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Abstract
The invention belongs to the preparation technology of an antibacterial agent, and in particular relates to a preparation and purification method of nano silver. The method comprises the following steps of: dissolving maltose in deionized water to prepare a maltose water solution with a proper concentration, dissolving silver nitrate in the deionized water to prepare a solution with a certain concentration, and then adding the silver nitrate solution to a certain amount of ammonia water under stirring to form a silver diamminonitrate solution, and regulating the pH value of the solution to a proper value; and then adding the silver diamminonitrate solution to the maltose water solution under stirring for full reaction, separating the nano silver from the reaction solution with a two-step purification method to obtain the nano silver with high purity, small grain size, less loss and high yield. The preparation method and purification process of the nano silver in the invention has the advantages of environmental protection, low toxicity of the used reagents, simplicity and easiness in preparation and low cost. The prepared nano silver can be used for the fields of medicine, plastics, ceramics, daily chemical industries.
Description
Technical field
The invention belongs to the antiseptic technology of preparing, be specifically related to a kind of preparation method and purifying process of Nano Silver.
Background technology
Nanometer silver antimicrobial power is strong, has a broad antifungal spectrum, and bacterium does not produce drug resistance to it, is used for the treatment of burn as externally applied drug, and the trauma surface infestation of wounds such as scald, bullet wound, knife wound has good effect, especially has a good application prospect in the military medicine field.
The preparation method of Nano Silver is broadly divided into physical method and chemical method; chemical method comprises the reducing agent method again; luminescence method; ultrasonic method; electrolysis etc.; being equipped with Nano Silver with the reducing agent legal system at present uses more extensive; promptly silver nitrate is reduced into Nano Silver with reducing agent; one of shortcoming of this method is to need to add macromolecule dispersant at present; be agglomerated into macroparticle with the Nano Silver that prevents to generate; though the adding of macromolecule dispersant has stabilization; but owing to its to Nano Silver shelter and the coating effect changes some physicochemical property of Nano Silver, antibacterial activity reduces.
In addition, need be purified especially as pharmaceutical Nano Silver, because in the reaction system that contains the end-product Nano Silver, except that Nano Silver, still contain a large amount of reactants and other product impurity, if these impurity are not removed and to be produced excitant and toxicity to the surface of a wound, influence the validity and the security of Nano Silver.The document that the reducing agent legal system is equipped with Nano Silver does not all propose practicable method to the purifying of Nano Silver but at present.
Chinese patent application 200410069105.9 discloses " a kind of preparation method of nano silver colloid aqueous solution "; this method is to adopt double injecting control technology; under the stirring of agitator; silver-colored ammonia spirit and two simultaneously injection of the reducing agent aqueous solution are contained in the reaction system of the protective agent aqueous solution; generate nano silver particles; through the ultrafiltration desalination, obtain the nano silver colloid aqueous solution of average grain diameter less than 50 nanometers.This method has only adopted the technology of a step ultrafiltration, and therefore, the recovery of Nano Silver is complete inadequately.And, in reaction system, needing to add protective agent, technology is complicated.
Summary of the invention
The present invention is directed to the defective of above-mentioned prior art, provide a kind of and needn't add the macromolecule protective agent, only can prepare the method for stabilized nano silver colloidal solution by the PH that adjusts reactant liquor; Nano Silver can be separated from reactant mixture with " two step method of purification " that the inventor studies voluntarily, the purity of the Nano Silver that obtains and yield are all higher.
Little, the narrowly distributing of Nano Silver particle diameter that said method obtains, stable in properties, antibacterial activity height.The method environmental protection of above-mentioned preparation and purifying Nano Silver, simple, with low cost is easy to enlarge and produces.
Technical scheme of the present invention is as follows: a kind of preparation method of Nano Silver and purifying process comprise the steps:
To not contain protectant reductant solution under stirring joins in the two amminos silver solution of pH value for 8-13; be stirred to and react completely; with " two step method of purification " impurity in the reaction mixture is removed, promptly got high-purity, small particle diameter Nano Silver, and the yield height of Nano Silver.
