CN107008245A - TiO for the processing of high slat-containing wastewater organic pollution2Carbon fiber composite photo-catalyst and its preparation - Google Patents
TiO for the processing of high slat-containing wastewater organic pollution2Carbon fiber composite photo-catalyst and its preparation Download PDFInfo
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- CN107008245A CN107008245A CN201710236709.5A CN201710236709A CN107008245A CN 107008245 A CN107008245 A CN 107008245A CN 201710236709 A CN201710236709 A CN 201710236709A CN 107008245 A CN107008245 A CN 107008245A
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- 239000002131 composite material Substances 0.000 title claims abstract description 87
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 57
- 239000002351 wastewater Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000012545 processing Methods 0.000 title claims abstract description 9
- 239000000835 fiber Substances 0.000 title description 12
- 239000004917 carbon fiber Substances 0.000 claims abstract description 99
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000000725 suspension Substances 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000002604 ultrasonography Methods 0.000 claims abstract description 3
- 239000003643 water by type Substances 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 63
- 239000003054 catalyst Substances 0.000 abstract description 59
- 235000002639 sodium chloride Nutrition 0.000 abstract description 44
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 40
- 238000006731 degradation reaction Methods 0.000 abstract description 18
- 239000010442 halite Substances 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 13
- 230000015556 catabolic process Effects 0.000 abstract description 12
- 238000000926 separation method Methods 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 36
- 239000002245 particle Substances 0.000 description 34
- 239000011780 sodium chloride Substances 0.000 description 18
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 17
- 229940012189 methyl orange Drugs 0.000 description 17
- 238000001179 sorption measurement Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 13
- 230000001699 photocatalysis Effects 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 239000005416 organic matter Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 239000012267 brine Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 8
- 239000002699 waste material Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- -1 salt ion Chemical class 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000001782 photodegradation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000004876 x-ray fluorescence Methods 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 230000008033 biological extinction Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 125000005909 ethyl alcohol group Chemical group 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 230000003760 hair shine Effects 0.000 description 4
- 238000001239 high-resolution electron microscopy Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000013081 microcrystal Substances 0.000 description 4
- 239000013618 particulate matter Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
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- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- 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
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of TiO handled for high slat-containing wastewater organic pollution2Carbon fiber composite photo-catalyst and its preparation, preparation comprise the following steps：(1) carbon fiber is scattered in absolute ethyl alcohol, and stirred in water bath with thermostatic control until forming dispersed suspension system；(2) stirring simultaneously butyl titanate is added into the suspension system, after the completion of by warming-in-water to more than 80 DEG C, stirring simultaneously deionized water, stirring reaction is slowly added dropwise；(3) be cooled to after room temperature wash, filter, dry TiO2Carbon fiber nanometer composite material；(4) by TiO2Carbon fiber nanometer composite material is mixed with water, ultrasound under formed after uniform suspension system move into autoclave in, it is closed after be heat-treated at 160 DEG C~180 DEG C；(5) separation, washing, drying and processing produce material after the cooling of heat treatment reaction solution.Catalyst of the present invention is used to effectively adsorb organic pollution in Halite water system, and has efficient degradation active in the case where Weak ultraviolet is excited.
Description
Technical field
The present invention relates to photocatalytic oxidation degradation pollutant field in composite photo-catalyst preparation and brine waste system,
Specifically related to a kind of TiO handled for high slat-containing wastewater organic pollution2The composite photo-catalyst of the faint photoresponse of-carbon fiber
Preparation method.
Background technology
China's industrial economy is developed rapidly, and brings numerous increasingly serious novel environmental pollution problems, and industrial or agricultural is given up
The water pollution containing organic pollution in water by representative of waste water from dyestuff is one of problem of environmental pollution anxious to be resolved.Due to
Industrial or agricultural species is various, and the waste water component that it is produced is extremely complex, and often contains a certain amount of salinity, such as coal in waste water
Salinity in chemical industry, chlorine industry and pesticide industry etc., its waste water is all higher (mostly more than 5%).These high saliferous
Organic pollution in waste water, it tends to be difficult to effectively degraded, thus can not met using traditional microbiological treatment technology
" zero-emission " requirement of country to the industry industrial wastewater such as coal chemical industry.With TiO2Nano material is urged for the new Multi-phase light of representative
The development of change technology, is provided a kind of possible for organic pollution in efficient process brine waste.
Because without added regent, green, low energy consumption and to the non-selectivity of organic pollution, multiphase photocatalysis technology is mesh
Preceding novel environmental administers the focus of direction research.The exploitation for developing various nano-photocatalysts is then extension multiphase photocatalysis technology
The key factor of practical application.But, high slat-containing wastewater system is a specific pollutant waste water system, to be obtained in the system
Effective photodegradative photochemical catalyst can be carried out, in addition it is also necessary to solve two hang-ups.First, photocatalytic process is along with catalyst pair
The adsorption process of degradation product, has substantial amounts of inorganic zwitterion in brine waste system, and these all can be in photochemical catalyst
Surface produces competitive Adsorption with organic pollution.If catalysis material is unable to Preferential adsorption organic matter, catalyst surface active position
It will be occupied by ion, so as to cause the reduction of catalytic activity or even disappear.Therefore, how to ensure in high slat-containing wastewater system
It is the matter of utmost importance for needing to solve that organic matter is occupied an leading position in the adsorption process of catalyst surface.Second, current photocatalysis is ground
The light source studied carefully is hundreds of watts of light intensity light source mostly, and not only cost is higher for this light source, and needs cooling device, which prevent
Multiphase photocatalysis technology further applying in actual improvement field.Solve this problem, it is necessary to photochemical catalyst have it is micro-
Dim light responding ability, and can guarantee that in the case where dim light is excited excellent catalytic activity.
