CN111151280A - Cerium-based ozone catalyst containing double active sites and preparation method and application thereof - Google Patents
Cerium-based ozone catalyst containing double active sites and preparation method and application thereof Download PDFInfo
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- 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
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- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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Abstract
The invention relates to a cerium-based ozone catalyst containing double active sites, a preparation method and application thereof, belonging to the technical field of advanced wastewater treatment and environmental catalysis. The preparation method of the cerium-based ozone catalyst comprises the following steps: 1) preparing a melamine solution; 2) adding cerium salt into the melamine solution obtained in the step 1), adding a polyhydroxycarboxylic acid assistant and hydrochloric acid, and stirring to obtain a mixture; 3) the mixture is dried and calcined to obtain Ce-g-C3N4A catalyst for the degradation of organic pollutants in wastewater. Compared with the prior art, the Ce-g-C prepared by the invention3N4The catalyst has simple preparation processThe raw materials are cheap and easy to obtain, and Ce-g-C3N4The catalyst is insoluble in acid, alkali and organic solvents, has high catalytic activity and stability, low dosage, wide applicable pH range and good recycling performance, has good mineralization promotion effect on various refractory organic pollutants, and has wide prospect in the advanced treatment of industrial wastewater.
Description
Technical Field
The invention belongs to the technical field of advanced wastewater treatment and environmental catalysis, and relates to Ce-g-C containing double active sites3N4An ozone catalyst, a preparation method and an application thereof.
Background
Industrial waste water is always an important environmental pollution treatment problem in China, and as most organic pollutants in industrial waste water have the characteristics of biological toxicity, complex and stable structure and the like, conventional biological treatment is not enough to achieve standard treatment of waste water. Ozone oxidation technology is an important representative of advanced oxidation technology, and has attracted extensive attention in the field of industrial wastewater treatment due to its advantages of strong oxidation effect, simple process application, and the like. The catalytic ozone oxidation technology aims to promote the decomposition process of ozone by using a catalyst, promote the generation of nonselective hydroxyl free radicals with the oxidation potential as high as 2.80V, and increase the process proportion of removing organic matters by an indirect oxidation way, thereby improving the utilization rate of ozone.
Catalytic ozone technologies can be divided into two main categories: one class of homogeneous catalysis represented by transition metal ions has the advantages of high catalytic activity, high reaction speed and the like, but also has the disadvantages of secondary pollution to wastewater, easy loss of the catalyst and the like. Another class is heterogeneous catalysis, represented by metal active components. The heterogeneous catalyst exists in a solid phase, is easy to separate and recover, avoids a large amount of loss of the catalyst, reduces the wastewater treatment cost, and has the characteristic of being more beneficial to engineering application, so that the heterogeneous catalysis ozone technology is more and more emphasized in the advanced treatment of wastewater.
Although the catalytic ozone technology has been greatly studied in recent years, various catalysts capable of effectively promoting the generation of free radicals have been reported, most of the research is limited to the removal of specific organic pollutants on the aspect of simple structural change, i.e. the increase and decrease of corresponding groups on the structure of the target organic matters only occur, so that the corresponding groups cannot be detected in a specific instrument, namely the removal is considered. Actually, more and more researches show that various oxidation intermediate products generated by incomplete oxidation of initial organic pollutants in water in various ozonization treatment processes aiming at refractory toxic industrial wastewater can cause treated effluent to have stronger biological toxicity. Therefore, the organic pollutants are finally and thoroughly mineralized by continuously improving the ozone oxidation capacity, so that the water safety is ensured, and the method is a large target for the development of the current catalytic ozone oxidation technology. However, most of the catalytic ozone materials reported at present have obvious defects in the aspect of improving the mineralization rate of wastewater treatment.
The ozone oxidation process is accompanied with the ring-opening and substituent oxidation process of various aromatic organic pollutants, so that C is generated in the treated water2-C5Short chain small molecule carboxylic acids (such as oxalic acid) as the main oxidation intermediate, and the intermediate has proved to have strong anti-oxidation property and is difficult to remove by continuous oxidation. More disadvantageously, the level of hydroxide ion concentration in water, which is a common ozonolysis initiator, is significantly insufficient due to the effect of the continuous accumulation of small-molecule carboxylic acids in the oxidation system or the acidic nature of the particular industrial effluent wastewater itself, further impairing the oxidation treatment capacity of ozone technology under acidic conditions. In addition, various main heterogeneous catalysts which take metal as an active component often have the problem of leaching a large amount of metal ions in an acid environment, so that the catalytic performance and the reutilization performance are greatly reduced, and secondary pollution is caused to wastewater. Therefore, how to improve the stability and catalytic activity of the heterogeneous catalyst under acidic conditions is also a great technical difficulty in heterogeneous catalysis of ozone.
Disclosure of Invention
The invention aims to solve the problems of low mineralization performance to organic matters, narrow pH application range, easy loss of active components of a catalyst under an acidic condition, poor recycling performance and the like in the existing heterogeneous catalyst, and provides a cerium-based heterogeneous ozone catalyst containing double active sites, a preparation method thereof and a method for removing pollutants by applying the catalyst in the field of catalytic ozone.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a cerium-based ozone catalyst containing double active sites comprises the following steps:
1) preparing a melamine solution;
2) adding cerium salt into the melamine solution obtained in the step 1), adding a polyhydroxycarboxylic acid assistant and hydrochloric acid, and stirring to obtain a mixture;
3) the mixture is dried and calcined to obtain Ce-g-C3N4A catalyst.
Ce-g-C3N4The catalyst is a heterogeneous ozone catalyst. In the preparation process, the thermal decomposition of the melamine and the polyhydroxy carboxylic acid auxiliary agent and the reduction of cerium are carried out simultaneously, and in the continuous pyrolysis and reduction process, the catalyst gradually forms a graphite-phase carbon nitride layered stacked structure, and cerium and oxygen are uniformly deposited on the surface. Ce-g-C3N4The size of the catalyst obtained by calcining after continuous pyrolysis and reduction reaction is about 100 nm.
Further, in step 1), the preparation process of the melamine solution is as follows: dissolving melamine in boiling water to prepare melamine solution with the concentration of 0.5-5 mol/L.
Further, in the step 2), the cerium salt is cerium nitrate, and the polyhydroxycarboxylic acid assistant is a fatty acid substance with a structure containing at least two hydroxyl groups; 0.1-1.0g of cerous nitrate, 10-20g of polyhydroxycarboxylic acid assistant and 4-6mL of hydrochloric acid with the concentration of 37 wt% are added into each 100mL of melamine solution. The molar ratio of the cerium nitrate to the melamine is 0.005-0.05: 1.
The polyhydroxycarboxylic acid adjuvant is preferably gluconic acid, ascorbic acid, tartaric acid or citric acid. The addition of the polyhydroxy carboxylic acid auxiliary agent with oxidation resistance prevents the oxidation of trivalent cerium in the high-temperature calcination process on the one hand, so that the surface Ce with the enhanced ozone decarboxylation mineralization capability3+The content is effectively improved, and on the other hand, the content is Ce-g-C3N4Introduction of hydroxyl group sites on the surface of the material provides the starting material.
Further, in the step 2), the stirring temperature is 98-100 ℃, and the stirring time is 25-35 min.
Further, in the step 3), the drying temperature is 60-100 ℃, and the drying time is 8-12 h; the calcining process comprises the following steps: the dried mixture is calcined in a tube furnace with a nitrogen flow of 50-150mL/min at a temperature of 450-550 ℃ for 1-2 h.
The cerium-based ozone catalyst containing the double active sites is prepared by the method.
Further, in the catalyst, carbon and nitrogen are in g-C3N4In the form of surface hydroxyl, oxygen in the form of surface hydroxyl and cerium doped in g-C3N4Ce in the crystal lattice3+The form exists. Ce-g-C3N4The catalyst has surface hydroxyl active sites for promoting the decomposition of ozone to generate hydroxyl radicals and surface trivalent cerium active sites for enhancing the decarboxylation and mineralization of organic matters.
