CN107385469B - The method for reducing tetravalence Theil indices in stannous sulfate - Google Patents
The method for reducing tetravalence Theil indices in stannous sulfate Download PDFInfo
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- CN107385469B CN107385469B CN201710554713.6A CN201710554713A CN107385469B CN 107385469 B CN107385469 B CN 107385469B CN 201710554713 A CN201710554713 A CN 201710554713A CN 107385469 B CN107385469 B CN 107385469B
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Abstract
The invention discloses a kind of methods of tetravalence Theil indices in reduction stannous sulfate, include the following steps: to be laid with one layer of tin granulosa at stannous sulfate electrolytic bath bottom；Oxygen scavenger is added in dilute sulfuric acid, dilute sulfuric acid after must handling；The dilute sulfuric acid after addition processing into stannous sulfate electrolytic cell, until dilute sulfuric acid liquid level did not had 2~4cm of cathode, control bath voltage < 2.4V after processing；As tin ion content >=85g/L in the electrolyte of stannous sulfate electrolytic bath bottom, electrolyte is put from exit to slot outlet, dilute sulfuric acid keeps tank liquor liquid level to former height after supplement process into slot while discharging electrolyte；When tin ion content drops to 80g/L in the electrolyte of stannous sulfate electrolytic bath bottom, stop the supplement of dilute sulfuric acid after the discharge and processing of above-mentioned electrolyte；Electrolyte is subjected to condensing crystallizing, gained crystal is dry after being eluted using eluent, obtains stannous sulfate.
Description
Technical field
The invention belongs to stannous sulfate preparation fields, and in particular to a kind of side for reducing tetravalence Theil indices in stannous sulfate
Method.
Background technique
Stannous sulfate is a kind of white or pale yellow crystals powder, can be dissolved in water and dilute sulfuric acid, and aqueous solution decomposes rapidly,
It will be slow oxidation in air, become yellowish, be a kind of important fine chemistry product, stannous sulfate is usually used in metal, alloy
With the acid electroplating of nonmetallic materials, aluminium alloy is electrolysed heat-tinting, hydrogen peroxide remover and is used in mixed way with nickel salt and does sealing of hole
Agent, many industries such as printed circuit board are all widely used.
Bivalent Tin stability in stannous sulfate is poor, is easy by the dioxygen oxidation in air into tetravalent tin, tetravalent tin is deposited
The jaundice of stannous sulfate product can be made hardened, shortening the shelf-life of product, it is stannic in plating, electrolytic coloring industry use
Accumulation can be such that tank liquor aging, precipitating increase, electrolytic coloring effect reduces.Therefore tetravalent tin in resulting stannous sulfate is prepared at present
Content is generally in 0.1-0.15%.When tetravalent tin reaches 0.15%, storage validity period is no more than half a year, when tetravalent tin reaches
When 0.1%, storage validity period is 1 year or so, and when tetravalent tin is less than 0.05%, the storage time is more than 2 years also non-discolouring.Cause
This tetravalence Theil indices seriously affects its store in a warehouse validity period and product appearance.
Domestic scholars endanger green (Five City University's journal, 2000,14,55-59) when being once reported in laboratory and preparing stannous sulfate
Need to control current density to inhibit tetravalent tin, but this method is obtained in laboratory condition intermittent electrolyzing, is industrialized big raw
It produces anodic area constantly to change, current density difficulty or ease accurately control, and are unsuitable for extensive consecutive production；Wu Ying (nothing
Machine salt industrial, 1995,1:9-11) temperature, acidity etc. are described, stannic influence is oxidized on Bivalent Tin, but paper does not consider
The influence that dissolved oxygen generates tetravalent tin in electrolyte；Chinese patent 201410846701.7 elaborates to add organic antioxidant
Method to extend stannous sulfate shelf life of products, but foreign matter is added in party's normal direction product, influence product quality；Du Jianzhong
(Food Science: 2005,26,397-399) describe stannic test method.
Therefore, it is badly in need of a kind of method that tetravalence Theil indices in stannous sulfate can be effectively reduced at present.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of methods that tetravalence Theil indices in stannous sulfate can be effectively reduced.
