CN108579397B - Fluorine fixing agent with high utilization rate and preparation method thereof - Google Patents

Fluorine fixing agent with high utilization rate and preparation method thereof Download PDF

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CN108579397B
CN108579397B CN201810381296.4A CN201810381296A CN108579397B CN 108579397 B CN108579397 B CN 108579397B CN 201810381296 A CN201810381296 A CN 201810381296A CN 108579397 B CN108579397 B CN 108579397B
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徐秀峰
李和健
潘燕飞
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Yantai University
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Abstract

The invention relates to a fluorine fixing agent with high utilization rate and a preparation method thereof. The method firstly synthesizes Al with a thin shell appearance2O3Adding aqueous solution of urea, manganese nitrate or cobalt nitrate, and rotating and crystallizing in a self-pressure reaction kettle to obtain Al with a thin shell shape2O3Loaded Mn2O3Or Co3O4The precursor of (1). Then, roasting in the air to prepare the Al with the thin shell appearance2O3Loaded with Mn2O3Or Co3O4A fluorine fixing agent. In which manganese or cobalt atoms are bound to Al2O3The mass ratio of the components is 3-8%, and the optimal mass ratio is 5%. The fluorine fixing agent prepared by the invention is used for decomposing nitrogen trifluoride waste gas discharged by the electronic industry, has high reaction activity and high utilization rate, the utilization rate is up to 98 percent at most, and the recovery of fluorine resources is realized.

Description

Fluorine fixing agent with high utilization rate and preparation method thereof
Technical Field
The invention relates to a fluorine fixing agent with high utilization rate and a preparation method thereof, which can be used for decomposing nitrogen trifluoride waste gas discharged by the electronic industry and belong to the field of environmental protection.
Background
The ground temperature is in a trend of rising due to greenhouse gases emitted by people, and the wide attention of the international society is attracted. Nitrogen trifluoride (NF) as etching gas and cleaning gas for electronic industry3) Is one of important greenhouse gases, has the potential value of 17200 for greenhouse effect and has the service life of about 740 years. NF after use3Exhaust gases, such as those directly released into the atmosphere, pose serious environmental hazards.
Current NF3The waste gas treatment method comprises the following steps: high temperature calcination, catalytic hydrolysis, anhydrous decomposition, and the like. Wherein, the high-temperature calcination method requires the treatment temperature to reach more than 1000 ℃ to obtain higher NF3The decomposition rate and the energy consumption are very high. Decomposition of NF by catalytic hydrolysis3The exhaust gas is hydrogen fluoride gas [ Takubo et al ] produced by the reaction of nitrogen trifluoride with water in the presence of a catalyst.Catal. Commun.2009, 11, 147-,Chem. Commun., 2003, 1244-1245]the hydrogen fluoride gas generates hydrofluoric acid when meeting water, has strong corrosion effect on the reactor, and has complex operation flow. The method has the advantages that nitrogen trifluoride directly reacts with metal oxide (fluorine fixing agent) under anhydrous condition, strong corrosive hydrogen fluoride gas is not generated, the operation is simple, the method is superior to a catalytic hydrolysis method, and fluorine in the nitrogen trifluoride is fixed in the form of metal fluoride (the metal fluoride is a useful chemical product, such as a fluxing agent for smelting aluminum, the melting temperature of an electrolyte is reduced, the conductivity of the electrolyte is improved), and the recovery of fluorine resources is realized.
In 1996, Vileno et alChem. Mater., 1996, 8, 1217-1221]NF under anhydrous conditions is reported3In Al2O3Decomposition reaction of N, N under 400 deg.C3In Al2O3Above is completely decomposed, but Al2O3The utilization of (2) is very low. This is because: al (Al)2O3And NF3During the reaction, the surface layer Al2O3Gradually converted into AlF with low pore volume and high density3Resulting in a gradual narrowing of the fluorine-fixing agent channels, NF3The gas diffusion becomes slower and slower, so that Al of the inner layer2O3Difficult to react with NF3And (4) reacting. X-ray diffraction analysis showed: only a part of Al2O3Is converted into AlF3(conversion of the surface layer to AlF3The inner layer is still Al2O3）。
Compared with the prior technical requirements, the Al is used2O3The utilization rate of the fluorine fixing agent of the method still does not meet the industrial requirement.
