CN106698585B - Utilize the method for graphene modified nano-titanium dioxide photocatalyst web regulation creek black and odorous water - Google Patents
Utilize the method for graphene modified nano-titanium dioxide photocatalyst web regulation creek black and odorous water Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 115
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 79
- -1 graphene modified nano-titanium dioxide Chemical class 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 55
- 230000033228 biological regulation Effects 0.000 title claims abstract description 6
- 239000000835 fiber Substances 0.000 claims abstract description 68
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 62
- 238000001035 drying Methods 0.000 claims abstract description 55
- 239000004411 aluminium Substances 0.000 claims abstract description 49
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 49
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002131 composite material Substances 0.000 claims abstract description 45
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 43
- 239000008240 homogeneous mixture Substances 0.000 claims abstract description 32
- 239000007888 film coating Substances 0.000 claims abstract description 30
- 238000009501 film coating Methods 0.000 claims abstract description 30
- 238000005286 illumination Methods 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 65
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 61
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
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- 239000011259 mixed solution Substances 0.000 claims description 14
- 230000008859 change Effects 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
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- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
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- 238000010792 warming Methods 0.000 claims description 9
- 230000004044 response Effects 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 230000003287 optical effect Effects 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 230000036961 partial effect Effects 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 238000007146 photocatalysis Methods 0.000 claims description 6
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- 239000004698 Polyethylene Substances 0.000 claims description 3
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 239000001301 oxygen Substances 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 12
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 5
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- 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 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
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- 241000196324 Embryophyta Species 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
-
- 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
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/02—Odour removal or prevention of malodour
-
- 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
- C02F2305/08—Nanoparticles or nanotubes
-
- 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
Abstract
Using the method for graphene modified nano-titanium dioxide photocatalyst web regulation creek black and odorous water, include the following steps: that (1) prepares redox graphene modified nano-titanium dioxide heterojunction structure composite photo-catalyst；(2) water-fast, impact resistance aluminium base crosslinking agent is manufactured, homogeneous mixture is formed with catalyst, is added in the fibre stuff of production hdpe fiber net, or and be fabricated to the hdpe fiber net with nano-photocatalytic film coating；(3) after spontaneously drying in air, then it is placed in constant temperature drying in drying chamber；(4) graphene modified nano-titanium dioxide photocatalyst web is arranged onto creek, is allowed to contact with the water surface, while receiving illumination, creek black and odorous water is renovated.The present invention is not necessarily to aeration oxygen replenishing, energy conservation and environmental protection, and cost is lower, and technique is simpler.
Description
Technical field
The present invention relates to water-treatment technology fields, and in particular to utilizes graphene modified nano-titanium dioxide photocatalyst fiber
The method of net regulation creek black and odorous water.
Background technique
It is black it is smelly be water body organic contamination a kind of extreme phenomenon, be due to water hypoxia, organic matter corruption and caused by.Water
The black smelly immediate cause of body is caused by dissolving hypoxgia as DO, and the discharge of pollutant is to cause the root of black and odorous water.
The black smelly phenomenon in river is a kind of Biochemical Phenomena in fact, the anaerobic decomposition of organic substance in water body.Think organic in water body
Substance oxygen consumption in decomposable process is greater than reoxygenation, causes anaerobic environment, and anaerobe decomposing organic matter generates a large amount of stink
The gas evolution water surface enters atmosphere, causes black and odorous water.
Particularly, black and odorous water mainly has the reason of the following aspects:
(1) water body organic contamination
Urban river not only supplies water, while also having become the primary discharge place of urban industry waste water, resident living sewage.
With a large amount of discharges of industrial wastewater and sanitary sewage, organic carbon pollutant (COD, BOD), organic based nitrogen contaminant in river
(NH3-N) and phosphorus-containing compound load continues to increase.Organic pollutant oxygen consumption in decomposable process is greater than reoxygenation, causes water body
Anoxic, anaerobe mass propagation and decomposing organic matter, which generate, largely odour such as methane (CH4), hydrogen sulfide (H2S), ammonia
(NH3) etc. the evolution water surface, which enters atmosphere, keeps water body smelly.Organic matter is primarily referred to as carbohydrate, protein, grease, amino acid, esters
Deng.
These substances are present in stain disease with suspended state or solubilised state.It can be decomposed under microbial action after being discharged into water body
At the simple inorganic matter such as CO2 and water, while consuming a large amount of oxygen.In addition to this, when in water body by organic carbon and organic nitrogen with
And when organic phosphorus contaminants, no matter wherein whether have sufficient DO, it all will be by aerobic actinomyces under suitable water temperature
Or the degradation of anaerobe, variety classes malodoring substance is given off, different degrees of black smelly of water body is caused.
The basic reason for causing black and odorous water is that organic contamination is got worse, and the gap of water body dilution self-cleansing ability is increasingly
Greatly.
(2) ammonia nitrogen, total phosphorus pollution
Various organic reducing nitrogen phosphorus substances slow aerobic degradation in water body in sanitary sewage leads to water body DO reduction.
The oxygen consumption of itrogenous organic substance degradation is much larger than the oxygen consumption of carbon organic matter degradation, and nitrogen phosphorus substance is joined together with general carbohydrate
With oxygen process, DO in water body is reduced, water quality deterioration is caused, is blacked smelly.
It is dirty that this water quality is dissected from pollutant oxygen consumption, contaminant degradation ability, water body oxygen balance and hydrologic condition etc.
The reason of dye, and then propose to solve the effective way of section water pollution control.Section DO is low, and local water body blacks smelly main
The reason is that NH3-N is too many in water body, caused by a large amount of DO consumed in water.
