CN114411206A - Composite anode for zinc electrodeposition and preparation method thereof - Google Patents
Composite anode for zinc electrodeposition and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 239000011701 zinc Substances 0.000 title claims abstract description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000004070 electrodeposition Methods 0.000 title claims description 7
- 239000002245 particle Substances 0.000 claims abstract description 33
- 238000005363 electrowinning Methods 0.000 claims abstract description 15
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000011812 mixed powder Substances 0.000 claims abstract description 7
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 7
- 238000003825 pressing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 abstract description 4
- 238000002791 soaking Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 239000003792 electrolyte Substances 0.000 description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 8
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 7
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000000105 evaporative light scattering detection Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C11/00—Alloys based on lead
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
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Abstract
本发明公开了一种锌电积用Pb‑ZnFe2O4@MnO2复合阳极及制备方法。该方法为：将ZnFe2O4颗粒分散在含Mn2+溶液中，浸泡12h；将吸附有Mn2+的ZnFe2O4颗粒转移至溶解有MnO4 ‑的溶液中，通过归中反应获得MnO2壳体；用混料机将铅粉、ZnFe2O4@MnO2混合均匀；将混合均匀的粉末样压制成型，然后采用烧结炉使Pb‑ZnFe2O4@MnO2生坯烧结，随炉冷却至室温。在烧结过程中，Pb粉熔融形成液相，冷却后形成以铅为连续相、ZnFe2O4@MnO2为分散相的复合阳极。利用MnO2包裹ZnFe2O4颗粒可以抑制ZnFe2O4的溶解。The invention discloses a Pb-ZnFe 2 O 4 @MnO 2 composite anode for zinc electrowinning and a preparation method. The method includes: dispersing ZnFe 2 O 4 particles in a solution containing Mn 2+ and soaking for 12 hours; transferring the ZnFe 2 O 4 particles adsorbed with Mn 2+ into a solution dissolving MnO 4 , and obtaining through neutralization reaction MnO 2 shell; lead powder and ZnFe 2 O 4 @MnO 2 are mixed uniformly with a mixer; the uniformly mixed powder sample is pressed and formed, and then a sintering furnace is used to sinter the Pb‑ZnFe 2 O 4 @MnO 2 green body, Cool to room temperature with the oven. During the sintering process, the Pb powder was melted to form a liquid phase, and after cooling, a composite anode with lead as the continuous phase and ZnFe 2 O 4 @MnO 2 as the dispersed phase was formed. The dissolution of ZnFe 2 O 4 can be suppressed by wrapping ZnFe 2 O 4 particles with MnO 2 .
Description
技术领域technical field
本发明涉及材料制备领域，尤其涉及一种锌电积用Pb-ZnFe2O4@MnO2复合阳极及其制备方法。The invention relates to the field of material preparation, in particular to a Pb-ZnFe 2 O 4 @MnO 2 composite anode for zinc electrowinning and a preparation method thereof.
背景技术Background technique
在锌电积过程中，阴极发生Zn2+的还原沉积，而阳极主要起导通电路的作用。因此，锌电积一般采用铅基惰性阳极。目前，Pb-Ag合金是锌电积用标准阳极。然而，Pb-Ag阳极存在Ag耗量大、成本高、耐腐蚀性不理想等缺点。近年来，铅-陶瓷复合阳极受到广泛关注。铅-陶瓷复合阳极由铅粉和具有析氧催化活性的陶瓷颗粒混匀压制烧结而成，具有良好的析氧活性。然而，电积用电解液中一般含有150g/L左右的硫酸。在酸性条件下，陶瓷颗粒容易发生溶解，复合阳极稳定性不理想。ZL201910040251.5提出一种锌电积用铅-铁酸锌复合阳极，由于铁酸锌颗粒的存在，该阳极具有良好的析氧活性，阳极电位低，可以起到降低锌电积能耗的作用。然而，在服役过程中，ZnFe2O4颗粒周边的Pb会发生电化学氧化为PbO2或PbSO4。由于Pb与氧化产物PbO2或PbSO4摩尔体积不一样，导致ZnFe2O4裸露，进而引发ZnFe2O4的溶解。During the zinc electrowinning process, the reduction deposition of Zn 2+ occurs at the cathode, while the anode mainly acts as a conducting circuit. Therefore, zinc electrowinning generally uses lead-based inert anodes. Currently, Pb-Ag alloys are the standard anodes for zinc electrowinning. However, Pb-Ag anodes have disadvantages such as large Ag consumption, high cost, and unsatisfactory corrosion resistance. In recent years, lead-ceramic composite anodes have received extensive attention. The lead-ceramic composite anode is made by mixing, pressing and sintering lead powder and ceramic particles with oxygen evolution catalytic activity, and has good oxygen evolution activity. However, the electrolytic solution for electrowinning generally contains about 150 g/L of sulfuric acid. Under acidic conditions, the ceramic particles are easily dissolved, and the stability of the composite anode is not ideal. ZL201910040251.5 proposes a lead-zinc ferrite composite anode for zinc electrowinning. Due to the existence of zinc ferrite particles, the anode has good oxygen evolution activity and low anode potential, which can reduce the energy consumption of zinc electrowinning. . However, during service, Pb around the ZnFe 2 O 4 particles will undergo electrochemical oxidation to PbO 2 or PbSO 4 . Because the molar volume of Pb and the oxidation products PbO 2 or PbSO 4 are not the same, ZnFe 2 O 4 is exposed, which in turn triggers the dissolution of ZnFe 2 O 4 .
