CN102962039A - Preparation method and application of modification polyanion sorption agent - Google Patents
Preparation method and application of modification polyanion sorption agent Download PDFInfo
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- CN102962039A CN102962039A CN2012105186243A CN201210518624A CN102962039A CN 102962039 A CN102962039 A CN 102962039A CN 2012105186243 A CN2012105186243 A CN 2012105186243A CN 201210518624 A CN201210518624 A CN 201210518624A CN 102962039 A CN102962039 A CN 102962039A
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Abstract
The invention discloses a preparation method of a modification polyanion sorption agent. The preparation method provided by the invention comprises the following steps of: adding paratoluenesulfonic acid in a 4-6 mol/L hydrochloric acid solution, and uniformly stirring so as to form a mixed solution; adding an aniline monomer in the paratoluenesulfonic acid the quality of which is 0.5-2 times, and stirring for 2-5 hours; then adding an initiating agent ammonium persulfate the quality of which is 2-5 times in the aniline monomer, and continuously stirring for 2-5 hours; and pumping filter, laundering a solid to deposit, drying and grinding, thus obtaining the modification polyanion sorption agent. The preparation method provided by the invention can be used for realizing hydrochloric acid and paratoluenesulfonic acid to modify the polyaniline, an inner porthole structure of a polymer is changed, and the adsorptive property and heat stability of the polyanion are strengthened; meanwhile, the adsorptive surface of the aniline is provided with a positive charge, and the independence selective adsorption action of an anionic dye is realized; and according to the experiment, the preparative modification polyanion sorption agent has strong adsorbability on the anionic dye and can be recycled, and the preparative modification polyanion sorption agent is used for purifying and processing the waste water of the anionic dye.
Description
Technical field
The invention belongs to technical field of polymer composite materials, relate to a kind of preparation of modified polyphenyl amine absorber, relate in particular to a kind of preparation that utilizes the polyaniline adsorbent of hydrochloric acid and p-methyl benzenesulfonic acid modification; The present invention also relates to the application of this modified polyphenyl amine absorber anionic dye in the absorption dyeing waste water simultaneously.
Background technology
Along with science and technology develops by leaps and bounds, the description of materials that dyeing uses is increasing.Chemical raw material has replaced original natural material gradually, and the difficulty for the treatment of of dyeing and printing is increased considerably.The change of water quality of dyeing waste water is complicated and violent, contain a large amount of organic pollutions, and its colourity is dark, the variation of pH value greatly, biodegradability can differ from and make, some or even carcinogenic, mutagenesis, clastogenic organic matter are to the threat of environment especially water environment with endanger increasing.
Absorption method is the method for modal treatment of dyeing and printing, is fit to the advanced treating of low concentration dyeing waste water, has the advantages that investment is little, method is easy, cost is low,, be fit to the processing of middle-size and small-size printing and dyeing mill waste water.Traditional adsorbent mainly is activated carbon, and activated carbon only has preferably absorption property to water-soluble dyes such as the dye of positive ion, direct dyes, acid dyes, reactive dye, possesses hardly adsorption capacity for anionic dye.
Polyaniline is a kind of high molecular synthetic material, is commonly called as conductive plastics.It has the density of plastics, have again the electric conductivity of metal and the machinability of plastics, also possess chemistry and chemical property that metal and plastics are short of, on can be used as stealth material, anti-corrosion material, be civilian, national defense industry can be used as anti-corrosion of metal corrosion material, anti-static material, electronic chemical product etc.Studies show that polyaniline has certain selection adsorption capacity to anionic dye, but its adsorbance is less, adsorption capacity is limited, can not satisfy the requirement of in the printing and dyeing industry anionic dye waste water being processed.
Summary of the invention
The objective of the invention is for problems of the prior art, a kind of preparation method who anionic dye is selected the modified polyphenyl amine absorber of high adsorption capacity is provided.
