CN110578153A - Electrolyte for electrolytic refining of crude bismuth and electrolysis method - Google Patents
Electrolyte for electrolytic refining of crude bismuth and electrolysis method Download PDFInfo
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- CN110578153A CN110578153A CN201910831284.1A CN201910831284A CN110578153A CN 110578153 A CN110578153 A CN 110578153A CN 201910831284 A CN201910831284 A CN 201910831284A CN 110578153 A CN110578153 A CN 110578153A
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- 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
- C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
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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
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Abstract
The invention relates to an electrolyte for electrorefining crude bismuth and an electrolysis method. The electrolyte and the electrolysis method are clean and energy-saving. The invention adopts a brand-new methanesulfonic acid solution system as the electrolyte for electrolysis, the methanesulfonic acid solution system has the characteristics of obvious environmental protection advantage, high conductivity, high bismuth solubility, no oxidability, high stability, no volatile gas and the like, and simultaneously has high current efficiency and low energy consumption. In the traditional crude bismuth electrolytic refining process of a fluosilicic acid and chloride system, the requirement on Sb impurities in the anode plate is higher, but the requirement on the anode plate is lower, the allowable range of the Sb impurities is larger, and the method is particularly suitable for electrolytic refining of high-antimony crude bismuth.
Description
Technical Field
The invention relates to an electrolyte for electrorefining crude bismuth and an electrolysis method, belonging to the technical field of wet metallurgy.
Background
The bismuth electrorefining method comprises two methods, namely chloride electrolysis and silicofluoride electrolysis. The electrolysis of chloride adopts bismuth trichloride and hydrochloric acid aqueous solution as electrolyte. The silicofluoride uses bismuth silicofluoride and free silicofluoride aqueous solution as electrolyte. The crude bismuth is initially refined by fire method and then cast into anode, and the cathode is cast by precipitated bismuth. During electrolysis, bismuth is dissolved from the anode, enters into the electrolyte and is separated out at the cathode; elements more electronegative than bismuth such as lead, tin, antimony and bismuth are dissolved into the electrolyte together, but because the elements are difficult to reduce, the elements are not precipitated at the cathode generally; elements of more positive electrical properties than bismuth, such as arsenic, copper, gold, silver, etc., do not dissolve to form anode sludge, which adheres to the surface of the anode or sinks to the bottom of the cell. Therefore, for crude bismuth containing high contents of lead, arsenic, antimony and copper, it is necessary to partially remove the bismuth before electrolytic refining.
The method is mainly characterized in that chloride electrolytic refining is adopted in 50 ~ 60 s in China, but fire refining is adopted at present, and the method is mainly used for (1) lead ions accumulated in electrolyte in the chloride electrolytic process are not removed in a feasible method in the presence of a lead chloride complex ion solution, a common method adopting lead sulfate precipitation has a quite poor effect due to the fact that the electrolyte contains a large amount of chloride ions, lead sulfate precipitation is added into the chloride electrolyte, the concentration of the lead ions in the precipitated electrolyte still reaches 5-10 g/L, and lead is inevitably precipitated at a cathode in the high-concentration lead ion electrolyte, so that the impurities of bismuth and lead at the cathode exceed the standard, and (2) the electrolytic waste liquid after impurity accumulation cannot be treated and is discharged up to the standard due to the fact that heavy metal ions cannot be completely precipitated due to the fact that the electrolyte contains a large amount of chloride ions.
The refined bismuth electrolysis process can be carried out by using the bismuth fluosilicate-fluorosilicic acid solution as an electrolyte. But instead of the other end of the tubeThe crude bismuth electrolytic refining adopts a solution system consisting of silicofluoric acid and bismuth silicofluoride as electrolyte for electrolysis, and the electrolysis has the main defects that: (1) silicofluoric acid is volatile and decomposes into toxic HF and SiF4A large amount of acid mist is formed on a working site due to gas, the smell is unpleasant, and the harm to human bodies and the environment is very large; (2) the current density is low and is generally lower than 70A/m2The current efficiency is low, generally lower than 95%; (3) compared with a chloride system, the dissolving performance of the fluosilicic acid system to the anode bismuth in the electrolysis process is slightly poor, the anode surface is irregularly dissolved and passivated after long-time electrolysis, and the anode surface needs to be regularly rinsed.
Disclosure of Invention
Aiming at the defects of the prior art, one of the purposes of the invention is to provide the electrolyte for the electrolytic refining of the crude bismuth, which has obvious environmental protection advantages and is easy to obtain high current efficiency; the second object of the present invention is to provide an electrolysis method.
In order to solve the technical problems, the technical scheme of the invention is as follows:
An electrolyte for electrorefining crude bismuth comprises water, bismuth methanesulfonate and free methanesulfonic acid.
further, the electrolyte consists of water, bismuth methanesulfonate and free methanesulfonic acid.
Further, in the electrolyte, Bi3+The concentration of (A) is 40 ~ 200g/L, generally 45 ~ 150g/L, preferably 50 ~ 135g/L, and the concentration of free methanesulfonic acid is 40 ~ 300g/L, generally 45 ~ 250g/L, preferably 50 ~ 200 g/L.
Based on the same invention concept, the invention also provides an electrolysis method for the electrolytic refining of crude bismuth, which is characterized in that a cathode plate and an anode plate of crude bismuth to be refined are oppositely inserted into the electrolyte, direct current is introduced for electrolysis, and refined bismuth is obtained on the cathode plate.
Further, before the electrolysis is started, an additive is added into the electrolyte, wherein the additive is one or more of animal glue, polyethylene glycol, polypropylene glycol, lignosulfonate and sodium dodecyl sulfate, and preferably, 0.2 ~ 1.5.5 kg of the additive is added for every 1t of crude bismuth refined through electrolysis.
Further, during electrolysis, the cathode current density was controlled to 60 ~ 500A/m2Typically 100 ~ 400A/m2Preferably 150 ~ 400A/m2The distance between the anode plate and the cathode plate of the crude bismuth is 30 ~ 120mm, generally 40 ~ 100mm, and the temperature of the electrolyte is 20 ~ 60 ℃, generally 25-55 ℃.
Further, the circulation amount of the electrolyte is controlled to be 10 ~ 40L/min, generally 15 ~ 35L/min, during electrolysis.
Optionally, the circulation mode of the electrolyte is up-in-down-out or down-in-up-out.
Further, the electrolysis time was 2 ~ 8 days, and generally, the electrolysis time was 2 ~ 6 days.
Furthermore, in the crude bismuth anode plate, the content of Bi is more than or equal to 92wt%, the content of Pb is less than or equal to 3wt%, the content of S is less than or equal to 0.5wt%, the content of Ag is less than or equal to 0.5wt%, the content of Sb is less than or equal to 8 wt%, the content of As is less than or equal to 0.5wt%, and the sum of the contents of Bi, Pb, S, Ag, Sb and As does not exceed 100.
Further, the cathode plate is a stainless steel plate, a pure bismuth plate or a pure titanium plate.
During electrolysis, the electrode reaction is as follows:
Cathode: bi3+-3e=Bi（1）
Anode: h2O+2e=1/2O2+2H+（2）
The toxicity of methanesulfonic acid (MSA) in the electrolyte of the present invention is lower than that of hydrochloric acid and silicofluoric acid. Under normal conditions, the MSA aqueous solution does not generate any dangerous volatile chemical substances, thereby avoiding generating smog such as HF, HCl and the like, and being beneficial to storage, transportation and use. Meanwhile, the methanesulfonic acid is easy to biodegrade, finally forms sulfate and carbon dioxide, and has small harm to the environment. MSA also has good electrical conductivity and is able to better dissolve the metallic bismuth.
In a chloride system, the pressure for purifying and removing the impurities of the lead enriched in the electrolyte is higher, but in the methylsulfonic acid electrolyte system, the lead enriched in the electrolyte is easier to remove.
Compared with the prior art, the invention has the following beneficial effects:
1) The electrolyte and the electrolysis method are clean and energy-saving. The invention adopts a brand-new methanesulfonic acid solution system as the electrolyte for electrolysis, the methanesulfonic acid solution system has the characteristics of obvious environmental protection advantage (characteristic of easy biodegradation), high conductivity, high bismuth solubility, no oxidability, high stability, no volatile gas and the like, and simultaneously, the current efficiency is high and the energy consumption is low.
2) In the traditional electrolytic refining process of crude bismuth of a fluosilicic acid and chloride system, the requirements on impurities such as Sb in an anode plate are high, but the requirements on the anode plate are low, the dissolubility of antimony by methanesulfonic acid is low, the allowable range of the Sb impurities in the crude bismuth is large, and the electrolytic refining process is particularly suitable for the electrolytic refining of high-antimony crude bismuth.
Detailed Description
The following description describes alternative embodiments of the invention to teach one of ordinary skill in the art how to make and use the invention.
Example 1
In this example, the electrolyte of the methylsulfonic acid solution system for electrorefining crude bismuth is composed of water, bismuth methylsulfonate and free methylsulfonic acid, wherein Bi3+The concentration is 50g/L, and the concentration of the free methanesulfonic acid is 100 g/L.
The electrolytic method for refining crude bismuth by adopting the electrolyte comprises the following specific steps: will contain Bi3+The electrolyte with the concentration of 50g/L and the concentration of free methanesulfonic acid of 100g/L, the anode plate and the cathode plate of the crude bismuth to be refined are placed in an electrolytic tank, then direct current is introduced, and the cathode current density is controlled to be 200A/m2The distance between the anode plate and the cathode plate of the crude bismuth is 100mm, the temperature of the electrolyte is 20 ℃, a mixture additive of animal glue and lignosulfonate with the mass ratio of 1:1 is added into the electrolyte, the total amount of the additive is 1.5 kg/t.Bi, and the crude bismuth is electrolyzed for 7 days under the process parameter conditions to produce cathode bismuth and anode mud. Wherein the crude bismuth anode plate is a crude bismuth anode plate which is formed by preliminary impurity removal casting through a pyrogenic process and comprises the following components in percentage by massComprises the following components: bi94.3%, Pb1.48%, Ag0.29%, S<0.5%，Sb3%，As<0.34 percent and Cu0.11 percent; the cathode plate is a 316L stainless steel plate; the electrolyte circulation mode of the methyl sulfonic acid solution system is top-in bottom-out.
In this example, the cell voltage was 0.26V, the current efficiency was 99.1%, and the DC power consumption per 1t of refined bismuth produced by electrolysis was 100.9 kw.h.
Comparative example 1
In this comparative example, the electrolyte of the methylsulfonic acid solution system for the electrolytic refining of crude bismuth consisted of water, bismuth methylsulfonate and free methanesulfonic acid, where Bi is present3+The concentration is 30g/L and the concentration of the free methanesulfonic acid is 100 g/L.
The electrolytic method for refining crude bismuth by adopting the electrolyte comprises the following specific steps: will contain Bi3+30g/L electrolyte with free methanesulfonic acid concentration of 100g/L, an anode plate and a cathode plate of crude bismuth to be refined are placed in an electrolytic tank, then direct current is introduced, and the cathode current density is controlled to be 200A/m2the distance between the anode plate and the cathode plate of the crude bismuth is 100mm, the temperature of the electrolyte is 20 ℃, a mixture additive of animal glue and lignosulfonate with the mass ratio of 1:1 is added into the electrolyte, the total amount of the additive is 1.5 kg/t.Bi, and the crude bismuth is electrolyzed for 7 days under the process parameter conditions to produce cathode bismuth and anode mud. The crude bismuth anode plate is a crude bismuth anode plate which is formed by preliminary impurity removal casting through a pyrogenic process and comprises the following components in percentage by mass: bi94.3%, Pb1.48%, Ag0.29%, S<0.5%，Sb3%，As<0.34 percent and Cu0.11 percent; the cathode plate is a 316L stainless steel plate; the electrolyte circulation mode of the methyl sulfonic acid solution system is top-in bottom-out.
In this example, the cell voltage was 0.28V, the cathode current efficiency was 80.1%, and the DC power consumption per 1t of refined bismuth produced by electrolysis was 134.5 kw.h.
Example 2
In this example, the electrolyte of the methylsulfonic acid solution system for electrorefining crude bismuth is composed of water, bismuth methylsulfonate and free methylsulfonic acid, wherein Bi3+The concentration is 120g/L, and the concentration of free methanesulfonic acid is 50 g/L.
The electrolytic method for refining crude bismuth by adopting the electrolyte comprises the following specific steps: will containBi3+The electrolyte with the concentration of 120g/L and the concentration of free methanesulfonic acid of 50g/L, the anode plate and the cathode plate of the crude bismuth to be refined are placed in an electrolytic tank, then direct current is introduced, and the cathode current density is controlled to be 300A/m2And electrolyzing for 3 days under the condition of the process parameters that the distance between the crude bismuth anode plate and the crude bismuth cathode plate is 80mm, the temperature of the electrolyte is 50 ℃, and the mass ratio of the additive to the mixture of the animal glue, the lignosulfonate and the polyethylene glycol is 1:1:1, and the total amount of the additive is 0.8 kg/t.Bi, so as to produce cathode bismuth and anode mud. The crude bismuth anode plate is a crude bismuth anode plate which is formed by preliminary impurity removal casting through a pyrogenic process and comprises the following components in percentage by mass: bi94.0%, Pb1.1%, Ag0.33%, S<0.5 percent, Sb3.4 percent, As0.48 percent and Cu0.19 percent; the negative plate is a pure titanium plate; the electrolyte circulation mode of the methyl sulfonic acid solution system is top-in bottom-out.
In this example, the cell voltage was 0.35V, the current efficiency was 98.8%, and the DC power consumption per 1t of refined bismuth produced by electrolysis was 136.3 kw.h.
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. An electrolyte for electrorefining crude bismuth, which is characterized by comprising water, bismuth methanesulfonate and free methanesulfonic acid.
2. The electrolyte for electrorefining crude bismuth as claimed in claim 1, wherein the electrolyte is composed of water, bismuth methanesulfonate and free methanesulfonic acid.
3. the electrolyte solution for electrorefining crude bismuth according to claim 1 or 2, wherein in the electrolyte solution, Bi is contained3+The concentration of (A) is 40 ~ 200g/L, generally 45 ~ 150g/L, preferably 50 ~ 135g/L, and the concentration of free methanesulfonic acid is 40 ~ 300g/L, generally 45 ~ 250g/L, preferably 50 ~ 200 g/L.
4. An electrolysis method for electrorefining crude bismuth, which is characterized in that a cathode plate and an anode plate of crude bismuth to be refined are oppositely inserted into the electrolyte of any one of claims 1 to 3, and direct current is introduced for electrolysis, so that refined bismuth is obtained on the cathode plate.
5. An electrolysis method for electrorefining crude bismuth according to claim 4, wherein before the electrolysis, an additive is added into the electrolyte, wherein the additive is one or more of glue, polyethylene glycol, polypropylene glycol, lignosulfonate and sodium dodecyl sulfate, and preferably 0.2 ~ 1.5.5 kg of the additive is added for each 1t of crude bismuth in the electrorefining.
6. The electrolytic process for electrorefining crude bismuth according to claim 4, wherein the cathode current density is controlled to be 60 ~ 500A/m during electrolysis2The distance between the anode plate and the cathode plate of the crude bismuth is 30 ~ 120mm, and the temperature of the electrolyte is 20 ~ 60 ℃.
7. An electrolysis method according to claim 4, wherein the circulation amount of the electrolyte is controlled to 10 ~ 40L/min during the electrolysis.
8. An electrolysis process for electrorefining crude bismuth according to any one of claims 4 to 7, wherein the electrolysis time is 2 ~ 8 days.
9. An electrolysis process for electrorefining crude bismuth according to any one of claims 4 to 7, wherein in the crude bismuth anode plate, Bi is 92wt% or more, Pb is 3wt% or less, S is 0.5wt% or less, Ag is 0.5wt% or less, Sb is 8 wt% or less, As is 0.5wt% or less, and the sum of the contents of Bi, Pb, S, Ag, Sb, As does not exceed 100 wt%.
