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
adsorption resin
surface area
specific surface
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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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Research Center for Eco Environmental Sciences of CAS
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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

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. synthetic method of removing the bigger serface large pore volume polymeric adsorbent of volatile organic contaminant, it is characterized in that, be that direct polymerization makes in mixed solvent, this mixed solvent is the mixed solution of dichloroethanes and another kind of organic solvent, and volume ratio is 2: 1～20: 1.
2. a kind of synthetic method of removing the bigger serface large pore volume polymeric adsorbent of volatile organic contaminant according to claim 1 is characterized in that the another kind of organic solvent in the mixed organic solvents is n-hexane, oxolane or benzene.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
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

Citations (2)

* Cited by examiner, † Cited by third party
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
Title
《Chinese Chemical Letters》 20081231 Si Guo Yuan et al. Facile synthesis and characterization of novel pseudo-hypercrosslinked resin 第611-614页 1-2 第19卷, *
《JOURNAL OF APPLIED POLYMER SCIENCE》 19731231 W.L.SEDEREL et al. Styrene-Divinylbenzene Copolymers. Construction of Porosity in Styrene Divinylbenzene Matrices 第2835-2846页 1-2 第17卷, *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
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 The application in adsorbing separation of a kind of multiporous biological matter resin
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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