WO2022215587A1 - パラジウムの回収方法 - Google Patents
パラジウムの回収方法 Download PDFInfo
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- WO2022215587A1 WO2022215587A1 PCT/JP2022/015286 JP2022015286W WO2022215587A1 WO 2022215587 A1 WO2022215587 A1 WO 2022215587A1 JP 2022015286 W JP2022015286 W JP 2022015286W WO 2022215587 A1 WO2022215587 A1 WO 2022215587A1
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- palladium
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- adsorbent
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- containing liquid
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 297
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 165
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 89
- 239000003463 adsorbent Substances 0.000 claims abstract description 64
- 239000000243 solution Substances 0.000 claims description 52
- 239000007800 oxidant agent Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 16
- 230000001590 oxidative effect Effects 0.000 claims description 16
- 238000005868 electrolysis reaction Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 150000002978 peroxides Chemical group 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 3
- 239000012433 hydrogen halide Substances 0.000 claims description 3
- -1 oxoacid salt Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 31
- 239000002184 metal Substances 0.000 abstract description 31
- 238000011084 recovery Methods 0.000 description 33
- 239000000084 colloidal system Substances 0.000 description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 15
- 239000002699 waste material Substances 0.000 description 11
- 125000003277 amino group Chemical group 0.000 description 9
- 125000003396 thiol group Chemical group [H]S* 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 239000012425 OXONE® Substances 0.000 description 1
- IAPCTXZQXAVYNG-UHFFFAOYSA-M Potassium 2,6-dihydroxytriazinecarboxylate Chemical compound [K+].[O-]C(=O)C1=NC(=O)NC(=O)N1 IAPCTXZQXAVYNG-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- IDDRQDSRIZZVSG-UHFFFAOYSA-N azanium;2-iodylbenzoate Chemical compound [NH4+].[O-]C(=O)C1=CC=CC=C1I(=O)=O IDDRQDSRIZZVSG-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 229940077239 chlorous acid Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 229950000193 oteracil Drugs 0.000 description 1
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
-
- 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
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
Definitions
- the present invention relates to a palladium recovery method for efficiently recovering palladium from a palladium-containing liquid.
- palladium which is a catalytic metal
- electroless plating is performed using the catalytic action.
- colloidal palladium particles are brought into contact with the surface of the etched material to adsorb palladium, and then the adsorbed palladium is activated.
- the surface of the material with which the colloidal palladium particles are brought into contact is washed with water. Palladium colloidal particles remain in the washing water and the waste liquid after washing.
- Patent Document 1 Since palladium is an expensive metal, methods for recovering palladium from washing water and waste liquid have been proposed (for example, Patent Document 1).
- Patent Document 1 In the method for recovering palladium disclosed in Patent Document 1, by increasing the pH of a hydrochloric acid solution containing tin palladium ions, palladium is precipitated together with tin hydroxide and separated from the hydrochloric acid acid solution to obtain palladium. are collected.
- Patent Document 1 The palladium recovery method of Patent Document 1 can be used for a solution with a relatively high concentration of palladium colloid particles to precipitate and separate them. However, it is not worth the cost when it is used in a solution with a low concentration of palladium colloid particles, such as the washing water and waste liquid.
- an object of the present invention is to provide a palladium recovery method capable of selectively and efficiently recovering palladium from a palladium-containing liquid.
- the method for recovering palladium according to the present invention is characterized by oxidizing a palladium-containing liquid and then bringing it into contact with an adsorbent to adsorb palladium on the adsorbent.
- the palladium recovery method according to the present invention is characterized by oxidizing a palladium-containing liquid using active oxygen generated by electrolysis.
- the palladium recovery method uses a first reservoir in which a palladium-containing liquid is stored and is connected to a flow path, and a second reservoir in which an oxidant is stored and is connected to a flow path.
- the palladium-containing liquid is oxidized by flowing the palladium-containing liquid and the oxidizing agent from the second reservoir into the flow path, respectively, and mixing them inside the flow path.
- the oxidizing agent is a peroxide or a substance having a peroxide structure, or an aqueous solution of oxoacid salt, halogen and hydrogen halide, nitric acid and related compounds, an oxygen group solution, and any of these It is characterized by being an aqueous solution mixed in proportions.
- the palladium recovery method according to the present invention is characterized by mixing the oxidizing agent in an amount of 1/10 to 1/10000 of the weight of the palladium-containing liquid.
- the palladium-containing liquid is oxidized and then brought into contact with an adsorbent to adsorb palladium to the adsorbent.
- the palladium-containing liquid is, for example, a tin-palladium colloidal liquid.
