CN107686893A - Tin stripping liquid, remove the method containing tin layers on base material and the method for reclaiming simple substance tin - Google Patents
Tin stripping liquid, remove the method containing tin layers on base material and the method for reclaiming simple substance tin Download PDFInfo
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- CN107686893A CN107686893A CN201710751695.0A CN201710751695A CN107686893A CN 107686893 A CN107686893 A CN 107686893A CN 201710751695 A CN201710751695 A CN 201710751695A CN 107686893 A CN107686893 A CN 107686893A
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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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/04—Obtaining tin by wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/30—Acidic compositions for etching other metallic material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a kind of method for reclaiming simple substance tin, this method includes：Removed using tin stripping liquid and contain tin layers on base material to obtain tin removal waste liquor, wherein, tin stripping liquid includes 5g/L 100g/L nitric acid, 70g/L 640g/L complexing agent, 10g/L 150g/L stabilizer and 0.5g/L 25g/L antioxidant, wherein, the stabilizer includes at least one of carboxylic acid compound, carbamide compounds and amino acid；Extractant is mixed with tin removal waste liquor and causes the nitric acid in tin removal waste liquor to enter extractant, and performs separation, with the tin removal waste liquor after being extracted and the extract comprising extractant and nitric acid；Diaphragm electrolysis is performed to the tin removal waste liquor after extraction, to obtain simple substance tin.Spent solution regeneration is had the advantages that according to the method for the recovery simple substance tin of the present invention, recycled, Zero discharge.
Description
Technical field
It is more particularly to a kind of to be returned using diaphragm electrolysis from tin removal waste liquor the present invention relates to a kind of method for reclaiming simple substance tin
The method for receiving simple substance tin.
Background technology
Printed circuit board (PCB) (Printed Circuit Board, PCB) is one of important component of electronics industry, is electronics
The supporter of component.Generally, the technique for manufacturing printed circuit board (PCB) contains tin layers including the use of on tin stripping liquid removal circuit board, from
And produce substantial amounts of tin removal waste liquor.At present, tin stripping liquid can be divided into fluoride type, strong base and nitric acid type etc. according to its main component
Three types.Fluoride type tin stripping liquid is due to its environmental index (fluoride high volatility, pollution are extremely heavy) and technical-economic index
It is poor, it has been eliminated substantially.Strong base tin stripping liquid is due to its technology, economic indicator is general, the cyanide toxicity that contains is big,
Harm in production process to operating personnel is very big, therefore less use strong base tin stripping liquid.Nitric acid type tin stripping liquid is manufacture
PCB leading formulation, Theil indices are higher in caused tin removal waste liquor, if it is arbitrarily discharged, have not only polluted environment but also caused resource
Waste.
The processing method of traditional tin removal waste liquor mainly includes plus alkali carries out neutralization precipitation, then filters, filter cake tin mud is sent
Enter smeltery's pyrometallurgical smelting, filtrate is discharged after then adding sulfide recovery copper.This not only produces substantial amounts of waste residue, and the utilization of resources is not
Fully, and processing cost is higher.In recent years, occur distillation recovery method, acidic precipitation agent facture etc., but these method meetings again
Substantial amounts of other waste liquids are produced, cause secondary pollution, and the control of complex process, condition is strict, processing cost is high.
The content of the invention
It is an object of the present invention to provide a kind of method for reclaiming simple substance tin.
It is an object of the invention to provide a kind of recovery simple substance tin that can solve the problem that at least one problem in problem above
Method.
Comprised the following steps according to the method for the recovery simple substance tin of the present invention：(a) containing on base material is removed using tin stripping liquid
Tin layers to obtain tin removal waste liquor, wherein, tin stripping liquid include 5g/L-100g/L nitric acid, 70g/L-640g/L complexing agent, 10g/
L-150g/L stabilizer and 0.5g/L-25g/L antioxidant, wherein, the stabilizer includes carboxylic acid compound, ureas
At least one of compound and amino acid；(b) mixing extractant with tin removal waste liquor causes the nitric acid in tin removal waste liquor to enter
Extractant, and perform separation, with the tin removal waste liquor after being extracted and the extract comprising extractant and nitric acid；And (c)
Diaphragm electrolysis is performed to the tin removal waste liquor after extraction, to obtain simple substance tin.
According to an aspect of the present invention, the stabilizer is included in carboxylic acid compound, carbamide compounds and amino acid
At least two.Cumulative volume based on tin stripping liquid, the content of the carboxylic acid compound can be 0g/L-40g/L, the ureas chemical combination
The content of thing can be 0g/L-30g/L, and the content of the amino acid can be 0g/L-100g/L.
According to an aspect of the present invention, the carboxylic acid compound is included in tartaric acid, citric acid and salicylic acid at least
One kind, the carbamide compounds include at least one of urea, glucosyl group urea, thiocarbamide, thiourea derivative and acylureas, institute
Stating amino acid includes at least one of glycine, alanine and lysine.
According to an aspect of the present invention, the carbamide compounds are thiocarbamide or thiourea derivative.Totality based on tin stripping liquid
Product, the content of the carbamide compounds can be 5g/L-20g/L.
According to an aspect of the present invention, the complexing agent includes at least one of pyrovinic acid and sulfamic acid.
According to an aspect of the present invention, the complexing agent includes pyrovinic acid and sulfamic acid.Totality based on tin stripping liquid
Product, the content of pyrovinic acid can be 50g/L-550g/L, and the content of sulfamic acid can be 20g/L-90g/L.
According to an aspect of the present invention, the antioxidant includes phenolic compound.Between the phenolic compound may include
At least one of benzenediol, catechol, hydroquinones and phloroglucin.
According to an aspect of the present invention, extractant includes 20wt%-40wt% tributyl phosphate and 60wt%-80wt%
Sulfonated kerosene.
According to an aspect of the present invention, the step of extractant being mixed with tin removal waste liquor is included according to 1-5:1 weight ratio
Extractant is mixed with tin removal waste liquor.
According to an aspect of the present invention, the step of performing diaphragm electrolysis to the tin removal waste liquor after extraction includes：After extracting
Tin removal waste liquor be added to the cathode chamber of the electrolytic cell separated by barrier film, the pyrovinic acid aqueous solution is added to the anode of electrolytic cell
Room, diaphragm electrolysis is carried out to the tin removal waste liquor after extraction, so as to the electro-deposition simple substance tin on negative electrode.
