CN111036932A - Method for preparing metal rhenium by liquid phase reduction - Google Patents
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- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
Abstract
The invention relates to the field of metal material preparation, in particular to a method for preparing metal rhenium by liquid phase reduction. The method comprises the following steps: 1) preparation of precursor liquid: dissolving a rhenium precursor in water to prepare a solution, adding polyvinylpyrrolidone and/or polyethylene glycol, and adding an alkali liquor to adjust the pH value of the solution to obtain a precursor solution; 2) preparing a reducing solution: dissolving a reducing agent in water to prepare a reducing solution; 3) reduction reaction: and slowly dropwise adding the prepared reducing solution into the precursor solution through a funnel, standing at constant temperature after the reducing solution is completely added, and filtering after the standing at constant temperature is finished to obtain the rhenium metal powder. The preparation process is simple and efficient, and is easy to popularize and use; the yield of the metal rhenium powder is high, and the waste of raw materials is less; the preparation is carried out at medium and low temperature, so that the preparation is safer, and part of materials can be recycled.
Description
Technical Field
The invention relates to the field of metal material preparation, in particular to a method for preparing metal rhenium by liquid phase reduction.
Background
Rhenium and rhenium alloys have become indispensable materials in the aerospace industry due to their special properties such as high melting point, high strength, good plasticity, and excellent mechanical stability. The rhenium content of the single crystal superalloy is a 'surrogate mark' of an aeroengine material, for example, the rhenium content of a fourth generation single crystal superalloy blade reaches 4.5-6%, so that the metal rhenium can be considered as a symptomatic medicine for relieving Chinese 'dynamic heart disease'.
However, rhenium is an extremely important strategic metal and is present in the earth's crust in extremely rare amounts. In particular, the largest rhenium producer in the world, the U.S. molybdenum metal company, monopolizes most of rhenium in chile, mexico, and hassakestan, in long-term contracts, reserving all indigenous products and a significant portion of imported products through U.S. indigenous reserve production technologies, rendering metallic rhenium expensive.
The extraction research of rhenium is started late in China. Currently, ammonium rhenate is only recovered and extracted from molybdenum smelting soot and copper smelting flue gas purification waste acid. The metal rhenium is mainly prepared by a high-temperature hydrogen reduction method in industry, and the process has the problems of high temperature, large energy consumption, low efficiency and the like, so that the production enterprises of the metal rhenium are few. In recent years, the price of the ammonium rhenate begins to drop due to the phenomenon of market lag, but the price of the metallic rhenium is always high. Therefore, research and development of a high-efficiency and low-energy-consumption metal rhenium preparation technology are extremely important for promoting the development of the rhenium industry and even the aerospace industry in China.
Since metallic rhenium belongs to the refractory metal, the subsequent processing thereof is generally carried out in a powder metallurgy process, and the preparation of metallic rhenium powder is therefore the basis for the production of rhenium alloys. Currently, the powdered metal rhenium is generally produced by taking ammonium rhenate as a raw material and carrying out multiple high-temperature hydrogen reductions. However, the rhenium oxide is volatile, and the preparation process is complicated.
The chinese patent office disclosed an invention patent application of a method for preparing rhenium metal in 2017, 3, 15, with application publication number CN 106498194A. The method comprises the steps of preparing high-purity metal rhenium powder by taking ammonium perrhenate as a raw material through a two-step method, preparing high-purity superfine ammonium perrhenate through ultrasonic-assisted crystallization and vacuum drying in the first step, and reducing the ammonium perrhenate into the high-purity metal rhenium powder through a hydrogen reduction method in the second step. The method has strong adaptability to raw materials, improves the utilization rate of the raw materials, and can prepare the high-purity metal rhenium powder by the ultrasonic crystallization-hydrogen reduction combined process. However, the invention also adopts the high-temperature hydrogen reduction process, still has the problems of high energy consumption, low efficiency and the like in the process, and the yield is reduced due to the volatilization of oxides in the high-temperature hydrogen reduction process.
The chinese patent office also discloses an invention patent application of a preparation method of high-purity rhenium powder in 2004, 11 month and 17 days, and the granted publication number is CN 1175951C. The method comprises the steps of heating and concentrating a high-purity ammonium rhenate solution to be in a supersaturated state, cooling to room temperature, continuously stirring in the cooling process, filtering, drying to prepare ammonium rhenate powder, and reducing the ammonium rhenate powder to high-purity rhenium powder in hydrogen at the temperature of (400-600 ℃). The invention does not need grinding and screening processes, adopts lower reduction temperature in the hydrogen reduction process, can reduce the content of impurity elements in rhenium powder, and can meet the requirement of industries of aerospace, electronics and the like on the purity of rhenium powder. Although the method has lower energy consumption compared with the common hydrogen thermal reduction, the oxide volatilization exists in the hydrogen reduction process, which causes the yield to be reduced.
