A method for adsorptive concentration of lutetium ions

Abstract

The application provides a method for adsorbing and concentrating lutetium ions, and belongs to the technical field of rare earth material separation. The method comprises the following steps: loading adsorption fillers into an adsorption column; adding hydrochloric acid to a water solution containing organic acid impurities and lutetium ions, adjusting the pH to 1-3, and loading the adjusted liquid into the adsorption column at a set linear velocity by using a liquid pump; using deionized water to perform elution on the adsorption column; using a dilute hydrochloric acid solution to perform elution on the adsorption column; the adsorption fillers are polymer microspheres; the polymer microspheres comprise a polymer and a surface modified aminocarboxylic acid; the polymer is a copolymer of an epoxy-containing monomer and an alkenyl-containing monomer; the aminocarboxylic acid is at least one selected from NTA, EDTA, DTPA, DOTA and NOTA. The application is based on the strong complexing capacity of the aminocarboxylic complexing agent to metal lutetium, can effectively adsorb lutetium, remove the organic acid impurities in the loading liquid, simultaneously plays a concentrating effect, and meets the medical lutetium chloride solution standard.

Description

Technical Field

[0001] This invention belongs to the technical field of rare earth material separation, and specifically relates to a method for lutetium ion adsorption and concentration. Background Technology

[0002] Chromatographic separation is a commonly used method for separating rare earth elements. It utilizes the different partition coefficients of different substances in a system composed of a stationary phase and a mobile phase. When the two phases move relative to each other, these substances move with the mobile phase and undergo repeated partitioning between the two phases, thus achieving separation. For example, in the preparation of lutetium-177, organic acids are used as eluents to separate lutetium and ytterbium. However, the obtained single lutetium-177 fraction contains organic acid eluents, such as α-hydroxyisobutyric acid, α-hydroxy-α-methylbutyric acid, lactic acid, citric acid, butyric acid, ethylenediaminetetraacetic acid (EDTA), and other hydroxycarboxylic acids and aminocarboxylic acids. This untreated lutetium-177 cannot be directly used as a radiopharmaceutical raw material. On the one hand, the organic carboxylic acids affect the labeling reaction of Lu-177; on the other hand, these organic carboxylic acids are harmful to the human body. Further processing is needed to remove the organic acids and convert it into a lutetium chloride solution. Conventional treatment uses sulfonic acid resin as an adsorbent and strong acid as an eluent, followed by further evaporation to dry the strong acid. However, strong acids are highly volatile and corrosive to the environment, requiring sophisticated equipment. Furthermore, the added processing steps increase the risk of radioactive dose loss. In addition, untreated lutetium-177 has a very low concentration, failing to meet medical standards; and since high-concentration acids are also unsuitable for medical use, a subsequent evaporation and acid removal step is necessary. Summary of the Invention

[0003] Therefore, the present invention aims to provide a lutetium ion adsorption and concentration method to solve at least one technical problem in the background art.

[0004] This invention is implemented as follows:

[0005] A method for lutetium ion adsorption and concentration, the method comprising the following steps:

[0006] The adsorption packing material is packed into the adsorption column;

[0007] Hydrochloric acid is added to an aqueous solution of lutetium ions containing organic acid impurities to adjust its pH to 1-3. The adjusted liquid is then fed into the adsorption column at a set linear velocity using an infusion pump, so that lutetium is adsorbed in the polymer microspheres.

[0008] The adsorption column was rinsed with deionized water to remove residual organic acids.

[0009] The adsorption column was eluted with dilute hydrochloric acid solution to desorb the lutetium adsorbed in the adsorption column.

[0010] The adsorption filler is a polymer microsphere; the polymer microsphere comprises a polymer and an aminocarboxylic acid modified on its surface.

[0011] The polymer is a copolymer containing epoxy-containing monomers and alkenyl-containing monomers;

[0012] The aminocarboxylic acid is selected from at least one of the following: nitrotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid, and 1,4,7-triazacyclononane-1,4,7-triacetic acid (NTA, EDTA, DTPA, DOTA, NOTA).