According to an aspect of the present invention, methods described also includes：Back extraction is carried out to extract using water and causes extract
In nitric acid enter water in, so as to obtain aqueous solution of nitric acid and back extraction after extractant；After back extraction being used in step (b)
Extractant；Aqueous solution of nitric acid is concentrated, and by the aqueous solution of nitric acid of concentration with the middle tin stripping liquid used in step (a).
Spent solution regeneration is had the advantages that according to the method for the recovery simple substance tin of the present invention, recycled, Zero discharge.This
Outside, the purity of the simple substance tin of the method according to the invention recovery is up to more than 99.5%.
Brief description of the drawings
By the description to exemplary embodiment below in conjunction with the accompanying drawings, these and/or other side will be clear and more
It is readily appreciated that, in the accompanying drawings：
Fig. 1 is the flow chart according to the method for the recovery simple substance tin of the exemplary embodiment of the present invention；
Fig. 2 is the schematic diagram of the electrolytic cell used in the method according to the recovery simple substance tin of the exemplary embodiment of the present invention.
Embodiment
Below in conjunction with accompanying drawing and exemplary embodiment, principle of the invention is described in further detail, so that the skill of the present invention
Art solution becomes apparent from.
Fig. 1 is the flow chart according to the method for the recovery simple substance tin of the exemplary embodiment of the present invention.Fig. 2 is according to this hair
The schematic diagram of the electrolytic cell used in the method for the recovery simple substance tin of bright exemplary embodiment.
Reference picture 1, removed according to the method for the recovery simple substance tin of the present invention using tin stripping liquid and contain tin layers on base material
(S100) (S200), is extracted to tin removal waste liquor and diaphragm electrolysis (S300) is carried out to the tin removal waste liquor after extraction.
Using tin stripping liquid remove base material on contain tin layers (S100) in, can utilize it is described below according to the present invention
Tin stripping liquid removes contains tin layers on base material, so as to obtain tin removal waste liquor.Here, the base material can refer in order to manufacture PCB and
The base material containing tin layers is electroplated in substrate.Can be tin layers, leypewter layer or gun-metal layer containing tin layers.However, the present invention is not
It is limited to this.
Include 5g/L-100g/L nitric acid, 70g/L-640g/ according to cumulative volume of the tin stripping liquid based on tin stripping liquid of the present invention
L complexing agent, 10g/L-150g/L stabilizer, 0.5g/L-25g/L antioxidant.In a preferred embodiment, according to this
Cumulative volume of the tin stripping liquid of invention based on tin stripping liquid includes 50g/L-100g/L nitric acid, 100g/L-600g/L complexing agent, 50g/
L-100g/L stabilizer, 5g/L-25g/L antioxidant.In more preferred embodiment, according to the tin stripping liquid of the present invention
Cumulative volume based on tin stripping liquid include 55g/L-95g/L nitric acid, 150g/L-500g/L complexing agent, 60g/L-90g/L it is steady
Determine agent, 7g/L-20g/L antioxidant.In the present invention, unit " g/L " refers to the quality of contained component in 1L tin stripping liquids.
Include as the above-mentioned nitric acid of active ingredient and solute, complexing agent, stabilizer and resist according to the tin stripping liquid of the present invention
Oxidant and the water as solvent.That is, it is tin stripper solution according to the tin stripping liquid of the present invention.
Nitric acid primarily serves oxidation dissolution containing tin layers (for example, tin layers, leypewter layer or gun-metal in tin stripping liquid
Layer) effect, its mechanism of action is：4Sn+10HNO3→4Sn(NO3)2+NH4NO3+3H2O。
In the present invention, " nitric acid " refers to the HNO as solute3.However, the present invention can be existed using such as mass fraction
60wt%-70wt% salpeter solution prepares tin stripping liquid, for example, the amount of the nitric acid needed for tin stripping liquid can be converted into matter
Amount of the fraction in 60wt%-70wt% salpeter solution is measured, determines the mass fraction needed for tin stripping liquid in 60wt%- with this
The amount of 70wt% salpeter solution.In an exemplary embodiment of the present invention, the content of nitric acid can 5g/L-100g/L,
In the range of 10g/L-95g/L, 20g/L-85g/L, 30g/L-75g/L, 40g/L-65g/L or 50g/L-55g/L, or above-mentioned give
In any range of the numerical definiteness gone out, for example, in 5g/L-55g/L, 10g/L-65g/L.
Complexing agent plays a part of maintaining the acidity of tin stripping liquid in tin stripping liquid, strengthens and move back tin, and and divalent tin ion
Complex compound is formed to stablize tin stripping liquid.During tin is moved back, tin is mainly with Sn2+Form exist in solution.Due to Sn2+
Sn is easily oxidized to by oxygen in the nitric acid and air in tin stripping liquid etc.4+, and Sn4+Facile hydrolysis produces β-stannic acid precipitation, so as to
Influence the removal containing tin layers (for example, tin layers and signal bronze layer).Therefore, in the present invention, can have by adding complexing agent
Effect ground suppresses the generation of precipitation.
At least one of pyrovinic acid and sulfamic acid can be included according to the complexing agent of the present invention, i.e. can only wrap
Pyrovinic acid is included, only including sulfamic acid, or including pyrovinic acid and sulfamic acid.Content of the complexing agent in tin stripping liquid exists
70g/L-640g/L, such as can be in 70g/L-600g/L, 100g/L-550g/L, 150g/L-500g/L, 200g/L-450g/
L, in the range of 250g/L-400g/L or 300g/L-350g/L, or in any range of the above-mentioned numerical definiteness provided, for example,
In 70g/L-500g/L, 100g/L-400g/L.
In an exemplary embodiment of the present invention, complexing agent includes pyrovinic acid and sulfamic acid, based on the total of tin stripping liquid
Volume, the content of pyrovinic acid can be 50g/L-550g/L, for example, can 100g/L-500g/L, 150g/L-450g/L,
In the range of 200g/L-400g/L or 300g/L-350g/L, or in any range of the above-mentioned numerical definiteness provided, for example,
In 55g/L-500g/L, 100g/L-400g/L；The content of sulfamic acid can be 20g/L-90g/L, for example, can be in 30g/
In the range of L-80g/L, 40g/L-70g/L or 50g/L-60g/L, or in any range of the above-mentioned numerical definiteness provided, example
Such as, in 25g/L-60g/L, 35g/L-50g/L.
In the present invention, sulfamic acid can also suppress point of nitric acid in addition to forming complex compound with divalent tin ion
Solution, so as to suppress to produce NO2, reduce the pollution to environment.
