WO2023016896A1 - Process for electrolytic production of metal powder - Google Patents
Process for electrolytic production of metal powder Download PDFInfo
- Publication number
- WO2023016896A1 WO2023016896A1 PCT/EP2022/071854 EP2022071854W WO2023016896A1 WO 2023016896 A1 WO2023016896 A1 WO 2023016896A1 EP 2022071854 W EP2022071854 W EP 2022071854W WO 2023016896 A1 WO2023016896 A1 WO 2023016896A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- electrolyte solution
- sulfonic acid
- metal
- silver
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 73
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 43
- 239000002184 metal Substances 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 239000000843 powder Substances 0.000 title claims abstract description 19
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 113
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 77
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 75
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052709 silver Inorganic materials 0.000 claims abstract description 46
- 239000004332 silver Substances 0.000 claims abstract description 46
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- 239000010949 copper Substances 0.000 claims abstract description 25
- 230000008021 deposition Effects 0.000 claims abstract description 21
- 239000002923 metal particle Substances 0.000 claims abstract description 18
- 238000004090 dissolution Methods 0.000 claims abstract description 8
- 238000002955 isolation Methods 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims abstract description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 18
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 9
- 150000003460 sulfonic acids Chemical class 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 230000003064 anti-oxidating effect Effects 0.000 claims description 3
- KVGOXGQSTGQXDD-UHFFFAOYSA-N 1-decane-sulfonic-acid Chemical compound CCCCCCCCCCS(O)(=O)=O KVGOXGQSTGQXDD-UHFFFAOYSA-N 0.000 claims description 2
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 claims description 2
- FUDAIDRKVVTJFF-UHFFFAOYSA-N butane-1,1-disulfonic acid Chemical compound CCCC(S(O)(=O)=O)S(O)(=O)=O FUDAIDRKVVTJFF-UHFFFAOYSA-N 0.000 claims description 2
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 claims description 2
- BRXCDHOLJPJLLT-UHFFFAOYSA-N butane-2-sulfonic acid Chemical compound CCC(C)S(O)(=O)=O BRXCDHOLJPJLLT-UHFFFAOYSA-N 0.000 claims description 2
- DBNBYVDVUHEYAX-UHFFFAOYSA-N ethane-1,1-disulfonate;hydron Chemical compound OS(=O)(=O)C(C)S(O)(=O)=O DBNBYVDVUHEYAX-UHFFFAOYSA-N 0.000 claims description 2
- AFAXGSQYZLGZPG-UHFFFAOYSA-N ethanedisulfonic acid Chemical compound OS(=O)(=O)CCS(O)(=O)=O AFAXGSQYZLGZPG-UHFFFAOYSA-N 0.000 claims description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 claims description 2
- FYAQQULBLMNGAH-UHFFFAOYSA-N hexane-1-sulfonic acid Chemical compound CCCCCCS(O)(=O)=O FYAQQULBLMNGAH-UHFFFAOYSA-N 0.000 claims description 2
- OPUAWDUYWRUIIL-UHFFFAOYSA-N methanedisulfonic acid Chemical compound OS(=O)(=O)CS(O)(=O)=O OPUAWDUYWRUIIL-UHFFFAOYSA-N 0.000 claims description 2
- RJQRCOMHVBLQIH-UHFFFAOYSA-N pentane-1-sulfonic acid Chemical compound CCCCCS(O)(=O)=O RJQRCOMHVBLQIH-UHFFFAOYSA-N 0.000 claims description 2
- CAXRKYFRLOPCAB-UHFFFAOYSA-N propane-1,1-disulfonic acid Chemical compound CCC(S(O)(=O)=O)S(O)(=O)=O CAXRKYFRLOPCAB-UHFFFAOYSA-N 0.000 claims description 2
- MGNVWUDMMXZUDI-UHFFFAOYSA-N propane-1,3-disulfonic acid Chemical compound OS(=O)(=O)CCCS(O)(=O)=O MGNVWUDMMXZUDI-UHFFFAOYSA-N 0.000 claims description 2
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims description 2
