CN104894599A - Recycling process of tin-removing waste liquid - Google Patents
Recycling process of tin-removing waste liquid Download PDFInfo
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- CN104894599A CN104894599A CN201510347537.XA CN201510347537A CN104894599A CN 104894599 A CN104894599 A CN 104894599A CN 201510347537 A CN201510347537 A CN 201510347537A CN 104894599 A CN104894599 A CN 104894599A
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-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/38—Nitric acid
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/14—Electrolytic production, recovery or refining of metals by electrolysis of solutions of tin
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a recycling process of tin-removing waste liquid. The method includes the steps of S1, feeding the tin-removing waste liquid into a distilling device, and performing pressure reduction distillation under the temperature of 65-80 DEG C and the pressure of (0.2-0.5)*1.03*10<5>Pa to recycle nitric acid; S2, feeding distillation residual liquid into an electrolytic tank with an ion exchange membrane for electrolysis, controlling current density and cathode potential to recycle copper in the residual liquid through electrolysis, acquiring tin dioxide at the anode of the electrolytic tank, and acquiring metal copper at the cathode of the electrolytic tank; S3, controlling current density to be unchanged after metal copper is recycled, and changing cathode potential to recycle tin through electrolysis, constantly adding sulfuric acid solution in a cathode chamber during the electrolysis process until the electrolysis is ended, acquiring the tin dioxide at the anode of the electrolytic tank, and acquiring metal tin at the cathode of the electrolytic tank, wherein the current density is 100-200A/m<2>. The recycling process has the advantages that no chemical reagent is added, and secondary pollution is avoided.
Description
Technical field
The present invention relates to a kind of recycling technique of moving back tin waste liquid, belong to environmental technology field.
Background technology
PCB, also known as printed circuit board (PCB), is the supplier of electronic devices and components electrical connection.Its development has the history of more than 100 year, its design mainly layout design, adopts the major advantage of circuit card to be the mistake greatly reducing wiring and assembling, improves the gentle productive labor rate of Automated water.Along with the development of information industry and the increase of electronic product demand, printed electronic circuit board industry is flourish.The making processes of pcb board has 20 multiple working procedures, can produce a large amount of liquid waste liquids in these operations, and the waste liquid wherein moving back the generation of tin operation is maximum.Tin stripping liquid optionally dissolves by etching agent the waste liquid that tin in copper clad layers or gun-metal produce when ensureing that Copper base material is not etched, and etching agent can be divided into fluorochemical type, nitric acid type and nitric acid alkylsulphonic acid type.Nitric acid spent solder stripper is the liquid in deep green smell with irritating, wherein contains the free nitric acid of 20 ~ 30, the tin of 60 ~ 80g/L, the copper of 5 ~ 10g/L and the iron of 25 ~ 40g/L, also has some other a small amount of metal ions in addition.The existence of these ions not only contaminate environment but also waste resource.How effectively process a difficult problem that tin stripping liquid has become pcb board enterprise to face, can Ye Shi enterprise the prerequisite of sustainable development.
Application number be 200910301263.5 Chinese patent disclose a kind of recovery method moving back tin in tin waste liquid, sodium carbonate solution neutralization is adopted to move back tin waste liquid, add alkali again and be converted into sodium stannate at 102 ~ 115 DEG C of temperature, in solution, carbonic acid gas is passed into after filtering, sodium stannate is made to be converted into metastannic acid, through washing after filtration, calcining obtains tindioxide, the method does not adopt Distillation recovery nitric acid, in needing to use a large amount of sodium carbonate to go and nitric acid, add cost, increased a large amount of SODIUMNITRATE waste water solution (wherein also may contain great amount of soluble impurity) newly simultaneously, these waste water also need further process, add the cost of enterprise.And in follow-up workshop section again calcining obtain tindioxide, lose to be separated and obtain the chance of sodium stannate.
Sichuan University of Science & Engineering refer to the method that the electrolytical method of underpressure distillation+add obtains tindioxide and sodium stannate in ZL101918133A.Huizhou Dayawan Huilu Environment Protection Service Co., Ltd. refer to and adds lime white and evaporation lane concentration method separating metal oxonium ion in patent No. ZL102086073A, and adds the full recycling processing method reclaimed of additive realization.Dongguan City New Energy Technology Co., Ltd. refer to chemical substance such as interpolation ionogen, flocculation agent etc. and is separated the method obtaining tin mud in patent CN102492860A with CN102515259A.The above treatment process reclaimed about tin stripper has a common feature to need to add chemical substance such as ionogen, flocculation agent, alkali neutralization, extraction agent etc. to be separated acquisition metallic cation.These methods add chemical reagent such as ionogen, flocculation agent, extraction agent unavoidably has the chemical composition of part to be entrained in the tin stripper of circulation, thus has influence on quality and the stability that circuit card moves back process of tin.
