Rhenium extraction agent, preparation method thereof and method for extracting and separating rhenium

Abstract

The invention provides a rhenium extraction agent, a preparation method thereof and a method for extracting and separating rhenium, and belongs to the field of metal extraction and separation in hydrometallurgy. According to the method, the extracting agent is composed of the secondary amine, the diphosphorus oxide and the diluent, the secondary amine and the diphosphorus oxide have a good synergistic effect, and high selectivity can be achieved on rhenate in the extraction process, so that rhenate containing other metals is directly extracted, the extracting agent does not need to be saponified or activated, and the extraction efficiency is improved. Acid-base or an oxidizing agent is not needed, so that the extraction process is simple and efficient, and meanwhile, the purity of the rhenate product obtained through purification and separation is high; different extractant formulas can be selected according to different rhenium molybdate systems, and the extractant is flexible and changeable; in addition, the secondary amine and the diphosphorus oxide are cheap and easy to obtain, the cost is low, and after reverse extraction, the extraction agent can be reused, and is green and environment-friendly.

Description

Technical Field

[0001] The invention relates to the field of metal extraction and separation in hydrometallurgy, and in particular to a rhenium extractant and a preparation method thereof, and a method for extracting and separating rhenium. Background Art

[0002] Rhenium is an extremely rare metal element on Earth. It has a very low abundance in the Earth's crust and is one of the least abundant nonferrous metals on Earth. It rarely forms independent minerals during the Earth's evolution. Most of it exists in other minerals in a similar manner. It is a typical dispersed element. Rhenium is widely used in aerospace, medical, information, chemical, metallurgical and national defense fields due to its high melting point, high density, excellent ductility, formability and anti-carburization properties.

[0003] Rhenium is present in very low concentrations in the earth's crust and is mainly found in molybdenite. However, since the atomic radius and ionic radius of rhenium and molybdenum are very similar, and their chemical properties such as coordination ability are also very similar, it is very difficult to separate rhenium from minerals. Therefore, the separation of rhenium and molybdenum is an important research field in separation science and has received extensive attention.

[0004] In the separation and purification methods of rhenium, the research is mainly aimed at the separation of rhenium and molybdenum, including precipitation method, ion exchange method and solvent extraction method. Among them, the solvent extraction method has the advantages of high separation efficiency, large processing capacity, low production cost and high product purity, and is becoming more and more popular in industry. However, there are many problems when using solvent extraction to separate and purify rhenium. For example, in patent CN101220418B, TiO2 solid is used and ultrasonic adsorption method is used at room temperature to separate the rhenium-containing solution. Although this method does not use organic solvents, it requires a large amount of acid and alkali to adjust the pH; in patent CN102251107B, the rhenium-containing raw material is mixed with an oxidant under normal pressure alkaline environment. After the reaction is completed, the reactant is filtered, and the filtrate obtained is passed through a strong alkaline After the anion exchange resin is adsorbed, the strong alkaline anion exchange resin is analyzed, and a large amount of oxidant is required in the process; in patent CN118086704A, molybdenum roasted sand is used as raw material, molybdenum and rhenium in the molybdenum roasted sand are leached, and a high-concentration sodium molybdate solution containing rhenium is obtained while leaching molybdenum, and the molybdenum and rhenium in the high-concentration sodium molybdate solution are separated by ion exchange adsorption, and rhenium is enriched by a special ion exchange analysis process to obtain a high-concentration ammonium rhenate solution. The production requirements are high and it is not conducive to industrial promotion. In summary, the existing solvent extraction method has problems such as low extraction efficiency, high cost of extractant and large wastewater discharge, which seriously limits its application in industrialization.

[0005] Therefore, how to provide a rhenium extractant with high efficiency, good economy and environmental protection has become a technical problem to be solved urgently in this field. Summary of the invention

[0006] The purpose of the present invention is to provide a rhenium extractant and a preparation method thereof and a method for extracting and separating rhenium. When the rhenium extractant provided by the present invention is used for extracting and separating rhenium, it is not necessary to saponify or activate the extractant, nor is it necessary to use an acid, alkali or oxidant. At the same time, the extraction rate of rhenium is high and the purity is high. In addition, the rhenium extractant can be reused after back extraction, which is green and environmentally friendly.

