CN101698235B - Method for preparing high-purity nano silver by gas assistance in liquid phase - Google Patents
Method for preparing high-purity nano silver by gas assistance in liquid phase Download PDFInfo
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- CN101698235B CN101698235B CN2009102367936A CN200910236793A CN101698235B CN 101698235 B CN101698235 B CN 101698235B CN 2009102367936 A CN2009102367936 A CN 2009102367936A CN 200910236793 A CN200910236793 A CN 200910236793A CN 101698235 B CN101698235 B CN 101698235B
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Abstract
The invention provides a method for preparing high-purity nano silver, namely a method that reducing agent direct reduces silver precursor to obtain elementary silver under the condition that dispersant is existed in liquid phase. The invention has the technical characteristic that gas is introduced as protective agent and assistant reducing agent in reaction process, gas protective agent firstly repels the most oxygen dissolved in reaction system, so that the whole reaction is carried out in low oxygen environment and purity of product is improved; under acid condition, the introduced gas assistant reducing agent can cause silver oxide power to be converted into sliver again, thus ensuring the purity of product. The nano silver powder made by the invention has narrow grain distribution, high crystallinity, regular appearance and high purity; silver powder grain can be controlled to be 10-100nm; and product yield is 90-99%. The invention has simple technology, easy control, no pollution low investment cost and short production period, and the whole reaction process can be automatically controlled, thus being applicable to large-scale industrialized production of high-purity nano silver.
Description
Technical field
The present invention relates to a kind of preparation method of high-purity nano silver, be applicable to the nano-scale silver powder that preparation is very easily oxidized.
Background technology
Nano-silver powder, because quantum size effect, small-size effect and skin effect, present many distinctive physics and chemical property, such as very high specific area, surface-active, surface energy and low-temperature sintering etc., make it have very high catalytic performance and electrical and thermal conductivity performance and good antibiotic and sterilizing activity, boundless application prospect is arranged at numerous areas such as catalyst material, electron ceramic material, low temperature Heat Conduction Material, conducting resinl and coating, inorganic antiseptics.China also has a certain distance at nano material this part with respect to external, therefore, and the high pure phase Nano Silver technology of the preparation that development and operation is simple, cost is low, for industry-by-industry, particularly electron trade can be brought technical revolution, has huge market potential and important meaning.
At present, the method for preparing nano-silver powder is a lot, mainly contains liquid phase chemical reduction method, electrochemical process, microemulsion method, laser vapor phase method etc.Wherein, the liquid phase chemical reduction method have that technology is simple, easy to operate, cost is relatively low, advantage such as suitability for industrialized production and being widely used in a large number.
But simple liquid phase chemical reduction legal system is equipped with Nano Silver, silver powder particle diameter wider distribution, and the average grain diameter difficulty reaches Nano grade, and the type looks are irregular; The process recovery ratio of preparation silver powder is low, separation difficulty; Because the Nano Silver particle diameter is little, oxidized easily, even in preparation process; add organic matter and cook protective agent, also be difficult to guarantee the purity of nano-silver powder, thereby; the silver powder that obtains aborning often contains impurity such as partial oxidation silver, has a strong impact on its some important application.
The existing liquid phase chemical reduction legal system that adopts is equipped with in the Nano Silver document, great majority adopt alkaline reducers or in alkaline environment the method in the silver-colored source of reduction obtain nano-silver powder; Besides under acid condition among the preparation method of fast restore, many employings only add reunion and the oxidation that dispersant and protectant method stop product.And this chemical reduction method that adopts gas to cook protective agent and assistant reducing agent under acid condition yet there are no report, and this research proves that also this method can solve above-mentioned simple liquid phase chemical reduction legal system and be equipped with variety of problems in the Nano Silver.
