CN105131163A - VOC (volatile organic compound) absorbent and preparation method thereof - Google Patents
VOC (volatile organic compound) absorbent and preparation method thereof Download PDFInfo
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- CN105131163A CN105131163A CN201510576050.9A CN201510576050A CN105131163A CN 105131163 A CN105131163 A CN 105131163A CN 201510576050 A CN201510576050 A CN 201510576050A CN 105131163 A CN105131163 A CN 105131163A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a VOC (volatile organic compound) absorbent and a preparation method thereof. The VOC absorbent is prepared by introducing a hydrophilic third monomer on the basis of styrene and butyl acrylate by virtue of cross-linking copolymerization. A most remarkable characteristic of the VOC absorbent is that the particle hardness is good, the absorbed particles are not bonded, a good particle shape can be maintained after the absorbent is recycled, the absorption multiplying power before and after the recycling is not obviously changed, the problems that the traditional absorbent is poor in recycling performance and the recycled particles are bonded and need to be crushed can be solved, and the application cost can be effectively reduced. The absorbent can be widely used for treating industrial waste water and waste liquid containing VOC solvent as well as treating the leakage and emergently absorbing the organic solvent in the chemical production, and is wide in development and application prospect.
Description
Technical field
The invention belongs to functional high polymer material field, relate to environmental pollution treatment technology, more specifically relate to a kind of VOC absorption agent and preparation method thereof.
Background technology
Volatile organic compounds (volatileorganiccompounds, VOC) has tremendous influence to HUMAN HEALTH, and VOC common in industry has benzene,toluene,xylene, vinyl acetic monomer, N-BUTYL ACETATE, trieline, chloroform, tetracol phenixin etc.In confirmed 900 multiple indoor chemical substances at present and biological material, volatile organic compounds is at least more than 350 kinds, wherein kind more than 20 is carcinogens or mutagen, and Long Term Contact can cause lung cancer, leukemia or cause miscarriage, fetal anomaly and growth retardation etc.
Utilize absorbing material to absorb process VOC and prevent and treat the important and effective approach that VOC solvent pollutes.Both at home and abroad to absorbing material preparation compared and studied widely, the absorbency of physical-chemical composite crosslinking high oil absorbing resin to benzene synthesized as adopted suspension polymerization reaches 10-15g/g(polymer journal, 2003, (1): 52-55), the absorbency of polymethacrylate high oil absorbing resin to toluene of suspension emulsion polymerization synthesis is adopted to reach 17.6g/g(PolymersforAdvancedTechnologies, 2011,22 (12): 1898-1904).Except receptivity, desorption regeneration after absorption agent uses is most important, the renovation process that oil-absorbing resin is relatively commonly used has extraction process, surfactant method and distillation method, more than 90% p-Xylol absorbed can be extracted as adopted alcohol extraction method, surfactant emulsifies method of reproduction is recyclable 10-20%(chemical propellant and macromolecular material also, 2008,6 (1): 56-58), ethanol distillation rule can toluene (Northwest Agricultural University's journal of desorption more than 99%, 1999,27 (3): 44-49).The present inventor place seminar proposes and adds hydrodistillation, this method is compared to more economy, the environmental protection of ethanol distillation method, more than 90% (study on the synthesis of vinylformic acid short-chain ester high oil absorbing resin, University of Fuzhou's master thesis, 2004) can be reached to the rate of recovery of Resin Absorbent toluene.But, the phenomenon that resin particle assembles bonding is often there is in resin in the process of regeneration, just can reuse after must carrying out fragmentation to regenerating resin, otherwise easily result in blockage or follow-up use difficulty, also cannot realize the in-situ regeneration of resin in absorption unit and utilize.
Summary of the invention
The object of the invention is to for problems such as the gathering bonding of absorption agent in regenerative process, on the basis ensureing product stability, provide a kind of VOC absorption agent and preparation method thereof.The present invention, by introducing hydrophilic monomer, abolishes the directed thinking that oil-absorbing resin adopts oleophylic monomer simply, by giving absorption agent certain wetting ability, makes absorbent grains be not easy to assemble bonding in regeneration removal process; Obtained absorption agent is spheroidal particle, has higher absorbency, absorbs rear surface non-caked, and regeneration still keeps good particle form after reclaiming.
