CN109055984B - Method for preparing rare earth metal samarium by electrolyzing samarium chloride serving as raw material at room temperature - Google Patents
Method for preparing rare earth metal samarium by electrolyzing samarium chloride serving as raw material at room temperature Download PDFInfo
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Abstract
The invention relates to a method for preparing rare earth metal samarium by using samarium chloride as a raw material through room-temperature electrolysis, belonging to the field of low-temperature extraction of rare earth metal. A method for preparing rare earth metal samarium by electrolyzing samarium chloride at room temperature comprises the following process steps: dissolving lithium nitrate in DMI at room temperature to obtain DMI electrolyte of the lithium nitrate; placing DMI electrolyte of lithium nitrate into an electrolytic tank, adding anhydrous samarium chloride into the electrolytic tank, stirring and mixing the solution in the electrolytic tank to form a uniform and transparent system, controlling the temperature of the whole system to be 25 +/-5 ℃, and controlling the electrolytic voltage range to be-1.8 to-2.4V vs Ag; in the electrolytic process, anhydrous samarium chloride is supplemented into the electrolytic cell at intervals, and the molar concentration of the samarium chloride is controlled to be +/-3% of the initial concentration. The method provided by the invention can be used for preparing the rare earth metal samarium efficiently, and simultaneously, the energy consumption and the production cost are obviously reduced.
Description
Technical Field
The invention relates to a method for preparing rare earth metal samarium by using samarium chloride as a raw material through room-temperature electrolysis, belonging to the field of low-temperature extraction of rare earth metal.
Background
Rare earth is a precious strategic resource, is called as industrial monosodium glutamate and a parent of a new material, and is widely applied to the fields of advanced science and technology and military industry. According to introduction of the ministry of industry and informatization, at present, functional materials such as rare earth permanent magnet, luminescence, hydrogen storage, catalysis and the like are indispensable raw materials for high and new technology industries such as advanced equipment manufacturing industry, new energy sources, emerging industries and the like, and are widely applied to electronics, petrochemical industry, metallurgy, machinery, new energy sources, light industry, environmental protection, agriculture and the like. In particular, samarium, a rare earth metal, is used as a raw material of samarium cobalt-based permanent magnets, which are used in lightweight electronic devices because of their size advantages, and have received much attention for their functions at high temperatures. In addition, samarium has nuclear property, can be used as a structural material, a shielding material and a control material of an atomic energy reactor, and enables the huge energy generated by nuclear fission to be safely utilized.
From the technical point of view, at present, metal vacuum thermal reduction and high-temperature molten salt electrolysis are the traditional preparation methods of rare earth metal samarium. However, both of them have the disadvantages of high energy consumption, serious pollution, long flow, strong corrosiveness, complex operation, high requirement on equipment and the like. With the increasing tension of energy and the increasing prominence of environmental protection problems, how to obtain high-quality rare earth metal samarium and simultaneously reduce the pollution to the environment to the maximum extent and save energy becomes the focus of attention of people. If the rare earth metal samarium can be prepared by electro-deposition at room temperature or near room temperature, the method is simple to operate, low in cost, reliable and safe. Because rare earth samarium is abnormally active and has negative oxidation-reduction potential, rare earth samarium ions cannot be directly reduced to rare earth samarium on an electrode in an aqueous solution system (hydrogen evolution shielding effect), and the system for electrodepositing the samarium is generally a non-aqueous solvent. As a kind of non-aqueous solvent, which is also called as low-temperature molten salt, ionic liquid has properties such as low melting point, low saturated vapor pressure, and stable electrochemical properties, and is widely used in research of electrochemical metallurgical processes. However, the synthesis process of the ionic liquid is complex, the exchange reaction is incomplete, competitive reaction and byproducts exist, and the obtained product needs to be purified and separated in multiple steps, so that the production cost of the ionic liquid and the possibility of environmental pollution are remarkably increased, and the green characteristic of the ionic liquid is reduced. The water content in the finally prepared ionic liquid product can not be ensured, and the process of preparing the active metal samarium by the ionic liquid electrodeposition is seriously influenced. In addition, the electrochemical window of the conventional ionic liquid is narrow, the dissolving capacity of the conventional ionic liquid to common chlorides (such as magnesium chloride, calcium chloride, rare earth chloride and the like) is limited, and some common ionic liquids have high viscosity and are easy to absorb water in air, so that the practical application of the ionic liquid is limited to a great extent. At present, the ionic liquid has been developed for hundreds of years, but is only limited to scientific research in the field of metal electrodeposition, and has no large-scale practical application background.
