CN117258820A - Carrier acidification N-doped Pt/TiO 2 Method for preparing-N catalyst and catalyst - Google Patents

Carrier acidification N-doped Pt/TiO 2 Method for preparing-N catalyst and catalyst Download PDF

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Publication number
CN117258820A
CN117258820A CN202311067954.XA CN202311067954A CN117258820A CN 117258820 A CN117258820 A CN 117258820A CN 202311067954 A CN202311067954 A CN 202311067954A CN 117258820 A CN117258820 A CN 117258820A
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tio
catalyst
carrier
doped
acidified
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吴锐
朱红太
李凯
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Beijing Fangxinlihua Technology Co ltd
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Beijing Fangxinlihua Technology Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/864Removing carbon monoxide or hydrocarbons
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/50Carbon oxides
    • B01D2257/502Carbon monoxide

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

The application discloses a carrier acidified N-doped Pt/TiO 2 -N catalyst manufacturing method and catalyst. The carrier acidizes N-doped Pt/TiO 2 the-N catalyst comprises: tiO is mixed with 2 Soaking in dilute sulfuric acid solution, drying the soaked slurry into powder, transferring the powder into a tube furnace, heating to a first preset temperature, treating in H2/Ar mixed gas for a first preset time, and then introducing NH3/Ar mixed gas for a second preset time to obtain a modified carrier; the treated modified carrier was taken out and placed in a reaction kettle, and Pt (NO) was impregnated with the modified carrier by an impregnation method 3 ) 2 Drying the solution and the immersed slurry into powder, and then placing the powder in a muffle furnace to bake for a third preset time to obtain the carrier acidified N-doped Pt/TiO 2 -an N catalyst. Through the application of the present applicationIs N-doped Pt/TiO 2 The catalyst prepared by the preparation method of the-N catalyst can reach higher CO conversion rate at 160-180 ℃ under the condition of 400,000h < -1 >, and SO at 200 ℃is realized 2 50ppm,H 2 Stable operation under the condition of O15%.

