CN115155611A - Single-phase spinel type magnetic high-entropy oxide catalyst and preparation method and application thereof - Google Patents
Single-phase spinel type magnetic high-entropy oxide catalyst and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 20
- 239000011029 spinel Substances 0.000 title claims abstract description 20
- 238000000498 ball milling Methods 0.000 claims abstract description 100
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- 239000011812 mixed powder Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 62
- 239000003546 flue gas Substances 0.000 claims description 62
- 238000000034 method Methods 0.000 claims description 45
- 230000008569 process Effects 0.000 claims description 26
- 238000007254 oxidation reaction Methods 0.000 claims description 25
- 238000007873 sieving Methods 0.000 claims description 15
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 103
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- 238000012360 testing method Methods 0.000 description 33
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- 238000006243 chemical reaction Methods 0.000 description 19
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- 239000007789 gas Substances 0.000 description 12
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- 238000005245 sintering Methods 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- 229910003321 CoFe Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
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- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 2
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/005—Spinels
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- 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
- B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
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- 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
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- B01J23/8892—Manganese
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Abstract
The invention provides a single-phase spinel type magnetic high-entropy oxide catalyst, which comprises a high-entropy oxide, wherein the chemical formula of the high-entropy oxide is MnFeCoCuZnOx. The preparation method of the catalyst comprises the following steps: s1, adding MnO 2 、Fe 2 O 3 、Co 2 O 3 Mixing CuO and ZnO according to a preset molar ratio to obtain a mixture; then ball milling the mixture to obtain a ball milling product; the ball milling rotation speed adopted by the ball milling treatment is 100-500rpm, and the ball milling time of the ball milling treatment is 10-40h; s2, for theSieving the ball-milling product to obtain mixed powder; s3, roasting the mixed powder to obtain the catalyst; the temperature of the roasting treatment is 600-1200 ℃, and the time of the roasting treatment is 2-8h. The catalyst provided by the invention has high and stable demercuration efficiency and high-concentration SO resistance 2 And (4) performance.
Description
Technical Field
The invention relates to the field of nano materials, in particular to a single-phase spinel type magnetic high-entropy oxide catalyst, and a preparation method and application thereof.
Background
China is the largest mercury-emitting country in the world and accounts for about 60% of the total mercury emission in the world. Non-ferrous metallurgy is one of the most important artificial mercury emission sources in China, and research of Qinghua university shows that about 30% of mercury in atmospheric environment comes from non-ferrous metallurgy. The mercury emission in the non-ferrous metal smelting industry is mainly focused on the heavy metal smelting process. In a typical zinc smelting process, more than 95% of mercury can be volatilized into flue gas to form 10mg/m 3 Mercury-containing flue gas of the above concentrations.
The mercury in the flue gas is mainly elemental mercury (Hg) 0 ) Mercury (Hg) in its oxidized state 2+ ) And particulate mercury (Hg) p ) In the form of (1), wherein 90% or more of Hg is present 0 But Hg 0 Is insoluble in water, low in activity and high in volatility, and is difficult to remove in the nonferrous smelting process. Hg is a mercury vapor 2+ And Hg p Complete removal can be basically realized on equipment or working sections such as a dust remover, a flue gas scrubber, wet desulphurization and the like. Thus, hg is added 0 Oxidized into Hg which is easily dissolved in water under the action of catalyst 2+ Is an effective means for mercury pollution control.
However, in the prior art, the smoke is removedHg 0 Oxidation to Hg 2+ The efficiency of (2) is low; furthermore, the sulfur content of the sulfide minerals in nonferrous metallurgy is high, and SO is formed 2 High sulfur flue gas with concentration of 1-16% causes that the conventional catalyst is easy to generate sulfur poisoning and deactivation.
In view of the above, there is a need to provide a single-phase spinel type magnetic high-entropy oxide catalyst to solve or mitigate the above-mentioned problem of Hg 0 The catalytic oxidation efficiency of the catalyst is low, and the conventional catalyst is easy to generate sulfur poisoning deactivation.
Disclosure of Invention
The invention mainly aims to provide a single-phase spinel type magnetic high-entropy oxide catalyst, a preparation method and application thereof, and aims to solve the problem of Hg in the conventional catalyst 0 The catalytic oxidation efficiency is low and the conventional catalyst is easy to generate sulfur poisoning deactivation.
In order to achieve the above object, the present invention provides a single-phase spinel type magnetic high-entropy oxide catalyst, which comprises a high-entropy oxide having a chemical formula of MnFeCoCuZnOx.
The invention also provides a preparation method of the catalyst, which comprises the following steps:
s1, adding MnO 2 、Fe 2 O 3 、Co 2 O 3 Mixing CuO and ZnO according to a preset molar ratio to obtain a mixture; then ball milling the mixture to obtain a ball milling product;
wherein the preset molar ratio is 0.8-2.0; the ball milling rotation speed adopted by the ball milling treatment is 100-500rpm, and the ball milling time of the ball milling treatment is 10-40h;
s2, sieving the ball-milled product to obtain mixed powder;
s3, roasting the mixed powder to obtain the catalyst; wherein the roasting treatment temperature is 600-1200 ℃, and the roasting treatment time is 2-8h.
Further, in the mixture, the preset molar ratio is 1.
Further, the ball milling treatment comprises a plurality of ball milling periods, the time duration of each ball milling period is 30-40min, and the interval time duration of the front ball milling period and the back ball milling period is 5-10min.
Further, in the step S1, before the ball milling treatment is performed, a ball milling medium is added to the mixture; wherein the ball milling medium comprises one or more of deionized water, absolute ethyl alcohol and isopropanol;
in the step S2, before the sieving treatment, the ball-milled product is dried.
Further, the screening process comprises: and (3) sieving the ball-milled product by a sieve with 50-100 meshes, and taking undersize to obtain the mixed powder.
Further, the temperature rise rate of the roasting treatment is 5-10 ℃/min.
The invention also provides a catalyst which is prepared by adopting the preparation method.
The invention also provides the application of the catalyst in mercury removal.
Further, the catalyst is adopted to catalyze Hg in flue gas 0 Oxidation reaction of (3); wherein the flue gas contains Hg 0 And SO 2 。
Compared with the prior art, the invention has at least the following advantages:
1. in the invention, mnO is used 2 、Fe 2 O 3 、Co 2 O 3 CuO and ZnO are used as raw materials, simple mechanical ball milling and subsequent roasting are adopted, high dispersion of elements on atomic scale is realized under the action of mechanical force and high-temperature self-propagating, the mixed configuration entropy is increased, a single-phase structure is facilitated to be formed, and the high-entropy oxide with the chemical formula of MnFeCoCuZnOx is obtained.
2. The high-entropy oxide prepared by the invention is single-phase spinel type magnetic high-entropy oxide, has a single-phase spinel structure, and is similar to typical Fd-3m spinel (CoFe) 2 O 4 ) A class of compounds of the same structure; moreover, the high-entropy oxide prepared by the method has a flaky shape, a mesoporous structure and a high ratioSurface area and small particle size distribution; in addition, the high-entropy oxide prepared by the method has strong magnetism, and is favorable for realizing recycling of materials.
3. The high-entropy oxide prepared by the invention has high stable demercuration efficiency and high-concentration SO resistance 2 The performance is that the mercury removal rate can reach about 85 percent when the mercury-containing flue gas at 100 ℃ is treated; when the mercury-containing and sulfur-containing flue gas at 100 ℃ is treated, the demercuration rate is only reduced by 10-20% within 60 min.
Drawings
In order to more clearly illustrate the embodiments or technical solutions of the present invention, the drawings used in the embodiments or technical solutions of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is XRD spectra of catalysts in example 1, comparative example 1 and comparative example 2 of the present invention;
FIG. 2 is SEM and TEM images of the catalyst in example 1 of the present invention; wherein (a) is an SEM image of the catalyst of example 1 and (b) is a TEM image of the catalyst of example 1;
FIG. 3 is an EDS diagram of the catalyst in example 1 of the present invention;
FIG. 4 is a graph of mercury removal performance in example 1, comparative example 1 and comparative example 2 of the present invention;
FIG. 5 is a graph showing the sulfur and mercury removal resistance of example 1, comparative example 1 and comparative example 2;
FIG. 6 is a graph showing the demercuration performance in example 2 of the present invention;
FIG. 7 is a graph showing the sulfur and mercury removal resistance of example 2 of the present invention;
FIG. 8 is an XRD pattern of the catalyst of example 3 of the present invention;
FIG. 9 is a graph showing the demercuration performance in example 3 of the present invention;
FIG. 10 is a graph showing the sulfur and mercury removal resistance of example 3 of the present invention;
FIG. 11 is a graph showing the demercuration performance in example 4 of the present invention;
FIG. 12 is a graph showing the sulfur and mercury removal resistance of example 4 of the present invention.
The implementation, functional features and advantages of the present invention will be further explained with reference to the accompanying drawings in conjunction with the embodiments.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive efforts based on the embodiments of the present invention, are within the scope of protection of the present invention.
It should be noted that all directional indicators (such as upper and lower 8230; etc.) in the embodiments of the present invention are only used for explaining the relative positional relationship between the components at a certain posture (as shown in the attached drawings), the motion situation, etc., and if the certain posture is changed, the directional indicator is also changed accordingly.
Moreover, the technical solutions in the embodiments of the present invention may be combined with each other, but it is necessary to be able to be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent, and is not within the protection scope of the present invention.
It should be understood that the high-entropy oxide refers to a material having a single phase, which is obtained by containing 5 or more elements and being solid-dissolved with each other at an equimolar or near molar ratio, and its unique configuration and functional controllability have attracted extensive attention of researchers.
It is also understood that the definition of high entropy oxides is not yet mature in the art, and that high entropy oxides are not necessarily obtained only at or near perfectly equimolar ratios. For example, in the present invention, a high-entropy oxide is also obtained with a molar ratio of 2.
The high entropy effect is beneficial to enhancing the configuration entropy of a system and forming a high entropy phase of a single solid solution structure; secondly, metal elements with different atomic radii are randomly distributed in the crystal lattice, which easily causes serious crystal lattice distortion and generates a large number of oxygen vacancies and active sites. The lattice distortion improves the atomic diffusion energy barrier, is beneficial to the formation of a nanometer grade high-entropy oxide, and the multi-site cooperation among all element components can enhance the catalytic activity and the sulfur resistance.
Different from the characteristics of the traditional oxide, the electronic structure of the high-entropy oxide is adjustable due to random distribution and high lattice distortion of multiple components, multi-defect coupling, surface oxygen activation, cooperative reinforcement of multiple active centers and the like.
Thus, the present invention provides a novel single-phase spinel type magnetic high-entropy oxide catalyst, which comprises a high-entropy oxide having a chemical formula of MnFeCoCuZnOx.
The exploration shows that MnFeCoCuZnOx has excellent catalytic property and can realize high-activity demercuration and sulfur resistance.
In order to obtain the catalyst capable of resisting sulfur and mercury removal, the invention also provides a preparation method of the catalyst, which comprises the following steps:
s1, adding MnO 2 、Fe 2 O 3 、Co 2 O 3 Mixing CuO and ZnO according to a preset molar ratio to obtain a mixture; then ball milling the mixture to obtain a ball milling product;
wherein the preset molar ratio is 0.8-2.0.8-1.2; the ball milling rotation speed adopted by the ball milling treatment is 100-500rpm, the ball milling time of the ball milling treatment is 10-40h, and it should be noted that the ball milling time in the embodiment is not counted as the pause time.
Specifically, the preset molar ratio can be 1.
The ball milling treatment comprises a plurality of ball milling periods, the duration of each ball milling period is 30-40min, and the interval duration of the two ball milling periods is 5-10min.
It is to be understood that prior to the ball milling process, a ball milling medium may be added to the mixture; wherein, the ball milling medium comprises one or more of deionized water, absolute ethyl alcohol and isopropanol.
S2, sieving the ball-milling product to obtain mixed powder.
In particular, the sieving treatment may comprise: and (3) sieving the ball-milled product by a sieve with 50-100 meshes, and taking undersize to obtain the mixed powder. In addition, before the sieving treatment, the ball-milled product may be dried, that is, the ball-milled product is dried.
And S3, roasting the mixed powder to obtain the catalyst, wherein the roasting temperature is 600-1200 ℃, and the roasting time is 2-8h. The temperature rise rate of the roasting treatment can be 5-10 ℃/min.
As the skilled person needs to know, the catalyst prepared by the preparation method is a single-phase spinel type magnetic high-entropy oxide catalyst with a chemical formula of MnFeCoCuZnOx. In addition, the catalyst also comprises a sheet morphology and a mesoporous structure, and has high specific surface area and small particle size distribution.
It is understood that the high-entropy oxide designed and synthesized by the invention is easy to cause serious lattice distortion due to different radiuses, bond lengths and electronegativity of each element, generates a large number of oxygen vacancies and active sites, and is beneficial to the reactant molecule Hg 0 Adsorption of (2). The lattice distortion improves the atomic diffusion energy barrier, is beneficial to forming nano-grade high-entropy oxide, provides rich pore channels and high specific surface area, and strengthens Hg 0 And (4) catalytic oxidation. The electronic structure of the high-entropy oxide is adjustable, multi-defect coupling, surface oxygen activation, synergistic enhancement of various active centers and the like due to the random distribution and high lattice distortion of multiple components of the high-entropy oxide, and the high-entropy oxide with the excellent catalytic properties is a key factor for realizing high-activity demercuration and sulfur resistance.
It is also understood that MnO 2 、Fe 2 O 3 、Co 2 O 3 And in the high-speed ball milling process of the CuO and ZnO powders on a planet ball mill, the mechanical force promotes the generation of bond breaking recombination of each oxide. In the high-temperature roasting process, the high-speed movement of each molecule is promoted, the configuration entropy and the structure of the system are increasedThe crystals form a high entropy oxide of uniform solid solution structure.
In addition, the spinel type high-entropy oxide with the lamellar mesoporous structure prepared by the method increases the specific surface area and available pore channels of the catalyst, so that reactant molecules are fully adsorbed on the high-entropy oxide, and Hg can be promoted 0 Catalytic oxidation of (2).
Further, the high-entropy oxide is an oxide having a single phase obtained by solid-dissolving five or more elements with each other. Similar atomic radii, similar bond lengths, and similar electronegativities of the respective elements make it easier to design and synthesize high-entropy oxides. When the high-entropy oxide catalyst is prepared, the intrinsic properties of the five elements of Mn, fe, co, cu and Zn are fully considered.
Based on the preparation method, the invention also provides a catalyst prepared by adopting the preparation method.
To realize the Hg convection 0 Oxidative conversion and removal, the invention also provides a use of a catalyst as described in any of the above in demercuration.
As the smoke usually contains Hg at the same time 0 And SO 2 The catalyst may be used to contain Hg during a particular application 0 And SO 2 And catalyzing Hg in the flue gas 0 To ensure Hg is present 0 Conversion and removal of (2); it is noted that the temperature of the flue gas is typically 100-300 ℃.
The Hg is actually measured when the catalyst provided by the invention is used for removing mercury 0 The conversion efficiency of the method can be maintained at about 85% for a long time; hg is used for sulfur-resistant demercuration by using the catalyst provided by the invention 0 The highest conversion efficiency of the method can reach about 85 percent, and the conversion efficiency can still reach about 70 percent within 60 min.
To facilitate a further understanding of the invention by those skilled in the art, reference will now be made to the following examples:
it should be understood that examples 1 to 4 and comparative examples 1 to 2, each of which prepared catalysts according to different schemes, are shown in the present invention. Except for the preparation and selection of the catalyst, the mercury removal activity evaluation tests of the catalysts in the examples and the comparative examples are carried out under the same conditions, and the mercury removal activity evaluation tests of the catalysts in the examples and the comparative examples are also carried out under the same conditions.
Example 1
1. Preparation of the catalyst
1. 0.4347g of MnO was weighed separately 2 、0.3547g Fe 2 O 3 、0.8293g Co 2 O 3 0.3978g of CuO and 0.4070g of ZnO powder; and mixing the weighed powder, putting the powder into a zirconia ball milling tank, adding 5mL of absolute ethyl alcohol into the ball milling tank, covering a sealing cover, and carrying out ball milling on a planetary ball mill to obtain a ball milling product, wherein the ball milling ratio is 10.
Wherein the ball milling rotation speed adopted in the ball milling process is 400rpm, the ball milling is suspended for 5min after each ball milling for 30min, and the total ball milling time is 10h except the suspension time.
2. And (3) drying the ball-milled product in a drying box at 60 ℃ for 12 hours, sieving the dried product by using a 100-mesh sieve, and taking undersize to obtain mixed powder.
3. Roasting the mixed powder in a muffle furnace at 800 ℃ for 2h, wherein the heating rate is 5 ℃/min; after the baking and sintering, the mixture is cooled to room temperature to obtain single-phase spinel type magnetic high-entropy oxide powder, namely the required catalyst in the invention.
The chemical formula of the high-entropy oxide prepared by the embodiment is MnFeCoCuZnOx.
Referring to FIG. 1, mnFeCoCuZnOx prepared in this example is a high entropy oxide of single phase solid solution, exhibiting typical Fd-3m spinel (CoFe) 2 O 4 ) And (5) structure.
Referring to fig. 2, the MnFeCoCuZnOx high entropy oxide prepared in this example has a flaky morphology with a grain size of about 50nm.
Referring to fig. 3 (converted from a color chart), the MnFeCoCuZnOx high-entropy oxide prepared in this example has highly uniform dispersion of each element.
In this example, the single-phase spinel-type magnetic high-entropy oxide has a mesoporous structure with a pore diameter of about 22nm and a specific surface area of 26m 2 /g。
2. Evaluation test of catalyst demercuration Activity
The evaluation of the mercury removal activity of the catalyst is completed by a quartz tube type fixed bed catalyst activity evaluation system arranged in a laboratory.
Mercury-containing flue gas composition: hg is a mercury vapor 0 130μg/m 3 ，O 2 6％，N 2 As a balance gas; space velocity of 78000h -1 (ii) a The temperature of the flue gas is 100 ℃; the single-phase spinel-type magnetic high-entropy oxide powder in this example was used as a catalyst.
The specific process is as follows: firstly, testing initial Hg in mercury-containing flue gas by a mercury analyzer 0 The flue gas was then switched to a reaction tube containing 100mg of catalyst to test the outlet Hg 0 The value is obtained. Hg is a mercury vapor 0 Efficiency of oxidation eta oxi Can be defined as:
wherein, the first and the second end of the pipe are connected with each other,
expressed as Hg at the inlet of the reaction tube 0 Concentration (initial Hg) 0 The value is 130. Mu.g/m 3 )，
Expressed as Hg at the outlet of the reaction tube 0 And (4) concentration.
Referring to fig. 4, the efficiency of demercuration (mercury oxidation efficiency) of the MnFeCoCuZnOx high-entropy oxide prepared by the present example is as high as 88%.
3. Evaluation test of catalyst activity for sulfur and mercury removal
The evaluation of the anti-sulfur and demercuration activity of the catalyst is completed on a quartz tube type fixed bed catalyst activity evaluation system arranged in a laboratory.
The mercury-containing and sulfur-containing flue gas comprises the following components: hg is a mercury vapor 0 130μg/m 3 ，O 2 6％，SO 2 6％，N 2 As a balance gas; space velocity of 78000h -1 (ii) a The temperature of the flue gas is 100 ℃; miningThe single-phase spinel-type magnetic high-entropy oxide powder in this example was used as a catalyst.
The specific process is as follows: firstly, testing initial Hg in mercury-containing flue gas by a mercury analyzer 0 The flue gas was then switched to a reaction tube containing 100mg of catalyst and the outlet Hg was tested 0 Value of Hg 0 The oxidation efficiency was calculated as in the second part of this example.
Referring to FIG. 5, the MnFeCoCuZnOx high entropy oxide prepared in this example was SO-reduced at 6% 2 When the mercury removing agent exists, the mercury removing efficiency can still reach about 75% within 60 min; also, the demercuration efficiency was only reduced to 68% even at 70 min.
Example 2
1. Preparation of the catalyst
1. 0.4347g of MnO was separately weighed 2 、0.3547g Fe 2 O 3 、0.8293g Co 2 O 3 0.3978g of CuO and 0.4070g of ZnO powder, mixing the weighed powders, putting the mixture into a zirconia ball milling tank, adding 5mL of absolute ethyl alcohol into the ball milling tank, covering a sealing cover, and carrying out ball milling on a planetary ball mill to obtain a ball-milled product, wherein the ball-to-material ratio is 10.
Wherein the ball milling rotation speed adopted in the ball milling process is 400rpm, the ball milling is suspended for 5min after each ball milling for 30min, and the total ball milling time is 10h except the suspension time.
2. And (3) drying the ball-milled product in a drying box at 60 ℃ for 12 hours, sieving the dried product by using a 100-mesh sieve, and taking undersize to obtain mixed powder.
3. And roasting the mixed powder in a muffle furnace at 600 ℃ for 2 hours at a heating rate of 5 ℃/min, and cooling to room temperature after roasting is finished to obtain single-phase spinel type magnetic high-entropy oxide powder, namely the catalyst required by the invention.
The chemical formula of the high-entropy oxide prepared by the embodiment is MnFeCoCuZnOx; in this example, the specific surface area of the single-phase spinel-type magnetic high-entropy oxide powder was 15m 2 In terms of/g, the pore diameter is approximately 22nm.
2. Evaluation test of catalyst demercuration Activity
The evaluation of the mercury removal activity of the catalyst is completed by a quartz tube type fixed bed catalyst activity evaluation system arranged in a laboratory.
Mercury-containing flue gas composition: hg is a mercury vapor 0 130μg/m 3 ，O 2 6％，N 2 As a balance gas; space velocity of 78000h -1 (ii) a The temperature of the flue gas is 100 ℃; the single-phase spinel-type magnetic high-entropy oxide powder in this example was used as a catalyst.
The specific process is as follows: firstly, testing initial Hg in mercury-containing flue gas by a mercury analyzer 0 The flue gas was then switched to a reaction tube containing 100mg of catalyst and the outlet Hg was tested 0 Value of Hg 0 The procedure for calculating the oxidation efficiency was the same as in example 1.
Referring to fig. 6, the efficiency of demercuration (mercury oxidation efficiency) of the MnFeCoCuZnOx high-entropy oxide prepared by the present example reaches 85%.
3. Evaluation test of catalyst sulfur-resistant and mercury-removing activity in mercury-containing and sulfur-containing flue gas
The evaluation of the anti-sulfur and demercuration activity of the catalyst is completed on a quartz tube type fixed bed catalyst activity evaluation system arranged in a laboratory.
The mercury-containing and sulfur-containing flue gas comprises the following components: hg is a mercury vapor 0 130μg/m 3 ，O 2 6％，SO 2 6％，N 2 As a balance gas; space velocity of 78000h -1 (ii) a The temperature of the flue gas is 100 ℃; the single-phase spinel-type magnetic high-entropy oxide powder in this example was used as a catalyst.
The specific process is as follows: firstly, testing initial Hg in mercury-containing flue gas by a mercury analyzer 0 The flue gas was then switched to a reaction tube containing 100mg of catalyst to test the outlet Hg 0 Value of Hg 0 The procedure for calculating the oxidation efficiency was the same as in example 1.
Referring to FIG. 7, the MnFeCoCuZnOx high entropy oxide prepared in this example was SO-reduced at 6% 2 When the mercury removing agent exists, the mercury removing efficiency can still reach about 70% within 60 min.
Example 3
1. Preparation of the catalyst
1. 0.8694g of MnO was weighed respectively 2 、0.3547g Fe 2 O 3 、0.8293g Co 2 O 3 0.3978g of CuO and 0.4070g of ZnO powder, mixing the weighed powders, putting the mixture into a zirconia ball milling tank, adding 5mL of absolute ethyl alcohol into the ball milling tank, covering a sealing cover, and carrying out ball milling on a planetary ball mill to obtain a ball-milled product, wherein the ball-to-material ratio is 10.
Wherein the ball milling rotation speed adopted in the ball milling process is 400rpm, the ball milling is suspended for 5min after each ball milling is carried out for 30min, and the total ball milling time is 10h except the suspension time.
2. And (3) drying the ball-milled product in a drying box at 60 ℃ for 12 hours, sieving the dried product by using a 100-mesh sieve, and taking undersize to obtain mixed powder.
3. Roasting the mixed powder in a muffle furnace at 800 ℃ for 2h, wherein the heating rate is 5 ℃/min; after the baking and sintering, the mixture is cooled to room temperature to obtain single-phase spinel type magnetic high-entropy oxide powder, namely the catalyst required by the invention.
The chemical formula of the high-entropy oxide prepared by the embodiment is MnFeCoCuZnOx.
Referring to FIG. 8, mnFeCoCuZnOx prepared in this example is a high entropy oxide of single phase solid solution, exhibiting typical Fd-3m spinel (CoFe) 2 O 4 ) And (5) structure.
In this example, the specific surface area of the single-phase spinel-type magnetic high-entropy oxide powder was 18m 2 In terms of a/g pore size of about 20nm.
2. Evaluation test of catalyst demercuration Activity
The mercury removal activity evaluation of the catalyst is completed by a quartz tube type fixed bed catalyst activity evaluation system arranged in a laboratory.
Mercury-containing flue gas composition: hg is a mercury vapor 0 130μg/m 3 ，O 2 6％，N 2 As a balance gas; space velocity of 78000h -1 (ii) a The temperature of the flue gas is 100 ℃; the single-phase spinel-type magnetic high-entropy oxide powder in this example was used as a catalyst.
The specific process is as follows: firstly, testing initial Hg in mercury-containing flue gas by a mercury analyzer 0 The flue gas was then switched to a reaction tube containing 100mg of catalyst to test the outlet Hg 0 Value of Hg 0 The procedure for calculating the oxidation efficiency was the same as in example 1.
Referring to fig. 9, the MnFeCoCuZnOx high-entropy oxide prepared in this example has demercuration efficiency (mercury oxidation efficiency) as high as 85%.
3. Evaluation test of catalyst activity for sulfur and mercury removal
The evaluation of the anti-sulfur and demercuration activity of the catalyst is completed on a quartz tube type fixed bed catalyst activity evaluation system arranged in a laboratory.
The mercury-containing and sulfur-containing flue gas comprises the following components: hg is a mercury vapor 0 130μg/m 3 ，O 2 6％，SO 2 6％，N 2 As a balance gas; space velocity of 78000h -1 (ii) a The temperature of the flue gas is 100 ℃; the single-phase spinel-type magnetic high-entropy oxide powder in this example was used as a catalyst.
The specific process is as follows: firstly, testing initial Hg in mercury-containing flue gas by a mercury analyzer 0 The flue gas was then switched to a reaction tube containing 100mg of catalyst to test the outlet Hg 0 Value of Hg 0 The procedure for calculating the oxidation efficiency was the same as in example 1.
Referring to FIG. 10, the MnFeCoCuZnOx high entropy oxide prepared in this example was SO-reduced at 6% 2 When the mercury removing agent exists, the mercury removing efficiency can still reach about 67% within 60 min.
Example 4
1. Preparation of the catalyst
1. 0.8694g of MnO was weighed respectively 2 、0.3547g Fe 2 O 3 、0.8293g Co 2 O 3 0.3978g of CuO and 0.4070g of ZnO powder, mixing the weighed powders, putting the mixture into a zirconia ball milling tank, adding 5mL of absolute ethyl alcohol into the ball milling tank, covering a sealing cover, and carrying out ball milling on a planetary ball mill to obtain a ball-milled product, wherein the ball-to-material ratio is 10.
The ball milling speed adopted in the ball milling process is 400rpm, the ball milling is suspended for 5min after 30min, and the total ball milling time is 10h except for the suspension time.
2. And (3) drying the ball-milled product in a drying box at 60 ℃ for 12 hours, sieving the dried product by using a 100-mesh sieve, and taking undersize to obtain mixed powder.
3. Roasting the mixed powder in a muffle furnace at 600 ℃ for 2h, wherein the heating rate is 5 ℃/min; after the baking and sintering, the mixture is cooled to room temperature to obtain single-phase spinel type magnetic high-entropy oxide powder, namely the catalyst required by the invention.
The chemical formula of the high-entropy oxide prepared by the embodiment is MnFeCoCuZnOx.
In this example, the specific surface area of the single-phase spinel-type magnetic high-entropy oxide powder was 18m 2 In terms of/g, the pore diameter is approximately 19nm.
2. Evaluation test of catalyst demercuration Activity
The evaluation of the mercury removal activity of the catalyst is completed by a quartz tube type fixed bed catalyst activity evaluation system arranged in a laboratory.
Mercury-containing flue gas composition: hg is a mercury vapor 0 130μg/m 3 ，O 2 6％，N 2 As a balance gas; space velocity of 78000h -1 (ii) a The temperature of the flue gas is 100 ℃; the single-phase spinel-type magnetic high-entropy oxide powder in this example was used as a catalyst.
The specific process is as follows: firstly, testing initial Hg in mercury-containing flue gas by a mercury analyzer 0 The flue gas was then switched to a reaction tube containing 100mg of catalyst to test the outlet Hg 0 Value of Hg 0 The procedure for calculating the oxidation efficiency was the same as in example 1.
Referring to fig. 11, the MnFeCoCuZnOx high-entropy oxide prepared in this example has demercuration efficiency (mercury oxidation efficiency) as high as 85%.
3. Evaluation test of catalyst activity for sulfur and mercury removal
The evaluation of the anti-sulfur and demercuration activity of the catalyst is completed on a quartz tube type fixed bed catalyst activity evaluation system arranged in a laboratory.
The mercury-containing and sulfur-containing flue gas comprises the following components: hg is a mercury vapor 0 130μg/m 3 ，O 2 6％，SO 2 6％，N 2 As a balance gas; space velocity of 78000h -1 (ii) a The temperature of the flue gas is 100 ℃; the single-phase spinel-type magnetic high-entropy oxide powder in this example was used as a catalyst.
The specific process is as follows: firstly, testing initial Hg in mercury-containing flue gas by a mercury analyzer 0 The flue gas was then switched to a reaction tube containing 100mg of catalyst and the outlet Hg was tested 0 Value of Hg 0 The procedure for calculating the oxidation efficiency was the same as in example 1.
Referring to FIG. 12, the MnFeCoCuZnOx high entropy oxide prepared in this example was determined by 6% SO 2 When the mercury removing agent exists, the mercury removing efficiency can still reach about 65% within 60 min.
Comparative example 1
1. Preparation of the catalyst
1. 0.4347g of MnO was weighed separately 2 、0.3547g Fe 2 O 3 、0.8293g Co 2 O 3 0.3978g of CuO and 0.4070g of ZnO powder, mixing the weighed powders, putting the mixture into a zirconia ball milling tank, adding 5mL of absolute ethyl alcohol into the ball milling tank, covering a sealing cover, and carrying out ball milling on a planetary ball mill to obtain a ball-milled product, wherein the ball-to-material ratio is 10.
The ball milling speed adopted in the ball milling process is 400rpm, the ball milling is suspended for 5min after 30min, and the total ball milling time is 10h except for the suspension time.
2. And (3) drying the ball-milled product in a drying box at 60 ℃ for 12 hours, sieving the dried product by using a 100-mesh sieve, and taking undersize to obtain mixed powder.
3. Roasting the mixed powder in a muffle furnace at 400 ℃ for 2h, wherein the heating rate is 5 ℃/min; after the baking and sintering, the mixture is cooled to room temperature to obtain mixed-phase magnetic oxide powder.
Referring to fig. 1, the MnFeCoCuZnOx catalyst prepared in the present comparative example exhibits a mixed phase, and a high entropy phase is not formed.
2. Evaluation test of catalyst demercuration Activity
The evaluation of the mercury removal activity of the catalyst is completed by a quartz tube type fixed bed catalyst activity evaluation system arranged in a laboratory.
Mercury-containing flue gas composition: hg 0 130μg/m 3 ，O 2 6％，N 2 As a balance gas; space velocity of 78000h -1 (ii) a The temperature of the flue gas is 100 ℃; the oxide powder in this comparative example was used as a catalyst.
The specific process is as follows: firstly, testing initial Hg in mercury-containing flue gas by a mercury analyzer 0 Value, the flue gas was then switched to a reaction tube containing 100mg of catalyst and testedOutlet Hg 0 Value of Hg 0 The procedure for calculating the oxidation efficiency was the same as in example 1.
Referring to fig. 4, the MnFeCoCuZnOx catalyst prepared in this comparative example has a demercuration efficiency (mercury oxidation efficiency) of only 54%.
3. Evaluation test of catalyst activity for sulfur and mercury removal
The evaluation of the anti-sulfur and demercuration activity of the catalyst is completed on a quartz tube type fixed bed catalyst activity evaluation system arranged in a laboratory.
The mercury-containing and sulfur-containing flue gas comprises the following components: hg is a mercury vapor 0 130μg/m 3 ，O 2 6％，SO 2 6％，N 2 As a balance gas; space velocity of 78000h -1 (ii) a The temperature of the flue gas is 100 ℃; the oxide powder in this comparative example was used as a catalyst.
The specific process is as follows: firstly, testing initial Hg in mercury-containing flue gas by a mercury analyzer 0 The flue gas was then switched to a reaction tube containing 100mg of catalyst and the outlet Hg was tested 0 Value of Hg 0 The procedure for calculating the oxidation efficiency was the same as in example 1.
Referring to FIG. 5, the MnFeCoCuZnOx catalyst prepared in this comparative example, was calculated at 6% SO 2 When the mercury exists, the mercury removal efficiency can be reduced to 30% within 60 min; at 70min, the time was further decreased to 25%.
Comparative example 2
1. Preparation of the catalyst
1. 0.4347g of MnO was weighed separately 2 、0.3547g Fe 2 O 3 、0.8293g Co 2 O 3 The preparation method comprises the following steps of mixing and loading weighed powder into a zirconia ball milling tank, adding 5mL of anhydrous ethanol into the ball milling tank, covering a sealing cover, and performing ball milling on a planet ball mill to obtain a ball milling product, wherein the ball milling ratio is 10.
Wherein the ball milling rotation speed adopted in the ball milling process is 400rpm, the ball milling is suspended for 5min after each ball milling is carried out for 30min, and the total ball milling time is 5h except the suspension time.
2. And (3) drying the ball-milled product in a drying box at 60 ℃ for 12 hours, sieving the dried product by using a 100-mesh sieve, and taking undersize to obtain mixed powder.
3. Roasting the mixed powder in a muffle furnace at 600 ℃ for 2h, wherein the heating rate is 5 ℃/min; after the baking and sintering, cooling to room temperature to obtain mixed-phase magnetic oxide powder.
Referring to fig. 1, the MnFeCoCuZnOx catalyst prepared in the present comparative example shows a mixed phase without forming a high entropy phase.
2. Evaluation test of catalyst Mercury Activity
The mercury activity evaluation of the catalyst is completed by a quartz tube type fixed bed catalyst activity evaluation system arranged in a laboratory.
Mercury-containing flue gas composition: hg is a mercury vapor 0 130μg/m 3 ，O 2 6％，N 2 As a balance gas; space velocity of 78000h -1 (ii) a The temperature of the flue gas is 100 ℃; the oxide powder in this comparative example was used as a catalyst.
The specific process is as follows: firstly, testing initial Hg in mercury-containing flue gas by a mercury analyzer 0 The flue gas was then switched to a reaction tube containing 100mg of catalyst to test the outlet Hg 0 Value of Hg 0 The procedure for calculating the oxidation efficiency (mercury oxidation efficiency) was the same as in example 1.
Referring to fig. 4, the MnFeCoCuZnOx catalyst prepared in this comparative example has a demercuration efficiency of only 42%.
3. Evaluation test of catalyst sulfur-resistant and mercury-removing activity
The evaluation of the anti-sulfur and demercuration activity of the catalyst is completed on a quartz tube type fixed bed catalyst activity evaluation system arranged in a laboratory.
The mercury-containing and sulfur-containing flue gas comprises the following components: hg is a mercury vapor 0 130μg/m 3 ，O 2 6％，SO 2 6％，N 2 As a balance gas; space velocity of 78000h -1 (ii) a The temperature of the flue gas is 100 ℃; the single-phase spinel-type magnetic high-entropy oxide powder in this comparative example was used as a catalyst.
The specific process is as follows: firstly, testing initial Hg in mercury-containing flue gas by a mercury analyzer 0 The flue gas was then switched to a reaction tube containing 100mg of catalyst to test the outlet Hg 0 Value of Hg 0 The procedure for calculating the oxidation efficiency was the same as in example 1.
Referring to FIG. 5, the MnFeCoCuZnOx catalyst prepared in this comparative example was calculated at 6% SO 2 When the mercury exists, the mercury removal efficiency can be reduced to 17% within 60 min; further, the time was 70min, which was still further decreased to 15%.
In the above technical solutions, the above are only preferred embodiments of the present invention, and the technical scope of the present invention is not limited thereby, and all the technical concepts of the present invention include the claims of the present invention, which are directly or indirectly applied to other related technical fields by using the equivalent structural changes made in the content of the description and the drawings of the present invention.
Claims (10)
1. A single-phase spinel type magnetic high-entropy oxide catalyst is characterized by comprising a high-entropy oxide, wherein the chemical formula of the high-entropy oxide is MnFeCoCuZnOx.
2. A method of preparing a catalyst, comprising the steps of:
s1, adding MnO 2 、Fe 2 O 3 、Co 2 O 3 Mixing CuO and ZnO according to a preset molar ratio to obtain a mixture; then ball milling the mixture to obtain a ball milling product;
wherein the preset molar ratio is 0.8-2.0.8-1.2; the ball milling rotation speed adopted by the ball milling treatment is 100-500rpm, and the ball milling time of the ball milling treatment is 10-40h;
s2, sieving the ball-milled product to obtain mixed powder;
s3, roasting the mixed powder to obtain the catalyst; wherein the roasting treatment temperature is 600-1200 ℃, and the roasting treatment time is 2-8h.
3. The preparation method according to claim 2, wherein the preset molar ratio is 1.
4. The preparation method of claim 2, wherein the ball milling treatment comprises a plurality of ball milling cycles, the duration of each ball milling cycle is 30-40min, and the interval between two ball milling cycles is 5-10min.
5. The method according to claim 2, wherein in step S1, a ball milling medium is added to the mixture before the ball milling treatment; wherein the ball milling medium comprises one or more of deionized water, absolute ethyl alcohol and isopropanol;
in the step S2, before the sieving treatment, the ball-milled product is dried.
6. The method of claim 2, wherein the screening process comprises: and (4) passing the ball-milled product through a screen with 50-100 meshes, and taking undersize to obtain the mixed powder.
7. The method according to claim 2, wherein the temperature increase rate of the baking treatment is 5 to 10 ℃/min.
8. A catalyst, characterized by being prepared by the preparation method according to any one of claims 2 to 7.
9. Use of a catalyst according to claim 1 or 8 for the demercuration.
10. Use according to claim 9, wherein the catalyst is used to catalyse Hg in flue gas 0 Oxidation reaction of (2); wherein the flue gas contains Hg 0 And SO 2 。
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