CN100480433C - 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 PDF

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CN100480433C
CN100480433C CNB2005100172297A CN200510017229A CN100480433C CN 100480433 C CN100480433 C CN 100480433C CN B2005100172297 A CNB2005100172297 A CN B2005100172297A CN 200510017229 A CN200510017229 A CN 200510017229A CN 100480433 C CN100480433 C CN 100480433C
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magnesium
rare earth
lanthanum
praseodymium cerium
lanthanum praseodymium
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CN1772964A (en
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孟健
张德平
房大庆
王军
唐定骧
鲁化一
赵连山
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Baishan City Tian An Metal Magnesium Mining Co Ltd
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Changchun Institute of Applied Chemistry of CAS
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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

The method of low temperature sinking liquid cathode electrolytic preparation magnesium rare earth intermediate alloy
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 the problem that exists at preparation traditional magnesium-rare earth intermediate alloy method, and to carry lanthanum praseodymium cerium chloride remaining cheapness, that remain to be utilized behind the neodymium, after dehydration, preparing content is (LPC) Cl of 8~30wt% 3As raw material, be that 5-8wt% magnesium-lanthanum praseodymium cerium master alloy is another kind of starting material with content, adopt lesser temps sinking liquid cathode electrolytic preparation than the preparation method of concentration up to magnesium-lanthanum praseodymium cerium master alloy of 8~30wt%.
Preparation method's of the present invention technical scheme is: the raw material with KCl, NaCl, lanthanum praseodymium cerium chloride is an ionogen, mass ratio KCl:NaCl: the raw material of lanthanum praseodymium cerium chloride is 50-40%: 42-30%: 30~8%, the raw material of described ionogen lanthanum praseodymium cerium chloride, it contains (LPC) Cl 3Amount is 8~30wt%, and through dehydration, water and water insoluble matter content are less than 15wt%; Above-mentioned ionogen is put into the electrolysis crucible through 100-200 ℃ of preheatings with the abundant according to the above ratio mixing of ionogen; In the electrolysis High Temperature Furnaces Heating Apparatus, temperature is under 700-900 ℃ of conditions, is that 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 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 5-20% ammonia chloride 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 magnesium-lanthanum praseodymium cerium master alloy of 8~30wt%, the detrimental impurity composition very low (seeing Table) of the magnesium of being made-lanthanum praseodymium cerium master alloy.
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-rich 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.Magnesium-lanthanum praseodymium cerium mischmetal the master 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 (LPC) Cl 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 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 (LPC) Cl 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 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 (LPC) Cl of weighing 25% by weight 345% 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 magnesium-lanthanum praseodymium cerium master alloy.Lanthanum praseodymium cerium mischmetal content is 30wt% in the alloy, and current efficiency reaches 73%.

Claims (2)

1, a kind of method of low temperature sinking liquid cathode electrolytic preparation magnesium rare earth intermediate alloy, it is characterized in that: the raw material with KCl, NaCl, lanthanum praseodymium cerium chloride is an ionogen, and mass ratio is KCl:NaCl: the raw material of lanthanum praseodymium cerium chloride is 50-40%:42-30%:30~8%; The raw material of described ionogen lanthanum praseodymium cerium chloride, it contains (LPC) Cl 3Amount is 8~30wt%, and through dehydration, water and water insoluble matter content are less than 15wt%, and above-mentioned ionogen is put into the electrolysis crucible through 100-200 ℃ of preheatings with the abundant according to the above ratio mixing of ionogen; In the electrolysis High Temperature Furnaces Heating Apparatus, temperature is under 700-900 ℃ of conditions, is that 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 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, the raw material of lanthanum praseodymium cerium chloride is to carry cheap lanthanum praseodymium cerium rare earth chloride remaining to be utilized behind the neodymium.
CNB2005100172297A 2005-10-28 2005-10-28 Process for producing Mg rare earth intermediate alloy by Submerged Liquid Cathode electrolysis under low-temperature Active CN100480433C (en)

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CN101914699B (en) * 2010-07-26 2012-07-04 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
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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US5118396A (en) * 1989-06-09 1992-06-02 The Dow Chemical Company Electrolytic process for producing neodymium metal or neodymium metal alloys

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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