CN115646476A - Sludge-loaded TiO 2 Preparation method of visible light photocatalytic material - Google Patents
Sludge-loaded TiO 2 Preparation method of visible light photocatalytic material Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention belongs to TiO 2 The technical field of photocatalytic materials, in particular to sludge-supported TiO 2 The preparation method of the visible light photocatalytic material comprises the following steps: s1, placing sludge in inorganic base, stirring for reaction, filtering, washing solid to be neutral, and drying to obtain modified sludge; by using hydrogen peroxide to TiO 2 Surface modification is carried out to prepare modified TiO 2 (ii) a S2, preparing the modified sludge and the modified TiO prepared by the S1 2 Stirring and mixing in water, standing, filtering, drying, and calcining to obtain the photocatalytic material. The invention uses sludge as a carrier and takes TiO as 2 Loaded on sludge by the treatment of sludge and TiO 2 Respectively modified to make sludge and TiO 2 Through hydrogen bond connection, the formation of the hydrogen bond can lead TiO to 2 The device has response to visible light, and avoids the problem of secondary pollution caused by dissolution of heavy metals in sludge by passivating the heavy metals in the sludge.
Description
Technical Field
The invention belongs to TiO 2 The technical field of photocatalytic materials, in particular to sludge-supported TiO 2 A preparation method of visible light photocatalytic material.
Background
Rapid development of economy has brought about serious environmental problems, and water pollution caused by organic matters is one of the problems. The existing common organic wastewater treatment methods can be roughly divided into physical methods, biological methods and chemical methods, the nature of pollutants is not changed in the process of treating wastewater by the physical methods, and the pollutants and water are separated by mechanical means, such as precipitation, filtration, adsorption and the like, and because the pollutants are not degraded, the pollutants separated from the water also face the problems of accumulation and secondary pollution. The chemical method is to separate the pollutants from the water by adding a chemical reagent to perform a chemical reaction with the pollutants, but the chemical reagent is used, so that the problem of whether the water body is secondarily polluted is solved, and the application range is small; the biological method is to decompose pollutants by using microorganisms, take the pollutants as microbial metabolic energy, and finally decompose the pollutants into carbon dioxide and water, but the method has slow degradation speed and selectivity on the decomposition of the pollutants.
In order to further improve the treatment effect of organic matter sewage, advanced oxidation methods, including photocatalytic oxidation, have been proposed. The photocatalytic oxidation technology utilizes light to degrade organic matters, has the characteristics of environmental protection and energy conservation, and is widely concerned. The catalytic mechanism is that after the catalyst is illuminated, valence band electrons in the catalyst are excited to a conduction band, correspondingly, holes and electrons are generated, and can react with oxygen, hydroxyl, water molecules and the like in water to generate hydroxyl free radicals and peroxide free radicals with extremely high oxidation capacity, and the free radicals can react with organic matters in the water to further oxidize and decompose the organic matters. It should be noted that the above process occurs on the premise that: the energy irradiated to the catalyst is larger than the forbidden band width of the catalyst.
TiO 2 Is a typical photocatalytic material, and the forbidden band width of the material is 3.0eV (rutile crystal form TiO) 2 ) Can only absorb ultraviolet light, and the ultraviolet light irradiated to the ground by sunlight is very little, so that TiO 2 The key points of the photocatalyst are as follows: how to improve the utilization rate of light.
In the prior art, by applying to TiO 2 Modifying (e.g., metal doping, nitrogen doping, etc.) the photoresponse of the material from the ultraviolet to the visible region to increase the amount of TiO 2 The utilization rate of light is improved, and the photocatalytic performance is improved. For example, patent CN104307545B discloses sludge-supported TiO 2 The preparation method of the visible light photocatalytic material selects sludge generated after sewage treatment as a carrier, and utilizes heavy metal in the sludge to react with TiO 2 Doping with TiO 2 The photoresponse range is extended to the visible region, and TiO is added 2 Loaded on sludge and improves TiO 2 The contact area of the sludge and the organic matters in water solves the problem of secondary pollution caused by sludge accumulation at present.
However, the above patents have the following problems: the heavy metal in the sludge is dissolved out by acid, and after the heavy metal is hydrothermally reacted with titanium salt, the heavy metal is re-reacted with TiO 2 After the hydrothermal reaction, a solid-liquid phase exists in the system, heavy metal ions which are not completely doped into the composite material can also remain in the liquid, and the heavy metal in the sludge is directly discharged into the cleaned water body after the solid-liquid separation, so that the hidden danger of heavy metal pollution is brought.
