CN108374194A - Method for removing iron ions in tinning solution and using system - Google Patents
Method for removing iron ions in tinning solution and using system Download PDFInfo
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- CN108374194A CN108374194A CN201810162314.XA CN201810162314A CN108374194A CN 108374194 A CN108374194 A CN 108374194A CN 201810162314 A CN201810162314 A CN 201810162314A CN 108374194 A CN108374194 A CN 108374194A
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- plating solution
- tin plating
- ion
- solution
- ion exchange
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 53
- -1 iron ions Chemical class 0.000 title claims abstract description 51
- 238000007747 plating Methods 0.000 claims abstract description 159
- 229910052718 tin Inorganic materials 0.000 claims abstract description 113
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 111
- 150000002500 ions Chemical class 0.000 claims abstract description 70
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 47
- 150000001768 cations Chemical class 0.000 claims abstract description 44
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 35
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 35
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001514 detection method Methods 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 63
- 238000010521 absorption reaction Methods 0.000 claims description 46
- 238000005342 ion exchange Methods 0.000 claims description 38
- 239000013049 sediment Substances 0.000 claims description 12
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 238000006722 reduction reaction Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000003795 desorption Methods 0.000 claims description 7
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 2
- 229930003268 Vitamin C Natural products 0.000 claims description 2
- 230000003750 conditioning effect Effects 0.000 claims description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 2
- 235000019154 vitamin C Nutrition 0.000 claims description 2
- 239000011718 vitamin C Substances 0.000 claims description 2
- 210000000952 spleen Anatomy 0.000 claims 1
- 210000002784 stomach Anatomy 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 11
- 238000001179 sorption measurement Methods 0.000 abstract description 11
- 239000011347 resin Substances 0.000 description 22
- 229920005989 resin Polymers 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000005028 tinplate Substances 0.000 description 11
- 238000003860 storage Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- AICMYQIGFPHNCY-UHFFFAOYSA-J methanesulfonate;tin(4+) Chemical compound [Sn+4].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O AICMYQIGFPHNCY-UHFFFAOYSA-J 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical group [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 150000005837 radical ions Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/16—Regeneration of process solutions
- C25D21/22—Regeneration of process solutions by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/30—Electroplating: Baths therefor from solutions of tin
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention provides a method and a using system for removing iron ions in a tinning solution, wherein the method comprises the following steps: passing a tin plating solution through an ion exchange resin, wherein metal cations in the tin plating solution are adsorbed by the ion exchange resin, and the ion exchange resin is a strong acid cation exchange resin; detecting the concentration of cations in the adsorbed tin plating solution, and finishing adsorption when the concentration of the cations is detected to be 1-5% of the concentration of the cations in the tin plating solution before adsorption; the cation comprises Sn2+Ions and Fe2+Ions; and when the adsorption is finished, desorbing the ion exchange resin adsorbed with the tin plating solution by using a sulfuric acid solution to obtain a regenerated solution. The method can be used for removing the iron ions in the tinning solution in the environment-friendly MSA tinning process, and can realize the removal of Sn in the tinning solution2+Ions and Fe2+the ion concentration detection shows that the removal rate of iron ion impurities in the plating solution is more than 80 percent, and the concentration of the iron ions in the tin plating solution is kept within 10 g/L all the time.
Description
Technical field
The invention belongs to the production technical field of metallurgy industry tin plate, more particularly to it is a kind of for iron in tin plating solution from
The method and use system that son removes.
Background technology
Tin plate is the main packaging material of food packaging industry, with the development of China's modernization, people's life water
Flat also increasingly to improve, the application range and dosage of tin plate are growing, and the type and kind of wherein packing material also increasingly increase
Add, people also increasingly improve the quality requirement of tin plate thus, and the clean-up performance of compactness and surface to tin coating proposes
Higher requirement.
