CN109550935B - Method for producing 5N metal rhenium by composite method - Google Patents
Method for producing 5N metal rhenium by composite method Download PDFInfo
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Abstract
The invention relates to a method for producing 5N metal rhenium by a composite method. The technical scheme is as follows: the method comprises the steps of utilizing commercially available metal rhenium powder with the purity of 4N, removing most of metal and non-metal impurities through high-pressure acidolysis, rinsing the obtained product, preparing ultrapure rhenium oxide through a sublimation method, and preparing ultrapure metal rhenium powder with the purity of more than 5N through metal reduction. The method solves the problems that the traditional high-temperature method cannot remove high-melting-point metal impurities and the mainstream ion exchange method is difficult to remove trace non-metal impurities, and has the advantages of short flow, easy reaction, simple and efficient operation and great scientific significance and application value.
Description
Technical Field
The invention belongs to the technical field of powder metallurgy manufacturing, and particularly relates to a method for producing rhenium metal with the purity of 99.999% (the purity of 99.999% is 5N for short) by adopting a high-pressure acidolysis and sublimation composite method.
Background
Rhenium is the most important strategic metal for human beings, and is widely applied to various fields of national economy, particularly military fields, due to high melting point, high-temperature strength, hardness, wear resistance and excellent heat conduction and electric conduction performance. From the 50 s of the last century, the rhenium industrial system has gradually developed from resource acquisition research to industrialization and practicability, and in recent years, due to the development of the electronic industry, an increasingly strong demand is provided for ultra-high purity rhenium with purity of 5N (purity of 99.999%) or more.
The rhenium metal is prepared by enriching rhenium-containing metal salt from flue gas or waste (tail) water during production of rhenium-containing molybdenum ore or copper-molybdenum ore, purifying and removing impurities, and reducing to obtain metal rhenium powder, wherein the rhenium metal with purity of 4N (purity of 99.99% is simply referred to as 4N) is mostly prepared at present, and the preparation process of the rhenium metal with purity of 4N is relatively mature. However, the preparation of rhenium with purity of more than 5N is usually complicated, multiple chemical means are used for repeated purification and purification at the stage of rhenium-containing metal salt, the process is complicated, the reliability is low, and the environmental pollution of chemicals is great, so that the difficulty in producing 5N ultrapure rhenium is great, the efficiency is low, the cost is high, and the requirement of the electronic industry on the ultrapure rhenium is difficult to meet.
Disclosure of Invention
The invention aims to overcome the defects and aims to bypass the complex purification process of rhenium-containing metal salt, directly remove trace impurities in the metal rhenium by a high-pressure acidolysis and sublimation composite method from commercial purity 4N metal rhenium, and produce the metal rhenium powder with the purity of more than 5N by the shortest process.
The technical scheme adopted by the invention is as follows: a method for producing 5N metal rhenium by a composite method, which adopts the composite method of high-pressure acidolysis and sublimation to produce the 5N metal rhenium, and comprises the following steps:
1) high-pressure acidolysis: mixing the raw material metal rhenium powder with acid liquor, placing the mixture in a high-pressure container, stirring the mixture for reaction for 1 to 3 hours at the pressure of 0.1 to 3.5MPa and the temperature of 120 ℃ and 180 ℃, cooling and filtering the mixture to obtain the impurity-removed rhenium powder after high-pressure acidolysis;
further, the purity of the raw metal rhenium powder is 99.99%, and the content of typical non-metallic elements is not more than 40ppm, such as: si content is not more than 10ppm, C content is not more than 40ppm, and S content is not more than 10 ppm.
Further, the acid solution is hydrochloric acid, nitric acid or hydrofluoric acid with the volume percentage concentration of 1-3%.
Furthermore, according to the feed-liquor ratio, the raw material metal rhenium powder and acid liquor are 1g (3-5) mL.
Further, the stirring speed is 30 to 80 rpm.
Further, the reaction is stirred for 1 to 3 hours under the pressure of 1.5 to 3.5MPa and the temperature of 140 ℃ and 180 ℃.
2) Rinsing: and (3) sequentially rinsing the perrhene-removed powder obtained in the step 1) after high-pressure acidolysis by using a neutralizing agent and deionized water until the pH value is 6-7.
Further, the neutralizing agent is ammonia water, and the deionized water resistance is 8-14 megaohms.
3) Sublimation and purification: putting the rinsed impurity-removed rhenium powder obtained in the step 2) into a sublimation furnace, introducing oxygen, and reacting for 1-3h at 400-;
further, the sublimation furnace is a rhenium tube, a rhenium-lined metal tube or a rhenium-lined quartz tube.
4) And (3) metal reduction: placing the rhenium oxide obtained in the step 3) in a specific tool, then placing the rhenium oxide in a reduction furnace, introducing hydrogen, heating to 400-500 ℃, and reducing for 1-2 hours; then the temperature is continuously raised to 900 ℃ for reduction for 1-2 hours.
