CN102513068A - Modified polyaniline adsorbent and application of modified polyaniline adsorbent in wastewater treatment - Google Patents
Modified polyaniline adsorbent and application of modified polyaniline adsorbent in wastewater treatment Download PDFInfo
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- CN102513068A CN102513068A CN2011103415099A CN201110341509A CN102513068A CN 102513068 A CN102513068 A CN 102513068A CN 2011103415099 A CN2011103415099 A CN 2011103415099A CN 201110341509 A CN201110341509 A CN 201110341509A CN 102513068 A CN102513068 A CN 102513068A
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Abstract
The invention provides a modified polyaniline adsorbent, and belongs to the technical field of polymer composite materials. According to the invention, an aniline monomer is modified by using sodium dodecylbenzene sulfonate and other surfactants containing a sulfonic group, and then is subjected to polymerization to obtain the adsorbent, wherein the polyaniline with unobvious adsorption performance is combined with the sodium dodecylbenzene sulfonate and other surfactants containing the sulfonic group, such that the polyaniline molecule chain is grafted with the sulfonic group with the cation adsorption performance, at the same time the surfactant exists, such that the internal pore structure of the polymer is changed so as to enhance the adsorption performance and the stability. The results of a plurality of experiments show that: the modified polyaniline adsorbent of the present invention provides good adsorption capacities for cationic dyes, heavy metal ions and phenol in wastewater. The adsorbent of the present invention has advantages of cheap and easily obtained raw materials, simple preparation process, low cost, good chemical stability, easy separation, capability of recycle, no secondary pollution on the environment, and the like, and is a potential sewage adsorption material.
Description
Technical field
The invention belongs to technical field of polymer composite materials, relate to a kind of modified polyaniline preparation of adsorbent, relate in particular to the polyaniline preparation of adsorbent that a kind of usefulness contains sulfonic surface-active modification; The present invention also relates to the application of this modified polyphenyl amine absorber dye of positive ion, heavy metal ion, phenolic material in absorption sewage simultaneously.
Background technology
Along with Increase of population and industrial expansion, water resources shortage, particularly water quality type lack of water phenomenon are serious day by day, and the effect of sewage disposal technology in producing and living is also increasing.
Textile printing and dyeing industry is the discharge of wastewater rich and influential family, accounts for 1/3 of whole discharged volume of industrial waste water.Become increasingly conspicuous so dyeing waste water pollutes the environmental problem that causes, the most dyestuffs such as the dyes of positive ion such as rhodamine B and methylene blue have certain toxicity and biological characteristic of concentration, are difficult to degraded under field conditions (factors).Dyeing waste water directly is discharged into water body, and it is attractive in appearance not only to influence water body, reduces the water body light transmittance, and destroys water ecosystem.Dye well wherein between metabolite contain multiple noxious material and can cause multiple harm the water body biology.The processing of dyeing waste water is mainly set about from the decolouring problem.At present, decoloration treatment method commonly used has neutralisation, oxidizing process, absorption method, hyperfiltration and Coagulation Method etc.
Aspect water pollution, heavy metal pollution is another problem that is difficult to effect a radical cure equally.Processing method to heavy metal wastewater thereby mainly comprises: absorption method, ion precipitation method, exchanger resin method or the like.Adopt chemical precipitation methods to handle heavy metal wastewater therebies in the industry, but the chemical precipitation method existence is prone to cause the water quality sclerosis more, not thorough to the heavy metal ion processing of low concentration, cause shortcomings such as secondary pollution easily.Ion-exchange-resin process can be transferred to heavy metal ion on the resin, but resin is difficult to separate with heavy metal ion, no matter be aspect the utilizing again of resin or all not enough to some extent aspect the recovery of precious metal.
In recent years, absorption method is more and more paid close attention to by people as the high-efficient treatment method of waste water from dyestuff and heavy metal containing sewage.Wherein to adopt merchandise active carbon be adsorbent more, and people attempt that research and development are more cheap at present, more effective sorbing material to be to replace active carbon and further improve adsorption efficiency and to reduce cost.
Summary of the invention
The objective of the invention is to the problem that exists in the prior art, a kind of modified polyphenyl amine absorber with heavy metal ion and phenol in the selective absorption dye of positive ion, the trade effluent is provided.
Modified polyaniline preparation of adsorbent of the present invention comprises following processing step:
1, a kind of modified polyphenyl amine absorber is to be formed by following prepared:
(1) it is soluble in water to contain sulfonic surfactant, stirs the mixed solution that is mixed with concentration 0.07 ~ 0.1mol/L.
