Niobium-indium oxide molecular sieve purification material and preparation method thereof
By using the molecular sieve material of the oxide, the problem of difficulty regenerating the existing molecular sieve after adsorption saturation is solved, the function of oxidizing organic matter under light under light, continuous adsorption and purifying pollutants, and improving the long -term use of materials efficiency.
Patent Information
- Application Number
- CN202411573644.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-06
- Publication Date
- 2025-01-28
AI Technical Summary
The existing molecular sieves are difficult to regenerate after adsorption and saturation, which limits their convenience for long-term use.
The molecular sieve material is used, which is a molecular sieve skeleton skeleton in the oxide and oxide group. It has a regular tract and cavity structure. It can be decomposed and regenerated that can be decomposed and regenerated under the light.
This material has a huge Kong Ronghe surface, which can continuously adsorb and purify organic pollutants, avoid regeneration difficulties after adsorption saturation, and improve the long -term use efficiency of materials.
Smart Images
Figure BDA0005121199420000041
Abstract
Description
Technical Field
[0001] The invention belongs to the field of environmental purification materials, and in particular relates to a niobium indium oxide molecular sieve purification material and a preparation method thereof. Background Art
[0002] Natural molecular sieves, also known as zeolites, are usually composed of crystalline aluminosilicates. The typical feature of molecular sieves is that they have uniform pore structures ranging from micrometers to nanometers. Common molecular sieves form a regular skeleton structure with aluminosilicates, which contains pores of regular sizes, i.e., the cavity structure of the molecular sieve. The cavity structure of the molecular sieve presents different forms from one-dimensional to three-dimensional, and has a specific opening size and cavity volume. Because of this special pore structure, molecular sieves usually have very rich pore volume and a large specific surface area.
[0003] One of the most widely used areas of molecular sieves is the adsorption of small molecules, including organic molecules and inorganic ions and molecules, and has been studied in depth in the field of pollution control. The performance of molecular sieves is mainly determined by the atoms and ions that make up their skeleton structure, as well as the volume and opening size of the cavities formed. Common natural and artificial molecular sieves often only have the function of adsorbing pollutant molecules, and can no longer continue to play an adsorption role after adsorption saturation. Molecular sieves that have been saturated with adsorption must be regenerated using special methods, which is very inconvenient for the long-term use of molecular sieves. Summary of the invention
[0004] In view of the problems existing in the prior art, the present invention aims to provide a method for preparing a niobium-indium oxide molecular sieve purification material. This material uses niobium oxide and indium oxide to form a molecular sieve framework, and forms regular channels and cavities inside the material, which can be used for the adsorption and purification of environmental pollutants.
[0005] A niobium indium oxide molecular sieve purification material, wherein the bulk density of the niobium indium oxide molecular sieve material is 2.1 to 2.3 g / cm 3 Specific surface area 185~206m 2 / g, pore volume 0.68~0.72cm 3 / g.
[0006] Furthermore, the atomic molar ratio of niobium to indium in the niobium indium oxide molecular sieve material is 1:1.
[0007] Furthermore, the niobium indium oxide molecular sieve material maintains stable structure and performance at a temperature below 530°C.
[0008] A method for preparing a niobium indium oxide molecular sieve purification material comprises the following process steps:
[0009] Step 1: Preparation of niobium precursor
[0010] 6.3-6.8 g of niobium tetrachloride, 3.1-3.5 g of emulsifier Tween 60 and 7-9 g of dodecyltrimethylammonium bromide were added to 300 mL of anhydrous ethanol respectively, and stirred to form a solution A; the solution A was heated to 55° C. and refluxed for 20 minutes to obtain a niobium precursor;
[0011] Step 2: Preparation of Indium Precursor
[0012] 8.1-8.6 g of indium nitrate was added to 150 mL of 0.2 mol / L sodium bicarbonate solution, and the mixture was stirred to form a solution B; 6.5-7.1 g of polyethylene glycol with a molecular weight of 6000 was added to the solution B, and the mixture was heated to 45° C. and refluxed for 20 min to obtain an indium precursor;
[0013] Step 3: Hydrothermal synthesis
[0014] The niobium precursor described in step 1 and the indium precursor described in step 2 are mixed and placed in a stainless steel hydrothermal reactor, 5-6 mL of tetrabutylammonium hydroxide methanol solution is added, the mixed solution is heated to 230-240° C., and the reaction is carried out for 65 hours; the obtained product is filtered, washed with pure water, and then mixed with 200 mL of pure water, ultrasonically dispersed for 30 minutes, and filtered to obtain solid A; the solid A is dried at 220° C. for 18 hours, and then calcined at 560-630° C. for 5 hours to obtain a niobium indium oxide molecular sieve.
