Method for selectively enriching and separating molybdenum and rhenium by using zirconium-based adsorbent

Abstract

The invention relates to the technical field of enrichment and separation of scattered metals, in particular to a method for selectively enriching and separating molybdenum and rhenium by using a zirconium-based adsorbent. According to the method, a zirconium-based metal organic framework material is used as a zirconium-based adsorbent, and molybdenum element enrichment, rhenium element enrichment, simultaneous molybdenum and rhenium enrichment or selective molybdenum and rhenium enrichment and separation are carried out from a solution to be treated. According to the method, the zirconium-based metal organic framework material is used as the zirconium-based adsorbent, the targets of efficiently enriching the molybdenum element from the solution, effectively extracting the rhenium element, enriching the molybdenum and the rhenium at the same time and effectively separating the molybdenum and the rhenium can be achieved through different paths, and the method has the advantages of being easy to operate, mild in condition and controllable.

Description

Technical Field

[0001] The present invention relates to the technical field of rare metal enrichment and separation, and particularly relates to a method for selectively enriching and separating molybdenum and rhenium by a zirconium-based adsorbent. Background Art

[0002] As important strategic metal resources, rare metals molybdenum and rhenium are highly regarded in industries such as aerospace, information technology, biomedicine, military, and high-tech equipment due to their special physical and chemical properties, and their mining and utilization have been increasingly emphasized. Molybdenum often exists in molybdenite, while rhenium hardly has independent deposits and is often associated with molybdenite and other deposits. The properties of molybdenum and rhenium are extremely similar. Therefore, it is not easy to simply and effectively enrich and separate molybdenum and rhenium elements. Currently, the methods for enriching and separating molybdenum and rhenium include extraction method, ion exchange method, precipitation method, crystallization method, etc. After continuous improvement, there are still problems such as long process, unsatisfactory molybdenum-rhenium separation effect, low enrichment efficiency at low concentration, and the problem of co-desorption of molybdenum and rhenium during separation, which are difficult to solve. Therefore, it is very crucial to develop a more effective method for enriching and separating molybdenum and rhenium.

[0003] The adsorption separation method has the advantages of simple operation, mild conditions, and low energy consumption. Due to the excellent properties of the adsorbent, it is often used for the enrichment and separation of target substances. As a new type of adsorbent, metal-organic framework (MOF) materials have shown excellent performance in the selective enrichment and recovery of some metal ions, as well as separation and removal. CN108394950B relates to a method for adsorbing precious metal gold ions using metal-organic framework ZIF-8, and its maximum adsorption capacity for gold exceeds 1000 mg / g. CN116178741A provides the preparation and synthesis of a zirconium-based MOF adsorbent and its application in enriching and removing copper ions from wastewater. The enrichment and removal rate of copper ions in wastewater by this zirconium-based MOF adsorbent can reach 98.86%. CN110354814B introduces a method for enriching and recovering vanadium ions from vanadium-containing wastewater using a zinc-based MOF adsorbent, and its enrichment and removal rate of vanadium can reach more than 90%. CN119177366A discloses a method for separating metal molybdenum and rhenium from a nickel-based superalloy electrochemical dissolution solution. In this method, the pH is first adjusted and the modified MTS9570 resin is used for adsorption to obtain a molybdenum desorption solution, then the pH of the solution after molybdenum adsorption is adjusted and the modified MTA1721 resin is used for adsorption to obtain a second-stage rhenium desorption solution. Finally, both are evaporated and concentrated for treatment to obtain metal molybdenum and rhenium. The Hubei Geological Experiment and Testing Center uses polyimide foam plastic as the material to selectively separate and enrich rhenium in geological samples, and combines ICP-MS detection to establish a new method for enriching and detecting rhenium in ICP-MS samples.

