CN113176350B - Microwave-ultraviolet combined VOCs waste gas catalytic combustion evaluation device - Google Patents
Microwave-ultraviolet combined VOCs waste gas catalytic combustion evaluation device Download PDFInfo
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- CN113176350B CN113176350B CN202110331948.5A CN202110331948A CN113176350B CN 113176350 B CN113176350 B CN 113176350B CN 202110331948 A CN202110331948 A CN 202110331948A CN 113176350 B CN113176350 B CN 113176350B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/74—Optical detectors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Physics & Mathematics (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a microwave-ultraviolet combined VOCs waste gas catalytic combustion evaluation device, which belongs to the technical field of volatile organic pollutant treatment and comprises a microwave-UV combined catalytic combustion assembly, wherein VOCs waste gas is introduced into an inner cavity of a vent pipe; the inner cavity of the microwave-UV combined catalytic combustion component is provided with a photocatalyst, and the gas outlet pipe of the microwave-UV combined catalytic combustion component is connected with a gas chromatograph. The microwave and the ultraviolet radiation inside the shell of the microwave-UV combined catalytic combustion assembly can break molecular bonds of volatile organic matters in the waste gas, and macromolecular organic matters are converted into micromolecular organic matters, so that the volatile organic matters can be combusted under the action of a photocatalyst; and finally, detecting the type of the exhaust gas through a gas chromatograph and verifying the catalytic combustion treatment effect. The invention utilizes ultraviolet rays and microwaves to radiate the internal waste gas for digestion treatment, completes the catalytic combustion of the waste gas, and can lead the decomposition of organic matters in the waste gas and the treatment of VOCs to be more thorough.
Description
Technical Field
The invention belongs to the technical field of volatile organic pollutant treatment, and particularly relates to a microwave-ultraviolet combined VOCs waste gas catalytic combustion evaluation device.
Background
In the production process of the chemical industry, organic waste gas mainly containing organic components such as benzene, cyclohexane and xylene is discharged; in the process of oil exploitation, oil field associated gas mainly containing methane and low-carbon chain hydrocarbon is discharged; in the coal seam mining process, methane-based gas is discharged. At present, 3 types of domestic waste gas treatment modes in China mainly comprise sanitary landfill, composting and incineration, and the landfill mode has the defects of large land resource occupation and consumption, dialysis liquid pollution, atmosphere pollution by landfill gas and the like. The composting mode has the defects of low separation efficiency, high content of biodegradable organic matters in waste gas which is more than 40 percent, poor fertilizer quality and the like. Catalytic combustion is increasingly widely used as an effective volume-reduction and weight-reduction waste gas treatment means.
However, the existing catalytic combustion exhaust gas has the problems of uneven heating, too slow heating, low heating efficiency and the like, and the exhaust gas treatment amount and treatment effect are influenced.
Disclosure of Invention
The invention aims to solve the technical problems of the prior art, and provides a microwave-ultraviolet combined VOCs waste gas catalytic combustion evaluation device, which solves the problems of uneven heating, too slow heating, low heating efficiency and the like, can effectively control the temperature of a shell, can enable the activity of a catalyst to reach the optimal degree, and can effectively accelerate the reaction process of catalytic combustion and the effect of treating VOCs.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a microwave-ultraviolet combined VOCs waste gas catalytic combustion evaluation device comprises a microwave-UV combined catalytic combustion assembly, wherein the microwave-UV combined catalytic combustion assembly is communicated with a vent pipe and is used for introducing VOCs waste gas into an inner cavity of the microwave-UV combined catalytic combustion assembly; the inner cavity of the shell of the microwave-UV combined catalytic combustion assembly is provided with a photocatalyst capable of contacting with VOCs waste gas, and the inner cavity of the shell of the microwave-UV combined catalytic combustion assembly can radiate ultraviolet rays and microwaves for digesting the waste gas; an air outlet pipe of the microwave-UV combined catalytic combustion assembly is connected with a gas chromatograph, and the type of the exhaust gas is detected and the catalytic combustion treatment effect is verified through the gas chromatograph.
Preferably, the microwave-UV combined catalytic combustion assembly comprises a shell, an electrodeless ultraviolet lamp tube arranged on the side wall of the shell, and a waveguide, wherein the waveguide is connected with a magnetron and is used for radiating microwaves into the shell; the two ends of the electrodeless ultraviolet lamp tube are arranged on the side wall of the shell, and the tube body of the electrodeless ultraviolet lamp tube is arranged in the shell and used for radiating ultraviolet light to the inner cavity of the shell; and the side wall of the shell is also provided with an ultraviolet intensity detector, a thermodetector and a pressure sensor, and the ultraviolet intensity detector, the thermodetector and the pressure sensor are used for controlling the temperature in the shell within the activity range of the photocatalyst.