For realizing the object of the invention, adopt following technical scheme:
A kind of VOC absorption agent, comprises the raw material of following parts by weight: vinylbenzene 100-200 part, butyl acrylate 30-100 part, wetting ability Third monomer 0-1.5 part, linking agent 0.1-2.0 part, initiator 0.3-1.5 part, polyvinyl alcohol 0.2-1.0 part, distilled water 300-400 part.
Described wetting ability Third monomer is the vinyl monomer with carboxyl or acid anhydrides on molecular structure;
Concrete, wetting ability Third monomer can be the composition of one or more in vinylformic acid, methacrylic acid, MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE.
Described linking agent is the composition of one or more in ethylene glycol dimethacrylate, N, N'-methylene-bisacrylamide, Vinylstyrene;
Described initiator is the composition of one or more in dibenzoyl peroxide, dilauroyl peroxide, Diisopropyl azodicarboxylate.
Prepare a method for VOC absorption agent as above, comprise the following steps:
1) add in there-necked flask by polyvinyl alcohol and distilled water, stirring and dissolving at 60-80 DEG C, is cooled to room temperature, more logical N
2deoxygenation;
2) vinylbenzene is mixed with butyl acrylate, then wetting ability Third monomer is added, stir, form monomer mixed solution;
3) in monomer mixed solution, add the linking agent of initiator and 0.1-1.0 part, add after stirring and dissolving in there-necked flask, dispersed with stirring;
4) control stirring velocity 250-350rpm, in the water-bath of 70-90 DEG C, react 4-8 hour, in reaction process, add the linking agent of residuals weight part;
5) by product vacuum suction filtration, then use the water washing of 50 DEG C-60 DEG C, be finally placed in the vacuum drying oven of 50 DEG C and carry out drying.
In step 4), the linking agent of residuals weight part first uses acetone solution, after reaction carries out 1-3 hour, is slowly added dropwise in reaction system.
The linking agent adopted in linking agent used and step 4) in step 3) can be different sorts.
Obtained VOC absorption agent is spheroidal particle, and regeneration is still the spheroidal particle of dispersion after reclaiming.
Described VOC absorption agent to the method for calculation of VOC solvent absorbency is: the dry box accurately taking certain mass, immerses in enough VOC solvent to be measured, to be absorbed saturated after take absorption agent absorb after quality, be calculated as follows absorbency:
。
remarkable advantage of the present invention is:
(1) oil-absorbing resin adopts oleophilic drainage monomer to prepare through copolymerzation with cross-linking usually, novelty of the present invention is to introduce hydrophilic monomer, overcome the technology prejudice that oil-absorbing resin always adopts oleophylic monomer, by giving absorption agent certain wetting ability, absorbent grains is made to be not easy to assemble bonding in regeneration removal process; Meanwhile, design being optimized to the crosslinking structure of absorbent grains, by adding linking agent stage by stage, particle surface being cross-linked again, improve surface crosslinking density, the rigidity of enhanced granule;
(2) absorption agent obtained by the present invention is spheroidal particle, there is higher absorbency, absorption rear surface is non-caked, still keep good particle form after regeneration recovery, solve existing absorption agent and absorb the not easily process of rear bonding mutually, the easy blocking pipe of absorption process and after reclaiming, need the problems such as fragmentation again;
(3) the VOC absorption agent that obtains of the present invention, particle bond phenomenon is there is not in regeneration removal process, resin regeneration still keeps good particle form after reclaiming, can use by repeated regeneration, and absorbency keeps stable, the problem that conventional absorbents reclaims bonding can be solved, improve recovery utilization rate, effective reduction use cost, industrial usability is good.
Accompanying drawing explanation
1)fig. 1 is the product form before the made VOC absorption agent of embodiment 1 absorbs;
2) Fig. 2 is the product form after the made VOC absorbent regeneration of embodiment 1 reclaims;
3) Fig. 3 is the product form before the made VOC absorption agent of comparative example 1 absorbs;
4) Fig. 4 is the product form after the made VOC absorbent regeneration of comparative example 1 reclaims.
