CN109316913B - Application of wet discharge reactor in removing sulfur dioxide gas in waste gas - Google Patents

Application of wet discharge reactor in removing sulfur dioxide gas in waste gas Download PDF

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CN109316913B
CN109316913B CN201811172082.2A CN201811172082A CN109316913B CN 109316913 B CN109316913 B CN 109316913B CN 201811172082 A CN201811172082 A CN 201811172082A CN 109316913 B CN109316913 B CN 109316913B
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absorption liquid
gas
discharge
electrode
shell
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CN109316913A (en
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黄立维
陈金媛
张宏华
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Zhejiang University of Technology ZJUT
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/32Separation 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/48Sulfur compounds
    • B01D53/50Sulfur oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75Multi-step processes

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  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention discloses an application of a wet discharge reactor in removing sulfur dioxide gas in waste gas, wherein the wet discharge reactor comprises a hollow shell, a discharge reaction zone in the shell and an absorption liquid circulating device connected with the discharge reaction zone through the shell, and absorption liquid can flow from top to bottom along a grounding electrode plate through the absorption liquid circulating device to form an absorption liquid film. The distance between the discharge electrode and the grounding electrode plate forms an airflow channel of treated gas, the space distance can be dynamically adjusted, the gas flow of gaseous pollutants containing sulfur dioxide passes through a gas discharge reaction zone between the electrode pair, the pollutants are oxidized and degraded, degradation products or intermediate products are absorbed by the liquid film of the absorption liquid, and the purified gas flow is discharged through a gas outlet.

Description

Application of wet discharge reactor in removing sulfur dioxide gas in waste gas
Technical Field
The invention relates to an application of a wet discharge reactor in removing sulfur dioxide gas in waste gas, belonging to the technical field of atmospheric pollution control and environmental protection.
Background
The large emissions of sulfur dioxide from human activities are a major cause of acid rain in the atmosphere. In which sulfur dioxide (SO) is produced by combustion of a fuel2) The ratio is more than 90%, and the second is the industrial process of metallurgy, sulfuric acid, oil refining, chemical industry, pharmacy and the like. The wet sulfur dioxide waste gas treatment technology is to adopt various water solutions to absorb and treat sulfur dioxide, and because the dissolution process of the sulfur dioxide in water is a reversible reaction, the absorption efficiency of the sulfur dioxide by adopting clear water as an absorbent is very low. The absorption method of lime/limestone and other alkali liquids is the main method for treating flue gas sulfur dioxide waste gas at present, but the system is complex, the equipment investment is large, and the desulfurization product is difficult to recycle.
Non-equilibrium plasma generated by gas discharge has begun to be applied in industrial processes as a new exhaust gas treatment technology, and the basic principle is to generate a large amount of energetic electrons, atoms and radicals by using gas discharge. These energetic electrons, atoms and radicals react with and oxidize or dissociate harmful gas molecules. The present inventors reported the results of experiments on sulfur dioxide removal using a pulsed corona discharge reactor (proceedings of the chemical industry, English edition 2011, 19 (3): 518- & 522). Although pulsed gas discharge is a very efficient way of generating plasma, it is difficult to apply pulsed power sources on a large scale in industry due to the high technical requirements.
Disclosure of Invention
The invention aims to provide an application of a wet discharge reactor in removing sulfur dioxide gas in waste gas.
