CN101265590B - Double flute paralleling process for electrolytic refining metal Zn - Google Patents

Double flute paralleling process for electrolytic refining metal Zn Download PDF

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CN101265590B
CN101265590B CN2008100609512A CN200810060951A CN101265590B CN 101265590 B CN101265590 B CN 101265590B CN 2008100609512 A CN2008100609512 A CN 2008100609512A CN 200810060951 A CN200810060951 A CN 200810060951A CN 101265590 B CN101265590 B CN 101265590B
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zinc
tank
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CN101265590A (en
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郑华均
顾正海
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Zhejiang University of Technology ZJUT
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Abstract

The invention provides a double-tank processing electrolytic refining metallic zinc process. The electrolyte tank is composed of a main refining tank and an auxiliary purifying tank, the main refining tank takes a zinc sheet obtained by casting zinc dross needing purifying as an anode, the auxiliary purifying tank takes insoluble ruthenium-titanium alloy as an anode, and meanwhile Zn<2+>-NH3-NH4C1-H2O solution system is taken as the electrolyte in the main refining tank and the auxiliary purifying tank to carry out the electrolytic reaction, so that purified zinc (cathode zinc) is obtained onthe negative plates of the main refining tank and the auxiliary purifying tank. The invention adopts the insoluble anode and the casting soluble anode to carry out double-tank processing electrolyticrefining metallic zinc, thereby, on one hand, having the advantages of simple process, saved equipment investment, and high production efficiency, and on the other hand, balancing the zinc concentration in the electrolyte and improving the recovery rate of zinc metal in the dross containing zinc by the parallel running of the insoluble anode electrolyte tank. The recycling can be carried out to the electrolyte in order to fully consume the metal in the casting anode and the anode slime, which meets the environmental requirement with higher economic benefit.

