JP2012011317A - System for treating mercury in exhaust gas - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a system for treating mercury in exhaust gas which can further remove residual mercury on the downstream side of a desulfurization device to remove the mercury concentration in the exhaust gas to a very low level.SOLUTION: The system for treating mercury in exhaust gas includes an ammonium chloride solution supply means 16 which sprays an NHCl solution 14 as a reduction-oxidation auxiliary agent into a flue 13 on the downstream of a boiler 11, a reduction-denitrification device 17 which has a denitration catalyst for reducing NOx in exhaust gas 12 with NHgas and oxidizing metal mercury (Hg) in the coexistence of HCl gas, a heat exchanger 18 which performs heat exchange of the denitrated exhaust gas 12, a dust collector 19 which removes soot in the denitrated exhaust gas 12, a wet desulfurization device 21 which removes divalent Hgoxidized in the reduction-denitrification device 17 by using lime gypsum slurry (alkali absorbing liquid) 20, and a finishing mercury removing device 70 which is installed inside or downstream of the wet desulfurization device 21 to remove mercury remaining in the exhaust gas.

Description

  The present invention relates to a mercury treatment system in exhaust gas capable of removing mercury in exhaust gas to an extremely low concentration.

The exhaust gas generated when burning coal-fired exhaust gas or heavy oil may contain metal mercury (Hg ⁰ ) in addition to soot, sulfur oxide (SOx), and nitrogen oxide (NOx). In recent years, various devices and methods for treating metallic mercury (Hg ⁰ ) have been devised in combination with a denitration device that reduces NOx and a wet desulfurization device that uses an alkaline absorbent as an SOx absorbent.

As a method for treating metallic mercury (Hg ⁰ ) in exhaust gas, a method has been proposed in which an NH ₄ Cl solution is sprayed in the flue and supplied into the flue in the upstream process of the reducing denitration device (for example, in the flue) (for example, (See Patent Documents 1 and 2.) When the NH ₄ Cl solution is sprayed in a liquid state in the flue, NH ₄ Cl is dissociated to generate ammonium (NH ₃ ) gas and hydrogen chloride (HCl) gas. NH ₃ gas acts as a reducing agent, and HCl gas acts as a mercury chlorinating agent. That is, NH ₃ undergoes a reduction reaction with NOx in the exhaust gas as represented by the following formula (1) on the denitration catalyst packed in the reducing denitrification apparatus, and HCl is contained in the exhaust gas as represented by the following formula (2). The oxidation reaction proceeds with Hg ⁰ . NH ₃ is reduced and denitrated on the denitration catalyst, and metal mercury (Hg ⁰ ) is oxidized to form water-soluble mercury chloride (HgCl ₂ ), and then HgCl ₂ is treated with water by a wet desulfurization device installed on the downstream side. To remove mercury contained in the exhaust gas.
4NO + 4NH ₃ + O ₂ → 4N ₂ + 6H ₂ O (1)
Hg ⁰ + 1 / 2O ₂ + 2HCl → HgCl ₂ + H ₂ O (2)

JP 2008-142602 A JP 2009-202107 A

By the way, in the conventional proposal for removing mercury in the exhaust gas, NH ₄ Cl solution is sprayed in liquid form in the upstream process of the reductive denitration device into the exhaust gas discharged from the boiler, and the mercury in the exhaust gas inside the denitration device. After being oxidized to divalent mercury (Hg ²⁺ ), mercury oxide is removed by a dust removal device and a desulfurization device. However, in the exhaust gas flowing into the desulfurization device, metal (elemental) mercury (Hg ⁰ ) is mainly used. ), but two kinds of mercury contained in the mercury oxide (Hg ^2+), can not be only absorbed and removed mercury oxide (Hg ²⁺⁾ is water-soluble in the desulfurization apparatus, the metallic mercury Hg ⁰ It cannot be removed and may be discharged from the chimney.
In addition, part of the mercury oxide Hg ²⁺ absorbed and removed may be reduced again to elemental mercury Hg ⁰ and similarly released from the chimney.

  Therefore, even in a system in which mercury is oxidized on the upstream side of the desulfurization apparatus, it is desired to further remove remaining mercury on the downstream side of the desulfurization apparatus and remove the mercury concentration in the exhaust gas to an extremely low concentration. .

  The present invention has been made in view of the above, and even in a system in which mercury is oxidized on the upstream side of the desulfurization apparatus, the remaining mercury is further removed on the downstream side of the desulfurization apparatus, and the mercury concentration in the exhaust gas An object of the present invention is to provide a mercury treatment system in exhaust gas capable of removing slag to an extremely low concentration.

  1st invention which solves the subject mentioned above and achieves an object sprays the solution containing the reduction oxidation auxiliary agent which produces hydrogen chloride and ammonia when it vaporizes in the flue which discharges the exhaust gas from a boiler. A reduction oxidation auxiliary agent supply means, a reduction denitration apparatus having a denitration catalyst that reduces nitrogen oxides in the exhaust gas with ammonia and oxidizes mercury in the presence of hydrogen chloride, and mercury oxidized in the reduction denitration apparatus A wet desulfurization apparatus that removes with an alkali absorbing liquid, and a finish mercury removal apparatus that is provided inside or on the downstream side of the wet desulfurization apparatus and that removes mercury remaining in the exhaust gas. Located in mercury processing system.

  According to a second invention, in the first invention, the finishing mercury removal device provided on the downstream side of the wet desulfurization device is at least one of a dust removal treatment device, an adsorption treatment device, or a gas-liquid contact treatment device. It is in the mercury treatment system in the exhaust gas characterized by

  A third invention is characterized in that, in the first invention, the finishing mercury removing device provided in the wet desulfurization device is an oxidant supply means for supplying an oxidant into the absorbent of the wet desulfurization device. It is in the mercury treatment system in the exhaust gas.

  The fourth invention is characterized in that, in the first invention, the finishing mercury removing device provided in the wet desulfurization device is an activated carbon supply means for supplying activated carbon into the absorbent of the wet desulfurization device. It is in the mercury treatment system in exhaust gas.

  A fifth invention is the mercury treatment system in exhaust gas according to the first invention, wherein either one or both of a reducing agent and a mercury chlorinating agent is further added to the reducing oxidation aid.

  A sixth invention is the mercury treatment system in exhaust gas according to the first invention, wherein the reducing oxidation aid is ammonium halide.

  A seventh invention is the mercury treatment system in exhaust gas according to the second or third invention, wherein the reducing agent is ammonia or urea.

  An eighth invention is the mercury treatment system in exhaust gas according to any one of the second to fourth inventions, wherein the mercury chlorinating agent is a hydrogen halide.

  According to a ninth invention, in the first invention, a solid-liquid separation means for separating a solid content and a liquid content in the desulfurization effluent discharged from the wet desulfurization apparatus, and a mercury removal means for removing mercury in the desulfurization effluent. And a treatment wastewater return means for returning at least part of the treated wastewater treated by the wastewater treatment device to the wet desulfurization device.

  In a tenth aspect based on the ninth aspect, the mercury removing means adds the aggregation aid to the separated liquid obtained by separating the solid matter in the desulfurization waste water by the first solid-liquid separation means. The mercury treatment system in exhaust gas has solid-liquid separation means for solidifying and separating solid mercury from the desulfurization effluent.

  An eleventh invention is the mercury treatment system in exhaust gas according to the ninth invention, characterized in that the waste water treatment apparatus has halogen ion removal means for removing halogen ions in the desulfurization waste water.

  In a twelfth aspect based on the ninth aspect, the flocculating aid is a sulfide, and the waste water treatment apparatus assists the oxidation treatment of the flocculating aid contained in the separated liquid from which the mercury solids are separated. It exists in the mercury processing system in waste gas characterized by having an agent oxidation means.

  According to a thirteenth aspect, in the ninth aspect, an air heater that is provided between the reductive denitration device and the wet desulfurization device, recovers heat of the exhaust gas, a path for supplying fuel to the boiler, and the interior of the boiler An exhaust gas, further comprising: a waste water supply means that is installed in at least one place inside the flue between the boiler and the air heater and supplies a part of the treated waste water treated by the waste water treatment device. In the mercury treatment system.

  In a fourteenth aspect based on the thirteenth aspect, a bypass pipe is provided in at least one of a position parallel to the flue from the reductive denitration device or a position parallel to the flue from the air heater, and the bypass pipe The mercury treatment system in the exhaust gas is characterized in that the waste water supply means is provided.

According to the present invention, mercury (mainly elemental mercury Hg ⁰ ) in the purified gas discharged from the desulfurization apparatus is efficiently removed, so that the mercury concentration remaining in the gas discharged from the exhaust gas treatment system is extremely low. It can be a concentration.

FIG. 1 is a schematic diagram showing a mercury treatment system in exhaust gas according to Embodiment 1 of the present invention. FIG. 2 is a diagram simply showing the configuration of the spray device. FIG. 3 is a schematic view showing a mercury treatment system in another exhaust gas according to Embodiment 1 of the present invention. FIG. 4 is a diagram simply showing the configuration of the spray device. FIG. 5 is a schematic view showing a mercury treatment system in another exhaust gas according to Embodiment 1 of the present invention. FIG. 6 is a schematic diagram showing a mercury treatment system in exhaust gas according to Embodiment 2 of the present invention. FIG. 7 is a schematic view showing a mercury treatment system in exhaust gas according to Embodiment 3 of the present invention. FIG. 8 is a schematic view showing a mercury treatment system in exhaust gas according to Embodiment 4 of the present invention. FIG. 9 is a diagram illustrating an example of the configuration of the waste water treatment apparatus according to the fourth embodiment. FIG. 10 is a diagram illustrating an example of the configuration of another wastewater treatment apparatus according to the fourth embodiment. FIG. 11 is a diagram illustrating an example of the configuration of another wastewater treatment apparatus according to the fourth embodiment. FIG. 12 is a schematic view showing a mercury treatment system in exhaust gas according to Embodiment 5 of the present invention.

