CN107686893B - The method of the method and recycling simple substance tin containing tin layers on tin stripping liquid, removal substrate - Google Patents
The method of the method and recycling simple substance tin containing tin layers on tin stripping liquid, removal substrate Download PDFInfo
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- CN107686893B CN107686893B CN201710751695.0A CN201710751695A CN107686893B CN 107686893 B CN107686893 B CN 107686893B CN 201710751695 A CN201710751695 A CN 201710751695A CN 107686893 B CN107686893 B CN 107686893B
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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 methods for recycling simple substance tin, this method comprises: containing tin layers using on tin stripping liquid removal substrate to obtain tin removal waste liquor, wherein, tin stripping liquid includes the antioxidant of the nitric acid of 5g/L-100g/L, the complexing agent of 70g/L-640g/L, the stabilizer of 10g/L-150g/L and 0.5g/L-25g/L, wherein, the stabilizer includes at least one of carboxylic acid compound, carbamide compounds and amino acid；Extractant is mixed with tin removal waste liquor so that the nitric acid in tin removal waste liquor enters extractant, and executes separation, to obtain tin removal waste liquor extracted and the extract liquor comprising extractant and nitric acid；Diaphragm electrolysis is executed to tin removal waste liquor extracted, to obtain simple substance tin.The method of recycling simple substance tin according to the present invention has many advantages, such as spent solution regeneration, recycles, Zero discharge.
Description
Technical field
It is the present invention relates to a kind of method for recycling simple substance tin, in particular to a kind of to be returned from tin removal waste liquor using diaphragm electrolysis
The method for receiving simple substance tin.
Background technique
Printed circuit board (Printed Circuit Board, PCB) is one of important component of electronics industry, is electronics
The supporter of component.In general, the technique of manufacture printed circuit board includes containing tin layers using on tin stripping liquid removal circuit board, from
And generate a large amount of tin removal waste liquor.Currently, 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 due to its technology, economic indicator is general, the cyanide toxicity that contains is big,
It is very big to the harm of operator in production process, therefore less use strong base tin stripping liquid.Nitric acid type tin stripping liquid is manufacture
The leading dosage form of PCB, Theil indices are higher in the tin removal waste liquor of generation, 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 that alkali is added to carry out neutralization precipitation, is then filtered, filter cake tin mud is sent
Enter smeltery's pyrometallurgical smelting, filtrate is discharged after sulfide recycling copper is then added.This not only generates a large amount of waste residue, and the utilization of resources is not
Sufficiently, and processing cost is higher.In recent years, and distillation recovery method, acidic precipitation agent facture occur etc., but these method meetings
A large amount of other waste liquids are generated, secondary pollution is caused, and the control of complex process, condition is stringent, processing cost is high.
Summary of the invention
It is an object of the present invention to provide a kind of methods for recycling simple substance tin.
The purpose of the present invention is to provide a kind of recycling simple substance tin of at least one problem being able to solve in problem above
Method.
The method of recycling simple substance tin according to the present invention includes the following steps: (a) using containing on tin stripping liquid removal substrate
Tin layers are to obtain tin removal waste liquor, wherein tin stripping liquid includes the nitric acid of 5g/L-100g/L, the complexing agent of 70g/L-640g/L, 10g/
The stabilizer of L-150g/L and the antioxidant of 0.5g/L-25g/L, wherein the stabilizer includes carboxylic acid compound, ureas
At least one of compound and amino acid；(b) extractant is mixed with tin removal waste liquor so that the nitric acid in tin removal waste liquor enters
Extractant, and separation is executed, to obtain tin removal waste liquor extracted and the extract liquor comprising extractant and nitric acid；And (c)
Diaphragm electrolysis is executed to tin removal waste liquor extracted, to obtain simple substance tin.
According to an aspect of the present invention, the stabilizer includes in carboxylic acid compound, carbamide compounds and amino acid
At least two.Total 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 object 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 include 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 methane sulfonic acid and sulfamic acid.
According to an aspect of the present invention, the complexing agent includes methane sulfonic acid and sulfamic acid.Totality based on tin stripping liquid
The content of product, methane sulfonic 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, hydroquinone and phloroglucin.
According to an aspect of the present invention, extractant includes the tributyl phosphate and 60wt%-80wt% of 20wt%-40wt%
Sulfonated kerosene.
According to an aspect of the present invention, the step of extractant being mixed with tin removal waste liquor includes the weight ratio according to 1-5:1
Extractant is mixed with tin removal waste liquor.
According to an aspect of the present invention, the step of executing diaphragm electrolysis to tin removal waste liquor extracted includes: will be after extraction
Tin removal waste liquor be added to the cathode chamber of the electrolytic cell separated by diaphragm, aqueous solution of methanesulfonic is added to the anode of electrolytic cell
Room carries out diaphragm electrolysis to tin removal waste liquor extracted, thus the electro-deposition simple substance tin on cathode.