10. An electrolysis process for electrorefining bismuth matte according to any one of claims 4 to 7, wherein the cathode plate is a stainless steel plate, a pure bismuth plate or a pure titanium plate.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113293409A (en) * | 2021-05-28 | 2021-08-24 | 中南大学 | Method for preparing compact and flat bismuth metal through electrolysis |
| CN114277405A (en) * | 2021-12-30 | 2022-04-05 | 中南大学 | Method for preparing metal bismuth by adopting tandem diaphragm electrodeposition module |
| CN114318418A (en) * | 2021-12-30 | 2022-04-12 | 中南大学 | Method for preparing metal bismuth by adopting parallel diaphragm electrodeposition module |
| CN114525550A (en) * | 2022-01-07 | 2022-05-24 | 中南大学 | Methanesulfonic acid system electrolyte solution and method for preparing metal bismuth by using same and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5227046A (en) * | 1991-10-07 | 1993-07-13 | Unisys Corporation | Low temperature tin-bismuth electroplating system |
| US6103088A (en) * | 1997-10-22 | 2000-08-15 | Goldschmidt Ag. | Process for preparing bismuth compounds |
| CN104746098A (en) * | 2015-03-24 | 2015-07-01 | 昆明理工大学 | Electrolyte and method for electrolyzing and refining crude lead |
| CN105220187A (en) * | 2015-10-30 | 2016-01-06 | 无锡市嘉邦电力管道厂 | A kind of pulse plating method plating bismuth electroplate liquid and bismuth thin film |
| CN106521577A (en) * | 2015-09-09 | 2017-03-22 | 罗门哈斯电子材料有限责任公司 | Bismuth electroplating baths and methods of electroplating bismuth on a substrate |
| CN107177865A (en) * | 2017-06-13 | 2017-09-19 | 中南大学 | Process for separating lead and bismuth from high-bismuth lead alloy |
-
2019
- 2019-09-04 CN CN201910831284.1A patent/CN110578153B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5227046A (en) * | 1991-10-07 | 1993-07-13 | Unisys Corporation | Low temperature tin-bismuth electroplating system |
| US6103088A (en) * | 1997-10-22 | 2000-08-15 | Goldschmidt Ag. | Process for preparing bismuth compounds |
| CN104746098A (en) * | 2015-03-24 | 2015-07-01 | 昆明理工大学 | Electrolyte and method for electrolyzing and refining crude lead |
| CN106521577A (en) * | 2015-09-09 | 2017-03-22 | 罗门哈斯电子材料有限责任公司 | Bismuth electroplating baths and methods of electroplating bismuth on a substrate |
| CN105220187A (en) * | 2015-10-30 | 2016-01-06 | 无锡市嘉邦电力管道厂 | A kind of pulse plating method plating bismuth electroplate liquid and bismuth thin film |
| CN107177865A (en) * | 2017-06-13 | 2017-09-19 | 中南大学 | Process for separating lead and bismuth from high-bismuth lead alloy |
Non-Patent Citations (2)
| Title |
|---|
| 云正宽: "《冶金工程设计 第2册 工艺设计》", 30 June 2006, 冶金工业出版社 * |
| 曲胜利: "《黄金冶金新技术》", 31 July 2018, 冶金工业出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113293409A (en) * | 2021-05-28 | 2021-08-24 | 中南大学 | Method for preparing compact and flat bismuth metal through electrolysis |
| US11913128B2 (en) | 2021-05-28 | 2024-02-27 | Central South University | Compact and flat bismuth metal preparation by electrolysis method |
| CN114277405A (en) * | 2021-12-30 | 2022-04-05 | 中南大学 | Method for preparing metal bismuth by adopting tandem diaphragm electrodeposition module |
| CN114318418A (en) * | 2021-12-30 | 2022-04-12 | 中南大学 | Method for preparing metal bismuth by adopting parallel diaphragm electrodeposition module |
| CN114318418B (en) * | 2021-12-30 | 2024-01-26 | 中南大学 | Method for preparing metal bismuth by adopting parallel diaphragm electrodeposition module |
| CN114525550A (en) * | 2022-01-07 | 2022-05-24 | 中南大学 | Methanesulfonic acid system electrolyte solution and method for preparing metal bismuth by using same and application thereof |
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