CN104017992B - A kind of zinc base alloy nickel plated copper melts the Slag recovering novel process after zinc - Google Patents
A kind of zinc base alloy nickel plated copper melts the Slag recovering novel process after zinc Download PDFInfo
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- CN104017992B CN104017992B CN201410218354.3A CN201410218354A CN104017992B CN 104017992 B CN104017992 B CN 104017992B CN 201410218354 A CN201410218354 A CN 201410218354A CN 104017992 B CN104017992 B CN 104017992B
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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
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Abstract
Zinc base alloy nickel plated copper melts the Slag recovering novel process after zinc, comprises following steps: nickel plated copper zinc base alloy residue is pulverized by (1), and cross 80 ~ 140 mesh sieves, after sieving, gained carries out magnetic separation; (2) nonmagnetics adds low temperature flux, melts out zinc ingot metal, the molten rear filtration of residue alkali, removing filter residue, and filtrate electrolysis obtains zinc ingot metal, and electrolytic solution returns and recycles as broad dose of alkali; (3) Magnetic Materials adds molten nickel solvent, oxygenant, and filter, in filter cake, gained is copper, becomes copper products after processing; Gained filtrate is solution containing nickel, filters after solution containing nickel is put in heavy nickel agent, obtains nickel product after the processing of gained filter cake; (4) regenerator is put into (3) gained filtrate, filter, gained filter cake is byproduct; Filtrate cycle is returned in step (3) as molten nickel agent uses.Present invention process flow process is simple and direct easy to operate, and cost is low, can reclaim waste liquid again, decreases the pollution of waste liquid to environment, useful matter and the fast recovery utilization rate of metal separation high, less investment, low cost, good in economic efficiency.
Description
Technical field
The present invention relates to a kind of metals recovery processes method, particularly a kind of zinc base alloy nickel plated copper melts the Slag recovering novel process after zinc.
Background technology
Zinc base alloy is be that base adds other elementary composition alloys with zinc.The alloying element often added has aluminium, copper, magnesium, cadmium, lead, titanium etc.Zinc base alloy fusing point is low, good fluidity, easy melting welding, and soldering and plastic working are corrosion-resistant in an atmosphere, and maimed material is convenient to reclaim and remelting.The zinc base alloy of nickel plated copper, when such zinc base alloy reclaims, through high temperature, zinc melting is gone out, reclaim remaining residue after zinc be zinc base alloy nickel plated copper melt zinc after residue, the iron of the zinc generally containing mass percent 60 ~ 70% in this residue, 5 ~ 9% bronze medals, 10 ~ 15% nickel and minute quantity and aluminium mixture.Separation method at present to zinc-copper nickel, has solvent extration; Dissolution method under non-oxidizable diluted acid medium, the ion exchange method etc. under acidic conditions.But these processing methodes are comparatively loaded down with trivial details, and cost is higher, as volatilely in solvent extration organic solvent to pollute.So melt zinc a small amount of in the residue after zinc, copper, a lot of factory of nickel all as offal treatment for zinc base alloy nickel plated copper.
Copper is a kind of chemical element, and its chemical symbol is Cu (Latin: Cuprum), and its ordination number is 29, is a kind of transition metal.Copper is one of mankind's metal of finding the earliest, is also the mankind's the first metal widely used.Copper and its some alloys have good corrosion resistance, again because glossy, easily process, and are therefore used to manufacture currency.Copper is also used to make weapons, vessel and cable.
Nickel is a kind of important industrial metal raw material, and its end-use is extensive.Nickel can be used to manufacture various stainless steel and forms the various alloy with the premium properties such as anticorrosive, high temperature resistant with metals such as copper, iron, chromium, cobalts, is widely used in aircraft, the aspects such as boats and ships, chemical industry, oil, electronics, electrical equipment.Active nickel powder is used as the catalyzer of hydrogenation reaction at Organic Chemical Industry.Single nickel salt is for the manufacture of mordant, the metallochrome of catalyzer especially, vat dyes; Nickel oxide is used for magneticsubstance, metallurgy, store battery and picture tube industry etc.