Description

Carrier acidification N-doped Pt/TiO 2 Method for preparing-N catalyst and catalyst
Technical Field
The application relates to the technical field of CO removal in the steel industry, in particular to a carrier acidification N-doped Pt/TiO 2 Preparation method of-N catalyst and carrier acidified N-doped Pt/TiO 2 -an N catalyst.
Background
With the continuous promotion of the prevention and control work of the air pollution in various areas, the conventional air pollutants are effectively managed and controlled, so that the quality of the ambient air is gradually improved. At the same time, however, some non-traditional contaminants, such as carbon monoxide (CO), have begun to receive widespread attention. Among them, the steel industry, in particular the steel sintering industry, is one of the main sources of carbon monoxide emissions. Therefore, the method has important significance for effectively treating and controlling the emission of carbon monoxide in the steel sintering industry and continuously improving the quality of the atmospheric environment. To facilitate this work, related policy documents have been issued, such as Tangshan, handy, and fen, to facilitate carbon monoxide remediation in the iron and steel industry.
The CO oxidation catalytic combustion is an effective CO emission control means. However, due to the complexity of the flue gas composition of the steel sintering industry, in particular SO 2 And H 2 The presence of O makes the CO catalyst very susceptible to deactivation, which greatly increases the difficulty of industrial application. The CO emission control requirements of the steel sintering industry are not met by the CO catalysts on the market at present in terms of performance and durability.
It is therefore desirable to have a solution that solves or at least alleviates the above-mentioned drawbacks of the prior art.
Disclosure of Invention
The invention aims to provide a carrier acidified N-doped Pt/TiO 2 -a method of manufacturing an N catalyst to solve at least one of the technical problems described above.
In one aspect of the invention, a carrier acidified N-doped Pt/TiO is provided 2 -N catalyst manufacturing method for treating sintering flue gas CO, the carrier acidifying N-doped Pt/TiO 2 the-N catalyst comprises:
TiO is mixed with 2 Is put in dilute sulfuric acid solutionSoaking in the liquid, drying the soaked slurry into powder, transferring the powder into a tube furnace, heating to a first preset temperature, and heating in H 2 Treating in Ar mixed gas for a first preset time, and then introducing NH 3 Treating the Ar mixed gas for a second preset time to obtain a modified carrier;
the treated modified carrier was taken out and placed in a reaction kettle, and Pt (NO) was impregnated with the modified carrier by an impregnation method 3 ) 2 Drying the solution and the immersed slurry into powder, and then placing the powder in a muffle furnace to bake for a third preset time to obtain the carrier acidified N-doped Pt/TiO 2 -an N catalyst.
Optionally, the impregnated sulfate is with TiO 2 The proportion of (2) is between 0.5 and 2%.
Optionally, the drying the impregnated slurry into a powder comprises:
drying the impregnated slurry in an air atmosphere at 120-150 ℃.
Optionally, the at H 2 The first preset time for processing in the Ar mixed gas comprises the following steps:
the mixture is treated in H2/Ar mixed gas for 1-2H, and the H2 concentration is 1%.
Optionally, the NH is introduced 3 The second preset time for treating the Ar mixed gas comprises the following steps:
introducing NH 3 Ar mixed gas, NH 3 The concentration is 1%, and the treatment is carried out for 3-5 hours.
Optionally, the mass proportion of the impregnated Pt is between 0.5-1%.
Optionally, drying the impregnated slurry into a powder comprises:
the impregnated slurry is dried at 120-150 ℃.
Optionally, roasting the mixture in a muffle furnace for a third preset time to obtain carrier acidified N-doped Pt/TiO 2 the-N catalyst comprises:
roasting for 3-5h at 500 ℃ in a muffle furnace under the air condition to obtain carrier acidification N-doped Pt/TiO 2 -an N catalyst.
The application also provides a carrier acidified N-doped Pt/TiO 2 -N catalyst, said support acidifying N-blendHybrid Pt/TiO 2 N catalyst acidification of N-doped Pt/TiO by means of a support as described above 2 The N catalyst is prepared by a preparation method.
Advantageous effects
Acidification of N-doped Pt/TiO by the support of the present application 2 The catalyst prepared by the preparation method of the-N catalyst can reach higher CO conversion rate at 160-180 ℃ under the condition of 400,000h < -1 >, and SO at 200 ℃is realized 2 50ppm,H 2 Stable operation under the condition of O15%.
Drawings
FIG. 1 is a schematic illustration of carrier acidified N-doped Pt/TiO according to an embodiment of the present application 2 -a schematic flow diagram of a process for the production of N catalyst.
FIG. 2 is a schematic representation of activity data for three examples of the present application.
FIG. 3 is a schematic diagram of resistance experiments for three examples of the present application.
Detailed Description