Disclosure of Invention
The invention aims to solve the technical problem of providing a fluorine fixing agent with high utilization rate and a preparation method thereof. The fluorine fixing agent is used for the anhydrous decomposition reaction of nitrogen trifluoride, the utilization rate of the fluorine fixing agent is up to 98 percent, and the purity of the fluorine fixing product is high.
One of the technical schemes provided by the invention is that the preparation method of the fluorine fixing agent with high utilization rate firstly synthesizes Al with thin shell appearance2O3Adding aqueous solution of urea, manganese nitrate or cobalt nitrate; moving to a self-pressure reaction kettle, rotating and crystallizing at 120-180 ℃, wherein the optimal crystallization temperature is 160 ℃, and obtaining the Al with the shape of a thin shell2O3Loaded Mn2O3Or Co3O4A precursor; then, 600C roasting is carried out in the air, and Al with a thin shell appearance2O3Mn of the surface2O3Or Co3O4The precursor is heated and decomposed to generate Al with a thin shell shape2O3Loaded with Mn2O3Or Co3O4Fluorine fixing agent; in which manganese or cobalt atoms are bound to Al2O3The mass ratio of the components is 3-8%, and the optimal mass ratio is 5%.
The second technical scheme provided by the invention is that the fluorine fixing agent with high utilization rate is prepared by the preparation method and is used for nitrogen trifluoride anhydrous decomposition reaction.
Experiments show that: thin shell morphology Al prepared using the preferred parameters of the present invention2O3Loaded with Mn2O3Or Co3O4The fluorine fixing agent is used for nitrogen trifluoride decomposition reaction, the utilization rate of the fluorine fixing agent is up to 98 percent and is obviously higher than that of the disclosed fluorine fixing agent [ Vileno and the like,Chem. Mater.1996, 8, 1217-; xuxifeng, etc., Chinese patent ZL200810158706.5, xuxifeng, etc., Chinese patent 201410111749.3; xuxifeng et al, Chinese patent 201710328263.9]。
The invention has the following characteristics:
(1) the invention uses hydrothermal synthesis method to prepare the Al with thin shell appearance2O3Loaded with Mn2O3Or Co3O4Fluorine-fixing agent, surface layer Mn thereof2O3Or Co3O4With matrix Al2O3The bonding acting force between the fluorine fixing agents is strong, the reaction activity and the utilization rate of the fluorine fixing agent are high, the quantity change is generated, and the utilization rate is up to 98 percent beyond the expectation of the technical personnel in the field.
Experiments show that: the bonding effect between the surface layer and the matrix of the fluorine fixing agent obtained by the previous research results of the applicant is weak, and the reaction activity and the utilization rate of the fluorine fixing agent are far lower than those of the fluorine fixing agent prepared by the hydrothermal synthesis method.
(2) The invention firstly synthesizes Al with a thin shell appearance2O3Then on Al2O3Surface synthesis of Mn2O3Or Co3O4The precursor is roasted to generate Al with a thin shell shape2O3Loaded with Mn2O3Or Co3O4A fluorine fixing agent. Wherein the shape of the thin shell is Al2O3Loaded with Mn2O3Or Co3O4The crystallization temperature of the precursor and the loading capacity of the auxiliary agent (manganese or cobalt) are key technologies of the invention.
Experiments show that: compared with the previous preparation method of the applicant, the preparation method has different guiding ideas, namely the crystallization temperature and the auxiliary agent loading capacity are selected, so that the prepared fluorine-fixing agent has high reaction activity and utilization rate, and the lower and higher crystallization temperature and auxiliary agent loading capacity can reduce the utilization rate of the fluorine-fixing agent.
The invention has the following outstanding advantages:
(1) the invention prepares raw materials of fluorine fixing agent, such as: glucose, aluminum nitrate, urea, manganese nitrate solution and cobalt nitrate, which are cheap and easily available and do no harm to human body and environment. The preparation process of the fluorine fixing agent is simple, and the preparation process parameters are easy to control.
