Classifications

• • 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
  • C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
• • 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
  • C25D21/20—Regeneration of process solutions of rinse-solutions
• • C—CHEMISTRY; METALLURGY
  • 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
  • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
• • 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
  • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
  • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
  • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
• • 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
  • C25D21/22—Regeneration of process solutions by ion-exchange

Definitions

• the present invention relates to a method for recovering noble metal ions from plating wastewater, and in particular, can recover noble metal ions with high efficiency from plating wastewater in plating recovery tanks and plating washing tanks, and to reduce the performance of plating objects.
• the present invention relates to a method for recovering precious metal ions from plating wastewater that can be suppressed.
• Precious metals are industrially very useful materials because they are excellent in physical properties, reliability, aesthetics, etc., and are used as plating materials in a wide range of fields, including electronic devices such as electronic parts and printed wiring boards. It's being used.
• noble metals are rare and very expensive materials. Therefore, it is required to collect and reuse the precious metal contained in the plating wastewater as much as possible.
• plating waste water is divided into waste water from a plating tank, a plating recovery tank, and a plating washing tank. Since the plating recovery tank serves as a primary cleaning tank after the plating treatment in the plating tank, the drainage from the plating recovery tank contains precious metal ions having a lower concentration than the drainage of the plating tank. In addition, since the plating washing tank serves as a secondary or tertiary washing tank, the drainage from the plating washing tank contains precious metal ions at a lower concentration than the drainage from the plating collection tank. Thus, the noble metal ion concentration of the plating waste water discharged from each tank is different.
• the plating collection tank is used to wash out precious metal ions and salt components that have excessively adhered to the object to be plated, and to suppress the generation of mold and fungi due to organic substances that are components of the plating solution. Management in the tank is required.
• an electrolytic recovery method As a method for recovering noble metal ions from plating waste water, an electrolytic recovery method, a resin recovery method, and an activated carbon adsorption recovery method are generally known.
• the electrolytic recovery method is excellent for recovering precious metal ions from plating wastewater with a high concentration of noble metal ions, the current density does not increase even if it is circulated in the electrolytic cell if it is low concentration plating wastewater. The recovery efficiency of noble metal ions is deteriorated.
• the resin recovery method and activated carbon adsorption recovery method are excellent for recovering precious metal ions from plating wastewater with low precious metal ion concentration, but precious metal ions are sufficiently recovered when flowing high concentration plating wastewater. Disappear. Therefore, it is necessary to manage the concentration of noble metal ions when draining from the plating washing tank.
• the concentration of noble metal ions in the liquid contained in the plating recovery tank does not always increase at a constant rate, and may increase rapidly depending on circumstances.
• the noble metal ion concentration of the accommodation liquid in the plating recovery tank varies in accordance with the production amount of the plating object. Therefore, when the plating waste water contains a relatively low concentration of noble metal ions, a sufficient current density cannot be obtained, and the recovery efficiency of noble metal ions by the electrolytic recovery method is deteriorated.
• An object of the present invention is to provide a method capable of efficiently recovering noble metal ions from a plating wastewater containing noble metal ions discharged from a plating recovery tank and a plating washing tank, and capable of suppressing poor performance of a plating object. There is.
• the present inventor has found that the noble metal ion concentration of the contained liquid in the plating recovery tank and the plating washing tank is maintained within a predetermined range, and based on such knowledge, the present invention is It came to be completed. That is, according to the present invention, the amount of drainage per one time from the plating recovery tank is within the range of 10 to 50% of the full capacity of the plating recovery tank, and the plating treatment object is immersed in the plating recovery tank. By maintaining the amount of noble metal ions in the plating solution in the plating recovery tank at a high concentration within a certain range, and the concentration of the noble metal ions in the plating solution in the plating washing tank is low.
• the electrolytic recovery method and the resin recovery method or the activated carbon adsorption recovery method are used in combination for the plating wastewater from the plating recovery tank in which the concentration of the noble metal ions is maintained within a certain range at a high concentration.