The effect of stabilizer be to promote the dissolving of tin, prevent during molten tin divalent tin ion be oxidized to tetravalent tin from
Son and/or the hydrolysis for preventing tetravalence tin ion.Therefore, stabilizer is particularly important for tin stripping liquid.
In an exemplary embodiment of the present invention, the content of stabilizer can 10g/L-150g/L, 20g/L-130g/L,
In the range of 30g/L-110g/L, 40g/L-90g/L, 50g/L-80g/L or 55g/L-75g/L, or the above-mentioned numerical value limit provided
In fixed any range, for example, in 10g/L-110g/L, 40g/L-150g/L.
Stabilizer in the tin stripping liquid of the present invention can include in carboxylic acid compound, carbamide compounds and amino acid
At least one.I.e., it is possible to only include carboxylic acid compound, only including carbamide compounds, only including amino acid, including carboxylic acids
Compound and carbamide compounds, including carboxylic acid compound and amino acid, including carbamide compounds and amino acid, or including carboxylic
Acid compounds, carbamide compounds and amino acid.Preferably, stabilizer can include carboxylic acid compound, carbamide compounds and
At least two in amino acid, i.e. including carboxylic acid compound and carbamide compounds, including carboxylic acid compound and amino acid,
Including carbamide compounds and amino acid, or including carboxylic acid compound, carbamide compounds and amino acid.It is it is highly preferred that stable
Agent can include carboxylic acid compound, carbamide compounds and amino acid.
Carboxylic acid compound can be by controlling the free acid content in tin stripping liquid, to suppress Sn4+Hydrolysis.In the present invention
Exemplary embodiment in, carboxylic acid compound can include at least one of tartaric acid, citric acid and salicylic acid, however this
Invention not limited to this.Cumulative volume based on tin stripping liquid, the content of carboxylic acid compound can be 0g/L-40g/L, for example, can be with
In the range of 2g/L-40g/L, 5g/L-35g/L, 10g/L-30g/L or 15g/L-25g/L, or the above-mentioned numerical definiteness provided
Any range in, for example, in 4g/L-25g/L, 8g/L-30g/L.
Carbamide compounds can suppress Sn2+It is oxidized to Sn4+.In an exemplary embodiment of the present invention, carbamide compounds can
With including at least one of urea, glucosyl group urea, thiocarbamide, thiourea derivative and acylureas, for example, can only include sulphur
Urea, only including thiourea derivative, including at least one of urea, glucosyl group urea and acylureas and thiocarbamide, or including urea,
At least one of glucosyl group urea and acylureas and thiourea derivative, however, the invention is not restricted to this.Totality based on tin stripping liquid
Product, the content of carbamide compounds can be 0g/L-30g/L, for example, can be in 5g/L-30g/L, 10g/L-25g/L or 15g/L-
In the range of 20g/L, or in any range of the above-mentioned numerical definiteness provided, for example, in 3g/L-20g/L, 6g/L-25g/L.
In the case where carbamide compounds include thiocarbamide or thiourea derivative, the thiocarbamide or thiourea derivative are in tin stripping liquid
In can function as current potential regulator.Specifically, thiocarbamide or thiourea derivative can be removed effectively containing tin layers (particularly copper
Tin alloy layers), so as to be effectively reduced the electrode potential containing tin layers.Cumulative volume based on tin stripping liquid, thiocarbamide or thiourea derivative
Content can be 5g/L-20g/L, for example, can be in the range of 5g/L-15g/L or 10g/L-15g/L, or above-mentioned provide
Numerical definiteness any range in, for example, in 10g/L-20g/L, 15g/L-20g/L.
Amino acid can promote the dissolving of tin.By adding amino acid into tin stripping liquid, move back tin speed not damaging and move back
In the case of tin amount, the 5g/L-100g/L nitric acid in tin stripping liquid (can be converted into quality hundred by the nitric acid that content can be utilized relatively low
Divide ratio about 0.5%-10%) handled move back tin.In addition, amino acid can also be complexed with divalent tin ion.
In an exemplary embodiment of the present invention, amino acid can be included in glycine, alanine and lysine at least
One kind, however, the invention is not restricted to this.Cumulative volume based on tin stripping liquid, the content of amino acid can be 0g/L-100g/L, example
Such as, can be in 6g/L-100g/L, 10g/L-90g/L, 20g/L-85g/L, 25g/L-80g/L, 30g/L-75g/L, 35g/L-
In the range of 70g/L, 40g/L-65g/L, 45g/L-60g/L or 50g/L-55g/L, or the above-mentioned numerical definiteness provided is any
In the range of, for example, in 5g/L-55g/L, 15g/L-65g/L.
At least two exemplary embodiment in stabilizer includes carboxylic acid compound, carbamide compounds and amino acid
In, at least two in carboxylic acid compound, carbamide compounds and amino acid, which can play a part of collaboration, promotes, that is,
Say, compared with the stabilizer of one pack system, it is contemplated that divalent tin ion is oxidized to during less than ground or significantly preventing molten tin
The hydrolysis of tetravalence tin ion and tetravalence tin ion, so as to be better protected from generating β-stannic acid precipitation.
The effect of antioxidant is to prevent Sn2+By the dioxygen oxidation in air into Sn4+.According to the exemplary of the present invention
Embodiment, antioxidant can include phenolic compound.Phenolic compound can include resorcinol, catechol, to benzene two
At least one of phenol and phloroglucin, however, embodiments of the invention not limited to this.
If based on the cumulative volume of tin stripping liquid, the content of antioxidant is less than 0.5g/L, then can not effectively prevent Sn2+Quilt
It is oxidized to Sn4+；If based on the cumulative volume of tin stripping liquid, the amount of antioxidant is higher than 25g/L, then can cause unnecessary waste, increases
Add cost of material.In an embodiment of the present invention, the content of antioxidant can be in 0.5g/L-25g/L, 1g/L-20g/L or 5g/
In the range of L-15g/L, or in any range of the above-mentioned numerical definiteness provided, for example, in 5g/L-20g/L, 10g/L-20g/L.
It can suppress Sn as at least one of the carboxylic acid compound of stabilizer and carbamide compounds2+It is oxidized to Sn4+
And/or Sn4+Hydrolysis；Antioxidant can suppress Sn2+By the dioxygen oxidation in air into Sn4+.Therefore, antioxidant and
Generation of the stabilizer including at least one of carboxylic acid compound and carbamide compounds for suppressing precipitation serves actively
Synergy.In addition, in the case where stabilizer includes amino acid, use can contain in the case where not influenceing to move back tin speed
Relatively low nitric acid is measured to carry out moving back tin.
