WO2013168799A1 - 亜鉛系めっき金属部材表面の硝酸活性処理溶液の再生方法及びそれを用いた再生処理装置 - Google Patents
亜鉛系めっき金属部材表面の硝酸活性処理溶液の再生方法及びそれを用いた再生処理装置 Download PDFInfo
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- WO2013168799A1 WO2013168799A1 PCT/JP2013/063166 JP2013063166W WO2013168799A1 WO 2013168799 A1 WO2013168799 A1 WO 2013168799A1 JP 2013063166 W JP2013063166 W JP 2013063166W WO 2013168799 A1 WO2013168799 A1 WO 2013168799A1
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1617—Purification and regeneration of coating baths
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1619—Apparatus for electroless plating
- C23C18/1628—Specific elements or parts of the apparatus
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1689—After-treatment
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/86—Regeneration of coating baths
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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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/16—Regeneration of process solutions
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
Definitions
- the present invention relates to a method for efficiently removing zinc ions mixed in a plating material surface activated nitric acid solution in galvanizing and trivalent chromium chemical conversion treatment of steel, regenerating and recycling the nitric acid activated treatment solution, and its
- the present invention relates to a reproduction processing apparatus.
- the activated nitric acid solution zinc ions gradually accumulate due to dissolution of galvanizing from the substrate surface due to activation and bringing in the plating solution to the product from the galvanizing process, and the activation effect is lost.
- the zinc concentration in the activated nitric acid solution is accumulated and the luster of the substrate surface after the activation treatment is lost, the entire amount of the nitric acid solution needs to be replaced, and the cost of nitric acid procurement and labor are required.
- Patent Document 1 a management method and apparatus for exchanging zinc ions dissolved in an activated nitric acid solution with hydrogen ions by ion exchange are known (Patent Document 1).
- Patent Document 1 a management method and apparatus for exchanging zinc ions dissolved in an activated nitric acid solution with hydrogen ions by ion exchange are known (Patent Document 1).
- this method requires time and effort for maintaining the function of the ion exchange resin, and still has problems in terms of economy, leaving room for improvement.
- the zinc-based plating of steel is replaced with a method of replacing the total amount of the nitric acid activation treatment solution after a predetermined time, which has been widely performed in the past.
- An object is to provide a reproduction method. It is another object of the present invention to provide a regeneration treatment apparatus for a nitric acid activation treatment solution on the surface of a zinc-based plated metal member that can efficiently carry out this regeneration method.
- the present invention solves the above problem by separating and removing zinc ions contained in the nitric acid activation treatment solution on the surface of the zinc-based plated metal member as an insoluble salt with a zinc ion flocculant in the nitric acid activation treatment solution containing zinc ions.
- It has a nitric acid activation treatment tank (1), a flocculation tank (2), a filtration device (4), and a recovery liquid storage tank (3) that can be achieved efficiently, and each part is connected in series through a pipe in this order. This is based on the knowledge that a circulation circuit is formed and that the above problem can be solved efficiently by using a regeneration treatment device having a pH control device (5) at a specific position.
- the present invention is a nitric acid activation treatment solution on the surface of a zinc-based plated metal member, wherein a zinc ion flocculant is added to a nitric acid activation treatment solution containing zinc ions, and the zinc ions in the solution are converted into insoluble salts.
- a method for regenerating a nitric acid activation treatment solution characterized by aggregating and separating and removing.
- the present invention also introduces zinc ions mixed in the nitric acid activation treatment tank (1) into the coagulation tank (2) as a zinc ion-containing nitric acid activation treatment solution, and the zinc ion coagulant in the coagulation tank (2). And then mixed with a zinc ion-containing nitric acid activation treatment solution to agglomerate and remove as an insoluble salt. The resulting zinc ion removal liquid is transferred to the recovered liquid storage (3) and stored, and then the tank (3)
- the method for regenerating a nitric acid activation treatment solution is characterized in that after the pH of the nitric acid activation treatment solution is adjusted, the solution is returned to the nitric acid activation treatment tank (1).
- the present invention also includes a nitric acid activation treatment tank (1) for performing an activation treatment on the surface of a zinc-based plated metal member using a nitric acid activation treatment solution, a zinc ion flocculant added to the nitric acid activation treatment solution, A coagulation tank (2) for aggregating zinc ions as an insoluble salt, a filtration device (4) for separating and removing the coagulated insoluble zinc salt, and a recovery liquid storage tank (3) for temporarily storing the filtrate, each part in this order
- a circulation circuit is formed by connecting through a pipe, and further, a recovery liquid storage tank (3), a nitric acid activation treatment tank (1), or a recovery liquid storage tank (3) and an activation treatment tank (1 1)
- a zinc-based plated metal member characterized in that at least one or more of the continuous pipes) has a pH control device (5) that maintains the pH of the nitric acid activation treatment solution according to the nitric acid concentration within a specified range.
