CN112316912A - Material for adsorbing carbon dioxide and VOCs (volatile organic compounds) gas - Google Patents

Material for adsorbing carbon dioxide and VOCs (volatile organic compounds) gas Download PDF

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CN112316912A
CN112316912A CN202011233190.3A CN202011233190A CN112316912A CN 112316912 A CN112316912 A CN 112316912A CN 202011233190 A CN202011233190 A CN 202011233190A CN 112316912 A CN112316912 A CN 112316912A
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carbon dioxide
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diatomite
adsorbing carbon
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曾伟杰
李国强
马能媛
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Guangzhou Taiwei Biotechnology Co ltd
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    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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Abstract

The invention discloses a material for adsorbing carbon dioxide and VOCs (volatile organic compounds) gas, which consists of the following raw materials: modified diatomite, mesoporous silica, zeolite, modified graphene oxide, chitosan, bentonite, a metal organic framework material and sodium lignosulfonate. The material for adsorbing carbon dioxide and VOCs gas can well adsorb carbon dioxide and VOCs gas, and has wide application prospect; 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; the material is formed by compounding multiple materials, wherein the modified diatomite and the modified graphene can obviously improve the adsorption effect on carbon dioxide and VOCs gas, and the metal organic framework material can obviously improve the adsorption effect on carbon dioxide.

Description

Material for adsorbing carbon dioxide and VOCs (volatile organic compounds) gas
Technical Field
The invention relates to the technical field of adsorption materials, in particular to a material for adsorbing carbon dioxide and VOCS (volatile organic compounds).
Background
Organic solvents used in analytical experiments, such as ethanol (alcohols), formaldehyde (aldehydes), acetone (ketones), toluene (aromatic hydrocarbons) and the like, are easily volatilized under atmospheric pressure, and gases thereof are flammable and explosive, have certain toxicity and pollution, and when the solvents are used, experimenters need to perform experiments in a fume hood with air draft and exhaust functions or in the environment. In an analysis experiment, hydroxide and buffer salt solvents are easy to react with carbon dioxide in the air to generate other substances, the acid value of the solution is changed to a certain extent, the stability of the solvent is seriously influenced, the storage life is shortened, and the accuracy of an experiment result is improved. In order to prevent air pollution and damage caused by organic solvent leakage or volatilization, the prior art is added with an exhaust device except that the solvent is stored in a sealing way, and gas is directly exhausted outdoors, and the two modes can not completely eliminate the leakage and the pollution fundamentally.
The existing adsorbing material has a single function, can only adsorb a single substance or a single kind of substance, is not ideal in adsorbing effect, and has a transient adsorbing effect and a non-lasting and stable adsorbing effect.
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: 30-50 parts of modified diatomite, 20-40 parts of mesoporous silica, 15-25 parts of zeolite, 10-20 parts of modified graphene oxide, 6-15 parts of chitosan, 4-10 parts of bentonite, 4-8 parts of metal organic framework material and 1-5 parts of sodium lignosulfonate.
As a preferable scheme, the material for adsorbing carbon dioxide and VOCs gas is composed of the following raw materials in parts by weight: 35-50 parts of modified diatomite, 25-40 parts of mesoporous silica, 16-25 parts of zeolite, 12-20 parts of modified graphene oxide, 8-15 parts of chitosan, 6-10 parts of bentonite, 5-8 parts of metal organic framework material and 2-5 parts of sodium lignosulfonate.
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:
immersing kieselguhr into a hydrochloric acid solution, stirring for the first time at the temperature of 40-50 ℃, filtering, drying, and calcining for 4-10 hours at the temperature of 500-600 ℃ to obtain pretreated kieselguhr; the weight of the hydrochloric acid solution is 6-10 times of that of the diatomite;
adding the pretreated kieselguhr and 2, 4-dinitrophenylhydrazine into a 5-15 wt% ferric nitrate solution, stirring for the second time, drying, and calcining at 500-600 ℃ for 6-12 hours to obtain modified kieselguhr; the weight ratio of the pretreated diatomite, the 2, 4-dinitrophenylhydrazine and the ferric nitrate solution is 1: 0.1-0.3: 6 to 10.
Preferably, the mass concentration of the hydrochloric acid is 4mol/L to 6 mol/L.
As a preferable scheme, the first stirring speed is 200-300 rpm, and the stirring time is 30-40 min; the second stirring speed is 100-200 rpm, and the stirring time is 20-40 min.
As a preferable scheme, the preparation method of the modified graphene oxide comprises the following steps:
dispersing 6-10 parts of graphene oxide in 80-100 parts of deionized water to form a graphene suspension;
adding 10-14 parts of tetradecyl trimethyl ammonium bromide, 2-5 parts of glycidyl methacrylate, 2-6 parts of activated carbon and 0.8-1.5 parts of a coupling agent, reacting in a water bath for 4-7 hours, performing suction filtration, and drying to constant weight to obtain the modified graphene oxide.
As a preferable scheme, the temperature of the water bath is 70-80 ℃.
As a preferred embodiment, the coupling agent is kh 550.
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, the 2, 4-dinitrophenylhydrazine and the ferric nitrate solution is 1: 0.2: 8.
the first stirring speed is 200rpm, and the stirring time is 35 min; the second stirring speed was 150rpm and the stirring time was 30 min.
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, the 2, 4-dinitrophenylhydrazine and the ferric nitrate solution is 1: 0.2: 8.
the first stirring speed is 200rpm, and the stirring time is 35 min; the second stirring speed was 150rpm and the stirring time was 30 min.
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 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, the 2, 4-dinitrophenylhydrazine and the ferric nitrate solution is 1: 0.2: 8.
the first stirring speed is 200rpm, and the stirring time is 35 min; the second stirring speed was 150rpm and the stirring time was 30 min.
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, the 2, 4-dinitrophenylhydrazine and the ferric nitrate solution is 1: 0.2: 8.
the first stirring speed is 200rpm, and the stirring time is 35 min; the second stirring speed was 150rpm and the stirring time was 30 min.
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, the 2, 4-dinitrophenylhydrazine and the ferric nitrate solution is 1: 0.2: 8.
the first stirring speed is 200rpm, and the stirring time is 35 min; the second stirring speed was 150rpm and the stirring time was 30 min.
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, the 2, 4-dinitrophenylhydrazine and the ferric nitrate solution is 1: 0.2: 8.
the first stirring speed is 200rpm, and the stirring time is 35 min; the second stirring speed was 150rpm and the stirring time was 30 min.
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 differs from example 1 in that comparative example 1 does not contain modified diatomaceous earth, and the rest 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.
Figure DEST_PATH_IMAGE001
As can be seen from table 1, the material of the present invention has a good adsorption effect on carbon dioxide and VOCs, and as can be seen from comparative examples 1 to 4, different ratios can affect the adsorption effect of the material on carbon dioxide and VOCs, wherein example 1 is an optimal ratio and has a 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 an optimal preparation ratio of modified graphene oxide; the comparative example 1 and the comparative examples 1 to 2 show that the modified diatomite can significantly improve the adsorption effect on carbon dioxide and VOCs gases, the comparative example 1 and the comparative examples 3 to 4 show that the modified graphene oxide can significantly improve the adsorption effect on carbon dioxide and VOCs gases, and the comparative example 1 and the comparative example 5 show that the metal-organic framework material (Mg-MOF-74) 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 again2The 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.

