CN110042240A - A kind of technique that vacuum thermit reduction produces lithium metal and magnesium metal simultaneously - Google Patents
A kind of technique that vacuum thermit reduction produces lithium metal and magnesium metal simultaneously Download PDFInfo
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- CN110042240A CN110042240A CN201910354300.2A CN201910354300A CN110042240A CN 110042240 A CN110042240 A CN 110042240A CN 201910354300 A CN201910354300 A CN 201910354300A CN 110042240 A CN110042240 A CN 110042240A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses the techniques that a kind of vacuum thermit reduction produces lithium metal and magnesium metal simultaneously, belong to magnesium metal smelting technical field.Process flow of the invention are as follows: Step 1: according to mass ratio by lithium aluminate, forge white and reducing agent aluminium powder and carry out ingredient；Step 2: by lithium aluminate with forge white qualified mixed powder and aluminium powder and pressed pellet and be sent into reductive jar after mixing；Step 3: carrying out reduction reaction in reductive jar, generates high temperature magnesium vapor, high temperature lithium vapor and solid state reduction slag, high temperature magnesium vapor and lithium vapor and collected by condensation respectively；Sodium aluminate solution is generated Step 4: solid state reduction slag is reacted with sodium carbonate liquor, and carbon point is carried out to sodium aluminate solution and is decomposed, obtains aluminium hydroxide and sodium carbonate liquor, sodium carbonate liquor is re-used in this step.The reducing slag that technical process of the invention generates can continue extraction aluminium powder as reducing agent for being recycled, and effectively reduce production cost and substantially reduce the discharge of solid-state waste residue.
Description
Technical field
The invention belongs to lithium metal and magnesium metal smelting technical fields, more specifically to a kind of vacuum aluminothermic reduction
The technique that method produces lithium metal and magnesium metal simultaneously.
Background technique
Fused salt electrolysis process is the industrial production most important method of lithium metal at present, but fused salt electrolysis process there are long flow path,
The disadvantages of energy consumption is high, environmental pollution is serious, lithium impurity is more；Vacuum-thermal method produces lithium metal to be had relative to fused salt electrolysis process
Cost is relatively low, impurity is less.Production of magnesium by pidgeonprocess is most popular magnesium metal smelting technique, it is in high temperature high vacuum condition
It is lower that metal magnesium vapor is produced with reduction by ferrosilicon dolime；However, there are energy consumption height, the discharge of solid state reduction slag for this technique
The problems such as big is measured, therefore, it is necessary to carry out Improvement to traditional magnesium-smelting silicothermic process technology.Aluminothermy for smelting Mg is using low-melting
Aluminium powder substitutes ferrosilicon as reducing agent, reduction temperature can be made to reduce, and shortens reduction cycle, has compared to ferrosilicon process certain excellent
Gesture, but aluminium powder price is more expensive than ferrosilicon, so that the application of this method obtains certain restrictions.
The more serious deficiency of lithium metal or magnesium metal higher cost, environmental pollution is prepared for existing, has the relevant technologies
Scheme discloses, such as number of patent application: 2017103208768, the applying date: on May 9th, 2017, a kind of invention and created name are as follows: carbon
Thermal method produces the technique of magnesium metal and calcium carbide, the preparation step of the program simultaneously are as follows: step 1, according to mass ratio of each component oxygen
Change magnesium, calcium oxide, carbonaceous reducing agent, fluorite catalyst and carries out ingredient；Configuration material is placed in band sieve by step 2 after mixing
Ball mill is ground and is sieved, and the material of different fineness is obtained；Step 3 is uniformly mixed material after screening, is then fed into height
Pressure suppresses balling-up to roll-in ball machine, and dries；Step 4 is placed in pelletizing in vacuum reactor, vacuumizes to vacuum reactor,
Certain pressure and at a temperature of produce metal magnesium vapor and calcium carbide calcium carbide.The program can be same using magnesia and calcium oxide
When produce magnesium and calcium carbide, saved the energy, reduced environmental pollution, improved raw material availability, but whether needed preparing
It prepares calcium carbide while magnesium also to need depending on the condition of production, use of the program in enterprise produces is limited.
For another example number of patent application: 2010105719751, the applying date: on December 2nd, 2010, invention and created name are as follows: a kind of
The method of preparing Mg-Li alloy by vacuum synchronous thermal reduction, the technical process of the program include: the stoichiometry according to reduction reaction
Configure reactant；By solid reactant powder and it is uniformly mixed；It by reactant powders briquet and is put into reductive jar, true
Reciprocal of duty cycle 1-20Pa carries out thermal reduction reaction at 950-1500 DEG C of temperature, collects the alloy steam that reaction generates, is coagulated after condensation
Poly- state Mg-Li alloy.Using the oxide of metal Mg and metal Li or its precursor as raw material in the program, pass through vacuum-thermal reduction
Realize metal Mg reduction synchronous with metal Li's, the alloy preparation technology route is short, and stock utilization is high, but directly obtain
It is Mg-Li alloy, and the waste residue for generating in thermal reduction reaction is not further processed, resource utilization is not high.
