CN114774991B - Method for recovering valuable metals by synergistic treatment of waste copper-nickel-tin alloy and waste etching solution - Google Patents
Method for recovering valuable metals by synergistic treatment of waste copper-nickel-tin alloy and waste etching solution Download PDFInfo
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- CN114774991B CN114774991B CN202210694201.0A CN202210694201A CN114774991B CN 114774991 B CN114774991 B CN 114774991B CN 202210694201 A CN202210694201 A CN 202210694201A CN 114774991 B CN114774991 B CN 114774991B
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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
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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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
- C22B25/00—Obtaining tin
- C22B25/04—Obtaining tin by wet processes
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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
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
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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
- 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 application provides a method for recovering valuable metals by coprocessing waste copper-nickel-tin alloy and waste etching solution, and relates to the field of solid waste recovery. The method for recovering valuable metals by the synergistic treatment of the waste copper-nickel-tin alloy and the waste etching solution comprises the following steps: carrying out suspension electrolysis on the waste copper-nickel-tin alloy by using an initial electrolyte to obtain an electrolyzed solution and a circulating electrolyte; hydrolyzing the electrolyzed solution to precipitate tin to obtain tin-rich slag and tin-precipitated solution; extracting the liquid after tin precipitation for copper removal to obtain a copper-rich organic phase and a liquid after copper removal; carrying out back extraction on the copper-rich organic phase to obtain back-extracted copper-rich liquid; removing impurities from the decoppered liquid by using resin to obtain purified liquid; neutralizing the purified liquid to precipitate nickel to obtain a nickel product and a nickel precipitated liquid; evaporating and crystallizing the liquid after nickel precipitation to obtain the industrial salt. The method for recovering valuable metals by the synergistic treatment of the waste copper nickel tin alloy and the waste etching solution realizes the synergistic treatment of the waste copper nickel tin alloy and the waste etching solution and the comprehensive recovery of the valuable metals.
Description
Technical Field
The application relates to the field of solid waste recovery, in particular to a method for recovering valuable metals by synergistic treatment of waste copper-nickel-tin alloy and waste etching solution.
Background
Copper-nickel, copper-tin, nickel-tin binary alloy and copper-nickel-tin ternary alloy are widely applied to the industrial industries of aerospace, electronic technology, weapon manufacturing, communication, intelligent manufacturing and the like due to the excellent comprehensive performance of the copper-nickel, copper-tin, nickel-tin binary alloy and copper-nickel-tin ternary alloy. With the increase of service life and mechanical wear, machines, equipment, vehicles, electrical appliances and the like are scrapped, and the recycling of waste alloys is concerned. Because of numerous alloy grades and large component differences, the alloy waste with single component is difficult to be separated and sorted out through disassembly for direct recycling, and the comprehensive recovery of valuable metals such as Cu, Ni, Sn and the like is the inevitable choice for recycling the waste alloy.
Printed Circuit Boards (PCBs) are important components of electronic and electrical products, and generally, 2-2.5L of etching solution is required for each square meter of PCB production, and with the development of the PCB industry, the safe disposal of a large amount of waste etching solution generated faces a great challenge. The etching solution is mainly divided into acidic etching solution and alkaline etching solution, the ratio is approximately 9:1, and therefore, the treatment of the acidic waste etching solution is particularly important. The waste acid etching solution usually contains 60-80 g/L hydrochloric acid, is not easy to be disposed and has high environmental risk, and also contains 80-150 g/L copper and a small amount of metal ions such as Sn, Ni, Fe, Zn and the like, so that the waste acid etching solution has high recycling value.
The waste alloy is generally treated by a pyrogenic process or a wet process, the pyrogenic process mainly adopts direct smelting, matte smelting and other treatments, and the obtained alloy, copper matte and slag are subjected to pyrogenic refining, vacuum refining or wet extraction to recover valuable metals; the wet process mainly adopts an oxidant to oxidize and dissolve the waste alloy, and then the waste alloy is separated and recovered by methods such as chemical precipitation, extraction or ion exchange and the like; the treatment of waste copper nickel tin alloys is rarely reported. The waste acidic etching solution usually adopts chemical precipitation, replacement and other processes to recover copper, and most of free acid, nickel, tin and other valuable metals except copper in the waste acidic etching solution are directly neutralized into neutralization slag.
Disclosure of Invention
The application aims to provide a method for recovering valuable metals by synergistic treatment of waste copper-nickel-tin alloy and waste etching solution, so as to solve the problems.
