CN108796244B - Method for preparing high-purity rubidium by one-step thermal reduction of metal calcium - Google Patents
Method for preparing high-purity rubidium by one-step thermal reduction of metal calcium Download PDFInfo
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Abstract
The invention discloses a method for preparing high-purity rubidium by one-step thermal reduction of metal calcium, which comprises the steps of taking metal calcium particles with the purity of more than 95% and rubidium chloride powder with the purity of 98.0-99.9% as raw materials, mixing the metal calcium particles with the rubidium chloride powder, taking stainless steel as a container, placing the container in a horizontal vacuum electric furnace to be heated to 842-1390 ℃ under inert atmosphere, carrying out thermal reduction displacement reaction, guiding metal rubidium steam to a condensation part under vacuum suction force through a heated straight-through pipeline, condensing the metal rubidium steam into liquid drops, and enabling the purity of the obtained liquid metal rubidium to reach 99.50-99.99%. The invention provides a process for preparing high-purity rubidium by adopting a reducing metal one-step heating method, complex processes such as multiple heating reduction, electrolysis, distillation and the like are not needed, and the process has the advantages of simple and feasible purification process, low cost, environmental friendliness, no pollution, safety and reliability, and is suitable for continuous industrialization. Compared with the prior art, the method has better practicability and industrialization advantages.
Description
Technical Field
The invention belongs to the field of metal purification, and particularly relates to a method for preparing high-purity rubidium by using metal calcium particles and rubidium chloride powder as raw materials and adopting one-step heating reduction.
Background
Because rubidium has unique performance, the rubidium plays an important role in both the traditional field and the new application field, and particularly has an increasingly obvious role in the high-tech field, so that the rubidium has wide application range and occupies an important position in national economy. In the traditional fields, such as catalyst, special glass, electronic devices, biological materials, etc., the development has been greatly increased in recent years. In new fields, such as rubidium atomic clock, magnetohydrodynamic power generation, energy and other fields, powerful vitality is further shown. At present, in developed countries, the ratio of rubidium used in high and new fields reaches 80%, and the ratio of rubidium used in traditional fields is 20%. Rubidium is an important raw material for manufacturing electronic devices (photomultiplier tubes and photoelectric tubes), spectrophotometers, automatic control, spectrometry, color movies, color televisions, radars, lasers, glass, ceramics, electronic clocks and the like; in terms of space technology, ion thrusters and thermionic energy converters require large amounts of rubidium; rubidium hydroxide and boride can be used as high-energy solid fuel; the radioactive rubidium can measure the mineral age; in addition, rubidium compounds are applied to the pharmaceutical industry and the paper making industry; rubidium may also act as a getter for vacuum systems.
Rubidium is a very active rare alkali metal, has a content of 0.028% in the earth crust, is extremely dispersed, has no separate mineral deposit, and is mainly present in lepidolite [ KRbLi (OH, F) Al2Si3O10Carnallite [ KCl MgCl ]2·6H2O, solid ore and salt lake brine. 55% of rubidium resources in China are stored in lepidolite, and Jiangxi Yichun, Hunan, Hubei, Henan, Guangdong, Sichuan and the like are main enrichment places of the rubidium resources in China. The content of rubidium in salt lake brine of Qinghai, Tibet plateau and other places and underground brine is also very rich, but the chemical property of rubidium is similar to the property of other coexisting metal ions, so that the industrial separation is difficult, the full utilization of rubidium resources is limited, and the yield of rubidium is low.
At present, the main production methods of metal rubidium are as follows: electrolytic processes, thermal decomposition processes and metallothermic processes. Bensen (Bunsen) and Chelchoff (Krichhoff) electrolyze molten rubidium chloride in an electrolytic cell consisting of a graphite anode and an iron cathode for the first time to successfully prepare metallic rubidium. Alternatively, rubidium amalgam is obtained by electrolysis from a melt having mercury as a cathode, and the metal rubidium is recovered from the rubidium amalgam. The most appropriate electrolyte system for molten rubidium metal electrolysis is a halide system, wherein the rubidium metal has a low boiling point and a high melting point, and a fluxing substance capable of reducing the melting point of the electrolyte is generally added into the halide. The activity of rubidium is strong, so that the collection process of preparing metal rubidium by electrolysis is very complicated, and the loss of metal rubidium in the collection process is large, therefore, the electrolysis method is not widely applied finally.
