Leverage resin, preparation method and application of Leverage resin in purification of ammonium molybdate

Abstract

The invention provides a levextrel resin, a preparation method and an application of the levextrel resin in purification of ammonium molybdate, and the levextrel resin is prepared by loading an alkyl phosphine oxide-primary amine mixed extraction agent on an inert support through vacuum stirring. Specifically, the specific surface area and porosity of the inert support are increased through swelling treatment, and the selective adsorption capacity of impurities in molybdate is enhanced through the synergistic effect of the mixed extraction agent; and the extraction agent is uniformly dispersed and firmly combined with the resin through vacuum stirring. The preparation method effectively solves the problems of non-uniform dispersion, easy loss, easy saturation and the like of the traditional extraction resin extraction agent, and provides a more efficient separation material for high-purity molybdenum production.

Description

Technical Field

[0001] The present application relates to the technical field of metal purification, and in particular to a leaching resin, a preparation method and an application thereof in purifying ammonium molybdate. Background Art

[0002] Molybdenum is a rare and dispersed metal with excellent properties. Metallic molybdenum has a high melting point, excellent electrical and thermal conductivity, corrosion resistance, and excellent resistance to thermal fatigue. Molybdenum has medium hardness and strong toughness and ductility. High-purity molybdenum can be used to prepare molybdenum targets. Sputtering deposits the target onto various substrates to form films, which are widely used in various electronic products. High-purity molybdenum can also be used in rocket nozzles, chemical reagents, and catalysts.

[0003] Currently, the production of high-purity molybdenum metal primarily involves the purification of ammonium molybdate through hydrometallurgical processes such as extraction, ion exchange, and temperature-controlled recrystallization. Extraction chromatography, a novel column chromatography method for inorganic separation, uses an extractant-adsorbed eluting resin as the stationary phase and an aqueous solution as the mobile phase to separate different substances. However, existing eluting resins still suffer from issues such as poor ammonium molybdate purification, uneven dispersion of the extractant, poor binding to the resin, easy loss, low adsorption and extraction capacity, and saturation. Summary of the Invention

[0004] To address the above-mentioned issues, the present invention provides a leaching resin, a preparation method, and its use in purifying ammonium molybdate. The leaching resin is prepared by loading an alkylphosphine oxide-primary amine mixed extractant onto an inert support through vacuum stirring. The swelling treatment increases the specific surface area and porosity of the inert support, while the synergistic effect of the mixed extractants enhances the adsorption capacity of impurities in the molybdate. The vacuum stirring ensures uniform dispersion of the extractant and a strong bond with the resin. This preparation method effectively addresses the issues of uneven dispersion, easy loss, and saturation of the extractant in conventional leaching resins, providing a more efficient separation material for high-purity molybdenum production.

[0005] In a first aspect, the present invention provides a method for preparing a leaching resin, the preparation method comprising: Immerse the inert support in the impregnation solution to allow it to fully swell; take an extractant and an appropriate amount of the impregnation solution and mix them to form a mixed solution; The mixed solution is mixed with the swollen inert support, and stirred under vacuum conditions to load the extractant on the swollen inert support. After drying, the leaching resin is obtained. wherein the inert support is selected from at least one of polystyrene, polystyrene-divinylbenzene, polyethylene, polyacrylate and polyurethane foam; The extractant is formed by mixing alkyl phosphine oxide and primary amine.

[0006] Optionally, the amount of the extractant is 30%-50% of the mass of the inert support.

[0007] Optionally, the alkyl phosphine oxide is trialkyl phosphine oxide or tri-n-octyl phosphine oxide; The primary amine is a secondary carbon primary amine or 3-(nonyloxy)propane-1-amine.

[0008] Optionally, the molar ratio of the alkyl phosphine oxide to the primary amine is (1-5):1.

[0009] Optionally, the inert support is polystyrene-divinylbenzene or polyacrylate.

[0010] Optionally, the impregnation liquid is selected from at least one of methanol, ethanol, dichloromethane and benzene.

[0011] Optionally, the stirring speed is 25 rpm-60 rpm, and the stirring time is 1 h-6 h.

[0012] In a second aspect, the present invention provides a leaching resin, which is obtained by the preparation method described in the first aspect.

[0013] In a third aspect, the present invention provides a use of a leaching resin in purifying ammonium molybdate, wherein the leaching resin is obtained by the preparation method described in the first aspect above, and the leaching resin is used to purify an ammonium molybdate solution having a concentration not exceeding 40 g / L, and obtain ammonium molybdate with a purity of at least 99.99%.

[0014] Optionally, the purification method comprises: The leaching resin is placed in deionized water, and after swelling, is loaded into a chromatography column; Passing dilute hydrochloric acid through the swollen leaching resin at a flow rate of 2 BV / h-5 BV / h to obtain an activated leaching resin; An ammonium molybdate solution having a concentration of no more than 40 g / L is passed through a chromatography column containing the activated leaching resin at a flow rate of 3 BV / h-7 BV / h to obtain ammonium molybdate with a purity of at least 99.99% after impurities are removed.

