CN104525227B - 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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- CN104525227B CN104525227B CN201410843675.2A CN201410843675A CN104525227B CN 104525227 B CN104525227 B CN 104525227B CN 201410843675 A CN201410843675 A CN 201410843675A CN 104525227 B CN104525227 B CN 104525227B
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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, be combined Ag/BiOX green deep water treatment agent particularly to a kind of CNT
Preparation method.
Background technology
The water in the whole world the most about 10% is directly used by the mankind.Lion's share, 70% for agricultural, and remaining 20% is work
Industry is used.The blowdown of China is about the 20% of the whole world, and it has to the fresh water of global 5%.Therefore, solve pollution to ask
Topic puts on the agenda.In textile printing and dyeing, leather, the paper industry course of processing, employ pollution environment and right in a large number
The auxiliary agent that human body is harmful, these auxiliary agents mostly discharge with the form of liquid and pollute environment, and biological degradability is poor, and toxicity is big,
Free formaldehyde content is high, the content overproof of heavy metal ion.Wherein, printing and dyeing dressing becomes water pollution the most undisputedly
Rich and influential family.From starching start to desizing, wash, scouring and bleaching, mercerising, then dyeing and printing, may also need coating, by this flow process
Every procedure is directed to washing, and every every kg of material of procedure needs 20L water consumption.Result be during dressing every kilogram former
Cotton water consumption adds up up to 200L.When showing at shopper window after the in men's style vest of a standard customizes, more than 2000L
Water production and processing it time used up (cloth: textile, 125g/m).
The currently used method processing waste water mainly has: physical partition method, biological degradation method, chemical decomposition method, but these
Method all has some limitations, and is unfavorable for sustainable development.Thus, people start to be devoted to exploitation efficiently, low energy consumption,
Applied widely and have the pollutant clearance technique of deep oxidation ability.In recent years, a lot of scholars by Ag/BiOX (X=Cl, Br,
I) for Degradation of Organo-pollutants in Water with Photo-catalysis, loading on CNT by Ag/BiOX (X=Cl, Br, I), preparation is efficiently
Photocatalyst become the focus of current research.
Summary of the invention
The technical problem to be solved is to provide a kind of CNT and is combined Ag/BiOX green deep water treatment agent
Preparation method, the method is simple to operate, with low cost, and the requirement to equipment is low；Water treatment agent is applicable to the deep of various waste water
Degree processes, environmental protection non-secondary pollution.
A kind of CNT of the present invention is combined the preparation method of Ag/BiOX green deep water treatment agent, including:
(1) by CNT at H2SO4And HNO3Room temperature ultrasonic reaction 30～60min in mixed liquor, washing is to neutrality, room temperature
Vacuum drying, obtains carboxylic carbon nano-tube；Then carboxylic carbon nano-tube is distributed in excess diethylenetriamine, adds
2-(7-azo BTA)-N, N, N', N'-tetramethylurea hexafluorophosphoric acid ester, 40～50 DEG C of reactions 5～6h, washing with alcohol, room
Temperature vacuum drying, obtains aminated carbon nano tube；Then by aminated carbon nano tube ultrasonic disperse to water and the mixed liquor of acetone
In, regulation pH value is 5～6, and ice-water bath dropping 2,4,6-tri-fluoro-5-chloropyrimide, regulation pH value is 6～6.5,20～30 DEG C
Ultrasonic reaction 24～48h, washing with alcohol, washing, room temperature in vacuo drying, irradiation is (under 222nm quasi-molecule ultraviolet source
Irradiation 3min) obtain response type CNT；
(2) the response type CNT in Ag/BiOX, stabilizer, template and step (1) is joined phosphate buffer
In, stir 30～60min, form suspension；Wherein, the mass ratio of Ag/BiOX and response type CNT be 1:5～
1:20；X is Cl, Br or I；
(3) regulating pH value with alkaline solution is 5～6, is heated to 80～100 DEG C of backflows 6～24h and filters, obtaining CNT multiple
Close Ag/BiOX green deep water treatment agent.
CNT in described step (1) and H2SO4And HNO3The ratio of mixed liquor is 10～20g:4L；Wherein, H2SO4
And HNO3Volume ratio be 1:1～5:1.
Carboxylic carbon nano-tube in described step (1) and 2-(7-azo BTA)-N, N, N', N'-tetramethylurea hexafluoro
The mass ratio of phosphoric acid is 5～8:0.1～0.6.
Aminated carbon nano tube in described step (1) is 4～4.5g:1L with the ratio of water and the mixed liquor of acetone；Wherein,
The volume ratio of water and acetone is 3:1～5:1.
Aminated carbon nano tube in described step (1) is 4～4.5:4～6 with the mass ratio of 2,4,6-tri-fluoro-5-chloropyrimide.
Described step (1) uses sodium carbonate liquor regulation pH value.
Ag/BiOX concentration in described step (2) is 0.01～0.2mol/L.
Stabilizer in described step (2) be disodiumedetate, tetrasodium ethylenediamine tetraacetate, sodium gluconate,
One in BTCA；Stabilizer concentration is 0.01～0.1mol/L.
The triblock polyether P123's that template is mass ratio 1:3 in described step (2) and triblock copolymer F127
Mixture；Template concentration is 0.01～0.1mol/L.
Phosphate buffer in described step (2) is by concentration 0.025～0.05mol/L sodium dihydrogen phosphate and 0.05～0.1mol/L
Dibastic sodium phosphate forms.
Alkaline solution in described step (3) is the water-soluble of concentration 0.5mol/L～the sodium hydroxide of 1.5mol/L or potassium hydroxide
Liquid.
CNT, as a kind of porous mass, has special interlayer characteristic, can at its area load Ag/BiOX microgranule,
It is prepared as loaded catalyst.This loaded photocatalyst can improve the dispersibility of photocatalyst, is beneficial to reclaim and repeats profit
With.
The photocatalysis of the features such as the present invention utilizes the porous of CNT, high adsorption capacity and water easily separated and Ag/BiOX is lived
Property combines, and is successfully loaded on CNT by nanometer Ag/BiOX (X=Cl, Br, I), is prepared as being suspended in
In waste water and the visible-light photocatalysis material of high catalytic activity that can be separated from water smoothly, and it is applied to waste water
Advanced treating, it is possible to achieve to water middle and high concentration organic pollution oxidation removal rather than transfer to elsewhere, is one
The Technology of environment-friendly type.
Beneficial effect
(1) present invention is with low cost, and preparation method is simple, and the requirement to equipment is low, and operability is good；
(2) water treatment agent of the present invention can remove water middle and high concentration organic pollution, it is adaptable to the advanced treating of various waste water,
Environmental protection non-secondary pollution, and there is antibacterial, deodorization, the advantages such as other heavy metal ion can be adsorbed；
(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 circulate and make
With.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments be merely to illustrate the present invention and
It is not used in restriction the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, people in the art
The present invention can be made various changes or modifications by member, and these equivalent form of values fall within the application appended claims equally and limited
Scope.
Embodiment 1
(1) it is the H of 1:1 by 10g CNT in 4L volume ratio2SO4And HNO3Room temperature ultrasonic reaction in mixed liquor
30min, washing to neutrality, room temperature in vacuo is dried 48h, is obtained 5g carboxylic carbon nano-tube；Then by carboxylated for above-mentioned 5g
CNT is distributed in excess diethylenetriamine, adds 100mg 2-(7-azo BTA)-N, N, N', N'-tetramethylurea
Hexafluorophosphoric acid ester, 40 DEG C of reaction 5h, washing with alcohol, room temperature in vacuo is dried 48h, is obtained 4g aminated carbon nano tube；?
After by 4g aminated carbon nano tube ultrasonic disperse in the mixed liquor of the water that 1L volume ratio is 3:1 and acetone, use sodium carbonate
Solution regulation pH value is 5, the ice-water bath dropping fluoro-5-chloropyrimide of 4g 2,4,6-tri-, is 6 with sodium carbonate liquor regulation pH value,
20 DEG C of ultrasonic reaction 24h, washing with alcohol, washing, room temperature in vacuo dries 48h, spoke under 222nm quasi-molecule ultraviolet source
Response type CNT is obtained according to 3min；
(2) by triblock polyether P123 and three blocks that Ag/BiOCl, disodiumedetate, mass ratio are 1:3
In the mixture of copolymer F127 and above-mentioned steps (1), response type CNT joins concentration is 0.025mol/L di(2-ethylhexyl)phosphate
In the buffer of hydrogen sodium and 0.05mol/L dibastic sodium phosphate composition, stir 30min, form suspension；Wherein Ag/BiOCl
Concentration be 0.01mol/L, the concentration of stabilizer be 0.01mol/L, the concentration of template be 0.05mol/L.
(3) pH value with the sodium hydrate aqueous solution above-mentioned suspension of regulation of concentration 0.5mol/L is 5, at heating 80 DEG C,
Backflow 6h, filters, obtains product；Wherein Ag/BiOCl is 1:5 with the mass ratio of CNT.
Embodiment 2
(1) it is the H of 3:1 by 10g CNT in 4L volume ratio2SO4And HNO3Room temperature ultrasonic reaction in mixed liquor
45min, washing to neutrality, room temperature in vacuo is dried 54h, is obtained 6.5g carboxylic carbon nano-tube；Then by above-mentioned 5g carboxyl
Carbon nano tube is distributed in excess diethylenetriamine, adds 300mg 2-(7-azo BTA)-N, N, N', N'-tetramethyl
Urea hexafluorophosphoric acid ester, 45 DEG C of reaction 5h, washing with alcohol, room temperature in vacuo is dried 48h, is obtained 4.2g aminated carbon nano tube；
Finally by 4.2g aminated carbon nano tube ultrasonic disperse in the mixed liquor of the water that 1L volume ratio is 4:1 and acetone, use carbonic acid
Sodium solution regulation pH value is 5.5, the ice-water bath dropping fluoro-5-chloropyrimide of 5g 2,4,6-tri-, with sodium carbonate liquor regulation pH value is
6.2,25 DEG C of ultrasonic reaction 36h, washing with alcohol, washing, room temperature in vacuo dries 48h, at 222nm Excimer UV light
Under source, irradiation 3min obtains response type CNT；
(2) by triblock polyether P123 and triblock copolymer that Ag/BiOBr, sodium gluconate, mass ratio are 1:3
In the mixture of F127 and above-mentioned steps (1) response type CNT join concentration be 0.03mol/L sodium dihydrogen phosphate and
In the buffer of 0.05mol/L dibastic sodium phosphate composition, stir 45min, form suspension；Wherein the concentration of Ag/BiOBr is
0.01mol/L, the concentration of stabilizer are 0.03mol/L, the concentration of template is 0.07mol/L.
(3) pH value with the sodium hydrate aqueous solution above-mentioned suspension of regulation of concentration 0.5mol/L is 7, at heating 90 DEG C,
Backflow 16h, filters, obtains product；Wherein Ag/BiOBr is 1:15 with the mass ratio of CNT.
Embodiment 3
(1) it is the H of 5:1 by 10g CNT in 4L volume ratio2SO4And HNO3Room temperature ultrasonic reaction in mixed liquor
60min, washing to neutrality, room temperature in vacuo is dried 60h, is obtained 8g carboxylic carbon nano-tube；Then by carboxylated for above-mentioned 8g
CNT is distributed in excess diethylenetriamine, adds 600mg 2-(7-azo BTA)-N, N, N', N'-tetramethylurea
Hexafluorophosphoric acid ester, 50 DEG C of reaction 5h, washing with alcohol, room temperature in vacuo is dried 48h, is obtained 4.5g aminated carbon nano tube；?
After by 4.5g aminated carbon nano tube ultrasonic disperse in the mixed liquor of the water that 1L volume ratio is 5:1 and acetone, use sodium carbonate
Solution regulation pH value is 6, the ice-water bath dropping fluoro-5-chloropyrimide of 6g 2,4,6-tri-, is 6.5 with sodium carbonate liquor regulation pH value,
30 DEG C of ultrasonic reaction 48h, washing with alcohol, washing, room temperature in vacuo dries 48h, spoke under 222nm quasi-molecule ultraviolet source
Response type CNT is obtained according to 3min；
(2) by triblock polyether P123 and triblock copolymer that Ag/BiOI, BTCA, mass ratio are 1:3
In the mixture of F127 and above-mentioned steps (1) response type CNT join concentration be 0.05mol/L sodium dihydrogen phosphate and
In the buffer of 0.1mol/L dibastic sodium phosphate composition, stir 60min, form suspension；The wherein concentration of Ag/BiOI
0.15mol/L, the concentration of stabilizer are 0.05mol/L, the concentration of template is 0.1mol/L.
(3) pH value with the potassium hydroxide aqueous solution above-mentioned suspension of regulation of concentration 1.5mol/L is 9, at heating 100 DEG C,
Backflow 24h, filters, obtains product；Wherein Ag/BiOI is 1:20 with the mass ratio of CNT.
The dyeing waste water of the printing and dyeing mill sampled with the same time, for processing object, is separately added into the enforcement of variable concentrations in waste water
The water treatment agent of example 1～3 gained, after 6 hours sun exposures, the water treatment agent percent of decolourization such as following table to dyeing waste water
Shown in:
| 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. CNT is combined a preparation method for Ag/BiOX green deep water treatment agent, including:
(1) by CNT at H2SO4And HNO3Room temperature ultrasonic reaction 30～60min in mixed liquor, washing is to neutrality, room temperature
Vacuum drying, obtains carboxylic carbon nano-tube；Then carboxylic carbon nano-tube is distributed in excess diethylenetriamine, adds
2-(7-azo BTA)-N, N, N', N'-tetramethylurea hexafluorophosphoric acid ester, 40～50 DEG C of reactions 5～6h, washing with alcohol, room
Temperature vacuum drying, obtains aminated carbon nano tube；Then by aminated carbon nano tube ultrasonic disperse to water and the mixed liquor of acetone
In, regulation pH value is 5～6, and ice-water bath dropping 2,4,6-tri-fluoro-5-chloropyrimide, regulation pH value is 6～6.5,20～30 DEG C
Ultrasonic reaction 24～48h, washing with alcohol, washing, room temperature in vacuo drying, under 222nm quasi-molecule ultraviolet source, irradiation obtains
To response type CNT；
(2) the response type CNT in Ag/BiOX, stabilizer, template and step (1) is joined phosphate buffer
In, stir 30～60min, form suspension；Wherein, the mass ratio of Ag/BiOX and response type CNT be 1:5～
1:20；X is Cl, Br or I；Wherein, stabilizer is disodiumedetate, tetrasodium ethylenediamine tetraacetate, glucose
One in acid sodium, BTCA；Template is the triblock polyether P123 and triblock copolymer F127 of mass ratio 1:3
Mixture；
(3) regulating pH value with alkaline solution is 5～6, is heated to reflux and filters, and obtains CNT and is combined Ag/BiOX green deeply
Degree water treatment agent.
A kind of CNT the most according to claim 1 is combined the preparation method of Ag/BiOX green deep water treatment agent, its
It is characterised by: the CNT in described step (1) and H2SO4And HNO3The ratio of mixed liquor is 10～20g:4L；Its
In, H2SO4And HNO3Volume ratio be 1:1～5:1.
A kind of CNT the most according to claim 1 is combined the preparation method of Ag/BiOX green deep water treatment agent, its
It is characterised by: the carboxylic carbon nano-tube in described step (1) and 2-(7-azo BTA)-N, N, N', N'-tetramethyl
The mass ratio of urea hexafluorophosphoric acid ester is 5～8:0.1～0.6.
A kind of CNT the most according to claim 1 is combined the preparation method of Ag/BiOX green deep water treatment agent, its
It is characterised by: the aminated carbon nano tube in described step (1) is 4～4.5g:1L with the ratio of water and the mixed liquor of acetone；
Wherein, the volume ratio of water and acetone is 3:1～5:1.
A kind of CNT the most according to claim 1 is combined the preparation method of Ag/BiOX green deep water treatment agent, its
It is characterised by: the aminated carbon nano tube in described step (1) is 4～4.5:4～6 with the mass ratio of 2,4,6-tri-fluoro-5-chloropyrimide.
A kind of CNT the most according to claim 1 is combined the preparation method of Ag/BiOX green deep water treatment agent, its
It is characterised by: described step (1) uses sodium carbonate liquor regulation pH value.
A kind of CNT the most according to claim 1 is combined the preparation method of Ag/BiOX green deep water treatment agent, its
It is characterised by: the stabilizer concentration in described step (2) is 0.01～0.1mol/L.
A kind of CNT the most according to claim 1 is combined the preparation method of Ag/BiOX green deep water treatment agent, its
It is characterised by: the template concentration in described step (2) is 0.01～0.1mol/L.
A kind of CNT the most according to claim 1 is combined the preparation method of Ag/BiOX green deep water treatment agent, its
Be characterised by: the phosphate buffer in described step (2) by concentration 0.025～0.05mol/L sodium dihydrogen phosphate and
0.05～0.1mol/L disodium hydrogen phosphate composition.
A kind of CNT the most according to claim 1 is combined the preparation method of Ag/BiOX green deep water treatment agent, its
It is characterised by: the alkaline solution in described step (3) is concentration 0.5mol/L～the sodium hydroxide of 1.5mol/L or potassium hydroxide
Aqueous solution.
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| CN104525227B true CN104525227B (en) | 2017-01-11 |
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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 |
| CN108560292B (en) * | 2018-05-04 | 2021-06-25 | 河北科技大学 | Method for applying surface modified carbon nano tube to multifunctional dyed wool |
| 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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| US6872681B2 (en) * | 2001-05-18 | 2005-03-29 | Hyperion Catalysis International, Inc. | Modification of nanotubes oxidation with peroxygen compounds |
| CN101230211B (en) * | 2007-12-27 | 2010-12-08 | 同济大学 | Method for preparing small-molecule imide modified carbon nano-tube |
| CN102500356A (en) * | 2011-11-11 | 2012-06-20 | 东华大学 | Preparation method for carbon nanotube-nano-bismuth vanadate composite photocatalyst |
| CN102430121A (en) * | 2011-11-18 | 2012-05-02 | 广东工业大学 | Method for preparing aminated carbon nano tube |
| CN102631936A (en) * | 2012-04-11 | 2012-08-15 | 中山大学 | BiOI composite material and preparation method and application of BiOI composite material |
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