In an exemplary embodiment of the present invention, tin stripping liquid is by the nitric acid of above-mentioned content, complexing agent, stabilizer and anti-oxidant
Agent and form as the water of solvent.In the another exemplary embodiment of the present invention, tin stripping liquid includes the nitre of above-mentioned content
Acid, complexing agent, stabilizer, antioxidant, the water as solvent and optional other components, for example, other in order to realize
Function and the other component added.
In the non-limiting example of the present invention, tin stripping liquid and containing on base material can be made by infusion method or spray process
Tin layers contact, and contain tin layers to obtain tin removal waste liquor on base material so as to remove, however, the invention is not restricted to this, can use and appoint
What suitable method makes tin stripping liquid be contacted with base material containing tin layers.
The method containing tin layers removed using infusion method on base material is described below.
In the exemplary embodiment, base material is cleaned and dried, then base material is dipped into tin stripping liquid with moving back
Tin liquor contacts.In more specifically exemplary implementation, by base material through sand paper (for example, 1200# abrasive paper for metallograph) fine grinding, acetone oil removing
Afterwards, it is immersed in the solvent of such as absolute ethyl alcohol and carries out cleaning 1min-5min, then performs drying；Base material is dipped into tin stripping liquid,
Then it can be removed at a temperature of 25 DEG C -40 DEG C and under agitation on base material and contain tin layers, so as to obtain tin removal waste liquor.
The method containing tin layers removed using spray process on base material is described below.
In the exemplary embodiment, tin is moved back to the base material spray that translational speed is 3m/min at a temperature of 25 DEG C -40 DEG C
Liquid, so as to obtain tin removal waste liquor.
Can be by the way that each component be dissolved in into water easily to prepare according to the tin stripping liquid of the present invention.
It can be obtained according to the tin stripping liquid of the present invention at least one in following effect：
1st, the stripping of tin layers is applicable not only to according to the tin stripping liquid of the present invention, applies also for leypewter layer, gun-metal
The stripping of layer etc., the moving back containing tin layers especially suitable for precision component and miniature parts in uneven thickness and high precision
Remove, to grounds such as copper, silver, gold without any damage, do not influence the glossiness of ground.
2nd, have that strip speed is fast, it is big to move back tin capacity according to the tin stripping liquid of the present invention, and using it is persistently effective the advantages that.
3rd, low content nitre can be used in the case where not influenceing to move back tin speed and move back tin amount according to the tin stripping liquid of the present invention
Acid, therefore course of reaction is gentleer, heat release is few, and odorlessness produces, poisonous and harmful without cyanide, peroxide and fluoride etc.
Composition, and the nitric acid of low content only generates N with tin reaction2Rather than NO2, therefore reduce the pollution to environment.
4th, the stability of the spent solder stripper obtained using the tin stripping liquid of the present invention is good, is not easy to precipitate, do not block up nozzle, and tin
It can for a long time be stored with bivalent form, be advantageous to use electrodeposition process to reclaim with simple substance form tin ion.
In (S200) is extracted to tin removal waste liquor, extractant is added into tin removal waste liquor to extract in tin removal waste liquor
Nitric acid, and separate oil phase (that is, the extract comprising nitric acid and extractant on upper strata) and aqueous phase (that is, the tin removal waste liquor of lower floor).
In the exemplary embodiment, the concentration of nitric acid in the tin removal waste liquor after extraction is less than 2g/L.
The weight of extractant and tin removal waste liquor ratio can be 1-5:1, for example, can be in 1-4:1 or 2-3:In the range of 1, or
In any range of the above-mentioned numerical definiteness provided, for example, can be in 2-4:In 1.If the weight of extractant and tin removal waste liquor
Than less than 1:1, then it can not fully extract the nitric acid in tin removal waste liquor；If the weight of extractant and tin removal waste liquor ratio is more than
5:1, then the concentration of nitric acid in extract can be caused relatively low or cause unnecessary waste.
Extractant can include 20wt%-40wt% tributyl phosphate and 60wt%-80wt% by weight percentage
Sulfonated kerosene, more specifically, 25wt%-35wt% tributyl phosphate and 65wt%-75wt% sulfonated kerosene, or
28wt%-32wt% tributyl phosphate and 68wt%-72wt% sulfonated kerosene, or 30wt% tributyl phosphate and
70wt% sulfonated kerosene.In the exemplary embodiment, extractant is made up of the tributyl phosphate and sulfonated kerosene of above-mentioned content.
Extractant including tributyl phosphate and sulfonated kerosene can be such that the nitric acid in tin removal waste liquor enters sufficiently into extractant.
In the present invention, the nitric acid in tin removal waste liquor can be fully removed by extraction.For example, nitric acid clearance is reachable
90%, so as to prevent Sn2+Metastannic acid precipitation is oxidized to, and is Sn2+It is not dissolved when being separated out with simple substance form and provides premise.
In an exemplary embodiment of the present invention, multistage (example can be carried out to the nitric acid in tin removal waste liquor using extractant
Such as, 2-6 levels) extraction.
, can be using electrolytic cell 100 come after to extraction in the tin removal waste liquor after to extraction carries out diaphragm electrolysis (S300)
Tin removal waste liquor carry out diaphragm electrolysis.As shown in Fig. 2 electrolytic cell 100 can include by barrier film 110 (such as cation-exchange membrane)
The anode chamber 120 separated and cathode chamber 130, the anode 140 in anode chamber 120, the negative electrode 150 in cathode chamber 130,
The power supply 160 that is connected with anode 140 and negative electrode 150 and optionally with the detector 170 (for example, thermometer) of detection temperature.
It is 3%- first by such as concentration when carrying out diaphragm electrolysis to the tin removal waste liquor after extraction using electrolytic cell 100
The pyrovinic acid aqueous solution of 15% (such as 5%) is added in anode chamber 120, and the tin removal waste liquor after extraction is added into cathode chamber
In 130, it may then pass through power supply 160 and be powered to anode 140 and negative electrode 150, at a constant temperature and in current density for for example
300A/m2-2000A/m2Under conditions of perform diaphragm electrolysis, so as to Sn2+Separated out in the form of simple substance on negative electrode 150.For example,
Current density can be in 300A/m2-1500A/m2、400A/m2-1200A/m2、500A/m2-1100A/m2、600A/m2-1000A/
m2Or 700A/m2-900A/m2In the range of, or in any range of the above-mentioned numerical definiteness provided, for example, 300A/m2-
500A/m2、300A/m2-700A/m2It is interior.