Disclosure of Invention
Aiming at the existing problems, the invention provides a method for preparing metal samarium by electrolyzing samarium chloride at room temperature by using lithium nitrate (the purity is more than 99.9%) as a supporting electrolyte and using a novel aprotic strong polar solvent 1, 3-dimethyl-2-imidazolidinone (DMI) (the purity is more than 99.0%). The method is a short-flow method for preparing high-purity metal samarium through electrodeposition by dissolving samarium chloride (the purity is not less than 99.9%) serving as a raw material in a DMI solvent containing 0.02-0.6 mol/L of lithium nitrate, and energy consumption and production cost are remarkably reduced while rare earth metal samarium is efficiently prepared.
A method for preparing rare earth metal samarium by electrolyzing samarium chloride at room temperature is an electrolysis method and comprises the following process steps:
s1, dissolving lithium nitrate in DMI at room temperature, wherein the molar concentration of the lithium nitrate in the DMI is 0.02-0.6 mol/L, and obtaining DMI electrolyte of the lithium nitrate, wherein the DMI is represented by the following structural formula:
s2, placing the DMI electrolyte of lithium nitrate into an electrolytic cell, adding anhydrous samarium chloride into the DMI electrolyte, and stirring and mixing the solution in the electrolytic cell to form a uniform and transparent system, wherein the molar concentration of the samarium chloride is 0.01-0.3 mol/L, the temperature of the whole system is controlled to be 25 +/-5 ℃, and the electrolytic voltage range is-1.8 to-2.4V vs Ag;
s3, in the electrolysis process, adding anhydrous samarium chloride into the electrolytic cell at intervals, and controlling the molar concentration of the samarium chloride to be +/-3% of the initial concentration.
In the technical scheme, the purity of the lithium nitrate and the purity of the samarium chloride are both not less than 99.9 percent; the DMI purity is not less than 99.0%.
The invention relates to a method for controlling the molar concentration of samarium chloride to be +/-3% of the initial concentration, which means that the molar concentration of the samarium chloride is controlled to be 97-103% of the initial concentration.
In the invention, the 'vs Ag' in the 'electrolysis voltage range of-1.8 to-2.4V vs Ag' refers to a silver electrode as a reference electrode.
Preferably, in the step S1, the molar concentration of lithium nitrate in the DMI is 0.05 to 0.5 mol/L.
Preferably, in the step S2, the molar concentration of samarium chloride is 0.02-0.2 mol/L.
Preferably, in the step S3, anhydrous samarium chloride is added to the electrolytic cell every 30min, and the molar concentration of the samarium chloride is controlled to be within ± 3% of the initial concentration.
Preferably, the method comprises a step S4 of scraping the metal samarium formed on the cathode plate into a closed vessel filled with dimethyl carbonate or kerosene by using a sliding rod-shaped scraper along the surface of the cathode plate every 60 min; and (4) reprocessing the collected rare earth metals according to requirements.
Preferably, the electrolysis process takes a high-purity graphite rod or tungsten rod or molybdenum rod (the purity is more than or equal to 99.9%) as an anode and a pure copper plate (the purity is more than or equal to 99.9%) as a cathode.
Preferably, the inter-polar distance between the anode and the cathode is 20 mm.
