CN109110789B - Method for preparing beryllium fluoride and method for preparing ultra-pure metallic beryllium - Google Patents
Method for preparing beryllium fluoride and method for preparing ultra-pure metallic beryllium Download PDFInfo
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- CN109110789B CN109110789B CN201811116378.2A CN201811116378A CN109110789B CN 109110789 B CN109110789 B CN 109110789B CN 201811116378 A CN201811116378 A CN 201811116378A CN 109110789 B CN109110789 B CN 109110789B
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22B35/00—Obtaining beryllium
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- 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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Abstract
The invention relates to a method for preparing beryllium fluoride and a mode for preparing ultra-pure metallic beryllium, wherein the beryllium fluoride is prepared by mixing and heating beryllium hydroxide and hydrofluoric acid, and the method comprises the following steps: and (2) pouring beryllium hydroxide and hydrofluoric acid into a reactor, sealing, electrifying, stirring, switching on a power supply, heating, drying the prepared beryllium fluoride material in a drying box to prepare beryllium fluoride crystal grains, pouring the beryllium fluoride crystal grains into a stainless steel pulverizer, pulverizing to obtain beryllium fluoride powder, and storing. And preparing beryllium fluoride powder into coarse beryllium powder, purifying and smelting into beryllium ingots. The method for preparing the beryllium fluoride and the mode for preparing the ultra-high-purity metal beryllium have the advantages of simple process, less introduced impurities, higher production efficiency than the traditional process, high purity of the obtained product, energy conservation, low treatment cost and high purity of the prepared beryllium.
Description
Technical Field
The invention relates to the field of purification of metal beryllium, in particular to a method for preparing beryllium fluoride and a mode for preparing ultra-high-purity metal beryllium.
Background
Beryllium is a material with special properties, and certain properties, particularly nuclear properties and physical properties of beryllium cannot be replaced by any other metal material. The beryllium has low density, the specific elastic modulus of the beryllium is at least 6 times that of any other metal, the beryllium has light weight, large rigidity and good thermal property, has excellent properties of high melting point, high specific heat, high thermal conductivity, proper thermal expansion rate and the like, and the sound propagation speed is higher than that of other metals. Therefore, the application range of beryllium is mainly focused in the fields of nuclear industry, weapon systems, aerospace industry, X-ray instruments, electronic information systems, automobile industry, household appliances and the like. With the progress of research, the application range of the method is also expanded. As a strategic key material, a basic strategic material with turning significance to war, beryllium is a marker post for national defense comprehensive strength and military industrial development level. In the civil field, beryllium is the cinnamon crown of the nuclear metal era.
Although the importance of beryllium is so significant, its technical threshold is high, especially for ultra-high purity metallic beryllium, and only one country in the united states in the world can produce small amounts of 99.99% metallic beryllium. They are technically strictly blocked, and the ultra-pure metal beryllium cannot be obtained in any country and is only shared by a family in the United states. Currently, only three countries in the world are capable of producing metallic beryllium of typical purity 99%, i.e., U.S., china, kazakhstan (a plant left by the former soviet union). According to the relevant data, as China cannot produce high-purity metal beryllium, but is particularly required by national defense, military industry and some civil high-end industries, part of the metal beryllium is imported from the United states every year. This situation has caused great restrictions on national defense industry and military high-end manufacturing industry in China. The united states monopolizes the beryllium market and the speaking right in the world by virtue of the high-end metallurgical technology of the metal beryllium which is high and ultra and mastered by the united states. Therefore, the method for preparing the high-purity metal beryllium has great practical significance for breaking U.S. monopoly, strengthening the national defense career of China and improving the military level of China.
At present, beryllium oxide and ammonium bifluoride are commonly used in industry to react to prepare ammonium fluoberyllate, and calcium carbonate solution, lead peroxide solution, ammonium polysulfide and the like are added to make other impurities, Mn2+Ion, CrO2 -Precipitating and separating out ions and other heavy metals, concentrating and crystallizing under the vacuum condition, heating and decomposing to prepare beryllium fluoride, and then preparing metal beryllium. The process is various and long, the equipment is multiple, the energy consumption is high, the cost is high, the introduced impurities are multiple, the impurity removal and the use of medicines are multiple, the production efficiency is low, and the ammonium fluoride generated by heating decomposition can cause environmental pollution.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a method for preparing beryllium fluoride, which has the advantages of simple process, less introduced impurities, higher production efficiency than the traditional process, high purity of the obtained product, energy conservation and low treatment cost.
The second technical problem to be solved by the invention is to provide a method for preparing ultrahigh-purity metallic beryllium, which has the advantages of simple process, less introduced impurities, higher production efficiency than the traditional process, high purity of the obtained product, energy conservation and low treatment cost.
In order to solve the first technical problem, the present invention provides a method for preparing beryllium fluoride, comprising the following steps:
the first step is as follows: preparing raw materials, wherein the raw materials comprise beryllium hydroxide and hydrofluoric acid;
the second step is that: heating the raw materials to prepare a beryllium fluoride material;
the third step: drying the beryllium fluoride material to prepare beryllium fluoride crystal grains;
the fourth step: and (4) crushing the beryllium fluoride crystal grains to obtain beryllium fluoride powder, and storing.
The invention has the beneficial effects that: the method for preparing the beryllium fluoride has the advantages of simple process, less introduced impurities, higher production efficiency than the traditional process, high purity of the obtained product, energy conservation and low treatment cost.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the purity of the beryllium hydroxide is greater than or equal to 99.8%; the mass fraction of the hydrofluoric acid is 40%.
Further, the mass of the beryllium hydroxide having a purity of 99.8% or more and the mass ratio of the hydrofluoric acid having a mass fraction of 40% are 11: 28.
Further, the heating method comprises the following steps: and pouring the heated raw materials into the reactor, and then sealing the reactor.
Further, the reactor is an enamel reaction kettle.
Further, starting a vacuum pump to vacuumize after the enamel reaction kettle is sealed, and electrifying and stirring after the vacuum degree is 0.05 Pa; and after the mixture is electrified and stirred, switching on a power supply for heating to prepare the beryllium fluoride material.
Further, the power is switched on to heat the reaction kettle to 90 ℃, and a vacuum pump is started to pump steam generated by heating into a liquid storage tank outside the reaction kettle.
Further, the electrified stirring is that the power supply is switched on to start the stirrer in the reaction kettle to stir.
Further, the time of electrifying and stirring is 20-45 minutes.
Further, stopping heating when the heating raw material is changed into a thick colloidal beryllium fluoride material, and cooling the beryllium fluoride material; and cooling the beryllium fluoride material to 40-50 ℃.
The adoption of the further beneficial effects is as follows: the reaction conditions are parameters obtained by experiments, and the smooth reaction can be ensured.
