Functionalized silicon dioxide adsorption material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of adsorption materials for metal separation, and provides a functionalized silicon dioxide adsorption material as well as a preparation method and application thereof. The functionalized silicon dioxide adsorption material comprises porous silicon dioxide and pyrophosphoryl which is coupled on the porous silicon dioxide through a silane coupling agent, the average pore volume of the porous silicon dioxide is 0.3-2 cm < 3 > / g, the average pore size is 1-20 nm, and the specific surface area is 100-1000 cm < 2 > / g. The functionalized silicon dioxide adsorption material disclosed by the invention takes porous silicon dioxide as a carrier, so that the functionalized silicon dioxide adsorption material has a relatively large specific surface area; meanwhile, the pyrophosphoryl is coupled to the porous silicon dioxide through the silane coupling agent, P = O and P-O bonds in the pyrophosphoryl preferentially form coordinate bonds with zirconium, so that the material has high selectivity, high adsorption capacity and high adsorption rate on zirconium, and the functionalized silicon dioxide adsorption material has high adsorption capacity on zirconium.

Description

Technical Field

[0001] The invention relates to the technical field of adsorption materials for metal separation, and in particular to a functionalized silicon dioxide adsorption material and a preparation method and application thereof. Background Art

[0002] Scandium is a rare earth element. Scandium and its compounds are mainly used in alloys, new electro-optical materials, laser materials, electronic materials and other fields, and have important strategic significance. With the development of modern science and technology, the purity requirements for scandium products are constantly increasing. According to the national standard for product grades and chemical composition of scandium oxide (GB / T 13219-2018), the content of ZrO2 in 99.99% Sc2O3 in the product grade Sc2O3-5N5 cannot exceed 0.0005%. In the process of purifying scandium, due to the similar properties of scandium and zirconium, the separation of zirconium is a major problem in the preparation of high-purity scandium oxide. At present, the methods used for purifying scandium include adsorption.

[0003] The related prior art discloses a method for preparing a resin and its application. The resin uses di(methacryloyloxyethyl) hydrogen phosphate as a monomer, dimethyl sulfoxide as a solvent, ethylene glycol dimethacrylate as a crosslinker, and azobisisobutylcyanide as an initiator. The resin is loaded into the micropores or on the surface of a support carrier by a crosslinking polymerization method to prepare a resin, which achieves effective separation of scandium and zirconium, and the resin can be regenerated and reused. However, the adsorption capacity of the resin for zirconium is low, only 0.3mmol / g (27.3mg / g). Summary of the invention

[0004] In view of this, the purpose of the present invention is to provide a functionalized silica adsorption material and a preparation method and application thereof. The functionalized silica adsorption material provided by the present invention has a high adsorption capacity for zirconium.

[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 functionalized silica adsorption material, comprising porous silica, and pyrophosphoryl groups coupled to the porous silica via a silane coupling agent;

[0007] The average pore volume of the porous silica is 0.3 to 2 cm 3 / g, average pore size of 1-20nm, specific surface area of ​​100-1000cm 2 / g.

[0008] The present invention also provides a method for preparing the functionalized silica adsorption material described in the above technical solution, comprising the following steps:

[0009] The porous silica, silane coupling agent, pyrophosphoryl chloride and organic solvent are mixed and subjected to coupling reaction to obtain the functionalized silica adsorption 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 the porous silica to pyrophosphoryl chloride is 0.5:1 to 1.8.

[0012] Preferably, the organic solvent comprises one or more of toluene, acetone, chloroform, dichloromethane and petroleum ether; and the usage ratio of the porous silica to the organic solvent is 0.5 g:40-100 mL.

[0013] Preferably, the mixing of porous silica, silane coupling agent, pyrophosphoryl chloride and organic solvent comprises 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 to 90° C. for 8 to 16 hours, and the coupling reaction is carried out in a closed container.

[0015] Preferably, after the coupling reaction, the method further comprises: performing solid-liquid separation on the obtained coupling reaction liquid, washing and drying the obtained solid in sequence to obtain the functionalized silica adsorption material; the washing reagent comprises ethanol, the drying is vacuum drying, the vacuum drying temperature is 50 to 80°C, and the time is 12 to 24 hours.

