CN113385189B - Preparation method of trace noble metal modified titanium-silicon nano porous material - Google Patents

Preparation method of trace noble metal modified titanium-silicon nano porous material Download PDF

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CN113385189B
CN113385189B CN202010167503.3A CN202010167503A CN113385189B CN 113385189 B CN113385189 B CN 113385189B CN 202010167503 A CN202010167503 A CN 202010167503A CN 113385189 B CN113385189 B CN 113385189B
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noble metal
porous material
modified titanium
silicon nano
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CN113385189A (en
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李克亮
刘昱
段全进
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Wuzhong Mudu Tuoke Environmental Protection Technology Service Department
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8678—Removing components of undefined structure
    • B01D53/8687—Organic components
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract

The invention discloses a preparation method of a trace noble metal modified titanium-silicon nano porous material. Comprising the following steps: (1) adjusting the pH value of an alcohol solution of tetraethoxysilane to be 0.5-3.0 at the temperature of 30-50 ℃, and then sequentially adding butyl titanate, yttrium nitrate and/or ferric nitrate to prepare a solution B; (2) dropwise adding the solution B into the template agent solution A to obtain a solution C; (3) dropwise adding the chloroplatinic acid solution D into the solution C to obtain a solution E; (4) and removing the solvent from the solution E and roasting to obtain the product. The modified titanium-silicon nano porous material has large specific surface area and has adsorption and desorption functions on VOC pollutants; the catalyst plays the maximum effect, and really achieves low cost and high efficiency. The application in the field of VOC catalytic purification can reach the atmospheric emission standard, save energy, save economy and protect environment, and meet the treatment requirements of customers. The noble metal dosage is small, the cost is saved, the preparation process is simple, and the productivity is improved.

Description

Preparation method of trace noble metal modified titanium-silicon nano porous material
Technical Field
The invention relates to a preparation method of a trace noble metal modified titanium-silicon nano porous material.
Background
At present, the national environmental management is more and more powerful, the industrial waste gas emission is more and more strictly managed, along with the release of new atmospheric emission standards, the phenomenon of catalyst deactivation or catalytic efficiency attenuation easily occurs in the purification and use process of the traditional Volatile Organic Compound (VOC) catalyst, the production cost of the VOC catalytic purification agent is higher and higher, and environmental pollution is easily caused in the production process.
The existing VOC catalytic cleaner coating material is prepared by mixing a plurality of oxide powders according to a required proportion, and then repeatedly ball-milling to prepare micron-sized slurry; the slurry is subjected to vacuum adsorption adhesion roasting method (the vacuum adsorption adhesion is needed for 2 times) to prepare the VOC catalytic purification agent coating material. The existing VOC catalytic cleaner coating materials have the following defects: (1) The noble metal dosage is 14-56g/ft 3 Resulting in higher costs required; (2) The preparation process is complex and tedious, has high cost and is easy to cause environmental pollution.
In addition, the existing VOC catalytic cleaner coating materials are various in multiple modes, and are adjusted on the production cost, so that the performance of the catalytic cleaner is affected, the catalytic efficiency can not be ensured sometimes, and the service life is short. At present, the demand of the domestic market for VOC catalytic purifying agents is conservatively estimated to be about 500 kiloliters, and as the management of industrial waste gas emission is more and more strict, the production cost of the traditional VOC catalysts is necessarily increased, and the emission standard cannot be completely reached.
Disclosure of Invention
The invention aims to overcome the defects of high noble metal consumption, high cost, complex and tedious preparation process and easy environmental pollution of the VOC catalytic purification agent coating material in the prior art, and provides a preparation method of a trace noble metal modified titanium-silicon nano porous material.
The invention solves the technical problems through the following technical proposal.