[0013] Furthermore, the structural schematics of the polymer microspheres are as follows: (I) to (V):

[0014]

[0015] Furthermore, the epoxy-containing monomer is selected from at least one of 3,4-epoxy-1-butene, allyl glycidyl ether, 2-(4-vinylphenyl)epoxy ethylene, and glycidyl methacrylate.

[0016] Furthermore, the alkenyl monomer is selected from at least one of styrene, divinylbenzene, vinylidene chloride, acrylic acid, acrylamide, methyl methacrylate, methyl acrylate, and trifluorochloroethylene.

[0017] Mix 20-30 mL of 1-bromododecane, 2.5-7.5 mL of 3,4-epoxy-1-butene, 15-25 mL of divinylbenzene, and 0.15-0.35 g of azobisisobutyronitrile until homogeneous. Mix the oil phase with 1 L of aqueous phase containing 1-4 g of polyvinyl alcohol and 10-15 g of sodium carbonate until homogeneous. Stir at 200-800 rpm and emulsify for 10-30 min. Increase the temperature to 60-80℃ and react for 3-6 h. Wash five times with ethanol and vacuum dry to obtain polymer microspheres. The pore size of the polymer microspheres is [missing information]. Particle size: 30-100 μm; pore volume: 0.5-1 cm³ 3 / g; specific surface area is 100-300m² 2 / g;

[0018] Add 1.0 g of the above polymer microspheres, 0.1–2.0 g of aminocarboxylic acid complexing agent and 0.15–3.0 g of alkaline catalyst to 10–30 mL of organic solvent, heat and stir at 40–120 °C for 8–48 hours, filter, and wash successively with methanol, water, 0.2 M hydrochloric acid solution, water and methanol. The obtained solid is vacuum dried in a drying oven at 40–80 °C for 8–24 hours to obtain the aminocarboxylic acid polymer material.

[0019] Further, the organic solvent is at least one of xylene, ethanol, N,N-dimethylformamide, dimethyl sulfoxide, and tetrahydrofuran.

[0020] Further, the aminocarboxylic acid complexing agent is at least one selected from the following: hypozonotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid, and 1,4,7-triazacyclononane-1,4,7-triacetic acid.

[0021] Furthermore, the alkaline catalyst is one of diisopropylethylamine, triethylamine, sodium hydroxide, sodium bicarbonate, potassium carbonate, and pyridine.

[0022] Furthermore, the amount of aminocarboxylic acid modification is 0.2 mmol / g to 1.2 mmol / g.

[0023] Furthermore, the linear velocity of the sample loading is 1 cm / min to 50 cm / min, and the temperature range is 0℃ to 80℃; the water used for rinsing is 3 to 20 column volumes, and the linear velocity of rinsing is not higher than the linear velocity of the sample loading.

[0024] Furthermore, the concentration of the dilute hydrochloric acid solution used for elution is <0.5M; the volume of the dilute hydrochloric acid solution used for elution is 2 to 8 column volumes; and the linear velocity of elution is 1 / 20 to 1 / 2 of the linear velocity of sample loading.

[0025] This invention is based on the strong complexing ability of aminocarboxylic acid complexing agents for lutetium metal, which can effectively adsorb lutetium, remove organic acid impurities in the sample solution, and at the same time achieve a concentration effect, meeting the standards for medical lutetium chloride solution.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] 1. This invention uses aminocarboxylic acid as the modification structure on the surface of polymer microspheres. Based on the strong complexing ability of aminocarboxylic acid complexing agent for lutetium metal, it can effectively adsorb lutetium, remove organic acid impurities in the sample solution, and at the same time achieve the effect of concentration (the volume can be concentrated by 10 to 100 times), meeting the medical standard for lutetium chloride solution.

[0028] 2. During elution, the adsorbent of the present invention can elute lutetium ions with a low-strength acid (<0.5M), and the resulting eluent can be directly used for subsequent labeling reactions without the need for evaporation to remove acid. Detailed Implementation

[0029] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0030] A method for lutetium ion adsorption and concentration includes the following steps 1 to 4:

[0031] Step 1: Installing the column

[0032] The adsorption packing material is pumped into the adsorption column using a gas compression pump. The volume of the column depends on the total amount of lutetium to be treated.

