Preparation method of a chelating resin and its application in purifying ammonium perrhenate

Abstract

The present invention provides a preparation method of a chelating resin and its application in the purification of ammonium perrhenate. By setting the ratio of the oil-phase mixture and the water-phase mixture and precise temperature control, a chelating resin with excellent performance is prepared. This chelating resin not only has a uniform dispersion of the extractant, a strong binding force with the resin, but also is not easily lost. When using this chelating resin to purify ammonium perrhenate solution in a chromatography column, by controlling the solution concentration and flow rate, ammonium perrhenate with a purity greater than 99.99% can be obtained. The chelating resin prepared by the method provided by the present invention can not only improve the purification efficiency and purity of ammonium perrhenate, but also reduce the generation of organic waste liquid, reduce the impact on the environment, and at the same time simplify the resin synthesis and regeneration process, so as to enhance the economy and environmental protection of the ammonium perrhenate refining technology, and provide a high-quality rhenium metal resource guarantee for the development of China's aerospace industry.

Description

Technical Field

[0001] The present application relates to the technical field of metal purification. Specifically, it relates to a preparation method of extraction resin and its application in the purification of ammonium perrhenate. Background Art

[0002] Metal rhenium has high melting point, high strength, high density, good plasticity and excellent mechanical stability. Ammonium perrhenate is the raw material for preparing high-purity metal rhenium, and the purity of ammonium perrhenate determines the quality of rhenium metal. Therefore, mastering the refining technology of ammonium perrhenate is of great significance for ensuring the strategic resource requirements for the development of China's aerospace industry.

[0003] At present, the main methods for refining and purifying ammonium perrhenate include extraction method, ion exchange method, recrystallization method, membrane separation technology, biochar adsorption method, etc. Among them, the extraction method and the ion exchange method are currently widely used methods. However, both the extraction method and the ion exchange method have certain limitations. The research and application of extraction resin have developed very rapidly in recent years. It is mainly applied in the fields of water treatment, rare earth separation, etc. The method is to prepare by adsorbing an extractant on a macroporous polymer carrier.

[0004] However, the currently applied extraction resin still has certain problems, such as poor purification effect of ammonium perrhenate by the existing extraction resin, uneven dispersion of the extractant, poor binding force with the resin, easy loss, etc. Summary of the Invention

[0005] To solve the above problems, the present invention provides a preparation method of extraction resin and its application in the purification of ammonium perrhenate. By setting the ratio of the oil-phase mixture and the water-phase mixture, and precise temperature control, an extraction resin with excellent performance is prepared. This extraction resin not only has uniform dispersion of the extractant, strong binding force with the resin, but also is not easy to lose. When using this extraction resin to purify ammonium perrhenate solution in a chromatography column, by controlling the solution concentration and flow rate, ammonium perrhenate with a purity greater than 99.99% can be obtained. The extraction resin prepared by the method provided by the present invention can not only improve the purification efficiency and purity of ammonium perrhenate, but also reduce the generation of organic waste liquid, reduce the impact on the environment. At the same time, it simplifies the synthesis and regeneration process of the resin, improves the economy and environmental protection of the ammonium perrhenate refining technology, and provides high-quality rhenium metal resource guarantee for the development of China's aerospace industry.

[0006] In the first aspect, the present invention provides a preparation method of extraction resin, and the method includes:

[0007] Adding resin particles into pure water with an equal volume and a temperature of 55 °C to 65 °C, adding an oil-phase mixture to the obtained system, stirring and cooling, then adding a water-phase mixture, and obtaining the extraction resin after stirring, filtering and washing;

[0008] Among them, the volume ratio of the resin particles to the oil-phase mixture is 1:(0.4 - 0.7); the volume ratio of the oil-phase mixture to the water-phase mixture is 1:(0.6 - 0.75).

[0009] The oil-phase mixture is composed of a diluent accounting for 65% - 80% by mass percentage, a lipid compound accounting for 20% - 30% by mass percentage, and sec-octanol accounting for 5% - 10% by mass percentage.

[0010] The water-phase mixture is composed of pure water accounting for 35% - 50% by mass percentage, ammonia water accounting for 25% - 45% by mass percentage, and sodium hydroxide accounting for 5% - 10% by mass percentage.

[0011] Optionally, the volume ratio of the resin particles to the oil-phase mixture is 1:(0.5 - 0.6).

[0012] Optionally, the lipid compound is diisooctyl phosphate and / or 2-ethylhexyl 2-ethylhexylphosphonate.

[0013] Optionally, the diluent is 260# sulfonated kerosene, n-dodecane or xylene.

[0014] Optionally, the preparation method of the resin particles includes:

[0015] Adding guar gum and gelatin into pure water at a temperature of 70 °C - 80 °C, adding a hydrocarbon compound, sodium dodecylbenzenesulfonate, an initiator, carboxymethylcellulose sodium and calcium sulfate into the obtained colloidal solution, mixing at 90 °C - 95 °C, keeping warm for 2 h - 4 h, cooling, filtering and washing to obtain the resin particles;

[0016] Among them, the hydrocarbon compound is at least one of styrene, methacrylic acid and divinylbenzene;

[0017] The initiator is a peroxide initiator or an azo initiator.