In order to solve the above technical problem, the present invention provides a kind of method (drops of tetravalence Theil indices in reduction stannous sulfate
The method of tetravalence Theil indices in low stannous sulfate production process), the cathode being used cooperatively is respectively equipped in stannous sulfate electrolytic cell
And anode, stannous sulfate bottom of electrolytic tank are equipped with outlet；Include the following steps:
1), one layer of tin granulosa is laid at stannous sulfate electrolytic bath bottom；
2) oxygen scavenger, is added in dilute sulfuric acid, dilute sulfuric acid after must handling；The amount ratio of dilute sulfuric acid and oxygen scavenger is 100ml/
0.05~0.1g；
The dilute sulfuric acid is the sulfuric acid solution that concentration is 1 ± 0.1mol/L；
3), into stannous sulfate electrolytic cell addition processing after dilute sulfuric acid, until processing after dilute sulfuric acid liquid level do not had cathode 2~
4cm controls bath voltage < 2.4V；
4), in the electrolyte at the stannous sulfate electrolytic bath slot bottom when tin ion content >=85g/L, from exit to slot
Outlet puts electrolyte, and into slot, dilute sulfuric acid keeps tank liquor liquid level to former height after supplement process while discharging electrolyte；
When tin ion content drops to 80g/L in electrolyte at the stannous sulfate electrolytic bath slot bottom, stop above-mentioned electricity
Solve liquid discharge and processing after dilute sulfuric acid supplement (when tank liquor build-up of fluid to former height, stopping processing after dilute sulfuric acid benefit
It fills)；
5), collection step 4) discharge electrolyte, carry out condensing crystallizing, gained crystal (is water-soluble molten using eluent
Agent) eluted after it is dry, obtain stannous sulfate.
As the improvement for reducing the method for tetravalence Theil indices in stannous sulfate of the invention: the oxygen scavenger is acetoxime
(preferably), sodium dithionite, sodium sulfite, hydrazine.
As the of the invention further improvements in methods for reducing tetravalence Theil indices in stannous sulfate: tin granulosa with a thickness of
1~4cm (preferably 2cm)；The D of tin grain50It is cotton-shaped tin for 1~10 μm (utilizing Malvern ParticleSizer test gained).
As the further improvements in methods for reducing tetravalence Theil indices in stannous sulfate of the invention: the eluent is alcohol
Class (preferably isopropanol), ketone (preferably butanone, acetone).
As the further improvements in methods for reducing tetravalence Theil indices in stannous sulfate of the invention: preferred bath voltage
For 1.8~2.2V, more preferably 1.8~2.0V.
As the further improvements in methods for reducing tetravalence Theil indices in stannous sulfate of the invention: in the step 5),
The electrolyte of collection carries out condensing crystallizing at a temperature of 0.08~0.09atm vacuum degree, 60~65 DEG C.
As the further improvements in methods for reducing tetravalence Theil indices in stannous sulfate of the invention: in the step 5),
Crystal is eluted (thus washing away entrainment free sulfuric acid) using eluent under centrifugal condition；Then in 85~90 DEG C under vacuum
It dries to constant weight.
Further improvements in methods as tetravalence Theil indices in reduction stannous sulfate of the invention: the dosage of eluent is
13~17% (preferably 15%) of crystal volume.
In the present invention, while using following 4 kinds of methods the regulation that links reduces tetravalent tin in stannous sulfate production process
Content:
1, by regulation voltage, inhibit high current density, anodic passivity and the tetravalent tin that causes generates:
Using suitable voltage, constantly changed with eliminating industrialized production anodic area, current density difficulty or ease
The problem of accurate control.Avoid to maximizing that anode potential is excessively high, tetravalent tin caused by anodic passivity generates with this condition；
2, tin grain is laid with by cell bottom, the tetravalent tin for restoring generation is Bivalent Tin:
Specific surface area can increase using tin grain of the invention, tetravalent tin is enable to be reduced into Bivalent Tin；
3, oxygen scavenger is added in dilute sulfuric acid, to remove the dissolved oxygen that can participate in oxidation in dilute sulfuric acid:
A small amount of efficient oxygen scavenger is added in dilute sulfuric acid, and the dissolved oxygen in dilute sulfuric acid is enable to remove in time；It is added
Acetoxime easily resolves into nitrogen and water (for volatile materials) in acid condition, to will not introduce in stannous sulfate newly
Impurity, therefore be recommended to use；
4, after eluting stannous sulfate crystal with solvent (eluent), raffinate aqueous, containing acid in crystal is removed, it is subsequent with benefit
Flash baking, reduce high-temperature oxydation of Bivalent Tin during baking material:
It is crystallized using alcohols, ketone water-soluble solvent elution stannous sulfate, preferably isopropanol, can both wash stannous sulfate
Aqueous, the raffinate containing acid after centrifuge separation in wet product reduce high temperature oxygen of Bivalent Tin during baking material with sharp flash baking
Change, and isopropanol is made full use of to not readily dissolve the characteristic in saline solns, be layered isopropanol can simply in water layer, passes through
Ji is safely recycled, is applied.
In conclusion the quality of stannous sulfate can be improved using method of the invention, reduction tetravalence Theil indices (≤
0.07%), extend the shelf-life of stannous sulfate.Method of the invention is at low cost, is conducive to the international competitiveness for improving market.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 is the schematic device that electrolysis method prepares stannous sulfate.
Specific embodiment
A kind of electrolysis method prepares the device of stannous sulfate, and as described in Figure 1, including stannous sulfate electrolytic cell is (hereinafter referred to as electric
Solve slot), outlet is equipped at the bottom of electrolytic cell, the outlet is for discharging electrolyte, and bottom is laid with one layer of tin in electrolytic cell
Granulosa；In order to avoid tin grain as electrolyte is flowed out from outlet, in exit, setting is for that can intercept the filter screen of tin grain, and makes
Outlet is slightly above the upper surface of tin granulosa, is generally higher by 1cm.
Cathode sheet tin (abbreviation cathode) and anode sheet tin (abbreviation anode) are equipped in electrolytic cell, anode is close to electrolytic cell
Lower part, cathode plate are located at the top of electrolytic cell, and distance between the two is about 10~12cm.Anode is at a distance from bottom in electrolytic cell
About 5cm.
The D of tin grain50It is cotton-shaped tin for 1~10 μm (utilizing Malvern ParticleSizer test gained).
It measures into electrolytic cell after dropwise addition processing when dilute sulfuric acid (that is, dilute sulfuric acid of the oxygen scavenger containing a certain concentration) with excessively not negative
2~4cm of pole is preferred, and is electrolysed after logical direct current control voltage.
Following embodiment is all made of the device.
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in
This.
Embodiment 1, a kind of method for reducing tetravalence Theil indices in stannous sulfate production process, include the following steps:
1), tin granulosa (the partial size D that a layer thickness is 2cm is laid at stannous sulfate electrolytic bath bottom50It is 2 μm)；
2) acetoxime as oxygen scavenger, dilute sulfuric acid after must handling, are added in dilute sulfuric acid；The use of dilute sulfuric acid and oxygen scavenger
Amount is than being 100ml/0.05g；
The dilute sulfuric acid is the sulfuric acid solution that concentration is 1mol/L；
3), into stannous sulfate electrolytic cell addition processing after dilute sulfuric acid, until processing after dilute sulfuric acid liquid level do not had cathode 2~
4cm, control bath voltage are 1.9V；
4), in the electrolyte at the stannous sulfate electrolytic bath slot bottom when tin ion content >=85g/L, from exit to slot
Outlet puts electrolyte, and into slot, dilute sulfuric acid keeps tank liquor liquid level to former height after supplement process while discharge；
When tin ion content drops to 80g/L in electrolyte at the stannous sulfate electrolytic bath slot bottom, it is simultaneously stopped
State the supplement of dilute sulfuric acid after the discharge and processing of electrolyte；
Rate of discharge=dilute sulfuric acid supplement rate of above-mentioned electrolyte, discharge amount per minute are original liquid in electrolytic cell
The 3~5% of body volume.