Preferably, a thermocouple connected with a temperature controller is further arranged on the side wall of the shell, and a measuring end of the thermocouple extends to the inner cavity of the shell and is used for monitoring the temperature inside the shell.
Preferably, the inner cavity of the shell is provided with guide pipes which are arranged up and down, and the top and the bottom of each guide pipe are respectively communicated with the vent pipe and the air outlet pipe at the upper side wall and the lower side wall of the shell; the middle part of the guide pipe is disconnected to form a waste gas combustion area; the photocatalyst is arranged in the middle of the waste gas combustion area; the waveguide opening, the electrodeless ultraviolet lamp tube and the thermocouple are all arranged on the side face of the waste gas combustion area; still be equipped with small-size camera on the lateral wall of casing for observe the inside photocatalyst behavior of casing.
Preferably, the waste gas pipe communicated with the VOCs waste gas and the air pipe communicated with the air are connected with the air inlet pipe through a three-way valve, and the air inlet pipe, the vent pipe and the air outlet pipe are connected with the gas chromatograph through a four-way valve.
Preferably, the waste gas pipe and the air pipe are both provided with a gas mass flow meter for controlling the mixing ratio of the VOCs waste gas and the air to be 1:2.
Preferably, the number of the electrodeless ultraviolet lamp tubes is four, and the electrodeless ultraviolet lamp tubes are transversely arranged on the left side and the right side of the photocatalyst in a front-back mode; the two waveguides are arranged on the left side and the right side of the shell in a staggered mode, and the waveguides are arranged on the outer side of the electrodeless ultraviolet lamp tube; the thermocouple is arranged between the two electrodeless ultraviolet lamp tubes on the same side; the temperature measuring instrument is arranged in front of the side wall of the shell, and the ultraviolet intensity detecting instrument is arranged on the side wall of the shell.
Preferably, the photocatalyst is a supported Co3O4-TiO2 photocatalyst.
Preferably, the microwave-UV combined catalytic combustion assembly is arranged in the box body, a door is arranged on the front side of the microwave-UV combined catalytic combustion assembly, and the vent pipe is fixed on the inner wall of the box body through a support; the waste gas pipe, the air pipe, the three-way valve, the gas mass flowmeter and the temperature controller are all arranged in the box body and are arranged on one side of the microwave-UV combined catalytic combustion assembly.
Preferably, a plurality of layers of partition plates are arranged on one side of the door, and the waste gas pipe, the air pipe, the gas mass flow meter and the temperature controller are respectively arranged on different partition plates; the three-way valve and the four-way valve are arranged on the side plate at the front part of the partition plate.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in: compared with the prior art, the microwave-UV combined catalytic combustion assembly adopts microwave excitation to start the electrodeless ultraviolet lamp tube; a photocatalyst is placed in an inner cavity of the microwave-UV combined catalytic combustion assembly, molecular bonds of volatile organic matters in the waste gas are broken by means of microwave and ultraviolet radiation, and macromolecular organic matters are converted into micromolecular organic matters, so that the waste gas can be combusted; and finally, detecting the type of the exhaust gas through a gas chromatograph and verifying the catalytic combustion treatment effect. The invention utilizes ultraviolet and microwave radiation to carry out digestion treatment on internal waste gas, completes catalytic combustion of the waste gas by heating, and leads the decomposition of organic matters in the waste gas to be more thorough and the treatment of VOCs to be more thorough. The invention can provide data support for industrial waste gas treatment.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Fig. 1 is a schematic structural diagram of a microwave-ultraviolet combined catalytic combustion evaluation device for VOCs exhaust gas according to an embodiment of the present invention.
Fig. 2 is a top view of a microwave-ultraviolet combined catalytic combustion evaluation apparatus for VOCs exhaust gas according to an embodiment of the present invention.
Fig. 3 is an external structural view of a catalytic combustion assembly in the microwave-ultraviolet combined catalytic combustion evaluation device for VOCs exhaust gas according to the embodiment of the present invention.
Fig. 4 is a spatial layout view of the internal structure of the catalytic combustion assembly of fig. 3.
FIG. 5 is a process diagram of the present invention.