The content of the invention
In view of the problems of prior art, the present invention provides a kind of in Halite water system, (more than 10% is dense
Degree NaCl) in can effectively adsorb organic pollution, and excite the lower photochemical catalyst with efficient degradation activity in Weak ultraviolet
And preparation method thereof.
A kind of TiO handled for high slat-containing wastewater organic pollution2The preparation method of-carbon fiber composite photo-catalyst,
Comprise the following steps：
(1) carbon fiber is scattered in absolute ethyl alcohol, and stirred in water bath with thermostatic control until forming dispersed suspension
System；
(2) stirring simultaneously butyl titanate is added into the suspension system, after the completion of by warming-in-water to 80 DEG C with
On, deionized water is slowly added dropwise simultaneously in stirring, is added dropwise to complete rear stirring reaction 4~6 hours；
(3) it is cooled to after room temperature, washing and filtering for several times is carried out to reaction product obtained by step (2) with deionized water, by institute
Obtain after product vacuum is dried and obtain TiO2- carbon fiber nanometer composite material；
(4) by gained TiO2- carbon fiber nanometer composite material is mixed with water, is formed after uniform suspension system and moved under ultrasound
Enter in autoclave, it is closed after be heat-treated at 160 DEG C~180 DEG C；
(5) it will be separated after step (4) gained heat treatment reaction solution cooling, TiO is obtained after scrubbed and drying and processing2- carbon is fine
Tie up optic catalytic composite material.
High slat-containing wastewater system is a specific pollutant waste water system, to obtain that effective light can be carried out in the system
The photochemical catalyst of degraded, in addition it is also necessary to solve two hang-ups：First, absorption of the photocatalytic process along with catalyst to degradation product
Journey, has substantial amounts of inorganic zwitterion in brine waste system, and these all can be in photocatalyst surface and organic contamination
Thing produces competitive Adsorption.If catalysis material is unable to Preferential adsorption organic matter, catalyst surface active position will be occupied by ion,
So as to cause the reduction of catalytic activity or even disappear.Therefore, how to ensure organic matter in catalyst in high slat-containing wastewater system
It is the matter of utmost importance for needing to solve that the adsorption process on surface, which is occupied an leading position,.Second, the light source of current photocatalysis research is mostly
Hundreds of watts of light intensity light source, not only cost is higher for this light source, and needs cooling device, and which prevent multiphase photocatalysis technology
Further applying in actual improvement field.This problem is solved, it is necessary to photochemical catalyst has faint light responding ability, and
And excellent catalytic activity is can guarantee that in the case where dim light is excited.
Salinity is very high in high-salt wastewater, and salt ion quantity is a lot, there is apparent interference, high salt to photocatalytic process
Photochemical catalyst is the primary determinant for lifting light degradation activity to the absorption property of organic matter in waste water system.The system of the present invention
Preparation Method is first with the hydrolysis of butyl titanate by TiO2Closely it is combined with carbon fiber, keeps the small particle TiO of generation2's
Dispersiveness.Solvothermal process is then utilized, makes TiO2Form the same of the anatase crystallization with excellent photocatalytic activity
When, reduce the oxide group of carbon fiber surface at high temperature under high pressure using reproducibility solvent.The catalyst finally obtained is in high salt
There is very strong Preferential adsorption ability in waste water system to organic molecule, thus salt ion drops to light in Photocatalytic Degradation Process
The interference of solution preocess is just few, and the catalytic activity under dim light is excited just can be lifted greatly.So as to obtain being given up in high salt
The composite photo-catalyst of simultaneously light degradation organic matter is effectively adsorbed in aqueous systems system.
The present invention can just complete the surface reduction of carbon fiber by the improvement to method in itself, i.e. solvothermal process
Processing and TiO2Two processes of crystallization are formed, two problems of high slat-containing wastewater body processing are solved.The preparation method of the present invention
It is a kind of dipping-absorption method, under stirring, is initially formed the carbon fiber suspension containing water, then butyl titanate is added dropwise, so
The TiO in hydrolytic process afterwards2Particle formation is simultaneously combined between carbon fiber surface.
Carbon fiber has two effects in composite catalyst of the present invention：1st, absorption of the composite catalyst to organic matter is promoted,
Then TiO2Can effectively degrade these absorption organic matter；2nd, carbon fiber can suppress TiO as carrier2Nano-particle is in system
Agglomeration in standby and application process.The present invention preparation preparation method using carbon fiber as carrier, can simplicity obtain TiO2
Content is higher, dispersed preferable composite catalyst, TiO2Higher content is efficient light degradation haline water system under relatively low light intensity
One of key factor of middle pollutant.