[0004] At present, there is no technology for selectively enriching and separating molybdenum- and rhenium-containing solutions using metal-organic framework materials. There is an urgent need to provide a new metal-organic framework material as an adsorbent to selectively enrich molybdenum and rhenium from molybdenum- and rhenium-containing solutions respectively and achieve the effective separation of molybdenum and rhenium. Summary of the Invention

[0005] To solve the above technical problems, the present invention provides a method for selectively enriching and separating molybdenum and rhenium using a zirconium-based adsorbent. The present invention uses a zirconium-based metal-organic framework material as the zirconium-based adsorbent, which can be achieved through the following four paths: selectively adsorbing only molybdenum elements in the solution; selectively adsorbing only rhenium elements in the solution; first enriching molybdenum elements in the solution and then enriching rhenium elements in the solution; selectively enriching and separating molybdenum and rhenium elements. By controlling condition parameters such as the type, dosage, temperature, and time of the adsorbent, effective enrichment of molybdenum elements, enrichment of rhenium elements, simultaneous enrichment of molybdenum and rhenium, and selective enrichment and separation of molybdenum and rhenium are respectively achieved, with the advantages of simple operation, mild conditions, and controllable method.

[0006] In the first aspect, the present invention provides an application of a zirconium-based adsorbent in selectively enriching and separating molybdenum and rhenium, which uses a zirconium-based metal-organic framework material as the zirconium-based adsorbent to enrich molybdenum elements, enrich rhenium elements, simultaneously enrich molybdenum and rhenium, or selectively enrich and separate molybdenum and rhenium from the solution to be treated. In the present invention, using the zirconium-based metal-organic framework material as an adsorbent can effectively enrich molybdenum and rhenium and simultaneously separate molybdenum and rhenium. By controlling the type, dosage, temperature, and time of the zirconium-based adsorbent, the goals of efficiently enriching molybdenum elements from the solution, effectively extracting rhenium elements, simultaneously enriching molybdenum and rhenium, and effectively separating molybdenum and rhenium can be respectively achieved through different paths, which can meet the requirements of different application scenarios and actual working conditions, and has the advantages of simple operation and mild conditions.

[0007] Preferably, the zirconium-based metal-organic framework material is a material with a porous structure formed by coordinating and self-assembling a zirconium or zirconium cluster as the metal center with an organic linker.

[0008] More preferably, the organic linker includes one or more of terephthalic acid, isophthalic acid, trimesic acid, 2-sulfoterephthalic acid, fumaric acid, isophthalic acid, 2-aminoterephthalic acid, 2,5-dihydroxyterephthalic acid, 2-hydroxyterephthalic acid, and tetrafluoroterephthalic acid. In the present invention, the types of organic linkers include, but are not limited to, terephthalic acid, isophthalic acid, trimesic acid, 2-sulfoterephthalic acid, fumaric acid, isophthalic acid, 2-aminoterephthalic acid, 2,5-dihydroxyterephthalic acid, 2-hydroxyterephthalic acid, and tetrafluoroterephthalic acid.

[0009] Further preferably, the zirconium-based adsorbent includes one or more of UiO-66, UiO-66-NH2, UiO-66-SO3H, UiO-66-OH, UiO-66-(OH)2, UiO-66-COOH, UiO-66-F4, and MOF-808. The types of zirconium-based adsorbents in the present invention include but are not limited to UiO-66-NH2, UiO-66-SO3H, UiO-66-OH, UiO-66-(OH)2, UiO-66-COOH, and MOF-808.

[0010] Preferably, the solution to be treated is a molybdenum-containing solution, a rhenium-containing solution, or a molybdenum-rhenium mixed solution.

[0011] In a second aspect, the present invention provides a method for selectively enriching and separating molybdenum and rhenium using a zirconium-based adsorbent, where the zirconium-based adsorbent is a zirconium-based metal-organic framework material; the method is any one of paths 1)-4): 1) Adding the zirconium-based adsorbent to the solution to be treated, and selectively adsorbing molybdenum elements in the solution at the treatment time and temperature.

[0012] 2) Adding the zirconium-based adsorbent to the solution to be treated, and selectively adsorbing rhenium elements in the solution at the treatment time and temperature.

[0013] 3) Adding a first zirconium-based adsorbent to the solution to be treated, first enriching molybdenum elements in the solution at the treatment time and temperature, and then adding a second zirconium-based adsorbent to enrich rhenium elements in the solution; where the first zirconium-based adsorbent and the second zirconium-based adsorbent are each independently selected from the zirconium-based adsorbent.