The thermal decomposition method is a method for preparing a small amount of high-purity metal rubidium. Neutralizing rubidium carbonate with azido acid, or reacting with barium azide and rubidium sulfate solution to obtain rubidium azide. Rubidium azide is stable in property, is easy to dissociate when heated, and decomposes at about 583K to release nitrogen. Carrying out thermal decomposition on rubidium azide under the vacuum pressure of 10Pa and the temperature of 773K to obtain the spectral pure metal rubidium without gas.
The metallothermic reduction method is the simplest method for preparing the metal rubidium and is the most mainstream method for preparing the metal rubidium at present. Rubidium hydroxide, rubidium carbonate, rubidium halide, rubidium sulfate, rubidium chromate and rubidium nitrate are used as raw materials, and metals with strong reducibility, such as lithium, sodium, calcium, magnesium, zirconium, aluminum or silicon, are used as reducing agents, and the reduction is carried out at high temperature. The reduction reaction was carried out in an inert atmosphere and the rubidium vapor was removed from the reaction apparatus by vacuum distillation. The rubidium metal steam is guided to a condensation part under vacuum pumping force, and flows into a collector after being condensed into liquid drops.
In the prior patent, the main technical route adopts metallothermic reduction to prepare high-purity rubidium, namely a vacuum reduction method or metallothermic reduction technology under high-pressure atmosphere. Patent CN107164641A describes a method for preparing high-purity metals rubidium and cesium, which uses pressurized inert gas (inert gas pressure is 0.4-0.5 MPa) to prepare high-purity rubidium, and this method requires that the preparation equipment can withstand high temperature and high pressure, so that the method has potential safety hazard, is not suitable for industrial popularization, and has huge investment. In addition, the patent is characterized in that a box-type resistance furnace is adopted, and the pipe wall is S-shaped, so that the method involved in the patent is complex to operate in the actual production process, the pipeline is difficult to clean, and continuous production cannot be realized. Patent CN105063375A discloses a method for preparing high-purity metal rubidium and cesium by vacuum thermal reduction, which adopts a metal thermal reduction method under vacuum environment, and has the disadvantages of complicated operation process, impracticality and inconvenience. Another disadvantage of the above patents relating to the preparation process is that: the above methods are all single furnace type and cannot complete continuous operation. Because rubidium can be explosively combusted when meeting water, oxygen and air, people desire a practical, safe, efficient and continuous preparation method of high-purity rubidium.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the background technology and providing a method for preparing high-purity rubidium by using metal calcium particles and rubidium chloride powder as raw materials and adopting one-step heating reduction.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for preparing high-purity rubidium by one-step thermal reduction of metal calcium comprises the following steps:
(1) replacing oxygen in the horizontal vacuum electric furnace by adopting a vacuum pumping and inert gas filling mode;
(2) uniformly mixing metal calcium particles and rubidium chloride powder according to the mass ratio of (1:2) - (4:1), placing the mixture into the horizontal vacuum electric furnace treated in the step (1), heating the mixture to 842-1390 ℃ under the condition of inert atmosphere and normal pressure, and preserving heat for 30-120 min; the melting point of calcium is 842 ℃, and the boiling point is 1484 ℃; the melting point of rubidium chloride is 718 ℃ and the boiling point of rubidium chloride is 1390 ℃.
(3) And after the display of the pressure gauge in the horizontal vacuum electric furnace rises, the vacuum pump is turned on, and the heated pipeline connected with the inner bore of the horizontal vacuum electric furnace guides the metal rubidium steam to a condensation part to obtain liquid metal rubidium. And (3) displacing the rubidium metal steam, starting a vacuum pump after a pressure gauge in the furnace is raised, guiding the rubidium metal steam to a condensation part through a heated straight-through pipeline under the vacuum pumping force, condensing into liquid drops, and then flowing into a collector to obtain liquid rubidium metal.
