CN108149280A - 一种旋流电解装置用钛基管网复合铅阳极及其制备方法 - Google Patents
一种旋流电解装置用钛基管网复合铅阳极及其制备方法 Download PDFInfo
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- 239000010936 titanium Substances 0.000 title claims abstract description 172
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 132
- 150000001875 compounds Chemical class 0.000 title claims abstract description 21
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 51
- 239000011248 coating agent Substances 0.000 claims abstract description 50
- 239000002131 composite material Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 19
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 16
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 16
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 11
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 10
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 8
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 30
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 claims description 30
- 239000002585 base Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- 230000002708 enhancing effect Effects 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910002651 NO3 Inorganic materials 0.000 claims description 14
- 229910006529 α-PbO Inorganic materials 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 238000004070 electrodeposition Methods 0.000 claims description 10
- 235000006408 oxalic acid Nutrition 0.000 claims description 10
- 239000012744 reinforcing agent Substances 0.000 claims description 10
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 239000011775 sodium fluoride Substances 0.000 claims description 9
- 229910000989 Alclad Inorganic materials 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 239000004576 sand Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000005488 sandblasting Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 claims description 5
- 238000005422 blasting Methods 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 235000014121 butter Nutrition 0.000 claims description 5
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 5
- 229940046892 lead acetate Drugs 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 238000002203 pretreatment Methods 0.000 claims description 5
- 230000002787 reinforcement Effects 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 235000013024 sodium fluoride Nutrition 0.000 claims description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 239000006004 Quartz sand Substances 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000007747 plating Methods 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 229910004074 SiF6 Inorganic materials 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 4
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000009854 hydrometallurgy Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 238000009527 percussion Methods 0.000 description 3
- 238000007788 roughening Methods 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 208000035404 Autolysis Diseases 0.000 description 1
- 206010057248 Cell death Diseases 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000028043 self proteolysis Effects 0.000 description 1
- 229910006531 α-PbO2 Inorganic materials 0.000 description 1
Classifications
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- 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
- C25C7/02—Electrodes; Connections thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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Abstract