The production of tin plate both at home and abroad is generally using sulfate type Acidic Bright Tin Plating Process at present.The technique has
Current efficiency is high, liberation of hydrogen is few, deposition rate is fast, current density range is wide, and tin plating solution ingredient is simple, raw material is easy to get, cost
The advantages that cheap.In sulfate pickling tin plating technique, since there are one to steel strip substrate for highly acid tin plating solution and pickle
Fixed corrosiveness, band steel corrosion generates ferrous ion and enters tin plating solution, and is accumulated in tin plating solution, causes tin plating
Iron concentration is substantially increased in solution, after the iron concentration in tin plating solution is more than to a certain degree, will make coating
Corrosion resistance, solderability and soft heat glossiness etc. substantially reduce；Sn in the tin plating solution of iron ion catalysis simultaneously2+Ion is to Sn4+From
The conversion of son forms tin mud, causes tin plating solution muddy, reduces the generation of the compactness and coating surface grey black of coating.Therefore
The iron ion content reduced in tin plating solution is most important to the corrosion resistance and surface quality of tin plate.To ensure the matter of tin coating
Amount, a large amount of research and practical production experience prove that the iron concentration in tin plating solution is not more than 10g/L.
The method that iron ions are gone in the solution of electrotinning mainly has：The precipitation method, freezing removal method etc. are several.
The precipitation method：The precipitation method be exactly a certain number of precipitating reagents are added in tin plating solution, by precipitating reagent with it is tin plating molten
Foreign ion reaction in liquid, generates the sediment for being insoluble in water, and by removing sediment, reaching reduces impurity in tin plating solution
The effect of ion.In tin plating solution, the movable metallic of iron and tin sequence close, the divalent and tetravalence hydrogen of tin in tin plating solution
The solubility product constant of oxide is far smaller than the solubility product constant of the divalent and trivalent hydroxide of corresponding iron, therefore with precipitation
Method inevitably results in a large amount of consumption of tin when removing iron.PH value by improving tin plating solution will be so that tin plating solution
Ingredient change, therefore the method cannot obtain satisfactory effect.
Freezing：In the tin plating solution containing iron ion, the acid energy in the relatively low tin plating solution of temperature and iron
Sediment can be formed, the method can effectively remove the iron ion in tin plating solution, will not be brought into solution any miscellaneous
Matter is small to the damage of tin plating solution.According to the feature of tin plating solution, the sediment in tin plating solution to be enable smoothly to be precipitated.
But this method can typically be only used to PSA tin plating solution systems, not be suitable for MSA tin plating solution systems.
Invention content
In view of the above-mentioned drawbacks in the prior art, the main purpose of the present invention is to provide one kind for iron in tin plating solution
The method of ion remaval and use system, using ion-exchange process, the iron ion that can effectively reduce in MSA tin plating solutions contains
Amount, iron ion removal of impurity is 80% or more.
In order to achieve the above object, the present invention adopts the following technical scheme that：One kind is removed for iron ions in tinplating solution
Method, include the following steps：
By tin plating solution by ion exchange resin, the metal cation in the tin plating solution is ion exchanged resin suction
Attached, the ion exchange resin is that strong acid washes cation exchange resin；
The cation concn in the tin plating solution after the absorption is detected, when detecting that the cation concn reaches absorption
In preceding tin plating solution cation concn 1~5% when, absorption complete；The cation includes Sn2+Ion and Fe2+Ion；
When the absorption is completed, the ion exchange resin after absorption tin plating solution is desorbed using sulfuric acid solution, is obtained again
Raw liquid.
As a further preference, flow control ranging from 5~10m/ that the tin plating solution passes through ion exchange resin
h。
As a further preference, the sulfuric acid concentration is 3~4N, and the speed that the sulfuric acid passes through ion exchange resin is
1~3m/h.
As a further preference, the method further includes：
The cation concn in the regenerated liquid is detected, the tin plating solution before detecting the cation concn less than absorption
Middle cation concn 10~30% when, desorption complete, it is described cation include Sn2+Ion and Fe2+Ion；
Ion exchange resin after the desorption is reused for the absorption of tin plating solution.
As a further preference, the method further includes：
Reducing agent is added in the regenerated liquid, the reducing agent is selected from sodium sulfite, sodium pyrosulfite, hydrazine hydrate and dimension
Raw element C.
As a further preference, the method further includes：
The pH value of the regenerated liquid is adjusted to 4.0~5.0, obtains Sn (OH)2Solid sediment；
By the Sn (OH)2Solid sediment rejoins the tin plating solution after ion exchange resin absorption
In, restore Sn in tin plating solution2+The concentration of ion.
