CN113318590B - Preparation method and application of high-surface-area high-dispersion manganese oxide coated aluminum oxide fluorine fixing agent - Google Patents
Preparation method and application of high-surface-area high-dispersion manganese oxide coated aluminum oxide fluorine fixing agent Download PDFInfo
- Publication number
- CN113318590B CN113318590B CN202110756073.3A CN202110756073A CN113318590B CN 113318590 B CN113318590 B CN 113318590B CN 202110756073 A CN202110756073 A CN 202110756073A CN 113318590 B CN113318590 B CN 113318590B
- Authority
- CN
- China
- Prior art keywords
- fixing agent
- fluorine
- temperature
- aluminum oxide
- coated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- B01D53/81—Solid phase processes
-
- 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
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method and application of a high-surface-area high-dispersion manganese oxide coated aluminum oxide fluorine fixing agent. Adding aqueous solution of hexamethylenetetramine and manganese nitrate into aluminum oxide, and rotating the mixture in a self-pressing kettle to react to obtain a manganese oxide precursor coated AlOOH. Then, roasting in the air to prepare the high-surface-area high-dispersion manganese oxide coated aluminum oxide fluorine fixing agent. The fluorine fixing agent prepared by the invention is used for decomposing nitrogen trifluoride waste gas discharged by the electronic industry, the reaction activity of the fluorine fixing agent is higher, and the application of the fluorine fixing agent is more beneficial to realizing the recovery of fluorine resources.
Description
Technical Field
The invention relates to a preparation method of a manganese oxide coated aluminum oxide fluorine fixing agent and application of the fluorine fixing agent, wherein the fluorine fixing agent is mainly used for decomposing nitrogen trifluoride (NF) discharged by the electronic industry 3 ) And (4) exhaust gas.
Background
NF 3 Is a novel etching gas and a cleaning gas used in the electronic industry, and the potential value of the greenhouse effect is 17200. NF after use 3 Exhaust gases, such as those directly released into the atmosphere, pose serious environmental hazards. Current NF 3 The waste gas treatment method mainly comprises the following steps: high temperature calcination, catalytic hydrolysis, and non-aqueous decomposition. Wherein, the high-temperature calcination method requires the treatment temperature to reach more than 1000 ℃ to obtain higher NF 3 The decomposition rate and the energy consumption are very high. The catalytic hydrolysis method is NF under the action of a catalyst 3 React with water to produce HF gas [ Takubo et al.Catal. Commun.2009, 11, 147-150, jeon, et al,Chem. Commun., 2003, 1244-1245]the main disadvantage is that HF gas generates hydrofluoric acid when meeting water, which has strong corrosion effect on the reactor. NF under anhydrous condition 3 Directly reacts with metal oxide (fluorine fixing agent), does not generate strong corrosive HF gas, has simple operation and NF 3 The fluorine element in the (C) is fixed in the form of metal fluoride (useful chemicals, such as fluxing agent used in smelting industry), and the recovery of fluorine resources can be realized.
VilenoEqual [ 2 ]Chem. Mater., 1996, 8, 1217-1221]NF under anhydrous conditions is reported 3 Decomposition reaction of (2), NF at 400 ℃ 3 May be at Al 2 O 3 Complete decomposition of (2 NF) 3 +Al 2 O 3 =NO+NO 2 +2AlF 3 ) However, al 2 O 3 The reactivity of (2) is very low. This is because: al (aluminum) 2 O 3 And NF 3 During reaction, surface layer Al 2 O 3 Gradually converted into highly dense AlF 3 Resulting in a gradual narrowing of the fluorine-fixing agent channels, NF 3 Gas diffusion is slower and slower, al of inner layer 2 O 3 Refractory NF 3 Reaction (AlF as the outer layer of the product) 3 The inner layer is still Al 2 O 3 ) Resulting in low reactivity of the fluorine-fixing agent.
The study of this group showed that: in Al 2 O 3 Surface supported Fe 2 O 3 、Co 3 O 4 NiO or Mn 2 O 3 The transition metal oxide, because of the fluorine/oxygen exchange effect between the surface and the matrix, can obviously improve the reaction activity of the fluorine fixing agent [ Xuxiu peak, etc.,J. Nat. Gas Chem., 2010, 19(5), 463;J. Environ. Chem. Eng., 2019, 7(3), 103192]。
the invention patent CN101406795B in China discloses an alumina-based defluorinating agent for nitrogen trifluoride anhydrous decomposition reaction and an application method thereof, which uses Fe (NO) under the conditions of normal temperature and normal pressure 3 ) 3 、Co(NO 3 ) 2 Or Ni (NO) 3 ) 2 Solution impregnation of Al 2 O 3 Base Al of the prepared fluorine-fixing agent 2 O 3 With the surface layer Fe 2 O 3 、Co 3 O 4 Or the bonding force of the NiO precursor is weak.
