CN109833857B - Preparation method of carrier silica gel for olefin catalysis - Google Patents
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Abstract
The invention relates to a preparation method of carrier silica gel for olefin catalysis, wherein the carrier silica gel takes silicate as a base solution, and the synthesis of silica sol is completed by adopting a parallel-flow adding mode of silicate and inorganic acid; simultaneously adding ethanol aqueous solution of alkali metal carbonate and aqueous solution of two kinds of metal nitrate in parallel flow to complete the synthesis of hydrotalcite. The process can greatly improve the specific surface area of the silica gel under the condition of not influencing the pore volume of the silica gel, thereby improving the basic physical properties of the carrier silica gel; the process preparation is simple to operate, good in repeatability and low in energy consumption, and provides technical support for industrial device production.
Description
Technical Field
The invention relates to a preparation method of carrier silica gel, in particular to a preparation method of carrier silica gel for olefin catalysis.
Background
When silica gel is used as a catalyst support, the high specific surface area can greatly improve the catalyst activity when the silica gel has an appropriate pore volume, pore diameter and distribution. In order to obtain a high specific surface area, the pore volume and pore size are mostly sacrificed in the conventional method for preparing the carrier silica gel, so that a new method is required to meet the preparation process requirements of the carrier silica gel for the catalyst. Hydrotalcite is a layered double hydroxide, which consists of magnesium octahedra and aluminum octahedra. The specific surface area of the uncalcined hydrotalcite is 5-20 m2The calcined hydrotalcite has a high specific surface area of 200-300 m2The specific surface area before and after calcination showed a geometric quantitative increase. The hydrotalcite has unique structural characteristics, so that the hydrotalcite can be used as a basic catalyst, a redox catalyst and a catalyst carrier. Therefore, water skiing can be adoptedThe stone modifies the carrier silica gel to increase the specific surface area of the carrier silica gel.
The supported silica gel is mainly used in conventional Ziegler-Natta catalysts and metallocene olefin polymerization catalysts. At present, a preparation method of carrier silica gel has been reported at home and abroad, for example, silicate is taken as mother liquor, and then the silicate and inorganic acid are added for reaction; or silicate and inorganic acid are taken as mother liquor, and the inorganic acid is added to adjust the PH value; or adding the silicate and the inorganic acid simultaneously for reaction in a parallel flow mode.
U.S. Pat. No. 5,5372983 discloses the preparation of SiO by azeotropic distillation2. Firstly, silicate reacts with dilute sulphuric acid to prepare hydrogel, impurities are removed by washing, then C5-C6 alcohol such as pentanol, hexanol or a mixture of the pentanol and the hexanol is added, and water in pores of the hydrogel is removed by azeotropic distillation to obtain xerogel. Roasting at 450-700 ℃ to obtain SiO product2. Physical property indexes are as follows: pore volume is 2.2cm3/g～2.5cm3Per g, specific surface area 420m2/g～550m2G, bulk density 0.18g/cm3～2.5g/cm3。
Us patent 5599762, 5576262 improves the process of azeotropic distillation thereof. It is essential to find some suitable organic compounds, such as alcohol ethers, alcohol ether esters and the like, including: ethyl ethoxyacetate, tert-butoxypropanol, propyl methoxyacetate, n-butoxypropanol, and ethyl ethoxypropionate, and the like. The use of these organic compounds for boiling distillation is not only cost effective, but also improves the performance of the polyethylene catalyst. Improved azeotropic distillation technology, and the prepared carrier SiO2And the catalyst properties are: SiO22Specific surface area of 520m2/g～530m2Per g, pore volume of 2.4cm3/g～2.6cm3The product melt index is 6.5g/10 min-6.5 g/10min, and the catalyst activity is 7000 PEg/gcat.h-8000 PEg/gcat.h.