In order to achieve the purpose, the following technical scheme is adopted in the application:
a method for recovering valuable metals by the synergistic treatment of waste copper-nickel-tin alloy and waste etching solution comprises the following steps:
carrying out suspension electrolysis on the waste copper-nickel-tin alloy by using an initial electrolyte to obtain an electrolyzed solution and a circulating electrolyte;
hydrolyzing the electrolyzed solution to precipitate tin to obtain tin-rich slag and tin-precipitated solution; extracting and decoppering the solution after tin precipitation to obtain a copper-rich organic phase and a decoppered solution;
carrying out back extraction on the copper-rich organic phase to obtain back-extracted copper-rich liquid; removing impurities from the decoppered liquid by using resin to obtain purified liquid;
neutralizing the purified liquid to precipitate nickel to obtain a nickel product and a nickel precipitated liquid; evaporating and crystallizing the nickel-precipitated liquid to obtain industrial salt;
the waste copper nickel tin alloy comprises one or more of waste copper nickel alloy, waste copper tin alloy, waste nickel tin alloy and waste copper nickel tin ternary alloy, and the initial electrolyte comprises the waste etching solution, the circulating electrolyte, the back extraction copper-rich solution, acid and water.
Preferably, the acid comprises hydrochloric acid and/or sulfuric acid;
h of the initial electrolyte + The concentration is 0.5g/L-3 g/L.
Preferably, the anode used for suspension electrolysis is a titanium-coated ruthenium plate or a lead alloy plate;
the cathode used for suspension electrolysis is a titanium plate or a copper plate, and the cathode is arranged in a diaphragm bag made of acid-proof filter cloth.
Preferably, in the suspension electrolysis process, the waste copper-nickel-tin alloy is added into the anode area of the suspension electrolysis cell;
and continuously adding the initial electrolyte into the anode region of the suspension electrolytic tank, and overflowing from the cathode region of the suspension electrolytic tank to the overflow tank through diaphragm permeation to obtain the electrolyzed solution and the circulating electrolyte.
Preferably, the concentration of Cu in the electrolyzed solution is 5g/L-40g/L, H + The concentration of the Sn-Ni alloy is 0.1-1 g/L, the concentrations of the Sn and the Ni are respectively 5-80 g/L independently, and the total amount of the Sn and the Ni is less than or equal to 150 g/L.
Preferably, the concentration of Cu in the electrolyzed solution is 15g/L-25 g/L;
in the suspension electrolysis process, the current density is 50A/m 2 -250A/m 2 The temperature is 20-60 ℃.
Preferably, the hydrolysis and tin precipitation comprises:
mixing the electrolyzed solution with alkali liquor, and carrying out solid-liquid separation;
the alkali in the alkali liquor comprises NaOH, KOH and Na 2 CO 3 、K 2 CO 3 The concentration of the alkali liquor is 50g/L-300 g/L;
the temperature of the hydrolysis tin precipitation is 20-95 ℃, and the end point pH value is 0.8-2.5;
carrying out the hydrolysis tin precipitation process, and adding a reducing agent when the pH value reaches 0.8-1.0;
the reducing agent comprises Na 2 SO 3 Sodium metabisulfite, SO 2 And one or more of iron powder, wherein the reducing agent is used for reducing Fe in the solution 3+ Reduction ofTo Fe 2+ 1.0-2.0 times of the theoretical amount required;
and (3) carrying out the hydrolysis tin precipitation process, and adding tin slag, wherein the adding amount of the tin slag is 1-20% of the total mass of the tin slag obtained by hydrolysis tin precipitation.
Preferably, the extraction stage number of the extraction decoppering is 2-5, and an alkali solution is added to adjust the pH value of the solution before the 2 nd, 3 th and 4 th stages of extraction, or saponification extraction is adopted, and the pH value of the solution after decoppering is controlled to be 0.5-3.0;
the extractant used for extracting and decoppering is any one of Lix984, Lix64, N910 and OPT 5510.
Preferably, the stripping comprises: back-extracting the copper-rich organic phase by using dilute sulfuric acid or dilute hydrochloric acid to obtain a back-extracted copper-rich liquid and an organic phase, back-extracting iron in the organic phase by using concentrated hydrochloric acid to obtain a purified organic phase, and returning the purified organic phase to be used for extraction decoppering;
the concentration of the dilute sulfuric acid is 150g/L-230g/L, the concentration of the dilute hydrochloric acid is 80g/L-150g/L, and the concentration of the concentrated hydrochloric acid is 6N-8N.
Preferably, the neutralization and nickel precipitation are carried out by using a dilute alkali solution, and the alkali in the dilute alkali solution comprises Na 2 CO 3 、NaHCO 3 、K 2 CO 3 、KHCO 3 The concentration of the dilute alkali liquor is 50g/L-300 g/L;
the temperature of the neutralization nickel deposition is 20-80 ℃, and the end point pH value is 7.0-9.5.
