CN107058757A - A kind of production method of the separation of Silver from silver-containing liquid waste - Google Patents
A kind of production method of the separation of Silver from silver-containing liquid waste Download PDFInfo
- Publication number
- CN107058757A CN107058757A CN201710182040.6A CN201710182040A CN107058757A CN 107058757 A CN107058757 A CN 107058757A CN 201710182040 A CN201710182040 A CN 201710182040A CN 107058757 A CN107058757 A CN 107058757A
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- Prior art keywords
- silver
- containing liquid
- liquid waste
- ion
- colored
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
Abstract
The invention discloses a kind of production method of the separation of Silver from silver-containing liquid waste, this method is filtered after silver-containing liquid waste is added into ammoniacal liquor complexing first, silver-colored ammonium salt solution is obtained after the hydroxide precipitation of inert metal ion is removed, then silver powder is obtained after being reduced using hydrazine hydrate to silver-colored ammonium salt solution, it is finally separating supernatant, with pure water silver powder for several times, filter, be dried to obtain the silver powder that purity is more than 98%.The present invention only needs to a small amount of plastic containers and filter cloth, complex device need not be put into, only need to two kinds of reagents of ammoniacal liquor and hydrazine hydrate, other base metals need not be introduced, without using halide precipitate silver, silver and the separation of other metal impurities can be just completed, the excessive reductant of addition can be eliminated by washing, obtain higher degree silver powder.Cost of the present invention is relatively low, simple to operate, efficiency is higher, can be suitably used for silver concentration is more than recovery and purification silver-colored in 0.1g/ml silver-containing liquid waste, and isolated silver-colored purity is high.
Description
Technical field
The invention belongs to silver recovery and purification technique field, and in particular to a kind of producer of the separation of Silver from silver-containing liquid waste
Method.
Background technology
With the development of science and technology, silver turns into indispensable important meals in modern science and technology and culture life
Material.But the natural resources of silver is increasingly reduced, and Oily wastewater is growing day by day, and its silver-colored grade is higher than raw ore, easily reclaims,
It is economical.At present, the method for silver is reclaimed from silver-containing liquid waste mainly the precipitation method, electrolysis, reduction method of substitution, ion exchange
Method and absorption method.
（1）The precipitation method：The silver that the precipitation method are reclaimed in silver-containing liquid waste is exactly to add appropriate anion in silver-containing liquid waste to make
Silver in waste liquid is enriched with coprecipitation mode.The precipitation form of silver is dried to obtain through filtering, washing.The silver sulfide precipitation method are by adding
Enter Na2S makes silver be changed into Ag2S precipitates and realized the enrichment of silver.Due to Na2S simultaneously also easily by other metal ions together
Is precipitated out if also containing other metal ions in silver-containing liquid waste, then the Ag obtained2It can also contain in S precipitations other
Precipitation by metallic ion thing, causes Ag2S precipitation purity is relatively low.So the method is mainly used in, species of metal ion is relatively simple to be contained
Silver-colored waste liquid such as waste fixer solution, laboratory waste liquid etc..Silver nitride precipitation rule is by adding NaC1 or HC1 solution to be changed into silver
AgC1 precipitate and to realize the enrichment of silver ion.It can overcome the defect that silver ion and other metal ions are co-precipitated.Cause
This, silver nitride precipitation method is that the prefered method of silver is reclaimed from the waste liquid for being contaminated with many kinds of metal ions.Sometimes for ensuring silver
Ion precipitation completely, can add the precipitating reagent Cl for the amount of skipping over-, but Cl-It is excessive also to form soluble chlorine silver complex and make dissolving
Degree increase.The silver powder of precipitation method generation contain higher Cl-, S2-, it is necessary to further be removed using thermal process.
（2）Electrolysis：Electrolysis is used for waste fixer solution and silver-plated waste liquid.The biggest advantage is that not introducing impurity.Together
When due to the electrode potential of silver it is high (+0.799V), therefore in electrolytic process, other metal ions are difficult to separate out, therefore can reclaim
To the higher argent of purity, for electroplating effluent, moreover it is possible to abolish a part of cyanogen while silver is reclaimed.But because electrolysis exists
Can not be carried out under low metal ion concentration conditions, when reclaiming silver, in accumulator tank silver-colored mass concentration preferably control 200 mg/L with
On.Therefore it is not suitable for the silver recovery of the silver-containing liquid waste of low concentration of silver ions and this method needs larger equipment investment.
