CN108468050A - A kind of stripping tin liquor and its application in tin divests - Google Patents
A kind of stripping tin liquor and its application in tin divests Download PDFInfo
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- CN108468050A CN108468050A CN201810424018.2A CN201810424018A CN108468050A CN 108468050 A CN108468050 A CN 108468050A CN 201810424018 A CN201810424018 A CN 201810424018A CN 108468050 A CN108468050 A CN 108468050A
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- Prior art keywords
- tin
- stripping
- tin liquor
- hydrogen peroxide
- liquor
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Classifications
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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
-
- 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
- C23F1/08—Apparatus, e.g. for photomechanical printing surfaces
-
- 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
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a kind of stripping tin liquors, it is characterised in that：Every liter of stripping tin liquor includes following material：20 60ML of hydrogen peroxide, 300 700ML/L of pyrovinic acid, it includes also 0 6g benzotriazole to be shelled at every liter in tin liquor, remaining is water.Stripping tin liquor disclosed in this invention is using hydrogen peroxide as oxidant; pyrovinic acid is low to ground copper corrosion performance simultaneously as organic acid offer strong acid environment; benzotriazole is added as ground copper protective agent; tin metal is carried out to divest; avoid a large amount of alkali consumption of conventional method; reduce waste discharge amount, energy conservation and environmental protection.
Description
Technical field
The present invention relates to tin metals to divest technical field, more particularly to a kind of stripping tin liquor and its application in tin divests.
Background technology
In the prior art, the divesting technology of tin metal generally uses nitric acid for the stripping tin liquor of principal component.Nitric acid is principal component
Stripping tin liquor generate chemical reaction when nitric acid decompose, generate penetrating odor, operating environment is poor, is unfavorable for the peace of operating personnel
Complete and environment purification.As environmental protection administration is more and more tighter to controls such as ammonia nitrogens in industrial wastewater discharge, and circuit board industry
Interior still very big to ammonium hydroxide, nitric acid usage amount, environmental protection pressure is very big.
For the waste liquid that this processing method generates in the prior art due to containing a large amount of nitric acid, wastewater treatment is difficult.Sillim
Category is dissolved in nitric acid, and recovery process is complicated, and wasting manpower and material resources be easy to cause environmental pollution.Stripping in existing circuit board plant
Tin waste liquid is recycled by producer, but shell washing nitrogen content after tin allows concentration of emission considerably beyond environmental protection administration, nitrogenous dense
It is outer processing of discharging or entrust after dilution is handled to spend in high waste water major part circuit board plant, and two methods cost is all higher, and
There are environmentally friendly risks.And shell tin waste liquid in existing stripping tin method and be not easy to recycle, waste of resource.
In order to solve the problems in the prior art, it needs to research and develop the stripping tin liquor that a kind of nitrogen content is low, environmentally friendly.
Invention content
Purpose of the present invention is to：Overcome the shortcomings of the prior art, solves problems of the prior art, one kind is provided
Tin liquor and its application in tin divests are shelled, nitric acid is free of, wastewater treatment is simple, reduces waste water and exhausted air quantity, environmental protection and energy saving.
The technical scheme is that：
A kind of stripping tin liquor, it is characterised in that：Every liter of stripping tin liquor includes following material：Hydrogen peroxide 20-60ML, methyl
Sulfonic acid 300-700ML/L, it includes also 0-6g benzotriazole to be shelled at every liter in tin liquor, remaining is water.
Preferably, the amount of contained hydrogen peroxide is 30-50ML in every liter of stripping tin liquor.
Preferably, the amount of contained pyrovinic acid is 400-600ML in every liter of stripping tin liquor.
Preferably, the amount of contained benzotriazole is 0-3 grams in every liter of stripping tin liquor.
A kind of application for shelling tin liquor in tin divests, it is characterised in that：It is inclined that hydrogen peroxide reacts production with pyrovinic acid with tin
Diluted acid is completed tin and is divested, and the reaction equation of the stripping tin liquor stripping tin is：
Sn+H2O2+2CH3SO3H→Sn(CH3SO3)2+2H2O
Sn(CH3SO3)2+H2O2+H2O→H2SnO3+2CH3SO3H。
Preferably, tin liquor is shelled in tin divests in application, also collocation centrifuge is practical, and separation solid phase is the inclined of reaction generation
Diluted acid, the direct recycling of liquid phase.
