Phosphorus-containing amino acid extractant modified silicon ball and preparation method and application thereof

Abstract

The invention relates to a phosphorus-containing amino acid extractant modified silicon ball as well as a preparation method and application thereof. The preparation method comprises the following steps: (1) reacting a phosphorus-containing amino acid compound as shown in a formula I with a silane coupling agent to obtain a coupling extractant, wherein one end, far away from a silane part, of the silane coupling agent is covalently connected to an N atom of the phosphorus-containing amino acid compound as shown in the formula I; and (2) reacting the coupling extraction agent with the silicon balls to obtain modified silicon balls, wherein the silane part of the silane coupling agent is connected to the silicon balls. The modified silicon ball can be used for extracting and separating yttrium, has the advantages of being large in adsorption capacity, high in selectivity and simple in preparation method, can be widely used for separating and preparing high-purity yttrium, and has good application prospects. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the technical field of yttrium extraction, and relates to a phosphorus-containing amino acid extractant modified silicon ball, a preparation method and application thereof. Background Art

[0002] Yttrium has a wide range of uses. Yttrium is often used as an additive in the smelting of steel and non-ferrous alloys, which can enhance the oxidation resistance and ductility of these alloys, and improve the conductivity and mechanical strength. High-yttrium structural alloys containing 90% yttrium can be used in aviation and other occasions requiring low density and high melting point. In recent years, high-purity yttrium has been used in laser materials, fluorescent powders for color TVs, microwave technology, and acoustic energy conversion technologies. In addition, in recent years, high-purity yttrium has also been used in high-temperature resistant spray materials, diluents for nuclear reactor fuels, permanent magnet material additives, and as getters in the electronics industry.

[0003] Yttrium and heavy rare earth elements constitute the yttrium group elements and are difficult to separate. Traditionally, yttrium separation mainly uses cyclopentane acid as an extractant for separation. However, with the improvement of the catalytic cracking process in the petroleum industry, the output of cyclopentane acid as a by-product is getting smaller and smaller, and during the separation process, cyclopentane acid must be used at a higher pH value to extract rare earths. Cyclopentane acid has a high solubility in water and is also prone to environmental pollution. After separation with cyclopentane acid, the separation coefficient of yttrium and light rare earth is also very low, resulting in subsequent separation is still very difficult.

[0004] At present, the extraction and separation of yttrium mainly adopts the liquid phase extraction system, and there is little in-depth research on the solid phase extraction system for extracting and separating yttrium. The solid phase extraction system produces less waste and is easy to separate solid and liquid. Therefore, it is of great significance to develop a solid phase extraction system and its preparation method that can selectively adsorb and separate yttrium. Summary of the invention

[0005] The present invention provides a modified silicon ball and a preparation method and application thereof. The modified silicon ball of the present invention can be used for extracting and separating yttrium, has the advantages of large adsorption capacity, strong selectivity and simple preparation method, can be widely used for separating and preparing high-purity yttrium, and has good application prospects.

[0006] In a first aspect, the present invention provides a method for preparing modified silicon spheres, the method comprising the following steps:

[0007] (1) reacting a phosphorus-containing amino acid compound of Formula I with a silane coupling agent to obtain a coupled extractant, wherein one end of the silane coupling agent away from the silane portion is covalently linked to the N atom of the phosphorus-containing amino acid compound of Formula I;

[0008]

[0009] in,

[0010] R 1 and R2 Each independently selected from C 1 -C 14 Alkyl, C 6 -C 10 Aryl, C 1 -C 4 Alkyl C 6 -C 10 Aryl and C 6 -C 10 Aryl C 1 -C 4 Alkyl, preferably selected from C 1 -C 8 Alkyl, phenyl, C 1 -C 4 Alkylphenyl and phenyl C 1 -C 4 alkyl;

[0011] R 3 Selected from hydrogen, C 1 -C 6 Alkyl, C 6 -C 12 Aryl, C 1 -C 4 Alkyl C 6 -C 10 Aryl and C 6 -C 10 Aryl C 1 -C 4 alkyl;

[0012] Z is C 1 -C 12 Alkylene, preferably C 1 -C 4 Alkylene;

[0013] R 4 and R 5 are each independently selected from hydrogen, C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 12 Aryl, C 1 -C 4 Alkyl C 6 -C 10 Aryl and C 6 -C 10 Aryl C 1 -C 4 Alkyl, carboxyl C 1 -C 4 alkyl;

[0014] or R4 and R 5 Together with the carbon atom to which it is attached, it forms C 3 -C 10 Cycloalkyl, especially C 5 -C 8 Cycloalkyl;

[0015] (2) reacting a coupling extractant with silica spheres to obtain modified silica spheres, wherein the silane portion of the silane coupling agent is connected to the silica spheres.

[0016] The method for preparing the modified silicon sphere of the present invention grafts the phosphorus-containing amino acid compound of formula I onto the surface of the silicon sphere through a silane coupling agent. The modified silicon sphere of the present invention has the advantages of large adsorption capacity, strong selectivity and simple preparation method, can be widely used for separation and preparation of high-purity yttrium, and has good application prospects.

[0017] The present invention is described in further detail below.

[0018] Phosphorus-containing amino acid compounds

[0019] In some embodiments, the phosphorus-containing amino acid compound of Formula I is a compound of the following general formula II:

[0020]

[0021] Among them, R 1 , R 2 , R 3 , R 4 and R 5 The definition of is the same as in Formula I.

