CN109954518A - A kind of magnetic graphene-TiO2Photochemical biological sewage treatment method and device - Google Patents
A kind of magnetic graphene-TiO2Photochemical biological sewage treatment method and device Download PDFInfo
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- CN109954518A CN109954518A CN201811540339.5A CN201811540339A CN109954518A CN 109954518 A CN109954518 A CN 109954518A CN 201811540339 A CN201811540339 A CN 201811540339A CN 109954518 A CN109954518 A CN 109954518A
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- 239000010865 sewage Substances 0.000 title claims abstract description 60
- 238000011282 treatment Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 238000005554 pickling Methods 0.000 claims abstract description 9
- 239000002351 wastewater Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 229960000892 attapulgite Drugs 0.000 claims description 23
- 229910052625 palygorskite Inorganic materials 0.000 claims description 23
- 235000019441 ethanol Nutrition 0.000 claims description 22
- 229920001661 Chitosan Polymers 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 206010013786 Dry skin Diseases 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 8
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 230000020477 pH reduction Effects 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 abstract description 13
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 230000003389 potentiating effect Effects 0.000 abstract description 3
- 238000003672 processing method Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- 239000003344 environmental pollutant Substances 0.000 description 17
- 231100000719 pollutant Toxicity 0.000 description 17
- 238000000227 grinding Methods 0.000 description 12
- 229960004756 ethanol Drugs 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 238000001514 detection method Methods 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000003463 adsorbent Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- 239000006210 lotion Substances 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- JUQPZRLQQYSMEQ-UHFFFAOYSA-N CI Basic red 9 Chemical compound [Cl-].C1=CC(N)=CC=C1C(C=1C=CC(N)=CC=1)=C1C=CC(=[NH2+])C=C1 JUQPZRLQQYSMEQ-UHFFFAOYSA-N 0.000 description 3
- 238000013313 FeNO test Methods 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229940052223 basic fuchsin Drugs 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 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
- 229940012189 methyl orange Drugs 0.000 description 3
- 229910001172 neodymium magnet Inorganic materials 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- BHQCQFFYRZLCQQ-UHFFFAOYSA-N (3alpha,5alpha,7alpha,12alpha)-3,7,12-trihydroxy-cholan-24-oic acid Natural products OC1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 BHQCQFFYRZLCQQ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004380 Cholic acid Substances 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- BHQCQFFYRZLCQQ-OELDTZBJSA-N cholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 BHQCQFFYRZLCQQ-OELDTZBJSA-N 0.000 description 1
- 229960002471 cholic acid Drugs 0.000 description 1
- 235000019416 cholic acid Nutrition 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- KXGVEGMKQFWNSR-UHFFFAOYSA-N deoxycholic acid Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 KXGVEGMKQFWNSR-UHFFFAOYSA-N 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses magnetic graphene-TiO2Photochemical biological sewage treatment method and device, the device include thin plate, magnetisable material, ultraviolet lamp, and thin plate, which is located between wastewater inlet and outlet, to be horizontally arranged, and several magnetisable materials is uniformly fixed under thin plate, and pole orientation is consistent, by magnetic graphene-TiO2Compound is uniformly dispersed on thin plate, and thin plate top two sides are evenly equipped with multiple ultraviolet lamps.Processing method is the following steps are included: 1) by magnetic graphene-TiO2Compound is uniformly dispersed on thin plate；2) sewage is imported into thin plate, water layer thickness is less than 5cm, and sewage flows on thin plate, and total residence time is discharged after reaching 3h；Daytime, night opened ultraviolet lamp using daylight as light source；3) after running 30 days, magnet is removed, by magnetic graphene-TiO2Compound rinses, and is dispersed on thin plate, repeats the above steps after pickling, alkali cleaning, alcohol are washed.Using the present invention when handling sewage of low concentration, graphene oxide plays potent adsorption capacity and captures organic molecule by TiO2Carry out photocatalysis Decomposition.
Description
Technical field
The invention belongs to environment-friendly materials sewage treatment fields, and in particular to a kind of magnetic graphene-TiO2Photochemical biology is dirty
Method for treating water and device.
Background technique
Sewage composition is complicated, and centralized processing can only be from total amount by pollutant process, but the pollution big to content hypotoxicity
The problem of object processing cost is high, poor processing effect always exists.It needs to find and inhales that treatment effeciency is high, convenient to use, reclaiming
Treated substance and method.
The surface of graphene oxide (GO) is dispersed with many oxygen-containing functional groups, has hydrophily, can in evenly dispersed water,
The groups such as hydroxyl, the carboxyl on its surface can be compounded to form composite material, and graphene oxide with son, polymer etc. in a measure
Plane mesh structure is highly suitable as adsorbent to adsorb organic molecule and heavy metal ion.But to pass through after the completion of adsorbent
The means recycling such as precipitating filtering, process are cumbersome time-consuming and laborious.It has been reported that the composite magnetic group on graphene oxide, passes through magnetic force
Recycling solves the problems, such as recycling；It is just ineffective after adsorption saturation but as adsorbent, subsequent processing generally there are two types of mode,
One is the adsorbent directly more renewed, used adsorbent does fixed-end forces, and another kind is by chemically or physically
Desorption is recycled.Both methods all has that same i.e. pollutant only concentrates it, and it is not converted to
Innocuous substance, and no matter take which kind of subsequent processing mode all not can avoid to generate new environmental problem.
