CN110732319B - Wood activated carbon body loaded titanium dioxide material and preparation method and application thereof - Google Patents

Wood activated carbon body loaded titanium dioxide material and preparation method and application thereof Download PDF

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CN110732319B
CN110732319B CN201911051874.9A CN201911051874A CN110732319B CN 110732319 B CN110732319 B CN 110732319B CN 201911051874 A CN201911051874 A CN 201911051874A CN 110732319 B CN110732319 B CN 110732319B
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titanium dioxide
activated carbon
wood
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CN110732319A (en
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刘文静
张明辉
王斌
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Inner Mongolia Agricultural University
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    • 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
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    • 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
    • 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
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
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    • C02F2101/36—Organic compounds containing halogen
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/40—Organic compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2305/10—Photocatalysts

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Abstract

The invention belongs to the technical field of activated carbon regeneration, and particularly relates to a wood activated carbon body loaded titanium dioxide material, and a preparation method and application thereof. According to the invention, a method that the wood activated carbon body is loaded with titanium dioxide is adopted, and the titanium dioxide is firmly attached to the inside of the activated carbon, so that the falling of the titanium dioxide is reduced, and the lasting regeneration of the activated carbon is realized; the carbon element generated in the carbonization process of the wood material realizes the self-doping of the titanium dioxide, the photoresponse area of the titanium dioxide is expanded to a visible light area, the recombination of photo-generated electrons and holes is inhibited, the visible light is effectively utilized, and the photocatalytic activity of the titanium dioxide is improved. The method can better exert the synergistic effect of strong adsorption of the active carbon and photocatalytic degradation of the titanium dioxide, and realize the high-efficiency regeneration of the active carbon. The preparation process is simple, the used chemical reagents are fewer in types, the environmental pollution is less, and the industrial production is easy to realize.

Description

Wood activated carbon body loaded titanium dioxide material and preparation method and application thereof
Technical Field
The invention relates to the technical field of activated carbon regeneration, in particular to a wood activated carbon body-loaded titanium dioxide material and a preparation method and application thereof.
Background
Under the background that the industrialization process is continuously accelerated, the environmental problem is increasingly prominent, and the adsorption of target pollutants becomes an important means for controlling the environment. Among many adsorbing materials, Activated Carbon (AC) is widely used because of its excellent physicochemical properties and stability. However, AC is mainly based on physical adsorption, and once the pores are filled to reach adsorption saturation, the AC faces the dilemma of being discarded, and the cost of the adsorption technology is greatly increased. Therefore, how to realize the durable and efficient regeneration of the adsorption saturated AC becomes a key problem which must be solved in AC application.
Currently, AC regeneration methods can be classified into thermal regeneration methods, chemical agent regeneration methods, biological regeneration methods, microwave regeneration methods, ultrasonic regeneration methods, electrochemical regeneration methods, supercritical extraction regeneration methods, photocatalytic regeneration methods, and the like. Among them, the photocatalytic regeneration method is highly appreciated by researchers because of its low regeneration cost, low energy consumption, no secondary pollution, simultaneous adsorption and regeneration (i.e., in-situ regeneration), and other features.
Titanium dioxide (TiO)2) Is a high-efficiency photocatalyst, and can degrade organic pollutants into nontoxic and harmless CO by photocatalytic oxidation2、H2O and other inorganic ions, which are inexpensive, stable in performance, and have an antibacterial effect, are often used for photocatalytic regeneration of AC.
At present, TiO2The process of compounding with AC can be classified into a physical method and a chemical method. The physical method is usually to directly react TiO by physical means2The powder is mixed with the AC powder and generally does not involve any chemical reaction. Zhang et al [ Zhang Z, Yu N, Yu F, et al2supported on AC under microwave irradiation[J].Journal ofHazardous Materials.2014,278:152-157.]First TiO is added2Adding the powder and the AC powder into deionized water according to a certain mass ratio, boiling for 30min under magnetic stirring, cooling, filtering, and performing heat treatment at 300 ℃ to obtain TiO2The AC sample was loaded. Chemical means TiO2The precursor is subjected to a series of physical and chemical changes to form TiO2And deposition on AC mainly includes sol-gel method, hydrothermal method, chemical deposition method and the like. Effect of TiO of Liu W, Zhao G2content on the microstructure and antibacterial activity of TiO2-loaded activated carbon fibers derived from liquefied wood[J].Surface and Interface Analysis.2015,47(10):931-937.]TiO is prepared by taking tetrabutyl titanate as a precursor by a sol-gel method2Sol, and adding TiO2The sol is coated on the active carbon, and the TiO is successfully prepared after heat treatment2Samples loaded with AC.