[0007] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0008] The invention provides a rhenium extractant, which comprises the following components by volume percentage: 5-50% of secondary amine, 20-60% of diphosphorus oxide and the remainder of diluent.

[0009] Preferably, the structure of the secondary amine is The R 1 and R 2 Each of the following groups is independently any one of a C1-C20 alkyl group, a C3-C6 cycloalkyl group and a C5-C10 aryl group.

[0010] Preferably, the structure of the diphosphorus oxide is The n is 1 to 20; the R 3 , R 4 , R 5 and R 6 Each of the following is independently any one of a C3-C30 alkyl group, a C3-C8 cycloalkyl group and a C5-C20 aryl group.

[0011] Preferably, the diluent comprises one or more of kerosene, sulfonated kerosene, n-hexane, cyclohexane, n-octane, isooctane, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, ethyl acetate, dichlorobenzene, trichlorobenzene, octanol, benzene, toluene and xylene.

[0012] The present invention provides a method for preparing the rhenium extractant described in the above technical solution, comprising: mixing a secondary amine, a diphosphorus oxide and a diluent to obtain the rhenium extractant.

[0013] The present invention also provides a method for extracting and separating rhenium, using a rhenium extractant to perform countercurrent extraction on an extract, and then performing back extraction to obtain a high-purity rhenate; the rhenium extractant is the rhenium extractant described in the above technical solution or the rhenium extractant prepared by the preparation method described in the above technical solution.

[0014] Preferably, the volume ratio of the rhenium extractant to the liquid to be extracted is 1:(1-10).

[0015] Preferably, the number of stages of the countercurrent extraction is 1 to 10; the temperature of the countercurrent extraction is 10 to 80°C.

[0016] Preferably, the stripping agent used for the stripping comprises one or more of water, ammonium carbonate solution, ammonium bicarbonate solution, ammonia solution, hydroxylamine solution, sodium carbonate solution and sodium bicarbonate solution.

[0017] Preferably, the number of stages of the stripping is 1 to 5; and the temperature of the stripping is 15 to 90°C.

[0018] The invention provides a rhenium extractant, which comprises the following components by volume percentage: 5-50% of secondary amine, 20-60% of diphosphorus oxide and the remainder of diluent. The invention adopts secondary amine, diphosphorus oxide and diluent to form the extractant, and the secondary amine and diphosphorus oxide have good synergistic effect, and can have high selectivity for rhenate in the extraction process, so as to directly extract rhenate containing other metals, without saponification or activation of the extractant, and without using acid, alkali or oxidant, so that the extraction process is simple and efficient, and the purity of the rhenate product obtained by purification and separation is high; different extractant formulas can be selected for different rhenium molybdate systems, and the extractant is flexible and changeable; in addition, the secondary amine and diphosphorus oxide are both cheap and easy to obtain, and the cost is low, and after stripping, the extractant can be reused, which is green and environmentally friendly, greatly reducing the production and use costs of the rhenium extractant, improving the market competitiveness of the rhenium extractant, and facilitating large-scale industrial promotion. The results of the embodiment show that after the mixed solution of sodium perrhenate and sodium molybdate is extracted by the rhenium extractant provided by the present invention, the extraction rate of sodium perrhenate is ≥90%, and can reach 98% at the highest. The purity of sodium perrhenate is high and the impurities are few, and the purity is ≥93%, and can reach 99.98% at the highest. DETAILED DESCRIPTION

[0019] The invention provides a rhenium extractant, which comprises the following components by volume percentage: 5-50% of secondary amine, 20-60% of diphosphorus oxide and the remainder of diluent.

[0020] The rhenium extractant provided by the present invention comprises 5 to 50% of a secondary amine by volume percentage. In the present invention, the structure of the secondary amine is preferably The R 1 and R 2 It is independently preferably any one of a C1-C20 alkyl group, a C3-C6 cycloalkyl group and a C5-C10 aryl group, and more preferably any one of a C6-C18 alkyl group, a C5-C6 cycloalkyl group and a C5-C8 aryl group.