Chinese published invention patent application CN103961985A discloses a composition and preparation method of a high activity defluorinating agent for nitrogen trifluoride anhydrous decomposition reaction, which is prepared by using Mn (NO) under normal temperature and pressure 3 ) 2 Solution impregnation of Al 2 O 3 Base Al of the prepared fluorine-fixing agent 2 O 3 And the surface layer Mn 2 O 3 The bonding force of the precursor is weak.
Chinese published patent application CN108579397A discloses a high-utilization fluorine-fixing agent and a preparation method thereof, wherein urea is hydrolyzed to generate CO 2 And NH 3 Generation of carbonate ion and manganese ion in Al 2 O 3 Reaction on the surface, and roasting and decomposing the reaction product into large-grain Mn 2 O 3 Coated Al 2 O 3 。
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method and application of a high-surface-area high-dispersion manganese oxide coated aluminum oxide fluorine fixing agent, improving the surface area of the fluorine fixing agent and accelerating NF (nitrogen fluoride) 3 The gas is diffused and decomposed, and the manganese oxide is in a high dispersion state on the surface of the aluminum oxide, so that the interaction between the manganese oxide and the aluminum oxide is enhanced, and the reaction activity of the fluorine fixing agent is further improved.
The technical scheme of the invention is as follows:
a preparation method of a high-surface-area high-dispersion manganese oxide coated aluminum oxide fluorine fixing agent is characterized by comprising the following steps: adding aqueous solution of hexamethylenetetramine and manganese nitrate into aluminum oxide, and performing rotation reaction at the reaction temperature of 120-180 ℃ to obtain a manganese oxide precursor coated AlOOH; and then, roasting in the air, and decomposing the manganese oxide precursor coated AlOOH by heating to generate the high-surface-area high-dispersion manganese oxide coated aluminum oxide fluorine fixing agent.
The preparation method of the alumina comprises the following steps: and hydrothermally synthesizing AlOOH by using carbon spheres as a template agent, and roasting in air to obtain the aluminum oxide.
The reaction temperature is preferably 150 ℃ to 160 ℃.
The roasting temperature is preferably 600 ℃ to 650 ℃.
The rotary reaction is preferably carried out in an autoclav and brought to the reaction temperature at a rate of rise of 10 ℃ per minute.
During calcination in air, the temperature is preferably raised to the calcination temperature at a rate of 2 ℃ per minute.
The fluorine fixing agent prepared by the preparation method of the high-surface-area high-dispersion manganese oxide coated aluminum oxide fluorine fixing agent is used for nitrogen trifluoride waste gas decomposition reaction under anhydrous condition.
The invention has the following positive effects:
firstly, the invention synthesizes aluminum oxide firstly, and then synthesizes manganese oxide precursor to coat AlOOH. The selection of the precipitating agent, the crystallization temperature of the precursor and the post-treatment condition are all key technologies of the invention. The manganese oxide of the fluorine fixing agent is in a high dispersion state on the surface of alumina, and has strong interaction with the alumina, so that the fluorine fixing agent is an important reason for high activity, and the fluorine fixing agent is a remarkable characteristic compared with the prior art.
Secondly, the raw materials for preparing the fluorine fixing agent of the invention are as follows: glucose, aluminum nitrate, hexamethylenetetramine and manganese nitrate solution are cheap and easily available, and do no harm to human bodies and the environment. The preparation process of the fluorine fixing agent is simple, and the process parameters are easy to control.
And thirdly, the high-surface-area high-dispersion manganese oxide coated alumina fluorine fixing agent prepared by the invention has the advantages of small crystal grains of manganese oxide on the surface of alumina, high dispersion degree, high specific surface area of the fluorine fixing agent and high reaction activity.
Fourthly, compared with the published patent application CN103961985A, the creativity of the invention is that under the conditions of 120-180 ℃ and high pressure, manganese ions can be tightly adsorbed on the surface of AlOOH, so that the binding force between a manganese oxide precursor on the surface layer and alumina of a matrix (AlOOH generated under hydrothermal conditions) is strong, and the binding force between the surface layer and the matrix of the prepared finished fluorine fixing agent is strong. Therefore, the fluorine fixing agent has higher reactivity.