The preparation of Nano Silver and purification process can also be: under stirring NaOH, maltose, ammoniacal liquor successively are dissolved in the deionized water, mixing forms the aqueous solution that contains NaOH, maltose, ammoniacal liquor; Stirring is dissolved in the silver nitrate solid in the above-mentioned solution down, is stirred to react completely, and with " two step method of purification " impurity in the reaction mixture is removed, and promptly gets high-purity, small particle diameter Nano Silver, and the yield height of Nano Silver.
The preparation of aforesaid Nano Silver and purification process, wherein, " two step method of purification " promptly successively removed impurity by two times of ultrafiltration and obtained high-purity nano silver, ultrafiltration for the first time is that reaction mixture is carried out ultrafiltration, contain Nano Silver in the concentrate that obtains after the ultrafiltration, except that Nano Silver, also contain impurity in the ultrafiltrate that obtains, Nano Silver in the ultrafiltrate is because of the aperture of particle diameter less than milipore filter, in ultra-filtration process, be lost in the ultrafiltrate, for the Nano Silver that reclaims this part loss can adopt following method: in ultrafiltrate, add nitric acid and stirring simultaneously, the nano silver particles polymerization is grown up, add the alkali neutralization then, carry out the ultrafiltration second time at last, the concentrate merging that concentrate that contains Nano Silver and the ultrafiltration for the first time that obtains after the ultrafiltration obtained gets final product.
The preparation of Nano Silver and purification process as mentioned above, wherein, reducing agent is maltose or citric acid or vitamin C or sodium borohydride or trisodium citrate or hydrazine hydrate.
The preparation of Nano Silver and purification process wherein, do not contain protectant reductant solution as mentioned above, are meant that needn't add the Nano Silver protective agent can prepare stabilized nano silver solution; Protective agent is meant that polyvinyl alcohol, polyvinylpyrrolidone etc. can stop Nano Silver to reunite, increase the material of Nano Silver stability.
Beneficial effect of the present invention is as follows: the preparation method of Nano Silver provided by the present invention and purifying process environmental protection, needn't add protective agent in the preparation process and can prepare stabilized nano silver, owing to there is not the biologically active that influences Nano Silver of macromolecule dispersant higher; Removed impurity by " two step method of purification ", made the security of Nano Silver higher; Nano Silver yield height; Agents useful for same toxicity is low; Prepare simple, under normal pressure and 50 ℃ of left and right sides conditions, can prepare particle diameter about 20nm, the narrower Nano Silver of distribution, cost of manufacture is low, is easy to suitability for industrialized production.
Description of drawings
Fig. 1 is a method flow diagram of the present invention.
Fig. 2 is the transmission electron microscope photo of the Nano Silver of preparation.Nano silver particles is the class sphere, and size is than homogeneous.
Fig. 3 is the Ma Erwen laser nano particle size analyzer measurement result of the Nano Silver of preparation, and number average bead diameter is 20nm.
The specific embodiment
Below in conjunction with drawings and Examples the present invention is described in detail.
As shown in Figure 1, the preparation of Nano Silver and purifying process comprise the steps:
Silver nitrate is dissolved in to make concentration in the deionized water be 1 * 10
-4Mol1
-1-4 * 10
-2Mol1
-1Solution, stir the ammoniacal liquor that adds 25%-28% down, make to form two amminos silver solution, the concentration of ammoniacal liquor in solution is 1 * 10
-3Mol1
-1-2.5 * 10
-2Mol1
-1Reducing agent is dissolved in to make concentration in the deionized water be 1 * 10
-3Mol1
-1-1 * 10
-1Mol1
-1Solution, 30-80 ℃, stir down reductant solution slowly to be joined in the two amminos silver solution it is fully reacted, make Nano Silver and other separating substances with " two step method of purification ", get highly purified Nano Silver.In the reductant solution reducing agent and two amminos silver solution in silver mol ratio be 2: 1-100: 1.
