Disclosure of Invention
The invention provides a material for adsorbing carbon dioxide and VOCs gas, which can effectively adsorb the carbon dioxide and the VOCs gas.
The invention adopts the following technical scheme for solving the technical problems:
a material for adsorbing carbon dioxide and VOCs gases comprises the following raw materials in parts by weight: 30 to 50 parts of modified diatomite, 20 to 40 parts of mesoporous silica, 15 to 25 parts of zeolite, 10 to 20 parts of modified graphene oxide, 6 to 15 parts of chitosan, 4 to 10 parts of bentonite, 4~8 parts of metal organic framework material and 1~5 parts of sodium lignosulphonate.
As a preferable scheme, the material for adsorbing carbon dioxide and VOCs gas is composed of the following raw materials in parts by weight: 35 to 50 parts of modified diatomite, 25 to 40 parts of mesoporous silica, 16 to 25 parts of zeolite, 12 to 20 parts of modified graphene oxide, 8 to 15 parts of chitosan, 6 to 10 parts of bentonite, 5~8 parts of metal organic framework material and 2~5 parts of sodium lignosulphonate.
As a preferable scheme, the material for adsorbing carbon dioxide and VOCs gas is composed of the following raw materials in parts by weight: 44 parts of modified diatomite, 32 parts of mesoporous silica, 20 parts of zeolite, 16 parts of modified graphene oxide, 10 parts of chitosan, 7 parts of bentonite, 6 parts of metal organic framework material and 3 parts of sodium lignosulfonate.
As a preferable scheme, the preparation method of the modified diatomite comprises the following steps:
soaking diatomite in a hydrochloric acid solution, stirring for the first time at the temperature of 40-50 ℃, filtering, drying, and calcining for 4-10h at the temperature of 500-600 ℃ to obtain pretreated diatomite; the weight of the hydrochloric acid solution is 6 to 10 times of that of the diatomite;
adding pretreated diatomite and 2,4-dinitrophenylhydrazine into 5-15wt% ferric nitrate solution, stirring for the second time, drying, and calcining at 500-600 ℃ for 6-12h to obtain modified diatomite; the weight ratio of the pretreated diatomite, 2,4-dinitrophenylhydrazine and the ferric nitrate solution is 1:0.1 to 0.3:6 to 10.
Preferably, the mass concentration of the hydrochloric acid is 4mol/L to 6mol/L.
As a preferable scheme, the first stirring speed is 200 to 300rpm, and the stirring time is 30 to 40min; the second stirring speed is 100 to 200rpm, and the stirring time is 20 to 40min.
As a preferable scheme, the preparation method of the modified graphene oxide comprises the following steps:
dispersing 6 to 10 parts of graphene oxide in 80 to 100 parts of deionized water to form a graphene suspension;
adding 10 to 14 parts of tetradecyl trimethyl ammonium bromide, 2~5 parts of glycidyl methacrylate, 2~6 parts of activated carbon and 0.8 to 1.5 parts of coupling agent, reacting in a water bath for 4 to 7 hours, carrying out suction filtration, and drying to constant weight to obtain the modified graphene oxide.
As a preferable scheme, the water bath temperature is 70 to 80 ℃.
As a preferred embodiment, the coupling agent is kh550.
Preferably, the metal-organic framework material is Mg-MOF-74.
The invention has the beneficial effects that: (1) The material for adsorbing carbon dioxide and VOCs gas can well adsorb carbon dioxide and VOCs gas, and has wide application prospect; (2) The material for adsorbing carbon dioxide and VOCs gas can be applied to a solvent storage bottle cap, can effectively carry out dead adsorption on an organic volatile solvent or carbon dioxide, and can effectively prevent the organic solvent from volatilizing and leaking and prevent the solvent from absorbing the carbon dioxide and deteriorating; (3) The material is formed by compounding various materials, wherein the modified diatomite and the modified graphene can obviously improve the adsorption effect on carbon dioxide and VOCs gases, and the metal organic framework material (Mg-MOF-74) can obviously improve the adsorption effect on carbon dioxide.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless otherwise stated, "parts" of the invention are parts by weight; the Mg-MOF-74 is an existing substance and is purchased from Xian Ruixi Biotechnology Limited, the graphene oxide is a common raw material in the market and is purchased from Shenzhen Guangdong Chuang evolution technology Limited, and other raw materials are common and available in the market.