一种旋流电解装置用钛基管网复合铅阳极及其制备方法，在钛管表面包裹钛网，再通过烧结法在钛基体上进行中间增强涂层(Ti/SnO2+Sb2O3/或Ti/SnO2+Sb2O3/MnO2)，然后分别在碱性环境和酸性环境下掺杂复镀(Ti/α‑PbO2‑RuO2‑REO‑CoO)层和(Ti/β‑PbO2‑CeO2‑ZrO2)层，可制得钛基管网复合铅阳极，由钛管、导电棒(铜管)、钛网、导电铅复合涂层组成。采用本发明的工艺和方法制造的旋流电解用钛基管网复合铅阳极能显著降低经济成本、降低能耗、能通过大电流导电性好、析氧过电位高、催化性能好、电化学活性高，在含F‑、Cl‑、ClO‑、NO3 ‑、SO4 2‑、CO3 2‑和SiF6 2‑的水溶液中使用都十分稳定，耐蚀性和长寿命，环保，不污染槽液，产品质量高。
Description
技术领域
本发明涉及湿法冶金及有色金属回收技术领域，特别是涉及一种旋流电解装置用钛基管网复合铅阳极及其制备方法。
背景技术
湿法冶金及有色金属的回收，大多数是靠电解工艺进行的。电解阳极，是电解过程必不可少的核心部件，它的质量好坏影响着电效、能耗及阴极产品的质量。传统电解糟中的阳极大多数为板状阳极，其工作电流密度高、且溶液在槽体中的流速缓慢，容易造成因浓差极化现象导致阴极产品质量下降。旋流电解法，是一种新型的湿法冶金提取金属的方法，它是利用高速旋流的溶液，在管状阳极的电催化作用下，阴极析出所需的金属。目前管状阳极是钛涂层贵金属氧化物阳极，此阳极的费用高、加工制作程度难，涂层的厚度一致性不均匀，容易在电解过程中，某处容易击穿，从而导致整个阳极导电失效。
发明内容
本发明的目的在于提供一种降低阳极费用，同时提高阳极的导电催化活性的旋流电解装置用钛基管网复合铅阳极及其制备方法。
为达到上述目的，本发明采用的技术方案是：
1)钛基体前处理：将钛网包裹于同样直径大小的钛管或钛包铜管或钛包铝管上焊接形成钛基复合管网，然后用5-10％NaOH溶液在60-80℃时进行碱侵蚀除油后再进行水洗得到钛基材，之后对钛基材进行喷砂处理，去除氧化皮；喷砂过程主要是利用高速沙流的冲击作用清理和粗化基体表面，将基体表面的钛氧化皮去除，露出原本的纯钛基体，并给予其表面一定的粗糙度；
2)草酸刻蚀：将钛基材用浓度为10-15％的草酸溶液进行沸腾煮2-3h后水洗；
3)中间增强层：按照摩尔比9:1配比将四氯化锡(SnCl4·5H2O)和三氯化锑(SbCl3)、硝酸锰Mn(NO3)2的一种或两种掺杂制成增强剂，然后按10:1的体积比将正丁醇或异丙醇和盐酸制成溶剂，将增强剂与溶剂按4:6的体积比混合得增强涂料，在步骤2)的钛基材表面涂覆增强涂料后在420-450℃进行烧结分解沉积层，得到中间增强涂层Ti/SnO2+Sb2O3或Ti/SnO2+Sb2O3+MnO2；
4)安装钛铜复合导电棒：将步骤3)处理好的钛基材与钛铜复合导电棒焊接，管网两端焊接密封制成钛铜复合导电棒；
5)碱性掺杂复镀Ti/α-PbO2-RuO2-REO-CoO层：将步骤4)处理好的钛铜复合导电棒置于碱性电镀液中，复镀钛基α-PbO2导电涂层，阴极选用不锈钢板或纯铅或钛板，电积温度为40-70℃，电流密度为1-5A/dm2，碱性电镀液中含有氧化铅(PbO)30-50g/L、氢氧化钠(NaOH)100-250g/L、碳酸钠(NaCO3)15-30g/L、硝酸镧(La(NO3)3·6H2O)8-25g/L、硝酸钴(Co(NO3)2)10-20g/L，纳米级二氧化钌粉末8-15g/L；
6)酸性掺杂复镀Ti/β-PbO2-CeO2-ZrO2层：将步骤5)的钛铜复合导电棒，在酸性电镀液中复镀钛基β-PbO2导电涂层，阴极选用不锈钢板或纯铅或钛板，电积温度为40-80℃，电流密度为2-8A/dm2，酸性电镀液含硝酸铅(Pb(NO3)2)150-250g/L、乙酸铅([(CH3COO)2Pb·3H2O])50-80g/L、硝酸铈(Ce(NO3)3)10-20g/L、纳米级二氧化锆粉末(ZrO2)8-15g/L、氟化钠(NaF2)3-8g/L；
7)热水水洗：将步骤6)处理好的钛铜复合导电棒用40-50℃的热水进行表面处理，将残留的杂质水洗干净，自然晾干得钛基管网复合铅阳极。
所述步骤1)钛网与钛管或钛包铜管或钛包铝管采用满焊方式，压平包裹于管表面，形成钛基复合管网。
所述步骤1)、步骤2)水洗温度为30-40℃。
所述的步骤1)喷砂处理采用粒度为100-180目的棕刚玉、钢砂或石英砂。
所述的步骤5)Ti/α-PbO2-RuO2-REO-CoO镀层厚度为150μm-350μm。
所述的步骤6)制的Ti/β-PbO2-CeO2-ZrO2镀层厚度为350μm-1000μm。
