CN109956529A - A kind of preparation method and application of FeOCl/CNT composite membrane - Google Patents
A kind of preparation method and application of FeOCl/CNT composite membrane Download PDFInfo
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- CN109956529A CN109956529A CN201910256986.1A CN201910256986A CN109956529A CN 109956529 A CN109956529 A CN 109956529A CN 201910256986 A CN201910256986 A CN 201910256986A CN 109956529 A CN109956529 A CN 109956529A
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- 239000012528 membrane Substances 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002238 carbon nanotube film Substances 0.000 claims abstract description 39
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004098 Tetracycline Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 22
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 22
- 229960002180 tetracycline Drugs 0.000 claims abstract description 21
- 229930101283 tetracycline Natural products 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 20
- 230000005611 electricity Effects 0.000 claims abstract description 17
- 238000011065 in-situ storage Methods 0.000 claims abstract description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 11
- 230000020477 pH reduction Effects 0.000 claims abstract description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 7
- 239000002105 nanoparticle Substances 0.000 claims abstract description 4
- 238000007654 immersion Methods 0.000 claims abstract description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- 235000019441 ethanol Nutrition 0.000 claims description 15
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 9
- 239000012498 ultrapure water Substances 0.000 claims description 9
- 238000002604 ultrasonography Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229940106691 bisphenol a Drugs 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 230000002572 peristaltic effect Effects 0.000 claims description 5
- 230000008439 repair process Effects 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 230000009514 concussion Effects 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 55
- 239000002041 carbon nanotube Substances 0.000 description 53
- 229910021393 carbon nanotube Inorganic materials 0.000 description 53
- 238000012545 processing Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 206010054949 Metaplasia Diseases 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000015689 metaplastic ossification Effects 0.000 description 4
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 208000035473 Communicable disease Diseases 0.000 description 1
- 208000001647 Renal Insufficiency Diseases 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 241001655322 Streptomycetales Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 201000006370 kidney failure Diseases 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940072172 tetracycline antibiotic Drugs 0.000 description 1
- 229940040944 tetracyclines Drugs 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The application in tetracycline is handled under continuous galvanic electricity Fenton-like system with it the invention discloses a kind of preparation method of FeOCl/CNT composite membrane to apply.The preparation method is that: the CNT after acidification is mixed with 1-Methyl-2-Pyrrolidone；Mixed liquor is filtered by vacuum to PTFE support membrane, CNT film is obtained；By FeCl3·6H2O is dissolved in ethanol solution, and CNT film is placed in FeCl3It is impregnated in/alcohol mixed solution；CNT film after immersion is placed in a vacuum drying oven to the FeCl for heating and making to load on CNT3Decomposition in situ and aoxidize form FeOCl nano particle, FeOCl/CNT composite membrane is made.The present invention is acted under applying electrical potential based on Fenton, and catalysis generates OH, is realized in the efficient removal for crossing membrane process Organic Pollutants In Water.
Description
Technical field
Present invention relates particularly to a kind of preparation method and application of FeOCl/CNT composite membrane, belong to water-treatment technology field.
Background technique
Tetracycline medication is a kind of by the semi-synthetic broad-spectrum antibiotic produced either by streptomycete generation.From 20 generation
It has recorded since being found the forties, is widely used in treating various germ infectious diseases.Tetracycline antibiotics enter hardly possible after human body
To be absorbed by stomach, about 75% can be discharged into environment in the form of parent compound, be common in the works such as sanitary sewage and pharmaceutical factory
In industry waste water.The presence of tetracycline or the exceeded certain micro-organisms growth that can make in soil and water body of content are suppressed even dead
It dies, it is also possible to human body be entered by enrichment, cause the diseases such as renal failure.And tetracycline is slightly soluble in water, in air
With in water property stablize, and easily with various soda acid forming salts, it is difficult to effectively degradation.The processing technique being widely used both at home and abroad at present
Including advanced oxidation processes, absorption method, photocatalytic method and electrochemical process etc., but all there is various shortcoming so that it cannot be applied to
In actual production.Tetracycline wastewater is efficiently treated through for example, the porous materials such as active carbon can be used in absorption method, but active carbon
Higher cost, and the pollution that is easily blocked.Fenton oxidation method can pass through Fe2+Catalytic action generate have high reaction activity hydroxyl
Base free radical (OH), can most of tetracyclines in the efficient oxidation degrading waste water, but there are many restrictions, such as must keep acid
Property environment, oxidation efficiency is limited and product easily causes secondary pollution etc..Therefore, develop efficient, low consumption, environmental protection Fourth Ring
Element processing new technology is particularly important.