Preferably, stripping tin liquor in tin divests in application, also set up cupric electrolysis retracting device, cupric electrolysis retracting device and stripping
Molten tin bath is connected to, for removing the copper ion in stripping molten tin bath.
Preferably, the stripping tin liquor further includes hydrogen peroxide on-line analysis device, hydrogen peroxide on-line analysis device and hydrogen peroxide
Automatic adding device is connected with stripping molten tin bath, for analyzing hydrogen peroxide surplus, and starts hydrogen peroxide certainly according to hydrogen peroxide surplus
Dynamic adding set adds hydrogen peroxide automatically.
Advantages of the present invention：
1, for stripping tin liquor disclosed in this invention using hydrogen peroxide as oxidant, pyrovinic acid provides strong acid environment as organic acid
Low to ground copper corrosion performance simultaneously, addition benzotriazole carries out tin metal and divests, avoid tradition as ground copper protective agent
The a large amount of alkali consumption of method, reduces waste discharge amount, energy conservation and environmental protection.
2, washing waste water is free of ammonia nitrogen after stripping tin liquor stripping tin disclosed in this invention, can be with direct emission, without especially place
Reason, is good for the environment, and saves environmental protection treatment cost.
3, by using centrifuge detach stripping tin generate metastannic acid, shell tin liquor energy cycling and reutilization, environmental protection, save at
This.
4, centrifuge is link-suspended basket centrifuge or tube centrifuge operating high speed, can be sufficiently separated metastannic acid.
5, the copper that ground copper corrosion introduces when stripping tin liquor disclosed in this invention eliminates stripping tin using cupric electrolysis retracting device
Ion completes recycling for stripping tin liquor, reduces discharge of wastewater.
6, stripping tin liquor disclosed in this invention consumes hydrogen peroxide and hydrogen peroxide easily decomposes, so more environmentally friendly；Institute of the present invention
Disclosed stripping tin liquor is stablized using hydrogen peroxide on-line analysis device and hydrogen peroxide automatic adding device control hydrogen peroxide concentration, it is ensured that
It is consistent to shell tin rate.High degree of automation simultaneously saves manpower.
Specific implementation mode
Technical solution of the present invention is described in detail with reference to preferred embodiment.
The present invention discloses a kind of stripping tin liquor, and every liter of stripping tin liquor includes following material：Hydrogen peroxide 20-60ML, methyl
Sulfonic acid 300-700ML/L, it includes also 0-6g benzotriazole to be shelled at every liter in tin liquor, remaining is water.Stripping disclosed in this invention
For tin liquor using hydrogen peroxide as oxidant, pyrovinic acid provides strong acid environment while, addition low to ground copper corrosion performance as organic acid
Benzotriazole carries out tin metal and divests as ground copper protective agent, avoids a large amount of alkali consumption of conventional method, reduces waste discharge
Amount, energy conservation and environmental protection.
Preferred embodiment, every liter of amount for shelling contained hydrogen peroxide in tin liquor is 30ML, and every liter is shelled contained methyl sulphur in tin liquor
The amount of acid is 600ML, and every liter of amount for shelling contained benzotriazole in tin liquor is 2 grams, remaining is water.Stripping tin disclosed in this invention
Liquid shell tin after washing waste water be free of ammonia nitrogen, can with direct emission, without especially processing, be good for the environment, save environmental protection treatment at
This.
Another preferred embodiment, every liter of amount for shelling contained hydrogen peroxide in tin liquor is 40ML, and every liter is shelled contained first in tin liquor
The amount of base sulfonic acid is 500ML, and every liter of amount for shelling contained benzotriazole in tin liquor is 1.5 grams, remaining is water.