Visible, how to avoid adding extra chemical reagent in tin stripping liquid reclaiming process, realize the cycling and reutilization of material in tin stripping liquid better, how to simplify production technique, reduce the energy consumption of moving back tin devil liquor recovery recycle process, accomplish real full recovery, zero release is the development core place of moving back the utilization of tin waste liquid circulation from now on.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of recycling technique of moving back tin waste liquid, this technique does not add any chemical reagent, can not cause secondary pollution.
The object of the invention is to be achieved through the following technical solutions:
Move back a recycling technique for tin waste liquid, comprise the steps:
S1. will move back tin waste liquid and pass into water distilling apparatus, at 65 ~ 80 DEG C, pressure 0.2 × 1.03 × 10
5pa ~ 0.5 × 1.03 × 10
5carry out underpressure distillation under Pa and reclaim nitric acid;
S2. above-mentioned still residue passes into electrolysis in the electrolyzer being provided with ion-exchange membrane, and control the copper in liquid more than current density and cathode potential electrolytic recovery, obtain tindioxide at the anode of electrolyzer, negative electrode obtains metallic copper;
S3. after treating that metallic copper has reclaimed, control current density is constant, changes cathode potential with electrolytic recovery tin, and carries out needing in process constantly to add sulphuric acid soln until electrolysis terminates in cathode compartment in electrolysis, obtain tindioxide at the anode of electrolyzer, negative electrode obtains metallic tin.
A kind of recycling technique of moving back tin waste liquid, also comprise the step of a circulation preparation tin stripping liquid: after step s 3, liquid more than electrolysis in extraction electrolyzer also filters, distill the nitric acid obtained in filtrate combining step S1 and obtain amalgamation liquid, then in amalgamation liquid, add additive make new tin stripping liquid.
Described additive is iron nitrate and sodium sulfonate class sustained release dosage; Described sulphuric acid soln be concentration 15 ~ 30%; Described current density is 100-200A/m
2; Cathode potential described in step S2 realizes by changing impressed voltage, and impressed voltage is 5 ~ 35V; Cathode potential described in step S3 also realizes by changing impressed voltage, and impressed voltage is 15 ~ 45V.
The nitric acid of the present invention first in low-temperature reduced-pressure Distillation recovery tin stripping liquid, then by electrolytic recovery copper and tin, finally adds reagent again and realizes nitric recycle utilization.Be provided with ion-exchange membrane in electrolyzer, ion-exchange membrane has ion-selective permeability, and namely anode membrane is only through positively charged ion, and cavity block is only through negatively charged ion.Positively charged ion enters cathodic area from positive column selectivity through anode membrane and reduction reaction occurs at negative electrode and separates out under electric field action.React as follows:
Anodic reaction is: 2H
2o-4e=O
2+ 4H
+Φ
0=1.23V
Sn
2+—2e=Sn
4+Φ
0=0.15V
Cathodic reaction is: Sn
2++ 2e=Sn Φ
0=0.136V
Sn
4++2e=Sn
2+Φ
0=0.15V
Cu
2++2e=Cu Φ
0=0.337V
H
++2e=H
2 Φ
0=0.0V
The Sn in anodic reaction can be derived according to standard potential (electrode reactions all in formula get be reduction potential)
2+oxidation will preferentially be carried out.Move back containing metallic copper in tin waste liquid, its standard electrode potential, higher than metallic tin, is separated out prior to tin at negative electrode, so can control cathode potential when producing, copper is separated out, and selects suitable cathode potential to reclaim tin, H in catholyte after waiting cupric electrolysis complete
+during concentration height also can with Sn
2+competitive precipitation, can force hydrogen to separate out by controlling hydrogen ion concentration.
The invention has the beneficial effects as follows: (1) the present invention first adopts the nitric acid in low-temperature reduced-pressure distil process recovery tin stripping liquid, copper, the tin in tin stripping liquid is reclaimed again by classification electro-deposition techniques, iron ion comes back in tin stripping liquid and recycles after regeneration, do not add any chemical reagent in whole process, can not secondary pollution be caused;
(2) the present invention is without any the discharging of waste liquid containing ammonia nitrogen, hydrogen ion, COD or metal ion in treating processes, is real zero release, zero injury, the environmental protection scheme of zero process, has great social environment health and is worth;
(3) simply, production cost is low, can obtain highly purified tindioxide, copper and metallic tin, without the need to carrying out secondary processing to product again for technological process of the present invention and processing unit.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described in further detail, but protection scope of the present invention is not limited to the following stated.
