CN113457703A - Catalyst manufacturing process and device - Google Patents
Catalyst manufacturing process and device Download PDFInfo
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- CN113457703A CN113457703A CN202110776428.5A CN202110776428A CN113457703A CN 113457703 A CN113457703 A CN 113457703A CN 202110776428 A CN202110776428 A CN 202110776428A CN 113457703 A CN113457703 A CN 113457703A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 126
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 239000011812 mixed powder Substances 0.000 claims abstract description 41
- 239000000843 powder Substances 0.000 claims abstract description 36
- 239000000835 fiber Substances 0.000 claims abstract description 30
- 238000005507 spraying Methods 0.000 claims abstract description 30
- 230000009471 action Effects 0.000 claims abstract description 26
- 239000011230 binding agent Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000009941 weaving Methods 0.000 claims abstract description 10
- 230000003213 activating effect Effects 0.000 claims abstract description 9
- 230000004913 activation Effects 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 239000006096 absorbing agent Substances 0.000 claims description 8
- 230000007797 corrosion Effects 0.000 claims description 8
- 238000005260 corrosion Methods 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 238000007865 diluting Methods 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 3
- 239000007921 spray Substances 0.000 abstract description 10
- 239000000853 adhesive Substances 0.000 description 17
- 230000001070 adhesive effect Effects 0.000 description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 239000002699 waste material Substances 0.000 description 14
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 9
- 229910010271 silicon carbide Inorganic materials 0.000 description 9
- 239000002912 waste gas Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 7
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000010453 quartz Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000007767 bonding agent Substances 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000000694 effects Effects 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
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- -1 phosphoric acid modified magnesium oxide Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001007 puffing effect Effects 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
- B01J27/228—Silicon carbide with phosphorus, arsenic, antimony or bismuth
-
- 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
- B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
-
- 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
-
- 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
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- B01J35/56—
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- B01J35/58—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
Abstract
The invention provides a catalyst manufacturing process and a device, wherein the process comprises the following steps: sequentially weaving target fiber filaments in the whole space of the multi-dimensional metal frame along the radial direction and the axial direction to form a target carrier; spraying the target binder into a target carrier under the action of an air compressor to form a target bonding carrier, and placing the target bonding carrier in a microwave cavity; spraying the target powder into the buffer cavity under the action of an air compressor to form target mixed powder, wherein the target mixed powder represents that the target powder is uniformly mixed with air; and spraying the target mixed powder onto a target bonding carrier in a microwave cavity, and then carrying out target drying and activating treatment to form the target catalyst. That is, the invention firstly forms a catalyst carrier based on the target fiber and the metal framework, and then sprays the target mixed powder after the target powder and the air are uniformly mixed onto the catalyst carrier sprayed with the binder for drying and activation to form the target catalyst, thereby improving the rapidity and the high efficiency of the catalyst preparation.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and relates to but is not limited to a catalyst manufacturing process and a catalyst manufacturing device.
Background
In the exhaust gas treatment, a catalyst is usually used to accelerate the reaction rate and improve the treatment efficiency. Therefore, how to efficiently and rapidly prepare the catalyst becomes one of the key problems which need to be solved at present.
In the prior art, titanium dioxide modified by phosphoric acid modified magnesium oxide is used as a carrier, waste three-way catalyst waste with an aluminum oxide coating on the surface and strength additives such as silicon carbide are used, magnesium is introduced, hydrothermal pretreatment is performed by phosphoric acid, waste three-way catalyst waste with an aluminum oxide coating on the surface and silicon carbide are introduced, aluminum phosphate is introduced to obtain a catalyst with high strength and wear resistance, and then the apparent framework of a honeycomb catalyst is changed on the basis to form the denitration catalyst.
However, in the prior art, when the catalyst is prepared, various materials such as titanium dioxide, waste gas catalyst waste, silicon carbide, three-way catalyst waste, aluminum phosphate and the like need to be introduced, so that the preparation process is complex and the process difficulty is high, and thus the preparation efficiency of the catalyst is not high.
Disclosure of Invention
The invention aims to provide a catalyst manufacturing process and a catalyst manufacturing device aiming at the defects in the denitration catalyst preparation process in the prior art, so as to solve the problem that the catalyst preparation efficiency is not high due to the complex manufacturing process and high process difficulty caused by the fact that various materials such as titanium dioxide, waste gas catalyst waste, silicon carbide, three-way catalyst waste, aluminum phosphate and the like need to be introduced when the catalyst is prepared in the prior art.
