A Fe adsorption 3+ Resin material and preparation method and application thereof

Abstract

The present invention provides a method for adsorbing Fe 3+ The resin material and its preparation method and application belong to the technical field of adsorption materials. 3+ The preparation method of the resin material comprises: mixing polyamide-amine modified silica or a derivative of polyamide-amine modified silica, a carboxylic acid containing a phosphorus-oxygen double bond, a solvent and a nucleophilic reagent, and performing an amidation reaction to obtain Fe adsorbent. 3+ The raw materials of the dendritic polymer polyamide-amine modified silica or its derivatives are easily available, which can reduce costs. At the same time, the dendritic polymer polyamide-amine modified silica or its derivatives have dendritic amino groups, which can react with the carboxylic acid groups in the carboxylic acid containing phosphorus and oxygen double bonds to obtain multiple active sites that bind to iron, thereby improving the adsorption of Fe 3+ The adsorption performance of resin materials on iron.

Description

Technical Field

[0001] The present invention belongs to the technical field of adsorption materials, and specifically relates to a method for adsorbing Fe 3+ Resin material, preparation method and application thereof. Background Art

[0002] In order to control and evaluate the radiation impact of nuclear power plants on the surrounding environment and residents, it is necessary to accurately and efficiently monitor the activity concentration of radionuclides in the nuclear power plant environment and effluents, and establish a separation and analysis process for each nuclide, especially those with a long half-life (β-nuclides). 90 Sr, 137 Cs, 134 Cs, 55 Fe, 63 The measurement of Ni) is of great significance to the emission monitoring and evaluation of liquid effluents from nuclear power plants. The beta nuclides in liquid effluents are generally of the following types: 3H (12.33a, 18.6 KeV), 90 Sr (28.79 a, 0.546 keV), 137 Cs (30.17 a, 512 KeV-94.6%, 1174KeV-5.4%), 55 Fe(2.7a, 5.9keV), 63 Ni (100.1 a, 16keV), 54Mn (312.12 d, 835 keV), 110m Ag(249.76d), 65 Zn(244.06 d), 58Co(71.8 d), 51 Cr(27.7 d), 131 I (8.05 d), etc. β-nuclides are more sensitive to liquid scintillation counter (LSC), but the measurement process is greatly affected by interfering nuclides, and sufficient separation and purification steps are required before measurement. 55 Fe decays to a stable state by emitting Auger electrons and low-energy X-rays through electron capture. 55 Mn, due to the low energy of decay emission (5.9keV, 16.5%), must be completely separated from interfering nuclides before measurement, which places higher requirements on adsorption and separation materials. 55 The most commonly used materials in the separation and purification of Fe are TRU resin and anion exchange resin.

[0003] TRU resin is currently a highly performing separation material. It is prepared by loading the extractant CMPO (n-octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide) onto a support. However, due to its physical loading, the CMPO loading decreases during use, resulting in poor iron adsorption capacity (3 mg per 2 mL of resin). Furthermore, the preparation cost of CMPO is high, making it expensive. Therefore, the development of a material with high iron selectivity at a low cost has become an urgent technical challenge in this field. Summary of the Invention

[0004] The object of the present invention is to provide a method for adsorbing Fe 3+ The resin material and its preparation method and application. The preparation method provided by the present invention reduces the cost, and the prepared Fe adsorption 3+ Resin material for Fe 3+ Possesses excellent selective adsorption capacity.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a method for adsorbing Fe 3+ A method for preparing a resin material, comprising:

[0007] The polyamide-amine modified silica or a derivative of the polyamide-amine modified silica, a carboxylic acid containing a phosphorus-oxygen double bond, a solvent and a nucleophilic reagent are mixed and subjected to an amidation reaction to obtain an adsorbent of Fe 3+ resin material.

[0008] Preferably, the structural formula of the carboxylic acid containing a phosphorus-oxygen double bond is as shown in Formula I:

[0009] Formula I;

[0010] In formula I, R1 and R2 are independently phenyl, cyclohexyl, C8H 17 , C4H9, 2-methoxyphenyl, methyl, ethoxy, C6H 13 、OC6H 13 , ethyl or methoxy.

[0011] Preferably, the molar ratio of the polyamide-amine modified silica or the derivative of the polyamide-amine modified silica to the carboxylic acid containing a phosphorus-oxygen double bond is 1:(1.8-2.2).

[0012] Preferably, the molar ratio of the polyamide-amine modified silica or the derivative of the polyamide-amine modified silica to the carboxylic acid containing a phosphorus-oxygen double bond is 1:(3.6-4.4).

[0013] Preferably, the molar ratio of the polyamide-amine modified silica or the derivative of the polyamide-amine modified silica to the carboxylic acid containing a phosphorus-oxygen double bond is 1:(5.4-6.6).

[0014] Preferably, the molar ratio of the polyamide-amine modified silica or the derivative of the polyamide-amine modified silica to the carboxylic acid containing a phosphorus-oxygen double bond is 1:(7.2-8.8).

[0015] Preferably, the amidation reaction temperature is 100-120° C., and the amidation reaction time is 30-50 min.

[0016] The present invention also provides the adsorbed Fe prepared by the preparation method described in the above technical solution 3+ resin material.