[embodiment 1] a kind of recycling technique of moving back tin waste liquid, comprises the steps:
S1. will move back tin waste liquid and pass into water distilling apparatus, at 65 DEG C, pressure 0.5 × 1.03 × 10
5carry out underpressure distillation under Pa and reclaim nitric acid;
S2. above-mentioned still residue passes into electrolysis in the electrolyzer being provided with ion-exchange membrane, and control the copper in liquid more than current density and cathode potential electrolytic recovery, obtain tindioxide at the anode of electrolyzer, negative electrode obtains metallic copper;
S3. after treating that metallic copper has reclaimed, control current density is constant, changes cathode potential with electrolytic recovery tin, and carries out needing in process constantly to add sulphuric acid soln until electrolysis terminates in cathode compartment in electrolysis, obtain tindioxide at the anode of electrolyzer, negative electrode obtains metallic tin.
A kind of recycling technique of moving back tin waste liquid, also comprise the step of a circulation preparation tin stripping liquid: after step s 3, liquid more than electrolysis in extraction electrolyzer also filters, distill the nitric acid obtained in filtrate combining step S1 and obtain amalgamation liquid, then in amalgamation liquid, add additive make new tin stripping liquid.
Described additive is iron nitrate and sodium sulfonate class sustained release dosage.
Described sulphuric acid soln volume is concentration 15%; Described current density is 100A/m
2.
Cathode potential described in step S2 realizes by changing impressed voltage, and impressed voltage is 5V.
Cathode potential described in step S3 also realizes by changing impressed voltage, and impressed voltage is 15V.
[embodiment 2] a kind of recycling technique of moving back tin waste liquid, comprises the steps:
S1. will move back tin waste liquid and pass into water distilling apparatus, at 70 DEG C, pressure 0.4 × 1.03 × 10
5carry out underpressure distillation under Pa and reclaim nitric acid;
S2. above-mentioned still residue passes into electrolysis in the electrolyzer being provided with ion-exchange membrane, and control the copper in liquid more than current density and cathode potential electrolytic recovery, obtain tindioxide at the anode of electrolyzer, negative electrode obtains metallic copper;
S3. after treating that metallic copper has reclaimed, control current density is constant, changes cathode potential with electrolytic recovery tin, and carries out needing in process constantly to add sulphuric acid soln until electrolysis terminates in cathode compartment in electrolysis, obtain tindioxide at the anode of electrolyzer, negative electrode obtains metallic tin.
A kind of recycling technique of moving back tin waste liquid, also comprise the step of a circulation preparation tin stripping liquid: after step s 3, liquid more than electrolysis in extraction electrolyzer also filters, distill the nitric acid obtained in filtrate combining step S1 and obtain amalgamation liquid, then in amalgamation liquid, add additive make new tin stripping liquid.
Described additive is iron nitrate and sodium sulfonate class sustained release dosage.
Described sulphuric acid soln be concentration 20%; Described current density is 120A/m
2.
Cathode potential described in step S2 realizes by changing impressed voltage, and impressed voltage is 10V.
Cathode potential described in step S3 also realizes by changing impressed voltage, and impressed voltage is 20V.
[embodiment 3] a kind of recycling technique of moving back tin waste liquid, comprises the steps:
S1. will move back tin waste liquid and pass into water distilling apparatus, at 75 DEG C, pressure 0.3 × 1.03 × 10
5carry out underpressure distillation under Pa and reclaim nitric acid;
S2. above-mentioned still residue passes into electrolysis in the electrolyzer being provided with ion-exchange membrane, and control the copper in liquid more than current density and cathode potential electrolytic recovery, obtain tindioxide at the anode of electrolyzer, negative electrode obtains metallic copper;
S3. after treating that metallic copper has reclaimed, control current density is constant, changes cathode potential with electrolytic recovery tin, and carries out needing in process constantly to add sulphuric acid soln until electrolysis terminates in cathode compartment in electrolysis, obtain tindioxide at the anode of electrolyzer, negative electrode obtains metallic tin.
A kind of recycling technique of moving back tin waste liquid, also comprise the step of a circulation preparation tin stripping liquid: after step s 3, liquid more than electrolysis in extraction electrolyzer also filters, distill the nitric acid obtained in filtrate combining step S1 and obtain amalgamation liquid, then in amalgamation liquid, add additive make new tin stripping liquid.
