CN108754607A - A kind of preparation method of electronic-grade sulfuric acid stannous crystal - Google Patents
A kind of preparation method of electronic-grade sulfuric acid stannous crystal Download PDFInfo
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- CN108754607A CN108754607A CN201810601312.6A CN201810601312A CN108754607A CN 108754607 A CN108754607 A CN 108754607A CN 201810601312 A CN201810601312 A CN 201810601312A CN 108754607 A CN108754607 A CN 108754607A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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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
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/02—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent
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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
Abstract
The present invention provides a kind of preparation methods of the electronic-grade sulfuric acid stannous crystal suitable for high-end electronic product, this method is first in anode prepares the electrolytic cell of the anode relic of stannous sulfate, electrolyte using stanniferous and antioxidant methanesulfonic acid solution using thick tin, cathode using thin sheet tin or diaphragm process, temperature is 20-40 DEG C, current density is in 0.5A/dm2‑5A/dm2Lower electrowinning cathode sheet tin；Cathode sheet tin is packed into the anode position of diaphragm cell again, cathode uses the sulfuric acid solution that thin sheet tin, electrolyte use mass concentration as 5%-9%, is 1.0A/dm in current density2‑2.0A/dm2With 25-35 DEG C at be electrolysed, when the stannous ion mass concentration of anode region is 5%-9%, the electrolyte of anode region is taken out, be concentrated in vacuo and vacuum drying after obtain electronic-grade sulfuric acid stannous crystal.The preparation method of the present invention, low energy consumption, electrolysis effectiveness is high, and the no earth of positive pole generates, stannous sulfate obtained by this method, and purity is high, the white clean, long shelf-life of appearance and at low cost.
Description
Technical field
The present invention relates to a kind of preparation method of sulfate more particularly to a kind of preparation methods of stannous sulfate, more specifically
It is to be related to a kind of preparation method of the electronic-grade sulfuric acid stannous crystal suitable for high-end electronic product.
Background technology
Stannous sulfate is one of important compound of tin, and appearance is white crystalline powder, can be dissolved in water and dilute sulfuric acid, water-soluble
Liquid decomposes rapidly, can slowly aoxidize become yellowish in air.The main application of stannous sulfate is PCB circuit board, electronics is inserted
Part, tinplate be tin plating or daily necessities decorative electroplating tin alloy and the coloring of aluminium electrolytic oxidation, in addition with environmental regulation
Requirement to harmful substance limitation, for stannous sulfate as the additive instead of cadmium, demand is also more next in lead-acid accumulator
It is bigger.
The maturation process for preparing stannous sulfate at present has chemical synthesis and diaphragm process.Chemical synthesis is with chlorination
Stannous is raw material, is first made stannous oxide, then with sulfuric acid dissolution stannous oxide, then evaporating, concentrating and crystallizing, be dried to obtain finished product
Stannous sulfate, chemical synthesis cannot reach the quality requirement of electron level since not only product purity is low for the stannous sulfate of acquisition,
And since process is tediously long, evaporating, emitting, dripping or leaking of liquid or gas probability of happening is larger, and the tin rate of recovery is low, and production cost is high, is eliminated substantially；Every
Membrane electrolysis is to be distinguished anode and cathode using ionic membrane, and metallic tin energization in anode region is dissolved into stannous sulfate solution, then by sulphur
Sour stannous solution through removal of impurities, filtering, condensing crystallizing, be dried to obtain finished product sulfuric acid stannous, due to diaphragm process have technique letter
Single, reaction is easy to control, and reaction speed is fast, with short production cycle, and products obtained therefrom impurity content is less, post-processes the advantages that simple, because
But the existing mainstream production technology for preparing stannous sulfate.