According to an aspect of the present invention, the method also includes: extract liquor is stripped using water so that extract liquor
In nitric acid enter in water, thus obtain aqueous solution of nitric acid and back extraction after extractant；After using back extraction in step (b)
Extractant；Aqueous solution of nitric acid is concentrated, and the aqueous solution of nitric acid of concentration is used in tin stripping liquid used in step (a)
In.
The method of recycling simple substance tin according to the present invention has many advantages, such as spent solution regeneration, recycles, Zero discharge.This
Outside, the purity of the simple substance tin recycled according to the method for the present invention is up to 99.5% or more.
Detailed description of the invention
By with reference to the accompanying drawing to the description of exemplary embodiment, these and/or other aspects be will be apparent and more
It is readily appreciated that, in the accompanying drawings:
Fig. 1 is the flow chart of the method for the recycling simple substance tin of an exemplary embodiment of the present invention；
Fig. 2 is the signal of electrolytic cell used in the method for the recycling simple substance tin of an exemplary embodiment of the present invention
Figure.
Specific embodiment
Below in conjunction with attached drawing and exemplary embodiment, the principle of the present invention is described in further detail, so that skill of the invention
Art solution is more clear.
Fig. 1 is the flow chart of the method for the recycling simple substance tin of an exemplary embodiment of the present invention.Fig. 2 is according to this hair
The schematic diagram of electrolytic cell used in the method for the recycling simple substance tin of bright exemplary embodiment.
Referring to Fig.1, the method for recycling simple substance tin according to the present invention contains tin layers including the use of on tin stripping liquid removal substrate
(S100), (S200) is extracted to tin removal waste liquor and diaphragm electrolysis (S300) is carried out to tin removal waste liquor extracted.
Using containing in tin layers (S100) on tin stripping liquid removal substrate, can use described below according to the present invention
Tin stripping liquid, which removes, contains tin layers on substrate, to obtain tin removal waste liquor.Here, the substrate can refer in order to manufacture PCB and
The substrate of stanniferous layer is electroplated in substrate.It can be tin layers, leypewter layer or gun-metal layer containing tin layers.However, the present invention is not
It is limited to this.
Total volume of the tin stripping liquid according to the present invention based on tin stripping liquid includes the nitric acid of 5g/L-100g/L, 70g/L-640g/
The complexing agent of L, the stabilizer of 10g/L-150g/L, 0.5g/L-25g/L antioxidant.In a preferred embodiment, according to this
Total volume of the tin stripping liquid of invention based on tin stripping liquid include the nitric acid of 50g/L-100g/L, 100g/L-600g/L complexing agent,
The antioxidant of the stabilizer of 50g/L-100g/L, 5g/L-25g/L.In more preferred embodiment, according to the present invention to move back
Total volume of the tin liquor based on tin stripping liquid includes the nitric acid of 55g/L-95g/L, the complexing agent of 150g/L-500g/L, 60g/L-90g/L
Stabilizer, 7g/L-20g/L antioxidant.In the present invention, unit " g/L " refers to the matter of contained component in 1L tin stripping liquid
Amount.
Tin stripping liquid according to the present invention includes as the above-mentioned nitric acid of effective component and solute, complexing agent, stabilizer and to resist
Oxidant and water as solvent.That is, tin stripping liquid according to the present invention is tin stripper solution.
Nitric acid primarily serves oxidation dissolution containing tin layers (for example, tin layers, leypewter layer or gun-metal in tin stripping liquid
Layer) effect, the mechanism of action are as follows: 4Sn+10HNO3→4Sn(NO3)2+NH4NO3+3H2O。
In the present invention, " nitric acid " refers to the HNO as solute3.Exist however, the present invention can use such as mass fraction
The nitric acid solution of 60wt%-70wt% prepares tin stripping liquid, for example, the amount of nitric acid needed for tin stripping liquid can be converted into matter
Score is measured in the amount of the nitric acid solution of 60wt%-70wt%, determines that mass fraction is in 60wt%- needed for tin stripping liquid with this
The amount of the nitric acid solution of 70wt%.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 numerical definiteness out, for example, in 5g/L-55g/L, 10g/L-65g/L.
Complexing agent plays the role 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 moving back tin, tin is mainly with Sn2+Form exist in solution.Due to Sn2+
It is easy to be oxidized to Sn by the oxygen etc. in the nitric acid and air in tin stripping liquid4+, and Sn4+Facile hydrolysis generates β-stannic acid precipitating, thus
Influence the removal for containing tin layers (for example, tin layers and copper-tin alloy layer).Therefore, in the present invention, can have by the way that complexing agent is added
Effect ground inhibits the generation of precipitating.
