CN114588892A - Titanium modified manganese-based catalyst and preparation method thereof - Google Patents
Titanium modified manganese-based catalyst and preparation method thereof Download PDFInfo
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- CN114588892A CN114588892A CN202210284842.9A CN202210284842A CN114588892A CN 114588892 A CN114588892 A CN 114588892A CN 202210284842 A CN202210284842 A CN 202210284842A CN 114588892 A CN114588892 A CN 114588892A
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- 239000010936 titanium Substances 0.000 title claims abstract description 31
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 26
- -1 Titanium modified manganese Chemical class 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- 229910052748 manganese Inorganic materials 0.000 claims abstract description 21
- 239000011572 manganese Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
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- 238000005516 engineering process Methods 0.000 claims abstract description 8
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- 238000001035 drying Methods 0.000 claims description 14
- 238000011068 loading method Methods 0.000 claims description 13
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- 239000000758 substrate Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 7
- UHWHMHPXHWHWPX-UHFFFAOYSA-J dipotassium;oxalate;oxotitanium(2+) Chemical compound [K+].[K+].[Ti+2]=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UHWHMHPXHWHWPX-UHFFFAOYSA-J 0.000 claims description 6
- 238000006703 hydration reaction Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention discloses a titanium modified manganese-based catalyst and a preparation method thereof, belonging to the technical field of formaldehyde catalytic oxidation. The titanium modified manganese-based catalyst adopts gamma-Al prepared by adopting an anodic oxidation technology2O3Al is used as a carrier, and non-noble metal is used as a load; wherein the non-noble metal is manganese or a titanium-manganese mixture. The process is safe and simple, has lower cost, has stable combination of the active component of the catalyst and the carrier, is not easy to fall off, and can be used for industrialized mass production; has an integrated structure convenient for replacement, can be applied to an air purifier filter element, can reduce the formaldehyde concentration from 0.9ppm to below 0.04ppm within 48min by using the manganese-titanium catalyst, and has the formaldehyde residual concentration lower than that of indoor places specified by the national standard so farMaximum limit for formaldehyde concentration: (<0.07mg/m3) The moisture resistance and formaldehyde treatment capacity of the catalyst are improved to a certain extent.
Description
Technical Field
The invention relates to the technical field of formaldehyde catalytic oxidation, in particular to a titanium modified manganese-based catalyst and a preparation method thereof.
Background
The world health organization international agency for research on cancer identified formaldehyde (HCHO) as a suspected carcinogen in 1995 and modified formaldehyde to a class of carcinogens with clear carcinogenic effects in 2004. Since 2004, China has become the first major country of formaldehyde consumption in the world, and the indoor formaldehyde pollution problem in China is becoming more severe due to the indoor decoration industry developed at a high speed and the wide use of formaldehyde-containing materials. In consideration of a plurality of cachexia caused by indoor formaldehyde pollution, the World Health Organization (WHO) has been out of regulation and recommended that the indoor formaldehyde concentration should not exceed 0.10mg/m3China also correspondingly goes out of GB/T18883-2002 'indoor air quality Standard' to stipulate that indoor formaldehyde should not exceed 0.10mg/m3And then further limiting the concentration of formaldehyde in indoor air of the civil buildings to 0.08mg/m in GB50325-2020 indoor environmental pollution control Standard of civil building engineering3The following. The survey on indoor environments of various domestic provinces and cities shows that the phenomenon that the concentration of formaldehyde in the indoor living environment of China seriously exceeds the standard generally exists. Studies have shown that chronic low-dose exposure to formaldehyde can cause chronic inflammatory reactions in the respiratory tract, and that higher doses of formaldehyde can cause more severe respiratory damage. It has been reported to be associated with the development of a range of chronic lung diseases, which can further cause dyspnea, and in severe cases, death. In addition, the chronic formaldehyde exposure can cause nervous and digestive system disorders, and typical symptoms comprise dizziness, nausea, vomiting, visual and auditory deterioration, dysmnesia and the like.
