CN104525227A - Preparation method for environment-friendly advanced water treatment agent by combining carbon nano tube and Ag/BiOX - Google Patents
Preparation method for environment-friendly advanced water treatment agent by combining carbon nano tube and Ag/BiOX Download PDFInfo
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Abstract
The invention relates to a preparation method for an environment-friendly advanced water treatment agent by combining a carbon nano tube and Ag/BiOX. The preparation method includes the steps that firstly, carboxylation, aminated modification and 2, 4, 6-trifluoro-5-chloropyrimidine modification are sequentially conducted on the carbon nano tube to obtain a reaction type carbon nano tube; secondly, the Ag/BiOX (X=C1, Br and I), a stabilizer, a template agent and the reaction type carbon nano tube are added into phosphate buffered saline to be stirred for 30 min-60 min to form turbid liquid; thirdly, the turbid liquid is filtered and dried to obtain the environment-friendly advanced water treatment agent. The preparation method is low in cost, simple, low in equipment requirement and good in operability. The water treatment agent can be used for removing high-concentration organic pollutants in water, is suitable for advanced treatment of various kinds of wastewater, environmentally friendly and free of secondary pollution and has the advantages of being antibacterial, deodorant, capable of adsorbing other heavy metal ions and the like.
Description
Technical field
The invention belongs to water treatment agent field, particularly a kind of preparation method of CNT compound Ag/BiOX green deep water treatment agent.
Background technology
The whole world only about 10% water be directly for the mankind used.Lion's share, 70% for agricultural, and remaining 20% is industrial.The blowdown of China is about 20% of the whole world, and it has to the fresh water of 5% of the whole world.Therefore, contaminated solution problem puts on the agenda.In textile printing and dyeing, leather, paper industry process, employ contaminated environment and harmful auxiliary agent in a large number, these auxiliary agents are the contaminated environment mainly with the form discharge of liquid greatly, biological degradability is poor, toxicity is large, and free formaldehyde content is high, the content overproof of heavy metal ion.Wherein, dressing of printing and dyeing becomes water pollutions rich and influential family especially undisputedly.From starching to destarch, wash, scouring and bleaching, mercerising, then dyeing and printing, also may need coating, all relate to washing by the every procedure of this flow process, and every every kg of material of procedure needs 20L water consumption.Result is that the water consumption of every kilogram of raw cotton in dressing process is added up nearly 200L.When showing at shopper window after the in men's style shirt customization of a standard, more than 2000L water production and processing it time used up (cloth: cotton textiles, 125g/m).
The method of the process waste water of current use mainly contains: physical partition method, biological degradation method, chemical decomposition method, but these methods all have some limitations, and are unfavorable for sustainable development.Thus, people start to be devoted to develop efficient, low energy consumption, applied widely and have the pollutant clearance technique of deep oxidation ability.In recent years, Ag/BiOX (X=Cl, Br, I) for Degradation of Organo-pollutants in Water with Photo-catalysis, loads on CNT by a lot of scholar by Ag/BiOX (X=Cl, Br, I), prepares the focus that efficient photochemical catalyst becomes current research.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of CNT compound Ag/BiOX green deep water treatment agent, and the method is simple to operate, with low cost, low to the requirement of equipment; Water treatment agent is applicable to the advanced treating of various waste water, environmental protection non-secondary pollution.