• the noble metal ions are recovered and the noble metal ions are recovered by the resin recovery method or the activated carbon adsorption recovery method for the plating wastewater from the plating washing tank in which the concentration of the noble metal ions is maintained within a certain range at a low concentration. can do.
• the precious metal ions can be efficiently recovered from the plating wastewater containing the precious metal ions discharged from the plating recovery tank and the plating washing tank without stopping the plating treatment of the plating object, and It is possible to suppress poor performance of the plating object.
• the present invention is a general plating process, that is, a step of plating by immersing the object to be plated in a plating tank containing a plating solution, and immersing the object to be processed in a liquid stored in the plating recovery tank. This is applied to the process of cleaning the object first, and the process including the process of immersing the object in the liquid stored in the plating cleaning tank and finally cleaning the object to be processed.
• the electrolytic recovery method and the resin recovery method or the activated carbon adsorption recovery method are used in combination to recover noble metal ions, while the plating wastewater from the plating washing tank is recovered by the resin recovery method or the activated carbon adsorption recovery method. Collect noble metal ions.
• the object to be processed is subjected to a plating process in a batch by repeating dipping and pulling processes in a product continuously plated with a pair of rolls, such as an electronic component or a printed wiring board, and a plating tank. It is a product.
• the storage liquid in the plating recovery tank and the plating cleaning tank is usually ion-exchanged water treated with an ion exchange resin. After collecting noble metal ions from the plating cleaning tank storage liquid, the activated carbon treatment and reverse osmosis membrane are performed. Treated pure water can also be used suitably.
• the amount of drainage per one time from the plating recovery tank is within a range of 10 to 50% of the full water volume of the plating recovery tank, and the plating treatment object is immersed in the plating recovery tank.
• the precious metal ion concentration of the containing liquid in the plating recovery tank is kept constant at a low concentration. Keep in the range.
• the electrolytic recovery method and the resin recovery method or activated carbon adsorption recovery method are used in combination.
• noble metal ions can be recovered by a resin recovery method or an activated carbon adsorption recovery method.
• the amount of drainage per one time from the plating collection tank is within the range of 10 to 50% of the full amount of water in the plating collection tank, and the amount that ensures the immersion of the object to be plated is ensured in the plating collection tank. It is preferable to do. If the amount of water discharged per time exceeds 50% of the full capacity of the plating recovery tank, the water temperature in the plating recovery tank will fluctuate significantly due to water injection, and excess precious metal ions and salt components adhering to the object to be plated will be recovered. In addition, molds, fungi, and the like are likely to propagate, and performance defects and yield due to adhesion to the object to be plated are reduced.
• the amount of discharged water per time is less than 10% of the full water amount, the management of the precious metal ion concentration and the drainage and water injection work in the plating recovery tank become complicated. In addition, management defects occur due to the complexity of work, and the efficiency of recovering excess precious metal ions and salt components adhering to the object to be plated is reduced, and not only the object to be plated is contaminated but also the recovery efficiency of precious metal ions is improved. May decrease. In addition, the reason why the amount of drainage per time is set to an amount that ensures the immersion of the object to be plated is to prevent the plating process from being stopped.
• the heated plating object and the plating solution adhering to the plating object move to the plating recovery tank, which causes the water temperature of the plating recovery tank to rise.
• Another cause of increasing the water temperature of the plating recovery tank is due to radiant heat from the plating tank because the plating tank and the plating recovery tank are continuously installed.
• an increase in the water temperature does not necessarily cause poor performance of the workpiece to be plated and a decrease in yield in the plating recovery tank.
• the water temperature of the liquid contained in the plating recovery tank is preferably 35 ° C. or higher, more preferably 40 ° C. or higher.
• the washing efficiency of the salt component is good and the growth of mold and fungi is suppressed.
