CN112023690A - VOCs waste gas treatment system and VOCs waste gas treatment method - Google Patents
VOCs waste gas treatment system and VOCs waste gas treatment method Download PDFInfo
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- CN112023690A CN112023690A CN202010870820.1A CN202010870820A CN112023690A CN 112023690 A CN112023690 A CN 112023690A CN 202010870820 A CN202010870820 A CN 202010870820A CN 112023690 A CN112023690 A CN 112023690A
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- spray tower
- stop valve
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- temperature plasma
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- 238000000034 method Methods 0.000 title claims abstract description 56
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
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- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
- B01D53/007—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by irradiation
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- 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
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1406—Multiple stage absorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1487—Removing organic compounds
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- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- B01J23/72—Copper
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- B01J35/391—
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/804—UV light
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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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
Abstract
The invention belongs to the field of environmental protection, and particularly relates to a VOCs waste gas treatment system and a VOCs waste gas treatment method. The treatment system provided by the invention comprises a first spray tower, a second spray tower, a low-temperature plasma reactor, a UV photocatalytic ozone reactor and an oxygen generator. The invention sets up the spray column at both ends respectively before and after the low-temperature plasma reactor, two spray columns circulate and connect and form the water circulation enrichment system; when the circulating water in the spray towers absorbs VOCs and is gradually saturated, the circulating water is pumped into the UV photocatalytic ozone reactor, a stop valve between the low-temperature plasma reactor and the two spray towers is closed, the low-temperature plasma reactor and the UV photocatalytic ozone reactor form a low-temperature plasma composite liquid-phase photocatalytic treatment system independent of the waste gas treatment system, high-activity free radicals associated in the low-temperature plasma are dissolved in a water body and then subjected to UV photocatalysis, and the deep mineralization treatment is carried out on the VOCs in the water body.
Description
Technical Field
The invention belongs to the field of environmental protection, and particularly relates to a VOCs waste gas treatment system and a VOCs waste gas treatment method.
Background
The traditional VOCs end treatment method has many forms, and mainly comprises two links of collection and destruction. Such as: activated carbon adsorption, zeolite wheel adsorption concentration, absorption method and condensation method; the destroying mode mainly comprises the following steps: direct combustion, catalytic oxidation, regenerative combustion (RTO), UV photocatalytic, biological, low temperature plasma processes.
As numerous small and medium-sized enterprises cannot bear the high construction cost and subsequent operation cost of zeolite rotating wheels and RTO (regenerative thermal oxidizer) or activated carbon adsorption and RTO, the low-temperature plasma treatment technology is used for treating VOCs (volatile organic chemicals) in a large scale due to low construction cost, good treatment effect and wide application range.
The traditional low-temperature plasma technology has the problems that the surface of a reactor is easy to be polluted, so that the degradation effect is reduced, secondary pollution to the environment caused by ozone generation exists in the treatment process, and the like. In response to these problems, those skilled in the art have made improvements in low temperature plasma technology, such as adding an ozone degradation catalyst at the end to eliminate the side effects of ozone, or adding water wash to eliminate ozone or to effect absorption of contaminants. However, these improvements are not effective in solving the waste of ozone as a strong oxidant and the water pollution caused by the transfer of pollutants, which increases the cost of wastewater treatment for enterprises.
Disclosure of Invention
In view of this, the present invention aims to provide a system and a method for treating VOCs waste gas, which have good effect of treating VOCs waste gas, can realize zero discharge of wastewater and ozone, and are low in operation cost, clean and environment-friendly.
The invention provides a VOCs waste gas treatment system, which comprises:
the first spray tower is provided with a gas inlet, a gas outlet, a spray liquid inlet and a tower kettle liquid outlet;
the low-temperature plasma reactor is provided with an air inlet and an air outlet; the gas inlet of the low-temperature plasma reactor is connected with the gas outlet of the first spray tower, and a first stop valve is arranged on a connecting pipeline of the low-temperature plasma reactor;
the second spray tower is provided with a gas inlet, a gas outlet, a spray liquid inlet, a first tower kettle liquid outlet, a second tower kettle liquid outlet and a tower kettle liquid reflux opening; the gas inlet of the second spray tower is connected with the gas outlet of the low-temperature plasma reactor, and a second stop valve is arranged on a connecting pipeline of the second spray tower; a spray liquid inlet of the second spray tower is connected with a tower kettle liquid outlet of the first spray tower, and a first circulating pump is arranged on a connecting pipeline of the second spray tower; a first tower kettle liquid outlet of the second spray tower is connected with a spray liquid inlet of the first spray tower, and a second circulating pump is arranged on a connecting pipeline of the second spray tower;
the UV photocatalytic ozone reactor is provided with an air inlet, an air outlet, a liquid inlet and a liquid outlet; a liquid inlet of the UV photocatalytic ozone reactor is connected with a second tower kettle liquid outlet of the second spray tower, and a third stop valve is arranged on a connecting pipeline of the UV photocatalytic ozone reactor; a liquid outlet of the UV photocatalytic ozone reactor is connected with a tower bottom liquid reflux port of the second spray tower, and a third circulating pump and a fourth stop valve are arranged on a connecting pipeline of the UV photocatalytic ozone reactor; the air inlet of the UV photocatalytic ozone reactor is connected with the air outlet of the low-temperature plasma reactor, and a fifth stop valve is arranged on a connecting pipeline of the UV photocatalytic ozone reactor; the gas outlet of the UV photocatalytic ozone reactor is connected with the gas inlet of the low-temperature plasma reactor, and a fourth circulating pump and a sixth stop valve are arranged on a connecting pipeline of the UV photocatalytic ozone reactor;
and an oxygen outlet of the oxygen generator is connected with an air inlet of the low-temperature plasma reactor, and a seventh stop valve is arranged on a connecting pipeline of the oxygen generator.
Preferably, the treatment system further comprises a pH control device for controlling the pH value of the first spray tower.
Preferably, the treatment system further comprises a liquid level compensation device for supplementing fresh process water into the UV photocatalytic ozone reactor.
Preferably, the treatment system further comprises a COD detection device for detecting the COD value of the water body in the UV photocatalytic ozone reactor.
Preferably, the catalyst filled in the UV photocatalytic ozone reactor is a monatomic catalyst.
Preferably, the monatomic catalyst is prepared according to the following steps:
a) mixing an active metal source compound, a single atom catalyst carrier and a solvent, stirring and drying to obtain a single atom catalyst precursor;
b) and reducing and calcining the monatomic catalyst precursor in a hydrogen-helium mixed atmosphere to obtain the monatomic catalyst.
Preferably, in step a), the monatomic catalyst support is prepared according to the following steps:
and carrying out solvothermal reaction on hexadecyl trimethyl ammonium bromide and a titanium source compound in a solvent to obtain the monatomic catalyst carrier.
Preferably, in step a), the active metal source compound includes one or more of a Cu source compound, a Fe source compound, an Au source compound, a Pt source compound, and a Pd source compound.
Preferably, in the step b), the calcining temperature is 100-400 ℃; the calcining time is 30-120 min.