(3) settling flux of bed mud and substrate
The characteristics of city rivers pollution is exactly that be not only its water quality heavily contaminated, and the pollution of its bed mud is also very tight
Weight.A large amount of pollutants in water body are precipitated and are accumulated in bed mud in river, and in some sense, bed mud is to be discharged into various dirts in river
One of Master Home of dye.A large amount of seriously polluted bed mud is adsorbed on bottom under a series of effects such as physics, chemistry and biology
Pollutant on mud particle is exchanged with pore water, to discharge pollutant into water, is caused secondary pollution of water, is led to river
Road water body is throughout the year black smelly；A large amount of bed mud also provides the breeding ground of breeding for microorganism, in these microorganisms, actinomyces and indigo plant
Algae contributes black and odorous water maximum.It is deposited on the sludge of riverbed bottom, due to the washing away of water flow, artificial disturbance, heavy construction
Construction and biological activity be responsible for sediments re-suspension.Sediment particles being suspended in water flow itself also play cause to water body
Black effect, main blackening ingredient be the ferrous sulfide being easily oxidized and vulcanization Asia manganese in suspended particulate substance, i.e., has color in itself
Then participation blackening.
Difference disturbs in the smelly influence research black to creek of lower sediments re-suspension, obtains as the increase of disturbance velocity can be with
Aggravate the black smelly degree of water quality of river.
(4) heat pollution of water
The thermal pollution of urban river refers to hot waste water of the river two sides factory to discharge into water, such as the cooling water in power station,
It can not only threaten the breeding and existence of aquatile in river, while it rises the water temperature in locally even entire river,
And water temperature is a key factor for promoting water body smelly.
Water temperature lower than 8 DEG C and be higher than 35 DEG C when, river do not generate generally it is black smelly, because of the unwrapping wire in this temperature section
Bacterium decomposing organic pollutant generates the activity that Qiaosi is narrowed and is suppressed.And at 25 DEG C, the breeding of actinomyces reaches highest, river
Black smelly also reach maximum.Therefore work as river by organic pollution and in the case that water temperature is suitable for, the strong activity of microorganism
The organic substance in water body can be made largely to decompose, generate various malodoring substances, in various degree black smelly occur so as to cause river.
(5) other factors
Such as heavy metal pollution: heavy metal pollution is also one kind of city rivers pollution type, smelly contribution master black to river
It is the concentration of iron in water body, manganese, and the iron, manganese in suspended material are important one of blackening factor.
Such as shipping: one of major function of urban river is exactly shipping.Pollution From Ships are a kind of comprehensive pollutions, but total
Discharge that is main and transporting the property of cargo, the sanitary sewage on ship, rubbish, excrement and waste oil is related for body.And shipping
Black smelly also one big contribution is generated to river, is exactly that it will lead to river deposit generation settling flux.
In addition, life, the random stacking of industrial refuse, urban storm runoff, tributary sluices or the sewage etc. of upstream is to river
The black of stream smelly all has different degrees of contribution.
It solves the problems, such as that creek water body DO dissolves hypoxgia at present, mainly there is following technical method:
One, direct oxygen increasing pump aeration oxygen replenishing, disadvantage need to expend a large amount of energy, and in aeration early period, have a large amount of
Foul smell come out, influence nearby residents normal life, citizen's opinion is big.Need daily 24 hours lasting aerations, the electricity charge at
This height.
Two, upstream moisturizing is increased, the disadvantage is that creek one is ebbed tide, the water of benefit flows away again.
Three, it excavates and walks creek bottom mud clearly, after the heavy rain that rains heavily, and wash away with rain dirt into creek.
Four, water weeds are planted in creek, influences the original function of creek, mosquito easy to breed, and plant itself is dead
After rot to form secondary pollution.
Five, it is black smelly can to reduce creek for microbial technique, but continues not for a long time.
Therefore, a kind of method for needing to study new regulation creek black and odorous water.
Summary of the invention
For the defects in the prior art, graphene modified nano-titanium dioxide photocatalyst is utilized the present invention provides a kind of
The method of web regulation creek black and odorous water.
The method for renovating creek black and odorous water using graphene modified nano-titanium dioxide photocatalyst web, including it is as follows
Step:
(1) by hydro-thermal-heat treatment-hydro-thermal method, redox graphene modified nano-titanium dioxide hetero-junctions is constructed
Structure composite photo-catalyst, using amorphous carbon as the nanocrystalline heterostructure interface between graphene two-dimensional surface of TiO2,
The composite effect for improving TiO2 and graphene improves its visible light catalysis activity；
(3) water-fast, impact resistance aluminium base crosslinking agent, and the redox graphene modified Nano that step (1) is obtained are manufactured
Titanium dioxide heterogeneous structure composite photochemical catalyst and the aluminium base crosslinking agent are prepared into homogeneous mixture, and homogeneous mixture is added
Into the fibre stuff of production hdpe fiber net, or to be attached to hdpe fiber together online, is fabricated to
Hdpe fiber net with nano-photocatalytic film coating；
(3) the hdpe fiber net for the nano-photocatalytic film coating for obtaining step (2) is natural in air
After drying, then it is placed in drying in drying chamber, obtains graphene modified nano-titanium dioxide photocatalyst web；
(4) it in the graphene modified nano-titanium dioxide photocatalyst web setting to creek obtained step (3), is allowed to
It is contacted with the water surface, while receiving illumination, creek black and odorous water is renovated.
As a kind of perferred technical scheme, step (1) detailed process are as follows:
Using crystalline flake graphite as raw material, with dense H2SO4And KMnO4Graphite oxide is first made by two-step method for oxidant, then
Graphene oxide is made by ultrasonic disperse；
By solvent-thermal method at 180 DEG C, with graphene oxide and Ti (OBu)4As initial reactant, in alcohol solvent
In, synthesize redox graphene modified nano-titanium dioxide heterojunction structure composite photo-catalyst.
As a kind of perferred technical scheme, the detailed process in step (2) are as follows:
Aluminic acid butyl ester first is diluted with dehydrated alcohol, adds the mixed solution of glacial acetic acid, dehydrated alcohol, water, mixed solution
The volume ratio of middle water and dehydrated alcohol is 1:10, is entered in mixer, and starting stirring is warming up to 70 DEG C -80 DEG C, stirs 10-30
Minute, the light yellow sol of stable and uniform clear is obtained, nano aluminium oxide suspension is then slowly added to, maintains the temperature at 40
DEG C, obtain water-fast, impact resistance aluminium base crosslinking agent；
Take aluminium base crosslinking agent, aluminium base crosslinking agent be warming up to 50 DEG C, after be slowly added to redox graphene modified Nano
Titanium dioxide heterogeneous structure composite photochemical catalyst suspension, aluminium base crosslinking agent is the 0.1-2wt% of total weight of the mixture, after adding
Continue stirring 15-20 minutes, obtains homogeneous mixture；
Then homogeneous mixture is added in the fibre stuff of production hdpe fiber net, or be attached to highly dense
It is online to spend polyethylene fibre, is fabricated to the hdpe fiber net with nano-photocatalytic film coating.