" two step method of purification " promptly successively removed impurity by two times of ultrafiltration and obtained high-purity nano silver, ultrafiltration for the first time is that reaction mixture is carried out ultrafiltration, contain Nano Silver in the concentrate that obtains after the ultrafiltration, except that Nano Silver, also contain impurity in the ultrafiltrate that obtains, Nano Silver in the ultrafiltrate is because of the aperture of particle diameter less than milipore filter, in ultra-filtration process, be lost in the ultrafiltrate, for the Nano Silver that reclaims this part loss can adopt following method: in ultrafiltrate, add nitric acid and stirring simultaneously, the nano silver particles polymerization is grown up, add the alkali neutralization then, carry out the ultrafiltration second time at last, the concentrate merging that concentrate that contains Nano Silver and the ultrafiltration for the first time that obtains after the ultrafiltration obtained gets final product.
It is even that embodiment 2 joins 46 ℃, 276L deionized water for stirring with certain density sodium hydroxide solution, make pH value of solution between 8-13, add maltose 1kg stirring and make its dissolving, the ammoniacal liquor that adds 178ml 27% under stirring makes and mixes, stir down will the 47g silver nitrate to add in the aforesaid liquid and make its dissolving, 46 ℃ are continued to be stirred to and react completely.Reaction mixture is carried out ultrafiltration (ultrafiltration for the first time), and it is standby to collect the ultrafiltrate that contains Nano Silver in the ultra-filtration process, and measures the pH of ultrafiltrate in good time, when treating that ultrafiltrate pH no longer is alkalescence, collects concentrate, stops ultrafiltration (ultrafiltration is for the first time finished).Measure the above-mentioned pH that contains the ultrafiltrate of Nano Silver, stir down and in the above-mentioned ultrafiltrate that contains Nano Silver, to add nitric acid (volume ratio of 16mol/L red fuming nitric acid (RFNA) and deionized water be 1: 1 formulated) 83ml-552ml and make its pH to 3-6, placed 20 minutes-2 hours, stir down to wherein adding the level of NaOH when the pH value being increased to do not add nitric acid, the above-mentioned ultrafiltrate that contains Nano Silver is carried out ultrafiltration (ultrafiltration for the second time), detect the pH value of ultrafiltrate in the ultra-filtration process in good time, when treating that the pH value no longer is alkalescence, collect concentrate, stop ultrafiltration (for the second time ultrafiltration finish), the concentrate that this time ultrafiltration is obtained merges with the concentrate of the gained of ultrafiltration for the first time and promptly gets the solution that contains high-purity nano silver.
Embodiment 3 accurately takes by weighing vitamin C 176g, with the 50L deionized water it is dissolved into vitamin c solution; Accurately take by weighing the 17g silver nitrate, it is dissolved, under agitation 62.5ml ammoniacal liquor is joined in the liquor argenti nitratis ophthalmicus, form two amminos silver solution with the 50L deionized water; 40 ℃, stir down vitamin c solution slowly to be added in the two amminos silver solution the two fully reacted, reaction mixture is carried out ultrafiltration (ultrafiltration for the first time), it is standby to collect the ultrafiltrate that contains Nano Silver in the ultra-filtration process, and measure the pH of ultrafiltrate in good time, when treating that ultrafiltrate pH no longer is alkalescence, collect concentrate, stop ultrafiltration (ultrafiltration is for the first time finished).Measure the above-mentioned pH that contains the ultrafiltrate of Nano Silver, stir down and in the above-mentioned ultrafiltrate that contains Nano Silver, to add nitric acid (volume ratio of 16mol/L red fuming nitric acid (RFNA) and deionized water be 1: 1 formulated) 30ml-2000ml and make its pH to 3-6, placed 20 minutes-2400 hours, stir down to wherein adding the level of NaOH when the pH value being increased to do not add nitric acid, the above-mentioned ultrafiltrate that contains Nano Silver is carried out ultrafiltration (ultrafiltration for the second time), detect the pH value of ultrafiltrate in the ultra-filtration process in good time, when treating that the pH value no longer is alkalescence, collect concentrate, stop ultrafiltration (for the second time ultrafiltration finish), the concentrate that this time ultrafiltration is obtained merges with the concentrate of the gained of ultrafiltration for the first time and promptly gets the solution that contains high-purity nano silver.