In order to make the purposes, technical solutions and advantages of the implementation of the present application more clear, the technical solutions in the embodiments of the present application will be described in more detail below with reference to the accompanying drawings in the embodiments of the present application. In the drawings, the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The described embodiments are some, but not all, of the embodiments of the present application. The embodiments described below by referring to the drawings are exemplary and intended for the purpose of explaining the present application and are not to be construed as limiting the present application. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application. Embodiments of the present application are described in detail below with reference to the accompanying drawings.
FIG. 1 is a schematic illustration of carrier acidified N-doped Pt/TiO according to an embodiment of the present application 2 -a schematic flow diagram of a process for the production of N catalyst.
Carrier acidified N-doped Pt/TiO as shown in FIG. 1 2 the-N catalyst comprises:
step 1: tiO is mixed with 2 Soaking in dilute sulfuric acid solution, drying the soaked slurry into powder, transferring the powder into a tube furnace, heating to a first preset temperature, and heating in H 2 Treating in Ar mixed gas for a first preset time, and then introducing NH 3 Treating the Ar mixed gas for a second preset time to obtain a modified carrier;
step 2: the treated modified carrier was taken out and placed in a reaction kettle, and Pt (NO) was impregnated with the modified carrier by an impregnation method 3 ) 2 Drying the solution and the immersed slurry into powder, and then placing the powder in a muffle furnace to bake for a third preset time to obtain the carrier acidified N-doped Pt/TiO 2 -an N catalyst.
The application of noble metal CO catalysts for CO treatment of sintering flue gas requires pursuing low temperature activity and sulfur resistance.
In this example, the present application utilizes surface sulfate to reduce adsorption of SO2, thereby improving sulfur resistance. Although the surface sulfation mode can greatly improve the sulfur resistance of the catalyst, the surface sulfate has a negative effect on the Pt-based catalyst in the CO oxidation reaction process, because part of Pt can be loaded on the sulfate to greatly weaken the activity, and the application also provides a second point mode for establishing an anchor point to avoid the situation. Specifically, the low-temperature activity is mainly reflected in how to disperse noble metals such as Pt, and meanwhile, the activity is prevented from weakening after sulfation, and the application proposes a method for preparing the catalyst by utilizing Pt-N to easily form stronger coordination effect on TiO 2 Surface pass H 2 And NH 3 Ti-N bonds appear in the treatment, N is used as an anchor point, and a great deal of N adsorbs the traversed Pt ions to form Pt-N bonds in the impregnation method, so that the dispersion of Pt on the surface of the carrier is realized, and meanwhile, the activity reduction caused by the dispersion of part of Pt on sulfate radical is avoided.
In this example, the impregnated sulfate is with TiO 2 The proportion of (2) is between 0.5 and 2%.
In this embodiment, the drying the impregnated slurry into a powder includes:
drying the impregnated slurry in an air atmosphere at 120-150 ℃.
In the present embodiment, the above-mentioned method is that 2 Ar mixed gasThe first preset time of the process comprises the following steps:
at H 2 Treating in Ar mixed gas for 1-2h, H 2 The concentration was 1%. In this way, the purpose of treating the surface with hydrogen is to let TiO 2 Partial reduction of Ti in Ti 3+ Oxygen vacancies are formed, only so that NH can be introduced 3 Ti-N bonds may be formed.
In the embodiment, the NH is introduced 3 The second preset time for treating the Ar mixed gas comprises the following steps:
introducing NH 3 Ar mixed gas, NH 3 The concentration is 1%, and the treatment is carried out for 3-5 hours. Based on the previous step, NH is introduced 3 Can let Ti 3+ Adsorption of NH 3 Ti-N bond is formed.
In this example, the mass proportion of the impregnated Pt is between 0.5 and 1%. In this example, the mass ratio here means the ratio of platinum to the total amount in the catalyst, calculated from the content of platinum in the platinum nitrate.
In this embodiment, the drying of the impregnated slurry to a powder comprises:
the impregnated slurry is dried at 120-150 ℃.
In this embodiment, the carrier acidified N-doped Pt/TiO is obtained by baking the mixture in a muffle furnace for a third preset time 2 the-N catalyst comprises:
roasting for 3-5h at 500 ℃ in a muffle furnace under the air condition to obtain carrier acidification N-doped Pt/TiO 2 -an N catalyst. Roasting in air, using O 2 N is removed by oxidation, and Pt-N is recovered to Pt-O, so that the CO oxidation catalytic performance can be ensured.
By the method, the acidity of the carrier is improved by sulfating the carrier, SO that SO can be greatly reduced 2 Is less adsorbed by SO 2 And H 2 The catalyst poisoning behavior caused by O.
By H 2 Treatment of TiO 2 Defect is generated on the surface, and then NH is introduced 3 The treatment of doped N element has strong coordination effect on Pt, is beneficial to the dispersion of Pt on the surface of a carrier, and increases active sitesThereby greatly improving the activity of the catalyst.
A method for preparing a carrier acidified N-doped Pt/TiO2-N catalyst for sintering flue gas CO treatment, which comprises the following steps:
1. carrying out carrier modification to obtain TiO 2 Soaking in dilute sulfuric acid solution. In this process, sulfate and TiO are impregnated 2 The ratio of (2) is maintained between 0.5 and 2%.
2. Drying the impregnated slurry into powder in air atmosphere at 120-150deg.C.
