CN111921374A - Method for catalytic degradation of chlorobenzene by using double-section discharge plasma and preparation method of used catalyst - Google Patents

Method for catalytic degradation of chlorobenzene by using double-section discharge plasma and preparation method of used catalyst Download PDF

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CN111921374A
CN111921374A CN202010822968.8A CN202010822968A CN111921374A CN 111921374 A CN111921374 A CN 111921374A CN 202010822968 A CN202010822968 A CN 202010822968A CN 111921374 A CN111921374 A CN 111921374A
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chlorobenzene
discharge
plasma
tio
gas
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姜理英
张瑜芬
黄武
姚志伟
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8659—Removing halogens or halogen compounds
    • B01D53/8662—Organic halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/88—Handling or mounting catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
    • B01D2259/818—Employing electrical discharges or the generation of a plasma

Abstract

The invention relates to a chlorobenzene degradation method, aiming at the problem of incomplete decomposition when low-temperature plasma removes chlorobenzene, and provides a method for catalyzing and degrading chlorobenzene by using double-section discharge plasma, wherein the discharge interval distance of the double-section discharge plasma is less than or equal to 10 cm, 0.1-0.3 g of catalyst is respectively placed in two discharge areas of a reactor, and chlorobenzene is added at the ratio of 200-400 mg/m3The concentration of chlorobenzene is entrained in the air and is introduced into a reactor, a power supply of the reactor is turned on to discharge, the peak voltage is 13-17 kV, and chlorobenzene stays in a discharge area for 1-3 s to degrade. The invention not only utilizes the advantages of low energy consumption, rapid chemical reaction, thorough purification, wide adaptability and the like of the low-temperature plasma, but also makes up for the pairThe treated pollutant has the defects of lack of selectivity, effectively reduces the generation of byproducts and improves CO2Selectivity and contaminant removal rate. The invention also provides a preparation method of the catalyst.

Description

Method for catalytic degradation of chlorobenzene by using double-section discharge plasma and preparation method of used catalyst
Technical Field
The invention relates to a chlorobenzene degradation method, in particular to a method for catalyzing and degrading chlorobenzene by using double-section discharge plasma and a preparation method of a used catalyst.
Background
Due to modern construction and rapid development of the urban and rural industries, more and more Volatile Organic Compounds (VOCs) are emitted into the environment, and chlorobenzene is one of the most typical pollutants. Chlorobenzene is widely used in various industrial applications, pollutes soil and water resources after being released into the environment, seriously threatens human health, and has adverse effects on the central nervous system and the like after being contacted with chlorobenzene for a long time. Chlorobenzene is chemically stable and difficult to degrade, and even if partial degradation is carried out in physical, chemical or biological processes, the degradation process can generate accumulation of intermediates, and the toxicity of the intermediates is three times higher than that of the intermediates per se, so that the research on the efficient treatment method of chlorobenzene becomes important.
Various methods for removing chlorobenzene from exhaust gases have been developed, including absorption, adsorption, membrane separation, catalytic combustion, photocatalytic oxidation, bio-trickling filter, and low temperature plasma. For example, Klecka GM et al use granular activated carbon fluidized bed bioreactors to degrade chlorobenzene-contaminated groundwater (Field evaluation of a granular activated carbon fluidized-bed bioreactor for treating chlorine in the ground, 1996, 15 (2): 93-107); tiehm A et al designed an anaerobic/aerobic biological granular activated carbon treatment apparatus that could operate stably for a long period of time, which was effective in removing substances including chlorobenzene (Sequential and/or aerobic biological adsorbed chlorinated hydrocarbons in activated carbon banks. Water Science and Technology: Water Supply, 2002, 2 (2): 51-58). Dilmeghai M et al combined UV, UV/H under aerobic and anaerobic conditions, respectively2O2、UV/O3The research on chlorobenzene degradation treatment has been carried out by advanced oxidation technologies (Kinetic and mechanism of chlorobenzene degradation in aqueous samples using advanced oxidation processes, 2001, 30 (6): 2062-2070), but the general process flow of the combined integration method is complicated, the working conditions are more limited, and the operation control is more complicated. Wherein the low-temperature plasma has simple process operation, short treatment flow, small occupied area and applicabilityWide application range, high removal efficiency and the like. However, low temperature plasma technology suffers from several disadvantages, particularly low energy efficiency, the production of large amounts of reactive species and ozone residues, incomplete oxidation of contaminants and the formation of undesirable by-products and secondary pollution. Accordingly, an ideal solution is needed.
Disclosure of Invention
The invention provides a method for catalyzing and degrading chlorobenzene by using a two-stage discharge plasma and a preparation method of a catalyst, aiming at overcoming the problem of incomplete decomposition when chlorobenzene is removed by using the low-temperature plasma, wherein the two-stage discharge plasma is combined with the catalyst, so that the advantages of low energy consumption, rapid chemical reaction, thorough purification, wide adaptability and the like of the low-temperature plasma are utilized, the defect of lack of selectivity on treated pollutants is overcome, the generation of byproducts is effectively reduced, and the CO is improved2Selectivity and contaminant removal rate.