[0016] The present invention also provides the use of the functionalized silica adsorption material described in the above technical solution or the functionalized silica adsorption material prepared by the preparation method described in the above technical solution in metal separation.

[0017] Preferably, the steps include:

[0018] placing the functionalized silica adsorption material in a solution containing metal elements for adsorption;

[0019] The functionalized silica adsorption material and the solution containing the metal element are used in a ratio of 1 to 5 mg: 1 mL;

[0020] The metal element includes zirconium and / or scandium.

[0021] The invention provides a functionalized silica adsorption material.

[0022] The functionalized silica adsorption material of the present invention uses porous silica as a carrier, so that the functionalized silica adsorption material has a large specific surface area; at the same time, the pyrophosphoryl group is coupled to the porous silica through a silane coupling agent, and the P=O and PO bonds in the pyrophosphoryl group will preferentially form coordination bonds with zirconium, so it has high selectivity, high adsorption capacity and high adsorption rate for zirconium, so that the functionalized silica adsorption material has a high adsorption capacity for zirconium.

[0023] The data in the examples show that the adsorption capacity of the functionalized silica adsorption material provided by the present invention for zirconium is 127-130 mg / L.

[0024] The present invention also provides a method for preparing the functionalized silica adsorbent material described in the above technical solution. The present 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 in one step through a one-pot method, which is denoted as DPO / SiO2-N. The preparation method provided by the present invention is simple to operate. DETAILED DESCRIPTION

[0025] The present invention provides a functionalized silica adsorption material, comprising porous silica, and pyrophosphoryl groups coupled to the porous silica via a silane coupling agent;

[0026] The average pore volume of the porous silica is 0.3 to 2 cm 3 / g, average pore size of 1-20nm, specific surface area of ​​100-1000cm 2 / g.

[0027] The functionalized silica adsorption material provided by the present invention comprises porous silica, wherein the average pore volume of the porous silica is 0.3 to 2 cm 3 / g, average pore size of 1-20nm, specific surface area of ​​100-1000cm 2 In the present invention, the use of the porous silica can increase the specific surface area of ​​the functionalized silica adsorbent material, thereby increasing the connection between the silane coupling agent and the pyrophosphoryl group, thereby achieving an increase in the adsorption capacity of the functionalized silica adsorbent material.

[0028] The functionalized silica adsorption material provided by the present invention comprises a pyrophosphoryl group coupled to the porous silica via a silane coupling agent. In the present invention, the type of the silane coupling agent is preferably described in the subsequent preparation method section and will not be repeated here.

[0029] The present invention also provides a method for preparing the functionalized silica adsorption material described in the above technical solution, comprising the following steps:

[0030] The porous silica, silane coupling agent, pyrophosphoryl chloride and organic solvent are mixed and subjected to coupling reaction to obtain the functionalized silica adsorption material.

[0031] Unless otherwise specified, the raw materials used in the present invention are preferably commercially available products.

[0032] In the present invention, the silane coupling agent preferably contains an amino group. In the present invention, the silane coupling agent further preferably includes one or more of 3-aminopropyltriethoxysilane and 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane. In the present invention, the mass ratio of the porous silica to the silane coupling agent is preferably 0.5:0.45 to 0.6, and specifically preferably 0.5:0.45, 0.5:0.5, 0.5:0.55 or 0.5:0.6. In the present invention, the silane coupling agent can realize the connection between porous silica and pyrophosphoryl groups. At the same time, in the present invention, the amino group in the silane coupling agent has higher reactivity than the silanol group, and can better realize the grafting of pyrophosphoryl groups. The mass ratio of porous silica to silane coupling agent is controlled to be 0.5:0.45-0.6, which can increase the specific surface area and the functional group content. Excessive use of silane coupling agent will cause the pores of porous silica to be blocked, reduce the specific surface area, and reduce the available functional group content.