Disclosure of Invention
In order to solve the technical problems in the patents, the invention provides sludge-supported TiO 2 The preparation method of the visible light photocatalytic material also takes sludge as a carrier and takes TiO as the carrier 2 Loaded on sludge, except that the preparation method can ensure that TiO not only can be used 2 Has responsiveness to visible light and can avoid heavy metal pollution in sludge. It is worth mentioning that the present invention makes TiO available 2 Strategy for responding to visible light and the aboveThe difference in the patent is that the invention is implemented by using sludge and TiO 2 Respectively modifying, and then compounding the two to obtain sludge and TiO 2 Through hydrogen bond connection, the formation of the hydrogen bond can lead TiO to 2 Has response to visible light, i.e. the invention does not utilize heavy metal in the sludge to TiO 2 The heavy metals in the sludge are passivated by the inorganic alkali instead of being dissolved out easily in the sludge, so that the problem of secondary pollution caused by the dissolution of the heavy metals in the sludge is avoided.
The sludge contains metal elements, wherein the metal elements comprise a plurality of heavy metals, and the heavy metals mainly exist in the sludge in the following forms: the sludge adopted by the invention is anaerobic digested sludge, wherein the content of zinc is higher and mainly exists in an unstable ion form, the distribution of various forms of nickel is more uniform, and copper mainly exists in a stable sulfide and organic combination state but also exists in an unstable state, and the content is about 10%; chromium is mainly in a stable residue state, and the unstable state of chromium is about 33 percent; mercury, cadmium, arsenic and lead almost exist in stable states; that is, the sludge contains various heavy metals in unstable forms, unlike the prior art patent CN104307545B, the invention also uses sludge to TiO 2 Loading is carried out, but heavy metal in the sludge is not utilized to carry out TiO 2 Doping is carried out to make the sludge and TiO have visible light responsiveness 2 Respectively modifying to make sludge and TiO 2 Through hydrogen bond connection, and the TiO is enabled to be formed by utilizing the hydrogen bond 2 The invention has response to visible light, and meanwhile, in order to prevent secondary pollution caused by unstable heavy metal in the sludge, the invention passivates the heavy metal, converts the unstable heavy metal into stable state, so that the unstable heavy metal is not released into a water body, thereby avoiding secondary pollution caused by dissolution of the heavy metal in the process of preparing and utilizing the sludge.
The invention is realized by the following technical scheme.
The invention provides sludge-supported TiO 2 The preparation method of the visible light photocatalytic material comprises the following steps:
s1, placing sludge in inorganic base, stirring at room temperature for reaction, filtering, washing solid to be neutral, and drying to obtain modified sludge;
when the sludge is reused, the sludge is placed in a water environment, because heavy metals in the sludge still have an unstable state, if the heavy metals in the state are not treated, water-soluble heavy metals in the sludge are easy to dissolve out, and secondary pollution is still caused to a water body.
By using hydrogen peroxide to TiO 2 Surface modification is carried out to prepare modified TiO 2 (ii) a By using hydrogen peroxide in TiO 2 forming-OOH on the surface, forming hydrogen bond with the oxygen element with lone pair electrons, wherein the formed hydrogen bond can make TiO 2 Has responsiveness to visible light.
S2, preparing the modified sludge and the modified TiO prepared by the S1 2 Stirring and mixing in water, drying, and calcining to obtain the photocatalytic material.
Modified sludge and modified TiO 2 Stirring and mixing in water to make TiO 2 Hydrogen bonds are formed between-OOH on the surface and oxygen elements with lone pair electrons in the sludge, and the oxygen elements are dried and calcined to evaporate and remove moisture and organic matters in the sludge and form a porous structure on a sludge carrier, so that organic pollutants can be adsorbed and TiO content is improved 2 The contact area of the catalyst is increased, and the catalytic effect is improved.
Preferably, in S1, the inorganic base is potassium hydroxide, sodium hydroxide or calcium hydroxide.
Preferably, in S1, the mass ratio of the sludge to the inorganic base is 1.
Preferably, in S1, the modified sludge is stirred for 1-3h at room temperature during preparation.
Preferably, in S1, tiO is added 2 Placing the mixture into hydrogen peroxide, stirring the mixture at room temperature for reaction for 8 to 12 hours, filtering, washing and drying the mixture to obtain modified TiO 2 。
Preferably, in S1, the mass percent of hydrogen peroxide is 3%, and TiO 2 And the dosage ratio of hydrogen peroxide is 1-3g:100mL.
Preferably, in S2, the modified sludge and the modified TiO 2 The mass ratio of (A) to (B) is 2:1-2.
Preferably, S2 is stirred and mixed at room temperature for 2 to 3 hours, and then is kept stand for 1 to 2 hours.
Preferably, in S2, the calcining temperature is 600-800 ℃, and the heat preservation time is 3-4h.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention firstly treats the sludge and the TiO respectively 2 The sludge is modified by an alkaline method, so that heavy metals can be passivated, and the content of oxygen elements in the sludge can be increased; tiO is oxidized by hydrogen peroxide 2 Rendering TiO to be TiO 2 The surface is rich in-OOH, and then the modified sludge and the modified TiO are added 2 The composition is carried out to form hydrogen bonds, and the formation of the hydrogen bonds can lead TiO to be 2 Anchored on the sludge and can make TiO 2 Is responsive to visible light; then calcining the composite material, volatilizing volatile components in the sludge in the calcining process, forming a pore structure in the composite material, and improving the adsorption capacity of organic pollutants so as to ensure that the organic pollutants and TiO are mixed 2 The catalyst is fully contacted, so that the catalytic decomposition effect is improved;
2. the invention fully utilizes the advantage of the sludge as a carrier and avoids the dissolution of heavy metals in the sludge in the preparation and subsequent application processes;
3. the preparation method has simple preparation process and reasonable design, for example, when the sludge is modified, the heavy metal in the sludge can be passivated by one-step alkaline modification, and the sludge can also be subjected to hydroxylation modification for subsequent reaction with TiO 2 Laying a foundation for compounding;
4. the invention uses sludge and TiO 2 Composite, improve TiO 2 The treatment effect on organic pollutants, and the required raw materials and equipment are easy to obtain, so that the method is very suitable for large-scale industrial application.
Drawings
FIG. 1 shows a sludge-supported TiO provided by the invention 2 A flow chart of a preparation method of the visible light photocatalytic material;
FIG. 2 is data of passivation effect of different alkali dosages on Zn;
FIG. 3 is passivation effect data of Cu with different alkali dosages;
FIG. 4 is passivation effect data of Cr with different alkali dosages;
FIG. 5 shows the effect data of different alkali dosages on the photocatalytic decomposition of rhodamine B at normal temperature;
FIG. 6 is data of photocatalytic decomposition effect of rhodamine B with different alkali dosages under heating conditions;
FIG. 7 shows the data of the photocatalytic decomposition effect on rhodamine B in example 1 and comparative example 7.
Detailed Description
In order to make the technical solutions of the present invention better understood and implemented by those skilled in the art, the present invention is further described below with reference to the following specific embodiments and the accompanying drawings, but the embodiments are not meant to limit the present invention.
The experimental methods and the detection methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The invention aims at the CN104307545B that sludge is used for loading TiO 2 When the modified water body is modified, the problem of secondary pollution of water body caused by heavy metal dissolution exists in the preparation process, and the following improvements are carried out, aiming at: not only can make TiO 2 The visible light responsivity can be realized, and the heavy metal pollution in the sludge can be avoided, specifically: the sludge used in the invention is sludge after anaerobic digestion, and the sludge and TiO are respectively treated firstly 2 The sludge is modified by an alkaline method, so that heavy metals can be passivated, and oxygen elements in the sludge can be enrichedA peptide; tiO is oxidized by hydrogen peroxide 2 Rendering TiO to be TiO 2 The surface is rich in-OOH, and then the modified sludge and the modified TiO are added 2 The composition is carried out to form hydrogen bonds, and the formation of the hydrogen bonds can ensure that TiO not only can 2 Anchored on the sludge and can make TiO 2 Is responsive to visible light; then calcining the composite material, volatilizing volatile components in the sludge in the calcining process, forming a pore structure in the composite material, and improving the adsorption capacity of organic pollutants so as to ensure that the organic pollutants and TiO are mixed 2 The catalyst is fully contacted, and the catalytic decomposition effect is improved.
The present invention will be described in detail with reference to the following examples.
TiO used in the examples described below 2 Is rutile crystal type TiO 2 Commercially available.
Example 1
Sludge-loaded TiO 2 The preparation method of the visible light photocatalytic material, as shown in fig. 1, comprises the following steps:
(1) Placing 10g of sludge into 25mL of sodium hydroxide aqueous solution (the concentration is 1 mol/L), stirring and reacting for 3h at room temperature, filtering, washing with water to be neutral, and drying the solid at 60 ℃ to obtain modified sludge;
(2) Adding 10g of TiO 2 Adding 1000mL of hydrogen peroxide solution with the mass percent of 3%, stirring and reacting for 8h at room temperature, then washing with water, and drying at 50 ℃ to obtain modified TiO 2 ；
(3) 20mL of water was added to 5g of the modified sludge, and the mixture was stirred to form a suspension, and then 5g of modified TiO was added 2 Stirring for 2h at room temperature, standing for 1h, filtering, and drying at 80 ℃ in a ventilated environment to obtain a composite material precursor;
(4) Calcining the prepared composite material precursor at 600 ℃, preserving heat for 3 hours, and cooling to room temperature to obtain the sludge-supported TiO 2 A visible light photocatalytic material.