- zinc can be efficiently recovered and removed from the nitric acid activation treatment solution in which zinc is accumulated, and the nitric acid activation treatment solution can be reused. Also, the recovered zinc can be roasted and contributed to effective utilization of resources as zinc oxide.
- FIG. 1 shows an outline of a reproduction processing apparatus of the present invention.
- the outline of the state at the start of the reproduction process of the present invention is shown.
- the outline of the state 22 hours after the start of the regeneration process of the present invention is shown.
- the outline of the state 24 hours after the start of the regeneration process of the present invention is shown.
- the nitric acid activation treatment solution targeted in the present invention is preferably a solution having a total nitric acid concentration of 0.5 to 80 g / L, a pH of 0.5 to 3.0, and a temperature of 0 to 50 ° C.
- a nitric acid activation treatment solution that satisfies this condition is preferable in that it can maintain the gloss on the surface of the zinc-based plated metal member.
- This nitric acid activation treatment solution may contain impurities. At this time, the impurities include organic ions contained in the plating solution in addition to metal ions such as iron and copper.
- the zinc ion aggregating agent for aggregating and precipitating zinc ions used in the present invention is soluble in a nitric acid active treatment solution and has a function of forming an insoluble or hardly soluble salt with the zinc ions in the treatment solution and aggregating them.
- a drug preferably oxalic acid (including hydrates such as anhydrides or dihydrates) or sodium oxalate, sodium hydrogen oxalate, ammonium oxalate, ammonium hydrogen oxalate Or an oxalate such as carbonate or carbonate such as sodium carbonate, sodium bicarbonate, ammonium carbonate, or ammonium bicarbonate.
- Oxalic acid or a salt thereof is more preferable, and oxalic acid is particularly preferable.
- the mixing amount of the zinc ion flocculant mixed with the nitric acid activation treatment solution is preferably 0.2 to 2 times the theoretical amount with respect to zinc ions, and more preferably 0.5 to 1.0 times.
- the theoretical amount of flocculant with respect to zinc is 1 mol of flocculant per mol of zinc. Therefore, 0.2 to 2 times the theoretical amount with respect to zinc is 0.2 to 2 mol of the flocculant per mol of zinc.
- a method of mixing the nitric acid activation treatment solution and the flocculant there is a method of stirring the nitric acid solution and adding the flocculant thereto, or adding the nitric acid solution while stirring the aqueous flocculant in the form of an aqueous solution or slurry. Any of these may be used.
- the mixing time of the nitric acid activation treatment solution and the flocculant is preferably 5 minutes to 24 hours, particularly preferably 10 minutes to 12 hours. When the amount falls within this range, the amount of impurities mixed into the flocculant zinc is suppressed, the formation of the agglomerates is sufficiently performed, and the recovered amount of zinc is improved. In addition, even if it mixes exceeding 24 hours, there is no difference in agglomeration and economic efficiency falls.
- the liquid temperature at the time of mixing the nitric acid activation treatment solution and the flocculant is preferably in the range of 0 to 90 ° C., but mixing at room temperature without adjusting the temperature is preferable from the viewpoint of energy cost.
- the precipitate is subjected to solid-liquid separation by filtration or the like.
- the filtrate from which the precipitate has been removed is reused as a nitric acid activation treatment solution.
- dilution is performed by adding water, or sodium hydroxide or the like is added to adjust within the range.
- the recovered precipitate (salt of coagulant and zinc) is preferably washed by a washing step in order to collect zinc with higher purity.
- water or a flocculant aqueous solution is preferably used as the cleaning liquid, but water includes pure water and ultrapure water, and the flocculant aqueous solution is preferably a flocculant aqueous solution having a concentration of 0.5 mol / l or less. .
- the salt of the flocculant and zinc is recovered immediately without washing after adding the flocculant, or when the washing is performed by a method other than filtration washing, the salt of the flocculant and zinc is separated into solid and liquid. This can be done by conventional filtration.
- the solid-liquid separated aggregate (a salt of a flocculant and zinc) can be roasted into zinc oxide.
- This roasting is preferably performed by directly heating the precipitate after the solid-liquid separation. Although it may be dried after solid-liquid separation and then roasted, direct baking is preferred from the viewpoint of energy cost, efficiency and the like.
- the roasting temperature is preferably 300 to 800 ° C, more preferably 400 to 700 ° C.
