CN114890498B - Operation method of circulating photocatalytic device - Google Patents
Operation method of circulating photocatalytic device Download PDFInfo
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- CN114890498B CN114890498B CN202210473341.5A CN202210473341A CN114890498B CN 114890498 B CN114890498 B CN 114890498B CN 202210473341 A CN202210473341 A CN 202210473341A CN 114890498 B CN114890498 B CN 114890498B
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- 238000000034 method Methods 0.000 title claims abstract description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000010842 industrial wastewater Substances 0.000 claims abstract description 43
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000002028 Biomass Substances 0.000 claims description 22
- 239000004408 titanium dioxide Substances 0.000 claims description 18
- 238000005192 partition Methods 0.000 claims description 15
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- 238000001914 filtration Methods 0.000 claims description 7
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- 239000002131 composite material Substances 0.000 abstract description 56
- 239000000463 material Substances 0.000 abstract description 23
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000004065 wastewater treatment Methods 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 241000209094 Oryza Species 0.000 description 16
- 235000007164 Oryza sativa Nutrition 0.000 description 16
- 235000009566 rice Nutrition 0.000 description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- 238000007146 photocatalysis Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 238000012545 processing Methods 0.000 description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- 239000004202 carbamide Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 235000015099 wheat brans Nutrition 0.000 description 8
- 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 7
- 229940012189 methyl orange Drugs 0.000 description 7
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- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
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- 239000002351 wastewater Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 238000001000 micrograph Methods 0.000 description 1
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- 238000010899 nucleation Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000010908 plant waste Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses an operation method of a circulating photocatalytic device, and the photocatalytic composite material has a spherical structure, so that the separation capability of photo-generated electron hole pairs can be improved, the utilization rate of the material to visible light is greatly improved, and the photocatalytic composite material has good catalytic performance under the visible light. The invention utilizes the light guiding column to guide the light irradiated by the surface of the filter plate between the two layers of filter plates through refraction, effectively solves the problem of poor contact between the light and anatase titanium dioxide particles during industrial wastewater treatment, can relieve the problem of poor catalysis caused by shielding of the filter plate and industrial wastewater on photocatalytic materials, and furthest plays the catalysis performance of the fluorocarbon co-doped anatase titanium dioxide composite material.
Description
Technical Field
The invention relates to the field of photocatalytic materials, in particular to an operation method of a circulating photocatalytic device.
Background
Semiconductor materials generally used as photocatalysts are mostly metal oxides, metal sulfides and metal nitrides, and have enough forbidden band width for catalytic reaction. The photocatalytic material must satisfy that the material itself has a certain reducing power in the energy band region H2O/OH < (e0= -2.8 v), and the material itself must have a certain stability. Titanium dioxide (eg=3.2 eV) has the advantages of high photocatalytic activity, chemical and biological inertness, chemical and photo corrosion resistance, low cost, abundant raw material sources and the like, so that titanium dioxide is one of the most widely studied, promising and focused semiconductor materials in photocatalytic materials. Because the forbidden bandwidth of the titanium dioxide is about 3.2eV, the photocatalytic reaction can only be carried out in the ultraviolet light region in sunlight, and the ultraviolet light part in the solar spectrum only occupies about 4 percent, so that the use of the titanium dioxide catalytic material is greatly limited. The nitrogen doping can lead the absorption of titanium dioxide to be red shifted, and has certain catalytic performance under visible light, but the synthesis process is relatively complex.
The titanium dioxide photocatalyst has wide application prospect in the fields of environmental pollution treatment and the like, but has high catalytic activity only under the excitation of ultraviolet light, and the energy share of the ultraviolet light in sunlight is lower than 5 percent, so that a great deal of research is devoted to expanding the photo-response area of the titanium dioxide to develop the photo-catalytic performance of the titanium dioxide photocatalyst under the irradiation of visible light in order to fully utilize the sunlight. Research shows that doping fluorine element into anatase titania photocatalyst crystal can shift the absorption wavelength of titania photocatalyst to red, so as to absorb in visible light range. Doping with carbon element can also cause red shift of absorption wavelength of the titanium dioxide photocatalyst.
The prior art adopts a high temperature or calcination mode to carry out physical doping of free carbon in the preparation of carbon doped anatase titanium dioxide, because the amorphous titanium dioxide needs to be converted into the anatase titanium dioxide, and the carbon element is also doped at high temperature or calcination, usually above 900 ℃, and the special structure and characteristic of the carbon element are destroyed in the high temperature or calcination process. The carbon doped anatase titanium dioxide produced by the calcination process does not involve chemical doping of the carbon-containing groups.