The wet discharge reactor adopted by the invention comprises a hollow shell, a discharge reaction zone in the shell and an absorption liquid circulating device connected with the discharge reaction zone through the shell, wherein the shell of the discharge reactor is of a hollow cuboid structure, the corresponding upper bottom surface and lower bottom surface of the cuboid structure form the same included angle with the horizontal plane, and the shell is provided with a gas inlet and a gas outlet; the shell is internally provided with an airflow channel parallel to the upper bottom surface, a discharge electrode and a grounding electrode which are parallel to each other are arranged in the airflow channel, the discharge electrode is close to the upper bottom surface and is parallel to the upper bottom surface, the grounding electrode is arranged on the lower bottom surface, and the discharge electrode consists of a discharge electrode plate and needle electrodes uniformly arranged on the discharge electrode plate; the grounding electrode is composed of a grounding electrode plate and water retaining ridges uniformly arranged on the grounding electrode plate; the needle electrodes are opposite to the water retaining ridges and are in one-to-one correspondence with the water retaining ridges; the high-voltage power supply is electrically connected with the discharge electrode; the upper end part of the lower bottom surface is provided with an absorption liquid inlet, and the lower end part of the lower bottom surface is provided with an absorption liquid outlet;
the absorption liquid circulating device comprises a liquid inlet pipe, a circulating pump, an absorption liquid circulating groove and a guide plate, wherein one end of the liquid inlet pipe is connected with the discharge reaction zone, the circulating pump is connected with the liquid inlet pipe, the other end of the liquid inlet pipe is communicated with the absorption liquid circulating groove through the circulating pump, an absorption liquid outlet is connected with the circulating groove, the guide plate is arranged at a liquid flow outlet of an absorption liquid inlet in the discharge reaction zone, and the guide plate is positioned to lead liquid flow entering the absorption liquid inlet to flow from top to bottom along the grounding electrode plate through the guide plate;
the needle electrode is electrically connected with a high-voltage power supply; the whole discharge reactor is hermetically closed.
Further, the application is as follows: applying high voltage to the discharge electrode, starting an absorption liquid circulating device, circulating the absorption liquid through a pressurizing pump, flowing into an inner cavity of the discharge reactor from an absorption liquid inlet along a grounding electrode plate, forming a layer of uniform absorption liquid film on the surface of the grounding electrode, introducing gas to be treated from a gas inlet at one end of the reactor, shortening the distance between the discharge electrode and the grounding electrode when the absorption liquid passes through the water retaining ridge, instantly ionizing the gas between the needle electrode and the liquid level of the water retaining ridge of the grounding electrode plate, oxidizing or degrading the gas to be treated in the gas flow, and absorbing water-soluble intermediate products or water-soluble end products in the degradation process by the absorption liquid film formed on the grounding electrode, thereby achieving the purpose of degradation; the absorption liquid comprises clear water or dilute sulfuric acid.
Furthermore, the gas to be treated is flue gas generated by burning fossil fuel or waste gas discharged by various production processes in metallurgy, sulfuric acid, oil refining or chemical pharmacy, and oxidants such as oxygen and water vapor or argon can be added to improve the oxidation rate of the sulfur dioxide, and the method is specifically adopted according to needs.
The absorption liquid can be generally clear water, alkali liquor or acid solution as an absorbent, and can be selected according to different treatment requirements, the clear water or dilute sulfuric acid solution can be used for recovering dilute sulfuric acid, and the alkaline absorption liquid has better effect but cannot recover the dilute sulfuric acid. The thickness of a liquid film formed on the surface of the electrode by the flow of the absorption liquid is generally 1-5 mm, and the thickness can be adjusted according to requirements.
Still further, the guide plate be rectangular plate, the guide plate with the earthing electrode board on half the formation contained angle, just the contained angle be the acute angle, the guide plate with earthing electrode board between leave and make absorption liquid pass through the guide plate along the gap that earthing electrode board flows, rectangular plate with the casing size phase-match.
Still further, the material of the discharge electrode and the grounding electrode plate is generally metal material with good conductivity, corrosion resistance and discharge resistance such as stainless steel, titanium, tungsten, lead and alloy, and related composite material, and the gas discharge performance of the material is substantially equivalent.
Furthermore, the power supply mode of the discharge electrode is generally direct current (including high-frequency pulse), and can also be pulse, the effect is generally equivalent, wherein the direct current power supply voltage is generally more than 1kV positive, or less than-1 kV negative, preferably 10kV minus 150kV, the positive voltage and the negative voltage are generally equivalent, the positive voltage is slightly better, the pulse repetition frequency of pulse power supply is generally more than 1Hz, preferably 10Hz to 500Hz, the frequency is increased, the input energy is increased, the conversion rate of the sulfur dioxide is improved, and when the pulse repetition frequency is more than 500Hz, the actual effect is not improved too much. The applied voltage of the electrodes is related to the distance between the electrodes, the larger the distance between the electrodes is, the higher the applied voltage can be, generally, the voltage can be increased by 5 kV-10 kV every 10mm of the distance between the electrodes, the high-energy release of the voltage is large, and the conversion rate of sulfur dioxide is high.
Furthermore, the retention time of the treated gas in the discharge reaction zone is generally more than 0.2s, the longer the retention time is, the better the effect is, preferably 3 s-120 s, and more than 120s, the improvement range of the oxidation conversion rate of sulfur dioxide is reduced.
Compared with the prior art, the invention has the advantages that: the gas is discharged by dynamically adjusting the distance between the grounding electrode plate and the discharge electrode, a direct-current power supply can be adopted to replace a high-voltage pulse power supply, the equipment investment and the use cost are reduced, the system operation reliability is improved, sulfur dioxide in the gas flow is oxidized into sulfur trioxide and then absorbed by an absorption liquid film on the surface of the grounding electrode, dilute sulfuric acid can be recovered, and the cyclic utilization of resources is realized.
Drawings
FIG. 1 is a schematic view of a wet discharge reactor employed in the present invention;
fig. 2 is a sectional view of a wet discharge reactor employed in the present invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
In the figure: 1 a gas inlet; 2 high-voltage power supply connecting wires; 3, a water return pipe; 4, a liquid inlet pipe; 5 a central electrode bar; 6, a flow guide plate; 7 a gas outlet; 8, a liquid adding port; 9 an absorption liquid circulating tank; 10 liquid discharge port; 11-pin electrodes; 12 a ground electrode plate; 13 circulating pump; 14 connecting pipes; 15 discharge electrode plates; 16 water blocking ridges.
Example 1:
a wet gas discharge reactor is shown in figures 1 and 2. The length of the discharge reactor is about 500mm, the width of the discharge reactor is about 250mm, the height of the discharge reactor is about 80mm, the effective length of a discharge reaction area is about 250mm, the discharge reaction area is integrally sealed, the air leakage rate is less than 1%, and the discharge reaction area is integrally placed in an inclined way at about 15 degrees so as to facilitate the flowing of an absorption liquid film. The gas flow channel is a single channel, the electrode pair is a needle-plate type, wherein the needle electrode 11 is fixed on a discharge electrode plate 15, 9 groups of needle electrodes (the distance between two discharge electrodes is about 20mm and is uniformly distributed) are respectively arranged along the air flow direction and the vertical air flow direction, the needle discharge electrode is alloy steel, the size is phi 3 multiplied by 20, positive or negative high voltage is applied, 9 water retaining ridges 16 (the vertical height is 15mm and the width is 5mm) are arranged on the other grounding electrode plate 12 and are symmetrically distributed with the needle electrode 11, a guide plate 6 is arranged at the front end of the grounding electrode plate 12, so that an absorption liquid film is formed on the surface of the grounding electrode plate 12 of the reactor, the flow rate of the absorption liquid can be adjusted according to a preset frequency along with time, and the distance between the electrode pair is changed when the absorption liquid flows through the water retaining ridges 16 of the grounding electrode plate 12. The absorption liquid is collected by an absorption liquid circulating groove at the lower part of the reactor and can be recycled by a circulating pump 13.
The treatment process comprises introducing the gas flow of the waste gas containing sulfur dioxide to be treated into the discharge reactor through a gas inlet 1, connecting a needle electrode 11 with a high-voltage power line 2 through a discharge electrode plate 15, grounding the grounding electrode plate 12, simultaneously introducing absorption liquid through a guide plate 6 to form an absorption liquid film on the surface of the grounding electrode plate 12, wherein the flow rate of the absorption liquid changes along with time according to a preset frequency, when the absorption liquid passes through a water retaining sill 16, the distance between the discharge electrode and the grounding electrode is shortened, the gas between the liquid levels of the discharge electrode 11 and the water retaining sill 16 of the grounding electrode plate 12 is instantly ionized, the gas is discharged, the gas flow containing gaseous pollutants introduced from the gas inlet passes through a gas discharge area between the electrode pairs, the gaseous pollutants containing sulfur, nitrogen and halogen in the gas flow are oxidized or degraded, and water-soluble degradation products or intermediate products are absorbed by the absorption liquid film on the surface of the grounding electrode, is removed from the gas stream and the purified gas stream is discharged through a gas outlet 7 arranged at the other end of the reactor, thereby achieving the purpose of gas purification. And the absorption liquid enters an absorption liquid circulating groove 9 through a water return pipe 3 at the lower part of the reactor, and then is guided into a guide plate 6 at the front part of the gas discharge reactor through a connecting pipe 15, a circulating pump 14 and a liquid inlet pipe 4 for recycling.
The experimental conditions were: the boiler burns flue gas with a flow of about 3m3A concentration of about 800mg/m sulfur dioxide gas inlet concentration of about 10% by volume, about 8% by volume oxygen, about 12% carbon dioxide, and about 10% moisture3The gas inlet of the flue gas flow is about 70 ℃, the initial absorption liquid is clear water, the adding frequency of the absorption liquid is 0.3 times/s, the cumulative flow of the absorption liquid is about 30L/h, the maximum liquid level height on a water retaining ridge is about 10mm, the electrode power supply mode is a positive direct current power supply, the voltage is about 25kV, the power supply power is about 60W, and the rotating speed of the rotating motor is about 50 revolutions per minute.
The experimental result is that the outlet concentration of the sulfur dioxide is about 15mg/m3
Example 2: the experimental setup was the same as in example 1. The gas flow is tail gas of a sulfuric acid plant, and the flow rate is about 3m3A concentration of about 1500mg/m at the sulfur dioxide inlet, wherein about 4% by volume of oxygen and about 20% by volume of water are present3The gas inlet of the gas stream was about 70 ℃, the initial absorption solution was a 5% dilute sulfuric acid solution, and 5% argon was added to the gas stream, under otherwise the same conditions as in example 4.
The experimental result is that the outlet concentration of the sulfur dioxide is about 41mg/m3
It should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and the scope of the present invention is not limited thereto. Any modification of the technical solutions described in the embodiments, or any equivalent replacement, modification, variation and improvement of the technical features thereof, which are within the spirit and principle of the present invention, should be included in the protection scope of the present invention.

Claims (11)

1. The application of a wet-type discharge reactor in removing sulfur dioxide gas in waste gas is characterized in that the discharge reactor comprises a hollow shell, a discharge reaction zone in the shell and an absorption liquid circulating device connected with the discharge reaction zone through the shell, the shell of the discharge reactor is of a hollow cuboid structure, the corresponding upper bottom surface and lower bottom surface of the cuboid structure form the same included angle with the horizontal plane, and the shell is provided with a gas inlet (1) and a gas outlet (7); a gas flow channel parallel to the upper bottom surface is formed in the shell, a discharge electrode and a grounding electrode which are parallel to each other are arranged in the gas channel, the discharge electrode is close to the upper bottom surface and is parallel to the upper bottom surface, the grounding electrode is arranged on the lower bottom surface, and the discharge electrode is composed of a discharge electrode plate (15) and needle electrodes (11) which are uniformly arranged on the discharge electrode plate (15); the grounding electrode is composed of a grounding electrode plate (12) and water retaining ridges (16) uniformly arranged on the grounding electrode plate (12); the needle electrodes (11) are opposite to the water retaining ridges (16) and are in one-to-one correspondence; the high-voltage power supply is electrically connected with the discharge electrode; the upper end part of the lower bottom surface is provided with an absorption liquid inlet, and the lower end part of the lower bottom surface is provided with an absorption liquid outlet;
the absorption liquid circulating device comprises a liquid inlet pipe (4) with one end connected with the discharge reaction zone, a circulating pump (13) connected with the liquid inlet pipe (4), an absorption liquid circulating groove (9) and a guide plate (6), wherein one end of the liquid inlet pipe (4) is connected with an absorption liquid inlet, the other end of the liquid inlet pipe is communicated with the absorption liquid circulating water tank through the circulating pump (13), an absorption liquid outlet is connected with the circulating water tank, the guide plate (6) is arranged at a liquid flow outlet of an absorption liquid inlet in the discharge reaction zone, and the guide plate (6) is positioned to lead liquid flow entering the absorption liquid inlet to flow from top to bottom along the grounding electrode plate (12) through the guide plate (6); the flow of the absorption liquid is adjusted according to a preset frequency along with time;
the needle electrode (11) is electrically connected with a high-voltage power supply; the whole discharge reactor is hermetically closed.
