CN108374095A - A method of recycling silver from silver-containing solution - Google Patents
A method of recycling silver from silver-containing solution Download PDFInfo
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- CN108374095A CN108374095A CN201810107412.3A CN201810107412A CN108374095A CN 108374095 A CN108374095 A CN 108374095A CN 201810107412 A CN201810107412 A CN 201810107412A CN 108374095 A CN108374095 A CN 108374095A
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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
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The method that the invention discloses a kind of to recycle silver from the silver-containing solution containing inorganic oxysulfide, the pH of the silver-containing solution containing inorganic oxysulfide is adjusted to 7 or more including the method, reducing agent adjustment solution oxide reduction potential is added into silver-containing solution to restore the silver in solution in 300mV or less, then inorganic polymer is added into silver-containing solution again makes the silver-colored flocculation sediment after reduction, by silver recovery.The method of the present invention just can efficiently recycle silver with high-recovery without complicated operation from the silver-containing solution containing the inorganic oxysulfide such as sodium sulfite, have many advantages, such as that stability is good, at low cost.
Description
Technical field
The present invention relates to non-ferrous metallurgy technology field, specifically a kind of method that silver is recycled from silver-containing solution.
Background technology
Silver and its Related product have ten in the industries such as photosensitive industrial, electronics and information industry, plating and chemical engineering industry
Divide extensive purposes, extracts the by-product that the raw material of silver is largely generated from nonferrous metallurgical process, such as copper（Lead）Sun
Pole mud etc..When handling these by-products, extracts reagent of the sodium sulfite as silver is commonly used, makes silver with stable complex form
Into solution, silver is restored with reducing agent again from the complex solution then, obtains the silver powder of higher degree.But
A large amount of low concentration silver-containing liquid waste is often will produce in the process, from wherein recycling silver then becomes urgently in high efficiency and low cost
The problem of solution.
Currently, from Ag-containing solution（Waste liquid）It is middle recycling silver method mainly have the precipitation method, electrolysis, solvent extraction, from
A variety of methods such as sub- exchange process and absorption method.A variety of differences can be used to recycle silver therein in general, handling all kinds of silver-containing liquid wastes
Method or method combination.For example, the method for recycling silver from fixing solution has the precipitation method, displacement method, hypochlorite method, boron hydrogen
Change sodium method, sodium dithionate method and electrolysis etc.（Poplar natural feet precious metals metallurgies product and deep processing [M], Central South University publish
Society, in 2005）.Wherein, 1. the precipitation method are that vulcanized sodium is added into fixing solution, make silver and S2-Reaction generate silver sulfide precipitation with
Solution detaches, and is then recycled from silver sulfide black precipitate with nitric acid dissolution method, roasting the methods of smelting process and iron powder replacement method
Silver.The precipitation method are simple and practicable, and silver recovery is complete, are suitable for using on a small scale, but have excessive vulcanized sodium in the solution after heavy silver,
Fixing solution cannot regenerate, and therefore, be mainly used for the relatively simple silver-containing liquid waste of species of metal ion.2. displacement method be with iron powder,
Zinc powder, aluminium powder make reducing agent, and silver in fixing solution is made to be reduced into elemental silver.This method is efficient, but substitution product is containing silver powder, iron
Powder and silver sulfide etc. will be purified further, while being replaced dissolving metal and being entered in solution, and fixing solution is made to be not easy to regenerate.In acidity
In medium, the thiosulfate anion in fixing solution can decompose, and generate elementary sulfur and sulfur dioxide.3. hypochlorite method is with secondary
Chlorate decomposes silver in waste fixer solution-thiosulfate anion complex, and silver forms silver nitride precipitation and detached with solution.This method
Because to aoxidize a large amount of thiosulfate anion, reagent consumption is larger.4. sodium dithionite method is that pH value of solution is adjusted in
Property, then sodium dithionite is added in waste fixer solution, 60 DEG C is heated to and stirs strongly, silver is precipitated from solution.