[0017] Preferably, it comprises silicon dioxide and active groups grafted onto the surface of the silicon dioxide;

[0018] The structural formula of the active group is shown in Formula II:

[0019] Formula II;

[0020] In formula II, R1 and R2 are independently phenyl, cyclohexyl, C8H 17 , C4H9, 2-methoxyphenyl, methyl, ethoxy, C6H 13 、OC6H 13 , ethyl or methoxy; R3 is H, ethyl, C4H9, CH(CH3)2C2H5, phenyl, OC6H 13 、C6H 13 、C8H 17 、C9H 19 、C 10 H 21 、C 12 H 25 、(CH2)2Ph、six-membered heterocyclic ring、(CH2)5NH2、C5H 11 or benzyl.

[0021] The present invention also provides the adsorption of Fe 3+ The resin material adsorbs Fe 3+ Application in.

[0022] The present invention provides a method for adsorbing Fe 3+ The preparation method of the resin material comprises: mixing polyamide-amine modified silica or a derivative of polyamide-amine modified silica, a carboxylic acid containing a phosphorus-oxygen double bond, a solvent and a nucleophilic reagent, and performing an amidation reaction to obtain Fe adsorbent. 3+The raw materials of the dendritic polymer polyamide-amine modified silica or its derivatives are easily available, which can reduce costs. At the same time, the dendritic polymer polyamide-amine modified silica or its derivatives have dendritic amino groups, which can react with the carboxylic acid groups in the carboxylic acid containing phosphorus and oxygen double bonds to obtain multiple active sites that bind to iron, thereby improving the adsorption of Fe 3+ The adsorption performance of the resin material on iron. The experimental results show that the adsorption of Fe 3+ The adsorption capacity of the resin material is 20 mg / g. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 The adsorption Fe provided by the present invention 3+ Schematic diagram of the structure of the resin material;

[0024] In the figure, R1 and R2 are independently phenyl, cyclohexyl, C8H 17 , C4H9, 2-methoxyphenyl, methyl, ethoxy, C6H 13 、OC6H 13 , ethyl or methoxy; R3 is H, ethyl, C4H9, CH(CH3)2C2H5, phenyl, OC6H 13 、C6H 13 、C8H 17 、C9H 19 、C 10 H 21 、C 12 H 25 、(CH2)2Ph、six-membered heterocyclic ring、(CH2)5NH2、C5H 11 or benzyl;

[0025] Figure 2 The adsorbed Fe prepared in Example 1 3+ Schematic diagram of the structure of the resin material;

[0026] Figure 3 is the hydrogen spectrum of the carboxylic acid containing a phosphorus-oxygen double bond in Example 1;

[0027] Figure 4 is the infrared spectrum of the carboxylic acid containing a phosphorus-oxygen double bond in Example 1;

[0028] Figure 5 This is an electron microscope image of the polyamidoamine-modified silica in Example 1;

[0029] Figure 6 The adsorbed Fe prepared in Example 1 3+ Electron microscope image of the resin material;

[0030] Figure 7The adsorbed Fe prepared in Example 1 3+ Static adsorption results of resin materials at different acidities;

[0031] Figure 8 The adsorbed Fe prepared in Example 1 3+ Selective adsorption diagram of resin materials;

[0032] Figure 9 The adsorbed Fe prepared in Examples 1 to 3 3+ Adsorption capacity curves of the resin material and the TRU resin of Comparative Example 1;

[0033] Figure 10 The adsorbed Fe prepared in Example 4 3+ Adsorption capacity curve of resin material. DETAILED DESCRIPTION

[0034] The present invention provides a method for adsorbing Fe 3+ A method for preparing a resin material, comprising:

[0035] The polyamide-amine modified silica or a derivative of the polyamide-amine modified silica, a carboxylic acid containing a phosphorus-oxygen double bond, a solvent and a nucleophilic reagent are mixed and subjected to an amidation reaction to obtain an adsorbent of Fe 3+ resin material.

[0036] The present invention has no particular limitation on the sources of the raw materials, and the raw materials may be prepared using commercially available products or well-known preparation methods known to those skilled in the art.

[0037] In the present invention, the solvent is preferably an ionic liquid; the ionic liquid is preferably 1-butyl-3-methylimidazolium bromide. The present invention has no particular limitation on the amount of the solvent, as long as it can dissolve the raw materials.

[0038] In the present invention, the preparation method of the polyamide-amine modified silica preferably comprises the following steps:

[0039] (1) Mixing silica, an organic solvent and a silane coupling agent, and performing a modification to obtain modified silica;

[0040] (2) The modified silica obtained in step (1) is subjected to secondary modification using polyamide-amine to obtain polyamide-amine-modified silica.

[0041] In the present invention, silicon dioxide, an organic solvent and a silane coupling agent are preferably mixed and modified once to obtain modified silicon dioxide.

[0042] The present invention has no particular limitation on the operation of mixing the silicon dioxide, organic solvent and silane coupling agent and performing a modification, and any operation well known to those skilled in the art can be used.

[0043] After obtaining the modified silica, the present invention preferably uses polyamide-amine to perform secondary modification on the modified silica to obtain polyamide-amine modified silica.

[0044] The present invention has no particular limitation on the operation of secondary modification of modified silica using polyamide-amine, and operations well known to those skilled in the art may be used.

[0045] The present invention uses readily available dendritic polymer polyamide-amine-modified silica or its derivatives to reduce costs, solving the problem of high preparation costs of the extractant CMPO. Furthermore, the silica contains dendritic amino groups that can react with carboxylic acids to obtain dendritic active sites, increasing the number of active sites and thereby improving the material's adsorption performance for iron. Furthermore, the silica can exist stably in nuclear wastewater.