[0018] Optionally, in the resin particles, the mass percentages of the guar gum, the gelatin, the hydrocarbon compound, the sodium dodecylbenzenesulfonate, the initiator, the carboxymethylcellulose sodium and the calcium sulfate are 5% - 10%, 25% - 40%, 15% - 30%, 10% - 15%, 5% - 10%, 2% - 6%, 1% - 5% in sequence.

[0019] Optionally, in the resin particles, the mass percentages of the guar gum, the gelatin, the hydrocarbon compound, the sodium dodecylbenzenesulfonate, the initiator, the sodium carboxymethyl cellulose, and the calcium sulfate are 7% - 9%, 30% - 35%, 20% - 25%, 11% - 13%, 6% - 8%, 2% - 6%, and 1% - 5% in sequence.

[0020] Optionally, the hydrocarbon compound is styrene, methacrylic acid, and divinylbenzene;

[0021] The mass percentages of the styrene, the methacrylic acid, and the divinylbenzene are (45 - 55)% : (20 - 25)% : (20 - 25)%.

[0022] Optionally, the peroxide initiator is benzoyl peroxide, dicumyl peroxide, or di - tert - butyl peroxide;

[0023] The azo initiator is azobisisobutyronitrile or azobisisoheptonitrile.

[0024] In a second aspect, the present invention provides an application of the extraction resin in purifying ammonium perrhenate. The extraction resin is prepared by the preparation method described in the first aspect above, and the extraction resin is used for purifying ammonium perrhenate;

[0025] The purification method includes:

[0026] Inject an ammonium perrhenate solution with a concentration not greater than 35 g / L into a chromatography column filled with the extraction resin at a flow rate of 2Bv - 7Bv, and ammonium perrhenate with a purity greater than 99.99% is obtained after passing through.

[0027] Beneficial technical effects:

[0028] 1. The present invention provides a preparation method of an extraction resin. By reacting resin particles with a specific proportion of oil - phase mixed solution and water - phase mixed solution at a temperature of 55 °C - 65 °C, a high - performance extraction resin is prepared. This resin has the characteristics of uniform dispersion of the extractant, strong binding force with the resin, and high stability, which can effectively reduce the loss of the extractant, reduce the generation of organic waste liquid, and thus reduce the impact on the environment. This method simplifies the resin synthesis process, improves the recycling efficiency of the resin, and provides a reliable material basis for the efficient purification of ammonium perrhenate;

[0029] 2. The present invention provides an application of extraction resin in the purification of ammonium perrhenate. When in application, an ammonium perrhenate solution with a concentration not greater than 35 g / L is injected into a chromatography column filled with extraction resin, and the flow rate is controlled within the range of 2 Bv to 7 Bv. Finally, ammonium perrhenate with a purity greater than 99.99% can be obtained. The extraction resin prepared by the preparation method provided by the present invention can not only improve the purification efficiency and product purity of ammonium perrhenate, but also avoid the limitations of traditional extraction methods and ion exchange methods, such as large loss of organic phase, complex resin synthesis, limited number of cycle regenerations, etc. At the same time, this process is simple to operate, environmentally friendly, reduces the discharge of organic waste liquid, and lowers the production cost, providing high-quality rhenium metal raw materials for fields such as aerospace, etc., and has important strategic significance and economic value. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the description of the embodiments of the present application will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0031] Figure 1 The flowchart of a preparation method of an extraction resin proposed by an embodiment of the present application is shown. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0032] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are some, but not all, of the embodiments of the present application. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present application without creative efforts shall fall within the protection scope of the present application.

[0033] In the drawings, sometimes for clarity, the sizes of the constituent elements, the thickness of the layers, or the regions may be exaggerated. Therefore, any implementation manner of the present disclosure is not necessarily limited to the dimensions shown in the drawings, and the shapes and sizes of the components in the drawings do not reflect the true proportions. In addition, the drawings schematically show ideal examples, and any implementation manner of the present disclosure is not limited to the shapes or values shown in the drawings, etc.

[0034] In the related art, rhenium metal has a high melting point, high strength, high density, good plasticity and excellent mechanical stability. It has very good heat shock resistance at high temperatures. At the same time, rhenium also has very good wear resistance, corrosion resistance and chemical inertness, and has good creep resistance under high temperature and rapid cooling and heating conditions. Due to its excellent properties, it is widely used in industries such as petrochemical, aerospace and electronics industries, especially playing an irreplaceable role in some high-tech fields related to national security and national development strategies. For example, rhenium is indispensable in the manufacture of single crystal turbine blades for aeroengines. However, trace impurities with low melting and boiling points in rhenium metal are likely to form inclusion cores, which can lead to the decay of the mechanical properties of single crystal superalloy materials, thus affecting the safety performance of aircraft. Therefore, extremely strict requirements are imposed on trace impurity elements in rhenium metal. And ammonium perrhenate is the raw material for preparing high-purity rhenium metal, and the purity of ammonium perrhenate determines the quality of rhenium metal. Therefore, mastering the purification technology of ammonium perrhenate is of great significance for ensuring the strategic resource requirements for the development of China's aerospace industry.

[0035] At present, the main methods for refining and purifying ammonium perrhenate include extraction method, ion exchange method, recrystallization method, membrane separation technology, biochar adsorption method, etc. Among them, the extraction method and the ion exchange method are currently more widely used methods. However, both the extraction method and the ion exchange method have certain limitations. For example, the organic phase loss of the extraction method is large and the organic waste liquid will have a certain impact on the environment. The ion exchange method has complex resin synthesis and limited cycle regeneration times, etc.

