CN102125823A - 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 PDF

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CN102125823A
CN102125823A CN2011100065996A CN201110006599A CN102125823A CN 102125823 A CN102125823 A CN 102125823A CN 2011100065996 A CN2011100065996 A CN 2011100065996A CN 201110006599 A CN201110006599 A CN 201110006599A CN 102125823 A CN102125823 A CN 102125823A
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volatile organic
pore volume
surface area
specific surface
adsorption resin
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CN102125823B (en
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郝郑平
豆宝娟
李进军
王海林
李鹏
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Research Center for Eco Environmental Sciences of CAS
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Abstract

本发明涉及一种去除挥发性有机污染物的大比表面积大孔容吸附树脂及其制备方法,属于挥发性有机污染物(VOCs)的去除领域。本吸附树脂是以交联剂在混合溶剂中直接聚合制得,混合溶剂既可作为溶剂,也可作为模板剂来调节孔径大小。本发明的吸附树脂具有多级孔结构,孔径可调,超高的比表面积(1500~1800cm2/g)和孔容(1.5~2.6cm3/g-1),传质阻力小,吸附容量大,具有强疏水性和亲有机物性,对挥发性有机物的吸附能力高达2400mg/g,在挥发性有机污染物控制领域具有广阔的应用前景。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, belonging to the field of removal of volatile organic pollutants (VOCs). The adsorption resin is prepared by direct polymerization of a crosslinking agent in a mixed solvent, and the mixed solvent can be used not only as a solvent but also as a template to adjust the pore size. The adsorption resin of the present invention has a multi-level pore structure, adjustable pore diameter, super high specific surface area (1500-1800cm 2 /g) and pore volume (1.5-2.6cm 3 /g -1 ), small mass transfer resistance, and high adsorption capacity Large, with strong hydrophobicity and organophilicity, the adsorption capacity of volatile organic compounds is as high as 2400mg/g, and has broad application prospects in the field of volatile organic pollutant control.

Description

A kind of bigger serface large pore volume polymeric adsorbent of removing volatile organic contaminant
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 big class, be meant 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 brought is severe day by day, therefore, works out the method that effect is good, cheap, technology 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 the control field at VOCs and be widely adopted.Active carbon has flourishing micropore, and adsorption capacity is big, 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 not high to organic selection adsorptivity, that adsorption capacity is limited.The organic backbone of polymeric adsorbent can provide good selectivity for organic matter, and pore structure of its prosperity and high-specific surface area can make it to have higher adsorption capacity.
The method that synthetic macromolecule polymeric adsorbent with high-specific surface area adopts mainly contains suspension polymerization, phase separation method, hard template method, additive-crosslinking method etc., and technology is loaded down with trivial details, the more high shortcoming of production cost but their synthetic method has.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, though this mesoporous polymer high adsorption capacity, specific area is relative with pore volume less.Adopt crosslinking agent direct polymerization under catalyst action can make polymeric adsorbent, this method is simple to operate, and the polymeric adsorbent specific area that makes is big.Patent 200810140986.7 discloses a kind of synthetic method of adsorbent resin with high specific surface area, with dichloride methyl aromatic compound self or with two kinds of materials of arene compounds be raw material, raw material and solvent, catalyst are joined in the reactor, and the heat temperature raising reaction makes; This polymeric adsorbent specific area height, but aperture less (mainly being to be micropore), resistance to mass tranfer is big, 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 that above-mentioned material and synthetic method exist.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 the organic matter dusty gas is had very high selectivity and big 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, treat to dissolve fully the back and add catalyst, be warming up to 60~80 ℃ after the stirring and reacted 8~16 hours, solid product is taken out in cable-styled extractor 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 a ferric trichloride.
Described crosslinking agent is the arene compounds that contains chloromethyl, 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 agent, thereby enlarges pore volume, increasing specific surface area; By regulating the addition of another kind of solvent, adjustable mesoporous pore size.
2) synthetic method of the present invention is an one-step polymerization technology, 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 rerum natura, helps the adsorption desorption process of big molecule VOCs.
Description of drawings
Fig. 1 is the nitrogen adsorption desorption thermoisopleth 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 for the synthetic polymeric adsorbent of embodiment 3 at the adsorption penetration curve map 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, add the 2.5mL n-hexane then, treat to dissolve fully the back and add 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 cable-styled extractor 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, add the 7.5mL oxolane then, treat to dissolve fully the back and add 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 cable-styled extractor 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, add the 10mL n-hexane then, treat to dissolve fully the back and add 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 cable-styled extractor 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, add 25mL benzene then, treat to dissolve fully the back and add 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 cable-styled extractor 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 adsorbs the static state of toluene:
Getting the foregoing description 3 synthetic polymeric adsorbents 0.1 restrains, adopt intelligent weight absorption 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 big 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 adsorbs the static state of steam:
Get synthetic polymeric adsorbents 0.1 gram of above-mentioned embodiment 3, adopt intelligent weight absorption 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 absorption 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 that this polymeric adsorbent is 93% under the drying condition to the adsorption capacity that penetrates of toluene.

Claims (2)

1.一种去除挥发性有机污染物的大比表面积大孔容吸附树脂的合成方法,其特征在于,是在混合溶剂中直接聚合制得,该混合溶剂为二氯乙烷和另一种有机溶剂的混合溶液,体积比为2∶1~20∶1。1. A synthetic method of a large specific surface area large pore volume adsorption resin for removing volatile organic pollutants is characterized in that it is prepared by direct polymerization in a mixed solvent, and the mixed solvent is ethylene dichloride and another organic The mixed solution of solvents has a volume ratio of 2:1 to 20:1. 2.根据权利要求1所述的一种去除挥发性有机污染物的大比表面积大孔容吸附树脂的合成方法,其特征在于,混合有机溶剂中的另一种有机溶剂为正己烷、四氢呋喃或苯。2. the synthetic method of a kind of large specific surface area large pore volume adsorption resin that removes volatile organic pollutants according to claim 1 is characterized in that, another kind of organic solvent in the mixed organic solvent is normal hexane, tetrahydrofuran or benzene.
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Cited By (5)

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CN103508508A (en) * 2012-06-29 2014-01-15 中国科学院大连化学物理研究所 Application of porous biomass resin in adsorptive separation
CN103509194A (en) * 2012-06-29 2014-01-15 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
CN113856652A (en) * 2021-10-28 2021-12-31 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

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103508508A (en) * 2012-06-29 2014-01-15 中国科学院大连化学物理研究所 Application of porous biomass resin in adsorptive separation
CN103509194A (en) * 2012-06-29 2014-01-15 中国科学院大连化学物理研究所 Porous biomass acidic solid material, and preparation and application thereof
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
CN103508508B (en) * 2012-06-29 2016-07-13 中国科学院大连化学物理研究所 Application of a Porous Biomass Resin in Adsorption Separation
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
CN113856652A (en) * 2021-10-28 2021-12-31 山东省计量科学研究院 VOCs (volatile organic compounds) high-molecular adsorption material and synthesis 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

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