This method and process is simple, efficient, the also renewable use of fixing solution, but when pH value is too low or temperature is more than 60 DEG C, Lian Erya
Sodium sulphate or sodium thiosulfate can decompose generation elementary sulfur.5. it is 6 ~ 7 that the silver in sodium borohydride recycling waste fixer solution, which is in pH value,
Under conditions of carry out, the addition of sodium borohydride is slowly added into depending on the silver content in solution in solution, generate silver
Black precipitate.Sodium borohydride has very strong reproducibility, is widely used in chemical analysis field in early days, is just applied to noble metal later
Separation and Extraction, have factory in this way instead of zinc powder, iron replacement method and the vulcanized sodium precipitation method, it is small quantities of in processing
Amount, low concentration silver-containing liquid waste when show its advantage.6. electrolysis recycles the silver in silver-containing liquid waste and fixing solution, in tank voltage
2 ~ 2.2V, 20 ~ 35 DEG C of liquid temperature, 175 ~ 193A/m of current density2Under conditions of, silver in the stoste of 2.5 ~ 9.3g/L of argentiferous can be dropped
Down to 0.5 ~ 0.7g/L.But electrolysis can not carry out under low consistency conditions, and silver-colored mass concentration need to control in solution
200mg/L or more.
The method that silver is recycled from electroplating effluent has electrolysis, the chlorination precipitation method, zinc replacement and active carbon adsorption
Deng since it typically is the solution containing cyanide（For the concentration of silver up to 10 ~ 12g/L, the total concentration of cyanogen root is 80 ~ 100g/L）,
Therefore this kind of waste liquid of processing cannot escape to avoid hydrogen cyanide in operation in acid condition, and cyanogen root concentration must reach related in tail washings
Standard.For example, electrolysis recycling electroplating effluent in silver when, obtain metallic silver in cathode, anode can be by the cyanogen root in solution
It destroys.For electrolytic process using stainless steel plate as cathode, graphite is anode, and after being passed through direct current, silver is precipitated in cathode, and anode releases oxygen
Gas, as the reduction of silver concentration in solution and tank voltage rise, in addition to precipitated oxygen, cyanogen root is also electrochemically oxidized anode（
CN— +2 OH— - 2e = CNO— + H2O, CNO— + 2H2O = NH4 + + CO3 2-, 2CNO— + 8OH— - 6e =
2CO3 2- + N2↑ + 4H2O ）.If still containing a small amount of cyanogen root after electrolysis in solution, it must be made to generate stabilization with ferrous sulfate
Ferrocyanide.
The method that silver is recycled from argentiferous waste emulsion is different and different according to its source.Wherein, the waste emulsion of photographic film
Just be conducive to containing large amount of organic, after need to being first isolated silver recycling, method can generally be divided into thermal process and
Wet processing two major classes.Thermal process includes four dehydration, dry, roasting, melting processes；Wet processing first heats waste emulsion
It to 55 DEG C and is diluted with water, then adding protease to be stirred makes organic matter decompose, and then uses sulfuric acid precipitation, then use sodium thiosulfate
Solution is leached, and finally electrolysis obtains thick silver.And the method that silver is recycled from the argentiferous emulsifier of electric elements and mirror-making factory,
Then since silver mainly exists in the form of silver nitrate, treatment process is relatively easy, i.e., is obtained using direct drying, melting, electrolysis pure
Silver, or dissolved silver therein with nitric acid, then produce silver nitrate.
Solvent extraction because its good economy and operability are widely adopted, but exist need to according to solution properties and
Extracting power, rate of extraction, durability etc. are considered to select extractant appropriate, and the organic extractant after use needs to carry out
The problems such as offal treatment.Using the absorption methods of the adsorbents such as activated carbon, ion exchange resin, there are the adsorption capacities of adsorbent
Small, absorption post-processing is cumbersome, adsorbent reactivation is difficult, and the adsorbent after need to suitably carry out offal treatment etc. and ask
Topic.