- a tin-palladium colloidal liquid By oxidizing this tin-palladium colloidal liquid, palladium is eluted and selectively adsorbed by an adsorbent. This method of recovering palladium can be applied to solutions with relatively low concentrations, and palladium can be efficiently recovered.
- FIG. 1 is a diagram schematically showing a palladium recovery apparatus (oxidizing agent mixed type) used in a palladium recovery method according to an embodiment of the present invention.
- FIG. 2 is a diagram schematically showing another palladium recovery apparatus (oxidizing agent mixed type) used in the palladium recovery method according to the embodiment of the present invention.
- FIG. 3 is a diagram schematically showing a palladium recovery apparatus (electrolytic type) used in the palladium recovery method according to the embodiment of the present invention.
- FIG. 1 A method for recovering palladium according to this embodiment will be described with reference to FIGS. 1 to 3.
- FIG. In the palladium recovery method of the present embodiment, after oxidizing a substance in a palladium-containing liquid, the oxidized liquid is brought into contact with a predetermined adsorbent, thereby causing the adsorbent to adsorb palladium.
- a method of mixing a palladium-containing liquid with an oxidizing agent and a method of electrolyzing a palladium-containing liquid will be described as methods of oxidizing substances in the palladium-containing liquid.
- a palladium recovery apparatus 1 is used for the palladium recovery method according to the present embodiment.
- the palladium recovery device 1 includes a palladium-containing liquid storage tank (first storage section) 10 in which a palladium-containing liquid L1 is stored, an oxidant storage tank (second storage section) 11 in which an oxidant L2 is stored, and one end side. , a channel 12 connected to the palladium-containing liquid storage tank 10 and the oxidant storage tank 11, an adsorbent column unit 13 connected to the other end of the channel 12, and a waste liquid channel 14.
- the palladium-containing liquid L1 is a liquid containing palladium, and the concentration of palladium is not limited.
- a liquid having a low palladium concentration for example, a dilute tin-palladium colloidal liquid discharged into a washing liquid in the manufacturing process of printed circuit boards and decorative plating of resin is used.
- the tin-palladium colloidal solution is a solution in which colloids in which tin ions are associated with palladium as nuclei are dispersed.
- an oxidizing agent use a peroxide or a substance having a peroxide structure or an oxoate aqueous solution, a halogen or hydrogen halide solution, an aqueous solution of nitric acid and related compounds, an oxygen group solution, or an aqueous solution in which these are mixed in an arbitrary ratio.
- hydrogen peroxide solution sodium peroxodisulfate aqueous solution, potassium peroxodisulfate aqueous solution, ammonium solution, potassium peroxymonosulfate (potassium oxonate) aqueous solution, iodine solution, bromine solution, hydrogen chloride solution, hydrogen iodide solution, Hydrogen bromide solution, perchloric acid solution, chloric acid solution, chlorous acid solution, hypochlorous acid solution, nitric acid, nitrate solution, nitrous acid, nitrite solution, ozonized water, or an aqueous solution mixed with any of these can be used.
- the adsorbent column unit 13 includes an adsorbent, and for this adsorbent, for example, a metal adsorbent modified with a compound having a thiol group or a metal adsorbent modified with a compound having an amino group can be used. can.
- a metal adsorbent 13A modified with a compound having an amino group and a metal adsorbent 13B modified with a compound having a thiol group are used.
- the metal adsorbent 13A and the metal adsorbent 13B are connected in series.
- Examples of the metal adsorbent 13A modified with a compound having an amino group include Propyl-N-dimethylenetriamine Trimethylsilyl (manufactured by DPS Co., Ltd.), Propyl-N-ethylenediamine Trimethylsilyl (manufactured by DPS Co., Ltd.), and thiol group-containing Mercaptpropyl Trimethylsilyl (manufactured by DPS Co., Ltd.), for example, can be used as the compound-modified metal adsorbent 13B.
- the adsorbents in the adsorbent column unit 13 are not limited to the types and combinations shown above, and only the metal adsorbent 13B modified with a compound having a thiol group may be used, or a plurality of metal adsorbents may be used in combination. can also be used. Note that propyl-N-diethylenetriamine and propyl-N-ethylenediamine adsorbents are recyclable and have the advantage of being reusable.
- Dilute tin palladium colloidal liquid (palladium-containing liquid L1) discharged into the washing liquid from the palladium-containing liquid storage tank 10 and hydrogen peroxide water (oxidizing agent L2) from the oxidant storage tank 11 are supplied to the flow path 12, respectively. Let it flow in and mix in channel 12 .