（3）Displacement method：Displacement method is typically, as reducing agent, the silver reduction deposition in waste liquid is got off using lossy metal
A kind of method.Because zinc and iron phase are to relatively inexpensive, therefore it is commonly used for lossy metal.Also it is lossy metal to have using aluminium,
Contain Ag in recovery2During the silver-containing liquid waste of S precipitation forms, the rate of recovery has reached 55%~60%.Reducing agent can also be other
The sodium borohydride of reagent, such as strong reducing property, is put into silver-containing liquid waste, and adjusts solution ph to 8, can be reduced directly recovery
Silver, the rate of recovery reaches 96%, reclaims obtained silver-colored purity and reaches 99.5%.Displacement method has the treatment of wastes with processes of wastes against one another, easy to use, behaviour
The advantages of making easy.Moreover, the silver that displacement method can be to exist in Recycling of waste liquid with precipitation form, such as AgC1, AgBr,
AgI、Ag2S etc..Iron and zinc are to AgI, Ag2The precipitation reducing power such as S is low, and by contrast, aluminium has stronger reducing power, can make
The activation energy of reduction silver compound is greatly reduced, and the silver compound that stability can be made high is reduced.But this method needs to add
The displacement metal of amount, causes the silver powder purity of generation low, it is necessary to further purification.
（4）Ion-exchange：Compared with the recovery method of above-mentioned common silver-containing liquid waste silver.Ion-exchange has energy
The advantage of trace silver in Recycling of waste liquid.During with the electroplating rinse water that the mass concentration of the method Processing Ag is 1.5 mg/L, silver can quilt
Reclaim completely.For the secondary treated wastewater containing Trace Silver, with cationic ion-exchange resin up to 80% or so clearance, if with the moon
Then clearance may be up to 91.7% to cation hybrid switching resin.The silver in silver-containing waste water, tool are reclaimed using ion exchange resin
Have that processing capacity is big, effluent quality is good, resin is renewable, it is simple to operate the features such as.But this method needs larger equipment investment.
（5）Absorption method：Absorption method reclaims the silver in silver-containing liquid waste, i.e., led to by the adsorbent activity surface being added in waste liquid
Physical chemistry effect adsorption and enrichment silver is crossed, then elemental silver is obtained by post processing recovery, its adsorption effect depends primarily on institute
The performance of the adsorbent used.The active charcoal of conventional adsorbent, NACF, chelating material and the polymer containing free radical
Deng.But this method needs larger equipment investment.
The content of the invention
The invention aims to solve technical problem present in prior art, there is provided a kind of low cost, operation letter
Single, high efficiency, and complex device need not be put into and the production method of separation of Silver from silver-containing liquid waste of other base metals is introduced into.
In order to achieve the above object, the present invention uses following technical scheme：A kind of production of the separation of Silver from silver-containing liquid waste
Method, this method comprises the following steps：
A) ammoniacal liquor is added into silver-containing liquid waste, the pH value of silver-containing liquid waste is adjusted to 9~10, makes the inert metal in silver-containing liquid waste
Ion hydrolysis hydrate precipitation, the silver-colored ammonium complex ion of silver ion generation, the hydroxide that filtering removes inert metal ion sink
Form sediment, obtain silver-colored ammonium salt solution.If the pH value of silver-containing liquid waste is less than 9 in the step, then silver ion can not generate silver-colored ammonium salt solution completely,
Silver ion part exists with silver oxide solid particle state, can be one while the hydroxide precipitation of inert metal ion is filtered
With getting rid of, silver-colored direct yield is reduced, and the percent hydrolysis of inert metal ion is low, and clearance is low.
B) excess hydrazine hydrate is added into silver-colored ammonium salt solution, until not having bubble generation in solution, silver ion is reduced completely
Into silver powder.
C) supernatant is separated, is for several times 7~8 to washing lotion pH value with pure water silver powder, now the ammoniacal liquor and water in silver powder
Close hydrazine to be washed off completely, while sodium, potassium isoreactivity metal ion are also fully washed off, filter, be dried to obtain purity more than 98%
Silver powder.