- zinc ions mixed into the nitric acid activation treatment tank (1) are introduced into the coagulation tank (2) as a zinc ion-containing nitric acid activation treatment solution, and the zinc ion coagulant is added to the coagulation tank (2).
- oxalic acid or a salt thereof and / or carbonic acid or a salt thereof is added and mixed with a zinc ion-containing nitric acid activation treatment solution to agglomerate and remove zinc ions as insoluble salts such as zinc oxalate and / or zinc carbonate. Then, the obtained zinc ion removing liquid is transferred to and stored in the collected liquid storage (3), and then the pH of the nitric acid activation treatment solution is adjusted in the tank (3) and then returned to the nitric acid activation treatment tank (1). Thus, it is preferable to regenerate the nitric acid activation treatment solution.
- a nitric acid activation treatment tank (1) for performing an activation treatment on the surface of a zinc-based plated metal member using a nitric acid activation treatment solution, a zinc ion flocculant being added to the nitric acid activation treatment solution,
- a coagulation tank (2) for coagulating zinc ions as an insoluble salt
- a filtration device (4) for separating and removing the aggregated insoluble zinc salt
- a recovery liquid storage tank (3) for temporarily storing the filtrate.
- a circulation circuit is formed by connecting the pipes in this order, and further, a recovery liquid storage tank (3), a nitric acid activation treatment tank (1), or a recovery liquid storage tank (3) and an activation treatment tank.
- the zinc-based plating characterized in that at least one or more of the continuous pipes of (1) has a pH control device (5) for maintaining the pH depending on the nitric acid concentration of the nitric acid activation treatment solution within a specified range.
- Regeneration treatment equipment for nitric acid activation treatment solution on metal member surface It is preferable to use.
- the nitric acid activation treatment of the plating material is performed in the nitric acid activation treatment solution tank (1).
- the pH increased by the treatment is adjusted to the designated pH by sending the nitric acid activation treatment solution after zinc removal stored in the recovery liquid storage tank (3) to the nitric acid activation treatment solution treatment tank (1) with a liquid feed pump. Is preferred.
- the pH is preferably controlled using a pH sensor. It is preferable that the nitric acid activation treatment solution after the removal of zinc is sent to the nitric acid activation treatment solution treatment tank (1) and surplus is sent to the coagulation tank (2) and accumulated.
- the zinc ion concentration in the solution is measured, and a theoretical amount of zinc ion coagulant for the zinc concentration ion concentration is stored in the coagulation tank (2). It is preferable to add and mix to coagulate and precipitate the insoluble salt. Thereafter, the nitric acid activation treatment solution in the coagulation tank (2) is filtered and transferred to the recovery liquid storage tank (3) to recover and remove insoluble salts accumulated in the coagulation tank (2). As described above, zinc ions mixed in the nitric acid activation treatment solution are added and mixed with a zinc ion flocculant to precipitate as an insoluble salt, and the precipitate is recovered by recovery.
- This step is performed in the aggregation tank (2).
- deposits on the plating material can be prevented when performing the activation treatment in the nitric acid activation treatment solution treatment tank (1).
- the nitric acid active treatment solution treatment tank (1 ) It is possible to return the nitric acid activation treatment solution after removal of zinc ions.
- the nitric acid activation treatment tank (1) has a pH control device (5), and the pH control based on the nitric acid concentration of the nitric acid activation treatment solution in the nitric acid activation treatment tank (1) It is preferable to carry out with the amount of liquid recovered from the tank (3).
- the pH control device (5) preferably comprises a pH sensor, a liquid feed pump, and a liquid feed amount control device.
- the pH of the nitric acid activation treatment solution is controlled within a specified value range, and when the zinc ion concentration is increased by the activation treatment, and as a result, the pH deviates from the specified value range,
- the nitric acid activation treatment solution in the treatment tank is transferred to the agglomeration tank (2), and the recovery treatment solution is transferred from the recovery liquid storage tank (3) to keep the pH of the nitric acid activation treatment solution in the treatment tank within the specified range. It is preferable to do this.
- the zinc ion flocculant is added to the nitric acid activation treatment solution having a zinc ion concentration transferred from the nitric acid activation treatment tank (1) in the coagulation tank (2), and the mixture is stirred. Is agglomerated as an insoluble salt, and the resulting suspension is transferred to a filtration device, and the filtrate from which zinc ions have been removed as an insoluble salt is transferred to a recovery liquid storage tank (3) as a recovery processing solution. Is preferred.
- the recovery processing solution is temporarily stored in the recovery liquid storage tank (3), and if necessary, the pH of the recovery processing solution is increased in the activation processing tank (1) by adding nitric acid or an alkaline aqueous solution.
