CN112387270B - Photocatalytic material for eliminating VOCs and ozone and multilayer-hole-plate type photocatalytic reactor - Google Patents
Photocatalytic material for eliminating VOCs and ozone and multilayer-hole-plate type photocatalytic reactor Download PDFInfo
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D—SEPARATION
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Abstract
The invention discloses a method for preparing VOCs and O3Eliminated photocatalytic material and a multi-layer orifice plate photocatalytic reactor. The preparation method of the composite photocatalytic material comprises the following steps: adopting a hydrothermal method to prepare nano YVO4Materials and nano TiO2The precursor is reacted to synthesize YVO in one step4/TiO2The composite material is loaded on the polytetrafluoroethylene net; YVO4/TiO2The surface of the composite material is impregnated by concentrated HCl to obtain the loaded YVO4/TiO2A composite photocatalytic material. Based on load type YVO4/TiO2The invention also provides a multilayer porous plate type reactor, which is used for solving the problems of insufficient light contact, low efficiency and the like in the application process of photocatalytic amplification. The multilayer pore plate type photocatalytic reactor provided by the invention has better airflow resistance and heat dissipation design, and is high in safety and reliability. The module is replaceable and easy to maintain. As an example of the application of photocatalysis amplification, the invention can treat polluted gas with large wind quantity.
Description
Technical Field
The invention relates to a photocatalytic material for eliminating VOCs and ozone and a multilayer-pore-plate type photocatalytic reactor.
Background
In recent years, with increasingly prominent environmental pollution, the air quality problem is more and more highlighted. Among them, benzene is a common aromatic volatile organic pollutant, and is determined as a strong carcinogen by the international organization. With TiO2The semiconductor photocatalytic oxidation technology which is mainly used is an ideal environmental pollution treatment technology gradually with the advantages of low cost, safety, no toxicity, mild reaction conditions, capability of thoroughly mineralizing organic pollutants and the like. Research shows that the photocatalysis technology can degrade benzene to a certain extent, so that pollution is treated, but common TiO2The photocatalyst has obviously low degradation efficiency to benzene, and needs ultraviolet light excitation, so that the practical application effect is greatly reduced. Therefore, it is needless to say that both theoretical and practical meanings of developing a photocatalyst capable of efficiently degrading aromatic volatile organic contaminants such as benzene under visible light irradiation are important.
TiO2Although the method has great disadvantages in practical application, the method has extremely strong chemical stability and compatibility and unique properties of Ti-O bonds, and conditions are created for further modification. Martra et al (Martra G., applied. catalysis A,2000,200(2):275-2And the absorption capacity to visible light realizes visible light excitation. Xie et al (Xie Y B., environ. Sci. Technol.,1995,29:841-843.) use high temperature calcination to intercalate metal ions into TiO2In the crystal lattice, the physical properties and the catalytic capability of the catalytic material are obviously improved. The two modification methods start from the angle of electron transfer, reduce the recombination rate of current carriers and effectively improve TiO2Photocatalytic activity of (1). In addition, highly active catalytic materials with a visible light response can also be obtained by surface modification, for example dyes prepared from Zhao Cheng et al (Wu T., ZHao J., et al, New J.chem.,2000,24:93-98.)Material photosensitization material and sulfuric acid acidification TiO of Zxianzhi et al (Zxianzhi et al, catalytic science 1999, 20(3):321-2The degradation performance is stronger in liquid phase and gas phase reactions respectively. However, the above modification methods introduce new problems such as decrease in stability, sharp increase in cost, complicated preparation, and the like to a greater or lesser extent. As such, semiconductor heterojunction photocatalytic materials have attracted much attention in the industry due to their remarkable promoting effects, excellent stability, and simple and easy-to-use preparation methods. On the other hand, the photocatalytic reaction is not widely applied, and the main reason is that after the scale-up, the existing reaction device and system cannot ensure sufficient light input quantity, and the photocatalytic reaction cannot be fully generated due to insufficient energy. The only use method at present is to spray photocatalytic liquid to form a film, so that the photocatalytic reaction can be ensured to be carried out under the condition of sufficient illumination, and related results are applied to the surface wall body, the indoor wall surface and the like of a building. However, the process results in a limited effective reaction volume and the contact of the reactants with the catalyst is dependent only on passive gas flow, thus resulting in inefficient reaction.