The preparation method of a kind of CNT compound Ag/BiOX green deep water treatment agent of the present invention, comprising:
(1) by CNT at H
2sO
4and HNO
3room temperature ultrasonic reaction 30 ~ 60min in mixed liquor, washing is to neutral, and room temperature in vacuo is dried, and obtains carboxylic carbon nano-tube; Then carboxylic carbon nano-tube is distributed in excessive diethylenetriamine, adds 2-(7-azo BTA)-N, N, N', N'-tetramethylurea hexafluorophosphoric acid ester, 40 ~ 50 DEG C of reaction 5 ~ 6h, ethanol washs, and room temperature in vacuo is dried, and obtains aminated carbon nano tube; Then by aminated carbon nano tube ultrasonic disperse in the mixed liquor of water and acetone, adjust ph is 5 ~ 6, ice-water bath drips 2,4,6-tri-fluoro-5-chlorine pyrimidine, adjust ph is 6 ~ 6.5,20 ~ 30 DEG C of ultrasonic reaction 24 ~ 48h, ethanol washs, washing, room temperature in vacuo is dried, and irradiation (under 222nm quasi-molecule ultraviolet source irradiation 3min) obtains response type CNT;
(2) the response type CNT in Ag/BiOX, stabilizing agent, template and step (1) is joined in phosphate buffer, stir 30 ~ 60min, form suspension; Wherein, the mass ratio of Ag/BiOX and response type CNT is 1:5 ~ 1:20; X is Cl, Br or I;
(3) be 5 ~ 6 by alkaline solution adjust ph, be heated to 80 ~ 100 DEG C of backflow 6 ~ 24h and filter, obtaining CNT compound Ag/BiOX green deep water treatment agent.
CNT in described step (1) and H
2sO
4and HNO
3the ratio of mixed liquor is 10 ~ 20g:4L; Wherein, H
2sO
4and HNO
3volume ratio be 1:1 ~ 5:1.
The mass ratio of the carboxylic carbon nano-tube in described step (1) and 2-(7-azo BTA)-N, N, N', N'-tetramethylurea hexafluorophosphoric acid is 5 ~ 8:0.1 ~ 0.6.
The ratio of the aminated carbon nano tube in described step (1) and the mixed liquor of water and acetone is 4 ~ 4.5g:1L; Wherein, the volume ratio of water and acetone is 3:1 ~ 5:1.
The mass ratio of the aminated carbon nano tube in described step (1) and 2,4,6-tri-fluoro-5-chlorine pyrimidine is 4 ~ 4.5:4 ~ 6.
Sodium carbonate liquor adjust ph is adopted in described step (1).
Ag/BiOX concentration in described step (2) is 0.01 ~ 0.2mol/L.
Stabilizing agent in described step (2) is the one in disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, gluconic acid sodium salt, BTCA; Stabilizer concentration is 0.01 ~ 0.1mol/L.
Template in described step (2) is the triblock polyether P123 of mass ratio 1:3 and the mixture of triblock copolymer F127; Template concentration is 0.01 ~ 0.1mol/L.
Phosphate buffer in described step (2) is made up of concentration 0.025 ~ 0.05mol/L sodium dihydrogen phosphate and 0.05 ~ 0.1mol/L dibastic sodium phosphate.
Alkaline solution in described step (3) is the NaOH of concentration 0.5mol/L ~ 1.5mol/L or the aqueous solution of potassium hydroxide.
CNT, as a kind of porous mass, has special interlayer characteristic, at its area load Ag/BiOX particulate, can be prepared into loaded catalyst.This loaded photocatalyst can improve the dispersiveness of photochemical catalyst, is beneficial to and recycles and reuses.
The present invention utilizes the porous of CNT, high adsorption capacity, combines with the photocatalytic activity of the feature such as water is easily separated and Ag/BiOX, by nanometer Ag/BiOX (X=Cl, Br, I) successfully load on CNT, be prepared into the visible-light photocatalysis material of the high catalytic activity that can be suspended in waste water and can be separated with water smoothly, and be applied to the advanced treating of waste water, can realize water middle and high concentration organic pollution oxidation removal, instead of transfer to other places, be the technology of an environment-friendly type.