In order to achieve the purpose, the invention adopts the following technical scheme: a method for catalytic degradation of chlorobenzene by a double-section discharge plasma is provided, the discharge interval distance of the double-section discharge plasma is less than or equal to 10 cm, 0.1-0.3 g of catalyst is respectively placed in two discharge areas of a double-section discharge plasma reactor, chlorobenzene is entrained in air and is introduced into the double-section discharge plasma reactor in a gas form, the inlet gas concentration of the chlorobenzene is 200-400 mg/m3And turning on a power supply of the plasma reactor for discharging, wherein the peak voltage is 13-17 kV, and chlorobenzene stays in a discharge area for 1-3 s for degradation. The presence of the catalyst in the plasma can reduce the activation energy of the pollutants and increase the mineralization of the pollutants, and has a synergistic effect on the removal of chlorobenzene. The double-section discharge plasma reactor has great improvement in the aspects of improving the energy efficiency and increasing the mineralization of chlorobenzene substances. The double-stage discharge plasma can increase current discharge under a certain input voltage by increasing the number of discharge stages, and generate more active substances for degrading chlorobenzene. Although it has been reported that the single two-stage discharge plasma can improve the degradation of toluene, the coupling of the catalyst in the two-stage reactor of the invention greatly improves the catalytic activity of the catalyst, promotes the deep oxidation of chlorobenzene, and simultaneously can reduce the catalytic activityAdverse effects of chlorinated deactivation of the agent.
Preferably, the low-temperature plasma reactor is a dielectric barrier discharge low-temperature plasma reactor, a quartz tube is used as a barrier medium, the internal electrode is a stainless steel iron rod, each plasma discharge unit in the two-stage discharge is a copper sheet, and the discharge interval is formed by connecting the two copper sheets in series and is connected with the grounding electrode.
Preferably, the quartz tube has an outer diameter of 2.53 cm, an inner diameter of 1.76 cm and a length of 40 cm, the stainless steel rod has a diameter of 0.6 cm, and the copper sheet has a size of 5X 10 cm.
Preferably, the discharge interval distance of the two-stage discharge plasma is 1 cm.
Preferably, the reaction is carried out in the following reaction apparatus: the reaction device consists of a gas distribution system, a plasma reaction system and an analysis system which are connected in sequence, wherein the gas distribution system is provided with two gas paths, compressed air is provided by an air pump, the first gas path is formed by sequentially connecting a first mass flow controller and a silica gel dryer in series, the second gas path is formed by sequentially connecting a second mass flow controller and a stripping bottle filled with constant-temperature water bath chlorobenzene liquid in series, and the two gas paths are connected in parallel, then introduced into a gas mixing bottle and then connected with a gas inlet of the plasma reactor; the plasma reactor is the double-section discharge plasma reactor and is provided with a high-voltage power supply; the gas outlet of the plasma reactor is connected with an analytical instrument, and the analytical instrument comprises a gas chromatographic analyzer and an oscilloscope.
The invention also provides a preparation method of the catalyst, which comprises the steps of dissolving manganese nitrate and cobalt acetate in distilled water, uniformly stirring, and then adding TiO2Stirring the powder for 2 hours at the temperature of 35-40 ℃, and then dropwise adding Na2CO3Stirring the solution for 4 h, filtering, washing with deionized water to neutrality, drying at 80 deg.C overnight, calcining at 350 deg.C for 5 h in muffle furnace to obtain Co-Mn/TiO2A catalyst. The Mn-based catalyst is widely applied to industrial catalysis as one of the most efficient and economic catalysts, the addition of metal Co can promote the electronic exchange among Mn with different valence states, the activity of the Mn-based catalyst is increased, meanwhile, the catalyst is poisoned due to the fact that chlorine-containing intermediate products are easily generated in the catalytic degradation of chlorobenzene, and TiO serving as a supporting material2The introduction of (2) can strengthen the pore diameter structure and slow down the catalyst poisoning.
Preferably, manganese nitrate, cobalt acetate and TiO2The ratio of the amounts of the substances of (a) to (b) is 1:1: 20.
Preferably, TiO is used2The powder is modified, and the preparation method comprises the following steps:
(1) sulfonation of beta-cyclodextrin: pouring beta-cyclodextrin into concentrated sulfuric acid, stirring for 2 hours at 0-5 ℃, pouring reaction liquid into water, adding calcium carbonate accounting for 0.5-0.6wt% of the beta-cyclodextrin to generate precipitation, filtering to obtain filtrate, adding 95% ethanol, standing at 0-5 ℃ for 12-14 hours, removing the precipitation, adjusting the pH of the filtrate to 10-11 by using sodium carbonate, filtering again, adjusting the filtrate to be neutral by using glacial acetic acid, performing rotary evaporation and concentration to 10% -30% of the original volume, adding absolute ethanol into the concentrated solution to generate precipitation, filtering, washing and performing vacuum drying to obtain powder, namely the product of the sulfonated-beta-cyclodextrin;
(2) dispersing TiO2 powder in methanol solvent and forming TiO by ultrasonic2Adding sulfonated-beta-cyclodextrin and nano-scale pyrophyllite into the slurry, and continuing to perform ultrasonic treatment to obtain a mixture, wherein TiO is2The mass ratio of the sulfonated-beta-cyclodextrin to the nano-scale pyrophyllite is 100 (5-20) to 10-30;
(3) the mixture is rotationally evaporated at the temperature of 10-20 ℃, washed, dried, crushed and sieved to obtain the modified TiO2And (3) powder.
TiO2After the powder is subjected to the modification treatment, the catalytic degradation effect on chlorobenzene is better. The two adjacent crystal layers of the pyrophyllite with the layered structure are connected only by Van der Waals force, the structure is easy to damage along the layers, and anions and cations can enter the layers, so the pyrophyllite and TiO2After mixing, the adsorption activity can be improved. On the one hand, the sulfonated-beta-cyclodextrin improves TiO2Bonding strength with pyrophyllite, and on the other hand, its sulfonate anion to TiO2Has inducing effect and can prevent TiO2And (4) agglomeration.