3. Transferring the dried powder into a tube furnace, and in H 2 Treating in Ar mixed gas for a certain time. In the process, the furnace temperature is increased to 400 ℃ and the treatment time is 1-2h, H 2 The concentration was 1%.
4. After the treatment is finished, NH is introduced again 3 And (3) treating the mixed gas of Ar for a certain time. In this process, NH 3 The concentration is 1%, and the treatment time is 3-5h.
5. The treated carrier was taken out and placed in a reaction vessel, and Pt (NO) was impregnated with the carrier by an impregnation method 3 ) 2 The mass proportion of Pt in the solution is kept between 0.5 and 1 percent.
6. Drying the impregnated slurry to powder at 120-150deg.C.
7. And finally, placing the powder in a muffle furnace, and roasting at 500 ℃ for 3-5 hours to obtain the catalyst.
The catalyst is characterized in that the acidity of the carrier is improved by sulfating the carrier, thereby greatly reducing SO 2 Is less adsorbed by SO 2 And H 2 The catalyst poisoning behavior caused by O. Since sulfate negatively affects Pt-based CO catalysts, the introduction reduces the performance of the catalyst, and the support requires further treatment to improve Pt dispersion. By H 2 Treatment of TiO 2 Defect is generated on the surface, and NH is introduced 3 The treatment of doped N element has strong coordination effect on Pt, improves the dispersion of Pt on the surface of a carrier and increases active sites, thereby avoiding the introduction of sulfate radicals to reduce the CO oxidation performance of the catalyst and greatly improving the activity of the catalyst.
The catalyst of the invention is used for 400,000h -1 Under the condition of 160-180 ℃ can reach higher CO conversion rate, and at 200 ℃, SO 2 50ppm,H 2 Stable operation under the condition of O15%.
Referring to fig. 2, fig. 2 is a graph of activity data for three examples, test conditions: 400,000h -1 ,CO 8000ppm,O 2 20% of N2 balance gas.
Referring to fig. 3, fig. 3 is a resistance experiment of three examples, test conditions: 400,000h -1 ,CO 8000ppm,SO 2 50ppm,H 2 O 15%,O 2 20%,N 2 Balance the qi.
Example 1
100g of TiO is first added 2 Dispersing the carrier in deionized water, and dripping dilute sulfuric acid, dilute sulfuric acid and TiO into the slurry 2 The proportion of (2) is 0.5%. The impregnated slurry was dried to a powder in an air atmosphere at 120 ℃. Transferring the dried powder into a tube furnace, and in H 2 Treating in Ar mixed gas for 1h. In the process, the furnace temperature is increased to 400 ℃, H 2 The concentration was 1%. After the treatment is finished, NH is introduced again 3 And (3) treating the mixed gas of Ar for 3 hours. In this process, NH 3 The concentration was 1%.
99g of the treated carrier was weighed and placed in a reaction kettle, and Pt (NO) was impregnated by an impregnation method 3 ) 2 The mass of Pt in the solution was 1g. The impregnated slurry was dried to a powder at 120 ℃.
And finally, placing the powder in a muffle furnace, and roasting at 500 ℃ for 5 hours to obtain the catalyst.
Example 2
100g of TiO is first added 2 Dispersing the carrier in deionized water, and dripping dilute sulfuric acid, dilute sulfuric acid and TiO into the slurry 2 The proportion of (2) is 1%. The impregnated slurry was dried to a powder in an air atmosphere at 120 ℃. Transferring the dried powder into a tube furnace, and in H 2 Treating in Ar mixed gas for 1h. In the process, the furnace temperature is increased to 400 ℃, H 2 The concentration was 1%. After the treatment is finished, NH is introduced again 3 And (3) treating the mixed gas of Ar for 3 hours. In this process, NH 3 The concentration was 1%.
99g of the treated carrier was weighed and placed in a reaction kettle, and Pt (NO) was impregnated by an impregnation method 3 ) 2 The mass of Pt in the solution was 1g. The impregnated slurry was dried to a powder at 120 ℃.
And finally, placing the powder in a muffle furnace, and roasting at 500 ℃ for 5 hours to obtain the catalyst.
Example 3
100g of TiO is first added 2 Dispersing the carrier in deionized water, and dripping dilute sulfuric acid, dilute sulfuric acid and TiO into the slurry 2 The proportion of (2%). The impregnated slurry was dried to a powder in an air atmosphere at 120 ℃. Transferring the dried powder into a tube furnace, and in H 2 Treating in Ar mixed gas for 1h. In the process, the furnace temperature is increased to 400 ℃, H 2 The concentration was 1%. After the treatment is finished, NH is introduced again 3 And (3) treating the mixed gas of Ar for 3 hours. In this process, NH 3 The concentration was 1%.
99g of the treated carrier was weighed and placed in a reaction kettle, and Pt (NO) was impregnated by an impregnation method 3 ) 2 The mass of Pt in the solution was 1g. The impregnated slurry was dried to a powder at 120 ℃.
And finally, placing the powder in a muffle furnace, and roasting at 500 ℃ for 5 hours to obtain the catalyst.
The application also provides a carrier acidified N-doped Pt/TiO 2 -N catalyst, the support acidifying N-doped Pt/TiO 2 N catalyst acidification of N-doped Pt/TiO by means of a support as described above 2 The N catalyst is prepared by a preparation method.
Furthermore, it is evident that the word "comprising" does not exclude other elements or steps. A plurality of units, modules or means recited in the apparatus claims can also be implemented by means of software or hardware by means of one unit or total means.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.

Claims (9)

1. Carrier acidification N-doped Pt/TiO 2 -N catalyst production method for treating sintering flue gas CO, characterized in that the carrier acidizes N-doped Pt/TiO 2 the-N catalyst comprises:
TiO is mixed with 2 Soaking in dilute sulfuric acid solution, drying the soaked slurry into powder, transferring the powder into a tube furnace, heating to a first preset temperature, and heating in H 2 Treating in Ar mixed gas for a first preset time, and then introducing NH 3 Treating the Ar mixed gas for a second preset time to obtain a modified carrier;
the treated modified carrier was taken out and placed in a reaction kettle, and Pt (NO) was impregnated with the modified carrier by an impregnation method 3 ) 2 Drying the solution and the immersed slurry into powder, and then placing the powder in a muffle furnace to bake for a third preset time to obtain the carrier acidified N-doped Pt/TiO 2 -an N catalyst.
2. The carrier acidified N-doped Pt/TiO of claim 1 2 The method for preparing the N catalyst is characterized in that sulfate radical and TiO are impregnated 2 The proportion of (2) is between 0.5 and 2%.
3. The carrier acidified N-doped Pt/TiO of claim 2 2 -N catalyst manufacturing method, characterized in that said drying the impregnated slurry into powder comprises:
drying the impregnated slurry in an air atmosphere at 120-150 ℃.
4. The carrier acidified N-doped Pt/TiO of claim 3 2 A process for preparing N catalyst, characterized in that 2 The first preset time for processing in the Ar mixed gas comprises the following steps:
at H 2 The mixture is treated in Ar mixed gas for 1-2h, and the concentration of H2 is 1%.
5. The carrier acidified N-doped Pt/TiO of claim 4 2 The method for preparing the N catalyst is characterized in that NH is introduced 3 The second preset time for treating the Ar mixed gas comprises the following steps:
introducing NH 3 Ar mixed gas, NH 3 The concentration is 1%, and the treatment is carried out for 3-5 hours.
6. The carrier acidified N-doped Pt/TiO of claim 5 2 -N catalyst production method characterized in that the mass proportion of impregnated Pt is between 0.5 and 1%.
7. The carrier acidified N-doped Pt/TiO of claim 6 2 -N catalyst making method, characterized in that the drying of the impregnated slurry into powder comprises:
the impregnated slurry is dried at 120-150 ℃.
8. The carrier acidified N-doped Pt/TiO of claim 7 2 The preparation method of the N catalyst is characterized in that the carrier acidified N-doped Pt/TiO is obtained by roasting in a muffle furnace for a third preset time 2 the-N catalyst comprises:
roasting for 3-5h at 500 ℃ in a muffle furnace under the air condition to obtain carrier acidification N-doped Pt/TiO 2 -an N catalyst.
9. Carrier acidification N-doped Pt/TiO 2 -N catalyst, characterized in that the support acidizes N-doped Pt/TiO 2 -N catalyst acidifying N-doped Pt/TiO by a support according to any one of claims 1 to 8 2 The N catalyst is prepared by a preparation method.
CN202311067954.XA 2023-08-23 2023-08-23 Carrier acidification N-doped Pt/TiO 2 Method for preparing-N catalyst and catalyst Pending CN117258820A (en)

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