Preparation of Schiff base modified ionic framework material and method for deep purification of lutetium nucleus-containing medical wastewater

Abstract

The present invention discloses a preparation method of a Schiff base modified ion framework material and a method for deep purification of medical wastewater containing lutetium nuclei, comprising: using common sponge as a base material, using the Schiff base reaction principle, using amine reagents as a "bridge", and aldehyde reagents as active excitation reaction monomers, preparing amino acid metal ion Schiff base modified ion framework materials by a one-pot method; using the Schiff base modified ion framework material to be column-filled for deep purification of medical wastewater containing lutetium nuclei. The material preparation process of the present invention is simple, the performance is stable, and the functionally modified material has an ion exchange function and excellent metal cation adsorption performance; in addition, the combined process method of the present invention has a good treatment effect on medical wastewater containing lutetium nuclei.

Description

Technical Field

[0001] The invention belongs to the technical field of wastewater treatment, and more specifically, relates to a preparation method of a Schiff base modified ion framework material and a method for deeply purifying medical wastewater containing lutetium nuclei. Background Art

[0002] With the development of modern medicine, the application of nuclear medicine in hospital diagnosis and treatment is becoming more and more common. With the increase in the use of medical isotopes, the existing natural decay method in hospitals can no longer meet the development needs of modern nuclear medicine. The natural decay method relies on decay pools to store radioactive waste liquid, allowing the waste liquid to decay naturally. The temporary storage time exceeds 10 times the longest half-life of the nuclide. Therefore, it has problems such as large area occupied by decay pools, small single processing volume, and long waste liquid storage cycle. These problems have become key technical issues that need to be solved in the rapid development of nuclear medicine in my country. At present, lutetium-177 labeled drugs have shown very significant clinical advantages in the treatment of prostate cancer and neurological tumors, while the method for treating medical wastewater containing lutetium nuclei still uses the natural decay method.

[0003] The present invention adopts a one-pot method to obtain a new type of Schiff base modified framework material, which can effectively adsorb lutetium, has an extremely fast adsorption rate and a high adsorption capacity. As a new generation of environmentally friendly materials, it has great application prospects and social and economic effects. Summary of the invention

[0004] An object of the present invention is to solve at least the above problems and / or disadvantages and to provide at least the advantages which will be described hereinafter.

[0005] In order to achieve these objects and advantages according to the present invention, a Schiff base modified ionic framework material is provided, having the following structural formula:

[0006]

[0007] Wherein M is one or a combination of metal cations selected from sodium, potassium, magnesium, calcium, aluminum and iron, and n is an integer of 1 to 3.

[0008] A method for preparing a Schiff base modified ionic framework material comprises the following steps:

[0009] S1. Cut the sponge base into a cuboid with a length of 5 to 20 mm and a width and thickness of 5 to 10 mm to obtain an unmodified sponge base; soak the sponge base in anhydrous ethanol, oscillate in an ultrasonic oscillator for 20 to 30 minutes, repeat 2 to 3 times, wash away impurities, and dry for later use;

[0010] S2, adding an appropriate amount of amine compound and aldehyde compound to an organic solvent and reacting at room temperature for a certain time, then adding an appropriate amount of ethyl acetate and dichloromethane, standing at room temperature for 10 to 30 minutes to obtain a precursor solution, then adding a certain amount of amino acid metal ion liquid to the precursor solution, using an oscillator to oscillate it to fully dissolve, and finally standing at room temperature for 5 to 10 minutes to obtain a functionalized reagent;

[0011] S3, placing the sponge substrate of S1 into the functionalized reagent of S2, allowing it to react at a certain temperature for a certain time, shaking it once every 2 to 5 minutes during the reaction, and obtaining a Schiff base modified ionic framework material after drying.

[0012] Preferably, in S2, the organic solvent includes but is not limited to any one or a combination of acetone, acetonitrile, ethanol, and dimethyl sulfoxide; the amine compounds include but are not limited to any one or a combination of ethylenediamine, triethylenetetramine, diethylenetriamine, tris(2-aminoethyl)amine, and cyclohexanediamine; the aldehyde compounds include but are not limited to any one or a combination of trimesic acid, terephthalaldehyde, isophthalaldehyde, and o-phthalaldehyde.

[0013] Preferably, in S2, the amino acid metal ion liquid includes but is not limited to any one or a combination of lysine, glycine, ornithine, cystine, and arginine metal ion liquids, wherein the metal ion includes but is not limited to any one or a combination of sodium, potassium, magnesium, calcium, aluminum, and iron.