Further, the drying method comprises the following steps: opening a discharge port at the bottom of the enamel reaction kettle, taking the prepared beryllium fluoride material by using a stainless steel supporting basin, placing the beryllium fluoride material in a drying box, closing a door, and heating by electrifying to prepare beryllium fluoride crystal grains; the stainless steel supporting basin is lined with a polypropylene plate; the drying box is characterized in that a rack is made of stainless steel materials and divided into a plurality of layers, and stainless steel supporting basins are arranged on the rack.
The adoption of the further beneficial effects is as follows: the beryllium fluoride has certain corrosivity, and the polypropylene plate can resist corrosion and heat up to 200 ℃ and prevent the stainless steel mop basin from being corroded.
Further, stopping heating after the beryllium fluoride material is changed into dry beryllium fluoride crystal grains, and cooling the beryllium fluoride crystal grains; and cooling the beryllium fluoride crystal grains to 40-50 ℃.
Further, the crushing method comprises the following steps: and taking out the stainless steel dragging basin, and pouring the beryllium fluoride crystal grains into a stainless steel pulverizer to be pulverized to obtain beryllium fluoride powder.
The adoption of the further beneficial effects is as follows: the beryllium fluoride powder obtained by physical crushing is beneficial to increasing the reaction area when the coarse beryllium powder is prepared in the next step of preparing the ultrahigh-purity metal beryllium, so that the raw materials are contacted more fully and the reaction is more uniform.
Further, the storage method comprises the following steps: filling the beryllium fluoride powder into a woven bag, and fastening a bag opening for storage; the woven bag is provided with a plastic lining.
The adoption of the further beneficial effects is as follows: the crushed beryllium fluoride powder is packaged by a woven bag with a plastic lining and is pricked into a bag opening, so that the contact between the material and air is reduced, and the oxidation is avoided.
Further, after the drying box is closed, a vacuum pump is started to vacuumize, and after the vacuum degree is 0.05Pa, the drying box is electrified and heated.
The adoption of the further beneficial effects is as follows: and the beryllium oxide is dried in a vacuum state, so that the beryllium oxide material is prevented from being oxidized, and the reaction for preparing the coarse beryllium powder in the next step for preparing the ultrahigh-purity metal beryllium is not influenced.
Further, the drying is firstly carried out by heating to 50 ℃, keeping the constant temperature for 30 minutes, then heating to 90 ℃, keeping the constant temperature for 30 minutes, and then heating to 120 ℃ and keeping the constant temperature until the materials are dried.
The adoption of the further beneficial effects is as follows: the beryllium oxide material is colloidal when beginning to be dried and has high water content, so the temperature is firstly raised to 50 ℃ to slowly volatilize the water, which is beneficial to the exhaust hole of the drying box to discharge the water vapor in time and avoids the water vapor from being condensed in the drying box and falling onto the beryllium fluoride material to influence the material quality.
In order to solve the second technical problem, the invention provides a method for preparing ultra-high-purity metallic beryllium, which comprises the following steps:
a method for preparing beryllium fluoride;
a method for preparing coarse beryllium powder;
a method for purifying crude beryllium powder into ingots.
The method for preparing beryllium fluoride is the method for preparing beryllium fluoride as described above.
The invention has the beneficial effects that: the method for preparing the beryllium fluoride has the advantages of simple process, less introduced impurities, higher production efficiency than the traditional process, high purity of the obtained product, energy conservation and low treatment cost.
On the basis of the technical scheme, the invention can be further improved as follows.
The method for preparing the coarse beryllium powder comprises the following steps:
the first step is as follows: preparing a reducing raw material, wherein the reducing raw material comprises beryllium fluoride and magnesium metal;
the second step is that: heating the reduction raw material to prepare a material slag cake;
the third step: crushing the material slag cake, and separating beryllium beads and magnesium fluoride slag;
the fourth step: and crushing the beryllium beads to obtain coarse beryllium powder.
The invention has the beneficial effects that: the method for preparing the coarse beryllium powder can reduce all beryllium fluoride at one time, is energy-saving and environment-friendly, has high reduction rate, greatly improves the direct recovery rate, has short time, does not contain other additional medicaments except magnesium, and has low cost.
Further, the beryllium fluoride is added in powder form; the magnesium metal is added in bulk.
The adoption of the further beneficial effects is as follows: beryllium fluoride is added in powder form, so that the beryllium fluoride can fully participate in the reaction, and the reduction rate of the beryllium fluoride is improved; the metal magnesium is added in a block shape, and coarse particles are beneficial to reducing the violent reaction strength and are convenient for controlling the temperature.
Further, the mass ratio of the beryllium fluoride to the metal magnesium is 60: 31.
The adoption of the further beneficial effects is as follows: the mass ratio of the beryllium fluoride to the metal magnesium is a parameter obtained by a test, so that the full reduction reaction can be ensured, the reaction speed can be controlled, and the production safety can be ensured.
Further, the method for heating the reduction raw material is a heating reduction method; the heating reduction method comprises the following steps: adding the reduced raw materials into a reduction furnace, closing the furnace, heating by electrifying, so that molten metal beryllium and magnesium fluoride are condensed and float to the surface of a charging material, injecting the condensed molten metal beryllium and magnesium fluoride into a casting mold, and cooling the casting mold to form a cake-shaped product to obtain a material slag cake, wherein the total recovery rate of beryllium is 98%; after the reducing furnace is closed, starting a vacuum pump to vacuumize, electrifying and heating to raise the temperature after the vacuum degree is 0.05 Pa; the method for heating by electrifying comprises the steps of heating to 650 ℃ in a gradient manner, keeping the temperature constant for 30 minutes, heating to 750 ℃, keeping the temperature constant for 30 minutes, heating to 800 ℃ for 60 minutes, heating to 1000 ℃ for 30 minutes, and heating to 1300 ℃ for 20 minutes; the reducing furnace is a high-frequency furnace with the power of 100 kw; the inner container of the reduction furnace is a graphite crucible; the size of the reduction furnace is 450 mm.
The adoption of the further beneficial effects is as follows: controlling gradient temperature rise to ensure that the reaction generated in each stage is carried out under the optimum condition, ensuring the production safety and simultaneously fully carrying out the reaction, completely melting the metal beryllium and the metal magnesium, and condensing the metal beryllium into beryllium beads and floating the beryllium beads on the magnesium fluoride melt.
Further, the method for crushing the material slag cake comprises the following steps: and (3) crushing the material slag cake into small blocks by using a stainless steel hammer.
The adoption of the further beneficial effects is as follows: the physical crushing is carried out instead of crushing, so that the beryllium beads and the magnesium fluoride slag can be conveniently separated.
Further, the separation method comprises the following steps: soaking and boiling the small blocks with hot water, and screening the small blocks by using a sieve after soaking and boiling to obtain separated beryllium beads and magnesium fluoride residues; the container used for hot water immersion and boiling is an enamel reaction kettle; the temperature of the hot water digestion is 100 ℃; the temperature of the hot water immersion is 1 h; the hot water digestion process is accompanied by agitation.