Reference numerals: 1. a housing; 2. a breather pipe; 3. a magnetron; 4. a waveguide; 5. an electrodeless ultraviolet lamp tube; 6. a thermocouple; 7. a temperature measuring instrument; 8. a small-sized camera; 9. a photocatalyst; 10. a microwave-UV combined catalytic combustion component;
11. a box body; 12. a support; 13. a gas mass flow meter; 14. a three-way valve; 15. a four-way valve;
16. a flow controller; 17. a temperature controller; 18. a conduit; 19. an air outlet pipe; 20. an exhaust gas pipe; 21. an air tube; 22. a gas chromatograph; 23. opening the door; 24-an air inlet pipe; 25-an insulating layer; 26-ultraviolet intensity detector.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in fig. 1-3, a microwave-ultraviolet combined catalytic combustion evaluation device for VOCs waste gas comprises a microwave-UV combined catalytic combustion assembly 10, wherein the microwave-UV combined catalytic combustion assembly 10 is communicated with a breather pipe 2 and is used for introducing VOCs waste gas into an inner cavity of a shell 1 of the microwave-UV combined catalytic combustion assembly 10; the inner cavity of the shell 1 of the microwave-UV combined catalytic combustion assembly 10 is provided with a photocatalyst 9 capable of contacting with VOCs waste gas, and the inner cavity of the shell 1 of the microwave-UV combined catalytic combustion assembly 10 can radiate ultraviolet rays and microwaves for digesting the waste gas; the gas outlet pipe 19 of the microwave-UV combined catalytic combustion assembly 10 is connected with a gas chromatograph 22, and the type of the exhaust gas is detected and the catalytic combustion treatment effect is verified through the gas chromatograph.
In one embodiment of the present invention, as shown in fig. 3 and 4, the microwave-UV combination catalytic combustion assembly 10 includes a housing 1, an electrodeless ultraviolet lamp tube 5 disposed on a side wall of the housing 1, and a waveguide 4, wherein the waveguide 4 is connected to a magnetron 3 and is configured to radiate microwaves into the housing 1; two ends of the electrodeless ultraviolet lamp tube 5 are arranged on the side wall of the shell 1, and a tube body of the electrodeless ultraviolet lamp tube 5 is arranged in the shell 1 and used for radiating ultraviolet light to an inner cavity of the shell 1; an ultraviolet intensity detector 26, a temperature detector 7 and a pressure sensor (not shown in the figure) are further arranged on the side wall of the shell 1, the ultraviolet intensity detector 26 is used for ensuring that the wavelength of ultraviolet rays emitted by the electrodeless ultraviolet lamp tube 5 is 185nm, the internal temperature of the shell 1 is controlled within the optimum activity range of the photocatalyst 9, and the pressure in the shell is controlled within a safety range. The process principle of this scheme is shown in figure 5.
During specific manufacturing, the thermometer is an infrared thermometer. The microwave heating mode is adopted to replace the traditional electric heating mode, so that the heating rate can be greatly increased, and the utilization rate of energy is improved. Meanwhile, the microwave can break molecular bonds of some volatile organic compounds, and macromolecular organic compounds are converted into micromolecular organic compounds, so that the combustion treatment of the micromolecular organic compounds is facilitated.
Further optimizing the technical scheme, as shown in fig. 3, a thermocouple 6 connected with a temperature controller 17 is further arranged on the side wall of the shell 1, and a measuring end of the thermocouple 6 extends to the inner cavity of the shell 1 for monitoring the internal temperature of the shell 1.
In one embodiment of the present invention, as shown in fig. 3 and 4, the inner cavity of the housing 1 is provided with a guide tube 18 arranged up and down, and the top and bottom of the guide tube 18 are respectively communicated with the vent tube 2 and the air outlet tube 19 at the upper and lower side walls of the housing 1; the middle part of the conduit 18 is broken to form a waste gas combustion area; the photocatalyst 9 is arranged in the middle of the waste gas combustion area; the opening of the waveguide 4, the electrodeless ultraviolet lamp tube 5 and the thermocouple 6 are all arranged on the side surface of the waste gas combustion area; still be equipped with small-size camera 8 on the lateral wall of casing 1 for observe the inside photocatalyst behavior of casing 1.