The present invention is carrier by carbon fiber, with the TiO of generation in butyl titanate hydrolytic process2Nano-particle process shape
Into combination, effectively suppress small particle TiO2Reunion of the particle during heat treatment and light degradation, keeps its excellent photocatalysis
Activity.So as to which lower lasting efficient degradation organic pollution can be being excited in dim light.
The catalyst tolerance of salinity that the present invention is prepared is significantly improved, and one is because the present invention uses carbon fiber for vehicle group
Divide and the adsorption capacity of organic matter is seldom disturbed by salt ion；Two be because carbon fiber can also make as carrier in the present invention
Catalyst contains the TiO of more small particle high activities2Component, excites lower effective degraded to be adsorbed in catalyst surface in dim light
Organic molecule.
Preparation method is improved using carbon fiber as carrier and further in the present invention, the stability of catalyst can be made to obtain significantly
Improve, significantly improving for stability can enable catalyst salt resistant character significantly improve.
The improvement of the present invention further to technological parameter, further improves the performance of gained catalyst.
High slat-containing wastewater of the present invention refers to the organic polluting water that salinity is more than or equal to 10%, and the present invention passes through
Experimental verification, the catalyst that the present invention is prepared is up to organic pollution in 15% organic polluting water for salinity
Clearance reaches as high as more than 90%.
Carbon fiber surface is hydrophilic, directly can be obtained by commercially available.The carbon fiber specific surface area is 10m2/ g~80m2/ g,
Carbon fiber is scattered in when in absolute ethyl alcohol with the mass volume ratio 5.0g/L of carbon fiber and absolute ethyl alcohol~10.0g/L proportionings.Enter
Preferably, carbon fiber addition is 5.0g/L~8.0g/L to one step；Most preferably 6.0g/L.
Carbon fiber addition is that 5.0g/L~10.0g/L refers to concentration of the carbon fiber in whole reaction system, i.e., every liter
5.0~10.0g carbon fibers are added in ethanol solution.
Preferably, in step (2) addition of butyl titanate with the matter of the absolute ethyl alcohol with forming the suspension system
Measure volume ratio 5g~15g:200mL is counted.More preferably 10g~15g:200mL；Most preferably 14~15g:200mL.
The suspension system of gained is all transferred in step (2) in the present invention, in step (1) reacts with butyl titanate, molten
The volume of matter can be neglected, i.e., the addition of butyl titanate can also with the mass volume ratio of suspension system 5g~15g:
200mL is counted.
The composite photo-catalyst that the present invention is obtained, TiO2The active component of photochemical catalyst, be determine activity it is crucial because
Element.Ratio between butyl titanate and carbon fiber determines TiO in composite catalyst2Content, so as to finally influence photochemical catalyst
Degradation property.
Preferably, bath temperature is 30 DEG C or so (25~35 DEG C) during stirring balance.
Preferably, deionized water is added dropwise in step (2) and keeps bath temperature to be 80~100 when dripping rear stirring reaction
℃.More preferably 80~90 DEG C, most preferably 80~85 DEG C.
Preferably, the deionized water volume and the volume ratio of absolute ethyl alcohol in the suspension system of dropwise addition are in step (2)
(2~5)：10, the drop rate of deionized water is 3~5mL per minute.
In the present invention, suspension system obtained by step (1) is all transferred in step (2), therefore, the dripping quantity of deionized water
Can be using the volume ratio of ionized water and suspension system as (2~5)：10 meters；More preferably (2.5~3.5)：10.
Mixing speed is 450~550 revs/min when deionized water being added dropwise in step (2), continue after being added dropwise to complete with
250~350 revs/min are stirred reaction.
Preferably, vacuum drying is dried 20~25 hours in vacuum drying oven in step (3), vacuum drying temperature 40~60
℃。
Preferably, TiO in step (4)2With 1~3g TiO when-carbon fiber nanometer composite material and water2- carbon fiber nanometer is multiple
Condensation material is scattered in 200mL deionized waters and fallen into a trap.
Preferably, heat treatment temperature is 160 DEG C~180 DEG C, heat treatment time 10-24 hours in step (4)；Further
It is preferred that, heat treatment temperature is 165 DEG C~175 DEG C, heat treatment time 10-15 hours；Most preferably preferably, heat treatment temperature is 170
DEG C, heat treatment time 12 hours.
The present invention also provides the TiO that a kind of preparation method as described is prepared2- carbon fiber composite photo-catalyst.
The present invention also provides a kind of TiO as described2- carbon fiber composite photo-catalyst is more than or equal to 10% in processing salinity
Waste water in application.Composite photo-catalyst that will be of the invention is added into polluted-water, and controlling reaction temperature is 25~35
DEG C, the irradiation of dim light light source is opened under no light after adsorption equilibrium, is reacted 2~4 hours.
Dim light light source is preferred to use 4W ultra-violet back light lamp：Wavelength 254nm, light intensity is 12 μ W/cm2；Organic dirt in waste water
The initial concentration of thing is contaminated in more than 20mg/L；Waste water salt content 15% or so.
The catalyst of the present invention when applying required light intensity further reduce, in waste water organic concentration further improve, it is resistance to
Salinity is significantly improved.
Described salinity and salt content of the invention refer to the mass fraction of sodium chloride in waste water.
