CN102433572A - Production process for preparing magnesium-gadolinium alloy by fused salt electrolysis method - Google Patents
Production process for preparing magnesium-gadolinium alloy by fused salt electrolysis method Download PDFInfo
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Abstract
The invention relates to a production process for preparing magnesium-gadolinium alloy by a fused salt electrolysis method. In the production process, pure magnesite containing more than 98% by weight of magnesium oxide or magnesium carbonate and gadolinium oxide or gadolinium chloride are used as raw materials, and metal tungsten or molybdenum is used as a cathode, and graphite is used as an anode; an electrolyte system is formed by combining gadolinium chloride with chloride and fluoride of alkali metal or alkaline earth metal; the electrolysis temperature is 900-1200 DEG C, the current intensity is 1000-10000A, the tank voltage is between 5V and 15V, the current efficiency is larger than 75%, the metal recovery rate is more than 95%, and the content of impurities in the magnesium-gadolinium alloy is less than 1%; and the magnesium-gadolinium alloy is directly produced in a fused salt electrolytic cell. Compared with the existing smelting doping method, the production process provided by the invention has the advantages that energy is saved, process flow is simplified, secondary burning loss of metal is not generated, and the like; and the electrolysis process is continuous, the alloy can be produced on a large scale, and the production cost of the magnesium-gadolinium alloy can be greatly reduced.
Description
Technical field
The present invention relates to a kind of production technique of magnesium gadolinium alloys, particularly in fused-salt bath, directly on negative electrode, produce the production technique of magnesium gadolinium alloys, belong to Non-ferrous Metallurgy fused salt electrolysis field.
Background technology
Magnesiumalloy is a kind of very important engineering materials; Compare with other material; Many performance advantages such as density is little, specific tenacity height are arranged, be applied in very early on the aerospace industry, other Application Areas is also quite extensive; Good etc. like good shock absorbing property, capability of electromagnetic shielding, heat radiation and the solidity to corrosion of magnesium alloy materials, its application in electronic products such as computingmachine, communication is constantly increased.The compound that REE and magnesium form is distributed in the as-cast structure crystal boundary and after extruding, distributes along the direction of extrusion, and different rare earth has Different Effects to the mechanical behavior under high temperature of alloy.Especially the rare earth-magnesium alloy novel material that with the rare-earth element gadolinium is representative has greatly improved on the performance of material, and its range of application is more and more wider.So magnesium gadolinium alloys will have comparatively wide application development prospect.
The preparation method of magnesium gadolinium alloys is main with melting to the method for mixing, and promptly forms mixing according to a certain percentage under molten state with pure magnesium and pure gadolinium.Like this, not only increase the hear rate of metal secondary remelting, also increased the oxidational losses of metal, caused the significant wastage of metal, increased the production cost of alloy.
Summary of the invention
The object of the invention provides the production technique that a kind of fused salt electrolysis process prepares magnesium gadolinium alloys, is to be raw material with the mass percent of Natural manganese dioxide or magnesiumcarbonate content greater than 98% pure magnesite and gadolinium sesquioxide or Gadolinium trichloride, and adopting tungsten or molybdenum is negative electrode; Graphite is anode, and electrolyte system is formed by the muriate and the fluoride combinations of gadolinium fluoride and basic metal or earth alkali metal, under 900～1200 ℃ of temperature; Strength of current is at 1000～10000A; Bath voltage is at 5-15V, and current efficiency is greater than 75%, and metal recovery rate is greater than 95%; The magnesium gadolinium alloys foreign matter content is less than 1%, direct production magnesium gadolinium alloys in fused-salt bath.
The present invention realizes through following technical scheme:
A kind of fused salt electrolysis process prepares the production technique of magnesium gadolinium alloys; Ionogen is that 95% the gadolinium fluoride and the muriate and the fluoride combinations of basic metal or earth alkali metal form by accounting for mass percent in the electrolyte system, is that the mass percent of 5% Natural manganese dioxide or magnesiumcarbonate content is a raw material greater than 98% pure magnesite and gadolinium sesquioxide or Gadolinium trichloride to account for mass percent; Adopting tungsten or molybdenum is negative electrode, and graphite is anode, uses floating electrolysis or sunk type electrolysis, and 900～1200 ℃ of temperature, under strength of current 1000～10000A, electrolysis time is at 4-2160 hour, direct production magnesium gadolinium alloys in fused-salt bath.