- HNDXKIMMSFCCFW-UHFFFAOYSA-N propane-2-sulphonic acid Chemical compound CC(C)S(O)(=O)=O HNDXKIMMSFCCFW-UHFFFAOYSA-N 0.000 claims description 2
- VHAHCPWLKNEDMC-UHFFFAOYSA-N but-1-ene-1,4-disulfonic acid Chemical compound OS(=O)(=O)CCC=CS(O)(=O)=O VHAHCPWLKNEDMC-UHFFFAOYSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 description 44
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 21
- 238000005265 energy consumption Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- -1 alkane sulfonic acids Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910001431 copper ion Inorganic materials 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 238000004626 scanning electron microscopy Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N beta-hydroxyethanesulfonic acid Natural products OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 235000012054 meals Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- KDKIWFRRJZZYRP-UHFFFAOYSA-N 1-hydroxypropane-2-sulfonic acid Chemical compound OCC(C)S(O)(=O)=O KDKIWFRRJZZYRP-UHFFFAOYSA-N 0.000 description 1
- NSRGOAGKXKNHQX-UHFFFAOYSA-N 2-hydroxybutane-1-sulfonic acid Chemical compound CCC(O)CS(O)(=O)=O NSRGOAGKXKNHQX-UHFFFAOYSA-N 0.000 description 1
- ZWLIPWXABAEXNY-UHFFFAOYSA-N 2-hydroxydecane-1-sulfonic acid Chemical compound CCCCCCCCC(O)CS(O)(=O)=O ZWLIPWXABAEXNY-UHFFFAOYSA-N 0.000 description 1
- VRWFADPPHBJBER-UHFFFAOYSA-N 2-hydroxydodecane-1-sulfonic acid Chemical compound CCCCCCCCCCC(O)CS(O)(=O)=O VRWFADPPHBJBER-UHFFFAOYSA-N 0.000 description 1
- CZFRHHAIWDBFCI-UHFFFAOYSA-N 2-hydroxyhexane-1-sulfonic acid Chemical compound CCCCC(O)CS(O)(=O)=O CZFRHHAIWDBFCI-UHFFFAOYSA-N 0.000 description 1
- RIYJUQDMHMUBMK-UHFFFAOYSA-N 2-hydroxypentane-1-sulfonic acid Chemical compound CCCC(O)CS(O)(=O)=O RIYJUQDMHMUBMK-UHFFFAOYSA-N 0.000 description 1
- HSXUNHYXJWDLDK-UHFFFAOYSA-N 2-hydroxypropane-1-sulfonic acid Chemical compound CC(O)CS(O)(=O)=O HSXUNHYXJWDLDK-UHFFFAOYSA-N 0.000 description 1
- RYKLZUPYJFFNRR-UHFFFAOYSA-N 3-hydroxypiperidin-2-one Chemical compound OC1CCCNC1=O RYKLZUPYJFFNRR-UHFFFAOYSA-N 0.000 description 1
- WQPMYSHJKXVTME-UHFFFAOYSA-N 3-hydroxypropane-1-sulfonic acid Chemical compound OCCCS(O)(=O)=O WQPMYSHJKXVTME-UHFFFAOYSA-N 0.000 description 1
- YEGPVWSPNYPPIK-UHFFFAOYSA-N 4-hydroxybutane-1-sulfonic acid Chemical compound OCCCCS(O)(=O)=O YEGPVWSPNYPPIK-UHFFFAOYSA-N 0.000 description 1
- LCWMHNKAZGZKAQ-UHFFFAOYSA-N 4-hydroxybutane-2-sulfonic acid Chemical compound OS(=O)(=O)C(C)CCO LCWMHNKAZGZKAQ-UHFFFAOYSA-N 0.000 description 1
- TVWPFDUIAAJJFO-UHFFFAOYSA-N 4-hydroxypentane-1-sulfonic acid Chemical compound CC(O)CCCS(O)(=O)=O TVWPFDUIAAJJFO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- VERAMNDAEAQRGS-UHFFFAOYSA-N butane-1,4-disulfonic acid Chemical compound OS(=O)(=O)CCCCS(O)(=O)=O VERAMNDAEAQRGS-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
- C25C7/08—Separating of deposited metals from the cathode
Definitions
- the present invention relates to a process for electrolytic production of metal powder and the metal powder obtained from the same.
- Fine metal powders such as copper powder and silver powder are widely used in various applications, for example in electronic pastes, lubricants, catalysts, medicines and biofilters. Electrolytic deposition of metal powders has always been an important industrial process, as the process can provide metal powders with high quality under mild conditions and does not impose high requirements of starting materials.
- an aqueous copper sulfate solution comprising sulfuric acid was generally adopted.
- the process needs certain measures for protection against corrosive sulfuric acid release from the electrolyte solution into ambient, particularly under an elevated process temperature.