In order to achieve the above purpose, the embodiment of the present invention adopts the following technical solutions:
in a first aspect, the present invention provides a catalyst manufacturing process, including:
sequentially weaving target fiber filaments in the whole space of the multi-dimensional metal frame along the radial direction and the axial direction to form a target carrier;
spraying a target binder into the target carrier under the action of an air compressor to form a target bonding carrier, and placing the target bonding carrier in a microwave cavity;
spraying target powder into the buffer cavity under the action of the air compressor to form target mixed powder; wherein the target mixed powder represents that the target powder is uniformly mixed with air;
and spraying the target mixed powder onto the target bonding carrier in the microwave cavity, and then carrying out target drying and activating treatment to form the target catalyst.
Optionally, a microwave source is arranged on the outer wall of the top of the microwave cavity, and a wave absorber is arranged at the bottom of the microwave cavity.
Optionally, the spraying the target mixed powder onto the target bonding carrier in the microwave cavity and then performing target drying activation treatment to form a target catalyst, includes:
spraying the target mixed powder onto the target bonding carrier in the microwave cavity to form a first target mixture;
under the low-power action of the microwave source, carrying out target drying treatment on the first target mixture to form a second target mixture;
and carrying out target activation treatment on the second target mixture under the high-power action of the microwave source to form the target catalyst.
Optionally, the target fiber filaments are made of a material which does not absorb microwaves, and is high-temperature resistant and corrosion resistant.
Optionally, both the radial direction and the transverse direction of the target carrier are the target filaments, and the distance between adjacent target filaments is adjustable.
Optionally, the target powder includes microwave absorber particles and metal oxide particles.
Optionally, the target binder comprises a binder that is resistant to high temperatures, gas corrosion, and microwave absorption after drying.
Optionally, the target binder comprises a product produced after diluting the binder with a diluent.
In a second aspect, the present invention provides a catalyst made using the catalyst making process of the first aspect.
In a third aspect, the present invention provides an exhaust gas treatment device comprising the catalyst of the second aspect.
The invention has the beneficial effects that: the invention relates to a catalyst manufacturing process and a device, wherein the catalyst manufacturing process comprises the following steps: sequentially weaving target fiber filaments in the whole space of the multi-dimensional metal frame along the radial direction and the axial direction to form a target carrier; spraying a target binder into the target carrier under the action of an air compressor to form a target bonding carrier, and placing the target bonding carrier in a microwave cavity; spraying target powder into the buffer cavity under the action of the air compressor to form target mixed powder; wherein the target mixed powder represents that the target powder is uniformly mixed with air; and spraying the target mixed powder onto the target bonding carrier in the microwave cavity, and then carrying out target drying and activating treatment to form the target catalyst. That is, the invention weaves the glass fiber yarn or quartz fiber yarn and other target fiber yarn on the metal frame along the radial direction and axial direction to form the catalyst carrier, then sprays the target mixed powder of microwave absorbing particles, metal oxide and other target powder and air to the catalyst carrier coated with the adhesive to be dried and activated, thus forming the target catalyst, the whole manufacturing process is simple and the needed raw materials are few, solving the problems that the manufacturing process is complex and the process difficulty is large and the preparation efficiency of the catalyst is not high caused by introducing titanium dioxide, waste gas catalyst waste, silicon carbide, three-way catalyst waste, aluminum phosphate and other materials when preparing the catalyst in the prior art, greatly improving the rapidity and high efficiency of manufacturing the catalyst, thus realizing the purpose of uniformly and efficiently distributing the catalyst in the whole three-dimensional space, not only the used materials are less, but also the cost is low; furthermore, when the variety of the target powder is more, the prepared catalyst can be used for treating various harmful gas molecules, so that the diversity and the reliability of the prepared catalyst are greatly improved; in addition, because the target catalyst is formed in the microwave cavity, the scattered catalyst can be recovered in time, so that materials are saved, the catalyst is recovered and reused, the manufacturing efficiency of the catalyst is greatly improved, and the waste gas treatment efficiency is also greatly improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic view of a process for preparing a catalyst according to an embodiment of the present invention;
FIG. 2 is a schematic illustration of the injection of a target bonding agent into a target carrier according to one embodiment of the present invention;
FIG. 3 is a schematic diagram of uniformly spraying the target powder into the buffer chamber according to an embodiment of the present invention;
fig. 4 is a schematic diagram of a microwave cavity according to an embodiment of the present invention;
FIG. 5 is a schematic view of a catalyst manufacturing apparatus according to another embodiment of the present invention;
fig. 6 is a schematic diagram of a catalyst manufacturing control apparatus according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings or the orientations or positional relationships that the products of the present invention are conventionally placed in use, and are only used for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the devices or elements referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," "third," and the like are used solely to distinguish one from another and are not to be construed as indicating or implying relative importance.
