A thiourea derivative for separating molybdenum and rhenium, a preparation method of the thiourea derivative, and an application method thereof

Abstract

This invention discloses a thiourea derivative for the separation of molybdenum and rhenium, a method for preparing the thiourea derivative, and its application method, belonging to the field of hydrometallurgical separation technology. The thiourea derivative has the structure shown in formula (1) ( ): R1 and R2 are each independently substituted or unsubstituted C6~C6. 18 Alkyl groups, substituted phenyl groups; wherein, when C6~C6... 18 When an alkyl group is substituted, the substituent is C1~C2. 12 Alkyl groups; when the phenyl group is substituted, the substituent is C4~C5. 18 The alkyl group. The thiourea derivatives provided by this invention can achieve efficient separation of molybdenum and rhenium in a molybdenum-rhenium coexisting system, and have good stability, reusability and environmental friendliness.

Description

Technical Field

[0001] This invention relates to a thiourea derivative for the separation of molybdenum and rhenium, a method for preparing the thiourea derivative, and a method for applying the derivative, belonging to the field of hydrometallurgical separation technology. Background Technology

[0002] Rhenium is an important strategic metal, playing an irreplaceable role in the manufacture of nickel-based single-crystal blades for aero-engines. Since rhenium has no independent deposits and is mainly found as a byproduct of molybdenite, its resource recovery is highly dependent on molybdenum metallurgical processes. During the oxidative roasting or pressure leaching of molybdenite, rhenium is extracted as perrhenate (ReO4). - It enters the solution in the form of molybdate (MoO4) and reacts with molybdate ions (MoO 2- Together, they form a mixed solution containing molybdenum and rhenium. Achieving efficient separation of molybdenum and rhenium from this mixed solution is the core technological step in rhenium resource recovery.

[0003] Currently, the main methods for separating molybdenum and rhenium include solvent extraction, ion exchange, and chemical precipitation. Solvent extraction is the most widely used method in industry, based on the difference in the partition ratios of molybdenum and rhenium between the organic and aqueous phases. Commonly used extractants include amine extractants (such as trioctylamine and trialkyl tertiary amines), phosphorus extractants (such as P204 and P507), and neutral extractants (such as TBP). However, existing extraction systems generally suffer from insufficient selectivity.

[0004] Molybdenum and rhenium have similar chemical properties, both existing as oxygen-containing anions in aqueous solutions. Many extractants have limited ability to extract these two substances, resulting in low separation coefficients (typically Re / Mo separation coefficients less than 50). Often, 5-8 stages of countercurrent extraction are required to achieve ideal separation, leading to long process flows and high equipment investment. Furthermore, some extraction systems suffer from problems such as high water solubility of the extractant, easy emulsification, and difficulty in back-extraction, affecting the stability and economic efficiency of the process.

[0005] Therefore, developing a foam extraction agent specifically for the separation of molybdenum and rhenium that has a simple preparation process, high selectivity, and high separation efficiency has significant industrial application value and theoretical innovation significance. Summary of the Invention

[0006] The present invention aims to overcome the problems of poor reagent selectivity and low separation efficiency in existing molybdenum-rhenium separation technologies. One of the objectives of the present invention is to provide a thiourea derivative for the separation of molybdenum and rhenium. This thiourea derivative can achieve efficient separation of molybdenum and rhenium in a molybdenum-rhenium coexisting system, and has good stability, reusability and environmental friendliness.

[0007] The second objective of this invention is to provide a method for preparing a thiourea derivative for the separation of molybdenum and rhenium. This method prepares a thiourea derivative agent that can specifically recognize rhenium ions by condensation reaction of amine compounds with carbon disulfide. Moreover, this preparation method does not require high-temperature and high-pressure equipment, is simple to operate, and is suitable for industrial production.

[0008] The third objective of this invention is to provide a method for the application of thiourea derivatives in the separation of molybdenum and rhenium. This method is simple and can be widely used in the resource recovery of systems such as molybdenite roasting leaching solution, pressurized leaching solution, and rhenium-containing waste catalyst leaching solution, and has good prospects for industrial application.

