CN114588892B - 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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- CN114588892B CN114588892B CN202210284842.9A CN202210284842A CN114588892B CN 114588892 B CN114588892 B CN 114588892B CN 202210284842 A CN202210284842 A CN 202210284842A CN 114588892 B CN114588892 B CN 114588892B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000010936 titanium Substances 0.000 title abstract description 27
- 229910052719 titanium Inorganic materials 0.000 title abstract description 22
- -1 Titanium modified manganese Chemical class 0.000 title abstract description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 295
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- MECMQNITHCOSAF-UHFFFAOYSA-N manganese titanium Chemical compound [Ti].[Mn] MECMQNITHCOSAF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 27
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- 239000012286 potassium permanganate Substances 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 16
- 238000011068 loading method Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 11
- 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 8
- 238000006703 hydration reaction Methods 0.000 claims description 8
- 150000002696 manganese Chemical class 0.000 claims description 7
- 238000007605 air drying Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 22
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052748 manganese Inorganic materials 0.000 abstract description 19
- 239000011572 manganese Substances 0.000 abstract description 19
- 229910000510 noble metal Inorganic materials 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 19
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 18
- 238000012360 testing method Methods 0.000 description 16
- 230000015556 catabolic process Effects 0.000 description 15
- 238000006731 degradation reaction Methods 0.000 description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 11
- 230000007613 environmental effect Effects 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000002077 nanosphere Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000001684 chronic effect Effects 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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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
- 238000001000 micrograph Methods 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
- 238000002203 pretreatment Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
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- 206010013975 Dyspnoeas Diseases 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 208000019693 Lung disease Diseases 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 1
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- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
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- 230000000593 degrading effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
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- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
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- 230000002441 reversible effect Effects 0.000 description 1
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- 231100000606 suspected carcinogen Toxicity 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 230000008673 vomiting Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
-
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Chemical Kinetics & Catalysis (AREA)
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- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention discloses a titanium modified manganese-based catalyst and a preparation method thereof, and belongs to the technical field of formaldehyde catalytic oxidation. The titanium modified manganese-based catalyst is prepared by adopting an anodic oxidation technology 2 O 3 Al is used as a carrier, and non-noble metal is used as a carrier; wherein the non-noble metal is manganese or a titanium manganese mixture. The process is safe and simple, has low cost, ensures that the active components of the catalyst are stably combined with the carrier, is not easy to fall off, and can be industrially produced in batches; the integrated structure is convenient to replace, the filter element of the air purifier can be used, the manganese-titanium catalyst can reduce the formaldehyde concentration from 0.9ppm to below 0.04ppm within 48min, and the residual formaldehyde concentration is lower than the highest requirement of the formaldehyde concentration limit value of the indoor place specified by the national standard so far<0.07mg/m 3 ) The moisture resistance and formaldehyde handling capacity of the catalyst are also improved to some 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 cancer research institute established formaldehyde (HCHO) as a suspected carcinogen in 1995 and revised formaldehyde as a class of carcinogens with definite carcinogenesis in 2004And (3) an object. Since 2004, china has become the first major world of formaldehyde consumption, and the wide use of formaldehyde-containing materials and interior decoration industry with high development makes the indoor formaldehyde pollution problem of China increasingly serious. In view of the many devil fruits caused by indoor formaldehyde pollution, world Health Organization (WHO) regulations recommend that the indoor formaldehyde concentration should not exceed 0.10mg/m 3 The national corresponding to the GB/T18883-2002 standard for indoor air quality specifies that the indoor formaldehyde should not exceed 0.10mg/m 3 And then further limiting the formaldehyde concentration of indoor air of civil buildings to 0.08mg/m in GB50325-2020 Standard for controlling indoor environmental pollution of civil building engineering 3 The following is given. Investigation of indoor environments in various provinces and cities in China shows that the phenomenon that the concentration of formaldehyde in indoor living environments in China seriously exceeds standard is commonly existing. Studies have shown that chronic inflammatory reactions of the respiratory tract can be induced by prolonged low doses of formaldehyde exposure, and more severe respiratory tract injury can be induced when exposed to higher formaldehyde doses. It has been reported to be associated with the development of a range of chronic lung diseases, which can further cause dyspnea and death in severe cases. In addition, chronic formaldehyde exposure can cause neurological and digestive disorders, and typical symptoms include dizziness, nausea, vomiting, and decreased vision, hearing, memory impairment, etc.
