CN115138351A - Synthetic method of adsorption catalyst with in-situ regeneration function - Google Patents

Synthetic method of adsorption catalyst with in-situ regeneration function Download PDF

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CN115138351A
CN115138351A CN202210561699.3A CN202210561699A CN115138351A CN 115138351 A CN115138351 A CN 115138351A CN 202210561699 A CN202210561699 A CN 202210561699A CN 115138351 A CN115138351 A CN 115138351A
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activated carbon
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tio
precursor solution
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CN115138351B (en
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陈飞
夏冰
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Beijing Fulaishibo Technology Development Co ltd
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    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3416—Regenerating or reactivating of sorbents or filter aids comprising free carbon, e.g. activated 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B01J35/39—
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses SiO with an in-situ regeneration function 2 /TiO 2 The preparation method of the/AC composite adsorption catalyst material comprises the following steps: 1) Preparing a silicon oxide precursor solution A; 2) By using N 2 H 4 ·H 2 O-modified activated carbon; 3) Will N 2 H 4 ·H 2 Adding the O modified activated carbon into the silicon precursor solution A to obtain pretreated activated carbon B; 4) Preparing a titanium oxide precursor solution C; 5) Adding the pretreated activated carbon B into the titanium oxide precursor solution C, mixing and drying to obtain SiO 2 /TiO 2 the/AC composite adsorption catalyst. The preparation method according to the invention does not need high-temperature sintering, so that the AC structure is not collapsed; on the other hand, using SiO 2 Bonding TiO as inert barrier 2 A molecular protective base material; at the same time, under the condition of optical excitation, the nano TiO 2 The adsorption sites of the activated carbon can be regenerated by exciting the active oxygen substances to degrade the organic molecules adsorbed on the activated carbon, so that the in-situ regeneration adsorption capacity is stable for a long time.

Description

Synthetic method of adsorption catalyst with in-situ regeneration function
Technical Field
The invention relates to the field of engineering nano material manufacturing, in particular to SiO with an in-situ regeneration function 2 /TiO 2 A method for synthesizing a composite adsorption catalyst material of active carbon.
Background
The adsorption separation and removal of pollutants by using Activated Carbon (AC) is the most extensive unit operation in industry, and has the advantages of broad spectrum, high efficiency and low cost. However, activated carbon with saturated adsorption presents a greater safety risk for storage and disposal as hazardous waste due to the enrichment of toxic and harmful pollutants.
The low-cost and high-efficiency active carbon in-situ regeneration technology and products always receive wide attention. The operation of chemical solvent regeneration is complex and generates a large concentrated waste stream. Electrochemical regeneration requires expensive chemicals, resulting in high operating costs. Microbial regeneration is often a time consuming and effective only biodegradable compound. Thermal regeneration is the most mature industrial disposal method, but the energy cost of thermal regeneration is still a serious constraint factor for the industry. At the same time, thermal regeneration requires off-site regeneration, which results in considerable carbon loss (5-10%), and incomplete regeneration if the activated carbon is saturated with non-volatile organic compounds. In addition, the large concentrated waste streams desorbed from the thermal regeneration process still require further purification treatment.
Application of traditional tetrabutyl titanate sol-gel process to TiO 2 the/AC compound usually needs a sintering crystallization process of about 500 ℃, which not only causes the structural collapse of AC and the reduction of specific surface area, tiO 2 High temperature crystal growth and aggregation also results in reduced photocatalyst activity. In addition, in TiO 2 In the catalytic oxidation process, the generated strong oxidizing substances such as OH free radicals and the like can also oxidize the substrate carbon material, so that the supported TiO 2 The molecules are shed.
For example, chinese patent CN114073934A discloses an activated carbon composite material and a preparation method thereof, which comprises compounding P25 titanium dioxide and metal nanoparticles having a surface plasmon resonance effect on the surface of activated carbon to form a composite material. The preparation method comprises the steps of firstly preparing a suspension of P25 titanium dioxide and a metal precursor with a surface plasma resonance effect, then adjusting a pH value to obtain the P25 titanium dioxide loaded with metal hydroxide particles, adhering the obtained P25 titanium dioxide loaded with the metal hydroxide particles on the surfaces of active carbon particles through a binder, and finally sintering to obtain the active carbon composite material.