beneficial effect
(1) the present invention is with low cost, and preparation method is simple, and low to the requirement of equipment, operability is good;
(2) water treatment agent of the present invention can remove water middle and high concentration organic pollution, is applicable to the advanced treating of various waste water, environmental protection non-secondary pollution, and has antibacterial, deodorizing, can adsorb the advantages such as other heavy metal ion;
(3) water treatment agent of the present invention can overcome the deficiency of existing bismuthino water treatment agent, and water treatment efficiency is good, can recycle.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
(1) be the H of 1:1 by 10g CNT in 4L volume ratio
2sO
4and HNO
4room temperature ultrasonic reaction 30min in mixed liquor, washing is to neutral, and room temperature in vacuo dries 48h, obtains 5g carboxylic carbon nano-tube; Then above-mentioned 5g carboxylic carbon nano-tube is distributed in excessive diethylenetriamine, adds 100mg 2-(7-azo BTA)-N, N, N', N'-tetramethylurea hexafluorophosphoric acid ester, 40 DEG C of reaction 5h, ethanol washs, and room temperature in vacuo dries 48h, obtains 4g aminated carbon nano tube; Finally by 4g aminated carbon nano tube ultrasonic disperse in 1L volume ratio is the water of 3:1 and the mixed liquor of acetone, be 5 by sodium carbonate liquor adjust ph, ice-water bath drips the fluoro-5-chlorine pyrimidine of 4g 2,4,6-tri-, be 6 by sodium carbonate liquor adjust ph, 20 DEG C of ultrasonic reaction 24h, ethanol washs, washing, room temperature in vacuo dries 48h, and under 222nm quasi-molecule ultraviolet source, irradiation 3min obtains response type CNT;
(2) be that in the triblock polyether P123 of 1:3 and the mixture of triblock copolymer F127 and above-mentioned steps (1), response type CNT joins concentration by Ag/BiOCl, disodium ethylene diamine tetraacetate, mass ratio be in the buffer solution of 0.025mol/L sodium dihydrogen phosphate and 0.05mol/L dibastic sodium phosphate composition, stir 30min, form suspension; Wherein the concentration of Ag/BiOCl is 0.01mol/L, the concentration of stabilizing agent is 0.01mol/L, the concentration of template is 0.05mol/L.
(3) regulate the pH value of above-mentioned suspension to be 5 with the sodium hydrate aqueous solution of concentration 0.5mol/L, at heating 80 DEG C, backflow 6h, filters, obtains product; Wherein the mass ratio of Ag/BiOCl and CNT is 1:5.
Embodiment 2
(1) be the H of 3:1 by 10g CNT in 4L volume ratio
2sO
4and HNO
4room temperature ultrasonic reaction 45min in mixed liquor, washing is to neutral, and room temperature in vacuo dries 54h, obtains 6.5g carboxylic carbon nano-tube; Then above-mentioned 5g carboxylic carbon nano-tube is distributed in excessive diethylenetriamine, adds 300mg 2-(7-azo BTA)-N, N, N', N'-tetramethylurea hexafluorophosphoric acid ester, 45 DEG C of reaction 5h, ethanol washs, and room temperature in vacuo dries 48h, obtains 4.2g aminated carbon nano tube; Finally by 4.2g aminated carbon nano tube ultrasonic disperse in 1L volume ratio is the water of 4:1 and the mixed liquor of acetone, be 5.5 by sodium carbonate liquor adjust ph, ice-water bath drips the fluoro-5-chlorine pyrimidine of 5g 2,4,6-tri-, be 6.2 by sodium carbonate liquor adjust ph, 25 DEG C of ultrasonic reaction 36h, ethanol washs, washing, room temperature in vacuo dries 48h, and under 222nm quasi-molecule ultraviolet source, irradiation 3min obtains response type CNT;
(2) be that in the triblock polyether P123 of 1:3 and the mixture of triblock copolymer F127 and above-mentioned steps (1), response type CNT joins concentration by Ag/BiOBr, gluconic acid sodium salt, mass ratio be in the buffer solution of 0.03mol/L sodium dihydrogen phosphate and 0.05mol/L dibastic sodium phosphate composition, stir 45min, form suspension; Wherein the concentration of Ag/BiOBr is 0.01mol/L, the concentration of stabilizing agent is 0.03mol/L, the concentration of template is 0.07mol/L.
(3) regulate the pH value of above-mentioned suspension to be 7 with the sodium hydrate aqueous solution of concentration 0.5mol/L, at heating 90 DEG C, backflow 16h, filters, obtains product; Wherein the mass ratio of Ag/BiOBr and CNT is 1:15.