The existing formaldehyde removal methods mainly comprise: ventilation, adsorption, green plants, plasma technology and catalytic oxidation. The catalytic oxidation technology has the advantages of low equipment operation cost, wide application range and more excellent formaldehyde removal effect, and embodies higher application advantages. However, most of the catalytic oxidation technologies highly depend on noble metal catalysts with high cost and scarce resources, and the popularization and application of the catalytic oxidation technologies are restricted by high cost.
Disclosure of Invention
Aiming at the technical problems, the invention provides a titanium modified manganese-based catalyst and a preparation method thereof, aiming at providing a catalyst preparation process with simple steps and mild conditions, trying to rapidly and efficiently degrade formaldehyde at room temperature by only using cheap manganese oxide, and greatly reducing the preparation cost of the catalyst by avoiding using raw materials containing noble metals, thereby meeting the requirement on the catalyst cost in the actual application link.
In order to achieve the purpose, the invention provides the following technical scheme:
the first technical scheme is as follows: a titanium modified manganese-based catalyst, which is gamma-Al prepared by adopting an anodic oxidation technology2O3Al is used as a carrier, and non-noble metal is used as a load; wherein the non-noble metal is manganese or a titanium-manganese mixture.
The second technical scheme is as follows: a preparation method of a titanium modified manganese-based catalyst comprises the following steps:
(1) roasting the anodized aluminum substrate, then carrying out a thermal hydration reaction, and roasting again to obtain the gamma-Al2O3a/Al carrier;
(2) in the presence of gamma-Al2O3And loading manganese or a titanium-manganese mixture on the Al carrier to prepare the titanium modified manganese-based catalyst for removing formaldehyde.
Further, the aluminum substrate in the step (1) is pretreated before use, and the pretreatment method comprises the following steps: sequentially using 5-15 wt% of NaOH solution and 5-15 wt% of HNO3The solution is used for pretreating the aluminum substrate for 1-5 min. The aluminum base material is 1060 type aluminum mesh.
Further, the anodizing condition in the step (1) is as follows: the electrolyte is 0.1-0.8mol/L oxalic acid solution, the temperature is 5-30 ℃, and the current density is 10-50A/m2The electrolysis time is 8-16 h.
Further, the roasting temperature in the step (1) is 200-; the temperature of the hot hydration reaction is 30-95 ℃ and the time is 1-2 h; the temperature of the secondary roasting is 300-600 ℃, and the time is 3-6 h.
The method comprises the steps of roasting an aluminum substrate obtained by anodic oxidation to obtain porous Anodic Aluminum Oxide (AAO); through hydrothermal synthesis reaction, hydroxyl-rich boehmite (AlOOH) is obtained; the gamma-Al with compact and ordered porous structure is obtained by secondary roasting2O3a/Al carrier.
Further, the loading process of step (2) is performed by any one of the following methods:
A. mixing gamma-Al2O3Putting the Al carrier in a mixed solution of potassium permanganate and ammonium oxalate, stirring and reacting for 12-96h at 50-100 ℃, washing and drying, and drying for 2-8h at 100-200 ℃;
B. mixing gamma-Al2O3Soaking Al carrier in potassium titanium oxalate solution at 50-100 deg.c for 1-12 hr, washing and drying, roasting at 350-550 deg.c for 3-6 hr; then placing the obtained product in a mixed solution of potassium permanganate and ammonium oxalate, stirring and reacting for 12-96h at 50-100 ℃, washing and drying, and drying for 2-8h at 100-200 ℃.
Furthermore, the concentration of the titanium potassium oxalate solution is 0.01-1 mol/L.
Further, the concentrations of the potassium permanganate and the ammonium oxalate in the scheme A and the scheme B are both 0.01-1mol/L, and the molar ratio is 1: 1.
In the scheme B, the carrier is modified by adopting titanium, and then the active component manganese is loaded.
The third technical scheme is as follows: the application of the titanium modified manganese-based catalyst in formaldehyde removal.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention adopts the structural integrated gamma-Al with stable property2O3The Al is used as a carrier, non-noble metal manganese is used as an active component, and the formaldehyde catalytic activity of the manganese-based catalyst is further improved by doping metal ion titanium, so that the catalytic decomposition of formaldehyde at normal temperature is realized.