[0015] In summary, the present invention has at least the following beneficial technical effects: 1. The present invention provides a method for preparing a leaching resin, comprising immersing an inert support in an impregnation liquid to fully swell it, then mixing an extractant with an appropriate amount of the impregnation liquid to form a mixed solution, mixing the mixed solution with the swollen inert support, stirring under vacuum conditions, so that the extractant is loaded onto the swollen inert support, and drying the mixture to produce the leaching resin. The present invention utilizes an inert support such as polystyrene or polystyrene-divinylbenzene, in combination with a mixed extractant consisting of an alkylphosphine oxide and a primary amine, and combines the mixture with vacuum stirring and loading to significantly enhance the purification effect of the leaching resin on ammonium molybdate. Specifically, the synergistic effect of the components in the mixed extractant enhances the selective adsorption capacity of impurities in molybdate, effectively solving the problem of low separation efficiency of traditional methods; through the swelling of the impregnation liquid combined with vacuum stirring, the uniform distribution and firm binding of the extractant on the inert support are achieved, significantly reducing the loss of the extractant. At the same time, the inert support after swelling treatment has a larger specific surface area and higher porosity, which can not only load more extractant, but also delay the saturation phenomenon, thereby greatly improving the adsorption capacity and use stability of the extractant resin, overcoming the defects of uneven dispersion of the extractant, easy saturation, and poor binding force.

[0016] 2. The present invention provides a leaching resin that utilizes an extractant composed of an alkylphosphine oxide and a primary amine, combined with an inert support, to achieve efficient and selective separation of ammonium molybdate solutions. The extractant is uniformly distributed and stably bound to the resin support, significantly improving its utilization efficiency and service life. The swelling-treated resin support exhibits superior pore structure and surface properties, effectively overcoming the limitations of conventional leaching resins in the ammonium molybdate purification process and providing a reliable separation material for the production of high-purity molybdenum products.

[0017] 3. The present invention provides the use of a leaching resin for the purification of ammonium molybdate. This leaching resin is suitable for the deep purification of low- to medium-concentration ammonium molybdate solutions, efficiently removing impurity elements and consistently producing ultra-high-purity ammonium molybdate products. The loaded extractant exhibits enhanced adsorption capacity for impurity ions in the solution, effectively reducing co-extraction of molybdate ions. In use, this leaching resin exhibits stable separation performance, excellent mass transfer efficiency, and long-term recyclability, enhancing the overall efficiency of the ammonium molybdate purification process. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following briefly introduces the drawings required for use in the description of the embodiments of the present application. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0019] Figure 1The following is a flow chart of the preparation method of the leaching resin proposed in the embodiment of the present application; Figure 2 The flowchart of the method for purifying ammonium molybdate with leaching resin proposed in the embodiment of the present application is shown. DETAILED DESCRIPTION

[0020] The following will be combined with the drawings in the embodiments of this application to clearly and completely describe the technical solutions in the embodiments of this application. Obviously, the embodiments described are part of the embodiments of this application, not all of them. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0021] In the drawings, the sizes of components, layer thicknesses, or regions may be exaggerated for clarity. Therefore, any implementation of the present disclosure is not necessarily limited to the dimensions shown in the drawings, and the shapes and sizes of components in the drawings do not reflect true proportions. Furthermore, the drawings schematically illustrate idealized examples, and any implementation of the present disclosure is not limited to the shapes or values shown in the drawings.

[0022] In related technologies, the purity of metallic molybdenum significantly impacts its electronic properties, directly impacting the application areas of high-purity molybdenum. For example, alkali metal impurities such as potassium and sodium easily become mobile ions in the molybdenum lattice, forming bad spots in the insulating layer that can easily lead to breakdown. Impurity elements such as iron and nickel can cause interfacial leakage or increase the presence of oxygen. Therefore, high-purity molybdenum metal has extremely strict requirements for trace impurities. The flat panel display coating and solar cell industries require a purity of 4N (99.99%) or higher for raw molybdenum, while the integrated circuit industry requires a purity of 5N (99.999%) or higher for high-purity molybdenum powder.

[0023] At present, the production of high-purity molybdenum metal mainly involves purification of ammonium molybdate through hydrometallurgical processes such as extraction, ion exchange, and temperature-controlled recrystallization. Among them, extraction and ion exchange are the most widely used methods. However, both extraction and ion exchange have certain limitations. For example, the organic phase loss in the extraction method is large, and the organic waste liquid has a certain impact on the environment, and causes an increase in the carbon content in the product; the ion exchange method has complex resin synthesis and a limited number of regeneration cycles. Another way is to purify the reduced metal molybdenum using powder metallurgy, electron beam melting, zone melting, etc. However, such methods often have the disadvantages of long production cycles, large equipment investment, and serious pollution, and it is difficult to effectively remove high-melting-point metals such as tungsten. Therefore, the present invention starts from the ammonium molybdate raw material and studies the removal of trace impurities, which can reduce the pressure of impurity removal at the back end.