[0014] Preferably, in S2, the volume of the organic solution is 5-10 mL; the molar ratio of the amine compound to the aldehyde compound is 2:5, the molar volume ratio of the amine compound to the organic solution is 0.3-0.5 mmol:5-10 mL; and the reaction time is 5-15 min.

[0015] Preferably, in S2, the volume ratio of ethyl acetate to dichloromethane to organic solvent is 1:1:8, the mass ratio of precursor solution to amino acid metal ion liquid is 50:1-100:1; the speed of the oscillator is set to 250-300 r / min; and the oscillation time is 5-10 min.

[0016] Preferably, in S3, the mass volume ratio of the sponge substrate to the functionalizing agent is 0.015:10 mL to 0.03 g:10 mL, the reaction temperature is 20 to 30° C., and the reaction time is 5 to 20 min.

[0017] A method for deep purification of lutetium nucleus-containing medical wastewater by using a Schiff base modified ionic framework material comprises: filling the Schiff base modified ionic framework material into a primary or multi-stage glass chromatography column by a wet method, wherein the mass ratio of the lutetium nucleus-containing medical wastewater to the Schiff base modified ionic framework material is 10:1 to 1000:1, and adsorption is performed in a series and / or parallel manner, the lutetium nucleus-containing medical wastewater enters the glass chromatography column in a bottom-in-top-out manner, and the flow rate of the lutetium nucleus-containing medical wastewater is controlled to be 0.01 to 100 L / h by adjusting a peristaltic pump.

[0018] Preferably, the glass chromatography column has a length of 5 to 200 cm, an inner diameter of 1 to 100 cm, and an outer diameter of 2 to 110 cm; and the concentration of lutetium in the medical wastewater containing lutetium nuclei ranges from 0.01 to 50 mg / L.

[0019] The present invention has at least the following beneficial effects:

[0020] (1) Using polyurethane sponge, melamine sponge, polyvinyl alcohol sponge, polyester sponge, carboxymethyl cellulose sponge, polypropylene sponge, etc. as matrix materials, adopting the Schiff base reaction principle, using amine reagents as "bridges", and aldehyde reagents as active excitation reaction monomers, a new type of Schiff base modified ion framework material of amino acid metal ions is prepared by a one-pot method; the material is packed in a column to deeply purify medical wastewater containing lutetium nuclei. The material preparation process of the present invention is simple, the performance is stable, and the functionally modified material has ion exchange function and excellent metal cation adsorption performance; in addition, the combined process method of the present invention has a good treatment effect on medical wastewater containing lutetium nuclei, is degradable, and is environmentally friendly;

[0021] (2) The modified material has a planar structure in space and can form a dense film layer in the pores of the sponge matrix, with a large contact area and a fast adsorption rate;

[0022] (3) After modification, the sponge has ion exchange function, and has a good treatment effect on real medical wastewater containing lutetium nuclei, and the physical and chemical properties of the modified sponge are stable;

[0023] (4) The synthesis method of the novel Schiff base modified framework material provided by the present invention is simple and easy to operate, does not require the introduction of other external conditions, and can achieve batch synthesis;

[0024] (5) The device used in the present invention does not require the addition of other chemicals to operate, does not introduce new impurities, and rarely generates subsequent waste.

[0025] The advantages, objectives and features of the present invention will be embodied in part through the following description, and in part will be understood by those skilled in the art through study and practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 A schematic diagram of the structure of a wastewater treatment device provided by the present invention;

[0027] Figure 2 This is a SEM image of the Schiff base modified ionic framework material prepared in Example 1 of the present invention;

[0028] Figure 3 This is a time gradient diagram of the adsorption of lutetium ions by the Schiff base modified ionic framework material prepared in Example 1 of the present invention;

[0029] Figure 4 This is a concentration gradient diagram of lutetium ions adsorbed by the Schiff base modified ionic framework material prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0030] The present invention is further described in detail below in conjunction with the accompanying drawings so that those skilled in the art can implement the invention with reference to the description.

[0031] It should be understood that terms such as “having”, “including” and “comprising” used herein do not exclude the existence or addition of one or more elements or combinations thereof.

