CN214168085U - Production system for preparing high-purity beryllium - Google Patents

Abstract

The utility model discloses a production system for preparing high-purity beryllium belongs to metallurgical material preparation technology technical field. The method comprises an alkali reaction tank, a primary filtering device, an acid reaction tank, a precipitation tank, a secondary filtering device, a drying device, an electrolytic furnace and the like, ensures that raw materials are subjected to alkali washing, primary filtering, acid washing, precipitation, secondary filtering, drying, melting electrolysis and post-treatment in a closed environment, realizes the preparation of high-purity beryllium (3N or more), and effectively ensures the stability, safety and controllability of a high-purity beryllium production process.

Description

Production system for preparing high-purity beryllium

Technical Field

The utility model relates to a production system for preparing high-purity beryllium belongs to metallurgical material preparation equipment technical field.

Background

The preparation of the high-purity metal material generally takes industrial-grade purity base metal or high-purity metal compound as a raw material and adopts corresponding physical and/or chemical methods to prepare the high-purity metal material, and the purity of the metal material is a key factor influencing the performance of the material. With the development of technologies in the key fields of aviation, aerospace, nuclear industry, war industry, semiconductors and the like, the application and market demand of high-purity metal materials are continuously increased, and various high-purity metal materials are used as strategic materials of high and new technologies and put higher requirements on the purity of the high-purity metal materials. The preparation, characterization and application of highly pure and ultrapure metals in the modern material science and engineering field belong to the new and growing field, wherein beryllium materials have the characteristics of high elastic modulus, high micro flexural strength, large specific heat and high thermal conductivity, good dimensional stability, etc., and have important applications in the fields of weapon systems, aerospace and nuclear power, etc., and are particularly widely used in large-diameter cylindrical tangential incidence telescopes and small-diameter X-ray microscopes with diameters ranging from tens of millimeters to 2000 millimeters, such as: the 5N beryllium material (with the purity of 99.999%) is mainly used for doping MBE sources in the manufacturing process of devices such as a cold infrared detector, a refrigeration double-color 384 multiplied by 288 focal plane detector and the like, and the purity of the beryllium material directly influences the yield and performance indexes of subsequent devices, influences the accuracy, detection range, night vision distance, definition and the like of weapons and equipment, so that the purity of the used material and the cleanliness of a production environment must be ensured in links such as raw material, crystal preparation, subsequent processing and the like to produce products with excellent performance.

At present, the beryllium material produced in China is mainly 99% (2N), the beryllium material with the purity of 99.9% (3N) can be produced rarely, and the standard of high-purity beryllium of 3N and above is lacked. In addition, the metallic beryllium and the beryllium-containing material have great difference with foreign countries in the levels of grade, process technology and material research and development, influence the development of the beryllium industrial chain and the autonomous supply of the beryllium material, and limit the development of beryllium-related application fields to a certain extent; meanwhile, 5N beryllium (ultra-high-purity beryllium) is very expensive to import. Therefore, it is urgently needed to rapidly improve the production level of China in the field, and basic research of the reinforced beryllium material is particularly needed, such as: the method comprises the following steps of high-purity beryllium smelting process technology, novel powder preparation technology, beryllium near-net-shape forming technology, rapid near-net-shape forming technology, novel beryllium alloy design and preparation technology and the like. In the existing preparation process of high-purity beryllium materials, the following technical problems exist:

firstly, because beryllium and compounds thereof are toxic, corresponding anti-virus equipment and anti-virus measures must be adopted in the whole preparation process, the dosage of beryllium is less, the market capacity of ultra-pure beryllium is about 100g, and the source of beryllium is basically dependent on import. Part of enterprises adopt a physical purification method to prepare high-purity beryllium, the product grade can generally meet 3N, the highest product grade can reach 4N, but the requirement of a beryllium product of 5N can hardly be met; some enterprises adopt a chemical method to prepare high-purity beryllium, the product grade can reach the requirement of 5N, but adverse effects on the environment are brought in the production process, so related environmental impact measures are required to be provided in the production process of preparing 5N ultrahigh-purity beryllium by adopting a chemical purification method;

secondly, the circuit of the preparation process of the high-purity beryllium is complex, the preparation process combining a chemical method and a physical method is adopted in the preparation process, the number of intermediate links is large, secondary pollution of intermediate products is easy to cause in the preparation process, and the intermediate products also need to be subjected to anti-toxic treatment;

thirdly, because beryllium dichloride has a high melting point (399.2-400 ℃), the structures of chlorination and rectification equipment need to be considered in chlorination rectification of high-purity beryllium, for example: the feeding mode, the residual liquid and residue treatment, a matched automatic control system and the like;

and fourthly, on the basis of the 4N high-purity beryllium production process, a vacuum melting process is added to produce 5N ultrahigh-purity beryllium, a vacuum melting furnace which is consistent with the ultrahigh-purity beryllium needs to be designed independently, the equipment structure and the process parameters are determined, the purification requirement of the ultrahigh-purity beryllium is met, the content of impurity elements in the beryllium product is further reduced, and the impurity content index and the use requirement of the 5N ultrahigh-purity beryllium are met.

In 26.03.2014, a patent document entitled "a method for producing purified beryllium hydroxide and a method for producing nuclear pure metallic beryllium beads using the same" having publication No. CN103663506A was disclosed, in which: the prepared refined beryllium hydroxide is used as a raw material, and a magnesium reduction method is adopted to produce nuclear-grade metal beryllium.

In 2019, 12 and 20, a patent document with publication number CN110589858A and name "a method for preparing beryllium fluoride from industrial-grade beryllium" is disclosed, wherein the patent document specifically discloses: (1) leaching industrial grade beryllium with an acid solution; (2) extracting the leachate by using an organic extractant to obtain a loaded organic phase; (3) washing the loaded organic phase with an acid solution; (4) extracting the loaded organic phase obtained in the step (3) by using an ammonium bifluoride aqueous solution, and collecting a water phase after extraction is finished; (5) adjusting the pH value of the water phase obtained in the step (4) to 5-8 by using ammonia water, and removing precipitates to obtain a filtrate; (6) concentrating and crystallizing the filtrate obtained in the step (5) at 70-130 ℃ to obtain ammonium fluoberyllate; (7) and calcining ammonium fluoberyllate at 850-1000 ℃ to obtain beryllium fluoride. The method combines acid leaching, extraction, acid washing, ammonium bifluoride aqueous solution extraction, ammonia water impurity removal, concentrated crystallization and calcination to prepare the beryllium fluoride in sequence, and the purity of the obtained beryllium fluoride is higher than 99.95 percent.

Disclosure of Invention

The utility model aims at solving the defects in the prior art and provides a production system for preparing high-purity beryllium. According to the technical scheme, the alkali reaction tank, the primary filtering device, the acid reaction tank, the precipitation tank, the secondary filtering device, the drying device, the electrolytic furnace and the like are arranged, alkali washing, primary filtering, acid washing, precipitation, secondary filtering, drying, melting electrolysis and post-treatment are carried out in a closed environment, the preparation of high-purity beryllium (3N or more) is realized, and the stability, the safety and the controllability of a high-purity beryllium production process are effectively guaranteed.

In order to achieve the technical purpose, the following technical scheme is proposed:

the production system for preparing the high-purity beryllium comprises a closed alkali reaction tank, a primary filtering device, a closed acid reaction tank, a settling tank, a secondary filtering device, a drying device and a closed electrolytic furnace, wherein the alkali reaction tank is connected with the primary filtering device;

the alkali reaction tank is connected with an alkali storage tank, the acid reaction tank is connected with an acid storage tank, and the precipitation tank is connected with a precipitant storage tank;

the front side of the station of the electrolytic furnace is provided with a stripping device for separating the metal beryllium from the electrolytic furnace, and the front side of the station of the stripping device is provided with a high-purity beryllium storage tank.

Furthermore, the alkali reaction tank, the acid reaction tank, the precipitation tank, the drying device and the electrolytic furnace are all connected with an emptying pipe, and a safety valve is arranged on the emptying pipe.

Furthermore, a platinum plate is arranged in the electrolytic furnace, the electrolytic furnace and the platinum plate are respectively connected with an electrolytic power supply, and a circuit for melting and electrolysis is formed among the electrolytic furnace, the electrolytic power supply and the platinum plate.

