CN115487823A - Preparation method and application of high-humidity-resistance ozonolysis catalyst - Google Patents
Preparation method and application of high-humidity-resistance ozonolysis catalyst Download PDFInfo
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- CN115487823A CN115487823A CN202211282235.5A CN202211282235A CN115487823A CN 115487823 A CN115487823 A CN 115487823A CN 202211282235 A CN202211282235 A CN 202211282235A CN 115487823 A CN115487823 A CN 115487823A
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
- B01D53/8675—Ozone
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- 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
Abstract
The invention relates to a preparation method and application of a high-humidity-resistance ozonolysis catalyst. The invention takes a plurality of transition metal salts as precursors, and prepares the ozonolysis catalyst with high moisture resistance through the processes of precipitation, drying and calcination. The prepared ozonolysis catalyst can realize that more than 99% of ozonolysis efficiency exceeds 1000h under the humidity of more than 80%, solves the problems of low activity, poor moisture resistance and poor long-term stability of the existing catalyst, and has great application potential in the aspects of treating ozone tail gas by industrial wastewater, treating ozone tail gas by drinking water, treating ozone tail gas by chemical waste gas, sterilizing and disinfecting machine ozone tail gas and treating ozone tail gas by an air purifier.
Description
Technical Field
The invention belongs to the technical field of ozonolysis, and particularly relates to a preparation method and application of a high-humidity-resistance ozonolysis catalyst.
Background
The near-surface ozone pollution problem has become one of the main pollutants of global atmospheric pollution. With the expansion of human activities and the large consumption of fossil energy, secondary ozone pollution is becoming more serious. Ozone, as a strong oxidizing substance, can cause damage to human respiratory tract, skin and mucous membrane, and can affect photosynthesis of plants. The traditional ozonolysis technology comprises activated carbon adsorption, thermal decomposition, medicament absorption and the like, and has the problems of high energy consumption, low efficiency, serious secondary pollution and the like, thereby limiting the large-scale application of the traditional ozonolysis technology. Therefore, the development of efficient, low-cost, pollution-free ozonolysis techniques is one of the challenges currently facing.
The catalytic ozonolysis technology accelerates the decomposition of ozone into oxygen through active sites on a catalyst, has the advantages of mild conditions and green products, and is widely concerned. At present, two types of ozone decomposition catalysts are mainly available on the market, and one type of ozone decomposition catalyst is a noble metal catalyst taking noble metal as an active site, and has good activity and stability but higher cost. The other type of catalyst is transition metal oxide catalyst with oxygen vacancy as active site, which has low cost, good activity but poor stability, and especially in high humidity environment, water molecule and ozone compete to adsorb on the oxygen vacancy to deactivate the oxygen vacancy. Therefore, the development of a highly moisture-resistant, highly stable ozonolysis catalyst is one of the keys to achieving efficient ozone treatment.
Disclosure of Invention
In order to solve the problems, the invention aims to develop a high-efficiency moisture-resistant ozonolysis catalyst, which realizes the ozonolysis efficiency of more than 99 percent under high humidity, high concentration and high space velocity, and has the stabilization time of more than 1000h.
In order to solve the above problems, the second objective of the present invention is to provide a simple and low-cost preparation route for high-moisture-resistance ozonolysis catalysts, reduce the production cost of the catalysts, and promote the popularization of catalytic ozonolysis technology.
In order to solve the technical problems, the invention adopts the following scheme:
a preparation method of a high-humidity-resistance ozonolysis catalyst is characterized by comprising the following steps:
(1) Mixing transition metal salt and water according to the proportion of (0.1-10 g): preparing a solution A by using the dosage ratio of 100 mL;
(2) Sodium hydroxide, urea and ammonia water are mixed according to the proportion of (0-50 g): (0-50 g): preparing a solution B by using the dosage ratio of 100 mL;
(3) Dropwise adding the solution A into an equal amount of the solution B, and stirring at constant temperature until a precipitate is generated;
(4) And drying and calcining the precipitate to obtain the catalyst.
Further, the transition metal salt is a mixture of nickel salt, iron salt, manganese salt, cobalt salt and cerium salt, and the proportion of the transition metal salt is (0.01-1): (0.01-1): (0.01-1): (0.01-1): (0.01-1).
Further, the anion of the transition metal salt is one or more of nitrate, sulfate, chloride and acetate.
Further, the preparation process comprises the following steps:
the dropping speed of the solution A into the solution B is 10-50 drops/min;
the stirring temperature at constant temperature is 10-80 ℃, and the stirring speed is 100-500r/min.
Further, the preparation process comprises the following steps:
the calcining temperature is 100-500 ℃, the calcining time is 0.5-5h, and the calcining atmosphere is one of air, argon and nitrogen.
The catalyst prepared by the preparation method is used for ozonolysis reaction under high humidity, high space velocity and high concentration.
