CN114540880A - Method for removing copper in silver electrolyte - Google Patents
Method for removing copper in silver electrolyte Download PDFInfo
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- CN114540880A CN114540880A CN202210102379.1A CN202210102379A CN114540880A CN 114540880 A CN114540880 A CN 114540880A CN 202210102379 A CN202210102379 A CN 202210102379A CN 114540880 A CN114540880 A CN 114540880A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 92
- 239000004332 silver Substances 0.000 title claims abstract description 92
- 239000003792 electrolyte Substances 0.000 title claims abstract description 91
- 239000010949 copper Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 51
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 48
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 46
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 239000002699 waste material Substances 0.000 claims abstract description 42
- 229910001923 silver oxide Inorganic materials 0.000 claims abstract description 28
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical group [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 22
- 239000010956 nickel silver Substances 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003723 Smelting Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910001868 water Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 238000000746 purification Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011133 lead Substances 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910003069 TeO2 Inorganic materials 0.000 description 1
- PEEDYJQEMCKDDX-UHFFFAOYSA-N antimony bismuth Chemical compound [Sb].[Bi] PEEDYJQEMCKDDX-UHFFFAOYSA-N 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SMBGWMJTOOLQHN-UHFFFAOYSA-N lead;sulfuric acid Chemical compound [Pb].OS(O)(=O)=O SMBGWMJTOOLQHN-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G5/00—Compounds of silver
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for removing copper in silver electrolyte, belonging to the technical field of non-ferrous metal smelting. Adding silver oxide into the waste silver electrolyte as a catalyst, adjusting the pH value of a reaction system to 4-5, introducing compressed air into the reaction system, reacting for 0.5-2 h in a heating state, and finally stopping heating, cooling and filtering to obtain the new silver electrolyte. The method can remove copper in the waste silver electrolyte to the maximum extent, improve the recovery rate of silver, remove other metal impurities and realize the purpose of purifying the waste silver electrolyte safely, environmentally and thoroughly.
Description
Technical Field
The invention belongs to the technical field of non-ferrous metal smelting, relates to purification of silver electrolyte, and particularly relates to a method for removing copper from waste silver electrolyte.
Background
The existing silver purification technology adopts an electrolytic refining method, in the electrolytic process, a silver anode is electrochemically dissolved, and silver, copper, lead, bismuth, antimony and other impurity elements in the anode enter silver electrolyte. Along with the increasing of the times of the electrolysis period, metals such as copper, bismuth, antimony, lead and the like in the silver electrolyte are accumulated continuously, so that the impurities of the silver powder exceed the standard, and the silver powder is blackened, yellowed and spongy, so that the silver powder can not reach the national standard. In the process of purifying silver by an electrolytic refining method, the purification of silver electrolyte is an important process, the traditional technology generally adopts a sulfuric acid lead removal method, a hydrolysis antimony bismuth removal method, a thermal decomposition copper removal method, a copper replacement method and a sodium chloride precipitation method to gradually remove various impurities in the silver electrolyte, but when the method is used, a large amount of corrosive gas can be generated to pollute the environment and corrode equipment, so that the field operation environment is poor, the process control difficulty is high, part of silver nitrate is volatilized and lost, the silver content in decomposed slag reaches about 10 percent, and the decomposed slag is not easy to recover. And because the purifying effect is not good, just need prepare new silver electrolyte again, but at the in-process of preparing new silver electrolyte again, will use a large amount of nitric acid to dissolve silver powder, will release a large amount of nitric oxide so, cause the pollution to the environment, silver powder also follows the loss of volatilizing simultaneously. Therefore, developing a new method for purifying silver electrolyte, simplifying the operation process, reducing environmental pollution, improving the purification efficiency, and reducing the silver loss is a problem to be solved in the technical field of silver purification.
Chinese patent CN1884623B discloses a method for purifying silver electrolyte, which comprises heating the silver electrolyte to be purified, forming hydrated ions Ag (OH) from Ag in water solution2-At this time, most of Pb, Cu, Bi, and Sb in the electrolyte are precipitated as hydroxides at the bottom of the electrolyte and removed. The method is simple to operate, short in purification time and free of additional addition of other chemical substances, but the content of Pb, Cu, Bi and Sb in the silver electrolyte obtained by the method can only be reduced to 10- 2g/L, the purifying effect of the product is still to be further improved.