[0046] In one embodiment of the present invention, the preparation method of the polyamide-amine modified silica comprises the following steps:

[0047] (1) Weigh 10 g of 100-200 μm silica particles, disperse them in 50 mL of anhydrous ethanol, transfer them to a 500 mL round-bottom flask, add 250 mL of anhydrous ethanol, and sonicate them for 30 min using an ultrasonic generator. Add 20 mL of 3-aminopropyltriethoxysilane (APTES) at the 20th minute of sonication, and continue until the end of sonication. Then, stir them with electromagnetic stirring for 15 h. The obtained product is washed with methanol in small amounts several times to obtain APTES-modified micron-sized silica particles.

[0048] (2) The APTES-modified micron-sized silica particles obtained in step (1) are placed in a 500 mL round-bottom flask, and a methyl acrylate / methanol solution with a volume ratio of 1:5 is prepared. 400 mL of the methyl acrylate / methanol solution is added to the aforementioned round-bottom flask, and the suspension is ultrasonicated in a water bath at room temperature for 7 h. After ultrasonic treatment, it is filtered and washed with methanol. The product is then rotary evaporated to remove excess methyl acrylate / methanol attached to the surface of the particles to obtain an intermediate product; an ethylenediamine / methanol solution with a volume ratio of 1:1 is prepared, and 80 mL of the ethylenediamine / methanol solution is added to the aforementioned intermediate product. The product is ultrasonicated in a water bath at room temperature for 7 h. The product is washed with methanol in small amounts multiple times to obtain a first-generation product; this step (2) is repeated once to obtain a second-generation product; this step (2) is repeated twice to obtain a third-generation product.

[0049] In the present invention, the polyamide-amine modified silica derivative is preferably obtained by hydrogen substitution of terminal amino groups of polyamide-amine modified silica.

[0050] In the present invention, the terminal amino group hydrogen substitution is preferably a hydrogen substitution on the terminal amino group; the terminal amino group hydrogen substitution substituent is preferably ethyl, C4H9, CH(CH3)2C2H5, phenyl, OC6H 13 、C6H 13 、C8H 17 、C9H 19 、C 10 H 21 、C 12 H 25 、(CH2)2Ph、six-membered heterocyclic ring、(CH2)5NH2、C5H 11 or benzyl.

[0051] In the present invention, the structural formula of the six-membered heterocycle is preferably as shown in Formula III:

[0052] Formula III.

[0053] The present invention has no particular limitation on the operation of hydrogen substitution of the terminal amino groups of the polyamidoamine-modified silica, and the preparation can be carried out using operations well known to those skilled in the art.

[0054] In the present invention, the structural formula of the carboxylic acid containing a phosphorus-oxygen double bond is preferably as shown in Formula I:

[0055] Formula I.

[0056] In the present invention, R1 and R2 are independently preferably phenyl, cyclohexyl, C8H 17 , C4H9, 2-methoxyphenyl, methyl, ethoxy, C6H 13 、OC6H 13 , ethyl or methoxy, more preferably phenyl. The carboxylic acid containing a phosphorus oxygen double bond in the present invention is used to provide adsorption of Fe 3+ The active sites of the polyamide-amine modified silica or the derivative of the polyamide-amine modified silica can react with the amino groups in the polyamide-amine modified silica to generate active sites.

[0057] In one embodiment of the present invention, the carboxylic acid containing a phosphorus-oxygen double bond is 2,2-(diphenylphosphino)acetic acid, and its structural formula is shown in Formula V:

[0058] Formula V.

[0059] In the present invention, the method for preparing the carboxylic acid containing a phosphorus-oxygen double bond preferably comprises:

[0060] A phosphorus-oxygen-containing compound, a halogenated carboxylic acid, an organic solvent and an alkaline solution are mixed and subjected to a substitution reaction to obtain a carboxylic acid containing a phosphorus-oxygen double bond. The substitution reaction of the present invention is to replace the hydrogen at the phosphorus position in the phosphorus-oxygen-containing compound.

[0061] In the present invention, the structural formula of the phosphorus-oxygen-containing compound is preferably as shown in Formula IV:

[0062] Formula IV.

[0063] In the present invention, R1 and R2 are independently preferably phenyl, cyclohexyl, C8H 17 , C4H9, 2-methoxyphenyl, methyl, ethoxy, C6H 13 、OC6H 13 , ethyl or methoxy, more preferably phenyl.

[0064] In one embodiment of the present invention, the phosphorus oxide-containing compound is diphenylphosphine oxide.

[0065] In the present invention, the halogenated carboxylic acid is preferably a chlorocarboxylic acid, more preferably monochloroacetic acid.

[0066] In the present invention, the organic solvent is preferably dimethyl sulfoxide. In the present invention, the organic solvent is used to dissolve the raw materials.

[0067] In the present invention, the alkaline solution is preferably a strong alkaline solution, more preferably a potassium hydroxide solution. In the present invention, the alkaline solution is used to provide an alkaline environment.

[0068] In the present invention, the solvent of the alkaline solution is preferably water. The present invention has no particular limitation on the amount of water used, as long as it can dissolve the raw materials.

[0069] In the present invention, the molar ratio of the phosphorus-oxygen-containing compound to the halogenated carboxylic acid is preferably (10-12):(11-13), more preferably 11:12. The molar ratio of the solute to the halogenated carboxylic acid in the alkaline solution is preferably (4-6):(1-2), more preferably 5:2. The amount of the organic solvent used is not particularly limited, as long as it dissolves the raw materials. Limiting the ratio of the raw materials to the above range can improve the reaction rate and thus the yield.

[0070] In the present invention, the mixture of the phosphorus-oxygen-containing compound, the halogenated carboxylic acid, the organic solvent and the alkaline solution is preferably:

[0071] The phosphorus-oxygen-containing compound, halogenated carboxylic acid and organic solvent are mixed, and then an alkaline solution is added dropwise.

