KR102164623B1 - Apparatus for simultaneous removing nitrogen oxide and sulfur oxides of flue gas - Google Patents

Abstract

The present invention relates to an apparatus for simultaneously removing nitrogen oxides and sulfur oxides of exhaust gas capable of oxidizing nitrogen monoxide (NO) contained in exhaust gas by spraying a liquid oxidizing agent, and simultaneously removing nitrogen oxides and sulfur oxides using an organic catalyst. will be.

Description

Simultaneous removal of nitrogen oxides (NOx) and sulfur oxides (SOx) from exhaust gas{APPARATUS FOR SIMULTANEOUS REMOVING NITROGEN OXIDE AND SULFUR OXIDES OF FLUE GAS}

The present invention relates to an apparatus for simultaneously removing nitrogen oxides and sulfur oxides from exhaust gas, and more particularly, to oxidize nitrogen monoxide (NO) contained in exhaust gas by spraying a liquid oxidizing agent, and using an organic catalyst It relates to an apparatus for simultaneously removing nitrogen oxides and sulfur oxides from exhaust gas capable of simultaneously removing sulfur oxides.

In the boiler, fossil fuels such as coal and air containing excess oxygen are injected to perform combustion, and as a result of combustion, fly ash, carbon dioxide (CO2), nitrogen oxides (NOx), and sulfur oxides ( By-products such as SOx), carbon monoxide (CO), and unburned carbon (HC) are generated with heat, and unreacted nitrogen (N2) and oxygen (O2) remain.

As such, when sulfur-containing fuel is burned, sulfur is released into the atmosphere in the form of sulfur dioxide (SO2), except that it is attached to the ash. Sulfur dioxide causes air pollution and causes acid rain to fall on the earth, which has a significant harmful effect on the environment as well as humans and animals.

In addition, nitrogen oxides are mainly produced by reacting between basic oxygen and nitrogen existing in the atmosphere at high temperatures where various processes (combustion) are performed, and are mainly released in the form of nitrogen monoxide (NO). These nitrogen oxides not only cause acid rain, but also form ozone and form photochemical smog.

Accordingly, in order to protect the environment, large-scale incineration facilities and power plants have generally been installed with a denitrification device and a desulfurization device for treating nitrogen oxides and sulfur oxides in exhaust gas.

Most of the denitrification devices are selective catalytic reduction devices (SCR), and the selective catalytic reduction devices select NOx in the exhaust gas into nitrogen and water vapor through ammonia reaction while simultaneously passing exhaust gas and ammonia (NH3) reducing agent in the catalyst layer. Reduce.

In addition, most of the desulfurization devices are wet flue gas desulfurization devices, and in the wet desulfurization process, the exhaust gas comes into gas-liquid contact with an absorption fluid containing an alkali such as lime, and thus sulfur dioxide is produced. It is absorbed and removed from the exhaust gas. At this time, it is classified into various types according to the gas-liquid contact method between the exhaust gas and the absorbed fluid, but the spray method is widely adopted worldwide.

As a result, sulfur dioxide absorbed from the exhaust gas forms sulfite in the absorbent fluid, and this sulfite is oxidized by blowing air into the absorbent fluid, usually to form gypsum as a by-product.

As described above, the conventional wet flue gas desulfurization system does not have the ability to remove nitrogen oxides in the exhaust gas, so a separate denitrification device is provided. Or, by using ammonia, this method is effective only in a narrow exhaust gas temperature range, has a relatively high cost, and is prone to dust generation.

Republic of Korea Public Utility Model Publication No. 1998-0030926 (published on August 17, 1998)

The present invention is to solve the above problems, by injecting a liquid oxidizing agent to oxidize nitrogen monoxide (NO) contained in exhaust gas, and using an organic catalyst to simultaneously remove nitrogen oxides and sulfur oxides of exhaust gas. An object of the present invention is to provide an apparatus for simultaneously removing nitrogen oxides and sulfur oxides.

The present invention for solving the above problems, an absorption tank in which an absorption solution containing an organic catalyst is stored, an absorption tower extending to an upper portion of the absorption tank, an exhaust gas inlet duct provided on one side of the absorption tower, An exhaust gas outlet duct provided on the other side of the absorption tower, a first injection unit installed in the absorption tower to inject the absorption solution, and a circulation pump for supplying the absorption solution in the absorption tank to the first injection unit And, a second injection unit installed in the inlet duct or the absorption tower to inject an oxidizing agent solution, an oxidizing agent supply unit supplying an oxidizing agent solution to the second injection unit, and an oxygen supply pipe supplying an oxygen-containing gas to the absorption tank. It provides an apparatus for simultaneously removing nitrogen oxides and sulfur oxides of exhaust gas including.

