CN106958021A - A kind of regeneration treating method of highly acidity Ni from waste etching FeCl 3 solution containing - Google Patents
A kind of regeneration treating method of highly acidity Ni from waste etching FeCl 3 solution containing Download PDFInfo
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- CN106958021A CN106958021A CN201710306127.XA CN201710306127A CN106958021A CN 106958021 A CN106958021 A CN 106958021A CN 201710306127 A CN201710306127 A CN 201710306127A CN 106958021 A CN106958021 A CN 106958021A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
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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
- C22B23/0469—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods by chemical substitution, e.g. by cementation
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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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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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Abstract
The invention discloses a kind of regeneration treating method of highly acidity Ni from waste etching FeCl 3 solution containing, comprise the following steps：(1), highly acidity Ni from waste etching FeCl 3 solution containing is electrolysed using eddy flow diaphragm process, anolyte and catholyte is obtained, gained anolyte is the regeneration etching solution that can be directly used for etching work procedure；(2) catholyte obtained by step (1), is evaporated crystallization, frerrous chloride crystal and nickelic mother liquor is obtained, hydrochloric acid is obtained after the steam that evaporative crystallization is produced is condensed；(3) iron powder, is added into nickelic mother liquor obtained by step (2) and enters line replacement reaction, is then filtered, filter residue and filtrate is obtained, gained filtrate is solution of ferrous chloride, and gained filter residue obtains iron nickel powder after drying.The regeneration treating method is simple to operate, low cost, recovery utilization rate high, and can coproduction frerrous chloride crystal and iron nickel powder.
Description
Technical field
Technical field is recycled the present invention relates to etching solution, and in particular to a kind of nickeliferous ferric trichloride etching of highly acidity is useless
The regeneration treating method of liquid.
Background technology
Liquor ferri trichloridi is due to certain oxidisability and acidity, having good corrosiveness to iron, nickel, thus
By it is substantial amounts of be applied in metal etch, the etching of such as fine circuit pattern, microelectronics Packaging it is stainless in ferric trichloride etching nickel
Steel shadow mask process.In etching process, FeCl3FeCl is reduced into by nickel and stainless steel2, while a small amount of metallic nickel can be oxidized with Ni2+
Form enters etching solution.In etching process, with FeCl in etching solution3The reduction of concentration and Ni2+The rise of concentration, the effect of etching
Rate can decline.In addition, Ni in etching solution2+The rise of concentration is also easy to cause product etching surface excessively coarse.
According to etch process quality requirement, the constituent content of ferric trichloride etching solution should reach claimed below：Ferric trichloride
Content >=35%, frerrous chloride content≤0.4%.Therefore, a large amount of used FeCl3Etching solution is due to that can not meet etch process
It is required that and being discharged from etch system in waste liquid form.Frerrous chloride content is 2.1%~7.2% in waste liquid composition, is also contained
2.3%~6.5% nickel chloride.If this waste liquid is discharged as danger wastes without processing, not only result in environment
Pollution, and the significant wastage to resource can be caused.Therefore how highly efficient regeneration utilization is current to Ni from waste etching FeCl 3 solution containing
Domestic and international relevant industries question of common concern.
Notification number is proposes a kind of recovery method of ferric trichloride etching solution in CNIO4131285A patent, using film
Electrolysis and extraction integrated technology.The technology particular content is：Amberplex is provided with a cell, and electrolytic cell is split into shape
Into anode chamber and cathode chamber, negative electrode is located in the cathode chamber and anode chamber of amberplex both sides respectively with anode, in cathode chamber
Interior addition ferric trichloride etching waste liquor carries out film electrolysis, by Fe3+Ion reduction is Fe2+Ion；Solution after being electrolysed to cathode chamber
Extraction imurity-removal metal is carried out, extraction phase solution and demetalization impurities phase solution is obtained, demetalization impurities phase solution delivers to sun
Pole room carries out film electrolysis, by Fe2+Ionic oxide formation is Fe3+Ion；The solution that anode chamber's electrolysis is obtained is reclaimed.The technique energy
Iron chloride etching solution is effectively reclaimed, still, occurs that localized ion concentration is too low in etching solution during the technique conventional electrolysis
Situation, there is the phenomenon of concentration polarization, be unfavorable for electrolysis progress；Extraction process has specific requirement to acidity, if erosion
Acid too high containing acid in liquid, too high is carved by the serious progress for hindering extraction process, it is necessary to additionally subsequently be located to etching waste liquor
Reason, untill the acidity in etching solution reaches that extraction is required；Using and reclaiming for extractant is also that the technique needs what is considered
One important economic factor, introduces extraction and back extraction process substantially increases the recovery process of etching waste liquor, multitple extraction
With the back extraction also tediously long complexity so that recovery process seems.