The scheme is further optimized, and the heat-insulating layer 25 is wrapped outside the guide pipe 18, so that the temperature required by catalytic combustion of waste gas can be effectively ensured; the small camera 8 is made of a temperature-resistant material; and an exhaust pipe is arranged on the side surface of the shell. The heat-insulating layer 25 can be a silicone oil heat-insulating layer, and can protect the conduit while ensuring the penetration of the microwave by virtue of the characteristics of good wave-transmitting property and poor wave-absorbing property of the silicone oil. Because ultraviolet light (UV light) with the wavelength of 185nm can react with oxygen in the air to generate ozone while digesting the organic waste gas, the ozone is retained in the cavity of the shell, the internal pressure of the shell can be increased, the pressure sensor can react the change of the pressure to a receiver (not shown in the figure), the receiver receives a signal of the pressure sensor and then controls a seal in the exhaust pipe to open, and meanwhile, an exhaust fan (not shown in the figure) is opened, so that the gas generated in the shell is timely discharged, and the internal pressure is reduced. By adopting the structure, the waste gas can flow through the inner cavity of the shell from top to bottom along the guide pipe, and the flowing waste gas can overcome the defects of small penetration depth and uneven heating of the microwave to a great extent.
In addition, in order to effectively utilize the ozone generated in the organic waste gas digestion process, an ozone oxidation chamber can be arranged at the junction of the air inlet pipe 24 and the guide pipe 18, the ozone generated in the ozone oxidation chamber is returned to the ozone oxidation chamber by a return pipe communicated with the shell, the organic waste gas conveyed by the air inlet pipe can be subjected to oxidation pretreatment, and the treatment effect of the organic waste gas is further improved.
In order to facilitate online monitoring of the concentration of VOCs in the exhaust gas entering the microwave-UV combined catalytic combustion assembly 10, the exhaust gas pipe 20 through which the VOCs exhaust gas is introduced and the air pipe 21 through which air is introduced are connected to the intake pipe 24 through the three-way valve 14, and the intake pipe 24, the vent pipe 2, and the outlet pipe 19 are connected to the gas chromatograph 22 through the four-way valve 14. Meanwhile, a gas mass flow meter 13 is attached to both the exhaust gas pipe 20 and the air pipe 21, and the mixing ratio of the VOCs exhaust gas and air is controlled to be 1:2. The waste gas pipe 20 and the air pipe 21 are both connected with the flow controller 16, and the two mass flow meters are controlled through the flow controller 16, so that the flow of VOCs (volatile organic compounds) in the waste gas pipe 20 and the flow of air in the air pipe 21 are respectively controlled, the VOCs waste gas is diluted and pretreated, and the concentration of waste gas entering the microwave-UV combined catalytic combustion assembly 10 can be controlled.
In one embodiment of the present invention, as shown in fig. 3 and 4, four electrodeless ultraviolet lamp tubes 5 are arranged laterally at the left and right sides of the photocatalyst 9; the two waveguides 4 are arranged on the left side and the right side of the shell 1 in a staggered manner, and the waveguides 4 are arranged on the outer side of the electrodeless ultraviolet lamp tube 5; the thermocouple 6 is arranged between the two electrodeless ultraviolet lamp tubes 5 on the same side; the temperature measuring instrument 7 is arranged in front of the side wall of the shell 1, and the ultraviolet intensity detector 26 is arranged on the side wall of the shell 1. In this embodiment, the power duty of the magnetron is 1KW. When the magnetron in the cavity of the shell is electrified, the magnetron starts working and radiates microwaves. The electrodeless ultraviolet lamp tube is excited to work under the action of microwaves to emit UV light, the UV light has a strong digestion effect on VOCs, the VOCs are subjected to the digestion effect of the UV light during catalytic oxidation, the VOCs can be decomposed more thoroughly, and the VOCs are treated more thoroughly.
In specific implementation, the photocatalyst is a supported Co3O4-TiO2 photocatalyst, and the preparation method comprises the following steps:
（1）TiO 2 preparation: tetrabutyl titanate and ammonia water are mixed according to the weight ratio of 8-10:1-3, the mass volume ratio is g/ml, the unit of the mass volume ratio is g/ml, and the mixture is heated in water bath until TiO is generated 2 A crystal grain; sterilizing the above mixture in a Teflon sterilizing container, drying at 100-130 deg.C to constant weight after sterilization, washing with deionized water, drying at 100-105 deg.C for 9-12 hr, and heat treating in a muffle furnace at 400-450 deg.C for 2-4 hr. Wherein the concentration of tetrabutyl titanate is 2.85mol/L, and the concentration of ammonia water is 9.52-11.11mol/L.
（2）Co 3 O 4 Preparation: slowly adding 10mM cobalt nitrate solution into 12mM sodium carbonate solution, magnetically stirring for 40-60min, centrifuging, alternately washing with deionized water and anhydrous ethanol, drying, and calcining at 400-450 deg.C in muffle furnace for 2-4 hr. Wherein the volume ratio of the cobalt nitrate solution to the sodium carbonate solution is 1:1-2.
(3) Adding TiO into the mixture 2 And Co 3 O 4 Mixing into paste, and coating onto Ni net to obtain supported Co 3 O 4 -TiO 2 A catalyst. Wherein, tiO 2 And Co 3 O 4 The mass ratio of (A) to (B) is 2-4:1-3.
The following are three specific examples:
example 1: (1) TiO2 2 Preparation: tetrabutyl titanate and ammonia water were mixed according to a ratio of 8:1, and heating in a water bath until the crystallization is complete. Hydrolysis product of tetrabutyl titanate in an aqueous ammonia system Ti (OH) 4 With the rising of the reaction temperature, the titanium oxide is dehydrated and condensed into titanic acid aggregate, the obtained aggregate generates growth elements, and with the change of the concentration, the growth elements are nucleated under the supersaturation environment, namely, the hydrothermal reaction generates TiO under the water bath heating environment 2 。
Wherein the concentration of tetrabutyl titanate is 2.85mol/L, and the concentration of ammonia water is 9.52mol/L.
Transferring the mixture into a Teflon sterilization container for sterilization, drying at 100 ℃ to constant weight after sterilization, then washing with deionized water, drying at 100 ℃ for 9h, and placing into a muffle furnace for heat treatment at 400 ℃ for 3h.
（2）Co 3 O 4 Preparation: slowly adding a 10mM cobalt nitrate solution into a 12mM sodium carbonate solution, magnetically stirring for about 50min, alternately washing with deionized water and absolute ethyl alcohol, drying, and calcining at 400 ℃ in a muffle furnace for 2h;
wherein the volume ratio of the cobalt nitrate solution to the sodium carbonate solution is 1:1.
(3) Adding TiO into the mixture 2 And Co 3 O 4 Mixing into paste, and coating onto Ni net to obtain supported Co 3 O 4 -TiO 2 A catalyst. Wherein, tiO 2 And Co 3 O 4 Is 2:1.
Example 2:
（1）TiO 2 preparation: tetrabutyl titanate and ammonia water are mixed according to the weight ratio of 9:2, stirring the mixture, wherein the unit of the mass-volume ratio is g/ml, and heating the mixture in a water bath until the crystallization is complete.
Wherein the concentration of tetrabutyl titanate is 2.85mol/L, and the concentration of ammonia water is 10mol/L.
Transferring the mixture into a Teflon sterilization container for sterilization, drying at 120 ℃ to constant weight after sterilization, washing with deionized water, drying at 103 ℃ for 11h, and placing into a muffle furnace for heat treatment at 450 ℃ for 2h.
（2）Co 3 O 4 Preparation: slowly adding a cobalt nitrate solution with the concentration of 10mM into a sodium carbonate solution with the concentration of 12mM, magnetically stirring for about 40min, alternately washing with deionized water and absolute ethyl alcohol, drying, and calcining for 3h at 430 ℃ in a muffle furnace;
wherein the volume ratio of the cobalt nitrate solution to the sodium carbonate solution is 1:2.
(3) Adding TiO into the mixture 2 And Co 3 O 4 Mixing into paste, and coating onto Ni net to obtain supported Co 3 O 4 -TiO 2 A catalyst. Wherein, tiO 2 And Co 3 O 4 3:2.
Example 3:
（1）TiO 2 preparation: tetrabutyl titanate and ammonia water were mixed according to a ratio of 10:3, stirring and mixing the materials in the mass-volume ratio of g/ml, and heating the mixture in a water bath until the crystallization is complete.
Wherein the concentration of tetrabutyl titanate is 2.85mol/L, and the concentration of ammonia water is 11.11mol/L.
Transferring the mixture into a Teflon sterilization container for sterilization, drying at 130 ℃ to constant weight after sterilization, then washing with deionized water, drying at 105 ℃ for 12h, and placing in a muffle furnace for heat treatment at 430 ℃ for 4h.
（2）Co 3 O 4 Preparation: slowly adding a cobalt nitrate solution with the concentration of 10mM into a sodium carbonate solution with the concentration of 12mM, magnetically stirring for about 60min, alternately washing with deionized water and absolute ethyl alcohol, drying, and calcining for 4h at 450 ℃ in a muffle furnace;
wherein the volume ratio of the cobalt nitrate solution to the sodium carbonate solution is 1:1.
(3) Adding TiO into the mixture 2 And Co 3 O 4 Mixing into paste, and coating onto Ni net to obtain supported Co 3 O 4 -TiO 2 A catalyst. Wherein, tiO 2 And Co 3 O 4 Is 4:3.
Wherein,the Ni net is woven by metal Ni into a net shape, and has good wave-absorbing performance. Mixing TiO with 2 And Co 3 O 4 Mixing with terpineol to obtain uniform paste, and coating on Ni net with thin brush pen, tiO 2 And Co 3 O 4 The proportion of (c) is adjusted according to the catalytic reaction.
In view of TiO 2 The surface is modified by semiconductor metal oxide, and when the surface is compounded with a semiconductor with small forbidden bandwidth and high conduction band position, photo-generated electrons can be quickly injected into TiO 2 The conduction band is beneficial to the separation and transfer of photo-generated electrons and holes, and the quantum efficiency is improved. And in the semiconductive metal oxide, co 3 O 4 Is in a mixed oxidation state of a spinel cubic structure, has better sensitivity to electromagnetic waves such as microwave and the like, is a good composite material, and simultaneously, in the photocatalysis process, co 3 O 4 Has a narrow band gap of 2.1 eV and excellent oxidation ability, and can be separated and transported from TiO by charge 2 The doped catalyst is formed, and the photocatalytic activity is improved.
The supported Co3O4-TiO2 photocatalyst passes through Co 3 O 4 With TiO 2 Doping can improve single TiO 2 The catalyst has sensitivity to Ultraviolet (UV) and Microwave (MW), can obtain a large amount of electromagnetically active oxidation groups in a microwave electromagnetic field, can generate a hotspot effect under the radiation of electromagnetic waves, has the actual temperature of a hotspot on the surface of the catalyst far higher than the apparent temperature, and has great promotion effect on catalytic reaction; simultaneously, ultraviolet light energy excited by microwave plasma enables the surface of the catalyst to generate electron-hole pairs, and the electron-hole pairs react with oxygen and water in the air to generate OH and HO 2 And isostrong oxidizing free radicals are adopted, so that organic matters (VOCs) are effectively converted into inorganic mineralized molecules, and the VOCs are thoroughly degraded. The supported Co3O4-TiO2 photocatalyst has excellent sensitivity to microwave and ultraviolet light, has higher catalytic efficiency in a microwave-ultraviolet field, and is more favorable for degrading organic pollutants.
In an embodiment of the present invention, as shown in fig. 1 and 2, the microwave-UV combination catalytic combustion assembly 10 is disposed in the box body 11, the front side of the microwave-UV combination catalytic combustion assembly 10 is provided with a door 23, and the vent pipe is fixed on the inner wall of the box body 11 through a bracket 12; the waste gas pipe 10, the air pipe 11, the three-way valve 14, the gas mass flow meter 13, the flow controller 16 and the temperature controller 17 are all arranged in the box body 11 and are arranged on one side of the microwave-UV combined catalytic combustion assembly 10. Adopt this structure can integrate each part in the box, overall structure is compacter, avoids the pipeline winding to lead to the scene chaotic.
In order to fully utilize the internal space of the box body, when in specific manufacture, a plurality of layers of partition plates are arranged on one side of the door, and the waste gas pipe 20, the air pipe 21, the gas mass flowmeter 13, the flow controller 16 and the temperature controller 17 are respectively arranged on different partition plates; the waste gas pipe 20 and the air pipe 21 are connected with an air inlet pipe 24 through a three-way valve 14, and the air inlet pipe 24, the vent pipe 2 and the air outlet pipe 19 are connected with a gas chromatograph 22 through a four-way valve 15; the three-way valve 14 and the four-way valve 15 are both arranged on the side plate at the front part of the partition board.
The specific working process of the invention is as follows:
VOCs (volatile organic compounds) enter through a waste gas pipe, air is blown in from an air pipe, gas in the waste gas pipe and the air pipe can be converged after passing through a three-way valve, namely the waste gas is mixed and diluted by 1:2 before entering a four-way valve and is used as pretreatment of the waste gas, and meanwhile, the flow of the two gases is controlled by two mass flowmeters so as to control the dilution ratio of the VOCs to be kept at about 1:2.
The diluted gas enters the shell after passing through the four-way valve. After the power supply is switched on and the switch of the magnetron is pressed, the magnetron works to radiate microwaves, the microwaves heat gas flowing into the shell and heat the inner cavity of the whole shell, and the silicone oil heat-insulating layer can effectively protect the guide pipe. In addition, a part of organic waste gas is digested by the radiation of the microwaves, the electrodeless ultraviolet lamp tubes are excited by the radiated microwaves, the electrodeless ultraviolet lamp tubes emit UV light after working and simultaneously digest VOCs, and the treatment effect on the VOCs is further improved under the combined treatment of the microwaves, the UV light and catalytic combustion.