- an aqueous silver nitrate electrolyte solution comprising nitric acid was generally adopted.
- the process also has the problem of nitric acid release from the electrolyte solution into ambient under elevated process temperature.
- the deposition of silver particles on the cathode is accompanied with quick growth of dendritic aggregates, especially at the corner of the cathode, in the conventional processes using a silver nitrate electrolyte solution.
- the dendritic aggregates may extend to anode and thus increase the risk of short circuit.
- a further object of the present invention is to provide a process for production of copper powder or silver powder with desirable or even smaller particle size.
- the present invention provides a process for production of a powder of metal in an electrolytic cell comprising an anode made of the metal, a cathode and an electrolyte solution, which comprises a) anodic dissolution to form ions of the metal in the electrolyte solution and cathodic deposition of metal particles from the electrolyte solution, b) removal of the metal particles from the cathode into the electrolyte solution, and c) isolation of the metal particles from the electrolyte solution, wherein
- the metal is copper or silver
- the electrolyte solution comprises (i) an alkane sulfonic acid or alkanol sulfonic acid and (ii) a soluble metal salt of an alkane sulfonic acid or alkanol sulfonic acid.
- the present invention provides the copper or silver powder obtained or obtainable by the process as described herein.
- the present invention provides use of an alkane sulfonic acid or alkanol sulfonic acid in an electrolyte solution for production of a silver or copper powder by electrolytic deposition.
- Fig. 1 shows an SEM image of the copper powder as produced by the process according to the present invention, as described in Example 1.1.
- Fig. 2 shows an SEM image of the copper powder as produced by a process not according to the present invention, as described in Comparative Example 1.1.
- Fig. 3 shows an SEM image of the silver powder as produced by the process according to the present invention, as described in Example 2.1.
- Fig. 4 shows a morphology picture of the silver deposit on the cathode as produced by the process according to the present invention, as described in Example 2.1.
- Fig. 5 shows an SEM image of the silver powder as produced by a process not according to the present invention, as described in Comparative Example 2.1.
- Fig. 6 shows a morphology picture of the silver deposit on the cathode as produced by a process not according to the present invention, as described in Comparative Example 2.1.
- Fig. 7 shows particle size D50 of the silver powder as produced by the process according to the present invention as described in Examples 2.1 to 2.3 and not according to the present invention as described in Comparative Examples 2.1 to 2.3.
- Fig. 8 shows particle size Dgo of the silver powder as produced by the process according to the present invention as described in Examples 2.1 to 2.3 and not according to the present invention as described in Comparative Examples 2.1 to 2.3.
- aqueous means that an electrolyte solution comprises a solvent containing at least 50% water. Preferably, at least 75%, more preferably 90% of the solvent is water. It can be contemplated that the solvent of the electrolyte solution consists essentially of water without any intentionally added organic solvent. Any type of water may be used, with preference to distilled or deionized water.
- the present invention provides a process for production of a powder of metal in an electrolytic cell comprising an anode made of the metal, a cathode and an electrolyte solution, which comprises a) anodic dissolution to form ions of the metal in the electrolyte solution and cathodic deposition of metal particles from the electrolyte solution, b) removal of the metal particles from the cathode into the electrolyte solution, and c) isolation of the metal particles from the electrolyte solution, wherein
- the metal is copper or silver
- the electrolyte solution comprises (i) an alkane sulfonic acid or alkanol sulfonic acid and (ii) a soluble metal salt of an alkane sulfonic acid or alkanol sulfonic acid.
- the anode is made of the metal to be deposited on cathode and thus supplies metal ions into the electrolyte solution continuously during the operation of the electrolytic cell.
- the anode may be made of the metal having a purity of at least 95%, for example at least 98% or at least 99%.
- the anode is made of copper or silver having a purity within above ranges.
- cathode there is no particular restriction to the material of cathode.
- the cathode useful for the process according to the present invention may be made of, for example, stainless steel or titanium.
- the anode and the cathode may be arranged at a distance of 1 cm to 10 cm, preferably 3 cm to 6 cm, for example 3 cm to 5.5 cm.
- the electrolyte solution comprising (i) an alkane sulfonic acid or alkanol sulfonic acid and (ii) a soluble metal salt of an alkane sulfonic acid or alkanol sulfonic acid is effective for producing silver and copper powders under an elevated electrolysis temperature, without the problem of acid release into ambient.
- Useful alkane sulfonic acids as the component (i) may be Ci-Ci2-alkane sulfonic acids, preferably Ci-Ce-alkane sulfonic acids.