Said to contain sulfonic surfactant be phenylbenzimidazole sulfonic acid salt such as neopelex, cetyl benzene sulfonic acid sodium salt, secondary sodium alkyl benzene sulfonate, chain sulfonated hydrocarbons such as methyl sodiosul foaliphatate, PFOS sodium.
(2) add the aniline monomer that contains 0.2 ~ 0.5 times of sulfonic surfactant quality, stirred 2 ~ 5 hours;
(3) initiator ammonium persulfate of adding aniline monomer equimolar amounts continues to stir 20 ~ 24 hours; Suction filtration, the wash solids deposition;
In order to make surfactant fully hydrolysis in water, behind the adding initiator ammonium persulfate, stirred 20 ~ 24 hours pH=2 ~ 3 of adjustment mixed solution again earlier; Suction filtration, the wash solids deposition.
(4) oven dry, grinding obtain modified polyphenyl amine absorber (PANSDBS).
Describe through infrared spectrum and thermogravimetric curve structure and performance below modified polyphenyl amine absorber of the present invention.
1, infrared spectrum
Fig. 1 is the infrared spectrogram of the PANSDBS adsorbent of the present invention's preparation.1202.81cm among Fig. 1
-1, 1036.32 cm
-1, 620.58 cm
-1The peak be sulfonic characteristic peak, successful grafting has been described in PANSDBS sulfonic group.
2, thermogravimetric analysis
Fig. 2 is the polyaniline of non-modified and the thermogravimetric data analysis figure of PANSDBS adsorbent.Wherein a is the polyaniline that non-modified is crossed; B is the PANSDBS adsorbent.As can beappreciated from fig. 2; PANSDBS adsorbent stability in temperature-rise period of the present invention's preparation obviously is better than the non-modified polyaniline; And when temperature was raised to 100 ℃, the decomposition amount of PANSDBS adsorbent was merely 2.6263%, explained that it at room temperature has good stability.
3, XRD test
Fig. 3 is the XRD resolution chart of the PANSDBS adsorbent of the present invention's preparation.As can beappreciated from fig. 3, PANSDBS does not have obvious crystal structure, is unformed shape.
In sum; The present invention contains sulfonic surfactant with script unconspicuous polyaniline of absorption property and neopelex etc. and mutually combines; Make the sulfonic group that has the absorption cationic properties in the grafting of polyaniline molecule chain, strengthened absorption property and stability because the existence of surfactant has changed the inside pore passage structure of polymer simultaneously.
Experiment showed, that in a large number modified polyphenyl amine absorber of the present invention to also the dye of positive ion being had the selection adsorptivity, all has better adsorption capacity to waste water from dyestuff and the trade effluent that contains heavy metal ion and phenol, therefore can be used for the processing of organic wastewater.This adsorbent low in raw material cost is easy to get simultaneously, and preparation technology is simple, and cost is low; Chemical stability is good, is easy to separate, and reusable edible does not cause advantages such as secondary pollution to environment, be a kind of very potential sewage sorbing material.
A large amount of experiment proofs; The ratio of the consumption of modified polyphenyl amine absorber of the present invention and pending wastewater flow rate is 1:1000 ~ 1:10000; Stir and leave standstill 30 ~ 60 minutes after 30 ~ 60 minutes with adsorbent and sewage Separation of Solid and Liquid, the sewage of handling reaches discharging standards; Material of the present invention can be widely used in the purification and the processing of industry and sanitary wastewater, have cost low, pollution-free, adsorb strong ability, be easy to promote, implement advantages such as convenient.
Description of drawings
Fig. 1 is the infrared spectrogram of the PANSDBS adsorbent of the present invention's preparation.
Fig. 2 is the polyaniline of non-modified and the thermogravimetric curve of the PANSDBS adsorbent that the present invention prepares.
Fig. 3 is the XRD resolution chart of the PANSDBS adsorbent of the present invention's preparation.
The specific embodiment
Be described further through the method for specific embodiment below preparation of adsorbent of the present invention and processing trade effluent.
Embodiment one: the modified polyaniline preparation of adsorbent
The 10g neopelex is dissolved in 500 ml waters, stirred 2 ~ 5 hours; Add 2g aniline (AN), continue to stir 2 ~ 5 hours; Add the 4.9g ammonium persulfate, the pH=2 of adjustment mixed solution continues to stir 24 hours earlier; Suction filtration, the wash solids deposition; Oven dry, grind into powder obtain the polyaniline adsorbent (PANSDBS) after the modification.