- nitric acid activation treatment solutions (A, B) were subjected to various conditions to remove zinc ions from the nitric acid activation treatment solution, and the performance of the regenerated solution was evaluated. Specifically, the flocculant shown in Table 2 was added, dissolved by stirring for 30 seconds, allowed to stand for each time, then filtered using No. 5C filter paper, and the concentration of zinc ions in the filtrate was measured. did. Further, zincate zinc plating (NZ-750, manufactured by Dipsol Co., Ltd.) was applied to a nitric acid activation treatment solution in which the pH of the filtrate was adjusted to the value before addition of the flocculant using sodium hydroxide and nitric acid.
- NZ-750 manufactured by Dipsol Co., Ltd.
- the activated M6 bolt material: iron
- the activated M6 bolt was immersed at 25 ° C. for 20 seconds to confirm the activation performance of the nitric acid activation treatment solution.
- evaluation of activation performance was performed by confirming the presence or absence of cloudiness to the plating raw material after activation treatment visually (hereinafter the same).
- Table 4 shows the removal rate of zinc and the activation performance of the regeneration solution for the results of Examples 1 to 10, and Table 5 summarizes the activation performance of the regeneration solution for the results of Comparative Examples 1 to 3. Show. Table 4
- Example 11 A method for regenerating a nitric acid activation treatment solution of the present invention using the apparatus for regenerating a nitric acid activation treatment solution on the surface of a zinc-based plated metal member shown in FIGS. 2-1 to 2-3 will be described. That is, Tables 6 to 8 show the operating conditions at the start of processing (see FIG. 2-1), 22 hours after the start (see FIG. 2-2) and 24 hours after the start (see FIG. 2-3), respectively. . Table 6
- the regeneration treatment apparatus for the nitric acid activation treatment solution on the surface of the zinc-based plating metal member used in Example 11 is a plating apparatus that operates continuously for 24 hours, and the amount of zinc accumulated in the nitric acid solution by the activation treatment on the plating material is The average is 62.5 g. Moreover, the precipitation removal process of zinc with oxalic acid is performed once a day, and oxalic acid to be mixed uses dihydrate. Even when the zinc concentration in the activated nitric acid solution is 10 g / L, the surface of the substrate after the activation treatment is sufficiently glossy, so the zinc concentration in the activation treatment tank (1) is maintained at 10 g / L. did.
- Table 6 shows the state of the nitric acid activation treatment solution treatment tank (activation treatment tank) (1), the aggregation tank (2), and the recovered liquid storage tank (3) at the start of activation treatment operation.
- activation treatment tank activation treatment tank
- the aggregation tank (2) the recovered liquid storage tank (3) at the start of activation treatment operation.
- a liquid feed pump is sent to the nitric acid activation treatment solution treatment tank (1) and adjusted to a designated pH.
- the average liquid flow to which this nitric acid solution is sent is 7.1 L / h.
- the surplus nitric acid solution after the zinc removal solution is sent to the nitric acid activation treatment solution treatment tank (1) is sent to the agglomerated layer (2) and accumulated, and as a result, the nitric acid activation treatment solution treatment is performed.
- the zinc concentration in the nitric acid solution in the tank (1) was maintained at 10 g / L.
- the states of the activation treatment tank (1), the flocculation tank (2), and the recovered liquid storage tank (3) are as shown in Table 7.
- the coagulation tank 156 L of the nitric acid solution sent from the activation treatment tank is accumulated, and the nitric acid solution in the recovered liquid storage tank is reduced to 44 L.
- oxalic acid is added and mixed in the coagulation tank to coagulate zinc oxalate.
- the amount of oxalic acid to be mixed is 1500 g of zinc dissolved per day, so that the theoretical amount of oxalic acid with respect to that amount of zinc is 2890 g. Thereafter, zinc oxalate was sufficiently coagulated and precipitated over 2 hours.
- the state is as shown in Table 8.
- the nitric acid solution in the coagulation tank has the same concentration as the nitric acid solution in the recovery liquid storage tank after zinc is removed.
- the liquid after zinc removal is sent from the coagulation tank to the recovered liquid storage tank while removing the floating zinc oxalate through filter filtration. Thereafter, the zinc nitrate collected in the coagulation tank (2) is recovered and removed, and a process for reusing it separately is performed.
- the recovered liquid storage tank is supplemented with the loss of the nitric acid solution due to the precipitation recovery and the process returns to the state shown in Table 6.