In addition to the above method, for the recycling of silver, many researchers have developed for a variety of of different solutions system
Method.For example, patent document CN1200407A discloses a kind of method of extraction and recycling silver, this method will contain microsolubility patina
It closes the raw material of object and contains S2-The organic solution of the organic phosphorus compound of ionic species molecular sulfur mixes, and keeps microsolubility silver compound molten
Silver is extracted into organic phase while solution, then with alkaline sulfite aqueous solution by silver from containing extraction silver organic phase in be stripped
It takes out, then silver is precipitated from anti-stripping agent by reduction reaction.Patent document CN103305700A disclose it is a kind of from
The method that silver is recycled in silver-containing waste water, this method control the pH value of silver-containing waste water 4 ~ 7, after resin adsorption is saturated, use ammonia
Water is desorbed；Light concentration desorption liquid is recycled to be used in the desorption of resin, and high concentration desorption liquid passes sequentially through ultrafiltration apparatus, desalination membrane dress
It sets and is detached, the concentrated water after desalination UF membrane adds the isolated elemental silver of reducing agent.Patent document CN1118015A is disclosed
Ferric trichloride, ferric sulphate solution or poly- will be added in a kind of method of recovering silver from micro-silver contained waste liquid, this method in silver-containing liquid waste
One kind in ferrum sulfuricum oxydatum solutum three is closed, is in iron-containing liquor and Ag-containing solution volume ratio（1.2~8）:1000, room temperature sinking silver,
Then iron is removed with dilute sulfuric acid in a heated condition, sodium carbonate, Boratex, sodium nitrate melting is finally added to obtain product silver.In addition, patent
Document CN101824546A is disclosed from a kind of method of recovering silver from lead-separating liquid of silver-separating residue of copper anode slime, and this method will divide lead liquid to add
Entering sodium hydroxide makes a point lead liquid pH be adjusted to 6 ~ 8, and lead is precipitated in the form of lead hydroxide, and leaded material and the first filter is obtained by filtration
Liquid；Sodium sulphate is added in first filtrate, until solution does not generate precipitation stops that sodium sulphate is added, filter residue and the second filter is obtained by filtration
Liquid；The second filtrate is adjusted into pH value to being not less than 11 with sodium hydroxide again, formaldehyde is added, silver powder and third filtrate is obtained by filtration,
Third filtrate is added hydrochloric acid adjustment pH value and is less than 1, and return divides splicer's sequence.Patent document CN102010036A discloses a kind of silver electricity
Liquid waste solution processing method is silver and copper to be extracted from waste silver electrolyte using cyclone electrolytic cell technology, and liquid reaches useless after making processing
Exclusive row's standard outside water.Waste silver electrolyte is first sent into concatenated cyclone electrolytic cell slot by this method, with low current density and medium stream
Amount（Circular flow 1m3/h~3m3/ h, current density 200A/m2~400A/m2's）It cleans；Then liquid is low in after cleaning
Current density and intermediate flow（Circular flow 2m3/h~5m3/ h, current density 200A/m2~500A/m2）Under the conditions of extract electrolysis
Silver powder；Deep purifying finally is carried out to electrolytic liquid（Circular flow 3m3/h~7m3/ h, current density 200A/m2~400A/m2）,
The waste liquid that makes that treated reaches arranges standard outside waste water.