Embodiment two: the modified polyaniline preparation of adsorbent
10g cetyl benzene sulfonic acid sodium salt is dissolved in 500 ml waters, stirred 2 ~ 5 hours; Add 2-4g aniline (AN), continue to stir 2 ~ 5 hours; Add the 8.2g ammonium persulfate, the pH=3 of adjustment mixed solution continues to stir 24 hours earlier; Suction filtration, the wash solids deposition; Oven dry, grind into powder obtain the polyaniline adsorbent after the modification.
Embodiment three, modified polyaniline preparation of adsorbent
10g PFOS sodium is dissolved in 500 ml waters, stirred 2 ~ 5 hours; Add 5g aniline (AN), continue to stir 2 ~ 5 hours; Add the 12.3g ammonium persulfate, the pH=2.5 of adjustment mixed solution continues to stir 24 hours earlier; Suction filtration, the wash solids deposition; Oven dry, grind into powder obtain the polyaniline adsorbent after the modification.
Embodiment four: the modified polyaniline preparation of adsorbent
The 10g methyl sodiosul foaliphatate is dissolved in 500 ml waters, stirred 2 ~ 5 hours; Add 5g aniline (AN), continue to stir 2 ~ 5 hours; Add the 8.8g ammonium persulfate, the pH=2-3 of adjustment mixed solution continues to stir 24 hours earlier; Suction filtration, the wash solids deposition; Oven dry, grind into powder obtain the polyaniline adsorbent after the modification.
Embodiment five: the modified polyphenyl amine absorber is to the adsorption test of methylene blue
Get 50mg modified polyphenyl amine absorber (PANSDBS); Drop into initial concentration and be in the 100ml methylene blue solution of 100mg/L stirring and adsorbing after 2 hours; Behind the centrifugation adsorbent; Measuring methylene blue concentration with ultraviolet specrophotometer (TU-1901 type) is 1.8 mg/L, and adsorption rate is 98.2%.
Embodiment six: the PANSDBS adsorbent is to the adsorption test of rhodamine B
Get 50 mg PANSDBS; Drop into initial concentration and be in the 100ml rhodamine B solution of 100 mg/L stirring and adsorbing after 2 hours; Behind the centrifugation adsorbent, measuring rhodamine B concentration with ultraviolet specrophotometer (TU-1901 type) is 3.4 mg/L, and adsorption rate is 93.2%.
Embodiment seven: PANSDBS adsorbent recycling experiment
Get 50 mgPANSDBS, drop into initial concentration and be in the 100 ml methylene blue solutions of 100 mg/L absorption after 2 hours under cushioning liquid the desorption dyestuff, circulating records PANSDBS after five times and can reach more than 90% the adsorption rate of the methylene blue of 100 mg/L.
Embodiment eight: the PANSDBS adsorbent is to AgNO
3The adsorption test of solution
Get 50 mg PANSDBS, dropping into initial concentration is that stirring and adsorbing is after 5 hours in the 100ml mercuric nitrate solution of 200 mmg/L; Behind the centrifugation adsorbent; With mercury ion and content in the Fo Erhadefa titration clear liquid, the result shows that adsorbent is 90.7% to the adsorption rate of mercury ion.
Embodiment nine: the adsorption test of PANSDBS adsorbent Pyrogentisinic Acid solution
Get 50 mg PANSDBS, dropping into initial concentration is in the 100ml phenol solution of 100mmg/L, stirring and adsorbing 4 hours; Behind the centrifugation adsorbent; With the content of phenol in the tetramino antipyrine method measurement solution, the result shows that PANSDBS adsorbent Pyrogentisinic Acid's adsorption rate is 92.3%.
Embodiment ten: the PANSDBS adsorbent is to the adsorption test of Lanzhou petrochemical wastewater
Get 50 mg PANSDBS, dropping into chemical industry center, CNPC Lanzhou provides among waste water 10 g, leaves standstill after stirring 10 min, and the thick material of black disappears, and solution becomes must be clarified, and stink disappears behind 0.5 h; COD (COD) is reduced to 20 mg/L by handling preceding 1100 mg/L, and total amount of organic is reduced to 0.8 mg/L by 1120 mg/L, and heavy metal ion adsorbed rate is more than 98.5%.
Claims (6)
1. modified polyphenyl amine absorber is to be formed by following prepared:
(1) it is soluble in water to contain sulfonic surfactant, stirs the mixed solution that is mixed with concentration 0.07 ~ 0.1mol/L;
(2) add the aniline monomer that contains 0.2 ~ 0.5 times of sulfonic surfactant quality, stirred 2 ~ 5 hours;
(3) initiator ammonium persulfate of adding aniline monomer equimolar amounts continues to stir 20 ~ 24 hours; Suction filtration, the wash solids deposition;
(4) oven dry, grinding obtain the modified polyphenyl amine absorber.
2. modified polyphenyl amine absorber according to claim 1 is characterized in that: in the step (3), add initiator ammonium persulfate after, stirred 20 ~ 24 hours pH=2 ~ 3 of adjustment mixed solution again earlier; Suction filtration, the wash solids deposition.
3. modified polyphenyl amine absorber according to claim 1 or claim 2 is characterized in that: said to contain sulfonic surfactant be phenylbenzimidazole sulfonic acid salt or chain sulfonated hydrocarbon.
4. the modified polyphenyl amine absorber heavy metal ion that is used for adsorbing trade effluent according to claim 1.
5. the modified polyphenyl amine absorber is used for adsorbing the phenol of trade effluent according to claim 1.
6. the modified polyphenyl amine absorber is used for adsorbing the dye of positive ion of trade effluent according to claim 1.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104801287A (en) * | 2015-04-03 | 2015-07-29 | 齐鲁工业大学 | Method for preparing phenol amine copolymer capable of capturing heavy metal ions by utilizing ethylidene amines |
| CN106311184A (en) * | 2016-08-23 | 2017-01-11 | 昆明理工大学 | Preparation method of polyaniline-carried modified activated carbon |
| CN106542686A (en) * | 2016-11-25 | 2017-03-29 | 东莞市联洲知识产权运营管理有限公司 | A kind of effective method for removing Ciprofloxacin in waste water |
| CN109939662A (en) * | 2019-03-28 | 2019-06-28 | 广东石油化工学院 | Dealkalize nitrogen absorber for light fraction obtained by the rectifying of ethylene production sump oil |
| CN110170310A (en) * | 2019-05-06 | 2019-08-27 | 天津科技大学 | Preparation method based on ammonium ion-polyphenol anion frame caesium adsorbent material |
| CN110404500A (en) * | 2019-06-18 | 2019-11-05 | 江门市泰汇环保科技有限公司 | A kind of multiple-effect compound type sewage-treating agent and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104801287A (en) * | 2015-04-03 | 2015-07-29 | 齐鲁工业大学 | Method for preparing phenol amine copolymer capable of capturing heavy metal ions by utilizing ethylidene amines |
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| CN106311184B (en) * | 2016-08-23 | 2019-09-27 | 昆明理工大学 | A kind of modified activated carbon preparation method loading polyaniline |
| CN106542686A (en) * | 2016-11-25 | 2017-03-29 | 东莞市联洲知识产权运营管理有限公司 | A kind of effective method for removing Ciprofloxacin in waste water |
| CN106542686B (en) * | 2016-11-25 | 2019-11-22 | 施小斌 | A kind of effective method for removing Ciprofloxacin in waste water |
| CN109939662A (en) * | 2019-03-28 | 2019-06-28 | 广东石油化工学院 | Dealkalize nitrogen absorber for light fraction obtained by the rectifying of ethylene production sump oil |
| CN109939662B (en) * | 2019-03-28 | 2021-11-16 | 广东石油化工学院 | Dealkalized nitrogen adsorbent for light fraction obtained by sump oil rectification in ethylene production process |
| CN110170310A (en) * | 2019-05-06 | 2019-08-27 | 天津科技大学 | Preparation method based on ammonium ion-polyphenol anion frame caesium adsorbent material |
| CN110170310B (en) * | 2019-05-06 | 2021-09-24 | 天津科技大学 | Preparation method of cesium adsorption material based on ammonium ion-polyphenol anion framework |
| CN110404500A (en) * | 2019-06-18 | 2019-11-05 | 江门市泰汇环保科技有限公司 | A kind of multiple-effect compound type sewage-treating agent and preparation method thereof |
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Application publication date: 20120627 Assignee: Jiangsu Fangzhou Chemical Co., Ltd. Assignor: Northwest Normal University Contract record no.: 2014320000599 Denomination of invention: Modified polyaniline adsorbent and application of modified polyaniline adsorbent in wastewater treatment Granted publication date: 20130724 License type: Exclusive License Record date: 20140722 |
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