Disclosure of Invention
The invention aims to provide a YVO4/TiO2C, and based on the catalytic material, a multi-layer pore plate type photocatalytic reactor is provided, which can degrade VOCs and eliminate ozone.
YVO provided by the invention4/TiO2The preparation method of the-C composite photocatalytic material comprises the following steps:
adopting a hydrothermal method to prepare nano YVO4Materials and nano TiO2The precursor is reacted to synthesize YVO in one step4/TiO2The composite material is loaded on the polytetrafluoroethylene net; the YVO4/TiO2The surface of the composite material is impregnated by concentrated HCl to obtain the loaded YVO4/TiO2-C composite photocatalytic material.
In the above preparation method, the hydrothermal method comprises the following steps:
the nano TiO is added2Transferring the precursor into a hydrothermal reaction kettle, adjusting the pH value to 3-4, and adding the precursorThe nanometer YVO4Dispersing materials by ultrasonic waves and continuously stirring for 12-24 hours; placing the polytetrafluoroethylene net in the hydrothermal reaction kettle, reacting at 180-220 ℃ for 24-36 h, sequentially washing with water, washing with alcohol, and drying overnight to obtain the loaded YVO4/TiO2A composite material;
the mesh number of the polytetrafluoroethylene net is 40-60 meshes;
the nanometer YVO4The material comprises the nanometer YVO4Materials and the nano TiO20.01 to 10%, preferably 0.01 to 5%, 0.01 to 2%, 0.01 to 1%, 0.01 to 0.5%, 0.01 to 0.1%, 0.1 to 5%, 0.1 to 2%, 0.1 to 1%, 0.1 to 0.5%, 0.01%, 0.1%, 0.5%, 1%, 2%, 5% or 10%, most preferably 0.1 to 2%, 0.1%, 0.5%, 1% or 2% of the total mass of the precursor.
In the above preparation method, the impregnation step is as follows:
subjecting the YVO to4/TiO2Placing the composite material in concentrated HCl, and sealing and soaking for 24-36 h in a dark place; then ventilating in dark place until concentrated HCl is completely volatilized, and drying to obtain the loaded YVO4/TiO2-C a composite photocatalytic material;
after the material surface is acidified, H helps VOCs decompose and Cl helps ozone elimination.
In the above preparation method, the nano TiO is prepared2The precursor comprises the following steps:
mixing TiCl4Dropwise adding the aqueous solution into NaOH aqueous solution, and stirring at 25-30 ℃ for 2-4 h to obtain nano TiO2A precursor;
wherein, TiCl4The molar ratio to NaOH is 1: 3.8 to 4.
In the preparation method, the nano YVO can be prepared according to a hydrothermal method4The material comprises the following specific steps:
mixing Y (NO)3)3The aqueous solution is added dropwise to NaOH and NH4VO3Stirring the mixed aqueous solution, transferring the mixed aqueous solution into a high-pressure reaction kettle, and reacting at 180-220 ℃ for 24-48 hours to obtain the product;
washing the precipitate with water, washing with alcohol, and oven drying overnight to obtain the final product;
wherein NaOH and NH4VO3In a molar ratio of 1: 0.9 to 1, NH4VO3And Y (NO)3)3In a molar ratio of 1: 0.9 to 1.1.
The load type YVO prepared by the method of the invention4/TiO2the-C composite photocatalytic material has strong visible light catalytic performance, the degradation rate of benzene reaches 70 percent, and CO is2The maximum generation amount can reach 1200 ppm; to O within 10 hours3The elimination rate of (A) is always maintained above 99%.
Based on the load type YVO4/TiO2The invention also provides a multilayer pore plate type reactor, which is used for solving the problems of insufficient light contact, low efficiency and the like in the application process of photocatalytic amplification.
Firstly, a multilayer pore plate type photocatalytic reaction module is provided, and comprises a plurality of metal pore plates A and metal pore plates B which are alternately arranged, wherein holes in the metal pore plates A and holes in the metal pore plates B are arranged in a staggered manner, so that a turbulent flow effect can be achieved, and reaction gas can be uniformly mixed; metal orifice plate A-load type YVO4/TiO2-C-the structure of the metal orifice plate B is a sandwich stacking structure;
the load type YVO is arranged between every two adjacent metal pore plates A and B4/TiO2-C a composite photocatalytic material;
a plurality of light sources are arranged at the hole interval part on the metal hole plate A; the light source and the load type YVO4/TiO2Gaps are arranged between the-C composite photocatalytic materials or the composite photocatalytic materials are in direct contact with the composite photocatalytic materials.
In the multilayer pore plate type photocatalytic reaction module, the metal pore plate A and the metal pore plate B are stainless steel pore plates, and the stainless steel pore plates not only have the functions of structural support and airflow guidance, but also have the function of radiating heat of a light source, so that the safety and the service life are improved;
the light source is an LED lamp bead, can be fixed by heat-conducting silica gel and is used for providing a reaction light source; due to the fact thatYVO4/TiO2The C catalyst has high visible light catalytic performance, so that the LED lamp bead can use a high-power visible light wave band, and the cost is low;
a plurality of the multilayer pore plate type photocatalytic reaction modules can be connected in series according to requirements, and finally the photocatalytic reaction modules are packaged in a closed box body to form a set of complete photocatalytic reactor.
The photocatalytic reactor can fully mix reaction gas under the condition of large air quantity, and the overall resistance is low. The reactor (three-layer reaction unit) is tested to have the photocatalytic oxidation rate of 65% for benzene and the elimination rate of 99% for ozone under the condition of long-time large air quantity, as shown in figure 8.
The invention has the following beneficial effects:
the invention is a load type YVO4/TiO2the-C composite photocatalytic material has higher decomposition capability on VOCs and simultaneously eliminates O3The function of (c). Based on the load type YVO4/TiO2The modular structure of the-C composite photocatalytic material can increase or decrease reaction units according to actual requirements, and has high degradation rate and good stability. The multilayer pore plate type photocatalytic reactor provided by the invention has better airflow resistance and heat dissipation design, and is high in safety and reliability. The module is replaceable and easy to maintain. As an example of the application of photocatalysis amplification, the invention can treat polluted gas with large wind quantity.
Drawings
FIG. 1 shows a load-type YVO of the present invention4/TiO2A preparation flow chart of the-C composite photocatalytic material.
FIG. 2 shows a supported YVO prepared in example 1 of the present invention4/TiO2-TEM image of the composite photocatalytic material C.
FIG. 3 shows YVO prepared in different proportions according to the present invention4/TiO2-XRD pattern of C.
FIG. 4 shows YVO in different proportions under visible light conditions4/TiO2-C degradation rate of benzene and CO2The amount of production.
FIG. 5 shows YVO prepared in example 1 of the present invention under visible light conditions4/TiO2-C elimination rate of ozone.
FIG. 6 is a schematic structural diagram of a multi-layer porous plate type photocatalytic reaction module according to the present invention;
the respective symbols in the figure are as follows:
1 metal orifice plate A,2 metal orifice plate B, 3 load type YVO4/TiO2-C composite photocatalytic material (polytetrafluoroethylene net), 4LED lamp beads.
Fig. 7 is a CFD simulation result of a multi-layer orifice plate type photocatalytic reactor.
FIG. 8 shows the efficiency of eliminating benzene and ozone in a multi-layer plate-type photocatalytic reactor.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1 YVO4/TiO2Preparation of-C composite photocatalytic material
Firstly, a hydrothermal method is adopted to prepare YVO4The nanometer semiconductor material is prepared, and the crystallinity and the light absorption characteristic of the nanometer semiconductor material are improved by adjusting the pH value of the water solvent; then, a hydrothermal method is utilized again to synthesize YVO with a specific composite ratio in one step4/TiO2And loaded to a polytetrafluoroethylene web; finally, the supported YVO can be obtained by concentrated HCl surface impregnation4/TiO2-C. The preparation flow is shown in figure 1:
(1) taking NaOH and NH4VO36mmol of each of them was dissolved in 10ml of deionized water, and dissolved by stirring thoroughly. Preparing 0.5mol/L Y (NO)3)313ml of the solution is dropwise added into the solution, stirred for 2 hours and transferred to a 100ml high-pressure reaction kettle and kept at 200 ℃ for 48 hours. Washing the obtained precipitate with water, washing with alcohol, drying overnight to obtain nanometer YVO4And (3) sampling. In this step, NaOH and NH4VO3In a molar ratio of 1: 1, NH4VO3And Y (NO)3)3In a molar ratio of 1: 1.
(2) 1mol/L of TiCl4Slowly dripping the aqueous solution into 60mol/L NaOHIn the water solution, continuously stirring and maintaining the temperature at 30 ℃ to generate nano TiO2And (3) precursor. In this step, TiCl4The molar ratio to NaOH is 1: 4.