Therefore, the invention has the following beneficial effects: the invention combines the two-stage discharge plasma with the catalyst, and exerts the advantages of low energy consumption, rapid chemical reaction, thorough purification, wide adaptability and the like of the low-temperature plasmaHas the advantages of making up the deficiency of lack of selectivity to the treated pollutants, effectively reducing the generation of by-products and improving CO2Selectivity and pollutant removal rate, and provides an efficient and economically feasible direction for the degradation of chlorobenzene. The mineralization rate of chlorobenzene increases with increasing voltage and reaches 93% already at 15 kV; Co-Mn/TiO2The catalyst can be recycled for many times, still has high catalytic activity after continuous 48-hour reaction, and can recover the activity by increasing voltage.
Drawings
FIG. 1 is a schematic view of a reaction apparatus used in the present invention.
FIG. 2 is a schematic view of the structure of the plasma reactor of the present invention.
Fig. 3 is a graph of current and voltage waveforms for the present invention.
FIG. 4 shows the chlorobenzene degradation rates (a) and CO according to the invention2Selectivity (b) is plotted as a function of input voltage.
FIG. 5 is a graph of the stability of the catalyst of the present invention in combination with a two-stage discharge plasma for chlorobenzene removal.
FIG. 6 shows the Co-Mn/TiO prepared by the present invention2SEM image (a) and TEM image (b) of the catalyst.
FIG. 7 shows the preparation of Co-Mn/TiO according to the present invention2X-ray diffraction (XRD) characterization of the catalyst.
FIG. 8 shows the chlorobenzene degradation rates (a) and CO according to the invention2Selectivity (b) is plotted as a function of distance of the two-stage discharge plasma.
In the figure: 1-air pump, 1-2-first glass rotameter, 1-3-silica gel dryer, 1-4-second glass rotameter, 1-5-air blowing bottle, 1-6-gas mixing bottle, 2-1-plasma reactor, 2-high voltage power supply, 3-1-gas chromatograph, 3-2-oscilloscope, 4-high voltage input end, 5-gas inlet, 6-stainless steel bar, 7-quartz tube, 8-copper sheet, 9-catalyst, 10-quartz wool, and 11-gas outlet.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
In the present invention, unless otherwise specified, all the raw materials and equipment used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
As shown in FIGS. 1 and 2, the reaction device used in the present invention comprises a gas distribution system, a plasma reaction system and an analysis system which are connected in sequence. The gas distribution system is provided with two gas paths, compressed air is provided by an air pump 1-1, the first gas path is formed by sequentially connecting a first mass flow controller, namely a first glass rotameter 1-2 and a silica gel dryer 1-3 in series, the second gas path is formed by sequentially connecting a second mass flow controller, namely a second glass rotameter 1-4 and a stripping bottle 1-5 filled with constant-temperature water bath chlorobenzene liquid in series, and the two gas paths are connected in parallel and then introduced into a gas mixing bottle 1-6. As shown in FIG. 2, the plasma reactor 2-1 is a dielectric barrier discharge two-stage discharge low-temperature plasma reactor, the gas inlet 5 of the plasma reactor 2-1 is connected with a gas mixing bottle 1-6, the gas outlet 11 is connected with an analyzer, and one side of the gas inlet 5 is provided with a high-voltage input end 4 connected with a high-voltage power supply 2-2. The plasma reactor 2-1 takes a quartz tube 7 as a barrier medium, and the quartz tube 7 has an outer diameter of 2.53 cm, an inner diameter of 1.76 cm and a length of 40 cm; the inner electrode is a stainless steel iron rod 6, and the diameter of the stainless steel iron rod 6 is 0.6 cm; each plasma discharge unit in the double-section discharge is a copper sheet 8, a discharge interval is formed by connecting two copper sheets 8 in series and is connected with a grounding electrode, and the size of each copper sheet 8 is 5 multiplied by 10 cm. The catalysts 9 are respectively and uniformly arranged in two discharge areas of the plasma reactor 2-1 and fixed by quartz cotton 10. The analyzer comprises a gas chromatographic analyzer 3-1 and an oscilloscope 3-2, wherein the gas chromatographic analyzer 3-1 is used for detecting chlorobenzene concentration and CO2Concentration, oscilloscope 3-2 can detect current and voltage.
The method for catalytic degradation of chlorobenzene comprises the following steps: respectively placing 0.1-0.3 g of catalyst 9 in two discharge regions of a double-section discharge plasma reactor 2-1, fixing with quartz wool 10, adjusting three gas paths to proper conditions, introducing the gas for half an hour stably, introducing chlorobenzene into the double-section discharge plasma reactor 2-1 in a gas form in the air with chlorobenzene entrained therein, and adjusting the inlet gas concentration of the chlorobenzene to 200-400 mg/m3Is openedDischarging by a high-voltage power supply 2-2 of the plasma reactor 2-1, wherein the distance between the discharge regions of the two-stage discharge plasma is less than or equal to 10 cm, the peak voltage is 13-17 kV, the gas flow continuously rushes into the discharge region at the flow rate of 1L/min for oxidative degradation, the chlorobenzene stays in the discharge region for 1-3 s, and finally, the reacted gas is connected with a detector for measuring the concentration of the chlorobenzene.
