CN104911683A - Method for side-stream removal of iron ions in zinc sulfate electroplating solution - Google Patents
Method for side-stream removal of iron ions in zinc sulfate electroplating solution Download PDFInfo
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- CN104911683A CN104911683A CN201510223103.9A CN201510223103A CN104911683A CN 104911683 A CN104911683 A CN 104911683A CN 201510223103 A CN201510223103 A CN 201510223103A CN 104911683 A CN104911683 A CN 104911683A
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Abstract
The invention discloses a method for side-stream removal of iron ions in a zinc sulfate electroplating solution. The method comprises the steps: side-stream leading out the zinc sulfate electroplating solution, adding a hydrogen peroxide solution or introducing ozone gas under normal temperature and pressure, carrying out a reaction for 10-20 min, firstly, oxidizing ferrous in the electroplating solution into tri-valent iron, then adding zinc oxide, carrying out a reaction for 10-15 min, raising the pH of the electroplating solution to 3.6-4.0, transforming tri-valent iron in the solution into a ferric hydroxide precipitate, then adding a non-ionic polyacrylamide flocculant, strengthening a precipitation effect, and allowing the electroplating solution after treatment to return to an electrogalvanizing system for recycling. The added oxidant has strong oxidation ability and fast reaction speed, the polyacrylamide flocculant is used for strengthening precipitation separation, the iron ion removal is more complete, the electroplating solution after treatment is recycled, no waste liquid is discharged to the outside, and the treatment process has the advantages of high efficiency and environmental protection.
Description
Technical field
The invention belongs to zinc sulfate electroplate liquid processing technology field, be specifically related to a kind of method that side line removes iron ion in zinc sulfate electroplate liquid.
Background technology
Sulfate zinc plating technique is widely used in the high speed electrogalvanizing production of sheet material and wire rod because of the excellent properties that it can work under high current density, is a kind of galvanizing technique generally adopted both at home and abroad at present.Main component due to zinc sulfate electroplate liquid is zinc sulfate and dilute sulphuric acid, the acidity of electroplate liquid is stronger, the iron of iron and steel plating piece substrate surface in electroplating process can be partly dissolved and enter electroplate liquid, add the reason of the industrial chemicals such as the sulfuric acid that molten zinc or electro-galvanizing system are supplemented because of aspects such as purity are inadequate, after all likely causing electro-galvanizing plating solution to run for some time, the content of the ferrous iron in plating solution and ferric ion can constantly be accumulated thus exceed its threshold concentration (total iron concentration reaches 3000 ~ 4000mg/L), once the content of iron ion exceeds threshold value, the quality of galvanized sheet will be had a strong impact on, coating occurs that crystallization is thick, pin hole, sticking power is weak, gloomy even without serious quality problems such as coating, and detrimentally affect is produced to the corrosion resisting property of galvanized sheet.Therefore, the impurity iron ion in electroplate liquid must be removed in order to the quality of stable galvanized sheet.
For reducing ferrous in electro-galvanizing plating solution and ferric content, ensure that the stable normal of technique runs, the method taked at present mainly contains periodic exhaustion plating solution method, active carbon adsorption, ion exchange method and oxidation-precipitation method.Do not exceed standard though periodic exhaustion plating solution method can maintain plating solution impurity, supplementing fresh plating solution on the one hand will improve running cost, and the plating solution of discharge on the other hand will increase environmental protection pressure; Gac can by the foreign metal ion in the micropore of its prosperity or mesopore selective adsorption electroplate liquid, thus the content of foreign metal ion in reduction electroplate liquid, although active carbon adsorption can remove the ferrous ion in electroplate liquid to a certain extent, but due to it, to there is loading capacity little, the not easily defect such as regeneration after the not high and adsorbing metal ions of selectivity, in the process of electroplate liquid, application is less separately; Ion exchange method such as Baoshan Iron and Steel Group adopts ion-exchange absorption technique to remove Fe in electro-galvanizing plating solution
2+, Fe
3+, this complete equipment is together introduced with zinc-plated production technique, and complete assembly is import ANDRITZ Products, and how the difficult point of ion exchange method improves the selectivity to object removal impurity; Oxidation-precipitation method is domestic has also carried out some useful exploration work in this respect, CN103695971A proposes a kind of method reducing total concentration of iron in zinc sulfate electroplate liquid, first the method adds zinc, molten zinc in zinc sulfate electroplate liquid, the pH of zinc sulfate electroplate liquid is promoted to 2.0 ~ 2.6, then excessive hydrogen peroxide is added, by Fe
2+be oxidized to Fe
3+, then add zinc carbonate suspension the pH value of plating solution is promoted to 2.8 ~ 3.5, stratification obtains total iron not higher than the electroplate liquid of 500mg/L, there are 3 weak points in the method, one is slow by the molten zinc speed of response of zinc sulfate electroplate liquid, and the molten zinc time is long, affects production efficiency; Two is, by molten zinc, pH is promoted to 2.0 ~ 2.6, reduces the oxidation rate that acidity also just reduces hydrogen peroxide; Three is add zinc carbonate suspension again that the pH value of plating solution is promoted to 2.8 ~ 3.5, pH is on the low side, and ferric hydroxide precipitate is incomplete, and iron ion removing is not thorough.