Fifth, in comparison with the published patent application CN108579397A, the inventive idea is that the precipitant is hexamethylenetetramine instead of urea, and the hexamethylenetetramine is hydrolyzed to form NH 3 The generated hydroxyl ions react with manganese ions adsorbed on the surface of AlOOH to generate a manganese oxide precursor coated AlOOH, and the reaction product is decomposed into small-grain manganese oxide coated aluminum oxide by roasting. Therefore, the fluorine fixing agent has higher reactivity.
Sixth, the experiment shows that: high surface area high dispersion prepared using the preparation method of the inventionManganese oxide coated alumina fluorine fixing agent for NF 3 The reaction activity of the decomposition reaction is obviously higher than that of the disclosed similar fluorine fixing agent [ Xuxiu peak, etc.; CN101406795B]。
Drawings
FIG. 1 is Al 2 O 3 NF of 3 Percentage decomposition data line graph.
FIG. 2 shows the preparation of MnOx coated Al by synthesis at 120 ℃ and calcination at 600 ℃ 2 O 3 NF of 3 Percentage decomposition data line graph.
FIG. 3 shows the preparation of MnOx coated Al by synthesis at 140 ℃ and calcination at 600 ℃ 2 O 3 NF of 3 Percentage decomposition data line plot.
FIG. 4 shows preparation of MnOx coated Al by synthesis at 150 ℃ and calcination at 600 ℃ 2 O 3 NF of 3 Percentage decomposition data line graph.
FIG. 5 is a process for preparing MnOx coated Al by synthesizing at 160 ℃ and roasting at 600 ℃ 2 O 3 NF on 3 Percentage decomposition data line plot.
FIG. 6 shows preparation of MnOx coated Al by synthesis at 170 ℃ and calcination at 600 ℃ 2 O 3 NF on 3 Percentage of decomposition data.
FIG. 7 shows preparation of MnOx coated Al by synthesis at 180 ℃ and calcination at 600 ℃ 2 O 3 NF on 3 Percentage decomposition data line plot.
FIG. 8 shows preparation of MnOx coated Al by synthesis at 150 ℃ and calcination at 650 ℃ 2 O 3 NF of 3 Percentage decomposition data line plot.
FIG. 9 shows preparation of MnOx coated Al by synthesis of urea at 150 ℃ and roasting at 650 ℃ 2 O 3 NF on 3 Percentage decomposition data line graph.
Detailed Description
The preparation method and the application effect of the high-surface-area high-dispersion manganese oxide coated aluminum oxide fluorine fixing agent are described in detail below by combining the examples and experimental data.
Specific surface area test conditions for each of the following examples: the test apparatus was an ASAP2020 physical adsorption apparatus manufactured by mack corporation, usa. Method for testingFirstly, drying the sample at 200 deg.C under reduced pressure for 4 hr to remove water and adsorbed impurities, and adding N 2 Adsorbing with adsorbent gas at-196 deg.C, and desorbing at room temperature. The specific surface area of the sample was calculated using the BET formula.
NF of each example 3 Decomposition reaction conditions: loading 2 g of fluorine-fixing agent into a reaction tube, placing into a reaction furnace, introducing reaction gas 2% 3 /98%He（NF 3 2%) of the reaction gas, and a total flow rate of the reaction gas was 50 ml/min. Reacting at constant temperature of 400 ℃. NF testing with gas chromatograph 3 Residual concentration, calculating NF 3 The decomposition rate.
The first embodiment is as follows: al as fluorine-fixing agent or raw material of subsequent embodiment 2 O 3 Preparation and NF thereof 3 And (4) carrying out decomposition reaction.
Dissolving 8 g of glucose in 45 ml of secondary distilled water to prepare a solution, moving the solution into a self-pressure kettle with a 100 ml polytetrafluoroethylene inner container, placing the self-pressure kettle into an oven, standing the self-pressure kettle, raising the temperature to 180 ℃ at a heating rate of 10 ℃/min, and reacting at constant temperature for 6 hours. The precipitate was washed alternately with redistilled water and ethanol. Drying at 80 ℃ for 12 hours to obtain the carbon spheres.