The chinese patent office also discloses an inventive patent application of a method for preparing metal rhenium by hydrothermal hydrogen liquid phase reduction in 2019, 2.19.8, with application publication number CN 109351985A. The preparation method comprises the following steps: 1) preparing a precursor solution, and concentrating until the precursor solution forms a supersaturated state; 2) carrying out induced regulation self-assembly on the supersaturated precursor solution, and controlling the conditions of polymer species, reaction temperature, reaction time length, molar ratio and the like in the process to prepare an intermediate; 3) directly carrying out hydrothermal hydrogen reduction on the intermediate to obtain nano rhenium powder slurry; 4) and (3) ageing, separating and drying the nano rhenium powder slurry, and removing the polymer to obtain the metal rhenium. According to the technical scheme, the metal rhenium powder can be prepared with low energy consumption, but the problems of complicated process, long whole preparation flow and low preparation efficiency still exist, and a certain potential safety hazard exists in the hydrothermal hydrogen reduction process in the technical scheme.
Disclosure of Invention
The invention provides a method for preparing rhenium metal by liquid-phase reduction, aiming at solving the problems that high-temperature hydrogen reduction is needed in the existing preparation method of rhenium metal, potential safety hazards exist, the whole process is complex and trivial, the energy consumption is high, the efficiency is low, the yield is reduced due to volatilization of oxides, and the like. The main purpose of it includes: firstly, the preparation process of the metal rhenium powder is simplified, and the preparation efficiency is improved; ensuring good preparation effect and improving the yield of the product metal rhenium powder; and thirdly, high-temperature hydrogen reduction is avoided, the full-process medium-low temperature reaction is realized to prepare the metal rhenium powder, the preparation safety is improved, the energy consumption is saved, the requirement on equipment is reduced, and the large-scale industrial production is realized.
In order to achieve the purpose, the invention adopts the following technical scheme.
A method for preparing metallic rhenium by liquid phase reduction, the method comprising the steps of:
1) preparation of precursor liquid: dissolving a rhenium precursor in water to prepare a solution, adding polyvinylpyrrolidone and/or polyethylene glycol, and adding an alkali liquor to adjust the pH value of the solution to obtain a precursor solution;
2) preparing a reducing solution: dissolving a reducing agent in water to prepare a reducing solution;
3) reduction reaction: and slowly dropwise adding the prepared reducing solution into the precursor solution through a funnel, standing at constant temperature after the reducing solution is completely added, and filtering after the standing at constant temperature is finished to obtain the rhenium metal powder.
In the technical scheme of the invention, firstly, a rhenium precursor is dissolved in water to prepare a solution, and at least one of polyvinylpyrrolidone and polyethylene glycol is added to form the protection and dispersion effects on the rhenium precursor. Rhenium precursors, especially rhenate substances, have poor solubility and stability in water, are easy to separate out, agglomerate and the like, can be prevented from agglomerating and separating out after polyvinylpyrrolidone and/or polyethylene glycol are added, and are promoted to be uniformly dispersed, so that potential safety hazards caused by overhigh heat released by single-point reaction in the subsequent reduction process are avoided, and impurities are easily introduced due to overlarge granular metal rhenium formed by the single-point reaction; in the subsequent reduction process, the high-valence rhenium is slowly reduced to the zero-valence rhenium metal by slowly dripping the reducing solution, the reaction process is high in controllability and can be stopped at any time so as to ensure the safety in the process of preparing the metal rhenium powder, the constant-temperature standing process is free from heating to high temperature, the energy consumption is saved, the medium-low temperature reaction in the whole process is realized, and the prepared metal rhenium powder has high purity.
Preferably, the rhenium precursor in step 1) comprises soluble rhenate, rhenic acid and perrhenic acid; the concentration of the rhenium precursor in the precursor liquid is 0.12-0.16 mol/L.
Rhenates, perrhenates, and the like may be used to enhance the rhenium source. The rhenium concentration in the precursor liquid is controlled to be at a lower level, so that the rhenium precursor can be ensured to be kept stable and not separated out in the solution, explosive reduction in the subsequent process of reducing rhenium metal powder can be avoided, and the safety is further improved.
