CN109954518B - Magnetic graphene-TiO2Photochemical biological sewage treatment method and device - Google Patents
Magnetic graphene-TiO2Photochemical biological sewage treatment method and device Download PDFInfo
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- 239000010865 sewage Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000005406 washing Methods 0.000 claims abstract description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 33
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 20
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
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- 229910052770 Uranium Inorganic materials 0.000 description 1
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- 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
- 229910052725 zinc Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- 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)
- Water Treatment By Electricity Or Magnetism (AREA)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses magnetic graphene-TiO2The photochemical biological sewage treating apparatus includes one sheet, one magnetic matter and one ultraviolet lamp, and the sheet is set horizontally between the sewage inlet and the sewage outlet and has several magnetic matters fixed homogeneously in the same magnetic pole direction and magnetic graphene-TiO2The composite is uniformly dispersed on the thin plate, and a plurality of ultraviolet lamps are uniformly distributed on two sides of the upper part of the thin plate. The processing method comprises the following steps: 1) mixing magnetic graphene-TiO2The compound is uniformly dispersed on the thin plate; 2) introducing sewage into the thin plate, wherein the thickness of a water layer is less than 5cm, the sewage flows on the thin plate, and the sewage is discharged after the total retention time reaches 3 hours; daylight is used as a light source in the daytime, and an ultraviolet lamp is turned on at night; 3) after 30 days of operation, the magnet is removed, and the magnetic graphene-TiO is added2And (4) washing the compound, washing the compound by acid, alkali and alcohol, and scattering the compound on the thin plate, and repeating the steps. When the method is used for treating low-concentration sewage, the graphene oxide exerts strong adsorption capacity to capture organic molecules from TiO2And carrying out photocatalytic decomposition.
Description
Technical Field
The invention belongs to the field of sewage treatment of environment-friendly materials, and particularly relates to magnetic graphene-TiO2A method and a device for treating photochemical biological sewage.
Background
The sewage has complex components, the centralized treatment can only treat pollutants from the total amount, but the problems of high treatment cost and poor treatment effect on the pollutants with low content and high toxicity always exist. There is a need to find a treatment substance and a method which have high adsorption treatment efficiency, are convenient to use, and are recyclable.
The surface of Graphene Oxide (GO) is distributed with a plurality of oxygen-containing functional groups, has hydrophilicity, can be uniformly dispersed in water, the hydroxyl, carboxyl and other groups on the surface of the graphene oxide can be compounded with a plurality of molecules, polymers and the like to form a composite material, and the graphene oxide plane network structure is very suitable to be used as an adsorbent to adsorb organic molecules and heavy metal ions. However, the adsorbent is recovered by means of precipitation, filtration and the like after the completion, and the process is complicated, time-consuming and labor-consuming. It has been reported that the recovery problem is solved by magnetic recovery by compounding a magnetic group on graphene oxide; however, as the adsorbent, the adsorbent loses its effect after being saturated by adsorption, and the subsequent treatment generally has two modes, one mode is to directly replace a new adsorbent, the used adsorbent is treated by solid waste, and the other mode is to desorb the adsorbent by a chemical or physical mode for recycling. Both methods have the same problem that pollutants are only concentrated and are not converted into harmless substances, and no matter which subsequent treatment mode is adopted, new environmental problems can be caused inevitably.
Chitosan (CS), also known as chitosan, has a significant characteristic of adsorption capacity. Many low molecular weight materials, such as metal ions, cholesterol, triglycerides, bile acids, and organic mercury, etc., can be adsorbed by chitosan. In particular, the chitosan can adsorb not only magnesium and potassium, but also zinc, calcium, mercury and uranium.
The attapulgite is a mineral material with good length-diameter ratio and rich internal pore channels, and is an ideal adsorbent due to very large specific surface area and ion exchange property. The attapulgite is organically modified by inorganic or organic salt, so that the performance of the attapulgite can be improved.
Nano TiO 22The photocatalysis technology has the characteristics of complete reaction and oxidation of organic matters at normal temperature and normal pressure, low cost, low toxicity and no secondary pollution, and a large number of researches prove that dyes, surfactants, organic halides, pesticides, oils, cyanides and the like can effectively carry out photocatalysis reaction, decoloration, detoxification and mineralization into inorganic micromolecular substances, thereby eliminating the pollution to the environment. But also has some problems to be solved, such as the nano catalyst is easy to agglomerate and can not reach the required specific surface area; if the concentration of the pollutants is low, the contact probability of the photocatalytic machine and pollutant molecules is reduced; in TiO2Poor adsorptivity of the surface of the photocatalytic machine, and reduced in practical applicationSolving the problem of slow speed; the catalyst is powdery, needs an adhesive to coat the surface of other materials, virtually reduces the specific surface area of the catalyst, and is disposable and cannot be replaced.
The invention patent of Jiangsu university application number 201107435884 introduces a preparation method and application of graphene/attapulgite/titanium dioxide, graphene oxide, tetrabutyl titanate, a surfactant and acid-treated attapulgite are subjected to hydrothermal reaction to prepare a compound, the compound is used as an adsorbent to statically adsorb and treat methylene blue dye solution, and the adsorption rate reaches 58.97-100%. Although the adsorption rate is high, which indicates that methylene blue is adsorbed by the adsorbent, the problem of pollutants still existing is not solved, and the treatment is temporary and permanent.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a method for preventing TiO2Agglomeration, reduction of TiO2The magnetic graphene-TiO magnetic material has the advantages that the crystal particle size can capture organic molecules in low-concentration sewage, organic molecules of pollutants are thoroughly decomposed into inorganic small molecules through sunlight or ultraviolet lamp irradiation, and the use is convenient2A photochemical biological sewage treatment method and a photochemical biological sewage treatment device.
In order to achieve the above object, the present invention is achieved by the following means.
Magnetic graphene-TiO2The photochemical biological sewage treatment device comprises a thin plate, magnetic substances and an ultraviolet lamp, wherein the thin plate is horizontally arranged between a sewage inlet and a sewage outlet, a plurality of magnetic substances are uniformly fixed under the thin plate, the directions of magnetic poles are consistent, and magnetic graphene-TiO is subjected to magnetic treatment2The composite is uniformly dispersed on the thin plate, and a plurality of ultraviolet lamps are uniformly distributed on two sides of the upper part of the thin plate. The continuous treatment is realized by using sunlight as a light source in the daytime and using an ultraviolet lamp as a light source at night.
Furthermore, the thin plates are arranged in a stepped mode, and the height difference between every two adjacent thin plates is 10-20 cm. The water flow is mixed with air in the process of discharging, dissolved oxygen in water is increased, and after the water flow enters a water ecosystem, the growth of organisms is facilitated.
Further, the thin plate is rectangular, water retaining strips are arranged on two sides of the thin plate, 8-10 thin plates form a group, a collecting pipe is arranged on the bottom thin plate of each group and connected with a lifting pump, and the lifting pump lifts sewage to the top thin plate of the next group.
The sheet metal is circular, and the sewage pipe is located each sheet metal centre of a circle and is umbelliform arranging, and the sewage pipe opening is in the superiors sheet metal top, and every layer of sheet metal is greater than the adjacent upper strata sheet metal diameter by 40~50cm, and 8~10 sheet metals are a set of, and every group is equipped with the pressure manifold bottom sheet metal, and the pressure manifold is connected with the elevator pump, and the elevator pump promotes sewage to next a set of sheet metal.
Further provides a magnetic graphene-TiO2An actinic biological sewage treatment method comprising the steps of:
1) mixing magnetic graphene-TiO2The compound is uniformly dispersed on the thin plate;
2) introducing sewage into the thin plate, wherein the thickness of a water layer is less than 5cm, the sewage flows on the thin plate, and the sewage is discharged after the total retention time reaches 3 hours; daylight is used as a light source in the daytime, and an ultraviolet lamp is turned on at night;
3) after 30 days of operation, the magnet is removed, and the magnetic graphene-TiO is added2And (4) washing the compound, washing the compound by acid, alkali and alcohol, and scattering the compound on the thin plate, and repeating the steps.