[0072] The present invention has no particular limitation on the operation of mixing the phosphorus-oxygen-containing compound, the halogenated carboxylic acid and the organic solvent, and the technical scheme for preparing the mixed material well known to those skilled in the art can be used.

[0073] The present invention has no particular limitation on the rate of the dripping, and the dripping operation well known to those skilled in the art can be used.

[0074] In the present invention, the substitution reaction temperature is preferably 50-60°C, more preferably 55°C; and the substitution reaction time is preferably 0.5-1.5 hours, more preferably 1 hour. Limiting the substitution reaction temperature and time within these ranges can increase the degree of substitution, thereby improving the yield.

[0075] After the substitution reaction is completed, the product obtained by the substitution reaction is preferably post-treated to obtain a carboxylic acid containing a phosphorus-oxygen double bond.

[0076] In the present invention, the post-treatment preferably includes dilution, acidification, extraction, drying, concentration and recrystallization in sequence. The post-treatment of the present invention can improve the purity of the carboxylic acid containing a phosphorus-oxygen double bond.

[0077] In the present invention, the diluent used for dilution is preferably water. The present invention has no particular limitation on the amount of water used, as long as the product is diluted.

[0078] In the present invention, the acidification is preferably carried out using dilute hydrochloric acid. The present invention has no particular limitation on the concentration and amount of the dilute hydrochloric acid, and the pH value of the solution can be adjusted to a range of 1 to 2.

[0079] In the present invention, the extraction agent used is preferably CHCl 3. The present invention has no special limitation on the amount of the extraction agent, which can be determined according to common sense.

[0080] In the present invention, the desiccant used for the drying is preferably MgSO 4 . The present invention has no particular limitation on the amount of the desiccant used, as long as it can remove moisture.

[0081] The present invention has no particular limitation on the concentration operation, and it can be determined based on common sense.

[0082] In the present invention, the solvent used for the recrystallization is preferably acetonitrile. The present invention has no particular limitation on the amount of acetonitrile used, as long as the product is completely dissolved.

[0083] In the present invention, the nucleophile is preferably triphenyl phosphite.

[0084] In one embodiment of the present invention, the molar ratio of the polyamidoamine-modified silica or its derivative to the carboxylic acid containing a phosphorus-oxygen double bond is preferably 1:(1.8-2.2), more preferably 1:2; and the molar ratio of the nucleophile to the polyamidoamine-modified silica or its derivative is preferably (0.8-1.2):(0.8-1.2), more preferably 1:1. In the present invention, the polyamidoamine-modified silica or its derivative contains a large number of amino groups. By controlling the molar ratio of the polyamidoamine-modified silica or its derivative to the carboxylic acid containing a phosphorus-oxygen double bond, the extent of the amidation reaction can be controlled.

[0085] The present invention has no particular limitation on the mixing operation of the polyamide-amine modified silica or the derivative of polyamide-amine modified silica, the carboxylic acid containing a phosphorus-oxygen double bond, the solvent and the nucleophilic reagent, and the technical scheme for preparing the mixed material well known to those skilled in the art can be adopted.

[0086] In the present invention, the temperature of the amidation reaction is preferably 100-120°C, more preferably 110°C; the time of the amidation reaction is preferably 30-50 minutes, more preferably 40 minutes. The present invention limits the temperature and time of the amidation reaction to the above ranges to increase the degree of amidation, thereby obtaining more active sites and further improving the adsorption of Fe 3+ The selective adsorption ability of the resin material.

[0087] In the present invention, the amidation reaction is preferably carried out under stirring conditions. The present invention has no particular limitation on the stirring operation, and any operation well known to those skilled in the art can be used.

[0088] After the amidation reaction is completed, the product obtained by the amidation reaction is preferably cooled, filtered and dried in sequence to obtain the adsorbed Fe 3+ resin material.

[0089] The present invention has no particular limitation on the cooling operation, and cooling to room temperature may be performed using an operation well known to those skilled in the art.

[0090] The present invention has no particular limitation on the filtering operation. The filtration operation well known to those skilled in the art can be used to remove the filtrate.

[0091] In the present invention, the drying is preferably carried out under vacuum conditions. The present invention uses drying to remove the solvent in the product. The present invention has no particular limitation on the specific operation of the drying, and the solvent can be removed.

[0092] In one embodiment of the present invention, the molar ratio of the polyamidoamine-modified silica or its derivative to the carboxylic acid containing a phosphorus-oxygen double bond is preferably 1:(3.6-4.4), more preferably 1:4; and the molar ratio of the nucleophile to the polyamidoamine-modified silica or its derivative is preferably (1.6-2.4):(0.8-1.2), more preferably 2:1. In the present invention, the polyamidoamine-modified silica or its derivative contains a large number of amino groups. By controlling the molar ratio of the polyamidoamine-modified silica or its derivative to the carboxylic acid containing a phosphorus-oxygen double bond, the extent of the amidation reaction can be controlled.

[0093] In the present invention, when the molar ratio of the polyamidoamine-modified silica or its derivative to the carboxylic acid containing a phosphorus-oxygen double bond is 1:(3.6-4.4), the carboxylic acid containing a phosphorus-oxygen double bond and the nucleophilic reagent are preferably added in two separate batches. The amounts of the carboxylic acid containing a phosphorus-oxygen double bond added in the two separate batches are preferably the same; and the amounts of the nucleophilic reagent added in the two separate batches are preferably the same. Adding the carboxylic acid containing a phosphorus-oxygen double bond in two separate batches allows for a more complete amidation reaction.