Further, the specific tool is a rhenium boat or a rhenium-lined molybdenum boat.
Further, the flow rate of hydrogen is 4 to 7m3In terms of hours.
Furthermore, the reduction furnace is a straight-through type non-link reduction furnace.
The invention has the beneficial effects that:
1. the method has the advantages of wide raw material source, short flow, simple operation, high reliability and more stable product quality, and can meet the requirements of the electronic industry and other precision technologies on 5N ultra-pure rhenium.
2. The method of the invention first removes most of the metallic and non-metallic impurities from the metallic rhenium powder by high pressure acidolysis.
3. According to the method, impurities are further removed from the metal rhenium powder subjected to high-pressure acidolysis through sublimation purification.
4. The method solves the problems that the traditional high-temperature method cannot remove high-melting-point metal impurities and the mainstream ion exchange method is difficult to remove trace non-metal impurities, and has the advantages of short flow, easy reaction, simple and efficient operation and great scientific significance and application value.
Drawings
FIG. 1 is a general process flow diagram of the present invention.
Detailed Description
Example l
1) Selecting materials: commercial general metal rhenium powder with the purity of 4N (the purity is 99.99 percent), the content of non-metal elements Si of less than 10ppm and the content of C of less than 20ppm is selected.
2) High-pressure acidolysis: mixing the raw material metal rhenium powder with a hydrochloric acid solution with the volume percentage concentration of 2% according to the material-to-liquid ratio of 1g:4mL, placing the mixture in a high-pressure container, reacting for 1 hour at the pressure of 0.2MPa, the temperature of 120 ℃ and 130 ℃ and the stirring speed of 40rpm, removing most of metal and non-metal impurities, cooling and filtering to obtain the perrhene removal powder after high-pressure acidolysis.
3) Rinsing: washing the deduplicated rhenium powder subjected to high-pressure acidolysis by using neutralizing agent ammonia water until the pH value is 9, and then washing the deduplicated rhenium powder by using deionized water with the resistance of 8-14 megaohms until the pH value is 6.5.
4) Sublimation and purification: putting the rinsed and high-pressure acidolyzed perrhene-removing powder obtained in the step 3) into a rhenium tube sublimation furnace, and introducing oxygen with the purity of 99.999 percent in an amount of 1.2m3And/h, reacting at 500 ℃ for 2h, and further removing impurities in the metal rhenium powder after high-pressure acidolysis to obtain the ultra-pure rhenium oxide.
5) And (3) metal reduction: placing the ultra-pure rhenium oxide obtained in the step 4) into a rhenium boat, placing the rhenium boat into a straight-through type non-linked reduction furnace, introducing hydrogen with the purity of 99.999 percent, and controlling the flow velocity of the hydrogen to be 4-7m3And/h, heating to 400 ℃ firstly, carrying out reduction reaction for 1 h, then continuing heating to 750 ℃ and carrying out reduction reaction for 1 h.
By the above method, the purity of the obtained rhenium powder is more than 99.999%, the oxygen content is 1900ppm, and the yield is 300 g/h.
Example 2
1) Selecting materials: commercial general metal rhenium powder with purity of 4N (purity of 99.99%), S content of less than 5ppm and Si content of less than 10ppm is selected.
2) High-pressure acidolysis: mixing raw material metal rhenium powder with a nitric acid solution with the volume percentage concentration of 2% according to the material-liquid ratio of 1g:4mL, placing the mixture in a high-pressure container, reacting for 1 hour at the pressure of 1.5MPa, the temperature of 130-.
3) Rinsing: washing the deduplicated rhenium powder subjected to high-pressure acidolysis by using neutralizing agent ammonia water until the pH value is 9, and then washing the deduplicated rhenium powder by using deionized water with the resistance of 12-14 megaohms until the pH value is 7.
4) Sublimation and purification: putting the rinsed and high-pressure acidolyzed rhenium-removing powder obtained in the step 3) into a rhenium-lined metal tube sublimation furnace, introducing oxygen with the purity of 99.999 percent, and introducing the oxygen with the amount of 1m3And/h, reacting for 3h at 500 ℃, and further removing impurities in the metal rhenium powder after high-pressure acidolysis to obtain the ultra-pure rhenium oxide.
5) And (3) metal reduction: placing the ultra-pure rhenium oxide obtained in the step 4) in a molybdenum boat lined with rhenium, and placing the molybdenum boat into a straight-through type non-link reduction furnaceIntroducing hydrogen with the purity of 99.999 percent at the flow rate of 4-7m3And/h, heating to 400 ℃ firstly, carrying out reduction reaction for 1 h, then continuing heating to 850 ℃ and carrying out reduction reaction for 1 h.
