CN101024252B - Production method for electrolyzing metal powder - Google Patents
Production method for electrolyzing metal powder Download PDFInfo
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- CN101024252B CN101024252B CN2007100031688A CN200710003168A CN101024252B CN 101024252 B CN101024252 B CN 101024252B CN 2007100031688 A CN2007100031688 A CN 2007100031688A CN 200710003168 A CN200710003168 A CN 200710003168A CN 101024252 B CN101024252 B CN 101024252B
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Abstract
The invention provides a manufacturing method of electronic metal powder. The anode and cathode are dipped into electrolyte including sulfuric acid solution containing metallic ion, direct current is supplied to perform electrolyse. The metal powder is separated from cathode to make electronic metal powder. The insoluble anode is used as anode and forms film containing electrode active material of noble metal or oxide thereof on the matrix surface made by metal forming film. The calcinating film of perfluoro fluro resin.
Description
Technical field
The present invention relates to by electrolysis with high-quality, make electrolyzing metal powders, the particularly method of cathode copper powder such as silver, copper with high yield.
Background technology
In the past, in making the field of electrolyzing metal powder, carry out electrolysis with metals such as the silver that becomes raw material, copper as anode, at this moment, separate out at minus plate by making, thereby produce metal dusts (for example referring to Patent Document 1) such as highly purified silver, copper from the argent or the copper of anode stripping.
But, making by said method in the method for cathode copper powder, adding electric weight ground from the anode stripping, be necessary to utilize other electrolysis to remove the unnecessary copper of stripping in order to make copper exceed institute, it is complicated that the manufacturing process of electrolyzing metal powder not only becomes, and be difficult to make high-quality metal dust.Usually the electrowinning that these other electrolysis is called copper stripping electrolysis or copper.In the past, this copper stripping electrolysis general using lead was as anode.
But when carrying out copper stripping electrolysis with stereotype as anode, the lead that comes off from the surface of anode lead is sneaked into the copper that negative electrode refines inevitably.Because it is low as commodity price to sneak into plumbous copper, so the situation of dissolving again as copper raw material is more usually.And since lead anode very heavy this be common issue, add its operating difficulties, so cause the inhomogeneous of CURRENT DISTRIBUTION in the electrolysis easily because of the consumption of lead anode is inhomogeneous, tough cathode separates out the bad problem that becomes thus.And because the pole plate of hard lead anode such as Pb-Sb itself is thicker and interpolar does not have distance, lead electrode is out of shape in electrolysis, so just the problem with the short trouble of negative electrode is arranged.
Therefore, in recent years, the anode that the use insoluble anode replaces stereotype to use as this copper stripping electrolysis is proposed, this insoluble anode is a matrix with the metal of formation overlay films such as titanium, tantalum, niobium, has arranged the overlay film (for example referring to Patent Document 2) of the electrode active material that contains noble metal or its oxide in its surface.
Patent documentation 1: TOHKEMY 2001-214291 communique
Patent documentation 2: TOHKEMY 2005-163096 communique
Summary of the invention
But, the inventor etc. use with titanium, tantalum, the metal of formation overlay films such as niobium is a matrix, the insoluble anode of having arranged the overlay film of the electrode active material that contains noble metal or its oxide on its surface is used as the anode of making the cathode copper powder, use contains the sulfuric acid solution of copper ion as electrolyte, repeatedly the result of repeated test shows, in the method, because the bubble that produces on the surface of insoluble anode is less, so this bubble swims in the electrolyte, and be involved in the copper powder that forms on the negative electrode, copper powder is because this bubble and oxidized has the shortcoming that quality abnormal takes place.
Trace it to its cause, it is generally acknowledged that stereotype electrode surface densification in the past, the bubble that the surface produces become big, and using metal to be matrix with formation overlay films such as titanium, tantalum, niobiums, when having arranged the insoluble anode of overlay film of the electrode active material that contains noble metal or its oxide on its surface, because its surperficial electrode active material becomes small three-dimensional structure, the space is many, so the cause that the bubble that the surface produces diminishes.And as mentioned above, as can be known if the bubble that the surface produces diminishes, when then bubble was from the surface evaporation of electrolyte, electrolyte spread to indoor, indoor environment and is destroyed significantly attached on the tiny bubble with bubble.