[0022] In some embodiments, in the general formula I and II, R 1 and R 2 The same or different. In addition, it is preferred that R 1 and R 2 The same, more preferably the same C 1 -C 8 Alkyl, phenyl, C 1 -C 4 Alkylphenyl and phenyl C 1 -C 4 alkyl.

[0023] In some embodiments, R 3 For hydrogen, C 1 -C 4 Alkyl or C 6 -C 10 Aryl, preferably hydrogen, C 1 -C 2 Alkyl, phenyl, benzyl, tolyl, ethylphenyl, xylyl.

[0024] In some embodiments, R 4 is hydrogen, R 5 Selected from hydrogen, C 1 -C 6 Alkyl, C 5 -C 7 Cycloalkyl, C 6 -C 10 Aryl, C 1 -C 4 Alkyl C 6 -C 10 Aryl, C 6 -C 10 Aryl C 1 -C 4 Alkyl and carboxyl C 1 -C 4 Alkyl, preferably hydrogen, C 1 -C 4 Alkyl, C 5 -C 7 Cycloalkyl, phenyl, benzyl, tolyl, ethylphenyl, xylyl, carboxyl C 1 -C 4 Alkyl; more preferably hydrogen, C 1 -C 2 Alkyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, benzyl, tolyl, ethylphenyl, xylyl, carboxyl C 1 -C 4 alkyl.

[0025] In particular, the phosphorus-containing amino acid compound is one or more selected from ((di(phenoxy)phosphoryl)methyl)glycine, ((di((benzyl)oxy)phosphoryl)methyl)glycine, ((di(phenoxy)phosphoryl)propyl)glycine, ((di(phenoxy)phosphoryl)methyl)phenylalanine, ((di((ethyl)oxy)phosphoryl)methyl)glycine, ((di((2-ethylhexyl)oxy)phosphoryl)(phenyl)methyl)glycine, ((di((2-ethylhexyl)oxy)phosphoryl)(phenyl)methyl)phenylalanine.

[0026] In the present invention, the phosphorus-containing amino acid compound of general formula I can also exist in the form of a salt. There is no particular limitation on the salt, as long as its cation has no adverse effect on the reaction. For example, it can be an ammonium salt, an alkali metal salt (such as a lithium salt, a sodium salt, a potassium salt) or an alkaline earth metal salt (such as a magnesium salt, a calcium salt), preferably an ammonium salt or a sodium salt.

[0027] The phosphorus-containing amino acid compound of formula I can be synthesized similarly to methods known in the prior art (eg, US4486359, CN115433842A, etc.) or the methods described below and in the examples.

[0028] For example, the phosphorus-containing amino acid compound of general formula I can be synthesized as follows, as shown in reaction formula 1:

[0029]

[0030] Wherein, compound II, compound III and compound IV are subjected to condensation reaction to obtain a phosphorus-containing amino acid compound of general formula I,

[0031] Among them, R 1 , R 2 , R 3 , R 4 , R 5 The definitions of and Z are the same as above.

[0032] The carbonyl compound III may be an aliphatic aldehyde (eg, formaldehyde, acetaldehyde, propionaldehyde, paraformaldehyde, etc.) or an aromatic aldehyde (eg, benzaldehyde, phenylacetaldehyde, etc.).

[0033] Compound II and Compound IV may be commercially available products or may be synthesized according to known methods in the prior art.

[0034] In some embodiments, compound II can be diphenyl phosphite, dimethyl phosphite, diethyl phosphite, di(n-propyl) phosphite, di(isopropyl) phosphite, di(2-ethylhexyl) phosphite, or di(2-methylhexyl) phosphite.

[0035] In some embodiments, compound IV can be any one or a combination of at least two selected from glycine, alanine, valine, leucine, isoleucine, tert-leucine, aspartic acid, phenylalanine, glutamic acid, and γ-aminobutyric acid, but is not limited thereto. The amino acids used here can be D-type, L-type, or a combination of the two.

[0036] The structures of some amino acids are shown in the following table:

[0037]

[0038] There is no particular limitation on the molar ratio of compounds II, III and IV, as long as the final target product can be obtained. Preferably, the molar ratio of compounds II, III and IV can be 1:0.1-5:0.1-5, such as 1:0.5-2:0.5-2, such as about 1:1:1.

[0039] The condensation reaction can be carried out in bulk or in an organic solvent. For example, the organic solvent can be any one selected from methanol, ethanol, acetonitrile, and tetrahydrofuran.

[0040] There is no particular limitation on the amount of the organic solvent, which can be appropriately selected by those skilled in the art. For example, the mass of the organic solvent can be 2-10 times the sum of the masses of compounds II, III and IV, such as 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times or 10 times, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0041] The condensation reaction can be carried out under stirring. Appropriate stirring is conducive to uniform mixing of the reactants and promotes the reaction. The stirring speed can be appropriately selected by those skilled in the art according to the reaction scale, reaction equipment, etc. For example, the stirring speed can be 100-500rpm, for example, 100rpm, 200rpm, 300rpm, 400rpm or 500rpm, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0042] The reaction time of the condensation reaction is not particularly limited, as long as the product can be obtained with an appropriate yield. The specific reaction time can be appropriately selected according to the reaction scale, reaction temperature, etc. For example, the reaction time can be 2-6 hours, for example, it can be 2 hours, 3 hours, 4 hours, 5 hours or 6 hours, but it is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0043] The reaction temperature of the condensation reaction is not particularly limited, as long as the reaction can occur to obtain the target product. For example, the reaction temperature can be 50-80°C, such as 50°C, 60°C, 70°C or 80°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0044] In addition, according to the structure of the phosphorus-containing amino acid compound of Formula I disclosed above, those skilled in the art can design a new synthesis route with reference to the synthesis methods known in the prior art. Therefore, the synthesis method of the phosphorus-containing amino acid compound of Formula I is not limited to the above method.