In the prior art, the anatase titanium dioxide can be prepared on the surface of the solid carrier by a wet-heat method, the wet-heat method needs to be prepared in a high-pressure reaction kettle at the temperature of 80-200 ℃, the conditions are harsh, the solid carrier cannot be carbonized at a lower temperature, free carbon is not generated, and carbon doping cannot be performed while the anatase titanium dioxide is formed by deposition.
In addition, when some existing granular photocatalytic materials are used for treating substrates such as industrial wastewater, certain space fixing is needed for the granular photocatalytic materials, the conventional method comprises the steps of binding fine granular materials into spheres, then immersing the spheres in water permeable bags for wastewater treatment, or pressing and clamping the spheres in filter plates to enable the industrial wastewater to finish wastewater treatment through the granular photocatalytic materials, so that although smaller granular materials can be prevented from escaping along with water flow, the contact area between the granular materials and the wastewater can be reduced to reduce the treatment efficiency, more importantly, due to shielding of the industrial wastewater and the filter plates, the conventional industrial wastewater treatment operation can cause light to difficultly enter the photocatalytic materials, the granular photocatalytic materials cannot fully contact visible light, even when the concentration of the wastewater is high, the illumination intensity of the surface of the photocatalytic materials is difficult to ensure, the photocatalytic materials cannot contact enough light, the catalytic efficiency is greatly reduced, and the application of the photocatalytic materials in the wastewater treatment is seriously affected.
Disclosure of Invention
The invention aims to solve the technical problems that: solves the problem of poor internal light transmission of the prior photocatalytic material in the application process.
In order to solve the technical problems, the invention provides the following technical scheme:
the operation method of the circulating photocatalytic device comprises the steps of filling biomass-based spherical anatase titanium dioxide particles into the circulating photocatalytic device to perform photocatalytic degradation on industrial wastewater, wherein the steps are as follows:
(1) Loading and fixing biomass-based spherical anatase titanium dioxide particles into a plate-shaped treatment unit, and then inserting the plate-shaped treatment unit into a circulating treatment tank;
(2) The industrial wastewater to be treated is circularly injected into the upper surface of the plate-shaped treatment unit, filtered by the plate-shaped treatment unit from top to bottom and enters a circulation tank, and the industrial wastewater in the circulation tank is repeatedly injected into the upper part of the plate-shaped treatment unit through a circulation system to finish repeated catalytic treatment;
(3) The industrial wastewater is circularly treated, a light source is arranged above the plate-shaped treatment unit, a plurality of light guide columns extend out of the top of the plate-shaped treatment unit, and the light guide columns are leveled with or extend out of the liquid level of the industrial wastewater to be treated.
Preferably, the biomass-based spherical anatase titanium dioxide particles are obtained by loading spherical anatase titanium dioxide on the surface of biomass; wherein the mass content of the biomass is 70-98%, the mass content of the spherical anatase titanium dioxide is 2-30%, and fluorine elements and carbon elements are doped in the spherical anatase titanium dioxide.
Preferably, the circulating photocatalytic device comprises a tank body, a plate-shaped processing unit is slidably connected to the upper portion of the tank body, a light source is arranged at the top of the tank body, the light source is arranged above the plate-shaped processing unit, when industrial wastewater is filtered through the plate-shaped processing unit from top to bottom, the plate-shaped processing unit introduces light into the interior of the plate-shaped processing unit to irradiate biomass-based spherical anatase titanium dioxide particles and photocatalytic-degrade industrial wastewater, a circulating groove is formed in the bottom of the tank body, a water outlet is formed in the bottom of the circulating groove, a circulating pipe is arranged on the water outlet, the upper end of the circulating pipe is opened at the top of the tank body, and a circulating pump is arranged in the middle of the circulating pipe.
Preferably, the platy treatment unit comprises a frame, the both sides of frame are equipped with the draw runner, the frame passes through draw runner and cell body upper portion sliding connection, the bottom sliding connection of frame has the lower filter plate, the top surface detachably of frame is connected with the upper filter plate, be equipped with a plurality of diaphragms and longitudinal baffle in the frame, diaphragm and longitudinal baffle divide into a plurality of square with frame internal partition, biomass-based spherical anatase titanium dioxide granule material fills in the square, the intersection of diaphragm and longitudinal baffle is equipped with the light-guiding column, the upper portion of light-guiding column wears out the upper filter plate and seals the grafting with the upper filter plate, the light source is located the top of light-guiding column and upper filter plate, still be equipped with the manger plate on the four walls of frame, be equipped with the inlet opening on the manger plate, the upper side is located to the inlet opening of circulating pipe is worn out by the inlet opening, the circulation tank is located and is down filter plate below.