Compared with the prior art, the beneficial effect of this application includes:
according to the method for recovering valuable metals by the synergistic treatment of the waste copper-nickel-tin alloy and the waste etching solution, the waste etching solution is used as an electrolyte, an oxidant is not required to be added when the waste copper-nickel-tin alloy is dissolved, the consumption of a reagent is reduced, and the valuable metals in the waste acid solution are recovered; by adopting suspension electrolysis, Cu ions in the waste etching solution are skillfully utilized to be separated out at the cathode and are matched with electrons lost by Sn and Ni electrochemical dissolution in the waste alloy in the anode area, so that a cathode copper product is obtained, meanwhile, hydrogen evolution side reaction is avoided, and the electrolytic process has low cell voltage and low power consumption; the cathode open-circuit liquid is subjected to wet separation through steps of hydrolysis tin precipitation, extraction decoppering, back extraction, resin impurity removal, neutralization nickel precipitation and the like, so that the comprehensive efficient recovery of valuable metals in waste copper-nickel-tin alloy and waste etching liquid is realized; the waste alloy and the waste acid liquid are cooperatively treated, so that the comprehensive and efficient recovery of valuable metals is realized while the dangerous waste acid liquid is consumed and treated, a new idea is provided for the resource utilization of solid waste and liquid waste, the environmental and economic benefits are remarkable, and the application prospect is wide.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments are briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
Fig. 1 is a schematic flow chart of a method for recovering valuable metals by synergistic treatment of waste copper-nickel-tin alloy and waste etching solution provided in an embodiment.
Detailed Description
A method for recovering valuable metals by the synergistic treatment of waste copper-nickel-tin alloy and waste etching solution comprises the following steps:
carrying out suspension electrolysis on the waste copper-nickel-tin alloy by using an initial electrolyte to obtain an electrolyzed solution and a circulating electrolyte;
hydrolyzing the electrolyzed solution to precipitate tin to obtain tin-rich slag and tin-precipitated solution; extracting and decoppering the solution after tin precipitation to obtain a copper-rich organic phase and a decoppered solution;
carrying out back extraction on the copper-rich organic phase to obtain back-extracted copper-rich liquid; removing impurities from the decoppered liquid by using resin to obtain purified liquid;
neutralizing the purified liquid to precipitate nickel to obtain a nickel product and a nickel precipitated liquid; evaporating and crystallizing the nickel-precipitated liquid to obtain industrial salt;
the waste copper nickel tin alloy comprises one or more of waste copper nickel alloy, waste copper tin alloy, waste nickel tin alloy and waste copper nickel tin ternary alloy, and the initial electrolyte comprises the waste etching solution, the circulating electrolyte, the back extraction copper-rich solution, acid and water.
The resin mainly removes trace impurity ions such as Zn, Pb and the like, and aims to improve the purity of subsequent nickel products.
In an alternative embodiment, the acid comprises hydrochloric acid and/or sulfuric acid;
h of the initial electrolyte + The concentration is 0.5g/L-3 g/L.
The initial electrolyte can be prepared in advance, and can also be proportionally supplemented to the anode area of the electrolytic cell in the suspension electrolysis process. It will be appreciated that in the initial stage, the initial electrolyte is predominantly spent etching solution.
In the present application, the waste etching solution refers to an acidic waste etching solution.
Optionally, H of the initial electrolyte + The concentration may be any value between 0.5g/L, 1.0g/L, 1.5g/L, 2.0g/L, 2.5g/L, 3.0g/L, or 0.5g/L to 3 g/L.
In an alternative embodiment, the anode used in the suspension electrolysis is a titanium-coated ruthenium or lead alloy plate;
the cathode used for suspension electrolysis is a titanium plate or a copper plate, and the cathode is arranged in a diaphragm bag made of acid-proof filter cloth.
On one hand, the cathode is placed in the diaphragm bag, the surface appearance of the cathode, or the quality of cathode copper is high (the flatness of the inner surface of direct ore pulp is poor), and on the other hand, the cathode is separated from the anode ore pulp area, so that the oxygen evolution and chlorine evolution reaction generated by the anode is used for dissolving waste alloy, and the influence on the electric efficiency due to the contact with the cathode is avoided.
In an alternative embodiment, during the suspension electrolysis, the waste copper nickel tin alloy is added to the suspension cell anode region;
and continuously adding the initial electrolyte into the anode region of the suspension electrolytic tank, and overflowing from the cathode region of the suspension electrolytic tank to the overflow tank through diaphragm permeation to obtain the electrolyzed solution and the circulating electrolyte.
The waste copper nickel tin alloy can be continuously or discontinuously added into the suspension electrolytic cell anode area according to the actual requirement.
In an alternative embodiment, after said electrolysisIn the solution, the concentration of Cu is 5g/L-40g/L, H + The concentration of the Sn-Ni alloy is 0.1-1 g/L, the concentrations of the Sn and the Ni are respectively 5-80 g/L independently, and the total amount of the Sn and the Ni is less than or equal to 150 g/L.
The control of the Cu concentration is based on: if the concentration is too low, the cathode can generate a powder growing phenomenon, or the cathode copper quality is poor; the copper concentration is too high, so that the subsequent open-circuit electrolyte extraction raffinate is high in acid and the amount of alkali required to be neutralized is large; the concentration of Sn and Ni is too low, the productivity of subsequent treatment is low, and the requirement is not needed; if the sum of the individual exceeds 80 or 2 exceeds 150, crystallization tends to occur.
In a preferred embodiment, the concentration of Cu in the post-electrolysis solution is 15g/L-25 g/L; at this concentration, the cathode copper obtained is of higher quality and the subsequent extraction load is smaller.
In the suspension electrolysis process, the current density is 50A/m 2 -250A/m 2 The temperature is 20-60 ℃.
Optionally, the concentration of Cu in the electrolyzed solution can be any value of 5g/L, 10g/L, 15g/L, 20g/L, 25g/L, 30g/L, 35g/L, 40g/L or 5g/L-40g/L, H + The concentration of (b) can be any value between 0.1g/L, 0.5g/L, 1g/L or 0.1g/L and 1g/L, the concentration of Sn and Ni can be any value between 5g/L, 10g/L, 20g/L, 30g/L, 40g/L, 50g/L, 60g/L, 70g/L, 80g/L or 5g/L and 80g/L independently of each other, and the total amount of Sn and Ni can be any value between 50g/L, 100g/L, 150g/L or less than or equal to 150 g/L; in the suspension electrolysis process, the current density can be 50A/m 2 、100A/m 2 、150A/m 2 、200A/m 2 、250A/m 2 Or 50A/m 2 -250A/m 2 The temperature can be any value between 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃ or any value between 20 ℃ and 60 ℃.
In an alternative embodiment, the hydrolytic tin precipitation comprises:
mixing the electrolyzed solution with alkali liquor, and carrying out solid-liquid separation;
the alkali in the alkali liquor comprises NaOH, KOH and Na 2 CO 3 、K 2 CO 3 One or more of (a), the baseThe concentration of the liquid is 50g/L-300 g/L;
the temperature of the hydrolysis tin precipitation is 20-95 ℃, and the end point pH value is 0.8-2.5;
in a preferred embodiment, the tin precipitation process temperature is 60-90 ℃, and the hydrolyzed tin slag has better filtering performance under the condition.
Optionally, the concentration of the alkali liquor can be any value between 50g/L, 100g/L, 150g/L, 200g/L, 250g/L, 300g/L or 50g/L-300 g/L; the temperature of the hydrolysis tin precipitation can be any value between 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 95 ℃ or 20 ℃ to 95 ℃, and the end point pH value can be any value between 0.8, 1.0, 1.5, 2.0, 2.5 or 0.8 to 2.5.
Carrying out the hydrolysis tin precipitation process, and adding a reducing agent when the pH value reaches 0.8-1.0;
the reducing agent comprises Na 2 SO 3 Sodium metabisulfite, SO 2 One or more of iron powder and reducing agent, wherein the reducing agent is used for reducing Fe in the solution 3+ Reduction to Fe 2+ 1.0-2.0 times of the theoretical amount required;
optionally, the reducing agent can be used in an amount that will reduce Fe in the solution 3+ Reduction to Fe 2+ 1.0, 1.5, 2.0 or any value between 1.0 and 2.0 times the theoretical amount required;
the reducing agent acts to convert Fe 3+ Reduction to Fe 2+ So as to avoid the entrainment of Fe in the tin slag.
And (3) carrying out the hydrolysis tin precipitation process, and adding tin slag, wherein the adding amount of the tin slag is 1-20% of the total mass of the tin slag obtained by hydrolysis tin precipitation.
The tin dross is for being the seed crystal, promotes growing up of heavy tin process granule, is convenient for filter and reduce tin dross filter cake moisture, and the test process adds more than 1% and has comparatively obvious effect promptly, and 5~20% have better effect, increases again and can increase the filtration volume.
Optionally, the addition amount of the tin dross may be 1%, 5%, 10%, 15%, 20% or any value between 1% and 20% of the total mass of the tin dross obtained by the hydrolysis tin precipitation.
The tin dross is used as a seed crystal for promoting Sn (OH) 2 Or Sn (OH) 4 The particles grow up and the filtering performance of the tin slag is improved.
In an optional embodiment, the extraction stage number of the extraction decoppering is 2-5, and an alkali solution is added to adjust the pH value of the solution before the 2 nd, 3 th and 4 th stages of extraction, or saponification extraction is adopted, and the pH value of the solution after decoppering is controlled to be 0.5-3.0;
the extractant used for the extraction decoppering comprises Lix 984.