Embodiment
The present invention's the following example further illustrates the present invention, but protection scope of the present invention is not limited to the following example.
embodiment 1
1) add in there-necked flask by polyvinyl alcohol 0.05g, stirring and dissolving in the 60g distilled water of 75 DEG C, is cooled to room temperature, more logical N
2deoxygenation;
2) accurately take vinylbenzene 21g, butyl acrylate 7g, composition mixing solutions, then add MALEIC ANHYDRIDE 0.09g, stirring and dissolving;
3) in monomer mixed solution, add dibenzoyl peroxide 0.12g and Vinylstyrene 0.04g(add linking agent for the first time), stirring and dissolving, adds in there-necked flask, dispersed with stirring;
4) control stirring velocity 300rpm, react after 2 hours in the water-bath of 80 DEG C, slowly add the second time of the Vinylstyrene 0.02g(after with acetone solution and add linking agent), continue reaction 2 hours, 85 DEG C of reactions 2 hours, then at 87 DEG C slaking half an hour;
5) product vacuum suction filtration, then use the water washing of 50 DEG C-60 DEG C, be finally placed in the vacuum drying oven of 50 DEG C and carry out drying, obtain VOC absorption agent;
The absorbency of this absorption agent Dichlorodiphenyl Acetate butyl ester is 13g/g, is 15g/g to the absorbency of toluene; Reclaim absorption agent by adding hydrodistillation, after regeneration, the absorbency of absorption agent Dichlorodiphenyl Acetate butyl ester is 12.7g/g, is 14.9g/g to the absorbency of toluene.
comparative example 1
1) add in there-necked flask by polyvinyl alcohol 0.05g, stirring and dissolving in the 60g distilled water of 75 DEG C, is cooled to room temperature, more logical N
2deoxygenation;
2) vinylbenzene 21g, butyl acrylate 7g is accurately taken, composition mixing solutions;
3) in monomer mixed solution, add dibenzoyl peroxide 0.12g and cross-linker divinylbenzene 0.06g, stirring and dissolving, add in there-necked flask, dispersed with stirring;
4) control stirring velocity 300rpm, react 4 hours in the water-bath of 80 DEG C, continue reactions 2 hours at 85 DEG C, then at 87 DEG C slaking half an hour;
5) product vacuum suction filtration, then use the water washing of 50 DEG C-60 DEG C, be finally placed in the vacuum drying oven of 50 DEG C and carry out drying, obtain VOC absorption agent;
The absorbency of this absorption agent Dichlorodiphenyl Acetate butyl ester is 11.7g/g, is 13.3g/g to the absorbency of toluene; Reclaim absorption agent by adding hydrodistillation, after regeneration, the absorbency of absorption agent Dichlorodiphenyl Acetate butyl ester is 11.2g/g, is 13g/g to the absorbency of toluene.
As can be seen from above-mentioned two comparative examples, the absorbency of embodiment 1 is better than comparative example 1.As can be seen from Fig. 1 and Fig. 3, before absorption VOC, the absorbent grains exterior appearance of two schemes synthesis, without larger difference, is all spheroidal particle; After absorbent regeneration recycling, as can be seen from Fig. 2 and Fig. 4, the absorption agent of embodiment 1 is still particle, and the absorption agent of comparative example 1 is bonded together, and destroys the pattern of particle.Visible, due to adding of hydrophilic monomer, and the optimization of linking agent feed postition, the absorption agent prepared by the present invention has good absorption and regenerability, practical.
embodiment 2
1) add in there-necked flask by polyvinyl alcohol 0.1g, stirring and dissolving in the 60g distilled water of 65 DEG C, is cooled to room temperature, more logical N
2deoxygenation;
2) accurately take vinylbenzene 21g, butyl acrylate 7g, composition mixing solutions, then add methacrylic acid 0.1g, stir;
3) in monomer mixed solution, add dibenzoyl peroxide 0.12g and Vinylstyrene 0.04g, stirring and dissolving, add in there-necked flask, dispersed with stirring;
4) control stirring velocity 300rpm, react after 2 hours in the water-bath of 80 DEG C, add by the Vinylstyrene 0.02g of acetone solution, continue reaction 2 hours, 85 DEG C of reactions 2 hours, then at 87 DEG C slaking half an hour;
5) product vacuum suction filtration, then use the water washing of 50 DEG C-60 DEG C, be finally placed in the vacuum drying oven of 50 DEG C and carry out drying, obtain VOC absorption agent.
embodiment 3
1) add in there-necked flask by polyvinyl alcohol 0.05g, stirring and dissolving in the 60g distilled water of 70 DEG C, is cooled to room temperature, more logical N
2deoxygenation;
2) accurately take vinylbenzene 20g, butyl acrylate 10g, composition mixing solutions, then add vinylformic acid 0.1g, stir;
3) in monomer mixed solution, add dibenzoyl peroxide 0.12g and Vinylstyrene 0.05g, stirring and dissolving, add in there-necked flask, dispersed with stirring;
4) control stirring velocity 300rpm, react after 2 hours in the water-bath of 80 DEG C, add by the Vinylstyrene 0.02g of acetone solution, continue reaction 2 hours, 85 DEG C of reactions 2 hours, then at 87 DEG C slaking half an hour;
5) product vacuum suction filtration, then use the water washing of 50 DEG C-60 DEG C, be finally placed in the vacuum drying oven of 50 DEG C and carry out drying, obtain VOC absorption agent.
embodiment 4
1) add in there-necked flask by polyvinyl alcohol 0.05g, stirring and dissolving in the 60g distilled water of 80 DEG C, is cooled to room temperature, more logical N
2deoxygenation;
2) accurately take vinylbenzene 25g, butyl acrylate 10g, composition mixing solutions, then add MALEIC ANHYDRIDE 0.1g, stirring and dissolving is even;
3) in monomer mixed solution, add dilauroyl peroxide 0.12g and Vinylstyrene 0.05g, stirring and dissolving, add in there-necked flask, dispersed with stirring;
4) control stirring velocity 300rpm, react 2 hours in the water-bath of 80 DEG C, add by the N of acetone solution, N'-methylene-bisacrylamide 0.02g, continue reaction 2 hours, 85 DEG C of reactions 2 hours, then at 87 DEG C slaking half an hour;
5) product vacuum suction filtration, then use the water washing of 50 DEG C-60 DEG C, be finally placed in the vacuum drying oven of 50 DEG C and carry out drying, obtain VOC absorption agent.
embodiment 5
1) add in there-necked flask by polyvinyl alcohol 0.1g, stirring and dissolving in the 60g distilled water of 75 DEG C, is cooled to room temperature, more logical N
2deoxygenation;
2) accurately take vinylbenzene 20g, butyl acrylate 8g, composition mixing solutions, then add FUMARIC ACID TECH GRADE 0.08g, stirring and dissolving is even;
3) in monomer mixed solution, add Diisopropyl azodicarboxylate 0.12g and Vinylstyrene 0.04g, stirring and dissolving, add in there-necked flask, dispersed with stirring;
4) control stirring velocity 300rpm, react 2 hours in the water-bath of 80 DEG C, add by the linking agent ethylene glycol dimethacrylate 0.02g of acetone solution, continue reaction 2 hours, 85 DEG C of reactions 2 hours, then at 87 DEG C slaking half an hour;
5) product vacuum suction filtration, then use the water washing of 50 DEG C-60 DEG C, be finally placed in the vacuum drying oven of 50 DEG C and carry out drying, obtain VOC absorption agent.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (7)
1. a VOC absorption agent, is characterized in that: the raw material comprising following parts by weight: vinylbenzene 100-200 part, butyl acrylate 30-100 part, wetting ability Third monomer 0-1.5 part, linking agent 0.1-2.0 part, initiator 0.3-1.5 part, polyvinyl alcohol 0.2-1.0 part, distilled water 300-400 part; Described wetting ability Third monomer is the vinyl monomer with carboxyl or acid anhydrides on molecular structure.
2. VOC absorption agent according to claim 1, is characterized in that: described wetting ability Third monomer is the composition of one or more in vinylformic acid, methacrylic acid, MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE.
3. VOC absorption agent according to claim 1, is characterized in that: described linking agent is the composition of one or more in ethylene glycol dimethacrylate, N, N'-methylene-bisacrylamide, Vinylstyrene.
4. VOC absorption agent according to claim 1, is characterized in that: described initiator is the composition of one or more in dibenzoyl peroxide, dilauroyl peroxide, Diisopropyl azodicarboxylate.