Example 2
Sludge-supported TiO 2 The preparation method of the visible light photocatalytic material comprises the following steps:
(1) Putting 10g of sludge into 30mL of sodium hydroxide aqueous solution (the concentration is 1 mol/L), stirring and reacting at room temperature for 1h, filtering, and drying the solid at 60 ℃ to prepare modified sludge;
(2) 30g of TiO 2 Adding the mixture into 1000mL of hydrogen peroxide solution with the mass percent of 3%, stirring and reacting for 12h at room temperature, then washing with water, and drying at 50 ℃ to obtain modified TiO 2 ；
(3) 20mL of water was added to 5g of the modified sludge, and the mixture was stirred to form a suspension, and then 2.5g of modified TiO was added 2 Stirring at room temperature for 3h, standing for 2h, filtering, and drying at 80 ℃ in a ventilated environment to obtain a composite material precursor;
(4) Calcining the prepared composite material precursor at 800 ℃, preserving the heat for 4 hours, and cooling to room temperature to obtain the sludge-supported TiO 2 A visible light photocatalytic material.
Example 3
Sludge-loaded TiO 2 The preparation method of the visible light photocatalytic material comprises the following steps:
(1) Putting 10g of sludge into 50mL of sodium hydroxide (2 g) aqueous solution (the concentration is 1 mol/L), stirring and reacting for 2h at room temperature, filtering, and drying the solid at 60 ℃ to obtain modified sludge;
(2) 20g of TiO 2 Adding the mixture into 1000mL of hydrogen peroxide solution with the mass percent of 3%, stirring and reacting for 10h at room temperature, then washing with water, and drying at 50 ℃ to obtain modified TiO 2 ；
(3) Adding 20mL of water into 5g of modified sludge, stirring to form a suspension, and then adding 3g of modified TiO 2 Stirring at room temperature for 3h, standing for 2h, filtering, and drying at 80 ℃ in a ventilated environment to obtain a composite material precursor;
(4) Calcining the prepared composite material precursor at 700 ℃, preserving the heat for 4 hours, and cooling to room temperature to obtain the sludge-supported TiO 2 A visible light photocatalytic material.
Example 4
Sludge-loaded TiO 2 Preparation method of visible light photocatalytic materialThe method comprises the following steps:
(1) Placing 10g of sludge into 40mL of sodium hydroxide aqueous solution (the concentration is 1 mol/L), stirring and reacting for 2h at room temperature, filtering, and drying the solid at 60 ℃ to obtain modified sludge;
(2) Adding 10g of TiO 2 Adding 1000mL of hydrogen peroxide solution with the mass percent of 3%, stirring and reacting for 10h at room temperature, then washing with water, and drying at 50 ℃ to obtain modified TiO 2 ；
(3) 20mL of water was added to 5g of the modified sludge, and the mixture was stirred to form a suspension, and then 4g of modified TiO was added 2 Stirring for 3h at room temperature, standing for 1h, filtering, and drying at 80 ℃ in a ventilated environment to obtain a composite material precursor;
(4) Calcining the prepared composite material precursor at 650 ℃, preserving the heat for 4 hours, and cooling to room temperature to obtain the sludge-supported TiO 2 A visible light photocatalytic material.
In order to investigate the influence of the amount of alkali added on the catalytic effect in the modification of sludge, the present invention also provides the following comparative examples. The reason why the following comparative examples were provided is that: the method adopts alkali to modify the sludge, and positive effects and negative effects exist in the action of the alkali, wherein the positive effects are as follows: the unstable heavy metals in the sludge can be passivated by alkali, the heavy metals are converted into hydroxide precipitates to be hidden in the sludge, the content of oxygen elements in the sludge is increased, and the hydroxide precipitates and the oxygen elements can be combined with modified TiO 2 Forming hydrogen bonds; negative effects: the increase of the alkali dosage can generate alkali wastewater; in addition, due to TiO 2 Is an amphoteric, slightly basic compound which can react with both acid and base, provided that there is an excess of unreacted base in the sludge, which, under certain conditions, is present with TiO 2 Risk of reaction, and thus passivation of TiO 2 The photocatalytic performance is degraded.