(3) adding TiO into the mixture2Transferring the precursor into a hydrothermal reaction kettle, adjusting the pH value to 3-4, and adding the nano YVO4Adding the materials into a hydrothermal reaction kettle according to a certain proportion, and ultrasonically dispersing and continuously stirring for 12 hours.
(4) Placing a polytetrafluoroethylene net (40-60 meshes) in a reaction kettle, and reacting for 24 hours at 200 ℃.
(5) Washing a polytetrafluoroethylene net with water, washing with alcohol, and drying at 50 ℃ to obtain the loaded YVO4/TiO2。
(6) Placing the obtained sample in concentrated HCl with the same volume, soaking for 24h in the dark, ventilating in the dark until the concentrated HCl is completely volatilized, and finally drying at 50 ℃ to obtain the loaded YVO4/TiO2-C。
Regulating nano YVO4The mass ratio of the materials is respectively 0.01 percent, 0.1 percent, 0.5 percent, 1 percent, 2 percent, 5 percent, 10 percent and 20 percent to obtain the load type YVO with different composite ratios4/TiO2-C。
Wherein YT0.5(0.5 represents nano YVO)4Material accounts for 0.5 percent of the total weight of the material) of a load type YVO4/TiO2TEM photograph of the-C material is shown in FIG. 2, and it can be seen that the composite material is small particles of around 10 nm; YVO4With TiO2The lattice stripes are uniformly dispersed and mutually connected, and the fact that a heterostructure appears in the composite material is proved, and the heterostructure is beneficial to transmission of photo-generated electrons and improvement of catalytic reaction performance.
YVO of different proportions4/TiO2The XRD pattern of the-C material is shown in figure 3 (peak A represents TiO)2Anatase type, R peak represents TiO2Rutile crystal form, B peak represents TiO2Brookite crystal form, Y peak represents YVO4Characteristic peak), it can be confirmed that TiO with good crystal form can be prepared by one-step hydrothermal method2And the crystallinity of each component in the composite material is higher.
Different proportions of YVO4/TiO2the-C material is used for catalyzing and degrading benzene, and the experimental conditions areThe results of the irradiation by light, the catalyst taking amount of 0.4g, the pollutant flow rate of 100ml/min and the benzene concentration of 100ppm are shown in figure 4, and it can be seen that the composite photocatalytic material of the invention has stronger visible light catalytic performance, the degradation rate of benzene reaches 70 percent (left figure), and CO is introduced2The maximum amount of the produced product can reach 1200ppm (right graph).
YVO of YT0.54/TiO2-C material for eliminating O3The experimental conditions were irradiation with visible light, catalyst amount of 0.4g, pollutant flow rate of 100ml/min, and ozone concentration of 100ppm, and the results are shown in FIG. 5, in which it can be seen that O is treated within 10 hours3The elimination rate of (A) is always maintained at about 99%.
Example 2 Modular multilayer Orifice plate photocatalytic reactor
Load type YVO prepared based on the invention4/TiO2The invention provides a multilayer-hole plate type photocatalytic reactor, which is formed by connecting a plurality of multilayer-hole plate type reaction modules in series and finally packaging the multilayer-hole plate type reaction modules in a closed box.
The structural schematic diagram of the multilayer orifice plate type reaction module is shown in fig. 6, and the multilayer orifice plate type reaction module is an orifice plate type sandwich structure, and comprises a plurality of stainless steel orifice plates a1 (2 in this embodiment) and a stainless steel orifice plate B2 (2 in this embodiment) which are arranged in parallel and alternately, holes in the stainless steel orifice plates are used for air flow to pass through, and the holes in the metal orifice plate a1 and the holes in the metal orifice plate B2 are arranged in a staggered manner, so that a turbulent flow effect can be achieved, and reaction gas can be uniformly mixed; metal orifice plate A1-load type YVO4/TiO2The structure of the C-metal orifice plate B2 is a sandwich stacking structure; the supported YVO prepared in the embodiment 1 of the invention is arranged between every two adjacent metal pore plates A1 and B24/TiO2-C composite photocatalytic material (polytetrafluoroethylene mesh) 3. The hole interval parts on the stainless steel hole plate A1 adopt heat-conducting silica gel to fix a plurality of LED lamp beads 4 for providing a reaction light source, and the LED lamp beads 4 and the load type YVO4/TiO2Gaps are arranged between the-C composite photocatalytic materials (polytetrafluoroethylene nets) 3 or the composite photocatalytic materials are in direct contact with the polytetrafluoroethylene nets.
