CN1318621C - Methpd for separating and recovering Sb and Bi - Google Patents
Methpd for separating and recovering Sb and Bi Download PDFInfo
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- CN1318621C CN1318621C CNB2005100742962A CN200510074296A CN1318621C CN 1318621 C CN1318621 C CN 1318621C CN B2005100742962 A CNB2005100742962 A CN B2005100742962A CN 200510074296 A CN200510074296 A CN 200510074296A CN 1318621 C CN1318621 C CN 1318621C
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Abstract
To provide a method by which Sb and Bi in a copper electrolytic solution can be separated and recovered using simple equipment with superior selectivity and the reuse of an eluate is made possible. The copper electrolytic solution is brought into contact with a chelate resin to make the chelate resin adsorb Sb and Bi, and a hydrochloric acid type eluate is brought into contact with the chelate resin to elute Sb and Bi. An Sb metal is recovered by dry treatment from Sb neutralized slag recovered by neutralizing the resultant Sb- and Bi-containing eluant within a pH range of 1.5 to 3.0. Then a Bi metal is recovered by dry treatment from Bi neutralized slag recovered by neutralizing the eluant within a pH range of 4 to 5. Further, the concentration of chlorine in the liquor after the Bi neutralization is regulated to 6 mol/L, and the liquor is reused as a chelate resin eluate.
Description
Technical field
The present invention relates to use resin absorption to remove and be contained in Sb in the employed copper electrolyte and Bi in the copper electrolyzing refining as impurity, when reclaiming Sb and Bi selectively from this resin elutriant then, the method that the elutriant that reclaims behind Sb, the Bi is re-used.
Background technology
In the copper electrolyte that in copper electrolyzing refining, uses, contain Sb or Bi, when these compositions in described copper electrolyte surpass finite concentration, will produce detrimentally affect quality as the electrolytic copper of product as impurity.
Therefore, make and in all sorts of ways to clean copper electrolyte.For example, as the method that reclaims Sb and Bi from copper electrolyte, just make copper electrolyte contact resin, absorption Sb and Bi on described resin, elutriant is contacted with resin and Sb and Bi are recovered in the elutriant, described elutriant is carried out sulfidizing, the method (patent documentation 1: special permission 2938285) that Sb and Bi are reclaimed as sulfide; Come this elutriant is carried out neutralizing treatment with alkali, with Sb and Bi as in the oxyhydroxide and the method (patent documentation 2: special permission 3431456 etc.) that reclaims of dregs.
On the other hand, also there is pair elutriant to carry out sulfidizing, after Sb reclaimed as sulfide, use electrolysis to collect the method (patent documentation 3: special fair 1-14317) that Bi is reclaimed as galvanic deposit Bi, carry out the Sb on the resin with EDTA solution, the wash-out of Bi, and by in and pH reclaim the method (patent documentation 4: special fair 2-33653) of Sb and Bi selectively, carry out the Bi on the resin with different elutriants, the wash-out of Sb collects to reclaim galvanic deposit Bi from each elutriant with electrolysis then, the method of galvanic deposit Sb (patent documentation 5: special permission 3350917, patent documentation 6: the spy opens flat 10-306331) etc.
In the method for patent documentation 1 and 2, existence is the problem of Separation and Recovery Sb and Bi effectively.In the method in patent documentation 3, existence will be used the problem of hydrogen sulfide.
In addition, in the method in patent documentation 4, wish in the draining treatment process, EDTA to be carried out discharging after the oxygenolysis, in the method in patent documentation 5 and 6, in equipment complexity and elutriant, contain the occasion of As, have the trouble that produces arsenic gas.
The resin ablution of [patent documentation 1] special permission 2938285[copper electrolyte]
[patent documentation 2] special permission 3431456[is adsorbed on the elution process of the Sb on the resin]
[patent documentation 3] special fair 1-14317[copper electrolyte method of cleaning]
[patent documentation 4] special fair 2-33653[is adsorbed on antimony in the resin and the wash-out recovery method of bismuth]
Antimony in the electrolytic solution of [patent documentation 5] special permission 3350917[copper electrolyzing refining, the selective recovery method of bismuth]
[patent documentation 6] spy opens flat 10-306331[optionally reclaims Sb and Bi from copper electrolyte method]
Summary of the invention
The object of the present invention is to provide the simple equipment of a kind of usefulness just can selectivity Sb and the Bi in the Separation and Recovery copper electrolyte preferably, and can re-use the method for elutriant.