[0015] Furthermore, in the reflux process in step 1, a straight condenser is used as a cooler, and tap water is introduced into the straight condenser as a cooling medium.
[0016] Furthermore, the pressure in the stainless steel hydrothermal reactor during the hydrothermal synthesis process in step 3 is less than 2.2 MPa.
[0017] Furthermore, the mass percentage of tetrabutylammonium hydroxide in the tetrabutylammonium hydroxide methanol solution in step 3 is 25%.
[0018] Compared with the prior art, the advantages of the present invention are:
[0019] The niobium indium oxide molecular sieve is composed of niobium oxide and indium oxide to form the molecular sieve skeleton. The basic unit of the molecular sieve skeleton structure is the niobium-oxygen-indium bond. The niobium-oxygen-indium bond constructs the regular pore and cavity structure of the molecular sieve, and its opening size is comparable to the size of most single-molecule organic molecules. The niobium indium oxide molecular sieve has a huge pore volume and specific surface area, can adsorb a variety of organic pollutants in the environment, and has a large adsorption saturation capacity. The niobium indium oxide molecular sieve can also oxidize the adsorbed organic molecules under light to achieve the decomposition of organic matter, releasing the occupied molecular sieve surface, so that the niobium indium oxide molecular sieve purification material can be continuously used for the purification of organic pollutants in the environment. DETAILED DESCRIPTION
[0020] The present invention will be further described below with reference to examples.
[0021] Example 1
[0022] A method for preparing a niobium indium oxide molecular sieve purification material comprises the following process steps:
[0023] Step 1: Preparation of niobium precursor
[0024] 6.3 g of niobium tetrachloride, 3.1 g of emulsifier Tween 60 and 7 g of dodecyltrimethylammonium bromide were added to 300 mL of anhydrous ethanol respectively, and the mixture was stirred to form a solution A. The solution A was heated to 55° C. and refluxed for 20 minutes to obtain a niobium precursor.
[0025] Step 2: Preparation of Indium Precursor
[0026] 8.1 g of indium nitrate was added to 150 mL of 0.2 mol / L sodium bicarbonate solution, and the mixture was stirred to form solution B. 6.5 g of polyethylene glycol with a molecular weight of 6000 was added to solution B, and the mixture was heated to 45° C. and refluxed for 20 min to obtain an indium precursor.
[0027] Step 3: Hydrothermal synthesis
[0028] The niobium precursor of step 1 and the indium precursor of step 2 are mixed and placed in a stainless steel hydrothermal reactor, 5-6 mL of tetrabutylammonium hydroxide methanol solution is added, the mixed solution is heated to 230° C., and the reaction is carried out for 65 hours; the obtained product is filtered, washed with pure water, and then mixed with 200 mL of pure water, ultrasonically dispersed for 30 minutes, and filtered to obtain solid A; solid A is dried at 220° C. for 18 hours, and then calcined at 560° C. for 5 hours to obtain niobium indium oxide molecular sieve.
[0029] The bulk density of the prepared niobium indium oxide molecular sieve material is 2.1 g / cm 3 , specific surface area 185m 2 / g, pore volume 0.68cm 3 / g.
[0030] Example 2
[0031] A method for preparing a niobium indium oxide molecular sieve purification material comprises the following process steps:
[0032] Step 1: Preparation of niobium precursor
[0033] 6.4 g of niobium tetrachloride, 3.2 g of emulsifier Tween 60 and 7.3 g of dodecyltrimethylammonium bromide were added to 300 mL of anhydrous ethanol respectively, and the mixture was stirred to form a solution A. The solution A was heated to 55° C. and refluxed for 20 minutes to obtain a niobium precursor.