In recent years, it can be applied to neutral and alkaline pH environment heterogeneous Fenton technology and receive researchers at home and abroad
Concern.Heterogeneous Fenton catalyst effectively overcomes iron and reveals the disadvantages such as low with reaction rate under natural environment, urges simultaneously
Agent can be separated and recovered and be recycled from water body, be shown in the practical application of processing Organic Pollutants In Water
Huge potentiality.And FeOCl not only has efficient oxidative function as outstanding person therein, additionally it is possible to solely by itself
Special molecular structure promotes Fe3+With Fe2+Between change, to continually generate new Fe2+Fenton reaction is participated in, effectively
Solve the problems, such as that material consumption is excessive.Meanwhile as electrochemical oxidation technology in recent years is increasingly by the blueness of researcher
It looks at, electro-catalysis Fenton method gradually replaces additional H2O2As research hotspot.FeOCl is combined with electrochemical oxidation technology,
DO transformation is in situ under conditions of applying electrical potential, in solution generates H2O2And Fenton reaction, a side occurs in FeOCl catalytic action
Reduce the additional H of reaction process in face2O2Cost；Still further aspect shortens FeOCl and H2O2The time required to contact, OH is avoided
Waste in transmittance process, to improve the utilization rate of OH.
Since FeOCl is a kind of loose, powdered substance soluble easily in water, it is difficult to control injected volume and timely and effective time
It receives, between the catalytic separation film system being concerned at present in water treatment field, catalytic process and membrane separating process is integrated in
In the same processing unit, is loaded in carrier film and used.And in the selection of carrier material, carbon-based material, zeolite and
There is synthetic resin etc. the material of the abundant and dispersed good characteristics of large specific surface area, good mechanical property, cellular structure to become
Primary investigation object.The new development in the field carbon nanotube (CNT) in recent years provides for the FeOCl filter membrane preparation of high-efficiency multi-function
New direction.CNT is a kind of monodimension nanometer material of tubular structure, and hole can be made by the methods of inversion of phases or physics suction filtration
Rate height (>85%), aperture small (<100nm) and have biggish specific surface area (>88m2/ g) three-dimensional self-supported membrane, can be used as
The excellent carrier of catalysis material.Since CNT film has excellent Physical Mechanical, chemical stability, flexibility, antibacterial resistance to soiling
And the physicochemical properties such as super-hydrophobicity, it is considered to be have promising separation material.
Summary of the invention
Problem to be solved by this invention is: the problem of existing Fenton oxidation method processing tetracycline condition harshness.
To solve the above-mentioned problems, the present invention provides a kind of preparation method of FeOCl/CNT composite membrane, feature exists
In, comprising the following steps:
Step 1): multi wall CNT and concentrated nitric acid agitating and heating are made into its acidification；
Step 2): the CNT after acidification is mixed with 1-Methyl-2-Pyrrolidone, and ultrasound is evenly dispersed；
Step 3): the mixed liquor that step 2) is obtained is filtered by vacuum to PTFE support membrane, then successively with ethyl alcohol, ultrapure
Water clean the surface impurity, obtains CNT film；
Step 4): by FeCl3·6H2O is dissolved in ethanol solution, and CNT film is placed in FeCl3In/alcohol mixed solution, lead to
Shaking table concussion is crossed uniformly to impregnate；
Step 5): the CNT film after immersion is placed in a vacuum drying oven to the FeCl for heating and making to load on CNT3In situ point
It solves and aoxidizes to form FeOCl nano particle, FeOCl/CNT composite membrane is made.
Preferably, the ratio of multi wall CNT and concentrated nitric acid is 1g:1L in the step 1)；CNT and 1- methyl-in step 2)
The ratio of 2-Pyrrolidone is 2g:5L；The mass ratio of ethyl alcohol and ultrapure water is 1:1.5 in step 3)；FeCl in step 4)3·
6H2The ratio of O and ethyl alcohol is (1~4) g:(2~3) L.