The beneficial effects obtained by the invention are as follows:
the invention uses urea as precipitant, sodium fluotitanate or ammonium fluotitanate as titanium source by homogeneous precipitation method under normal pressure, uses rice husk, rice straw, wheat husk, wheat straw and other material surfaces and edges with a large amount of oxygen-containing functional groups (such as hydroxyl, carboxyl and the like) as nucleation centers, and self-assembles at low temperature (100 ℃) to generate the fluorocarbon co-doped anatase type titanium dioxide composite material. The main raw materials of the invention are derived from crop wastes, and the invention is energy-saving and environment-friendly. The photocatalytic composite material has a spherical structure, so that the separation capability of photo-generated electron hole pairs can be improved, the utilization rate of the material on visible light is greatly improved, and the photocatalytic composite material has good catalytic performance under visible light.
The invention adopts the light guiding column to guide the light irradiated by the surface of the filter plate between the two layers of filter plates through refraction, effectively solves the problem of poor contact between the light and anatase titanium dioxide particles during industrial wastewater treatment, can relieve the problem of poor catalysis caused by shielding of the filter plate and industrial wastewater on photocatalytic materials, and furthest plays the catalysis performance of the fluorocarbon co-doped anatase titanium dioxide composite material.
Drawings
FIG. 1 is a field emission scanning electron microscope image of the photocatalytic composite material prepared in example 1;
FIG. 2 is an XRD pattern of the photocatalytic composite material prepared in example 1;
FIG. 3 is an ultraviolet-visible diagram of the photocatalytic composite material prepared in example 1;
fig. 4 is a graph showing the effect of photocatalytic methyl orange under visible light excitation of the photocatalytic composite material prepared in example 1.
FIG. 5 is a schematic diagram of the overall structure of a circulating photocatalytic device;
FIG. 6 is a top view of a circulating photocatalytic device;
FIG. 7 is a cross-sectional view taken along B-B in FIG. 6;
FIG. 8 is a cross-sectional view taken along line C-C of FIG. 6;
fig. 9 is a schematic view of the internal structure of the plate-shaped processing unit.
The device comprises a 1-groove body, a 11-circulation groove, a 12-water outlet, a 2-frame, a 21-lower filter plate, a 22-slide bar, a 23-diaphragm plate, a 24-light-guiding column, a 25-water inlet, a 26-water baffle, a 27-longitudinal baffle plate, a 28-upper filter plate, a 3-light source, a 4-circulation pipe and a 41-circulation pump.
Detailed Description
The following description of the embodiments of the present invention is provided to facilitate a more complete, accurate and thorough understanding of the present invention's inventive concepts and technical solutions by those skilled in the art.
Example 1: the novel photocatalytic composite material is prepared according to the following method:
(1) Cleaning and drying rice hulls to obtain clean rice hulls;
(2) 0.6mol/L ammonium fluotitanate, 0.6mol/L urea and 0.02wt% hydrogen peroxide are mixed according to the ratio of 2.2L: mixing 100g of the mixture with the rinsed rice hulls, and soaking for 1h at 26 ℃ to obtain a composite material precursor; in the invention, hydrogen peroxide is used as a bleaching agent, and urea is used as a precipitant.
(3) Heating the reaction liquid to 90 ℃, reacting for 3 hours, and filtering to obtain a photocatalysis composite material;
(4) Washing, drying and crushing the obtained photocatalysis composite material to obtain biomass-based spherical anatase titanium dioxide particles.
As can be seen from fig. 2: the XRD spectra of the prepared composite materials were all matched with those of anatase titania, and fig. 2 shows that no characteristic peaks of rutile phase and brookite titania were found in the prepared samples, and no carbon atom peaks were found, probably because the carbon material surface was covered with a large amount of titania nanoparticles and grown at specific positions. Firstly, the titanium dioxide crystal is wrapped on the surface of the rice husk, so that the exposed peak of the rice husk is shielded by the peak of the titanium dioxide crystal, secondly, as can be seen from an SEM image, the substrate is the rice husk, and the surface of the substrate is wrapped by a large amount of titanium dioxide crystal.
The structure of the photocatalytic composite material was observed using a field emission scanning electron microscope, and the result is shown in fig. 1. As can be seen from fig. 1: the surface of the rice hull is covered with a layer of spherical titanium dioxide nano particles, the special morphology of the surface of the rice hull provides guiding conditions for the formation of the titanium dioxide nano particles, and finally the photocatalytic composite material is obtained, wherein the spherical titanium dioxide is supported on the surface of the flaky rice hull.
Fig. 3 shows the uv-vis absorption spectrum of the photocatalytic composite material according to the present embodiment, and the result is shown in fig. 3. As can be seen from fig. 3, the photocatalytic composite material absorbs in the entire uv-visible region, indicating that the photocatalytic composite material has a certain activity under visible light.
The application of the photocatalytic composite material prepared in the embodiment to simulated industrial wastewater comprises the following steps:
0.01g of the photocatalytic composite material is ultrasonically dispersed into a 50mL beaker which is filled with 20mg/L of methyl orange and is cooled by circulating water, sampling is carried out every 15 minutes under the irradiation of simulated visible light, the ultraviolet-visible absorption spectrum of the photocatalytic composite material is measured by an ultraviolet-visible spectrophotometer, and the degradation condition of the photocatalytic composite material is observed. The photocatalytic composite material of the example can degrade methyl orange to below 20% in 90 minutes under the excitation of visible light.
Example 2 a method for preparing a photocatalytic composite material:
(1) Primarily cutting, cleaning and drying the rice straw to obtain clean rice straw;
(2) 0.15mol/L ammonium fluotitanate, 0.3mol/L urea and 0.01wt% hydrogen peroxide are mixed according to the following ratio of 1.8L: mixing 100g of the mixture with the rinsed rice straw, and soaking the mixture at 24 ℃ for 0.5h to obtain a composite material precursor;
(3) Heating the reaction liquid to 80 ℃, reacting for 0.5h, and filtering to obtain a photocatalysis composite material;
(4) Washing, drying and crushing the obtained photocatalysis composite material to obtain biomass-based spherical anatase titanium dioxide particles.
The application of the photocatalytic composite material prepared in the embodiment to simulated industrial wastewater comprises the following steps:
0.01g of the photocatalytic composite material is ultrasonically dispersed into a 50mL beaker which is filled with 20mg/L of methyl orange and is cooled by circulating water, sampling is carried out every 15 minutes under the irradiation of simulated visible light, the ultraviolet-visible absorption spectrum of the photocatalytic composite material is measured by an ultraviolet-visible spectrophotometer, and the degradation condition of the photocatalytic composite material is observed. The photocatalytic composite material of the example can degrade methyl orange to below 25% in 90 minutes under the excitation of visible light.
Example 3 a method for preparing a photocatalytic composite material:
(1) Cleaning wheat bran, and drying to obtain clean wheat bran;
(2) 0.8mol/L of sodium fluotitanate, 0.8mol/L of urea and 0.025wt% of hydrogen peroxide are mixed according to the following ratio of 2.5L: mixing 100g of the mixture with rinsed wheat bran, and soaking at 28 ℃ for 1.5 hours to obtain a composite material precursor;
(3) Heating the reaction liquid to 95 ℃, reacting for 4 hours, and filtering to obtain a photocatalysis composite material;
(4) Washing, drying and crushing the obtained photocatalysis composite material to obtain biomass-based spherical anatase titanium dioxide particles.
The application of the photocatalytic composite material prepared in the embodiment to simulated industrial wastewater comprises the following steps:
0.01g of the photocatalytic composite material is ultrasonically dispersed into a 50mL beaker which is filled with 20mg/L of methyl orange and is cooled by circulating water, sampling is carried out every 15 minutes under the irradiation of simulated visible light, the ultraviolet-visible absorption spectrum of the photocatalytic composite material is measured by an ultraviolet-visible spectrophotometer, and the degradation condition of the photocatalytic composite material is observed. The photocatalytic composite material of the example can degrade methyl orange to below 15% in 90 minutes under the excitation of visible light.
Example 4 a method for preparing a photocatalytic composite material:
(1) Cleaning wheat straw, and drying to obtain clean wheat bran;
(2) 0.1mol/L ammonium fluotitanate, 0.1mol/L urea and 0.01wt% hydrogen peroxide are mixed according to the following ratio of 1L: mixing 100g of the mixture with the rinsed wheat straw, and soaking the mixture at 22 ℃ for 0.5h to obtain a composite material precursor;
(3) Heating the reaction liquid to 70 ℃, reacting for 0.5h, and filtering to obtain a photocatalysis composite material;
(4) Washing, drying and crushing the obtained photocatalysis composite material to obtain biomass-based spherical anatase titanium dioxide particles.
Example 5 a method for preparing a photocatalytic composite material:
(1) Cleaning wheat bran, and drying to obtain clean wheat bran;
(2) 1mol/L sodium fluotitanate, 6.0mol/L urea and 0.03wt% hydrogen peroxide are mixed according to the following proportion of 3L: mixing 100g of the mixture with rinsed wheat bran, and soaking for 0.5h at 30 ℃ to obtain a composite material precursor;
(3) Heating the reaction liquid to 100 ℃, reacting for 0.5h, and filtering to obtain a photocatalysis composite material;
(4) Washing, drying and crushing the obtained photocatalysis composite material to obtain biomass-based spherical anatase titanium dioxide particles.
Example 6 a method for preparing a photocatalytic composite material:
(1) Cleaning rice hulls, and drying to obtain clean wheat bran;
(2) 0.01mol/L ammonium fluotitanate, 0.1mol/L urea and 0.01wt% hydrogen peroxide are mixed according to the following ratio of 1L: mixing 10g of the mixture with the rinsed rice hulls, and soaking for 2 hours at 20 ℃ to obtain a composite material precursor;
(3) Heating the reaction liquid to 65 ℃, reacting for 5 hours, and filtering to obtain a photocatalysis composite material;
(4) Washing, drying and crushing the obtained photocatalysis composite material to obtain biomass-based spherical anatase titanium dioxide particles.
Example 7: the biomass-based spherical anatase titanium dioxide particles prepared in examples 1 to 6 are filled into a circulating photocatalytic device to perform photocatalytic degradation on industrial wastewater.
The circulating photocatalytic device adopted in the invention comprises a tank body 1, wherein the upper part of the tank body 1 is connected with a plate-shaped processing unit in a sliding manner, the top of the tank body 1 is provided with a light source 3, the light source 3 is arranged above the plate-shaped processing unit, the bottom of the tank body 1 is provided with a circulating groove 11, the bottom of the circulating groove 11 is provided with a water outlet 12, the water outlet 12 is provided with a circulating pipe 4, the upper end of the circulating pipe 4 is opened at the top of the tank body 1, and the middle part of the circulating pipe 4 is provided with a circulating pump 41.
The plate-shaped treatment unit comprises a frame 2, slide bars 22 are arranged on two sides of the frame 2, the frame 2 is in sliding connection with the upper portion of the tank body 1 through the slide bars 22, a lower filter plate 21 is in sliding connection with the bottom of the frame 2, an upper filter plate 28 is detachably connected to the top surface of the frame 2, a plurality of transverse partition plates 23 and longitudinal partition plates 27 are arranged in the frame 2, the transverse partition plates 23 and the longitudinal partition plates 27 divide the interior of the frame 2 into a plurality of square grids, a light guiding column 24 is arranged at the intersection of the transverse partition plates 23 and the longitudinal partition plates 27, the upper portion of the light guiding column 24 penetrates out of the upper filter plate 28 and is in sealing connection with the upper filter plate 28, a light source 3 is arranged above the light guiding column 24 and the upper filter plate 28, a water baffle 26 is further arranged on the four walls of the frame 2, a water inlet 25 is arranged on the water baffle 26, an upper port of the circulating pipe 4 penetrates out of the water inlet 25, and the circulating groove 11 is arranged below the lower filter plate 21. The lower part of the light-guiding column 24 is contacted with biomass-based spherical anatase titanium dioxide granules in the square, and the light-guiding column 24, the transverse partition plate 23 and the longitudinal partition plate 27 are made of transparent plastics or transparent glass, so that light can be refracted and transmitted efficiently.
The specific flow of carrying out photocatalysis treatment on industrial wastewater by using the circulating photocatalysis device is as follows:
firstly, the upper filter plate 28 is taken down, the lower filter plate 21 is installed, the biomass-based spherical anatase titanium dioxide particles are uniformly filled in the square, the upper filter plate 28 is covered, the upper filter plate 28 is provided with jacks corresponding to the light-guiding columns 24, the light-guiding columns 24 penetrate out of the jacks and are in sealing connection with the upper filter plate 28 during plugging, and the assembly preparation of the device is completed after the installed plate-shaped processing units are inserted into the groove body 1.
