CN106732599A - A kind of fiber/CNT/MgFe2O4Three-dimensional recyclable efficient catalytic material and its preparation and application - Google Patents
A kind of fiber/CNT/MgFe2O4Three-dimensional recyclable efficient catalytic material and its preparation and application Download PDFInfo
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- CN106732599A CN106732599A CN201611096511.3A CN201611096511A CN106732599A CN 106732599 A CN106732599 A CN 106732599A CN 201611096511 A CN201611096511 A CN 201611096511A CN 106732599 A CN106732599 A CN 106732599A
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- 239000000835 fiber Substances 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 34
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000005406 washing Methods 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 16
- 239000002351 wastewater Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 238000005470 impregnation Methods 0.000 claims abstract description 9
- 239000004753 textile Substances 0.000 claims abstract description 9
- 239000004744 fabric Substances 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000012467 final product Substances 0.000 claims abstract description 6
- 238000010276 construction Methods 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000003381 stabilizer Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- ZXQBXHYVVKUTOV-UHFFFAOYSA-N C(CCCCC)I.[F] Chemical class C(CCCCC)I.[F] ZXQBXHYVVKUTOV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 5
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical class [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 5
- 239000001488 sodium phosphate Substances 0.000 claims description 5
- 235000011008 sodium phosphates Nutrition 0.000 claims description 5
- 229920000428 triblock copolymer Polymers 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical class [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000008363 phosphate buffer Substances 0.000 claims description 4
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 3
- 239000000176 sodium gluconate Substances 0.000 claims description 3
- 235000012207 sodium gluconate Nutrition 0.000 claims description 3
- 229940005574 sodium gluconate Drugs 0.000 claims description 3
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 3
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 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
- NCSHGROOCJHAFK-UHFFFAOYSA-N [Cl].N#CC#N Chemical compound [Cl].N#CC#N NCSHGROOCJHAFK-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims 1
- 238000005829 trimerization reaction Methods 0.000 claims 1
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 4
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 2
- 239000002781 deodorant agent Substances 0.000 abstract description 2
- 238000004043 dyeing Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- BULLJMKUVKYZDJ-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-6-iodohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I BULLJMKUVKYZDJ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process 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
- 239000002131 composite material Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000009990 desizing Methods 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 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
- 238000009992 mercerising Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 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
- 238000004065 wastewater treatment 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B01J35/39—
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The present invention relates to a kind of fiber/CNT/MgFe2O4Three-dimensional recyclable efficient catalytic material and its preparation and application, multifunctional carbon nanotube are loaded with a nanometer MgFe in textile fabric surface construction three-dimensional continuous structure, wherein multifunctional nano pipe surface2O4;Prepare:Fiber impregnation is combined MgFe to containing CNT2O4In polyethylene glycol 2000 dispersion liquid, 60 80 DEG C of 2 4h of reaction, drying, washing, repeated impregnations, drying and water-washing process 35 times are obtained final product.Of the invention with low cost, preparation method is simple, and the requirement to equipment is low, and operability is good;Water treatment agent of the invention can go remove water middle and high concentration organic pollution, it is adaptable to the advanced treating of various waste water, environmentally friendly non-secondary pollution, and have the advantages that antibacterial, it is deodorant, other heavy metal ion can be adsorbed.
Description
Technical field
The invention belongs to catalyst material and its preparation and application field, more particularly to a kind of fiber/CNT/
MgFe2O4Three-dimensional recyclable efficient catalytic material and its preparation and application.
Background technology
The water in the whole world only about 10% is directly used by the mankind.Lion's share, 70% is used for agricultural, and remaining 20% is
It is industrial.The blowdown of China is about the 20% of the whole world, and it has to the fresh water of global 5%.Therefore, pollution problem is solved
Put on the agenda.In textile printing and dyeing, leather, paper industry process, pollution environment has largely been used and to human body
Harmful auxiliary agent, these auxiliary agents pollute environment with the form discharge of liquid mostly, and biological degradability is poor, and toxicity is big, first of dissociating
Aldehyde is high, the content overproof of heavy metal ion.Wherein, printing and dyeing dressing is even more and turns into water pollution rich and influential family undisputedly.From
Starching start to desizing, wash, scouring and bleaching, mercerising, then dyeing and printing, may also need coating, all related to per procedure by this flow
And washing, and need 20L water consumptions per every kilogram of material of procedure.Result is that the water consumption of every kilogram of raw cotton during dressing has added
Carry out up to 200L.When showing in shopper window after an in men's style shirt customization for standard, it is being produced and processed more than 2000L water
When by (cloth of having used up:Pure cotton, 125g/m).