Dissolving 2.53 g of aluminum nitrate and 1.62 g of urea in 45 ml of secondary distilled water, adding the mixture into 1 g of carbon spheres, stirring and carrying out ultrasonic treatment for 10 minutes, moving the mixture into a self-pressure kettle with a 100 ml of polytetrafluoroethylene inner container, putting the self-pressure kettle into an oven, rotating the self-pressure kettle, increasing the temperature to 120 ℃ at the heating rate of 10 ℃/min, carrying out constant-temperature reaction for 4 hours, washing a product with the secondary distilled water and ethanol, and drying the product at 80 ℃ for 12 hours. Raising the temperature to 600 ℃ at the heating rate of 2 ℃/min in the air, and roasting at constant temperature for 4 hours to obtain Al 2 O 3 As fluorine fixing agent or raw material of the subsequent embodiment.
The specific surface area was found to be 164.0m 2 (iv) g. For NF 3 Free of water decomposition reaction, NF 3 The percentage decomposition data are shown in FIG. 1.
Example two: mnO as fluorine-fixing agent x Coated Al 2 O 3 Preparation and NF 3 And (4) decomposition reaction.
Taking 0.16 g as mass concentration50% manganese nitrate solution, 0.13 g hexamethylenetetramine in 45 ml of water, to 0.5 g of Al from "Ex.I 2 O 3 Stirring and ultrasonic processing for 10 minutes, moving the mixture into a self-pressure kettle with a 100 ml polytetrafluoroethylene inner container, putting the self-pressure kettle into an oven, rotating the self-pressure kettle, raising the temperature to 120 ℃ at the temperature rise rate of 10 ℃/min, reacting at constant temperature for 4 hours, washing the product with secondary distilled water, and drying at 80 ℃ for 12 hours. Raising the temperature to 600 ℃ at the temperature rise rate of 2 ℃/min in the air, and roasting at constant temperature for 4 hours to obtain MnO used as a fluorine fixing agent x Coated with Al 2 O 3 (wherein the mass of manganese represents 5% of the mass of the alumina).
The specific surface area was measured to be 182.6m 2 (iv) g. For NF 3 Free of water decomposition reaction, NF 3 The percentage decomposition data are shown in FIG. 2.
Example three: mnO as fluorine fixing agent x Coated Al 2 O 3 Preparation and NF 3 And (4) decomposition reaction.
At a heating rate of 10 ℃ per minute to 140 ℃, mnO x Coated with Al 2 O 3 Other steps and parameters were the same as in example two.
The specific surface area was found to be 236.0m 2 (ii) in terms of/g. For NF 3 Non-aqueous decomposition reaction, NF 3 The percentage decomposition data are shown in FIG. 3.
Example four: mnO as fluorine-fixing agent x Coated with Al 2 O 3 Preparation and NF 3 And (4) carrying out decomposition reaction.
At a heating rate of 10 ℃ per minute to 150 ℃, mnO x Coated with Al 2 O 3 Other steps and parameters were the same as in example two.
The specific surface area was found to be 237.1m 2 (iv) g. For NF 3 Free of water decomposition reaction, NF 3 The percentage decomposition data is shown in FIG. 4.
Example five: mnO as fluorine-fixing agent x Coated with Al 2 O 3 Preparation and NF 3 And (4) carrying out decomposition reaction.
At a heating rate of 10 ℃ per minute to 160 ℃, mnO x Coated with Al 2 O 3 Other steps and parameters were the same as in example two.
The specific surface area was found to be 181.8m 2 (iv) g. For NF 3 Free of water decomposition reaction, NF 3 The percentage decomposition data are shown in FIG. 5.
Example six: mnO as fluorine-fixing agent x Coated Al 2 O 3 Preparation and NF 3 And (4) carrying out decomposition reaction.
At a heating rate of 10 ℃ per minute to 170 ℃, mnO x Coated with Al 2 O 3 Other steps and parameters were the same as in example two.
The specific surface area was found to be 176.0m 2 (ii) in terms of/g. For NF 3 Non-aqueous decomposition reaction, NF 3 The percentage decomposition data is shown in figure 6.
Example seven: mnO as fluorine-fixing agent x Coated Al 2 O 3 Preparation and NF 3 And (4) carrying out decomposition reaction.
At a heating rate of 10 ℃ per minute to 180 ℃, mnO x Coated with Al 2 O 3 Other steps and parameters were the same as in example two.
The specific surface area was found to be 141.6m 2 (iv) g. For NF 3 Non-aqueous decomposition reaction, NF 3 The percentage decomposition data is shown in FIG. 7.
Example eight: mnO as fluorine-fixing agent x Coated with Al 2 O 3 Preparation and NF 3 And (4) carrying out decomposition reaction.