The present invention provides in order to address the above problem:
(1) separation and recovery method of a kind of Sb and Bi, wherein, copper electrolyte is contacted with resin, absorption Sb and Bi on resin, and the elutriant that makes the salt acids contacts this resin and comes wash-out Sb and Bi, the elutriant of resulting Sb of containing and Bi then neutralizes, the pH that makes this elutriant is in 1.5～3.0 scope, reclaim the Sb metal from the Sb that is recovered to and in the dregs by dry process at last, described dry process is in 850 ℃～950 ℃ temperature range, Sb that use yellow soda ash and charcoal carry out and the separation and recovery method of Bi.
(2) in 850 ℃～950 ℃ temperature range, use yellow soda ash and charcoal carry out on note (1) described dry process, use sodium hydroxide under 700 ℃～800 ℃ temperature, to handle the Sb of impurity and the separation and recovery method of Bi then.
(3) it is characterized in that, salt acids elutriant to described Sb of containing of last note (1) and Bi carries out neutralizing treatment, then this elutriant of only having isolated Sb is carried out neutralizing treatment, the pH that makes this elutriant is 4～5, at last by the Sb of dry process recovery Bi metal from the Bi that is recovered to and in the dregs and the separation and recovery method of Bi.
(4) go up note (3) described dry process and be to use sodium hydroxide and charcoal, Sb that under 850 ℃～950 ℃ temperature, carries out and the separation and recovery method of Bi.
(5) upwards add hydrochloric acid in the solution after note (3) described neutralizing treatment, after adjusting total cl concn and being 5～6mol/L, Sb that re-uses as the elutriant of resin and the separation and recovery method of Bi.
By implementing the present invention, can access following effect.
(1) only carries out simple neutralizing treatment, just Sb and the Bi in the separation eluent effectively.
(2) by among the Sb that recovery is obtained and among dregs or the Bi and dregs and solvent, and carry out dry process, can stop Sb, Bi and be discharged to outside the system as Sb raw material, Bi raw material.
(3) and then, by adding hydrochloric acid in the elutriant after neutralizing treatment, adjust total cl concn, can re-use as elutriant.
Description of drawings
Fig. 1 represents the treatment scheme of Separation and Recovery Sb of the present invention and Bi.
Fig. 2 represents to add alkali (sodium hydroxide) in the elutriant that contains Sb and Bi of resin, in carrying out and the time in and the Sb in pH and the elutriant and the curve of Bi concentration relationship.
Fig. 3 represents the Bi in the solution behind the wash-out, the concentration of Sb in order to obtain the eluting rate that re-uses elutriant.
Embodiment
According to Fig. 1 treatment scheme of the present invention is described.
Make copper electrolyte contact resin, absorption Sb and Bi on resin (* absorption among Fig. 1: dot).
As this resin, can use エ Port テ ス MX-2 (ミ ヨ シ grease corporate system), Purolite S950 (PUROLITE corporate system) etc.
The elutriant of salt acids is contacted with the resin that has adsorbed Sb and Bi,, make it to flow out in the elutriant (* wash-out among Fig. 1) from resin wash-out Sb and Bi.At this moment, the hydrochloric acid soln that total cl concn is modulated to 5～6mol/L uses as elutriant.
The processing of dregs (among the Sb and)
In the elutriant that contains Sb and Bi, add alkali and adjust pH, only make Sb form oxyhydroxide in and dregs (being to neutralize in the 1st step among Fig. 1).As the alkali that adds this moment,, use sodium hydroxide for the purpose that re-uses chlorion.
In addition, as shown in Figure 2,, Bi is remained in the elutriant, and remove Sb, separate Bi and Sb by in 1.5～3.0 pH scope, carrying out neutralizing treatment.
This be because, at pH less than 1.5 occasion, during Sb is not recycled to and in the dregs, thus not preferred, and if pH greater than 3.0, during then Bi also is recycled to dregs in cause.
To among the Sb and after the dregs solid-liquid separation of implement filtering etc., it is reclaimed as solid substance.
Forming with dregs among the Sb of this moment is Sb:25～30mass%, As:9～11mass%, Bi:1.5～2.5mass%, Cu:0.1～0.2mass%.
