CN109457273A - A kind of environmental type tin electrorefining electrolyte - Google Patents
A kind of environmental type tin electrorefining electrolyte Download PDFInfo
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- CN109457273A CN109457273A CN201811620105.1A CN201811620105A CN109457273A CN 109457273 A CN109457273 A CN 109457273A CN 201811620105 A CN201811620105 A CN 201811620105A CN 109457273 A CN109457273 A CN 109457273A
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- electrolyte
- tin
- glucosides
- sulfonic acid
- benzene sulfonate
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/14—Electrolytic production, recovery or refining of metals by electrolysis of solutions of tin
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention discloses a kind of environmental type tin electrorefining electrolyte, the electrolyte contains 20 ~ 120g/L H2SO4、4~40g/L Sn2+, 5 ~ 50mg/L glucosides, 1 ~ 20g/L benzene sulfonate, 0.1 ~ 2 g/L betanaphthol, 0.1 ~ 5g/L latex.Toluene phenol sulfonic acid is added in traditional tin electrorefining electrolyte generally to inhibit Sn in electrolyte2+Oxidation, improve and electrolyte stability and improve cathode tin pattern.However cresol sulfonic acid smell is big, poisonous and harmful, deterioration potroom operating environment.Based on this, the present invention proposes a kind of environmental type tin electrorefining electrolyte.The electrolyte has the advantages that safe and non-toxic, efficient, the improvement smooth consistency of cathode tin, can be applicable in tin electrorefining industry.
Description
Technical field
The invention belongs to non-ferrous metallurgy fields, are related to a kind of environmental type tin electrorefining electrolyte.
Background technique
By consulting domestic and international related data discovery, the main technique that nowadays enterprise carries out tin smelting is hydrosulphate tin
Electrolysis system.Pyro-refining is compared, which has the advantages that work flow is short, cathode tin is with high purity, is suitable for handling miscellaneous
The higher thick tin of matter content.The phenol sulfonic acids such as additive cresol sulfonic acid employed in the system have electrolyte stability it is good,
The advantages that refining cathode tin crystals.Pertinent literature report and previous experiments are research shows that cresol sulfonic acid improves tin cathode run
The mechanism of action there are mainly two types of, first is that phenolic hydroxyl group in cresol sulfonic acid molecule has reproducibility, inhibit Sn in electrolyte2+Oxidation
At Sn4+, block α-SnO2·H2The generation of O and β-stannic acid precipitating, avoids plating solution from performance that is muddy, influencing electrolyte occur, leads
The generation for phenomena such as causing rougher cathode sedimentary, loose and reduction current efficiency；Second is that the sulfonic group in cresol sulfonic acid molecule
It is adsorbed on cathode surface, blocks Sn2+Fast deposition, make the smooth densification of cathode tin.
But the additives such as cresol sulfonic acid pollute environment, and have certain irritation and toxic to human and environment, it is unfavorable
In electrolysis operation.So needing to find a kind of green non-poisonous and efficient additive, to replace the additives such as cresol sulfonic acid.
Summary of the invention
, pollution workshop labourer heavy, poisonous and harmful for the cresol sulfonic acid smell that is added in traditional tin electrorefining electrolyte
The problem of environment, the present invention propose a kind of environmentally friendly, efficient tin electrorefining compound additive.
Environmental type tin electrorefining electrolyte of the present invention contains 20 ~ 120g/L H2SO4、4~40g/L Sn2 +(SnSO4Form be added), 5 ~ 50mg/L glucosides, 1 ~ 20g/L benzene sulfonate, 0.1 ~ 2g/L betanaphthol, 0.1 ~ 5g/L latex.
Further, the glucosides and benzene sulfonate mass ratio should control within the scope of 1:4000 ~ 1:20.
Further, the glucosides is selected from one or both of Resveratrol, quercitin.Select Resveratrol, quercitrin
The reason of glycosides is that the two has stronger antioxidant activity.
Further, the glucosides is Resveratrol.It is preferred that the reason of Resveratrol is the antioxidant activity of Resveratrol
It is more preferable with water solubility.