The invention provides a preparation method of a trace noble metal modified titanium silicon nano porous material, which comprises the following steps:
(1) Adjusting the pH value of an alcohol solution of tetraethoxysilane to be 0.5-3.0 at the temperature of 30-50 ℃, sequentially adding butyl titanate, yttrium nitrate and/or ferric nitrate, and carrying out a mixing reaction to obtain a solution B; wherein the pH value regulator is nitric acid solution with the concentration of 60-70%, and the mass ratio of the tetraethoxysilane to the butyl titanate is (50-65): (1000-1200);
when the solution B contains the yttrium nitrate, the mass ratio of the tetraethoxysilane to the yttrium nitrate is (50-65): (10-20); when the solution B contains the ferric nitrate, the mass ratio of the tetraethoxysilane to the ferric nitrate is (50-65): (5-10);
(2) Dropwise adding the solution B into the template agent solution A to obtain a solution C; wherein the mass ratio of the template agent to the tetraethoxysilane is (150-250): (50-65);
(3) Dropwise adding the chloroplatinic acid solution D into the solution C to obtain a solution E; wherein the mass ratio of the template agent to the chloroplatinic acid is (150-250): (1-5);
(4) And removing the solvent from the solution E, and roasting to obtain the product.
In the step (1), the solvent used in the alcohol solution of ethyl orthosilicate may be an alcohol solvent conventional in the art, preferably absolute ethanol.
In step (1), the mass ratio of ethyl orthosilicate to solvent in the alcoholic solution of ethyl orthosilicate may be conventional in the art, preferably (50-65): (800-1000), e.g. 58:900.
In the step (1), the water content of the nitric acid solution with the concentration of 60-70% is 30-40%. The mass ratio of the nitric acid solution with the concentration of 60-70% to the tetraethoxysilane is preferably (60-90): (50-65).
In step (1), the pH is preferably 2.
In step (1), the operation and conditions of the mixing reaction may be conventional in the art, which is a hydrolysis reaction of ethyl orthosilicate. In the course of the mixing reaction, the stirring speed is preferably 150 to 300 revolutions/min. The mixing reaction time is preferably 25 to 45 minutes.
In step (1), the solution B is preferably prepared by: 50-65 g of ethyl orthosilicate is added into 800-1000 g of absolute ethyl alcohol at the temperature of 30-50 ℃ and the stirring speed of 150-300 r/min, the mixture is stirred for 20-30 min, 8-15 g of nitric acid is added to adjust the pH value to 0.5-3.0, 5-8 g of ethyl orthosilicate is added, the mixture is stirred for 20-40 min at the stirring speed of 150-300 r/min, 1000-1200 g of butyl titanate, 10-20 g of yttrium nitrate and/or 5-10 g of ferric nitrate are added, and the mixture is stirred for 25-45 min.
In the step (1), the mass ratio of the tetraethoxysilane to the tetrabutyl titanate may be 58:1100.
in the step (1), when the solution B contains the yttrium nitrate, the mass ratio of the tetraethyl orthosilicate to the yttrium nitrate may be 58:16.
In the step (1), when the solution B contains the ferric nitrate, the mass ratio of the tetraethyl orthosilicate to the ferric nitrate may be 58:6.
In the step (2), the operation and conditions of the dripping may be those conventional in the art, and the dripping is generally performed by using a peristaltic pump for liquid.
In the step (2), stirring is preferably performed during the dropping process. The stirring speed may be conventional in the art, preferably 150 to 300 revolutions/min.
In step (2), the dropping speed may be conventional in the art, preferably 2 to 5g/min, more preferably 3g/min.
In the step (2), after the solution B is added dropwise, stirring is preferably continued for 1-2 hours.
In step (2), the solvent of the template solution A may be a solvent capable of dissolving the template as is conventional in the art, preferably absolute ethanol.
In the step (2), the mass ratio of the template agent to the solvent in the template agent solution a may be conventional in the art, and is preferably (150 to 250): (600-800), e.g., 200:700.
In step (2), the template solution A is preferably prepared by the steps of: at 30-50 ℃, 150-250 g of template agent is added into 600-800 g of absolute ethyl alcohol, and the mixture is stirred until the template agent is completely dissolved. The stirring speed may be conventional in the art, preferably 150 to 300 revolutions/min.
