CN105879839A - Novel multifunctional air purification material and preparation method thereof - Google Patents
Novel multifunctional air purification material and preparation method thereof Download PDFInfo
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- CN105879839A CN105879839A CN201410611998.9A CN201410611998A CN105879839A CN 105879839 A CN105879839 A CN 105879839A CN 201410611998 A CN201410611998 A CN 201410611998A CN 105879839 A CN105879839 A CN 105879839A
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Abstract
The invention provides a novel multifunctional air purification material and a preparation method thereof, and aims to solve the problem that the adsorption capacity of porous carbon on pollutants in the air and heavy metals is not large. The provided novel multifunctional air purification material can simultaneously and efficiently remove trace acidic pollutant gas in the air such as sulfur dioxide, sulfur trioxide, nitrogen dioxide, and the like, and heavy metal lead (II). The provided porous carbon composite material comprises multiple amine groups; common substances such as porous carbon, nitric acid, triethylenetetramine, and the like are taken as the raw materials; and the composite material is obtained through carboxylation and molecular copolycondensation reactions. The air purification material comprises many channels, a large specific surface area, and abundant amine groups on the surface, and thus has a strong adsorption performance on acidic gas such as oxynitride, sulfur oxides, and the like, and heavy metal lead. The air purification material can simultaneously remove a plurality of acidic gas and heavy metal lead. The application range is wide, the effect is strong, moreover, the preparation technology is simple, and the method is easy to perform, and can be applied to massive production.
Description
Technical field
The invention belongs to nonmetallic materials science and technology branch, be applied to gas absorption and separation field, specifically
Relate to one can the most efficiently remove in air simultaneously the pollutant acid gas such as micro nitrogen oxide, oxysulfide and
Multifunction material for air purification of heavy metal lead and preparation method thereof.
Background technology
Air environmental pollution is the important environmental problem of facing mankind, and the quality of air quality, to whole ecology
Directly affect with human health.According to World Health Organization (WHO) (WHO), atmospheric pollution is caused Disease Spectrum
Evaluation, have more than every year the premature death of 2,000,000 owing to city outdoor and room air pollution.China is big
Gas pollutant mainly have particulate pollutant, nitrogen oxysulfide and heavy metal etc..Wherein, with coal and oil
Population of China is good for by the heavy metal lead of nitrogen oxides, oxysulfide and vehicle exhaust release that burning discharges
Health impact is bigger.
The carbonaceous porous agent such as activated carbon are adsorbing materials conventional in air cleaning, but normal activated carbon is with micro-
Kong Weizhu, Surface chemical functional group of wood content is few, and polarity is little, to nitrogen oxides, oxysulfide, weight in air
Metal ion isopolarity pollutant adsorption capacity is little, poor selectivity.The present invention is by dividing with polyamines with porous charcoal
Son is presoma, by nitric acid oxidation with shrink poly-and etc. simple reaction, polyamine molecule is grafted to porous charcoal
Material duct and surface, enhance the absorption of the alkalescence on porous carbon material surface, beneficially sour gas, and
The polyamine group of material surface grafting, can quickly fix the lead ion in air by complexing, thus
Prepare acid pollutions such as simultaneously can the most efficiently removing in air trace sulfur dioxide, sulfur trioxide, nitrogen dioxide
Multifunction material for air purification of gas and heavy metal lead (II) and preparation method thereof
Summary of the invention
The present invention is directed to the practical problem that existing porous charcoal is little to gas pollutant and heavy metal adsorption capacity,
One is provided can the most efficiently to remove trace sulfur dioxide, sulfur trioxide, nitrogen dioxide etc. in air acid dirty
Multifunction material for air purification of dye gas and heavy metal lead (II) and preparation method thereof.This New Polyamine
Base porous carbon composite material is with Common materials such as porous charcoal, nitric acid, three second tetramines as raw material, by carboxylated
Prepare with molecule copolycondensation, have that duct is many, specific surface area big, surface polyamine group rich content,
The sour gas such as nitrogen oxides, oxysulfide and heavy metal lead in air all there is stronger absorbability.
This material for air purification can remove multiple sour gas and heavy metal lead, applied range simultaneously, and effect is strong,
And there is the advantages such as preparation technology is simple, easy to implement, can high-volume large-scale production.