In an exemplary embodiment of the present invention, anode 140 is the titanium plate coated with rare precious metal, here, rare precious metal
Can be tantalum or iridium；Negative electrode 150 is stainless steel plate.
In an exemplary embodiment of the present invention, tin work can be moved back by being added into the tin removal waste liquor after diaphragm electrolysis
The component lost in skill, extraction process and/or diaphragm electrolysis technique is (for example, nitric acid, complexing agent, stabilizer and/or anti-oxidant
Agent etc.), the requirement of tin stripping liquid is reached, so as to realize spent solution regeneration, recycles, realizes Zero discharge, help
In enterprise clean production.
The method according to the invention, the tin removal waste liquor after extraction is placed in by barrier film (such as cation-exchange membrane) 110
In cathode chamber, anode caused O nearby can be avoided2Promote the Sn in the tin removal waste liquor after extraction2+Oxidation deterioration is to form
H2SnO3Precipitation, so as to ensure that Sn2+Separated out with simple substance form on negative electrode.
In an exemplary embodiment of the present invention, extraction to including extractant and nitric acid can also be included by reclaiming the method for tin
The step of taking liquid to be handled to reclaim nitric acid (S400).
The exemplary reality of (S400) handled the extract comprising extractant and nitric acid to reclaim nitric acid the step of
Apply in example, first, the extract comprising extractant and nitric acid is stripped using water, it is mixed comprising water and nitric acid to obtain
Close liquid, i.e. aqueous solution of nitric acid.Specifically, can be 1-5 according to the weight ratio of water and the extract comprising extractant and nitric acid:
1 (for example, 1.5-4.5:1、2-4:1 or 2.5-3.5:1) add water in the extract comprising extractant and nitric acid and carry out instead
Extraction, nitric acid is taken out to be stripped from the extract comprising extractant and nitric acid, so as to obtain the mixed liquor comprising water and nitric acid,
Such as obtained mixed liquor can be the aqueous solution of nitric acid that concentration is 10g/L-30g/L.Here, the extraction for taking out nitric acid is stripped by water
Take agent to may return in step (S200) to reuse.Here it is possible to using water to including the extract of extractant and nitric acid
Carry out multistage (for example, 2-5 levels) back extraction.
Selectively, then, the mixed liquor comprising water and nitric acid can be concentrated using electroosmose process.It can utilize
Anion-exchange membrane and can be 300A/m in current density2-500A/m2Under conditions of to comprising water and nitric acid mixed liquor carry out
Concentration, until the concentration of nitric acid reaches such as more than 100g/L.Here, the nitric acid obtained may return to moving back in step (S100)
Reused in tin liquor.Here it is possible to multistage (for example, 2-5 levels) electrodialysis concentration is carried out to the mixed liquor comprising water and nitric acid.
It can be obtained according to the method for the recovery simple substance tin of the present invention at least one in following effect：
1st, the method according to the invention, the nitric acid in tin removal waste liquor can be separated by extraction, for example, tin removal waste liquor
The clearance of middle nitric acid is up to more than 90%.
2nd, the method according to the invention, concentrated by the nitric acid separated to back extraction, can be by the concentration of nitric acid
More than 100g/L is concentrated to, so as to be used as the main addition raw material of production tin stripping liquid.
3rd, the method according to the invention, remove the tin removal waste liquor after nitric acid realizes Sn by diaphragm electrolysis2+With simple substance shape
Formula reclaims, and simple substance tin is deposited on the surface of negative electrode in the form of tinfoil paper layer, and purity bright in color, is easily peeled off up to more than 99.5%.
4th, the method according to the invention, the energy consumption reclaimed needed for tin is low, Sn2+Oxidized probability is few, is advantageous to enterprise
It is energy-saving, reduce cost.
5th, the method according to the invention, Sn is reclaimed2+Waste liquid afterwards can be moved back in tin, extraction, electrodeposition process by adding
The active principle (for example, nitric acid, complexing agent, stabilizer and/or antioxidant etc.) of loss, reaches the requirement of tin stripping liquid,
So as to realize spent solution regeneration, recycle, realize Zero discharge, contribute to enterprise clean production.
The method of the recovery simple substance tin according to the present invention is described in more detail with reference to embodiment.
Embodiment 1：The preparation of tin stripping liquid
50g nitric acid, 200g pyrovinic acids, 20g citric acids, 20g thiocarbamides, 60g glycine and 5g resorcinols are dissolved in water
In, so that 1L tin stripping liquid is made.
Embodiment 2：The preparation of tin stripping liquid
By 75g nitric acid, 150g pyrovinic acids, 12.5g salicylic acids, 27.5g acylureas, 30g alanine and 10g catechols
It is soluble in water, so that 1L tin stripping liquid is made.
Embodiment 3：The preparation of tin stripping liquid
100g nitric acid, 300g pyrovinic acids, 70g sulfamic acids, 50g tartaric acid, 0.5g hydroquinones is soluble in water, with
1L tin stripping liquid is made.
Embodiment 4：The preparation of tin stripping liquid
30g nitric acid, 90g sulfamic acids, 35g tartaric acid, 90g alanine and 10g resorcinols is soluble in water, to be made
1L tin stripping liquid.
Embodiment 5：The preparation of tin stripping liquid
30g nitric acid, 70g sulfamic acids, 40g citric acids, 20g thiocarbamides and 80g lysines and 15g resorcinols are dissolved in water
In, so that 1L tin stripping liquid is made.
Embodiment 6：The preparation of tin stripping liquid
85g nitric acid, 150g pyrovinic acids, 20g thiocarbamides, 10g resorcinols is soluble in water, so that 1L tin stripping liquid is made.
Embodiment 7：The preparation of tin stripping liquid
90g nitric acid, 180g pyrovinic acids, 25g urea, 20g glycine and 10g phloroglucins is soluble in water, to be made
1L tin stripping liquid.
Embodiment 8：The preparation of tin stripping liquid
100g nitric acid, 250g pyrovinic acids, 40g citric acids, 25g acylureas and 5g resorcinols is soluble in water, with system
Obtain 1L tin stripping liquid.
Embodiment 9：The preparation of tin stripping liquid
70g nitric acid, 550g pyrovinic acids, 15g thiocarbamides, 35g alanine and 25g resorcinols is soluble in water, to be made
1L tin stripping liquid.
Embodiment 10：The preparation of tin stripping liquid
In addition to stabilizer is 100g thiocarbamides, tin stripping liquid is prepared according to the method for embodiment 1.
Embodiment 11：The preparation of tin stripping liquid
In addition to stabilizer is 70g acylureas, tin stripping liquid is prepared according to the method for embodiment 2.
Embodiment 12：The preparation of tin stripping liquid
In addition to stabilizer is 30g tartaric acid and 20g acylureas, tin stripping liquid is prepared according to the method for embodiment 3.
Embodiment 13：The preparation of tin stripping liquid
In addition to stabilizer is 35g tartaric acid and 10g urea, tin stripping liquid is prepared according to the method for embodiment 4.
Embodiment 14：The preparation of tin stripping liquid
In addition to stabilizer is 140g citric acids, tin stripping liquid is prepared according to the method for embodiment 5.
Embodiment 15：The preparation of tin stripping liquid
In addition to stabilizer is 65g acylureas, tin stripping liquid is prepared according to the method for embodiment 8.
Comparative example 1：The preparation of tin stripping liquid
In addition to not including antioxidant, tin stripping liquid is manufactured according to the method for embodiment 6.
Comparative example 2：The preparation of tin stripping liquid
450g nitric acid, 180g pyrovinic acids, 25g urea is soluble in water, so that 1L tin stripping liquid is made.
Comparative example 3：The preparation of tin stripping liquid
230g nitric acid, 550g pyrovinic acids, 15g thiocarbamides is soluble in water, so that 1L tin stripping liquid is made.
Embodiment 16：Reclaim simple substance tin
Move back process of tin：Spray and lead to the Copper base material (surface has tin layers) that translational speed is 3m/min at a temperature of 40 DEG C
The tin stripping liquid that embodiment 1 obtains is crossed, cleaning 15s is carried out to base material with water afterwards.Thus evaluate the performance of tin stripping liquid, as a result exist
Shown in following table 1.
Extraction process：Tin removal waste liquor is entered using extractant (30wt% tributyl phosphate and 70wt% sulfonated kerosene)
Row extracts, so that the concentration of nitric acid in the tin removal waste liquor after extraction is less than 1.5g/L.Wherein, the weight of extractant and tin removal waste liquor
Than for 2.5:1.
Anti-extraction process：The extract comprising nitric acid and extractant is stripped using water, to obtain comprising water and
The mixed liquor of nitric acid, the concentration of nitric acid is 20g/L in mixed liquor；Wherein, the weight of water and the extract comprising nitric acid and extractant
Amount is than being 2.5:1.It is 300A/m in current density2, anion-exchange membrane area be 2m2Under conditions of to including water and nitric acid
Mixed liquor carry out two-stage electrodialysis concentration.The concentration of nitric acid being concentrated to give is about 150g/L, may return in tin stripping liquid and uses.
Diaphragm electrolysis technique：Tin removal waste liquor after extraction is added in the cathode chamber 130 of electrolytic cell 100, is by concentration
The 5% pyrovinic acid aqueous solution is added in the anode chamber 120 of electrolytic cell 100, and in constant temperature, current density 400A/m2
Under conditions of carry out diaphragm electrolysis, simple substance Sn is separated out on negative electrode.Wherein, negative electrode is stainless steel plate, and anode is coated with tantalum iridium
Titanium plate.As a result show in table 2.
Embodiment 17：Reclaim simple substance tin
Move back process of tin：Spray and lead to the Copper base material (surface has tin layers) that translational speed is 3m/min at a temperature of 40 DEG C
The tin stripping liquid that embodiment 2 obtains is crossed, cleaning 15s is carried out to base material with water afterwards.Thus evaluate the performance of tin stripping liquid, as a result exist
Shown in following table 1.
Extraction process：Tin removal waste liquor is entered using extractant (40wt% tributyl phosphate and 60wt% sulfonated kerosene)
Row extracts, so that the concentration of nitric acid in the tin removal waste liquor after extraction is less than 1.2g/L.Wherein, the weight of extractant and tin removal waste liquor
Than for 3:1.
Anti-extraction process：The extract comprising nitric acid and extractant is stripped using water, to obtain comprising water and
The mixed liquor of nitric acid, the concentration of nitric acid is 15g/L in mixed liquor.Wherein, the weight of water and the extract comprising nitric acid and extractant
Amount is than being 4:1.It is 500A/m in current density2, anion-exchange membrane area be 5m2Under conditions of to comprising water and nitric acid
Mixed liquor carries out two-stage electrodialysis concentration.The concentration of nitric acid being concentrated to give is 120g/L, may return in tin stripping liquid and uses.
Diaphragm electrolysis technique：Tin removal waste liquor after extraction is added in the cathode chamber 130 of electrolytic cell 100, is by concentration
The 5% pyrovinic acid aqueous solution is added in the anode chamber 120 of electrolytic cell 100, and in constant temperature, current density 500A/m2
Under conditions of carry out diaphragm electrolysis, simple substance Sn is separated out on negative electrode.Wherein, negative electrode is stainless steel plate, and anode is coated with tantalum iridium
Titanium plate.As a result show in table 2.
Embodiment 18-23：Reclaim simple substance tin
In addition to moving back and obtaining tin removal waste liquor using embodiment 3-8 tin stripping liquid in process of tin, according to embodiment 16
Mode identical mode reclaims simple substance tin.
Embodiment 24-30：Reclaim simple substance tin
In addition to moving back and obtaining tin removal waste liquor using embodiment 9-15 tin stripping liquid in process of tin, according to embodiment 17
Mode identical mode reclaims simple substance tin.
Comparative example 4：Reclaim simple substance tin
In addition to moving back and obtaining tin removal waste liquor using the tin stripping liquid of comparative example 1 in process of tin, according to the side with embodiment 16
Formula identical mode reclaims simple substance tin.
Comparative example 5：Reclaim simple substance tin
In addition to moving back and obtaining tin removal waste liquor using the tin stripping liquid of comparative example 2 in process of tin, according to the side with embodiment 17
Formula identical mode reclaims simple substance tin.However, due to generating substantial amounts of precipitation in the tin removal waste liquor, thus can not be to extraction after
Tin removal waste liquor carry out diaphragm electrolysis processing.
Comparative example 6：Reclaim simple substance tin
In addition to moving back and obtaining tin removal waste liquor using the tin stripping liquid of comparative example 3 in process of tin, according to the side with embodiment 17
Formula identical mode reclaims simple substance tin.