Preferably, in the step (1), the specific operations of replacing oxygen in the horizontal vacuum electric furnace by vacuumizing and filling inert gas are as follows: controlling the vacuum degree in the horizontal vacuum electric furnace at 0.01Pa, charging inert gas to normal pressure state (the pressure gauge shows as 0), vacuumizing, and charging inert gas, and repeatedly vacuumizing and charging inert gas to replace oxygen in the horizontal vacuum electric furnace for more than 3 times.
In the method, preferably, the discharge pipe in the horizontal vacuum electric furnace is designed to form an included angle of 3-5 degrees with the horizontal plane; all metal rubidium steam recovery pipelines in the horizontal vacuum electric furnace adopt a straight-through type.
In the above method, preferably, the heated pipe is heated by circulating water heating, resistance heating or gas heating. Preferably, circulating water is used for heating, and a heat source utilizes a horizontal vacuum electric furnace to heat and replace the residual heat of rubidium. The circulating water is an outer layer pipeline of a water pump water inlet metal rubidium recovery pipeline in a water storage tank, a water outlet is connected to an outer layer water jacket layer of the hearth wall and then enters the water storage tank, so that a circulating water path is formed, water in the outer layer water jacket of the hearth wall transfers waste heat of reduced metal rubidium of the horizontal vacuum electric furnace out, so that the waste heat is continuously circulated to heat the recovery pipeline, and the circulating water has the characteristics of environmental protection and low cost. In addition, when the heated pipeline recovers rubidium metal, the rubidium metal can release a large amount of heat, and the temperature of the recovery pipeline exceeds the tolerance temperature of a human body, and the circulating water pipeline adopted in the invention has the function of preventing the human body from being scalded.
In the above method, preferably, the purity of the calcium metal particles is greater than 95%. If the purity of the metal calcium is too low, other impurities with low melting point can be brought in, the preparation of high-purity rubidium is not facilitated, and the price of the metal calcium with the purity of 95% is moderate.
In the above method, preferably, the particle size of the calcium metal particles is less than 5 mm. The particle size of the calcium metal particles is too large and the uniformity of the mixed rubidium chloride powder is poor.
In the above method, preferably, the particle size of the calcium metal particles is less than 2 mm. The particle size of the calcium metal particles is too large and the uniformity of the mixed rubidium chloride powder is poor. Smaller calcium particles are better, but not too small, and too fine metallic calcium is difficult to prepare and expensive.
In the above method, the purity of the rubidium chloride powder is preferably 98.0% to 99.9%. The purity of rubidium chloride is higher, the purity of metallic rubidium is higher, and impurities which are difficult to remove are brought in when the purity of rubidium chloride is lower than 98%.
In the above method, the purity of the rubidium chloride powder is preferably 99.0% to 99.9%. The purity of the rubidium chloride is higher, the purity of metal rubidium is higher, and volatile impurities are reduced.
In the above method, preferably, the inert gas is one of argon, nitrogen or helium.
In the method, the purity of the obtained liquid metal rubidium is preferably 99.50-99.99%.
The invention has the beneficial effects that:
the invention adopts the process of preparing high-purity rubidium by a one-step heating method, omits complex procedures of multiple heating purification, electrolysis, distillation and the like, has the advantages of simple and easy purification process, low cost, environmental protection, no pollution, safety and reliability, and particularly adopts a straight-through type recovery pipeline, thereby facilitating the metal steam to enter the recovery pipeline, reducing the pipeline resistance and the adsorption on the pipeline, and leading the recovery rate of the metal rubidium to be extremely high. In addition, the impurities adsorbed on the pipeline are convenient to clean, so that the requirement of industrial production can be met.
Compared with the prior art, the invention has the advantages that:
(1) according to the method, the purification temperature of the metal rubidium is above the melting point of metal calcium and below the boiling point of rubidium chloride, the metal calcium and the rubidium chloride in a molten state are fully combined to obtain metal rubidium steam, the metal rubidium steam is guided to a condensation part under vacuum suction, and the metal rubidium steam is condensed into liquid drops and flows into a collector to obtain liquid metal rubidium. The molten state has the advantages of full reaction of calcium metal and rubidium chloride, high displacement reaction rate of rubidium metal, high direct yield and the like.
(2) The rubidium metal recovery pipeline provided by the invention is a straight-through pipeline (the melting point of rubidium metal is 38.89 ℃, and the rubidium metal cannot be collected by a pipeline with too low temperature), the collection pipeline can be heated by adopting modes of circulating water heating, resistance heating, gas heating and the like, the circulating water is preferably heated in the invention, and the heat source is used for replacing the residual heat of rubidium by heating with a horizontal vacuum electric furnace.
(3) The method for preparing high-purity rubidium by one-step metal calcium thermal reduction saves the processes of multiple heating purification, electrolysis, distillation and the like, adopts a one-step heating purification mode, reduces the technological process, utilizes waste heat to circularly heat a recovery pipeline, saves the cost, and has no air pollution problem in the purification process.
(4) The horizontal vacuum electric furnace is adopted, the furnace inner chamber is in a horizontal cylindrical shape, the vacuumizing pipeline, the inflating pipeline and the metal rubidium steam recovery pipeline are connected to the side face of the cylindrical furnace inner chamber, meanwhile, the recovery pipeline is in a straight-through type, the metal rubidium recovery rate is high by matching with the special equipment, the cleaning is convenient, and the horizontal vacuum electric furnace is suitable for continuous industrialization.
(5) The invention provides a method for continuously preparing high-purity rubidium under the protection of inert gas in a normal-pressure environment, does not need high-pressure container equipment, and has the characteristics of continuity, convenience, practicability, simplicity, safety and low cost.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a structural view of a horizontal vacuum electric furnace used in the present invention.
(1, furnace bladder; 2, furnace cover; 3, inner sealing ring; 4, discharge pipe; 5, pre-vacuum pipe; 6, inflation pipe)
FIG. 2 is a graph showing samples of comparative example 3 of the present invention for preparing high purity rubidium.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
taking 50 g of rubidium chloride powder (99.5 percent, white) and 50 g of metal calcium particles (99.9 percent, average particle size of 5mm, silver white), uniformly mixing, putting into a stainless steel plate, putting into a horizontal vacuum electric furnace, controlling the vacuum degree in the furnace to be 0.01Pa before heating, flushing inert gases such as argon and the like to be in a normal pressure state, vacuumizing, flushing the inert gases, repeatedly replacing oxygen in the horizontal vacuum electric furnace for more than 3 times by using vacuum and inert gases, heating the material to 750 ℃ in the normal pressure state under the inert atmosphere, keeping the temperature for 60min, collecting liquid metal rubidium by using a wide-mouth bottle filled with liquid paraffin, and enabling no liquid metal to flow out. After the heat preservation, the heating device was closed, the furnace cover was opened after the furnace temperature was cooled to room temperature, and white powder was covered around the furnace wall and was found to be rubidium chloride powder.
The invention adopts a horizontal vacuum electric furnace, and the structure is shown as attached figure 1. In order to obtain high-purity rubidium, the horizontal vacuum electric furnace is specially designed:
(1) the furnace pipe 1 is designed into a horizontal cylinder shape and is horizontally arranged;
(2) in order to prevent rubidium metal steam from escaping around after reaction, a furnace sealing ring 3 is designed between a furnace cover 2 and a furnace pipe 1, the sealing ring 3 is made of a stainless steel sheet with good rigidity, the thickness is controlled to be 1.0-2.0 mm, and the sealing ring has high-temperature resistance elasticity;
(3) the discharge pipe 4 and the pre-vacuumizing pipe 5 do not share one pipeline, and the discharge pipe 4 is specially designed to form an included angle of 3-5 degrees with the horizontal plane, so that rubidium metal is prevented from flowing back into the furnace cavity;
(4) the gas-filled pipeline 6 is lengthened to the lower part of the material containing frame, so that the raw materials are prevented from being blown away during ventilation;
(5) all the rubidium metal steam recovery pipelines adopt a straight-through type, and the equipment is simple and easy to clean.
Comparative example 1:
taking 50 g of rubidium chloride powder (99.5 percent, white) and 50 g of metal calcium particles (99.9 percent, average particle size of 5mm, silver white), uniformly mixing, putting into a stainless steel plate, putting into a horizontal vacuum electric furnace, controlling the vacuum degree in the furnace to be 0.01Pa before heating, flushing inert gases such as argon and the like to be in a normal pressure state, vacuumizing, flushing the inert gases, repeatedly replacing oxygen in the horizontal vacuum electric furnace for more than 3 times by using vacuum and inert gases, heating the material to 800 ℃ in the normal pressure state under the inert atmosphere, keeping the temperature for 60min, changing the gas pressure in the whole reaction process, collecting liquid metal rubidium by using a wide-mouthed bottle filled with liquid paraffin, and enabling no liquid metal to flow out. After the heat preservation is finished, the heating device is closed, the furnace cover is opened when the temperature of the furnace is cooled to the room temperature, white powder covers the periphery of the furnace wall, and the powder is found to be rubidium chloride powder, which indicates that the change of the air pressure in the reaction process is caused by rubidium chloride steam.
Comparative example 2:
taking 50 g of rubidium chloride powder (99.5 percent, white) and 50 g of metal calcium particles (99.9 percent, average particle size of 5mm, silver white), uniformly mixing, putting into a stainless steel disc, putting into a horizontal vacuum electric furnace, controlling the vacuum degree in the furnace to be 0.01Pa before heating, flushing inert gases such as argon and the like to be in a normal pressure state, vacuumizing, flushing the inert gases, repeatedly replacing oxygen in the horizontal vacuum electric furnace for more than 3 times by using vacuum and inert gases, heating the material to 850 ℃ in the normal pressure state under the inert atmosphere, keeping the temperature for 60min, obviously changing the gas pressure in the whole reaction process, collecting liquid metal rubidium by using a wide-mouth bottle filled with liquid paraffin, estimating that the metal rubidium is about 20 g, the direct yield of the metal rubidium is 57.14 percent, and detecting the purity of the metal rubidium by adopting ICP-AES to be more than 99.90 percent, which is shown in Table 2.
Comparative example 3:
taking 50 g of rubidium chloride powder (99.5 percent, white) and 50 g of metal calcium particles (99.9 percent, average particle size of 5mm, silver white), uniformly mixing, putting into a stainless steel disc, putting into a horizontal vacuum electric furnace, controlling the vacuum degree in the furnace to be 0.01Pa before heating, flushing inert gases such as argon and the like into the furnace to be in a normal pressure state, vacuumizing, flushing the inert gases into the furnace, repeatedly replacing oxygen in the horizontal vacuum electric furnace for more than 3 times by using vacuum and inert gases, heating the material to 900 ℃ in the normal pressure state under the inert atmosphere, keeping the temperature for 60min, obviously changing the gas pressure in the whole reaction process, collecting liquid metal rubidium by using a wide-mouth bottle filled with liquid paraffin, and showing a sample diagram in figure 2, wherein about 27 g of metal rubidium is estimated, and the direct yield of the metal rubidium is 77.15 percent.
Example 2:
taking 50 g of rubidium chloride powder (99.5 percent, white) and 50 g of metal calcium particles (99.9 percent, average particle size of 5mm, silver white), uniformly mixing, putting into a stainless steel plate, putting into a horizontal vacuum electric furnace, controlling the vacuum degree in the furnace to be 0.01Pa before heating, flushing inert gases such as argon and the like into the furnace to be in a normal pressure state, vacuumizing, flushing the inert gases into the furnace, repeatedly replacing oxygen in the horizontal vacuum electric furnace for more than 3 times by using vacuum and inert gases, heating the material to 850 ℃ in the normal pressure state under the inert atmosphere, keeping the temperature for 120min, obviously changing the gas pressure in the whole reaction process, collecting liquid metal rubidium by using a wide-mouth bottle filled with liquid paraffin, and estimating that the metal rubidium is about 25 g and the metal rubidium yield is 71.43 percent.
Comparative example 4:
taking 50 g of rubidium chloride powder (99.5 percent, white) and 50 g of metal calcium particles (99.9 percent, average particle size of 5mm, silver white), uniformly mixing, putting into a stainless steel plate, putting into a horizontal vacuum electric furnace, controlling the vacuum degree in the furnace to be 0.01Pa before heating, flushing inert gases such as argon and the like into the furnace to be in a normal pressure state, vacuumizing, flushing the inert gases into the furnace, repeatedly replacing oxygen in the horizontal vacuum electric furnace for more than 3 times by using vacuum and inert gases, heating the material to 850 ℃ in the normal pressure state under the inert atmosphere, preserving the temperature for 30min, obviously changing the gas pressure in the whole reaction process, collecting liquid metal rubidium by using a wide-mouth bottle filled with liquid paraffin, and estimating that the metal rubidium is about 18 g and the metal rubidium yield is 51.43 percent.