However, TiO can be produced by any of the above methods2Substantially all only load the AC surface and do not form a firm bond with the AC, therebyIn the process of liquid phase adsorption and regeneration of AC, TiO2Is easy to fall off from the AC surface, and affects TiO2Durability of loaded AC regeneration performance. Yuan et al [ Yuan R, Guan R, Shen W, et al, Photoclatalytic degradation of methyl blue by a combination of TiO2 and activated carbon fibers [ J].Journal of Colloid and Interface Science.2005,282(1):87-91.]The experimental result shows that TiO2After 4 times of tests, the loaded activated carbon fiber basically loses the adsorption degradation effect on methylene blue. Ao et al [ Ao Y, Xu J, Fu D, et al. Low temperature preparation of anatase TiO2-coated activated carbon [ J].Colloids and SurfacesA:Physicochemical and EngineeringAspects.2008,312(2-3):125-130.]The experiment shows that TiO2After 6 cycles of testing (8 hours each) of loaded AC, the degradation rate of phenol decreased by about 20%. Bhosale et al [ Bhosale R, Pujari S R, Lande M K, et al, Photocosmetic activity and characterization of sol-gel-derived Ni-doped TiO2-coated active carbon composites[J].Applied Surface Science.2012,261:835-841.]Discovery of Ni-doped TiO2The loaded AC required only 4 hours initially to completely degrade a 50ppm methylene blue solution, but as the number of tests increased, the time required for the sample to degrade the same concentration, volume of methylene blue became longer and longer until complete degradation was not achieved. Hou et al [ Hou D, Feng L, Zhang J, et al, preparation, characterization and performance of a novel visual light activated carbon-supported and Er3+:YFeO3-doped TiO2photocatalyst[J].Journal ofHazardous Materials.2012,199:301-308.]Shows Er3+:YFeO3Modified TiO2After 4 times of tests, the degradation rate of the loaded AC to the methyl orange is reduced from 74 percent to 28 percent. Therefore, how to firmly bond TiO2Load on AC is one of the key issues in achieving sustained regeneration of AC.
Secondly, the AC strongly adsorbs the formed high concentration target pollutants, which is helpful for improving TiO2The rate of photocatalytic reaction, thus forming a continuous cyclic synergistic process of adsorption-degradation-activation-reabsorption-redegration [ Kanghongping, Sunzyao, Liujian Yong, etc.. Ag+-TiO2Visible light adsorption-photocatalysis synergistic effect of/AC composite material [ J]Environmental engineering report 2015,9(4):1620 and 1624.]. However, the conventional AC surface-supported TiO compound2Method of (2), TiO2The particles are substantially attached to the surface of the AC, blocking the pores of most of the AC, and affecting the synergy of the two. Therefore, how to better exert strong AC adsorption and TiO2The synergistic effect of photocatalytic degradation is the research on TiO2Another key issue faced by efficient regeneration of load AC.
Thirdly, TiO2The forbidden band width of the film is 3.2eV, only ultraviolet light with the wavelength less than 387nm can be absorbed, the visible light utilization is very little, the light quantum efficiency is low, and TiO2The photocatalytic activity is weak, and the popularization and application of photocatalytic regeneration are limited.
To increase TiO2The firmness of the bond with AC has been studied by researchers. Sun and Liu et al [ Sun J, Wang X, Sun J, et al, Photocosmetic degradation and kinetics of Orange G using nano-sized Sn (IV)/TiO2/AC photocatalyst[J].Journal of Molecular Catalysis A:Chemical.2006,260(1-2):241-246.Liu S,Chen X,Chen X.A TiO2/AC composite photocatalyst with high activity and easy separation prepared by a hydrothermal method[J].Journal of Hazardous Materials.2007,143(1-2):257-263.]Respectively using HNO3And HCl for pretreating AC to improve TiO by removing impurities attached to AC surface and pores and exposing or increasing some reactive groups2Firmness of bonding with AC. Liu and Libo et al [ Liu J, Yang R, Li S.preparation and application of Effect TiO2/ACFs photocatalyst[J]The science of the environment newspaper: english version 2006,18(5):979-2Study on influencing factors of photocatalytic degradation of formaldehyde [ J]On-line China scientific and technical thesis 2008,3(5): 347-.]Respectively irradiating TiO with UV2Suspension of sol and AC or means for repeated coating to make more TiO2Loaded on AC to reduce TiO2Impact of sloughing on sample performance. TiO22The size and surface area of the particles are also believed to affect the TiO2And AC important factor for the firmness between the two. Generally speaking, TiO with smaller particle size and larger specific surface area2Helping to improve the firmness of the bond with AC, researchers have adjusted the viscosity of the sol-gel process, the pH of the reaction, the temperature of the heat treatment and the TiO2Loading rate and other preparation processes to obtain TiO with smaller grain diameter2[Weng Y,Wang Y,Asbury J,et al.Back Electron Transfer from TiO2Nanoparticles to FeIII(CN)63-:Origin of Non-Single-Exponential and Particle Size Independent Dynamics[J].Journal of Physical Chemistry B.2000,104(1):92-104.Li Y,Li X,Li J,et al.TiO2-coated active carbon composites with increased photocatalytic activityprepared by a properly controlled sol-gel method[J].Materials Letters.2005,59(21):2659-2663.]. Also, the preparation of mesoporous TiO by using template and ultrasonic wave auxiliary technology2Addition of TiO2Surface area to increase TiO2Binding force to AC [ Liu C, Li Y, Li M, et al. controlled synthesis of ordered mesoporous TiO2-supported on activated carbon and pore-pore synergistic photocatalytic performance[J].Materials Chemistry and Physics.2015,149-150:69-76.]. The above studies have increased TiO to some extent2Firmness of bonding with AC, or reduction of TiO2The influence caused by the shedding is mostly focused on the modification of the interface of two different substances, the required process is relatively complex, and the problems of strong AC adsorption and TiO adsorption cannot be solved2The synergistic effect of photocatalytic degradation is enhanced.
In the improvement of TiO2In the aspect of visible light catalytic activity, a great deal of research has been carried out, and the main methods include noble metal deposition, ion doping and the like. The noble metal deposition is mainly to modify TiO by utilizing noble metals such as Ag, Pt, Au, Pd and the like2Changing the electron distribution in the system, affecting TiO2And further improve its photocatalytic activity. The ion doping is to modify TiO with metal and non-metal ions and the like2Ions are introduced into the crystal lattice to influence the motion state of photogenerated electrons and holes. Although the modification method has been studied relativelyThe method has the advantages of good effect, relatively complex preparation process and high cost of precious metal deposition raw materials.
Thus, TiO2Low photocatalytic activity and TiO22Weak fixation on AC surface, strong AC adsorption and TiO2The problems of insufficient exertion of the synergistic effect of photocatalytic degradation and the like need to be solved urgently.
Disclosure of Invention
The invention aims to provide a wood activated carbon body-loaded titanium dioxide material, and a preparation method and application thereof, wherein the method can simultaneously solve the problem of TiO2Low photocatalytic activity and TiO22Weak fixation on AC surface, strong AC adsorption and TiO2The synergistic effect of photocatalytic degradation is not sufficiently exerted.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a wood activated carbon body loaded titanium dioxide material, which comprises the following steps:
carrying out hydrothermal treatment on a wood material to obtain a pretreated test material;
placing the pretreated test material in tetrabutyl titanate solution, carrying out first impregnation treatment, and sequentially carrying out moisture absorption and drying on the obtained test material to obtain a first dry test material;
carbonizing the first dry test material to obtain a carbonized test material;
placing the carbonized test material in a phosphoric acid solution, performing second dipping treatment, and drying to obtain a second dry test material;
and activating the second dry test material to obtain the wood activated carbon body loaded titanium dioxide material.
Preferably, the temperature of the hydrothermal treatment is 60-100 ℃, and the time is 1-4 h.
Preferably, the tetrabutyl titanate solution is an ethanol solution of tetrabutyl titanate, and the mass ratio of tetrabutyl titanate to ethanol is 0.5-6: 1; the mass ratio of the wood material to the tetrabutyl titanate is 1: 0.5-4.
Preferably, the tetrabutyl titanate solution also comprises a nitrogen source, wherein the nitrogen source is urea, ammonium chloride or melamine; the mass ratio of the nitrogen source to the tetrabutyl titanate is 1: 5-30.
Preferably, the first impregnation treatment mode is normal pressure impregnation, vacuum impregnation or pressure impregnation, the pressure of the vacuum impregnation is 0.05-0.1 MPa, and the pressure of the pressure impregnation is 0.5-1 MPa;
the first dipping treatment is carried out at normal temperature for 12-48 h.
Preferably, the carbonization treatment temperature is 400-500 ℃, and the time is 1-2 h.
Preferably, the volume fraction of the phosphoric acid solution is 10-50%, the second dipping treatment is normal-pressure dipping, the temperature of the second dipping treatment is normal temperature, and the time is 12-48 h.
Preferably, the temperature of the activation treatment is 600-800 ℃, and the time is 1-3 h.
The invention provides a wood activated carbon body loaded titanium dioxide material prepared by the preparation method in the technical scheme.
The invention provides the application of the wood activated carbon body loaded titanium dioxide material in the technical scheme in photocatalytic degradation of organic matters.
The invention provides a preparation method of a wood activated carbon body loaded titanium dioxide material, which comprises the following steps: carrying out hydrothermal treatment on a wood material to obtain a pretreated test material; placing the pretreated test material in tetrabutyl titanate solution, carrying out first impregnation treatment, and sequentially carrying out moisture absorption and drying on the obtained test material to obtain a first dry test material; carbonizing the first dry test material to obtain a carbonized test material; placing the carbonized test material in a phosphoric acid solution, performing second dipping treatment, and drying to obtain a second dry test material; and activating the second dry test material to obtain the wood activated carbon body loaded titanium dioxide material.
The method directly takes the wooden material as the raw material, impregnates the precursor solution of the titanium source in the wooden material through impregnation treatment, and then directly synthesizes the titanium dioxide in the wooden material through carbonization treatment, so that the titanium dioxide can be present in the internal structure of the activated carbon, namely, the method of loading the titanium dioxide on the wooden activated carbon body is adopted, and the titanium dioxide is firmly attached to the inside of the activated carbon, thereby reducing the falling of the titanium dioxide, reducing the blockage of the surface pores of the activated carbon, better playing the synergistic effect of strong adsorption of the activated carbon and photocatalytic degradation of the titanium dioxide, and realizing the high-efficiency regeneration of the activated carbon.
The method for loading titanium dioxide on the wood activated carbon body can enable carbon elements generated in the carbonization process of the wood material to realize self-doping of the titanium dioxide (the carbon elements are doped in the titanium dioxide), expand the photoresponse region of the titanium dioxide to a visible light region, inhibit the recombination of photo-generated electrons and holes, effectively utilize visible light and improve the photocatalytic activity of the titanium dioxide.
The preparation process is simple, the used chemical reagents are fewer in types, the environmental pollution is less, and the industrial production is easy to realize.
Drawings
FIG. 1 is an SEM image of a titania-loaded wood based activated carbon body made in example 3;
FIG. 2 is an EDX diagram of a body of wood activated carbon loaded with a titanium dioxide material prepared in example 3;
FIG. 3 is an XRD pattern of a titania-loaded bulk wood activated carbon as prepared in example 3;
FIG. 4 is a nitrogen adsorption drawing of the titania material loaded wood based activated carbon body prepared in example 3.
Detailed Description
The invention provides a preparation method of a wood activated carbon body loaded titanium dioxide material, which comprises the following steps:
carrying out hydrothermal treatment on a wood material to obtain a pretreated test material;
placing the pretreated test material in tetrabutyl titanate solution, carrying out first impregnation treatment, and sequentially carrying out moisture absorption and drying on the obtained test material to obtain a first dry test material;
carbonizing the first dry test material to obtain a carbonized test material;
placing the carbonized test material in a phosphoric acid solution, performing second dipping treatment, and drying to obtain a second dry test material;
and activating the second dry test material to obtain the wood activated carbon body loaded titanium dioxide material.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
The method carries out hydrothermal treatment on the wood material to obtain the pretreated test material. In the present invention, the wooden material is preferably a branch or a shrub; the branch material preferably comprises poplar branch material or pinus sylvestris branch material, and the shrub comprises salix mongolica.
Before the hydrothermal treatment, the wood material is preferably cut to a diameter of less than 5cm, and the length of the wood material is preferably adjusted according to the height of the used hydrothermal treatment equipment. In the invention, the temperature of the hydrothermal treatment is preferably 60-100 ℃, more preferably 80-90 ℃, and the time is preferably 1-4 hours, more preferably 2-3 hours. In the present invention, the hydrothermal treatment apparatus is preferably a crucible. The present invention removes some extractives, such as sugars, tannins and inorganic salts, from the woody material by hydrothermal treatment.
After the pre-treated test material is obtained, the pre-treated test material is placed in tetrabutyl titanate solution for first dipping treatment, and the obtained test material is sequentially subjected to moisture absorption and drying to obtain a first dry test material. In the invention, the tetrabutyl titanate solution is preferably an ethanol solution of tetrabutyl titanate, and the ethanol in the ethanol solution of tetrabutyl titanate is preferably absolute ethanol; the mass ratio of tetrabutyl titanate to ethanol is preferably 0.5-6: 1, more preferably 1-4: 1, and most preferably 2-3: 1. In the invention, the mass ratio of the wood material to tetrabutyl titanate is preferably 1: 0.5-4, more preferably 1: 1-3, and most preferably 1: 2.
In the invention, the tetrabutyl titanate solution preferably further comprises a nitrogen source, and the nitrogen source is preferably urea, ammonium chloride or melamine; the mass ratio of the nitrogen source to tetrabutyl titanate is preferably 1: 5-30, more preferably 1: 10-20, and most preferably 1: 12-16.
In the invention, the first impregnation treatment is preferably normal pressure impregnation, vacuum impregnation or pressure impregnation, the pressure of the vacuum impregnation is preferably 0.05-0.1 MPa, more preferably 0.06-0.08 MPa, and the pressure of the pressure impregnation is preferably 0.5-1 MPa, more preferably 0.06-0.08 MPa; the temperature of the first dipping treatment is preferably normal temperature, the time is preferably 12-48 h, more preferably 15-30 h, and most preferably 20-24 h. During the impregnation process, the ethanol solution of tetrabutyl titanate is fully impregnated into the wood material.
In the invention, the moisture absorption mode is preferably natural moisture absorption, the moisture absorption environment humidity is preferably equal to or more than 70%, and the time is preferably 24-48 h. In the moisture absorption process, tetrabutyl titanate is hydrolyzed in an ethanol medium to generate Ti (OH)4。
In the invention, the drying temperature is preferably 105 ℃, the drying time is preferably more than or equal to 8h, and the drying time is preferably enough to completely dry the materials. In the present invention, the drying is preferably performed in a forced air drying oven.
After the first dry test material is obtained, the first dry test material is carbonized to obtain a carbonized test material.
In the invention, the temperature of the carbonization treatment is preferably 400-500 ℃, more preferably 420-460 ℃, and the time is preferably 1-2 h. The equipment used for the carbonization treatment is not particularly limited, and equipment well known to those skilled in the art can be selected. In the carbonization process, Ti (OH)4Reacting to generate titanium dioxide; carbonizing the components (including cellulose, hemicellulose and lignin) of the wood material to obtain the carbon material.
After the carbonized test material is obtained, the carbonized test material is placed in a phosphoric acid solution for second dipping treatment and drying to obtain a second dry test material. In the invention, the volume fraction of the phosphoric acid solution is preferably 10-50%, more preferably 20-30%, the second immersion treatment is preferably normal pressure immersion, the temperature of the second immersion treatment is preferably normal temperature, and the time is preferably 12-48 h, more preferably 20-36 h. In the second dipping treatment process, phosphoric acid is used as an activating agent to be dipped into the carbonized test material, so that more pores can be formed on the carbonized test material in the subsequent activation treatment process, and the adsorption performance of the material is improved.
In the present invention, the drying conditions after the second dipping treatment are preferably identical to the drying conditions after the first dipping treatment, and are not described herein again.