Because of YVO prepared by the invention4/TiO2the-C catalyst is higherThe visible light has the photocatalytic performance, so that the LED of the reactor can use a visible light wave band with higher power, and the cost is low.
The stainless steel pore plate in the reactor not only has the functions of structural support and airflow guidance, but also can dissipate heat of the LED, improve the safety and prolong the service life.
Aiming at the aims of gas flow direction, resistance, diffusion and the like, the structure of the reactor is optimized by adopting a CFD simulation technology, and the result is shown in fig. 7, wherein fig. 7(a) shows the appearance of the reactor and two metal pore plates (A and B), fig. 7(B) shows a pressure simulation diagram of each part when the reactor is filled with the polluted gas, fig. 7(c) shows an internal gas flow simulation diagram when the reactor is filled with the polluted gas, and fig. 7(d) shows an internal flow velocity simulation diagram when the reactor is filled with the polluted gas.
The reactor of the invention can fully mix the reaction gas under the condition of large air quantity, and the integral resistance is lower. As shown in FIG. 8, the reactor (YVO loaded with YT 0.5) was tested4/TiO2for-C material) has 65 percent of photocatalytic degradation rate on benzene and 99 percent of elimination rate on ozone under the condition of long-time large wind quantity.
Claims (6)
1. Load type YVO4/TiO2The preparation method of the composite photocatalytic material comprises the following steps:
adopting a hydrothermal method to prepare nano YVO4Materials and nano TiO2The precursor is reacted to synthesize YVO in one step4/TiO2The composite material is loaded on the polytetrafluoroethylene net; the YVO4/TiO2The surface of the composite material is impregnated by concentrated HCl to obtain the loaded YVO4/TiO2A composite photocatalytic material;
the hydrothermal method comprises the following steps:
the nano TiO is added2Transferring the precursor into a hydrothermal reaction kettle, adjusting the pH value to 3-4, and adding the nano YVO4Dispersing materials by ultrasonic waves and continuously stirring for 12-24 hours; placing the polytetrafluoroethylene net in the hydrothermal reaction kettle, and reacting at 180-220 ℃ for 24-36 h to obtain YVO4/TiO2A composite material;
the nanometer YVO4The mass of the material is YVO4/TiO20.01-10% of the total mass of the composite material;
the impregnation steps are as follows:
subjecting the YVO to4/TiO2Placing the composite material in concentrated HCl with the same volume, and sealing and soaking for 24-36 h in a dark place; then ventilating in dark place until concentrated HCl is completely volatilized, and drying to obtain the loaded YVO4/TiO2A composite photocatalytic material;
preparing the nano TiO2The precursor comprises the following steps:
mixing TiCl4And dropwise adding the aqueous solution into the NaOH aqueous solution, and stirring for 2-4 h at 25-30 ℃ to obtain the aqueous solution.
2. Supported YVO prepared by the method of claim 14/TiO2A composite photocatalytic material.
3. A multilayer orifice plate type photocatalytic reaction module comprises a plurality of metal orifice plates A and metal orifice plates B which are alternately arranged, wherein holes in the metal orifice plates A and holes in the metal orifice plates B are arranged in a staggered mode;
the load type YVO of claim 2 is arranged between every two adjacent metal pore plates A and B4/TiO2A composite photocatalytic material;
a plurality of light sources are arranged at the hole interval part on the metal hole plate A; the light source and the load type YVO4/TiO2The composite photocatalytic materials are arranged in a gap or in direct contact.
4. The multi-layer aperture plate photocatalytic reaction module according to claim 3, characterized in that: the metal pore plate A and the metal pore plate B are both stainless steel pore plates;
the light source is a visible light LED lamp bead.
5. A multi-layer perforated plate type photocatalytic reactor, comprising a plurality of multi-layer perforated plate type photocatalytic reaction modules of claim 3 or 4 connected in series and arranged in a closed box.
6. The supported YVO of claim 24/TiO2Composite photocatalytic material, multi-layer pore plate type photocatalytic reaction module of claim 3 or 4 or multi-layer pore plate type photocatalytic reactor of claim 5 for degrading VOCs and eliminating O3The use of (1).
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