[0009] To achieve the above objectives, a first aspect of the present invention is to provide a thiourea derivative for the separation of molybdenum and rhenium, wherein the thiourea derivative is used to separate molybdenum and rhenium;

[0010] The thiourea derivative has the structure shown in formula (1):

[0011] Equation (1);

[0012] R1 and R2 are each independently substituted or unsubstituted C6~C. 18 Alkyl groups, substituted phenyl groups;

[0013] Among them, when C6~C 18 When an alkyl group is substituted, the substituent is C1~C2. 12 Alkyl groups; when the phenyl group is substituted, the substituent is C4~C5. 18 Alkyl groups.

[0014] ReO4 - The hydration energy (approximately -250 kJ / mol) is significantly lower than that of MoO4. 2- (Approximately -400 kJ / mol), this originates from ReO4 - It possesses a larger ionic radius, lower charge density, and weaker hydrophilicity. This difference in hydration energy makes ReO4... - It is easier to dehydrate and coordinate with thiourea derivatives, while MoO4 2- These tend to remain in the aqueous phase. However, this invention has found that the thiourea derivatives provided by this invention have an inherent difference in their binding ability to molybdenum and rhenium. The sulfur atoms in the thiourea derivatives bind to ReO4. - There are strong soft-soft interactions between rhenium atoms, while for MoO4... 2- The effect is relatively weak. Furthermore, by introducing R1 and R2 groups into the thiourea skeleton, a suitable hydrophobic microenvironment can be constructed, reducing ReO4 levels. - The degree of hydration after coordination amplifies the dehydration effect, enhances the interfacial enrichment capacity of thiourea derivatives, and improves the steric hindrance to ReO4. -Selective identification enables highly selective capture of rhenium. This invention achieves this by reducing ReO4. - The degree of hydration after coordination amplifies the dehydration effect; enhances the enrichment capacity of thiourea derivatives at the gas-liquid interface and improves the receptivity to ReO4 through steric hindrance. - The selective recognition of multiple synergistic effects enables the Re / Mo separation coefficient to reach over 200, which is much higher than that of existing solvent extraction systems (usually less than 50), and the ideal separation effect can be achieved with single-stage extraction without the need for multi-stage countercurrent operation.

[0015] As a preferred embodiment, the total number of carbon atoms in the thiourea derivative is no more than 37. Experiments have shown that an excessive number of carbon atoms leads to overly strong hydrophobicity in the thiourea derivative, reducing the separation efficiency of molybdenum and rhenium.

[0016] As a preferred solution, R1 and R2 are each independently C8 ~ C 18 Alkyl groups, substituted phenyl groups, where the phenyl group is substituted and the substituent is C4 ~ C5. 12 Alkyl groups.

[0017] As a more preferred embodiment, the thiourea derivative has the structure shown in formula (1-1):

[0018] Equation (1-1);

[0019] R3, R4, R5, R6, R7, and R8 are H or C4 ~ C 12 Alkyl groups, and not all of them are H.

[0020] As a further preferred option, in equation (1-1), R3, R5, R6, and R8 are H, and R4 and R7 are C4 ~ C. 12 Alkyl groups. Experiments have shown that, under this preferred condition, molybdenum and rhenium exhibit superior separation performance.

[0021] A second aspect of the present invention provides a method for preparing a thiourea derivative for the separation of molybdenum and rhenium, comprising the following steps:

[0022] (1) In the presence of a catalyst, an amine compound is condensed with carbon disulfide to obtain a reaction solution; the condensation reaction is carried out at a temperature of 70 ~ 80 °C for a time of 4 ~ 6 h.

[0023] (2) After cooling the reaction solution, the solid is purified to obtain the final product;

[0024] The amine compound is R1-NH2 and / or R2-NH2, where R1 and R2 are each independently substituted or unsubstituted C6~C. 18 Alkyl groups, substituted phenyl groups;

[0025] Among them, when C6~C 18 When an alkyl group is substituted, the substituent is C1~C2. 12 Alkyl groups; when the phenyl group is substituted, the substituent is C4~C5. 18 Alkyl groups.

[0026] As a preferred solution, R1 and R2 are each independently C8 ~ C 18 Alkyl groups, substituted phenyl groups, where the substituent is C4 to C5 when the phenyl group is substituted. 12 Alkyl groups.

[0027] As a preferred embodiment, the amine compound has the structure shown in formula (A):

[0028] Formula (A);

[0029] In equation (A), R a R b R c For H or C4 ~ C 12 Alkyl groups, and not all of them are H.

[0030] As a more preferred option, in equation (A), R a R b R c For H or C4 ~ C 12 Straight-chain or branched alkyl groups.

[0031] As a better option, R a and R c For H, R b For C4 ~ C 12 Alkyl groups. Experiments have shown that under this preferred condition, the separation efficiency of molybdenum and rhenium can be further improved.

[0032] As a preferred embodiment, after cooling the reaction solution, the solid is coarsely crushed, then an acidic detergent is added for extraction, followed by washing with water until neutral, and then freeze-drying after solid-liquid separation to obtain a thiourea derivative for molybdenum-rhenium separation.

[0033] As a preferred embodiment, the freeze-drying temperature is -50 ~ -5℃, and the time is 45 ~ 50 h.

[0034] As a preferred embodiment, the catalyst is selected from at least one of a mixture of sulfur and sodium carbonate, a mixture of sulfur and surfactant, and sulfonic acid resin.

[0035] As a preferred embodiment, the surfactant is a nonionic surfactant and / or anionic surfactant. The nonionic surfactant is OP-10, and the anionic surfactant is sodium dodecylbenzenesulfonate.

[0036] It should be noted that the present invention does not have any special requirements on the specific amount of catalyst used; any amount known in the art that can synthesize thiourea derivatives can be used.

[0037] As a preferred embodiment, the molar ratio of the amine compound to the carbon disulfide is 1.5 to 2.5:1.

[0038] As a preferred option, the washing is done with an acidic detergent.

[0039] As a preferred embodiment, the acidic detergent is selected from at least one of hydrochloric acid solution, sulfuric acid solution, and nitric acid solution. The present invention does not have special requirements regarding the concentration of the acidic detergent; any detergent known in the art may be used.

[0040] A third aspect of the present invention is to provide a method for applying the thiourea derivative obtained by the preparation method described in the second aspect above in the separation of molybdenum and rhenium, comprising the following steps:

[0041] (a) The thiourea derivative was reacted with a mixed solution containing molybdenum and rhenium by stirring to obtain the reacted material;

[0042] (b) In the presence of the enriched phase, the post-reaction material is subjected to foam adsorption separation to obtain a rhenium-rich organic phase and a molybdenum-rich aqueous phase.

[0043] As a preferred embodiment, the volume ratio of the enriched phase to the mixed solution containing molybdenum and rhenium is 1:5 to 1:50.

[0044] As a preferred embodiment, the molar ratio of the thiourea derivative to rhenium in the mixed solution is 2-4:1. Experiments have shown that under this preferred condition, molybdenum and rhenium exhibit superior separation performance. Excessive use of the thiourea derivative can react with molybdenum, increasing the molybdenum loss rate.

[0045] As a preferred embodiment, the stirring reaction time is 30 to 60 minutes.

[0046] As a preferred embodiment, the foam adsorption separation method includes: placing the reacted material in a foam extraction reactor, adding an enriched phase at the top of the foam extraction reactor, and performing foam extraction at a gas rate of 40-100 mL / min for 30-60 min.

[0047] As a preferred embodiment, the volume fraction of 2-octanol in the enriched phase is 10% to 30%, with the balance being sulfonated kerosene.

[0048] As a preferred embodiment, the mixed solution containing molybdenum and rhenium is selected from at least one of molybdenite oxidative roasting leaching solution, molybdenite pressure leaching solution, and rhenium-containing waste catalyst leaching solution, wherein the concentration of molybdenum in the mixed solution containing molybdenum and rhenium is 5 to 100 g / L and the concentration of rhenium is 10 to 100 mg / L.

[0049] As a preferred embodiment, the rhenium-rich organic phase is back-extracted and evaporated to crystallize, yielding ammonium perrylate product.