The organic catalyst may be oil-derived sulfoxides produced from oil.

The oxidizing agent may be made of at least one of H2O2, NaClO2, KMnO4, and P4O10.

The exhaust gas flowing into the inlet duct may first contact the oxidizing agent solution injected by the second injection unit, and may secondly contact the absorption solution injected by the first injection unit.

The oxidizing agent supply unit may include a storage tank in which an oxidizing agent solution is stored and a supply pump for supplying the oxidizing agent solution stored in the storage tank to the second injection unit.

The second spraying unit may be formed of a tray provided with a plurality of nozzles through which an oxidizing agent solution is sprayed.

Each of the plurality of nozzles may be installed with an ultrasonic mist maker.

The tray may be provided with a solution inlet for supplying an oxidizing agent solution to the plurality of nozzles.

The trays are formed in plural, and may be installed alternately on one side and the other side of the absorption tower.

A flow control valve may be installed on an oxidant supply line through which an oxidant solution is supplied from the storage tank to the second injection unit.

In addition, a concentration measuring device for measuring the concentration of nitrogen monoxide (NO) in the exhaust gas introduced into the inlet duct may be further included.

In addition, it may further include a control unit for controlling the injection amount of the oxidizing agent solution injected through the second injection unit in accordance with the nitrogen monoxide (NO) concentration of the exhaust gas measured by the concentration meter.

When the concentration of nitrogen monoxide (NO) in the exhaust gas measured by the concentration meter exceeds a reference value, the control unit may increase the injection amount of the oxidizing agent solution injected through the second injection unit.

When the concentration of nitrogen monoxide (NO) in the exhaust gas measured by the concentration meter does not exceed a reference value, the control unit may reduce the injection amount of the oxidizing agent solution injected through the second injection unit.

The flow control valve may be an electric valve.

Further, according to another embodiment of the present invention, it may further include a turbulence generator installed in the inlet duct or the absorption tower.

In addition, according to another embodiment of the present invention, a neutralization tank for neutralizing nitric acid and sulfuric acid discharged from the absorption tank may be further included.

The neutralizing agent for neutralization may be made of at least one of aqueous ammonia, urea, and aqueous calcium carbonate.

According to the present invention, nitrogen monoxide (NO) contained in exhaust gas is oxidized by spraying a liquid oxidizing agent, so that nitrogen oxides and sulfur oxides can be simultaneously removed using an organic catalyst.

In this way, by adding a denitrification capability to a conventional wet flue gas desulfurization apparatus, denitrification and desulfurization can be simultaneously performed at low cost with one apparatus and process.

The effects of the present invention are not limited to the above effects, and should be understood to include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.

1 is a schematic diagram showing a device according to a first embodiment of the present invention.
Figure 2 is a front view of the second injection unit of Figure 1;
3 is an AA cross-sectional view of FIG. 2.
4 is a schematic diagram showing an apparatus according to a second embodiment of the present invention.
5 is a schematic diagram showing a device according to a third embodiment of the present invention.
Figure 6 is a front view of the turbulence generator of Figure 5;

Hereinafter, a preferred embodiment of an apparatus for simultaneously removing nitrogen oxides and sulfur oxides from exhaust gas of the present invention will be described with reference to the accompanying drawings.

In addition, terms to be described later are terms defined in consideration of functions in the present invention and may vary according to the intention or custom of users and operators, and the following examples do not limit the scope of the present invention, It is merely illustrative of the components presented in the claims.

In order to clearly describe the present invention, parts irrelevant to the description have been omitted, and the same reference numerals are assigned to the same or similar components throughout the specification. Throughout the specification, when a certain part "includes" a certain component, it means that other components may be further provided without excluding other components unless otherwise stated.

The apparatus of the present invention is for removing sulfur oxides and nitrogen oxides from exhaust gas such as a boiler by gas-liquid contact between an absorption solution and exhaust gas. Most of the nitrogen oxides in the exhaust gas are in the form of nitrogen monoxide (NO) and some are in the form of nitrogen dioxide (NO2). In addition, most of the sulfur oxides in the exhaust gas are in the form of sulfur dioxide (SO2), and about 1-2% is in the form of sulfur trioxide (SO3).

First, an apparatus for simultaneously removing nitrogen oxides and sulfur oxides from exhaust gas according to a first embodiment of the present invention will be described with reference to FIGS. 1 to 3.

