CN107313072A - A kind of method of comprehensive utilization of silver anode cloth bag wash water - Google Patents
A kind of method of comprehensive utilization of silver anode cloth bag wash water Download PDFInfo
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- CN107313072A CN107313072A CN201710515325.7A CN201710515325A CN107313072A CN 107313072 A CN107313072 A CN 107313072A CN 201710515325 A CN201710515325 A CN 201710515325A CN 107313072 A CN107313072 A CN 107313072A
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- filtrate
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
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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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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a kind of method of comprehensive utilization of silver anode cloth bag wash water, comprise the following steps：(1) silver anode cloth bag wash water is filtered, the first filtrate and filter residue is collected respectively；(2) sodium hydroxide solution is added and reacted in the first filtrate, the second filtrate and silver oxide are collected in filtering respectively；(3) filtered after silver oxide is washed with clear water, wet oxidation silver and wash water are collected respectively；Wet oxidation silver is added in pending silver electrolyte, reaction purification silver electrolyte, it is to be clean after the completion of, the silver electrolyte of filtering respectively after collection and purification slag and purification；(4) acidity will be adjusted after the silver electrolyte dilution after purification, finally returns to silver-colored electrolytic cell.The processing method of the present invention is simple, pollution-free, and the silver ion of pilot process is used as the supplement of electrolyte silver ion, improves the direct yield and comprehensive utilization ratio of silver, silver-colored direct yield is up to 96%.
Description
Technical field
The present invention relates to metal technical field of wet metallurgy, and in particular to a kind of comprehensive utilization side of silver anode cloth bag wash water
Method.
Background technology
Electrolytic refining process is the common method for preparing high pure metal.It is to make anode with thick silver such as the electrorefining processes of silver,
Titanium plate makees negative electrode, and silver nitrate aqueous solution makees electrolyte, in 1.5~3.5V of DC voltage, 250~300A/m of electric current2Under conditions of
The silver of refining available 99.99%.In silver-colored electrolytic process, there are several places to produce Ag-containing solution, and silver content is very high, for example：Silver
Powder pickling and rinsing solution (60~85g/L), silver anode cloth bag aqueous solution (175~285g/L of concentration of silver ions), it is most of
When, because silver powder pickling and rinsing solution are purer silver nitrate solution, it is often used as electrolyte replenisher.
Thick silver typically all contains the plurality of impurities such as Au, Pt, Pd and base metal Pb, Cu, Bi before electrolysis.In electrolytic process
In, the electrode potential gold bigger than silver and platinum group metal will not largely dissolve and precipitate, the electrode potential low-priced gold smaller than silver
A category impurity part, which can form oxide or basic salt, can also be precipitated, and these sediments are fallen into anode.Time one is grown
Anode cloth bag can be blocked by these sediments, so that the flowing of electrolyte is hindered, so necessary periodic cleaning anode cloth bag,
So as to obtain anode cloth bag wash water.The processing to anode cloth bag wash water is periodically silver to avale in the prior art, returns to silver-colored smelting
Refining system, melting again, this considerably increases cost recovery.The present invention proposes a kind of comprehensive utilization side of silver anode cloth bag wash water
Method, has recycled the silver in silver-colored electrolytic process to the full extent.
The content of the invention
In view of this, it is an object of the invention to propose a kind of method of comprehensive utilization of silver anode cloth bag wash water, this method
Silver in Comprehensive Recovery of Ag electrolytic process, is directly used in silver-colored electrolysis system, reduces energy consumption, simple to operate, what pilot process was produced
Waste liquid is environment-friendly, disposable.
A kind of method of comprehensive utilization of the silver anode cloth bag wash water provided based on above-mentioned purpose, the present invention, including following step
Suddenly：
(1) processing of silver anode cloth bag wash water
By the filtering of silver anode cloth bag wash water, the first filtrate and filter residue are collected respectively；
(2) synthesis of silver oxide
Sodium hydroxide solution is added and reacted in the first filtrate, the second filtrate and silver oxide are collected in filtering respectively；
(3) purification of silver electrolyte
Filtered after silver oxide is washed with clear water, wet oxidation silver and wash water are collected respectively；Wet oxidation silver is added into silver electrolysis
In liquid, reaction purification silver electrolyte, it is to be clean after the completion of, filtering respectively collection and purification slag and purification after silver electrolyte；
(4) pre-treatment that silver electrolyte is returned
Acidity will be adjusted after silver electrolyte dilution after purification, finally return to silver-colored electrolytic cell.
In the present invention, silver oxide is cleaned with clear water, washes away the sodium nitrate of entrainment, prevent sodium ion from entering system.
In the present invention, it is preferred to, by the filter residue it is silver anode slime in step (1), filter residue is returned into silver anode slime system
System.
In the present invention, it is preferred to, silver ion and copper ion, silver ion, copper are included described in step (2) in the first filtrate
The amount ratio of the material of ion and sodium hydroxide is：n(Ag+2Cu):N (NaOH)=1:0.8~1.2；By sodium hydroxide solution progressively
Add in the first filtrate, stirring reaction 1~2 hour.
In the present invention, it is preferred to, add aqueous slkali in the second filtrate in step (2) and carry out heavy silver, reclaim silver precipitation,
And silver precipitation is returned into silver-colored smelting system.
In the present invention, it is preferred to, the moisture in step (3) in wet oxidation silver is 48%~52%；The wash water
Return to wastewater treatment.
In the present invention, it is preferred to, the composition of pending silver electrolyte is described in step (3)：Ag:280.07~
285.12g/L, Cu:20.12~22.32g/L, Bi:0.2023~0.2265g/L, Pb:0.2081~0.2258g/L, Pd:
0.1012~0.1235g/L, acidity:8.05~8.36g/L；According to the nitric acid and the thing of silver oxide in pending silver electrolyte
The amount of matter is：n(HNO3):N (AgO)=2:1, the quality of silver oxide is calculated, then the moisture in wet oxidation silver
Converse the quality for the wet oxidation silver for needing to add；The amount of the material of nitric acid in wherein pending silver electrolyte is pending
Silver electrolyte in nitric acid material the summation of the amount of the material of nitric acid that comes out plus copper water solution of amount.
In the present invention, it is preferred to, the temperature of silver electrolyte is 88~92 DEG C in step (3), and wet oxidation silver is divided
Step is added in 88~92 DEG C of silver electrolyte, 1~4 hour purification silver electrolyte of stirring reaction.
In the present invention, it is preferred to, in step (4) by the silver electrolyte after purification be diluted to the concentration of silver ion for 80~
120g/L, is 7~9g/L by the silver electrolyte nitric acid regulation acidity after dilution.
Compared with prior art, the invention has the advantages that：
(1) method of comprehensive utilization of silver anode cloth bag wash water of the present invention is simple to operate, raw materials used directly middle for production
Process product, improves raw material availability.
(2) present invention will not produce harmful waste water, and the solution partial neutral of output is nontoxic, benefit reason, environmental protection.
(3) present invention is using the Ag-containing solution during silver-colored electrolysis production, and final silver ion returns to silver electrolysis again after processing
In liquid, the process is to have handled the impurity in silver electrolyte, while supplementing the silver ion in silver electrolyte again, is achieved many things at one stroke,
The direct yield of silver is improved, silver-colored direct yield is up to 96%, and the comprehensive utilization ratio of silver ion is high.
Brief description of the drawings
Fig. 1 is a kind of process chart of the method for comprehensive utilization of silver anode cloth bag wash water of the present invention.
Embodiment
For the object, technical solutions and advantages of the present invention are more clearly understood, below in conjunction with specific embodiment, to this
Invention is further described.
The present invention relates to a kind of method of comprehensive utilization of silver anode cloth bag wash water, specific method is：Silver anode cloth bag is washed
The earth of positive pole suspended in water is filtered out, then in filtrate add equimolar than sodium hydroxide solution, synthesize silver oxide, filtering
Afterwards, storage tank will be returned containing a small amount of silver-colored filtrate to be recycled, filtering after silver oxide is washed with clear water finally obtains wet oxidation silver, by oxygen
Change silver to add according to a certain percentage in pending silver electrolyte, reaction purification silver electrolyte (90 DEG C are reacted 1~4 hour) is treated
After the completion of purification, the silver electrolyte being filtrated to get is diluted after the electrolyte (regulation concentration of silver ions), last nitric acid regulation acidity
Return to silver-colored electrolytic cell.
Embodiment 1
Referring to Fig. 1, it is the process chart of the method for comprehensive utilization of silver anode cloth bag wash water of the embodiment of the present invention.
A kind of method of comprehensive utilization of silver anode cloth bag wash water comprises the following steps：
(1) processing of silver anode cloth bag wash water
10L silver anode cloth bag wash waters are taken, filters, the first filtrate and filter residue is collected respectively, filter residue (i.e. silver anode slime) is returned
Return the concentration (Ag of silver ion and copper ion in silver anode slime heap, the first filtrate of detection:261g/L, Cu:16g/L).
(2) synthesis of silver oxide
According to silver ion in the first filtrate and the concentration (Ag of copper ion:261g/L, Cu:16g/L) calculate Ag and Cu thing
The amount of matter, be according to the amount ratio of the material of silver ion, copper ion and sodium hydroxide：n(Ag+2Cu):N (NaOH)=1:1, calculate
Go out the amount of the material of sodium hydroxide, be specifically calculated as：Sodium hydroxide n (NaOH)=24+2.5 × 2=29mol (i.e. 1160g),
1160g sodium hydroxides are dissolved in water, are then gradually adding in filtrate, and stirring reaction synthesizes silver oxide after 1 hour, and filtering is received respectively
Collection obtains silver oxide and the second filtrate, and the second filtrate now contains addition in a small amount of silver ion (0.1132g/L), the second filtrate
Aqueous slkali progress is heavy silver-colored, and recovery silver is precipitated, and silver is precipitated into liquid return wastewater treatment after the silver-colored smelting system of return, heavy silver.
(3) purification of silver electrolyte
Silver oxide is washed away to the sodium nitrate solution for removing entrainment with clear water, it is to avoid sodium nitrate enters in silver oxide, then filters,
Wet oxidation silver and wash water are collected respectively, and the wash water returns to wastewater treatment；The moisture in silver oxide is drained as far as possible, obtains wet oxidation silver
6170g, it is 50% to measure the silver-colored moisture of wet oxidation；Take pending silver electrolyte 10L (Ag:283.07g/L, Cu:21.58g/L,
Bi:0.2265g/L, Pb:0.2158g/L, Pd:0.1235g/L, acidity:8.29g/L), the pending silver electrolytes of 10L are calculated
The quality of the middle wet oxidation silver for needing to add, specific calculating process is：The nitric acid amount that pending silver electrolyte contains in itself
(8.29g/L), the nitric acid amount that copper water solution can go out is calculated according to reaction equation：Cu(NO3)2+2H2O=Cu (OH)2+2HNO3, 215.8/
The amount of the material of total nitric acid in 64 × 2 × 63=424.86g/L, i.e., pending silver electrolyte is：8.29/63+424.86/
63=6.88mol, be then according to the amount ratio of nitric acid and the material of silver oxide：Nitric acid:Silver oxide=2:1, calculate silver oxide
The amount of material be 3.44mol, it is necessary to which the quality for adding silver oxide is：3.44 × 231.73=797g, is converted into 50% wet oxygen
The quality for changing silver is 1595g；Pending silver electrolyte is heated, when temperature is 90 DEG C, wet oxidation silver substep is added pending
Silver electrolyte in, stirring reaction 2 hours, it is to be clean after the completion of, filter while hot, clean, respectively collection and purification slag and purification after
Silver electrolyte (Ag:258.59g/L, Cu:0.9848g/L).
(4) pre-treatment that silver electrolyte is returned
Silver electrolyte after purification is diluted to Ag 120g/L, it is 9g/L to adjust electrolyte acidity with nitric acid, finally should
The electrolyte handled well returns to silver-colored electrolytic cell.