But diaphragm process prepares stannous sulfate and also encounters many problems in production practices these years, wherein relatively more prominent
The problem of going out has：1, the residual anode ratio of anode plate is high, leads to that increased production cost；2, the generation of the earth of positive pole increases the fiber crops of subsequent filter
It is tired；3, tetravalence Theil indices are high in product, make the shortened shelf life of product；Since the nineties in last century, just have successively many special
Profit and document propose the method solved these problems, and such as domestic stannous sulfate technical staff Wang Su is loyal（Popular science and technology, 2012,
1, total 149th phase:180~181）Once the shape and casting process by changing anode plate were had studied so that the anode scrap of anode plate
Rate is reduced to 34.05% from 54.32%, to reduce the expense for melting tin casting anode plate again, while decreasing because again
Founding tin anode anode scrap and the pot face slag generated, but the technique cannot thoroughly solve the problems, such as to generate tin oxide during molten tin,
So that stannous sulfate metallic tin direct recovery rate is low, there are still the problems that production cost is high；Lu Danyan etc. has studied diaphragm electricity
Solution produces the earth of positive pole generated during stannous sulfate（Popular science and technology, 2014,9, total 181st phase:150~151）, research knot
Fruit shows that decomposition voltage, tin anode plate impurity content have a significant impact the yield of the earth of positive pole, when tin anode plate Theil indices are
When 99.98% or more, under optimal Electrolytic conditions, the yield of an electrolytic cell production line Anodic mud can be from 360
Kilogram/month is reduced to 210 kilograms/month, there is the bigger range of decrease, but still has up to 200 kilograms of the earth of positive pole, stannous sulfate solution
Need multistage filtering that could carry out condensing crystallizing, the direct utilization rate of tin metal is poor, and production cost is also high；Publication No. CN
The Chinese patent application of 104591266 A discloses a kind of method extending stannous sulfate shelf life of products, and this method is to sulphur
Sour stannous crystallization is impregnated with ethyl alcohol, and antioxidant is used again after drying（Hydroquinone, β-naphthol solution, benzotriazole solution）
Coating is carried out, although the stannous sulfate that this method obtains effectively extends the shelf-life, after client use, organic carbon
It can be constantly enriched with, and organic carbon is very big to electroplate liquid murder by poisoning, cannot meet the tin plating requirement of high-end electronic product；Publication number
A kind of method reducing tetravalence Theil indices in stannous sulfate is disclosed for the Chinese patent application of CN107385469A, this method
It has main steps that, is laid with one layer of tin granulosa in cell bottom, oxygen scavenger is added in dilute sulfuric acid, pretreated dilute sulfuric acid is added
Enter electrolytic cell to 2~4cm of cathode is flooded, controls bath voltage<2.4V, when stannous sulfate bottom of electrolytic tank tin ion content is big
When equal to 85 grams/L, low four can be obtained by taking out after electrolyte carries out Concentrated and crystallized in vacuum, centrifugation, organic solvent elution, drying
The stannous sulfate of valence Theil indices, it is not only of high cost since the technique pours into a mould tin anode plate and tin grain using refined tin, but also be electrolysed
Journey earth of positive pole yield is still larger, this is because refined tin is by pyrometallurgical smelting gained, in refuse casting tin anode plate
When, tin is easy to form sull on surface at high temperature, this layer of oxide film is easy the process for making tin anode plate in electrolysis
The middle generation earth of positive pole, and due to the presence of the earth of positive pole, tank voltage increases, and side reaction, the oxygen that side reaction generates easily occur for anode
The Bivalent Tin in stannous sulfate solution is easily oxidized to tetravalent tin, the stannous sulfate appearance prepared is easy to turn yellow, dissolubility
It is deteriorated so that the requirement of electron level is not achieved in product quality.
Invention content
To overcome the problems, such as present on, the object of the present invention is to provide a kind of preparation sides of electronic-grade sulfuric acid stannous crystal
Method, this method production cost is low and the avoidable earth of positive pole generates and anode anode scrap melts down founding again.