The apparatus according to the first embodiment of the present invention largely includes an absorption tank 100, an absorption tower 200, an exhaust gas inlet duct 210, an exhaust gas outlet duct 220, a first injection unit 300, and circulation. A pump 320, a second injection unit 400, an oxidizing agent supply unit 500, an oxygen supply pipe 600, a control unit 700, and a concentration meter 800 may be included.

Specifically, an absorption solution including an organic catalyst is stored in the absorption tank 100, and the absorption tank 100 may be formed to have various cross-sections such as a circle or a square. In this embodiment, a description will be made based on a square tank.

In this case, in the present embodiment, the organic catalyst may be made of oil-derived organic sulfoxides. The organic sulfoxide corresponds to an acidic extraction material, and in particular, corresponds to an organic sulfoxide obtained through oxidation of organic sulfides contained in oil.

That is, the absorption solution is a solution in which the organic sulfoxide and water are mixed (water-in-organic sulfoxides), and the weight ratio of water and organic sulfoxide may be variously formed from 10:90 to 90:10, It is preferably from 10:90 to 50:50.

The absorption tower 200 extends above the absorption tank 100 and may be integrally formed with the absorption tank 100.

One side of the absorption tower 200 is provided with an exhaust gas inlet duct 210 through which exhaust gas is introduced, and the other side of the absorption tower 200 is an exhaust gas outlet duct 220 through which the purified exhaust gas is discharged. Is provided.

In this embodiment, the inlet duct 210 is provided on the upper left side of the absorption tower 200 based on FIG. 1, and the outlet duct 220 is provided on the lower right side of the absorption tower 200. . Accordingly, the exhaust gas flowing through the inlet duct 210 flows downward in the absorption tower 200 and is discharged through the outlet duct 220.

The positions of the inlet duct 210 and the outlet duct 220 are not limited thereto, but the exhaust gas introduced through the inlet duct 210 is absorbed by the first injection unit 300 as described later. It is preferable that they are provided to be discharged through the outlet duct 220 after contacting the solution and the oxidizing agent solution sprayed by the second injection unit 400, respectively.

A second spraying part 400 for spraying an oxidizing agent solution is installed in the absorption tower 200, and the oxidizing agent supplying part 500 is for supplying an oxidizing agent solution to the second spraying part 400.

In this case, the oxidizing agent may be formed of at least one of H2O2, NaClO2, KMnO4, and P4O10.

The oxidizing agent supply unit 500 includes a storage tank 520 in which an oxidizing agent solution is stored, and a delivery pump 540 for supplying the oxidizing agent solution stored in the storage tank 520 to the second injection unit 400. .

Furthermore, a flow control valve V1 is installed on the oxidizing agent supply line through which the oxidizing agent solution is supplied from the storage tank 520 to the second injection unit 400 to prevent the oxidizing solution supplied to the second injection unit 400. Allow the flow rate to be adjusted. Hereinafter, the flow rate control of the oxidizing agent solution supplied to the second injection unit 400 will be described in detail below.

In the present embodiment, the second spraying unit 400 includes a tray provided with a plurality of nozzles 410 through which an oxidizing agent solution is sprayed. Specifically, as shown in Figs. 2 and 3, the tray is made of a grid pattern in which the plurality of nozzles 410 are provided at each point, but is not limited thereto, and the plurality of nozzles 410 It may be formed in various shapes such as a plate shape provided.

At this time, an ultrasonic mist maker 420 may be installed on each of the plurality of nozzles 410, and accordingly, the oxidizing agent solution is sprayed with mist through the nozzle 410 to pass through the second spraying unit 400. Gas-liquid contact may be made with the exhaust gas over a wider area, and oxidation efficiency may be improved.

To this end, the tray is provided with a solution inlet 430 for supplying an oxidizing agent solution to the plurality of nozzles 410. That is, the inlet port 430 is provided on one side of the tray, and an oxidizing agent solution may be supplied from the storage tank 520 to the inlet port 430 through the oxidant supply line. In addition, although not shown in the drawing, the tray may also be provided with an outlet through which the oxidizing agent solution is discharged.

In addition, the trays are formed in plural, and may be installed alternately on one side and the other side of the absorption tower 200, respectively. In this embodiment, as shown in FIG. 1, two trays forming the second spraying unit 400 are provided, but are installed on one side of the absorption tower 200 and a side facing the absorption tower 200, respectively. . However, the two trays are installed at different heights. However, the present invention is not limited thereto, and of course, one tray may be installed in the entire area of the cross-section of the absorption tower 200.