In step (2), the template may be a molding template conventional in the art in the preparation of porous materials, preferably a polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer (i.e., a template of P123), available from Sigma-Aldrich.
In the step (2), the mass ratio of the template agent to the tetraethyl orthosilicate is preferably 200:58.
in the step (3), the operation and conditions of the dripping may be those conventional in the art, and the dripping is generally performed by using a peristaltic pump for liquid.
In the step (3), stirring is preferably performed during the dropping process. The stirring speed may be conventional in the art, preferably 150 to 300 revolutions/min.
In step (3), the dropping speed may be conventional in the art, preferably 2 to 5g/min, more preferably 3g/min. The dripping process is an embedding process of filling the effective substance on the net structure of the template agent, and if the dripping speed is less than 2g/min or is more than 5g/min, the dripping speed can cause the effective substance to be excessively filled or excessively reduced, and the solution can be layered.
In the step (3), after the solution D is added dropwise, stirring is preferably continued for 1 to 2 hours.
In step (3), the solution D is preferably prepared by: and adding 1-5 g of chloroplatinic acid into 30-50 g of absolute ethyl alcohol at the stirring speed of 150-300 rpm, and stirring until the chloroplatinic acid is completely dissolved.
In the step (3), the mass percentage of the chloroplatinic acid in the total amount of the solution D in the solution D may be conventional in the art, and is preferably (1 to 5): (3 to 50), more preferably 4:40.
in step (3), the solvent in the solution D may be a solvent capable of dissolving chloroplatinic acid as is conventional in the art, preferably absolute ethanol.
In the step (3), the mass ratio of the template agent to the chloroplatinic acid is preferably 200:4.
in step (4), the solvent removal operation and conditions may be conventional in the art, preferably by vacuum plating the solution E onto a support and drying.
Wherein the support may be conventional in the art, preferably a cordierite honeycomb ceramic support. The carrier is purchased from Jiangxi Jitai environmental protection ceramic limited company or Jiangsu Yixing prince ceramic limited company. The pressure of the vacuum plating is preferably-0.08 to 0MPa. Preferably, the carrier is pretreated before vacuum plating, and the pretreatment is to load a layer of alumina on the carrier. The drying operation and conditions may be those conventional in the art. The temperature of the drying is preferably 40 to 60 ℃. The drying time is preferably 3 to 5 hours.
Wherein, the operation and condition of vacuum plating can be the conventional operation and condition in the field, generally means that the solution is adsorbed onto the carrier from bottom to top or from top to bottom under the vacuum condition, and a layer of nano film is formed on the carrier after drying and roasting, and is integrated with the carrier.
In step (4), the operation and conditions of the calcination may be conventional in the art. The temperature of the calcination is preferably 600 to 800 ℃. The calcination time is preferably 15 to 20 hours.
In the invention, the dosage of the template agent directly influences the filling amount of each effective substance in a molecular sieve structure system, and the raw material screening in the synthesis process takes the molecular diameter of each substance as a reference, so that the substances can be mutually embedded to form solid solution. Therefore, the proportion of the template agent, the butyl titanate and the ethyl orthosilicate has the most important effect on preparing the porous material. Moreover, for the addition sequence of the ethyl orthosilicate and the butyl titanate, the ethyl orthosilicate and the butyl titanate must be added first, and if the addition is carried out simultaneously or in reverse order, the generation of nano particles and the size of the nano particles are affected.
The invention also provides a trace noble metal modified titanium-silicon nano porous material prepared by the preparation method.
The trace noble metal modified titanium-silicon nano porous material contains wide and non-concentrated pore size distribution, the pore diameter is 2-500 nm (micropores, mesopores and macropores), the particle size is 10-19 nm, and the crystal form is spinel.