(2) The fluorine fixing agent has high reaction activity, high utilization rate and high purity of fluorine fixing products.
The chemical principle of the invention is as follows:
NF3in Al2O3Loaded with Mn2O3Or Co3O4NF during decomposition on fluorine-fixing agent3And the surface layer Mn2O3Or Co3O4Reacting to produce MnF3Or CoF2(as shown in the following chemical reaction formulas 1 and 2, whereinrG is calculated as the reaction Gibbs free energy at 400C):
2NF3+Mn2O3=NO+NO2+2MnF3,rG= 405.9 kJ/mol (1)
4NF3+2Co3O4=2NO+2NO2+O2+6CoF2, rG=418.5 kJ/mol (2)
surface layer MnF3Or CoF2Then with the matrix Al2O3Generates AlF by the 'fluorine/oxygen exchange reaction' between the two3(as shown in the following chemical reaction formulas 3 and 4, whereinrG is calculated as the reaction Gibbs free energy at 400C):
Al2O3+2MnF3=2AlF3+Mn2O3,rG= 176.0 kJ/mol (3)
Al2O3+3CoF2 =2AlF3+3CoO, rG= 63.4 kJ/mol (4)
therefore, the surface layer Mn2O3Or Co3O4The fluorination of (A) promotes the matrix Al2O3Thereby improving the reactivity and the utilization rate of the fluorine fixing agent.
The invention is from the project on the foundation of the Shandong province 'transition metal oxide/Al' natural science2O3Composite fluorine-fixing agent in NF3Fluorine/oxygen exchange effect and reactivity between "surface/substrate" in decomposition reaction (project approval No.: ZR2017MB 020). The creativity of the invention is that in the method step, the crystallization temperature is 120-180 ℃ and is higher than the normal pressure, namely, the pressure generated by water vaporization enhances the bonding acting force of the matrix alumina and the surface layer manganese oxide or cobalt hydroxide, and the manganese ions or cobalt ions can be tightly adsorbed on the surface of the thin-shell aluminum oxide to form a layered tight bonding layer, thereby the thin-shell Al is prepared by roasting2O3Loaded with Mn2O3Or Co3O4Base body Al of2O3And the surface layer Mn2O3Or Co3O4The binding action force is strong, which is beneficial to the generation of fluorine/oxygen exchange reaction, therefore, the reactivity and the utilization rate of the fluorine fixing agent are high, which exceed the expectation imagination of the technical personnel in the field, and the utilization rate can reach 98 percent at most.
Drawings
FIG. 1 shows the morphology of thin shell Al2O3NF of3Percentage of decomposition data.
FIG. 2 shows a 120C synthesized thin-shell morphology Al2O3Loaded with Co3O4（5%Co/Al2O3) NF of3Percentage of decomposition data.
FIG. 3 shows a 120C synthesized thin shell morphology Al2O3Loaded with Mn2O3（5%Mn/Al2O3) NF of3Percentage of decomposition data.
FIG. 4 shows a thin-shelled Al alloy synthesized at 140C2O3Loaded with Mn2O3（5%Mn/Al2O3) NF of3Decomposition ofPercentage data.
FIG. 5 is a 160C synthesized thin shell morphology Al2O3Loaded with Mn2O3（5%Mn/Al2O3) NF of3Percentage of decomposition data.
FIG. 6 shows a thin-shelled Al synthesized at 180C2O3Loaded with Mn2O3（5%Mn/Al2O3) NF of3Percentage of decomposition data.
FIG. 7 shows 190C synthesized thin shell morphology Al2O3Loaded with Mn2O3（5%Mn/Al2O3) NF of3Percentage of decomposition data.
FIG. 8 is a 160C synthesized thin shell morphology Al2O3Loaded with Mn2O3（8%Mn/Al2O3) NF of3Percentage of decomposition data.
FIG. 9 shows a 160C synthesized thin shell morphology Al2O3Loaded with Mn2O3（3%Mn/Al2O3) NF of3Percentage of decomposition data.
FIG. 10 shows a 160C synthesized thin shell morphology Al2O3Loaded with Mn2O3（2%Mn/Al2O3) NF of3Percentage of decomposition data.
