CN114392653A - Spraying industry waste gas treatment method taking ozone catalytic function ceramic membrane as catalytic separation material - Google Patents
Spraying industry waste gas treatment method taking ozone catalytic function ceramic membrane as catalytic separation material Download PDFInfo
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- CN114392653A CN114392653A CN202111677639.XA CN202111677639A CN114392653A CN 114392653 A CN114392653 A CN 114392653A CN 202111677639 A CN202111677639 A CN 202111677639A CN 114392653 A CN114392653 A CN 114392653A
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- ozone
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- 239000012528 membrane Substances 0.000 title claims abstract description 121
- 239000000919 ceramic Substances 0.000 title claims abstract description 89
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 87
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000002912 waste gas Substances 0.000 title claims abstract description 62
- 238000000926 separation method Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000005507 spraying Methods 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title claims abstract description 21
- 238000011282 treatment Methods 0.000 title claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 32
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000013078 crystal Substances 0.000 claims abstract description 22
- 239000013207 UiO-66 Substances 0.000 claims abstract description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 41
- 239000007789 gas Substances 0.000 claims description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229910001882 dioxygen Inorganic materials 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- 239000008213 purified water Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 abstract description 5
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012855 volatile organic compound Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910007926 ZrCl Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000011866 long-term treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
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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
- B01D53/22—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 by diffusion
- B01D53/228—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 by diffusion characterised by specific membranes
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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
- B01D53/22—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 by diffusion
- B01D53/229—Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
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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
- B01D53/46—Removing components of defined structure
- B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
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- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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Abstract
The invention discloses a spraying industry waste gas treatment method taking an ozone catalytic function ceramic membrane as a catalytic separation material, which comprises the steps of preparing the ozone catalytic function ceramic membrane; the ozone catalytic function ceramic membrane is used as catalystThe separation material is used for treating waste gas in the spraying industry. The method for preparing the ozone catalytic function ceramic membrane comprises the following steps: pretreating a substrate ceramic membrane; preparing UiO-66 seed crystal; preparing a UiO-66 separation layer; finally preparing Co3O4And a catalytic layer. The invention can effectively separate two main components of benzene and pyridine in the waste gas of the spraying industry by using the ozone catalytic function ceramic membrane. Moreover, the substrate ceramic membrane and the catalytic layer provide high mechanical strength and high catalytic performance for the ozone catalytic function ceramic membrane, so that the ozone catalytic function ceramic membrane can be applied to the waste gas treatment process for a long time.
Description
Technical Field
The invention relates to the technical field of advanced oxidation treatment of waste gas, in particular to a spraying industry waste gas treatment method taking an ozone catalytic function ceramic membrane as a catalytic separation material.
Background
Volatile Organic Compounds (VOCs) generally refer to Volatile Organic Compounds having a boiling point below 250 ℃ at atmospheric pressure (101.325 kPa). Among the VOCs emitted by human activities, waste gas of VOCs generated in industrial processes is the most dominant source. And most VOCs discharged by industrial production are mixtures and often contain refractory and highly toxic components such as aromatic hydrocarbons, nitrogen/sulfur-containing compounds and the like. Besides strong toxicity and carcinogenicity, the VOCs can also cause the formation of secondary pollutants such as PM2.5 and the like after being discharged into the atmosphere, thereby causing serious threat to human health. Therefore, the pollution of VOCs discharged by industry is effectively remediated, and the pollution is related to the quality of the earth atmosphere and the health of all human beings.
The main components of the waste gas discharged by the spraying industry are benzene and pyridine. Among them, pyridine is a heterocyclic aromatic hydrocarbon containing N, and nitrogen oxides are generated under strong oxidation to be discharged into the atmosphere. Therefore, if the waste gas in the spraying industry is directly subjected to catalytic ozone oxidation treatment, a large amount of secondary pollution is generated. This indicates that the single gas phase oxidation technology can not clean the waste gas in the spraying industry. Therefore, if the pyridine component can be separated and collected while oxidizing the benzene component, the actual treatment process of the waste gas in the spraying industry can be cleaner and more efficient.
Disclosure of Invention
The invention aims to provide an ozone catalytic function ceramic membrane, which is used for separating and collecting pyridine components in the process of efficiently degrading waste gas in the spraying industry so as to clean and treat the waste gas in the spraying industry.
In order to achieve the aim, the application provides a spraying industry waste gas treatment method taking an ozone catalytic function ceramic membrane as a catalytic separation material, which comprises the steps of preparing the ozone catalytic function ceramic membrane; and treating the waste gas in the spraying industry by using the ozone catalytic function ceramic membrane as a catalytic separation material.
Further, the method for preparing the ozone catalytic function ceramic membrane comprises the following steps: pretreating a substrate ceramic membrane; preparing UiO-66 seed crystal; preparing a UiO-66 separation layer; finally preparing Co3O4And a catalytic layer.
Further, the method for pretreating the substrate ceramic membrane comprises the following steps: respectively ultrasonically cleaning the substrate ceramic membrane for multiple times by using deionized water and ethanol to remove impurities on the surface of the substrate ceramic membrane; and then placing the mixture into a muffle furnace, roasting the mixture for a period of time at a set temperature, naturally cooling the mixture, and placing the cooled mixture into a dryer for later use. The aperture of the used substrate ceramic membrane is about 0.1 μm.
Further, the method for preparing the UiO-66 seed crystal comprises the following steps: weighing ZrCl4And H2BDC, adding the BDC into DMF respectively, and carrying out ultrasonic treatment until the BDC is dissolved; then mixing the two solutions, and adding acetic acid to enable the concentration of the acetic acid in the solution to reach a set value; after fully and uniformly stirring, transferring the mixed solution into a high-pressure reaction kettle, and carrying out hydrothermal treatment at a set temperature for a period of time; after the reaction is finished, slowly cooling to room temperature, and obtaining white powder in the reaction kettle through centrifugation; the white powder was washed with DMF and ethanol, respectively, and finally dried under vacuum to obtain UiO-66 seed crystals.
Further, the method for preparing the UiO-66 separation layer comprises the following steps:
mixing the seed crystal powder with DMF at a ratio of 1:19, and continuously performing ultrasonic oscillation to fully disperse the seed crystal powder;
fixing the pretreated substrate ceramic membrane on a dipping-drawing machine, setting the lifting speed and the dipping time, and drying after finishing one-time drawing; then keeping the lifting speed unchanged, lifting for a few seconds again, and naturally drying at normal temperature; finally, calcining is carried out to increase the bonding force between the crystal seed layer and the supporting layer;
weighing ZrCl4And H2BDC, adding the BDC into DMF respectively, and carrying out ultrasonic treatment to completely dissolve the BDC; followed byThen mixing the two solutions, adding acetic acid and purified water into the two solutions, stirring the two solutions at room temperature, and transferring the mixture into a high-pressure reaction kettle; horizontally placing the substrate ceramic membrane loaded with the seed crystal layer at the bottom of the reaction kettle for synthesis; naturally cooling to room temperature after the reaction is finished, taking out the membrane, washing the membrane with DMF (dimethyl formamide), and washing with ethanol; finally, vacuum drying is carried out, and the mixture is taken out and placed in a dryer for standby.
Further, preparing Co3O4The method of the catalytic layer comprises the following steps:
preparation of Co (NO)3)3·6H2Slowly dripping the O solution into the citric acid solution under the condition of vigorous stirring, then stirring for a period of time, and cooling to room temperature for later use;
prepared Co (NO)3)3·6H2Uniformly dripping O gel liquid on the surface of the ceramic membrane loaded with the UiO-66 separation layer, setting the rotating speed and time of a spin coater, drying for multiple times after the time is up, sintering in a muffle furnace, cooling to room temperature, and placing in a dryer for later use.
Furthermore, the method for treating the waste gas in the spraying industry by using the ozone catalytic function ceramic membrane as a catalytic separation material comprises the following steps: and putting the ozone catalytic function ceramic membrane into a cylindrical membrane module, wherein the ozone catalytic function ceramic membrane comprises a catalytic layer, a separation layer and a substrate ceramic membrane which are sequentially arranged, the side coated with the catalytic layer is communicated with the gas inlet end of the membrane module, and the side coated with the substrate ceramic membrane is communicated with the gas outlet end of the membrane module.
Furthermore, the waste gas is provided by a waste gas source tank, passes through a waste gas pressure reducing valve and a waste gas flow controller and then enters the gas inlet end of the membrane component; meanwhile, after oxygen flowing out of the oxygen gas source tank passes through the oxygen pressure reducing valve and the oxygen flow controller, ozone gas which is oxidized into a certain concentration by the ozone generator enters the gas inlet end of the membrane component along with the waste gas; subsequently, the benzene component in the exhaust gas is trapped by the separation layer and degraded by ozone in the catalytic layer to produce CO2And H2And O and pyridine components penetrate through the ozone catalytic function ceramic membrane and are discharged from the gas outlet end of the membrane module.
Compared with the prior art, the technical scheme adopted by the invention has the advantages that: the invention can effectively separate two main components of benzene and pyridine in the waste gas of the spraying industry by using the ozone catalytic function ceramic membrane. Moreover, the substrate ceramic membrane and the catalytic layer provide high mechanical strength and high catalytic performance for the ozone catalytic function ceramic membrane, so that the ozone catalytic function ceramic membrane can be applied to the waste gas treatment process for a long time. Compared with the waste gas treatment technology in the spraying industry, the method can realize efficient separation treatment and catalytic ozonation on two main pollutants in the waste gas in the spraying industry, and is expected to become an ideal choice for the waste gas treatment technology in the spraying industry.
Drawings
FIG. 1 is a schematic diagram of a structure of a ceramic membrane with an ozone catalytic function;
FIG. 2 is a schematic diagram of the structure of a waste gas treatment device in the spraying industry;
the sequence numbers in the figures illustrate: 1, a waste gas source tank; 2, an oxygen source tank; 3 a waste gas pressure reducing valve; 4 an oxygen pressure reducing valve; 5 an exhaust gas flow controller; 6 an oxygen flow controller; 7 an ozone generator; 8, the gas inlet end of the membrane module; 9 a condensing unit; 10, gas outlet end of the membrane module; 11 a detector; 12 a catalytic layer; 13 separating the layers; 14 substrate ceramic membrane.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application 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 for purposes of illustration only and are not intended to limit the application, i.e., the embodiments described are only a subset of, and not all embodiments of the application. The components of the embodiments of the present application, generally described and illustrated in the figures herein, can be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present application, presented in the accompanying drawings, is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present application without making any creative effort, shall fall within the protection scope of the present application.
Example 1
The embodiment provides a spraying industry waste gas treatment method taking an ozone catalytic function ceramic membrane as a catalytic separation material, which comprises the following steps:
A. preparing an ozone catalytic function ceramic membrane;
B. and treating the waste gas in the spraying industry by using the ozone catalytic function ceramic membrane as a catalytic separation material.
Preferably, as shown in fig. 1, the method for preparing the ozone catalytic function ceramic membrane comprises the following steps:
(1) pretreatment of substrate ceramic membranes
The aperture of the ceramic membrane used as the substrate of the invention is about 0.1 μm. Before preparation, the substrate ceramic membrane is ultrasonically cleaned for a plurality of times (at least 3 times) by using deionized water and ethanol respectively so as to remove impurities on the surface of the substrate ceramic membrane. Then placing the mixture into a muffle furnace, roasting the mixture for 3.5 to 4 hours at the temperature of 580-600 ℃, naturally cooling the mixture, and placing the mixture into a dryer for standby.
(2) Preparation of UiO-66 seed crystals
About 0.149g of ZrCl can be weighed4And about 0.106g of H2BDC was added to 40-50mL of DMF separately and sonicated to dissolve. The two solutions are then combined and about 2.745mL of acetic acid may be added to bring the concentration of acetic acid in the solution to the set point (e.g., 1.2 mol/L). After fully and uniformly stirring, transferring the mixed solution into a high-pressure reaction kettle for hydrothermal treatment for 24-25h under the conditions of 100 ℃ and 120 ℃. After completion of the reaction, white powder in the reaction kettle was obtained by centrifugation while slowly cooling to room temperature. The white powder is washed for a plurality of times (at least 3 times) by DMF and ethanol respectively, and finally dried in vacuum at the temperature of 100 ℃ and 110 ℃ for 24-25h to obtain the UiO-66 seed crystal.
(3) Preparation of a UiO-66 separating layer
Preparation of liquid crystal
Mixing the seed crystal powder with DMF at a ratio of 1:19, and continuously performing ultrasonic oscillation for 1.5-2.5h to fully disperse the seed crystal powder.
Preparation of seed layer
And preparing the seed crystal layer by adopting a dipping-pulling method. Fixing the pretreated substrate ceramic membrane on a dipping-pulling machine, setting the lifting speed to be 1-3cm/s and the dipping time to be 10-12s, and drying for 3-4h under the conditions of 100-120 ℃ after finishing one time. And then keeping the lifting speed unchanged, lifting for 3-5s again, and naturally drying at normal temperature. Finally, calcining for 1.5-2h under the conditions of 200-230 ℃ to increase the bonding force between the seed crystal layer and the support layer.
Preparation of UiO-66 separation layer
About 0.121g of ZrCl can be weighed4And about 0.086g of H2BDC was added to 10mL DMF separately and sonicated for 20-25min to dissolve completely. Subsequently, the two solutions were mixed, to which 4.46mL of acetic acid and 9mg of purified water were added, stirred at room temperature for 30-40min, and then transferred to an autoclave. The substrate ceramic membrane loaded with the seed crystal layer is horizontally placed at the bottom of the reaction kettle, and the synthesis is carried out for 3-3.5h at the temperature of 100 ℃ and 120 ℃. After the reaction is finished, the membrane is naturally cooled to room temperature, taken out and washed with DMF for a plurality of times (at least 3 times), and then washed with ethanol for a plurality of times (at least 3 times). Finally vacuum drying at 20-25 deg.C for 24-25h, taking out and placing in a dryer for use.
(4) Preparation of Co3O4Catalytic layer
①Co(NO3)3·6H2Preparation of O-gel liquid
Co (NO) of about 0.5mol/L can be prepared3)3·6H2And slowly dripping the O solution into about 0.5mol/L citric acid solution under vigorous stirring, then stirring for 0.8-1h at the temperature of 60-80 ℃, and cooling to room temperature for later use.
②Co3O4Preparation of catalytic layer
Introducing a catalyst layer to the surface of the membrane by adopting a spin coating method: prepared Co (NO)3)3·6H2The O gel liquid is uniformly dripped on the surface of the ceramic membrane loaded with the UiO-66 separation layer, and the rotation speed of the spin coater is 4000-. Drying at 90-95 deg.C for 0.8-1 hr, and repeating for multiple times (at least 3 times). Finally, sintering the mixture for 2.8 to 3 hours in a muffle furnace at the temperature of 400 ℃ and 420 ℃, cooling the mixture to room temperature, and placing the mixture in a dryer for standby.
Preferably, the ozone catalytic function ceramic membrane is used as a catalytic separation material to treat waste gas in the spraying industry, and specifically comprises the following steps:
ceramics with ozone catalysis functionThe ceramic membrane is placed in a cylindrical membrane module, the ozone catalysis function ceramic membrane comprises a catalysis layer, a separation layer and a substrate ceramic membrane which are sequentially arranged, the side of the ceramic membrane coated with the catalysis layer is communicated with the gas inlet end 8 of the membrane module, and the side of the substrate ceramic membrane is communicated with the gas outlet end 11 of the membrane module. In the operation process of the device, waste gas is provided by a waste gas source tank 1, passes through a waste gas reducing valve 3 and a waste gas flow controller 5 and then enters a membrane component gas inlet end 8. Meanwhile, oxygen flowing out of the oxygen gas source tank 2 passes through the oxygen pressure reducing valve 4 and the oxygen flow controller 6, and is oxidized into ozone gas with a certain concentration by the ozone generator 7, and the ozone gas enters the inlet end 8 of the membrane component along with the waste gas. Subsequently, the benzene component in the exhaust gas is trapped by the separation layer and degraded by ozone in the catalytic layer to produce CO2And H2And O. The pyridine component can permeate the ozone catalytic function ceramic membrane and is discharged from the gas outlet end 11 of the membrane module for subsequent detection. The step is implemented in a spraying industry exhaust gas treatment device.
The waste gas treatment device in the spraying industry comprises a waste gas source tank, an oxygen source tank and a membrane module, wherein the waste gas source tank is connected to the gas inlet end of the membrane module through a waste gas conveying pipeline, and a waste gas pressure reducing valve, a waste gas flow controller and a valve are sequentially arranged on the waste gas conveying pipeline; the oxygen source tank is connected to the air inlet end of the membrane component through an oxygen conveying pipeline, and an oxygen pressure reducing valve, an oxygen flow controller and an ozone generator are sequentially arranged on the oxygen conveying pipeline; the gas outlet end of the membrane module is connected to a detector, and an ozone catalytic function ceramic membrane is placed in the membrane module.
The ozone catalytic function ceramic membrane comprises a catalytic layer, a separation layer and a substrate ceramic membrane which are sequentially arranged, wherein the catalytic layer is positioned at an air inlet end, and the substrate ceramic membrane is positioned at an air outlet end. The separation layer is a UiO-66 separation layer, the thickness is 500nm, and the roughness is between 250 and 300 nm; the catalyst layer is Co3O4A catalyst layer with the thickness more than or equal to 8mm and the roughness between 130 and 180 nm; the substrate ceramic membrane is flaky alpha-Al2O3The roughness of the ceramic film is between 120-180 nm.
The aperture of the separating layer of the ceramic membrane with the ozone catalysis function is
Between the molecular diameters of benzene and pyridine.
A valve is arranged in front of the gas inlet end of the membrane component, and the membrane component is connected with a condensing device through another valve.
The membrane module is cylindrical, and the ozone catalysis function ceramic membrane is fixed by bolts.
The concentration is 200mg/m by adopting the method3In the long-term treatment process of the waste gas in the spraying industry, the concentration of the introduced ozone is maintained to be 4g/m3The average removal rate of the benzene component of the ceramic membrane with the ozone catalysis function can reach 89 percent. The gas at the gas outlet end consists of pyridine and CO2And H2O, can be collected and processed by adopting a proper technology.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (8)
1. A spraying industry waste gas treatment method taking an ozone catalytic function ceramic membrane as a catalytic separation material is characterized by comprising the steps of preparing the ozone catalytic function ceramic membrane; and treating the waste gas in the spraying industry by using the ozone catalytic function ceramic membrane as a catalytic separation material.
2. The method for treating the waste gas in the spraying industry by taking the ozone catalytic function ceramic membrane as the catalytic separation material according to claim 1, wherein the method for preparing the ozone catalytic function ceramic membrane comprises the following steps: pretreating a substrate ceramic membrane; preparing UiO-66 seed crystal; preparing a UiO-66 separation layer; finally preparingCo3O4And a catalytic layer.
3. The spraying industry waste gas treatment method taking the ozone catalytic function ceramic membrane as the catalytic separation material according to claim 2, wherein the method for pretreating the substrate ceramic membrane comprises the following steps: respectively ultrasonically cleaning the substrate ceramic membrane for multiple times by using deionized water and ethanol to remove impurities on the surface of the substrate ceramic membrane; and then placing the mixture into a muffle furnace, roasting the mixture for a period of time at a set temperature, naturally cooling the mixture, and placing the cooled mixture into a dryer for later use.
4. The spraying industry waste gas treatment method taking the ozone catalytic function ceramic membrane as the catalytic separation material according to claim 2, wherein the method for preparing the UiO-66 crystal seeds comprises the following steps: weighing ZrCl4And H2BDC, adding the BDC into DMF respectively, and carrying out ultrasonic treatment until the BDC is dissolved; then mixing the two solutions, and adding acetic acid to enable the concentration of the acetic acid in the solution to reach a set value; after fully and uniformly stirring, transferring the mixed solution into a high-pressure reaction kettle, and carrying out hydrothermal treatment at a set temperature for a period of time; after the reaction is finished, slowly cooling to room temperature, and obtaining white powder in the reaction kettle through centrifugation; the white powder was washed with DMF and ethanol, respectively, and finally dried under vacuum to obtain UiO-66 seed crystals.
5. The spraying industry waste gas treatment method taking the ozone catalytic function ceramic membrane as the catalytic separation material according to claim 2, wherein the method for preparing the UiO-66 separation layer comprises the following steps:
mixing the seed crystal powder with DMF at a ratio of 1:19, and continuously performing ultrasonic oscillation to fully disperse the seed crystal powder;
fixing the pretreated substrate ceramic membrane on a dipping-drawing machine, setting the lifting speed and the dipping time, and drying after finishing one-time drawing; then keeping the lifting speed unchanged, lifting for a few seconds again, and naturally drying at normal temperature; finally, calcining is carried out to increase the bonding force between the crystal seed layer and the supporting layer;
weighing ZrCl4And H2BDC, adding into DMF, and ultrasonic treatingTreating to completely dissolve; then mixing the two solutions, adding acetic acid and purified water into the two solutions, stirring the two solutions at room temperature, and transferring the mixture into a high-pressure reaction kettle; horizontally placing the substrate ceramic membrane loaded with the seed crystal layer at the bottom of the reaction kettle for synthesis; naturally cooling to room temperature after the reaction is finished, taking out the membrane, washing the membrane with DMF (dimethyl formamide), and washing with ethanol; finally, vacuum drying is carried out, and the mixture is taken out and placed in a dryer for standby.
6. The method for treating waste gas in the spraying industry by using the ceramic membrane with the ozone catalysis function as the catalytic separation material according to claim 2, wherein Co is prepared3O4The method of the catalytic layer comprises the following steps:
preparation of Co (NO)3)3·6H2Slowly dripping the O solution into the citric acid solution under the condition of vigorous stirring, then stirring for a period of time, and cooling to room temperature for later use;
prepared Co (NO)3)3·6H2Uniformly dripping O gel liquid on the surface of the ceramic membrane loaded with the UiO-66 separation layer, setting the rotating speed and time of a spin coater, drying for multiple times after the time is up, sintering in a muffle furnace, cooling to room temperature, and placing in a dryer for later use.
7. The method for treating the waste gas in the spraying industry by using the ozone catalytic function ceramic membrane as the catalytic separation material according to claim 1, wherein the method for treating the waste gas in the spraying industry by using the ozone catalytic function ceramic membrane as the catalytic separation material comprises the following steps: and putting the ozone catalytic function ceramic membrane into a cylindrical membrane module, wherein the ozone catalytic function ceramic membrane comprises a catalytic layer, a separation layer and a substrate ceramic membrane which are sequentially arranged, the side coated with the catalytic layer is communicated with the gas inlet end of the membrane module, and the side coated with the substrate ceramic membrane is communicated with the gas outlet end of the membrane module.
8. The method for treating the waste gas in the spraying industry by using the ceramic membrane with the ozone catalytic function as the catalytic separation material as claimed in claim 7, wherein the waste gas is provided by a waste gas source tank and passes through a waste gas pressure reducing valve and a waste gas flow controller and then enters a spraying industryEntering the gas inlet end of the membrane component; meanwhile, after oxygen flowing out of the oxygen gas source tank passes through the oxygen pressure reducing valve and the oxygen flow controller, ozone gas which is oxidized into a certain concentration by the ozone generator enters the gas inlet end of the membrane component along with the waste gas; subsequently, the benzene component in the exhaust gas is trapped by the separation layer and degraded by ozone in the catalytic layer to produce CO2And H2And O and pyridine components penetrate through the ozone catalytic function ceramic membrane and are discharged from the gas outlet end of the membrane module.
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