The purpose of the present invention can be reached by following measures:
A kind of New Polyamine base carbonaceous material for air purification utilizing porous charcoal to produce with polyamine molecule and preparation thereof
Method, comprises the steps:
1) porous charcoal is stirred more than 2 hours at 30~80 DEG C, through after purification with the hydrochloric acid solution of 10%
Porous charcoal powder add 100~the 10 of 500ml~the nitric acid stirring 1~10 hours of 50%, after completion of the reaction
By product washing to neutral, filtering drying must be rich in the porous charcoal of carboxylic acid group.
2) weigh the above-mentioned carboxylated biomass carbon of 5g, distribute it in 50~200ml polyamine molecule modifying agent,
To be mixed uniformly after, add N, N '-dicyclohexylcarbodiimide, back flow reaction 6~96 hours.
3) above-mentioned product is first slightly washed with ethanol, then clean with ether, then in nitrogen protection or vacuum
Drying is to New Polyamine base carbonaceous material for air purification.
Above-mentioned steps 1) in, described porous charcoal is that mesoporous carbon, biomass carbon, activated carbon or graphite are dilute
Kind, preferably mesopore proportion > 30%, mesopore volume > 0.3cm3The mesoporous biological matter Carbon Materials of/g;
Above-mentioned steps 2) in, described polyamine molecule modifying agent refers to three second tetramines.
The core of such scheme be the selection of polyamine molecule, the mesoporous pore volume of porous charcoal content with carboxylated and
Shrink and gather and the selection of reaction condition.The purpose of nitric acid oxidation is to increase porous carbon material carboxylic acid group's content;Relatively
High mesoporous pore volume can not only be effectively improved porous charcoal hydroxy-acid group content, and can be carboxylic acid group and modified polyamine
Molecule shrinks and builds up the reaction offer useful space.
The excellent results of the present invention is as follows:
1) present invention is former material with originate biomass carbon, activated carbon or mesoporous carbon widely, purified pretreatment,
Nitric acid oxidation and shrink poly-and wait simple reaction, can be grafted to polyamine molecule in porous charcoal, synthesis work
Skill is simple, invests little, economic and environment-friendly, it is easy to implement, and produces and meets recycling economy development needs, can scale
Change and produce in enormous quantities.
2) the amination carbonaceous porous air scavenging material that prepared by the present invention, specific surface area is big, rich in polyamine group,
The sour gas such as the oxysulfide in gas, nitrogen oxides and heavy metal lead all there are is stronger affinity interaction,
Can be used for removing the low-concentration acid gas in air and heavy metal lead, applied range, have wide application
Prospect.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but is not limited to this.
Example 1
By 5.0g mesoporous carbon (BET specific surface 870m2/ g, mesopore volume is 0.313ml/g) use mass fraction
Be 10% HCl solution at 60 DEG C of stirring purification 5 hours, add after drying 600ml 32.5% nitre
Acid stirring 5 hours, adds the three second tetramines of 100ml subsequently, agitating heating uniformly after, add 5 grams of N, N '-
Dicyclohexylcarbodiimide, back flow reaction 48 hours.By product washes clean, after drying, obtain Multifunction
Material for air purification.
The infrared spectrogram of Multifunction material for air purification is as shown in Figure 1.It will be seen from figure 1 that system
Standby amination modifying biomass carbon contains the nitrilo group become apparent from, and shows that modified three second tetramines are by success
Guided on mesoporous carbon sample;Its surface group content is measured by Boehm titrimetry, and result shows
Its basic group content is increased to 2.69mmol/g by the 0.035mmol/g before modifying.
Sulfur dioxide, nitrogen dioxide are demonstrated by out in absorption test by above-mentioned material with heavy metal lead ion
The absorption property of color.Being 30% in humidity, flue gas flow is 200L/h, sulfur dioxide and content of nitrogen dioxide
When being respectively 30ppm and 15ppm, above-mentioned material centering SO2And NO2Equilibrium adsorption capacities be respectively
87mg/g and 69mg/g.In Staticadsorption experiment, when pH value of solution is 5, above-mentioned material is to 50mg/L
The equilibrium adsorption capacity of lead (II) be 156mg/g.
Example 2:
By 10g bagasse based biomass charcoal (BET specific surface 987m2/ g, mesopore volume 0.371cm3/ g), use matter
Amount mark be that the HCl solution of 10% stirs purification 5 hours at 60 DEG C, then add 500ml 32.5% nitre
Acid stirring 5 hours, weighs the powdered carbon 5g after above-mentioned nitric acid oxidation, adds 100ml tri-second tetramine, agitating heating
After Jun Yun, add 5 grams of N, N '-dicyclohexylcarbodiimides, back flow reaction 48 hours.By product washes clean,
Multifunction material for air purification is obtained after drying.
Sulfur dioxide, nitrogen dioxide are demonstrated by out in absorption test by above-mentioned material with heavy metal lead ion
The absorption property of color.Being 30% in humidity, flue gas flow is 200L/h, sulfur dioxide and content of nitrogen dioxide
When being respectively 30ppm and 15ppm, above-mentioned material centering SO2And NO2Equilibrium adsorption capacities be respectively
97mg/g and 79mg/g.In Staticadsorption experiment, when pH value of solution is 5, above-mentioned material is to 50mg/L
The equilibrium adsorption capacity of lead (II) be 133mg/g.
Example 3:
By 10g activated carbon powder (BET specific surface 937m2/ g, mesopore volume is 0.26ml/g) end 10%HCl
Solution stirs 5 hours at 60 DEG C, and purified charcoal powder adds the nitric acid of the 32.5% of 300ml again
Stir 5 hours, be washed till neutral drying.Weigh above-mentioned powder 5g, add the three second tetramines of 100ml, stirring
After heating, add N, N '-dicyclohexylcarbodiimide, back flow reaction 36 hours.Product is cleaned and dries,
Obtain Multifunction material for air purification.
Above-mentioned material is demonstrated by good absorption property to nitrogen dioxide, sulfur dioxide with heavy metal lead ion.
Being 35% in humidity, flue gas flow is 200L/h, sulfur dioxide and content of nitrogen dioxide be respectively 30ppm and
During 15ppm, above-mentioned material centering SO2And NO2Equilibrium adsorption capacities be respectively 75mg/g and 63mg/g.?
In Staticadsorption experiment, when pH value of solution is 5, the above-mentioned material equilibrium adsorption capacity to the lead (II) of 100mg/L
For 121mg/g.
Example 4
The HCl solution that dilute for 5g graphite mass fraction is 5% is stirred purification 3 hours at 50 DEG C, dries
Add after Gan 500ml 32.5% nitric acid stir 5 hours, add the three second tetramines of 100ml subsequently, stirring
After homogeneous heating, add 5 grams of N, N '-dicyclohexylcarbodiimides, back flow reaction 48 hours.Product is washed
Wash clean, after drying, obtain Multifunction material for air purification.
Above-mentioned material is demonstrated by good absorption property to nitrogen dioxide, sulfur dioxide with heavy metal lead ion.
Being 35% in humidity, flue gas flow is 200L/h, sulfur dioxide and content of nitrogen dioxide be respectively 30ppm and
During 15ppm, above-mentioned material centering SO2And NO2Equilibrium adsorption capacities be respectively 93mg/g and 71mg/g.?
In Staticadsorption experiment, when pH value of solution is 5, the above-mentioned material equilibrium adsorption capacity to the lead (II) of 100mg/L
For 106mg/g.
Example 5
By 5g biomass carbon (BET specific surface 937m2/ g, mesopore volume is 0.26ml/g) use mass fraction
Be 5% HCl solution at 60 DEG C of stirring purification 3 hours, add after drying 100ml 32.5% nitric acid
Stir 5 hours, add the three second tetramines of 100ml subsequently, after agitating heating is uniform, add 5 grams of N, N '-two
Carbodicyclo hexylimide, back flow reaction 24 hours.By product washes clean, obtain Multifunction after drying empty
Gas scavenging material.
Above-mentioned material is demonstrated by good absorption property to nitrogen dioxide, sulfur dioxide with heavy metal lead ion.
Being 35% in humidity, flue gas flow is 200L/h, sulfur dioxide and content of nitrogen dioxide be respectively 30ppm and
During 15ppm, above-mentioned material centering SO2And NO2Equilibrium adsorption capacities be respectively 81mg/g and 69mg/g.?
In Staticadsorption experiment, when pH value of solution is 5, the above-mentioned material equilibrium adsorption capacity to the lead (II) of 100mg/L
For 129mg/g.
Claims (7)
1. can the most efficiently remove Multifunction material for air purification of the pollutant acid gas such as micro nitrogen oxide, oxysulfide and heavy metal lead and preparation method thereof in air for one kind, it is characterized in that with porous charcoal as raw material, with hydrochloric acid, nitric acid, three second tetramines as modifying agent, by carbonization, carboxylated step preparation is a kind of with molecule copolycondensation etc. can the sour gas such as nitrogen dioxide, sulfur dioxide and the modified polyamine carbonaceous multifunctional air purifying material of heavy metal lead (II) in efficient absorption air.
The most according to claim 1, one can the most efficiently remove Multifunction material for air purification of the sour gas such as trace nitrogen dioxide, sulfur dioxide and heavy metal lead (II) and preparation method thereof in air, it is characterized in that the method includes porous charcoal purification, carboxylated, amination, cleans, dries, specifically comprise the following steps that
A), by porous charcoal use certain density hydrochloric acid solution, at 30~80 DEG C, stir purification more than 2 hours;
B) adding certain density salpeter solution in porous charcoal, after purification, heated and stirred, by product washing to neutrality, filtering drying after question response;
C), weigh a certain amount of through step B) porous charcoal powder after nitric acid oxidation, be distributed in a certain amount of ethylenediamine solution, to be mixed uniformly after, add N, N '-dicyclohexylcarbodiimide, back flow reaction a period of time;
D), above-mentioned product is first slightly washed with ethanol, then clean with ether, dry at a certain temperature to constant weight.
The most according to claim 2, one can the most efficiently remove Multifunction material for air purification of the pollutant acid gas such as trace nitrogen dioxide, sulfur dioxide, sulfur trioxide in air and heavy metal lead (II) and preparation method thereof simultaneously, it is characterised in that A) described in porous charcoal be that biomass carbon, activated carbon, graphite is dilute or mesoporous carbon.
The most according to claim 2, one can the most efficiently remove Multifunction material for air purification of the pollutant acid gas such as trace nitrogen dioxide, sulfur dioxide and heavy metal lead (II) and preparation method thereof in air simultaneously, it is characterised in that B) described in concentration of nitric acid be 10~50%.
The most according to claim 2, one can the most efficiently remove Multifunction material for air purification of the pollutant acid gas such as trace nitrogen dioxide, sulfur dioxide and heavy metal lead (II) and preparation method thereof in air simultaneously, it is characterised in that C) described carboxylated porous charcoal is 1 with the ratio of three second tetramines: (10~50).
The most according to claim 2, one can the most efficiently remove Multifunction material for air purification of the pollutant acid gas such as trace nitrogen dioxide, sulfur dioxide, sulfur trioxide in air and heavy metal lead (II) and preparation method thereof simultaneously, it is characterized in that E) described in reflux time be 6~96h, preferably 48h.
The most according to claim 2, one can the most efficiently remove Multifunction material for air purification of the pollutant acid gas such as trace nitrogen dioxide, sulfur dioxide, sulfur trioxide in air and heavy metal lead (II) and preparation method thereof simultaneously, it is characterized in that E) in the mass ratio of N, N '-dicyclohexylcarbodiimide and biomass carbon be 0.5-2.
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Cited By (2)
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CN111375383A (en) * | 2018-12-31 | 2020-07-07 | 中国石油化工股份有限公司 | SO (SO)2Preparation method and application of adsorbing material |
CN111578275A (en) * | 2020-04-03 | 2020-08-25 | 乐清市亿得利燃烧器有限公司 | Combustor with low emission of nitrogen oxides |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN111375383A (en) * | 2018-12-31 | 2020-07-07 | 中国石油化工股份有限公司 | SO (SO)2Preparation method and application of adsorbing material |
CN111375383B (en) * | 2018-12-31 | 2023-07-04 | 中国石油化工股份有限公司 | SO (SO) device 2 Preparation method and application of adsorption material |
CN111578275A (en) * | 2020-04-03 | 2020-08-25 | 乐清市亿得利燃烧器有限公司 | Combustor with low emission of nitrogen oxides |
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Application publication date: 20160824 |