Embodiment 4 accurately takes by weighing trisodium citrate 295g, with the 50L deionized water it is dissolved; Accurately take by weighing the 17g silver nitrate, it is dissolved, under agitation 62.5ml ammoniacal liquor is joined in the liquor argenti nitratis ophthalmicus, form two amminos silver solution with the 50L deionized water; 50 ℃, stir down citric acid three sodium solution slowly to be added in the two amminos silver solution the two fully reacted, reaction mixture is carried out ultrafiltration (ultrafiltration for the first time), it is standby to collect the ultrafiltrate that contains Nano Silver in the ultra-filtration process, and measure the pH of ultrafiltrate in good time, when treating that ultrafiltrate pH no longer is alkalescence, collect concentrate, stop ultrafiltration (ultrafiltration is for the first time finished).Measure the above-mentioned pH that contains the ultrafiltrate of Nano Silver, stir down and in the above-mentioned ultrafiltrate that contains Nano Silver, to add nitric acid (volume ratio of 16mol/L red fuming nitric acid (RFNA) and deionized water be 1: 1 formulated) 30ml-2000ml and make its pH to 3-6, placed 20 minutes-2400 hours, stir down to wherein adding the level of NaOH when the pH value being increased to do not add nitric acid, the above-mentioned ultrafiltrate that contains Nano Silver is carried out ultrafiltration (ultrafiltration for the second time), detect the pH value of ultrafiltrate in the ultra-filtration process in good time, when treating that the pH value no longer is alkalescence, collect concentrate, stop ultrafiltration (for the second time ultrafiltration finish), the concentrate that this time ultrafiltration is obtained merges with the concentrate of the gained of ultrafiltration for the first time and promptly gets the solution that contains high-purity nano silver.
Embodiment 5 accurately takes by weighing maltose 1kg, with the 139L deionized water it is dissolved; Accurately take by weighing the 47g silver nitrate, it is dissolved, under agitation 173ml ammoniacal liquor is joined in the liquor argenti nitratis ophthalmicus, form two amminos silver solution with the 138L deionized water; 50 ℃, stir down maltose solution slowly to be added in the two amminos silver solution the two fully reacted, reaction mixture is carried out ultrafiltration (ultrafiltration for the first time), it is standby to collect the ultrafiltrate that contains Nano Silver in the ultra-filtration process, and measure the pH of ultrafiltrate in good time, when treating that ultrafiltrate pH no longer is alkalescence, collect concentrate, stop ultrafiltration (ultrafiltration is for the first time finished).Measure the above-mentioned pH that contains the ultrafiltrate of Nano Silver, stir down and in the above-mentioned ultrafiltrate that contains Nano Silver, to add nitric acid (volume ratio of 16mol/L red fuming nitric acid (RFNA) and deionized water be 1: 1 formulated) 83ml-5500ml and make its pH to 3-6, placed 20 minutes-2400 hours, stir down to wherein adding the level of NaOH when the pH value being increased to do not add nitric acid, the above-mentioned ultrafiltrate that contains Nano Silver is carried out ultrafiltration (ultrafiltration for the second time), detect the pH value of ultrafiltrate in the ultra-filtration process in good time, when treating that the pH value no longer is alkalescence, collect concentrate, stop ultrafiltration (for the second time ultrafiltration finish), the concentrate that this time ultrafiltration is obtained merges with the concentrate of the gained of ultrafiltration for the first time and promptly gets the solution that contains high-purity nano silver.