(2) Book (I)The preparation process of the catalyst prepared by the invention is safe and simple, the cost is lower, the combination of the active component of the catalyst and the carrier is stable, the catalyst is not easy to fall off, and the catalyst can be industrially produced in batch; has an integrated structure convenient for replacement, and can be applied to an air purifier filter element. The catalyst can remove formaldehyde at normal temperature, and the concentration of the formaldehyde in the pure manganese catalyst is reduced from 0.9ppm to 0.05ppm within 80min at room temperature. The manganese-titanium catalyst can reduce the formaldehyde concentration from 0.9ppm to less than 0.04ppm within 48min, and the residual concentration of the formaldehyde is lower than the highest requirement of the limit value of the formaldehyde concentration of indoor places specified by the national standard (<0.07mg/m3) The moisture resistance and formaldehyde treatment capacity of the catalyst are improved to a certain extent.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a scanning electron microscope image of the morphology of the catalyst supports prepared in examples 1-3;
FIG. 2 is a scanning electron microscope image of the morphology of the catalysts prepared in examples 1-6; wherein a is catalyst 1 prepared in example 1, B is catalyst 2 prepared in example 2, C is catalyst 3 prepared in example 3, D is catalyst 4 prepared in example 4, E is catalyst 5 prepared in example 5, and F is catalyst 6 prepared in example 6;
FIG. 3 is an XRD pattern of the support and different catalysts before and after modification prepared in examples 1-6; wherein a is the carrier gamma-Al of example 12O3Al, b is example 5 modified support Ti1.9/γ-Al2O3Al, c is catalyst 3 prepared in example 3, d is catalyst 4 prepared in example 4, e is catalyst 5 prepared in example 5, f is catalyst 6 prepared in example 6;
FIG. 4 shows the formaldehyde removal effect of the catalysts prepared in examples 1-3 at room temperature;
FIG. 5 shows the formaldehyde removal effect of the catalyst prepared in example 3 at different wind speeds;
FIG. 6 shows the formaldehyde removal effect of the catalyst prepared in example 3 at different humidities;
FIG. 7 shows the formaldehyde removal effect of the catalysts prepared in examples 3-6 at room temperature;
FIG. 8 shows the formaldehyde removal effect of the catalyst prepared in example 5 at different wind speeds;
FIG. 9 shows the formaldehyde removal effect of the catalyst prepared in example 5 at different humidities;
fig. 10 is the results of the stability test of the catalyst prepared in example 5.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including but not limited to.
The "parts" described in the following examples are all "parts by mass".
A titanium modified manganese-based catalyst, which is gamma-Al prepared by adopting an anodic oxidation technology2O3Al is used as a carrier, and non-noble metal is used as a load; wherein the non-noble metal is manganese or a titanium-manganese mixture.
A preparation method of a titanium modified manganese-based catalyst comprises the following steps:
(1) roasting the anodized aluminum substrate, then carrying out a thermal hydration reaction, and roasting again to obtain the gamma-Al2O3A Al carrier;
(2) in the presence of gamma-Al2O3And loading manganese or a titanium-manganese mixture on the Al carrier to prepare the titanium modified manganese-based catalyst for removing formaldehyde.
The aluminum substrate in the step (1) is pretreated before use, and the pretreatment method comprises the following steps: sequentially using 5-15 wt% of NaOH solution and 5-15 wt% of HNO3The solution is used for pretreating the aluminum substrate for 1-5 min. The aluminum base material is 1060 type aluminum mesh.
The condition of the anodic oxidation in the step (1) is as follows: the electrolyte is 0.1-0.8mol/L oxalic acid solution, the temperature is 5-30 ℃, and the current density is 10-50A/m2The electrolysis time is 8-16 h.
The roasting temperature in the step (1) is 200-; the temperature of the hot hydration reaction is 30-95 ℃ and the time is 1-2 h; the temperature of the secondary roasting is 300-600 ℃, and the time is 3-6 h.