The temperature controller is connected with the small thermocouple, and the temperature in the shell can be monitored in real time according to the numerical value displayed on the temperature controller. Meanwhile, the infrared thermometer and the pressure sensor can monitor the internal temperature condition and the pressure condition in real time, and the ultraviolet intensity detector is used for detecting the ultraviolet intensity in the shell. And a small high-definition camera is utilized to monitor the use change condition of the internal photocatalyst in real time. Through the blast pipe of following the opening at the casing afterbody installation, when casing internal pressure was too high, pressure sensor can react the receiver with changing, and the solenoid valve on the receiver received pressure sensor's signal back control blast pipe, and the exhaust fan is opened simultaneously in the import of control blast pipe, in time gets rid of the gas that produces in the casing inside, reduces internal pressure.
The waste gas after catalytic combustion treatment is discharged through the four-way valve through the gas outlet pipe, and the type of the exhaust gas is detected and the treatment effect is verified through the gas chromatograph.
In conclusion, the microwave-ultraviolet combined VOCs waste gas catalytic combustion evaluation device provided by the invention has the following beneficial effects:
1. the invention is based on the catalytic combustion technology, utilizes the heating advantages of microwave selectivity, penetrability and instantaneity, directly acts microwave energy on organic pollutants, breaks molecular bonds of macromolecular organic pollutants, converts the macromolecular organic pollutants into micromolecular substances, and can be combusted.
2. The electrodeless ultraviolet lamp tube is excited and generated in a microwave electromagnetic radiation mode, is quickly started and closed, can quickly emit ultraviolet light to clear up VOCs, can better enhance the clearing up effect on the VOCs under the action of UV light and microwave energy, and is assisted by the catalytic action of the catalyst, so that the catalytic combustion effect of the whole device is more obvious, and the treatment effect on the VOCs is better.
3. The invention controls the running number of the magnetrons by controlling the power supply buttons of the magnetrons, further controls the heating power of the device, and simultaneously monitors the temperature change condition inside the device at any time by means of the infrared thermometer and the pressure sensor; and the thermocouple is inserted in the catalyst cavity for measuring temperature, and temperature data can be transmitted to the temperature controller, so that the temperature conditions in the whole catalytic combustion device and the cavity can be monitored simultaneously. The pressure sensor can feed back the pressure condition in the device to the receiver, and the receiver can control gaseous discharge through the mode of controlling opening and close of blast pipe and the work of air discharge fan, and the inside temperature of whole device, pressure can obtain effective control.
4. The small-sized camera made of the high-temperature resistant material can monitor the working change condition of the photocatalyst in the shell at any time and can monitor the actual condition of catalytic combustion in real time.
In the description above, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and thus the present invention is not limited to the specific embodiments disclosed above.
Claims (6)
1. The utility model provides a microwave-ultraviolet allies oneself with VOCs waste gas catalytic combustion evaluation device which characterized in that: the microwave-UV combined catalytic combustion component is communicated with a breather pipe and is used for introducing VOCs waste gas into an inner cavity of a shell of the microwave-UV combined catalytic combustion component; the inner cavity of the shell of the microwave-UV combined catalytic combustion assembly is provided with a photocatalyst capable of contacting VOCs waste gas, and the inner cavity of the shell of the microwave-UV combined catalytic combustion assembly can radiate ultraviolet rays and microwaves for digesting the waste gas; the gas outlet pipe of the microwave-UV combined catalytic combustion assembly is connected with a gas chromatograph, and the type of the discharged gas is detected and the catalytic combustion treatment effect is verified through the gas chromatograph; the microwave-UV combined catalytic combustion assembly comprises a shell, and an electrodeless ultraviolet lamp tube and a waveguide which are arranged on the side wall of the shell, wherein the waveguide is connected with a magnetron and is used for radiating microwaves into the shell; the two ends of the electrodeless ultraviolet lamp tube are arranged on the side wall of the shell, and the tube body of the electrodeless ultraviolet lamp tube is arranged in the shell and used for radiating ultraviolet light to the inner cavity of the shell; the side wall of the shell is also provided with an ultraviolet intensity detector, a temperature measuring instrument and a pressure sensor, and the ultraviolet intensity detector, the temperature measuring instrument and the pressure sensor are used for controlling the internal temperature of the shell within the activity range of the photocatalyst;
the side wall of the shell is also provided with a thermocouple connected with a temperature controller, and the measuring end of the thermocouple extends to the inner cavity of the shell and is used for monitoring the internal temperature of the shell; the top and the bottom of the guide pipe are respectively communicated with the vent pipe and the air outlet pipe at the upper side wall and the lower side wall of the shell;
the middle part of the guide pipe is disconnected to form a waste gas combustion area; the photocatalyst is arranged in the middle of the waste gas combustion area; the waveguide opening, the electrodeless ultraviolet lamp tube and the thermocouple are all arranged on the side surface of the waste gas combustion area; the side wall of the shell is also provided with a small camera for observing the working condition of the photocatalyst in the shell;
the photocatalyst is supported Co 3 O 4 -TiO 2 The preparation method of the photocatalyst comprises the following steps:
（1）TiO 2 preparation: tetrabutyl titanate and ammonia water are mixed according to the ratio of 8-10:1-3, the mass volume ratio is g/ml, the unit of the mass volume ratio is g/ml, and the mixture is heated in water bath until TiO is generated 2 A crystal grain; sterilizing the mixture in a Teflon sterilization container, drying at 100-130 deg.C to constant weight after sterilization, washing with deionized water, drying at 100-105 deg.C for 9-12 hr, and heat treating in a muffle furnace at 400-450 deg.C for 2-4 hr;
wherein the concentration of tetrabutyl titanate is 2.85mol/L, and the concentration of ammonia water is 9.52-11.11mol/L;
（2）Co 3 O 4 preparation: slowly adding a cobalt nitrate solution with the concentration of 10mM into a sodium carbonate solution with the concentration of 12mM, magnetically stirring for 40-60min, then performing centrifugal separation, alternately washing with deionized water and absolute ethyl alcohol, drying, and calcining for 2-4h at 400-450 ℃ in a muffle furnace;
wherein the volume ratio of the cobalt nitrate solution to the sodium carbonate solution is 1:1-2;
(3) Adding TiO into the mixture 2 And Co 3 O 4 Mixing into paste, and coating onto Ni net to obtain supported Co 3 O 4 -TiO 2 A catalyst;
wherein, tiO 2 And Co 3 O 4 The mass ratio of (A) to (B) is 2-4:1-3.
2. The microwave-ultraviolet combined catalytic combustion evaluation device for VOCs exhaust gas of claim 1, wherein: the waste gas pipe that leads to there is the VOCs waste gas and the air hose that leads to there is the air pass through the three-way valve and link to each other with the intake pipe, breather pipe and outlet duct link to each other with gas chromatograph through the cross valve.
3. The microwave-ultraviolet combined catalytic combustion evaluation device for VOCs exhaust gas of claim 2, wherein: and gas mass flowmeters are arranged on the waste gas pipe and the air pipe respectively and are used for controlling the mixing ratio of the VOCs waste gas and the air to be 1:2.
4. The microwave-ultraviolet combined catalytic combustion evaluation device for VOCs exhaust gas of claim 1, wherein: the four electrodeless ultraviolet lamp tubes are transversely arranged on the left side and the right side of the photocatalyst in a front-back mode; the two waveguides are arranged on the left side and the right side of the shell in a staggered mode, and the waveguides are arranged on the outer side of the electrodeless ultraviolet lamp tube; the thermocouple is arranged between the two electrodeless ultraviolet lamp tubes on the same side; the temperature measuring instrument is arranged in front of the side wall of the shell, and the ultraviolet intensity detecting instrument is arranged on the side wall of the shell.
5. The microwave-ultraviolet combined catalytic combustion evaluation device for VOCs exhaust gas of claim 3, wherein: the microwave-UV combined catalytic combustion assembly is arranged in the box body, a door is arranged on the front side of the microwave-UV combined catalytic combustion assembly, and the vent pipe is fixed on the inner wall of the box body through a support; the waste gas pipe, the air pipe, the three-way valve, the gas mass flow meter and the temperature controller are all arranged in the box body and are arranged on one side of the microwave-UV combined catalytic combustion assembly.
6. The microwave-ultraviolet combined VOCs exhaust gas catalytic combustion evaluation device of claim 5, characterized in that: a plurality of layers of partition plates are arranged on one side of the door, and the waste gas pipe, the air pipe, the gas mass flowmeter and the temperature controller are respectively arranged on different partition plates; the waste gas pipe and the air pipe are connected with an air inlet pipe through a three-way valve, and the air inlet pipe, the vent pipe and the air outlet pipe are connected with the gas chromatograph through a four-way valve; the three-way valve and the four-way valve are arranged on the side plate at the front part of the partition plate.
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