[0034] Step 2: Preparation of Indium Precursor
[0035] 8.2 g of indium nitrate was added to 150 mL of 0.2 mol / L sodium bicarbonate solution, and the mixture was stirred to form solution B. 6.6 g of polyethylene glycol with a molecular weight of 6000 was added to solution B, and the mixture was heated to 45° C. and refluxed for 20 min to obtain an indium precursor.
[0036] Step 3: Hydrothermal synthesis
[0037] The niobium precursor of step 1 and the indium precursor of step 2 are mixed and placed in a stainless steel hydrothermal reactor, 5.2 mL of tetrabutylammonium hydroxide methanol solution is added, the mixed solution is heated to 232° C., and the reaction is carried out for 65 hours; the obtained product is filtered, washed with pure water, and then mixed with 200 mL of pure water, ultrasonically dispersed for 30 minutes, and filtered to obtain solid A; solid A is dried at 220° C. for 18 hours, and then calcined at 570° C. for 5 hours to obtain niobium indium oxide molecular sieve.
[0038] The bulk density of the prepared niobium indium oxide molecular sieve material is 2.1 g / cm 3 , specific surface area 191m 2 / g, pore volume 0.69cm 3 / g.
[0039] Example 3
[0040] A method for preparing a niobium indium oxide molecular sieve purification material comprises the following process steps:
[0041] Step 1: Preparation of niobium precursor
[0042] 6.5 g of niobium tetrachloride, 3.2 g of emulsifier Tween 60 and 8 g of dodecyltrimethylammonium bromide were added to 300 mL of anhydrous ethanol respectively, and the mixture was stirred to form a solution A. The solution A was heated to 55° C. and refluxed for 20 minutes to obtain a niobium precursor.
[0043] Step 2: Preparation of Indium Precursor
[0044] 8.3 g of indium nitrate was added to 150 mL of 0.2 mol / L sodium bicarbonate solution, and the mixture was stirred to form solution B. 6.7 g of polyethylene glycol with a molecular weight of 6000 was added to solution B, and the mixture was heated to 45° C. and refluxed for 20 min to obtain an indium precursor.
[0045] Step 3: Hydrothermal synthesis
[0046] The niobium precursor of step 1 and the indium precursor of step 2 are mixed and placed in a stainless steel hydrothermal reactor, 5.5 mL of tetrabutylammonium hydroxide methanol solution is added, the mixed solution is heated to 235° C., and the reaction is carried out for 65 hours; the obtained product is filtered, washed with pure water, and then mixed with 200 mL of pure water, ultrasonically dispersed for 30 minutes, and filtered to obtain solid A; solid A is dried at 220° C. for 18 hours, and then calcined at 580° C. for 5 hours to obtain a niobium indium oxide molecular sieve.
[0047] The bulk density of the prepared niobium indium oxide molecular sieve material is 2.2 g / cm 3 , specific surface area 196m 2 / g, pore volume 0.69cm 3 / g.
[0048] Example 4
[0049] A method for preparing a niobium indium oxide molecular sieve purification material comprises the following process steps:
[0050] Step 1: Preparation of niobium precursor
[0051] 6.8 g of niobium tetrachloride, 3.5 g of emulsifier Tween 60 and 9 g of dodecyltrimethylammonium bromide were added to 300 mL of anhydrous ethanol respectively, and the mixture was stirred to form a solution A. The solution A was heated to 55° C. and refluxed for 20 minutes to obtain a niobium precursor.
[0052] Step 2: Preparation of Indium Precursor
[0053] 8.6 g of indium nitrate was added to 150 mL of 0.2 mol / L sodium bicarbonate solution, and the mixture was stirred to form solution B. 7.1 g of polyethylene glycol with a molecular weight of 6000 was added to solution B, and the mixture was heated to 45° C. and refluxed for 20 min to obtain an indium precursor.