Furthermore, the terms "horizontal", "vertical" and the like do not imply that the components are required to be absolutely horizontal or pendant, but rather may be slightly inclined. For example, "horizontal" merely means that the direction is more horizontal than "vertical" and does not mean that the structure must be perfectly horizontal, but may be slightly inclined.
In the description of the present invention, it should also be noted that, unless otherwise explicitly specified or limited, the terms "disposed," "mounted," "connected," and "connected" are to be construed broadly and may, for example, be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Here, the terms related to the present invention are explained:
the microwave is an electric wave with a frequency of 300 megahertz to 300 gigahertz, and water molecules in the heated medium material are polar molecules. Under the action of a rapidly changing high-frequency point magnetic field, the polarity orientation of the magnetic field changes along with the change of an external electric field. The effect of mutual friction motion of molecules is caused, at the moment, the field energy of the microwave field is converted into heat energy in the medium, so that the temperature of the material is raised, and a series of physical and chemical processes such as thermalization, puffing and the like are generated to achieve the aim of microwave heating.
Fig. 1 is a schematic flow chart of an indoor air purification method according to an embodiment of the present invention; FIG. 2 is a schematic illustration of the injection of a target bonding agent into a target carrier according to one embodiment of the present invention; FIG. 3 is a schematic diagram of uniformly spraying the target powder into the buffer chamber according to an embodiment of the present invention; fig. 4 is a schematic diagram of a microwave cavity according to an embodiment of the present invention; FIG. 5 is a schematic view of a catalyst manufacturing apparatus according to another embodiment of the present invention; fig. 6 is a schematic diagram of a catalyst manufacturing control apparatus according to an embodiment of the present invention. The following describes the catalyst manufacturing process provided by the embodiment of the present invention in detail with reference to fig. 1 to 6.
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the catalyst manufacturing process provided by the embodiment of the present invention, as shown in fig. 1, the catalyst manufacturing process may include the following steps:
and S101, sequentially weaving the target fiber yarns in the whole space of the multi-dimensional metal frame along the radial direction and the axial direction to form a target carrier.
Wherein, the target fiber yarn is a material which does not absorb microwave, is high temperature resistant and is corrosion resistant. Illustratively, the target filament may include a fiberglass filament, a quartz filament, or the like.
The multidimensional metal frame can be a three-dimensional metal frame, such as a cubic metal frame.
Specifically, the frame is made of metal to form the multi-dimensional metal frame, and then the target fiber yarns are used to weave the whole space of the multi-dimensional metal frame in sequence like weaving or knitting a sweater, and during the specific weaving, the target fiber yarns can be woven in sequence along the radial direction and then woven in sequence along the axial direction, or the target fiber yarns are woven in sequence along the axial direction and then woven in sequence along the radial direction until the whole space of the multi-dimensional metal frame is completely filled with the target fiber yarns, so that the target carrier can be formed. That is, the object carrier may have a multi-dimensional cubic space structure and may be composed of a plurality of small multi-dimensional cubes densely arranged in a microscopic view, and both the radial direction and the lateral direction of the object carrier may be the object filaments, and the interval between the adjacent object filaments may be adjustable.
In the actual processing process, the whole space of the target carrier is densely and hemp-like covered with the target fiber yarns, and the space or gap between the adjacent target fiber yarns can be controlled or adjusted in the radial direction or the transverse direction. And the thickness of each target fiber filament can be controlled or adjusted according to the size or intensity of the wind speed, so that each target fiber filament cannot be blown off by wind.
And S102, spraying a target bonding agent into the target carrier under the action of an air compressor to form a target bonding carrier, and placing the target bonding carrier into a microwave cavity.
