WO2021135399A1 - 一种气态共冷凝法生产镁锂合金的方法 - Google Patents

一种气态共冷凝法生产镁锂合金的方法 Download PDF

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WO2021135399A1
WO2021135399A1 PCT/CN2020/115864 CN2020115864W WO2021135399A1 WO 2021135399 A1 WO2021135399 A1 WO 2021135399A1 CN 2020115864 W CN2020115864 W CN 2020115864W WO 2021135399 A1 WO2021135399 A1 WO 2021135399A1
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lithium
magnesium
chamber
temperature
condensing chamber
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English (en)
French (fr)
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周君
张广立
杨培
干勇
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四川万邦胜辉新能源科技有限公司
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Priority to EP20910104.7A priority Critical patent/EP3960337B1/en
Priority to US17/596,417 priority patent/US20220307108A1/en
Priority to JP2022514762A priority patent/JP7381140B2/ja
Publication of WO2021135399A1 publication Critical patent/WO2021135399A1/zh

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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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
    • B01D5/0033—Other features
    • B01D5/0036—Multiple-effect condensation; Fractional condensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • 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
    • 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
    • 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
    • C22B5/16—Dry methods smelting of sulfides or formation of mattes with volatilisation or condensation of the metal being produced
    • 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
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/02—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
    • 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
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/04—Refining by applying a vacuum
    • 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
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B5/00—Muffle furnaces; Retort furnaces; Other furnaces in which the charge is held completely isolated
    • F27B5/04—Muffle furnaces; Retort furnaces; Other furnaces in which the charge is held completely isolated adapted for treating the charge in vacuum or special atmosphere
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D7/00—Forming, maintaining, or circulating atmospheres in heating chambers
    • F27D7/06—Forming or maintaining special atmospheres or vacuum within heating chambers
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • 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

Definitions

  • the invention belongs to the technical field of light metal alloy material preparation, and relates to a new method for manufacturing magnesium-lithium alloy with high purity, ultra-fine crystal grains and uniform alloy, and is specifically a method for producing magnesium-lithium alloy by a gaseous co-condensation method.
  • the atomic number of lithium metal is 3, the nucleus is composed of three protons and four neutrons, there are three electrons around the nucleus, and there are two electrons on the K electron layer.
  • the electron layer structure is 1S 2 2S 1 , and the chemical properties of lithium are very Active, the compound is a polar molecule that easily absorbs water, making it difficult to extract the metal. This metal forms a very important compound with many elements, solid solution and other alloys, forming an alloy with good deformability and easy processing.
  • the melting point of metallic lithium is 180.54°C and the boiling point is 1327 ⁇ 10°C.
  • the melting point is relatively low, while the melting point of magnesium, aluminum, calcium, silver, and bismuth is relatively high. At the melting temperature, these gases have a certain vapor pressure. These metals Gases are mutually soluble and coexistent. It can be condensed into alloys with different contents. The obtained alloy phase is uniform, and the physical and chemical properties are stable and consistent.
  • magnesium-lithium alloys are divided into magnesium-rich alloys and lithium-rich alloys.
  • Magnesium-rich alloys such as ⁇ -phase alloys are commonly used.
  • Magnesium-lithium alloys generally adopt the "pair doping method", in which the lithium obtained by electrolysis is fused and doped with other metals, or electrolytically deposited. Since the melting point of alloy elements far exceeds the melting point of lithium, the electrolysis temperature is generally higher At 800°C, the vapor pressure of pure metallic lithium reaches 390.6Pa, and the nature of lithium is very active.
  • the method of industrial production of lithium is still the high-temperature electrolytic lithium chloride-potassium chloride molten salt method.
  • the raw materials used in this method are expensive and strict.
  • the fixed investment in the construction of a factory is huge, and the equipment is easily corroded. Due to the generation of chlorine gas, it is environmentally friendly.
  • the investment is large, the production environment is poor, the yield is not high, the K and Na contained in the lithium are relatively high, and the removal is difficult, which makes the manufacturing cost of metallic lithium high and increases the manufacturing cost of the alloy.
  • Lithium and lithium alloys have many excellent properties and are irreplaceable in many fields.
  • thermonuclear reactions, intercontinental missiles, artificial satellites, lithium and some lithium compounds are also a high-energy fuel used in space rockets and artificial Satellites, supersonic aircraft, missiles, submarines, etc.; alloys made of lithium, magnesium, and aluminum are the lightest structural materials.
  • Lithium and lithium compounds are ideal battery materials for a wide range of applications. Lithium alloys also have good Deformation performance and processing performance, application prospects are very broad.
  • the present invention provides a method for producing magnesium-lithium alloy by gaseous co-condensation method.
  • the purity of the magnesium-lithium alloy prepared by this method is as high as 99.0wt%-99.95%, which can be applied to more fields; in addition, the method is easy to realize industrialization, reduces the cost of manufacturing magnesium-lithium alloy, and is more energy-saving compared to the prior art Environmental protection.
  • a method for producing magnesium-lithium alloy by gaseous co-condensation method which comprises the following steps:
  • the industrial tube furnace is an industrial tube furnace with a crucible for vapor deposition of nitrogen and carbon compounds.
  • the particle size of lithium salt, flux inhibitor and catalyst before forming agglomerate is less than 100um.
  • the size of the industrial tube furnace is ⁇ 150- ⁇ 330mm*3300mm.
  • the lithium salt is lithium-containing carbonate, nitrate, sulfate, silicate or lithium-containing sulfide;
  • the flux inhibitor is CaO, Al 2 O 3 , MgO, etc.;
  • the catalyst is Sb 2 O 3 , Bi 2 O 3 and so on.
  • the molar ratio of the lithium salt, the flux inhibitor and the catalyst is 1: (1.4-1.8): (0.2-0.8).
  • 25-35g spheres need to be pressed into an apricot core shape, thick in the middle and thin on both sides, which is conducive to the emission of carbon dioxide during thermal decomposition, and the spheres maintain a certain shape during high-temperature decomposition to prevent solid particles Falling off, in the industrial tube furnace, the control vacuum degree is 10-20pa, the temperature is 860-950°C, and the thermal decomposition rate can reach more than 99%.
  • step 2) The unsaturated composite oxide, magnesium oxide, reducing agent and flux produced in step 1) are respectively pulverized and ball milled to a particle size of 40-100um, and pressed into a pellet of 25-35g/piece under the condition of 30-45Mpa , The shape resembles an apricot kernel type.
  • the reducing agent is high-silicon ferrosilicon, aluminum powder with Al content ⁇ 99wt%, aluminum powder with active aluminum >70wt% and particle size less than 8um, aluminum-silicon powder or carbon powder with aluminum-silicon content ⁇ 98wt%, preferably Ferrosilicon with grade greater than 75%; flux is CaF 2 with grade> 97.5%.
  • the mass ratio of unsaturated composite oxide to magnesium oxide is 3-80:20-97, the total mass of unsaturated composite oxide and magnesium oxide, and the mass ratio of reducing agent to flux is 76-87:15- 23:1-3.
  • step 2) Put the pellets in step 2) into an industrial heat-resistant steel tube furnace, and control the vacuum degree of 1-20pa and the temperature of 900-1300°C. At this time, the reduction product is gaseous and carries solid materials; thermal reduction rate ⁇ 99%.
  • the size of the industrial heat-resistant steel tube furnace is ⁇ 159- ⁇ 330mm*3300mm.