Summary of the invention
The present invention is intended to overcome prior art defect, and object is to provide a kind of method that side line removes iron ion in zinc sulfate electroplate liquid.
For achieving the above object, the technical solution used in the present invention comprises the following steps:
(1) lead in reactor by zinc sulfate electroplate liquid, add superoxol or pass into ozone gas under normal temperature and pressure, reaction 10 ~ 20min, by the ferrous ion complete oxidation in electroplate liquid to ferric ion;
(2) in the electroplate liquid of step (1) gained, add zinc oxide reaction 10 ~ 15min, the pH of electroplate liquid is risen to 3.6 ~ 4.0, makes the ferric iron in solution be converted into ironic hydroxide;
(3) in the ironic hydroxide suspension of step (2) gained, add organic polymer coargulator again, promote ironic hydroxide flocculating settling;
(4) precipitation of step (3) gained filtered, the filtrate of gained clarification is the electroplate liquid after removing iron ion, and the electroplate liquid after process is back to the recycle of electro-galvanizing system.
The aqueous hydrogen peroxide solution of described superoxol to be mass percentage concentration be 27wt% or 30wt%;
Described ozone is mass body volume concentrations is 30 ~ 35g/m
3ozone gas.
Described organic polymer coargulator is non-ionic polyacrylamide.
Owing to adopting technique scheme, the present invention compared with prior art has following positively effect:
(1) side line that the present invention relates to removes the method for iron ion in zinc sulfate electroplate liquid, draw containing the zinc sulfate electroplate liquid compared with ferric ion concentration by side line, adopt the method that oxidation bonding flocculation reinforced deposition is separated, iron ion in plating solution removes more thorough, electroplate liquid after process is back to the recycle of electro-galvanizing system, arrange outward without waste liquid, treating processes high-efficiency environment friendly.
(2) side line that the present invention relates to removes the method for iron ion in zinc sulfate electroplate liquid, employing be hydrogen peroxide or ozone strong oxidizing agent, oxidation capacity is strong, speed of response is fast, and the reduzate of the two is water molecules does not introduce new impurity.
(3) side line that the present invention relates to removes the method for iron ion in zinc sulfate electroplate liquid, electroplate liquid after oxidation adds the free hydrogen ionic reaction in zinc oxide and electroplate liquid, generate solution composition zinc sulfate and water molecules, this process both have adjusted the pH value of electroplate liquid, supplement again the effective constituent in electroplate liquid, and introduce without new impurity.
(4) side line that the present invention relates to removes the method for iron ion in zinc sulfate electroplate liquid, non-ionic polyacrylamide flocculation agent is added in the electroplate liquid suspension after adjustment pH, reinforced deposition effect, and the precipitation generated is filtered, iron ion removes more complete.