At this stage, the base material that electronics industry and stainless steel decoration industry are commonly used is nickeliferous, chromium stainless steel.Its chemical composition
Middle Ni accounts for 8.0%~11.0%, Fe and accounts for 65.0%~70.0%.Contain Ni in waste liquid after etching2+、Fe3+Ion and not anti-
The FeCl answered3, hydrochloric acid.If etching waste liquor is directly discharged without processing can cause the pollution of water environment, and a large amount of valuable nickel,
Chromium, iron resource are by slatterning in vain.And etching waste liquor processing qualified discharge can increase the cost of scale wastewater treatment.Cause
This, it is very necessary to seek a kind of economic, effective stainless steel etching waste liquor comprehensive utilization method.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcomings of to mention with defect that there is provided one in background above technology
Planting can coproduction frerrous chloride crystal and the high nickeliferous ferric trichloride of highly acidity of iron nickel powder, simple to operate, low cost, recovery utilization rate
The regeneration treating method of etching waste liquor.
In order to solve the above technical problems, technical scheme proposed by the present invention is：
A kind of regeneration treating method of highly acidity Ni from waste etching FeCl 3 solution containing, comprises the following steps：
(1), highly acidity Ni from waste etching FeCl 3 solution containing is electrolysed using eddy flow diaphragm process, anolyte is obtained
And catholyte, gained anolyte is the regeneration etching solution that can be directly used for etching work procedure；
(2) catholyte obtained by step (1), is evaporated crystallization, frerrous chloride crystal and nickelic mother liquor, evaporation knot is obtained
Hydrochloric acid is obtained after the steam of crystalline substance generation is condensed；
(3) iron powder, is added into nickelic mother liquor obtained by step (2) and enters line replacement reaction, then filters, obtains filter residue and filter
Liquid, gained filtrate is solution of ferrous chloride, and gained filter residue obtains iron nickel powder after drying.
The present invention can be made high-purity hydrochloric acid, high-purity can be also made while realizing that etching waste liquor is recycled
Frerrous chloride product and iron nickel powder, can directly sell.It is constant that whole flow process of the present invention maintains original system, without introducing body
System includes the chemical reagent outside ion, and Superacid System is also suitable.Meanwhile, whole flow process pollution on the environment pole
It is few, meet the theory of metallurgical clean manufacturing now, and the nickel element in etching waste liquor has effectively been reclaimed, realize etching waste liquor
Regeneration.
The present invention handles etching waste liquor using the method for diaphragm electrolysis, with the progress of electrolysis, Fe3+In anode enrichment, Fe2 +Fe in cathodic enrichment, anolyte3+Concentration can reach more than 2.9801mol/L, and Fe2+Concentration can be decreased to
Below 0.0019mol/L, Ni2+Concentration is less than 0.02mol/L, and gained anolyte meets in etch process to ferric trichloride etching solution
Quality requirement, can directly recycle.Meanwhile, crystallization treatment is evaporated to catholyte, frerrous chloride crystal is reclaimed, enters
One step recycles iron resource.Ni in filtrate after evaporative crystallization2+Content is high, and using iron replacement, iron is dried to obtain after filtering
Nickel powder, filtrate is solution of ferrous chloride.The regeneration treating method whole process of the present invention is simple to operate, with low cost, to etching
The recovery utilization rate of waste liquid is high, can coproduction frerrous chloride crystal and iron nickel powder, and three-waste free discharge.
Space in cell body is divided into sun by the electrolytic cell that eddy flow diaphragm process is used, including cell body, anion-exchange membrane
Pole room and cathode chamber, anode chamber are communicated with anode hopper, and cathode chamber is communicated with negative electrode hopper.In electrolytic process, anode
The Ni from waste etching FeCl 3 solution containing of side is circulated between anode chamber and anode hopper, the nickeliferous trichlorine of negative electrode side
Change iron etching waste liquor to circulate between cathode chamber and negative electrode hopper, and the Cl in cathode chamber-Selectivity through it is cloudy from
Proton exchange enters in anode chamber.The reaction mainly occurred in electrolytic process is as follows：
Anode reaction：2Cl-→Cl2↑+2e- (I)
Fe2+→Fe3++e- (II)
Cathode reaction：Fe3++e-→Fe2+ (III)。
Above-mentioned regeneration treating method, it is preferred that solution of ferrous chloride obtained by step (3) is back in step (1)
Electrolysis processing is carried out in the anode slot of eddy flow diaphragm electrolysis again, resource utilization is further increased.
Above-mentioned regeneration treating method, it is preferred that in step (1), the decomposition voltage that the eddy flow diaphragm electrolysis is used for
3.5v~4.5v.During using this voltage, negative and positive two-stage is enabled to occur required electrode reaction, while reducing other secondary
Reaction.As further preferred, the decomposition voltage is 3.5v.Under this voltage, current efficiency highest reaches 93.18%.Electricity
The solution time is not less than 3h.The current density of electrolytic process Anodic electrode is 130A/m2~190A/m2.It is positive under this current density
Fe in pole room2+It is oxidized to Fe3+Efficiency highest.
Above-mentioned regeneration treating method, it is preferred that in step (2), the evaporation and crystal process is under nitrogen protection atmosphere
Carry out, and the intake of nitrogen is controlled in 6L/min~7L/min.Frerrous chloride is avoided to be oxidized.
Above-mentioned regeneration treating method, it is preferred that in step (2), the evaporation and crystal process is carried out under condition of negative pressure,
Its vacuum degree control is controlled at 76 DEG C~80 DEG C in 0.084MPa~0.086MPa, evaporating temperature.Evaporate and reach after supersaturation, mistake
Saturated solution is directly entered crystallizer, the crystallisation by cooling in crystallizer, and Vacuum filtration device is entered after the completion of crystallization and carries out solid-liquid
Isolate the recovery of frerrous chloride crystal.Evaporated under condition of negative pressure, it is possible to decrease evaporating temperature, evaporation and crystal process can be reduced
Energy consumption.It is further preferred that vacuum be 0.085MPa, temperature be 78 DEG C under the conditions of, HCl recovery rate reaches up to about 84.3%,
The concentration of regenerated acid is about 0.89mol/L, and color is colourless.
Above-mentioned regeneration treating method, it is preferred that in step (3), the iron powder is reduced iron powder, and iron powder can be with Ni2+
Reaction so that Ni2+It is replaced out, is separated out in the form of elemental nickel.The excess coefficient of iron powder addition is (i.e. whole by nickel in theory
The multiple of iron powder needed for displacement) it is preferably 2.8.Ni can be made by adding excessive iron powder2+It is replaced out completely.Experiment discovery, when
When iron powder excess coefficient is 2.8, the Ni after evaporation in liquid2+Substantially it is replaced completely.The reaction time of the displacement reaction for 2~
3h, on this condition displacement reaction is carried out completely, and a large amount of nickel ions are converted into elemental nickel.The drying is vacuum drying, vacuum
Dry temperature is 90 DEG C~100 DEG C, and vacuum drying time is not less than 2h.
Above-mentioned regeneration treating method, it is preferred that in step (1), acidity >=100g/L of the etching waste liquor, is peracid
Spend etching waste liquor.
Above-mentioned regeneration treating method, it is preferred that in step (1), the etching waste liquor is to use ferric trichloride etching solution
Etching waste liquor produced by after to being handled containing nickel and stainless steel, its main chemical compositions are Fe3+、Fe2+、Ni2+、H+And Cl-。
Above-mentioned regeneration treating method, it is preferred that in step (1), the barrier film that the eddy flow diaphragm electrolysis is used is homogeneous
Anion-exchange membrane, homogeneous-phase anion exchange film has more preferable electro-chemical activity.The anode electrode that eddy flow diaphragm electrolysis is used
For metal Ti electrode, metal Ti electrode cannot participate in anode reaction, and electrolytic efficiency is higher.
Above-mentioned regeneration treating method, it is preferred that in step (3), the content of the solution of ferrous chloride ferrous ions
For 150g/L~200g/L, the content of nickel ion is less than 1g/L, except nickel rate is more than the mass fraction of nickel in 95%, the iron nickel powder
More than 30%.
Compared with prior art, the advantage of the invention is that：Nickel ion of the invention by being introduced in effective control system
With the material balance of the nickel ion cemented out, the namely regenerated ferric trichloride etching solution of anolyte obtained through electrolysis, wherein Fe3+
Concentration can reach 2.9801mol/L, Fe2+Concentration is less than 0.0019mol/L, Ni2+Concentration is less than 0.02mol/L.Meet etching
To the quality requirement of ferric trichloride etching solution in technique, etch process can be directly used for.Meanwhile, catholyte is real by iron replacement
The open circuit of existing nickel, then utilize the catholyte rich in frerrous chloride to prepare frerrous chloride crystal by vacuum distillation method, further return
Receipts utilize iron resource.Nickel ion in etching waste liquor is mainly enriched with liquid after evaporation, and nickel simple substance is converted into after iron replacement,
Product is iron nickel powder after filtration washing, can be sold；Filtrate main component after filtering can return to anolyte for frerrous chloride
Recycle.The production technology that the present invention is used, whole process is simple to operate, with low cost, and etching waste liquor can be recycled, right
Iron and nickel recovery utilization rate in etching waste liquor is high, and three-waste free discharge.
Brief description of the drawings
Fig. 1 is the process chart of the regeneration treating method of highly acidity Ni from waste etching FeCl 3 solution containing of the present invention.
Embodiment
For the ease of understanding the present invention, more complete is made to the present invention below in conjunction with Figure of description and preferred embodiment
Face, meticulously describe, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art
It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention
Protection domain.
Unless otherwise specified, various raw material, reagent, instrument and equipment used in the present invention etc. can be by city
Field is commercially available or can prepared by existing method.
Embodiment 1：
A kind of embodiment of the regeneration treating method of highly acidity Ni from waste etching FeCl 3 solution containing of the present invention, its technological process
As shown in Figure 1.Using certain electronic enterprise etch invar produce etching waste liquor as raw material, comprehensive utilization of resources production iron nickel powder and
Frerrous chloride crystal product.Main component in etching waste liquor is through analyzing as Fe3+：156g/L；Fe2+：18g/L；Ni2+：10g/L；
H+：3.2g/L；Cl-：160g/L.The acidity of etching waste liquor is 114g/L.
The regeneration treating method of the highly acidity Ni from waste etching FeCl 3 solution containing specifically includes following steps：
(1) added after etching waste liquor 5L is measured in the anode and cathode groove of eddy flow diaphragm cell, cathode can 1.5L, anode slot
3.5L, opens booster pump, regulates anode and cathode circular flow, and remaining stable with cathode can and anode slot liquid level is not changed into judging mark
It is accurate.The barrier film that eddy flow diaphragm electrolysis is used is homogeneous-phase anion exchange film, and the anode electrode used is metal Ti electrode.
(2) flow straightener is started, regulation voltage is to 3.5v, and timing starts, and Fe in catholyte is titrated with titration3+Concentration,
Until Fe in catholyte3+Fe is reduced into completely2+When stop cell reaction, the cell reaction time be 3.5h, the electricity of anode electrode
Current density is 152A/m2, anolyte directly reclaimed as regeneration etching solution, and catholyte squeezed into vacuum distillation device.
(3) nitrogen is passed through during vacuum distillation, nitrogen intake is 6L/min~7L/min, and vacuum distillation device is true
Reciprocal of duty cycle is that 0.085MPa, temperature are 78 DEG C, and hydrochloric acid is reclaimed in condensation on this condition, after after solution supersaturation, by supersaturated solution
Move in crystallizer, carry out frerrous chloride crystallization and reclaim.
(4) crystallisation by cooling in crystallizer, it is 15r/min~25r/min to control mixing speed, maintains 40 DEG C of temperature constant
5~6h, have it is substantial amounts of crystallization produce, it is to be crystallized after the completion of enter Vacuum filtration device carry out separation of solid and liquid, isolate protochloride
Iron crystal is reclaimed, and detects obtained frerrous chloride crystalline product, and product all technical is up to standard, its technical parameter such as table
Shown in 1.
(5) excessive reduced iron powder is added into liquid after crystallization (nickelic mother liquor), the excess coefficient of reduced iron powder is 2.8, water
Bath is heated to after 85 DEG C of reaction 2h, and washing and filtering obtains filtrate and filter residue, and filtrate is solution of ferrous chloride, returns it to rotation
Electrolysis processing is carried out again in the anode slot for flowing diaphragm electrolysis.After tested, in solution of ferrous chloride ferrous content 150g/L~
200g/L, nickel content is less than 1g/L, except nickel rate reaches more than 95%.Filter residue is dried in vacuo, vacuum drying temperature is
100 DEG C, vacuum drying 2h obtains the mass fraction of nickel in iron nickel powder, iron nickel powder more than 30%.
The technical parameter of frerrous chloride crystal product obtained by the present embodiment of table 1
| Index name | Index request | Testing result | |
| 1 | Outward appearance | Green-blue crystals | Green-blue crystals |
| 2 | Frerrous chloride content (FeCl2.4H2O)≥ | 96 | 98.21 |
| 3 | Chlorination iron content (FeCl3)≤ | 0.5 | 0.18 |
| 4 | Water insoluble matter content≤ | 0.5 | 0.02 |
| 5 | Free acid (in terms of HCl) content≤ | 0.5 | 0.15 |
| 6 | Arsenic (As) content≤ | 0.002 | 0.001 |
| 7 | Lead (Pb) content≤ | 0.004 | 0.002 |
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of regeneration treating method of highly acidity Ni from waste etching FeCl 3 solution containing, comprises the following steps：
(1), highly acidity Ni from waste etching FeCl 3 solution containing is electrolysed using eddy flow diaphragm process, anolyte and the moon is obtained
Pole liquid, gained anolyte is the regeneration etching solution available for etching work procedure；
(2) catholyte obtained by step (1), is evaporated crystallization, frerrous chloride crystal and nickelic mother liquor, evaporative crystallization production is obtained
Hydrochloric acid is obtained after raw steam is condensed；
(3) iron powder, is added into nickelic mother liquor obtained by step (2) and enters line replacement reaction, then filters, obtains filter residue and filtrate,
Gained filtrate is solution of ferrous chloride, and gained filter residue obtains iron nickel powder after drying.
2. the regeneration treating method of highly acidity Ni from waste etching FeCl 3 solution containing according to claim 1, it is characterised in that：
Carried out again at electrolysis in the anode slot for the eddy flow diaphragm electrolysis that solution of ferrous chloride obtained by step (3) is back in step (1)
Reason.
3. the regeneration treating method of highly acidity Ni from waste etching FeCl 3 solution containing according to claim 1, it is characterised in that：
In step (1), the decomposition voltage that the eddy flow diaphragm electrolysis is used is 3.5v~4.5v, and electrolysis time is not less than 3h, is electrolysed
The current density of journey Anodic electrode is 130A/m2~190A/m2。
4. the regeneration treating method of highly acidity Ni from waste etching FeCl 3 solution containing according to claim 1, it is characterised in that：
In step (2), the evaporation and crystal process is carried out under nitrogen protection atmosphere, and nitrogen intake control 6L/min~
7L/min。
5. the regeneration treating method of highly acidity Ni from waste etching FeCl 3 solution containing according to claim 4, it is characterised in that：
In step (2), the evaporation and crystal process is carried out under condition of negative pressure, its vacuum degree control in 0.084MPa~0.086MPa,
Evaporating temperature is controlled at 76 DEG C~80 DEG C.
6. the regeneration treating method of highly acidity Ni from waste etching FeCl 3 solution containing according to claim 1, it is characterised in that：
In step (3), the iron powder be reduced iron powder, iron powder addition excess coefficient be 2.8, it is described displacement reaction reaction time be
2~3h, the drying is vacuum drying, and vacuum drying temperature is 90 DEG C~100 DEG C, and vacuum drying time is not less than 2h.
7. the regeneration treating method of highly acidity Ni from waste etching FeCl 3 solution containing according to claim 1, it is characterised in that：
In step (1), acidity >=100g/L of the etching waste liquor.
8. the regeneration treating method of highly acidity Ni from waste etching FeCl 3 solution containing according to claim 7, it is characterised in that：
In step (1), the etching waste liquor is the etching produced by after using ferric trichloride etching solution to being handled containing nickel and stainless steel
Waste liquid, its main chemical compositions are Fe3+、Fe2+、Ni2+、H+And Cl-。
9. the regeneration treating method of highly acidity Ni from waste etching FeCl 3 solution containing according to claim 1, it is characterised in that：
In step (1), the barrier film that the eddy flow diaphragm electrolysis is used is homogeneous-phase anion exchange film, the anode that eddy flow diaphragm electrolysis is used
Electrode is metal Ti electrode.
10. according to the regeneration treatment side of highly acidity Ni from waste etching FeCl 3 solution containing according to any one of claims 1 to 9
Method, it is characterised in that：In step (3), the contents of the solution of ferrous chloride ferrous ions is 150g/L~200g/L, nickel from
The content of son is less than 1g/L, except the mass fraction that nickel rate is more than nickel in 95%, the iron nickel powder is more than 30%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107385220A (en) * | 2017-08-04 | 2017-11-24 | 俞振元 | A kind of method of the reclaiming high purity nickel from waste nickel catalyst |
| CN109208039A (en) * | 2018-09-30 | 2019-01-15 | 广州市吉池环保科技有限公司 | A method of aging copper electrolyte is purified with diaphragm process |
| CN110218878A (en) * | 2019-07-01 | 2019-09-10 | 陕西安信显像管循环处理应用有限公司 | A kind of method of acidic etching liquid displacement production frerrous chloride |
| CN112251755A (en) * | 2020-09-27 | 2021-01-22 | 深圳市祺鑫环保科技有限公司 | Recovery processing method and recovery processing system for ferric trichloride etching waste liquid |
| CN114990339A (en) * | 2022-05-23 | 2022-09-02 | 广东鑫菱环境科技有限公司 | Method for recovering and recycling semiconductor copper alloy etching solution |
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| CN107385220A (en) * | 2017-08-04 | 2017-11-24 | 俞振元 | A kind of method of the reclaiming high purity nickel from waste nickel catalyst |
| CN109208039A (en) * | 2018-09-30 | 2019-01-15 | 广州市吉池环保科技有限公司 | A method of aging copper electrolyte is purified with diaphragm process |
| CN109208039B (en) * | 2018-09-30 | 2020-04-03 | 广州市吉池环保科技有限公司 | Method for purifying aged copper electrolyte by diaphragm electrolysis method |
| CN110218878A (en) * | 2019-07-01 | 2019-09-10 | 陕西安信显像管循环处理应用有限公司 | A kind of method of acidic etching liquid displacement production frerrous chloride |
| CN112251755A (en) * | 2020-09-27 | 2021-01-22 | 深圳市祺鑫环保科技有限公司 | Recovery processing method and recovery processing system for ferric trichloride etching waste liquid |
| CN112251755B (en) * | 2020-09-27 | 2022-04-29 | 深圳市祺鑫环保科技有限公司 | Recovery processing method and recovery processing system for ferric trichloride etching waste liquid |
| CN114990339A (en) * | 2022-05-23 | 2022-09-02 | 广东鑫菱环境科技有限公司 | Method for recovering and recycling semiconductor copper alloy etching solution |
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