The invention provides a method for treating VOCs waste gas in a treatment system in the technical scheme, which comprises the following steps:
A) opening a first stop valve and a second stop valve, starting a first circulating pump and a second circulating pump, and then sending VOCs waste gas into a gas inlet of a first spray tower, wherein the VOCs waste gas is washed by water in the first spray tower, low-temperature plasma in a low-temperature plasma reactor and secondary water in a second spray tower in sequence, and treated waste gas is obtained at a gas outlet of the second spray tower;
B) in the VOCs waste gas treatment process, the washing liquid in the first spray tower and the second spray tower is gradually absorbed and saturated, and the washing effect is reduced; when the concentration of VOCs in the treated waste gas discharged from the gas outlet of the second spray tower exceeds a set value, closing the second circulating pump, opening a third stop valve, pumping tower bottom liquid in the first spray tower into the second spray tower through the first circulating pump, and then entering the UV photocatalytic ozone reactor along with the tower bottom liquid of the second spray tower;
C) after the first spray tower kettle liquid and the second spray tower kettle liquid are all fed into the UV photo-catalytic ozone reactor, closing the first circulating pump, the first stop valve, the second stop valve and the third stop valve, opening the fifth stop valve, the sixth stop valve and the seventh stop valve, starting the oxygen generator to inject a certain amount of oxygen into the low-temperature plasma reactor, closing the oxygen generator and the seventh stop valve, carrying out plasma generation on the injected oxygen in the low-temperature plasma reactor, feeding the low-temperature plasma generated by the oxygen into the UV photo-catalytic ozone reactor, starting a UV irradiation device of the UV photo-catalytic ozone reactor, and carrying out synergistic treatment on the water in the UV photo-catalytic ozone reactor by using the low-temperature plasma generated by the oxygen and the UV light; during the period, the fourth circulating pump is started, and the gas in the system flows through the fourth circulating pump to form a closed loop;
D) in the cooperative treatment process, the COD value of the water body in the UV photocatalytic ozone reactor is gradually reduced, when the COD value is lower than a set value, the UV irradiation devices of the low-temperature plasma reactor and the UV photocatalytic ozone reactor are closed, after the ozone in the closed loop is metabolized to be completely decomposed, the fifth stop valve, the sixth stop valve and the fourth circulating pump are closed, the fourth stop valve is opened, the third circulating pump is started, the water body in the UV photocatalytic ozone reactor is pumped back to the second spray tower, and the third circulating pump and the fourth stop valve are closed after the pumping is finished; and then carrying out the next round of the operations A) to D).
Compared with the prior art, the invention provides a VOCs waste gas treatment system and a VOCs waste gas treatment method. The treatment system provided by the invention comprises a first spray tower, wherein an air inlet, an air outlet, a spray liquid inlet and a tower bottom liquid outlet are formed in the first spray tower; the low-temperature plasma reactor is provided with an air inlet and an air outlet; the gas inlet of the low-temperature plasma reactor is connected with the gas outlet of the first spray tower, and a first stop valve is arranged on a connecting pipeline of the low-temperature plasma reactor; the second spray tower is provided with a gas inlet, a gas outlet, a spray liquid inlet, a first tower kettle liquid outlet, a second tower kettle liquid outlet and a tower kettle liquid reflux opening; the gas inlet of the second spray tower is connected with the gas outlet of the low-temperature plasma reactor, and a second stop valve is arranged on a connecting pipeline of the second spray tower; a spray liquid inlet of the second spray tower is connected with a tower kettle liquid outlet of the first spray tower, and a first circulating pump is arranged on a connecting pipeline of the second spray tower; a first tower kettle liquid outlet of the second spray tower is connected with a spray liquid inlet of the first spray tower, and a second circulating pump is arranged on a connecting pipeline of the second spray tower; the UV photocatalytic ozone reactor is provided with an air inlet, an air outlet, a liquid inlet and a liquid outlet; a liquid inlet of the UV photocatalytic ozone reactor is connected with a second tower kettle liquid outlet of the second spray tower, and a third stop valve is arranged on a connecting pipeline of the UV photocatalytic ozone reactor; a liquid outlet of the UV photocatalytic ozone reactor is connected with a tower bottom liquid reflux port of the second spray tower, and a third circulating pump and a fourth stop valve are arranged on a connecting pipeline of the UV photocatalytic ozone reactor; the air inlet of the UV photocatalytic ozone reactor is connected with the air outlet of the low-temperature plasma reactor, and a fifth stop valve is arranged on a connecting pipeline of the UV photocatalytic ozone reactor; the gas outlet of the UV photocatalytic ozone reactor is connected with the gas inlet of the low-temperature plasma reactor, and a fourth circulating pump and a sixth stop valve are arranged on a connecting pipeline of the UV photocatalytic ozone reactor; and an oxygen outlet of the oxygen generator is connected with an air inlet of the low-temperature plasma reactor, and a seventh stop valve is arranged on a connecting pipeline of the oxygen generator. The specific process for treating the VOCs waste gas in the system comprises the following steps of A) opening a first stop valve and a second stop valve, starting a first circulating pump and a second circulating pump, and then sending the VOCs waste gas into a gas inlet of a first spray tower, wherein the VOCs waste gas is washed by water in the first spray tower, low-temperature plasma in a low-temperature plasma reactor and secondary water in a second spray tower in sequence, and treated waste gas is obtained at a gas outlet of the second spray tower; B) in the VOCs waste gas treatment process, the washing liquid in the first spray tower and the second spray tower is gradually absorbed and saturated, and the washing effect is reduced; when the concentration of VOCs in the treated waste gas discharged from the gas outlet of the second spray tower exceeds a set value, closing the second circulating pump, opening a third stop valve, pumping tower bottom liquid in the first spray tower into the second spray tower through the first circulating pump, and then entering the UV photocatalytic ozone reactor along with the tower bottom liquid of the second spray tower; C) after the first spray tower kettle liquid and the second spray tower kettle liquid are all fed into the UV photo-catalytic ozone reactor, closing the first circulating pump, the first stop valve, the second stop valve and the third stop valve, opening the fifth stop valve, the sixth stop valve and the seventh stop valve, starting the oxygen generator to inject a certain amount of oxygen into the low-temperature plasma reactor, closing the oxygen generator and the seventh stop valve, carrying out plasma generation on the injected oxygen in the low-temperature plasma reactor, feeding the low-temperature plasma generated by the oxygen into the UV photo-catalytic ozone reactor, starting a UV irradiation device of the UV photo-catalytic ozone reactor, and carrying out synergistic treatment on the water in the UV photo-catalytic ozone reactor by using the low-temperature plasma generated by the oxygen and the UV light; during the period, the fourth circulating pump is started, and the gas in the system flows through the fourth circulating pump to form a closed loop; D) in the cooperative treatment process, the COD value of the water body in the UV photocatalytic ozone reactor is gradually reduced, when the COD value is lower than a set value, the UV irradiation devices of the low-temperature plasma reactor and the UV photocatalytic ozone reactor are closed, after the ozone in the closed loop is metabolized to be completely decomposed, the fifth stop valve, the sixth stop valve and the fourth circulating pump are closed, the fourth stop valve is opened, the third circulating pump is started, the water body in the UV photocatalytic ozone reactor is pumped back to the second spray tower, and the third circulating pump and the fourth stop valve are closed after the pumping is finished; and then carrying out the next round of the operations A) to D). The treatment system provided by the invention is characterized in that spray towers are respectively arranged at the front end and the rear end of a low-temperature plasma reactor, the two spray towers are circularly connected to form a water circulation enrichment system for removing dust, paint mist, water-soluble VOCs, acid-base gas, regenerated water-soluble VOCs, ozone and the like in flue gas, and the ozone collected by the tail spray tower is used for cooperatively treating the water-soluble VOCs dissolved in the pretreated flue gas and a regenerated water-soluble byproduct generated by low-temperature plasma decomposition; when the circulating water in the spray towers absorbs VOCs and is gradually saturated, the circulating water is pumped into the UV photo-catalytic ozone reactor, a stop valve between the low-temperature plasma reactor and the two spray towers is closed, so that the low-temperature plasma reactor and the UV photo-catalytic ozone reactor form a liquid-phase photo-catalytic treatment system independent of the waste gas treatment system, then a certain amount of oxygen is injected into the low-temperature plasma reactor, the oxygen in the system continuously circulates between the low-temperature plasma reactor and the UV photo-catalytic ozone reactor, the oxygen and water vapor brought out from the UV photo-catalytic ozone reactor due to the oxygen circulation generate a large amount of ozone and active hydroxyl radicals through the low-temperature plasma reactor, under the UV photo-catalytic condition, the VOCs in the water body in the UV photo-catalytic ozone reactor are deeply mineralized and treated, and after the treatment of the VOCs in the water body is finished, the UV irradiation devices of the low-temperature plasma reactor and the UV photo-catalytic ozone reactor are closed, continuously circulating until the concentration of the ozone in the system is zero, and then entering the next treatment period. The treatment system provided by the invention integrates a low-temperature plasma technology and a liquid-phase photocatalysis technology, has a good VOCs waste gas treatment effect, can realize zero wastewater discharge and zero ozone discharge, is low in operation cost, is clean and environment-friendly, and has a very wide market prospect.