When industrial wastewater is treated, the industrial wastewater is injected into the circulating groove 11, the industrial wastewater is pumped into the surface of the upper filter plate 28 from the circulating groove 11 through the circulating pipe 4 and the circulating pump 41, the water baffle 26 is used for accumulating the industrial wastewater with a certain depth, so that the industrial wastewater can uniformly pass through the plate-shaped treatment unit from top to bottom, but the depth of the industrial wastewater on the surface of the upper filter plate 28 is controlled, the top end of the light guide column 24 is preferably flush with the water surface of the industrial wastewater or the top end of the light guide column 24 is higher than the water surface of the industrial wastewater, the light source 3 is turned on, the industrial wastewater continuously permeates and filters the biomass-based spherical anatase titanium dioxide particles in the square, the light guide column 24 guides the upper light into the square around the square through the refraction effect and irradiates the biomass-based spherical anatase titanium dioxide particles, the irradiation intensity of the internal particles is greatly improved, and favorable conditions are provided for playing the photocatalytic degradation effect of the particles to the maximum extent. After the industrial wastewater is treated, the frame 2 is pulled out, and then the lower filter plate 21 is pulled out, so that the used particles can be conveniently removed or replaced.
The above embodiments are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by the above embodiments, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the present invention; the technology not related to the invention can be realized by the prior art.
Claims (1)
1. The operation method of the circulating photocatalytic device is characterized in that the circulating photocatalytic device comprises a tank body (1), a platy treatment unit is connected to the upper portion of the tank body (1) in a sliding mode, a light source (3) is arranged at the top of the tank body (1), the light source (3) is arranged above the platy treatment unit, when industrial wastewater is filtered through the platy treatment unit from top to bottom, the platy treatment unit introduces light into the inside of the platy treatment unit to irradiate biomass-based spherical anatase titanium dioxide particles and photocatalytic degrade the industrial wastewater, a circulating groove (11) is formed in the bottom of the tank body (1), a water outlet (12) is formed in the bottom of the circulating groove (11), a circulating pipe (4) is arranged on the water outlet (12), the upper end of the circulating pipe (4) is opened at the top of the tank body (1), and a circulating pump (41) is arranged in the middle of the circulating pipe (4);
the plate-shaped treatment unit comprises a frame (2), slide bars (22) are arranged on two sides of the frame (2), the frame (2) is in sliding connection with the upper part of a tank body (1) through the slide bars (22), a lower filter plate (21) is in sliding connection with the bottom of the frame (2), an upper filter plate (28) is detachably connected with the top surface of the frame (2), a plurality of transverse partition plates (23) and longitudinal partition plates (27) are arranged in the frame (2), the interior of the frame (2) is divided into a plurality of square grids by the transverse partition plates (23) and the longitudinal partition plates (27), a light guiding column (24) is arranged at the junction of the transverse partition plates (23) and the longitudinal partition plates (27), the upper part of the light guiding column (24) penetrates out of the upper filter plate (28) and is in sealing connection with the upper filter plate (28), a plurality of water blocking plates (26) are further arranged on four walls of the frame (2), a water blocking plate (26) is arranged on the upper filter plate (28), a water inlet port (25) is arranged on the water blocking plate (25), the circulating groove (11) is arranged below the lower filter plate (21);
the operation method of the circulating photocatalytic device specifically comprises the following steps:
the method comprises the steps of removing an upper filter plate (28), installing a lower filter plate (21), uniformly filling biomass-based spherical anatase titanium dioxide particles in squares, covering the upper filter plate (28), enabling a light guide column (24) to penetrate out of an insertion hole and be in sealing connection with the upper filter plate (28), inserting an installed platy treatment unit into a groove body (1), injecting industrial wastewater into a circulating groove (11) when industrial wastewater is treated, pumping the industrial wastewater into the surface of the upper filter plate (28) through the circulating groove (4) and a circulating pump (41), accumulating the industrial wastewater in a water baffle (26), enabling the top end of the light guide column (24) to be flush with the industrial wastewater surface or enabling the top end of the light guide column (24) to be higher than the industrial wastewater surface, enabling the industrial wastewater to continuously permeate through platy treatment units from top to bottom, filtering the light source (3), enabling the upper light guide column (24) to guide the light of the biomass-based spherical anatase titanium dioxide particles in the square to be introduced into the periphery of the square through refraction effect, and irradiating the biomass-based spherical titanium dioxide particles, and removing the industrial wastewater after the industrial wastewater is pumped out of the frame (21), and removing the industrial wastewater particles after the industrial wastewater is completely removed.
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