Invention content
When handling the by-product that nonferrous metallurgical process generates, extracts reagent of the sodium sulfite as silver is commonly used, is made
Silver is entered in the form of stable complex in solution, then with the reagents such as inorganic acid by the solution acidification of argentiferous make silver from
It precipitates in polymer solution, in the silver-colored precipitation into after acidification, after argentiferous precipitates again oxidized purification and reduction treatment
Obtain the silver powder of higher degree.But it also will produce the silver-containing liquid waste of big volume low-concentration during this.Due to including in waste liquid
A large amount of inorganic oxysulfides, silver-colored reduction do not carry out fully, and even if reduction is abundant but since there are inorganic oxysulfides
Silver can be caused insufficient with the flocculation reaction of flocculant, the rate of recovery so as to cause silver is low.Therefore, it is desirable to develop can from containing
Have in the silver-containing liquid waste of the inorganic oxysulfide such as sodium sulfite in the method for high-recovery recycling silver.In view of the foregoing, this hair
Bright is designed to provide a kind of operation without complexity and can be aoxidized from containing inorganic sulfurs such as sodium sulfites with high-recovery
The method that silver is recycled in the silver-containing solution of object.
A kind of method recycling silver from silver-containing solution provided by the invention, includes the following steps：
（1）The pH of silver-containing solution containing inorganic oxysulfide is adjusted to 7 ~ 10；
（2）To step（1）In silver-containing solution in addition reducing agent nano zero valence iron keep solution oxide reduction potential-
In 500mV ~ -300mV ranges, make silver-colored reduction；
（3）To step（2）In silver-containing solution in addition inorganic polymer make the silver-colored flocculation sediment after reduction, by silver recovery；
The inorganic oxysulfide is the salt of at least one of sulphite and bisulfites or more.
Further, in the silver-containing solution containing inorganic oxysulfide inorganic oxysulfide mass concentration be 180 ~
300g/L。
Further, mass concentration silver-colored in the silver-containing solution containing inorganic oxysulfide is 30 ~ 200mg/L.
Further, in the silver-containing solution containing inorganic oxysulfide metal impurities mass concentration be gold 5 ~
20mg/L, 20 ~ 100mg/L of arsenic, 10 ~ 100mg/L of copper.
Further, the inorganic polymer is bodied ferric sulfate and aluminium polychloride.
Further, in the silver-containing solution containing inorganic oxysulfide the content of bodied ferric sulfate in 0.5 ~ 1g/L models
In enclosing, the content of aluminium polychloride is within the scope of 10 ~ 50mg/L.
Compared with prior art, advantages of the present invention and generation good effect are：
A kind of method recycling silver from silver-containing solution provided by the invention, just can be with high-recovery without complicated operation
Efficiently recycling is silver-colored from the silver-containing solution containing the inorganic oxysulfide such as sodium sulfite；The method of the present invention adapt to it is complicated at
Different water simultaneously has preferable stability, simple process and low cost.
Specific implementation mode
Silver-colored reduction and flocculation reaction are difficult to carry out in the silver-containing solution containing the inorganic oxysulfide such as sodium sulfite
The reason of be, Ag-containing solution（Waste liquid）Present in the inorganic oxysulfide such as sodium sulfite form stable complex compound with silver.
Applicant has found by numerous studies, if in the range of the pH of silver-containing liquid waste is adjusted to regulation, addition reducing agent keeps molten
When oxidation reduction potential is less than -300mV, by the fully reduction of the silver in solution, and add after inorganic polymer makes reduction
Silver flocculation is abundant, being capable of efficient recycling silver.
A kind of method recycling silver from silver-containing solution provided by the present invention, basic technology scheme include following step
Suddenly：
（1）The pH of silver-containing solution containing inorganic oxysulfide is adjusted to 7 or more；
Preferably, it is 7 ~ 10 to be adjusted to pH value；It is highly preferred that it is 8 ~ 9 to be adjusted to pH value；
（2）To step（1）In silver-containing solution in addition reducing agent nano zero valence iron keep solution oxide reduction potential-
In 500mV ~ -300mV ranges, make silver-colored reduction；
（3）To step（2）In silver-containing solution in addition inorganic polymer make the silver-colored flocculation sediment after reduction, by silver recovery.
In the method for the present invention, the solution of the object as silver recovery processing is that the argentiferous containing inorganic oxysulfide is water-soluble
Liquid, from being to leach reagent to take the leachate after Leaching of Silver, and acid is carried out by acidizing reagents such as inorganic acids with sodium sulfite
The waste liquid obtained after silver precipitation is isolated after change processing.
Wherein, acidizing reagent can be selected from such as sulfur dioxide gas or sulfuric acid, hydrochloric acid, sulfurous acid inorganic acid.It is above-mentioned
Inorganic oxysulfide specifically can be selected from the salt of at least one of sulphite and bisulfites or more.It is returned as silver
It is silver-colored to be not particularly limited containing concentration in the silver-containing solution for receiving the object of processing, can be any concentration.It is necessary to illustrate
, in acidified treated the silver-containing solution of leachate of silver, silver-colored content is usually 30 ~ 200mg/L.Inorganic sulfur oxygen
The concentration of compound is not particularly limited, and inorganic oxysulfide is usual in acidified treated the silver-containing solution of leachate of silver
For 180 ~ 300g/L.In addition, the compound impurities that can also be formed in the solution containing sulfurous acid and metal, such as sulfurous acid gold
The mass concentration of the sulfurous acid metal compounds such as sodium, sulfurous acid arsenic sodium, sulfurous acid copper sodium, metal impurities is 5 ~ 20mg/L of gold, arsenic
20 ~ 100mg/L, 10 ~ 100mg/L of copper.
The pH of silver-containing solution that will be first dealt with objects as the present invention be adjusted to 7 or more, be preferably adjusted to pH value be 7 ~
10, it is 8 ~ 9 to be more preferably adjusted to pH value；Reducing agent is recycled to carry out the reduction of silver, then adding inorganic polymer makes to be reduced
Silver-colored flocculation sediment out so just can be dramatically improved and recycle silver from the silver-containing solution containing inorganic oxysulfide
The rate of recovery.When pH value is more than 10, even if adding large excess of reducing agent, reduction reaction will not be carried out fully, reducing agent
Utilization ratio declines, and silver raising recovery rate reduces.On the other hand, when pH value is less than 7, pH carries out reduction process after adjusting and then needs to put into
A large amount of reducing agents, silver-colored reduction efficiency are low.It must be obtained it is noted that being isolated after the acidified processing of leachate of silver after silver precipitates
Waste liquid（Silver-containing solution i.e. in the method for the present invention as the object of silver recovery processing）PH value be 3 ~ 6 or so.In order to incite somebody to action
The pH of silver-containing solution is adjusted to 7 or more, pH adjusting agent can be added into the silver-containing solution, pH adjusting agent does not limit, excellent
Choosing uses economically viable sodium hydroxide to adjust reagent as pH.
Used reducing agent is restored, it is preferable to use nano zero valence iron as by silver in silver-containing solution.The nanometer zero
Valence iron is not particularly limited, its general grain size is 10 ~ 200nm.In the present invention, by adding reducing agent zeroth order Nanoscale Iron by solution
Oxidation-reduction potential be adjusted to -300mV ~ -500mV.In the range of the oxidation-reduction potential of solution is -300mV ~ -500mV
When, the silver in solution can efficiently be restored.Further preferred oxidation-reduction potential is -350mV ~ -450mV.It is added also
When the oxidation-reduction potential of former agent adjustment solution is higher than -300mV, then the silver reduction in solution is insufficient, and silver-colored reduction efficiency is low.Separately
On the one hand, when adjusting the oxidation-reduction potential of solution and being less than -500mV, then need to add further amounts of go back original reagent, in cost
It rises.Above-mentioned reduction process carries out at normal temperatures, and processing time when reaction is usually 15 ~ 60 minutes or so.It must be noted that
Oxidation-reduction potential is to measure reference electrode to use silver-silver chloride electrode, the benchmark being inserted into aqueous solution electricity in the present invention
It is worth obtained from the potential difference of pole and metal electrode（mV）.