The object of the present invention is to provide following technology: when making electrolyzing metal powder, quality with the raising metal dust is a purpose, becoming big by the bubble that anode is produced also can easily come out from electrolyte, can prevent that the bubble that anode produces is involved in the metal dust of separating out on the negative electrode, thereby improve the quality and the yield of metal dust, meanwhile, when bubble is evaporated from electrolyte, can prevent that electrolyte from scattering with bubble, and then prevent the pollution of the environment.
And, the present invention in order to achieve the above object, provide anode and cathode dipping in the electrolyte that comprises the sulfuric acid solution that contains metal ion, feed DC current and carry out electrolysis, pulverous metal dust is separated out on above-mentioned negative electrode and make the manufacture method of electrolyzing metal powder, wherein, use insoluble anode as above-mentioned anode, this insoluble anode has the overlay film of the electrode active material that contains noble metal or its oxide on by the metal matrix surface that forms overlay film, form the calcining overlay film of perfluor class fluororesin in its surface, and wherein to make the coating weight of the calcining overlay film of above-mentioned perfluor class fluororesin be 1～400g/m
2
In addition, the solution of the 2nd problem is that to make the above-mentioned sulfuric acid solution that contains metal ion be the sulfuric acid solution that contains copper ion, and above-mentioned pulverous metal powder is a copper powder.
And the solution of the 3rd problem is that to make above-mentioned noble metal or its oxide be yttrium oxide.
In addition, the solution of the 4th problem is that to make above-mentioned perfluor class fluororesin be the perfluor class fluororesin that contains polytetrafluoroethylene (PTFE).
And the solution of the 5th problem is that to make above-mentioned perfluor class fluororesin be the perfluor class fluororesin that contains the perfluorinated sulfonic acid copolymer.
When electrolyzing metal powder constructed in accordance, because the insoluble anode that uses is to have formed in its surface behind the calcining overlay film of perfluor class fluororesin, so the calcining overlay film of above-mentioned perfluor class fluororesin has small three-dimensional structure, enter in a part of space on more insoluble anode surface, space, this voidage reduces, so the bubble that anode surface is produced becomes big, becoming big bubble can easily break away from from electrolyte at short notice, so shortcoming in the time of can preventing to use insoluble electrode, promptly can prevent to be involved in the quality decline that electrolyzing metal powder causes, thereby can improve the quality of product electrolyzing metal powder because of the bubble that anode surface produces.And, can easily from electrolyte, break away from short notice owing to become big bubble, so when bubble evaporate, electrolyte did not scatter, and have only bubble to evaporate, so just can prevent the environmental pollution that the distribution because of electrolyte causes.
The present invention not only goes for the cathode copper powder, also is applicable to the manufacturing process of other electrolyzing metal powder, and obviously can be applied in electrolytic metal refinement field.
Description of drawings
Fig. 1 is the ideograph of the electrolytic cell of the expression manufacturing installation that is used for electrolyzing metal powder among the present invention.
Fig. 2 is illustrated in the manufacture method of electrolyzing metal powder of the present invention, and anode produces the ideograph of bubble.
Fig. 3 is illustrated in the manufacture method of electrolyzing metal powder in the past, and anode produces the ideograph of bubble.
Fig. 4 is the ideograph that expression is used to make the electrolytic cell of electrolytic copper powder among the present invention.
In addition, the material that is expressed as follows respectively of the reference numeral among the figure.
1: anode
2: negative electrode
3: electrolyte
4: electrolytic cell
5: rectifier
6: bubble
7: electrolytic cell
8: positive plate
9: minus plate
The specific embodiment
Be the base description embodiments of the present invention below with Fig. 1.
In the present invention, as shown in Figure 1, in electrolytic cell 4, add and comprise the sulfuric acid solution electrolyte 3 that contains metal ion, to form the overlay film of the electrode active material that contains noble metal or its oxide on by the metal matrix surface that forms overlay film, on this overlay film surface, formed perfluor class fluororesin the calcining overlay film insoluble anode 1 and be immersed in this electrolyte 3 by the negative electrode 2 that the titanium plate is made, feed DC current by rectifier 5 and carry out electrolysis, pulverous metal dust is separated out on above-mentioned negative electrode 2, thereby make electrolyzing metal powder.Manufacturing is during as the electrolytic copper powder of electrolyzing metal powder, and the electrolyte 3 that comprises the sulfuric acid solution that contains metal ion can be with the sulfuric acid solution that contains copper ion.
As the example of the metal that forms overlay film, can enumerate titanium, tantalum, niobium, zirconium or their alloy etc.
As the example of the electrode active material that contains noble metal or its oxide, can enumerate iridium, platinum, ruthenium, palladium, osmium, gold, silver or their oxide, in the electrolysis of sulfuric acid solution of the present invention, most preferably to the indefatigable yttrium oxide of sulfuric acid solution.
As perfluor class fluororesin, must patience be arranged to sulfuric acid electrolyte, preferably polytetrafluoroethylene (PTFE) or perfluorinated sulfonic acid copolymer, as this perfluor class fluororesin, can use the PTFE30-J of Mitsui デ ュ Port Application Off ロ ロ ケ ミ カ Le Co., Ltd. manufacturing, the Na Off ィ ォ Application (registered trade mark) 117 that Wako Pure Chemical Industries, Ltd. makes etc.In addition, the coating weight as perfluor class fluororesin is necessary for 1～400g/m
2Thickness, when at 1g/m
2When following, the electrolyte that comprises the sulfuric acid solution that contains metal ion is not had patience, will be corroded, and not be durable in several hours.On the other hand, if the coating weight of perfluor class fluororesin is too much, the calcining overlay film of then above-mentioned perfluor class fluororesin covers the surface of insoluble anode fully, can not bring into play the electrode catalyst performance as insoluble anode, so perfluor class fluororesin (coating weight) is preferably at 400g/m
2Below.
Embodiment
Then, enumerate embodiment and comparative example specifically describes the present invention.But the present invention is not limited to these embodiment.
Embodiment 1
With the pickling of titanium plate, after the drying, the solution coat that will contain iridium chloride in its surface, heating and calcining, obtain having formed on the surface of titanium plate the insoluble anode of the overlay film of the electrode active material that contains yttrium oxide, the polytetrafluoroethylene (PTFE) that to make as the PTFE30-J that is made by Mitsui デ ュ Port Application Off ロ ロ ケ ミ カ Le Co., Ltd. of perfluor class fluororesin dilutes 2 times with deionized water, 3 times, 4 times solution is coated through hairbrush coating and infusion process on the surface of DSE of ペ Le メ レ ッ ク Electricity Very Co., Ltd. manufacturing, after under 60 ℃ dry 15 minutes, calcined 10 minutes down at 330 ℃, form the calcining overlay film of perfluor class fluororesin, preparation anode 1～6.
With the anode 1～6 of the calcining overlay film that as above on the surface of DSE, forms with perfluor class fluororesin as anode, with the Ti plate as negative electrode, in the sulfuric acid solution of 180g/l, with 36 ℃, 10A/dm
2For condition is implemented electrolysis.
The result as shown in Figure 2, it is big that the bubble that anode produces becomes, bubble presents the state that breaks away from easily from electrolyte.
The initial stage coating weight and the residual quantity after electrolysis in 4000 hours of perfluor class fluororesin in the table 1 expression present embodiment 1, as shown in table 1, the initial stage coating weight is 8.6～32.9g/m
2, after 4000 hours electrolysis, the coating weight of perfluor class fluororesin reduces to 4.4～30.6g/m
2, but the huge property of the bubble that anode 1～6 produces in the present embodiment 1 is good, and its size is maintained and preliminary phase size together.