- the alkane sulfonic acids may be monosulfonic acids and disulfonic acids.
- Examples of alkane monosulfonic acids include, but are not limited to methanesulfonic acid, 1-ethanesulfonic acid, 1-propanesulfonic acid, 2-propanesulfonic acid, 1-butanesulfonic acid, 2-butanesulfonic acid, 1 -pentanesulfonic acid, 1 -hexanesulfonic acid,
- alkane disulfonic acids include, but are not limited to methanedisulfonic acid, 1 ,1 -ethanedisulfonic acid, 1 ,2- ethanedisulfonic acid, 1 ,1-propanedisulfonic acid, 1 ,3-propanedisulfonic acid, 1 ,1- butanedisulfonic acid and 1 ,4-butanedisulfonic acid.
- One alkane sulfonic acid or any mixture of two or more alkane sulfonic acids may be used in the electrolyte solution in the process according to the invention.
- Useful alkanol sulfonic acids as the component (i) may be C2-Ci2-alkanol sulfonic acids, preferably C2-Ce-alkanol sulfonic acids, i.e., hydroxy substituted C2-C12-, preferably C2-C6- alkane sulfonic acids.
- the hydroxy may be on a terminal or internal carbon of alkyl chain of the alkane sulfonic acids.
- Examples of useful alkanol sulfonic acids include, but are not limited to
- 2-hydroxy-1 -ethanesulfonic acid 1-hydroxy-2-propanesulfonic acid, 2-hydroxy-1- propanesulfonic acid, 3-hydroxy-1-propanesulfonic acid, 2-hydroxy- 1-butanesulfonic acid, 4- hydroxy-1-butanesulfonic acid, 4-hydroxy-2-butanesulfonic acid, 2-hydroxy-1 -pentanesulfonic acid, 4-hydroxy-1-pentanesulfonic acid, 2-hydroxy- 1 -hexanesulfonic acid, 2-hydroxy-1- decanesulfonic acid and 2-hydroxy-1-dodecanesulfonic acid.
- One alkanol sulfonic acid or any mixture of two or more alkanol sulfonic acids may be used in the electrolyte solution in the process according to the invention.
- the alkane sulfonic acids and alkanol sulfonic acids may be those prepared by any methods known in the art or commercially available ones without particular restrictions.
- the alkane sulfonic acid or alkanol sulfonic acid as the component (i) may be comprised in the electrolyte solution at a concentration in a range of 1 to 200 grams per liter (g/L) of the electrolyte solution, particularly 5 to 180 g/L, preferably 10 to 150 g/L.
- the soluble metal salt of an alkane sulfonic acid or alkanol sulfonic acid as the component (ii) refers to a soluble silver or copper salt of alkane sulfonic acid or alkanol sulfonic acid.
- the soluble silver or copper salt of alkane sulfonic acid or alkanol sulfonic acid will also be referred to as soluble metal sulfonate hereinbelow.
- the alkane sulfonic acid or alkanol sulfonic acid from which the soluble metal sulfonate is derived may be same as or different from the alkane sulfonic acid or alkanol sulfonic acid as the component (i), and selected from those as described hereinabove for the component (i).
- the soluble metal sulfonate is a soluble silver or copper salt of the alkane sulfonic acid or alkanol sulfonic acid as the component (i).
- the electrolyte solution may comprise methanesulfonic acid as the component (i) and copper or silver methanesulfonate as the component (ii).
- the soluble metal sulfonate as the component (ii) may be comprised in the electrolyte solution at a concentration in a range of 1 to 200 g/L of the electrolyte solution, particularly 5 to 150 g/L, preferably 5 to 120 g/L, calculated as the metal ions.
- the electrolyte solution may be prepared by any known processes, for example by dissolving the metal (i.e. , copper or silver), an oxide of the metal, a hydroxide of the metal, or a carbonate of the metal in a solution of the alkane sulfonic acid or alkanol sulfonic acid as described hereinabove, to provide a solution with desired concentrations of the metal ions and the sulfonic acid.
- the metal i.e. , copper or silver
- an oxide of the metal i.e. , copper or silver
- a hydroxide of the metal a carbonate of the metal
- alkane sulfonic acid or alkanol sulfonic acid as described hereinabove
- the electrolyte solution may optionally comprise one or more additives known useful in the art, for example, gelatins derived from collagen (e.g., animal glue), glucose, urea. Some inorganic additives may also be mentioned, for example cupric chloride to improve the electrical conductivity or adjust the pH of the electrolyte solution in the copper powder production.