Summary of the invention
1. technical problems to be solved by the inivention
It is an object of the invention to overcome, existing to prepare lithium metal or magnesium metal higher cost, environmental pollution more serious
Deficiency, provide a kind of vacuum thermit reduction while producing the technique of lithium metal and magnesium metal, this method by Vacuum Heat also
The two independent industrial processes of former legal system lithium and aluminothermy magnesium are combined into one, and can produce lithium metal and magnesium metal simultaneously,
And it can reduce a ton magnesium coal consumption for recycling by extraction reducing agent in reducing slag, largely reduce the discharge of solid state reduction slag,
It increases economic efficiency.
2. technical solution
In order to achieve the above objectives, technical solution provided by the invention are as follows:
The technique that a kind of vacuum thermit reduction of the invention produces lithium metal and magnesium metal simultaneously, comprising the following steps:
Step 1: carrying out ingredient according to mass ratio of each component: 30~40 parts of lithium aluminates and 45~55 parts forge the mixed of white composition
Powder, 12~16 parts of reducing agent aluminium powder are closed, gross mass number is 100 parts；
Step 2: by lithium aluminate with forge white qualified mixed powder and aluminium powder and pressed pellet and be sent into reduction after mixing
In tank；
Step 3: reductive jar is evacuated to absolute pressure lower than 100Pa, adjustment reductive jar temperature carries out reduction reaction,
It generates high temperature magnesium vapor, high temperature lithium vapor and solid state reduction slag, high temperature magnesium vapor and high temperature lithium vapor and flows to reductive jar respectively
It is collected after condensation in the magnesium crystallizer and lithium crystallizer of top setting；；
Step 4: sodium aluminate solution is generated by reacting after the solid state reduction slag grinding in step 3 with sodium carbonate liquor, and
Carbon point is carried out to sodium aluminate solution to decompose, and obtains aluminium hydroxide and sodium carbonate liquor, sodium carbonate liquor is re-used in this step.
As further improvement of the present invention, the vertical setting of reductive jar described in step 3, the magnesium crystallizer and lithium
Crystallizer is sequentially arranged by magnesium vapor, lithium vapor flow direction.
As further improvement of the present invention, the condensation-crystallization temperature of high temperature magnesium vapor described in step 3 is 630~650
DEG C, high temperature lithium vapor condensation-crystallization temperature is 160~180 DEG C.
As further improvement of the present invention, calcined aluminium hydroxide obtained in step 4 to obtain aluminium oxide,
The metallic aluminium that electrolysis of aluminum oxide obtains is used to prepare the reducing agent aluminium powder in step 1.
As further improvement of the present invention, qualification mixed powder described in step 2 is by lithium aluminate and to forge white mix
It closes powder to be ground and sieved in band sieve ball mill, obtains the material that granularity is 100~200 mesh.
As further improvement of the present invention, reductive jar temperature is risen to 1100~1200 DEG C in step 3 and is restored
React 120~360min.
As further improvement of the present invention, in step 2 by lithium aluminate, forge white qualified mixed powder and aluminium powder mixes
It is squeezed into pelletizing with ball press after closing uniformly, qualified pelletizing equivalent diameter is no more than 50mm.
As further improvement of the present invention, the sodium carbonate liquor that is reacted in step 4 with solid state reduction slag by the external world into
Row supplement.
As further improvement of the present invention, the sodium carbonate liquor concentration that reacts in step 4 with solid state reduction slag
For 100~130g/L, solution temperature is 80~95 DEG C.
As further improvement of the present invention, the temperature calcined to aluminium hydroxide obtained in step 4 is 1000
~1200 DEG C, calcination time is 120~360min.
3. beneficial effect
Using technical solution provided by the invention, compared with prior art, there is following remarkable result:
(1) a kind of vacuum thermit reduction of the invention produces the technique of lithium metal and magnesium metal simultaneously, utilizes lithium aluminate
With forge it is white produce lithium metal and magnesium metal simultaneously, by vacuum-thermal reduction legal system lithium and two, aluminothermy magnesium independent industrial production mistakes
Journey is combined into one, and is made raw material that can produce lithium metal and magnesium metal by a temperature-rise period, is simplified production technology road
Line.
(2) the vertical setting of reductive jar in the present invention, magnesium crystallizer and lithium crystallizer by magnesium vapor, lithium vapor flow direction according to
Secondary arrangement, the magnesium vapor scurried into lithium crystallizer are condensed to powdered, are then fallen under gravity into reductive jar and are added
Heat is vapor state, and magnesium vapor again passes by magnesium crystallizer and condensed, and realizes the circulating condensing of magnesium vapor, to ensure that magnesium lithium is mixed
The separating effect for closing steam, is conducive to the magnesium metal for obtaining high-purity and lithium metal.