[0021] As an embodiment of the present invention, the volume percentage of the secondary amine can be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50%; the secondary amine can be N-butylcyclohexylamine (CAS: 10108-56-2), dicyclohexylamine (CAS: 101-83-7), di-n-butylamine (CAS: 111-92-2), di-n-octylamine (CAS: 1120-48-5), N-cyclopentylcyclohexylamine (CAS: 40649-25-0), N-cyclopropylmethylcyclohexylamine (CAS: 99175-40-3), 4,4'-dimethyldicyclohexylamine (CAS: 109667-09-6) or diphenylamine (CAS: 122-39-4).

[0022] The rhenium extractant provided by the present invention comprises 20 to 60% of diphosphorus oxide by volume. In the present invention, the structure of the diphosphorus oxide is preferably The n is preferably 1 to 20, more preferably 1 to 10; the R 3 , R 4 , R 5 and R 6 Preferably, they are independently any one of C3-C30 alkyl, C3-C8 cycloalkyl and C5-C20 aryl, and more preferably any one of C4-C10 alkyl, C4-C6 cycloalkyl and C5-C10 aryl.

[0023] As an embodiment of the present invention, the volume percentage of the bisphosphorus oxide may be 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55% or 60%; the bisphosphorus oxide may be butane-1,4-diylbis(diphenylphosphine oxide) (CAS: 4151-27-3), propane-1,3-diylbis(diphenylphosphine oxide) (CAS: 16524-41-7), 1,2-bis(diphenylphosphineoxy)ethane (CAS: 4141-50-8) , 4-dimethylphosphinoyl-1-diphenylphosphinoylpropane (CAS: 89807-21-6), 4-diethylphosphinoyl-1-diphenylphosphinoylpropane (CAS: 89807-22-7), 4-dimethylphosphinoyl-1-dimethylphosphinoylbutane (CAS: 98543-48-7), 1,6-diphosphinoylbicyclo[4.3.3]octane (CAS: 342824-55-9) or dibutyl[4-(butylphenylphosphinoyl)butyl]phosphinoyl (CAS: 199284-22-5).

[0024] The rhenium extractant provided by the present invention includes a balance of diluent by volume percentage. In the present invention, the diluent preferably includes one or more of kerosene, sulfonated kerosene, n-hexane, cyclohexane, n-octane, isooctane, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, ethyl acetate, dichlorobenzene, trichlorobenzene, octanol, benzene, toluene and xylene, and more preferably one or more of kerosene, sulfonated kerosene, cyclohexane, dichloroethane, chloroform, dichlorobenzene, trichlorobenzene, octanol, toluene and xylene. In the present invention, the diluent is mainly used to provide a liquid environment for secondary amines and diphosphorus oxides, so as to facilitate the subsequent extraction of rhenate.

[0025] The invention adopts secondary amine, diphosphorus oxide and diluent to form an extractant. The secondary amine and diphosphorus oxide have good synergistic effect, can have high selectivity for rhenate in the extraction process, so as to directly extract rhenate containing other metals, does not need to saponify or activate the extractant, and does not need to use acid, alkali or oxidant, so that the extraction process is simple and efficient, and the purity of the rhenate product obtained by purification and separation is high; different extractant formulas can be selected for different rhenium molybdate systems, and the extractant is flexible and changeable; in addition, the secondary amine and diphosphorus oxide are both cheap and easy to obtain, and the cost is low; after stripping, the extractant can be reused, which is green and environmentally friendly, greatly reduces the production and use costs of the rhenium extractant, improves the market competitiveness of the rhenium extractant, and is conducive to large-scale industrial promotion.

[0026] The present invention also provides a method for preparing the rhenium extractant described in the above technical solution, comprising: mixing a secondary amine, a diphosphorus oxide and a diluent to obtain the rhenium extractant.

[0027] The present invention has no particular limitation on the specific operation of the mixing, as long as the secondary amine, the diphosphorus oxide and the diluent can be mixed uniformly.

[0028] The preparation method provided by the invention is simple, does not require special equipment, and is conducive to its industrial large-scale promotion.

