CN103184476A - Technique adopting basic magnesium carbonate to produce rare-earth magnesium alloy - Google Patents
Technique adopting basic magnesium carbonate to produce rare-earth magnesium alloy Download PDFInfo
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- CN103184476A CN103184476A CN2013100757977A CN201310075797A CN103184476A CN 103184476 A CN103184476 A CN 103184476A CN 2013100757977 A CN2013100757977 A CN 2013100757977A CN 201310075797 A CN201310075797 A CN 201310075797A CN 103184476 A CN103184476 A CN 103184476A
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Abstract
The invention discloses a technique adopting basic magnesium carbonate to produce rare-earth magnesium alloy. Hydrous magnesium chloride and hydrous rare earth chloride are taken as electrolytic raw materials, a molybdenum rod is taken as a negative electrode or liquid metal rare-earth or liquid magnesium-rare earth is taken as a sinking negative electrode, a graphite crucible is taken as a positive electrode and subjected to DC electrolysis through the molten salt electrolysis method, and the magnesium-rare earth is obtained at the negative electrode, a mixture of potassium chloride and sodium chloride of which the mass ratio is 1:(1-3) is taken as the electrolyte, and the hydrous magnesium chloride is prepared from basic magnesium carbonate. The preparation method comprises the following steps: (1) basic magnesium carbonate is soaked in acid to obtain magnesium chloride solution; and (2) magnesium chloride is subjected to evaporative crystallization to obtain magnesium chloride hexahydrate crystals. According to the invention, basic magnesium carbonate is taken as the raw material and subjected to acid-soaking pretreatment, and on the basis of acquiring a high-purity magnesium chloride hexahydrate intermediate product, DC electrolysis is conducted to obtain magnesium-rare earth containing more than 5-90 percent of rare earth. The technique has the advantages of smooth process, low cost, stable product quality and good quality and has very high popularization and application values.
Description
Technical field
The present invention relates to a kind of magnesium basic carbonate and produce the processing method of magnesium-rare earth, the highly purified magnesium chloride hexahydrate of intermediate product that is specially dc electrolysis magnesium basic carbonate in the chloride electrolyte prepares the method for magnesium-rare earth.Belong to the rare earth metallurgy technical field.
Background technology
Magnesium alloy has low density, high specific strength, high specific stiffness, high elastic coefficient, high damping properties, also has characteristics such as good machinability, thermal conductivity and anti-electromagnetic interference.Magnesium alloy is easy to reclaim than aluminium alloy, can accomplish the recycling of 100 %, so magnesium alloy materials is described as " green engineering structural metallic materials ".Rare earth element is owing to have unique configuration of extra-nuclear electron, show unique character, O, S and other non-metallic elements there is stronger avidity, in metallurgical, material field, unique effect is arranged, have the alloy solution of purification, improve alloy structure, improve alloy room temperature and mechanical behavior under high temperature, function such as enhancing alloy corrosion resistance energy.Magnesium-rare earth not only has the intrinsic advantage of magnesium alloy, also have simultaneously anti-oxidant, anticorrosive, high-temperature capability is high, high temperature resistance wriggling and reclaim advantages such as pollution-free, can satisfy Aeronautics and Astronautics, automobile, military project to loss of weight and requirements of saving energy, and replace engineering plastics to 3C(computer, communication, consumer electronics) requirements such as light, thin, little, highly integrated and environmental protection of product, application prospect is very extensive.
China is magnesium resource big country, reserves occupy first place in the world, rare earth accounts for the world and has verified more than 80% of rare earth reserves, magnesium and rare earth are the resources advantages that China shows unique characteristics, therefore, the exploitation magnesium-rare earth has special advantages in China, constantly improves existing magnesium-rare earth and is, and develop low cost, high performance novel rare-earth magnesium alloy, will have great pushing effect to the development in China's magnesium alloy materials and rare earth material field.
The preparation method of magnesium-rare earth mainly is smelting process and fused salt electrolysis process.Smelting process is to carry out melting with MAGNESIUM METAL and metal-rare-earth, obtains forming suitable alloy, uses various forming technique moulding then, makes component.Fused salt electrolysis process generally is in atmosphere, is anode with graphite, is negative electrode with metal molybdenum or tungsten, or is negative electrode with liquid metal magnesium, liquid metal rare earth, liquid magnesium-rare earth, the electrolytic preparation magnesium-rare earth.Wherein, have tangible unpolarizing with liquid cathode electrolytic preparation magnesium-rare earth, make rare earth ion be easy to separate out at negative electrode, be conducive to improve current efficiency, reduce bath voltage and power consumption.The liquid cathode electrolytic process comprises come-up negative electrode and two kinds of methods of sinking negative electrode, the former can produce the low magnesium-rare earth of content of rare earth, even MAGNESIUM METAL, the latter can produce the high magnesium-rare earth of content of rare earth, be convenient to the separation of electrolysate, simultaneously can reduce power consumption, improve the output of magnesium-rare earth.Fused salt electrolysis process prepares magnesium-rare earth and has advantages such as alloying constituent reduced in segregation, quality product height, preparation cost are low, has been subjected to widely and has paid close attention to.