按以上制备方法制成的旋流电解装置用钛基管网复合铅阳极，包括钛管、钛包铜管或钛包铝管以及包裹在其上的钛网层，在钛网层上依次复镀有Ti/α-PbO2-RuO2-REO-CoO和Ti/β-PbO2-CeO2-ZrO2镀层形成管网复合镀层铅阳极。
本发明用钛基铅阳极来替代贵金属涂层阳极。铅及铅基合金阳极，在湿法冶金及金属回收、电镀行业应用广泛，因此它是具有优势的。但同时它的缺点也是很多，例如铅的自身溶解、强度底、使用容易弯曲、导电性不好，不能通过大电流。钛基铅阳极是利用钛作为基材，通过化学法、涂层法、烧结法、电镀法等综合过程制备而成，此阳极继承了铅阳极的性质，改善了铅阳极的自身的缺陷，提高了实际利用价值。
本发明与现有技术相比，具有以下优点：本发明工艺简单，采用本发明的方法制备的旋流电解钛基管网复合铅阳极，可以有效的降低传统旋流电解用的钛基贵金属氧化物涂层阳极(DSA)的价格，具体表现在：(1)造价便宜，成本低；(2)导电性好、析氧过电位高、催化性能好、电化学活性高，在含F-、Cl-、ClO-、NO3 -、SO4 2-、CO3 2-和SiF6 2-的水溶液中都十分稳定；(3)能通过大电流，耐蚀性和长寿命；(4)环保，不污染槽液，产品质量高。(4)硬度大，耐磨损。
附图说明
图1为Ti/α-PbO2-RuO-ReO-CoO镀层的SEM图。
图2为Ti/β-PbO2-CeO2-ZrO2镀层的SEM图。
具体实施方式
下面结合附图对本发明作进一步说明。
实施例1：
1)钛基体前处理：取钛管钛网将钛网焊接包裹于钛管管上，形成钛基复合管网，然后用5％NaOH溶液在80℃时进行碱侵蚀除油后再要40℃水洗得到钛基材，之后对钛基材采用粒度为100-180目的棕刚玉进行喷砂处理，去除氧化皮；喷砂过程主要是利用高速沙流的冲击作用清理和粗化基体表面，将基体表面的钛氧化皮去除，露出原本的纯钛基体，并给予其表面一定的粗糙度；
2)草酸刻蚀：将钛基材用浓度为12％的草酸溶液进行沸腾煮2.5h后在35℃水洗；
3)中间增强层：按照摩尔比9:1配比将四氯化锡(SnCl4·5H2O)和三氯化锑(SbCl3)制成增强剂，然后按10:1的体积比将正丁醇或异丙醇和盐酸制成溶剂，将增强剂与溶剂按4:6的体积比混合得增强涂料，在步骤2)的钛基材表面涂覆增强涂料后在420、℃进行烧结分解沉积层，得到中间增强涂层Ti/SnO2+Sb2O3；
4)安装钛铜复合导电棒：将步骤3)处理好的钛基材与钛铜复合导电棒焊接，管网两端焊接密封制成钛铜复合导电棒；
5)碱性掺杂复镀Ti/α-PbO2-RuO2-REO-CoO层：将步骤4)处理好的钛铜复合导电棒置于碱性电镀液中，复镀钛基α-PbO2导电涂层，得到Ti/α-PbO2-RuO2-REO-CoO厚度为180μm的镀层，阴极选用不锈钢板或纯铅或钛板，电积温度为40℃，电流密度为3A/dm2，碱性电镀液中含有氧化铅(PbO)45g/L、氢氧化钠(NaOH)180g/L、碳酸钠(NaCO3)20g/L、硝酸镧(La(NO3)3·6H2O)15g/L、硝酸钴(Co(NO3)2)15g/L，纳米级二氧化钌粉末8g/L；
由图1可以看出在碱性环境下掺杂(Ti/α-PbO2-RuO2-REO-CoO)复镀层具有一定粗糙度，它作为外部镀层的有力粘结剂，可以促进在酸性环境下掺杂(Ti/β-PbO2-CeO2-ZrO2)复镀层的挂载，增强两镀层间内部结合力。
6)酸性掺杂复镀Ti/β-PbO2-CeO2-ZrO2层：将步骤5)的钛铜复合导电棒，在酸性电镀液中复镀钛基β-PbO2导电涂层，得到Ti/β-PbO2-CeO2-ZrO2厚度为600μm的镀层，阴极选用不锈钢板或纯铅或钛板，电积温度为60℃，电流密度为5A/dm2，酸性电镀液含硝酸铅(Pb(NO3)2)200g/L、乙酸铅([(CH3COO)2Pb·3H2O])50g/L、硝酸铈(Ce(NO3)3)12g/L、纳米级二氧化锆粉末(ZrO2)10g/L、氟化钠(NaF2)5g/L；
由图2可以看出(Ti/β-PbO2-CeO2-ZrO2)镀层明显均匀致密，目的在于电化学析氧反应过程，氧气对电极镀层冲刷，同时缓解新生态氧原子进入钛基体，导致基体钝化，从而增强阳极的使用寿命。
7)热水水洗：将步骤6)处理好的钛铜复合导电棒用45℃的热水进行表面处理，将残留的杂质水洗干净，自然晾干得钛基管网复合铅阳极。
