CN114392653B - Waste gas treatment method for spraying industry by taking ozone catalytic functional ceramic membrane as catalytic separation material - Google Patents
Waste gas treatment method for spraying industry by taking ozone catalytic functional ceramic membrane as catalytic separation material Download PDFInfo
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Abstract
The invention discloses a waste gas treatment method in the spraying industry by taking an ozone catalytic functional ceramic membrane as a catalytic separation material, which comprises the steps of preparing the ozone catalytic functional ceramic membrane; and treating waste gas in the spraying industry by taking the ozone catalytic functional ceramic membrane as a catalytic separation material. The method for preparing the ozone catalytic function ceramic membrane comprises the following steps: firstly, pretreating a substrate ceramic film; preparing UiO-66 seed crystal; preparing a UiO-66 separation layer; finally preparing Co 3 O 4 A catalytic layer. The invention can effectively separate benzene and pyridine in waste gas in spraying industry by utilizing the ozone catalytic ceramic membrane. Moreover, the substrate ceramic membrane and the catalytic layer provide larger mechanical strength and better catalytic performance for the ozone catalytic functional ceramic membrane, so that the ozone catalytic functional 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 waste gas treatment method in the spraying industry, which takes an ozone catalytic functional ceramic membrane as a catalytic separation material.
Background
Volatile organic compounds (Volatile Organic Compounds, VOCs) are generally volatile organic compounds having a boiling point below 250℃at atmospheric pressure (101.325 kPa). Among the VOCs gas emitted by human activities, the VOCs off-gas generated in industrial processes is the most dominant source. And most VOCs discharged by industrial production are mixtures, and often contain undegraded and highly toxic components such as aromatic hydrocarbons, nitrogen/sulfur 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 global atmosphere quality and the health of all human beings are related.
The main components of the waste gas discharged by the spraying industry are benzene and pyridine. Wherein, pyridine is a heterocyclic aromatic hydrocarbon containing N, and nitrogen oxides are generated and discharged into the atmosphere under the strong oxidation. Therefore, if the waste gas in the spraying industry is directly subjected to catalytic ozonation treatment, a large amount of secondary pollution can be generated. This suggests that a single gas phase oxidation technique cannot clean the exhaust gas from the spray industry. Therefore, if the pyridine component can be separated and collected while the benzene oxide component is formed, 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 ceramic membrane, which can separate and collect 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 above purpose, the application provides a method for treating exhaust gas in spraying industry by taking an ozone catalytic functional ceramic membrane as a catalytic separation material, which comprises the steps of preparing the ozone catalytic functional ceramic membrane; and treating waste gas in the spraying industry by taking the ozone catalytic functional ceramic membrane as a catalytic separation material.
Further, the method for preparing the ozone catalytic function ceramic membrane comprises the following steps: firstly, pretreating a substrate ceramic film; preparing UiO-66 seed crystal; preparing a UiO-66 separation layer; finally preparing Co 3 O 4 A catalytic layer.
Further, the method for preprocessing the substrate ceramic membrane comprises the following steps: ultrasonically cleaning the substrate ceramic membrane with deionized water and ethanol for multiple times to remove impurities on the surface of the substrate ceramic membrane; then placing the mixture into a muffle furnace, roasting for a period of time at a set temperature, naturally cooling, and placing the mixture into a dryer for standby. The pore size of the base ceramic membrane used was about 0.1 μm.
Further, the method for preparing the UiO-66 seed crystal comprises the following steps: weighing ZrCl 4 And H 2 BDC is respectively added into DMF and is sonicated until dissolved; then mixing the two solutions, and adding acetic acid to enable the concentration of the acetic acid in the solutions 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 for a period of time at a set temperature; after the reaction is completed, slowly cooling to room temperature, and obtaining white powder in a reaction kettle by centrifugation; the white powder was washed with DMF and ethanol, respectively, and finally dried in vacuo to give UiO-66 seed crystals.
Further, the method for preparing the UiO-66 separation layer comprises the following steps:
mixing seed crystal powder with DMF in a ratio of 1:19, and continuously carrying out ultrasonic vibration to fully disperse the seed crystal powder;
fixing the pretreated substrate ceramic film on an impregnating-pulling machine, setting lifting speed and impregnating time, and drying after one-time pulling is finished; then, keeping the lifting speed unchanged, lifting for a few seconds again, and then naturally airing at normal temperature; finally calcining to increase the binding force between the seed crystal layer and the supporting layer;
weighing ZrCl 4 And H 2 BDC is respectively added into DMF, and is fully dissolved by ultrasonic treatment; then, mixing the two solutions, adding acetic acid and purified water into the mixture, stirring the mixture at room temperature, and transferring the mixture into a high-pressure reaction kettle; placing the substrate ceramic film loaded with the seed crystal layer on the bottom of the reaction kettle horizontally for synthesis; naturally cooling to room temperature after the reaction is finished, taking out the membrane, washing with DMF, and washing with ethanol; finally, vacuum drying is carried out, and the product is taken out and placed in a dryer for standby.
Further, co is prepared 3 O 4 The method of the catalytic layer comprises the following steps:
preparation of Co (NO) 3 ) 3 ·6H 2 Slowly dropwise adding the O solution into the citric acid solution under intense stirring, stirring for a period of time, and cooling to room temperature for standby;
co (NO) 3 ) 3 ·6H 2 O gel solution is uniformly dropped on the substrateSetting the rotating speed and time of a spin coater on the surface of a ceramic membrane loaded with a UiO-66 separation layer, drying for multiple times after the time is up, sintering in a muffle furnace, cooling to room temperature, and placing in a dryer for standby.
Furthermore, the ozone catalytic functional ceramic membrane is used as a catalytic separation material to treat waste gas in the spraying industry, and specifically comprises the following steps: the ozone catalytic functional ceramic membrane is placed in a cylindrical membrane assembly, and comprises a catalytic layer, a separation layer and a base ceramic membrane which are sequentially arranged, wherein the side coated with the catalytic layer is communicated with the air inlet end of the membrane assembly, and the side of the base ceramic membrane is communicated with the air outlet end of the membrane assembly.
Further, the waste gas is provided by a waste gas source tank, and enters the air inlet end of the membrane component after passing through a waste gas pressure reducing valve and a waste gas flow controller; meanwhile, after the oxygen flowing out of the oxygen source tank passes through the oxygen pressure reducing valve and the oxygen flow controller, the oxygen is oxidized into ozone gas with certain concentration by the ozone generator, and the ozone gas enters the air inlet end of the membrane component along with the waste gas; subsequently, benzene components in the exhaust gas are trapped by the separation layer and degraded by ozone in the catalytic layer to produce CO 2 And H is 2 O, pyridine components permeate the ozone catalytic functional ceramic membrane and are discharged from the gas outlet end of the membrane component.
Compared with the prior art, the technical scheme adopted by the invention has the advantages that: the invention can effectively separate benzene and pyridine in waste gas in spraying industry by utilizing the ozone catalytic ceramic membrane. Moreover, the substrate ceramic membrane and the catalytic layer provide larger mechanical strength and better catalytic performance for the ozone catalytic functional ceramic membrane, so that the ozone catalytic functional 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 high-efficiency separation treatment and catalytic ozone oxidation on two main pollutants in the waste gas in the spraying industry, and is expected to become an ideal choice of the waste gas treatment technology in the spraying industry.
Drawings
FIG. 1 is a schematic diagram of an ozone catalytic function ceramic membrane structure;
FIG. 2 is a schematic diagram of the construction of an exhaust treatment device in the spray industry;
the serial numbers in the figures illustrate: 1 an exhaust gas source tank; 2 an oxygen source tank; 3 an exhaust 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, an air inlet end of the membrane component; 9 condensing means; 10, an air outlet end of the membrane component; a detector 11; a catalytic layer 12; 13 separating layers; 14 a base ceramic membrane.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be further described in detail with reference to the accompanying drawings and examples. 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 merely some, but not all, of the embodiments of the application. The components of the embodiments of the present application, which are 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 application, as provided in the accompanying drawings, is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present application without making any inventive effort, are intended to be within the scope of the present application.
Example 1
The embodiment provides a method for treating waste gas in spraying industry by taking an ozone catalytic function ceramic membrane as a catalytic separation material, which comprises the following steps:
A. preparing an ozone catalytic ceramic membrane;
B. and treating waste gas in the spraying industry by taking the ozone catalytic functional ceramic membrane as a catalytic separation material.
Preferably, as shown in fig. 1, the ozone catalytic function ceramic membrane is prepared by the following steps:
(1) Pretreatment of substrate ceramic membranes
The pore size of the base ceramic membrane used in the present invention is about 0.1. Mu.m. Before preparation, the substrate ceramic membrane is ultrasonically cleaned with deionized water and ethanol for multiple times (at least 3 times) 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 to 600 ℃, naturally cooling the mixture, and placing the mixture into a dryer for standby.
(2) Preparation of UiO-66 seed crystals
ZrCl can be weighed about 0.149g 4 About 0.106g of H 2 BDC was added to 40-50mL DMF, respectively, and sonicated to dissolution. The two solutions are then mixed and about 2.745mL of acetic acid may be added to give the acetic acid concentration in the solution at the set point (e.g., 1.2 mol/L). After fully and uniformly stirring, transferring the mixed solution into a high-pressure reaction kettle, and carrying out hydrothermal treatment for 24-25h at the temperature of 100-120 ℃. After the reaction was completed, white powder in the reaction vessel was obtained by centrifugation at room temperature with slow cooling. The white powder was washed with DMF and ethanol, respectively, multiple times (at least 3 times) and finally dried under vacuum at 100-110℃for 24-25h to obtain UiO-66 seed crystals.
(3) Preparation of UiO-66 separation layer
(1) Preparation of seed solution
The seed powder was mixed with DMF in a ratio of 1:19 and continuously sonicated for 1.5-2.5h to allow for adequate dispersion.
(2) Preparation of seed layer
The seed layer is prepared using a dip-pull process. Fixing the pretreated substrate ceramic film on a dipping-pulling machine, setting the lifting speed to be 1-3cm/s, the dipping time to be 10-12s, and drying for 3-4h at 100-120 ℃ after one time. Then the lifting speed is kept unchanged, the lifting is carried out for 3 to 5 seconds again, and the natural air drying is carried out at normal temperature. Finally calcining for 1.5-2h at 200-230 ℃ to increase the binding force between the seed crystal layer and the supporting layer.
(3) Preparation of UiO-66 separation layer
About 0.121g of ZrCl can be weighed out 4 About 0.086g H 2 BDC was added to 10mL DMF 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 transferred into an autoclave. And (3) placing the substrate ceramic film loaded with the seed crystal layer on the bottom of the reaction kettle, and synthesizing for 3-3.5h at 100-120 ℃. Naturally cooling to room temperature after the reaction is finished, taking out the membrane, washing the membrane with DMF for multiple times (at least 3 times), and then using ethyl acetateAlcohol rinse multiple times (at least 3 times). Finally, vacuum drying is carried out for 24-25h at 20-25 ℃, and the dried product is taken out and placed in a dryer for standby.
(4) Preparation of Co 3 O 4 Catalytic layer
①Co(NO 3 ) 3 ·6H 2 Preparation of O-gel solution
Co (NO) may be formulated at about 0.5mol/L 3 ) 3 ·6H 2 The O solution is slowly added into about 0.5mol/L citric acid solution in a dropwise manner under vigorous stirring, then stirred for 0.8-1h at 60-80 ℃, and cooled to room temperature for standby.
②Co 3 O 4 Preparation of the catalytic layer
Introducing a catalytic layer to the surface of the membrane by adopting a spin coating method: co (NO) 3 ) 3 ·6H 2 O gel liquid is uniformly dropped on the surface of the ceramic membrane loaded with the UiO-66 separation layer, and the rotating speed of a spin coater can be set to 4000-5000rpm for 10-15s. Drying at 90-95deg.C for 0.8-1 hr, and repeating for several times (at least 3 times). Finally sintering for 2.8-3h in a muffle furnace at 400-420 ℃, cooling to room temperature, and placing in a dryer for standby.
Preferably, the ozone catalytic functional ceramic membrane is used as a catalytic separation material to treat waste gas in the spraying industry, and specifically comprises the following steps:
the ozone catalytic functional ceramic membrane is placed in a cylindrical membrane assembly, and comprises a catalytic layer, a separation layer and a base ceramic membrane which are sequentially arranged, wherein the side coated with the catalytic layer is communicated with an air inlet end 8 of the membrane assembly, and the side of the base ceramic membrane is communicated with an air outlet end 11 of the membrane assembly. During the operation of the device, the waste gas is provided by the waste gas source tank 1, and enters the air inlet end 8 of the membrane component after passing through the waste gas pressure reducing valve 3 and the waste gas flow controller 5. Meanwhile, the oxygen flowing out from the oxygen 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 then enters the air inlet end 8 of the membrane component along with the waste gas. Subsequently, benzene components in the exhaust gas are trapped by the separation layer and degraded by ozone in the catalytic layer to produce CO 2 And H is 2 O. Pyridine components can permeate through the ozone catalytic ceramic membrane and are discharged from the gas outlet end 11 of the membrane componentAnd (3) performing subsequent detection. This step is implemented in the spray industry exhaust gas treatment device.
The waste gas treatment device in the spraying industry comprises a waste gas source tank, an oxygen gas source tank and a membrane assembly, wherein the waste gas source tank is connected to the air inlet end of the membrane assembly 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 component is connected to the detector, and an ozone catalytic functional ceramic membrane is placed in the membrane component.
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 250-300 nm; the catalytic layer is Co 3 O 4 The thickness of the catalytic layer is more than or equal to 8mm, and the roughness is between 130 and 180 nm; the substrate ceramic film is flaky alpha-Al 2 O 3 Ceramic film with roughness of 120-180 nm.
The aperture of the separation layer of the ozone catalytic functional ceramic membrane isBetween benzene and pyridine molecular diameters.
The front of the air inlet end of the membrane component is provided with a valve, and the membrane component is connected with the condensing device through another valve.
The membrane component is cylindrical, and the ozone catalytic function ceramic membrane is fixed by bolts.
The method is adopted to obtain the concentration of 200mg/m 3 In the long-term treatment process of waste gas in the spraying industry, the concentration of the ozone introduced is maintained to be 4g/m 3 The removal rate of benzene components by the ozone catalytic ceramic membrane can reach 89% on average. The gas at the gas outlet end is composed of pyridine component and CO 2 H and H 2 O, which can be collected and processed by appropriate techniques.
The foregoing descriptions of specific exemplary embodiments of the present invention are 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 the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various 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 (3)
1. A method for treating waste gas in spraying industry by taking an ozone catalytic functional ceramic membrane as a catalytic separation material is characterized by comprising the steps of preparing the ozone catalytic functional ceramic membrane; benzene and pyridine in waste gas in spraying industry are treated by taking the ozone catalytic functional ceramic membrane as a catalytic separation material; the method for preparing the ozone catalytic function ceramic membrane comprises the following steps: firstly, pretreating a substrate ceramic film; preparing UiO-66 seed crystal; preparing a UiO-66 separation layer; finally preparing Co 3 O 4 A catalytic layer;
the method for preprocessing the substrate ceramic membrane comprises the following steps: ultrasonically cleaning the substrate ceramic membrane with deionized water and ethanol for multiple times to remove impurities on the surface of the substrate ceramic membrane; then placing the mixture into a muffle furnace, roasting for a period of time at a set temperature, naturally cooling, and placing the mixture into a dryer for standby;
the method for preparing the UiO-66 seed crystal comprises the following steps: weighing ZrCl 4 And H 2 BDC is respectively added into DMF and is sonicated until dissolved; then mixing the two solutions, and adding acetic acid to enable the concentration of the acetic acid in the solutions 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 for a period of time at a set temperature; after the reaction is completed, slowly cooling to room temperature, and obtaining white powder in a reaction kettle by centrifugation; respectively cleaning the white powder by using DMF and ethanol, and finally vacuum drying to obtain UiO-66 seed crystals;
the preparation method of the UiO-66 separation layer comprises the following steps:
mixing seed crystal powder with DMF in a ratio of 1:19, and continuously carrying out ultrasonic vibration to fully disperse the seed crystal powder;
fixing the pretreated substrate ceramic film on an impregnating-pulling machine, setting lifting speed and impregnating time, and drying after one-time pulling is finished; then, keeping the lifting speed unchanged, lifting for a few seconds again, and then naturally airing at normal temperature; finally calcining to increase the binding force between the seed crystal layer and the supporting layer;
weighing ZrCl 4 And H 2 BDC is respectively added into DMF, and is fully dissolved by ultrasonic treatment; then, mixing the two solutions, adding acetic acid and purified water into the mixture, stirring the mixture at room temperature, and transferring the mixture into a high-pressure reaction kettle; placing the substrate ceramic film loaded with the seed crystal layer on the bottom of the reaction kettle horizontally for synthesis; naturally cooling to room temperature after the reaction is finished, taking out the membrane, washing with DMF, and washing with ethanol; finally, vacuum drying, taking out and placing in a dryer for standby;
preparation of Co 3 O 4 The method of the catalytic layer comprises the following steps:
preparation of Co (NO) 3 ) 3 ·6H 2 Slowly dropwise adding the O solution into the citric acid solution under intense stirring, stirring for a period of time, and cooling to room temperature for standby;
co (NO) 3 ) 3 ·6H 2 O gel liquid is evenly dripped on the surface of a ceramic membrane loaded with a UiO-66 separation layer, the rotating speed and the time of a spin coater are set, drying is carried out for a plurality of times after the time is up, then the mixture is sintered in a muffle furnace, and finally the mixture is cooled to room temperature and then is placed in a dryer for standby.
2. The method for treating waste gas in the spraying industry by taking the ozone catalytic functional ceramic membrane as a catalytic separation material according to claim 1, which is characterized by comprising the following steps of: the ozone catalytic functional ceramic membrane is placed in a cylindrical membrane assembly, and comprises a catalytic layer, a separation layer and a base ceramic membrane which are sequentially arranged, wherein the side coated with the catalytic layer is communicated with the air inlet end of the membrane assembly, and the side of the base ceramic membrane is communicated with the air outlet end of the membrane assembly.
3. The method for treating waste gas in spraying industry by taking an ozone catalytic ceramic membrane as a catalytic separation material according to claim 2, wherein the waste gas is provided by a waste gas source tank, and enters an air inlet end of a membrane assembly after passing through a waste gas pressure reducing valve and a waste gas flow controller; meanwhile, after the oxygen flowing out of the oxygen source tank passes through the oxygen pressure reducing valve and the oxygen flow controller, the oxygen is oxidized into ozone gas with certain concentration by the ozone generator, and the ozone gas enters the air inlet end of the membrane component along with the waste gas; subsequently, benzene components in the exhaust gas are trapped by the separation layer and degraded by ozone in the catalytic layer to produce CO 2 And H is 2 O, pyridine components permeate the ozone catalytic functional ceramic membrane and are discharged from the gas outlet end of the membrane component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111677639.XA CN114392653B (en) | 2021-12-31 | 2021-12-31 | Waste gas treatment method for spraying industry by taking ozone catalytic functional ceramic membrane as catalytic separation material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111677639.XA CN114392653B (en) | 2021-12-31 | 2021-12-31 | Waste gas treatment method for spraying industry by taking ozone catalytic functional ceramic membrane as catalytic separation material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114392653A CN114392653A (en) | 2022-04-26 |
| CN114392653B true CN114392653B (en) | 2024-01-12 |
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| US20180043656A1 (en) * | 2017-09-18 | 2018-02-15 | LiSo Plastics, L.L.C. | Oriented Multilayer Porous Film |
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