5), collection step 4) discharge electrolyte, carried out at a temperature of 0.08~-0.09atm vacuum degree, 60~65 DEG C
Condensing crystallizing, gained crystal use the isopropanol for accounting for crystal volume 15% to be eluted as eluent under centrifugal condition, so
Drying to constant weight in 85-90 DEG C in bipyramid vacuum oven (vacuum degree 0.08-0.09atm) afterwards, obtains stannous sulfate.Measure four
Valence Theil indices are 0.05%.
Embodiment 2, a kind of method for reducing tetravalence Theil indices in stannous sulfate production process:
The partial size D of tin grain50It is 10 μm；
The acetoxime as oxygen scavenger, dilute sulfuric acid after must handling are added in dilute sulfuric acid；The dosage of dilute sulfuric acid and oxygen scavenger
Than for 100ml/0.08g；
Control bath voltage is 2.0V；
Use acetone as eluent；
Remaining is equal to embodiment 1.
Tetravalence Theil indices are 0.04% in resulting stannous sulfate.
Embodiment 3, a kind of method for reducing tetravalence Theil indices in stannous sulfate production process:
The partial size D of tin grain50It is 1 μm；
The diamine as oxygen scavenger, dilute sulfuric acid after must handling are added in dilute sulfuric acid；The amount ratio of dilute sulfuric acid and oxygen scavenger
For 100ml/0.08g；
Control bath voltage is 1.8V；
Use butanone as eluent；
Remaining is equal to embodiment 1.
Tetravalence Theil indices are 0.07% in resulting stannous sulfate.
Embodiment 4, a kind of method for reducing tetravalence Theil indices in stannous sulfate production process:
The partial size D of tin grain50It is 5 μm；
The acetoxime as oxygen scavenger, dilute sulfuric acid after must handling are added in dilute sulfuric acid；The dosage of dilute sulfuric acid and oxygen scavenger
Than for 100ml/0.08g；
Control bath voltage is 2.0V；
Use isopropanol as eluent；
Remaining is equal to embodiment 1.
Tetravalence Theil indices are 0.03% in resulting stannous sulfate.
Embodiment 5, a kind of method for reducing tetravalence Theil indices in stannous sulfate production process:
The partial size D of tin grain50It is 2 μm；
The acetoxime as oxygen scavenger, dilute sulfuric acid after must handling are added in dilute sulfuric acid；The dosage of dilute sulfuric acid and oxygen scavenger
Than for 100ml/0.1g；
Control bath voltage is 1.9V；
Use isopropanol as eluent；
Remaining is equal to embodiment 1.
Tetravalence Theil indices are 0.01% in resulting stannous sulfate.
Comparative example 1, a kind of method for reducing tetravalence Theil indices in stannous sulfate production process:
Cancel the use of tin granulosa；
Oxygen scavenger is added in cancellation in dilute sulfuric acid, that is, directly uses dilute sulfuric acid；
Control bath voltage is 2.4V；
Cancel the use of eluent, that is, drying to constant weight in 85~90 DEG C directly in bipyramid vacuum oven by crystal；
Remaining is equal to embodiment 1.
Tetravalence Theil indices are 0.25% in resulting stannous sulfate.
Comparative example 2, a kind of method for reducing tetravalence Theil indices in stannous sulfate production process:
The partial size D of tin grain50It is 2 μm；
Oxygen scavenger is added in cancellation in dilute sulfuric acid, that is, directly uses dilute sulfuric acid；
Control bath voltage is 2.0V；
Cancel the use of eluent, that is, drying to constant weight in 85~90 DEG C directly in bipyramid vacuum oven by crystal；
Remaining is equal to embodiment 1.
Tetravalence Theil indices are 0.17% in resulting stannous sulfate.
Comparative example 3, a kind of method for reducing tetravalence Theil indices in stannous sulfate production process:
Cancel the use of eluent, that is, drying to constant weight in 85~90 DEG C directly in bipyramid vacuum oven by crystal；
Remaining is equal to embodiment 1.
Tetravalence Theil indices are 0.12% in resulting stannous sulfate.
Comparative example 4, a kind of method for reducing tetravalence Theil indices in stannous sulfate production process:
The partial size D of tin grain50It is 1000 μm；
The sodium dithionite as oxygen scavenger, dilute sulfuric acid after must handling are added in dilute sulfuric acid；Dilute sulfuric acid and oxygen scavenger
Amount ratio be 100ml/0.05g；
Control bath voltage is 2.4V；
Use methanol as eluent；
Remaining is equal to embodiment 1.
Tetravalence Theil indices are 0.19% in resulting stannous sulfate.
Comparative example 5, a kind of method for reducing tetravalence Theil indices in stannous sulfate production process:
The partial size D of tin grain50It is 100 μm；
The sodium sulfite as oxygen scavenger, dilute sulfuric acid after must handling are added in dilute sulfuric acid；The use of dilute sulfuric acid and oxygen scavenger
Amount is than being 100ml/0.05g；
Control bath voltage is 2.2V；
Use isopropanol as eluent；
Remaining is equal to embodiment 1.
Tetravalence Theil indices are 0.15% in resulting stannous sulfate.
Comparative example 6, a kind of method for reducing tetravalence Theil indices in stannous sulfate production process:
The partial size D of tin grain50It is 5 μm；
The acetoxime as oxygen scavenger, dilute sulfuric acid after must handling are added in dilute sulfuric acid；The dosage of dilute sulfuric acid and oxygen scavenger
Than for 100ml/0.09g；
Control bath voltage is 1.6V；
Use isopropanol as eluent；
Remaining is equal to embodiment 1.
Tetravalence Theil indices are 0.13% in resulting stannous sulfate.
Comparative example 7, a kind of method for reducing tetravalence Theil indices in stannous sulfate production process:
The partial size D of tin grain50It is 5 μm；
Oxygen scavenger is added in cancellation in dilute sulfuric acid, that is, directly uses dilute sulfuric acid；
Control bath voltage is 2.0V；
Use isopropanol as eluent；
Remaining is equal to embodiment 1.
Tetravalence Theil indices are 0.19% in resulting stannous sulfate.
Comparative example 8, a kind of method for reducing tetravalence Theil indices in stannous sulfate production process:
Cancel the use of tin granulosa；
The acetoxime as oxygen scavenger, dilute sulfuric acid after must handling are added in dilute sulfuric acid；The dosage of dilute sulfuric acid and oxygen scavenger
Than for 100ml/0.08g；
Control bath voltage is 2.0V；
Use butanone as eluent；
Remaining is equal to embodiment 1.
Tetravalence Theil indices are 0.11% in resulting stannous sulfate.
Comparative example 9, a kind of method for reducing tetravalence Theil indices in stannous sulfate production process:
Oxygen scavenger is changed to hydroquinone by acetoxime, content is constant；
Remaining is equal to embodiment 1.
Tetravalence Theil indices are 0.09% in resulting stannous sulfate.
Comparative example 10, a kind of method for reducing tetravalence Theil indices in stannous sulfate production process:
Oxygen scavenger is changed to β-phenol by acetoxime, content is constant；
Remaining is equal to embodiment 1.
Tetravalence Theil indices are 0.11% in resulting stannous sulfate.
Comparative example 11, a kind of method for reducing tetravalence Theil indices in stannous sulfate production process:
Oxygen scavenger is changed to phenylpropyl triazole by acetoxime, content is constant；
Remaining is equal to embodiment 1.
Tetravalence Theil indices are 0.10% in resulting stannous sulfate.
Table 1
The above list is only a few specific embodiments of the present invention for finally, it should also be noted that.Obviously, this hair
Bright to be not limited to above embodiments, acceptable there are many deformations.Those skilled in the art can be from present disclosure
All deformations for directly exporting or associating, are considered as protection scope of the present invention.
Claims (9)
1. the method for reducing tetravalence Theil indices in stannous sulfate, be respectively equipped in stannous sulfate electrolytic cell the cathode being used cooperatively and
Anode, stannous sulfate bottom of electrolytic tank are equipped with outlet；It is characterized in that including the following steps:
1), one layer of tin granulosa is laid at stannous sulfate electrolytic bath bottom；
2) oxygen scavenger, is added in dilute sulfuric acid, dilute sulfuric acid after must handling；The amount ratio of dilute sulfuric acid and oxygen scavenger is 100ml/0.05
~0.1g；
The dilute sulfuric acid is the sulfuric acid solution that concentration is 1 ± 0.1mol/L；
The oxygen scavenger is acetoxime, sodium dithionite, sodium sulfite, hydrazine；
3) dilute sulfuric acid after, addition is handled into stannous sulfate electrolytic cell, until dilute sulfuric acid liquid level did not had 2~4cm of cathode after processing,
Control bath voltage < 2.4V；
4), in the electrolyte at the stannous sulfate electrolytic bath slot bottom when tin ion content >=85g/L, from exit to slot outlet
Electrolyte is put, dilute sulfuric acid keeps tank liquor liquid level to former height after supplement process into slot while discharging electrolyte；
When tin ion content drops to 80g/L in electrolyte at the stannous sulfate electrolytic bath slot bottom, stop above-mentioned electrolyte
Discharge and processing after dilute sulfuric acid supplement；
5), collection step 4) discharge electrolyte, carry out condensing crystallizing, gained crystal is dry after being eluted using eluent,
Obtain stannous sulfate.
2. the method according to claim 1 for reducing tetravalence Theil indices in stannous sulfate, it is characterized in that:
Tin granulosa with a thickness of 1~4cm；The D of tin grain50It is 1~10 μm.
3. the method according to claim 2 for reducing tetravalence Theil indices in stannous sulfate, it is characterized in that:
The eluent is alcohols, ketone.
4. the method according to claim 3 for reducing tetravalence Theil indices in stannous sulfate, it is characterized in that:
The alcohols is isopropanol, and the ketone is acetone, butanone.
5. the method according to claim 3 for reducing tetravalence Theil indices in stannous sulfate, it is characterized in that:
Bath voltage is 1.8~2.2V.
6. the method according to claim 3 for reducing tetravalence Theil indices in stannous sulfate, it is characterized in that:
In the step 5), the electrolyte of collection carries out concentration knot at a temperature of 0.08~0.09atm vacuum degree, 60~65 DEG C
It is brilliant.
7. the method according to claim 6 for reducing tetravalence Theil indices in stannous sulfate, it is characterized in that:
In the step 5), crystal is eluted under centrifugal condition using eluent；Then in 85~90 DEG C of dryings under vacuum
To constant weight.
8. the method according to claim 7 for reducing tetravalence Theil indices in stannous sulfate, it is characterized in that: the eluent
Dosage is the 13~17% of crystal volume.
9. any method for reducing tetravalence Theil indices in stannous sulfate according to claim 1~8, it is characterized in that: tin grain
Partial size D50It is 2 μm；The acetoxime as oxygen scavenger, dilute sulfuric acid after must handling, dilute sulfuric acid and oxygen scavenger are added in dilute sulfuric acid
Amount ratio be 100ml/0.1g；Control bath voltage is 1.9V；Use isopropanol as eluent.
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| CN108754607A (en) * | 2018-06-12 | 2018-11-06 | 广东光华科技股份有限公司 | A kind of preparation method of electronic-grade sulfuric acid stannous crystal |
| CN114890456A (en) * | 2022-04-20 | 2022-08-12 | 柳州华锡有色设计研究院有限责任公司 | Method for deeply reducing stannic tin in stannous sulfate solution |
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| CN103014786A (en) * | 2013-01-22 | 2013-04-03 | 广州博泉环保材料科技有限公司 | Electroplating liquid, method for manufacturing same and tin plating process by applying electroplating liquid |
| CN105481005A (en) * | 2016-01-20 | 2016-04-13 | 广东光华科技股份有限公司 | Preparation method of reagent-grade stannous chloride dehydrate crystals |
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Denomination of invention: Methods for reducing the content of tin (IV) in Tin(II) sulfate Effective date of registration: 20230707 Granted publication date: 20190226 Pledgee: Taizhou Huangyan Sub branch of China Construction Bank Co.,Ltd. Pledgor: FINE CHEMICALS GROUP Co.,Ltd. Registration number: Y2023980047758 |