Disclosure of Invention
Aiming at the problems, the invention provides a method for removing copper in silver electrolyte, which achieves the purposes of safely, environmentally and thoroughly purifying waste silver electrolyte by the steps of preparing silver oxide and removing copper, and simultaneously avoids the problems of silver loss and new silver electrolyte reconstruction caused by poor operating environment and high silver content of precipitated slag.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for removing copper in silver electrolyte comprises the following steps:
s1, preparing silver oxide;
s2, copper removal of the waste silver electrolyte: and (4) heating the waste silver electrolyte, adding the silver oxide obtained in the step S1 into the waste silver electrolyte in a stirring state until the pH value of a reaction system is 4-5, introducing compressed air, stirring for 0.5-2 h, stopping heating, cooling and filtering, wherein the filtrate is the silver electrolyte after copper removal.
In the method for removing copper from waste silver electrolyte, the chemical reactions mainly occur as follows:
2Ag++2OH-＝2Ag2O↓+H2O；
Ag2O+2H+＝2Ag++H2O；
2Cu2++O2＝2CuO↓；
Cu2++2OH-＝CuO↓+H2O；
2Pb2++O2＝2PbO↓
Pb2++2OH-＝PbO↓+H2O；
4Bi3++3O2＝2Bi2O3↓；
2Bi3++6OH-＝Bi2O3↓+3H2O；
4Sb3++3O2＝2Sb2O3↓；
2Sb3++6OH-＝Sb2O3↓+3H2O；
Te4++O2＝2TeO2↓；
Te4++4OH-＝TeO2↓+2H2O；
the silver oxide in step S1 may be commercial or analytically pure silver oxide, or silver oxide prepared by a conventional silver oxide preparation method may be selected, and it is only necessary to ensure that no new impurities which are difficult to remove are introduced into step S2.
Preferably, the method for preparing silver oxide in step S1 is as follows: slowly adding an alkaline substance into the waste silver electrolyte while stirring, continuously stirring for 0.5-2 h after the alkaline substance is added, and filtering to obtain filter residues which are silver oxide.
Further preferably, the method for preparing silver oxide in step S1 is as follows: and slowly adding an alkaline substance into the waste silver electrolyte while stirring to adjust the pH value of the waste silver electrolyte to 5-6, continuously stirring for 0.5-2 h after the alkaline substance is added, filtering, and washing filter residues for 3-4 times to obtain the silver oxide.
According to the invention, a part of waste silver electrolyte is used for preparing silver oxide, and the prepared silver oxide is used for purifying the other part of waste silver electrolyte, so that the waste silver electrolyte resource is fully utilized, the loss of silver is greatly reduced, and the recovery rate of silver in the waste silver electrolyte is improved. The purity of the basic substance is not particularly required, and it is only necessary to ensure that no new impurities which are difficult to remove are introduced into step S2.
Further preferably, in step S1, the alkaline substance is slowly added to the waste silver electrolyte while stirring to adjust the pH of the waste silver electrolyte to 5.5.
Further preferably, the basic substance is an alkali metal oxide or an alkali metal hydroxide.
Still more preferably, the alkali metal oxide is sodium oxide or potassium oxide; the alkali metal hydroxide is one of sodium hydroxide solid, potassium hydroxide solid, sodium hydroxide solution or potassium hydroxide solution.
Preferably, the reaction system has a pH of 5 in step S2.
Preferably, the waste silver electrolyte is heated to a temperature of 80 ℃ or higher in step S2.