Accordingly, the exhaust gas introduced through the inlet duct 210 flows downward from the inside of the absorption tower 200, passes through the two trays in sequence, and is injected through the second injection unit 400. It comes into gas-liquid contact with the oxidizing agent solution. The oxidizing agent solution oxidizes nitrogen monoxide (NO) present in the exhaust gas to nitrogen dioxide (NO2). That is, nitrogen monoxide (NO) is mostly in the exhaust gas before passing through the second injection unit 400, but nitrogen dioxide (NO2) is mostly in the exhaust gas that has passed through the second injection unit 400. .

This is because nitrogen monoxide (NO) does not dissolve well in water and does not form a compound with water or alkali, so that nitrogen monoxide (NO) contained in exhaust gas is oxidized to nitrogen dioxide (NO2) in order to be absorbed by the absorption solution. Because it does.

Specifically, the following oxidation reaction occurs according to the type of oxidizing agent.

(1) NO + H2O2 -> NO2 + H2O

(2) 2NO + NaClO2 -> 2NO2 + NaCl

(3) 2NO + KMnO4 -> 2NO2 + KMnO2

(4) P4 + O2 -> P4O + O

P4O + xO2 -> P4O10 + mO

O + O2 -> O3

NO + O3 -> NO2 + O2

P4O10 + 6H2O -> 4H3PO4

In addition, a first injection part 300 for spraying the absorption solution is installed in the absorption tower 200, and the circulation pump 320 recovers the absorption solution in the absorption tank 100 It is for supplying to the injection unit 300.

In this case, the second injection unit 400 may be installed in the absorption tower 200 in parallel with the first injection unit 300, and in this embodiment, the second injection unit 400 is 1 It is formed above the injection part 300.

Accordingly, the exhaust gas introduced into the inlet duct 210 flows to the lower portion of the absorption tower 200 and is in primary contact with the oxidizing agent solution injected by the second injection unit 400, and the first injection unit It may be in secondary contact with the absorption solution sprayed by (300).

That is, the exhaust gas that has passed through the second injection unit 400 as described above is raised by the circulation pump 320 to come into gas-liquid contact with the absorption solution sprayed through the first injection unit 300, The absorption solution absorbs nitrogen dioxide (NO2) and sulfur dioxide (SO2) present in the exhaust gas.

Specifically, the following reaction is performed with respect to nitrogen dioxide (NO2).

(5) 2NO2 + H2O → HNO2 + HNO3

(6) 3HNO2 → HNO3 + 2NO + H2O

In addition, when both nitrogen monoxide (NO) and nitrogen dioxide (NO2) are present in the exhaust gas, the following reaction occurs.

(7) NO + NO2 → N2O3

(8) N2O3 + H2O → 2HNO2

(9) 3HNO2 → HNO3 + 2NO + H2O

As described above, nitrogen dioxide (NO2) or nitrogen monoxide (NO) and nitrogen dioxide (NO2) react with water to produce nitrous acid (HNO2) or nitric acid (HNO3) (reactions (1), (3), (4)), Since the nitrous acid (HNO2) corresponds to an unstable intermediate product, it is decomposed again before being stably oxidized, and nitrogen monoxide (NO) is released (reactions (2), (5)).

Accordingly, since the absorption solution of the present invention contains an organic catalyst, particularly an organic sulfoxide in the present embodiment, the organic sulfoxide may combine with an unstable intermediate product to form a stable complex. That is, the organic sulfoxide forms a complex with the unstable nitrous acid (HNO2) to stabilize it and prevent decomposition. Specifically, free electron pairs of sulfur (S) atoms in the organic sulfoxide bind to the nitrous acid (HNO2) to prevent its decomposition.

In addition, the following reaction occurs in relation to sulfur dioxide (SO2).

(10) SO2 + H2O → H2SO3

As described above, sulfur dioxide (SO2) is dissolved in water to produce sulfurous acid (H2SO3), and since the sulfurous acid (H2SO3) is also an unstable intermediate product, the reaction is reversed as the temperature rises before stably oxidizing. SO2) can be released again. That is, the solubility of sulfur dioxide (SO2) decreases as the temperature increases.

At this time, in order to enhance the absorption of the sulfur dioxide (SO2), the sulfurous acid (H2SO3) is decomposed, and not to release sulfur dioxide again, the organic sulfoxide in the absorption solution may form a stable complex with sulfur dioxide (SO2). Specifically, it may be bonded 1:1 through a coordination bond between an oxygen (O) atom in the organic sulfoxide and a free electron pair in the sulfur (S) atom of the sulfur dioxide (SO2). Therefore, sulfur dioxide (SO2) can be removed from the exhaust gas using the organic sulfoxide.