  DESCRIPTION OF EMBODIMENTS Hereinafter, modes (hereinafter referred to as examples) for suitably carrying out the present invention will be described in detail with reference to the drawings. In addition, this invention is not limited by the content described in the following Examples. In addition, constituent elements in the following embodiments described below include those that can be easily assumed by those skilled in the art, those that are substantially the same, and those in a so-called equivalent range. Furthermore, the constituent elements disclosed in the following embodiments described below can be appropriately combined.

A mercury treatment system in exhaust gas according to Embodiment 1 of the present invention will be described with reference to the drawings. FIG. 1 is a schematic diagram showing a mercury treatment system in exhaust gas according to Embodiment 1 of the present invention. As shown in FIG. 1, the mercury treatment system 10 </ b> A in the exhaust gas according to the present embodiment is an Hg removal system that removes Hg contained in the exhaust gas 12 from the boiler 11, and in the flue 13 downstream of the boiler 11. In addition, an ammonium chloride (NH ₄ Cl) solution supply means (reduction oxidation assistant supply means) 16 for spraying an NH ₄ Cl solution 14 containing ammonium chloride (NH ₄ Cl) as a reduction oxidation aid, and NOx in the exhaust gas 12 Is reduced with NH ₃ gas, and a reduction denitration device (reduction denitration means) 17 having a denitration catalyst that oxidizes metallic mercury (Hg ⁰ ) in the presence of HCl gas, and a heat exchanger that exchanges heat between the denitrated exhaust gas 12 (Air heater: AH) 18, a dust collector (ESP: Electrostatic Precipitator) 19 that removes soot and dust in the denitrated exhaust gas 12, and a bivalent oxidized in the reducing denitration device 17 The wet desulfurization system 21 be removed using lime gypsum slurry (alkaline absorbing solution) 20 hg ^2+, provided inside or rear flow side of the wet desulfurization system, finishing mercury removing mercury remaining in the flue gas 12 And a removing device 70.

In the mercury treatment system 10A in the exhaust gas according to the present embodiment, NH ₄ Cl is used as an example of the reduction oxidation aid, but this embodiment is not limited to this, and the reduction oxidation aid. Can be used as long as it generates an oxidizing gas and a reducing gas when vaporized. In this embodiment, the reducing oxidation assistant is an oxidation assistant used to oxidize metallic mercury (Hg ⁰ ) in the presence of an oxidizing gas, and a reducing agent that reduces NOx with the reducing gas. That which functions. In this embodiment, HCl gas is used as the oxidizing gas, and NH ₃ gas is used as the reducing gas.

The flue gas 12 discharged from the boiler 11, solution _of NH ₄ Cl 14 is supplied from the solution _of NH ₄ Cl supply unit 16. The NH ₄ Cl solution supply means 16 includes a spray device 23A for oxidizing Hg ⁰ contained in the exhaust gas 12, and an ammonium chloride (NH ₄ Cl) solution that supplies the NH ₄ Cl solution 14 in a liquid state to the spray device 23A. having a supply pipe 24, and a solution _of NH ₄ Cl 14 air supply pipe 26 for supplying air 25 to spray compressed into spray device 23A into the flue 13.

The spraying device 23 </ b> A is a two-fluid nozzle that is provided in the flue 13 and injects the NH ₄ Cl solution 14 and the air 25 into the flue 13 at the same time. The spraying device 23 </ b> A includes a blowing pipe 27 and a nozzle head 28. FIG. 2 is a diagram simply showing the configuration of the spraying device 23A. As shown in FIG. 2, the blow-in pipe 27 is inserted into the flue 13 and is formed in a double pipe structure including an inner pipe 29 and an outer pipe 30. The inner tube 29 is a tube used for feeding the NH ₄ Cl solution 14. The outer tube 30 is a tube that is provided so as to cover the outer periphery of the inner tube 29 and is used to feed the air 25 into the space with the inner tube 29.

The NH ₄ Cl solution 14 is fed from the NH ₄ Cl solution tank 38 to the blowing pipe 27 through the NH ₄ Cl solution supply pipe 24. The flow rate of the NH ₄ Cl solution 14 supplied from the NH ₄ Cl solution supply pipe 24 is adjusted by the control valve V1. The NH ₄ Cl solution 14 is adjusted to a predetermined concentration in the NH ₄ Cl solution tank 38. The NH ₄ Cl solution 14 can be generated by dissolving ammonium chloride (NH ₄ Cl) powder in water. By adjusting the supply amounts of the NH ₄ Cl powder and water, the NH ₄ Cl solution 14 having a predetermined concentration can be adjusted. The NH ₄ Cl solution 14 may be generated by mixing an HCl solution and an NH ₃ solution at a predetermined concentration ratio.

The air 25 is supplied from the air supply unit 39 to the blowing pipe 27 through the air supply pipe 26 and used as compression air when the NH ₄ Cl solution 14 is sprayed from the nozzle head 28. By atomizing solution _of NH ₄ Cl 14 by a gas stream of air 25, a solution _of NH ₄ Cl 14 ejected from the nozzle head 28 can be sprayed as fine droplets into the flue 13. The flow rate of the air 25 supplied from the air supply pipe 26 is adjusted by the control valve V2. The size of the droplets of the NH ₄ Cl solution 14 sprayed from the nozzle holes of the nozzle head 28 can be adjusted by the flow rate of the air 25 supplied from the air supply pipe 26. In addition, the flow rate of the air 25 ejected from the nozzle head 28 is preferably set to, for example, an air / water ratio of 100 to 10,000 (volume ratio). This is because the NH ₄ Cl solution 14 ejected from the nozzle head 28 is sprayed into the flue 13 as fine droplets.

Since the air 25 flows through the space between the inner tube 29 and the outer tube 30, the air 25 serves to cool the NH ₄ Cl solution 14, and the heat of the exhaust gas 12 in the flue 13 is heated by the air 25 to the NH ₄ Cl solution. 14 can be suppressed. Since the NH ₄ Cl solution 14 can be suppressed from being heated by the heat of the exhaust gas 12, the liquid state can be maintained until immediately before the NH ₄ Cl solution 14 is jetted.

FIG. 3 is a schematic view showing a mercury treatment system in another exhaust gas according to Embodiment 1 of the present invention. FIG. 4 is a schematic view of another form of spraying apparatus. As shown in FIGS. 3 and 4, a mercury treatment system 10B in other exhaust gas according to the first embodiment is further provided outside the outer tube 30 as a spray device 23B instead of the spray device 23A according to the first embodiment. An outer cylinder 31 is provided, and two types of first air 25A and second air 25B are supplied to supply air. That is, NH sprayed from the nozzle head 28 by injecting the second air 25B between the outer tube 30 and the outer cylinder 31 and injecting the second air 25B from the gap at the tip of the outer cylinder. The droplets of ₄ Cl solution 14 can be further dispersed in the flue 13.
The air 25A and 25B are supplied from the air supply units 39A and 39B to the blowing pipe 27 via the air supply pipes 26A and 26B.

The second air 25B injected from the gap at the tip of the outer cylinder 31 prevents the NH ₄ Cl solution 14 injected from the nozzle head 28 from adhering to the outer cylinder 31, Is used to prevent boiling of the NH ₄ Cl solution 14 and precipitation of ammonium chloride particles.

Further, since the second air 25B flows between the outer cylinder 31 and the outer pipe 30, it acts as air for cooling the NH ₄ Cl solution 14, and the heat of the hot exhaust gas 12 in the flue 13 is heated by the outer cylinder. Transmission from the outside of 31 into the outer tube 30 can be prevented. For this reason, it is possible to prevent the NH ₄ Cl solution 14 from boiling in the outer cylinder 31 by preventing the temperature rise in the outer cylinder 31 and preventing the NH ₄ Cl solution 14 from being heated. The liquid state can be maintained until immediately before the NH ₄ Cl solution 14 is jetted. Further, corrosion of the nozzle head 28 can be prevented.

The droplets of the NH ₄ Cl solution 14 sprayed from the nozzle head 28 into the flue 13 are evaporated and vaporized by the high-temperature ambient temperature of the exhaust gas 12 to generate fine NH ₄ Cl solid particles. As in 3), it decomposes into HCl and NH ₃ and sublimes. Therefore, the NH ₄ Cl solution 14 sprayed from the spraying device 23A (23B) is decomposed to generate HCl and NH ₃ , and the NH ₃ gas and HCl gas can be supplied into the flue 13.
NH ₄ Cl → NH ₃ + HCl (3)

The droplet diameter of the NH ₄ Cl solution 14 sprayed from the nozzle head 28 is preferably a fine droplet having an average of 1 nm to 100 μm. By generating fine droplets of 1 nm or more and 100 μm or less on average, NH ₄ Cl solid particles generated from the droplets of the sprayed NH ₄ Cl solution 14 can be converted into NH ₃ , HCl in the exhaust gas 12 with a short residence time. It can be decomposed and sublimated. Thereby, since it is not necessary to heat the NH ₄ Cl solution 14 in advance, it is possible to prevent the flue 13 and the nozzle head 28 from being lowered and corroded.

For example, when the droplet temperature is 20 ° C., the concentration of the NH ₄ Cl solution 14 is preferably 20 wt% or more and 30 wt% or less. Table 1 shows the relationship between the temperature of the droplets of the NH ₄ Cl solution 14, the solubility, and the concentration. This is because the solubility of the NH ₄ Cl solution 14 is roughly determined according to the temperature of the droplet, as shown in Table 1.

  Although the temperature of the exhaust gas 12 in the flue 13 depends on the combustion conditions of the boiler 11, it is preferably 320 ° C. or higher and 420 ° C. or lower, more preferably 320 ° C. or higher and 380 ° C. or lower, and further preferably 350 ° C. or higher and 380 ° C. or lower. . This is because NOx denitration reaction and Hg oxidation reaction can be efficiently generated on the denitration catalyst in these temperature zones.