Ionogen is by MgF
2And GdF
3, MgCl
2, LiF, LiCl, KCl, KF, BaF
2, BaCl
2, CaF
2, CaCl
2, two kinds or two or more combining among the NaF, NaCl, shared separately mass percent: MgF
2Be 5-80%, GdF
3Be 10-90%, MgCl
2For 5-70%, LiF are that 5-80%, LiCl are that 5-50%, KCl are that 5-50%, KF are 5-80%, BaF
2Be 5-80%, BaCl
2Be 5-60%, CaF
2Be 5-80%, CaCl
2For 5-50%, NaF are that 5-70%, NaCl are 5-50%.
The mass percent of the solubleness of Natural manganese dioxide in electrolyte system is 1～5%, and the solubleness of gadolinium sesquioxide in electrolyte system is that mass percent is 1～5%, and the solubleness of Gadolinium trichloride in electrolyte system is that mass percent is 1～25%; Controlled oxidation magnesium and the proportionlity of gadolinium sesquioxide in ionogen when being the raw material electrolysis with Natural manganese dioxide and gadolinium sesquioxide are guaranteeing that Natural manganese dioxide and the gadolinium sesquioxide mass ratio in ionogen is between 1: 1～1: 15 under the situation that mg ion and gadolinium ion common deposited are separated out; Controlled oxidation magnesium and the proportionlity of Gadolinium trichloride in ionogen when being the raw material electrolysis with Natural manganese dioxide and Gadolinium trichloride are guaranteeing that Natural manganese dioxide and the Gadolinium trichloride mass ratio in ionogen is between 1: 1～1: 8 under the situation that mg ion and gadolinium ion common deposited are separated out.
Degree according to each ionogen component is different, and electrolyte density is with the magnitude relationship of alloy density, and floating electrolysis or sunk type electrolysis in the employing when electrolyte density is bigger than alloy density, adopt alloy to float over the last floating electrolysis above the ionogen; When electrolytical density than the density of alloy hour, adopt alloy to sink to the sunk type electrolysis of bottom of electrolytic tank; Pole span is 15-30cm, and bath voltage is at 5-15V.
Normal electrolysis under electrolytic condition; Every interval 10-45 branch clockwise electrolyzer replenish to add mass percent be the mass percent of 0.5% Natural manganese dioxide or magnesiumcarbonate content greater than 98% pure magnesite and gadolinium sesquioxide or Gadolinium trichloride raw material, guarantee that electrolysis carries out continually and steadily.
Magnesia amount ratio content is in the magnesium gadolinium alloys of being produced: 1-99%, and the gadolinium quality than content is: 1-99%, other impurity component content is less than 1%, and metal recovery rate is greater than 95%.
When being raw material with Natural manganese dioxide and gadolinium sesquioxide or Gadolinium trichloride, the quality percentage composition of impurity component is in its Natural manganese dioxide: Fe＜0.1%, P＜0.1%, Si＜0.1%; V＜0.02%, the quality percentage composition of major impurity composition is in the gadolinium sesquioxide: Fe＜0.01%, C＜0.1%, Si＜0.1%; W＜0.1%, V＜0.02%, the quality percentage composition of major impurity composition is in the Gadolinium trichloride: Fe＜0.01%, C＜0.1%; Si＜0.1%, W＜0.1%, V＜0.02%.
With Natural manganese dioxide and gadolinium sesquioxide is raw material, and Natural manganese dioxide and gadolinium sesquioxide are decomposed in the electrolytic process, and mg ion and gadolinium ion precipitate on negative electrode jointly separates out, and forms magnesium gadolinium alloys, and Natural manganese dioxide and gadolinium sesquioxide decomposition reaction are: 2MgO → 2Mg+O
2, 2Gd
2O
3→ 4Gd+3O
2The gas that produces on the anode is O
2, O
2Generate CO with the graphite anode reaction
2, CO gas; With Natural manganese dioxide and Gadolinium trichloride is raw material, and Natural manganese dioxide and Gadolinium trichloride are decomposed in the electrolytic process, and mg ion and gadolinium ion precipitate on negative electrode jointly separates out, and forms magnesium gadolinium alloys, and Natural manganese dioxide and Gadolinium trichloride decomposition reaction are: 2MgO → 2Mg+O
2, 2GdCl
3→ 2Gd+3Cl
2The gas that produces on the anode is O
2And Cl
2, O
2Generate CO with the graphite anode reaction
2, CO gas.
When being raw material greater than 98% magnesite with magnesiumcarbonate quality percentage; Its other foreign matter content is: Fe＜0.2%, P＜0.1%, Ca＜0.2%, Si＜0.5%; It decomposes generation MgO under 900 ℃～1200 ℃ electrolytic condition, chemical equation is: MgCO
3→ MgO+CO
2
Advantage and effect: through the enforcement of technical scheme of the present invention, can produce the uniform magnesium gadolinium alloys of composition as required, alloying constituent is by electrolysis time and proportioning raw materials decision.Solve the method for producing magnesium gadolinium alloys now well and have shortcomings such as hear rate is big, the oxidational losses of alloyed metal is big, Metal Production cost height.
Production technique of the present invention is a raw material with the MgO of cheapness or purer magnesite (magnesiumcarbonate quality percentage composition＞98%) and gadolinium sesquioxide or Gadolinium trichloride, and direct production goes out the uniform magnesium gadolinium alloys of composition in fused-salt bath.Can reduce the production cost of alloy significantly, reduce working strength of workers.Simultaneously, electrolytic process is continuous, and metal recovery rate is greater than 95%, can the scale operation composition evenly, the magnesium gadolinium alloys of reduced in segregation, be a kind of short flow process, alloy production technology cheaply.
Embodiment
The production technique that fused salt electrolysis process prepares magnesium gadolinium alloys is raw material with the mass percent of Natural manganese dioxide or magnesiumcarbonate content greater than 98% pure magnesite and gadolinium sesquioxide or Gadolinium trichloride; Adopting tungsten or molybdenum is negative electrode; Graphite is anode, and electrolyte system is formed by the muriate and the fluoride combinations of gadolinium fluoride and basic metal or earth alkali metal, 900～1200 ℃ of temperature; Under 1000～10000A, direct production magnesium gadolinium alloys in fused-salt bath.Process is following: ionogen is by MgF
2And GdF
3, MgCl
2, LiF, LiCl, KCl, KF, BaF
2, BaCl
2, CaF
2, CaCl
2, two kinds or two or more combining among the NaF, NaCl.Accurately take by weighing each ionogen moity according to a certain percentage,, choose floating or sunk type electrolysis structure according to the difference of ionogen with alloy density.At high temperature molten electrolyte adds raw material, energized, beginning electrolysis.Certain hour at interval, mg ion and gadolinium ion concentration are a stable scope in the electrolyzer to keep to add raw material, and the assurance electrolysis is normally carried out.
Electrolysis temperature: form difference according to ionogen, Controllable Temperature is between 900 ℃～1200 ℃, and electrolytical liquidus temperature is different, and 20 ℃～100 ℃ that can be chosen on the electrolyte primary crystal temperature are carried out electrolysis.
Raw materials of magnesium oxide requires: the quality percentage composition of impurity component is in the Natural manganese dioxide: Fe＜0.1%, P＜0.1%, Si＜0.1%, V＜0.02%.
Magnesiumcarbonate quality percentage greater than 98% magnesite ingredient requirement is: other foreign matter content is: Fe＜0.2%, P＜0.1%, Ca＜1%, Si＜0.5%; It is under 900 ℃～1200 ℃ electrolytic condition; Decompose generation MgO, chemical equation is: MgCO
3→ MgO+CO
2
The gadolinium sesquioxide ingredient requirement is: the quality percentage composition of its major impurity composition is: Fe＜0.01%, C＜0.1%, Si＜0.1%, W＜0.1%, V＜0.02%.
The Gadolinium trichloride ingredient requirement is: the quality percentage composition of its major impurity composition is: Fe＜0.01%, C＜0.1%, Si＜0.1%, W＜0.1%, V＜0.02%.
Embodiment 1:
With MgF
2-GdF
3-LiF is an electrolyte system, and the mass percent of each composition is respectively 5%, 65%, 25%; With Natural manganese dioxide and gadolinium sesquioxide is raw material, and the mass percent that accounts in the electrolyte system is 5%, and Natural manganese dioxide and gadolinium sesquioxide mass ratio are 1: 5; With the metal tungsten bar is negative electrode, and graphite is anode, selects the sunk type negative electrode; Electrolysis temperature is 1180 ℃, and pole span is 15cm, and strength of current is 3000A; It is every that to replenish the adding mass percent at a distance from 30 fens clockwise electrolyzers be 0.5% Natural manganese dioxide and gadolinium sesquioxide (Natural manganese dioxide and gadolinium sesquioxide mass ratio are 1: 5); Electrolysis through 4 hours; Produced the uniform magnesium gadolinium alloys of composition at bottom of electrolytic tank; The Mg content mass percent has reached 76.6% in the alloy, and the gadolinium concentrations mass percent reaches 23.3%, metal recovery rate 94.3%.Emit CO in the electrolytic process
2, CO does not have other gas and generates.
Embodiment 2:
With GdF3-LiF-KCl is electrolyte system, and the mass percent of each composition is respectively 20%, 30%, 45%; Adopting the magnesiumcarbonate mass percent is raw material greater than 98% magnesite and Gadolinium trichloride, and the mass percent that accounts in the electrolyte system is 5%, and Natural manganese dioxide (magnesiumcarbonate is scaled the Natural manganese dioxide quality) and Gadolinium trichloride mass ratio are 1: 3; With the metal tungsten bar is negative electrode, and graphite is anode, has selected the sunk type negative electrode; Electrolysis temperature is 920 ℃, and pole span is 20cm, and strength of current is 1500A; It is every that to replenish the adding mass percent at a distance from 30 fens clockwise electrolyzers be 0.5% magnesite and Gadolinium trichloride (Natural manganese dioxide and Gadolinium trichloride mass ratio are 1: 3); Through 120 hours electrolysis, produced the uniform magnesium gadolinium alloys of composition at bottom of electrolytic tank, the Mg content mass percent has reached 55.7% in the alloy, and the gadolinium concentrations mass percent reaches 44.1%, metal recovery rate 96%.Emit CO in the electrolytic process
2, CO and chlorine.
Embodiment 3:
With GdF
3-BaF
2-CaF
2-LiF is an electrolyte system, and the mass percent of each composition is respectively 10%, 55%, 15% and 15%; With Natural manganese dioxide and gadolinium sesquioxide is raw material, and the mass percent that accounts in the electrolyte system is 5%, and Natural manganese dioxide and gadolinium sesquioxide mass ratio are 1: 4; With the metal molybdenum bar is negative electrode, and graphite is anode, has selected last floating negative electrode; Electrolysis temperature is 1050 ℃, and pole span is 30cm, and strength of current is 9000A; It is every that to replenish the adding mass percent at a distance from 10 fens clockwise electrolyzers be 0.5% Natural manganese dioxide and gadolinium sesquioxide (Natural manganese dioxide and gadolinium sesquioxide mass ratio are 1: 5); Electrolysis through 1000 hours; In electrolyzer, produced the uniform magnesium gadolinium alloys of composition; The Mg content mass percent has reached 64.7% in the alloy, and the gadolinium concentrations mass percent reaches 35.1%, metal recovery rate 98.4%.Only emit CO in the electrolytic process
2, CO does not have other gas and generates.
Embodiment 4:
With GdF
3-BaF
2-KCl-LiF is an electrolyte system, and the mass percent of each composition is respectively 15%, 60%, 10% and 10%; With Natural manganese dioxide and Gadolinium trichloride is raw material, and the mass percent that accounts in the electrolyte system is 5%, and Natural manganese dioxide and Gadolinium trichloride mass ratio are 1: 6; With the metal tungsten bar is negative electrode, and graphite is anode, has selected last floating negative electrode; Electrolysis temperature is 1050 ℃, and pole span is 20cm, and strength of current is 4000A; It is every that to replenish the adding mass percent at a distance from 30 fens clockwise electrolyzers be 0.5% Natural manganese dioxide and Gadolinium trichloride (Natural manganese dioxide and Gadolinium trichloride mass ratio are 1: 6); , through 1400 hours electrolysis, in electrolyzer, produced the uniform magnesium gadolinium alloys of composition, the Mg content mass percent has reached 32.6% in the alloy, and the gadolinium concentrations mass percent reaches 67.1%, metal recovery rate 97.3%.Emit CO in the electrolytic process
2, CO and chlorine.
Embodiment 5:
With GdF
3-LiF is an electrolyte system, and the mass percent of each composition is 65% and 30%; With Natural manganese dioxide and Gadolinium trichloride is raw material, and the mass percent that accounts in the electrolyte system is 5%, and Natural manganese dioxide and Gadolinium trichloride mass ratio are 1: 4; With the metal tungsten bar is negative electrode, and graphite is anode, has selected the sunk type negative electrode; Electrolysis temperature is 1100 ℃, and pole span is 25cm, and strength of current is 3000A; It is every that to replenish the adding mass percent at a distance from 30 fens clockwise electrolyzers be 0.5% Natural manganese dioxide and Gadolinium trichloride (Natural manganese dioxide and Gadolinium trichloride mass ratio are 1: 4); Through 2000 hours electrolysis, produced the uniform magnesium gadolinium alloys of composition at bottom of electrolytic tank, the Mg content mass percent has reached 68.5% in the alloy, and the gadolinium concentrations mass percent reaches 31.1%, metal recovery rate 94%.Emit CO in the electrolytic process
2, CO and chlorine.
Embodiment 6:
With GdF
3-MgF
2-LiF-KCl is an electrolyte system, and the mass percent of each composition is respectively 20%, 20%, 10% and 45%; With magnesite (the magnesiumcarbonate mass percent is greater than 98%) and gadolinium sesquioxide is raw material, and the mass percent that accounts in the electrolyte system is 5%, and Natural manganese dioxide (magnesiumcarbonate is scaled the Natural manganese dioxide quality) and gadolinium sesquioxide mass ratio are 1: 8; With the metal tungsten bar is negative electrode, and graphite is anode, has selected the sunk type negative electrode; Electrolysis temperature is 950 ℃, and pole span is 24cm, and strength of current is 2000A; It is every that to replenish the adding mass percent at a distance from 45 fens clockwise electrolyzers be 0.5% magnesite and gadolinium sesquioxide (Natural manganese dioxide and Gadolinium trichloride mass ratio are 1: 8); Through 1100 hours electrolysis, produced the uniform magnesium gadolinium alloys of composition at bottom of electrolytic tank, the Mg content mass percent has reached 21.2% in the alloy, and the gadolinium concentrations mass percent reaches 78.1%, metal recovery rate 95.6%.Emit CO in the electrolytic process
2, CO.
Embodiment 7:
With GdF
3-MgF-LiF-KCl is an electrolyte system, and the mass percent of each composition is 25%, 10%, 10% and 50%; With Natural manganese dioxide and Gadolinium trichloride is raw material, and the mass percent that accounts in the electrolyte system is 5%, and Natural manganese dioxide and Gadolinium trichloride mass ratio are 1: 5; With the metal tungsten bar is negative electrode, and graphite is anode, has selected the sunk type negative electrode; Electrolysis temperature is 950 ℃, and pole span is 20cm, and strength of current is 7000A; It is every that to replenish the adding mass percent at a distance from 20 fens clockwise electrolyzers be 0.5% Natural manganese dioxide and Gadolinium trichloride (Natural manganese dioxide and Gadolinium trichloride mass ratio are 1: 5); Through 240 hours electrolysis, produced the uniform magnesium gadolinium alloys of composition at bottom of electrolytic tank, the Mg content mass percent has reached 54.5% in the alloy, and the gadolinium concentrations mass percent reaches 45.1%, metal recovery rate 96%.Emit CO in the electrolytic process
2, CO and chlorine.