Furthermore, a vacuum smelting furnace is arranged on the front side of the station of the stripping device and is connected with a high-purity beryllium storage tank.

Further, the stripping device is arranged on the rear side of the station of the alkali reaction tank.

Based on the production system for preparing high-purity beryllium, the method for preparing high-purity beryllium from industrial beryllium is provided, and under the protection of inert gas, the method comprises the following steps:

A. alkali washing: putting industrial beryllium into a 10-20% sodium hydroxide aqueous solution, and stirring until the industrial beryllium is completely dissolved to obtain a sodium beryllium solution;

B. primary filtration: filtering the obtained sodium beryllide solution, and removing impurities (the impurities are impurities which do not react with OH < - >) such as Mg, Fe, Cu, Zn, Mn, Ni, Pb, Cr, Ag, Si, B and the like in the sodium beryllide solution to obtain primary filtrate and primary filter residue;

C. acid washing: introducing the obtained primary filtrate into a hydrochloric acid solution with the concentration of 10-20%, and reacting to obtain a beryllium chloride solution;

D. and (3) precipitation: introducing excessive weak base into the obtained beryllium chloride solution to generate a beryllium hydroxide solution with white precipitates;

E. secondary filtration: filtering the obtained beryllium hydroxide solution to remove NaCl and NH in the beryllium hydroxide solution₄Cl、AlCl₃The impurities (the partial impurities are H and H)⁺Is not reacted with OH^-Impurities of the reaction) to obtain a secondary filtrate and a secondary filter residue;

F. and (3) drying: placing the obtained secondary filter residue under the constant temperature condition of 100-130 ℃, and drying to obtain powdery beryllium hydroxide;

G. melting electrolysis: uniformly mixing the powdery beryllium hydroxide and sodium hydroxide powder with equal molar weight, putting the powdery beryllium hydroxide and the sodium hydroxide powder into an electrolytic furnace, heating the electrolytic furnace to 420 ℃ at the speed of 5 ℃/min, melting the beryllium hydroxide and the sodium hydroxide, and controlling the temperature in the electrolytic furnace to be constant;

keeping the temperature at the constant temperature of 420 ℃ for 0.5h, taking the electrolytic furnace as a positive electrode, taking a platinum plate in the electrolytic furnace as a negative electrode, connecting the positive electrode and the negative electrode with an electrolytic power supply, and setting the voltage to be 2.5-3V, so that the generated metal beryllium is attached to the platinum plate;

when the electrolysis current is 0.5A, setting the electrolysis power supply as a constant current, and keeping for 0.5 h;

H. and (3) post-treatment: stopping electrolysis, and reducing the current to 0A; and taking out the platinum plate, and stripping the metal beryllium from the platinum plate to obtain a high-purity beryllium product.

Further, the method for preparing high-purity beryllium from industrial beryllium further comprises the following steps: detecting the metal beryllium stripped in the step H, and if the metal beryllium is qualified, storing the metal beryllium in vacuum for later use; unqualified, placing the stripped metal beryllium into a vacuum melting furnace, vacuumizing to 5Pa, heating to 1300 ℃, keeping the vacuum degree of 5Pa, preserving heat for 2h, and slowly cooling to obtain a high-purity beryllium product; or, recycling unqualified metal beryllium as an industrial beryllium raw material, and then performing the operations of the steps A-H until a qualified high-purity beryllium product is obtained.

Further, the inert gas is argon.

Further, in the step A, the sodium hydroxide aqueous solution is of high-grade purity, and the molar ratio of industrial beryllium to sodium ions is 1: 2.

Further, in the step C, the hydrochloric acid solution is of high-grade purity, and the molar ratio of the industrial beryllium to the dilute hydrochloric acid is 1: 2.

Further, in step D, the weak base comprises ammonia gas. Since beryllium hydroxide is an amphoteric compound, it reacts to form beryllium acid salts if strong base is encountered.

Further, in step G, the sodium hydroxide powder is analytically pure, and the electrolytic furnace is a stainless steel 316L electrolytic furnace.