At this time, the first injection unit 300 and the second injection unit 400 are provided with the absorption tower 200 so that the exhaust gas passing through the absorption tower 200 does not come into contact with the absorption solution and the oxidizing agent solution and does not pass through. ) Is preferably formed uniformly at all positions in the cross section.

Accordingly, the exhaust gas from which nitrogen oxides and sulfur oxides have been removed is discharged through the outlet duct 220, and the absorption solution absorbing nitrogen oxides (nitrogen dioxide) and sulfur oxides (sulfur dioxide) is returned to the absorption tank 100. Falls inside.

At this time, moisture (mist) is contained in the exhaust gas flowing toward the outlet duct 220 through the first injection unit 300 and the second injection unit 400, and the outlet duct A moisture eliminator 230 may be installed in the 220.

The absorption tank 100 is provided with an oxygen supply pipe 600 for supplying an oxygen-containing gas and air in this embodiment.

As air is supplied into the absorption solution of the absorption tank 100 by the oxygen supply pipe 600, the oxidation reaction of nitrous acid (HNO2) and sulfurous acid (H2SO3) is performed in the absorption tank 100.

Specifically, the following reaction is made.

(11) HNO2 + 1/2 O2 → HNO3

(12) H2SO3 + 1/2 O2 → H2SO4

As described above, as unstable nitrous acid (HNO2) and sulfurous acid (H2SO3) are oxidized to stable nitric acid (HNO3) and sulfuric acid (H2SO4), the organic sulfoxide that has been bonded therewith is decomposed and again combined with new nitrous acid and sulfurous acid. As such, the organic catalyst can be continuously reused.

A stirrer 120 for agitating the absorbent solution may be further installed in the absorption tank 100, and the oxygen supply pipe 600 as a rotational flow is formed in the absorption tank 100 by the stirrer 120. ) Can be finely divided, the contact area and time between the air and the absorption solution can be increased, and the oxidation efficiency can be improved.

In addition, according to another embodiment of the present invention, a plurality of the oxygen supply pipes are disposed to be spaced apart from each other along the circumferential direction of the absorption tank 100, so that they are inclined in the same direction along the circumferential direction of the absorption tank 100. It may be arranged, and accordingly, the absorption of the absorption solution may be stirred by air supplied through the plurality of oxygen supply pipes without a separate stirrer.

After the reaction occurs as described above, the absorption solution is mixed with an aqueous phase and an oily layer to completely remove nitrogen oxides and sulfur oxides absorbed into the absorption solution by discharging oxidized nitric acid (HNO3) and sulfuric acid (H2SO4). sulfoxide phase).

As a result, since nitric acid and sulfuric acid have very high solubility in water, nitric acid and sulfuric acid are present in the aqueous layer, and oil organic sulfoxide is present in the oily layer.

Accordingly, the nitric acid and sulfuric acid can be completely removed by separating and discharging only the aqueous layer from the absorption tank 100, and the oily layer can be combined with fresh water to be used again as an absorption solution.

Furthermore, a neutralization tank 900 for neutralizing nitric acid and sulfuric acid discharged from the absorption tank 100 may be further included.

That is, after phase separation of the absorption solution, the aqueous layer may be discharged from the absorption tank 100 to the neutralization tank 900, and nitric acid and sulfuric acid may be neutralized through a neutralizing agent to form nitrate and sulfate.

In this case, the neutralizing agent for neutralization may be an aqueous ammonia solution. Specifically, the following reaction is made.

(13) HNO3 + NH4OH → NH4NO3 + H2O

(14) H2SO4 + 2NH4OH → (NH4)2SO4 + 2H2O

Alternatively, the neutralizing agent for neutralization may be urea water. Specifically, the following reaction is made.

(15) 2HNO3 + (NH2)2CO + H2O → 2NH4NO3 + CO2

(16) H2SO4 + (NH2)2CO + H2O → (NH4)2SO4 + CO2

As a result, ammonium nitrate fertilizer and ammonium sulfate fertilizer can be obtained.

In addition, although not shown in the drawings, the neutralizing agent may be supplied from a separate neutralizing agent storage tank into the neutralization tank 900 by a supply pump.

However, the present invention is not limited thereto, and the neutralization tank 900 may be omitted, and the neutralization agent for neutralization may be directly supplied into the absorption tank 100. Accordingly, the neutralization reaction of nitric acid and sulfuric acid is performed in the absorption tank 100 as shown in Reaction Formulas (13), (14) or (15), (16), and nitrate and sulfate are added to the absorption tank 100. Can be discharged from That is, nitrogen oxides and sulfur oxides in the exhaust gas can be absorbed and neutralized at the same time.