Further the magnetic graphene-TiO2A method of preparing a composite comprising the steps of:
1) dissolving chitosan in acetic acid solution, adding nano Fe3O4Glutaraldehyde, adjusting the pH value of the solution to 9-10, stirring for reaction, separating insoluble substances, washing and drying to obtain Fe3O4-CS; the chitosan and the nano Fe3O4The weight ratio of (A) to (B) is 5: 1-2;
2) mixing Fe3O4Placing CS in an acetic acid solution, adding graphene oxide, adjusting the pH of the solution to 9-10, stirring for reaction, separating insoluble substances, washing and drying to obtain Fe3O4-CS-GO; said Fe3O4The weight ratio of CS to graphene oxide is 3-5: 1;
3) acidizing attapulgite by hydrochloric acid, and washing to be neutral for later use; dissolving tetrabutyl titanate in ethanol, adding tributyl titanatePreparing sol from ethanolamine and nitric acid, adding the acidified attapulgite into the sol, uniformly stirring, aging for 6-8 h to obtain gel, and then performing heat treatment at 650 ℃ for 4-5 h to obtain TiO2-ATP; the weight ratio of the attapulgite to the tetrabutyl titanate is 1: 15-20;
4) mixing Fe3O4-CS-GO with TiO2Mixing ATP, dispersing in deionized water, heating, mixing, separating insoluble substances, and drying to obtain Fe3O4-CS-GO-TiO2-ATP; said Fe3O4-CS-GO with TiO2The weight ratio of ATP is 1-2: 3-5. Because the attapulgite has large specific surface area and strong adsorption force, TiO positioned between the attapulgite2Grain growth is hindered and therefore the TiO is distributed on the attapulgite2The average particle size of the particles was about 30nm relative to the unsupported TiO2The average particle size of the particles is 5-10 nm, and the particles are uniformly distributed without agglomeration; mixing graphene oxide with nano TiO2The attapulgite is compounded, and when low-concentration sewage is treated, the graphene oxide exerts strong adsorption capacity to capture organic molecules from TiO2Carrying out photocatalytic decomposition; compound magnetic chitosan on graphite oxide can fix the compound on other material surfaces through magnetic force, and is fixed labour saving and time saving than traditional gluing agent, does not reduce the specific surface area of compound moreover, when needing to be changed the compound, only needs to remove the magnetic substance, washes cleanly, installs the magnetic substance again and spreads the compound can on other material surfaces.
Further dissolving chitosan in 2% (w/w) acetic acid solution in the step 1), and adding nano Fe3O4And 50% (v/v) glutaraldehyde, stirring vigorously to react for 1-2 h, adjusting the pH of the solution to 9-10 by using a 10% (w/w) NaOH solution, stirring vigorously in a 50 ℃ water bath to react for 1-2 h, centrifuging to separate out insoluble substances, washing with ethanol and deionized water respectively to be neutral, and drying at 60 ℃.
Further adding Fe in the step 2)3O4Placing CS in 2% (w/w) acetic acid solution, adding graphene oxide, stirring and reacting for 1-2 h in 50 ℃ water bath, adjusting the pH of the solution to 9-10 by using 10% (w/w) NaOH solution, heating the water bath to 80 ℃, and continuing to reactStirring and reacting for 4-5 h, centrifugally separating insoluble substances, washing the insoluble substances to be neutral by using ethanol and deionized water respectively, and drying the insoluble substances at the temperature of 60 ℃.
Further, in the step 3), firstly, the attapulgite is sieved by a 200-mesh sieve, 10% (w/w) hydrochloric acid solution is added, high-speed stirring is carried out for 10min, standing is carried out for 24h, centrifugal separation is carried out, and deionized water is used for washing until Cl is obtained-(ii) a Adding Fe with the amount of 0.1-0.5% of Ti substance into an ethanol solution of tetrabutyl titanate3+(ii) a And (3) carrying out heat treatment on the gel at 200 ℃ for 30min, then heating to 400 ℃ for heat treatment for 1.5-2 h, and finally heating to 650 ℃ for heat treatment for 2 h. Fe3+The doping can introduce defect positions on the surface of the semiconductor or change the crystallinity, and the doping can become traps of electrons or holes to prolong the service life so as to promote the photocatalytic reaction.
Further adding Fe in the step 4)3O4-CS-GO with TiO2And mixing and dispersing ATP in deionized water, ultrasonically mixing, putting into a pressure kettle, heating to the pressure of 0.5-2 MPa, keeping for 2-5 h, and then decompressing, cooling and separating insoluble substances.
Has the advantages that: compared with the prior art, the invention has the advantages that:
1) nano TiO loaded with attapulgite as carrier2Particles of TiO2Average particle size of the particles relative to unsupported TiO2The average particle size of the particles is 5-10 nm, and the particles are uniformly distributed without agglomeration;
2) mixing graphene oxide with nano TiO2The attapulgite is compounded, and when low-concentration sewage is treated, the graphene oxide exerts strong adsorption capacity to capture organic molecules from TiO2Carrying out photocatalytic decomposition;
3) the magnetic chitosan is compounded on the graphene oxide, so that the compound can be fixed on the surfaces of other materials through magnetic force, the time and labor are saved compared with the traditional adhesive, the specific surface area of the compound is not reduced, and when the compound needs to be replaced, the magnetic substance is removed, washed clean, reinstalled and spread on the surfaces of other materials;
4) the thin plates are arranged in a gradient manner, and the water flow is mixed with air in the process of discharging, so that the dissolved oxygen in water is increased.
Drawings
FIG. 1 is a schematic view (in part) of a flat plate sewage apparatus;
FIG. 2 is a schematic diagram of the arrangement of magnets on the back of a flat plate;
FIG. 3 is a schematic view (partially) of an umbrella type sewage apparatus;
wherein, 1, thin plate; 2. a magnetic graphene oxide photocatalytic complex; 3. an ultraviolet lamp; 4. and a magnet.
