CN109821524B - Preparation method of photo-degradable organic toxic gas multistage nano composite material - Google Patents
Preparation method of photo-degradable organic toxic gas multistage nano composite material Download PDFInfo
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- CN109821524B CN109821524B CN201910219602.9A CN201910219602A CN109821524B CN 109821524 B CN109821524 B CN 109821524B CN 201910219602 A CN201910219602 A CN 201910219602A CN 109821524 B CN109821524 B CN 109821524B
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002341 toxic gas Substances 0.000 title claims abstract description 27
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010936 titanium Substances 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 239000011941 photocatalyst Substances 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 12
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 10
- 238000012986 modification Methods 0.000 claims abstract description 10
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- 239000002131 composite material Substances 0.000 claims abstract description 6
- 238000013329 compounding Methods 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 10
- 229910003472 fullerene Inorganic materials 0.000 claims description 10
- GPQWKLDEDGOJQH-UHFFFAOYSA-N ethane-1,1,1,2-tetramine Chemical compound NCC(N)(N)N GPQWKLDEDGOJQH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 53
- 238000006243 chemical reaction Methods 0.000 description 52
- 238000010298 pulverizing process Methods 0.000 description 43
- 230000035484 reaction time Effects 0.000 description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 17
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- 238000003756 stirring Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 230000031700 light absorption Effects 0.000 description 5
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- 229960000892 attapulgite Drugs 0.000 description 2
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- 239000006185 dispersion Substances 0.000 description 2
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Abstract
The invention discloses a preparation method of a multistage nano composite material with photodegradable organic toxic gas, which comprises the following steps: montmorillonite is crushed to have an average particle size of 50-200 nm by a mechanical crushing method and an air flow method; preliminary preparation of the nano composite material: compounding the montmorillonite and the titanium photocatalyst material at low temperature to obtain a compound, adding the compound into water or alcohol, reacting at low temperature, and then adding a nitrogen source or a carbon source for reacting to obtain a primary nano composite material; modification of the multistage nanocomposite: cooling the primary nano composite material, and then adding a modifier for modification, wherein the modifier accounts for 0.2-2% of the total mass of the composite/water or alcohol/nitrogen source or carbon source system; the modifier comprises glycerol or triethanolamine.
Description
Technical Field
The invention belongs to the technical field of functional nano powder, and particularly relates to a preparation method of a multistage nano composite material capable of photo-degrading organic toxic gas.
Background
Titanium catalysts have a long research history, researches show that titanium dioxide has a good photocatalytic effect when the titanium dioxide is below 20nm, but an effective light source of the titanium dioxide is limited to ultraviolet excitation, so that the application of the titanium dioxide is limited, and researches on modifying the titanium dioxide are carried out on the titanium dioxide, specifically, a noble metal or rare earth metal element is adopted to dope an anatase titanium dioxide catalyst, so that the photocatalytic stability of the anatase titanium dioxide catalyst can be improved, but the improvement on the wave absorbing range of the anatase titanium dioxide catalyst is limited, and the doping of the rare earth metal can bring the pollution of associated heavy metal ions, so that the complete health and environmental protection can not be realized, and the function of enriching harmful gases is not increased in the existing photocatalyst modification process, so that the efficiency of photocatalytic degradation of organic and toxic gases can not be maximally improved And (6) obtaining.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made in view of the above-mentioned technical drawbacks.
Therefore, as one aspect of the present invention, the present invention overcomes the disadvantages of the prior art and provides a method for preparing a multistage nanocomposite material with photodegradable organic toxic gas.
In order to solve the technical problems, the invention provides the following technical scheme: a method for preparing a multistage nano composite material with photodegradable organic toxic gas comprises the following steps,
preparing porous layered nano montmorillonite: montmorillonite is crushed to have an average particle size of 50-200 nm by a mechanical crushing method and an air flow method;
preliminary preparation of the nano composite material: compounding the montmorillonite and the titanium photocatalyst material at low temperature to obtain a compound, adding the compound into water or alcohol, reacting at low temperature, and then adding a nitrogen source or a carbon source for reacting to obtain a primary nano composite material; the mass ratio of the montmorillonite to the titanium photocatalyst material is 1: (10-50); the mass ratio of the compound to water or alcohol is 1: (5-20), wherein the nitrogen source or the carbon source accounts for 0.1-5% of the total mass of the compound and water or alcohol;
modification of the multistage nanocomposite: cooling the primary nano composite material, and then adding a modifier for modification, wherein the modifier accounts for 0.2-2% of the total mass of the composite/water or alcohol/nitrogen source or carbon source system; the modifier comprises glycerol or triethanolamine.