Zinc base alloy nickel plated copper melts still containing zinc, copper, nickel in the residue after zinc, and directly abandoning one is make the wasting of resources, and another is can to environment.Now along with the development of chemical industry, metal waste is also in the trend constantly risen, and people also more and more focus on the recycling to it.Therefore, how to solve the zinc that can reclaim in residue, copper, nickel, recovery process not only comparatively simply, does not cause secondary pollution, cost recovery but also lower problem, needs solution badly.
Summary of the invention
The present invention utilizes simple processing method, lower cost, realizes the recovery of zinc base alloy nickel plated copper being melted to copper, nickel and the residual zinc contained in the residue after zinc, makes the copper in residue, nickel and residual zinc to realize second stage employ, while turning waste into wealth, decrease the pollution to environment.
Technical solution of the present invention is as follows:
Zinc base alloy nickel plated copper melts the Slag recovering novel process after zinc, comprises following operation steps:
(1) zinc base alloy nickel plated copper is melted the residue after zinc to pulverize, cross 80 ~ 140 mesh sieves, after sieving, gained carries out magnetic separation;
(2) nonmagnetics after magnetic separation is added low temperature flux, melt out zinc ingot metal, after molten zinc, residue carries out that then alkali is molten filters, and removing filter residue gained filtrate is carried out electrolysis and obtained zinc ingot metal, and electrolytic solution returns the molten step of alkali and recycles as broad dose of alkali;
(3) Magnetic Materials adds molten nickel solvent, oxygenant, and filter, in filter cake, gained is copper, after processing, become copper products; Gained filtrate is solution containing nickel, and solution containing nickel is put in heavy nickel agent, stirs and then filters, and makes nickel ion form compound precipitation, filters, and namely obtains nickel product after the processing of gained filter cake;
(4) regenerator is put into step (3) and add the rear gained filtrate of heavy nickel agent filtration, form precipitation, filter again, gained filter cake is packaged into byproduct after processing; Filtrate cycle is returned in step (3) and is reused as molten nickel agent.
Wherein, low temperature flux add-on described in step (2) is that zinc base alloy nickel plated copper melts 8 ~ 15% of residue weight after zinc.
Wherein, the low temperature flux described in step (2) comprises following component: Repone K and magnesium chloride, and the weight ratio of described Repone K and described magnesium chloride is 1:1 ~ 1:1.3.
Wherein, the oxygenant described in step (2) is the one in oxygen, hydrogen peroxide.
Wherein, the molten nickel solvent described in step (2) is the salt of hydrochloric acid or copper ions.
Wherein, described heavy nickel agent is calcium carbonate.
Wherein, described regenerator is sulfuric acid.
Wherein, step (3) is washed with being processed as described in step (4), drying, being pulverized.
Wherein, described being filtered into is filtered with plate-and-frame filter press or vacuum filter.
Wherein, directly carry out electrolysis in step (3) or by gained solution containing nickel and obtain nickel metal, can directly obtain nickel metal without the need to putting into heavy nickel agent and carrying out step (4).
Use molten nickel solvent described above, oxygenant, that heavy nickel agent all needs is excessive, regenerant consumption and the material reacted with it are the relation of 1:1.
In addition, when the salt for copper ions added in step (2), without the need to adding oxygenant.
Compared with prior art, beneficial effect of the present invention:
Present invention process method is simple and direct easy to operate, institute's with medicament, equipment is comparatively conventional, be easy to get, melt to zinc base alloy nickel plated copper a small amount of zinc, copper, the nickel that contain in the residue after zinc to reclaim respectively, cost recovery is lower, recovery process is simple to operation, and the residue after making zinc base alloy nickel plated copper melt zinc can reduce again the pollution to environment while turning waste into wealth; Wherein low temperature agent is intended to protect zinc in molten zinc process not oxidized, reduces smelting temperature and strengthens mobility simultaneously, such that zinc is not oxidized, quality is better.