In the preferred technical scheme of the invention, the monatomic catalyst prepared by a specific method is used as the catalyst filled in the UV photocatalytic ozone reactor, and the atom utilization rate and the cost of the monatomic catalyst adopted by the invention are far lower than those of a common catalyst; the dynamic size of the catalyst is about 500nm, the catalyst presents a sea urchin-shaped three-dimensional structure, the catalyst is more in accordance with a bionic structure, a homogeneous solution can be quickly formed with the solution, and meanwhile, the catalyst can be quickly settled in a static state, so that the catalyst can more fully absorb light energy under the irradiation of UV light and promote the reaction; in addition, the carrier surface of the catalyst has a large number of defect sites in the crystallization process, so that the active phase metal can be promoted to be bonded on the carrier surface in a monoatomic form, and the catalyst has longer service life and electron transfer rate.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a process flow diagram of a VOCs exhaust treatment system according to an embodiment of the present invention;
FIG. 2 is a scanning electron microscope transmission mode (STEM) view of a titania carrier provided in example 2 of the present invention;
FIG. 3 is a scanning electron microscopy transmission mode (STEM) view of the monatomic catalyst provided in example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be 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.
The invention provides a VOCs waste gas treatment system, which comprises:
the first spray tower is provided with a gas inlet, a gas outlet, a spray liquid inlet and a tower kettle liquid outlet;
the low-temperature plasma reactor is provided with an air inlet and an air outlet; the gas inlet of the low-temperature plasma reactor is connected with the gas outlet of the first spray tower, and a first stop valve is arranged on a connecting pipeline of the low-temperature plasma reactor;
the second spray tower is provided with a gas inlet, a gas outlet, a spray liquid inlet, a first tower kettle liquid outlet, a second tower kettle liquid outlet and a tower kettle liquid reflux opening; the gas inlet of the second spray tower is connected with the gas outlet of the low-temperature plasma reactor, and a second stop valve is arranged on a connecting pipeline of the second spray tower; a spray liquid inlet of the second spray tower is connected with a tower kettle liquid outlet of the first spray tower, and a first circulating pump is arranged on a connecting pipeline of the second spray tower; a first tower kettle liquid outlet of the second spray tower is connected with a spray liquid inlet of the first spray tower, and a second circulating pump is arranged on a connecting pipeline of the second spray tower;
the UV photocatalytic ozone reactor is provided with an air inlet, an air outlet, a liquid inlet and a liquid outlet; a liquid inlet of the UV photocatalytic ozone reactor is connected with a second tower kettle liquid outlet of the second spray tower, and a third stop valve is arranged on a connecting pipeline of the UV photocatalytic ozone reactor; a liquid outlet of the UV photocatalytic ozone reactor is connected with a tower bottom liquid reflux port of the second spray tower, and a third circulating pump and a fourth stop valve are arranged on a connecting pipeline of the UV photocatalytic ozone reactor; the air inlet of the UV photocatalytic ozone reactor is connected with the air outlet of the low-temperature plasma reactor, and a fifth stop valve is arranged on a connecting pipeline of the UV photocatalytic ozone reactor; the gas outlet of the UV photocatalytic ozone reactor is connected with the gas inlet of the low-temperature plasma reactor, and a fourth circulating pump and a sixth stop valve are arranged on a connecting pipeline of the UV photocatalytic ozone reactor;
and an oxygen outlet of the oxygen generator is connected with an air inlet of the low-temperature plasma reactor, and a seventh stop valve is arranged on a connecting pipeline of the oxygen generator.
Referring to fig. 1, fig. 1 is a process flow diagram of a VOCs waste gas treatment system according to an embodiment of the present invention, in fig. 1, 1 denotes a first spray tower, 2 denotes a low-temperature plasma reactor, 3 denotes a second spray tower, 4 denotes a UV photo-catalytic ozone reactor, 5 denotes an oxygen generator, 6 denotes a pH control device, 7 denotes a liquid level compensation device, 8 denotes a COD detection device, 9-1 denotes a first cut-off valve, 9-2 denotes a second cut-off valve, 9-3 denotes a third cut-off valve, 9-4 denotes a fourth cut-off valve, 9-5 denotes a fifth cut-off valve, 9-6 denotes a sixth cut-off valve, 9-7 denotes a seventh cut-off valve, 10-1 denotes a first circulation pump, 10-2 denotes a second circulation pump, 10-3 denotes a third circulation pump, and 10-4 denotes a fourth circulation pump.
The VOCs waste gas treatment system provided by the invention comprises a first spray tower 1, a low-temperature plasma reactor 2, a second spray tower 3, a UV photocatalytic ozone reactor 4 and an oxygen generator 5. Wherein, the first spray tower 1 is provided with an air inlet, an air outlet, a spray liquid inlet and a tower bottom liquid outlet.
In the treatment system provided by the invention, the low-temperature plasma reactor 2 is provided with an air inlet and an air outlet. In the invention, the gas inlet of the low-temperature plasma reactor 2 is connected with the gas outlet of the first spray tower 1, and the connecting pipeline of the low-temperature plasma reactor is provided with a first stop valve 9-1. In one embodiment provided by the present invention, the low temperature plasma generation form of the low temperature plasma reactor 2 is a dual dielectric barrier discharge.
In the treatment system provided by the invention, the second spray tower 3 is provided with an air inlet, an air outlet, a spray liquid inlet, a first tower bottom liquid outlet, a second tower bottom liquid outlet and a tower bottom liquid reflux opening. In the invention, the air inlet of the second spray tower 3 is connected with the air outlet of the low-temperature plasma reactor 2, and the connecting pipeline of the second spray tower is provided with a second stop valve 9-2; a spray liquid inlet of the second spray tower 3 is connected with a tower kettle liquid outlet of the first spray tower 1, and a first circulating pump 10-1 is arranged on a connecting pipeline of the second spray tower 3; the first tower bottom liquid outlet of the second spray tower 3 is connected with the spray liquid inlet of the first spray tower 1, and a second circulating pump 10-2 is arranged on the connecting pipeline.
In the treatment system provided by the invention, the UV photocatalytic ozone reactor 4 is provided with an air inlet, an air outlet, a liquid inlet and a liquid outlet, a UV irradiation device is arranged in an inner cavity, the power of the UV irradiation device is preferably 2kW, and the irradiation wavelength is preferably less than or equal to 185 nm. In the invention, a liquid inlet of the UV photocatalytic ozone reactor 4 is connected with a second tower kettle liquid outlet of the second spray tower 3, and a third stop valve 9-3 is arranged on a connecting pipeline of the UV photocatalytic ozone reactor; a liquid outlet of the UV photocatalytic ozone reactor 4 is connected with a tower bottom liquid return port of the second spray tower 3, and a third circulating pump 10-3 and a fourth stop valve 9-4 are arranged on a connecting pipeline of the UV photocatalytic ozone reactor 4; an air inlet of the UV photocatalytic ozone reactor 4 is connected with an air outlet of the low-temperature plasma reactor 2, and a fifth stop valve 9-5 is arranged on a connecting pipeline of the UV photocatalytic ozone reactor 4; the air outlet of the UV photocatalytic ozone reactor 4 is connected with the air inlet of the low-temperature plasma reactor 2, and a fourth circulating pump 10-4 and a sixth stop valve 9-6 are arranged on the connecting pipeline of the UV photocatalytic ozone reactor.
In the treatment system provided by the invention, the oxygen generator 5 is provided with an oxygen outlet. In the invention, an oxygen outlet of the oxygen generator 5 is connected with an air inlet of the low-temperature plasma reactor 2, and a connecting pipeline of the oxygen generator is provided with seventh stop valves 9-7.
In the treatment system provided by the invention, the system preferably further comprises a pH control device 6, and the pH control device 6 is connected with the first spray tower 1 and is used for controlling the pH value of the first spray tower 1.
In the treatment system provided by the present invention, the system preferably further comprises a liquid level compensation device 7, wherein the liquid level compensation device 7 is connected to the UV photo-catalytic ozone reactor 4, and is used for supplementing fresh process water into the UV photo-catalytic ozone reactor 4 to maintain the liquid level of the UV photo-catalytic ozone reactor 4, and further maintain the liquid levels of the tower bottoms of the first spray tower 1 and the second spray tower 3.
In the treatment system provided by the invention, the system preferably further comprises a COD detection device 8, wherein the COD detection device 8 is connected with the UV photocatalytic ozone reactor 4 and is used for detecting the COD value of the water body in the UV photocatalytic ozone reactor 4.
In the treatment system provided by the invention, the catalyst filled in the UV photocatalytic ozone reactor 4 is preferably a monatomic catalyst prepared according to the following steps:
a) mixing an active metal source compound, a single atom catalyst carrier and a solvent, stirring and drying to obtain a single atom catalyst precursor;
b) and reducing and calcining the monatomic catalyst precursor in a hydrogen-helium mixed atmosphere to obtain the monatomic catalyst.
In the preparation step of the monatomic catalyst provided by the present invention, a monatomic catalyst carrier is first prepared, and the monatomic catalyst carrier is preferably prepared according to the following steps:
cetyl Trimethyl Ammonium Bromide (CTAB) and a titanium source compound are subjected to solvothermal reaction in a solvent to obtain the monatomic catalyst carrier.
In the above-mentioned preparation step of the monoatomic catalyst support provided by the present invention, the titanium source compound preferably includes titanium trichloride; the solvent preferably comprises n-hexane and/or n-pentanol, and the volume ratio of the n-hexane to the n-pentanol is preferably (3-10): 1, more preferably 6: 1; the preferable dosage ratio of CTAB to the solvent is (100-1000) g: 7L, more preferably 600 g: 7L; the dosage ratio of the titanium source compound to the solvent is preferably (10-50) g: 7L, specifically 10 g: 7L, 15 g: 7L, 20 g: 7L, 25 g: 7L, 30 g: 7L, 35 g: 7L, 40 g: 7L, 45 g: 7L or 50 g: 7L; the specific process of the solvothermal reaction preferably comprises: firstly, mixing cetyl trimethyl ammonium bromide with a solvent, then mixing the mixture with a titanium salt aqueous solution, then heating for reaction, and finally carrying out solid-liquid separation, cleaning and drying on a product obtained by the reaction to obtain the monatomic catalyst carrier. Wherein the reaction temperature is preferably 170-250 ℃, and more preferably 200 ℃; the reaction time is preferably 1-12 h.
In the above-mentioned monatomic catalyst preparation step provided by the present invention, after the monatomic catalyst carrier is obtained, the monatomic catalyst carrier, the active metal source compound, and the solvent are mixed. Wherein the active metal source compound preferably comprises one or more of a Cu source compound, a Fe source compound, an Au source compound, a Pt source compound, and a Pd source compound, and more preferably comprises one or more of copper nitrate, iron nitrate, chloroauric acid, chloroplatinic acid, and palladium nitrate; the solvent is preferably ethanol; the preferred dosage ratio of the monatomic catalyst carrier to the solvent is (5-30) g: 4L, more preferably (10-15) g: 4L; the metal atom in the active metal source compound accounts for 0.01-0.1 wt% of the mass of the single-atom catalyst carrier, and more preferably accounts for 0.05 wt%; the specific process of mixing preferably comprises: the monatomic catalyst support and the solvent are first ultrasonically mixed, and then ultrasonically mixed with an aqueous solution of an active metal source compound. And after uniformly mixing, stirring and drying to obtain the monatomic catalyst precursor.
In the preparation step of the monatomic catalyst provided by the invention, after the monatomic catalyst precursor is obtained, the monatomic catalyst precursor is subjected to reduction calcination in a hydrogen-helium mixed atmosphere. Wherein, the hydrogen content in the hydrogen-helium mixed atmosphere is preferably 5-15 vol%, and more preferably 10 vol%; the calcination temperature is preferably 100-400 ℃, and specifically can be 100 ℃, 125 ℃, 150 ℃, 175 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃ or 400 ℃; the calcination time is preferably 30-120 min, and specifically can be 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min or 120 min. And after reduction, calcination and sintering, cooling to obtain the monatomic catalyst.
The treatment system provided by the invention integrates a low-temperature plasma technology and a liquid-phase photocatalysis technology, has a good VOCs waste gas treatment effect, can realize zero wastewater discharge and zero ozone discharge, is low in operation cost, is clean and environment-friendly, and has a very wide market prospect. More specifically, the abatement system provided by the invention has at least the following advantages:
1) the treatment system provided by the invention can reduce solid waste generated by using a filter bag in the flue gas pretreatment process by arranging the spray towers in front of and behind the low-temperature plasma reactor to form a water circulation enrichment system, and can realize the primary treatment of VOCs in water by utilizing ozone resources through water circulation enrichment, thereby achieving zero ozone emission.
2) The treatment system provided by the invention can realize closed cycle of the low-temperature plasma reactor and the UV photocatalytic ozone reactor through the control of the stop valve and the pump, then a certain amount of oxygen is injected into the low-temperature plasma reactor, the oxygen is continuously circulated between the low-temperature plasma reactor and the UV photocatalytic ozone reactor, the oxygen and water vapor brought out from the UV photocatalytic ozone reactor due to the circulation of the oxygen pass through the low-temperature plasma reactor to generate a large amount of ozone and active hydroxyl radicals, under the UV photocatalytic condition, deep mineralization treatment is carried out on VOCs in a water body in the UV photocatalytic ozone reactor, after the treatment of the VOCs in the water body is finished, the UV irradiation devices of the low-temperature plasma reactor and the UV photocatalytic ozone reactor are closed, the circulation is continuously carried out until the concentration of the ozone in the system is zero, and then the next treatment period is carried out. The invention can realize zero discharge of wastewater and ozone through the closed cycle, has low operation cost, and is clean and environment-friendly.
3) In the preferred technical scheme of the invention, the monatomic catalyst prepared by a specific method is used as the catalyst filled in the UV photocatalytic ozone reactor, and the atom utilization rate and the cost of the monatomic catalyst adopted by the invention are far lower than those of a common catalyst; the dynamic size of the catalyst is about 500nm, the catalyst presents a sea urchin-shaped three-dimensional structure, the catalyst is more in accordance with a bionic structure, a homogeneous solution can be quickly formed with the solution, and meanwhile, the catalyst can be quickly settled in a static state, so that the catalyst can more fully absorb light energy under the irradiation of UV light and promote the reaction; in addition, the carrier surface of the catalyst has a large number of defect sites in the crystallization process, so that the active phase metal can be promoted to be bonded on the carrier surface in a monoatomic form, and the catalyst has longer service life and electron transfer rate.