Compared with prior art, the present invention has the advantages that：
1) carbon fiber and TiO are passed through2The intermolecular forces of particle, effectively can suppress TiO in water-heat process2Between particle
Reunion, obtain the anatase TiO of small particle, high activity2Nano-particle, so as to lift catalyst in the case where Weak ultraviolet is excited
Light degradation activity.
2) using the excellent adsorption capacity in high-salt wastewater to organic pollutant molecule of carbon fiber, rutile titania is effectively facilitated
Ore deposit TiO2As active component lower high efficiency photocatalysis activity is excited in dim light.
3) preparation method is simple, it is easy to operate, and cost is low.Can be easily by changing using the preparation method of the present invention
React with heat treatment condition to regulate and control the structure and performance of composite photo-catalyst.
Brief description of the drawings
Fig. 1 a~Fig. 1 d are the TiO prepared by the embodiment of the present invention 1~42The ESEM of-carbon fiber composite photo-catalyst
(SEM) photo.
Fig. 2 a~Fig. 2 d are the TiO prepared by the embodiment of the present invention 1~42The high-resolution of-carbon fiber composite photo-catalyst is saturating
Penetrate (HRTEM) photo.
Fig. 3 is the TiO prepared by the embodiment of the present invention 1~42The x-ray fluorescence analysis of-carbon fiber composite photo-catalyst
(XPS) figure.
Fig. 4 is the TiO prepared by the embodiment of the present invention 1~42The X-ray diffraction (XRD) of-carbon fiber composite photo-catalyst
Figure.
Fig. 5 is the TiO prepared by the embodiment of the present invention 1~42- carbon fiber composite photo-catalyst and Degussa P25 type light
The clearance (reaction 3 hours) of catalyst Photodegradation of Methyl Orange in high slat-containing wastewater system.
Fig. 6 is the Adsorption of Phenol rate that the embodiment of the present invention 1~4 prepares catalyst catalyst surface in high salt
Result figure.
Fig. 7 be the catalyst for preparing of the embodiment of the present invention 1~4 with Degussa commercialization photochemical catalyst P25 in height
Light degradation process compares figure in salt waste water.
Embodiment
Be described below for the present invention more preferred embodiment, be not used to limitation of the invention.
Embodiment 1
(1) catalyst preparation
Take 1.5g that there is carbon fiber and 200mL absolute ethyl alcohols to be placed in flask, the stirring and adsorbing in 30 DEG C of water-baths.Add
In round-bottomed flask, and stirred in water bath with thermostatic control until forming dispersed suspension system ultrasonic disperse.By 5.000g metatitanic acids
Four butyl esters, are slowly dropped in carbon fiber/absolute ethyl alcohol suspension system, after completion of dropping under (300 turns/min) effects of stirring,
By warming-in-water to 80 DEG C, 60mL deionized waters are slowly added dropwise, drop rate is 3mL/min, stirred at 80 DEG C (300 turns/
Min) react 5 hours.After the completion of reaction, carry out filtering and washing and obtain powder sample, as TiO after drying2- carbon fiber is combined
Material.
By 2gTiO2- carbon fibre composite and 200mL deionized waters add to the reaction under high pressure that liner is polytetrafluoroethylene (PTFE)
It is put into air dry oven, is heat-treated 12 hours at 170 DEG C after kettle, sealing.After terminating, take out reactor and placed
Temperature fall is allowed at room temperature, is then down to after room temperature, and powder-like is obtained after removing suction filtration, redisperse, washing and drying
Product, are TiO2- carbon fiber composite photo-catalyst.
(2) light degradation process in Halite water system (15%NaCl)
Weigh the TiO obtained in 0.50g case study on implementation 12- carbon fiber composite photo-catalyst, is uniformly mixed in 800mL dense
The Halite water system (15%NaCl) for 20.0mg/L methyl oranges is spent, is placed in the reactor with magnetic agitation, water-bath is controlled
Temperature is 30 DEG C, absorption 1 hour of turning off the light.After adsorption equilibrium, (the 4W ultra-violet back light lamp under the irradiation of dim light light source：Wavelength
254nm, light intensity is 12 μ W/cm2), reaction is sampled after 3 hours, is centrifuged, is taken supernatant liquor, purple using TU-19 series
Outer visible spectrophotometer (Beijing Puxi General Instrument Co., Ltd determines wavelength 490nm), determines the extinction of methyl orange
Spend and obtain its change in concentration.
TiO prepared by the present embodiment2ESEM (SEM) photo of-carbon fiber composite photo-catalyst is as shown in Figure 1a.
TiO prepared by the present embodiment2High-resolution-ration transmission electric-lens (TEM) photo of-carbon fiber composite photo-catalyst is as schemed
Shown in 2a.
TiO prepared by the present embodiment2X-ray fluorescence analysis (XPS) figure such as Fig. 3 institutes of-carbon fiber composite photo-catalyst
Show.
TiO prepared by the present embodiment2X-ray diffraction (XRD) figure of-carbon fiber composite photo-catalyst is as shown in Figure 4.
TiO prepared by the present embodiment2- carbon fiber composite photo-catalyst light in Halite water system (15%NaCl) drops
Solve the clearance (reaction 3 hours) of methyl orange as shown in Figure 5.
