CN1209500C - Method for removing copper stannous and lead ions from used tin soldering liquid - Google Patents
Method for removing copper stannous and lead ions from used tin soldering liquid Download PDFInfo
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- CN1209500C CN1209500C CN 02127827 CN02127827A CN1209500C CN 1209500 C CN1209500 C CN 1209500C CN 02127827 CN02127827 CN 02127827 CN 02127827 A CN02127827 A CN 02127827A CN 1209500 C CN1209500 C CN 1209500C
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Abstract
The present invention relates to a resource utilization treatment method in preparation process of electronic industry, such as waste tin stripping liquid or waste tin and lead stripping liquid of a lead frame or a printed circuit board. In the method, copper ions, stannous ions and plumbous ions in waste liquid are removed by the steps that the copper ions are electrolyzed and reduced into metal copper at low temperature, the stannous ions and the plumbous ions form precipitates of oxide and hydroxide of lead and tin, etc. Thus, waste liquid after the removal of the cations is suitable for being prepared into fresh tin stripping solutions or fresh tin and lead stripping solutions, and the complete resource utilization of the waste liquid is realized.
Description
(1) technical field
The relevant a kind of electronic industry processing procedure that is used for of the present invention, the recycling processing method of the stripping tin of lead frame or printed circuit board (PCB) or tin-lead soldering waste liquid for example, specifically, relevant a kind of method of removing copper, Ya Xi and lead ion in stripping tin or the tin-lead soldering waste liquid.
(2) background technology
In the manufacturing processed of general printed circuit board (PCB), usually need be on the copper layer eleetrotinplate or tin lead with protective layer as alkali etching.After the logicalnot circuit etched removal of copper layer partly, the tin-lead soldering liquid with nitric acid series divests eleetrotinplate or tin lead layer usually, so that copper wire displays.The major ingredient of the tin-lead soldering liquid of nitric acid series is nitric acid and iron nitrate, in stripping tin or tin-lead soldering process, and when the free nitric acid content in the solution is lower than 4N or stanniferous amount and is higher than 100g/L, promptly must be with new liquid displacement, thereby form the tin-lead soldering waste liquid.Since contain in the tin-lead soldering waste liquid 2-15g/L cupric ion, 1-40g/L iron ion or ferrous ion, 10-120g/L stannous ion or tin ion (when waste liquid in storing or transporting in the process, stannous ion can be oxidized to tin ion and form stannic oxide or stannic hydroxide precipitation is separated out, therefore the stannous ion content in the waste liquid can be lower than 10g/L sometimes), 0-5g/L lead ion or lead ion and the free nitric acid of 2.0-6.0N, therefore, be necessary to deal carefully with the tin-lead soldering waste liquid to avoid causing environmental pollution.
Present treatment process is added in the sodium hydroxide and contained free nitric acid in the tin-lead soldering waste liquid for utilizing, adjusting the pH value makes most heavy metal cation form oxide compound or precipitation of hydroxide is separated out to 8-13, filter gained oxide compound or hydroxide solids, again with smelting process refining metallic tin, filtrate then through evaporative crystallization to make the SODIUMNITRATE crystal.Yet the shortcoming of this technology consumes a large amount of sodium hydroxide for palpus and crystallization gained SODIUMNITRATE crystal does not have commercial value.In denomination of invention is No. the 177911st, the Taiwan patent announcement of " method that reclaims metallic tin from stripping tin waste liquid ", disclosed the mode of adding neutralizing agent, precipitation agent and reductive agent of utilizing, make discharge water after the processing reach environmental protection standard and make stannous ion in the waste liquid or tin ion is reduced into metallic tin and reclaims, but be similar to the technology that the front was put forward, this treatment process still must consume a large amount of neutralizing agents and reductive agent, is the unfavorable treatment process of economy therefore.In addition disclosed a kind of ion exchange resin that utilizes to separate iron, chromium, tin plasma in the plating bath in No. the 258758th, the Taiwan patent announcement of " the reclaiming method and the device of tin plating electrolyte " in denomination of invention, method with zinc-plated auxiliary agent of reclaiming and metallic tin, yet, this method has the quite numerous and diverse shortcoming for the treatment of processes, and is not suitable for processing tin-lead soldering waste liquid.
(3) summary of the invention
Therefore, purpose of the present invention is for providing a kind of method of removing copper, Ya Xi and lead ion in stripping tin or the tin-lead soldering waste liquid.
The method of copper, Ya Xi and lead ion is characterized in removal stripping tin of the present invention or the tin-lead soldering waste liquid, comprising: (i) carry out the electrolytic reduction step in-5～40 ℃ temperature range, cupric ion in the waste liquid is reduced into metallic copper; And (ii) in 45～90 ℃ temperature range, carry out the electrolytic oxidation step, with stannous ion in the waste liquid and lead ion oxidation to form the oxide compound and the oxyhydroxide of plumbous and tin.
For further specifying purpose of the present invention, constructional feature and effect, the present invention is described in detail below with reference to accompanying drawing.
(4) description of drawings
Fig. 1 is that the method according to this invention handles the process block diagram of tin-lead soldering waste liquid, and wherein the dotted line square is represented the step that can depending on the circumstances or the needs of the situation increase.
(5) embodiment
Fig. 1 is a tin-lead soldering liquid waste disposal process block diagram, as shown in Figure 1, technology of the present invention mainly is to utilize electrolysis process to handle the tin-lead soldering waste liquid, this method comprises that (i) carries out the electrolytic reduction step at low temperatures, cupric ion is reduced into metallic copper, reach and (ii) at high temperature carry out the electrolytic oxidation step, stannous ion and lead ion are oxidized to tin and plumbous oxide compound and oxyhydroxide, and with the cupric ion in the waste liquid, stannous ion and lead ion are removed, make the waste liquid behind these positively charged ions of removal be suitable for being mixed with again fresh tin-lead soldering liquid, and realize the waste liquid complete resource.
In the method for the invention, the electrolytic reduction step is to carry out under-5～40 ℃ low temperature, and having the electrolytic reduction of inhibition hydrogen ion like this is that hydrogen and nitrate ion are oxynitride (NO
X) effect, and under the cryogenic situation that heals, the electrolytic reduction cupric ion is that the efficient of metallic copper is high more, but being principle under the situation of not freezing, the potential difference of anode and cathode is being preferable between 1～5V in the electrolytic reduction process; In addition, electrolytic oxidation reaction is to carry out under 45～90 ℃ high temperature, has fast the effect that stannous ion in the waste liquid and lead ion is oxidized to tetravalent tin ion and tetravalence lead ion like this, and form tin rapidly and separate out with precipitation with plumbous oxide compound and oxyhydroxide, utilize any solid-liquid separating method that throw out is separated again.If employed temperature is high more in the electrolytic oxidation step, then the effect of electrolytic oxidation is good more, but is principle not make the waste liquid oxynitride of acutely emerging, and in electrolytic acid cleaning oxydation process, the potential difference of anode and cathode is being good between 2～6V.In the method for the present invention, electrolytic reduction and electrolytic oxidation step there is no certain precedence requirement, also can alternately reuse.
Utilization the technology of the present invention can be removed cupric ion, stannous ion and lead ion most in the tin-lead soldering waste liquid easily, concentration that make to handle institute's copper ions, stannous ion and lead ion in the tin-lead soldering waste liquid of back is lower than 1g/L, 10g/L and 1g/L respectively, and is applicable to and is mixed with fresh tin-lead soldering liquid again.For making the advantage of more knowing the technology of the present invention, be described as follows to implement profit now:
Embodiment 1:
Get 600mL tin-lead soldering waste liquid, in carrying out electrolytic reduction under 15 ℃ and under 70 ℃, carry out electrolytic oxidation, the detailed process condition and handle before and after in the tin-lead soldering waste liquid content of institute's copper ions, stannous ion and lead ion be as shown in table 1.Find out by knowing in the table 1, handle back tin-lead soldering waste liquid and only contain 1.0g/L cupric ion, 7.3g/L stannous ion and 9.59ppm lead ion, therefore be applicable to be mixed with fresh tin-lead soldering liquid again.
Table 1
| Analytical results | |||||||
| Voltage | Electric current | Temperature | Cu 2+ | Fe 3+/Fe 2+ | Sn 2+ | Pb 2+ | |
| Stoste | - | - | - | 7.58g/L | 20.1g/L | 30.9g/L | 9.71ppm |
| Electrolytic reduction for the first time | 3.0V | 3.5A | 15℃ | 2.05g/L | 17g/L | 7.66g/L | 13ppm |
| Electrolytic oxidation | 4.0V | - | 70℃ | ||||
| Electrolytic reduction for the second time | 3.0V | 3.0A | 15℃ | 1.0g/L | 15g/L | 7.3g/L | 9.59ppm |
Embodiment 2:
Get 2.5L tin-lead soldering waste liquid, in carrying out electrolytic reduction under 15 ℃ and under 65 ℃, carry out electrolytic oxidation, the detailed process condition and handle before and after in the tin-lead soldering waste liquid content of institute's copper ions, stannous ion and lead ion be as shown in table 2.Find out by knowing in the table 2, handle back tin-lead soldering waste liquid and only contain 0.34g/L cupric ion, 5.77g/L stannous ion and 2.81ppm lead ion, therefore also be applicable to be mixed with fresh tin-lead soldering liquid again.
Table 2
| Analytical results | |||||||
| Voltage | Electric current | Temperature | Cu 2+ | Fe 3+/Fe 2+ | Sn 2+ | Pb 2+ | |
| Stoste | - | - | - | 5.77g/L | 19.32g/L | 34.6g/L | 5.58ppm |
| Electrolytic reduction for the first time | 3.0V | 5.0A | 15℃ | 2.77g/L | 13.7g/L | 1.68g/L | 2.41ppm |
| Electrolytic oxidation | 4.0V | - | 65℃ | ||||
| Electrolytic reduction for the second time | 3.0V | 10.0A | 15℃ | 0.34g/L | 14.0g/L | 5.77g/L | 2.81ppm |
Certainly, those of ordinary skill in the art will be appreciated that, above embodiment is used for illustrating the present invention, and be not to be used as limitation of the invention, as long as in connotation scope of the present invention, all will drop in the scope of claims of the present invention variation, the modification of the above embodiment.
Claims (5)
1, a kind of method of removing copper, Ya Xi and lead ion in stripping tin or the tin-lead soldering waste liquid is characterized in that, comprising: (i) carry out the electrolytic reduction step in-5～40 ℃ temperature range, cupric ion in the waste liquid is reduced into metallic copper; And (ii) in 45～90 ℃ temperature range, carry out the electrolytic oxidation step, with stannous ion in the waste liquid and lead ion oxidation to form the oxide compound and the oxyhydroxide of plumbous and tin.
2, the method for claim 1 is characterized in that, in the electrolytic reduction step, the anode and cathode potential difference remains on 1～5V.
3, method as claimed in claim 1 or 2 is characterized in that, in the electrolytic oxidation step, the anode and cathode potential difference remains on 2～6V.
4, method as claimed in claim 1 or 2 is characterized in that, further comprises metallic copper and the oxide compound of plumbous and tin and the step that oxyhydroxide carries out solid-liquid separation that will be generated.
5, the method for claim 1 is characterized in that, electrolytic reduction and electrolytic oxidation step do not have precedence.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02127827 CN1209500C (en) | 2002-08-01 | 2002-08-01 | Method for removing copper stannous and lead ions from used tin soldering liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02127827 CN1209500C (en) | 2002-08-01 | 2002-08-01 | Method for removing copper stannous and lead ions from used tin soldering liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1472362A CN1472362A (en) | 2004-02-04 |
| CN1209500C true CN1209500C (en) | 2005-07-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02127827 Expired - Lifetime CN1209500C (en) | 2002-08-01 | 2002-08-01 | Method for removing copper stannous and lead ions from used tin soldering liquid |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI120052B (en) * | 2007-04-13 | 2009-06-15 | Yara Suomi Oy | A method for treating and reusing an etching solution |
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- 2002-08-01 CN CN 02127827 patent/CN1209500C/en not_active Expired - Lifetime
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| CN1472362A (en) | 2004-02-04 |
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