CN107268007A - A kind of method of tin removal waste liquor circular regeneration - Google Patents
A kind of method of tin removal waste liquor circular regeneration Download PDFInfo
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- CN107268007A CN107268007A CN201710458430.1A CN201710458430A CN107268007A CN 107268007 A CN107268007 A CN 107268007A CN 201710458430 A CN201710458430 A CN 201710458430A CN 107268007 A CN107268007 A CN 107268007A
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- tin
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- removal waste
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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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
-
- 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
- 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
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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 provides a kind of method of tin removal waste liquor circular regeneration, including implement to move back that tin produces and produce tin removal waste liquor moves back tin production operation step A；Collect the storage operating procedure B of tin removal waste liquor；Pre-treatment is carried out to tin removal waste liquor, tin removal waste liquor can be divided into sn rich phase and lean tin phase, be respectively delivered to carry tin device and the operating procedure C except ketone device；Copper removal operating procedure D for reducing copper content in tin removal waste liquor；For will reclaim metallic tin and removed the preparing solution after metallic copper into the regenerative operation step E for moving back the new liquid of tin；The storage operating procedure F of the new liquid of tin is moved back for storing, and tin operating procedure G is carried by what the tin in stanniferous concentrate became tin product.The method for the tin removal waste liquor circular regeneration that the present invention is provided, not only device structure is simple, production and processing cost is low, field conduct operation is easy, can more accomplish the cycling and reutilization of material, is a set of environment-friendly type production equipment that disclosure satisfy that clean manufacturing requirement.
Description
Technical field
The invention belongs to the cycling and reutilization field of heavy metal acid waste liquid, more particularly to a kind of tin removal waste liquor circular regeneration
Method.
Background technology
With the development of electronics industry and associated metal material, tin plating application increasingly increases on metallic copper, on metallic copper
The recovery of tin is also widely used.Annual domestic tin removal waste liquor amount reaches millions of tons, and in existing processing method, fails
Accomplish the reuse of tin stripper, simply simple and crudely after recovery section tin, be discharged to outside in natural environment, pollute extremely serious, and
There are substantial amounts of tin decoction direct losses of moving back to fall.
Tin stripping liquid, also known as tin stripper or stripping tin liquor, are one of primary chemical materials for using in printed wiring board production,
Stripping for tin coating, leypewter coating and soldered joint.Suitable for electronic component, copper table in circuit board manufacturing process
The stripping of the tin/layer of lead-tin alloy in face, such as, in wiring board manufacture, using alkaline etching process, wherein just having tin plating and moving back
The process of tin, can be operated with immersion or mechanical spraying method.As the removing agent of tin/layer of lead-tin alloy of copper/nickel surface,
Requirement to tin stripping liquid is higher, it is desirable to which it is to Copper substrate and Ni substrate almost not damaged, and can remove patina mark makes Copper substrate
Light is such as new and corrosion-free to base resin and plastic cement and ink word etc..In addition, also require tin stripping liquid to move back tin amount big,
Move back tin speed fast, and can persistently be efficiently used.
Printed wiring board industry is to produce a more industry of tin removal waste liquor, especially in recent years, printed wiring board
And related industry is quickly grown, a large amount of tin removal waste liquors can be produced in electrotinning and the production for moving back tin.In printed wiring board production
During, tenor and acidity are higher in the tin removal waste liquor discharged, and its main component is as shown in table 1.
The main component of the tin removal waste liquor of table 1
| Component | Actual constituent | Content (wt) % |
| Inorganic acid | Nitric acid, sulfonic acid, hydrofluoric acid | 20-30 |
| Metal salt | Copper nitrate, ferric nitrate, former stannic acid | 10-20 |
| It is other | Additive, stabilizer, copper-protection agent | 6-20 |
It can be seen that, tin removal waste liquor has following feature：
1) Theil indices are high, concentration of nitric acid is big and system is complicated.Waste liquid amount is produced in Tui Xishi printed wiring boards enterprise maximum
One of process, heavy metal in waste liquid species is more and content is high, and pollution index is high, and contained in traditional nitric acid spent solder stripper
Stabilizer, additive, copper-protection agent etc. contain substantial amounts of organic compound, including multiple ring aromatic compound, heterocyclic compound,
High molecular polymer etc., along with the nitric acid of big concentration, environmental hazard is very big.