The catalyst is used in the ozone decomposition reaction process, the humidity is not lower than 80%, and the space velocity is not lower than 10000h -1 The ozone concentration is not lower than 100ppm, and the temperature is-5-80 ℃.
The catalyst is used in the ozone decomposition reaction process, and has humidity of over 80% and 10000h -1 Under the conditions of the space velocity and the ozone concentration of 100ppm, the time of the ozone decomposition efficiency of more than 99 percent exceeds 1000h.
The application scene of the catalyst for the ozonolysis reaction comprises the treatment of ozone tail gas in industrial wastewater treatment, the treatment of ozone tail gas in drinking water treatment, the treatment of ozone tail gas in chemical waste gas treatment, the treatment of ozone tail gas in a sterilization and disinfection machine and the treatment of ozone tail gas in an air purifier.
The invention has the beneficial effects that: at present, both noble metal catalysts and transition metal oxide catalysts are easy to deactivate under high humidity conditions, and multiple activation treatments are needed to ensure the activity and stability of the catalysts, which undoubtedly increases the treatment cost. The ozonolysis catalyst of the invention utilizes a multi-valence transitionThe electron transfer process between metals and the alkali treatment to regulate the electron gaining and losing capacity of active sites, promote the adsorption of ozone and inhibit the adsorption of water molecules. In addition, the steric hindrance effect between anions is utilized to regulate and control the pore structure of the catalyst, so that the specific surface area is increased, and the exposure of active sites is increased. The ozone decomposition catalyst can realize the humidity of more than 80 percent and 10000h -1 Under the conditions of the above airspeed and 100ppm ozone concentration, the time of more than 99% of the ozone decomposition efficiency exceeds 1000h, which is expected to promote the practicability of the catalytic ozone decomposition technology and create a good environment for the people.
Drawings
FIG. 1 is an SEM image of an ozonolysis catalyst according to the invention;
FIG. 2 is a graph showing the ozonolysis activity of the ozonolysis catalyst according to the invention at a humidity of 80%;
Detailed Description
The technical solution of the present invention will be described in detail below for better understanding the technical features, objects and advantages of the present invention, but the present invention is not to be construed as being limited to the applicable scope of the present invention
This example provides a method for preparing a highly moisture resistant ozonolysis catalyst.
Example 1:
mixing nickel nitrate, ferric chloride, manganese acetate, cobalt chloride and cerium nitrate according to the proportion of 1:1:1:1:1, weighing 2g of the mixture, and dissolving the mixture in 100mL of water to obtain a solution A; dissolving 10g of sodium hydroxide and 5g of urea in 100mL of ammonia water solution to obtain a solution B; slowly dripping the solution A into the solution B, stirring at 25 drops/min, and stirring at 25 ℃ and 150r/min until a precipitate is generated; and (3) drying the precipitate, and calcining at 350 ℃ for 5 hours in a nitrogen atmosphere to obtain the ozonolysis catalyst.
FIG. 1 is an SEM topography of the ozonolysis catalyst obtained in example 1. As can be seen from the figure, the catalyst presents a porous spherical shape, and the surface of the catalyst is uneven, which is beneficial to the adsorption and decomposition of ozone.
FIG. 2 is a graph showing the activity of the ozonolysis catalyst obtained in example 1 at 80% humidity. As can be seen from the figure, the catalyst can achieve an ozonolysis efficiency of 1250h of more than 99%.
Example 2:
mixing nickel chloride, ferrous sulfate, manganese chloride, cobalt nitrate and cerium nitrate according to the proportion of 1:0.5:1:0.1: after mixing according to the proportion of 0.1, weighing 5g of the mixture and dissolving the mixture in 100mL of water to obtain a solution A; dissolving 5g of sodium hydroxide and 5g of urea in 100mL of ammonia water solution to obtain a solution B; slowly dripping the solution A into the solution B, stirring at 15 drops/min, and stirring at 50 ℃ and 250r/min until a precipitate is generated; and (3) drying the precipitate, and calcining the dried precipitate at 250 ℃ for 3h in a nitrogen atmosphere to obtain the ozonolysis catalyst.
Example 3:
nickel acetate, ferrous sulfate, manganese acetate, cobalt chloride and cerium nitrate are mixed according to a ratio of 0.5:0.1:1:0.1: after mixing according to the proportion of 0.1, 3g of the mixture is weighed and dissolved in 100mL of water to obtain a solution A; dissolving 5g of sodium hydroxide and 10g of urea in 100mL of ammonia water solution to obtain a solution B; slowly dripping the solution A into the solution B, stirring at the speed of 30 drops/min, and stirring at 70 ℃ and 300r/min until a precipitate is generated; and drying the precipitate, and calcining at 150 ℃ for 5 hours in a nitrogen atmosphere to obtain the ozonolysis catalyst.
Comparative example 1:
mixing nickel nitrate, ferric chloride, manganese acetate, cobalt chloride and cerium nitrate according to the proportion of 1:0:0:0:0, weighing 10g of the mixture, and dissolving the mixture in 100mL of water to obtain a solution A; dissolving 10g of sodium hydroxide and 10g of urea in 100mL of ammonia water solution to obtain a solution B; slowly dripping the solution A into the solution B, stirring at the speed of 50 drops/min, and stirring at the temperature of 25 ℃ and at the speed of 500r/min until precipitation is generated; and drying the precipitate, and calcining at 500 ℃ for 5 hours in a nitrogen atmosphere to obtain the ozonolysis catalyst.
Comparative example 2:
nickel acetate, ferrous sulfate, manganese acetate, cobalt chloride and cerium nitrate are mixed according to the proportion of 0:1:1:1:0, weighing 5g of the mixture, and dissolving the mixture in 100mL of water to obtain a solution A; dissolving 5g of sodium hydroxide and 5g of urea in 100mL of ammonia water solution to obtain a solution B; slowly dripping the solution A into the solution B, stirring at the speed of 80 drops/min, and stirring at the temperature of 50 ℃ and at the speed of 300r/min until precipitation is generated; and (3) drying the precipitate, and calcining the dried precipitate at 450 ℃ for 5 hours in a nitrogen atmosphere to obtain the ozonolysis catalyst.
Table 1 shows the comparison between the different examples and the different comparative examples, and it can be seen from the table that the ozonolysis catalyst obtained by the present invention can achieve no decline of the activity for more than 1000 hours at 80% humidity, while the comparative example has not only low activity but also poor stability at 60% humidity.
TABLE 1 comparison of catalytic ozonolysis Performance between different examples and different comparative examples
The present invention is not limited to the above examples, and can achieve excellent ozonolysis efficiency at high humidity by modifying the catalyst active site and modifying the pore structure by changing the preparation conditions and the precursor ratio.
Processes, methods, and apparatus not described in the embodiments of the present invention are known in the art. And will not be described in detail herein.
The above embodiments are provided to further explain the objects, technical solutions and advantages of the present invention in detail, it should be understood that the above embodiments are merely exemplary embodiments of the present invention and are not intended to limit the scope of the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A preparation method of a high-humidity-resistance ozonolysis catalyst is characterized by comprising the following steps:
(1) Mixing transition metal salt and solvent according to the proportion of (0.1-10 g): preparing a solution A by using the dosage ratio of 100 mL;
(2) Sodium hydroxide, urea and ammonia water are mixed according to the proportion of (0-50 g): (0-50 g): preparing a solution B by using the dosage ratio of 100 mL;
(3) Dropwise adding the solution A into an equal amount of the solution B, and stirring at constant temperature until a precipitate is generated;
(4) And drying and calcining the precipitate to obtain the catalyst.
2. The method for preparing the catalyst for highly resistance to wet ozonolysis according to claim 1, wherein the transition metal salt is a mixture of nickel salt, iron salt, manganese salt, cobalt salt and cerium salt, and the ratio is (0.01-1):
(0.01～1)：(0.01～1)：(0.01～1)：(0.01～1)。
3. the transition metal salt mixture of claim 2, wherein the anion of the transition metal salt is one or more of nitrate, sulfate, acetate.
4. The method for preparing a highly moisture-resistant ozonolysis catalyst according to claim 1, characterized in that:
the dropping rate of the solution A into the solution B is 10-50 drops/min;
the stirring temperature at constant temperature is 10-80 ℃, and the stirring speed is 100-500r/min.
5. The method for preparing a highly moisture-resistant ozonolysis catalyst according to claim 1, characterized in that:
the calcining temperature is 100-500 ℃, the calcining time is 0.5-5h, and the calcining atmosphere is one of air, argon and nitrogen.
6. Use of the catalyst obtained by the preparation method according to any one of claims 1 to 5, characterized in that the catalyst is used for ozonolysis reaction under high humidity, high space velocity and high concentration.
7. The use of claim 6, wherein the catalyst is used in the ozonolysis reaction process, the humidity is not lower than 80%, and the space velocity is not lower than 10000h -1 The concentration of ozone is not less than 100ppm, and the temperature is-5-80 ℃.
8. According to claim6, the use is characterized in that the catalyst is used in the ozone decomposition reaction process, and the humidity is more than 80% and the time is 10000h -1 Under the conditions of the space velocity and the ozone concentration of 100ppm, the time of the ozone decomposition efficiency of more than 99 percent exceeds 1000h.
9. The use of claim 6, wherein the application scenarios of the catalyst for the ozonolysis reaction include treatment of industrial wastewater treatment ozone tail gas, drinking water treatment ozone tail gas, chemical waste gas treatment ozone tail gas, sterilization disinfection machine ozone tail gas, and air purifier ozone tail gas.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116351424A (en) * | 2023-03-31 | 2023-06-30 | 西南石油大学 | Preparation method and application of high-moisture-resistance LDH@graphene ozonolysis catalyst |
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