[0032] Example 1

[0033] This embodiment provides a method for deep purification of lutetium-containing medical wastewater using a Schiff base modified ionic framework material, comprising the following steps:

[0034] Step 1: preparing the Schiff base modified ionic framework material Lys-Na@MF, specifically comprising:

[0035] S1, cutting the original sponge into a cuboid with a length of 10 mm and a width and thickness of 5 mm to obtain an unmodified sponge base;

[0036] S2, soak the sponge base in anhydrous ethanol, then put it into an ultrasonic oscillator for 20 minutes, repeat this process 3 times to wash away possible impurities, and finally dry it in an oven at 50°C;

[0037] S3, synthesizing a functionalized reagent at room temperature; wherein the functionalized reagent is prepared by using 14 mL of ethanol as a solvent, adding 1 mmol of tris(2-aminoethyl)amine and 2.5 mmol of terephthalaldehyde to react, and the reaction time is 10 min; then taking 5 mL of the reacted reagent into a reactor, adding 1 mL of ethyl acetate and 1 mL of dichloromethane, and standing at room temperature for 10 min, then adding 0.2 mmol of lysine-sodium ion liquid, placing it on an oscillator, setting the speed of the oscillator to 250 r / min, and the oscillation time to 10 min, so that it is fully dissolved in the reagent, and then standing at room temperature for 10 min to obtain a functionalized reagent;

[0038] S4. Load the sponge substrate with functional reagents. Place 15 mg of the cleaned and dried sponge substrate into 10 mL of the functional reagent and allow to react for 15 min at room temperature. Shake the sponge every 3 min during the reaction to obtain a Schiff base-modified sponge. Then take out the sponge and dry it in an oven at 60 ° C. Turn it over every 5 min during the drying process to obtain a Schiff base-modified ionic framework material Lys-Na@MF. The SEM image of the Schiff base-modified ionic framework material prepared in this embodiment is shown in FIG. Figure 2 shown.

[0039] Step 2: Place 20 g of the dried Schiff base modified ion framework material into a glass chromatography column, and use anhydrous ethanol to completely permeate the glass chromatography column containing the Schiff base modified ion framework material until the anhydrous ethanol completely soaks the Schiff base modified ion framework material;

[0040] Step 3: Adjust the peristaltic pump flow rate to 2 mL / min, pass the lutetium nucleus-containing medical wastewater into a glass chromatography column with an inner diameter of 5 cm and an effective height of 20 cm, collect the wastewater, and complete the deep purification of the lutetium nucleus-containing medical wastewater. In this embodiment, the lutetium concentration in the initial nuclear medical wastewater is 10 mg / L, the volume of the nuclear medical wastewater is 1 L, and the lutetium concentration after purification is 0.04 mg / L.

[0041] like Figure 3 As shown, at room temperature (25°C), 15 mg of the modified Schiff base ion framework material prepared in this embodiment was added to 25 mL of lutetium solution with a lutetium concentration of 100 mg / L, and the pH of the lutetium solution was 6.7. It can be seen from the curve of the adsorption amount changing with time that the modified Schiff base ion framework material has a fast adsorption rate for lutetium and can reach equilibrium in about 10 minutes.

[0042] like Figure 4 As shown, at room temperature (25°C), 15 mg of the modified Schiff base ion framework material prepared in this embodiment was added to 25 mL of lutetium solution of different concentrations, the pH of the lutetium solution was 6.7, and the adsorption time was 6 hours. It can be seen from the curve of the adsorption amount changing with the lutetium ion concentration in the solution that the modified Schiff base ion framework material still has good adsorption performance for high concentration lutetium ion solution.

[0043] Example 2

[0044] This embodiment provides a method for deep purification of lutetium-containing medical wastewater using a Schiff base modified ionic framework material, comprising:

[0045] Step 1: preparing the Schiff base modified ionic framework material Lys-Na@MF, specifically comprising:

[0046] S1, cutting the original sponge into a cuboid with a length of 15 mm and a width and thickness of 10 mm to obtain an unmodified sponge base;

[0047] S2, soak the sponge base in anhydrous ethanol, then put it into an ultrasonic oscillator for 20 minutes, repeat this process 3 times to wash away possible impurities, and finally dry it in an oven at 50°C;

[0048] S3, synthesizing a functionalized reagent at room temperature; wherein the functionalized reagent is prepared by using 7 mL of ethanol as a solvent, adding 0.5 mmol of tris(2-aminoethyl)amine and 1.25 mmol of terephthalaldehyde to react, and the reaction time is 10 min; then taking 5 mL of the reacted reagent into a reactor, adding 1 mL of ethyl acetate and 1 mL of dichloromethane, and standing at room temperature for 20 min, then adding 0.2 mmol of lysine-sodium ion liquid, placing it on an oscillator, setting the speed of the oscillator to 250 r / min, and the oscillation time to 10 min, so that it is fully dissolved in the reagent, and then standing at room temperature for 10 min to obtain a functionalized reagent;

[0049] S4. Load the sponge substrate with functional reagents. Place 15 mg of the cleaned and dried sponge substrate into 10 mL of the functional reagent and allow it to react for 20 minutes at room temperature. During the reaction, shake it every 5 minutes to obtain a Schiff base-modified sponge. Then take out the sponge and dry it in an oven at 60°C. Turn it over every 5 minutes during the drying process to obtain a Schiff base-modified ionic framework material.