The patent of preparation super fine silver powder is a lot of both at home and abroad at present, publication number CN1387968 has just set forth a kind of method, PH transfers to 1-7 with liquor argenti nitratis ophthalmicus, other joins reducing solution, and it is close that the reducing solution temperature is transferred to liquor argenti nitratis ophthalmicus, under the stirring condition with the two mixing, get silver-colored sediment, with deionized water and absolute ethanol washing, 50-80 ℃ of following vacuum drying can get the silver powder of 0.3-3.0um.The Nano Silver particle diameter wider distribution that this method makes does not reach nanoscale; The particle dispersiveness is relatively poor, and part is reunited and be oxidized on a small quantity; Be reducing agent and solvent reduction silver nitrate under 120-190 ℃ then among the publication number CN1903946A with ethylene glycol or glycerine, also need above-mentioned solution to be washed, separates after being cooled to room temperature with organic solvent, and repeated multiple times, 50-60 ℃ of following vacuum drying gets nano-scale silver powder.This method adopts volume to be organic solvent, and reaction temperature is also higher, and Nano Silver is better dispersed, but according to the back its XRD figure that provides, find out there is oxide in the product that purity is not enough.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of high-purity nano silver, promptly adopt in liquid phase and directly to reduce silver-colored presoma with reducing agent and obtain the method for silver precipitation, introduce gas in course of reaction and cooked protective agent and acid assistant reducing agent, most oxygen in the reaction system is driven away in the gas shield agent, entire reaction course is all carried out under the condition of hypoxemia, can improve the purity of product; Under the acid condition of assistant reducing agent, the gas of feeding can make the silver powder of oxidation be converted into simple substance silver again, to guarantee the purity of product.
The concrete preparation method of high-purity nano silver is as follows
A. the concentration with Ag presoma and deionized water preparation is the oxidation liquid of 0.1-1.5mol/L; With deionized water and reducing agent compound concentration is the reducing solution of 0.05-0.5mol/L;
The reducing solution for preparing is moved into reactor, add dispersant, regulate its pH value to 1-5, feed protective gas and drive oxygen in the solution, temperature of reactor is risen to 30-100 ℃ with assistant reducing agent;
Described reducing agent is: NaH
2PO
2, KH
2PO
2Or the 1-2 kind in the trisodium citrate; Described assistant reducing agent is: H
2SO
4, HCl or NH
41-2 kind among the Cl, its concentration are 1-4mol/L; Described dispersant is: one or more in polyvinyl pyrrolidone, AEO-3, the basic sodium sulfonate of dodecane, class of department 20, class of department 80, stearic acid, the four butyl bromation amine; Its addition is the 1-15% of silver-colored presoma quality.
B. be 1 in the Oxidizing and Reducing Agents mol ratio: the ratio of 0.25-0.85, with oxidation liquid with 5-60 drip/min speed is added drop-wise in the reactor of steps A, stir while dripping, the pH with alkalies control reaction system makes its maintenance constant in the course of reaction simultaneously, keeping reaction temperature is 30-100 ℃, drip the back and continue reaction 10-80min, be cooled to room temperature, stop logical protective gas; Filter, spend deionised water 2-4 time, with ethanol washing 2-5 time, vacuum drying obtains nano-silver powder again.
The described Ag presoma of steps A is silver nitrate, silver acetate or AgC
2O
4In the 1-2 kind; The described alkalies of step B is: NH
3H
2O, sodium carbonate or H
2O
2In the 1-2 kind.
Protective gas described in steps A and the B is: H
2, N
2Or the 1-2 kind among the Ar.
The XRD of product and TEM testing result are seen Fig. 1, Fig. 2, are shown by Fig. 1-2: product purity is very high, the particle diameter narrow distribution, and the pattern rule, better dispersed between particle.
Advantage of the present invention is: the nano-silver powder narrow diameter distribution of preparation, degree of crystallinity height, pattern rule, any surface finish, and purity is very high; The silver powder controllable granularity is built in 10-100nm; Product yield is 90%-99%.Technology of the present invention is simple, easy to control, do not pollute, cost of investment is low, with short production cycle, but entire reaction course automation control is suitable for the large-scale industrial production high-purity nano silver.
The present invention at catalyst material, electron ceramic material, antistatic material, low temperature superconducting material, electric slurry, inorganic antibacterial material, biomaterial, partially absorb fields such as ultraviolet materials and have wide practical use.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of Nano Silver powder.
Fig. 2 is the transmission electron microscope collection of illustrative plates of Nano Silver powder.