The invention also provides application of the trace noble metal modified titanium-silicon nano porous material in preparing the VOC catalytic purification agent coating material.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that:
the trace noble metal modified titanium-silicon nano porous material has large specific surface area and has adsorption and desorption functions on VOC pollutants; the coating of the VOC catalytic purification agent is prepared by adopting a vacuum adsorption plating roasting method, and only needs to be plated for 1 time, so that the effective matters can be uniformly distributed on the carrier, the catalyst can exert the maximum effect, and the low cost and the high efficiency are really realized. The application in the field of VOC catalytic purification can reach the atmospheric emission standard, save energy, save economy and protect environment, and meet the treatment requirements of customers. In addition, the noble metal dosage is only 5.6-42g/ft 3 The cost is saved, the preparation process is simple, no pollution is caused, and the productivity is improved.
Drawings
FIG. 1 is a graph showing pore size distribution of a trace amount of noble metal-modified titanium-silicon nanoporous material obtained in example 3.
Fig. 2 is a TEM electron microscope image of the micro noble metal modified titanium silicon nano porous material obtained in example 3.
FIG. 3 is a graph showing the conversion rate of xylene at different reaction temperatures of the trace noble metal-modified titanium-silicon nanoporous materials obtained in examples 1 to 3.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
The templates used in the following examples and comparative examples were polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymers (i.e., templates for P123), purchased from Sigma-Aldrich; the carrier is cordierite honeycomb ceramic carrier purchased from Jiangxi Jitai environmental protection ceramic Co., ltd or Jiangsu Yixing prince ceramic Co., ltd.
Example 1
1. 600g of absolute ethyl alcohol is weighed and placed in a 1000ml beaker, stirred (150 revolutions per minute) and heated to 30 ℃, 250g of template agent is added, and stirred for 20 minutes to be completely dissolved, so that A liquid is prepared;
2. weighing 800g of absolute ethyl alcohol, placing the absolute ethyl alcohol into a 2000ml beaker, stirring (150 revolutions per minute), adding 50g of tetraethoxysilane, stirring for 20 minutes, adding 60g of nitric acid to adjust the pH value of the solution to 0.5, adding 1000g of butyl titanate, sequentially adding 15g of yttrium nitrate and 10g of ferric nitrate, and stirring for 25 minutes to obtain solution B;
3. dropwise adding the solution B (2 g/min) into the solution A, stirring for 1h after the dropwise adding is completed to prepare solution C,
4. 30g of absolute ethyl alcohol is weighed and placed in a 100ml beaker to be stirred (150 revolutions per minute), 1.5g of chloroplatinic acid (0.57 g of platinum) is added, and after complete dissolution, solution D is prepared;
5. dropwise adding the solution D (2 g/min) into the solution C, and stirring for 1h after the dropwise adding is finished to obtain solution E;
6. and quantitatively and vacuum plating the synthesized E liquid (the vacuum plating pressure is-0.08-0 MPa) on a cordierite honeycomb ceramic carrier, drying at 40 ℃ for 3h, and roasting at 400 ℃ for 4h to obtain the modified titanium-silicon nano porous material.
Example 2
1. 800g of absolute ethyl alcohol is weighed and placed in a 1000ml beaker, stirred (300 revolutions per minute) and heated to 50 ℃, 150g of template agent is added, and stirring is carried out for 40 minutes, so that the solution A is prepared.
2. Weighing 1000g of absolute ethyl alcohol, placing the absolute ethyl alcohol into a 2000ml beaker, stirring (300 revolutions per minute), adding 65g of tetraethoxysilane, stirring for 30 minutes, adding 90g of nitric acid to adjust the pH value of the solution to 3.0, adding 1200g of butyl titanate and 8g of ferric nitrate, and stirring for 45 minutes to prepare solution B;
3. dropwise adding the solution B (5 g/min) into the solution A, and stirring for 1h after the dropwise adding is finished to prepare solution C;
4. 50g of absolute ethyl alcohol is weighed and placed in a 100ml beaker to be stirred (300 revolutions per minute), 2.5g of chloroplatinic acid (0.95 g of platinum) is added, and after complete dissolution, solution D is prepared;
5. dropwise adding the solution D (5 g/min) into the solution C, and stirring for 1h after the dropwise adding is finished to obtain solution E;
6. and quantitatively and vacuum plating the synthesized E liquid (the vacuum plating pressure is-0.08-0 MPa) on a cordierite honeycomb ceramic carrier, drying for 5h at 60 ℃, and roasting for 4h at 600 ℃ to obtain the modified titanium-silicon nano porous material.