In Fig. 1 a electromicroscopic photograph, bar material is carbon fiber, and the particulate matter on its surface is TiO2The pattern of particle.From figure
In it can be seen that the present embodiment prepare TiO2Particle is all relatively uniformly dispersed throughout the surface of carbon carbon fibre material.High resolution electron microscopy shines
Piece Fig. 2 a are shown, the TiO that anatase is crystallized can be obtained by hydro-thermal method2Particle, and carbon fiber is to TiO2With good protection
TiO after effect, hydro-thermal2The size of microcrystal of particle is also maintained at 20nm or so.Fig. 3 further surface of XPS collection of illustrative plates, composite
Middle TiO2The presence of particle.Fig. 4 XRD spectrum shows TiO in composite photo-catalyst2Uniform Detitanium-ore-type is also all presented in particle
Crystallization.
Clearance (the reaction of composite photo-catalyst Photodegradation of Methyl Orange in brine waste system prepared by the present embodiment
3 hours) as shown in Figure 5.As shown in Figure 5, composite catalyst manufactured in the present embodiment exists in brackish water system (15%NaCl)
Methyl orange organic pollution is efficiently removed under faint ultraviolet excitation, clearance is up to more than 80% after 3 hours, far above commercialization
P25 photochemical catalysts.
Embodiment 2
(1) catalyst preparation
Take 1.5g that there is carbon fiber and 200mL absolute ethyl alcohols to be placed in flask, the stirring and adsorbing in 30 DEG C of water-baths.Add
In round-bottomed flask, and stirred in water bath with thermostatic control until forming dispersed suspension system ultrasonic disperse.By 10.000g metatitanic acids
Four butyl esters, are slowly dropped in carbon fiber/absolute ethyl alcohol suspension system, after completion of dropping under stirring, by warming-in-water
To 80 DEG C, 60mL deionized waters are slowly added dropwise, drop rate is 3mL/min, stirring reaction 5 hours at 80 DEG C.Reaction is completed
Afterwards, carry out filtering and washing and obtain powder sample, as TiO after drying2- carbon fibre composite.
By 2g TiO2- carbon fibre composite and 200mL deionized waters add to the reaction under high pressure that liner is polytetrafluoroethylene (PTFE)
It is put into air dry oven, is heat-treated 12 hours at 170 DEG C after kettle, sealing.After terminating, take out reactor and placed
Temperature fall is allowed at room temperature, is then down to after room temperature, and powder-like is obtained after removing suction filtration, redisperse, washing and drying
Product, are TiO2- carbon fiber composite photo-catalyst.
(2) light degradation process in Halite water system (15%NaCl)
Weigh the TiO obtained in 0.50g case study on implementation 22- carbon fiber composite photo-catalyst, is uniformly mixed in 800mL dense
The Halite water system (15%NaCl) for 20.0mg/L methyl oranges is spent, is placed in the reactor with magnetic agitation, water-bath is controlled
Temperature is 30 DEG C, absorption 1 hour of turning off the light.After adsorption equilibrium, (the 4W ultra-violet back light lamp under the irradiation of dim light light source：Wavelength
254nm, light intensity is 12 μ W/cm2), reaction is sampled after 3 hours, is centrifuged, is taken supernatant liquor, purple using TU-19 series
Outer visible spectrophotometer (Beijing Puxi General Instrument Co., Ltd determines wavelength 490nm), determines the extinction of methyl orange
Spend and obtain its change in concentration.
TiO prepared by the present embodiment2ESEM (SEM) photo of-carbon fiber composite photo-catalyst is as shown in Figure 1 b.
TiO prepared by the present embodiment2High-resolution-ration transmission electric-lens (TEM) photo of-carbon fiber composite photo-catalyst is as schemed
Shown in 2b.
TiO prepared by the present embodiment2X-ray fluorescence analysis (XPS) figure such as Fig. 3 institutes of-carbon fiber composite photo-catalyst
Show.
TiO prepared by the present embodiment2X-ray diffraction (XRD) figure of-carbon fiber composite photo-catalyst is as shown in Figure 4.
TiO prepared by the present embodiment2- carbon fiber composite photo-catalyst light in Halite water system (15%NaCl) drops
Solve the clearance (reaction 3 hours) of methyl orange as shown in Figure 5.
In Fig. 1 b electromicroscopic photograph, bar material is carbon fiber, and the particulate matter on its surface is TiO2The pattern of particle.From figure
In it can be seen that the present embodiment prepare TiO2Particle is all relatively uniformly dispersed throughout the surface of carbon carbon fibre material.High resolution electron microscopy shines
Piece Fig. 2 b are shown, the TiO that anatase is crystallized can be obtained by hydro-thermal method2Particle, and carbon fiber is to TiO2With good protection
TiO after effect, hydro-thermal2The size of microcrystal of particle is also maintained at 20nm or so.Fig. 3 further surface of XPS collection of illustrative plates, composite
Middle TiO2The presence of particle.Fig. 4 XRD spectrum shows TiO in composite photo-catalyst2Uniform Detitanium-ore-type is also all presented in particle
Crystallization.
Clearance (the reaction of composite photo-catalyst Photodegradation of Methyl Orange in brine waste system prepared by the present embodiment
3 hours) as shown in Figure 5.As shown in Figure 5, composite catalyst manufactured in the present embodiment exists in brackish water system (15%NaCl)
Methyl orange organic pollution is efficiently removed under faint ultraviolet excitation, clearance is up to more than 85% after 3 hours, far above commercialization
P25 photochemical catalysts.
Embodiment 3
(1) catalyst preparation
Take 1.5g that there is carbon fiber and 200mL absolute ethyl alcohols to be placed in flask, the stirring and adsorbing in 30 DEG C of water-baths.Add
In round-bottomed flask, and stirred in water bath with thermostatic control until forming dispersed suspension system ultrasonic disperse.By 15.000g metatitanic acids
Four butyl esters, are slowly dropped in carbon fiber/absolute ethyl alcohol suspension system, after completion of dropping under stirring, by warming-in-water
To 80 DEG C, 60mL deionized waters are slowly added dropwise, drop rate is 3mL/min, stirring reaction 5 hours at 80 DEG C.Reaction is completed
Afterwards, carry out filtering and washing and obtain powder sample, as TiO after drying2- carbon fibre composite.
By 2g TiO2- carbon fibre composite and 200mL deionized waters add to the reaction under high pressure that liner is polytetrafluoroethylene (PTFE)
It is put into air dry oven, is heat-treated 12 hours at 170 DEG C after kettle, sealing.After terminating, take out reactor and placed
Temperature fall is allowed at room temperature, is then down to after room temperature, and powder-like is obtained after removing suction filtration, redisperse, washing and drying
Product, are TiO2- carbon fiber composite photo-catalyst.
(2) light degradation process in Halite water system (15%NaCl)
Weigh the TiO obtained in 0.50g case study on implementation 32- carbon fiber composite photo-catalyst, is uniformly mixed in 800mL dense
The Halite water system (15%NaCl) for 20.0mg/L methyl oranges is spent, is placed in the reactor with magnetic agitation, water-bath is controlled
Temperature is 30 DEG C, absorption 1 hour of turning off the light.After adsorption equilibrium, (the 4W ultra-violet back light lamp under the irradiation of dim light light source：Wavelength
254nm, light intensity is 12 μ W/cm2), reaction is sampled after 3 hours, is centrifuged, is taken supernatant liquor, purple using TU-19 series
Outer visible spectrophotometer (Beijing Puxi General Instrument Co., Ltd determines wavelength 490nm), determines the extinction of methyl orange
Spend and obtain its change in concentration.
TiO prepared by the present embodiment2ESEM (SEM) photo of-carbon fiber composite photo-catalyst is as illustrated in figure 1 c.
TiO prepared by the present embodiment2High-resolution-ration transmission electric-lens (TEM) photo of-carbon fiber composite photo-catalyst is as schemed
Shown in 2c.
TiO prepared by the present embodiment2X-ray fluorescence analysis (XPS) figure such as Fig. 3 institutes of-carbon fiber composite photo-catalyst
Show.
TiO prepared by the present embodiment2X-ray diffraction (XRD) figure of-carbon fiber composite photo-catalyst is as shown in Figure 4.
TiO prepared by the present embodiment2- carbon fiber composite photo-catalyst light in Halite water system (15%NaCl) drops
Solve the clearance (reaction 3 hours) of methyl orange as shown in Figure 5.
In Fig. 1 c electromicroscopic photograph, bar material is carbon fiber, and the particulate matter on its surface is TiO2The pattern of particle.From figure
In it can be seen that the present embodiment prepare TiO2Particle is all relatively uniformly dispersed throughout the surface of carbon carbon fibre material.High resolution electron microscopy shines
Piece Fig. 2 c are shown, the TiO that anatase is crystallized can be obtained by hydro-thermal method2Particle, and carbon fiber is to TiO2With good protection
TiO after effect, hydro-thermal2The size of microcrystal of particle is also maintained at 20nm or so.Fig. 3 further surface of XPS collection of illustrative plates, composite
Middle TiO2The presence of particle.Fig. 4 XRD spectrum shows TiO in composite photo-catalyst2Uniform Detitanium-ore-type is also all presented in particle
Crystallization.
Clearance (the reaction of composite photo-catalyst Photodegradation of Methyl Orange in brine waste system prepared by the present embodiment
3 hours) as shown in Figure 5.As shown in Figure 5, composite catalyst manufactured in the present embodiment exists in brackish water system (15%NaCl)
Methyl orange organic pollution is efficiently removed under faint ultraviolet excitation, clearance is up to more than 90% after 3 hours, far above commercialization
P25 photochemical catalysts.
Embodiment 4
(1) catalyst preparation
Take 1.5g that there is carbon fiber and 200mL absolute ethyl alcohols to be placed in flask, the stirring and adsorbing in 30 DEG C of water-baths.Add
In round-bottomed flask, and stirred in water bath with thermostatic control until forming dispersed suspension system ultrasonic disperse.By 15.000g metatitanic acids
Four butyl esters, are slowly dropped in carbon fiber/absolute ethyl alcohol suspension system, after completion of dropping under stirring, by warming-in-water
To 80 DEG C, 60mL deionized waters are slowly added dropwise, drop rate is 3mL/min, stirring reaction 5 hours at 80 DEG C.Reaction is completed
Afterwards, carry out filtering and washing and obtain powder sample, as TiO after drying2- carbon fibre composite.