Table 1
| Anode 1 | |
|
|
|
Anode 6 | |
| |
2 |
3 |
4 |
2 |
3 |
4 times |
| Coating process | The hairbrush coating | The hairbrush coating | The hairbrush coating | Dipping | Dipping | Dipping |
| Initial stage coating weight (g/m 2) | 32.9 | 28.6 | 12.9 | 35.7 | 12.9 | 8.6 |
| (g/m after 4000 hours 2) | 28.1 | 23.6 | 8.7 | 30.6 | 10.4 | 4.4 |
| The huge property of bubble | Well | Well | Well | Well | Well | Well |
Method by embodiment 1 will be coated on the DSE that has used the manufacturing of ペ Le メ レ ッ Network Electricity Very Co., Ltd. with the solution of 2 times, 3 times, 4 times of deionized water dilutions as the perfluorinated sulfonic acid polymer that Na Off ィ ォ Application 117 (registered trade marks) by Wako Pure Chemical Industries, Ltd.'s manufacturing of perfluor class fluororesin are made through the hairbrush rubbing method, after under 60 ℃ dry 15 minutes, calcined 10 minutes down at 130 ℃, form the calcining overlay film of perfluor class fluororesin, preparation anode 7～9.
Under the condition identical, carry out electrolysis with above-mentioned anode 7～9 with embodiment 1.
The initial stage coating weight and the residual quantity after electrolysis in 800 hours of perfluor class fluororesin in the table 2 expression present embodiment 2, as shown in table 2, the initial stage coating weight is 1.14～4.00g/m
2Even after 800 hours electrolysis, the coating weight of perfluor class fluororesin does not reduce yet, the huge property of the bubble that anode 7～9 produces in the present embodiment 2 is good, and its size is maintained and preliminary phase size together.
Table 2
| |
Anode 8 | Anode 9 | |
| |
2 |
3 |
4 times |
| Coating process | The hairbrush coating | The hairbrush coating | The hairbrush coating |
| Initial stage coating weight (g/m 2) | 4 | 1.14 | 1.29 |
| Anode 7 | Anode 8 | Anode 9 | |
| (g/m after 800 hours 2) | 4 | 1.14 | 1.29 |
| The huge property of bubble | Well | Well | Well |
Comparative example 1
On the surface of the DSE that ペ Le メ レ ッ ク Electricity Very Co., Ltd. of making by the method for embodiment 1 makes, do not form the calcining overlay film of perfluor class fluororesin, it as anode, is carried out electrolysis under other all identical with embodiment 1 conditions.
Its result as shown in Figure 3, the bubble that anode produces diminishes, bubble does not break away from from electrolyte, bubble presents the state that contacts negative electrode.
Use electrolytic cell shown in Figure 4, make electrolytic copper powder.The size of electrolytic cell 7 is 120cm * 120cm * 150cm, and the size of positive plate 8 and minus plate 9 is 100cm * 100cm.As positive plate 8, the anode of anode 3 same structures of making among use and the embodiment 1 uses the Ti plate as minus plate 9, carries out 30 days electrolysis.The Cu concentration that makes electrolyte is 15～5g/l, and sulfuric acid concentration is 130～100g/l, current density: negative electrode is 12.0～8.0A/dm
2, anode is 12.0～8.0A/dm
2In addition, implement down for 35～28 ℃ in the liquid temperature.Electrolytic condition and result thereof are as shown in table 3.
It is good that consequently the electrolytic copper powder surface does not have the qualities such as amount of oxygen of color spot, powder, and its yield is 99%.
And, can easily from electrolyte, break away from short notice owing to become big bubble, so when bubble evaporate, do not have the distribution of electrolyte, and have only the bubble evaporation, so can prevent the environmental pollution that the distribution because of electrolyte causes.
Table 3
Comparative example 2
On the surface of the DSE that ペ Le メ レ ッ ク Electricity Very Co., Ltd. of making by the method for embodiment 1 makes, do not form the calcining overlay film of perfluor class fluororesin, it as anode, is carried out electrolysis under other all identical with embodiment 3 conditions.