As a kind of perferred technical scheme, in step (2), the technical requirements of the homogeneous mixture are as follows: shape, liquid
State 2-5%；Crystal form, anatase titanium dioxide；Content, 97.5%；Partial size ,≤10nm；Surface group, carboxyl, carbonate；Optical response range,
300nm-550nm；Surface characteristic, it is hydrophilic；PH (1% aqueous solution), 3-4；Specific surface area, 400m2/g。
As a kind of perferred technical scheme, in step (2), the nano-photocatalytic film coating with a thickness of 0.5um-
50um。
As a kind of perferred technical scheme, in step (2), the size of hdpe fiber net be can according to need
It is selected, but best width is 1 meter, 1.5 meters or 2 meters.Hdpe fiber net under the width is convenient for subsequent
Working process and installation, while light-catalysed efficiency is also obtained into maximum promotion.
As a kind of perferred technical scheme, in step (2), the homogeneous for being obtained step (1) by the way of spraying is mixed
Close the surface that object is attached to hdpe fiber net.
As a kind of perferred technical scheme, when spraying, using high-pressure spray gun, and using the side of repeatedly a small amount of even application
Formula.Herein, repeatedly refer at least three times, and refer to each quantity for spray on a small quantity and be no more than the one third of spray paint total amount.
As a kind of perferred technical scheme, in step (2), hdpe fiber net is directly mixed equipped with homogeneous
Close extracted many times in the bucket of object.
As a kind of perferred technical scheme, in step (2), hdpe fiber net is directly mixed equipped with homogeneous
It closes and is extracted 3-7 times in the bucket of object.
As a kind of perferred technical scheme, in step (3), when drying in drying chamber, drying temperature uses 55-65 DEG C,
Drying time uses 25-35 hours.
As a kind of perferred technical scheme, in step (3), when drying in drying chamber, drying temperature uses 60 DEG C of constant temperature,
Drying time uses 30 hours.
The present invention is prepared for Ti0 using hydro-thermal method2It is nanocrystalline, by be heat-treated have adjusted sample surfaces carbon film thickness and
Interface disorder degree.Then by carbon-coated Ti02It is compound with graphene progress, obtain a series of heterojunction structure composite samples.
TiO2The amorphous carbon on surface can be used as excellent heterojunction structure compound interface in the state of certain thickness and the degree of disorder, rise
The bridge joint TiO arrived2With graphene and the effect for inhibiting photo-generated carrier compound.The result that inventor tests in photocatalytic activity
It has been shown that, redox graphene modified nano-titanium dioxide heterojunction structure composite photo-catalyst can get lower thickness and lower table
The carbon film of the face degree of disorder is conducive to the photocatalytic activity for promoting heterojunction structure compound.After the processing of 4h visible light exposure, to first
The degradation rate of base orange is 5.2 times of titanium dioxide, and 1.9 times of P25 and graphene complex.In addition, in oxygen reduction fossil
In black alkene modified nano-titanium dioxide heterojunction structure composite photo-catalyst, TiO2 can be adequately bonded with graphene, therefore
The dispersibility of TiO2 improves, and the efficiency of transmission of photo-generated carrier is also improved, and more light induced electrons can pass through height
Effect interface is transported from Ti02 to graphene, inhibits the compound of photo-generated carrier, and it is living to result in higher photocatalysis
Property.
As shown from the above technical solution, the invention has the following advantages:
The present invention is graphene modified nano-titanium dioxide photocatalyst solution, and utilization is water-fast, impact resistance aluminium base crosslinking agent system
At nano-photocatalytic film coating, every square meter is sprayed or is impregnated by a certain percentage, and membrane is online to hdpe fiber,
Produce a kind of novel graphene modified nano-titanium dioxide photocatalyst web.By graphene modified nano-titanium dioxide light
Catalyst web is directly installed at creek, can be carried out photocatalysis treatment to the black and odorous water in creek, be exposed without oxygen increasing pump
Gas oxygenation reduces the waste of the energy, will not influence resident's normal life, at the moisturizing and dredging for carrying out upstream
Reason, the time of continuous action is longer, will not cause secondary pollution to creek.
Although traditional titanium dioxide can effectively absorb ultraviolet light, photo-catalysis capability is not had, essential reason is it
The photo-generated carrier service life is short, and combined efficiency is high, can not oxygen molecule to surrounding and hydrone provides light induced electron and photoproduction is empty
Cave can not be generated for redox reactive hydroxyl radical.There is also similarly ask in nano-titania photocatalyst
Topic, heterogeneous structural nano photocatalyst of titanium dioxide improves this problem to a certain extent, but the reason of water process is often not achieved
It wants to claim.Graphene is a kind of typical two-dimensional layer high conductive material, and there is very excellent load capacity and charge to transmit
Ability.The present invention just utilizes graphene modified nano-titanium dioxide, and heterocrystal synthesis three dimensional pattern is changed into multi-layer nano
Membrane structure two-dimensional model is utilized high-quality graphene as crucial photo-generated carrier conducting shell, photocatalysis efficiency is promoted
Several geometry magnitudes, not only can also decompose water oxygen with decomposing organic matter, have visible light-responded.Graphene is one
The typical two-dimensional layer high conductive material of kind, has very excellent load capacity and charge transport ability.Graphene is used for
Photocatalyst catalytic capability is increased to a new height, effectively reduced by modified nano-titanium dioxide heterojunction structure photocatalyst
The recombination rate of photo-generated carrier, nano coating can large-scale application in current water process environment.The present invention is using real
Natural two-dimensional material, structure " zero-fault ", is different from the graphene of oxidation, reduction, can guarantee efficient photo-generated carrier
Transfer, is not affected by contaminants, and can carry out in-situ treatment to black smelly water.Creek oxygen in water DO can be increased.Photocatalyst is to receive
Meter level titanium dioxide, as long as there is visible light to decompose the noxious material in water, decomposes water system by photocatalysis principle technology
Oxygen, allows water body to restore self-purification capacity again, and black smelly water becomes clear water.