Using the method for the present embodiment, silver-colored direct yield is that can reach 96.0%.
Embodiment 2
Referring to Fig. 1, it is the process chart of the method for comprehensive utilization of silver anode cloth bag wash water of the embodiment of the present invention.
A kind of method of comprehensive utilization of silver anode cloth bag wash water comprises the following steps：
(1) processing of silver anode cloth bag wash water
10L silver anode cloth bag wash waters are taken, filters, the first filtrate and filter residue is collected respectively, filter residue (i.e. silver anode slime) is returned
Return the concentration (Ag of silver ion and copper ion in silver anode slime heap, the first filtrate of detection:285g/L, Cu:20g/L).
(2) synthesis of silver oxide
According to silver ion in the first filtrate and the concentration (Ag of copper ion:285g/L, Cu:20g/L) calculate Ag and Cu thing
The amount of matter, be according to the amount ratio of the material of silver ion, copper ion and sodium hydroxide：n(Ag+2Cu):N (NaOH)=1:1, calculate
Go out the amount of the material of sodium hydroxide, be specifically calculated as：Sodium hydroxide n (NaOH)=26+3.1 × 2=32.2mol (i.e. 1288g),
1288g sodium hydroxides are dissolved in water, are then gradually adding in filtrate, and stirring reaction synthesizes silver oxide after 2 hours, and filtering is received respectively
Collection obtains silver oxide and the second filtrate, and the second filtrate now contains addition in a small amount of silver ion (0.1242g/L), the second filtrate
Aqueous slkali progress is heavy silver-colored, and recovery silver is precipitated, and silver is precipitated into liquid return wastewater treatment after the silver-colored smelting system of return, heavy silver.
(3) purification of silver electrolyte
Silver oxide is washed away to the sodium nitrate solution for removing entrainment with clear water, it is to avoid sodium nitrate enters in silver oxide, then filters,
Wet oxidation silver and wash water are collected respectively, and the wash water returns to wastewater treatment；The moisture in silver oxide is drained as far as possible, obtains wet oxidation silver
7270g, it is 48% to measure the silver-colored moisture of wet oxidation；Take pending silver electrolyte 10L (Ag:280.07g/L, Cu:20.12g/L,
Bi:0.2023g/L, Pb:0.2081g/L, Pd:0.1012g/L, acidity:8.05g/L), the pending silver electrolytes of 10L are calculated
The quality of the middle wet oxidation silver for needing to add, specific calculating process is：The nitric acid amount that pending silver electrolyte contains in itself
(8.05g/L), the nitric acid amount that copper water solution can go out is calculated according to reaction equation：Cu(NO3)2+2H2O=Cu (OH)2+2HNO3, 201.8/
The amount of the material of total nitric acid in 64 × 2 × 63=397.29g/L, i.e., pending silver electrolyte is：8.05/63+397.29/
63=6.44mol, be then according to the amount ratio of nitric acid and the material of silver oxide：Nitric acid:Silver oxide=2:1, calculate silver oxide
The amount of material be 3.22mol, it is necessary to which the quality for adding silver oxide is：3.22 × 231.73=746g, is converted into 48% wet oxygen
The quality for changing silver is 1435g；Pending silver electrolyte is heated, when temperature is 88 DEG C, wet oxidation silver substep is added pending
Silver electrolyte in, stirring reaction 1 hour, it is to be clean after the completion of, filter while hot, clean, respectively collection and purification slag and purification after
Silver electrolyte (Ag:242.55g/L, Cu:0.8348g/L).
(4) pre-treatment that silver electrolyte is returned
Silver electrolyte after purification is diluted to Ag 90g/L, it is 7g/L to adjust electrolyte acidity with nitric acid, finally should
The electrolyte handled well returns to silver-colored electrolytic cell.
Using the method for the present embodiment, silver-colored direct yield is that can reach 95.5%.
Embodiment 3
Referring to Fig. 1, it is the process chart of the method for comprehensive utilization of silver anode cloth bag wash water of the embodiment of the present invention.
A kind of method of comprehensive utilization of silver anode cloth bag wash water comprises the following steps：
(1) processing of silver anode cloth bag wash water
10L silver anode cloth bag wash waters are taken, filters, the first filtrate and filter residue is collected respectively, filter residue (i.e. silver anode slime) is returned
Return the concentration (Ag of silver ion and copper ion in silver anode slime heap, the first filtrate of detection:175g/L, Cu:15g/L).
(2) synthesis of silver oxide
According to silver ion in the first filtrate and the concentration (Ag of copper ion:175g/L, Cu:15g/L) calculate Ag and Cu thing
The amount of matter, be according to the amount ratio of the material of silver ion, copper ion and sodium hydroxide：n(Ag+2Cu):N (NaOH)=1:1, calculate
Go out the amount of the material of sodium hydroxide, be specifically calculated as：Sodium hydroxide n (NaOH)=16+2.3 × 2=20.6mol (i.e. 824g),
824g sodium hydroxides are dissolved in water, are then gradually adding in filtrate, and stirring reaction synthesizes silver oxide after 1.5 hours, filters, respectively
Collection obtains silver oxide and the second filtrate, the second filtrate now contain in a small amount of silver ion (0.1042g/L), the second filtrate plus
Enter the heavy silver of aqueous slkali progress, reclaim silver and precipitate, and silver precipitation is returned into liquid after silver-colored smelting system, heavy silver and return to wastewater treatment.
(3) purification of silver electrolyte
Silver oxide is washed away to the sodium nitrate solution for removing entrainment with clear water, it is to avoid sodium nitrate enters in silver oxide, then filters,
Wet oxidation silver and wash water are collected respectively, and the wash water returns to wastewater treatment；The moisture in silver oxide is drained as far as possible, obtains wet oxidation silver
4235g, it is 52% to measure the silver-colored moisture of wet oxidation；Take pending silver electrolyte 10L (Ag:285.12g/L, Cu:22.32g/L,
Bi:0.2265g/L, Pb:0.2258g/L, Pd:0.1235g/L, acidity:8.36g/L), the pending silver electrolytes of 10L are calculated
The quality of the middle wet oxidation silver for needing to add, specific calculating process is：The nitric acid amount that pending silver electrolyte contains in itself
(8.36g/L), the nitric acid amount that copper water solution can go out is calculated according to reaction equation：Cu(NO3)2+2H2O=Cu (OH)2+2HNO3, 223.2/
The amount of the material of total nitric acid in 64 × 2 × 63=439.43g/L, i.e., pending silver electrolyte is：8.36/63+439.43/
63=7.11mol, be then according to the amount ratio of nitric acid and the material of silver oxide：Nitric acid:Silver oxide=2:1, calculate silver oxide
The amount of material be 3.56mol, it is necessary to which the quality for adding silver oxide is：3.56 × 231.73=825g, is converted into 52% wet oxygen
The quality for changing silver is 1719g；Pending silver electrolyte is heated, when temperature is 92 DEG C, wet oxidation silver substep is added pending
Silver electrolyte in, stirring reaction 3 hours, it is to be clean after the completion of, filter while hot, clean, respectively collection and purification slag and purification after
Silver electrolyte (Ag:241.45g/L, Cu:0.9632g/L).
(4) pre-treatment that silver electrolyte is returned
Silver electrolyte after purification is diluted to Ag 80g/L, it is 8g/L to adjust electrolyte acidity with nitric acid, finally should
The electrolyte handled well returns to silver-colored electrolytic cell.
Using the method for the present embodiment, silver-colored direct yield is that can reach 95.8%.
Embodiment 4
Referring to Fig. 1, it is the process chart of the method for comprehensive utilization of silver anode cloth bag wash water of the embodiment of the present invention.
A kind of method of comprehensive utilization of silver anode cloth bag wash water comprises the following steps：
(1) processing of silver anode cloth bag wash water
10L silver anode cloth bag wash waters are taken, filters, the first filtrate and filter residue is collected respectively, filter residue (i.e. silver anode slime) is returned
Return the concentration (Ag of silver ion and copper ion in silver anode slime heap, the first filtrate of detection:200g/L, Cu:18g/L).