The application of a cerium-based ozone catalyst containing double active sites is used for degrading organic pollutants in wastewater. Ce-g-C3N4The catalyst has good improvement effect on the ozone mineralization removal of aromatic and non-aromatic organic pollutants, and has universality.
Further, the application process is as follows: the catalyst is added into the wastewater, then ozone is introduced and stirred, and the catalyst catalyzes the ozone to degrade organic pollutants in the wastewater in the gas-liquid-solid three-phase mass transfer process. The catalyst has good stability, and the Ce-g-C in the waste water3N4The catalyst can be put into other reactors again for use after natural precipitation and separation, the high catalytic activity can be still maintained after the catalyst is repeatedly used for five times, and the catalyst has good effect of improving the ozone mineralization and removal of various organic matters in the wastewater.
Further, the adding amount of the catalyst is 50-200mg/L, the pH value of the wastewater is 3.5-9.0, and the ozone introducing speed is 3-6 mg/min.
The cerium-based ozone catalyst containing double active sites prepared by the invention can obviously promote the cracking, decarboxylation and mineralization of organic pollutants and improve the effect of ozone on the ores of the organic pollutants in the process of catalyzing ozone to oxidize waterThe efficiency is improved. The Ce-g-C3N4The preparation process of the catalyst is simple, the raw materials are cheap and easy to obtain, and the Ce-g-C3N4The catalyst is insoluble in acid, alkali and organic solvents, has high catalytic activity and stability, low dosage, wide applicable pH range and good recycling performance, has good mineralization promotion effect on various refractory organic pollutants, and has wide prospect in the advanced treatment of industrial wastewater.
The invention adopts a mixed calcination method to prepare Ce-g-C3N4The catalyst, because the pyrolysis of melamine and the reduction of cerium occur simultaneously at high temperature in the preparation process, gradually forms a special surface structure in which cerium atoms are stably doped in the graphite phase carbon nitride crystal lattice. Ce-g-C3N4On one hand, the catalyst has small size, good dispersibility and high activity, and is beneficial to improving the catalytic degradation efficiency of various organic pollutants; on the other hand, due to Ce-g-C3N4Is insoluble in acid, alkali and organic solvent, has good structural stability, can be repeatedly utilized, and is suitable for catalytic ozonation technology.
Ce-g-C in the present invention3N4The catalyst not only overcomes the problems of slow oxidation rate and low mineralization rate efficiency when the pollutants are removed by ozone alone, but also solves the problems that the homogeneous catalyst can not be recycled and reused, secondary pollution is introduced and the like. And the problems that the pH application range of the existing catalyst taking metal as an active component is small, the mineralization improving capability is limited, the active component is easy to lose and the like are also solved. In the preparation process, cheap common chemical raw materials of melamine, polyhydroxy carboxylic acid auxiliary agent and trace cerium salt are used as raw materials for preparing the material, so that the capability of mineralizing organic matters in wastewater can be greatly improved. Ce-g-C3N4The catalyst provides an efficient and simple method for improving the mineralization efficiency of organic pollutants in the wastewater.
The core of the invention is that cerium element with excellent ozone activation characteristic is organically combined with graphite phase nitrogen carbide carrier structure with super-stable doped metal, surface hydroxyl sites for promoting ozone decomposition to generate hydroxyl radicals and surface for enhancing decarboxylation and mineralization of organic matters are effectively introducedA trivalent cerium site. On one hand, the problems that the traditional homogeneous cerium ion and cerium-based material is easy to lose and dissolve out to cause inactivation in the ozone activation process are solved, and the structural stability of the catalyst is greatly enhanced; on the other hand, by adding the polyhydroxy carboxylic acid auxiliary agent, the problems of easy oxidation and Ce existing in the traditional cerium-based material in the calcining process are solved3+The content is low, and the hydroxyl group density on the surface of the traditional graphite phase carbon nitride catalyst is greatly increased. Under the synergistic effect of the double active sites, Ce-g-C3N4The catalyst realizes that the cerium-based material and the graphite-phase carbon nitride can improve the ozone mineralization capability of 1+1>2 "in the composition.