• the processing amount of the plating object when the processing amount of the plating object is small, the conventional time management method, the overflow method, and the total amount replacement method cause excessive drainage and water injection, which causes a decrease in water temperature. Therefore, in the present invention, as will be described later, by installing an electrode in the plating recovery tank and estimating the noble metal ion concentration from the current value using a calibration curve, the processing amount of the plating object is estimated, and from the plating recovery tank. It is important that the amount of drainage per time is in the range of 10 to 50% of the full water volume of the plating recovery tank. For example, when the water temperature of the plating recovery tank is 50 ° C. by calorie calculation, when 50% of the full water amount is replaced with water injection at 20 ° C., the water temperature falls within a range of 10 ° C. The water temperature is controlled so that it does not fall below 35 ° C even when there is little water.
• the noble metal ion concentration of the containing liquid in the plating recovery tank is maintained at a high concentration within a certain range. It is preferable to use the electrolytic recovery method and the resin recovery method or the activated carbon adsorption recovery method for waste water maintained at a high concentration in a certain range.
• maintaining a high concentration within a certain range means maintaining the noble metal ion concentration of the liquid contained in the plating cleaning tank at a high concentration compared to maintaining the noble metal ion concentration within a certain range at a low concentration. .
• the number of electrolytic recovery devices installed, the filling amount of resin and activated carbon, and the like are suitably selected according to the concentration of noble metal ions and the processing amount per unit time. If the noble metal ion recovery method of the present invention is used, even if the plating drainage from a plurality of plating recovery tanks installed in parallel contains the same noble metal ions, each plating drainage is routed through one path. It is possible to collect and collect electrolytically.
• the noble metal ion concentration is maintained within a certain range when it is put into the recovery facility.
• recovery facilities such as the number of electrolytic recovery devices installed are designed according to the concentration of precious metal ions during drainage of the plating apparatus and the amount of wastewater treated per unit of time.
• the electrolytic recovery is set according to the circulation time, and the circulation time is appropriately adjusted with respect to the fluctuation of the noble metal ion concentration. Therefore, a certain range is to maintain a concentration suitable for the processing performance of the recovery equipment designed for precious metal ions, and if it exceeds a certain range, the recoverable capacity in the resin or activated carbon adsorption recovery after electrolytic recovery is increased. The recovery efficiency will decrease. On the other hand, below a certain range, the recovery efficiency at low concentration is low in electrolytic recovery, and the recovery efficiency per unit time is reduced. From the above, maintaining the concentration of noble metal ions in the containing liquid within a certain range at a high concentration can make maximum use of the recovery efficiency of the recovery equipment, and as a result, a high yield can be realized.
• the current density may not be sufficiently increased depending on the type of the plating liquid, and an electrolyte such as caustic soda may be optionally added to increase the current density.
• an electrolyte such as caustic soda
• the precious metal ions contained in the plating recovery tank defined in the present invention are maintained at a high concentration within a certain range, it is preferably maintained within a range of 10 to 200 mg / L. If the concentration of precious metal ions in the plating solution in the plating recovery tank exceeds 200 mg / L, the precious metal ions will not be recovered sufficiently even if the electrolytic recovery method and the resin recovery method or activated carbon adsorption recovery method are used in combination.
• the concentration of noble metal ions in the plating collection tank is less than 10 mg / L
• the combined use of the electrolytic recovery method and the resin recovery method or the activated carbon adsorption recovery method is overdesigned and economically inefficient. It becomes.
• the concentration of the noble metal ions contained in the liquid contained in the plating recovery tank is less than 10 mg / L.
• the noble metal concentration of the liquid contained in the plating cleaning tank is such that the noble metal ions in the plating cleaning tank moving from the plating recovery tank have a low concentration by maintaining the noble metal ion concentration in a certain concentration range in the plating recovery tank.
• the stored liquid after the stored liquid in the plating recovery tank is processed by the electrolytic recovery method is also maintained in a certain range at a low concentration. Since both are maintained in a certain range at a low concentration, the filling amount of the resin and activated carbon is suitably selected according to the precious metal ion concentration and the processing amount per unit time.
• the noble metal ion concentration in the liquid contained in the plating recovery tank is 200 mg / L at the maximum, and therefore the maximum concentration of excess noble metal ions attached to the object to be plated sent from the plating recovery tank is 200 mg.
• the noble metal ion concentration when diluted 25 times is 8 mg / L, and when diluted 50 times, it is 4 mg / L. And maintained at 10 mg / L or less.
• anode used examples include an electrode made of a Pt-plated Ti material, an Ir sintered Ti material, or a ferrite material
• examples of the cathode include an electrode made of a Ti material, an SUS material, or a ferrite material.
• the type of electrode and the current density are appropriately set depending on the type of plating solution and the type of noble metal ion.
• an Ir sintered Ti material electrode is used for drainage of a cyan plating solution because cyan ions dissolve Pt.
• the resin recovery method is a method in which plating wastewater is passed through a resin to collect noble metal ions, and the resin is incinerated to recover the noble metal.
• the resin used in the resin recovery method include a cation exchange resin, an anion exchange resin, a chelate resin, and a synthetic adsorbent, and those that efficiently recover noble metal ions are preferable.
• an anion exchange resin for example, a strongly basic ion exchange resin having a quaternary ammonium base (trimethylammonium base, dimethylethanolammonium base, etc.), a primary, secondary or tertiary amino group
• a weakly basic ion exchange resin having a cation exchange resin such as a strong acid ion exchange resin having a sulfonic acid group, a super strong acid ion exchange resin having a fluorinated alkylsulfonic acid group, a carboxyl group, a phosphonic acid group, Weakly acidic ion exchange resins having phosphinic acid groups, etc .; chelate resins such as imidinoacetic acid type chelate resins and polyamine type chelate resins are preferred.
• the activated carbon adsorption recovery method used together with the electrolytic recovery method is a method of collecting precious metal ions using activated carbon, burning the activated carbon to make it ash, and collecting the precious metal ions from the obtained ash.
• the plating waste water is impregnated with activated carbon, or the plating waste water is passed through the activated carbon packed in the column.
• the resin recovery method or the activated carbon adsorption recovery method is as described above.
• a current is applied between the electrodes installed in the plating recovery tank at a constant voltage or a constant current, and the current value or potential value and the stored liquid in the plating recovery tank
• a calibration curve indicating the relationship with the concentration of noble metal ions contained is prepared in advance, and a current or potential value between the electrodes is applied between the electrodes installed in the plating recovery tank by applying a constant voltage or a constant current.
• the noble metal ion concentration of the liquid contained in the plating recovery tank is quantified, and when the obtained quantitative value reaches a predetermined set value, the plating recovery is performed.
• the concentration of the noble metal ions in the liquid contained in the plating recovery tank is maintained within a certain range at a high concentration.
• the electrode is preferably an electrode made of Pt-plated Ti material, Ir sintered Ti material, or ferrite material that does not elute when the current density is increased for the anode, and the cathode is made of Ti material, SUS material, or ferrite material.
• An electrode is preferred.
• the shape of the electrode can be appropriately selected from a flat plate, a round bar, a cylinder, a net, and the like, but a round bar and a cylinder are more preferable in view of electrode facing during mounting.
• the electrode shape of the electrodes installed in the plating recovery tank, the electrode length, the distance between the electrodes, and About an applied voltage it selects suitably according to the electrical conductivity of the plating waste_water
• the conductivity of the plating wastewater is the conductivity of the entire plating wastewater including noble metal ions and other electrolytes. If the noble metal ion concentration is high, the conductivity is high.
• the slope of the precious metal ion concentration-current value curve of the plating wastewater is large, a relatively low voltage is applied, the electrode diameter is small, the electrodes are short, and the distance between the electrodes can be widened.
• the inclination when the inclination is small, the inclination can be adjusted by applying a relatively high voltage, the electrode diameter is large, the electrodes are long, and the distance between the electrodes is wide.
• the applied voltage can be set to 12 to 24 V
• the current value corresponding to the upper limit value of the noble metal ion concentration can be set to 200 to 800 mA
• the current value corresponding to the lower limit value of the noble metal ion concentration can be set to 100 to 500 mA.
• Electrode conditions that can manage the difference between the upper and lower values of the noble metal ion concentration and the lower limit within a range of 100 to 300 mA are preferably selected.