Accompanying drawing explanation
Fig. 1 is present invention process schema.
Embodiment
Further describe the present invention referring to embodiment, to make those skilled in the art can implement according to this with reference to specification sheets word, scope is not limited by embodiments of the present invention.In embodiment, Repone K, magnesium chloride, sulfuric acid, hydrochloric acid are all commercially available.
Embodiment 1
Take the Repone K of 0.5kg, the magnesium chloride of 0.5kg mixes and stirs, make low temperature flux for subsequent use, 10kg zinc base alloy nickel plated copper melts the residue after zinc, include the zinc of mass percent 60 ~ 70%, 5 ~ 9% bronze medals, the iron of 10 ~ 15% nickel and minute quantity and aluminium mixture, zinc base alloy nickel plated copper is melted the residue after zinc pulverize, 100 mesh sieves are crossed after pulverizing, ground-slag after sieving is passed in dry separation cartridge type low intensity magnetic separator and carries out magnetic separation, after magnetic separation, nonmagnetics and zinc are discharged outside magnetic separator and are added the above-mentioned low temperature flux prepared, then put into after smelting furnace melts with zinc mix and blend and be pressed into zinc ingot metal, after molten zinc, to carry out alkali molten for residue, alkaline solution used is sodium hydroxide solution, after alkali is molten, solution is passed into vacuum filter to filter, remove filter residue, gained filtrate is put into electrolyzer and is carried out electrolysis, separate out zinc, be zinc ingot metal, electrolytic solution returns the molten step cycle of alkali and uses.After magnetic separation, Magnetic Materials i.e. great majority are copper, nickel mixture, add the hydrochloric acid of 3kg and excessive oxygen in the mixture, oxygen is as oxygenant, promote that nickel dissolves and form nickel ion solution, copper not with hydrochloric acid reaction still for solid exists in solution, passed into by this mixing solutions in the plate-and-frame filter press of 1# hydraulic compression and filter, in filter cake, material is copper, after pulverizing after copper washing, oven dry, namely obtain copper products; Gained filtrate is nickel solution, calcium carbonate is put into filtrate, nickel ion is precipitated, then pass in the plate-and-frame filter press of 2# hydraulic compression and filter, gained filter cake is nickeliferous product, is carried out being packaged into nickel product by nickeliferous product after washing, oven dry and pulverizing; Gained filtrate contains Ca
2+, Cl
-etc. the sulfuric acid adding with reactant the amount being 1:1, make Ca
2+generate precipitation calcium salt, Cl
-generate hydrochloric acid, passed into by this solution in the plate-and-frame filter press of 3# hydraulic compression and filter, gained filter cake is calcium precipitation, is packed by calcium precipitation, become byproduct after washing, oven dry; Filtrate is hydrochloric acid, recycles as molten nickel agent.
Embodiment 2
Take the Repone K of 0.37kg, the magnesium chloride of 0.43kg mixes and stirs, make low temperature flux for subsequent use, 10kg zinc base alloy nickel plated copper melts the residue after zinc, include the zinc of mass percent 60 ~ 70%, 5 ~ 9% bronze medals, the iron of 10 ~ 15% nickel and minute quantity and aluminium mixture, zinc base alloy nickel plated copper is melted the residue after zinc pulverize, 80 mesh sieves are crossed after pulverizing, ground-slag after sieving is passed in dry separation cartridge type low intensity magnetic separator and carries out magnetic separation, after magnetic separation, nonmagnetics and zinc are discharged outside magnetic separator and are added the above-mentioned low temperature flux prepared, then put into after smelting furnace melts with zinc mix and blend and be pressed into zinc ingot metal, after molten zinc, to carry out alkali molten for residue, alkaline solution used is sodium hydroxide solution, after alkali is molten, solution is passed into vacuum filter to filter, remove filter residue, gained filtrate is put into electrolyzer and is carried out electrolysis, separate out zinc, be zinc ingot metal, electrolytic solution returns the molten step cycle of alkali and uses.After magnetic separation, Magnetic Materials i.e. great majority are copper, nickel mixture, and it is excessive to add in the mixture; Cupric Chloride Solution, promotion nickel dissolves and forms nickel ion solution, and separate out cupric ion, passed in 3# vacuum filter by this mixing solutions and filter, in filter cake, material is copper, after pulverizing after copper washing, oven dry, namely obtain copper products; Gained filtrate is nickel solution, is passed into by nickel solution in electrolyzer and carries out electrolysis, obtains nickel simple substance.