Traditional fused salt electrolysis process is produced magnesium-rare earth, and the electrolysis raw material that adopts is Magnesium Chloride Anhydrous, but Magnesium Chloride Anhydrous is because preparing difficulty, the production cost height, thus cause the magnesium-rare earth cost height produced, lack the market competitiveness.Chinese invention patent application number 201110191455.2 discloses a kind of preparation method of magnesium-rare earth, its feature comprises: adopt closing down magnesium electrolysis bath, be that 2% ~ 15% mixture is the ionogen fused salt with magnesium eletrolysis molten salt system and rare earth chloride content, carry out electrolysis at 650 ℃ ~ 720 ℃, simultaneously add weight ratio in the closing down magnesium electrolysis bath and be (1.5 ~ 11): 1 Magnesium Chloride Anhydrous and rare earth chloride, because this processing method must adopt Magnesium Chloride Anhydrous and anhydrous chlorides of rase earth elements, thereby manufacturing cost is higher, and the content of the magnesium-rare earth middle-weight rare earths that obtains is lower, is no more than 10%.Chinese invention patent application number 201010100139.5 discloses a kind of method with hydrated magnesium chloride and rare earth chloride electrolytic preparation magnesium-rare earth alloy, and it is characterized in that: this method is with MgC1
22H
2O and CeCl
33H
2O or MgC1
22H
2O and NdC1
33H
2O is the electrolysis raw material, with MgC1
2-NaCl-KCl-CeC1
3System or MgC1
2-NaCl-KCl-NdC1
3System is ionogen, is that sinking negative electrode, graphite are anode with the molybdenum bar, is that 4.0 ~ 8.0V, temperature are to carry out dc electrolysis under 680 ~ 800 ℃ the condition at voltage, obtains magnesium-rare earth at negative electrode.This process using not exclusively magnesium chloride dihydrate and the three water rare earth chlorides of dehydration is the electrolysis raw material, has avoided removing in the traditional method water of constitution in the muriate crystal, simplifies technological process, has reduced the raw material production cost.Chinese invention patent application number 200910117402.9 discloses a kind of method of preparing magnesium-rare earth alloy by fused salt electrolysis process, it is characterized in that with hydrated magnesium chloride and moisture rare earth chloride be the electrolysis raw material, be ionogen with Repone K, be negative electrode with the molybdenum bar or be the sinking negative electrode with liquid metal rare earth or liquid magnesium-rare earth, exhausting with the graphite mandarin orange is anode, be 1000 ~ 2000A in electric current, voltage is 5 ~ 15V, temperature is to carry out dc electrolysis under 800 ~ 1000 ℃, obtain containing the magnesium-rare earth of rare earth 5 ~ 95wt% at negative electrode, this processing method even can adopt magnesium chloride hexahydrate and seven water rare earth chlorides are the electrolysis raw material, significantly reduced the preparation cost of electrolysis raw material, and the magnesium-rare earth product that obtains is formed evenly, segregation-free, quality is good, thereby certain technical superiority is arranged.The preparation method of above magnesium-rare earth is main electrolysis raw material at the magnesium chloride of anhydrous, partial dehydration or six water etc., can not directly contain the feedstock production magnesium-rare earth of magnesium with other.
Can though China is magnesium resource big country, China mainly concentrates on the salt lake, Qinghai for the preparation of the magnesium chloride raw material of magnesium-rare earth, for being main raw material with the magnesium basic carbonate, prepare magnesium-rare earth, then is in technological gap.
Summary of the invention
The object of the present invention is to provide a kind of magnesium basic carbonate to produce the processing method of magnesium-rare earth, adopting magnesium basic carbonate is raw material through the intermediates magnesium chloride hexahydrate after transforming, and uses fused salt electrolysis process to prepare magnesium-rare earth.The present invention directly adopts the electrolysis of intermediates magnesium chloride hexahydrate, has reduced production cost, its technology smoothness, and benefit is more remarkable, and constant product quality is easy to utilize.