Preferably, the addition amount of the polyvinylpyrrolidone and/or the polyethylene glycol in the precursor liquid in the step 1) is 5-15 wt% of the total mass of the rhenium precursor.
The polyvinylpyrrolidone and/or polyethylene glycol with too low concentration can not realize good protection and dispersion effects, while the rhenium concentration is reduced and the reduction process is slow due to too high concentration, so that the rhenium yield is reduced, and the optimal preparation effect can be realized within the dosage range.
Preferably, the alkali liquor in the step 1) is ammonia water; the pH value of the precursor liquid is adjusted to 5-11 in the pH value adjusting process.
It is comparatively stable when pH value is adjusted to the aqueous ammonia, be difficult for introducing impurity, can not produce the rhenium thing and deposit, and on the other hand can improve the solubility of rhenium precursor to a certain extent behind the dropwise add aqueous ammonia, further ensures that it can not appear, and the aqueous ammonia can absorb the following a large amount of heats that reduction reaction released, releases the ammonia after the absorption and can collect, carries out the recycle that relapses, material saving more.
Preferably, the reducing agent in step 2) comprises hydrazine hydrate and/or sodium borohydride.
Hydrazine hydrate and sodium borohydride are both high-efficiency strong reducing agents, and nitrogen or boric acid is produced after reduction; in the invention, the reducing agent is preferably hydrazine hydrate, which has stronger reducibility and quicker reaction, and harmless nitrogen generated after reduction can be directly discharged.
Preferably, the concentration of the reducing agent in the reducing solution in the step 2) is 0.18-0.28 mol/L.
Too high a concentration of reducing agent can lead to too violent a reaction process; too low a concentration leads to slow reduction and lower yields of metal rhenium powder.
Preferably, the volume ratio of the reducing solution to the precursor solution used in step 3) is 1: (4.5-6).
The concentration of the reducing agent in the reducing solution is controlled to enable the reducing agent and the reducing solution to have a proper volume ratio, so that the situation that the precursor solution is continuously diluted during the generation of violent reaction and the dropping of the reducing solution can be avoided, and the problem that the rhenium concentration is reduced and is difficult to reduce is caused.
Preferably, the constant-temperature standing in the step 3) is carried out at the temperature of 20-80 ℃.
The metal rhenium powder can be quickly and stably reduced and prepared within the temperature range, and the temperature range is at medium and low temperature, so that the energy consumption is lower and the method is safer.
The invention has the beneficial effects that:
1) the preparation process is simple and efficient, and is easy to popularize and use;
2) the yield of the metal rhenium powder is high, and the utilization rate of raw materials is high;
3) the preparation is carried out at medium and low temperature, so that the preparation is safer, and part of materials can be recycled.
Detailed Description
The present invention will be described in further detail with reference to specific examples. Those skilled in the art will be able to implement the invention based on these teachings. Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Unless otherwise specified, the raw materials used in the examples of the present invention are all commercially available or available to those skilled in the art; unless otherwise specified, the methods used in the examples of the present invention are all those known to those skilled in the art.
Example 1
A method for preparing metallic rhenium by liquid phase reduction, the method comprising the steps of:
1) preparation of precursor liquid: dissolving rhenic acid in water to prepare a solution, adding polyvinylpyrrolidone with the total mass of the rhenic acid being 5 wt% and ammonia water to adjust the pH value of the solution to 6 to obtain a precursor solution, wherein the initial concentration of the rhenic acid in the precursor solution is 0.12 mol/L;
2) preparing a reducing solution: dissolving hydrazine hydrate in water to prepare 0.18mol/L reducing solution;
3) reduction reaction: according to the volume ratio of the reducing liquid to the precursor liquid of 1: 5.5, slowly dripping the prepared reducing solution into the precursor solution through a funnel, dripping 5% of the total volume of the reducing solution every minute in the dripping process, standing at the constant temperature of 60 ℃ for 30min after the reducing solution is completely added, filtering to obtain metal rhenium powder after the constant-temperature standing reaction is finished, and carrying out XRD analysis on the metal rhenium powder;
4) and (3) heat treatment: placing the prepared metal rhenium powder in inert gas, heating to 100 ℃ at the speed of 6 ℃/min, preserving heat for 1h, then heating to 200 ℃ at the speed of 6 ℃/min, preserving heat for 3h, and furnace cooling to obtain heat-treated rhenium powder;
5) and carrying out XRD analysis on the heat-treated rhenium powder.