Further, in step G, the electrolysis current was adjusted every 0.5h until the constant current was 50A.

In the alkaline cleaning of the technical scheme, the reaction equation is as follows: (wherein Al is an impurity in industrial beryllium)

Be+2NaOH→Na₂BeO₂+H₂↑

2Al+2NaOH+6H₂O→2[NaAl(OH)₄]+3H₂↑

In the acid washing of the technical scheme, the reaction equation is as follows:

Na₂BeO₂+4HCl→2NaCl+BeCl₂+2H₂O

2[NaAl(OH)₄]+8HCl→2NaCl+2AlCl₃+8H₂O

in the precipitation of the technical scheme, the reaction equation is as follows:

BeCl₂+2NH₃.H₂O→Be(OH)₂↓+2NH₄Cl

in the melt electrolysis of the technical scheme, the reaction equation is as follows:

because beryllium is easy to oxidize and beryllium oxide is toxic (other compounds of beryllium are toxic), in the process for preparing high-purity beryllium by using industrial beryllium according to the technical scheme, the preparation process is carried out under the protection of inert gas, and related operators need to wear primary protective clothing (safety helmets, work clothes with breathing masks and integrated atmosphere, safety shoes and the like) so as to improve the safety in the production process of high-purity beryllium; according to actual requirements, operating in an argon atmosphere glove box; according to the actual requirement, the production system is connected with an inert gas storage tank, so that the production of high-purity beryllium under the protective atmosphere is ensured.

According to the technical scheme, according to actual requirements and conditions of factory building space, the equipment components (particularly an alkali reaction tank, a primary filtering device, an acid reaction tank, a precipitation tank, a secondary filtering device, a drying device and the like) can be connected and controlled through high-purity polytetrafluoroethylene pipelines, pollution-free transportation of the main material beryllium dichloride in each process is realized, the introduction of material purity and external impurities at each inlet is effectively controlled through an automatic control technology, and the purity of a final beryllium product is ensured to reach 5N grade on the basis of coupling and cascade combination synergistic purification of optimized process parameters of each process.

In the description of the present technical solution, it should be noted that unless explicitly specified or limited otherwise, positional relationships such as "front side of station" and "rear side of station" are defined according to actual use conditions, and are conventional terms in the technical field and conventional terms during actual use by those skilled in the art.

In the description of the present technical solution, it should be noted that, unless explicitly stated or limited otherwise, the terms "disposed" and "connected" should be interpreted broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood in specific cases to those skilled in the art.

By adopting the technical scheme, the beneficial technical effects brought are as follows:

1) the utility model discloses in, according to beryllium characteristic in the raw materials industry beryllium, each impurity kind and its chemical and physical properties to and through setting up such as alkali retort, one-level filter equipment, acid retort, settling tank, second grade filter equipment, drying device and electrolytic furnace, carry out alkali wash, one-level filtration, pickling, deposit, second grade filtration, drying, melting electrolysis and aftertreatment under inert gas's protection, realize the preparation technology of high-purity beryllium, especially realize the preparation of high-purity beryllium (3N and above), and effectively guarantee the stability, security and the controllability of high-purity beryllium production technology;

2) the utility model discloses in, through the cooperation between arranging of each equipment unit in the system, guarantee high-purity beryllium preparation technology's stability, controllable going on. The preparation system ensures the pollution-free transfer of the intermediate and the target among all the working procedures, and effectively controls the purity of each inlet material and the introduction of impurities;

3) the utility model discloses in, the arrangement of each equipment subassembly in this system, reasonable in design is rigorous according to the principle, is suitable for the industrialization large-scale production. According to the actual situation, the influence rule of each process parameter such as alkali washing, acid washing, purification, drying, melting electrolysis and the like on the migration, distribution and product purity of impurities can be researched by carrying out online sampling in each process section and combining with the test means such as ICP-MS, a nitrogen oxygen hydrogen analyzer, a carbon oxygen analyzer and the like; then, on-line real-time monitoring of the concentration of the beryllium hydroxide is utilized to research the melting electrolysis thermodynamics and the reaction mechanism of the beryllium hydroxide, and the evolution and the trend of the occurrence state of impurity elements and the rule and the mechanism of influence of process parameters on the beryllium purity are revealed by combining means such as XPS, ICP-MS, a nitrogen oxygen hydrogen analyzer, a carbon oxygen analyzer and an XRD structure fine modification, so that the coupled process parameters of each procedure and the position layout of each stage pipeline are optimized, and meanwhile, the coupling control and the cascade combination synergistic purification of each procedure are realized by adopting an automatic control technology to prepare high-purity beryllium with the purity of 3N or more;