Comparative example 5:
taking 50 g of rubidium chloride powder (99.5 percent, white) and 50 g of metal calcium particles (99.9 percent, average particle size-5 mm, silver white), uniformly mixing, putting into a stainless steel plate, putting into a horizontal vacuum electric furnace, controlling the vacuum degree in the furnace to be 0.01Pa before heating, flushing inert gases such as argon and the like into the furnace to be in a normal pressure state, vacuumizing, flushing the inert gases into the furnace, repeatedly replacing oxygen in the horizontal vacuum electric furnace for more than 3 times by using vacuum and inert gases, heating the material to 850 ℃ in the normal pressure state under the inert atmosphere, preserving the temperature for 10min, changing the gas pressure in the whole reaction process, collecting no liquid metal rubidium by using a wide-mouth bottle filled with liquid paraffin, reacting to generate metal rubidium, and collecting no liquid metal rubidium due to short replacement time.
Example 3:
taking 50 g of rubidium chloride powder (99.5 percent, white) and 25 g of metal calcium particles (99.9 percent, average particle size of 5mm, silver white), uniformly mixing, putting into a stainless steel plate, putting into a horizontal vacuum electric furnace, controlling the vacuum degree in the furnace to be 0.01Pa before heating, flushing inert gases such as argon and the like into the furnace to be in a normal pressure state, vacuumizing, flushing the inert gases into the furnace, repeatedly replacing oxygen in the horizontal vacuum electric furnace for more than 3 times by using vacuum and inert gases, heating the material to 850 ℃ in the normal pressure state under the inert atmosphere, keeping the temperature for 60min, obviously changing the gas pressure in the whole reaction process, collecting liquid metal rubidium by using a wide-mouth bottle filled with liquid paraffin, and estimating that the metal rubidium is about 12 g and the direct yield of the metal rubidium is 34.29 percent.
Comparative example 6:
taking 50 g of rubidium chloride powder (99.5 percent, white) and 12.5 g of metal calcium particles (99.9 percent, average particle size of 5mm and silver white), uniformly mixing, putting the mixture into a stainless steel plate, putting the stainless steel plate into a horizontal vacuum electric furnace, controlling the vacuum degree in the furnace to be 0.01Pa before heating, flushing inert gases such as argon and the like into the furnace to be in a normal pressure state, vacuumizing the furnace, flushing the inert gases into the furnace, repeatedly replacing oxygen in the horizontal vacuum electric furnace by vacuum and inert gases for more than 3 times, heating the material to 850 ℃ in the normal pressure state under the inert atmosphere, keeping the temperature for 60min, changing the gas pressure in the whole reaction process, collecting no liquid metal rubidium by using a wide-mouth bottle filled with liquid paraffin, reacting to generate metal rubidium, and collecting no liquid metal rubidium due to less reducing agent.
Example 4:
taking 50 g of rubidium chloride powder (99.5 percent, white) and 50 g of metal calcium particles (98.0 percent, average particle size of 5mm, silver white), uniformly mixing, putting into a stainless steel disc, putting into a horizontal vacuum electric furnace, controlling the vacuum degree in the furnace to be 0.01Pa before heating, flushing inert gases such as argon and the like to be in a normal pressure state, vacuumizing, flushing the inert gases, repeatedly replacing oxygen in the horizontal vacuum electric furnace for more than 3 times by using vacuum and inert gases, heating the material to 850 ℃ in the normal pressure state under the inert atmosphere, keeping the temperature for 60min, obviously changing the gas pressure in the whole reaction process, collecting liquid metal rubidium by using a wide-mouth bottle filled with liquid paraffin, and estimating that the metal rubidium is about 19 g and the metal rubidium yield is 54.29 percent.