Example 1
(1) Preparation of Co-Mn/TiO2Catalyst: 0.29 g of manganese nitrate and 0.29 g of cobalt acetate are dissolved in 50 mL of distilled water and stirred to form a uniform solution, and 2 g of TiO is slowly added2Adding the powder into the solution, stirring at 35-40 deg.C for 2 hr, and slowly adding 25 mL Na dropwise into the mixture2CO3Solution (0.2 mol/L), stirring the precipitate for 4 h, filtering and washing with deionized water to neutrality, drying at 80 deg.C overnight, calcining at 350 deg.C (3 deg.C/min) for 5 h in a muffle furnace to obtain Co-Mn/TiO2A catalyst. The resulting Co-Mn/TiO2SEM and TEM images of the catalyst are shown in FIG. 6, XRD is shown in FIG. 7, and Co-Mn/TiO can be seen2The specific surface area of the catalyst was 51.03 m2(g) metal oxide uniformly distributed on TiO2A surface.
(2) Catalytic degradation of chlorobenzene: the distance between the discharge regions of the two-stage discharge plasma is 1 cm, the length of each discharge region is 5 cm, the total length of the two discharge regions is 10 cm, and 0.15 g of Co-Mn/TiO is respectively placed in the two discharge regions2Fixing the catalyst with quartz wool, adjusting three gas paths to proper conditions, introducing gas stably for half an hour, introducing chlorobenzene in the form of gas in the air into the two-stage discharge plasma reactor, wherein the inlet concentration of chlorobenzene is 300 mg/m3And turning on the power supply of the plasma reactor to discharge. Adjusting the peak voltage of the plasma to 15 kV, continuously flushing airflow into a discharge area at the flow rate of 1L/min for oxidative degradation, staying chlorobenzene in the discharge area for 2 s, and finally connecting the reacted gas with a detector to measure the concentration of the chlorobenzene.
Example 2
The difference from example 1 is that the peak voltage of the plasma was 14 kV.
Example 3
The difference from example 1 is that the peak voltage of the plasma is 16 kV.
Example 4
The difference from example 1 is that the peak voltage of the plasma was 17 kV.
Example 5
The difference from the example 1 is that the distance between the discharge intervals of the two-stage discharge plasma was 0.5 cm.
Example 6
The difference from the example 1 is that the discharge interval distance of the two-stage discharge plasma is 2 cm.
Example 7
The difference from the example 1 is that the discharge interval distance of the two-stage discharge plasma is 3 cm.
Example 8
The difference from the example 1 is that the discharge interval distance of the two-stage discharge plasma is 4 cm.
Example 9
The difference from the example 1 is that the discharge interval distance of the two-stage discharge plasma is 7 cm.
Example 10
The difference from the example 1 is that the discharge interval distance of the two-stage discharge plasma is 10 cm.
Example 11
The difference from example 1 is that TiO2The powder is modified, and the preparation method comprises the following steps:
(1) sulfonation of beta-cyclodextrin: weighing 10 g of beta-cyclodextrin, putting the beta-cyclodextrin into a 100mL round-bottom flask, putting the round-bottom flask into an ice-water mixture, pouring 30mL of concentrated sulfuric acid with the mass fraction of 80%, uniformly stirring the mixture by using a glass rod, stirring the mixture for 2 hours at 0-5 ℃ by using a magnetic stirrer, pouring a reaction solution into 500 mL of water, adding 60 g of calcium carbonate to generate a large amount of white precipitate, filtering the generated calcium sulfate by using a Buchner funnel, washing the calcium sulfate by using water, combining filtrates, adding 100mL of ethanol with the volume fraction of 95%, standing the reaction solution for 14 hours at 0-5 ℃, removing the precipitate, adjusting the pH of the filtrate to 10 by using sodium carbonate, filtering the filtrate, adjusting the pH value to 7.0 by using glacial acetic acid, carrying out rotary evaporation and concentration to 30% of the original volume, adding 500 mL of anhydrous ethanol into the concentrated solution to generate a large amount of white precipitate, filtering, washing the product by respectively using, vacuum drying to obtain white powder, i.e. the product of sulfonated-beta-cyclodextrin;
(2) adding TiO into the mixture2Ultrasonic forming TiO by dispersing powder in methanol solvent2Adding sulfonated-beta-cyclodextrin and nano-scale pyrophyllite into the slurry, and continuing to perform ultrasonic treatment to obtain a mixture, wherein TiO is2The mass ratio of the sulfonated-beta-cyclodextrin to the nanoscale pyrophyllite is 100:20: 30;
(3) the mixture is rotationally evaporated at the temperature of 20 ℃, washed, dried, crushed and sieved to obtain the modified TiO2And (3) powder.
Example 12
(1) Preparation of modified TiO2: 1) sulfonation of beta-cyclodextrin: weighing 10 g of beta-cyclodextrin, putting the beta-cyclodextrin into a 100mL round-bottom flask, putting the round-bottom flask into an ice-water mixture, pouring 30mL of concentrated sulfuric acid with the mass fraction of 80%, uniformly stirring the mixture by using a glass rod, stirring the mixture for 2 hours at 0-5 ℃ by using a magnetic stirrer, pouring a reaction solution into 500 mL of water, adding 55 g of calcium carbonate to generate a large amount of white precipitate, filtering the generated calcium sulfate by using a Buchner funnel, washing the calcium sulfate by using water, combining filtrates, adding 100mL of ethanol with the volume fraction of 95%, standing the reaction solution for 12 hours at 0-5 ℃, removing the precipitate, adjusting the pH of the filtrate to 10.5 by using sodium carbonate, filtering the filtrate, adjusting the pH value to 7.0 by using glacial acetic acid, carrying out rotary evaporation and concentration to 20% of the original volume, adding 500 mL of anhydrous ethanol into the concentrated solution to generate a large amount of white precipitate, filtering, respectively washing the product by using, vacuum drying to obtain white powder, i.e. the product of sulfonated-beta-cyclodextrin;
2) adding TiO into the mixture2Ultrasonic forming TiO by dispersing powder in methanol solvent2Adding sulfonated-beta-cyclodextrin and nano-scale pyrophyllite into the slurry, and continuing to perform ultrasonic treatment to obtain a mixture, wherein TiO is2The mass ratio of the sulfonated-beta-cyclodextrin to the nanoscale pyrophyllite is 100:15: 20;
3) the mixture is rotationally evaporated at 15 ℃, washed to remove impurities, dried by high-purity nitrogen, crushed and sieved to obtain the modified TiO2And (3) powder.
（2）Preparation of Co-Mn/TiO2Catalyst: 0.29 g of manganese nitrate and 0.29 g of cobalt acetate are dissolved in 50 mL of distilled water and stirred to form a uniform solution, and 2 g of modified TiO is slowly added2Adding the powder into the solution, stirring at 35-40 deg.C for 2 hr, and slowly adding 25 mL Na dropwise into the mixture2CO3Solution (0.2 mol/L), stirring the precipitate for 4 h, filtering and washing with deionized water to neutrality, drying at 80 deg.C overnight, calcining at 350 deg.C (3 deg.C/min) for 5 h in a muffle furnace to obtain Co-Mn/TiO2A catalyst.
(3) Catalytic degradation of chlorobenzene: the distance between the discharge regions of the two-stage discharge plasma is 1 cm, the length of each discharge region is 5 cm, the total length of the two discharge regions is 10 cm, and 0.1 g of Co-Mn/TiO is respectively placed in the two discharge regions2Fixing the catalyst with quartz wool, adjusting three gas paths to proper conditions, introducing gas stably for half an hour, introducing chlorobenzene in the form of gas in the air into the two-stage discharge plasma reactor, wherein the inlet concentration of chlorobenzene is 200 mg/m3And turning on the power supply of the plasma reactor to discharge. Adjusting the peak voltage of the plasma to 15 kV, continuously flushing airflow into a discharge area at the flow rate of 1L/min for oxidative degradation, staying chlorobenzene in the discharge area for 3 s, and finally connecting the reacted gas with a detector to measure the concentration of the chlorobenzene.
Example 13
(1) Preparation of modified TiO2: 1) sulfonation of beta-cyclodextrin: weighing 10 g of beta-cyclodextrin, putting the beta-cyclodextrin into a 100mL round-bottom flask, putting the round-bottom flask into an ice-water mixture, pouring 30mL of concentrated sulfuric acid with the mass fraction of 80%, uniformly stirring the mixture by using a glass rod, stirring the mixture for 2 hours at 0-5 ℃ by using a magnetic stirrer, pouring a reaction solution into 500 mL of water, adding 50 g of calcium carbonate to generate a large amount of white precipitate, filtering the generated calcium sulfate by using a Buchner funnel, washing the calcium sulfate by using water, combining filtrates, adding 100mL of ethanol with the volume fraction of 95%, standing the reaction solution for 13 hours at 0-5 ℃, removing the precipitate, adjusting the pH of the filtrate to 11 by using sodium carbonate, filtering the filtrate, adjusting the pH value to 7.0 by using glacial acetic acid, carrying out rotary evaporation and concentration to 10% of the original volume, adding 500 mL of anhydrous ethanol into the concentrated solution to generate a large amount of white precipitate, filtering, washing the product by respectively using, trueDrying in air to obtain white powder, namely the product of sulfonated-beta-cyclodextrin;
2) adding TiO into the mixture2Ultrasonic forming TiO by dispersing powder in methanol solvent2Adding sulfonated-beta-cyclodextrin and nano-scale pyrophyllite into the slurry, and continuing to perform ultrasonic treatment to obtain a mixture, wherein TiO is2The mass ratio of the sulfonated-beta-cyclodextrin to the nanoscale pyrophyllite is 100:5: 10;
3) the mixture is rotationally evaporated at 10 ℃, washed, dried, crushed and sieved to obtain the modified TiO2And (3) powder.
(2) Preparation of Co-Mn/TiO2Catalyst: 0.29 g of manganese nitrate and 0.29 g of cobalt acetate are dissolved in 50 mL of distilled water and stirred to form a uniform solution, and 2 g of modified TiO is slowly added2Adding the powder into the solution, stirring at 35-40 deg.C for 2 hr, and slowly adding 25 mL Na dropwise into the mixture2CO3Solution (0.2 mol/L), stirring the precipitate for 4 h, filtering and washing with deionized water to neutrality, drying at 80 deg.C overnight, calcining at 350 deg.C (3 deg.C/min) for 5 h in a muffle furnace to obtain Co-Mn/TiO2A catalyst.
(3) Catalytic degradation of chlorobenzene: the distance between the discharge regions of the two-stage discharge plasma is 1 cm, the length of each discharge region is 5 cm, the total length of the two discharge regions is 10 cm, and 0.3 g of Co-Mn/TiO is respectively placed in the two discharge regions2Fixing the catalyst with quartz wool, adjusting three gas paths to proper conditions, introducing gas stably for half an hour, introducing chlorobenzene in the form of gas in the air into the two-stage discharge plasma reactor, wherein the inlet concentration of chlorobenzene is 400 mg/m3And turning on the power supply of the plasma reactor to discharge. Adjusting the peak voltage of the plasma to 15 kV, continuously flushing airflow into a discharge area at the flow rate of 1L/min for oxidative degradation, staying chlorobenzene in the discharge area for 1 s, and finally connecting the reacted gas with a detector to measure the concentration of the chlorobenzene.
Comparative example 1
The difference from example 1 is that a single-stage discharge plasma reactor is used: 0.3 g of Co-Mn/TiO from example 1 was placed in the discharge region2Fixing catalyst with quartz wool, regulating three gas paths to proper conditions, and stably ventilatingWhen the reaction is carried out for a while, the chlorobenzene is entrained in the air and is introduced into the double-section discharge plasma reactor in a gas form, and the inlet gas concentration of the chlorobenzene is 300 mg/m3And turning on the power supply of the plasma reactor to discharge. Adjusting the peak voltage of the plasma to 15 kV, continuously flushing airflow into a discharge area at the flow rate of 1L/min for oxidative degradation, staying chlorobenzene in the discharge area for 2 s, and finally connecting the reacted gas with a detector to measure the concentration of the chlorobenzene.
Comparative example 2
The difference from example 5 is that no catalyst is added.
Analysis of results
(1) Comparing example 1 with comparative example 1, as shown in FIG. 3, the peak value of the discharge current of the two-stage discharge was higher than that of the single-stage discharge at an input voltage of 15 kV, when the plasma was mixed with Co-Mn/TiO2When the catalyst is coupled, the current intensity of the discharge area is weakened, and the change in the two-section discharge is more obvious, but Co-Mn/TiO2The presence of the catalyst enhances surface discharge and thus the plasma area, which, while weakening the current intensity, can increase the density of the current pulse to promote rapid degradation of chlorobenzene.
(2) In comparative examples 1 to 4, as shown in FIG. 4, the effect of the treatment with chlorobenzene by the plasma increased as the input voltage increased. Chlorobenzene degradation rate and CO of two-stage discharge plasma at low voltage input2Selectivity is significantly better than single-stage discharge, with the advantages becoming less pronounced as the input voltage increases, probably because the higher input voltage has a higher electron density and the introduction of a two-stage discharge has no apparent increase in the number of electrons. The treatment effect of the double-stage discharge on chlorobenzene is close to that of a single-stage discharge synergistic catalyst system. Co-Mn/TiO2The addition of the catalyst can effectively increase the degradation rate of chlorobenzene and CO on the basis of single plasma2Selectivity, in which a two-stage discharge plasma is Co-operative with Co-Mn/TiO2When the input voltage of the catalyst system is 15 kV, the degradation rate and CO of the chlorobenzene are reduced2The selectivity can reach 93.1 percent and 64.3 percent respectively, and is improved by 37.3 percent and 30.2 percent respectively compared with single-stage plasma without adding a catalyst. This is probably due to the microporous structure of the catalystThe chlorobenzene is better dispersed, so that the retention time of the chlorobenzene is prolonged, active sites on the surface can adsorb the chlorobenzene, active substances can fully react with the chlorobenzene, and high chlorobenzene degradation rate and CO are promoted2And (4) selectivity.
(3) Comparing example 1, examples 5-10 and comparative example 2, as shown in fig. 8, the distance between the discharge zones affects the removal of chlorobenzene waste gas by the two-stage low-temperature plasma, and the effect of the two-stage discharge plasma with different discharge zone distances on the removal of chlorobenzene was tested to pass the chlorobenzene removal efficiency and CO removal efficiency2The selectivity was evaluated and the Co-Mn/TiO from example 1 was added in two stages2The catalyst was tested at 0.15 g each. The length of the discharge area is two sections of 5 cm, the two sections are added and have the same length with the single section, the residence time of chlorobenzene in the discharge area is 2 s, and the inlet gas concentration is 300 mg/m3The input voltage was 15 kV. The result shows that the two-stage discharge distance is within<Chlorobenzene removal at 7 cm and CO2The selectivity is obviously better than that of single-stage discharge (distance = 0), the effect is more obvious when the distance between discharge intervals is closer, and when the discharge distance is 0.5 cm without adding a catalyst, the degradation rate and CO of chlorobenzene are reduced2The selectivity is increased by 26.3% and 20.2% compared with single-stage discharge respectively. The addition of the catalyst can increase the chlorobenzene removal effect of the two-stage discharge plasma and maintain higher CO2And (4) selectivity. When the two-step distance increases (>4 cm), the second copper sheet cannot be punctured due to the fact that the input voltage is kept unchanged, the discharge amount cannot be completely covered, at the moment, the device discharges in only one section, namely a discharge section with the length of 5 cm is formed, and the chlorobenzene treatment effect is gradually reduced. Due to the average placement of the two-stage discharge catalyst (0.15 g for each stage) and 0.3 g for the single-stage plasma catalyst, the chlorobenzene treatment effect of the two-stage discharge plasma in cooperation with the Co-Mn/TiO2 catalyst is inferior to that of the single-stage plasma under the condition of only single-stage breakdown discharge. On the premise of not influencing the discharge in the two-section interval, in order to better see the discharge condition of the two-section discharge, the test is preferably carried out with the discharge interval distance of 1 cm.
(4) Comparative example 1 and examples 11-13 to TiO in catalyst2After modification, the degradation rate of the chlorobenzene is improved from 93 percent to 96 percent98% (98% for example 11, 96% for example 12, 97% for example 13) of TiO2After the powder is modified, the catalytic degradation effect on chlorobenzene is better. The two adjacent crystal layers of the pyrophyllite with the layered structure are connected only by Van der Waals force, the structure is easy to damage along the layers, and anions and cations can enter the layers, so the pyrophyllite and TiO2After mixing, the adsorption activity can be improved. On the one hand, the sulfonated-beta-cyclodextrin improves TiO2Bonding strength with pyrophyllite, and on the other hand, its sulfonate anion to TiO2Has inducing effect and can prevent TiO2And (4) agglomeration.
(5) The invention also researches the synergy of the two-stage discharge plasma and the Co-Mn/TiO under two voltages (13 kV and 15 kV)2Stability of the catalyst in chlorobenzene catalytic systems. As shown in FIG. 5, the two-stage discharge CO-catalyst can maintain high level of chlorobenzene degradation rate (over 87%) and CO no matter under high voltage or low voltage2Selectivity (over 60%). When the input voltage is 13 kV in the first 12 h reaction, the activity of the catalyst is kept stable, the chlorobenzene degradation rate and CO are reduced2The selectivity is respectively maintained at 92% and 63%; the catalyst activity was also substantially stabilized at a level of 95% chlorobenzene degradation and 66% CO2 selectivity at an input voltage of 15 kV for the second 12 h reaction. When the input voltage is reduced from 15 kV to 13 kV, the activity of the catalyst is obviously reduced, and the chlorobenzene removal rate is reduced by 6 percent compared with the initial 12 h reaction. This result may be due to the deposition of chlorobenzene by-product on the catalyst under low voltage conditions. The activity of the catalyst increased when the voltage was again increased to 15 kV. Wherein Co-Mn/TiO2CO of p-chlorobenzene under synergistic two-stage discharge plasma condition of catalyst2The selectivity can be kept stable under different input voltages.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (8)

1. A method for catalytic degradation of chlorobenzene by using a two-stage discharge plasma is characterized in that the discharge interval distance of the two-stage discharge plasma is less than or equal to 10 cm, 0.1-0.3 g of catalyst is respectively placed in two discharge areas of a two-stage discharge plasma reactor, chlorobenzene is entrained in air and is introduced into the two-stage discharge plasma reactor in a gas form, and the inlet gas concentration of the chlorobenzene is 200-400 mg/m3And turning on a power supply of the plasma reactor for discharging, wherein the peak voltage is 13-17 kV, and chlorobenzene stays in a discharge area for 1-3 s for degradation.
2. The method for catalytic degradation of chlorobenzene by using two-stage discharge plasma according to claim 1, wherein the low-temperature plasma reactor is a dielectric barrier discharge low-temperature plasma reactor, a quartz tube is used as a barrier medium, the inner electrode is a stainless steel iron rod, each plasma discharge unit in the two-stage discharge is a copper sheet, and a discharge interval is formed by connecting two copper sheets in series and is connected with a grounding electrode.
3. The method for catalytic degradation of chlorobenzene by using a two-stage discharge plasma as claimed in claim 2, wherein the quartz tube has an outer diameter of 2.53 cm, an inner diameter of 1.76 cm and a length of 40 cm, the stainless steel rod has a diameter of 0.6 cm, and the copper sheet has a size of 5 x 10 cm.
4. The method for catalytic degradation of chlorobenzene by using the two-stage discharge plasma according to claim 1, wherein the distance between discharge intervals of the two-stage discharge plasma is 1 cm.
5. The method for catalytic degradation of chlorobenzene by using two-stage discharge plasma according to claim 1, characterized in that the method is carried out in the following reaction device: the reaction device consists of a gas distribution system, a plasma reaction system and an analysis system which are connected in sequence, wherein the gas distribution system is provided with two gas paths, compressed air is provided by an air pump, the first gas path is formed by sequentially connecting a first mass flow controller and a silica gel dryer in series, the second gas path is formed by sequentially connecting a second mass flow controller and a stripping bottle filled with constant-temperature water bath chlorobenzene liquid in series, and the two gas paths are connected in parallel, then introduced into a gas mixing bottle and then connected with a gas inlet of the plasma reactor; the plasma reactor is the double-section discharge plasma reactor and is provided with a high-voltage power supply; the gas outlet of the plasma reactor is connected with an analytical instrument, and the analytical instrument comprises a gas chromatographic analyzer and an oscilloscope.
6. A method for preparing the catalyst used in the method for catalytic degradation of chlorobenzene by double-stage discharge plasma as claimed in any of claims 1 to 5, wherein manganese nitrate and cobalt acetate are dissolved in distilled water and stirred uniformly, and TiO is added2Stirring the powder for 2 hours at the temperature of 35-40 ℃, and then dropwise adding Na2CO3Stirring the solution for 4 h, filtering, washing with deionized water to neutrality, drying at 80 deg.C overnight, calcining at 350 deg.C for 5 h in muffle furnace to obtain Co-Mn/TiO2A catalyst.
7. The method for catalytic degradation of chlorobenzene by using double-stage discharge plasma as claimed in claim 6, wherein manganese nitrate, cobalt acetate and TiO2The ratio of the amounts of the substances of (a) to (b) is 1:1: 20.
8. The method for preparing the catalyst used in the method for catalytic degradation of chlorobenzene by using the double-stage discharge plasma according to claim 6 or 7, wherein the TiO is TiO2The powder is modified, and the preparation method comprises the following steps: (1) sulfonation of beta-cyclodextrin: pouring beta-cyclodextrin into concentrated sulfuric acid, stirring at 0-5 deg.C for 2 hr, pouring the reaction solution into water, adding calcium carbonate 0.5-0.6wt% of beta-cyclodextrin to generate precipitate, filtering to obtain filtrate, adding 95% ethanol, standing at 0-5 deg.C for 12-14 hr, removing precipitate, adjusting pH of the filtrate to 1 with sodium carbonate0-11, filtering again, adjusting the filtrate to be neutral by using glacial acetic acid, performing rotary evaporation and concentration to 10% -30% of the original volume, adding absolute ethyl alcohol into the concentrated solution to generate precipitate, filtering, washing and performing vacuum drying to obtain powder, namely the product of the sulfonated-beta-cyclodextrin;
(2) dispersing TiO2 powder in methanol solvent and forming TiO by ultrasonic2Adding sulfonated-beta-cyclodextrin and nano-scale pyrophyllite into the slurry, and continuing to perform ultrasonic treatment to obtain a mixture, wherein TiO is2The mass ratio of the sulfonated-beta-cyclodextrin to the nano-scale pyrophyllite is 100 (5-20) to 10-30;
(3) the mixture is rotationally evaporated at the temperature of 10-20 ℃, washed, dried, crushed and sieved to obtain the modified TiO2And (3) powder.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113070012A (en) * 2021-03-16 2021-07-06 浙江理工大学 Reaction device and method for generating methanol by using carbon dioxide and hydrogen
CN113458138A (en) * 2021-07-07 2021-10-01 合肥学院 Experimental method for repairing fluorene contaminated soil
CN113600180A (en) * 2021-07-16 2021-11-05 浙江工业大学 MnO based on KOH modification2Composite TiO2Preparation method and application of composite catalyst
CN114918242A (en) * 2022-05-07 2022-08-19 浙江大学 Micro-plastic contaminated soil remediation device and method based on coaxial DBD plasma technology

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030070931A (en) * 2002-02-27 2003-09-03 한국에너지기술연구원 Multi layer non-thermal plasma/catalyst reactor
CN103933897A (en) * 2014-04-09 2014-07-23 杭州尊邦科技有限公司 Embedded-type plasma reactor for performing adsorption catalysis on VOCs (volatile organic chemicals) as well as method
CN108355486A (en) * 2018-03-07 2018-08-03 广州握胜环保科技有限公司 Low-temperature plasma synergistic catalytic unit
CN108543537A (en) * 2018-04-18 2018-09-18 清华大学 It a kind of cobalt Mn complex oxide catalyst and its prepares and the method for coupled plasma cleaning organic waste gas
CN109364706A (en) * 2018-12-13 2019-02-22 浙江省环境保护科学设计研究院 The device and method of double-dielectric barrier discharge plasma excitation catalytic gas phase reaction processing organic exhaust gas
CN209576241U (en) * 2018-12-13 2019-11-05 浙江省环境保护科学设计研究院 The device of double-dielectric barrier discharge plasma excitation catalytic gas phase reaction processing organic exhaust gas
CN111467960A (en) * 2020-05-22 2020-07-31 上海大学 Novel low-temperature plasma catalyzing device

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030070931A (en) * 2002-02-27 2003-09-03 한국에너지기술연구원 Multi layer non-thermal plasma/catalyst reactor
CN103933897A (en) * 2014-04-09 2014-07-23 杭州尊邦科技有限公司 Embedded-type plasma reactor for performing adsorption catalysis on VOCs (volatile organic chemicals) as well as method
CN108355486A (en) * 2018-03-07 2018-08-03 广州握胜环保科技有限公司 Low-temperature plasma synergistic catalytic unit
CN108543537A (en) * 2018-04-18 2018-09-18 清华大学 It a kind of cobalt Mn complex oxide catalyst and its prepares and the method for coupled plasma cleaning organic waste gas
CN109364706A (en) * 2018-12-13 2019-02-22 浙江省环境保护科学设计研究院 The device and method of double-dielectric barrier discharge plasma excitation catalytic gas phase reaction processing organic exhaust gas
CN209576241U (en) * 2018-12-13 2019-11-05 浙江省环境保护科学设计研究院 The device of double-dielectric barrier discharge plasma excitation catalytic gas phase reaction processing organic exhaust gas
CN111467960A (en) * 2020-05-22 2020-07-31 上海大学 Novel low-temperature plasma catalyzing device

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113070012A (en) * 2021-03-16 2021-07-06 浙江理工大学 Reaction device and method for generating methanol by using carbon dioxide and hydrogen
CN113070012B (en) * 2021-03-16 2023-02-10 浙江理工大学 Reaction device and method for generating methanol by using carbon dioxide and hydrogen
CN113458138A (en) * 2021-07-07 2021-10-01 合肥学院 Experimental method for repairing fluorene contaminated soil
CN113600180A (en) * 2021-07-16 2021-11-05 浙江工业大学 MnO based on KOH modification2Composite TiO2Preparation method and application of composite catalyst
CN114918242A (en) * 2022-05-07 2022-08-19 浙江大学 Micro-plastic contaminated soil remediation device and method based on coaxial DBD plasma technology
CN114918242B (en) * 2022-05-07 2023-06-23 浙江大学 Microplastic polluted soil restoration device and method based on coaxial DBD plasma technology

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