[0094] In the present invention, when the carboxylic acid containing a phosphorus-oxygen double bond and the nucleophilic agent are added twice, it is preferred that the first amidation reaction be carried out after the first addition of the carboxylic acid containing a phosphorus-oxygen double bond and the nucleophilic agent, and then the second amidation reaction be carried out after the second addition of the carboxylic acid containing a phosphorus-oxygen double bond and the nucleophilic agent.

[0095] In the present invention, the operations of the first amidation reaction and the second amidation reaction are independently preferably the same as those of the aforementioned amidation reaction, and are not described in detail herein.

[0096] In one embodiment of the present invention, the molar ratio of the polyamidoamine-modified silica or its derivative to the carboxylic acid containing a phosphorus-oxygen double bond is preferably 1:(5.4-6.6), more preferably 1:6; and the molar ratio of the nucleophile to the polyamidoamine-modified silica or its derivative is preferably (2.4-3.6):(0.8-1.2), more preferably 3:1. In the present invention, the polyamidoamine-modified silica or its derivative contains a large number of amino groups. By controlling the molar ratio of the polyamidoamine-modified silica or its derivative to the carboxylic acid containing a phosphorus-oxygen double bond, the extent of the amidation reaction can be controlled.

[0097] In the present invention, when the molar ratio of the polyamidoamine-modified silica or its derivative to the carboxylic acid containing a phosphorus-oxygen double bond is 1:(5.4-6.6), the carboxylic acid containing a phosphorus-oxygen double bond and the nucleophilic reagent are preferably added in three separate batches. The amounts of the carboxylic acid containing a phosphorus-oxygen double bond added in these three batches are preferably the same; and the amounts of the nucleophilic reagent added in these three batches are preferably the same. Adding the carboxylic acid containing a phosphorus-oxygen double bond in these three batches allows for a more complete amidation reaction.

[0098] In the present invention, when the carboxylic acid containing a phosphorus-oxygen double bond and the nucleophilic reagent are added three times, preferably, the first amidation reaction is carried out after the first addition of the carboxylic acid containing a phosphorus-oxygen double bond and the nucleophilic reagent, and then the carboxylic acid containing a phosphorus-oxygen double bond and the nucleophilic reagent are added for the second time to carry out the second amidation reaction, and then the carboxylic acid containing a phosphorus-oxygen double bond and the nucleophilic reagent are added for the third time to carry out the third amidation reaction.

[0099] In the present invention, the operations of the first amidation reaction, the second amidation reaction and the third amidation reaction are independently preferably the same as the operations of the aforementioned amidation reaction, and are not described in detail herein.

[0100] In one embodiment of the present invention, the molar ratio of the polyamidoamine-modified silica or its derivative to the carboxylic acid containing a phosphorus-oxygen double bond is preferably 1:(7.2-8.8), more preferably 1:8; and the molar ratio of the nucleophile to the polyamidoamine-modified silica or its derivative is preferably (3.2-4.8):(0.8-1.2), more preferably 4:1. In the present invention, the polyamidoamine-modified silica or its derivative contains a large number of amino groups. By controlling the molar ratio of the polyamidoamine-modified silica or its derivative to the carboxylic acid containing a phosphorus-oxygen double bond, the extent of the amidation reaction can be controlled.

[0101] In the present invention, when the molar ratio of the polyamidoamine-modified silica or its derivative to the carboxylic acid containing a phosphorus-oxygen double bond is 1:(7.2-8.8), the carboxylic acid containing a phosphorus-oxygen double bond and the nucleophilic reagent are preferably added in four separate batches. The amounts of the carboxylic acid containing a phosphorus-oxygen double bond added in the four separate batches are preferably the same, and the amounts of the nucleophilic reagent added in the four separate batches are preferably the same. Adding the carboxylic acid containing a phosphorus-oxygen double bond in the present invention in four separate batches allows for a more complete amidation reaction.

[0102] In the present invention, when the carboxylic acid containing a phosphorus-oxygen double bond and the nucleophilic reagent are added four times, preferably, the first amidation reaction is carried out after the first addition of the carboxylic acid containing a phosphorus-oxygen double bond and the nucleophilic reagent, and then the carboxylic acid containing a phosphorus-oxygen double bond and the nucleophilic reagent are added for the second time to carry out the second amidation reaction, followed by the third addition of the carboxylic acid containing a phosphorus-oxygen double bond and the nucleophilic reagent to carry out the third amidation reaction, and then the fourth addition of the carboxylic acid containing a phosphorus-oxygen double bond and the nucleophilic reagent to carry out the fourth amidation reaction.

[0103] In the present invention, the operations of the first amidation reaction, the second amidation reaction, the third amidation reaction and the fourth amidation reaction are independently preferably the same as the operations of the aforementioned amidation reaction, and are not described in detail herein.

[0104] In the present invention, the adsorbed Fe 3+ The resin material is the first generation of Fe adsorption 3+ Resin material, the first generation adsorption of Fe 3+ The resin material contains unreacted amino groups, which can continue to react with carboxyl groups to obtain n-generation products. The present invention uses multiple amidation reactions to further improve the adsorption of Fe 3+ The number of active sites in the resin material increases, thereby increasing the adsorption of Fe 3+ The adsorption properties of resin materials.

[0105] The raw materials of the dendritic polymer polyamide-amine modified silica or its derivatives of the present invention are easily available, which can reduce costs. At the same time, the dendritic polymer polyamide-amine modified silica or its derivatives have dendritic amino groups that can react with carboxylic acids to obtain multiple active sites that bind to trivalent iron ions, thereby improving the material's adsorption performance for iron.

