CN113477246A - Manganese-containing integral electrically-assisted metal honeycomb catalyst and preparation method and application thereof - Google Patents
Manganese-containing integral electrically-assisted metal honeycomb catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000011572 manganese Substances 0.000 title claims abstract description 79
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 73
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 60
- 239000002184 metal Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 13
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 13
- 239000008103 glucose Substances 0.000 claims abstract description 13
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 13
- 238000002791 soaking Methods 0.000 claims abstract description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000005949 ozonolysis reaction Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical group [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 40
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000003421 catalytic decomposition reaction Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 6
- 229910000838 Al alloy Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000003746 solid phase reaction Methods 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- -1 iron-chromium-aluminum Chemical compound 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims 1
- 230000033116 oxidation-reduction process Effects 0.000 claims 1
- 238000004887 air purification Methods 0.000 abstract description 2
- 241000264877 Hippospongia communis Species 0.000 description 40
- 230000000694 effects Effects 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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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
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
- B01D53/8675—Ozone
-
- 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
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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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 & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- 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 belongs to the technical field of air purification, and discloses a manganese-containing integral electrically-assisted metal honeycomb catalyst, and a preparation method and application thereof. The method comprises the following operation steps: performing surface pretreatment on a metal honeycomb substrate; mixing and stirring potassium permanganate, acetic acid and glucose solution to obtain manganese-containing precursor liquid; soaking the pretreated metal honeycomb substrate in a manganese-containing precursor solution, and carrying out hydrothermal reaction at 100-200 ℃ for 5-40 h; then taking out and carrying out ultrasonic treatment in distilled water for 2-20 min; and finally, drying at 50-150 ℃ for 5-20h to obtain the manganese-containing integral electrically-assisted metal honeycomb catalyst, wherein the mass percent of manganese is 10-70 wt.%. The manganese-containing active component in the catalyst can be firmly supported on the surface of the metal honeycomb substrate and uniformly dispersed; the catalyst has excellent conductivity, and the stability and the water resistance of the catalyst in the ozonolysis reaction can be effectively improved in a direct current auxiliary mode.
Description
Technical Field
The invention belongs to the technical field of air purification, and particularly relates to a manganese-containing integral electrically-assisted metal honeycomb catalyst, a preparation method thereof and ozone (O)3) Application in catalytic decomposition.
Background
Ozone (O)3) Because of strong oxidizing property, the ozone is often widely used as a disinfectant, a bactericide, a deodorant and the like, but the ozone is not high in utilization efficiency in the using process and causes more residues. The untreated ozone is directly discharged into the atmosphere and can cause harm to various living bodies and living environments thereof, so that the 1-hour mean value of the ozone in the environmental air is not more than 0.16mg/m in clear regulations of environmental air quality standards (GB3095-2012) in China3。
The existing methods for treating ozone mainly comprise an activated carbon method, a pyrolysis method, a plasma decomposition method and a catalytic decomposition method. The activated carbon method removes ozone by adsorption, but has disadvantages of low adsorption capacity and requiring frequent replacement. Pyrolysis decomposes ozone by combustion, but only high concentration ozone treatment is applicable. The plasma decomposition method decomposes ozone by generating plasma by high-voltage discharge, but has disadvantages of complicated operation, high power consumption, and the like. The catalytic decomposition method can well make up the defects of the method, has higher ozone removal rate, and is the ozone treatment method which is most researched and applied at present.
In the prior art, the ozone decomposition catalyst mainly comprises a noble metal catalyst, a transition metal oxide-containing catalyst and a manganese-containing catalyst. The noble metal catalyst limits the large-scale industrial application due to high price; the low-temperature ozonolysis efficiency of the catalyst containing the transition metal oxide is not high enough. In contrast, the manganese-containing catalyst can effectively enhance the low-temperature ozonolysis efficiency of the catalyst by doping a single manganese dioxide system with noble metals, non-noble metal elements, transition metal elements and the like. However, the manganese-containing catalyst has the disadvantages of short service life and poor water resistance in practical application, mainly because of the low chemical valence state of Mn in the catalyst in the oxidizing atmosphere of ozonolysis reaction3+Is oxidized into Mn of high chemical valence state4+Is relatively fast, and Mn4+Reduction to Mn3+Is relatively slow, thereby causing Mn in the catalyst3+With Mn4+The mutual conversion rate is unbalanced, so that the number of active oxygen vacancies on the surface of the catalyst is continuously reduced, and the catalyst is gradually lostAnd (6) alive. The current researchers mainly enhance Mn in the catalyst by doping and modifying the manganese-containing catalyst4+To Mn3+Thereby maintaining the number of surface active oxygen vacancies and improving the service life of the catalyst. However, the service life and the water resistance of the manganese-containing catalyst are improved in the ozonolysis reaction by a simple direct current auxiliary mode, and reports are not found at present.