Complexing agent according to the present invention may include at least one of methane sulfonic acid and sulfamic acid, that is, can only wrap
Methane sulfonic acid is included, only includes sulfamic acid, or including methane sulfonic 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 methane sulfonic acid and sulfamic acid, based on the total of tin stripping liquid
Volume, the content of methane sulfonic 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 inhibit point of nitric acid other than forming complex compound with divalent tin ion
Solution, to inhibit to generate NO2, reduce the pollution to environment.
The effect of stabilizer be to promote the dissolution 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 provided limits
In fixed any range, for example, in 10g/L-110g/L, 40g/L-150g/L.
Stabilizer in tin stripping liquid according to the present invention may include in carboxylic acid compound, carbamide compounds and amino acid
At least one.Only include carbamide compounds i.e., it is possible to only include carboxylic acid compound, only includes 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 may include carboxylic acid compound, carbamide compounds and
At least two in amino acid, that is, 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 highly preferred that stablizing
Agent may include carboxylic acid compound, carbamide compounds and amino acid.
Carboxylic acid compound can be by the free acid content in control tin stripping liquid, to inhibit Sn4+Hydrolysis.In the present invention
Exemplary embodiment in, carboxylic acid compound may include at least one of tartaric acid, citric acid and salicylic acid, however this
It invents without being limited thereto.Total 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 inhibit Sn2+It is oxidized to Sn4+.In an exemplary embodiment of the present invention, carbamide compounds can
To include at least one of urea, glucosyl group urea, thiocarbamide, thiourea derivative and acylureas, for example, can only include sulphur
Urea only includes at least one of thiourea derivative, including urea, glucosyl group urea and acylureas and thiocarbamide, or including urine
At least one of element, glucosyl group urea and acylureas and thiourea derivative, however, the invention is not limited thereto.Based on tin stripping liquid
Total volume, the contents of carbamide compounds can be 0g/L-30g/L, for example, can in 5g/L-30g/L, 10g/L-25g/L or
In the range of 15g/L-20g/L or in any range of the above-mentioned numerical definiteness provided, for example, 3g/L-20g/L, 6g/L-
In 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.In particular, thiocarbamide or thiourea derivative can be effectively removed containing tin layers (especially copper
Tin alloy layers), to be effectively reduced the electrode potential containing tin layers.Total volume based on tin stripping liquid, thiocarbamide or thiourea derivative
Content can be 5g/L-20g/L, for example, in the range of 5g/L-15g/L or 10g/L-15g/L or above-mentioned can provide
Numerical definiteness any range in, for example, in 10g/L-20g/L, 15g/L-20g/L.
Amino acid can promote the dissolution of tin.By the way that amino acid is added into tin stripping liquid, moves back tin speed not damaging and move back
In the case where tin amount, can use the lower nitric acid of content (can be converted into quality hundred for the 5g/L-100g/L nitric acid in tin stripping liquid
Point than be about 0.5%-10%) Lai Jinhang move back tin processing.In addition, amino acid can also be complexed with divalent tin ion.
In an exemplary embodiment of the present invention, amino acid may include in glycine, alanine and lysine at least
One kind, however, the invention is not limited thereto.Total volume based on tin stripping liquid, the content of amino acid can be 0g/L-100g/L, example
It 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 it is any
In range, for example, in 5g/L-55g/L, 15g/L-65g/L.
It include at least two exemplary embodiment in carboxylic acid compound, carbamide compounds and amino acid in stabilizer
In, at least two in carboxylic acid compound, carbamide compounds and amino acid, which can play the role of collaboration, promotes, that is,
It says, compared with the stabilizer of one pack system, it is contemplated that less than ground or significant divalent tin ion during molten tin is prevented to be oxidized to
The hydrolysis of tetravalence tin ion and tetravalence tin ion generates β-stannic acid precipitating to be better protected from.
The effect of antioxidant is to prevent Sn2+By the dioxygen oxidation in air at Sn4+.It is according to the present invention exemplary
Embodiment, antioxidant may include phenolic compound.Phenolic compound may include resorcinol, catechol, to benzene two
At least one of phenol and phloroglucin, however, embodiments of the present invention are not limited thereto.
If the total volume based on tin stripping liquid, the content of antioxidant is lower than 0.5g/L, then can not be effectively prevented Sn2+Quilt
It is oxidized to Sn4+；If the total volume based on tin stripping liquid, the amount of antioxidant is higher than 25g/L, it will cause unnecessary waste,
Increase cost of material.In an embodiment of the present invention, the content of antioxidant can in 0.5g/L-25g/L, 1g/L-20g/L or
In the range of 5g/L-15g/L or in any range of the above-mentioned numerical definiteness provided, for example, 5g/L-20g/L, 10g/L-
In 20g/L.
Sn is able to suppress as at least one of the carboxylic acid compound of stabilizer and carbamide compounds2+It is oxidized to Sn4+
And/or Sn4+Hydrolysis；Antioxidant is able to suppress Sn2+By the dioxygen oxidation in air at Sn4+.Therefore, antioxidant and
Stabilizer including at least one of carboxylic acid compound and carbamide compounds is for inhibiting the generation of precipitating to play actively
Synergistic effect.In addition, use can contain in the case where not influencing to move back tin speed in the case where stabilizer includes amino acid
Lower 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
It agent and forms as the water of solvent.In another exemplary embodiment of the 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 being added.
In non-limiting embodiment of the invention, tin stripping liquid and containing on substrate can be made by infusion method or spray process
Tin layers contact contains tin layers on substrate to remove to obtain tin removal waste liquor, however, the invention is not limited thereto, can use and appoint
What suitable method makes tin stripping liquid and contacting on substrate containing tin layers.
It is described below using the method containing tin layers on infusion method removal substrate.
In the exemplary embodiment, substrate is washed and dried, then by substrate be dipped into tin stripping liquid with move back
Tin liquor contact.In more specific exemplary implementation, by substrate 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 dehydrated alcohol and carries out cleaning 1min-5min, then execute drying；Substrate is dipped into and moves back tin
Liquid, then can 25 DEG C -40 DEG C at a temperature of and remove contain tin layers on substrate under agitation, so that it is useless to obtain moving back tin
Liquid.
It is described below using the method containing tin layers on spray process removal substrate.
In the exemplary embodiment, 25 DEG C -40 DEG C at a temperature of to movement speed be 3m/min substrate spray move back tin
Liquid, to obtain tin removal waste liquor.
Tin stripping liquid according to the present invention can easily be prepared by the way that each component is dissolved in water.
Tin stripping liquid according to the present invention can obtain at least one of following effect:
1, tin stripping liquid according to the present invention is applicable not only to the stripping of tin layers, applies also for leypewter layer, gun-metal
The stripping of layer etc., especially suitable for precision component and the moving back containing tin layers of small parts in uneven thickness and high precision
It removes, to grounds such as copper, silver, gold without any damage, does not influence the glossiness of ground.
2, tin stripping liquid according to the present invention has many advantages, such as that strip speed is fast, it is big and long-lasting use effective to move back tin capacity.
3, tin stripping liquid according to the present invention can use low content nitre in the case where not influencing to move back tin speed and move back tin amount
Acid, therefore reaction process is milder, heat release is few, and odorlessness generates, poisonous and harmful without cyanide, peroxide and fluoride etc.
Ingredient, and the nitric acid of low content reacts with tin and only generates N2Rather than NO2, therefore reduce the pollution to environment.
4, the stability of the spent solder stripper obtained using tin stripping liquid of the invention is good, is not easy to precipitate, do not block up nozzle, and tin
It can be stored for a long time with bivalent form, be conducive to use electrodeposition process to recycle with simple substance form tin ion.
Tin removal waste liquor is being extracted in (S200), extractant is being added into tin removal waste liquor to extract in tin removal waste liquor
Nitric acid, and separate oily phase (that is, the extract liquor comprising nitric acid and extractant on upper layer) and water phase (that is, tin removal waste liquor of lower layer).
In the exemplary embodiment, the concentration of nitric acid in tin removal waste liquor extracted is lower than 2g/L.
The weight ratio of extractant and tin removal waste liquor can be 1-5:1, for example, can in the range of 1-4:1 or 2-3:1, or
In any range of the above-mentioned numerical definiteness provided, for example, can be in 2-4:1.If the weight of extractant and tin removal waste liquor
Than being less than 1:1, then the nitric acid in tin removal waste liquor is extracted with being unable to fully；If the weight ratio of extractant and tin removal waste liquor is greater than
5:1, it is lower it will cause the concentration of nitric acid in extract liquor or cause unnecessary waste.
Extractant may include the tributyl phosphate and 60wt%-80wt% of 20wt%-40wt% by weight percentage
Sulfonated kerosene, more specifically, the sulfonated kerosene of the tributyl phosphate of 25wt%-35wt% and 65wt%-75wt%, or
The tributyl phosphate of the tributyl phosphate of 28wt%-32wt% and the sulfonated kerosene of 68wt%-72wt% or 30wt% and
The sulfonated kerosene of 70wt%.In the exemplary embodiment, extractant is made 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 removal rate can
Up to 90%, to prevent Sn2+It is oxidized to metastannic acid precipitating, and is Sn2+Offer is provided when being precipitated with simple substance form
Premise.