Chitosan (CS) is also known as chitosan, its significant properties is adsorption capacity.Many low molecular weights
Material, such as metal ion, cholesterol, triglycerides, cholic acid and organic mercury etc. can be adsorbed by chitosan.Especially shell
Glycan can not only adsorb magnesium, potassium, but also can adsorb zinc, calcium, mercury and uranium.
Attapulgite is the mineral material with preferable draw ratio and inner duct abundant, due to very big ratio
Surface area and ion exchangeable, therefore be ideal adsorbent.With inorganic or organic salt to Organic Surface Modification of Attapulgite, energy
Enough promote the performance of attapulgite.
Nano-TiO2Photocatalysis technology, thorough with reaction, oxidation of organic compounds under normal temperature and pressure, expense is low, toxicity is low, nothing
The characteristics of secondary pollution, numerous studies confirm that dyestuff, surfactant, organohalogen compounds, pesticide, oils, cyanide etc. can
Effective to carry out light-catalyzed reaction, decoloration, detoxification, mineralising is inorganic molecules substance, to eliminate the pollution to environment.But
There are some problems to need to solve, and if nanocatalyst is easy to reunite, required specific surface area is not achieved；If pollutant concentration is low,
Photocatalysis machine and contaminant molecule contact probability decline；In TiO2The adsorptivity on photocatalysis machine surface is poor, exists in practical application
The slow problem of degradation rate；Catalyst be it is powdered, need adhesive be coated on other materials surface, be virtually reduced and urged
The specific surface area of agent, and to be disposable, it can not replace.
Application No. is 201107435884 patents of invention to describe graphene/attapulgite/titanium dioxide for Jiangsu University
Preparation method and applications, by graphene oxide, butyl titanate, surfactant and acid processing attapulgite through hydro-thermal
Compound is made in reaction, handles methylene blue dye solution as adsorbent Static Adsorption, adsorption rate is up to 58.97~100%.Though
The problem of right adsorption rate is very high, shows that methylene blue is adsorbed by the adsorbent, but still unresolved pollutant still remains, temporary solution is not
It effects a permanent cure.
Summary of the invention
To overcome above-mentioned technical problem, the present invention provides one kind to prevent TiO2Reunite, reduce TiO2Crystal particle diameter while energy
Organic molecule in sewage of low concentration is enough captured, is completely decomposed into pollutant organic molecule by daylight or ultraviolet light irradiation inorganic
Small molecule, a kind of magnetic graphene-TiO easy to use2Photochemical biological sewage treatment method and processing unit.
In order to achieve the above objectives, the present invention is achieved by the following technical solutions.
A kind of magnetic graphene-TiO2Photochemical biology sewage treatment equipment, including thin plate, magnetisable material, ultraviolet lamp, thin plate
It is horizontally arranged between wastewater inlet and outlet, several magnetisable materials is uniformly fixed under thin plate, and pole orientation is consistent, it will
Magnetic graphene-TiO2Compound is uniformly dispersed on thin plate, and thin plate top two sides are evenly equipped with multiple ultraviolet lamps.Daytime is with daylight
Light source, night using ultraviolet lamp as light source, realize continuous processing.
Further the thin plate has muti-piece, arranges in step, 10~20cm of height difference between adjacent two pieces of thin plates.Water flow
Under let out during mix with air, increase dissolved oxygen in water, wait enter aquatic ecosystem after, be conducive to biological growth.
Further the thin plate is rectangle, and thin plate two sides are equipped with water bar, and 8~10 pieces of thin plates are one group, and every group most
Next piece of thin plate is equipped with header, and header is connect with elevator pump, and elevator pump is by sewage lifting to next group of most upper one piece of thin plate.
The thin plate is circle, and sewage pipe is located at each thin plate center of circle and arranges in umbrella, and sewage pipe is opened on top layer's thin plate
Top, every layer of thin plate are 40~50cm bigger than adjacent upper layer thin plate diameter, and 8~10 pieces of thin plates are one group, every group most next piece thin
Plate is equipped with header, and header connect with elevator pump, and elevator pump is by sewage lifting to next group of thin plate.
Further provide a kind of magnetic graphene-TiO2Photochemical biological sewage treatment method, comprising the following steps:
1) by magnetic graphene-TiO2Compound is uniformly dispersed on thin plate；
2) sewage is imported into thin plate, water layer thickness is less than 5cm, and sewage flows on thin plate, and total residence time reaches 3h heel row
Out；Daytime, night opened ultraviolet lamp using daylight as light source；
3) after running 30 days, magnet is removed, by magnetic graphene-TiO2Compound rinses, after pickling, alkali cleaning, alcohol are washed
It is dispersed on thin plate, repeats the above steps.