[0045] Silane coupling agent

[0046] In the present invention, the silane coupling agent acts as a connecting group, which is connected to the silicon sphere through the action of the silane group and the surface group of the silicon sphere on the one hand, and is covalently connected to the phosphorus-containing amino acid compound through the other end, thereby grafting the phosphorus-containing amino acid compound to the silicon sphere to obtain a modified silicon sphere.

[0047] The silane coupling agent can be any silane coupling agent that can achieve the above-mentioned purpose.

[0048] In some embodiments, the silane coupling agent has a functional group that can directly react with the amine group in the phosphorus-containing amino acid compound structure of Formula I. In this case, the silane coupling agent can be directly reacted with the phosphorus-containing amino acid compound of Formula I so that one end of the silane coupling agent is directly covalently linked to the amine group in the phosphorus-containing amino acid compound structure of Formula I.

[0049] In some embodiments, the silane coupling agent is represented by the following formula V:

[0050]

[0051] Among them, R 6 , R 7 and R 8 Each independently selected from C 1 -C 4 Alkyl and C 1 -C 4 Alkoxy, and at least one is an alkoxy; preferably each independently selected from C 1 -C 2 Alkyl and C 1 -C 2 Alkoxy groups, at least one of which is an alkoxy group;

[0052] R 9 is selected from halogen (especially Cl, bromine and iodine), epoxy (ie oxirane), epoxymethoxy (ie glycidyloxy) and isocyanate;

[0053] n is an integer from 1 to 8.

[0054] In some embodiments, the silane coupling agent is selected from epoxy silane, halogen silane, isocyanate silane, which respectively have epoxy groups, halogen groups and isocyanate groups that can react with amine groups. These silanes can be trialkoxy silanes, dialkoxy silanes or monoalkoxy silanes.

[0055] Epoxysilane refers to a silane coupling agent having at least one epoxy group in the molecule. For example, epoxysilane may be 3-(2,3-epoxypropyloxy)propyltrimethoxysilane (GPTS), 5,6-epoxyhexyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-(2,3-epoxypropyloxy)propyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-[(2,3)-epoxypropyloxy]propylmethyldimethoxysilane, 3-(2,3-epoxypropyloxy)propyltrimethoxysilane, (3-epoxypropyloxy)dimethylethoxysilane, etc., but is not limited thereto.

[0056] In the case of using epoxy silane, the epoxy group in the silane coupling agent can undergo an addition reaction with the amine group in the phosphorus-containing amino acid compound structure of Formula I to open the ring and allow one end of the silane coupling agent to be covalently connected to the amine group in the phosphorus-containing amino acid compound structure of Formula I.

[0057] Halogen silane refers to a silane coupling agent with at least one halogen group in the molecule. Halogen includes fluorine, chlorine, bromine and iodine. The halogen groups particularly common in silane coupling agents are chlorine and bromine. For example, the halogen silane can be 3-bromopropyltrimethoxysilane, 4-bromobutyltrimethoxysilane, 5-bromopentyltrimethoxysilane, 7-bromoheptyltrimethoxysilane, 3-chloroisopropyltrimethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, 3-chloropropyltrimethoxysilane (CPTS), 3-chloropropyltriethoxysilane, 3-iodopropyltrimethoxysilane, chloromethylmethyldiethoxysilane, 3-chloropropylmethyldiethoxysilane, 3-chloropropylmethyltrimethoxysilane, chloromethyldimethylethoxysilane, chloromethyldimethylmethoxysilane, but are not limited thereto.

[0058] In the case of using halogen silane, the silane coupling agent can be used as a halogenated hydrocarbon to undergo an amination reaction with the amine group in the phosphorus-containing amino acid compound structure of Formula I, thereby removing the halogen group and making one end of the silane coupling agent covalently connected to the amine group in the phosphorus-containing amino acid compound structure of Formula I. In order to promote the amination reaction, it can be carried out in the presence of an acid binding agent. Common acid binding agents are, for example, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), but are not limited thereto.

[0059] Isocyanate silane refers to a silane coupling agent with at least one isocyanate in the molecule. For example, the isocyanate silane can be 3-isocyanate propyl triethoxy silane, 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl methyl diethoxy silane, 3-isocyanate propyl methyl dimethoxy silane, etc., but is not limited thereto.

[0060] In the case of using isocyanate silane, the isocyanate group in the silane coupling agent can undergo a nucleophilic addition reaction with the amine group in the phosphorus-containing amino acid compound structure of Formula I to generate a urea group and covalently connect one end of the silane coupling agent to the amine group in the phosphorus-containing amino acid compound structure of Formula I.

[0061] The silane coupling agent can also be hydroxysilane, aldehyde silane, carboxyl silane, etc., and one end of the silane coupling agent is covalently connected to the amine group in the phosphorus-containing amino acid compound structure of formula I through the reaction of hydroxyl, aldehyde, carboxyl and other groups with amine groups.

[0062] In other embodiments, the silane coupling agent does not have a functional group that can directly react with the amine group in the structure of the phosphorus-containing amino acid compound of Formula I. In this case, one end of the silane coupling agent can be covalently connected to the amine group in the structure of the phosphorus-containing amino acid compound of Formula I through a connecting group by adding another compound that plays a connecting role as a connecting agent, or the silane coupling agent can be modified to have a functional group that can directly react with the amine group in the structure of the phosphorus-containing amino acid compound of Formula I.

