CN113813966A - Novel biomass charcoal-based functional material for catalytic oxidation of formaldehyde and preparation method and application thereof - Google Patents
Novel biomass charcoal-based functional material for catalytic oxidation of formaldehyde and preparation method and application thereof Download PDFInfo
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000002028 Biomass Substances 0.000 title claims abstract description 74
- 239000000463 material Substances 0.000 title claims abstract description 65
- 239000003610 charcoal Substances 0.000 title claims abstract description 40
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 32
- 230000003647 oxidation Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims description 17
- 229910016978 MnOx Inorganic materials 0.000 claims description 14
- 229910002451 CoOx Inorganic materials 0.000 claims description 13
- 235000013399 edible fruits Nutrition 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 241000208140 Acer Species 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- 239000011592 zinc chloride Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910001868 water Inorganic materials 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 230000010718 Oxidation Activity Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 15
- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- 239000012855 volatile organic compound Substances 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000003546 flue gas Substances 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 229910002521 CoMn Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
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- 241000196324 Embryophyta Species 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000007084 catalytic combustion reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
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- 239000003208 petroleum Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
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- 231100000086 high toxicity Toxicity 0.000 description 1
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000211 teratogenicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- 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
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Abstract
The invention discloses a novel biomass charcoal-based functional material for catalytic oxidation of formaldehyde, which relates to the technical field of gas purification and consists of an active component and a carrier; the active component is a transition metal oxide; the carrier is porous biomass activated carbon. The preparation method disclosed by the invention is simple and easy to popularize and apply, and the prepared biomass charcoal-based functional material shows high HCHO catalytic oxidation activity and stability, and has good water resistance and sulfur resistance.
Description
Technical Field
The invention relates to the technical field of gas purification, in particular to a novel biomass charcoal-based functional material for catalytic oxidation of formaldehyde and a preparation method and application thereof.
Background
Traditional Volatile Organic Compounds (VOCs) are volatile organic compounds with a saturated vapor pressure of greater than 70Pa at room temperature, or a boiling point of 260 ℃ or less at atmospheric pressure. With the continuous improvement of modern economic level, industries such as petroleum, chemical engineering, decoration, automobiles, pharmacy and the like are rapidly developed, and simultaneously, a large amount of VOCs are generated. HCHO is an important member of VOCs and is of great interest due to its high toxicity and carcinogenic teratogenicity, its source being largely divided into indoor and outdoor sources. In recent years, with the improvement of the quality of life of people, the attention on indoor decoration conditions is higher and higher, and in order to reduce the harm, a great deal of research is carried out, and certain effect is achieved in the aspect of indoor HCHO treatment. In contrast to outdoor sources in the petroleum and chemical production industries and the like, tons of VOCs such as HCHO and the like discharged every year serve as the chief causes of PM2.5 and O3. Therefore, effective control of industrial-source HCHO emissions is of great importance to the protection of human health and atmospheric environment.
At present, the removal method of HCHO mainly comprises an adsorption method, a biological method, a photocatalytic method, catalytic combustion and a catalytic oxidation method. Adsorption processes themselves have limited absorption capacity; the living conditions required by bacteria and microorganisms required by a biological method are harsh, and the efficiency is low; the catalytic combustion has high energy consumption and is difficult to popularize in a large area; the photocatalysis method generally needs high-energy ultraviolet light, has high energy consumption and is easy to cause secondary pollution; in contrast, the catalytic oxidation method is the best choice for the HCHO treatment technology due to the advantages of high purification efficiency, low energy consumption, wide application range, no secondary pollution and the like. The method can be used for catalytically oxidizing HCHO into non-toxic micromolecule substances such as CO2, H2O and the like, and is an HCHO treatment technology which is economical, environment-friendly and has great prospect.