By 2g TiO2- carbon fibre composite and 200mL deionized waters add to the reaction under high pressure that liner is polytetrafluoroethylene (PTFE)
It is put into air dry oven, is heat-treated 12 hours at 170 DEG C after kettle, sealing.After terminating, take out reactor and placed
Temperature fall is allowed at room temperature, is then down to after room temperature, and powder-like is obtained after removing suction filtration, redisperse, washing and drying
Product, are TiO2- carbon fiber composite photo-catalyst.
(2) light degradation process in Halite water system (15%NaCl)
Weigh the TiO obtained in 0.50g case study on implementation 32- carbon fiber composite photo-catalyst, is uniformly mixed in 800mL dense
The Halite water system (15%NaCl) for 20.0mg/L methyl oranges is spent, is placed in the reactor with magnetic agitation, water-bath is controlled
Temperature is 30 DEG C, absorption 1 hour of turning off the light.After adsorption equilibrium, (the 4W ultra-violet back light lamp under the irradiation of dim light light source：Wavelength
254nm, light intensity is 12 μ W/cm2), reaction is sampled after 3 hours, is centrifuged, is taken supernatant liquor, purple using TU-19 series
Outer visible spectrophotometer (Beijing Puxi General Instrument Co., Ltd determines wavelength 490nm), determines the extinction of methyl orange
Spend and obtain its change in concentration.
TiO prepared by the present embodiment2ESEM (SEM) photo of-carbon fiber composite photo-catalyst is as shown in Figure 1 d.
TiO prepared by the present embodiment2High-resolution-ration transmission electric-lens (HRTEM) photo of-carbon fiber composite photo-catalyst is such as
Shown in Fig. 2 d.
TiO prepared by the present embodiment2X-ray fluorescence analysis (XPS) figure such as Fig. 3 institutes of-carbon fiber composite photo-catalyst
Show.
TiO prepared by the present embodiment2X-ray diffraction (XRD) figure of-carbon fiber composite photo-catalyst is as shown in Figure 4.
TiO prepared by the present embodiment2- carbon fiber composite photo-catalyst light in Halite water system (15%NaCl) drops
Solve the clearance (reaction 3 hours) of methyl orange as shown in Figure 5.
In Fig. 1 d electromicroscopic photograph, bar material is carbon fiber, and the particulate matter on its surface is TiO2The pattern of particle.From figure
In it can be seen that the present embodiment prepare TiO2Particle is all relatively uniformly dispersed throughout the surface of carbon carbon fibre material.High resolution electron microscopy shines
Piece Fig. 2 d are shown, the TiO that anatase is crystallized can be obtained by hydro-thermal method2Particle, and carbon fiber is to TiO2With good protection
TiO after effect, hydro-thermal2The size of microcrystal of particle is also maintained at 20nm or so.Fig. 3 further surface of XPS collection of illustrative plates, composite
Middle TiO2The presence of particle.Fig. 4 XRD spectrum shows TiO in composite photo-catalyst2Uniform Detitanium-ore-type is also all presented in particle
Crystallization.
Clearance (the reaction of composite photo-catalyst Photodegradation of Methyl Orange in brine waste system prepared by the present embodiment
3 hours) as shown in Figure 5.As shown in Figure 5, composite catalyst manufactured in the present embodiment exists in brackish water system (15%NaCl)
Methyl orange organic pollution is efficiently removed under faint ultraviolet excitation, clearance is up to more than 90% after 3 hours, far above commercialization
P25 photochemical catalysts.
Fig. 6 is the Adsorption of Phenol rate result that above example prepares catalyst catalyst surface in high salt
Figure, it can be seen that untreated composite catalyst surface is due to containing many hydrophilic radicals, causing the suction of its Pyrogentisinic Acid
Attached rate is relatively low.And after by solvothermal, the hydrophilic radical of catalyst surface is largely reduced, pair of composite catalyst
The absorption of phenol is obviously improved, so as to ensure that the light degradation activity of subsequent catalyst.
Fig. 7 be the catalyst for preparing of above example with Degussa commercialization photochemical catalyst P25 in high-salt wastewater
Middle light degradation process compares figure, and as can be seen from the figure the degradation efficiency for each catalyst that patent of the present invention is obtained is substantially better than
Commercial P25 catalyst.The 3h clearances of P25 catalyst are only 13% or so.P25 is purchased from German match company of Germany, its TiO2Have
Anatase and rutile-type composition (1:4 ratio), the particle diameter of particle is 25nm, and the specific surface area of catalyst is 50m2·g-1。
The specific implementation case of patent of the present invention is the foregoing is only, but the technical characteristic of patent of the present invention is not limited to
This, any those skilled in the relevant art are in the field of the invention, and the change or modification made all are covered in the special of the present invention
Among sharp scope.
Claims (9)
1. a kind of TiO handled for high slat-containing wastewater organic pollution2The preparation method of-carbon fiber composite photo-catalyst, it is special
Levy and be, comprise the following steps：
(1) carbon fiber is scattered in absolute ethyl alcohol, and stirred in water bath with thermostatic control until forming dispersed suspension system；
(2) stirring simultaneously adds butyl titanate into the suspension system, stirs warming-in-water to more than 80 DEG C after adding
Mix while deionized water is slowly added dropwise, continue stirring reaction after being added dropwise to complete 4~6 hours；
(3) it is cooled to after room temperature, washing and filtering for several times is carried out to reaction product obtained by step (2) with deionized water, gained is produced
TiO is obtained after thing vacuum drying2- carbon fiber nanometer composite material；
(4) by gained TiO2- carbon fiber nanometer composite material is mixed with water, is formed under ultrasound and height is moved into after uniform suspension system
Press in kettle, it is closed to be heat-treated afterwards；
(5) it will be separated after step (4) gained heat treatment reaction solution cooling, TiO is obtained after scrubbed and drying and processing2- carbon fiber light is urged
Change composite.