(3) a kind of vacuum thermit reduction of the invention produces the technique of lithium metal and magnesium metal, reducing slag and carbon simultaneously
CO is passed through after acid sodium solution Leach reaction2Gas obtains aluminium hydroxide, and aluminium hydroxide calcined dehydration obtains aluminium oxide, then to oxygen
Change aluminium electroloysis and obtain metallic aluminium, metallic aluminium realizes the recycling of reducing agent, effectively as the raw material for preparing reducing agent aluminium powder
Reduce production cost, increase economic efficiency.
(4) a kind of vacuum thermit reduction of the invention produces the technique of lithium metal and magnesium metal, CO simultaneously2With reducing slag
Leach reaction generate sodium carbonate liquor, be circularly used for processing solid state reduction slag, realize the recycling of sodium carbonate liquor,
And reduce the discharge of solid-state waste residue.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the flow chart for the technique that a kind of vacuum thermit reduction of the invention produces lithium metal and magnesium metal simultaneously.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.Therefore, below to the embodiment of the present invention provided in the accompanying drawings
Detailed description be not intended to limit the range of claimed invention, but be merely representative of selected embodiment of the invention.
Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts all
Other embodiments shall fall within the protection scope of the present invention.
To further appreciate that the contents of the present invention, the present invention is described in detail in conjunction with the accompanying drawings and embodiments.
Embodiment 1
In conjunction with Fig. 1, a kind of vacuum thermit reduction of the present embodiment produces the technique of lithium metal and magnesium metal simultaneously, including
Following steps:
Step 1: ingredient is carried out according to mass ratio of each component, wherein 35 parts of lithium aluminates and 50 parts are forged white be uniformly mixed
To mixed powder, then weigh that the reducing agent aluminium powder that 15 parts of granule sizes are 160 mesh, purity is 99% is spare, three kinds of materials it is total
Mass fraction is 100 parts；
Step 2: lithium aluminate is squeezed into ball press with white qualified mixed powder is forged with 15 parts of aluminium powders after mixing
Pelletizing, qualified pelletizing equivalent diameter are 40mm, and then pelletizing is sent into reductive jar；In the present embodiment qualified mixed powder be by
35 parts of lithium aluminate and 50 parts of white sieve in ball mill in band of forging are ground and are sieved, and acquisition granularity is 100~200 purpose objects
Material；
Step 3: reductive jar is taken out sealing, simultaneously vacuum to absolute pressure is lower than 100Pa, and adjustment reductive jar temperature rises to 1100
DEG C carry out reduction reaction, reaction time 120min lithium aluminate and forges white reaction generation high temperature lithium vapor, high temperature magnesium vapor in pelletizing
With solid state reduction slag, high temperature magnesium vapor and high temperature lithium vapor flow to the magnesium crystallizer being arranged at the top of reductive jar and lithium crystallization respectively
It is collected after condensation in device；
Since the process requirement carries out under high vacuum environment, therefore it is equipped with and takes out in the metal condensation end of reductive jar low-temperature space
Gas system is to maintain the vacuum state in reductive jar, and mixed vapour that reduction reaction generates is from reductive jar high-temperature area to low-temperature space
Domain is flowed, and passes through the magnesium crystallizer and lithium crystallizer being sequentially arranged in flow process respectively.High temperature magnesium vapor condensation-crystallization temperature
It is 630~650 DEG C, is specifically in the present embodiment 650 DEG C, high temperature magnesium vapor is collected to obtain solid metallic by condensation-crystallization
Magnesium；High temperature lithium vapor condensation-crystallization temperature is 160~180 DEG C, is specifically in the present embodiment 180 DEG C, high temperature lithium vapor passes through
Condensation-crystallization is collected to obtain solid metallic lithium；
Further, in this embodiment the vertical setting of reductive jar, i.e., be arranged along the direction on substantially vertical ground, magnesium crystallization
Device and lithium crystallizer are sequentially arranged by magnesium vapor, lithium vapor flow direction, it is worth noting that, small part magnesium vapor may be because
Flowing velocity is too fast to cause it not condense sufficiently and run away to lithium crystallizer in magnesium crystallizer, so that a small amount of magnesium vapor is mixed
It is condensed to lithium vapor and in lithium crystallizer；Since the temperature being arranged at lithium crystallizer is 160~180 DEG C, it is far below magnesium vapor
630~650 DEG C of crystallization temperature, magnesium vapor is condensed under low-temperature condition to powdered, is then fallen under gravity into vertical
In the reductive jar of setting, powdered solid-state magnesium granules are heated to be vapor state again by the high-temperature region of reductive jar, and magnesium vapor is again
It is secondary to be condensed by magnesium crystallizer, realize the circulating condensing of magnesium vapor, to ensure the separating effect of magnesium lithium mixed vapour, favorably
In obtaining the magnesium metal and lithium metal of high-purity.