[0033] In the present invention, the mass ratio of the porous silica to pyrophosphoryl chloride is preferably 0.5:1 to 1.8, and is 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. In the present invention, the mass ratio of the porous silica to pyrophosphoryl chloride is controlled to be 0.5:1 to 1.8, so that the content of pyrophosphoryl in the functionalized silica adsorbent is high, and the selectivity and adsorption of pyrophosphoryl to zirconium are better exerted, and finally the adsorption capacity of the functionalized silica adsorbent to zirconium and the scandium-zirconium separation coefficient are improved.

[0034] In the present invention, the organic solvent preferably includes one or more of toluene, acetone, chloroform, dichloromethane and petroleum ether. In the present invention, the amount ratio of the porous silica and the organic solvent is preferably 0.5g:40-100mL, specifically preferably 0.5g:40mL, 0.5g:50mL, 0.5g:60mL, 0.5g:70mL, 0.5g:80mL, 0.5g:90mL or 0.5g:100mL. In the present invention, the organic solvent can achieve uniform dispersion of porous silica to promote its contact and connection with the silane coupling agent and pyrophosphoryl chloride.

[0035] In the present 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; adding silane coupling agent and pyrophosphoryl chloride to the porous silica dispersion in sequence. In the present invention, the dispersion temperature is preferably room temperature, the dispersion is preferably carried out under stirring, and the stirring time is preferably 10 to 30 minutes, specifically preferably 10 minutes, 15 minutes, 20 minutes, 25 minutes or 30 minutes. In the present invention, after the addition of pyrophosphoryl chloride is completed, it is preferably further stirred at room temperature for 10 to 30 minutes, specifically preferably 10 minutes, 15 minutes, 20 minutes, 25 minutes or 30 minutes.

[0036] In the present invention, the temperature of the coupling reaction is preferably 80-90°C, specifically preferably 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 8-16h, specifically preferably 8h, 12h or 16h; the coupling reaction is preferably carried out in a closed container. In the present invention, the coupling reaction is preferably carried out under static conditions.

[0037] After the coupling reaction, the present invention preferably further comprises: performing solid-liquid separation on the obtained coupling reaction feed liquid, washing and drying the obtained solid in sequence, to obtain the functionalized silica adsorption material. In the present invention, the washing reagent preferably comprises ethanol, and the ethanol is preferably anhydrous ethanol. In the present invention, the drying is preferably vacuum drying, and the temperature of the vacuum drying is preferably 50 to 80°C, specifically preferably 50°C, 60°C, 70°C or 80°C, and the time is preferably 12 to 24h, specifically preferably 12h, 18h or 24h.

[0038] The present invention also provides the use of the functionalized silica adsorption material described in the above technical solution or the functionalized silica adsorption material prepared by the preparation method described in the above technical solution in metal separation.

[0039] In the present invention, the application preferably comprises the following steps:

[0040] The functionalized silica adsorption material is placed in a solution containing metal elements for adsorption.

[0041] In the present invention, the usage ratio of the functionalized silica adsorbent material and the solution containing the metal element is preferably 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 the present invention, the metal element includes zirconium and / or scandium.

[0043] In the present invention, the adsorption temperature is preferably room temperature. In the present invention, the adsorption is preferably carried out under shaking conditions, and the shaking rate is preferably 100-300 rpm, and specifically preferably 100 rpm, 200 rpm or 300 rpm.

[0044] The functionalized silica adsorption material provided by the present invention and its preparation method and application are described in detail below in conjunction with the examples, but they 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 cm 3 / g, average pore diameter of 6.51nm, specific surface area of ​​756cm 2 / g) was mixed with toluene at a solid-liquid ratio of 0.5g:40mL, and the mixture was stirred at room temperature for 15min. Then, 0.45g of 3-aminopropyltriethoxysilane and 1.8g of pyrophosphoryl chloride were added in sequence, and the mixture was stirred at room temperature for 15min to obtain a suspension.

[0047] 2) The suspension in step 1) is transferred to a sealed pressure-resistant container, and heated at 80° C. for 12 h. After heating, solid-liquid separation is performed to obtain a solid product.