2. preparation method according to claim 1, it is characterised in that carbon fiber specific surface area described in step (1) is 10m2/g
~80m2/ g, carbon fiber is scattered in when in absolute ethyl alcohol with mass volume ratio 5.0g/L~10.0g/ of carbon fiber and absolute ethyl alcohol
L is matched.
3. preparation method according to claim 1, it is characterised in that in step (2) addition of butyl titanate with shape
Into mass volume ratio 5g~15g of the absolute ethyl alcohol of the suspension system：200mL is counted.
4. preparation method according to claim 1, it is characterised in that deionized water is added dropwise in step (2) and is stirred after dripping
It is 80~100 DEG C that bath temperature is kept when mixing reaction.
5. preparation method according to claim 1, it is characterised in that the deionized water volume being added dropwise in step (2) with it is described
The volume ratio of absolute ethyl alcohol is (2~5) in suspension system：10, the drop rate of deionized water is 3~5mL per minute.
6. preparation method according to claim 1, it is characterised in that TiO in step (4)2- carbon fiber nanometer composite material with
With 1~3g TiO during water mixing2- carbon fiber nanometer composite material is scattered in 200mL deionized waters and fallen into a trap.
7. preparation method according to claim 1, it is characterised in that heat treatment temperature is 160 DEG C~175 DEG C in step (4),
Heat treatment time is 10-24 hours.
8. the TiO that a kind of preparation method as described in claim 1~7 any claim is prepared2- carbon fiber complex light is urged
Agent.
9. a kind of TiO as claimed in claim 82- carbon fiber composite photo-catalyst is more than in 10% waste water in processing salinity
Using.
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| CN109847734A (en) * | 2018-11-30 | 2019-06-07 | 黄山学院 | A kind of preparation method of carbon fiber loaded titania nanotube composite material |
| CN112206757A (en) * | 2020-10-13 | 2021-01-12 | 武汉理工大学 | High-activity hydroxyl-rich suspensible TiO2Simple preparation method of nanocrystalline photocatalytic material |
| CN113828293A (en) * | 2021-10-22 | 2021-12-24 | 四川轻化工大学 | Improve TiO2Method for surface photovoltage |
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| CN105540733A (en) * | 2016-01-26 | 2016-05-04 | 浙江工商大学 | TiO2-reduced graphene composite and preparation method thereof and application of TiO2-reduced graphene composite to artificial sea water system |
| CN105618050A (en) * | 2016-01-26 | 2016-06-01 | 杭州久和环保科技有限公司 | Visible-light responded compound catalyst for degrading organic pollutants in salt-containing wastewater and preparation method of visible-light responded compound catalyst |
| CN105749762A (en) * | 2016-01-26 | 2016-07-13 | 浙江工商大学 | Macromolecular composite membrane material with photocatalysis activity and preparation method thereof |
| CN106040213A (en) * | 2016-05-26 | 2016-10-26 | 河海大学 | TiO2/CNCs composite photocatalyst and preparation method and application thereof |
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| CN105540733A (en) * | 2016-01-26 | 2016-05-04 | 浙江工商大学 | TiO2-reduced graphene composite and preparation method thereof and application of TiO2-reduced graphene composite to artificial sea water system |
| CN105618050A (en) * | 2016-01-26 | 2016-06-01 | 杭州久和环保科技有限公司 | Visible-light responded compound catalyst for degrading organic pollutants in salt-containing wastewater and preparation method of visible-light responded compound catalyst |
| CN105749762A (en) * | 2016-01-26 | 2016-07-13 | 浙江工商大学 | Macromolecular composite membrane material with photocatalysis activity and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109847734A (en) * | 2018-11-30 | 2019-06-07 | 黄山学院 | A kind of preparation method of carbon fiber loaded titania nanotube composite material |
| CN109847734B (en) * | 2018-11-30 | 2021-10-29 | 黄山学院 | Preparation method of carbon fiber loaded titanium dioxide nanotube composite material |
| CN112206757A (en) * | 2020-10-13 | 2021-01-12 | 武汉理工大学 | High-activity hydroxyl-rich suspensible TiO2Simple preparation method of nanocrystalline photocatalytic material |
| CN112206757B (en) * | 2020-10-13 | 2023-08-29 | 武汉理工大学 | High-activity hydroxyl-rich suspendable TiO (titanium dioxide) 2 Simple preparation method of nanocrystalline photocatalytic material |
| CN113828293A (en) * | 2021-10-22 | 2021-12-24 | 四川轻化工大学 | Improve TiO2Method for surface photovoltage |
| CN113828293B (en) * | 2021-10-22 | 2023-05-05 | 四川轻化工大学 | TiO (titanium dioxide) improving agent 2 Method for surface photovoltage |
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