Preferably, the ultrasonic power in the step 2) is 50~200W, 20~60min of ultrasonic time.
Preferably, the molar ratio of Fe and CNT is 0.003~0.13 in the step 4).
Preferably, the heating temperature in the step 5) is 180~240 DEG C, and heating time is 0.5~3h.
The present invention also provides FeOCl/CNT composite membranes made from a kind of preparation method of above-mentioned FeOCl/CNT composite membrane
The application in tetracycline is handled under continuous galvanic electricity Fenton-like system.
Preferably, above-mentioned application the following steps are included:
Step 6): using FeOCl/CNT composite membrane made from step 5) as cathode, CNT film made from step 3) is as sun
Continuous galvanic electricity Fenton-like system is made in pole, and being passed through the solution containing tetracycline with the flow velocity of 0.5-5mL/min by peristaltic pump should
Continuous galvanic electricity Fenton-like system is filtered.It is acted on based on potential, DO transformation is in situ to generate H2O2Fenton occurs with FeOCl to react,
A large amount of OH are continually generated, are realized in the efficient removal for crossing membrane process Organic Pollutants In Water.
Preferably, the potential of the cathode is 0.1~1Vvs.Ag/AgCl, and pH value range is 2~12.
Preferably, the organic pollutant is any one or a few in tetracycline, bisphenol-A and methylene blue.
Preferably, after the continuous galvanic electricity Fenton-like system adsorption saturation, pass through H2O2It impregnates or filtering is regenerated.CNT film
It can be in H2O2Strengthen with realization desorption performance under applying electrical potential, accelerates the method for regeneration rate.
It is highly preferred that regenerative process, i.e. FeOCl/CNT composite membrane can be accelerated by applying reverse potential in the regenerative process
As anode, for CNT film as cathode, the potential that regenerative process is applied is no more than 0.8V.
The H that FeOCl/CNT composite membrane and power-up generate2O2Fenton reaction occurs；And Fe can be effectively promoted3+With Fe2+
Between transfer efficiency, to accelerate Fenton reaction rate.
The present invention using impregnate and heat resolve again synthetic method by FeCl3It is sequestered on CNT and in-situ oxidation is formed
Nanometer Fe OCl particle is filtered to FeOCl/CNT composite membrane is made on polytetrafluoroethylene (PTFE) (PTFE) film.Under applying electrical potential, it is based on
Fenton effect, catalysis generate OH, realize in the efficient removal for crossing membrane process Organic Pollutants In Water.
Compared with the prior art, the present invention has the following beneficial effects:
(1) Fenton technology is combined with membrane separation technique, traditional particle is replaced with continuous flow membrane filtration pattern
Shape catalyst, the effect of mass transmitting during intensified response improve degradation efficiency；
(2) the FeOCl/CNT composite membrane prepares that raw material is simple and easy to get, manufacturing cycle is shorter, preparation condition is mild, raw material
It is all lower with the cost of preparation；
(3) FeCl is chelated using carboxyl and hydroxyl3, vacuum oven heating and decomposition in situ synthetic method will be received again
In meter level FeOCl particulate load to CNT, nanometer Fe OCl is evenly distributed and partial size is small (< 10nm), can react and provide for Fenton
More active site；
(4) it using CNT network structure as the carrier of FeOCl nano particle, is increased compared to pellet type catalyst and compares table
Area and porosity, improve the ferriferous oxide load capacity of unit carrier, while solving what pellet type catalyst was difficult to recycle
Problem；
(5) FeOCl has been solved perfectly traditional Fenton catalyst and has been only applicable to acidity as a kind of heterogeneous catalysis
pH、Fe3+The problems such as transformation efficiency is low further increases oxidative function；
(6) after composite membrane saturation, filtering can be cleaned by H2O2 and anti-power-up gesture is regenerated, there is good desorption speed
Rate and persistently use function.
Detailed description of the invention
Fig. 1 is the transmission electron microscope figure of FeOCl/CNT composite membrane made from embodiment 1；
Fig. 2 is the photo of FeOCl/CNT composite membrane made from embodiment 1；
Fig. 3 is the schematic diagram of continuous galvanic electricity Fenton-like system；
Fig. 4 is comparison diagram of the FeOCl/CNT composite membrane with pure CNT film to the treatment effect of tetracycline in embodiment 2.