Comparative example 7:
taking 50 g of rubidium chloride powder (99.5 percent, white) and 50 g of metal calcium particles (95.0 percent, average particle size of 5mm and silver white), uniformly mixing, putting the mixture into a stainless steel disc, putting the stainless steel disc into a horizontal vacuum electric furnace, controlling the vacuum degree in the furnace to be 0.01Pa before heating, flushing inert gases such as argon and the like to be in a normal pressure state, vacuumizing, flushing the inert gases, repeatedly replacing oxygen in the horizontal vacuum electric furnace for more than 3 times by using vacuum and inert gases, heating the material to 850 ℃ in the normal pressure state under the inert atmosphere, keeping the temperature for 60min, obviously changing the gas pressure in the whole reaction process, collecting liquid metal rubidium by using a wide-mouth bottle filled with liquid paraffin, estimating that the metal rubidium is about 17 g, the metal rubidium yield is 48.57 percent, and detecting the purity of the metal rubidium by adopting ICP-AES to be more than 99.50 percent, which is shown in Table 2.
Example 5:
taking 50 g of rubidium chloride powder (99.0 percent, white) and 50 g of metal calcium particles (99.9 percent, average particle size of 5mm, silver white), uniformly mixing, putting into a stainless steel disc, putting into a horizontal vacuum electric furnace, controlling the vacuum degree in the furnace to be 0.01Pa before heating, flushing inert gases such as argon and the like to be in a normal pressure state, vacuumizing, flushing the inert gases, repeatedly replacing oxygen in the horizontal vacuum electric furnace for more than 3 times by using vacuum and inert gases, heating the material to 850 ℃ in the normal pressure state under the inert atmosphere, keeping the temperature for 60min, obviously changing the gas pressure in the whole reaction process, collecting liquid metal rubidium by using a wide-mouth bottle filled with liquid paraffin, estimating that the metal rubidium is about 21 g, the direct yield of the metal rubidium is 60.00 percent, detecting the purity of the metal rubidium by adopting ICP-AES to be more than 99.50 percent, and showing in a table 2.
Comparative example 8:
taking 50 g of rubidium chloride (99.9 percent, white) and 50 g of metal calcium particles (99.9 percent, average particle size of 5mm, silver white), uniformly mixing, putting into a stainless steel disc, putting into a horizontal vacuum electric furnace, controlling the vacuum degree in the furnace to be 0.01Pa before heating, flushing inert gases such as argon and the like to be in an ordinary pressure state, vacuumizing, flushing the inert gases, repeatedly replacing oxygen in the horizontal vacuum electric furnace for more than 3 times by using vacuum and inert gases, heating the material to 850 ℃ in the ordinary pressure state under the inert atmosphere, preserving the temperature for 60min, obviously changing the gas pressure in the whole reaction process, collecting liquid metal rubidium by using a wide-mouth bottle filled with liquid paraffin, estimating that the metal rubidium is about 22.5 g, the direct yield of the metal rubidium is 64.29 percent, detecting the purity of the metal rubidium to be 99.99 percent by adopting ICP-AES (inductively coupled plasma-atomic emission Spectrometry) and showing in a table 2.
The process of each example and the yield of high purity rubidium prepared are shown in table 1, and the purity of high purity rubidium prepared is shown in table 2. From tables 1 and 2, it can be seen that: (1) the liquid metal rubidium can be collected only when the reaction temperature is 850 ℃ and above; (2) the yield of liquid metal rubidium is in direct proportion to the holding time of the highest temperature; (3) in order to obtain liquid metal rubidium, the mass ratio of metal calcium particles serving as a reducing agent to rubidium chloride powder cannot be lower than 1: 2; (4) the higher the purity of the metal calcium and the rubidium chloride is, the higher the purity of the obtained liquid metal rubidium is.