Embodiment 3
Take the Repone K of 0.65kg, the magnesium chloride of 0.85kg mixes and stirs, make low temperature flux for subsequent use, 10kg zinc base alloy nickel plated copper melts the residue after zinc, include the zinc of mass percent 60 ~ 70%, 5 ~ 9% bronze medals, the iron of 10 ~ 15% nickel and minute quantity and aluminium mixture, zinc base alloy nickel plated copper is melted the residue after zinc pulverize, 140 mesh sieves are crossed after pulverizing, ground-slag after sieving is passed in dry separation cartridge type low intensity magnetic separator and carries out magnetic separation, after magnetic separation, nonmagnetics and zinc are discharged outside magnetic separator and are added the above-mentioned low temperature flux prepared, then put into after smelting furnace melts with zinc mix and blend and be pressed into zinc ingot metal, after molten zinc, to carry out alkali molten for residue, alkaline solution used is ammoniacal liquor, after alkali is molten, solution is passed into vacuum filter to filter, remove filter residue, gained filtrate is put into electrolyzer and is carried out electrolysis, separate out zinc, be zinc ingot metal, electrolytic solution returns the molten step cycle of alkali and uses.After magnetic separation, Magnetic Materials i.e. great majority are copper, nickel mixture, add excessive hydrochloric acid, hydrogen peroxide in the mixture, hydrogen peroxide is as oxygenant, promote that nickel dissolves and form nickel ion solution, copper not with hydrochloric acid reaction still for solid exists in solution, passed into by this mixing solutions in the plate-and-frame filter press of 1# hydraulic compression and filter, in filter cake, material is copper, after pulverizing after copper washing, oven dry, namely obtain copper products; Gained filtrate is nickel solution, calcium carbonate is put into filtrate, nickel ion is precipitated, then pass in the plate-and-frame filter press of 2# hydraulic compression and filter, gained filter cake is nickeliferous product, is carried out being packaged into nickel product by nickeliferous product after washing, oven dry and pulverizing; Gained filtrate contains Ca
2+, Cl
-etc. the sulfuric acid adding with reactant the amount being 1:1, make Ca
2+generate precipitation calcium salt, Cl
-generate hydrochloric acid, passed into by this solution in the plate-and-frame filter press of 3# hydraulic compression and filter, gained filter cake is calcium precipitation, is packed by calcium precipitation, become byproduct after washing, oven dry; Filtrate is hydrochloric acid, recycles as molten nickel agent.
Present invention process method is simple and direct easy to operate, institute's with medicament, equipment is comparatively conventional, be easy to get, melt to zinc base alloy nickel plated copper a small amount of zinc, copper, the nickel that contain in the residue after zinc to reclaim respectively, cost recovery is lower, recovery process is simple to operation, and the residue after making zinc base alloy nickel plated copper melt zinc can reduce again the pollution to environment while turning waste into wealth; Wherein low temperature agent is intended to protect zinc in molten zinc process not oxidized, reduces smelting temperature and strengthens mobility simultaneously, such that zinc is not oxidized, quality is better.