Further, ammoniacal liquor is the mass concentration 25%-28% pure rank of analysis in the step a).
Further, hydrazine hydrate is the pure rank of analysis of mass concentration 80% in the step b).
The present invention has the advantages that compared with the prior art：Silver-containing liquid waste is added mistake after ammoniacal liquor complexing by the present invention
Filter, is obtained silver-colored ammonium salt solution after the hydroxide precipitation of inert metal ion is removed, then silver-colored ammonium salt solution is entered using hydrazine hydrate
Silver powder is obtained after row reduction, supernatant is finally separating, filters with pure water silver powder for several times, be dried to obtain purity more than 98%
Silver powder.The present invention only needs to a small amount of plastic containers and filter cloth, it is not necessary to put into complex device, it is only necessary to two kinds of ammoniacal liquor and hydrazine hydrate
Reagent, it is not necessary to introduce other base metals, without using halide precipitate silver, can just complete silver and the separation of other metal impurities,
The excessive reductant of addition can be eliminated by washing, obtain higher degree silver powder.Cost of the present invention is relatively low, simple to operate, effect
Rate is higher, can be suitably used for silver concentration is more than silver-colored recovery and purification, isolated silver-colored purity in 0.1g/ml silver-containing liquid waste
It is high.
Brief description of the drawings
Fig. 1 is process chart of the invention.
Embodiment
The invention will be further described with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
As shown in figure 1, a kind of production method of the separation of Silver from silver-containing liquid waste, this method comprises the following steps：
A) it is the 25%, ammoniacal liquor of the pure rank of analysis that mass concentration is added into silver-containing liquid waste, adjusts the pH value of silver-containing liquid waste to 9,
The inert metal ion in silver-containing liquid waste is set to hydrolyze hydrate precipitation, the silver-colored ammonium complex ion of silver ion generation, filtering removes lazy
Property metal ion hydroxide precipitation, obtain silver-colored ammonium salt solution；
B) it is the 80%, hydrazine hydrate of the pure rank of analysis that extra mass concentration is added into silver-colored ammonium salt solution, until not having gas in solution
Bubble is produced, and silver ion is reduced into silver powder completely；
C) supernatant is separated, is for several times 7 to washing lotion pH value with pure water silver powder, now the ammoniacal liquor in silver powder and hydrazine hydrate quilt
Wash off completely, while sodium, potassium isoreactivity metal ion are also fully washed off, filter, be dried to obtain the silver powder that purity is 98.6%.
Embodiment 2
As shown in figure 1, a kind of production method of the separation of Silver from silver-containing liquid waste, this method comprises the following steps：
A) it is the 28%, ammoniacal liquor of the pure rank of analysis that mass concentration is added into silver-containing liquid waste, adjusts the pH value of silver-containing liquid waste to 10,
The inert metal ion in silver-containing liquid waste is set to hydrolyze hydrate precipitation, the silver-colored ammonium complex ion of silver ion generation, filtering removes lazy
Property metal ion hydroxide precipitation, obtain silver-colored ammonium salt solution；
B) it is the 80%, hydrazine hydrate of the pure rank of analysis that extra mass concentration is added into silver-colored ammonium salt solution, until not having gas in solution
Bubble is produced, and silver ion is reduced into silver powder completely；
C) supernatant is separated, is for several times 8 to washing lotion pH value with pure water silver powder, now the ammoniacal liquor in silver powder and hydrazine hydrate quilt
Wash off completely, while sodium, potassium isoreactivity metal ion are also fully washed off, filter, be dried to obtain the silver powder that purity is 98.9%.
Claims (3)
1. a kind of production method of the separation of Silver from silver-containing liquid waste, it is characterised in that this method comprises the following steps：
A) ammoniacal liquor is added into silver-containing liquid waste, the pH value of silver-containing liquid waste is adjusted to 9~10, makes the inert metal in silver-containing liquid waste
Ion hydrolysis hydrate precipitation, the silver-colored ammonium complex ion of silver ion generation, the hydroxide that filtering removes inert metal ion sink
Form sediment, obtain silver-colored ammonium salt solution；
B) excess hydrazine hydrate is added into silver-colored ammonium salt solution, until not having bubble generation in solution, silver ion is reduced into silver completely
Powder；
C) supernatant is separated, is for several times 7~8 to washing lotion pH value with pure water silver powder, filters, be dried to obtain purity more than 98%
Silver powder.