The method can be used independently or combined with other water treatment processes. Compared with the traditional single ozone oxidation technology and the homogeneous catalysis ozone oxidation technology, the invention has the following advantages:
1)Ce-g-C3N4in the preparation method of the catalyst, the pyrolysis condensation process of melamine and the polyhydroxycarboxylic acid auxiliary agent and the crystal lattice doping reduction process of cerium are carried out simultaneously, so that active components cerium and hydroxyl groups can form stable chemical bonds on the surface of a material, the material is not easy to run off, the preparation raw materials are cheap and easy to obtain, and the synthesis is simple.
2)Ce-g-C3N4The catalyst has wide pH application range for catalyzing ozone oxidation reaction, can obtain good ozone mineralization promotion effect within the pH range of 3.5-9.0, and widens the application range.
3) By using heterogeneous Ce-g-C3N4The catalyst obviously promotes the preliminary cracking degree of organic pollutants in the ozonization process, greatly improves the removal rate of small molecular carboxylic acid oxidation intermediate products, and ensures that most of organic matters in wastewater are finally and completely mineralized into nontoxic and harmless CO2And H2And O, effectively preventing the generation of toxic intermediate byproducts.
4)Ce-g-C3N4The material has good dispersibility in water, surface hydroxyl groups and trivalent cerium sites which are uniformly distributed on the surface of the material respectively decompose and convert ozone into hydroxyl free radicals, and decarboxylation and mineralization of small molecular carboxylic acid haveHigh catalytic activity. Thus, lower catalyst loadings result in good mineralization enhancement for the ozonation process.
5)Ce-g-C3N4The material has good structural stability, is insoluble in strong acid, strong base and organic solvent, and the active component cerium is basically not dissolved out after reaction, so that the secondary pollution of water can not be introduced. The catalyst still has stable catalytic effect after being repeatedly used for many times under the catalytic ozone reaction condition.
Drawings
FIG. 1 shows Ce-g-C prepared in example 13N4TEM images of the catalyst.
FIG. 2 is a graph showing the removal rate of TOC from oxalic acid waste water obtained in example 4. in FIG. 2, ■ represents the removal curve of TOC by ozone alone, ▲ represents the removal curve of TOC by the action of catalyst Ce-CN-1, ● represents the removal curve of TOC by the action of catalyst Ce-CN-2, and XX represents the removal curve of TOC by the action of catalyst Ce-CN-3.
FIG. 3 is a graph showing the removal rate of TOC from the waste water of p-chlorobenzoic acid in example 7. in FIG. 3, ■ represents the TOC removal curve with ozone alone, ● represents the catalyst Ce-g-C3N4TOC removal profile on action.
FIG. 4 is a graph showing the change of oxalic acid production concentration in the waste water of p-chlorobenzoic acid in example 7. in FIG. 4, ■ represents the change of oxalic acid production concentration in the system under the action of ozone alone, ● represents the presence of catalyst Ce-g-C3N4The change curve of the generated concentration of oxalic acid in the system when in action.
FIG. 5 is a graph showing oxalic acid/TOC removal rate of oxalic acid waste water of example 8 in FIG. 5, ■ represents an oxalic acid removal rate curve, and ● represents a mineralization rate curve (i.e., TOC removal rate curve).
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
By a mixed calcination methodTo Ce-g-C3N4Catalyst, Ce-g-C is added into simulated wastewater and actual wastewater of aromatic and aromatic non-aromatic organic matters3N4Catalyst and ozone are introduced to carry out catalytic oxidation reaction for a certain time, the water quality is analyzed by sampling according to a certain time interval, and the Ce-g-C is evaluated through the removal rate of Total Organic Carbon (TOC) and Chemical Oxygen Demand (COD) of the wastewater3N4The catalytic performance of the material and the optimization of process conditions form a new method for advanced wastewater treatment.
Ce-g-C3N4The catalyst was characterized by X-ray diffractometer (XRD), X-ray photoelectron spectroscopy (XPS), and electron Transmission Electron Microscopy (TEM).