After the second dry test material is obtained, the second dry test material is activated to obtain the wood activated carbon body loaded titanium dioxide material. In the invention, the temperature of the activation treatment is preferably 600-800 ℃, more preferably 650-750 ℃, and the time is preferably 1-3 hours, more preferably 1.5-2.5 hours. The activation temperature used by the invention is lower, and the energy consumption and the cost can be reduced. According to the invention, the pores are formed in the wooden material through the activation treatment, so that the wooden material is endowed with better adsorption performance.
After the activation treatment is finished, the obtained material is preferably washed to be neutral by using distilled water and dried to obtain the wood activated carbon body loaded titanium dioxide material. The drying process is not particularly limited in the present invention, and may be a process known to those skilled in the art.
The invention provides a wood activated carbon body loaded titanium dioxide material prepared by the preparation method in the technical scheme. In the invention, in the titanium dioxide material loaded on the wood activated carbon body, the average particle size of titanium dioxide is 8-15 nm, and the specific surface area of the titanium dioxide material loaded on the wood activated carbon body is 150-500 m2The pore volume is 0.09-0.25 cm3/g。
The invention provides the application of the wood activated carbon body loaded titanium dioxide material in the technical scheme in photocatalytic degradation of organic matters. The application method of the wood activated carbon body-loaded titanium dioxide material in photocatalytic degradation of organic matters is not particularly limited, and the method known by the technical personnel in the field can be selected.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Cutting a salix mongolica material with the diameter of 1cm into wood with the length of 2cm, and carrying out hydrothermal treatment for 3h at 100 ℃ to obtain a pretreated salix mongolica material;
placing the pretreated salix mongolica material into a mixed solution of tetrabutyl titanate and absolute ethyl alcohol (the mass ratio of the tetrabutyl titanate to the absolute ethyl alcohol is 1: 1; the mass ratio of the salix mongolica material to the tetrabutyl titanate is 1:2), carrying out normal-pressure impregnation for 48 hours, carrying out moisture absorption treatment on the impregnated test material for 24 hours (the ambient humidity is 80%), and drying at 105 ℃ to be absolute dry to obtain a first dry test material;
carbonizing the first dry test material at the temperature of 450 ℃ for 2h to obtain a carbonized test material;
placing the carbonized test material in a phosphoric acid solution with the volume fraction of 10%, soaking for 12h under normal pressure, and drying at 105 ℃ to be absolutely dry to obtain a second dry test material;
and (3) activating the second dry test material at 600 ℃ for 1h, washing the obtained product to be neutral by using distilled water, and drying to obtain the wood activated carbon body loaded titanium dioxide material.
Example 2
Cutting a poplar branch wood with the diameter of 2cm into a wood with the diameter of 2cm, and carrying out hydrothermal treatment at 100 ℃ for 3h to obtain a pretreated poplar branch wood;
placing the pretreated poplar branch wood into a mixed solution of tetrabutyl titanate and absolute ethyl alcohol (the mass ratio of tetrabutyl titanate to absolute ethyl alcohol is 3: 1; the mass ratio of poplar branch wood to tetrabutyl titanate is 1:3), carrying out normal-pressure impregnation for 48h, carrying out moisture absorption treatment on the impregnated test wood for 24h (the ambient humidity is 80%), and drying at 105 ℃ to be absolutely dry to obtain a first dry test wood;
carbonizing the first dry test material at the temperature of 450 ℃ for 2h to obtain a carbonized test material;
placing the carbonized test material in a phosphoric acid solution with the volume fraction of 10%, soaking for 12h under normal pressure, and drying at 105 ℃ to be absolutely dry to obtain a second dry test material;
and (3) activating the second dry test material at 600 ℃ for 1h, washing the obtained product to be neutral by using distilled water, and drying to obtain the wood activated carbon body loaded titanium dioxide material.
Example 3
Cutting the pinus sylvestris branch wood with the diameter of 1cm into wood with the diameter of 2cm, and carrying out hydrothermal treatment for 3h at 100 ℃ to obtain pretreated pinus sylvestris branch wood;
placing the pinus sylvestris branches into a mixed solution of tetrabutyl titanate and absolute ethyl alcohol (the mass ratio of the tetrabutyl titanate to the absolute ethyl alcohol is 2: 1; the mass ratio of the pinus sylvestris branches to the tetrabutyl titanate is 1:2), and soaking for 48 hours at normal pressure; carrying out moisture absorption treatment on the soaked test material for 24 hours (the ambient humidity is 80%), and drying the test material at 105 ℃ to be absolute dry to obtain a first dry test material;
carbonizing the first dry test material at 400 ℃ for 2h to obtain a carbonized test material;
placing the carbonized test material in a phosphoric acid solution with the volume fraction of 15%, soaking for 12h under normal pressure, and drying at 105 ℃ to be absolutely dry to obtain a second dry test material;
and (3) activating the second dry test material at 600 ℃ for 1h, washing the obtained product to be neutral by using distilled water, and drying to obtain the wood activated carbon body loaded titanium dioxide material.
Comparative example
Sawing the salix mongolica into test materials with the length of 9cm for later use;
putting the salix mongolica test material into a resistance furnace, heating to the required carbonization temperature (400 ℃), and carbonizing for 1h to obtain a carbonized test material;
heating the carbonized test material to 800 ℃ in a resistance furnace by using KOH as an activating agent, and activating for 1 h; repeatedly washing the activated carbon to be neutral by using deionized water to obtain activated carbon;
20g of tetrabutyl titanate (Ti (OC)4H9)4) 3g diethanolamine (NH (C)2H4OH)2) Dissolved in 20g of absolute ethanol (C)2H5OH), stirring with a magnetic stirrer for 5min to dissolve completely to obtain solutionA; adding 1g of glacial acetic acid (CH)3COOH), 7g of water, 10g of absolute ethanol (C)2H5OH) to obtain a solution B. Dropwise adding the solution B into the solution A under magnetic stirring, and continuously stirring for 1h to form TiO2Sol;
take 4g TiO2And uniformly stirring the sol and 1g of the activated carbon, putting the sol and the activated carbon into a drying oven at 100 ℃ for drying, and then putting the dried sol and the activated carbon into a resistance furnace for heat treatment (450 ℃ for 2 hours) to obtain the titanium dioxide sol loaded activated carbon material.
Comparative example 1 a titania-supported activated carbon material was prepared by the existing method, and in the prepared material, titania sol was supported on the surface of activated carbon.
Performance testing
1) The material prepared in example 3 is characterized, fig. 1 is an SEM image of the wood activated carbon body loaded titanium dioxide material prepared in example 3, and it can be seen from the figure that the wood activated carbon body loaded titanium dioxide maintains the shape of the original wood material and is easily recycled.
Fig. 2 is an EDX diagram of the titania-loaded wood-based activated carbon body prepared in example 3, in which a is an SEM diagram of the titania-loaded wood-based activated carbon body, b is a C element distribution diagram, C is an N element distribution diagram, d is a P element distribution diagram, e is an O element distribution diagram, and f is a Ti element distribution diagram. As can be seen from the figure, the C, N, P, O elements in b-e are basically present in the cell walls of the raw wood material based on the corresponding positions in a, and the cell walls and the cell cavities in f contain titanium elements, which proves that the titanium dioxide is successfully attached to the cell walls and the cell cavities, and the material prepared by the method realizes the firm attachment of the titanium elements in the activated carbon.
Fig. 3 is an XRD chart of the titanium dioxide-supported material on the wood-based activated carbon bulk prepared in example 3, and it can be seen from the XRD chart that the sample shows anatase crystal planes at positions 2 θ of 25.27 °, 37.86 °, 48.04 °, 54.04 °, 55.09 °, and 62.80 °, which correspond to the (101), (004), (200), (105), (211), and (204) crystal planes of titanium dioxide, respectively. The characteristic peak at 27.50 ° 2 θ corresponds to the crystal plane of rutile (110). The graphite film has a turbostratic graphite structure in the vicinity of 2 θ of 23 °. According to the obtained data and the formula, the average particle size range of titanium dioxide in the titanium dioxide material loaded on the wood activated carbon body is 8-15 nm.
The material prepared in example 3 was subjected to nitrogen adsorption test, and fig. 4 is a nitrogen adsorption drawing showing that the wood activated carbon body prepared in example 3 supports a titanium dioxide material. According to the calculation of a BET method, the specific surface area of the titanium dioxide material loaded on the wood activated carbon body is 174m2Per g, pore volume of 0.09cm3/g。
2) The materials prepared in examples 1-3 were tested for their synergistic photocatalytic regeneration performance:
taking 0.1g of the material prepared in the embodiment 1-3, putting the material into a methylene blue solution of 50mg/L, carrying out dark treatment for 24h to ensure that the material is saturated in adsorption, the concentration of the methylene blue in the solution is reduced, then carrying out illumination for 12h, continuously reducing the concentration of the methylene blue in the solution, and calculating the regeneration performance of the material according to the reduction value of the concentration of the methylene blue.