[0106] The current price of TRU resin is high. The present invention uses basic conventional reagents to synthesize it, which is low in cost. 3+ It brings great convenience to the separation and analysis work.

[0107] The present invention also provides the adsorbed Fe prepared by the preparation method described in the above technical solution 3+ resin material.

[0108] In the present invention, the adsorption of Fe 3+ The resin material preferably includes silicon dioxide and active groups grafted onto the surface of the silicon dioxide.

[0109] In the present invention, the structural formula of the active group is preferably as shown in Formula II:

[0110] Formula II.

[0111] In the present invention, R1 and R2 are independently preferably phenyl, cyclohexyl, C8H 17 , C4H9, 2-methoxyphenyl, methyl, ethoxy, C6H 13 、OC6H 13 , ethyl or methoxy, more preferably phenyl.

[0112] In the present invention, the R3 is preferably H, ethyl, C4H9, CH(CH3)2C2H5, phenyl, OC6H 13 、C6H 13 、C8H 17 、C9H 19 、C 10 H 21 、C 12 H 25 、(CH2)2Ph、six-membered heterocyclic ring、(CH2)5NH2、C5H 11 or benzyl, more preferably H.

[0113] In the present invention, the adsorption of Fe 3+ The resin material is preferably a spherical material; the adsorption of Fe 3+ The particle size of the resin material is preferably 50 to 500 μm.

[0114] The adsorption Fe provided by the present invention 3+ The resin material has excellent adsorption performance for Fe 3+ The adsorption capacity is high, ≥20mg / g, which is much higher than the adsorption capacity of existing materials, and the cost is less than one-tenth of it.

[0115] The adsorption Fe provided by the present invention 3+ The structural diagram of the resin material is as follows Figure 1 As shown, R1 and R2 are independently phenyl, cyclohexyl, C8H 17 , C4H9, 2-methoxyphenyl, methyl, ethoxy, C6H 13 、OC6H 13 , ethyl or methoxy; R3 is H, ethyl, C4H9, CH(CH3)2C2H5, phenyl, OC6H 13 、C6H 13 、C8H 17 、C9H 19 、C 10 H 21 、C 12 H 25 、(CH2)2Ph、six-membered heterocyclic ring、(CH2)5NH2、C5H 11 or benzyl.

[0116] from Figure 1It can be seen that the adsorption of Fe 3+ The resin material contains multiple active sites.

[0117] The present invention also provides the adsorption of Fe 3+ The resin material adsorbs Fe 3+ Application in.

[0118] The present invention is to adsorb Fe 3+ The resin material adsorbs Fe 3+ There is no particular limitation on the operations used, and any operation well known to those skilled in the art may be used.

[0119] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions of the present invention. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0120] Example 1

[0121] Adsorption of Fe 3+ The preparation method of the resin material comprises the following steps:

[0122] (1) Weigh 10 g of 100-200 μm silica particles, disperse them in 50 mL of anhydrous ethanol, transfer them to a 500 mL round-bottom flask, add 250 mL of anhydrous ethanol, and sonicate them with an ultrasonic generator for 30 min. At the 20th minute of sonication, add 20 mL of APTES and continue sonicating until the end of the process. Then, stir the mixture with electromagnetic stirring for 15 h. The resulting product is washed with methanol in small amounts several times to obtain APTES-modified micron-sized silica particles.

[0123] (2) The APTES-modified micron-sized silica particles obtained in step (1) are placed in a 500 mL round-bottom flask, and a methyl acrylate / methanol solution with a volume ratio of 1:5 is prepared. 400 mL of the methyl acrylate / methanol solution is added to the aforementioned round-bottom flask, and the suspension is ultrasonicated in a water bath at room temperature for 7 hours. After ultrasonic treatment, it is filtered and washed with methanol. The product is then rotary evaporated to remove excess methyl acrylate / methanol attached to the surface of the particles to obtain an intermediate product; an ethylenediamine / methanol solution with a volume ratio of 1:1 is prepared, and 80 mL of the ethylenediamine / methanol solution is added to the aforementioned intermediate product. The product is ultrasonicated in a water bath at room temperature for 7 hours. The product is washed with methanol in small amounts multiple times to obtain polyamide-amine modified silica;

[0124] (3) 22 mmol of diphenylphosphinoyl and 24 mmol of ClCH2COOH were added to 10 mL of DMSO. KOH solution (60 mmol of KOH dissolved in 4 mL of water) was added dropwise to the mixture while cooling in a water bath. The mixture turned brown and was heated at 55°C for 1 h to undergo a substitution reaction. The mixture was then diluted with 40 mL of H2O and acidified to pH 1 with 20 mL of dilute hydrochloric acid (the volume ratio of concentrated hydrochloric acid to water was 1:5). The mixture was extracted with CHCl3 and dried over MgSO4. The mixture was then concentrated to obtain an oily product. The product was recrystallized from acetonitrile to obtain 4.10 g of a white powder, which was a carboxylic acid containing a phosphorus-oxygen double bond, 2,2-(diphenylphosphino)acetic acid, with a yield of 65.3%. The structural formula is shown in Formula V:

[0125] Formula V;

[0126] (4) 1.04 g (2 mmol) of the polyamidoamine-modified silica obtained in step (2) and 1.04 g (4 mmol) of the carboxylic acid containing a phosphorus-oxygen double bond obtained in step (3) were stirred at 110° C. for 40 min in the presence of 1.31 g (6 mmol) of 1-butyl-3-methylimidazolium bromide and 0.62 g (2 mmol) of triphenyl phosphite for amidation reaction, and then cooled to room temperature and filtered. The solvent was then removed in vacuo to obtain a white solid, which was Fe adsorbed. 3+ The resin material is marked as G1-1.