By adding inorganic polymer into above-mentioned silver-containing solution, make the silver-colored flocculation sediment after reduction, to return silver
It receives.Remain inorganic oxysulfide in the silver-containing solution, which can hinder flocculant to be brought
Silver flocculating effect, interfere silver flocculation, inorganic polymer need be added.As the inorganic polymeric for improving silver-colored flocculating effect
Object is, it is preferable to use bodied ferric sulfate and aluminium polychloride.It is stirred to react 5 ~ 10 minutes, is then added poly- after bodied ferric sulfate is added
It closes object aluminium chloride and is stirred for reaction 5 ~ 10 minutes, then silver-colored flocculation is promoted, and the silver-colored rate of recovery improves.Inorganic polymer is added
Preceding processing method is to put into inorganic polymer while stirring in the container for filling water, continues addition water and continues to stir to this
Inorganic polymer all dissolves.The content of bodied ferric sulfate is within the scope of 0.5 ~ 1g/L in the silver-containing solution, polyaluminium
The content of aluminium is within the scope of 10 ~ 50mg/L.
Embodiment 1
The pH of the silver-containing solution containing inorganic oxysulfide is adjusted to 7 using sodium hydroxide, it is water-soluble to state argentiferous then up
Reducing agent nano zero valence iron adjustment solution oxide reduction potential is added in liquid to -300mV, is stirred to react 30 minutes, then to containing
Inorganic polymer bodied ferric sulfate 500mg/L is added in silver-colored aqueous solution, is stirred to react 5 minutes, is then added aluminium polychloride
10mg/L is stirred to react 10 minutes.The pH value for wherein containing the silver-containing solution of inorganic oxysulfide is 5, silver-colored mass concentration
Mass concentration for 100mg/L, sodium hydrogensulfite is 220g/L.The rate of recovery of silver is 98.5%.
Embodiment 2
The pH of the silver-containing solution containing inorganic oxysulfide is adjusted to 8 using sodium hydroxide, it is water-soluble to state argentiferous then up
Reducing agent nano zero valence iron adjustment solution oxide reduction potential is added in liquid to -350mV, is stirred to react 20 minutes, then to containing
Inorganic polymer bodied ferric sulfate 600mg/L is added in silver-colored aqueous solution, is stirred to react 10 minutes, is then added aluminium polychloride
20mg/L is stirred to react 5 minutes.The pH value for wherein containing the silver-containing solution of inorganic oxysulfide is 5, and silver-colored mass concentration is
The mass concentration of 100mg/L, sodium hydrogensulfite are 220g/L.The rate of recovery of silver is 98.2%.
Embodiment 3
The pH of the silver-containing solution containing inorganic oxysulfide is adjusted to 9 using sodium hydroxide, it is water-soluble to state argentiferous then up
Reducing agent nano zero valence iron adjustment solution oxide reduction potential is added in liquid to -400mV, is stirred to react 40 minutes, then to containing
Inorganic polymer bodied ferric sulfate 500mg/L is added in silver-colored aqueous solution, is stirred to react 10 minutes, is then added aluminium polychloride
20mg/L is stirred to react 5 minutes.The pH value for wherein containing the silver-containing solution of inorganic oxysulfide is 4, and silver-colored mass concentration is
The mass concentration of 100mg/L, sodium hydrogensulfite are 220g/L.The rate of recovery of silver is 99.0%.
Embodiment 4
The pH of the silver-containing solution containing inorganic oxysulfide is adjusted to 8 using sodium hydroxide, it is water-soluble to state argentiferous then up
Reducing agent nano zero valence iron adjustment solution oxide reduction potential is added in liquid to -350mV, is stirred to react 20 minutes, then to containing
Inorganic polymer bodied ferric sulfate 800mg/L is added in silver-colored aqueous solution, is stirred to react 10 minutes, is then added aluminium polychloride
40mg/L is stirred to react 5 minutes.The pH value for wherein containing the silver-containing solution of inorganic oxysulfide is 5, and silver-colored mass concentration is
The mass concentration of 100mg/L, sodium hydrogensulfite are 220g/L.The rate of recovery of silver is 98.4%.