In addition, improving the cold of steam by installing fin additional in magnesium lithium crystallizer to increase condensation area in the present embodiment
Solidifying efficiency, so that the separating effect for preventing high temperature mixed vapour from generating because flowing velocity is too fast, the scale of construction is larger is bad, further
, in order to further increase the separating effect of magnesium lithium vapor, pre-cooling can also be preset in reductive jar flow of vapor exit
Device, the high-temperature vapour first generated to reductive jar are cooled down in advance, and precooling temperature is slightly larger than the crystallization temperature of magnesium vapor,
Then so that mixed vapour is entered magnesium again, carry out condensation-crystallization respectively in lithium crystallizer, obtain the magnesium metal and metal of higher degree
Lithium.
Step 4: sodium aluminate solution is generated by reacting after the solid state reduction slag grinding in step 3 with sodium carbonate liquor, and
Carry out carbon point to sodium aluminate solution to decompose, obtain aluminum hydroxide precipitation and sodium carbonate liquor, sodium carbonate liquor it is reusable in
The Leach reaction of reducing slag in this step, the sodium carbonate liquor reacted with solid state reduction slag can also be according to actual use situations by outer
Boundary carries out reasonable supplement.
Ore raw materials is lithium aluminate and forges white in the present embodiment, and chemical molecular formula is lithium aluminate LiAlO2, forge white
CaOMgO by lithium aluminate and forges white weigh by weight ratio and mixes and smash and grind into 100~200 purposes in step 2 first
Powdery, it is agglomerating with press machine extruding after then being mixed in proportion with aluminium powder, the pelletizing being pressed into is put into reductive jar.This implementation
In example by lithium aluminate, forge white qualified mixed powder and aluminium powder and be squeezed into pelletizing after mixing, qualified pelletizing equivalent diameter is
40mm, specifically, qualified pelletizing can be the sphere structure of regular shape, or walnut shape, pincushion, elliposoidal or cylinder
The blocks of solid of the non-regular shapes such as shape, equivalent diameter refer to that the diameter of the volume same sphere of blocks of solid is 40mm.
Specifically, the chemical reaction that pelletizing occurs in reductive jar in step 3 in the present embodiment is as follows:
LiAlO2+CaO·MgO+Al→Li↑+Mg↑+CaO·Al2O3；
It is leached after being ground the solid state reduction slag that above-mentioned reaction process generates in step 4 with sodium carbonate liquor
Reaction generates sodium aluminate solution, and the chemical reaction of generation is as follows:
CaO·Al2O3+Na2CO3+4H2O→2NaAl(OH)4+CaCO3↓；
The sodium carbonate liquor concentration to react in step 4 with solid state reduction slag is 110g/L, and solution temperature is 80 DEG C.
The CaCO generated in the present embodiment3Precipitating and NaAl (OH)4Solution obtains pure sodium aluminate solution by solid-liquor separation
Liquid.At this time to carbon point decomposition is carried out in sodium aluminate solution, aluminum hydroxide precipitation and sodium carbonate liquor are obtained, can must be consolidated after filtering
State Al (OH)3And the Leach reaction for continuing on for solid state reduction slag can be recycled in sodium carbonate liquor, sodium carbonate liquor.The process
The chemical reaction of generation is as follows:
2NaAl(OH)4+CO2→Na2CO3+2Al(OH)3↓+H2O；
A kind of vacuum thermit reduction of the present embodiment produces the technique of lithium metal and magnesium metal simultaneously, will obtain in step 4
To aluminum hydroxide precipitation be separated by filtration after calcined to obtain aluminium oxide again, the metallic aluminium that electrolysis of aluminum oxide obtains is for making
Reducing agent aluminium powder in standby step 1, realizes the recycling of reducing agent.Specifically, solid-state Al (OH)3It is forged at 1000 DEG C
Burn 150min, Al (OH)3Al is obtained after calcined dehydration2O3, the chemical reaction of generation is as follows:
2Al(OH)3→Al2O3+3H2O。
Lithium aluminate in the present embodiment forges the white resource utilization that waste residue is realized with the reduction reaction of reducing agent aluminium powder；Reduction
CO is passed through after slag and sodium carbonate liquor Leach reaction2Gas obtains aluminium hydroxide, and aluminium hydroxide calcined dehydration obtains aluminium oxide,
Metallic aluminium is obtained to alumina eltrolysis again, as the raw material for preparing reducing agent aluminium powder, the circulation for realizing reducing agent makes metallic aluminium
With effectively reducing production cost, increase economic efficiency.