Described additive is iron nitrate and sodium sulfonate class sustained release dosage.
Described sulphuric acid soln be concentration 25%; Described current density is 160A/m
2.
Cathode potential described in step S2 realizes by changing impressed voltage, and impressed voltage is 15V.
Cathode potential described in step S3 also realizes by changing impressed voltage, and impressed voltage is 25V.
[embodiment 4] a kind of recycling technique of moving back tin waste liquid, comprises the steps:
S1. will move back tin waste liquid and pass into water distilling apparatus, at 75 DEG C, pressure 0.25 × 1.03 × 10
5carry out underpressure distillation under Pa and reclaim nitric acid;
S2. above-mentioned still residue passes into electrolysis in the electrolyzer being provided with ion-exchange membrane, and control the copper in liquid more than current density and cathode potential electrolytic recovery, obtain tindioxide at the anode of electrolyzer, negative electrode obtains metallic copper;
S3. after treating that metallic copper has reclaimed, control current density is constant, changes cathode potential with electrolytic recovery tin, and carries out needing in process constantly to add sulphuric acid soln until electrolysis terminates in cathode compartment in electrolysis, obtain tindioxide at the anode of electrolyzer, negative electrode obtains metallic tin.
A kind of recycling technique of moving back tin waste liquid, also comprise the step of a circulation preparation tin stripping liquid: after step s 3, liquid more than electrolysis in extraction electrolyzer also filters, distill the nitric acid obtained in filtrate combining step S1 and obtain amalgamation liquid, then in amalgamation liquid, add additive make new tin stripping liquid.
Described additive is iron nitrate and sodium sulfonate class sustained release dosage.
Described sulphuric acid soln be concentration 28%; Described current density is 190A/m
2.
Cathode potential described in step S2 realizes by changing impressed voltage, and impressed voltage is 25V.
Cathode potential described in step S3 also realizes by changing impressed voltage, and impressed voltage is 35V.
[embodiment 5] a kind of recycling technique of moving back tin waste liquid, comprises the steps:
S1. will move back tin waste liquid and pass into water distilling apparatus, at 80 DEG C, pressure 0.2 × 1.03 × 10
5carry out underpressure distillation under Pa and reclaim nitric acid;
S2. above-mentioned still residue passes into electrolysis in the electrolyzer being provided with ion-exchange membrane, and control the copper in liquid more than current density and cathode potential electrolytic recovery, obtain tindioxide at the anode of electrolyzer, negative electrode obtains metallic copper;
S3. after treating that metallic copper has reclaimed, control current density is constant, changes cathode potential with electrolytic recovery tin, and carries out needing in process constantly to add sulphuric acid soln until electrolysis terminates in cathode compartment in electrolysis, obtain tindioxide at the anode of electrolyzer, negative electrode obtains metallic tin.
A kind of recycling technique of moving back tin waste liquid, also comprise the step of a circulation preparation tin stripping liquid: after step s 3, liquid more than electrolysis in extraction electrolyzer also filters, distill the nitric acid obtained in filtrate combining step S1 and obtain amalgamation liquid, then in amalgamation liquid, add additive make new tin stripping liquid.
Described additive is iron nitrate and sodium sulfonate class sustained release dosage.
Described sulphuric acid soln be concentration 30%; Described current density is 200A/m
2.
Cathode potential described in step S2 realizes by changing impressed voltage, and impressed voltage is 35V.
Cathode potential described in step S3 also realizes by changing impressed voltage, and impressed voltage is 45V.
Claims (7)
1. move back a recycling technique for tin waste liquid, it is characterized in that, comprise the steps:
S1. will move back tin waste liquid and pass into water distilling apparatus, at 65 ~ 80 DEG C, pressure 0.2 × 1.03 × 10
5pa ~ 0.5 × 1.03 × 10
5carry out underpressure distillation under Pa and reclaim nitric acid;
S2. above-mentioned still residue passes into electrolysis in the electrolyzer being provided with ion-exchange membrane, and control the copper in liquid more than current density and cathode potential electrolytic recovery, obtain tindioxide at the anode of electrolyzer, negative electrode obtains metallic copper;
S3. after treating that metallic copper has reclaimed, control current density is constant, changes cathode potential with electrolytic recovery tin, and carries out needing in process constantly to add sulphuric acid soln until electrolysis terminates in cathode compartment in electrolysis, obtain tindioxide at the anode of electrolyzer, negative electrode obtains metallic tin.