Example 3
1. Weighing 700g of absolute ethyl alcohol, placing the absolute ethyl alcohol into a 1000ml beaker, stirring (300 revolutions per minute), heating to 30 ℃, adding 200g of template agent, and stirring for 20 minutes to completely dissolve the template agent to prepare solution A;
2. weighing 900g of absolute ethyl alcohol, placing the absolute ethyl alcohol into a 2000ml beaker, stirring (150 revolutions per minute), adding 58g of tetraethoxysilane, stirring for 20 minutes, adding nitric acid to adjust the pH value of the solution to 2, adding 1100g of butyl titanate, sequentially adding 16g of yttrium nitrate and 6g of ferric nitrate, and stirring for 45 minutes to obtain solution B;
3. dropwise adding the solution B (3 g/min) into the solution A, and stirring for 1h after the dropwise adding is finished to prepare solution C;
4. 40g of absolute ethyl alcohol is weighed and placed in a 100ml beaker to be stirred (300 revolutions per minute), 4g of chloroplatinic acid (1.52 g of platinum) is added, and after complete dissolution, solution D is prepared;
5. dropwise adding the solution D (3 g/min) into the solution C, and stirring for 1h after the dropwise adding is finished to obtain solution E;
6. and quantitatively and vacuum plating the synthesized E liquid (the vacuum plating pressure is-0.08-0 MPa) on a cordierite honeycomb ceramic carrier, drying at 60 ℃ for 3h, and roasting at 600 ℃ for 4h to obtain the modified titanium-silicon nano porous material.
Comparative example 1
1. Weighing 800g of 95% ethanol (95% purity), placing in a 1000ml beaker, stirring (300 rpm) and heating to 50 ℃, adding 120g of template agent, stirring for 40min to completely dissolve, and obtaining solution A;
2. weighing 1000g of absolute ethyl alcohol, placing the absolute ethyl alcohol into a 2000ml beaker, stirring (300 revolutions per minute), adding 65g of tetraethoxysilane, stirring for 30 minutes, adding 90g of nitric acid to adjust the pH value of the solution to 3.0, adding 1200g of butyl titanate and 8g of ferric nitrate, and stirring for 45 minutes to prepare solution B;
3. dropwise adding the solution B (5 g/min) into the solution A, and stirring for 1h after the dropwise adding is finished to prepare solution C;
4. weighing 50g of absolute ethyl alcohol, placing the absolute ethyl alcohol into a 100ml beaker, stirring (300 revolutions per minute), adding 6g of chloroplatinic acid, and preparing solution D after complete dissolution;
5. dropwise adding the solution D (5 g/min) into the solution C, and stirring for 1h after the dropwise adding is finished to obtain solution E;
6. and quantitatively and vacuum plating the synthesized E liquid (the vacuum plating pressure is-0.08-0 MPa) on a cordierite honeycomb ceramic carrier, drying for 5h at 60 ℃, and roasting for 4h at 600 ℃ to obtain the modified titanium-silicon nano porous material.
The content of platinum in the modified titanium-silicon nano porous material prepared in the comparative example is 38%.
Effect example 1
FIG. 1 is a graph showing pore size distribution of a trace amount of noble metal-modified titanium-silicon nanoporous material obtained in example 3. Wherein the ordinate is the cumulative mercury injection curve in mL (milliliter)/g (gram). Indicating the pore size and below, all pores, and how much mercury is contained in total. The abscissa indicates the pore size in nanometers. As can be seen from the above FIG. 1, the trace noble metal modified titanium-silicon nano porous material prepared by the invention has wide and non-concentrated pore size distribution; the aperture is 2-500 nm (micropores, mesopores and macropores), the crystal form is spinel Dan Xing (the detection method is mercury intrusion method).