Preferably, the temperature reduction is to reduce the temperature of the reaction system after the reaction to be less than or equal to 50 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) the Cu content in the new silver electrolyte obtained by removing copper from the waste silver electrolyte by adopting the method is less than or equal to 1g/L, and the Ag content is more than or equal to 105 g/L;
(2) in the copper removing process, silver oxide is used as a catalyst, and compressed air is introduced in the reaction process, so that copper ions in the waste silver electrolyte can be oxidized and precipitated, other impurities can be oxidized and precipitated together, and the problems that the traditional purifying method is incomplete in impurity removal, poor in production environment and needs to rebuild new silver electrolyte are solved;
(3) the silver oxide used in the copper removing process has low requirement on purity, and the silver oxide is prepared by adopting the waste silver electrolyte, so that the utilization rate of the waste silver electrolyte is improved to a greater extent compared with the prior art, and the loss of silver is greatly reduced.
Detailed Description
The technical solution of the present invention is described in detail and fully with reference to the following examples, it is obvious that the described examples are only a part of the examples of the present invention, and not all of the examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention. Any equivalent changes or substitutions by those skilled in the art according to the following embodiments are within the scope of the present invention.
Example 1
The method for removing copper in the silver electrolyte in the embodiment comprises the following steps:
s1 preparation of silver oxide
Will be 15m3Placing the scrapped silver electrolyte with the impurity content exceeding the standard into a reaction kettle, slowly adding sodium hydroxide solid while stirring until the pH value of the solution is 5, continuously stirring for 0.5h after the sodium hydroxide solid is added, opening a valve at the bottom of the reaction kettle, and filtering the reacted material A1 in a vacuum filter barrel to obtain black Ag2Rinsing the O residues for 3 times by using pure water, and performing suction filtration until the O residues are drained;
s2, pumping 15m3Delivering the waste silver electrolyte with the impurity content exceeding the standard to a reaction kettle, opening a steam valve, heating to 80 ℃, stirring and adding the waste silver electrolyte into the step S1 for preparationAg of (A)2And O, introducing compressed air into the reaction kettle until the pH value of the reaction system is 4, continuously stirring for 0.5h, closing a steam valve to stop heating when the reaction system becomes colorless, clear and transparent, opening a cooling water valve to cool the reaction kettle, opening a valve at the bottom of the reaction kettle when the temperature of the reaction system is reduced to 50 ℃, filtering the reacted material B1 in a vacuum filter barrel, and filtering the filtrate to obtain new silver electrolyte after impurities are removed.
Example 2
The method for removing copper in the silver electrolyte in the embodiment comprises the following steps:
s1 preparation of silver oxide
20m is put3Placing the scrapped silver electrolyte with the impurity content exceeding the standard into a reaction kettle, slowly adding a sodium hydroxide solution while stirring until the pH value of the solution is 5.5, continuously stirring for 1h after the solution is added, opening a valve at the bottom of the reaction kettle, and filtering a reacted material A2 in a vacuum filter barrel to obtain black Ag2Rinsing the O residues with pure water for 4 times, and performing suction filtration until the O residues are drained;
s2, pumping 30m3Delivering the waste silver electrolyte with the impurity content exceeding the standard to a reaction kettle, opening a steam valve, heating to 85 ℃, and adding the Ag prepared in the step S1 while stirring2And O, introducing compressed air into the reaction kettle until the pH value of the reaction system is 5, continuously stirring for 1h, closing a steam valve to stop heating when the reaction system becomes colorless, clear and transparent, opening a cooling water valve to cool the reaction kettle, opening a valve at the bottom of the reaction kettle when the temperature of the reaction system is reduced to 40 ℃, filtering the reacted material B2 in a vacuum filter barrel, and filtering the filtrate to obtain a new silver electrolyte after impurities are removed.