Embodiment 2
A kind of vacuum thermit reduction of the present embodiment produces the technique of lithium metal and magnesium metal, step and implementation simultaneously
Example 1 is essentially identical, the difference is that:
Step 1: ingredient is carried out according to mass ratio of each component, wherein 33 parts of lithium aluminates and 55 parts are forged white be uniformly mixed
To mixed powder, then weigh that the reducing agent aluminium powder that 12 parts of granule sizes are 170 mesh, purity is 99% is spare, three kinds of materials it is total
Mass fraction is 100 parts；
Step 2: lithium aluminate is squeezed into ball press with white qualified mixed powder is forged with 12 parts of aluminium powders after mixing
Pelletizing, qualified pelletizing equivalent diameter are 30mm, and then pelletizing is sent into reductive jar；In the present embodiment qualified mixed powder be by
33 parts of lithium aluminate and 55 parts of white sieve in ball mill in band of forging are ground and are sieved, and acquisition granularity is 100~200 purpose objects
Material；
Step 3: reductive jar is taken out sealing, simultaneously vacuum to absolute pressure is lower than 100Pa, and adjustment reductive jar temperature rises to 1150
DEG C carry out reduction reaction, reaction time 180min lithium aluminate and forges white reaction generation high temperature lithium vapor, high temperature magnesium vapor in pelletizing
With solid state reduction slag, it is specifically 640 DEG C that high temperature magnesium vapor condensation-crystallization temperature is 630~650 DEG C in the present embodiment, high temperature
Magnesium vapor is collected to obtain solid metallic magnesium by condensation-crystallization；High temperature lithium vapor condensation-crystallization temperature is 160~180 DEG C, specifically
It is in the present embodiment 170 DEG C, high temperature lithium vapor is collected to obtain solid metallic lithium by condensation-crystallization；
Step 4: sodium aluminate solution is generated by reacting after the solid state reduction slag grinding in step 3 with sodium carbonate liquor, and
Carry out carbon point to sodium aluminate solution to decompose, obtain aluminum hydroxide precipitation and sodium carbonate liquor, sodium carbonate liquor it is reusable in
The Leach reaction of reducing slag in this step, the sodium carbonate liquor reacted with solid state reduction slag can also be according to actual use situations by outer
Boundary carries out reasonable supplement.
Ore raw materials is lithium aluminate and forges white in the present embodiment, and chemical molecular formula is lithium aluminate LiAlO2, forge white
CaOMgO by lithium aluminate and forges white weigh by weight ratio and mixes and smash and grind into 100~200 purposes in step 2 first
Powdery, it is agglomerating with press machine extruding after then being mixed in proportion with aluminium powder, the pelletizing being pressed into is put into reductive jar.This implementation
In example by lithium aluminate, forge white qualified mixed powder and aluminium powder and be squeezed into pelletizing after mixing, qualified pelletizing equivalent diameter is
30mm。
Specifically, the chemical reaction that pelletizing occurs in reductive jar in step 3 in the present embodiment is as follows:
LiAlO2+CaO·MgO+Al→Li↑+Mg↑+CaO·Al2O3；
It is leached after being ground the solid state reduction slag that above-mentioned reaction process generates in step 4 with sodium carbonate liquor
Reaction generates sodium aluminate solution, and the chemical reaction of generation is as follows:
CaO·Al2O3+Na2CO3+4H2O→2NaAl(OH)4+CaCO3↓；
The sodium carbonate liquor concentration to react in step 4 with solid state reduction slag is 100g/L, and solution temperature is 90 DEG C.
The CaCO generated in the present embodiment3Precipitating and NaAl (OH)4Solution obtains pure sodium aluminate solution by solid-liquor separation
Liquid.At this time to carbon point decomposition is carried out in sodium aluminate solution, aluminum hydroxide precipitation and sodium carbonate liquor are obtained, can must be consolidated after filtering
State Al (OH)3And the Leach reaction for continuing on for solid state reduction slag can be recycled in sodium carbonate liquor, sodium carbonate liquor.The process
The chemical reaction of generation is as follows:
2NaAl(OH)4+CO2→Na2CO3+2Al(OH)3↓+H2O；
Again by solid-state Al (OH) obtained in step 43360min, Al (OH) are calcined at 1150 DEG C3After calcined dehydration
To Al2O3, the chemical reaction of generation is as follows:
2Al(OH)3→Al2O3+3H2O。
Obtained aluminium oxide is further electrolysed in the present embodiment and obtains metallic aluminium, as the original for preparing reducing agent aluminium powder
Material.
In the present embodiment using lithium aluminate and forge it is white produce lithium metal and magnesium metal simultaneously, by vacuum-thermal reduction legal system lithium and
The two independent industrial processes of aluminothermy magnesium are combined into one, and make raw material that can produce metal by a temperature-rise period
Lithium and magnesium metal, and the reducing slag generated can continue extraction aluminium powder as reducing agent for being recycled, and effectively reduce production
Cost and the discharge for substantially reducing solid-state waste residue.