The present invention is not necessarily to aeration oxygen replenishing, energy conservation and environmental protection, and production cost is lower, and production technology is simpler, is easy to large quantities of
Amount production.
The present invention is directly spread out, can be determined size according to the developed width or situation of creek, can be bundled in city
The stern that pipe ring is defended can also fix bank, using simple, operate easy.
Detailed description of the invention
Fig. 1 is the reaction principle for synthesizing redox graphene modified nano-titanium dioxide heterojunction structure composite photo-catalyst
Schematic diagram；
Fig. 2 is the XRD diagram of the composite photo-catalyst under the differential responses time；
Fig. 3 is the XRD diagram of the composite photo-catalyst under redox graphene Different adding amount；
Fig. 4 is that the SEM of composite photo-catalyst schemes；
Fig. 5 is that the TEM of composite photo-catalyst schemes；
Fig. 6 is that the HRTEM of composite photo-catalyst schemes；
Fig. 7 is that the FET of composite photo-catalyst schemes；
Fig. 8 is influence knot of the extracting times to the hdpe fiber net catalytic performance of nano-photocatalytic film coating
Fruit figure；
Fig. 9 is the influence result figure of nano-photocatalytic film coating and powdered titanium dioxide to catalytic performance；
Figure 10 is the hdpe fiber net use repeatly effect picture of nano-photocatalytic film coating.
Specific embodiment
It is described in detail below in conjunction with embodiment of the specific embodiment to technical solution of the present invention.Following embodiment
It is only used for clearly illustrating technical solution of the present invention, therefore is only used as example, and it is of the invention to cannot be used as a limitation limitation
Protection scope.
Embodiment one
The method for renovating creek black and odorous water using graphene modified nano-titanium dioxide photocatalyst web, including it is as follows
Step:
(1) using crystalline flake graphite as raw material, with dense H2SO4And KMnO4Oxidation stone is first made by two-step method for oxidant
Ink, then graphene oxide is made by ultrasonic disperse；By solvent-thermal method at 180 DEG C, with 30mg graphene oxide and 3mL
Ti(OBu)4As initial reactant, in alcohol solvent, reacts 6 hours, synthesize redox graphene modified nano-silica
Change titanium heterojunction structure composite photo-catalyst, reaction principle constructs as shown in Figure 1, to by hydro-thermal-heat treatment-hydro-thermal method
Redox graphene modified nano-titanium dioxide heterojunction structure composite photo-catalyst, it is nanocrystalline using amorphous carbon as TiO2
With the heterostructure interface between graphene two-dimensional surface, the composite effect of TiO2 and graphene is improved, it is visible to improve its
Photocatalytic activity；
(2) water-fast, impact resistance aluminium base crosslinking agent is manufactured, first aluminic acid butyl ester is diluted with dehydrated alcohol, adds glacial acetic acid, nothing
The mixed solution of water-ethanol, water, the volume ratio of water and dehydrated alcohol is 1:10 in mixed solution, is entered in mixer, starting is stirred
It mixes, is warming up to 70 DEG C, stir 10 minutes, obtain the light yellow sol of stable and uniform clear, be then slowly added to nano oxidized
Aluminium suspension maintains the temperature at 40 DEG C, obtains water-fast, impact resistance aluminium base crosslinking agent；Aluminium base crosslinking agent is taken, by aluminium base crosslinking agent liter
Temperature to 50 DEG C, after be slowly added to redox graphene modified nano-titanium dioxide heterojunction structure composite photo-catalyst suspension,
Aluminium base crosslinking agent is the 0.1wt% of total weight of the mixture, continues stirring 15 minutes after adding, obtains homogeneous mixture；And it will step
Suddenly the redox graphene modified nano-titanium dioxide heterojunction structure composite photo-catalyst and the aluminium base crosslinking agent that (1) obtains
Homogeneous mixture is added in the fibre stuff of production hdpe fiber net, finally by the homogeneous mixture being prepared into
Hdpe fiber net is prepared, wherein the size of hdpe fiber net, which can according to need, is selected, this
Select width for 1 meter in embodiment.Hdpe fiber net under the width is convenient for subsequent working process and installation,
Light-catalysed efficiency is also obtained into maximum promotion simultaneously；
The technical requirements of the homogeneous mixture are as follows:
| Character | Liquid 2-5% |
| Crystal form | Anatase titanium dioxide |
| Content | 97.5% |
| Partial size | ≤10nm |
| Surface group | Carboxyl, carbonate |
| Optical response range | 300nm-550nm |
| Surface characteristic | It is hydrophilic |
| PH (1% aqueous solution) | 3-4 |
| Specific surface area | 400m2/g |
(3) the hdpe fiber net for the nano-photocatalytic film coating for obtaining step (2) is natural in air
After drying, then it is placed in drying in drying chamber, when drying in drying chamber, drying temperature uses 55 DEG C of constant temperature, and drying time is small using 25
When, obtain graphene modified nano-titanium dioxide photocatalyst web；
(4) it in the graphene modified nano-titanium dioxide photocatalyst web setting to creek obtained step (3), is allowed to
It is contacted with the water surface, while receiving illumination, creek black and odorous water is renovated, the present embodiment is used to handle petroleum work in practice
Industry waste water.Oil industry wastewater mainly include generated in oil exploitation and refining process it is useless containing various inorganic salts and organic matter
Water, ingredient is extremely complex, and processing difficulty is big.Graphene modified nano-titanium dioxide photocatalyst web can be by crude oil waste water
It is separated into the water phase and oil-free salt water phase of rich oil, then rich oil is added in fresh water supply and enters back into washing oil process,
Crude oil had not only been recycled in this way but also had been saved uses water.And it is fine using the graphene modified nano-titanium dioxide photocatalyst of the present embodiment
The removal efficiency of net not only phenol is tieed up up to 95% or more, and at low pressures can efficiently by waste water cadmium, nickel, mercury,
The removing of the heavy metals high valence ion such as titanium, expense are more much lower than the methods of reverse osmosis.
Embodiment two
The method for renovating creek black and odorous water using graphene modified nano-titanium dioxide photocatalyst web, including it is as follows
Step:
(1) using crystalline flake graphite as raw material, with dense H2SO4And KMnO4Oxidation stone is first made by two-step method for oxidant
Ink, then graphene oxide is made by ultrasonic disperse；By solvent-thermal method at 180 DEG C, with 30mg graphene oxide and 3mL
Ti(OBu)4As initial reactant, in alcohol solvent, reacts 6 hours, synthesize redox graphene modified nano-silica
Change titanium heterojunction structure composite photo-catalyst, so that it is modified to construct redox graphene by hydro-thermal-heat treatment-hydro-thermal method
Nano titanium dioxide heterogeneous structure composite photochemical catalyst, using amorphous carbon as TiO2 it is nanocrystalline with graphene two-dimensional surface it
Between heterostructure interface, improve the composite effect of TiO2 and graphene, improve its visible light catalysis activity；
(2) water-fast, impact resistance aluminium base crosslinking agent is manufactured, first aluminic acid butyl ester is diluted with dehydrated alcohol, adds glacial acetic acid, nothing
The mixed solution of water-ethanol, water, the volume ratio of water and dehydrated alcohol is 1:10 in mixed solution, is entered in mixer, starting is stirred
It mixes, is warming up to 80 DEG C, stir 30 minutes, obtain the light yellow sol of stable and uniform clear, be then slowly added to nano oxidized
Aluminium suspension maintains the temperature at 40 DEG C, obtains water-fast, impact resistance aluminium base crosslinking agent；Aluminium base crosslinking agent is taken, by aluminium base crosslinking agent liter
Temperature to 50 DEG C, after be slowly added to redox graphene modified nano-titanium dioxide heterojunction structure composite photo-catalyst suspension,
Aluminium base crosslinking agent is the 2wt% of total weight of the mixture, continues stirring 20 minutes after adding, obtains homogeneous mixture；And by step
(1) the redox graphene modified nano-titanium dioxide heterojunction structure composite photo-catalyst obtained and the aluminium base crosslinking agent system
It is standby at homogeneous mixture be attached to that hdpe fiber is online together, be fabricated to have and be urged with a thickness of the nanometer light of 50um
Change the hdpe fiber net of film coating, wherein the size of hdpe fiber net, which can according to need, is selected
It selects, the present embodiment selects width for 1.5 meters.Hdpe fiber net under the width convenient for subsequent working process and
Installation, while light-catalysed efficiency is also obtained into maximum promotion；
In the present embodiment, by hdpe fiber net, directly in the bucket equipped with homogeneous mixture, (be open big plastic barrel
In) in extracted many times, using extraction 7 times,
The technical requirements of the homogeneous mixture are as follows:
| Character | Liquid 2-5% |
| Crystal form | Anatase titanium dioxide |
| Content | 97.5% |
| Partial size | ≤10nm |
| Surface group | Carboxyl, carbonate |
| Optical response range | 300nm-550nm |
| Surface characteristic | It is hydrophilic |
| PH (1% aqueous solution) | 3-4 |
| Specific surface area | 400m2/g |
(3) the hdpe fiber net for the nano-photocatalytic film coating for obtaining step (2) is natural in air
After drying, then it is placed in drying in drying chamber, when drying in drying chamber, drying temperature uses 65 DEG C of constant temperature, and drying time is small using 35
When, obtain graphene modified nano-titanium dioxide photocatalyst web；
(4) it in the graphene modified nano-titanium dioxide photocatalyst web setting to creek obtained step (3), is allowed to
It is contacted with the water surface, while receiving illumination, creek black and odorous water is renovated.The black smelly water of creek is chemical fibre, print in the present embodiment
Industrial wastewater is contaminated, by thick dyestuff slurries after the processing of graphene modified nano-titanium dioxide photocatalyst web, dyestuff can be rich
Collection, and the concentration of inorganic salts declines, salt rejection rate is greater than 98%, and percentage dye loss can be transported at high temperature less than 0.1%
Row.
Embodiment three
The method for renovating creek black and odorous water using graphene modified nano-titanium dioxide photocatalyst web, including it is as follows
Step:
(1) using crystalline flake graphite as raw material, with dense H2SO4And KMnO4Oxidation stone is first made by two-step method for oxidant
Ink, then graphene oxide is made by ultrasonic disperse；By solvent-thermal method at 180 DEG C, with 30mg graphene oxide and 3mL
Ti(OBu)4As initial reactant, in alcohol solvent, reacts 6 hours, synthesize redox graphene modified nano-silica
Change titanium heterojunction structure composite photo-catalyst, so that it is modified to construct redox graphene by hydro-thermal-heat treatment-hydro-thermal method
Nano titanium dioxide heterogeneous structure composite photochemical catalyst, using amorphous carbon as TiO2 it is nanocrystalline with graphene two-dimensional surface it
Between heterostructure interface, improve the composite effect of TiO2 and graphene, improve its visible light catalysis activity；
(2) water-fast, impact resistance aluminium base crosslinking agent is manufactured, first aluminic acid butyl ester is diluted with dehydrated alcohol, adds glacial acetic acid, nothing
The mixed solution of water-ethanol, water, the volume ratio of water and dehydrated alcohol is 1:10 in mixed solution, is entered in mixer, starting is stirred
It mixes, is warming up to 75 DEG C, stir 20 minutes, obtain the light yellow sol of stable and uniform clear, be then slowly added to nano oxidized
Aluminium suspension maintains the temperature at 40 DEG C, obtains water-fast, impact resistance aluminium base crosslinking agent；Aluminium base crosslinking agent is taken, by aluminium base crosslinking agent liter
Temperature to 50 DEG C, after be slowly added to redox graphene modified nano-titanium dioxide heterojunction structure composite photo-catalyst suspension,