[0127] From the perspective of the synthesis steps, the silica is first modified to obtain polyamide-amine modified silica; then diphenylphosphine is reacted with monochloroacetic acid to generate a carboxylic acid containing a phosphorus-oxygen double bond; then the polyamide-amine modified silica reacts with the carboxylic acid containing a phosphorus-oxygen double bond to obtain Fe adsorbent. 3+ resin material.

[0128] Example 1 prepared adsorbed Fe 3+ The structural diagram of the resin material is as follows Figure 2 shown.

[0129] from Figure 2 It can be seen that multiple active sites are grafted onto the silica surface.

[0130] The carboxylic acid containing phosphorus oxygen double bond prepared in Example 1 was subjected to hydrogen spectrum and infrared detection, and the results were as follows: Figure 3 and 4 shown; among them, Figure 3 is the hydrogen spectrum of the carboxylic acid containing a phosphorus-oxygen double bond in Example 1; Figure 4 This is the infrared spectrum of the carboxylic acid containing a phosphorus-oxygen double bond in Example 1.

[0131] Carboxylic acids containing phosphorus-oxygen double bonds 1 H NMR (400 MHz, Chloroform-d): δ=10.92 (s, 1H), 7.77-7.70 (m, 4H), 7.48-7.31 (m, 6H), 3.51 (d, J=14.1 Hz, 2H).

[0132] from Figure 3 It can be seen that the present invention successfully synthesizes carboxylic acid containing a phosphorus-oxygen double bond with high purity.

[0133] The peak positions of the carboxylic acid containing a phosphorus-oxygen double bond prepared in Example 1 are as follows: 3300 cm -1 The left and right are the vibration peaks of hydrogen on the carboxyl group; 3125~3030cm -1 =CH stretching vibration on the benzene ring, multiple peaks; 1700cm -1 The left and right sides are carboxyl-C=O stretching vibrations, which have high polarity and strong absorption peaks; 1600~1450cm -1 It is the C=C stretching vibration on the benzene ring, 2 to 4 peaks with different intensities; 1300~1100cm -1 It is the characteristic peak of carboxyl-CO; 1200~1000cm -1 It is the P=O absorption peak, which is weak but clearly visible.

[0134] from Figure 3 and 4 It can be seen that the present invention successfully synthesized 2,2-(diphenylphosphino)acetic acid.

[0135] In Example 1, the polyamidoamine-modified silica and the adsorbed Fe 3+ The electron microscope image of the resin material is as follows Figure 5 and 6 As shown; Figure 5 This is an electron microscope image of the polyamidoamine-modified silica in Example 1; Figure 6 The adsorbed Fe prepared in Example 1 3+ SEM image of the resin material.

[0136] from Figures 5 and 6 It can be seen that the surface of polyamidoamine-modified silica is smoother, while the adsorption of Fe 3+ The surface of the resin material is obviously rougher and has some protrusions in some parts, which can also help explain the adsorption of Fe 3+ The successful synthesis of resin materials.

[0137] Example 2

[0138] The adsorbed Fe prepared in Example 1 3+The resin material G1-1 and 1.04 g (4 mmol) of the carboxylic acid containing a phosphorus-oxygen double bond obtained in step (3) of Example 1 were stirred at 110° C. for 40 min in the presence of 1.31 g (6 mmol) of 1-butyl-3-methylimidazolium bromide and 0.62 g (2 mmol) of triphenyl phosphite for amidation reaction, and then cooled to room temperature and filtered. The solvent was then removed in vacuo to obtain Fe adsorbent. 3+ The resin material is marked as G1-2.

[0139] Example 3

[0140] The adsorbed Fe prepared in Example 2 3+ The resin material G1-2 was reacted with 1.04 g (4 mmol) of the carboxylic acid containing a phosphorus-oxygen double bond obtained in step (3) of Example 1, in the presence of 1.31 g (6 mmol) of 1-butyl-3-methylimidazolium bromide and 0.62 g (2 mmol) of triphenyl phosphite, under stirring at 110° C. for 40 min for amidation reaction, and then cooled to room temperature and filtered. The solvent was then removed in vacuo to obtain Fe adsorbent. 3+ The resin material is marked as G1-3.

[0141] Example 4

[0142] The adsorbed Fe prepared in Example 3 3+ The resin material G1-3 was reacted with 1.04 g (4 mmol) of the carboxylic acid containing a phosphorus-oxygen double bond obtained in step (3) of Example 1, in the presence of 1.31 g (6 mmol) of 1-butyl-3-methylimidazolium bromide and 0.62 g (2 mmol) of triphenyl phosphite, under stirring at 110° C. for 40 min for amidation reaction, and then cooled to room temperature and filtered. The solvent was then removed in vacuo to obtain Fe adsorbent. 3+ The resin material is marked as G1-4.

[0143] Comparative Example 1

[0144] Commercially available TRU resin

[0145] The adsorbed Fe prepared in Example 1 3+ The acidity effect test of the resin material was carried out with a solid-liquid ratio of 1g / L. The adsorption of Fe at different acidities was 3+ The static adsorption results of the resin material are as follows Figure 7 shown.

[0146] from Figure 7 It can be seen that with the increase of nitric acid concentration, the adsorption of Fe 3+ Resin material for Fe 3+ The adsorption effect is getting better and better, indicating that the adsorption of Fe 3+The resin material can be used under strong acid conditions.