The current formaldehyde removal method mainly comprises the following steps: ventilation, adsorption, green plant, plasma technology and catalytic oxidation. The catalytic oxidation technology has lower equipment operation cost, wide application range and more excellent formaldehyde removal effect, and shows higher application advantages. However, most catalytic oxidation technologies are highly dependent on expensive and resource-scarce noble metal catalysts, and the popularization and application of the catalytic oxidation technologies are restricted by the high cost.
Disclosure of Invention
Aiming at the technical problems, the invention provides a titanium modified manganese-based catalyst and a preparation method thereof, and aims to provide a catalyst preparation process which is simple and convenient in steps and mild in conditions, and the catalyst preparation process tries to quickly and efficiently degrade formaldehyde at room temperature by only using low-cost manganese oxide, and the preparation cost of the catalyst is greatly reduced by avoiding using raw materials containing noble metals, so that the requirement of the catalyst cost in the practical application link is met.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the technical scheme is as follows: titanium modified manganese-based catalyst prepared by anodic oxidation technology 2 O 3 Al is used as a carrier, and non-noble metal is used as a carrier; wherein the non-noble metal is manganese or a titanium manganese mixture.
The second technical scheme is as follows: a method for preparing a titanium modified manganese-based catalyst, comprising the steps of:
(1) Roasting the anodized aluminum substrate, performing a thermal hydration reaction, and performing secondary roasting to obtain gamma-Al 2 O 3 An Al carrier;
(2) In gamma-Al 2 O 3 and/Al carrier is loaded with manganese or a titanium-manganese mixture to prepare the titanium-modified manganese-based catalyst for formaldehyde removal.
Further, the aluminum substrate in step (1) is pretreated before use, and the pretreatment method comprises the following steps: with 5-15wt% NaOH solution followed by 5-15wt% HNO 3 The solution is used for respectively carrying out pretreatment on the aluminum substrate for 1-5 min. The aluminum base material is 1060-type aluminum net.
Further, the conditions of the anodic oxidation in the step (1) are as follows: the electrolyte is oxalic acid solution with the concentration of 0.1-0.8mol/L, the temperature is 5-30 ℃ and the current density is 10-50A/m 2 The electrolysis time is 8-16h.
Further, the roasting temperature in the step (1) is 200-600 ℃ and the time is 1-3h; the temperature of the thermal hydration reaction is 30-95 ℃ and the time is 1-2h; the temperature of the secondary roasting is 300-600 ℃ and the time is 3-6h.
The method comprises the steps of roasting an aluminum substrate obtained by anodic oxidation to obtain porous Anodic Aluminum Oxide (AAO); through a thermal hydration reaction, a boehm body (AlOOH) rich in hydroxyl is obtained; through secondary roasting, gamma-Al with compact ordered porous structure is obtained 2 O 3 An Al carrier.
Further, the loading process of step (2) is performed by any one of the following methods:
A. gamma-Al 2 O 3 Placing the Al carrier in a mixed solution of potassium permanganate and ammonium oxalate, stirring and reacting for 12-96h at 50-100 ℃, flushing and airing, and drying for 2-8h at 100-200 ℃;
B. gamma-Al 2 O 3 Immersing Al carrier in potassium titanium oxalate solution, immersing at 50-100deg.C for 1-12 hr, washing, air drying, and calcining at 350-550deg.C for 3-6 hr; then the obtained product is placed into a mixed solution of potassium permanganate and ammonium oxalate, stirred and reacted for 12-96 hours at 50-100 ℃, washed and dried for 2-8 hours at 100-200 ℃.
Further, the concentration of the potassium titanium oxalate solution is 0.01-1mol/L.
Further, in the scheme A and the scheme B, the concentration of the potassium permanganate and the ammonium oxalate is 0.01-1mol/L, and the molar ratio is 1:1.
In scheme B, titanium is adopted to modify the carrier, and then active component manganese is loaded.