Example 1
A material for adsorbing carbon dioxide and VOCs gases comprises the following raw materials in parts by weight: 44 parts of modified diatomite, 32 parts of mesoporous silica, 20 parts of zeolite, 16 parts of modified graphene oxide, 10 parts of chitosan, 7 parts of bentonite, 6 parts of metal organic framework material and 3 parts of sodium lignosulfonate.
The preparation method of the modified diatomite comprises the following steps:
immersing diatomite into a hydrochloric acid solution with the mass concentration of 5mol/L, stirring for the first time at the temperature of 45 ℃, filtering, drying, and calcining for 6 hours at the temperature of 550 ℃ to obtain pretreated diatomite; the weight of the hydrochloric acid solution is 9 times of that of the diatomite;
adding the pretreated diatomite and 2,4-dinitrophenylhydrazine into 8wt% ferric nitrate solution, stirring for the second time, drying, and calcining at 550 ℃ for 10 hours to obtain modified diatomite; the weight ratio of the pretreated diatomite, 2,4-dinitrophenylhydrazine and the ferric nitrate solution is 1:0.2:8.
the first stirring speed is 200rpm, and the stirring time is 35min; the second stirring speed was 150rpm, and the stirring time was 30min.
The preparation method of the modified graphene oxide comprises the following steps:
dispersing 7 parts of graphene oxide in 93 parts of deionized water to form a graphene suspension;
adding 11 parts of tetradecyl trimethyl ammonium bromide, 2 parts of glycidyl methacrylate, 4 parts of activated carbon and 1.2 parts of kh550, reacting for 5 hours in a water bath at 75 ℃, filtering, and drying to constant weight to obtain the modified graphene oxide.
The metal organic framework material is Mg-MOF-74.
Example 2
A material for adsorbing carbon dioxide and VOCs gases comprises the following raw materials in parts by weight: 30 parts of modified diatomite, 20 parts of mesoporous silica, 15 parts of zeolite, 10 parts of modified graphene oxide, 6 parts of chitosan, 4 parts of bentonite, 4 parts of metal organic framework material and 1 part of sodium lignosulfonate.
The preparation method of the modified diatomite comprises the following steps:
immersing diatomite into a hydrochloric acid solution with the mass concentration of 5mol/L, stirring for the first time at the temperature of 45 ℃, filtering, drying, and calcining for 6 hours at the temperature of 550 ℃ to obtain pretreated diatomite; the weight of the hydrochloric acid solution is 9 times of that of the diatomite;
adding the pretreated diatomite and 2,4-dinitrophenylhydrazine into 8wt% ferric nitrate solution, stirring for the second time, drying, and calcining at 550 ℃ for 10 hours to obtain modified diatomite; the weight ratio of the pretreated diatomite, 2,4-dinitrophenylhydrazine and ferric nitrate solution is 1:0.2:8.
the first stirring speed is 200rpm, and the stirring time is 35min; the second stirring speed was 150rpm and the stirring time was 30min.
The preparation method of the modified graphene oxide comprises the following steps:
dispersing 7 parts of graphene oxide in 93 parts of deionized water to form a graphene suspension;
adding 11 parts of tetradecyl trimethyl ammonium bromide, 2 parts of glycidyl methacrylate, 4 parts of activated carbon and 1.2 parts of kh550, reacting for 5 hours in a water bath at 75 ℃, filtering, and drying to constant weight to obtain the modified graphene oxide.
The metal organic framework material is Mg-MOF-74.
Example 3
A material for adsorbing carbon dioxide and VOCs gases comprises the following raw materials in parts by weight: 50 parts of modified diatomite, 40 parts of mesoporous silica, 25 parts of zeolite, 20 parts of modified graphene oxide, 15 parts of chitosan, 10 parts of bentonite, 8 parts of metal organic framework material and 5 parts of sodium lignosulfonate.