Consequently spot appears in the surface of electrolytic copper powder, inferior quality.And the bubble of generation is little, and when bubble evaporated, electrolyte spread to indoor with bubble, so indoor distribution because of electrolyte is significantly polluted.
Describe the present invention in detail with reference to specific embodiment, but on the basis that does not break away from aim of the present invention and scope, can add various changes or modification, this is apparent to those skilled in the art.
The Japanese patent application (Japanese Patent Application 2006-042702) of the application to propose on February 20th, 2006, and its content taken in the present invention as reference.
Claims (5)
1. the manufacture method of an electrolyzing metal powder, its be with anode and cathode dipping in the electrolyte that comprises the sulfuric acid solution that contains metal ion, feed DC current and carry out electrolysis, pulverous metal dust is separated out on described negative electrode and make the manufacture method of electrolyzing metal powder
Wherein, use insoluble anode as described anode, this insoluble anode forms the overlay film of the electrode active material that contains noble metal or its oxide on by the metal matrix surface that forms overlay film, forms the calcining overlay film of perfluor class fluororesin on this overlay film surface
Wherein, the coating weight of the calcining overlay film of described perfluor class fluororesin is 1～400g/m
2
2. the manufacture method of electrolyzing metal powder according to claim 1, the wherein said sulfuric acid solution that contains metal ion is the sulfuric acid solution that contains copper ion, described pulverous metal dust is a copper powder.
3. the manufacture method of electrolyzing metal powder according to claim 1, wherein said oxide is a yttrium oxide.
4. the manufacture method of electrolyzing metal powder according to claim 1, wherein said perfluor class fluororesin is the perfluor class fluororesin that contains polytetrafluoroethylene (PTFE).
5. the manufacture method of electrolyzing metal powder according to claim 1, wherein said perfluor class fluororesin is the perfluor class fluororesin that contains the perfluorinated sulfonic acid copolymer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006042702A JP4632966B2 (en) | 2006-02-20 | 2006-02-20 | Method for producing electrolytic metal powder |
| JP2006042702 | 2006-02-20 | ||
| JP2006-042702 | 2006-02-20 |
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| Publication Number | Publication Date |
|---|---|
| CN101024252A CN101024252A (en) | 2007-08-29 |
| CN101024252B true CN101024252B (en) | 2010-11-03 |
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| CN (1) | CN101024252B (en) |
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| CN106854768B (en) * | 2016-11-21 | 2019-03-26 | 西北矿冶研究院 | electrodeposition preparation method of superfine copper powder |
| CN106757174B (en) * | 2017-02-23 | 2020-08-21 | 黄芃 | Method for preparing metal powder by electrodeposition |
| CN111826682A (en) * | 2020-07-15 | 2020-10-27 | 深圳市祺鑫环保科技有限公司 | Method for recovering metal powder |
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| JP2568838B2 (en) * | 1987-03-31 | 1997-01-08 | 古河電池株式会社 | Modified electrode and its manufacturing method |
| JPH02145788A (en) * | 1988-11-25 | 1990-06-05 | N E Chemcat Corp | Water-repellent electrode |
| JP3774262B2 (en) * | 1996-05-27 | 2006-05-10 | 日鉱金属株式会社 | Manufacturing method of high purity electrolytic copper |
| JP4323297B2 (en) * | 2003-12-02 | 2009-09-02 | 日鉱金属株式会社 | Method for producing electrolytic copper powder |
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| JP平2-145788A 1990.06.05 |
| JP昭63-244565A 1988.10.12 |
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| Publication number | Publication date |
|---|---|
| JP2007217780A (en) | 2007-08-30 |
| JP4632966B2 (en) | 2011-02-16 |
| CN101024252A (en) | 2007-08-29 |
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Address after: Kanagawa, Japan Patentee after: DE NORA PERMELEC LTD Patentee after: Fukuda Metal Foil & POwder Co., Ltd. Address before: Kanagawa, Japan Patentee before: Permelec Electrode Ltd. Patentee before: Fukuda Metal Foil & POwder Co., Ltd. |
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