CN1772964A - Process for producing Mg rare earth intermediate alloy by Submerged Liquid Cathode electrolysis under low-temperature - Google Patents
Process for producing Mg rare earth intermediate alloy by Submerged Liquid Cathode electrolysis under low-temperature Download PDFInfo
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- CN1772964A CN1772964A CN 200510017229 CN200510017229A CN1772964A CN 1772964 A CN1772964 A CN 1772964A CN 200510017229 CN200510017229 CN 200510017229 CN 200510017229 A CN200510017229 A CN 200510017229A CN 1772964 A CN1772964 A CN 1772964A
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- praseodymium
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Abstract
The present invention belongs to a preparation process of magnesium-rare earth intermediate alloy, belonging to the field of fused salt electrolysis metallurgical technology. It is characterized by that it uses the lanthanum-praseodymium-cerium chloride (LPC) cl3 which is residual after neodymium extraction and whose content is 8-30 wt% after it is dehydrated as raw material, its electrolyte system is Kcl (50-40)% : NaCl (42-30) %: (8-30%) of (LPC) Cl3, and its solvent is Kcl and Nacl, and (LPC) Cl3 is solute. Said invention adopts magnesium-lanthanum-praseodymium-cerium intermediate alloy whose rare earth content is 5-8 wt% as initial subsidence liquid cathode, and the mass ratio of said intermediate alloy and total electrolyte is 1:4-5, under the condition of 700-900 deg.C said invention utilizes the electrolysis process to prepare magnesium-(8-30) wt% lanthanum-praseodymium-cerium intermediate alloy with high rare earth content.
Description
Technical field
The present invention relates to the method for low temperature sinking liquid cathode electrolytic preparation magnesium rare earth intermediate alloy.Belong to the fused salt electrolysis metallurgical technology field.
Background technology
The invention belongs to the preparation method of magnesium-rare earth intermediate alloy.Magnesium-rare earth intermediate alloy is that preparation is heat-resisting, the basic raw material of high temperature resistant creep, anti-corrosion advanced magnesium alloys.Preparation magnesium-rare earth intermediate alloy mainly contained following three kinds of methods in the past: the one, vacuum melting or fused salt cover down to the method for mixing, the 2nd, calciothermy, the 3rd, the liquid cathode that floats electrolytic process.Vacuum melting or fused salt cover the high and raw material costliness of equipment valency that the method for mixing is required down, and refining temperature height, single furnace output are less, have fused salt to be mingled with unavoidably in the fused salt covering consolute method alloy product.Because the proportion and the fusing point of most rare earth metals and MAGNESIUM METAL differ greatly, no matter which kind of all is difficult to obtain the uniform master alloy of composition to the method for mixing; Calciothermy reduction temperature height, the crucible material requirements of reaction usefulness is higher, and these two kinds of methods all belong to discontinuous production; Come-up liquid cathode electrolytic process exists product to disperse, bad collection, and electrolytic process makes alloy disperse, be easy to and the effect of anodic product chlorine because electrolytic solution seethes, and causes current efficiency to descend.
Summary of the invention
The present invention provides a kind of method of low temperature sinking liquid cathode electrolytic preparation magnesium rare earth intermediate alloy.
Problem to be solved by this invention is at the problem that the traditional magnesium of preparation-the rare earth intermediate alloy method exists, and contains (LPC) CL with lanthanum praseodymium cerium chloride remaining cheapness, that remain to be utilized after carrying neodymium through dewatering to prepare
3Amount is 8～30wt%'s (LPC) CL
3Being a kind of raw material, is that 5-8wt% magnesium-lanthanum-praseodymium-cerium master alloy is another kind of starting material with content, adopts lesser temps sinking liquid cathode electrolytic preparation than the preparation method of concentration up to the magnesium-lanthanum-praseodymium-cerium master alloy of 8～30wt%.
Preparation method's of the present invention technical scheme is: with KCl, NaCl, (LPC) CL
3Be ionogen, mass ratio KCl: NaCl: (LPC) CL
3Be 50-40%: 42-30%: 30～8%, described (LPC) CL
3Be electrolytical containing of (LPC) CL
3Amount is 8～30wt% and process dehydration, and water and water insoluble matter content are less than 15wt%; Above-mentioned ionogen is put into the electrolysis crucible through 100-200 ℃ of preheating with the abundant according to the above ratio mixing of ionogen; In the electrolysis High Temperature Furnaces Heating Apparatus, temperature is under the 700-900 ℃ of condition, is that the magnesium-lanthanum-praseodymium-cerium master alloy of 5-8wt% is made the sinking negative electrode with content, and this magnesium-lanthanum-praseodymium-cerium master alloy and total electrolytical total mass ratio are 1: 4～5, and cathode current density is 1～1.5A/cm
2, agitation as appropriate in the electrolytic process; The tapping temperature of product is controlled between 750-850 ℃; Require cathode alloy density greater than electrolyte density, all the time be in the sinking state, the rare earth metal of separating out on the liquid cathode surface in the electrolytic process is to the alloy internal divergence, speed of separating out and its velocity of diffusion to liquid cathode of rare earth are complementary, obtain the magnesium-lanthanum-praseodymium-cerium master alloy at a lower temperature.
Described raw material is to carry cheap lanthanum praseodymium cerium rare earth chloride remaining to be utilized behind the neodymium, and its dehydration method is:
Cheap lanthanum praseodymium cerium rare earth chloride to be drained off and the ammonia chloride of 5-20% are ground abundant mixing; Put into pallet, heating (vacuum tightness 9 * 10 in the vacuum hydro-extraction stove
-3MP); At 100-200 ℃, through 4-10 hour, make the lanthanum praseodymium cerium rare earth chloride raw material of dehydration, wherein water and water insoluble matter content are less than 15wt%.
The concentration of method preparation of the present invention is up to the lanthanum praseodymium cerium composition analysis (seeing Table two) of the magnesium-lanthanum-praseodymium-cerium master alloy of 8～30wt%, the detrimental impurity composition of the magnesium-lanthanum-praseodymium-cerium master alloy of being made very low (seeing Table).
Table one Mg-LPC master alloy impurity component is analyzed
| Kind | Y(wt.％) | Sm(wt.％) | Fe(wt.％) | Cu(wt.％) | Si(wt.％) | Ni(wt.％) |
| Mg-LPC | ＜0.003 | ＜0.003 | 0.013 | 0.005 | 0.019 | 0.001 |
The composition analysis of table dichloride lanthanum praseodymium cerium
| Lanthanum trichloride praseodymium cerium component content | Water and water-insoluble (wt%) | Other rare earth chlorides (wt%) |
| (LPC) CL of 8～30wt% 3 | 3-15％ | ＜1％ |
The method of low temperature sinking liquid cathode electrolytic preparation magnesium rare earth intermediate alloy of the present invention can be used for continuous large-scale production.Lanthanum praseodymium cerium rare earth chloride process dehydration remaining cheapness, that remain to be utilized back makes full use of resource as raw material after adopting mixed light rare earth to carry neodymium; The energy utilization rate height, current efficiency is greater than 70%; The magnesium rare earth intermediate alloy had magnesium-lanthanum, magnesium-cerium, magnesium-neodymium, magnesium-yttrium and magnesium-Fu yttrium etc. several in the past, and the present invention can prepare cheap magnesium-lanthanum-praseodymium-cerium master alloy, and its lanthanum praseodymium cerium mischmetal content composition is adjustable at 8-30wt%, and composition is even; Utilize the affluent resources advantage of China magnesium ore deposit and rare-earth mineral, adopt our advanced technologies production high-quality, cheapness, handy magnesium-lanthanum-praseodymium-cerium novel rare-earth master alloy, help the rapid exploitation of rare earth-magnesium alloy, utilize again for china natural resources and make contributions.The magnesium-lanthanum-praseodymium-cerium rare earth intermediate alloy of method preparation of the present invention is that the preparation preparation is heat-resisting, the basic raw material of high temperature resistant creep, anti-corrosion advanced magnesium alloys.
Embodiment
Embodiment one:
With commercially available chemical pure Repone K, sodium-chlor, through 8 ~ 30wt% (LPC) CL after the dehydration
3As starting material, % is than the LPCCl of weighing 10% by weight
350% KCl; 40% NaCl is as ionogen, through 100 ℃ of preheatings 3 hours, fully mixing again with another kind of raw material magnesium-5wt% lanthanum praseodymium cerium master alloy, its quality is 1: 4 with total electrolytic condenser, putting into diameter is 10cm, highly is in the electrolysis crucible of cylinder shape opening of 16cm, is warming up to 700-900 ℃, after treating added electrolyte melting, the beginning electrolysis.Agitation as appropriate in the electrolytic process, electrolysis end and to leave standstill for some time and make tapping temperature be controlled at 750 ℃ of products to come out of the stove, prepare the magnesium-lanthanum-praseodymium-cerium master alloy.Lanthanum praseodymium cerium mischmetal content is 18wt% in the alloy, and current efficiency reaches 71%.
Embodiment two:
With commercially available chemical pure Repone K, sodium-chlor, through 8 ~ 30wt% (LPC) CL after the dehydration
3As starting material, % is than the LPCCl of weighing 15% by weight
348% KCl; 37% NaCl is as ionogen, through 100 ℃ of preheatings 3 hours, fully mixing again with another kind of raw material magnesium-6wt% lanthanum praseodymium cerium master alloy, its quality is 1: 4.5 with total ionogen, putting into diameter is 10cm, highly is in the electrolysis crucible of cylinder shape opening of 16cm, is warming up to 700-900 ℃, after treating added electrolyte melting, the beginning electrolysis.Agitation as appropriate in the electrolytic process, electrolysis end and to leave standstill for some time and make tapping temperature be controlled at 780 ℃ of products to come out of the stove, prepare the magnesium-lanthanum-praseodymium-cerium master alloy.Lanthanum praseodymium cerium mischmetal content is 25wt% in the alloy, and current efficiency reaches 72%.
Embodiment three:
With commercially available chemical pure Repone K, sodium-chlor, through 8 ~ 30wt% (LPC) CL after the dehydration
3As starting material, % is than the LPCCl of weighing 25% by weight
3: 45% KCl; 30% NaCl is as ionogen, through 200 ℃ of preheatings 3 hours, fully mixing again with another kind of raw material magnesium-8wt% lanthanum praseodymium cerium master alloy, its quality is 1: 5 with total ionogen, putting into diameter is 10cm, highly is in the electrolysis crucible of cylinder shape opening of 16cm, is warming up to 700-900 ℃, after treating added electrolyte melting, the beginning electrolysis.Agitation as appropriate in the electrolytic process, electrolysis end and to leave standstill for some time and make tapping temperature be controlled at 820 ℃ of products to come out of the stove, prepare the magnesium-lanthanum-praseodymium-cerium master alloy.Lanthanum praseodymium cerium mischmetal content is 30wt% in the alloy, and current efficiency reaches 73%.
Claims (3)
1, a kind of method of low temperature sinking liquid cathode electrolytic preparation magnesium rare earth intermediate alloy is characterized in that: with KCl, NaCl, (LPC) CL
3Be ionogen, mass ratio KCl: NaCl: (LPC) CL
3Be 50-40%: 42-30%: 30～8%, described (LPC) CL
3Be electrolytical containing of (LPC) CL
3Amount is 8～30wt% and process dehydration, and water and water insoluble matter content are less than 15wt%; Above-mentioned ionogen is put into the electrolysis crucible through 100-200 ℃ of preheating with the abundant according to the above ratio mixing of ionogen; In the electrolysis High Temperature Furnaces Heating Apparatus, temperature is under the 700-900 ℃ of condition, is that the magnesium-lanthanum-praseodymium-cerium master alloy of 5-8wt% is made the sinking negative electrode with content, and this magnesium-lanthanum-praseodymium-cerium master alloy and total electrolytical total mass ratio are 1: 4～5, and cathode current density is 1～1.5A/cm
2, agitation as appropriate in the electrolytic process; The tapping temperature of product is controlled between 750-850 ℃, can obtain the magnesium-lanthanum-praseodymium-cerium master alloy.