The invention also provides a method for treating the VOCs waste gas in the treatment system in the technical scheme, which comprises the following steps:
A) opening a first stop valve 9-1 and a second stop valve 9-2, starting a first circulating pump 10-1 and a second circulating pump 10-2, and then sending VOCs waste gas into a gas inlet of a first spray tower 1, wherein the VOCs waste gas is washed by water of the first spray tower 1, low-temperature plasma treatment of a low-temperature plasma reactor 2 and secondary water of a second spray tower 3 in sequence, and treated waste gas is obtained at a gas outlet of the second spray tower 3;
B) in the VOCs waste gas treatment process, the washing liquid in the first spray tower 1 and the second spray tower 3 is gradually absorbed and saturated, and the washing effect is reduced; when the concentration of VOCs in the treated waste gas discharged from the gas outlet of the second spray tower 3 exceeds a set value, closing the second circulating pump 10-2, opening the third stop valve 9-3, pumping tower bottom liquid in the first spray tower 1 into the second spray tower 3 through the first circulating pump 10-1, and then entering the UV photocatalytic ozone reactor 4 along with tower bottom liquid in the second spray tower 3;
C) after the tower bottom liquid of the first spray tower 1 and the tower bottom liquid of the second spray tower 3 are all fed into the UV photocatalytic ozone reactor 4, closing a first circulating pump 10-1, a first stop valve 9-1, a second stop valve 9-2 and a third stop valve 9-3, opening a fifth stop valve 9-5, a sixth stop valve 9-6 and a seventh stop valve 9-7, starting the oxygen generator 5 to inject a certain amount of oxygen into the low-temperature plasma reactor 2, then closing the oxygen generator 5 and the seventh stop valve 9-7, carrying out plasma generation on the injected oxygen in the low-temperature plasma reactor, then enabling low-temperature plasma generated by the oxygen to enter the UV photocatalytic ozone reactor 4, starting a UV irradiation device of the UV photocatalytic ozone reactor 4, and carrying out synergistic treatment on the water in the UV photocatalytic ozone reactor 4 by using the low-temperature plasma generated by the oxygen and UV light; during the period, the fourth circulating pump 10-4 is started, and the gas in the system flows through the fourth circulating pump 10-4 to form a closed loop;
D) in the cooperative treatment process, the COD value of the water in the UV photocatalytic ozone reactor 4 is gradually reduced, when the COD value is lower than a set value, the UV irradiation devices of the low-temperature plasma reactor 2 and the UV photocatalytic ozone reactor 4 are closed, after the ozone in the closed loop is metabolized to be completely decomposed, the fifth stop valve 9-5, the sixth stop valve 9-6 and the fourth circulating pump 10-4 are closed, then the fourth stop valve 9-4 is opened, the third circulating pump 10-3 is started, the water in the UV photocatalytic ozone reactor is pumped back to the second spray tower 3, and after the pumping is finished, the third circulating pump 10-3 and the fourth stop valve 9-4 are closed; and then carrying out the next round of the operations A) to D).
In the treatment method provided by the invention, in the operation process of the first spray tower 1 and the second spray tower 3, the pH value of the spray liquid is preferably regulated, and the pH value of the tower bottom liquid of the first spray tower 1 is more preferably regulated; the pH regulation range is preferably 2-12, and more preferably about 7. In the present invention, the pH control is preferably performed by a pH control device 6.
In the treatment method provided by the invention, in the operation process of the first spray tower 1 and the second spray tower 3, liquid storage sections are required to be arranged at the bottom ends of the first spray tower 1 and the second spray tower 3, and the volumes of the liquid storage sections are preferably 1.1-1.2 times of the liquid phase volumes corresponding to the minimum liquid-gas ratio when the first spray tower 1 and the second spray tower 3 operate respectively. In the present invention, it is preferable to maintain the liquid levels of the first and second spray towers 1 and 3 during operation by increasing the amount of liquid in the entire system by supplementing fresh process water into the UV photocatalytic ozone reactor 4, and it is more preferable to realize the liquid level compensation device 7. In one embodiment of the present invention, when the liquid level in the UV photo-catalytic ozone reactor 4 is lower than a predetermined value, the liquid level compensation device 7 automatically supplies fresh process water to the UV photo-catalytic ozone reactor 4.
In the treatment method provided by the invention, the COD value of the water body in the UV photocatalytic ozone reactor 4 is preferably monitored by a COD detection device 8.
In the treatment method provided by the invention, in the step B), no rigid requirement is required for the set value of the concentration of the VOCs, and the set value can be set to be 5-50 mg/m under certain treatment working conditions3More specifically, it may be 10mg/m3。
In the abatement method provided by the present invention, in step C), the amount of oxygen injected is not particularly limited, and the amount of oxygen injected into the system in an integrated manner may be matched with the circulation air volume set by the fourth circulation pump 10-4.
In the treatment method provided by the invention, in the step D), no rigid requirement is required for the set value of the COD value, and the set value can be set to be 500-2000 mg/L, more specifically 1000mg/L under certain treatment working conditions.
The treatment method provided by the invention treats the VOCs waste gas in the treatment system provided by the invention, has good VOCs waste gas treatment effect, can realize zero discharge of waste water and zero discharge of ozone, has low operation cost, and is clean and environment-friendly.
For the sake of clarity, the following examples are given in detail.
Example 1
(1) A VOCs exhaust treatment system as shown in FIG. 1 specifically includes: the device comprises a first spray tower 1, a low-temperature plasma reactor 2, a second spray tower 3, a UV photocatalytic ozone reactor 4, an oxygen generator 5, a pH regulation and control device 6, a liquid level compensation device 7 and a COD detection device 8;
wherein, the first spray tower 1 is provided with a gas inlet, a gas outlet, a spray liquid inlet and a tower bottom liquid outlet;
the low-temperature plasma generation form of the low-temperature plasma reactor 2 is double-medium barrier discharge, and an air inlet and an air outlet are arranged on the low-temperature plasma reactor; the gas inlet of the low-temperature plasma reactor 2 is connected with the gas outlet of the first spray tower 1, and a first stop valve 9-1 is arranged on a connecting pipeline of the low-temperature plasma reactor;
the second spray tower 3 is provided with a gas inlet, a gas outlet, a spray liquid inlet, a first tower kettle liquid outlet, a second tower kettle liquid outlet and a tower kettle liquid reflux opening; the gas inlet of the second spray tower 3 is connected with the gas outlet of the low-temperature plasma reactor 2, and a second stop valve 9-2 is arranged on a connecting pipeline of the second spray tower; a spray liquid inlet of the second spray tower 3 is connected with a tower kettle liquid outlet of the first spray tower 1, and a first circulating pump 10-1 is arranged on a connecting pipeline of the second spray tower 3; a first tower kettle liquid outlet of the second spray tower 3 is connected with a spray liquid inlet of the first spray tower 1, and a second circulating pump 10-2 is arranged on a connecting pipeline of the first spray tower and the second spray tower;
the UV photocatalytic ozone reactor 4 is provided with an air inlet, an air outlet, a liquid inlet and a liquid outlet, a UV irradiation device is arranged in an inner cavity, the power of the UV irradiation device is 2kW, and the irradiation wavelength is less than or equal to 185 nm; a liquid inlet of the UV photocatalytic ozone reactor 4 is connected with a second tower kettle liquid outlet of the second spray tower 3, and a third stop valve 9-3 is arranged on a connecting pipeline of the UV photocatalytic ozone reactor; a liquid outlet of the UV photocatalytic ozone reactor 4 is connected with a tower bottom liquid return port of the second spray tower 3, and a third circulating pump 10-3 and a fourth stop valve 9-4 are arranged on a connecting pipeline of the UV photocatalytic ozone reactor 4; an air inlet of the UV photocatalytic ozone reactor 4 is connected with an air outlet of the low-temperature plasma reactor 2, and a fifth stop valve 9-5 is arranged on a connecting pipeline of the UV photocatalytic ozone reactor 4; an air outlet of the UV photocatalytic ozone reactor 4 is connected with an air inlet of the low-temperature plasma reactor 2, and a connecting pipeline of the UV photocatalytic ozone reactor 4 is provided with a fourth circulating pump 10-4 and a sixth stop valve 9-6;
an oxygen outlet is arranged on the oxygen generator 5, the oxygen outlet of the oxygen generator 5 is connected with the air inlet of the low-temperature plasma reactor 2, and a seventh stop valve 9-7 is arranged on a connecting pipeline of the oxygen generator 5;
the pH regulating device 6 is connected with the first spray tower 1; the liquid level compensation device 7 is connected with the UV photocatalytic ozone reactor 4; the COD detection device 8 is connected with the UV photocatalytic ozone reactor 4.
