CN1287217C - Process for preparing nano silver colloidal water solution - Google Patents
Process for preparing nano silver colloidal water solution Download PDFInfo
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- CN1287217C CN1287217C CN 200410069105 CN200410069105A CN1287217C CN 1287217 C CN1287217 C CN 1287217C CN 200410069105 CN200410069105 CN 200410069105 CN 200410069105 A CN200410069105 A CN 200410069105A CN 1287217 C CN1287217 C CN 1287217C
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Abstract
The present invention relates to a method for preparing nanometer silver colloidal water solution. The method adopts double injection control technology. Silver ammonia water solution and reducing agent water solution are simultaneously injected in a reaction system containing protective agent water solution while a stirrer stirs the reaction system in order to generate nanometer silver particles. The reaction system is ultra-filtered and desalted in order to obtain nanometer silver colloidal water solution of which the average particle diameter is less than 50 nanometers. The nanometer silver colloidal water solution obtained by the method has the advantages of high stability, high dispersivity, small particle diameter and uniform distribution. The method has the advantages of high automation, short production periods and low cost, and is suitable for commercial production.
Description
Technical field
The present invention relates to a kind of preparation method of nano silver colloid aqueous solution.
Background technology
Existing thousands of years of the application of silver has the simple substance of multiple silver and compound to be used for antibacterial therapy to the thirties in 20th century.Discover in a large number, silver be used for antibacterial therapy have nontoxic, do not have irritated, have no drug resistance, do not have and intersect plurality of advantages such as medicine interference, it is broad-spectrum sterilization and do not injure beneficial bacterium and normal cell why, be because pathogen is a unicellular organism, it has respiratory enzyme to survive, silver runs into respiratory enzyme and combines with it, makes bacterium death.Compare with common silver, the nanometer state sterilizing ability of silver has down produced qualitative leap, and only the Nano Silver with minute quantity can produce powerful bactericidal action, but in aspect widespread uses such as environmental protection, weaving dress ornament, fruit freshness preserving, food hygiene, beauty treatments.
Chinese patent CN1266761A discloses a kind of preparation method of nano-scale silver powder; this method is that silver nitrate is made silver ammino solution; under agitation join gradually and contain in protectant reductant solution; silver in the silver ammino solution is reduced into nano level silver powder; washing after filtration; vacuum drying obtains the nano-silver powder of mean grain size in 50～100 nanometers.But because this nano-silver powder is a powder body material, when using, there is the problem of disperseing once more, thereby limited the application of product.
A kind of method of utilizing illumination method to prepare elargol is disclosed in " photographic science and the photochemistry " of the 19th the 1st phase of volume of calendar year 2001 " photochemistry preparation and resonance scattering spectroscopy thereof green and yellow silver glue are studied "; 1999 the 27th the 2nd phases of volume " Shaanxi Normal University's journal (natural science edition) " " making of nano silver gelatin composite membrane " discloses a kind of preparation method of nano silver colloid, this method is with behind silver nitrate and the sodium borohydride hybrid reaction generation nanometer elargol, it is joined in the gelatin solution again and makes film after the dispersion.
What above preparation method used is single dropping method of annotating.Single dropping method of annotating adopts the mode that drips at a slow speed to come realization response thing low concentration to participate in reaction usually, though this has reduced wherein a kind of concentration of reactants to a certain extent, but two kinds of reactants are all reacted with low concentration, can not reduce to amplitude peak the speed of growth of particle, and lack the auxiliary reactant concentration problem that solves of corresponding corollary apparatus, finally cause the particle that generates bigger, wider distribution.Adopt single dropping method of annotating, make the production cycle longer, be not suitable for suitability for industrialized production; And in above preparation method, owing to lack corresponding desalting processing technology, reaction by product and unnecessary ion can't be removed, and have restricted the moulding of product, influence the stable and dispersed of product simultaneously, also needed further improvement aspect preparation technology and the preparation facilities.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of nano silver colloid aqueous solution adopts that the nano silver colloid aqueous solution that this method obtains is stable, good dispersion, particle diameter is little and be evenly distributed.
Technical scheme of the present invention is: a kind of preparation method of nano silver colloid aqueous solution; it is characterized in that; adopt double injecting control technology; under the stirring of stirrer; silver-colored ammonia spirit and two simultaneously injection of reductive agent aqueous solution are contained in the reaction system of protective agent aqueous solution; generate nano silver particles,, obtain the nano silver colloid aqueous solution of mean grain size less than 50 nanometers through the ultrafiltration desalination.
A kind of preferred version, wherein said reductive agent are ascorbic acid, sodium borohydride or trisodium citrate.
A kind of preferred version, wherein said protective agent are one or more in amino acid, polyvinylpyrrolidone or the polyvinyl alcohol (PVA).
A kind of preferred version, wherein said stirrer are the rotor stirrers.
A kind of preferred version, wherein said stirrer are that the patent No. is the stirrer of ZL01278630.6.
The preparation method of nano silver colloid aqueous solution of the present invention; be to adopt double injecting control technology; under the stirring of stirrer; silver-colored ammonia spirit and two simultaneously injection of reductive agent aqueous solution are contained in the reaction system of protective agent aqueous solution; generate nano silver particles; through the ultrafiltration desalination, obtain the nano silver colloid aqueous solution of mean grain size less than 50 nanometers.
Among the present invention, the reaction system before the beginning is for containing protectant aqueous solution, and protective agent wherein is one or more in amino acid, polyvinylpyrrolidone or the polyvinyl alcohol (PVA); Reaction system is furnished with stirrer, this stirrer is that pre-dilution function, rotor stirrer that mixed performance is good are arranged, under the turning effort of stirrer rotor high-speed, silver ammonia spirit and reductive agent aqueous solution are injected in the stirrer stator simultaneously by charge pipe, and mix with the water-soluble liquid phase of a large amount of systems respectively, make reaction density obtain dilution.Afterwards, the silver ammino ion of low concentration and reductive agent molecule meet in the stator exit, and redox reaction takes place fast.Because reactant concentration is very low, thereby the silver particles that generates is tiny; Simultaneously, protective agent protects the nano silver particles that generates, and has effectively prevented the gathering between the silver particles, finally obtains the little nano silver particles of particle diameter.Reaction finishes back ultrafiltration desalination, obtains the nano silver colloid aqueous solution of stability and favorable dispersibility.
Ultrafiltration desalting technology among the present invention be with solution under certain pressure by having the ultrafiltration post of certain molecular cut off, leach the particle and the foreign ion of small-molecular weight, thereby obtain the method for the colloidal solution of desired molecule amount.
Among the present invention, being fit to reductive agent of the present invention can be ascorbic acid, sodium borohydride, hydrazine hydrate, trisodium citrate, formaldehyde or hydrogen peroxide, preferred ascorbic acid, sodium borohydride or trisodium citrate.
Double injecting control technology of the present invention is the double injecting control technology that adopts in the emulsion preparation, and this technology is disclosed in the U.S. Pat 4439215.
In the preparation process of Nano Silver, the effect of stirrer is extremely important, and suitable stirrer of the present invention is the rotor stirrer, and the preferred patent No. is the stirrer of ZL01278630.6.
Specific practice is:
2～6 parts of silver nitrates (quality, down with) are dissolved in 200～1000 parts of pure water, add concentration and be 25～28% ammoniacal liquor and be made into silver-colored ammonia spirit for 5～40 parts; 2～8 parts of reductive agents are dissolved in 200～1000 parts of pure water, are made into the reductive agent aqueous solution; In reaction pot, 2～10 parts of protective agents are added pure water and be made into aqueous solution for 300～600 parts; the rotor stirrer is housed in the reaction pot; this stirrer is made up of stator and rotor; the stator upper and lower port respectively has circular charging aperture; side has the outlet of perps type; the rotor of stirrer is divided into two-layer up and down by a disk, dilute solution is played in two chambeies up and down.When stirrer turns round, aqueous solution in a large amount of systems is inhaled into the inner chamber of stirrer, simultaneously silver-colored ammonia spirit and reductive agent aqueous solution enter the stirrer stator interior by charging aperture up and down respectively by charge pipe, reactant at inner chamber respectively by system aqueous solution, dilution.Afterwards, the silver ammino ion of low concentration and reductive agent molecule meet in the exit of perps type when being thrown away stator by rotor, and redox reaction takes place fast, and moment generates silver particles.Wherein, speed of agitator is 1500～2500 rev/mins, and two liquid are at the uniform velocity two to be annotated 60～180 minutes, injected the end back and continued reaction 20～60 minutes.Through the ultrafiltration desalination, obtain the nano silver colloid aqueous solution of mean grain size then less than 50 nanometers.
The Nano Silver mean grain size that adopts the inventive method preparation is taupe during the nano silver colloid aqueous solution high concentration less than 50 nanometers, and the dilution back is a golden transparent solution, and stability and favorable dispersibility.
Beneficial effect
In the present invention, owing to adopt double injecting control technology and pre-dilution function, rotor stirrer that mixed performance is good are arranged, the nano silver particles particle diameter that obtains is little and be evenly distributed nano silver colloid aqueous solution stability, favorable dispersibility.The inventive method automaticity height, with short production cycle, cost is low, is applicable to suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiment 1
Silver nitrate 200 gram is dissolved in 19.5 liters of pure water, adds concentration and be 25～28% ammoniacal liquor and be made into silver-colored ammonia spirit for 500 milliliters; 500 gram trisodium citrates are dissolved in 20 liters of pure water, are made into trisodium citrate aqueous solution; In reaction pot, amino acid 300 grams are added pure water and be made into aqueous solution for 50 liters.Set rotor stirrer (patent No. is ZL01278630.6) in the reaction pot.When stirrer turns round, aqueous solution liquid in a large amount of systems is inhaled into the inner chamber of stirrer, simultaneously silver-colored ammonia spirit and trisodium citrate aqueous solution enter the stirrer stator interior by charging aperture up and down respectively by charge pipe, at inner chamber respectively by system aqueous solution, dilution.Afterwards, the silver ammino ion of low concentration and trisodium citrate molecule meet in the exit when being thrown away stator by rotor, and moment generates silver particles.Wherein, speed of agitator is 1500 rev/mins, and two liquid are at the uniform velocity two to be annotated 140 minutes, injected the end back and continued reaction 20 minutes; Ultrafiltration desalination then obtains the nano silver colloid aqueous solution that mean grain size is 35 nanometers.
Embodiment 2
Silver nitrate 500 gram is dissolved in 99.25 liters of pure water, adds concentration and be 25～28% ammoniacal liquor and be made into silver-colored ammonia spirit for 750 milliliters; 600 gram ascorbic acid are dissolved in 100 liters of pure water, are made into aqueous ascorbic acid; In reaction pot, amino acid/11 00 gram and polyvinylpyrrolidone 700 grams are added pure water and be made into aqueous solution for 500 liters.Set rotor stirrer (patent No. is ZL01278631.4) in the reaction pot.When stirrer turns round, aqueous solution liquid in a large amount of systems is inhaled into the inner chamber of stirrer, simultaneously silver ammino solution and ascorbic acid solution enter the stirrer stator interior by charging aperture up and down respectively by charge pipe, reactant at inner chamber respectively by system aqueous solution, dilution.Afterwards, the silver ammino ion of low concentration and ascorbic acid molecule meet in the exit when being thrown away stator by rotor, and moment generates silver particles.Wherein, speed of agitator is 2500 rev/mins, and two liquid are at the uniform velocity two to be annotated 180 minutes, injected the end back and continued reaction 40 minutes; Through the ultrafiltration desalination, obtain the nano silver colloid aqueous solution that mean grain size is 30 nanometers then.
Embodiment 3
Silver nitrate 340 gram is dissolved in 48.6 liters of pure water, adds concentration and be 25～28% ammoniacal liquor and be made into silver-colored ammonia spirit for 1400 milliliters; 200 gram sodium borohydrides are dissolved in 50 liters of pure water, are made into sodium borohydride aqueous solution; In reaction pot, amino acid 200 gram and polyvinyl alcohol (PVA) 400 grams are added pure water and be made into aqueous solution for 100 liters.Set rotor stirrer (patent No. is ZL01278630.6) in the reaction pot.When stirrer turns round, aqueous solution liquid in a large amount of systems is inhaled into the inner chamber of stirrer, simultaneously silver ammino solution and sodium borohydride solution enter the stirrer stator interior by charging aperture up and down respectively by charge pipe, reactant at inner chamber respectively by system aqueous solution, dilution.Afterwards, the silver ammino ion of low concentration and sodium borohydride molecule meet in the exit when being thrown away stator by rotor, and moment generates silver particles.Wherein, speed of agitator is 2000 rev/mins, and two liquid are at the uniform velocity two to be annotated 80 minutes, injected the end back and continued reaction 60 minutes; Through the ultrafiltration desalination, obtain the nano silver colloid aqueous solution that mean grain size is 45 nanometers then.
