A functionalized silica adsorbent material, its preparation method and use
Functionalized silica adsorbent materials were prepared by coupling silane coupling agents and pyrophosphoryl groups onto porous silica, which solved the problem of low adsorption capacity of existing resins for zirconium and achieved a highly efficient scandium-zirconium separation effect.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- GUANGXI UNIV
- Filing Date
- 2024-12-16
- Publication Date
- 2026-06-19
AI Technical Summary
Existing resins have low adsorption capacity for zirconium, making it difficult to meet the requirements for effective separation of scandium and zirconium in the preparation of high-purity scandium oxide.
Functionalized silica adsorbents were prepared by coupling silane coupling agents and pyrophosphoryl groups onto porous silica, resulting in a high specific surface area and high selectivity, thereby achieving high adsorption capacity and high adsorption rate of zirconium.
Functionalized silica adsorbents exhibit significantly improved adsorption capacity for zirconium, reaching 127–130 mg/L, and demonstrate excellent scandium-zirconium separation with low scandium loss and a high scandium-zirconium separation coefficient.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of adsorption materials for metal separation, and particularly to a functionalized silica adsorption material, its preparation method, and its application. Background Technology
[0002] Scandium is a rare earth element, and its compounds are mainly used in alloys, new electric light source materials, laser materials, and electronic materials, among other fields, holding significant strategic importance. With the development of modern technology, the purity requirements for scandium products are constantly increasing. According to the national standard for scandium oxide product grades and chemical composition (GB / T 13219-2018), the ZrO2 content in 99.99% Sc2O3 of product grade Sc2O3-5N5 cannot exceed 0.0005%. In the scandium purification process, due to the similar properties of scandium and zirconium, the separation of zirconium is a major challenge in the preparation of high-purity scandium oxide. Currently, methods used for scandium purification include adsorption.
[0003] Existing technologies disclose a resin preparation method and its application. This resin uses di(methacryloyloxyethyl) hydrogen phosphate as a monomer, dimethyl sulfoxide as a solvent, ethylene glycol dimethacrylate as a crosslinking agent, and azobisisobutyl cyanide as an initiator. It is prepared by crosslinking polymerization and loading the resin onto the micropores or surface of a support, achieving effective separation of scandium and zirconium. The resin is regenerable and reusable. However, this resin has a low adsorption capacity for zirconium, only 0.3 mmol / g (27.3 mg / g). Summary of the Invention
[0004] In view of this, the purpose of this invention is to provide a functionalized silica adsorbent material, its preparation method, and its application. The functionalized silica adsorbent material provided by this invention has a high adsorption capacity for zirconium.
[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:
[0006] This invention provides a functionalized silica adsorbent material comprising porous silica, wherein pyrophosphoryl groups are coupled to the porous silica via a silane coupling agent.
[0007] The average pore volume of the porous silica is 0.3–2 cm³. 3 / g, average pore size of 1–20 nm, specific surface area of 100–1000 cm³ 2 / g.
[0008] This invention also provides a method for preparing the functionalized silica adsorbent material described in the above technical solution, comprising the following steps:
[0009] Porous silica, silane coupling agent, pyrophosphoryl chloride and organic solvent are mixed and coupled to obtain the functionalized silica adsorbent material.
[0010] Preferably, the silane coupling agent contains an amino group, and the silane coupling agent includes one or more of 3-aminopropyltriethoxysilane and 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane; the mass ratio of the porous silica to the silane coupling agent is 0.5:0.45-0.6.
[0011] Preferably, the mass ratio of porous silica to pyrophosphoryl chloride is 0.5:1 to 1.8.
[0012] Preferably, the organic solvent includes one or more of toluene, acetone, chloroform, dichloromethane, and petroleum ether; the ratio of porous silica to organic solvent is 0.5g:40-100mL.
[0013] Preferably, the mixing of porous silica, silane coupling agent, pyrophosphoryl chloride and organic solvent includes the following steps: dispersing porous silica in an organic solvent to form a porous silica dispersion; and sequentially adding silane coupling agent and pyrophosphoryl chloride to the porous silica dispersion.
[0014] Preferably, the coupling reaction is carried out at a temperature of 80–90°C for 8–16 hours in a closed container.
[0015] Preferably, after the coupling reaction, the method further includes: performing solid-liquid separation on the obtained coupling reaction solution, washing and drying the obtained solid sequentially to obtain the functionalized silica adsorbent material; the washing reagent includes ethanol, the drying is vacuum drying, and the vacuum drying temperature is 50-80℃ for 12-24 hours.
[0016] The present invention also provides the application of the functionalized silica adsorbent material described in the above technical solution or the functionalized silica adsorbent material prepared by the preparation method described in the above technical solution in metal separation.
[0017] Preferably, it includes the following steps:
[0018] The functionalized silica adsorbent material is placed in a solution containing metal elements for adsorption.
[0019] The ratio of the functionalized silica adsorbent material to the solution containing metal elements is 1-5 mg: 1 mL.
[0020] The metallic elements include zirconium and / or scandium.
[0021] This invention provides a functionalized silica adsorbent material.
[0022] The functionalized silica adsorbent of the present invention uses porous silica as a carrier, which gives the functionalized silica adsorbent a large specific surface area. At the same time, pyrophosphoryl groups are coupled to porous silica through a silane coupling agent. The P=O and PO bonds in the pyrophosphoryl groups will preferentially form coordination bonds with zirconium, thus exhibiting high selectivity, high adsorption capacity and high adsorption rate for zirconium, resulting in a high adsorption capacity for zirconium in the functionalized silica adsorbent.
[0023] Data from the embodiments show that the functionalized silica adsorbent material provided by the present invention has an adsorption capacity of 127-130 mg / L for zirconium.
[0024] This invention also provides a method for preparing the functionalized silica adsorbent material described in the above technical solution. This invention uses porous silica as a carrier, pyrophosphoryl chloride (P2O3Cl4) as a modifier, and a silane coupling agent as a coupling agent to synthesize the functionalized silica adsorbent material, denoted as DPO / SiO2-N, in a one-pot, one-step process. The preparation method provided by this invention is simple to operate. Detailed Implementation
[0025] This invention provides a functionalized silica adsorbent material comprising porous silica, wherein pyrophosphoryl groups are coupled to the porous silica via a silane coupling agent.
[0026] The average pore volume of the porous silica is 0.3–2 cm³. 3 / g, average pore size of 1–20 nm, specific surface area of 100–1000 cm³ 2 / g.
[0027] The functionalized silica adsorbent material provided by this invention comprises porous silica, wherein the average pore volume of the porous silica is 0.3–2 cm³. 3 / g, average pore size of 1–20 nm, specific surface area of 100–1000 cm³ 2 / g. In this invention, the use of porous silica can increase the specific surface area of the functionalized silica adsorbent material, thereby improving the connection between the silane coupling agent and the pyrophosphoryl group, and thus increasing the adsorption capacity of the functionalized silica adsorbent material.
[0028] The functionalized silica adsorbent material provided by this invention comprises pyrophosphoryl groups coupled to the porous silica via a silane coupling agent. In this invention, the preferred type of silane coupling agent will be described in the subsequent preparation method section and will not be repeated here.
[0029] This invention also provides a method for preparing the functionalized silica adsorbent material described in the above technical solution, comprising the following steps:
[0030] Porous silica, silane coupling agent, pyrophosphoryl chloride and organic solvent are mixed and coupled to obtain the functionalized silica adsorbent material.
[0031] Unless otherwise specified, the raw materials used in this invention are preferably commercially available products.
[0032] In this invention, the silane coupling agent preferably contains an amino group. Further preferably, the silane coupling agent comprises one or more of 3-aminopropyltriethoxysilane and 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane. In this invention, the mass ratio of the porous silica to the silane coupling agent is preferably 0.5:0.45 to 0.6, specifically preferably 0.5:0.45, 0.5:0.5, 0.5:0.55, or 0.5:0.6. In this invention, the silane coupling agent enables the connection between porous silica and pyrophosphoryl groups. Furthermore, in this invention, the amino group in the silane coupling agent exhibits higher reactivity than the silanol group, allowing for better grafting of the pyrophosphoryl groups. Controlling the mass ratio of porous silica to silane coupling agent to 0.5:0.45–0.6 increases the specific surface area and functional group content. Excessive use of the silane coupling agent can lead to pore blockage in the porous silica, reducing the specific surface area and the content of usable functional groups.
[0033] In this invention, the preferred mass ratio of porous silica to pyrophosphoryl chloride is 0.5:1 to 1.8, specifically preferably 0.5:1, 0.5:1.1, 0.5:1.2, 0.5:1.3, 0.5:1.4, 0.5:1.5, 0.5:1.6, 0.5:1.7, or 0.5:1.8. Controlling the mass ratio of porous silica to pyrophosphoryl chloride to 0.5:1 to 1.8 ensures a higher content of pyrophosphoryl groups in the functionalized silica adsorbent material, better utilizing the selectivity and adsorption properties of pyrophosphoryl groups for zirconium, and ultimately improving the adsorption capacity of the functionalized silica adsorbent material for zirconium and the scandium-zirconium separation coefficient.
[0034] In this invention, the organic solvent preferably includes one or more of toluene, acetone, chloroform, dichloromethane, and petroleum ether. In this invention, the preferred ratio of porous silica to organic solvent is 0.5g:40-100mL, specifically 0.5g:40mL, 0.5g:50mL, 0.5g:60mL, 0.5g:70mL, 0.5g:80mL, 0.5g:90mL, or 0.5g:100mL. In this invention, the organic solvent enables uniform dispersion of the porous silica, thereby promoting its contact and connection with the silane coupling agent and pyrophosphoryl chloride.
[0035] In this invention, the mixing of porous silica, silane coupling agent, pyrophosphoryl chloride, and organic solvent preferably includes the following steps: dispersing porous silica in an organic solvent to form a porous silica dispersion; and sequentially adding the silane coupling agent and pyrophosphoryl chloride to the porous silica dispersion. In this invention, the dispersion temperature is preferably room temperature, and the dispersion is preferably carried out under stirring conditions. The stirring time is preferably 10–30 min, specifically 10 min, 15 min, 20 min, 25 min, or 30 min. In this invention, after the pyrophosphoryl chloride is added, it is preferable to further stir at room temperature for 10–30 min, specifically 10 min, 15 min, 20 min, 25 min, or 30 min.
[0036] In this invention, the temperature of the coupling reaction is preferably 80–90°C, specifically 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C, or 90°C; the time is preferably 8–16 hours, specifically 8 hours, 12 hours, or 16 hours; the coupling reaction is preferably carried out in a closed container. In this invention, the coupling reaction is preferably carried out under static conditions.
[0037] Following the coupling reaction, the present invention preferably further includes: solid-liquid separation of the obtained coupling reaction solution, and sequential washing and drying of the obtained solid to obtain the functionalized silica adsorbent material. In this invention, the washing reagent preferably includes ethanol, and the ethanol is preferably anhydrous ethanol. In this invention, the drying is preferably vacuum drying, the vacuum drying temperature is preferably 50–80°C, specifically 50°C, 60°C, 70°C, or 80°C, and the time is preferably 12–24 hours, specifically 12 hours, 18 hours, or 24 hours.
[0038] The present invention also provides the application of the functionalized silica adsorbent material described in the above technical solution or the functionalized silica adsorbent material prepared by the preparation method described in the above technical solution in metal separation.
[0039] In this invention, the application preferably includes the following steps:
[0040] The functionalized silica adsorbent material is placed in a solution containing metal elements for adsorption.
[0041] In this invention, the preferred ratio of the functionalized silica adsorbent material to the solution containing metal elements is 1-5 mg:1 mL, specifically 1 mg:1 mL, 2 mg:1 mL, 3 mg:1 mL, 4 mg:1 mL or 5 mg:1 mL.
[0042] In this invention, the metallic element includes zirconium and / or scandium.
[0043] In this invention, the adsorption temperature is preferably room temperature. In this invention, the adsorption is preferably carried out under oscillation conditions, and the oscillation rate is preferably 100–300 rpm, specifically 100 rpm, 200 rpm, or 300 rpm.
[0044] The functionalized silica adsorbent material, its preparation method, and its application provided by the present invention will be described in detail below with reference to the embodiments. However, these should not be construed as limiting the scope of protection of the present invention.
[0045] Example 1
[0046] 1) Porous silica (average pore volume 1.12 cm³) 3 / g, with an average pore size of 6.51nm and a specific surface area of 756cm². 2 Mix 0.5 g of 3-aminopropyltriethoxysilane and 1.8 g of pyrophosphoryl chloride with toluene at a solid-liquid ratio of 0.5 g: 40 mL, stir at room temperature for 15 min, then add 0.45 g of 3-aminopropyltriethoxysilane and 1.8 g of pyrophosphoryl chloride sequentially, and stir at room temperature for 15 min to obtain a suspension.
[0047] 2) Transfer the suspension from step 1) to a sealed pressure-resistant container, heat it at 80°C for 12 hours, and then perform solid-liquid separation to obtain the solid product.
[0048] 3) The solid product obtained in step 2) was washed several times with anhydrous ethanol and dried under vacuum at 50°C for 24 hours to obtain the functionalized silica adsorbent material, denoted as DPO / SiO2-N.
[0049] Example 2
[0050] 1) Porous silica (average pore volume 1.7 cm³) 3 / g, with an average pore size of 7.20nm and a specific surface area of 824cm². 2 Mix 0.5 g of 3-aminopropyltrimethoxysilane and 1 g of pyrophosphoryl chloride with acetone at a solid-liquid ratio of 0.5 g: 100 mL, stir at room temperature for 30 min, then add 0.6 g of 3-aminopropyltrimethoxysilane and 1 g of pyrophosphoryl chloride in sequence, and stir at room temperature for 30 min to obtain a suspension.
[0051] 2) Transfer the suspension from step 1) to a sealed pressure-resistant container, heat it at 90°C for 8 hours, and then perform solid-liquid separation to obtain a solid product.
[0052] 3) The solid product obtained in step 2) was washed several times with anhydrous ethanol and dried under vacuum at 80°C for 12 hours to obtain the functionalized silica adsorbent material, denoted as DPO / SiO2-N.
[0053] Example 3
[0054] 1) Porous silica (average pore volume 0.7 cm³) 3 / g, with an average pore size of 4.57nm and a specific surface area of 456cm². 2 Mix 0.5 g of 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane and 1.3 g of pyrophosphoryl chloride at a solid-liquid ratio of 0.5 g: 60 mL, stir at room temperature for 20 min, and then add 0.45 g of 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane and 1.3 g of pyrophosphoryl chloride in sequence. Stir at room temperature for 20 min to obtain a suspension.
[0055] 2) Transfer the suspension from step 1) to a sealed pressure-resistant container, heat it at 80°C for 16 hours, and then perform solid-liquid separation to obtain the solid product.
[0056] 3) The solid product obtained in step 2) was washed several times with anhydrous ethanol and dried under vacuum at 80°C for 12 hours to obtain the functionalized silica adsorbent material, denoted as DPO / SiO2-N.
[0057] Comparative Example 1
[0058] 1) Porous silica (average pore volume 1.12 cm³) 3 / g, with an average pore size of 6.51nm and a specific surface area of 756cm². 2 Mix 0.5 g of 3-aminopropylbis(trimethylsiloxy)methylsilane and 1.8 g of pyrophosphoryl chloride at a solid-liquid ratio of 0.5 g: 40 mL, stir at room temperature for 30 min, then add 0.95 g of 3-aminopropylbis(trimethylsiloxy)methylsilane and 1.8 g of pyrophosphoryl chloride, stir at room temperature for 20 min to obtain a suspension.
[0059] 2) Transfer the suspension from step 1) to a sealed pressure-resistant container, heat it at 80°C for 1 hour, and then perform solid-liquid separation to obtain a solid product.
[0060] 3) The solid product obtained in step 2) was washed several times with anhydrous ethanol and dried under vacuum at 50°C for 24 h to obtain DPO / SiO2-N.
[0061] Comparative Example 2
[0062] 1) Porous silica (average pore volume 1.12 cm³) 3 / g, with an average pore size of 6.51nm and a specific surface area of 756cm². 2 (g) was mixed with toluene at a solid-liquid ratio of 0.5g:40mL and stirred at room temperature for 15min. Then, 1.8g of pyrophosphoryl chloride was added and reacted at room temperature for 48h. After the reaction was completed, solid-liquid separation was performed to obtain the solid product.
[0063] 2) The solid product obtained in step 2) was washed several times with anhydrous ethanol and dried under vacuum at 50°C for 24 hours to obtain DPO / SiO2.
[0064] Comparative Example 3
[0065] The difference from Example 1 is that the mass of 3-aminopropyltriethoxysilane is 0.9g, otherwise it is the same as Example 1.
[0066] Comparative Example 4
[0067] The difference from Example 1 is that the mass of 3-aminopropyltriethoxysilane is 0.3g, otherwise it is the same as Example 1.
[0068] Comparative Example 5
[0069] The difference from Example 1 is that the mass of pyrophosphoryl chloride is 0.5g, otherwise it is the same as Example 1.
[0070] Comparative Example 6
[0071] The difference from Example 1 is that the mass of pyrophosphoryl chloride is 2g, otherwise it is the same as Example 1.
[0072] Performance testing
[0073] 1. The adsorption capacity test for zirconium is performed as follows:
[0074] In a solution with a nitric acid concentration of 6 mol / L and a zirconium concentration of 400 μg / mL, an adsorbent (the material obtained in the examples and comparative examples) was added at a solid-liquid ratio of 10–40 mg / 10 mL. The solution was shaken for 12 h at room temperature and a shaking speed of 200 rpm. The concentration of ions after adsorption was measured by ICP, and the adsorption capacity of the adsorbent for zirconium was calculated. The results are shown in Table 1.
[0075] 2. The specific process for separating scandium and zirconium is as follows:
[0076] In a solution with a nitric acid concentration of 1–6 mol / L, a zirconium concentration of 1 mmol / L, and a scandium concentration of 1 mmol / L, an adsorbent (the material obtained in the examples and comparative examples) was added at a solid-liquid ratio of 10–40 mg / 10 mL. The solution was shaken for 12 h at room temperature and a shaking speed of 200 rpm. The concentration of ions after adsorption was measured by ICP, and the adsorption capacity of the adsorbent for zirconium was calculated. The results are shown in Table 1.
[0077] The zirconium removal rate, scandium recovery rate, and scandium-zirconium separation coefficient are shown in Table 1.
[0078] Table 1. Performance test results of materials obtained in the examples and comparative examples.
[0079]
[0080] As can be seen from Table 1, the functionalized silica adsorbent material provided by the present invention has a high adsorption capacity for zirconium and a good separation effect for scandium and zirconium, with a low scandium loss rate and a large scandium-zirconium separation coefficient.
[0081] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A method for preparing a functionalized silica adsorbent material, characterized in that, The functionalized silica adsorbent material includes porous silica and pyrophosphoryl groups coupled to the porous silica by a silane coupling agent. The average pore volume of the porous silica is 0.3~2 cm³. 3 / g, average pore size of 1~20nm, specific surface area of 100~1000cm³ 2 / g; The preparation method of the functionalized silica adsorbent material includes the following steps: Porous silica, silane coupling agent, pyrophosphoryl chloride and organic solvent are mixed and coupled to obtain the functionalized silica adsorbent material. The mass ratio of the porous silica to the silane coupling agent is 0.5:0.45~0.6; The mass ratio of the porous silica to pyrophosphoryl chloride is 0.5:1~1.8; The silane coupling agent contains an amino group, and the silane coupling agent includes one or more of 3-aminopropyltriethoxysilane, 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane and 3-aminopropylbis(trimethylsiloxy)methylsilane.
2. The preparation method according to claim 1, characterized in that, The organic solvent includes one or more of toluene, acetone, chloroform, dichloromethane, and petroleum ether; the ratio of porous silica to organic solvent is 0.5g:40~100mL.
3. The preparation method according to claim 1, characterized in that, The process of mixing porous silica, silane coupling agent, pyrophosphoryl chloride and organic solvent includes the following steps: dispersing porous silica in an organic solvent to form a porous silica dispersion; and sequentially adding silane coupling agent and pyrophosphoryl chloride to the porous silica dispersion.
4. The preparation method according to claim 1, characterized in that, The coupling reaction is carried out at a temperature of 80-90°C for 8-16 hours in a closed container.
5. The preparation method according to claim 1 or 4, characterized in that, The coupling reaction further includes: solid-liquid separation of the obtained coupling reaction solution, washing and drying the obtained solid sequentially to obtain the functionalized silica adsorbent material; the washing reagent includes ethanol, the drying is vacuum drying, the vacuum drying temperature is 50~80℃, and the time is 12~24h.
6. The functionalized silica adsorbent material prepared by the preparation method according to any one of claims 1 to 5.
7. The application of the functionalized silica adsorbent material according to claim 6 in metal separation.
8. The application according to claim 7, characterized in that, Includes the following steps: The functionalized silica adsorbent material is placed in a solution containing metal elements for adsorption. The ratio of the functionalized silica adsorbent material to the solution containing metal elements is 1~5 mg: 1 mL; The metallic elements include zirconium and / or scandium.