[0024] The present invention has discovered that extraction chromatography is a novel column chromatography method for inorganic separation. It uses an extractant-adsorbed inert support, prepared as a leaching resin, as the stationary phase, and an aqueous solution as the mobile phase to achieve the separation of different substances. By impregnating and adsorbing the extractant onto a weakly polar macroporous adsorption resin, this method combines the high selectivity and efficiency of solvent extraction with the simplicity and pollution-free nature of ion exchange technology. It also overcomes the shortcomings of some extractants, such as difficulty in demixing, high organic residues, and the limitation of the separation limit to the extraction equilibrium. It also offers better selectivity than ion exchange resins.

[0025] However, existing leaching resins still have certain problems, such as poor purification effect of ammonium molybdate, uneven dispersion of the extractant, poor binding force with the resin, easy loss, small adsorption and extraction dosage, and easy saturation.

[0026] Based on the problems existing in related technologies, see Figure 1 The present invention provides a method for preparing a leaching resin, the preparation method comprising: Step S1: Immerse the inert support in an impregnation solution to fully swell it; take an extractant and an appropriate amount of the impregnation solution and mix them to form a mixed solution; wherein the inert support is selected from at least one of polystyrene, polystyrene-divinylbenzene, polyethylene, polyacrylate and polyurethane foam; In this invention, polymer materials such as polystyrene and polystyrene-divinylbenzene are used as inert supports, creating a synergistic effect with the impregnation liquid and extractant loading, significantly improving the overall performance of the leaching resin. This inert support moderately swells in the presence of the impregnation liquid, forming a uniform pore structure. This not only enhances the dispersibility of the extractant but also strengthens its binding strength through intermolecular forces, significantly reducing the risk of extractant loss. Furthermore, the polystyrene-based material's adsorption of organic matter, synergistically with the extractant, further optimizes the selective adsorption capacity of impurities, ensuring that the leaching resin possesses both high capacity and high stability during the purification process.

[0027] Cross-linked polymers such as polystyrene-divinylbenzene, combined with their rigid skeleton and moderate swelling properties, ensure the stability of the support structure. Leachable resins prepared using these inert supports combine excellent mechanical strength, high specific surface area, and stable extractant retention, effectively addressing the issues of low extractant loading and easy loss associated with traditional leaching resins.

[0028] In specific implementation, the inert support can be selected from one of polystyrene, polystyrene-divinylbenzene, polyethylene, polyacrylate and polyurethane foam plastic, or a combination of any of them.

[0029] In the present invention, the inert support is polystyrene-divinylbenzene or polyacrylate.

[0030] The cross-linked structure of polystyrene-divinylbenzene provides a stable three-dimensional network and an optimal pore size distribution, enabling controlled swelling in the impregnation solution and creating an optimal loading environment for the extractant. Polyacrylate, on the other hand, enhances its affinity for the extractant due to its structural characteristics. These two inert supports not only possess excellent chemical stability and mechanical strength, but their unique surface properties also promote uniform dispersion and strong binding of the extractant, effectively resolving the issues of uneven distribution and easy loss of extractants in traditional resins.

[0031] In the present invention, the impregnation liquid is at least one selected from methanol, ethanol, dichloromethane and benzene.

[0032] Using solvents such as methanol and ethanol, or organic solvents such as dichloromethane and benzene as the impregnation liquid can effectively promote the swelling process of the inert support and enhance the openness of its pore structure. When impregnating the extractant, the impregnation liquid composed of the above components also facilitates uniform dispersion of the extractant in the inert support, improving the binding strength between the extractant molecules and the inert support. In the present invention, the appropriate impregnation liquid can be selected for different extractant components to optimize their loading efficiency, thereby producing a leaching resin with more uniform extractant distribution and stronger binding.

[0033] In the present invention, the inert support may be immersed in the impregnation liquid for 1 h to 3 h; for example, the inert support may be immersed in the impregnation liquid for 1 h, 1.5 h, 2 h, 2.5 h, or 3 h to allow the inert support to fully swell; In the present invention, the amount of the extractant is 30%-50% of the mass of the inert support.

[0034] In specific implementations, the amount of the extractant can be 30%, 35%, 40%, 45%, or 50% of the mass of the inert support.

[0035] In the present invention, by controlling the amount of extractant to within 30%-50% of the inert support mass, the pore capacity of the inert support is fully utilized while avoiding agglomeration or loss caused by excessive extractant. This allows the extractant molecules to be fully and evenly distributed within the pore structure of the inert support, forming a stable binding state. This solves the problems of uneven extractant distribution, easy saturation, and easy loss in traditional preparation methods, resulting in a leaching resin with superior adsorption selectivity and a longer service life during the ammonium molybdate purification process.

[0036] In the present invention, the extractant is formed by mixing an alkyl phosphine oxide and a primary amine.

[0037] The synergistic effect of a composite extractant composed of alkylphosphine oxide and primary amine is maximized through the use of a polystyrene inert support and controlled loading. The protonated amine extractant enhances selectivity for polyacid impurities that are prone to forming in ammonium molybdate. The introduction of the alkylphosphine oxide also strengthens the interaction between the extractant molecules and the inert support, further reducing extractant loss and significantly improving the separation factor. This addresses the issues of single extractant saturation and impurity co-adsorption.

[0038] In the present invention, the alkyl phosphine oxide is trialkyl phosphine oxide or tri-n-octyl phosphine oxide; The primary amine is a secondary carbon primary amine or 3-(nonyloxy)propane-1-amine.

[0039] In specific implementation, the extractant can be composed of trialkylphosphine oxide and secondary carbon primary amine, or trialkylphosphine oxide and 3-(nonyloxy)propane-1-amine, or tri-n-octylphosphine oxide and secondary carbon primary amine, or tri-n-octylphosphine oxide and 3-(nonyloxy)propane-1-amine.

[0040] In the present invention, trialkylphosphine oxide compounds, due to their long-chain alkyl structures, are highly compatible with the hydrophobicity of the polystyrene-divinylbenzene inert support. They also form hydrogen bonds with amines, enhancing binding stability and strengthening nonpolar interactions with the polyacrylate inert support. Combining these alkylphosphine oxides with primary amines ensures that the extractant remains stable at loadings of 30%-50%. This not only improves the adsorption capacity and purity of ammonium molybdate (≥99.99%) but also reduces extractant loss to extremely low levels through intermolecular synergy, resolving the issues of poor selectivity and susceptibility to loss associated with leaching resins prepared using traditional methods.

[0041] In the present invention, the molar ratio of the alkyl phosphine oxide to the primary amine is (1-5):1.

[0042] In a specific implementation, the molar ratio of the alkyl phosphine oxide to the primary amine can be 1:1, 2:1, 3:1, 4:1, or 5:1.

[0043] In the present invention, the molar ratio of alkylphosphine oxide to primary amine is controlled between (1-5):1. This is based on the chemical properties of trialkylphosphine oxide / tri-n-octylphosphine oxide and primary amines with specific structures. The two extractants, when mixed, exhibit a synergistic effect, achieving greater selectivity for impurities than a single extractant alone. Under the adsorption effect of the non-polar skeleton of the inert support and the swelling effect of the impregnation solution, combined with vacuum loading and an extractant loading of 30%-50%, the extractant is orderly arranged within the pores of the inert support. The long-chain alkyl groups of the alkylphosphine oxide are tightly adsorbed to the inert support skeleton. At the same time, hydrogen bonding enhances the adsorption stability of the primary amine, whose polarity increases after protonation. This solves the problems of low extractant adsorption stability and insufficient selectivity in traditional processes, enabling the leaching resin to combine high adsorption capacity, ultra-high selectivity, and long-term stability in the ammonium molybdate purification process.

[0044] Step S2: mixing the mixed solution with the swollen inert support, stirring under vacuum conditions to load the extractant on the swollen inert support, and drying to obtain the leaching resin.

[0045] In a specific implementation, the mixed solution and the swollen inert support are mixed into an eggplant-shaped bottle, which is placed in a rotary evaporator. The vacuum and room temperature environment provided by the rotary evaporator is used for rotational stirring to allow the mixed solution to be fully immersed in the swollen inert support.

[0046] In the present invention, the stirring speed is 25 rpm-60 rpm, and the stirring time is 1 h-6 h.

[0047] In a specific implementation, the stirring speed can be 25 rpm, 30 rpm, 35 rpm, 40 rpm, 45 rpm, 50 rpm, 55 rpm, or 60 rpm, and the time can be 1 h, 2 h, 3 h, 4 h, 5 h, or 6 h.

[0048] In this invention, by setting the vacuum stirring speed within the range of 25-60 rpm and the duration within the range of 1-6 hours, the impregnation liquid is ensured to fully penetrate the pores of the inert support while avoiding uneven distribution of the extractant caused by high-speed shearing. This 1-6 hour duration, combined with a (1-5:1) extractant ratio and a loading of 30%-50%, allows trialkylphosphine oxides and other compounds to gradually form a stable assembly structure with primary amine molecules, achieving uniform molecular-level anchoring of the extractant on the inert support framework, thereby reducing extractant loss. Furthermore, by maintaining the integrity of the alkylphosphine oxide active sites, the adsorption selectivity of the leaching resin for ammonium molybdate is enhanced, providing process support for the industrial production of high-purity molybdenum products of grade 4N and above.