A kind of application for shelling tin liquor in tin divests, it is characterised in that：It is inclined that hydrogen peroxide reacts production with pyrovinic acid with tin
Diluted acid is completed tin and is divested, and the reaction equation of the stripping tin liquor stripping tin is：
Sn+H2O2+2CH3SO3H→Sn(CH3SO3)2+2H2O
Sn(CH3SO3)2+H2O2+H2O→H2SnO3+2CH3SO3H.Stripping tin liquor disclosed in this invention is oxidation with hydrogen peroxide
Agent, pyrovinic acid is low to ground copper corrosion performance simultaneously as organic acid offer strong acid environment, and addition benzotriazole is as ground
Copper protective agent carries out tin metal and divests, and avoids a large amount of alkali consumption of conventional method, reduces waste discharge amount, energy conservation and environmental protection.Copper is tin
Underlying metal, stripping tin liquor be easy copper ion.
Preferably, tin liquor is shelled in tin divests in application, also collocation centrifuge is practical, and separation solid phase is the inclined of reaction generation
Diluted acid, the direct recycling of liquid phase.The metastannic acid that stripping tin generates is detached by using centrifuge, stripping tin liquor can recycle again sharp
With environmental protection is cost-effective.Centrifuge is link-suspended basket centrifuge or tube centrifuge operating high speed, can be sufficiently separated metastannic acid.
Preferably, stripping tin liquor in tin divests in application, also set up cupric electrolysis retracting device, cupric electrolysis retracting device and stripping
Molten tin bath is connected to, for removing the copper ion in stripping molten tin bath.Stripping tin liquor disclosed in this invention is eliminated using cupric electrolysis retracting device
The copper ion that ground copper corrosion introduces when shelling tin completes recycling for stripping tin liquor, reduces discharge of wastewater.
Preferably, the stripping tin liquor further includes hydrogen peroxide on-line analysis device, hydrogen peroxide on-line analysis device and hydrogen peroxide
Automatic adding device is connected with stripping molten tin bath, for analyzing hydrogen peroxide surplus, and starts hydrogen peroxide certainly according to hydrogen peroxide surplus
Dynamic adding set adds hydrogen peroxide automatically.Stripping tin liquor disclosed in this invention consumes hydrogen peroxide and hydrogen peroxide easily decomposes, so than
It is more environmentally friendly；Stripping tin liquor disclosed in this invention controls dioxygen using hydrogen peroxide on-line analysis device and hydrogen peroxide automatic adding device
Water concentration is stablized, it is ensured that stripping tin rate is consistent.High degree of automation simultaneously saves manpower.
Washing waste water is free of ammonia nitrogen after stripping tin liquor stripping tin disclosed in this invention, can be handled without special with direct emission,
It is good for the environment, saves environmental protection treatment cost.
Tin cost recovery is reduced when stripping tin liquor stripping tin disclosed in this invention, so that production cost is big in circuit board plant
Amplitude reduction.
Tradition stripping tin liquor shells tin method with nitric acid and carries out liquid waste processing, and nitric acid is neutralized using NAOH, tin mud (metastannic acid) point
From nitrogen can not be disposed completely.
Traditional industry wet method metastannic acid uses following equation for reaction principle：
Metastannic acid generates 3Sn+4HNO3+H2O→3H2SnO3+4NO
Exhaust-gas treatment 4NO+O2→2NO2
Exhaust-gas treatment 2NO2+Na2CO3→NaNO2+NaNO3+CO2
This obtained waste liquid of conventional method needs to carry out denitrogenation processing, of high cost, not environmentally.
The reaction that the present invention shells tin liquor stripping tin uses following chemical principle,
Sn+H2O2+2CH3SO3H→Sn(CH3SO3)2+2H2O
Sn(CH3SO3)2+H2O2+H2O→H2SnO3+2CH3SO3H
Metastannic acid in stripping tin liquor is extracted by the above chemical principle and is used as metastannic acid semi-finished product, and it is de- to neutralize centrifugal drying
Finished product is metastannic acid colloid or powder after water.Washing waste water is free of ammonia nitrogen after shelling tin, can be handled without special with direct emission,
It is good for the environment, saves environmental protection treatment cost.It shells tin ability to stablize, the content of tin in stripping tin time control pharmacy bath will not be because of medicine
Theil indices increase by two and cause to shell the decline of tin ability in bath.
And the stripping tin liquor of the present invention, make to shell tin liquor cycling and reutilization when shelling tin, further reduce waste water and exhausted air quantity,
Environmental protection and energy saving.
Still there are many embodiment, all technical sides formed using equivalents or equivalent transformation by the present invention
Case is within the scope of the present invention.
Claims (8)
1. a kind of stripping tin liquor, it is characterised in that：Every liter of stripping tin liquor includes following material：Hydrogen peroxide 20-60ML, methyl sulphur
Sour 300-700ML/L, it includes also 0-6g benzotriazole to be shelled at every liter in tin liquor, remaining is water.
2. stripping tin liquor according to claim 1, it is characterised in that：The amount of contained hydrogen peroxide is 30- in every liter of stripping tin liquor
50ML。
3. stripping tin liquor according to claim 1, it is characterised in that：The amount of contained pyrovinic acid is 400- in every liter of stripping tin liquor
600ML。
4. stripping tin liquor according to claim 1, it is characterised in that：The amount of contained benzotriazole is 0- in every liter of stripping tin liquor
3 grams.
5. a kind of application of stripping tin liquor in tin divests, it is characterised in that：It is partially dilute that hydrogen peroxide reacts production with pyrovinic acid with tin
Acid is completed tin and is divested, and the reaction equation of the stripping tin liquor stripping tin is：
Sn+H2O2+2CH3SO3H→Sn(CH3SO3)2+2H2O
Sn(CH3SO3)2+H2O2+H2O→H2SnO3+2CH3SO3H。
6. application of the stripping tin liquor according to claim 5 in tin divests, it is characterised in that：Stripping tin liquor is answered in tin divests
Used time, centrifuge of also arranging in pairs or groups is practical, and separation solid phase is the inclined diluted acid that reaction generates, the direct recycling of liquid phase.
7. application of the stripping tin liquor according to claim 5 in tin divests, it is characterised in that：Stripping tin liquor is answered in tin divests
Used time, also set up cupric electrolysis retracting device, cupric electrolysis retracting device be connected to stripping molten tin bath, for remove shell copper in molten tin bath from
Son.
8. application of the stripping tin liquor according to claim 5 in tin divests, it is characterised in that：The stripping tin liquor further includes double
Oxygen water on-line analysis device, hydrogen peroxide on-line analysis device is connect with hydrogen peroxide automatic adding device and stripping molten tin bath, for analyzing
Hydrogen peroxide surplus, and hydrogen peroxide automatic adding device is started according to hydrogen peroxide surplus and adds hydrogen peroxide automatically.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810424018.2A CN108468050A (en) | 2018-05-07 | 2018-05-07 | A kind of stripping tin liquor and its application in tin divests |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810424018.2A CN108468050A (en) | 2018-05-07 | 2018-05-07 | A kind of stripping tin liquor and its application in tin divests |
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| Publication Number | Publication Date |
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| CN108468050A true CN108468050A (en) | 2018-08-31 |
Family
ID=63260985
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|---|---|---|---|
| CN201810424018.2A Pending CN108468050A (en) | 2018-05-07 | 2018-05-07 | A kind of stripping tin liquor and its application in tin divests |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109440109A (en) * | 2018-11-13 | 2019-03-08 | 南通赛可特电子有限公司 | A kind of tin stripping liquid and preparation method thereof |
| CN112111741A (en) * | 2020-09-25 | 2020-12-22 | 深圳市祺鑫环保科技有限公司 | Tin stripping liquid copper protecting agent and tin stripping liquid |
| CN112499670A (en) * | 2020-12-10 | 2021-03-16 | 广东臻鼎环境科技有限公司 | Method for preparing stannous chloride crystals by using PCB tin stripping waste liquid |
| CN112663063A (en) * | 2020-12-10 | 2021-04-16 | 广东臻鼎环境科技有限公司 | Tin stripping liquid and method for recycling tin stripping liquid after application |
| CN114323885A (en) * | 2021-12-06 | 2022-04-12 | 万华化学集团股份有限公司 | Double-phase stainless steel etching agent and etching method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112499670A (en) * | 2020-12-10 | 2021-03-16 | 广东臻鼎环境科技有限公司 | Method for preparing stannous chloride crystals by using PCB tin stripping waste liquid |
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| CN114323885A (en) * | 2021-12-06 | 2022-04-12 | 万华化学集团股份有限公司 | Double-phase stainless steel etching agent and etching method |
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Application publication date: 20180831 |