Another object of the present invention provides this modified polyphenyl amine absorber in the application of anionic dye in the absorption dyeing waste water.
(1) preparation of modified polyphenyl amine absorber
The preparation method of modified polyphenyl amine absorber of the present invention is first aniline monomer to be joined in the hydrochloric acid solution of 4 ~ 6 mol/L, and the room temperature lower magnetic force stirs 20 ~ 30 min; The p-methyl benzenesulfonic acid that adds again 0.2 ~ 4 times of aniline monomer quality stirs 2 ~ 5 h; Then the ammonium persulfate that adds 2 ~ 5 times of aniline monomer quality continues to stir 2 ~ 5 h; Separate, the washing solids of sedimentation, oven dry is ground, and obtains the modified polyphenyl amine absorber.
In order to control the polymerization speed of polyaniline, serious reunion does not occur, with the molten first water dissolved dilution of ammonium persulfate, dropwise join in the mixed system again.
In order to make the abundant polymerization of polyaniline, improve productive rate, add ammonium persulfate after, adjust first the pH=0.5 of mixed solution ~ 1.0, stir again suction filtration, washing solids of sedimentation.
Described separation is centrifugation under 4000 ~ 8000 Zhuan ∕ min.
Described drying is at 80 ~ 100 ℃ of lower vacuum drying 5 ~ 12 h
Describe below by infrared spectrum, thermogravimetric curve and XRD collection of illustrative plates structure and the performance to modified polyphenyl amine absorber of the present invention.
1, infrared spectrum
Fig. 1 is the infrared spectrogram of the polyaniline adsorbent for preparing of the present invention.1570.1 cm from the infrared spectrogram of Fig. 1 polyaniline composite material
-1, 1481.3 cm
-1, 1300.0 cm
-1, 1240.2 cm
-1, 1116.8 cm
-1With 802.4 cm
-1The characteristic peak that the place occurs is respectively stretching vibration and C-H out-of-plane bending vibration absworption peak in the C-H plane that causes of quinoid structure N=Q=N eigen vibration, benzene formula structure N-B-N eigen vibration, polyaniline skeleton C-N stretching vibration, doped polyaniline C-N stretching vibration, protonation process, is the characteristic peak of doped polyaniline.The PANI of the existence explanation composite of stretching vibration and C-H out-of-plane bending vibration absworption peak is generated by the contraposition polymerization in the C-H plane simultaneously.
2, thermogravimetric analysis
Fig. 2 is the thermogravimetric collection of illustrative plates of the modified polyphenyl amine absorber for preparing of the present invention.Polyaniline sorbing material weightlessness only is 4.69% in 100 ℃ as seen from Figure 2.Mainly be because adsorbent internal physical state evaporation of water, along with the rising of temperature from 100 ℃ to 600 ℃, the polyaniline nano material has obvious weightlessness, this mainly is because polyaniline molecule chain generation thermal decomposition.Illustrate that from the thermogravimetric collection of illustrative plates it at room temperature has good stability.
3, XRD test
Fig. 3 is the XRD resolution chart of the polyaniline adsorbent for preparing of the present invention.As can be seen from Figure 3, polyaniline is amorphous state, illustrates that composite does not have obvious crystal structure, meets the general features of polymer.
(2) the modified polyphenyl amine absorber is to the absorption property of anionic dye
1, the anionic dye absorption property is tested: get 100mg modified polyphenyl amine absorber, dropping into initial concentration is in the 100 ml anionic dye solution of 100 mg/L, behind 25 ℃ of stirring and adsorbing 2 h, behind the centrifugation adsorbent, measure the concentration of each anions dyestuff with ultraviolet specrophotometer (TU-1901 type), and calculate adsorption rate.Concrete outcome sees Table 1.