The method of the treatment waste water for using at present mainly has:Physical partition method, biological degradation method, chemical decomposition method, but this
A little methods all have some limitations, and are unfavorable for sustainable development.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of fiber/CNT/MgFe2O4Three-dimensional is recyclable efficient
Catalysis material and its preparation and application, the inventive method are simple to operate, with low cost, and the requirement to equipment is low;Water treatment agent is fitted
For the advanced treating of various waste water, environmentally friendly non-secondary pollution.
A kind of fiber/CNT/MgFe of the invention2O4The recyclable efficient catalytic material of three-dimensional, multifunctional carbon nanotube
In textile fabric surface construction three-dimensional continuous structure, wherein multifunctional nano pipe surface is loaded with a nanometer MgFe2O4, formation fiber/
CNT/MgFe2O4The recyclable catalysis material of three-dimensional.
The specific surface area of multifunctional nano pipe is 20~150m2/g;The nanometer MgFe2O4It is monoclinic form structure, crystal grain
Size is 15~200nm;Textile fabric is flexible textile fiber;Nanometer MgFe2O4It is 1 with the mass ratio of multifunctional nano pipe:5
~20.
A kind of fiber/CNT/MgFe of the invention2O4The preparation method of the recyclable efficient catalytic material of three-dimensional, bag
Include:
(1) by MgFe2O4, stabilizer, template, multifunctional carbon nanotube be added in phosphate buffer, stirring 30~
60min, forms suspension, then alkali lye regulation pH=5~6,180 DEG C of 3~5h of reaction, obtains multifunctional carbon nanotube and is combined
MgFe2O4;Wherein MgFe2O4It is 1 with the mass ratio of multifunctional carbon nanotube:5~1:20;
(2) fiber impregnation to 0.05~0.75g/L CNTs is combined MgFe2O4With the poly- second two of 0.025~0.375g/L
In the dispersion liquid of alcohol 2000,60-80 DEG C of reaction 2-4h, drying, washing, repeated impregnations, drying and water-washing process 3-5 times obtain final product fibre
Dimension/CNT/MgFe2O4The recyclable efficient catalytic material of three-dimensional.
MgFe in suspension in the step (1)2O4Concentration is 0.01~0.2mol/L;Stabilizer is ethylenediamine tetra-acetic acid
One kind in disodium, tetrasodium ethylenediamine tetraacetate, sodium gluconate, BTCA, stabilizer concentration is 0.01~0.1mol/
L。
Template is mass ratio 1 in the step (1):3 triblock polyether P123's and triblock copolymer F127 is mixed
Compound;Template agent concentration is 0.01~0.1mol/L.