Further magnetic graphene-the TiO2The preparation method of compound, comprising the following steps:
1) chitosan is dissolved in acetum, nanometer Fe is added3O4, glutaraldehyde, adjust pH value of solution be 9~10, be stirred to react,
Separate insoluble matter, washed dry Fe3O4-CS；The chitosan and nanometer Fe3O4Weight ratio be 5:1~2；
2) by Fe3O4- CS is placed in acetum, and graphene oxide is added, and adjusting pH value of solution is 9~10, is stirred to react, and is separated
Insoluble matter, washed dry Fe3O4-CS-GO；The Fe3O4The weight ratio of-CS and graphene oxide is 3~5:1；
3) attapulgite is acidified through hydrochloric acid, is washed to neutrality, it is spare；Butyl titanate is dissolved in ethyl alcohol, be added triethanolamine,
Colloidal sol is made in nitric acid, and the attapulgite after acidification is added in colloidal sol and is stirred evenly, and 6~8h of ageing obtains gel, and then 650 DEG C
4~5h of lower heat treatment, obtains TiO2-ATP；The weight ratio of the attapulgite and butyl titanate is 1:15~20；
4) by Fe3O4- CS-GO and TiO2- ATP mixing is scattered in deionized water, heating mixing, separation insoluble matter, dry
Fe3O4-CS-GO-TiO2-ATP；The Fe3O4- CS-GO and TiO2The weight ratio of-ATP is 1~2:3~5.Due to attapulgite
With big specific surface area and strong adsorption capacity, so that the TiO between attapulgite2Grain growth is obstructed, therefore is distributed in recessed
TiO on convex stick soil2The average grain diameter of particle is about 30nm, relative to non-loaded TiO2Small 5~the 10nm of mean particle size,
And it is evenly distributed without agglomerating phenomenon；By graphene oxide and carry nano-TiO2It is attapulgite clay compounded, it is dirty in processing low concentration
When water, graphene oxide plays potent adsorption capacity and captures organic molecule by TiO2Carry out photocatalysis Decomposition；In graphite oxide
Compound can be fixed on other materials surface by magnetic force by composite magnetic chitosan on alkene, more fixed than traditional adhesive to save
Shi Shengli, and the specific surface area of compound is not reduced, when needing replacing compound, magnetisable material need to only be removed, be rinsed dry
Only, magnetisable material is reinstalled and in other materials surface spreading compound.
Further chitosan is dissolved in the acetum of 2% (w/w) in the step 1), nanometer Fe is added3O4、
50% (v/v) glutaraldehyde, is vigorously stirred 1~2h of reaction, and adjusting pH value of solution with the NaOH solution of 10% (w/w) is 9~10,50 DEG C
Water-bath is vigorously stirred 1~2h of reaction, is centrifugated out insoluble matter, is washed respectively with ethyl alcohol, deionized water to neutrality, and 60 DEG C dry
It is dry.
Further by Fe in the step 2)3O4- CS is placed in the acetum of 2% (w/w), and graphene oxide is added,
50 DEG C of stirring in water bath react 1~2h, and adjusting pH value of solution with the NaOH solution of 10% (w/w) is 9~10, warming-in-water to 80 DEG C after
It is continuous to be stirred to react 4~5h, it is centrifugated insoluble matter, is washed respectively with ethyl alcohol, deionized water to neutrality, 60 DEG C of dryings.
Attapulgite is first further crossed into 200 meshes in the step 3), the hydrochloric acid solution of 10% (w/w) is added, it is high
Speed stirring 10min, stands for 24 hours, and centrifuge separation is washed with deionized to Cl-；It is added in the ethanol solution of butyl titanate
The Fe of the amount 0.1~0.5% of Ti substance3+；Gel first in 200 DEG C of heat treatment 30min, then be warming up to 400 DEG C be heat-treated 1.5~
2h is finally warming up to 650 DEG C of heat treatment 2h. Fe3+Doping can semiconductor surface introduce defective locations or change crystallinity,
Both it can become the trap of electronics or hole and extend the service life to promote light-catalyzed reaction.
Further by Fe in the step 4)3O4- CS-GO and TiO2- ATP mixing is scattered in deionized water, and ultrasound is mixed
It after conjunction, is put into autoclave, is heated to 0.5~2MPa of pressure, keep 2~5h, then pressure release refrigerated separation insoluble matter.
The utility model has the advantages that compared with the prior art, the advantages of the present invention are as follows:
1) with attapulgite for carrier loaded nano-TiO2Particle, TiO2The average grain diameter of particle is relative to non-loaded TiO2?
The grain small 5~10nm of average grain diameter, and be evenly distributed without agglomerating phenomenon；
2) by graphene oxide and load nano-TiO2It is attapulgite clay compounded, when handling sewage of low concentration, graphene oxide hair
Potent adsorption capacity is waved to capture organic molecule by TiO2Carry out photocatalysis Decomposition；
3) compound can be fixed on other materials surface by magnetic force by the composite magnetic chitosan on graphene oxide, than passing
The adhesive fixation of system is time saving and energy saving, and does not reduce the specific surface area of compound, only need to will be magnetic when needing replacing compound
Substance removes, and rinses well, reinstalls magnetisable material and in other materials surface spreading compound；
4) thin plate step is arranged, and is mixed with air during letting out under water flow, and dissolved oxygen in water is increased.
