A porous ion-imprinted imine adsorption material for nuclear medical waste liquid purification and preparation method thereof

Abstract

The invention discloses a porous ion-imprinted imine adsorption material for nuclear medical waste liquid purification and a preparation method thereof, comprising: block copolymerizing a polyamino α-carboxylate with metal ions, a rigid structure dialdehyde, and a flexible triamino cross-linking agent by a one-step solution processing method to obtain an ionic imine material with metal ion compatibility, and carrying the ionic imine material on a substrate material with a three-dimensional porous skeleton by solution processing combined with an in-situ polymerization method to obtain a porous ion-imprinted imine adsorption material. The porous ion-imprinted imine adsorption material obtained by the invention can be used for rapid and efficient adsorption and deep purification of low-concentration lutetium-177 ions in nuclear medical waste liquid, and has the advantages of a green preparation process, scalability, no need for additional initiators, and no need for high temperature and high pressure conditions.

Description

Technical Field

[0001] The invention belongs to the technical field of waste liquid purification materials, and more specifically, the invention relates to a porous ion-imprinted imine adsorption material for nuclear medical waste liquid purification and a preparation method thereof. Background Art

[0002] With the increase in the use of medical isotopes and the gradual improvement of the national standards for the discharge of radioactive waste liquid, the existing natural decay method of waste liquid treatment (storing 10 half-lives of nuclides, usually more than 180 days) and the capacity of the hospital decay pool directly restrict the number of patients admitted to the nuclear medicine department. The expansion of existing decay pools is usually restricted by the site, and there is currently no mature and reliable emergency treatment technology reserve and capacity for rapid treatment of nuclear medical waste liquid at home and abroad. Therefore, there is an urgent need to develop rapid and efficient treatment materials for nuclear medical waste liquid, and to clarify the enrichment and separation mechanism of materials for nuclides in nuclear medical waste liquid, so as to ensure the high-quality and sustainable development of my country's nuclear medicine industry.

[0003] Lutetium-177( 177 Lu) is an emerging beta medical isotope produced in batches at the Curie level in my country. 177 Lu radiopharmaceuticals ( 177 Lu-PSMA-617, 177 Lu-DOTATATE, etc.) has been widely used to treat prostate cancer, neuroendocrine tumors, etc., and has broad application prospects. 177 Lu and customized targeting molecules. 3+ In addition to ions, there are also 177 Lu and non-off-target molecules complex. In addition, lutetium is the largest heavy rare earth metal element, and its complex 4f orbital makes Lu 3+ It has strong coordination and diverse coordination forms. It can form chelate clusters with protein molecules (amino acids) and small molecular organic acids in body fluids, and form hydrated ion pairs with oxygen-containing inorganic salts through Coulombic action and coordination action. Therefore, in addition to low waste liquid activity concentration and large volume, lutetium-containing medical waste liquid also has diverse nuclide occurrence forms. Changes in the microscopic coordination environment and charge distribution give nuclear medical waste liquid 177 The separation and removal of Lu poses challenges.

[0004] One of the existing technologies is the separation and recovery technology of lutetium: In the existing separation and recovery technology of lutetium, there are a number of patents (utility models) designed and developed a series of implementation schemes for separating and recovering lutetium from other substances (CN118527120A; CN118600251A; CN117563419A; CN117018864A; CN116864178A; CN212799951U; CN106834685A; CN106929675A; CN118345258A; CN117659323A). Among them, CN118527120A discloses a method for enriching rare earth lutetium ions using a multifunctional functional group-modified MXene-based adsorbent. CN118600251A designs a method for purifying ytterbium and enriching thulium and lutetium, using active metals to reduce the ytterbium in thulium ytterbium lutetium chloride to divalent, and then by virtue of the difference in solubility between divalent ytterbium ions and trivalent thulium and lutetium ions in the solution, the remaining thulium and lutetium can be enriched to a great extent. CN117563419A proposes a multi-stage continuous separation system for carrier-free lutetium-177, which realizes continuous multi-stage separation of carrier-free lutetium-177 through a continuous separation system such as a first multi-way valve, a second multi-way valve, multiple separation columns, a third multi-way valve, a fourth multi-way valve and a fifth multi-way valve. CN117018864A discloses a method for preparing carrier-free lutetium-177 by multi-stage continuous separation and purification, which can realize multi-stage and continuous separation and preparation of carrier-free lutetium-177 by using multi-stage nitric acid solution filtration and elution. CN116864178A discloses a system and method for preparing a carrier-free lutetium-177 solution. The system utilizes a multi-stage continuous separation unit, including a multi-stage separation column filled with a phosphate elution resin and a DGA resin, to achieve the separation of ytterbium and lutetium in the production of lutetium-177. CN212799951U utility model discloses a filtering and treating device for high-purity lutetium oxide production wastewater, which achieves the filtering and treating of high-purity lutetium oxide production wastewater through a two-stage treatment box structure and a filtering and treating system. CN106834685A develops a method for extracting and purifying lutetium oxide, which re-purifies the low-purity lutetium oxide collected by the existing rough processing through the steps of configuring the liquid to be purified, configuring the intermediate agent, preparing the separation column, transforming the elution column, adsorption operation, elution ion exchange operation, etc. CN106929675A invention provides a method for enriching 14 kinds of rare earth elements (including lutetium) respectively, the method is to use N, N, N', N'-tetraoctyl-3-oxoglutaramide abbreviated as TODGA as an extractant in a sulfuric acid system, kerosene as a diluent, and utilize the differences of rare earth elements in different extraction acidity, extractant concentration, extraction volume ratio, etc. to achieve the enrichment and purification of rare earth elements in a single system of 14 kinds of rare earth elements. CN118345258A provides a method for recovering rare earths from lutetium yttrium silicate crystal waste, using multi-step acid-base dissolution and soaking to recover lutetium from lutetium-containing crystal waste.CN117659323A discloses a core-shell material based on a covalent organic framework, and uses it in solid phase extraction for carrier-free 177Lu purification and separation. CN114011384A discloses a film for heavy metal ion removal and fluorescence detection in water, which can achieve adsorption and removal of metal ions such as lutetium in water after being soaked in water.