Technical scheme of the present invention is: a kind of magnesium basic carbonate is produced the processing method of magnesium-rare earth, be the electrolysis raw material with hydrated magnesium chloride and moisture rare earth chloride, be negative electrode with the molybdenum bar or be the sinking negative electrode with liquid metal rare earth or liquid magnesium rare earth alloy, be that anode carries out dc electrolysis by fused salt electrolysis process with the plumbago crucible, obtain magnesium-rare earth at negative electrode, be that the Repone K of 1:1 ~ 3 and the mixture of sodium-chlor are ionogen with the mass ratio
Described hydrated magnesium chloride is prepared by magnesium basic carbonate, and the preparation method is:
(1) magnesium basic carbonate acidleach: to magnesium basic carbonate 4MgCO
3Mg (OH)
24H
2Adding HCl among the O carries out stirring reaction obtain magnesium chloride solution after solid dissolves fully;
(2) magnesium chloride evaporative crystallization: be 40.0% ~ 41.3% with the gained magnesium chloride solution through heating evaporation, the massfraction that is concentrated into magnesium chloride, controlling speed of cooling then is 2 ~ 4 ℃/min, and crystallisation by cooling, suction filtration separate, and drying obtains the magnesium chloride hexahydrate crystal.
In the described step (1), 4MgCO
3Mg (OH)
24H
2The mol ratio of O and HCl is 1:11 ~ 14.
Temperature in the described step (2) during crystallisation by cooling is 20 ~ 40 ℃.
Electrolysis raw material hydrated magnesium chloride and moisture rare earth chloride are that 1:0.10 ~ 1:12 mixes according to weight ratio, in the plumbago crucible of packing into, feed intake through being added drop-wise in the ionogen continuously after the heat fused.
Electric current is 1000 ~ 1600A during electrolysis, and voltage is 5 ~ 15V, and temperature is 800 ~ 1100 ℃.
Better parameter is: described electric current is 1200 ~ 1500A, and voltage is 7 ~ 13V, and temperature is 850 ~ 1000 ℃.
Described step (2), crystallisation by cooling temperature are 25 ~ 35 ℃.
Described step (3), the mass ratio of magnesium chloride hexahydrate and moisture rare earth chloride are 1:0.30 ~ 1.
Beneficial effect:
1, is the raw material production magnesium-rare earth with the magnesium basic carbonate, solved the source problem that comes of magnesium chloride raw material;
2, with acidleach-electrolysis production magnesium-rare earth, its technology smoothness, be easy to suitability for industrialized production;
3, directly adopted the electrolysis of intermediates magnesium chloride hexahydrate, constant product quality has reduced production cost, thereby has application value, has a extensive future.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
Further set forth the present invention by the following examples, these embodiment are only presented for purposes of illustration, do not limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example is usually according to normal condition.
A kind of magnesium basic carbonate is produced the processing method of magnesium-rare earth, and concrete steps are:
(1) magnesium basic carbonate acidleach: magnesium basic carbonate is put into stirred autoclave, add hydrochloric acid and carry out stirring reaction, stir and after solid dissolves fully, obtain magnesium chloride solution; Proper ratio can be according to 4MgCO
3Mg (OH)
24H
2The mol ratio of O and HCl is that 1:10 ~ 1:15 adding concentration is 30% hydrochloric acid.
(2) magnesium chloride evaporative crystallization: be 40.0% ~ 41.3% through heating evaporation, the massfraction that is concentrated into magnesium chloride with the gained magnesium chloride solution, controlling speed of cooling then is 2 ~ 4 ℃/min, be cooled to 20 ~ 40 ℃ and separate out crystal, separate through suction filtration, obtain highly purified magnesium chloride hexahydrate crystal at 70 ~ 80 ℃ of drying 1 ~ 1.5h;
(3) mixed material feeding: be the electrolysis raw material with the highly purified magnesium chloride hexahydrate of evaporative crystallization gained and moisture rare earth chloride, be that 1:0.10 ~ 1:12 mixes according to weight ratio, pack in the plumbago crucible, feed intake through being added drop-wise in the ionogen continuously after the heat fused;
(4) dc electrolysis: the Repone K and the sodium chloride mixture that with the mass ratio are 1:1 ~ 1:3 are ionogen, be the sinking negative electrode with liquid magnesium-rare earth, be anode with the plumbago crucible, be 1000 ~ 1600A at electric current, voltage is 5 ~ 15V, temperature is to carry out dc electrolysis under 800 ~ 1100 ℃ of conditions, obtains magnesium-rare earth at negative electrode.