Further, as shown in FIG. 1, the exhaust gas 12 contains HCl gas and NH ₃ gas generated from droplets of the NH ₄ Cl solution 14 sprayed into the flue 13 from the NH ₄ Cl solution supply means 16. Then, it is fed to the reduction denitration device 17. In the reductive denitration device 17, NH ₃ gas generated by decomposition of NH ₄ Cl is used for reductive denitration of NOx, HCl gas is used for oxidation of Hg, and NOx and Hg are removed from the exhaust gas 12.

That is, NH ₃ gas reduces and denitrates NOx as shown in the following equation (4) on the denitration catalyst filled in the denitration catalyst layer 48 filled in the reduction denitration device 17, and HCl gas expresses the following formula ( Hg is mercury-oxidized as in 5).
4NO + 4NH ₃ + O ₂ → 4N ₂ + 6H ₂ O (4)
Hg + 1 / 2O ₂ + 2HCl → HgCl ₂ + H ₂ O (5)

  The reductive denitration device 17 includes one denitration catalyst layer 48. However, the present embodiment is not limited to this, and the reductive denitration device 17 appropriately determines the number of denitration catalyst layers 48 according to the denitration performance. Can be changed.

  The exhaust gas 12 is reduced by NOx in the exhaust gas 12 and oxidized by Hg in the reductive denitration device 17, and then passes through the air heater 18 and the dust collector (ESP) 19 and is supplied to the wet desulfurization device 21. Further, a heat recovery device may be provided between the air heater 18 and the dust collector (ESP) 19.

  Next, after dust is removed by the dust collector (ESP) 19, the exhaust gas 12 is sent to the wet desulfurization device 21 and subjected to desulfurization treatment. In this wet desulfurization apparatus 21, the exhaust gas 12 is fed from the bottom wall surface inside the apparatus main body 49, and the lime gypsum slurry 20 used as the alkali absorbent is supplied into the apparatus main body 49 through the absorption liquid supply line 50. The nozzle 51 is jetted toward the tower top side. The exhaust gas 12 rising from the bottom side in the apparatus main body 49 and the lime-gypsum slurry 20 jetting down from the nozzle 51 are brought into gas-liquid contact with each other, and HgCl and sulfur oxide (SOx) in the exhaust gas 12 are brought into contact with each other. Is absorbed in the lime gypsum slurry 20, separated and removed from the exhaust gas 12, and the exhaust gas 12 is purified. The exhaust gas 12 purified by the lime gypsum slurry 20 is discharged from the top of the tower, further removes remaining mercury by the finishing mercury removing device 70, and then discharged from the chimney 53 as the purified gas 52 to the outside of the system.

The lime gypsum slurry 20 used for the desulfurization of the exhaust gas 12 includes a lime slurry CaCO ₃ in which limestone powder is dissolved in water, a gypsum slurry CaSO _{4 in} which lime and SOx in the exhaust gas 12 are reacted and further oxidized, and water. Produced by mixing. As the lime gypsum slurry 20, for example, a pumped liquid stored in the tower bottom 54 of the apparatus main body 49 of the wet desulfurization apparatus 21 is used. In the apparatus main body 49, SOx in the exhaust gas 12 reacts with lime (CaCO ₃ ) in the lime-gypsum slurry 20 as shown in the following formula (6).
CaCO ₃ + SO ₂ + 0.5H ₂ O → CaSO ₃ .0.5H ₂ O + CO ₂ (6)

On the other hand, the lime-gypsum slurry 20 that has absorbed SOx in the exhaust gas 12 is mixed with the water 55 supplied into the apparatus main body 49 and oxidized by the air 56 supplied to the tower bottom 54 of the apparatus main body 49. At this time, the lime gypsum slurry 20 that has flowed down in the apparatus main body 49 undergoes a reaction such as the following formula (7) with water 55 and air 56.
CaSO ₃ · 0.5H ₂ O + 0.5O ₂ + 1.5H ₂ O → CaSO ₄ · 2H ₂ O (7)
In this way, SO _x in the exhaust gas 12 is captured in the form of gypsum CaSO ₄ .2H ₂ O in the wet desulfurization apparatus 21.
At this time, since mercury chloride (HgCl ₂ ) in the exhaust gas 12 is water-soluble, it is transferred to the lime gypsum slurry 20 side.

  The lime gypsum slurry 20 used for desulfurization stored in the tower bottom 54 of the wet desulfurization apparatus 21 is extracted from the tower bottom 54 after being oxidized. The extracted lime gypsum slurry 20 is fed to a dehydrator 57 and then discharged out of the system as a dehydrated cake (gypsum) 58 containing mercury chloride (HgCl). As the dehydrator 57, for example, a belt filter or the like is used. Further, the dehydrated filtrate (dehydrated filtrate) is subjected to wastewater treatment such as removal of suspensions in the dehydrated filtrate, heavy metals, and pH adjustment of the dehydrated filtrate. A part of the dewatered filtrate subjected to the wastewater treatment is returned to the wet desulfurization apparatus 21, and the other part of the dehydrated filtrate is treated as wastewater.

  In this embodiment, the lime gypsum slurry 20 is used as the alkali absorbing liquid, but other solutions can be used as the alkali absorbing liquid as long as it can absorb HgCl in the exhaust gas 12.

  The supply method of the lime gypsum slurry 20 is not limited to the method of jetting from the nozzle 51 toward the tower top side, and may be caused to flow down from the nozzle 51 so as to face the exhaust gas 12, for example.

A flow meter 61 for measuring the flow rate of the exhaust gas 12 is provided on the upstream side of the spraying device 23A (23B). The flow rate of the exhaust gas 12 is measured by the flow meter 61. The flow rate value of the exhaust gas 12 measured by the flow meter 61 is sent to the control device 62, and the flow rate, angle, initial velocity, etc. of the NH ₄ Cl solution 14 injected from the nozzle head 28 based on the flow rate value of the exhaust gas 12 are determined. Can be adjusted.

NOx concentration meters 63-1 and 63-2 are provided on the inlet side and the outlet side of the reductive denitration device 17. The value of the NOx concentration in the purified gas 52 measured by the NOx concentration meters 63-1 and 63-2 is transmitted to the control device 62. The control device 62 can confirm the NOx reduction ratio in the reducing denitration device 17 from the value of the NOx concentration in the purified gas 52 measured by the NOx concentration meters 63-1, 63-2. Therefore, by controlling the NH ₄ Cl concentration, supply flow rate, etc. of the NH ₄ Cl solution 14 from the value of the NOx concentration in the purified gas 52 measured by the NOx concentration meters 63-1, 63-2, the spray device 23A ( 23B), the NH ₄ Cl concentration of the NH ₄ Cl solution 14 sprayed can satisfy the predetermined denitration performance.

The flue 13 is provided with mercury (Hg) concentration meters 64-1, 64-2, and 64-3 for measuring the Hg content in the exhaust gas 12 discharged from the boiler 11. The Hg concentration meter 64-1 is provided in the flue 13 between the boiler 11 and the nozzle head 28, and the Hg concentration meter 64-2 is provided between the reductive denitration device 17 and the heat exchanger 18, and Hg The densitometer 64-3 is provided on the downstream side of the wet desulfurization apparatus 21. The value of the Hg concentration in the exhaust gas 12 measured by the Hg densitometers 64-1, 64-2, and 64-3 is transmitted to the control device 62. The control device 62 can confirm the content of Hg contained in the exhaust gas 12 from the value of the Hg concentration in the exhaust gas 12 measured by the Hg concentration meters 64-1, 64-2, and 64-3. By controlling the NH ₄ Cl concentration and supply flow rate of the NH ₄ Cl solution 14 from the value of the Hg concentration in the exhaust gas 12 measured by the Hg concentration meters 64-1, 64-2, and 64-3, The NH ₄ Cl concentration and the supply flow rate of the sprayed NH ₄ Cl solution 14 can satisfy the predetermined denitration performance and maintain the Hg oxidation performance.

  Further, an oxidation-reduction potential measurement control device (ORP controller) 66 that measures the oxidation-reduction potential of the lime gypsum slurry 20 is provided at the tower bottom 54 of the wet desulfurization apparatus 21. The ORP controller 66 measures the value of the oxidation-reduction potential of the lime-gypsum slurry 20. Based on the measured oxidation-reduction potential value, the supply amount of the air 56 supplied to the tower bottom 54 of the wet desulfurization apparatus 21 is adjusted. By adjusting the supply amount of the air 56 supplied to the tower bottom 54, the oxidized Hg collected in the lime gypsum slurry 20 stored in the tower bottom 54 of the wet desulfurization apparatus 21 is reduced. And can be prevented from being diffused from the chimney 53.

The oxidation-reduction potential of the lime gypsum slurry 20 in the wet desulfurization apparatus 21 is preferably in the range of, for example, 0 mV or more and +600 mV or less in order to prevent re-scattering of Hg from the lime gypsum slurry 20. This is because, if the oxidation-reduction potential is within the above range, Hg collected as HgCl ₂ in the lime-gypsum slurry 20 is a stable region, and re-scattering into the atmosphere can be prevented.

Further, in the mercury treatment system 10A in the exhaust gas according to the present embodiment, NH ₄ Cl is used as a reduction oxidation aid, but ammonium bromide (NH ₄ Br) other than NH ₄ Cl, ammonium iodide ( A solution dissolved in water using ammonium halide such as NH ₄ I) as a reduction oxidation aid may be used.

In the present embodiment, a finishing mercury removing device 70 is provided on the downstream side of the wet desulfurization device 21 so as to further remove mercury remaining in the exhaust gas 12 discharged from the wet desulfurization device 21.
In the present embodiment, on the upstream side of the wet desulfurization apparatus 21, the mercury metal in the exhaust gas 12 is oxidized to be converted into a divalent mercury Hg ²⁺ form as mercury chloride (HgCl ₂ ) and removed by about 90%. However, since metallic mercury cannot be completely oxidized, about 10% of metallic mercury remains.
Thus, the remaining zero-valent metallic mercury Hg ⁰ that cannot be processed by the wet desulfurization apparatus 21 is removed to an extremely low concentration by the finishing mercury removing apparatus 70.

In the present invention, as described above, the ammonium chloride (NH ₄ Cl) solution 14 is supplied on the upstream side of the reductive denitration device 17, and the NH ₃ gas generated by the decomposition of NH ₄ Cl is reduced by the reductive denitration device 17. It is used for NOx reductive denitration, and HCl gas is used for Hg oxidation to remove NOx and Hg from the high-temperature exhaust gas 12. Since the reductive denitration device 17 is filled with a denitration catalyst, NH ₃ reductively denitrates NOx on the denitration catalyst, HCl oxidizes metal Hg ⁰ to mercury chloride (HgCl ₂ ), and then wet. Divalent mercury is removed by the desulfurization device 21. Thereafter, the remaining zero-valent mercury is removed by the finishing mercury removing device 70, thereby reducing the mercury concentration.
Thereby, compared with the case where metal mercury in the exhaust gas 12 is removed for the first time on the downstream side of the wet desulfurization apparatus 21, the processing apparatus can be made more compact and the processing cost can be reduced.

  Here, as the finishing mercury removing device 70, at least one of a dust removal processing means, an adsorption processing means, and a gas-liquid contact processing means can be mentioned.

Examples of the dust removal processing means include a gravitational dust collection device that separates dust from a gas by gravity, a dry electrostatic dust collection device (ESP) that charges dust and adsorbs it to a reversely charged electrode plate, or wet electrostatic dust collection. Treatment device (WESP), inertia type dust removal processing device (mist eliminator, cyclone) that changes the gas flow direction and separates dust by inertia, collision type dust removal treatment that separates dust by providing a collision plate etc. in the gas flow direction Examples include an apparatus (for example, a packed tower), a cleaning dust collecting apparatus that separates the liquid by spraying and adsorbing the liquid, but the present invention is not limited thereto.
By removing the metallic mercury remaining in the exhaust gas together with soot dust by this dust removal processing means, the mercury concentration is reduced.

Examples of the adsorption treatment means include physical adsorption treatment such as activated carbon treatment equipment, sulfide-type adsorbent treatment equipment, and chelate-type adsorbent treatment equipment, but the present invention is limited to these. is not.
The mercury concentration is reduced by adsorbing and removing the metallic mercury remaining in the exhaust gas by this adsorption processing means.

Examples of the gas-liquid contact treatment means include a scrubber device that sprays an oxidant solution, but the present invention is not limited to these. As other gas-liquid contact treatment means, various contact means such as a liquid column tower, a spray tower, a packed tower, and a grid tower can be applied.
Examples of the oxidizing agent include a solution containing an oxidizing agent (hypochlorous acid solution, hydrogen peroxide solution), a chelating agent, a sulfur-based agent (S ² -compound), and the like. It is not limited to these.

After the finishing mercury removing device 70 is performed, final processing such as waste water treatment and detoxification processing is performed by the final processing device.
As the waste water treatment in this final treatment device, a known final treatment device such as a sulfide coagulation sedimentation treatment device, a chelating agent treatment device, a chelate resin treatment device, an ion exchange resin treatment device, or an activated carbon treatment device is applied. do it.
Moreover, as a detoxification processing apparatus, a cement solidification processing apparatus can be mentioned, for example.

Thus, when processing the mercury in the exhaust gas 12 from the boiler 11, on the upstream side of the processing system, the mercury in the exhaust gas is oxidized to form water-soluble divalent mercury Hg ²⁺ , In the wet desulfurization apparatus 21, approximately 90% of mercury is removed, and then a finishing mercury removal apparatus 70 is further provided on the downstream side of the wet desulfurization apparatus 21. Mercury (mainly elemental mercury Hg ⁰ ) in the exhaust gas 12 can be removed.
As a result, the mercury concentration in the flue gas discharged from the chimney 53 can be reduced to an extremely low concentration.

A suitable combination in the above-described finishing mercury removal apparatus 70 is 1) a combination of an inertia dust removal treatment apparatus (cyclone, mist eliminator, etc.) and wastewater treatment, 2) a combination of an electrostatic precipitator and wastewater treatment, and 3) gas-liquid contact. A combination of treatment and wastewater treatment is preferable.
In particular, the combination of the inertia dust removal processing device and the waste water treatment is economical because the electrical loss is small and the pressure loss is small as in the case of the electrostatic dust collection treatment and the waste water treatment.

FIG. 5 is a schematic view showing a mercury treatment system in another exhaust gas according to Embodiment 1 of the present invention.
In addition, as shown in FIG. 5, the mercury treatment system 10C in the other exhaust gas according to the first embodiment has an arbitrary NH ₃ solution 81 and an HCl solution 82 in addition to the NH ₄ Cl solution 14. The liquid mixture 84 is supplied at a ratio, mixed in the mixing unit 83 to adjust the liquid mixture 84, and the adjusted liquid mixture 84 is supplied into the flue 13 of the boiler 11.

(Preparation of NH ₄ Cl solution)
First, an NH ₄ Cl solution 14 having a predetermined concentration used as a reduction oxidation aid is prepared. The concentration of the NH ₄ Cl solution 14 is greater than 0 wt% and preferably 43 wt% or less, more preferably 10 wt% or more and 23 wt% or less, further preferably 18 wt% or more and 23 wt% or less, and most preferably around 20 wt%. This is because the NH ₄ Cl powder needs to be dissolved at least in water at room temperature (for example, around 20 ° C.), and it is necessary that the NH ₄ Cl is not more than a saturated dissolution concentration in water. In general, when the solution temperature is around 0 ° C., the saturation concentration at which NH ₄ Cl powder can be dissolved in water is about 23 wt%, and when around 100 ° C., the saturation concentration at which NH ₄ Cl powder can be dissolved in water is It is about 43 wt%. Therefore, the concentration of the NH ₄ Cl solution 14 needs to be greater than 0 wt% and not greater than 43 wt%.

(Preparation of NH ₃ solution)
First, NH ₃ solution 81 obtained by dissolving NH ₃ used as the reducing agent is adjusted by NH ₃ dissolving tank 85. The concentration of NH ₃ is preferably adjusted to be in the range of greater than 0 wt% and 28 wt%, for example.

(Preparation of HCl solution)
First, an HCl solution 82 in which HCl used as a reduction oxidation aid is dissolved is adjusted by an HCl dissolution tank 86. The concentration of HCl is preferably adjusted to be in the range of, for example, greater than 0 wt% and 38 wt% or less.

Here, the added amount of the NH ₄ Cl solution 14 and the supply flow rate of the HCl solution 82 are controlled by combining the HCl gas generated by dissociation from the NH ₄ Cl solution 14 and the HCl gas generated by the vaporization of the HCl solution 82. Thus, the mercury oxidation rate (Hg ²⁺ / Hg ^T ) at the outlet of the reductive denitration device 17 is preferably 95% or more, or the metal mercury concentration (Hg ⁰ ) is 1 μg / Nm ³ or less. Hg ^T refers to the total mercury concentration and is represented by the sum of the metal mercury (Hg ⁰ ) concentration and the mercury oxide (Hg ²⁺ ) concentration as shown in the following formula (8).
Hg ^T = Hg ⁰ + Hg ²⁺ (8)

Further, the respective contents of NOx, Hg, and HCl contained in the high temperature exhaust gas 12 are determined from the coal properties of the coal used in the boiler 11, and each of the NH ₄ Cl solution 14, the NH ₃ solution 81, and the HCl solution 82 is obtained. The supply amount may be determined. That is, the contents of NOx, Hg, and HCl contained in the high-temperature exhaust gas 12 are determined by burning the coal properties in the boiler 11. Then, by maximizing the combustion of coal in the boiler 11, the maximum amount of NOx, Hg, HCl contained in the high temperature exhaust gas 12 can be obtained from the combustion amount of the boiler 11. Therefore, the respective contents of NOx, Hg, and HCl contained in the high-temperature exhaust gas 12 are determined from the coal properties of the coal used in the boiler 11, and the NH ₄ Cl solution 14, the NH ₃ solution 81, and the HCl solution 82 are obtained. The supply amount can be determined.

Therefore, the mercury treatment system 10C in the exhaust gas according to the present embodiment has NH ₄ Cl in the flue 13 in accordance with the balance of NOx and Hg concentrations in the high temperature exhaust gas 12 discharged from the combustion equipment such as the boiler 11. The solution 14, the NH ₃ solution 81, and the HCl solution 82 can be supplied, and the required amount of HCl or NH ₃ can be adjusted and supplied.

(Supply amount control method)
The control device 62 determines the required NH ₃ based on the analysis results of the NOx concentration and the Hg concentration in the high temperature exhaust gas 12 measured by the NOx concentration meters 63-1, 63-2 and the Hg concentration meters 64-1, 64-2. Determine the amount of HCl. The controller 62 determines the supply amounts of the NH ₄ Cl solution 14, the NH ₃ solution 81, and the HCl solution 82 from the obtained concentrations of NH ₃ and HCl. The control device 62 adjusts the supply amounts of the NH ₄ Cl solution 14, NH ₃ solution 81, and HCl solution 82 by controlling the opening and closing of the control valves V 1, V 3, V ₄ . The computing device 62 calculates the flow rate and flow velocity of the mixed solution 84 based on the flow rate of the mixed solution 84 measured by the flow meter 61, and controls the opening and closing of the control valve V5, thereby supplying the supply amount of the mixed solution 84. Adjust.

Further, when the mercury oxidation rate (Hg ²⁺ / Hg ^T ) is smaller than 0.95 or the metal mercury concentration (Hg ⁰ ) is larger than 1 μg / Nm ³ by the Hg concentration meters 64-1 and 64-2. In some cases, the amount of HCl added is increased. The addition amount of HCl can be performed by increasing the supply amount of the HCl solution 82, for example.