• the drainage and / or water injection of the plating recovery tank can be performed by, for example, a method in which the drainage and water injection motor valves are activated simultaneously, a method in which the drainage motor valve is in operation and the drainage is completed, and then a water injection motor valve is in operation. It adopts a system that operates a water injection motor valve and automatically controls it with a control panel. In addition, what has the same function, such as a solenoid valve, can be used instead of a motor operated valve.
• the water injection motor is activated.When the current value of the liquid stored in the plating recovery tank reaches the set upper limit, only the drainage motor valve Is activated and drained to the minimum water level. At this time, there is no change in the current value of the stored liquid. When drainage is completed, the water injection motor is operated, and stops when the water injection reaches the full water level.
• the upper limit value of noble metal ion concentration is controlled by controlling the timing of drainage according to the current value of the liquid stored in the plating recovery tank, and the lower limit value of noble metal ion concentration is controlled by measuring the amount of drainage and water injection by measuring the water level. to manage.
• the method of operating the water injection valve during drainage is that when the current value of the liquid stored in the plating recovery tank reaches the set upper limit value, the water discharge valve is activated, and the water injection motor valve is in the drainage. When the current value reaches the set lower limit value, the operation of the drainage and water injection motor-operated valves is stopped, and the water injection ends.
• the timing of drainage and water injection is controlled by the current value of the liquid stored in the plating recovery tank, and the upper and lower limits of the noble metal ion concentration are managed.
• the noble metal ion of the noble metal ion to be collected is Au, Pd, Ag, Pt, or Rh. Therefore, the type of the plating solution to be processed on the plating object is a plating solution containing at least one of Au, Pd, Ag, Pt and Rh, such as Ni, Co, Fe, Zn, etc.
• An alloy plating solution containing a non-noble metal may be used. Examples of the plating method include cyan plating, non-cyan plating, electrolytic plating, and electroless plating.
• the plating solution stored in the plating tank is usually one having a noble metal ion concentration of 1 to 70 g / L.
• the upper limit value of the Au ion concentration of the contained liquid is set to 50 to 59 mg / L, and the lower limit value is set to 34 to 43 mg / L, the electrode, electrode shape, electrode length, and electrode installed in the plating recovery tank
• the applied voltage is 24 V
• the current value indicating the upper limit value of the Au ion concentration is 350 mA
• the current value indicating the lower limit value is 250 mA
• Au As an optimal electrode in which the difference between the upper limit value and the lower limit management value of the ion concentration is managed in a current value range of 100 mA, an anode made of a Pt-plated Ti material, a Ti material, or the like A becomes a cathode, a round bar shape, electrode diameter 15 mm, electrode length 23 mm, interelectrode distance 35mm are exemplified.
• the drainage and water injection of the plating recovery tank are carried out by a method in which the drainage and water injection motor valves are operated simultaneously, when the upper limit of 350 mA is reached, the water discharge and water injection motor valves are simultaneously operated, When the lower limit of 250 mA is reached, the operation of the drainage and water injection motor-operated valves is stopped. Therefore, the drained Au ion concentration is in the range of the upper limit concentration of 50 to 59 mg / L and the lower limit concentration of 34 to 43 mg / L, and 20% of the stored liquid in the plating recovery tank is replaced. The Au ion concentration of the adhering liquid adhering to the workpiece to be plated washed in the plating recovery tank is 59 mg / L at the maximum.
• the Au ion concentration is 10 mg / L. Maintained at a low concentration of L or less.
• the water temperature of the poured water was approximately 20 ° C., and the water temperature of the plating recovery tank during continuous operation was 44 to 46 ° C.
• Electrolytic recovery of high-concentration Au ions contained in plating wastewater from the plating recovery tank is an electrolytic recovery device with a circulation processing capacity of about 200 L consisting of an anode made of Ir sintered Ti material and a cathode electrode made of Ti material (Tanaka Kikinzoku Kogyo) Au ion was collected at an electrolytic density of 130 to 200 mA / dm 2 using a mini recovery vessel.