[0050] As a preferred embodiment, the molybdenum-rich aqueous phase is purified, evaporated, and crystallized to obtain ammonium molybdate product.

[0051] Compared with the prior art, the present invention has at least the following advantages:

[0052] (1) Significantly improved selectivity for molybdenum and rhenium: This invention is based on molybdate (MoO4) 2- ) and perrhenate (ReO4) - The essential difference in hydration energy (ReO4) - Hydration energy is approximately -250 kJ / mol, MoO4 2- Hydration energy is approximately -400 kJ / mol), combining sulfur atoms in thiourea derivatives with ReO4. - The soft-soft interactions between rhenium atoms enable highly selective capture of rhenium. Furthermore, this invention constructs a suitable hydrophobic microenvironment by introducing appropriate carbon chains into the thiourea framework, exerting multiple synergistic effects: reducing ReO4 content... - The degree of hydration after coordination amplifies the dehydration effect; enhances the enrichment capacity of thiourea derivatives at the gas-liquid interface; and improves the receptivity to ReO4 through steric hindrance. - Selective recognition. The foam extraction of thiourea derivatives prepared using this invention can achieve a Re / Mo separation coefficient of over 200, which is much higher than that of existing solvent extraction systems (usually less than 50). Ideal separation results can be achieved with single-stage extraction, without the need for multi-stage countercurrent operation.

[0053] (2) The preparation process of thiourea derivatives is simple and has good recycling performance: This invention uses an atmospheric pressure reflux method to synthesize thiourea derivatives through foam extraction. The reaction temperature is 70-80℃ and the reaction time is 4-6 hours. No high-temperature and high-pressure equipment is required, making the operation simple and suitable for industrial production. The catalyst system can be selected from at least one of the following: a mixture of sulfur and sodium carbonate, a mixture of sulfur and compound surfactants, or macroporous sulfonic acid resin. The raw materials are widely available and inexpensive. The prepared foam-extracted thiourea derivatives have good chemical stability. After acid washing and water washing purification, the product has high purity and can be stored for a long time. In the application process, the rhenium-rich organic phase can be back-extracted to regenerate and recycle the thiourea derivatives, effectively reducing the consumption of thiourea derivatives and process costs.

[0054] (3) The foam-extracted thiourea derivative prepared by the present invention can achieve efficient separation in the molybdenum and rhenium coexistence system, and has good stability, reusability and environmental friendliness. It can be widely used in the resource treatment of molybdenite roasting leaching solution, pressurized leaching solution and rhenium-containing waste catalyst leaching solution, etc., and has good industrial application prospects. Attached Figure Description

[0055] Figure 1 This is a process flow diagram of Embodiment 1 of the present invention. Detailed Implementation

[0056] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0057] The present invention will be further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited to the following specific embodiments. Obviously, the embodiments described below are only a part of the embodiments, and all other embodiments obtained by those skilled in the art without creative effort are still within the scope of protection of the present invention.

[0058] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this invention can be purchased from the market or prepared by existing methods.

[0059] Example 1

[0060] 4-Octoylaniline: .

[0061] 4-Octylaniline (R) a R cFor H, R b (CH2)7CH3 was added to a reaction vessel. In the presence of a catalyst, a mixture of sulfur and a compound surfactant (OP-10 and sodium dodecylbenzenesulfonate in a volume ratio of 1:2) was added dropwise to carbon disulfide at a molar ratio of 1.5:1. The mixture was refluxed at 70°C for 6 hours to obtain a reaction solution. The reaction solution was poured off while hot and allowed to cool and solidify naturally to obtain a crude product of the foam-extracted thiourea derivative. The crude product was pulverized, and sulfuric acid (30wt%) was added to wash away the alkaline substances. It was then washed with water until neutral. After solid-liquid separation, the product was freeze-dried at -50°C for 45 hours to obtain the thiourea derivative.

[0062] A pressure leaching solution of molybdenite was used as a mixed solution containing molybdenum and rhenium, with a molybdenum concentration of 80 g / L and a rhenium concentration of 80 mg / L. The aforementioned thiourea derivative was added to this mixed solution, with the molar amount of the thiourea derivative being four times the molar amount of rhenium in the mixed solution. The mixture was stirred for 30 minutes to obtain the reacted material. The reacted material was transferred to a foam extraction reactor. An enrichment phase consisting of 85% sulfonated kerosene and 15% sec-octanol (volume ratio of enrichment phase to the mixed solution containing molybdenum and rhenium was 1:30) was added to the top of the reactor. Foam extraction was performed at a gas flow rate of 100 mL / min for 30 minutes to obtain a rhenium-rich organic phase and a molybdenum-rich aqueous phase.

[0063] The Re / Mo separation coefficient was 228, the rhenium extraction rate was 97.5%, and the molybdenum loss rate was less than 2.0%.

[0064] Example 2

[0065] p-Dodecylaniline: .

[0066] p-Dodecylaniline (R) a R c For H, R b -(CH2) 11 CH3) was added to a reaction vessel. In the presence of a macroporous sulfonic acid resin catalyst, carbon disulfide was added dropwise at a molar ratio of 2.5:1 to 4-dodecylamine compound. The mixture was refluxed at 80°C for 4 hours to obtain a reaction solution. The reaction solution was poured off while hot and allowed to cool and solidify naturally to obtain a crude product of the foam-extracted thiourea derivative. The crude product was pulverized, and dilute nitric acid (25wt%) was added to wash away the alkaline substances. It was then washed with water until neutral. After solid-liquid separation, it was freeze-dried at -45°C for 50 hours to obtain the thiourea derivative.

[0067] The leachate from the rhenium-containing spent catalyst was used as a mixed solution containing molybdenum and rhenium, with a molybdenum concentration of 30 g / L and a rhenium concentration of 100 mg / L. The aforementioned thiourea derivative was added to this mixed solution, with the molar amount of the thiourea derivative being twice the molar amount of rhenium in the mixed solution. The mixture was stirred for 60 minutes to obtain the reaction product. The reaction product was transferred to a foam extraction reactor. An enrichment phase consisting of 85% sulfonated kerosene and 15% sec-octanol (volume ratio of enrichment phase to the mixed solution containing molybdenum and rhenium was 1:10) was added to the top of the reactor. Foam extraction was performed at a gas flow rate of 40 mL / min for 60 minutes to obtain a rhenium-rich organic phase and a molybdenum-rich aqueous phase.

[0068] The Re / Mo separation coefficient was 235, the rhenium extraction rate was 98.2%, and the molybdenum loss rate was less than 1.8%.

[0069] Example 3

[0070] 4-Octylaniline and p-dodecylaniline were mixed at a mass ratio of 2:1 as amine compound raw materials. In the presence of a catalyst, a mixture of sulfur and a compound surfactant (OP-10 and sodium dodecylbenzenesulfonate in a volume ratio of 1:4) was added dropwise to the mixture at a molar ratio of amine compound to carbon disulfide of 1.8:1. The mixture was refluxed at 78°C for 5.5 hours to obtain a reaction solution. The reaction solution was poured off while hot and allowed to cool and solidify naturally to obtain a crude product of the foam-extracted thiourea derivative. The crude product was pulverized, and dilute hydrochloric acid (15wt%) was added to wash away alkaline substances. It was then washed with water until neutral. After solid-liquid separation, the product was freeze-dried at -40°C for 46 hours to obtain the thiourea derivative.

[0071] A pressure leaching solution of molybdenite was used as a mixed solution containing molybdenum and rhenium, with a molybdenum concentration of 60 g / L and a rhenium concentration of 15 mg / L. The aforementioned thiourea derivative was added to this mixed solution, with the molar amount of the thiourea derivative being 2.5 times the molar amount of rhenium in the mixed solution. The mixture was stirred for 40 minutes to obtain the reacted material. The reacted material was transferred to a foam extraction reactor. A enriched phase consisting of 85% sulfonated kerosene and 15% sec-octanol (volume ratio of enriched phase to the mixed solution containing molybdenum and rhenium was 1:15) was added to the top of the reactor. Foam extraction was performed at a gas flow rate of 60 mL / min for 50 minutes to obtain a rhenium-rich organic phase and a molybdenum-rich aqueous phase.

[0072] The Re / Mo separation coefficient was 220, the rhenium extraction rate was 96.2%, and the molybdenum loss rate was less than 2.2%.

[0073] Example 4

[0074] The preparation method of the thiourea derivative was similar to that in Example 2, except that p-dodecylaniline was replaced with an equal mass of dodecylamine (CH3(CH2)). 11 NH2).

[0075] A pressure leaching solution of molybdenite was used as a mixed solution containing molybdenum and rhenium, with a molybdenum concentration of 60 g / L and a rhenium concentration of 15 mg / L. The aforementioned thiourea derivative was added to this mixed solution at a dosage 2.5 times the molar amount of rhenium in the solution. The mixture was stirred for 40 minutes to obtain the reacted material. This reacted material was transferred to a foam extraction reactor. A enriched phase consisting of 85% sulfonated kerosene and 15% sec-octanol (volume ratio of enriched phase to the molybdenum and rhenium-containing mixed solution was 1:15) was added to the top of the reactor. Foam extraction was performed at a gas flow rate of 60 mL / min for 50 minutes to obtain a rhenium-rich organic phase and a molybdenum-rich aqueous phase.

[0076] The Re / Mo separation coefficient was 185, the rhenium extraction rate was 93.2%, and the molybdenum loss rate was 4.2%.

[0077] Example 5

[0078] This embodiment is carried out using a method similar to that of Example 1, except that the molar amount of the thiourea derivative is adjusted to be 5 times the molar amount of rhenium in the mixed solution.

[0079] The Re / Mo separation coefficient was 160, the rhenium extraction rate was 96.4%, and the molybdenum loss rate was 8.32%.

[0080] Comparative Example 1

[0081] Extraction experiment of molybdenum and rhenium using the traditional N263 extraction system.

[0082] The leaching liquid from the oxidative roasting of molybdenite was used as a mixed solution containing molybdenum and rhenium, with a molybdenum concentration of 50 g / L and a rhenium concentration of 50 mg / L. Extraction was performed at room temperature with shaking for 10 minutes under the following conditions: an O / A ratio of 1:1, a N263 volume concentration of 10%, a sec-octanol volume concentration of 5%, and sulfonated kerosene as a diluent. After extraction, the mixture was allowed to stand and separate into two phases: a loaded organic phase and a raffinate aqueous phase. The Re / Mo separation coefficient was 42, the rhenium extraction rate was 87.5%, and the molybdenum loss rate was 42.0%.

[0083] Comparative Example 2

[0084] In this comparative example, the preparation method of the thiourea derivative used to separate molybdenum and rhenium was similar to that in Example 1, except that 4-octylaniline was replaced with an equimolar amount of p-propylaniline. p-propylaniline (R...) a R c For H, Rb (for -(CH2)2CH3).

[0085] p-Propylaniline: .

[0086] The Re / Mo separation coefficient was 32, the rhenium extraction rate was 47.3%, and the molybdenum loss rate was 1.98%.

[0087] Comparative Example 3

[0088] In this comparative example, the preparation method of the thiourea derivative used to separate molybdenum and rhenium was similar to that in Example 1, except that 4-octylaniline was replaced with an equimolar amount of propylamine.

[0089] The Re / Mo separation coefficient was 12, the rhenium extraction rate was 17.6%, and the molybdenum loss rate was 0.48%.

[0090] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A thiourea derivative for the separation of molybdenum and rhenium, characterized in that: Thiourea derivatives were used to separate molybdenum and rhenium; The thiourea derivative has the structure shown in formula (1): Equation (1); R1 and R2 are each independently substituted or unsubstituted C6~C. 18 Alkyl groups, substituted phenyl groups; Among them, when C6~C 18 When an alkyl group is substituted, the substituent is C1~C2. 12 Alkyl groups; when the phenyl group is substituted, the substituent is C4~C5. 18 Alkyl groups.

2. A thiourea derivative for molybdenum-rhenium separation according to claim 1, characterized in that: R1 and R2 are each independently C8 ~ C 18 Alkyl groups and substituted phenyl groups, where the phenyl group is substituted and the substituent is C4 to C5. 12 Alkyl groups.

3. A thiourea derivative for molybdenum-rhenium separation according to claim 2, characterized in that: The thiourea derivative has the structure shown in formula (1-1): Equation (1-1); R3, R4, R5, R6, R7, and R8 are H or C4 ~ C 12 Alkyl groups, and not all of them are H.

4. A thiourea derivative for molybdenum-rhenium separation according to claim 3, characterized in that: In equation (1-1), R3, R5, R6, and R8 are H, and R4 and R7 are C4 ~ C. 12 Alkyl groups.

5. A method for preparing a thiourea derivative for the separation of molybdenum and rhenium, characterized in that: Includes the following steps: (1) In the presence of a catalyst, an amine compound is condensed with carbon disulfide to obtain a reaction solution; the condensation reaction is carried out at a temperature of 70 ~ 80 °C for a time of 4 ~ 6 h. (2) After cooling the reaction solution, the solid is purified to obtain the final product; The amine compound is R1-NH2 and / or R2-NH2, where R1 and R2 are each independently substituted or unsubstituted C6~C. 18 Alkyl groups, substituted phenyl groups; Among them, when C6~C 18 When an alkyl group is substituted, the substituent is C1~C2. 12 Alkyl groups; when the phenyl group is substituted, the substituent is C4~C5. 18 Alkyl groups; Preferably, R1 and R2 are each independently C8 ~ C 18 Alkyl groups and substituted phenyl groups, where the substituent is C4~C5 when the phenyl group is substituted. 12 Alkyl groups.

6. The method for preparing a thiourea derivative for molybdenum-rhenium separation according to claim 5, characterized in that: The amine compound has the structure shown in formula (A): Formula (A); In equation (A), R a R b R c For H or C4 ~ C 12 Alkyl groups, and not all of them are H; Preferably, R a and R c For H, R b For C4 ~ C 12 Alkyl groups.

7. A method for preparing a thiourea derivative for molybdenum-rhenium separation according to claim 6, characterized in that: The catalyst is selected from at least one of a mixture of sulfur and sodium carbonate, a mixture of sulfur and surfactant, and sulfonic acid resin. And / or, the molar ratio of the amine compound to the carbon disulfide is 1.5~2.5:1; And / or, the washing is done with an acidic detergent.

8. The method for applying the thiourea derivative prepared by the preparation method according to any one of claims 6 to 7 in the separation of molybdenum and rhenium, characterized in that: Includes the following steps: (a) The thiourea derivative was reacted with a mixed solution containing molybdenum and rhenium by stirring to obtain the reacted material; (b) In the presence of the enriched phase, the post-reaction material is subjected to foam adsorption separation to obtain a rhenium-rich organic phase and a molybdenum-rich aqueous phase.

9. The method for applying the thiourea derivative according to claim 8 in the separation of molybdenum and rhenium, characterized in that: The molar ratio of the thiourea derivative to the rhenium in the mixed solution is 2~4:1; And / or, the foam adsorption separation method includes: placing the reacted material in a foam extraction reactor, adding an enriched phase at the top of the foam extraction reactor, and performing foam extraction at a gas rate of 40-100 mL / min for 30-60 min; And / or, the volume fraction of 2-octanol in the enriched phase is 10%~30%, with the balance being sulfonated kerosene; And / or, the mixed solution containing molybdenum and rhenium is selected from at least one of molybdenite oxidative roasting leaching solution, molybdenite pressure leaching solution, and rhenium-containing waste catalyst leaching solution, wherein the concentration of molybdenum in the mixed solution containing molybdenum and rhenium is 5 to 100 g / L and the concentration of rhenium is 10 to 100 mg / L.

10. The method for applying the thiourea derivative according to claim 8 or 9 in the separation of molybdenum and rhenium, characterized in that: The rhenium-rich organic phase was back-extracted and evaporated to crystallize, yielding ammonium perrylate product; And / or, the molybdenum-rich aqueous phase is purified, evaporated and crystallized to obtain ammonium molybdate product.

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