Detailed Description
The present invention will be described in further detail with reference to examples. The raw materials used in the invention are all commercial products.
Example 1
As shown in figures 1 and 2, a magnetic graphene-TiO2The photochemical biological sewage treatment device comprises a thin plate, a magnetic substance and an ultraviolet lamp; the thin plate is made of industrial polyethylene and is 5mm thick, water retaining strips are arranged on two sides of the thin plate, the thin plate is horizontally arranged between a sewage inlet and a sewage outlet, a plurality of button-shaped neodymium-iron-boron strong magnets are uniformly fixed under the thin plate, the directions of magnetic poles are consistent, and the magnetic graphene-TiO is subjected to magnetic field2The compound is uniformly dispersed on the thin plate, and ultraviolet lamps are uniformly distributed on two sides of the upper part of the thin plate; the sheet metal has the polylith for square, is the step and arranges, and the difference in height 15cm between every level, 9 sheet metals are a set of, and every group is the bottom sheet metal and is equipped with the pressure manifold, and the pressure manifold is connected with the elevator pump, and the elevator pump promotes sewage to a set of top sheet metal down, and sheet metal length, width and group number set up according to the volume of coming water.
Magnetic graphene-TiO2An actinic biological sewage treatment method comprising the steps of:
1) mixing magnetic graphene-TiO2The compound is uniformly dispersed on the thin plate;
2) introducing sewage into the thin plate, wherein the thickness of a water layer is less than 5cm, the sewage flows on the thin plate, and the sewage is discharged after the total retention time reaches 3 hours; daylight is used as a light source in the daytime, and an ultraviolet lamp is turned on at night;
3) after 30 days of operation, the magnet is removed, and the magnetic graphene-TiO is added2And (4) washing the compound, washing the compound by acid, alkali and alcohol, and scattering the compound on the thin plate, and repeating the steps.
Magnetic graphene-TiO2A method of preparing a composite comprising the steps of:
1) 5g of chitosan is dissolved in 200mL of 2% (w/w) acetic acid solution, and 1g of nano Fe is added3O450mL of 50% (v/v) glutaraldehyde, vigorously stirring for reaction for 1h, adjusting the pH of the solution to 9-10 by using 10% (w/w) NaOH solution, vigorously stirring for reaction for 1h in a water bath at 50 ℃, centrifugally separating out insoluble substances, washing the insoluble substances to be neutral by using ethanol and deionized water respectively, drying the insoluble substances at 60 ℃, and grinding the insoluble substances to obtain Fe3O4-CS；
2) 3g of Fe3O4Placing CS in 200mL of 2% (w/w) acetic acid solution, adding 1g of graphene oxide prepared by a Hummers method, stirring and reacting for 1h in water bath at 50 ℃, adjusting the pH of the solution to 9-10 by using 10% (w/w) NaOH solution, heating the solution to 80 ℃ in water bath, continuing stirring and reacting for 4h, centrifugally separating insoluble substances, washing the insoluble substances to be neutral by using ethanol and deionized water respectively, drying the insoluble substances at 60 ℃, and grinding the insoluble substances to obtain Fe3O4-CS-GO；
3) Sieving attapulgite with 200 mesh sieve, adding 10% (w/w) hydrochloric acid solution, high-speed stirring with high shear dispersion emulsifying machine for 10min, standing for 24 hr, centrifuging, washing with deionized water to AgNO3Detection of Cl-free-Drying for later use; dissolving 10g of tetrabutyl titanate in 100mL of absolute ethanol, adding 5mL of triethanolamine and 0.03mmol of FeNO3Uniformly stirring, then dripping 5% (w/w) nitric acid under rapid stirring to form transparent yellow sol, adding 2g of acidified attapulgite into the sol, uniformly stirring, then adding 0.5g of polyethylene glycol, stirring for 1h, then ultrasonically mixing for 1h, and aging for 6h to obtain gel; putting the gel into a muffle furnace, heating to 200 ℃ for heat treatment for 30min, heating to 400 ℃ for heat treatment for 1.5h, heating to 650 ℃ for heat treatment for 2h, cooling, and grinding to obtain TiO2-ATP；
4) Mixing 1g of Fe3O4-CS-GO with 3g TiO2Mixing and dispersing ATP in deionized water, putting the mixture into a pressure kettle, heating the mixture to the pressure of 0.5MPa, starting ultrasound, mixing for 2 hours, then decompressing and cooling, centrifugally separating insoluble substances, drying at 50 ℃, and grinding to obtain the magnetic graphene-TiO2And (c) a complex.
The sewage that will contain different pollutants passes through the device to be handled, detects that pollutant concentration calculates the clearance before sewage treatment and after handling, and the aquatic dissolved oxygen volume calculates the increase rate before detecting the processing, and the data is shown in the following table:
| contaminants | Initial concentration mg/L | Removal rate% | Increase rate of dissolved oxygen% |
| 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 the magnetic graphene oxide photocatalyst composite is used for 30 days, the magnet is removed, the magnetic graphene oxide photocatalyst composite is washed down, collected and concentrated, and the magnetic graphene oxide photocatalyst composite is dispersed on a thin plate after acid washing, alkali washing and alcohol washing and is reused; and collecting the washing liquid, carrying out reduced pressure concentration, detecting the components of the washing liquid, and detecting the undetected pollutants to prove that the pollutants are basically decomposed by the magnetic graphene oxide photocatalytic compound.
Example 2
As shown in FIG. 3, a magnetic graphene-TiO2The photochemical biological sewage treatment device comprises thin plates, magnetic substances and ultraviolet lamps, wherein the thin plates are horizontally placed in a circular shape, sewage pipes are arranged at the circle centers of the thin plates in an umbrella shape, the height difference between every two stages is 10cm, and the openings of the sewage pipes are arranged at the mostThe upper thin plate top, every layer of thin plate is 40~50cm more than the adjacent upper thin plate diameter, 10 thin plates are a set of, and every group is the bottom thin plate to be equipped with the pressure manifold, and the pressure manifold is connected with the elevator pump, and the elevator pump promotes sewage to next a set of thin plate, and the thin plate diameter sets up according to the volume of coming with the group number, evenly fixes a plurality of button shape neodymium iron boron strong magnets under the thin plate, and the magnetic pole direction is unanimous, with magnetism graphite alkene-TiO2The composite is uniformly dispersed on the thin plate, and ultraviolet lamps are uniformly distributed on two sides of the upper part of the thin plate.
Magnetic graphene-TiO2An actinic biological sewage treatment method comprising the steps of:
1) mixing magnetic graphene-TiO2The compound is uniformly dispersed on the thin plate;
2) introducing sewage into the thin plate, wherein the thickness of a water layer is less than 5cm, the sewage flows on the thin plate, and the sewage is discharged after the total retention time reaches 3 hours; daylight is used as a light source in the daytime, and an ultraviolet lamp is turned on at night;
3) after 30 days of operation, the magnet is removed, and the magnetic graphene-TiO is added2And (4) washing the compound, washing the compound by acid, alkali and alcohol, and scattering the compound on the thin plate, and repeating the steps.
Magnetic graphene-TiO2A method of preparing a composite comprising the steps of:
1) 5g of chitosan is dissolved in 200mL of 2% (w/w) acetic acid solution, and 2g of nano Fe is added3O450mL of 50% (v/v) glutaraldehyde, vigorously stirring for reacting for 2h, adjusting the pH of the solution to 9-10 with 10% (w/w) NaOH solution, vigorously stirring for reacting for 2h in a 50 ℃ water bath, centrifugally separating out insoluble substances, washing the insoluble substances to be neutral with ethanol and deionized water respectively, drying at 60 ℃, and grinding to obtain Fe3O4-CS；
2) Mixing 5g of Fe3O4Placing CS in 200mL of 2% (w/w) acetic acid solution, adding 1g of graphene oxide prepared by a Hummers method, stirring and reacting for 2h in water bath at 50 ℃, adjusting the pH of the solution to 9-10 by using 10% (w/w) NaOH solution, heating the solution to 80 ℃ in water bath, continuing stirring and reacting for 5h, centrifugally separating insoluble substances, washing the insoluble substances to be neutral by using ethanol and deionized water respectively, drying the insoluble substances at 60 ℃, and grinding the insoluble substances to obtain Fe3O4-CS-GO；
3) Sieving attapulgite with 200 mesh sieve, adding 10% (w/w) hydrochloric acid solution, high-speed stirring with high shear dispersion emulsifying machine for 10min, standing for 24 hr, centrifuging, washing with deionized water to AgNO3Detection of Cl-free-Drying for later use; dissolving 20g of tetrabutyl titanate in 100mL of absolute ethanol, adding 5mL of triethanolamine and 0.3mmol of FeNO3Uniformly stirring, then dripping 5% (w/w) nitric acid under rapid stirring to form transparent yellow sol, adding 2g of acidified attapulgite into the sol, uniformly stirring, then adding 0.5g of polyethylene glycol, stirring for 1h, then ultrasonically mixing for 1h, and aging for 8h to obtain gel; putting the gel into a muffle furnace, heating to 200 ℃ for heat treatment for 30min, heating to 400 ℃ for heat treatment for 2h, heating to 650 ℃ for heat treatment for 2h, cooling, and grinding to obtain TiO2-ATP；
4) 2g of Fe3O4-CS-GO with 5g TiO2Mixing and dispersing ATP in deionized water, putting the mixture into a pressure kettle, heating to the pressure of 2MPa, starting ultrasound, mixing for 5 hours, then decompressing and cooling, centrifugally separating insoluble substances, drying at 50 ℃, and grinding to obtain the magnetic graphene-TiO2And (c) a complex.
The sewage that will contain different pollutants passes through the device to be handled, detects that pollutant concentration calculates the clearance before sewage treatment and after handling, and the aquatic dissolved oxygen volume calculates the increase rate before detecting the processing, and the data is shown in the following table:
| contaminants | Initial concentration mg/L | Removal rate% | Increase rate of dissolved oxygen% |
| 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 the magnetic graphene oxide photocatalyst composite is used for 30 days, the magnet is removed, the magnetic graphene oxide photocatalyst composite is washed down, collected and concentrated, and the magnetic graphene oxide photocatalyst composite is dispersed on a thin plate after acid washing, alkali washing and alcohol washing and is reused; and collecting the washing liquid, carrying out reduced pressure concentration, detecting the components of the washing liquid, and detecting the undetected pollutants to prove that the pollutants are basically decomposed by the magnetic graphene oxide photocatalytic compound.
Example 3
Magnetic graphene-TiO2The photochemical biological sewage treatment device comprises a thin plate, a magnetic substance and an ultraviolet lamp, wherein the thin plate is horizontally arranged between a sewage inlet and a sewage outlet, a plurality of button-shaped neodymium-iron-boron strong magnets are uniformly fixed under the thin plate, the directions of the magnetic poles are consistent, and the magnetic graphene-TiO are2The compound is uniformly dispersed on the thin plate, and ultraviolet lamps are uniformly distributed on two sides of the upper part of the thin plate; the sheet metal has the polylith for square, is the step and arranges, and the difference in height 20cm between every level, 8 sheet metals are a set of, and every group is the bottom sheet metal and is equipped with the pressure manifold, and the pressure manifold is connected with the elevator pump, and the elevator pump promotes sewage to a set of top sheet metal down, and sheet metal length, width and group number set up according to the volume of coming water.
Magnetic graphene-TiO2An actinic biological sewage treatment method comprising the steps of:
1) mixing magnetic graphene-TiO2The compound is uniformly dispersed on the thin plate;
2) introducing sewage into the thin plate, wherein the thickness of a water layer is less than 5cm, the sewage flows on the thin plate, and the sewage is discharged after the total retention time reaches 3 hours; daylight is used as a light source in the daytime, and an ultraviolet lamp is turned on at night;
3) after 30 days of operation, the magnet is removed, and the magnetic graphene-TiO is added2Under the washing of the compoundThen, the thin plate is dispersed on the thin plate after acid washing, alkali washing and alcohol washing, and the steps are repeated.
Magnetic graphene-TiO2A method of preparing a composite comprising the steps of:
1) 5g of chitosan is dissolved in 200mL of 2% (w/w) acetic acid solution, and 1.5g of nano Fe is added3O450mL of 50% (v/v) glutaraldehyde, vigorously stirring for reacting for 1h, adjusting the pH of the solution to 9-10 by using 10% (w/w) NaOH solution, vigorously stirring for reacting for 2h in a 50 ℃ water bath, centrifugally separating out insoluble substances, washing the insoluble substances to be neutral by using ethanol and deionized water respectively, drying the insoluble substances at 60 ℃, and grinding the insoluble substances to obtain Fe3O4-CS；
2) 4g of Fe3O4Placing CS in 200mL of 2% (w/w) acetic acid solution, adding 1g of graphene oxide prepared by a Hummers method, stirring and reacting for 1h in water bath at 50 ℃, adjusting the pH of the solution to 9-10 by using 10% (w/w) NaOH solution, heating the solution to 80 ℃ in water bath, continuing stirring and reacting for 5h, centrifugally separating insoluble substances, washing the insoluble substances to be neutral by using ethanol and deionized water respectively, drying the insoluble substances at 60 ℃, and grinding the insoluble substances to obtain Fe3O4-CS-GO；
3) Sieving attapulgite with 200 mesh sieve, adding 10% (w/w) hydrochloric acid solution, high-speed stirring with high shear dispersion emulsifying machine for 10min, standing for 24 hr, centrifuging, washing with deionized water to AgNO3Detection of Cl-free-Drying for later use; dissolving 15g of tetrabutyl titanate in 100mL of absolute ethanol, adding 5mL of triethanolamine and 0.12mmol of FeNO3Uniformly stirring, then dripping 5% (w/w) nitric acid under rapid stirring to form transparent yellow sol, adding 2g of acidified attapulgite into the sol, uniformly stirring, then adding 0.5g of polyethylene glycol, stirring for 1h, then ultrasonically mixing for 1h, and aging for 7h to obtain gel; putting the gel into a muffle furnace, heating to 200 ℃ for heat treatment for 30min, heating to 400 ℃ for heat treatment for 2h, heating to 650 ℃ for heat treatment for 2h, cooling, and grinding to obtain TiO2-ATP；
4) 2g of Fe3O4-CS-GO with 3g TiO2Mixing ATP, dispersing in deionized water, placing in a pressure kettle, heating to 1MPa, turning on ultrasonic wave, mixing for 4 hr, relieving pressure, cooling, and centrifuging to separate insoluble substanceDrying the mixture at 50 ℃, and grinding the dried mixture to obtain the magnetic graphene-TiO2And (c) a complex.