Embodiment 5
The pH of the silver-containing solution containing inorganic oxysulfide is adjusted to 8 using sodium hydroxide, it is water-soluble to state argentiferous then up
Reducing agent nano zero valence iron adjustment solution oxide reduction potential is added in liquid to -500mV, is stirred to react 20 minutes, then to containing
Inorganic polymer bodied ferric sulfate 900mg/L is added in silver-colored aqueous solution, is stirred to react 10 minutes, is then added aluminium polychloride
20mg/L is stirred to react 5 minutes.The pH value for wherein containing the silver-containing solution of inorganic oxysulfide is 3, and silver-colored mass concentration is
The mass concentration of 30mg/L, sodium hydrogensulfite are 180g/L.The rate of recovery of silver is 98.0%.
Embodiment 6
The pH of the silver-containing solution containing inorganic oxysulfide is adjusted to 9 using sodium hydroxide, it is water-soluble to state argentiferous then up
Reducing agent nano zero valence iron adjustment solution oxide reduction potential is added in liquid to -400mV, is stirred to react 30 minutes, then to containing
Inorganic polymer bodied ferric sulfate 1000mg/L is added in silver-colored aqueous solution, is stirred to react 10 minutes, is then added polyaluminium
Aluminium 30mg/L is stirred to react 10 minutes.The pH value for wherein containing the silver-containing solution of inorganic oxysulfide is 4, and silver-colored quality is dense
Degree is 200mg/L, and the mass concentration of sodium hydrogensulfite is 300g/L.The rate of recovery of silver is 98.6%.
Embodiment 7
The pH of the silver-containing solution containing inorganic oxysulfide is adjusted to 8 using sodium hydroxide, it is water-soluble to state argentiferous then up
Reducing agent nano zero valence iron adjustment solution oxide reduction potential is added in liquid to -500mV, is stirred to react 30 minutes, then to containing
Inorganic polymer bodied ferric sulfate 700mg/L is added in silver-colored aqueous solution, is stirred to react 10 minutes, is then added aluminium polychloride
30mg/L is stirred to react 10 minutes.The pH value for wherein containing the silver-containing solution of inorganic oxysulfide is 5, silver-colored mass concentration
Mass concentration for 200mg/L, sodium hydrogensulfite is 220g/L.The rate of recovery of silver is 98.7%.
Above-described embodiment is only the more excellent embodiment of the present invention, every according to the technical essence of the invention to implementing above
Any simple modification, modification and the alternate variation that example is made, belong in the range of technical solution of the present invention.
Claims (6)
1. a kind of method recycling silver from silver-containing solution, it is characterised in that：Include the following steps：
（1）The pH of silver-containing solution containing inorganic oxysulfide is adjusted to 7 ~ 10；
（2）To step（1）In silver-containing solution in addition reducing agent nano zero valence iron keep solution oxide reduction potential-
In 500mV ~ -300mV ranges, make silver-colored reduction；
（3）To step（2）In silver-containing solution in addition inorganic polymer make the silver-colored flocculation sediment after reduction, by silver recovery；
The inorganic oxysulfide is the salt of at least one of sulphite and bisulfites or more.
2. a kind of method recycling silver from silver-containing solution according to claim 1, it is characterised in that：It is described containing whether there is or not
The mass concentration of inorganic oxysulfide is 180 ~ 300g/L in the silver-containing solution of machine oxysulfide.
3. a kind of method recycling silver from silver-containing solution according to claim 1, it is characterised in that：It is described containing whether there is or not
Silver-colored mass concentration is 30 ~ 200mg/L in the silver-containing solution of machine oxysulfide.