2, the method for a kind of low temperature sinking liquid cathode electrolytic preparation magnesium rare earth intermediate alloy as claimed in claim 1 is characterized in that described (LPC) CL
3Raw material is to carry cheap lanthanum praseodymium cerium rare earth chloride remaining to be utilized behind the neodymium.
3, the method for low temperature sinking liquid cathode electrolytic preparation magnesium rare earth intermediate alloy as claimed in claim 1 or 2, described raw material is to carry cheap lanthanum praseodymium cerium rare earth chloride remaining to be utilized behind the neodymium, it is characterized in that this carries cheap lanthanum praseodymium cerium rare earth chloride remaining to be utilized behind the neodymium through processed, its water and water insoluble matter content are less than 15wt%.
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| CN100480433C CN100480433C (en) | 2009-04-22 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914699A (en) * | 2010-07-26 | 2010-12-15 | 中国科学院长春应用化学研究所 | Fused salt electrosynthesis method of hydrogen storage alloy containing magnesium, lithium, sodium and potassium |
| CN103590073A (en) * | 2013-11-14 | 2014-02-19 | 扬州宏福铝业有限公司 | Method for preparing mixed intermediate alloy of magnesium and light rare earth with double-cathode method |
| CN104388986A (en) * | 2014-11-26 | 2015-03-04 | 江西理工大学 | Production process for preparing copper-magnesium alloy by virtue of molten salt electrolysis method |
| CN104894603A (en) * | 2014-03-05 | 2015-09-09 | 中国科学院青海盐湖研究所 | Method for preparing magnesium-lead alloy through electrolysis |
| CN114015904A (en) * | 2021-08-03 | 2022-02-08 | 南昌大学 | Multistage continuous impurity removal method for rare earth magnesium intermediate alloy |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB647228A (en) * | 1946-11-13 | 1950-12-06 | Gustave Ferriere | Method for the obtention of an extra light alloy |
| US5118396A (en) * | 1989-06-09 | 1992-06-02 | The Dow Chemical Company | Electrolytic process for producing neodymium metal or neodymium metal alloys |
-
2005
- 2005-10-28 CN CNB2005100172297A patent/CN100480433C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914699A (en) * | 2010-07-26 | 2010-12-15 | 中国科学院长春应用化学研究所 | Fused salt electrosynthesis method of hydrogen storage alloy containing magnesium, lithium, sodium and potassium |
| CN103590073A (en) * | 2013-11-14 | 2014-02-19 | 扬州宏福铝业有限公司 | Method for preparing mixed intermediate alloy of magnesium and light rare earth with double-cathode method |
| CN104894603A (en) * | 2014-03-05 | 2015-09-09 | 中国科学院青海盐湖研究所 | Method for preparing magnesium-lead alloy through electrolysis |
| CN104388986A (en) * | 2014-11-26 | 2015-03-04 | 江西理工大学 | Production process for preparing copper-magnesium alloy by virtue of molten salt electrolysis method |
| CN114015904A (en) * | 2021-08-03 | 2022-02-08 | 南昌大学 | Multistage continuous impurity removal method for rare earth magnesium intermediate alloy |
| CN114015904B (en) * | 2021-08-03 | 2022-06-21 | 南昌大学 | Multistage continuous impurity removal method for rare earth magnesium intermediate alloy |
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|---|---|
| CN100480433C (en) | 2009-04-22 |
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Effective date of registration: 20170227 Address after: Chinese magnesium Valley Park in Jilin province 134300 Baishan City Hunjiang District No. 1 Patentee after: Baishan City Tian An metal magnesium Mining Co., Ltd. Address before: 130022 Changchun people's street, Jilin, No. 5625 Patentee before: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences |