CN214345475U - Experimental device for low temperature plasma and wet-type washing jointly get rid of VOCs - Google Patents
Experimental device for low temperature plasma and wet-type washing jointly get rid of VOCs Download PDFInfo
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Abstract
The utility model discloses an experimental apparatus for VOCs is jointly got rid of to low temperature plasma and wet-type washing, including VOCs gas distribution system, low temperature plasma discharge system, wet-type washing system and detection analytic system, the export of VOCs gas distribution system and the access connection of low temperature plasma discharge system, the export of low temperature plasma discharge system with the access connection of wet-type washing system, low temperature plasma discharge system with the export of wet-type washing system all connects detection analytic system; the utility model connects the wet washing system in series with the low-temperature plasma discharge system, and the obtained experimental device has the characteristics of high reaction rate, almost no secondary pollution and the like; the utility model discloses a low temperature plasma and wet-type washing's combined technology has realized VOCs's high-efficient degradation, has reached 1+1 > 2 degradation effect.
Description
Technical Field
The utility model relates to an exhaust-gas treatment technical field specifically is a low temperature plasma and wet-type washing jointly get rid of VOCs's experimental apparatus.
Background
Volatile Organic Compounds (VOCs) are air pollutants widely discharged in the production process of the chemical, ceramic, paint and electroplating industries, and it is proved that some VOCs can react with nitrogen oxides under certain conditions to form photochemical smog pollution or react with free radicals in the atmosphere to form secondary aerosol, which is an important cause of composite air pollution such as urban dust haze and the like, and the toxicity, mutagenicity and carcinogenicity of the VOCs can threaten human health.
The low-temperature plasma technology has attracted extensive attention due to its strong oxidizing power, mild reaction conditions and simple operation, and has gradually been applied to the treatment of industrial VOCs. However, the low temperature plasma technology still has the disadvantages of incomplete oxidation, low mineralization, low energy efficiency, and low utilization rate of high energy electrons when treating VOCs. In order to improve the mineralization degree of pollutants by low-temperature plasma, researchers fill a catalyst in a plasma reactor, but the catalyst is inactivated after being used for a period of time and needs to be replaced or regenerated, so that the cost is increased. Therefore, in order to solve the problem that the effect of degrading the VOCs by using a single low-temperature plasma technology is not ideal, a low-temperature plasma combination device needs to be developed to achieve the purpose of efficiently degrading the VOCs.
The current wet scrubbing technology isA novel VOCs treatment technology mainly utilizes active oxidation groups (. OH) to convert VOCs into carbon dioxide and water. However, when VOCs are purified by a single wet scrubbing technique, the life of the hydroxyl radicals is short (t)1/2<1 mus) in the treatment of organic waste gas flowing continuously, if the removal efficiency is kept high, a large amount of oxidant needs to be injected continuously, which greatly increases the operation cost and has high energy consumption.
SUMMERY OF THE UTILITY MODEL
In order to solve the problem that low temperature plasma discharges and produces residual pollutant among the prior art, the utility model provides a low temperature plasma jointly gets rid of VOCs's experimental apparatus with wet-type washing, the device combines low temperature plasma discharge system and wet-type washing system, utilizes the accessory substance ozone that low temperature plasma discharge system discharged the production as follow-up wet-type washing system's oxidant source, carries out the secondary degradation to VOCs and the intermediate product that low temperature plasma discharge system was not completely degraded through wet-type washing system to reach high-efficient degradation VOCs's purpose.
In order to achieve the above object, the utility model provides a following technical scheme: the experimental device for removing VOCs by combining low-temperature plasma and wet washing comprises a VOCs gas distribution system, a low-temperature plasma discharge system, a wet washing system and a detection analysis system, wherein an outlet of the VOCs gas distribution system is connected with an inlet of the low-temperature plasma discharge system, an outlet of the low-temperature plasma discharge system is connected with an inlet of the wet washing system, and outlets of the low-temperature plasma discharge system and the wet washing system are connected with the detection analysis system.
Further, VOCs gas distribution system includes simulation air gas cylinder, mass flow controller, mixing bottle, constant temperature water bath and syringe pump, and wherein, the gas outlet and the mass flow controller air inlet of simulation air gas cylinder are connected, and mass flow controller's gas outlet passes through gaseous honeycomb duct and mixing bottle access connection, and the export and the mixing bottle access connection of syringe pump, the export of mixing bottle pass through gaseous honeycomb duct with the entry linkage of low temperature plasma discharge system, the mixing bottle is placed in constant temperature water bath.
Further, the low-temperature plasma discharge system comprises a DBD reactor and a high-voltage alternating-current power supply, wherein an outlet of the VOCs gas distribution system is connected with an inlet of the DBD reactor, and an outlet of the DBD reactor is connected with inlets of the wet type washing system and the detection analysis system.
Furthermore, the DBD reactor is a bobbin type dielectric barrier reactor, a discharge electrode bar is arranged in the DBD reactor, the discharge electrode bar is placed in the center inside the DBD reactor, an outer electrode is arranged outside the DBD reactor, the outer electrode is wound on the outer wall of the DBD reactor and grounded, the discharge electrode bar is connected with a high-voltage alternating-current power supply, and the DBD reactor controls the discharge voltage of the discharge electrode bar through the high-voltage alternating-current power supply.
Further, the DBD reactor is made of quartz glass, and the inner diameter of the DBD reactor is 10 mm; the discharge electrode rod is a stainless steel rod, and the diameter of the discharge electrode rod is 2 mm; the outer electrode is a copper sheet, and the width of the copper sheet is 50 mm.
Further, the wet-type washing system comprises a wet-type scrubber and an aeration head, the outlet of the low-temperature plasma discharging system is connected with the inlet of the wet-type scrubber, and the outlet of the wet-type scrubber is connected with the inlet of the detection and analysis system.
Furthermore, deionized water solution is filled in the wet scrubber, the aerator is arranged in the wet scrubber, one end of the aerator is connected with a glass tube, the glass tube extends out of the wet scrubber and is connected with an outlet of the low-temperature plasma discharge system, and the aerator is used for generating bubbles and uniformly distributing gas in the deionized water solution.
Further, an ozone catalytic oxidation reaction layer is further arranged inside the wet scrubber, a catalyst is filled in the ozone catalytic oxidation reaction layer, catalyst baffles are arranged on the upper side and the lower side of the ozone catalytic oxidation reaction layer, and holes are formed in the catalyst baffles.
Furthermore, the diameter of the bubbles generated by the aeration head is 0.1mm-10 mm.
Further, the detection analysis system comprises a gas chromatograph and an ozone analyzer.
Compared with the prior art, the utility model discloses following beneficial effect has at least:
the utility model provides an experimental apparatus for VOCs is jointly got rid of in low temperature plasma and wet-type washing establishes ties wet-type washing system behind low temperature plasma discharge system, and the experimental apparatus who obtains has that reaction rate is fast, does not have characteristics such as secondary pollution almost, not only can improve VOCs's clearance and mineralization degree, still can catch the gaseous phase accessory substance that discharges and produce simultaneously like NOx, O3And organic intermediate products and the like, thereby avoiding the problem of secondary pollution of gas phase in a low-temperature plasma discharge system.
The utility model discloses the accessory substance ozone of well low temperature plasma discharge system can regard as the source of hydroxyl free radical in the wet-type scrubbing system, and the reuse of ozone has improved the energy utilization of low temperature plasma discharge system, and the active group that continuously produces in the well wet-type scrubber of the utility model enables reaction liquid normal position regeneration, and circulated use, no waste liquid discharges, has reduced the energy consumption, and has reduced the running cost;
the utility model discloses the ozone that well low temperature plasma discharge system produced passes through the aeration head and gets into wet scrubber, multiplicable gas-liquid mass transfer makes the ozone density increase of water to impel the OH of more strong oxidizing property to generate, be favorable to explaiing the VOCs molecule, further improve VOCs's degradation rate.
The solution in the wet scrubber of the utility model can effectively avoid the inactivation problem of the catalyst by the scouring action of the solution on the catalyst, thereby reducing the cost of the reaction device;
the utility model discloses a low temperature plasma and wet-type washing's combined technology has realized VOCs's high-efficient degradation, has reached 1+1 > 2 degradation effect.
Drawings
FIG. 1 shows an experimental apparatus for removing VOCs-containing waste gas by combining low-temperature plasma and wet scrubbing;
FIG. 2 is a detailed view of a DBD reactor of the present invention;
FIG. 3 is a detailed view of a mid-wet scrubber of the present invention;
in the drawings: the device comprises a simulated air cylinder 1, a mass flow controller 2, a mixing cylinder 3, a constant-temperature water bath kettle 4, an injection pump 5, a discharge electrode 6, a copper sheet 7, a DBD reactor 8, a high-voltage alternating-current power supply 9, a wet scrubber 10, an aeration head 11, a catalyst 12, a catalyst baffle 13, an ozone catalytic oxidation reaction layer 14, a gas chromatograph 15 and an ozone analyzer 16.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and the detailed description.
As shown in FIG. 1, the utility model provides a low temperature plasma and wet-type washing jointly get rid of VOCs's experimental apparatus, whole experimental apparatus divide into four bibliographic categories and divide into, specifically include VOCs gas distribution system, low temperature plasma discharge system, wet-type washing system and detection and analysis system. The VOCs gas distribution system comprises a simulated air gas cylinder 1, a mass flow controller 2, a mixing cylinder 3, a constant-temperature water bath kettle 4 and an injection pump 5; the low-temperature plasma discharge system comprises a discharge electrode 6, a copper sheet 7, a DBD reactor 8 and a high-voltage alternating-current power supply 9; the wet scrubbing system comprises a wet scrubber 10, an aeration head 11, a catalyst 12, a catalyst baffle 13 and an ozone catalytic oxidation reaction layer 14; the detection analysis system includes a gas chromatograph 15 and an ozone analyzer 16.
Preferably, the air outlet of the simulated air cylinder 1 is connected to the air inlet of the mass flow controller 2, the air outlet of the mass flow controller 2 is connected with the inlet of the mixing cylinder 3 through the gas guide pipe, the mixing cylinder 3 is placed in the constant temperature environment of the constant temperature water bath kettle 4, and the constant temperature is controlled to be 78 +/-1 ℃;
preferably, the simulated air cylinder 1 contains 79% N2And 21% of O2In volume fraction;
preferably, the outlet of the injection pump 5 is connected with the inlet of the mixing bottle 3, the injection pump 5 is used for injecting VOCs into the mixing bottle 3, and the VOCs is mixed with air in the mixing bottle 3;
preferably, the outlet of the mixing bottle 3 is connected with the inlet of the DBD reactor 8 through a gas guide pipe, and the outlet of the DBD reactor 8 is connected with the inlet of a gas chromatography detector 15 and the inlet of an ozone analyzer 16;
preferably, as shown in fig. 2, the DBD reactor 8 is a bobbin-type dielectric barrier reactor, which is made of quartz glass and has an inner diameter of 10mm, a discharge electrode rod 6 is disposed in the DBD reactor 8, the discharge electrode rod 6 is a stainless steel rod and has a diameter of 2mm, the discharge electrode rod 6 is disposed in the center of the inside of the DBD reactor 8, an outer electrode is disposed outside the DBD reactor 8, the outer electrode is a copper sheet 7 with a width of 50mm, and the copper sheet 7 is wound around the outer wall of the DBD reactor 8 and grounds the DBD reactor 8;
preferably, the discharge electrode rod 6 is connected to a high voltage ac power supply 9, and the DBD reactor 8 controls the discharge voltage of the discharge electrode rod 6 by the high voltage ac power supply 9.
Preferably, the discharge voltage of the high-voltage ac power supply 9 is 15 KV.
The degradation process of the DBD reactor 8 can be divided into two steps:
after the high-voltage alternating current power supply 9 is turned on, high-energy electrons generated by discharging directly impact VOCs molecules, and when the energy given to the high-energy electrons by an electric field is greater than the C-C bond energy of the VOCs, the C-C bonds are broken, so that the organic matter structure is damaged;
from high-energy electrons to N in gas2、O2The active substances such as ions, free radicals, excited particles and the like generated by collision can react with VOCs or organic intermediate products in series and decompose the VOCs to finally generate CO2、H2O and other degradation products, and the like.