Further, the benzene sulfonate is selected from one or both of benzene sulfonic acid sodium salt, benzene sulfonic acid calcium.Select benzene sulfonic acid
The reason of sodium, benzene sulfonic acid calcium is that the two has stronger complexing power and Surface flat.
Further, the benzene sulfonate is benzene sulfonic acid sodium salt.It is preferred that the reason of benzene sulfonic acid sodium salt is the complexing energy of benzene sulfonic acid sodium salt
Power and Surface flat are stronger, and its price is more cheap.
Using the method for above-mentioned electrolyte electrolytic tin, following steps are specifically included.
(1) with SnSO4For the main salt in electrolyte, glucosides is antioxidant, and benzene sulfonate is leveling agent, the electrolyte
In contain 20 ~ 120g/L H2SO4、4~40 g/LSn2+, 5 ~ 50mg/L glucosides, 1 ~ 20g/L benzene sulfonate, 0.1 ~ 2g/L β-naphthalene
Phenol, 0.1 ~ 5g/L latex.
(2) in 20 ~ 40 DEG C of constant temperature, 40 ~ 120A/m of current density2Under the conditions of, electrolysis take cathode to be rinsed, do afterwards for 24 hours
Each component content in dry, weighing, calculating current efficiency, observation cathode tin pattern and detection solution.In the present invention, glucosides provides
Hydroxyl can be used as reducing agent inhibit Sn2+Oxidation；Sulfonic group in benzene sulfonate can play retardance cathode tin deposition
Effect.Add glucosides and the obtained cathode tin densification flatness of benzene sulfonate compound additive and addition cresol sulfonic acid electrolyte
System it is suitable.
The present invention proposes that the compound additive formed using glucosides and benzene sulfonate substitutes cresol sulfonic acid, obtains green ring
Guarantor's type tin electrorefining electrolyte, can improve operating environment, reduce cost, while maintain the smooth densification of cathode tin, have important
Commercial introduction value.
Specific embodiment
The contents of the present invention are described in detail with the following Examples.
Comparative example 1
(1) with SnSO4For the main salt in electrolyte, cresol sulfonic acid is antioxidant, 60g/L H in the electrolyte2SO4、15g/
L Sn2+(with SnSO4Supplying), 10g/L cresol sulfonic acid, 0.2g/L betanaphthol, 1.0g/L latex.
(2) at 35 DEG C of constant temperature, anode and cathode pole span 5cm, current density 100A/m2Under the conditions of, electrolysis take cathode to carry out afterwards for 24 hours
Rinsing, drying, weighing, and calculating current efficiency.By operating above, it is obtaining the result is that: current efficiency 98.84%, and yin
The smooth densification of pole tin, but there is obvious irritation smell in workshop.Sn in the electrolyte of electrolysis front and back2+Concentration be respectively 10.03g/L and
9.52g/L, variation fluctuation are 0.51g/L.The concentration of total Sn is respectively 14.68g/L and 14.75g/L, variation fluctuation in electrolyte
About 0.07g/L.H in electrolyte+Concentration divides table to be 0.98g/L and 0.96g/L, and variation fluctuation is about 0.02g/L.
Comparative example 2
(1) with SnSO4For the main salt in electrolyte, Resveratrol is antioxidant, and benzene sulfonic acid sodium salt is leveling agent, the electrolyte
Middle 60g/L H2SO4、15g/L Sn2+(with SnSO4Supplying), Resveratrol 30mg/L, benzene sulfonic acid sodium salt 0.5g/L, 0.2g/L β-naphthalene
Phenol, 1.0g/L latex.