Specific embodiment
In order to make the present invention more obvious and understandable, hereby with preferred embodiment, and attached drawing is cooperated to be described in detail below.
Embodiment 1
A kind of preparation method of FeOCl/CNT composite membrane:
(1) 20mg multi wall CNT nitric acid (> 98wt%) the soaking and stirring 12h at 70 DEG C is taken, is filtered by vacuum and is used in combination for bulk
Ultrapure water washes away extra acid solution；
(2) CNT after acidification is dissolved in 40mL 1-Methyl-2-Pyrrolidone, ultrasound makes its dispersion；
(3) obtained dispersion liquid is filtered by vacuum on the PTFE support membrane for being 47mm to diameter, CNT film is made；
(4) 33mg FeCl is added into 20mL ethyl alcohol3·6H2O powder simultaneously stirs evenly, by CNT film in FeCl3Ethyl alcohol is molten
1h is impregnated in liquid, makes FeCl3It is chelated on CNT film；
(5) load there is into FeCl3CNT film heat 1.5h in 220 DEG C of vacuum oven, make FeCl3Decomposition in situ is again
FeOCl is generated, so that FeOCl/CNT composite membrane be made.
The quality of above-mentioned composite membrane is 68.42mg, specific surface area 163.4m2/ g, about twice of CNT specific surface area
(88.5m2/ g), as shown in Figure 1, 2.
Embodiment 2
A kind of method of continuous galvanic electricity Fenton-like system processing tetracycline:
(1) 30mg multi wall CNT nitric acid (> 98wt%) the soaking and stirring 12h at 70 DEG C is taken, is filtered by vacuum and is used in combination for bulk
Ultrapure water washes away extra acid solution；
(2) CNT after acidification is dissolved in 60mL 1-Methyl-2-Pyrrolidone, ultrasound makes its dispersion；
(3) obtained dispersion liquid is filtered by vacuum to the PTFE support membrane of diameter 47mm, CNT film is made；
(4) 25mg FeCl is added into 20mL ethyl alcohol3·6H2O powder simultaneously stirs evenly, by CNT film in FeCl3Ethyl alcohol is molten
1h is impregnated in liquid, makes FeCl3It is chelated on CNT film；
(5) load there is into FeCl3CNT film heat 1h in 220 DEG C of vacuum oven, make FeCl3Decomposition in situ oxygen again
FeOCl/CNT composite membrane is made at FeOCl in metaplasia.
Above-mentioned compound film quality is 59.87mg, specific surface area 192.6m2/ g, about twice of CNT specific surface area
(88.5m2/g)。
(6) as shown in figure 3, FeOCl/CNT composite membrane 1 is placed on a bilayer as anode as cathode, CNT film 2
In film filter shell 3, under applying electrical potential, by the way of continuous flow filtering, 20mg/L is contained by Fourth Ring by peristaltic pump
With the flow velocity of 1.5mL/min, the direction of filled arrows in Fig. 3 enters the double-deck film filter shell 3 to the waste water of element, and leads to
It crosses FeOCl/CNT composite membrane 1 (it is 38 ± 1mg/L, pH=5.9, applying electrical potential -0.6V that reaction condition, which is set as DO concentration), it is suitable
The direction outflow of hollow arrow in Fig. 3.
Comparative example 1
This comparative example and embodiment 2 the difference is that, cathode replaces FeOCl/CNT composite membrane using CNT film.
Comparative example 2
This comparative example and embodiment 2 the difference is that, FeOCl/CNT composite membrane does not apply potential
Embodiment 2 and the experimental data of comparative example 1,2 are as shown in Figure 4.From fig. 4, it can be seen that implementing under Fenton effect
The degradation rate of tetracycline is > 99% in example 2, and the degradation rate of tetracycline is about 18% in comparative example 1, tetracycline in comparative example 2
Degradation rate be about 53%.