A kind of use system for iron ions in tinplating solution removal, including：
Ion exchange column is adsorbed for tin plating solution circulation；
Tin plating solution collector unit, is connected to ion exchange column, for collecting the tin plating solution after adsorbing；
First ion concentration detection unit, is connected to respectively with tin plating solution collector unit and ion exchange column, for detecting
Cation concn after the absorption in tin plating solution；
Regenerated liquid collector unit, for collecting the regenerated liquid obtained through sulfuric acid maldi ion exchange column.
As a further preference, the system also includes：Second ion concentration detection unit, respectively with the regenerated liquid
Collector unit is connected to ion exchange column, for detecting the cation concn in the regenerated liquid.
As a further preference, the system also includes：Reduction reaction unit connects with the regenerated liquid collector unit
It is logical, reduction reaction occurs with reducing agent for accommodating regenerated liquid.
As a further preference, the system also includes：PH value adjust unit, with the regenerated liquid collector unit or also
Former reaction member connection carries out pH value adjusting for accommodating regenerated liquid and PH conditioning agents.
As a further preference, the system also includes：Separative element adjusts unit with the pH value and is connected to, is used for
Detach the sediment in the regenerated liquid after pH value is adjusted.
The beneficial effects of the invention are as follows：The method that the present invention is used for iron ions in tinplating solution removal, includes the following steps：
By tin plating solution by ion exchange resin, the metal cation in the tin plating solution is ion exchanged resin adsorption, described
Ion exchange resin is that strong acid washes cation exchange resin；The cation concn in the tin plating solution after the absorption is detected, when
When detecting 1~5% of the cation concn before the cation concn reaches absorption in tin plating solution, absorption is completed；It is described
Cation includes Sn2+Ion and Fe2+Ion；When the absorption is completed, the ion exchange resin after absorption tin plating solution is used
Sulfuric acid solution desorbs, and obtains regenerated liquid, ensure that the exchange capacity and efficiency of ion exchange resin；The present invention can be used for environment-friendly type
MSA tin plating techniques in tin plating solution iron ion removing, the present invention using ion exchange technique removal plating solution in iron ion,
Realize the purification of plating solution；And Sn in plating solution may be implemented2+Ion and Fe2+Iron ion in plating solution is realized in the detection of ion concentration
Impurity effectively removes, and iron ion removal of impurity is 80% or more.The concentration of iron ion in tin plating electrolyte always 10g/L with
It is interior, a generation for rust class defect is avoided, the corrosion resistance and surface quality of tin plate are substantially increased, it is tin plating for production high-quality
Plate is laid a good foundation.
Description of the drawings
Fig. 1 is the system structure diagram that the embodiment of the present invention 1 is used for iron ions in tinplating solution removal.
Fig. 2 is the system structure diagram that the embodiment of the present invention 2 is used for iron ions in tinplating solution removal.
What is marked in attached drawing is described as follows：Pump is added in 1- plating solution storage tanks, 2- plating solutions, and 3- flowmeters, 4- ion exchange columns enter
Expect valve, 5- ion exchange column outlet valves, 6- ion exchange columns, 7- sulfuric acid storage tanks, 8- ion exchange column exhaust-valves, the first ions of 9-
Concentration detecting unit, 10- the second ion concentration detection units, 11- regenerated liquid collector units, 12- reduction reaction units, 13 reduction
Agent storage tank, 14-pH values adjust unit, 15- alkali liquor storage tanks, 16- separative elements, 17- plating solution collector units, 18- filter presses, 19-
Deposition generator, 20- settling tanks.
Specific implementation mode
The present invention solves existing MSA by providing a kind of method and system for iron ions in tinplating solution removal
The defect that iron ion cannot be removed effectively in the plating solution of tin plating technique.
In order to solve drawbacks described above, the main thought of the embodiment of the present invention is：
The method that the embodiment of the present invention is used for iron ions in tinplating solution removal, includes the following steps：
By tin plating solution by ion exchange resin, the metal cation in the tin plating solution is ion exchanged resin suction
Attached, the ion exchange resin is that strong acid washes cation exchange resin；
The cation concn in the tin plating solution after the absorption is detected, when detecting that the cation concn reaches absorption
Cation concn in preceding tin plating solution 1~5% when, absorption is completed；The cation includes Sn2+Ion and Fe2+Ion；
When the absorption is completed, the ion exchange resin after absorption tin plating solution is desorbed using sulfuric acid solution, is obtained again
Raw liquid.
5~10m/h of flow control range that above-mentioned tin plating solution passes through ion exchange resin.
Above-mentioned sulfuric acid concentration is 3~4N, and the speed that the sulfuric acid passes through ion exchange resin is 1~3m/h.
The system that the embodiment of the present invention is used for iron ions in tinplating solution removal, including：
Ion exchange column is adsorbed for tin plating solution circulation；
Tin plating solution collector unit, is connected to ion exchange column, for collecting the tin plating solution after adsorbing；
First ion concentration detection unit, is connected to respectively with tin plating solution collector unit and ion exchange column, for detecting
Cation concn after the absorption in tin plating solution；
Regenerated liquid collector unit, for collecting the regenerated liquid obtained through sulfuric acid maldi ion exchange column.
It confirms, is applied to using present invention method and system tin plating molten in MSA tin plating techniques through practical application
In liquid, the removal of iron ion impurity in plating solution, iron of the iron ion removal of impurity in 80% or more, tin plating electrolyte are effectively realized
The concentration of ion is always within 10g/L；In addition, can handle regenerated liquid so that Sn2+The consumption of ion is below 5%.
In order to which above and other purpose, feature and the advantage of the present invention can be clearer and more comprehensible, number cited below particularly is implemented
Example carrys out the method and system for iron ions in tinplating solution removal described in the present invention will be described in detail.
Embodiment 1
The system that the embodiment of the present invention is used for iron ions in tinplating solution removal, including：Ion exchange column, tin plating solution are received
Collect unit, the first ion concentration detection unit, regenerated liquid collector unit and relevant component, specifically as shown in Figure 1, including：
Pump 2, flowmeter 3, ion exchange column pan feeding valve 4, ion exchange column outlet valve 5, ion exchange column is added in plating solution storage tank 1, plating solution
6, sulfuric acid storage tank 7, ion exchange column exhaust-valve 8, the first ion concentration detection unit 9, the second ion concentration detection unit 10, then
Raw liquid collector unit 11, plating solution collector unit 17 etc..
The method that the embodiment of the present invention is used for iron ions in tinplating solution removal, includes the following steps：
1) iron-containing tin plating solution is driven by flowmeter 3 equipped with cation exchange tree from plating bath tank 1 through plating liquid pump 2
The ion exchange column absorption tower of fat, tin plating solution (or plating solution) enters from the bottom of ion exchange column 6, from ion exchange column 6
Top is flowed out, and for all metal cations in plating solution by resin adsorption, the plating solution after ion exchange resin adsorbs passes through overflow
Return to plating solution collector unit 17, the flow control range 10m/h that plating solution passes through resin.
2) ion exchange resin of absorption is that strong acid washes cation exchange resin, which is Shanghai Hua Zhen companies
The HZ016 strong cation-exchanging resins of production.
3) after cationic exchange resin adsorption, plating solution detects plating solution through online first ion concentration detection unit 9, inspection
It surveys by the Sn in absorption plating solution2+Ion and Fe2+Ion, after the first ion concentration detection unit 9 detects absorption in plating solution
Sn2+Ion and Fe2+It after ion reaches the 5% of former plating solution, is defined as absorption and completes, resin adsorption saturation, resin needs to carry out again
It is raw.
4) above-mentioned ion exchange resin is regenerated by sulfuric acid, and the sulfuric acid concentration of regeneration is 3N concentration.Regeneration sulphur
Acid is squeezed by metering pump from the bottom of ion exchange column 6 from sulfuric acid storage tank 8, and regenerated liquid is flowed out from the top of ion exchange column 6,
Regenerated liquid is detected through online second ion concentration detection unit 10, when detecting Sn in regenerated liquid2+Ion and Fe2+Ion concentration
After the 10% of former plating solution, it is defined as desorption and completes, resin can be reused for the absorption of plating solution.Sulfuric acid passes through ion exchange column
Speed be 1m/h.
5) the plating solution cation of ion exchange column absorption, most ion enters sulfuric acid solution after sulfuric acid desorbs,
Major metal salt is ferric sulfate and STANNOUS SULPHATE CRYSTALLINE in actified solution.
In addition, can also handle regenerated liquid, the present embodiment system may also include：Reduction reaction unit, pH value are adjusted
Unit, separative element and their associated components, such as the reduction reaction unit 12 in Fig. 1, reducing agent storage tank 13, pH value are adjusted
Unit 14, alkali liquor storage tank 15, separative element (centrifugal separator) 16 etc..
Correspondingly, present invention method may also include the steps of：
6) due to the Sn in regenerated liquid2+And Fe2+All it is the metal ion easily aoxidized, to prevent these Ion cups from aoxidizing,
Removal effect is influenced, needs that a certain amount of reducing agent is added in regenerated liquid, available reducing agent is：Sodium sulfite, coke
Sodium sulfite, hydrazine hydrate, vitamin C, the present embodiment are selected as hydrazine hydrate.
7) regenerated liquid carries out the adjusting of pH value in pH value adjusts unit 14 using sodium hydroxide solution, for adjusting regeneration
A concentration of the 30% of the sodium hydroxide solution of liquid is driven into pH value by metering pump and adjusts tank, and pH value adjusts tank band agitating device,
Suitable mixing speed is 40rpm.Sodium hydroxide solution is added continuously in regenerated liquid, 4.0, at this moment the pH value of solution controls
Sn in solution2+With OH-Ionic reaction generates Sn (OH)2Precipitation, and the Fe in solution at this time2+Still it is present in ionic condition
In solution.
8) regenerated liquid after pH value is adjusted enters centrifugal separator 16 (i.e. separative element) by way of overflow, leads to
The Sn ion concentrations crossed in the clear liquid that the regenerated liquid after pH value is adjusted is obtained by centrifugal separation unit are less than 1000ppm, Fe2+From
Sub- concentration is more than 40000ppm, the waste water treatment system of the solution discharge such as factory.
9) sediment in centrifugal separator 16, the filter press 18 connected by tank bottom, the solids after press filtration directly add
Entering to plating solution collector unit 17, solids is reacted in the state of stirring with absorption plating solution, and tin methane sulfonate is generated, this
Tin plating solution tank is returned to after solution is qualified after testing, participates in the cycle of tin plating electrolyte.
Embodiment 2
Certain tin plating unit produces ferrostan using MSA soluble anodes, and the design production capacity of unit is to produce 400000 tons per year
Tin plate, the concentration of the iron ion in tin plating electrolyte is always in 16g/L or more, since the volume iron concentration in plating solution surpasses always
Mark, on tin-plated product quality, there are serious influences, and the defect of appearance point rust class, cannot be satisfied the life of high-quality tin plate often
At requiring, the present embodiment method and system is used to tin plating electrolyte handle except iron thus.
Unit circulating bath amount is about 80m3, to ensure that plating solution removes the effect of iron, the plating liquid measure extracted from bath trough is
3m3/ h, such basic guarantee can be by plating solution circulation primaries in 24 hours.
As shown in Fig. 2, the present embodiment system shares three radical ion exchange columns, 1 pillar is for adsorbing in the course of work, separately
Two pillars are then desorbing.System is controlled using PLC, automatically switches solenoid valve according to the plating solution ion concentration detected by PLC,
Realize pillar from the switching being adsorbed onto between desorption.
In conjunction with attached system shown in Fig. 2, the present embodiment method includes the following steps：
1) iron-containing tin plating solution enters from the bottom of ion exchange column 6, is flowed out from the top of ion exchange column 6, plating solution
In all metal cations by resin adsorption, plating solution after ion exchange resin adsorbs by overflow return to plating solution collect it is single
Member 17.Plating solution is chosen to be 5m/h by the flow velocity of resin, and a diameter of 500mm of ion exchange column, ion are determined according to the flow velocity
The height of exchange column is 5000mm.
2) ion exchange resin of absorption is that strong acid washes cation exchange resin, and resin selects the production of Shanghai Hua Zhen companies
HZ016 strong cation-exchanging resins.