In order to achieve the above object, the preparation method of the electronic-grade sulfuric acid stannous crystal of the present invention, in turn includes the following steps：
（1）The preparation of stannous sulfate tin anode plate：It is dense for 25-45 grams/L, pyrovinic acid that tin ion concentration is added in a cell
Degree be 120-180 grams/L, the electrolyte that antioxidant concentration be 0.5-1.5 grams/L, and anode is using thick tin, and cathode is using thin sheet tin
Or diaphragm process prepares the anode relic of stannous sulfate, temperature is 20-40 DEG C, current density is in 0.5A/dm2-5A/dm2's
Under the conditions of electrorefining, when cathode plate thickness reaches 35-50mm, stop electrorefining, cathode plate is dismantled, is cleaned with pure water
Cathode sheet tin is obtained behind surface；
（2）The preparation of stannous sulfate solution：By step（1）The cathode sheet tin of gained is packed into the anode position of diaphragm cell, cloudy
Pole uses thin sheet tin, electrolyte to use mass concentration for the sulfuric acid solution of 5%-9%, and diaphragm uses anion out-phase exchange membrane, leads to
Enter direct current, is 1.0A/dm in current density2-2.0A/dm2, temperature be 25-35 DEG C at be electrolysed, when the stannous ion of anode region
When mass concentration is 5%-9%, the electrolyte of anode region is taken out, stannous sulfate solution is obtained；
（3）The preparation of electronic-grade sulfuric acid stannous crystal：By step（2）The stannous sulfate solution of gained is concentrated in vacuo, lazy
It is centrifuged under property gas shield, obtains stannous sulfate crystal, then stannous sulfate crystal is put by nitrogen displaced air
It in vacuum dryer, is dried in vacuo at 60~80 DEG C, obtains electronic-grade sulfuric acid stannous crystal of the content 99% or more.
In above-mentioned preparation method, step（1）Electrolyte be that pyrovinic acid, stannous methanesulfonate pure water and antioxidant are matched
It makes.
Enter electrolyte to more preferably prevent impurity, in above-mentioned preparation method, step（1）Thick tin anode be cased with polypropylene
Diaphragm bag.
In above-mentioned preparation method, step（1）The preferred hydroquinone of antioxidant.
In above-mentioned preparation method, step（1）And step（2）Thin sheet tin thickness be 3mm-6mm.
In above-mentioned preparation method, step（2）After the electrolyte for taking out anode region, the sulphur that mass concentration is 5-9% is refilled
Acid solution continues to be electrolysed, until anode plate thickness in 5-10mm, replaces anode plate.
In order to cost-effective, in above-mentioned preparation method, step（1）The anode relic that cathode uses is step（2）Under replacement
The anode plate relic come.
In above-mentioned preparation method, step（1）The electrolyte of electrolytic cell, which dissociates when pyrovinic acid is less than 120 grams/L, adds methyl
Sulfonic acid so that free pyrovinic acid maintains 120 grams/L or more.
The preparation method of the electronic-grade sulfuric acid stannous crystal of the present invention, using thick tin as raw material, in pyrovinic acid system
High-purity is prepared using electrolytic refining process and is electrolysed sheet tin, not only low energy consumption, electrolytic efficiency is good, sheet tin is readily cleaned, but also the height
Purity electrolysis sheet tin needs not move through remelting, casting can regard the anode plate use that electrolysis prepares stannous sulfate, and using should
Tin anode of the anode plate as diaphragm electrolysis, entire electrolytic process cell voltage fluctuation amplitude very little, the no earth of positive pole generates, by the party
Stannous sulfate made from method, purity is high, the white clean, long shelf-life of appearance, meets the requirement of electronic-grade sulfuric acid stannous, with traditional diaphragm
Electrolysis prepares stannous sulfate technique and compares, and tin anode does not need the processes such as high temperature melting, casting, and electrolytic process is without anode
The generation of mud ensure that the stabilization of stannous sulfate quality；In addition, cathode beginning piece of the remaining anode as electrolytic deposition refined tin process
It uses, without melting down founding again, improves the direct utilization rate of metallic tin, reduce production cost, also greatly reduce
The labor intensity and high temperature of worker scalds equivalent risk, is that electronic-grade sulfuric acid stannous that is a kind of practical and being worth of widely use is brilliant
The preparation method of body.
Specific implementation mode
Here is several specific embodiments of electronic-grade sulfuric acid stannous crystal preparation method of the present invention, these embodiments are
The present invention is prepared by stannous sulfate crystal is illustrated, not limiting the scope of the invention.