In an exemplary embodiment of the present invention, it can use extractant and multistage (example carried out to the nitric acid in tin removal waste liquor
Such as, 2-6 grades) extraction.
Tin removal waste liquor extracted can use electrolytic cell 100 in diaphragm electrolysis (S300) and come to after extraction
Tin removal waste liquor carry out diaphragm electrolysis.As shown in Fig. 2, electrolytic cell 100 may include by diaphragm 110 (such as cation-exchange membrane)
The anode chamber 120 separated and cathode chamber 130, the anode 140 in anode chamber 120, the cathode 150 in cathode chamber 130,
The power supply 160 that is connect with anode 140 and cathode 150 and optionally in the detector 170 (for example, thermometer) of detection temperature.
It is first 3%- by such as concentration when carrying out diaphragm electrolysis to tin removal waste liquor extracted using electrolytic cell 100
The aqueous solution of methanesulfonic of 15% (such as 5%) is added in anode chamber 120, and tin removal waste liquor extracted is added to cathode chamber
In 130, it may then pass through power supply 160 and be powered to anode 140 and cathode 150, be at a constant temperature and in current density for example
300A/m2-2000A/m2Under conditions of execute diaphragm electrolysis, thus Sn2+It is precipitated on cathode 150 in the form of simple substance.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 any range of the above-mentioned numerical definiteness provided in, 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
It can be tantalum or iridium；Cathode 150 is stainless steel plate.
In an exemplary embodiment of the present invention, tin work can be moved back by adding 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, is recycled, Zero discharge is realized, helps
In enterprise clean production.
According to the method for the present invention, tin removal waste liquor extracted is placed in by diaphragm (such as cation-exchange membrane) 110
In cathode chamber, the O that anode nearby generates can be avoided2Promote the Sn in tin removal waste liquor extracted2+Oxidation deterioration is to form
H2SnO3Precipitating, to ensure that Sn2+It is precipitated on cathode with simple substance form.
In an exemplary embodiment of the present invention, the method for recycling tin can also include to the extraction comprising extractant and nitric acid
The step of taking liquid to be handled to recycle nitric acid (S400).
In the exemplary reality of the step of being handled the extract liquor for including extractant and nitric acid to recycle nitric acid (S400)
It applies in example, it is mixed comprising water and nitric acid to obtain firstly, be stripped using water to the extract liquor comprising extractant and nitric acid
Close liquid, i.e. aqueous solution of nitric acid.In particular, can be 1-5 according to the weight ratio of water and the extract liquor comprising extractant and nitric acid:
1 (for example, 1.5-4.5:1,2-4:1 or 2.5-3.5:1) is added water in the extract liquor comprising extractant and nitric acid and is carried out instead
Extraction takes out nitric acid to be stripped from the extract liquor comprising extractant and nitric acid, so that the mixed liquor comprising water and nitric acid is obtained,
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
It takes agent to may return in step (S200) to reuse.Here it is possible to using water to the extract liquor comprising extractant and nitric acid
Carry out multistage (for example, 2-5 grades) back extraction.
Selectively, then, the mixed liquor comprising water and nitric acid can be concentrated using electroosmose process.It can use
Anion-exchange membrane and can current density be 300A/m2-500A/m2Under conditions of to the mixed liquor comprising water and nitric acid into
Row concentration, until the concentration of nitric acid reaches such as 100g/L or more.Here, the nitric acid obtained may return in step (S100)
Tin stripping liquid in reuse.Here it is possible to carry out multistage (for example, 2-5 grades) electrodialysis to the mixed liquor comprising water and nitric acid
Concentration.
The method of recycling simple substance tin according to the present invention can obtain at least one of following effect:
1, according to the method for the present invention, the nitric acid in tin removal waste liquor can be separated by extraction, for example, tin removal waste liquor
The removal rate of middle nitric acid is up to 90% or more.
2, it according to the method for the present invention, is concentrated by the nitric acid separated to back extraction, it can be by the concentration of nitric acid
It is concentrated to 100g/L or more, so as to use as the main adding raw materials of production tin stripping liquid.
3, the tin removal waste liquor after according to the method for the present invention, removing nitric acid realizes Sn by diaphragm electrolysis2+With simple substance shape
Formula recycling, simple substance tin are deposited on the surface of cathode in the form of tinfoil paper layer, and purity is easy to shell up to 99.5% or more, bright in color
From.
4, according to the method for the present invention, low energy consumption needed for recycling tin, Sn2+The probability being oxidized is few, is conducive to enterprise
It is energy-saving, reduce cost.
5, Sn according to the method for the present invention, is recycled2+Waste liquid afterwards can move back tin, extraction, in 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, recycles, realize Zero discharge, facilitate enterprise clean production.
