CN112941565A - Preparation method of high-purity tin - Google Patents
Preparation method of high-purity tin Download PDFInfo
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- CN112941565A CN112941565A CN202110205951.2A CN202110205951A CN112941565A CN 112941565 A CN112941565 A CN 112941565A CN 202110205951 A CN202110205951 A CN 202110205951A CN 112941565 A CN112941565 A CN 112941565A
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 79
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000005028 tinplate Substances 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 5
- 239000012498 ultrapure water Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 59
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000002738 chelating agent Substances 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 230000010287 polarization Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- BZOVBIIWPDQIHF-UHFFFAOYSA-N 3-hydroxy-2-methylbenzenesulfonic acid Chemical compound CC1=C(O)C=CC=C1S(O)(=O)=O BZOVBIIWPDQIHF-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 229920001429 chelating resin Polymers 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000011049 filling Methods 0.000 abstract description 3
- 210000004027 cell Anatomy 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000012535 impurity Substances 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 7
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
Abstract
A preparation method of high-purity tin comprises the following steps: first electrolysis preparation: firstly, injecting a sulfuric acid solution into an electrolytic cell, wherein the solvent of the sulfuric acid solution is ultrapure water, then placing a crude tin plate in the sulfuric acid solution in the electrolytic cell to be used as an anode, then placing a conductive plate into a diaphragm bag, after the conductive plate is placed into the diaphragm bag, the top end of the conductive plate is higher than the top bag opening of the diaphragm bag, then placing the diaphragm bag in the sulfuric acid solution in the electrolytic cell, and then fully filling the diaphragm bag with the sulfuric acid solution, wherein at the moment, the conductive plate is a cathode; first electrolysis: firstly, connecting the thick tin plate and the conductive plate with the positive and negative electrodes of a direct current power supply respectively, then starting the power supply and adjusting the current density to carry out electrolysis, and stopping the electrolysis until the tin concentration in the electrolytic bath reaches 50-80g/L, wherein the liquid in the electrolytic bath is tin solution. The design has the advantages of low energy consumption, high capacity and high production efficiency.
Description
Technical Field
The invention relates to the field of inorganic compound preparation methods, in particular to a preparation method of high-purity tin, which is mainly suitable for solving the problems of high energy consumption, low productivity and low production efficiency.
Background
Tin is a metal element, an inorganic substance, white tin in a common form is a low-melting-point metal with silvery white luster, and high-purity tin is a novel metal material, is widely applied to aspects of alloy manufacturing in aerospace, semiconductor materials in electronic information and the like, and becomes a key material for supporting high-tech development of human beings.
The invention discloses a preparation method of high-purity tin, which is provided by the invention patent with the publication number of CN102296189A and the publication date of 2011, 12 and 28, wherein the preparation method of the high-purity tin is advanced in process technology, high in generation efficiency, high in purity of the prepared high-purity tin, low in impurity content, capable of meeting the needs of the electronic industry and widely applied, but the following defects still exist: the distillation mode is high in energy consumption, low in yield, long in time required in the whole distillation process, low in production efficiency, high in impurity content of the prepared high-purity tin, and pollution caused by the reduced chemical product.
Disclosure of Invention
The invention aims to overcome the defects and problems of high energy consumption, low capacity and low production efficiency in the prior art, and provides a preparation method of high-purity tin with low energy consumption, high capacity and high production efficiency.