The preparation method of the modified diatomite comprises the following steps:
immersing diatomite into a hydrochloric acid solution with the mass concentration of 5mol/L, stirring for the first time at the temperature of 45 ℃, filtering, drying, and calcining for 6 hours at the temperature of 550 ℃ to obtain pretreated diatomite; the weight of the hydrochloric acid solution is 9 times of that of the diatomite;
adding pretreated diatomite and 2,4-dinitrophenylhydrazine into 8wt% ferric nitrate solution, stirring for the second time, drying, and calcining at 550 ℃ for 10 hours to obtain modified diatomite; the weight ratio of the pretreated diatomite, 2,4-dinitrophenylhydrazine and the ferric nitrate solution is 1:0.2:8.
the first stirring speed is 200rpm, and the stirring time is 35min; the second stirring speed was 150rpm and the stirring time was 30min.
The preparation method of the modified graphene oxide comprises the following steps:
dispersing 7 parts of graphene oxide in 93 parts of deionized water to form a graphene suspension;
adding 11 parts of tetradecyl trimethyl ammonium bromide, 2 parts of glycidyl methacrylate, 4 parts of activated carbon and 1.2 parts of kh550, reacting for 5 hours in a water bath at 75 ℃, filtering, and drying to constant weight to obtain the modified graphene oxide.
The metal organic framework material is Mg-MOF-74.
Example 4
A material for adsorbing carbon dioxide and VOCs gases comprises the following raw materials in parts by weight: 32 parts of modified diatomite, 28 parts of mesoporous silica, 18 parts of zeolite, 12 parts of modified graphene oxide, 8 parts of chitosan, 5 parts of bentonite, 5 parts of metal organic framework material and 2 parts of sodium lignosulfonate.
The preparation method of the modified diatomite comprises the following steps:
immersing diatomite into a hydrochloric acid solution with the mass concentration of 5mol/L, stirring for the first time at the temperature of 45 ℃, filtering, drying, and calcining for 6 hours at the temperature of 550 ℃ to obtain pretreated diatomite; the weight of the hydrochloric acid solution is 9 times of that of the diatomite;
adding the pretreated diatomite and 2,4-dinitrophenylhydrazine into 8wt% ferric nitrate solution, stirring for the second time, drying, and calcining at 550 ℃ for 10 hours to obtain modified diatomite; the weight ratio of the pretreated diatomite, 2,4-dinitrophenylhydrazine and the ferric nitrate solution is 1:0.2:8.
the first stirring speed is 200rpm, and the stirring time is 35min; the second stirring speed was 150rpm and the stirring time was 30min.
The preparation method of the modified graphene oxide comprises the following steps:
dispersing 7 parts of graphene oxide in 93 parts of deionized water to form a graphene suspension;
adding 11 parts of tetradecyl trimethyl ammonium bromide, 2 parts of glycidyl methacrylate, 4 parts of activated carbon and 1.2 parts of kh550, reacting for 5 hours in a water bath at 75 ℃, filtering, and drying to constant weight to obtain the modified graphene oxide.
The metal organic framework material is Mg-MOF-74.
Example 5
A material for adsorbing carbon dioxide and VOCs gases comprises the following raw materials in parts by weight: 32 parts of modified diatomite, 28 parts of mesoporous silica, 18 parts of zeolite, 12 parts of modified graphene oxide, 8 parts of chitosan, 5 parts of bentonite, 5 parts of metal organic framework material and 2 parts of sodium lignosulfonate.
The preparation method of the modified diatomite comprises the following steps:
immersing diatomite into a hydrochloric acid solution with the mass concentration of 5mol/L, stirring for the first time at the temperature of 45 ℃, filtering, drying, and calcining for 6 hours at the temperature of 550 ℃ to obtain pretreated diatomite; the weight of the hydrochloric acid solution is 9 times of that of the diatomite;
adding the pretreated diatomite and 2,4-dinitrophenylhydrazine into 8wt% ferric nitrate solution, stirring for the second time, drying, and calcining at 550 ℃ for 10 hours to obtain modified diatomite; the weight ratio of the pretreated diatomite, 2,4-dinitrophenylhydrazine and the ferric nitrate solution is 1:0.2:8.
the first stirring speed is 200rpm, and the stirring time is 35min; the second stirring speed was 150rpm and the stirring time was 30min.
The preparation method of the modified graphene oxide comprises the following steps:
dispersing 6 parts of graphene oxide in 80 parts of deionized water to form a graphene suspension;
adding 10 parts of tetradecyl trimethyl ammonium bromide, 2 parts of glycidyl methacrylate, 2 parts of activated carbon and 0.8 part of coupling agent, reacting for 4 hours in a water bath, filtering, and drying to constant weight to obtain the modified graphene oxide.