Accompanying drawing explanation
Fig. 1 is a kind of process flow diagram of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described further, the restriction not to its protection domain.
embodiment 1
A kind of side line removes the method for iron ion in zinc sulfate electroplate liquid.Described side line removes the method for iron ion in zinc sulfate electroplate liquid, and the method comprises the following steps:
(1) lead in reactor by 50L zinc sulfate electroplate liquid (total iron concentration is 3560mg/L), add superoxol under normal temperature and pressure, reaction 10 ~ 20min, by the ferrous ion complete oxidation in electroplate liquid to ferric ion;
(2) in the electroplate liquid of step (1) gained, add zinc oxide reaction 10 ~ 15min, the pH of electroplate liquid is risen to 3.6 ~ 4.0, makes the ferric iron in solution be converted into ironic hydroxide;
(3) in the ironic hydroxide suspension of step (2) gained, add organic polymer coargulator again, promote ironic hydroxide flocculating settling;
(4) precipitation of step (3) gained filtered, the filtrate of gained clarification is the electroplate liquid after removing iron ion, and the electroplate liquid after process is back to the recycle of electro-galvanizing system.
The aqueous hydrogen peroxide solution of described superoxol to be mass percentage concentration be 30wt%.
Described organic polymer coargulator is non-ionic polyacrylamide.
Total iron concentration in zinc sulfate electroplate liquid after the present embodiment process drops to 152 mg/L, far below the threshold concentration scope of zinc sulfate electroplating process to plating solution impurity, can return the recycle of electro-galvanizing system.
embodiment 2
A kind of side line removes the method for iron ion in zinc sulfate electroplate liquid.Except following technical parameter, all the other are with embodiment 1:
Described zinc sulfate electroplate liquid (total iron concentration is 2580mg/L).
The aqueous hydrogen peroxide solution of described superoxol to be mass percentage concentration be 27wt%.
Total iron concentration in zinc sulfate electroplate liquid after the present embodiment process drops to 103 mg/L, far below the threshold concentration scope of zinc sulfate electroplating process to plating solution impurity, can return the recycle of electro-galvanizing system.
embodiment 3
A kind of side line removes the method for iron ion in zinc sulfate electroplate liquid.Described side line removes the method for iron ion in zinc sulfate electroplate liquid, and the method comprises the following steps:
(1) lead in reactor by 50L zinc sulfate electroplate liquid (total iron concentration is 3862mg/L), pass into ozone gas under normal temperature and pressure, reaction 10 ~ 20min, by the ferrous ion complete oxidation in electroplate liquid to ferric ion;
(2) in the electroplate liquid of step (1) gained, add zinc oxide reaction 10 ~ 15min, the pH of electroplate liquid is risen to 3.6 ~ 4.0, makes the ferric iron in solution be converted into ironic hydroxide;
(3) in the ironic hydroxide suspension of step (2) gained, add organic polymer coargulator again, promote ironic hydroxide flocculating settling;
(4) precipitation of step (3) gained filtered, the filtrate of gained clarification is the electroplate liquid after removing iron ion, and the electroplate liquid after process is back to the recycle of electro-galvanizing system.
Described ozone is mass body volume concentrations is 35g/m
3ozone gas.
Described organic polymer coargulator is non-ionic polyacrylamide.
Total iron concentration in zinc sulfate electroplate liquid after the present embodiment process drops to 169mg/L, far below the threshold concentration scope of zinc sulfate electroplating process to plating solution impurity, can return the recycle of electro-galvanizing system.
embodiment 4
A kind of side line removes the method for iron ion in zinc sulfate electroplate liquid.Except following technical parameter, all the other are with embodiment 1:
Described zinc sulfate electroplate liquid (total iron concentration is 2768mg/L).
Described ozone is mass body volume concentrations is 30g/m
3ozone gas.
Total iron concentration in zinc sulfate electroplate liquid after the present embodiment process drops to 115 mg/L, far below the threshold concentration scope of zinc sulfate electroplating process to plating solution impurity, can return the recycle of electro-galvanizing system.
Above-mentioned embodiment is the present invention's preferably embodiment, but embodiments of the present invention are not restricted to the described embodiments, change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify, all should be equivalence.