4. a kind of method recycling silver from silver-containing solution according to claim 1, it is characterised in that：It is described containing whether there is or not
In the silver-containing solution of machine oxysulfide the mass concentration of metal impurities be 5 ~ 20mg/L of gold, 20 ~ 100mg/L of arsenic, copper 10 ~
100mg/L。
5. a kind of method recycling silver from silver-containing solution according to claim 1, it is characterised in that：It is described inorganic poly-
It is bodied ferric sulfate and aluminium polychloride to close object.
6. a kind of method recycling silver from silver-containing solution according to claim 1, it is characterised in that：It is described containing whether there is or not
The content of bodied ferric sulfate is within the scope of 0.5 ~ 1g/L in the silver-containing solution of machine oxysulfide, and the content of aluminium polychloride is 10
Within the scope of ~ 50mg/L.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467272A (en) * | 2018-12-19 | 2019-03-15 | 河北德龙环境工程股份有限公司 | A kind of sewage-treatment plant and method |
| 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 |
| CN114150153A (en) * | 2021-11-03 | 2022-03-08 | 深圳市世清环保科技有限公司 | Method for recycling silver-containing waste nitric acid and recovering silver |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02243726A (en) * | 1988-10-24 | 1990-09-27 | E I Du Pont De Nemours & Co | Process for recovering silver |
| CN1648063A (en) * | 2004-12-21 | 2005-08-03 | 李迎来 | Mixed flocculant for treating waste water containing oil |
| CN102583689A (en) * | 2012-02-22 | 2012-07-18 | 同济大学 | Method and device for removing heavy metal in electroplating wastewater through nanoscale zero-valent iron-electromagnetic system |
| CN102951749A (en) * | 2012-11-12 | 2013-03-06 | 同济大学 | Method and device for removing heavy metals in industrial wastewater by nanoscale zero-valent iron-multilevel reversed filter type system |
| CN105154685A (en) * | 2015-06-04 | 2015-12-16 | 昆山鸿福泰环保科技有限公司 | Technology for recovering gold by potentiometer control method |
| CN105814216A (en) * | 2013-12-03 | 2016-07-27 | 田中贵金属工业株式会社 | Method for collecting palladium |
-
2018
- 2018-02-02 CN CN201810107412.3A patent/CN108374095B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02243726A (en) * | 1988-10-24 | 1990-09-27 | E I Du Pont De Nemours & Co | Process for recovering silver |
| CN1648063A (en) * | 2004-12-21 | 2005-08-03 | 李迎来 | Mixed flocculant for treating waste water containing oil |
| CN102583689A (en) * | 2012-02-22 | 2012-07-18 | 同济大学 | Method and device for removing heavy metal in electroplating wastewater through nanoscale zero-valent iron-electromagnetic system |
| CN102951749A (en) * | 2012-11-12 | 2013-03-06 | 同济大学 | Method and device for removing heavy metals in industrial wastewater by nanoscale zero-valent iron-multilevel reversed filter type system |
| CN105814216A (en) * | 2013-12-03 | 2016-07-27 | 田中贵金属工业株式会社 | Method for collecting palladium |
| CN105154685A (en) * | 2015-06-04 | 2015-12-16 | 昆山鸿福泰环保科技有限公司 | Technology for recovering gold by potentiometer control method |
Non-Patent Citations (1)
| Title |
|---|
| 孙宏主编: "《表面活性剂在分析化学和环境上的应用》", 31 January 2006, 哈尔滨：哈尔滨地图出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467272A (en) * | 2018-12-19 | 2019-03-15 | 河北德龙环境工程股份有限公司 | A kind of sewage-treatment plant and method |
| 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 |
| CN114150153A (en) * | 2021-11-03 | 2022-03-08 | 深圳市世清环保科技有限公司 | Method for recycling silver-containing waste nitric acid and recovering silver |
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