Embodiment 3
A kind of method of continuous galvanic electricity Fenton-like system processing bisphenol-A:
(1) 20mg multi wall CNT nitric acid (> 98wt%) the soaking and stirring 12h at 75 DEG C is taken, is filtered by vacuum and is used in combination for bulk
Ultrapure water washes away extra acid solution；
(2) CNT after acidification is dissolved in 50mL 1-Methyl-2-Pyrrolidone, ultrasound makes its dispersion；
(3) obtained dispersion liquid is filtered by vacuum to the PTFE support membrane of diameter 47mm, CNT film is made；
(4) 20mg FeCl is added into 20mL ethyl alcohol3·6H2O powder simultaneously stirs evenly, by CNT film in FeCl3Ethyl alcohol is molten
1h is impregnated in liquid, makes FeCl3It is chelated on CNT film；
(5) load there is into FeCl3CNT film heat 1h in 200 DEG C of vacuum oven, make FeCl3Decomposition in situ oxygen again
FeOCl/CNT composite membrane is made at FeOCl in metaplasia.
The specific surface area of above-mentioned composite membrane is 185.3m2/g。
(6) Shanghai sampling of ground water is taken, measurement learns that its bisphenol A concentration is 23mg/L, pH=8.31.Step (5) are made
The FeOCl/CNT composite membrane obtained is made identical continuous galvanic electricity Fenton-like system in embodiment 2 and handles water sample, will by peristaltic pump
Solution, by device, uses electrochemical workstation applying electrical potential -0.6V with the flow velocity of 3mL/min.
After handling 2h, the concentration of bisphenol-A is less than 4mg/L, pH=6.3 in sample.
Embodiment 4
A kind of method of continuous galvanic electricity Fenton-like system processing methylene blue:
(1) 30mg multi wall CNT nitric acid (> 98wt%) the soaking and stirring 12h at 70 DEG C is taken, is filtered by vacuum and is used in combination for bulk
Ultrapure water washes away extra acid solution；
(2) CNT after acidification is dissolved in 60mL 1-Methyl-2-Pyrrolidone, ultrasound makes its dispersion；
(3) obtained dispersion liquid is filtered by vacuum to the PTFE support membrane of diameter 47mm, CNT film is made；
(4) 10.25mg FeCl is added into 20mL ethyl alcohol3·6H2O powder simultaneously stirs evenly, by CNT film in FeCl3Second
Alcohol solution for soaking 1h, makes FeCl3It is chelated on CNT film；
(5) load there is into FeCl3CNT film heat 1h in 220 DEG C of vacuum oven, make FeCl3Decomposition in situ oxygen again
FeOCl/CNT composite membrane is made at FeOCl in metaplasia；
(6) identical continuous galvanic electricity Fenton-like system in embodiment 2 is made in FeOCl/CNT composite membrane made from step (5)
And processing is the waste water of 10mg/L methylene blue containing concentration, processing parameter is the same as embodiment 2.
After handling 2h, the degradation rate of methylene blue is 86.5%.
Embodiment 5
A kind of method of continuous galvanic electricity Fenton-like system processing tetracycline:
(1) 30mg multi wall CNT nitric acid (> 98wt%) the soaking and stirring 12h at 70 DEG C is taken, is filtered by vacuum and is used in combination for bulk
Ultrapure water washes away extra acid solution；
(2) CNT after acidification is dissolved in 60mL 1-Methyl-2-Pyrrolidone, ultrasound makes its dispersion；
(3) obtained dispersion liquid is filtered by vacuum to the PTFE support membrane of diameter 47mm, CNT film is made；
(4) 16.5mg FeCl is added into 20mL ethyl alcohol3·6H2O powder simultaneously stirs evenly, by CNT film in FeCl3Ethyl alcohol
1h is impregnated in solution, makes FeCl3It is chelated on CNT film；
(5) load there is into FeCl3CNT film heat 1h in 220 DEG C of vacuum oven, make FeCl3Decomposition in situ oxygen again
FeOCl/CNT composite membrane is made at FeOCl in metaplasia.
(6) identical continuous galvanic electricity Fenton-like system in same embodiment 2 is made in FeOCl/CNT composite membrane obtained above,
The solution containing the tetracycline that concentration is 20mg/L is passed through into equipment (electrochemistry with the flow velocity of 1.5mL/min by peristaltic pump
The potential range that work station is applied is -1V).
Comparative example 3
The difference of this comparative example and embodiment 5 with do not apply potential when handling the solution containing tetracycline.