Claims (3)
1. side line removes a method for iron ion in zinc sulfate electroplate liquid, it is characterized in that, the method comprises the following steps:
(1) lead in reactor by zinc sulfate electroplate liquid, add superoxol or pass into ozone gas under normal temperature and pressure, reaction 10 ~ 20min, by the ferrous ion complete oxidation in electroplate liquid to ferric ion;
(2) in the electroplate liquid of step (1) gained, add zinc oxide reaction 10 ~ 15min, the pH of electroplate liquid is risen to 3.6 ~ 4.0, makes the ferric iron in solution be converted into ironic hydroxide;
(3) in the ironic hydroxide suspension of step (2) gained, add organic polymer coargulator again, promote ironic hydroxide flocculating settling;
(4) precipitation of step (3) gained filtered, the filtrate of gained clarification is the electroplate liquid after removing iron ion, and the electroplate liquid after process is back to the recycle of electro-galvanizing system.
2. side line as claimed in claim 1 removes the method for iron ion in zinc sulfate electroplate liquid, it is characterized in that described superoxol to be mass percentage concentration be the aqueous hydrogen peroxide solution of 27wt% or 30wt%; Described ozone is mass body volume concentrations is 30 ~ 35g/m
3ozone gas.
3. side line as claimed in claim 1 removes the method for iron ion in zinc sulfate electroplate liquid, it is characterized in that described organic polymer coargulator is non-ionic polyacrylamide.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108796595A (en) * | 2018-06-22 | 2018-11-13 | 武汉钢铁有限公司 | The method for efficiently removing iron ion in zinc sulfate plating solution |
| CN108950624A (en) * | 2018-08-28 | 2018-12-07 | 王志伟 | A kind of connection rod of automobile engine automation electro-brush plating reparation liquid purification process |
| CN109576511A (en) * | 2018-12-05 | 2019-04-05 | 核工业北京化工冶金研究院 | A kind of In Pregnant Solution From In-situ Leaching method for removing iron |
| CN110373706A (en) * | 2019-08-22 | 2019-10-25 | 电子科技大学 | A kind of on-line maintenance method of acid bright copper plating electroplate liquid |
| CN110484738A (en) * | 2019-06-12 | 2019-11-22 | 张家港市骏马钢帘线有限公司 | Zinc recovering utilizes method in a kind of cadmia |
| CN111634948A (en) * | 2020-06-19 | 2020-09-08 | 厦门钨业股份有限公司 | Method for eliminating black spot foreign matter in ammonium paratungstate product |
| CN113913626A (en) * | 2021-09-30 | 2022-01-11 | 昆明理工大学 | Method for removing impurity iron in zinc hydrometallurgy solution by ultrasonic and ozone oxidation |
| WO2022007505A1 (en) * | 2020-07-09 | 2022-01-13 | 江苏兴达钢帘线股份有限公司 | Cleaning method used for replacing phosphating for thermal diffusion electroplated wire |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108796595A (en) * | 2018-06-22 | 2018-11-13 | 武汉钢铁有限公司 | The method for efficiently removing iron ion in zinc sulfate plating solution |
| CN108950624A (en) * | 2018-08-28 | 2018-12-07 | 王志伟 | A kind of connection rod of automobile engine automation electro-brush plating reparation liquid purification process |
| CN109576511A (en) * | 2018-12-05 | 2019-04-05 | 核工业北京化工冶金研究院 | A kind of In Pregnant Solution From In-situ Leaching method for removing iron |
| CN110484738A (en) * | 2019-06-12 | 2019-11-22 | 张家港市骏马钢帘线有限公司 | Zinc recovering utilizes method in a kind of cadmia |
| CN110373706A (en) * | 2019-08-22 | 2019-10-25 | 电子科技大学 | A kind of on-line maintenance method of acid bright copper plating electroplate liquid |
| CN110373706B (en) * | 2019-08-22 | 2021-05-14 | 电子科技大学 | Online maintenance method of acidic bright copper plating electroplating solution |
| CN111634948A (en) * | 2020-06-19 | 2020-09-08 | 厦门钨业股份有限公司 | Method for eliminating black spot foreign matter in ammonium paratungstate product |
| WO2022007505A1 (en) * | 2020-07-09 | 2022-01-13 | 江苏兴达钢帘线股份有限公司 | Cleaning method used for replacing phosphating for thermal diffusion electroplated wire |
| CN113913626A (en) * | 2021-09-30 | 2022-01-11 | 昆明理工大学 | Method for removing impurity iron in zinc hydrometallurgy solution by ultrasonic and ozone oxidation |
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Application publication date: 20150916 |