2. a kind of recycling technique of moving back tin waste liquid according to claim 1, it is characterized in that, also comprise the step of a circulation preparation tin stripping liquid: after step s 3, liquid more than electrolysis in extraction electrolyzer also filters, distill the nitric acid obtained in filtrate combining step S1 and obtain amalgamation liquid, then in amalgamation liquid, add additive make new tin stripping liquid.
3. a kind of recycling technique of moving back tin waste liquid according to claim 2, is characterized in that, described additive is iron nitrate and sodium sulfonate class sustained release dosage.
4. a kind of recycling technique of moving back tin waste liquid according to claim 1, is characterized in that, the concentration of described sulphuric acid soln is 15 ~ 30%.
5. a kind of recycling technique of moving back tin waste liquid according to claim 1, it is characterized in that, described current density is 100-200A/m
2.
6. a kind of recycling technique of moving back tin waste liquid according to claim 1, is characterized in that, the cathode potential described in step S2 realizes by changing impressed voltage, and impressed voltage is 5 ~ 35V.
7. a kind of recycling technique of moving back tin waste liquid according to claim 1, is characterized in that, the cathode potential described in step S3 also realizes by changing impressed voltage, and impressed voltage is 15 ~ 45V.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510347537.XA CN104894599A (en) | 2015-06-23 | 2015-06-23 | Recycling process of tin-removing waste liquid |
| PCT/CN2016/077067 WO2016206418A1 (en) | 2015-06-23 | 2016-03-23 | Recycling and reusing process for spent tin stripper solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510347537.XA CN104894599A (en) | 2015-06-23 | 2015-06-23 | Recycling process of tin-removing waste liquid |
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| Publication Number | Publication Date |
|---|---|
| CN104894599A true CN104894599A (en) | 2015-09-09 |
Family
ID=54027542
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510347537.XA Pending CN104894599A (en) | 2015-06-23 | 2015-06-23 | Recycling process of tin-removing waste liquid |
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| WO (1) | WO2016206418A1 (en) |
Cited By (14)
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|---|---|---|---|---|
| CN105648472A (en) * | 2016-01-22 | 2016-06-08 | 张黎 | Recycling method and system for tin in tin stripping waste liquid and tin stripping waste liquid |
| CN106007152A (en) * | 2016-08-09 | 2016-10-12 | 成都虹华环保科技股份有限公司 | Nitric acid deplating water cyclic regeneration system |
| CN106241882A (en) * | 2016-08-27 | 2016-12-21 | 盛隆资源再生（无锡）有限公司 | A kind of method of spent solder stripper resource |
| WO2016206418A1 (en) * | 2015-06-23 | 2016-12-29 | 成都虹华环保科技股份有限公司 | Recycling and reusing process for spent tin stripper solution |
| CN106637297A (en) * | 2016-12-20 | 2017-05-10 | 深圳市胜瑞电路科技有限公司 | Treatment method of tin removing waste solution |
| CN108070721A (en) * | 2017-11-10 | 2018-05-25 | 河海大学 | A kind of nitric acid spent solder stripper tin copper recycling and regeneration method |
| CN108070720A (en) * | 2017-11-10 | 2018-05-25 | 河海大学 | A kind of comprehensive recovering process of tin removal waste liquor |
| CN108468050A (en) * | 2018-05-07 | 2018-08-31 | 昆山市新溢诚电子科技有限公司 | A kind of stripping tin liquor and its application in tin divests |
| CN109536982A (en) * | 2018-12-27 | 2019-03-29 | 广东先导稀材股份有限公司 | Preparation method of nano tin dioxide |
| CN110055537A (en) * | 2019-05-22 | 2019-07-26 | 惠州市臻鼎环保科技有限公司 | A kind of method for reclaiming of PCB nitric acid spent solder stripper |
| CN110129799A (en) * | 2019-04-30 | 2019-08-16 | 广东工业大学 | Recycling method of tin stripping waste liquid based on sulfuric acid-ferric salt system |
| CN111268843A (en) * | 2020-02-28 | 2020-06-12 | 河北大鹏医药化工有限公司 | Process for recovering nitric acid from nitrified wastewater |
| CN112011689A (en) * | 2019-05-30 | 2020-12-01 | 惠州Tcl环境科技有限公司 | Method for recovering substances from waste tin stripping waste liquid of nitric acid system |
| CN115449634A (en) * | 2022-08-26 | 2022-12-09 | 湖北永绍科技股份有限公司 | Treatment method for recycling tin stripping waste liquid |
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