TABLE 1 statistical table of the process and yield of highly pure rubidium prepared in each example
TABLE 2 purity of the highly pure rubidium prepared
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The method for preparing high-purity rubidium by one-step thermal reduction of metal calcium is characterized by comprising the following steps:
(1) replacing oxygen in the horizontal vacuum electric furnace by adopting a vacuum pumping and inert gas filling mode;
(2) uniformly mixing metal calcium particles and rubidium chloride powder according to the mass ratio of (1:2) - (4:1), placing the mixture into the horizontal vacuum electric furnace treated in the step (1), heating to 850-1390 ℃ under the condition of inert atmosphere and normal pressure, and preserving heat for 30-120 min;
(3) after the display of a pressure gauge in the horizontal vacuum electric furnace rises, a vacuum pump is started, and metal rubidium steam is guided to a condensation part through a heated pipeline connected with the inner bore of the horizontal vacuum electric furnace to obtain liquid metal rubidium;
the furnace pipe of the horizontal vacuum electric furnace is in a horizontal cylindrical shape, the side surface of the furnace pipe is connected with a metal rubidium steam recovery pipeline, a vacuum pumping pipeline and an inflation pipeline, the metal rubidium steam recovery pipeline is a straight-through pipeline, one end, extending out of the horizontal vacuum electric furnace, of the metal rubidium steam recovery pipeline is arranged in a downward inclined mode, a discharging pipe and the horizontal plane form an included angle of 3-5 degrees, a material containing frame is arranged in the inner cavity, the inflation pipeline extends to the lower portion of the material containing frame, and a sealing ring is arranged between the furnace pipe of the horizontal vacuum electric furnace and the furnace cover;
the outer layer of the furnace chamber wall of the horizontal vacuum electric furnace is provided with a water jacket, the outer layer of the rubidium metal steam recovery pipeline is provided with an outer layer pipeline, the horizontal vacuum electric furnace further comprises an electronic water pump, the water inlet end of the electronic water pump is connected with a water storage tank, the water outlet end of the electronic water pump is communicated with the outer layer pipeline of the rubidium metal steam recovery pipeline, the outer layer pipeline is communicated with the water jacket on the outer layer of the furnace chamber wall, and the water jacket is connected with the water storage tank.
2. The method for preparing high-purity rubidium by one-step thermal reduction of metal calcium as claimed in claim 1, wherein in the step (1), the specific operation of replacing oxygen in the horizontal vacuum electric furnace by means of vacuumizing and filling inert gas is as follows: controlling the vacuum degree in the horizontal vacuum electric furnace at 0.01Pa, charging inert gas to normal pressure, vacuumizing, and charging inert gas, and repeatedly replacing oxygen in the horizontal vacuum electric furnace for more than 3 times by vacuumizing and charging inert gas.
3. The method for preparing high-purity rubidium by one-step thermal reduction of metal calcium according to claim 1, wherein a discharge pipe in a horizontal vacuum electric furnace is designed to form an included angle of 3-5 degrees with the horizontal plane; all metal rubidium steam recovery pipelines in the horizontal vacuum electric furnace adopt a straight-through type.
4. The method for preparing high-purity rubidium by one-step thermal reduction of calcium metal according to claim 1, wherein the heated pipeline is heated by circulating water heating, resistance heating or gas heating.
5. The method for preparing high-purity rubidium by carrying out thermal reduction on calcium metal according to any one of claims 1-4, wherein the purity of the calcium metal particles is more than 95%.
6. The method for preparing high-purity rubidium by carrying out thermal reduction on calcium metal according to any one of claims 1-4, wherein the particle size of calcium metal particles is less than 5 mm.
7. The method for preparing high-purity rubidium by carrying out thermal reduction on calcium metal according to claim 6, wherein the particle size of calcium metal particles is less than 2 mm.
8. The method for preparing high-purity rubidium by one-step thermal reduction of metal calcium as claimed in any one of claims 1 to 4, wherein the purity of the rubidium chloride powder is 98.0-99.9%.
9. The method for preparing high-purity rubidium by one-step thermal reduction of metal calcium as claimed in claim 8, wherein the purity of the rubidium chloride powder is 99.0% -99.9%.
10. The method for preparing high-purity rubidium by one-step calcium thermal reduction according to any one of claims 1-4, wherein the inert gas is one of argon, nitrogen or helium; the purity of the obtained liquid metal rubidium is 99.50-99.99%.
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| CN1067071A (en) * | 1991-05-23 | 1992-12-16 | 颜志明 | The industrialized producing technology technology and the equipment thereof of the vacuum-thermal method of non-ferrous metal such as strontium and barium |
| CN102131942A (en) * | 2008-07-31 | 2011-07-20 | 澳大利亚联邦科学与工业研究组织 | Production process |
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