Step (1) phosphate buffer by 0.025~0.05mol/L of concentration sodium dihydrogen phosphates and 0.05~
0.1mol/L dibastic sodium phosphates are constituted;Alkali lye is:The NaOH of 0.5mol/L~1.5mol/L or the aqueous solution of potassium hydroxide
The preparation method of multifunctional carbon nanotube in the step (1), including:
A CNT CNTs is added to FeCl by ()2In solution, pH=3 is adjusted, be subsequently adding H2O2, room temperature ultrasound 0.5-
2h, room temperature magnetic agitation 6-8h, suction filtration washing to neutrality, suction filtration, vacuum drying obtain product a;Wherein CNT CNTs,
FeCl2Solution, the ratio of H2O2 are 150~200mg:30~40mL:30~40mL;It is preferred that CNT CNTs, FeCl2Solution,
The ratio of H2O2 is 200mg:4 0mL:40mL;Wherein it is vacuum dried to be vacuum dried 24h at 60 DEG C;
B () in there-necked flask is dried, product a is scattered in solvent DMF, frozen water under the conditions of leading under condition of nitrogen gas
Bath cooling, 0 DEG C of addition NaH, stirs 20-30min, is then gradually warmed up to 85-90 DEG C, is added dropwise over 1- perfluor fluorine hexyl iodides,
Ultrasonic reaction 18-24h, add water quenching reaction, washing, in vacuum drying oven 50 DEG C dry 96h, obtain black particle product b;Its
Middle product a, solvent, the ratio of NaH, 1- perfluor fluorine hexyl iodide are 1.5~3g:100~200mL:300~522mg:2-3mL;
Preferred product a, solvent, the ratio of NaH, 1- perfluor fluorine hexyl iodide are 3g:200mL:522mg:3mL;
C be dispersed in water for product b by (), add NaOH, 0.5~1h of ultrasonic disperse, Cyanuric Chloride to add after being dispersed in water
Enter in reaction system, 0~5 DEG C of stirring reaction 24-48h, centrifuge washing (successively with water and ethanol centrifuge washing), 25 DEG C of vacuum are dried
Dry 96h, obtains product c;Wherein product b, NaOH, the ratio of Cyanuric Chloride are 1~2g:300~438mg:1~2g;It is preferred that producing
Thing b, NaOH, the ratio of Cyanuric Chloride are 2g:438mg:2g;
Under (d) logical condition of nitrogen gas, product c, triethylamine, DMF, ice-water bath cooling, at 0 DEG C are added in there-necked flask is dried
It is added dropwise over acryloyl chloride (by volume 1:10 are dissolved in DMF), ultrasonic reaction 12-24h, centrifuge washing (successively with ethanol and
Water centrifuge washing), room temperature in vacuo drying obtains black solid product d;Wherein product c, triethylamine, DMF, the ratio of acryloyl chloride
Example is 1~1.5g:3~2.4mL:100~150mL:0.5~1mL;It is preferred that:Product c, triethylamine, DMF, the ratio of acryloyl chloride
It is 1.5g:2.4mL:150mL:1mL;
(e) product d, dimethylphosphite, DMF mixing, it (is by volume 0.3 that DBU is dissolved in into solvent:20 are dissolved in solvent
In DMF) in after be added dropwise in reaction system, 25 DEG C of ultrasonic reaction 24-48h, centrifuge washing (successively with second alcohol and water be centrifuged wash
Wash (300mL × 3 time)), room temperature in vacuo drying obtains multifunctional carbon nanotube;Wherein product d, methyl phosphite, the ratio of DBU
Example is 1g, 300~415mg:0.5mol;Wherein preferred product d, methyl phosphite, the ratio of DBU are 1g:415mg:0.5mol.
FeCl in the step (a)2The mass percentage concentration of solution is 30%.
Sodium carbonate liquor regulation pH value in the step (a).
A kind of fiber/CNT/MgFe of the invention2O4The application of the recyclable efficient catalytic material of three-dimensional, at water
The application of agent is managed, for the treatment of waste water, specially by fiber/CNT/MgFe2O4The recyclable efficient catalytic material of three-dimensional
In addition waste water, daylight illumination 3-8h.
CNT as a kind of porous mass, with special interlayer characteristic, can be in its area load MgFe2O4Particulate,
It is prepared into loaded catalyst.This loaded photocatalyst can improve the dispersiveness of photochemical catalyst, and profit is repeated beneficial to reclaiming
With.The present invention constructs nano semiconductor material in high specific area carbon pipe surface, then will load the Gao Bibiao of semi-conducting material
Area carbon pipe constructs three-dimensional continuous structure in fabric face, then forms new textile fabric/CNT/heterogeneous semiconductor
Continuous grids structure, using the porous and capillary effect of flexible fibrous material, makes fiber to adsorb pollutant, while again
Can be by adsorbing pollutant in fiber surface enrichment for nano-photocatalyst material provides high concentration reactant bad border, this is very big
Photocatalytic degradation reaction rate is accelerated in degree.Additionally, the suction-operated of fiber is also possible to make photocatalytic degradation react generation
Intermediate by-products generation when be adsorbed and be further oxided to be degraded to simple inorganic matter, such as carbon dioxide and water.
So fiber can not only concentration pollutant, accelerate photocatalytic degradation reaction, and intermediate by-products can be reduced, in time release
Product, constantly advances degradation reaction.The effective discrete nucleation material of high-specific surface area of CNT is also given full play to simultaneously, is increased
Plus catalyst and the contact interface of pollutant, for light-catalyzed reaction provides more reactivity points, and guarantee to realize light
Give birth to the directional transmissions of electronics, effectively improve itself and hole separative efficiency, improve its photocatalytic activity.
The features such as present invention is using the porous of CNT, high adsorption capacity and easily separated water and MgFe2O4Photocatalysis
Activity combines, by nanometer MgFe2O4Successfully load on CNT, being prepared into can be suspended in waste water and can
The visible-light photocatalysis material of the high catalytic activity to be smoothly separated from water, and it is applied to the advanced treating of waste water, can
It is a technique for environment-friendly type rather than being transferred to elsewhere to realize to water middle and high concentration organic pollution oxidation removal
Technology.
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 invention can go to remove water middle and high concentration organic pollution, it is adaptable to the depth of various waste water
Treatment, environmentally friendly non-secondary pollution, and have the advantages that antibacterial, it is deodorant, other heavy metal ion can be adsorbed;
(3) water treatment agent of the invention can overcome the shortcomings of existing silver orthophosphate composite water disposal agent, and water treatment efficiency is good,
Can recycle.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
(1) 150mg CNTs are added to the mass percentage concentration 30%FeCl of 30mL2In solution, pH=3 is adjusted, then
Add 30mL H2O2, room temperature ultrasound 0.5h, room temperature magnetic agitation 6h, add water 500mL, suction filtration washing to neutrality, suction filtration.At 60 DEG C
Lower vacuum drying 24h obtains product a;
Under logical condition of nitrogen gas, 1.5g products a is being scattered in 100mL DMF in drying there-necked flask, ice-water bath is cold
But, 0 DEG C of addition NaH 300mg, continues to stir 20min.Then 85 DEG C are gradually warmed up to, 2mL 1- perfluor fluorine hexyls are added dropwise over
Iodine, ultrasonic reaction 18h, plus a small amount of water quenching is reacted, successively DMF, second alcohol and water centrifuge washing.The black particle product b for obtaining
50 DEG C dry 96h in vacuum drying oven;
1g black products b is dispersed in 50mL water, 300mg NaOH, ultrasonic disperse 0.5h, 1g Cyanuric Chloride point is added
It is dispersed in 50mL water, in addition there-necked flask, 0 DEG C of stirring reaction 24h.Water and ethanol centrifuge washing are used successively.25 DEG C of vacuum are dried
Dry 96h, obtains product c;Under logical condition of nitrogen gas, 1g product c, triethylamine 2.4mL, DMF are added in there-necked flask is dried
100mL.Ice-water bath is cooled down, and acryloyl chloride 0.5mL (being dissolved in 10mL DMF), ultrasonic reaction 12h are added dropwise at 0 DEG C.Use successively
Second alcohol and water centrifuge washing.The black solid product d for obtaining, room temperature in vacuo drying;
1g product d, dimethylphosphite 300mg, DMF 150mL are added in there-necked flask, by 0.3mL DBU (0.5mol)
It is dissolved in 20mL DMF, is added dropwise in above-mentioned there-necked flask, 25 DEG C of ultrasonic reaction 24h.Second alcohol and water centrifuge washing is used successively
(300mL × 3 time) room temperature in vacuo is dried, and obtains multifunctional carbon nanotube e.