Example 1:
Ce-g-C3N4preparation of the catalyst:
dissolving melamine powder in 100mL of boiling water to prepare a melamine solution with the concentration of 0.5 mol/L; 1.0gCe (NO)3)3·6H2Adding O powder into a melamine solution with the concentration of 0.5mol/L, then adding 15g of gluconic acid and 5mL of 37 wt% hydrochloric acid, and mechanically stirring for 30min in a constant-temperature water bath at 100 ℃; mechanically stirring, and drying the obtained mixture at 60 ℃ for 8 h; calcining the dried solid in a tubular furnace with the nitrogen flow of 50mL/min at the temperature of 450 ℃ for 1h to obtain Ce-g-C3N4The catalyst material is named as Ce-CN-1. The TEM image is shown in figure 1, and the catalyst is in a layered stacked structure and has the size of about 100 nm.
Example 2:
Ce-g-C3N4preparation of the catalyst:
dissolving melamine powder in 100mL of boiling water to prepare a melamine solution with the concentration of 5 mol/L; 0.1gCe (NO)3)3·6H2Adding O powder into 5mol/L melamine solution, then adding 10g ascorbic acid and 5mL 37 wt% hydrochloric acid, and mechanically stirring in 100 ℃ constant temperature water bath for 30 min; the mixture obtained after mechanical stirring is dried for 12h at 100 ℃; calcining the dried solid in a tubular furnace with the nitrogen flow of 100mL/min at the temperature of 500 ℃ for 2h to obtain Ce-g-C3N4The catalyst material is named as Ce-CN-2.
Example 3:
Ce-g-C3N4preparation of the catalyst:
dissolving melamine powder in 100mL of boiling water to prepare a melamine solution with the concentration of 2 mol/L; 0.5gCe (NO)3)3·6H2Adding O powder into 2mol/L melamine solution, then adding 20g citric acid and 5mL 37 wt% hydrochloric acid, and mechanically stirring in 100 ℃ constant temperature water bath for 30 min; the mixture obtained after mechanical stirring is dried for 10 hours at 80 ℃; calcining the dried solid in a tubular furnace with the nitrogen flow of 150mL/min at the temperature of 550 ℃ for 1.5h to obtain Ce-g-C3N4The catalyst material is named as Ce-CN-3.
Example 4:
Ce-g-C3N4the catalyst is used for catalyzing ozone to treat the oxalic acid wastewater:
a typical non-aromatic carboxylic acid, namely oxalic acid, is used as a target pollutant to prepare simulated wastewater with the water sample pH of 3.5 and the concentration of 50 mg/L. 2L of simulated wastewater is taken to be put into a 2.5L organic glass reactor with the inner diameter of 80mm and the height of 500mm, and the Ce-g-C in the embodiments 1, 2 and 3 are respectively added3N450mg/L of catalyst, introducing 3mg/min of ozone at room temperature, mechanically stirring, reacting for 30min, and sampling and detecting wastewater TOC at 5min, 10min, 15min, 20min, 25min and 30min of reaction. Comparison of Ce-g-C under different preparation conditions3N4TOC removal rate at different reaction times. The results are shown in FIG. 2, where three groups of Ce-g-C were added3N4The ozone mineralization effect of the catalyst is obviously higher than that of single ozone, and Ce-CN-2 has the highest catalytic activity in the three catalysts. Synthetic heterogeneous catalyst Ce-g-C3N4The catalytic ozone mineralization degrades oxalic acid, has high catalytic activity, can remove 100% of mineralization of oxalic acid wastewater after reaction is carried out for 30min, and is improved by 48.7% compared with a single ozone experimental group without a catalyst.