(2) VOCs waste gas treatment is carried out in the system, and the specific operation steps comprise:
A) opening a first stop valve 9-1 and a second stop valve 9-2, starting a first circulating pump 10-1 and a second circulating pump 10-2, and then sending VOCs waste gas into a gas inlet of a first spray tower 1, wherein the VOCs waste gas is washed by water of the first spray tower 1, low-temperature plasma treatment of a low-temperature plasma reactor 2 and secondary water of a second spray tower 3 in sequence, and treated waste gas is obtained at a gas outlet of the second spray tower 3;
B) in the VOCs waste gas treatment process, the washing liquid in the first spray tower 1 and the second spray tower 3 is gradually absorbed and saturated, and the washing effect is reduced; when the concentration of VOCs in the treated waste gas discharged from the gas outlet of the second spray tower 3 exceeds a set value, closing the second circulating pump 10-2, opening the third stop valve 9-3, pumping tower bottom liquid in the first spray tower 1 into the second spray tower 3 through the first circulating pump 10-1, and then entering the UV photocatalytic ozone reactor 4 along with tower bottom liquid in the second spray tower 3;
C) after the tower bottom liquid of the first spray tower 1 and the tower bottom liquid of the second spray tower 3 are all fed into the UV photocatalytic ozone reactor 4, closing a first circulating pump 10-1, a first stop valve 9-1, a second stop valve 9-2 and a third stop valve 9-3, opening a fifth stop valve 9-5, a sixth stop valve 9-6 and a seventh stop valve 9-7, starting an oxygen generator 5, injecting a certain amount of oxygen into a low-temperature plasma reactor 2, then closing the oxygen generator 5 and the seventh stop valve 9-7, carrying out plasma generation on the injected oxygen in the low-temperature plasma reactor, then introducing low-temperature plasma generated by the oxygen into a UV photocatalytic ozone reactor 4, starting a UV irradiation device of the UV photocatalytic ozone reactor 4, and carrying out synergistic treatment on water in the UV photocatalytic ozone reactor 4 by using the low-temperature plasma generated by the oxygen and UV light; during the period, the fourth circulating pump 10-4 is started, and the gas in the system flows through the fourth circulating pump 10-4 to form a closed loop;
D) in the cooperative treatment process, the COD value of the water in the UV photocatalytic ozone reactor 4 is gradually reduced, when the COD value is lower than a set value, the UV irradiation devices of the low-temperature plasma reactor 2 and the UV photocatalytic ozone reactor 4 are closed, after the ozone in the closed loop is metabolized to be completely decomposed, the fifth stop valve 9-5, the sixth stop valve 9-6 and the fourth circulating pump 10-4 are closed, then the fourth stop valve 9-4 is opened, the third circulating pump 10-3 is started, the water in the UV photocatalytic ozone reactor is pumped back to the second spray tower 3, and after the pumping is finished, the third circulating pump 10-3 and the fourth stop valve 9-4 are closed; then carrying out the next round of operations A) to D);
in this embodiment, in the operation process of the first spray tower 1 and the second spray tower 3, the pH value of the tower bottom liquid of the first spray tower 1 is regulated and controlled by the pH regulating and controlling device 6, so that the pH value is maintained at 7;
in this embodiment, the liquid level in the UV photocatalytic ozone reactor 4 is monitored and compensated by the liquid level compensation device 7, the compensation method is to automatically supplement fresh process water into the UV photocatalytic ozone reactor 4, so as to maintain the volume of the liquid storage section in the operation process of the first spray tower 1 and the second spray tower 3, and the volume of the liquid storage section is set to be 1.1 to 1.2 times of the volume of the liquid phase corresponding to the minimum liquid-gas ratio in the operation process of the first spray tower 1 and the second spray tower 3;
in this embodiment, the COD value of the water in the UV photocatalytic ozone reactor 4 is monitored by the COD detection device 8.
Example 2
Simulated flue gas was treated using the abatement system and operating procedure described in example 1. Wherein the simulated flue gas is a mixed gas of toluene and air (toluene concentration is 100 mg/m)3) The air volume is 50Nm3The water circulation amount is 200L/h; when the concentration of the toluene in the waste gas discharged from the gas outlet of the second spray tower 3 reaches 10mg/m3When the step B) is started to be executed; the oxygen production amount of the oxygen generator 5 in the step C) is 5Nm3The gas circulation flow rate of the fourth circulation pump 10-4 is 50Nm3H; when the COD value of the water body in the UV photocatalytic ozone reactor 4 reaches 1000mg/L, starting to execute the step D); 15g of single atom Pt/TiO catalyst is filled in the UV photocatalytic ozone reactor 42The catalyst is prepared according to the following steps:
heating and stirring n-hexane and n-pentanol at a volume ratio of 6L:1L at 65 ℃, adding 600g of Cetyl Trimethyl Ammonium Bromide (CTAB) until dissolved, and adding 150mL of titanium trichloride solution (with the concentration of 15 wt%); carrying out solvothermal reaction for 1h in a hydrothermal reaction kettle at the temperature of 200 ℃, carrying out solid-liquid separation after the reaction is finished, carrying out alcohol washing, and carrying out vacuum drying for 2h at the temperature of 45 ℃ to obtain a titanium dioxide carrier with a three-dimensional structure;
ultrasonically dispersing 15g of the titanium dioxide carrier into 4L of ethanol solution, dropwise adding 1mg/mL chloroplatinic acid solution into the ethanol solution until the mass fraction of Pt atoms in the titanium dioxide carrier reaches 0.05 wt%, ultrasonically drying for 30min, and stirring to dry at 45 ℃ and 250r/min to obtain a monoatomic catalyst precursor;
subjecting the monatomic catalyst precursor to H at 125 DEG C2Reducing and calcining the hydrogen-helium mixed gas with the content of 10 vol% for 1h, and naturally cooling to room temperature to obtain the monatomic Pt/TiO2A catalyst.
Respectively aligning the prepared titanium dioxide carrier and the monoatomic Pt/TiO2STEM characterization of the catalyst was carried out, and the results are shown in FIGS. 2 and 3, in which FIG. 2 is a STEM of the titania carrier provided in example 2 of the present invention, and FIG. 3 is a STEM of the monatomic catalyst provided in example 2 of the present invention.
The toluene removal effect of the first spray tower 1, the low-temperature plasma reactor 2, the second spray tower 3 and the UV photocatalytic ozone reactor 4 in the flue gas treatment process is evaluated, and the result is as follows: the first-stage water washing (the first spray tower 1) can absorb about 10% of methylbenzene, the removal rate of the methylbenzene by the low-temperature plasma reactor 2 can reach 75%, the second-stage tail-end water washing (the second spray tower 3) can absorb about 10% of methylbenzene and intermediate products of the methylbenzene degraded by plasma, and the removal rate of organic matters such as the methylbenzene in the water body by the UV photocatalytic ozone reactor 4 can reach 95% (obtained by calculation according to the COD value variation of the water body).