As a preferred scheme of the preparation method of the photo-degradable organic toxic gas multistage nano composite material, the preparation method comprises the following steps: the mechanical crushing method has the crushing time of 0.5-1 h and the rotating speed of 400-1200 rpm.
As a preferred scheme of the preparation method of the photo-degradable organic toxic gas multistage nano composite material, the preparation method comprises the following steps: the airflow crushing has the gas flow of 2-4 m3/min, the gas pressure of 0.7-1.5 MPa and the crushing efficiency of 10-30 Kg/h.
As a preferred scheme of the preparation method of the photo-degradable organic toxic gas multistage nano composite material, the preparation method comprises the following steps: the montmorillonite and the titanium photocatalyst material are compounded at low temperature, wherein the titanium photocatalyst material comprises titanium tetrachloride.
As a preferred scheme of the preparation method of the photo-degradable organic toxic gas multistage nano composite material, the preparation method comprises the following steps: the montmorillonite and the titanium photocatalyst material are compounded at a low temperature of 1-5 ℃.
As a preferred scheme of the preparation method of the photo-degradable organic toxic gas multistage nano composite material, the preparation method comprises the following steps: adding the compound into water or alcohol, and reacting at a low temperature of 1-5 ℃ for 10-50 min; the alcohol comprises ethanol.
As a preferred scheme of the preparation method of the photo-degradable organic toxic gas multistage nano composite material, the preparation method comprises the following steps: the nitrogen source comprises triamino ethylamine, ethylenediamine and ammonia water.
As a preferred scheme of the preparation method of the photo-degradable organic toxic gas multistage nano composite material, the preparation method comprises the following steps: the carbon source comprises fullerene, graphene and citric acid; the citric acid is a pure substance modified by sodium salt.
As a preferred scheme of the preparation method of the photo-degradable organic toxic gas multistage nano composite material, the preparation method comprises the following steps: and adding a nitrogen source or a carbon source for reaction, wherein the reaction temperature is 120-180 ℃, and the reaction time is 4-8 h.
As a preferred scheme of the preparation method of the photo-degradable organic toxic gas multistage nano composite material, the preparation method comprises the following steps: the carbon source has a molecular average particle size of 2-5 nm.
The invention has the beneficial effects that: the porous montmorillonite material adopted by the multistage nano composite material for photo-degrading organic toxic gas has uniform gap distribution, can be used as a reaction carrier for preparing a small-size titanium catalyst, and plays roles in controllable preparation and controllable dispersion of the nitrogen or carbon element doped titanium photocatalyst nano material in size. The nano composite material is subjected to surface modification, so that the powder can be uniformly dispersed in a water system and the effect of preventing coprecipitation is achieved. Compared with the existing materials, the material has wide light absorption range, can absorb the light wavelength range of 200-900 nm, basically covers ultraviolet-visible light and near infrared regions, has high energy utilization rate, improves the photodegradation efficiency, and simultaneously realizes the enrichment of organic toxic gas by the porous structure in the multistage nano structure, thereby greatly improving the catalytic efficiency of the titanium photocatalyst.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 shows the formaldehyde degradation rate of the nanocomposite prepared in example 1 of the present invention, wherein the formaldehyde degradation rate reaches 95% after 0.5h of reaction.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1:
pulverizing 10Kg montmorillonite by mechanical pulverizing method at 800rpm for 45min, and pulverizing for 1 time by air flow method at pulverizing pressure of 1.0MPa and gas flow of 3m3And/min, the crushing efficiency is 20Kg/h, the particle size is measured to be 180nm, 4g of titanium tetrachloride is weighed and added into 50g of processed porous montmorillonite, the operation condition is that the titanium tetrachloride is gradually added and operated in a low-temperature box, the operation temperature is 3 ℃, a compound is obtained, 10g of the compound is added into 100ml of deionized water, the low-temperature hydrolysis reaction is carried out, the reaction time is 30min, the reaction temperature is 3 ℃, 0.5g of fullerene with the particle size of 5nm is added after the reaction, the reaction is carried out at 160 ℃, the reaction time is 6h, 1.5g of triethanolamine is added after the temperature is reduced to the normal temperature, and the nano composite material is obtained after the stirring is uniform.