It is described in more detail below with reference to method of the embodiment to recycling simple substance tin according to the present invention.
Embodiment 1: the preparation of tin stripping liquid
50g nitric acid, 200g methane sulfonic acid, 20g citric acid, 20g thiocarbamide, 60g glycine and 5g resorcinol are dissolved in water
In, the tin stripping liquid of 1L is made.
Embodiment 2: the preparation of tin stripping liquid
By 75g nitric acid, 150g methane sulfonic acid, 12.5g salicylic acid, 27.5g acylureas, 30g alanine and 10g catechol
It is soluble in water, the tin stripping liquid of 1L is made.
Embodiment 3: the preparation of tin stripping liquid
100g nitric acid, 300g methane sulfonic acid, 70g sulfamic acid, 50g tartaric acid, 0.5g hydroquinone is soluble in water, with
The tin stripping liquid of 1L is made.
Embodiment 4: the preparation of tin stripping liquid
30g nitric acid, 90g sulfamic acid, 35g tartaric acid, 90g alanine and 10g resorcinol is soluble in water, to be made
The tin stripping liquid of 1L.
Embodiment 5: the preparation of tin stripping liquid
30g nitric acid, 70g sulfamic acid, 40g citric acid, 20g thiocarbamide and 80g lysine and 15g resorcinol are dissolved in water
In, the tin stripping liquid of 1L is made.
Embodiment 6: the preparation of tin stripping liquid
85g nitric acid, 150g methane sulfonic acid, 20g thiocarbamide, 10g resorcinol is soluble in water, the tin stripping liquid of 1L is made.
Embodiment 7: the preparation of tin stripping liquid
90g nitric acid, 180g methane sulfonic acid, 25g urea, 20g glycine and 10g phloroglucin is soluble in water, to be made
The tin stripping liquid of 1L.
Embodiment 8: the preparation of tin stripping liquid
100g nitric acid, 250g methane sulfonic acid, 40g citric acid, 25g acylureas and 5g resorcinol is soluble in water, with system
Obtain the tin stripping liquid of 1L.
Embodiment 9: the preparation of tin stripping liquid
70g nitric acid, 550g methane sulfonic acid, 15g thiocarbamide, 35g alanine and 25g resorcinol is soluble in water, to be made
The tin stripping liquid of 1L.
Embodiment 10: the preparation of tin stripping liquid
In addition to stabilizer is 100g thiocarbamide, 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 acid, 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
Other than 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 methane sulfonic acid, 25g urea is soluble in water, the tin stripping liquid of 1L is made.
Comparative example 3: the preparation of tin stripping liquid
230g nitric acid, 550g methane sulfonic acid, 15g thiocarbamide is soluble in water, the tin stripping liquid of 1L is made.
Embodiment 16: recycling simple substance tin
Move back process of tin: 40 DEG C at a temperature of it is logical to Copper base material (surface have tin layers) spray that movement speed is 3m/min
The tin stripping liquid that embodiment 1 obtains is crossed, cleaning 15s is carried out to substrate with water later.Thus it evaluates the performance of tin stripping liquid, as a result exists
It is shown in following table 1.
Extraction process: using extractant (tributyl phosphate of 30wt% and the sulfonated kerosene of 70wt%) to tin removal waste liquor into
Row extraction, so that the concentration of nitric acid in tin removal waste liquor extracted is lower than 1.5g/L.Wherein, the weight of extractant and tin removal waste liquor
Than for 2.5:1.
Anti-extraction process: being stripped the extract liquor comprising nitric acid and extractant 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 liquor 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 get is about 150g/L, and may return in tin stripping liquid makes
With.
Diaphragm electrolysis technique: tin removal waste liquor extracted is added in the cathode chamber 130 of electrolytic cell 100, is by concentration
5% aqueous solution of methanesulfonic 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 precipitated on cathode.Wherein, cathode is stainless steel plate, and anode is coated with tantalum iridium
Titanium plate.As a result it shows in table 2.
Embodiment 17: recycling simple substance tin
Move back process of tin: 40 DEG C at a temperature of it is logical to Copper base material (surface have tin layers) spray that movement speed is 3m/min
The tin stripping liquid that embodiment 2 obtains is crossed, cleaning 15s is carried out to substrate with water later.Thus it evaluates the performance of tin stripping liquid, as a result exists
It is shown in following table 1.
Extraction process: using extractant (tributyl phosphate of 40wt% and the sulfonated kerosene of 60wt%) to tin removal waste liquor into
Row extraction, so that the concentration of nitric acid in tin removal waste liquor extracted is lower than 1.2g/L.Wherein, the weight of extractant and tin removal waste liquor
Than for 3:1.
Anti-extraction process: being stripped the extract liquor comprising nitric acid and extractant 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 liquor 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 get is 120g/L, may return in tin stripping liquid and uses.
Diaphragm electrolysis technique: tin removal waste liquor extracted is added in the cathode chamber 130 of electrolytic cell 100, is by concentration
5% aqueous solution of methanesulfonic 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 precipitated on cathode.Wherein, cathode is stainless steel plate, and anode is coated with tantalum iridium
Titanium plate.As a result it shows in table 2.
Embodiment 18-23: recycling simple substance tin
Other than moving back and obtaining tin removal waste liquor using the tin stripping liquid of embodiment 3-8 in process of tin, according to embodiment 16
The identical mode of mode recycles simple substance tin.
Embodiment 24-30: recycling simple substance tin
Other than moving back and obtaining tin removal waste liquor using the tin stripping liquid of embodiment 9-15 in process of tin, according to embodiment 17
The identical mode of mode recycles simple substance tin.
Comparative example 4: recycling simple substance tin
Other than 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
The identical mode of formula recycles simple substance tin.
Comparative example 5: recycling simple substance tin
Other than 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
The identical mode of formula recycles simple substance tin.However, due to producing a large amount of precipitating in the tin removal waste liquor, can not be to extraction after
Tin removal waste liquor carry out diaphragm electrolysis processing.
Comparative example 6: recycling simple substance tin
Other than 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
The identical mode of formula recycles simple substance tin.
Table 1
In table 1, waste liquid refers to the mixture of tin stripping liquid with the tin layers removed from Copper base material；Inoxidizability can be with
It is investigated over one month by placing waste liquid under conditions of blow-by.
Referring to table 1, by embodiment according to the present invention 6 compared with comparative example 1, inoxidizability of the invention is higher than comparative example
Inoxidizability.
In addition, as it can be seen from table 1 the tin stripping liquid of embodiment according to the present invention 7 and 9 move back tin speed, move back tin amount with
And metal Sn is converted to 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 the nitric acid of 450g/L, and the tin stripping liquid of comparative example 3 needs the nitric acid of 230g/L.As it can be seen that tin stripping liquid according to the present invention exists
It does not damage and moves back tin speed, move back tin capacity and metal is converted to Sn2+Ratio in the case where, nitric acid can be reduced in tin stripping liquid
Content, 70% or more can be reduced by being computed.
In addition, by the tin removal waste liquor obtained using the tin stripping liquid of embodiment 1-5,8 and 10-15 preparation respectively in blow-by
Under the conditions of place the variation for observing each tin removal waste liquor after a certain period of time, as a result: 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 that stabilizer through the invention contains two or more components obtains
Higher than the stability for the tin removal waste liquor that the tin stripping liquid that stabilizer through the invention contains a kind of component obtains.In addition, according to this
No matter the stabilizer in the tin stripping liquid of invention is given up including a kind of component or including two or more components by the tin that moves back that it is obtained
The stability of liquid is above the stability of the tin removal waste liquor obtained by the tin stripping liquid of comparative example 1-3.Therefore, through the invention
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 quality of finally obtained simple substance tin and the ratio of the Sn mass in initial tin removal waste liquor
Rate.
Referring to table 2, the rate of recovery and electrolytic efficiency of embodiment according to the present invention 16-30 are higher than the recycling of comparative example 4 and 6
Rate and electrolytic efficiency, for example, the rate of recovery of simple substance tin according to the method for the present invention is 95.4% or more, electrolytic efficiency exists
79.8% or more.
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, material needed for recycling tin according to the method for the present invention and energy consumption are low, favorably
It lowers consumption in industry energy conservation, reduces cost.
Further, since there is a large amount of precipitating in the tin removal waste liquor that comparative example 5 obtains, therefore tin can not be moved back to extracted
Waste liquid carries out diaphragm electrolysis processing.The tin removal waste liquor that tin stripping liquid according to the present invention obtains can be deposited for a long time in the form of stannous
Store up and without precipitating, so for tin ion use diaphragm electrolysis with simple substance form carry out recycle provide the foundation.
Although the present invention is specifically illustrated in and described referring to exemplary embodiment of the present invention, this field is general
It is logical the skilled person will understand that, not departing from the spirit and scope of the present invention as defined by claim and their equivalent
In the case of, it can be in form and details can be made herein various changes.Should only in the sense that descriptive rather than for
The purpose of limitation considers embodiment.Therefore, the scope of the present invention is not limited by a specific embodiment of the invention,
It is defined by the claims, all differences within the scope of this are to be interpreted as being included in the invention.