Example 2
A method for preparing metallic rhenium by liquid phase reduction, the method comprising the steps of:
1) preparation of precursor liquid: dissolving perrhenic acid in water to prepare a solution, adding polyethylene glycol accounting for 11 wt% of the total mass of a rhenium precursor, adding ammonia water to adjust the pH value of the solution to 7, and obtaining a precursor solution, wherein the initial concentration of the perrhenic acid in the precursor solution is 0.15 mol/L;
2) preparing a reducing solution: dissolving sodium borohydride in water to prepare 0.28mol/L reducing solution;
3) reduction reaction: according to the volume ratio of the reducing liquid to the precursor liquid of 1: 4.5, slowly dripping the prepared reducing solution into the precursor solution through a funnel, wherein 3% of the total volume of the reducing solution is dripped every minute in the dripping process, standing at the constant temperature of 80 ℃ for 35min after the reducing solution is completely added, filtering to obtain metal rhenium powder after the constant-temperature standing reaction is finished, and carrying out XRD analysis on the metal rhenium powder;
4) and (3) heat treatment: placing the prepared metal rhenium powder in inert gas, heating to 100 ℃ at the speed of 5 ℃/min, preserving heat for 1h, then heating to 200 ℃ at the speed of 6 ℃/min, preserving heat for 3h, and furnace cooling to obtain heat-treated rhenium powder;
5) and carrying out XRD analysis on the heat-treated rhenium powder.
Example 3
A method for preparing metallic rhenium by liquid phase reduction, the method comprising the steps of:
1) preparation of precursor liquid: dissolving ammonium rhenate in water to prepare a solution, adding a mixture of polyvinylpyrrolidone and polyethylene glycol with the total mass of the ammonium rhenate being 15 wt%, wherein the mass ratio of the polyvinylpyrrolidone to the polyethylene glycol in the mixture is 1: 1, adding ammonia water to adjust the pH value of a solution to 11 to obtain a precursor solution, wherein the concentration of ammonium rhenate in the precursor solution is 0.16 mol/L;
2) preparing a reducing solution: dissolving hydrazine hydrate in water to prepare 0.28mol/L reducing solution;
3) reduction reaction: according to the volume ratio of the reducing liquid to the precursor liquid of 1: 5, slowly dripping the prepared reducing solution into the precursor solution through a funnel, dripping 5% of the total volume of the reducing solution every minute in the dripping process, standing at a constant temperature of 20 ℃ for 40min after the reducing solution is completely added, filtering to obtain metal rhenium powder after the constant-temperature standing reaction is finished, and carrying out XRD analysis on the metal rhenium powder;
4) and (3) heat treatment: placing the prepared metal rhenium powder in inert gas, heating to 100 ℃ at the speed of 6 ℃/min, preserving heat for 1h, then heating to 200 ℃ at the speed of 6 ℃/min, preserving heat for 3h, and furnace cooling to obtain heat-treated rhenium powder;
5) and carrying out XRD analysis on the heat-treated rhenium powder.
Example 4
A method for preparing metallic rhenium by liquid phase reduction, the method comprising the steps of:
1) preparation of precursor liquid: dissolving ammonium rhenate in water to prepare a solution, adding polyvinylpyrrolidone and polyethylene glycol with the total mass of 10 wt% of the ammonium rhenate, wherein the mass ratio of the polyvinylpyrrolidone to the polyethylene glycol in the mixture is 1: 4, adding ammonia water to adjust the pH value of the solution to 9 to obtain a precursor solution, wherein the concentration of ammonium rhenate in the precursor solution is 0.14 mol/L;
2) preparing a reducing solution: dissolving hydrazine hydrate or sodium borohydride in water to prepare 0.28mol/L reducing solution;
3) reduction reaction: according to the volume ratio of the reducing liquid to the precursor liquid of 1: 6, slowly dripping the prepared reducing solution into the precursor solution through a funnel, dripping 5% of the total volume of the reducing solution every minute in the dripping process, standing at a constant temperature of 60 ℃ for 30min after the reducing solution is completely added, filtering to obtain metal rhenium powder after the constant-temperature standing reaction is finished, and carrying out XRD analysis on the metal rhenium powder;
4) and (3) heat treatment: placing the prepared metal rhenium powder in inert gas, heating to 100 ℃ at the speed of 6 ℃/min, preserving heat for 1h, then heating to 200 ℃ at the speed of 6 ℃/min, preserving heat for 3h, and furnace cooling to obtain heat-treated rhenium powder;
5) and carrying out XRD analysis on the heat-treated rhenium powder.
