CN110241308A - The recovery method and system of tin metal in a kind of nitric acid type tin-stripping wastewater - Google Patents
The recovery method and system of tin metal in a kind of nitric acid type tin-stripping wastewater Download PDFInfo
- Publication number
- CN110241308A CN110241308A CN201910275995.5A CN201910275995A CN110241308A CN 110241308 A CN110241308 A CN 110241308A CN 201910275995 A CN201910275995 A CN 201910275995A CN 110241308 A CN110241308 A CN 110241308A
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- Prior art keywords
- tin
- solution
- nitric acid
- metal
- acid type
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The present invention provides the recovery methods and system of tin metal in a kind of nitric acid type tin-stripping wastewater, pass through legal and flocculence in combination, in a certain range by system pH control, then precipitate metal ion is realized by addition high polymer coagulant, the Theil indices that can be realized in stannic hydroxide product are higher than 50%, it is all substantially reduced compared to required alkaline solution dosage during a kind of simple tin recovery processing for only carrying out tin removal waste liquor with method and flocculant usage, alkaline solution dosage is about traditional 1/2, and flocculant usage is about traditional 1/3.
Description
Technical field
This application involves the recycling fields of renewable resource utilization and non-ferrous metal, more particularly to a kind of nitric acid type is moved back
The recovery method and system of tin metal in tin waste water.
Background technique
Tin removal waste liquor is a kind of acid waste water generated in printed wiring board production process, containing a large amount of nitric acid, tin,
The gas chromatographies such as the metal ions such as iron, copper and copper inhibitor, tin suspending agent, are directly discharged to not only result in environment
The waste of tin, and would seriously pollute the environment, it is all very big to the harm of the mankind and environment.Neutralisation is that recovery train plate moves back tin
The conventional method of tin in waste liquid, but neutralisation in the prior art, often there is precipitating pH higher, alkaline solution dosage is big
Defect, other heavy metal ion such as iron, copper in the tin precipitated containing more content cause that tin purity is low, Theil indices
Not high problem, and directly strainability is poor, and production time higher cost seriously affects the recycling of tin, at present to nitre
There are many deficiencies for the recovery technology of tin metal in acid type tin-stripping wastewater.
Summary of the invention
In order to solve above-mentioned deficiency, technical concept of the application based on traditional neutralisation, providing a kind of nitric acid type, to move back tin useless
The recovery method and system of tin metal in water, by legal and flocculence in combination, in a certain range by system pH control,
Then precipitate metal ion is realized by addition high polymer coagulant, and then recycles tin metal.
First aspect present invention provides a kind of recovery method of tin metal in nitric acid type tin-stripping wastewater, comprising:
Alkaline solution is added into the nitric acid type tin-stripping wastewater of tin metal to be recycled to set feed speed, forms pH value
In 0.5 to 0.8 mixed solution；
The flocculant of setting content is added after preset duration into the mixed solution, forms precipitated phase product and liquid phase produces
Object；
The precipitated phase product is extracted and washed, stanniferous metal product is obtained.
In certain embodiments, the alkaline solution is NaOH solution, Na2CO3Solution and NaHCO3One of solution
Or it is a variety of.
In certain embodiments, the mass fraction of the flocculant is less than 3 ‰.
In certain embodiments, the preset duration is greater than 30 minutes.
In certain embodiments, it is described set charging rate as can be formed in 40-60 minutes the mixed solution into
Expect speed.
Second aspect of the present invention provides a kind of recovery system of tin metal in nitric acid type tin-stripping wastewater, comprising:
Device is neutralized, alkaline solution is added to set feed speed into the nitric acid type tin-stripping wastewater of tin metal to be recycled,
Form the mixed solution that pH value is in 0.5 to 0.8；
The flocculant of setting content is added after preset duration into the mixed solution for settler, forms precipitated phase and produces
Object and liquid product；
Wash mill extracts and washs the precipitated phase product, obtains stanniferous metal product.
Beneficial effects of the present invention are as follows:
The present invention provides the recovery method and system of tin metal in a kind of nitric acid type tin-stripping wastewater, by legal in combination and
Then flocculence in a certain range by system pH control realizes precipitate metal ion, energy by addition high polymer coagulant
It enough realizes that the Theil indices in stannic hydroxide product are higher than 50%, is only returned with the tin that a kind of method carries out tin removal waste liquor compared to simple
It receives required alkaline solution dosage and flocculant usage in treatment process all to substantially reduce, alkaline solution dosage is about traditional 1/
2, flocculant usage is about traditional 1/3, and realize real cost of production has obtained effective control, and at actual production
The wastewater flow rate of generation again during reason also greatly reduces, and shortens the process cycle of tin removal waste liquor.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 shows a kind of process signal of the recovery method of tin metal in nitric acid type tin-stripping wastewater in the embodiment of the present application
Figure.