[0033] The adsorption filler is a polymer microsphere, comprising a polymer and its surface-modified aminocarboxylic acid. The polymer is a copolymer of an epoxy-containing monomer and an alkenyl-containing monomer. The epoxy-containing monomer is selected from at least one of 3,4-epoxy-1-butene, allyl glycidyl ether, 2-(4-vinylphenyl)epoxyethylene, and glycidyl methacrylate. The alkenyl-containing monomer is selected from at least one of styrene, divinylbenzene, vinylidene chloride, acrylic acid, acrylamide, methyl methacrylate, methyl acrylate, and trifluorochloroethylene. The aminocarboxylic acid is selected from at least one of hypozoxytriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid, and 1,4,7-triazacyclononane-1,4,7-triacetic acid. Studies have shown that both monomers are essential for the polymer microspheres; polymerization using a single monomer makes it difficult to form microspheres, or the resulting polymer may not achieve surface group modification or adsorption functionality.

[0034] This invention modifies various aminocarboxylic acid chelating groups onto polymer microspheres and optimizes the bonding density of the groups. These chelating groups can form chelates (complexes) with metal ions. Their interaction with metals is moderate, and lutetium ions can be eluted with low-strength acids (≤0.5M). The resulting eluent can be directly used for subsequent labeling reactions without the need for evaporation to remove acid.

[0035] The structural schematics of polymer microspheres are shown in equations (I) to (V):

[0036]

[0037] The pore size of the polymer microspheres is Particle size ranges from 30 to 100 μm; pore volume ranges from 0.5 to 1 cm³. 3 / g; specific surface area is 100-300m² 2 / g;

[0038] The amount of aminocarboxylic acid modification ranges from 0.2 mmol / g to 1.2 mmol / g.

[0039] Step 2, Sample preparation and loading

[0040] Add an appropriate amount of hydrochloric acid to the aqueous solution containing lutetium ions and organic carboxylic acids to adjust its pH to 1-3; if there are insoluble substances in the solution, it needs to be filtered to prevent clogging of the adsorption column; the adsorption capacity of lutetium ions can reach 1.0 mg / g to 6.0 mg / g, and the total amount of lutetium should not exceed 2 / 3 of the adsorption column's processing capacity, otherwise it will cause material loss.

[0041] The conditioned liquid is fed into the adsorption column at a set linear velocity using any type of infusion pump, allowing lutetium to be adsorbed within the polymer microspheres. During the loading process, both temperature and flow rate need to be set, depending on the size of the adsorption column and the concentration of lutetium ions in the solution. Generally, the loading flow rate is a linear velocity, ranging from 1 cm / min to 50 cm / min, and the temperature range is 0℃ to 80℃. The linear velocity during loading can be 5 cm / min, 25 cm / min, or 50 cm / min; the temperature can be 0℃ to 10℃, 25℃ to 35℃, or 70℃ to 80℃; however, these values ​​are not limited to these listed values, and other unlisted values ​​within the same range are also applicable.

[0042] Step 3, Rinse

[0043] Deionized water is passed through an adsorption column by any type of infusion pump to wash the adsorption column and remove residual organic acids. The organic acids are then carried away by the water flow to form waste liquid.

[0044] The amount of water used for rinsing is 3 to 20 column volumes. The rinsing speed can be the same as or slightly lower than the loading speed for better results.

[0045] Step 4, Washing

[0046] The adsorption column was eluted with a low-concentration dilute hydrochloric acid solution (<0.5M) to desorb the adsorbed lutetium and obtain concentrated lutetium. The elution volume was 2 to 8 column volumes. The elution linear velocity was 1 / 20 to 1 / 2 of the loading linear velocity.

[0047] After steps 1 to 4 are completed, the packing material in the adsorption column can be regenerated. The regeneration process is as follows: use high-concentration hydrochloric acid (>1M) to completely remove any residual trace amounts of lutetium in the adsorption column, thus ensuring it will not affect the next use. The flow rate of the regeneration solution is relatively flexible, but it is recommended to be 1 / 10 to 1 of the loading linear velocity; the volume of the regeneration solution is generally higher than one column volume; the regeneration process is not mandatory, and if the adsorption column is for single use, the regeneration step can be omitted.

[0048] Example 1

[0049] This embodiment uses polymer microspheres to adsorb and concentrate lutetium, specifically including the following steps:

[0050] S1. Preparation of polymer microspheres as adsorption fillers

[0051] 25 mL of 1-bromododecane, 5 mL of 3,4-epoxy-1-butene, 20 mL of divinylbenzene, and 0.25 g of azobisisobutyronitrile were mixed thoroughly (oil phase). The oil phase was then mixed thoroughly with 1 L of an aqueous phase containing 2.5 g of polyvinyl alcohol and 12.5 g of sodium carbonate. The mixture was stirred at 800 rpm and emulsified for 20 min. The temperature was then increased to 60 °C, and the reaction was carried out for 6 h. The mixture was washed five times with ethanol and vacuum dried to obtain polymer microspheres. The pore size of the polymer microspheres was [insert pore size here]. Particle size 30-50μm; pore volume 0.5cm³ 3 / g; specific surface area is 280m² 2 / g;

[0052] 1.0 g of the above polymer microspheres, 0.52 g of hypozinogenyl triacetic acid (NTA), and 0.59 g of sodium bicarbonate were added to 15 mL of N,N-dimethylformamide. The mixture was heated and stirred at 90 °C for 24 hours, filtered, and washed successively with methanol, water, 0.2 M hydrochloric acid solution, water, and methanol. The resulting solid was vacuum dried in a drying oven at 60 °C for 16 hours to obtain the NTA-modified polymer material. The NTA modification amount was 0.8 mmol / g.

[0053] Polymer microspheres with the following structure were obtained:

[0054]

[0055] Polymer microspheres were used as adsorption packing material and pumped into an adsorption column with an inner diameter of 10 mm and a length of 100 mm using a gas compression pump. The volume of the column depended on the total amount of lutetium to be treated.

[0056] S2, Sample preparation and loading

[0057] In 1L of an aqueous solution of 50mM α-hydroxyisobutyric acid containing 0.2ppm lutetium ions (pH 4.3), an appropriate amount of 2M hydrochloric acid was added to adjust the pH to approximately 3. The adjusted liquid was then fed into the adsorption column at a temperature of 25℃~35℃ and a linear velocity of 25cm / min by an infusion pump, so that lutetium was adsorbed in the polymer microspheres.

[0058] S3, Rinse

[0059] The infusion pump passes approximately 10 column volumes of deionized water through the adsorption column at a linear velocity of approximately 25 cm / min to wash the adsorption column and remove residual organic acids. The organic acids are then carried away by the water flow to form waste liquid.

[0060] S4, Washing

[0061] The adsorption column was eluted with a dilute hydrochloric acid solution of about 0.4 M and about 4 column volumes at a linear velocity of about 10 cm / min to desorb the lutetium adsorbed in the adsorption column and obtain concentrated lutetium.

[0062] Example 2

[0063] The main difference between Example 2 and Example 1 is that the monomers and aminocarboxylic acid complexing agents used to prepare the copolymer are different.

[0064] In Example 2, the epoxy-containing monomer of the S1 copolymer was selected from allyl glycidyl ether, and the alkenyl monomer was selected from vinylidene chloride. 25 mL of 1-bromododecane, 5 mL of allyl glycidyl ether, 20 mL of vinylidene chloride, and 0.25 g of azobisisobutyronitrile were mixed thoroughly. The oil phase and 1 L of aqueous phase containing 2.5 g of polyvinyl alcohol and 12.5 g of sodium carbonate were mixed thoroughly. The remaining reaction conditions were the same as in Example 1. The final polymer microspheres obtained had a pore size of [missing information]. Particle size is 50-70 μm; pore volume is 0.5 cm³. 3 / g; specific surface area is 150m² 2 / g;

[0065] The aminocarboxylic acid complexing agent used for polymer surface modification was replaced with ethylenediaminetetraacetic acid (EDTA), and the remaining reaction conditions were the same as in Example 1. The amount of EDTA modification was 0.7 mmol / g.

[0066] Polymer microspheres with the following structure were obtained:

[0067]

[0068] Using the polymer microspheres as the adsorption packing material, lutetium ions were adsorbed and concentrated through steps such as column packing, sample loading, rinsing, and elution. The specific process and conditions were the same as in Example 1.

[0069] Example 3

[0070] The main difference between Example 3 and Example 1 is that the monomers and aminocarboxylic acid complexing agents used to prepare the copolymer are different.

[0071] In Example 3, the S1 copolymer used an epoxy-containing monomer selected from 2-(4-vinylphenyl)ethylene oxide and an alkenyl monomer selected from styrene. 30 mL of 1-bromododecane, 5 mL of 2-(4-vinylphenyl)ethylene oxide, 20 mL of styrene, and 0.25 g of azobisisobutyronitrile were mixed thoroughly. The oil phase and 1 L of aqueous phase containing 3 g of polyvinyl alcohol and 12.5 g of sodium carbonate were mixed thoroughly. The mixture was stirred at 400 rpm and emulsified for 20 min. The temperature was then raised to 80 °C and the reaction was carried out for 5 h. The final polymer microspheres obtained had a pore size of [missing information]. Particle size is 70-85 μm; pore volume is 0.8 cm³.3 / g; specific surface area is 100m² 2 / g.

[0072] The aminocarboxylic acid complexing agent used for polymer surface modification was diethylenetriaminepentaacetic acid (DPTA), and the remaining reaction conditions were the same as in Example 1. The modification amount of DPTA was 0.9 mmol / g.

[0073] Polymer microspheres with the following structure were obtained:

[0074]

[0075] Using the polymer microspheres as the adsorption packing material, lutetium ions were adsorbed and concentrated through steps such as column packing, sample loading, rinsing, and elution. The specific process and conditions were the same as in Example 1.

[0076] Example 4

[0077] The main difference between Example 4 and Example 1 is that the monomers and aminocarboxylic acid complexing agents used to prepare the copolymer are different.

[0078] In Example 4, the S1 copolymer used an epoxy-containing monomer selected from glycidyl methacrylate and an alkenyl monomer selected from acrylamide. 20 mL of 1-bromododecane, 5 mL of glycidyl methacrylate, 20 mL of acrylamide, and 0.25 g of azobisisobutyronitrile were mixed thoroughly. The oil phase and 1 L of aqueous phase containing 4 g of polyvinyl alcohol and 12.5 g of sodium carbonate were mixed thoroughly. The mixture was stirred at 800 rpm and emulsified for 30 min. The temperature was then raised to 60 °C and the reaction was carried out for 3 h. The resulting polymer microspheres had a pore size of [missing information]. The particle size is 30 μm; the pore volume is 0.7 cm³. 3 / g; specific surface area is 180m² 2 / g;

[0079] The aminocarboxylic acid complexing agent used for polymer surface modification was 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA), and the remaining reaction conditions were the same as in Example 1. The modification amount of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) was 0.5 mmol / g.

[0080] Polymer microspheres with the following structure were obtained:

[0081]

[0082] Using the polymer microspheres as the adsorption packing material, lutetium ions were adsorbed and concentrated through steps such as column packing, sample loading, rinsing, and elution. The specific process and conditions were the same as in Example 1.

[0083] Example 5

[0084] The difference between Example 5 and Example 1 is that the monomers and aminocarboxylic acid complexing agents used to prepare the copolymer are different, while the other processes and conditions are the same as in Example 1.

[0085] In Example 5, the S1 copolymer used an epoxy-containing monomer selected from glycidyl methacrylate and an alkenyl monomer selected from methyl methacrylate. 25 mL of 1-bromododecane, 5 mL of glycidyl methacrylate, 18 mL of methyl methacrylate, and 0.25 g of azobisisobutyronitrile were mixed thoroughly. The oil phase and 1 L of aqueous phase containing 3 g of polyvinyl alcohol and 12.5 g of sodium carbonate were mixed thoroughly. The mixture was stirred at 300 rpm and emulsified for 15 min. The temperature was then raised to 70 °C and the reaction was carried out for 6 h. The resulting polymer microspheres had a pore size of [missing information]. The particle size is 80 μm; the pore volume is 0.9 cm³. 3 / g; specific surface area is 170m² 2 / g;

[0086] The aminocarboxylic acid complexing agent used for polymer surface modification was 1,4,7-triazacyclononane-1,4,7-triacetic acid (NOTA), and the remaining reaction conditions were the same as in Example 1. The modification amount of 1,4,7-triazacyclononane-1,4,7-triacetic acid (NOTA) was 0.5 mmol / g.

[0087] Polymer microspheres with the following structure were obtained:

[0088]

[0089] Using the polymer microspheres as adsorption packing material, lutetium ions are adsorbed and concentrated through steps such as column packing, sample loading, rinsing, and elution.

[0090] Example 6

[0091] The main difference between Example 6 and Example 1 is that the monomers used to prepare the copolymer are different, and the amount of NTA bonding is different.

[0092] In Example 6, the S1 copolymer used an epoxy-containing monomer selected from allyl glycidyl ether and an alkenyl monomer selected from methyl acrylate. 30 mL of 1-bromododecane, 5 mL of allyl glycidyl ether, 15 mL of methyl acrylate, and 0.30 g of azobisisobutyronitrile were mixed thoroughly. The oil phase and 1 L of aqueous phase containing 1.5 g of polyvinyl alcohol and 15 g of sodium carbonate were mixed thoroughly. The mixture was stirred at 200 rpm and emulsified for 10 min. The temperature was then raised to 80 °C and the reaction was carried out for 6 h. The pore size of the polymer microspheres was [not specified]. Particle size: 80-100 μm; pore volume: 0.4 cm³ 3 / g; specific surface area is 140m² 2 / g;

[0093] The aminocarboxylic acid complexing agent used for polymer surface modification was NTA, the basic catalyst was pyridine, the reaction temperature was 60°C, and the remaining reaction conditions were the same as in Example 1. The amount of NTA modification was 0.3 mmol / g.

[0094] Using the polymer microspheres as the adsorption packing material, lutetium ions were adsorbed and concentrated through steps such as column packing, sample loading, rinsing, and elution. The specific process and conditions were the same as in Example 1.

[0095] Example 7

[0096] The difference between Example 7 and Example 1 is that the linear speed of sample loading and rinsing is adjusted to 5 cm / min, while the other processes and conditions are the same as in Example 1.

[0097] Example 8

[0098] The difference between Example 8 and Example 1 is that the linear speed of sample loading and rinsing is adjusted to 50 cm / min, while the other processes and conditions are the same as in Example 1.

[0099] Example 9

[0100] The difference between Example 9 and Example 1 is that the sample loading temperature is adjusted to 0℃~10℃, while the other processes and conditions are the same as in Example 1.

[0101] Example 10

[0102] The difference between Example 10 and Example 1 is that the sample loading temperature is adjusted to 70℃~80℃, while the other conditions are the same as in Example 1.

[0103] Comparative Example 1

[0104] The difference between Comparative Example 1 and Example 1 is that the adsorbent used is a conventional cation exchange material - polystyrene sulfonic acid cation exchange resin, while the other processes and conditions are the same as in Example 1.

[0105] Comparative Example 2

[0106] The difference between Comparative Example 2 and Example 1 is that the surface of the polymer microspheres does not contain the modification of the aminocarboxylic acid structure, while the other processes and conditions are the same as in Example 1.

[0107] The adsorption effects of lutetium ions in Examples 1 to 11 and Comparative Examples 1 to 4 were compared. The amount of lutetium ions adsorbed was the mass of lutetium adsorbed per unit volume of the packing material. The lutetium ion adsorption efficiency was the adsorbed lutetium ions divided by the total amount of lutetium. The desorption efficiency was the desorbed lutetium ion mass divided by the adsorbed amount. The results are shown in Table 1.

[0108] Table 1

[0109]

[0110]

[0111] As shown in Table 1, Examples 1 to 11 of this invention use polymer microspheres with surface-modified aminocarboxylic acid structures as adsorbents, which can efficiently adsorb concentrated lutetium ions, making the product meet the standards for medical lutetium chloride solutions. Examples 1 to 7 use different monomers and different aminocarboxylic acids as complexing agents, and it can be seen that all of them can effectively adsorb lutetium.

[0112] A comparison of Examples 1, 7, and 8 shows that the adsorption effect deteriorates as the linear velocity of the sample increases. This is because the contact time between lutetium ions and the adsorbent becomes shorter, resulting in insufficient adsorption.

[0113] A comparison of Examples 1, 9 and 10 shows that the adsorption effect deteriorates as the loading temperature increases. This is because the chelating ability of the adsorbent for lutetium ions weakens with increasing temperature.

[0114] As can be seen from the comparison between Example 1 and Comparative Example 1, conventional strong cation exchange materials have a better adsorption effect on lutetium ions. However, low concentrations of inorganic acids make it difficult to remove lutetium ions from the adsorbent. Thus, Comparative Example 1 has a high adsorption efficiency but a very poor desorption efficiency.

[0115] As can be seen from the comparison between Example 1 and Comparative Example 2, the polymer microspheres without aminocarboxylic acid group modification have no adsorption effect on lutetium ions.

[0116] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. A method for lutetium ion adsorption and concentration, characterized in that, The method includes the following steps: The adsorption packing material is packed into the adsorption column; Add 0.5-12M hydrochloric acid to an aqueous solution of lutetium ions containing organic acid impurities to adjust the pH to 1-3. Then, use a pump to feed the adjusted liquid into the adsorption column at a set linear velocity, so that lutetium is adsorbed in the polymer microspheres. The adsorption column was rinsed with deionized water to remove residual organic acids. The adsorption column was eluted with dilute hydrochloric acid solution to desorb the lutetium adsorbed in the adsorption column. The adsorption filler is a polymer microsphere; the polymer microsphere comprises a polymer and an aminocarboxylic acid modified on its surface. The polymer is a copolymer containing epoxy-containing monomers and alkenyl-containing monomers; The aminocarboxylic acid modified raw material is selected from at least one or more of the following: nitrotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid, and 1,4,7-triazacyclononane-1,4,7-triacetic acid.

2. The lutetium ion adsorption and concentration method according to claim 1, characterized in that, The structural schematic of the polymer microspheres is shown in at least one or more of the following formulas (I) to (V):

3. The lutetium ion adsorption and concentration method according to claim 1 or 2, characterized in that, The epoxy-containing monomer is selected from at least one or more of 3,4-epoxy-1-butene, allyl glycidyl ether, 2-(4-vinylphenyl)epoxy ethylene, and glycidyl methacrylate.

4. The lutetium ion adsorption and concentration method according to claim 1 or 2, characterized in that, The alkenyl monomer is selected from at least one or more of styrene, divinylbenzene, vinylidene chloride, acrylic acid, acrylamide, methyl methacrylate, methyl acrylate, and trifluorochloroethylene.

5. The lutetium ion adsorption and concentration method according to claim 1 or 2, characterized in that, The pore size of the polymer microspheres is Particle size: 30-100 μm; pore volume: 0.5-1 cm³ 3 / g; specific surface area is 100-300m² 2 / g.

6. The lutetium ion adsorption and concentration method according to claim 1 or 2, characterized in that, The amount of aminocarboxylic acid modification is 0.2 mmol / g to 1.2 mmol / g.

7. The lutetium ion adsorption and concentration method according to claim 1, characterized in that, The linear velocity of the sample loading is 1 cm / min to 50 cm / min, and the temperature range is 0℃ to 80℃.

8. The lutetium ion adsorption and concentration method according to claim 1 or 7, characterized in that, The amount of water used for rinsing is 3 to 20 column volumes, and the rinsing linear velocity is not higher than (less than or equal to) the sample loading linear velocity, which can be 1 cm / min to 50 cm / min.

9. The lutetium ion adsorption and concentration method according to claim 1 or 7, characterized in that, The concentration of the dilute hydrochloric acid solution used for elution is ≤0.5M, preferably 0.15-0.3M; the volume of the dilute hydrochloric acid solution used for elution is 2 to 8 column volumes; the elution linear velocity is 1 / 20 to 1 / 2 of the loading linear velocity.

10. The lutetium ion adsorption and concentration method according to claim 1, characterized in that, The composition of the lutetium ion aqueous solution containing organic acid impurities is as follows: the concentration of lutetium ions is 0.1 ppb-100 ppm, the concentration of organic acid is 0.01-2 mol / L, and the organic acid is at least one or more of α-hydroxyisobutyric acid, α-hydroxy-α-methylbutyric acid, lactic acid, citric acid, butyric acid, and ethylenediaminetetraacetic acid (EDTA).

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