(2) synthesis of silver oxide
According to silver ion in the first filtrate and the concentration (Ag of copper ion:200g/L, Cu:18g/L) calculate Ag and Cu thing
The amount of matter, be according to the amount ratio of the material of silver ion, copper ion and sodium hydroxide：n(Ag+2Cu):N (NaOH)=1:1, calculate
Go out the amount of the material of sodium hydroxide, be specifically calculated as：Sodium hydroxide n (NaOH)=18.5+2.8 × 2=24.1mol is (i.e.
964g), 964g sodium hydroxides are dissolved in water, are then gradually adding in filtrate, and stirring reaction synthesizes silver oxide, mistake after 1.8 hours
Filter, collects obtain silver oxide and the second filtrate respectively, the second filtrate now contains a small amount of silver ion (0.1085g/L), second
The heavy silver of aqueous slkali progress is added in filtrate, silver is reclaimed and precipitates, and silver precipitation is returned into liquid after silver-colored smelting system, heavy silver and returns to waste water
Processing.
(3) purification of silver electrolyte
Silver oxide is washed away to the sodium nitrate solution for removing entrainment with clear water, it is to avoid sodium nitrate enters in silver oxide, then filters,
Wet oxidation silver and wash water are collected respectively, and the wash water returns to wastewater treatment；The moisture in silver oxide is drained as far as possible, obtains wet oxidation silver
5235g, it is 50% to measure the silver-colored moisture of wet oxidation；Take pending silver electrolyte 10L (Ag:283.56g/L, Cu:21.52g/L,
Bi:0.2145g/L, Pb:0.2181g/L, Pd:0.1125g/L, acidity:8.25g/L), the pending silver electrolytes of 10L are calculated
The quality of the middle wet oxidation silver for needing to add, specific calculating process is：The nitric acid amount that pending silver electrolyte contains in itself
(8.25g/L), the nitric acid amount that copper water solution can go out is calculated according to reaction equation：Cu(NO3)2+2H2O=Cu (OH)2+2HNO3, 215.2/
The amount of the material of total nitric acid in 64 × 2 × 63=423.68g/L, i.e., pending silver electrolyte is：8.25/63+423.68/
63=6.86mol, be then according to the amount ratio of nitric acid and the material of silver oxide：Nitric acid:Silver oxide=2:1, calculate silver oxide
The amount of material be 3.43mol, it is necessary to which the quality for adding silver oxide is：3.43 × 231.73=795g, is converted into 50% wet oxygen
The quality for changing silver is 1590g；Pending silver electrolyte is heated, when temperature is 90 DEG C, wet oxidation silver substep is added pending
Silver electrolyte in, stirring reaction 4 hours, it is to be clean after the completion of, filter while hot, clean, respectively collection and purification slag and purification after
Silver electrolyte (Ag:250.25g/L, Cu:0.9582g/L).
(4) pre-treatment that silver electrolyte is returned
Silver electrolyte after purification is diluted to Ag 110g/L, it is 8.5g/L to adjust electrolyte acidity with nitric acid, finally will
The electrolyte handled well returns to silver-colored electrolytic cell.
Using the method for the present embodiment, silver-colored direct yield is that can reach 96.0%.
In summary, the method for comprehensive utilization of silver anode cloth bag wash water of the present invention is simple to operate, raw materials used directly to make a living
Pilot process product is produced, raw material availability is improved.The present invention will not produce harmful waste water, and the solution partial neutral of output is nontoxic, good
Processing, environmental protection.The present invention is using the Ag-containing solution during silver-colored electrolysis production, and final silver ion returns to silver electrolyte again after processing
In, the process is to have handled the impurity in silver electrolyte, while supplementing the silver ion in silver electrolyte again, achieves many things at one stroke, carries
The high direct yield of silver, silver-colored direct yield is up to 96%, and the comprehensive utilization ratio of silver ion is high.