  • the gas carrying solid materials is passed through the centrifugal separator in the dust collector, and then enters the first condensing chamber in the temperature control device.
  • the condenser in the first condensing chamber adopts a double-tube type cooler, which is used in the interlayer
  • the constant temperature gas flow velocity is 1.2-1.8m/sec, and the temperature in the centrifugal separator and the first condenser is controlled to be 850-900°C.
  • the gas is passed through a 0.5um micron ceramic filter, and more than 99.95% of the carried dust is purified, and the gas temperature at the outlet of the micron ceramic filter is controlled at 700-750°C.
  • the condenser in the second condensing chamber is a double-layer sleeve-type cooler.
  • the outer layer uses a low-temperature cooling liquid of less than -100 degrees to exchange heat with the metal gas to cool
  • the center of the device takes away the heat transferred to the inner wall through the gas of 1.5-4m/sec.
  • the metal ratio of the cooling area to the condensed phase is 0.4-0.7dm 3 /kg, which can quickly condense the metal gas into the condensed phase of the alloy.
  • the quenching temperature control device includes a reaction zone, a dust removal chamber, a first condensation chamber, a second condensation chamber, a dust removal chamber slag discharge hole and a vacuum tube.
  • the reaction zone is connected to the dust removal chamber; a centrifugal separator is installed in the dust removal chamber.
  • a funnel is set at the lower end; the heating zone inlet 1 is set at the lower end of one side of the funnel, and the bottom of the funnel is the slag discharge hole of the dust removal chamber; the heating zone outlet 1 is set at the upper end of the dust removal chamber, and the first condensation chamber is set on the top of the dust removal chamber.
  • the second heating zone outlet is set, and the ceramic micron filter is set in the first condensing chamber; the first condensing chamber is connected to the second condensing chamber; and the first condensing chamber is connected to the second condensing chamber
  • the connecting position is provided with heating zone inlet two; a vacuum tube is provided at the connection between the second condensing chamber and the first condensing chamber, and a cooling liquid inlet, a cooling air inlet, a cooling liquid outlet and a cooling air outlet are respectively arranged on both sides of the second condensing chamber.
  • the crude magnesium-lithium alloy is used in the distillation device to control the lower temperature of the distiller at 850-950°C, the middle temperature at 700-800°C, the upper temperature ⁇ 100°C, and the lower part to remove high melting point impurities, such as Fe, Ni, Co, Si , Ca, etc.; the upper part removes low melting point metal impurities, such as k, Na, etc., and the middle liquid is 99.95% magnesium-lithium alloy.
  • magnesium-lithium alloy ingot is cast, and the magnesium-lithium alloy is finished.
  • the preferred raw material lithium salt is lithium carbonate; lithium carbonate is a thermal decomposition reaction, and the reaction formula is Li 2 CO 3 ⁇ (heating) Li 2 O+CO 2 .
  • the antimony and bismuth oxides do not participate in the chemical reaction.
  • the added antimony trioxide and bismuth oxide only act to adsorb liquid lithium carbonate when the initial decomposition temperature of the reaction is lower than 850°C, making it impossible or liquid Beads become smaller, which is conducive to the thermal decomposition of lithium carbonate, that is, to increase the thermal decomposition surface area of lithium carbonate.
  • the temperature in the thermal decomposition furnace rises to 860-900°C, antimony trioxide and bismuth oxide will increase Vaporization and sublimation leave the product, reducing the amount of calcium oxide added, so that a stable Li 2 O(2-x)CaO is formed as an unsaturated oxide, where x is less than 0.5, which can increase the unit production capacity.
  • the reaction temperature is lowered, and the main effect is that the area of the reaction interface increases, and the reaction speed is increased, without affecting the quality of the product. Under the same conditions, the decomposition rate can be increased by 12-15%.
  • the vapor deposition temperature is greater than 1000°C, the deposition thickness is ⁇ 0.2-0.3um, the surface is smooth and defect-free, and the framework chooses high-melting-point metals, nickel-based alloys, and titanium alloys.
  • the use of pure nickel-based alloys and titanium alloys will form a strong bond, which is deposited as a compound of carbon and nitrogen or Al 2 O 3 .
  • both domestic and foreign crucible materials are made of high-purity graphite. Because high-purity graphite is prone to Bootle reaction, the life of the crucible is only 5-6 times. The product can be contaminated by the shed carbon. Using spraying technology to repair, the service life is more than 20 times longer than that of high-purity graphite.
  • Centrifugal precipitation can only remove 95-97% of the dust. Micron ceramic filtration can remove more than 99.99% of the dust. It must be used in conjunction. If only centrifugation is used, impurities will not be removed. If only micron ceramics are used, the filter life cycle is too long. Short, the filter needs to be regenerated frequently, and when used in conjunction, it can remove more than 99.99% of dust, and the reprocessing cycle can be increased by more than 15 times.
  • the cryogenic liquid is combined with cold air.
  • the cooling temperature is from 700 to 750°C, and it is cooled to below 150°C within 0.5 to 1.5 minutes, turning it into agglomerates.
  • the cryogenic liquid has a strong heat absorption capacity, and the flow rate is The 1.5-4M/sec cold wind can quickly take away the absorbed heat to achieve a rapid cooling effect.
  • the use of this technology to build a 1,000 tons/year metal magnesium lithium plant requires a fixed investment of no more than 60 million yuan, which is only one-third of the fixed asset investment of a lithium plant of the same scale, which is comparable to the electrolytic method.
  • the manufacturing cost can be reduced by 20-30%, the source of raw materials is abundant, and the yield of lithium magnesium can be improved.
  • the magnesium-lithium alloy does not segregate to form a stable ⁇ -phase solid solution or compound, and the purity is improved to 99.95%.
  • this research has overcome the difficulties encountered in the industrialization of metal lithium and achieved industrialization, and the magnesium-lithium alloy is prepared by this technology, and the purity has been increased from 99% to 99.95%.
  • the co-condensation method produces alloys, unifies metal extraction and alloying in one process, makes full use of thermal energy for dust removal and purification, and the rapid cooling of the gas phase into a condensed phase makes the alloying elements of the alloy evenly distributed without segregation.
  • Ferrosilicon is used as the reducing agent in this application, first because of its low price and sufficient market; second, the gaseous lithium produced by the reaction is relatively mild, so that almost 100% of the metal is collected; third, the use of the vacuum pump can be extended life.
  • Fig. 1 is a schematic diagram of the process flow of the method for producing magnesium-lithium alloy by gaseous co-condensation according to the present invention.
  • Fig. 2 is a schematic diagram of the structure of the quenching device of the present invention.
  • 1 Reaction zone
  • 2 Dust removal chamber
  • 3 First condensation chamber
  • 4 Syncond condensation chamber
  • 5 Dust removal chamber slag hole
  • 6 Vacuum tube
  • 7 Inlet of heating zone One, 8-heating zone outlet one, 9-heating zone inlet two, 10-heating zone outlet two, 11-coolant outlet, 12-coolant inlet, 13-cooling air inlet, 14- Cooling air outlet, 15-ceramic micron filter.
  • the quenching temperature control device includes a reaction zone, a dust removal chamber, a first condensation chamber, a second condensation chamber, a slag discharge hole in the dust removal chamber, and a vacuum tube, and the reaction zone is connected to the dust removal chamber;
  • a centrifugal separator is installed in the dust removal chamber, and a funnel is set at the lower end of the dust removal chamber;
  • a heating zone inlet 1 is set at the lower end of one side of the funnel, and the bottom of the funnel is a slag discharge hole in the dust removal chamber;
  • a heating zone outlet 1 is set at the upper end of the dust removal chamber.