(2) it is 1 by MgFe2O4, disodium ethylene diamine tetraacetate, mass ratio:3 triblock polyether P123 and triblock copolymer
Multifunctional carbon nanotube e is added to concentration for 0.025mol/L sodium dihydrogen phosphates in the mixture and above-mentioned steps (1) of thing F127
In the buffer solution constituted with 0.05mol/L dibastic sodium phosphates, 30min is stirred, form suspension;The wherein concentration of MgFe2O4 is
0.01mol/L, the concentration of stabilizer are 0.01mol/L, the concentration of template is 0.05mol/L.
(3) pH value for adjusting above-mentioned suspension with the sodium hydrate aqueous solution of concentration 0.5mol/L is 5, at 80 DEG C of heating,
Backflow 6h, filtering obtains the compound MgFe of CNT2O4;Wherein MgFe2O4 is 1 with the mass ratio of CNT:5.
(4) flaxen fiber is impregnated into and is combined MgFe containing 0.05g/L CNTs2O4With 0.025g/L polyethylene glycol 2000s
In dispersion liquid, 60 DEG C of reaction 2h, drying, washing, repeated impregnations, drying and water-washing process 3 times, obtain final product fiber/CNT/
MgFe2O4The recyclable efficient catalytic material of three-dimensional.
Embodiment 2
(1) 175mg CNTs are added to the 30%FeCl of 35mL2In solution, pH=3 is adjusted, be subsequently adding 35mL
H2O2, room temperature ultrasound 1.5h, room temperature magnetic agitation 87h, add water 500mL, suction filtration washing to neutrality, suction filtration.The vacuum at 60 DEG C
Dry 24h and obtain product a;
Under logical condition of nitrogen gas, 2.5g products a is being scattered in 150mL DMF in drying there-necked flask, ice-water bath is cold
But, 0 DEG C of addition NaH 411mg, continues to stir 30min.Then 88 DEG C are gradually warmed up to, be added dropwise over 2.5mL 1- perfluors fluorine oneself
Base iodine, ultrasonic reaction perfluoro-hexyl iodide, ultrasonic reaction 20h.Plus a small amount of water quenching reaction, DMF, second alcohol and water are centrifuged and wash successively
Wash.The black particle product b for obtaining dries 96h for 50 DEG C in vacuum drying oven;
1.5g products b is dispersed in 50mL water, 438mg NaOH, the dispersion of ultrasonic disperse 1h, 1.5g Cyanuric Chloride is added
In 50mL water, in addition there-necked flask, 2.5 DEG C of stirring reaction 36h.Water and ethanol centrifuge washing are used successively.25 DEG C of vacuum are dried
Dry 96h, obtains product c;
Under logical condition of nitrogen gas, 1.5g product c, triethylamine 2.8mL, DMF 125mL are added in there-necked flask is dried.Frozen water
Bath cooling, is added dropwise over acryloyl chloride 0.75mL (being dissolved in 10mL DMF), ultrasonic reaction 18h at 0 DEG C.Successively with second alcohol and water from
The heart is washed.The black solid product d for obtaining, room temperature in vacuo drying;Product 1g d, dimethylphosphite are added in there-necked flask
350mg, DMF 150mL, 0.18mL DBU (0.3mol) are dissolved in 20mL DMF, are added dropwise in above-mentioned there-necked flask, 25
DEG C ultrasonic reaction 36h.Dried with second alcohol and water centrifuge washing (300mL × 3 time) room temperature in vacuo successively, obtain multifunctional C nanometer
Pipe e;
(2) it is 1 by MgFe2O4, sodium gluconate, mass ratio:3 triblock polyether P123 and triblock copolymer F127
Mixture and above-mentioned steps (1) in multifunctional carbon nanotube e be added to concentration for 0.03mol/L sodium dihydrogen phosphates and
In the buffer solution of 0.05mol/L dibastic sodium phosphates composition, 45min is stirred, form suspension;The wherein concentration of MgFe2O4 is
0.01mol/L, the concentration of stabilizer are 0.03mol/L, the concentration of template is 0.07mol/L.