Embodiment 6 accurately takes by weighing sodium borohydride 100g, with the 132L deionized water it is dissolved; Accurately take by weighing the 22.5g silver nitrate, it is dissolved, under agitation 83ml ammoniacal liquor is joined in the liquor argenti nitratis ophthalmicus, form two amminos silver solution with the 66L deionized water; 50 ℃, stir down sodium borohydride solution slowly to be added in the two amminos silver solution the two fully reacted, reaction mixture is carried out ultrafiltration (ultrafiltration for the first time), it is standby to collect the ultrafiltrate that contains Nano Silver in the ultra-filtration process, and measure the pH of ultrafiltrate in good time, when treating that ultrafiltrate pH no longer is alkalescence, collect concentrate, stop ultrafiltration (ultrafiltration is for the first time finished).Measure the above-mentioned pH that contains the ultrafiltrate of Nano Silver, stir down and in the above-mentioned ultrafiltrate that contains Nano Silver, to add nitric acid (volume ratio of 16mol/L red fuming nitric acid (RFNA) and deionized water be 1: 1 formulated) 59ml-4000ml and make its pH to 3-6, placed 20 minutes-2400 hours, stir down to wherein adding the level of NaOH when the pH value being increased to do not add nitric acid, the above-mentioned ultrafiltrate that contains Nano Silver is carried out ultrafiltration (ultrafiltration for the second time), detect the pH value of ultrafiltrate in the ultra-filtration process in good time, when treating that the pH value no longer is alkalescence, collect concentrate, stop ultrafiltration (for the second time ultrafiltration finish), the concentrate that this time ultrafiltration is obtained merges with the concentrate of the gained of ultrafiltration for the first time and promptly gets the solution that contains high-purity nano silver.
Claims (6)
1. the preparation of a Nano Silver and purification process comprise the steps:
To not contain protectant reductant solution under stirring joins in the two amminos silver solution of pH value for 8-13; be stirred to and react completely; with " two step method of purification " impurity in the reaction mixture is removed, promptly got high-purity, small particle diameter Nano Silver, and the yield height of Nano Silver.
2. the preparation of a Nano Silver and purification process comprise the steps:
Under stirring NaOH, maltose, ammoniacal liquor successively are dissolved in the deionized water, mixing forms the aqueous solution that contains NaOH, maltose, ammoniacal liquor; Stirring is dissolved in the silver nitrate solid in the above-mentioned solution down, is stirred to react completely, and with " two step method of purification " impurity in the reaction mixture is removed, and promptly gets high-purity, small particle diameter Nano Silver, and the yield height of Nano Silver.
3. the preparation of Nano Silver as claimed in claim 1 or 2 and purification process, it is characterized in that: " two step method of purification " promptly successively removed impurity by two times of ultrafiltration and obtained high-purity nano silver, ultrafiltration for the first time is that reaction mixture is carried out ultrafiltration, contain Nano Silver in the concentrate that obtains after the ultrafiltration, except that Nano Silver, also contain impurity in the ultrafiltrate that obtains, Nano Silver in the ultrafiltrate is because of the aperture of particle diameter less than milipore filter, in ultra-filtration process, be lost in the ultrafiltrate, for the Nano Silver that reclaims this part loss can adopt following method: in ultrafiltrate, add nitric acid and stirring simultaneously, the nano silver particles polymerization is grown up, add the alkali neutralization then, carry out the ultrafiltration second time at last, the concentrate merging that concentrate that contains Nano Silver and the ultrafiltration for the first time that obtains after the ultrafiltration obtained gets final product.
4. as the preparation and the purification process of Nano Silver as described in claims 1 or 2, it is characterized in that: " two step method of purification " is not only applicable to the purifying with the Nano Silver of preparation method's preparation of the present invention, also can be used for the purifying of the Nano silver solution of other method preparation.