In order to achieve the above purpose, the technical solution of the invention is as follows: a preparation method of high-purity tin comprises the following steps:
first electrolysis preparation: firstly, injecting a sulfuric acid solution into an electrolytic cell, wherein the solvent of the sulfuric acid solution is ultrapure water, then placing a crude tin plate in the sulfuric acid solution in the electrolytic cell to be used as an anode, then placing a conductive plate into a diaphragm bag, after the conductive plate is placed into the diaphragm bag, the top end of the conductive plate is higher than the top bag opening of the diaphragm bag, then placing the diaphragm bag in the sulfuric acid solution in the electrolytic cell, and then fully filling the diaphragm bag with the sulfuric acid solution, wherein at the moment, the conductive plate is a cathode;
first electrolysis: firstly, respectively connecting a thick tin plate and a conductive plate to the positive electrode and the negative electrode of a direct-current power supply, then starting the power supply and adjusting the current density to carry out electrolysis, and stopping the electrolysis until the concentration of tin in an electrolytic bath reaches 50-80g/L, wherein the liquid in the electrolytic bath is a tin solution;
second electrolysis preparation: firstly, taking out the tin solution obtained in the first electrolysis, placing the tin solution in a beaker, taking out the tin solution, then taking out the electrolytic bath as an empty bath, adding a polarizing agent, a chelating agent A, an antioxidant and a filtering agent into the beaker, uniformly stirring to obtain a mixed solution, then placing the mixed solution until the mixed solution turns from turbid to clear, filtering to obtain a clear solution, then returning the clear solution to the electrolytic bath, then placing the crude tin plate after the first electrolysis in a diaphragm bag to be used as an anode, after placing, enabling the top end of the crude tin plate to be higher than the top bag opening of the diaphragm bag, then filling the chelating agent A into the diaphragm bag, and then placing a conductive plate in the clear solution in the electrolytic bath to be used as a cathode;
and (3) second electrolysis: and respectively connecting the crude tin plate and the conductive plate with the positive electrode and the negative electrode of a power supply, turning on the power supply, adjusting the current density to carry out continuous electrolysis, collecting the product tin precipitated on the conductive plate, and cleaning and drying the product tin to obtain the high-purity tin.
The concentration of the sulfuric acid solution in the first electrolytic preparation is 150-200 g/L.
The current density in the first electrolysis is 100-120A/m2。
The current density in the second electrolysis is 60-90A/m2。
The polarization agent in the second electrolysis preparation is sodium chloride, and the concentration of the polarization agent is 0.02-0.1 g/L; the chelating agent is 201-7 chelating resin, and the concentration of the chelating agent is 0.5-1L/L.
The antioxidant in the second electrolytic preparation is cresolsulfonic acid or an organic reagent with reducing groups such as phenolic hydroxyl groups, the concentration of the organic reagent is 0.1-0.5g/L, and the filtering agent is analytically pure activated carbon powder, and the concentration of the filtering agent is 5-10 g/L.
The conductive plate in the first electrolysis preparation is any one of a graphite plate, a titanium plate (foil), a stainless steel plate and a platinum wire.
The purity of the crude tin plate in the first electrolytic preparation was 99%.
The purity of the high-purity tin in the second electrolysis is more than 99.999 percent.
The distance between the part of the conductive plate connected with the power supply and the part of the thick tin plate connected with the power supply is 2-6 cm.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method of the high-purity tin comprises the steps of preparing the electrolyte, carrying out first electrolysis to obtain a tin solution, adding the polarizing agent, the chelating agent A, the antioxidant and the filtering agent to remove impurities, carrying out second electrolysis to obtain the high-purity tin, and extracting the high-purity tin by two electrolysis methods. Therefore, the invention has low energy consumption, large capacity and high production efficiency.
2. In the preparation method of the high-purity tin, the high-purity tin is obtained by liquid preparation and two-time electrolysis, the whole preparation process is short, fractionation and purification are not needed, the operation is simple and convenient in the liquid preparation and electrolysis processes, the high-purity tin is conveniently prepared, the operation environment is easy to obtain, the adaptability of the high-purity tin preparation is improved, the high-purity tin preparation is more convenient, the concentration of a sulfuric acid solution in the first electrolysis preparation is 150-200g/L, the tin divalent ions are prevented from being hydrolyzed, the purity of an electrolysis product tin is improved, the hydrogen evolution phenomenon caused by direct dissolution of a crude tin plate is avoided, and the current density in the first electrolysis is 100-120A/m2The current density in the second electrolysis is 60-90A/m2The current density in the first electrolysis is convenient to prepare the tin solution quickly, the production efficiency is further improved, and the small current density is used for the second electrolysis, so that the cell voltage is convenient to control, and impurity ions with similar electrochemical potentials are separated. Therefore, the method has the advantages of short flow, simple and convenient operation and wide adaptability.
3. In the preparation method of the high-purity tin, the high-purity tin is prepared by two-time electrolysis, compared with the existing chlorination method, the method has the advantages that the requirement on raw materials is lower, the raw materials are easy to obtain, numerous complicated chemical processes such as oxidation, chlorination and reduction electrolysis are not needed, the produced metal compounds, waste water and waste gas are less, the influence on the environment is smaller, the method is more friendly to the surrounding environment, the resource utilization rate is high, the labor productivity is improved, and the prepared high-purity tin has higher purity by the two-time electrolysis preparation method. Therefore, the invention is environment-friendly and has higher tin purity.
Drawings
FIG. 1 is a schematic view of the first electrolysis structure of the present invention.
FIG. 2 is a schematic view of the second electrolysis structure of the present invention.
In the figure: the electrolytic bath comprises an electrolytic bath 1, a sulfuric acid solution 2, a crude tin plate 3, a diaphragm bag 4, a conductive plate 5 and a clarifying solution 6.
Detailed Description
The present invention will be described in further detail with reference to the following description and embodiments in conjunction with the accompanying drawings.
Referring to fig. 1 to 2, a method for preparing high purity tin, the method comprising the steps of:
first electrolysis preparation: firstly, injecting a sulfuric acid solution 2 into an electrolytic cell 1, wherein the solvent of the sulfuric acid solution 2 is ultrapure water, then placing a crude tin plate 3 into the sulfuric acid solution 2 in the electrolytic cell 1 to be used as an anode, then placing a conductive plate 5 into a diaphragm bag 4, after the crude tin plate is placed, the top end of the conductive plate 5 is higher than the top bag opening of the diaphragm bag 4, then placing the diaphragm bag 4 into the sulfuric acid solution 2 in the electrolytic cell 1, and then pouring the sulfuric acid solution 2 into the diaphragm bag 4, wherein the conductive plate 5 is a cathode, the electrolytic cell 1 is a 200 x 200mm organic glass cell, and the diaphragm bag 4 is of a U-shaped structure;
first electrolysis: firstly, respectively connecting the crude tin plate 3 and the conductive plate 5 with the positive electrode and the negative electrode of a direct current power supply, then starting the power supply and adjusting the current density to carry out electrolysis, and stopping the electrolysis until the tin concentration in the electrolytic bath 1 reaches 50-80g/L, wherein the liquid in the electrolytic bath 1 is tin solution;
second electrolysis preparation: firstly, taking out the tin solution obtained in the first electrolysis, placing the tin solution in a beaker, taking out the tin solution, then placing an electrolytic tank 1 which is an empty tank, adding a polarizing agent, a chelating agent A, an antioxidant and a filtering agent into the beaker, uniformly stirring to obtain a mixed solution, then placing the mixed solution for 30min until the mixed solution is clear from turbidity, filtering to obtain a clear solution 6, then returning the clear solution 6 to the electrolytic tank 1, then placing a crude tin plate 3 after the first electrolysis in a diaphragm bag 4 to be used as an anode, after placing, enabling the top end of the crude tin plate 3 to be higher than a top bag opening of the diaphragm bag 4, then pouring the chelating agent A into the diaphragm bag 4, and then placing a conductive plate 5 in the clear solution 6 in the electrolytic tank 1 to be used as a cathode;
and (3) second electrolysis: firstly, respectively connecting the coarse tin plate 3 and the conductive plate 5 with the positive electrode and the negative electrode of a direct current power supply, then starting the power supply and adjusting the current density for electrolysis, collecting tin products precipitated on the conductive plate 5 in the electrolysis process, cleaning and drying the tin products to obtain high-purity tin, and filtering the electrolyte at intervals.
The concentration of sulfuric acid solution 2 in the first electrolytic preparation is 150-200 g/L.
The current density in the first electrolysis is 100-120A/m2。
The current density in the second electrolysis is 60-90A/m2。
The polarization agent in the second electrolysis preparation is sodium chloride, and the concentration of the polarization agent is 0.02-0.1 g/L; the chelating agent is 201-7 chelating resin, and the concentration of the chelating agent is 0.5-1L/L.
The antioxidant in the second electrolytic preparation is cresolsulfonic acid or an organic reagent with reducing groups such as phenolic hydroxyl groups, the concentration of the organic reagent is 0.1-0.5g/L, and the filtering agent is analytically pure activated carbon powder, and the concentration of the filtering agent is 5-10 g/L.
The conductive plate 5 in the first electrolysis preparation is any one of a graphite plate, a titanium plate (foil), a stainless steel plate and a platinum wire.
The purity of the crude tin plate 3 in the first electrolytic preparation was 99%, and the size of the crude tin plate 3 was 200 × 8 mm.
The purity of the high-purity tin in the second electrolysis is more than 99.999 percent.
The distance between the part of the conductive plate 5 connected with the power supply and the part of the thick tin plate 3 connected with the power supply is 2-6 cm.
The principle of the invention is illustrated as follows:
the design mainly comprises the steps of preparing electrolyte, carrying out first electrolysis to obtain a tin solution, adding a polarizing agent, a chelating agent A, an antioxidant and a filtering agent to remove impurities, carrying out second electrolysis to obtain high-purity tin, and extracting the high-purity tin by two electrolysis modes.
When the electrolyte is prepared, the concentration of the sulfuric acid solution is 150-200g/L, the hydrolysis of tin divalent ions is avoided, the hydrolysis of the tin divalent ions can occur when the concentration is lower than 150g/L, the tin purity of an electrolysis product is influenced, the direct dissolution of the anode tin plate by acid can be caused when the concentration is higher than 200g/L, and a serious hydrogen evolution phenomenon is caused at the same time, wherein the electrolysis density of the first electrolysis is 100-120A/m2Is used for preparing electrolyte rapidly, and the electrolyte is higher than 120A/m2Lead ion concentration is too high, the current density is lower than the lead ion concentration, copper or nickel ion concentration is too high, and the second electrolysis density is 60-90A/m2The method is to conveniently control the cell voltage to further separate impurity ions with similar electrochemical potentials, stop electrolysis after the tin concentration reaches 50-80g/L in the first electrolysis, calculate the required time according to the theoretical electrolysis equivalent, thereby judging whether the tin concentration of the first electrolysis reaches 50-80g/L, the tin ion concentration is more than 80g/L to cause the cell voltage to rise, so that the impurity ions are separated out and the power consumption is increased, the ion concentration is less than 50g/L to cause the probability of separating out the ions with similar potentials to increase, so that the content of the impurity ions is increased, the distance between a conductive plate and a crude tin plate is 2-6cm, when the distance is more than 6cm, the impurity ions with similar electrochemical potentials are easily separated out, a diaphragm with the distance of less than 2cm is easy to be pierced by grown tin dendrites to cause short circuit, and the electrolyte is filtered at the middle interval of 12h in the second electrolysis process, thereby reusing the filtered filtrate and further ensuring the normal operation of electrolytic purification.
Example 1:
referring to fig. 1 to 2, preparing a 200 x 200mm organic glass tank as an electrolytic tank, adding 2.5L of water into a 5L beaker, slowly adding 1000g of sulfuric acid along the cup wall, continuously stirring, finally supplementing to 5L, cooling the prepared sulfuric acid solution to room temperature, and pouring the solution into the electrolytic tank; placing the crude tin plate in an electrolytic tank, connecting the crude tin plate with a positive electrode of a direct-current power supply, then manufacturing an anion diaphragm bag, placing a graphite plate in the anion diaphragm bag, and integrally placing the graphite plate in the electrolytic tank; pouring a sulfuric acid solution into a part of the diaphragm bag, and connecting the graphite plate with the negative electrode of the direct-current power supply; is connected withAfter the connection is finished, the direct current power supply is started, and the current density is adjusted to be 100A/m2Electrolyzing for 3.5h to obtain a tin solution with the concentration of 70 g/L; after obtaining a tin solution, transferring the solution to a beaker, adding 0.25g of sodium chloride, 2.5L of 201X 7 resin, 1g of cresolsulfonic acid and 25g of activated carbon, stirring for 5min, standing for 30min, and returning the filtered solution to an electrolytic cell; placing the crude tin plate used for liquid making in a newly prepared anion diaphragm bag, adding 2.5L of 201 x 7 resin again, and connecting the crude tin plate with the positive electrode of a power supply; placing titanium foil in an electrolytic bath to serve as a cathode plate and be connected with a power supply cathode, and keeping the distance between the coarse tin plate and the titanium foil to be 4 cm; turning on the power supply, regulating the current density to 80A/m2Starting electrolysis, continuing the electrolysis for 48h (extracting and filtering the electrolyte once every 12 h), and then collecting the product tin on the titanium foil; the obtained tin was washed twice with hydrochloric acid having an acidity of 0.5 and then with ultrapure water, and then dried in an oven of 80 ° and subjected to GDMS detection on the sample after the drying, and the following results were obtained.
Note: sn-05 Sn-06 Sn-07 is an industry standard for tin of 99.999%, 99.9999%, 99.99999%, with units in the table being ppm, sample 1 being a sample of the product of example 1.
Example 2:
the basic contents are the same as example 1, except that:
referring to fig. 1 to 2, firstly, a coarse tin plate is placed in an electrolytic bath and connected with a positive electrode of a direct current power supply, then an anion diaphragm bag is manufactured, a graphite plate is placed in the anion diaphragm bag, and the whole tin plate is placed in the electrolytic bath; then pouring sulfuric acid solution into a part of the diaphragm bag, connecting the graphite plate with the negative electrode of a direct current power supply, starting the direct current power supply after the connection is finished, and adjusting the current density to 120A/m2Electrolyzing for 3 hours to obtain a tin solution with the concentration of 80 g/L; after obtaining a tin solution, transferring the solution to a beaker, adding 0.5g of sodium chloride, 5L of 201 x 7 resin, 2g of cresolsulfonic acid and 50g of activated carbon, stirring for 5min, standing for 30min, and filtering the solution to return to an electrolytic cell; placing the crude tin plate used for liquid making in the new preparationAdding 2.5L of 201X 7 resin into the anion diaphragm bag again, and connecting the anion diaphragm bag with the positive electrode of a power supply; placing titanium foil in an electrolytic bath to serve as a cathode plate and be connected with a power supply cathode, and keeping the distance between the coarse tin plate and the titanium foil to be 4 cm; turning on the power supply, regulating the current density to 60A/m2After the electrolysis was started and the drying was completed, the GDMS detection was performed on the sample, and the following results were obtained.
Note: sn-05 Sn-06 Sn-07 is an industry standard for tin of 99.999%, 99.9999%, 99.99999%, with units in the table being ppm, sample 2 being a sample of the product of example 2.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above embodiment, but equivalent modifications or changes made by those skilled in the art according to the present disclosure should be included in the scope of the present invention as set forth in the appended claims.