  • a first condensing chamber is set on the top of the dust removal chamber, a heating zone outlet 2 is set at the upper end of the connection between the first condensing chamber and the dust removal chamber, and a ceramic micron filter is set in the first condensing chamber; the first condensing chamber is connected to the second condensing chamber ; Set the heating zone inlet two at the position where the first condensing chamber is connected with the second condensing chamber; set a vacuum tube at the connection between the second condensing chamber and the first condensing chamber, and set the cooling liquid inlet and cooling air on both sides of the second condensing chamber Inlet, coolant outlet and cooling air outlet.
  • Both the first condensing chamber and the second condensing chamber are double-layer double-pipe type coolers.
  • the distillation separation technology is the existing technology.
  • a method for producing magnesium-lithium alloy by gaseous co-condensation method the steps of which are:
  • the total mass of oxide and magnesium oxide, ferrosilicon and CaF 2 are respectively crushed and ball milled to a particle size of 60um, mixed according to the mass ratio of 80:18:2, and compressed at 30Mpa into 28g/piece pellets.
  • step 3 Put the pellets in step 2) into a ⁇ 330mm*3300mm industrial heat-resistant steel tube furnace with a vacuum of 1pa and a temperature of 1185°C. At this time, the reduction product is gaseous and carries solid materials.
  • the recovery rate of magnesium reduction is> 95%, the reduction rate of lithium is 99%.
  • the first condensation chamber has an interlayer.
  • the gas with a gas flow velocity of 1.5m/sec is used to control the centrifugal separator and the first condensation.
  • the room temperature is at 880°C.
  • the gas with 98% solid particles that is larger than 20um is removed when it passes through the first condensing chamber, and the dust that is >99.95 when it passes through the 0.5um micron ceramic filter is purified, and the outlet temperature is controlled at 730°C
  • the pure metal gas passes through the second condensing chamber of the quenching device.
  • the temperature of the inner layer of the double-tube cooler in the second condensing chamber is controlled at 60°C, and the outer layer is carried out with low-temperature cooling liquid and metal gas at -110°C.
  • the center of the cooler takes away the heat transferred to the inner wall through the gas of 3m/sec.
  • the cooling area is 0.65dm 3 /kg, which can quickly condense the metal gas into the condensation phase of the alloy.
  • magnesium-lithium alloy ingot is cast and stored after surface treatment.
  • the obtained magnesium-lithium alloy is tested according to the national standard, and the mass percentage content of each element is as follows:
  • the purity of the magnesium-lithium alloy obtained by this method reaches 99.95% by weight, and a stable and uniform ⁇ and ⁇ -phase solid solution and compounds of the magnesium-lithium alloy are formed, which has good workability and can meet the current applications in various industrial fields.
  • the manufacturing cost is 20-30% lower, the source of raw materials is abundant, the segregation phenomenon is overcome, the purity is improved, the alloy properties are improved, and the industrialization is realized.
  • a method for producing magnesium-lithium alloy by gaseous co-condensation method the steps of which are:
  • Lithium oxide and flux inhibitors generate unsaturated composite oxides.
  • the vacuum degree of the industrial tube furnace is 10pa and the temperature is 860°C. After 5 hours of high-temperature decomposition, the decomposition rate of lithium carbonate into lithium oxide is 99.3%, and the yield of metallic lithium reaches 99.5%.
  • the mass ratio of the unsaturated composite oxide and magnesium oxide formed by the lithium oxide and the flux inhibitor obtained in step 1) is 87.7:12.3, and the total mass of the unsaturated composite oxide and magnesium oxide is compared with ferrosilicon and CaF 2 Crush the ball mill to a particle size of 60um, mix according to the mass ratio of 79:19:2, and press at 30Mpa into 28g/piece pellets.
  • step 3 Put the pellets in step 2) into an industrial heat-resistant steel pipe furnace of ⁇ 330mm*3300mm, control the vacuum degree to 3pa and the temperature to 1200°C. At this time, the reduction product is gaseous and carries solid materials. The recovery rate of magnesium reduction >95.1%, the reduction rate of lithium is 99.1%.
  • the first condensing chamber has an interlayer.
  • a constant temperature gas with a flow velocity of 1.6m/sec is used to control the centrifugal separator and the first condensing chamber.
  • the temperature of the condensing chamber is 900°C.
  • the gas carrying 98% solid particles larger than 20um is removed when passing through the first condensing chamber.
  • the airborne dust >99.95 is purified, and the outlet temperature is controlled at 740°C.
  • the pure metal gas passes through the quenched second condensing chamber.
  • the condenser is a double-layer sleeve cooler.
  • the temperature of the inner layer is controlled at 65°C.
  • the outer layer uses a low-temperature cooling liquid less than -105°C for heat exchange with the metal gas.
  • the center of the cooler takes away the heat transferred to the inner wall through the gas of 4m/sec.
  • the cooling area is 0.7dm 3 /kg, which can quickly condense the metal gas into the condensed phase of the alloy.
  • the obtained magnesium-lithium alloy is tested according to the national standard, and the mass percentage content of each element is as follows:
  • a method for producing magnesium-lithium alloy by gaseous co-condensation method the steps of which are:
  • the mass ratio of the unsaturated composite oxide and MgO formed by the lithium oxide obtained in step 1) is 79.5:20.5, and the total mass of the unsaturated composite oxide and the magnesium oxide and the ferrosilicon and CaF 2 are pulverized to a particle size of 60um, mix the ingredients according to the mass ratio of 80:18:2, and press at 35Mpa into apricot core-shaped pellets of 30g/piece.
  • step 3 Put the pellets in step 2) into an industrial heat-resistant steel tube furnace of ⁇ 330mm*3300mm, with a vacuum of 3pa and a temperature of 1200°C. At this time, the reduction product is gaseous, and solid materials are to be carried. The magnesium is reduced The recovery rate was 88.6%, and the lithium reduction rate was 89.3%.
  • the pure metal gas passes through the quenched second condensing chamber.
  • the condenser is a double jacketed cooler.
  • the internal temperature is controlled at 60°C.
  • the outer layer -110°C low-temperature cooling liquid exchanges heat with the metal gas.
  • the cooling liquid center The 4m/sec gas takes away the heat transferred to the inner wall, and the cooling area is 0.55dm 3 /kg, which can quickly condense the metal gas into the condensed phase of the alloy.
  • the crude magnesium-lithium alloy is distilled and separated.
  • the temperature of the lower part is controlled at 880°C
  • the temperature in the middle part is controlled at 730°C
  • the temperature of the upper part is controlled at 80°C
  • the lower part removes high melting point impurities
  • the upper part removes Fe, Ni, Co, Si, Ca, etc.
  • Low melting point metal impurities such as k, Na, etc., are discharged as Mg-Li alloy in the middle.
  • the obtained magnesium-lithium alloy is tested according to the national standard, and the mass percentage content of each element is as follows:
  • Lithium nitrate has a longer decomposition time in the thermal decomposition process.
  • the direct thermal decomposition results in low lithium yield and high energy consumption. It is decomposed into unsaturated composite oxides formed by lithium oxide, MgO and ferrosilicon, and CaF 2 is crushed.
  • the mixing process is difficult. The mixing is uneven, the proportion of the pellets made into apricot nucleus is uneven, and the reduction rate is reduced.
  • the links in the whole process are complicated, and the yield is lower than that of lithium carbonate, resulting in an increase in manufacturing costs.
  • the mass ratio of the unsaturated composite oxide and MgO formed by the lithium oxide obtained in step 1) is 80.2:19.8, and the total mass of the unsaturated composite oxide and the magnesium oxide and the ferrosilicon and CaF 2 are pulverized to a particle size of 60um, mix the ingredients according to the mass ratio of 80:18:2, and press at 35Mpa into apricot core-shaped pellets of 30g/piece.
  • step 3 Put the pellets in step 1) into an industrial heat-resistant steel tube furnace of ⁇ 330mm*3300mm, with a vacuum of 3pa and a temperature of 1220°C. At this time, the reduction product is gaseous, and solid materials, magnesium The reduction recovery rate is >90.2%, and the lithium reduction rate is 88.2%.
  • the gas carrying solid materials is passed through the gas with a gas flow velocity of 1.45m/sec, the temperature of the dust removal with a jacket for centrifugal separation is controlled at 920°C, and the gas carrying 98% solid particles greater than 20um is passed through the first condensing chamber.
  • the carried dust >99.95 is purified, and the gas temperature at the outlet is controlled at 740°C.
  • the pure metal gas passes through the quenched second condensing chamber.
  • the condenser is a double jacketed cooler.
  • the internal temperature is controlled at 65°C.
  • the outer layer of -110°C low-temperature cooling liquid exchanges heat with the metal gas.
  • the cooling liquid center The 2.8m/sec gas takes away the heat transferred to the inner wall, and the cooling area is 0.6dm 3 /kg, which can quickly condense the metal gas into the condensed phase of the alloy.
  • the crude magnesium-lithium alloy is distilled and separated, the temperature of the lower part is controlled at 870°C, the temperature of the middle part is controlled at 720°C, the temperature of the upper part is controlled at 70°C, and the lower part removes high melting point impurities, such as Fe, Ni, Co, Si, Ca, etc., The low melting point metal impurities k, Na, etc. are removed, and the middle part is discharged as Mg-Li alloy.
  • the obtained magnesium-lithium alloy is tested according to the national standard, and the mass percentage content of each element is as follows:
  • the impurity content of magnesium-lithium alloy is better than GB/T5153-2016 standard and GB/T33141-2016 standard.
  • Lithium sulfate is more difficult to decompose than lithium carbonate and cannot be completely decomposed.
  • the direct thermal decomposition results in lower lithium yield, higher energy consumption, longer thermal decomposition time, and decomposition into unsaturated composite oxides formed by lithium oxide, MgO and silicon
  • the process of crushing and mixing iron and CaF 2 is difficult, the mixing is not uniform, the proportion of the pellets made into apricot nucleus is not uniform, and the reduction rate is reduced.
  • the intermediate links of the whole process are complicated, and the yield is lower than that of lithium carbonate, which causes an increase in manufacturing costs.
  • Example 1 The experiment was carried out using the raw materials and method steps in Example 1, and only the temperature of the first condensation chamber and the second condensation chamber in the temperature control device were changed. The remaining conditions were the same as in Example 1.
  • the specific test conditions and results are as follows:
  • the second condensing chamber (degrees) form Test effect 980 800 90 Fluffy Condensed Metal general 880 730 65 Condensed metal, easy to collect good 780 650 40 Condensed metal, not easy to collect not good
  • Example 1 The experiment was carried out using the raw materials and method steps in Example 1, only the reduction conditions were changed, and the rest of the conditions were the same as in Example 1, and the influence of different reduction conditions on the application was tested.
  • the specific test conditions and results are as follows:
  • Example 1 The experiment was carried out using the raw materials and method steps in Example 1, only the temperature of the still in the refining step was changed, and the remaining conditions were the same as in Example 1.
  • the specific test conditions and results are as follows:
  • the refining test conditions are as follows:
  • magnesium-lithium alloy The results of magnesium-lithium alloy are as follows:
  • the temperature is 780°C, stirred for 15 minutes, argon 99.99%, to reach the ideal melting temperature, so that the molten magnesium-lithium alloy does not segregate and form a stable ⁇ + ⁇ phase, if the temperature is too low It will cause segregation and instability in the magnesium-lithium alloy, and the oxides in the product will increase.

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Abstract

一种气态共冷凝法生产镁锂合金的方法，包括步骤1）将锂盐、阻熔剂和催化剂混合后压力制团，热分解形成不饱和复合氧化物；2）将不饱和的复合氧化物、氧化镁与还原剂、助熔剂分别粉碎球磨后制团；3）将球团真空还原；4）将气体通过控温装置的第一冷凝室（3），并进行净化；5）净化后纯的金属气体通过急冷装置的第二冷凝室（4）冷凝为合金的凝聚相；6）熔炼，熔剂精炼，得到纯度为99.5％以上的镁锂合金，最后进行蒸馏提纯。该方法得到的镁锂合金不偏析，形成稳定的β相固溶体或化合物，纯度提升，达到99.95％。

Description

一种气态共冷凝法生产镁锂合金的方法 技术领域
本发明属于轻金属合金材料制备技术领域，涉及纯度高，晶粒超细、合金均匀的一种镁锂合金制造的新方法，具体为一种气态共冷凝法生产镁锂合金的方法。
背景技术
金属锂原子序数为3，原子核由三个质子和四个中子组成，核的周围有三个电子，在K电子层上有2个电子，电子层结构为1S 22S 1,锂的化学性质非常活泼，化合物是极性分子易吸水，使提取金属困难，这种金属与许多元素形成非常重要的化合物，固溶体等合金，形成合金可变形性能好，易加工。
金属锂的熔点为180.54℃，沸点为1327±10℃，熔点偏低，而镁、铝、钙、银、铋等熔点偏高，在熔炼温度时，这些气体都具有一定的蒸汽压，这些金属气体互溶共存。可供冷凝凝聚成含量不同的合金。得到的合金相均匀，物理和化学性质稳定一致。
我们国家的锂资源比较丰富，目前金属锂和其他金属元素形成的合金，例如镁锂合金，镁锂合金又分为富镁合金与富锂合金，现在普遍应用的还是富镁合金例如β相的LA141、LA91。镁锂合金普遍采用的是“对掺法”，将用电解法得到的锂与其他金属熔融对掺，或电解沉积，由于合金元素的熔点远远超过锂的熔点，对掺，电解温度一般较高，800℃时，纯金属锂的蒸汽压就达到了390.6Pa，而锂的性质非常活泼，在合金化时会与空气中的氧、氮、氢等起反应， 造成锂的大量损失；锂的密度仅是0.53g/cm 3，其他合金元素密度远远大于锂，在合金化时造成偏析，影响其加工性能和应用领域。
目前工业上生产锂的方法仍是高温电解氯化锂-氯化钾熔融盐法，这种方法所用原料价格高，要求严，建工厂固定投资巨大，设备易被腐蚀，因有氯气产生，环保投入大，生产环境恶劣，收率也不高，锂中含有的K、Na偏高，去除困难，因而使得金属锂的制造成本居高不下，提高了合金的制造成本。
锂和锂的合金具有许多优异的性能，在许多领域有不可替代性，在原子能工业、热核反应、洲际导弹、人造卫星，锂及一些锂的化合物还是一种高能燃料，用于宇宙火箭、人造卫星、超音速飞机、导弹、潜水艇等；锂和镁、铝等制造出来的合金是最轻的结构材料，锂及锂的化合物更是理想的广泛应用的电池材料，锂合金还具有良好的变形性能和加工性能，应用前景非常广泛。
发明内容
本发明根据以上技术问题，提供一种气态共冷凝法生产镁锂合金的方法。该方法制备得到的镁锂合金纯度高达到99.0wt％-99.95％，可应用到更多的领域；另外，该方法易于实现工业化，降低制造镁锂合金的成本，相比现有技术，更节能环保。
为了实现以上发明目的，本发明的具体技术方案如下：
一种利用气态共冷凝法生产镁锂合金的方法，其包括以下步骤：
1)将锂盐、阻熔剂和催化剂按比例混合，并在35-45Mpa的压力条件下制团；将制作好的物质放在工业管式炉内进行热分解，催化剂升华冷凝后再利用，氧化锂与阻熔剂生成不饱和的复合氧化物。
作为优选，所述的工业管式炉为内置有气相沉积氮碳化合物坩埚的工业管 式炉。
锂盐、阻熔剂和催化剂在制团前的粒度<100um。
作为优选，工业管式炉的尺寸为φ150-φ330mm*3300mm。
所述的锂盐为含锂的碳酸盐、硝酸盐、硫酸盐、硅酸盐或含锂的硫化物；所述的阻熔剂为CaO、Al 2O 3、MgO等；所述的催化剂为Sb 2O 3、Bi 2O 3等。
作为优选，锂盐、阻熔剂和催化剂的摩尔比为1：(1.4-1.8)：(0.2-0.8)。
制团的时候，需压成的球体25-35g/个，成杏核状，中间厚，两边薄，有利于热分解时二氧化碳的排出，并且球体在高温分解时保持一定形状，防止固体颗粒的脱落，在工业管式炉内，控制真空度为10-20pa，温度在860-950℃，其热分解率可达99％以上。
2)分别将步骤1)中生成的不饱和复合氧化物、氧化镁、还原剂与助熔剂分别粉碎球磨至粒度40-100um，在30-45Mpa的条件下压制成25-35g/个的球团，形状似杏核型。
所述的还原剂为高硅的硅铁，Al含量≥99wt％的铝粉，活性铝>70wt％且粒度小于8um的铝粉，铝硅合量≥98wt％的铝硅粉或碳粉，优选品位大于75％的硅铁；助熔剂为CaF 2，其品位>97.5％。
作为优选，不饱和复合氧化物与氧化镁的质量比为3-80:20-97，不饱和复合氧化物与氧化镁的总质量、还原剂与助熔剂的质量比为76-87:15-23:1-3。
3)将步骤2)中的球团装入工业耐热钢管式炉内，控制其真空度1-20pa，温度900-1300℃，此时还原产物为气态，并携带有固体物料；热还原率≥99％。