Example 3
The method for removing copper in the silver electrolyte in the embodiment comprises the following steps:
s1 preparation of silver oxide
Will be 25m3Placing the scrapped silver electrolyte with the impurity content exceeding the standard into a reaction kettle, slowly adding a sodium hydroxide solution while stirring until the pH value of the solution is 6, continuously stirring for 2 hours after the solution is added, opening a valve at the bottom of the reaction kettle, and reactingFiltering the material A3 in a vacuum filter vat to obtain black Ag2Rinsing the O residues with pure water for 4 times, and performing suction filtration until the O residues are drained;
s2, pumping 30m3Delivering the waste silver electrolyte with the impurity content exceeding the standard to a reaction kettle, opening a steam valve, heating to 90 ℃, and adding the Ag prepared in the step S1 while stirring2And O, introducing compressed air into the reaction kettle until the pH value of the reaction system is 5, continuously stirring for 2 hours, turning off a steam valve to stop heating when the reaction system becomes colorless, clear and transparent, opening a cooling water valve to cool the reaction kettle, opening a valve at the bottom of the reaction kettle when the temperature of the reaction system is reduced to 30 ℃, filtering the reacted material B3 in a vacuum filter barrel, and filtering the filtrate to obtain a new silver electrolyte after impurities are removed.
Example 4
The method for removing copper in the silver electrolyte in the embodiment comprises the following steps:
s1 preparation of silver oxide
Will be 30m3Placing the scrapped silver electrolyte with the excessive impurity content into a reaction kettle, slowly adding a sodium hydroxide solution while stirring until the pH value of the solution is 6, continuously stirring for 2 hours after the addition is finished, opening a valve at the bottom of the reaction kettle, and filtering a reacted material A4 in a vacuum filter barrel to obtain black Ag2Rinsing the O residues with pure water for 4 times, and performing suction filtration until the O residues are drained;
s2, pumping 30m3Delivering the waste silver electrolyte with the impurity content exceeding the standard to a reaction kettle, opening a steam valve, heating to 85 ℃, and adding the Ag prepared in the step S1 while stirring2And O, introducing compressed air into the reaction kettle until the pH value of the reaction system is 4, continuously stirring for 2 hours, turning off a steam valve to stop heating when the reaction system becomes colorless, clear and transparent, opening a cooling water valve to cool the reaction kettle, opening a valve at the bottom of the reaction kettle when the temperature of the reaction system is reduced to 25 ℃, filtering the reacted material B4 in a vacuum filter barrel, and filtering the filtrate to obtain a new silver electrolyte after impurities are removed.
Comparative example 1
The method for removing copper from the silver electrolyte in this comparative example is substantially the same as that of example 1, except that: in step S2, compressed air was not introduced during the reaction, and stirring was carried out for 12 hours.
Comparative example 2
The method for removing copper from the silver electrolyte in this comparative example is substantially the same as that of example 1, except that: in step S1, sodium hydroxide solid was added slowly with stirring until the solution pH was 8.
Comparative example 3
The method for removing copper from the silver electrolyte in this comparative example is substantially the same as that of example 1, except that: the reaction system in step S2 had a pH of 6.
The silver electrolytes obtained after copper removal in examples 1 to 4 and comparative examples 1 to 3 were respectively used and tested according to the following method, and the test results are shown in table 1.
The detection method comprises the following steps:
taking 5mL of silver electrolyte, adding 20mL of analytically pure concentrated hydrochloric acid and 20mL of pure water, placing on an electric hot plate, boiling until no precipitate appears, filtering, using deionized water to fix the volume to 100mL, and placing in an ICP (inductively coupled plasma) device (model: ICP-8000) for detection.
Table 1 detection data before and after copper removal of waste silver electrolyte
As can be seen from Table 1, the method of the invention removes copper from the waste silver electrolyte, the copper removal efficiency reaches more than 95%, and the Cu content in the electrolyte after copper removal is lower than 1 g/L. In comparative example 1, when compressed air was not introduced during the copper removal process, the impurity removal effect was significantly deteriorated, and the copper removal rate was reduced by 7.22%; in comparative example 3, when the pH value was not within the limited range during the copper removal, the impurity removal effect was also deteriorated, and the copper removal rate was reduced by 4.18%; in comparative example 2, if the pH was adjusted to be alkaline when preparing silver oxide, the copper removal rate decreased by 4.36%; finally, the Cu content in the silver electrolyte after copper removal in the comparative examples 1-3 is higher than 1g/L and reaches 1.5g/L at least. Therefore, the method for removing the copper in the waste silver electrolyte can realize the thorough purification of the waste silver electrolyte, furthest realize the waste utilization and improve the recovery utilization rate of the silver.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. The present invention may be subject to various modifications and changes by any person skilled in the art. Any simple equivalent changes and modifications made in accordance with the protection scope of the present application and the content of the specification are intended to be included within the protection scope of the present invention.