Description

A kind of double flute paralleling process for electrolytic refining metal Zn
(1) technical field
The present invention relates to a kind of double flute paralleling process for electrolytic refining metal Zn, be mainly used in and from industrial residue, reclaim the preparation high purity zinc.
(2) background technology
Electrorefining technology is because technical process is short, and facility investment is little, the current efficiency height, and power consumption is low and be subjected to paying close attention to widely.When the anode in the electrolyzer adopts soluble metal, enter electrolytic solution by the metal ion electrolysis on the anode, metal ion is owing to the consumption of separating out at negative electrode in the constantly additional electrolytic solution.If metal is in meltage on the anode and the amount of separating out imbalance on negative electrode, the concentration of metal ion will change in the electrolytic solution, and this variation is understood increasingly along with electrolytic, causes the collapse of electrolysis system at last.Usually, chemical dissolution and electrochemical dissolution take place in soluble anode simultaneously, its current efficiency is higher than 100%, and the negative electrode of metal is separated out the competition that often is accompanied by hydrogen and is separated out and the foreign ion codeposition, metal often is lower than 100% in the current efficiency of cathodic deposition, thereby carry out along with electrolytic, the concentration of metal ion improves constantly in the electrolytic solution.
When the anode in the electrolyzer adopted insoluble anode, anodic reaction was generally the oxidation of gas and separates out (as oxygen, chlorine); Metal ion can carry out and constantly reduces along with cathodic process in the electrolytic solution, therefore, constantly adds metal ion in the electrolyzer and could guarantee higher current efficiency and the quality of purifying metals.
Zn 2+-NH 3-NH 4Cl-H 2The hydrometallurgy field that the O electrolyte ties up to the zinc metal has demonstrated great potentiality.This system is strong to the adaptability of material, especially when handling the high raw material of foreign matter contents such as silicon, chlorine, calcium, has only when directly leaching and can could dissolve with the metal that ammonia forms title complex, and modal impurity iron can not leach, and reduces purification burden greatly; Anode material adopts ruthenium titanium anode in the electrolytic deposition process, can not produce pollution by anticathode zinc, and power consumption is 2400-2600kW h, save power consumption about 20% than traditional sulfuric acid system, in addition, ammonia-ammonium chloride system zinc does not take place anti-molten, cathode zinc peel off also simple and convenient.
(3) summary of the invention
Purpose of the present invention is exactly the advantage of comprehensive insoluble anode electrolyzer and founding solvability anode electrolytic tank, simplifies technological process, improves the rate of recovery of metallic zinc, reduces energy expenditure, and a kind of double flute paralleling process for electrolytic refining metal Zn is provided.
The technical solution used in the present invention is:
A kind of double flute paralleling process for electrolytic refining metal Zn, electrolyzer is made up of main refining groove and secondary purification groove, the zine plate that the cadmia casting that described main refining groove is purified with needs obtains (adopting the zine plate of fusion industry zinc slag casting usually) is anode, is negative electrode with the aluminium sheet, and described secondary purification groove is with insoluble ruthenium titanium plate (the titanium plate surface-coated RuO normally that is coated with 2, can adopt commercial commodity) for anode, be negative electrode with the aluminium sheet, described main refining groove and secondary purification groove are by pipeline connection, with Zn 2+-NH 3-NH 4Cl-H 2The O solution system is an electrolytic solution, carries out electrolytic reaction in main refining groove and secondary purification groove, the cathode zinc product after obtaining purifying on main refining groove and the secondary purification groove negative plate simultaneously; NH in the described electrolytic solution 3Concentration is 1.5～2.5mol/L, NH 4Cl concentration is 1.5～2.5mol/L, Zn 2+Concentration is 0.3～0.4mol/L.
Technology of the present invention is intended to the zinc concentration by solution in the balance electrorefining process, guarantee electrorefining operation steady in a long-term, improve the rate of recovery of metallic zinc, adopt insoluble anode and founding solvability anode double flute paralleling electrolysis process to carry out the comprehensive recovery of commercial zinc waste residue.Zine ion in the main refining groove electrolytic solution is mainly derived from the dissolving of anode zinc; Zine ion in the secondary purification groove electrolytic solution is mainly derived from main refining groove, and the purpose of secondary purification groove mainly is zinc ion concentration in the BES and the pH in the solution, improves the total yield of metallic zinc simultaneously.