[0014] 4) Adding the zirconium-based adsorbent to the solution to be treated, and selectively enriching and separating molybdenum and rhenium elements at the treatment time and temperature.

[0015] In the present invention, using the zirconium-based metal-organic framework material as the zirconium-based adsorbent, paths 1), 2), 3), and 4) can be respectively regulated and achieved by changing condition parameters such as the type, dosage, time, and temperature of the zirconium-based adsorbent, so as to achieve the goals of efficiently enriching molybdenum elements from the solution, effectively extracting rhenium elements, simultaneously enriching molybdenum and rhenium, and effectively separating molybdenum and rhenium.

[0016] Preferably, the zirconium-based metal-organic framework material is a material with a porous structure formed by coordinating and self-assembling a zirconium or zirconium cluster as the metal center with an organic linker; preferably, the organic linker includes one or more of terephthalic acid, isophthalic acid, trimesic acid, 2-sulfoterephthalic acid, fumaric acid, isophthalic acid, 2-aminoterephthalic acid, 2,5-dihydroxyterephthalic acid, 2-hydroxyterephthalic acid, tetrafluoroterephthalic acid, etc.

[0017] Further preferably, the organic linker is selected from one or more of terephthalic acid, trimesic acid, 2-sulfoterephthalic acid, 2-aminoterephthalic acid, 2,5-dihydroxyterephthalic acid, and 2-hydroxyterephthalic acid.

[0018] Further preferably, the zirconium-based adsorbent is selected from one or more of UiO-66, UiO-66-NH2, UiO-66-SO3H, UiO-66-OH, UiO-66-(OH)2, UiO-66-COOH, UiO-66-F4, and MOF-808.

[0019] In the present invention, by changing the type and dosage of the zirconium-based adsorbent, time, temperature and other condition parameters, the efficient enrichment of molybdenum element, the effective extraction of rhenium element, the simultaneous enrichment of molybdenum and rhenium, and the effective separation of molybdenum and rhenium are respectively regulated and achieved from the solution.

[0020] Preferably, the dosage of the zirconium-based adsorbent is 0.1 to 1000 times the mass of molybdenum element and / or rhenium element in the solution to be treated. For example, 0.1 times, 1 time, 1.5 times, 2 times, 2.5 times, 2.6 times, 2.7 times, 3 times, 10 times, 20 times, 25 times, 29 times, 29.5 times, 30 times, 35 times, 39 times, 40 times, 41 times, 50 times, 60 times, 80 times, 100 times, 120 times, 125 times, 130 times, 150 times, 160 times, 200 times, 300 times, 400 times, 800 times, 900 times, 1000 times, etc.

[0021] Further preferably, the treatment temperature is 5 to 80 °C. For example, all temperatures within the ranges such as 5 °C, 10 °C, 13 °C, 25 °C, 27 °C, 40 °C, 45 °C, 50 °C, 60 °C, 80 °C, etc.

[0022] Further preferably, the treatment time is 1 to 1440 min. For example, all times within the ranges such as 1 min, 10 min, 33 min, 60 min, 120 min, 450 min, 600 min, 1440 min, etc.

[0023] The beneficial effects of the present invention are at least as follows: The method for selective enrichment and separation of molybdenum and rhenium provided by the present invention uses a zirconium-based metal-organic framework material as an adsorbent, and can controllably and selectively enrich molybdenum element, rhenium element, simultaneously enrich molybdenum and rhenium elements, and effectively separate molybdenum and rhenium elements from a molybdenum / rhenium-containing solution or a molybdenum-rhenium mixed solution. This method has the advantages of simple operation, mild conditions, good selectivity, and high enrichment efficiency. Description of the Drawings

[0024] To more clearly illustrate the technical solutions in the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0025] Figure 1 It is a flow chart for the enrichment and separation of molybdenum / rhenium and molybdenum-rhenium mixed solution provided by the embodiments of the present invention. Detailed implementation manners

[0026] To make the objectives, technical solutions and advantages of the present invention clearer, the following will clearly and completely describe the technical solutions in the present invention. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.

[0027] In the ranges disclosed in the present invention, the endpoints and any values are not limited to the exact ranges or values. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed in the present invention.

[0028] For those not specifying specific technologies or conditions in the embodiments of the present invention, they shall be in accordance with the technologies or conditions described in the literature in the field or in accordance with the product specifications. For those devices, instruments, reagents, etc. not indicating the manufacturers, they are all conventional products that can be obtained through regular channels. The experimental reagents and raw materials involved are all commercially available products, and the reagents are all analytical pure products.

[0029] The method for selectively enriching and separating molybdenum and rhenium by the zirconium-based adsorbent provided by some embodiments of the present invention, as Figure 1 shown, is achieved through the following four paths: Path 1: By adding a certain dose of zirconium-based adsorbent, at a certain time and temperature, only selectively adsorb the molybdenum element in the solution; Path 2: By adding a certain dose of zirconium-based adsorbent, at a certain time and temperature, only selectively adsorb the rhenium element in the solution; Path 3: By first adding a certain dose of zirconium-based adsorbent, at a certain time and temperature, first enrich the molybdenum element in the solution, and then add a certain amount of zirconium-based adsorbent to enrich the rhenium element in the solution; Path 4: By adding a certain dose of zirconium-based adsorbent, at a certain time and temperature, selectively enrich and separate the molybdenum and rhenium elements.

[0030] In the following embodiments of the present invention, the CAS number of UiO-66-SO3H is 1334722-07-4, and the organic linker is 2-sulfoterephthalic acid, which is formed by coordination self-assembly with zirconium or zirconium clusters. The CAS number of MOF-808 is 1579984-19-2, and the organic linker is trimesic acid, which is formed by coordination self-assembly with zirconium or zirconium clusters.

[0031] Example 1 A method for selectively enriching and separating molybdenum and rhenium by a zirconium-based adsorbent provided in this example. In this example, Path 1 is adopted. The specific operation is as follows: Weigh 40 mg of UIO-66-SO3H and add it to 20 mL of a solution containing 1 g / L of molybdenum. Adsorb for 2 hours at 45 °C, and then perform solid-liquid separation to obtain the post-adsorption solution. Under these conditions, the post-adsorption solution contains 148.7 mg / L of molybdenum, and the molybdenum adsorption rate is 85.13%. The dosage of UIO-66-SO3H is 2 times the mass of molybdenum, which can effectively enrich molybdenum.

[0032] Example 2 A method for selectively enriching and separating molybdenum and rhenium by a zirconium-based adsorbent provided in this example. In this example, Path 2 is adopted. The specific operation is as follows: Weigh 50 mg of MOF-808 and add it to 20 mL of a solution containing 1 g / L of rhenium. Adsorb for 2 hours at 45 °C, and then perform solid-liquid separation to obtain the post-adsorption solution. Under these conditions, the post-adsorption solution contains 597.8 mg / L of rhenium, and the rhenium adsorption rate is 40.22%. The dosage of MOF-808 is 2.5 times the mass of rhenium, which can enrich rhenium.

[0033] Example 3 A method for selectively enriching and separating molybdenum and rhenium by a zirconium-based adsorbent provided in this example. In this example, Path 3 is adopted. The specific operation is as follows: Weigh 50 mg of UIO-66-SO3H and add it to 20 mL of a mixed solution of molybdenum and rhenium (46.9 mg / L of molybdenum and 37.8 mg / L of rhenium). Adsorb for 1 hour at 50 °C, and then perform solid-liquid separation to obtain a first-stage post-adsorption solution containing 0.13 mg / L of molybdenum and 37.3 mg / L of rhenium. At this time, the molybdenum adsorption rate is 99.7%, and the rhenium adsorption rate is 1.4%. The dosage of UIO-66-SO3H is 29.5 times the total mass of molybdenum and rhenium. Subsequently, add 30 mg of MOF-808 again, adsorb for 1 hour at 50 °C, and then perform solid-liquid separation. Under these conditions, the second-stage post-adsorption solution contains 0.005 mg / L of rhenium, and the rhenium adsorption rate is 99.9%. The dosage of MOF-808 is 40.2 times the mass of rhenium. This example shows that by controlling factors such as temperature, dosage, and type, it is possible to first enrich molybdenum and then enrich rhenium.

[0034] Example 4 A method for selective enrichment and separation of molybdenum and rhenium by a zirconium-based adsorbent provided in this example. In this example, Path 4 is adopted, and the specific operation is as follows: Weigh 50 mg of UiO-66-SO3H and add it to 20 mL of a mixed solution containing molybdenum and rhenium (988 mg / L of molybdenum and 918 mg / L of rhenium). Stir and adsorb at room temperature for 1 hour, and then perform solid-liquid separation to obtain the post-adsorption solution. Under these conditions, the post-adsorption solution contains 909 mg / L of rhenium and 121 mg / L of molybdenum. The molybdenum adsorption rate is 87.75%, the rhenium adsorption rate is 0.98%, and the molybdenum-rhenium selectivity is 723.7. The dosage of UiO-66-SO3H is 1.3 times the total mass of molybdenum and rhenium, which can effectively enrich molybdenum elements and achieve the separation of molybdenum and rhenium.

[0035] Example 5 A method for selective enrichment and separation of molybdenum and rhenium by a zirconium-based adsorbent provided in this example. In this example, Path 4 is adopted, and the specific operation is as follows: Weigh 50 mg of MOF-808 and add it to 20 mL of a mixed solution containing molybdenum and rhenium (0.01 g / L of molybdenum and 0.01 g / L of rhenium). Stir and adsorb at room temperature for 1 hour, and then perform solid-liquid separation to obtain the post-adsorption solution. Under these conditions, the post-adsorption solution contains 0.008 mg / L of rhenium and 0.009 mg / L of molybdenum. The molybdenum adsorption rate is 99.9%, and the rhenium adsorption rate is 99.9%. The dosage of MOF-808 is 125 times the total mass of molybdenum and rhenium, which can enrich both molybdenum and rhenium elements simultaneously.

[0036] Example 6 A method for selective enrichment and separation of molybdenum and rhenium by a zirconium-based adsorbent provided in this example. In this example, Path 4 is adopted, and the specific operation is as follows: Weigh 50 mg of MOF-808 and add it to 20 mL of a mixed solution containing molybdenum and rhenium (874.3 mg / L of molybdenum and 86.8 mg / L of rhenium). Stir and adsorb at 40 °C for 2 hours, and then perform solid-liquid separation to obtain the post-adsorption solution. Under these conditions, the post-adsorption solution contains 86.5 mg / L of rhenium and 175.1 mg / L of molybdenum. The molybdenum adsorption rate is 79.97%. The rhenium adsorption rate is 0.29%, and the molybdenum-rhenium selectivity is 389.65. The dosage of MOF-808 is 2.6 times the total mass of molybdenum and rhenium, which can effectively enrich molybdenum elements in a solution with high molybdenum and low rhenium and achieve the separation of molybdenum and rhenium.

[0037] Example 7 A method for selectively enriching and separating molybdenum and rhenium by a zirconium-based adsorbent provided in this embodiment. This embodiment adopts Path 4, and the specific operation is as follows: Weigh 50 mg of MOF-808 and add it to 20 mL of a mixed solution containing molybdenum and rhenium (96 mg / L of molybdenum and 845 mg / L of rhenium). Stir and adsorb at 40 °C for 2 hours, and then perform solid-liquid separation to obtain the post-adsorption liquid. Under these conditions, the post-adsorption liquid contains 638.7 mg / L of rhenium and 0.00228 mg / L of molybdenum, and the molybdenum adsorption rate is 99.998%. The rhenium adsorption rate is 24.4%, and the molybdenum-rhenium selectivity is 129920.5. The dosage of MOF-808 is 2.7 times the total mass of molybdenum and rhenium. It can still effectively enrich molybdenum elements in a solution with high rhenium and low molybdenum, and at the same time obtain a high-purity rhenium-containing solution, realizing the separation of molybdenum and rhenium.

[0038] As can be seen from the above embodiments, Embodiment 1 and Embodiment 2 illustrate that the zirconium-based adsorbent has a good adsorption effect on a single molybdenum element solution and also has a certain adsorption performance on a single rhenium element solution, and the implementation methods of Path 1 and Path 2 proposed in the present invention can be realized; Embodiment 3 can illustrate that by reasonably regulating parameters such as dosage, type, temperature, and time, the goal of first enriching molybdenum and then enriching rhenium can be completed in stages, realizing the implementation method of Path 3 proposed in the present invention; Embodiments 4, 5, 6, and 7 illustrate that according to different concentrations and ratios of molybdenum-rhenium mixed solutions, by reasonably regulating parameters such as dosage, type, temperature, and time, the simultaneous enrichment, selective enrichment, and separation of molybdenum and rhenium elements can be achieved.

[0039] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. Application of a zirconium-based adsorbent in the selective enrichment and separation of molybdenum and rhenium, characterized in that: Zirconium-based metal organic framework materials are used as zirconium-based adsorbents to enrich molybdenum elements, enrich rhenium elements, enrich molybdenum and rhenium simultaneously, or selectively enrich and separate molybdenum and rhenium from the solution to be treated.

2. The use according to claim 1, characterized in that: The zirconium-based metal organic framework material is a material with a porous structure formed by using zirconium or a zirconium cluster as a metal center and by coordination self-assembly with an organic connector.

3. The use according to claim 2, characterized in that: The organic linker includes one or more of terephthalic acid, isophthalic acid, trimesic acid, 2-sulfonateterephthalic acid, fumaric acid, isophthalic acid, 2-aminoterephthalic acid, 2,5-dihydroxyterephthalic acid, 2-hydroxyterephthalic acid, tetrafluoroterephthalic acid and the like.

4. The use according to any one of claims 1 to 3, characterized in that: The zirconium-based adsorbent includes one or more of UiO-66, UiO-66-NH2, UiO-66-SO3H, UiO-66-OH, UiO-66-(OH)2, UiO-66-COOH, UiO-66-F4, and MOF-808.

5. A method for selectively enriching and separating molybdenum and rhenium using a zirconium-based adsorbent, characterized in that: The zirconium-based adsorbent adopts a zirconium-based metal organic framework material; the method is any one of the paths 1)-4): 1) adding the zirconium-based adsorbent to the solution to be treated, and selectively adsorbing the molybdenum element in the solution under the treatment time and temperature; 2) adding the zirconium-based adsorbent to the solution to be treated, and selectively adsorbing the rhenium element in the solution under the treatment time and temperature; 3) adding a first zirconium-based adsorbent to the solution to be treated, first enriching the molybdenum element in the solution under the treatment time and temperature, and then adding a second zirconium-based adsorbent to enrich the rhenium element in the solution; wherein the first zirconium-based adsorbent and the second zirconium-based adsorbent are independently selected from the zirconium-based adsorbent; 4) Adding the zirconium-based adsorbent to the solution to be treated, and selectively enriching and separating the molybdenum and rhenium elements under the treatment time and temperature.

6. The method according to claim 5, characterized in that The zirconium-based metal organic framework material is a material with a porous structure formed by self-assembly with zirconium or a zirconium cluster as the metal center and an organic linker; the organic linker includes one or more of terephthalic acid, isophthalic acid, trimesic acid, 2-sulfonateterephthalic acid, fumaric acid, isophthalic acid, 2-aminoterephthalic acid, 2,5-dihydroxyterephthalic acid, 2-hydroxyterephthalic acid, tetrafluoroterephthalic acid, etc.

7. The method according to claim 6, characterized in that The zirconium-based adsorbent is selected from one or more of UiO-66, UiO-66-NH2, UiO-66-SO3H, UiO-66-OH, UiO-66-(OH)2, UiO-66-COOH, UiO-66-F4, and MOF-808.

8. The method according to any one of claims 5 to 7, characterized in that: The amount of the zirconium-based adsorbent used is 0.1 to 1000 times the mass of the molybdenum element and / or the rhenium element in the solution to be treated.

9. The method according to any one of claims 5 to 8, characterized in that: The processing temperature is 5~80℃.

10. The method according to any one of claims 5 to 9, characterized in that: The processing time is 1~1440min.

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