WO2014196458A1 - Device for desulfurization with seawater and system for desulfurization with seawater - Google Patents

Abstract

A device equipped with: a desulfurization absorption tower 11 in which a discharge gas 18 containing sulfur oxides is contacted with seawater 17 to desulfurize the discharge gas; a discharge gas inlet 12 through which the discharge gas containing the sulfur oxides is introduced into the desulfurization absorption tower; a first seawater ejection means 13 which has been disposed in the desulfurization absorption tower above the discharge gas inlet and which ejects the seawater in the form of liquid columns to make flows that are opposed to the discharge gas which has been introduced through the discharge gas inlet and is moving upward; and a backflow prevention means 14 which has been disposed between the discharge gas inlet and the first seawater ejection means and with which the seawater that has been ejected by the first seawater ejection means and is falling is prevented from flowing backward into the discharge gas inlet.

Description

Seawater desulfurization apparatus and seawater desulfurization system

The present invention relates to a seawater desulfurization apparatus and a seawater desulfurization system.

Conventionally, in a power plant using coal, crude oil or the like as fuel, combustion exhaust gas (hereinafter referred to as “exhaust gas”) discharged from a boiler is sulfur dioxide (SO ₂ ) or the like contained in the exhaust gas. Sulfur oxide (SOx) is removed before being released to the atmosphere. As a desulfurization method of a desulfurization apparatus that performs such a desulfurization treatment, for example, a limestone gypsum method, a spray dryer method, a seawater method, and the like are known.

Among these, a desulfurization apparatus (hereinafter referred to as “seawater desulfurization apparatus”) employing the seawater method is a desulfurization system that uses seawater as an absorbent. In this system, for example, by supplying seawater and boiler exhaust gas into a desulfurization absorption tower having a cylindrical shape or a square shape such as a substantially cylindrical shape, a wet-based gas-liquid contact is generated using seawater as an absorbent. To remove sulfur oxides.

The desulfurized seawater (spent seawater) used as an absorbent in the desulfurization absorption tower described above, for example, flows and drains through a long waterway (Seawater Oxidation Treatment System: SOTS) with an open top. Decarboxylation (explosion) is performed by an aeration process in which fine bubbles flow out from an aeration apparatus installed on a part of the bottom (Patent Documents 1 to 3).

JP 2006-055779 A JP 2009-028570 A JP 2009-028572 A

However, in a seawater desulfurization system that employs a seawater desulfurization device, when the amount of treated gas decreases, or when there is a load fluctuation or load stoppage on the system, spent seawater is discharged into the exhaust gas inlet duct of the desulfurization absorption tower. There is a problem of backflow.

When the used seawater flows backward to the exhaust gas inlet duct, which is the exhaust gas inlet, the spent seawater has a high acidity (about pH 2 to 5), which promotes corrosion of the exhaust gas inlet duct. As corrosion progresses, cracks occur in the exhaust gas inlet duct, and there is a concern that the used seawater flows out of the system from the cracked part.

Therefore, the advent of a seawater desulfurization apparatus that suppresses the backflow of spent seawater to the exhaust gas inlet duct of the desulfurization absorption tower and a seawater desulfurization system equipped with the apparatus are desired.

In view of the above problems, an object of the present invention is to provide a seawater desulfurization apparatus that suppresses the backflow of spent seawater to the exhaust gas inlet of a desulfurization absorption tower and a seawater desulfurization system including the apparatus.

According to a first aspect of the present invention, there is provided a desulfurization absorption tower that desulfurizes the exhaust gas by bringing the exhaust gas containing sulfur oxide into contact with seawater, and an exhaust gas inlet that introduces the exhaust gas containing the sulfur oxide into the desulfurization absorption tower. A first seawater spraying means provided above the exhaust gas inlet in the desulfurization absorption tower, spraying seawater in a liquid column shape and creating a flow opposed to the exhaust gas introduced from the exhaust gas inlet and moving upward; A backflow preventing means provided between the exhaust gas inlet and the first seawater spraying means for preventing the seawater falling after being sprayed by the first seawater spraying means from flowing back to the exhaust gas inlet; Is a seawater desulfurization apparatus.

The second invention is the seawater desulfurization device according to the first invention, wherein the backflow prevention means is a grid having a plurality of open passages in the vertical direction.

According to a third invention, in the first invention, the backflow prevention means is a grid having a plurality of open passages in a vertical direction, and in the grid, at least in the vicinity of the exhaust gas inlet of the plurality of open passages. It is a seawater desulfurization device provided with an inclined member inclined downward in the open passage.