发明内容SUMMARY OF THE INVENTION
针对Pb-ZnFe2O4复合阳极存在ZnFe2O4颗粒易溶解，稳定性不高的缺点，本发明提出一种Pb-ZnFe2O4@MnO2复合阳极及其制备方法。Aiming at the shortcomings of easy dissolution of ZnFe 2 O 4 particles and low stability in the Pb-ZnFe 2 O 4 composite anode, the present invention provides a Pb-ZnFe 2 O 4 @MnO 2 composite anode and a preparation method thereof.
本发明提出的一种锌电积用Pb-ZnFe2O4@MnO2复合阳极，该复合阳极由Pb和ZnFe2O4@MnO2组成，其中，Pb为连续相，包裹有MnO2壳层的ZnFe2O4为分散相，Pb与ZnFe2O4@MnO2通过压制-烧结实现冶金结合。The present invention proposes a Pb-ZnFe 2 O 4 @MnO 2 composite anode for zinc electrowinning. The composite anode is composed of Pb and ZnFe 2 O 4 @MnO 2 , wherein Pb is a continuous phase and is wrapped with a MnO 2 shell. The ZnFe 2 O 4 is the dispersed phase, and the metallurgical bonding of Pb and ZnFe 2 O 4 @MnO 2 is achieved by pressing-sintering.
优选地，Pb-ZnFe2O4@MnO2复合阳极中ZnFe2O4@MnO2的质量百分数为0.50～10.00wt.％。Preferably, the mass percentage of ZnFe 2 O 4 @MnO 2 in the Pb-ZnFe 2 O 4 @MnO 2 composite anode is 0.50-10.00 wt.%.
本发明提出的一种如上述任一项所述的锌电积用Pb-ZnFe2O4@MnO2复合阳极的制备方法，包括以下步骤：The present invention proposes a method for preparing a Pb-ZnFe 2 O 4 @MnO 2 composite anode for zinc electrowinning as described in any of the above, comprising the following steps:
将ZnFe2O4颗粒分散在含Mn2+溶液中，浸泡12h；Disperse ZnFe 2 O 4 particles in a solution containing Mn 2+ and soak for 12h;
将吸附有Mn2+的ZnFe2O4颗粒转移至溶解有MnO4 -的溶液中，通过归中反应获得MnO2壳体；Transferring the ZnFe 2 O 4 particles adsorbed with Mn 2+ into the solution dissolving MnO 4 - , and obtaining the MnO 2 shell through the neutralization reaction;
用混料机将铅粉、ZnFe2O4@MnO2混合均匀；Mix lead powder and ZnFe 2 O 4 @MnO 2 evenly with a mixer;
将混合均匀的粉末样压制成型，然后采用烧结炉使Pb-ZnFe2O4@MnO2生坯烧结，随炉冷却至室温。The uniformly mixed powder sample was pressed into shape, and then the Pb-ZnFe 2 O 4 @MnO 2 green body was sintered in a sintering furnace, and cooled to room temperature with the furnace.
优选地，铅粉颗粒粒径为100nm～1000μm；ZnFe2O4颗粒粒径为50nm～1000μm。Preferably, the particle size of the lead powder is 100 nm˜1000 μm; the particle size of the ZnFe 2 O 4 particle is 50 nm˜1000 μm.
优选地，含Mn2+溶液中Mn2+浓度为0.05-1.50mol/L。Preferably, the Mn 2+ concentration in the Mn 2+ -containing solution is 0.05-1.50 mol/L.
优选地，含MnO4 -溶液中MnO4 -浓度为0.01-0.05mol/L。Preferably, the MnO 4 - concentration in the MnO 4 --containing solution is 0.01-0.05 mol/L.
优选地，压制成型压力为10～30MPa，烧结温度为327～337℃。Preferably, the pressing pressure is 10-30MPa, and the sintering temperature is 327-337°C.