The adoption of the further beneficial effects is as follows: and (4) screening and separating the beryllium beads and the magnesium fluoride slag with different densities and particle sizes through a screen.
Further, the crushing method comprises the following steps: sending the beryllium balls obtained in the third step into a jet mill for crushing, washing to be neutral after cold soaking, and drying to obtain coarse beryllium powder; the beryllium balls are cleaned and dried before being sent into a jet mill; introducing nitrogen as protective gas before the beryllium balls are sent into a jet mill; the beryllium beads are sent into a jet mill to be crushed into particles with the size smaller than 1 mm; the immersion liquid used in the cold leaching is concentrated nitric acid; the cold soaking time is 10-15 minutes; the washing method is to use purified water for quick washing; the drying method after the beryllium bead crushing, cold soaking and washing is to place the beryllium bead in a stainless steel basin for drying.
The adoption of the further beneficial effects is as follows: the nitrogen is used as a protective gas, so that the metal beryllium can be prevented from being oxidized.
Further, the beryllium fluoride can be recycled, and the method comprises the following steps: (1) putting the separated magnesium chloride slag and the smoke generated by heating into an enamel reaction kettle; the enamel reaction kettle is made of polypropylene; (2) adding hydrofluoric acid into the reaction kettle, heating and boiling to obtain filter residue and filtrate; (3) cleaning and drying the filter residue in the sun to obtain dried magnesium fluoride; (4) and (4) purifying the filtrate to obtain beryllium oxide thick slurry, and preparing a reduction raw material for recycling.
The adoption of the further beneficial effects is as follows: the beryllium fluoride can be recycled, and the recovery rate of beryllium is improved.
Further, heating, stewing and then carrying out filter pressing, and stewing again after filter pressing to obtain filter residue and filtrate; the time for warming and digesting is 1.5 hours each time.
The adoption of the further beneficial effects is as follows: and the leaching rate is improved by two times of leaching.
Further, the mass fraction of the hydrofluoric acid is 40%; adding the hydrofluoric acid until the pH value of the liquid is less than 0.5; if the acidity becomes light in the process of soaking and boiling the magnesium chloride slag and the smoke dust, hydrofluoric acid is added to ensure that the pH value is less than 0.5.
The adoption of the further beneficial effects is as follows: the pH value is kept to be less than 0.5, so that the concentration of hydrofluoric acid reaches the requirement of dissolving beryllium particles, and beryllium dissolution is ensured.
And further, the filtrate purification method comprises the steps of adding calcium carbonate while stirring until the pH value reaches 6.5-7, filtering, removing impurities, and adding the filtrate into an enamel reaction kettle for concentration to obtain beryllium oxide thick slurry.
The adoption of the further beneficial effects is as follows: impurities are added into the filtrate in the treatment process, so that calcium carbonate is added, part of the impurities become carbon dioxide to overflow, and the rest calcium oxide precipitates are generated and then filtered to remove the impurities.
Further, the smoke dust is collected into the bag dust collector from the gas outlet pipe of the reducing furnace through the Venturi ejector.
The adoption of the further beneficial effects is as follows: the magnesium reduction process of the beryllium fluoride can generate some smoke dust which is easy to damp and agglomerate, the smoke dust is collected into the bag dust collector from the air outlet pipe of the reduction furnace through the venturi, the furnace is kept clean, the collected beryllium fluoride is recycled, the magnesium fluoride is recycled, the recovery rate of the beryllium is improved, and the environment is protected.
The method for purifying the crude beryllium powder into ingots is a method for purifying the crude beryllium powder into ingots by using a thermal dissociation reactor for purifying the crude beryllium powder;
the thermal dissociation reactor for purifying the crude beryllium powder comprises an iodine containing furnace, a low-temperature reactor and a high-temperature reactor, wherein the iodine containing furnace is communicated with the low-temperature reactor; the low temperature reactor is communicated with the high temperature reactor.
The invention has the beneficial effects that: iodine is changed into steam in the iodine containing furnace, the iodine steam enters the low-temperature reactor and reacts with the coarse beryllium powder to generate beryllium iodide steam, the beryllium iodide steam rises from the low-temperature reactor to the high-temperature reactor, thermal dissociation is carried out under the high-temperature condition to generate metal beryllium and iodine steam, and the pure beryllium powder is obtained through collection. The reactor has reasonable structure and simple assembly, can collect purified beryllium by controlling the amount and the proportion of reaction raw materials and the temperatures of the iodine holding furnace, the low-temperature reactor and the high-temperature reactor, and is convenient to use.
Further, a first thermocouple is arranged in the iodine containing furnace; the inlet of the low-temperature reactor is communicated with the outlet of the iodine containing furnace; the inlet of the low-temperature reactor is communicated with the outlet of the iodine containing furnace through a porcelain tube; a second thermocouple is arranged in the low-temperature reactor; the inlet of the high-temperature reactor is communicated with the outlet of the low-temperature reactor; the inlet of the high-temperature reactor is communicated with the outlet of the low-temperature reactor through an iodine vapor hole; and a third thermocouple is arranged in the high-temperature reactor.
The adoption of the further beneficial effects is as follows: the iodine containing furnace, the low-temperature reactor and the high-temperature reactor are respectively heated and controlled by different power supplies, so that the flow of beryllium iodide steam and iodine steam can be accurately controlled.
Further, an iodine containing basin is arranged in the iodine containing furnace; a helium pipe is arranged above the iodine containing basin; a first valve is arranged at the joint of the helium pipe and the iodine containing furnace to control the helium to enter; the low-temperature reactor is isolated from the iodine containing furnace through a first partition plate; a stainless steel frame and a stainless steel basin are arranged in the low-temperature reactor; the stainless steel basin is used for containing coarse beryllium powder; the stainless steel basin is made of 80% of nickel and 20% of chromium alloy; the high-temperature reactor is isolated from the low-temperature reactor through a second partition plate; the first partition plate and the second partition plate are made of ceramics; a cylinder is arranged in the high-temperature reactor; the iodine containing furnace, the low-temperature reactor and the high-temperature reactor are isolated from the outside by metal plates; the metal plate is made of NI-Cr alloy; the metal plate is filled with a heating rod; the metal plate is sealed by an insulating layer; the heat-insulating layer is sealed by a red brick layer; a main switch is arranged outside the heat preservation layer; the master switch controls the power supply of the whole reaction system.
The adoption of the further beneficial effects is as follows: the structure is reasonable, the assembly is simple, and the installation, the disassembly and the maintenance are convenient.