Embodiment 8:
With GdF
3-LiF-BaF
2Be electrolyte system, the mass percent of each composition is respectively 20%, 30%, 45%; Employing magnesiumcarbonate mass percent is a raw material greater than 98% magnesite and gadolinium sesquioxide, and the mass percent that accounts in the electrolyte system is 5%, and Natural manganese dioxide (magnesiumcarbonate is scaled the Natural manganese dioxide quality) and gadolinium sesquioxide mass ratio are 1: 4; With the metal molybdenum bar is negative electrode, and graphite is anode, has selected last floating negative electrode; Electrolysis temperature is 1050 ℃, and pole span is 30cm, and strength of current is 5000A; It is every that to replenish the adding mass percent at a distance from 30 fens clockwise electrolyzers be 0.5% magnesite and gadolinium sesquioxide (Natural manganese dioxide and gadolinium sesquioxide mass ratio are 1: 4); Through 480 hours electrolysis, in electrolyzer, produced the uniform magnesium gadolinium alloys of composition, the Mg content mass percent has reached 38.6% in the alloy, and the gadolinium concentrations mass percent reaches 61.1%, metal recovery rate 95.3%.Emit CO in the electrolytic process
2, CO.
Claims (9)
1. a fused salt electrolysis process prepares the production technique of magnesium gadolinium alloys; It is characterized in that: ionogen is that 95% the gadolinium fluoride and the muriate and the fluoride combinations of basic metal or earth alkali metal form by accounting for mass percent in the electrolyte system, is that the mass percent of 5% Natural manganese dioxide or magnesiumcarbonate content is a raw material greater than 98% pure magnesite and gadolinium sesquioxide or Gadolinium trichloride to account for mass percent; Adopting tungsten or molybdenum is negative electrode, and graphite is anode, uses floating electrolysis or sunk type electrolysis, 900～1200 ℃ of temperature, and under strength of current 1000～10000A, direct production magnesium gadolinium alloys in fused-salt bath.
2. a kind of fused salt electrolysis process according to claim 1 prepares the production technique of magnesium gadolinium alloys, it is characterized in that: ionogen is by MgF
2And GdF
3, MgCl
2, LiF, LiCl, KCl, KF, BaF
2, BaCl
2, CaF
2, CaCl
2, two kinds or two or more combining among the NaF, NaCl, shared separately mass percent: MgF
2Be 5-80%, GdF
3Be 10-90%, MgCl
2For 5-70%, LiF are that 5-80%, LiCl are that 5-50%, KCl are that 5-50%, KF are 5-80%, BaF
2Be 5-80%, BaCl
2Be 5-60%, CaF
2Be 5-80%, CaCl
2For 5-50%, NaF are that 5-70%, NaCl are 5-50%.
3. a kind of fused salt electrolysis process according to claim 1 prepares the production technique of magnesium gadolinium alloys; It is characterized in that: the mass percent of the solubleness of Natural manganese dioxide in electrolyte system is 1～5%; The solubleness of gadolinium sesquioxide in electrolyte system is that mass percent is 1～5%, and the solubleness of Gadolinium trichloride in electrolyte system is that mass percent is 1～25%; Controlled oxidation magnesium and the proportionlity of gadolinium sesquioxide in ionogen when being the raw material electrolysis with Natural manganese dioxide and gadolinium sesquioxide are guaranteeing that Natural manganese dioxide and the gadolinium sesquioxide mass ratio in ionogen is between 1: 1～1: 15 under the situation that mg ion and gadolinium ion common deposited are separated out; Controlled oxidation magnesium and the proportionlity of Gadolinium trichloride in ionogen when being the raw material electrolysis with Natural manganese dioxide and Gadolinium trichloride are guaranteeing that Natural manganese dioxide and the Gadolinium trichloride mass ratio in ionogen is between 1: 1～1: 8 under the situation that mg ion and gadolinium ion common deposited are separated out.
4. a kind of fused salt electrolysis process according to claim 1 prepares the production technique of magnesium gadolinium alloys; It is characterized in that: the degree according to each ionogen component is different; Electrolyte density is with the magnitude relationship of alloy density; Floating electrolysis or sunk type electrolysis in the employing when electrolyte density is bigger than alloy density, adopt alloy to float over the last floating electrolysis above the ionogen; When electrolytical density than the density of alloy hour, adopt alloy to sink to the sunk type electrolysis of bottom of electrolytic tank; Pole span is 15-30cm, and bath voltage is at 5-15V, electrolysis time 4-2160 hour.
5. a kind of fused salt electrolysis process according to claim 1 prepares the production technique of magnesium gadolinium alloys; It is characterized in that: normal electrolysis under electrolytic condition; Every interval 10-45 branch clockwise electrolyzer replenish to add mass percent be the mass percent of 0.5% Natural manganese dioxide or magnesiumcarbonate content greater than 98% pure magnesite and gadolinium sesquioxide or Gadolinium trichloride raw material, guarantee that electrolysis carries out continually and steadily.
6. a kind of fused salt electrolysis process according to claim 1 prepares the production technique of magnesium gadolinium alloys; It is characterized in that: magnesia amount ratio content is in the magnesium gadolinium alloys of being produced: 1-99%; The gadolinium quality than content is: 1-99%, and other impurity component content is less than 1%, and metal recovery rate is greater than 95%.
7. a kind of fused salt electrolysis process according to claim 1 prepares the production technique of magnesium gadolinium alloys, it is characterized in that: when being raw material with Natural manganese dioxide and gadolinium sesquioxide or Gadolinium trichloride, the quality percentage composition of impurity component is in its Natural manganese dioxide: Fe＜0.1%, P＜0.1%; Si＜0.1%, V＜0.02%, the quality percentage composition of major impurity composition is in the gadolinium sesquioxide: Fe＜0.01%; C＜0.1%, Si＜0.1%, W＜0.1%; V＜0.02%, the quality percentage composition of major impurity composition is in the Gadolinium trichloride: Fe＜0.01%, C＜0.1%; Si＜0.1%, W＜0.1%, V＜0.02%.
8. a kind of fused salt electrolysis process according to claim 1 prepares the production technique of magnesium gadolinium alloys; It is characterized in that: with Natural manganese dioxide and gadolinium sesquioxide is raw material; Natural manganese dioxide and gadolinium sesquioxide are decomposed in the electrolytic process; Mg ion and gadolinium ion precipitate on negative electrode jointly separates out, and forms magnesium gadolinium alloys, and Natural manganese dioxide and gadolinium sesquioxide decomposition reaction are: 2MgO → 2Mg+O
2, 2Gd
2O
3→ 4Gd+3O
2The gas that produces on the anode is O
2, O
2Generate CO with the graphite anode reaction
2, CO gas; With Natural manganese dioxide and Gadolinium trichloride is raw material, and Natural manganese dioxide and Gadolinium trichloride are decomposed in the electrolytic process, and mg ion and gadolinium ion precipitate on negative electrode jointly separates out, and forms magnesium gadolinium alloys, and Natural manganese dioxide and Gadolinium trichloride decomposition reaction are: 2MgO → 2Mg+O
2, 2GdCl
3→ 2Gd+3Cl
2The gas that produces on the anode is O
2And Cl
2, O
2Generate CO with the graphite anode reaction
2, CO gas.
9. a kind of fused salt electrolysis process according to claim 1 prepares the production technique of magnesium gadolinium alloys; It is characterized in that: when being raw material greater than 98% magnesite with magnesiumcarbonate quality percentage; Its other foreign matter content is: Fe＜0.2%, P＜0.1%, Ca＜0.2%, Si＜0.5%; It decomposes generation MgO under 900 ℃～1200 ℃ electrolytic condition, chemical equation is: MgCO
3→ MgO+CO
2
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3855087A (en) * | 1972-10-11 | 1974-12-17 | Shinetsu Chemical Co | Method for producing rare earth metal-containing alloys |
| JP2004315891A (en) * | 2003-04-16 | 2004-11-11 | Toyohashi University Of Technology | Method for manufacturing magnesium alloy containing rare earth metal |
| CN1884629A (en) * | 2006-05-26 | 2006-12-27 | 杨少华 | Process for preparing magnesium alloy |
| CN101058891A (en) * | 2006-04-20 | 2007-10-24 | 有研稀土新材料股份有限公司 | Method of preparing high rare-earth content magnesium intermediate alloy |
| CN101117723A (en) * | 2007-07-30 | 2008-02-06 | 赣南师范学院 | Method for preparing Gd-Mg intermediate alloy by fluorination system coelectrodeposition |
| CN102220607A (en) * | 2011-05-25 | 2011-10-19 | 中国科学院青海盐湖研究所 | Molten salt electrolyte composition for preparing magnesium-rare earth alloy by using water-containing chloride to electrolyze |
| CN102268693A (en) * | 2011-07-08 | 2011-12-07 | 中国科学院长春应用化学研究所 | Method for preparing rare-earth magnesium alloy |
-
2011
- 2011-12-26 CN CN2011104424593A patent/CN102433572A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3855087A (en) * | 1972-10-11 | 1974-12-17 | Shinetsu Chemical Co | Method for producing rare earth metal-containing alloys |
| JP2004315891A (en) * | 2003-04-16 | 2004-11-11 | Toyohashi University Of Technology | Method for manufacturing magnesium alloy containing rare earth metal |
| CN101058891A (en) * | 2006-04-20 | 2007-10-24 | 有研稀土新材料股份有限公司 | Method of preparing high rare-earth content magnesium intermediate alloy |
| CN1884629A (en) * | 2006-05-26 | 2006-12-27 | 杨少华 | Process for preparing magnesium alloy |
| CN101117723A (en) * | 2007-07-30 | 2008-02-06 | 赣南师范学院 | Method for preparing Gd-Mg intermediate alloy by fluorination system coelectrodeposition |
| CN102220607A (en) * | 2011-05-25 | 2011-10-19 | 中国科学院青海盐湖研究所 | Molten salt electrolyte composition for preparing magnesium-rare earth alloy by using water-containing chloride to electrolyze |
| CN102268693A (en) * | 2011-07-08 | 2011-12-07 | 中国科学院长春应用化学研究所 | Method for preparing rare-earth magnesium alloy |
Non-Patent Citations (4)
| Title |
|---|
| 《稀有金属材料与工程》 20071231 杨少华等 熔盐电解法制取Al-Mg-RE三元合金 1-9 第36卷, 第3期 * |
| 彭光怀等: "氟化物熔盐共电沉积制备Gd-Mg中间合金研究", 《昆明理工大学学报》, vol. 35, no. 2, 30 April 2010 (2010-04-30) * |
| 杨少华等: "熔盐电解法制取Al—Mg—RE三元合金", 《稀有金属材料与工程》, vol. 36, no. 3, 31 December 2007 (2007-12-31) * |
| 赵飞等: "氧化钆电解制备钆铁合金工艺试验", 《内蒙古石油化工》, no. 11, 31 December 2007 (2007-12-31) * |
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| CN103184476A (en) * | 2013-03-11 | 2013-07-03 | 南京航空航天大学 | Technique adopting basic magnesium carbonate to produce rare-earth magnesium alloy |
| WO2014194746A1 (en) * | 2013-06-04 | 2014-12-11 | 中国科学院过程工程研究所 | Method for preparing magnesium alloy by electrolysis using magnesium oxide as raw material |
| CN104213154A (en) * | 2013-06-04 | 2014-12-17 | 中国科学院过程工程研究所 | Method using magnesium oxide as raw material for electrolytic preparation of magnesium alloy |
| CN104213154B (en) * | 2013-06-04 | 2017-08-04 | 中国科学院过程工程研究所 | Utilize the method that magnesia is raw material electrolytic preparation magnesium alloy |
| CN108878814A (en) * | 2018-06-15 | 2018-11-23 | 江西理工大学 | A method of preparing lithium ion battery negative material Sn-Co alloy |
| CN110106532A (en) * | 2019-05-20 | 2019-08-09 | 开化祥盛磁业有限公司 | A kind of method that molten-salt electrolysis prepares terbium ferroalloy |
| CN112030193A (en) * | 2020-08-27 | 2020-12-04 | 包头稀土研究院 | Method for reducing segregation of gadolinium-yttrium-magnesium alloy |
| CN112030193B (en) * | 2020-08-27 | 2021-11-09 | 包头稀土研究院 | Method for reducing segregation of gadolinium-yttrium-magnesium alloy |
| CN116856023A (en) * | 2023-09-04 | 2023-10-10 | 中石油深圳新能源研究院有限公司 | Preparation method of battery connector, battery connector and battery |
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