Electrolytic process regularly detects the concentration of electrolyte ph and ammoniacal liquor.In order to reduce the volatilization of ammoniacal liquor, should above electrolyzer, seal device.The anode of periodic filtering separaitng electrolytic tank bottom is to guarantee the quality of cathode zinc.Its cycle of operation can be 1～6 day, promptly continues electrorefining after 1～6 day, peels the spelter on negative plate surface, in addition, also should change anode in the electrorefining process, the anode that changes is through cleaning, dry, remove surface attachments, and new positive plate is made in fusion again.The rate of recovery of zinc metal is about 80% in this main electrorefining process cadmia.
For obtaining compact structure, smooth surface, high quality zinc that foreign matter content is few, also can add gelatin and Sodium dodecylbenzene sulfonate in the described electrolytic solution as mixed additive, the gelatin addition is 0.1g/L, the Sodium dodecylbenzene sulfonate addition is 0.05g/L.
Described electrolytic process can carry out according to this area normal condition, and preferred, described main refining groove electrolytic process parameter is as follows: 30～40 ℃ of temperature, and with interpole gap 12～14cm, current density 200～300A/m 2, bath voltage 0.9～1.1V.Described secondary purification groove electrolytic process parameter is as follows: 30～40 ℃ of temperature, and with interpole gap 14～16cm, current density 150～200A/m 2, bath voltage 3.0～3.3V.
Preferably, NH in the described electrolytic solution 3Starting point concentration is 2.0mol/L, NH 4The Cl starting point concentration is 2.0mol/L, Zn 2+Starting point concentration is 0.31mol/L, owing to can separate out nitrogen on the anode in the electrolytic process, so regularly adding ammoniacal liquor keeps NH in the electrolytic process 3Concentration is 2.0mol/L.
Be to keep the operation steady in a long-term of electrorefining process, keep the stable of zinc ion concentration and electrolytic solution potential of hydrogen in the electrolytic solution, the present invention in founding solvability anode master electrorefining, the parallel secondary purification groove of electrolysis that adopts insoluble anode.By the electrolysis of the secondary purification groove of insoluble anode, consume the zine ion of being on the increase in the electrolytic solution, and keep pH stable.Adopt the ruthenium titanium alloy as insoluble anode, the reaction that takes place at this electrode is the nitrogen evolution reaction, can consume the ammonia in the electrolytic solution, can regularly add ammoniacal liquor and come balance.The deposition potential of nitrogen is about 1.1V, and well below the deposition potential of oxygen, for this reason, the power consumption of this technology saves 25% than traditional sulfuric acid system electrolysis production metallic zinc.The electrolytic solution of the low zinc ion concentration that this electrolyzer overflows can circulate and be used for the leaching of the anode sludge, and leach liquor returns secondary purification groove electrolytic recovery cathode zinc.Like this, the leaching yield of the anode sludge reaches 90%, and total rate of recovery of zinc metal can reach 95% in the cadmia.
Beneficial effect of the present invention is mainly reflected in: adopt insoluble anode and founding solvability anode double flute paralleling at Zn 2+-NH 3-NH 4Cl-H 2O electrolyte system electrolytic refining metal Zn, guarantee that founding solvability anode electrolytic tank technology is simple on the one hand, low equipment investment, advantage of high production efficiency, run parallel by the insoluble anode electrolyzer on the other hand, come the zinc concentration in the BES, improve the rate of recovery of zinc metal in the utilising zinc containing waste residue.Adopt the double flute electrolysis process can recycle electrolytic solution, fully consume the metal in the founding anode and the anode sludge, both compliance with environmental protection requirements has high economic benefit again.
(4) description of drawings
Fig. 1 is a process flow sheet of the present invention;
Fig. 2 is the energy spectrogram (EDS) of founding cadmia;
Fig. 3 is RuO 2-Ti anodic XRD figure;
Fig. 4 is the energy spectrogram of soluble-anode electrolysis cathode zinc;
Fig. 5 be can not the soluble-anode electrolysis cathode zinc can spectrogram;
(5) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1:
1, founding zinc anode plate
Fig. 2 is the energy spectrogram (EDS) of founding cadmia, and the result shows that the impurity in the fusion industry cadmia is mainly aluminium, iron, oxygen, silicon, calcium.Concrete content is as shown in table 1.Not high to the most significant iron level of founding influence.Therefore, cadmia is heated to 600 ℃ in reducing atmosphere, can direct pouring becomes positive plate.The specification of mould is 8cm * 8cm * 1cm (a length x width x thickness).