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Abstract
Description
活性化硝酸溶液は、活性化による素地表面からの亜鉛めっきの溶解や、亜鉛めっき工程からの製品へのめっき液付着による持ち込みにより次第に亜鉛イオンが蓄積して活性化の効果が失われてしまう。活性化硝酸溶液中の亜鉛濃度が蓄積され、活性化処理後の素地表面の光沢が失われた時点で、硝酸溶液の全量入れ替えが必要となり、硝酸の調達費用や作業の手間が必要になる。
本発明は、又、この再生方法を効率よく実施できる亜鉛系めっき金属部材表面の硝酸活性処理溶液の再生処理装置を提供することを目的とする。
すなわち、本発明は、亜鉛系めっき金属部材表面の硝酸活性処理溶液であって、亜鉛イオンを含有する硝酸活性処理溶液に、亜鉛イオン凝集剤を添加し、該溶液中の亜鉛イオンを不溶性塩として凝集させて分離除去することを特徴とする硝酸活性処理溶液の再生方法を提供する。
本発明は、又、硝酸活性処理溶液を用いて亜鉛系めっき金属部材表面の活性処理を行う硝酸活性化処理槽(1)、硝酸活性処理溶液に亜鉛イオン凝集剤を添加し、該溶液中の亜鉛イオンを不溶性塩として凝集させる凝集槽(2)、凝集した不溶性亜鉛塩を分離除去する濾過装置(4)、ろ液を一時貯蔵する回収液貯蔵槽(3)を有し、各部がこの順に配管を介して連設して循環回路を形成しており、更に、回収液貯蔵槽(3)、硝酸活性化処理槽(1)、又は回収液貯蔵槽(3)と活性化処理槽(1)の連設配管のいずれかに少なくとも1以上に、硝酸活性処理溶液の硝酸濃度によるpHを規定範囲に維持させるpH制御装置(5)を有してなることを特徴とする亜鉛系めっき金属部材表面の硝酸活性処理溶液の再生処理装置を提供する。
この硝酸活性処理溶液には不純物が含まれていても良い。このとき不純物として、鉄、銅などの金属イオンの他、めっき液に含まれる有機物があげられる。
本発明で用いる亜鉛イオンを凝集させて沈殿させる亜鉛イオン凝集剤としては、硝酸活性処理溶液中で可溶性であり、処理液中の亜鉛イオンと不溶性もしくは難溶性塩を形成し凝集しうる機能を持つ薬剤であれば特に制限はないが、好ましくは、シュウ酸(無水物又は二水和物等の水和物を含む)、またはシュウ酸ナトリウム、シュウ酸水素ナトリウム、シュウ酸アンモニウム、シュウ酸水素アンモニウムなどのシュウ酸塩、もしくは、炭酸、または炭酸ナトリウム、炭酸水素ナトリウム、炭酸アンモニウム、炭酸水素アンモニウムなどの炭酸塩である。より好ましくはシュウ酸またはその塩であり、特に好ましくはシュウ酸である。
硝酸活性処理溶液と凝集剤との混合の方法としては、硝酸溶液を攪拌し、これに凝集剤を添加する方法の他、水溶液又はスラリー状の凝集剤を攪拌しつつ硝酸溶液を添加する方法があげられるが、これらの何れによっても良い。
硝酸活性処理溶液と凝集剤との混合時間は、5分~24時間とするのが好ましく、10分~12時間が特に好ましい。この範囲内とすると凝集剤亜鉛への不純物の混入量が抑えられ、凝集の生成が十分に行われ、亜鉛の回収量が向上する。尚、24時間を超えて混合しても凝集生成に差異はなく、経済効率が低下する。
このように、活性化硝酸溶液と凝集剤とを混合し、沈殿を生成させた後、沈殿物はろ過などにより固液分離を行う。沈殿を取り除いたろ液に関しては、硝酸活性処理溶液として再利用する。この際、前述の硝酸活性処理溶液の通常のpH範囲よりもpHが低い場合は、水を添加し希釈を行うか、水酸化ナトリウムなどを添加し範囲内に調整する。範囲よりも高い場合は、硝酸を添加し範囲内に調整をするのがよい。
回収した沈殿物(凝集剤と亜鉛との塩)は、亜鉛をより高純度で回収するため洗浄工程により洗浄するのが好ましい。この際の洗浄液としては水又は凝集剤水溶液を用いるのが好ましいが、水は純水、超純水を含み、また、凝集剤水溶液としては0.5mol/l以下の濃度の凝集剤水溶液が好ましい。
尚、凝集剤添加後、洗浄を行なうことなく直ちに凝集剤と亜鉛との塩を回収する場合、又は、ろ過洗浄以外の方法で洗浄を行なったときには、凝集剤と亜鉛との塩を固液分離することとなるが、これは通常のろ過により可能である。
本発明では、又、硝酸活性化処理槽(1)に混入してくる亜鉛イオンを、亜鉛イオン含有硝酸活性処理溶液として凝集槽(2)に導入し、凝集槽(2)に亜鉛イオン凝集剤、例えばシュウ酸またはその塩及び/又は炭酸またはその塩を添加し、亜鉛イオン含有硝酸活性処理溶液と混合して亜鉛イオンを不溶性塩、例えばシュウ酸亜鉛及び/又は炭酸亜鉛として凝集させて除去し、得られた亜鉛イオン除去液を回収液貯蔵(3)に移行して貯蔵し、次いで槽(3)で硝酸活性処理溶液のpHを調整した後、硝酸活性化処理槽(1)に返還して、硝酸活性処理溶液を再生方するのが好ましい。