The invention is realized by roasting the anodized aluminum substrate,obtaining porous Anodic Aluminum Oxide (AAO); through hydrothermal synthesis reaction, hydroxyl-rich boehmite (AlOOH) is obtained; the gamma-Al with compact and ordered porous structure is obtained by secondary roasting2O3a/Al carrier.
The loading process of the step (2) is carried out by any one of the following methods:
A. mixing gamma-Al2O3Placing the Al carrier in a mixed solution of potassium permanganate and ammonium oxalate, reacting for 12-96h at 50-100 ℃, washing and drying, and drying for 2-8h at 100-200 ℃;
B. mixing gamma-Al2O3Soaking Al carrier in potassium titanium oxalate solution at 50-100 deg.c for 1-12 hr, air drying, roasting at 350-550 deg.c for 3-6 hr; then placing the obtained product in a mixed solution of potassium permanganate and ammonium oxalate, reacting for 12-96h at 50-100 ℃, washing and drying, and drying for 2-8h at 100-200 ℃;
the concentration of the titanium potassium oxalate solution is 0.01-1 mol/L.
In the scheme A and the scheme B, the concentrations of the potassium permanganate and the ammonium oxalate are both 0.01-1mol/L, and the molar ratio is 1: 1.
Scheme B firstly adopts titanium to modify the carrier, and then loads the active component manganese.
The titanium modified manganese-based catalyst is applied to formaldehyde removal.
Example 1
(1) Using 10 wt% NaOH solution and 10 wt% HNO3Pretreating aluminum mesh with the solution for 4min and 2min, respectively, placing in an anodic oxidation tank, and placing at 20 deg.C under a current density of 25A/m2Anodizing in oxalic acid solution with the concentration of 0.4mol/L for 10 hours, air-drying and roasting at 350 ℃ for 1 hour; then hydrating in deionized water at 80 ℃ for 1h, and drying at normal temperature; then roasting for 4 hours at 500 ℃ to obtain gamma-Al2O3a/Al carrier.
(2) Scheme A. reacting gamma-Al2O3Putting the/Al carrier in a reaction solution of potassium permanganate and ammonium oxalate, adding the potassium permanganate and the ammonium oxalate in a plurality of batches during the reaction, controlling the initial concentration of each batch of the potassium permanganate to be 0.05mol/L and the molar ratio of the ammonium oxalate to the potassium permanganate to be 1:1, and carrying out thermostatic water bath at 90 DEG CThe reaction was carried out for 24h with stirring. After cooling, washing and slight wiping to remove manganese dioxide precipitate which is loosely combined on the surface of the aluminum net, airing, and drying at 105 ℃ for 6 hours to obtain the manganese-based catalyst which is marked as catalyst 1.
Example 2
The same as example 1, except that the reaction time was 48h, a manganese-based catalyst was prepared, and was designated as catalyst 2.
Example 3
The difference from example 1 is that the reaction time is 72 h. A manganese-based catalyst was prepared, designated catalyst 3.
Example 4
The difference from example 1 is that in step (2), scheme B is selected, and first, gamma-Al is added2O3Putting the/Al carrier in a titanium potassium oxalate solution with the concentration of 0.15mol/L, keeping stirring, carrying out constant-temperature water bath at 85 ℃ for 4h, airing, then roasting at 500 ℃ for 4h to obtain a titanium modified carrier, which is marked as Ti1.1/γ-Al2O3and/Al. And then placing the mixture into a reaction solution of potassium permanganate and ammonium oxalate, adding potassium permanganate and ammonium oxalate in multiple batches during the reaction, controlling the initial concentration of each batch of potassium permanganate to be 0.05mol/L and the molar ratio of ammonium oxalate to potassium permanganate to be 1:1, reacting for 72 hours under stirring in a constant-temperature water bath at 90 ℃, washing and drying, and drying at 105 ℃ for 6 hours to obtain the titanium modified manganese-based catalyst, which is marked as catalyst 4. (Ti)x/γ-Al2O3Al, wherein x represents the loading (wt%) of titanium element).
Example 5
The same as example 4, except that the concentration of the potassium titanium oxalate solution was changed to 0.23mol/L, a titanium-modified support was obtained, which was denoted as Ti1.9/γ-Al2O3Al, and then placing the mixture into a reaction solution of potassium permanganate and ammonium oxalate to prepare a manganese-based catalyst, which is marked as catalyst 5.
Example 6
The same as example 4, except that the concentration of the potassium titanium oxalate solution was changed to 0.35mol/L, a titanium-modified support was obtained, which was denoted as Ti2.5/γ-Al2O3Al, then placing the mixture into a reaction solution of potassium permanganate and ammonium oxalate,a manganese-based catalyst was prepared and is identified as catalyst 6.
FIG. 1 is a scanning electron microscope image of the morphology of the catalyst supports prepared in examples 1 to 3, from which FIG. 1 the support γ -Al can be observed2O3The Al surface is rich in sponge-like pore channel structure, which shows that the carrier has higher specific surface area and rich active sites, which is beneficial to the loading and growing process of manganese dioxide.
FIG. 2 is a scanning electron microscope image of the microstructure and morphology of the catalysts prepared in examples 1 to 6, from which it can be seen that smooth, nano-spherical cluster structures with diameters of 50 to 200nm can be observed on the surface of the catalyst after loading manganese dioxide. Further viewing the graphs B and C, as the loading of the catalyst manganese increases, the nanoclusters gradually grow and the diameter gradually increases to 200-500nm, because the nucleation amount of manganese dioxide is small when the reducing agent is in a small excess amount, and thus the nanoclusters tend to grow along the outer edge of the original nanospheres. Comparing fig. C with fig. D, it can be seen that the titanium modification has a significant effect on the subsequent manganese dioxide loading. The surface of the catalyst 4 does not form nanosphere manganese dioxide clusters with the diameter of more than 500nm, but is mainly uniformly distributed in the form of microspheres with the diameters of 20-100nm, which shows that the manganese dioxide dispersibility is obviously improved under the action of titanium. In addition, fluffy manganese dioxide colonies with a width of 1 to 1.5 μm were observed on the surface of all 3 catalysts. This is probably because the formation of fine crystal nuclei during the crystallization of manganese dioxide is promoted by titanium dioxide, thereby preventing the formation of a large-sized nanosphere structure.
FIG. 3 is an XRD pattern of the supports and different catalysts prepared in examples 1-6 before and after modification, and it can be seen from FIG. 3 that the diffraction peaks at 25.2 DEG and 48.0 DEG for the titanium modified support compared to the unmodified support can indicate anatase TiO2. The catalyst 3(c) showed diffraction peaks at 12.3 °, 36.8 ° and 65.7 °, pointing to birnessite type MnO respectively2The (002), (006) and (119) planes of (1). With TiO2Further increase in the supported amount, the intensity of the (002), (006), (119) plane diffraction peak was significantly decreased, indicating that TiO2The doping can promote the formation of birnessite type crystal nucleus to ensure that MnO is not easy to generate2Is uniformly distributed on the surface of the carrier.
Test example 1
In order to explore the effect of the prepared catalyst in catalyzing formaldehyde oxidation at room temperature, the catalyst is selected to be 3m3The evaluation test of formaldehyde catalytic activity is carried out in a cubic bin. During testing, the ambient temperature is controlled to be 25 +/-2 ℃, the ambient relative humidity is controlled to be 40% +/-5%, the air speed of the air purifier is set to be 1.80m/s, and the initial concentration of formaldehyde in the cabin is controlled to be about 0.9 ppm. The results are shown in FIG. 4.
FIG. 4 shows the results of examples 1 to 3 when the catalyst is at 3m3And (5) evaluating the activity of formaldehyde removal in the closed test bin. As can be seen from the observation of FIG. 4, the catalytic activity of catalyst 1 is relatively poor, the formaldehyde concentration is reduced from 0.88ppm to 0.12ppm within 100min, and the formaldehyde conversion rate is 86%. The catalytic effect of the catalyst 2 is similar to that of the catalyst 3, the concentration of the formaldehyde is reduced from about 0.87ppm to 0.05ppm within 100min, and the conversion rate of the formaldehyde reaches 94%.
Test example 2
FIG. 5 shows the formaldehyde degradation activity of the catalyst prepared in example 3 under different wind speed conditions. In the experiment, a manganese-based catalyst 3 with optimal formaldehyde degradation is taken to measure the reaction activity of the catalyst at different wind speed gears of the opening of a purifier; the evaluation result of the formaldehyde degradation activity shows that the formaldehyde removal rate is slightly reduced along with the increase of the wind speed. When the wind speeds are 1.20m/s and 1.80m/s, the catalyst has basically consistent formaldehyde degradation efficiency under the two wind speeds, the formaldehyde concentration is degraded to 0.05ppm from about 0.9ppm initially in the reaction time of 100min, and the formaldehyde degradation rate reaches 94%. The formaldehyde degradation efficiency is reduced slightly when the wind speed is further increased to 2.40 m/s.
Test example 3
FIG. 6 shows the formaldehyde degradation activity of the catalyst prepared in example 3 at different ambient humidity. The environmental humidity was controlled at three levels for activity evaluation testing: low humidity environment (20-30%), medium humidity environment (40-50%), high humidity environment (70-80%). As can be seen from the observation of FIG. 6, the influence of the environmental humidity on the catalytic activity of formaldehyde in the catalyst prepared by the invention is significant. The formaldehyde catalysis effect of the catalyst 3 in the low humidity (relative humidity 20%) and medium humidity (relative humidity 40%) environment is basically consistent. The catalytic effect of the catalyst formaldehyde is obviously reduced along with the rise of the environmental humidity to 80 percent. At a reaction time of 40min, the conversion of formaldehyde was only 53%. At 80min after the start of the purifier, the conversion of formaldehyde was only 72%.
Test example 4
FIG. 7 shows the results of the catalytic activity test at room temperature for the catalysts prepared in examples 3 to 6. The catalyst 5 has the highest formaldehyde catalytic oxidation efficiency, the residual formaldehyde concentration is reduced from 0.9ppm to 0.08ppm when the reaction time is 40min, and the formaldehyde conversion rate reaches 91%. The reaction time is continuously prolonged, the concentration of the residual formaldehyde in the bin is always lower than 0.04ppm from the 48 th min after the purifier is started, and the formaldehyde conversion rate reaches 96%. Compared with catalyst 3, the formaldehyde conversion rates at 40min and 80min of reaction time are 67% and 84%, respectively, which are lower than the formaldehyde conversion rate at 5 and the same reaction time. As the titanium loading increased from 1.9 wt% to 2.5 wt%, the formaldehyde catalytic activity of catalyst 6 was poor, probably because the catalyst manganese loading was low and the channel structure on the surface of the support was partially destroyed during the preparation process, which was not good for the formaldehyde adsorption capture process. The evaluation result of the catalytic activity of the formaldehyde shows that the catalyst loaded with the titanium dioxide has higher catalytic oxidation activity of the formaldehyde, the titanium dioxide improves the dispersity of the manganese dioxide, the catalytic oxidation reaction of the formaldehyde surface is obviously promoted, and the method is favorable for the catalytic oxidation process of the formaldehyde at room temperature.
Test example 5
FIG. 8 shows the formaldehyde degradation activity of the catalyst prepared in example 5 under different wind speed conditions. Referring to fig. 5, comparing formaldehyde degradation efficiencies of catalyst 5 and catalyst 3 at different wind speeds shows that the catalyst loaded with titanium dioxide has similar formaldehyde degradation activity at three wind speeds, and the phenomenon of reduction in formaldehyde removal rate of the catalyst at high gas flux disappears, because the formaldehyde removal rate of the catalyst is increased after the catalyst is loaded with titanium.
Test example 6
FIG. 9 shows formaldehyde degradation activity of catalysts prepared in example 5 at different ambient humidity. In order to investigate the influence of the presence of titanium dioxide on the sensitivity of the formaldehyde degradation catalyst prepared by the invention to environmental humidity, the formaldehyde degradation activity of the catalyst 5 was measured at different environmental humidities. The results of the formaldehyde activity evaluation test at different ambient humidities are shown in fig. 9. Comparing the test result of the influence of the environmental humidity on the activity of the pure manganese catalyst in fig. 6, the decrease of the formaldehyde degradation rate of the catalyst 5 loaded with titanium dioxide in the high humidity environment is reduced in comparison with the catalyst 3 without titanium dioxide at 80 min. The formaldehyde degradation rate is reduced from 96% to 89% at the 80 th min, and the conversion rate is reduced by 7%. Compared with catalyst 3, the formaldehyde degradation rate is reduced from 92% to 72% and the conversion rate is reduced by 20% at the same reaction time, which shows that the catalyst has enhanced resistance to high humidity environment after loading titanium dioxide.
Test example 7
Fig. 10 is the results of the stability test of the catalyst prepared in example 5. In order to explore the influence of the loaded titanium dioxide on the stability of the catalyst for removing the formaldehyde activity for a long time, the catalyst 5 with the optimal activity is selected to carry out a formaldehyde catalytic stability evaluation experiment, and the change condition of the catalytic activity of the catalyst under the condition of long-term heavy load use is investigated. As can be seen from the observation of FIG. 10, the formaldehyde catalytic effect of the catalyst 5 slightly decreased with the increase of the cumulative treatment amount of formaldehyde. By observing the formaldehyde concentration-time change curve after cumulatively treating 25ppm of formaldehyde gas, the conversion rate of formaldehyde of the catalyst 5 still reaches 87.5 percent within 100 min. After washing, airing and regenerating, the formaldehyde conversion rate of the catalyst at 100min is recovered to 96%, which indicates that the activity loss is still reversible.
In conclusion, the catalyst 5 prepared by the invention has excellent room-temperature formaldehyde catalytic activity and stability, and meanwhile, the regeneration step is simple and easy, so that the catalyst is suitable for being used in common places such as residential houses and the like, and has higher application value.
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 and improvements made within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. The titanium modified manganese-based catalyst is characterized in that the catalyst is prepared from gamma-Al prepared by adopting an anodic oxidation technology2O3Al is used as a carrier, and non-noble metal is used as a load; wherein the content of the first and second substances,the non-noble metal is manganese or a titanium-manganese mixture.
2. A method for preparing the titanium-modified manganese-based catalyst according to claim 1, comprising the steps of:
(1) roasting the anodized aluminum substrate, then carrying out a thermal hydration reaction, and roasting again to obtain the gamma-Al2O3a/Al carrier;
(2) in the presence of gamma-Al2O3And loading manganese or a titanium-manganese mixture on the Al carrier to prepare the titanium modified manganese-based catalyst for removing formaldehyde.
3. The method of claim 2, wherein the aluminum substrate of step (1) is pretreated prior to use by: sequentially using 5-15 wt% of NaOH solution and 5-15 wt% of HNO3The solution is used for pre-treating the aluminum substrate for 1-5min respectively.
4. The method according to claim 2, wherein the anodizing in the step (1) is carried out under the following conditions: the electrolyte is 0.1-0.8mol/L oxalic acid solution, the temperature is 5-30 ℃, and the current density is 10-50A/m2The electrolysis time is 8-16 h.
5. The preparation method according to claim 2, wherein the roasting temperature in step (1) is 200-600 ℃, and the time is 1-3 h; the temperature of the hot hydration reaction is 30-95 ℃, and the time is 1-2 h; the temperature of the secondary roasting is 300-600 ℃, and the time is 3-6 h.
6. The production method according to claim 2, wherein the supporting process of step (2) is carried out by any one of the following methods:
A. mixing gamma-Al2O3Putting the Al carrier in a mixed solution of potassium permanganate and ammonium oxalate, and reacting for 12-96h at 50-100 ℃;
B. mixing gamma-Al2O3Soaking Al material carrier in potassium titanium oxalate solution at 50-100 deg.cSoaking for 1-12h, drying, and roasting at 350-550 ℃ for 3-6 h; then placing the obtained product in a mixed solution of potassium permanganate and ammonium oxalate, and reacting for 12-96h at 50-100 ℃.
7. The method according to claim 6, wherein the concentration of the potassium titanium oxalate solution in the embodiment B is 0.01-1 mol/L.
8. The method of claim 6, wherein the concentrations of potassium permanganate and ammonium oxalate in scheme A, B are 0.01-1mol/L and the molar ratio is 1: 1.
9. Use of the titanium-modified manganese-based catalyst of claim 1 for formaldehyde removal.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115253670A (en) * | 2022-08-04 | 2022-11-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for accelerating catalytic degradation of formaldehyde by using ammonia water and manganese-based catalyst |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101590403A (en) * | 2009-06-11 | 2009-12-02 | 上海交通大学 | Multifunctional coupling catalyst and preparation method thereof |
| CN105771993A (en) * | 2016-05-03 | 2016-07-20 | 华东理工大学 | Fischer-Tropsch synthesis catalyst for preparing liquid hydrocarbon from syngas and preparation method of Fischer-Tropsch synthesis catalyst |
| CN107537473A (en) * | 2017-07-20 | 2018-01-05 | 中山大学 | A kind of nanometer Mn catalyst of room temperature catalytic oxidation formaldehyde and preparation method thereof |
| US20200391183A1 (en) * | 2018-01-22 | 2020-12-17 | Sasol Germany Gmbh | Catalyst Support Comprising Homogeneously Distributed Titanium Dioxide and Method for Production |
| CN112604686A (en) * | 2020-11-20 | 2021-04-06 | 珠海格力电器股份有限公司 | Normal-temperature formaldehyde removal catalyst, and preparation method and application thereof |
| CN112742417A (en) * | 2021-01-15 | 2021-05-04 | 华东理工大学 | Noble metal catalyst and preparation method and application thereof |
| CN112915988A (en) * | 2021-01-26 | 2021-06-08 | 天津大学 | Titanium dioxide/carbon/manganese dioxide composite photocatalyst material, and preparation method and application thereof |
-
2022
- 2022-03-22 CN CN202210284842.9A patent/CN114588892B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101590403A (en) * | 2009-06-11 | 2009-12-02 | 上海交通大学 | Multifunctional coupling catalyst and preparation method thereof |
| CN105771993A (en) * | 2016-05-03 | 2016-07-20 | 华东理工大学 | Fischer-Tropsch synthesis catalyst for preparing liquid hydrocarbon from syngas and preparation method of Fischer-Tropsch synthesis catalyst |
| CN107537473A (en) * | 2017-07-20 | 2018-01-05 | 中山大学 | A kind of nanometer Mn catalyst of room temperature catalytic oxidation formaldehyde and preparation method thereof |
| US20200391183A1 (en) * | 2018-01-22 | 2020-12-17 | Sasol Germany Gmbh | Catalyst Support Comprising Homogeneously Distributed Titanium Dioxide and Method for Production |
| CN112604686A (en) * | 2020-11-20 | 2021-04-06 | 珠海格力电器股份有限公司 | Normal-temperature formaldehyde removal catalyst, and preparation method and application thereof |
| CN112742417A (en) * | 2021-01-15 | 2021-05-04 | 华东理工大学 | Noble metal catalyst and preparation method and application thereof |
| CN112915988A (en) * | 2021-01-26 | 2021-06-08 | 天津大学 | Titanium dioxide/carbon/manganese dioxide composite photocatalyst material, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 董冰岩;黄尝伟;江小华;周海金;施志勇;兰水荣;: "脉冲放电协同负载型氧化物催化剂降解甲醛", 环境工程学报, no. 10 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115253670A (en) * | 2022-08-04 | 2022-11-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for accelerating catalytic degradation of formaldehyde by using ammonia water and manganese-based catalyst |
| CN115253670B (en) * | 2022-08-04 | 2024-02-13 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for accelerating catalytic degradation of formaldehyde by using ammonia water to accelerate manganese-based catalyst |
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