- the additives if present, may be comprised in the electrolyte solution at concentration of up to 20 g/L, more preferably up to 10 g/L.
- the present invention provides a process for production of silver powder in an electrolytic cell comprising an anode made of silver, a cathode and an electrolyte solution, wherein the electrolyte solution comprises (i) an alkane sulfonic acid or alkanol sulfonic acid and (ii) a soluble silver alkane sulfonate or alkanol sulfonate.
- the alkane sulfonic acid or alkanol sulfonic acid as the component (i) is preferably comprised in the electrolyte solution at a concentration in a range of 1 to 50 grams per liter (g/L) of the electrolyte solution, particularly 5 to 30 g/L, preferably 10 to 20 g/L.
- the soluble silver alkane sulfonate or alkanol sulfonate as the component (ii) is preferably comprised in the electrolyte solution at a concentration in a range of 50 to 200 g/L of the electrolyte solution, particularly 60 to 150 g/L, preferably 80 to 120 g/L, calculated as silver ions.
- the present invention provides a process for production of copper powder in an electrolytic cell comprising an anode made of copper, a cathode and an electrolyte solution, wherein the electrolyte solution comprises (i) an alkane sulfonic acid or alkanol sulfonic acid and (ii) a soluble copper alkane sulfonate or alkanol sulfonate.
- the alkane sulfonic acid or alkanol sulfonic acid as the component (i) is preferably comprised in the electrolyte solution at a concentration in a range of 50 to 200 grams per liter (g/L) of the electrolyte solution, particularly 80 to 200 g/L, preferably 100 to 160 g/L.
- the soluble copper alkane sulfonate or alkanol sulfonate as the component (ii) is preferably comprised in the electrolyte solution at a concentration in a range of 1 to 50 g/L of the electrolyte solution, particularly 5 to 30 g/L, preferably 5 to 15 g/L, calculated as copper ions.
- the anodic dissolution and cathodic deposition may be carried out at an ambient temperature or an elevated temperature, depending on the temperature of electrolyte solution.
- the process may be carried out at a temperature in the range of 20 °C to 70 °C, preferably 30 °C to 60 °C, more preferably 40 to 50 °C.
- the electrolyte solution may be pumped at a flow rate of about 5 to 20 liters per minute (L/min) during step a).
- the electrolyte solution may be pumped from a reservoir into the electrolytic cell from the top and exit from the bottom of the electrolytic cell, or may be pumped into the electrolytic cell from the bottom and exit from the top of the electrolytic cell.
- Step a) may be carried out at a current density in the range of 2 to 20 A/dm 2 (ASD), particularly 3 to 15 A/dm 2 , for example 3 to 10 A/dm 2 for the production of silver powder, and 8 to 15 A/dm 2 for the production of copper powder.
- ASD A/dm 2
- 3 to 15 A/dm 2 for example 3 to 10 A/dm 2 for the production of silver powder
- 8 to 15 A/dm 2 for the production of copper powder.
- the anodic dissolution and cathodic deposition in step a) are generally carried out for a period of 10 to 60 mins, for example 10 to 30 mins, before removing the metal particles deposited on the cathode in step b).
- the metal particles may be removed from the cathode into the electrolyte solution by any mechanical means as well known in the art without any restriction.
- step c) the electrolyte solution comprising the metal particles as obtained from step b) are subjected to an isolation to provide the metal powder.
- the isolated meal powder may further be subjected to a post treatment including washing, drying and/or anti-oxidation treatment.
- the post treatment may be carried out with any conventional means.
- the isolated meal powder may be washed with deionized water, dried under vacuum and reduced under an atmosphere of hydrogen.
- the process according to the present invention may further comprises following steps: d) washing the metal particles isolated from step c), preferably with deionized water, e) vacuum drying, and f) anti-oxidation of the metal particles, preferably reduction under an atmosphere of hydrogen.
- the present invention provides a process for production of a silver powder in an electrolytic cell comprising an anode made of silver, a cathode and an electrolyte solution, which comprises a) anodic dissolution to form silver ions in the electrolyte solution and cathodic deposition of silver particles from the electrolyte solution, b) removal of the silver particles from the cathode into the electrolyte solution, and c) isolation of the silver particles from the electrolyte solution, wherein the electrolyte solution comprises (i) a Ci-Ce-alkane sulfonic acid or alkanol sulfonic acid and (ii) a soluble silver Ci-Ce-alkane sulfonate or Ci-Ce-alkanol sulfonate.