この装置において、めっき素材の硝酸活性化処理は、硝酸活性処理溶液理槽(1)で行われる。処理により上昇したpHは、回収液貯蔵槽(3)に貯蔵してある亜鉛除去後の硝酸活性処理溶液を送液ポンプで硝酸活性処理溶液処理槽(1)に送って指定のpHに調整するのが好ましい。この際、pHはpHセンサーを用いて管理するのが好ましい。亜鉛除去後の硝酸活性処理溶液が硝酸活性処理溶液処理槽(1)に送られて余剰となった硝酸活性処理溶液は、凝集槽(2)に送られて蓄積するのが好ましい。
上述の通り硝酸活性処理溶液に混入した亜鉛イオンを、亜鉛イオン凝集剤を添加し混合させ不溶性塩として沈降させ、沈殿物を回収することで除去する。この工程は、凝集槽(2)で行われる。硝酸活性処理溶液処理槽(1)と別の槽で本工程を行うことにより、硝酸活性処理溶液処理槽(1)で活性化処理を行う際、めっき素材への沈殿物付着を防ぐことができる。また、亜鉛除去後の液を回収液貯蔵槽(3)に移液貯蔵し、ここに亜鉛イオン凝集剤を添加し混合して不溶性塩として沈降させる工程中も、硝酸活性処理溶液処理槽(1)へ、亜鉛イオン除去後の硝酸活性処理溶液を返還することが可能となる。
さらに、上記装置では、硝酸活性化処理槽(1)がpH制御装置(5)を有し、硝酸活性化処理槽(1)中の硝酸活性処理溶液の硝酸濃度によるpH制御を、回収液貯蔵槽(3)からの回収液の送液量で行うのが好ましい。
上記装置では、硝酸活性化処理槽(1)において、硝酸活性処理溶液のpHは規定値範囲に管理されており、活性処理により亜鉛イオン濃度が上昇しその結果pHが規定値範囲を逸脱すると、処理槽中の硝酸活性処理溶液を凝集槽(2)に移送すると共に、回収液貯蔵槽(3)から回収処理溶液を移送し、処理槽中の硝酸活性処理溶液のpHを規定値範囲に保持するのが好ましい。
上記装置では、凝集槽(2)において、硝酸活性化処理槽(1)から移送された亜鉛イオン濃度が規定値以上の硝酸活性処理溶液に、亜鉛イオン凝集剤を添加、混合攪拌し、亜鉛イオンを不溶性塩として凝集させた後、得られた懸濁液をろ過装置に移送し、亜鉛イオンが不溶性塩として除去された後のろ液を回収処理溶液として回収液貯蔵槽(3)に移送するのが好ましい。
上記装置では、回収液貯蔵槽(3)において、回収処理溶液が一時保存されると共に、必要に応じて硝酸もしくはアルカリ水溶液を添加して回収処理溶液のpHが活性化処理槽(1)中の硝酸活性処理液と同等の規定値範囲に管理されており、必要に応じて硝酸活性化処理槽(1)に再生活性処理液として移送されるのが好ましい。
次に実施例に基づいて本発明をさらに具体的に説明する。
図2-1~図2-3に示した亜鉛系めっき金属部材表面の硝酸活性処理溶液の再生処理装置を用いた本発明の硝酸活性処理溶液の再生方法を示す。すなわち、処理開始時(図2-1参照)、開始から22時間後(図2-2参照)及び開始から24時間後(図2-3参照)の運転条件を、それぞれ表6~8に示す。
表6
表6は、活性化処理稼働開始時の硝酸活性処理溶液処理槽(活性化処理槽)(1)、凝集槽(2)、回収液貯蔵槽(3)の状態である。上述の通り、めっき素材の活性化処理が活性化処理槽で行われて硝酸活性処理溶液中に亜鉛イオンが溶解、蓄積しpHが上昇すると、回収液貯蔵槽に貯蔵してある亜鉛除去後の液を送液ポンプが硝酸活性処理溶液処理槽(1)に送られて指定のpHに調整される。この硝酸溶液が送られる平均液流は7.1L/hとなる。また、亜鉛除去後の液が硝酸活性処理溶液処理槽(1)に送られることで余剰となった硝酸溶液は、凝集層(2)に送られて蓄積され、その結果、硝酸活性処理溶液処理槽(1)の硝酸溶液中の亜鉛濃度は10g/Lに維持された。
以上のような再生処理装置を用いることにより、工程の簡素化、低コストで3価クロム化成処理の品質を一定に管理し、硝酸の廃棄を可能な限り少なくすることが可能となるとの工業上の優れた効果が得られる。
Claims (12)
- 亜鉛系めっき金属部材表面の硝酸活性処理溶液であって、亜鉛イオンを含有する硝酸活性処理溶液に、亜鉛イオン凝集剤を添加し、該溶液中の亜鉛イオンを不溶性塩として凝集させて分離除去することを特徴とする硝酸活性処理溶液の再生方法。
- 亜鉛イオン凝集剤がシュウ酸またはその塩及び/又は炭酸又はその塩である請求項1記載の硝酸活性処理溶液の再生方法。