3) plating solution after cationic exchange resin adsorption, through Shanghai Wu Bao Electromechanical Technology Co., Ltd develop it is online from
Sub- detector (the first ion concentration detection unit 9) detection is by the Sn in absorption plating solution2+And Fe2+Ion, when ion detection instrument is examined
Measure the Sn in plating solution after adsorbing2+And Fe2+After ion reaches the 1% of stoste, show that resin adsorption is saturated, resin enters row
Regeneration stage.
4) regeneration of resin is using the sulfuric acid of a concentration of 4N, and regeneration sulfuric acid is from sulfuric acid storage tank 7 by metering pump from ion
The bottom of exchange column is squeezed into, and regenerated liquid is flowed out from the top of ion exchange column, and the regenerated liquid of top outflow is through online ion concentration
Detector (the second ion concentration detection unit 10) detects, when detecting Sn and Fe ion concentrations in regenerated liquid less than stoste
After 30%, the at this moment desorption of resin is completed, and resin can be reused for the absorption of plating solution.
5) regenerated liquid carries out the adjusting of pH value, hydrogen in pH value adjusts unit 14 using the sodium hydroxide solution of 30% concentration
Sodium oxide molybdena is driven into pH value by metering pump and adjusts unit, and the mixing speed for adjusting agitating paddle in unit is 60rpm, sodium hydroxide
Pump is added in solution and pH meter is chain, by the control of the pH value of regenerated liquid between 1.8~2.0, the regenerated liquid after pH value is adjusted
By overflowing to deposition generator 19.
7) solution that unit overflow goes out is adjusted from pH value, it is molten that a concentration of 30% sodium sulfite is added by pipe-line mixer
Liquid, addition are the 5% of regenerated liquid total flow.
8) regenerated liquid of sodium sulfite solution is added in deposition generator 19, continues through sodium hydroxide and adjusts pH value,
The pH value of solution is adjusted to 4.5, the mixing speed of agitating paddle is 60rpm in deposition generator 19, at this moment Sn in solution2+With
OH-Ionic reaction generates the precipitation of Sn (OH) 2, and solution is creamy white.
9) regenerated liquid after pH value is adjusted enters settling tank 20 by way of overflow, this solution is in settling tank
Heart down-comer flows into, the Sn (OH) of solid2It is deposited in the bottom of settling tank 20, supernatant is flowed by way of overflow from top
Go out, the Sn ion concentrations in supernatant are less than 1000ppm, Fe2+Ion concentration is more than 40000ppm, the solution discharge such as factory
Waste water treatment system.
10) sediment in settling tank 20, by the filter press 18 of pot bottom, the solids after press filtration is added directly into plating
Liquid collector unit 17, solids are reacted in the state of stirring with absorption plating solution, and tin methane sulfonate, this solution warp are generated
Tin plating solution tank is returned to after detection is qualified, participates in the cycle of tin plating electrolyte.
This system can fast implement the removal of iron ion impurity in plating solution, and iron ion removal of impurity is 90%, Sn2+From
The consumption of son is 3%.
Technical solution in above-mentioned the embodiment of the present application, at least has the following technical effect that or advantage：
The method that the present invention is used for iron ions in tinplating solution removal, includes the following steps：Tin plating solution is passed through into ion
Exchanger resin, the metal cation in the tin plating solution are ion exchanged resin adsorption, and the ion exchange resin is strong acid
Wash cation exchange resin；The cation concn in the tin plating solution after the absorption is detected, when detecting that the cation is dense
When degree reaches 1~5% of the cation concn in the preceding tin plating solution of absorption, absorption is completed；The cation includes Sn2+Ion and
Fe2+Ion；When the absorption is completed, the ion exchange resin after absorption tin plating solution is desorbed using sulfuric acid solution, is obtained again
Raw liquid, ensure that the exchange capacity and efficiency of ion exchange resin；The plating that the present invention can be used in the MSA tin plating techniques of environment-friendly type
Solution of tin iron ion removing, the present invention realize the purification of plating solution using the iron ion in ion exchange technique removal plating solution；And
Sn in plating solution may be implemented2+Ion and Fe2+The detection of ion concentration realizes that iron ion impurity effectively removes in plating solution, iron from
Sub- removal of impurity is 80% or more.The concentration of iron ion in tin plating electrolyte within 10g/L, avoids a rust class defect always
Generation, substantially increase the corrosion resistance and surface quality of tin plate, lay a good foundation for production high-quality tin plate.