Wherein, the outer wall of the top of the microwave cavity can be provided with a microwave source, and the bottom of the microwave cavity can be provided with a wave absorber which can be made of microwave absorbing material; for example, the absorber may be silicon carbide particles. Also, the target binder may include a binder that is resistant to high temperatures after drying, resistant to gas corrosion, and non-absorbing to microwaves, resistant to gas corrosion may be non-corrosive to other gases such as nitrogen oxides, sulfur oxides, hydrochloric acid, sulfuric acid, and the like, and resistant to high temperatures may include withstanding temperatures between 300 ℃ and 400 ℃ or temperatures below 110 ℃. For example, the target adhesive may include a product obtained by diluting the adhesive with a diluent, such as a product obtained by diluting silicone acrylate with rubber water or copper.
Specifically, as shown in fig. 2, the operation of spraying the target adhesive onto the target carrier may be performed in a predetermined chamber, thereby preventing environmental pollution. Moreover, the preset cavity can also be made of a material which is high temperature resistant, gas corrosion resistant and does not absorb microwaves. When it is determined that the target adhesive is uniformly and sufficiently adhered to each target filament in the entire space of the target carrier placed in the preset cavity under the action of the air compressor and the spray gun, it may be determined that the target adhesive carrier is formed, and at this time, the target adhesive carrier may be further placed in the microwave cavity.
It should be noted that, the air compressor and the spray gun are used for spraying the target binder on the target carrier, because the air compressor can generate high pressure, air pressure is high and can be used as power, and when the spray gun is combined for spraying, the target binder can be fully and uniformly sprayed on each target fiber yarn in the whole multidimensional space of the target carrier, thereby laying a foundation for the subsequent generation of the catalyst with high catalytic efficiency.
Step S103, spraying target powder into a buffer cavity under the action of the air compressor to form target mixed powder; and the target mixed powder represents that the target powder is uniformly mixed with air.
The target powder can be all catalyst particles which are commercially available and can be used for waste gas treatment, the target powder can comprise microwave absorbent particles and metal oxide particles, the microwave absorbent particles can comprise manganese oxide particles, copper oxide particles, silicon carbide particles and the like, and the metal oxide can comprise nickel-based catalyst particles and titanium dioxide nanoparticles.
Specifically, as shown in fig. 3, the target powder is uniformly sprayed into the buffer cavity under the action of the air compressor and the spray gun, so that the target powder and the air are uniformly mixed in the buffer cavity in proportion to form the target mixed powder. Wherein, the uniform mixing of the air and the target powder can prevent the target powder from being blown away or scattered by a blast of wind. And the mixing ratio of the target powder and the air is adjustable. For example, the target powder can be weighed in proportion and then placed in a buffer chamber, and then the target powder and air are uniformly mixed under the action of an air compressor and a spray gun.
And step S104, spraying the target mixed powder onto the target bonding carrier in the microwave cavity, and then carrying out target drying and activating treatment to form the target catalyst.
Specifically, when the step S104 is implemented, the method may specifically include: as shown in fig. 4, the door or the nozzle of the buffer chamber may be opened first, so that the target mixed powder in the buffer chamber is sprayed onto the target bonding carrier in the microwave chamber through the door of the microwave chamber to form a first target mixture, where the first target mixture may indicate that the target mixed powder has been uniformly and sufficiently bonded to the target bonding carrier, for example, the target mixed powder is uniformly and sufficiently sprayed on each target fiber filament in the entire space of the target bonding carrier; under the action of low power of the microwave source, the first target mixture can be subjected to target drying treatment, namely a wave absorber at the bottom of the microwave cavity can absorb microwaves under the condition of low microwave power of the microwave source and then heat the first mixture to perform target drying treatment, so that a second target mixture is formed; and finally, under the high-power action of the microwave source, target activation treatment can be carried out on the second target mixture, namely, the wave absorber at the bottom of the microwave cavity can absorb the microwaves under the high-power condition of the microwave source and then carry out activation treatment on the second target mixture, so that a target catalyst can be formed.
It should be noted that, because the target catalyst is formed in the microwave cavity, if there is the scattered target catalyst, the target catalyst can be recycled, for example, put into the buffer cavity for use, so as to not pollute the environment, but also save the material.
The invention provides a catalyst preparation process, which comprises the following steps: sequentially weaving target fiber filaments in the whole space of the multi-dimensional metal frame along the radial direction and the axial direction to form a target carrier; spraying a target binder into the target carrier under the action of an air compressor to form a target bonding carrier, and placing the target bonding carrier in a microwave cavity; spraying target powder into the buffer cavity under the action of the air compressor to form target mixed powder; wherein the target mixed powder represents that the target powder is uniformly mixed with air; and spraying the target mixed powder onto the target bonding carrier in the microwave cavity, and then carrying out target drying and activating treatment to form the target catalyst. That is, the invention weaves the glass fiber yarn or quartz fiber yarn and other target fiber yarn on the metal frame along the radial direction and axial direction to form the catalyst carrier, then sprays the target mixed powder of microwave absorbing particles, metal oxide and other target powder and air to the catalyst carrier coated with the adhesive to be dried and activated, thus forming the target catalyst, the whole manufacturing process is simple and the needed raw materials are few, solving the problems that the manufacturing process is complex and the process difficulty is large and the preparation efficiency of the catalyst is not high caused by introducing titanium dioxide, waste gas catalyst waste, silicon carbide, three-way catalyst waste, aluminum phosphate and other materials when preparing the catalyst in the prior art, greatly improving the rapidity and high efficiency of manufacturing the catalyst, thus realizing the purpose of uniformly and efficiently distributing the catalyst in the whole three-dimensional space, not only the used materials are less, but also the cost is low; furthermore, when the variety of the target powder is more, the prepared catalyst can be used for treating various harmful gas molecules, so that the diversity and the reliability of the prepared catalyst are greatly improved; in addition, because the target catalyst is formed in the microwave cavity, the scattered catalyst can be recovered in time, so that materials are saved, the catalyst is recovered and reused, the manufacturing efficiency of the catalyst is greatly improved, and the waste gas treatment efficiency is also greatly improved.
In another embodiment, the present invention also provides a catalyst that can be fabricated using the catalyst fabrication process described in the previous embodiment.
It should be noted that, for the descriptions of the same steps and the same contents in this embodiment as those in other embodiments, reference may be made to the descriptions in other embodiments, which are not described herein again.
In another embodiment, the present invention further provides an exhaust gas treatment device, which may include other exhaust gas treatment equipment such as a VOCS treatment equipment, a desulfurization and denitrification equipment, a dioxin treatment equipment, and the like, and the exhaust gas treatment device may include the catalyst described in the foregoing embodiments, for example, the catalyst may be placed in the exhaust gas treatment device.
Fig. 5 shows a catalyst production apparatus provided in an embodiment of the present invention, and as shown in fig. 5, the apparatus includes: carrier forming module 501, adhesive module 502, mixed powder forming module 503 and catalyst forming module 504, wherein: the carrier forming module 501 is used for sequentially weaving target fiber yarns in the whole space of the multi-dimensional metal frame along the radial direction and the axial direction to form a target carrier; the adhesive module 502 is used for spraying target adhesive into the target carrier under the action of an air compressor to form a target adhesive carrier, and placing the target adhesive carrier in a microwave cavity; a mixed powder forming module 503, configured to spray the target powder into the buffer cavity under the action of the air compressor to form target mixed powder; wherein the target mixed powder represents that the target powder is uniformly mixed with air; and a catalyst forming module 504, configured to spray the target mixed powder into the microwave cavity with the target bonding carrier built therein to perform target drying and activating treatment, so as to form a target catalyst.
It should be noted that, for the descriptions of the same steps and the same contents in this embodiment as those in other embodiments, reference may be made to the descriptions in other embodiments, which are not described herein again.
The present invention provides a catalyst production apparatus, including: the device comprises: the carrier forms module, glues binder module, mixed powder and forms module and catalyst and form the module, wherein: the carrier forming module is used for sequentially weaving the target fiber yarns in the multi-dimensional metal frame along the radial direction and the axial direction to form a target carrier; the adhesive module is used for spraying a target adhesive into the target carrier under the action of an air compressor to form a target adhesive carrier, and placing the target adhesive carrier in a microwave cavity; the mixed powder forming module is used for spraying target powder into the buffer cavity under the action of the air compressor to form target mixed powder; wherein the target mixed powder represents that the target powder is uniformly mixed with air; and the catalyst forming module is used for spraying the target mixed powder into the microwave cavity with the target bonding carrier inside to carry out target drying and activating treatment so as to form the target catalyst. That is, according to the invention, glass fiber filaments or quartz fiber filaments and other target fiber filaments are sequentially woven on a metal frame along the radial direction and the axial direction to form a catalyst carrier, then target mixed powder obtained by uniformly mixing target powder such as microwave absorption particles and metal oxides with air is sprayed onto the catalyst carrier coated with a binder, and then the target mixed powder is dried and activated, so that the target catalyst can be formed, the whole manufacturing process is simple, the required raw materials are few, the problems that in the prior art, when the catalyst is prepared, various materials such as titanium dioxide, waste gas catalyst waste, silicon carbide, three-way catalyst waste, aluminum phosphate and the like need to be introduced, the manufacturing process is complex, the process difficulty is large, and the preparation efficiency of the catalyst is not high are solved, and the rapidness and the high efficiency of the catalyst are greatly improved; furthermore, when the variety of the target powder is more, the prepared catalyst can be used for treating various harmful gas molecules, so that the diversity and the reliability of the prepared catalyst are greatly improved; in addition, because the target catalyst is formed in the microwave cavity, the scattered catalyst can be recovered in time, so that materials are saved, the catalyst is recovered and reused, the manufacturing efficiency of the catalyst is greatly improved, and the waste gas treatment efficiency is also greatly improved.
Fig. 6 is a schematic diagram of a catalyst manufacturing control apparatus according to another embodiment of the present invention, where the control apparatus may be integrated in a terminal device or a chip of the terminal device, and the apparatus includes: memory 601, processor 602.
The memory 601 is used for storing programs, and the processor 602 calls the programs stored in the memory 601 to execute the above method embodiments. The specific implementation and technical effects are similar, and are not described herein again.
Preferably, the present invention also provides a computer readable storage medium comprising a program which, when executed by a processor, is adapted to perform the above-described method embodiments.
In the embodiments provided in the present invention, it should be understood that the disclosed apparatus and method may be implemented in other ways. For example, the above-described apparatus embodiments are merely illustrative, and for example, a division of a unit is merely a logical division, and an actual implementation may have another division, for example, a plurality of units or components may be combined or integrated into another system, or some features may be omitted, or not executed. In addition, the shown or discussed mutual coupling or direct coupling or communication connection may be an indirect coupling or communication connection through some interfaces, devices or units, and may be in an electrical, mechanical or other form.
Units described as separate parts may or may not be physically separate, and parts displayed as units may or may not be physical units, may be located in one place, or may be distributed on a plurality of network units. Some or all of the units can be selected according to actual needs to achieve the purpose of the solution of the embodiment.
In addition, functional units in the embodiments of the present invention may be integrated into one processing unit, or each unit may exist alone physically, or two or more units are integrated into one unit. The integrated unit can be realized in a form of hardware, or in a form of hardware plus a software functional unit.
The integrated unit implemented in the form of a software functional unit may be stored in a computer readable storage medium. The software functional unit is stored in a storage medium and includes several instructions to enable a computer device (which may be a personal computer, a server, or a network device) or a processor (processor) to execute some steps of the methods according to the embodiments of the present invention. And the aforementioned storage medium includes: a U disk, a removable hard disk, a Read-Only Memory (ROM), a Random Access Memory (RAM), a magnetic disk or an optical disk, and other various media capable of storing program codes.
Claims (10)
1. A catalyst manufacturing process, comprising:
sequentially weaving target fiber filaments in the whole space of the multi-dimensional metal frame along the radial direction and the axial direction to form a target carrier;
spraying a target binder into the target carrier under the action of an air compressor to form a target bonding carrier, and placing the target bonding carrier in a microwave cavity;
spraying target powder into the buffer cavity under the action of the air compressor to form target mixed powder; wherein the target mixed powder represents that the target powder is uniformly mixed with air;
and spraying the target mixed powder onto the target bonding carrier in the microwave cavity, and then carrying out target drying and activating treatment to form the target catalyst.
2. The process for preparing catalyst according to claim 1, wherein the microwave source is disposed on the outer wall of the top of the microwave cavity, and the absorber is disposed on the bottom of the microwave cavity.
3. The catalyst production process according to claim 2, wherein the target mixed powder is sprayed onto the target bonding carrier in the microwave cavity and then subjected to target drying and activating treatment to form the target catalyst, and the target catalyst production process includes:
spraying the target mixed powder onto the target bonding carrier in the microwave cavity to form a first target mixture;
under the low-power action of the microwave source, carrying out target drying treatment on the first target mixture to form a second target mixture;
and carrying out target activation treatment on the second target mixture under the high-power action of the microwave source to form the target catalyst.
4. The process of claim 1, wherein the target fiber is a material that is non-microwave absorbing and is resistant to high temperatures and corrosion.
5. The catalyst production process according to claim 1, wherein the target carrier has both a radial direction and a transverse direction of the target fiber filaments, and a pitch between adjacent target fiber filaments is adjustable.
6. The process of claim 1, wherein the target powder comprises microwave absorber particles and metal oxide particles.
7. The process of claim 1, wherein the target binder comprises a binder that is resistant to high temperatures, gas corrosion, and microwave absorption after drying.
8. The catalyst preparation process of claim 1, wherein the target binder comprises a product produced by diluting a binder with a diluent.
9. A catalyst, wherein the catalyst is made using the catalyst making process of any of the preceding claims 1-8.
10. An exhaust gas treatment device, characterized in that the device comprises the catalyst as recited in claim 9.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN203184206U (en) * | 2013-03-27 | 2013-09-11 | 江苏帕艾尼尔科技有限公司 | Continuous microwave drying device of three-way catalyst for vehicle |
| CN104001555A (en) * | 2014-05-21 | 2014-08-27 | 姚光纯 | Catalyst or carrier woven by coated wires and production method for catalyst or carrier |
| CN104998694A (en) * | 2015-05-29 | 2015-10-28 | 万华化学集团股份有限公司 | Cladding type catalyst carrier, preparation method thereof and cladding type catalyst |
| CN105251542A (en) * | 2015-11-13 | 2016-01-20 | 青岛华世洁环保科技有限公司 | Ceramic-fiber-based catalyst carrier and preparing method thereof |
| CN106378180A (en) * | 2016-10-28 | 2017-02-08 | 姚光纯 | Method for preparing catalyst by steeping active component into target material in targeting manner |
| CN109364701A (en) * | 2018-10-05 | 2019-02-22 | 萍乡市三力科技有限责任公司 | It is a kind of for handling the composite silicon carbide ceramic pipe and preparation method of high-temp waste gas |
| CN110368952A (en) * | 2019-08-06 | 2019-10-25 | 东莞市三聚氢能科技有限公司 | A kind of preparation method of jet printing type production sodium borohydride catalyst for preparing hydrogen |
| CN111558371A (en) * | 2020-04-20 | 2020-08-21 | 上海海庭环境工程有限公司 | Catalyst preparation method based on ceramic matrix and carbon-based mixture as carrier and matched flat plate type ozone oxidation reactor |
-
2021
- 2021-07-09 CN CN202110776428.5A patent/CN113457703A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN203184206U (en) * | 2013-03-27 | 2013-09-11 | 江苏帕艾尼尔科技有限公司 | Continuous microwave drying device of three-way catalyst for vehicle |
| CN104001555A (en) * | 2014-05-21 | 2014-08-27 | 姚光纯 | Catalyst or carrier woven by coated wires and production method for catalyst or carrier |
| CN104998694A (en) * | 2015-05-29 | 2015-10-28 | 万华化学集团股份有限公司 | Cladding type catalyst carrier, preparation method thereof and cladding type catalyst |
| CN105251542A (en) * | 2015-11-13 | 2016-01-20 | 青岛华世洁环保科技有限公司 | Ceramic-fiber-based catalyst carrier and preparing method thereof |
| CN106378180A (en) * | 2016-10-28 | 2017-02-08 | 姚光纯 | Method for preparing catalyst by steeping active component into target material in targeting manner |
| CN109364701A (en) * | 2018-10-05 | 2019-02-22 | 萍乡市三力科技有限责任公司 | It is a kind of for handling the composite silicon carbide ceramic pipe and preparation method of high-temp waste gas |
| CN110368952A (en) * | 2019-08-06 | 2019-10-25 | 东莞市三聚氢能科技有限公司 | A kind of preparation method of jet printing type production sodium borohydride catalyst for preparing hydrogen |
| CN111558371A (en) * | 2020-04-20 | 2020-08-21 | 上海海庭环境工程有限公司 | Catalyst preparation method based on ceramic matrix and carbon-based mixture as carrier and matched flat plate type ozone oxidation reactor |
Non-Patent Citations (1)
| Title |
|---|
| 北京市环境保护科学研究所, 合肥：中国科学技术大学出版社 * |
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