The utility model discloses well single low temperature plasma discharge system degradation VOCs efficiency is about 43%.
Preferably, the outlet of the DBD reactor 8 is connected to the inlet of the wet scrubber 10 through a gas flow guide pipe, and the outlet of the wet scrubber 10 is connected to the gas chromatograph 15 and the ozone analyzer 16.
Preferably, as shown in fig. 3, the volume of the wet scrubber 10 is 1L, the interior of the wet scrubber 10 is filled with a deionized water solution, an ozone catalytic oxidation reaction layer 14 is disposed in the wet scrubber 10, a catalyst 12 is filled in the ozone catalytic oxidation reaction layer 14, and the catalyst 12 is used for promoting the decomposition of ozone to generate hydroxyl radicals; an aeration head 11 is arranged in the wet scrubber 10, one end of the aeration head 11 is connected with a glass tube, the glass tube extends out of the wet scrubber 10 and is connected with an air outlet of the DBD reactor through a gas guide pipe, gaseous byproducts generated by discharge of the DBD reactor enter the wet scrubber 10 through the aeration head 11, and bubbles are uniformly distributed in a deionized water solution by the aeration head 11 to start catalytic ozonation reaction;
preferably, a catalyst baffle 13 is disposed on both the upper and lower sides of the ozone catalytic oxidation reaction layer 14, and a plurality of holes are disposed on the catalyst baffle 13, and the holes are used for releasing bubbles, so that the bubbles are fully contacted with the catalyst 12 in the ozone catalytic oxidation reaction layer 14, and the catalyst can catalyze the ozone oxidation reaction.
Preferably, the aeration head 1 can generate air bubbles with the diameter of 0.1mm-10mm, and the air bubbles can increase the distribution density and the residence time of ozone in water, thereby promoting the generation of more OH, and being beneficial to the degradation of pollutants.
The utility model provides an experimental apparatus's application method specifically as follows:
1) opening a simulated air cylinder 1, controlling the flow of air to be 1L/min by a mass flow device 2, and then introducing the air into a mixing cylinder 3; meanwhile, injecting organic matters such as liquid toluene or liquid ethyl acetate and the like into the mixing bottle 3 by using an injection pump 5 to simulate VOCs, placing the mixing bottle 3 in a constant-temperature water bath 4, and volatilizing the VOCs under the push of air;
2) VOCs volatilized from the mixing bottle 3 enter a DBD reactor 8, a high-voltage alternating-current power supply 9 controls the discharge voltage to be 15Kv, and a large amount of high-energy electrons, O, OH and O generated by discharge3Active particles with strong oxidizing property, which are oxidized with VOCs to generate intermediate products of low molecular alcohol, acid, lipid and the like which are easy to dissolve in water, and a byproduct O3。
3) The gas discharged from the DBD reactor 8 comprises residual VOCs, intermediate products and O3The gas is introduced into the wet scrubber 10 through the aeration head 11, and the by-product O generated by the discharge is generated3Hydroxyl radicals are generated under the action of the catalyst 13, and the residual VOCs and intermediate products are oxidized by the hydroxyl radicals.
The utility model provides an experimental apparatus can realize VOCs's high-efficient degradation, and the clearance reaches more than 90%.
Example 1
Controlling the gas flow in a simulated air cylinder 1 at 1L/min through a mass flow controller 2, introducing the gas into a mixing bottle 3, introducing liquid toluene into the mixing bottle 3 through an injection pump, placing the mixing bottle 3 in a constant-temperature water bath 4, controlling the temperature of the constant-temperature water bath 4 at 78 +/-1 ℃, further introducing the toluene into a DBD reactor 8 after being volatilized under the pushing of air, and detecting that the initial concentration of VOCs at an inlet of the DBD reactor 8 is controlled at about 60ppm through a gas chromatograph 15; and then starting a high-voltage alternating-current power supply 9, controlling the discharge voltage at 15kV, detecting gas collection at the outlet of the DBD reactor 8 15min after the experiment begins, and evaluating the degradation effect of the single low-temperature plasma on the VOCs.
TABLE 1 Effect of single low-temperature plasma technique on toluene degradation
The VOCs removal rate calculation formula is as follows:
in conclusion, the toluene is degraded by only adopting a single low-temperature plasma technology, and the removal rate of the toluene is only 43.3%.
Example 2
Under the same experimental conditions as in example 1, the DBD reactor 8 was followed by a wet scrubber 10, to which wet scrubber 10 100gMn/Al was added2O3Sampling and detecting the catalyst at the gas outlet of the wet scrubber 10 for 15min after the experiment begins, and evaluating the reduction of the toluene in the low-temperature plasma combined wet scrubbingAnd (5) effect solving.
TABLE 2 degradation of toluene by low temperature plasma combined with wet scrubbing
The VOCs removal rate calculation formula is as follows:
in conclusion, the toluene is degraded by the combination of low-temperature plasma and wet washing, and the removal rate of the toluene reaches 94.2%.
The combination of the experimental results in tables 1 and 2 shows that when the initial toluene concentration is controlled to be 60ppm, the toluene removal rate of the low-temperature plasma combined wet washing experimental device can reach 94.2%, and the degradation effect is obviously superior to the toluene removal rate of 43.3% by using a single low-temperature plasma technology;
calculate the ozone utilization by combining the DBD reactor outlet ozone concentration and the wet scrubber outlet ozone concentration in table 1 and table 2:
in conclusion, the utilization rate of the wet scrubber on ozone reaches 89.6%, and the low-temperature plasma combined wet scrubbing experimental device can efficiently utilize ozone and reduce the emission of ozone.
Example 3
Controlling the gas flow in a simulated air cylinder 1 at 1L/min through a mass flow controller 2, introducing the gas flow into a mixing bottle 3, introducing liquid ethyl acetate into the mixing bottle 3 by using an injection pump, placing the mixing bottle 3 in a constant-temperature water bath 4, controlling the temperature of the constant-temperature water bath 4 at 78 +/-1 ℃, further introducing the ethyl acetate into a DBD reactor 8 after the ethyl acetate is volatilized under the pushing of air, and detecting that the initial concentration of the ethyl acetate at an inlet of the DBD reactor 8 is controlled at 60ppm by using a gas chromatograph 15; and then starting a high-voltage alternating-current power supply 9, controlling the discharge voltage at 15kV, detecting gas collection at an outlet of the DBD reactor 8 after 15min from the beginning of the experiment, and evaluating the degradation effect of the single low-temperature plasma on the ethyl acetate.
TABLE 3 Effect of single low temperature plasma technique on Ethyl acetate degradation
The VOCs removal rate calculation formula is as follows:
in conclusion, it can be concluded that the ethyl acetate is degraded by only using a single low-temperature plasma technology, and the removal rate of the ethyl acetate is only 46.7%.
Example 4
Under the same experimental conditions as in example 3, a wet scrubber 10 was connected to the back of the DBD reactor 8, 100gMn/Al2O3 catalyst was added to the wet scrubber 10, and sampling and detection were performed at the outlet of the wet scrubber 10 15min after the start of the experiment to evaluate the effect of the low-temperature plasma combined with wet scrubbing on the degradation of ethyl acetate.
TABLE 4 Effect of low temperature plasma in combination with wet scrubbing on ethyl acetate degradation
In conclusion, the ethyl acetate is degraded by the combination of low-temperature plasma and wet washing, and the removal rate of the ethyl acetate reaches 98%.
The combination of the experimental results in tables 3 and 4 shows that when the initial ethyl acetate concentration is controlled to be 60ppm, the ethyl acetate removal rate of the low-temperature plasma combined wet washing experimental device can reach 98%, and the degradation effect is obviously superior to 46.7% of the ethyl acetate removal rate of a single low-temperature plasma technology;
calculate the ozone utilization by combining the DBD reactor outlet ozone concentration and the wet scrubber outlet ozone concentration in tables 3 and 4:
combining tables 3 and 4, the wet scrubber achieved a 96.7% ozone utilization.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solutions of the present invention can be modified or replaced with equivalents without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The experimental device for removing VOCs by combining low-temperature plasma and wet washing is characterized by comprising a VOCs gas distribution system, a low-temperature plasma discharge system, a wet washing system and a detection analysis system, wherein an outlet of the VOCs gas distribution system is connected with an inlet of the low-temperature plasma discharge system, an outlet of the low-temperature plasma discharge system is connected with an inlet of the wet washing system, and outlets of the low-temperature plasma discharge system and the wet washing system are connected with the detection analysis system.
