CN102125823B - Adsorption resin with large specific surface area and large pore volume for removing volatile organic pollutants - Google Patents
Adsorption resin with large specific surface area and large pore volume for removing volatile organic pollutants Download PDFInfo
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- CN102125823B CN102125823B CN2011100065996A CN201110006599A CN102125823B CN 102125823 B CN102125823 B CN 102125823B CN 2011100065996 A CN2011100065996 A CN 2011100065996A CN 201110006599 A CN201110006599 A CN 201110006599A CN 102125823 B CN102125823 B CN 102125823B
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Abstract
The invention relates to an adsorption resin with large specific surface area and large pore volume for removing volatile organic pollutants and a preparation method thereof, and belongs to the field of removal of volatile organic pollutants (VOCs). The adsorption resin is prepared by direct polymerization with a cross linker in a mixed solvent, wherein the mixed solvent can be used as a solvent and can also be used as a template agent for adjusting the size of aperture. The adsorption resin has multistage pore structure, adjustable aperture, ultrahigh specific surface area (1,500 to 1,800 cm<2>/g) and pore volume (1.5 to 2.6cm<3>/g<-1>), low mass transfer resistance, high adsorption capacity, strong hydrophobic property and organic substance affinity; the adsorption capacity of the adsorption resin on the volatile organic substances reaches 2,400mg/g; and the adsorption resin has broad application prospect in the field of control of the volatile organic pollutants.
Description
Technical field
The present invention relates to a kind of bigger serface large pore volume polymeric adsorbent and preparation method thereof, also belong to the removal field of volatile organic contaminant simultaneously.
Background technology
Volatile organic matter (volatile organic compounds, be called for short VOCs) be the important atmosphere pollution of a large class, refer to that saturated vapour pressure at normal temperatures surpasses boiling point under 70.91Pa, the normal pressure less than 260 ℃ organic compound, its main component is hydro carbons, oxygen hydro carbons, contain halohydrocarbon, nitrogen hydrocarbon and sulphur hydro carbons etc.The harm of VOCs mainly comprises and generates photochemical fog, damages the ozone layer, is detrimental to health etc.In recent years, the air pollution problems inherent that VOCs brings is increasingly severe, therefore, works out the method that effect is good, cheap, technique is simply removed VOCs and is of practical significance very much.In numerous VOCs improvement technology, the recyclable most of VOCs of adsorption process, and easy to operate, operating cost is cheap, pollute control field at VOCs and be widely adopted.Active carbon has flourishing micropore, and adsorption capacity is large, but its heat and hydrothermal stability are poor, and hydrophilic, the hole is easily stopped up, the regeneration difficulty, and in engineering is used, have inflammable security hidden trouble, these deficiencies have limited its application to a certain extent.The inorganic molecule sieve is to then existing shortcomings such as organic Selective adsorption are not high, adsorption capacity is limited.The organic backbone of polymeric adsorbent can provide well selective for organic matter, and the pore structure of its prosperity and high-specific surface area can make it to have higher adsorption capacity.
The method that synthetic preparation with high-specific surface area adopts mainly contains suspension polymerization, phase separation method, hard template method, additive-crosslinking method etc., but their synthetic method has the shortcomings such as technique is loaded down with trivial details, production cost is higher.Patent 200710056021.5 discloses a kind of mesoporous polydivinylbenezene material with superpower characterization of adsorption, and synthetic by solvent thermal process, method is simple and easy, although this mesoporous polymer high adsorption capacity, specific area and pore volume less.Adopt crosslinking agent direct polymerization under catalyst action can make polymeric adsorbent, the method is simple to operate, and the polymeric adsorbent specific area that makes is large.Patent 200810140986.7 discloses a kind of synthetic method of adsorbent resin with high specific surface area, take dichloride methyl aromatic compound self or with two kinds of materials of arene compounds as raw material, raw material and solvent, catalyst are joined in the reactor, and the heat temperature raising reaction makes; This polymeric adsorbent specific area is high, but aperture less (mainly being to be micropore), resistance to mass tranfer is large, is difficult to the macromolecular adsorption desorption process of volatile organic matter.
Summary of the invention
The objective of the invention is provides a kind of polymeric adsorbent of effective processing volatile organic contaminant in order to overcome the defective of above-mentioned material and synthetic method existence.This polymeric adsorbent has hierarchical porous structure, and the aperture is adjustable, the specific area of superelevation and pore volume, and hydrophobicity is strong, and Organic Pollution gas is had very high selective and large adsorption capacity.
To achieve these goals, the present invention has taked following technical scheme.The synthetic method of polymeric adsorbent provided by the invention is, crosslinking agent is distributed in the mixed organic solvents, add until completely dissolved catalyst, be warming up to 60～80 ℃ after the stirring and reacted 8～16 hours, solid product is taken out in the Soxhlet extraction device successively with acetone, acetone and hydrochloric acid, distilled water and is washed 8 hours.
Described mixed organic solvents is the mixed solution of dichloroethanes and another kind of organic solvent, and volume ratio is 2: 1～20: 1.
Another kind of organic solvent in the described mixed organic solvents is n-hexane, oxolane or benzene.
Described catalyst is ferric trichloride.
Described crosslinking agent is the arene compounds that contains chloromethyl, such as xylylene dichlorides, dichloromethyl biphenyl or dichloromethyl anthracene.
The present invention has following beneficial effect:
1) mixed solution that adopts dichloroethanes and another kind of organic solvent in the synthetic method of the present invention is as solvent, and wherein dichloroethanes is as solvent, and another kind of organic solvent can be used as mesoporous template, thereby enlarges pore volume, increasing specific surface area; By regulating the addition of another kind of solvent, can regulate and control mesoporous pore size.
2) synthetic method of the present invention is one-step polymerization technique, and operation is simple.
3) polymeric adsorbent that synthesizes of the present invention has hierarchical porous structure, and the aperture is adjustable, the specific area (1500～1800cm of superelevation
2g
-1) and pore volume (1.5～2.6cm
3g
-1), the aperture is wider distribution in mesoporous scope, and resistance to mass tranfer is little, has very strong hydrophobicity and close Organic Compound, is conducive to the adsorption desorption process of large molecule VOCs.
Description of drawings
Fig. 1 is nitrogen Adsorption and desorption isotherms and the BJH pore size distribution figure of the synthetic polymeric adsorbent of embodiment 3.
Fig. 2 is the infrared spectrum analysis figure of the synthetic polymeric adsorbent of embodiment 3.
Fig. 3 is the synthetic polymeric adsorbent of embodiment 3 adsorption isotherm line chart to toluene under different temperatures.
Fig. 4 is the synthetic polymeric adsorbent of embodiment 3 adsorption isotherm line chart to steam under different temperatures.
Fig. 5 is the synthetic polymeric adsorbent of embodiment 3 at the adsorption breakthrough curve figure that has under steam and the anhydrous steam condition toluene.
The specific embodiment
Following illustrative example illustrates preparation method and institute's synthetic material absorption property of the Large ratio surface large pore volume polymeric adsorbent that the present invention relates to.
Embodiment 1: 5g is dissolved in the 50ml dichloroethanes the dichloromethyl benzene monomer, then add the 2.5mL n-hexane, add until completely dissolved the 2.645g ferric chloride catalyst, stir and be warming up to 60 ℃ after 2 hours, carry out Friedel-Crafts reaction 8 hours, after the room temperature cooling, solid product is taken out in the Soxhlet extraction device successively with acetone, acetone and hydrochloric acid, distilled water and is washed 8 hours.The BET specific area of this polymeric adsorbent is 1526cm
2g
-1, total pore volume is 1.687cm
3g
-1
Embodiment 2: with 5g 4,4 '-dichloromethyl biphenyl monomer is dissolved in the 50ml dichloroethanes, then add the 7.5mL oxolane, add until completely dissolved the 2.70g ferric chloride catalyst, stir and be warming up to 70 ℃ in 2 hours, carry out Friedel-Crafts reaction 10 hours, after the room temperature cooling, solid product is taken out in the Soxhlet extraction device successively with acetone, acetone and hydrochloric acid, distilled water and is washed 8 hours.The BET specific area of this polymeric adsorbent is 1756cm
2g
-1, total pore volume is 2.28cm
3g
-1
Embodiment 3: with 5g 4,4 '-dichloromethyl biphenyl monomer is dissolved in the 50ml dichloroethanes, then add the 10mL n-hexane, add until completely dissolved the 3.22g ferric chloride catalyst, stir and be warming up to 80 ℃ after 2 hours, carry out Friedel-Crafts reaction 12 hours, after the room temperature cooling, solid product is taken out in the Soxhlet extraction device successively with acetone, acetone and hydrochloric acid, distilled water and is washed 8 hours.The BET specific area of this polymeric adsorbent is 1592cm
2g
-1, total pore volume is 2.526cm
3g
-1
Embodiment 4: with 5g 9,10-dichloromethyl anthracene monomer is dissolved in the 50ml dichloroethanes, then add 25mL benzene, add until completely dissolved the 3.22g ferric chloride catalyst, stir and be warming up to 80 ℃ after 2 hours, carry out Friedel-Crafts reaction 14 hours, after the room temperature cooling, solid product is taken out in the Soxhlet extraction device successively with acetone, acetone and hydrochloric acid, distilled water and is washed 8 hours.The BET specific area of this polymeric adsorbent is 1638cm
2g
-1, total pore volume is 1.158cm
3g
-1
Embodiment 5: Large ratio surface large pore volume polymeric adsorbent is to the Static Adsorption of toluene:
Getting above-described embodiment 3 synthetic polymeric adsorbents 0.1 restrains, adopt intelligent weight adsorption instrument IGA-002 to measure under the different temperatures adsorption isotherm (accompanying drawing 3) to toluene, the result shows that this polymeric adsorbent has very large adsorption capacity to organic matter, and the equilibrium adsorption capacity to toluene under 25 ℃ of conditions reaches 2400mg/g.
Embodiment 6: Large ratio surface large pore volume polymeric adsorbent is to the Static Adsorption of steam:
Get synthetic polymeric adsorbents 0.1 gram of above-mentioned embodiment 3, adopt intelligent weight adsorption instrument IGA-002 to measure under the different temperatures the adsorption isotherm (accompanying drawing 4) of steam, the result shows that this polymeric adsorbent has good hydrophobicity.
Embodiment 7: Large ratio surface large pore volume polymeric adsorbent is to the Dynamic Adsorption of toluene:
Get the synthetic polymeric adsorbents 0.1 gram dress post of above-mentioned embodiment 3, at room temperature, will containing toluene concentration, to be about the dry air of 800ppm or relative humidity be that 28% humid air is with 15000h
-1Air speed by this adsorption column (accompanying drawing 5).The result shows, this polymeric adsorbent is 93% under the drying condition to the adsorption capacity that penetrates of toluene.
Claims (1)
1. bigger serface large pore volume polymeric adsorbent of removing volatile organic contaminant, it is characterized in that: the specific area of polymeric adsorbent is 1500～1800cm
2G
-1, pore volume is 1.5～2.6cm
3G
-1Described polymeric adsorbent is to be made by the crosslinking agent direct polymerization in mixed organic solvents; Described mixed organic solvents is made by dichloroethanes and the mixing of another kind of organic solvent, and both volume ratios are 2: 1～20: 1, and described another kind of organic solvent is n-hexane, oxolane or benzene; Described crosslinking agent is the arene compounds that contains chloromethyl, and the described arene compounds that contains chloromethyl is xylylene dichlorides, dichloromethyl biphenyl or dichloromethyl anthracene.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508508B (en) * | 2012-06-29 | 2016-07-13 | 中国科学院大连化学物理研究所 | The application in adsorbing separation of a kind of multiporous biological matter resin |
| CN103509194B (en) * | 2012-06-29 | 2015-07-15 | 中国科学院大连化学物理研究所 | Porous biomass acidic solid material, and preparation and application thereof |
| CN111318271A (en) * | 2020-03-10 | 2020-06-23 | 中科创景(广州)环保科技有限公司 | Macroporous adsorption resin columnar particles for adsorbing VOCs and preparation method thereof |
| CN113856652B (en) * | 2021-10-28 | 2024-01-26 | 山东省计量科学研究院 | VOCs (volatile organic compounds) high-molecular adsorption material and synthesis method thereof |
| CN116328739A (en) * | 2023-02-22 | 2023-06-27 | 东洋和光净化材料(江苏)有限公司 | Hydrophobic VOC adsorbent and production method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101288841A (en) * | 2008-06-11 | 2008-10-22 | 山东鲁抗立科药物化学有限公司 | Macroporous adsorption resin special for extracting cephalosporin C and its preparation method |
| CN101338019A (en) * | 2008-08-11 | 2009-01-07 | 郑州大学 | Method for synthesizing high specific surface area polymeric adsorbent and uses thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101288841A (en) * | 2008-06-11 | 2008-10-22 | 山东鲁抗立科药物化学有限公司 | Macroporous adsorption resin special for extracting cephalosporin C and its preparation method |
| CN101338019A (en) * | 2008-08-11 | 2009-01-07 | 郑州大学 | Method for synthesizing high specific surface area polymeric adsorbent and uses thereof |
Non-Patent Citations (2)
| Title |
|---|
| Si Guo Yuan et al..Facile synthesis and characterization of novel pseudo-hypercrosslinked resin.《Chinese Chemical Letters》.2008,第19卷第611-614页. * |
| W.L.SEDEREL et al..Styrene-Divinylbenzene Copolymers. Construction of Porosity in Styrene Divinylbenzene Matrices.《JOURNAL OF APPLIED POLYMER SCIENCE》.1973,第17卷第2835-2846页. * |
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