作为优选，工业耐热钢管式炉的尺寸为φ159-φ330mm*3300mm。
4)将携带有固体物料的气体通过除尘器中的离心分离器，然后进入控温装置中的第一冷凝室，第一冷凝室内的冷凝器采用双层套管式冷却器，在夹层 中用恒温的气流速度为1.2-1.8m/sec的气体，控制离心分离器与第一冷凝器中的温度为850-900℃。除尘器中进行除尘后，超过98wt％粒度大于20um的固体颗粒被除掉。再将气体通过0.5um的微米陶瓷过滤器，大于99.95％的携带尘被净化，微米陶瓷过滤器出口的气体温度控制在700-750℃。
5)纯的金属气体通过急冷装置的第二冷凝室，第二冷凝室内的冷凝器为双层套管式冷却器，外层用小于-100度的低温冷却液体与金属气体进行热交换，冷却器中心通过1.5-4m/sec的气体带走传热到内壁的热量，冷却面积与凝聚相的金属比为0.4-0.7dm 3/kg，可迅速使金属气体冷凝为合金的凝聚相。
所述急冷控温装置包括反应区、除尘室、第一冷凝室、第二冷凝室、除尘室排渣孔和真空管，其反应区与除尘室连通；除尘室内设离心分离器，在除尘室的下端设置漏斗；在漏斗的一侧下端设置加热区进口一，漏斗的底部为除尘室排渣孔；在除尘室一侧的上端设置加热区出口一，在除尘室的顶部设置第一冷凝室，在第一冷凝室与除尘室连接的位置上端设置加热区出口二，在第一冷凝室内设置陶瓷微米过滤器；第一冷凝室与第二冷凝室连通；在第一冷凝室内与第二冷凝室连接的位置设置加热区进口二；在第二冷凝室内与第一冷凝室连接处设置真空管，在第二冷凝室两侧分别设置冷却液进口和冷却风进口、冷却液出口和冷却风出口。
6)将凝聚相的镁锂合金在井式炉内在Ar气保护并搅拌下进行熔剂熔炼，精炼，得到纯度为99.5％的粗镁锂合金。
7)将粗镁锂合金进行蒸馏分离，即得纯度99.95％以上的镁锂合金。
作为优选，粗镁锂合金在蒸馏装置中，控制蒸馏器下部温度在850-950℃，中部温度700-800℃，上部温度<100℃，下部除去高熔点杂质，如Fe、Ni、Co、 Si、Ca等；上部除去低熔点金属杂质，如k、Na等，中部液体为99.95％的镁锂合金。
最后将镁锂合金铸锭，镁锂合金成品。
在本申请中，优选的原料锂盐为碳酸锂；碳酸锂是热分解反应，反应式为Li 2CO 3→(加热)Li 2O+CO 2。
在本申请中，锑、铋氧化物不参与化学反应，加入的三氧化二锑、氧化铋仅仅是反应初期分解温度低于850℃时起到吸附液态碳酸锂的作用，使之不能或使液珠变小，有利于碳酸锂的热分解，也就是使碳酸锂的热分解表面积增加，当分解完成后，热分解炉内温度提升到860-900℃时，三氧化二锑和氧化铋又会汽化升华离开生成物，减少了氧化钙加入量，使形成稳定Li 2O(2-x)CaO为不饱和氧化物，其中x小于0.5，可增加单位生产能力。反应温度降低，主要作用由于反应界面面积增加，提高反应速度，对产品质量没有影响，相同条件下可提高分解率12～15％。气相沉积温度大于1000℃，沉积厚度≮0.2-0.3um，表面光滑无缺陷，骨架选择高熔点金属，镍基合金，钛合金。用纯镍基合金、钛合金会形成牢固粘结，沉积为碳和氮的化合物或Al 2O 3。目前国内外坩埚材质均采用高纯石墨，由于高纯石墨易发生布特尔反应，坩埚寿命仅为5～6次，脱落下的碳污染产品，沉积形成的坩埚与物料不反应，而坩埚可以采用喷涂技术进行修补，使用寿命比高纯石墨提高20倍以上。
离心沉淀只能除去尘的95～97％，微米级陶瓷过滤可除去尘的99.99％以上，必须配合使用，若仅使用离心，杂质除不净，若仅使用微米级陶瓷，过滤器使用周期太短，需对过滤器经常再生处理，配合使用可除尘99.99％以上，再处理周期可提高15倍以上。
急冷装置中，低温液体和冷风相结合，冷却温度从700-750℃，在0.5～1.5 分钟内冷到150℃以下，使之变成凝聚体，低温液体有很强的吸热能力，流速为1.5-4M/sec的冷风可迅速带走被吸收的热量，达到急冷的效果。
与对掺法，电解制备合金相比，采用本技术建设1000吨/年金属镁锂厂，固定投资不大于6000万元，仅为相同规模锂厂固定资产投资的三分之一，与电解法相比制造成本可降低20-30％，原料来源丰富、提高锂镁的收率。镁锂合金不偏析形成稳定的β相固溶体或化合物，纯度提升，达到99.95％。与现有国内外其他研究相比较，本研究克服了金属锂工业化遇到的困难，实现了产业化，并且采用该技术制备出镁锂合金，纯度由99％提高到99.95％。
本发明的积极效果体现在：
(一)共冷凝法生产合金，把金属提取和合金化统一在一个工艺中，充分利用了热能进行了除尘和净化，气相的迅速冷却成凝聚相使合金的合金元素分布均匀，不偏析。
(二)、利用真空热还原得到的锂与合金元素的混合蒸汽通过离心沉降除尘，微米陶瓷深度过滤完全可以得到理想纯度的金属蒸汽，再通过现有技术中的蒸馏、精炼,宜于工业化。同时，在我国皮江法炼镁技术、设备都非常成熟，可用许多镁冶炼的定型设备，减少了固定资产投资，易于实现工业化。
(三)、提高了合金加工性能，改善了合金的力学性能，反应罐的改进使工业化、机械化、自动化成为可能，同时原料来源广泛，固定投资少，生产成本低，节能环保，缩短了流程，具有良好的经济效益。
(四)、本申请中采用硅铁作为还原剂，一是因为其价格低，市场充足；二是反应产生的气态锂比较温和，使几乎100％的金属收集回来；三是可以延长真空泵的使用寿命。
附图说明：
图1为本发明所述利用气态共冷凝法生产镁锂合金方法的工艺流程示意图。
图2为本发明所述急冷装置的结构示意图。
其中，1——反应区、2——除尘室、3——第一冷凝室、4——第二冷凝室、5——除尘室排渣孔、6——真空管、7——加热区进口一、8——加热区出口一、9——加热区进口二、10——加热区出口二、11——冷却液出口、12——冷却液进口、13——冷却风进口、14——冷却风出口、15——陶瓷微米过滤器。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，下面结合具体实施方式对本发明作进一步的详细描述，但不应将此理解为本发明上述主题的范围仅限于下述实施例。
以下实施例中使用急冷装置的结构为：所述急冷控温装置包括反应区、除尘室、第一冷凝室、第二冷凝室、除尘室排渣孔和真空管，其反应区与除尘室连通；除尘室内设离心分离器，在除尘室的下端设置漏斗；在漏斗的一侧下端设置加热区进口一，漏斗的底部为除尘室排渣孔；在除尘室一侧的上端设置加热区出口一，在除尘室的顶部设置第一冷凝室，在第一冷凝室与除尘室连接的位置上端设置加热区出口二，在第一冷凝室内设置陶瓷微米过滤器；第一冷凝室与第二冷凝室连通；在第一冷凝室内与第二冷凝室连接的位置设置加热区进口二；在第二冷凝室内与第一冷凝室连接处设置真空管，在第二冷凝室两侧分别设置冷却液进口和冷却风进口、冷却液出口和冷却风出口。
第一冷凝室和第二冷凝室均为双层套管式冷却器。
蒸馏分离技术为现有技术。
实施例1：
一种利用气态共冷凝法生产镁锂合金的方法，其步骤为：
1)按比例称取原料，其中碳酸锂的粒度为89um，氧化钙的粒度为74um，将碳酸锂、CaO和催化剂Sb 2O 3按摩尔比1：1.6：0.4的比例混合，并在35Mpa的压力条件下制团；团块28克/个，团形状为杏核状。将制作好的球团放在φ330mm*3300mm带有气相沉积氮碳化合物坩埚的工业管式炉中进行热分解，催化剂升华冷凝后可再利用，氧化锂与阻熔剂生成不饱和的复合氧化物。工业管式炉的真空度为10pa，温度860℃。高温分解时间5小时，碳酸锂分解成氧化锂的分解率99.2％，金属锂收率达到99.5％。
2)分别将步骤1)中得到的氧化锂和阻熔剂形成的不饱和复合氧化物与氧化镁的质量比为88.2:11.8，(复合氧化物中MgO:CaO＝1:1),不饱和复合氧化物与氧化镁的总质量与硅铁、CaF 2分别粉碎球磨至粒度60um，按照质量比80:18:2配料混合，在30Mpa压制成28g/个的球团。
3)将步骤2)中的球团装入φ330mm*3300mm的工业耐热钢管式炉内，真空度1pa，温度1185℃，此时还原产物为气态，并携带有固体物料，镁还原回收率>95％,锂的还原率99％。
4)将携带有固体物料的气体通过除尘室中的离心过滤器与第一冷凝室，第一冷凝室带有夹层，用气流速度为1.5m/sec的气体，控制离心分离器与第一冷凝室温度在880℃。携带大于20um的98％的固体颗粒气体通过第一冷凝室时被除去，通过0.5um的微米陶瓷过滤器时>99.95的携带尘被净化，出口温度控制在730℃
5)纯的金属气体通过急冷装置的第二冷凝室，在第二冷凝室的双层套管式冷却器内层温度控制在60℃，外层用-110℃的低温冷却液体与金属气体进行热 交换，冷却器中心通过3m/sec的气体带走传热到内壁的热量，冷却面积为0.65dm 3/kg，可迅速使金属气体冷凝为合金的凝象相。
6)将凝聚相的镁锂合金在井式炉内在Ar气保护并搅拌下进行熔剂熔炼，精炼，得到纯度为99.5％的粗镁锂合金。
7)将粗镁锂合金进行蒸馏分离，控制蒸馏器下部温度为900℃，中部温度控制在750℃，上部温度控制在70℃，下部除去高熔点杂质Fe、Ni、Co、Si、Ca等；上部除去低熔点金属杂质k、Na等，中部排出为Mg-Li合金。
最后将镁锂合金铸锭，表面处理后保存。
将得到的镁锂合金按照国标进行检测，各元素的质量百分含量如下：
Mg Li Fe Ni Cu Al Mn
90.752 9.2 0.0015 0.00045 0.00035 0.004 0.0005
Ti Ca Si Zn K Na 其他
0.0003 0.015 0..0055 0.0008 0.0046 0.009 0.006
由以上可知，通过本方法得到的镁锂合金纯度达到99.95wt％，并形成了稳定均匀的镁锂合金的α与β相固溶体和化合物，具有良好的可加工性，可满足目前各工业领域应用，与对掺法相比，制造成本低20-30％，原料来源丰富，克服了偏析现象，提高了纯度，提高了合金性质，实现了工业化。
实施例2：
一种利用气态共冷凝法生产镁锂合金的方法，其步骤为：
1)按比例称取原料，其中碳酸锂的粒度为89um，氧化钙的粒度为74um，将碳酸锂、CaO+MgO、Al 2O 3和催化剂Sb 2O 3按摩尔比1：1.45:0.2：0.4的比例混合，并在40Mpa的压力条件下制团；团块28克/个，团形状为杏核状。将制作好的球团放在φ330mm*3300mm的工业管式炉内，气相沉积氮碳化合物的坩埚中进行热分解，催化剂升华冷凝后再利用，氧化锂与阻熔剂生成不饱和的复合氧化物。工业管式炉的真空度为10pa，温度860℃。高温分解时间5小时，碳酸 锂分解成氧化锂的分解率99.3％，金属锂收率达到99.5％。
2)分别将步骤1)中得到的氧化锂和阻熔剂形成的不饱和复合氧化物与氧化镁的质量比为87.7:12.3，不饱和复合氧化物与氧化镁的总质量与硅铁、CaF 2分别粉碎球磨至粒度60um，按照质量比79:19:2配料混合，在30Mpa压制成28g/个的球团。
3)将步骤2)中的球团装入φ330mm*3300mm的工业耐热钢管式炉内，控制真空度3pa，温度1200℃，此时还原产物为气态，并携带有固体物料，镁还原回收率>95.1％,锂的还原率99.1％。
4)将携带有固体物料的气体通过除尘室中的离心过滤器与第一冷凝室，第一冷凝室带有夹层，用气流速度为1.6m/sec的恒温气体，控制离心分离器与第一冷凝室温度在900℃。携带大于20um的98％的固体颗粒气体通过第一冷凝室时被除去，通过0.5um的微米陶瓷过滤器时>99.95的携带尘被净化，出口温度控制在740℃。
5)纯的金属气体通过急冷的第二冷凝室，冷凝器为双层套管式冷却器，内层温度控制在65℃，外层用小于-105℃的低温冷却液体与金属气体进行热交换，冷却器中心通过4m/sec的气体带走传热到内壁的热量，冷却面积为0.7dm 3/kg，可迅速使金属气体冷凝为合金的凝聚相。
6)将凝聚相的镁锂合金在井式炉内在Ar气保护并搅拌下进行熔剂熔炼，精炼，得到纯度为99.5％的粗镁锂合金。
7)将粗镁锂合金进行蒸馏分离。控制蒸馏器下部温度控制在930℃，中部温度控制在780℃，上部温度控制在70℃，下部除去高熔点杂质Fe、Ni、Co、Si、Ca等；上部除去低熔点金属杂质k、Na等；中部排出为Mg-Li合金。
将得到的镁锂合金按照国标进行检测，各元素的质量百分含量如下：
Mg Li Fe Ni Cu Al Mn
90.151 9.8 0.0013 0.00032 0.00038 0.006 0.0005
Ti Ca Si Zn K Na 其他
0.0003 0.016 0.0038 0.0007 0.0047 0.008 0.007
实施例3：
一种利用气态共冷凝法生产镁锂合金的方法，其步骤为：
1)将工业级硝酸锂，在无压团情况下焙烧，温度在680℃，时间为7小时，形成稳定的Li 2O.1.75CaO，硝酸锂分解成氧化锂分解率为98.1％，金属锂收率达到90.1％。
2)分别将步骤1)中得到的氧化锂形成的不饱和复合氧化物、MgO的质量比为79.5：20.5，不饱和复合氧化物与氧化镁的总质量与硅铁、CaF 2粉碎至粒度为60um，按照质量比80:18:2配料混合，在35Mpa压制成30g/个的杏核型球团。
3)将步骤2)中的球团装入φ330mm*3300mm的工业耐热钢管式炉内，真空度为3pa，温度为1200℃，此时还原产物为气态，并携待有固体物料，镁还原回收率为88.6％，锂还原率89.3％。
4)将携带有固体物料的气体通过气流速度为1.4/sec的气体，带有夹套离心分离除尘温度控制在910℃，携带大于20um的98％的固体颗粒气体通过第一冷凝室时被除去，通过0.5um的微米陶瓷过滤器时>99.95的携带尘被净化，出口的气体温度控制在720℃。
5)纯的金属气体通过急冷的第二冷凝室，冷凝器为双层套式冷却器，内温控制在60℃，外层-110℃的低温冷却液体与金属气体进行热交换，冷却液中心通过4m/sec的气体带走传热到内壁的热量，冷却面积为0.55dm 3/kg，可迅速使金属气体冷凝为合金的凝聚相。
6)将凝聚相的镁锂合金在井式炉内在Ar气保护并搅拌下进行熔剂熔炼，精炼，得到纯度为99.5％的粗镁锂合金。
7)将粗镁锂合金进行蒸馏分离，下部温度控制在880℃，中部温度控制在730℃，上部温度控制在80℃，下部除去高熔点杂质，Fe、Ni、Co、Si、Ca等上部除去低熔点金属杂质k、Na等，中部排出为Mg-Li合金。
将得到的镁锂合金按照国标进行检测，各元素的质量百分含量如下：
Mg Li Fe Ni Cu Al Mn
89.651 10.3 0.0015 0.00045 0.00035 0.003 0.0008
Ti Ca Si Zn K Na 其他
0.0003 0.018 0.0067 0.0008 0.0031 0.009 0.005
硝酸锂在热分解过程中比较分解时间较长，直接进行的热分解造成锂收率偏低，能耗比较高，分解成氧化锂形成的不饱和复合氧化物、MgO与硅铁、CaF 2粉碎混合过程比较困难混料不均匀，制成杏核状的球团中比例不均匀，还原率降低。与碳酸锂对比整个工艺过程中环节复杂，收率比碳酸锂低，造成制造成本的增加。
实施例4：
1)将工业级硫酸锂，在无压团的情况下温度在920℃，时间为8小时，形成稳定的Li 2O.1.85CaO(MgO)，硫酸锂分解成氧化锂分解率为95.1％，金属锂收率达到96.1％。
2)分别将步骤1)中得到的氧化锂形成的不饱和复合氧化物、MgO的质量比为80.2:19.8，不饱和复合氧化物与氧化镁的总质量与硅铁、CaF 2粉碎至粒度为60um，按照质量比80:18:2配料混合，在35Mpa压制成30g/个的杏核型球团。
3)分别将步骤1)中的球团装入φ330mm*3300mm的工业耐热钢管式炉内，真空度为3pa，温度为1220℃，此时还原产物为气态，并携待有固体物料，镁还原回收率>90.2％，锂还原率为88.2％。
4)将携带有固体物料的气体通过气流速度为1.45m/sec的气体，带有夹套离心分离除尘温度控制在920℃，携带大于20um的98％的固体颗粒气体通过第 一冷凝室时被除去，通过0.5um的微米陶瓷过滤器时>99.95的携带尘被净化，出口的气体温度控制在740℃。