[0005] In the prior art, that is, the separation and recovery technology of lutetium mentioned in the above background technology, it can be roughly divided into three categories.

[0006] The first type of solution (such as CN117563419A, CN116864178A, CN212799951U, CN118345258A, etc.) achieves the purification and separation of lutetium through the combination of multiple processes and devices, using acid and alkali leaching and other methods from an engineering design perspective, combined with process technology optimization.

[0007] The second type of solution (such as CN116864178A, CN106834685A, CN106929675A, etc.) uses filtering devices such as resins and ion exchange materials to achieve continuous adsorption and separation of lutetium ions through column separation and adsorption.

[0008] The third type of solution (such as CN118527120A, CN117659323A, CN114011384A, etc.) invents a new adsorption material with binding properties and porous adsorption properties for lutetium metal ions, and uses the properties of the material itself to complete the adsorption of lutetium ions and purification of related waste liquids.

[0009] Regarding the adsorption and purification of lutetium-177 in nuclear medical waste liquid, as described in the technical background, lutetium in nuclear medical waste liquid is not a simple carrier-free lutetium ion (Lu 3+ ) exists in the form of a lutetium-carrier composite molecule containing a customized targeting molecule. In addition, the sources of lutetium in nuclear medical waste liquid are complex, including: drug residual waste liquid generated during medication, medical equipment and drug container cleaning wastewater, clinical medication patient washing and showering wastewater, and human excrement discharged, etc. The wastewater contains interfering organic small molecules with coordination and chelation effects such as organic acids. Therefore, the separation and adsorption of lutetium in nuclear medical waste liquid requires materials with high binding selectivity and strong binding ability, specificity and competitiveness for the separation of lutetium in lutetium-carrier composite molecules, and the volume of nuclear medical waste liquid is large and the lutetium concentration in the waste liquid is low, so the material needs to have a fast binding rate for the separation of lutetium, and the process must be green and environmentally friendly without secondary pollution.

[0010] In this regard, among the above three types of technical solutions, the first type of solution uses engineering technology optimization to separate lutetium and other wastes by using the strong solubility of acid / base. Its disadvantages are: due to the relatively complex process, it does not meet the treatment needs of large-scale nuclear medical waste liquid, and also produces secondary pollution such as acid and alkali waste liquid.

[0011] The second technical solution uses column separation to adsorb and separate unsupported lutetium. Its disadvantages are that the materials used are commercially available ion exchange resins, fibers, activated carbon, etc., and the main application objects are unsupported Lu. 3+ Ions, lutetium in the lutetium-carrier composite molecule is difficult to exchange with ions on the ion exchange material because its coordination environment and outer charge environment are changed, and its effect does not meet the requirements of fast and efficient treatment of nuclear medical waste liquid.

[0012] The third technical solution is to synthesize a series of Lu 3+ A new material with specific binding effect on ions, using simple adsorption separation method to achieve carrier-free Lu 3+ ion separation. 3+ The specific functional groups and structures of the ions may therefore produce a certain separation effect on the lutetium-carrier complex molecules in the nuclear medical waste liquid. However, the series of materials obtained in the existing related technical solutions, such as MXene-based adsorbents, core-shell materials of covalent organic frameworks, ion removal film materials, etc., all have their own shortcomings when applied to nuclear medical waste liquid. The disadvantage is that the pore-type functionalized materials such as MXene-based adsorbents and core-shell materials of covalent organic frameworks are in the form of powder materials on a macro scale. In the large-scale and high-efficiency treatment requirements of nuclear medical waste liquid, there will be serious material loss problems. Due to the limitation of its membrane flux, the ion removal film material cannot meet the requirements of efficient and rapid separation of nuclear medical waste liquid.

[0013] In order to solve the shortcomings of the above-mentioned solution 1 in the prior art, it is necessary to develop new technologies and new materials based on adsorption method to solve the current demand for efficient and rapid treatment of nuclear medical waste liquid.

[0014] In order to solve the shortcomings of the second solution in the above-mentioned prior art one, it is necessary to develop new materials and new adsorption methods that have efficient competitive adsorption capacity for lutetium-carrier composite molecules in nuclear medical waste liquid.

[0015] In order to solve the shortcomings of the third solution in the above-mentioned prior art one, it is necessary to develop a material that has specific binding sites for lutetium, and at the same time, the material has strong processability and scalability, and the macroscopic form of the material should avoid powder form.

[0016] Prior art 2 Ion imprinting material preparation technology: Ion imprinting refers to the technology of directly constructing the adsorption sites in the functional groups into a specific coordination environment and microstructure for the target ions to be adsorbed during the material preparation stage. Since the most stable adsorption sites are pre-constructed thermodynamically, the adsorbent based on ion imprinting technology can significantly improve the adsorption competitiveness of the material for the target ions. Therefore, ion imprinting technology has been well applied in the treatment of metal ions in water (CN101905151A; CN104558674A; CN108212114A; CN108816204A; CN109174034A; CN111450805A; CN115010845A; CN118496445A). Among them, CN101905151A discloses a magnetic metal ion surface imprinted polymer, which is synthesized through four steps including preparing nano-ferroferric oxide magnetic fluid by co-precipitation method, pre-assembly of template ions, forming a pre-polymer solution for ion imprinting, magnetic field separation and ion elution. CN104558674A invention provides a magnetic copper ion imprinted material prepared using steel pickling waste liquid. The preparation process includes adding steel pickling waste liquid to chitosan acid solution, heating reaction to produce black precipitate, separating the precipitate and placing it in a copper salt solution, washing the product, magnetic separation, etc. CN108212114A invention discloses a copper ion imprinted composite adsorption material and a preparation method thereof. The preparation of the copper ion imprinted composite adsorption material involves reacting chitosan acetic acid solution with sodium carboxymethyl cellulose / sodium hydroxide coagulation solution to form balls, and then subjecting the chitosan acetic acid solution to Cu 2+ and Cu 2+. 2+ Blotting, glutaraldehyde cross-linking, acid elution of Cu 2+ The invention of CN108816204A provides a copper ion imprinted cross-linked chitosan microsphere, the preparation method of which comprises: preparing a copper acetate-chitosan solution and solidifying it with ammonia water to obtain Cu 2+ Imprinted chitosan microspheres, then cross-linked with epichlorohydrin and eluted with Cu 2+ to neutral, and finally obtain Cu 2+ Imprinted cross-linked chitosan microspheres. The invention of CN109174034A provides a method for preparing a copper ion imprinted chitosan / sodium carboxymethyl cellulose composite adsorbent, which comprises preparing a sodium carboxymethyl cellulose solution and sequentially adding an acid solution, chitosan, and a copper salt, adjusting the pH to precipitate gel particles, and then cross-linking, acid washing to remove copper, alkali solidification, washing, and drying to obtain a copper ion imprinted chitosan / sodium carboxymethyl cellulose composite adsorbent. The invention of CN111450805A relates to a chitosan-based lead ion imprinted adsorbent, and the preparation method thereof comprises mixing CS and EDTA-2Na in dilute hydrochloric acid, adjusting the pH, adding EDC■HCl in an ice bath to react to obtain an EDTA-CS gel, and reacting the gel with Pb 2+ Adsorption, glutaraldehyde crosslinking, elution of Pb 2+And drying and crushing, finally obtaining an adsorbent. CN115010845A provides a magnetic thallium ion imprinted polymer and a preparation method thereof, the preparation method involves mixing a Ti(I) ion template solution with magnetic nanoparticles, adding a functional monomer, an initiator and a crosslinking agent, ultrasonically treating, polymerizing under an inert atmosphere, and then washing and drying to obtain a magnetic thallium ion imprinted polymer. CN118496445A discloses a multi-responsive core-shell lead ion imprinted polymer, the invention uses ferroferric oxide composite graphene oxide as a matrix material, N-isopropylacrylamide as a temperature-responsive functional monomer, vinylphosphonic acid as a copolymerization functional monomer, and bisacrylamide as a crosslinking agent, and uses an aqueous solution polymerization method to prepare the lead ion surface imprinted polymer.

[0017] In the second prior art, that is, the ion imprinting material preparation technology mentioned in the above background technology, its technical features can be summarized into the following three points.

[0018] Preparation technology feature 1: Introduction and removal of template ions. In the preparation process, the target ions need to be introduced as templates first, and specific imprinting sites are constructed by forming coordination complexes or other interactions with functional groups. After the preparation is completed, the template ions are removed, leaving specific imprinting sites.

[0019] Preparation technology feature 2: multi-step synthesis and cross-linking. Existing preparation technologies usually involve multiple steps, including template ion pre-assembly, functional monomer polymerization, cross-linking, and post-processing (such as elution). Cross-linking agents (such as glutaraldehyde and epichlorohydrin) are used in these processes to enhance the structural stability and mechanical strength of the material and ensure the stability and effectiveness of the imprinting site.

[0020] Preparation technology feature three: Use of special matrices or composite materials. In the existing preparation process, special matrices (such as magnetic nanoparticles, chitosan, sodium carboxymethyl cellulose) or composite materials are used to improve the functionality and processing efficiency of the material. These matrices or composites can give the material specific physical and chemical properties, such as magnetic separation ability, multiple responsiveness, etc., and the obtained material is usually in the form of powder.

[0021] Through the analysis of the above-mentioned characteristics of the prior art, the existing problems and defects when the prior art is applied to the treatment of nuclear medical waste liquid are as follows: I. A special preparation process with multiple steps is required, including the introduction and removal of template ions, ion pre-assembly, the use of additional additives, etc. The synthesis process involves conditions such as high temperature and high pressure, and the feasibility of large-scale preparation of materials is low, which makes it difficult to meet the large-scale and large-volume treatment needs of nuclear medical waste liquid; II. Material synthesis requires acid / alkaline solutions and the like for ion elution, and the preparation process produces additional acidic or alkaline waste liquid, causing secondary pollution; III. The obtained material form is mostly in powder form. When used for the purification and treatment of nuclear medical waste liquid, the powder form will cause the loss of material, which is not conducive to practical application.

[0022] In order to solve the three problems and defects in the above-mentioned prior art 2, the ion imprinted material preparation technology that needs to meet the following requirements at the same time is: (1) the material synthesis steps are simple, no extreme conditions such as high temperature and high pressure are required, no additional additives are required, and no separate design of the introduction and removal process of the template ion is required; (2) at the same time, the synthesis process does not require acidic or alkaline solvents, and no secondary waste liquid pollution is generated; (3) at the same time, the material is finally presented in the form of a block or film material, which can be prepared on a large scale so that it can be subsequently used in the adsorption and separation of lutetium-177 in nuclear medical waste liquid. Therefore, the design and implementation of the obtained ion imprinted material for nuclear medical waste liquid purification is relatively difficult. Summary of the invention

[0023] 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.

[0024] In order to achieve these purposes and advantages according to the present invention, a porous ion-imprinted imine adsorption material for nuclear medical waste liquid purification is provided, which comprises a substrate with a three-dimensional pore structure and an ion-imprinted imine carried on the substrate; the porous ion-imprinted imine adsorption material has the following chemical formula:

[0025]

[0026] Wherein, M is one or a combination of, including but not limited to, sodium, lithium, potassium, silver, magnesium, calcium, titanium, iron, copper, cobalt, nickel, lutetium, and aluminum, and n is an integer of 1 to 3.

[0027] A method for preparing a porous ion-imprinted imine adsorption material for purification of nuclear medical waste liquid comprises: block copolymerizing polyamino α-carboxylates with metal ions, rigid structure dialdehydes and flexible triamino crosslinking agents through a one-step solution processing method to obtain an ionic imine material compatible with metal ions; and carrying the ionic imine material onto a base material with a three-dimensional porous skeleton through solution processing combined with in-situ polymerization to obtain a porous ion-imprinted imine adsorption material.

[0028] Preferably, the polyamino α-carboxylate having metal ions has the following chemical formula:

[0029]

[0030] Wherein, M is one or a combination of, including but not limited to, sodium, lithium, potassium, silver, magnesium, calcium, titanium, iron, copper, cobalt, nickel, lutetium, and aluminum; n is an integer of 1 to 3; and q is an integer of 1 to 5.

[0031] Preferably, the rigid structure dialdehyde has the following chemical formula:

[0032]

[0033] Wherein, X is one of CH, N, S, and P, and p is an integer of 1 to 3; when p≥2, X is one of CH, N, S, and P or a combination thereof.

[0034] Preferably, the flexible triamino cross-linking agent has the following chemical formula:

[0035]

[0036] Here, i is an integer from 1 to 3.

[0037] Preferably, the matrix having a three-dimensional pore structure is any one or more of a porous structure of polyacrylamide, polypropylene, polyvinyl alcohol, low-density polyether, multi-walled carbon nanotubes, single-walled carbon nanotubes, melamine formaldehyde resin, and wood cellulose.

[0038] Preferably, the method specifically comprises the following steps:

[0039] Step 1: dissolving a polyamino α-carboxylate having metal ions in ethanol to obtain a polyamino α-carboxylate ethanol solution; then adding a rigid structure dialdehyde to the polyamino α-carboxylate ethanol solution, and ultrasonicating for 5 to 30 minutes to react the polyamino α-carboxylate with the rigid structure dialdehyde to promote the dissolution of the rigid structure dialdehyde to obtain a solution A;

[0040] Step 2: dissolving a flexible triamino cross-linking agent in ethanol to obtain a solution B;

[0041] Step 3, mixing solution A and solution B, and subjecting solution A and solution B to ultrasonic treatment for 10 to 60 minutes to allow solution A and solution B to fully react, thereby obtaining an ion-imprinted imine block copolymer precursor solution C;

[0042] Step 4: immersing the substrate having a three-dimensional pore structure in an ion-imprinted imine block copolymer precursor solution C, wherein the volume ratio of the ion-imprinted imine block copolymer precursor solution C to the substrate is 1.2:1 to 2:1, and the bubbles in the substrate are expelled by squeezing and ultrasound to allow the ion-imprinted imine block copolymer precursor solution C to fully enter the cavity of the substrate;

[0043] Step 5: Place the substrate with a three-dimensional pore structure soaked in the precursor solution C in a ventilated place at 30° C., and after the ethanol solvent evaporates naturally, a porous ion-imprinted imine adsorption material is obtained.

[0044] Preferably, the molar ratio of the polyamino α-carboxylate to the flexible triamino crosslinking agent is 0.1-0.9:0.9-0.1, and the molar ratio of the amino groups in the polyamino α-carboxylate and the flexible triamino crosslinking agent to the molar ratio of the aldehyde groups in the rigid structure dialdehyde is 1:1;

[0045] In the step 1, the molar volume ratio of the polyamino α-carboxylate to ethanol is 0.4-0.6 mmol: 2-5 mL;

[0046] In the step 2, the molar volume ratio of the flexible triamino cross-linking agent to ethanol is 0.2-0.4 mmol: 2-5 mL.

[0047] The invention discloses an application of a porous ion-imprinted imine adsorption material for purifying nuclear medical waste liquid. The porous ion-imprinted imine adsorption material is applied to purifying nuclear medical waste liquid.

[0048] Preferably, the porous ion-imprinted imine adsorption material for purifying nuclear medical waste liquid comprises the following steps:

[0049] Filling a porous ion-imprinted imine adsorption material into a cylindrical chromatography column to obtain an adsorption column filled with the material;

[0050] Fix 1 to 4 adsorption columns on the stand in a manner perpendicular to the horizontal plane, and use an electric peristaltic pump to extract the radioactive waste liquid into the adsorption columns. When the number of adsorption columns is ≥ 2, the adsorption columns are connected in series end to end using pipes, with the upper end of one adsorption column connected to the lower end of the next adsorption column, and the liquid in all adsorption columns flows from bottom to top;

[0051] The effluent from the top of the last adsorption column is transported to the filtrate container through an electric peristaltic pump; the total α and total β radioactive activities of the purified liquid after purification are compared with those of the radioactive waste liquid before purification, so as to determine the purification effect of the porous ion-imprinted imine adsorption material on nuclear medical waste liquid.

[0052] The porous ion-imprinted imine adsorption material provided by the present invention can be used for purifying the nuclear medical waste liquid, which is the radioactive waste liquid generated after the use of medical isotope lutetium-177 and its series of radioactive drugs; the radioactive drugs include [ 177 Lu]Lu-DOTATATE (trade name: Lutathera), [ 177 Lu] Lu-PSMA-617 (trade name: Pluvicto), [ 177 Lu]Lu-PSMA-I&T, [ 177The radioactive waste liquid generated after the use of medical isotope lutetium-177 and its series of radioactive drugs includes residual drug waste liquid generated by intravenous injection / oral administration, medical equipment and drug container disinfection wastewater, clinical drug patients' washing and showering wastewater and human excrement discharged, etc.

[0053] The present invention has at least the following beneficial effects:

[0054] 1. The porous ion-imprinted imine adsorption material for nuclear medical waste liquid purification provided by the present invention is a porous block structure in which the functionalized ion-imprinted imine is in situ polymerized on a substrate with a porous structure by solution processing. The material has good uniformity and structural stability, and the whole presents a porous block structure. In addition, the solution processing process has strong scalability, and the size of the material can be changed at will according to the size of the porous substrate, and the scalability is strong.

[0055] The present invention and design solve the problem that the current waste liquid treatment technology cannot meet the treatment and purification of nuclear medical waste liquid by designing and preparing this porous ion-imprinted imine material, and at the same time solves the problems and defects in the preparation technology of ion-imprinted materials. The synthesis process is green and easy to prepare on a large scale, and has great commercial value.

[0056] 2. The porous ion-imprinted polyimine adsorption material for nuclear medical waste liquid purification provided by the present invention can be synthesized by a one-step solution processing method, and the preparation process is simple and scalable.

[0057] 3. In the preparation process of porous ion-imprinted imine adsorption materials, no additional additives or acid-base eluents are required. Ion-imprinting sites can be constructed by in-situ polymerization of imine. The preparation process is green and has no secondary pollution.

[0058] 4. The porous ion-imprinted imine adsorption material maintains a block shape in macroscopic morphology and can change arbitrarily with the three-dimensional pore structure matrix, and has good processability and practicality.

[0059] 5. The porous ion-imprinted imine adsorbent material has specific ion-imprinting sites for the complex nuclide lutetium-177 in nuclear medical waste liquid. Combined with the three-dimensional pore structure, it can achieve efficient and rapid purification of multiple types of lutetium-177 drugs in nuclear medical waste liquid and waste liquid generated from various sources during the use of these drugs.

[0060] 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

[0061] Figure 1This is a scanning electron microscope image of a porous ion-imprinted imine adsorbent material having lutetium ion imprinting prepared in Example 3 of the present invention;

[0062] Figure 2 It is a photograph of the porous ion-imprinted imine adsorbent material with iron ion imprinting having different volume sizes prepared in Example 4 of the present invention;

[0063] Figure 3 This is a schematic flow chart of a nuclear medical waste liquid purification device used in Example 5 of the present invention;

[0064] Figure 4 This is a data diagram of radioactivity of nuclear medical waste liquid before and after purification in Example 5 of the present invention;

[0065] Figure 5 This is a data diagram of the filtration efficiency before and after purification of nuclear medical waste liquid in Example 5 of the present invention;

[0066] Figure 6 Schematic diagram of waste liquid flow in a setup with four adsorption columns. DETAILED DESCRIPTION

[0067] 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.

[0068] 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.

[0069] Example 1

[0070] This embodiment provides a method for preparing a porous ion-imprinted imine adsorbent material having sodium ion imprinting, comprising the following steps:

[0071] Step 1: dissolving 0.5 mmol of 1,5-diamino α-pentanecarboxylic acid sodium salt in 3 ml of ethanol, then adding 1.1 mmol of biphenyl dicarboxaldehyde having a rigid structure to the ethanol solution of 1,5-diamino α-carboxylic acid sodium salt, and ultrasonicating the solution for 10 minutes to promote the dissolution of biphenyl dicarboxaldehyde to obtain a mixed ethanol solution A of the two;

[0072] Step 2: dissolving 0.4 mmol of tris(2-aminoethyl)amine in 2 ml of ethanol to obtain solution B;

[0073] Step 3, mixing solution A and solution B, and subjecting solution A and solution B to ultrasonic treatment for 15 minutes to fully react, thereby obtaining a monovalent sodium ion ion-imprinted imine block copolymer precursor solution C;

[0074] Step 4: Soak a lignocellulose substrate with a three-dimensional pore structure of 10*10*20 mm in an ion-imprinted imine block copolymer precursor solution C, wherein the volume ratio of the ion-imprinted imine block copolymer precursor solution C to the substrate is 1.2:1, and expel the bubbles in the substrate by squeezing 5 times and ultrasonicating for 10 minutes, so that the ion-imprinted imine block copolymer precursor solution C fully enters the cavity of the substrate;

[0075] Step 5: Place the lignocellulose substrate soaked in the ion-imprinted imine block copolymer precursor solution C in a ventilated place at 30 degrees Celsius for 12 hours, and after the ethanol solvent evaporates naturally, a porous ion-imprinted imine adsorption material with sodium ion imprinting is obtained.

[0076] Example 2

[0077] The present embodiment provides a method for preparing a porous ion-imprinted imine adsorbent material with divalent magnesium ion imprinting, which is different from that of Example 1 in that: in step 1, 1,9-diamino α-nonanecarboxylic acid magnesium salt is used as the polyamino α-carboxylate with metal ions, and 1,4-dialdehyde pyridine is used as the rigid structure dialdehyde; in step 4, polyacrylamide is used as the matrix with a three-dimensional pore structure, and the volume ratio of the ion-imprinted imine block copolymer precursor solution C to the matrix is ​​2:1; the process parameters of the remaining steps are the same as those of Example 1;

[0078] Finally, after the ethanol solvent evaporates naturally, a porous ion-imprinted imine adsorption material with divalent magnesium ion imprinting is obtained.

[0079] Example 3

[0080] This embodiment provides a method for preparing a porous ion-imprinted imine adsorption material having lutetium ion imprinting, comprising the following steps:

[0081] Step 1: dissolving 0.6 mmol of 1,7-diamino α-heptyl carboxylate lutetium salt in 5 ml of ethanol, then adding 0.9 mmol of [1,1':4',1"-terphenyl]-4,4"-diformaldehyde having a rigid structure to the ethanol solution of 1,7-diamino α-heptyl carboxylate lutetium salt, ultrasonicating the solution for 30 minutes to promote the dissolution of [1,1':4',1"-terphenyl]-4,4"-diformaldehyde, and obtaining a mixed ethanol solution A of the two;

[0082] Step 2: dissolving 0.2 mmol of tri(4-aminobutyl)amine in 2 ml of ethanol to obtain solution B;

[0083] Step 3, mixing solution A and solution B, and subjecting solution A and solution B to ultrasonic treatment for 15 minutes to fully react, thereby obtaining a trivalent lutetium ion-imprinted imine block copolymer precursor solution C;

[0084] Step 4: Immerse a melamine formaldehyde resin matrix with a three-dimensional pore structure of 10*10*20 mm in a trivalent lutetium ion ion-imprinted imine block copolymer precursor solution C, wherein the volume ratio of the ion-imprinted imine block copolymer precursor solution C to the matrix is ​​1.5:1; expel the bubbles in the matrix by squeezing 10 times and ultrasonicating for 20 minutes, so that the trivalent lutetium ion ion-imprinted imine block copolymer precursor solution C fully enters the matrix cavity;

[0085] Step 5: Place the melamine formaldehyde resin matrix soaked in the ion-imprinted imine block copolymer precursor solution C with trivalent lutetium ions in a ventilated place at 30 degrees Celsius for 24 hours, and after the ethanol solvent evaporates naturally, a porous ion-imprinted imine adsorption material with lutetium ion imprinting is obtained.

[0086] The microstructure of the porous ion-imprinted imine adsorbent material with lutetium ion imprinting in the embodiment of the present invention was observed by scanning electron microscopy. Figure 1 As shown, it was found that polyimine with lutetium ion imprinting was uniformly loaded on the surface of the porous substrate of melamine formaldehyde resin, and the material had a good three-dimensional cavity structure.

[0087] Example 4

[0088] This embodiment provides a method for preparing a porous ion-imprinted imine adsorbent material with iron ion imprinting, and its macroscopic morphology and volume can be changed according to the size of the matrix with a three-dimensional pore structure. The specific steps of the preparation process are as follows:

[0089] Step 1: dissolving 0.1 mmol of 1,6-diamino α-hexanecarboxylic acid iron salt in 4 ml of ethanol, then adding 1.6 mmol of 2,2'-bipyridine-5,5'-dicarboxaldehyde having a rigid structure to the ethanol solution of 1,6-diamino α-hexanecarboxylic acid iron salt, and ultrasonicating the solution for 20 minutes to promote the dissolution of 2,2'-bipyridine-5,5'-dicarboxaldehyde to obtain a mixed ethanol solution A of the two;

[0090] Step 2: dissolving 1.0 mmol of tris(3-aminopropyl)amine in 3 ml of ethanol to obtain solution B;

[0091] Step 3, mixing solution A and solution B, and subjecting solution A and solution B to ultrasonic treatment for 60 minutes to fully react, thereby obtaining an ion-imprinted imine block copolymer precursor solution C of trivalent iron ions;

[0092] Step 4: Soak low-density polyether substrates with three-dimensional pore structures of sizes of 10*10*20 mm and 10*10*40 mm in ion-imprinted imine block copolymer precursor solution C of trivalent iron ions, respectively, with a volume ratio of the ion-imprinted imine block copolymer precursor solution C to the substrate being 1.6:1, and expel bubbles in the substrate by ultrasound for 10 minutes to allow the ion-imprinted imine block copolymer precursor solution C of trivalent iron ions to fully enter the cavities of the two substrates;

[0093] Step 5: Place the two sizes of low-density polyether substrates soaked in the ion-imprinted imine block copolymer precursor solution C at 30 degrees Celsius in a ventilated place for 48 hours, and after the ethanol solvent evaporates naturally, obtain porous ion-imprinted imine adsorption materials with iron ion imprinting of sizes of 10*10*20 mm and 10*10*40 mm, respectively. The two sizes of porous ion-imprinted imine adsorption materials are as follows: Figure 2 shown.

[0094] Example 5

[0095] The porous ion-imprinted imine adsorbent material with lutetium ions obtained in Example 3 was filled into a chromatography column and Figure 3 The purification experiment of nuclear medical waste liquid was carried out in the manner shown. Figure 3 In the method, a structure of two adsorption columns is adopted, and the porous ion-imprinted imine adsorption material is filled into a cylindrical chromatography column to obtain an adsorption column filled with the material;

[0096] Two adsorption columns are fixed on the stand in a manner perpendicular to the horizontal plane, and the radioactive waste liquid in the waste liquid inlet container is pumped into the adsorption columns by an electric peristaltic pump. The adsorption columns are connected in series end to end by pipes, and the upper end of one adsorption column is connected to the lower end of the next adsorption column. The liquid in all adsorption columns flows from bottom to top;

[0097] The effluent from the top of the last adsorption column is transported to the filtrate container through an electric peristaltic pump; the total α and total β radioactive activities of the purified liquid after purification are compared with those of the radioactive waste liquid before purification, so as to determine the purification effect of the porous ion-imprinted imine adsorption material on nuclear medical waste liquid.

[0098] Schematic diagram of waste liquid flow in the 4-column setting Figure 6 shown.

[0099] The source of the nuclear medical waste liquid used in this example is the nuclear medicine department of a tertiary hospital. 177 Lu] Lu-DOTATATE (commercial name: Lutathera) clinical trial, the patient's disinfection water and excrement produced by body fluid circulation. The purification experimental steps of nuclear medical waste liquid include:

[0100] (1) 2.5 liters of the collected nuclear medical waste liquid containing lutetium-177 was placed in a 4-liter beaker, 100 grams of a chemical flocculant was added, and the mixture was stirred thoroughly and allowed to stand for 24 hours to allow the solid suspended matter in the nuclear medical waste liquid to flocculate and precipitate;

[0101] (2) Take the supernatant in the 2-L beaker, divide it into two equal parts, and store them in two 2-L beakers respectively. Label them as liquid A for the experimental group and liquid B for the control group. The volume of liquid A and liquid B is 1 L each.

[0102] (3) Figure 3 The flow tube in the experiment group is placed in the A solution, and the nuclear medical waste liquid in the A solution is transferred to the chromatography column filled with porous ion-imprinted imine adsorbent material by an electric peristaltic pump, with a pump flow rate of 10 ml per minute;

[0103] (4) Collect the experimental group A solution after chromatographic column adsorption filtration, and determine the total α and total β radioactivity of the filtrate, and simultaneously determine the total α and total β radioactivity of the control group B solution;

[0104] (5) Figure 4 As shown in the figure, the total α of the filtrate of the experimental group A liquid was 0.011 Bq / L, and the total β was 2.37 Bq / L, and the total α of the control group B liquid was 1.743 Bq / L, and the total β was 6954.63 Bq / L. Figure 5 As shown, it is calculated that the purification effect of the porous ion-imprinted imine adsorbent material with lutetium ion imprinting on the nuclear medical waste liquid is 99.4% in total α filtration efficiency and 99.9% in total β filtration efficiency.

[0105] 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.

[0106] 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 porous ion-imprinted imine adsorption material for purification of nuclear medical waste liquid, characterized in that: The preparation method thereof comprises: Step 1: dissolving a polyamino α-carboxylate having metal ions in ethanol to obtain a polyamino α-carboxylate ethanol solution; then adding a rigid structure dialdehyde to the polyamino α-carboxylate ethanol solution, and ultrasonicating for 5 to 30 minutes to react the polyamino α-carboxylate with the rigid structure dialdehyde to promote the dissolution of the rigid structure dialdehyde to obtain a solution A; Step 2, dissolving a flexible triamino crosslinking agent in ethanol to obtain a solution B; the molar ratio of the polyamino α-carboxylate to the triamino crosslinking agent is 0.1-0.9:0.9-0.1, and the molar ratio of the amino groups in the polyamino α-carboxylate and the triamino crosslinking agent to the aldehyde groups in the rigid structure dialdehyde is 1:1; Step 3, mixing solution A and solution B, and subjecting solution A and solution B to ultrasonic treatment for 10 to 60 minutes to allow solution A and solution B to fully react, thereby obtaining an ion-imprinted imine block copolymer precursor solution C; Step 4: immersing the substrate having a three-dimensional pore structure in an ion-imprinted imine block copolymer precursor solution C, wherein the volume ratio of the ion-imprinted imine block copolymer precursor solution C to the substrate is 1.2:1 to 2:1, and expelling bubbles in the substrate by squeezing and ultrasound to allow the ion-imprinted imine block copolymer precursor solution C to fully enter the cavity of the substrate; Step 5: Place the substrate with a three-dimensional pore structure soaked in the precursor solution C in a ventilated place at 30° C., and after the ethanol solvent evaporates naturally, a porous ion-imprinted imine adsorption material is obtained; The structural formula of the polyamino α-carboxylate with metal ions is: Wherein, M is selected from one of sodium, lithium, potassium, silver, magnesium, calcium, titanium, iron, copper, cobalt, nickel, lutetium, and aluminum, n is an integer of 1 to 3, and q is an integer of 1 to 5; The structural formula of the rigid structure dialdehyde is: Wherein, X is one of CH and N, and p is an integer of 1 to 3; when p≥2, X is one of CH and N; The structural formula of the flexible triamino crosslinking agent is: Wherein, i is an integer from 1 to 3; The matrix with a three-dimensional pore structure is any one or more combinations of porous polyacrylamide, polypropylene, polyvinyl alcohol, low-density polyether, multi-walled carbon nanotubes, single-walled carbon nanotubes, melamine formaldehyde resin, and wood cellulose.

2. A method for preparing a porous ion-imprinted imine adsorbent material for purification of nuclear medical waste liquid according to claim 1, characterized in that: The following steps are involved: Step 1, dissolving a polyamino α-carboxylate having metal ions in ethanol to obtain a polyamino α-carboxylate ethanol solution; Subsequently, the rigid structure dialdehyde is added to the polyamino α-carboxylate ethanol solution, and ultrasonication is performed for 5 to 30 minutes to allow the polyamino α-carboxylate to react with the rigid structure dialdehyde, thereby promoting the dissolution of the rigid structure dialdehyde to obtain solution A; Step 2: dissolving a flexible triamino cross-linking agent in ethanol to obtain a solution B; Step 3, mixing solution A and solution B, and subjecting solution A and solution B to ultrasonic treatment for 10 to 60 minutes to allow solution A and solution B to fully react, thereby obtaining an ion-imprinted imine block copolymer precursor solution C; Step 4: immersing the substrate having a three-dimensional pore structure in an ion-imprinted imine block copolymer precursor solution C, wherein the volume ratio of the ion-imprinted imine block copolymer precursor solution C to the substrate is 1.2:1 to 2:1, and expelling bubbles in the substrate by squeezing and ultrasound to allow the ion-imprinted imine block copolymer precursor solution C to fully enter the cavity of the substrate; Step 5: Place the substrate with a three-dimensional pore structure soaked in the precursor solution C in a ventilated place at 30° C., and after the ethanol solvent evaporates naturally, a porous ion-imprinted imine adsorption material is obtained.

3. The method for preparing a porous ion-imprinted imine adsorbent material for purification of nuclear medical waste liquid according to claim 2, characterized in that: In the step 1, the molar volume ratio of the polyamino α-carboxylate to ethanol is 0.4-0.6 mmol: 2-5 mL; In the step 2, the molar volume ratio of the flexible triamino cross-linking agent to ethanol is 0.2-0.4 mmol:2-5 mL.

4. An application of the porous ion-imprinted imine adsorption material for purification of nuclear medical waste liquid according to claim 1, characterized in that: The porous ion-imprinted imine adsorption material is applied to the purification of nuclear medical waste liquid.

5. The use of the porous ion-imprinted imine adsorption material for purification of nuclear medical waste liquid according to claim 4, characterized in that: The porous ion-imprinted imine adsorption material for purifying nuclear medical waste liquid comprises the following steps: Filling a porous ion-imprinted imine adsorption material into a cylindrical chromatography column to obtain an adsorption column filled with the material; Fix 1 to 4 adsorption columns on the stand in a manner perpendicular to the horizontal plane, and use an electric peristaltic pump to extract the radioactive waste liquid into the adsorption columns. When the number of adsorption columns is ≥ 2, use pipes to connect the adsorption columns end to end in series, with the upper end of one adsorption column connected to the lower end of the next adsorption column, and the liquid in all adsorption columns flows from bottom to top; The effluent from the top of the last adsorption column is transported to the filtrate container through an electric peristaltic pump; the total α and total β radioactive activities of the purified liquid after purification are compared with those of the radioactive waste liquid before purification, so as to determine the purification effect of the porous ion-imprinted imine adsorption material on nuclear medical waste liquid.

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