Claims (9)
1. The method for removing copper in the silver electrolyte is characterized by comprising the following steps:
s1, preparing silver oxide;
s2, copper removal of the waste silver electrolyte: and (4) heating the waste silver electrolyte, adding the silver oxide obtained in the step S1 into the waste silver electrolyte in a stirring state until the pH value of a reaction system is 4-5, introducing compressed air, stirring for 0.5-2 h, stopping heating, cooling and filtering, wherein the filtrate is the silver electrolyte after copper removal.
2. The method for removing copper in silver electrolyte according to claim 1, wherein the step S1 is to prepare silver oxide by: slowly adding an alkaline substance into the waste silver electrolyte while stirring, continuously stirring for 0.5-2 h after the alkaline substance is added, and filtering to obtain filter residues which are silver oxide.
3. The method for removing copper in silver electrolyte according to claim 2, wherein the step S1 is to prepare silver oxide by: and slowly adding an alkaline substance into the waste silver electrolyte while stirring to adjust the pH value of the waste silver electrolyte to 5-6, continuously stirring for 0.5-2 h after the alkaline substance is added, filtering, and washing filter residues for 3-4 times to obtain the silver oxide.
4. The method of claim 3, wherein the pH of the waste silver electrolyte is adjusted to 5.5 by slowly adding the alkaline substance to the waste silver electrolyte while stirring in step S1.
5. The method for removing copper from silver electrolyte according to any one of claims 2 to 4, wherein the alkaline substance is an alkali metal oxide or an alkali metal hydroxide.
6. The method of claim 5, wherein the alkali metal oxide is sodium oxide or potassium oxide; the alkali metal hydroxide is one of sodium hydroxide solid, potassium hydroxide solid, sodium hydroxide solution or potassium hydroxide solution.
7. The method for removing copper from silver electrolyte according to claim 1, wherein the reaction system has a pH of 5 in step S2.
8. The method for removing copper in silver electrolyte according to claim 1, wherein the waste silver electrolyte is heated to a temperature of 80 ℃ or higher in step S2.
9. The method for removing copper in the silver electrolyte according to claim 1, wherein the temperature reduction is to reduce the temperature of a reaction system after the reaction to be less than or equal to 50 ℃.
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| CN202210102379.1A CN114540880A (en) | 2022-01-27 | 2022-01-27 | Method for removing copper in silver electrolyte |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884623A (en) * | 2006-05-21 | 2006-12-27 | 郴州市金贵有色金属有限公司 | Purifying method for silver electrolytic solution |
| CN101113526A (en) * | 2006-07-28 | 2008-01-30 | 上海银城佘山白银开发有限公司 | Method for purifying silver electrolytic solution during high-purity silver production process |
| JP2008162823A (en) * | 2006-12-27 | 2008-07-17 | Nittetsu Mining Co Ltd | Method for producing cupric oxide from waste copper etching solution |
| CN112479334A (en) * | 2020-10-27 | 2021-03-12 | 深圳市众恒隆实业有限公司 | Purification treatment method of silver electrolyte |
-
2022
- 2022-01-27 CN CN202210102379.1A patent/CN114540880A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884623A (en) * | 2006-05-21 | 2006-12-27 | 郴州市金贵有色金属有限公司 | Purifying method for silver electrolytic solution |
| CN101113526A (en) * | 2006-07-28 | 2008-01-30 | 上海银城佘山白银开发有限公司 | Method for purifying silver electrolytic solution during high-purity silver production process |
| JP2008162823A (en) * | 2006-12-27 | 2008-07-17 | Nittetsu Mining Co Ltd | Method for producing cupric oxide from waste copper etching solution |
| CN112479334A (en) * | 2020-10-27 | 2021-03-12 | 深圳市众恒隆实业有限公司 | Purification treatment method of silver electrolyte |
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Application publication date: 20220527 |