Elevated to 650 ℃ MnO at a rate of 2 ℃/min in air x Coated with Al 2 O 3 Other steps and parameters were the same as in example four.
The specific surface area was found to be 232.1m 2 (iv) g. For NF 3 Non-aqueous decomposition reaction, NF 3 The percentage decomposition data is shown in FIG. 8.
Example nine: mnO as fluorine-fixing agent x Coated Al 2 O 3 Preparation and NF 3 And (4) carrying out decomposition reaction.
0.16 g of a 50% strength by weight manganese nitrate solution and 0.11 g of urea are dissolved in 45 ml of water and added to 0.5 g of the solution obtained in "example oneAl 2 O 3 Stirring and ultrasonic processing for 10 minutes, moving the mixture into a self-pressure kettle with a 100 ml polytetrafluoroethylene inner container, putting the self-pressure kettle into an oven, rotating the self-pressure kettle, raising the temperature to 150 ℃ at the temperature rise rate of 10 ℃/min, reacting at constant temperature for 4 hours, washing the product with secondary distilled water, and drying at 80 ℃ for 12 hours. Raising the temperature to 650 ℃ at the temperature rise rate of 2 ℃/min in the air, and roasting at constant temperature for 4 hours to obtain MnO used as a fluorine fixing agent x Coated with Al 2 O 3 (wherein the mass of manganese is 5% of the mass of alumina).
The specific surface area was measured to be 167.8m 2 (iv) g. For NF 3 Free of water decomposition reaction, NF 3 The percentage decomposition data is shown in FIG. 9.
As can be seen from fig. 1 to 8: first, mnO x Coated with Al 2 O 3 The reactivity of the fluorine fixing agent is higher than that of pure Al 2 O 3 . Secondly, mnO prepared at the hydrothermal temperature of 150-160 DEG C x Coated Al 2 O 3 The fluorine fixing agent has the highest reaction activity. Thirdly, mnO preparation by raising the calcination temperature from 600 ℃ to 650 ℃ x Coated Al 2 O 3 The reaction activity of the fluorine fixing agent is not reduced. Accordingly, the reaction temperature is preferably 150 ℃ to 160 ℃, and the calcination temperature is preferably 600 ℃ to 650 ℃.
Comparing example eight and example nine with fig. 8 and fig. 9, it can be seen that: mnO prepared from hexamethylenetetramine as precipitator x Coated with Al 2 O 3 The specific surface area and the reaction activity of the fluorine fixing agent are obviously higher than those of the fluorine fixing agent prepared by selecting urea as a precipitator.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included therein.
Claims (3)
1. A preparation method of a high-surface-area high-dispersion manganese oxide coated aluminum oxide fluorine fixing agent is characterized by comprising the following steps: adding aqueous solution of hexamethylenetetramine and manganese nitrate into aluminum oxide, and performing rotary reaction at the reaction temperature of 150-160 ℃ to obtain a manganese oxide precursor coated AlOOH; then, roasting in the air, and heating and decomposing AlOOH coated by the manganese oxide precursor to generate the high-surface-area high-dispersion manganese oxide coated aluminum oxide fluorine fixing agent; the rotation reaction is carried out in a self-pressure kettle, and the temperature is increased to the reaction temperature at the temperature rising rate of 10 ℃ per minute; the roasting temperature is 600-650 ℃; the temperature was raised to the calcination temperature at a ramp rate of 2 ℃ per minute.
2. The method of claim 1, wherein the alumina is prepared by the following steps: and hydrothermally synthesizing AlOOH by using carbon spheres as a template agent, and roasting in air to obtain the aluminum oxide.