[0050] Step 2: Place 20 g of the dried Schiff base modified ion framework material into a glass chromatography column, and use anhydrous ethanol to completely permeate the glass chromatography column containing the Schiff base modified ion framework material until the anhydrous ethanol completely soaks the Schiff base modified ion framework material;

[0051] Step 3: Adjust the peristaltic pump flow rate to 5 mL / min, pass the lutetium-containing medical wastewater into a glass chromatography column with an inner diameter of 5 cm and an effective height of 20 cm, collect the wastewater, and complete the deep purification of the lutetium-containing medical wastewater. In this embodiment, the initial lutetium concentration in the nuclear medical wastewater is 10 mg / L, the volume of the nuclear medical wastewater is 1 L, and the lutetium concentration after purification is 0.10 mg / L.

[0052] Example 3

[0053] This embodiment provides a method for deep purification of lutetium-containing medical wastewater using a Schiff base modified ionic framework material, comprising:

[0054] Step 1: preparing the Schiff base modified ionic framework material Lys-Na@MF, specifically comprising:

[0055] S1, cutting the original sponge into a cuboid with a length of 20 mm, a width of 10 mm, and a thickness of 10 mm to obtain an unmodified sponge base;

[0056] S2, soak the sponge base in anhydrous ethanol, then put it into an ultrasonic oscillator for 30 minutes, repeat this process 3 times to wash away possible impurities, and finally dry it in an oven at 50°C;

[0057] S3, synthesizing a functionalized reagent at room temperature; wherein the functionalized reagent is prepared by using 14 mL of ethanol as a solvent, adding 0.5 mmol of tris(2-aminoethyl)amine and 1.25 mmol of terephthalaldehyde to react, and the reaction time is 20 min; then taking 10 mL of the reacted reagent into a reactor, adding 1 mL of ethyl acetate and 1 mL of dichloromethane, standing at room temperature for 20 min, then adding 0.2 mmol of lysine-sodium ion liquid, placing it on an oscillator, setting the speed of the oscillator to 250 r / min, and the oscillation time to 10 min, so that it is fully dissolved in the reagent, and then standing at room temperature for 20 min to obtain a functionalized reagent;

[0058] S4. Load the sponge substrate with functional reagents. Place 15 mg of cleaned and dried sponges into 10 mL of functional reagents and allow to react at room temperature for 30 minutes. Shake the sponges every 5 minutes during the reaction to obtain a Schiff base-modified sponge. Then take out the sponge and dry it in an oven at 60°C. Turn the sponge over every 5 minutes during the drying process to obtain a Schiff base-modified ionic framework material.

[0059] Step 2: Place 20 g of the dried Schiff base modified ion framework material into a glass chromatography column, and use anhydrous ethanol to completely permeate the glass chromatography column containing the Schiff base modified ion framework material until the anhydrous ethanol completely soaks the Schiff base modified ion framework material;

[0060] Step 3: Adjust the peristaltic pump flow rate to 5 mL / min, pass the lutetium nucleus-containing medical wastewater into a glass chromatography column with an inner diameter of 5 cm and an effective height of 20 cm, collect the wastewater, and complete the deep purification of the lutetium nucleus-containing medical wastewater. In this embodiment, the initial lutetium concentration in the nuclear medical wastewater is 10 mg / L, the volume of the nuclear medical wastewater is 1 L, and the lutetium concentration after purification is 0.08 mg / L.

[0061] Example 4

[0062] The Schiff base modified ionic framework material used to purify the nuclear medical wastewater in Example 1 is subjected to a reduction treatment, and the specific method includes:

[0063] Weigh 1.0 g of Schiff base modified ionic framework material and 1.0 g of Schiff base modified ionic framework material after adsorbing lutetium, respectively, put the Schiff base modified ionic framework materials into crucibles, and put them into a muffle furnace for reduction treatment. The setting program of the muffle furnace is as follows: the temperature of the heating section is 800°C, the heating time is 100 min, the heating rate is 8°C / min, the temperature of the constant temperature section is 800°C, and the constant temperature time is 300 min.

[0064] The device for deep purification of lutetium-containing medical wastewater used in Examples 1 to 3 is as follows: Figure 1 As shown, its structure includes:

[0065] A wastewater inlet tank connected to a peristaltic pump via a pipeline;

[0066] A two-stage glass chromatography exchange column, wherein the lower end of the first-stage glass chromatography exchange column is connected to the peristaltic pump through a pipeline, and the upper end of the other-stage glass chromatography exchange column is connected to a wastewater tank;

[0067] A wastewater tank, whose water inlet is connected to the glass chromatography exchange column through a pipeline, and whose water outlet is connected to an intelligent peristaltic pump;

[0068] The wastewater inlet tank is used to hold nuclear medical wastewater, which is pumped into the two-stage glass chromatography exchange column through a peristaltic pump for chromatography purification. The wastewater enters the two-stage glass chromatography column from the bottom and then flows out from the bottom of the second-stage glass chromatography column to the wastewater tank. The entire purification device, combined with the use of Schiff base modified frame materials, achieves deep purification of lutetium-containing medical wastewater, which can make the lutetium concentration in the final effluent ≤0.10mg / L.

[0069] The number of devices and processing scales described here are used to simplify the description of the present invention. Applications, modifications and variations of the present invention will be obvious to those skilled in the art.

[0070] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and the implementation modes, and they can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to the specific details and the illustrations shown and described herein.

Claims

1. A method for deep purification of lutetium-containing medical wastewater using Schiff base modified ionic framework materials, characterized in that: include: The Schiff base modified ion framework material is wet-filled into a primary or multi-stage glass chromatography column, the mass ratio of the lutetium nucleus-containing medical wastewater to the Schiff base modified ion framework material is 10:1-1000:1, and the adsorption is performed in series and / or parallel mode, the lutetium nucleus-containing medical wastewater enters the glass chromatography column in a bottom-in-top-out mode, and the flow rate of the lutetium nucleus-containing medical wastewater is controlled to be 0.01-100 L / h by adjusting the peristaltic pump; The preparation method of the Schiff base modified ionic framework material comprises: S1, cutting the sponge matrix into a cuboid with a length of 5-20 mm, a width and a thickness of 5-10 mm; Soak the sponge matrix in anhydrous ethanol, oscillate in an ultrasonic oscillator for 20-30 minutes, repeat 2-3 times, wash away impurities, and dry for later use; S2, adding an amine compound and an aldehyde compound to an organic solvent to react at room temperature, adding ethyl acetate and dichloromethane, and standing at room temperature for 10 to 30 minutes to obtain a precursor solution, and then adding an amino acid metal ion liquid to the precursor solution, shaking with an oscillator, and standing at room temperature for 5 to 10 minutes to obtain a functionalized reagent; the organic solvent includes any one of acetone, acetonitrile, ethanol, and dimethyl sulfoxide or a combination thereof; the amine compound is tris (2-aminoethyl) amine; the aldehyde compound is terephthalaldehyde; the amino acid metal ion liquid is lysine, and the metal ion includes any one of sodium, potassium, magnesium, calcium, aluminum, and iron or a combination thereof; S3, placing the sponge matrix into the functionalized reagent, allowing it to react at 20-30 °C for 5-20 min, shaking it every 2-5 min during the reaction, and drying to obtain the Schiff base modified ionic framework material; the dosage ratio of the sponge matrix to the functionalized reagent is 0.015 g:10 mL-0.03 g:10 mL; The structural formula of the Schiff base modified ionic framework material is: Wherein M is one or a combination of metal cations selected from sodium, potassium, magnesium, calcium, aluminum and iron, and n is an integer of 1 to 3.

2. The method for deep purification of lutetium-containing medical wastewater using the Schiff base modified ionic framework material according to claim 1, characterized in that: In S2, the volume of the organic solution is 5-10 mL; the molar ratio of the amine compound to the aldehyde compound is 2:5, and the molar volume ratio of the amine compound to the organic solution is 0.3-0.5 mmol:5-10 mL; and the reaction time is 5-15 min.

3. The method for deep purification of lutetium-containing medical wastewater using the Schiff base modified ionic framework material according to claim 1, characterized in that: In S2, the volume ratio of ethyl acetate to dichloromethane to organic solvent is 1:1:8, the mass ratio of precursor solution to amino acid metal ion liquid is 50:1-100:1; the rotation speed of the oscillator is set to 250-300 r / min; and the oscillation time is 5-10 min.

4. The method for deep purification of lutetium-containing medical wastewater using the Schiff base modified ionic framework material according to claim 1, characterized in that: The glass chromatography column has a length of 5 to 200 cm, an inner diameter of 1 to 100 cm, and an outer diameter of 2 to 110 cm; the concentration range of lutetium in the medical wastewater containing lutetium nuclei is 0.01 to 50 mg / L.

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