(the 2 step dry process of Sb)
In above-mentioned Sb and dregs add as the yellow soda ash of solvent and do the timber (for example charcoal) of charcoal, and be heated to 850 ℃～950 ℃, reclaim thick Sb metal (the Sb dry process among Fig. 1: be illustrated in claim 2).The thick Sb metal that recovery obtains is formed, for example about Sb:75mass%, As:9mass%, Bi:5mass%, Cu:0.5mass%.
And find: especially the note that goes up of using yellow soda ash is handled, even it is under 950 ℃ high temperature, also inequality with the processing of using sodium hydroxide, a little less than the oxidizing power to As, Sb, As, Sb are not oxidized, the not oxidized maintenance metallic state of Sb, and As remains in the metal.
Then use sodium hydroxide to remove impurity.By thick Sb metal and NaOH are fused again, the As composition can be reduced to about 0.1mass%.
This is preferably 700 ℃～800 ℃ of melting temperature (Tm)s again.Be in order not make the Sb volatilization.(be equivalent to claim 3.)。
The processing of dregs (among the Bi and)
In the elutriant of having removed Sb, add alkali, adjust pH, make Bi form oxyhydroxide in and dregs (being to neutralize in the 2nd step among Fig. 1).As the alkali that adds this moment,, use sodium hydroxide for the purpose that re-uses chlorion.
In addition, as shown in Figure 2, in 4～5 pH scope, carry out neutralizing treatment.
This be because, at pH less than 4 occasion, during Bi is not recycled to and in the dregs, thus not preferred, and if pH greater than 5, As dissolved cause more then.
To among the Bi and the dregs solid-liquid separation also implementing to filter etc., it is reclaimed as solid substance.
Forming with dregs among the Bi of this moment is Bi:20～30mass%, As:8～10mass%, Sb:0.1～0.2mass%, Cu:4～5mass%.
(the 2 step dry process of Bi)
To among this Bi and dregs, also can add as the yellow soda ash of solvent and do the timber of charcoal, and be heated to 850 ℃～950 ℃, reclaim thick Bi metal (the Bi dry process among Fig. 1 :).
The thick Bi metal that recovery obtains is formed, for example about Bi:70mass%, As:14mass%, Sb:1mass%, Cu:14mass%.
For the impurity of removing in the described metal preferably carries out alkaline purification.That is, fuse again, the As composition can be reduced to about 0.6mass% by making thick Bi metal and NaOH.
The treatment temp of this moment is 700 ℃～800 ℃.
(the 1 step dry process of Bi)
But, because Bi also will be difficult to volatilization (oxidation) than Sb, even so will remove as basic salt after the As oxidation, the rate of recovery that also may not be certain Bi descends, so better method is to utilize this point, only finish in the utilization and the reducing and smelting of dregs and the operation that As is sloughed in alkaline purification, and be preferred in industrial this method with 1 step.
That is, solvent yellow soda ash used instead be sodium hydroxide, under 850 ℃～950 ℃, carry out described dry process.(be equivalent to claim 5.)
Be because can enoughly can remove impurity A s, Sb thus, and the volatilization of Bi is few, can reclaim Bi effectively once going on foot.Thereby, can just can obtain the finished product by the 1 step dry process that does not need to carry out sodium-hydroxide treatment at low temperatures, be a kind of preferable methods therefore.
Re-use (adjustment Cl concentration among Fig. 1) as elutriant after adding hydrochloric acid in the solution after reclaiming Bi, after the neutralization of the 2nd step.At this moment, total cl concn is adjusted at 5～6mol/L.
Because if total cl concn is below the 5mol/L, then from the deterioration of efficiency of resin wash-out Sb, Bi, even be made as more than the 6mol/L, elution efficiency is also constant substantially.
[embodiment]
(embodiment 1)
(going on foot dry process with dregs 2 among the Sb)
Resin (Purolite S950) behind absorption Sb, the Bi with 6N hydrochloric acid soln wash-out, has been recovered to the elutriant with composition as shown in table 1.
Table 1 elutriant is formed
| As | Sb | Bi | Cu | |
| [g/l] | [g/l] | [g/l] | [g/l] | |
| Concentration | 0.8 | 3.1 | 1.1 | 0.2 |
Above-mentioned elutriant is neutralized to pH with NaOH carries out solid-liquid separation after 2, be recovered among the Sb and dregs.
Then, be to carry out solid-liquid separation after filtrate after 2 the neutralization is neutralized to pH4 with NaOH with pH, be recovered among the Bi and dregs.As shown in table 2 in each with the composition of dregs.Can from Sb, reclaim the Sb of concentration up to 29.0mass% with dregs.From Bi He in the dregs, reclaimed the Bi of concentration up to 25.0mass%.