US.3959174 discloses the preparation of SiO with large specific surface area and pore volume2A method. Mainly reduces SiO in the preparation process2Solubility or solvating auxiliaries, rendering SiO2In the prepared hydrosol system, the solubility of SiO2 is reducedForming hydrogel, and then preparing SiO2 by aging, water washing, drying and roasting. The auxiliary agent is ammonia, monohydric alcohol, dihydric alcohol, ketone and salt. They lower the dielectric constant in aqueous sol systems, thereby rendering SiO2Precipitating to form gel. SiO22The physical property indexes of (1): specific surface area 300m2/g～450m2G, pore volume of 1.2cm3/g～2.8cm3/g。
Phillips oil company also discloses a number of patents, us 4081407, 4152503, 3099457, 3948806, 4436883, 4246139, etc., which discuss azeotropic distillation techniques in an attempt to avoid pore shrinkage and collapse when water is removed from a hydrogel. In addition, a method of removing water by replacement with an organic solvent has been attempted.
The above method has obvious advantages and disadvantages. The azeotropic distillation method has the problems of long time for removing water by distillation, expensive solvent, large energy consumption and the like; the organic solvent replacement method has the disadvantages of complicated operation steps, large solvent consumption, difficult recovery and the like.
Disclosure of Invention
The invention aims to provide a method for preparing carrier silica gel for olefin catalysis, which has appropriate pore volume and pore diameter and greatly improved specific surface area.
Therefore, the invention provides a preparation method of carrier silica gel for olefin catalysis, which takes silicate and inorganic acid as raw materials and comprises the following preparation processes:
1) taking a silicate aqueous solution as a base solution;
2) adding a silicate aqueous solution and an inorganic acid aqueous solution in a concurrent flow manner, and simultaneously adding an ethanol aqueous solution of an alkali metal carbonate and a mixed aqueous solution of two kinds of metal nitrates in a concurrent flow manner;
3) adjusting the pH value of the reaction solution to 10-12;
4) adding an organic alcohol aqueous solution of inorganic acid, wherein the volume ratio of the organic alcohol to the water is 1: 5-1: 30, and adjusting the pH value of the reaction solution to 9-10;
5) carrying out hydrothermal reaction at 70-100 ℃;
6) and acidifying, washing, drying and activating to obtain a silica gel product.
Specifically, the preparation method of the carrier silica gel comprises the following steps:
1) adding 30-60 ml of silicate aqueous solution with the concentration of 1.0-3.0 mol/L into a reaction kettle, and heating to 40-60 ℃ under the condition of stirring;
2) adding 1.0-3.0 mol/L silicate aqueous solution and 1.0-3.0 mol/L inorganic acid aqueous solution in a parallel flow manner, controlling the flow rate to be 3-6 ml/min, simultaneously adding 3-10% by mass of ethanol aqueous solution of alkali metal carbonate and 10-30 ml of mixed aqueous solution of two kinds of metal nitrates in a mass fraction of 2-8% in a parallel flow manner, and controlling the flow rate to be 4-7 ml/min; the volume ratio of ethanol to water in the ethanol aqueous solution of the alkali metal carbonate is 1: 1-1: 10, preferably 1: 5-1: 9;
3) when the pH value of the reaction solution reaches 10-12, stopping adding the mixed solution, and reacting at constant temperature for 1.0-2.5 h;
4) adding an organic alcohol aqueous solution of inorganic acid with the concentration of 1.0-3.0 mol/L, controlling the flow rate to be 4-9 ml/min, adjusting the pH value of the solution to be 9-10, and reacting at constant temperature for 1.0-2.5 h, wherein the volume ratio of the organic alcohol to the water is 1: 5-1: 30, preferably 1: 10-1: 20;
5) carrying out hydrothermal reaction for 3.0-5.0 h at 70-100 ℃;
6) and after the reaction is finished, adding 1.0-3.0 mol/L of inorganic acid aqueous solution, adjusting the pH value of the solution to 3-6, cooling the reaction system to normal temperature, washing by using distilled water or a mixed solution of distilled water and ethanol, drying at 300-335 ℃, and activating for 3.0-6.0 h at 400-600 ℃ under the condition of inert gas to obtain the carrier silica gel.