5. prepare a method for VOC absorption agent as claimed in claim 1, it is characterized in that: comprise the following steps:
1) add in there-necked flask by polyvinyl alcohol and distilled water, stirring and dissolving at 60-80 DEG C, is cooled to room temperature, more logical N
2deoxygenation;
2) vinylbenzene is mixed with butyl acrylate, then wetting ability Third monomer is added, stir, form monomer mixed solution;
3) in monomer mixed solution, add the linking agent of initiator and 0.1-1.0 part, add after stirring and dissolving in there-necked flask, dispersed with stirring;
4) control stirring velocity 250-350rpm, in the water-bath of 70-90 DEG C, react 4-8 hour, in reaction process, add the linking agent of residuals weight part;
5) by product vacuum suction filtration, then use the water washing of 50 DEG C-60 DEG C, be finally placed in the vacuum drying oven of 50 DEG C and carry out drying.
6. the preparation method of VOC absorption agent according to claim 5, is characterized in that: in step 4), the linking agent of residuals weight part first uses acetone solution, after reaction carries out 1-3 hour, is slowly added dropwise in reaction system.
7. the preparation method of VOC absorption agent according to claim 5, is characterized in that: the linking agent adopted in linking agent used and step 4) in step 3) can be different sorts.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106925238A (en) * | 2017-04-10 | 2017-07-07 | 福州大学 | A kind of sponge support type organic solvent absorbent and preparation method thereof |
| CN108310933A (en) * | 2018-02-25 | 2018-07-24 | 段宝荣 | The preparation method of the remover of VOC in leather finish workshop |
| CN110983771A (en) * | 2019-12-27 | 2020-04-10 | 上海市纺织科学研究院有限公司 | VOC remover for vehicle composite fabric |
| CN112920505A (en) * | 2019-12-05 | 2021-06-08 | 苏州荣昌复合材料有限公司 | Environment-friendly low-volatility polypropylene composite material and preparation method thereof |
| CN115138349A (en) * | 2022-08-02 | 2022-10-04 | 扬州工业职业技术学院 | Amphiphilic porous polymer material for treating aromatic compound-containing wastewater |
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| WO1993012167A1 (en) * | 1991-12-19 | 1993-06-24 | The Dow Chemical Company | Seeded porous copolymers and ion-exchange resins prepared therefrom |
| WO2013119936A2 (en) * | 2012-02-09 | 2013-08-15 | Life Technologies Corporation | Hydrophilic polymeric particles and methods for making same |
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| WO1993012167A1 (en) * | 1991-12-19 | 1993-06-24 | The Dow Chemical Company | Seeded porous copolymers and ion-exchange resins prepared therefrom |
| WO2013119936A2 (en) * | 2012-02-09 | 2013-08-15 | Life Technologies Corporation | Hydrophilic polymeric particles and methods for making same |
| CN103752289A (en) * | 2014-01-26 | 2014-04-30 | 福州大学 | Organic solvent absorbing agent and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106925238A (en) * | 2017-04-10 | 2017-07-07 | 福州大学 | A kind of sponge support type organic solvent absorbent and preparation method thereof |
| CN106925238B (en) * | 2017-04-10 | 2019-04-09 | 福州大学 | A kind of sponge support type organic solvent absorbent and preparation method thereof |
| CN108310933A (en) * | 2018-02-25 | 2018-07-24 | 段宝荣 | The preparation method of the remover of VOC in leather finish workshop |
| CN108310933B (en) * | 2018-02-25 | 2020-10-02 | 烟台大学 | Preparation method of VOC remover in leather finishing workshop |
| CN112920505A (en) * | 2019-12-05 | 2021-06-08 | 苏州荣昌复合材料有限公司 | Environment-friendly low-volatility polypropylene composite material and preparation method thereof |
| CN110983771A (en) * | 2019-12-27 | 2020-04-10 | 上海市纺织科学研究院有限公司 | VOC remover for vehicle composite fabric |
| CN115138349A (en) * | 2022-08-02 | 2022-10-04 | 扬州工业职业技术学院 | Amphiphilic porous polymer material for treating aromatic compound-containing wastewater |
| CN115138349B (en) * | 2022-08-02 | 2023-09-29 | 扬州工业职业技术学院 | Amphiphilic porous polymer material for aromatic compound-containing wastewater treatment |
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