CN104525115A - Preparation method for environment-friendly advanced water treatment agent by combining carbon nano tube and WO3 - Google Patents
Preparation method for environment-friendly advanced water treatment agent by combining carbon nano tube and WO3 Download PDFInfo
- Publication number
- CN104525115A CN104525115A CN201410843671.4A CN201410843671A CN104525115A CN 104525115 A CN104525115 A CN 104525115A CN 201410843671 A CN201410843671 A CN 201410843671A CN 104525115 A CN104525115 A CN 104525115A
- Authority
- CN
- China
- Prior art keywords
- treatment agent
- water treatment
- preparation
- carbon nano
- cnt
- 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.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 17
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 17
- 239000003381 stabilizer Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- -1 CNT compound Chemical class 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 5
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 5
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 5
- 239000001488 sodium phosphate Substances 0.000 claims description 5
- 235000011008 sodium phosphates Nutrition 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229920000428 triblock copolymer Polymers 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000008363 phosphate buffer Substances 0.000 claims description 4
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 3
- MSXHSNHNTORCAW-GGLLEASOSA-M sodium;(2s,3s,4s,5r,6s)-3,4,5,6-tetrahydroxyoxane-2-carboxylate Chemical compound [Na+].O[C@H]1O[C@H](C([O-])=O)[C@@H](O)[C@H](O)[C@H]1O MSXHSNHNTORCAW-GGLLEASOSA-M 0.000 claims description 3
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 2
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 9
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 2
- 238000006757 chemical reactions by type Methods 0.000 abstract 2
- GOYNRDSJTYLXBU-UHFFFAOYSA-N 5-chloro-2,4,6-trifluoropyrimidine Chemical compound FC1=NC(F)=C(Cl)C(F)=N1 GOYNRDSJTYLXBU-UHFFFAOYSA-N 0.000 abstract 1
- 230000021523 carboxylation Effects 0.000 abstract 1
- 238000006473 carboxylation reaction Methods 0.000 abstract 1
- 239000002781 deodorant agent Substances 0.000 abstract 1
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 abstract 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 239000002953 phosphate buffered saline Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 13
- 238000004043 dyeing Methods 0.000 description 6
- 238000007639 printing Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000009992 mercerising Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009955 starching Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Water Treatment By Sorption (AREA)
- Physical Water Treatments (AREA)
Abstract
The invention relates to a preparation method for an environment-friendly advanced water treatment agent by combining a carbon nano tube and WO3. 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 nano WO3, 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 CNT compound WO
3the preparation method of 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, a lot of scholar is by WO
3for Degradation of Organo-pollutants in Water with Photo-catalysis, by WO
3load on CNT, prepare 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 CNT compound WO
3the preparation method of green deep water treatment agent, 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.
A kind of CNT compound WO of the present invention
3the preparation method of 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 (under 222nm quasi-molecule ultraviolet source irradiation 3min) obtains response type CNT;
(2) by nanometer WO
3, stabilizing agent, response type CNT in template and step (1) join in phosphate buffer, stir 30 ~ 60min, form suspension; Wherein, nanometer WO
3be 1:5 ~ 1:20 with the mass ratio of response type CNT;
(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 WO3 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).
Nanometer WO in described step (2)
3concentration 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, can at its area load nanometer WO
3particulate, is prepared into loaded catalyst.This loaded photocatalyst can improve the dispersiveness of photochemical catalyst, is beneficial to and recycles and reuses.
The present invention utilize the porous of CNT, high adsorption capacity, with feature and the nanometer WO such as water is easily separated
3photocatalytic activity combine, by nanometer WO
3successfully 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) by nanometer WO
3, disodium ethylene diamine tetraacetate, mass ratio 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 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 nanometer WO
3concentration be 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 nanometer WO
3be 1:5 with the mass ratio of CNT.
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) by nanometer WO
3, gluconic acid sodium salt, mass ratio 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 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 nanometer WO
3concentration be 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 nanometer WO
3be 1:15 with the mass ratio of CNT.
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) by nanometer WO
3, BTCA, mass ratio 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 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 nanometer WO
3concentration 0.15mol/L, stabilizing agent concentration be 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 nanometer WO
3be 1:20 with the mass ratio of CNT.