• the same resin can be used to recover the low concentration Au ions contained in the waste liquid after the electrolytic recovery and the plating waste water from the plating washing tank, respectively, and an ion exchange resin device filled with an anion exchange resin (Tanaka Kikinzoku Kogyo) Au ions were collected using a company manufactured by Eagle RE).
• the residual Au ion concentration after the recovery process in this embodiment was less than 0.2 mg / L.
• the current value indicating the upper limit value of Au ion concentration is 370 mA
• the current value indicating the lower limit value is 270 mA
• the upper limit value and lower limit value of the Au ion concentration are
• the optimum electrode for which the difference is managed in a current value range of 100 mA is an anode made of a Pt-plated Ti material, a cathode made of a Ti material, and has a round bar shape, an electrode diameter of 15 mm, an electrode length of 23 mm, During distance 35mm are exemplified.
• the Au ion concentration of the adhering liquid adhering to the workpiece to be plated washed in the plating recovery tank is 63 mg / L at the maximum.
• the Au ion concentration is 10 mg / L.
• the water temperature of the poured water was approximately 20 ° C., and the water temperature of the plating recovery tank during continuous operation was 44 to 46 ° C.
• Electrolytic recovery of high-concentration Au ions contained in plating wastewater from the plating recovery tank is an electrolytic recovery device with a circulation processing capacity of about 200 L consisting of an anode made of Ir sintered Ti material and a cathode electrode made of Ti material (Tanaka Kikinzoku Kogyo) Au ion was collected at an electrolytic density of 130 to 200 mA / dm 2 using a mini recovery vessel.
• the same resin can be used to recover the low concentration Au ions contained in the waste liquid after the electrolytic recovery and the plating waste water from the plating washing tank, respectively, and an ion exchange resin device filled with an anion exchange resin (Tanaka Kikinzoku Kogyo) Au ions were collected using a company manufactured by Eagle RE).
• the residual Au ion concentration after the recovery process in this embodiment was less than 0.2 mg / L.
• the optimum conditions for the electrode, electrode shape, electrode length, distance between electrodes, and applied voltage to be installed in the plating recovery tank As an example, when the applied voltage is 12 V, the current value indicating the upper limit value of the Au ion concentration is 450 mA, the current value indicating the lower limit value is 350 mA, and the upper limit value and the lower limit value of the Au ion concentration.
• the anode made of Pt-plated Ti material, the cathode made of Ti material, round bar shape, electrode diameter ⁇ 15 mm, electrode length 23 mm, distance between electrodes 35mm are exemplified.
• the drainage and water injection of the plating recovery tank are carried out by a method in which the drainage and water injection motor valves are operated simultaneously, when the upper limit of 450 mA is reached, the drainage and water injection motors are used. When the valves operate simultaneously and reach the lower limit of 350 mA, the operation of the drainage and water injection motor-operated valves is stopped.
• the drained Au ion concentration is in the range of 28 to 95 mg / L as the upper limit concentration and 17 to 74 mg / L as the lower limit concentration, and 20% of the stored liquid in the plating recovery tank is replaced.
• the Au ion concentration of the adhering liquid adhering to the object to be plated washed in the plating recovery tank is 95 mg / L at maximum.
• the Au ion concentration is 10 mg / L.
• the following low concentrations are maintained.
• the water temperature of the poured water was approximately 20 ° C., and the water temperature of the plating recovery tank during continuous operation was 44 to 46 ° C.
• Electrolytic recovery of high-concentration Au ions contained in plating wastewater from the plating recovery tank is an electrolytic recovery device with a circulation processing capacity of about 200 L consisting of an anode made of Ir sintered Ti material and a cathode electrode made of Ti material (Tanaka Kikinzoku Kogyo) Au ion was collected at an electrolytic density of 130 to 200 mA / dm 2 using a mini recovery vessel.
• the same resin can be used to recover the low concentration Au ions contained in the waste liquid after the electrolytic recovery and the plating waste water from the plating washing tank, respectively, and an ion exchange resin device filled with an anion exchange resin (Tanaka Kikinzoku Kogyo) Au ions were collected using a company manufactured by Eagle RE).
• the residual Au ion concentration after the recovery process in this embodiment was less than 0.2 mg / L.