2. a kind of production method of separation of Silver from silver-containing liquid waste according to claim 1, it is characterised in that：The step
A) ammoniacal liquor is the mass concentration 25%-28% pure rank of analysis in.
3. a kind of production method of separation of Silver from silver-containing liquid waste according to claim 1, it is characterised in that：The step
B) hydrazine hydrate is the pure rank of analysis of mass concentration 80% in.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710182040.6A CN107058757A (en) | 2017-03-24 | 2017-03-24 | A kind of production method of the separation of Silver from silver-containing liquid waste |
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| CN201710182040.6A CN107058757A (en) | 2017-03-24 | 2017-03-24 | A kind of production method of the separation of Silver from silver-containing liquid waste |
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| CN107058757A true CN107058757A (en) | 2017-08-18 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111348793A (en) * | 2018-12-24 | 2020-06-30 | 荆门市格林美新材料有限公司 | Treatment method of hydrazine hydrate liquid-phase reduction silver powder waste liquid |
| CN112730142A (en) * | 2020-12-02 | 2021-04-30 | 昆山鸿福泰环保科技有限公司 | Method for detecting silver content in silver-containing waste liquid based on gravimetric method |
| CN114107665A (en) * | 2021-11-03 | 2022-03-01 | 韶关鹏瑞环保科技有限公司 | Film desilvering recovery process |
| CN114453589A (en) * | 2022-02-18 | 2022-05-10 | 贵研铂业股份有限公司 | Preparation method of high-purity gold |
| CN114620879A (en) * | 2022-03-14 | 2022-06-14 | 苏州诺菲纳米科技有限公司 | Method for recycling waste liquid from silver nanowire production |
| CN115286143A (en) * | 2022-08-17 | 2022-11-04 | 清远先导材料有限公司 | Method for recovering silver from silver-containing waste liquid |
Citations (3)
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| JP2015045066A (en) * | 2013-08-28 | 2015-03-12 | 住友金属鉱山株式会社 | Production method of silver powder and production apparatus of silver powder |
| JP2016113700A (en) * | 2015-12-22 | 2016-06-23 | 住友金属鉱山株式会社 | Production method for silver powder |
| 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 |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2015045066A (en) * | 2013-08-28 | 2015-03-12 | 住友金属鉱山株式会社 | Production method of silver powder and production apparatus of silver powder |
| JP2016113700A (en) * | 2015-12-22 | 2016-06-23 | 住友金属鉱山株式会社 | Production method for silver powder |
| 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 |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111348793A (en) * | 2018-12-24 | 2020-06-30 | 荆门市格林美新材料有限公司 | Treatment method of hydrazine hydrate liquid-phase reduction silver powder waste liquid |
| CN111348793B (en) * | 2018-12-24 | 2022-01-07 | 荆门市格林美新材料有限公司 | Treatment method of hydrazine hydrate liquid-phase reduction silver powder waste liquid |
| CN112730142A (en) * | 2020-12-02 | 2021-04-30 | 昆山鸿福泰环保科技有限公司 | Method for detecting silver content in silver-containing waste liquid based on gravimetric method |
| CN114107665A (en) * | 2021-11-03 | 2022-03-01 | 韶关鹏瑞环保科技有限公司 | Film desilvering recovery process |
| CN114453589A (en) * | 2022-02-18 | 2022-05-10 | 贵研铂业股份有限公司 | Preparation method of high-purity gold |
| CN114453589B (en) * | 2022-02-18 | 2022-11-29 | 贵研铂业股份有限公司 | Preparation method of high-purity gold |
| CN114620879A (en) * | 2022-03-14 | 2022-06-14 | 苏州诺菲纳米科技有限公司 | Method for recycling waste liquid from silver nanowire production |
| CN115286143A (en) * | 2022-08-17 | 2022-11-04 | 清远先导材料有限公司 | Method for recovering silver from silver-containing waste liquid |
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Application publication date: 20170818 |