- the inflow rate of the dilute tin-palladium colloidal solution into the channel 12 is 10 L/hr to 150 L/hr
- the inflow rate of the hydrogen peroxide solution into the channel 12 is 10 ml/hr to 1500 ml/hr.
- the amount of hydrogen peroxide solution mixed with the dilute tin-palladium colloid solution is preferably 1/10 to 1/10000.
- the mixed liquid is oxidized in the flow path 12 to break the colloid and separate the tin from the palladium.
- the oxidized liquid mixture is passed through the adsorbent column unit 13 .
- liquid is passed through a column provided with metal adsorbent 13A modified with a compound having an amino group, and then metal adsorbent 13B modified with a compound having a thiol group is provided. Allow the liquid to flow through the column with the The mixed liquid after passing through it is made to flow into the waste liquid channel 14 and treated as a waste liquid.
- the palladium recovery device 2 can also be used in the palladium recovery method according to the present embodiment.
- the palladium recovery device 2 includes a mixed liquid reservoir (third reservoir) 15, as shown in FIG.
- the same components as those of the palladium recovery device 1 are denoted by the same reference numerals, and descriptions thereof are omitted.
- one end of the channel 12 communicates with the palladium-containing liquid storage tank 10 and the oxidant storage tank 11 , and the other end of the channel 12 communicates with the mixed liquid storage tank 15 .
- the adsorbent column unit 13 is connected to the liquid mixture storage tank 15 via the channel 16 .
- a stirring member may be provided in the liquid mixture storage tank 15 to stir the liquid mixture.
- the dilute tin-palladium colloidal liquid L1 flowing from the palladium-containing liquid storage tank 10 and the hydrogen peroxide solution L2 flowing from the oxidizing agent storage tank 11 are mixed in the flow path 12, and then mixed.
- the liquid is caused to flow into the mixed liquid storage tank 15 .
- the liquid mixture is passed through the adsorbent column unit 13 through the flow path 16 .
- the mixed liquid after passing through it is made to flow into the waste liquid channel 14 and treated as a waste liquid.
- Example 1 300 ⁇ L of hydrogen peroxide (30%) was added to 500 mL of dilute tin palladium colloid solution (catalyst solution), which is the washing water used for decorative plating, and allowed to flow at 0.6 mL/min. was passed through a metal adsorbent modified with or a metal adsorbent modified with a compound having a thiol group.
- the amount of palladium adsorbed by each adsorbent was measured from the concentration of palladium metal at the inlet through which each adsorbent was passed and the concentration of palladium metal at the outlet discharged from each adsorbent.
- the inlet concentration of the adsorbent is about 4 ppm
- the outlet concentration of the metal adsorbent modified with a compound having an amino group is about 0.80 to 2 ppm. .40 ppm
- the outlet concentration of the metal adsorbent modified with a compound having a thiol group was about 3.80 ppm to 3.90 ppm.
- Example 2 Add 1 mL of sodium hypochlorite solution (available chlorine 5% or more) to 100 mL of dilute tin palladium colloid solution (catalyst solution) used as washing water, flow at 0.6 mL/min, and then have an amino group. A liquid was passed through a metal adsorbent modified with a compound and a metal adsorbent modified with a compound having a thiol group. The same evaluation as in Example 1 was performed.
- the concentration at the inlet of the adsorbent was about 4 ppm, whereas the concentration at the outlet of the metal adsorbent modified with amino groups was from about 0.20 to 0.75 ppm, and the outlet concentration of the thiol-modified metal adsorbent was about 0.20 ppm to 0.50 ppm.
- tin is separated from palladium in the dilute tin-palladium colloidal liquid L1 by mixing the dilute tin-palladium colloidal liquid L1 and hydrogen peroxide L2 in the flow path 12 . Then, in this state, the adsorbent column unit 13 is made to pass through, and the eluted palladium is selectively adsorbed by the adsorbent. Therefore, palladium can be efficiently and selectively recovered from the dilute tin-palladium colloid solution.
- the hydrogen peroxide solution (oxidizing agent) L2 is mixed at a ratio of 1/10 to 1/10000 of the weight of the dilute tin-palladium colloidal liquid L1 to remove tin from palladium. Separation can be promoted and palladium can be efficiently recovered.
- the liquid mixture is stored in the liquid mixture storage tank 15 for a predetermined period of time.
- Palladium can also be recovered by allowing the solution to pass through the adsorbent column unit 13 after allowing it to stand still. Further, if necessary, the liquid mixture may be stirred for a predetermined period of time by a stirring member in the liquid mixture storage tank 15 .
- the palladium recovery device 3 as shown in FIG. 3, has an electrolysis device 20 using platinum-plated titanium rods as electrodes.