本发明的发明构思及技术原理如下：The inventive concept and technical principle of the present invention are as follows:
MnO2在酸性溶液中既具有良好的化学稳定性，又具有较高的电化学稳定性。通过归中反应，在ZnFe2O4表面形成MnO2包裹壳层，可以在电解过程中抑制ZnFe2O4的化学溶解，提高阳极的稳定性和服役寿命。值得注意的是，MnO2层的厚度需要调控在1μm以下，否则ZnFe2O4的析氧活性无法发挥出来。然而，Mn2+与MnO4 -反应很快，很容易形成单独的MnO2颗粒或过厚的MnO2壳层。因此，在制备MnO2壳层的时候，需要先在ZnFe2O4吸附一些Mn2+，然后将颗粒转移至含MnO4 -溶液中，通过优化Mn2+浓度、浸泡时间、MnO4 -浓度，可以获得具有合适厚度的MnO2壳层。综上，本发明提出的Pb-ZnFe2O4@MnO2复合阳极具备耐腐蚀性能好、能耗低的优点，具有较大的工业应用价值。 MnO2 has both good chemical stability and high electrochemical stability in acidic solution. Through the neutralization reaction, a MnO2 - encapsulated shell is formed on the surface of ZnFe2O4 , which can inhibit the chemical dissolution of ZnFe2O4 during the electrolysis process and improve the stability and service life of the anode. It is worth noting that the thickness of the MnO 2 layer needs to be controlled below 1 μm, otherwise the oxygen evolution activity of ZnFe 2 O 4 cannot be exerted. However, Mn 2+ reacts quickly with MnO 4 - and it is easy to form individual MnO 2 particles or an excessively thick MnO 2 shell. Therefore, when preparing the MnO 2 shell, it is necessary to adsorb some Mn 2+ in ZnFe 2 O 4 first, and then transfer the particles to the MnO 4 - containing solution. By optimizing the Mn 2+ concentration, soaking time, MnO 4 - concentration , a MnO2 shell with suitable thickness can be obtained. In conclusion, the Pb-ZnFe 2 O 4 @MnO 2 composite anode proposed by the present invention has the advantages of good corrosion resistance and low energy consumption, and has great industrial application value.
具体实施方式Detailed ways
结合以下实施例对本发明的内容进行详细说明。The content of the present invention will be described in detail with reference to the following examples.
实施例1Example 1
将平均粒径为220nm的ZnFe2O4颗粒分散在含0.05mol/L Mn2+溶液中，浸泡12h；将吸附有Mn2+的ZnFe2O4颗粒转移至溶解有0.05mol/L MnO4 -的溶液中，通过归中反应获得MnO2壳体，壳体厚度为0.52μm；用混料机将200nm铅粉、ZnFe2O4@MnO2混合均匀，ZnFe2O4@MnO2质量分数为1.0wt％。将混合均匀的粉末样在30Mpa下压制成型，然后在327℃下保温烧结2h，随炉冷却至室温。该复合阳极在模拟锌电积电解液中恒流极化(500A m-2)72h后，电解液ICP-MASS检测未检测出Fe2+和Fe3+，阳极电位相较传统Pb-Ag板低72mV。Disperse ZnFe 2 O 4 particles with an average particle size of 220nm in a solution containing 0.05mol/L Mn 2+ and soak for 12h; transfer the ZnFe 2 O 4 particles with Mn 2+ adsorption to a solution containing 0.05mol/L MnO 4 - MnO 2 shell was obtained by neutralization reaction, and the shell thickness was 0.52 μm; 200nm lead powder, ZnFe 2 O 4 @MnO 2 were mixed uniformly with a mixer, and the mass fraction of ZnFe 2 O 4 @MnO 2 was uniform. 1.0 wt%. The uniformly mixed powder samples were pressed and formed at 30Mpa, then kept sintered at 327°C for 2h, and cooled to room temperature with the furnace. After the composite anode was galvanostatic polarization (500A m -2 ) for 72h in the simulated zinc electrodeposition electrolyte, no Fe 2+ and Fe 3+ were detected by ICP-MASS detection of the electrolyte, and the anode potential was higher than that of the traditional Pb-Ag plate. 72mV low.