Chinese patent CN110302804B discloses a VS 4 -TiO 2 /AC photocatalyst comprising VS 4 、TiO 2 And activated carbon, said VS 4 And TiO 2 The composite material is loaded on active carbon, and the preparation method comprises the following steps: pretreatment of activated carbon and hydrothermal reaction for preparing VS 4 Adding tetrabutyl titanate solution into the powder particles, adjusting the pH value to acidity, adding pretreated activated carbon, stirring to obtain a mixture of the activated carbon and gel, and performing after-treatment processes such as aging, drying, calcining and the like to obtain VS 4 -TiO 2 a/AC photocatalyst.
Chinese patent CN110732319 discloses 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, and performing first dipping treatment; carbonizing the first dry test material to obtain a carbonized test material; placing the carbonized test material in a phosphoric acid solution, performing second impregnation 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.
Therefore, the existing preparation method of the titanium dioxide and activated carbon composite material is usually a mixing and calcining process, but the catalyst prepared by the process can cause considerable carbon loss during regeneration, the service life of the catalyst in recycling is short, and the energy consumption in the preparation process is relatively high.
The photocatalytic regeneration isThe most interesting activated carbon regeneration technology has the following advantages by utilizing photocatalytic regeneration: firstly, the energy requirement is low, and the solar radiation can be used for assisting; secondly, highly oxidizing chemicals are not required to be added, and the reduction of the adsorption capacity of the activated carbon is minimum; thirdly, the process operation can adopt an on-site or in-situ regeneration mode; finally, the adsorbed pollutants can be mineralized directly into CO due to the photocatalytic process 2 And H 2 And O, and the pollutants generated by desorption do not need to be further treated subsequently. TiO2 2 The method has the characteristics of high efficiency, low cost and good chemical stability, and is the most widely applied photocatalyst material, so that the synthesized TiO2/AC composite material realizes the effective photocatalysis regeneration of the adsorbent and is widely concerned.
TiO 2 In the reaction mechanism of the photocatalytic process for regenerating and adsorbing saturated activated carbon, active oxygen species such as hydroxyl radicals generated in the light excitation process are mainly depended on to diffuse to the adsorption position of the inert activated carbon to oxidize adsorbed pollutant molecules. However, the active oxygen species such as hydroxyl radical and the like have the characteristics of short service life and short diffusion distance, so that the adsorption photocatalysis synthesis needs to controllably synthesize TiO in micro-nano scale 2 Composite of/AC, simple mixed TiO 2 And AC will not produce AC effectively regenerated by photocatalytic process, it is desirable to realize TiO based on AC 2 And (4) in-situ synthesis. Therefore, there is a need to develop TiO compounds having AC protection function 2 The low-temperature processing technology of the/AC compound.
Disclosure of Invention
In view of the problems of the prior art, one object of the present invention is to provide an SiO with in-situ regeneration function according to one aspect of the present invention 2 /TiO 2 A low-temperature manufacturing method of an/AC composite adsorption catalyst material.
In order to achieve the above object of the present invention, the SiO with in-situ regeneration function of the present invention 2 /TiO 2 The preparation method of the/AC composite adsorption catalyst material comprises the following steps:
1) Adding Tetraethoxysilane (TEOS) into a solvent, then regulating the pH value to 1-5 by using hydrochloric acid, and stirring the mixed solution at 15-35 ℃ for 30-120 minutes to obtain a silicon oxide precursor solution A;
2) Adding activated carbon into N 2 H 4 ·H 2 Stirring and adsorbing in O solution for 10-60 min, and filtering with qualitative filter paper of Buchner funnel to obtain N 2 H 4 ·H 2 O-modified activated carbon;
3) N is to be 2 H 4 ·H 2 Adding the O-modified activated carbon into the silicon oxide precursor solution A obtained in the step 1), and stirring for 30-120 minutes to obtain pretreated activated carbon B;
4) 1 volume of TiCl under vigorous stirring in an ice-water bath 4 Dropwise addition to pure water, and adjustment of the pH of the above solution to 7 with NaOH solution gave a white precipitate which was washed five times with 20 volumes of purified water each time. The precipitate was then dispersed in 40 volumes of pure water, to which was added 30% by weight of H 2 O 2 Stirring the solution under the ice-water bath condition for reaction for 1 to 2 hours to obtain an orange transparent titanium oxide precursor solution C;
5) Under the condition of ice-water bath, adding pretreated activated carbon B into titanium oxide precursor solution C, uniformly mixing, transferring the obtained paste into a drying oven at 120-180 ℃ for drying reaction for 1-3 h to obtain SiO 2 /TiO 2 the/AC composite adsorption catalyst.