Comparative example 1
The dosage of alkali is less, the mass ratio of the sludge to the inorganic alkali is 1:
(1) Placing 10g of sludge into 17.5mL of sodium hydroxide aqueous solution (the concentration is 1 mol/L), stirring and reacting for 3 hours at room temperature, and then drying the reaction mixed solution at 60 ℃ to prepare modified sludge;
(2) Adding 10g of TiO 2 Adding 1000mL of hydrogen peroxide solution with the mass percent of 3%, stirring and reacting for 8h at room temperature, then washing with water, and drying at 50 ℃ to obtain modified TiO 2 ；
(3) 20mL of water was added to 5g of the modified sludge, and the mixture was stirred to form a suspension, and then 5g of modified TiO was added 2 Stirring for 2h at room temperature, standing for 1h, filtering, and drying at 80 ℃ in a ventilated environment to obtain a composite material precursor;
(4) Calcining the prepared composite material precursor at 600 ℃, preserving heat for 3 hours, and cooling to room temperature to obtain the sludge-supported TiO 2 A visible light photocatalytic material.
Comparative example 2
The dosage of alkali is more, the mass ratio of the sludge to the inorganic alkali is 1:
(1) 10g of sludge is placed in 62.5mL of sodium hydroxide aqueous solution (the concentration is 1 mol/L), stirred and reacted for 3 hours at room temperature, and then the reaction mixed solution is dried at 60 ℃ to prepare modified sludge;
(2) Adding 10g of TiO 2 Adding the mixture into 1000mL of hydrogen peroxide solution with the mass percent of 3%, stirring and reacting for 8h at room temperature, then washing with water, and drying at 50 ℃ to obtain modified TiO 2 ；
(3) 20mL of water was added to 5g of the modified sludge, and the mixture was stirred to form a suspension, and then 5g of modified TiO was added 2 Stirring at room temperature for 2h, standing for 1h, filtering, and drying at 80 ℃ in a ventilated environment to obtain a composite material precursor;
(4) Calcining the prepared composite material precursor at 600 ℃, preserving the heat for 3 hours, and cooling to room temperature to obtain the sludge-supported TiO 2 A visible light photocatalytic material.
Comparative example 3
The using amount of alkali is less, the mass ratio of the sludge to the inorganic alkali is 1:
(1) Placing 10g of sludge into 2.5mL of sodium hydroxide aqueous solution (the concentration is 1 mol/L), stirring at room temperature for reaction for 3 hours, and then drying the reaction mixed solution at 60 ℃ to prepare modified sludge;
(2) 10g of TiO 2 Adding 1000mL of hydrogen peroxide solution with the mass percent of 3%, stirring and reacting for 8h at room temperature, then washing with water, and drying at 50 ℃ to obtain modified TiO 2 ；
(3) 20mL of water was added to 5g of the modified sludge, and the mixture was stirred to form a suspension, and then 5g of modified TiO was added 2 Stirring at room temperature for 2h, standing for 1h, filtering, and drying at 80 ℃ in a ventilated environment to obtain a composite material precursor;
(4) Calcining the prepared composite material precursor at 600 ℃, preserving heat for 3 hours, and cooling to room temperature to obtain the sludge-supported TiO 2 A visible light photocatalytic material.
Comparative example 4
The dosage of alkali is more, the mass ratio of the sludge to the inorganic alkali is 1:
(1) 10g of sludge is placed in 500mL of sodium hydroxide aqueous solution (the concentration is 1 mol/L), stirred at room temperature and reacted for 3 hours, and then the reaction mixed solution is dried at 60 ℃ to prepare modified sludge;
(2) 10g of TiO 2 Adding the mixture into 1000mL of hydrogen peroxide solution with the mass percent of 3%, stirring and reacting for 8h at room temperature, then washing with water, and drying at 50 ℃ to obtain modified TiO 2 ；
(3) Adding 20mL of water into 5g of modified sludge, stirring to form a suspension, and adding 5g of modified TiO 2 Stirring at room temperature for 2h, standing for 1h, filtering, and drying at 80 ℃ in a ventilated environment to obtain a composite material precursor;
(4) Calcining the prepared composite material precursor at 600 ℃, preserving heat for 3 hours, and cooling to room temperature to obtain the sludge-supported TiO 2 A visible light photocatalytic material.
Comparative example 5
The dosage of alkali is less, the mass ratio of the sludge to the inorganic alkali is 1:
(1) 10g of sludge is placed in 12.5mL of sodium hydroxide aqueous solution (the concentration is 1 mol/L), stirred at room temperature and reacted for 3 hours, and then the reaction mixed solution is dried at 60 ℃ to prepare modified sludge;
(2) 10g of TiO 2 Adding 1000mL of hydrogen peroxide solution with the mass percent of 3%, stirring and reacting for 8h at room temperature, then washing with water, and drying at 50 ℃ to obtain modified TiO 2 ；
(3) Adding 20mL of water into 5g of modified sludge, stirring to form a suspension, and adding 5g of modified TiO 2 Stirring for 2h at room temperature, standing for 1h, filtering, and drying at 80 ℃ in a ventilated environment to obtain a composite material precursor;
(4) Calcining the prepared composite material precursor at 600 ℃, preserving heat for 3 hours, and cooling to room temperature to obtain the sludge-supported TiO 2 A visible light photocatalytic material.