The high-temperature reactor is connected with the cooling box; the outlet of the high-temperature reactor is communicated with the inlet of the cooling box; the outlet of the high-temperature reactor is connected with the inlet of the cooling box through a pipeline; a second valve is arranged on a pipeline for communicating the high-temperature reactor with the cooling box; a liquid storage tank is connected under the cooling tank; the liquid storage tank is connected to the position right below the cooling tank through a pipeline; one side of the liquid storage tank is connected with a vacuum pump, and a third valve is arranged at the joint; the vacuum pump is also connected with one side of the iodine containing furnace, and a fourth valve is arranged at the joint.
The adoption of the further beneficial effects is as follows: the iodine vapor is cooled in the cooling box, high-purity iodine crystals are accumulated in the liquid storage box, the content of the high-purity iodine crystals is more than 99.99%, the iodine is not leaked or volatilized, the iodine can return to the low-temperature reactor through the vacuum pump to continue to react, almost no loss is caused, the recycling rate is high, the iodine vapor is recycled, and the energy-saving and environment-friendly effects are achieved.
Further, the cylinders have 2-3 cylinders and are used for bearing the adhesion of pure beryllium powder; the cylinders are respectively hung on the hooks above the cylinders; a tungsten wire is arranged in the cylinder; the cylinder is made of NI-Cr alloy; each cylinder has the diameter of 20cm and the length of 80cm, and bears the adhesion of less than or equal to 20 kilograms of metal beryllium powder.
The adoption of the further beneficial effects is as follows: the cylinder is made of nickel-chromium alloy, so that the cylinder can resist high temperature, cannot react with iodine and beryllium, and ensures the purity of the beryllium.
A method for purifying crude beryllium powder into ingots using a thermal dissociation reactor for purifying the crude beryllium powder comprises the steps of: the first step is as follows: preparing raw materials, wherein the raw materials comprise coarse beryllium powder and iodine; the mass ratio of the coarse beryllium powder to the iodine is 5: 1; the second step is that: reacting the crude beryllium powder and iodine in a thermal dissociation reactor for purifying the crude beryllium powder to generate beryllium iodide steam, thermally dissociating and decomposing the beryllium iodide steam into metal beryllium and iodine steam, and collecting the metal beryllium and iodine steam to obtain pure beryllium powder; the third step: smelting the pure beryllium powder into a beryllium ingot; secondly, the step of reacting the crude beryllium powder and iodine in the thermal dissociation reactor for purifying the crude beryllium powder comprises the following steps: the stainless steel basin is placed on the stainless steel frame; the stainless steel basin is filled with the coarse beryllium powder; the thickness of the coarse beryllium powder contained in the stainless steel basin is 30-50 mm; the iodine containing basin is placed in the iodine containing furnace; the iodine is added into the iodine containing basin; starting the vacuum pump to maintain the vacuum degree at 0.05 pa; switching on the power supply of the iodine containing furnace, heating and raising the temperature to change iodine into steam, wherein the iodine steam enters the low-temperature reactor through the porcelain tube; switching on a power supply of the low-temperature reactor, heating and raising the temperature, and reacting the coarse beryllium powder and the iodine vapor in the low-temperature reactor to generate beryllium iodide vapor; when the beryllium iodide vapor appears in the low-temperature reactor, switching on a power supply of the high-temperature reactor, and heating to raise the temperature; when the beryllium iodide steam appears in the high-temperature reactor, opening a second valve for communicating the cooling box with the high-temperature reactor, thermally dissociating the beryllium iodide steam into metallic beryllium and iodine steam, and flushing the dissociated iodine steam into the cooling box to start circulating flow; when the iodine vapor becomes thin and little crude beryllium powder remains, ending the reaction, turning off a power supply, stopping heating, and collecting pure beryllium powder; stopping heating and cooling until the furnace temperature is reduced to below 350 ℃; the method for collecting the pure beryllium powder comprises the steps of taking down the cylinder, scraping beryllium adhered to the cylinder wall by using a scraper, and obtaining the pure beryllium powder; the scraper is a sharp stainless steel knife.
The invention has the beneficial effects that: the method for purifying the crude beryllium powder into the ingot by using the thermal dissociation reactor for purifying the crude beryllium powder has the advantages of simple operation, medicament saving, energy saving, environmental protection and low cost, and the purity of the beryllium can reach 99.999%. Iodine is changed into steam in the iodine containing furnace, the iodine steam enters the low-temperature reactor and reacts with the coarse beryllium powder to generate beryllium iodide steam, the beryllium iodide steam rises from the low-temperature reactor to the high-temperature reactor, thermal dissociation is carried out under the high-temperature condition to generate metal beryllium and iodine steam, and the pure beryllium powder is obtained through collection. The method for purifying the crude beryllium powder can collect the purified beryllium by controlling the amount and the proportion of the reaction raw materials and the temperatures of the iodine holding furnace, the low-temperature reactor and the high-temperature reactor, and is convenient to use.
Further, heating in the low-temperature reactor to 300 ℃ at a speed of 20 ℃/minute, keeping the constant temperature for 30 minutes, and then heating to 500 ℃ at a speed of 20 ℃/minute; heating in the high-temperature reactor is carried out by gradient heating to 500 ℃, keeping the constant temperature for 30 minutes, then heating to 500 ℃, keeping the constant temperature for 30 minutes, and then heating to 1100 ℃.
The adoption of the further beneficial effects is as follows: by adopting the temperature rising mode, when the reactor is used for the first time, the reactor needs to be dried, so that the reactor is dried more thoroughly, and the moisture is reduced to the minimum extent to ensure the vacuum degree of the furnace.
Further, the third step of the reaction for smelting the pure beryllium powder into beryllium ingots comprises the following steps: the first step is as follows: feeding the pure beryllium powder into an electron beam melting furnace; the vacuum degree of the electron beam smelting furnace is 0.05 pa; the melting speed of the electron beam melting furnace is 30 g/min; the specific electric energy of the electron beam smelting furnace is 0.6 kg/kw.h; the pure beryllium powder is sent into an electron beam melting furnace by a vibration pusher; the second step is that: electrifying the electron beam smelting furnace, and melting the pure beryllium powder into a beryllium melt by an electron gun; the third step: the beryllium melt flows into an ingot mold and is solidified into a beryllium ingot after a period of time; the ingot mold is made of beryllium oxide; the fourth step: pulling a dummy bar, deflating and taking out the beryllium ingot; the fifth step: smelting the beryllium ingot twice to obtain a beryllium ingot smelted twice; the second smelting method comprises the steps of feeding the beryllium ingot into an electron beam smelting furnace, electrifying, smelting again to obtain a second smelted beryllium melt, enabling the second smelted beryllium melt to flow into the ingot mold, and obtaining a second smelted beryllium ingot after a period of time; and a sixth step: and removing impurities on the surface of the beryllium ingot smelted in the second step to obtain the ultra-high-purity metal beryllium ingot, wherein the purity is over 99.999 percent.
The adoption of the further beneficial effects is as follows: further improving the purity of the metallic beryllium. Before electron beam melting, the purity of metallic beryllium can only reach 99.99%, the impurities in the metallic beryllium are mainly oxygen, nitrogen, hydrogen and other gases, and the affinity of the impurities and the beryllium is very strong. The impurity gases can be decomposed by electron beam melting under the action of high-temperature heat, and the impurity gases are not doped with the metal beryllium in the short time period from the melting of the beryllium to the dropping to the solidification of the beryllium into a beryllium ingot, so that the aim of clean degassing is fulfilled, and the purity of the metal beryllium is improved to more than 99.999 percent.
Drawings
Fig. 1 is a flow chart of a method for preparing ultra-high purity metallic beryllium according to the present invention.
FIG. 2 is a flow chart of a method for preparing beryllium fluoride according to the invention.
FIG. 3 is a flow chart of a method for preparing coarse beryllium powder according to the present invention.
FIG. 4 is a flow chart of a method for purifying crude beryllium powder into ingots according to the present invention.
FIG. 5 is a schematic view of a thermal dissociation reactor for purifying crude beryllium powder according to the present invention.
In the drawings, the components represented by the respective reference numerals are listed below:
1 cooling box, 2 liquid storage box, 3 vacuum pump, 4 main switch, 5 pothook, 6 red brick layer, 7 heat preservation layer, 8 cylinder, 9 heating rod, 10 third thermocouple, 11 metal plate, 12 tungsten filament, 13 high temperature reactor, 14 iodine vapor hole, 15 stainless steel basin, 16 thick beryllium powder, 17 second thermocouple, 18 porcelain tube, 19 first thermocouple, 20 helium pipe, 21 iodine containing basin, 22 low temperature reactor, 23 iodine containing furnace, 24 first valve, 25 second valve, 26 third valve, 27 fourth valve, 28 second clapboard, 29 first clapboard.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
As shown in fig. 1, the method for preparing ultra-high-purity metallic beryllium of the invention comprises the following steps:
a method for preparing beryllium fluoride;
a method for preparing coarse beryllium powder;
a method for purifying crude beryllium powder into ingots.
As shown in fig. 2, the specific synthesis of beryllium fluoride can be prepared by the following steps:
the first step is as follows: preparing raw materials, wherein the raw materials comprise beryllium hydroxide and hydrofluoric acid;
the second step is that: heating the raw materials to prepare a beryllium fluoride material;
the third step: drying the beryllium fluoride material to prepare beryllium fluoride crystal grains;
the fourth step: and (4) crushing the beryllium fluoride crystal grains to obtain beryllium fluoride powder, and storing.
The purity of the beryllium hydroxide is greater than or equal to 99.8%;
the mass fraction of the hydrofluoric acid is 40%;
the mass of the beryllium hydroxide with the purity of 99.8% is 44kg, and the mass of the hydrofluoric acid with the mass fraction of 40% is 112 kg.
The heating method comprises the following steps: pouring the heated raw materials into a reactor, sealing, electrifying, stirring, and then switching on a power supply for heating to obtain a beryllium fluoride material;
the reactor is an enamel reaction kettle;
after the enamel reaction kettle is closed, starting a vacuum pump to vacuumize, and electrifying and stirring the enamel reaction kettle until the vacuum degree is 0.05 Pa;
the step of electrifying and stirring is to switch on a power supply to start a stirrer in the reaction kettle so that the materials are stirred under the vacuum condition;
the time of electrifying and stirring is 20-45 minutes;
preferably, the energization stirring time is 30 minutes.
The power is switched on to heat the reaction kettle to 90 ℃, a vacuum pump is started to introduce steam generated by heating into a cooling tank outside the reaction kettle, the steam is condensed into water, and the water is injected into a liquid storage tank along a water pipe.
And stopping heating when the heating raw material is changed into a thick colloidal beryllium fluoride material (about 2 hours), and cooling the beryllium fluoride material.
And cooling the beryllium fluoride material to 40-50 ℃.
The drying method comprises the following steps: opening a discharge port at the bottom of the enamel reaction kettle, taking the prepared beryllium fluoride material by using a stainless steel supporting basin, placing the beryllium fluoride material in a drying box, closing a door, and heating by electrifying to prepare beryllium fluoride crystal grains;
the stainless steel supporting basin is lined with a polypropylene plate;
the tray made of the polypropylene material is preferably used for accommodating materials in a vacuum drying box due to the size of the tray, and preferably, the polypropylene material box is 500mm long, 400mm wide and 200mm high and is rectangular, and 5 trays are filled with beryllium fluoride.
The drying box is characterized in that a rack is made of stainless steel materials and divided into a plurality of layers, and stainless steel supporting basins are arranged on the rack. The obtained product is placed in a mop basin of a drying oven in five layers with a distance of 100mm between each layer.
After the drying box is closed, starting a vacuum pump to vacuumize, and electrifying and heating after the vacuum degree is 0.05 Pa;
and the drying is firstly carried out by heating to 50 ℃, keeping the constant temperature for 30 minutes, then heating to 90 ℃, keeping the constant temperature for 30 minutes, and then heating to 120 ℃ and keeping the constant temperature until the materials are dried.
And stopping heating after the beryllium fluoride material is changed into dry beryllium fluoride crystal grains, and cooling the beryllium fluoride crystal grains.
And cooling the beryllium fluoride crystal grains to 40-50 ℃.
The dried material is colorless crystal grains, has partial plate, and is crushed.
The crushing method comprises the following steps: and taking out the stainless steel dragging basin, and pouring the beryllium fluoride crystal grains into a stainless steel pulverizer to be pulverized to obtain beryllium fluoride powder.
The storage method comprises the following steps: and (3) filling the beryllium fluoride powder into a woven bag, and fastening the bag opening for storage.
The package is sealed against moisture, and the dry beryllium fluoride content is 50 kg.
The woven bag is provided with a plastic lining.
As shown in fig. 3, the specific synthesis of the crude beryllium powder can be prepared by the following steps:
the first step is as follows: preparing a reducing raw material, wherein the reducing raw material comprises beryllium fluoride and magnesium metal;
the second step is that: heating the reduction raw material to prepare a material slag cake;
the third step: crushing the material slag cake, and separating beryllium beads and magnesium fluoride slag;
the fourth step: and crushing the beryllium beads to obtain coarse beryllium powder.
In the first step, the beryllium fluoride is added in powder form;
the metal magnesium is added in a block shape;
the mass ratio of the beryllium fluoride to the metal magnesium is 60: 31;
the mass of the beryllium fluoride is 60kg, and the mass of the metal magnesium is 31 kg.
60kg of beryllium fluoride powder is put into a graphite crucible, then 31kg of metal magnesium blocks are added, stirred by a clean plastic rod and mixed evenly.