- 亜鉛イオン凝集剤の添加量が、硝酸活性処理溶液中の亜鉛イオン濃度に対し、シュウ酸またはその塩では0.5~1モル倍の範囲、炭酸又はその塩では0.5~2モル倍の範囲、両者の混合物では0.5~2モル倍の範囲である請求項2記載の硝酸活性処理溶液の再生方法。
- 硝酸活性処理溶液に亜鉛イオン凝集剤を温度0~90℃の範囲で添加混合し、同温度でさらに5分~24時間攪拌して亜鉛イオンを不溶性塩として凝集させ、次いで分離除去する請求項1~3のいずれか1項に記載の硝酸活性処理溶液の再生方法。
- 硝酸活性処理溶液のpHが0.5~3.0の範囲にあり、不溶性塩を分離除去したろ液の回収硝酸活性溶液のpHを0.5~3.0の範囲にpH調整し、硝酸活性溶液として再生させる請求項1~4のいずれか1項に記載の硝酸活性処理溶液の再生方法。
- 硝酸活性化処理槽(1)に混入してくる亜鉛イオンを、亜鉛イオン含有硝酸活性処理溶液として凝集槽(2)に導入し、凝集槽(2)に亜鉛イオン凝集剤を添加し、亜鉛イオン含有硝酸活性処理溶液と混合して亜鉛イオンを不溶性塩として凝集させて除去し、得られた亜鉛イオン除去液を回収液貯蔵槽(3)に移行して貯蔵し、次いで槽(3)で硝酸活性処理溶液のpHを調整した後、硝酸活性化処理槽(1)に返還することを特徴とする硝酸活性処理溶液の再生方法。
- 硝酸活性処理溶液を用いて亜鉛系めっき金属部材表面の活性処理を行う硝酸活性化処理槽(1)、硝酸活性処理溶液に亜鉛イオン凝集剤を添加し、該溶液中の亜鉛イオンを不溶性塩として凝集させる凝集槽(2)、凝集した不溶性亜鉛塩を分離除去する濾過装置(4)、ろ液を一時貯蔵する回収液貯蔵槽(3)を有し、各部がこの順に配管を介して連設して循環回路を形成しており、更に、回収液貯蔵槽(3)、硝酸活性化処理槽(1)、又は回収液貯蔵槽(3)と活性化処理槽(1)の連設配管のいずれかに少なくとも1以上に、硝酸活性処理溶液の硝酸濃度によるpHを規定範囲に維持させるpH制御装置(5)を有してなることを特徴とする亜鉛系めっき金属部材表面の硝酸活性処理溶液の再生処理装置。
- 硝酸活性化処理槽(1)がpH制御装置(5)を有し、硝酸活性化処理槽(1)中の硝酸活性処理溶液の硝酸濃度によるpH制御を、回収液貯蔵槽(3)からの回収液の送液量で行う請求項7に記載の再生処理装置。
- pH制御装置(5)が、pHセンサーと液送ポンプと送液量制御装置よりなる請求項7に記載の再生処理装置。
- 硝酸活性化処理槽(1)において、硝酸活性処理溶液のpHは規定値範囲に管理されており、活性処理により亜鉛イオン濃度が上昇しその結果pHが規定値範囲を逸脱すると、処理槽中の硝酸活性処理溶液を凝集槽(2)に移送すると共に、回収液貯蔵槽(3)から回収処理溶液を移送し、処理槽中の硝酸活性処理溶液のpHを規定値範囲に保持することを含む請求項1~9のいずれか1項に記載の再生処理装置。
- 凝集槽(2)において、硝酸活性化処理槽(1)から移送された亜鉛イオン濃度が規定値以上の硝酸活性処理溶液に、亜鉛イオン凝集剤を添加、混合攪拌し、亜鉛イオンを不溶性塩として凝集させた後、得られた懸濁液をろ過装置に移送し、亜鉛イオンが不溶性塩として除去された後のろ液を回収処理溶液として回収液貯蔵槽(3)に移送することを含む請求項1~10のいずれか1項に記載の再生処理装置。
- 回収液貯蔵槽(3)において、回収処理溶液が一時保存されると共に、必要に応じて回収処理溶液のpHが活性化処理槽(1)中の硝酸活性処理液と同等の規定値範囲に管理されており、必要に応じて硝酸活性化処理槽(1)に再生活性処理液として移送されることを含む請求項1~11のいずれか1項に記載の再生処理装置。
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JP2006316330A (ja) * | 2005-05-16 | 2006-11-24 | Sanshin Seisakusho:Kk | めっき素材表面活性化硝酸溶液の機能維持方法と装置 |
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JPS5214230B2 (ja) * | 1974-10-11 | 1977-04-20 | ||
CN1045956A (zh) * | 1989-03-27 | 1990-10-10 | 吉林市金刚化工厂 | 用碳酸氢铵沉淀法制取碱式碳酸锌及活性氧化锌 |