The metal organic framework material is Mg-MOF-74.
Example 6
A material for adsorbing carbon dioxide and VOCs gases comprises the following raw materials in parts by weight: 32 parts of modified diatomite, 28 parts of mesoporous silica, 18 parts of zeolite, 12 parts of modified graphene oxide, 8 parts of chitosan, 5 parts of bentonite, 5 parts of metal organic framework material and 2 parts of sodium lignosulfonate.
The preparation method of the modified diatomite comprises the following steps:
immersing diatomite into a hydrochloric acid solution with the mass concentration of 5mol/L, stirring for the first time at the temperature of 45 ℃, filtering, drying, and calcining for 6 hours at the temperature of 550 ℃ to obtain pretreated diatomite; the weight of the hydrochloric acid solution is 9 times of that of the diatomite;
adding the pretreated diatomite and 2,4-dinitrophenylhydrazine into 8wt% ferric nitrate solution, stirring for the second time, drying, and calcining at 550 ℃ for 10 hours to obtain modified diatomite; the weight ratio of the pretreated diatomite, 2,4-dinitrophenylhydrazine and the ferric nitrate solution is 1:0.2:8.
the first stirring speed is 200rpm, and the stirring time is 35min; the second stirring speed was 150rpm and the stirring time was 30min.
The preparation method of the modified graphene oxide comprises the following steps:
dispersing 10 parts of graphene oxide in 100 parts of deionized water to form a graphene suspension;
adding 14 parts of tetradecyl trimethyl ammonium bromide, 5 parts of glycidyl methacrylate, 6 parts of activated carbon and 1.5 parts of coupling agent, reacting for 7 hours in a water bath, filtering, and drying to constant weight to obtain the modified graphene oxide.
The metal organic framework material is Mg-MOF-74.
Comparative example 1
Comparative example 1 is different from example 1 in that comparative example 1 does not contain modified diatomaceous earth, and the other is the same.
Comparative example 2
Comparative example 2 is different from example 1 in that comparative example 2 replaces modified diatomaceous earth with diatomaceous earth, and the others are the same.
Comparative example 3
Comparative example 3 is different from example 1 in that comparative example 3 does not contain modified graphene oxide, and the others are the same.
Comparative example 4
Comparative example 4 is different from example 1 in that comparative example 4 replaces the modified graphene oxide with graphene oxide, and the others are the same.
Comparative example 5
Comparative example 5 differs from example 1 in that comparative example 5 does not contain a metal organic framework material, i.e. does not contain Mg-MOF-74, and is otherwise identical.
To further demonstrate the effect of the present invention, the following test methods were provided:
1. the adsorption capacity data was determined using a fixed bed at an adsorption temperature of 70 ℃ and a simulated gas flow of 50ml/min, three times per measurement, and the results are shown in Table 1.
As can be seen from table 1, the material of the present invention has a good adsorption effect on carbon dioxide and VOCs, as can be seen from comparative example 1~4, different ratios can affect the adsorption effect of the material on carbon dioxide and VOCs, wherein example 1 is the best ratio and has the best adsorption effect, and as can be seen from comparative examples 1, 5 and 6, different preparation ratios of modified graphene oxide can affect the adsorption effect on carbon dioxide and VOCs, wherein example 1 is the best preparation ratio of modified graphene oxide; it can be known from comparative example 1 and comparative example 1~2 that the modified diatomite of the present invention can significantly improve the adsorption effect on carbon dioxide and VOCs, and from comparative example 1 and comparative example 3~4 that the modified graphene oxide of the present invention can significantly improve the adsorption effect on carbon dioxide and VOCs, and from comparative example 1 and comparative example 5 that the metal-organic framework material (Mg-MOF-74) of the present invention can significantly improve the adsorption effect on carbon dioxide.
2. The material prepared in example 1 was adsorbed with carbon dioxide three times, and then the amount of adsorbed carbon dioxide, CO, was measured again 2 The adsorption amount =2.9 mmol/g, and it can be seen that the material has a sustained and stable adsorption effect.
In light of the foregoing description of preferred embodiments according to the invention, it is clear that many changes and modifications can be made by the person skilled in the art without departing from the scope of the invention. The technical scope of the present invention is not limited to the contents of the specification, and must be determined according to the scope of the claims.