(2) at 35 DEG C of constant temperature, anode and cathode pole span 5cm, current density 100A/m2Under the conditions of, electrolysis take cathode to carry out afterwards for 24 hours
Rinsing, drying, weighing, and calculating current efficiency.By operating above, it is obtaining the result is that: current efficiency 98.42% is lower than
Comparison example 1, the smooth low density of cathode tin.Sn in the electrolyte of electrolysis front and back2+Concentration be respectively 9.75g/L and 9.18g/L,
Variation fluctuation is 0.57g/L.The concentration of total Sn is respectively 14.39g/L and 14.76g/L in electrolyte, and variation fluctuation is 0.37g/
L.H in electrolyte+Concentration divides table to be 0.74g/L and 0.73g/L, and variation fluctuation is 0.01g/L.
Embodiment 1
(1) with SnSO4For the main salt in electrolyte, Resveratrol is antioxidant, and benzene sulfonic acid sodium salt is leveling agent, the electrolyte
Middle 60g/L H2SO4、15g/L Sn2+(with SnSO4Supplying), Resveratrol 30mg/L, benzene sulfonic acid sodium salt 8g/L, 0.2g/L β-naphthalene
Phenol, 1.0g/L latex.
(2) at 35 DEG C of constant temperature, anode and cathode pole span 5cm, current density 100A/m2Under the conditions of, electrolysis take cathode to carry out afterwards for 24 hours
Rinsing, drying, weighing, and calculating current efficiency.By operating above, it is obtaining the result is that: current efficiency 98.65%, it is slightly lower
In comparison example 1, slightly above comparison example 2, but the smooth consistency of cathode tin is better than comparative example 1 and comparison example 2, and vehicle
It is interior without obvious smell.Sn in the electrolyte of electrolysis front and back2+Concentration be respectively 9.87g/L and 9.42g/L, variation fluctuation is about
0.45g/L is slightly less than comparative example 1 and comparative example 2.In electrolyte the concentration of total Sn be respectively 14.39g/L and
14.46g/L, variation fluctuation are about 0.07g/L, quite with comparative example 1, but are less than comparative example 2.H in electrolyte+It is dense
Degree divides table to be 0.74g/L and 0.73g/L, and variation fluctuation is 0.01g/L, suitable with comparative example 1 and comparative example 2.
Embodiment 2
(1) with SnSO4For the main salt in electrolyte, Resveratrol is antioxidant, and benzene sulfonic acid sodium salt is leveling agent, the electrolyte
Middle 60g/L H2SO4、15g/L Sn2+(with SnSO4Supplying), Resveratrol 20mg/L, benzene sulfonic acid sodium salt 8g/L, 0.2g/L β-naphthalene
Phenol, 1.0g/L latex.
(2) at 35 DEG C of constant temperature, anode and cathode pole span 5cm, current density 100A/m2Under the conditions of, electrolysis take cathode to carry out afterwards for 24 hours
Rinsing, drying, weighing, and calculating current efficiency.By operating above, it is obtaining the result is that: current efficiency 98.21% is lower than
Comparison example 1, the smooth consistency of cathode tin are slightly worse than comparative example 1, but without obvious smell in workshop.Electrolysis front and back electrolyte
Middle Sn2+Concentration be respectively 9.65g/L and 8.78g/L, variation fluctuation is 0.87g/L, slightly above comparative example 1.Electrolyte
In the concentration of total Sn be respectively 14.42g/L and 14.68g/L, variation fluctuation is 0.26g/L, is better than comparative example 1.Electrolyte
Middle H+Concentration divides table to be 0.74g/L and 0.73g/L, and variation fluctuation is 0.01g/L, suitable with comparative example 1.
Claims (7)
1. a kind of environmental type tin electrorefining electrolyte, which is characterized in that the electrolyte contains 20 ~ 120 g/L
H2SO4、4~40 g/L Sn2+, 5 ~ 50mg/L glucosides, 1 ~ 20 g/L benzene sulfonate, 0.1 ~ 2 g/L betanaphthol, 0.1 ~ 5g/L cream
Glue.
2. electrolyte according to claim 1, which is characterized in that the glucosides and benzene sulfonate mass ratio should be controlled 1:
4000 ~ 1:20.
3. electrolyte according to claim 1, which is characterized in that the glucosides in Resveratrol, quercitin one
Kind or two kinds.
