CN115624969A - Photo-thermal synergistic catalyst and solar energy purifying, ventilating and cooling composite wall structure - Google Patents
Photo-thermal synergistic catalyst and solar energy purifying, ventilating and cooling composite wall structure Download PDFInfo
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- CN115624969A CN115624969A CN202211326218.7A CN202211326218A CN115624969A CN 115624969 A CN115624969 A CN 115624969A CN 202211326218 A CN202211326218 A CN 202211326218A CN 115624969 A CN115624969 A CN 115624969A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 33
- 238000001816 cooling Methods 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000009423 ventilation Methods 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 28
- 238000000746 purification Methods 0.000 claims abstract description 22
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 45
- 230000003197 catalytic effect Effects 0.000 claims description 34
- 238000005338 heat storage Methods 0.000 claims description 32
- 239000011248 coating agent Substances 0.000 claims description 31
- 238000000576 coating method Methods 0.000 claims description 31
- 239000011521 glass Substances 0.000 claims description 22
- 238000006555 catalytic reaction Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 14
- 230000002153 concerted effect Effects 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- YMKHJSXMVZVZNU-UHFFFAOYSA-N manganese(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YMKHJSXMVZVZNU-UHFFFAOYSA-N 0.000 claims description 8
- 239000002957 persistent organic pollutant Substances 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 230000000593 degrading effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 11
- 239000003344 environmental pollutant Substances 0.000 abstract description 10
- 231100000719 pollutant Toxicity 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 230000005855 radiation Effects 0.000 description 20
- 230000000694 effects Effects 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 13
- 230000009471 action Effects 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000009413 insulation Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 210000001503 joint Anatomy 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000004887 air purification Methods 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/38—Removing components of undefined structure
- B01D53/44—Organic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
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-
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- 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
- B01J35/39—Photocatalytic properties
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
- F24F5/00—Air-conditioning systems or apparatus not covered by F24F1/00 or F24F3/00, e.g. using solar heat or combined with household units such as an oven or water heater
- F24F5/0046—Air-conditioning systems or apparatus not covered by F24F1/00 or F24F3/00, e.g. using solar heat or combined with household units such as an oven or water heater using natural energy, e.g. solar energy, energy from the ground
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
- F24F5/00—Air-conditioning systems or apparatus not covered by F24F1/00 or F24F3/00, e.g. using solar heat or combined with household units such as an oven or water heater
- F24F5/0096—Air-conditioning systems or apparatus not covered by F24F1/00 or F24F3/00, e.g. using solar heat or combined with household units such as an oven or water heater combined with domestic apparatus
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- F24—HEATING; RANGES; VENTILATING
- F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
- F24F7/00—Ventilation
- F24F7/003—Ventilation in combination with air cleaning
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
- F24F7/00—Ventilation
- F24F7/04—Ventilation with ducting systems, e.g. by double walls; with natural circulation
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
- F24F8/00—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying
- F24F8/10—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by separation, e.g. by filtering
- F24F8/15—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by separation, e.g. by filtering by chemical means
- F24F8/167—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by separation, e.g. by filtering by chemical means using catalytic reactions
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S10/00—Solar heat collectors using working fluids
- F24S10/40—Solar heat collectors using working fluids in absorbing elements surrounded by transparent enclosures, e.g. evacuated solar collectors
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S10/00—Solar heat collectors using working fluids
- F24S10/70—Solar heat collectors using working fluids the working fluids being conveyed through tubular absorbing conduits
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- F24—HEATING; RANGES; VENTILATING
- F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
- F24F5/00—Air-conditioning systems or apparatus not covered by F24F1/00 or F24F3/00, e.g. using solar heat or combined with household units such as an oven or water heater
- F24F5/0046—Air-conditioning systems or apparatus not covered by F24F1/00 or F24F3/00, e.g. using solar heat or combined with household units such as an oven or water heater using natural energy, e.g. solar energy, energy from the ground
- F24F2005/0064—Air-conditioning systems or apparatus not covered by F24F1/00 or F24F3/00, e.g. using solar heat or combined with household units such as an oven or water heater using natural energy, e.g. solar energy, energy from the ground using solar energy
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
- F24F2221/00—Details or features not otherwise provided for
- F24F2221/18—Details or features not otherwise provided for combined with domestic apparatus
- F24F2221/183—Details or features not otherwise provided for combined with domestic apparatus combined with a hot-water boiler
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Abstract
The invention discloses a photo-thermal synergistic catalyst and solar energy purification, ventilation and cooling composite wall structure. The invention relates to a photo-thermal assistantWith catalyst consisting of MnOx-CeO 2 Powder with TiO 2 The photo-thermal synergistic catalyst is applied to the wall structure, compared with the traditional wall with single function, the wall structure combines purification, heating, hot water preparation and ventilation, runs different modes in different seasons, is beneficial to building energy conservation on one hand, and realizes the treatment of indoor pollutants on the other hand.
Description
Technical Field
The invention belongs to the technical field of solar energy utilization and building walls, and particularly relates to a photo-thermal synergistic catalyst and a solar energy purification, ventilation and cooling composite wall structure.
Background
In recent years, improvement of indoor environment and improvement of energy utilization rate become hot problems concerned by people, clean energy is a hot point in the field of human energy development, solar energy is an energy form widely applied to clean energy, and although China is rich in territorial area and rich in solar energy resources, the development and utilization of solar building integration are insufficient, so that the development of a novel purifying and ventilating solar building has a huge application prospect.
In addition, formaldehyde treatment methods include adsorption, biological incineration, photocatalytic oxidation, and thermal catalytic oxidation. The photocatalytic oxidation purification technology is a technology that photocatalytic degradation is carried out on indoor pollutants by a photocatalyst under the drive of ultraviolet light, the thermal catalytic oxidation purification technology is a technology that the indoor pollutants are thermally degraded by a thermal catalyst under the drive of heat, and the two technologies are advanced active air purification technologies. However, the photocatalytic technology is mainly carried out by ultraviolet light, the thermal catalytic technology needs certain energy as the activation energy of the reaction, and if the photocatalytic oxidation technology and the thermal catalytic oxidation technology can be combined together, the photo-thermal synergistic catalyst is prepared, and the catalyst is combined with a solar wall, so that the application value is very high.
Disclosure of Invention
The invention aims to provide a solar purifying, ventilating and cooling composite wall structure based on photo-thermal catalysis, which organically combines a photo-thermal concerted catalysis technology and a solar heat collecting and ventilating wall, and aims to solve the problems that the existing building has high indoor pollutant content and the existing heat collecting and ventilating wall has single function.
The invention further aims to provide a photo-thermal synergistic catalyst, and a preparation method and application thereof.
The invention is realized by a preparation method of a photo-thermal synergistic catalyst, which comprises the following steps:
(1) Adding manganese nitrate hexahydrate, potassium permanganate and ammonium ceric nitrate into deionized water, and uniformly stirring to obtain a mixed solution A;
(2) Dropwise adding an alkali solution into the mixed solution A to adjust the pH value to 10.5, stirring for 3-4 h to obtain a brown precipitate, aging for 1-3 h at 45-55 ℃, filtering, drying and grinding the obtained filter cake, and roasting the obtained powder for 5-7 h at 480-520 ℃ to obtain black MnOx-CeO 2 Powder, and mixing the components in a mass ratio of 3-9: 1 MnOx-CeO 2 Powder with TiO 2 And mechanically mixing the powder to obtain the photo-thermal synergistic catalyst.
Preferably, in the step (1), the mass-to-volume ratio of the manganese nitrate hexahydrate, the potassium permanganate, the ammonium ceric nitrate and the deionized water is 1.72g:0.63g:5.48g: 90-110 mL.
Preferably, in the step (2), the MnOx-CeO 2 Powder with TiO 2 The mass ratio of the powder is 9:1; the alkali solution is 2moL/L potassium hydroxide solution; the drying is carried out in a drying oven at 110 ℃ for 12h.
The invention further discloses the photo-thermal synergistic catalyst obtained by the preparation method.
The invention further discloses an application of the photo-thermal synergistic catalyst in degrading organic pollutants, wherein the organic pollutants comprise formaldehyde.
The invention further discloses a solar energy purification ventilation cooling composite wall structure based on photo-thermal catalysis, which is arranged as a side wall between a bottom plate and a top plate of each layer in a building, and comprises a heat storage wall body at the indoor direction side and a glass cover plate at the outdoor direction side, wherein an air flow channel is formed between the heat storage wall body and the glass cover plate, lower vent holes are respectively arranged between the heat storage wall body, the glass cover plate and the bottom plate, each lower vent hole is provided with a lower baffle plate, upper vent holes are respectively arranged between the heat storage wall body, the glass cover plate and the top plate, and each upper vent hole is provided with an upper baffle plate; in the direction towards the outside of the room, a heat collecting layer and a photo-thermal catalytic coating formed by coating the photo-thermal synergistic catalyst in the claim 5 are sequentially arranged on the heat storage wall body, a heat collecting water pipe is arranged in the heat collecting layer, the water inlet end of the heat collecting water pipe is butted with an indoor or outdoor water pipe, and the water outlet end of the heat collecting water pipe is connected into an indoor heat collecting water tank; the photo-thermal catalytic coating performs photo-thermal concerted catalytic reaction under the irradiation of sunlight and degrades organic pollutants in the air flow channel.
Preferably, the thickness of the air flow channel is 15 cm-20 cm.
Preferably, the thickness of the photo-thermal catalytic coating is 2 μm to 50 μm.
The invention overcomes the defects of the prior art and provides a composite wall structure with photo-thermal synergistic catalyst and solar energy purification, ventilation and cooling functions. The preparation method of the photo-thermal synergistic catalyst comprises the following steps: mixing manganese nitrate hexahydrate (Mn (NO) 3 ) 2 ·6H 2 O), potassium permanganate (KMnO) 4 ) And cerium ammonium nitrate ((NH) 4 ) 2 Ce(NO 3 ) 6 ) Adding into a certain amount of deionized water, stirring with a magnetic stirrer to obtain a mixed solution A, dropwise adding potassium hydroxide (KOH) solution into the solution A to adjust pH to alkalinity, stirring, filtering, aging, drying, and roasting to obtain black MnOx-CeO 2 Powder of MnOx-CeO 2 Powder with TiO 2 The powder is mechanically mixed to obtain the photo-thermal synergistic catalyst.
Under the sunlight irradiation condition, namely the light and heat condition, the photo-thermal synergistic catalyst can efficiently degrade indoor organic pollutants such as formaldehyde and the like, so that the photo-thermal synergistic catalyst can be well applied to a wall structure.
On the basis, the invention further discloses a solar energy purification ventilation cooling composite wall structure which is arranged as a side wall between a bottom plate and a top plate of each layer in a building, and comprises a heat storage wall body at the indoor direction side and a glass cover plate at the outdoor direction side, wherein an air flow channel is formed between the heat storage wall body and the glass cover plate, lower ventilation openings are respectively arranged between the heat storage wall body, the glass cover plate and the bottom plate, each lower ventilation opening is provided with a lower baffle, upper ventilation openings are respectively arranged between the heat storage wall body, the glass cover plate and the top plate, and each upper ventilation opening is provided with an upper baffle; in the direction towards the outside of the room, a heat collecting layer and a photo-thermal catalytic coating formed by coating the photo-thermal synergistic catalyst are sequentially arranged on the heat storage wall body, a heat collecting water pipe is arranged in the heat collecting layer, the water inlet end of the heat collecting water pipe is in butt joint with an indoor or outdoor water pipe, and the water outlet end of the heat collecting water pipe is connected into an indoor heat collecting water tank; the photo-thermal catalytic coating carries out photo-thermal concerted catalytic reaction under the irradiation of sunlight and degrades organic pollutants in the air flow channel.
The wall structure comprises four operation modes: the wall comprises four operation modes:
(1) The first mode of operation is a heating-purifying mode
In the heating season, under the action of solar radiation, on one hand, the temperature of the photothermal catalytic coating on the heat storage wall rises after solar radiation, air in an air flow channel is heated to generate natural convection, on the other hand, the photothermal catalytic coating adsorbs pollutants such as formaldehyde in indoor air, and the formaldehyde is degraded into CO through photothermal concerted catalytic reaction on the surface of the photothermal catalytic coating 2 And H 2 O, enabling the purified warm air to flow into the room to realize the functions of purification and heating;
(2) The second operating mode is a hot water-cleaning mode
In non-heating seasons, under the action of solar radiation, one part of energy is transferred into the heat collection water pipe to increase the temperature of water in the water pipe, and the other part of energy is absorbed by the photo-thermal catalytic coating to generate a formaldehyde photo-thermal synergistic catalytic degradation reaction, so that indoor cold load is reduced while indoor air is purified, and the effects of purifying, cooling and preparing domestic hot water are realized;
(3) The third operation mode is a heat preservation mode
In a transition season, the four baffles are completely closed, and because the heat conductivity coefficient of air is low, the air in the air flow channel forms a heat insulation layer, so that the heat insulation effect is realized;
(4) The fourth mode of operation is a purge-vent mode
In a transition season, the baffle is opened, indoor air and outdoor air can circulate, stale indoor air flows outdoors, fresh outdoor air flows indoors, ventilation is achieved, meanwhile, the photo-thermal catalytic coating can also receive energy of solar radiation, indoor polluted air is purified, and purification is achieved.
Compared with the defects and shortcomings of the prior art, the invention has the following beneficial effects:
(1) The photo-thermal synergistic catalyst is prepared by a simple method, and is applied to a solar wall, so that the organic combination of a photo-thermal synergistic catalysis technology and a heat collection ventilation wall is realized; under the action of solar radiation, indoor air flows through the air flow channel from the air vent at the lower part of the heat storage wall body, harmful gases such as formaldehyde and the like undergo photocatalysis and thermocatalysis cooperative catalytic purification reaction through the photo-thermal catalytic coating on the heat storage wall body, the harmful gases such as formaldehyde and the like are catalytically degraded into clean air, and the purified air flows into the room from the upper part of the main wall body so as to realize the purification effect of the wall body;
(2) Compared with the traditional wall with single function, the invention combines the functions of purification, heating, hot water preparation and ventilation, runs in different modes in different seasons, is beneficial to building energy conservation on one hand, and realizes the treatment of indoor pollutants on the other hand. Under the effect of solar radiation, on the one hand, the water temperature in the water pipe is driven to rise, the effect of preparing hot water is realized, and on the other hand, the photothermal catalytic coating transfers heat to the heat storage wall body while purifying harmful gas, so that the effects of purification and heating are realized. In addition, in a transition season, the baffle below the heat storage wall body and the baffle above the glass cover plate can be opened, and stale air in a room flows to the outside through the air flow channel, so that the ventilation effect is realized.
Drawings
FIG. 1 is a schematic cross-sectional view of a solar energy purifying ventilation wall according to the present invention;
FIG. 2 is a layout view of hot water pipes in a heat collecting layer in the solar energy purifying ventilation wall body;
FIG. 3 is a schematic view of the solar energy purifying ventilation wall of the present invention operating in a hot water-purifying mode;
FIG. 4 is a schematic view of the solar energy purifying ventilation wall of the present invention operating in heating-purifying mode;
FIG. 5 is a schematic view of the solar energy purifying ventilation wall of the present invention operating in a thermal insulation mode;
FIG. 6 is a schematic view of the solar energy purifying ventilation wall of the present invention operating in a purifying-ventilating mode;
wherein: 1-heat storage wall; 2-heat collecting layer; 2-1-cold water inlet end; 2-hot water outlet end; 3-photo-thermal catalytic coating; 4-air flow channel; 5, a glass cover plate; 6-top plate; 7-a bottom plate; 8, a circulating water pump; 9-a heat collecting water tank; 10-a first upper baffle; 11-a second upper baffle; 12-a first lower baffle; 13-second lower baffle.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Example 1
(1) 172g of manganese nitrate hexahydrate (Mn (NO) 3 ) 2 ·6H 2 O), 63g potassium permanganate (KMnO) 4 ) And 548g of cerium ammonium nitrate ((NH) 4 ) 2 Ce(NO 3 ) 6 ) Adding the mixture into 1L of deionized water, and uniformly stirring to obtain a mixed solution A;
(2) Dropwise adding 2moL/L potassium hydroxide (KOH) solution into the mixed solution A to adjust the pH value to 10.5, stirring for 3-4 h to obtain brown precipitate, aging for 2h at 50 ℃, filtering, drying the obtained filter cake for 12h at 110 ℃ in a drying oven, grinding, roasting the obtained powder for 6h at 500 ℃ to obtain black MnOx-CeO 2 Powder, and 90g of MnOx-CeO 2 Powder with 10g TiO 2 The powders are mechanically mixed to obtain the photothermal synergistic catalyst 1.
Example 2
(1) 170g of manganese nitrate hexahydrate (Mn (NO) 3 ) 2 ·6H 2 O) and 60g potassium permanganate (KMnO) 4 ) And 550g of cerium ammonium nitrate ((NH) 4 ) 2 Ce(NO 3 ) 6 ) Adding the mixture into 1.1L of deionized water, and uniformly stirring to obtain a mixed solution A;
(2) Dropwise adding 2moL/L potassium hydroxide (KOH) solution into the mixed solution A to adjust the pH value to 10.5, stirring for 3h to obtain brown precipitate, aging for 1h at 45 ℃, filtering, drying the obtained filter cake in a drying oven at 110 ℃ for 12h, grinding, roasting the obtained powder at 480 ℃ for 5h to obtain black MnOx-CeO 2 Powder, 30g of MnOx-CeO 2 Powder with 10kg TiO 2 The powder is mechanically mixed to obtain the photo-thermal synergistic catalyst 2.
Example 3
(1) 175g of manganese nitrate hexahydrate (Mn (NO) 3 ) 2 ·6H 2 O), 65g of potassium permanganate (KMnO) 4 ) And 545g of cerium ammonium nitrate ((NH) 4 ) 2 Ce(NO 3 ) 6 ) Adding the mixture into 0.9L of deionized water, and uniformly stirring to obtain a mixed solution A;
(2) Dropwise adding 2moL/L potassium hydroxide (KOH) solution into the mixed solution A to adjust the pH value to 10.5, stirring for 4h to obtain a brown precipitate, aging for 3h at 55 ℃, filtering, drying the obtained filter cake in a drying oven for 12h at 110 ℃, grinding, roasting the obtained powder for 7h at 520 ℃ to obtain black MnOx-CeO 2 Powder of 50g of MnOx-CeO 2 Powder with 10kg TiO 2 And mechanically mixing the powder to obtain the photothermal synergistic catalyst 3.
Application examples
A solar energy based on photo-thermal catalysis purifies the ventilation cooling composite wall structure, this structure sets up as the side wall between bottom plate 7 and roof 6 of every floor in the building, as shown in figure 1, this structure includes heat storage wall 1 and glass cover 5 of the outdoor direction side of indoor direction side, form the air runner 4 between said heat storage wall 1, glass cover 5, have lower vent between bottom plate 7 and the heat storage wall 1, glass cover 5, every lower vent sets up the lower baffle, specifically the first lower baffle 12 of the lower vent of the glass cover 5, the second lower baffle 13 of the lower vent of the heat storage wall 1, there are upper vents between said heat storage wall 1, glass cover 5 and roof 6, every upper vent sets up the upper baffle, specifically the first upper baffle 10 of the upper vent of the glass cover 5, the second upper baffle 11 of the upper vent of the heat storage wall 1; in the direction towards the outside of the room, a heat collecting layer 2 and a photo-thermal synergistic catalyst 1 prepared in the embodiment 1 are sequentially arranged on the heat storage wall body 1 and coated to form a photo-thermal catalytic coating 3 with the thickness of 2-50 microns, a heat collecting water pipe is distributed in the heat collecting layer 2, a cold water inlet end 2-1 of the heat collecting water pipe is in butt joint with an indoor or outdoor water pipe, and a hot water outlet end 2-2 of the heat collecting water pipe is connected to an indoor heat collecting water tank 9; the photo-thermal catalytic coating 3 performs photo-thermal concerted catalytic reaction under the irradiation of sunlight and degrades organic pollutants in the air flow channel 4.
In the embodiment of the invention, the heat collecting water pipe is arranged in the heat collecting layer 2 in an S-shaped pipeline, as shown in FIG. 2, the inner pipe wall of the S-shaped pipe is in a spiral groove shape, water flow is blocked and guided near the wall of the spiral groove of the S-shaped pipe and flows in a rotating way along spiral grains, so that a fluid boundary layer is weakened, the heat exchange effect of cold water and solar radiation is enhanced, and the water inlet end and the water outlet end are positioned at the lower end and the upper end of the heat collecting pipe; in non-heating seasons, power is provided through the circulating water pump 8, the hot water pipeline absorbs energy of solar radiation, and obtained domestic hot water is stored in the heat collecting water tank 9.
In the embodiment of the invention, the thickness of the air flow channel 4 is 10 cm-12 cm, so that the air can normally flow under the action of buoyancy.
In the embodiment of the invention, the photo-thermal concerted catalysis technology is organically combined with the solar heat collection ventilation wall body, the photo-thermal concerted catalyst is coated on the outer surface of the heat storage wall body 1, the thickness of the photo-thermal concerted catalyst is 2-50 mu m, and the photo-thermal concerted catalysis coating 3 can absorb the energy of solar radiation to carry out photo-thermal concerted catalysis purification reaction for purifying indoor pollutants and can effectively utilize the energy of solar radiation to purify indoor pollutantsUltraviolet rays are used for realizing the antioxidation. The performance of the optimal photothermal synergistic catalyst is as follows, formaldehyde has single-pass rates of 31.03%, 26.41% and 22.72% at a temperature of 20 ℃, 33.33%, 33.96% and 25.97% at a temperature of 40 ℃, and 34.51%, 35.29% and 27.91% at a temperature of 60 ℃ at typical indoor formaldehyde concentrations of 300ppb, 500ppb and 700ppb, respectively; the ultraviolet intensity is 0mW/cm respectively 2 、0.5mW/cm 2 、1.5mW/cm 2 And 2.9mW/cm 2 The apparent reaction activation energies of formaldehyde were 5388J/mol, 8484J/mol, 7348J/mol, 6112J/mol, and 5388J/mol.
By adopting the technical scheme, the wall body comprises four operation modes:
(1) Heating-purifying mode
In the heating season, under the action of solar radiation, on one hand, the temperature of the photothermal catalytic coating 3 on the heat storage wall body 1 rises after solar radiation, air in the air flow channel 4 is heated to generate natural convection, on the other hand, the photothermal catalytic coating 3 adsorbs pollutants such as formaldehyde in indoor air, and the formaldehyde is degraded into CO through photothermal concerted catalytic reaction on the surface of the photothermal catalytic coating 3 2 And H 2 And O, enabling the purified warm air to flow into the room, and realizing the functions of purification and heating.
As shown in fig. 3, for the hot water-purification mode, the cold water inlet end 2-1 and the hot water outlet end 2-2 are opened, and then the second lower baffle 13 and the second upper baffle 11 of the thermal storage wall 1 are opened; cold water is pressurized by a circulating water pump 8 to obtain energy of solar radiation from a heat collection pipeline, the obtained hot water is stored in a heat collection water tank 9, the effect of preparing domestic hot water is achieved, meanwhile, energy of another part in the solar radiation irradiates on a photo-thermal catalytic coating 3, photo-thermal catalytic reaction is carried out on photo-thermal synergistic catalyst on the coating and air polluted indoors, the obtained clean air flows into the indoor through an upper ventilation opening of a heat storage wall body 1, the indoor pollutants are purified, in addition, most energy is obtained due to the fact that the hot water is hot water, the solar radiation enters the indoor energy through a maintenance structure to be reduced, indoor cold load is reduced, and the effect of cooling the wall body is achieved.
(2) Hot water-cleaning mode
In non-heating seasons, under the action of solar radiation, one part of energy is transferred to the heat collection water pipe to increase the temperature of water in the water pipe, and the other part of energy is absorbed by the photo-thermal catalytic coating 3 to generate a formaldehyde photo-thermal synergistic catalytic degradation reaction, so that indoor cold load is reduced while indoor air is purified, and the effects of purifying, cooling and preparing domestic hot water are realized.
As shown in fig. 4, for the heating-purifying mode, the second lower baffle 13 and the second upper baffle 11 of the thermal storage wall 1 are opened, and the water inlet end and the water outlet end are closed; indoor air to be purified enters the air flow channel 4 from the ventilation opening at the lower part of the main wall body, under the action of solar radiation, indoor polluted air in the air flow channel 4 reacts with the photo-thermal catalytic coating 3, pollutants in the indoor air are decomposed under the action of photo-thermal concerted catalysis, and the purified air is introduced into the room through the ventilation opening at the upper part of the main wall body, so that the purification function of the wall body is realized; meanwhile, the heat storage wall body 1 absorbs heat of solar radiation and conducts the heat to the indoor space, and the heating effect is achieved.
(3) Heat preservation mode
In a transition season, the four baffles are completely closed, and because the heat conductivity coefficient of air is low, the air in the air flow channel 4 forms a heat insulation layer, so that the heat insulation effect is realized.
For the heat preservation mode, as shown in fig. 5, when all the vent baffles are closed, that is, the first upper baffle 10, the second upper baffle 11, the first lower baffle 12 and the second lower baffle 13 are closed, the air in the air flow channel 4 cannot be exchanged with the air inside and outside the room, so that the air flow channel 4 forms a closed cavity, but because the thermal conductivity of the air is low, the closed cavity also forms a heat preservation layer, and the heat preservation effect is achieved.
(4) Purge-vent mode
In a transition season, the baffle is opened, indoor air and outdoor air can circulate, stale indoor air flows outdoors, fresh outdoor air flows indoors, ventilation effect is achieved, meanwhile, the photo-thermal catalytic coating 3 can also receive energy of solar radiation, indoor polluted air is purified, and purification effect is achieved.
In the purification-ventilation mode, as shown in fig. 6, all the ventilation opening baffles are opened, that is, the first upper baffle 10, the second upper baffle 11, the first lower baffle 12 and the second lower baffle 13 are opened, the indoor air to be purified enters the air flow channel 4 from the lower baffle of the thermal storage wall 1 and is mixed with the outdoor fresh air flowing in from the ventilation opening at the lower part of the glass cover plate 5, under the action of solar radiation, the indoor polluted air in the air flow channel 4 and the photothermal catalytic coating 3 undergo a catalytic degradation reaction, and the purified air can flow into the room or flow out of the room through the upper baffle of the glass cover plate 5, so that the functions of purification and ventilation of the wall are realized.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. A preparation method of a photothermal synergistic catalyst is characterized by comprising the following steps:
(1) Adding manganese nitrate hexahydrate, potassium permanganate and ammonium ceric nitrate into deionized water, and uniformly stirring to obtain a mixed solution A;
(2) Dropwise adding an alkali solution into the mixed solution A to adjust the pH value to 10.5, stirring for 3-4 h to obtain a brown precipitate, aging for 1-3 h at 45-55 ℃, filtering, drying and grinding the obtained filter cake, and roasting the obtained powder for 5-7 h at 480-520 ℃ to obtain black MnOx-CeO 2 Powder, and then mixing the following materials in a mass ratio of 3-9: 1 MnOx-CeO 2 Powder with TiO 2 And mechanically mixing the powder to obtain the photo-thermal synergistic catalyst.
2. The preparation method according to claim 1, wherein in the step (1), the mass-to-volume ratio of the manganese nitrate hexahydrate, the potassium permanganate, the ammonium ceric nitrate and the deionized water is 1.72g:0.63g:5.48g: 90-110 mL.
3. Such as rightThe production method according to claim 1, wherein in the step (2), the MnOx-CeO 2 Powder with TiO 2 The mass ratio of the powder is 9:1; the alkali solution is 2moL/L potassium hydroxide solution; the drying is drying for 12 hours in a drying oven at 110 ℃.
4. A photothermal synergistic catalyst obtained by the production method according to any one of claims 1 to 3.
5. Use of the photothermal synergistic catalyst of claim 4 for degrading organic pollutants, including formaldehyde.
6. A solar energy based on photo-thermal catalysis purifies, ventilates and cools the compound wall structure, the structure sets up as the side wall between bottom plate and roof of every floor in the building, characterized by that, the structure includes the heat storage wall of the indoor direction side and glass cover plate of the outdoor direction side, form the air flow path between said heat storage wall, glass cover plate, have lower vents between said heat storage wall, glass cover plate and bottom plate, every lower vent has lower back plates, there are upper vents between said heat storage wall, glass cover plate and roof, every upper vent has upper back plates; in the direction towards the outside of the room, a heat collecting layer and a photo-thermal catalytic coating formed by coating the photo-thermal synergistic catalyst in the claim 5 are sequentially arranged on the heat storage wall body, a heat collecting water pipe is arranged in the heat collecting layer, the water inlet end of the heat collecting water pipe is butted with an indoor or outdoor water pipe, and the water outlet end of the heat collecting water pipe is connected into an indoor heat collecting water tank; the photo-thermal catalytic coating carries out photo-thermal concerted catalytic reaction under the irradiation of sunlight and degrades organic pollutants in the air flow channel.
7. The composite wall structure of claim 6, wherein the air channel has a thickness of 15-20 cm.
8. The solar purification, ventilation and cooling composite wall structure of claim 6, wherein the thickness of the photothermal catalytic coating is 2 μm to 50 μm.
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