- the electrolyte solution comprises (i) a Ci-Ce-alkane sulfonic acid or alkanol sulfonic acid at a concentration in a range of 1 to 50 g/L of the electrolyte solution, and (ii) a soluble silver Ci- Ce-alkane sulfonate or Ci-Ce-alkanol sulfonate at a concentration of 50 to 200 g/L of the electrolyte solution.
- the electrolyte solution comprises (i) a Ci-Ce-alkane sulfonic acid or alkanol sulfonic acid at a concentration in a range of 5 to 30 g/L, preferably 10 to 20 g/L of the electrolyte solution, and (ii) a soluble silver Ci-Ce-alkane sulfonate or Ci-Ce-alkanol sulfonate at a concentration of 60 to 150 g/L of the electrolyte solution, calculated as silver ions.
- the electrolyte solution comprises (i) a Ci-Ce-alkane sulfonic acid or alkanol sulfonic acid at a concentration in a range of 5 to 30 g/L, preferably 10 to 20 g/L of the electrolyte solution, and (ii) a soluble silver Ci-Ce-alkane sulfonate or Ci-Ce-alkanol sulfonate at a concentration of 80 to 120 g/L of the electrolyte solution, calculated as silver ions.
- step a) is carried out at a temperature in the range of 40 to 50 °C, preferably 45 to 50°C.
- the present invention provides a process for production of copper powder in an electrolytic cell comprising an anode made of copper, a cathode and an electrolyte solution, which comprises a) anodic dissolution to form copper ions the in the electrolyte solution and cathodic deposition of copper particles from the electrolyte solution, b) removal of the copper particles from the cathode into the electrolyte solution, and c) isolation of the copper particles from the electrolyte solution, wherein the electrolyte solution comprises (i) a Ci-Ce-alkane sulfonic acid or alkanol sulfonic acid and (ii) a soluble copper Ci-Ce-alkane sulfonate or Ci-Ce-alkanol sulfonate.
- the electrolyte solution comprises (i) a Ci-Ce-alkane sulfonic acid or alkanol sulfonic acid at a concentration in a range of 50 to 200 g/L of the electrolyte solution, and (ii) a soluble silver Ci- Ce-alkane sulfonate or Ci-Ce-alkanol sulfonate at a concentration of 1 to 50 g/L of the electrolyte solution.
- the electrolyte solution comprises (i) a Ci-Ce-alkane sulfonic acid or alkanol sulfonic acid at a concentration in a range of 80 to 200 g/L, preferably 100 to 160 g/L of the electrolyte solution, and (ii) a soluble silver Ci-Ce-alkane sulfonate or Ci-Ce-alkanol sulfonate at a concentration of 5 to 30 g/L of the electrolyte solution, calculated as copper ions.
- the electrolyte solution comprises (i) a Ci-Ce-alkane sulfonic acid or alkanol sulfonic acid at a concentration in a range of 80 to 200 g/L, preferably 100 to 160 g/L of the electrolyte solution, and (ii) a soluble silver Ci-Ce-alkane sulfonate or Ci-Ce-alkanol sulfonate at a concentration of 5 to 15 g/L of the electrolyte solution, calculated as copper ions.
- step a) is carried out at a temperature in the range of 40 to 50 °C.
- the present invention provides the copper or silver powder obtained or obtainable by the process according to the present invention as described herein.
- the copper powder obtained or obtainable by the process according to the present invention has a particle size D50 in the range of 20 to 120 microns (pm), preferably 30 to 100 pm, more preferably 40 to 90 pm, most preferably 40 to 80 pm.
- the silver powder obtained or obtainable by the process according to the present invention has a particle size D50 in the range of 100 to 600 microns (pm), preferably 150 to 500 pm, more preferably 200 to 400 pm.
- the silver powder obtained or obtainable by the process according to the present invention has a particle size D90 in the range of 200 to 1 ,000 microns (pm), preferably 400 to 800 pm.
- D50 is the diameter value at which 50 % of the total number of particles as characterized consists of particles with a diameter less than the value, as measured by a particle size laser analyzer.
- D90 is the diameter at which 90% of the total number of particles as characterized consists of particles with a diameter less than this value, as measured by a particle size laser analyzer.
- the present invention provides use of an alkane sulfonic acid or alkanol sulfonic acid in an electrolyte solution for production of a silver or copper powder by electrolytic deposition.