4. electrolyte according to claim 1, which is characterized in that the glucosides is Resveratrol.
5. electrolyte according to claim 1, which is characterized in that the benzene sulfonate is selected from benzene sulfonic acid sodium salt, benzene sulfonic acid calcium
One or both of.
6. electrolyte according to claim 1, which is characterized in that the benzene sulfonate is benzene sulfonic acid sodium salt.
7. a kind of method using electrolyte electrolytic tin of any of claims 1-6, which is characterized in that including following
Step:
(1) with SnSO4For the main salt in electrolyte, glucosides is antioxidant, and benzene sulfonate is leveling agent, is contained in the electrolyte
There is 20 ~ 120g/L H2SO4、4~40 g/LSn2+, 5 ~ 50mg/L glucosides, 1 ~ 20g/L benzene sulfonate, 0.1 ~ 2g/L betanaphthol,
0.1 ~ 5g/L latex；
(2) in 20 ~ 40 DEG C of constant temperature, 40 ~ 120A/m of current density2Under the conditions of, electrolysis take cathode to be rinsed, dry, claim afterwards for 24 hours
Each component content in weight, calculating current efficiency, observation cathode tin pattern and detection solution.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811620105.1A CN109457273A (en) | 2018-12-28 | 2018-12-28 | A kind of environmental type tin electrorefining electrolyte |
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| CN201811620105.1A CN109457273A (en) | 2018-12-28 | 2018-12-28 | A kind of environmental type tin electrorefining electrolyte |
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| CN109457273A true CN109457273A (en) | 2019-03-12 |
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| CN102418123A (en) * | 2011-11-25 | 2012-04-18 | 上海应用技术学院 | High-speed electroplating luminous tin-plating electroplating liquid as well as preparation method and application thereof |
| CN103898570A (en) * | 2012-12-27 | 2014-07-02 | 罗门哈斯电子材料有限公司 | Tin or tin alloy plating liquid |
| CN104091796A (en) * | 2014-07-23 | 2014-10-08 | 苏州日月新半导体有限公司 | Electronic chip shielding layer structure |
| CN106676594A (en) * | 2016-06-10 | 2017-05-17 | 太原工业学院 | Low-cost cyanide-free copper-zinc-tin alloy electroplating solution and copper-zinc-tin alloy electroplating technology thereof |
| CN107675209A (en) * | 2017-10-18 | 2018-02-09 | 江西理工大学 | A kind of green tin electrorefining electrolyte |
| CN108342763A (en) * | 2018-03-05 | 2018-07-31 | 佛山市海化表面处理科技有限公司 | A kind of list pink salt electrolytic coloring additive and its application |
-
2018
- 2018-12-28 CN CN201811620105.1A patent/CN109457273A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102418123A (en) * | 2011-11-25 | 2012-04-18 | 上海应用技术学院 | High-speed electroplating luminous tin-plating electroplating liquid as well as preparation method and application thereof |
| CN103898570A (en) * | 2012-12-27 | 2014-07-02 | 罗门哈斯电子材料有限公司 | Tin or tin alloy plating liquid |
| CN104091796A (en) * | 2014-07-23 | 2014-10-08 | 苏州日月新半导体有限公司 | Electronic chip shielding layer structure |
| CN106676594A (en) * | 2016-06-10 | 2017-05-17 | 太原工业学院 | Low-cost cyanide-free copper-zinc-tin alloy electroplating solution and copper-zinc-tin alloy electroplating technology thereof |
| CN107675209A (en) * | 2017-10-18 | 2018-02-09 | 江西理工大学 | A kind of green tin electrorefining electrolyte |
| CN108342763A (en) * | 2018-03-05 | 2018-07-31 | 佛山市海化表面处理科技有限公司 | A kind of list pink salt electrolytic coloring additive and its application |
Non-Patent Citations (1)
| Title |
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| 王丽丽 等: "Sn和Sn-Pb合金电镀", 《电镀与精饰》 * |
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Application publication date: 20190312 |