Alternatively, the neutralizing agent for neutralization may be an aqueous calcium carbonate (CaCO3) solution, and as a result, gypsum may be obtained. Specifically, the following reaction is made.

(17) H2SO4 + CaCO3 + H2O → CaSO4·2H2O + CO2

In addition, in order to control the flow rate of the oxidizing agent solution supplied to the second injection unit 400, that is, to control the injection amount of the oxidizing agent solution injected through the second injection unit 400, the present invention is the control unit 700 And a concentration meter 800.

The concentration meter 800 is for measuring the concentration of nitrogen monoxide (NO) in the exhaust gas flowing into the inlet duct 210, and the control unit 700 is used for measuring the concentration of the exhaust gas measured by the concentration meter 800. The injection amount of the oxidizing agent solution injected through the second injection unit 400 may be controlled according to the concentration of nitrogen monoxide (NO).

At this time, the flow rate control valve V1 is composed of an electric valve and receives an electrical signal to adjust the flow rate by adjusting the opening degree, and the control unit 700 generates an electrical signal to control the opening degree of the flow control valve V1. can send.

Specifically, the control unit 700, when the nitrogen monoxide concentration of the exhaust gas measured by the concentration meter 800 exceeds a reference value, the injection amount of the oxidizing agent solution injected through the second injection unit 400 Can increase That is, the control unit 700 may increase the flow rate of the oxidizing agent solution supplied to the second injection unit 400 by sending an electrical signal to open the flow rate control valve V1.

In addition, the control unit 700, when the nitrogen monoxide concentration of the exhaust gas measured by the concentration meter 800 does not exceed a reference value, the injection amount of the oxidizing agent solution injected through the second injection unit 400 Can be reduced. That is, the control unit 700 may reduce the flow rate of the oxidizing agent solution supplied to the second injection unit 400 by sending an electrical signal to close the flow rate control valve V1.

That is, the amount of the oxidizing agent required to oxidize nitrogen monoxide (NO) in the exhaust gas to nitrogen dioxide (NO2) can be supplied.

As described above, by controlling the injection amount of the oxidizing agent solution injected through the second injection unit 400 according to the nitrogen monoxide concentration of the exhaust gas, oxidation of nitrogen monoxide contained in the exhaust gas can be efficiently performed, and the oxidizing agent solution By adjusting the injection amount of the operating cost can be reduced.

Next, an apparatus according to a second embodiment of the present invention will be described with reference to FIG. 4.

The apparatus according to the second embodiment of the present invention is largely an absorption tank 100, a first absorption tower 1200, a second absorption tower 2200, an exhaust gas inlet duct 210, and an exhaust gas outlet duct 220. , A first injection unit 300, a circulation pump 320, a second injection unit 400, an oxidizing agent supply unit 500, an oxygen supply pipe 600, a control unit 700, and a concentration meter 800. have.

In this case, only the structure of the plurality of absorption towers, that is, the first absorption tower 1200 and the second absorption tower 2200 is different from that of the first embodiment, and all other configurations are the same, focusing on different parts. Let me explain.

The first absorption tower 1200 and the second absorption tower 2200 are formed to extend above the absorption tank 100, extend parallel to each other, and may be integrally formed with the absorption tank 100.

One side of the absorption tower 200 is provided with an exhaust gas inlet duct 210 through which exhaust gas is introduced, and the other side of the absorption tower 200 is an exhaust gas outlet duct 220 through which the purified exhaust gas is discharged. Is provided, in the present embodiment, the inlet duct 210 is provided in the upper left of the first absorption tower 1200 based on FIG. 4, and the outlet duct 220 is the second absorption tower 2200 ) Is provided in the upper right.

Accordingly, the exhaust gas flowing into the first absorption tower 1200 through the inlet duct 210 flows downward in the first absorption tower 1200 and crosses the absorption tank 100 to a second Exhaust gas flowing into the absorption tower 2200 may flow upward in the second absorption tower 2200.

At this time, the first injection unit 300 and the second injection unit 400 are installed in the first absorption tower 1200 as in the first embodiment, and the first injection unit 300 and the second The injection unit 400 is installed in parallel in the first absorption tower 1200, and the second injection unit 400 is formed above the first injection unit 300.