Example 3
Simulated flue gas was treated using the abatement system and operating procedure described in example 1. Wherein the simulated flue gas is a mixed gas of toluene and air (toluene concentration is 100 mg/m)3) The air volume is 50Nm3The water circulation amount is 200L/h; when the concentration of the toluene in the waste gas discharged from the gas outlet of the second spray tower 3 reaches 10mg/m3When the step B) is started to be executed; the oxygen production amount of the oxygen generator 5 in the step C) is 5Nm3The gas circulation flow rate of the fourth circulation pump 10-4 is 50Nm3H; when the COD value of the water body in the UV photocatalytic ozone reactor 4 reaches 1000mg/L, starting to execute the step D); the catalyst filled in the UV photocatalytic ozone reactor 4 is 15g of monoatomic Cu/TiO2The catalyst is prepared according to the following steps:
heating and stirring n-hexane and n-pentanol at a volume ratio of 6L:1L at 65 ℃, adding 600g of Cetyl Trimethyl Ammonium Bromide (CTAB) until dissolved, and adding 150mL of titanium trichloride solution (with the concentration of 15 wt%); carrying out solvothermal reaction for 1h in a hydrothermal reaction kettle at the temperature of 200 ℃, carrying out solid-liquid separation after the reaction is finished, carrying out alcohol washing, and carrying out vacuum drying for 2h at the temperature of 45 ℃ to obtain a titanium dioxide carrier with a three-dimensional structure;
ultrasonically dispersing 15g of the titanium dioxide carrier into 4L of ethanol solution, dropwise adding 1mg/mL of copper nitrate into the ethanol solution until the mass fraction of Cu atoms in the titanium dioxide carrier reaches 0.05 wt%, ultrasonically drying for 30min, and stirring to dry at 45 ℃ at 250r/min to obtain a monoatomic catalyst precursor;
subjecting the monatomic catalyst precursor to H at 125 DEG C2Reducing and calcining the hydrogen-helium mixed gas with the content of 10 vol% for 1h, and naturally cooling to room temperature to obtain monoatomic Cu/TiO2A catalyst.
The toluene removal effect of the first spray tower 1, the low-temperature plasma reactor 2, the second spray tower 3 and the UV photocatalytic ozone reactor 4 in the flue gas treatment process is evaluated, and the result is as follows: the first-stage water washing (the first spray tower 1) can absorb about 10% of methylbenzene, the removal rate of the methylbenzene by the low-temperature plasma reactor 2 can reach 75%, the second-stage tail-end water washing (the second spray tower 3) can absorb about 10% of methylbenzene and intermediate products of the methylbenzene degraded by plasma, and the removal rate of organic matters such as the methylbenzene in the water body by the UV photocatalytic ozone reactor 4 can reach 75% (obtained by calculation according to the COD value variation of the water body).
Example 4
Simulated flue gas was treated using the abatement system and operating procedure described in example 1. Wherein the simulated flue gas is a mixed gas of toluene and air (toluene concentration is 200 mg/m)3) The air volume is 100Nm3The water circulation amount is 200L/h; when the concentration of the toluene in the waste gas discharged from the gas outlet of the second spray tower 3 reaches 10mg/m3When the step B) is started to be executed; the oxygen production amount of the oxygen generator 5 in the step C) is 5Nm3The gas circulation flow rate of the fourth circulation pump 10-4 is 50Nm3H; when the COD value of the water body in the UV photocatalytic ozone reactor 4 reaches 1000mg/L, starting to execute the step D); 15g of single atom Pt/TiO catalyst is filled in the UV photocatalytic ozone reactor 42The catalyst, the preparation method thereof and the example 2 are the same, and the description is omitted.
The toluene removal effect of the first spray tower 1, the low-temperature plasma reactor 2, the second spray tower 3 and the UV photocatalytic ozone reactor 4 in the flue gas treatment process is evaluated, and the result is as follows: the first-stage water washing (the first spray tower 1) can absorb about 10% of methylbenzene, the removal rate of the methylbenzene by the low-temperature plasma reactor 2 can reach 55%, the second-stage tail-end water washing (the second spray tower 3) can absorb about 15% of methylbenzene and intermediate products of the methylbenzene degraded by plasma, and the removal rate of organic matters such as the methylbenzene in the water body by the UV photocatalytic ozone reactor 4 can reach 90% (obtained by calculation according to the COD value variation of the water body).
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A VOCs exhaust treatment system, comprising:
the first spray tower is provided with a gas inlet, a gas outlet, a spray liquid inlet and a tower kettle liquid outlet;
the low-temperature plasma reactor is provided with an air inlet and an air outlet; the gas inlet of the low-temperature plasma reactor is connected with the gas outlet of the first spray tower, and a first stop valve is arranged on a connecting pipeline of the low-temperature plasma reactor;
the second spray tower is provided with a gas inlet, a gas outlet, a spray liquid inlet, a first tower kettle liquid outlet, a second tower kettle liquid outlet and a tower kettle liquid reflux opening; the gas inlet of the second spray tower is connected with the gas outlet of the low-temperature plasma reactor, and a second stop valve is arranged on a connecting pipeline of the second spray tower; a spray liquid inlet of the second spray tower is connected with a tower kettle liquid outlet of the first spray tower, and a first circulating pump is arranged on a connecting pipeline of the second spray tower; a first tower kettle liquid outlet of the second spray tower is connected with a spray liquid inlet of the first spray tower, and a second circulating pump is arranged on a connecting pipeline of the second spray tower;
the UV photocatalytic ozone reactor is provided with an air inlet, an air outlet, a liquid inlet and a liquid outlet; a liquid inlet of the UV photocatalytic ozone reactor is connected with a second tower kettle liquid outlet of the second spray tower, and a third stop valve is arranged on a connecting pipeline of the UV photocatalytic ozone reactor; a liquid outlet of the UV photocatalytic ozone reactor is connected with a tower bottom liquid reflux port of the second spray tower, and a third circulating pump and a fourth stop valve are arranged on a connecting pipeline of the UV photocatalytic ozone reactor; the air inlet of the UV photocatalytic ozone reactor is connected with the air outlet of the low-temperature plasma reactor, and a fifth stop valve is arranged on a connecting pipeline of the UV photocatalytic ozone reactor; the gas outlet of the UV photocatalytic ozone reactor is connected with the gas inlet of the low-temperature plasma reactor, and a fourth circulating pump and a sixth stop valve are arranged on a connecting pipeline of the UV photocatalytic ozone reactor;
and an oxygen outlet of the oxygen generator is connected with an air inlet of the low-temperature plasma reactor, and a seventh stop valve is arranged on a connecting pipeline of the oxygen generator.
2. The abatement system of claim 1, further comprising a pH control device for controlling the pH of the first spray tower.
3. The abatement system of claim 1, further comprising a level compensation device for replenishing fresh process water into the UV photocatalytic ozone reactor.
4. The remediation system of claim 1 further comprising a COD detection means for detecting a COD value of a body of water within the UV photocatalytic ozone reactor.
5. The abatement system of claim 1, wherein the catalyst packed in the UV photocatalytic ozone reactor is a monatomic catalyst.
6. The abatement system of claim 5, wherein the monatomic catalyst is prepared by:
a) mixing an active metal source compound, a single atom catalyst carrier and a solvent, stirring and drying to obtain a single atom catalyst precursor;
b) and reducing and calcining the monatomic catalyst precursor in a hydrogen-helium mixed atmosphere to obtain the monatomic catalyst.
7. The abatement system of claim 6, wherein in step a), the monatomic catalyst support is prepared according to the following steps:
and carrying out solvothermal reaction on hexadecyl trimethyl ammonium bromide and a titanium source compound in a solvent to obtain the monatomic catalyst carrier.
8. The abatement system of claim 6, wherein in step a), the active metal source compound comprises one or more of a Cu source compound, a Fe source compound, an Au source compound, a Pt source compound and a Pd source compound.
9. The remediation system of claim 6 wherein in step b) the calcination temperature is from 100 to 400 ℃; the calcining time is 30-120 min.