Embodiment 3
A kind of vacuum thermit reduction of the present embodiment produces the technique of lithium metal and magnesium metal, step and implementation simultaneously
Example 1 is essentially identical, the difference is that:
Step 1: ingredient is carried out according to mass ratio of each component, wherein 31 parts of lithium aluminates and 53 parts are forged white be uniformly mixed
To mixed powder, then weigh that the reducing agent aluminium powder that 16 parts of granule sizes are 170 mesh, purity is 99% is spare, three kinds of materials it is total
Mass fraction is 100 parts；
Step 2: lithium aluminate is squeezed into ball press with white qualified mixed powder is forged with 16 parts of aluminium powders after mixing
Pelletizing, qualified pelletizing equivalent diameter are 50mm, and then pelletizing is sent into reductive jar；In the present embodiment qualified mixed powder be by
31 parts of lithium aluminate and 53 parts of white sieve in ball mill in band of forging are ground and are sieved, and acquisition granularity is 100~200 purpose objects
Material；
Step 3: reductive jar is taken out sealing, simultaneously vacuum to absolute pressure is lower than 100Pa, and adjustment reductive jar temperature rises to 1150
DEG C carry out reduction reaction, reaction time 360min lithium aluminate and forges white reaction generation high temperature lithium vapor, high temperature magnesium vapor in pelletizing
With solid state reduction slag, it is specifically 640 DEG C that high temperature magnesium vapor condensation-crystallization temperature is 630~650 DEG C in the present embodiment, high temperature
Magnesium vapor is collected to obtain solid metallic magnesium by condensation-crystallization；High temperature lithium vapor condensation-crystallization temperature is 160~180 DEG C, specifically
It is in the present embodiment 160 DEG C, high temperature lithium vapor is collected to obtain solid metallic lithium by condensation-crystallization；
Step 4: sodium aluminate solution is generated by reacting after the solid state reduction slag grinding in step 3 with sodium carbonate liquor, and
Carry out carbon point to sodium aluminate solution to decompose, obtain aluminum hydroxide precipitation and sodium carbonate liquor, sodium carbonate liquor it is reusable in
The Leach reaction of reducing slag in this step, the sodium carbonate liquor reacted with solid state reduction slag can also be according to actual use situations by outer
Boundary carries out reasonable supplement.
Further, in this embodiment the sodium carbonate liquor concentration to react with solid state reduction slag is 120g/L, solution
Temperature is 85 DEG C.
The solid-state Al (OH) for again obtaining step 4 in the present embodiment3200min, Al (OH) are calcined at 1100 DEG C3Calcining
Al is obtained after dehydration2O3, Al2O3Further electrolysis obtains metallic aluminium, as the raw material for preparing reducing agent aluminium powder.
Embodiment 4
A kind of vacuum thermit reduction of the present embodiment produces the technique of lithium metal and magnesium metal, step and implementation simultaneously
Example 1 is essentially identical, the difference is that:
Step 1: ingredient is carried out according to mass ratio of each component, wherein 40 parts of lithium aluminates and 45 parts are forged white be uniformly mixed
To mixed powder, then weigh that the reducing agent aluminium powder that 15 parts of granule sizes are 165 mesh, purity is 99% is spare, three kinds of materials it is total
Mass fraction is 100 parts；
Step 2: lithium aluminate is squeezed into ball press with white qualified mixed powder is forged with 15 parts of aluminium powders after mixing
Pelletizing, qualified pelletizing equivalent diameter are 35mm, and then pelletizing is sent into reductive jar；In the present embodiment qualified mixed powder be by
40 parts of lithium aluminate and 45 parts of white sieve in ball mill in band of forging are ground and are sieved, and acquisition granularity is 100~200 purpose objects
Material；
Step 3: reductive jar is taken out sealing, simultaneously vacuum to absolute pressure is lower than 100Pa, and adjustment reductive jar temperature rises to 1200
DEG C carry out reduction reaction, reaction time 220min lithium aluminate and forges white reaction generation high temperature lithium vapor, high temperature magnesium vapor in pelletizing
With solid state reduction slag, it is specifically 630 DEG C that high temperature magnesium vapor condensation-crystallization temperature is 630~650 DEG C in the present embodiment, high temperature
Magnesium vapor is collected to obtain solid metallic magnesium by condensation-crystallization；High temperature lithium vapor condensation-crystallization temperature is 160~180 DEG C, specifically
It is in the present embodiment 160 DEG C, high temperature lithium vapor is collected to obtain solid metallic lithium by condensation-crystallization；
Step 4: sodium aluminate solution is generated by reacting after the solid state reduction slag grinding in step 3 with sodium carbonate liquor, and
Carry out carbon point to sodium aluminate solution to decompose, obtain aluminum hydroxide precipitation and sodium carbonate liquor, sodium carbonate liquor it is reusable in
The Leach reaction of reducing slag in this step, the sodium carbonate liquor reacted with solid state reduction slag can also be according to actual use situations by outer
Boundary carries out reasonable supplement.
