EP2401422A2 - Procédé et dispositif de régénération de solutions de décapage contenant du peroxodisulfate - Google Patents
Procédé et dispositif de régénération de solutions de décapage contenant du peroxodisulfateInfo
- Publication number
- EP2401422A2 EP2401422A2 EP10722522A EP10722522A EP2401422A2 EP 2401422 A2 EP2401422 A2 EP 2401422A2 EP 10722522 A EP10722522 A EP 10722522A EP 10722522 A EP10722522 A EP 10722522A EP 2401422 A2 EP2401422 A2 EP 2401422A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- copper
- anode
- pickling
- cathode
- peroxodisulfate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000005554 pickling Methods 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 54
- 125000005385 peroxodisulfate group Chemical group 0.000 title claims abstract description 28
- 230000001172 regenerating effect Effects 0.000 title claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052802 copper Inorganic materials 0.000 claims abstract description 43
- 239000010949 copper Substances 0.000 claims abstract description 43
- 238000004064 recycling Methods 0.000 claims abstract description 37
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910003460 diamond Inorganic materials 0.000 claims description 26
- 239000010432 diamond Substances 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 230000008929 regeneration Effects 0.000 claims description 14
- 238000011069 regeneration method Methods 0.000 claims description 14
- 238000005341 cation exchange Methods 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 8
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005275 alloying Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910001200 Ferrotitanium Inorganic materials 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 230000008878 coupling Effects 0.000 claims 1
- 238000010168 coupling process Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- 229910052715 tantalum Inorganic materials 0.000 claims 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 3
- 239000003518 caustics Substances 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 30
- 229910052697 platinum Inorganic materials 0.000 description 18
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 14
- 230000007062 hydrolysis Effects 0.000 description 12
- 238000006460 hydrolysis reaction Methods 0.000 description 12
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 235000011152 sodium sulphate Nutrition 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000009533 lab test Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910000570 Cupronickel Inorganic materials 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 230000028161 membrane depolarization Effects 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 2
- 238000010405 reoxidation reaction Methods 0.000 description 2
- BUFQZEHPOKLSTP-UHFFFAOYSA-M sodium;oxido hydrogen sulfate Chemical compound [Na+].OS(=O)(=O)O[O-] BUFQZEHPOKLSTP-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 101150006573 PAN1 gene Proteins 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002146 bilateral effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 208000035269 cancer or benign tumor Diseases 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000002999 depolarising effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000275 quality assurance Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000005514 two-phase flow Effects 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
-
- 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
- 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
- C25B1/01—Products
- C25B1/28—Per-compounds
- C25B1/29—Persulfates
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
-
- 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
-
- 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
Definitions
- the invention relates to a method and an electrolysis cell for regenerating pickling solutions containing peroxosulphate for copper and copper materials, on the one hand, the redeemed copper recovered, on the other hand, the mordant Peroxodisul- fat and / or Peroxomonosulfat can be regenerated.
- pickling is to be understood below all other based on similar principles chemically abrasive surface treatment methods, such as firing, etching, glazing, demetallizing, deburring u. a.
- demetallizing z For example, the dissolution of layers consisting of copper and nickel by means of peroxosulfate demetallization solutions is in principle equivalent to the pickling of copper-nickel alloys.
- the new regeneration process is intended to make it easy to pickle copper and copper alloys in a closed loop process, to completely or partially regenerate the etch chemicals, and to recover the redeemed copper and possibly other alloying constituents.
- the recovered metals can be reused, the consumption of pickling chemicals drastically reduced and the accumulation of exhausted pickling solutions that can be disposed of only with great effort, be completely avoided.
- the peroxodisulfate regeneration takes place at high anodic current densities of 40 to 70 A / dm 2 and a high total sulfate content (sulfuric acid / sulfate concentrations) of preferably> 3 mol / l and with additional use of potential-enhancing additives. Since only maximum current densities of 1, 5 to 2.5 A / dm 2 are possible to recover the copper from the spent pickling solutions in a compact, firmly adhering form, using conventional, simple plate electrolysis cells, there is a required current density ratio for the Anodic Persulfate Formation for Cathodic Copper Deposition from 20 to 30. These extremely different requirements for both electrode reactions are the main reason why it has not been possible to combine both electrode processes in a simply constructed electrolysis cell divided by cation exchange membranes.