One, embodiment
Embodiment 1
Pyrovinic acid, stannous methanesulfonate, pure water and hydroquinone are added in liquid pool, is made into hydroquinone a concentration of 0.5
Gram/L, tin ion concentration be 25 grams/L, a concentration of 130 grams/L of pyrovinic acid initial electrolysis liquid, filtering, be added to equipped with thick tin
Anode, the pure tin thin plate of making do cathode beginning piece（Thickness 3mm-6mm）Electrolytic cell in, thick tin anode is cased with polypropylene diaphragm
Bag, temperature be 20 DEG C, current density 0.5A/dm2Under conditions of be electrolysed, when pyrovinic acid concentration is reduced to 120 in slot
Gram/L when, add pyrovinic acid to 130 grams/L, stop electrolysis when cathode sheet tin thickness is 35mm, cathode sheet tin is dismantled, use
After pure water cleans surface, cathode sheet tin is filled to the anode Board position of the diaphragm cell of the sulfuric acid solution of 6% mass concentration,
The cathode of diaphragm cell is thin sheet tin（Thickness 3mm-6mm）, diaphragm use anion out-phase exchange membrane, be passed through direct current, adjust
Whole current density is 1.0A/dm2, when electrolysis to anode region tin ion mass concentration is 5% under 25 DEG C of water-baths are kept the temperature, by anode
Area's electrolyte takes out, and refills 6% sulfuric acid solution, continues to be electrolysed, and when anode tin plate thickness becomes 5mm, replaces anode
Plate, entire electrolytic process cell voltage fluctuation amplitude are generated in ± 0.1V, the no earth of positive pole；The anode region electrolyte vacuum of taking-up is dense
Contracting obtains stannous sulfate crystallization；First use inert gas（Nitrogen）Air in displacement drying equipment, then stannous sulfate crystal is put
Enter in drying equipment, supplement nitrogen, be dried in vacuo at a temperature of 60 DEG C, obtains the electronic-grade sulfuric acid stannous that content is 99.1%
Finished product.
Embodiment 2
Pyrovinic acid, stannous methanesulfonate, pure water and hydroquinone are added in liquid pool, be made into a concentration of 1 gram of hydroquinone/
L, tin ion concentration is the initial electrolysis liquid of 35 grams/L, a concentration of 150 grams/L of pyrovinic acid, and filtering is added to equipped with thick tin system
Anode, 1 diaphragm process of example of work prepare anode relic obtained by stannous sulfate process and do in the electrolytic cell of cathode beginning piece, thick tin
Anode is cased with polypropylene diaphragm bag, temperature be 30 DEG C, current density 1A/dm2Under conditions of be electrolysed, when methyl sulphur in slot
When acid concentration is reduced to 120 grams/L, pyrovinic acid is added to 150 grams/L, it is heavy to stop electrolysis when cathode sheet tin thickness is 50mm
Product, cathode sheet tin is dismantled, surface is cleaned with pure water；Cathode sheet tin is filled to the diaphragm of the sulfuric acid solution equipped with 9% mass concentration
Anode electrolytic cell Board position, diaphragm cell cathode are thin sheet tin（Thickness 3mm-6mm）, diaphragm is using the exchange of anion out-phase
Film, is passed through direct current, and adjustment current density is 2.0A/dm2, in 30 DEG C of water-bath heat preservation electrolysis to anode region tin ion mass concentration
When being 9%, anode region electrolyte is taken out, refills 9% sulfuric acid solution, continues to be electrolysed, when anode tin plate thickness becomes
When 10mm, anode plate is replaced, whole process cell voltage fluctuation amplitude is generated in ± 0.1V, the no earth of positive pole；By the anode region of taking-up
Electrolyte vacuum concentrates, and obtains stannous sulfate crystallization；First use inert gas（Nitrogen）Air in displacement drying equipment, then by sulphur
Sour stannous crystal is put into drying equipment, is supplemented nitrogen, is dried in vacuo at a temperature of 70 DEG C, and the electricity that content is 99.5% is obtained
Sub- grade stannous sulfate finished product.
