JP2010269248A - Apparatus for desulfurizing/absorbing flue gas, and method of treating flue gas - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an apparatus for desulfurizing/absorbing a flue gas, capable of efficiently treating sea water having absorbed a sulfur component present in a flue gas in a tower constituting the apparatus for desulfurizing/absorbing a flue gas, and a method of treating a flue gas. <P>SOLUTION: The first apparatus 10A for desulfurizing/absorbing a flue gas relating to Example 1 of the apparatus for desulfurizing/absorbing a flue gas that makes SO<SB>2</SB>present in a flue gas 11 to contact with sea water 12 and washes the SO<SB>2</SB>, includes a contact section 13 that brings the flue gas 11 to contact with the sea water 12, a tower-bottom section 15 for storing an absorbent liquid 14 for a sulfur component having absorbed SO<SB>2</SB>present in the flue gas 11 by making the flue gas 11 to contact with the sea water 12 in the contact section 13, and an ACF tank 17 that is formed of an ACF layer 16 comprised of ACF and is disposed in the tower-bottom section 15. By utilizing the catalytic action of the ACF by submerging the ACF tank 17 in the absorbent liquid 14 for a sulfur component, the oxidation of a sulfite ion present in the absorbent liquid 14 for a sulfur component is accelerated and the sulfite ion is efficiently oxidized. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a flue gas desulfurization absorption apparatus and an exhaust gas treatment method for desulfurizing sulfur oxide in exhaust gas discharged from an industrial combustion facility using seawater.

  A desulfurization apparatus is provided to remove sulfur contained in exhaust gas generated by burning fossil fuel such as coal. In addition, power plants are often constructed in locations facing the sea because they require a large amount of cooling water, and desulfurization is performed using seawater as an absorbent from the viewpoint of reducing the operating cost of desulfurization treatment. Seawater desulfurization that performs this is attracting attention (see, for example, Patent Document 1).

The flue gas desulfurization absorption apparatus using seawater as the absorption liquid is lower in cost than the lime-gypsum method, and is therefore used in thermal power plants and the like. In addition, since a large amount of seawater is used as cooling water in the condenser of the boiler, a part of the seawater effluent discharged from the condenser is supplied to the desulfurizer and used for removing SO _{2 in} the exhaust gas. It is done.

JP 2006-55779 A

Here, in the conventional flue gas desulfurization apparatus, the exhaust gas and seawater are counter-contacted to absorb SO ₂ in the exhaust gas into the sea water. However, the SO ₂ absorbed in the sea water reacts with the sea water. Since hydrogen ions (H ⁺ ) are generated, the pH of the sulfur-absorbing liquid that is seawater that has absorbed SO ₂ is, for example, about 3.0 to 3.5. For this reason, in order to oxidize the sulfite ions generated by the dissolution of SO ₂ absorbed in the sulfur-absorbing solution into sulfate ions, a pH adjuster is supplied in the main body of the flue gas desulfurization device. In addition, it is necessary to adjust the pH of the sulfur component absorbing solution to a range that can be oxidized.

  However, since a large amount of seawater is supplied in the apparatus body, when adjusting the pH of the sulfur absorbent using a pH adjuster, dilute with a large amount of seawater or supply a large amount of pH adjuster. There is a problem that needs to be done.

  Therefore, there is a demand for a method for efficiently and effectively treating the sulfur content in the exhaust gas absorbed in the seawater in the flue gas desulfurization absorber.

  In view of the above problems, the present invention has an object to provide a flue gas desulfurization absorber and an exhaust gas treatment method capable of efficiently treating seawater that has absorbed sulfur content in the flue gas in the flue gas desulfurization absorber tower. To do.

  1st invention of this invention for solving the subject mentioned above is a flue gas desulfurization absorption device which makes a sulfur content in exhaust gas contact and wash with seawater, and a contact part which makes the exhaust gas and seawater contact, In the contact portion, the exhaust gas and the seawater are brought into contact with each other to store a sulfur content absorbing solution that has absorbed the sulfur content in the exhaust gas, and an active carbon fiber disposed in the storage portion and made of activated carbon fiber. And an activated carbon fiber tank formed of a carbon fiber layer.

  According to a second aspect of the present invention, there is provided a flue gas desulfurization absorption device for cleaning the sulfur content in the exhaust gas by bringing it into contact with sea water, and a contact portion for bringing the exhaust gas into contact with the sea water, and the exhaust gas and the sea water in the contact portion. A storage part for storing a sulfur-absorbing solution that absorbs the sulfur content in the exhaust gas by contact with the storage part, and a metal-containing activated carbon fiber molding that is dispersed in the storage part and formed by containing activated carbon fibers with metal. The flue gas desulfurization absorption device includes a body and an activated carbon fiber recovery unit that is provided in the storage unit and recovers the metal-containing activated carbon fiber molded body.

  According to a third aspect of the present invention, there is provided the flue gas desulfurization absorption device according to the second aspect, wherein the activated carbon fiber recovery unit is a magnet or an electromagnet.

  A fourth invention is the flue gas desulfurization absorption apparatus according to the second or third invention, wherein the metal is iron or nickel.

  A fifth invention is characterized in that, in any one of the second to fourth inventions, the shape of the metal-containing activated carbon fiber molded body is any one of a comb shape, a warm shape, a saw shape, or a spherical shape. Located in flue gas desulfurization absorber.

  According to a sixth invention, in any one of the second to fifth inventions, a filter for preventing the metal-containing activated carbon fiber molded body from flowing out of the apparatus main body is provided in the storage portion. It is in the flue gas desulfurization absorption device.

  A seventh aspect of the invention is the flue gas desulfurization absorption device according to any one of the first to sixth aspects, the dilution seawater supply line that supplies the seawater as dilution water to the flue gas desulfurization absorption device, and the flue gas An oxidation tank that oxidizes and decarboxylates the sulfur content in the sulfur content absorbent discharged from the desulfurization absorber and restores the water quality, and a sulfur content absorbent discharge line that discharges the sulfur content absorbent to the oxidation tank A part of the dilution seawater is supplied to the oxidation tank as the first dilution seawater and mixed with the sulfur absorbent, and a part of the dilution seawater And a second dilution seawater supply line that joins with the water quality recovered seawater recovered in the oxidation tank as the second dilution seawater.