5)纯的金属气体通过急冷的第二冷凝室，冷凝器为双层套式冷却器，内温控制在65℃，外层-110℃的低温冷却液体与金属气体进行热交换，冷却液中心通过2.8m/sec的气体带走传热到内壁的热量，冷却面积为0.6dm 3/kg，可迅速使金属气体冷凝为合金的凝聚相。
6)将凝聚相的镁锂合金在井式炉内在Ar气保护并搅拌下进行熔剂熔炼，精炼，得到纯度为99.5％的粗镁锂合金。
7)将粗镁锂合金进行蒸馏分离，下部温度控制在870℃，中部温度控制在720℃，上部温度控制在70℃，下部除去高熔点杂质，Fe、Ni、Co、Si、Ca等，上部除去低熔点金属杂质k、Na等，中部排出为Mg-Li合金。
将得到的镁锂合金按照国标进行检测，各元素的质量百分含量如下：
Mg Li Fe Ni Cu Al Mn
91.05 8.9 0.0016 0.0002 0.0005 0.0041 0.0006
Ti Ca Si Zn K Na 其他
0.0004 0.016 0.0059 0.0009 0.0048 0.009 0.006
通过多次验证，镁锂合金其中的杂质含量均优于GB/T5153-2016标准和GB/T33141-2016标准。
硫酸锂分解比碳酸锂困难，不能完全被分解，直接进行的热分解造成锂收率偏低，能耗比较高，热分解时间长，分解成氧化锂形成的不饱和复合氧化物、MgO与硅铁、CaF 2粉碎混合过程比较困难,混料不均匀，制成杏核状的球团中比例不均匀，还原率降低。与碳酸锂对比整个工艺过程中间环节复杂，收率比碳酸锂低，造成制造成本的增加。
实验1：
采用实施例1中的原料和方法步骤进行实验，仅改变控温装置中第一冷凝室和第二冷凝室的温度，其余条件均同实施例1，具体测试条件和结果如下：
第一冷凝室(度) 第一冷凝室出口(度) 第二冷凝室(度) 形态 试验效果
980 800 90 蓬松状凝聚态金属 一般
880 730 65 凝聚态金属、易收集 良
780 650 40 凝聚态金属、不好收集 不好
通过试验可知，当第一冷凝室温度在880℃，第二冷凝室温度在65℃时形成的镁锂合金的凝聚态金属最好、易收集。而第一冷凝室和第二冷凝室的温度越高会使形成的镁锂合金蓬松且形态一般。第一冷凝室和第二冷凝室的温度太低会使形成的凝聚态金属不好收集，形不成一个团块。
实验2：
采用实施例1中的原料和方法步骤进行实验，仅改变还原条件，其余条件均同实施例1，测试不同的还原条件对本申请的影响。具体测试条件和结果如下：
Figure PCTCN2020115864-appb-000001
从表中我们可以看出，当还原温度在1190℃，还原时间为10小时，产品还原率达到99.2％，镁的还原率达到95.1％。降低还原温度反而会使形成镁锂合金的比例有偏差，还原率降低，收率降低，尽而造成制造成本的增加。
实验3：
采用实施例1中的原料和方法步骤进行实验，仅改变精炼步骤中蒸馏器的温度，其余条件均同实施例1，具体测试条件和结果如下：
精炼试验条件如下表：
温度(℃) 搅拌时间(min) 氩气99.99％(Mpa) 合成锭
780 15 0.2 1#
680 30 0.2 2#
580 60 0.2 3#
镁锂合金的结果如下表：
Figure PCTCN2020115864-appb-000002
通过表中我们可以看出温度在780℃，搅拌15分钟，氩气99.99％，达到比较理想的熔炼温度，使熔铸出的镁锂合金不偏析，形成稳定的α+β相，如温度过低会造成镁锂合金有偏析不稳定，产品中的氧化物会增加。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (10)

  1. 一种利用气态共冷凝法生产镁锂合金的方法，其特征在于包括以下步骤：
    1)将锂盐、阻熔剂和催化剂按比例混合后压力制团；制团后的混合物放置在工业管式炉内进行热分解，氧化锂与阻熔剂生成不饱和的复合氧化物，催化剂升华冷凝后再利用；
    2)将步骤1)中生成的不饱和的复合氧化物，和氧化镁、还原剂与助熔剂分别粉碎球磨后制团；
    3)将步骤2)中的球团装入工业耐热管式炉内进行真空还原，此时还原产物为气态，并携带有固体物料；
    4)将步骤3)中携带有固体物料的气体通过可控温装置除尘室中的离心过滤器，然后进入第一冷凝室，用气流速度为1.2-1.8m/sec的气体，控制离心分离器与第一冷凝室温度在850-950℃；使绝大部分的固体颗粒被除掉；再将其通过微米陶瓷过滤器，使大于99.95％的固体颗粒携带尘被净化，出口温度控制在700-750℃；
    5)被净化后纯的金属气体通过急冷装置的第二冷凝室，第二冷凝室内的冷凝器外层用小于-100℃的冷却液体与金属气体进行热交换，冷却器中心的气体带走传热到内壁的热量，迅速使金属气体冷凝为合金的凝聚相；
    6)将凝聚相的镁锂合金在井式炉内，并在Ar气保护下进行熔剂熔炼，精炼，得到纯度为99.5％以上的镁锂合金；
    7)将粗镁锂合金进行蒸馏分离，得到纯度99.95％以上的镁锂合金。
  2. 根据权利要求1所述的方法，其特征在于：所述的锂盐为含锂的碳酸盐、硝酸盐、硫酸盐、硅酸盐或含锂的硫化物；所述的阻熔剂为CaO、Al 2O 3或MgO；所述的催化剂为Sb 2O 3或Bi 2O 3；锂盐、阻熔剂与催化剂的摩尔比为1：1.4-1.8：0.2-0.8。
  3. 根据权利要求1所述的方法，其特征在于：步骤1)中锂盐、阻熔剂和催化剂的粒度均小于100um，制团要求为杏核形，25-35g/个重，压力制团的条件为35-45Mpa，热分解温度为860-900℃。
  4. 根据权利要求1所述的方法，其特征在于：步骤2)中不饱和的复合氧化物、氧化镁、还原剂与助熔剂分别粉碎球磨后制团，其球磨后的粒度为40-100um，制团的条件为：在30-45Mpa压制成25-35g/个，杏核形。
  5. 根据权利要求1所述的方法，其特征在于：所述的还原剂为高硅的硅铁，Al含量≥99wt％的铝粉，活性占70wt％且粒度小于8um的铝粉，铝硅合量大于等于98％的铝硅粉或碳粉，助熔剂为CaF 2，其纯度为97.5％，不饱和复合氧化物与氧化镁的质量比为3-80:20-97，不饱和复合氧化物与氧化镁的总质量、还原剂与助熔剂的质量比为76-87:15-23:1-3。
  6. 根据权利要求1所述的方法，其特征在于：热分解工业管式炉的真空度为10-20pa，温度860-950℃，尺寸为φ159-φ330mm*3300mm，热分解率≥99％。
  7. 根据权利要求1所述的方法，其特征在于：热还原工业耐热钢管式炉的尺寸为159-φ330mm*3300mm，真空度为1-20pa，温度900-1300℃，热还原率≥99％。
  8. 根据权利要求1所述的方法，其特征在于：所述急冷控温装置包括反应区(1)、除尘室(2)、第一冷凝室(3)、第二冷凝室(4)、除尘室排渣孔(5)真空管(6)；反应区(1)与除尘室(2)连通；除尘室(2)内设离心分离器，在除尘室(2)的下端设置漏斗；在漏斗的一侧下端设置加热区进口(7)，漏斗的底部为除尘室排渣孔(5)；在除尘室(2)一侧的上端设置加热区出口一(8)，在除尘室(2)的顶部设置第一冷凝室(3)，在第一冷凝室(3)与除尘室(2)连接的位置上端设置加热区出口二(10)，在第一冷凝室(3)内 设置陶瓷微米过滤器(15)；第一冷凝室(3)与第二冷凝室(4)连通；在第一冷凝室(3)内与第二冷凝室(4)连接的位置设置加热区进口二(9)；在第二冷凝室(4)内与第一冷凝室(3)连接处设置真空管(6)，在第二冷凝室(4)两侧分别设置冷却液进口(12)和冷却风进口(13)、冷却液出口(11)和冷却风出口(14)。
  9. 根据权利要求8所述的方法，其特征在于：所述的第一冷凝室(3)和第二冷凝室(4)均为双层套管式冷却器，第二冷凝室(4)内冷却器中心的气体流速为1.5-4m/sec，冷却面积与凝聚相的金属比为0.4-0.7dm 3/kg。
  10. 根据权利要求8所述的方法，其特征在于：精炼步骤中，控制蒸馏塔下部温度850-950℃，中部温度700-800℃，上部温度<100℃，然后进行蒸馏分离，中部液体为99.95％的镁锂合金，铸锭得镁锂合金成品。
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