Further, in this embodiment the sodium carbonate liquor concentration to react with solid state reduction slag is 130g/L, solution
Temperature is 95 DEG C.
The solid-state Al (OH) for again obtaining the step in the present embodiment3300min, Al (OH) are calcined at 1200 DEG C3Calcining
Al is obtained after dehydration2O3, Al2O3Further electrolysis obtains metallic aluminium, as the raw material for preparing reducing agent aluminium powder.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
Invention is explained in detail, those skilled in the art should understand that: it still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these modification or
Replacement, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (10)
1. the technique that a kind of vacuum thermit reduction produces lithium metal and magnesium metal simultaneously, it is characterised in that: the following steps are included:
Step 1: carrying out ingredient according to mass ratio of each component: 30~40 parts of lithium aluminates and 45~55 parts forge the mixed powder of white composition
Material, 12~16 parts of reducing agent aluminium powder, gross mass number are 100 parts；
Step 2: by lithium aluminate with forge white qualified mixed powder and aluminium powder and pressed pellet and be sent into reductive jar after mixing
It is interior；
Step 3: reductive jar is evacuated to absolute pressure lower than 100Pa, adjustment reductive jar temperature carries out reduction reaction, generates
High temperature magnesium vapor, high temperature lithium vapor and solid state reduction slag, high temperature magnesium vapor and high temperature lithium vapor are flowed to respectively at the top of reductive jar
It is collected after condensation in the magnesium crystallizer and lithium crystallizer of setting；
Step 4: generating sodium aluminate solution for reacting after the solid state reduction slag grinding in step 3 with sodium carbonate liquor, and to aluminium
Acid sodium solution carries out carbon point and decomposes, and obtains aluminium hydroxide and sodium carbonate liquor, sodium carbonate liquor is re-used in this step.
2. a kind of vacuum thermit reduction according to claim 1 produces the technique of lithium metal and magnesium metal simultaneously, special
Sign is: the vertical setting of reductive jar described in step 3, and the magnesium crystallizer and lithium crystallizer press magnesium vapor, lithium vapor flowing side
To being sequentially arranged.
3. a kind of vacuum thermit reduction according to claim 1 produces the technique of lithium metal and magnesium metal simultaneously, special
Sign is: the condensation-crystallization temperature of high temperature magnesium vapor described in step 3 is 630~650 DEG C, high temperature lithium vapor condensation-crystallization temperature
It is 160~180 DEG C.
4. a kind of vacuum thermit reduction according to claim 1 produces the technique of lithium metal and magnesium metal simultaneously, special
Sign is: aluminium hydroxide obtained in step 4 being calcined to obtain aluminium oxide, the metallic aluminium that electrolysis of aluminum oxide obtains is used for
Reducing agent aluminium powder in preparation step one.
5. a kind of vacuum thermit reduction according to claim 1 produces the technique of lithium metal and magnesium metal simultaneously, special
Sign is: qualification mixed powder described in step 2 be by lithium aluminate and forge white mixed powder band sieve ball mill in grind
It grinds and sieves, obtain the material that granularity is 100~200 mesh.
6. a kind of vacuum thermit reduction according to claim 1 produces the technique of lithium metal and magnesium metal simultaneously, special
Sign is: reductive jar temperature being risen to 1100~1200 DEG C of 120~360min of progress reduction reaction in step 3.
7. a kind of vacuum thermit reduction according to claim 1 produces the technique of lithium metal and magnesium metal simultaneously, special
Sign is: in step 2 by lithium aluminate, forge white qualified mixed powder and aluminium powder is squeezed into pelletizing with ball press after mixing,
Qualified pelletizing equivalent diameter is no more than 50mm.
8. a kind of vacuum thermit reduction according to claim 1 produces the technique of lithium metal and magnesium metal simultaneously, special
Sign is: the sodium carbonate liquor reacted in step 4 with solid state reduction slag is supplemented by the external world.
9. a kind of vacuum thermit reduction according to claim 1 produces the technique of lithium metal and magnesium metal simultaneously, special
Sign is: the sodium carbonate liquor concentration to react in step 4 with solid state reduction slag is 100~130g/L, solution temperature 80
~95 DEG C.