Optionally, the pH of the solution after decoppering may be any value between 0.5, 1.0, 1.5, 2.0, 2.5, 3.0 or 0.5-3.0.
In an alternative embodiment, the stripping comprises: back-extracting the copper-rich organic phase by using dilute sulfuric acid or dilute hydrochloric acid to obtain a back-extracted copper-rich liquid and an organic phase, back-extracting iron by using concentrated hydrochloric acid to obtain a purified organic phase, and returning the purified organic phase to be used for the extraction decoppering;
the concentration of the dilute sulfuric acid is 150g/L-230g/L, the concentration of the dilute hydrochloric acid is 80g/L-150g/L, and the concentration of the concentrated hydrochloric acid is 6N-8N.
Optionally, the concentration of the dilute hydrochloric acid may be any value between 150g/L, 200g/L, 230g/L or 150g/L-230g/L, the concentration of the dilute hydrochloric acid may be any value between 80g/L, 90g/L, 100g/L, 110g/L, 120g/L, 130g/L, 140g/L, 150g/L or 80g/L-150g/L, and the concentration of the concentrated hydrochloric acid may be any value between 6N, 7N, 8N or 6N-8N.
In an alternative embodiment, the neutralization and nickel precipitation are carried out using a dilute alkali solution, wherein the alkali in the dilute alkali solution comprises Na 2 CO 3 、NaHCO 3 、K 2 CO 3 、KHCO 3 The concentration of the dilute alkali liquor is 50g/L-300 g/L;
the temperature of the neutralization nickel deposition is 20-80 ℃, and the final pH value is 7.0-9.5.
Optionally, the concentration of the dilute alkali liquor can be any value between 50g/L, 100g/L, 150g/L, 200g/L, 250g/L, 300g/L or 50g/L-300 g/L; the temperature of the neutralization nickel deposition can be any value between 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or 20 ℃ to 80 ℃, and the end point pH value can be any value between 7.0, 7.5, 8.0, 8.5, 9.0, 9.5 or 7.0 to 9.5.
Embodiments of the present application will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
According to different purposes, the grades of copper-nickel, copper-tin, nickel-tin binary alloy and copper-nickel-tin ternary alloy are multiple, the components are various, and the components of the waste copper-nickel-tin alloy obtained by disassembling are also greatly fluctuated; different PCB production enterprises and different treatment processes generate acidic waste etching solutions Cu, HCl, Sn, Ni, Fe and the like with larger component fluctuation; the following examples are only given by taking certain alloy waste and waste etching solution as examples (as shown in table 1), and the similar effects of other waste copper, nickel, tin alloy, or electronic circuit board waste, waste acid etching solution, and waste acid containing heavy metal are all within the protection scope of the method.
TABLE 1 composition table of waste copper-nickel-tin alloy and waste etching solution in examples
| Item | Cu | Ni | Sn | Fe | Zn | HC l | N a |
| Waste alloy/% | ~ 12 | ~ 40 | ~ 45 | ~ 2.3 | ~ 0.2 | - | - |
| g/L of waste acid liquid | ~ 95 | ~ 0.03 | ~ 0.15 | 3.5 | 0.15 | 72 | 45 |
Note: in the table, "-" represents that the amount of the ingredient is about the numerical value as written. In addition, the balance of the spent alloy and spent acid solution, excluding the components listed in the table, is negligible impurities.
Example 1
As shown in fig. 1, this embodiment provides a method for recovering valuable metals by using a waste copper-nickel-tin alloy and a waste etching solution in a synergistic manner, which includes the following steps:
(a) preparing an electrolyte: 65L of waste etching solution, 25L (Cu-70.77 g/L) of back-extraction copper solution and 160L (Cu-20 g/L, Ni-44.48 g/L, Sn-50.11 g/L) of circulating electrolyte are uniformly mixed to obtain 250L of pre-electrolysis solution;
(b) and suspension electrolysis of waste copper-nickel-tin alloy: 100L of electrolyte is filled into the suspension electrolytic cell, 10kg of waste copper-nickel-tin alloy is added, and the concentration is 200A/m 2 Carrying out electrolytic conversion under the current density, simultaneously supplementing electrolyte to an anode area of the electrolytic cell by a circulating pump according to 0.5-2.0L/min, and overflowing from a cathode area and returning to the electrolytic cell; after the electrolysis is finished, 7.35kg (Cu-99.90%) of cathode copper and 250L (Cu-20 g/L, Ni-44.48 g/L, Sn-50.11 g/L, Fe-5.08 g/L) of electrolyte are obtained, wherein 160L is used as circulating electrolyte and is used as next electrolytic solution; in addition, 90L (Cu-20 g/L, Ni-44.48 g/L, Sn-50.11 g/L) is opened to the next step;
(c) hydrolyzing and precipitating tin: hydrolyzing the 90L open-circuit electrolyte obtained in the step (b) at 80 ℃ by using 200g/L NaOH solution as a neutralizing agent, adding 300g of tin slag (Sn-64% in dry content) as seed crystals when the pH value is 0.5, and adding 600g of Na when the pH value is 0.8 2 SO 3 Controlling the pH value of the end point to be 1.5 as a reducing agent, filtering and washing to obtain 7.0kg (dry basis, Sn-64.42% and Fe-0.65%) of tin slag and 90.5L (Cu-19.87 g/L and Ni-44.05 g/L) of tin-precipitated liquid; carrying out post-treatment on the tin slag to obtain tin dioxide;
(d) and extraction and decoppering: extracting the tin-precipitated liquid obtained in the step (c) by using 4-level Lix984 for decoppering, adding a small amount of NaOH solution into the second raffinate and the third raffinate to adjust raffinate residual acid, and controlling the pH value of the final raffinate to be 1.5; obtaining a copper-rich organic phase and 91L (Ni-43.81 g/L, Cu-0.05 g/L) of copper-removed liquid;
(e) and back extraction: carrying out back extraction on the copper-negative organic phase obtained in the step (d) by using 130g/L of dilute hydrochloric acid to obtain 25L (Cu-70.76 g/L) of copper-rich liquid, and directly returning to the electrolyte preparation process; performing reverse extraction on iron by adopting 220g/L hydrochloric acid solution after reverse extraction of copper to obtain 10L of reverse iron solution (ferric chloride solution, Fe-36.6 g/L), recycling iron by opening a circuit, and returning the organic solution to the step (d) of extraction and decoppering;
(f) resin adsorption: removing impurities such as Pb, Zn and the like from the decoppered liquid obtained in the step (d) through a weak-base anion resin column to obtain adsorbed liquid;
(g) neutralizing and precipitating nickel: adding 200 ℃ to the solution obtained in the step (f) after adsorption at 60 DEG Cg/L of Na 2 CO 3 Neutralizing and precipitating nickel, controlling the pH value of the end point to be 8.5, and filtering to obtain 8.72kg of nickel carbonate (dry basis, Ni-45.72%) and a nickel precipitation solution;
(h) and concentrating and crystallizing: concentrating and crystallizing the nickel-precipitated liquid obtained in the step (g) to obtain crude industrial salt;
the recovery rates of Cu, Sn and Ni in the whole process are all more than 99 percent.
Example 2
Sulfuric acid is adopted for back extraction in the back extraction process, and the back extraction copper-rich liquid controls Cu to be less than 60g/L, so that copper sulfate crystallization caused by overhigh Cu concentration is avoided; the other examples were the same as example 1.
Specifically, the method comprises the following steps:
(a) preparing an electrolyte: 65L of waste etching solution, 35L (Cu-56.23 g/L) of back extraction copper solution and 160L (Cu-20 g/L, Ni-40.03 g/L, Sn-45.10 g/L) of circulating electrolyte are uniformly mixed to obtain 260L of pre-electrolysis solution;
(b) and suspension electrolysis of waste copper-nickel-tin alloy: 100L of electrolyte is filled into the suspension electrolytic cell, 10kg of waste copper-nickel-tin alloy is added, and the concentration is 200A/m 2 Carrying out electrolytic conversion under the current density, simultaneously supplementing electrolyte to an anode area of the electrolytic cell by a circulating pump according to 0.5-2.0L/min, and overflowing from a cathode area and returning to the electrolytic cell; after the electrolysis is finished, 7.358kg (Cu-99.90%) of cathode copper and 260L (Cu-20 g/L, Ni-40.03 g/L, Sn-45.10 g/L, Fe-4.58 g/L) of electrolyte are obtained, wherein 160L is used as circulating electrolyte and is used as next electrolyte supplement; 100L (Cu-20 g/L, Ni-40.03 g/L, Sn-45.10 g/L) open circuit to the next step;
(c) hydrolyzing and precipitating tin: hydrolyzing the 100L open-circuit electrolyte obtained in the step (b) at 80 ℃ by using 200g/L NaOH solution as a neutralizing agent, adding 300g of tin slag (Sn-64% in dry content) as seed crystals when the pH value is 0.5, and adding 600g of Na when the pH value is 0.8 2 SO 3 Controlling the pH value of the end point to be 1.5 as a reducing agent, filtering and washing to obtain 7.0kg (calculated in dry terms, Sn is 64.43%, Fe is 0.65%) of tin slag and 100.5L (Cu is 19.88g/L, Ni is 39.67g/L) of tin-precipitated liquid; carrying out post-treatment on the tin slag to obtain tin dioxide;
(d) and extraction and decoppering: extracting the tin-precipitated liquid obtained in the step (c) by using 4-level Lix984 for decoppering, adding a small amount of NaOH solution into the second raffinate and the third raffinate to adjust raffinate residual acid, and controlling the pH value of the final raffinate to be 1.5; obtaining 100.5L (Ni-39.671 g/L, Cu-0.1 g/L) of a copper-rich organic phase and a copper-removed liquid;
(e) and back extraction: carrying out back extraction on the copper-negative organic phase obtained in the step (d) by using 200g/L dilute sulfuric acid to obtain 35L (Cu-56.23 g/L) of copper-rich liquid, and directly returning to the electrolyte preparation process; and (3) performing reverse extraction on iron by adopting 220g/L hydrochloric acid solution after reverse extraction on copper to obtain 10L of reverse iron solution (Fe-41.18 g/L), recycling iron by opening a circuit, and returning the organic solution to the step (d) of extraction and decoppering after reverse extraction.