(3) pH value for adjusting above-mentioned suspension with the sodium hydrate aqueous solution of concentration 0.5mol/L is 7, at 90 DEG C of heating,
Backflow 16h, filtering obtains the compound MgFe of CNT2O4;Wherein MgFe2O4 is 1 with the mass ratio of CNT:15.
(4) polyster fibre is impregnated into and is combined MgFe containing 0.375g/L CNTs2O4With 0.15g/L polyethylene glycol
In 2000 dispersion liquids, 70 DEG C of reaction 3h, drying, washing, repeated impregnations, drying and water-washing process 4 times obtain final product fiber/carbon nanometer
Pipe/MgFe2O4The recyclable efficient catalytic material of three-dimensional.
Embodiment 3
(1) 200mg CNTs are added to the 30%FeCl of 40mL2In solution, pH=3 is adjusted, be subsequently adding 40mL
H2O2, room temperature ultrasound 2h, room temperature magnetic agitation 8h, add water 500mL, suction filtration washing to neutrality, suction filtration.It is vacuum dried at 60 DEG C
24h obtains product a;
Under logical condition of nitrogen gas, 3g products a is being scattered in 200mL DMF in drying there-necked flask, ice-water bath cooling,
0 DEG C of addition NaH 522mg, continues to stir 30min.Then 90 DEG C are gradually warmed up to, 3mL 1- perfluor fluorine hexyl iodides are added dropwise over,
Ultrasonic reaction perfluoro-hexyl iodide, ultrasonic reaction 24h.Plus a small amount of water quenching reaction, DMF, second alcohol and water centrifuge washing successively.Obtain
Black particle product b dry 96h for 50 DEG C in vacuum drying oven;
2g products b is dispersed in 50mL water, adds 438mg NaOH, ultrasonic disperse 1h, 2g Cyanuric Chloride to be dispersed in
In 50mL water, in addition there-necked flask, 0~5 DEG C of stirring reaction 48h.Water and ethanol centrifuge washing are used successively.25 DEG C of vacuum dryings
96h, obtains product c;
Under logical condition of nitrogen gas, 1.5g product c, triethylamine 2.4mL, DMF 150mL are added in there-necked flask is dried.Frozen water
Bath cooling, is added dropwise over acryloyl chloride 1mL (being dissolved in 10mL DMF), ultrasonic reaction 24h at 0 DEG C.It is centrifuged with second alcohol and water successively
Washing.The black solid product d for obtaining, room temperature in vacuo drying;
Product d1g, dimethylphosphite 415mg, DMF 150mL are added in there-necked flask, by 0.3mL DBU (0.5mol)
It is dissolved in 20mL DMF, is added dropwise in above-mentioned there-necked flask, 25 DEG C of ultrasonic reaction 48h.Second alcohol and water centrifuge washing is used successively
(300mL × 3 time) room temperature in vacuo is dried, and obtains multifunctional carbon nanotube e;
(2) it is 1 by MgFe2O4, BTCA, mass ratio:3 triblock polyether P123 and triblock copolymer F127
Mixture and above-mentioned steps (1) in multifunctional carbon nanotube e be added to concentration for 0.05mol/L sodium dihydrogen phosphates and
In the buffer solution of 0.1mol/L dibastic sodium phosphates composition, 60min is stirred, form suspension;The concentration 0.15mol/ of wherein MgFe2O4
L, the concentration of stabilizer are 0.05mol/L, the concentration of template is 0.1mol/L.
(3) pH value for adjusting above-mentioned suspension with the potassium hydroxide aqueous solution of concentration 1.5mol/L is 9, at 100 DEG C of heating,
Backflow 24h, filtering obtains the compound MgFe of CNT2O4;Wherein MgFe2O4 is 1 with the mass ratio of CNT:20.
(4) aramid fiber is impregnated into and is combined MgFe containing 0.75g/L CNTs2O4With 0.375g/L polyethylene glycol
In 2000 dispersion liquids, 80 DEG C of reaction 4h, drying, washing, repeated impregnations, drying and water-washing process 5 times obtain final product fiber/carbon nanometer
Pipe/MgFe2O4The recyclable efficient catalytic material of three-dimensional.