Preferably, the solvent in step 1) is selected from methanol, ethanol or propanol, more preferably methanol.
Preferably, the volume ratio of said Tetraethoxysilane (TEOS) to solvent in step 1) is from 1.
Preferably, the hydrochloric acid concentration in step 1) is 0.02mol/L to 0.1mol/L, more preferably 0.055mol/L.
Preferably, said N in step 2) 2 H 4 ·H 2 The concentration of the O solution is 1.5mol/L to 4mol/L, and more preferably 3mol/L.
Preferably, the activated carbon and the N in step 2) 2 H 4 ·H 2 The mass to volume ratio of the O solution was 1g.
Preferably, said N in step 3) 2 H 4 ·H 2 O-modified activated carbon and the use thereofThe mass-to-volume ratio of the silicon precursor solution a is 1g.
Preferably, tiCl in step 4) 4 Volume ratio to pure water 10.
Preferably, the concentration of the NaOH solution in the step 4) is 60g/L to 80g/L, and more preferably 75g/L.
Preferably, tiCl in step 4) 4 And H 2 O 2 The volume ratio of the solution is 10.
Preferably, the mass to volume ratio of the pretreated activated carbon B to the titanium oxide precursor solution C in step 5) is from 10g to 10g.
Preferably, the oven temperature in step 5) is 150 ℃, and the reaction is dried for 2h.
According to another aspect of the present invention, another object of the present invention is to provide a SiO 2 /TiO 2 The composite adsorption catalyst is prepared according to the preparation method.
According to another aspect of the present invention, it is another object of the present invention to provide the SiO 2 /TiO 2 The application of the/AC composite adsorption catalyst in the aspect of catalyzing and degrading organic pollutants.
Preferably, the organic pollutants are mainly natural organic substances in the form of carbohydrates, proteins, amino acids, fats, etc., and some other biodegradable synthetic organic substances.
Advantageous effects
Compared with the preparation method in the prior art, the method adopts a tetraethoxysilane-hydrazine hydrate-titanium peroxide compound system to synthesize SiO 2 /TiO 2 an/AC complex. Among them, N having basicity and strong reducibility 2 H 4 ·H 2 The O molecule being functional SiO 2 With TiO 2 Molecular bifunctional initiator: n is a radical of 2 H 4 ·H 2 The O molecule can be used for driving tetraethoxysilane to hydrolyze by using alkalinity to generate SiO 2 As the adhesion protective layer, reduction and peroxidation may be usedTitanium oxidation reduction reaction to produce nano TiO 2 Molecule as photocatalytic functional layer, synthesized TiO 2 AC adsorption photocatalytic material. The synthesis method according to the invention does not require high-temperature sintering on the one hand, and therefore does not collapse the structure of the AC; on the other hand, siO is used 2 Bonding TiO as inert barrier 2 A molecular protective base material; at the same time, under the condition of optical excitation, the nano TiO 2 The active carbon adsorption site can be regenerated by exciting active oxygen substances to degrade organic molecules adsorbed on the active carbon, so that the in-situ regeneration adsorption capacity is stable for a long time.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is the SiO prepared in example 1 2 /TiO 2 The transmission electron microscope images of the/AC composite adsorption catalyst at different magnifications;
FIG. 2 is the SiO prepared in example 1 2 /TiO 2 Typical powder XRD pattern of/AC composite adsorption catalyst;
FIG. 3 is SiO prepared in example 1 2 /TiO 2 Results of cycle testing of the/AC composite adsorption catalyst for the reproducible degradation of MO.