实施例2：
1)钛基体前处理：取钛包铜管钛网将钛网焊接包裹于钛包铜管上，形成钛基复合管网，然后用8％NaOH溶液在70℃时进行碱侵蚀除油后再要30℃水洗得到钛基材，之后对钛基材采用粒度为100-180目的钢砂进行喷砂处理，去除氧化皮；喷砂过程主要是利用高速沙流的冲击作用清理和粗化基体表面，将基体表面的钛氧化皮去除，露出原本的纯钛基体，并给予其表面一定的粗糙度；
2)草酸刻蚀：将钛基材用浓度为15％的草酸溶液进行沸腾煮3h后在30℃水洗；
3)中间增强层：按照摩尔比9:1配比将四氯化锡(SnCl4·5H2O)和三氯化锑(SbCl3)、硝酸锰Mn(NO3)2制成增强剂，然后按10:1的体积比将正丁醇或异丙醇和盐酸制成溶剂，将增强剂与溶剂按4:6的体积比混合得增强涂料，在步骤2)的钛基材表面涂覆增强涂料后在435℃进行烧结分解沉积层，得到中间增强涂层Ti/SnO2+Sb2O3+MnO2；
4)安装钛铜复合导电棒：将步骤3)处理好的钛基材与钛铜复合导电棒焊接，管网两端焊接密封制成钛铜复合导电棒；
5)碱性掺杂复镀Ti/α-PbO2-RuO2-REO-CoO层：将步骤4)处理好的钛铜复合导电棒置于碱性电镀液中，复镀钛基α-PbO2导电涂层，得到Ti/α-PbO2-RuO2-REO-CoO厚度为150μm的镀层，阴极选用不锈钢板或纯铅或钛板，电积温度为60℃，电流密度为5A/dm2，碱性电镀液中含有氧化铅(PbO)50g/L、氢氧化钠(NaOH)250g/L、碳酸钠(NaCO3)15g/L、硝酸镧(La(NO3)3·6H2O)25g/L、硝酸钴(Co(NO3)2)10g/L，纳米级二氧化钌粉末12g/L；
6)酸性掺杂复镀Ti/β-PbO2-CeO2-ZrO2层：将步骤5)的钛铜复合导电棒，在酸性电镀液中复镀钛基β-PbO2导电涂层，得到Ti/β-PbO2-CeO2-ZrO2厚度为350μm的镀层，阴极选用不锈钢板或纯铅或钛板，电积温度为40℃，电流密度为2A/dm2，酸性电镀液含硝酸铅(Pb(NO3)2)150g/L、乙酸铅([(CH3COO)2Pb·3H2O])70g/L、硝酸铈(Ce(NO3)3)20g/L、纳米级二氧化锆粉末(ZrO2)15g/L、氟化钠(NaF2)8g/L；
7)热水水洗：将步骤6)处理好的钛铜复合导电棒用50℃的热水进行表面处理，将残留的杂质水洗干净，自然晾干得钛基管网复合铅阳极。
实施例3：
1)钛基体前处理：取钛包铝管钛网将钛网焊接包裹于钛包铝管上，形成钛基复合管网，然后用10％NaOH溶液在60℃时进行碱侵蚀除油后再要35℃水洗得到钛基材，之后对钛基材采用粒度为100-180目的石英砂进行喷砂处理，去除氧化皮；喷砂过程主要是利用高速沙流的冲击作用清理和粗化基体表面，将基体表面的钛氧化皮去除，露出原本的纯钛基体，并给予其表面一定的粗糙度；
2)草酸刻蚀：将钛基材用浓度为10％的草酸溶液进行沸腾煮2h后在40℃水洗；
3)中间增强层：按照摩尔比9:1配比将四氯化锡(SnCl4·5H2O)和三氯化锑(SbCl3)、硝酸锰Mn(NO3)2制成增强剂，然后按10:1的体积比将正丁醇或异丙醇和盐酸制成溶剂，将增强剂与溶剂按4:6的体积比混合得增强涂料，在步骤2)的钛基材表面涂覆增强涂料后在450℃进行烧结分解沉积层，得到中间增强涂层Ti/SnO2+Sb2O3+MnO2；
4)安装钛铜复合导电棒：将步骤3)处理好的钛基材与钛铜复合导电棒焊接，管网两端焊接密封制成钛铜复合导电棒；
5)碱性掺杂复镀Ti/α-PbO2-RuO2-REO-CoO层：将步骤4)处理好的钛铜复合导电棒置于碱性电镀液中，复镀钛基α-PbO2导电涂层，得到Ti/α-PbO2-RuO2-REO-CoO厚度为350μm的镀层，阴极选用不锈钢板或纯铅或钛板，电积温度为70℃，电流密度为1A/dm2，碱性电镀液中含有氧化铅(PbO)30g/L、氢氧化钠(NaOH)100g/L、碳酸钠(NaCO3)30g/L、硝酸镧(La(NO3)3·6H2O)8g/L、硝酸钴(Co(NO3)2)20g/L，纳米级二氧化钌粉末15g/L；