The silicate is selected from one or more of sodium silicate, potassium silicate and water glass, and the concentration of the silicate aqueous solution is preferably 1.0-1.5 mol/L.
The inorganic acid is selected from one or more of sulfuric acid, hydrochloric acid and nitric acid, and the concentration of the inorganic acid aqueous solution is preferably 1.0-1.3 mol/L.
The alkali metal carbonate is selected from one or more of potassium carbonate and sodium carbonate, and the preferable mass fraction is 4-7%.
The two kinds of metal nitrates are selected from two kinds of magnesium nitrate, aluminum nitrate, nickel nitrate, manganese nitrate, cobalt nitrate, chromium nitrate, terbium nitrate and cerium nitrate, preferably the mixture of magnesium nitrate and aluminum nitrate or the mixture of zinc nitrate and aluminum nitrate, wherein the molar ratio of the two kinds of nitrates is 1: 1-1: 2, preferably 1: 1-1: 1.5.
The organic alcohol is at least one selected from n-butanol, isobutanol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-1-butanol, 2-dimethyl-1-propanol, preferably n-butanol and 1, 3-butanediol.
The invention adopts sol-gel reaction to prepare carrier silica gel, takes silicate as base solution, and adopts a mode of adding silicate and inorganic acid in a parallel flow manner to complete the synthesis of silica sol; simultaneously adding ethanol aqueous solution of alkali metal carbonate and aqueous solution of two kinds of metal nitrate in parallel flow to complete the synthesis of hydrotalcite. The process can ensure that two kinds of particles are fully contacted from primary particles, and hydrotalcite particles are completely dispersed in a silica sol network along with the growth of the silica sol particles, so that the specific surface area of the silica gel is increased on the premise of not influencing the performance of the carrier silica gel. During the gel reaction, the pH value of the reaction solution is adjusted by adding an organic alcohol aqueous solution of inorganic acid, and the preparation of the silica gel is completed through a high-temperature hydrothermal reaction. The double-layered hydrotalcite can greatly improve the specific surface area of the carrier silica gel, because CO is continuously removed between layers when the hydrotalcite is heated2And water, the ordered layered structure is destroyed, the surface area is increased, and the pore volume is increased. The ethanol is added in the process to better precipitate hydrotalcite, and the organic alcohol is added to improve the pore volume and distribution of the silica gel. The process can greatly improve the specific surface area of the silica gel under the condition of not influencing the pore volume of the silica gel, thereby improving the basic physical properties of the carrier silica gel; the process preparation is simple to operate, good in repeatability and low in energy consumption, and provides technical support for industrial device production.
Detailed Description
The technical effects of the present invention are further illustrated and demonstrated by the following examples, which should not be construed as limiting the invention.
In an embodiment, the relevant indexes are tested according to the following method:
specific surface area: gas adsorption BET method test, GB/T19587-2004.
Pore volume: BJH (Barrett-Joyner-Halenda) method, ISO 15901-2.
The average pore diameter d is 4V/A, A is the specific surface area, V is the pore volume, and d is the pore diameter.
Example 1
50ml of water glass water solution with the concentration of 1.2mol/L is added into the reaction kettle, the stirring is started, and the temperature is increased to 50 ℃. Adding 1.1mol/L sodium silicate aqueous solution and 1.25mol/L sulfuric acid aqueous solution at the flow rate of 4ml/min in a concurrent flow manner, simultaneously adding 25ml of ethanol aqueous solution (the volume ratio of ethanol to water is 1:6) with the mass fraction of 6% sodium carbonate and mixed aqueous solution (the molar ratio of two nitrates is 1:1) of magnesium nitrate and aluminum nitrate with the mass fraction of 4% in a concurrent flow manner at the flow rate of 5ml/min, stopping adding the mixed solution when the pH value of the solution in the reaction kettle reaches 11, and reacting at constant temperature for 2.0 h. Adding 1.0mol/L aqueous solution of n-butanol sulfate (n-butanol to water volume ratio of 1:15) at flow rate of 6ml/min, stopping adding the solution of n-butanol sulfate when pH value of the solution is 9, and reacting at constant temperature for 2.0 h. The reaction system is heated to 85 ℃ and reacts for 5.0h at constant temperature. Adding 1.0mol/L sulfuric acid water solution, and stopping adding when the pH value of the solution is 4. Cooling to room temperature, washing for three times by respectively using distilled water, a mixed solution of distilled water and ethanol, drying at 335 ℃, and activating for 4 hours at 600 ℃ under the protection of inert gas to obtain a carrier silica gel product. The test results are shown in table 1.
Example 2
The procedure is as in example 1, except that 50ml of a 1.2mol/L aqueous potassium silicate solution are charged into the reactor, the stirring is switched on and the temperature is raised to 50 ℃. A1.1 mol/L aqueous potassium silicate solution and a 1.25mol/L aqueous sulfuric acid solution were concurrently added at a flow rate of 4ml/min, while a 6% by mass aqueous ethanol solution of potassium carbonate (ethanol to water volume ratio of 1:6) was concurrently added at a flow rate of 5 ml/min. Other conditions were the same as in example 1. The test results are shown in table 1.
Example 3
The preparation process is the same as that of example 1, except that 1.1mol/L sodium silicate aqueous solution and 1.3mol/L nitric acid aqueous solution are added in a concurrent flow manner at a flow rate of 4ml/min, simultaneously ethanol aqueous solution with the mass fraction of 6% sodium carbonate (the volume ratio of ethanol to water is 1:5) and 25ml zinc nitrate and aluminum nitrate mixed aqueous solution with the mass fraction of 4% (the molar ratio of two nitrates is 1:1.2) are added in a concurrent flow manner at a flow rate of 5ml/min, when the pH value of the solution in the reaction kettle reaches 11, the addition of the mixed solution is stopped, and the constant temperature reaction is carried out for 2.0 hours. Adding 1.0mol/L aqueous solution of n-butanol nitrate at the flow rate of 6ml/min (the volume ratio of n-butanol to water is 1:10), stopping adding the n-butanol nitrate solution when the pH value of the solution is 9, and reacting at constant temperature for 2.0 h. The reaction system is heated to 85 ℃ and reacts for 5.0h at constant temperature. Adding 1.0mol/L nitric acid aqueous solution, and stopping adding when the pH value of the solution is 4. Other conditions were the same as in example 1. The test results are shown in table 1.
Example 4
The procedure is as in example 1, except that 50ml of a 1.2mol/L aqueous solution of water glass are added to the reactor, the mixture is stirred and the temperature is raised to 50 ℃. Adding 1.1mol/L sodium silicate aqueous solution and 1.25mol/L sulfuric acid aqueous solution at the flow rate of 4ml/min in a concurrent flow manner, simultaneously adding 25ml of ethanol aqueous solution (the volume ratio of ethanol to water is 1:9) with the mass fraction of 6% sodium carbonate and mixed aqueous solution (the molar ratio of two nitrates is 1:1.7) of magnesium nitrate and aluminum nitrate with the mass fraction of 4% in a concurrent flow manner at the flow rate of 5ml/min, stopping adding the mixed solution when the pH value of the solution in the reaction kettle reaches 12, and reacting at constant temperature for 2.0 hours. Adding 1.0mol/L aqueous solution of n-butanol sulfate (n-butanol to water volume ratio of 1:20) at flow rate of 6ml/min, stopping adding the solution of n-butanol sulfate when pH value of the solution is 10, and reacting at constant temperature for 2.0 h. Other conditions were the same as in example 1. The test results are shown in table 1.
Example 5
The preparation process is the same as that of example 1, except that 25ml of an ethanol aqueous solution with 6% of sodium carbonate by mass fraction (ethanol-water volume ratio of 1:6) and 25ml of a magnesium nitrate and aluminum nitrate mixed aqueous solution with 4% of sodium carbonate by mass fraction (molar ratio of two nitrates of 1:1.5) are added in parallel at 5ml/min, and the other conditions are the same as those of example 1. The test results are shown in table 1.
Example 6
The preparation process is the same as example 1, except that 1.0mol/L sulfuric acid 1, 3-butanediol aqueous solution (1, 3-butanediol/water volume ratio is 1:15) is added at the flow rate of 6ml/min, the addition of the sulfuric acid 1, 3-butanediol aqueous solution is stopped when the pH value of the solution is 9, and the reaction is carried out for 2.0 hours at constant temperature. Other conditions were the same as in example 1. The test results are shown in table 1.
Example 7
The preparation process is the same as example 1, except that the temperature of the reaction system is raised to 90 ℃, and the reaction is carried out for 5 hours at constant temperature. A1.0 mol/L aqueous sulfuric acid solution was added, and the addition was stopped at a pH of 3. Other conditions were the same as in example 1. The test results are shown in table 1.
Comparative example 1
50ml of water glass water solution with the concentration of 1.2mol/L is added into the reaction kettle, the stirring is started, and the temperature is increased to 50 ℃. Adding 1.1mol/L sodium silicate aqueous solution and 1.25mol/L sulfuric acid aqueous solution at the flow rate of 4ml/min in parallel, stopping adding the two mixed solutions when the pH value of the solution in the reaction kettle reaches 11, and reacting for 2.0 hours at constant temperature. Adding 1.0mol/L sulfuric acid aqueous solution at the flow rate of 6ml/min, stopping adding the sulfuric acid solution when the pH value of the solution is 9, and reacting for 2.0h at constant temperature. The reaction system is heated to 85 ℃ and reacts for 5.0h at constant temperature. Adding 1.0mol/L sulfuric acid water solution, and stopping adding when the pH value of the solution is 4. Cooling to room temperature, washing for three times by respectively using distilled water, a mixed solution of distilled water and ethanol, drying at 335 ℃, and activating for 4 hours at 600 ℃ under the protection of inert gas to obtain a carrier silica gel product. The test results are shown in table 1.
Comparative example 2
50ml of water glass water solution with the concentration of 1.2mol/L is added into the reaction kettle, the stirring is started, and the temperature is slowly increased to 50 ℃. Adding 1.1mol/L sodium silicate aqueous solution and 1.25mol/L sulfuric acid aqueous solution at the flow rate of 4ml/min in a concurrent flow manner, simultaneously adding 25ml of 6 mass percent sodium carbonate aqueous solution and 4 mass percent magnesium nitrate and aluminum nitrate mixed aqueous solution (the molar ratio of two nitrates is 1:2.5) at the flow rate of 5ml/min in a concurrent flow manner, stopping adding the mixed solution when the pH value of the solution in the reaction kettle reaches 11, and reacting at constant temperature for 2.0 hours. Adding 1.0mol/L aqueous solution of n-butanol sulfate (n-butanol to water volume ratio of 1:15) at flow rate of 6ml/min, stopping adding the solution of n-butanol sulfate when pH value of the solution is 9, and reacting at constant temperature for 2.0 h. The reaction system is heated to 85 ℃ and reacts for 5.0h at constant temperature. Adding 1.0mol/L sulfuric acid water solution, and stopping adding when the pH value of the solution is 4. Cooling to room temperature, washing for three times by respectively using distilled water, a mixed solution of distilled water and ethanol, drying at 335 ℃, and activating for 4 hours at 600 ℃ under the protection of inert gas to obtain a carrier silica gel product. The test results are shown in table 1.
Comparative example 3
50ml of water glass water solution with the concentration of 1.2mol/L is added into the reaction kettle, the stirring is started, and the temperature is slowly increased to 50 ℃. Adding 1.1mol/L sodium silicate aqueous solution and 1.25mol/L sulfuric acid aqueous solution at the flow rate of 4ml/min in a concurrent flow manner, simultaneously adding 25ml of ethanol aqueous solution (the volume ratio of ethanol to water is 1:6) with the mass fraction of 6% sodium carbonate and mixed aqueous solution (the molar ratio of two nitrates is 1:0.5) of magnesium nitrate and aluminum nitrate with the mass fraction of 4% in a concurrent flow manner at the flow rate of 5ml/min, stopping adding the mixed solution when the pH value of the solution in the reaction kettle reaches 11, and reacting at constant temperature for 2.0 hours. Adding 1.0mol/L sulfuric acid aqueous solution at the flow rate of 6ml/min, stopping adding the sulfuric acid solution when the pH value of the solution is 9, and reacting for 2.0h at constant temperature. The reaction system is heated to 85 ℃ and reacts for 5.0h at constant temperature. Adding 1.0mol/L sulfuric acid water solution, and stopping adding when the pH value of the solution is 4. Cooling to room temperature, washing for three times by respectively using distilled water, a mixed solution of distilled water and ethanol, drying at 335 ℃, and activating for 4 hours at 600 ℃ under the protection of inert gas to obtain a carrier silica gel product. The test results are shown in table 1.
Comparative example 4
50ml of water glass water solution with the concentration of 1.2mol/L is added into the reaction kettle, the stirring is started, and the temperature is slowly increased to 50 ℃. Adding 1.1mol/L sodium silicate aqueous solution and 1.25mol/L sulfuric acid aqueous solution at the flow rate of 4ml/min in a concurrent flow manner, simultaneously adding 25ml of aqueous solution of sodium carbonate with the mass fraction of 6% and mixed aqueous solution of magnesium nitrate and aluminum nitrate with the mass fraction of 4% (the molar ratio of the two nitrates is 1:1) at the flow rate of 5ml/min in a concurrent flow manner, stopping adding the mixed solution when the pH value of the solution in the reaction kettle reaches 11, and reacting at constant temperature for 2.0 hours. Adding 1.0mol/L sulfuric acid aqueous solution at the flow rate of 6ml/min, stopping adding the sulfuric acid aqueous solution when the pH value of the solution is 9, and reacting for 2.0h at constant temperature. The reaction system is heated to 85 ℃ and reacts for 5.0h at constant temperature. Adding 1.0mol/L sulfuric acid water solution, and stopping adding when the pH value of the solution is 4. Cooling to room temperature, washing for three times by respectively using distilled water, a mixed solution of distilled water and ethanol, drying at 335 ℃, and activating for 4 hours at 600 ℃ under the protection of inert gas to obtain a carrier silica gel product. The test results are shown in table 1.
TABLE 1 test results of physical Properties of Carrier silica gel
| Item | Specific surface area/(m)2/g) | Pore volume/(cm)3/g) | Pore size/nm |
| Example 1 | 533.1 | 2.28 | 17.11 |
| Example 2 | 527.6 | 2.23 | 16.91 |
| Example 3 | 530.3 | 2.19 | 16.52 |
| Example 4 | 524.5 | 2.21 | 16.85 |
| Example 5 | 526.2 | 2.23 | 16.95 |
| Example 6 | 525.3 | 2.22 | 16.90 |
| Example 7 | 526.3 | 2.24 | 17.02 |
| Comparative example 1 | 276.4 | 1.38 | 19.97 |
| Comparative example 2 | 388.4 | 1.79 | 18.43 |
| Comparative example 3 | 401.8 | 1.72 | 17.12 |
| Comparative example 4 | 378.2 | 1.62 | 17.13 |
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (12)
1. A preparation method of carrier silica gel for olefin catalysis is characterized in that silicate and inorganic acid are used as raw materials, and the preparation process is as follows:
1) taking a silicate aqueous solution as a base solution;
2) adding a silicate aqueous solution and an inorganic acid aqueous solution in a concurrent manner, and simultaneously adding an ethanol aqueous solution of an alkali metal carbonate and a mixed aqueous solution of two kinds of metal nitrates in a concurrent manner, wherein the mixed aqueous solution of the metal nitrates is selected from a mixed aqueous solution of magnesium nitrate and aluminum nitrate or a mixed aqueous solution of zinc nitrate and aluminum nitrate;
3) adjusting the pH value of the reaction solution to 10-12;
4) adding an organic alcohol aqueous solution of inorganic acid, wherein the volume ratio of the organic alcohol to the water is 1: 5-1: 30, and adjusting the pH value of the reaction solution to 9-10;
5) carrying out hydrothermal reaction at 70-100 ℃;
6) and acidifying, washing, drying and activating to obtain a silica gel product.
2. The method of claim 1, wherein the method comprises the following steps:
1) adding 30-60 ml of silicate aqueous solution with the concentration of 1.0-3.0 mol/L into a reaction kettle, and heating to 40-60 ℃ under the condition of stirring;
2) adding 1.0-3.0 mol/L silicate aqueous solution and 1.0-3.0 mol/L inorganic acid aqueous solution in a parallel flow manner, controlling the flow rate to be 3-6 ml/min, simultaneously adding 3-10% by mass of ethanol aqueous solution of alkali metal carbonate and 10-30 ml of mixed aqueous solution of two kinds of metal nitrates in a mass fraction of 2-8% in a parallel flow manner, and controlling the flow rate to be 4-7 ml/min; in an ethanol water solution of alkali metal carbonate, the volume ratio of ethanol to water is 1: 1-1: 10;
3) when the pH value of the reaction solution reaches 10-12, stopping adding the mixed solution, and reacting at constant temperature for 1.0-2.5 h;
4) adding an organic alcohol aqueous solution of inorganic acid with the concentration of 1.0-3.0 mol/L, controlling the flow rate to be 4-9 ml/min, controlling the volume ratio of the organic alcohol to the water to be 1: 5-1: 30, adjusting the pH value of the solution to be 9-10, and reacting at constant temperature for 1.0-2.5 h;
5) carrying out hydrothermal reaction for 3.0-5.0 h at 70-100 ℃;
6) and after the reaction is finished, adding 1.0-3.0 mol/L of inorganic acid aqueous solution, adjusting the pH value of the solution to 3-6, cooling the reaction system to normal temperature, washing by using distilled water or a mixed solution of distilled water and ethanol, drying at 300-335 ℃, and activating for 3.0-6.0 h at 400-600 ℃ under the condition of inert gas to obtain the carrier silica gel.
3. The method for preparing the carrier silica gel according to claim 2, wherein in the step 2), the volume ratio of ethanol to water is 1: 5-1: 9; in the preparation step 4), the volume ratio of the organic alcohol to the water is 1: 10-1: 20.
4. The method for preparing the carrier silica gel according to claim 1 or 2, wherein the silicate is selected from one or more of sodium silicate, potassium silicate and water glass, and the concentration of the silicate aqueous solution is 1.0 to 1.5 mol/L.
5. The method of claim 3, wherein the silicate is water glass.
6. The method for preparing the carrier silica gel according to claim 1 or 2, wherein the inorganic acid is one or more selected from sulfuric acid, hydrochloric acid and nitric acid, and the concentration of the aqueous solution of the inorganic acid is 1.0 to 1.3 mol/L.
7. The method of claim 6, wherein the inorganic acid is sulfuric acid.
8. The method for preparing carrier silica gel according to claim 1 or 2, characterized in that the alkali metal carbonate is selected from one or more of potassium carbonate and sodium carbonate, and the mass fraction is 4-7%.
9. The method for preparing the carrier silica gel according to claim 1 or 2, wherein the two metal nitrates are selected from a mixture of magnesium nitrate and aluminum nitrate or a mixture of zinc nitrate and aluminum nitrate, and the molar ratio of the two nitrates is 1:1 to 1:2.
10. The method of claim 9, wherein the molar ratio of the two metal nitrates is 1:1 to 1: 1.5.
11. The method of claim 1 or 2, wherein the organic alcohol is at least one selected from n-butanol, i-butanol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-1-butanol, 2, 2-dimethyl-1-propanol.
12. The method of claim 1 or 2, wherein the organic alcohol is selected from n-butanol and 1, 3-butanediol.
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