  The eighth invention uses a boiler, exhaust gas discharged from the boiler as a heat source for generating steam, a steam turbine that drives a generator using the generated steam, and water condensed in the steam turbine. A condenser for collecting and circulating, a flue gas denitration device for denitrating exhaust gas discharged from the boiler, a dust collecting device for removing soot in the exhaust gas, and a seawater desulfation treatment device of the seventh invention And a chimney for discharging the purified gas desulfurized by the flue gas desulfurization absorber to the outside.

  According to a ninth aspect of the present invention, there is provided an exhaust gas treatment method in which exhaust gas is brought into contact with seawater to absorb sulfur in the exhaust gas into the seawater, and the exhaust gas is washed. An activated carbon fiber tank formed of an activated carbon fiber layer made of carbon fibers is immersed, and the activated carbon fibers promote the oxidation of the sulfur content in the sulfur content absorbing liquid that has absorbed the sulfur content. Exhaust gas treatment method.

  According to a tenth aspect of the present invention, there is provided an exhaust gas treatment method in which an exhaust gas is brought into contact with seawater to absorb a sulfur content in the exhaust gas into the seawater, and the exhaust gas is washed. An exhaust gas characterized by dispersing a metal-containing activated carbon fiber molded body in which a metal is contained in carbon fiber, and oxidizing the sulfur content in the sulfur-absorbing liquid by contacting with the metal-containing activated carbon fiber molded body. It is in the processing method.

  An eleventh invention is the exhaust gas treatment method according to the tenth invention, wherein the metal-containing activated carbon fiber molded body in the sulfur component absorbing liquid is recovered by an activated carbon fiber recovery part.

  A twelfth aspect of the invention is an exhaust gas treatment method according to the eleventh aspect of the invention, wherein the activated carbon fiber recovery section is a magnet or an electromagnet.

  A thirteenth invention is the exhaust gas treatment method according to the eleventh or twelfth invention, wherein the metal is iron or nickel.

  According to the present invention, since the activated carbon fiber tank formed of the activated carbon fiber layer made of activated carbon fibers is disposed in the sulfur component absorbing liquid that is seawater used for desulfurization, the activated carbon fiber tank is absorbed in the seawater. By contacting the sulfur component and the activated carbon fiber, oxidation of the sulfur component in the sulfur absorbent can be promoted, and the sulfur component can be processed efficiently.

Moreover, according to the present invention, since the metal-containing activated carbon fiber molded body is dispersed in the sulfur-absorbing liquid that is seawater used for desulfurization, the sulfur content absorbed in seawater and the metal-containing activated carbon fiber are dispersed. The contact efficiency with the activated carbon fiber of the molded body can be improved, and the sulfur content in the sulfur content absorbing liquid can be oxidized efficiently and uniformly.
In addition, since the metal-containing activated carbon fiber molded body can be recovered by the activated carbon fiber recovery section provided in the storage section in which the sulfur component absorbing liquid is stored, the recovered metal-containing activated carbon fiber molded body is regenerated. Can be reused.

FIG. 1 is a schematic view of a flue gas desulfurization absorption apparatus according to Embodiment 1 of the present invention. FIG. 2 is a diagram showing a configuration of the activated carbon fiber layer. FIG. 3 is a schematic view of a flue gas desulfurization absorption device according to Embodiment 2 of the present invention. FIG. 4 is a partially enlarged view of the flue gas desulfurization absorber shown in FIG. FIG. 5 is a diagram showing an example of a method for recovering activated carbon fibers. FIG. 6 is a diagram showing another example of a method for recovering activated carbon fibers. FIG. 7 is a diagram showing another shape of the activated carbon fiber. FIG. 8 is a diagram showing another shape of the activated carbon fiber. FIG. 9 is a view showing another shape of the activated carbon fiber. FIG. 10 is a diagram showing another shape of the activated carbon fiber. FIG. 11 is a schematic view of a flue gas desulfurization absorption device according to Embodiment 3 of the present invention. FIG. 12 is a schematic diagram illustrating a configuration of a power generation system according to Embodiment 4 of the present invention.

  Hereinafter, the present invention will be described in detail with reference to the drawings. Note that the present invention is not limited to the embodiments. In addition, constituent elements in the following embodiments include those that can be easily assumed by those skilled in the art or those that are substantially the same.

A flue gas desulfurization absorber according to Embodiment 1 of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic view of a flue gas desulfurization absorption device according to Embodiment 1 of the present invention, and FIG. 2 is a diagram showing a configuration of an activated carbon fiber layer.
As shown in FIGS. 1 and 2, a first flue gas desulfurization absorption device 10 </ _b > A according to this embodiment is a flue gas desulfurization absorption device that cleans SO _{2 in} flue gas 11 in contact with seawater 12. A contact portion 13 that makes contact with the seawater 12, and a tower bottom portion (reservoir) 15 in which the sulfur-absorbing liquid 14 that has absorbed SO ₂ in the exhaust gas 11 by contacting the exhaust gas 11 and the seawater 12 at the contact portion 13 is stored. And an activated carbon fiber tank (ACF tank) 17 formed by an activated carbon fiber layer (ACF layer) 16 made of activated carbon fiber (ACF). Is.
Moreover, in this invention, a storage part means the fixed area | region in the apparatus main body 18 which has stored the sulfur content absorption liquid 14, and in a present Example, the tower bottom part 15 by which the sulfur content absorption liquid 14 is stored is used. Say.

The SO ₂ contained in the exhaust gas 11 is subjected to seawater desulfurization using seawater 12 drawn from the sea. The exhaust gas 11 is fed into the apparatus main body 18 from the wall surface on the tower bottom 15 side of the apparatus main body 18 through the exhaust gas supply line 21. On the other hand, the seawater 12 is fed into the apparatus main body 18 from the tower top 23 side of the apparatus main body 18 via the seawater supply line 22. The exhaust gas 11 introduced from the tower bottom in the apparatus main body 18 and the seawater 12 supplied from the watering nozzle 24 are opposed to each other in gas-liquid contact, so that the contact portion 13 in the apparatus main body 18 contains the exhaust gas 11 in the exhaust gas 11. SO ₂ is absorbed into the seawater 12, and the SO ₂ is converted to sulfite ions (HSO ₃ ⁻ ) and stored in the tower bottom 15 of the apparatus main body 18.
In the present embodiment, the sulfur absorbent 14 refers to seawater containing a high concentration of sulfur such as SO ₂ and sulfite ions produced by seawater desulfurization, and the apparatus main body 18 absorbed the sulfur. It refers to the falling water of seawater.