Comparative example 6
The dosage of alkali is more, the mass ratio of the sludge to the inorganic alkali is 1:
(1) Placing 10g of sludge into 250mL of sodium hydroxide aqueous solution (the concentration is 1 mol/L), stirring at room temperature for reaction for 3 hours, and then drying the reaction mixed solution at 60 ℃ to prepare modified sludge;
(2) 10g of TiO 2 Adding the mixture into 1000mL of hydrogen peroxide solution with the mass percent of 3%, stirring and reacting for 8h at room temperature, then washing with water, and drying at 50 ℃ to obtain modified TiO 2 ；
(3) Adding 20mL of water into 5g of modified sludge, stirring to form a suspension, and adding 5g of modified TiO 2 Stirring at room temperature for 2h, standing for 1h, filtering, and drying at 80 ℃ in a ventilated environment to obtain a composite material precursor;
(4) Calcining the prepared composite material precursor at 600 ℃, preserving heat for 3 hours, and cooling to room temperature to obtain the sludge-supported TiO 2 A visible light photocatalytic material.
Comparative example 7
A material prepared according to the method in patent CN 104307545B.
The catalysts prepared in the above examples and comparative examples were subjected to performance characterization as follows.
Firstly, detecting the effect of modified sludge, and evaluating the passivation effect of heavy metals in the sludge, wherein the specific method comprises the following steps: 5g of the modified sludge prepared in example 1, example 3, comparative example 1, comparative example 2, comparative example 3, comparative example 4, comparative example 5 and comparative example 6 (and the sludge which is not modified is used as a control) are respectively taken and placed in 30mL of water, the mixture is stirred for 1h at room temperature, and is kept stand and filtered, the filtrate is taken, and the content of heavy metal in the filtrate is detected.
The change of Zn, cu and Cr contents is taken as a representative to explain the heavy metal passivation effect, and the determination method comprises the following steps:
the method comprises the steps of determining the Zn content by adopting an atomic absorption spectrophotometry, preparing a Zn standard solution with the Zn concentration of 20 mug/mL, putting 1mL, 2mL, 3mL, 4mL and 5mL of the solution into 5 volumetric flasks with 25mL respectively, diluting the solution to a scale with deionized water, determining the absorbance at the wavelength of 213.9nm by adopting the atomic absorption spectrophotometry, drawing a working curve, determining the solution to be detected by adopting the same method, determining the absorbance at the wavelength of 213.9nm, and correspondingly calculating the Zn concentration on the working curve.
Measuring the content of Cu by adopting an atomic absorption method, preparing a Cu standard solution, diluting the Cu standard solution by using nitric acid with the mass concentration of 1%, enabling the concentration of Cu to be respectively 0 mu g/mL, 0.5 mu g/mL, 1.0 mu g/mL, 2.0 mu g/mL and 4.0 mu g/mL, respectively measuring the absorbance of the Cu standard solution at the wavelength of 324.8nm, drawing a working curve, measuring the absorbance of the solution to be detected at the wavelength of 324.8nm, and calculating the concentration of Cu by using the working curve.
Measuring the Cr content by adopting an atomic absorption spectrometry, respectively adding 0mL, 1mL, 2mL, 3mL, 4mL and 5mL of Cr standard solution (100 mu g/mL) into a 50mL volumetric flask, diluting with water to a scale, measuring the absorbance at the wavelength of 357.9nm by adopting an atomic absorption spectrophotometer, drawing a working curve, measuring the absorbance at the wavelength of 357.9nm of the solution to be detected, and calculating the Cr content by utilizing the working curve.