Detailed Description
The invention provides a fluorine fixing agent with high utilization rate and a preparation method thereof. Firstly synthesizing Al with thin shell appearance2O3Adding aqueous solution of urea, manganese nitrate or cobalt nitrate; rotating and crystallizing at 120-180 ℃ to obtain Al with a thin shell shape2O3Loaded Mn2O3Or Co3O4A precursor; roasting of 600C in air, Mn2O3Or Co3O4The precursor is heated and decomposed to prepare Al with a thin shell shape2O3Loaded with Mn2O3Or Co3O4Fluorine fixing agent; in which manganese or cobalt atoms are bound to Al2O3The mass ratio of (A) is 3% -8%.
The method comprises the following specific operations:
1) taking glucose as a raw material to synthesize carbon spheres by hydrothermal synthesis; then adding a mixed aqueous solution of aluminum nitrate and urea into the carbon spheres, wherein the mass ratio of aluminum atoms to the carbon spheres is 0.109-0.207, and the molar ratio of urea molecules to the aluminum atoms is 3.5-5; then hydrothermally synthesizing aluminum hydroxide on the surface of the carbon sphere, wherein the crystallization temperature is 110-130 ℃; then 600C in the air is roasted to remove carbon spheres to obtain Al with a thin shell appearance2O3。
2) In the shape of thin shell Al2O3Adding aqueous solution of urea, manganese nitrate or cobalt nitrate, mixing and stirring, carrying out ultrasonic treatment for 10-30 minutes, moving the mixture into an autogenous pressure kettle with a polytetrafluoroethylene inner container, placing the autogenous pressure kettle into an oven, rotating the autogenous pressure kettle, raising the temperature to 120-180 ℃ at the temperature rise rate of 5 ℃ per minute, crystallizing at constant temperature for 4 hours, washing the product with deionized water, drying at 80 ℃ for 12 hours to obtain the product, namely the Al with the shape of a thin shell2O3Loaded Mn2O3Or Co3O4A precursor;
then, the temperature is raised to 600 ℃ in the air at the heating rate of 5 ℃ per minute, the product is roasted for 4 hours at constant temperature, and the shape of the thin shell Al is thin2O3Mn of the surface2O3Or Co3O4The precursor is heated and decomposed to generate Al with a thin shell shape2O3Loaded with Mn2O3Or Co3O4Fluorine fixing agent;
wherein manganese or cobalt atoms are bonded to Al2O3The mass ratio of (3-8): 100.
the invention relates to a fluorine-fixing agent with high utilization rate and a preparation method thereof.
Example one
Dissolving 8 g of glucose in 45 ml of deionized water to prepare a solution, moving the solution into a self-pressure kettle with a 100 ml of polytetrafluoroethylene inner container, placing the self-pressure kettle into an oven, standing the self-pressure kettle, increasing the temperature to 180 ℃ at a heating rate of 10 ℃ per minute, and reacting at constant temperature for 6 hours. The precipitate was washed alternately with deionized water and ethanol. And drying for 12 hours at 80 ℃ to obtain the carbon spheres.
2.5321 g of aluminum nitrate and 1.6216 g of urea are dissolved in 45 ml of deionized water, added into 1 g of carbon spheres, stirred and ultrasonically treated for 10 minutes, moved into an autogenous pressure kettle with a 100 ml of polytetrafluoroethylene inner container, the autogenous pressure kettle is placed in an oven, the autogenous pressure kettle rotates, the temperature is increased to 120 ℃ at the heating rate of 10 ℃ per minute, the reaction is carried out at the constant temperature for 4 hours, the product is washed by the deionized water and ethanol, and dried at 80 ℃ for 12 hours. Heating to 600 ℃ at a heating rate of 5 ℃ per minute in air, and roasting the product at a constant temperature for 4 hours to obtain the Al with the thin shell appearance2O3. For NF3Non-aqueous decomposition reaction, NF3The percentage decomposition data are shown in FIG. 1.
NF3Decomposition reaction conditions: 2 g of fluorine fixing agent is put into a reaction tube and is put into a reaction furnace, and reaction gas of 2.8 percent NF is introduced3/97.2%He（NF3The volume concentration of (b) was 2.8%), and the reaction gas flow rate was 50 ml/min. Reacting at constant temperature of 400 ℃. NF testing with gas chromatograph3Residual concentration, calculating NF3The decomposition rate. NF of each example3The decomposition reaction conditions were the same.
Example two
0.1235 g of cobalt nitrate and 0.1019 g of urea are dissolved in 45 ml of water and added into 0.5 g of thin-shell alumina prepared in the first embodiment, the mixture is stirred and ultrasonically treated for 10 minutes and then is moved into an autogenous pressure kettle with a 100 ml of polytetrafluoroethylene inner container, the autogenous pressure kettle is placed into an oven and rotated, the temperature is increased to 120 ℃ at the rate of 5 ℃ per minute, the reaction is carried out at constant temperature for 4 hours, the product is washed by deionized water, and the product is dried at 80 ℃ for 12 hours. Heating to 600 ℃ at a heating rate of 5 ℃ per minute in the air, and roasting the product at a constant temperature for 4 hours to obtain the Al with the thin shell morphology as the defluorinating agent2O3Loaded with Co3O4And is noted as 5% Co/Al2O3(wherein the mass of cobalt is 5% of the mass of alumina). For NF3Non-aqueous decomposition reaction, NF3Decomposition conditions were the same as in example one, NF3The percentage decomposition data are shown in FIG. 2.
EXAMPLE III
Taking 0.1628 g of the mixture with the mass concentration of 50 percentManganese nitrate solution and 0.1093 g of urea are dissolved in 45 ml of water, added into 0.5 g of aluminum oxide with a thin shell shape prepared in the first embodiment, stirred and ultrasonically treated for 10 minutes, moved into an auto-pressing kettle with a 100 ml of polytetrafluoroethylene inner container, placed into an oven, rotated to raise the temperature to 120 ℃ at the temperature raising rate of 5 ℃ per minute, reacted at constant temperature for 4 hours, the product is washed by deionized water, and dried at 80 ℃ for 12 hours. Heating to 600 ℃ at a heating rate of 5C/min in the air, and roasting the product at a constant temperature for 4 hours to obtain the thin-shell-shaped Al serving as the defluorinating agent2O3Loaded with Mn2O35% Mn/Al2O3(wherein the mass of manganese is 5% of the mass of alumina). For NF3Non-aqueous decomposition reaction, NF3Decomposition conditions were the same as in example one, NF3The percentage decomposition data are shown in FIG. 3.
Example four
0.1628 g of a 50% manganese nitrate solution and 0.1093 g of urea by mass are dissolved in 45 ml of water, added to 0.5 g of the aluminum oxide with the shape of a thin shell prepared in the first embodiment, stirred and ultrasonically treated for 10 minutes, transferred to an autoclave provided with a 100 ml polytetrafluoroethylene inner container, heated to 140 ℃ at a heating rate of 5 ℃ per minute, reacted at a constant temperature for 4 hours, the product is washed with deionized water, and dried at 80 ℃ for 12 hours. Heating to 600 ℃ at a heating rate of 5C/min in the air, and roasting the product at a constant temperature for 4 hours to obtain the thin-shell-shaped Al serving as the defluorinating agent2O3Loaded with Mn2O35% Mn/Al2O3(wherein the mass of manganese is 5% of the mass of alumina). For NF3Non-aqueous decomposition reaction, NF3Decomposition conditions were the same as in example one, NF3The percentage decomposition data are shown in FIG. 4.
EXAMPLE five
Dissolving 0.1628 g of manganese nitrate solution with the mass concentration of 50% and 0.1093 g of urea in 45 ml of water, adding the solution into 0.5 g of aluminum oxide with the shape of a thin shell prepared in the first embodiment, stirring and ultrasonically treating the solution for 10 minutes, moving the solution into a self-pressure kettle provided with a 100 ml polytetrafluoroethylene inner container, placing the self-pressure kettle into an oven, rotating the self-pressure kettleThe temperature is increased to 160 ℃ at the temperature rising rate of 5 ℃ per minute, the reaction is carried out for 4 hours at constant temperature, and the product is washed by deionized water and dried for 12 hours at 80 ℃. Heating to 600 ℃ at a heating rate of 5C/min in the air, and roasting the product at a constant temperature for 4 hours to obtain the thin-shell-shaped Al serving as the defluorinating agent2O3Loaded with Mn2O35% Mn/Al2O3(wherein the mass of manganese is 5% of the mass of alumina). For NF3Non-aqueous decomposition reaction, NF3Decomposition conditions were the same as in example one, NF3The percentage decomposition data are shown in figure 5.
EXAMPLE six
0.1628 g of a manganese nitrate solution with the mass concentration of 50% and 0.1093 g of urea are dissolved in 45 ml of water, added into 0.5 g of the thin-shell aluminum oxide prepared in the first embodiment, stirred and ultrasonically treated for 10 minutes, moved into an auto-pressure kettle with a 100 ml polytetrafluoroethylene inner container, the auto-pressure kettle is placed in an oven, rotated, heated to 180 ℃ at the heating rate of 5 ℃ per minute, reacted at a constant temperature for 4 hours, a product is washed with deionized water, and dried at 80 ℃ for 12 hours. Heating to 600 ℃ at a heating rate of 5C/min in the air, and roasting the product at a constant temperature for 4 hours to obtain the thin-shell-shaped Al serving as the defluorinating agent2O3Loaded with Mn2O35% Mn/Al2O3(wherein the mass of manganese is 5% of the mass of alumina). For NF3Non-aqueous decomposition reaction, NF3Decomposition conditions were the same as in example one, NF3The percentage decomposition data are shown in FIG. 6.
EXAMPLE seven
0.1628 g of a manganese nitrate solution with the mass concentration of 50% and 0.1093 g of urea are dissolved in 45 ml of water, added into 0.5 g of the thin-shell aluminum oxide prepared in the first embodiment, stirred and ultrasonically treated for 10 minutes, moved into an auto-pressure kettle with a 100 ml polytetrafluoroethylene inner container, the auto-pressure kettle is placed in an oven, rotated, heated to 190 ℃ at the heating rate of 5 ℃ per minute, reacted at a constant temperature for 4 hours, a product is washed by deionized water, and dried at 80 ℃ for 12 hours. Heating to 600 deg.C at a rate of 5 deg.C/min in air, and calcining the product at constant temperature for 4 hr to obtain the final productThin shell morphology Al as defluorinating agent2O3Loaded with Mn2O35% Mn/Al2O3(wherein the mass of manganese is 5% of the mass of alumina). For NF3Non-aqueous decomposition reaction, NF3Decomposition conditions were the same as in example one, NF3The percentage decomposition data are shown in FIG. 7.
Example eight
0.2606 g of manganese nitrate solution with the mass concentration of 50% and 0.1749 g of urea are dissolved in 45 ml of water, added into 0.5 g of thin-shell aluminum oxide prepared in the first embodiment, stirred and ultrasonically treated for 10 minutes, moved into an autogenous pressure kettle with a 100 ml polytetrafluoroethylene inner container, the autogenous pressure kettle is placed in an oven, rotated, heated to 160 ℃ at the heating rate of 5 ℃ per minute, reacted at constant temperature for 4 hours, the product is washed by deionized water, and dried at 80 ℃ for 12 hours. Heating to 600 ℃ at a heating rate of 5C/min in the air, and roasting the product at a constant temperature for 4 hours to obtain the thin-shell-shaped Al serving as the defluorinating agent2O3Loaded with Mn2O38% Mn/Al2O3(wherein the mass of manganese represents 8% of the mass of alumina). For NF3Non-aqueous decomposition reaction, NF3Decomposition conditions were the same as in example one, NF3The percentage decomposition data are shown in FIG. 8.
Example nine
0.0977 g of manganese nitrate solution with the mass concentration of 50% and 0.065 g of urea are dissolved in 45 ml of water, added into 0.5 g of thin-shell aluminum oxide prepared in the first embodiment, stirred and ultrasonically treated for 10 minutes, moved into an autogenous pressure kettle with a 100 ml polytetrafluoroethylene inner container, the autogenous pressure kettle is placed into an oven, the autogenous pressure kettle rotates, the temperature rises to 160 ℃ at the temperature rising rate of 5 ℃ per minute, the reaction is carried out for 4 hours at constant temperature, the product is washed by deionized water, and the product is dried for 12 hours at 80 ℃. Heating to 600 ℃ at a heating rate of 5C/min in the air, and roasting the product at a constant temperature for 4 hours to obtain the thin-shell-shaped Al serving as the defluorinating agent2O3Loaded with Mn2O33% Mn/Al2O3(wherein the mass of manganese represents 3% of the mass of alumina). For NF3Without water decomposition reactionOf interest, NF3Decomposition conditions were the same as in example one, NF3The percentage decomposition data are shown in FIG. 9.
Example ten
0.0651 g of manganese nitrate solution with the mass concentration of 50% and 0.0437 g of urea are dissolved in 45 ml of water, added into 0.5 g of thin-shell aluminum oxide prepared in the first embodiment, stirred and ultrasonically treated for 10 minutes, moved into an autogenous pressure kettle with a 100 ml polytetrafluoroethylene inner container, the autogenous pressure kettle is placed in an oven, rotated, heated to 160 ℃ at the heating rate of 5 ℃ per minute, reacted at constant temperature for 4 hours, the product is washed by deionized water, and dried at 80 ℃ for 12 hours. Heating to 600 ℃ at a heating rate of 5C/min in the air, and roasting the product at a constant temperature for 4 hours to obtain the thin-shell-shaped Al serving as the defluorinating agent2O3Loaded with Mn2O32% Mn/Al2O3(wherein the mass of manganese represents 2% of the mass of alumina). For NF3Non-aqueous decomposition reaction, NF3Decomposition conditions were the same as in example one, NF3The percentage decomposition data are shown in FIG. 10.
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 (1)

1. A fluorine fixing agent with high utilization rate for nitrogen trifluoride anhydrous decomposition reaction is characterized by being prepared according to the following method, and comprising the following steps:
1) synthesizing carbon spheres by taking glucose as a raw material at 180 ℃; then, excessively dipping a mixed aqueous solution of aluminum nitrate and urea on the surface of the carbon spheres, wherein the mass ratio of aluminum atoms to the carbon spheres is 0.109-0.207, and the molar ratio of urea molecules to the aluminum atoms is 3.5-5; then synthesizing aluminum hydroxide on the surface of the carbon sphere at the synthesis temperature of 110-130 ℃; then, roasting at 600 ℃ in air to remove carbon spheres to obtain the Al with the thin shell appearance2O3；
2) In the shape of thin shell Al2O3Water added with urea and manganese nitrateSolution, or Al in thin shell morphology2O3Adding aqueous solution of urea and cobalt nitrate, mixing, stirring, carrying out ultrasonic treatment for 10-30 minutes, moving to an autogenous pressure kettle with a polytetrafluoroethylene inner container, placing the autogenous pressure kettle in an oven, rotating the autogenous pressure kettle, increasing the temperature to 120-180 ℃ at the temperature rise rate of 5 ℃/min, carrying out constant temperature crystallization for 4 hours, washing with deionized water, drying at 80 ℃ for 12 hours to obtain a product, namely the Al product with the shape of a thin shell2O3Loaded Mn2O3Or Co3O4The amount of the precursor is controlled by the amount of the precursor,
wherein manganese or cobalt atoms are bonded to Al2O3The mass ratio of (3-8): 100, respectively;
3) then, raising the temperature to 600 ℃ in the air at a heating rate of 5 ℃/min, and roasting the product obtained in the step 2) at a constant temperature for 4 hours to obtain Al with a thin shell appearance2O3Mn of the surface2O3Or Co3O4The precursor is heated and decomposed to generate Al with a thin shell shape2O3Loaded with Mn2O3Or Co3O4A fluorine fixing agent.
CN201810381296.4A 2018-04-25 2018-04-25 Fluorine fixing agent with high utilization rate and preparation method thereof Active CN108579397B (en)

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