Embodiment 3
(1) be the H of 5:1 by 10g CNT in 4L volume ratio
2sO
4and HNO
4room temperature ultrasonic reaction 60min in mixed liquor, washing is to neutral, and room temperature in vacuo dries 60h, obtains 8g carboxylic carbon nano-tube; Then above-mentioned 8g carboxylic carbon nano-tube is distributed in excessive diethylenetriamine, adds 600mg 2-(7-azo BTA)-N, N, N', N'-tetramethylurea hexafluorophosphoric acid ester, 50 DEG C of reaction 5h, ethanol washs, and room temperature in vacuo dries 48h, obtains 4.5g aminated carbon nano tube; Finally by 4.5g aminated carbon nano tube ultrasonic disperse in 1L volume ratio is the water of 5:1 and the mixed liquor of acetone, be 6 by sodium carbonate liquor adjust ph, ice-water bath drips the fluoro-5-chlorine pyrimidine of 6g 2,4,6-tri-, be 6.5 by sodium carbonate liquor adjust ph, 30 DEG C of ultrasonic reaction 48h, ethanol washs, washing, room temperature in vacuo dries 48h, and under 222nm quasi-molecule ultraviolet source, irradiation 3min obtains response type CNT;
(2) be that in the triblock polyether P123 of 1:3 and the mixture of triblock copolymer F127 and above-mentioned steps (1), response type CNT joins concentration by Ag/BiOI, BTCA, mass ratio be in the buffer solution of 0.05mol/L sodium dihydrogen phosphate and 0.1mol/L dibastic sodium phosphate composition, stir 60min, form suspension; Wherein the concentration 0.15mol/L of Ag/BiOI, the concentration of stabilizing agent are 0.05mol/L, the concentration of template is 0.1mol/L.
(3) regulate the pH value of above-mentioned suspension to be 9 with the potassium hydroxide aqueous solution of concentration 1.5mol/L, at heating 100 DEG C, backflow 24h, filters, obtains product; Wherein the mass ratio of Ag/BiOI and CNT is 1:20.
With the dyeing waste water of the printing and dyeing mill of same time sampling for handling object, add the water treatment agent of embodiment 1 ~ 3 gained of variable concentrations in waste water respectively, after 6 hours of daylight irradiate, the percent of decolourization of water treatment agent to dyeing waste water is as shown in the table:
| Percent of decolourization | COD clearance | |
| Embodiment 1 | 99.4％ | 91.2％ |
| Embodiment 2 | 99.3％ | 91.3％ |
| Embodiment 3 | 99.5％ | 92.6％ |
Claims (10)
1. a preparation method for CNT compound Ag/BiOX green deep water treatment agent, comprising:
(1) by CNT at H
2sO
4and HNO
3room temperature ultrasonic reaction 30 ~ 60min in mixed liquor, washing is to neutral, and room temperature in vacuo is dried, and obtains carboxylic carbon nano-tube; Then carboxylic carbon nano-tube is distributed in excessive diethylenetriamine, adds 2-(7-azo BTA)-N, N, N', N'-tetramethylurea hexafluorophosphoric acid ester, 40 ~ 50 DEG C of reaction 5 ~ 6h, ethanol washs, and room temperature in vacuo is dried, and obtains aminated carbon nano tube; Then by aminated carbon nano tube ultrasonic disperse in the mixed liquor of water and acetone, adjust ph is 5 ~ 6, ice-water bath drips 2,4,6-tri-fluoro-5-chlorine pyrimidine, adjust ph is 6 ~ 6.5,20 ~ 30 DEG C of ultrasonic reaction 24 ~ 48h, ethanol washs, washing, room temperature in vacuo is dried, and irradiation obtains response type CNT;
(2) the response type CNT in Ag/BiOX, stabilizing agent, template and step (1) is joined in phosphate buffer, stir 30 ~ 60min, form suspension; Wherein, the mass ratio of Ag/BiOX and response type CNT is 1:5 ~ 1:20; X is Cl, Br or I;
(3) be 5 ~ 6 by alkaline solution adjust ph, add hot reflux and filter, obtaining CNT compound Ag/BiOX green deep water treatment agent.