Claims (7)
1. zinc base alloy nickel plated copper melts the Slag recovering novel process after zinc, it is characterized in that, comprises following operation steps:
(1) zinc base alloy nickel plated copper is melted the residue after zinc to pulverize, cross 80 ~ 140 mesh sieves, after sieving, gained carries out magnetic separation;
(2) nonmagnetics after magnetic separation is added low temperature flux, melt out zinc ingot metal, after molten zinc, residue carries out that then alkali is molten filters, removing filter residue gained filtrate is carried out electrolysis and is obtained zinc ingot metal, electrolytic solution returns the molten step of alkali and recycles as broad dose of alkali, wherein, described low temperature flux comprises following component: Repone K and magnesium chloride; The weight ratio of described Repone K and described magnesium chloride is 1:1 ~ 1:1.3;
(3) Magnetic Materials after magnetic separation is added molten nickel solvent, oxygenant, filter, in filter cake, gained is copper, after processing, become copper products; Gained filtrate is solution containing nickel, and solution containing nickel is put in heavy nickel agent, filters, and namely obtain nickel product after the processing of gained filter cake, wherein, described molten nickel solvent is the salt of hydrochloric acid or copper ions;
(4) regenerator is put into step (3) and add the rear gained filtrate of heavy nickel agent filtration, filter again, gained filter cake is packaged into byproduct after processing; Filtrate cycle is returned in step (3) and is reused as molten nickel agent, and wherein, described regenerator is sulfuric acid.
2. zinc base alloy nickel plated copper melts the Slag recovering novel process after zinc according to claim 1, it is characterized in that: low temperature flux add-on described in step (2) is that zinc base alloy nickel plated copper melts 8 ~ 15% of residue weight after zinc.
3. zinc base alloy nickel plated copper melts the Slag recovering novel process after zinc according to claim 1, it is characterized in that: the oxygenant described in step (3) is the one in oxygen, hydrogen peroxide.
4. zinc base alloy nickel plated copper melts the Slag recovering novel process after zinc according to claim 1, it is characterized in that: described heavy nickel agent is calcium carbonate.
5. zinc base alloy nickel plated copper melts the Slag recovering novel process after zinc according to claim 1, it is characterized in that: step (3) is washed with being processed as described in step (4), drying, being pulverized.
6. zinc base alloy nickel plated copper melts the Slag recovering novel process after zinc according to claim 1, it is characterized in that: being filtered into described in step (3) and step (4) is filtered with plate-and-frame filter press or vacuum filter.
7. zinc base alloy nickel plated copper melts the Slag recovering novel process after zinc according to claim 1, it is characterized in that: directly carry out electrolysis in step (3) or by gained solution containing nickel and obtain nickel metal, can directly obtain nickel metal without the need to putting into heavy nickel agent and carrying out step (4).
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| CN201410218354.3A CN104017992B (en) | 2014-05-22 | 2014-05-22 | A kind of zinc base alloy nickel plated copper melts the Slag recovering novel process after zinc |
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| CN201410218354.3A CN104017992B (en) | 2014-05-22 | 2014-05-22 | A kind of zinc base alloy nickel plated copper melts the Slag recovering novel process after zinc |
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| CN104017992B true CN104017992B (en) | 2016-03-02 |
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| CN113981233A (en) * | 2021-11-15 | 2022-01-28 | 西安西热锅炉环保工程有限公司 | System and method for recovering metal by using non-metal mother liquor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4149945A (en) * | 1978-04-13 | 1979-04-17 | Kennecott Copper Corporation | Hydrometallurgical brass dust reclamation |
| CN102011006A (en) * | 2010-11-17 | 2011-04-13 | 厦门火炬特种金属材料有限公司 | Method for performing vacuum separation and purification on coating-containing zinc alloy |
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2014
- 2014-05-22 CN CN201410218354.3A patent/CN104017992B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4149945A (en) * | 1978-04-13 | 1979-04-17 | Kennecott Copper Corporation | Hydrometallurgical brass dust reclamation |
| CN102011006A (en) * | 2010-11-17 | 2011-04-13 | 厦门火炬特种金属材料有限公司 | Method for performing vacuum separation and purification on coating-containing zinc alloy |
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Granted publication date: 20160302 Termination date: 20210522 |