3. The fluorine fixing agent prepared by the preparation method of the high-surface-area high-dispersion manganese oxide coated aluminum oxide fluorine fixing agent according to claim 1 or 2 is used for nitrogen trifluoride waste gas decomposition reaction under anhydrous conditions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110756073.3A CN113318590B (en) | 2021-07-05 | 2021-07-05 | Preparation method and application of high-surface-area high-dispersion manganese oxide coated aluminum oxide fluorine fixing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110756073.3A CN113318590B (en) | 2021-07-05 | 2021-07-05 | Preparation method and application of high-surface-area high-dispersion manganese oxide coated aluminum oxide fluorine fixing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113318590A CN113318590A (en) | 2021-08-31 |
| CN113318590B true CN113318590B (en) | 2022-12-02 |
Family
ID=77425505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110756073.3A Active CN113318590B (en) | 2021-07-05 | 2021-07-05 | Preparation method and application of high-surface-area high-dispersion manganese oxide coated aluminum oxide fluorine fixing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113318590B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115845793B (en) * | 2023-01-05 | 2024-03-29 | 烟台大学 | Preparation method and application of ordered mesoporous fluorine fixing agent with high surface area and high pore volume |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA883238A (en) * | 1971-10-12 | F. Hilton Raymond | Coating of the interior surfaces of porous materials | |
| CN107235571B (en) * | 2016-03-28 | 2021-02-19 | 宝山钢铁股份有限公司 | Method and device for efficiently removing SCOD (selective catalytic oxidation) in coking reverse osmosis concentrated water |
| CN106512936B (en) * | 2016-11-11 | 2018-10-02 | 镇江市高等专科学校 | A kind of hydro-thermal method prepares de-fluoridation adsorbent and its application |
| CN107321352B (en) * | 2017-07-19 | 2021-04-09 | 武汉凯迪工程技术研究总院有限公司 | Circulating fluidized bed nickel-based reforming catalyst and preparation method and application thereof |
| CN108579397B (en) * | 2018-04-25 | 2021-09-21 | 烟台大学 | Fluorine fixing agent with high utilization rate and preparation method thereof |
| CN110453097B (en) * | 2019-09-17 | 2021-12-17 | 广东先导稀材股份有限公司 | Method for distilling and extracting germanium from fluorine-containing germanium concentrate |
-
2021
- 2021-07-05 CN CN202110756073.3A patent/CN113318590B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113318590A (en) | 2021-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109482175B (en) | Manganese-potassium ore type manganese dioxide catalyst with yolk-shell structure and preparation method and application thereof | |
| CN109012656B (en) | Ordered mesoporous gamma-MnO2Catalyst, preparation method and application thereof | |
| CN112337504B (en) | Simultaneously containing HCN and AsH during treatment3Industrial tail gas production method | |
| CN106745170B (en) | A kind of cobalt doped cerium oxide nano materials of laminated structure and its preparation and application | |
| CN111889101A (en) | Modified composite oxide catalyst for synergistic purification of VOCs and NO and preparation method thereof | |
| CN113318590B (en) | Preparation method and application of high-surface-area high-dispersion manganese oxide coated aluminum oxide fluorine fixing agent | |
| CN113042066B (en) | Flue gas denitration catalyst and preparation method thereof | |
| CN106732581A (en) | A kind of Ru/CeTiO for low-temperature SCR reactionXThe preparation method of catalyst | |
| CN112337460A (en) | Method for preparing Mn-based spinel low-temperature denitration catalyst by using complex acid solution | |
| CN108579397B (en) | Fluorine fixing agent with high utilization rate and preparation method thereof | |
| CN113387908A (en) | Application of magnesium cobaltate catalyst in selective oxidation reaction of styrene | |
| CN110947396B (en) | Spherical manganese oxide coated iron oxide core shell structural composite, preparation method and application | |
| CN114832848B (en) | Catalyst and preparation method and application thereof | |
| CN115364868B (en) | Catalyst for catalytically decomposing ozone and preparation method thereof | |
| CN114308052B (en) | Preparation method of strong-effect water-resistant and sulfur-resistant denitration catalyst | |
| CN113649032B (en) | Vinylidene fluoride catalyst and preparation method thereof | |
| CN115845793B (en) | Preparation method and application of ordered mesoporous fluorine fixing agent with high surface area and high pore volume | |
| CN113000045B (en) | Manganese-based catalyst and preparation method and application thereof | |
| CN107376915B (en) | Carbon dioxide methanation catalyst and preparation method thereof | |
| CN113680354B (en) | High-temperature denitration catalyst of titanyl sulfate-loaded niobium pentoxide | |
| CN115608364B (en) | Oxygen carrier material for methane chemical-looping hydrogen production and large-scale preparation method | |
| CN111545191B (en) | Lithium potassium manganese composite oxide catalyst capable of being regenerated in heating mode and used for ozonolysis and preparation method thereof | |
| CN115722246B (en) | SO resistance suitable for medium and low temperature condition 2 Combined denitration mercury-removal catalyst and preparation method thereof | |
| JP3760076B2 (en) | Adsorbent such as nitrogen oxide, method for producing the same, and method for removing nitrogen oxide and the like | |
| CN113070072B (en) | Catalyst for desulfurization and denitrification and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |