CN114959796B - Additive for electrolytic manganese metal and application of additive in electrolytic manganese - Google Patents
Additive for electrolytic manganese metal and application of additive in electrolytic manganese Download PDFInfo
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- CN114959796B CN114959796B CN202210546646.4A CN202210546646A CN114959796B CN 114959796 B CN114959796 B CN 114959796B CN 202210546646 A CN202210546646 A CN 202210546646A CN 114959796 B CN114959796 B CN 114959796B
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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
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
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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
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention provides an additive for electrolytic manganese metal and application thereof in electrolytic manganese, wherein the additive for electrolytic manganese metal is an ionic liquid containing an imidazole structure, and the ionic liquid containing the imidazole structure is a monosubstituted, disubstituted or trisubstituted imidazole ionic liquid. The application of the additive for electrolytic manganese metal in electrolytic manganese comprises the following steps: preparing a mixed solution of manganese sulfate, ammonium sulfate and an ionic liquid containing an imidazole structure; ammonia water is adopted to adjust the pH value to 7-7.8; lead alloy is used as an anode, a stainless steel plate is used as a cathode in a diaphragm electrolytic tank, and electrolysis is performed after current, voltage and temperature are regulated; and after the electrolysis is completed, passivating and cleaning the metal manganese of the cathode and then stripping. The method solves the problem of industrial application, and has the advantages of no environmental pollution, high purity of manganese metal, high current efficiency and the like.
Description
Technical Field
The invention relates to the technical field of preparation of anode materials of manganese electrolytic tanks, in particular to an additive for electrolytic manganese metal and application of the additive in electrolytic manganese.
Background
Manganese metal has wide application, in the iron and steel industry, manganese is used in an amount which is inferior to iron, 90% of manganese is used in the iron and steel industry, and 10% of manganese is used in nonferrous metallurgy, chemical industry, electronics, batteries, agriculture and other industries. The manganese ore resources in China are rich, and the reserves are large, and are mainly distributed in areas such as Guangxi, hunan, chongqing and Guizhou. In the process of electrolytic manganese, the power consumption of electrolytic manganese production is an important index, and the traditional process adopts the addition of SeO2 or SO2 to improve the current efficiency.
The domestic enterprises generally add the additive SeO 2 But SeO 2 Is easy to generate a series of hydrolysis reactions, seO 2 Can promote manganese electrolysis reaction and inhibit hydrogen evolution reaction, and hydrolyze SeO in electrolyte 2 Added to the electrolyte to dissolve, and used in the following problems: (1) according to international researches on selenium toxicity and toxicity, excessive selenium intake by human body can cause selenium poisoning, which is manifested by fatigue, emesis, dysphoria, alopecia, nail drop, nervous system injury, liver cirrhosis, pulmonary edema, coordination weakening, paralysis, nervous system disorder, and serious even death; for other organisms in nature, excessive selenium intake can cause nervous system disorders, and fish and waterfowl in water environment can be deformed or even die; (2) selenium dioxide can form selenium sediment to block the diaphragm in the electrolytic process, so that the process operation is affected; (3) selenium dioxide is reduced at a cathode, and forms alloy with manganese to enter a product, so that the purity and quality of the product are affected; (4) part of selenium is remained in the waste water, anode mud and manganese slag of electrolytic manganese, which causes environmental pollution.
SO is adopted in the process of electrolytic manganese by some foreign manufacturers 2 As an additive, SO 2 The following problems mainly exist as additives: (1) its overpotential increases less than that of SeO 2 The hydrogen evolution reaction is easy to cause, the current efficiency is lower, and the production cost is higher; (2) the metal manganese is not easy to deposit in the early stage of electrolysis, and the requirements on the polishing treatment of a cathode plate and the management level of the electrolysis process are high. (3) SO in the electrolytic process 2 Gas evolution causes deterioration of the plant environment.
Electrolytic experiments are carried out on the Jishou university by adopting thiophene organic matters containing sulfur heteroatoms as additives; chongqing university Sun Dagui adopts low-content SO 2 As main additive, 5 kinds of auxiliary additives A, B, C, D, E are added, and the deposited manganese crystal form is alpha-Mn; yang Weijun from Hunan university adopts a composite additive consisting of 50g/L sodium citrate and 40mg/L sodium thiosulfate to electrolyze manganese metal; the compound additive of thiourea and organic matter Y screened by the university of south and middle school Yang Ping can be used as the electrolytic manganese additive.
In the prior art, related industrial application is not seen, the imidazole ionic liquid is used as an additive in the electrolytic manganese process, and the method has the advantages of no environmental pollution, high purity of metal manganese and the like.
Disclosure of Invention
The invention provides an additive for electrolytic manganese metal and application thereof in electrolytic manganese, which solves the problem of industrial application.
In order to solve the problems, one of the purposes of the invention is to provide an additive for electrolytic manganese metal, which is an ionic liquid containing an imidazole structure, wherein the ionic liquid containing the imidazole structure is a mono-substituted, di-substituted and tri-substituted imidazole ionic liquid.
The invention also provides an application of the additive for electrolytic manganese metal in electrolytic manganese, which comprises the following steps:
s1: preparing a mixed solution of manganese sulfate, ammonium sulfate and an ionic liquid containing an imidazole structure;
s2: ammonia water is adopted to adjust the pH value to 7-7.8;
s3: lead alloy is used as an anode, a stainless steel plate is used as a cathode in a diaphragm electrolytic tank, and electrolysis is performed after current, voltage and temperature are regulated;
s4: and after the electrolysis is completed, passivating and cleaning the metal manganese of the cathode and then stripping.
Further, the ionic liquid containing the imidazole structure is one or more of the combination of the ionic liquid containing the imidazole structure, namely the ionic liquid containing the imidazole structure is mono-substituted, di-substituted and tri-substituted imidazole ionic liquid.
Further, the concentration of manganese ions in the manganese sulfate is 5-50g/L, the concentration of ammonium sulfate is 40-140g/L, and the concentration of the imidazole ionic liquid is 0.01-3g/L.
Further, the cell voltage is 3-6V and the cathode current density is 250-400A/m2.
Further, the electrolysis temperature is 10-60 ℃.
Further, the electrolysis time is 6-48h.
The one or more technical schemes of the invention have the following technical effects:
the additive for electrolytic manganese metal and the application thereof in electrolytic manganese solve the industrial application problem and have the following technical advantages: (1) the imidazole ionic liquid containing the imidazole structure has higher ionic conductivity, wider electrochemical window, good thermal stability and chemical stability, no hydrogen and other gases are generated in the electrolysis process, certain catalytic activity is realized, the metal manganese deposition is catalyzed, and the current efficiency is higher; (2) relative to additive SeO 2 And SO 2 The saturated vapor pressure of the ionic liquid containing the imidazole structure is almost zero, the ionic liquid is not volatilized, and the environment is not polluted; (3) the ionic liquid with the imidazole structure has large heat capacity, the temperature is stable and easy to control in the electrolysis process, and the process conditions are stable; (4) the ionic liquid containing the imidazole structure is used as an additive, so that the solubility of various metal salts can be improved, the viscosity is low, and the space-time yield and the current efficiency are improved; (5) the ionic liquid containing the imidazole structure does not contain sulfur and selenium element, has no pollution to metal manganese, and the purity of the metal manganese is not less than 99.9 percent, thereby reaching the high-purity standard.
Drawings
FIG. 1 is a flow chart of the application of an additive for electrolytic manganese metal in electrolytic manganese;
FIG. 2 is an SEM image of manganese metal of example 1 of the present invention;
FIG. 3 is an EDS spectrum of manganese metal of example 1 of the present invention;
fig. 4 is an XRD pattern of manganese metal according to example 1 of the present invention.
Detailed Description
The embodiment of the invention provides an additive for electrolytic manganese metal and application thereof in electrolytic manganese, solves the problem of industrial application, and has the advantages of no environmental pollution, high purity of manganese metal, high current efficiency and the like.
In order to make the objects and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following examples and the accompanying drawings, 1 and 4. It should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
Preparing a mixed solution of manganese sulfate, ammonium sulfate and 1-butyl-3-methylimidazole chloride, wherein the concentration of manganese ions is 35g/L, the concentration of ammonium sulfate is 110g/L, the concentration of 1-butyl-3-methylimidazole chloride is 0.09g/L, regulating the pH value to 7.5 by ammonia water, using lead alloy as an anode and a stainless steel plate as a cathode in a diaphragm electrolytic tank, and regulating the current density to 360A/m 2 The cell voltage is 5.1V, electrolysis is carried out at 40 ℃ for 6 hours, the metal manganese of the cathode is subjected to passivation cleaning and then stripping weighing, the current efficiency is calculated to be 64.7%, and the purity of the metal manganese is measured to be 99.9%.
Example 2
Preparing a mixed solution of manganese sulfate, ammonium sulfate and 1-butyl-3-methylimidazole chloride, wherein the concentration of manganese ions is 35g/L, the concentration of ammonium sulfate is 110g/L, the concentration of 1-butyl-3-methylimidazole chloride is 0.09g/L, regulating the pH value to 7.5 by ammonia water, using lead alloy as an anode and a stainless steel plate as a cathode in a diaphragm electrolytic tank, and regulating the current density to 390A/m 2 The cell voltage is 5.23V, electrolysis is carried out at 40 ℃ for 6 hours, the metal manganese of the cathode is subjected to passivation cleaning and then stripping weighing, the current efficiency is calculated to be 62.0%, and the purity of the metal manganese is measured to be 99.9%.
Example 3
Preparing a mixed solution of manganese sulfate, ammonium sulfate, 1-ethyl-2, 3-dimethyl imidazole chloride and 1-butyl-3-methyl imidazole chloride, wherein the concentration of manganese ions is 40g/L, the concentration of ammonium sulfate is 100g/L, the concentration of the mixed solution of 1-ethyl-2, 3-dimethyl imidazole chloride and 1-butyl-3-methyl imidazole chloride is 0.12g/L, regulating the pH value to 7.5 by ammonia water,in the diaphragm electrolytic tank, lead alloy is used as anode, stainless steel plate is used as cathode, and current density is regulated to 360A/m 2 And (3) carrying out electrolysis at the tank voltage of 5.0V and the temperature of 42 ℃ for 24 hours, passivating and cleaning the metal manganese of the cathode, then stripping and weighing, and calculating the current efficiency to be 67% and the purity of the metal manganese to be 99.9%.
Example 4
Preparing a mixed solution of manganese sulfate, ammonium sulfate, 1-butyl-3-methylimidazole chloride and 1-ethyl-2, 3-dimethylimidazole chloride, wherein the concentration of manganese ions is 40g/L, the concentration of ammonium sulfate is 120g/L, the concentration of the mixed solution of 1-butyl-3-methylimidazole chloride and 1-ethyl-2, 3-dimethylimidazole chloride is 0.15g/L, regulating the pH value to be 7.5 by ammonia water, taking lead alloy as an anode and stainless steel plates as cathodes in a diaphragm electrolytic tank, and regulating the current density to be 380A/m 2 And (3) carrying out electrolysis at the cell voltage of 5.1V and the temperature of 40 ℃ for 24 hours, passivating and cleaning the metal manganese of the cathode, then stripping and weighing, and calculating the current efficiency to be 70 percent and the purity of the metal manganese to be 99.9 percent.