Fig. 2 shows the module signals of the recovery system of tin metal in nitric acid type tin-stripping wastewater a kind of in the embodiment of the present application
Figure.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Tin removal waste liquor is a kind of acid waste water generated in printed wiring board production process, containing a large amount of nitric acid, tin,
The gas chromatographies such as the metal ions such as iron, copper and copper inhibitor, tin suspending agent, are directly discharged to not only result in environment
The waste of tin, and would seriously pollute the environment, it is all very big to the harm of the mankind and environment.During PCB moves back tin, according to nitre
The composition and operating temperature of acid type tin stripper, tin are mainly under the conditions of pro-oxidant by the principle of nitric acid type tin stripper " backing off "
Oxidation of the dust technology to tin (0 valence), equation such as formula (1):
Sn+HNO3+H2O→Sn(H2O)6 2++HNO2 (1)
Sn(H2O)6 2+It is initially present form for move back tin ion after tin, while there is also some in tin removal waste liquor system
Electricity is right: Fe2+/Fe3+、Cu2+/Cu+、HNO3/HNO2、O2/H2O etc., their electrode potential is all compared with Sn4+/Sn2+Want high.So Sn
(H2O)6 2+Easily it is oxidized to Sn (H2O)6 4+, when system acidity reduces, it is hydrolyzed into Sn (H2O)2(OH)4(the positive stannic acid precipitating of white,
Both sexes dissolve in acid or alkali).Positive stannic acid becomes metastannic acid after placing dehydration, and metastannic acid has α, β two types, medium-sized α-
Metastannic acid be it is unformed, dissolve in soda acid, it is not soluble in water.β-type metastannic acid is crystalline structure, is insoluble in soda acid, not soluble in water.
General newly formed metastannic acid is α type, and β type is converted into after the long period.So newly going out in the tin-stripping wastewater of cylinder, largely
Valuable metal tin be in the form of positive stannic acid or metastannic acid exist, have the dioxy formed after minute quantity β type metastannic acid and dehydration
Change tin.The technology of existing line plate tin removal waste liquor processing mainly has neutralisation, the way of distillation, electrolysis method, membrane separation process, solvent extraction
Method.Wherein neutralisation is more mature, and application is relatively broad, brings economic benefit and environmental benefit to a certain extent, but existing
Neutralisation in technology generally existing following two problem at present: first is that pH higher when precipitating tin ion, usually 1.0~2.0
Between, this is needed using a large amount of alkaline solution, and the tin ion precipitated under the conditions of the pH often includes some other gold
Belong to ion, impurity content is high, and the purity of tin ion is lower.
There is precipitating pH higher, the big defects of alkaline solution dosage, in the tin precipitated for neutralisation by the application
Other heavy metal ion such as iron, copper containing more content, cause that tin purity is low, Theil indices are not high and direct strainability
Difference, production time higher cost, the problems such as seriously affecting the recycling of tin.Related improvement has been carried out to traditional neutralisation, has been led to
The pH value for overregulating system is in 0.5 to 0.8, while speed is added in strict control alkaline solution, then a certain amount of by adding
Flocculant improve filtrate strainability, compared at present need to adjust pH value between 1-2, can be realized stannic hydroxide produce
Theil indices in product are higher than 50%, and alkaline solution dosage is about traditional 1/2, optimizes tin recovery process, improves tin
Mud grade.
Embodiments herein is described in detail with reference to the accompanying drawing.
Fig. 1 shows the stream of the recovery method of tin metal in the nitric acid type tin-stripping wastewater in the application first aspect embodiment
Journey schematic diagram.
The recovery method of tin metal specifically includes in nitric acid type tin-stripping wastewater in the application first aspect embodiment:
S100: being added alkaline solution to set feed speed into the nitric acid type tin-stripping wastewater of tin metal to be recycled, is formed
PH value is in 0.5 to 0.8 mixed solution.
S200: after preset duration into the mixed solution be added setting content flocculant, formed precipitated phase product and
Liquid product.
S300: extracting and washs the precipitated phase product, obtains stanniferous metal product.