The sewage that will contain different pollutants passes through the device to be handled, detects that pollutant concentration calculates the clearance before sewage treatment and after handling, and the aquatic dissolved oxygen volume calculates the increase rate before detecting the processing, and the data is shown in the following table:
| contaminants | Initial concentration mg/L | Removal rate% | Increase rate of dissolved oxygen% |
| 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 the magnetic graphene oxide photocatalyst composite is used for 30 days, the magnet is removed, the magnetic graphene oxide photocatalyst composite is washed down, collected and concentrated, and the magnetic graphene oxide photocatalyst composite is dispersed on a thin plate after acid washing, alkali washing and alcohol washing and is reused; and collecting the washing liquid, carrying out reduced pressure concentration, detecting the components of the washing liquid, and detecting the undetected pollutants to prove that the pollutants are basically decomposed by the magnetic graphene oxide photocatalytic compound.
The present invention has been described in terms of the above embodiments, and it should be understood that the above embodiments are not intended to limit the present invention in any way, and all technical solutions obtained by using equivalents or equivalent changes fall within the protection scope of the present invention.
Claims (5)
1. Magnetic graphene-TiO2The photochemical biological sewage treatment device is characterized by comprising a thin plate, magnetic substances and an ultraviolet lamp, wherein the thin plate is horizontally arranged between a sewage inlet and a sewage outlet, a plurality of magnetic substances are uniformly fixed under the thin plate, the directions of magnetic poles are consistent, and magnetic graphene-TiO is subjected to magnetic field excitation2The compound is uniformly dispersed on the thin plate, and a plurality of ultraviolet lamps are uniformly distributed on two sides of the upper part of the thin plate; the plurality of thin plates are arranged in a step shape, and the height difference between every two adjacent thin plates is 10-20 cm;
the magnetic graphene-TiO2A method of preparing a composite comprising the steps of:
1) dissolving chitosan in 2% w/w acetic acid solution, adding nanometer Fe3O450% v/v glutaraldehyde, vigorously stirring and reacting for 1-2 h, adjusting the pH of the solution to 9-10 with 10% w/w NaOH solution, vigorously stirring and reacting for 1-2 h in a water bath at 50 ℃, centrifugally separating out insoluble substances, washing the insoluble substances to be neutral with ethanol and deionized water respectively, and drying at 60 ℃ to obtain Fe3O4-CS; the chitosan and the nano Fe3O4The weight ratio of (A) to (B) is 5: 1-2;
2) mixing Fe3O4Placing CS in 2% w/w acetic acid solution, adding graphene oxide, stirring and reacting for 1-2 h in 50 ℃ water bath, adjusting the pH of the solution to 9-10 by using 10% w/w NaOH solution, heating to 80 ℃ in water bath, continuing stirring and reacting for 4-5 h, centrifugally separating insoluble substances, washing to be neutral by using ethanol and deionized water respectively, and drying at 60 ℃ to obtain Fe3O4-CS-GO; said Fe3O4The weight ratio of CS to graphene oxide is 3-5: 1;
3) sieving attapulgite with 200 mesh sieve, adding 10% w/w hydrochloric acid solution, stirring at high speed for 10min, standing for 24 hr, centrifuging, washing with deionized water to Cl-(ii) a Adding Fe with the amount of 0.1-0.5% of Ti substance into an ethanol solution of tetrabutyl titanate3+(ii) a Carrying out heat treatment on the gel at 200 ℃ for 30min, then heating to 400 ℃ for heat treatment for 1.5-2 h, and finally heating to 650 ℃ for heat treatment for 2 h; to obtain TiO2-ATP; the weight ratio of the attapulgite to the tetrabutyl titanate is1:15~20；
4) Mixing Fe3O4-CS-GO with TiO2Mixing and dispersing ATP in deionized water, ultrasonically mixing, putting into a pressure kettle, heating to the pressure of 0.5-2 MPa, keeping for 2-5 h, then decompressing, cooling, separating insoluble substances, and drying to obtain Fe3O4-CS-GO-TiO2-ATP; said Fe3O4-CS-GO with TiO2The weight ratio of ATP is 1-2: 3-5.