Table 1 is that this modified polyphenyl amine absorber is to the absorption property of anionic dye
| Anionic dye | Orange G | Alizarin Green | Congo red |
| The concentration (mg/L) of dyestuff after the absorption | 0.15 | 0.83 | 0.94 |
| Adsorption rate (%) | 99.85 | 99.17 | 99.06 |
Above-mentioned experiment shows that the modified polyphenyl amine absorber of the present invention's preparation has very strong adsorptivity ability to anionic dye, thereby, can be used for purification and the processing of anionic dye waste water.
2, dye of positive ion absorption property is tested: get 100mg modified polyphenyl amine absorber, dropping into initial concentration is in the 100ml dye of positive ion solution of 100 mg/L, behind 25 ℃ of stirring and adsorbing 2 h, behind the centrifugation adsorbent, measure the concentration of the dye of positive ion in each solution with ultraviolet specrophotometer (TU-1901 type), and calculate adsorption rate.Concrete outcome sees Table 2.
Table 2 is that this modified polyphenyl amine absorber is to the absorption property of the dye of positive ion
| The dye of positive ion | Methylene blue | Rhodamine B | Malachite green |
| The concentration (mg/L) of dyestuff after the absorption | 99.82 | 99.16 | 99.37 |
| Adsorption rate (%) | 0.18 | 0.84 | 0.63 |
Above-mentioned experiment shows that the modified polyphenyl amine absorber of the present invention's preparation does not have suction-operated substantially to the dye of positive ion.
3, recycling experiment:
Get 100 mg modified polyphenyl amine absorbers, dropping into initial concentration is in the 100ml orange G solution of 100 mg/L, behind 25 ℃ of stirring and adsorbing 2 h, and desorption dyestuff under cushioning liquid; Circulate after five times, measure the modified polyphenyl amine absorber to the adsorption rate of orange G in the solution according to the method for experiment 1, can reach more than 90%.The modified polyphenyl amine absorber that shows this present invention's preparation is easy to separate, and can be recycled.
4, the modified polyphenyl amine absorber is tested the absorption property of anionic dye under the different temperatures: get 100mg modified polyphenyl amine absorber, dropping into initial concentration is in the 100 ml orange G solution of 100 mg/L, behind 2 h of stirring and adsorbing under the different temperatures, behind the centrifugation adsorbent, measure the concentration of each anions dyestuff with ultraviolet specrophotometer (TU-1901 type), and calculate adsorption rate.Concrete outcome sees Table 3.
Table 3 is that this modified polyphenyl amine absorber is to the absorption property of anionic dye
| Different temperatures | 25℃ | 35℃ | 45℃ | 55℃ |
| The concentration (mg/L) of dyestuff after the absorption | 0.15 | 0.89 | 1.02 | 1.67 |
| Adsorption rate (%) | 99.85 | 99.11 | 98.98 | 98.33 |
Above-mentioned experiment shows that modified polyphenyl amine absorber adsorptivity ability to the anionic dye orange G under different temperature of the present invention's preparation is different, and its absorption property is best at normal temperatures.
The present invention is relative, and prior art has the following advantages:
1, the present invention utilizes hydrochloric acid and p-methyl benzenesulfonic acid p-poly-phenyl amine to carry out modification, has changed the inside pore passage structure of polymer, has strengthened absorption property and the heat endurance of polyaniline; Simultaneously, make the surface band positive charge of aniline absorption, thereby realize the autonomous selection type suction-operated to anionic dye.
2, the preparation technology of modified polyaniline of the present invention is simple, and raw material is cheap and easy to get, and cost is low;
3, the modified polyaniline chemical stability of the present invention's preparation is good, is easy to separate, and reusable edible does not cause the advantages such as secondary pollution to environment, be a kind of very potential sewage sorbing material.
Description of drawings
Fig. 1 is the infrared spectrogram of the modified polyphenyl amine absorber for preparing of the present invention;
Fig. 2 is the thermogravimetric curve of the modified polyphenyl amine absorber for preparing of the present invention;
Fig. 3 is the XRD resolution chart of the modified polyphenyl amine absorber for preparing of the present invention.
The specific embodiment
Be described further below by the preparation of specific embodiment to modified polyphenyl amine absorber of the present invention.
Embodiment one
2.00 g aniline are added in the hydrochloric acid solution of 100 mL, 4 mol/L, 25 ℃ of lower magnetic forces stir 30 min, add 4.00 g p-methyl benzenesulfonic acid again and continue to stir 2 h; 4.91 g ammonium persulfates are dissolved in 20 mL redistilled waters and add in the mentioned solution stirring reaction 2 h; Mixed solution is turned centrifugal under the ∕ min 8000 obtain blackish green precipitation, fully wash until till not measuring chlorion with the liquor argenti nitratis ophthalmicus inspection with redistilled water; Precipitation is put into 80 ℃ of lower dry 12 h of vacuum drying oven, obtain the modified polyphenyl amine absorber by grinding.
The modified polyphenyl amine absorber can reach more than 96% anionic dye orange G, Alizarin Green, Congo red adsorption rate.
Embodiment two
1.00 g aniline are added in the hydrochloric acid solution of 80 mL, 3.5 mol/L, 25 ℃ of lower magnetic forces stir 30 min, add 2.00 g p-methyl benzenesulfonic acid again and continue to stir 3 h; 2.52 g ammonium persulfates are dissolved in 20 mL redistilled waters and add in the mentioned solution 25 ℃ of stirring reaction 3 h; Adjust the pH=0.5 of mixed solution; Obtain blackish green precipitation with mixed solution is centrifugal under 6000 Zhuan ∕ min, fully wash with redistilled water, and with absolute ethanol washing 5 times; Precipitation is put into 80 ℃ of lower dry 12 h of vacuum drying oven, obtain the modified polyphenyl amine absorber by grinding.
The modified polyphenyl amine absorber can reach more than 99% anionic dye orange G, Alizarin Green, Congo red adsorption rate.
Embodiment three
1.80 g aniline are added in the hydrochloric acid solution of 100 mL, 3.8 mol/L, 25 ℃ of lower magnetic forces stir 30 min, add 3.50 g p-methyl benzenesulfonic acid again and continue to stir 2 h; 4.05 g ammonium persulfates are dissolved in 20 mL redistilled waters and add in the mentioned solution 25 ℃ of stirring reaction 2 h; Adjust the pH=1.0 of mixed solution; Mixed solution is turned centrifugal under the ∕ min 8000 obtain blackish green precipitation, fully wash until till not measuring chlorion with the liquor argenti nitratis ophthalmicus inspection with redistilled water; Precipitation is put into 80 ℃ of lower dry 12 h of vacuum drying oven, obtain the modified polyphenyl amine absorber by grinding.
The modified polyphenyl amine absorber can reach more than 93% anionic dye orange G, Alizarin Green, Congo red adsorption rate.
Embodiment four
2.00 g aniline are added in the hydrochloric acid solution of 100 mL, 4 mol/L, 25 ℃ of lower magnetic forces stir 30 min, add 4.00 g p-methyl benzenesulfonic acid again and continue to stir 2 h; 4.91 g ammonium persulfates are dissolved in 20 mL redistilled waters and add in the mentioned solution stirring reaction 2 h; Obtain blackish green precipitation with mixed solution is centrifugal under 8000 Zhuan ∕ min, fully wash with redistilled water, and with absolute ethanol washing 8 times; Precipitation is put into 80 ℃ of lower dry 12 h of vacuum drying oven, obtain the modified polyphenyl amine absorber by grinding.
The modified polyphenyl amine absorber can reach more than 98% anionic dye orange G, Alizarin Green, Congo red adsorption rate.
Claims (6)
1. the preparation method of a modified polyphenyl amine absorber is first aniline monomer to be joined in the hydrochloric acid solution of 4 ~ 6 mol/L, and the room temperature lower magnetic force stirs 20 ~ 30 min; The p-methyl benzenesulfonic acid that adds again 0.2 ~ 4 times of aniline monomer quality stirs 2 ~ 5 h; Then the ammonium persulfate that adds 2 ~ 5 times of aniline monomer quality continues to stir 2 ~ 5 h; Separate, the washing solids of sedimentation, oven dry is ground, and obtains the modified polyphenyl amine absorber.
2. the preparation method of modified polyphenyl amine absorber as claimed in claim 1 is characterized in that: with the molten first water dissolving of ammonium persulfate, join in the mixed system again.
3. the preparation method of modified polyphenyl amine absorber as claimed in claim 1 or 2 is characterized in that: after adding ammonium persulfate, adjust first the pH=0.5 of mixed solution ~ 1, stir suction filtration, washing solids of sedimentation again.
4. the preparation method of modified polyphenyl amine absorber as claimed in claim 1 or 2, it is characterized in that: described separation is to turn centrifugation under the ∕ min 4000 ~ 8000.
5. the preparation method of modified polyphenyl amine absorber as claimed in claim 1 or 2, it is characterized in that: described drying is at 80 ~ 100 ℃ of lower vacuum drying 5 ~ 12 h.
6. the modified polyphenyl amine absorber of method preparation is used for the anionic dye of absorption dyeing waste water as claimed in claim 1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107983323A (en) * | 2017-12-06 | 2018-05-04 | 福州大学 | A kind of polyaniline nano-compound adsorbent of Nanometer Copper modification and preparation method and application |
| 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 |
| CN114425310A (en) * | 2020-10-29 | 2022-05-03 | 伊斯拓通用设备江苏有限公司 | Modified polyaniline adsorbent and preparation method and application thereof |
| CN115282932A (en) * | 2022-06-30 | 2022-11-04 | 南京林业大学 | Adsorption method of lignin-based adsorbent for dye wastewater |
| CN115557584A (en) * | 2021-06-15 | 2023-01-03 | 济南约瑟夫环保科技有限公司 | Preparation method and application of paint-water separating agent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6982345B2 (en) * | 2002-02-13 | 2006-01-03 | Council Of Scientific & Industrial Research | Process for preparation of cinnamates using polyaniline salts as catalysts |
| CN102430399A (en) * | 2011-11-02 | 2012-05-02 | 西北师范大学 | Modified polyaniline-palygorskite composite adsorbent and application |
-
2012
- 2012-12-06 CN CN2012105186243A patent/CN102962039A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6982345B2 (en) * | 2002-02-13 | 2006-01-03 | Council Of Scientific & Industrial Research | Process for preparation of cinnamates using polyaniline salts as catalysts |
| CN102430399A (en) * | 2011-11-02 | 2012-05-02 | 西北师范大学 | Modified polyaniline-palygorskite composite adsorbent and application |
Non-Patent Citations (2)
| Title |
|---|
| 《硅酸盐学报》 20100430 姚超等 "聚苯胺/凹凸棒石纳米复合材料对甲基橙的吸附性能" 第1.1,1.2节，第1-2段 1-6 第38卷, 第4期 * |
| 姚超等: ""聚苯胺/凹凸棒石纳米复合材料对甲基橙的吸附性能"", 《硅酸盐学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107983323A (en) * | 2017-12-06 | 2018-05-04 | 福州大学 | A kind of polyaniline nano-compound adsorbent of Nanometer Copper modification and preparation method and application |
| 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 |
| CN114425310A (en) * | 2020-10-29 | 2022-05-03 | 伊斯拓通用设备江苏有限公司 | Modified polyaniline adsorbent and preparation method and application thereof |
| CN115557584A (en) * | 2021-06-15 | 2023-01-03 | 济南约瑟夫环保科技有限公司 | Preparation method and application of paint-water separating agent |
| CN115282932A (en) * | 2022-06-30 | 2022-11-04 | 南京林业大学 | Adsorption method of lignin-based adsorbent for dye wastewater |
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Application publication date: 20130313 |