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 | 99.3％ | 90.8％ |
| Embodiment 2 | 99.4％ | 91.2％ |
| Embodiment 3 | 99.5％ | 91.9％ |
Claims (10)
1. a CNT compound WO
3the preparation method of 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) by nanometer WO
3, stabilizing agent, response type CNT in template and step (1) join in phosphate buffer, stir 30 ~ 60min, form suspension; Wherein, nanometer WO
3be 1:5 ~ 1:20 with the mass ratio of response type CNT;
(3) be 5 ~ 6 by alkaline solution adjust ph, add hot reflux and filter, obtaining CNT compound WO
3green deep water treatment agent.
2. a kind of CNT compound WO according to claim 1
3the preparation method of green deep water treatment agent, 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. a kind of CNT compound WO according to claim 1
3the preparation method of green deep water treatment agent, it is characterized in that: the carboxylic carbon nano-tube in described step (1) and 2-(7-azo BTA)-N, the mass ratio of N, N', N'-tetramethylurea hexafluorophosphoric acid is 5 ~ 8:0.1 ~ 0.6.
4. a kind of CNT compound WO according to claim 1
3the preparation method of green deep water treatment agent, 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. a kind of CNT compound WO according to claim 1
3the preparation method of green deep water treatment agent, is characterized in that: 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.
6. a kind of CNT compound WO according to claim 1
3the preparation method of green deep water treatment agent, is characterized in that: adopt sodium carbonate liquor adjust ph in described step (1).
7. a kind of CNT compound WO according to claim 1
3the preparation method of green deep water treatment agent, 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. a kind of CNT compound WO according to claim 1
3the preparation method of green deep water treatment agent, 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. a kind of CNT compound WO according to claim 1
3the preparation method of green deep water treatment agent, 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. a kind of CNT compound WO according to claim 1
3the preparation method of green deep water treatment agent, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410843671.4A CN104525115B (en) | 2014-12-25 | 2014-12-25 | A kind of CNT is combined WO3the preparation method of green deep water treatment agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410843671.4A CN104525115B (en) | 2014-12-25 | 2014-12-25 | A kind of CNT is combined WO3the preparation method of green deep water treatment agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104525115A true CN104525115A (en) | 2015-04-22 |
| CN104525115B CN104525115B (en) | 2016-08-17 |
Family
ID=52840848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410843671.4A Expired - Fee Related CN104525115B (en) | 2014-12-25 | 2014-12-25 | A kind of CNT is combined WO3the preparation method of green deep water treatment agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104525115B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105664919A (en) * | 2015-12-31 | 2016-06-15 | 浙江农林大学 | Sn-doped TiO2/CNTs/WO3 composite photocatalyst and preparation method thereof |
| CN106513054A (en) * | 2016-12-02 | 2017-03-22 | 东华大学 | Fiber/carbon nanotube/WO3 three-dimensional recyclable high-efficiency catalytic material, and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102228829A (en) * | 2011-04-12 | 2011-11-02 | 东华大学 | Method for preparing bentonite self-assembled green bismuth vanadate advanced water treatment agent |
| CN102247809A (en) * | 2010-08-03 | 2011-11-23 | 福建师范大学 | Preparation method of bio-adsorbent with using camellia oleifera shell |
| CN102304847A (en) * | 2011-06-20 | 2012-01-04 | 武汉纺织大学 | Fiber material with heavy metal removing and sterilizing functions and application of fiber material |
| CN102587133A (en) * | 2012-01-16 | 2012-07-18 | 天津工业大学 | Preparation method of functional fiber capable of adsorbing heavy metal ions and organic pollutants at same time |
| US20140213427A1 (en) * | 2013-01-31 | 2014-07-31 | Sunpower Technologies Llc | Photocatalyst for the Reduction of Carbon Dioxide |
-
2014
- 2014-12-25 CN CN201410843671.4A patent/CN104525115B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102247809A (en) * | 2010-08-03 | 2011-11-23 | 福建师范大学 | Preparation method of bio-adsorbent with using camellia oleifera shell |
| CN102228829A (en) * | 2011-04-12 | 2011-11-02 | 东华大学 | Method for preparing bentonite self-assembled green bismuth vanadate advanced water treatment agent |
| CN102304847A (en) * | 2011-06-20 | 2012-01-04 | 武汉纺织大学 | Fiber material with heavy metal removing and sterilizing functions and application of fiber material |
| CN102587133A (en) * | 2012-01-16 | 2012-07-18 | 天津工业大学 | Preparation method of functional fiber capable of adsorbing heavy metal ions and organic pollutants at same time |
| US20140213427A1 (en) * | 2013-01-31 | 2014-07-31 | Sunpower Technologies Llc | Photocatalyst for the Reduction of Carbon Dioxide |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105664919A (en) * | 2015-12-31 | 2016-06-15 | 浙江农林大学 | Sn-doped TiO2/CNTs/WO3 composite photocatalyst and preparation method thereof |
| CN105664919B (en) * | 2015-12-31 | 2017-12-29 | 浙江农林大学 | Sn adulterates TiO2/CNTs/WO3Composite photo-catalyst and preparation method thereof |
| CN106513054A (en) * | 2016-12-02 | 2017-03-22 | 东华大学 | Fiber/carbon nanotube/WO3 three-dimensional recyclable high-efficiency catalytic material, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104525115B (en) | 2016-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104525173B (en) | A kind of CNT composite Ti O2the preparation method of green deep water treatment agent | |
| CN104437466B (en) | A kind of CNT is combined the preparation method of pucherite green deep water treatment agent | |
| CN104525227B (en) | Preparation method for environment-friendly advanced water treatment agent by combining carbon nano tube and Ag/BiOX | |
| CN104475100B (en) | A kind of CNT is combined the preparation method of bismuth molybdate green deep water treatment agent | |
| CN102500356A (en) | Preparation method for carbon nanotube-nano-bismuth vanadate composite photocatalyst | |
| CN105727901A (en) | Preparation method of titanium dioxide photocatalytic adsorbing material | |
| CN102489290A (en) | Preparation method of nano bismuth vanadate photocatalyst loaded on active carbon fiber | |
| CN102228829A (en) | Method for preparing bentonite self-assembled green bismuth vanadate advanced water treatment agent | |
| CN104528865B (en) | A kind of CNT composite S rFeO3the preparation method of green deep water treatment agent | |
| CN104525222B (en) | A kind of CNT is combined ZnIn2s4the preparation method of green deep water treatment agent | |
| CN110946147A (en) | Safe and environment-friendly sewage disinfection powder and preparation method and application thereof | |
| CN104528866B (en) | A kind of preparation method of carbon nanotube compound bismuth tungstate green deep water conditioner | |
| CN104437639B (en) | A kind of CNT is combined the preparation method of tetrasulfonic acid iron-phthalocyanine green deep water treatment agent | |
| CN105964248A (en) | Preparation method of coal ash microsphere loaded modified nanometer titanium dioxide composite photocatalyst | |
| CN105688929A (en) | Neutral advanced oxidation catalyst with pelelith as carrier and preparing method of neutral advanced oxidation catalyst | |
| CN104525115B (en) | A kind of CNT is combined WO3the preparation method of green deep water treatment agent | |
| CN105642368B (en) | A kind of modified TiO2/ CNTs composite catalysts and preparation method thereof | |
| CN102489291B (en) | Method for preparing expanded graphite load nanometer bismuth vanadate photochemical catalyst | |
| CN106622260A (en) | Preparation method and application of catalyst for treating low-concentration formaldehyde wastewater | |
| CN102513091A (en) | Preparation method for graphene self-assembled nanometer bismuth vanadate photocatalyst | |
| CN103934014B (en) | The preparation method of N doping indium sesquioxide nanometer rods/graphene oxide composite photo-catalyst | |
| CN104528867B (en) | A kind of preparation method of carbon nanotube compound ferric vandate green deep water conditioner | |
| CN102247831A (en) | Method for preparing activated carbon self-assembled bismuth vanadate water treatment agent | |
| CN103521183A (en) | Adsorbent for treating acrylonitrile waste water as well as preparation method and application thereof | |
| CN102847519B (en) | Composite absorbing material for removing chlorate in water and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160817 Termination date: 20171225 |