Fig. 2 is a TEM electron microscope image of the micro noble metal modified titanium silicon nano porous material obtained in example 3. As can be seen from FIG. 2, the particle size of the material is 10 to 19nm.
Table 1 shows the specific surface areas, pore size ranges, particle diameters and metal amounts of the products obtained in examples 1 to 3 and comparative example 1.
TABLE 1
Effect example 2
FIG. 3 is a graph showing the conversion rate of xylene at different reaction temperatures of the trace noble metal-modified titanium-silicon nanoporous materials obtained in examples 1 to 3. The specific test method comprises the following steps: in a pretreatment atmosphere (20% O) 2 ，N 2 Balance gas), the temperature is increased to 500 ℃ at a heating rate of 10 ℃/min for 30min, the temperature is reduced to 80 ℃ for stabilization, and the temperature is increased to 550 ℃ at a heating rate of 10 ℃/min for VOC reaction. Specific evaluation conditions are shown in table 2:
TABLE 2
Table 3 shows the conversion of xylene at 275℃light-off temperature of the trace amount of noble metal-modified titanium-silicon nanoporous material obtained in examples 1 to 3 and comparative example 1.
TABLE 3 Table 3

Claims (14)

1. The preparation method of the trace noble metal modified titanium-silicon nano porous material is characterized by comprising the following steps of:
(1) Adjusting the pH value of an alcohol solution of tetraethoxysilane to be 0.5-3.0 at the temperature of 30-50 ℃, sequentially adding butyl titanate, yttrium nitrate and/or ferric nitrate, and carrying out a mixing reaction to obtain a solution B; wherein the pH value regulator is nitric acid solution with the concentration of 60-70%, and the mass ratio of the tetraethoxysilane to the butyl titanate is (50-65): (1000-1200);
when the solution B contains the yttrium nitrate, the mass ratio of the tetraethoxysilane to the yttrium nitrate is (50-65): (10-20); when the solution B contains the ferric nitrate, the mass ratio of the tetraethoxysilane to the ferric nitrate is (50-65): (5-10);
(2) Dropwise adding the solution B into the template agent solution A to obtain a solution C; wherein the mass ratio of the template agent to the tetraethoxysilane is (150-250): (50-65);
(3) Dropwise adding the chloroplatinic acid solution D into the solution C to obtain a solution E; wherein the mass ratio of the template agent to the chloroplatinic acid is (150-250): (1-5);
(4) And removing the solvent from the solution E, and roasting to obtain the product.
2. The method for preparing a trace amount of noble metal modified titanium silicon nano porous material according to claim 1, wherein in the step (1), absolute ethyl alcohol is adopted as a solvent in the alcohol solution of the ethyl orthosilicate;
and/or in the step (1), in the alcohol solution of the ethyl orthosilicate, the mass ratio of the ethyl orthosilicate to the solvent is (50-65) (800-1000);
and/or, in the step (1), the mass ratio of the nitric acid solution with the concentration of 60-70% to the tetraethoxysilane is (60-90): (50-65);
and/or, in step (1), the pH is 2;
and/or in the step (1), in the process of the mixing reaction, the stirring speed is 150-300 r/min; the time of the mixing reaction is 25-45 min.
3. The method for preparing a trace amount of noble metal modified titanium silicon nano-porous material according to claim 1, wherein in the step (1), the mass ratio of the ethyl orthosilicate to the solvent in the alcohol solution of the ethyl orthosilicate is 58:900.
4. The method for preparing a trace amount of noble metal modified titanium silicon nano-porous material according to claim 1, wherein in the step (1), the solution B is prepared by the steps of: adding 50-65 g of ethyl orthosilicate into 800-1000 g of absolute ethyl alcohol at the temperature of 30-50 ℃ and the stirring speed of 150-300 r/min, stirring for 20-30 min, adding 8-15 g of nitric acid to adjust the pH value to 0.5-3.0, adding 5-8 g of ethyl orthosilicate, stirring for 20-40 min at the stirring speed of 150-300 r/min, adding 1000-1200 g of butyl titanate, 10-20 g of yttrium nitrate and/or 5-10 g of ferric nitrate, and stirring for 25-45 min;
and/or, in the step (1), the mass ratio of the tetraethoxysilane to the butyl titanate is 58:1100, a method for manufacturing the same;
and/or, in the step (1), when the yttrium nitrate is contained in the solution B, the mass ratio of the tetraethoxysilane to the yttrium nitrate is 58:16;
and/or, in the step (1), when the solution B contains the ferric nitrate, the mass ratio of the tetraethoxysilane to the ferric nitrate is 58:6.