Table 1
In table 1, waste liquid refers to tin stripping liquid and the mixture of the tin layers removed from Copper base material；Inoxidizability can be with
Investigated by the way that waste liquid is placed under conditions of blow-by over one month.
, will be according to an embodiment of the invention 6 compared with comparative example 1 with reference to table 1, inoxidizability of the invention is higher than comparative example
Inoxidizability.
In addition, as it can be seen from table 1 according to an embodiment of the invention 7 and 9 tin stripping liquid move back tin speed, move back tin amount with
And metal Sn changes into Sn2+Ratio it is roughly the same with the relevant parameter of comparative example 2 and 3 respectively, however, comparative example 2 moves back tin
Liquid needs 450g/L nitric acid, and the tin stripping liquid of comparative example 3 needs 230g/L nitric acid.It can be seen that existed according to the tin stripping liquid of the present invention
Do not damage and move back tin speed, move back tin capacity and metal changes into Sn2+Ratio in the case of, nitric acid can be reduced in tin stripping liquid
Content, be computed that more than 70% can be reduced.
In addition, the tin removal waste liquor that the tin stripping liquid prepared using embodiment 1-5,8 and 10-15 is obtained is respectively in blow-by
Under the conditions of place certain time after observe the change of each tin removal waste liquor, its result is：Obtained using embodiment 3,10,11,14 and 15
There is muddiness after placing about three months in the tin removal waste liquor arrived, and moves back tin using what embodiment 1,2,4,5,8,12 and 13 obtained
Waste liquid just occurs muddy after placing about six months.
Therefore, the stability for the tin removal waste liquor that the tin stripping liquid for containing two or more components by the stabilizer of the present invention obtains
Higher than the stability that the stabilizer by the present invention contains the tin removal waste liquor that a kind of tin stripping liquid of component obtains.In addition, according to this
No matter the stabilizer in the tin stripping liquid of invention, including a kind of component or including two or more components, the tin that moves back obtained by it gives up
The stability of liquid is above the stability of the tin removal waste liquor obtained by comparative example 1-3 tin stripping liquid.Therefore, pass through the present invention's
The tin removal waste liquor that tin stripping liquid obtains can be stored for a long time in the form of stannous.
Table 2
The Sn rate of recovery in table 2 is the ratio of the quality and the Sn mass in initial tin removal waste liquor of the simple substance tin finally given
Rate.
With reference to table 2, the 16-30 rate of recovery and electrolytic efficiency are higher than the recovery of comparative example 4 and 6 according to an embodiment of the invention
Rate and electrolytic efficiency, for example, the rate of recovery of the simple substance tin of the method according to the invention, more than 95.4%, electrolytic efficiency exists
More than 79.8%.
In addition, by embodiment 22 and 24 respectively compared with comparative example 5 and 6, extraction times needed for extraction process less than pair
Extraction times needed for ratio 5 and 6, therefore, the material and energy expenditure needed for the method according to the invention recovery tin are low, favorably
Lowered consumption in industry energy conservation, reduce cost.
Further, since substantial amounts of precipitation in the tin removal waste liquor that comparative example 5 obtains be present, therefore can not be to moving back tin after extraction
Waste liquid carries out diaphragm electrolysis processing.It can be deposited for a long time in the form of stannous according to the tin removal waste liquor that the tin stripping liquid of the present invention obtains
Store up and without precipitation, provided the foundation so using diaphragm electrolysis to carry out recovery with simple substance form for tin ion.
Although being specifically illustrated in reference to the exemplary embodiment of the present invention and describing the present invention, this area is general
Logical technical staff will be understood that, not being departed from the spirit and scope of the present invention limited such as claim and their equivalent
In the case of, the various changes in form and details can be made herein.Should only in the sense that descriptive rather than for
The purpose of limitation considers embodiment.Therefore, the scope of the present invention is limited by the embodiment of the present invention, but
It is defined by the claims, all differences in the range of this are to be interpreted as being included in the invention.
Claims (17)
1. a kind of tin stripping liquid, it is characterised in that the tin stripping liquid includes 5g/L-100g/L nitric acid, 70g/L-640g/L network
Mixture, 10g/L-150g/L stabilizer, 0.5g/L-25g/L antioxidant and the water as solvent,
Wherein, the complexing agent includes at least one of pyrovinic acid and sulfamic acid,
The stabilizer includes at least one of carboxylic acid compound, carbamide compounds and amino acid,
The carboxylic acid compound includes at least one of tartaric acid, citric acid and salicylic acid, and the carbamide compounds include
At least one of urea, glucosyl group urea, thiocarbamide, thiourea derivative and acylureas, the amino acid include glycine, the third ammonia
At least one of acid and lysine.
2. tin stripping liquid according to claim 1, wherein, the tin stripping liquid includes 50g/L-100g/L nitric acid, 70g/L-
The antioxidant of 640g/L complexing agent, 40g/L-150g/L stabilizer and 0.5g/L-25g/L.
3. tin stripping liquid according to claim 2, wherein, the tin stripping liquid includes 55g/L-95g/L nitric acid, 100g/L-
The antioxidant of 600g/L complexing agent, 40g/L-110g/L stabilizer and 1g/L-20g/L.
4. tin stripping liquid according to claim 3, wherein, the tin stripping liquid includes 65g/L-95g/L nitric acid, 150g/L-
The antioxidant of 500g/L complexing agent, 50g/L-100g/L stabilizer and 5g/L-20g/L.
5. tin stripping liquid according to claim 1, wherein, the stabilizer include carboxylic acid compound, carbamide compounds and
At least two in amino acid,
Cumulative volume based on tin stripping liquid, the content of the carboxylic acid compound is 0g/L-40g/L, and the carbamide compounds contain
Measure as 0g/L-30g/L, the content of the amino acid is 0g/L-100g/L.
6. tin stripping liquid according to claim 5, wherein, the carbamide compounds are thiocarbamide or thiourea derivative,
Cumulative volume based on tin stripping liquid, the content of the carbamide compounds is 5g/L-20g/L.
7. tin stripping liquid according to claim 1, wherein, the complexing agent includes pyrovinic acid and sulfamic acid,
Cumulative volume based on tin stripping liquid, the content of pyrovinic acid is 50g/L-550g/L, and the content of sulfamic acid is 20g/L-
90g/L。
8. tin stripping liquid according to claim 1, it is characterised in that the antioxidant includes phenolic compound.