Detailed Description
Hereinafter, the present invention will be described in detail. Before the description is made, it should be understood that the terms used in the present specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description proposed herein is just a preferable example for the purpose of illustrations only, not intended to limit the scope of the invention, so it should be understood that other equivalents and modifications could be made thereto without departing from the spirit and scope of the invention.
In this document, the terms "comprising," "including," "having," "containing," or any other similar term, are intended to be open-ended franslational phrase (open-ended franslational phrase) and are intended to cover non-exclusive inclusions. For example, a composition or article comprising a plurality of elements is not limited to only those elements recited herein, but may include other elements not expressly listed but generally inherent to such composition or article. In addition, unless expressly stated to the contrary, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or". For example, the condition "a or B" is satisfied in any of the following cases: a is true (or present) and B is false (or not present), a is false (or not present) and B is true (or present), both a and B are true (or present). Moreover, in this document, the terms "comprising," "including," "having," "containing," and "containing" are to be construed as specifically disclosed and also cover both closed and semi-closed conjunctions, such as "consisting of 8230; and" consisting essentially of 8230.
All features or conditions defined herein as numerical ranges or percentage ranges are for brevity and convenience only. Accordingly, the description of a range of values or percentages should be considered to cover and specifically disclose all possible subranges and individual values within the range, particularly integer values. For example, a description of a range of "1 to 8" should be considered to have specifically disclosed all subranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, and so on, particularly subranges bounded by all integer values, and should be considered to have specifically disclosed individual values such as 1, 2, 3, 4, 5, 6, 7, 8, and so on, within the range. Unless otherwise indicated, the foregoing explanatory methods apply to all matters contained in the entire disclosure, whether broad or not.
If an amount or other value or parameter is expressed as a range, preferred range, or a list of upper and lower limits, it is to be understood that all ranges subsumed therein for any pair of the upper or preferred value of the range and the lower or preferred value of the range are specifically disclosed herein, regardless of whether ranges are separately disclosed. Further, when a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.
Numerical values are herein understood to have the precision of the number of significant digits in the value, provided that the object of the invention is achieved. For example, the number 40.0 should be understood to cover a range from 39.50 to 40.49.
For carbon-based adsorption catalysts, the main technical difficulties of the prior art are two, one is that the traditional TiO is 2 Thermochemical crystallization usually requires a high-temperature sintering process, but the high-temperature sintering process is very easy to cause structural damage of a carbon substrate, so that the low-temperature in-situ synthesis of nano TiO in the carbon substrate is required 2 The damage to the carbon substrate caused by the high-temperature process is avoided as much as possible; second, active nano TiO 2 The active oxygen substances generated in the excitation process have oxidation corrosion effect on the carbon substrate, and the active oxygen substances are firmly adhered to the carbon substrate through the inert bonding layer, so that the active nano TiO caused by the corrosion of the carbon substrate is avoided 2 Falling off and the catalytic performance is reduced. The preparation method according to the invention is realized by introducing N which has both alkalinity and reducibility 2 H 4 ·H 2 The O molecule and the alkalinity can promote the siloxane precursor adsorbed on the surface of the carbon substrate to be hydrolyzed to form SiO 2 Layer, reducing directly on SiO by reducing an oxidizing titanium peroxide precursor 2 TiO formed on the surface of the layer 2 Thereby making TiO into 2 The titanium-modified activated carbon is attached to the surface of the activated carbon modified by the silicon dioxide in situ, so that the titanium atoms are dispersed more uniformly, and the integrity of an AC structure is ensured. On one hand, the adsorption function of the activated carbon can be displayed, and on the other hand, the regeneration capability of the catalyst can also be improved.
SiO obtained by the preparation method of the invention 2 /TiO 2 the/AC composite adsorption catalyst material fully utilizes the adsorption capacity of the active carbon and simultaneously utilizes TiO 2 The organic pollutants adsorbed on the active carbon are effectively decomposed by the photo-catalytic decomposition, and the adsorption capacity of the active carbon is realizedRegeneration of (2). The in-situ regeneration of the catalyst can be realized through illumination, and the service cycle of the catalyst is effectively prolonged.