In the second step, the heating method of the reduction raw material is a heating reduction method;
the heating reduction method comprises the following steps: adding the reduction raw material into a reduction furnace, and closing a door; the reducing furnace is a high-frequency furnace with the power of 100 kw; the inner container of the reduction furnace is a graphite crucible; the size of the reduction furnace is 450 mm; after the reducing furnace is closed, starting a vacuum pump to vacuumize, electrifying and heating to raise the temperature after the vacuum degree is 0.05 Pa; and (3) electrifying, heating, raising the temperature, raising the initial temperature slowly, keeping the temperature constant in the temperature section for 30 minutes when the temperature is raised to 650 ℃, then continuing raising the temperature to 750 ℃ for another half hour, then directly raising the furnace temperature to 800 ℃, keeping the constant temperature for 60 minutes, and keeping the material reduction reaction in the temperature section to be most violent. After the reaction is finished, the temperature of the furnace is raised to 1300 ℃, under the high-temperature state, the metal beryllium and the metal magnesium are completely melted, meanwhile, the metal beryllium is condensed, and the metal beryllium is condensed into beryllium beads and then floats on the magnesium fluoride melt because the density of the metal beryllium beads is smaller than that of the magnesium fluoride; after molten metal beryllium and magnesium fluoride are condensed and float up to the surface of a charging material, the molten metal beryllium and magnesium fluoride are quickly injected into a casting mold, and the molten metal beryllium and magnesium fluoride are cooled into a cake shape after half an hour to obtain a material slag cake, wherein the total recovery rate of beryllium is 98 percent; the heating furnace is a vacuum high-frequency furnace with the power of 50 kw.
Note that it is not advisable to add too much beryllium fluoride and magnesium metal at a time to control the exothermic energy and reaction rate. The amount of beryllium fluoride which does not exceed 70 kg is preferably reduced for each time, and the operation is carried out correctly according to the operation steps.
In the third step, the method for crushing the material slag cake comprises the following steps: crushing the material slag cake into small blocks by using a stainless steel hammer;
the separation method comprises the following steps: soaking and boiling the small blocks with hot water, and screening the small blocks by using a sieve after soaking and boiling to obtain separated beryllium beads and magnesium fluoride residues; the container used for hot water immersion and boiling is an enamel reaction kettle; the enamel reaction kettle is made of polypropylene; the temperature of the hot water digestion is 100 ℃; the temperature of the hot water immersion is 1 h; the hot water digestion process is accompanied by agitation. Beryllium fluoride, which has not been reduced, dissolves in water, and magnesium fluoride is insoluble in water and remains in the slag together with the beryllium beads.
And (4) firstly screening the crushed slag through a 80-mesh sieve according to the size of the crushed slag blocks. The objects trapped on the screen surface are beryllium balls, the vast majority of the materials passing through the screen holes are magnesium fluoride, and the small part of the materials are beryllium balls with finer particles. And in the second screening, a 150-mesh screen is selected, the vast majority of the screened materials are magnesium fluoride, metal beryllium is little, the particles are also fine, and the vast majority of the materials left on the screen surface are beryllium beads. In order to better separate the part of the material, the part of the material is poured into a plastic basin, a little clear water is added, the part of the material is scrubbed by a stainless steel brush, impurities adhered to the surfaces of beryllium beads are scrubbed as much as possible, finally the beryllium beads are sieved by a 150-mesh sieve, the part of the beryllium beads left on the beryllium beads is added into the beryllium beads sieved in the first step, and the sieved part of the material is added into the material of magnesium fluoride.
In the fourth step, the crushing method comprises the following steps: sending the beryllium balls obtained in the third step into a jet mill for crushing, washing to be neutral after cold soaking, and drying to obtain coarse beryllium powder; the beryllium beads are sent into a jet mill to be crushed into particles with the size smaller than 1 mm; the beryllium balls are cleaned and dried before being sent into a jet mill; the beryllium balls are fed into a jet mill and filled with nitrogen as protective gas before being fed into the jet mill, so that the beryllium balls are prevented from being oxidized; beryllium powder obtained by impact grinding is polygonal and has higher purity, and then the beryllium powder is cleaned and dried; the immersion liquid used in the cold leaching is concentrated nitric acid; the cold soaking time is 10-15 minutes, and a plastic rod is used for stirring for a plurality of times; the washing method is to use purified water for quick washing; the drying method after the beryllium bead crushing, cold soaking and washing is to place the beryllium bead in a stainless steel basin for drying.
The beryllium fluoride can be recycled, and comprises the following steps:
(1) putting the separated magnesium chloride slag and the smoke generated by heating into an enamel reaction kettle; the smoke dust is collected into a bag dust collector from an air outlet pipe of the reducing furnace by a Venturi ejector;
(2) adding hydrofluoric acid into the reaction kettle, heating, boiling, filter-pressing, and boiling again after filter-pressing to obtain filter residue and filtrate; the mass fraction of the hydrofluoric acid is 40%; adding the hydrofluoric acid until the pH value of the liquid is less than 0.5; the time for heating and soaking is 1.5 hours each time; if the acidity becomes light in the process of soaking and boiling the magnesium chloride slag and the smoke dust, adding hydrofluoric acid to ensure that the pH value is less than 0.5;
through the secondary soaking and boiling, the beryllium content of the smoke dust and the residue is lower than 0.1 percent, and the leaching rate is higher than 98 percent;
(3) cleaning and drying the filter residue in the sun to obtain dried magnesium fluoride; cleaning, drying in the air, and packaging for sale;
(4) purifying the filtrate to obtain beryllium oxide thick slurry, and preparing a reduction raw material for recycling; adding calcium carbonate, stirring while adding, heating to 80 ℃, standing for several hours after 60 minutes, naturally settling the impurities, filtering after the pH value reaches 6.5-7, carrying out solid-liquid separation, removing the impurities, adding the impurities into the enamel reaction kettle for concentration, adding the mixture into the enamel reaction kettle, vacuumizing, electrifying, heating to 90 ℃, and carrying out evaporation concentration until the thick beryllium oxide slurry is formed; and opening the discharge port, taking out the material, and conveying the material to a magnesium reduction process for reduction.
In the method for forming ingots by purifying the crude beryllium powder, a thermal dissociation reactor for purifying the crude beryllium powder is firstly arranged, as shown in fig. 5, the thermal dissociation reactor comprises an iodine containing furnace 23, a low-temperature reactor 22 and a high-temperature reactor 13, wherein the iodine containing furnace 23 is communicated with the low-temperature reactor 22; the low temperature reactor 22 communicates with the high temperature reactor 13. The crude beryllium powder 16 reacts with iodine vapor in the low temperature reactor 22 to produce beryllium iodide vapor. The beryllium iodide vapor rises from the low-temperature reactor 22 to the high-temperature reactor 13, and is thermally dissociated under high-temperature conditions into metallic beryllium and iodine vapor.
The high-temperature reactor 13 is connected with the cooling box 1; a liquid storage tank 2 is connected under the cooling tank 1; one side of the liquid storage tank 2 is connected with a vacuum pump 3; the vacuum pump 3 is also connected with one side of the iodine containing furnace 23. The iodine vapor dissociated in the high-temperature reactor 13 is cooled by the cooling box 1, stored in the liquid storage box 2, returned to the low-temperature reactor 22 again, and re-reacted with the crude beryllium powder to synthesize beryllium iodide, and rises to the high-temperature reactor 13 again under the driving of concentration difference and temperature difference, and the circulation is not carried out until the crude beryllium powder is completely reacted. Iodine does not leak, does not volatilize and theoretically has no loss, but has little loss in actual operation. And after the first batch of crude beryllium powder is treated, adding a new batch of crude beryllium powder and iodine, and continuously purifying.
A first thermocouple 19 is arranged in the iodine containing furnace 23; the inlet of the low-temperature reactor 22 is communicated with the outlet of the iodine containing furnace 23; a second thermocouple 17 is arranged in the low-temperature reactor; the inlet of the high temperature reactor 13 is communicated with the outlet of the low temperature reactor 22; the inlet of the high-temperature reactor 13 is communicated with the outlet of the low-temperature reactor 22 through an iodine vapor hole 14; a third thermocouple 10 is arranged in the high-temperature reactor 13. The iodine containing furnace, the low-temperature reactor and the high-temperature reactor are respectively heated, and the flow of beryllium iodide steam and iodine steam is accurately controlled through the control of different power supplies.
An iodine containing basin 21 is arranged in the iodine containing furnace 23; a helium pipe 20 is arranged above the iodine containing basin 21; a first valve 24 is arranged at the joint of the helium pipe 20 and the iodine containing furnace 23 to control the helium to enter; the low-temperature reactor 22 is separated from the iodine containing furnace 23 through a first partition plate 29; the inlet of the low-temperature reactor 22 is communicated with the outlet of the iodine containing furnace 23 through a porcelain tube 18; a stainless steel frame and a stainless steel basin 15 are arranged in the low-temperature reactor; the stainless steel basin 15 is used for containing coarse beryllium powder 16; the high temperature reactor 13 is isolated from the low temperature reactor 22 by a second partition 28; a cylinder 8 is arranged in the high-temperature reactor 13; 2-3 cylinders 8 are used for bearing the adhesion of pure beryllium powder; the cylinders 8 are respectively hung on the hooks 5 above; a tungsten wire 12 is arranged in the cylinder 8; the iodine containing furnace 23, the low-temperature reactor 22 and the high-temperature reactor 13 are isolated from the outside by metal plates 11; the metal plate 11 is filled with a heating rod 9; the metal plate 11 is sealed by an insulating layer 7; the outside of the heat-insulating layer 7 is sealed by a red brick layer 6; a main switch 4 is arranged outside the heat-insulating layer 7; the main switch 4 controls the power supply of the whole reaction system; the outlet of the high-temperature reactor 13 is communicated with the inlet of the cooling box 1; the outlet of the high-temperature reactor 13 is connected with the inlet of the cooling box 1 through a pipeline; a second valve 25 is arranged on a pipeline for communicating the high-temperature reactor 13 with the cooling box 1; the liquid storage tank 2 is connected to the position right below the cooling tank 1 through a pipeline; a third valve 26 is arranged at the joint of the liquid storage tank and the vacuum pump 3; a fourth valve 27 is arranged at the joint of the vacuum pump 3 and the iodine containing furnace 23.
The stainless steel basin 15 is made of 80% of nickel and 20% of chromium alloy; the material of the cylinder 8 is NI-Cr alloy; the metal plate 11 is made of NI-Cr alloy; the first separator 29 and the second separator 28 are made of ceramic.
Each cylinder 8 has the diameter of 20cm and the length of 80cm, and bears the adhesion of less than or equal to 20 kilograms of metal beryllium powder.
As shown in fig. 4, the method for purifying crude beryllium powder by using the thermal dissociation reactor for purifying crude beryllium powder and smelting the crude beryllium powder into beryllium ingots comprises the following steps:
putting coarse beryllium powder 16 into a stainless steel basin 15, wherein the thickness of the beryllium powder is 30-50mm, and then putting the beryllium powder on a stainless steel frame of the low-temperature reactor; adding iodine into the iodine containing basin 21, and placing the iodine containing basin 21 into the iodine containing furnace 23;
starting the vacuum pump to maintain the vacuum degree at 0.05pa and the air leakage rate less than 1.3 × 10-1Pa., L.S; switching on a power supply of the iodine containing furnace 23, heating and raising the temperature to change iodine into steam, wherein the iodine steam enters the low-temperature reactor 22 through the porcelain tube 18;
switching on a power supply of the low-temperature reactor 22, heating to raise the temperature, wherein the initial temperature raising speed is slow, the temperature is raised to 300 ℃ at the raising speed of 20 ℃ per minute, then the temperature is kept constant for 30 minutes in the temperature section, the temperature is not raised again when the temperature reaches 500 ℃, and the temperature is kept until the reaction is finished;
when beryllium iodide vapor appears in the low-temperature reactor 22, switching on a power supply of the high-temperature reactor 13, heating, keeping the temperature for 30 minutes when the temperature is raised to 500 ℃, keeping the temperature for 30 minutes when the temperature is raised to 800 ℃, then keeping the temperature for 1100 ℃, and keeping the temperature until the work is finished;
when the beryllium iodide vapor gradually rises to the high-temperature reactor 13, a small amount of helium is introduced under the condition that the vacuum degree is stabilized at 0.05pa, so that the beryllium iodide vapor carries more beryllium into the high-temperature reactor 13. Simultaneously, opening a cooling box 1 and a second valve 25 of the high-temperature reactor 13, so that dissociated iodine vapor rushes into the cooling box 1 to start circulating flow;
the input amount of helium is smaller initially, but when beryllium iodide vapor is increased gradually, the input amount of helium is increased, so that the input amount of helium is in direct proportion to the input amount of beryllium iodide vapor and is adjusted according to the input amount of beryllium iodide vapor;
because the reaction of beryllium and iodine is slow, the time required by the reaction is long, and the operation is continuously operated for 30 hours;
and when the iodine vapor becomes thin and the coarse beryllium powder 16 remains a little, stopping the reaction, turning off the power supply, stopping heating, cooling to the temperature of the furnace to be lower than 350 ℃, taking down the cylinder 8, scraping the beryllium adhered to the cylinder wall by using a sharp stainless steel scraper, and collecting the pure beryllium powder.
After the thermal dissociation purification of iodine, the purity of the metallic beryllium reaches 99.99 percent, and the metallic beryllium is further purified by electron beam vacuum melting.