The manganese-containing catalyst mainly comprises a granular catalyst and a monolithic catalyst in macroscopic morphology. Wherein the pressure drop of the granular catalyst bed is high, which is not suitable for processing high space velocity ozone gas. For the monolithic catalyst, the activated carbon honeycomb, the ceramic honeycomb and the metal honeycomb are usually used as regular carriers, for example, Chinese patents CN102600861B and CN109261164A are that catalyst powder is prepared firstly, then catalyst slurry is prepared, and finally the catalyst slurry is loaded on the honeycomb carrier through a soaking-coating process to prepare the formed monolithic catalyst, so that the pressure drop of a bed layer can be effectively reduced when the catalyst is used, and ozone can be effectively removed under the conditions of low temperature, high airspeed and high humidity. Compared with activated carbon honeycombs and ceramic honeycombs, the surface of a metal honeycomb carrier is generally smooth and non-porous, the specific surface area is very low, and a manganese-containing catalytic active component is difficult to uniformly and firmly load by adopting a traditional soaking-coating process. However, the metal substrate has the advantages of higher processability and stronger shock resistance, and the metal honeycomb has excellent conductivity, so that the metal honeycomb is more suitable for enhancing the stability and the water resistance of the manganese-containing catalyst by adopting a direct current auxiliary mode.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the preparation method of the manganese-containing integral electrically-assisted metal honeycomb catalyst, the preparation method is simple to operate and suitable for metal substrates in any shapes, and the manganese-containing active component in the prepared catalyst is firmly and uniformly loaded on the metal substrate and has the characteristics of high activity, good conductivity and easiness in industrial application.
The invention further aims to provide the manganese-containing integral electrically-assisted metal honeycomb catalyst prepared by the preparation method.
The invention also aims to provide application of the manganese-containing monolithic electrically-assisted metal honeycomb catalyst in catalytic oxidation decomposition of ozone under the direct current-assisted condition, and the manganese-containing monolithic electrically-assisted metal honeycomb catalyst has the characteristics of high reaction stability and strong water resistance.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a manganese-containing monolithic electrically-assisted metal honeycomb catalyst comprises the following operation steps:
(1) surface pretreatment of a metal substrate: soaking the metal honeycomb substrate in 0.5-2.0mol/L hydrochloric acid solution, removing surface oxides by ultrasonic treatment for 3-20min, and then washing the metal honeycomb substrate with water;
(2) preparing a manganese-containing precursor liquid: mixing potassium permanganate, acetic acid and glucose solution, continuously stirring for 0.5-4h to obtain manganese-containing precursor liquid, and placing the manganese-containing precursor liquid in a hydrothermal reaction kettle; the concentrations of potassium permanganate, acetic acid and glucose in the manganese-containing precursor liquid are respectively 0.05-0.30mol/L, 0.05-1.20mol/L and 0.01-0.10 mol/L;
(3) soaking the metal honeycomb substrate pretreated in the step (1) in the manganese-containing precursor liquid obtained in the step (2), and carrying out hydrothermal reaction at 100-; then taking out and carrying out ultrasonic treatment in distilled water for 2-20 min; and finally, drying at 50-150 ℃ for 5-20h to obtain the manganese-containing integral electrically-assisted metal honeycomb catalyst, wherein the mass percent of manganese is 10-70 wt.%.
The material of the metal honeycomb substrate is stainless steel, iron-chromium-aluminum alloy, nickel-chromium alloy, metal aluminum or aluminum alloy.
The concentration of the hydrochloric acid solution in the step (1) is 0.8-1.3mol/L, and the ultrasonic time is 8-15 min.
The rotating speed of the stirring in the step (2) is 600-1500r/min, and the stirring time is 1.5-2 h.
The hydrothermal reaction temperature in the step (3) is 120-160 ℃, and the hydrothermal time is 10-24 h.
In the step (3), the ultrasonic time is 5-10min, and the drying temperature is 80-120 ℃.
The manganese-containing monolithic electrically-assisted metal honeycomb catalyst prepared by the preparation method is characterized in that: the mass percentage of manganese element in the catalyst is 10-70%.
The manganese-containing integral electrically-assisted metal honeycomb catalyst is applied to catalytic decomposition of ozone.
The catalytic decomposition of ozone is carried out on a gas-solid phase reaction device: putting the manganese-containing integral electrically-assisted metal honeycomb catalyst into a reaction tube, and connecting two ends of the catalyst with leads to connect a direct-current power supply; when ozone gas is introduced for reaction, a stable current is applied to the catalyst through a direct current power supply to assist in regulating the electron gain and loss rate of the redox reaction in the catalyst, and further control Mn in the catalyst3+With Mn4+The mutual conversion rate reaches dynamic balance, the number of surface active oxygen vacancies is maintained, and the reaction stability and the water resistance of the catalyst for ozone decomposition are improved.
The method is essentially different from the traditional soaking-coating process for preparing the monolithic manganese-containing catalyst. The traditional soaking-coating process for preparing the monolithic manganese-containing catalyst generally needs to prepare manganese-containing active component powder in advance, and then load the powder on a honeycomb carrier through coating. The invention does not need to prepare manganese-containing active component powder in advance, but only needs to directly place the metal honeycomb in manganese-containing precursor liquid, and utilizes the reducibility of the metal substrate as an inducer, so that the manganese-containing precursor is preferentially reduced and separated out on the surface of the metal substrate to form manganese oxide crystal nuclei, and the manganese oxide crystal nuclei are further gradually grown up under the guidance of a soft template agent in the solution around the manganese oxide crystal nuclei, and finally manganese-containing active component particles with specific crystal forms and shapes are formed on the surface of the metal substrate. By using the manganese oxide crystal nucleus preferentially generated on the surface of the metal substrate as a base point for subsequent growth, the newly formed manganese-containing active component particles can be uniformly dispersed on the surface of the metal substrate and can be firmly combined on the surface of the metal substrate.
Compared with the prior art, the invention has the following advantages and effects:
(1) the manganese-containing active component in the catalyst can be firmly supported on the surface of the metal honeycomb substrate and uniformly dispersed;
(2) the prepared catalyst has excellent conductivity, and the stability and the water resistance of the catalyst in the ozonolysis reaction can be effectively improved in a direct current auxiliary mode;
(3) the preparation method of the catalyst is simple, the operation is convenient, the shape of the metal component is not required, and the applicability to various metal substrates is strong.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
Soaking a metallic aluminum honeycomb substrate with the length, width and height of 12 multiplied by 8mm and the weight of about 0.23g in a 0.8mol/L hydrochloric acid solution, removing surface oxides by ultrasonic treatment for 15min, and then washing the substrate clean by water; mixing potassium permanganate, acetic acid and glucose solution, continuously stirring for 1.5h at 1000r/min to obtain manganese-containing precursor solution (the concentrations of potassium permanganate, acetic acid and glucose in the manganese-containing precursor solution are respectively 0.14mol/L, 0.56mol/L and 0.04mol/L), and placing the manganese-containing precursor solution in a hydrothermal reaction kettle; soaking the pretreated metal honeycomb in a manganese-containing precursor solution, and carrying out hydrothermal reaction at 140 ℃ for 24 hours; then taking out and carrying out ultrasonic treatment for 5min in distilled water; and finally, drying at 100 ℃ for 10h to obtain the manganese-containing integral electrically-assisted metal honeycomb catalyst with the manganese element content of 52% by mass.
The catalyst sample obtained in the embodiment is placed in a reaction tube, two ends of the catalyst sample are connected with a lead to be connected with a direct current power supply, and when ozone gas is introduced for reaction, stable current is applied to the catalyst through the direct current power supply, so that a direct current auxiliary reaction mode is realized, and the method is used for testing catalytic decomposition activity of ozone.
Example 2
Soaking an aluminum alloy honeycomb substrate with the length, width and height of 12 multiplied by 8mm and the weight of about 0.25g in a 1.3mol/L hydrochloric acid solution, removing surface oxides by ultrasonic treatment for 8min, and then washing the substrate clean by water; mixing potassium permanganate, acetic acid and glucose solution, continuously stirring for 1h at 1500r/min to obtain manganese-containing precursor solution (the concentrations of potassium permanganate, acetic acid and glucose in the manganese-containing precursor solution are respectively 0.30mol/L, 1.20mol/L and 0.10mol/L), and placing the manganese-containing precursor solution in a hydrothermal reaction kettle; soaking the pretreated metal honeycomb in a manganese-containing precursor solution, and carrying out hydrothermal reaction at 120 ℃ for 24 hours; then taking out and carrying out ultrasonic treatment for 5min in distilled water; and finally, drying at 80 ℃ for 20h to obtain the manganese-containing integral electrically-assisted metal honeycomb catalyst with the manganese element content of 67 percent by mass.
The catalyst sample obtained in the embodiment is placed in a reaction tube, two ends of the catalyst sample are connected with a lead to be connected with a direct current power supply, and when ozone gas is introduced for reaction, stable current is applied to the catalyst through the direct current power supply, so that a direct current auxiliary reaction mode is realized, and the method is used for testing catalytic decomposition activity of ozone.
Example 3
Soaking a metallic aluminum honeycomb substrate with the length, width and height of 12 multiplied by 8mm and the weight of about 0.23g in a 1.0mol/L hydrochloric acid solution, removing surface oxides by ultrasonic treatment for 10min, and then washing the substrate clean by water; mixing potassium permanganate, acetic acid and glucose solution, continuously stirring for 2h at 600r/min to obtain manganese-containing precursor solution (the concentrations of potassium permanganate, acetic acid and glucose in the manganese-containing precursor solution are respectively 0.05mol/L, 0.05mol/L and 0.01mol/L), and placing the manganese-containing precursor solution in a hydrothermal reaction kettle; soaking the pretreated metal honeycomb in a manganese-containing precursor solution, and carrying out hydrothermal reaction at 160 ℃ for 30 h; then taking out and carrying out ultrasonic treatment for 10min in distilled water; and finally drying the catalyst for 5 hours at 120 ℃ to obtain the manganese-containing integral electrically-assisted metal honeycomb catalyst with the manganese element content of 23 percent by mass.
The catalyst sample obtained in the embodiment is placed in a reaction tube, two ends of the catalyst sample are connected with a lead to be connected with a direct current power supply, and when ozone gas is introduced for reaction, stable current is applied to the catalyst through the direct current power supply, so that a direct current auxiliary reaction mode is realized, and the method is used for testing catalytic decomposition activity of ozone.
Example 4
Soaking a cylindrical iron-chromium-aluminum honeycomb substrate with the diameter of 14mm and the height of 8mm and the weight of 2.40g in a 1.2mol/L hydrochloric acid solution, removing surface oxides by ultrasonic treatment for 10min, and then washing the substrate clean by water; mixing potassium permanganate, acetic acid and glucose solution, continuously stirring for 3h at 1200r/min to obtain manganese-containing precursor solution (the concentrations of potassium permanganate, acetic acid and glucose in the manganese-containing precursor solution are respectively 0.25mol/L, 1.00mol/L and 0.05mol/L), and placing the manganese-containing precursor solution in a hydrothermal reaction kettle; soaking the pretreated metal honeycomb in a manganese-containing precursor solution, and carrying out hydrothermal reaction at 140 ℃ for 12 hours; then taking out and carrying out ultrasonic treatment for 5min in distilled water; and finally, drying at 100 ℃ for 10h to obtain the manganese-containing integral electrically-assisted metal honeycomb catalyst with the manganese element content of 15% by mass.
The catalyst sample obtained in the embodiment is placed in a reaction tube, two ends of the catalyst sample are connected with a lead to be connected with a direct current power supply, and when ozone gas is introduced for reaction, stable current is applied to the catalyst through the direct current power supply, so that a direct current auxiliary reaction mode is realized, and the method is used for testing catalytic decomposition activity of ozone.
Application example 1 (without DC-assisted reaction)
The catalyst obtained in example 1 was examined for catalytic decomposition activity of ozone without direct current assistance on a self-made gas-solid phase reaction apparatus. The reaction is carried out at normal pressure and room temperature, the concentration of ozone at an inlet is 20ppm, the relative humidity is 90 percent, and the space velocity is 50000h-1And detecting the outlet ozone concentration by using an ozone detector.
The results show that: the ozonolysis catalyst prepared in example 1 rapidly reduced the ozone conversion efficiency from 95% to 45% within 0.5h under high humidity reaction conditions without the aid of direct current. Therefore, the catalyst prepared by the invention has poor service life and water resistance when no direct current is used for assisting reaction.
Application example 2 (with DC-assisted reaction)
The catalyst obtained in example 1 was examined for catalytic decomposition activity of ozone with dc assistance in a self-made gas-solid phase reaction apparatus, that is, a method in which a monolithic metal honeycomb catalyst was placed in a reaction tube, both ends of the catalyst were connected to a lead wire to connect a dc power supply, and when ozone gas was introduced to perform a reaction, a stable current was applied to the catalyst by the dc power supply, thereby achieving a dc-assisted reaction. The reaction is carried out at normal pressure and room temperature, the concentration of ozone at an inlet is 20ppm, the relative humidity is 90 percent, and the space velocity is 50000h-1And detecting the outlet ozone concentration by using an ozone detector.
The results show that: the ozonolysis catalyst prepared in example 1 was reacted for 10 hours under high humidity conditions with the aid of direct current, and the ozone conversion efficiency fluctuated from 92 to 95%, and remained substantially unchanged. Therefore, the catalyst prepared by the invention has excellent reaction stability and water resistance even under high humidity reaction conditions when a direct current auxiliary reaction is carried out.
The ozonolysis catalysts prepared in examples 2 to 4 were also subjected to the ozonolysis test with or without a direct current-assisted reaction, and activity test results similar to those of example 1 were obtained: namely, when the direct current auxiliary reaction is carried out, the catalyst prepared by the invention has excellent reaction stability and water resistance.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A preparation method of a manganese-containing monolithic electrically-assisted metal honeycomb catalyst is characterized by comprising the following operation steps:
(1) surface pretreatment of a metal substrate: soaking the metal honeycomb substrate in 0.5-2.0mol/L hydrochloric acid solution, removing surface oxides by ultrasonic treatment for 3-20min, and then washing the metal honeycomb substrate with water;
(2) preparing a manganese-containing precursor liquid: mixing potassium permanganate, acetic acid and glucose solution, continuously stirring for 0.5-4h to obtain manganese-containing precursor liquid, and placing the manganese-containing precursor liquid in a hydrothermal reaction kettle; the concentrations of potassium permanganate, acetic acid and glucose in the manganese-containing precursor liquid are respectively 0.05-0.30mol/L, 0.05-1.20mol/L and 0.01-0.10 mol/L;
(3) soaking the metal honeycomb substrate pretreated in the step (1) in the manganese-containing precursor liquid obtained in the step (2), and carrying out hydrothermal reaction at 100-; then taking out and carrying out ultrasonic treatment in distilled water for 2-20 min; and finally, drying at 50-150 ℃ for 5-20h to obtain the manganese-containing integral electrically-assisted metal honeycomb catalyst, wherein the mass percent of manganese is 10-70 wt.%.
2. The method of claim 1, wherein: the material of the metal honeycomb substrate is stainless steel, iron-chromium-aluminum alloy, nickel-chromium alloy, metal aluminum or aluminum alloy.
3. The method of claim 1, wherein: the concentration of the hydrochloric acid solution in the step (1) is 0.8-1.3mol/L, and the ultrasonic time is 8-15 min.
4. The method of claim 1, wherein: the rotating speed of the stirring in the step (2) is 600-1500r/min, and the stirring time is 1.5-2 h.
5. The method of claim 1, wherein: the hydrothermal reaction temperature in the step (3) is 120-160 ℃, and the hydrothermal time is 10-24 h.
6. The method of claim 1, wherein: in the step (3), the ultrasonic time is 5-10min, and the drying temperature is 80-120 ℃.
7. A manganese-containing monolithic electrically-assisted metal honeycomb catalyst prepared by the preparation method according to any one of claims 1 to 6, characterized in that: the mass percentage of manganese element in the catalyst is 10-70%.
8. Use of the manganese-containing monolithic electrically-assisted metal honeycomb catalyst of claim 7 in catalytic ozonolysis.
9. Use according to claim 8, characterized in that: the catalytic decomposition of ozone is carried out on a gas-solid phase reaction device: putting the manganese-containing integral electrically-assisted metal honeycomb catalyst into a reaction tube, and connecting two ends of the catalyst with leads to connect a direct-current power supply; when ozone gas is introduced for reaction, a stable current is applied to the catalyst through a direct current power supply to assist in regulating and controlling the oxidation reduction in the catalystThe electron gain and loss rate of the reaction is controlled, and further Mn in the catalyst is controlled3+With Mn4+The mutual conversion rate reaches dynamic balance, and the reaction stability and the water resistance of the catalyst for ozonolysis are improved.
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