Example 5:
Ce-g-C3N4the material is used for catalyzing ozone to treat wastewater of a chemical industrial park:
2L of effluent of a biological treatment secondary sedimentation tank of a sewage treatment plant in a certain chemical industry park is taken to be arranged in a 2.5L organic glass reactor with the inner diameter of 80mm and the height of 500mm, the pH value of the water sample is 7.35, and the initial COD is 88.2 mg/L. 150mg/L of Ce-g-C prepared in example 2 was added separately3N4Introducing 5mg/min ozone at room temperature, mechanically stirring for 40min, and sampling for COD detection at 10min, 20min, 30min and 40 min. Comparing ozone alone with Ce-g-C3N4The experimental group removes COD in the wastewater at different reaction times. The results obtained are shown in table 1 below, and the catalytic ozone was more effective than ozone alone in degrading ozone when samples were taken at different time points. After the reaction is carried out for 20min, the COD of the ozone alone is not reduced, the COD in the catalytic ozone reaction is gradually reduced along with the reaction time, and after the reaction is finished for 40min, the COD is 45.6mg/L and reaches the first-class A emission standard.
TABLE 1 effect of wastewater treatment in a chemical park
Example 6:
Ce-g-C3N4the catalyst is used for catalyzing ozone to treat printing and dyeing wastewater:
taking 2L of wastewater of a certain printing and dyeing enterprise in a 2.5L organic glass reactor with the inner diameter of 80mm and the height of 500mm, wherein the pH value of a water sample is 9.0, and the initial COD is 380.9 mg/L. 200mg/L of Ce-g-C prepared in example 2 was added separately3N4Introducing 6mg/min ozone at room temperature, mechanically stirring for 40min, and sampling for reaction for 10min, 20min, 30min and 40min to detect COD. Comparing ozone alone with Ce-g-C3N4The experimental group removes COD in the wastewater at different reaction times. The results obtained are shown in Table 2 below, and the catalytic ozone was better than ozone alone in degrading ozone when samples were taken at different time points. The COD of the catalytic ozone reaction is gradually reduced along with the reaction time, and the COD is reduced by 70 percent at the end of the reaction for 40 min.
TABLE 2 treatment Effect of certain printing and dyeing wastewater
Example 7:
Ce-g-C3N4the catalyst is used for catalyzing ozone to treat p-chlorobenzoic acid wastewater:
a typical aromatic carboxylic acid, namely p-chlorobenzoic acid, is taken as a target pollutant to prepare simulated wastewater with the water sample concentration of 50 mg/L. 2 parts of 2L of simulated wastewater are placed in a 2.5L plexiglass reactor with an inner diameter of 80mm and a height of 500mm, the pH is adjusted to 6.0, and 100mg/L of Ce-g-C prepared in example 2 is added3N44mg/min of ozone is introduced at room temperature, mechanical stirring is carried out, the TOC and the OA concentration of the wastewater are sampled and detected after 5min, 10min, 15min, 20min, 25min and 30min of reaction time, and the results are shown in figure 3 and figure 4. The experimental result shows that Ce-g-C3N4The addition of (2) obviously promotes the removal of the ozone mineralization of the p-chlorobenzoic acid with the initial concentration of 50 mg/L. And the change of the oxalic acid concentration can be seen, Ce-g-C3N4The addition of the catalyst promotes the initial cracking process of the p-chlorobenzoic acid in an ozonization system, the p-chlorobenzoic acid parent organic matter is cracked into oxalic acid more quickly, and meanwhile, the oxalic acid is also removed quickly in the process, so that the concentration of the oxalic acid in the system is not accumulated after 5min, and the TOC removal rate is promoted.
Example 8:
Ce-g-C3N4catalyst recycling efficiency:
oxalic acid is used as a target pollutant to prepare simulated wastewater with the water sample concentration of 50 mg/L. 1 part of 2L of simulated wastewater is placed in a 2.5L plexiglass reactor with an inner diameter of 80mm and a height of 500mm, the pH is adjusted to 3.5, and 100mg/L Ce-g-C prepared in example 1 is added3N4And introducing 5mg/min ozone at room temperature, mechanically stirring, and sampling to detect the concentration of oxalic acid and TOC after the reaction time is 30 min. After the reaction is finished, Ce-g-C3N4And after natural precipitation and separation, the mixture can be put into other reactors again for the next round of use, five rounds of recycling are carried out, and the experimental result is shown in figure 5. Ce-g-C3N4Catalyst in five-round reutilization for ozonizerThe removal rate of oxalic acid OA and TOC in the system can reach more than 95 percent. The results show that Ce-g-C3N4The catalytic ozonation degradation of the oxalic acid wastewater has a very obvious catalytic effect, and the catalytic performance is stable after repeated for many times.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of a cerium-based ozone catalyst containing double active sites is characterized by comprising the following steps:
1) preparing a melamine solution;
2) adding cerium salt into the melamine solution obtained in the step 1), adding a polyhydroxycarboxylic acid assistant and hydrochloric acid, and stirring to obtain a mixture;
3) the mixture is dried and calcined to obtain Ce-g-C3N4A catalyst.