The results of the Zn, cu, and Cr contents detected by the above method are shown in FIGS. 2 to 4. As can be seen from FIGS. 2-4, the unmodified sludge has the highest Zn, cu and Cr contents in the filtrate obtained by the above method, which indicates that heavy metals in the sludge can be eluted; comparative examples 1, 3 and 3In 5, the dosage of alkali is less than that in the embodiment 1 and the embodiment 3, in particular 0.07, 0.01 and 0.05 times of the mass of the sludge, and the content of Zn, cu and Cr contained in the filtrate is reduced relative to the unmodified sludge but is higher than that in the embodiment 1, the embodiment 3, the comparative example 2, the comparative example 4 and the comparative example 6, which shows that the dosage of heavy metal in the sludge can be reduced by using the alkali, the method is feasible, but the dosage of the alkali does not completely passivate the heavy metal in the sludge, and part of Zn, cu and Cr is dissolved; in comparative example 2, comparative example 4 and comparative example 6, the dosage of alkali is more, which is 0.25, 2 and 1 times of the mass of the sludge respectively, compared with example 1 and example 3, the contents of Zn, cu and Cr in the filtrate are further reduced, which shows that the heavy metal in the sludge can be further passivated by increasing the dosage of alkali, and the elution amount of the heavy metal from the sludge is reduced; it is noted that although the increase of the alkali dosage can reduce the elution amount of heavy metals and passivate the heavy metals better, the excessive alkali can also be eluted from the sludge in the subsequent use process to cause secondary pollution to water bodies, and TiO causes secondary pollution 2 Compounds which are amphoteric partial bases, capable of reacting with both acids and bases, and which, under certain conditions, for example under the action of heat, react with TiO in excess of base 2 The catalytic performance of the catalyst is reduced, that is, although the catalyst and the alkali react slowly at normal temperature, the risk of being affected by the alkali still exists, so that on the premise of meeting the requirement of good heavy metal passivation effect, the reduction of the use amount of the alkali is also the key of the catalyst with high catalytic performance, and therefore, the catalytic performance of the catalyst is also detected by the invention, which is specifically described below.
(II) 0.2g of the catalysts prepared in example 1, example 3, comparative example 1, comparative example 2 and comparative example 4 are respectively added into 2000mL of rhodamine B aqueous solution (15 mg/L) and modified TiO modified sludge (in example 1) and modified TiO 2 As a control (in example 1), 5 parallel samples were set for each group, and in order to improve the accuracy of the experiment, before the light experiment, the system was stirred in the dark for 1h, and then irradiated with a 300W lamp with an ultraviolet filter to filter the ultraviolet light,the influence of ultraviolet light is eliminated, the stirring state of the system is also kept in the illumination process, the influence on the experimental result due to unevenness is avoided, 5mL of samples are randomly sampled at regular intervals in the illumination process, centrifugation is carried out, clear liquid is detected, the absorbance is measured by adopting an ultraviolet-visible spectrophotometer (the corresponding rhodamine B concentration is calculated according to a drawn standard curve, and the ratio of the rhodamine B concentration to the initial concentration is calculated, the calculation method is a conventional method, and the detailed description is omitted), and the result is shown in figure 5.
In FIG. 5, modified sludge and modified TiO are shown 2 Group, rhodamine B content did not change over time, indicating that rhodamine B was not degraded, modified sludge and modified TiO 2 Without catalytic activity, i.e. only TiO 2 In which-OOH is contained, and TiO is not allowed to be present 2 Has responsiveness to visible light. In other groups, the content of rhodamine B is in a descending trend along with the prolonging of time, which indicates that the catalyst has a catalytic effect, and further indicates that the modified sludge and the modified TiO are mixed 2 After the two are compounded, the prepared catalyst has responsiveness to visible light, which shows that the two are compounded to generate the catalyst capable of enabling TiO to be used 2 As proved by analysis of substances responding to visible light, the modified sludge is rich in OH oxygen elements and contains lone-pair electrons due to the addition of alkali, and the modified TiO 2 The sludge modified by hydrogen peroxide contains-OOH which can generate hydrogen bonds with OH in the sludge, so that the fact that TiO is caused by the hydrogen bonds generated by the-OOH and the OH in the sludge can be inferred 2 The visible light response can be realized, so that the photocatalysis effect is exerted, and the specific mechanism can be inferred as follows: oxygen and Ti atoms in the hydrogen bond generate electronic transition, and generated holes are transmitted through O-H-O, so that the separation of the electrons and the holes is realized, and the composite catalyst has responsiveness to visible light. In addition, in FIG. 5, the amount of the base added in comparative example 1 is smaller than that in examples 1 and 3, which provides less oxygen lone pair and has a low catalytic effect, which is in accordance with the law, and in comparative examples 2 and 4, although the amount of the base added is much higher than that in examples 1 and 3, the catalytic effect is not much different from that in examples 1 and 3, which may be the case that the base is added to TiO at room temperature 2 The effect of (a) is not significant.