[0063] Preparation of coupling extractant

[0064] The reaction of the phosphorus-containing amino acid compound of formula I with the silane coupling agent in step (1) is as described above, and the specific conditions can be appropriately selected according to the reaction type in combination with techniques known in the art.

[0065] The molar ratio of the phosphorus-containing amino acid compound of formula I to the silane coupling agent is not particularly limited, as long as the final target product can be obtained. Preferably, the molar ratio of the silane coupling agent to the phosphorus-containing amino acid compound of formula I can be 1:0.5-2, for example, 1:0.5, 1:0.75, 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0066] The reaction of the phosphorus-containing amino acid compound of formula I with the silane coupling agent can be carried out in bulk or in an organic solvent. For example, the organic solvent can be any one or more selected from methanol, ethanol, acetonitrile, and toluene.

[0067] There is no particular restriction on the amount of the organic solvent, which can be appropriately selected by those skilled in the art. For example, the mass of the organic solvent can be 2-5 times the sum of the phosphorus-containing amino acid compound of Formula I and the silane coupling agent, for example, 2 times, 3 times, 4 times, 5 times, but is not limited to the listed values, and other unlisted values ​​within the numerical range are equally applicable.

[0068] In some embodiments, the reaction can be carried out under stirring. Appropriate stirring is conducive to uniform mixing of the reactants and promotes the reaction. The stirring speed can be appropriately selected by those skilled in the art according to the reaction scale, reaction equipment, etc. For example, the stirring speed is 100-500rpm, for example, it can be 100rpm, 200rpm, 300rpm, 400rpm or 500rpm, but it is not limited to the listed values, and other values ​​not listed in the numerical range are also applicable.

[0069] The reaction time of the reaction is not particularly limited, as long as the product can be obtained with an appropriate yield. The specific reaction time can be appropriately selected according to the reaction scale, reaction temperature, etc. For example, the reaction time can be 24-72h, for example, 24h, 36h, 48h, 60h or 72h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0070] The reaction temperature of the reaction is not particularly limited, as long as the reaction can occur to obtain the target product. For example, the reaction temperature can be 60-90°C, such as 60°C, 65°C, 70°C, 75°C, 80°C, 85°C or 90°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0071] In some embodiments, the prepared coupling extractant is selected from the following compounds:

[0072]

[0073]

[0074] Among them, R 1 To R 5 and Z are the same as those in Formula I, R 6 To R 8 and n are defined as in Formula V.

[0075] In some embodiments, the prepared coupling extractant is selected from the following compounds:

[0076]

[0077]

[0078] Among them, R 1 To R 5 The definition is the same as in Formula II, R 6 To R 8 and n are defined as in Formula V.

[0079] Reaction of coupling extractant with silica spheres

[0080] In the reaction between the coupling extractant and the silica spheres in step (2), the silane groups of the coupling extractant will hydrolyze and react with the OH groups on the surface of the silica spheres, ultimately forming a covalent bond.

[0081] The silica spheres herein refer to silica microspheres. There are no particular restrictions on the silica spheres, as long as they are suitable for use as a chromatographic column substrate. For example, the silica spheres may have a particle size of 100-200 mesh, and / or 400-500 m 2 / g specific surface area, but not limited thereto.

[0082] In step (2), the mass ratio of the silicon sphere to the coupling extractant is not particularly limited, as long as an appropriate amount of the coupling extractant can be grafted onto the silicon sphere. For example, the mass ratio of the silicon sphere to the coupling extractant can be 1:1-2, such as 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0083] Step (2) can be carried out in an organic solvent. For example, the organic solvent can be any one or more selected from dimethylformamide, toluene, and dimethyl sulfoxide.

[0084] There is no particular limitation on the amount of the organic solvent, which can be appropriately selected by those skilled in the art. For example, the mass of the organic solvent can be 2-5 times the sum of the mass of the coupling extractant and the silica spheres, for example, 2 times, 3 times, 4 times, 5 times, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0085] The reaction can be carried out under stirring. Appropriate stirring is conducive to uniform mixing of the reactants and promotes the reaction. The stirring speed can be appropriately selected by those skilled in the art according to the reaction scale, reaction equipment, etc. For example, the stirring speed can be 100-500rpm, for example, 100rpm, 200rpm, 300rpm, 400rpm or 500rpm, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0086] The reaction time of the reaction is not particularly limited, as long as the product can be obtained with an appropriate yield. The specific reaction time can be appropriately selected according to the reaction scale, reaction temperature, etc. For example, the reaction time is 1-100h, such as 24-72h, for example, it can be 24h, 36h, 48h, 60h or 72h, but it is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0087] There is no particular restriction on the reaction temperature of the reaction, as long as the reaction can occur to obtain the target product. For example, the reaction temperature is 90-110°C, for example, it can be 90°C, 95°C, 100°C, 105°C or 110°C, but it is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable. The reaction temperature may affect the efficiency of the coupling extractant grafted to the surface of the silica sphere. When the reaction temperature is low, the coupling extractant is grafted to the surface of the silica sphere slowly, and it is impossible to obtain silica spheres with good performance in a short time, requiring too long a reaction time. When the reaction temperature is high, it will cause the reaction to be too intense, and it is not easy to control the progress of the reaction. Too long a reaction time can easily disconnect the phosphorus-containing amino acid extractant from the coupling agent, greatly reducing the performance of the silica sphere.

[0088] Step (2) may further include a purification step. The purification step may include saponifying the obtained reaction product, and then washing it with deionized water and ethanol respectively to obtain the modified silicon sphere. The saponification may be performed using an alkali, such as sodium hydroxide, sodium carbonate, etc.

[0089] In a second aspect, the present invention provides a modified silicon sphere, which is obtained by the preparation method described in the first aspect.

[0090] CN115433842A discloses that the phosphorus-containing amino acid compound of formula I has different extraction rates for yttrium and lanthanide elements, and the separation coefficient βLn / Y of lanthanide elements (Ln) and yttrium is large, so it can be used as an extractant to extract and separate yttrium. However, the phosphorus-containing amino acid compound of CN115433842A is mainly used for solvent extraction, and CN115433842A only generally mentions that the phosphorus-containing amino acid compound can be prepared into a solid phase extraction system, but no corresponding embodiments are provided. The preferred solid phase extraction system prepared by impregnation and in-situ polymerization does not involve changes in the molecular structure and spatial stereostructure of the extractant.

[0091] In the modified silicon sphere of the present invention, the amine group of the phosphorus-containing amino acid compound of formula I is covalently connected to the silane coupling agent and grafted into the silicon sphere, thereby changing the electron cloud distribution at the amine group and the corresponding spatial structure. At present, the mechanism of extracting and separating rare earth elements for the phosphorus-containing amino acid compound of formula I is still unknown. Therefore, it is impossible to infer whether the modified silicon sphere of the present invention can still extract rare earth elements, especially whether it still has different extraction rates for yttrium and lanthanide elements, so that it can be used as an extractant to extract and separate yttrium.

[0092] In addition, in the case of CN115433842A, the phosphorus-containing amino acid compound of formula I must have sufficiently low water solubility to be used in solvent extraction and solid phase extraction systems. For example, if the phosphorus-containing amino acid compound of formula I is water-soluble, it will directly dissolve in the rare earth element liquid and cannot produce an extraction effect, or if the phosphorus-containing amino acid compound of formula I can be used for extraction, but has high water solubility, resulting in excessive dissolution losses during the production process, and is therefore not suitable for production.

[0093] Surprisingly, the inventors have confirmed through experiments that the modified silicon spheres of the present invention can extract rare earth elements, have different extraction rates for yttrium and lanthanide elements, and can be used as an extractant to extract and separate yttrium. In addition, in the case of the modified silicon spheres of the present invention, there is no requirement for the water solubility of the phosphorus-containing amino acid compound of formula I, so that a wider range of phosphorus-containing amino acid compounds of formula I can be applied, reducing production costs and even improving extraction efficiency.

[0094] Therefore, in a third aspect, the present invention provides a use of the modified silicon spheres as described in the second aspect as a solid phase extractant for separating yttrium from lanthanide elements. In other words, the present invention provides the use of the modified silicon spheres as a solid phase extractant for preparing an extraction system for separating yttrium from lanthanide elements in a rare earth element solution.

[0095] In addition, during the experiment, it was found that the modified silica balls of the present invention as solid phase extractants have different extraction rates and distribution ratios for different lanthanide elements, and thus can be used to separate different lanthanide elements in rare earth element liquid by solid-liquid extraction. For example, it can be used to group lanthanide elements, such as light, medium, and heavy rare earth elements, or separate them into groups containing two or more (for example, two, three, four, etc.) similar lanthanide elements, or to separate a single lanthanide element.

[0096] Therefore, the present invention also provides the use of the modified silica spheres as a solid phase extractant for separating lanthanide elements. In other words, the present invention provides the use of the modified silica spheres as a solid phase extractant for preparing an extraction system for separating lanthanide elements.

[0097] In order to achieve the extraction, the rare earth element liquid can be contacted with the modified silicon spheres of the present invention, thereby achieving the separation.

[0098] Beneficial Effects

[0099] Compared with the prior art, the present invention has the following beneficial effects:

[0100] The present invention grafts a phosphorus-containing amino acid extractant onto the surface of a silicon ball in situ through a coupling agent to obtain a modified silicon ball having a selective adsorption effect on rare earth elements. The modified silicon ball of the present invention has a simple preparation method, is selective in a mixed rare earth solution, can be used to separate and prepare high-purity yttrium, and has good application prospects. Compared with the current separation technology, the modified silicon ball of the present invention has a stronger selective adsorption effect and has great potential in the preparation of high-purity yttrium.

[0101] the term

[0102] In the present invention, "separation of yttrium" refers to the extraction of yttrium (i.e., trivalent yttrium (III) or trivalent yttrium ion Y 3 + ) and other rare earth elements (i.e. lanthanide elements or trivalent lanthanide ions Ln 3+ ) separated.

[0103] In the present invention, rare earth elements refer to lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium and scandium, among which light rare earths refer to lanthanum, cerium, praseodymium and neodymium; medium and heavy rare earths refer to samarium, europium, gadolinium, terbium, dysprosium, holmium, europium, erbium, thulium, ytterbium, lutetium, yttrium and scandium.

[0104] The term C used in the present invention 1 -C 14 Alkyl refers to a straight or branched chain alkyl group containing 1 to 14 carbon atoms, such as a straight or branched chain alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 carbon atoms, including but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, n-pentyl, neopentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, etc. 1 ~C 8 Alkyl, C 1 ~C 4 The meanings of alkyl and the like are similar.

[0105] The term C used in the present invention 6 -C 10 Aryl refers to an aromatic group containing 6 to 12 carbon atoms in the ring, for example, an aromatic group having 6, 7, 8, 9, 10, 11 or 12 carbon atoms in the ring, including but not limited to phenyl and naphthyl.

[0106] The term C used in this invention 1 -C 4 Alkyl C 6 -C 10 Examples of the aryl group include tolyl, ethylphenyl, xylyl, mesityl and the like.

[0107] The term C used in this invention 6 -C 10 Aryl C 1 -C 4 The alkyl group includes, for example, benzyl, phenethyl and the like.

[0108] The term C used in this invention 3 -C 10 Cycloalkyl refers to a saturated cyclic alkyl group containing 3 to 10 carbon atoms, including but not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and the like.

[0109] Unless otherwise stated, the numerical values ​​in the present invention represent approximate measurements or limitations of the range of embodiments including slight deviations from given values ​​and having approximately the mentioned values ​​and having the mentioned exact values. Except for the last example described in detail, all numerical values ​​of parameters (e.g., quantities or conditions) in this application document (including the appended claims) should be understood as modified by the term "approximately" in all cases, regardless of whether "approximately" actually appears before the numerical value. "Approximately" means that the numerical value described allows for slight imprecision (some close to precision in the value; approximately or reasonably close to the value; approximately). If the imprecision provided by "approximately" is not understood in this ordinary sense in the art, the "approximately" used herein at least represents the changes that can be produced by ordinary methods of measuring and using these parameters. For example, "approximately" can include less than or equal to 15%, less than or equal to 10%, less than or equal to 5%, less than or equal to 4%, less than or equal to 3%, less than or equal to 2%, less than or equal to 1%, less than or equal to 0.5%, less than or equal to 0.1% of the change, and in some aspects, less than or equal to 0.01% of the change.

[0110] The present invention has been described above in detail, but the present invention is not limited to the above contents. BRIEF DESCRIPTION OF THE DRAWINGS

[0111] Figure 1 This is a scanning electron microscope image of the modified silicon sphere prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0112] To facilitate understanding of the present invention, the technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0113] Reagents and sources:

[0114] (1) Diphenyl phosphite and diethyl phosphite were purchased from Shanghai Laiyashi Chemical Co., Ltd.

[0115] (2) Paraformaldehyde, benzaldehyde, glycine, aspartic acid, phenylalanine, triethylamine, potassium hydroxide, methanol, toluene, xylene, heptane and other reagents were purchased from Aladdin Reagent Co., Ltd.

[0116] (3) 3-(2,3-Epoxypropyl)propyltrimethoxysilane (GPTS) and 3-chloropropyltrimethoxysilane (CPTS) were purchased from MacLean Co.

[0117] (4) Silica spheres were purchased from Qingdao Jiyida Silica Sphere Reagent Factory, with a particle size of 100-200 mesh and a specific surface area of ​​400-500 m 2 / g.

[0118] (5) The rare earth liquid was prepared in the laboratory.

[0119] (6) Other reagents (such as acids) were all commercially available analytical grade reagents.

[0120] The rare earth ion concentrations were measured using ICP-OES (instrument model: Optical-8000, manufacturer: Perkin Elmer).

[0121] Example 1

[0122] The preparation method of the modified silicon sphere is shown in the following reaction formula, but the reaction formula is only illustrative and is not intended to limit the present invention.

[0123]

[0124] The preparation method comprises the following steps:

[0125] (1) diphenyl phosphite, glycine and paraformaldehyde are mixed in tetrahydrofuran in the presence of triethylamine at a molar ratio of 1:1:1 (the mass ratio of the total drug to tetrahydrofuran is 1:4), stirred at 60° C. and 200 rpm for 4 h, and the product is separated and purified to obtain a phosphorus-containing amino acid extractant;

[0126] (2) The phosphorus-containing amino acid extractant obtained in step (1) is mixed with GPTS in methanol (the mass ratio of the total drug to methanol is 1:2), and the mixture is stirred at 65° C. and 200 rpm for 48 h to react. The product is spin-dried to obtain the methanol to obtain a coupled extractant.

[0127] (3) The coupling extractant obtained in step (2) is mixed with silica spheres in toluene (the mass ratio of the total drug to toluene is 1:3), stirred at 95°C at a speed of 200 rpm for 72 hours, filtered, saponified with 0.15 mol / L sodium carbonate solution for 3 hours, washed with deionized water until neutral, washed with anhydrous ethanol for 3 times, and vacuum dried at 60°C for 24 hours to obtain the modified silica spheres.

[0128] Modified silica ball: 1 H NMR (500 MHz, CDCl 3 )δ7.13-5.55(m,Ph-H), 4.00-1.80(m,Si-H,Si-OH), 1.37-0.61(m,CH,CH 2 ,CH 3 ).

[0129] Figure 1 Scanning electron microscopy images of the prepared modified silica spheres are shown.

[0130] Example 2

[0131] The only difference between this embodiment and embodiment 1 is that, except for stirring at 70° C. and 100 rpm for 3 h in step (1), the rest is the same as embodiment 1.

[0132] Modified silica ball: 1 H NMR (500 MHz, CDCl 3 )δ7.07-6.12(m,Ph-H), 4.23-1.74(m,Si-H,Si-OH), 1.41-0.76(m,CH,CH 2 ,CH 3 ).

[0133] Example 3

[0134] The preparation method of the modified silicon sphere is shown in the following reaction formula, but the reaction formula is only illustrative and is not intended to limit the present invention.

[0135]

[0136] The only difference between this embodiment and embodiment 1 is that, except for replacing "glycine" with "aspartic acid" in step (1), the rest is the same as embodiment 1.

[0137] Modified silica ball: 1 H NMR (500 MHz, CDCl 3 )δ6.84-5.50(m,Ph-H), 4.16-1.89(m,Si-H,Si-OH), 1.62-0.84(m,CH,CH 2 ,CH 3 ).

[0138] Example 4

[0139] The preparation method of the modified silicon sphere is shown in the following reaction formula, but the reaction formula is only illustrative and is not intended to limit the present invention.

[0140]

[0141] The only difference between this embodiment and embodiment 1 is that, except for replacing "GPTS" in step (2) with "CPTS", the rest is the same as embodiment 1.

[0142] Modified silica ball: 1 H NMR (500 MHz, CDCl 3 )δ6.78-6.94(m,Ph-H), 5.71-3.34(m,Si-H,Si-OH), 3.28(m,Cl-CH 2 -R), 1.79-0.81(m,CH,CH 2 ,CH 3 ).

[0143] Example 5

[0144] The preparation method of the modified silicon sphere is shown in the following reaction formula, but the reaction formula is only illustrative and is not intended to limit the present invention.

[0145]

[0146] The only difference between this embodiment and embodiment 1 is that, except that "diphenyl phosphite" in step (1) is replaced by "diethyl phosphite", the rest is the same as embodiment 1.

[0147] Modified silica ball: 1 H NMR (500 MHz, CDCl 3 )δ4.81-3.44(m,Si-H,Si-OH), 1.42-0.86(m,CH,CH 2 ,CH 3 ).

[0148] Example 6

[0149] The preparation method of the modified silicon sphere is shown in the following reaction formula, but the reaction formula is only illustrative and is not intended to limit the present invention.

[0150]

[0151] The only difference between this embodiment and embodiment 1 is that, except that "paraformaldehyde" in step (1) is replaced by "acetone", the rest is the same as embodiment 1.

[0152] Modified silica ball: 1 H NMR (500 MHz, CDCl 3 )δ7.07-6.79(m,Ph-H), 5.08-3.87(m,Si-H,Si-OH), 1.71-0.79(m,CH,CH 2,CH 3 ).

[0153] Example 7

[0154] The difference between this embodiment and embodiment 1 is that, except for the mixing in acetonitrile in step (2), the reaction is stirred at 80° C. and 200 rpm for 48 h, the rest is the same as embodiment 1.

[0155] Modified silica ball: 1 H NMR (500 MHz, CDCl 3 )δ7.11-6.91(m,Ph-H), 5.01-3.74(m,Si-H,Si-OH), 1.64-0.72(m,CH,CH 2 ,CH 3 ).

[0156] Example 8

[0157] The difference between this embodiment and embodiment 1 is that, except for the mixing in dimethylformamide in step (3), the reaction is stirred at 90° C. and 200 rpm for 72 h, the rest is the same as embodiment 1.

[0158] Modified silica ball: 1 H NMR (500 MHz, CDCl 3 )δ7.05-6.87(m,Ph-H), 4.87-3.56(m,Si-H,Si-OH), 1.74-0.86(m,CH,CH 2 ,CH 3 ).

[0159] Extraction Example

[0160] Weigh 0.1 g of the modified silicon spheres prepared in Examples 1-8 respectively and place them in conical flasks, add 5 mL of a rare earth element solution containing fifteen rare earth ions, namely La(III), Ce(III), Pr(III), Nd(III), Sm(III), Eu(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III), Lu(III) and Y(III), and the concentration of each rare earth element solution is 1 mmol / L and the pH value is 4 to the conical flask, and shake on a constant temperature shaker at an oscillation rate of 200 rpm for 24 hours for static adsorption; after sampling and filtering the solution in the conical flask, the ion concentration in the solution is detected by an ICP instrument.

[0161] The extraction rate E%, distribution ratio D and separation coefficient β between lanthanide elements (Ln) and yttrium are calculated as follows: Ln / Y :

[0162]

[0163]

[0164]

[0165] Among them, [M] (aq,init) and [M] (aq) are the initial concentration and equilibrium concentration of metal ions in the aqueous phase, D Ln is the distribution ratio of lanthanide elements, D Y is the distribution ratio of yttrium.

[0166] The separation coefficients and adsorption capacities of La(III), Ce(III), Pr(III), Nd(III), Sm(III), Eu(III), Gd(III), Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III), and Lu(III) for Y(III) are shown in Table 1.

[0167] Table 1

[0168]

[0169] From the data in Table 1, it can be seen that modified silicon spheres with selective adsorption are obtained in Examples 1-8. The preparation method of the modified silicon spheres is simple, can be used in industrial production, and are widely used for selective adsorption and separation of yttrium, and have good application prospects.

[0170] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing modified silicon spheres, the method comprising the following steps: (1) reacting a phosphorus-containing amino acid compound of Formula I with a silane coupling agent to obtain a coupled extractant, wherein one end of the silane coupling agent away from the silane portion is covalently linked to the N atom of the phosphorus-containing amino acid compound of Formula I; in, R1 and R2 are each independently selected from C1-C 14 Alkyl, C6-C 10 Aryl, C1-C4 alkyl, C6-C 10 Aryl and C6-C 10 Aryl C1-C4 alkyl, preferably selected from C1-C8 alkyl, phenyl, C1-C4 alkylphenyl and phenyl C1-C4 alkyl; R3 is selected from hydrogen, C1-C6 alkyl, C6-C 12 Aryl, C1-C4 alkyl, C6-C 10 Aryl and C6-C 10 Aryl C1-C4 alkyl; Z is C1-C 12 Alkylene, preferably C1-C4 alkylene; R4 and R5 are each independently selected from hydrogen, C1-C 10 Alkyl, C3-C 10 Cycloalkyl, C6-C 12 Aryl, C1-C4 alkyl, C6-C 10 Aryl and C6-C 10 Aryl C1-C4 alkyl, carboxyl C1-C4 alkyl; Or R4 and R5 and the carbon atom to which they are connected together form a C3-C 10 Cycloalkyl, especially C5-C8 cycloalkyl; (2) reacting a coupling extractant with silica spheres to obtain modified silica spheres, wherein the silane portion of the silane coupling agent is connected to the silica spheres.