The pure beryllium powder is conveyed into a furnace by a vibrating pusher, an isolating switch of a power supply cabinet is closed, a vacuum system is opened in an empty mode, a manual indicator lamp is turned on within 10 seconds, a vacuum gauge on the instrument power supply cabinet is opened, the system is evacuated, then a 'auxiliary high-voltage filament in the power supply cabinet is opened in an empty mode' and then a 'main high-voltage filament in the power supply cabinet is closed in an empty mode', a direct-current power supply in the instrument power supply cabinet is opened for smelting, an electronic gun melts the pure beryllium powder into beryllium melt, the molten beryllium melt is dripped into an ingot mold downwards, after more than 30 minutes, the melt is solidified and cast into beryllium ingots, a dummy bar is pulled, and the beryllium ingots are taken out after air is discharged;
during smelting, the vacuum degree of the furnace is kept at 0.05pa, the smelting speed is about 30 g/min per minute, and the specific electric energy of the electron beam smelting furnace is 0.6 kg/kw.h.
Carrying out second smelting on the beryllium ingot smelted in the first step, feeding the beryllium ingot into an electron beam smelting furnace, electrifying, smelting again to obtain a second smelted beryllium melt, and allowing the second smelted beryllium melt to flow into the ingot mold to obtain a second smelted beryllium ingot after a period of time; and removing impurities on the surface of the beryllium ingot smelted in the second step to obtain the ultra-high-purity metal beryllium ingot, wherein the purity is over 99.999 percent.
After the two electron beam melting, the impurity content of the metal beryllium is (%):
aluminium<2×10-4；
Carbon (C)<3×10-4；；
Hydrogen<0.3×10-4；
Molybdenum (Mo)<2×10-4；
Copper (Cu)<1×10-4；
Iron<1×10-4；
Nitrogen is present in<2×10-4；
Oxygen gas<5×10-4；
Nickel (II)<4×10-4；
Silicon<1×10-4；
Titanium (IV)<3×10-4；
The purity of the metallic beryllium is more than 99.999 percent.
The above embodiments are only for illustrating the inventive concept of the present invention, and not for limiting the protection of the claims of the present invention, and the insubstantial modifications of the present invention using the inventive concept shall fall within the protection scope of the present invention.
Claims (8)
1. A method for preparing beryllium fluoride, which is characterized by comprising the following steps:
the first step is as follows: preparing raw materials, wherein the raw materials comprise beryllium hydroxide and hydrofluoric acid;
the second step is that: heating the raw materials to prepare a beryllium fluoride material;
the third step: drying the beryllium fluoride material to prepare beryllium fluoride crystal grains;
the fourth step: crushing the beryllium fluoride crystal grains to obtain beryllium fluoride powder, and storing;
in the first step, the purity of the beryllium hydroxide is greater than or equal to 99.8%;
the mass fraction of the hydrofluoric acid is 40%;
the mass of the beryllium hydroxide with the purity of more than or equal to 99.8 percent and the mass ratio of the hydrofluoric acid with the mass fraction of 40 percent are 11: 28;
in the second step, the heating method comprises the following steps: pouring the heated raw materials into a reactor, sealing, electrifying, stirring, and then switching on a power supply for heating to obtain a beryllium fluoride material;
the reactor is an enamel reaction kettle;
the electrified stirring is to switch on a power supply to start a stirrer in the reaction kettle for stirring;
the time of electrifying and stirring is 20-45 minutes;
stopping heating when the heating raw material is changed into a thick colloidal beryllium fluoride material, and cooling the beryllium fluoride material;
in the third step, the drying method comprises the following steps: opening a discharge port at the bottom of the enamel reaction kettle, taking the prepared beryllium fluoride material by using a stainless steel supporting basin, placing the beryllium fluoride material in a drying box, closing a door, and heating by electrifying to prepare beryllium fluoride crystal grains;
stopping heating after the beryllium fluoride material is changed into dry beryllium fluoride crystal grains, and cooling the beryllium fluoride crystal grains;
in the fourth step, the crushing method comprises the following steps: taking out the stainless steel dragging basin, and pouring the beryllium fluoride crystal grains into a stainless steel pulverizer to be pulverized to obtain beryllium fluoride powder;
the storage method comprises the following steps: filling the beryllium fluoride powder into a woven bag, and fastening a bag opening for storage;
in the second step, after the enamel reaction kettle is closed, starting a vacuum pump to vacuumize, and electrifying and stirring the enamel reaction kettle until the vacuum degree is 0.05 Pa; and in the third step, after the drying box is closed, starting a vacuum pump to vacuumize, and electrifying and heating after the vacuum degree is 0.05 Pa.
2. The method for preparing beryllium fluoride according to claim 1, wherein:
in the second step, the power is switched on to heat the mixture to 90 ℃, and a vacuum pump is started to pump steam generated by heating the mixture into a liquid storage tank outside the reaction kettle;
and in the third step, the drying is firstly carried out by heating to 50 ℃, keeping the constant temperature for 30 minutes, then heating to 90 ℃, keeping the constant temperature for 30 minutes, and then heating to 120 ℃ and keeping the constant temperature until the materials are dried.
3. The method for preparing beryllium fluoride according to claim 1, wherein:
in the second step, the temperature of the beryllium fluoride material is reduced to 40-50 ℃;
in the third step, the temperature of the beryllium fluoride crystal grains is reduced to 40-50 ℃.
4. The method for preparing beryllium fluoride according to claim 1, wherein:
the stainless steel supporting basin is lined with a polypropylene plate.
5. The method for preparing beryllium fluoride according to claim 1, wherein:
the drying box is characterized in that a rack is made of stainless steel materials and divided into a plurality of layers, and stainless steel supporting basins are arranged on the rack.
6. The method for preparing beryllium fluoride according to claim 1, wherein:
the woven bag is provided with a plastic lining.
7. The method for preparing beryllium fluoride according to claim 1, wherein:
the mass of the beryllium hydroxide with the purity of more than or equal to 99.8 percent is 44 kg;
the mass of the hydrofluoric acid with the mass fraction of 40% is 112 kg.
8. A method for preparing ultrahigh-purity metallic beryllium is characterized by comprising the following steps:
a method for preparing beryllium fluoride;
a method for preparing coarse beryllium powder;
a method for purifying crude beryllium powder into ingots;
the method for producing beryllium fluoride is a method for producing beryllium fluoride as described in any one of claims 1 to 7.
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| CN113186397B (en) * | 2021-04-16 | 2022-11-15 | 钢研晟华科技股份有限公司 | Preparation method of metallic beryllium beads |
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| GB496773A (en) * | 1937-04-17 | 1938-12-06 | Seri Holding S A | Process for the manufacture of anhydrous beryllium fluoride free from oxide |
| GB519199A (en) * | 1937-09-18 | 1940-03-19 | Seri Holding Sa | Process for the manufacture of anhydrous metal flourides free from oxide |
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