By the test data of embodiment 5 and comparative example 3 it is found that after the processing of comparative example 3 2h, the degradation rate of tetracycline in solution
It is 60%；After embodiment 5 handles 2h, the degradation rate of tetracycline reaches 99% or more in solution, illustrates DO power-up in the solution
Generate H2O2, reacted with FeOCl and promote Fe3+With Fe2+Between conversion, to enhance degradation rate.
By the H after the FeOCl/CNT composite membrane adsorption saturation in embodiment 5 by 10mmol/L2O2Solution filtering cleaning is again
Raw, the degradation rate after regeneration is regenerated with second for the first time is respectively the 92% and 83% of first adsorbance.Third time regeneration is applied
Add reverse potential, i.e. CNT film is as cathode, and for FeOCl/CNT composite membrane as anode, application potential is -0.4V.Third time regenerates
FeOCl/CNT composite membrane adsorbance afterwards is the 90% of first adsorbance.
Claims (11)
1. a kind of preparation method of FeOCl/CNT composite membrane, which comprises the following steps:
Step 1): multi wall CNT and concentrated nitric acid agitating and heating are made into its acidification；
Step 2): the CNT after acidification is mixed with 1-Methyl-2-Pyrrolidone, and ultrasound is evenly dispersed；
Step 3): the mixed liquor that step 2) is obtained is filtered by vacuum to PTFE support membrane, then successively clear with ethyl alcohol, ultrapure water
Surface impurity is washed, CNT film is obtained；
Step 4): by FeCl3·6H2O is dissolved in ethanol solution, and CNT film is placed in FeCl3In/alcohol mixed solution, by shaking
Bed concussion is uniformly impregnated；
Step 5): the CNT film after immersion is placed in a vacuum drying oven to the FeCl for heating and making to load on CNT3Decomposition in situ and oxygen
Change forms FeOCl nano particle, and FeOCl/CNT composite membrane is made.
2. the preparation method of FeOCl/CNT composite membrane as described in claim 1, which is characterized in that multi wall in the step 1)
The ratio of CNT and concentrated nitric acid is 1g:1L；The ratio of CNT and 1-Methyl-2-Pyrrolidone is 2g:5L in step 2)；In step 3)
The mass ratio of ethyl alcohol and ultrapure water is 1:1.5；FeCl in step 4)3·6H2The ratio of O and ethyl alcohol is (1~4) g:(2~3) L.
3. the preparation method of FeOCl/CNT composite membrane as described in claim 1, which is characterized in that super in the step 2)
Acoustical power is 50~200W, 20~60min of ultrasonic time.
4. the preparation method of FeOCl/CNT composite membrane as described in claim 1, which is characterized in that in the step 4) Fe with
The molar ratio of CNT is 0.003~0.13.
5. the preparation method of FeOCl/CNT composite membrane as described in claim 1, which is characterized in that adding in the step 5)
Hot temperature is 180~240 DEG C, and heating time is 0.5~3h.
6. FeOCl/CNT made from a kind of preparation method of FeOCl/CNT composite membrane described in claim 1-5 any one is multiple
It closes film and handles the application in tetracycline under continuous galvanic electricity Fenton-like system.
7. application as claimed in claim 6, which comprises the following steps:
Step 6): using FeOCl/CNT composite membrane made from step 5) as cathode, CNT film made from step 3) is as anode system
At continuous galvanic electricity Fenton-like system, being passed through the solution containing organic pollutant with the flow velocity of 0.5-5mL/min by peristaltic pump should
Continuous galvanic electricity Fenton-like system is filtered.
8. the use as claimed in claim 7, which is characterized in that the potential of the cathode is 0.1~1Vvs.Ag/AgCl, pH value
Range is 2~12.
9. the use as claimed in claim 7, which is characterized in that the organic pollutant is tetracycline, bisphenol-A and methylene blue
In any one or a few.
10. the use as claimed in claim 7, which is characterized in that after the continuous galvanic electricity Fenton-like system adsorption saturation, pass through
H2O2It impregnates or filtering is regenerated.
11. application as claimed in claim 10, which is characterized in that applying reverse potential in the regenerative process can accelerate again
Raw process, i.e. FeOCl/CNT composite membrane is as anode, and as cathode, the potential that regenerative process is applied is no more than CNT film
0.8V。
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