[0048] 3) The solid product obtained in step 2) was washed several times with anhydrous ethanol, and vacuum dried at 50° C. for 24 h to obtain a functionalized silica adsorption material, which was recorded as DPO / SiO2-N.

[0049] Example 2

[0050] 1) Porous silica (average pore volume 1.7 cm 3 / g, average pore diameter of 7.20nm, specific surface area of ​​824cm 2 / g) was mixed with acetone at a solid-liquid ratio of 0.5g:100mL, and the mixture was stirred at room temperature for 30min. Then, 0.6g of 3-aminopropyltrimethoxysilane and 1g of pyrophosphoryl chloride were added in sequence, and the mixture was stirred at room temperature for 30min to obtain a suspension.

[0051] 2) The suspension in step 1) is transferred to a sealed pressure-resistant container, and heated at 90° C. for 8 h. After heating, solid-liquid separation is performed to obtain a solid product.

[0052] 3) The solid product obtained in step 2) was washed several times with anhydrous ethanol, and vacuum dried at 80° C. for 12 h to obtain a functionalized silica adsorption material, which was recorded as DPO / SiO2-N.

[0053] Example 3

[0054] 1) Porous silica (average pore volume 0.7 cm 3 / g, average pore diameter of 4.57nm, specific surface area of ​​456cm 2 / g) was mixed with chloroform at a solid-liquid ratio of 0.5g:60mL, and the mixture was stirred at room temperature for 20min. Then, 0.45g of 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane and 1.3g of pyrophosphoryl chloride were added in sequence, and the mixture was stirred at room temperature for 20min to obtain a suspension.

[0055] 2) The suspension in step 1) is transferred to a sealed pressure-resistant container, and heated at 80° C. for 16 h. After heating, solid-liquid separation is performed to obtain a solid product.

[0056] 3) The solid product obtained in step 2) was washed several times with anhydrous ethanol, and vacuum dried at 80° C. for 12 h to obtain a functionalized silica adsorption material, which was recorded as DPO / SiO2-N.

[0057] Comparative Example 1

[0058] 1) Porous silica (average pore volume 1.12 cm 3 / g, average pore diameter of 6.51nm, specific surface area of ​​756cm 2 / g) and toluene at a solid-liquid ratio of 0.5g:40mL were mixed, and the mixture was stirred at room temperature for 30min. Then, 0.95g of 3-aminopropylbis(trimethylsilyloxy)methylsilane and 1.8g of pyrophosphoryl chloride were added in sequence, and the mixture was stirred at room temperature for 20min to obtain a suspension.

[0059] 2) The suspension in step 1) is transferred to a sealed pressure-resistant container, and heated at 80° C. for 1 h. After heating, solid-liquid separation is performed 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 cm 3 / g, average pore diameter of 6.51nm, specific surface area of ​​756cm 2 / g) was mixed with toluene at a solid-liquid ratio of 0.5g:40mL, stirred at room temperature for 15min, 1.8g of pyrophosphoryl chloride was added, and the mixture was reacted at room temperature for 48h. After the reaction was completed, solid-liquid separation was performed to obtain a solid product.

[0063] 2) The solid product obtained in step 2) was washed several times with anhydrous ethanol and vacuum dried at 50° C. for 24 h to obtain DPO / SiO2.

[0064] Comparative Example 3

[0065] The difference from Example 1 is that the mass of 3-aminopropyltriethoxysilane is 0.9 g, and the rest is the same as Example 1.

[0066] Comparative Example 4

[0067] The difference from Example 1 is that the mass of 3-aminopropyltriethoxysilane is 0.3 g, and the rest is the same as Example 1.

[0068] Comparative Example 5

[0069] The difference from Example 1 is that the mass of pyrophosphoryl chloride is 0.5 g, and the rest is the same as Example 1.

[0070] Comparative Example 6

[0071] The difference from Example 1 is that the mass of pyrophosphoryl chloride is 2 g, and the rest is the same as Example 1.