Step (1), 4MgCO
3Mg (OH)
24H
2The optimum mole ratio of O and HCl is 1:11 ~ 1:14, and best stir speed (S.S.) is 20 ~ 30r/min.
Described step (2), crystallization when being cooled to 25 ~ 35 ℃.
Described step (3), the optimum weight ratio of highly purified magnesium chloride hexahydrate and moisture rare earth chloride are 1:0.30 ~ 1:1.
Described step (4), electric current the best are 1200 ~ 1500A, and voltage the best is 7 ~ 13V, and temperature the best is 850 ~ 1000 ℃.
Embodiment 1:
Be the magnesium basic carbonate of 41.7%wt with MgO content, put into stirred autoclave, add hydrochloric acid and carry out stirring reaction, treat to obtain magnesium chloride solution after solid dissolves fully, be 40.1% through heating evaporation, the massfraction that is concentrated into magnesium chloride, be cooled to 20 ℃ with the speed of 2 ℃/min then and separate out crystal, suction filtration separates, and dry 1.5h obtains highly purified magnesium chloride hexahydrate crystal.Be that 1:0.10 mixes with the highly purified magnesium chloride hexahydrate of gained and seven water Lanthanum trichlorides according to weight ratio, as the electrolysis raw material, pack in the plumbago crucible, the Repone K and the sodium chloride mixture that with the mass ratio are 1:1 are ionogen, be the sinking negative electrode with liquid magnesium-rare earth, be anode with the plumbago crucible, to be added drop-wise in the ionogen continuously through the electrolysis raw material after the heat fused, be 1000A at electric current, voltage is 5V, and temperature is to carry out dc electrolysis under 800 ℃ of conditions, obtains magnesium-rare earth at negative electrode, detect through EDS, the lanthanum content of magnesium-rare earth is about 5%.
Embodiment 2:
Be 42% magnesium basic carbonate with MgO content, put into stirred autoclave, according to 4MgCO
3Mg (OH)
24H
2The mol ratio of O and HCl is that 1:15 adding hydrochloric acid carries out stirring reaction, stirring is treated to obtain magnesium chloride solution after solid dissolves fully, be 40.2% through heating evaporation, the massfraction that is concentrated into magnesium chloride, be cooled to 40 ℃ with the speed of 4 ℃/min then and separate out crystal, suction filtration separates, and obtains highly purified magnesium chloride hexahydrate crystal at 80 ℃ of dry 1h.Be that 1:12 mixes with the highly purified magnesium chloride hexahydrate of gained and three water Neodymium trichlorides according to weight ratio, as the electrolysis raw material, pack in the plumbago crucible, the Repone K and the sodium chloride mixture that with the mass ratio are 1:3 are ionogen, be the sinking negative electrode with liquid magnesium-rare earth, be anode with the plumbago crucible, to be added drop-wise in the ionogen continuously through the electrolysis raw material after the heat fused, be 1500A at electric current, voltage is 15V, and temperature is to carry out dc electrolysis under 1100 ℃ of conditions, obtains magnesium-rare earth at negative electrode, detect through EDS, the neodymium content of magnesium-rare earth is more than 90%.
Table 1 is the reaction conditions tabulation that embodiment 3～embodiment 5 adopts.
Table 1
The MgO content of a=magnesium basic carbonate in the table 1; B=4MgCO
3Mg (OH)
24H
2The mol ratio of O and HCl; The c=stir speed (S.S.); D=is concentrated into the massfraction of magnesium chloride; The e=speed of cooling; The f=recrystallization temperature; The g=bake out temperature; The h=drying time; The kind of the moisture rare earth chloride of i=; The weight ratio of j=magnesium chloride hexahydrate and moisture rare earth chloride; The mass ratio of k=Repone K and sodium-chlor; The l=Faradaic current; The m=electrolysis voltage; The n=electrolysis temperature.Except the listed condition of table 1, all the other contents are with embodiment 1.
Table 2 is content of rare earth of the magnesium-rare earth for preparing of embodiment 3～embodiment 8.By the content of rare earth data of magnesium-rare earth listed in embodiment 1, embodiment 2 and the table 2 as can be seen, constant product quality of the present invention, content of rare earth is more than 5% ~ 90%.
