CN114031212A - Method and system for recycling waste copper sulfate plating solution - Google Patents
Method and system for recycling waste copper sulfate plating solution Download PDFInfo
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- CN114031212A CN114031212A CN202111326727.5A CN202111326727A CN114031212A CN 114031212 A CN114031212 A CN 114031212A CN 202111326727 A CN202111326727 A CN 202111326727A CN 114031212 A CN114031212 A CN 114031212A
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- China
- Prior art keywords
- copper sulfate
- plating solution
- sulfate plating
- waste copper
- recycling
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 229910000365 copper sulfate Inorganic materials 0.000 title claims abstract description 66
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 title claims abstract description 66
- 238000007747 plating Methods 0.000 title claims abstract description 64
- 239000002699 waste material Substances 0.000 title claims abstract description 45
- 238000004064 recycling Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 29
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 10
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 10
- 238000001514 detection method Methods 0.000 claims abstract description 10
- 238000011084 recovery Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000001556 precipitation Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 238000004448 titration Methods 0.000 claims description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910001868 water Inorganic materials 0.000 description 10
- 239000011324 bead Substances 0.000 description 5
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- -1 iron ions Chemical class 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 229910001432 tin ion Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229960004887 ferric hydroxide Drugs 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 3
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 3
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 3
- 229910000906 Bronze Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a method and a system for recycling waste copper sulfate plating solution, which belong to the technical field of sewage recovery and specifically comprise the following steps: collecting waste copper sulfate plating solution discharged by a chemical plating operation line; adding hydrogen peroxide into the waste copper sulfate plating solution, stirring simultaneously, and carrying out ferrous ion detection until the ferrous ion detection result is zero; adding cuprous oxide into the waste copper sulfate plating solution added with hydrogen peroxide while stirringPIncreasing the H value to 4 +/-0.3, and stopping stirring to obtain a solid-liquid mixture; the solid-liquid mixture is filtered, and the liquid part is reserved for preparing the copper sulfate solution.
Description
Technical Field
The invention relates to a method and a system for recycling waste copper sulfate plating solution, in particular to a method for recycling plating solution for removing ferrous ions in copper sulfate plating solution, and belongs to the technical field of sewage recovery.
Background
The bead wire is a framework material widely used in the tire industry at present, mainly plays a role in restraining the extension of a bead part and firmly fixing a hub in the tire, and is one of important safety parts of the tire.
At present, chemical copper plating is mainly used for producing the tire bead steel wire, and after the steel wire passes through a copper sulfate plating solution with a certain concentration, the surface of the steel wire and copper ions and tin ions in the copper sulfate solution generate a replacement reaction to form a bronze alloy plating layer on the surface of the tire bead steel wire. With the continuous progress of chemical reaction, the ferrous ion concentration in the copper sulfate solution is higher and higher, and in order to ensure the quality of the bead wire bronze coating, the ferrous ion in the plating solution needs to be controlled, the prior art generally adopts the steps of discharging part of the plating solution and then supplementing water, copper sulfate, stannous sulfate and sulfuric acid to keep the stability of the plating solution. The discharged waste plating solution contains components such as sulfuric acid, copper sulfate, stannous sulfate, ferrous sulfate and the like, and the waste plating solution is treated according to the copper-containing wastewater, so that the treatment cost is higher, the environment is also harmed, and products such as copper sulfate, stannous sulfate and the like with useful values can cause waste.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a method and a system for recycling waste copper sulfate plating solution, and improves the effective utilization rate of copper sulfate in the waste copper sulfate plating solution.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides a method for recycling waste copper sulfate plating solution, which comprises the following steps:
collecting waste copper sulfate plating solution discharged by a chemical plating operation line;
adding hydrogen peroxide into the waste copper sulfate plating solution, stirring simultaneously, and carrying out ferrous ion detection until the ferrous ion detection result is zero;
adding cuprous oxide into the waste copper sulfate plating solution added with hydrogen peroxide while stirringPIncreasing the H value to 4 +/-0.3, and stopping stirring to obtain a solid-liquid mixture;
and filtering the solid-liquid mixture, and reserving a liquid part for preparing the copper sulfate solution.
With reference to the first aspect, further, the ferrous ion detection includes determining the end point of the reaction by titrating the ferrous concentration.
Further, the stirring time is not less than 10 minutes.
Further, the concentration of the hydrogen peroxide is not less than 27.5%.
Furthermore, the cuprous oxide has industrial-grade purity.
In a second aspect, the invention also provides a system for recycling waste copper sulfate plating solution, which uses the method of any one of the preceding claims and comprises a collecting tank, a reaction settling tank, a filter and a recycling storage tank which are connected in sequence;
the collecting tank is provided with an inlet and is used for collecting waste copper sulfate plating solution discharged by a chemical plating operation line;
the reaction precipitation tank is used for sequentially adding hydrogen peroxide and cuprous oxide into the waste copper sulfate plating solution for reaction to obtain a solid-liquid mixture;
the filter is used for filtering a solid-liquid mixture obtained in the reaction precipitation tank;
the recovery storage tank is provided with an outlet, and the liquid part of the solid-liquid mixture after filtration is reserved for preparing the copper sulfate solution.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a method and a system for recycling waste copper sulfate plating solution, which treat ferrous ions in the waste plating solution by a chemical means, precipitate the ferrous ions into solid waste residue, and keep copper sulfate with useful value in the treated plating solution for recycling while not introducing new impurities;
the method can recycle the waste plating solution which is directly discharged in the past, improves the effective utilization rate of copper sulfate and pure water, reduces environmental pollution and saves cost at the same time.
Drawings
FIG. 1 is a flow chart of a system for recycling waste copper sulfate plating solution according to an embodiment of the present invention.
Detailed Description
The invention is further described below. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
The invention specifically discloses a method for recycling waste copper sulfate plating solution, which specifically comprises the following steps:
step 1: collecting waste copper sulfate plating solution discharged by a chemical plating operation line;
step 2: adding hydrogen peroxide into the waste copper sulfate plating solution, simultaneously stirring for 10-30 minutes to complete oxidation-reduction reaction, completely oxidizing ferrous ions in the waste copper sulfate plating solution into ferric ions, and detecting the ferrous ions after stirring until the ferrous ion detection result is zero.
The detection of ferrous ions comprises determining the end point of the reaction by measuring the ferrous concentration by a titration method.
And step 3: adding cuprous oxide into the waste copper sulfate plating solution added with hydrogen peroxide through stirring for 10-30 minutesPAnd increasing the H value to 4 +/-0.3, and stopping stirring to obtain a solid-liquid mixture.
Adding hydrogen peroxide solution to the waste copper sulfate plating solutionPH value is about 1, and with the addition of cuprous oxidePThe H value gradually increases.
And 4, step 4: and filtering the solid-liquid mixture, and reserving a liquid part for preparing the copper sulfate solution.
The concentration of the hydrogen peroxide used in the recovery process is about 27.5 percent, and the cuprous oxide has industrial-grade purity.
In addition, in the reaction process, after the iron ions and the tin ions in the water are precipitated and filtered, copper sulfate and water with continuous use value are reserved, and copper sulfate can be added again to prepare a new plating solution; improves the utilization rate of copper sulfate and water and reduces the discharge of pollutants.
According to the method for recycling the waste copper sulfate plating solution, all oxidation is carried out to high-valence metal ions through oxidation-reduction reaction, then the high-valence metal ions are removed by using the principle of hydrolysis and precipitation of the high-valence metal ions, and finally copper sulfate and water are reserved for recycling, so that the effective utilization rate of copper sulfate and pure water is improved, the environmental pollution is reduced, and the cost is saved.
The invention also provides a system for recycling the waste copper sulfate plating solution, which is a flow chart of the system as shown in figure 1 and comprises a collecting tank, a reaction precipitation tank, a filter and a recycling storage tank which are connected in sequence. The collecting tank, the reaction settling tank and the recovery storage tank are respectively connected by pipelines.
Wherein the collecting tank is provided with an inlet for collecting the waste copper sulfate plating solution discharged by the chemical plating operation line.
Pumping the waste copper sulfate plating solution to be treated into a reaction precipitation tank, and oxidizing ferrous ions and stannous ions into iron ions and tin ions respectively by using hydrogen peroxide; adding cuprous oxide into the reaction precipitation tank to react to remove hydrogen ions, and reactingPThe H value is controlled to be 4 +/-0.3, so that iron ions and tin ions respectively generate ferric hydroxide and tin hydroxide precipitates, and the ferric hydroxide and the tin hydroxide precipitates enter the solid waste residue.
Then a filter is used for filtering out ferric hydroxide and tin hydroxide precipitates, ferrous ions which influence the quality of the chemical copper plating product are removed, copper sulfate and water with useful values are recovered, and the obtained copper sulfate solution is pumped into a recovery storage tank, namely the recovery of the copper sulfate plating solution is completed.
Furthermore, the recovery storage tank is provided with an outlet pipeline for reserving the liquid part after the solid-liquid mixture is filtered, and the recovery storage tank can be directly used for preparing the copper sulfate solution.