Those of ordinary skills in the art should understand that：The discussion of any of the above embodiment is exemplary only, not
It is intended to imply that the scope of the present disclosure (including claim) is limited to these examples；Under the thinking of the present invention, above example
Or can also not be combined between the technical characteristic in be the same as Example, and there is the different aspect of the present invention as described above
Many other changes, in order to it is concise they provided not in details.Therefore, within the spirit and principles of the invention,
Any omission, modification, equivalent substitution, improvement for being made etc., should be included in the scope of the protection.
Claims (8)
1. a kind of method of comprehensive utilization of silver anode cloth bag wash water, it is characterised in that comprise the following steps：
(1) processing of silver anode cloth bag wash water
By the filtering of silver anode cloth bag wash water, the first filtrate and filter residue are collected respectively；
(2) synthesis of silver oxide
Sodium hydroxide solution is added and reacted in the first filtrate, the second filtrate and silver oxide are collected in filtering respectively；
(3) purification of silver electrolyte
Filtered after silver oxide is washed with clear water, wet oxidation silver and wash water are collected respectively；Wet oxidation silver is added into pending silver
In electrolyte, reaction purification silver electrolyte, it is to be clean after the completion of, filtering respectively collection and purification slag and purification after silver electrolyte；
(4) pre-treatment that silver electrolyte is returned
Acidity will be adjusted after silver electrolyte dilution after purification, finally return to silver-colored electrolytic cell.
2. the method for comprehensive utilization of silver anode cloth bag wash water according to claim 1, it is characterised in that will in step (1)
The filter residue is silver anode slime, and filter residue is returned into silver anode slime system.
3. the method for comprehensive utilization of silver anode cloth bag wash water according to claim 1, it is characterised in that institute in step (2)
State and silver ion and copper ion are included in the first filtrate, the amount ratio of the material of silver ion, copper ion and sodium hydroxide is：n(Ag+
2Cu):N (NaOH)=1:0.8~1.2；Sodium hydroxide solution is gradually added in the first filtrate, stirring reaction 1~2 hour.
4. the method for comprehensive utilization of silver anode cloth bag wash water according to claim 1, it is characterised in that in step (2)
Aqueous slkali is added in second filtrate and carries out heavy silver, silver precipitation is reclaimed, and silver precipitation is returned into silver-colored smelting system.
5. the method for comprehensive utilization of silver anode cloth bag wash water according to claim 1, it is characterised in that wet in step (3)
Moisture in silver oxide is 48%~52%；The wash water returns to wastewater treatment.
6. the method for comprehensive utilization of silver anode cloth bag wash water according to claim 1, it is characterised in that institute in step (3)
The composition for stating pending silver electrolyte is：Ag:280.07~285.12g/L, Cu:20.12~22.32g/L, Bi:0.2023
~0.2265g/L, Pb:0.2081~0.2258g/L, Pd:0.1012~0.1235g/L, acidity:8.05~8.36g/L；According to
The amount of the material of nitric acid and silver oxide in pending silver electrolyte is：n(HNO3):N (AgO)=2:1, calculate silver oxide
Quality, then according to wet oxidation silver in moisture converse need add wet oxidation silver quality；It is wherein pending
Silver electrolyte in the amount of material of nitric acid be that the amount of material of nitric acid in pending silver electrolyte comes out plus copper water solution
Nitric acid material amount summation.
7. the method for comprehensive utilization of silver anode cloth bag wash water according to claim 1, it is characterised in that silver-colored in step (3)
The temperature of electrolyte is 88~92 DEG C, and wet oxidation silver substep is added in 88~92 DEG C of silver electrolyte, stirring reaction 1~
4 hours purification silver electrolytes.
8. the method for comprehensive utilization of silver anode cloth bag wash water according to claim 1, it is characterised in that will in step (4)
The concentration that silver electrolyte after purification is diluted to silver ion is 80~120g/L, and the silver electrolyte after dilution is adjusted into acid with nitric acid
Spend for 7~9g/L.
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| CN115074783A (en) * | 2022-05-19 | 2022-09-20 | 云南铜业股份有限公司西南铜业分公司 | Preparation method of 5N high-purity silver |
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