The removal of HCHO by the catalytic oxidation method is to convert HCHO into carbon dioxide and water by catalytic oxidation, is not limited by ultraviolet rays or biological conditions, and has no defect of adsorption saturation by an adsorption method. The current catalysts for removing HCHO can be largely classified into noble metal catalysts and transition metal oxide catalysts. Although the noble metal catalyst has high activity and a lower reaction temperature window, the noble metal catalyst is expensive and is easy to sinter at a higher temperature, so that the loss of active components is caused, and the catalytic activity is reduced, so that the noble metal catalyst cannot be widely applied, Chinese patent CN113083324A discloses a catalyst for catalytic oxidation of HCHO at room temperature, wherein the loading amount of Pt as a catalyst component is 0.1-1 wt.%, but the huge amount of the catalyst used in industrial practical application has too high cost, and the noble metal catalyst is not easy to popularize. The transition metal oxide catalyst has become a research hotspot in the field of current industrial catalysis due to rich sources, low price and huge potential of catalytic performance.
The transition metal oxide catalyst is mainly a supported catalyst. For example, Chinese patent CN110433855A discloses a transition metal base/molecular sieve catalyst used for catalytic oxidation of volatile organic compounds in coal-fired flue gas, but the reaction temperature (T90) when the removal rate reaches 90% is 350 ℃, the temperature is higher, and the energy consumption is larger. In contrast, carbon-based catalysts using activated carbon as a carrier have much attention because they have more excellent low-temperature catalytic activity. The production raw materials of the traditional activated carbon are non-renewable fossil fuels such as coal, and in contrast, the preparation of the biomass activated carbon by using renewable biomass (fruit shells, fruit peels and the like) with wide sources and low cost has practical significance. Research shows that the variety of the plant-based precursor is closely related to the physicochemical properties of the prepared activated carbon product, and when the looser precursors such as peanut shells, straws and the like are adopted, the prepared activated carbon has larger pore diameter and higher porosity. While activated carbons prepared from some hard precursors such as walnut shells, coconut shells, and the like tend to have smaller pore sizes. Therefore, the carbon material prepared by one precursor is often single in pore structure and difficult to meet the diversified requirements in the field of catalysis.
Disclosure of Invention
The invention aims to solve the defects in the prior art, the adsorption capacity of the activated carbon prepared by adopting various biomasses can reach the effect of accumulation of the adsorption capacity of the activated carbon prepared by a single raw material, and the activated carbon has a multi-level pore structure with a specific micropore-mesopore-macropore ratio, can exert the advantages of all levels of pores, is more beneficial to the mass transfer of reactants and products, and provides a novel biomass charcoal-based functional material for catalyzing and oxidizing formaldehyde, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a novel biomass charcoal-based functional material for catalytic oxidation of formaldehyde comprises an active component and a carrier; the active component is a transition metal oxide; the carrier is porous biomass activated carbon.
Further, the active component accounts for 3-15% by weight, and the balance is a carrier.
Further, the transition metal oxide is formed of CoOxAnd MnOxAnd (4) forming.
Further, the CoOxAnd MnO with MnOxIs 0.5.
Further, the carrier is porous biomass activated carbon prepared by mixing maple fruits and orange peels.
Further, the specific surface area of the biomass charcoal-based functional material is more than 1000m2Per g, pore volume greater than 0.6cm3/g。
A preparation method of a novel biomass charcoal-based functional material for catalytic oxidation of formaldehyde comprises the following steps:
(1) cleaning maple fruit and orange peel respectively, drying at 105 deg.C for 12 hr, pulverizing respectively, sieving, and sealing;
(2) uniformly mixing the two crushed materials treated in the step (1), and mixing the mixed powder with 10mol/L ZnCl2The solution is mixed and prepared into ZnCl2Activating the material for later use;
(3) reacting ZnCl2Drying the activated material at 110 deg.C for 24 hr, and using tubular typeFurnace in N2Under protection, controlling the temperature at 750 ℃ for carbonization for 2 h;
(4) respectively using 5mol/L HNO3Washing the material obtained in the step (3) with a solution and a 5mol/L NaOH solution for 3-5 times, then rinsing the material with deionized water to be neutral, and finally drying and sieving the material to obtain porous biomass activated carbon for later use;
(5) putting the porous biomass activated carbon obtained in the step (4) into a cobalt salt and manganese salt precursor solution for soaking for 24 hours, taking out the porous biomass activated carbon, drying the porous biomass activated carbon, and then adding N2Under protection, calcining for 4.5h at the temperature of 550 ℃ to obtain the finished product of the biomass carbon-based functional material.
Further, the powder material in the step (2) is mixed with ZnCl2The corresponding weight ratio is 3: 4; the cobalt salt is cobalt nitrate, and the manganese salt is manganese acetate.
An application of a novel biomass charcoal-based functional material for catalytic oxidation of formaldehyde is used for catalytic oxidation removal of formaldehyde.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a novel biomass charcoal-based functional material for catalytic oxidation of formaldehyde, which is characterized in that two plant precursors are compounded to prepare biomass activated carbon, the biomass activated carbon has a multi-level pore structure with a high specific surface area and a specific micropore-mesopore-macropore ratio, and the multi-level pore structure can exert the advantages of all levels of pores, is beneficial to mass transfer of reactants and products, and has remarkable advantages in the field of catalysis. The preparation method disclosed by the invention is simple and easy to popularize and apply, and the prepared biomass charcoal-based functional material shows high HCHO catalytic oxidation activity and stability, and has good water resistance and sulfur resistance and great popularization and application values.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is a SEM characterization result chart in experiment 1 of the present invention;
FIG. 2 is a graph of data from experiment 1 according to the present invention;
FIG. 3 is a graph of data from experiment 2 according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example 1
A novel biomass charcoal-based functional material for catalytic oxidation of formaldehyde comprises an active component and a carrier; the active component is transition metal oxide; the carrier is porous biomass activated carbon.
The active component accounts for 3 percent by weight, and the balance is carrier.
Transition metal oxide made of CoOxAnd MnOxAnd (4) forming.
CoOxAnd MnO with MnOxIs 0.5.
The carrier is porous biomass activated carbon prepared by mixing maple fruit and orange peel.
The specific surface area of the biomass charcoal-based functional material is more than 1000m2Per g, pore volume greater than 0.6cm3/g。
Example 2
A novel biomass charcoal-based functional material for catalytic oxidation of formaldehyde comprises an active component and a carrier; the active component is transition metal oxide; the carrier is porous biomass activated carbon.
The active component accounts for 6 percent by weight, and the balance is carrier.
Transition metal oxide made of CoOxAnd MnOxAnd (4) forming.
CoOxAnd MnO with MnOxIs 0.5.
The carrier is porous biomass activated carbon prepared by mixing maple fruit and orange peel.
The specific surface area of the biomass charcoal-based functional material is more than 1000m2Per g, pore volume greater than 0.6cm3/g。
Example 3
A novel biomass charcoal-based functional material for catalytic oxidation of formaldehyde comprises an active component and a carrier; the active component is transition metal oxide; the carrier is porous biomass activated carbon.
The active component accounts for 9 percent by weight, and the balance is carrier.
Transition metal oxide made of CoOxAnd MnOxAnd (4) forming.
CoOxAnd MnO with MnOxIs 0.5.
The carrier is porous biomass activated carbon prepared by mixing maple fruit and orange peel.
The specific surface area of the biomass charcoal-based functional material is more than 1000m2Per g, pore volume greater than 0.6cm3/g。
Example 4
A novel biomass charcoal-based functional material for catalytic oxidation of formaldehyde comprises an active component and a carrier; the active component is transition metal oxide; the carrier is porous biomass activated carbon.
The active component accounts for 12 percent by weight, and the balance is carrier.
Transition metal oxide made of CoOxAnd MnOxAnd (4) forming.
CoOxAnd MnO with MnOxIs 0.5.
The carrier is porous biomass activated carbon prepared by mixing maple fruit and orange peel.
The specific surface area of the biomass charcoal-based functional material is more than 1000m2Per g, pore volume greater than 0.6cm3/g。
The specific surface area of the material of the present example was 815.798m2(g) total pore volume of 0.508cm3In terms of/g, the mean pore diameter is 2.489 nm.
0.2g of the material of the embodiment is taken, and the simulated flue gas atmosphere comprises 60.0 +/-2.0 ppm of HCHO and 6 percent of O within the temperature range of 100-400 DEG C2And equilibrium gas N2(99.99%). The test results show that the removal efficiency of HCHO is the best at 260 ℃, 97.7%.
Example 5
A novel biomass charcoal-based functional material for catalytic oxidation of formaldehyde comprises an active component and a carrier; the active component is transition metal oxide; the carrier is porous biomass activated carbon.
The active component accounts for 15 percent by weight, and the balance is carrier.
Transition metal oxide made of CoOxAnd MnOxAnd (4) forming.
CoOxAnd MnO with MnOxIs 0.5.
The carrier is porous biomass activated carbon prepared by mixing maple fruit and orange peel.
The specific surface area of the biomass charcoal-based functional material is more than 1000m2Per g, pore volume greater than 0.6cm3/g。
The preparation method of the material is the preparation method of the embodiment 6.
Comparative example 1
This comparative example 1 is compared with example 5 with the only difference that the active ingredient content is increased to 18% by weight and the remaining process steps are identical.
Example 6
A preparation method of a novel biomass charcoal-based functional material for catalytic oxidation of formaldehyde comprises the following steps:
(1) cleaning maple fruit and orange peel respectively, drying at 105 deg.C for 12 hr, pulverizing respectively, sieving, and sealing;
(2) uniformly mixing the two crushed materials treated in the step (1), and mixing the mixed powder with 10mol/L ZnCl2The solution is mixed and prepared into ZnCl2Activating the material for later use;
(3) reacting ZnCl2Drying the activated material at 110 deg.C for 24 hr, and heating in a tubular furnace in N2Under protection, controlling the temperature at 750 ℃ for carbonization for 2 h;
(4) respectively using 5mol/L HNO3Washing the material obtained in the step (3) with a solution and a 5mol/L NaOH solution for 3-5 times, then rinsing the material with deionized water to be neutral, and finally drying and sieving the material to obtain porous biomass activated carbon for later use;
(5) will be described in detail(4) Soaking the obtained porous biomass activated carbon in a cobalt salt and manganese salt precursor solution for 24 hours, taking out the porous biomass activated carbon, drying the porous biomass activated carbon, and then adding N2Under protection, calcining for 4.5h at the temperature of 550 ℃ to obtain the finished product of the biomass carbon-based functional material.
The powder and ZnCl in the step (2)2The corresponding weight ratio is 3: 4; the cobalt salt is cobalt nitrate and the manganese salt is manganese acetate.
Experiment 1:
taking the materials corresponding to the above examples 1-5 and comparative example 1 as experimental objects, weighing 0.2g, and simulating the flue gas atmosphere including 60.0 + -2.0 ppm HCHO and 6% O within the temperature range of 100-400 DEG C2And equilibrium gas N2(99.99%). Test results indicate that a moderate amount of metal oxide loading favors HCHO removal, while too little or too much metal oxide reduces HCHO removal. In addition, through the SEM characterization results (fig. 1 of the specification, in which (a) is original MBAC, (b) is 6 wt.% CoMn/MBAC, (c) is 12 wt.% CoMn/MBAC, and (d) is 18% CoMn/MBAC), it can be seen that the introduction of the metal oxide greatly changes the surface structure of the original MBAC, when many carbon surfaces are still unused on the sample with the metal oxide loading of 6 wt.%, and the agglomeration phenomenon of the metal oxide occurs on the sample with the excess loading of 18 wt.% even blocks part of the cell channels, while the distribution of the metal oxide on the sample with the metal oxide loading of 12 wt.% CoMn/MBAC is relatively uniform, which can provide sufficient active sites for the catalytic reaction, thereby having the highest HCHO removal efficiency. The specific test result is shown in the attached figure 2 of the specification.
Experiment 2:
the types of prepared carriers were changed with the optimum loading of 12 wt.% as a standard (i.e., the material of example 4), i.e., the carriers were biomass charcoal prepared from maple fruit (LBAC), biomass charcoal prepared from orange peel (OBAC), and biomass charcoal carrier prepared by compounding two raw Materials (MBAC). The following applies: 0.2g of the carbon-based functional material prepared in the embodiment 4 is used as an experimental object, and the simulated flue gas atmosphere comprises 60.0 +/-2.0 ppm of HCHO and 6% of O within the temperature range of 100-400 DEG C2And equilibrium gas N2(99.99％)。
The result shows that the biomass charcoal-based functional material prepared by the double precursors has better removal effect than the biomass charcoal-based functional material prepared by the single precursor, and the biomass charcoal-based functional material prepared by the double precursors has a hierarchical pore structure with a specific micropore-mesopore-macropore ratio, is favorable for mass transfer of reactants and products, is favorable for dispersion of active metal oxides, is favorable for increasing active sites, and is favorable for carrying out catalytic oxidation reaction. The specific result is shown in figure 3 in the specification.
Experiment 3:
simulating H in flue gas on the premise of ensuring optimal reaction temperature2O and SO2The atmospheric conditions of (1). The following applies:
in this example 4, 0.2g of 12 wt.% CoMn/MBAC was used as an experimental subject, the temperature program was controlled within the range of 100-400 ℃, and the simulated flue gas atmosphere included 60.0. + -. 2.0ppm HCHO and 6% O2、300ppmSO2、8％H2O and equilibrium gas N2(99.99%). As a result, the removal efficiency of HCHO reached 86.3%. The porous biomass charcoal-based functional material designed by the invention has excellent performance of catalytic oxidation of HCHO and also has good water resistance and sulfur resistance.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. A novel biomass charcoal-based functional material for catalytic oxidation of formaldehyde is characterized by comprising an active component and a carrier; the active component is a transition metal oxide; the carrier is porous biomass activated carbon.
2. The novel biomass charcoal-based functional material for catalytic oxidation of formaldehyde as claimed in claim 1, wherein the active component is 3-15 wt%, and the balance is carrier.
3. The novel biomass charcoal-based functional material for catalyzing oxidation of formaldehyde according to claim 1, wherein the transition metal oxide is formed from CoOxAnd MnOxAnd (4) forming.
4. The novel biomass charcoal-based functional material for catalyzing oxidation of formaldehyde according to claim 3, wherein the CoO is selected from the group consisting ofxAnd MnO with MnOxIs 0.5.
5. The novel biomass charcoal-based functional material for catalytic oxidation of formaldehyde as claimed in claim 1, wherein the carrier is porous biomass activated carbon prepared by mixing maple fruit and orange peel.
6. The novel biomass charcoal-based functional material for catalyzing oxidation of formaldehyde according to claim 1, wherein the specific surface area of the biomass charcoal-based functional material is greater than 1000m2Per g, pore volume greater than 0.6cm3/g。
7. The preparation method of the novel biomass charcoal-based functional material for catalytic oxidation of formaldehyde according to any one of claims 1 to 6, characterized by comprising the following steps:
(1) cleaning maple fruit and orange peel respectively, drying at 105 deg.C for 12 hr, pulverizing respectively, sieving, and sealing;
(2) uniformly mixing the two crushed materials treated in the step (1), and mixing the mixed powder with 10mol/L ZnCl2The solution is mixed and prepared into ZnCl2Activating the material for later use;
(3) reacting ZnCl2Drying the activated material at 110 deg.C for 24 hr, and heating in a tubular furnace in N2Under protection, controlling the temperature at 750 ℃ for carbonization for 2 h;
(4) respectively using 5mol/L HNO3Washing the material obtained in the step (3) with a solution and a 5mol/L NaOH solution for 3-5 times, rinsing the material with deionized water to be neutral, and finally performingDrying and sieving to obtain porous biomass activated carbon for later use;
(5) putting the porous biomass activated carbon obtained in the step (4) into a cobalt salt and manganese salt precursor solution for soaking for 24 hours, taking out the porous biomass activated carbon, drying the porous biomass activated carbon, and then adding N2Under protection, calcining for 4.5h at the temperature of 550 ℃ to obtain the finished product of the biomass carbon-based functional material.
8. The method for preparing the novel biomass charcoal-based functional material for catalyzing and oxidizing formaldehyde according to claim 7, wherein the powder in the step (2) is mixed with ZnCl2The corresponding weight ratio is 3: 4; the cobalt salt is cobalt nitrate, and the manganese salt is manganese acetate.
9. The application of the novel biomass charcoal-based functional material for catalytic oxidation of formaldehyde is characterized in that the material is used for catalytic oxidation removal of formaldehyde.
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