4) the utility model discloses in, the arrangement of each equipment unit and the setting of each sealing equipment in the preparation system, reasonable in design guarantees in the whole process, and beryllium and other reaction product all go on under inert gas's atmosphere, have effectively stopped beryllium and compound to the pollution of environment, guarantee personal safety to be favorable to the environmental protection.

Drawings

FIG. 1 is a schematic diagram of the logic connection of the preparation system of the present invention;

fig. 2 is a schematic flow diagram of a process for producing high purity beryllium in accordance with the present invention;

in the figure: 1. the device comprises an alkali reaction tank, 2, a primary filtering device, 3, an acid reaction tank, 4, a settling tank, 5, a secondary filtering device, 6, a drying device, 7, an electrolytic furnace, 8, a drain pipe, 9, an alkali storage tank, 10, an acid storage tank, 11, a precipitant storage tank, 12, a stripping device, 13, a high-purity beryllium storage tank, 14 and a vacuum smelting furnace.

Detailed Description

In the following, the technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. Based on the embodiments in the present invention, all other embodiments obtained by a person skilled in the art without creative efforts belong to the protection scope of the present invention.

Example 1

As shown in fig. 1: the production system for preparing the high-purity beryllium comprises a closed alkali reaction tank 1, a primary filtering device 2, a closed acid reaction tank 3, a settling tank 4, a secondary filtering device 5, a drying device 6 and a closed electrolytic furnace 7, wherein the alkali reaction tank 1 is connected with the primary filtering device 2, a filtrate outlet on the primary filtering device 2 is connected with the acid reaction tank 3, the acid reaction tank 3 is connected with the settling tank 4, the settling tank 4 is connected with the secondary filtering device 5, a residue filter outlet on the secondary filtering device 5 is connected with the drying device, and the drying device is connected with the electrolytic furnace 7;

the alkali reaction tank 1 is connected with an alkali storage tank 9, the acid reaction tank 3 is connected with an acid storage tank 10, and the precipitation tank 4 is connected with a precipitant storage tank 11;

a stripping device 12 for separating metal beryllium from the electrolytic furnace 7 is arranged on the front side of the station of the electrolytic furnace 7, and a high-purity beryllium storage tank 13 is arranged on the front side of the station of the stripping device 12.

Example 2

Based on the embodiment 1, the present embodiment is further,

the alkali reaction tank 1, the acid reaction tank 3, the precipitation tank 4, the drying device 6 and the electrolytic furnace 7 are all connected with an emptying pipe 8, and a safety valve is arranged on the emptying pipe 8.

Example 3

Based on examples 1-2, this example was further,

a platinum plate is arranged in the electrolytic furnace 7, the electrolytic furnace 7 and the platinum plate are respectively connected with an electrolytic power supply, and a circuit for melting electrolysis is formed among the electrolytic furnace 7, the electrolytic power supply and the platinum plate.

Example 4

Based on examples 1-3, this example was further,

and a vacuum smelting furnace 14 is arranged on the front side of the station of the stripping device 12, and the vacuum smelting furnace 14 is connected with a high-purity beryllium storage tank 13.

Example 5

Based on examples 1-4, this example was further,

the stripping device 12 is arranged at the rear side of the station of the alkali reaction tank 1.