JP3332374B1 (ja) * | 2001-11-30 | 2002-10-07 | ディップソール株式会社 | 亜鉛及び亜鉛合金めっき上に六価クロムフリー防錆皮膜を形成するための処理溶液、六価クロムフリー防錆皮膜及びその形成方法。 |
JP3332373B1 (ja) * | 2001-11-30 | 2002-10-07 | ディップソール株式会社 | 亜鉛及び亜鉛合金めっき上に六価クロムフリー防錆皮膜を形成するための処理溶液、六価クロムフリー防錆皮膜及びその形成方法。 |
DE10256884A1 (de) * | 2002-12-05 | 2004-06-17 | Henkel Kgaa | Verfahren zur Phosphatierung von Metalloberflächen mit verbesserter Phosphat-Rückgewinnung |
JP2004263240A (ja) * | 2003-02-28 | 2004-09-24 | Nitto Seiko Co Ltd | 黒色六価クロムフリー鍍金処理システム |
JP4446233B2 (ja) * | 2004-03-03 | 2010-04-07 | ディップソール株式会社 | 3価クロメート処理溶液用の皮膜総合摩擦係数低減剤、3価クロメート処理溶液及びその製造方法、並びに総合摩擦係数が低減した3価クロメート皮膜及びその製造方法 |
US20060127291A1 (en) * | 2004-12-09 | 2006-06-15 | Abazajian Armen N | High density, high stability, sized metal oxide powder and process for making same |
JP5198727B2 (ja) * | 2005-10-07 | 2013-05-15 | ディップソール株式会社 | 亜鉛又は亜鉛合金上に黒色の6価クロムフリー化成皮膜を形成するための処理溶液 |
WO2009129271A1 (en) * | 2008-04-14 | 2009-10-22 | Akridge James R | System for the sustainable recovery of metals from electronic waste |
TWI555880B (zh) * | 2011-04-01 | 2016-11-01 | 迪普索股份有限公司 | 3價鉻化學轉換被膜用整理加工劑及黑色3價鉻化學轉換被膜之整理加工方法 |
CN102295308A (zh) * | 2011-08-15 | 2011-12-28 | 昆山德阳新材料科技有限公司 | 一种以含锌废液为原料制备氧化锌的方法 |
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JPS55161074A (en) * | 1979-06-04 | 1980-12-15 | Hitachi Ltd | Recovering method for waste chromate solution |
JP2006316330A (ja) * | 2005-05-16 | 2006-11-24 | Sanshin Seisakusho:Kk | めっき素材表面活性化硝酸溶液の機能維持方法と装置 |
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TW201402867A (zh) | 2014-01-16 |
TWI558852B (zh) | 2016-11-21 |
JP5877423B2 (ja) | 2016-03-08 |
CN104321466A (zh) | 2015-01-28 |
US20150096461A1 (en) | 2015-04-09 |
KR102088542B1 (ko) | 2020-03-12 |
JP2013234371A (ja) | 2013-11-21 |
KR20150008084A (ko) | 2015-01-21 |
EP2848713A4 (en) | 2016-02-10 |
US9249509B2 (en) | 2016-02-02 |
EP2848713B1 (en) | 2018-12-19 |
CN104321466B (zh) | 2017-04-12 |
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