The system is used for recycling the waste copper sulfate plating solution, the waste plating solution is subjected to reaction and precipitation, then is filtered to remove insoluble impurities, and is conveyed to a recycling plating solution storage tank for storage through a pipeline, other impurity ions are not introduced into the used reagent, and the used reagent is finally converted into copper sulfate, water and oxygen, so that the discharge of water and copper sulfate can be reduced.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A method for recycling waste copper sulfate plating solution is characterized by comprising the following steps:
collecting waste copper sulfate plating solution discharged by a chemical plating operation line;
adding hydrogen peroxide into the waste copper sulfate plating solution, stirring simultaneously, and carrying out ferrous ion detection until the ferrous ion detection result is zero;
adding cuprous oxide into the waste copper sulfate plating solution added with hydrogen peroxide while stirringPIncreasing the H value to 4 +/-0.3, and stopping stirring to obtain a solid-liquid mixture;
and filtering the solid-liquid mixture, and reserving a liquid part for preparing the copper sulfate solution.
2. The method as claimed in claim 1, wherein the detection of ferrous ions comprises determining the end point of the reaction by measuring the ferrous concentration by titration.
3. The method for recycling waste copper sulfate plating solution according to claim 1, wherein the stirring time is not less than 10 minutes.
4. The method for recycling the waste copper sulfate plating solution as claimed in claim 1, wherein the concentration of the hydrogen peroxide is not less than 27.5%.
5. The method for recycling the waste copper sulfate plating solution according to claim 1, wherein the cuprous oxide has industrial grade purity.
6. A system for recycling waste copper sulfate plating solution, which is characterized in that the method of any one of claims 1 to 5 is used, and comprises a collecting tank, a reaction settling tank, a filter and a recycling storage tank which are connected in sequence;
the collecting tank is provided with an inlet and is used for collecting waste copper sulfate plating solution discharged by a chemical plating operation line;
the reaction precipitation tank is used for sequentially adding hydrogen peroxide and cuprous oxide into the waste copper sulfate plating solution for reaction to obtain a solid-liquid mixture;
the filter is used for filtering a solid-liquid mixture obtained in the reaction precipitation tank;
the recovery storage tank is provided with an outlet, and the liquid part of the solid-liquid mixture after filtration is reserved for preparing the copper sulfate solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111326727.5A CN114031212A (en) | 2021-11-10 | 2021-11-10 | Method and system for recycling waste copper sulfate plating solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111326727.5A CN114031212A (en) | 2021-11-10 | 2021-11-10 | Method and system for recycling waste copper sulfate plating solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114031212A true CN114031212A (en) | 2022-02-11 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111326727.5A Pending CN114031212A (en) | 2021-11-10 | 2021-11-10 | Method and system for recycling waste copper sulfate plating solution |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020136685A1 (en) * | 2001-03-20 | 2002-09-26 | Julio Huato | Process for producing stable cupric hydroxide and basic cupric salts |
| CN102503009A (en) * | 2011-10-09 | 2012-06-20 | 成都大中华焊接材料有限公司 | Recycling method of chemical copper plating waste liquid |
| CN202912790U (en) * | 2012-10-25 | 2013-05-01 | 中冶东方工程技术有限公司上海分公司 | Copper plating waste liquid regeneration system |
| CN104233452A (en) * | 2014-09-29 | 2014-12-24 | 天津市永昌焊丝有限公司 | Method for cyclically treating welding wire copper plating waste liquid and device used in method |
| CN106757179A (en) * | 2016-12-01 | 2017-05-31 | 沈阳有色金属研究院 | A kind of cupric electrolysis tail washings purifies the process of decopper(ing) removal of impurities |
-
2021
- 2021-11-10 CN CN202111326727.5A patent/CN114031212A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020136685A1 (en) * | 2001-03-20 | 2002-09-26 | Julio Huato | Process for producing stable cupric hydroxide and basic cupric salts |
| CN102503009A (en) * | 2011-10-09 | 2012-06-20 | 成都大中华焊接材料有限公司 | Recycling method of chemical copper plating waste liquid |
| CN202912790U (en) * | 2012-10-25 | 2013-05-01 | 中冶东方工程技术有限公司上海分公司 | Copper plating waste liquid regeneration system |
| CN104233452A (en) * | 2014-09-29 | 2014-12-24 | 天津市永昌焊丝有限公司 | Method for cyclically treating welding wire copper plating waste liquid and device used in method |
| CN106757179A (en) * | 2016-12-01 | 2017-05-31 | 沈阳有色金属研究院 | A kind of cupric electrolysis tail washings purifies the process of decopper(ing) removal of impurities |
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Application publication date: 20220211 |
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