Embodiment 3
Pyrovinic acid, stannous methanesulfonate, pure water and hydroquinone are added in liquid pool, is made into hydroquinone a concentration of 1.5
Gram/L, tin ion concentration is 45 grams/L, and the methanesulfonic acid solution of a concentration of 160 grams/L of pyrovinic acid filters, and is added to equipped with thick
Anode, 2 diaphragm process of example of tin making prepare anode relic obtained by stannous sulfate process and do in the electrolytic cell of cathode beginning piece,
Thick tin anode is cased with polypropylene diaphragm bag, is 40 DEG C in temperature, current density 0.5A/dm2Under conditions of be electrolysed, when in slot
When pyrovinic acid concentration is reduced to 120 grams/L, pyrovinic acid is added to 160 grams/L, stops electricity when cathode plate thickness is 40mm
Solution deposition, cathode sheet tin is dismantled, surface is cleaned with pure water；Cathode sheet tin is filled to the sulfuric acid solution equipped with 8% mass concentration
Diaphragm cell anode Board position, diaphragm cell cathode are thin sheet tin（Thickness 3mm-6mm）, diaphragm is using the friendship of anion out-phase
Film is changed, direct current is passed through, adjustment current density is 1.5A/dm2, dense to anode region tin ion quality in 35 DEG C of water-bath heat preservation electrolysis
When degree is 7%, anode region electrolyte is taken out, 8% sulfuric acid solution is refilled, continues to be electrolysed, when anode tin plate thickness becomes
When 8mm, anode plate is replaced, whole process cell voltage fluctuation amplitude is generated in ± 0.1V, the no earth of positive pole；By the anode region electricity of taking-up
It solves liquid to be concentrated in vacuo, obtains stannous sulfate crystallization；First use inert gas（Nitrogen）Air in displacement drying equipment, then by sulfuric acid
Stannous crystal is put into drying equipment, is supplemented nitrogen, is dried in vacuo at a temperature of 80 DEG C, and the electronics that content is 99.8% is obtained
Grade stannous sulfate finished product.
Comparative example
Refined tin ingot is melted, sheet tin is cast into, then sheet tin is filled to equipped with the diaphragm cell that mass concentration is 9% sulfuric acid solution
Anode Board position, diaphragm cell cathode are thin sheet tin（Thickness 3mm-6mm）, it is passed through direct current, adjustment current density is 2.0A/
dm2, when 35 DEG C of water-bath heat preservation electrolysis to anode region tin ion mass concentrations is 7%, anode region electrolyte is taken out, is noted again
The sulfuric acid solution for entering 9% continues to be electrolysed, and when anode tin plate thickness becomes 5mm, replaces anode plate, remaining anode weight is first
The 35% of beginning anode weight needs to melt down founding again into the tin anode plate that thickness is 20-50mm, and entire electrolytic process anode has
The earth of positive pole generation of black, yellow, voltage increase 0.5V；After the anode region electrolyte filtering of taking-up, then it is concentrated in vacuo to obtain
Stannous sulfate crystallizes, and stannous sulfate crystal is put into the vacuum dryer by nitrogen displaced air, in 60 DEG C of temperature
Lower vacuum drying obtains the stannous sulfate finished product that content is 99 %.
Two, quality testing
Quality testing is carried out to the stannous sulfate crystal that embodiment 1-3 and comparative example preparation method are obtained, as a result such as following table：
As can be seen from the above results, since the preparation method of the present invention is it is possible to prevente effectively from electrolysis prepares stannous sulfate anode
The generation of mud so that the content of high tin greatly reduces, and clarity is also obviously improved, metal impurities（Especially iron, lead and comparison
Example is compared）Very little meets the quality requirement of electronic-grade sulfuric acid stannous crystal, and diaphragm electrolysis prepares the residual of stannous sulfate process
Anode is stayed to be used as the cathode beginning piece of electrolytic deposition refined tin process, it is not only at low cost, but also avoid anode anode scrap and return again
The process of stove founding, while the generation of scruff in fusion-casting process is also avoided, significantly reduce the labor intensity and height of worker
Temperature scald equivalent risk.The preparation method of the present invention, the temperature of electrolytic deposition refined tin process is low, and product purity is high, long shelf-life, by
Stannous sulfate prepared by the method for the present invention has more the market competitiveness.