5. as the preparation and the purification process of Nano Silver as described in claims 1, it is characterized in that: reducing agent is maltose or citric acid or vitamin C or sodium borohydride or trisodium citrate or hydrazine hydrate.
6. as the preparation and the purification process of Nano Silver as described in claims 1, it is characterized in that: do not contain protectant reductant solution, be meant that needn't add the Nano Silver protective agent can prepare stabilized nano silver solution; Protective agent is meant that polyvinyl alcohol, polyvinylpyrrolidone etc. can stop Nano Silver to reunite, increase the material of Nano Silver stability.
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| CN103146758A (en) * | 2013-02-22 | 2013-06-12 | 北京科技大学 | Method for preparing nano silver particles through microbial surface reduction |
| CN103203466A (en) * | 2013-03-25 | 2013-07-17 | 中国人民解放军济南军区第四0一医院 | Method for preparing nano silver different in grain diameter |
| CN103752847A (en) * | 2014-01-25 | 2014-04-30 | 华南理工大学 | Method for preparing hemicellulose/nano-silver colloid rapidly |
| CN103878386A (en) * | 2014-03-28 | 2014-06-25 | 黑龙江大学 | Method for preparing fluorescent silver nano-clusters |
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| CN103203466A (en) * | 2013-03-25 | 2013-07-17 | 中国人民解放军济南军区第四0一医院 | Method for preparing nano silver different in grain diameter |
| CN103752847B (en) * | 2014-01-25 | 2016-03-02 | 华南理工大学 | A kind of fast preparation method of hemicellulose/nano silver colloidal sol |
| CN103752847A (en) * | 2014-01-25 | 2014-04-30 | 华南理工大学 | Method for preparing hemicellulose/nano-silver colloid rapidly |
| CN103878386A (en) * | 2014-03-28 | 2014-06-25 | 黑龙江大学 | Method for preparing fluorescent silver nano-clusters |
| CN104741621A (en) * | 2015-04-24 | 2015-07-01 | 北京化工大学 | Preparation method of nano-silver colloid with antibacterial property |
| CN104772471A (en) * | 2015-04-24 | 2015-07-15 | 北京化工大学 | Preparation method of nano-silver colloid with preservation performance |
| CN107529760A (en) * | 2015-05-18 | 2018-01-02 | 柿原秀己 | The manufacture method of antibacterial material, liquid antiseptic and liquid antiseptic |
| KR20180008432A (en) * | 2015-05-18 | 2018-01-24 | 히데미 카키하라 | Method for producing antimicrobial substance and liquid antimicrobial agent and liquid antimicrobial agent |
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| CN105108169A (en) * | 2015-09-09 | 2015-12-02 | 深圳市芭田生态工程股份有限公司 | Antibacterial agent used for fertilizer and application thereof |
| CN105478796A (en) * | 2015-12-23 | 2016-04-13 | 广东省微生物研究所 | Method for preparing nano-silver through tea tree essential oil and nano-silver solution prepared through method |
| CN105478796B (en) * | 2015-12-23 | 2018-01-05 | 广东省微生物研究所 | A kind of Nano silver solution for the method and its preparation that Nano Silver is prepared using tea tree ethereal oil |
| CN105862397A (en) * | 2016-03-31 | 2016-08-17 | 上海洋帆实业有限公司 | A preparing method of an antibacterial environmental friendly cotton fabric |
| CN105817645A (en) * | 2016-05-13 | 2016-08-03 | 溧阳市立方贵金属材料有限公司 | Ultra-pure silver powder preparation method capable of controlling particle size |
| CN107322005A (en) * | 2017-06-20 | 2017-11-07 | 北京大学 | A kind of SERS substrate fabrication method based on nano-Ag particles |
| CN109434132A (en) * | 2018-12-07 | 2019-03-08 | 陕西煤业化工技术研究院有限责任公司 | A method of purifying ultra-fine silver nanowires |
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Application publication date: 20110406 |