- the same components as those of the palladium recovery device 1 are denoted by the same reference numerals, and descriptions thereof are omitted.
- the dilute tin-palladium colloidal liquid L1 is electrolyzed for a predetermined time by the electrolysis device 20 to generate active oxygen.
- the tin-palladium colloid in the dilute tin-palladium colloid solution is oxidized by this active oxygen.
- a dilute tin-palladium colloid solution that has been electrolyzed is passed through the column unit 13 via the passage 12 . After passing the solution, the solution flows into the waste liquid channel 14 and is treated as a waste liquid.
- An oxidizing agent (aqueous hydrogen peroxide) L2 may be added to the dilute tin-palladium colloidal liquid after the electrolysis treatment, and the liquid may be passed through the adsorbent column unit 13 .
- the dilute tin-palladium colloid solution may be oxidized by adding a solution containing active oxygen generated by electrolysis to the dilute tin-palladium colloid solution.
- Example 3 100 mL of the dilute tin-palladium colloid solution (catalyst solution) used as washing water was electrolyzed for 6 minutes. 80 mL of the dilute tin-palladium colloid solution after the electrolysis treatment was allowed to flow at 0.6 mL/min to pass through the metal adsorbent modified with an amino group and the metal adsorbent modified with a thiol group. Evaluation similar to Examples 1 and 2 was performed.
- the concentration at the inlet of the adsorbent was about 4 ppm, while the concentration at the outlet of the metal adsorbent modified with amino groups was about 0.60 to 1.00 ppm. and the outlet concentration of the thiol-modified metal adsorbent was about 0 ppm to 0.50 ppm.
- tin is separated from palladium in the dilute tin-palladium colloid liquid L1 by oxidizing the dilute palladium colloid liquid by electrolysis, and the eluted palladium is selected as an adsorbent. effectively adsorbed. Therefore, palladium can be efficiently and selectively recovered from the dilute tin-palladium colloid solution.
- the present embodiment has been described, but in addition to this, it is possible to select the configurations mentioned in the above embodiments or to change them to other configurations as appropriate without departing from the gist of the present invention.
- the colloid stabilizer or the like in the palladium-containing liquid L1 affects the colloid
- the amount of the oxidizing agent L2 is appropriately adjusted because the colloid is less likely to break.
- Palladium recovery device 10 Palladium-containing liquid storage tank (first storage unit) 11 Oxidant storage tank (second storage unit) 12 Channel 13 Adsorbent column units 13A, 13B Metal adsorbent 14 Waste liquid channel 15 Mixed liquid reservoir (third reservoir) 16 flow path 20 electrolyzer L1 palladium-containing liquid L2 oxidizing agent
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Abstract
Description
