CN102513068B - 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
- Publication number
- CN102513068B CN102513068B CN 201110341509 CN201110341509A CN102513068B CN 102513068 B CN102513068 B CN 102513068B CN 201110341509 CN201110341509 CN 201110341509 CN 201110341509 A CN201110341509 A CN 201110341509A CN 102513068 B CN102513068 B CN 102513068B
- Authority
- CN
- China
- Prior art keywords
- adsorbent
- modified
- polyaniline
- hours
- amine absorber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
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.Its middle metabolite of dye well contains multiple noxious material and can cause multiple harm to the water body biology.The processing of dyeing waste water is mainly set about from the decolouring problem.At present, Chang Yong decoloration treatment method 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.The industrial chemical precipitation method that adopts is handled heavy metal wastewater thereby more, but the chemical precipitation method existence easily causes the water quality sclerosis, and is not thorough to the heavy metal ion processing of low concentration, causes 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 more cheap, the more effective sorbing material of research and development to replace active carbon and further improve adsorption efficiency and to reduce cost at present.
Summary of the invention
The objective of the invention is at problems of 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 prepared from by following technology:
(1) it is soluble in water to contain sulfonic surfactant, stirs the mixed solution that is mixed with concentration 0.07 ~ 0.1mol/L.
Described 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, washing solid precipitation;
In order to make surfactant fully hydrolysis in water, behind the adding initiator ammonium persulfate, adjust pH=2 ~ 3 of mixed solution earlier, stirred again 20 ~ 24 hours; Suction filtration, washing solid precipitation.
(4) oven dry, grinding obtain modified polyphenyl amine absorber (PANSDBS).
Describe below by infrared spectrum and thermogravimetric curve structure and performance 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 be seen from Figure 2, the PANSDBS adsorbent of the present invention's preparation is stable significantly better than the non-modified polyaniline in temperature-rise period, and when temperature was raised to 100 ℃, the decomposition amount of PANSDBS adsorbent only was 2.6263%, illustrated 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 be seen from Figure 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.
Experimental results demonstrate that modified polyphenyl amine absorber of the present invention all has better adsorption capacity to also the dye of positive ion being had the selection adsorptivity 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 raw material is cheap and 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.
Experimental results demonstrate, 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 below by the method for specific embodiment 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, adjust the pH=2 of mixed solution earlier, continue to stir 24 hours; Suction filtration, washing solid precipitation; 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, adjust the pH=3 of mixed solution earlier, continue to stir 24 hours; Suction filtration, washing solid precipitation; 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, adjust the pH=2.5 of mixed solution earlier, continue to stir 24 hours; Suction filtration, washing solid precipitation; 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, adjust the pH=2-3 of mixed solution earlier, continue to stir 24 hours; Suction filtration, washing solid precipitation; 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 (5)
1. modified polyphenyl amine absorber is to be prepared from by following technology:
(1) it is soluble in water to contain sulfonic surfactant, stirs the mixed solution that is mixed with concentration 0.07 ~ 0.1mol/L; It is described that to contain sulfonic surfactant be neopelex, cetyl benzene sulfonic acid sodium salt, methyl sodiosul foaliphatate or 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, washing solid precipitation;
(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, adjust pH=2 ~ 3 of mixed solution earlier, stirred again 20 ~ 24 hours; Suction filtration, washing solid precipitation.
3. the modified polyphenyl amine absorber heavy metal ion that is used for adsorbing trade effluent according to claim 1.
4. the modified polyphenyl amine absorber is used for adsorbing the phenol of trade effluent according to claim 1.
5. the modified polyphenyl amine absorber is used for adsorbing the dye of positive ion of trade effluent according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110341509 CN102513068B (en) | 2011-11-02 | 2011-11-02 | Modified polyaniline adsorbent and application of modified polyaniline adsorbent in wastewater treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110341509 CN102513068B (en) | 2011-11-02 | 2011-11-02 | Modified polyaniline adsorbent and application of modified polyaniline adsorbent in wastewater treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102513068A CN102513068A (en) | 2012-06-27 |
| CN102513068B true CN102513068B (en) | 2013-07-24 |
Family
ID=46284285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110341509 Expired - Fee Related CN102513068B (en) | 2011-11-02 | 2011-11-02 | Modified polyaniline adsorbent and application of modified polyaniline adsorbent in wastewater treatment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102513068B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104801287B (en) * | 2015-04-03 | 2017-07-28 | 齐鲁工业大学 | A kind of ethylene-amines can catch the preparation method of heavy metal ion phenol amine copolymer thing |
| CN106311184B (en) * | 2016-08-23 | 2019-09-27 | 昆明理工大学 | A kind of modified activated carbon preparation method loading polyaniline |
| CN106542686B (en) * | 2016-11-25 | 2019-11-22 | 施小斌 | A kind of effective method for removing Ciprofloxacin in waste water |
| 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 |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041124A (en) * | 2007-04-28 | 2007-09-26 | 同济大学 | Diaminobenzenesulfonate polymerization modification polymer materials -PAN Hg ion sorbent and the preparing method |
| CN101191017A (en) * | 2007-11-20 | 2008-06-04 | 沈阳化工学院 | Preparation for polyaniline mesoporous molecular screen composite |
| CN101928048A (en) * | 2010-08-27 | 2010-12-29 | 陕西科技大学 | Method for purifying humic acid pollutants in water by utilizing polyaniline |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4693123B2 (en) * | 2006-08-28 | 2011-06-01 | 住友精化株式会社 | Gold adsorbent and method for selective separation and recovery of gold |
-
2011
- 2011-11-02 CN CN 201110341509 patent/CN102513068B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041124A (en) * | 2007-04-28 | 2007-09-26 | 同济大学 | Diaminobenzenesulfonate polymerization modification polymer materials -PAN Hg ion sorbent and the preparing method |
| CN101191017A (en) * | 2007-11-20 | 2008-06-04 | 沈阳化工学院 | Preparation for polyaniline mesoporous molecular screen composite |
| CN101928048A (en) * | 2010-08-27 | 2010-12-29 | 陕西科技大学 | Method for purifying humic acid pollutants in water by utilizing polyaniline |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2008-49315A 2008.03.06 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102513068A (en) | 2012-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102513068B (en) | Modified polyaniline adsorbent and application of modified polyaniline adsorbent in wastewater treatment | |
| Ma et al. | Ultrahigh adsorption capacities for anionic and cationic dyes from wastewater using only chitosan | |
| CN102430399A (en) | Modified polyaniline-palygorskite composite adsorbent and application | |
| Wei et al. | Role of extracellular polymeric substances in biosorption of dye wastewater using aerobic granular sludge | |
| Wu et al. | Characteristics of Elovich equation used for the analysis of adsorption kinetics in dye-chitosan systems | |
| Singh et al. | Poly (acrylamide) functionalized chitosan: an efficient adsorbent for azo dyes from aqueous solutions | |
| CN104258816B (en) | The preparation method of the exfoliated Nano composite material of montmorillonite of a kind of magnetic for wastewater treatment | |
| Sadhasivam et al. | Exploitation of Trichoderma harzianum mycelial waste for the removal of rhodamine 6G from aqueous solution | |
| Wawrzkiewicz et al. | Equilibrium and kinetic studies on the adsorption of acidic dye by the gel anion exchanger | |
| CN103977757B (en) | The preparation method of a kind of organic wastewater absorption degradation agent | |
| CN102050554A (en) | Treatment method of high-concentration resin desorption liquid after deep purification of wastewater | |
| CN103663661A (en) | Treatment method of hexavalent chromium ion containing industrial wastewater | |
| Siddiqui et al. | Decolorization of textile wastewater using composite materials | |
| CN101310853B (en) | Calcium adsorbing material and its preparation method | |
| Rizzi et al. | Applicative study (part I): the excellent conditions to remove in batch direct textile dyes (direct red, direct blue and direct yellow) from aqueous solutions by adsorption processes on low-cost chitosan films under different conditions | |
| Fu et al. | Comparative investigation of N, N′-bis-(dithiocarboxy) piperazine and diethyldithiocarbamate as precipitants for Ni (II) in simulated wastewater | |
| CN102059100A (en) | Method for preparing magnetic saccharomyces cerevisiae and technique for processing printing and dying wastewater by using same | |
| CN105688795A (en) | Anionic dye adsorbent composite material as well as preparation method and application thereof | |
| CN101249415A (en) | Barium based adsorption material and method of preparing the same | |
| AU2020103640A4 (en) | Porous Biomass Adsorbing Material, And Application Thereof | |
| CN111499068B (en) | Phenol-containing wastewater treatment system and treatment method thereof | |
| CN113578253A (en) | Self-floating adsorbent based on hollow glass beads and preparation method and application thereof | |
| CN102671617B (en) | Preparation method of material for adsorption of non-biodegradable organic pollutant | |
| CN108772050B (en) | Adsorbent, preparation method and application thereof | |
| CN106630054A (en) | Application of polyferric compound in phenol sewage treatment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
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 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130724 Termination date: 20141102 |
|
| EXPY | Termination of patent right or utility model |