2. The use of claim 1, wherein: the application is as follows: applying high voltage to the discharge electrode, starting an absorption liquid circulating device, enabling the absorption liquid to flow into an inner cavity of the discharge reactor from an absorption liquid inlet along a ground electrode plate (12) through circulation of a pressurizing pump, forming a layer of uniform absorption liquid film on the surface of the ground electrode, introducing gas to be treated from a gas inlet at one end of the reactor, shortening the distance between the discharge electrode and the ground electrode when the absorption liquid passes through the water retaining sill (16), instantly ionizing the gas between the needle electrode (11) and the liquid level of the water retaining sill (16) of the ground electrode plate (12), oxidizing or degrading the gas to be treated in the gas flow, and absorbing a water-soluble intermediate product or a water-soluble final product in the degradation process by the absorption liquid film formed on the ground electrode so as to achieve the degradation purpose; the absorption liquid comprises clear water or dilute sulfuric acid.
3. Use according to claim 2, characterized in that: the gas to be treated is fossil fuel combustion flue gas, waste gas discharged by metallurgy, building materials or chemical pharmaceutical production process.
4. Use according to claim 2, characterized in that: the guide plate (6) be rectangular plate, guide plate (6) with the earthing electrode board (12) first half form the contained angle, just the contained angle be the acute angle, guide plate (6) with earthing electrode board (12) between leave and make absorption liquid pass through guide plate (6) and follow earthing electrode board (12) the gap that flows, rectangular plate with shell size phase-match.
5. Use according to claim 2, characterized in that: the water retaining ridge (16) is perpendicular to the central axis of the cuboid structure along the airflow direction.
6. Use according to claim 2, characterized in that: the material of the discharge electrode or the grounding electrode comprises titanium, zirconium, tantalum, tungsten, lead or alloy.
7. Use according to claim 2, characterized in that: the power supply mode of the discharge electrode is direct current, pulse or alternating current.
8. The use of claim 7, wherein: the voltage of the direct current power supply is +/-10 kV to +/-150 kV; the voltage of the pulse power supply is +/-10 kV to +/-150 kV, and the pulse repetition frequency of the pulse power supply is 10Hz to 500 Hz; the voltage of the alternating current power supply is 1kV to 300kV, and the frequency is 10Hz to 1000 Hz.
9. Use according to claim 2, characterized in that: the retention time of the gas to be treated in the discharge reaction zone is 3 s-120 s.
10. Use according to claim 2, characterized in that: the thickness of the absorption liquid film is 1-5 mm.
11. The use of claim 6, wherein: the discharge electrode or the grounding electrode is made of stainless steel.
CN201811172082.2A 2018-10-09 2018-10-09 Application of wet discharge reactor in removing sulfur dioxide gas in waste gas Active CN109316913B (en)

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