Among table 2 Sb and among dregs and the Bi and dregs
| As | Sb | Bi | Cu | |
| mass％ | mass％ | mass％ | mass％ | |
| Among the Sb and dregs | 11.0 | 29.0 | 2.3 | 0.2 |
| Among the Bi and dregs | 8.4 | 0.2 | 25.0 | 4.3 |
With among the Sb and dregs with in and dregs: Na
2CO
3: the ratio of powdered carbon=10: 2: 1 mixes, and 900 ℃ of dissolvings down, has been recovered to Sb metal as shown in table 3 (Sb is 75.0mass%).
Among table 3 Sb and dregs dry process result
| Partition ratio | ||||||||||
| Weight | As | Sb | Bi | Cu | As | Sb | Bi | Cu | ||
| g | mass ％ | mass ％ | mass ％ | mass ％ | ％ | ％ | ％ | ％ | ||
| Drop into | In and dregs | 54.7 | 11.0 | 29.0 | 2.3 | 0.2 | 100 | 100 | 100 | 100 |
| Na 2CO 3 | 10.9 | |||||||||
| C | 5.5 | |||||||||
| Subtotal | 71.2 | 100 | 100 | 100 | 100 | |||||
| Output | Metal | 17.5 | 9.5 | 75.0 | 5.4 | 0.6 | 27.6 | 82.7 | 75.1 | 95.9 |
| Residue | 28.1 | 5.0 | 2.1 | 0.1 | - | 23.3 | 3.7 | 2.2 | 0.0 | |
| Subtotal | 45.6 | 50.9 | 86.4 | 77.3 | 95.9 | |||||
Then, for the Sb metal separation As from being recovered to, the described metal that is recovered to is being carried out alkaline purification (with dissolving again after NaOH mixes) under 750 ℃, having reclaimed As＜0.01mass%, Sb is the Sb metal of 79mass%.Sb loss during alkaline purification is 4%.
(embodiment 2)
(going on foot dry process with dregs 1 among the Sb)
In 1 step dry process, in order to reduce the As in the Sb metal that is recovered to, with solvent Na
2CO
3Use instead and be NaOH, with in and dregs: NaOH: the ratio of powdered carbon=4: 2: 1 mixes, and 950 ℃ of dissolvings down, has been recovered to the Sb metal of forming shown in the following note table 4 (Sb is 85mass%).Also have, because under 950 ℃ high temperature, handle, so when As removed as basic salt, Sb is voloxidation also, has only 48%, extremely low to the Sb of Sb metal mobility.Though As can be removed, because the rate of recovery of Sb is very poor as described above, so be used in industrial being difficult to.
Among table 4 Sb and dregs dry process result (NaOH processing)
| As | Sb | Bi | Cu | |
| mass％ | mass％ | mass％ | mass％ | |
| The Sb metal | 0.1 | 85.0 | 12.0 | 1.4 |
When reclaiming the Sb metal, if in finishing with 1 step and the reducing and smelting of dregs and the operation that As is removed as basic salt, then as mentioned above, Sb volatilization when As is removed, so rate of recovery variation preferably, reclaims metal shape Sb earlier in reducing atmosphere, then, under 700 ℃～800 ℃ low temperature, use 2 step dry process that NaOH handles in order to remove impurity such as As
(embodiment 3)
(going on foot dry process with dregs 2 among the Bi)
To among the Bi and dregs, with among the Sb and dregs in the same manner, implement solubility test after also can reclaiming metal with dry process.
During the ratio that will be in harmonious proportion is made as and dregs: Na
2CO
3: powdered carbon=15: 14: 2, under 900 ℃ of temperature, handle.
As shown in table 5 below, Bi was 70.0mass% during the recovery metal was formed.
Among table 5 Bi and dregs dry process result
| As | Sb | Bi | Cu | |
| mass％ | mass％ | mass％ | mass％ | |
| The Bi metal | 14.0 | 0.33 | 70.0 | 14.0 |
Then, in order to slough As, described recovery metal has been carried out alkaline purification (mix with NaOH, dissolve) at 750 ℃ from the Bi metal that is recovered to.
As shown in table 6 below, it is 80.0mass% that the metal after the alkaline purification is formed.
Among table 6 Bi and dregs dry process result (NaOH processing)
| As | Sb | Bi | Cu | |
| mass％ | mass％ | mass％ | mass％ | |
| The Bi metal | 0.44 | 0.01 | 80.0 | 16.0 |
Think in this treatment process, can remove impurity A s and Sb effectively, but owing to needed for 2 steps handled, so industrial not preferred, preferably, the mode of embodiment 4 as follows.Also having, through 2 steps, is 75～80% to the Bi of the Bi metal rate of dividing a word with a hyphen at the end of a line.
(embodiment 4)
(Bi 1 step dry process)
Different with embodiment 3, with among the dissolving Bi and the solvent during dregs use instead and be NaOH, with in and dregs: NaOH: the ratio of powdered carbon=4: 2: 1 mixes, and is as shown in table 7 below 950 ℃ of dissolvings down, reclaimed the Bi metal that consists of 81.0mass%.
If use this method, then can from and dregs reclaim the Bi metal of high density immediately, so preferably.Bi is different with Sb, even also do not have the decline of the rate of recovery that causes because of volatilization, the possibility so pyroprocessing becomes under 950 ℃ pyroprocessing.
Among table 7 Bi and dregs dry process result
| Partition ratio | ||||||||||
| Weight | As | Sb | Bi | Cu | As | Sb | Bi | Cu | ||
| g | mass ％ | mass ％ | mass ％ | mass ％ | ％ | ％ | ％ | ％ | ||
| Drop into | In and dregs | 20.0 | 8.4 | 0.2 | 25.0 | 4.3 | 100 | 100 | 100 | 100 |
| NaOH | 10.0 | |||||||||
| C | 5.0 | |||||||||
| Subtotal | 35.0 | 100 | 100 | 100 | 100 | |||||
| Output | Metal | 4.9 | 0.6 | 0.6 | 81.0 | 15.0 | 1.9 | 73.5 | 79.4 | 85.5 |
| Residue | 22.8 | 5.0 | ＜0.1 | 0.7 | 0.2 | 67.9 | ＜57.0 | 3.1 | 5.3 | |
| Subtotal | 27.7 | 69.7 | ＜130.5 | 82.5 | 90.8 | |||||
(embodiment 5)
Add hydrochloric acid in the elutriant after reclaiming Sb and Bi, total cl concn is adjusted into 6mol/L as shown in table 8ly by neutralizing treatment.
The adjustment result of Cl concentration in the elutriant after table 8 neutralizing treatment
The neutralization solution of chelating elutriant
1.32L
Then, use the elutriant behind the described adjustment cl concn, carry out the wash-out of resin.
Its result as shown in Figure 3.
Also have, in order to confirm to re-use the eluting rate of elutriant, use re-uses elutriant wash-out eluted resins once more, and use untapped 6N hydrochloric acid soln wash-out once more, elution amount in elution amount from re-use elutriant and the 6N hydrochloric acid soln is obtained the eluting rate that re-uses elutriant as shown in table 9.
The eluting rate of Sb is 80%, and the eluting rate of Bi is up to 97%.
Table 9 re-uses the eluting rate of elutriant
| Elution amount (g/L-R) | Elution efficiency | |||
| Sb | Bi | Sb | Bi | |
| Employing re-uses the wash-out of solution | 15.31 | 4.56 | 80％ | 97％ |
| After employing re-uses the elutriant wash-out, with 6N HCL wash-out | 3.90 | 0.14 | 20％ | 3％ |
| Amount to | 19.21 | 4.70 | 100％ | 100％ |
Can confirm: even add hydrochloric acid in the elutriant after reclaiming Sb and Bi, total cl concn is adjusted into elutriant behind the 6mol/L by neutralizing treatment, also can from resin fully wash-out go out Sb and Bi.
Claims (5)
1. the separation and recovery method of Sb and Bi, it is characterized in that, copper electrolyte is contacted with resin, absorption Sb and Bi on resin, and make the elutriant of salt acids contact wash-out Sb and Bi with this resin, the elutriant of resulting Sb of containing and Bi then neutralizes, the pH that makes this elutriant is in 1.5～3.0 scope, reclaim the Sb metal from the Sb that is recovered to and in the dregs by dry process at last, described dry process is in 850 ℃～950 ℃ temperature range, uses yellow soda ash and charcoal to carry out.
2. the separation and recovery method of Sb according to claim 1 and Bi is characterized in that,
After described dry process, further use sodium hydroxide under 700 ℃～800 ℃ temperature, to handle impurity.