10. A method of remediating waste gases from VOCs in a remediation system according to any one of claims 1 to 9, comprising the steps of:
A) opening a first stop valve and a second stop valve, starting a first circulating pump and a second circulating pump, and then sending VOCs waste gas into a gas inlet of a first spray tower, wherein the VOCs waste gas is washed by water in the first spray tower, low-temperature plasma in a low-temperature plasma reactor and secondary water in a second spray tower in sequence, and treated waste gas is obtained at a gas outlet of the second spray tower;
B) in the VOCs waste gas treatment process, the washing liquid in the first spray tower and the second spray tower is gradually absorbed and saturated, and the washing effect is reduced; when the concentration of VOCs in the treated waste gas discharged from the gas outlet of the second spray tower exceeds a set value, closing the second circulating pump, opening a third stop valve, pumping tower bottom liquid in the first spray tower into the second spray tower through the first circulating pump, and then entering the UV photocatalytic ozone reactor along with the tower bottom liquid of the second spray tower;
C) after the first spray tower kettle liquid and the second spray tower kettle liquid are all fed into the UV photo-catalytic ozone reactor, closing the first circulating pump, the first stop valve, the second stop valve and the third stop valve, opening the fifth stop valve, the sixth stop valve and the seventh stop valve, starting the oxygen generator to inject a certain amount of oxygen into the low-temperature plasma reactor, closing the oxygen generator and the seventh stop valve, carrying out plasma generation on the injected oxygen in the low-temperature plasma reactor, feeding the low-temperature plasma generated by the oxygen into the UV photo-catalytic ozone reactor, starting a UV irradiation device of the UV photo-catalytic ozone reactor, and carrying out synergistic treatment on the water in the UV photo-catalytic ozone reactor by using the low-temperature plasma generated by the oxygen and the UV light; during the period, the fourth circulating pump is started, and the gas in the system flows through the fourth circulating pump to form a closed loop;
D) in the cooperative treatment process, the COD value of the water body in the UV photocatalytic ozone reactor is gradually reduced, when the COD value is lower than a set value, the UV irradiation devices of the low-temperature plasma reactor and the UV photocatalytic ozone reactor are closed, after the ozone in the closed loop is metabolized to be completely decomposed, the fifth stop valve, the sixth stop valve and the fourth circulating pump are closed, the fourth stop valve is opened, the third circulating pump is started, the water body in the UV photocatalytic ozone reactor is pumped back to the second spray tower, and the third circulating pump and the fourth stop valve are closed after the pumping is finished; and then carrying out the next round of the operations A) to D).
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Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1021375A1 (en) * | 1997-09-10 | 2000-07-26 | Brian Edward Butters | System and method for photocatalytic treatment of contaminated media |
| JP2010036147A (en) * | 2008-08-07 | 2010-02-18 | Techno Ryowa Ltd | System for removing water-soluble organic compound |
| CN204563851U (en) * | 2015-04-02 | 2015-08-19 | 赵同强 | A kind of equipment of the casting of the plasma treatment with demister waste gas |
| CN204996289U (en) * | 2015-09-29 | 2016-01-27 | 东莞市龙洋环保科技有限公司 | Waste gas treatment system sprays paint based on plasma purification techniques |
| CN205435426U (en) * | 2015-12-17 | 2016-08-10 | 宜宾海丝特纤维有限责任公司 | Treatment system of waste gas in viscose fiber production process |
| CN206152538U (en) * | 2016-09-23 | 2017-05-10 | 浙江卓锦环保科技股份有限公司 | Washing powder production process discharged waste gas processing system |
| CN106865736A (en) * | 2015-12-11 | 2017-06-20 | 中国石油天然气股份有限公司 | A kind of processing method and processing device of industrial wastewater |
| CN206730825U (en) * | 2017-04-12 | 2017-12-12 | 浙江奇彩环境科技股份有限公司 | A kind of system for handling foul gas |
| CN107469506A (en) * | 2016-06-07 | 2017-12-15 | 中国石油化工股份有限公司 | The method and device of low temperature plasma pyrolysis oxidization reactor for treatment foul waste gas |
| CN207405000U (en) * | 2017-10-10 | 2018-05-25 | 成都清境环境科技有限公司 | A kind of compound advanced oxidation technology handles the device of high COD waste liquids |
| CN108217819A (en) * | 2018-01-19 | 2018-06-29 | 河海大学常州校区 | Atmosphere pressure plasma jet flow collaboration ultrasound and the water treatment facilities of catalysis |
| US20180345264A1 (en) * | 2015-09-23 | 2018-12-06 | University Of Ulsan Foundation For Industry Cooperation | Photocatalyst having high visible-light activity |
| CN109908899A (en) * | 2019-03-14 | 2019-06-21 | 浙江师范大学 | A kind of TiO2Load the preparation method and applications of monatomic Co catalyst |
| CN111013626A (en) * | 2019-12-18 | 2020-04-17 | 中钢集团鞍山热能研究院有限公司 | Monoatomic metal graphene catalyst based on needle coke and preparation method thereof |
| CN111151246A (en) * | 2020-01-14 | 2020-05-15 | 天津科技大学 | Gold atom/titanium dioxide composite material, preparation method and application thereof |
| CN111215060A (en) * | 2018-11-25 | 2020-06-02 | 中国科学院大连化学物理研究所 | Preparation of supported platinum group metal monatomic catalyst and application thereof in deoxidation reaction |
-
2020
- 2020-08-26 CN CN202010870820.1A patent/CN112023690B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1021375A1 (en) * | 1997-09-10 | 2000-07-26 | Brian Edward Butters | System and method for photocatalytic treatment of contaminated media |
| JP2010036147A (en) * | 2008-08-07 | 2010-02-18 | Techno Ryowa Ltd | System for removing water-soluble organic compound |
| CN204563851U (en) * | 2015-04-02 | 2015-08-19 | 赵同强 | A kind of equipment of the casting of the plasma treatment with demister waste gas |
| US20180345264A1 (en) * | 2015-09-23 | 2018-12-06 | University Of Ulsan Foundation For Industry Cooperation | Photocatalyst having high visible-light activity |
| CN204996289U (en) * | 2015-09-29 | 2016-01-27 | 东莞市龙洋环保科技有限公司 | Waste gas treatment system sprays paint based on plasma purification techniques |
| CN106865736A (en) * | 2015-12-11 | 2017-06-20 | 中国石油天然气股份有限公司 | A kind of processing method and processing device of industrial wastewater |
| CN205435426U (en) * | 2015-12-17 | 2016-08-10 | 宜宾海丝特纤维有限责任公司 | Treatment system of waste gas in viscose fiber production process |
| CN107469506A (en) * | 2016-06-07 | 2017-12-15 | 中国石油化工股份有限公司 | The method and device of low temperature plasma pyrolysis oxidization reactor for treatment foul waste gas |
| CN206152538U (en) * | 2016-09-23 | 2017-05-10 | 浙江卓锦环保科技股份有限公司 | Washing powder production process discharged waste gas processing system |
| CN206730825U (en) * | 2017-04-12 | 2017-12-12 | 浙江奇彩环境科技股份有限公司 | A kind of system for handling foul gas |
| CN207405000U (en) * | 2017-10-10 | 2018-05-25 | 成都清境环境科技有限公司 | A kind of compound advanced oxidation technology handles the device of high COD waste liquids |
| CN108217819A (en) * | 2018-01-19 | 2018-06-29 | 河海大学常州校区 | Atmosphere pressure plasma jet flow collaboration ultrasound and the water treatment facilities of catalysis |
| CN111215060A (en) * | 2018-11-25 | 2020-06-02 | 中国科学院大连化学物理研究所 | Preparation of supported platinum group metal monatomic catalyst and application thereof in deoxidation reaction |
| CN109908899A (en) * | 2019-03-14 | 2019-06-21 | 浙江师范大学 | A kind of TiO2Load the preparation method and applications of monatomic Co catalyst |
| CN111013626A (en) * | 2019-12-18 | 2020-04-17 | 中钢集团鞍山热能研究院有限公司 | Monoatomic metal graphene catalyst based on needle coke and preparation method thereof |
| CN111151246A (en) * | 2020-01-14 | 2020-05-15 | 天津科技大学 | Gold atom/titanium dioxide composite material, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 谢焕玲: "高级氧化技术处理有机废水的研究进展", 《重庆理工大学学报(自然科学)》 * |
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