4th invention is 2nd seawater spray which sprays seawater separately from the seawater sprayed in the said liquid column shape between the said waste gas inlet and said 1st seawater spray means in 1st or 2nd invention. A seawater desulfurization apparatus provided with means.

The fifth invention is a seawater desulfurization system comprising the seawater desulfurization device according to the first or second invention.

6th invention comprises the seawater desulfurization apparatus as described in 1st or 2nd invention, Furthermore, the dilution mixing tank which dilutes the used seawater discharged | emitted from the said desulfurization absorption tower with the seawater for dilution, The said dilution A seawater desulfurization system comprising: an aeration tank for aeration of diluted used seawater discharged from a mixing tank.

The present invention produces an effect that a seawater desulfurization device that suppresses the backflow of spent seawater to the exhaust gas inlet duct portion of the desulfurization absorption tower and a seawater desulfurization system including the device can be provided.

FIG. 1 is a schematic diagram illustrating an example of a seawater desulfurization system including the seawater desulfurization apparatus according to the first embodiment. FIG. 2 is an enlarged schematic view showing an example of the backflow prevention means in FIG. 3 is a cross-sectional view showing a cross section AA in FIG. FIG. 4 is a cross-sectional view illustrating an example of a backflow prevention unit in the second embodiment. FIG. 5 is a schematic diagram illustrating an example of a seawater desulfurization system including the seawater desulfurization apparatus according to the third embodiment.

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 seawater desulfurization system including a drainage channel of a seawater desulfurization apparatus according to an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a schematic diagram illustrating an example of a seawater desulfurization system including the seawater desulfurization apparatus according to the first embodiment. FIG. 2 is an enlarged schematic view showing an example of the backflow prevention means in FIG. 3 is a cross-sectional view showing a cross section AA in FIG.

(Seawater desulfurization equipment)
As shown in FIG. 1, a seawater desulfurization apparatus 10A includes a desulfurization absorption tower 11 that makes an exhaust gas containing sulfur oxides contact with seawater to desulfurize the exhaust gas, and the desulfurization absorption tower 11 contains the sulfur oxide. In the desulfurization absorption tower 11, the exhaust gas inlet 12 for introducing the exhaust gas is provided above the exhaust gas inlet 12, sprayed with seawater in a liquid column shape, introduced from the exhaust gas inlet 12, and moved upward. The first seawater spraying means 13 for creating a flow opposite to the gas generator 18 is provided between the exhaust gas inlet 12 and the first seawater spraying means 13 and is sprayed by the first seawater spraying means 13 and then dropped. 14 A of backflow prevention means which prevents the seawater 17 to flow back to the exhaust gas inlet 12 is provided.

The desulfurization absorption tower 11 is a liquid column type absorption tower in which the exhaust gas 18 and the seawater 17 are brought into contact with each other and sulfur oxide (SO _X ) contained in the exhaust gas 18 is desulfurized from the exhaust gas 18.

An exhaust gas inlet 12 into which exhaust gas discharged after a combustion reaction in a boiler or the like is introduced is provided on the side surface from the lower side from the center of the desulfurization absorption tower 11. The exhaust gas inlet 12 is embodied, for example, as an exhaust gas inlet duct. The exhaust gas 18 introduced from the exhaust gas inlet 12 moves upward in the desulfurization absorption tower 11 and is discharged from an exhaust gas outlet (not shown) provided at the top of the desulfurization absorption tower 11.

On the side surface of the desulfurization absorption tower 11, a dewatering seawater supply line L ₃ for supplying seawater 17 is connected above the exhaust gas inlet 12. In this embodiment, the seawater (unused seawater) 17 pumped from the sea surface by the pump P ₁ is passed through the seawater supply line L ₁ and the desulfurization seawater supply line L ₃ by the pump P ₂ in the desulfurization absorption tower 11. To be introduced. The seawater 17 introduced into the desulfurization absorption tower 11 is sprayed upward in a liquid column shape from the seawater spray nozzle 13a. Here, the seawater spray nozzle 13a is provided at a predetermined position of the pipe 13 in the desulfurization absorption tower 11 connected to the de-diverted seawater supply line L _3. Accordingly, the pipe 13 and the seawater spray nozzle 13a constitute a first seawater spray means (hereinafter collectively referred to as “first seawater spray means 13” unless otherwise specified).