2. The method for preparing the cerium-based ozone catalyst with the double active sites as claimed in claim 1, wherein the melamine solution is prepared in step 1) by: dissolving melamine in boiling water to prepare melamine solution with the concentration of 0.5-5 mol/L.
3. The method for preparing the cerium-based ozone catalyst containing the double active sites as claimed in claim 1, wherein in the step 2), the cerium salt is cerium nitrate, and the polyhydroxycarboxylic acid adjuvant is a fatty acid substance containing at least two hydroxyl groups in the structure; 0.1-1.0g of cerous nitrate, 10-20g of polyhydroxycarboxylic acid assistant and 4-6mL of hydrochloric acid with the concentration of 37 wt% are added into each 100mL of melamine solution.
4. The method for preparing the cerium-based ozone catalyst containing the double active sites as claimed in claim 1, wherein the stirring temperature in step 2) is 98-100 ℃ and the stirring time is 25-35 min.
5. The method for preparing the cerium-based ozone catalyst containing the double active sites as claimed in claim 1, wherein in the step 3), the drying temperature is 60-100 ℃, and the drying time is 8-12 h; the calcining process comprises the following steps: the dried mixture is calcined in a tube furnace with a nitrogen flow of 50-150mL/min at a temperature of 450-550 ℃ for 1-2 h.
6. A cerium-based ozone catalyst containing dual active sites, prepared by the method of any one of claims 1 to 5.
7. The cerium-based ozone catalyst with dual active sites as claimed in claim 6, wherein the carbon and nitrogen are in g-C3N4In the form of surface hydroxyl, oxygen in the form of surface hydroxyl and cerium doped in g-C3N4Ce in the crystal lattice3+The form exists.
8. Use of a cerium-based ozone catalyst containing dual active sites according to claim 6, wherein said catalyst is used for the degradation of organic pollutants in wastewater.
9. The use of a dual active site-containing cerium-based ozone catalyst as claimed in claim 8, wherein the application process comprises: adding the catalyst into the wastewater, then introducing ozone and stirring, wherein the catalyst catalyzes the ozone to degrade organic pollutants in the wastewater.
10. The use of the cerium-based ozone catalyst containing the double active sites as claimed in claim 9, wherein the dosage of the catalyst is 50-200mg/L, the pH of the wastewater is 3.5-9.0, and the ozone is introduced at a rate of 3-6 mg/min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112246268A (en) * | 2020-10-12 | 2021-01-22 | 四川旭航新材料有限公司 | Novel efficient ozone catalytic material and preparation method thereof |
| CN114011397A (en) * | 2021-11-23 | 2022-02-08 | 中国科学院江西稀土研究院 | Rare earth monoatomic catalyst, preparation method and use thereof |
| CN114225956A (en) * | 2021-12-29 | 2022-03-25 | 南京大学环境规划设计研究院集团股份公司 | Preparation method and application of composite photocatalytic material for degrading antibiotics and hexavalent chromium |
| CN118079980A (en) * | 2024-02-23 | 2024-05-28 | 广东卓信环境科技股份有限公司 | Carbon-nitrogen doped ceria/tourmaline ozone oxidation catalyst and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104289216A (en) * | 2014-09-09 | 2015-01-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Ozone catalyst for catalysis of degradation of surfactants, and preparation and application thereof |
| CN105312061A (en) * | 2014-06-24 | 2016-02-10 | 江苏瑞丰科技实业有限公司 | Normal-temperature ozone-removal catalytic material |
| US20160158730A1 (en) * | 2013-07-10 | 2016-06-09 | Zhenmeng Peng | Functional gas-assisted impregnation method for producing noble metal alloy catalysts with defined morphology |