3. the separation and recovery method of Sb according to claim 1 and Bi, it is characterized in that, to only having isolated among the Sb and this elutriant of dregs carries out neutralizing treatment again, the pH that makes this elutriant is 4～5, reclaim the Bi metal from the Bi that is recovered to and in the dregs by dry process at last, this last dry process is to use yellow soda ash or sodium hydroxide and charcoal, carries out under 850 ℃～950 ℃ temperature.
4. the separation and recovery method of Sb according to claim 3 and Bi is characterized in that,
Described last dry process is to use sodium hydroxide and charcoal to carry out.
5. the separation and recovery method of Sb according to claim 3 and Bi is characterized in that,
Add hydrochloric acid in the solution after described neutralizing treatment, after adjusting total cl concn and being 5～6mol/L, re-use as the elutriant of resin.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004277129A JP2006089809A (en) | 2004-09-24 | 2004-09-24 | METHOD FOR SEPARATING AND RECOVERING Sb AND Bi |
| JP2004277129 | 2004-09-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1752235A CN1752235A (en) | 2006-03-29 |
| CN1318621C true CN1318621C (en) | 2007-05-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100742962A Expired - Fee Related CN1318621C (en) | 2004-09-24 | 2005-06-02 | Methpd for separating and recovering Sb and Bi |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2006089809A (en) |
| CN (1) | CN1318621C (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5004077B2 (en) * | 2007-03-30 | 2012-08-22 | Ｊｘ日鉱日石金属株式会社 | How to collect Sb and Bi |
| JP5110421B2 (en) * | 2007-03-30 | 2012-12-26 | Ｊｘ日鉱日石金属株式会社 | Bi recovery method |
| JP5589854B2 (en) * | 2011-01-07 | 2014-09-17 | 住友金属鉱山株式会社 | How to recover bismuth |
| JP2013155432A (en) * | 2012-01-31 | 2013-08-15 | Mitsubishi Materials Corp | Recovery method of bismuth |
| CN102534257A (en) * | 2012-02-15 | 2012-07-04 | 四会市鸿明贵金属有限公司 | Novel bismuth smelting separation method |
| CN106731008B (en) * | 2015-11-20 | 2020-05-05 | 南京大学 | Composition and method for eluting antimony and bismuth from solid phase |
| CN105603218B (en) * | 2015-12-28 | 2018-08-24 | 赛恩斯环保股份有限公司 | Copper making process bismuth is enriched with the method with recycling |
| CN107841769B (en) * | 2017-11-17 | 2019-11-08 | 金川集团股份有限公司 | A method of antimony, bismuth are selectively removed from induction decopper(ing) liquid |
| CN108517538B (en) * | 2018-04-08 | 2019-11-29 | 长沙华时捷环保科技发展股份有限公司 | The method of waste solution of copper electrolysis synthetical recovery processing |
| CN109055742B (en) * | 2018-11-14 | 2019-02-22 | 长沙华时捷环保科技发展股份有限公司 | A method of recycling antimony bismuth |
| CN112322910A (en) * | 2020-11-06 | 2021-02-05 | 金川集团股份有限公司 | Method for removing antimony from new nickel electrodeposition liquid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087687A (en) * | 1992-12-02 | 1994-06-08 | 北京有色金属研究总院 | A kind of processing method of cleaning copper electrolyte |
| JP2938285B2 (en) * | 1992-09-16 | 1999-08-23 | 同和鉱業株式会社 | Chelate resin solution for copper electrolyte |
| CN1492079A (en) * | 1995-01-12 | 2004-04-28 | ס�ѽ�����ɽ��ʽ���� | Method for recovering stibium and bismuth from copper electrolyte |
-
2004
- 2004-09-24 JP JP2004277129A patent/JP2006089809A/en active Pending
-
2005
- 2005-06-02 CN CNB2005100742962A patent/CN1318621C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2938285B2 (en) * | 1992-09-16 | 1999-08-23 | 同和鉱業株式会社 | Chelate resin solution for copper electrolyte |
| CN1087687A (en) * | 1992-12-02 | 1994-06-08 | 北京有色金属研究总院 | A kind of processing method of cleaning copper electrolyte |
| CN1492079A (en) * | 1995-01-12 | 2004-04-28 | ס�ѽ�����ɽ��ʽ���� | Method for recovering stibium and bismuth from copper electrolyte |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006089809A (en) | 2006-04-06 |
| CN1752235A (en) | 2006-03-29 |
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