2. the preparation method of a kind of CNT compound Ag/BiOX green deep water treatment agent according to claim 1, is characterized in that: the CNT in described step (1) and H
2sO
4and HNO
3the ratio of mixed liquor is 10 ~ 20g:4L; Wherein, H
2sO
4and HNO
3volume ratio be 1:1 ~ 5:1.
3. the preparation method of a kind of CNT compound Ag/BiOX green deep water treatment agent according to claim 1, it is characterized in that: the carboxylic carbon nano-tube in described step (1) and 2-(7-azo BTA)-N, N, the mass ratio of N', N'-tetramethylurea hexafluorophosphoric acid is 5 ~ 8:0.1 ~ 0.6.
4. the preparation method of a kind of CNT compound Ag/BiOX green deep water treatment agent according to claim 1, is characterized in that: the ratio of the aminated carbon nano tube in described step (1) and the mixed liquor of water and acetone is 4 ~ 4.5g:1L; Wherein, the volume ratio of water and acetone is 3:1 ~ 5:1.
5. the preparation method of a kind of CNT compound Ag/BiOX green deep water treatment agent according to claim 1, it is characterized in that: the aminated carbon nano tube and 2 in described step (1), the mass ratio of 4,6-tri-fluoro-5-chlorine pyrimidine is 4 ~ 4.5:4 ~ 6.
6. the preparation method of a kind of CNT compound Ag/BiOX green deep water treatment agent according to claim 1, is characterized in that: adopt sodium carbonate liquor adjust ph in described step (1).
7. the preparation method of a kind of CNT compound Ag/BiOX green deep water treatment agent according to claim 1, is characterized in that: the stabilizing agent in described step (2) is the one in disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, gluconic acid sodium salt, BTCA; Stabilizer concentration is 0.01 ~ 0.1mol/L.
8. the preparation method of a kind of CNT compound Ag/BiOX green deep water treatment agent according to claim 1, is characterized in that: the template in described step (2) is the triblock polyether P123 of mass ratio 1:3 and the mixture of triblock copolymer F127; Template concentration is 0.01 ~ 0.1mol/L.
9. the preparation method of a kind of CNT compound Ag/BiOX green deep water treatment agent according to claim 1, is characterized in that: the phosphate buffer in described step (2) is made up of concentration 0.025 ~ 0.05mol/L sodium dihydrogen phosphate and 0.05 ~ 0.1mol/L dibastic sodium phosphate.
10. the preparation method of a kind of CNT compound Ag/BiOX green deep water treatment agent according to claim 1, is characterized in that: the alkaline solution in described step (3) is the NaOH of concentration 0.5mol/L ~ 1.5mol/L or the aqueous solution of potassium hydroxide.
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Cited By (4)
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| CN106732790A (en) * | 2016-12-02 | 2017-05-31 | 东华大学 | A kind of fiber/CNT/Ag3PO4 three-dimensional recyclable efficient catalytic material and its preparation and application |
| CN106732789A (en) * | 2016-12-02 | 2017-05-31 | 东华大学 | A kind of fiber/CNT/AgBiOX three-dimensional recyclable efficient catalytic material and its preparation and application |
| CN108560292A (en) * | 2018-05-04 | 2018-09-21 | 河北科技大学 | A kind of surface-modified carbon nanotubes are applied to the method for multifunctional dyeing wool |
| CN114405531A (en) * | 2022-03-07 | 2022-04-29 | 广西民族大学 | Z-type heterojunction photocatalytic nano material with crystal face synergistic effect and preparation method and application thereof |
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| CN106732790A (en) * | 2016-12-02 | 2017-05-31 | 东华大学 | A kind of fiber/CNT/Ag3PO4 three-dimensional recyclable efficient catalytic material and its preparation and application |
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| CN108560292A (en) * | 2018-05-04 | 2018-09-21 | 河北科技大学 | A kind of surface-modified carbon nanotubes are applied to the method for multifunctional dyeing wool |
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| CN114405531B (en) * | 2022-03-07 | 2022-12-13 | 广西民族大学 | Z-type heterojunction photocatalytic nano material with crystal face synergistic effect and preparation method and application thereof |
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