[0054] Step 3: Hydrothermal synthesis
[0055] The niobium precursor of step 1 and the indium precursor of step 2 are mixed and placed in a stainless steel hydrothermal reactor, 6 mL of tetrabutylammonium hydroxide methanol solution is added, the mixed solution is heated to 240° C., and the reaction is carried out for 65 hours; the obtained product is filtered, washed with pure water, and then mixed with 200 mL of pure water, ultrasonically dispersed for 30 minutes, and filtered to obtain solid A; solid A is dried at 220° C. for 18 hours, and then calcined at 630° C. for 5 hours to obtain niobium indium oxide molecular sieve.
[0056] The bulk density of the prepared niobium indium oxide molecular sieve material is 2.3 g / cm 3 , specific surface area 206m 2 / g, pore volume 0.72cm 3 / g.
[0057] Prepare 300mL of 5mg / L ofloxacin solution, add 100mg of niobium indium oxide molecular sieve prepared in Example 1-4, stir for 30min in a dark place, measure the concentration of ofloxacin solution and calculate the adsorption rate of ofloxacin by the material. Then place the solution under 20W ultraviolet germicidal lamp for irradiation, take a sample after 50min to measure the concentration of ofloxacin solution, and calculate the degradation rate of ofloxacin. The results are shown in the table below.
[0058]
[0059] The results show that the niobium indium oxide molecular sieves prepared in Examples 1-4 have a strong capacity for adsorbing organic matter and can quickly and completely degrade organic pollutants under light.
Claims
1. A niobium indium oxide molecular sieve purification material, characterized in that: The bulk density of the niobium indium oxide molecular sieve material is 2.1-2.3 g / cm 3 Specific surface area 185~206m 2 / g, pore volume 0.68~0.72cm 3 / g.
2. A niobium indium oxide molecular sieve purification material according to claim 1, characterized in that: The atomic molar ratio of niobium to indium in the niobium indium oxide molecular sieve material is 1:
1.
3. The niobium indium oxide molecular sieve purification material according to claim 1, characterized in that: The niobium indium oxide molecular sieve material maintains stable structure and performance at a temperature below 530°C.
4. A method for preparing a niobium indium oxide molecular sieve purification material according to any one of claims 1 to 3, characterized in that: The process steps include: Step 1: Preparation of niobium precursor 6.3-6.8 g of niobium tetrachloride, 3.1-3.5 g of emulsifier Tween 60 and 7-9 g of dodecyltrimethylammonium bromide were added to 300 mL of anhydrous ethanol respectively, and stirred to form solution A; The solution A is heated to 55° C. and refluxed for 20 minutes to obtain a niobium precursor; Step 2: Preparation of Indium Precursor Add 8.1-8.6 g of indium nitrate to 150 mL of 0.2 mol / L sodium bicarbonate solution and stir to form solution B; Add 6.5-7.1 g of polyethylene glycol with a molecular weight of 6000 to the solution B, heat to 45° C., and reflux for 20 min to obtain an indium precursor; Step 3: Hydrothermal synthesis The niobium precursor described in step 1 and the indium precursor described in step 2 are mixed and placed in a stainless steel hydrothermal reactor, 5-6 mL of tetrabutylammonium hydroxide methanol solution is added, the mixed solution is heated to 230-240° C., and the reaction is carried out for 65 hours; the obtained product is filtered, washed with pure water, and then mixed with 200 mL of pure water, ultrasonically dispersed for 30 minutes, and filtered to obtain solid A; the solid A is dried at 220° C. for 18 hours, and then calcined at 560-630° C. for 5 hours to obtain a niobium indium oxide molecular sieve.
5. The method for preparing a niobium indium oxide molecular sieve purification material according to claim 4, characterized in that: The reflux process described in step 1 uses a straight condenser as a cooler, and tap water is passed into the straight condenser as a cooling medium.
6. The method for preparing a niobium indium oxide molecular sieve purification material according to claim 4, characterized in that: During the hydrothermal synthesis process in step 3, the pressure in the stainless steel hydrothermal reactor is less than 2.2 MPa.
7. The method for preparing a niobium indium oxide molecular sieve purification material according to claim 4, characterized in that: The mass percentage of tetrabutylammonium hydroxide in the tetrabutylammonium hydroxide methanol solution in step 3 is 25%.