[0029] The present invention also provides a method for extracting and separating rhenium, using a rhenium extractant to perform countercurrent extraction on an extract, and then performing back extraction to obtain a high-purity rhenate; the rhenium extractant is the rhenium extractant described in the above technical solution or the rhenium extractant prepared by the preparation method described in the above technical solution.

[0030] In the present invention, the liquid to be extracted is a mixed solution of rhenate and molybdate; the rhenate is preferably a soluble rhenate, more preferably sodium perrhenate (NaO4Re); the molybdate is preferably a soluble molybdate, more preferably sodium molybdate; the concentration of rhenium element in the mixed solution is preferably 5-500 g / L, and the concentration of molybdenum element is preferably 0.1-50 g / L.

[0031] As an embodiment of the present invention, the concentration of rhenium element in the mixed solution can be 5g / L, 10g / L, 20g / L, 30g / L, 50g / L, 80g / L, 100g / L, 150g / L, 200g / L, 250g / L, 300g / L, 350g / L, 400g / L, 450g / L or 500g / L; the concentration of molybdenum element in the mixed solution can be 0.1g / L, 1g / L, 2g / L, 3g / L, 5g / L, 10g / L, 15g / L, 20g / L, 25g / L, 30g / L, 35g / L, 40g / L, 45g / L or 50g / L.

[0032] In the present invention, the volume ratio of the rhenium extractant to the liquid to be extracted is preferably 1:(1-10), more preferably 1:(1-5). The present invention can ensure that the rhenium extractant extracts the rhenium element in the liquid to be extracted by controlling the concentration of the rhenium extractant and the liquid to be extracted and the volume ratio of the two.

[0033] As an embodiment of the present invention, the volume ratio of the rhenium extractant to the liquid to be extracted can be 1:2, 1:3 or 1:4.

[0034] In the present invention, the countercurrent extraction is preferably carried out in a mixing and settling tank, an extraction tower or a centrifuge. The present invention has no particular limitation on the specific model and source of the mixing and settling tank, the extraction tower or the centrifuge, and a commercially available mixing and settling tank, the extraction tower or the centrifuge well known to those skilled in the art can be used.

[0035] In the present invention, the number of stages of the countercurrent extraction is preferably 1 to 10; the temperature of the countercurrent extraction is preferably 10 to 80° C. The present invention uses countercurrent extraction to extract the rhenate solution, which can improve the extraction rate of rhenium; by controlling the number of stages and temperature of the countercurrent extraction, the extraction rate of rhenium can be further improved.

[0036] As an embodiment of the present invention, the level of the countercurrent extraction can be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; the temperature of the countercurrent extraction can be 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C or 80°C; the time of the countercurrent extraction can be 3min, 5min, 8min, 10min, 12min, 15min, 18min or 20min.

[0037] In the present invention, the stripping agent used for the stripping preferably includes one or more of water, ammonium carbonate solution, ammonium bicarbonate solution, ammonia solution, hydroxylamine solution, sodium carbonate solution and sodium bicarbonate solution. The present invention has no special limitation on the concentration of the ammonium carbonate solution, ammonium bicarbonate solution, ammonia solution, hydroxylamine solution, sodium carbonate solution and sodium bicarbonate solution. It can be determined according to the technical common sense of those skilled in the art that the rhenate can be stripped out from the extractant. As an embodiment of the present invention, the mass concentration of the ammonium carbonate solution, ammonium bicarbonate solution, ammonia solution, hydroxylamine solution, sodium carbonate solution and sodium bicarbonate solution can be 5%, 10%, 15%, 20%, 25%, 30%, 35% or 40%.

[0038] In the present invention, the number of stages of the stripping is preferably 1 to 5; the temperature of the stripping is preferably 15 to 90° C. The present invention has no special limitation on the stripping time, which can be determined according to the technical common sense of those skilled in the art as long as the rhenate can be stripped from the extractant. The present invention can improve the stripping efficiency by controlling the stripping temperature.

[0039] As an embodiment of the present invention, the number of stripping stages may be 1, 2, 3, 4 or 5; the stripping temperature may be 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C or 90°C; the stripping time may be 1 min, 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min or 10 min.

[0040] In the present invention, the rhenium extractant after stripping is preferably continuously recycled. The rhenium extractant provided by the present invention contains very few impurities after stripping and can be continuously used for countercurrent extraction of the extract to be extracted, thereby reducing production costs.

[0041] The method for extracting and separating rhenium provided by the present invention has a simple extraction process, which only has two processes, extraction and stripping. The equipment used is conventional equipment, and the extraction conditions are simple, which can be at room temperature or properly heated. The extractant does not need to be pretreated by saponification, etc., which reduces the use of reagents such as acids and alkalis, has low requirements on equipment, and is economical.

[0042] The technical solutions in the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0043] Example 1

[0044] A rhenium extractant, which is composed of 5% secondary amine, 20% diphosphorus oxide and the balance diluent, by volume percentage;

[0045] The secondary amine is N-butylcyclohexylamine (CAS: 10108-56-2), the bisphosphorus oxide is butane-1,4-diylbis(diphenylphosphine oxide) (CAS: 4151-27-3), and the diluent is sulfonated kerosene;

[0046] The preparation method of the rhenium extractant is as follows: secondary amine, diphosphorus oxide and a diluent are mixed at room temperature and then stirred evenly to obtain the rhenium extractant.

[0047] Application Example 1

[0048] A method for extracting and separating rhenium, comprising: in a mixing and settling tank, using the rhenium extractant of Example 1 to perform countercurrent extraction on an extract, and then performing stripping to obtain a high-purity rhenate;

[0049] The liquid to be extracted is a mixed solution of sodium perrhenate and sodium molybdate; the concentration of rhenium in the mixed solution is 10 g / L, and the concentration of molybdenum is 2 g / L;

[0050] The volume ratio of the rhenium extractant to the liquid to be extracted is 1:1:

[0051] The countercurrent extraction stage is 3, the countercurrent extraction temperature is 20°C, and the countercurrent extraction time is 10 min;

[0052] The stripping agent used in the stripping is water, the stripping level is 1, the stripping temperature is 30° C., the stripping time is 3 minutes, and the rhenium extractant after stripping is continuously recycled.

[0053] Example 2

[0054] A rhenium extractant, which is composed of 5% secondary amine, 60% diphosphorus oxide and the balance diluent, by volume percentage;

[0055] The secondary amine is dicyclohexylamine (CAS: 101-83-7), the bisphosphorus oxide is propane-1,3-diylbis(diphenylphosphine oxide) (CAS: 16524-41-7), and the diluent is xylene;

[0056] The preparation method of the rhenium extractant is as follows: secondary amine, diphosphorus oxide and a diluent are mixed at room temperature and then stirred evenly to obtain the rhenium extractant.

[0057] Application Example 2

[0058] A method for extracting and separating rhenium, comprising: using the rhenium extractant of Example 2 to perform countercurrent extraction on an extract in a centrifugal extractor, and then performing back extraction to obtain a high-purity rhenate;

[0059] The liquid to be extracted is a mixed solution of sodium perrhenate and sodium molybdate; the concentration of rhenium in the mixed solution is 30 g / L, and the concentration of molybdenum is 3 g / L;

[0060] The volume ratio of the rhenium extractant to the liquid to be extracted is 2:1:

[0061] The countercurrent extraction stage is 5, the countercurrent extraction temperature is 25°C, and the countercurrent extraction time is 10 min;

[0062] The stripping agent used in the stripping is ammonium carbonate solution, the mass concentration of the ammonium carbonate solution is 15%, the stripping level is 1, the stripping temperature is 35° C., the stripping time is 3 minutes, and the rhenium extractant after stripping is continuously recycled.

[0063] Example 3

[0064] A rhenium extractant, which is composed of 15% secondary amine, 45% diphosphorus oxide and the balance diluent, by volume percentage;

[0065] The secondary amine is di-n-butylamine (CAS: 111-92-2), the bisphosphorus oxide is 1,2-bis(diphenylphosphino)ethane (CAS: 4141-50-8), and the diluent is trichlorobenzene;

[0066] The preparation method of the rhenium extractant is as follows: secondary amine, diphosphorus oxide and a diluent are mixed at room temperature and then stirred evenly to obtain the rhenium extractant.

[0067] Application Example 3

[0068] A method for extracting and separating rhenium, comprising: using the rhenium extractant of Example 3 to perform countercurrent extraction on an extract in a centrifugal extractor, and then performing back extraction to obtain a high-purity rhenate;

[0069] The liquid to be extracted is a mixed solution of sodium perrhenate and sodium molybdate; the concentration of rhenium in the mixed solution is 25 g / L, and the concentration of molybdenum is 1 g / L;

[0070] The volume ratio of the rhenium extractant to the liquid to be extracted is 3:1:

[0071] The countercurrent extraction stage is 4, the countercurrent extraction temperature is 45°C, and the countercurrent extraction time is 10 min;

[0072] The stripping agent used in the stripping is ammonia water, the mass concentration of the ammonia water is 20%, the stripping level is 1, the stripping temperature is 40° C., the stripping time is 2 minutes, and the rhenium extractant after stripping is continuously recycled.

[0073] Example 4

[0074] A rhenium extractant, which is composed of 20% secondary amine, 35% diphosphorus oxide and the balance diluent, by volume percentage;

[0075] The secondary amine is di-n-octylamine (CAS: 1120-48-5), the diphosphorus oxide is 4-dimethylphosphine-1-diphenylphosphine oxide (CAS: 89807-21-6), and the diluent is octanol;

[0076] The preparation method of the rhenium extractant is as follows: secondary amine, diphosphorus oxide and a diluent are mixed at room temperature and then stirred evenly to obtain the rhenium extractant.

[0077] Application Example 4

[0078] A method for extracting and separating rhenium, comprising: using the rhenium extractant of Example 4 to perform countercurrent extraction on an extract in a centrifugal extractor, and then performing back extraction to obtain a high-purity rhenate;

[0079] The liquid to be extracted is a mixed solution of sodium perrhenate and sodium molybdate; the concentration of rhenium in the mixed solution is 15 g / L, and the concentration of molybdenum is 1 g / L;

[0080] The volume ratio of the rhenium extractant to the liquid to be extracted is 2:1:

[0081] The countercurrent extraction stage is 3, the countercurrent extraction temperature is 50°C, and the countercurrent extraction time is 10 min;

[0082] The stripping agent used in the stripping is hydroxylamine solution, the mass concentration of the hydroxylamine solution is 20%, the stripping level is 1, the stripping temperature is 50° C., the stripping time is 1 minute, and the rhenium extractant after stripping is continuously recycled.

[0083] Example 5

[0084] A rhenium extractant, which is composed of 30% secondary amine, 30% diphosphorus oxide and the balance diluent, by volume percentage;

[0085] The secondary amine is N-cyclopentylcyclohexylamine (CAS: 40649-25-0), the diphosphorus oxide is 4-diethylphosphine-1-diphenylphosphine oxide (CAS: 89807-22-7), and the diluent is n-hexane;

[0086] The preparation method of the rhenium extractant is as follows: secondary amine, diphosphorus oxide and a diluent are mixed at room temperature and then stirred evenly to obtain the rhenium extractant.

[0087] Application Example 5

[0088] A method for extracting and separating rhenium, comprising: using the rhenium extractant of Example 5 to perform countercurrent extraction on an extract liquid in a centrifugal extractor, and then performing back extraction to obtain a high-purity rhenate;

[0089] The liquid to be extracted is a mixed solution of sodium perrhenate and sodium molybdate; the concentration of rhenium in the mixed solution is 15 g / L, and the concentration of molybdenum is 1 g / L;

[0090] The volume ratio of the rhenium extractant to the liquid to be extracted is 2:1:

[0091] The countercurrent extraction stage is 3, the countercurrent extraction temperature is 60°C, and the countercurrent extraction time is 10 min;

[0092] The stripping agent used in the stripping is sodium carbonate solution, the mass concentration of the sodium carbonate solution is 20%, the stripping level is 1, the stripping temperature is 70° C., the stripping time is 1 minute, and the rhenium extractant after stripping is continuously recycled.