Aluminium base crosslinking agent is the 1wt% of total weight of the mixture, continues stirring 18 minutes after adding, obtains homogeneous mixture；And by step
(1) the redox graphene modified nano-titanium dioxide heterojunction structure composite photo-catalyst obtained and the aluminium base crosslinking agent system
It is standby at homogeneous mixture be attached to that hdpe fiber is online together, be fabricated to have and be urged with a thickness of the nanometer light of 30um
Change the hdpe fiber net of film coating, wherein the size of hdpe fiber net, which can according to need, is selected
It selects, selects width for 1.5 meters in the present embodiment.Hdpe fiber net under the width convenient for subsequent working process with
And installation, while light-catalysed efficiency is also obtained into maximum promotion；
In the present embodiment, by hdpe fiber net directly equipped with homogeneous mixture bucket in extracted many times, adopt
With extraction 7 times,
The technical requirements of the homogeneous mixture are as follows:
| Character | Liquid 2-5% |
| Crystal form | Anatase titanium dioxide |
| Content | 97.5% |
| Partial size | ≤10nm |
| Surface group | Carboxyl, carbonate |
| Optical response range | 300nm-550nm |
| Surface characteristic | It is hydrophilic |
| PH (1% aqueous solution) | 3-4 |
| Specific surface area | 400m2/g |
(3) the hdpe fiber net for the nano-photocatalytic film coating for obtaining step (2) is natural in air
After drying, then it is placed in drying in drying chamber, when drying in drying chamber, drying temperature uses 60 DEG C of constant temperature, and drying time is small using 30
When, obtain graphene modified nano-titanium dioxide photocatalyst web；
(4) it in the graphene modified nano-titanium dioxide photocatalyst web setting to creek obtained step (3), is allowed to
It is contacted with the water surface, while receiving illumination, creek black and odorous water is renovated.Creek black and odorous water is) paper waste, graphene
Modified nano-titanium dioxide photocatalyst web can more effectively remove dark lignin.The chlorination that pulp bleaching process generates
Lignin is electronegative, the easy graphene modified nano-titanium dioxide photocatalyst web retention by negatively charged, and
Pollution will not be generated to net.
Example IV
The method for renovating creek black and odorous water using graphene modified nano-titanium dioxide photocatalyst web, including it is as follows
Step:
(1) using crystalline flake graphite as raw material, with dense H2SO4And KMnO4Oxidation stone is first made by two-step method for oxidant
Ink, then graphene oxide is made by ultrasonic disperse；By solvent-thermal method at 180 DEG C, with 30mg graphene oxide and 3mL
Ti(OBu)4As initial reactant, in alcohol solvent, reacts 6 hours, synthesize redox graphene modified nano-silica
Change titanium heterojunction structure composite photo-catalyst, so that it is modified to construct redox graphene by hydro-thermal-heat treatment-hydro-thermal method
Nano titanium dioxide heterogeneous structure composite photochemical catalyst, using amorphous carbon as TiO2 it is nanocrystalline with graphene two-dimensional surface it
Between heterostructure interface, improve the composite effect of TiO2 and graphene, improve its visible light catalysis activity；
(2) water-fast, impact resistance aluminium base crosslinking agent is manufactured, first aluminic acid butyl ester is diluted with dehydrated alcohol, adds glacial acetic acid, nothing
The mixed solution of water-ethanol, water, the volume ratio of water and dehydrated alcohol is 1:10 in mixed solution, is entered in mixer, starting is stirred
It mixes, is warming up to 72 DEG C, stir 10 minutes, obtain the light yellow sol of stable and uniform clear, be then slowly added to nano oxidized
Aluminium suspension maintains the temperature at 40 DEG C, obtains water-fast, impact resistance aluminium base crosslinking agent；Aluminium base crosslinking agent is taken, by aluminium base crosslinking agent liter
Temperature to 50 DEG C, after be slowly added to redox graphene modified nano-titanium dioxide heterojunction structure composite photo-catalyst suspension,
Aluminium base crosslinking agent is the 0.1-2wt% of total weight of the mixture, continues stirring 17 minutes after adding, obtains homogeneous mixture；And it will
The redox graphene modified nano-titanium dioxide heterojunction structure composite photo-catalyst and the aluminium base that step (1) obtains are crosslinked
It is online that the homogeneous mixture that agent is prepared into is attached to hdpe fiber together, and being fabricated to has with a thickness of 0.5um-50um
Nano-photocatalytic film coating hdpe fiber net, wherein the size of hdpe fiber net can basis
It is selected, but best width is 1 meter, 1.5 meters or 2 meters.Hdpe fiber net under the width is convenient for
Subsequent working process and installation, while light-catalysed efficiency is also obtained into maximum promotion；
In the present embodiment, the homogeneous mixture that step (1) obtains is attached to high density polyethylene (HDPE) by the way of spraying
The surface of web, when spraying, using high-pressure spray gun, and by the way of five a small amount of even applications, each quantity for spray is not
More than the one third of spray paint total amount；
The technical requirements of the homogeneous mixture are as follows:
| Character | Liquid 2-5% |
| Crystal form | Anatase titanium dioxide |
| Content | 97.5% |
| Partial size | ≤10nm |
| Surface group | Carboxyl, carbonate |
| Optical response range | 300nm-550nm |
| Surface characteristic | It is hydrophilic |
| PH (1% aqueous solution) | 3-4 |
| Specific surface area | 400m2/g |
(3) the hdpe fiber net for the nano-photocatalytic film coating for obtaining step (2) is natural in air
After drying, then it is placed in drying in drying chamber, when drying in drying chamber, drying temperature uses 58 DEG C, and drying time uses 27 hours, obtains
To graphene modified nano-titanium dioxide photocatalyst web；
(4) it in the graphene modified nano-titanium dioxide photocatalyst web setting to creek obtained step (3), is allowed to
It is contacted with the water surface, while receiving illumination, creek black and odorous water is renovated.