5. The method for preparing a trace noble metal modified titanium-silicon nano porous material according to claim 1, wherein in the step (2), stirring is performed in the dropping process, and the stirring speed is 150-300 rpm;
and/or in the step (2), the dropping speed is 2-5 g/min;
and/or in the step (2), after the solution B is added dropwise, stirring is continued for 1-2 h;
and/or, in the step (2), the solvent of the template agent solution A is absolute ethyl alcohol.
6. The method for preparing a trace amount of noble metal modified titanium silicon nano-porous material according to claim 1, wherein in the step (2), the dropping speed is 3g/min.
7. The method for preparing a trace noble metal modified titanium silicon nano porous material according to claim 1, wherein in the step (2), the mass ratio of the template agent to the solvent in the template agent solution A is (150-250): (600-800);
and/or, in the step (2), the template solution A is prepared by the following steps: adding 150-250 g of template agent into 600-800 g of absolute ethyl alcohol at 30-50 ℃, and stirring until the template agent is completely dissolved;
and/or, in the step (2), the template agent is a polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer;
and/or, in the step (2), the mass ratio of the template agent to the tetraethoxysilane is 200:58.
8. the method for preparing a trace noble metal modified titanium-silicon nano-porous material according to claim 1, wherein in the step (2), the mass ratio of the template agent to the solvent in the template agent solution A is 200:700.
9. The method for preparing a trace noble metal modified titanium-silicon nano porous material according to claim 1, wherein in the step (3), stirring is performed in the dropping process, and the stirring speed is 150-300 rpm;
and/or in the step (3), the dropping speed is 2-5 g/min;
and/or in the step (3), after the solution D is added dropwise, stirring is continued for 1-2 h.
10. The method for preparing a trace amount of noble metal modified titanium silicon nano-porous material according to claim 1, wherein in the step (3), the dropping speed is 3g/min.
11. The method for preparing a trace amount of noble metal modified titanium silicon nano-porous material according to claim 1, wherein in the step (3), the solution D is prepared by the steps of: adding 1-5 g of chloroplatinic acid into 30-50 g of absolute ethyl alcohol at the stirring speed of 150-300 rpm, and stirring until the chloroplatinic acid is completely dissolved;
and/or, in the step (3), in the solution D, the mass percentage of chloroplatinic acid in the total amount of the solution D is (1-5): (3-50);
and/or, in the step (3), the solvent in the solution D is absolute ethyl alcohol;
and/or, in the step (3), the mass ratio of the template agent to the chloroplatinic acid is 200:4.
12. the method for preparing a trace amount of noble metal modified titanium silicon nano-porous material according to claim 11, wherein in the step (3), the mass percentage of chloroplatinic acid in the solution D is 4:40.
13. the method for preparing a trace amount of noble metal modified titanium silicon nano-porous material according to claim 1, wherein in the step (4), the operation of removing the solvent is to dry the solution E by vacuum plating on a carrier;
and/or, in the step (4), the roasting temperature is 600-800 ℃;
and/or in the step (4), the roasting time is 15-20 h.
14. The method for preparing a trace amount of noble metal modified titanium silicon nano porous material according to claim 13, wherein the carrier is a cordierite honeycomb ceramic carrier;
and/or the vacuum plating pressure is-0.08-0 MPa;
and/or, pre-treating the carrier before vacuum plating, wherein the pre-treating is to load a layer of alumina on the carrier;
and/or, the temperature of the drying is 40-60 ℃;
and/or the drying time is 3-5 h.
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