2. The experimental device for removing VOCs jointly by low-temperature plasma and wet scrubbing according to claim 1, wherein the gas distribution system for VOCs comprises a simulated air cylinder (1), a mass flow controller (2), a mixing cylinder (3), a constant-temperature water bath (4) and an injection pump (5), wherein an air outlet of the simulated air cylinder (1) is connected with an air inlet of the mass flow controller (2), an air outlet of the mass flow controller (2) is connected with an inlet of the mixing cylinder (3) through a gas guide pipe, an outlet of the injection pump (5) is connected with an inlet of the mixing cylinder (3), an outlet of the mixing cylinder (3) is connected with an inlet of the low-temperature plasma discharge system through a gas guide pipe, and the mixing cylinder (3) is placed in the constant-temperature water bath (4).
3. A combined low temperature plasma and wet scrubber experimental apparatus for removing VOCs as claimed in claim 1, wherein the low temperature plasma discharge system comprises a DBD reactor (8) and a high voltage ac power supply (9), wherein the outlet of the VOCs gas distribution system is connected with the inlet of the DBD reactor (8), and the outlet of the DBD reactor (8) is connected with the inlets of the wet scrubber system and the detection and analysis system.
4. The experimental apparatus for removing VOCs jointly by low-temperature plasma and wet scrubbing according to claim 3, wherein the DBD reactor (8) is a bobbin-type dielectric barrier reactor, a discharge electrode rod (6) is arranged in the DBD reactor (8), the discharge electrode rod (6) is placed in the center of the inside of the DBD reactor (8), an outer electrode is arranged outside the DBD reactor (8), the outer electrode is wound on the outer wall of the DBD reactor (8) and grounded, the discharge electrode rod (6) is connected with a high-voltage alternating-current power supply (9), and the DBD reactor (8) controls the discharge voltage of the discharge electrode rod (6) through the high-voltage alternating-current power supply (9).
5. A combined low temperature plasma and wet scrubbing VOCs experimental apparatus as claimed in claim 4, wherein the DBD reactor (8) is made of quartz glass, and the inner diameter of the DBD reactor (8) is 10 mm; the discharge electrode bar (6) is a stainless steel bar, and the diameter of the discharge electrode bar (6) is 2 mm; the outer electrode is a copper sheet (7), and the width of the copper sheet (7) is 50 mm.
6. A combined cryogenic plasma and wet scrubber experimental apparatus for removal of VOCs as claimed in claim 1, wherein the wet scrubber system comprises a wet scrubber (10) and an aerator (11), the outlet of the cryogenic plasma discharge system is connected to the inlet of the wet scrubber (10), and the outlet of the wet scrubber (10) is connected to the inlet of the detection and analysis system.
7. A low temperature plasma and wet scrubbing combined VOCs experimental apparatus according to claim 6, wherein the interior of said wet scrubber (10) is filled with deionized water solution, said aeration head (11) is disposed inside said wet scrubber (10), one end of said aeration head (11) is connected to a glass tube, said glass tube extends out of said wet scrubber (10) and is connected to the outlet of said low temperature plasma discharge system, and said aeration head (11) is used for generating bubbles to uniformly distribute gas in deionized water solution.
8. The experimental apparatus for removing VOCs by combining low-temperature plasma and wet scrubbing according to claim 6, wherein an ozone catalytic oxidation reaction layer (14) is further disposed inside the wet scrubber (10), the ozone catalytic oxidation reaction layer (14) is filled with a catalyst (12), catalyst baffles (13) are disposed on both upper and lower sides of the ozone catalytic oxidation reaction layer (14), and holes are disposed on the catalyst baffles (13).
9. A low temperature plasma and wet scrubbing combined VOCs experimental apparatus according to claim 6, wherein said aeration head (11) generates bubbles with a diameter of 0.1mm-10 mm.
10. A combined low temperature plasma and wet scrubbing VOCs removal experimental apparatus as claimed in claim 1, wherein said detection and analysis system comprises a gas chromatograph (15) and an ozone analyzer (16).
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