实施例2Example 2
将平均粒径为1.96μm的ZnFe2O4颗粒分散在含0.10mol/L Mn2+溶液中，浸泡12h；将吸附有Mn2+的ZnFe2O4颗粒转移至溶解有0.03mol/L MnO4 -的溶液中，通过归中反应获得MnO2壳体，壳体厚度为0.91μm；用混料机将200nm铅粉、ZnFe2O4@MnO2混合均匀，ZnFe2O4@MnO2质量分数为1.0wt％。将混合均匀的粉末样在25Mpa下压制成型，然后在327℃下保温烧结2h，随炉冷却至室温。该复合阳极在模拟锌电积电解液中恒流极化(500A m-2)72h后，电解液ICP-MASS检测未检测出Fe2+和Fe3+，阳极电位相较传统Pb-Ag板低25mV。The ZnFe 2 O 4 particles with an average particle size of 1.96 μm were dispersed in a solution containing 0.10 mol/L Mn 2+ and soaked for 12 h; the ZnFe 2 O 4 particles with Mn 2+ adsorbed were transferred to a solution containing 0.03 mol/L MnO In the solution of 4- , MnO 2 shell was obtained by neutralization reaction, and the shell thickness was 0.91 μm; 200nm lead powder, ZnFe 2 O 4 @MnO 2 were mixed uniformly with a mixer, and the mass of ZnFe 2 O 4 @MnO 2 was uniform. The fraction is 1.0 wt%. The uniformly mixed powder samples were pressed and formed at 25Mpa, then kept sintered at 327°C for 2h, and cooled to room temperature with the furnace. After the composite anode was galvanostatic polarization (500A m -2 ) for 72h in the simulated zinc electrodeposition electrolyte, no Fe 2+ and Fe 3+ were detected by ICP-MASS detection of the electrolyte, and the anode potential was higher than that of the traditional Pb-Ag plate. 25mV lower.
对比例1Comparative Example 1
将平均粒径为1.96μm的ZnFe2O4颗粒分散在含1.00mol/L Mn2+溶液中，浸泡12h；将吸附有Mn2+的ZnFe2O4颗粒转移至溶解有0.05mol/L MnO4 -的溶液中，通过归中反应获得MnO2壳体，壳体厚度为2.30μm；用混料机将200nm铅粉、ZnFe2O4@MnO2混合均匀，ZnFe2O4@MnO2质量分数为1.0wt％。将混合均匀的粉末样在25Mpa下压制成型，然后在327℃下保温烧结2h，随炉冷却至室温。该复合阳极在模拟锌电积电解液中恒流极化(500A m-2)72h后，电解液ICP-MASS检测未检测出Fe2+和Fe3+，阳极电位较传统Pb-Ag阳极高50mV。The ZnFe 2 O 4 particles with an average particle size of 1.96 μm were dispersed in a solution containing 1.00 mol/L Mn 2+ and soaked for 12 h; the ZnFe 2 O 4 particles with adsorbed Mn 2+ were transferred to a solution containing 0.05 mol/L MnO In the solution of 4- , a MnO 2 shell was obtained through the neutralization reaction, and the shell thickness was 2.30 μm; 200 nm lead powder, ZnFe 2 O 4 @MnO 2 were mixed uniformly with a mixer, and the mass of ZnFe 2 O 4 @MnO 2 was uniform. The fraction is 1.0 wt%. The uniformly mixed powder samples were pressed and formed at 25Mpa, then kept sintered at 327°C for 2h, and cooled to room temperature with the furnace. After the composite anode was galvanostatic polarization (500A m -2 ) for 72h in the simulated zinc electrodeposition electrolyte, no Fe 2+ and Fe 3+ were detected in the electrolyte by ICP-MASS detection, and the anode potential was higher than that of the traditional Pb-Ag anode. 50mV.
对比例2Comparative Example 2
将平均粒径为18.5μm的ZnFe2O4颗粒分散在含1.5mol/L Mn2+溶液中，浸泡12h；将吸附有Mn2+的ZnFe2O4颗粒转移至溶解有0.08mol/L MnO4 -的溶液中，ZnFe2O4颗粒表面未获得MnO2壳体；用混料机将200nm铅粉、处理后的ZnFe2O4颗粒混合均匀，处理后的ZnFe2O4质量分数为1.0wt％。将混合均匀的粉末样在30Mpa下压制成型，然后在327℃下保温烧结2h，随炉冷却至室温。该复合阳极在模拟锌电积电解液中恒流极化(500A m-2)72h后，电解液采用ICP-MASS检测出0.28mg/L Fe3+，阳极电位与传统Pb-Ag阳极相当。The ZnFe 2 O 4 particles with an average particle size of 18.5 μm were dispersed in a solution containing 1.5 mol/L Mn 2+ and soaked for 12 h; the ZnFe 2 O 4 particles with adsorbed Mn 2+ were transferred to a solution containing 0.08 mol/L MnO In the solution of 4- , MnO2 shells were not obtained on the surface of ZnFe2O4 particles ; 200nm lead powder and treated ZnFe2O4 particles were mixed evenly with a mixer, and the mass fraction of treated ZnFe2O4 was 1.0 wt%. The uniformly mixed powder samples were pressed and formed at 30Mpa, then kept sintered at 327°C for 2h, and cooled to room temperature with the furnace. After the composite anode was galvanostatically polarized (500A m -2 ) for 72h in a simulated zinc electrodeposition electrolyte, the electrolyte detected 0.28mg/L Fe 3+ by ICP-MASS, and the anode potential was comparable to that of the traditional Pb-Ag anode.
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