The specific embodiment
Embodiment 1
With 0.85gAgNO
3Be made into 0.5mol/L oxidation liquid with deionized water, keep in Dark Place; With 0.11gNaH
2PO
2Be made into the 0.1mol/L reducing solution with deionized water; Again reducing solution is moved into four-hole boiling flask, add 0.085g dispersant A EO-3, with the H of 1mol/L
2SO
4Regulate its pH value to 2, begin to feed H
2, regulate air-flow and make 1/4 glass tube exit H in the solution
2Flow velocity is 60 bubble/min, after temperature rises to 45 ℃, the speed of oxidation liquid with 6/min is added in the reducing solution, and reaction temperature keeps 45 ℃, uses NH in the course of reaction simultaneously
3H
2O control pH value of reaction system is about 2; Drip the back and continue reaction 30min, be cooled to room temperature, stop to feed H
2Centrifugal, deionization washing 3 times, ethanol is washed 3 times, vacuum drying.Obtain nano-silver powder 0.5130g, gravimetric method counting yield yield is 95%, and particle diameter is at 25-35nm.
Embodiment 2
With 0.85gAgNO
3Be made into 0.5mol/L oxidation liquid with deionized water, keep in Dark Place; With 0.242gNaH
2PO
2Be made into the 0.5mol/L reducing solution with deionized water; Again reducing solution is moved into four-hole boiling flask, add dispersant A EO-3, with the H of 1mol/L
2SO
4Regulate its pH value to 4, begin to feed N
2, regulate air-flow and make 1/4 glass tube exit N in the solution
2Flow velocity is after 30 bubble/min temperature rise to 55 ℃, and the speed of oxidation liquid with 30/min is added in the reducing solution, and reaction temperature keeps 55 ℃, uses NH in the course of reaction simultaneously
3H
2O control pH value of reaction system is about 4; Drip the back and continue reaction 15min, be cooled to room temperature, stop to feed N
2Centrifugal, deionization washing 3 times, ethanol is washed 3 times, vacuum drying.Obtain nano-silver powder 0.4970g, gravimetric method counting yield yield is 92%, and particle diameter is at 35-50nm.
The sample that obtains is carried out characterization result see Fig. 1, Fig. 2, from the nano-silver powder narrow diameter distribution that Fig. 1-2 obtains as can be seen, the nano-silver powder of pattern rule.
Embodiment 3
With 0.85gAgNO
3Be made into 0.5mol/L oxidation liquid with deionized water, keep in Dark Place; With 0.234gKH
2PO
2Be made into the 0.5mol/L reducing solution with deionized water; Again reducing solution is moved into four-hole boiling flask, add the dispersant neopelex, regulate its pH value to 3, begin to feed N with the HCl of 2mol/L
2, regulate air-flow and make 1/4 glass tube exit N in the solution
2Flow velocity is 60 bubble/min, after temperature rises to 60 ℃, the speed of oxidation liquid with 60/min is added in the reducing solution, and reaction temperature keeps 60 ℃, uses NH in the course of reaction simultaneously
3H
2O control pH value of reaction system is about 3; Drip the back and continue reaction 15min, be cooled to room temperature, stop to feed N
2Pumping rate, deionization washing 3 times, ethanol is washed 3 times, vacuum drying.Obtain nano-silver powder 0.5022g, gravimetric method counting yield yield is 93%, and particle diameter is at 20-30nm.
Embodiment 4
With 0.85gAgNO
3Be made into 1mol/L oxidation liquid with deionized water, keep in Dark Place; With 0.286gKH
2PO
2Be made into the 0.5mol/L reducing solution with deionized water; Again reducing solution is moved into four-hole boiling flask, add the polyethylene of dispersing agent pyrrolones, regulate its pH value to 1, begin to feed H with the HCl of 1mol/L
2, regulate air-flow and make 1/4 glass tube exit H in the solution
2Flow velocity is 40 bubble/min, after temperature rises to 70 ℃, the speed of oxidation liquid with 50/min is added in the reducing solution, and reaction temperature keeps 70 ℃, controls pH value of reaction system about 1 with sodium carbonate in the course of reaction simultaneously; Drip the back and continue reaction 45min, be cooled to room temperature, stop to feed H
2Pumping rate, deionization washing 3 times, ethanol is washed 3 times, vacuum drying.Obtain nano-silver powder 0.5292g, gravimetric method counting yield yield is 98%, and particle diameter is at 50-80nm.
Embodiment 5
0.85g silver acetate and deionized water are made into 1mol/L oxidation liquid, keep in Dark Place; With 0.338gKH
2PO
2Be made into the 0.5mol/L reducing solution with deionized water; Again reducing solution is moved into four-hole boiling flask, add the polyethylene of dispersing agent pyrrolones, with the NH of 1mol/L
4Cl regulates its pH value to 1, begins to feed N
2, regulate air-flow and make 1/4 glass tube exit N in the solution
2Flow velocity is 20 bubble/min, after temperature rises to 80 ℃, the speed of oxidation liquid with 10/min is added in the reducing solution, and reaction temperature keeps 80 ℃, controls pH value of reaction system about 1 with sodium carbonate in the course of reaction simultaneously; Drip the back and continue reaction 45min, be cooled to room temperature, stop to feed N
2Centrifugal, deionization washing 3 times, ethanol is washed 3 times, vacuum drying.Obtain nano-silver powder 0.5076g, gravimetric method counting yield yield is 94%, and particle diameter is at 60-80nm.
Embodiment 6
0.85g silver acetate and deionized water are made into 2mol/L oxidation liquid, keep in Dark Place; 1.00g trisodium citrate and deionized water are made into the 2mol/L reducing solution; Again reducing solution is moved into four-hole boiling flask, add class of dispersant department 20, with the HSO of 1mol/L
4Regulate its pH value to 5, begin to feed H
2, regulate air-flow and make 1/4 glass tube exit H in the solution
2Flow velocity is 10 bubble/min, after temperature rises to 60 ℃, the speed of oxidation liquid with 8/min is added in the reducing solution, and reaction temperature keeps 60 ℃, controls pH value of reaction system about 5 with sodium carbonate in the course of reaction simultaneously; Drip the back and continue reaction 45min, be cooled to room temperature, stop to feed H
2Centrifugal, deionization washing 3 times, ethanol is washed 3 times, vacuum drying.Obtain nano-silver powder 0.5022g, gravimetric method counting yield yield is 93%, and particle diameter is at 30-50nm.
Embodiment 7
0.85g silver acetate and deionized water are made into 4mol/L oxidation liquid, keep in Dark Place; 0.67g trisodium citrate and deionized water are made into the 1mol/L reducing solution; Again reducing solution is moved into four-hole boiling flask, add class of dispersant department 80, HCl with 1mol/L regulates its pH value to 4, begin to feed Ar, regulate air-flow and make that 1/4 glass tube exit Ar flow velocity is 30 bubble/min in the solution, after temperature rises to 50 ℃, in the speed adding reducing solution of oxidation liquid with 6/min, reaction temperature keeps 50 ℃, controls pH value of reaction system about 4 with sodium carbonate in the course of reaction simultaneously; Drip the back and continue reaction 60min, be cooled to room temperature, stop to feed Ar; Centrifugal, deionization washing 3 times, ethanol is washed 3 times, vacuum drying.Obtain nano-silver powder 0.4914g, gravimetric method counting yield yield is 91%, and particle diameter is at 30-40nm.
Embodiment 8
With 0.85g AgC
2O
4Be made into 4mol/L oxidation liquid with deionized water, keep in Dark Place; With 0.39gKH
2PO
2Be made into the 3mol/L reducing solution with deionized water; Again reducing solution is moved into four-hole boiling flask, add the dispersant stearic acid, with the NH of 1mol/L
4Cl regulates its pH value to 3, begin to feed Ar, regulate air-flow and make that 1/4 glass tube exit Ar flow velocity is 60 bubble/min in the solution, after temperature rises to 65 ℃, the speed of oxidation liquid with 6/min is added in the reducing solution, reaction temperature keeps 65 ℃, controls pH value of reaction system about 3 with sodium carbonate in the course of reaction simultaneously; Drip the back and continue reaction 30min, be cooled to room temperature, stop to feed Ar; Pumping rate, deionization washing 3 times, ethanol is washed 3 times, vacuum drying.Obtain nano-silver powder 0.5184g, gravimetric method counting yield yield is 96%, and particle diameter is at 20-50nm.