| CN106672899A (en) * | 2016-12-28 | 2017-05-17 | 安徽工业大学 | Method for catalyzing hydrazine hydrate dehydrogenation with RhNiFe/CeO2@C3N4 nanometer catalyst |
| CN107207274A (en) * | 2015-02-15 | 2017-09-26 | 天津大学 | A kind of micron cerium oxide particle with the common shell structure of multinuclear and preparation method thereof |
| CN108246329A (en) * | 2018-01-09 | 2018-07-06 | 杭州诚洁环保有限公司 | It is a kind of to mix N graphenes-cerium oxide composite catalyst and its application in acid refractory wastewater |
| CN109721148A (en) * | 2019-02-20 | 2019-05-07 | 北京林业大学 | A kind of catalytic ozonation water treatment technology and application method that ability is cut down with bromate of heterojunction boundary electron transmission induction |
| CN110420657A (en) * | 2019-09-05 | 2019-11-08 | 西南石油大学 | A kind of nickel cerium/graphite phase carbon nitride composite catalyst and the preparation method and application thereof |
-
2019
- 2019-12-30 CN CN201911404026.1A patent/CN111151280A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160158730A1 (en) * | 2013-07-10 | 2016-06-09 | Zhenmeng Peng | Functional gas-assisted impregnation method for producing noble metal alloy catalysts with defined morphology |
| CN105312061A (en) * | 2014-06-24 | 2016-02-10 | 江苏瑞丰科技实业有限公司 | Normal-temperature ozone-removal catalytic material |
| CN104289216A (en) * | 2014-09-09 | 2015-01-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Ozone catalyst for catalysis of degradation of surfactants, and preparation and application thereof |
| CN107207274A (en) * | 2015-02-15 | 2017-09-26 | 天津大学 | A kind of micron cerium oxide particle with the common shell structure of multinuclear and preparation method thereof |
| CN106672899A (en) * | 2016-12-28 | 2017-05-17 | 安徽工业大学 | Method for catalyzing hydrazine hydrate dehydrogenation with RhNiFe/CeO2@C3N4 nanometer catalyst |
| CN108246329A (en) * | 2018-01-09 | 2018-07-06 | 杭州诚洁环保有限公司 | It is a kind of to mix N graphenes-cerium oxide composite catalyst and its application in acid refractory wastewater |
| CN109721148A (en) * | 2019-02-20 | 2019-05-07 | 北京林业大学 | A kind of catalytic ozonation water treatment technology and application method that ability is cut down with bromate of heterojunction boundary electron transmission induction |
| CN110420657A (en) * | 2019-09-05 | 2019-11-08 | 西南石油大学 | A kind of nickel cerium/graphite phase carbon nitride composite catalyst and the preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| YU XIE ET AL.: "Enhanced mineralization of oxalate by highly active and Stable Ce(III)-Doped g-C3N4 catalyzed ozonation", 《CHEMOSPHERE》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112246268A (en) * | 2020-10-12 | 2021-01-22 | 四川旭航新材料有限公司 | Novel efficient ozone catalytic material and preparation method thereof |
| CN114011397A (en) * | 2021-11-23 | 2022-02-08 | 中国科学院江西稀土研究院 | Rare earth monoatomic catalyst, preparation method and use thereof |
| CN114011397B (en) * | 2021-11-23 | 2024-03-05 | 中国科学院江西稀土研究院 | Rare earth monoatomic catalyst and preparation method and application thereof |
| CN114225956A (en) * | 2021-12-29 | 2022-03-25 | 南京大学环境规划设计研究院集团股份公司 | Preparation method and application of composite photocatalytic material for degrading antibiotics and hexavalent chromium |
| CN118079980A (en) * | 2024-02-23 | 2024-05-28 | 广东卓信环境科技股份有限公司 | Carbon-nitrogen doped ceria/tourmaline ozone oxidation catalyst and preparation method and application thereof |
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