It is process object with the dyeing waste water of the printing and dyeing mill of same time sampling, in containing 0.2g/l waste water from dyestuff respectively
The water treatment agent of the gained of embodiment 1~3 of concentration 5g/l catalysis fibre materials is added, by after 6 hours solar radiations, water process
Agent is as shown in the table to the percent of decolourization of dyeing waste water:
Claims (10)
1. a kind of fiber/CNT/MgFe2O4The recyclable efficient catalytic material of three-dimensional, it is characterised in that:Multifunctional C nanometer
Pipe is loaded with a nanometer MgFe in textile fabric surface construction three-dimensional continuous structure, wherein multifunctional nano pipe surface2O4, form fine
Dimension/CNT/MgFe2O4The recyclable catalysis material of three-dimensional.
2. a kind of fiber/CNT/MgFe according to claim 12O4The recyclable efficient catalytic material of three-dimensional, it is special
Levy and be:The specific surface area of multifunctional nano pipe is 20~150m2/g;The nanometer MgFe2O4It is monoclinic form structure, crystal grain
Size is 15~200nm;Textile fabric is flexible textile fiber;Nanometer MgFe2O4It is 1 with the mass ratio of multifunctional nano pipe:5
~20.
3. a kind of fiber/CNT/MgFe as described in claim 1-2 is any2O4The recyclable efficient catalytic material of three-dimensional
Preparation method, including:
(1) by MgFe2O4, stabilizer, template, multifunctional carbon nanotube be added in phosphate buffer, stirring 30~
60min, forms suspension, then alkali lye regulation pH=5~6,180 DEG C of 3~5h of reaction, obtains the compound MgFe of CNT2O4;
Wherein MgFe2O4It is 1 with the mass ratio of multifunctional carbon nanotube:5~1:20;
(2) fiber impregnation is combined MgFe to containing 0.05~0.75g/L CNTs2O4With the poly- second two of 0.025~0.375g/L
In the dispersion liquid of alcohol 2000,60-80 DEG C of reaction 2-4h, drying, washing, repeated impregnations, drying and water-washing process 3-5 times obtain final product fibre
Dimension/CNT/MgFe2O4The recyclable efficient catalytic material of three-dimensional.
4. a kind of fiber/CNT/MgFe according to claim 32O4The preparation of the recyclable efficient catalytic material of three-dimensional
Method, it is characterised in that:MgFe in suspension in the step (1)2O4Concentration is 0.01~0.2mol/L;Stabilizer is second two
One kind in amine tetraacethyl disodium, tetrasodium ethylenediamine tetraacetate, sodium gluconate, BTCA, stabilizer concentration is 0.01
~0.1mol/L.
5. a kind of fiber/CNT/MgFe according to claim 32O4The preparation of the recyclable efficient catalytic material of three-dimensional
Method, it is characterised in that:Template is mass ratio 1 in the step (1):3 triblock polyether P123 and triblock copolymer
The mixture of F127;Template agent concentration is 0.01~0.1mol/L.
6. a kind of fiber/CNT/MgFe according to claim 32O4The preparation of the recyclable efficient catalytic material of three-dimensional
Method, it is characterised in that:Step (1) phosphate buffer is by 0.025~0.05mol/L of concentration sodium dihydrogen phosphates and 0.05
~0.1mol/L dibastic sodium phosphates are constituted;Alkali lye is:The NaOH of 0.5mol/L~1.5mol/L or the aqueous solution of potassium hydroxide.