6)酸性掺杂复镀Ti/β-PbO2-CeO2-ZrO2层：将步骤5)的钛铜复合导电棒，在酸性电镀液中复镀钛基β-PbO2导电涂层，得到Ti/β-PbO2-CeO2-ZrO2厚度为1000μm的镀层，阴极选用不锈钢板或纯铅或钛板，电积温度为80℃，电流密度为8A/dm2，酸性电镀液含硝酸铅(Pb(NO3)2)250g/L、乙酸铅([(CH3COO)2Pb·3H2O])80g/L、硝酸铈(Ce(NO3)3)10g/L、纳米级二氧化锆粉末(ZrO2)8g/L、氟化钠(NaF2)3g/L；
7)热水水洗：将步骤6)处理好的钛铜复合导电棒用40℃的热水进行表面处理，将残留的杂质水洗干净，自然晾干得钛基管网复合铅阳极。
Claims (7)
1.一种旋流电解装置用钛基管网复合铅阳极的制备方法，其特征在于包括以下步骤：
1)钛基体前处理：将钛网包裹于同样直径大小的钛管或钛包铜管或钛包铝管上焊接形成钛基复合管网，然后用5-10％NaOH溶液在60-80℃时进行碱侵蚀除油后再进行水洗得到钛基材，之后对钛基材进行喷砂处理，去除氧化皮；喷砂过程主要是利用高速沙流的冲击作用清理和粗化基体表面，将基体表面的钛氧化皮去除，露出原本的纯钛基体，并给予其表面一定的粗糙度；
2)草酸刻蚀：将钛基材用浓度为10-15％的草酸溶液进行沸腾煮2-3h后水洗；
3)中间增强层：按照摩尔比9:1配比将四氯化锡(SnCl4·5H2O)和三氯化锑(SbCl3)、硝酸锰Mn(NO3)2的一种或两种掺杂制成增强剂，然后按10:1的体积比将正丁醇或异丙醇和盐酸制成溶剂，将增强剂与溶剂按4:6的体积比混合得增强涂料，在步骤2)的钛基材表面涂覆增强涂料后在420-450℃进行烧结分解沉积层，得到中间增强涂层Ti/SnO2+Sb2O3或Ti/SnO2+Sb2O3+MnO2；
4)安装钛铜复合导电棒：将步骤3)处理好的钛基材与钛铜复合导电棒焊接，管网两端焊接密封制成钛铜复合导电棒；
5)碱性掺杂复镀Ti/α-PbO2-RuO2-REO-CoO层：将步骤4)处理好的钛铜复合导电棒置于碱性电镀液中，复镀钛基α-PbO2导电涂层，阴极选用不锈钢板或纯铅或钛板，电积温度为40-70℃，电流密度为1-5A/dm2，碱性电镀液中含有氧化铅(PbO)30-50g/L、氢氧化钠(NaOH)100-250g/L、碳酸钠(NaCO3)15-30g/L、硝酸镧(La(NO3)3·6H2O)8-25g/L、硝酸钴(Co(NO3)2)10-20g/L，纳米级二氧化钌粉末8-15g/L；
6)酸性掺杂复镀Ti/β-PbO2-CeO2-ZrO2层：将步骤5)的钛铜复合导电棒，在酸性电镀液中复镀钛基β-PbO2导电涂层，阴极选用不锈钢板或纯铅或钛板，电积温度为40-80℃，电流密度为2-8A/dm2，酸性电镀液含硝酸铅(Pb(NO3)2)150-250g/L、乙酸铅([(CH3COO)2Pb·3H2O])50-80g/L、硝酸铈(Ce(NO3)3)10-20g/L、纳米级二氧化锆粉末(ZrO2)8-15g/L、氟化钠(NaF2)3-8g/L；
7)热水水洗：将步骤6)处理好的钛铜复合导电棒用40-50℃的热水进行表面处理，将残留的杂质水洗干净，自然晾干得钛基管网复合铅阳极。
2.根据权利要求1所述的旋流电解装置用钛基管网复合铅阳极的制备方法，其特征在于：所述步骤1)钛网与钛管或钛包铜管或钛包铝管采用满焊方式，压平包裹于管表面，形成钛基复合管网。
3.根据权利要求1所述的旋流电解装置用钛基管网复合铅阳极的制备方法，其特征在于：所述步骤1)、步骤2)水洗温度为30-40℃。
4.根据权利要求1所述的旋流电解装置用钛基管网复合铅阳极的制备方法，其特征在于：所述的步骤1)喷砂处理采用粒度为100-180目的棕刚玉、钢砂或石英砂。
5.根据权利要求1所述的旋流电解装置用钛基管网复合铅阳极的制备方法，其特征在于：所述的步骤5)Ti/α-PbO2-RuO2-REO-CoO镀层厚度为150μm-350μm。
6.根据权利要求1所述的旋流电解装置用钛基管网复合铅阳极的制备方法，其特征在于：所述的步骤6)制的Ti/β-PbO2-CeO2-ZrO2镀层厚度为350μm-1000μm。
7.根据权利要求1所述的制备方法制成的旋流电解装置用钛基管网复合铅阳极，其特征在于：包括钛管、钛包铜管或钛包铝管以及包裹在其上的钛网层，在钛网层上依次复镀有Ti/α-PbO2-RuO2-REO-CoO和Ti/β-PbO2-CeO2-ZrO2镀层形成管网复合镀层铅阳极。
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