Embodiment 9
With 0.85g AgC
2O
4Be made into 1.5mol/L oxidation liquid with deionized water, keep in Dark Place; With 0.26gKH
2PO
2Be made into the 0.2mol/L reducing solution with deionized water; Again reducing solution is moved into four-hole boiling flask, add the dispersant four butyl bromation amine, with the H of 1mol/L
2SO
4Regulate its pH value to 4, begin to feed Ar, regulate air-flow and make that 1/4 glass tube exit Ar flow velocity is 20 bubble/min in the solution, after temperature rises to 80 ℃, the speed of oxidation liquid with 45/min is added in the reducing solution, reaction temperature keeps 80 ℃, controls pH value of reaction system about 4 with sodium carbonate in the course of reaction simultaneously; Drip the back and continue reaction 60min, be cooled to room temperature, stop to feed Ar; Centrifugal, deionization washing 3 times, ethanol is washed 3 times, vacuum drying.Obtain nano-silver powder 0.5130g, gravimetric method counting yield yield is 95%, and particle diameter is at 80-90nm.
Claims (2)
1. the method for preparing high-purity nano silver by gas assistance in the liquid phase, concrete preparation method is as follows
A. the concentration with Ag presoma and deionized water preparation is the oxidation liquid of 0.1-1.5mol/L; With deionized water and reducing agent compound concentration is the reducing solution of 0.05-0.5mol/L; Described Ag presoma is silver nitrate, silver acetate or AgC
2O
4In the 1-2 kind;
The reducing solution for preparing is moved into reactor, add dispersant, regulate its pH value to 1-5, feed protective gas and drive oxygen in the solution, temperature of reactor is risen to 30-100 ℃ with assistant reducing agent;
Described reducing agent is: NaH
2PO
2, KH
2PO
2Or the 1-2 kind in the trisodium citrate; Described assistant reducing agent is: H
2SO
4, HCl or NH
41-2 kind among the Cl, its concentration are 1-4mol/L; Described dispersant is: one or more in polyvinyl pyrrolidone, AEO-3, the basic sodium sulfonate of dodecane, class of department 20, class of department 80, stearic acid, the four butyl bromation amine; Its addition is the 1-15% of silver-colored presoma quality;
B. be 1 in the Oxidizing and Reducing Agents mol ratio: the ratio of 0.25-0.85, with oxidation liquid with 5-60 drip/min speed is added drop-wise in the reactor of steps A, stir while dripping, the pH with alkalies control reaction system makes its maintenance constant in the course of reaction simultaneously, keeping reaction temperature is 30-100 ℃, drip the back and continue reaction 10-80min, be cooled to room temperature, stop logical protective gas; Filter, spend deionised water 2-4 time, with ethanol washing 2-5 time, vacuum drying obtains nano-silver powder again;
Described alkalies is: NH
3H
2O or sodium carbonate.
2. according to the method for preparing high-purity nano silver by gas assistance in the described liquid phase of claim, it is characterized in that the protective gas described in steps A and the B is: H
2, N
2Or the 1-2 kind among the Ar.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102059347B (en) * | 2010-12-31 | 2013-01-02 | 中科院广州化学有限公司 | Nano silver capable of being scattered in hydrophobic system and preparation method and application thereof |
| RU2448810C1 (en) * | 2011-04-05 | 2012-04-27 | Государственное образовательное учреждение высшего профессионального образования "Башкирский государственный университет" (ГОУ ВПО БашГУ) | Method of producing silver nanoparticles |
| CN104174864B (en) * | 2013-05-21 | 2016-06-01 | 中国科学院理化技术研究所 | The preparation method of a kind of nanometer or submicron order Argent grain powder |
| CN104689770A (en) * | 2015-02-26 | 2015-06-10 | 江汉大学 | Gas phase/liquid phase membrane reaction method for preparing nano material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1387968A (en) * | 2001-05-26 | 2003-01-01 | 西北稀有金属材料研究院 | Prepn of superfine spherical silver powder |
| CN1686646A (en) * | 2005-04-26 | 2005-10-26 | 四川大学 | Preparation method of grain size controllable single dispersed nano silver powder |
| CN1785558A (en) * | 2005-11-21 | 2006-06-14 | 东南大学 | Preparation method of micron grade ball shape silver powder for conductive silver paste |
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2009
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1387968A (en) * | 2001-05-26 | 2003-01-01 | 西北稀有金属材料研究院 | Prepn of superfine spherical silver powder |
| CN1686646A (en) * | 2005-04-26 | 2005-10-26 | 四川大学 | Preparation method of grain size controllable single dispersed nano silver powder |
| CN1785558A (en) * | 2005-11-21 | 2006-06-14 | 东南大学 | Preparation method of micron grade ball shape silver powder for conductive silver paste |
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