[0036] The research and application of extraction resin have developed very rapidly in recent years. It is mainly applied in fields such as water treatment and rare earth separation. The method is to adsorb the extractant on a macroporous polymer carrier for preparation, which combines the high selectivity and high efficiency of the solvent extraction method and the simplicity and pollution-free of the ion exchange technology. At the same time, it also overcomes the advantages of difficult phase separation of some extractants, complex synthesis of ion exchange resins and chelating resins, etc. However, there are still certain problems with extraction resin, such as the poor purification effect of existing extraction resin on ammonium perrhenate, uneven dispersion of the extractant, poor binding force with the resin, and easy loss, etc.

[0037] In view of the problems existing in the related art, the present invention provides a preparation method of extraction resin, see Figure 1 , the method includes:

[0038] Step S1: Add resin particles into pure water with an equal volume and a temperature of 55 °C to 65 °C, and add an oil-phase mixed solution to the obtained system, stir and cool;

[0039] Step S2: Add an aqueous-phase mixed solution, stir, filter and wash to obtain the extraction resin;

[0040] Among them, the volume ratio of the resin particles to the oil-phase mixture is 1:(0.4 - 0.7); the volume ratio of the oil-phase mixture to the water-phase mixture is 1:(0.6 - 0.75);

[0041] The oil-phase mixture is composed of a diluent with a mass percentage of 65% - 80%, a lipid compound with 20% - 30%, and sec-octanol with 5% - 10% mixed together;

[0042] The water-phase mixture is composed of pure water with a mass percentage of 35% - 50%, ammonia water with 25% - 45%, and sodium hydroxide with 5% - 10% mixed together.

[0043] It should be noted that the resin particles are styrene gel-type resins;

[0044] The pore size of the resin particles is 0.5 nm - 5 nm;

[0045] The oil-phase mixture and the water-phase mixture form an extractant, and the molecules in the oil-phase mixture and the water-phase mixture are loaded in the pores of the resin particles;

[0046] The temperature of the pure water can be 55 °C, 56 °C, 57 °C, 58 °C, 59 °C, 60 °C, 61 °C, 62 °C, 63 °C, 64 °C, 65 °C; within this temperature range, the resin particles can fully swell, expanding their pore size to facilitate the entry of the extractant (the oil-phase mixture and the water-phase mixture) into the interior of the resin and its uniform dispersion; also, a higher temperature helps to reduce the viscosity of the subsequent oil-phase mixture, making it easier for the lipid compound and sec-octanol to disperse on the surface and inside the resin; also, an increase in temperature can accelerate the chemical reaction rate between the ammonia water and sodium hydroxide and the resin surface or the extractant, promoting the firm binding of the extractant to the resin;

[0047] The volume ratio of the resin particles to the oil-phase mixture can be 1:0.4, 1:0.5, 1:0.6, 1:0.7;

[0048] The volume ratio of the oil-phase mixture to the water-phase mixture can be 1:0.6, 1:0.65, 1:0.7, 1:0.75;

[0049] The mass percentage of the diluent can be 65%, 70%, 75%, 80%; the diluent can reduce the viscosity of the oil-phase mixture, making it easier to disperse on the surface and inside the resin. At the same time, the diluent can also adjust the polarity of the oil-phase mixture to make it more suitable for binding with the resin particles;

[0050] The mass percentage of the lipid compound can be 20%, 22%, 24%, 26%, 28%, 30%; the lipid compound is the main component of the extractant, and it can selectively form a complex with the rhenium ion in ammonium perrhenate, thereby realizing the separation and purification of rhenium;

[0051] The mass percentage of sec-octanol can be 5%, 6%, 7%, 8%, 9%, 10%; as a cosolvent and surfactant, sec-octanol can enhance the dispersibility of the extractant (oil phase and water phase) on the resin surface and improve the binding force between the extractant and the resin, reducing the loss of the extractant;

[0052] The mass percentage of pure water can be 35%, 40%, 45%, 50%; pure water is used as a solvent to dissolve sodium hydroxide and provide a reaction medium;

[0053] The mass percentage of ammonia water can be 25%, 30%, 35%, 40%, 45%; the main function of ammonia water is to adjust the pH value of the aqueous phase mixture to make it alkaline. Under alkaline conditions, ammonium perrhenate is more likely to exist in the form of perrhenate ions (ReO 4- ), which is convenient for selective adsorption by the extractant;

[0054] The mass percentage of sodium hydroxide can be 5%, 6%, 7%, 8%, 9%, 10%; sodium hydroxide can further strengthen the alkaline environment of the aqueous phase mixture, and at the same time react with the functional groups on the resin surface to enhance the adsorption capacity of the resin for the extractant;

[0055] Stirring in step S1 can make the resin particles fully contact with the oil phase mixture, ensuring that the extractant is evenly dispersed on the surface and inside of the resin;

[0056] The cooling process in step S1 helps the resin particles to solidify, making the extractant firmly bound to the resin and preventing its loss in subsequent steps;

[0057] Filtration in step S2 is to separate the unadsorbed oil phase mixture and aqueous phase mixture to obtain the loaded extraction resin;

[0058] Washing in step S2 is to remove the residual unreacted substances and impurities on the resin surface and improve the purity of the extraction resin.

[0059] In the present invention, by controlling the ratio of resin particles to the oil-phase mixture and the ratio of the oil-phase mixture to the water-phase mixture, the extractant can be uniformly dispersed and firmly bound on the resin carrier, so as to reduce the loss of the extractant during application. Among them, the combination of the diluent, lipid compound and sec-octanol in the oil-phase mixture, and the ratio of pure water, ammonia water and sodium hydroxide in the water-phase mixture further enhance the adsorption capacity and selectivity of the extraction resin, and can improve the purity of ammonium perrhenate during application.

[0060] The preparation method provided by the present invention is not only simple to operate, but also reduces the generation of organic waste liquid, reduces the impact on the environment, and has high industrial application value. The prepared extraction resin can be applied to the purification of ammonium perrhenate. By adjusting the ratio of resin particles, oil-phase and water-phase mixtures and the process conditions, the adsorption capacity and selectivity of the extraction resin can be effectively improved, the loss of the extractant can be reduced, and the purification effect of ammonium perrhenate can be enhanced.

[0061] In some embodiments, the volume ratio of the resin particles to the oil-phase mixture is 1:(0.5 - 0.6).

[0062] It should be noted that the volume ratio of the resin particles to the oil-phase mixture can be 1:0.5, 1:0.52, 1:0.54, 1:0.56, 1:0.58, 1:0.6; by precisely controlling the amount of the oil-phase mixture, it helps to reduce the waste of organic solvents, reduce the generation amount of organic waste liquid, thereby reducing production costs and environmental pollution, which is in line with the development concept of green chemistry.

[0063] In the present invention, by setting the volume ratio of the resin particles to the oil-phase mixture, while ensuring the uniform dispersion of the extractant on the surface and inside of the resin and improving the adsorption performance of the extraction resin, it can also make the combination of the extractant and the resin more compact, reduce the loss of the extractant during subsequent use, and improve the stability and service life of the extraction resin. The uniform dispersion and firm binding of the extractant on the resin can further improve the selective adsorption ability of the extraction resin for ammonium perrhenate.

[0064] In some embodiments, the lipid compound is diisooctyl phosphate and / or 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester.

[0065] It should be noted that the lipid compound can be diisooctyl phosphate or 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester; the lipid compound can be diisooctyl phosphate and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester.

[0066] In the present invention, both diisooctyl phosphate and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester are highly efficient selective extractants for perrhenate ions (ReO 4-)(It) has extremely strong complexing ability and can form stable complexes with rhenium ions in ammonium perrhenate, thereby improving the selective adsorption ability of extraction resin for ammonium perrhenate. These two extractants not only have higher selectivity for rhenium, but also can effectively reduce the interference of other impurity ions (such as molybdenum, tungsten, etc.), thereby improving the purification efficiency of ammonium perrhenate.

[0067] In specific implementation, diisooctyl phosphate and mono-2-ethylhexyl 2-ethylhexylphosphonate have long carbon chain structures and strong polar groups (such as phosphate groups), which can form stronger chemical bonds or physical adsorption with the functional groups on the resin surface, reduce the loss of extractant during the purification process, and improve the stability and service life of the extraction resin.

[0068] In specific implementation, diisooctyl phosphate and mono-2-ethylhexyl 2-ethylhexylphosphonate have good solubility and low viscosity, can form a homogeneous oil-phase mixture with diluent and sec-octanol, help the extractant to be evenly dispersed in the resin particles, and avoid problems such as local overloading or underloading.

[0069] In specific implementation, the above two extractants have high chemical stability under alkaline conditions (provided by ammonia water and sodium hydroxide in the aqueous-phase mixture), are not easily decomposed or inactivated, and thus ensure the long-term use performance of the extraction resin.

[0070] In some embodiments, the diluent is 260# sulfonated kerosene, n-dodecane or xylene.

[0071] In the present invention, 260# sulfonated kerosene, n-dodecane and xylene all have good solubility and low viscosity, can effectively dissolve lipid compounds and sec-octanol to form a homogeneous oil-phase mixture, thus helping the extractant to be evenly dispersed in the resin particles, avoiding problems such as local overloading or underloading, improving the adsorption performance of the extraction resin, further improving the adsorption capacity and selectivity, and thus being able to improve the purification efficiency and purity of the extraction resin for ammonium perrhenate.

[0072] In specific implementation, the above diluents have appropriate polarity and surface tension, can form good interactions with the functional groups on the resin surface, and enhance the binding force between the extractant and the resin. Especially 260# sulfonated kerosene, due to its containing sulfonated groups, can form stronger physical or chemical adsorption with the polar groups (such as carboxyl groups, etc.) on the resin surface, thereby reducing the loss of extractant during the purification process.

[0073] In some embodiments, the method for preparing the resin particles includes: adding guar gum and gelatin into pure water at a temperature of 70 °C to 80 °C, adding a hydrocarbon compound, sodium dodecylbenzenesulfonate, an initiator, sodium carboxymethylcellulose, and calcium sulfate into the obtained colloidal solution, mixing at 90 °C to 95 °C, holding for 2 h to 4 h, and obtaining the resin particles after cooling, filtering, and washing;

[0074] Wherein, the hydrocarbon compound is at least one of styrene, methacrylic acid, and divinylbenzene;

[0075] The initiator is a peroxide initiator or an azo initiator.

[0076] It should be noted that the temperature of the pure water can be 70 °C, 72 °C, 74 °C, 76 °C, 78 °C, 80 °C;

[0077] Guar gum and gelatin, as the colloidal matrix, are mainly used to form the basic framework of the resin particles. Both have good gelling properties and biocompatibility, and can improve the mechanical strength and chemical stability of the resin particles; Guar gum and gelatin can act synergistically with sodium carboxymethylcellulose and calcium sulfate to further enhance the structural stability of the resin particles;

[0078] Sodium dodecylbenzenesulfonate is a surfactant, mainly used to emulsify the hydrocarbon compound, so that it is uniformly dispersed in the colloidal solution, thereby forming uniform resin particles;

[0079] Sodium carboxymethylcellulose and calcium sulfate, as reinforcing agents, are mainly used to improve the mechanical strength and stability of the resin particles. Sodium carboxymethylcellulose can increase the flexibility of the resin particles, while calcium sulfate can enhance the hardness and wear resistance of the resin particles;

[0080] After adding the hydrocarbon compound, sodium dodecylbenzenesulfonate, the initiator, sodium carboxymethylcellulose, and calcium sulfate into the obtained colloidal solution, it can be mixed at 90 °C, 91 °C, 92 °C, 93 °C, 94 °C, 95 °C, and held for 2 h, 2.5 h, 3 h, 3.5 h, 4 h.

[0081] In the present invention, by using guar gum and gelatin as the colloidal matrix and combining sodium carboxymethylcellulose and calcium sulfate as the reinforcing agents, the mechanical strength and stability of the prepared resin particles are significantly improved, so that they can withstand higher operating pressures, reduce breakage and wear during the purification process, and extend the service life of the final product extraction resin.

[0082] In specific implementation, the addition of hydrocarbon compounds, combined with the action of initiators, can form macroporous resin particles with a uniform pore size distribution and a high specific surface area. This structure is beneficial to the uniform dispersion and firm binding of extractants in the resin particles, thereby improving the adsorption performance of extraction resins. In specific implementation, guar gum and gelatin, as natural polymer materials, have good chemical stability and biocompatibility. Combined with the emulsifying effect of sodium dodecylbenzenesulfonate, the resin particles exhibit excellent chemical stability under alkaline conditions (provided by ammonia water and sodium hydroxide in the aqueous phase mixture) during the preparation of extraction resins and are not easily decomposed or inactivated.

[0083] In some embodiments, in the resin particles, the mass percentages of the guar gum, the gelatin, the hydrocarbon compounds, the sodium dodecylbenzenesulfonate, the initiator, the carboxymethyl cellulose sodium, and the calcium sulfate are 5% - 10%, 25% - 40%, 15% - 30%, 10% - 15%, 5% - 10%, 2% - 6%, and 1% - 5% in sequence.

[0084] It should be noted that the mass percentage of guar gum can be 5%, 6%, 7%, 8%, 9%, 10%;

[0085] The mass percentage of gelatin can be 25%, 27%, 29%, 30%, 32%, 35%, 37%, 40%;

[0086] The mass percentage of hydrocarbon compounds can be 15%, 17%, 20%, 23%, 25%, 27%, 30%;

[0087] The mass percentage of sodium dodecylbenzenesulfonate can be 10%, 11%, 12%, 13%, 14%, 15%;

[0088] The mass percentage of the initiator can be 5%, 6%, 7%, 8%, 9%, 10%;

[0089] The mass percentage of carboxymethyl cellulose sodium can be 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%;

[0090] The mass percentage of calcium sulfate can be 1%, 2%, 3%, 4%, 5%.

[0091] In the present invention, guar gum and gelatin serve as the colloidal matrix, providing the basic framework of the resin particles. The high proportion of gelatin ensures the mechanical strength and toughness of the resin particles, while the addition of guar gum further enhances the stability and pressure resistance of the particles. Sodium carboxymethyl cellulose and calcium sulfate are used as reinforcing agents to further increase the hardness and wear resistance of the resin particles, enabling them to withstand higher operating pressures and reducing breakage and wear during the purification process. The proportion of hydrocarbon compounds is adjusted to form a uniform macroporous structure during the polymerization reaction. This structure has a high specific surface area, which is beneficial to the uniform dispersion and firm binding of the extractant in the resin particles, thereby improving the adsorption performance of the extraction resin. Sodium dodecylbenzenesulfonate is used as a surfactant to ensure the uniform dispersion of hydrocarbon compounds in the colloidal solution, thus forming resin particles with a stable structure. The proportion of the initiator is set to effectively control the rate of the polymerization reaction, avoiding problems of uneven resin structure caused by too fast or too slow reaction, thereby improving the chemical stability of the resin particles.

[0092] In some embodiments, in the resin particles, the mass percentages of the guar gum, the gelatin, the hydrocarbon compounds, the sodium dodecylbenzenesulfonate, the initiator, the sodium carboxymethyl cellulose, and the calcium sulfate are 7% - 9%, 30% - 35%, 20% - 25%, 11% - 13%, 6% - 8%, 2% - 6%, and 1% - 5% in sequence.

[0093] In the present invention, by optimizing the mass percentages of each component, while achieving the best effects of each component, the dosage of the components can be reduced, thereby avoiding waste of resources, saving costs, reducing the production of waste liquid, and reducing the impact on the environment.

[0094] In some embodiments, the hydrocarbon compounds are styrene, methacrylic acid, and divinylbenzene;

[0095] The mass percentages of the styrene, the methacrylic acid, and the divinylbenzene are (45 - 55)% : (20 - 25)% : (20 - 25)%.

[0096] It should be noted that the mass percentages of styrene, methacrylic acid, and divinylbenzene can be (45:20:20)%, (50:22:21)%, (50:20:25)%, (55:25:25)%, etc.

[0097] In the present invention, styrene, as the main monomer, can form resin particles with larger pore diameters and higher specific surface areas. This structure is conducive to the uniform dispersion and firm binding of the extractant in the resin particles, thereby improving the adsorption performance of the extraction resin. Methacrylic acid and divinylbenzene further regulate the pore size distribution and crosslinking degree of the resin particles, making them have more uniform pore sizes and higher mechanical strength.

[0098] In specific implementation, the copolymerization of styrene and divinylbenzene can form a crosslinked structure, thereby improving the mechanical strength and chemical stability of the resin particles. Such high-strength resin particles can withstand higher operating pressures, reduce breakage and wear during the purification process, and help extend the service life of the extraction resin.

[0099] In specific implementation, the addition of methacrylic acid introduces carboxyl functional groups, which can form stronger chemical bonds with other functional groups on the resin surface, further enhancing the chemical stability of the resin particles.

[0100] In some embodiments, the peroxide initiator is benzoyl peroxide, diisopropylbenzene peroxide or di-tert-butyl peroxide;

[0101] The azo initiator is azobisisobutyronitrile or azobisisoheptonitrile.

[0102] In the present invention, the peroxide initiator and the azo initiator have different decomposition temperatures and reaction activities, and the appropriate initiator can be selected according to the process requirements, so as to precisely control the rate and degree of the polymerization reaction, avoid the problem of uneven resin structure caused by too fast or too slow polymerization reaction, and thus form resin particles with uniform pore size distribution and high specific surface area.

[0103] In specific implementation, the peroxide initiator and the azo initiator can effectively initiate the polymerization reaction of styrene, methacrylic acid and divinylbenzene to form a crosslinked structure and obtain high-strength resin particles.

[0104] The present invention also provides an application of the extraction resin in the purification of ammonium perrhenate. The extraction resin is prepared by the above preparation method, and the extraction resin is used for purifying ammonium perrhenate;

[0105] The purification method includes:

[0106] Inject an ammonium perrhenate solution with a concentration not greater than 35 g / L into a chromatography column filled with the extraction resin at a flow rate of 2Bv~7 Bv, and ammonium perrhenate with a purity greater than 99.99% is obtained after passing through.

[0107] It should be noted that selecting an ammonium perrhenate solution with a concentration not greater than 35 g / L can ensure the adsorption efficiency and selectivity of the extraction resin for ammonium perrhenate;

[0108] The flow rate can be set to 2 Bv, 3 Bv, 4 Bv, 5 Bv, 6 Bv, 7 Bv; the flow rate is one of the key factors affecting the purification effect of the chromatography column; too fast a flow rate (>7 Bv) may result in insufficient contact time between the ammonium perrhenate solution and the extraction resin, reducing the adsorption efficiency; too slow a flow rate (<2 Bv) will lead to low production efficiency; a flow rate range of 2 Bv - 7 Bv can improve production efficiency while ensuring the adsorption efficiency.

[0109] After use, the extraction resin can be regenerated with an eluent (such as dilute acid or dilute alkali solution) to remove the adsorbed impurity ions and restore its adsorption capacity. The regenerated extraction resin can be recycled multiple times, thereby reducing production costs and environmental impact.

[0110] In the present invention, the Figure 1 extraction resin prepared by the preparation method shown is used to purify ammonium perrhenate, which can significantly improve the purification efficiency and purity of ammonium perrhenate compared with traditional extraction resins. The high selectivity and strong adsorption capacity of the extraction resin for ammonium perrhenate ensure that impurity ions (such as molybdenum, tungsten, etc.) in the ammonium perrhenate solution are effectively removed, thereby obtaining an ammonium perrhenate product with a purity greater than 99.99%.

[0111] Specifically, the operation method of the chromatography column proposed in the present invention is simple and easy to implement, with high operability and repeatability. By controlling the flow rate within the range of 2 Bv - 7 Bv, problems such as insufficient adsorption caused by too fast a flow rate or low production efficiency caused by too slow a flow rate can be avoided.

[0112] In summary, the purification method of the present invention can obtain an ammonium perrhenate product with a purity greater than 99.99%, meeting the strict requirements for high-performance rhenium materials in fields such as aerospace. This high-purity ammonium perrhenate is a key raw material for preparing high-purity metallic rhenium, which is of great significance for ensuring the strategic resource needs of China's aerospace industry.

[0113] To make those skilled in the art understand the present invention more clearly, the following examples are used to detail the preparation method of an extraction resin and its application in the purification of ammonium perrhenate described in the present invention.

[0114] Example 1

[0115] Prepare an extraction resin, including:

[0116] (1) Mix 50 ml of ultrapure water, 40 ml of ammonia water, and 10 g of sodium hydroxide to obtain an aqueous phase mixture;

[0117] (2) Mix 75 ml of 260# sulfonated kerosene, 20 ml of diisooctyl phosphate, and 5 ml of sec-octanol to obtain an oil phase mixture;

[0118] (3) Add 5 g of guar gum and 35 g of gelatin into pure water at 80 °C, stir and dissolve them. Then, add 15 g of styrene, 8 g of divinylbenzene, 7 g of methacrylic acid, 13 g of sodium dodecylbenzenesulfonate, 4 g of sodium carboxymethylcellulose, 3 g of calcium sulfate and 10 g of azodiisobutyronitrile into the obtained colloidal solution in sequence. Heat it to 95 °C, then stir and mix well, keep it warm for 2 h, and then cool, filter and wash to obtain the required solid resin particles;

[0119] (4) Add the obtained solid resin particles into pure water with the same volume, control the temperature of pure water at 60 °C, slowly add the above oil-phase mixture into the obtained system, stir slightly during the adding process, and the volume ratio of the solid particles to the added oil-phase mixture is 1:0.6. Stir for 30 min, keep it warm for 1 h, then cool to room temperature, and then add the above-prepared water-phase mixture, and the adding amount is 17.5% of the volume of the added oil-phase mixture. Stir slightly during the adding process, and the stirring time is 20 min. Then filter, and wash with pure water until it is clear and the pH is neutral to obtain the extraction resin.

[0120] Provide an application of the extraction resin prepared in Example 1 in purifying ammonium perrhenate, specifically including:

[0121] Take the ammonium perrhenate solution in the copper smelting system with a concentration of 28 g / L, inject it into the chromatography column filled with the extraction resin prepared in Example 1 above. After passing through at a flow rate of 2Bv, a high-purity ammonium perrhenate solution is obtained. Heat it for crystallization and wash it to obtain ammonium perrhenate products. Analyze and measure it, and the results are shown in Table 1 below:

[0122] Table 1 Analysis and measurement results (I)

[0123]

[0124] According to Table 1, it can be obtained that for the extraction resin prepared in Example 1 of the present invention, after the two samples are purified, the purity of the ammonium perrhenate products both reaches ≥99.99%, indicating that the extraction resin prepared by the present invention has a very significant purification effect on ammonium perrhenate and can improve the purity of ammonium perrhenate to an extremely high level.

[0125] Example 2

[0126] Prepare an extraction resin, including:

[0127] (1) Mix 50 ml of ultrapure water, 45 ml of ammonia water and 5 g of sodium hydroxide to obtain an aqueous phase mixture;

[0128] (2) Mix 75 ml of 260# sulfonated kerosene, 20 ml of diisooctyl phosphate and 5 ml of sec-octanol to obtain an oil phase mixture;

[0129] (3) Add 5 g of guar gum and 40 g of gelatin into pure water at 80 °C, stir and dissolve. Then, sequentially add 10 g of styrene, 5 g of divinylbenzene, 5 g of methacrylic acid, 15 g of sodium dodecylbenzenesulfonate, 5 g of sodium carboxymethylcellulose, 5 g of calcium sulfate and 10 g of benzoyl peroxide into the obtained colloidal solution. Heat to 95 °C, then stir thoroughly and mix well, and then keep warm for 2 h. Then cool, filter and wash to obtain the required solid resin particles;

[0130] (4) Add the obtained solid resin particles into pure water with an equal volume, control the temperature of the pure water at 60 °C, slowly add the above-mentioned oil-phase mixture into the obtained system, stir slightly during the addition process. The volume ratio of the solid particles to the added oil-phase mixture is 1:0.6. Stir for 30 min, keep warm for 1 h, then cool to room temperature, and then add the above-prepared water-phase mixture. The addition amount is 15% of the volume of the added oil-phase mixture. Stir slightly during the addition process, and the stirring time is 20 min. Then filter and wash with pure water until it is clear and the pH is neutral to obtain the extraction resin.

[0131] Provide an application of the extraction resin prepared in Example 2 in purifying ammonium perrhenate, which specifically includes: Take the ammonium perrhenate solution in the molybdenum smelting system with a concentration of 5 g / L, inject it into the chromatography column filled with the above-mentioned extraction resin. After passing through at a flow rate of 5 Bv, a high-purity ammonium perrhenate solution is obtained. Heat it for crystallization and wash it to obtain the ammonium perrhenate product, and conduct analysis and determination on it. The results are shown in the following table:

[0132] Table 2 Analysis and determination results (II)

[0133]

[0134] It can be obtained from Table 2 that the differences between Example 1 and Example 2 lie in slightly different component contents, preparation parameters, etc. The extraction resin prepared in Example 2 still has a very significant purification effect on the two samples, and ammonium perrhenate with a purity greater than 99.99% can be obtained, indicating that by restricting the dosage of each component in the present invention, the adsorption performance of the prepared extraction resin for ammonium perrhenate is stronger than that of the traditional extraction resin, and it can be better applied to the purification of ammonium perrhenate.

[0135] In summary, the extraction resin obtained by the preparation method provided by the present invention can remove impurity components in ammonium perrhenate with high selectivity and high efficiency, obtain high-purity ammonium perrhenate products, and the extractant can be uniformly and highly loaded on the resin with stable properties and a large loading capacity, increasing the number of cycle service life times. This extraction resin combines the advantages of the extractant and the resin.

[0136] Each embodiment in this specification is described in a progressive manner. Each embodiment focuses on the differences from other embodiments. For the same or similar parts among the embodiments, reference can be made to each other.

[0137] Although the preferred embodiments of the embodiments of the present application have been described, those skilled in the art can make additional changes and modifications to these embodiments once they know the basic creative concept. Therefore, the appended claims are intended to be construed to include the preferred embodiments and all changes and modifications that fall within the scope of the embodiments of the present application.

[0138] Finally, it should also be noted that in this text, relational terms such as "first" and "second" are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the term "comprising", "including" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, article or terminal device comprising a series of elements not only includes those elements, but also includes other elements not expressly listed, or also includes elements inherent to such process, method, article or terminal device. Without further limitation, an element defined by the statement "comprising an..." does not exclude the existence of additional identical elements in the process, method, article or terminal device comprising the element.

[0139] The above provides a detailed introduction to a method for preparing extraction resin and its application in purifying ammonium perrhenate. Specific examples are used in this article to elaborate on the principle and implementation manner of the present application. The description of the above embodiments is only used to help understand the method and its core idea of the present application; at the same time, for those of ordinary skill in the art, according to the idea of the present application, there will be changes in the specific implementation manner and application scope. In summary, the content of this specification should not be construed as a limitation to the present application.

Claims

1. An application of a leaching resin in purifying ammonium rhenate, characterized in that: The preparation method of the leaching resin comprises: The resin particles are added to an equal volume of pure water at a temperature of 55°C to 65°C, the oil phase mixture is added to the obtained system, stirred, cooled, and then the water phase mixture is added, stirred, filtered, and washed to obtain the leaching resin; The method for preparing the resin particles comprises: Gul gum and gelatin are added to pure water at a temperature of 70°C to 80°C, hydrocarbon compounds, sodium dodecylbenzene sulfonate, an initiator, sodium carboxymethyl cellulose and calcium sulfate are added to the obtained colloidal solution, mixed at 90°C to 95°C, kept warm for 2 h to 4 h, cooled, filtered and washed to obtain the resin particles; Wherein, the volume ratio of the resin particles to the oil phase mixed liquid is 1:(0.4-0.7); the volume ratio of the oil phase mixed liquid to the water phase mixed liquid is 1:(0.6-0.75); The oil phase mixed liquid is composed of 65% to 80% by weight of a diluent, 20% to 30% by weight of a lipid compound and 5% to 10% by weight of octanol, and the sum of the mass percentages of each component is 100%; the lipid compound is diisooctyl phosphate and / or 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester; The aqueous phase mixed liquid is composed of 35% to 50% pure water, 25% to 45% ammonia water and 5% to 10% sodium hydroxide in percentage by mass, and the sum of the percentages by mass of each component is 100%.

2. The use of the leaching resin in purifying ammonium rhenate according to claim 1, characterized in that: The volume ratio of the resin particles to the oil phase mixed liquid is 1:(0.5-0.6).

3. The use of the leaching resin in purifying ammonium rhenate according to claim 1, characterized in that: The diluent is 260# sulfonated kerosene, n-dodecane or xylene.

4. The use of the leaching resin in purifying ammonium rhenate according to claim 1, characterized in that: The hydrocarbon compound is at least one of styrene, methacrylic acid and divinylbenzene; The initiator is a peroxide initiator or an azo initiator.

5. The use of the leaching resin in purifying ammonium rhenate according to claim 1, characterized in that: In the resin particles, the mass percentages of the gul gum, the gelatin, the hydrocarbon compound, the sodium dodecylbenzene sulfonate, the initiator, the sodium carboxymethyl cellulose and the calcium sulfate are 5% to 10%, 25% to 40%, 15% to 30%, 10% to 15%, 5% to 10%, 2% to 6%, and 1% to 5%, respectively, and the sum of the mass percentages of each component is 100%.

6. The use of the leaching resin in purifying ammonium rhenate according to claim 1, characterized in that: In the resin particles, the mass percentages of the guar gum, the gelatin, the hydrocarbon compound, the sodium dodecylbenzene sulfonate, the initiator, the sodium carboxymethyl cellulose and the calcium sulfate are 7% to 9%, 30% to 35%, 20% to 25%, 11% to 13%, 6% to 8%, 2% to 6%, and 1% to 5%, respectively, and the sum of the mass percentages of the components is 100%.

7. The use of the leaching resin in purifying ammonium rhenate according to claim 6, characterized in that: The hydrocarbon compounds are styrene, methacrylic acid and divinylbenzene; The mass percentages of the styrene, the methacrylic acid and the divinylbenzene are (45-55) %: (20-25) %: (20-25) %, and the sum of the mass percentages of the components is 100 %.

8. The use of the leaching resin in purifying ammonium rhenate according to claim 4, characterized in that: The peroxide initiator is benzoyl peroxide, dicumyl peroxide or di-tert-butyl peroxide; The azo initiator is azobisisobutyronitrile or azobisisoheptanenitrile.

9. The use of the leaching resin in purifying ammonium rhenate according to claim 1, characterized in that: The method for purifying ammonium rhenate by leaching resin comprises: An ammonium rhenate solution with a concentration of no more than 35 g / L is injected into a chromatography column containing the leaching resin, and ammonium rhenate with a purity greater than 99.99% is obtained after passing through.

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