[0093] Example 6

[0094] A rhenium extractant, which is composed of 50% secondary amine, 30% diphosphorus oxide and the balance diluent, by volume percentage;

[0095] The secondary amine is N-cyclopropylmethylcyclohexylamine (CAS: 99175-40-3), the diphosphorus oxide is 4-dimethylphosphine-1-dimethylphosphine oxide butane (CAS: 98543-48-7), and the diluent is chloroform;

[0096] The preparation method of the rhenium extractant is as follows: secondary amine, diphosphorus oxide and a diluent are mixed at room temperature and then stirred evenly to obtain the rhenium extractant.

[0097] Application Example 6

[0098] A method for extracting and separating rhenium, comprising: in an extraction tower, using the rhenium extractant of Example 6 to perform countercurrent extraction on an extract, and then performing stripping to obtain a high-purity rhenate;

[0099] The liquid to be extracted is a mixed solution of sodium perrhenate and sodium molybdate; the concentration of rhenium in the mixed solution is 150 g / L, and the concentration of molybdenum is 1 g / L;

[0100] The volume ratio of the rhenium extractant to the liquid to be extracted is 5:1:

[0101] The countercurrent extraction stage is 3, the countercurrent extraction temperature is 48°C, and the countercurrent extraction time is 20 min;

[0102] The stripping agent used in the stripping is ammonium bicarbonate solution, the mass concentration of the ammonium bicarbonate solution is 30%, the stripping level is 1, the stripping temperature is 50° C., the stripping time is 5 minutes, and the rhenium extractant after stripping is continuously recycled.

[0103] Example 7

[0104] A rhenium extractant, which is composed of 17% secondary amine, 42% diphosphorus oxide and the balance diluent, by volume percentage;

[0105] The secondary amine is 4,4'-dimethyldicyclohexylamine (CAS: 109667-09-6), the diphosphorus oxide is 1,6-diphosphobicyclo[4.3.3]octane (CAS: 342824-55-9), and the diluent is cyclohexane;

[0106] The preparation method of the rhenium extractant is as follows: secondary amine, diphosphorus oxide and a diluent are mixed at room temperature and then stirred evenly to obtain the rhenium extractant.

[0107] Application Example 7

[0108] A method for extracting and separating rhenium, comprising: in a mixing and settling tank, using the rhenium extractant of Example 7 to perform countercurrent extraction on an extract, and then performing back extraction to obtain a high-purity rhenate;

[0109] The liquid to be extracted is a mixed solution of sodium perrhenate and sodium molybdate; the concentration of rhenium in the mixed solution is 300 g / L, and the concentration of molybdenum is 20 g / L;

[0110] The volume ratio of the rhenium extractant to the liquid to be extracted is 1:1:

[0111] The countercurrent extraction stage is 6, the countercurrent extraction temperature is 25°C, and the countercurrent extraction time is 15 minutes;

[0112] The stripping agent used in the stripping is a sodium bicarbonate solution, the mass concentration of the sodium bicarbonate solution is 20%, the stripping level is 3, the stripping temperature is 35° C., the stripping time is 3 minutes, and the rhenium extractant after stripping is continuously recycled.

[0113] Example 8

[0114] A rhenium extractant, which is composed of 40% secondary amine, 40% diphosphorus oxide and the remainder diluent, by volume percentage;

[0115] The secondary amine is diphenylamine (CAS: 122-39-4), the bisphosphorus oxide is dibutyl [4-(butylphenylphosphine oxide) butyl]phosphine oxide (CAS: 199284-22-5), and the diluent is ethyl acetate;

[0116] The preparation method of the rhenium extractant is as follows: secondary amine, diphosphorus oxide and a diluent are mixed at room temperature and then stirred evenly to obtain the rhenium extractant.