Claims (8)
1. a kind of preparation method of electronic-grade sulfuric acid stannous crystal, in turn includes the following steps：
（1）The preparation of stannous sulfate tin anode plate：It is dense for 25-45 grams/L, pyrovinic acid that tin ion concentration is added in a cell
Degree be 120-180 grams/L, the electrolyte that antioxidant concentration be 0.5-1.5 grams/L, and anode is using thick tin, and cathode is using thin sheet tin
Or diaphragm process prepares the anode relic of stannous sulfate, temperature is 20-40 DEG C, current density is in 0.5A/dm2-5A/dm2's
Under the conditions of electrorefining, when cathode plate thickness reaches 35-50mm, stop electrorefining, cathode plate is dismantled, is cleaned with pure water
Cathode sheet tin is obtained behind surface；
（2）The preparation of stannous sulfate solution：By step（1）The cathode sheet tin of gained is packed into the anode position of diaphragm cell, cloudy
Pole uses thin sheet tin, electrolyte to use mass concentration for the sulfuric acid solution of 5%-9%, and diaphragm uses anion out-phase exchange membrane, leads to
Enter direct current, is 1.0A/dm in current density2-2.0A/dm2, temperature be 25-35 DEG C at be electrolysed, when the stannous ion of anode region
When mass concentration is 5%-9%, the electrolyte of anode region is taken out, stannous sulfate solution is obtained；
（3）The preparation of electronic-grade sulfuric acid stannous crystal：By step（2）The stannous sulfate solution of gained is concentrated in vacuo, in nitrogen
It is centrifuged under gas shielded, obtains stannous sulfate crystal, then stannous sulfate crystal is put into the vacuum by nitrogen displaced air
It in drying equipment, is dried in vacuo at 60~80 DEG C, obtains electronic-grade sulfuric acid stannous crystal of the content 99% or more.
2. the preparation method of electronic-grade sulfuric acid stannous crystal according to claim 1, it is characterised in that：The preparation method
In, step（1）Electrolyte be that pyrovinic acid, stannous methanesulfonate pure water and antioxidant are formulated.
3. the preparation method of electronic-grade sulfuric acid stannous crystal according to claim 1 or 2, it is characterised in that：The preparation
In method, step（1）Thick tin anode be cased with polypropylene diaphragm bag.
4. the preparation method of electronic-grade sulfuric acid stannous crystal according to claim 3, it is characterised in that：The preparation method
In, step（1）Antioxidant be hydroquinone.
5. the preparation method of electronic-grade sulfuric acid stannous crystal according to claim 4, it is characterised in that：The preparation method
In, step（1）And step（2）Thin sheet tin thickness be 3mm-6mm.
6. the preparation method of electronic-grade sulfuric acid stannous crystal according to claim 5, it is characterised in that：The preparation method
In, step（2）After the electrolyte for taking out anode region, the sulfuric acid solution that mass concentration is 5-9% is refilled, continues to be electrolysed, until
Anode plate thickness replaces anode plate in 5-10mm.
7. the preparation method of electronic-grade sulfuric acid stannous crystal according to claim 6, it is characterised in that：The preparation method
In, step（1）The anode relic that cathode uses is step（2）Replaced anode plate relic.
8. the preparation method of electronic-grade sulfuric acid stannous crystal according to claim 7, it is characterised in that：The preparation method
In, step（1）The electrolyte of electrolytic cell, which dissociates when pyrovinic acid is less than 120 grams/L, adds pyrovinic acid so that free methyl sulphur
Acid maintains 120 grams/L or more.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110387540A (en) * | 2019-08-30 | 2019-10-29 | 江苏上达电子有限公司 | Stannous replenishment system and method in a kind of tin dissolving slot |
| CN110817941A (en) * | 2019-11-29 | 2020-02-21 | 广东光华科技股份有限公司 | Refining method of stannous fluoride |
| CN111302387A (en) * | 2020-03-26 | 2020-06-19 | 深圳市星河环境技术有限公司 | Preparation method of high-purity potassium stannate |
| CN112941565A (en) * | 2021-02-24 | 2021-06-11 | 恩施市致纯电子材料有限公司 | Preparation method of high-purity tin |
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| CN110817941A (en) * | 2019-11-29 | 2020-02-21 | 广东光华科技股份有限公司 | Refining method of stannous fluoride |
| CN111302387A (en) * | 2020-03-26 | 2020-06-19 | 深圳市星河环境技术有限公司 | Preparation method of high-purity potassium stannate |
| CN112941565A (en) * | 2021-02-24 | 2021-06-11 | 恩施市致纯电子材料有限公司 | Preparation method of high-purity tin |
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