(III) to further confirm the influence of the added excessive alkali, the invention also additionally carries out the following detection, the detection method is the same as the rhodamine B catalytic decomposition experiment, except that the system is also heated during the light irradiation process, and the result is shown in FIG. 6. As can be seen from FIG. 6, the modified sludge and the modified TiO 2 The catalyst has no catalytic activity, the content of rhodamine B in other groups is in a descending trend, but the descending amplitude is different, the content of rhodamine B in example 1 and example 3 is less after 120min, which shows that the catalytic effect of the catalyst in example 1 and example 3 is better than that of comparative example 1, comparative example 2 and comparative example 4, the addition amount of alkali in comparative example 1 is less than that of example 1 and example 3, the provided oxygen lone pair electrons are less, the catalytic effect is low, and the result is in line with the result in FIG. 5. In contrast, the amount of the base used in comparative example 2 and comparative example 4 was higher than that of example 1 and example 3, but the catalytic rate was lower than that of example 1 and example 3, which indicates that an increase in the amount of the base does not necessarily promote the catalytic effect, because: firstly, it is proved that uncleaned alkali exists in the sludge, which is probably because the sludge contains positively charged substances which are adsorbed from the sludge by hydroxide anions through the action of positive and negative charges, and the hydroxide anions are not cleaned in the process of modifying the sludge; secondly, when the modified sludge is mixed with the modified TiO 2 After the composition is carried out, the hydroxide radical can react with TiO due to the increase of the system temperature 2 The influence is caused, but the catalytic effect is reduced, namely the formation of hydrogen bonds and the excessive alkali on TiO 2 Are two factors that need to be balanced. This shows that although the influence range is not large at room temperature, if excessive alkali is added after warming, the catalytic effect is still affected and risks, so based on the above consideration, the present invention limits the dosage range of sludge and alkali to 1.1-0.2, and only within this range, the effect is good regardless of room temperature or elevated temperature: not only can minimize the dissolution of heavy metal and ensure the formation of hydrogen bonds, but also can prevent alkali from dissolving TiO 2 The catalytic effect is ensured, and the cost is reduced.
Taking example 1 as an example, the method is performed with comparative example 7 in the second stepThe result of the rhodamine B decomposition experiment is shown in FIG. 7. From the results in fig. 7, it can be seen that the catalytic effects in example 1 are equivalent to and slightly different from those in comparative example 7, but the method in example 1 can avoid the risk of heavy metal ion elution, so that example 1 does not bring about the problem of secondary pollution of heavy metal under the premise of having certain catalytic performance, and sludge and TiO in the case of sludge and TiO in example 1 2 The composite utilization field makes progress. It should be noted that the performances of the composite catalysts prepared in examples 2 and 4 are similar to those of examples 1 and 3, and are not repeated.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, it is intended that such changes and modifications be included as fall within the scope of the appended claims and their equivalents.
Claims (9)
1. Sludge-supported TiO 2 The preparation method of the visible light photocatalytic material is characterized by comprising the following steps of:
s1, placing sludge in inorganic base, stirring at room temperature for reaction, filtering, washing solid to be neutral, and drying to obtain modified sludge;
by using hydrogen peroxide to TiO 2 Surface modification is carried out to prepare modified TiO 2 ；
S2, preparing the modified sludge and the modified TiO prepared by the S1 2 Stirring and mixing in water, standing, filtering, drying, and calcining to obtain the photocatalytic material.
2. The sludge-supported TiO of claim 1 2 The preparation method of the visible light photocatalytic material is characterized in that in S1, the inorganic base is potassium hydroxide, sodium hydroxide or calcium hydroxide.
3. The sludge-supported TiO of claim 1 2 The preparation method of the visible light photocatalytic material is characterized in that in S1, the mass ratio of the sludge to the inorganic base is 1:0.1-0.2.
4. The sludge-supported TiO of claim 1 2 The preparation method of the visible light photocatalytic material is characterized in that in S1, the modified sludge is stirred for 1-3 hours at room temperature during preparation.
5. The sludge-supported TiO of claim 1 2 The preparation method of the visible light photocatalytic material is characterized in that in S1, tiO is added 2 Placing in hydrogen peroxide, stirring at room temperature for 8-12h, filtering, washing, and drying to obtain modified TiO 2 。
6. The sludge-supported TiO of claim 5 2 The preparation method of the visible light photocatalytic material is characterized in that in S1, the mass percent of hydrogen peroxide is 3 percent, and TiO is 2 And the dosage ratio of hydrogen peroxide is 1-3g:100mL.
7. The sludge-supported TiO of claim 1 2 The preparation method of the visible light photocatalytic material is characterized in that in S2, modified sludge and modified TiO are added 2 The mass ratio of (A) to (B) is 2:1-2.
8. The sludge-supported TiO of claim 1 2 The preparation method of the visible light photocatalytic material is characterized in that in S2, the mixture is stirred and mixed for 2 to 3 hours at room temperature and then stands for 1 to 2 hours.
9. The sludge-supported TiO of claim 1 2 The preparation method of the visible light photocatalytic material is characterized in that in S2, the calcining temperature is 600-800 ℃, and the heat preservation time is 3-4h.
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