Table 2
| Embodiment | 3 | 4 | 5 | 6 | 7 | 8 |
| The content of rare earth of magnesium-rare earth | Cerium 55% | Praseodymium 6% | Gadolinium 64% | Dysprosium 85% | Scandium 8% | Yttrium 28% |
Claims (8)
1. a magnesium basic carbonate is produced the processing method of magnesium-rare earth, be the electrolysis raw material with hydrated magnesium chloride and moisture rare earth chloride, be negative electrode with the molybdenum bar or be the sinking negative electrode with liquid metal rare earth or liquid magnesium rare earth alloy, be that anode carries out dc electrolysis by fused salt electrolysis process with the plumbago crucible, obtain magnesium-rare earth at negative electrode, it is characterized in that, be that the Repone K of 1:1 ~ 3 and the mixture of sodium-chlor are ionogen with the mass ratio
Described hydrated magnesium chloride is prepared by magnesium basic carbonate, and the preparation method is:
(1) magnesium basic carbonate acidleach: to magnesium basic carbonate 4MgCO
3Mg (OH)
24H
2Adding HCl among the O carries out stirring reaction obtain magnesium chloride solution after solid dissolves fully;
(2) magnesium chloride evaporative crystallization: be 40.0% ~ 41.3% with the gained magnesium chloride solution through heating evaporation, the massfraction that is concentrated into magnesium chloride, controlling speed of cooling then is 2 ~ 4 ℃/min, and crystallisation by cooling, suction filtration separate, and drying obtains the magnesium chloride hexahydrate crystal.
2. magnesium basic carbonate according to claim 1 is produced the processing method of magnesium-rare earth, it is characterized in that, and in the described step (1), 4MgCO
3Mg (OH)
24H
2The mol ratio of O and HCl is 1:11 ~ 14.
3. magnesium basic carbonate according to claim 1 is produced the processing method of magnesium-rare earth, it is characterized in that, the temperature in the described step (2) during crystallisation by cooling is 20 ~ 40 ℃.
4. magnesium basic carbonate according to claim 1 is produced the processing method of magnesium-rare earth, it is characterized in that, electrolysis raw material hydrated magnesium chloride and moisture rare earth chloride are that 1:0.10 ~ 1:12 mixes according to weight ratio, pack in the plumbago crucible, feed intake through being added drop-wise in the ionogen continuously after the heat fused.
5. magnesium basic carbonate according to claim 1 is produced the processing method of magnesium-rare earth, it is characterized in that electric current is 1000 ~ 1600A during electrolysis, and voltage is 5 ~ 15V, and temperature is 800 ~ 1100 ℃.
6. magnesium basic carbonate according to claim 5 is produced the processing method of magnesium-rare earth, it is characterized in that described electric current is 1200 ~ 1500A, and voltage is 7 ~ 13V, and temperature is 850 ~ 1000 ℃.
7. magnesium basic carbonate according to claim 1 is produced the processing method of magnesium-rare earth, it is characterized in that described step (2), crystallisation by cooling temperature are 25 ~ 35 ℃.
8. magnesium basic carbonate according to claim 1 is produced the processing method of magnesium-rare earth, it is characterized in that, and described step (3), the mass ratio of magnesium chloride hexahydrate and moisture rare earth chloride is 1:0.30 ~ 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109964341A (en) * | 2016-08-12 | 2019-07-02 | 波士顿电冶公司 | No leakage collector assembly and manufacturing method for metallurgical tank |
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| CN101613864A (en) * | 2009-07-29 | 2009-12-30 | 中国科学院青海盐湖研究所 | The method of preparing magnesium-rare earth alloy by fused salt electrolysis process |
| CN102433572A (en) * | 2011-12-26 | 2012-05-02 | 江西理工大学 | Production process for preparing magnesium-gadolinium alloy by fused salt electrolysis method |
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2013
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| US3855087A (en) * | 1972-10-11 | 1974-12-17 | Shinetsu Chemical Co | Method for producing rare earth metal-containing alloys |
| CN101613864A (en) * | 2009-07-29 | 2009-12-30 | 中国科学院青海盐湖研究所 | The method of preparing magnesium-rare earth alloy by fused salt electrolysis process |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109964341A (en) * | 2016-08-12 | 2019-07-02 | 波士顿电冶公司 | No leakage collector assembly and manufacturing method for metallurgical tank |
| CN109964341B (en) * | 2016-08-12 | 2022-07-05 | 波士顿电冶公司 | Leakless current collector assembly for metallurgical vessels and method of manufacture |
| US12050059B2 (en) | 2016-08-12 | 2024-07-30 | Boston Electrometallurgical Corporation | Leak free current collector assemblage for metallurgical vessel and methods of manufacture |
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Application publication date: 20130703 |