Detailed description of the invention
The flat sewage device schematic diagram (part) of Fig. 1；
Fig. 2 plate back side distribution of magnets schematic diagram；
Fig. 3 umbrella-type sewage device schematic diagram (part)；
Wherein, 1. thin plate；2. magnetic oxygenated graphene photocatalysis compound；3. ultraviolet lamp；4. magnet.
Specific embodiment
Below with reference to example, the present invention is described in further detail.Raw material used in the present invention is commercial product.
Embodiment 1
A kind of magnetic graphene-TiO as shown in Figure 1, 22Photochemical biology sewage treatment equipment, including it is thin plate, magnetisable material, ultraviolet
Lamp；Thin plate is commercial polyethylene, and thickness 5mm, equipped with water bar, thin plate is located at horizontal between wastewater inlet and outlet for thin plate two sides
It places, several button-type neodymium iron boron strong magnets is uniformly fixed under thin plate, and pole orientation is consistent, by magnetic graphene-TiO2
Compound is uniformly dispersed on thin plate, and thin plate top two sides are evenly equipped with ultraviolet lamp；The thin plate has muti-piece to be rectangular, arranges in step
Cloth, height difference 15cm between every grade, 9 pieces of thin plates are one group, and every group of most next piece of thin plate is equipped with header, header and elevator pump
Sewage lifting to next group of most upper one piece of thin plate, thin plate length, width and group number are arranged by water is carried out for connection, elevator pump.
A kind of magnetic graphene-TiO2Photochemical biological sewage treatment method, comprising the following steps:
1) by magnetic graphene-TiO2Compound is uniformly dispersed on thin plate；
2) sewage is imported into thin plate, water layer thickness is less than 5cm, and sewage flows on thin plate, and total residence time reaches 3h heel row
Out；Daytime, night opened ultraviolet lamp using daylight as light source；
3) after running 30 days, magnet is removed, by magnetic graphene-TiO2Compound rinses, after pickling, alkali cleaning, alcohol are washed
It is dispersed on thin plate, repeats the above steps.
Magnetic graphene-TiO2The preparation method of compound, comprising the following steps:
1) 5g chitosan is dissolved in the acetum of 200mL2% (w/w), 1g nanometer Fe is added3O4, 50mL50% (v/v)
Glutaraldehyde is vigorously stirred reaction 1h, and adjusting pH value of solution with the NaOH solution of 10% (w/w) is that 9~10,50 DEG C of water-baths are vigorously stirred
1h is reacted, insoluble matter is centrifugated out, is washed respectively with ethyl alcohol, deionized water to neutrality, 60 DEG C of dryings obtain Fe after grinding3O4-
CS；
2) by 3g Fe3O4- CS is placed in the acetum of 200mL 2% (w/w), and the oxidation of 1g Hummers method preparation is added
Graphene, 50 DEG C of stirring in water bath react 1h, and adjusting pH value of solution with the NaOH solution of 10% (w/w) is 9~10, warming-in-water to 80
DEG C continue to be stirred to react 4h, is centrifugated insoluble matter, is washed respectively with ethyl alcohol, deionized water to neutrality, 60 DEG C of dryings, after grinding
Obtain Fe3O4-CS-GO；
3) attapulgite is crossed into 200 meshes, the hydrochloric acid solution of 10% (w/w) is added, with high-shearing dispersion emulsifying machine high-speed stirred
10min, stands for 24 hours, and centrifuge separation is washed with deionized to AgNO3Detection is without Cl-, it is dried for standby；By 10g butyl titanate
It is dissolved in 100mL dehydrated alcohol, 5mL triethanolamine and 0.03mmol FeNO is added3, stir evenly, then quickly stirring
The lower nitric acid for instilling 5% (w/w), forms glassy yelloe colloidal sol, and the attapulgite after 2g acidification is added in colloidal sol, stirring
Uniformly, 0.5g polyethylene glycol is then added, stirs 1h, then ultrasonic mixing 1h, obtains gel after being aged 6h；Gel is put into Muffle
In furnace, 200 DEG C of heat treatment 30min are first warming up to, 400 DEG C of heat treatment 1.5h is then heated to, is finally warming up to 650 DEG C of heat treatments
2h obtains TiO after grinding after cooling2-ATP；
4) by 1g Fe3O4- CS-GO and 3g TiO2- ATP mixing is scattered in deionized water, is put into autoclave, is heated to pressing
Power 0.5MPa, unlatching ultrasound, mixes 2h, and then pressure release is cooling, is centrifugated insoluble matter, and 50 DEG C of dryings obtain magnetic stone after grinding
Black alkene-TiO2Compound.
To be handled containing the sewage of different pollutants by the device, before detection sewage treatment with pollutant concentration after processing
Removal rate is calculated, dissolved oxygen in water calculates increment rate before and after detection processing, and data see the table below:
| Pollutant | Initial concentration mg/L | Removal rate % | Dissolved oxygen increment rate % |
| Methyl orange | 84 | 60.28~89.34 | 5.3~6.2 |
| Crystal violet | 68 | 53.63~87.16 | 5.4~6.5 |
| Methylene blue | 27 | 61.31~91.27 | 5.3~6.1 |
| Basic fuchsin | 13 | 54.98~84.36 | 5.1~6.5 |
After 30 days, remove magnet, magnetic oxygenated graphene photocatalysis compound rinsed, collect concentrate, through pickling,
Alkali cleaning, alcohol are dispersed on thin plate after washing, and are reused；It collects washing lotion and is concentrated under reduced pressure, detect washing lotion ingredient, the pollution being not detected
Object, it was demonstrated that pollutant is decomposed by magnetic oxygenated graphene photocatalysis compound substantially.
Embodiment 2
As shown in figure 3, a kind of magnetic graphene-TiO2Photochemical biology sewage treatment equipment, including it is thin plate, magnetisable material, ultraviolet
Lamp, thin plate are circular horizontal placement, and sewage pipe is located at each thin plate center of circle and arranges in umbrella, height difference 10cm between every grade, sewage pipe
It is opened on above top layer's thin plate, every layer of thin plate is 40~50cm bigger than adjacent upper layer thin plate diameter, and 10 pieces of thin plates are one group, often
Group most next piece of thin plate is equipped with header, and header is connect with elevator pump, and elevator pump is by sewage lifting to next group of thin plate, thin plate
Diameter and group number uniformly fix several button-type neodymium iron boron strong magnets, and pole orientation is consistent by water setting is carried out under thin plate,
By magnetic graphene-TiO2Compound is uniformly dispersed on thin plate, and thin plate top two sides are evenly equipped with ultraviolet lamp.
A kind of magnetic graphene-TiO2Photochemical biological sewage treatment method, comprising the following steps:
1) by magnetic graphene-TiO2Compound is uniformly dispersed on thin plate；
2) sewage is imported into thin plate, water layer thickness is less than 5cm, and sewage flows on thin plate, and total residence time reaches 3h heel row
Out；Daytime, night opened ultraviolet lamp using daylight as light source；
3) after running 30 days, magnet is removed, by magnetic graphene-TiO2Compound rinses, after pickling, alkali cleaning, alcohol are washed
It is dispersed on thin plate, repeats the above steps.
Magnetic graphene-TiO2The preparation method of compound, comprising the following steps:
1) 5g chitosan is dissolved in the acetum of 200mL2% (w/w), 2g nanometer Fe is added3O4, 50mL50% (v/v) penta
Dialdehyde is vigorously stirred reaction 2h, and adjusting pH value of solution with the NaOH solution of 10% (w/w) is that 9~10,50 DEG C of water-baths are vigorously stirred instead
2h is answered, insoluble matter is centrifugated out, is washed respectively with ethyl alcohol, deionized water to neutrality, 60 DEG C of dryings obtain Fe after grinding3O4-CS；
2) by 5g Fe3O4- CS is placed in the acetum of 200mL 2% (w/w), and the oxidation of 1g Hummers method preparation is added
Graphene, 50 DEG C of stirring in water bath react 2h, and adjusting pH value of solution with the NaOH solution of 10% (w/w) is 9~10, warming-in-water to 80
DEG C continue to be stirred to react 5h, is centrifugated insoluble matter, is washed respectively with ethyl alcohol, deionized water to neutrality, 60 DEG C of dryings, after grinding
Obtain Fe3O4-CS-GO；
3) attapulgite is crossed into 200 meshes, the hydrochloric acid solution of 10% (w/w) is added, with high-shearing dispersion emulsifying machine high-speed stirred
10min, stands for 24 hours, and centrifuge separation is washed with deionized to AgNO3Detection is without Cl-, it is dried for standby；By 20g butyl titanate
It is dissolved in 100mL dehydrated alcohol, 5mL triethanolamine and 0.3mmol FeNO is added3, stir evenly, then under fast stirring
The nitric acid of 5% (w/w) is instilled, glassy yelloe colloidal sol is formed, the attapulgite after 2g acidification is added in colloidal sol, stirring is equal
It is even, 0.5g polyethylene glycol is then added, stirs 1h, then ultrasonic mixing 1h, obtains gel after being aged 8h；Gel is put into Muffle furnace
It is interior, 200 DEG C of heat treatment 30min are first warming up to, 400 DEG C of heat treatment 2h are then heated to, are finally warming up to 650 DEG C of heat treatment 2h,
TiO is obtained after grinding after cooling2-ATP；
4) by 2g Fe3O4- CS-GO and 5g TiO2- ATP mixing is scattered in deionized water, is put into autoclave, is heated to pressing
Power 2MPa, unlatching ultrasound, mixes 5h, and then pressure release is cooling, is centrifugated insoluble matter, and 50 DEG C of dryings obtain magnetic graphite after grinding
Alkene-TiO2Compound.
To be handled containing the sewage of different pollutants by the device, before detection sewage treatment with pollutant concentration after processing
Removal rate is calculated, dissolved oxygen in water calculates increment rate before and after detection processing, and data see the table below:
| Pollutant | Initial concentration mg/L | Removal rate % | Dissolved oxygen increment rate % |
| Methyl orange | 84 | 66.82~92.37 | 8.9~11.5 |
| Crystal violet | 68 | 63.35~94.16 | 8.7~10.6 |
| Methylene blue | 27 | 74.13~95.27 | 9.4~11.3 |
| Basic fuchsin | 13 | 68.14~96.63 | 8.4~10.8 |
After 30 days, remove magnet, magnetic oxygenated graphene photocatalysis compound rinsed, collect concentrate, through pickling,
Alkali cleaning, alcohol are dispersed on thin plate after washing, and are reused；It collects washing lotion and is concentrated under reduced pressure, detect washing lotion ingredient, the pollution being not detected
Object, it was demonstrated that pollutant is decomposed by magnetic oxygenated graphene photocatalysis compound substantially.
Embodiment 3
A kind of magnetic graphene-TiO2Photochemical biology sewage treatment equipment, including thin plate, magnetisable material, ultraviolet lamp, thin plate are located at
It is horizontally arranged between wastewater inlet and outlet, several button-type neodymium iron boron strong magnets, and pole orientation is uniformly fixed under thin plate
Unanimously, magnetic graphene-TiO2Compound is uniformly dispersed on thin plate, and thin plate top two sides are evenly equipped with ultraviolet lamp；The thin plate is
It is rectangular to have muti-piece, it arranges in step, height difference 20cm between every grade, 8 pieces of thin plates are one group, and every group of most next piece of thin plate is equipped with afflux
Pipe, header connect with elevator pump, and elevator pump is by sewage lifting to next group of most upper one piece of thin plate, thin plate length, width and group
Number is arranged by water is carried out.
A kind of magnetic graphene-TiO2Photochemical biological sewage treatment method, comprising the following steps:
1) by magnetic graphene-TiO2Compound is uniformly dispersed on thin plate；
2) sewage is imported into thin plate, water layer thickness is less than 5cm, and sewage flows on thin plate, and total residence time reaches 3h heel row
Out；Daytime, night opened ultraviolet lamp using daylight as light source；
3) after running 30 days, magnet is removed, by magnetic graphene-TiO2Compound rinses, after pickling, alkali cleaning, alcohol are washed
It is dispersed on thin plate, repeats the above steps.
Magnetic graphene-TiO2The preparation method of compound, comprising the following steps:
1) 5g chitosan is dissolved in the acetum of 200mL2% (w/w), 1.5g nanometer Fe is added3O4, 50% (v/ of 50mL
V) glutaraldehyde is vigorously stirred reaction 1h, and adjusting pH value of solution with the NaOH solution of 10% (w/w) is that 9~10,50 DEG C of water-baths are acutely stirred
Reaction 2h is mixed, insoluble matter is centrifugated out, is washed respectively with ethyl alcohol, deionized water to neutrality, 60 DEG C of dryings, after grinding
Fe3O4-CS；
2) by 4g Fe3O4- CS is placed in the acetum of 200mL 2% (w/w), and the oxidation of 1g Hummers method preparation is added
Graphene, 50 DEG C of stirring in water bath react 1h, and adjusting pH value of solution with the NaOH solution of 10% (w/w) is 9~10, warming-in-water to 80
DEG C continue to be stirred to react 5h, is centrifugated insoluble matter, is washed respectively with ethyl alcohol, deionized water to neutrality, 60 DEG C of dryings, after grinding
Obtain Fe3O4-CS-GO；
3) attapulgite is crossed into 200 meshes, the hydrochloric acid solution of 10% (w/w) is added, with high-shearing dispersion emulsifying machine high-speed stirred
10min, stands for 24 hours, and centrifuge separation is washed with deionized to AgNO3Detection is without Cl-, it is dried for standby；By 15g butyl titanate
It is dissolved in 100mL dehydrated alcohol, 5mL triethanolamine and 0.12mmol FeNO is added3, stir evenly, then quickly stirring
The lower nitric acid for instilling 5% (w/w), forms glassy yelloe colloidal sol, and the attapulgite after 2g acidification is added in colloidal sol, stirring
Uniformly, 0.5g polyethylene glycol is then added, stirs 1h, then ultrasonic mixing 1h, obtains gel after being aged 7h；Gel is put into Muffle
In furnace, 200 DEG C of heat treatment 30min are first warming up to, 400 DEG C of heat treatment 2h is then heated to, is finally warming up to 650 DEG C of heat treatments
2h obtains TiO after grinding after cooling2-ATP；
4) by 2g Fe3O4- CS-GO and 3g TiO2- ATP mixing is scattered in deionized water, is put into autoclave, is heated to pressing
Power 1MPa, unlatching ultrasound, mixes 4h, and then pressure release is cooling, is centrifugated insoluble matter, and 50 DEG C of dryings obtain magnetic graphite after grinding
Alkene-TiO2Compound.
To be handled containing the sewage of different pollutants by the device, before detection sewage treatment with pollutant concentration after processing
Removal rate is calculated, dissolved oxygen in water calculates increment rate before and after detection processing, and data see the table below:
| Pollutant | Initial concentration mg/L | Removal rate % | Dissolved oxygen increment rate % |
| Methyl orange | 84 | 65.43~90.12 | 5.3~6.2 |
| Crystal violet | 68 | 59.17~91.65 | 5.4~6.5 |
| Methylene blue | 27 | 68.46~93.24 | 5.3~6.1 |
| Basic fuchsin | 13 | 74.98~94.14 | 5.1~6.5 |
After 30 days, remove magnet, magnetic oxygenated graphene photocatalysis compound rinsed, collect concentrate, through pickling,
Alkali cleaning, alcohol are dispersed on thin plate after washing, and are reused；It collects washing lotion and is concentrated under reduced pressure, detect washing lotion ingredient, the pollution being not detected
Object, it was demonstrated that pollutant is decomposed by magnetic oxygenated graphene photocatalysis compound substantially.
The present invention is illustrated according to above-described embodiment, it should be understood that above-described embodiment does not limit this in any form
Invention, it is all to use equivalent substitution or equivalent transformation mode technical solution obtained, it is within the scope of the present invention.
Claims (10)
1. a kind of magnetic graphene-TiO2Photochemical biology sewage treatment equipment, which is characterized in that including thin plate, magnetisable material, purple
Outer lamp, thin plate, which is located between wastewater inlet and outlet, to be horizontally arranged, and several magnetisable materials, and magnetic pole side are uniformly fixed under thin plate
To consistent, by magnetic graphene-TiO2Compound is uniformly dispersed on thin plate, and thin plate top two sides are evenly equipped with multiple ultraviolet lamps.
2. a kind of magnetic graphene-TiO according to claim 12Photochemical biology sewage treatment equipment, which is characterized in that institute
Stating thin plate has muti-piece, arranges in step, 10 ~ 20cm of height difference between adjacent two pieces of thin plates.
3. a kind of magnetic graphene-TiO according to claim 22Photochemical biology sewage treatment equipment, which is characterized in that institute
Stating thin plate is rectangle, and thin plate two sides are equipped with water bar, and 8 ~ 10 pieces of thin plates are one group, and every group of most next piece of thin plate is equipped with afflux
Pipe, header connect with elevator pump, and elevator pump is by sewage lifting to next group of most upper one piece of thin plate.
4. a kind of magnetic graphene-TiO according to claim 22Photochemical biology sewage treatment equipment, which is characterized in that institute
Thin plate is stated as circle, sewage pipe is located at each thin plate center of circle and arranges in umbrella, and sewage pipe is opened on above top layer's thin plate, every layer thin
Plate is 40 ~ 50cm bigger than adjacent upper layer thin plate diameter, and 8 ~ 10 pieces of thin plates are one group, and every group of most next piece of thin plate is equipped with header,
Header is connect with elevator pump, and elevator pump is by sewage lifting to next group of thin plate.
5. a kind of magnetic graphene-TiO2Photochemical biological sewage treatment method, which comprises the following steps:
1) by magnetic graphene-TiO2Compound is uniformly dispersed on thin plate；
2) sewage is imported into thin plate, water layer thickness is less than 5cm, and sewage flows on thin plate, and total residence time is discharged after reaching 3h；
Daytime, night opened ultraviolet lamp using daylight as light source；
3) after running 30 days, magnet is removed, by magnetic graphene-TiO2Compound rinses, and dissipates after pickling, alkali cleaning, alcohol are washed
On thin plate, repeat the above steps.
6. a kind of magnetic graphene-TiO according to claim 52Photochemical biological sewage treatment method, which is characterized in that institute
State magnetic graphene-TiO2The preparation method of compound, comprising the following steps:
1) chitosan is dissolved in acetum, nanometer Fe is added3O4, glutaraldehyde, adjust pH value of solution be 9 ~ 10, be stirred to react, point
From insoluble matter, washed dry Fe3O4-CS；The chitosan and nanometer Fe3O4Weight ratio be 5:1 ~ 2；
2) by Fe3O4- CS is placed in acetum, and graphene oxide is added, and adjusting pH value of solution is 9 ~ 10, is stirred to react, and separation is not
Molten object, washed dry Fe3O4-CS-GO；The Fe3O4The weight ratio of-CS and graphene oxide is 3 ~ 5:1；
3) attapulgite is acidified through hydrochloric acid, is washed to neutrality, it is spare；Butyl titanate is dissolved in ethyl alcohol, be added triethanolamine,
Colloidal sol is made in nitric acid, and attapulgite after acidification is added in colloidal sol and is stirred evenly, and 6 ~ 8h of ageing obtains gel, then at 650 DEG C
It is heat-treated 4 ~ 5h, obtains TiO2-ATP；The weight ratio of the attapulgite and butyl titanate is 1:15 ~ 20；
4) by Fe3O4- CS-GO and TiO2- ATP mixing is scattered in deionized water, heating mixing, separation insoluble matter, dry
Fe3O4-CS-GO-TiO2-ATP；The Fe3O4- CS-GO and TiO2The weight ratio of-ATP is 1 ~ 2:3 ~ 5.
7. a kind of magnetic graphene-TiO according to claim 62Photochemical biological sewage treatment method, which is characterized in that institute
State in step 1) and chitosan be dissolved in 2%(w/w) acetum in, be added nanometer Fe3O4, 50%(v/v) glutaraldehyde, acutely stir
1 ~ 2h of reaction is mixed, adjusting pH value of solution with the NaOH solution of 10%(w/w) is that 9 ~ 10,50 DEG C of water-baths are vigorously stirred 1 ~ 2h of reaction, is centrifuged
Insoluble matter is isolated, is washed respectively with ethyl alcohol, deionized water to neutrality, 60 DEG C of dryings.