2. The method according to claim 1, wherein: The phosphorus-containing amino acid compound of formula I is a compound of the following general formula II: Wherein, the definitions of R1, R2, R3, R4 and R5 are the same as those in Formula I.

3. The method according to claim 1 or 2, wherein: R1 and R2 are the same, preferably the same C1-C8 alkyl, phenyl, C1-C4 alkylphenyl and phenyl C1-C4 alkyl; and / or R3 is hydrogen, C1-C4 alkyl or C6-C 10 Aryl, preferably hydrogen, C1-C2 alkyl, phenyl, benzyl, tolyl, ethylphenyl, xylyl; and / or R4 is hydrogen, R5 is selected from hydrogen, C1-C6 alkyl, C5-C7 cycloalkyl, C6-C 10 Aryl, C1-C4 alkyl, C6-C 10 Aryl, C6-C 10 Aryl C1-C4 alkyl and carboxyl C1-C4 alkyl, preferably hydrogen, C1-C4 alkyl, C5-C7 cycloalkyl, phenyl, benzyl, tolyl, ethylphenyl, xylyl, carboxyl C1-C4 alkyl; more preferably hydrogen, C1-C2 alkyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, benzyl, tolyl, ethylphenyl, xylyl, carboxyl C1-C4 alkyl; In particular, the phosphorus-containing amino acid compound of formula I is one or more selected from ((di(phenoxy)phosphoryl)methyl)glycine, ((di((benzyl)oxy)phosphoryl)methyl)glycine, ((di(phenoxy)phosphoryl)propyl)glycine, ((di(phenoxy)phosphoryl)methyl)phenylalanine, ((di((ethyl)oxy)phosphoryl)methyl)glycine, ((di((2-ethylhexyl)oxy)phosphoryl)(phenyl)methyl)glycine, ((di((2-ethylhexyl)oxy)phosphoryl)(phenyl)methyl)phenylalanine.

4. The method according to claim 1, wherein: The silane coupling agent is shown in the following formula V: Wherein, R6, R7 and R8 are each independently selected from C1-C4 alkyl and C1-C4 alkoxy, and at least one is an alkoxy; preferably, they are each independently selected from C1-C2 alkyl and C1-C2 alkoxy, and at least one is an alkoxy; R9 is selected from halogen (especially Cl, bromine and iodine), epoxy, epoxymethoxy and isocyanate; n is an integer from 1 to 8; Alternatively, the silane coupling agent is selected from epoxy silane, halogen silane, isocyanate silane; In particular, the epoxysilane is selected from 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 5,6-epoxyhexyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-[(2,3)-epoxypropoxy]propylmethyldimethoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, (3-epoxypropoxypropyl)dimethylethoxysilane; The halogen silane is selected from 3-bromopropyltrimethoxysilane, 4-bromobutyltrimethoxysilane, 5-bromopentyltrimethoxysilane, 7-bromoheptyltrimethoxysilane, 3-chloroisopropyltrimethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-iodopropyltrimethoxysilane, chloromethylmethyldiethoxysilane, 3-chloropropylmethyldiethoxysilane, 3-chloropropylmethyltrimethoxysilane, chloromethyldimethylethoxysilane, chloromethyldimethylmethoxysilane; The isocyanate silane is selected from 3-isocyanate propyl triethoxy silane, 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl methyl diethoxy silane, and 3-isocyanate propyl methyl dimethoxy silane.

5. The method according to claim 1, wherein: In step (1), The molar ratio of the silane coupling agent to the phosphorus-containing amino acid compound of formula I is 1:0.5-2; and / or The reaction of the phosphorus-containing amino acid compound of formula I and the silane coupling agent is carried out in an organic solvent, in particular, the organic solvent is any one or more selected from methanol, ethanol, acetonitrile, and toluene; and / or the mass of the organic solvent is 2-5 times the sum of the phosphorus-containing amino acid compound of formula I and the silane coupling agent; and / or The reaction time is 24-72 hours; and / or The reaction temperature is 60-90°C.

6. The method according to claim 1, wherein: In step (2), The silicon spheres have a particle size of 100-200 mesh, and / or 400-500 m 2 / g specific surface area; and / or The mass ratio of silica spheres to coupling extractant is 1:1-2; and / or Step (2) is carried out in an organic solvent, in particular, the organic solvent is any one or more selected from dimethylformamide, toluene, and dimethyl sulfoxide; and / or the mass of the organic solvent is 2-5 times the sum of the mass of the coupling extractant and the silica spheres; and / or The reaction time is 1-100h, for example 24-72h; and / or The reaction temperature is 90-110°C.

7. The method according to claim 1, wherein: Step (2) also includes a purification step; in particular, the purification step includes saponifying the obtained reaction product and then washing it with deionized water and ethanol respectively to obtain the modified silicon spheres.

8. A modified silicon sphere obtained by the method according to any one of claims 1 to 7.

9. Use of the modified silica spheres according to claim 8 as a solid phase extractant for separating yttrium from lanthanide elements.

10. Use of the modified silica spheres according to claim 8 as a solid phase extractant for separating lanthanide elements.

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