Example 6

Based on examples 1-5, this example proposes a method for producing highly pure beryllium from industrial beryllium (as shown in fig. 2 below), under the protection of an inert gas, comprising the following steps:

A. alkali washing: dissolving 88g of analytically pure sodium hydroxide powder in deionized water to prepare 20% sodium hydroxide aqueous solution, adding 8g of industrial beryllium, and stirring at the temperature of 30-50 ℃ for half an hour (heating is limited here, the reaction rate can be improved), so as to obtain 447.85g of sodium beryllium solution with partial particles;

B. primary filtration: filtering the obtained sodium beryllide solution through a funnel, putting undissolved particles (first-stage filter residue) into a filter residue collecting tank, and putting first-stage filtrate into an acid reaction tank 3;

C. acid washing: adding 800mL of 20% dilute hydrochloric acid into an acid reaction tank 3 during slow stirring, stirring for half an hour, and then adding into a precipitation tank 4;

D. and (3) precipitation: 2.2mol of ammonia gas is filled into the precipitation tank 4, and the mixture is stirred at a low speed to generate white precipitate, so that beryllium hydroxide solution which is mixed liquid is obtained;

E. secondary filtration: filtering the mixed solution to obtain a precipitate (secondary filter residue) and a secondary filtrate, and putting the precipitate into a drying furnace;

F. and (3) drying: keeping the temperature of the precipitate at 80-130 ℃ for half an hour to obtain 24.85g of white powdery beryllium hydroxide;

G. melting electrolysis: uniformly mixing 24.85g of beryllium hydroxide powder and 4g of sodium hydroxide powder, putting the mixture into an electrolytic furnace 7, heating the mixture to 420 ℃ at the speed of 5 ℃/min, and preserving the heat for half an hour; turning on an electrolytic power supply, adjusting the electrolytic power supply to a constant voltage mode, slowly adjusting the voltage to 2.5-3V, observing an ammeter, and adjusting the electrolytic power supply to a constant current mode when the current is 0.5A; after half an hour, slowly increasing the current intensity to 1A, adjusting the current every half an hour, superposing the number of electrolytic ampere hours, stopping electrolysis when the number of ampere hours exceeds 53.6Ah, lifting the cathode platinum plate, and stopping heating;

H. after the electrolytic furnace 7 is cooled, the beryllium film on the platinum plate is scraped off, and then weighing and detection are carried out, so that 7.8g of high-purity beryllium product is obtained.

Claims (5)

1. The production system for preparing high-purity beryllium is characterized by comprising a closed alkali reaction tank (1), a first-stage filtering device (2), a closed acid reaction tank (3), a precipitation tank (4), a second-stage filtering device (5), a drying device (6) and a closed electrolytic furnace (7), wherein the alkali reaction tank (1) is connected with the first-stage filtering device (2), a filtrate outlet on the first-stage filtering device (2) is connected with the acid reaction tank (3), the acid reaction tank (3) is connected with the precipitation tank (4), the precipitation tank (4) is connected with the second-stage filtering device (5), a filtrate outlet on the second-stage filtering device (5) is connected with the drying device, and the drying device is connected with the electrolytic furnace (7);

the alkali reaction tank (1) is connected with an alkali storage tank (9), the acid reaction tank (3) is connected with an acid storage tank (10), and the precipitation tank (4) is connected with a precipitant storage tank (11);

a stripping device (12) for separating the metal beryllium from the electrolytic furnace (7) is arranged on the front side of the station of the electrolytic furnace (7), and a high-purity beryllium storage tank (13) is arranged on the front side of the station of the stripping device (12).

2. The production system for preparing high-purity beryllium according to claim 1, wherein the alkali reaction tank (1), the acid reaction tank (3), the precipitation tank (4), the drying device (6) and the electrolytic furnace (7) are all connected with a drain pipe (8), and a safety valve is arranged on the drain pipe (8).

3. The production system for preparing high-purity beryllium according to claim 1, wherein a platinum plate is arranged in the electrolytic furnace (7), the electrolytic furnace (7) and the platinum plate are respectively connected with an electrolytic power supply, and a circuit for melting and electrolyzing is formed among the electrolytic furnace (7), the electrolytic power supply and the platinum plate.

4. The production system for preparing high-purity beryllium according to claim 1, wherein a vacuum smelting furnace (14) is arranged at the front side of the station of the stripping device (12), and the vacuum smelting furnace (14) is connected with a high-purity beryllium storage tank (13).

5. The production system for preparing high-purity beryllium according to claim 1, wherein the stripping device (12) is arranged at the rear side of the station of the alkali reaction tank (1).

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