Compared with the existing method for preparing metal samarium, the method provided by the invention has the following advantages:
(1) the process flow is shortened, the production energy consumption is obviously reduced, the production cost is reduced, and the operating environment is improved;
(2) the novel low-temperature aprotic strong-polarity solvent is adopted for electrodeposition, the defects of high energy consumption, high temperature and serious equipment corrosion when high-temperature molten salt electrolyte is adopted can be reduced and eliminated, the operation is easy, and in addition, the DMI solvent has the characteristics of excellent solubility and high dielectric constant for samarium chloride, no toxicity, good chemical and thermal stability, no corrosion to copper and iron, high boiling point, high flash point, low melting point, easy recovery and good safety performance. Importantly, the DMI solvent has a large-scale chemical production background, the cost is greatly reduced compared with a molten salt system and ionic liquid, and in addition, the DMI can be synthesized by waste plastics and greenhouse gas carbon dioxide, so that the DMI solvent is obvious in green property and has large-scale application capability and prospect. The method and the process can prepare the rare earth metal samarium through electrodeposition at low temperature, the obtained product has high purity and lower requirement on equipment, and the method and the process can be used for large-scale production to improve the efficiency and the yield and provide technical reserve and theoretical support for the green preparation of the rare earth metal with low cost.
Drawings
FIG. 1 is an SEM image of the product obtained in example 8 on a copper cathode plate.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The purity of the anhydrous samarium chloride, the purity of the lithium nitrate and the purity of the DMI adopted in the embodiment of the invention are respectively 99.9 percent, 99.9 percent and 99.0 percent.
In the embodiment of the invention, the Shanghai Chenghua electrochemical workstation is used as an electrolysis power supply.
In the embodiment of the invention, the anode is a high-purity graphite rod or a tungsten rod or a molybdenum rod (the purity is more than or equal to 99.9%), the diameter is 0.5cm, the depth of the inserted liquid level is 1cm, the cathode is a high-purity copper plate (the purity is more than or equal to 99.9%), and the area of the cathode is 1cm2The reference electrode is silver wire (purity is more than or equal to 99.99%, diameter is 0.05 cm).
In the embodiment of the invention, the content of samarium element is detected by adopting ICP (inductively coupled plasma atomic emission spectrometry); the characterization means includes SEM (scanning electron microscope) and EDS (electron-dispersive spectroscopy) energy spectrum analysis.
The method for preparing rare earth metal samarium by electrolyzing samarium chloride at room temperature in the following embodiment is an electrolysis method and comprises the following process steps:
s1, dissolving lithium nitrate in DMI at room temperature, wherein the molar concentration of the lithium nitrate in the DMI is 0.02-0.6 mol/L, and thus obtaining DMI electrolyte of the lithium nitrate;
s2, placing the DMI electrolyte of lithium nitrate into an electrolytic cell, adding anhydrous samarium chloride into the DMI electrolyte, and stirring and mixing the solution in the electrolytic cell to form a uniform and transparent system, wherein the molar concentration of the samarium chloride is 0.01-0.3 mol/L, the temperature of the whole system is controlled to be 25 +/-5 ℃, and the electrolytic voltage range is-1.8 to-2.4V vs Ag;
s3, in the electrolysis process, adding anhydrous samarium chloride into the electrolytic cell at intervals, and controlling the molar concentration of the samarium chloride to be +/-3% of the initial concentration.
Example 1
The method comprises the steps of preparing electrolyte raw materials of samarium chloride and lithium nitrate and a solvent DMI, and stirring and mixing the electrolyte raw materials in an electrolytic tank to form an electrolyte system, wherein the molar concentrations of the samarium chloride and the lithium nitrate are 0.01mol/L and 0.03mol/L respectively. Controlling the constant temperature of an electrolyte system to be 25 +/-5 ℃, the electrolytic voltage to be-1.8V (vs Ag), and the anode material to be graphite; after 30min of electrolysis, adding samarium chloride once to make the concentration of the samarium chloride in the system be 0.01 mol/L; and collecting and storing the deposit on the substrate after the electrolysis for 60min, and reprocessing the collected deposit according to requirements. The characterization and detection result shows that the metal samarium can be effectively deposited, and the total content of samarium element detected by ICP is 96.63%.
Example 2
Preparing electrolyte raw materials of samarium chloride and lithium nitrate and a solvent DMI, and stirring and mixing the electrolyte raw materials and the solvent DMI in an electrolytic tank to form an electrolyte system, wherein the molar concentrations of the samarium chloride and the lithium nitrate are 0.05mol/L and 0.15mol/L respectively. Controlling the constant temperature of an electrolyte system to be 25 +/-5 ℃, the electrolytic voltage to be-1.9V (vs Ag), and the anode material to be a tungsten rod; after 30min of electrolysis, adding samarium chloride once to ensure that the concentration of the samarium chloride in the system is 0.05 mol/L; and collecting and storing the deposit on the substrate after the electrolysis for 60min, and reprocessing the collected deposit according to requirements. The characterization and detection result shows that the metal samarium can be effectively deposited, and the total content of samarium element in ICP detection is 97.76%.
Example 3
Preparing electrolyte raw materials of samarium chloride and lithium nitrate and a solvent DMI, and stirring and mixing the electrolyte raw materials and the solvent DMI in an electrolytic tank to form an electrolyte system, wherein the molar concentrations of the samarium chloride and the lithium nitrate are 0.1mol/L and 0.1mol/L respectively. Controlling the constant temperature of the electrolyte system to be 25 +/-5 ℃, the electrolytic voltage to be-2.0V (vs Ag), and the anode material to be a molybdenum rod; after 30min of electrolysis, adding samarium chloride once to make the concentration of the samarium chloride in the system be 0.1 mol/L; and collecting and storing the deposit on the substrate after the electrolysis for 60min, and reprocessing the collected deposit according to requirements. The characterization and detection result shows that the metal samarium can be effectively deposited, and the total content of samarium element detected by ICP is 93.84%.
Example 4
Preparing electrolyte raw materials of samarium chloride and lithium nitrate and a solvent DMI, and stirring and mixing the electrolyte raw materials and the solvent DMI in an electrolytic tank to form an electrolyte system, wherein the molar concentrations of the samarium chloride and the lithium nitrate are 0.15mol/L and 0.15mol/L respectively. Controlling the constant temperature of an electrolyte system to be 25 +/-5 ℃, the electrolytic voltage to be-2.1V (vs Ag), and the anode material to be a graphite rod; after 30min of electrolysis, adding samarium chloride once to ensure that the concentration of the samarium chloride in the system is 0.15 mol/L; and collecting and storing the deposit on the substrate after the electrolysis for 60min, and reprocessing the collected deposit according to requirements. The characterization and detection result shows that the metal samarium can be effectively deposited, and the total content of samarium element detected by ICP is 97.56%.
Example 5
Preparing electrolyte raw materials of samarium chloride and lithium nitrate and a solvent DMI, and stirring and mixing the electrolyte raw materials and the solvent DMI in an electrolytic tank to form an electrolyte system, wherein the molar concentrations of the samarium chloride and the lithium nitrate are 0.20mol/L and 0.2mol/L respectively. Controlling the constant temperature of an electrolyte system to be 25 +/-5 ℃, the electrolytic voltage to be-2.2V (vs Ag), and the anode material to be a tungsten rod; after 30min of electrolysis, adding samarium chloride once to ensure that the concentration of the samarium chloride in the system is 0.20 mol/L; and collecting and storing the deposit on the substrate after the electrolysis for 60min, and reprocessing the collected deposit according to requirements. The characterization and detection result shows that the metal samarium can be effectively deposited, and the total content of samarium element detected by ICP is 98.82%.
Example 6
Preparing electrolyte raw materials of samarium chloride and lithium nitrate and a solvent DMI, and stirring and mixing the electrolyte raw materials and the solvent DMI in an electrolytic tank to form an electrolyte system, wherein the molar concentrations of the samarium chloride and the lithium nitrate are 0.25mol/L and 0.3mol/L respectively. Controlling the constant temperature of the electrolyte system to be 25 +/-5 ℃, the electrolytic voltage to be-2.3V (vs Ag), and the anode material to be a molybdenum rod; after 30min of electrolysis, adding samarium chloride once to make the concentration of the samarium chloride in the system be 0.25 mol/L; and collecting and storing the deposit on the substrate after the electrolysis for 60min, and reprocessing the collected deposit according to requirements. The characterization and detection result shows that the metal samarium can be effectively deposited, and the total content of samarium element detected by ICP is 98.51%.
Example 7
Preparing electrolyte raw materials of samarium chloride and lithium nitrate and a solvent DMI, and stirring and mixing the electrolyte raw materials and the solvent DMI in an electrolytic tank to form an electrolyte system, wherein the molar concentrations of the samarium chloride and the lithium nitrate are 0.3mol/L and 0.6mol/L respectively. Controlling the constant temperature of an electrolyte system to be 25 +/-5 ℃, the electrolytic voltage to be-2.4V (vs Ag), and the anode material to be a graphite rod; after 30min of electrolysis, adding samarium chloride once to ensure that the concentration of the samarium chloride in the system is 0.3 mol/L; and collecting and storing the deposit on the substrate after the electrolysis for 60min, and reprocessing the collected deposit according to requirements. The characterization and detection result shows that the metal samarium can be effectively deposited, and the total content of samarium element detected by ICP is 99.86%.
Example 8
Preparing electrolyte raw materials of samarium chloride and lithium nitrate and a solvent DMI, and stirring and mixing the electrolyte raw materials and the solvent DMI in an electrolytic tank to form an electrolyte system, wherein the molar concentrations of the samarium chloride and the lithium nitrate are 0.05mol/L and 0.15mol/L respectively. Controlling the constant temperature of an electrolyte system to be 25 +/-5 ℃, the electrolytic voltage to be-2.4V (vs Ag), and the anode material to be a tungsten rod; after 30min of electrolysis, adding samarium chloride once to ensure that the concentration of the samarium chloride in the system is 0.05 mol/L; and collecting and storing the deposit on the substrate after the electrolysis for 60min, and reprocessing the collected deposit according to requirements. The characterization and detection result shows that the metal samarium can be effectively deposited, and the total content of samarium element detected by ICP is 99.97%.
Claims (7)
1. A method for preparing rare earth metal samarium by using samarium chloride as a raw material through room temperature electrolysis is characterized by comprising the following steps: the method is an electrolytic method and comprises the following process steps:
s1, dissolving lithium nitrate in DMI at room temperature, wherein the molar concentration of the lithium nitrate in the DMI is 0.02-0.6 mol/L, and obtaining DMI electrolyte of the lithium nitrate, wherein the DMI is represented by the following structural formula:
s2, placing the DMI electrolyte of lithium nitrate into an electrolytic cell, adding anhydrous samarium chloride into the electrolytic cell, and stirring and mixing the solution in the electrolytic cell to form a uniform and transparent system, wherein the molar concentration of the samarium chloride is 0.01-0.3 mol/L, the temperature of the whole system is controlled to be 25 +/-5 ℃, and the electrolytic voltage range is-1.8 to-2.4V vs Ag;
s3, in the electrolysis process, adding anhydrous samarium chloride into the electrolytic cell at intervals, and controlling the molar concentration of the samarium chloride to be +/-3% of the initial concentration.
2. The method of claim 1, wherein: in the step S1, the molar concentration of lithium nitrate in DMI is 0.05-0.5 mol/L.
3. The method of claim 1, wherein: in the step S2, the molar concentration of the samarium chloride is 0.02-0.2 mol/L.
4. The method of claim 1, wherein: and S3, supplementing anhydrous samarium chloride into the electrolytic cell every 30min, and controlling the molar concentration of the samarium chloride to be +/-3% of the initial concentration.
5. The method of claim 1, wherein: the method comprises the steps of S4, scraping metal samarium formed on a cathode plate into a closed vessel filled with dimethyl carbonate or kerosene by using a sliding rod-shaped scraper along the surface of the cathode plate every 60 min; and (4) reprocessing the collected rare earth metals according to requirements.
6. The method of claim 1, wherein: in the electrolysis process, a high-purity graphite rod or a tungsten rod or a molybdenum rod is used as an anode, and a pure copper plate is used as a cathode.
7. The method of claim 6, wherein: the inter-polar distance between the anode and the cathode was 20 mm.
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| Electrodeposition of Aluminum from 1,3-Dimethyl-2-Imidazolidinone/AlCl3 baths;Atsushi Endo等;《Electrochimica Acta》;20140614;第137卷;第471页 * |
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