8. a kind of magnetic graphene-TiO according to claim 62Photochemical biological sewage treatment method, which is characterized in that institute
It states Fe in step 23O4- CS is placed in 2%(w/w) acetum in, be added graphene oxide, 50 DEG C of stirring in water bath reaction 1 ~
2h, adjusting pH value of solution with the NaOH solution of 10%(w/w) is 9 ~ 10, and warming-in-water continues to be stirred to react 4 ~ 5h, centrifugation point to 80 DEG C
It from insoluble matter, is washed respectively with ethyl alcohol, deionized water to neutrality, 60 DEG C of dryings.
9. a kind of magnetic graphene-TiO according to claim 62Photochemical biological sewage treatment method, which is characterized in that institute
State in step 3) and attapulgite first to be crossed into 200 meshes, 10%(w/w is added) hydrochloric acid solution, high-speed stirred 10min stands for 24 hours,
Centrifuge separation, is washed with deionized to Cl-；The amount 0.1 ~ 0.5% of Ti substance is added in the ethanol solution of butyl titanate
Fe3+；Gel is first in 200 DEG C of heat treatment 30min, then is warming up to 400 DEG C of 1.5 ~ 2h of heat treatment, is finally warming up to 650 DEG C of heat treatments
2h。
10. a kind of magnetic graphene-TiO according to claim 62Photochemical biological sewage treatment method, which is characterized in that
By Fe in the step 4)3O4- CS-GO and TiO2- ATP mixing is scattered in deionized water, after ultrasonic mixing, is put into autoclave
In, it is heated to 0.5 ~ 2MPa of pressure, keeps 2 ~ 5h, then pressure release refrigerated separation insoluble matter.
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| CN113628778B (en) * | 2021-06-17 | 2023-12-08 | 福建工程学院 | Method for transferring and adsorbing radioactive elements in tailings in high-cold and high-altitude areas |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580287A (en) * | 2009-06-12 | 2009-11-18 | 东北电力大学 | Rotary-type photocatalysed or adsorptive reactor |
| CN101823778A (en) * | 2010-05-24 | 2010-09-08 | 哈尔滨工程大学 | Continuous photocatalytic reaction device |
| CN102319590A (en) * | 2011-05-27 | 2012-01-18 | 湖北富邦科技股份有限公司 | Tri-iron tetroxide/shitosan/TiO 2The nano composite photocatalytic preparation methods |
| US20140178759A1 (en) * | 2012-12-21 | 2014-06-26 | Lawrence Livermore National Security, Llc | Graphene-supported metal oxide monolith |
| CN105413647A (en) * | 2015-12-10 | 2016-03-23 | 福建师范大学福清分校 | Method for preparing functionalized graphene |
| CN105749915A (en) * | 2015-11-12 | 2016-07-13 | 天津工业大学 | Method for preparing magnetic graphene-based titanium dioxide composite |
| CN106824081A (en) * | 2017-03-06 | 2017-06-13 | 西华大学 | A kind of Graphene titanium dioxide attapulgite composite material and its preparation method and application |
| CN107910426A (en) * | 2017-11-14 | 2018-04-13 | 广东金源照明科技股份有限公司 | A kind of magnetic fluorescence powder composite material and its flat coating method |
-
2018
- 2018-11-09 CN CN201811328529.0A patent/CN109158130A/en active Pending
- 2018-12-17 CN CN201811540339.5A patent/CN109954518B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580287A (en) * | 2009-06-12 | 2009-11-18 | 东北电力大学 | Rotary-type photocatalysed or adsorptive reactor |
| CN101823778A (en) * | 2010-05-24 | 2010-09-08 | 哈尔滨工程大学 | Continuous photocatalytic reaction device |
| CN102319590A (en) * | 2011-05-27 | 2012-01-18 | 湖北富邦科技股份有限公司 | Tri-iron tetroxide/shitosan/TiO 2The nano composite photocatalytic preparation methods |
| US20140178759A1 (en) * | 2012-12-21 | 2014-06-26 | Lawrence Livermore National Security, Llc | Graphene-supported metal oxide monolith |
| CN105749915A (en) * | 2015-11-12 | 2016-07-13 | 天津工业大学 | Method for preparing magnetic graphene-based titanium dioxide composite |
| CN105413647A (en) * | 2015-12-10 | 2016-03-23 | 福建师范大学福清分校 | Method for preparing functionalized graphene |
| CN106824081A (en) * | 2017-03-06 | 2017-06-13 | 西华大学 | A kind of Graphene titanium dioxide attapulgite composite material and its preparation method and application |
| CN107910426A (en) * | 2017-11-14 | 2018-04-13 | 广东金源照明科技股份有限公司 | A kind of magnetic fluorescence powder composite material and its flat coating method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114055590A (en) * | 2021-11-03 | 2022-02-18 | 阜阳大可新材料股份有限公司 | Ultraviolet-resistant fiberboard for outdoor decoration |
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