In addition, the reagents and solvents disclosed below were purchased from innochem, beijing, unless otherwise indicated. TEM was obtained by using a Japanese electron JEM-2100 transmission electron microscope, XRD was obtained by using a D8 Focus polycrystal X-ray diffractometer of Bruker, germany, and methylene blue absorbance was measured by an ultraviolet-visible spectrophotometer (Shimadzu UV 2550).
The following examples are given by way of illustration of embodiments of the invention and are not to be construed as limiting the invention, as those skilled in the art will appreciate that various modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.
Example 1
1) Sequentially adding 1.00mL of Tetraethoxysilane (TEOS) into 10.00mL of methanol solution, then adding 0.5mL of HCl solution with the concentration of 0.055mol/L, adjusting the pH value to 1, and stirring the mixed solution at 25 ℃ (room temperature) for 60 minutes to obtain a silicon oxide precursor solution A;
2) 1g of activated carbon was added with 10mL of 3mol/L N 2 H 4 ·H 2 Stirring and adsorbing in O solution for 30min, and filtering with qualitative filter paper of Buchner funnel to obtain N 2 H 4 ·H 2 O-modified activated carbon;
3) 25 deg.C (room temperature) adding 1g N 2 H 4 ·H 2 Adding the O-modified activated carbon into 10mL of silicon precursor solution A, and stirring for 60 minutes to obtain pretreated activated carbon B;
4) 10mL of TiCl under the condition of vigorous stirring in ice-water bath at 0 DEG C 4 Adding dropwise into 390mL of pure water, adjusting pH of the solution to 7 with 75g/L NaOH solution to obtain white precipitate, filtering and washing the precipitate with 20mL of pure water for five times, dispersing the precipitate in 40mL of pure water, and adding 15mL of H 2 O 2 (the mass percentage concentration is 30%) and stirring the solution for reaction for 1h under the condition of ice-water bath at the temperature of 0 ℃ to obtain an orange transparent titanium oxide precursor solution C;
5)0adding 10g of pretreated activated carbon B into 10mL of titanium oxide precursor solution C under the condition of ice-water bath at the temperature of 10 ℃, uniformly mixing, transferring the obtained paste into a drying oven at the temperature of 150 ℃ for reaction for 2h to obtain SiO 2 /TiO 2 the/AC composite adsorption catalyst.
FIG. 1 is SiO 2 /TiO 2 Transmission electron microscope images of the/AC composite adsorption catalyst at different magnifications show that the SiO prepared by the embodiment can be seen from the transmission electron microscope image in FIG. 1 2 /TiO 2 the/AC composite adsorption catalyst is nano-particles with good dispersibility. As shown in the figure, ultrafine TiO 2 The nanoparticles are uniformly dispersed on the in-situ formed amorphous carbon matrix. Show SiO 2 /TiO 2 HRTEM 0.35nm lattice fringes of/AC complex are well resolved, which is comparable to tetragonal anatase TiO 2 Are uniformly spaced from each other.
FIG. 2 is SiO 2 /TiO 2 Typical powder XRD pattern of/AC composite adsorption catalyst, all peaks can be combined with anatase structure TiO 2 Correspondingly, it was confirmed that the obtained nanocrystalline particles were anatase-structured TiO2. In addition, since the activated carbon and SiO2 in the catalyst are amorphous, they are not shown in the XRD patterns.
Example 2
Except that SiO is not used 2 TiO was prepared in the same manner as in example 1 except for the modification, i.e., without steps 1) and 3) 2 the/AC composite adsorption catalyst.
Example 3
Except that N is not used 2 H 4 ·H 2 SiO was prepared in the same manner as in example 1 except for O treatment 2 /TiO 2 the/AC composite adsorption catalyst.
Example 4
Except that in step 4) no H is used 2 O 2 SiO was prepared in the same manner as in example 1, except that the precursor of Ti was treated 2 /TiO 2 the/AC composite adsorption catalyst.
Test example 1: testing the in-situ regeneration performance of the adsorption catalyst:
the adsorption photocatalytic test was performed at room temperature. 5mg/L methylene blue aqueous solution is adopted as the target dye solution. To 100mL of each dye solution was added 25mg of the composite adsorption catalyst prepared in examples 1 to 4. The adsorption was carried out in the dark, while the photocatalytic activity was carried out under irradiation with 4 UV lamps of 5W and a peak wavelength of 352nm. At given time intervals (10 minutes), the concentration of methylene blue was recorded by measuring the absorbance of the solution at 664nm on a UV-vis spectrophotometer (Shimadzu UV 2550) until the concentration of methylene blue in the solution had dropped to zero.
In order to evaluate the in-situ regeneration performance of the catalyst, the composite adsorption catalysts prepared in examples 1 to 4 were subjected to a methylene blue degradation regeneration degradation experiment. The adsorption degradation method of each round was performed in the manner as in test example 1, and after the first round of adsorption degradation, the composite adsorption catalyst was subjected to filtrate filtration and collection, and then the recovered composite adsorption catalyst was added to the same methylene blue aqueous solution as in the first cycle to perform the second round of photocatalytic test. Thus, the results of the composite adsorption catalyst prepared in example 1 after five rounds of photocatalysis are shown in fig. 3. SiO prepared in example 1 2 /TiO 2 In the first cycle, 96.6% of methylene blue was removed in the/AC composite adsorption catalyst. The efficiency decreased slightly with increasing recovery time. After 5 cycles, the catalytic efficiency remained 94.2%. It can be concluded that SiO prepared according to the synthesis method of the invention 2 /TiO 2 The adsorption catalytic capability of the/AC composite adsorption catalyst is hardly reduced. Since it is difficult to avoid that the catalyst material is not lost at all in the experiment, the decrease in catalytic ability can be attributed to a slight loss of the composite adsorption catalyst. On the other hand, tiO 2 Deposition on AC gives little release or dissolution into solution, indicating that the composite catalyst is very stable.
The regeneration performances of examples 2 to 4 are shown in Table 1, and the adsorption effect is better in the first test, and basically more than 90%. But after the second test, the performance dropped dramatically because the adsorbent could not be effectively regenerated using photocatalysis.
TABLE 1
Rate of degradation Test No. 1 2 nd test Test No. 3 Test No. 4 5 th test
Example 2 94.6％ 65.3％ 32.1％ 21.3％ 21.5％
Example 3 93.2％ 38.2％ 32.1％ 21.3％ 23.2％
Example 4 96.5％ 13.2％ 4.5％ 2.1％ 2.5％
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (10)

1. SiO possessing in-situ regeneration function 2 /TiO 2 The preparation method of the/AC composite adsorption catalyst material comprises the following steps:
1) Adding Tetraethoxysilane (TEOS) into a solvent, then regulating the pH value to 1-5 by using hydrochloric acid, and stirring the mixed solution at the temperature of 15-35 ℃ for 30-120 minutes to obtain a silicon oxide precursor solution A;
2) Adding activated carbon into N 2 H 4 ·H 2 Stirring and adsorbing in O solution for 10-60 min, and filtering with qualitative filter paper of Buchner funnel to obtain N 2 H 4 ·H 2 O-modified activated carbon;
3) Will N 2 H 4 ·H 2 Adding the O modified activated carbon into the silicon oxide precursor solution A obtained in the step 1), and stirring for 30-120 minutes to obtain pretreated activated carbon B;
4) 1 volume of TiCl under vigorous stirring in an ice-water bath 4 Dropwise adding into pure water, adjusting pH to 7 with NaOH solution to obtain white precipitate, filtering and washing the precipitate with 20 volumes of purified water for five times, dispersing the precipitate in 40 volumes of purified water, and adding 30 wt% H 2 O 2 Stirring the solution under the ice-water bath condition for reaction for 1 to 2 hours to obtain an orange transparent titanium oxide precursor solution C;
5) Under the condition of ice-water bath, adding pretreated activated carbon B into titanium oxide precursor solution C, uniformly mixing, transferring the obtained paste into an oven with the temperature of 120-180 ℃, and carrying out drying reaction for 1-3 h to obtain SiO 2 /TiO 2 /AC compoundingAdsorbing the catalyst.
2. The method according to claim 1, wherein the solvent in step 1) is selected from methanol, ethanol or propanol, more preferably methanol.
3. The method according to claim 1, wherein the volume ratio of the Tetraethoxysilane (TEOS) to the solvent in step 1) is 1.
4. The method according to claim 1, wherein the hydrochloric acid concentration in step 1) is 0.02mol/L to 0.1mol/L, and more preferably 0.055mol/L.
5. The method according to claim 1, wherein N is the same as N in step 2) 2 H 4 ·H 2 The concentration of the O solution is 1.5mol/L to 4mol/L, and more preferably 3mol/L.
6. The method according to claim 1, wherein the activated carbon and the N are used in the step 2) 2 H 4 ·H 2 The mass to volume ratio of the O solution was 1g.
7. The method according to claim 1, wherein N is the same as N in step 3) 2 H 4 ·H 2 The mass-to-volume ratio of the O-modified activated carbon to the silicon precursor solution a is 1g;
preferably, tiCl in step 4) 4 Volume ratio to pure water 10;
preferably, the concentration of the NaOH solution in the step 4) is 60g/L to 80g/L, and more preferably 75g/L;
preferably, tiCl in step 4) 4 And H 2 O 2 The volume ratio of the solution is 10 to 10, more preferably 10;
preferably, the mass-to-volume ratio of the pretreated activated carbon B to the titanium oxide precursor solution C in step 5) is from 10g to 10g, more preferably, from 10g to 10ml;
preferably, the oven temperature in the step 5) is 150 ℃, and the drying reaction is carried out for 2h.
8. The method of claim 1, wherein the method is performed by:
1) Sequentially adding 1.00mL of Tetraethoxysilane (TEOS) into 10.00mL of methanol solution, then adding 0.5mL of HCl solution with the concentration of 0.055mol/L, adjusting the pH value to 1, and stirring the mixed solution at 25 ℃ (room temperature) for 60 minutes to obtain a silicon oxide precursor solution A;
2) 1g of activated carbon was added with 10mL of 3mol/L N 2 H 4 ·H 2 Stirring and adsorbing in O solution for 30min, and filtering with qualitative filter paper of Buchner funnel to obtain N 2 H 4 ·H 2 O-modified activated carbon;
3) 25 deg.C (room temperature) adding 1g N 2 H 4 ·H 2 Adding the O modified activated carbon into 10mL of silicon precursor solution A, and stirring for 60 minutes to obtain pretreated activated carbon B;
4) 10mL of TiCl under the condition of vigorous stirring in ice-water bath at 0 DEG C 4 Adding dropwise into 390mL of pure water, adjusting pH of the solution to 7 with 75g/L NaOH solution to obtain white precipitate, filtering and washing the precipitate with 20mL of pure water for five times, dispersing the precipitate in 40mL of pure water, and adding 15mL of H 2 O 2 (the mass percentage concentration is 30%) and stirring the solution for reaction for 1h under the condition of ice-water bath at the temperature of 0 ℃ to obtain an orange transparent titanium oxide precursor solution C;
5) Adding 10g of pretreated activated carbon B into 10mL of titanium oxide precursor solution C under the condition of ice-water bath at 0 ℃, uniformly mixing, transferring the obtained paste into a drying oven at 150 ℃ for reaction for 2h to obtain SiO 2 /TiO 2 the/AC composite adsorption catalyst.
9. SiO (silicon dioxide) 2 /TiO 2 a/AC composite adsorption catalyst, the SiO 2 /TiO 2 the/AC composite adsorption catalyst according to any one of claims 1 to 8The preparation method of (1).
10. SiO as claimed in claim 9 2 /TiO 2 The use of the/AC composite adsorption catalyst in the aspect of catalyzing and degrading organic pollutants;
preferably, the organic pollutants are mainly natural organic substances in the form of carbohydrates, proteins, amino acids, fats and the like, and some other biodegradable artificially synthesized organic substances.
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