Claims (13)
1. a kind of tin stripping liquid, which is characterized in that the tin stripping liquid includes the network of the nitric acid of 50g/L-100g/L, 70g/L-640g/L
Mixture, the stabilizer of 40g/L-150g/L, the antioxidant of 0.5g/L-25g/L and the water as solvent,
Wherein, the complexing agent is at least one of methane sulfonic acid and sulfamic acid,
The stabilizer is at least two in 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,
The antioxidant includes at least one of resorcinol, catechol, hydroquinone and phloroglucin.
2. tin stripping liquid according to claim 1, wherein the tin stripping liquid includes the nitric acid of 55g/L-95g/L, 100g/L-
The antioxidant of the complexing agent of 600g/L, the stabilizer of 40g/L-110g/L and 1g/L-20g/L.
3. tin stripping liquid according to claim 2, wherein the tin stripping liquid includes the nitric acid of 65g/L-95g/L, 150g/L-
The antioxidant of the complexing agent of 500g/L, the stabilizer of 50g/L-100g/L and 5g/L-20g/L.
4. tin stripping liquid according to claim 1, wherein the total volume based on tin stripping liquid, the carboxylic acid compound contain
Amount is 0g/L-40g/L, and the content of the carbamide compounds is 0g/L-30g/L, and the content of the amino acid is 0g/L-100g/
L。
5. tin stripping liquid according to claim 4, wherein the carbamide compounds are thiocarbamide or thiourea derivative,
Total volume based on tin stripping liquid, the content of the carbamide compounds are 5g/L-20g/L.
6. tin stripping liquid according to claim 1, wherein the complexing agent is methane sulfonic acid and sulfamic acid,
Total volume based on tin stripping liquid, the content of methane sulfonic acid are 50g/L-550g/L, and the content of sulfamic acid is 20g/L-
90g/L。
7. a kind of method containing tin layers on removal substrate, the method includes making institute according to any one of claims 1 to 6
The tin stripping liquid stated and being contacted containing tin layers on substrate.
8. according to the method described in claim 7, the tin layers that contain are tin layers, leypewter layer or gun-metal layer.
9. a kind of method for recycling simple substance tin, described method includes following steps:
I) contain tin layers using on the tin stripping liquid removal substrate described according to any one of claims 1 to 6 to obtain moving back tin
Waste liquid；
Ii) extractant is mixed with tin removal waste liquor so that the nitric acid in tin removal waste liquor enters extractant, and executes separation, to obtain
Tin removal waste liquor extracted and extract liquor comprising extractant and nitric acid；And
Iii diaphragm electrolysis) is executed to tin removal waste liquor extracted, to obtain simple substance tin.
10. according to the method described in claim 9, wherein, extractant include 20wt%-40wt% tributyl phosphate and
The sulfonated kerosene of 60wt%-80wt%.
11. according to the method described in claim 9, wherein, the step of extractant is mixed with tin removal waste liquor includes according to 1-5:1
Weight ratio extractant is mixed with tin removal waste liquor.
12. according to the method described in claim 9, wherein, including: to the step of tin removal waste liquor extracted execution diaphragm electrolysis
Tin removal waste liquor extracted is added to the cathode chamber of the electrolytic cell separated by diaphragm, aqueous solution of methanesulfonic is added to
The anode chamber of electrolytic cell carries out diaphragm electrolysis to tin removal waste liquor extracted, thus the electro-deposition simple substance tin on cathode.
13. according to the method described in claim 9, wherein, the method also includes:
Extract liquor is stripped using water so that the nitric acid in extract liquor enters in water, to obtain aqueous solution of nitric acid and anti-
Extractant extracted；
The extractant after back extraction is used in step ii)；
Aqueous solution of nitric acid is concentrated, and the aqueous solution of nitric acid of concentration is used in tin stripping liquid used in step i).
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| CN107557801B (en) * | 2017-07-21 | 2018-06-05 | 深圳市祺鑫天正环保科技有限公司 | The processing method of tin removal waste liquor |
| CN108300872A (en) * | 2018-04-28 | 2018-07-20 | 昆山雅鑫化工有限公司 | The devices and methods therefor of tin is recycled for circuit board |
| CN108707901B (en) * | 2018-06-08 | 2020-09-01 | 深圳市瑞世兴科技有限公司 | Recyclable tin stripping solution and preparation method and use method thereof |
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| CN112011689A (en) * | 2019-05-30 | 2020-12-01 | 惠州Tcl环境科技有限公司 | Method for recovering substances from waste tin stripping waste liquid of nitric acid system |
| 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 |
| 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 |
| CN113174488B (en) * | 2021-05-06 | 2023-02-03 | 广东明方科技有限公司 | Method for extracting tin metal from waste circuit board by using sulfamic acid |
| 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 |
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|---|---|
| CN106048653B (en) | 2017-09-12 |
| CN107686893A (en) | 2018-02-13 |
| CN106048653A (en) | 2016-10-26 |
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