The seawater sprayed from the seawater spray nozzle 13a is blown up to a predetermined height T to form a so-called liquid column, but after reaching the predetermined height T, it naturally falls downward and oxidizes sulfur in the exhaust gas 18. After absorbing the material, a spent seawater pool 19 is formed in the desulfurization absorption tower 11. When the blown-up seawater falls downward from the predetermined height T, gas-liquid contact is made to face the exhaust gas 18 moving upward in the desulfurization absorption tower 11, and the exhaust gas 18 can be efficiently desulfurized. . As a result, the exhaust gas 18 introduced into the desulfurization absorption tower 11 is converted into purified gas 18A by being subjected to seawater desulfurization. Here, the predetermined height T can be appropriately selected according to the size of the desulfurization absorption tower, the exhaust gas treatment amount, the amount of seawater used, and the like.

At this time, in the desulfurization absorption tower 11, sulfur oxides are absorbed by the reaction represented by the formula (I), and used seawater containing sulfite ions (HSO ₃ ⁻ ) and hydrogen ions (H ⁺ ) is generated. .
SO ₂ (G) + H ₂ O → H ₂ SO ₃ (L) → HSO ₃ ⁻ + H ⁺
... (I)

Accordingly, the spent seawater containing hydrogen ions (H ⁺ ) has a low pH value, which causes corrosion of the exhaust gas inlet duct due to backflow and the like.

Flue gas 18 to be processed in the seawater desulfurization apparatus 10A, and when it is introduced from the combustion device such as a boiler through an exhaust gas supply line L ₄ to the seawater desulfurization apparatus 10A, the amount of exhaust gas discharged from a boiler or the like is reduced, When the entire system including the seawater desulfurization device 10A is stopped (when the load is stopped) or when the load fluctuates, the exhaust gas supply line L ₄ may become negative pressure. At this time, is sucked into the exhaust gas supply line L _4, which used seawater 17A desulfurization absorption tower 11 is a negative pressure, used seawater 17A is the tail gas supply line L ₄ ends the exhaust gas inlet duct (exhaust gas inlet 12) A so-called reverse flow phenomenon occurs.

In this embodiment, the grid-like backflow prevention means 14A is provided in the desulfurization absorption tower 11 for the purpose of suppressing the inflow of the used seawater 17A into the exhaust gas inlet duct due to the backflow phenomenon. 14 A of backflow prevention means are provided in the desulfurization absorption tower 11 above the exhaust gas inlet 12 and below the first seawater spraying means 13. With this configuration, the used seawater 17A descending toward the used seawater reservoir 19 after contact with the exhaust gas 18 is prevented from interfering with the exhaust gas 18 and the seawater 17 sprayed in a liquid column shape after the exhaust gas 18 contacts the exhaust gas inlet duct ( The backflow phenomenon flowing into the exhaust gas inlet 12) can be suppressed.

FIG. 2 is an enlarged schematic view showing an example of the backflow prevention means in FIG. As shown in FIG. 2, the backflow prevention means 14A in the present embodiment is configured as a grid structure having an opening passage 14b partitioned by a plurality of partition walls 14a in the vertical direction. 3 is a cross-sectional view showing a cross section AA in FIG. As shown in FIG. 3, the exhaust gas 18 moves through each of the plurality of open passages 14b from the lower side to the upper side of the backflow preventing unit 14A. On the other hand, the used seawater 17A that has come into contact with the exhaust gas 18 that has passed through the backflow prevention means 14A and has risen above the backflow prevention means 14A passes through each of the plurality of open passages 14b from the top to the bottom of the grid. Fall. As described above, by providing the backflow prevention means 14A above the exhaust gas inlet, even when the exhaust gas supply line L ₄ has a negative pressure, the used seawater 17A that falls in the desulfurization absorption tower 11 falls. Can be prevented from immediately flowing into the exhaust gas inlet duct (exhaust gas inlet 12).

(Seawater desulfurization system)
Hereinafter, a seawater desulfurization system including a seawater desulfurization apparatus will be described with reference to FIGS. In FIGS. 1 and 2, the description of the parts already described is omitted.

As shown in FIG. 1, the seawater desulfurization system 100A in this embodiment includes a desulfurization absorption tower 11 that makes gas-liquid contact between exhaust gas 18 and seawater 17 to desulfurize SO ₂ to sulfurous acid (H ₂ SO ₃ ), and desulfurization. Provided on the downstream side of the absorption tower 11, diluted and mixed tank 20 for diluting and mixing the used seawater 17A containing sulfur with the diluted seawater 17a, and provided on the downstream side of the diluted mixing tank 20 and diluted. And an aeration tank 30 having an aeration device (aeration device) 36 for performing water quality recovery processing of the used seawater 17B. Reference numeral L ₆ is a discharge line for discharging the used seawater 17A to the dilution mixing tank 20.

In seawater desulfurization system 100A, by gas-liquid contact with the flue gas 18 by using the seawater 17 supplied through a seawater supply line L ₁ in the desulfurization absorption tower 11 as an absorbent for desulfurization step, the sulfur oxide in the flue gas 18 The object (SO ₂ ) is absorbed by the seawater 17. And the used seawater 17A which absorbed the sulfur content in the desulfurization absorption tower 11 is supplied to the dilution mixing tank 20 provided on the downstream side of the desulfurization absorption tower 11 via the line L _2. Unused seawater) 17a. Thus, the pH of the used seawater at the time of processing with the aeration tank 30 can be adjusted by diluting the used seawater 17A with low pH with the unused seawater 17a. In this embodiment, the used seawater 17A having a pH of about 2 to 6 can be used as a diluted used seawater 17B having a pH of about 3 to 7.

Using pH is diluted with a dilution mixing tank 20 is prepared seawater 17B is sent through a line L ₇ into the aeration tank 30 which is provided on the downstream side of the dilution mixing tank 20, supplied from the aeration air blower 31 The supplied air 32 is supplied by an aeration nozzle 33 to recover the water quality, and then discharged to the sea as drainage 34.

Here, in the aeration tank 30, reactions represented by the formulas (II) and (III) occur.
HSO ₃ ⁻ + 1 / 2O ₂ → SO ₄ ² + H ⁺ (II)
HCO ₃ ⁻ + H ⁺ → CO ₂ + H ₂ O (III)

In this way, sulfite ions (HSO ₃ ⁻ ) generated by the reaction in the desulfurization absorption tower 11 become soluble sulfate (SO ₄ ²⁻ ) in the aeration tank 30 and are released into seawater. On the other hand, hydrogen ions generated by the oxidation reaction of sulfite ions react with carbonate ions (HCO ₃ ⁻ ) in seawater and are released out of the system as carbon dioxide and water. That is, oxidation and decarboxylation reactions occur in the aeration tank 30.

In FIG. 1, 32a bubbles, 35 diffuser tube, L ₁ is seawater supply line, L ₂ is diluted seawater supply line, L ₃ is seawater supply line for desulfurization, L ₄ is the exhaust gas supply line, L ₅ is Air supply line.

Example 2 will be described with reference to FIG. FIG. 4 is a cross-sectional view illustrating an example of a backflow prevention unit in the second embodiment. In addition, about the member same as the structural member shown in FIG.1, FIG2 and FIG.3, the same code | symbol is attached | subjected and the description is abbreviate | omitted.

In the first embodiment, the backflow prevention means 14A is configured as a grid structure having a plurality of opening passages 14b in the vertical direction, whereas the backflow prevention means 14B in the second embodiment is a grid structure having a plurality of opening passages 14b in the vertical direction. Are provided at least in the opening passage 14b on the exhaust gas inlet 12 (FIG. 1) side, an inclined member 14c for inclining the vertical section of the opening passage 14b downward.

The inclined member 14c is provided so that the opening passage 14b is inclined downward. It is preferable that the inclination direction is gradually inclined from the upper wall surface closest to the exhaust gas inlet to the lower wall surface farthest from the exhaust gas inlet in one opening passage. This is to improve the backflow prevention effect of the used seawater 17A having a small pH value. As the inclined member 14c, for example, a member in which an inclined plate or the like is fitted in the opening passage 14b of the grid opening in the vertical direction used in the first embodiment can be used. Or what formed a part of partition wall which forms the opening channel | path 14b of a grid diagonally, etc. may be sufficient. In the illustrated example, among the partition walls 14a constituting the opening passage 14b, the partition wall 14a in the vicinity of the exhaust gas inlet 12 (FIG. 1) is also inclined.

By providing such an inclined member 14c, the movement path of the exhaust gas 18 from the lower side to the upper side of the backflow prevention means 14B is secured, while the open passage near the exhaust gas inlet side from the upper side to the lower side of the backflow prevention means 14B. The falling direction of the droplets of the used seawater 17 </ b> A to go can be changed to a direction away from the exhaust gas inlet. Therefore, the backflow prevention effect of used seawater can be further improved.

The opening passage 14b provided with the inclined member 14c can be appropriately selected according to the application in consideration of the size of the desulfurization absorption tower, the flow rate of the exhaust gas, the spray amount of seawater, and the like.

FIG. 5 is a schematic diagram illustrating an example of a seawater desulfurization system including the seawater desulfurization apparatus according to the third embodiment. In addition, about the member same as the structural member shown in FIG. 1, the same code | symbol is attached | subjected and the description is abbreviate | omitted.

As shown in FIG. 5, the seawater desulfurization apparatus 10B according to the seawater desulfurization system 100B according to the third embodiment includes a first seawater spraying means 13 that constitutes a seawater spraying means, a backflow prevention means 14B, and a desulfurization absorption tower 11. In between, the 2nd seawater spraying means 15 which sprays seawater separately from the seawater sprayed in the liquid column shape is provided.

In the example shown in the drawing, seawater (unused seawater) 17 pumped from the sea surface by a pump P ₁ is diluted seawater (unused seawater) 17 a via a supply line L ₂ , and further diluted with a seawater branch line L ₈ for dilution. Then, it is introduced into the desulfurization absorption tower 11 and sprayed into the desulfurization absorption tower 11 by the second seawater spraying means 15.

Second seawater spraying means 15 is a pipe in the desulfurization absorption tower 11 which is connected from the dilution seawater branch line L _8, has upper, lower, or the spray nozzle 15a which can be sprayed sea water 17 in both Yes. The spray nozzle 15a of the present embodiment sprays unused seawater 17a downward, but the present invention is not limited to this, and an upward spray form and upward and downward spray forms may be employed. .

The second seawater spraying means 15 adds the unused seawater 17a to the used seawater 17A that comes into contact with the exhaust gas 18 and descends toward the used seawater pool 19 to thereby pass the seawater 17 passing through the vicinity of the exhaust gas inlet 12. Is used for the purpose of increasing the pH of the gas and further improving the corrosion prevention effect near the exhaust gas inlet 12. Therefore, since the seawater 17 sprayed from the second seawater spraying means 15 may be added to the used seawater before passing through the vicinity of the exhaust gas inlet 12, a large spray pressure like the first seawater spraying means 13 is required. It is not necessary to be sprayed in a liquid column shape, and the spraying direction is not limited.

10 (10A, 10B) Seawater desulfurization device 11 Desulfurization absorption tower 12 Exhaust gas inlet 13 First seawater spraying means 14 (14A, 14B) Backflow prevention means 14a Partition wall 14b Opening passage 14c Inclined member 15 Second seawater spraying means 17 Seawater 18 Exhaust gas 20 Dilution mixing tank 30 Aeration tank 100 (100A, 100B) Seawater desulfurization system

Claims (6)

A desulfurization absorption tower for desulfurizing the exhaust gas by contacting exhaust gas containing sulfur oxide with seawater;
An exhaust gas inlet for introducing the exhaust gas containing the sulfur oxide into the desulfurization absorption tower;
In the desulfurization absorption tower, a first seawater spraying means is provided above the exhaust gas inlet, sprays seawater in a liquid column shape, and creates a flow facing the exhaust gas introduced from the exhaust gas inlet and moving upward;
Backflow prevention means provided between the exhaust gas inlet and the first seawater spraying means for preventing seawater falling after being sprayed by the first seawater spraying means from flowing back to the exhaust gas inlet;
A seawater desulfurization apparatus comprising: The seawater desulfurization apparatus according to claim 1, wherein the backflow prevention means is a grid having a plurality of open passages in the vertical direction. The backflow prevention means is a grid having a plurality of open passages in the vertical direction,
2. The seawater desulfurization device according to claim 1, wherein in the grid, an inclined member that is inclined downward is provided in at least an opening passage in the vicinity of the exhaust gas inlet among the plurality of opening passages. The seawater desulfurization according to claim 1 or 2, wherein a second seawater spraying means is provided between the exhaust gas inlet and the first seawater spraying means to spray seawater separately from the seawater sprayed in the liquid column shape. apparatus. A seawater desulfurization system comprising the seawater desulfurization apparatus according to claim 1 or 2. It comprises the seawater desulfurization device according to claim 1 or 2,
Furthermore, a dilution mixing tank for diluting the used seawater discharged from the desulfurization absorption tower with seawater for dilution,
An aeration tank for aeration of diluted used seawater discharged from the dilution mixing tank;
A seawater desulfurization system comprising:

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