- the current efficiency (q) was calculated in accordance with the following equation: in which q represents current efficiency, expressed in %; m represents mass of the metal powder deposited per cell over a period of t, expressed in g;
- I electric current intensity, expressed in A
- t period of electroplating, expressed in hour
- q electrochemical equivalent of the metal, which is 1.186 g/(A h) for copper and 4.025 g/(A h) for silver.
- W energy consumption, expressed in kW h/t
- q current efficiency, expressed in %
- II average bath voltage, expressed in V.
- Black CuO was dissolved in an aqueous diluent solution of methanesulfonic acid (MSA) to provide a solution containing 12 g/L of copper ions and 140 g/L of free methanesulfonic acid as the electrolyte solution.
- MSA methanesulfonic acid
- the solution was poured into an electrolytic cell and kept at a temperature of 40 °C.
- An anode of phosphorus copper plate and a cathode of titanium plate were arranged in the electrolytic cell at a distance of 5 cm.
- the electrolytic deposition was conducted by applying a direct current with the current density of 13 A/dm 2 for 15mins.
- the obtained copper particles were removed from the cathode and isolated from the electrolyte solution.
- the collected copper particles were filtered with vacuum filtration and washed by DI water, dried at a temperature of 60 °C in a vacuum drying oven, then subjected to reduction treatment by heating to 500 °C in
- the bath voltage is 2.3V, as determined by Kocour power supply, the current efficiency (q) is 89.32% and the electrical energy consumption (W) is 2171 kW h/t. Sparse and thin dendritic crystals were observed via SEM for the copper powder, as shown in Figure 1.
- the copper powder has a particle size D50 of 79.5 pm.
- the bath voltage is 2.8 V
- the current efficiency (q) is 82.7%
- the electrical energy consumption (W) is 2854 kW h/t.
- the particle size D50 of the copper powder is 81.6pm.
- the bath voltage is 2.5 V
- the current efficiency (q) is 85.1%
- the electrical energy consumption (W) is 2476 kW h/t.
- the particle size D50 of the copper powder is 89.2 pm.
- the bath voltage is 2.6 V
- the current efficiency (q) is 87.8%
- the electrical energy consumption (W) is 2496 kW h/t.
- the particle size D50 of the copper powder is 100.9pm.
- the bath voltage is 2.35 V
- the current efficiency (q) is 89.16%
- the electrical energy consumption (W) is 2222 kW h/t.
- the particle size D50 of the copper powder is 78.4pm.
- the bath voltage is 2.2 V
- the current efficiency (q) is 91.53%
- the electrical energy consumption (W) is 2026 kW h/t.
- the particle size D50 of the copper powder is 46.3 pm.
- Copper sulfate pentahydrate was dissolved in an aqueous sulfuric acid solution to obtain a solution containing 12 g/L copper ions and 142 g/L free sulfuric acid as the electrolyte solution.
- the solution was poured into the electrolytic cell and kept at a temperature of 25 °C.
- An anode of phosphorus copper plate and a cathode of titanium plate were arranged in the electrolytic cell at a distance of 5 cm.
- the electrolytic deposition was conducted by applying a direct current with a current density of 13 A/dm 2 for 15 minutes. Then, the obtained copper particles were removed from the cathode and isolated from the electrolyte solution.
- the collected copper particles were filtered with vacuum filtration and washed by DI water, dried at a temperature of 60 °C in a vacuum drying oven, and then subjected to a reduction treatment by heating to 500 °C in a reducing atmosphere of hydrogen.
- the bath voltage is 2.3V, as determined by Kocour power supply, the current efficiency (q) is 79.86% and the electrical energy consumption (W) is 2428 kW h/t. Thick dendritic crystals were observed via SEM for the copper powder, as shown in Figure 2.
- the copper powder has a particle size D50 of 99.3 pm.
- Black Ag2 ⁇ D was dissolved in an aqueous diluent solution of methanesulfonic acid (MSA) to provide a solution containing 108 g/L of silver ions and 15.25 g/L of free methanesulfonic acid as the electrolyte solution.
- MSA methanesulfonic acid
- the solution was poured into the electrolytic cell and kept at a temperature of 50 °C.
- An anode of pure silver plate and a cathode of stainless steel plate were arranged in the electrolytic cell at a distance of 3.5 cm.
- the electrolytic deposition was conducted by applying a direct current with the current density of 5 A/dm 2 for 15mins.