[0147] The adsorbed Fe prepared in Example 1 3+ The resin material is selectively adsorbed and tested. The test method is: prepare three groups of samples containing interfering ions (Ni, Co, Cu, Zn, Eu, Sr, Cr, Y, Al) and Fe 3+ The mixed solution, solid-liquid ratio (adsorbed Fe 3+ The mass ratio of the resin material to the volume of the prepared mixed solution was 1g / L, and the static adsorption experiments were carried out under 8mol / L HNO3 conditions; among them, Fe 3+ The concentration of each interfering ion is 2ppm. The concentration of each interfering ion in the first group is 200ppm (i.e. 200:2), the concentration of each interfering ion in the second group is 20ppm (i.e. 20:2), and the concentration of each interfering ion in the third group is 2ppm (i.e. 2:2). The results are as follows Figure 8 shown.

[0148] from Figure 8 It can be seen that the adsorption of Fe 3+ Resin material for Fe 3+ It has good selectivity and can detect Fe even when the interfering ions are 100 times more abundant. 3+ It has excellent selectivity and the adsorption rate is close to 100%, which can achieve the removal of Fe 3+ Efficient separation.

[0149] The adsorbed Fe prepared in Examples 1 to 4 3+ The adsorption capacity of the resin material and the TRU of comparative example 1 was tested by static experiment at different initial concentrations of Fe(III). The adsorption capacity curve is shown in FIG. Figure 9 and Figure 10 shown.

[0150] Figure 9 The adsorbed Fe prepared in Examples 1 to 3 3+ Adsorption capacity curves of the resin material and comparative example 1 TRU in 8M nitric acid; Figure 10 The adsorbed Fe prepared in Example 4 3+ Adsorption capacity curves of the resin materials in 8M and 10M nitric acid, respectively.

[0151] from Figure 9 It can be seen that the adsorbed Fe 3+ The resin material has excellent adsorption performance. With the increase of the final reaction generation, the adsorption of Fe 3+ The adsorption capacity of the resin material is significantly improved.

[0152] The maximum adsorption capacity of the TRU resin in Comparative Example 1 is 5 mg / g; the adsorbed Fe 3+ The maximum adsorption capacity of the resin material is 5 mg / g; the adsorption Fe prepared in Example 2 3+ The maximum adsorption capacity of the resin material is 13 mg / g; the adsorbed Fe prepared in Example 3 3+ The maximum adsorption capacity of the resin material is 20 mg / g.

[0153] from Figure 10 It can be seen that the adsorbed Fe 3+ The resin material has excellent adsorption properties.

[0154] Example 4: Adsorbed Fe 3+ The adsorption capacity of the resin material for Fe(III) in 10 M nitric acid system reaches 16 mg / g.

[0155] In summary, the adsorption of Fe 3+ The adsorption capacity of the resin material is 20 mg / g, and there is still a lot of room for improvement; with the increase of the final reaction generation, the adsorption of Fe 3+ The adsorption capacity of the resin material is significantly improved, indicating that if the adsorption of Fe 3+ The resin material is optimized to produce more active end groups, so there will be more active sites for Fe 3+ The greater the adsorption capacity.

[0156] It can be seen from the above examples that the preparation method provided by the present invention reduces the cost, and the adsorbed Fe 3+ The resin material has excellent selective adsorption capacity for iron.

[0157] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A resin material adsorbs Fe 3+ The application is characterized in that The method for preparing the resin material comprises: The polyamidoamine-modified silica, a carboxylic acid containing a phosphorus-oxygen double bond, a solvent and a nucleophilic reagent are mixed to carry out an amidation reaction to obtain a resin material; The structural formula of the carboxylic acid containing a phosphorus-oxygen double bond is shown in Formula I: Formula I; In formula I, R1 and R2 are independently phenyl, cyclohexyl, C8H 17 , C4H9, 2-methoxyphenyl, methyl, ethoxy, C6H 13 、OC6H 13 , ethyl or methoxy.

2. The use according to claim 1, characterized in that The molar ratio of the polyamide-amine modified silica to the carboxylic acid containing a phosphorus-oxygen double bond is 1:(1.8-2.2).

3. The use according to claim 1, characterized in that The molar ratio of the polyamide-amine modified silica to the carboxylic acid containing a phosphorus-oxygen double bond is 1:(3.6-4.4).

4. The use according to claim 1, characterized in that The molar ratio of the polyamide-amine modified silica to the carboxylic acid containing a phosphorus-oxygen double bond is 1:(5.4-6.6).

5. The use according to claim 1, characterized in that The molar ratio of the polyamide-amine modified silica to the carboxylic acid containing a phosphorus-oxygen double bond is 1:(7.2-8.8).

6. The use according to claim 1, characterized in that The temperature of the amidation reaction is 100-120° C., and the time of the amidation reaction is 30-50 minutes.

7. The use according to claim 1, characterized in that The resin material includes silicon dioxide and active groups grafted onto the surface of the silicon dioxide; The structural formula of the active group is shown in Formula II: Formula II; In formula II, R1 and R2 are independently phenyl, cyclohexyl, C8H 17 , C4H9, 2-methoxyphenyl, methyl, ethoxy, C6H 13 、OC6H 13 , ethyl or methoxy; R3 is H, ethyl, C4H9, CH(CH3)2C2H5, phenyl, OC6H 13 、C6H 13 、C8H 17 、C9H 19 、C 10 H 21 、C 12 H 25 、(CH2)2Ph、six-membered heterocyclic ring、(CH2)5NH2、C5H 11 or benzyl.

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