2) the solution difficulty of traditional nitric acid type tin stripper, its complex disposal process, and contaminant component is big, processing cost
Height, environmentally friendly cost is heavy.
At present, the international and domestic main methods to tin removal waste liquor are neutralization precipitation method, concentration method and latest report
Oxalate precipitation method.
Neutralization precipitation method is neutralized using alkaline materials such as sodium hydroxide, calcium hydroxide, ammoniacal liquor, sodium carbonate, sodium acid carbonates and moved back
Nitric acid in tin waste liquid, metal is separated in the form of hydroxide is precipitated, obtain various metals hydroxide it is mixed
Compound.Though neutralization precipitation method can reach the purpose for neutralizing nitric acid, reclaiming metal, ammonium nitrate, sodium nitrate etc. are generated again simultaneously
New nitrate, subsequent treatment still highly difficult difficulty certainly will cause serious azotate pollution, and alkali consumption is big, cost
Height, discharged wastewater met the national standard difficulty is big.
Concentration method is filtered after tin removal waste liquor is boiled, and is added sulfur-containing compound in filtrate, is sufficiently stirred for making in filtrate
Metal ion reaction generation precipitation, it is to be precipitated completely after add flocculant, be further separated by filtration, after measured in clear liquid
Tin, copper content can be down to below 2g/L.There are two big defects in concentration method, one is that thermophilic digestion can cause nitric acid largely to decompose,
The danger of nitrogen oxides is bigger, and more difficult processing；Two be that added sulfur-containing compound can introduce new element sulphur
To moving back in tin recovered liquid, with the increase of cycle-index, the enriching quantity of element sulphur is also more and more, and influence at last is recycled
Decoction effect.
Oxalate precipitation method, is added in tin removal waste liquor using oxalic acid as release agent and is chemically treated, and can not only be produced
Copper, tin sediment so that the copper in the tin removal waste liquor, tin ion to be reclaimed, and by tin removal waste liquor it is chemically treated after produce
Reaction solution carry out adjustment of formula, obtain new tin stripper, this has not only accomplished that this waste water is handled to reaction solution, and
Realize twice laid.But, oxalate precipitation method introduces a large amount of oxalic acid during separation copper and tin, and oxalic acid has reduction nitre
The effect of acid oxidase, can not thoroughly be removed from recovered liquid, and the material of recycling, which can be substantially reduced, to move back tin effect and move back
Tin speed.Moreover, the granularity of cupric oxalate and tin oxalate is very small, it is also difficult to be completely separated from liquid phase.
To solve above-mentioned neutralization precipitation method, concentration method and the defect of oxalate precipitation method, Sichuan Lv Yuan cumulatives environmental protection science and technology has
Limit responsible company (Sichuan GREEN Green Sci-Tech Co., Ltd) puts into substantial amounts of manpower and materials and tackled key problems the problem,
And achieve excellent achievement --- a kind of method of tin removal waste liquor circular regeneration is invented, for the time being referred to as GREEN-TRT skills
Art, can realize that directly using tin removal waste liquor be that raw material extracts metallic tin therein and metallic copper, and will extract the medicine after metal
Liquid, which is reclaimed, to carry out the new liquid of tin stripper and prepares again, then will move back the new liquid of tin and be recycled to and move back in tin producing line, tin life is moved back for normal
Production is used.
The invention provides a kind of method of tin removal waste liquor circular regeneration, the tin in tin removal waste liquor, copper are reclaimed respectively, its
Its composition returns to production system, and does not introduce new material, so as to ensure that the stability and high efficiency for moving back the new liquid of tin.The invention
Creation not only realizes the recovery of copper, tin resource, also achieves the cycling and reutilization of other compositions in tin removal waste liquor, and reaction
Mild condition, other methods processing energy consumption and cost than having reported are significantly reduced, and non-secondary pollution thing is discharged out, are a kind of
Environmentally friendly technical method.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of method of tin removal waste liquor circular regeneration, it is intended to which reduction is moved back
The processing energy consumption and cost of tin waste liquid, while eliminating secondary pollution, reduce the harm to the mankind, other biological and environment, and in fact
The recycling of existing resource.