By the method, the purity of the obtained rhenium powder is more than 99.999 percent, the oxygen content is 1500ppm, and the yield is 600 g/h.
Example 3
1) Selecting materials: commercial general metal rhenium powder with the purity of 4N (the purity is 99.99 percent), the content of non-metal elements Si of less than 7ppm and the content of C of less than 35ppm is selected.
2) High-pressure acidolysis: mixing raw material metal rhenium powder with hydrofluoric acid solution with the volume percentage concentration of 2% according to the material-to-liquid ratio of 1g:5mL, placing the mixture in a high-pressure container, reacting for 1 hour at the pressure of 3MPa, the temperature of 130-.
3) Rinsing: washing the deduplicated rhenium powder subjected to high-pressure acidolysis by using neutralizing agent ammonia water until the pH value is 9, and then washing the deduplicated rhenium powder by using deionized water with the resistance of 12-14 megaohms until the pH value is 7.5.
4) Sublimation and purification: putting the rinsed rhenium-removing powder obtained in the step 3) into a quartz tube sublimation furnace lined with rhenium, and introducing oxygen with the purity of 99.999 percent in an amount of 1.5m3And h, reacting at 500 ℃ for 2.5h, and further removing impurities in the metal rhenium powder after high-pressure acidolysis to obtain the ultra-pure rhenium oxide.
5) And (3) metal reduction: placing the ultra-pure rhenium oxide obtained in the step 4) into a rhenium boat, placing the rhenium boat into a straight-through type non-linked reduction furnace, introducing hydrogen with the purity of 99.999 percent, and controlling the flow velocity of the hydrogen to be 4-7m3And/h, heating to 400 ℃ firstly, carrying out reduction reaction for 1 h, then continuing heating to 900 ℃, and carrying out reduction reaction for 1 h.
By the above method, the purity of the obtained rhenium powder is more than 99.999%, the oxygen content is 1000ppm, and the yield is 500 g/h.
Claims (8)
1. The method for producing 5N metal rhenium by a composite method is characterized in that the 5N metal rhenium is produced by the composite method of high-pressure acidolysis and sublimation, and comprises the following steps:
1) high-pressure acidolysis: mixing the raw material metal rhenium powder with acid liquor, placing the mixture in a high-pressure container, stirring the mixture for reaction for 1 to 3 hours at the pressure of 0.1 to 3.5MPa and the temperature of 120 ℃ and 180 ℃, cooling and filtering the mixture to obtain the impurity-removed rhenium powder after high-pressure acidolysis;
2) rinsing: rinsing the deduplicated rhenium powder obtained in the step 1) after high-pressure acidolysis with a neutralizer and deionized water in sequence until the pH is = 6-7;
3) sublimation and purification: putting the rinsed impurity-removed rhenium powder obtained in the step 2) into a sublimation furnace, introducing oxygen, and reacting for 1-3h at 400-;
4) and (3) metal reduction: placing the rhenium oxide obtained in the step 3) into a rhenium boat or a molybdenum boat lined with rhenium, then placing the rhenium oxide into a reduction furnace, introducing hydrogen, heating to 400-500 ℃, and reducing for 1-2 hours; then the temperature is continuously raised to 900 ℃ for reduction for 1-2 hours.
2. A method for producing rhenium from 5N metal by a composite process as claimed in claim 1, wherein: in the step 1), the purity of the raw material metal rhenium powder is 99.99%.
3. A method for producing rhenium from 5N metal by a composite process as claimed in claim 1, wherein: in the step 1), the raw material metal rhenium powder is acid solution =1g (3-5) mL according to the feed-to-liquid ratio.
4. A method for producing rhenium from 5N metal by a composite process as claimed in claim 1, wherein: in the step 1), the stirring speed is 30-80 rpm.
5. A method for producing rhenium from 5N metal by a composite process as claimed in claim 1, wherein: step 1) high-pressure acidolysis: mixing the raw material metal rhenium powder with acid liquor, placing the mixture in a high-pressure container, stirring the mixture for reaction for 1 to 3 hours at the pressure of 1.5 to 3.5MPa and the temperature of 140 ℃ and 180 ℃, cooling and filtering the mixture to obtain the impurity-removed rhenium powder after high-pressure acidolysis.
6. A method for producing rhenium from 5N metal by a composite process as claimed in claim 1, wherein: in the step 2), the neutralizer is ammonia water, and the deionized water resistance is 8-14 megaohms.
7. A method for producing rhenium from 5N metal by a composite process as claimed in claim 1, wherein: in the step 3), the sublimation furnace is a rhenium tube, a rhenium-lined metal tube or a rhenium-lined quartz tube.
8. A method for producing rhenium from 5N metal by a composite process as claimed in claim 1, wherein: in the step 4), the flow rate of the hydrogen is 4-7m3In terms of hours.
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