- the obtained silver particles were removed from the cathode and isolated from the electrolyte solution.
- the collected silver particles were filtered with vacuum filtration and washed by DI water, dried at a temperature of 60 °C in a vacuum drying oven.
- the bath voltage is 1.23V, as determined by Kocour power supply, the current efficiency (q) is 98% and the electrical energy consumption (W) is 312 kW h/t.
- Granular crystals were observed via SEM for the silver powder, as shown in Figure 3.
- the particle size D50 of the silver powder is 328.8 pm and D90 is 525.4pm.
- the bath voltage is 1.5 V
- the current efficiency (q) is 95%
- the electrical energy consumption (W) is 392 kW h/t.
- the particle size D50 of the silver powder is 545.1 pm and D90 is 966.9pm.
- the bath voltage is 1.26 V
- the current efficiency (q) is 96%
- the electrical energy consumption (W) is 326 kW h/t.
- the particle size D 5 o of the silver powder is 571.5 pm and Dgo is 920.1 pm.
- Black Ag2 ⁇ D was dissolved in an aqueous diluent solution of nitric acid (HNO3) to provide a solution containing 108 g/L silver ions and 10 g/L free nitric acid as the electrolyte solution.
- the solution was poured into the electrolytic cell and kept at a temperature of 25 °C.
- An anode of pure silver plate and a cathode of stainless steel plate were arranged in the electrolytic cell at a distance of 3.5 cm.
- the electrolytic deposition was conducted by applying a direct current with a current density of 5 A/dm 2 for 15 minutes. Then, the obtained silver particles were removed from the cathode and isolated from the electrolyte solution.
- the collected silver particles were filtered with vacuum filtration and washed by DI water, dried at a temperature of 60 °C in a vacuum drying oven.
- the bath voltage is 1.4V
- the current efficiency (q) is 95.04%
- the electrical energy consumption (W) is 366 kW h/t.
- Granular crystals were observed via SEM for the silver powder, as shown in Figure 5.
- the particle size D50 of the silver powder is 78.7 pm and Dgo is 758.6 pm.
- the bath voltage is 1.11V
- the current efficiency (q) is 96%
- the electrical energy consumption (W) is 287 kW h/t.
- the particle size D50 of the silver powder is 395.2 pm and Dgo is 648.1 pm.
- the bath voltage is 1.04V
- the current efficiency (q) is 98%
- the electrical energy consumption (W) is 264 kW h/t.
- the particle size D50 of the silver powder is 340.3 pm and Dgo is 1167.3 pm.
- the silver powders produced according to the present invention at a temperature of above 40 °C have particle sizes at least comparable to those of the silver powders produced conventionally with the nitric acid electrolyte system.
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KR1020247004671A KR20240038984A (en) | 2021-08-13 | 2022-08-03 | Electrolytic manufacturing method of metal powder |
CN202280055407.7A CN117813420A (en) | 2021-08-13 | 2022-08-03 | Method for producing metal powder by electrolysis |
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US6183545B1 (en) * | 1998-07-14 | 2001-02-06 | Daiwa Fine Chemicals Co., Ltd. | Aqueous solutions for obtaining metals by reductive deposition |
JP2003342775A (en) * | 2002-05-24 | 2003-12-03 | Murata Mfg Co Ltd | Method of producing silver powder, silver powder and electronic parts |
WO2015095664A2 (en) * | 2013-12-20 | 2015-06-25 | Greene Lyon Group, Inc. | Method and apparatus for recovery of noble metals, including recovery of noble metals from plated and/or filled scrap |
CN106629738B (en) * | 2017-01-12 | 2019-03-22 | 东莞珂洛赫慕电子材料科技有限公司 | A method of extracting silver from crystal silicon solar plate |
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US6183545B1 (en) * | 1998-07-14 | 2001-02-06 | Daiwa Fine Chemicals Co., Ltd. | Aqueous solutions for obtaining metals by reductive deposition |
JP2003342775A (en) * | 2002-05-24 | 2003-12-03 | Murata Mfg Co Ltd | Method of producing silver powder, silver powder and electronic parts |
WO2015095664A2 (en) * | 2013-12-20 | 2015-06-25 | Greene Lyon Group, Inc. | Method and apparatus for recovery of noble metals, including recovery of noble metals from plated and/or filled scrap |
CN106629738B (en) * | 2017-01-12 | 2019-03-22 | 东莞珂洛赫慕电子材料科技有限公司 | A method of extracting silver from crystal silicon solar plate |
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