• the optimum conditions for the electrode, electrode shape, electrode length, distance between electrodes, and applied voltage to be installed in the plating recovery tank As an example, when the applied voltage is 12 V, the current value indicating the upper limit value of Pd ion concentration is 550 mA, the current value indicating the lower limit value is 450 mA, and the upper limit value and the lower limit value of Pd ion concentration.
• the optimum electrode whose difference is controlled in the range of 100 mA in current value is an anode made of a Pt-plated Ti material, a cathode electrode made of a Ti material, and has a round bar shape, a diameter of 15 mm, an electrode length of 2 mm, interelectrode distance 45mm are exemplified.
• the drained Pd ion concentration is in the range of 129 to 157 mg / L, which is the upper limit concentration.
• the Pd ion concentration of the adhering liquid adhering to the workpiece to be plated washed in the plating recovery tank is 157 mg / L at the maximum.
• the Pd ion concentration is 10 mg / L.
• the following low concentrations are maintained.
• the water temperature of the injected water was approximately 20 ° C., and the water temperature of the plating recovery tank during continuous operation was 40 to 42 ° C.
• Electrolytic recovery of high-concentration Pd ions contained in the plating wastewater from the plating recovery tank is an electrolytic recovery device with a circulation processing capacity of about 200 L consisting of an anode made of Pt-plated Ti material and a cathode electrode made of Ti material (Tanaka Kikinzoku Kogyo Co., Ltd.) Pd ions were collected at an electrolytic density of 100 to 270 mA / dm 2 .
• the same resin can be used to recover the low concentration Pd ions contained in the waste liquid after the electrolytic recovery and the plating waste water from the plating washing tank, respectively, and an ion exchange resin apparatus (manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) filled with a chelate resin. : Eagle RE) was used to recover Pd ions.
• the residual Pd ion concentration after the recovery treatment in this embodiment was less than 0.5 mg / L.
• the electrodes installed in the plating recovery tank As an example of the optimum conditions, when the applied voltage is 12 V, the current value indicating the upper limit value of the Ag ion concentration is 650 mA, the current value indicating the lower limit value is 550 mA, and the upper limit value of the Ag ion concentration and Optimal electrodes in which the difference between the lower limit values is managed in a current value range of 100 mA include an anode made of a Pt-plated Ti material and a cathode electrode made of a Ti material, having a round bar shape, a diameter of 15 mm, an electrode length 3 mm, interelectrode distance 55mm are exemplified.
• the upper limit value is 650 mA.
• the drainage electric valve is operated, and when 50% of the full water is drained, the water injection motor is operated and stopped when the water is full. Therefore, the drained Ag ion concentration is in the range of 148 to 195 mg / L, which is the upper limit concentration.
• the Ag ion concentration of the adhering liquid adhering to the workpiece to be plated washed in the plating washing tank is a maximum of 195 mg / L.
• the Ag ion concentration is 10 mg / L.
• the following low concentrations are maintained.
• the water temperature of the poured water was approximately 20 ° C.
• the water temperature of the plating recovery tank during continuous operation was 39 to 41 ° C.
• Electrolytic recovery of high-concentration Ag ions contained in plating wastewater from the plating recovery tank is an electrolytic recovery device (Tanaka Kikinzoku Kogyo Co., Ltd.) with a circulation treatment capacity of about 200 L consisting of an anode made of Ir sintered Ti material and a cathode electrode made of Ti material.
• Ag ion was collected at an electrolytic density of 130 to 200 mA / dm 2 using a mini-recovery cell.
• the same resin can be used for the recovery of low-concentration Ag ion resin contained in the waste liquid after electrolytic recovery and the plating waste water from the plating washing tank, respectively, and an ion exchange resin device (Tanaka Kikinzoku Kogyo Co., Ltd.) filled with an anion exchange resin.
• Ag ions were collected using a company manufactured by Eagle RE).
• the residual Ag ion concentration after the recovery process in this embodiment was less than 0.2 mg / L.