Accordingly, the exhaust gas flowing into the inlet duct 210 flows downward in the first absorption tower 1200 and is in primary contact with the oxidizing agent solution injected by the second injection unit 400, and the It may be in secondary contact with the absorption solution sprayed by the first injection unit 300, it is possible to obtain the same reaction and effect as in the first embodiment.

In addition, only the first injection unit 300 is installed in the second absorption tower 2200, and the exhaust gas introduced into the second absorption tower 2200 flows to the top thereof and the first injection unit 300 It can be in third contact with the absorption solution sprayed by ).

At this time, since the second injection unit 400 is not installed in the second absorption tower 2200, the spray height of the absorption solution sprayed from the first injection unit 300 installed in the second absorption tower 2200 is It may be formed higher than the spray height of the absorption solution sprayed from the first spray unit 300 installed in the first absorption tower 1200.

Accordingly, after passing through the first absorption tower 1200 in the second absorption tower 2200, additional absorption of nitrogen dioxide and sulfur dioxide remaining in the exhaust gas may be performed, and denitrification and desulfurization efficiency may be improved.

Finally, an apparatus according to a third embodiment of the present invention will be described with reference to FIGS. 5 and 6.

The apparatus according to the third embodiment of the present invention is largely, an absorption tank 100, an absorption tower 200, an exhaust gas inlet duct 3210, an exhaust gas outlet duct 3220, a first injection part 3300, and circulation. A pump 320, a second injection unit 3400, an oxidant supply unit 500, an oxygen supply pipe 600, a control unit 700, a concentration meter 800, and a turbulence generator 3240 may be included.

At this time, in this embodiment, the structure of the exhaust gas inlet duct 3210 and the outlet duct 3220, the first injection part 3300 and the second injection part 3400, and the turbulence generator 3240 are further included. Only the structure described above is different from the first embodiment, and all other configurations are the same, and thus different parts will be mainly described.

In this embodiment, the inlet duct 3210 extends from the upper side of the absorption tower 200 to the inside thereof, as shown in FIG. 5, and may extend from the central portion of the absorption tower 200. . In addition, the outlet duct 3220 is formed on one side of the upper portion of the absorption tower 200.

Accordingly, the exhaust gas flowing into the absorption tower 200 through the inlet duct 3210 is precisely the exhaust gas flowing down the absorption tower 200 through the inlet duct 3210 is the absorption tower It flows upward within 200 and is discharged through the outlet duct 3220.

In this case, the second injection part 3400 is installed inside the inlet duct 3210, and the first injection part 3300 is installed inside the absorption tower 200. In this embodiment, the first injection part 3300 is installed in all parts of the absorption tower 200 except for the inlet duct 3210, but is not limited thereto, and the inlet duct 3210 It can be installed inside.

In addition, it further includes a turbulence generator 3240 installed in the inlet duct 3210. The turbulence generator 3240 is formed above the second injection part 3400, and accordingly, the turbulence generator 3240 generates turbulence of the exhaust gas introduced through the inlet duct 3210 to generate the first 2 The oxidizing agent solution sprayed through the injection unit 3400 is mixed by turbulence, so that the oxidation efficiency can be increased. To this end, a driving unit (not shown) for driving the turbulence generator 3240 may be further included.

In this way, the exhaust gas flowing into the absorption tower 200 through the inlet duct 3210 passes through the inlet duct 3210 and is in primary contact with the oxidizing agent solution injected by the second injection unit 3400. , It flows from the inside of the absorption tower 200 to the top and may be in secondary contact with the absorption solution sprayed by the first injection unit 3300, and the same reactions and effects as in the first embodiment can be obtained. .

However, the present invention is not limited thereto, and of course, the turbulence generator may be installed in the absorption tower 200 in the first embodiment.

According to the present invention, nitrogen monoxide (NO) contained in exhaust gas is oxidized by spraying a liquid oxidizing agent, so that nitrogen oxides and sulfur oxides can be simultaneously removed using an organic catalyst.

In this way, by adding a denitrification capability to a conventional wet flue gas desulfurization apparatus, denitrification and desulfurization can be simultaneously performed at low cost with one apparatus and process. In addition, low-temperature denitrification is possible.

The present invention is not limited to the specific embodiments and description described above, and any person with ordinary knowledge in the technical field to which the present invention pertains without departing from the gist of the present invention claimed in the claims can implement various modifications And, such modifications are within the scope of protection of the present invention.