Example 5
A method for preparing metallic rhenium by liquid phase reduction, the method comprising the steps of:
1) preparation of precursor liquid: dissolving ammonium rhenate in water to prepare a solution, adding polyvinylpyrrolidone and polyethylene glycol with the total mass of 10 wt% of the ammonium rhenate, wherein the mass ratio of the polyvinylpyrrolidone to the polyethylene glycol in the mixture is 3: 2, adding ammonia water to adjust the pH value of the solution to 9.5 to obtain a precursor solution, wherein the concentration of ammonium rhenate in the precursor solution is 0.15 mol/L;
2) preparing a reducing solution: dissolving hydrazine hydrate or sodium borohydride in water to prepare 0.28mol/L reducing solution;
3) reduction reaction: according to the volume ratio of the reducing liquid to the precursor liquid of 1: 5, slowly dripping the prepared reducing solution into the precursor solution through a funnel, dripping 5% of the total volume of the reducing solution every minute in the dripping process, standing at the constant temperature of 65 ℃ for 30min after the reducing solution is completely added, filtering to obtain metal rhenium powder after the constant-temperature standing reaction is finished, and carrying out XRD analysis on the metal rhenium powder;
4) and (3) heat treatment: placing the prepared metal rhenium powder in inert gas, heating to 100 ℃ at the speed of 6 ℃/min, preserving heat for 1h, then heating to 200 ℃ at the speed of 6 ℃/min, preserving heat for 3h, and furnace cooling to obtain heat-treated rhenium powder;
5) and carrying out XRD analysis on the heat-treated rhenium powder.
The test results of the sampling analysis of examples 1 to 5 are shown in table 1 below, and all the test results are the average of the effective values of ten tests.
Table 1 results of sampling analysis in examples 1 to 5.
It is obvious from the above table that the metal rhenium prepared by the method has extremely high purity, wherein the content of impurity elements is low, and the purity of the metal rhenium prepared after reduction can be further improved after heat treatment and crystallization, and the whole preparation process is simple and safe.
Claims (8)
1. A method for preparing metallic rhenium by liquid phase reduction, characterized in that the method comprises the following steps:
1) preparation of precursor liquid: dissolving a rhenium precursor in water to prepare a solution, adding polyvinylpyrrolidone and/or polyethylene glycol, and adding an alkali liquor to adjust the pH value of the solution to obtain a precursor solution;
2) preparing a reducing solution: dissolving a reducing agent in water to prepare a reducing solution;
3) reduction reaction: and slowly dropwise adding the prepared reducing solution into the precursor solution through a funnel, standing at constant temperature after the reducing solution is completely added, and filtering after the standing at constant temperature is finished to obtain the rhenium metal powder.
2. The method for preparing metallic rhenium through liquid-phase reduction according to claim 1, wherein the rhenium precursor in the step 1) comprises soluble rhenate, rhenic acid and perrhenic acid; the concentration of the rhenium precursor in the precursor liquid is 0.12-0.16 mol/L.
3. The method for preparing rhenium metal by liquid-phase reduction according to claim 1 or 2, wherein the addition amount of polyvinylpyrrolidone and/or polyethylene glycol in the precursor liquid in the step 1) is 5-15 wt% of the total mass of the rhenium precursor.
4. The method for preparing metallic rhenium by liquid phase reduction according to claim 1 or 2, characterized in that the alkali liquor in step 1) is ammonia water; the pH value of the precursor liquid is adjusted to 5-11 in the pH value adjusting process.
5. The method for preparing metallic rhenium through liquid-phase reduction according to claim 1, wherein the reducing agent in the step 2) comprises hydrazine hydrate and/or sodium borohydride.
6. The method for preparing rhenium metal by liquid-phase reduction according to claim 1 or 5, wherein the concentration of the reducing agent in the reducing solution in the step 2) is 0.18-0.28 mol/L.
7. The method for preparing rhenium metal by liquid-phase reduction according to claim 1, wherein the volume ratio of the reducing liquid to the precursor liquid used in the step 3) is 1: (4.5-6).
8. The method for preparing rhenium metal by liquid-phase reduction according to claim 1, wherein the constant-temperature standing in the step 3) is carried out at 20-80 ℃.
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