[0117] Application Example 8

[0118] A method for extracting and separating rhenium, comprising: using the rhenium extractant of Example 8 to perform countercurrent extraction on an extract in a centrifugal extractor, and then performing back extraction to obtain a high-purity rhenate;

[0119] The liquid to be extracted is a mixed solution of sodium perrhenate and sodium molybdate; the concentration of rhenium in the mixed solution is 200 g / L, and the concentration of molybdenum is 17 g / L;

[0120] The volume ratio of the rhenium extractant to the liquid to be extracted is 2:1:

[0121] The countercurrent extraction stage is 6, the countercurrent extraction temperature is 25°C, and the countercurrent extraction time is 5 minutes;

[0122] The stripping agent used in the stripping is sodium carbonate solution, the mass concentration of the sodium carbonate solution is 20%, the stripping level is 2, the stripping temperature is 30° C., the stripping time is 1 minute, and the rhenium extractant after stripping is continuously recycled.

[0123] The extraction rate of sodium perrhenate and the purity of sodium perrhenate obtained in Application Examples 1 to 8 are shown in Table 1:

[0124] Table 1 Extraction rate of sodium perrhenate and purity of sodium perrhenate obtained in Application Examples 1 to 8

[0125] Example Extraction rate of sodium perrhenate / % Purity of Sodium Perrhenate / % Application Example 1 90 95 Application Example 2 92 97 Application Example 3 97 99 Application Example 4 98 99.98 Application Example 5 98 99.98 Application Example 6 91 93 Application Example 7 92 96 Application Example 8 97 99

[0126] Among them, the purity test uses an ICP-MS instrument to measure the content of sodium perrhenate and sodium molybdate in the solution to obtain the purity of sodium perrhenate.

[0127] It can be seen from Table 1 that after the mixed solution of sodium perrhenate and sodium molybdate is extracted by the rhenium extractant provided by the present invention, the extraction rate of sodium perrhenate is ≥90%, and can reach 98% at the highest. Sodium perrhenate has high purity and few impurities, and the purity is ≥93%, and can reach 99.98% at the highest. This shows that the rhenium extractant provided by the present invention can be used for the extraction of rhenium element and can achieve a good extraction effect.

[0128] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A rhenium extractant, comprising the following components by volume percentage: 5-50% of a secondary amine, 20-60% of a diphosphorus oxide and the remainder of a diluent.

2. The rhenium extractant according to claim 1, characterized in that The structure of the secondary amine is The R 1 and R 2 Each of the following groups is independently any one of a C1-C20 alkyl group, a C3-C6 cycloalkyl group and a C5-C10 aryl group.

3. The rhenium extractant according to claim 1, characterized in that The structure of the diphosphorus oxide is The n is 1 to 20; the R 3 , R 4 , R 5 and R 6 Each of the following is independently any one of a C3-C30 alkyl group, a C3-C8 cycloalkyl group and a C5-C20 aryl group.

4. The rhenium extractant according to claim 1, characterized in that The diluent includes one or more of kerosene, sulfonated kerosene, n-hexane, cyclohexane, n-octane, isooctane, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, ethyl acetate, dichlorobenzene, trichlorobenzene, octanol, benzene, toluene and xylene.

5. The method for preparing the rhenium extractant according to any one of claims 1 to 4, comprising: The secondary amine, the diphosphorus oxide and the diluent are mixed to obtain the rhenium extractant.

6. A method for extracting and separating rhenium, characterized in that: The extract is subjected to countercurrent extraction using a rhenium extractant, and then stripped to obtain a high-purity rhenate; the rhenium extractant is the rhenium extractant described in any one of claims 1 to 4 or the rhenium extractant prepared by the preparation method described in claim 5.

7. The method according to claim 6, characterized in that The volume ratio of the rhenium extractant to the liquid to be extracted is 1:(1-10).

8. The method according to claim 6, characterized in that The number of the countercurrent extraction stages is 1 to 10; the temperature of the countercurrent extraction is 10 to 80°C.

9. The method according to claim 6, characterized in that The stripping agent used in the stripping includes one or more of water, ammonium carbonate solution, ammonium bicarbonate solution, ammonia solution, hydroxylamine solution, sodium carbonate solution and sodium bicarbonate solution.

10. The method according to claim 6, characterized in that The number of the stripping stages is 1 to 5; the stripping temperature is 15 to 90°C.

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