The 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 uses the structured integrated gamma-Al with stable property 2 O 3 and/Al is used as a carrier, non-noble metal manganese is used as an active component, and the catalytic activity of formaldehyde 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) The preparation process of the catalyst prepared by the invention is safe and simple, has lower cost, ensures that the active components of the catalyst are stably combined with the carrier and are not easy to fall off, and can be industrially produced in batches; the integrated structure is convenient to exchange, and the air purifier filter element can be applied. The catalyst can remove formaldehyde at normal temperature, and the pure manganese catalyst reduces the formaldehyde concentration from 0.9ppm to 0.05ppm in 80min at room temperature. The manganese-titanium catalyst can reduce the formaldehyde concentration from 0.9ppm to below 0.04ppm within 48min, and the residual formaldehyde concentration is lower than the highest requirement of the indoor formaldehyde concentration limit value specified by national standard so far<0.07mg/m 3 ) Moisture resistance and formaldehyde resistance of the catalystThe throughput load capacity is also improved to some extent.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are 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 other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of the morphology of the catalyst support prepared in examples 1-3;
FIG. 2 is a scanning electron micrograph of the catalyst 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 shows XRD patterns of the supports and different catalysts before and after modification prepared in examples 1-6; wherein a is the carrier gamma-Al of example 1 2 O 3 Al, b is the modified support of example 5 Ti 1.9 /γ-Al 2 O 3 Al, c is the catalyst 3 prepared in example 3, d is the catalyst 4 prepared in example 4, e is the catalyst 5 prepared in example 5, and f is the 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 formaldehyde removal by the catalyst prepared in example 3 at different humidities;
FIG. 7 shows formaldehyde removal at room temperature for the catalysts prepared in examples 3-6;
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 a test result of the stability of the catalyst prepared in example 5.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions 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. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, 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 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 invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The "parts" described in the following examples are all "parts by mass".
Titanium modified manganese-based catalyst prepared by anodic oxidation technology 2 O 3 Al is used as a carrier, and non-noble metal is used as a carrier; wherein the non-noble metal is manganese or a titanium manganese mixture.
A method for preparing a titanium modified manganese-based catalyst, comprising the steps of:
(1) Roasting the anodized aluminum substrate, performing a thermal hydration reaction, and performing secondary roasting to obtain gamma-Al 2 O 3 An Al carrier;
(2) In gamma-Al 2 O 3 and/Al carrier is loaded with manganese or a titanium-manganese mixture to prepare the titanium-modified manganese-based catalyst for formaldehyde removal.
The aluminum substrate in the step (1) is pretreated before use, and the pretreatment method comprises the following steps: with 5-15wt% NaOH solution followed by 5-15wt% HNO 3 The solution is used for respectively carrying out pretreatment on the aluminum substrate for 1-5 min. The aluminum base material is 1060-type aluminum net.
The conditions of the anodic oxidation in the step (1) are as follows: the electrolyte is oxalic acid solution with the concentration of 0.1-0.8mol/L, the temperature is 5-30 ℃ and the current density is 10-50A/m 2 The electrolysis time is 8-16h.
The roasting temperature in the step (1) is 200-600 ℃ and the time is 1-3h; the temperature of the thermal hydration reaction is 30-95 ℃ and the time is 1-2h; the temperature of the secondary roasting is 300-600 ℃ and the time is 3-6h.
The invention obtains porous Anodic Aluminum Oxide (AAO) by roasting the anodic oxidized aluminum substrate; through a thermal hydration reaction, a boehm body (AlOOH) rich in hydroxyl is obtained; through secondary roasting, gamma-Al with compact ordered porous structure is obtained 2 O 3 An Al carrier.
The loading process of the step (2) is performed by any one of the following methods:
A. gamma-Al 2 O 3 Placing the Al carrier in a mixed solution of potassium permanganate and ammonium oxalate, reacting for 12-96h at 50-100 ℃, washing and airing, and drying for 2-8h at 100-200 ℃;
B. gamma-Al 2 O 3 Impregnating Al support with titanium oxalateSoaking in potassium solution at 50-100deg.C for 1-12 hr, air drying, and roasting at 350-550deg.C for 3-6 hr; then placing the obtained product into a mixed solution of potassium permanganate and ammonium oxalate, reacting for 12-96 hours at 50-100 ℃, washing and airing, and drying for 2-8 hours at 100-200 ℃;
the concentration of the potassium titanium oxalate solution is 0.01-1mol/L.
In the scheme A and the scheme B, the concentrations of the potassium permanganate and the ammonium oxalate are 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 application of the titanium modified manganese-based catalyst in formaldehyde removal.
Example 1
(1) With 10wt% NaOH solution followed by 10wt% HNO 3 The solution is respectively pretreated for 4min and 2min, and is placed into an anodic oxidation tank, and is placed at 20 ℃ with current density of 25A/m 2 Anodic oxidation is carried out for 10 hours in oxalic acid solution with the concentration of 0.4mol/L, and roasting is carried out for 1 hour at the temperature of 350 ℃ after air drying; hydrating in deionized water at 80deg.C for 1 hr, and drying at normal temperature; then roasting for 4 hours at 500 ℃ to obtain gamma-Al 2 O 3 An Al carrier.
(2) Scheme A. Gamma. -Al 2 O 3 The Al carrier is placed in a reaction solution of potassium permanganate and ammonium oxalate, the potassium permanganate and the ammonium oxalate are added in a plurality of batches during the reaction, the initial concentration of the potassium permanganate in each batch is 0.05mol/L, the molar ratio of the ammonium oxalate to the potassium permanganate is controlled to be 1:1, and the reaction is carried out for 24 hours under the stirring of a constant-temperature water bath at 90 ℃. After cooling, rinsing and slightly wiping to remove manganese dioxide precipitate which is not firmly combined on the surface of the aluminum mesh, airing and drying at 105 ℃ for 6 hours, and obtaining a manganese-based catalyst which is marked as a catalyst 1.
Example 2
The same procedure as in example 1 was followed except that the reaction time was 48 hours, to prepare a manganese-based catalyst, designated as catalyst 2.
Example 3
The difference from example 1 is that the reaction time is 72h. A manganese-based catalyst, designated catalyst 3, was produced.
Example 4
As in example 1, the difference is that in step (2) option B, γ -Al is first added 2 O 3 placing/Al carrier in 0.15mol/L potassium titanium oxalate solution, stirring, standing at 85deg.C in constant temperature water bath for 4 hr, air drying, and calcining at 500deg.C for 4 hr to obtain titanium modified carrier, denoted as Ti 1.1 /γ-Al 2 O 3 Al. Then placing the titanium-modified manganese-based catalyst into a reaction solution of potassium permanganate and ammonium oxalate, adding the potassium permanganate and the ammonium oxalate into a plurality of batches during the reaction, controlling the initial concentration of the potassium permanganate to be 0.05mol/L in each batch, controlling the molar ratio of the ammonium oxalate to the potassium permanganate to be 1:1, reacting for 72 hours under the stirring of a constant-temperature water bath at 90 ℃, flushing and airing, and drying for 6 hours at 105 ℃, thus obtaining the titanium-modified manganese-based catalyst, which is denoted as a catalyst 4. (Ti) x /γ-Al 2 O 3 Al, wherein x represents the loading (wt%) of titanium element.
Example 5
As in example 4, except that the concentration of the potassium titanium oxalate solution was changed to 0.23mol/L, a titanium-modified carrier, designated as Ti, was produced 1.9 /γ-Al 2 O 3 Al, then put it in a reaction solution of potassium permanganate and ammonium oxalate to prepare a manganese-based catalyst, designated as catalyst 5.
Example 6
As in example 4, except that the concentration of the potassium titanium oxalate solution was changed to 0.35mol/L, a titanium-modified carrier, designated as Ti, was produced 2.5 /γ-Al 2 O 3 Al, then put it in a reaction solution of potassium permanganate and ammonium oxalate to prepare a manganese-based catalyst, designated as catalyst 6.
FIG. 1 is a scanning electron microscope image of the morphology of the catalyst support prepared in examples 1-3, from which FIG. 1 shows the observation of the support gamma-Al 2 O 3 The porous structure with rich Al surface shows that the carrier has relatively high specific surface area and rich active sites, and is favorable to the loading and growth of manganese dioxide.
FIG. 2 is a scanning electron micrograph of the microstructure and morphology of the catalysts prepared in examples 1-6. As can be seen from FIG. A, smooth nanosphere cluster structures with diameters of 50-200nm can be observed on the catalyst surface after loading with manganese dioxide. Further looking at fig. B and C, as the catalyst manganese loading increases, nanoclusters grow gradually, increasing in diameter to 200-500nm, due to the small nucleation number of manganese dioxide with less excess reducing agent and thus a greater propensity to grow along the outer edges of the original nanospheres. Comparing graph C with graph D, it can be seen that titanium modification has a significant effect on the loading of subsequent manganese dioxide. The surface of the catalyst 4 is not formed with nanosphere manganese dioxide clusters with diameters of more than 500nm, but is mainly uniformly distributed in the form of microspheres with diameters of 20-100nm, which shows that the dispersibility of manganese dioxide is obviously improved under the action of titanium. Further, a fluffy manganese dioxide colony having a width of 1 to 1.5 μm was observed on the surface of each of the 3 catalysts. This is probably due to the promotion of the formation of micro-nuclei during crystallization of manganese dioxide by the titanium dioxide, thereby avoiding the formation of large-sized nanosphere structures.
FIG. 3 shows XRD patterns of the supports and the different catalysts before and after modification prepared in examples 1 to 6, and it can be seen from FIG. 3 that diffraction peaks of the titanium modified support at 25.2℃and 48.0℃indicate anatase TiO as compared with the unmodified support 2 . Catalyst 3 (c) showed diffraction peaks at 12.3 °, 36.8 ° and 65.7 °, pointing to birnessite type MnO, respectively 2 (002), (006), (119). With TiO 2 Further increases in loading, significant decreases in the intensity of the (002), (006), (119) plane diffraction peaks, indicate TiO 2 Can promote the formation of birnessite crystal nucleus and lead MnO to be formed 2 Uniformly distributed on the surface of the carrier.
Test example 1
To explore the effect of the prepared catalyst in catalyzing formaldehyde oxidation at room temperature, a catalyst of 3m is selected 3 The formaldehyde catalytic activity evaluation test was performed in the cubic bin. The environmental temperature is controlled at 25+/-2 ℃ and the relative humidity is controlled at 40+/-5%, the wind 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 catalyst prepared in examples 1-3 at 3m 3 And (5) measuring and evaluating the formaldehyde removal activity in the closed test bin. As can be seen from an examination of FIG. 4, the catalytic activity of catalyst 1 was relatively poor and the formaldehyde concentration was high within 100minThe degree was reduced from 0.88ppm to 0.12ppm, and the formaldehyde conversion was 86%. The catalytic effect of the catalyst 2 is similar to that of the catalyst 3, the formaldehyde concentration is reduced from about 0.87ppm to 0.05ppm within 100min, and the formaldehyde conversion rate reaches 94%.
Test example 2
FIG. 5 shows the formaldehyde degrading activity of the catalyst prepared in example 3 under different wind speeds. In the experiment, a manganese-based catalyst 3 with optimal formaldehyde degradation is taken to measure the reactivity of the catalyst under different wind speed gears when the purifier is started; the formaldehyde degradation activity evaluation result shows that the formaldehyde removal rate is reduced slightly with the increase of wind speed. When the wind speeds are 1.20m/s and 1.80m/s, the catalyst has basically consistent formaldehyde degradation efficiency at the two wind speeds, and the formaldehyde concentration is degraded from about 0.9ppm to 0.05ppm initially within the reaction time of 100min, and the formaldehyde degradation rate reaches 94%. The degradation efficiency of formaldehyde is reduced slightly as the wind speed is further increased to 2.40 m/s.
Test example 3
FIG. 6 shows formaldehyde degradation activity of the catalyst prepared in example 3 under different environmental humidity conditions. The activity evaluation test was performed with the ambient humidity controlled at three levels: low humidity environment (20-30%), medium humidity environment (40-50%), high humidity environment (70-80%). As can be seen from fig. 6, the environmental humidity has a significant effect on the formaldehyde catalytic activity of the catalyst prepared by the present invention. 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 formaldehyde catalysis effect of the catalyst is obviously reduced along with the rise of the environmental humidity to 80 percent. At 40min of reaction time, the conversion of formaldehyde was only 53%. At 80min after the purifier was turned on, the formaldehyde conversion was only 72%.
Test example 4
FIG. 7 shows the results of the catalytic activity test at room temperature of 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%. And the reaction time is continuously prolonged, the residual formaldehyde concentration in the bin is always lower than 0.04ppm from 48min after the purifier is started, and the formaldehyde conversion rate reaches 96%. Compared with the catalyst 3, the formaldehyde conversion rates at the reaction time of 40min and 80min are 67% and 84%, respectively, which are lower than the formaldehyde conversion rate of the catalyst 5 at the same reaction time. As the titanium loading increased from 1.9wt% to 2.5wt%, the formaldehyde catalytic activity of catalyst 6 was poor, probably due to the lower manganese loading of the catalyst, the pore structure of the support surface had been partially destroyed during the preparation process, which was detrimental to the formaldehyde adsorption capture process. The formaldehyde catalytic activity evaluation result shows that the titanium dioxide-loaded catalyst has higher formaldehyde catalytic oxidation activity, the titanium dioxide improves the dispersibility of manganese dioxide, the formaldehyde surface catalytic oxidation reaction is obviously promoted, and the method is beneficial to the room-temperature formaldehyde catalytic oxidation process.
Test example 5
FIG. 8 shows the formaldehyde degradation activity of the catalyst prepared in example 5 under different wind speeds. Referring to fig. 5, comparing the formaldehyde degradation efficiency of catalyst 5 with that of catalyst 3 at different wind speeds shows that the catalyst after titanium dioxide loading has similar formaldehyde degradation activity at three wind speeds, and the phenomenon that the formaldehyde removal rate of the catalyst is reduced at high gas flux disappears, because the formaldehyde removal rate of the catalyst is improved after titanium loading.
Test example 6
FIG. 9 shows formaldehyde degradation activity of the catalyst prepared in example 5 under various environmental humidities. To investigate the influence of the presence of titanium dioxide on the sensitivity of the formaldehyde degradation catalyst prepared according to the invention to environmental humidity, the formaldehyde degradation activity of catalyst 5 was determined at different environmental humidities. The results of the activity evaluation test of formaldehyde under different environmental humidity are shown in fig. 9. Comparing the test results of the influence of the environmental humidity on the activity of the pure manganese catalyst in fig. 6, the reduction range of the formaldehyde degradation rate of the catalyst 5 under the high humidity environment at 80min after the titanium dioxide is loaded is reduced compared with the catalyst 3 without the titanium dioxide. At 80min, the formaldehyde degradation rate is reduced from 96% to 89%, and the conversion rate is reduced by 7%. The formaldehyde degradation rate is reduced from 92% to 72% at the same reaction time compared with catalyst 3, and the conversion rate is reduced by 20%, which shows that the tolerance of the catalyst to high humidity environment is enhanced after titanium dioxide is loaded.
Test example 7
FIG. 10 is a test result of the stability of the catalyst prepared in example 5. In order to explore the influence of the supported titanium dioxide on the stability of the catalyst for removing formaldehyde activity for a long time, an activity optimal catalyst 5 is selected to carry out a formaldehyde catalytic stability evaluation experiment, and the change condition of the catalytic activity of the catalyst under the long-term heavy-load use is investigated. As can be seen from an examination of fig. 10, the catalyst 5 showed a slight decrease in the catalytic effect of formaldehyde over a long period of time as the cumulative formaldehyde treatment amount increased. The formaldehyde concentration-time change curve after cumulative treatment of 25ppm formaldehyde gas is observed, and the conversion rate of formaldehyde in the catalyst 5 still reaches 87.5% within 100 min. After washing, airing and regenerating, the formaldehyde conversion rate of the catalyst is recovered to 96% in 100min, which indicates that the activity loss is still reversible.
The catalyst 5 prepared by the method has excellent room temperature formaldehyde catalytic activity and stability, and simultaneously has simple and easy regeneration steps, is suitable for being used in general places such as residential houses and the like, and has higher application value.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (5)
1. A method for preparing a titanium-modified manganese-based catalyst, comprising the steps of:
(1) Roasting the anodized aluminum substrate, performing a thermal hydration reaction, and performing secondary roasting to obtain gamma-Al 2 O 3 An Al carrier;
(2) In gamma-Al 2 O 3 Loading a titanium-manganese mixture on an Al carrier to prepare a titanium-modified manganese-based catalyst for formaldehyde removal;
the loading process is carried out by the following method:
gamma-Al 2 O 3 Immersing Al carrier in potassium titanium oxalate solution, immersing at 50-100deg.C for 1-12 hr, air drying, and calcining at 350-550deg.C for 3-6 hr; then the obtained product is placed in a mixed solution of potassium permanganate and ammonium oxalate to react at 50-100 ℃ for 12-96h；
The concentration of the potassium titanium oxalate solution is 0.01-1mol/L;
the concentration of the potassium permanganate and the ammonium oxalate is 0.01-1mol/L, and the molar ratio is 1:1.
2. The method of claim 1, wherein the aluminum substrate in step (1) is pretreated before use by the following steps: with 5-15wt% NaOH solution followed by 5-15wt% HNO 3 The solution is used for respectively carrying out pretreatment on the aluminum substrate for 1-5 min.
3. The method according to claim 1, wherein the conditions for the anodic oxidation in step (1) are: the electrolyte is oxalic acid solution with the concentration of 0.1-0.8mol/L, the temperature is 5-30 ℃ and the current density is 10-50A/m 2 The electrolysis time is 8-16h.
4. The method according to claim 1, wherein the firing temperature in step (1) is 200 to 600 ℃ for 1 to 3 hours; the temperature of the thermal hydration reaction is 30-95 ℃ and the time is 1-2h; the temperature of the secondary roasting is 300-600 ℃ and the time is 3-6h.
5. Use of a titanium-modified manganese-based catalyst prepared by the preparation method of any one of claims 1 to 4 in formaldehyde removal.
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