And (3) testing: 0.1ml of solution is added into 10ml of formaldehyde solution, and the reaction is carried out for 0.5h under the irradiation of visible light, and the degradation rate of formaldehyde reaches 95 percent. The nano composite material has a wide light absorption range, and can absorb light with a wavelength of 200-900 nm.
According to the invention, researches show that the hydrolysis speed of titanium tetrachloride is controlled, the photocatalyst material with small particle size can be prepared, and the triethanolamine modifies the composite material system, so that the coprecipitation of the multistage nano material can be effectively prevented, the stability of the multistage nano material in a water system is increased, and the dispersibility is obviously improved. The nano composite material prepared by the invention has the function of efficiently photodegrading organic toxic gas.
Example 2:
pulverizing 10Kg montmorillonite by mechanical pulverizing method at 800rpm for 45min, and pulverizing for 1 time by air flow method at pulverizing pressure of 1.0MPa and gas flow of 3m3And/min, the crushing efficiency is 20Kg/h, the particle size is measured to be 180nm, 4g of titanium tetrachloride is weighed and added into 50g of processed porous montmorillonite, the operation condition is that the titanium tetrachloride is gradually added and operated in a low-temperature box, the operation temperature is 3 ℃, a compound is obtained, 10g of the compound is added into 100ml of deionized water, the low-temperature hydrolysis reaction is carried out, the reaction time is 30min, the reaction temperature is 3 ℃, 0.5g of fullerene with the particle size of 5nm is added after the reaction, the reaction is carried out at 160 ℃, the reaction time is 6h, the reaction time is reduced to the normal temperature, 1.5g of glycerol is added and the mixture is uniformly stirred, and the nano composite material is obtained.
And (3) testing: 0.1ml of solution is added into 10ml of formaldehyde solution, and the reaction is carried out for 0.5h under the irradiation of visible light, and the degradation rate of formaldehyde reaches 80 percent. The nano composite material has a wide light absorption range, and can absorb light with a wavelength of 200-900 nm.
Example 3:
pulverizing 10Kg montmorillonite by mechanical pulverizing method at 800rpm for 45min, and pulverizing for 1 time by air flow method at pulverizing pressure of 1.0MPa and gas flow of 3m3And/min, the crushing efficiency is 20Kg/h, the particle size is measured to be 180nm, 4g of titanium tetrachloride is weighed and added into 50g of processed porous montmorillonite, the operation condition is that the titanium tetrachloride is gradually added and operated in a low-temperature box, the operation temperature is 3 ℃, a compound is obtained, 10g of the compound is added into 100ml of deionized water, the low-temperature hydrolysis reaction is carried out, the reaction time is 30min, the reaction temperature is 3 ℃, 0.5g of triamino-ethylamine with the particle size of 5nm is added after the reaction, the reaction is carried out at 160 ℃, the reaction time is 6h, 1.5g of triethanolamine is added after the temperature is reduced to the normal temperature, and the nano composite material is obtained after the stirring is uniform.
And (3) testing: 0.1ml of solution is added into 10ml of formaldehyde solution, and the reaction is carried out for 0.5h under the irradiation of visible light, and the degradation rate of formaldehyde reaches 87%. . The nano composite material has a wide light absorption range, and can absorb light with a wavelength of 200-900 nm.
Example 4:
pulverizing 10Kg montmorillonite by mechanical pulverizing method at 800rpm for 45min, and pulverizing for 1 time by air flow method at pulverizing pressure of 1.0MPa and gas flow of 3m3And/min, the crushing efficiency is 20Kg/h, the particle size is measured to be 180nm, 4g of titanium tetrachloride is weighed and added into 50g of processed porous montmorillonite, the operation condition is that the titanium tetrachloride is gradually added and operated in a low-temperature box, the operation temperature is 3 ℃, a compound is obtained, 10g of the compound is added into 100ml of deionized water, the low-temperature hydrolysis reaction is carried out, the reaction time is 30min, the reaction temperature is 3 ℃, 0.5g of triamino-ethylamine with the particle size of 5nm is added after the reaction, the reaction is carried out at 120 ℃, the reaction time is 6h, 1.5g of triethanolamine is added after the temperature is reduced to the normal temperature, and the nano composite material is obtained after the stirring is uniform.