- a disadvantage was the relatively high expenditure on equipment for the rotating cathode and the required division of the anode compartment into a larger number of small-volume anode pockets, which in conjunction with the relatively low current capacity of a single cell with a rotating cathode to a high equipment cost for a complete technical Recycling plant led.
- the problem to be solved by the invention therefore consists in avoiding the disadvantages of the known persulfate recycling methods and by the combination of both electrolysis processes in a comparatively simply constructed recycling electrolysis cell with planar cathodes, dispensing with the use of rotation Cathodes significantly reduce the equipment required and thereby significantly improve the efficiency of the recycling process.
- the insensitivity of the diamond-coated anodes with respect to existing peroxomonosulfates can also be used according to the invention so that a partial stream of the spent pickling solution can be fed directly into the anode chambers, bypassing the catholyte circuit, without reducing the anodic current efficiency of the peroxodisulfate regeneration.
- This procedure is advantageous in that, in addition, copper passes into the cathode space through the transfer of copper ions through the cation exchange membranes and can be deposited there. A corresponding amount of spent pickling solution then needs to be fed to compensate for the copper balance less in the catholyte cycle. However, even less residual peroxodisulfate is fed into the catholyte, as a result of which an even greater proportion of the remaining peroxodisulfate remains in the regenerate and can be used further for the pickling process.
- the sulfates / peroxosulfates used are in particular those of the alkali metals and ammonium, preferably the sodium sulfate / peroxosulfate.
- sulfates / peroxosulfates of other metals alone or in admixture with sulfates / peroxosulfates of the alkali metals.
- the metal sulfates of alloy constituents such as nickel, zinc or even iron itself, which are enriched in pickling of alloys in the pickling bath, are capable of forming peroxodisulfates which are capable of completely or partially replacing the sodium peroxosulfate in the regenerate.
- magnesium sulphate / peroxosulphate as the pickling medium, less as an alloy constituent but as a substitute for sodium sulphate / peroxosulphate. This has particular advantages with regard to a room temperature more than twice as high molar solubility of magnesium sulfate compared to sodium sulfate.
- planar cathodes to be used according to the invention it is possible to use both sheets made of copper, stainless steel or titanium, and copper expanded metals, in one or more layers or in combination with cathode sheets.
- the electrochemically active surface can be increased and also the amount of copper to be deposited per cathode surface can be increased until the cathode is changed.
- FIG. 1 shows a cross-section illustrating the arrangement of the rod-divided anode within the anode pocket to the planar cathode (with stylized streamline profile).
- the recycling electrolysis cell consists of the cell container 3, in which a bilaterally acting planar cathode 4 and two anode cassettes 5 are arranged.
- the cathode-facing sides of the anode cassettes consist of vertical slotted plates in which the cation exchange membranes 6 are clamped.
- the niobium anodes 7 of 5 to 12 mm width, which are subdivided into vertical strips or rods, are provided with a coating of doped diamond 8. They are arranged at a distance of 50 to 70 mm from the slots in the edge plates of the anode casings, as illustrated in FIG. 2 using the example of an anode which is subdivided into bars and a planar cathode which acts only on one side.
- the exhausted pickling solution is fed from the pickling tank 1 by means of the metering pump 2 into the catholyte circuit, which is circulated by means of the catholyte circulation pump 10 out of the catholyte circulation vessel 9 via the cathode chamber.
- One of the metered amount of pickling solution corresponding proportion of the stationary catholyte enters at 11 in the anode cassettes 5, flows through them and passes through a gas separator as reclaim back into the pickling pan 1.
- the metering pump 14 an additional amount of a peroxodisulfate solution from the container 13, also to compensate for leaching losses to pickling solution.
- the anulfate regeneration anodes process was investigated using a pre-decarburized pickling solution still containing peroxosulfate, using the diamond-coated anodes to be used in the invention in comparison to the smooth platinum anodes.
- the laboratory test cell had an effective anode area of 30 cm 2 .
- the cathode consisted of several stainless steel expanded mesh, the separation of anolyte and catholyte was a NAFION N450 cation exchange membrane.
- the catholyte used was dil.
- Sulfuric acid, the anolyte solution had the following basic composition: 250 g / l sodium sulfate 50 g / l sodium peroxodisulfate
- Experiment 2 Diamond electrode as in verse 1, but after previous hydrolysis.