Claims (1)
1. The application of the additive for electrolyzing metal manganese in the electrolytic manganese is characterized by comprising the following steps:
s1: preparing manganese sulfate solution with manganese ion concentration of 5-50g/L, ammonium sulfate concentration of 40-140g/L, 1-butyl-3-methylimidazole, 1-ethyl-2, 3-dimethylimidazole chloride salt mixture or 1-butyl-3-methylimidazole chloride salt and 1-ethyl-2, 3-dimethylimidazole chloride salt mixture, wherein the concentration of the mixture is 0.01-3g/L;
s2: ammonia water is adopted to adjust the pH value to 7-7.8;
s3: the lead alloy is used as an anode, the stainless steel plate is used as a cathode, and the current density is adjusted to be 250-400A/m 2 Carrying out electrolysis after the cell voltage is 3-6V and the temperature is 10-60 ℃;
s4: electrolyzing for 6-48h, passivating and cleaning the metal manganese of the cathode, and then stripping.
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| CN202210546646.4A CN114959796B (en) | 2022-05-18 | 2022-05-18 | Additive for electrolytic manganese metal and application of additive in electrolytic manganese |
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| CN202210546646.4A CN114959796B (en) | 2022-05-18 | 2022-05-18 | Additive for electrolytic manganese metal and application of additive in electrolytic manganese |
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| CN114959796B true CN114959796B (en) | 2023-09-29 |
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Citations (6)
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|---|---|---|---|---|
| CN103436921A (en) * | 2013-08-30 | 2013-12-11 | 昆明理工大学 | Method for forming aluminum-manganese-titanium alloy through electrodeposition of ionic liquid |
| CN103540952A (en) * | 2012-07-17 | 2014-01-29 | 吉首大学 | Cyclic organic additive containing nitrogen for efficiently producing electrolytic manganese metal |
| CN105603454A (en) * | 2016-01-25 | 2016-05-25 | 吉首大学 | Method for environmentally-friendly and efficient production of electrolytic metal manganese and electrolytic additive |
| CN106914276A (en) * | 2015-12-24 | 2017-07-04 | 于志勇 | It is a kind of for acetylene add hcl reaction without mercury catalyst and preparation method |
| CN108315763A (en) * | 2018-05-09 | 2018-07-24 | 东北大学 | A method of preparing metallic zinc using ionic liquid electrolytic oxidation zinc |
| CN109518226A (en) * | 2019-01-23 | 2019-03-26 | 东北大学 | A kind of method that urea-disubstituted imidazole-aluminium chloride ionic liquid prepares aluminium |
-
2022
- 2022-05-18 CN CN202210546646.4A patent/CN114959796B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103540952A (en) * | 2012-07-17 | 2014-01-29 | 吉首大学 | Cyclic organic additive containing nitrogen for efficiently producing electrolytic manganese metal |
| CN103436921A (en) * | 2013-08-30 | 2013-12-11 | 昆明理工大学 | Method for forming aluminum-manganese-titanium alloy through electrodeposition of ionic liquid |
| CN106914276A (en) * | 2015-12-24 | 2017-07-04 | 于志勇 | It is a kind of for acetylene add hcl reaction without mercury catalyst and preparation method |
| CN105603454A (en) * | 2016-01-25 | 2016-05-25 | 吉首大学 | Method for environmentally-friendly and efficient production of electrolytic metal manganese and electrolytic additive |
| CN108315763A (en) * | 2018-05-09 | 2018-07-24 | 东北大学 | A method of preparing metallic zinc using ionic liquid electrolytic oxidation zinc |
| CN109518226A (en) * | 2019-01-23 | 2019-03-26 | 东北大学 | A kind of method that urea-disubstituted imidazole-aluminium chloride ionic liquid prepares aluminium |
Non-Patent Citations (1)
| Title |
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| Manganese-containing ionic liquids: synthesis, crystal structures and electrodeposition of manganese films and nanoparticles;Jeroen Sniekers et al;Dalton Trans;第46卷;2497–2509 * |
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