And (3) testing: 0.1ml of solution is added into 10ml of formaldehyde solution, and the reaction is carried out for 0.5h under the irradiation of visible light, and the formaldehyde degradation rate is 76%.
Example 5 (comparative example):
pulverizing 10Kg montmorillonite by mechanical pulverizing method at 800rpm for 45min, and pulverizing for 1 time by air flow method at pulverizing pressure of 1.0MPa and gas flow of 3m3And/min, the crushing efficiency is 20Kg/h, the particle size is measured to be 180nm, 1g of titanium tetrachloride is weighed and added into 50g of processed porous montmorillonite, the operation condition is that the titanium tetrachloride is gradually added and operated in a low-temperature box, the operation temperature is 3 ℃, a compound is obtained, 10g of the compound is added into 100ml of deionized water, the low-temperature hydrolysis reaction is carried out, the reaction time is 30min, the reaction temperature is 3 ℃, 0.5g of fullerene with the particle size of 5nm is added after the reaction, the reaction is carried out at 160 ℃, the reaction time is 6h, the reaction time is reduced to the normal temperature, 1.5g of triethanolamine is added, and the nano composite material is obtained after the stirring is uniform.
And (3) testing: 0.1ml of solution is added into 10ml of formaldehyde solution, and the reaction is carried out for 0.5h under the irradiation of visible light, and the formaldehyde degradation rate is 70 percent.
Example 6 (comparative example):
pulverizing 10Kg montmorillonite by mechanical pulverizing method at 900rpm for 55min, and pulverizing by airflow method for 3 times at pulverizing pressure of 1.2MPa and gas flow of 3m3And/min, the crushing efficiency is 25Kg/h, the particle size is measured to be 80nm, 4g of titanium tetrachloride is weighed and added into 50g of processed porous montmorillonite, the operation condition is that the titanium tetrachloride is gradually added and operated in a low-temperature box, the operation temperature is 3 ℃, a compound is obtained, 10g of the compound is added into 100ml of deionized water, the low-temperature hydrolysis reaction is carried out, the reaction time is 30min, the reaction temperature is 3 ℃, 0.5g of fullerene with the particle size of 5nm is added after the reaction, the reaction is carried out at 160 ℃, the reaction time is 6h, 1.5g of triethanolamine is added after the temperature is reduced to the normal temperature, and the nano composite material is obtained after the stirring is uniform.
And (3) testing: 0.1ml of solution is added into 10ml of formaldehyde solution, and the reaction is carried out for 0.5h under the irradiation of visible light, and the formaldehyde degradation rate reaches 83 percent. The analysis reason is that after the montmorillonite is excessively crushed, the original gap structure of the montmorillonite can be damaged, the porosity is too low, the structure of the composite material is influenced, the composite efficiency is reduced, the multi-stage nano structure is not formed, the montmorillonite is changed into the blending of two substances, the superposition effect is not formed, and the degradation efficiency is reduced.
Example 7 (comparative example):
pulverizing 10Kg attapulgite by mechanical pulverizing method at 800rpm for 45min, and pulverizing by airflow method for 1 time at pulverizing pressure of 1.0MPa and gas flow of 3m3And/min, the crushing efficiency is 20Kg/h, the particle size is measured to be 180nm, 4g of titanium tetrachloride is weighed and added into 50g of processed attapulgite, the operation condition is that the titanium tetrachloride is gradually added and operated in a low-temperature box, the operation temperature is 3 ℃, a compound is obtained, 10g of the compound is added into 100ml of deionized water to carry out low-temperature hydrolysis reaction, the reaction time is 30min, the reaction temperature is 3 ℃, 0.5g of fullerene with the particle size of 5nm is added after the reaction, the reaction is carried out at 160 ℃, the reaction time is 6h, 1.5g of triethanolamine is added after the reaction is cooled to the normal temperature, and the nano composite material is obtained after the stirring is uniform.