[0049] In the present invention, the drying process in step S2 includes rotary evaporation and drying; Wherein, rotary evaporation comprises: The stirred mixed system was heated to 40°C and subjected to rotary evaporation to fully volatilize the impregnating agent until the resin was dispersed solid. The drying process includes: transferring the dispersed solid obtained by rotary evaporation to an oven at 30°C-60°C and drying for 6 hours-12 hours to obtain the leaching resin.

[0050] In the present invention, a rotary evaporation treatment is first performed at 40°C to allow the impregnation liquid to evaporate gently, thereby preventing high temperature from damaging the molecular structure of the alkylphosphine oxide-primary amine composite extractant and ensuring that the extractant loaded on the inert support is evenly distributed. Subsequently, a low-temperature drying process is performed at 30°C-60°C for 6 hours-12 hours, which is connected to the stirring process at 25 rpm-60 rpm to form a process connection, so that the extractant forms a stable bond with the inert support at a ratio of (1-5):1.

[0051] The above-mentioned segmented drying method not only completely preserves the active sites of the extractant, but also prevents the enrichment of the extractant in micro-regions by controlling the volatilization rate, so that the final leaching resin obtained still maintains excellent pore structure and surface properties at a loading amount of 30%-50% of the extractant.

[0052] In summary, the method for preparing a leaching resin provided by the present invention involves immersing an inert support in an impregnation solution to fully swell it, relaxing the polymer chains and expanding the pore structure, thereby increasing the specific surface area and internal accessibility of the inert support. This allows the subsequently loaded extractant to be more evenly distributed within and on the surface of the inert support, avoiding localized overloading or uncovered areas, and addressing the uneven dispersion problem of conventional extractants.

[0053] The swollen inert support and mixed solution are stirred under vacuum conditions to promote the diffusion of extractant molecules into the inert support. This enhances physical adsorption and chemical bonding between the extractant and the inert support, reduces the risk of extractant loss, increases extractant loading, and delays saturation.

[0054] A mixed extractant of alkylphosphine oxide and primary amine is used. Protonation of the primary amine significantly enhances selectivity for impurities, while the coordination and hydrogen bonding of the phosphine oxide significantly enhance the stability of the extractant and its adsorption strength on the support. This improves the purification efficiency of ammonium molybdate while reducing interference from competitive adsorption. Highly cross-linked polymers such as polystyrene-divinylbenzene are used as inert supports. Their three-dimensional network structure and chemical inertness allow them to withstand strong acidic and alkaline environments, thereby enhancing the mechanical strength and chemical stability of the extractant resin, maintaining its structural integrity during long-term cyclic use and reducing extractant loss due to damage. Drying slowly removes the impregnation solution, allowing the extractant molecules to form a stable solid layer within the pores of the inert support, further reducing elution losses during use and extending the resin's service life.

[0055] The present invention also provides a leaching resin, which is obtained by the above-mentioned preparation method.

[0056] This leaching resin has high impurity selectivity, high adsorption capacity and long-term stability, and can stably produce ammonium molybdate with a purity of ≥99.99%. It solves the problems of traditional leaching resin extractant loss, easy saturation and low separation efficiency, and provides a reliable material basis for the industrial production of high-purity molybdenum.

[0057] The present invention also provides a use of a leaching resin in purifying ammonium molybdate. The leaching resin is obtained by the above-described preparation method. The leaching resin is used to purify an ammonium molybdate solution having a concentration not exceeding 40 g / L, and to obtain ammonium molybdate having a purity of at least 99.99%.

[0058] The leaching resin prepared by this invention is suitable for the efficient purification of ammonium molybdate solutions with a concentration of ≤40 g / L. During use, the 3D pore structure of the leaching resin and the alkylphosphine oxide-primary amine active sites synergistically achieve highly selective capture of impurity ions. Furthermore, the 30%-50% extractant loading ensures sufficient adsorption capacity. This leaching resin solves the problems of incomplete impurity removal and resin deactivation in traditional processes, enabling the stable production of ultra-high-purity ammonium molybdate exceeding 99.99%.

[0059] See also Figure 2 In the present invention, the purification method includes: Step S11: placing the leaching resin in deionized water, and loading it into a chromatography column after swelling; Step S21: passing dilute hydrochloric acid through the swollen leaching resin at a flow rate of 2 BV / h-5 BV / h to obtain an activated leaching resin; In a specific implementation, the dilute hydrochloric acid can pass through the swollen leaching resin at a flow rate of 2 BV / h, 3 BV / h, 4 BV / h, or 5 BV / h.

[0060] In the present invention, after activation, the protonated amine extractant exists in the form of ion pairs, and the extraction mechanism is mainly ion association mechanism, which makes it easier to preferentially extract the isopolyacid and heteropolyacid anions formed by impurities, so that the impurity ions are efficiently adsorbed, thereby improving the separation coefficient of the leaching resin.