  Further, when the exhaust gas 11 supplied into the apparatus main body 18 reaches the tower top 23 of the apparatus main body 18, since the sulfur content in the exhaust gas 11 is absorbed into the seawater 12, the exhaust gas 11 is removed from the tower top 23. A purified purified gas 25 containing almost no sulfite ions is discharged from the tower top 23 of the apparatus main body 18 to the outside.

  Further, in the flue gas desulfurization apparatus 10A according to the present embodiment, an ACF tank 17 formed of an ACF layer 16 made of activated carbon fiber (ACF) as activated carbon is immersed in the storage unit 15. In addition, as shown in FIG. 2, the ACF tank 17 includes an ACF layer 16 constituting the ACF tank 17 and a flat plate activated carbon fiber sheet (flat plate ACF sheet) 16a and a corrugated activated carbon fiber sheet (corrugated plate). An ACF sheet) 16b is joined to form a triangular passage 16c, for example. In the present embodiment, the cross section of the passage 16c has a triangular shape, but is not limited thereto, and may have a rectangular shape or the like.

Oxygen contained in the sulfur absorbent 14 even under oxidation conditions of pH 3.0 or more and 3.5 or less by adsorbing sulfite ions in the sulfur absorbent 14 to the ACF and utilizing the catalytic action of ACF Thus, sulfite ions are oxidized and reacted with the seawater 12 supplied into the apparatus main body 18 to obtain sulfuric acid (H ₂ SO ₄ ). Therefore, sulfite ions in the sulfur absorbent 14 are oxidized by contacting and adsorbing the sulfite ions in the sulfur absorbent 14 at the bottom 15 of the surface of the ACF layer 16 forming the ACF tank 17. It can promote and treat sulfite ions efficiently.

The sulfurous acid ions in the sulfur absorbent 14 are oxidized to sulfuric acid (H ₂ SO ₄ ) and then discharged from the seawater discharge line 28 to the outside of the apparatus body 18.

  Further, in the first flue gas desulfurization absorption apparatus 10A according to the present embodiment, the seawater 12 is supplied into the apparatus main body 18 from the tower top 23 side of the apparatus main body 18 by the watering nozzle 24, but the present invention. However, the seawater 12 is jetted toward the tower top 23 in the apparatus main body 18 so that the seawater 12 that has flowed down and the exhaust gas 11 supplied from the tower bottom side are brought into countercurrent contact. May be.

Thus, the first flue gas desulfurization absorbing device 10A according to the present embodiment, the contact in the flue gas desulfurization absorber for washing the SO ₂ in the flue gas 11 is contacted with sea water 12, the exhaust gas 11 and the seawater 12 The contact portion 13 to be stored, the storage portion 15 in which the exhaust gas 11 and the seawater 12 are brought into contact with each other at the contact portion 13 to store the SO ₂ in the exhaust gas 11, and the storage portion 15. And an ACF tank 17 formed of the ACF layer 16. Therefore, according to the first flue gas desulfurization absorption apparatus 10A according to the present example, the ACF tank 17 is immersed in the sulfur content absorption liquid 14 used for the desulfurization in the tower bottom 15, so that the catalytic action of ACF is increased. By using this, the sulfite ions in the sulfur component absorbing liquid 14 come into contact with and adsorb to the ACF on the surface of the ACF layer 16, thereby promoting the oxidation of the sulfite ions in the sulfur component absorbing solution 14 and making the sulfite ions efficient. Can be processed well.

Further, in the first flue gas desulfurization absorption apparatus 10A according to the present embodiment, the case of SO ₂ as the sulfur content in the exhaust gas 11 has been described, but the present invention is not limited to this, and the sulfur content is The same applies to other sulfur oxides such as SO ₃ .

  In the first flue gas desulfurization absorption apparatus 10A according to the present embodiment, the exhaust gas 11 containing the sulfur content discharged from the combustion facility has been described. However, the flue gas desulfurization absorption apparatus according to the present invention is limited to this. However, it can also be used for exhaust gas treatment containing sulfur oxides contained in exhaust gas discharged from factories, power plants, boilers and the like in various industries.

A flue gas desulfurization absorption apparatus according to Embodiment 2 of the present invention will be described with reference to the drawings.
Since the configuration of the flue gas desulfurization absorption device is the same as that of the flue gas desulfurization absorption device according to the first embodiment of the present invention, the same components as those in the first embodiment are denoted by the same reference numerals, and redundant description is omitted.
FIG. 3 is a schematic view of the flue gas desulfurization absorber according to Embodiment 2 of the present invention, and FIG. 4 is a partially enlarged view of the flue gas desulfurization absorber shown in FIG.
The second flue gas desulfurization absorption apparatus 10B according to the present embodiment is in the sulfur content absorption liquid 14 used for desulfurization at the tower bottom 15 of the first flue gas desulfurization absorption apparatus 10A according to the first embodiment shown in FIG. The activated carbon fiber molded body (ACF molded body) molded with ACF is dispersed in the sulfur content absorbing liquid 14 in place of the ACF tank 17 immersed in the ACF.

That is, as shown in FIGS. 3 and 4, the second flue gas desulfurization absorption device 10B according to the present embodiment is an exhaust gas desulfurization absorption device that cleans SO ₂ in the flue gas 11 in contact with the seawater 12 for cleaning. 11 and the seawater 12 and the contact portion 13 contacting the, column bottom of the exhaust gas 11 and the seawater 12 and the sulfur absorbent solution 14 is contacted to absorb the SO ₂ in the flue gas 11 is stored in the contact portion 13 (reservoir ) 13, a metal-containing activated carbon fiber molded body (metal-containing ACF molded body) 26 </ b> A that is dispersed in the tower bottom 15 and formed by containing iron (Fe) in ACF, and is provided on the tower bottom 15. And an electromagnet (active carbon fiber recovery part) 27A for recovering the contained ACF molded body 26A.

  Since the sulfur absorbent 14 used for the desulfurization is supplied from the watering nozzle 24 provided on the tower top 23 side, the sulfur absorbent 14 flowing down to the tower bottom 15 causes the sulfur in the tower bottom 15 to flow. Natural convection is generated in the minute absorbent 14. For this reason, the metal-containing ACF molded body 26 </ b> A can be dispersed in the sulfur absorbent 14.

Since the metal-containing ACF molded body 26A can be dispersed in the sulfur-absorbing liquid 14 by natural convection generated in the sulfur-absorbing liquid 14 stored in the tower bottom 15, the sulfur-absorbing liquid 14 in the sulfur-absorbing liquid 14 in the tower bottom 15 can be dispersed. The contact efficiency between the sulfite ions and the ACF of the metal-containing ACF molded body 26A can be improved. Therefore, the sulfite ions in the sulfur content absorbing liquid 14 are brought into contact with the metal-containing ACF molded body 26A dispersed in the sulfur content absorbing liquid 14 to be uniformly oxidized, react with the seawater 12, and react with H ₂ SO _4. And can be processed efficiently and uniformly in the sulfur component absorbing liquid 14.

  Further, in the first flue gas desulfurization absorption apparatus 10A according to the first embodiment as shown in FIG. 1, as shown in FIG. 2, the ACF layer 16 constituting the ACF tank 17 is composed of the flat plate portion ACF sheet 16a and the corrugated plate. The ACF sheet 16b is joined to form a triangular passage 16c. For this reason, when the sulfur component absorbing liquid 14 is circulated in the passage 16c, if the ventilation resistance in the passage 16c is different for each passage 16c, the passage amount of the sulfur absorbing solution 14 is different for each passage 16c, and the sulfur absorption is performed. In some cases, the liquid 14 cannot be uniformly passed through the plurality of passages 16c.

  On the other hand, according to the second flue gas desulfurization absorption device 10B according to the present embodiment, the metal-containing ACF molded body 26A can be dispersed in the sulfur content absorption liquid 14 at the tower bottom 15, so that the sulfur content absorption. By improving the contact efficiency between the sulfite ions in the liquid 14 and the metal-containing ACF molding 26A, the metal-containing ACF molding 26A in which the sulfite ions in the sulfur-absorbing liquid 14 are dispersed in the sulfur-absorbing liquid 14 Can be uniformly oxidized, and can be efficiently and uniformly treated in the sulfur absorbent 14.

  In addition, as an example of a method for producing the metal-containing ACF molded body 26A, the ACF molded body is immersed in a solution containing iron ions so that iron ions are contained in the ACF molded body. For example, heat treatment is performed in a furnace at a temperature of 1000 ° C. or higher and 1200 ° C. or lower for about 1 hour. As a result, the iron ions are contained in the ACF molded body in a state of being metallic iron or carbide, and the metal-containing ACF molded body 26A is manufactured. When the ACF molded body contains a metal other than iron, the ACF molded body is dipped in a solution containing metal ions other than iron ions and pulled up from the solution containing metal ions other than iron ions. It heat-processes similarly to. Thereby, a metal-containing ACF molded body in which a metal other than iron is contained in the ACF molded body can be manufactured. The method for containing the metal in the ACF compact is not limited to this, and as another method, for example, an electron gun may be used to contain the metal in the ACF compact.

  The metal content in the metal-containing ACF molded body 26 </ b> A is preferably higher in specific gravity than the seawater 12 in order to maintain the dispersibility of the metal-containing ACF molded body 26 </ b> A in the sulfur absorbent 14. The metal content in the metal-containing ACF molded body 26A is, for example, preferably 0.1 wt% or more and 20.0 wt% or less, more preferably 0.1 wt% or more and 1.5 wt% or less, and further preferably 0. 3 wt% or more and 1.5 wt% or less are more preferable, and 0.5 wt% or more and 1.5 wt% or less are most preferable. This is because if the metal content in the metal-containing ACF compact 26A is less than 0.1 wt%, the metal-containing ACF compact 26A is difficult to be attracted to the electromagnet 27A, as will be described later. Further, if the metal content in the metal-containing ACF molded body 26A is larger than 20.0 wt%, the metal-containing ACF molded body 26A is likely to precipitate on the bottom of the tower bottom portion 15.

For example, when the seawater amount is about 100 m ² / min, the gas amount is about 100,000 m ³ / h, the SO ₂ content is about 1000 ppm, and the seawater amount in the tower is about 326 m ³ , as shown in FIG. In the case of a honeycomb-shaped ACF that has been conventionally used, an ACF of about 3.0 to 3.3 t is required. On the other hand, if the metal-containing ACF molded body 26A is used, an ACF of about 0.8 to 1.0 t is sufficient. In addition, the dispersion concentration of ACF in the sulfur content absorbing liquid 14 is about 3 to 5 wt% in the case of a honeycomb-shaped ACF that has been conventionally used. On the other hand, in the case of the metal-containing ACF molded body 26A, it is about 0.2 to 2.0 wt%. Therefore, if the metal-containing ACF compact 26A is used, the amount of ACF used in the tower can be greatly reduced.

  An electromagnet 27A for collecting the metal-containing ACF molded body 26A is provided on the inner wall 15a of the tower bottom portion 15. Since the metal-containing ACF compact 26A contains Fe, the metal-containing ACF compact 26A can be adsorbed to the electromagnet 27A provided on the inner wall 15a of the tower bottom 15.

  Further, a movable part that can move the electromagnet 27A in the vertical direction is provided on the inner wall 15a, and the electromagnet 27A is moved upward so as not to adhere to the sulfur component absorbing liquid 14, and then the electromagnet 27A is taken out of the apparatus main body 18 and is electromagnetized. The metal-containing ACF molded body 26 </ b> A adsorbed on 27 </ b> A may be discharged out of the apparatus main body 18.

  Moreover, an example of the collection | recovery method of 26 A of metal containing ACF molded objects is shown in FIG. As shown in FIG. 5, a rotatable electromagnet 27B is provided on the inner wall 15a of the apparatus main body 18, a metal-containing ACF molded body 26A is adsorbed to the electromagnet 27B, and the electromagnet 27B is rotated to rotate the electromagnet 27B. The contained ACF molded body 26A may be discharged and the metal-containing ACF molded body 26A adsorbed on the electromagnet 27B may be taken out using the scraper 30 or the like. Further, a liquid leakage preventing member 31 is provided on the inner wall 15 a of the apparatus main body 18 so that the sulfur component absorbing liquid 14 does not leak outside the apparatus main body 18.

  Furthermore, another example of the recovery method of the metal-containing ACF molded body 26A is shown in FIG. As shown in FIG. 6, the metal-containing ACF in the sulfur component absorbing liquid 14 using a conveyor 33 including a pair of electromagnets 27 </ b> B and 24 </ b> C and a magnetic belt 32 wound around the electromagnets 27 </ b> B and 24 </ b> C. The molded body 26A may be recovered. In addition, the electromagnets 27B and 24C are excited by turning on the power and flowing current, and demagnetized by turning off the power. The electromagnet 27B is excited, and the metal-containing ACF compact 26A is attracted to the surface of the belt 32 that is in contact with the electromagnet 27B. Then, the metal-containing ACF molded body 26A adsorbed on the belt 32 is transported to the outside of the apparatus main body 18 by the belt 32 as the electromagnet 27B rotates. The metal-containing ACF molded body 26A conveyed to the outside of the apparatus main body 18 by the belt 32 is detached from the belt 32 by demagnetizing the electromagnet 27C, and the metal-containing ACF molded body 26A can be collected in the collection container 34. Further, the belt 32 may be energized by turning on the power and passing a current. Thereby, the metal-containing ACF molded body 26 </ b> A can be stably conveyed to the outside of the apparatus main body 18.

  The metal-containing ACF molded body 26A adsorbed on the electromagnet 27A is recovered outside the apparatus main body 18, the metal-containing ACF molded body 26A recovered from the apparatus main body 18 is regenerated, and again in the sulfur component absorbing liquid 14 in the apparatus main body 18. It can be reused by putting it in. The recovered metal-containing ACF molded body 26A can be regenerated by washing with, for example, seawater or dilute sodium hydroxide (NaOH) aqueous solution. It can also be regenerated by immersing it in wastewater containing iron ions.

  In the second flue gas desulfurization absorber 10B according to the present embodiment, iron is contained in the ACF. However, any metal having magnetism that can be adsorbed by the electromagnet 27A may be used. For example, nickel (Ni ), Cobalt (Co), or other metals may be used.

  Moreover, in the flue gas desulfurization absorption processing apparatus 10B according to the present embodiment, an electromagnet is used as the activated carbon fiber recovery unit, but the present invention is not limited to this, and has magnetism that can adsorb metals. Any material can be used. For example, a magnet can be used.

Further, in the second flue gas desulfurization absorption device 10B according to the present embodiment, the metal-containing ACF molded body 26A in which the shape of the ACF is formed into a felt-like rectangular shape is used, but the present invention is limited to this. It is not something. For example, as shown in FIG. 7, a metal-containing ACF molded body 26B in which a metal such as Fe is contained in a warm-shaped ACF molded body may be used. Further, as shown in FIG. 8, a metal-containing ACF molded body 26C in which a metal such as Fe is contained in an interdigital ACF molded body may be used. In addition, as shown in FIG. 9, a metal-containing ACF molded body 26D in which a metal such as Fe is contained in a sawtooth ACF molded body may be used. Further, a plurality of the metal-containing ACF molded bodies 26D may be provided in a shelf shape in the sulfur content absorbing liquid 14 at the tower bottom 15. Furthermore, as shown in FIG. 10, a metal-containing ACF molded body 26E in which a metal such as Fe is contained in a spherical ACF molded body may be used. Since the contact efficiency between the sulfite ions and the ACF in the sulfur content absorbing liquid 14 can be increased by using the metal-containing ACF molded bodies 26B to 23E as shown in FIGS. 7 to 10, the sulfur content absorbing liquid 14 The sulfite ions therein can be more efficiently and uniformly oxidized and reacted with water to form H ₂ SO ₄ .

  The tower bottom 15 is provided with a filter 34 that prevents the metal-containing ACF molded body 26 </ b> A from flowing out of the apparatus main body 18. By the filter 34, the tower bottom 15 is partitioned into an ACF reaction chamber 35 and a seawater drainage chamber 36, and only the sulfur component absorbing liquid 14 can flow between the ACF reaction chamber 35 and the seawater drainage chamber 36. Therefore, by providing the filter 34 at the tower bottom 15, when the sulfur content absorbing liquid 14 is discharged from the seawater discharge line 28, the metal-containing ACF molded body 26 </ b> A dispersed in the sulfur content absorbing liquid 14 is replaced with the sulfur content absorbing liquid. 14 can be prevented from being discharged from the apparatus main body 18.

Above, the contact second flue gas desulphurization absorber 10B according to this embodiment, in the flue gas desulfurization absorber for washing the SO ₂ in the flue gas 11 is contacted with sea water 12, contacting the flue gas 11 and the seawater 12 Part 13, a tower bottom 15 in which a sulfur absorbent 14 that has absorbed SO ₂ in the exhaust gas 11 is stored, a metal-containing ACF molded body 26 A dispersed in the tower bottom 15 and containing Fe in ACF, An electromagnet 27A is provided at the tower bottom 15 and collects the metal-containing ACF molded body 26A. The metal-containing ACF molded body 26A is dispersed in the sulfur absorbent 14 used for desulfurization. Therefore, according to the second flue gas desulfurization absorption apparatus 10B according to the present embodiment, the metal-containing ACF molded body 26A is dispersed in the sulfur absorbent 14 used for desulfurization in the tower bottom 15, so that the tower bottom 15, the contact efficiency between the sulfite ions in the sulfur absorbent 14 and the ACF of the metal-containing ACF molded body 26 </ b> A can be improved. Further, the metal-containing ACF molded body 26A can be attracted to the electromagnet 27A provided on the inner wall 15a of the tower bottom portion 15 and recovered.
Therefore, the oxidation treatment of the sulfite ions in the sulfur component absorbing liquid 14 in the apparatus main body 18 can be made uniform and can be efficiently processed, and the metal-containing ACF molded body 26A can be recovered, and the recovered metal-containing content can be recovered. The ACF compact 26A can be regenerated and reused.

A flue gas desulfurization absorber according to Example 3 of the present invention will be described with reference to the drawings.
Since the configuration of the flue gas desulfurization absorption device is the same as that of the flue gas desulfurization absorption device according to the first and second embodiments of the present invention, the same components as those of the first and second embodiments are denoted by the same reference numerals and redundant descriptions. Is omitted. Moreover, since the structure of the ACF molded object used with the flue gas desulfurization absorption apparatus which concerns on a present Example is the same as that of FIGS. 7-10, drawing is abbreviate | omitted.
As shown in FIG. 11, the third flue gas desulfurization absorption apparatus 10C according to the present embodiment uses an ACF that does not contain a metal, and has a warm shape, a comb shape, and a saw shape as shown in FIGS. In addition, an activated carbon fiber molded body (ACF molded body) 37 obtained by molding ACF into any one of spherical shapes is dispersed in the sulfur component absorbing liquid 14 in the apparatus main body 18.

That is, as shown in FIG. 11, the third flue gas desulfurization absorption device 10 </ _b > C according to this embodiment is a flue gas desulfurization absorption device that cleans SO ₂ in the flue gas 11 in contact with seawater 12. A contact portion 13 that makes contact with the seawater 12, and a tower bottom portion (reservoir) 15 in which the sulfur-absorbing liquid 14 that has absorbed SO ₂ in the exhaust gas 11 by contacting the exhaust gas 11 and the seawater 12 at the contact portion 13 is stored. And an activated carbon fiber molded body (ACF molded body) 37 that is dispersed in the tower bottom 15 and molded with ACF. The ACF molded body 37 is molded into any one of a warm shape (see FIG. 7), a comb shape (see FIG. 8), a saw shape (see FIG. 9), and a spherical shape (see FIG. 10).

  The shape of the ACF molded body 37 is any one of a warm shape, a comb shape, a saw shape, and a spherical shape as shown in FIGS. 7 to 10, so that the sulfur content is absorbed even if a metal such as Fe is not contained in the ACF. The ACF molded body 37 can be immersed in the liquid 14, and the ACF molded body 37 can be recovered from the sulfur component absorbing liquid 14. As a method for recovering the ACF molded body 37, for example, there is a method of recovering the ACF molded body 37 from the sulfur content absorbing liquid 14 by raising a net or the like previously placed in the sulfur content absorbing liquid 14.

Moreover, the surface area of the ACF molded body 37 is increased by making the shape of the ACF molded body 37 one of a warm, interdigital, slatted, and spherical shape as shown in FIGS. Since the contact area with the liquid 14 can be increased, the contact efficiency between the sulfite ions and the ACF in the sulfur-absorbing liquid 14 can be increased. For this reason, by immersing the ACF molded body 37 in the sulfur content absorbing liquid 14, the sulfite ions in the sulfur content absorbing liquid 14 are efficiently and uniformly oxidized and reacted with water to form H ₂ SO _4. it can.

A power generation system according to Embodiment 4 of the present invention will be described with reference to the drawings.
As the seawater desulfation treatment apparatus applied to the power generation system according to the present embodiment, the flue gas desulfurization absorption apparatus according to the first embodiment is used.
FIG. 12 is a schematic diagram illustrating a configuration of a power generation system according to Embodiment 4 of the present invention. In addition, about the member similar to Example 1, the same code | symbol is attached | subjected and the description is abbreviate | omitted.
As shown in FIG. 12, the power generation system 40 according to this embodiment includes a boiler 43 that is burned by a burner (not shown) using air 42 preheated by an air preheater (AH) 41, and exhaust gas discharged from the boiler 43. 11 is used as a heat source for generating steam, and a steam turbine 46 that drives a generator 45 using the generated steam 44, and a condenser 48 that recovers and circulates water 47 condensed by the steam turbine 46, and , A flue gas denitration device 49 for denitrating the exhaust gas 11 discharged from the boiler 43, a dust collector 50 for removing the soot in the exhaust gas 11 discharged from the boiler 43, and the seawater 12 Seawater desulfurization using the seawater desulfurization treatment apparatus 51 for performing water quality recovery treatment of the sulfur content absorbing solution 14 containing a high concentration of sulfur content generated by seawater desulfurization, and seawater desulfurization Processor exhaust gas 11 at 51 is composed of the chimney 52 for discharging the purified gas 25 desulfurized outside.
In addition, in a present Example, a sulfur content absorption liquid means the flowing-down liquid of the seawater which absorbed the sulfur content in 10 A of 1st flue gas desulfurization absorption apparatuses.

  The air 42 supplied from the outside is supplied to the air preheater 41 by the pushing fan 53 and preheated. For example, fuel (not shown) supplied from an oil tank or the like and air 42 preheated by an air preheater 41 are supplied to the burner, and the fuel is combusted in a boiler 43 and steam 44 for driving a steam turbine 46. Is generated.

  Exhaust gas 11 generated by combustion in the boiler 43 is sent to a flue gas denitration device 49. At this time, the exhaust gas 11 exchanges heat with the water 47 discharged from the condenser 48 and is used as a heat source for generating steam 44, and the generated steam 44 drives the generator 45 of the steam turbine 46. The water 47 condensed by the steam turbine 46 is returned to the boiler 43 and circulated.

  Then, the exhaust gas 11 discharged from the boiler 43 and guided to the flue gas denitration device 49 is denitrated in the flue gas denitration device 49, exchanges heat with the air 42 in the air preheater 41, and then is sent to the dust collector 50. The dust in the exhaust gas 11 is removed. The exhaust gas 11 removed by the dust collector 50 is supplied into the first flue gas desulfurization absorption treatment apparatus 10 </ b> A by the induction fan 54. At this time, after the exhaust gas 11 is heat-exchanged with the purified gas 25 desulfurized and discharged by the first flue gas desulfurization absorption processing apparatus 10A in the heat exchanger 55, the main body of the first flue gas desulfurization absorption processing apparatus 10A. 18 is supplied. Further, the exhaust gas 11 may be directly supplied to the first flue gas desulfurization absorption treatment apparatus 10 </ b> A without exchanging heat with the purified gas 25 by the heat exchanger 55.

  In the power generation system 40 to which the first flue gas desulfurization absorption treatment apparatus 10A according to the present embodiment is applied, the seawater desulfurization treatment apparatus 51 includes the first flue gas desulfurization absorption apparatus 10A and the seawater 12 as the first exhaust gas. Seawater supply line L1 supplied to the smoke desulfurization absorber 10A and an oxidation tank that oxidizes and decarboxylates the sulfur content in the sulfur absorbent 14 discharged from the first flue gas desulfurization absorber 10A and restores the water quality 56, a sulfur absorption liquid discharge line L2 for feeding the sulfur absorption liquid 14 to the oxidation tank 56, and a first dilution for supplying a part of the seawater 12 to the oxidation tank 56 as the first dilution seawater 12B. It has a seawater supply line L3 and a second dilution seawater supply line L4 for joining a part of the dilution seawater with the water quality recovery seawater 57 recovered in the oxidation tank 56 as the second dilution seawater 12C. is there.

  In the present embodiment, of the seawater 12, seawater used for seawater desulfurization by the first flue gas desulfurization absorber 10A is seawater 12A, and seawater used for dilution of the sulfur absorbent 14 is first dilution seawater 12B. The seawater used for dilution of the water quality recovery seawater 57 is used as the second dilution seawater 12C.

  In the first flue gas desulfurization absorption apparatus 10 </ b> A, seawater desulfurization is performed using the seawater 12 pumped up from the sea 58 by sulfur contained in the exhaust gas 11. Further, the seawater 12 is pumped up from the sea 58 by the pump 59, and the seawater 12 discharged by exchanging heat in the condenser 48 is the first flue gas desulfurization absorption by the pump 60 via the seawater supply line L1 as seawater 12A. It is sent to the device 10A.

In the first flue gas desulfurization absorption device 10A, the exhaust gas 11 and the sea water 12A supplied via the sea water supply line L1 are brought into gas-liquid contact to absorb SO ₂ in the exhaust gas 11 into the sea water 12. The first flue gas desulfurization absorption device 10A uses the flue gas desulfurization absorption device according to Example 1 described above. Since the ACF tank 17 is immersed in the sulfur component absorbent 14 used for desulfurization in the first flue gas desulfurization absorber 10A, the catalytic action of ACF is used in the first flue gas desulfurization absorber 10A. Oxidation of the sulfite ions in the sulfur content absorption liquid 14 can be promoted to be H ₂ SO _4, and the sulfite ions in the sulfur content absorption liquid 14 can be efficiently processed.

  Further, in the power generation system 40 according to the present embodiment, the first flue gas desulfurization absorption device 10A according to the first embodiment is used as the flue gas desulfurization absorption device, but the present invention is not limited to this. A second flue gas desulfurization absorption device 10B as shown in FIG. 3 and a third flue gas desulfurization absorption device as shown in FIG. 11 may be used.

  The exhaust gas 11 purified by the first flue gas desulfurization absorber 10A becomes the purified gas 25 and is discharged to the outside from the chimney 52 through the purified gas discharge line L5.

  In addition, the seawater 12 pumped from the sea 58 is supplied to the apparatus body 18 as a seawater 12A by using a part of the seawater 12 that is discharged as a result of heat exchange in the condenser 48, and is used for seawater desulfurization. However, the seawater 12 drawn from the sea 58 may be directly fed to the first flue gas desulfurization absorber 10A through the seawater supply line L1 and used for seawater desulfurization.

Further, in the first flue gas desulfurization absorption apparatus 10A, hydrogen ions (H ⁺ ) generated by the gas-liquid contact between the seawater 12A and the exhaust gas 11 due to seawater desulfurization are released into the seawater 12A, so that the pH is lowered and the sulfur content is absorbed. The liquid 14 absorbs a large amount of sulfur. At this time, the pH of the sulfur component absorbing liquid 14 is, for example, about 3 to 6.

  Moreover, in the seawater desulfation processing apparatus 51 which concerns on a present Example, it branches from the seawater supply line L1, and a part of seawater 12 is used as the 1st dilution seawater 12B via the 1st dilution seawater supply line L3. It is fed to the upstream side of the oxidation tank 56. The first dilution seawater 12 </ b> B is supplied before the inflow plate 56 a provided on the upstream side of the oxidation tank 56.

Then, air 62 is supplied from the oxidizing air blower 61 into the oxidation tank 56 from the oxidation air nozzle 64 through the diffuser pipe 63, and sulfite ions (HSO ₃ ⁻ ) in the sulfur absorbent 14 are supplied in the oxidation tank 56. By oxidizing and desorbing carbon dioxide (CO ₂ ) by a decarboxylation reaction, the sulfur-absorbing liquid 14 is recovered in water quality to become water quality recovered seawater 57. In addition, since the sulfite ion in the sulfur component absorbing liquid 14 can be changed to H ₂ SO ₄ in the apparatus main body 18, the amount of air supplied from the oxidation air blower 61 to the oxidation tank 56 can be reduced.

  Further, a part of the seawater 12 from the seawater supply line L1 is used as the second dilution seawater 12C, and the downstream of the outflow plate 55b provided on the downstream side of the oxidation tank 56 via the second dilution seawater supply line L4. Supply to the side. By supplying the second dilution seawater 12C to the water quality recovery seawater 57, the water quality recovery seawater 57 is further diluted. As a result, the pH of the water quality recovery seawater 57 is increased, the pH of the seawater drainage is increased to near the seawater, the drainage standard for the pH of the seawater drainage (pH 6.0 or more) is satisfied, and COD can be reduced. In addition, the pH and COD of the water quality reforming recovery solution 57 can be released as a level at which seawater can be discharged. And the water quality recovery seawater 57 is discharged | emitted by the sea 58 as seawater waste liquid via the seawater discharge line L6.

Thus, according to the power generation system 40 to which the seawater desulfation treatment apparatus 51 according to the present embodiment is applied, the ACF tank 17 is included in the sulfur component absorbent 14 used for desulfurization in the first flue gas desulfurization absorption apparatus 10A. In the first flue gas desulfurization absorption device 10A, the catalytic action of ACF is utilized in the first flue gas desulfurization absorption device 10A to promote the oxidation of the sulfite ions in the sulfur content absorption liquid 14, thereby efficiently treating the sulfite ions. be able to. Moreover, since the sulfite ion in the sulfur component absorbing liquid 14 can be changed to H ₂ SO ₄ in the apparatus main body 18, the amount of air supplied to the oxidation tank 56 can be reduced.
Therefore, the oxidation equipment cost and running cost used in the power generation system 40 can be suppressed.

  In addition, the power generation system 40 according to the present embodiment includes sulfur oxidation contained in exhaust gas discharged from factories in various industries, power plants such as large and medium-sized thermal power plants, large boilers for electric utilities, or general industrial boilers. It can be used for removal of sulfur content in the sulfur content absorption solution produced by seawater desulfurization of the product.

  As described above, the flue gas desulfurization absorption device according to the present invention is useful for oxidizing sulfur contained in seawater used for seawater desulfurization, and flue gas desulfurization absorption that purifies exhaust gas using seawater. Suitable for use in equipment.

10A-10C 1st-3rd flue gas desulfurization absorption device 11 Exhaust gas 12 Seawater 13 Contact part 14 Sulfur content absorption liquid 15 Tower bottom part (storage part)
16 Activated carbon fiber layer (ACF layer)
17 Activated carbon fiber tank (ACF tank)
DESCRIPTION OF SYMBOLS 18 Main body 21 Exhaust gas supply line 22 Seawater supply line 23 Tower top part 24 Sprinkling nozzle 25 Purified gas 26A-26E Metal containing activated carbon fiber molded object (metal containing ACF molded object)
27A-27C electromagnet (activated carbon fiber recovery part)
28 Seawater discharge line 30 Scraper 31 Liquid leakage prevention member 32 Belt 33 Conveyor 34 Filter 35 ACF reaction chamber 36 Seawater drainage chamber 37 Activated carbon fiber molded body (ACF molded body)
40 Power generation system 41 Air preheater (AH)
42 air 43 boiler 44 steam 45 generator 46 steam turbine 47 water 48 condenser 49 flue gas denitration device 50 dust collector 51 seawater desulfation treatment device 52 chimney 53 pushing fan 54 induction fan 55 heat exchanger 56 oxidation tank 56a inflow Plate 56b Outflow plate 57 Water quality recovery seawater 58 Sea 59, 60 Pump 61 Oxidizing air blower 62 Air 63 Air diffuser pipe 63 Oxidizing air nozzle L1 Seawater supply line L2 Sulfur component absorbing liquid discharge line L3 First dilution seawater supply line L4 Second dilution seawater supply line L5 Purified gas discharge line L6 Seawater discharge line

Claims (13)

In a flue gas desulfurization absorption device that cleans sulfur in exhaust gas by contacting with seawater,
A contact portion for bringing the exhaust gas into contact with the seawater;
A storage part in which the sulfur-absorbing liquid that has absorbed the sulfur content in the exhaust gas by bringing the exhaust gas into contact with the seawater in the contact part is stored;
An activated carbon fiber tank disposed in the reservoir and formed of an activated carbon fiber layer made of activated carbon fibers;
A flue gas desulfurization absorption device comprising: In a flue gas desulfurization absorption device that cleans sulfur in exhaust gas by contacting with seawater,
A contact portion for bringing the exhaust gas into contact with the seawater;
A storage part in which the sulfur-absorbing liquid that has absorbed the sulfur content in the exhaust gas by bringing the exhaust gas into contact with the seawater in the contact part is stored;
A metal-containing activated carbon fiber molded article that is dispersed in the reservoir and molded by containing metal in activated carbon fiber; and
An activated carbon fiber recovery unit that is provided in the storage unit and recovers the metal-containing activated carbon fiber molded body;
A flue gas desulfurization absorption device comprising: In claim 2,
The activated carbon fiber recovery part is a magnet or an electromagnet. In claim 2 or 3,
The flue gas desulfurization absorption device, wherein the metal is iron or nickel. In any one of Claims 2 thru | or 4,
The flue gas desulfurization absorption device, wherein the shape of the metal-containing activated carbon fiber molded body is any one of interdigital shape, warmth shape, scallop shape, or spherical shape. In any one of Claims 2 thru | or 5,
A flue gas desulfurization absorption device, wherein a filter for preventing the metal-containing activated carbon fiber molded body from flowing out of the apparatus main body is provided in the storage portion. A flue gas desulfurization absorber according to any one of claims 1 to 6,
A dilution seawater supply line for supplying the seawater as dilution seawater to the flue gas desulfurization absorber;
An oxidation tank that oxidizes and decarboxylates the sulfur content in the sulfur content absorbent discharged from the flue gas desulfurization absorber, and performs water quality recovery;
A sulfur absorption liquid discharge line for discharging the sulfur absorption liquid to the oxidation tank;
A part of the dilution seawater is supplied to the oxidation tank as first dilution seawater, and the first dilution seawater supply line is mixed with the sulfur absorbent,
A second dilution seawater supply line that joins a part of the dilution seawater as the second dilution seawater with the water quality recovered seawater recovered in the oxidation tank;
A seawater desulfation treatment apparatus characterized by comprising: With a boiler,
Using the exhaust gas discharged from the boiler as a heat source for steam generation, and a steam turbine for driving a generator using the generated steam;
A condenser for collecting and circulating the water condensed in the steam turbine;
A flue gas denitration device for denitrating exhaust gas discharged from the boiler;
A dust collector for removing the dust in the exhaust gas;
A seawater desulfation treatment apparatus according to claim 7;
A chimney for discharging the purified gas desulfurized by the flue gas desulfurization absorption device to the outside;
A power generation system comprising: In the exhaust gas treatment method of contacting exhaust gas with seawater to absorb sulfur content in the exhaust gas into the seawater and cleaning the exhaust gas,
Immerse the activated carbon fiber tank formed by the activated carbon fiber layer made of activated carbon fiber in the sulfur absorbing solution that has absorbed the sulfur,
An exhaust gas treatment method characterized by accelerating oxidation of the sulfur content in the sulfur content absorbing solution that has absorbed the sulfur content by the activated carbon fiber. In the exhaust gas treatment method of contacting exhaust gas with seawater to absorb sulfur content in the exhaust gas into the seawater and cleaning the exhaust gas,
A metal-containing activated carbon fiber molded body in which a metal is contained in activated carbon fiber is dispersed in the sulfur-absorbing liquid that has absorbed the sulfur content, and the sulfur content in the sulfur-absorbing liquid is molded into the metal-containing activated carbon fiber molding. An exhaust gas treatment method comprising oxidizing by contacting with a body. In claim 10,
An exhaust gas treatment method, wherein the activated carbon fiber recovery unit recovers the metal-containing activated carbon fiber molded body in the sulfur component absorbing liquid. In claim 11,
The exhaust carbon treatment method, wherein the activated carbon fiber recovery unit is a magnet or an electromagnet. In claim 11 or 12,
The exhaust gas treatment method, wherein the metal is iron or nickel.

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