The present invention is achieved in that a kind of method of tin removal waste liquor circular regeneration, including for being carried out to tin removal waste liquor
Pre-treatment, can make sn-containing compound in tin removal waste liquor be concentrated to sn rich phase, and tin removal waste liquor is divided into sn rich phase and lean tin phase,
It is respectively delivered to carry tin device and the operating procedure C except ketone device；Copper removal for reducing copper content in tin removal waste liquor operates step
Rapid D；For will reclaim metallic tin with except the preparing solution after metallic copper is into the regenerative operation step E for moving back the new liquid of tin；And will
What the tin in stanniferous concentrate became tin product carries tin operating procedure G；It is also possible that to move back tin for implementation and produce and produce and moves back
Tin waste liquid moves back tin production operation step A；It is also possible that the storage operating procedure B for collecting tin removal waste liquor；It is also possible to bag
Include the storage operating procedure F that the new liquid of tin is moved back for storing.
It is preferred that, each operating procedure is sequentially carried out：
After tin removal waste liquor is by tin removal waste liquor pre-treatment operating procedure, tin removal waste liquor is divided into sn rich phase and lean tin phase；
Sn rich phase carries out carrying tin by putting forward tin operating procedure, obtains stanniferous product；
Lean tin carries out copper removal by copper removal operating procedure, obtains regenerated liquid and metallic copper；
And/or regenerated liquid can be allocated by moving back the new liquid regenerative operation step of tin, must move back the new liquid of tin；
And/or the new liquid of tin is moved back by moving back the new liquid storage operating procedure storage of tin, in case moving back tin production；
And/or tin removal waste liquor stores operating procedure by tin removal waste liquor and stored, in case tin removal waste liquor pre-treatment.
It is preferred that, the tin removal waste liquor pre-treatment operating procedure is operated by tin removal waste liquor pre-treatment, is made in tin removal waste liquor
Sn-containing compound is condensed into sn rich phase, and the difference of sn rich phase and lean tin mutually because of density and composition has obvious line of demarcation, and leads to
Tin removal waste liquor pre-treatment operation is crossed to produce it respectively.Generally, the density of the density ratio tin removal waste liquor of sn rich phase is big, and lean tin is mutually close
Degree is smaller than the density of tin removal waste liquor.
It is preferred that, the proportion of the lean tin phase is 1.00g/cm3-1.35g/cm3, the proportion of the sn rich phase is 1.10g/
cm3-1.80g/cm3。
It is preferred that, it is described to put forward tin operating procedure, it is to be sufficiently mixed heavy tin agent with sn rich phase, when sn-containing compound is from solution
After middle precipitation, sn-containing compound is reclaimed.
It is preferred that, the copper removal operating procedure is to remove the copper electrochemical reduction in lean tin phase into elemental copper, after copper removal
The namely regenerated liquid of solution.
It is preferred that, the copper removal operating procedure, its electrochemical reduction current density is 80A/ ㎡ -800A/ ㎡.
It is preferred that, it is described to move back the new liquid regenerative operation step of tin, refer to use nitric acid and/or copper-protection agent and/or stabilizer
And/or water is allocated to regenerated liquid, move back the new liquid performance indications of tin to reach or meet production requirement.
It is preferred that, move back the new liquid regenerative operation step of tin, it is characterised in that contain three in the copper-protection agent and/or stabilizer
Valency Fe3+。
It is preferred that, the storage operating procedure is by tin removal waste liquor or moves back the new liquid of tin and is stored in acid resistance, resistance to oxidation
In the container of property and corrosion resistance.
It is preferred that, the material conveying between each operating procedure can use pipeline or other any mode of movements.
Compared with prior art, the beneficial effects of the present invention are：The tin removal waste liquor circulation regeneration method that the present invention is provided,
Operating procedure is handled before also including tin removal waste liquor in prior art basis, tin operating procedure is put forward, copper removal operating procedure, and/or
The new liquid regenerative operation step of tin is moved back, and/or moves back the new liquid storage operating procedure of tin, and/or tin removal waste liquor storage operating procedure.Utilize
Tin removal waste liquor pre-treatment operating procedure just can obtain sn rich phase and lean tin phase；Subsidence effect is produced to tin using heavy tin agent, tin is carried
Just the tin in sn rich phase can be recovered in operating procedure in stanniferous product；Using copper removal operating procedure, make in nitric acid screener
Under, the copper content in lean tin phase can be down to below 5.0g/L, decoction is reached regeneration level, and reclaim to obtain metallic copper
Product；Proceed adjustment of formula to reclaiming the regenerated liquid after copper using the new liquid regenerative operation step of tin is moved back, prepare new move back
Xi Shui, is referred to as to move back the new liquid of tin, is stored in and moves back in the new liquid storage operating procedure of tin, in case moving back tin production and application.