9. tin stripping liquid according to claim 8, it is characterised in that the phenolic compound includes resorcinol, adjacent benzene two
At least one of phenol, hydroquinones and phloroglucin.
10. a kind of method containing tin layers removed on base material, methods described includes making according to any one of claim 1 to 9
Described tin stripping liquid contacts with base material containing tin layers.
11. according to the method for claim 10, the tin layers that contain are tin layers, leypewter layer or gun-metal layer.
12. a kind of method for reclaiming simple substance tin, methods described comprise the following steps：
I) removed using the tin stripping liquid according to any one of claim 1 to 9 and contain tin layers on base material to obtain moving back tin
Waste liquid；
Ii) mixing extractant with tin removal waste liquor causes the nitric acid in tin removal waste liquor to enter extractant, and performs separation, to obtain
Tin removal waste liquor after extraction and the extract comprising extractant and nitric acid；And
Iii diaphragm electrolysis) is performed to the tin removal waste liquor after extraction, to obtain simple substance tin.
13. according to the method for claim 12, wherein, the tributyl phosphate of extractant including 20wt%-40wt% and
60wt%-80wt% sulfonated kerosene.
14. according to the method for claim 12, wherein, the step of extractant is mixed with tin removal waste liquor, is including according to 1-5:
1 weight ratio mixes extractant with tin removal waste liquor.
15. according to the method for claim 12, wherein, to after extraction tin removal waste liquor perform diaphragm electrolysis the step of wrap
Include：
Tin removal waste liquor after extraction is added to the cathode chamber of the electrolytic cell separated by barrier film, the pyrovinic acid aqueous solution is added to
The anode chamber of electrolytic cell, diaphragm electrolysis is carried out to the tin removal waste liquor after extraction, so as to the electro-deposition simple substance tin on negative electrode.
16. according to the method for claim 12, wherein, methods described also includes：
Carrying out back extraction to extract using water causes the nitric acid in extract to enter in water, so as to obtain aqueous solution of nitric acid and anti-
Extractant after extraction；
In step ii) the middle extractant using after back extraction；
Aqueous solution of nitric acid is concentrated, and the aqueous solution of nitric acid of concentration is used in the tin stripping liquid used in step i).
17. a kind of tin stripper solution, it is characterised in that the tin stripper solution includes 50g/L-100g/L nitric acid, 70g/L-
The antioxidant of 640g/L complexing agent, 40g/L-150g/L stabilizer and 0.5g/L-25g/L,
Wherein, the complexing agent includes at least one of pyrovinic acid and sulfamic acid,
The stabilizer is at least one of carboxylic acid compound, carbamide compounds and amino acid or at least two,
The carboxylic acid compound includes at least one of tartaric acid, citric acid and salicylic acid, and the carbamide compounds include
At least one of urea, glucosyl group urea, thiocarbamide, thiourea derivative and acylureas, the amino acid include glycine, the third ammonia
At least one of acid and lysine,
The antioxidant includes at least one of resorcinol, catechol, hydroquinones and phloroglucin.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5512201A (en) * | 1995-02-13 | 1996-04-30 | Applied Chemical Technologies, Inc. | Solder and tin stripper composition |
| CN101962776A (en) * | 2010-09-01 | 2011-02-02 | 济南德锡科技有限公司 | Solder stripping agent and preparation method thereof |
| CN105401151A (en) * | 2015-11-30 | 2016-03-16 | 惠州市博美化工制品有限公司 | Iron substrate plating neutral stripping agent |
| CN105648472A (en) * | 2016-01-22 | 2016-06-08 | 张黎 | Recycling method and system for tin in tin stripping waste liquid and tin stripping waste liquid |
| CN105734620A (en) * | 2016-03-11 | 2016-07-06 | 深圳市松柏实业发展有限公司 | Tin stripping and tin plating liquid, preparing method of tin stripping and tin plating liquid and cyclic regeneration method for adopting tin stripping and tin plating liquid for recycling metal tin |
-
2016
- 2016-07-28 CN CN201610604683.0A patent/CN106048653B/en active Active
- 2016-07-28 CN CN201710751695.0A patent/CN107686893B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5512201A (en) * | 1995-02-13 | 1996-04-30 | Applied Chemical Technologies, Inc. | Solder and tin stripper composition |
| CN101962776A (en) * | 2010-09-01 | 2011-02-02 | 济南德锡科技有限公司 | Solder stripping agent and preparation method thereof |
| CN105401151A (en) * | 2015-11-30 | 2016-03-16 | 惠州市博美化工制品有限公司 | Iron substrate plating neutral stripping agent |
| CN105648472A (en) * | 2016-01-22 | 2016-06-08 | 张黎 | Recycling method and system for tin in tin stripping waste liquid and tin stripping waste liquid |
| CN105734620A (en) * | 2016-03-11 | 2016-07-06 | 深圳市松柏实业发展有限公司 | Tin stripping and tin plating liquid, preparing method of tin stripping and tin plating liquid and cyclic regeneration method for adopting tin stripping and tin plating liquid for recycling metal tin |
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| CN108707901A (en) * | 2018-06-08 | 2018-10-26 | 深圳市瑞世兴科技有限公司 | A kind of tin stripper of recyclable regenerative and preparation method thereof and application method |
| CN109609974A (en) * | 2019-01-29 | 2019-04-12 | 长江师范学院 | Conducive to the method for reducing Zinc electrolysis tank voltage and energy consumption |
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| CN110760922B (en) * | 2019-10-30 | 2021-08-17 | 昆山金易得环保科技有限公司 | Tin stripping liquid, method for removing tin-containing layer on substrate and method for recovering tin |
| CN110938837A (en) * | 2019-11-22 | 2020-03-31 | 中南大学 | Method for separating and recovering tin coating of PCB (printed circuit board) by two-stage method |
| CN113088973A (en) * | 2021-04-08 | 2021-07-09 | 广东连发助剂厂有限公司 | Tin stripping solution and production process thereof |
| CN113088973B (en) * | 2021-04-08 | 2022-05-10 | 广东连发助剂厂有限公司 | Tin stripping solution and production process thereof |
| CN113463101A (en) * | 2021-07-15 | 2021-10-01 | 广东恒锦通科技有限公司 | Tin stripping water stabilizer |
| CN113564602A (en) * | 2021-07-15 | 2021-10-29 | 广东越凯新材料有限公司 | Single-liquid tin stripping liquid for circuit board and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106048653A (en) | 2016-10-26 |
| CN106048653B (en) | 2017-09-12 |
| CN107686893B (en) | 2019-07-30 |
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