[First embodiment]
100: absorption tank 120: stirrer
200: absorption tower 210: exhaust gas inlet duct
220: exhaust gas outlet duct 230: moisture remover
300: first injection unit 320: circulation pump
400: second injection unit 410: a plurality of nozzles
420: mist maker 430: inlet
500: oxidant supply unit 520: storage tank
540: supply pump 600: oxygen supply pipe
700: control unit 800: concentration meter
900: Chinese tank
[Second Example]
1200: first absorption tower 2200: second absorption tower
[Third Example]
3210: inlet duct 3220: outlet duct
3240: turbulence generator 3300: first injection unit
3400: second injection unit

Claims (18)

An absorption tank in which an absorption solution containing an organic catalyst is stored;
An absorption tower extending above the absorption tank;
An exhaust gas inlet duct provided on one side of the absorption tower;
An exhaust gas outlet duct provided on the other side of the absorption tower;
A first spray unit installed in the absorption tower to spray the absorption solution;
A circulation pump for supplying the absorption solution in the absorption tank to the first injection unit;
A second spray unit installed in the absorption tower to spray an oxidizing agent solution;
An oxidizing agent supply unit supplying an oxidizing agent solution to the second injection unit; And
Includes; an oxygen supply pipe for supplying an oxygen-containing gas to the absorption tank,
The exhaust gas flowing into the inlet duct first contacts the oxidizing agent solution injected by the second injection unit, and secondly contacts the absorption solution injected by the first injection unit,
The oxidizing agent supply unit,
A storage tank in which an oxidant solution is stored; And
Including; a feed pump for supplying the oxidizing agent solution stored in the storage tank to the second injection unit,
The second spray unit is made of a tray provided with a plurality of nozzles through which an oxidizing agent solution is sprayed, and the trays are formed in plural and are alternately installed on one side and the other side of the absorption tower
An apparatus for simultaneously removing nitrogen oxides and sulfur oxides of exhaust gas, wherein an ultrasonic mist maker is installed at each of the plurality of nozzles. The method of claim 1,
The organic catalyst is an organic sulfoxide generated from oil (oil-derived sulfoxides), the simultaneous removal of nitrogen oxides and sulfur oxides of exhaust gas. The method of claim 1,
The oxidizing agent is composed of at least one of H2O2, NaClO2, KMnO4, P4O10, the simultaneous removal of nitrogen oxides and sulfur oxides of exhaust gas. delete delete delete delete The method of claim 1,
The tray is provided with a solution inlet for supplying the oxidizing agent solution to the plurality of nozzles, the simultaneous removal of nitrogen oxides and sulfur oxides of exhaust gas. delete The method of claim 1,
A flow control valve is installed on an oxidizing agent supply line through which an oxidizing agent solution is supplied from the storage tank to the second injection unit, and a device for simultaneously removing nitrogen oxides and sulfur oxides of exhaust gas. The method of claim 10,
A concentration meter for measuring the concentration of nitrogen monoxide (NO) in the exhaust gas flowing into the inlet duct;
An apparatus for simultaneously removing nitrogen oxides and sulfur oxides of exhaust gas comprising a further. The method of claim 11,
A control unit controlling an injection amount of the oxidizing agent solution injected through the second injection unit according to the nitrogen monoxide (NO) concentration of the exhaust gas measured by the concentration measuring device;
An apparatus for simultaneously removing nitrogen oxides and sulfur oxides of exhaust gas comprising a further. The method of claim 12,
The control unit, when the nitrogen monoxide (NO) concentration of the exhaust gas measured by the concentration meter exceeds a reference value, increases the injection amount of the oxidizing agent solution injected through the second injection unit, nitrogen oxide of the exhaust gas and Simultaneous removal of sulfur oxides. The method of claim 12,
When the concentration of nitrogen monoxide (NO) in the exhaust gas measured by the concentration measuring device does not exceed a reference value, the control unit reduces the injection amount of the oxidizing agent solution injected through the second injection unit, and Simultaneous removal of sulfur oxides. The method of claim 12,
The flow control valve is an electric valve, an apparatus for simultaneously removing nitrogen oxides and sulfur oxides of exhaust gas. The method of claim 1,
A turbulence generator installed in the inlet duct or the absorption tower;
An apparatus for simultaneously removing nitrogen oxides and sulfur oxides of exhaust gas comprising a further. The method of claim 1,
A neutralization tank for neutralizing nitric acid and sulfuric acid discharged from the absorption tank;
An apparatus for simultaneously removing nitrogen oxides and sulfur oxides of exhaust gas comprising a further. The method of claim 17,
The neutralizing agent for neutralization is composed of at least one of ammonia water, urea water, and calcium carbonate aqueous solution, simultaneously removing nitrogen oxides and sulfur oxides from exhaust gas.

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