In traditional neutralisation, a large amount of experimental data is shown: since the partial size of stannic hydroxide powder is smaller, in pH <
Iron ion in 0.8 range in waste liquid can not be co-precipitated, and then hinder the formation of ferric hydroxide macroaggregate colloid, lead to it
Strainability is very poor, and the time cost of production is higher.The present embodiment is in 0.5 to 0.8 by adjusting pH, makes to have in mixed solution
There is the lesser stannic hydroxide powder of a large amount of partial sizes, then makes stannic hydroxide powder form cotton-shaped bulky grain glue by flocculant
Body, the effect of flocculant plays the role of the iron ion in traditional neutralisation, and then does not need when pH is in 0.5 to 0.8
Iron ion in waste liquid participates in the formation of colloidal substance, on the one hand can effectively realize the precipitating of stannic hydroxide, on the other hand heavy
(or containing minute quantity) iron ion is not contained in starch, further improves the tin purity in stannic hydroxide product, and then make
It obtains Theil indices and is higher than 50%.Simultaneously as pH is in 0.5 to 0.8, required alkaline solution dosage is substantially reduced, alkaline solution
Dosage is about traditional 1/2.Further, since it is only necessary to reach and the iron ion phase in waste liquid for the flocculant in the application
The tin hydroxide colloid to form co-precipitation seldom can be realized in same effect degree, dosage, and the dosage of flocculant is few, compared to biography
It unites flocculence (directly addition flocculant), dosage only needs traditional 1/3.
In the present embodiment, the charging speed for setting charging rate as the mixed solution can be formed in 40-60 minutes
Degree.Speed is added by strict control alkaline solution in the present embodiment, to avoid because local alkaline solution excessive concentration causes it
The localized precipitation of his metal.
In an alternative embodiment, alkaline solution can for it is conventional in alkalinity and side reaction it is few or without the molten of side reaction
Liquid, such as NaOH solution, Na2CO3Solution and NaHCO3One of solution is a variety of.
In addition, in one embodiment, the mass fraction of the flocculant is less than 3 ‰.Flocculant usage in the present embodiment
Far below traditional flocculence, select mass fraction that the embodiment of the present application can be realized less than 3 ‰.
Further, after the preset duration is greater than 30 minutes, 30 minutes, the pH value of mixed solution is evenly distributed, this
When be added flocculant be conducive to homogeneous precipitation.
Based on technical concept identical with the application first aspect embodiment, the application second aspect embodiment provides one kind
The recovery system of tin metal in nitric acid type tin-stripping wastewater, as shown in Figure 2, comprising:
Device 100 is neutralized, is added with to set feed speed into the nitric acid type tin-stripping wastewater of tin metal to be recycled alkaline molten
Liquid forms the mixed solution that pH value is in 0.5 to 0.8；
The flocculant of setting content is added after preset duration into the mixed solution for settler 200, forms precipitated phase
Product and liquid product；
Wash mill 300 extracts and washs the precipitated phase product, obtains stanniferous metal product.
Neutralizing device 100 can be traditional stirred tank or blending tank etc., and the application is with no restrictions.Alkaline solution
Feeding manner can be and be pumped into blending tank or reactor tank by micropump, by adjusting the revolving speed of micropump, and then adjust
Setting speed is the charging rate that the mixed solution can be formed in 40-60 minutes, i.e., adjusts pH value in 2-3 minutes
To 0.5 to 0.8.
Settler 200 can be subsider etc., and wherein on upper layer, precipitated phase product is located at lower layer and forms filter liquid product
Cake.
Wash mill 300 can be the filter of supersound washing slot, centrifuge washing device or routine, by crossing diafiltration
It washs, the application is without being limited thereto.
Based on technical concept same as the previously described embodiments, in preferred or optional embodiment, the matter of the flocculant
It is NaOH solution, Na greater than 30 minutes, the alkaline solution that score, which is measured, less than the 3 ‰, preset duration2CO3Solution and
NaHCO3One of solution is a variety of, and details are not described herein.
The recovery system of tin metal in the nitric acid type tin-stripping wastewater that present aspect embodiment provides can be realized stannic hydroxide production
Theil indices in product are higher than 50%, needed for during a kind of simple tin recovery processing for only carrying out tin removal waste liquor with method
Alkaline solution dosage and flocculant usage is wanted all to substantially reduce, alkaline solution dosage is about traditional 1/2, and flocculant usage is about
Traditional 1/3 realizes the effective control that obtained of real cost of production, and the production again in actual production treatment process
Raw wastewater flow rate also greatly reduces, and shortens the process cycle of tin removal waste liquor.
The above embodiments of the present application are described in detail below with reference to concrete scene, it is to be understood that, following scenes mention
Specific experiment parameter is supplied, but it's not limited to that by the application, those skilled in the art can rationally adjust according to the actual situation
Try out suitable parameter.
Implement scene 1
Tin removal waste liquor 1000mL is taken, under agitation, lye is controlled by micropump, speed is added, 4mol/L is added
Liquid alkaline solution, adjusting pH value is 0.5,3 ‰ flocculant is added after stirring 30min, until reacting after there is apparent layering
It is separated by solid-liquid separation after 30min, uses mass ratio to wash for the tap water of 1:3 filter cake, be then separated by solid-liquid separation, filtered
Theil indices are 50.8% in cake, and tin is not measured in filtrate.Filtrate obtained in experimentation all can be used at subsequent salkali waste
The neutralization raw material or thinned water of science and engineering skill.
Implement scene 2
Tin removal waste liquor 1000mL is taken, under agitation, lye is controlled by micropump, speed is added, 6mol/L is added
Liquid alkaline solution, adjusting pH value is 0.7,3 ‰ flocculant is added after stirring 30min, until reacting after there is apparent layering
It is separated by solid-liquid separation after 30min, uses mass ratio to wash for the tap water of 1:3 filter cake, be then separated by solid-liquid separation, filtered
Theil indices are 51.4% in cake, and tin is not measured in filtrate.Filtrate obtained in experimentation all can be used at subsequent salkali waste
The neutralization raw material or thinned water of science and engineering skill.
Implement scene 3
Tin removal waste liquor 1000mL is taken, under agitation, lye is controlled by micropump, speed is added, 8mol/L is added
Liquid alkaline solution, adjusting pH value is 0.8,3 ‰ flocculant is added after stirring 30min, until reacting after there is apparent layering
It is separated by solid-liquid separation after 30min, uses mass ratio to wash for the tap water of 1:3 filter cake, be then separated by solid-liquid separation, filtered
Theil indices are 54.6% in cake, and tin is not measured in filtrate.Filtrate obtained in experimentation all can be used at subsequent salkali waste
The neutralization raw material or thinned water of science and engineering skill.
Implement scene 4
Tin removal waste liquor 1000mL is taken, under agitation, lye is controlled by micropump, speed is added, 10mol/ is added
The liquid alkaline solution of L, adjusting pH value is 0.8, and 3 ‰ flocculant is added after stirring 30min, until reacting after there is apparent layering
It is separated by solid-liquid separation after 30min, uses mass ratio to wash for the tap water of 1:3 filter cake, be then separated by solid-liquid separation, filtered
Theil indices are 53.6% in cake, and tin is not measured in filtrate.Filtrate obtained in experimentation all can be used at subsequent salkali waste
The neutralization raw material or thinned water of science and engineering skill.
It could be aware that by above-mentioned implement scene, the recovery method of tin metal in nitric acid type tin-stripping wastewater provided by the present application
And system, it can be realized the Theil indices in stannic hydroxide product and be higher than 50%, the mass fraction of flocculant can be using 3 ‰
Can, and alkaline solution dosage is about traditional 1/2, and flocculant usage is about traditional 1/3.
All the embodiments in this specification are described in a progressive manner, same and similar portion between each embodiment
Dividing may refer to each other, and each embodiment focuses on the differences from other embodiments.Especially for system reality
For applying example, since it is substantially similar to the method embodiment, so being described relatively simple, related place is referring to embodiment of the method
Part explanation.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is contained at least one embodiment or example of this specification embodiment.In the present specification, to the signal of above-mentioned term
Property statement be necessarily directed to identical embodiment or example.
In addition, without conflicting with each other, those skilled in the art can be by difference described in this specification
The feature of embodiment or example and different embodiments or examples is combined.The foregoing is merely this specification implementations
The embodiment of example, is not limited to this specification embodiment.To those skilled in the art, this specification is implemented
Example can have various modifications and variations.All any modifications made within the spirit and principle of this specification embodiment are equal
Replacement, improvement etc., should be included within the scope of the claims of this specification embodiment.
Claims (10)
1. the recovery method of tin metal in a kind of nitric acid type tin-stripping wastewater characterized by comprising
Alkaline solution is added into the nitric acid type tin-stripping wastewater of tin metal to be recycled to set feed speed, forms pH value and is in
0.5 to 0.8 mixed solution；
The flocculant of setting content is added after preset duration into the mixed solution, forms precipitated phase product and liquid product；
The precipitated phase product is extracted and washed, stanniferous metal product is obtained.
2. recovery method according to claim 1, which is characterized in that the alkaline solution is NaOH solution, Na2CO3Solution
And NaHCO3One of solution is a variety of.
3. recovery method according to claim 1, which is characterized in that the mass fraction of the flocculant is less than 3 ‰.
4. recovery method according to claim 1, which is characterized in that the preset duration is greater than 30 minutes.
5. recovery method according to claim 1-4, which is characterized in that the charging rate that sets is can be
The charging rate of the mixed solution is formed in 40-60 minutes.
6. the recovery system of tin metal in a kind of nitric acid type tin-stripping wastewater characterized by comprising
Device is neutralized, alkaline solution is added to set feed speed into the nitric acid type tin-stripping wastewater of tin metal to be recycled, is formed
PH value is in 0.5 to 0.8 mixed solution；
The flocculant of setting content is added after preset duration into the mixed solution for settler, formed precipitated phase product and
Liquid product；
Wash mill extracts and washs the precipitated phase product, obtains stanniferous metal product.
7. recovery system according to claim 6, which is characterized in that the alkaline solution is NaOH solution, Na2CO3Solution
And NaHCO3One of solution is a variety of.
8. recovery system according to claim 6, which is characterized in that the mass fraction of the flocculant is less than 3 ‰.
9. recovery system according to claim 6, which is characterized in that the preset duration is greater than 30 minutes.
10. according to the described in any item recovery systems of claim 6-9, which is characterized in that the charging rate that sets is can be
The charging rate of the mixed solution is formed in 40-60 minutes.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910275995.5A CN110241308B (en) | 2019-04-08 | 2019-04-08 | Method and system for recovering tin metal in nitric acid type tin stripping wastewater |
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| CN201910275995.5A CN110241308B (en) | 2019-04-08 | 2019-04-08 | Method and system for recovering tin metal in nitric acid type tin stripping wastewater |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110484736A (en) * | 2019-09-29 | 2019-11-22 | 湖南仁发材料科技有限公司 | A method of copper removal is purified for zinc sulfate leaching liquid |
| CN111875146A (en) * | 2020-08-10 | 2020-11-03 | 清远市新绿环境技术有限公司 | Resource utilization system and method for tin-stripping wastewater |
| CN112573698A (en) * | 2020-11-26 | 2021-03-30 | 苏州美源达环保科技股份有限公司 | Method for recovering tin in PCB production process |
| CN112624181A (en) * | 2020-12-30 | 2021-04-09 | 惠州Tcl环境科技有限公司 | Method for preparing tin hydroxide by using tin-containing waste liquid |
| CN115557635A (en) * | 2022-09-30 | 2023-01-03 | 广东工业大学 | Method for treating nitric acid type tin stripping wastewater |
| CN115849434A (en) * | 2022-12-19 | 2023-03-28 | 昆山中环实业有限公司 | Method for purifying tin hydroxide from tin-stripping waste liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102351344A (en) * | 2011-07-08 | 2012-02-15 | 无锡市霄鹰环境科技有限公司 | Tin-bearing waste liquid recovery system and recovery technology |
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2019
- 2019-04-08 CN CN201910275995.5A patent/CN110241308B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351344A (en) * | 2011-07-08 | 2012-02-15 | 无锡市霄鹰环境科技有限公司 | Tin-bearing waste liquid recovery system and recovery technology |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110484736A (en) * | 2019-09-29 | 2019-11-22 | 湖南仁发材料科技有限公司 | A method of copper removal is purified for zinc sulfate leaching liquid |
| CN110484736B (en) * | 2019-09-29 | 2021-06-04 | 湖南仁发材料科技有限公司 | Method for purifying zinc sulfate leaching solution to remove copper |
| CN111875146A (en) * | 2020-08-10 | 2020-11-03 | 清远市新绿环境技术有限公司 | Resource utilization system and method for tin-stripping wastewater |
| CN111875146B (en) * | 2020-08-10 | 2021-04-16 | 清远市新绿环境技术有限公司 | Resource utilization system and method for tin-stripping wastewater |
| CN112573698A (en) * | 2020-11-26 | 2021-03-30 | 苏州美源达环保科技股份有限公司 | Method for recovering tin in PCB production process |
| CN112624181A (en) * | 2020-12-30 | 2021-04-09 | 惠州Tcl环境科技有限公司 | Method for preparing tin hydroxide by using tin-containing waste liquid |
| CN115557635A (en) * | 2022-09-30 | 2023-01-03 | 广东工业大学 | Method for treating nitric acid type tin stripping wastewater |
| CN115849434A (en) * | 2022-12-19 | 2023-03-28 | 昆山中环实业有限公司 | Method for purifying tin hydroxide from tin-stripping waste liquid |
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| CN110241308B (en) | 2021-04-09 |
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