Table 1: various impurity and content thereof in the founding cadmia
The impurity title Aluminium Iron Oxygen Calcium Silicon
Content (wt%) 4.34 1.39 2.08 0.69 0.38
2, titanium plating ruthenium insoluble anode
The anode of insoluble anode electrolyzer adopts titanium plating ruthenium alloy.Fig. 3 is RuO 2The XRD figure of-Ti anode (chemical industry limited liability company product is reached in Shaanxi), RuO 2, TiO 2With Ti all respectively at 26.5 °, 35 °, 37.5 ° and 55 ° have the obvious characteristics peak.Illustrate that the electrode materials composition mainly is is matrix with the titanium, surface-coated RuO 2And TiO 2The dimensionally stable anode of crystallite mixture.
Embodiment 2: the double flute paralleling electrolytic refining metal Zn
The electrolytic cycle of double flute paralleling is set at 1 day, the dissolving anode adopts the positive plate of embodiment 1 preparation, negative plate adopts pure aluminum plate, specification is 10cm * 10cm * 1cm (a length x width x thickness), consisting of of electrolytic solution: ammoniacal liquor (25wt%) 2mol/L, ammonium chloride 2mol/L, zinc ion concentration 20g/L; Additive is the mixed additive of gelatin and Sodium dodecylbenzene sulfonate, and addition is respectively 0.1g/L and 0.05g/L.The insoluble anode material adopts embodiment 1 ruthenium titanium anode, the specification of insoluble anode is 12cm * 12cm * 0.3cm (a length x width x thickness), negative plate adopts aluminium sheet as negative plate, its specification is 10cm * 10cm * 1cm (a length x width x thickness), electrolytic solution and the electrolysis of founding cadmia are joined, for with a kind of electrolytic solution, the test parameter of electrolytic process is as shown in table 2.
Produce in a certain amount of anode sludge (about 5wt%) in the soluble-anode electrolysis process, wherein, the content of zinc is about 20wt%, and the content of impurity aluminum and iron is respectively up to 15wt% and 7.8wt%, and this shows that the impurity major part in the cadmia has all entered in the anode sludge in the electrolytic process.
Various technical parameters in the comprehensive accounting electrolytic process, concrete outcome is as shown in table 3.
Table 2: the setting of double flute paralleling electrolytic process parameter
Figure G2008100609512D00061
Table 3: double flute paralleling electrolysis tech index result
Figure G2008100609512D00062
Fig. 4 and Fig. 5 be respectively soluble-anode electrolysis in the double flute paralleling electrolytic process why not the cathode zinc that soluble-anode electrolysis obtains EDAX results as can be seen, on cathode zinc after testing less than the iron in the cadmia, calcium, impurity such as silicon only contain micro-aluminium in the product.Wherein, the content of zinc can reach 99.89% and 99.90% respectively.
Embodiment 3:
The electrolytic cycle of double flute paralleling is set at 3 days, and other conditions are identical with embodiment 2.Produce in a certain amount of anode sludge (about 10wt%) in the soluble-anode electrolysis process, wherein, the content of zinc is about 25wt%, and the content of impurity aluminum and iron reaches 15wt% and 9.3wt% respectively.The purity of cathode zinc keeps identical substantially with embodiment 2 gained results, but the degree of roughness on cathode zinc surface will be higher than embodiment 2 gained cathode zincs.
Table 4: double flute paralleling electrolysis tech index result
Figure G2008100609512D00063
Figure G2008100609512D00071
Various technical parameters in the comprehensive accounting electrolytic process, concrete outcome is as shown in table 4.As seen, compare with embodiment 2, cathode efficiency slightly reduces in the soluble-anode electrolysis groove, power consumption slightly raises, the waste residue rate that produces but has obvious reduction, and the direct yield of zinc slightly reduces, and the current efficiency of insoluble anode electrolytic process is constant substantially, power consumption slightly raises, and the total yield of the electrolytic zinc of double flute paralleling still remains on 94%.
Embodiment 4:
The electrolytic cycle of double flute paralleling is set at 5 days, and other conditions are identical with embodiment 2.Produce in a certain amount of anode sludge (about 11wt%) in the soluble-anode electrolysis process, wherein, the content of zinc is about 24.5wt%, and the content of impurity aluminum and iron reaches 15.6wt% and 9.7wt% respectively.The quality of gained cathode zinc is substantially the same manner as Example 3.
Various technical parameters in the comprehensive accounting electrolytic process, concrete outcome is as shown in table 5.As seen, compare with embodiment 3, all technical indicator results are basic identical, and this every technical indicator that shows the double flute paralleling electrolysis process tends towards stability.
Table 4: double flute paralleling electrolysis tech index result
Figure G2008100609512D00072