Further, the NOx concentration meter 63-1, NOx concentration in the high-temperature exhaust gas 12 at the outlet side of the reduction denitrator 17, NH ₃ concentration is measured, if NH ₃ concentration measured during the high temperature exhaust gas 12 is greater than 1ppm For this, the amount of NH ₃ added is decreased. Further, when the NOx concentration in the high temperature exhaust gas 12 measured by the NOx concentration meter 63-1 is smaller than 1 ppm, the NH ₃ addition amount is increased. However, the NH ₃ concentration is the ratio of the number of moles of NH _{3 to} the number of moles of NOx in the high temperature exhaust gas 12 (NH ₃ / NOx mole ratio) with respect to the NOx mole flow rate (mol / H) on the inlet side of the high temperature exhaust gas 12. However, the value is set to 1 or less according to the required denitration performance. The NH ₃ addition amount can be performed by increasing or decreasing the supply amount of the NH ₃ solution 81, for example.

As described above, according to the mercury treatment system 10C in the exhaust gas according to the present embodiment, the mixed solution 84 obtained by mixing the NH ₄ Cl solution 14, the NH ₃ solution 81, and the HCl solution 82 is used as the flue of the boiler 11 by the spraying device 23A. By spraying in the gas, the NH ₄ Cl solution 14, the NH ₃ solution 81, and the HCl solution 82 are vaporized to become HCl gas and NH ₃ gas, which oxidizes Hg in the high-temperature exhaust gas 12 on the denitration catalyst and NOx Can be reduced. Further, by adjusting the supply amount of the NH ₄ Cl solution 14, NH ₃ solution 81, and HCl solution 82 in the mixed solution 84, the reducing agent and the mercury chlorinating agent are set to appropriate amounts according to the gas properties of the high temperature exhaust gas 12. Can be supplied arbitrarily.
Thereby, optimization of mercury oxidation according to the mercury concentration in the exhaust gas can be achieved.
Therefore, the mercury removal rate in the wet desulfurization apparatus 21 can be improved, and the finishing mercury removal apparatus 70 can be made compact.

FIG. 6 is a schematic diagram showing a mercury treatment system in exhaust gas according to Embodiment 2 of the present invention. In addition, the same code | symbol is attached | subjected to the structure same as Example 1 mentioned above, and the duplicate description is abbreviate | omitted. As shown in FIG. 6, the mercury treatment system 10 </ b> D in the exhaust gas according to the present embodiment includes an oxidant supply unit that introduces a mercury oxidant 90 into the lime gypsum slurry 20 at the bottom of the apparatus main body 49 of the wet desulfurization apparatus 21. Provided. By introducing the mercury oxidizing agent 90, metallic mercury in the lime-gypsum slurry 20 is oxidized and becomes divalent mercury.
As a result, as the concentration of metallic mercury in the liquid decreases, the concentration of metallic mercury that re-scatters to the exhaust gas side also decreases. As a result, the mercury concentration in the exhaust gas 12 discharged from the wet desulfurization device 21 is reduced. Reduction can be achieved.
Here, examples of the oxidizing agent include hypochlorous acid, peracetic acid, hydrogen peroxide water, and the like. Moreover, you may make it throw in Hg absorption liquid etc. instead of an oxidizing agent.

FIG. 7 is a schematic view showing a mercury treatment system in exhaust gas according to Embodiment 3 of the present invention. In addition, the same code | symbol is attached | subjected to the structure same as Examples 1-2 mentioned above, and the overlapping description is abbreviate | omitted. As shown in FIG. 7, the mercury treatment system 10 </ b> E in the exhaust gas according to the present embodiment adds activated carbon 91 to the lime gypsum slurry 20 at the bottom of the apparatus main body 49 of the wet desulfurization apparatus 21, and adds mercury to the activated carbon 91. After adsorbing and feeding to the dehydrator 57, the dehydrated cake (gypsum) 58 containing activated carbon 91 containing mercury chloride (HgCl) may be discharged out of the system.
As a result, the amount of mercury on the lime gypsum slurry 20 side in the wet desulfurization apparatus 21 can be reduced, and the concentration of metallic mercury re-scattered to the exhaust gas 12 side also decreases as the mercury concentration in the liquid decreases. As a result, the mercury concentration in the exhaust gas 12 discharged from the wet desulfurization apparatus 21 can be reduced.

FIG. 8 is a schematic view showing a mercury treatment system in exhaust gas according to Embodiment 4 of the present invention. In addition, the same code | symbol is attached | subjected to the structure same as Examples 1-3 mentioned above, and the duplicate description is abbreviate | omitted. As shown in FIG. 8, the mercury treatment system 10F in the exhaust gas according to the present embodiment is the same as the mercury treatment system 10A in the exhaust gas according to the first embodiment, such as mercury from the desulfurization waste water 201 discharged from the wet desulfurization apparatus 21. Waste water treatment device 202 for removing the harmful substances, and a replenishment water line 204 which is a treated waste water return means for returning at least a part of the treated waste water 203 treated by the waste water treatment device 202 to the wet desulfurization device 21. Yes.
Then, the treated wastewater 203 (203A, 203B, 203C) after removing harmful substances such as mercury contained in the desulfurization wastewater 201 discharged from the wet desulfurization device 21 is returned to the wet desulfurization device 21 side. The waste water 203 is circulated between the waste water treatment apparatus 202 and the mercury concentration of the absorbent used in the wet desulfurization apparatus 21 is reduced by the above-described configuration.

In addition, as described above, the lime gypsum slurry 20 is obtained by pumping the liquid stored in the tower bottom 54 of the wet desulfurization apparatus 21. With operation, gypsum CaSO ₄ .2H ₂ O is mixed. Hereinafter, this lime-gypsum slurry (lime slurry mixed with gypsum) 20 to be pumped is referred to as an absorbent.

The absorption liquid (lime gypsum slurry) used for desulfurization is discharged to the outside from the tower bottom 54 of the wet desulfurization apparatus 21 as desulfurization drainage 201 and sent to the wastewater treatment apparatus 202 via the desulfurization drainage line 205. In addition to gypsum, the desulfurization waste water 201 contains heavy metals such as mercury and halogen ions such as Cl ⁻ , Br ⁻ , I ⁻ and F ⁻ .

In the above-described wet desulfurization apparatus 21, mercury is removed by adsorbing mercury Hg to the gypsum CaSO ₄ .2H ₂ O crystal to be generated. Here, the ratio of the mercury removal amount with respect to the amount of gypsum produced varies depending on the properties of limestone, the halogen ion concentration, the operating conditions of the desulfurization apparatus, and the like, and is approximately 1 to 10 mg / kg (Hg removal amount / CaSO ₄ · 2H _2. O production amount). And in the high mercury content ratio (or low sulfur content ratio) coal whose weight ratio is 1-10 mg / kg or more, mercury may not be fully adsorbed in the gypsum particles. In this case, the mercury concentration in the supernatant water of the lime gypsum slurry 20 increases in the wet desulfurization apparatus 21, and a part of the mercury scatters from the supernatant water to the gas phase (exhaust gas) due to gas-liquid equilibrium. For this reason, it is necessary to reduce the mercury concentration in the supernatant water in order to prevent the scattering of mercury. Therefore, as described below, the desulfurization wastewater 201 is sent to the wastewater treatment device 202, and after performing a wastewater treatment process including solid-liquid separation treatment and mercury removal treatment, the treated wastewater 203 is returned to the wet desulfurization device 21 again. In this way, the treated wastewater 203 is circulated between the wet desulfurization device 21 and the wastewater treatment device 202, thereby reducing the mercury concentration of the absorption liquid.

  FIG. 9 is a diagram illustrating a configuration example of the waste water treatment apparatus 202 according to the fourth embodiment. The waste water treatment apparatus 202A illustrated in FIG. 9 includes a first solid-liquid separation unit 211 that separates the solid content including gypsum in the desulfurization waste water 201 and the liquid content, mercury, boron remaining in the desulfurization waste water 201, A means 214 for removing a substance such as selenium (hereinafter referred to as “mercury removing means 214”) is included.

  As the first solid-liquid separation means 211, for example, a belt filter, a centrifugal separator, a decanter centrifugal sedimentator, or the like is used. The desulfurization waste water 201 discharged from the wet desulfurization apparatus 21 is separated from the gypsum 212 by the first solid-liquid separation means 211. At that time, mercury chloride in the desulfurization waste water 201 is separated from the liquid together with the gypsum 212 in a state of being adsorbed by the gypsum. The separated gypsum 212 is discharged to the outside of the mercury treatment system 10F in the exhaust gas (hereinafter referred to as “outside of the system”). On the other hand, the separation liquid 213 contains a trace amount of mercury, boron, selenium, or other substances that could not be adsorbed on the gypsum 212 (hereinafter, described only for mercury). These substances are removed by the next mercury removing means 214.

  The mercury removing unit 214 solidifies mercury contained in the separation liquid 213 and separates the mercury solid material 217 and the like from the separation liquid 213. In order to perform mercury removal with high accuracy, in the example shown in FIG. 9, mercury removal processing is configured by means having multiple stages. The mercury removing unit 214 includes an auxiliary agent mixing unit 216a for mixing the aggregation auxiliary agent 215, a second solid-liquid separation unit (concentration unit) 216b, a third solid-liquid separation unit (dehydration unit) 216c, and precision processing. Means 216d. First, in the auxiliary agent mixing means 216a, mercury is solidified by mixing the coagulating auxiliary agent 215 with the separation liquid 213, and then in the second solid-liquid separation means (concentration means) 216b, the mercury solids 217 and particulates are formed. Concentrate material. As the concentration means, gravity sedimentation, sand filtration or the like is used. Next, in the third solid-liquid separation means (dehydration means) 216c, the concentrated mercury solid 217, particulate matter, and the like are dehydrated. Centrifugation, a belt filter, etc. are used as a dehydrating means. The solid mercury 217 after dehydration is discharged out of the system. The separation liquid 218 produced by the third solid-liquid separation means (dehydration means) 216c is mixed with the separation liquid 219 separated by the second solid-liquid separation means (concentration means) 216b and sent to the precision processing means 216d. A trace amount of mercury solids 220 and particulate matter remaining in the separation liquid 219 are removed. As the precision treatment, a method such as cyclone or membrane separation is used. The mercury solid material 220 and the like removed by the precision processing means 216d is discharged out of the system.

  The treated wastewater 203A from which the mercury solids 217 and 220 have been removed by the mercury removing means 214 described above is returned to the wet desulfurization device 21 as make-up water for the wet desulfurization device 21 via the make-up water line 204. The treated wastewater 203A returned to the wet desulfurization apparatus 21 is used as an absorbing solution, and then repeatedly treated by the wastewater treatment apparatus 202A. That is, the treated wastewater 203 </ b> A circulates between the wet desulfurization device 21 and the wastewater treatment device 202. Here, the amount of treated wastewater 203A to be circulated through the wastewater treatment device 202A (return amount of the treated wastewater 203A) is determined by how much the mercury concentration and halogen ion concentration of the absorbent in the wet desulfurization device 21 are set. For example, when the mercury concentration of the absorbing solution is lowered, the return amount of the treated wastewater 203A is increased.

  In FIG. 9, a part of the treated wastewater 203A treated by the wastewater treatment apparatus 202A is supplied to the spray water line 240 described later. This corresponds to an example described later. The drainage 203 </ b> A is not supplied to the spray water line 240.

  That is, in Example 4, when the treated wastewater 203A treated by the wastewater treatment apparatus 202A is the same as or lower than the preset value of the makeup water amount, the wet desulphurization apparatus uses all the treated wastewater 203A as makeup water. Return to 21. On the other hand, when the amount of the treated wastewater 203A is larger than the preset value of the makeup water amount, the surplus treated wastewater 203A is discharged out of the system.

  As described above, the mercury treatment system 10F in the exhaust gas of this example includes the first solid-liquid separation unit 211 and the desulfurization for separating the solid content and the liquid content in the desulfurization waste water 201 discharged from the wet desulfurization apparatus 21. A waste water treatment device 202 having a mercury removal means 214 for removing mercury in the waste water 201 and a makeup water line 204 for returning at least a part of the treated waste water 203 treated by the waste water treatment device 202 to the wet desulfurization device 21 are provided. It has a configuration. Thus, the desulfurization waste water 201 discharged from the wet desulfurization device 21 is sent to the waste water treatment device 202 to remove mercury, and at least a part of the treated waste water 203A after removing the mercury is returned to the wet desulfurization device 21. Since the treated wastewater 203A is circulated between the wet desulfurization apparatus 21 and the wastewater treatment apparatus 202, the mercury concentration of the absorbent in the wet desulfurization apparatus 21 can be reduced. As a result, it is possible to suppress a situation in which mercury in the absorbing liquid moves from the liquid phase to the gas phase inside the wet desulfurization apparatus 21 and the mercury is scattered in the exhaust gas 12.

Next, another treatment system for wastewater treatment will be described. FIG. 10 is a diagram illustrating a configuration example of the waste water treatment apparatus 202B according to another aspect. The waste water treatment apparatus 202B shown in FIG. 10 has a chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), iodine ion (I ⁻ ), fluorine ion in addition to the configuration of the waste water treatment apparatus 202A shown in FIG. A means 230 for removing halogen ions such as (F ⁻ ) (hereinafter referred to as “halogen ion removing means 230”) is provided.

The above halogen ions such as chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), iodine ion (I ⁻ ), and fluorine ion (F ⁻ ) are converted into gypsum during the desulfurization process in the wet desulfurization apparatus 21. It has the property of suppressing adsorption. For this reason, if the halogen ion concentration in the treated wastewater returned to the wet desulfurization apparatus 21 is high, the mercury concentration in the supernatant water of the absorption liquid increases, and a phenomenon occurs in which part of the mercury is scattered into the gas phase (exhaust gas). Therefore, it is preferable to remove halogen ions from the separation liquid 231 separated by the mercury removing unit 214 by the halogen ion removing unit 230 to reduce the halogen ion concentration. Examples of the halogen ion removing means 230 include concentrating means using a reverse osmosis membrane, concentrating means using an ion exchange membrane, concentrating means using an electrodialysis method, distillation, crystallization, and the like.

  The processing in the halogen ion removing unit 230 may be performed each time the separation liquid 231 is supplied from the mercury removing unit 214. However, the halogen ion concentration of the separation liquid 231 is measured, and the halogen ion concentration is set. The halogen ion removal process may be performed only when the value exceeds the value, and the process by the halogen ion removal unit 230 may be omitted when the halogen ion concentration is less than the set value.

  The treated wastewater 203B from which the halogen ions have been concentrated and removed by the halogen ion removing means 230 is returned to the wet desulfurization device 21 as make-up water for the wet desulfurization device 21 via the make-up water line 204. As described above, the amount of the treated wastewater 203B circulated through the wastewater treatment device 202B is determined by how much the mercury concentration and the halogen ion concentration of the absorption liquid in the wet desulfurization device 21 are set.

  In FIG. 10, a part of the treated wastewater 203B treated by the wastewater treatment apparatus 202B is supplied to the spray water line 240 described later. This corresponds to an aspect described later. The drainage 203B is not supplied to the spray water line 240. In FIG. 10, the concentrated liquid 241 generated by the halogen ion removing means 230 is mixed in the spray water line 240 described later. This also corresponds to another example described later. In this example, the concentrated liquid 241 is concentrated. The liquid 241 is discharged out of the system.

  Similarly to the above, when the treated wastewater 203B treated by the wastewater treatment device 202B is equal to or lower than the preset value of the amount of makeup water, all the treated wastewater 203B is wetted as makeup water. Return to the desulfurizer 21. On the other hand, if the amount of the treated wastewater 203B is larger than the preset value of the makeup water amount, the surplus treated wastewater 203B is discharged out of the system.

As described above, the waste water treatment apparatus 202B of the present example has a chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), The apparatus includes a halogen ion removing means 230 such as iodine ion (I ⁻ ) or fluorine ion (F ⁻ ). According to the mercury treatment system 10F in the exhaust gas configured as described above, in addition to the actions and effects described above, the halogen ion concentration in the treated wastewater 20B3 can be further reduced. While promoting the transition (solidification), it is possible to suppress scattering into the gas phase.

Next, another treatment system for wastewater treatment will be described. FIG. 11 is a diagram illustrating a configuration example of a wastewater treatment apparatus 202C according to another aspect. The wastewater treatment apparatus 202C shown in FIG. 11 has a configuration in which an auxiliary agent oxidation means 250 is provided in addition to the configuration of the wastewater treatment apparatus 202B shown in FIG. In the auxiliary agent admixing step of the mercury removing means 214, hydrogen sulfide H ₂ S, sodium sulfide Na ₂ S, sodium hydrogen sulfide NaHS, metal sulfide M _x S _y (M is a metal element, such as Mn, Fe, etc.) , X and y are numbers), etc., when the treated wastewater 203C is returned to the wet desulfurization apparatus 21, the coagulant aid 215 contained in the treated wastewater 203C becomes a reducing agent and inhibits oxidation. there is a possibility.
For this reason, when sulfide is used as the agglomeration aid 215, it is preferable to oxidize the agglomeration aid 215 contained in the separation liquid 231 separated by the precision treatment means 216d by the aid oxidation means 250. Specifically, as the oxidation treatment, an oxidant is added, and a treatment of reacting the sulfide with the oxidant is performed. Examples of the oxidizing agent include air, oxygen O ₂ , hydrogen peroxide H ₂ O ₂ , ozone O ₃ , chloric acid compound, manganese compound, and iron compound.

  Halogen ions are concentrated and removed by the halogen ion removing means 230 from the separation liquid 251 that has been processed by the auxiliary oxidizing means 250. The treated wastewater 203C from which the halogen ions have been removed is returned to the wet desulfurization device 21 as make-up water for the wet desulfurization device 21 via the make-up water line 204. As described above, the amount of the treated wastewater 203C circulated through the wastewater treatment device 202C is determined by how much the mercury concentration and the halogen ion concentration of the absorbent in the wet desulfurization device 21 are set.

  In FIG. 11, a part of the treated wastewater 203C treated by the wastewater treatment apparatus 202C is supplied to the spray water line 240 described later. This corresponds to an example described later. The drainage 203 </ b> C is not supplied to the spray water line 240. In FIG. 11, the concentrated liquid 241 generated by the halogen ion removing means 230 is mixed in the spray water line 240 described later. This also corresponds to the example described later. 241 is discharged out of the system.

  Similarly to the above, when the treated wastewater 203C processed by the wastewater treatment apparatus 202C is equal to or lower than the preset value of the supplementary water amount, all the treated wastewater 203C is wetted as supplementary water. Return to the desulfurizer 21. On the other hand, if the amount of the treated wastewater 203C is larger than the preset value of the makeup water amount, the surplus treated wastewater 203C is discharged out of the system.

  As described above, the waste water treatment apparatus 202C in the mercury treatment system 10F in the exhaust gas of the present example includes the auxiliary oxidation means 250 for oxidizing the aggregation aid 215 in addition to the configuration of the waste water treatment apparatus 202B described above. It has a configuration. With the above-described configuration, in addition to the above-described actions and effects, when the treated wastewater 203C is returned to the wet desulfurization apparatus 21, the coagulation aid 215 contained in the treated wastewater 203C becomes a reducing agent and the oxidation is inhibited. Can be prevented.

  In addition, the structure of the waste water treatment equipment 202A-202C illustrated in FIGS. 9-11 is an example, and can be suitably changed according to the property etc. of the desulfurization waste water 201. FIG. For example, in the example shown in FIGS. 9 to 11, mercury is removed with high accuracy by configuring the mercury removal means 214 in multiple stages of a concentration process, a dehydration process, and a precision treatment process, but it is not always necessary to have multiple stages. Instead, any one of these steps may be selected and performed. For example, the mercury concentration in the separation liquid 219 may be measured, and when the mercury concentration is less than the threshold value, the precision processing unit 216d may be omitted. Of course, when the coagulation aid 215 other than sulfide is used, the oxidation treatment (detoxification treatment) of the coagulation aid 215 may be omitted.

  Further, the order of the processing in the first solid-liquid separation unit 211, the processing in the mercury removing unit 214, and the processing in the halogen ion removing unit 230 is not limited to the example shown in FIG. For example, the first solid-liquid separation unit 211 may be performed after the processing by the mercury removing unit 214, or the processing by the mercury removing unit 214 may be performed after the processing by the halogen ion removing unit 230. May be.

FIG. 12 is a schematic view showing a mercury treatment system in exhaust gas according to Embodiment 5 of the present invention. In addition, the same code | symbol is attached | subjected to the structure same as Examples 1-4 mentioned above, and the duplicate description is abbreviate | omitted.
As shown in FIG. 12, the mercury treatment system 10G in the exhaust gas according to the present embodiment is a part of the treated wastewater 203 (203A, 203B, 203C) in the mercury treatment system 10A in the exhaust gas according to the first embodiment. The fuel F is supplied to the boiler 11, the inside of the furnace of the boiler 11, the inside of the flue 13 between the boiler 11 and the air heater 18, and at least one place inside the bypass pipes 13a and 13b.

  The mercury treatment system 10G in the exhaust gas illustrated in FIG. 12 includes the above-described boiler 11, reduction denitration device 17, air heater 18, dust collector 19, wet desulfurization device 21, wastewater treatment device 202 (202A, 202B, 202C), In addition to the makeup water line 204, a spray water line 240 and a drain spray device 261 are provided. Further, a bypass pipe 13 a that connects the upstream side and downstream side flue 13 of the reducing denitration device 17 is provided at a position parallel to the flue 13 from the reduction denitration device 17. Similarly, a bypass pipe 13 b that connects the upstream side and downstream side flue 13 of the air heater 18 is provided at a position parallel to the flue 13 from the air heater 18. By setting it as the said structure, the treated waste_water | drain 203 (203A, 203B, 203C) can be sprayed also in the waste gas 12 which distribute | circulates the inside of each bypass pipe 13a, 13b. Each bypass pipe 13a, 13b is configured such that the amount of exhaust gas flowing through the inside thereof is about several percent of the amount of exhaust gas flowing through the flue 13.

  Of the treated wastewater 203 (203A, 203B, 203C) to be treated by the wastewater treatment apparatus 202 (202A, 202B, 202C), a predetermined amount is returned to the wet desulfurization apparatus 21 via the makeup water line 204, but the treated wastewater 203 Even if (203A, 203B, 203C) is returned to the wet desulfurization apparatus 21, there may still be excess treated wastewater 203 (203A, 203B, 203C). In such a case, the remaining treatment wastewater 203 </ b> A (203 </ b> B, 203 </ b> C) is supplied to the spray water line 240, stored in the drainage tank 260, and a path for supplying the fuel F to the boiler 11 by the wastewater spray device 261. In the furnace, in the flue 13, and in the bypass pipes 13a and 13b.

For example, when the amount of treated wastewater 203A (203B, 203C) treated by the wastewater treatment apparatus 202A (202B, 202C) is equal to or less than the preset value of the makeup water amount, the treated wastewater 203A ( 203B, 203C) are all returned to the wet desulfurization apparatus 21 as makeup water.
On the other hand, when the amount of the treated wastewater 203A (203B, 203C) is larger than the preset value of the makeup water amount, the surplus treated wastewater 203A (203B, 203C) is supplied to the spray water line 240 to spray the wastewater. The fuel is supplied to the boiler 11 by the device 261, the boiler 11, the flue 13, and the bypass pipes 13a and 13b. Furthermore, the amount of treated wastewater 203A (203B, 203C) to be treated by the wastewater treatment apparatus 202A (202B, 202C) is larger than the sum of the preset value of the makeup water amount and the preset value of the spray water amount. In that case, the surplus treated wastewater 203A (203B, 203C) is discharged out of the system.

  Here, in the same manner as described above, the amount of treated wastewater (makeup water) 203A (203B, 203C) returned to the wet desulfurization device 21 depends on how much the mercury concentration and the halogen ion concentration of the absorption liquid in the wet desulfurization device 21 are. It depends on the setting. On the other hand, the amount of treated wastewater (spray water) 203A (203B, 203C) sprayed inside the furnace of the boiler 11, inside the flue 13, and inside the bypass pipes 13a, 13b is proportional to the amount of exhaust gas 12 to be treated. It is determined by the amount of the treated wastewater 203A (203B, 203C) generated and the limit amount of the treated wastewater 203A (203B, 203C) that can be discharged out of the system.

  The wastewater treatment apparatus 202A (202B, 202C) applies any of the configurations described in the above-described example (FIGS. 9 to 11). For example, when the waste water treatment apparatus 202 is constituted by the first solid-liquid separation means 211 and the mercury removal means 214 as shown in FIG. 9, a part of the treated waste water 203A treated by the mercury removal means 214 is sprayed water. Supply to line 240.

Further, when the waste water treatment apparatus 202 is constituted by the first solid-liquid separation means 211, the mercury removal means 214, and the halogen ion removal means 230 as shown in FIG. 10, the separation liquid 231 treated by the mercury removal means 214 is used. Alternatively, a liquid obtained by mixing the concentrated liquid 241 of halogen ions with the separated liquid 231 is supplied to the spray water line 240 as the treated waste water 203B. For example, when the treated wastewater 203B is sprayed into the flue 13 upstream of the reductive denitration device 17, a mixed liquid of the halogen ion concentrate 241 and the separation liquid 231 is treated with the treated wastewater 203B as shown in FIG. Is supplied to the spray water line 240 and sprayed into the flue 13. Thereby, since the chlorine ion concentration in the exhaust gas 12 can be increased, the conversion efficiency of mercury chloride in the reductive denitration device 17 can be increased.
On the other hand, when the treated wastewater 203B is sprayed into the flue 13 or the bypass pipes 13a and 13b on the downstream side of the reductive denitration device 17, the concentrated solution 241 of halogen ions is not mixed and only the separated solution 231 is treated. It supplies to the spray water line 240 as 203B, and this is sprayed in the flue 13 and bypass pipe 13a, 13b. The same applies to the case where the waste water treatment apparatus 202 is constituted by the first solid-liquid separation means 211, the mercury removal means 214, the auxiliary oxidation means 250, and the halogen ion removal means 230 as shown in FIG.

  The waste water spray device 261 is connected to the waste water treatment device 202 via the spray water line 240, and is connected to the waste water tank 260 for storing treated waste water (spray water) 203A (203B, 203C), and the waste water tank 260. The wastewater 203A (203B, 203C) stored in the boiler is supplied to the boiler 11 with the fuel F, the furnace inside the boiler 11, the flue 13, and the bypass pipes 13a, 13b. Drainage supply pipes (drainage supply means) P0 to P5. Nozzles N1 to N5 for spraying the treated wastewater 203 are provided at the tips of the drainage supply pipes P1 to P5.

  The drainage supply pipes P <b> 0 to P <b> 5 are installed at a position where the high-temperature exhaust gas 12 before the heat is recovered by the air heater 18, that is, upstream of the air heater 18. In the example shown in FIG. 12, the drainage supply pipe P <b> 1 is connected to the boiler 11, and the nozzle N <b> 1 is installed inside the furnace of the boiler 11. Specifically, the nozzle N1 is installed on the side wall of the furnace or the furnace wall at the top of the furnace, and the desulfurization waste water 201 is jetted from the nozzle N1 toward the flame portion in the center of the furnace or above the flame. Further, the drainage supply pipe P <b> 2 is connected to the flue 13 between the boiler 11 and the reduction denitration device 17, and the nozzle N <b> 2 is installed inside the flue 13. The drainage supply pipe P3 is connected to a bypass pipe 13a that connects the upstream side flue 13 and the downstream side flue 13 of the reductive denitration device 17, and the nozzle N3 is installed inside the bypass pipe 13a. Further, the drainage supply pipe P <b> 4 is connected to the flue 13 between the reducing denitration device 17 and the air heater 18, and the nozzle N <b> 4 is installed inside the flue 13. The drainage supply pipe P5 is connected to a bypass pipe 13b connecting the upstream side flue 13 and the downstream side flue 13 of the air heater 18, and the nozzle N5 is installed inside the bypass pipe 13b.

  As the nozzles N1 to N5, for example, a two-fluid nozzle, a rotary atomizer, or the like is used. The mist diameters of the nozzles N1 to N5 are preferably a maximum particle diameter of 200 μm or less and an average particle diameter of 30 to 70 μm. Thereby, the contact efficiency with the exhaust gas 12 is improved, and the evaporation efficiency can be improved.

  Since the exhaust gas temperature in the furnace of the boiler 11 in which the nozzle N1 is installed is as high as about 800 ° C. to 1200 ° C., it is possible to evaporate the most treated waste water 203A (203B, 203C). The exhaust gas temperature inside the flue 13 where the nozzle N2 is installed is about 500 ° C., and the exhaust gas temperature inside the flue 13 where the nozzle N4 is installed and the bypass pipes 13a and 13b where the nozzles N3 and N5 are installed are In any case, the temperature is about 350 ° C. to 400 ° C., and although the temperature is lower than the inside of the furnace of the boiler 11, the treated wastewater 203 can be reliably evaporated. On the other hand, the temperature of the exhaust gas 12 that has passed through the air heater 18 decreases to about 150 ° C., and the treated wastewater 203 cannot be sufficiently evaporated.

  Further, the drainage supply pipe P0 is installed in a path for supplying the fuel F to the boiler 11. Here, the path for supplying the fuel F to the boiler 11 is specifically the inside of a fuel supply apparatus (not shown), piping for connecting the fuel supply apparatus and the boiler 11, or the like. The treated wastewater 203 supplied to the fuel F from the wastewater supply pipe P0 is mixed with the fuel F, and is put into the boiler 11 together with the fuel F, and then evaporates in the boiler 11.