Example 3
The NaOH solution is adopted to precipitate nickel, and the recovery effect is similar.
Specifically, the method comprises the following steps: (a) the procedures of (b), (c), (d) and (e) are as in example 1, (g) nickel is precipitated by NaOH solution;
(g) neutralizing and depositing nickel: and (f) adding 200g/L NaOH into the adsorbed liquid obtained in the step (f) at 60 ℃ to neutralize and precipitate nickel, controlling the pH value of the end point to be 8.5, and filtering to obtain 6.31kg of nickel hydroxide (dry basis, Ni-63.2%) and the nickel-precipitated liquid.
Comparative example 1
The concentration of Cu ions (to 5g/L) in the open-circuit electrolyte is controlled, otherwise, as in the embodiment 1, the obtained cathode copper has a small amount of Sn and Ni impurities, the grade of the cathode copper is low, and part of nickel and tin are lost.
Wherein, the steps b and e are as follows:
(b) and suspension electrolysis of waste copper-nickel-tin alloy: 100L of electrolyte is filled into the suspension electrolytic cell, 10kg of waste copper-nickel-tin alloy is added, and the concentration is 200A/m 2 Carrying out electrolytic conversion under the current density, simultaneously supplementing electrolyte to an anode area of the electrolytic cell by a circulating pump according to 0.5-2.0L/min, and overflowing from a cathode area and returning to the electrolytic cell; after the electrolysis is finished, 7.495kg (Cu-98%) of cathode copper and 250L (Cu-5 g/L, Ni-44.48 g/L, Sn-50.11 g/L, Fe-5.08 g/L) of electrolyte are obtained, wherein 160L of the electrolyte is used as circulating electrolyte and is used as next electrolyte supplement; in addition, 90L (Cu-5 g/L, Ni-44.48 g/L, Sn-50.11 g/L) is opened to the next step;
(e) and back extraction: and (d) carrying out back extraction on the copper-negative organic phase obtained in the step (d) by using 130g/L of dilute hydrochloric acid to obtain 25L (Cu-16.82 g/L) of copper-rich liquid, and directly returning to the electrolyte preparation process.
Comparative example 2
No reducing agent is added in the tin precipitation process, and other steps are as in example 1, the inclusion amount of iron in the tin slag is large, and the grade of the tin slag is slightly low.
Wherein, the step c is as follows:
(c) hydrolyzing and precipitating tin: and (c) hydrolyzing the 90L of open-circuit electrolyte obtained in the step (b) at 80 ℃ by using 200g/L of NaOH solution as a neutralizer, adding 300g of tin slag (Sn-64% in dry terms) as seed crystals when the pH value reaches 0.5, controlling the end point pH value to be 1.5, and filtering and washing to obtain 7.3kg of tin slag (Sn-61.78% in dry terms and Fe-3.76%) and 90.5L of after-tin-deposition liquid (Cu-19.87 g/L, Ni-44.05 g/L).
Comparative example 3
The extraction process does not adjust the pH value for direct extraction, and other cases are that the copper concentration of raffinate is high as in example 1, and copper needs to be further removed subsequently.
Wherein, the step d is as follows:
(d) and extraction decoppering: extracting the tin-precipitated liquid obtained in the step (c) by using 4-grade Lix984 for decoppering; obtaining a copper-rich organic phase and 91L (Ni-43.81 g/L, Cu-5 g/L) of copper-removed liquid.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.
Moreover, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (9)
1. A method for recovering valuable metals by the synergistic treatment of waste copper-nickel-tin alloy and waste etching solution is characterized by comprising the following steps:
carrying out suspension electrolysis on the waste copper-nickel-tin alloy by using an initial electrolyte to obtain an electrolyzed solution and a circulating electrolyte;
hydrolyzing the electrolyzed solution to precipitate tin to obtain tin-rich slag and tin-precipitated solution; extracting and decoppering the solution after tin deposition to obtain a copper-rich organic phase and a decoppered solution; the hydrolysis tin deposition comprises the following steps: mixing the electrolyzed solution with alkali liquor, and carrying out solid-liquid separation; the alkali in the alkali liquor comprises NaOH, KOH and Na 2 CO 3 、K 2 CO 3 The concentration of the alkali liquor is 50g/L-300 g/L; the temperature of the hydrolysis tin precipitation is 20-95 ℃, and the end point pH value is 0.8-2.5; carrying out the hydrolysis tin precipitation process, and adding a reducing agent when the pH value reaches 0.8-1.0; the reducing agent comprises Na 2 SO 3 Sodium metabisulfite, SO 2 And one or more of iron powder, wherein the reducing agent is used for reducing Fe in the solution 3+ Reduction to Fe 2+ 1.0-2.0 times of the theoretical amount required; carrying out the hydrolysis tin precipitation process, and adding tin slag, wherein the adding amount of the tin slag is 1% -20% of the total mass of the tin slag obtained by hydrolysis tin precipitation;
carrying out back extraction on the copper-rich organic phase to obtain back-extracted copper-rich liquid; removing impurities from the decoppered liquid by using resin to obtain purified liquid;
neutralizing the purified liquid to precipitate nickel to obtain a nickel product and a nickel precipitated liquid; evaporating and crystallizing the nickel-precipitated liquid to obtain industrial salt;
the waste copper nickel tin alloy comprises one or more of waste copper nickel alloy, waste copper tin alloy, waste nickel tin alloy and waste copper nickel tin ternary alloy, and the initial electrolyte comprises the waste etching solution, the circulating electrolyte, the back extraction copper-rich solution, acid and water.
2. The method of claim 1, wherein the acid comprises hydrochloric acid and/or sulfuric acid;
h of the initial electrolyte + The concentration is 0.5g/L-3 g/L.
3. The method according to claim 1, wherein the anode used in the suspension electrolysis is a titanium-coated ruthenium plate or a lead alloy plate;
the cathode used for suspension electrolysis is a titanium plate or a copper plate, and the cathode is arranged in a diaphragm bag made of acid-proof filter cloth.
4. The method according to claim 1, characterized in that during the suspension electrolysis, the scrap copper nickel tin alloy is added to the suspension cell anode area;
and continuously adding the initial electrolyte into the anode region of the suspension electrolytic tank, and overflowing from the cathode region of the suspension electrolytic tank to the overflow tank through diaphragm permeation to obtain the electrolyzed solution and the circulating electrolyte.
5. The method according to claim 4, wherein the concentration of Cu in the post-electrolysis solution is 5g/L to 40g/L, and H is + The concentration of the Sn-Ni alloy is 0.1g/L-1g/L, the concentrations of the Sn and the Ni are respectively 5g/L-80g/L independently, and the total amount of the Sn and the Ni is less than or equal to 150 g/L.
6. The method according to claim 5, wherein the concentration of Cu in the post-electrolysis solution is 15g/L to 25 g/L;
in the suspension electrolysis process, the current density is 50A/m 2 -250A/m 2 The temperature is 20-60 ℃.
7. The method as claimed in claim 1, wherein the extraction stage number of the extraction decoppering is 2-5, and the pH value of the solution is adjusted by adding alkali solution before the extraction of the 2 nd, 3 rd and 4 th stages, or the pH value of the solution after decoppering is controlled to be 0.5-3.0 by saponification extraction;
the extractant used for extracting and decoppering is any one of Lix984, Lix64, N910 and OPT 5510.
8. The method of claim 1, wherein the stripping comprises: back-extracting the copper-rich organic phase by using dilute sulfuric acid or dilute hydrochloric acid to obtain a back-extracted copper-rich liquid and an organic phase, back-extracting iron by using concentrated hydrochloric acid to obtain a purified organic phase, and returning the purified organic phase to be used for the extraction decoppering;
the concentration of the dilute sulfuric acid is 150g/L-230g/L, the concentration of the dilute hydrochloric acid is 80g/L-150g/L, and the concentration of the concentrated hydrochloric acid is 6N-8N.
9. The method of any one of claims 1 to 8, wherein the neutralization and nickel precipitation are carried out using a dilute alkali solution, wherein the alkali in the dilute alkali solution comprises Na 2 CO 3 、NaHCO 3 、K 2 CO 3 、KHCO 3 The concentration of the dilute alkali liquor is 50g/L-300 g/L;
the temperature of the neutralization nickel deposition is 20-80 ℃, and the end point pH value is 7.0-9.5.
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