- Experiment 3 Comparative experiment with smooth platinum anode, without previous hydrolysis and without potential-increasing additives.
- Example 1 In the same divided laboratory test cell of Example 1, the following starting solutions with different cations and total sulfate contents were electrolyzed with the diamond-coated anode under the same conditions (current density 40 A / dm 2 , electrolysis time 90 min) (in contrast to Example 1 without starting persulfate contents).
- a recycling electrolysis cell was used, which was equipped with two double-acting cathode plates made of stainless steel with an electrochemically effective total area of 200 dm 2 .
- the three anode cassettes each contained 10 vertical, 8 mm wide diamond coated niobium anode strips.
- the middle anode pocket was bilateral and contained two NAFION cation exchange membranes clamped in two plastic plates each fitted with vertical slots opposite the anode strips.
- the two edge-anode cassettes were constructed analogously, but they each contained only one cation exchange membrane and were unilateral.
- the total electrochemically active anode area was 24 dm 2 . This results in a cathode / anode area ratio of 8.33.
- the stationary catholyte was circulated by circulation pump.
- a metering pump 55 l of the pickling solution from the pickling tank were fed into the catholyte cycle every hour.
- This pickling solution had the following composition:
- the 55 l / h catholyte solution fed with 13 g / l NaPS into the anode cassettes was anodically concentrated to 65.5 g / l NaPS. This corresponds to an amount of sodium peroxodisulfate regenerate of 3,603 g / h fed into the pickling bath. Of these anodically 2.888 g / h were formed, corresponding to a real current yield of 65.0%. Including in the calculation the amount of NaPS residual contained in the catholyte fed in, which would have had to be completely reduced in previous recycling processes, results in an apparent anodic current efficiency of 81.1%.
- the NaPS consumption without recycling was about 4,400 g / h, including the carry-over and decomposition losses, which remained approximately constant with and without recycling.
- about 81.9% of the amount of NaPS used without recycling could be recovered by the recycling process, in addition to the recovery of 561 g / h of copper.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
L'invention a pour objet de régénérer, par un procédé de circulation, des solutions de décapage contenant du peroxodisulfate épuisées destinées à des matériaux de cuivre, dans une cellule électrolytique de recyclage compartimentée, le cuivre dissous étant tout d'abord déposé sur la cathode, puis le peroxodisulfate de décapage étant réoxydé au niveau de l'anode. Selon l'invention, on fait appel à une solution de décapage qui est mise en circulation en passant par le bain de décapage et la cellule électrolytique de recyclage et contient, en plus de 0,2 à 1,0 mol/l de peroxodisulfate, du sulfate en excès et de l'acide sulfurique libre avec une teneur totale en sulfate de 1 à 3 mol/l. A partir de la solution de décapage épuisée, dans le cellule électrolytique de recyclage compartimentée, le cuivre dissous est récupéré au niveau de cathodes planes avec des densités de courant cathodiques de 4 à 7 A/dm2, et le catholyte contenant du peroxosulfate résiduel parcourt ensuite les espaces anodiques dans lesquels le peroxodisulfate est réoxydé avec des densités de courant de 20 à 50 A/dm2, au niveau des anodes qui se composent de métal valve revêtu de diamant et se subdivisent en bandes ou barres perpendiculaires de largeur de 5 à 10 mm. L'invention permet une mise en oeuvre efficace du procédé de régénération de solutions de décapage sans adjonction de substance augmentant le potentiel et sans que le peroxosulfate subsistant dans le bain de décapage épuisé doive être complètement supprimé avant la réoxydation anodique. De cette manière, et grâce à l'utilisation d'une cellule électrolytique de recyclage de structure relativement simple, ce procédé permet d'obtenir une bonne rentabilité pour une qualité toujours aussi élevée des surfaces traitées.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE200910004155 DE102009004155A1 (de) | 2009-01-09 | 2009-01-09 | Verfahren und Vorrichtung zum Regenerieren von Peroxodisulfat-Beizlösungen |
| PCT/DE2010/000007 WO2010078866A2 (fr) | 2009-01-09 | 2010-01-07 | Procédé et dispositif de régénération de solutions de décapage contenant du peroxodisulfate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2401422A2 true EP2401422A2 (fr) | 2012-01-04 |
Family
ID=42243552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP10722522A Withdrawn EP2401422A2 (fr) | 2009-01-09 | 2010-01-07 | Procédé et dispositif de régénération de solutions de décapage contenant du peroxodisulfate |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP2401422A2 (fr) |
| DE (1) | DE102009004155A1 (fr) |
| WO (1) | WO2010078866A2 (fr) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102013114881A1 (de) | 2013-12-25 | 2015-06-25 | Brose Fahrzeugteile Gmbh & Co. Kommanditgesellschaft, Hallstadt | Steuersystem für eine motorische Verschlusselementanordnung eines Kraftfahrzeugs |
| CN108531914A (zh) * | 2018-06-15 | 2018-09-14 | 哈尔滨工业大学深圳研究生院 | 一种h2so4/s2o82-微蚀刻废液的铜回收及同步再生微蚀刻液系统及方法 |
| CN113088981B (zh) * | 2021-04-10 | 2022-06-24 | 贵州丝域环能科技有限公司 | 一种不锈钢酸洗钝化液的制备、处理及再生方法 |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD211129B1 (de) | 1982-11-05 | 1986-12-17 | Hermann Matschiner | Kreislaufverfahren zum beizen von kupfer und kupferlegierungen |
| DE3469041D1 (en) * | 1983-10-06 | 1988-03-03 | Olin Corp | Process for cleaning copper base materials and regenerating the cleaning solution |
| DE4137022C2 (de) | 1991-11-11 | 1993-11-25 | Eilenburger Chemie Werk Gmbh | Verfahren und Vorrichtung zur Regenerierung schwefelsaurer, kupferhaltiger Peroxodisulfat-Beizlösungen |
| DE4211555C1 (de) * | 1992-04-06 | 1993-12-02 | Eilenburger Chemie Werk Gmbh | Bipolare Filterpressenzelle zur Herstellung von Peroxodisulfaten |
| DE19506832A1 (de) | 1995-02-28 | 1996-08-29 | Eilenburger Elektrolyse & Umwelttechnik Gmbh | Kreislaufverfahren zum Beizen von Kupfer und Kupferlegierungen |
| DE19850530A1 (de) * | 1998-11-03 | 2000-05-25 | Eilenburger Elektrolyse & Umwelttechnik Gmbh | Kreislaufverfahren zum Beizen von Kupfer und Kupferlegierungen |
| DE19948184C2 (de) | 1999-10-06 | 2001-08-09 | Fraunhofer Ges Forschung | Elektrochemische Herstellung von Peroxo-dischwefelsäure unter Einsatz von diamantbeschichteten Elektroden |
| DE29919231U1 (de) * | 1999-11-02 | 2000-01-27 | Eilenburger Elektrolyse Und Um | Geteilte Elektrolysezelle zur kathodischen Metallrückgewinnung und/oder zur anodischen Oxidation |
| DE19962672A1 (de) | 1999-12-23 | 2001-06-28 | Eilenburger Elektrolyse & Umwelttechnik Gmbh | Verfahren und Vorrichtung zur Herstellung oder Regenerierung von Peroxodisulfaten |
| DE10019683A1 (de) | 2000-04-20 | 2001-10-25 | Degussa | Verfahren zur Herstellung von Alkalimetall- und Ammoniumperoxodisulfat |
| DE10112075C1 (de) | 2001-03-12 | 2002-10-31 | Eilenburger Elektrolyse & Umwelttechnik Gmbh | Verfahren und Vorrichtung zur Rückgewinnung von Metallen, auch in Kombination mit anodischen Koppelprozessen |
| DE10219688A1 (de) * | 2002-05-02 | 2003-11-20 | Condias Gmbh | Verfahren und Vorrichtung zur oxidativen Behandlung von Oberflächen |
| DE102004027623A1 (de) * | 2004-06-05 | 2005-12-22 | Degussa Initiators Gmbh & Co. Kg | Verfahren zur Herstellung von Peroxodisulfaten in wässriger Lösung |
-
2009
- 2009-01-09 DE DE200910004155 patent/DE102009004155A1/de active Pending
-
2010
- 2010-01-07 WO PCT/DE2010/000007 patent/WO2010078866A2/fr not_active Ceased
- 2010-01-07 EP EP10722522A patent/EP2401422A2/fr not_active Withdrawn
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2010078866A2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010078866A3 (fr) | 2010-10-14 |
| DE102009004155A1 (de) | 2010-07-15 |
| WO2010078866A2 (fr) | 2010-07-15 |
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