The tin removal waste liquor circulation regeneration method that the present invention is provided, realizes tin stripping liquid cycling and reutilization, and will constantly dissolve
Tin element into tin stripping liquid all becomes stanniferous Product recycling, and copper is then reclaimed in the form of electrodeposit metals copper, moves back tin
Other compositions in liquid can be recycled infinitely, and the introducing of non-secondary pollution thing, eliminate secondary pollution, be reduced to people
The harm of class, other biological and environment, and realize recycling for resource.
Compact arrangement of equipment involved by the inventive method rationally, is effectively utilized the various materials in tin removal waste liquor, and
And serialization steady production can be realized, operating also, more safety is easily-controllable, is the innovation and creation with practical application.
Brief description of the drawings
By the way that shown in accompanying drawing, the above of the invention and purpose, feature and advantage will become apparent from, in accompanying drawing and word
Identical operating procedure code name indicates identical part in description.Accompanying drawing deliberately is not drawn by true form, size equal proportion,
But be purport of the invention is shown, it is not intended to limit the present invention.
Fig. 1 is the process flow diagram of tin removal waste liquor circulation regeneration method provided in an embodiment of the present invention.It is each in accompanying drawing
Plant the explanation of code name.
Operating procedure code name explanation：
Operating procedure A --- move back tin production operation step.
Operating procedure B --- tin removal waste liquor stores operating procedure, for collecting and/or storing tin removal waste liquor.
Operating procedure C --- tin removal waste liquor pre-treatment operating procedure, pre-treatment is carried out for the tin removal waste liquor to collection, with
Sn-containing compound is set in tin removal waste liquor to be condensed into sn rich phase, and Theil indices reduction turns into lean tin phase in remaining decoction, and by richness
The tin phase operating procedure mutually separated with lean tin.
Operating procedure D --- except ketone operating procedure, the II that adds materials in proportion (nitric acid screener and/or water), for dropping
The operating procedure of copper content in low tin removal waste liquor.
Operating procedure E --- the new liquid regenerative operation step of tin is moved back, for by (or copper content is up to standard) after lean tin phase copper removal
Solution, the III that adds materials in proportion (nitric acid and/or copper-protection agent and/or stabilizer and/or water) is agitated to dissolve and be well mixed
Obtain moving back the operating procedure of the new liquid of tin afterwards.
Operating procedure F --- the new liquid storage operating procedure of tin is moved back, the operating procedure of the new liquid of tin is moved back for storing.
Operating procedure G --- tin operating procedure is put forward, the I that adds materials in proportion (heavy tin agent and/or water), by stanniferous concentrate
In tin become tin product.
Product designation explanation：
Product is 1. --- stanniferous product.
Product is 2. --- metal copper products.
Product is 3. --- tin part is moved back, i.e., object, material after top layer tin is decorporated.
Material code name explanation：
Material I --- heavy tin agent and/or water.
Material II --- nitric acid screener and/or water.
Material III --- nitric acid and/or copper-protection agent and/or stabilizer and/or water.
Material IV --- tin plating part and/or tin part is covered, such as tin plate, tin coating water tank, cover tin copper material.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.
Many details are elaborated in the following description to facilitate a thorough understanding of the present invention, still the present invention can be with
Using implementing different from other manner described herein, those skilled in the art can be in the feelings without prejudice to intension of the present invention
Similar popularization is done under condition, therefore following public specific embodiment is not intended to limit the present invention.
Secondly, the present invention is described in detail with reference to schematic diagram, when the embodiment of the present invention is described in detail, for purposes of illustration only, right
Material mode of movement in method may use pumping or other addition manners, arrange and like according to the equipment at user scene
Good, the selection of mode of movement has diversity, it is thus impossible to because whether provided with pumping or whether pipeline and limit this hair
The scope of bright protection.
Just as described in the background section, or existing tin removal waste liquor treatment technology does not just account for following for waste liquid at all
Ring is recycled, or introducing secondary pollution in metal recovery process, or produces new discarded object；Just introduce new thing
Expect and move back in tin system, directly influence and the stability of the new liquid of tin is moved back during reuse and tin effect is moved back.
To find out its cause, the nitric acid content being primarily due in tin stripper is excessive, complicated components, various metals salt are miscible in together
In one system, organic matter and inorganic matter coexist and cause each component in tin stripper to reclaim difficult.Normal operating conditions moves back tin
In water, the nitric acid containing mass fraction 25%-35%, the copper-protection agent containing 4.5-30%, 0.5%-20% stabilizer, with
The Theil indices more and more higher in the progress of tin production, solution, i.e. metallic tin is moved back ceaselessly to occur to chemically react and be dissolved in reaction solution
In.Therefore, appropriate ferric ion Fe can be added in the process for preparation of nitric acid type tin stripping liquid of the present invention3+, it is acted on
Predominantly by Sn2+Further reaction generates Sn4+, so as to avoid the redox reaction of nitric acid and metallic tin generation and generate nitrogen
Oxide.
Shown in the reaction mechanism that metallic tin and Bivalent Tin change in the solution such as reaction equation (1)~reaction equation (3)：
Sn+2HNO3=Sn (NO3)2+H2↑ (1)
Sn2++2Fe3+=Sn4++2Fe2+ (2)
Sn4++4H2O=H4SnO4↓+4H+ (3)
So, reaction end gas is mainly hydrogen, and final stanniferous product is stannic acid.
The Fe produced in reaction equation (2)2+, it is not sufficiently stable in atmosphere, ferric iron can be generated with the oxygen reaction in air
Ion Fe3+, such as shown in reaction equation (4).
4Fe2++4H++O2(air)=2H2O+4Fe3+ (4)
In addition, because the tin on tin plating part is covered in other metallic substrates, especially printed wiring
Board industry, most sheet material is all that tin is overlayed on copper, so during tin is moved back, it is desirable to which tin should be moved back to clean try one's best again not
Copper-based bottom is injured, this just has compared with strict requirements to the erosion copper speed of tin stripper, i.e., on the premise of satisfaction moves back tin speed, lost
Copper speed is more low better.Shown in reaction mechanism such as reaction equation (5)~reaction equation (8) of tin stripper erosion copper：
Cu+4NHO3(dense)=Cu (NO3)2+2NO2↑+2H2O (5)
Cu+4H++2NO3 -=Cu2++2NO2↑+2H2O (6)
Cu+Fe3+=Cu++Fe2+ (7)
Cu2++ Cu=2Cu+ (8)
In fact, move back tin production when, in order to prevent reaction heat accumulation and cause system temperature is raised suddenly, cause nitric acid divide
Solve or move back sheet tin the phenomenon such as to grow dim, tin temperature control can will be typically moved back at 0-35.0 DEG C, in this temperature range, ferrous ion
Fe2+With oxygen reaction generation ferric ion Fe in air3+Efficiency be than relatively low, generally (to be moved back after tin stripper failure
In tin waste liquid) have substantial amounts of ferrous ion Fe2+It is present in decoction.In addition, with univalent copper ion Cu+Increase, medicine
The tin performance of moving back of liquid is gradually reduced, as univalent copper ion Cu+When concentration exceedes some value, move back tin speed and drastically decline, so, must
The univalent copper ion Cu in decoction must be controlled+Content is in reduced levels.
Inventor is after above analyzing in detail and experimental verification its reaction mechanism has been done, it is believed that：The failure of whole decoction is former
Because one side is because the reduction of free nitric acid, to cause decoction oxidation susceptibility to decline, moves back tin and slow；On the other hand be because
Increase for Theil indices in decoction, cause to move back the decline of tin effect, may can also produce the phenomenon that copper face grows dim, cause in useless plate rate
Rise；It is exactly univalent copper ion Cu to have again+Increase cause the drastically decline of decoction oxidation susceptibility；Finally, ferrous ion Fe2+'s
Increase causes the drastically decline of decoction oxidation susceptibility to be also important factor in order.
Therefore, inventor considers：Using lossless separation method, i.e., do not additionally introduce on the influential material of tin stripping liquid performance
Into decoction system, it can not produce other accessory substance during separation and cause secondary pollution, effective reuse of decoction should be ensured
Again can be by the recovery of tin in system and copper, and by the ferrous ion Fe in system2+Oxidation regeneration is into ferric ion Fe3 +。
In order to meet above-mentioned requirements, inventor organically combines the physics of each material component in tin removal waste liquor, chemistry and electrification
Property is learned, and moves back the performance of each composition in the new liquid of tin, from additive, stabilizer, the heavy formula such as tin agent and nitric acid screener source
Set about on head, redesign and optimization of C/C composites, and each related tin stripping liquid of formula moves back tin performance indications, followed by verification experimental verification
Ring regeneration retreat the new liquid of tin move back tin performance indications, the heavy tin effect of heavy tin agent, influence of the nitric acid screener to acid copper with
And the influence to moving back the new liquid of tin etc..
So-called electro-deposition copper removal, is by lean tin phase transfer into copper removal device, to add nitric acid screener to shield nitric acid
Strong oxidizing property, then the copper in solution is deposited on minus plate under the conditions of low voltage high current, reaction mechanism such as reaction equation
(9) shown in~reaction equation (11)：
Anode reaction：Fe2+=Fe3++e- (9)
Cathode reaction：Cu2++2e-=Cu (10)
Overall reaction：Cu2++2Fe2+=Cu+2Fe3+(under power on condition) (11)
By the electrochemistry copper-removing method, while the copper ion in solution is changed into metallic copper, also by solution
Fe2+Oxidation regeneration is into Fe3+, the problem of solving reducing substances oxidation regeneration in tin removal waste liquor.
With reference to above-mentioned thought, the present invention implements to disclose a kind of method of tin removal waste liquor circular regeneration, i.e. obligee is referred to as
For GREEN-TRT technology, detailed description is carried out to this method using specific embodiment below.
Embodiment
As shown in figure 1, a kind of method for tin removal waste liquor circular regeneration that the present invention is provided, including implementation move back tin and produce and produce
That gives birth to tin removal waste liquor moves back tin production operation step A；Collect the storage operating procedure B of tin removal waste liquor；Tin removal waste liquor to collection is entered
The operating procedure C of row pre-treatment, can make sn-containing compound in tin removal waste liquor be concentrated to sn rich phase, and tin removal waste liquor is divided into richness
Tin phase and lean tin phase, are respectively delivered to carry tin device and except ketone device；Copper removal for reducing copper content in tin removal waste liquor is operated
Step D；For will reclaim metallic tin and removed the preparing solution after metallic copper into the regenerative operation step E for moving back the new liquid of tin；For
The storage tank F of the new liquid of tin is moved back in storage, and carries tin operating procedure G by what the tin in stanniferous concentrate became tin product.
Specifically, after tin removal waste liquor is by tin removal waste liquor pre-treatment operating procedure, tin removal waste liquor is divided into sn rich phase and poor
Tin phase；Sn rich phase carries out carrying tin by putting forward tin operating procedure, obtains stanniferous product；Lean tin is removed by copper removal operating procedure
Copper, obtains regenerated liquid and metallic copper；Regenerated liquid is allocated by moving back the new liquid regenerative operation step of tin, must move back the new liquid of tin；Move back tin new
Liquid stores operating procedure storage by moving back the new liquid of tin, in case moving back tin production；Tin removal waste liquor stores operating procedure by tin removal waste liquor
Storage, in case tin removal waste liquor pre-treatment.
Specifically, operating procedure G includes the formulation operations step, heavy tin operating procedure and product collection operation of heavy tin agent
The several parts of step, after heavy tin agent is prepared, are pumped into heavy tin device and are mixed with stanniferous rich phase materials, stirring, stanniferous chemical combination
Thing is then precipitated, and the material fixed band liquid pump after precipitating completely enters in Product recycling device, collects in product, product
Stanniferous amount is 5-90%.Clear liquid can be with reuse, to allocate new heavy tin agent.
Specifically, operating procedure D is mainly electro-deposition copper removal, as needed appropriate addition nitric acid screener, electro-deposition
Operation temperature can be controlled in -20-120 DEG C, preferably 0 DEG C -20 DEG C of scopes, and operating pressure is normal pressure, current density be 80A/ ㎡ -
800A/ ㎡, preferably 80-100A/ ㎡.The setting of any operating condition or parameter is not intended to limit the present invention.
Specifically, operating procedure E is mainly used as preparation and moves back the new liquid of tin, in the regenerated liquid after except tin, copper removal, adds in proportion
Plus stabilizer, nitric acid, copper-protection agent and water, the new liquid of tin is moved back with being made, the new liquid of tin is moved back and belongs to acidic products, its proportion is 0.90g/cm3-
1.35g/cm3, outward appearance is in yellow green or yellow liquid.Appearance attribute of institute's preparating liquid etc. is not intended to limit the present invention.
Specifically, in each operating procedure material transfer can using pumping conveying, Geldart-D particle, it is artificial carry topple over etc. appoint
Meaning mode, and the mode of material conveying transfer is not intended to limit the present invention.
Specifically, if production scene, which is mismatched, moves back the new liquid regenerating unit of tin, but regenerated liquid is sent to otherwise allotment
Into moving back the new liquid of tin, although scene does not appear to move back the new liquid regenerative operation of tin, but in fact should be regarded as having used the inventive method, institute
So that it is that outward transport or situ regeneration are not intended to limit the present invention that the new liquid of tin is moved back in actual production.
Similarly, each operating procedure is to carry out or carried out in different places in same place, is not used in restriction
The present invention.
Specifically, in practical operation, if not matching special tin removal waste liquor storage device or moving back the new liquid storage dress of tin
Put, then do not store operating procedure B and operating procedure F, so, the presence or absence of operating procedure is stored in actual production and is not used to limit
The fixed present invention.
The method for the tin removal waste liquor circular regeneration that the present invention is provided, not only involved device structure is simple, field conduct
Operation is easy, can more accomplish the cycling and reutilization of material, is a kind of environment-friendly type production method that disclosure satisfy that clean manufacturing requirement.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Any modifications, equivalent substitutions and improvements made within principle etc., should be included in the scope of the protection.
Claims (10)
1. a kind of method of tin removal waste liquor circular regeneration, it is characterised in that including following operating procedure：Tin removal waste liquor pre-treatment is grasped
Make step, put forward tin operating procedure, copper removal operating procedure, and/or move back the new liquid regenerative operation step of tin, and/or move back the new liquid storage of tin
Operating procedure, and/or tin removal waste liquor storage operating procedure.
2. the method described in claim 1, each operating procedure is sequentially carried out, it is characterised in that：
After tin removal waste liquor is by tin removal waste liquor pre-treatment operating procedure, tin removal waste liquor is divided into sn rich phase and lean tin phase；
Sn rich phase carries out carrying tin by putting forward tin operating procedure, obtains stanniferous product；
Lean tin carries out copper removal by copper removal operating procedure, obtains regenerated liquid and metallic copper；
And/or regenerated liquid is allocated by moving back the new liquid regenerative operation step of tin, must move back the new liquid of tin；
And/or the new liquid of tin is moved back by moving back the new liquid storage operating procedure storage of tin, in case moving back tin production；
And/or tin removal waste liquor stores operating procedure by tin removal waste liquor and stored, in case tin removal waste liquor pre-treatment.
3. the method described in claim 1, it is characterised in that the tin removal waste liquor pre-treatment operating procedure, is by tin removal waste liquor
In sn-containing compound concentrated so that sn-containing compound be enriched with together into sn rich phase, other less things of stanniferous amount
Material turns into lean tin phase, and the operating procedure that sn rich phase and lean tin are mutually produced respectively.
4. the method described in claim 1, it is characterised in that described to put forward tin operating procedure, is that heavy tin agent and sn rich phase is abundant
Mixing, after sn-containing compound is separated out from solution, reclaims sn-containing compound.
5. the method described in claim 1, it is characterised in that the copper removal operating procedure, is by the copper electrochemical in lean tin phase
It is reduced into the namely regenerated liquid of solution after elemental copper removing, copper removal.
6. the method described in claim 1, it is characterised in that described to move back the new liquid regenerative operation step of tin, refer to nitric acid and/or
Copper-protection agent and/or stabilizer and/or water are allocated to regenerated liquid, and need are produced to reach to move back the new liquid performance indications of tin or meet
Ask.
7. the method described in claim 1, it is characterised in that the storage operating procedure is by tin removal waste liquor or moves back the new liquid of tin
It is stored in the container with acid resistance, oxidative resistance and corrosion resistance.
8. tin removal waste liquor pre-treatment operating procedure described in claim 2, it is characterised in that the proportion of the lean tin phase is 1.00g/
cm3-1.35g/cm3, the proportion of the sn rich phase is 1.10g/cm3-1.80g/cm3。
9. move back the new liquid regenerative operation step of tin described in claim 6, it is characterised in that in the copper-protection agent and/or stabilizer
Contain trivalent Fe3+。
10. the copper removal operating procedure described in claim 5, its electrochemical reduction current density is 80A/ ㎡ -800A/ ㎡.
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