[0061] Step S31: passing an ammonium molybdate solution having a concentration of no more than 40 g / L through a chromatography column containing the activated leaching resin at a flow rate of 3 BV / h-7 BV / h to obtain ammonium molybdate with a purity of at least 99.99% after impurities are removed.

[0062] In a specific implementation, the ammonium molybdate solution can pass through the chromatography column containing the activated leaching resin at a flow rate of 3 BV / h, 4 BV / h, 5 BV / h, 6 BV / h, or 7 BV / h.

[0063] In summary, in the purification method provided by the present invention, the leaching resin is activated with dilute hydrochloric acid, protonating the primary amine groups into positively charged active sites. This allows for efficient adsorption of anionic impurities through an ion association mechanism, while the alkylphosphine oxide enhances the stability of the extractant through hydrogen bonding and coordination, resulting in a synergistic effect superior to that of a single extractant, ultimately achieving a stable ammonium molybdate purity of over 99.99%. This improves the separation coefficient between impurities and molybdate, reducing the cost of high-purity molybdenum production and improving resource utilization.

[0064] In order to enable those skilled in the art to more clearly understand the present invention, the following examples are used to describe in detail a leaching resin, a preparation method and its application in purifying ammonium molybdate according to the present invention.

[0065] Example 1 AB-8 macroporous adsorption resin was used as an inert support. The skeleton component of AB-8 macroporous adsorption resin was polystyrene-divinylbenzene. The impregnation liquid was anhydrous ethanol. The AB-8 macroporous adsorption resin was placed in the impregnation liquid and soaked for 2 hours to allow it to fully swell. Trialkylphosphine oxide (TRPO) and secondary carbon primary amine are mixed in a molar ratio of 1:1 to obtain an extractant, and the extractant is added to an appropriate amount of anhydrous ethanol and mixed thoroughly to form a mixed solution; The mixed solution was added to anhydrous ethanol containing a swollen inert support, wherein the amount of the extractant was 50% of the mass of the inert support. The resulting mixed system was placed in an eggplant-shaped flask, which was transferred to a rotary evaporator. The mixture was stirred at 45 rpm under vacuum and room temperature for 1 hour to ensure that the mixed solution was fully immersed in the swollen inert support and the extractant was loaded on the swollen inert support. After sufficient loading, the internal temperature of the rotary evaporator was raised to 40°C for rotary evaporation. When the impregnating agent was fully volatilized until the resin was a dispersed solid, it was transferred to a 30°C oven for drying for 12 hours to complete the drying process and obtain the leaching resin for purification of ammonium molybdate.

[0066] The leaching resin prepared in Example 1 was swollen in deionized water and then loaded into a chromatography column. A 28 g / L ammonium molybdate solution from a copper smelting system was injected into the chromatography column containing the leaching resin at a flow rate of 2 Bv / h to obtain a high-purity ammonium molybdate solution. After heating, crystallization, and washing, an ammonium molybdate product was obtained. The product was analyzed and determined, and the results are shown in Table 1 below: Table 1. Determination results of ammonium molybdate products (I)

[0067] Table 1 shows that, for crude ammonium molybdate raw materials of varying initial purity, the leaching resin can consistently produce a high-purity product with a purity of ≥99.99% under industrial conditions of pH 5.2-5.5. Calculations show that the leaching resin prepared in Example 1 has a separation coefficient of 112 for purifying ammonium molybdate, demonstrating its highly selective adsorption capacity for impurity ions.

[0068] Example 2 AB-8 macroporous adsorption resin was used as an inert support. The skeleton component of AB-8 macroporous adsorption resin was polystyrene-divinylbenzene. The impregnation liquid was anhydrous ethanol. The AB-8 macroporous adsorption resin was placed in the impregnation liquid and soaked for 2 hours to allow it to fully swell. Tri-n-octylphosphine oxide (TOPO) and secondary carbon primary amine are mixed in a molar ratio of 2:1 to obtain an extractant, and the extractant is added to an appropriate amount of anhydrous ethanol and mixed thoroughly to form a mixed solution; The mixed solution was added to anhydrous ethanol containing a swollen inert support, wherein the amount of the extractant was 30% of the mass of the inert support. The resulting mixed system was placed in an eggplant-shaped flask, which was transferred to a rotary evaporator and stirred at 50 rpm under vacuum and room temperature for 1.5 hours to ensure that the mixed solution was fully immersed in the swollen inert support and the extractant was loaded on the swollen inert support. After sufficient loading, the internal temperature of the rotary evaporator was raised to 40°C for rotary evaporation. When the impregnating agent was fully volatilized until the resin was a dispersed solid, it was transferred to a 65°C oven for drying for 6 hours to complete the drying process and obtain the leaching resin for purification of ammonium molybdate.

[0069] The leaching resin prepared in Example 2 was swollen in deionized water and then loaded into a chromatography column. Dilute hydrochloric acid was passed through the chromatography column at a flow rate of 3 Bv / h to activate the leaching resin. Then, an ammonium molybdate solution with a concentration of 5 g / L from a molybdenum smelting system was injected into the chromatography column containing the activated leaching resin and passed through the column at a flow rate of 5 Bv / h to obtain a high-purity ammonium molybdate solution. After heating, crystallization, and washing, an ammonium molybdate product was obtained. The ammonium molybdate product was analyzed and determined. The results are shown in Table 2 below: Table 2. Ammonium molybdate product test results (II)

[0070] Table 2 shows that, for crude ammonium molybdate raw materials from molybdenum smelters of varying initial purity, under operating conditions of pH 5.4-5.5, the resin can stably produce ultra-high-purity ammonium molybdate with a purity of ≥99.99%. Calculations show that the leaching resin prepared in Example 2 has a separation coefficient of 155 for the purification of ammonium molybdate. This high separation coefficient demonstrates that the leaching resin exhibits significantly superior selective adsorption of impurities compared to conventional materials. In particular, the synergistic effect of the branched structure of the secondary carbon primary amine and the long alkyl chain of the TOPO significantly enhances the separation coefficient of the leaching resin, improving its adsorption capacity for impurities and yielding high-purity ammonium molybdate.

[0071] Example 3 XAD-7 macroporous adsorption resin was used as an inert support. The skeleton component of XAD-7 macroporous adsorption resin was polyacrylate. The impregnation liquid was anhydrous ethanol. XAD-7 macroporous adsorption resin was placed in the impregnation liquid and immersed for 3 hours to allow it to fully swell. Trialkylphosphine oxide (TRPO) and secondary carbon primary amine are mixed in a molar ratio of 2:1 to obtain an extractant, and the extractant is added to an appropriate amount of anhydrous ethanol and mixed thoroughly to form a mixed solution; The mixed solution was added to anhydrous ethanol containing a swollen inert support, wherein the amount of the extractant was 30% of the mass of the inert support. The resulting mixed system was placed in an eggplant-shaped flask, which was transferred to a rotary evaporator. The evaporator was stirred at 40 rpm under vacuum and room temperature for 1 hour to ensure that the mixed solution was fully immersed in the swollen inert support and the extractant was loaded on the swollen inert support. After sufficient loading, the internal temperature of the rotary evaporator was raised to 40°C for rotary evaporation. When the impregnating agent was fully volatilized until the resin was a dispersed solid, it was transferred to a 30°C oven for drying for 12 hours to complete the drying process and obtain the leaching resin for purification of ammonium molybdate.

[0072] The leaching resin prepared in Example 3 was swollen in deionized water and then loaded into a chromatography column. A 20 g / L ammonium molybdate solution from a molybdenum smelting system was injected into the chromatography column containing the leaching resin at a flow rate of 5 Bv / h to obtain a high-purity ammonium molybdate solution. The solution was heated for crystallization and washed to obtain an ammonium molybdate product, which was analyzed and measured. The results are shown in Table 3 below: Table 3. Ammonium molybdate product test results (III)

[0073] Table 3 shows that the leaching resin prepared in Example 3, through the synergistic effect of a polyacrylate support (XAD-7) and a trialkylphosphine oxide (TRPO) / secondary carbon primary amine composite extractant, consistently yields a high-purity product with a purity of ≥99.99% from crude ammonium molybdate starting material with an initial purity of 98.75%-99.15% at pH 5.4-5.5. Calculations show that the leaching resin prepared in Example 3 achieves a separation coefficient of 162 for the purification of ammonium molybdate. Compared to the 5 g / L solution treated in Example 2, Example 3 maintains high separation efficiency at a high concentration of 20 g / L, demonstrating that the synergistic effect of the polyacrylate's non-polar backbone and TRPO is more suitable for mass transfer in high-concentration systems. The XAD-7 backbone structure facilitates extractant adsorption, while the short-chain alkyl structure of TRPO offers superior compatibility with the resin. The synergistic effect of these two enhances impurity retention.

[0074] Example 4 The only difference between Example 4 and Example 1 is that the molar ratio of trialkylphosphine oxide to secondary carbon primary amine is different. In Example 4, the molar ratio of trialkylphosphine oxide to secondary carbon primary amine is 5:1.