本実施形態に係るパラジウムの回収方法には、図1に示すように、パラジウム回収装置1を使用する。パラジウム回収装置1は、パラジウム含有液L1が貯留されたパラジウム含有液貯留槽(第一貯留部)10と、酸化剤L2が貯留された酸化剤貯留槽(第二貯留部)11と、一端側でパラジウム含有液貯留槽10及び酸化剤貯留槽11と連なった流路12と、流路12の他端側に接続される吸着剤カラムユニット13と、廃液流路14とを備えている。
アミノ基を有する化合物が修飾された金属吸着剤13Aには、例えば、Prоpyl-N-diethylenetriamine Trimethylsilyl(株式会社DPS社製)、Prоpyl-N-ethylenediamine Trimethylsilyl(株式会社DPS社製)、チオール基を有する化合物が修飾された金属吸着剤13Bには、例えば、Mercaptоprоpyl Trimethylsilyl(株式会社DPS社製)を使用することができる。
なお、希薄スズパラジウムコロイド液に対して混合する過酸化水素水の量は、1/10から1/10000とすることが好ましい。
装飾メッキに使用された水洗水である希薄スズパラジウムコロイド液(カタリスト液)500mLに、過酸化水素(30%)300μLを添加し、0.6mL/minでフローさせた後、アミノ基を有する化合物が修飾された金属吸着剤、またはチオール基を有する化合物が修飾された金属吸着剤に通液させた。評価は、各吸着剤に通液させる入口における金属パラジウム濃度と、各吸着剤から排出される出口における金属パラジウム濃度から、各吸着剤に吸着されたパラジウムの量を測定した。
なお、比較として、過酸化水素水を未添加の希薄スズパラジウムコロイド液(以下、未添加希薄スズパラジウムコロイド液とも記す)の入口、出口の金属パラジウムの濃度を測定した。
一方、未添加希薄スズパラジウムコロイド液においては、吸着剤の入口の濃度は約4ppmであるのに対し、アミノ基を有する化合物が修飾された金属吸着剤の出口の濃度は約0.80から2.40ppmであり、チオール基を有する化合物が修飾された金属吸着剤の出口の濃度は約3.80ppmから3.90ppmであった。
水洗水として使用した希薄スズパラジウムコロイド液(カタリスト液)100mLに、次亜塩素酸ナトリウム溶液(有効塩素5%以上)1mLを添加し、0.6mL/minでフローさせた後、アミノ基を有する化合物が修飾された金属吸着剤、チオール基を有する化合物が修飾された金属吸着剤に通液させた。実施例1と同様の評価を行った。
次に、パラジウム回収装置3を用いたパラジウムの回収方法について説明する。パラジウム回収装置3は、図3に示すように、白金メッキ付チタン棒を電極とする電気分解装置20を備えている。パラジウム回収装置3において、パラジウム回収装置1と同じ構成には同符号を付し、説明は省略する。
なお、電気分解処理後の希薄スズパラジウムコロイド液に酸化剤(過酸化水素水)L2を添加し、吸着剤カラムユニット13に通液させてもよい。また、電気分解により発生する活性酸素を含む溶液を希薄スズパラジウムコロイド溶液に加えることで、希薄スズパラジウムコロイド溶液を酸化してもよい。
水洗水として使用した希薄スズパラジウムコロイド液(カタリスト液)100mLを6分間、電気分解処理を行った。電気分解処理後の希薄スズパラジウムコロイド液80mLを0.6mL/minでフローさせ、アミノ基が修飾された金属吸着剤、チオール基が修飾された金属吸着剤に通液させた。実施例1及び2と同様の評価を行った。
例えば、パラジウム含有液L1中のコロイド安定化剤等の影響があるときは、コロイドが壊れにくくなっているため、酸化剤L2の量を適宜調整する。
10 パラジウム含有液貯留槽(第一貯留部)
11 酸化剤貯留槽(第二貯留部)
12 流路
13 吸着剤カラムユニット
13A,13B 金属吸着剤
14 廃液流路
15 混合液貯留槽(第三貯留部)
16 流路
20 電気分解装置
L1 パラジウム含有液
L2 酸化剤
Claims (5)
- パラジウム含有液を酸化させた後、吸着剤に接触させることで、パラジウムを前記吸着剤に吸着させる、
ことを特徴とするパラジウムの回収方法。 - 電気分解で発生させた活性酸素を利用して、前記パラジウム含有液を酸化させる、
ことを特徴とする請求項1に記載のパラジウムの回収方法。 - 前記パラジウム含有液が貯留され、流路に連なった第一貯留部及び酸化剤が貯留され、前記流路に連なった第二貯留部を用い、
前記第一貯留部から前記パラジウム含有液を、前記第二貯留部から前記酸化剤を、それぞれ前記流路に流入させ、前記流路の内部で混合させることで、前記パラジウム含有液を酸化させる、
ことを特徴とする請求項1に記載のパラジウムの回収方法。 - 前記酸化剤が、過酸化物またはペルオキシド構造を有する物質、またはオクソ酸塩、ハロゲンおよびハロゲン化水素、硝酸および関連化合物の水溶液、酸素類水溶液および、これらを混合した水溶液である、
ことを特徴とする請求項3に記載のパラジウムの回収方法。 - 前記酸化剤が、前記パラジウム含有液の重量の1/10から1/10000の量で混合させる、
ことを特徴とする請求項3または請求項4に記載のパラジウムの回収方法。
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JPH11229050A (ja) * | 1998-02-12 | 1999-08-24 | Kawasaki Kasei Chem Ltd | パラジウムの回収方法およびパラジウムの回収装置 |
JP2001279343A (ja) * | 2000-03-29 | 2001-10-10 | Toppan Printing Co Ltd | 貴金属の回収装置および貴金属の回収方法 |
JP2004083926A (ja) * | 2001-07-13 | 2004-03-18 | Kojima Kagaku Yakuhin Kk | パラジウム含有溶液からのパラジウムの回収方法 |
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JPH11229050A (ja) * | 1998-02-12 | 1999-08-24 | Kawasaki Kasei Chem Ltd | パラジウムの回収方法およびパラジウムの回収装置 |
JP2001279343A (ja) * | 2000-03-29 | 2001-10-10 | Toppan Printing Co Ltd | 貴金属の回収装置および貴金属の回収方法 |
JP2004083926A (ja) * | 2001-07-13 | 2004-03-18 | Kojima Kagaku Yakuhin Kk | パラジウム含有溶液からのパラジウムの回収方法 |
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