2. The magnetic graphene-TiO according to claim 12The photochemical biological sewage treatment device is characterized in that the thin plate is rectangular, water retaining strips are arranged on two sides of the thin plate, 8-10 thin plates form a group, a collecting pipe is arranged on the lowest thin plate of each group and connected with a lifting pump, and the lifting pump lifts sewage to the highest thin plate of the next group.
3. The magnetic graphene-TiO according to claim 12The photochemical biological sewage treatment device is characterized in that the thin plates are circular, the sewage pipes are arranged in an umbrella shape at the circle center of each thin plate, the sewage pipes are opened above the uppermost thin plate, the diameter of each thin plate is 40-50 cm larger than that of the adjacent upper thin plate, 8-10 thin plates are in one group, the lowest thin plate in each group is provided with a collecting pipe, the collecting pipe is connected with a lifting pump, and the lifting pump lifts sewage to the next group of thin plates.
4. Use of the magnetic graphene-TiO according to claim 12Magnetic graphene-TiO (titanium dioxide) treatment device for photochemical biological sewage2The method for treating the photochemical biological sewage is characterized by comprising the following steps:
1) mixing magnetic graphene-TiO2The compound is uniformly dispersed on the thin plate;
2) introducing sewage into the thin plate, wherein the thickness of a water layer is less than 5cm, the sewage flows on the thin plate, and the sewage is discharged after the total retention time reaches 3 hours; daylight is used as a light source in the daytime, and an ultraviolet lamp is turned on at night;
3) after 30 days of operation, the magnet is removed, and the magnetic graphene-TiO is added2Compound punchAnd washing, dispersing on the thin plate after acid washing, alkali washing and alcohol washing, and repeating the steps.
5. The magnetic graphene-TiO of claim 42The photochemical biological sewage treatment method is characterized in that the magnetic graphene-TiO2A method of preparing a composite comprising the steps of:
1) dissolving chitosan in 2% w/w acetic acid solution, adding nanometer Fe3O450% v/v glutaraldehyde, vigorously stirring and reacting for 1-2 h, adjusting the pH of the solution to 9-10 with 10% w/w NaOH solution, vigorously stirring and reacting for 1-2 h in a water bath at 50 ℃, centrifugally separating out insoluble substances, washing the insoluble substances to be neutral with ethanol and deionized water respectively, and drying at 60 ℃ to obtain Fe3O4-CS; the chitosan and the nano Fe3O4The weight ratio of (A) to (B) is 5: 1-2;
2) mixing Fe3O4Placing CS in 2% w/w acetic acid solution, adding graphene oxide, stirring and reacting for 1-2 h in 50 ℃ water bath, adjusting the pH of the solution to 9-10 by using 10% w/w NaOH solution, heating to 80 ℃ in water bath, continuing stirring and reacting for 4-5 h, centrifugally separating insoluble substances, washing to be neutral by using ethanol and deionized water respectively, and drying at 60 ℃ to obtain Fe3O4-CS-GO; said Fe3O4The weight ratio of CS to graphene oxide is 3-5: 1;
3) sieving attapulgite with 200 mesh sieve, adding 10% w/w hydrochloric acid solution, stirring at high speed for 10min, standing for 24 hr, centrifuging, washing with deionized water to Cl-(ii) a Adding Fe with the amount of 0.1-0.5% of Ti substance into an ethanol solution of tetrabutyl titanate3+(ii) a Carrying out heat treatment on the gel at 200 ℃ for 30min, then heating to 400 ℃ for heat treatment for 1.5-2 h, and finally heating to 650 ℃ for heat treatment for 2 h; to obtain TiO2-ATP; the weight ratio of the attapulgite to the tetrabutyl titanate is 1: 15-20;
4) mixing Fe3O4-CS-GO with TiO2Mixing and dispersing ATP in deionized water, ultrasonically mixing, putting into a pressure kettle, heating to the pressure of 0.5-2 MPa, keeping for 2-5 h, then decompressing, cooling, separating insoluble substances, and drying to obtain Fe3O4-CS-GO-TiO2-ATP; said Fe3O4-CS-GO with TiO2The weight ratio of ATP is 1-2: 3-5.
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| 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 |
| 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 |
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| CN109954518A (en) | 2019-07-02 |
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