Claims (4)
1. the preparation method of a nano silver colloid aqueous solution; it is characterized in that, adopt double injecting control technology, under the stirring of stirrer; silver-colored ammonia spirit and two simultaneously injection of reductive agent aqueous solution are contained in the reaction system of protective agent aqueous solution; generate nano silver particles, wherein, stirring rate is 1500～2500 rev/mins; two liquid are at the uniform velocity two to be annotated 60～180 minutes; inject and finish back continuation reaction 20～60 minutes,, obtain the nano silver colloid aqueous solution of mean grain size less than 50 nanometers then through the ultrafiltration desalination.
2. the preparation method of nano silver colloid aqueous solution according to claim 1 is characterized in that, wherein said reductive agent is ascorbic acid, sodium borohydride or trisodium citrate.
3. the preparation method of nano silver colloid aqueous solution according to claim 1 is characterized in that, wherein said protective agent is one or more in amino acid, polyvinylpyrrolidone or the polyvinyl alcohol (PVA).
4. the preparation method of nano silver colloid aqueous solution according to claim 1 is characterized in that, wherein said stirrer is the rotor stirrer.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410069105 CN1287217C (en) | 2004-07-06 | 2004-07-06 | Process for preparing nano silver colloidal water solution |
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| CN 200410069105 CN1287217C (en) | 2004-07-06 | 2004-07-06 | Process for preparing nano silver colloidal water solution |
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| CN1586774A CN1586774A (en) | 2005-03-02 |
| CN1287217C true CN1287217C (en) | 2006-11-29 |
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100420528C (en) * | 2005-12-28 | 2008-09-24 | 中国科学院理化技术研究所 | Method for preparing redispersible Ag nanoparticle by using silver halide precrystallization reduction process |
| CN101869988A (en) * | 2010-05-06 | 2010-10-27 | 复旦大学 | Method for preparing water base nano silver |
| CN101885072A (en) * | 2010-07-01 | 2010-11-17 | 苏州永拓环境科技有限公司 | Preparation method of nano-silver sol |
| CN102019432A (en) * | 2010-10-15 | 2011-04-20 | 安徽师范大学 | Preparation method of metal icosahedral nanoparticles |
| CN102366838A (en) * | 2011-09-16 | 2012-03-07 | 王利兵 | Preparation method of silver nano-particle with uniformity in particle size and favorable monodisperse stability |
| CN102585743A (en) * | 2011-12-23 | 2012-07-18 | 烟台德邦电子材料有限公司 | Conductive adhesive and preparation method thereof |
| CN103066160B (en) * | 2013-01-15 | 2016-01-20 | 浙江大学 | A kind of method of solar cell silicon wafer Surface Creation porous silicon |
| 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 |
| CN105295132A (en) * | 2015-12-01 | 2016-02-03 | 芜湖豫新世通汽车空调有限公司 | Anti-bacterial rubber tube for automobile air conditioner and preparation method of anti-bacterial rubber tube |
| CN107929902A (en) * | 2016-03-21 | 2018-04-20 | 周中南 | Trachea cannula tube core and preparation method thereof |
| JP6857166B2 (en) * | 2017-12-15 | 2021-04-14 | Ｄｏｗａエレクトロニクス株式会社 | Spherical silver powder and its manufacturing method |
| CN108555428B (en) * | 2018-05-29 | 2019-12-31 | 北京交通大学 | Preparation method and application of metal-based nano composite solder |
| CN109128211B (en) * | 2018-08-16 | 2021-10-26 | 山东大学 | Method for preparing micro-nano silver particles in aqueous solution system |
| CN113275584B (en) * | 2021-05-20 | 2023-11-14 | 苏州星翰新材料科技有限公司 | Micro-nano silver powder and preparation method and application thereof |
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Owner name: CHINA LUCKY GROUP CORPORATION Free format text: FORMER NAME: CHINESE LEKAI FILM GROUP CO |
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Address after: South Street, new urban lucky 071054 Hebei province Baoding City No. 6 Patentee after: China Lucky Group Corporation Address before: 071054 No. 1 Jianshe South Road, Hebei, Baoding Patentee before: Chinese Lekai Film Group Co |