7. a kind of fiber/CNT/MgFe according to claim 32O4The preparation of the recyclable efficient catalytic material of three-dimensional
Method, it is characterised in that:The preparation method of multifunctional carbon nanotube in the step (1), including:
A CNT CNTs is added to FeCl by ()2In solution, pH=3 is adjusted, be subsequently adding H2O2, room temperature ultrasound 0.5-2h,
Room temperature magnetic agitation 6-8h, suction filtration washing to neutrality, suction filtration, vacuum drying obtains product a;Wherein CNT CNTs, FeCl2
Solution, the ratio of H2O2 are 150~200mg:30~40mL:30~40mL;
B be scattered in product a in solvent under logical condition of nitrogen gas by (), ice-water bath cooling, 0 DEG C of addition NaH, stirs 20-30min,
Then 85~90 DEG C are gradually warmed up to, 1- perfluor fluorine hexyl iodides are added dropwise over, ultrasonic reaction 18-24h, the quenching that adds water is reacted, washed
Wash, dry, obtain product b;Wherein product a, solvent, the ratio of NaH, 1- perfluor fluorine hexyl iodide are 1.5~3g:100~
200mL:300~522mg:2-3mL;
C be dispersed in water for product b by (), add NaOH, 0.5~1h of ultrasonic disperse, Cyanuric Chloride to be added after being dispersed in water anti-
Answer in system, 0~5 DEG C of stirring reaction 24-48h, centrifuge washing, vacuum drying obtains product c;Wherein product b, NaOH, trimerization
The ratio of chlorine cyanogen is 1~2g:300~438mg:1~2g;
D under () logical condition of nitrogen gas, product c, triethylamine, DMF, ice-water bath cooling is added dropwise over acryloyl chloride at 0 DEG C, ultrasound is anti-
12-24h is answered, centrifuge washing, room temperature in vacuo drying obtains product d;The wherein ratio of product c, triethylamine, DMF, acryloyl chloride
It is 1~1.5g:3~2.4mL:100~150mL:0.5~1mL;
E () product d, dimethylphosphite, DMF mixing is added dropwise in reaction system after DBU is dissolved in solvent, 25 DEG C surpass
Phonoresponse 24-48h, centrifuge washing, room temperature in vacuo drying obtains multifunctional carbon nanotube;Wherein product d, methyl phosphite,
The ratio of DBU is 1g, 300~415mg:0.5mol.
8. a kind of fiber/CNT/MgFe according to claim 72O4The preparation of the recyclable efficient catalytic material of three-dimensional
Method, it is characterised in that:FeCl in the step (a)2The mass percentage concentration of solution is 30%.
9. a kind of fiber/CNT/MgFe according to claim 72O4The preparation of the recyclable efficient catalytic material of three-dimensional
Method, it is characterised in that:Sodium carbonate liquor regulation pH value in the step (a).
10. a kind of fiber/CNT/MgFe as described in claim 1-2 is any2O4The recyclable efficient catalytic material of three-dimensional
Application, it is characterised in that:As the application of water treatment agent, for the treatment of waste water, specially by fiber/CNT/
MgFe2O4The recyclable efficient catalytic material of three-dimensional is added in waste water, daylight illumination 3-8h.
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CN102151567A (en) * | 2011-02-25 | 2011-08-17 | 哈尔滨工业大学 | Catalyst for oxidation and decomposition of organic pollutants in water with ozone and method thereof for catalyzing sewage treatment with ozone |
CN103030208A (en) * | 2013-01-08 | 2013-04-10 | 哈尔滨工业大学 | Application of spinel ferrite catalyst and method for urging persulfate to generate free radicals to catalytically degrade organic matters |
CN104528865A (en) * | 2014-12-25 | 2015-04-22 | 东华大学 | Method for preparing carbon nano tube composite SrFeO3 green deep water treatment agent |
CN106064102A (en) * | 2016-06-06 | 2016-11-02 | 东华大学 | A kind of textile fabric/Graphene/MgFe2o4the preparation method of combinational environment catalysis material |
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CN102151567A (en) * | 2011-02-25 | 2011-08-17 | 哈尔滨工业大学 | Catalyst for oxidation and decomposition of organic pollutants in water with ozone and method thereof for catalyzing sewage treatment with ozone |
CN103030208A (en) * | 2013-01-08 | 2013-04-10 | 哈尔滨工业大学 | Application of spinel ferrite catalyst and method for urging persulfate to generate free radicals to catalytically degrade organic matters |
CN104528865A (en) * | 2014-12-25 | 2015-04-22 | 东华大学 | Method for preparing carbon nano tube composite SrFeO3 green deep water treatment agent |
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