Embodiment five
The method for renovating creek black and odorous water using graphene modified nano-titanium dioxide photocatalyst web, including it is as follows
Step:
(1) using crystalline flake graphite as raw material, with dense H2SO4And KMnO4Oxidation stone is first made by two-step method for oxidant
Ink, then graphene oxide is made by ultrasonic disperse；By solvent-thermal method at 180 DEG C, with 30mg graphene oxide and 3mL
Ti(OBu)4As initial reactant, in alcohol solvent, reacts 6 hours, synthesize redox graphene modified nano-silica
Change titanium heterojunction structure composite photo-catalyst, so that it is modified to construct redox graphene by hydro-thermal-heat treatment-hydro-thermal method
Nano titanium dioxide heterogeneous structure composite photochemical catalyst, using amorphous carbon as TiO2 it is nanocrystalline with graphene two-dimensional surface it
Between heterostructure interface, improve the composite effect of TiO2 and graphene, improve its visible light catalysis activity；
(2) water-fast, impact resistance aluminium base crosslinking agent is manufactured, first aluminic acid butyl ester is diluted with dehydrated alcohol, adds glacial acetic acid, nothing
The mixed solution of water-ethanol, water, the volume ratio of water and dehydrated alcohol is 1:10 in mixed solution, is entered in mixer, starting is stirred
It mixes, is warming up to 78 DEG C, stir 10 minutes, obtain the light yellow sol of stable and uniform clear, be then slowly added to nano oxidized
Aluminium suspension maintains the temperature at 40 DEG C, obtains water-fast, impact resistance aluminium base crosslinking agent；Aluminium base crosslinking agent is taken, by aluminium base crosslinking agent liter
Temperature to 50 DEG C, after be slowly added to redox graphene modified nano-titanium dioxide heterojunction structure composite photo-catalyst suspension,
Aluminium base crosslinking agent is the 0.1wt% of total weight of the mixture, continues stirring 20 minutes after adding, obtains homogeneous mixture；And it will step
Suddenly the redox graphene modified nano-titanium dioxide heterojunction structure composite photo-catalyst and the aluminium base crosslinking agent that (1) obtains
The homogeneous mixture being prepared into is attached to that hdpe fiber is online together, is fabricated to the nanometer light with a thickness of 50um
The hdpe fiber net of catalytic film coating, wherein the size of hdpe fiber net can according to need progress
Selection, width are 2 meters.Hdpe fiber net under the width is convenient for subsequent working process and installation, while
Light-catalysed efficiency is obtained into maximum promotion；In the present embodiment, hdpe fiber net is directly mixed equipped with homogeneous
Close object bucket in extracted many times, using extraction 3 times,
The technical requirements of the homogeneous mixture are as follows:
| Character | Liquid 2-5% |
| Crystal form | Anatase titanium dioxide |
| Content | 97.5% |
| Partial size | ≤10nm |
| Surface group | Carboxyl, carbonate |
| Optical response range | 300nm-550nm |
| Surface characteristic | It is hydrophilic |
| PH (1% aqueous solution) | 3-4 |
| Specific surface area | 400m2/g |
(3) the hdpe fiber net for the nano-photocatalytic film coating for obtaining step (2) is natural in air
After drying, then it is placed in drying in drying chamber, when drying in drying chamber, drying temperature uses 65 DEG C, and drying time uses 25 hours, obtains
To graphene modified nano-titanium dioxide photocatalyst web；
(4) it in the graphene modified nano-titanium dioxide photocatalyst web setting to creek obtained step (3), is allowed to
It is contacted with the water surface, while receiving illumination, creek black and odorous water is renovated.
Test example one
This test example is urged for step (1) redox graphene modified nano-titanium dioxide heterojunction structure complex light
The optimum condition of agent is selected and is carried out.
As shown in the table
| Project | Graphene oxide (mg) | Ti(OBu)4(ml) | Reaction time (hour) |
| A | 30 | 3 | 3 |
| B | 30 | 3 | 6 |
| C | 30 | 3 | 12 |
| D | 20 | 3 | 6 |
| E | 40 | 3 | 6 |
The product of preparation is characterized by binary complex of the means such as XRD, TEM, SEM, XPS to preparation, is such as schemed
Shown in 2- Fig. 7.
From above, it is apparent that when the amount for the graphene oxide that use is for 30mg, when the amount of Ti (OBu) 4 is 3ml,
The characterize data that the redox graphene modified nano-titanium dioxide heterojunction structure composite photo-catalyst of acquisition obtains is best.
Test example two
This test example prepares the best item of graphene modified nano-titanium dioxide photocatalyst web for step (2)
Part selection and carry out.
In order to determine optimal extracting times, this test is on the basis of other conditions are identical, only to extraction time
Number is adjusted, and the present embodiment selects extracting times N=1,3,5,7,9 and 11 time.And test high density polyethylene (HDPE) fibre
The nano-photocatalytic film coating that the online different extracting times of dimension obtain is to the catalytic degradation efficiency of methyl orange, as a result such as Fig. 8 institute
Show.
As seen from Figure 8, as the time increases, the degradation rate of methyl orange is continuously increased；With the increase of coating times,
Nano-photocatalytic film coating first increases the catalytic degradation efficiency of methyl orange to be reduced afterwards, and when coating layers are 7, effect is best,
Its most degradation rate can achieve 78% or so.According to its surface microscopic topographic it is found that during plated film, with plated film
Several increases, plated film are increasingly difficult to keep uniformly, and are applied in the nano-photocatalytic film of hdpe fiber net
Layer is more loose, when dry, shrinks, nano-photocatalytic film coating cracks, or even falls off.And it is attached to it
Particle elder generation free growth, with the increase for mentioning number, presoma is reduced in leaching liquor, and particle is dissolved in leaching liquor again, leads
It causes attaching particles to become smaller, reduces.
Therefore, the present invention is preferably 7 extractions.
Meanwhile for more membranaceous and powdered titanium dioxide catalytic effect, height is attached to when weighing with seven plated films
The titania powder of the online nano-photocatalytic film coating phase homogenous quantities of density polyethylene fibres compares test, as a result
As shown in Figure 9.Obviously, nano-photocatalytic film coating catalytic efficiency more high-efficient than powdered Titanium Dioxide 16%, and
Catalysis Rate is faster.So the photocatalytic degradation effect of plated film is more preferable.Powder is easy to happen reunion in the drying process, keeps it anti-
Contact surface is answered to reduce, so its catalytic degradation efficiency is lower.
Extracting times are selected to carry out repeated experiment, experiment for seven nano-photocatalytic film coatings according to experimental conditions
The results are shown in Figure 10, and load has the weight change situation of the stainless steel cloth of titanium deoxid film as shown in the table in experiment.
As seen from Figure 10, it is higher to there is first time catalytic degradation efficiency in pure and nano-photocatalytic film coating.
This is because the poor titanium dioxide of the online adhesive force of hdpe fiber can generate in first time catalysis degeneration experiment
It falls off, the amount for the catalyst for participating in catalysis degeneration experiment in subsequent repetitive test is caused to be reduced.It can from table
It arrives, first use causes catalyst adhesion amount to reduce by 40% and 36% respectively.Antigravity system in repeated experiment in table simultaneously
Weight change situation shows that only first use will cause catalyst attachment and significantly reduce, during being used for multiple times later, catalysis
Agent adhesion amount is basically unchanged.
By Figure 10 it can also be seen that again since being tested second, pure titinium dioxide film and graphene modified Nano two
The catalytic degradation efficiency of titanium dioxide photocatalyst web is all basically unchanged.And table also indicates that hdpe fiber net is attached on the net
The amount of titanium deoxid film remain unchanged.Illustrate that nano-photocatalytic film coating is firmly attached to high density polyethylene (HDPE) fibre
Net surface is tieed up, will not fall off, can reuse for a long time.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme should all cover within the scope of the claims and the description of the invention.
Claims (7)
1. using the method for graphene modified nano-titanium dioxide photocatalyst web regulation creek black and odorous water, feature exists
In including the following steps:
(1) using crystalline flake graphite as raw material, with dense H2SO4And KMnO4Graphite oxide is first made by two-step method for oxidant, then
Graphene oxide is made by ultrasonic disperse；
By solvent-thermal method at 180 DEG C, with graphene oxide and Ti (OBu)4As initial reactant, in alcohol solvent, close
At redox graphene modified nano-titanium dioxide heterojunction structure composite photo-catalyst；
(2) water-fast, impact resistance aluminium base crosslinking agent, and the redox graphene modified nano-silica that step (1) is obtained are manufactured
Change titanium heterojunction structure composite photo-catalyst and the aluminium base crosslinking agent is prepared into homogeneous mixture, homogeneous mixture is added to life
In the fibre stuff for producing hdpe fiber net, or to be attached to hdpe fiber online, is fabricated to nanometer
The hdpe fiber net of photocatalysis film coating；
Its detailed process are as follows:
Aluminic acid butyl ester first is diluted with dehydrated alcohol, adds the mixed solution of glacial acetic acid, dehydrated alcohol, water, water in mixed solution
Volume ratio with dehydrated alcohol is 1:10, is entered in mixer, and starting stirring is warming up to 70 DEG C -80 DEG C, stirs 10-30 minutes,
The light yellow sol for obtaining stable and uniform clear, is then slowly added to nano aluminium oxide suspension, maintains the temperature at 40 DEG C, obtain
To water-fast, impact resistance aluminium base crosslinking agent；
Take aluminium base crosslinking agent, aluminium base crosslinking agent be warming up to 50 DEG C, after be slowly added to redox graphene modified nano-silica
Change titanium heterojunction structure composite photo-catalyst suspension, aluminium base crosslinking agent is the 0.1-2wt% of total weight of the mixture, is continued after adding
Stirring 15-20 minutes, obtains homogeneous mixture；
Then homogeneous mixture is added in the fibre stuff of production hdpe fiber net, or is attached to high density and gathers
Vinyl fiber is online, is fabricated to the hdpe fiber net with nano-photocatalytic film coating；Wherein, the homogeneous is mixed
The technical requirements for closing object are as follows: shape, liquid 2-5%；Crystal form, anatase titanium dioxide；Content, 97.5%；Partial size ,≤10nm；Surface base
Group, carboxyl, carbonate；Optical response range, 300nm-550nm；Surface characteristic, it is hydrophilic；PH is 3-4 with 1% aqueous solution；Than
Surface area, 400m2/g；
(3) the hdpe fiber net for the nano-photocatalytic film coating that step (2) obtains is spontaneously dried in air
Afterwards, then it is placed in constant temperature drying in drying chamber, obtains graphene modified nano-titanium dioxide photocatalyst web；
(4) it in the graphene modified nano-titanium dioxide photocatalyst web setting to creek obtained step (3), is allowed to and water
Face contact, while receiving illumination, creek black and odorous water is renovated.
2. renovating creek black and odorous water using graphene modified nano-titanium dioxide photocatalyst web as described in claim 1
Method, which is characterized in that in step (2), the nano-photocatalytic film coating with a thickness of 0.5 μm -50 μm.
3. renovating creek black and odorous water using graphene modified nano-titanium dioxide photocatalyst web as described in claim 1
Method, which is characterized in that in step (2), the width of hdpe fiber net is 1 meter, 1.5 meters or 2 meters.
4. renovating creek black and odorous water using graphene modified nano-titanium dioxide photocatalyst web as described in claim 1
Method, which is characterized in that in step (2), the homogeneous mixture that step (2) obtains is attached to by the way of spraying highly dense
Spend the surface of polyethylene web；When spraying, using high-pressure spray gun, and by the way of multiple a small amount of even application.
5. renovating creek black and odorous water using graphene modified nano-titanium dioxide photocatalyst web as described in claim 1
Method, which is characterized in that by hdpe fiber net directly equipped with homogeneous mixture bucket in extracted many times.
6. renovating creek black and odorous water using graphene modified nano-titanium dioxide photocatalyst web as claimed in claim 5
Method, which is characterized in that by hdpe fiber net directly equipped with homogeneous mixture bucket in extract 3-7 times.
7. renovating creek black and odorous water using graphene modified nano-titanium dioxide photocatalyst web as described in claim 1
Method, which is characterized in that in step (3), when being dried in drying chamber, drying temperature use 55-65 DEG C, drying time use
25-35 hours.
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