The methylene blue removal rates of the materials prepared in examples 1-3 were calculated to be 90%, 70% and 60%, respectively.
3) The materials prepared in example 1 and comparative example were tested for their performance in the photocatalytic regeneration:
taking 0.1g of the material prepared in the examples 1-3 and the comparative example, putting the material into a methylene blue solution of 50mg/L, carrying out dark treatment for 24 hours to ensure that the material is saturated in adsorption, the concentration of the methylene blue in the solution is reduced, then carrying out illumination for 12 hours, continuously reducing the concentration of the methylene blue in the solution, and calculating the regeneration performance of the material according to the reduction value of the concentration of the methylene blue.
It was calculated that the material prepared in example 1 had a methylene blue removal rate of 90% and the material prepared in comparative example 1 had a methylene blue removal rate of 45%. Through comparison, the synergistic photocatalytic regeneration performance of the material prepared by the method for loading titanium dioxide on the wood activated carbon body is greatly superior to that of the material prepared by the surface loading method in the comparative example 1.
The embodiment can show that the invention provides a wood activated carbon body loaded titanium dioxide material, and a preparation method and application thereof. The wood active carbon body-loaded titanium dioxide material prepared by the method for loading the wood active carbon body with the titanium dioxide has better synergistic photocatalytic regeneration performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of a wood activated carbon body loaded titanium dioxide material is characterized by comprising the following steps:
carrying out hydrothermal treatment on a wood material to obtain a pretreated test material; the wood material is a branch material or a shrub; the branch material comprises poplar branch material or pinus sylvestris branch material, and the shrub comprises salix mongolica;
placing the pretreated test material in tetrabutyl titanate solution, carrying out first impregnation treatment, and sequentially carrying out moisture absorption and drying on the obtained test material to obtain a first dry test material;
carbonizing the first dry test material to obtain a carbonized test material;
placing the carbonized test material in a phosphoric acid solution, performing second dipping treatment, and drying to obtain a second dry test material;
and activating the second dry test material to obtain the wood activated carbon body loaded titanium dioxide material.
2. The method according to claim 1, wherein the hydrothermal treatment is carried out at a temperature of 60 to 100 ℃ for 1 to 4 hours.
3. The preparation method according to claim 1, wherein the tetrabutyl titanate solution is an ethanol solution of tetrabutyl titanate, and the mass ratio of tetrabutyl titanate to ethanol is 0.5-6: 1; the mass ratio of the wood material to the tetrabutyl titanate is 1: 0.5-4.
4. The method according to claim 3, wherein the tetrabutyl titanate solution further comprises a nitrogen source, wherein the nitrogen source is urea, ammonium chloride or melamine; the mass ratio of the nitrogen source to the tetrabutyl titanate is 1: 5-30.
5. The production method according to claim 1, wherein the first impregnation treatment is atmospheric impregnation, vacuum impregnation or pressure impregnation, wherein the pressure of the vacuum impregnation is 0.05 to 0.1MPa, and the pressure of the pressure impregnation is 0.5 to 1 MPa;
the first dipping treatment is carried out at normal temperature for 12-36 h.
6. The preparation method according to claim 1, wherein the carbonization treatment is performed at a temperature of 400 to 500 ℃ for 1 to 2 hours.
7. The preparation method according to claim 1, wherein the volume fraction of the phosphoric acid solution is 10 to 50%, the second impregnation is performed at normal pressure, the temperature of the second impregnation is normal temperature, and the time is 12 to 48 hours.
8. The method according to claim 1, wherein the temperature of the activation treatment is 600 to 800 ℃ and the time is 1 to 3 hours.
9. A wood activated carbon body loaded with a titanium dioxide material prepared by the preparation method of any one of claims 1 to 8.
10. Use of the woody activated carbon body loaded titanium dioxide material of claim 9 in photocatalytic degradation of organic matter.
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