Claims (10)

1. The material for adsorbing carbon dioxide and VOCs gases is characterized by comprising the following raw materials in parts by weight: 30-50 parts of modified diatomite, 20-40 parts of mesoporous silica, 15-25 parts of zeolite, 10-20 parts of modified graphene oxide, 6-15 parts of chitosan, 4-10 parts of bentonite, 4-8 parts of metal organic framework material and 1-5 parts of sodium lignosulfonate.
2. The material for adsorbing carbon dioxide and VOCs gas according to claim 1, wherein the material for adsorbing carbon dioxide and VOCs gas comprises the following raw materials in parts by weight: 35-50 parts of modified diatomite, 25-40 parts of mesoporous silica, 16-25 parts of zeolite, 12-20 parts of modified graphene oxide, 8-15 parts of chitosan, 6-10 parts of bentonite, 5-8 parts of metal organic framework material and 2-5 parts of sodium lignosulfonate.
3. The material for adsorbing carbon dioxide and VOCS gas according to claim 1, wherein the material for adsorbing carbon dioxide and VOCs gas comprises the following raw materials 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.
4. The material for adsorbing carbon dioxide and VOCs gas according to claim 1, wherein the modified diatomite is prepared by the following steps:
immersing kieselguhr into a hydrochloric acid solution, stirring for the first time at the temperature of 40-50 ℃, filtering, drying, and calcining for 4-10 hours at the temperature of 500-600 ℃ to obtain pretreated kieselguhr; the weight of the hydrochloric acid solution is 6-10 times of that of the diatomite;
adding the pretreated kieselguhr and 2, 4-dinitrophenylhydrazine into a 5-15 wt% ferric nitrate solution, stirring for the second time, drying, and calcining at 500-600 ℃ for 6-12 hours to obtain modified kieselguhr; the weight ratio of the pretreated diatomite, the 2, 4-dinitrophenylhydrazine and the ferric nitrate solution is 1: 0.1-0.3: 6 to 10.
5. The material for adsorbing carbon dioxide and VOCs gas according to claim 4, wherein the hydrochloric acid has a mass concentration of 4 to 6 mol/L.
6. The material for adsorbing carbon dioxide and VOCs gas according to claim 4, wherein the first stirring speed is 200-300 rpm, and the stirring time is 30-40 min; the second stirring speed is 100-200 rpm, and the stirring time is 20-40 min.
7. The material for adsorbing carbon dioxide and VOCs gas according to claim 1, wherein the preparation method of the modified graphene oxide comprises:
dispersing 6-10 parts of graphene oxide in 80-100 parts of deionized water to form a graphene suspension;
adding 10-14 parts of tetradecyl trimethyl ammonium bromide, 2-5 parts of glycidyl methacrylate, 2-6 parts of activated carbon and 0.8-1.5 parts of a coupling agent, reacting in a water bath for 4-7 hours, performing suction filtration, and drying to constant weight to obtain the modified graphene oxide.
8. The material for adsorbing carbon dioxide and VOCs gas according to claim 7, wherein the water bath temperature is 70-80 ℃.
9. The material for adsorbing carbon dioxide and VOCs gas according to claim 7, wherein said coupling agent is kh 550.
10. The material for adsorbing carbon dioxide and VOCs gas according to claim 1, wherein the metal-organic framework material is Mg-MOF-74.
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