Claims (10)
1. The preparation method of the high-purity tin is characterized by comprising the following steps of:
first electrolysis preparation: firstly, injecting a sulfuric acid solution (2) into an electrolytic tank (1), wherein the solvent of the sulfuric acid solution (2) is ultrapure water, then placing a crude tin plate (3) into the sulfuric acid solution (2) in the electrolytic tank (1) to be used as an anode, then placing a conductive plate (5) into a diaphragm bag (4), after the conductive plate is placed, the top end of the conductive plate (5) is higher than the top bag opening of the diaphragm bag (4), then placing the diaphragm bag (4) into the sulfuric acid solution (2) in the electrolytic tank (1), then pouring the sulfuric acid solution (2) into the diaphragm bag (4), and at the moment, the conductive plate (5) is a cathode;
first electrolysis: firstly, respectively connecting a coarse tin plate (3) and a conductive plate (5) with the positive and negative electrodes of a direct-current power supply, then starting the power supply and adjusting the current density to carry out electrolysis until the concentration of tin in the electrolytic bath (1) reaches 50-80g/L, and then stopping electrolysis, wherein the liquid in the electrolytic bath (1) is a tin solution;
second electrolysis preparation: firstly, taking out the tin solution obtained in the first electrolysis, placing the tin solution in a beaker, taking out the tin solution, then placing an electrolytic tank (1) as an empty tank, adding a polarizing agent, a chelating agent A, an antioxidant and a filtering agent into the beaker, uniformly stirring to obtain a mixed solution, then placing the mixed solution until the mixed solution turns from turbid to clear, filtering to obtain a clear solution (6), then returning the clear solution (6) to the electrolytic tank (1), then placing a crude tin plate (3) after the first electrolysis in a diaphragm bag (4) to be used as an anode, after placing, the top end of the crude tin plate (3) is higher than the top bag opening of the diaphragm bag (4), then pouring the chelating agent A into the diaphragm bag (4), and then placing a conductive plate (5) in the clear solution (6) in the electrolytic tank (1) to be used as a cathode;
and (3) second electrolysis: firstly, respectively connecting the crude tin plate (3) and the conductive plate (5) with the positive and negative electrodes of a direct current power supply, then starting the power supply and adjusting the current density for electrolysis, collecting the product tin precipitated on the conductive plate (5) in the electrolysis process, and cleaning and drying the product tin to obtain high-purity tin.
2. The method for preparing high-purity tin according to claim 1, wherein the method comprises the following steps: the concentration of the sulfuric acid solution (2) in the first electrolytic preparation is 150-200 g/L.
3. The method for preparing high purity tin according to claim 1 or 2, characterized in that: the current density in the first electrolysis is 100-120A/m2。
4. The method for preparing high purity tin according to claim 1 or 2, characterized in that: the current density in the second electrolysis is 60-90A/m2。
5. The method for preparing high purity tin according to claim 1 or 2, characterized in that: the polarization agent in the second electrolysis preparation is sodium chloride, and the concentration of the polarization agent is 0.02-0.1 g/L; the chelating agent is 201-7 chelating resin, and the concentration of the chelating agent is 0.5-1L/L.
6. The method for preparing high-purity tin according to claim 5, characterized in that: the antioxidant in the second electrolytic preparation is cresolsulfonic acid or an organic reagent with reducing groups such as phenolic hydroxyl groups, the concentration of the organic reagent is 0.1-0.5g/L, and the filtering agent is analytically pure activated carbon powder, and the concentration of the filtering agent is 5-10 g/L.
7. The method for preparing high purity tin according to claim 1 or 2, characterized in that: the conductive plate (5) in the first electrolysis preparation is any one of a graphite plate, a titanium plate (foil), a stainless steel plate and a platinum wire.
8. The method for preparing high purity tin according to claim 1 or 2, characterized in that: the purity of the crude tin plate (3) in the first electrolytic preparation was 99%.
9. The method for preparing high purity tin according to claim 1 or 2, characterized in that: the purity of the high-purity tin in the second electrolysis is more than 99.999 percent.
10. The method for preparing high purity tin according to claim 1 or 2, characterized in that: the distance between the part of the conductive plate (5) connected with the power supply and the part of the thick tin plate (3) connected with the power supply is 2-6 cm.
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