[0072] Performance Testing

[0073] 1. Test the adsorption capacity of zirconium. The specific process is as follows:

[0074] In a solution with a nitric acid acidity of 6 mol / L and a zirconium concentration of 400 μg / mL, an adsorbent (the adsorbent is the material obtained in the embodiment and the comparative example) is added at a solid-liquid ratio of 10 to 40 mg / 10 mL, and the solution is shaken for 12 hours at room temperature and a shaking speed of 200 rpm. The adsorbed solution is tested for the ion concentration after adsorption using ICP, and the adsorption capacity of the adsorbent for zirconium is calculated. The results are shown in Table 1.

[0075] 2. The specific process of separation of scandium and zirconium is as follows:

[0076] In a solution with a nitric acid acidity of 1-6 mol / L, a zirconium concentration of 1 mmol / L, and a scandium concentration of 1 mmol / L, an adsorbent (the adsorbent is the material obtained in the embodiment and the comparative example) is added at a solid-liquid ratio of 10-40 mg / 10 mL, and the solution is shaken at room temperature and a shaking speed of 200 rpm for 12 hours. The adsorbed solution is tested for the ion concentration after adsorption using ICP, and the adsorption capacity of the adsorbent for zirconium is calculated. The results are shown in Table 1.

[0077] The obtained 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 Examples and Comparative Examples

[0079]

[0080] It can be seen from Table 1 that the functionalized silica adsorption material provided by the present invention has a high adsorption capacity for zirconium and has a good separation effect for scandium and zirconium, a low scandium loss rate, and a large scandium-zirconium separation coefficient.

[0081] 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 principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A functionalized silica adsorption material, characterized in that: The method comprises porous silica, wherein a pyrophosphoryl group is coupled to the porous silica via a silane coupling agent; The average pore volume of the porous silica is 0.3 to 2 cm 3 / g, average pore size of 1-20nm, specific surface area of ​​100-1000cm 2 / g.

2. The method for preparing the functionalized silica adsorption material according to claim 1, characterized in that: The following steps are involved: The porous silica, silane coupling agent, pyrophosphoryl chloride and organic solvent are mixed and subjected to coupling reaction to obtain the functionalized silica adsorption material.

3. The preparation method according to claim 2, characterized in that: The silane coupling agent contains amino groups, and includes one or more of 3-aminopropyltriethoxysilane, 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane and 3-aminopropylbis(trimethylsiloxy)methylsilane; the mass ratio of the porous silica to the silane coupling agent is 0.5:0.45-0.

6.

4. The preparation method according to claim 2, characterized in that: The mass ratio of the porous silica to pyrophosphoryl chloride is 0.5:1-1.

8.

5. The preparation method according to claim 2, characterized in that: The organic solvent includes one or more of toluene, acetone, chloroform, dichloromethane and petroleum ether; the usage ratio of the porous silica to the organic solvent is 0.5g:40-100mL.

6. The preparation method according to claim 2, characterized in that: The mixing of porous silica, silane coupling agent, pyrophosphoryl chloride and organic solvent comprises the following steps: dispersing porous silica in organic solvent to form porous silica dispersion; and sequentially adding silane coupling agent and pyrophosphoryl chloride into the porous silica dispersion.

7. The preparation method according to claim 2, characterized in that: The coupling reaction is carried out at a temperature of 80 to 90° C. for 8 to 16 hours in a sealed container.

8. The preparation method according to claim 2 or 7, characterized in that: After the coupling reaction, the method further comprises: performing solid-liquid separation on the obtained coupling reaction liquid, washing and drying the obtained solid in sequence to obtain the functionalized silica adsorption material; the washing reagent comprises ethanol, the drying is vacuum drying, the vacuum drying temperature is 50 to 80° C., and the time is 12 to 24 hours.

9. Use of the functionalized silica adsorption material according to claim 1 or the functionalized silica adsorption material prepared by the preparation method according to any one of claims 2 to 8 in metal separation.

10. The use according to claim 9, characterized in that: The following steps are involved: placing the functionalized silica adsorption material in a solution containing metal elements for adsorption; The functionalized silica adsorption material and the solution containing the metal element are used in a ratio of 1 to 5 mg: 1 mL; The metal element includes zirconium and / or scandium.

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