It should be noted last that the above specific implementation mode is merely illustrative of the technical solution of the present invention and unrestricted,
Although being described the invention in detail with reference to example, it will be understood by those of ordinary skill in the art that, it can be to the present invention
Technical solution be modified or replaced equivalently, without departing from the spirit of the technical scheme of the invention and range, should all cover
In the scope of the claims of the present invention.
Claims (10)
1. a kind of method for iron ions in tinplating solution removal, it is characterised in that：Include the following steps：
By tin plating solution by ion exchange resin, the metal cation in the tin plating solution is inhaled by the ion exchange resin
Attached, the ion exchange resin is that strong acid washes cation exchange resin；
The cation concn in the tin plating solution after the absorption is detected, the plating before detecting that the cation concn reaches absorption
In solution of tin cation concn 1~5% when, absorption complete；The cation includes Sn2+Ion and Fe2+Ion；
When the absorption is completed, the ion exchange resin after absorption tin plating solution is desorbed using sulfuric acid solution, obtains regenerated liquid.
2. the method according to claim 1 for iron ions in tinplating solution removal, it is characterised in that：It is described tin plating molten
Flow control ranging from 5~10m/h that liquid passes through ion exchange resin.
3. the method according to claim 1 for iron ions in tinplating solution removal, it is characterised in that：The method is also
Including：
The cation concn in the regenerated liquid is detected, the tin plating solution middle-jiao yang, function of the spleen and stomach before detecting the cation concn less than absorption
Ion concentration 10~30% when, desorption complete, it is described cation include Sn2+Ion and Fe2+Ion；
Ion exchange resin after the desorption is reused for the absorption of tin plating solution.
4. the method according to claim 1 for iron ions in tinplating solution removal, it is characterised in that：The method is also
Including：
Reducing agent is added in the regenerated liquid, the reducing agent is selected from sodium sulfite, sodium pyrosulfite, hydrazine hydrate and vitamin
C。
5. the method according to claim 1 or 4 for iron ions in tinplating solution removal, it is characterised in that：The side
Method further includes：
The pH value of the regenerated liquid is adjusted to 4.0~5.0, obtains Sn (OH)2Solid sediment；
By the Sn (OH)2Solid sediment rejoins in the tin plating solution after ion exchange resin absorption, restores
Sn in tin plating solution2+The concentration of ion.
6. the use system of the method as described in any one in claim 1-5 for iron ions in tinplating solution removal, special
Sign is：Including：
Ion exchange column is adsorbed for tin plating solution circulation；
Tin plating solution collector unit, is connected to ion exchange column, for collecting the tin plating solution after adsorbing；
First ion concentration detection unit, is connected to tin plating solution collector unit and ion exchange column respectively, described for detecting
Cation concn after absorption in tin plating solution；
Regenerated liquid collector unit, for collecting the regenerated liquid obtained through sulfuric acid maldi ion exchange column.
7. the use system of the method according to claim 6 for iron ions in tinplating solution removal, it is characterised in that：
The system also includes：Second ion concentration detection unit is connected to the regenerated liquid collector unit and ion exchange column respectively,
For detecting the cation concn in the regenerated liquid.
8. the use system of the method according to claim 6 for iron ions in tinplating solution removal, it is characterised in that：
The system also includes：Reduction reaction unit is connected to the regenerated liquid collector unit, is sent out with reducing agent for accommodating regenerated liquid
Raw reduction reaction.
9. the use system of the method for iron ions in tinplating solution removal according to claim 6 or 8, feature exist
In：The system also includes：PH value adjusts unit, is connected to the regenerated liquid collector unit or reduction reaction unit, for holding
Receiving regenerated liquid and PH conditioning agents carries out pH value adjusting.
10. the use system of the method according to claim 9 for iron ions in tinplating solution removal, feature exist
In：The system also includes：Separative element adjusts unit with the pH value and is connected to, for detaching the regenerated liquid after pH value is adjusted
In sediment.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810162314.XA CN108374194A (en) | 2018-02-27 | 2018-02-27 | Method for removing iron ions in tinning solution and using system |
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| CN201810162314.XA CN108374194A (en) | 2018-02-27 | 2018-02-27 | Method for removing iron ions in tinning solution and using system |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| 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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