And (3) testing: 0.1ml of solution is added into 10ml of formaldehyde solution, and the reaction is carried out for 0.5h under the irradiation of visible light, and the formaldehyde degradation rate is 86 percent.
Example 8 (comparative example):
pulverizing 10Kg montmorillonite by mechanical pulverizing method at 800rpm for 45min, and pulverizing for 1 time by air flow method at pulverizing pressure of 1.0MPa and gas flow of 3m3And/min, the crushing efficiency is 20Kg/h, the particle size is measured to be 180nm, 4g of titanium tetrachloride is weighed and added into 50g of processed montmorillonite under the operating condition that the titanium tetrachloride is gradually added and operated in a low-temperature box at the operating temperature of 10 ℃ to obtain a compound, 10g of the compound is added into 100ml of deionized water to perform low-temperature hydrolysis reaction for 30min at the reaction temperature of 10 ℃, 0.5g of fullerene with the particle size of 5nm is added after the reaction, the reaction is performed at the temperature of 160 ℃ for 6h, and 1.5g of triethanolamine is added after the reaction is cooled to the normal temperature and is uniformly stirred to obtain the nano composite material.
And (3) testing: 0.1ml of solution is added into 10ml of formaldehyde solution, and the reaction is carried out for 0.5h under the irradiation of visible light, and the formaldehyde degradation rate is 79 percent. The hydrolysis reaction speed is too high at a higher temperature, and the particle size of the formed titanium dioxide is larger, so that the formaldehyde degradation efficiency is reduced.
Example 9 (comparative example):
pulverizing 10Kg montmorillonite by mechanical pulverizing method at 800rpm for 45min, and pulverizing for 1 time by air flow method at pulverizing pressure of 1.0MPa and gas flow of 3m3And/min, the crushing efficiency is 20Kg/h, the measured particle size is 180nm, 4g of titanium tetrachloride is weighed and added into 50g of processed porous montmorillonite, the operation condition is that the titanium tetrachloride is gradually added and operated in a low-temperature box, the operation temperature is 3 ℃, a compound is obtained, 10g of the compound is added into 100ml of deionized water, the low-temperature hydrolysis reaction is carried out, the reaction time is 30min, the reaction temperature is 3 ℃, 0.5g of glucose is added after the reaction, the reaction is carried out at 160 ℃, the reaction time is 6h, 1.5g of triethanolamine is added after the temperature is reduced to the normal temperature, and the nano composite material is obtained after the stirring.
And (3) testing: 0.1ml of solution is added into 10ml of formaldehyde solution, and the reaction is carried out for 0.5h under the irradiation of visible light, and the formaldehyde degradation rate is 82 percent.
Example 10 (comparative example):
pulverizing 10Kg montmorillonite by mechanical pulverizing method at 800rpm for 45min, and pulverizing by air flow methodCrushing for 1 time at a crushing pressure of 1.0MPa and a gas flow of 3m3And/min, the crushing efficiency is 20Kg/h, the particle size is measured to be 180nm, 4g of titanium tetrachloride is weighed and added into 50g of processed porous montmorillonite, the operation condition is that the titanium tetrachloride is gradually added and operated in a low-temperature box, the operation temperature is 3 ℃, a compound is obtained, 10g of the compound is added into 100ml of deionized water, the low-temperature hydrolysis reaction is carried out, the reaction time is 30min, the reaction temperature is 3 ℃, 0.5g of fullerene with the particle size of 5nm is added after the reaction, the reaction is carried out at 160 ℃, the reaction time is 6h, the temperature is reduced to the normal temperature, then 1.5g of EDTAs are added, and the nano composite material is obtained after the uniform stirring.
And (3) testing: 0.1ml of solution is added into 10ml of formaldehyde solution, and the reaction is carried out for 0.5h under the irradiation of visible light, and the degradation rate of formaldehyde reaches 87%.
Example 11 (comparative example):
pulverizing 10Kg montmorillonite by mechanical pulverizing method at 800rpm for 45min, and pulverizing for 1 time by air flow method at pulverizing pressure of 1.0MPa and gas flow of 3m3And/min, the crushing efficiency is 20Kg/h, the particle size is measured to be 180nm, 4g of titanium tetrachloride is weighed and added into 50g of processed porous montmorillonite, the operation condition is that the titanium tetrachloride is gradually added and operated in a low-temperature box, the operation temperature is 3 ℃, a compound is obtained, 10g of the compound is added into 100ml of deionized water, the low-temperature hydrolysis reaction is carried out, the reaction time is 30min, the reaction temperature is 3 ℃, 0.5g of fullerene with the particle size of 5nm is added after the reaction, the reaction is carried out at 160 ℃, and the nano composite material is obtained after the reaction for 6 h.
And (3) testing: 0.1ml of solution is added into 10ml of formaldehyde solution, and the reaction is carried out for 0.5h under the irradiation of visible light, and the formaldehyde degradation rate is 77 percent.
In conclusion, the multi-stage nano composite material for photo-degrading organic toxic gas adopts the porous montmorillonite material, the gaps of which are uniformly distributed, and the multi-stage nano composite material can be used as a reaction carrier for preparing a small-size titanium catalyst, thereby playing the roles of controllable preparation and controllable dispersion of the nitrogen or carbon element doped titanium photocatalyst nano material. The nano composite material is subjected to surface modification, so that the powder can be uniformly dispersed in a water system and the effect of preventing coprecipitation is achieved. Compared with the existing materials, the material has wide light absorption range, can absorb the light wavelength range of 200-900 nm, basically covers ultraviolet-visible light and near infrared regions, has high energy utilization rate, improves the photodegradation efficiency, and simultaneously realizes the enrichment of organic toxic gas by the porous structure in the multistage nano structure, thereby greatly improving the catalytic efficiency of the titanium photocatalyst.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (6)
1. A method for preparing a multistage nano composite material with photodegradable organic toxic gas is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
preparing porous layered nano montmorillonite: montmorillonite is crushed to have an average particle size of 50-200 nm by a mechanical crushing method and an air flow method;
preliminary preparation of the nano composite material: compounding the montmorillonite and the titanium photocatalyst material at a low temperature of 1-5 ℃ to obtain a compound, adding the compound into water or alcohol, reacting at a low temperature of 1-5 ℃ for 10-50 min, and then adding a nitrogen source or a carbon source to react at a temperature of 120-180 ℃ for 4-8 h to obtain a primary nano composite material; the mass ratio of the montmorillonite to the titanium photocatalyst material is 1 (10-50); the mass ratio of the compound to water or alcohol is 1 (5-20), the mass ratio of a nitrogen source or a carbon source accounts for 0.1-5% of the total mass of the compound and the water or alcohol, and the raw material of the titanium photocatalyst material is titanium tetrachloride;
modification of the multistage nanocomposite: cooling the primary nano composite material, and then adding a modifier for modification, wherein the modifier accounts for 0.2-2% of the total mass of the composite/water or alcohol/nitrogen source or carbon source system; the modifier comprises glycerol or triethanolamine; the average molecular particle size of the carbon source is 2-5 nm.
2. The method of preparing the multistage nanocomposite with photodegradable organic toxic gas according to claim 1, wherein the method comprises the following steps: the mechanical crushing method has the crushing time of 0.5-1 h and the rotating speed of 400-1200 rpm.
3. The method for preparing the multistage nanocomposite with photodegradable organic toxic gas according to claim 1 or 2, wherein the method comprises the following steps: the gas flow method has the gas flow of 2-4 m3Min, gas pressure of 0.7-1.5 MPa, and crushing efficiency of 10-30 Kg/h.
4. The method of preparing the multistage nanocomposite with photodegradable organic toxic gas according to claim 1, wherein the method comprises the following steps: adding the compound into water or alcohol, and reacting at low temperature, wherein the alcohol is ethanol.
5. The method of preparing the multistage nanocomposite with photodegradable organic toxic gas according to claim 1, wherein the method comprises the following steps: the nitrogen source comprises one or more of triaminoethylamine, ethylenediamine and ammonia water.
6. The method of preparing the multistage nanocomposite with photodegradable organic toxic gas according to claim 1, wherein the method comprises the following steps: the carbon source comprises one or more of fullerene, graphene and citric acid; the citric acid is a pure substance modified by sodium salt.
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