Claims (7)

1. double flute paralleling process for electrolytic refining metal Zn, electrolyzer is made up of main refining groove and secondary purification groove, the zine plate that the cadmia casting that described main refining groove is purified with needs obtains is anode, is negative electrode with the aluminium sheet, described secondary purification groove with insoluble to be coated with ruthenium titanium plate be anode, be negative electrode with the aluminium sheet, described main refining groove and secondary purification groove are by pipeline connection, with Zn 2+-NH 3-NH 4Cl-H 2The O solution system is that electrolytic solution carries out electrolysis, obtains cathode zinc on main refining groove and secondary purification groove negative plate; NH in the described electrolytic solution 3Concentration is 1.5～2.5mol/L, NH 4Cl concentration is 1.5～2.5mol/L,
Zn 2+Concentration is 0.3～0.4mol/L.
2. technology as claimed in claim 1 is characterized in that: also add gelatin and Sodium dodecylbenzene sulfonate additive in the described electrolytic solution, the gelatin addition is 0.1g/L, and the Sodium dodecylbenzene sulfonate addition is 0.05g/L.
3. technology as claimed in claim 1 or 2 is characterized in that: described main refining groove electrolytic process parameter is as follows: 30～40 ℃ of temperature, and with interpole gap 12～14cm, current density 200～300A/m 2, bath voltage 0.9～1.1V.
4. technology as claimed in claim 1 or 2 is characterized in that: described secondary purification groove electrolytic process parameter is as follows: 30～40 ℃ of temperature, and with interpole gap 14～16cm, current density 150～200A/m 2, bath voltage 3.0～3.3V.
5. technology as claimed in claim 1 is characterized in that: the zine plate with the casting of fusion industry zinc slag is the anode of main refining groove.
6. technology as claimed in claim 1 is characterized in that: NH in the described electrolytic solution 3Starting point concentration is 2.0mol/L, NH 4The Cl starting point concentration is 2.0mol/L, Zn 2+Starting point concentration is 0.31mol/L, and regularly adding ammoniacal liquor keeps NH in the electrolytic process 3Concentration is 2.0mol/L.
7. technology as claimed in claim 1 is characterized in that: the used for electrolyte of the low zinc ion concentration of the part that produces in the secondary purification groove is in the scrap anode of main refining groove electrolysis generation and the leaching of the anode sludge, and leach liquor returns secondary purification groove electrolytic recovery cathode zinc.
CN2008100609512A 2008-04-11 2008-04-11 Double flute paralleling process for electrolytic refining metal Zn Expired - Fee Related CN101265590B (en)

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CN101698952B (en) * 2009-10-30 2012-02-15 施熊飞 Process for preparing zinc powder by wet method
CN102080236B (en) * 2010-12-20 2015-11-25 湘西自治州矿产与新材料技术创新服务中心 A kind of electrolytic solution impurity-removing method producing high purity zinc
CN107268026B (en) * 2017-06-14 2023-07-18 昆明理工大学 Device for extracting zinc through double-electrolytic-cell electro-deposition and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4183794A (en) * 1977-03-14 1980-01-15 Ross Richard H C L Zinc extraction method
CN1071714A (en) * 1991-10-14 1993-05-05 昆明工学院 A kind of electrolytic refining process of producing pure zinc by crude zinc
US6500229B1 (en) * 1998-04-08 2002-12-31 Recupac Method for treating steel works dust by wet process
CN101054686A (en) * 2007-02-14 2007-10-17 浙江工业大学 Process for purifying zinc from casting zinc residue

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4183794A (en) * 1977-03-14 1980-01-15 Ross Richard H C L Zinc extraction method
CN1071714A (en) * 1991-10-14 1993-05-05 昆明工学院 A kind of electrolytic refining process of producing pure zinc by crude zinc
US6500229B1 (en) * 1998-04-08 2002-12-31 Recupac Method for treating steel works dust by wet process
CN101054686A (en) * 2007-02-14 2007-10-17 浙江工业大学 Process for purifying zinc from casting zinc residue

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