• the current value indicating the upper limit value of the Pt ion concentration is 500 mA
• the current value indicating the lower limit value is 400 mA
• the difference between the upper limit value and the lower limit value of the Pt ion concentration is exemplified.
• the drainage and water injection of the plating recovery tank are carried out in such a way that the water injection is activated during drainage, when the upper limit of 500 mA is reached, the drainage motor operated, and the water injection motor operated during drainage.
• the lower limit of 400 mA the operation of the drainage and water injection motor-operated valves is stopped. Therefore, the drained Pt ion concentration is in the range of 96 to 120 mg / L as the upper limit concentration and 45 to 63 mg / L as the lower limit concentration, and 40% of the stored liquid in the plating recovery tank is replaced.
• the Pt ion concentration of the adhering liquid adhering to the workpiece to be plated washed in the plating washing tank is 120 mg / L at the maximum.
• Electrolytic recovery of high-concentration Pt ions contained in plating wastewater from the plating recovery tank is an electrolytic recovery device with a circulation treatment capacity of about 200 L consisting of an anode made of Pt-plated Ti material and a cathode electrode made of Ti material (Tanaka Kikinzoku Kogyo Co., Ltd.) Pt ions were collected at an electrolytic density of 30 to 140 mA / dm 2 .
• the resin recovery of the low concentration Pt ions contained in the waste liquid after the electrolytic recovery and the plating waste water from the plating washing tank can use the same resin, respectively, and an ion exchange resin device filled with a cation exchange resin (Tanaka Kikinzoku Kogyo) Pt ions were collected using a company manufactured by Eagle RE).
• the residual Pt ion concentration after the recovery process in this embodiment was less than 0.5 mg / L.
• Embodiment 7 When plating using a Rh plating solution (trade name: RH221; Rh3 to 5 g / L, manufactured by NE Chemicat), the water temperature of the storage solution in the plating recovery tank is 50 ° C.
• the upper limit value of Rh ion concentration is set to 42 to 60 mg / L and the lower limit value is set to 16 to 32 mg / L, the optimum electrode, electrode shape, electrode length, distance between electrodes, and applied voltage are set in the plating recovery tank.
• the current value indicating the upper limit value of the Rh ion concentration is 450 mA
• the current value indicating the lower limit value is 350 mA
• the upper limit value and the lower limit value of the Rh ion concentration are exemplified.
• Embodiment 6 when the drainage and water injection of the plating recovery tank are carried out in such a manner that the water injection is activated during the drainage, when the upper limit value of 450 mA is reached, the electric drainage valve operates and the water is discharged. When the water injection motor valve operates and reaches the lower limit of 350 mA, the operation of the drainage and water injection motor valves is stopped. Therefore, the drained Rh ion concentration is in the range of the upper limit concentration of 42 to 60 mg / L and the lower limit concentration of 16 to 32 mg / L, and 30% of the stored liquid in the plating recovery tank is replaced.
• the Rh ion concentration of the adhesion liquid adhering to the workpiece to be plated washed in the plating washing tank is a maximum of 60 mg / L. By diluting this adhesion liquid with water in the plating washing tank, the concentration is less than 10 mg / L or less. Maintained.
• the temperature of the poured water was approximately 20 ° C., and the temperature of the plating recovery tank during continuous operation was 42 to 44 ° C.
• Electrolytic recovery of high-concentration Rh ions contained in the plating wastewater from the plating recovery tank is an electrolytic recovery device with a circulation processing capacity of about 200 L consisting of an anode made of Pt-plated Ti material and a cathode electrode made of Ti material (Tanaka Kikinzoku Kogyo Co., Ltd.) Rh ions were collected at an electrolytic density of 30 to 140 mA / dm 2 .
• the same resin can be used to recover the low concentration Rh ion contained in the waste liquid after the electrolytic recovery and the plating waste water from the plating washing tank, respectively.
• An ion exchange resin device filled with a cation exchange resin (Tanaka Kikinzoku Kogyo) Rh ions were collected using a company manufactured by Eagle RE). The residual Rh ion concentration after the recovery treatment in this embodiment was less than 0.5 mg / L.

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• 2010
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