[0075] Example 5 Polystyrene and polyurethane foam plastics were used as inert supports. The impregnation liquid was a mixture of methanol and ethanol. The polystyrene and polyurethane foam plastics were placed in the impregnation liquid and immersed for 3 hours to allow them to fully swell. trialkylphosphine oxide and 3-(nonyloxy)propane-1-amine are mixed in a molar ratio of 1:1 to obtain an extractant, and the extractant is added to an appropriate amount of the impregnation solution and mixed thoroughly to form a mixed solution; The mixed solution was added to anhydrous ethanol containing a swollen inert support, wherein the amount of the extractant was 40% of the mass of the inert support. The resulting mixed system was placed in an eggplant-shaped flask, which was transferred to a rotary evaporator and stirred at 45 rpm under vacuum and room temperature for 3 hours to ensure that the mixed solution was fully impregnated into the swollen inert support and the extractant was loaded onto the swollen inert support. After sufficient loading, the internal temperature of the rotary evaporator was raised to 40°C for rotary evaporation. When the impregnating agent was fully volatilized until the resin was a dispersed solid, it was transferred to a 30°C oven for drying for 12 hours to complete the drying process and obtain the leaching resin for purification of ammonium molybdate.

[0076] In summary, the present invention provides a leaching resin, a preparation method, and its use in purifying ammonium molybdate. A swelling treatment increases the specific surface area and porosity of the inert support. The synergistic effect of the mixed extractants enhances the selective adsorption of impurities in molybdate. Vacuum stirring ensures uniform dispersion and strong binding of the extractants. This preparation method effectively addresses the issues of uneven dispersion, easy loss, and saturation of conventional leaching resin extractants, providing a more efficient separation material for high-purity molybdenum production.

[0077] The various embodiments in this specification are described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the various embodiments can be referenced to each other.

[0078] Although preferred embodiments of the present invention have been described, those skilled in the art may make additional changes and modifications to these embodiments once they become aware of the basic inventive concepts. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the embodiments of the present invention.

[0079] Finally, it should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprises," "includes," or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article, or terminal device that includes a series of elements includes not only those elements, but also other elements not explicitly listed, or elements that are inherent to such process, method, article, or terminal device. In the absence of further restrictions, an element defined by the phrase "comprises a ..." does not exclude the presence of additional identical elements in the process, method, article, or terminal device that includes the element.

[0080] The above is a detailed introduction to a leaching resin, a preparation method and its application in purifying ammonium molybdate provided by the present application. Specific examples are used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the method and core idea of the present application. At the same time, for those skilled in the art, according to the ideas of the present application, there will be changes in the specific implementation methods and application scopes. In summary, the content of this specification should not be understood as limiting the present application.

Claims

1. A method for preparing a leaching resin, characterized in that: The preparation method comprises: Immerse the inert support in the impregnation solution to allow it to fully swell; take an extractant and an appropriate amount of the impregnation solution and mix them to form a mixed solution; The mixed solution is mixed with the swollen inert support, and stirred under vacuum conditions to load the extractant on the swollen inert support. After drying, the leaching resin is obtained. wherein the inert support is selected from at least one of polystyrene, polystyrene-divinylbenzene, polyethylene, polyacrylate and polyurethane foam; The extractant is formed by mixing alkyl phosphine oxide and primary amine.

2. The method for preparing the leaching resin according to claim 1, wherein The amount of the extractant is 30%-50% of the mass of the inert support.

3. The method for preparing the leaching resin according to claim 1, wherein The alkyl phosphine oxide is trialkyl phosphine oxide or tri-n-octyl phosphine oxide; The primary amine is a secondary carbon primary amine or 3-(nonyloxy)propane-1-amine.

4. The method for preparing the leaching resin according to claim 1 or 3, wherein: The molar ratio of the alkyl phosphine oxide to the primary amine is (1-5):

1.

5. The method for preparing the leaching resin according to claim 1, wherein The inert support is polystyrene-divinylbenzene or polyacrylate.

6. The method for preparing the leaching resin according to claim 1, wherein The impregnation liquid is selected from at least one of methanol, ethanol, dichloromethane and benzene.

7. The method for preparing the leaching resin according to claim 1, wherein The stirring speed is 25 rpm-60 rpm, and the stirring time is 1 h-6 h.

8. A leaching resin, characterized in that The leaching resin is obtained by the preparation method described in any one of claims 1 to 7.

9. An application of a leaching resin in purifying ammonium molybdate, characterized in that: The leaching resin is obtained by the preparation method according to any one of claims 1 to 7 above, and the leaching resin is used to purify an ammonium molybdate solution with a concentration not exceeding 40 g / L, and obtain ammonium molybdate with a purity of at least 99.99%.

10. Use of the leaching resin in purifying ammonium molybdate according to claim 9, characterized in that: The method of purification comprises: The leaching resin is placed in deionized water, and after swelling, is loaded into a chromatography column; Passing dilute hydrochloric acid through the swollen leaching resin at a flow rate of 2 BV / h-5 BV / h to obtain an activated leaching resin; An ammonium molybdate solution having a concentration of no more than 40 g / L is passed through a chromatography column containing the activated leaching resin at a flow rate of 3 BV / h-7 BV / h to obtain ammonium molybdate with a purity of at least 99.99% after impurities are removed.

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