  The drainage supply pipes P0 to P5 are provided with opening / closing valves V10 to V15, respectively. By controlling the opening / closing amounts of these opening / closing valves V10 to V15, the treated wastewater 203 supplied to the drainage supply pipes P0 to P5 is controlled. The flow rate is adjusted. The treated wastewater 203 stored in the drainage tank 260 is a path for supplying the fuel F to the boiler 11 via the drainage supply pipes P0 to P5, inside the furnace of the boiler 11, inside the flue 13, and bypass pipes 13a and 13b. Each is sprayed inside.

  The treated wastewater 203 sprayed into the high-temperature exhaust gas 12 from the nozzles N1 to N5 evaporates to become water vapor, and is then sent into the wet desulfurization device 21 together with the exhaust gas 12. Since the temperature in the wet desulfurization apparatus 21 is about 30 ° C. to 50 ° C., most of the water vapor introduced into the wet desulfurization apparatus 21 is liquefied and mixed with the lime gypsum slurry 20 at the tower bottom 54. On the other hand, the water vapor that has not been liquefied is discharged from the chimney 53 together with the purified gas 52.

  As described above, the temperature of the exhaust gas 12 varies depending on the location of the flue 13, and the evaporation efficiency of the desulfurized waste water 201 also varies. Therefore, the open / close amounts of the open / close valves V10 to V15 are optimized in consideration of the dry particle transfer efficiency and the exhaust gas 12 evaporation efficiency.

  As described above, in the mercury treatment system 10G in the exhaust gas of the fifth embodiment, in addition to the configurations of the first to fourth embodiments, the path for supplying the fuel F to the boiler 11, the furnace interior of the boiler 11, the flue 13 It is set as the structure which installed the waste_water | drain supply pipes P0-P5 which supply process waste_water | drain 203A (203B, 203C) in at least one place inside the inside of the bypass pipes 13a and 13b. Then, at least a part of the treated wastewater 203 treated by the wastewater treatment apparatus 202 is returned to the wet desulfurization apparatus 21 as make-up water, while a part of the treated wastewater 203 is supplied to the boiler 11 through a path for supplying the fuel F. The inside of the furnace and the flue 13 are supplied. That is, in this embodiment, in addition to returning the treated wastewater 203A (203B, 203C) to the wet desulfurization apparatus 21 as make-up water, a part of the treated wastewater 203A (203B, 203C) is passed to the boiler 11, the flue 13, and the like. In addition to the effects of the first to fourth embodiments, the treated wastewater 203A (203B, 203C) treated by the wastewater treatment apparatus 202A (202B, 202C) can be reused to the maximum. Thus, all of the treated wastewater 203A (203B, 203C) can be reused in the mercury treatment system 10G in the exhaust gas. As a result, it becomes possible to remarkably reduce the amount of discharged wastewater to the outside of the system or achieve complete drainage.

  Further, since the treated wastewater 203A (203B, 203C) is directly sprayed into the high-temperature exhaust gas 12 before heat is recovered by the air heater 18, the treated wastewater 203A (203B, 203C) from the nozzles N1 to N5 is sprayed. Even if the spray amount is large, the treated wastewater 203A (203B, 203C) can be reliably evaporated, and the amount of the treated wastewater 203 returned into the flue 13 per unit time can be increased. As a result, since the amount of the desulfurization waste water 201 per unit time can be increased, it is possible to increase the processing amount of the exhaust gas 12 per unit time as compared with the conventional case.

  Further, bypass pipes 13a and 13b are respectively provided at a position parallel to the reducing denitration device 17 and a position parallel to the air heater 18, and the treated wastewater 203 is sprayed and evaporated in the exhaust gas 12 inside the bypass pipes 13a and 13b. As a result, dry particles such as ash generated by the evaporation of the treated wastewater 203A (203B, 203C) pass through the reduction denitration device 17 and the air heater 18 to reduce the function of these devices. In this case, the dry particles can be efficiently conveyed to the downstream side of the reducing denitration device 17 and the air heater 18 via the bypass pipes 13a and 13b.

  In addition, the structure of the waste_water | drain spraying apparatus 261 shown in FIG. 12 is an example, and the installation number and installation position of the waste_water | drain supply pipes P0-P5 are not limited to this, The quantity of treated waste_water | drain 203A (203B, 203C) It can be appropriately changed according to the type of the exhaust gas 12 or the like. That is, the fuel F may be installed in at least one of the path for supplying the fuel F to the boiler 11, the furnace interior of the boiler 11, the flue 13 from the outlet of the boiler 11 to the inlet of the air heater 18, and the bypass pipes 13a and 13b. .

  Further, the amount of harmful substances and solids contained in the treated wastewater 203A (203B, 203C) is very small, and the treated wastewater 203A (203B, 203C) is sprayed into the flue 13 upstream of the reductive denitration device 17 and the air heater 18. However, if there is no risk of reducing the function of these devices, the bypass pipes 13a and 13b are not necessarily provided. Furthermore, in the waste water spray device 261 shown in FIG. 12, the treated waste water 203 from the waste water treatment device 202 is temporarily stored in the drain tank 260, and the treated waste water 203 is supplied from the drain tank 260 to the waste water supply pipes P0 to P5. However, the treated wastewater 203 supplied from the wastewater treatment device 202 via the spray water line 240 may be directly supplied to the wastewater supply pipes P0 to P5.

  Thus, according to the mercury treatment systems 10A to 10G in the exhaust gas to which the spraying apparatus according to the present embodiment is applied, even in the system oxidized with mercury on the upstream side of the wet desulfurization apparatus, on the downstream side of the desulfurization apparatus, Further, remaining mercury can be removed, and the mercury concentration in the exhaust gas can be removed to an extremely low concentration.

  As described above, according to the mercury treatment system in the exhaust gas according to the present invention, the mercury concentration in the absorption liquid used in the desulfurization apparatus can be reduced, so that mercury is scattered in the exhaust gas in the desulfurization apparatus. It can be greatly suppressed.

10A-10G Mercury treatment system in exhaust gas 11 Boiler 12 Exhaust gas 13 Flue 14 Ammonium chloride (NH ₄ Cl) solution 16 Ammonium chloride (NH ₄ Cl) solution supply means (reduction oxidation aid supply means)
17 Reduction denitration equipment (reduction denitration means)
18 Heat exchanger (air heater)
19 dust collector 20 limestone gypsum slurry 21 wet desulfurization system 23A~23B spray device 24 ammonium chloride (NH ₄ Cl) within solution supply pipe 25,56 air 26 air supply pipe 27 blow pipe 28 nozzle head 29 tube 30 outer tube

Claims (14)

A reduction oxidation aid supply means for spraying a solution containing a reduction oxidation aid that generates hydrogen chloride and ammonia when vaporized in a flue that discharges exhaust gas from the boiler;
A reduction denitration apparatus having a denitration catalyst that reduces nitrogen oxides in the exhaust gas with ammonia and oxidizes mercury in the presence of hydrogen chloride;
A wet desulfurization apparatus for removing mercury oxidized in the reductive denitration apparatus with an alkali absorbing solution;
A mercury treatment system in exhaust gas, comprising a finishing mercury removal device that is provided inside or on the downstream side of the wet desulfurization device and removes mercury remaining in the exhaust gas. In claim 1,
The mercury treatment system in exhaust gas, wherein the finishing mercury removal device provided on the downstream side of the wet desulfurization device is at least one of dust removal treatment means, adsorption treatment means, and gas-liquid contact treatment means. In claim 1,
The mercury treatment system in exhaust gas, wherein the finishing mercury removing device provided in the wet desulfurization device is an oxidant supply means for supplying an oxidant into the absorption liquid of the wet desulfurization device. In claim 1,
The mercury treatment system in exhaust gas, wherein the finishing mercury removing device provided in the wet desulfurization device is an activated carbon supply means for supplying activated carbon into the absorption liquid of the wet desulfurization device. In claim 1,
One or both of a reducing agent and a mercury chlorinating agent are further added to the reducing oxidation aid, and the mercury treatment system in exhaust gas is characterized in that: In claim 1,
A mercury treatment system in exhaust gas, characterized in that the reducing oxidation aid is ammonium halide. In claim 2 or 3,
A mercury treatment system in exhaust gas, wherein the reducing agent is ammonia or urea. In any one of Claims 2 thru | or 4,
A mercury treatment system in exhaust gas, wherein the mercury chlorinating agent is hydrogen halide. In claim 1,
A wastewater treatment apparatus having solid-liquid separation means for separating solids and liquids in the desulfurization effluent discharged from the wet desulfurization apparatus, and mercury removal means for removing mercury in the desulfurization effluent;
Treated wastewater returning means for returning at least a part of the treated wastewater treated by the wastewater treatment device to the wet desulfurization device;
A mercury treatment system in exhaust gas, comprising: In claim 9,
The mercury removing means solidifies the mercury by adding a coagulant aid to the separated liquid obtained by separating the solid in the desulfurized wastewater by the first solid-liquid separating means, and separates the mercury solid from the desulfurized wastewater. A mercury treatment system in exhaust gas, characterized by having a solid-liquid separation means. In claim 9,
The waste water treatment device is
A mercury treatment system in exhaust gas, comprising halogen ion removing means for removing halogen ions in the desulfurization waste water. In claim 9,
The agglomeration aid is a sulfide,
The said waste water treatment apparatus has the auxiliary agent oxidation means which performs the oxidation process of the said coagulant auxiliary agent contained in the separation liquid which isolate | separated the said mercury solid substance, The mercury processing system in waste gas characterized by the above-mentioned. In claim 9,
An air heater provided between the reductive denitration device and the wet desulfurization device, and recovering heat of the exhaust gas;
Waste water that is installed in at least one place inside the boiler, inside the boiler, and inside the flue between the boiler and the air heater, and supplies part of the treated waste water treated by the waste water treatment device. A mercury treatment system in exhaust gas, further comprising a supply means. In claim 13,
A bypass pipe is provided in at least one of a position parallel to the flue from the reduction denitration apparatus or a position parallel to the flue from the air heater, and the drainage supply means is provided in the bypass pipe. Mercury treatment system in exhaust gas.

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