10. a kind of vacuum thermit reduction according to claim 4 produces the technique of lithium metal and magnesium metal simultaneously, special
Sign is: the temperature calcined to aluminium hydroxide obtained in step 4 is 1000~1200 DEG C, calcination time is 120~
360min。
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111057850A (en) * | 2020-01-03 | 2020-04-24 | 四川万邦胜辉新能源科技有限公司 | Method for preparing high-purity lithium metal by vacuum thermal reduction method |
| CN112267018A (en) * | 2020-09-29 | 2021-01-26 | 朱广东 | Aluminum magnesium co-production process |
| CN112981098A (en) * | 2021-02-02 | 2021-06-18 | 朱广东 | Dolomite smelting device and smelting method thereof |
| WO2021135399A1 (en) * | 2020-01-03 | 2021-07-08 | 四川万邦胜辉新能源科技有限公司 | Method for producing magnesium-lithium alloy by means of gaseous co-condensation |
| CN114317964A (en) * | 2022-01-05 | 2022-04-12 | 重庆赛迪热工环保工程技术有限公司 | Process and device for reducing zinc-containing material by vacuum low-temperature aluminothermic process |
| CN114485148A (en) * | 2022-01-14 | 2022-05-13 | 中南大学 | High-temperature reaction-evaporative crystallization integrated smelting equipment and smelting method based on smelting equipment |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005097648A (en) * | 2003-09-22 | 2005-04-14 | Mitsui Mining & Smelting Co Ltd | Method for recovering magnesium-based alloy waste material |
| CN101845550A (en) * | 2010-04-12 | 2010-09-29 | 东北大学 | Method for extracting aluminum hydroxide and aluminum oxide from side product obtained by preparing magnesium metal by taking aluminum or aluminum alloy as reducing agent |
| CN102011021A (en) * | 2010-12-02 | 2011-04-13 | 重庆大学 | Method for reduction preparation of Mg-Li-Sr alloy by vacuum heat |
| CN102080164A (en) * | 2010-12-02 | 2011-06-01 | 重庆大学 | Method for preparing Mg-Li alloy by vacuum synchronous thermal reduction |
| CN102181670A (en) * | 2011-04-25 | 2011-09-14 | 东北大学 | Method for preparing titanium sponge through magnesium and chlorine recycling |
| CN109536751A (en) * | 2018-12-04 | 2019-03-29 | 辽宁科技学院 | A kind of method of aluminothermic reduction production magnesium lithium alloy by-product magnesium aluminate spinel |
-
2019
- 2019-04-29 CN CN201910354300.2A patent/CN110042240A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005097648A (en) * | 2003-09-22 | 2005-04-14 | Mitsui Mining & Smelting Co Ltd | Method for recovering magnesium-based alloy waste material |
| CN101845550A (en) * | 2010-04-12 | 2010-09-29 | 东北大学 | Method for extracting aluminum hydroxide and aluminum oxide from side product obtained by preparing magnesium metal by taking aluminum or aluminum alloy as reducing agent |
| CN102011021A (en) * | 2010-12-02 | 2011-04-13 | 重庆大学 | Method for reduction preparation of Mg-Li-Sr alloy by vacuum heat |
| CN102080164A (en) * | 2010-12-02 | 2011-06-01 | 重庆大学 | Method for preparing Mg-Li alloy by vacuum synchronous thermal reduction |
| CN102181670A (en) * | 2011-04-25 | 2011-09-14 | 东北大学 | Method for preparing titanium sponge through magnesium and chlorine recycling |
| CN109536751A (en) * | 2018-12-04 | 2019-03-29 | 辽宁科技学院 | A kind of method of aluminothermic reduction production magnesium lithium alloy by-product magnesium aluminate spinel |
Non-Patent Citations (2)
| Title |
|---|
| 苏联奥斯特罗什科等: "《锂的化学与工艺学》", 31 May 1965 * |
| 郑笑芳等: "真空硅热直接还原制备镁锂合金研究", 《真空科学与技术学报》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111057850B (en) * | 2020-01-03 | 2020-12-25 | 四川万邦胜辉新能源科技有限公司 | Method for preparing high-purity lithium metal by vacuum thermal reduction method |
| WO2021135399A1 (en) * | 2020-01-03 | 2021-07-08 | 四川万邦胜辉新能源科技有限公司 | Method for producing magnesium-lithium alloy by means of gaseous co-condensation |
| JP2022547287A (en) * | 2020-01-03 | 2022-11-11 | スーチュァン ユニオン シャイン ニュー エネルギー サイ－テック カンパニー リミテッド | Magnesium Lithium Alloy Production Method by Gas State Coaggregation Method |
| JP7381140B2 (en) | 2020-01-03 | 2023-11-15 | スーチュァン ユニオン シャイン ニュー エネルギー サイ－テック カンパニー リミテッド | Magnesium lithium alloy production method using gas state co-aggregation method |
| CN112267018A (en) * | 2020-09-29 | 2021-01-26 | 朱广东 | Aluminum magnesium co-production process |
| CN112981098A (en) * | 2021-02-02 | 2021-06-18 | 朱广东 | Dolomite smelting device and smelting method thereof |
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