TW201840353A

TW201840353A - Desulfurizing method and desulfurizing device

Info

Publication number: TW201840353A
Application number: TW107106762A
Authority: TW
Inventors: 亀田孝雄; 丸川浩伸
Original assignee: 日商千代田化工建設股份有限公司
Priority date: 2017-03-09
Filing date: 2018-03-01
Publication date: 2018-11-16
Also published as: JP2018144011A; JP6837355B2; WO2018163733A1

Abstract

This desulfurizing method for exhaust gas is provided with: a contacting step in which a gas to be treated containing sulfur oxides is introduced into an alkaline agent-containing liquid accommodated in a reaction tank, oxygen is supplied to the alkaline agent-containing liquid, products generated by a reaction of the sulfur oxides, oxygen, and the alkaline agent in the alkaline agent-containing liquid are precipitated in the alkaline agent-containing liquid; a first extracting step in which slurry containing the alkaline agent-containing liquid and the precipitated products is extracted from a first region in the reaction tank; a second extracting step of extracting a fluid, which can reduce the slurry, from a second region which is in the reaction tank or communicates with the reaction tank; a mixing step of mixing the slurry extracted from the first extracting step and the fluid extracted from the second extracting step; and a separating and recovering step in which solid content is separated and recovered from the mixture of the slurry and the fluid mixed in the mixing step.

Description

脫硫方法及脫硫裝置Desulfurization method and desulfurization device

本發明有關噴射鼓泡(jet bubbling)方式的脫硫方法及脫硫裝置。The present invention relates to a jet bubbling method for desulfurization and a desulfurization device.

從燃煤爐或燃煤火力發電廠排出的燃燒廢氣中含有硫氧化物(SOx)，此硫氧化物會藉由脫硫裝置被去除。作為從含有硫氧化物的燃燒廢氣將硫氧化物除去之脫硫裝置，已知有噴射鼓泡方式或噴霧(spray)方式等，噴射鼓泡方式的脫硫裝置其脫硫性能優良因此廣受使用。所謂噴射鼓泡方式的脫硫裝置，係於反應槽內將含有硫氧化物的廢氣在含鹼劑液中起泡，令硫氧化物與氧與鹼劑反應而將硫氧化物除去者。The combustion exhaust gas discharged from a coal-fired furnace or a coal-fired thermal power plant contains sulfur oxides (SOx), which are removed by a desulfurization device. As a desulfurization apparatus that removes sulfur oxides from a combustion exhaust gas containing sulfur oxides, a jet bubbling method or a spray method is known, and a debubbing device of a jet bubbling method is excellent in desulfurization performance and thus is widely affected. use. In the defoaming apparatus of the jet bubbling system, the exhaust gas containing sulfur oxides is foamed in the alkali containing agent solution in the reaction tank, and the sulfur oxides are reacted with oxygen and an alkali agent to remove the sulfur oxides.

噴射鼓泡方式的脫硫裝置中，藉由反應而生成之石膏會蓄積於反應槽中，因此含有生成的石膏之漿體(slurry)會從反應槽中被抽出。然後，被抽出的漿體會被固液分離，固體成分亦即石膏會被回收。另一方面，藉由固液分離而石膏被回收後的回收殘液，至少一部分會從脫硫裝置被排出。　　此處，從反應槽中抽出的漿體中含有之液，為高氧化環境且高pH，因此含有氧化性物質或6價硒(Se⁶⁺ )。氧化性物質會引起排水處理裝置的劣化，此外，6價硒在世界各國都被限制排出。鑑此，會藉由排水處理裝置進行排水處理，去除氧化性物質或6價硒。不過，會需要排水處理裝置的設置成本或處理時間，因此盼望減低氧化性物質或6價硒，已有許多人嘗試將系統內的環境從高氧化環境變為低氧化環境(趨近還原環境之狀態)。In the jet bubbling type desulfurization apparatus, the gypsum generated by the reaction is accumulated in the reaction tank, and therefore the slurry containing the generated gypsum is extracted from the reaction tank. Then, the extracted slurry is separated by solid and liquid, and the solid component, that is, gypsum, is recovered. On the other hand, at least a part of the recovered residual liquid after the gypsum is recovered by solid-liquid separation is discharged from the desulfurization apparatus. Here, since the liquid contained in the slurry extracted from the reaction tank has a high oxidation atmosphere and a high pH, it contains an oxidizing substance or hexavalent selenium (Se ⁶⁺ ). Oxidizing substances cause deterioration of the drainage treatment device, and in addition, hexavalent selenium is restricted from being discharged in various countries around the world. In view of this, the drainage treatment device performs drainage treatment to remove oxidizing substances or hexavalent selenium. However, the installation cost or treatment time of the drainage treatment device may be required, and thus it is expected to reduce the oxidizing substance or the hexavalent selenium. Many people have tried to change the environment in the system from a high oxidation environment to a low oxidation environment (to approach the reduction environment). status).

例如，專利文獻1中記載之噴射鼓泡方式的濕式脫硫裝置中，在反應槽內設置隔壁，藉此讓反應槽被區隔成受到充分的氧供給之完全氧化域、及未受到充分的氧供給之不完全氧化域。按照此專利文獻1之脫硫裝置，實現了在完全氧化域確保高脫硫率，並且在不完全氧化域減低氧化性物質。　　然而專利文獻1的脫硫裝置中，必須在反應槽的內部設置許多的追加構件，如將反應槽區隔成完全氧化域與不完全氧化域之隔壁、或可對各域供給相異量的氧之氧供給手段、設於各域之攪拌機等。此外，內部設有該些追加構件之反應槽，其機構會複雜化。For example, in the wet desulfurization apparatus of the jet bubbling method described in Patent Document 1, a partition wall is provided in the reaction tank, whereby the reaction tank is partitioned into a complete oxidation domain that is sufficiently supplied with oxygen, and is not sufficiently The incomplete oxidation domain of the oxygen supply. According to the desulfurization apparatus of Patent Document 1, it is achieved that a high desulfurization rate is ensured in the complete oxidation domain, and an oxidizing substance is reduced in the incomplete oxidation domain. However, in the desulfurization apparatus of Patent Document 1, it is necessary to provide a plurality of additional members inside the reaction tank, such as partitioning the reaction tank into a partition wall of a complete oxidation domain and an incomplete oxidation domain, or supplying different amounts to each domain. Oxygen oxygen supply means, a mixer provided in each domain, and the like. Further, the reaction tanks of the additional members are provided inside, and the mechanism is complicated.

另一方面，專利文獻2中記載之噴射鼓泡方式的濕式脫硫裝置中，從反應槽暫且被抽出之高氧化環境的漿體，藉由和含有硫氧化物之燃燒廢氣接觸而被還原，成為了低氧化環境後再次從反應槽被抽出，被排出至裝置外而回收。也就是說，再次從反應槽被抽出的漿體，藉由和含有硫氧化物之燃燒廢氣接觸，會比最初從反應槽被抽出時被還原成更低氧化環境。是故，按照專利文獻2之脫硫裝置，能夠以簡單的構成，達成抑制對排水處理裝置的負荷與生成物的高回收率化及高純度化。　　不過近年來，排水限制益發強化，強烈盼望一種藉由做出低氧化環境來抑制氧化性物質或6價硒的生成，並且具有優良的脫硫性能，簡易的構成之噴射鼓泡方式的脫硫方法及脫硫裝置。 [先前技術文獻] [專利文獻]On the other hand, in the wet desulfurization apparatus of the jet bubbling method described in Patent Document 2, the slurry in the highly oxidizing environment temporarily extracted from the reaction tank is reduced by contact with the combustion exhaust gas containing sulfur oxides. After being in a low oxidation environment, it is again taken out from the reaction tank and discharged to the outside of the apparatus for recovery. That is to say, the slurry which is again withdrawn from the reaction tank is brought into contact with the combustion exhaust gas containing sulfur oxides to be reduced to a lower oxidation environment than when it is initially withdrawn from the reaction tank. Therefore, according to the desulfurization apparatus of the patent document 2, it is possible to suppress the load on the wastewater treatment apparatus and the high recovery rate and high purity of the product with a simple configuration. However, in recent years, drainage restrictions have been strengthened, and there is a strong desire for a desulfurization by a jet bubbling method that suppresses the formation of oxidizing substances or hexavalent selenium by making a low-oxidation environment, and has excellent desulfurization performance. Method and desulfurization device. [Prior Technical Literature] [Patent Literature]

[專利文獻1]　日本特許第4269379號公報　　[專利文獻2]　日本特開2015-71141號公報[Patent Document 1] Japanese Patent No. 4269379 (Patent Document 2) Japanese Patent Laid-Open Publication No. 2015-71141

[發明所欲解決之問題][The problem that the invention wants to solve]

鑑此，本發明之目的在於提供一種抑制氧化性物質或6價硒的生成，並且具有優良的脫硫性能，簡易的構成之脫硫方法及脫硫裝置。 [解決問題之技術手段]Accordingly, an object of the present invention is to provide a desulfurization method and a desulfurization apparatus which are capable of suppressing the formation of an oxidizing substance or hexavalent selenium and having excellent desulfurization performance, a simple configuration. [Technical means to solve the problem]

本發明的一個實施形態之脫硫方法，其特徵為，具備：接觸工程，將含有硫氧化物的被處理氣體，導入至收容於反應槽內之含鹼劑液中，對該含鹼劑液供給氧，令前述含鹼劑液中析出藉由前述硫氧化物和前述氧和前述含鹼劑液中的鹼劑之反應而產生的生成物；及第1抽出工程，從前述反應槽內的第1區域，抽出含有前述含鹼劑液與前述析出的生成物之漿體；及第2抽出工程，抽出前述反應槽內的、或是從和前述反應槽連通之第2區域，抽出能夠將前述漿體還原之流體；及混合工程，將前述第1抽出工程中抽出的前述漿體、與前述第2抽出工程中抽出的前述流體予以混合；及分離回收工程，從該混合工程中混合的前述漿體與前述流體之混合物，將固體成分予以分離回收。A desulfurization method according to an embodiment of the present invention, comprising: contacting a process, introducing a gas to be treated containing sulfur oxides into an alkali-containing agent liquid contained in a reaction tank, and the alkali-containing agent liquid Supplying oxygen to precipitate a product produced by the reaction between the sulfur oxide and the alkali agent in the alkali agent solution; and the first extraction process from the reaction tank In the first region, the slurry containing the alkali-containing solution and the precipitated product is extracted; and the second extraction process is performed, and the second region in the reaction tank or connected to the reaction vessel is extracted, and the extraction can be performed. The slurry for reducing the slurry; and the mixing process, mixing the slurry extracted in the first extraction project and the fluid extracted in the second extraction project; and separating and recovering the mixture, and mixing the mixture from the mixing process The mixture of the slurry and the fluid described above separates and recovers the solid component.

此外，本發明的另一個實施形態之脫硫裝置，其特徵為，具備：反應槽，具有：被處理氣體導入路、及從該被處理氣體導入路供含有硫氧化物的被處理氣體導入之被處理氣體導入室、及設於該被處理氣體導入室的下側而供含鹼劑液收容於其下部之含鹼劑液室、及將被導入至前述被處理氣體導入室的前述被處理氣體供給至收容於前述含鹼劑液室的前述含鹼劑液中之氣體下降管；及氧供給管，對收容於前述含鹼劑液室之前述含鹼劑液中供給氧；及第1抽出部，從前述含鹼劑液室內的第1區域，抽出含有前述含鹼劑液與藉由前述硫氧化物和前述氧和前述含鹼劑液中的鹼劑之反應而產生的生成物當中析出至前述含鹼劑液中的析出物之漿體；及第2抽出部，抽出前述反應槽內的、或是從和前述反應槽連通之第2區域，抽出能夠將前述漿體還原之流體；及混合槽，將前述第1抽出部抽出的前述漿體、與前述第2抽出部中抽出的前述流體予以混合；及分離回收部，從該混合槽中被混合的前述漿體與前述流體之混合物，將固體成分予以分離回收。 [發明之功效]Further, a desulfurization apparatus according to another embodiment of the present invention includes a reaction tank having a gas introduction path to be treated, and a gas to be treated containing sulfur oxides introduced from the process gas introduction path. a gas to be treated chamber, an alkali-containing solution liquid chamber provided in a lower portion of the gas-introducing chamber to be contained in the lower portion of the to-be-processed gas introduction chamber, and an alkali-containing liquid to be contained in the lower portion of the to-be-processed gas introduction chamber; a gas supply pipe that supplies the gas to the alkali-containing agent liquid contained in the alkali-containing agent liquid chamber; and an oxygen supply pipe that supplies oxygen to the alkali-containing agent liquid contained in the alkali-containing agent liquid chamber; and the first The extracting unit extracts a product containing the alkali-containing agent liquid and the reaction between the sulfur oxide and the oxygen and the alkali agent in the alkali-containing agent liquid from the first region in the alkali-containing liquid chamber. a slurry which is precipitated in the alkali-containing agent liquid; and a second extraction unit that extracts a second region in the reaction tank or communicates with the reaction tank, and extracts a fluid capable of reducing the slurry ; and mixing tank, will The slurry extracted by the first extraction portion and the fluid extracted from the second extraction portion are mixed; and the separation and recovery portion is a mixture of the slurry and the fluid mixed from the mixing tank to form a solid component It is separated and recovered. [Effects of the invention]

按照本發明，能夠提供一種抑制氧化性物質或6價硒的生成，並且具有優良的脫硫性能，簡易的構成之脫硫方法及脫硫裝置。According to the present invention, it is possible to provide a desulfurization method and a desulfurization apparatus which are excellent in desulfurization performance, have a simple configuration, and which are excellent in desulfurization performance.

[第1實施形態] 〈脫硫裝置〉　　一面參照圖1一面說明本發明第1實施形態之噴射鼓泡方式的脫硫裝置。　　圖1為本發明第1實施形態之噴射鼓泡方式的脫硫裝置的一例示意模型圖。所謂噴射鼓泡方式，係指對被收容於反應槽的下部之含鹼劑液中導入被處理氣體及氧，一面令被處理氣體與含鹼劑液氣液接觸而形成泡沫(froth)層一面令它們反應，來除去硫氧化物之方式。[First Embodiment] <Desulfurization Apparatus> A defoaming apparatus of the injection bubbling method according to the first embodiment of the present invention will be described with reference to Fig. 1 . Fig. 1 is a schematic model diagram showing an example of a jet bubbling type desulfurization apparatus according to a first embodiment of the present invention. The jet bubbling method is a method in which a gas to be treated and oxygen are introduced into an alkali-containing liquid contained in a lower portion of a reaction tank, and a gas to be treated is brought into contact with an alkali-containing liquid to form a froth layer. Let them react to remove the sulfur oxides.

(硫氧化物、被處理氣體) 　　本發明中作為硫氧化物(SOx)，例如可舉出亞硫酸氣體、或是亞硫酸氣體溶解於水而成之物等各種形態的二氧化硫等。此外，作為含有硫氧化物之氣體(被處理氣體)，可舉出從燃煤爐或燃煤火力發電廠排出的燃燒廢氣等。另，例如在煤的燃燒廢氣中一般而言來自煤的硒會含有一定量，本發明的其中一個目的是抑制來自這樣的被處理氣體中含有的硒之6價硒的生成。是故，本發明實施形態之脫硫裝置中作為訂為對象之被處理氣體，並不限於煤的燃燒廢氣，例如煤以外的燃料的燃燒廢氣且為含有硒及硫氧化物之氣體等種種廢氣，得涵括於其對象。(Sulfur Oxide, Processed Gas) In the present invention, as the sulfur oxide (SOx), for example, sulfur dioxide gas or sulfur dioxide gas or a sulfuric acid gas dissolved in water, and the like can be used. In addition, examples of the gas containing sulfur oxides (processed gas) include combustion exhaust gas discharged from a coal-fired furnace or a coal-fired thermal power plant. Further, for example, in the combustion exhaust gas of coal, selenium from coal generally contains a certain amount, and one of the objects of the present invention is to suppress the formation of hexavalent selenium from selenium contained in such a gas to be treated. Therefore, the gas to be treated which is the target of the desulfurization apparatus according to the embodiment of the present invention is not limited to the combustion exhaust gas of coal, and is a combustion exhaust gas of a fuel other than coal, and is a gas containing selenium and sulfur oxides. , must be included in its object.

(反應槽) 　　如圖1所示，噴射鼓泡方式的脫硫裝置100，具有噴射鼓泡方式的反應槽11。另，第1實施形態中的反應槽11為圓筒狀，但反應槽11不限於圓筒狀，能夠做成箱形狀(直方體形狀)等任意形狀。　　反應槽11，具有被處理氣體導入室14、含鹼劑液室16、被處理氣體排出室17。此外，反應槽11中，設有被處理氣體導入路12、被處理氣體排出口13。(Reaction Tank) As shown in Fig. 1, the jet bubbling type desulfurization apparatus 100 has a reaction tank 11 that sprays a bubbling method. In addition, the reaction tank 11 in the first embodiment is cylindrical, but the reaction tank 11 is not limited to a cylindrical shape, and may have any shape such as a box shape (a rectangular shape). The reaction tank 11 has a gas to be treated chamber 14, an alkali-containing liquid chamber 16, and a gas to be treated chamber 17. Further, in the reaction tank 11, a gas to be treated 12 and a gas discharge port 13 to be treated are provided.

被處理氣體導入路12，在反應槽11的側壁中央部附近突出設置，將被處理氣體導入被處理氣體導入室14。　　被處理氣體導入室14，設於反應槽11的內部的鉛直方向中央部，供含有硫氧化物之被處理氣體從被處理氣體導入路12導入。　　含鹼劑液室16，設於被處理氣體導入室14的下側，構成為在下部可收容含鹼劑液15。　　被處理氣體排出室17，設於被處理氣體導入室14的上側，和被處理氣體排出口13連通。　　被處理氣體排出口13，在反應槽11的側壁上部突出設置，將在含鹼劑液室16已受脫硫處理之被處理氣體，從被處理氣體排出室17排出。The gas to be treated 12 is protruded in the vicinity of the central portion of the side wall of the reaction vessel 11, and the gas to be treated is introduced into the gas to be treated chamber 14. The to-be-processed gas introduction chamber 14 is provided in the center of the inside of the reaction tank 11 in the vertical direction, and the gas to be treated containing sulfur oxide is introduced from the to-be-processed gas introduction path 12. The alkali-containing agent liquid chamber 16 is provided on the lower side of the gas-introducing chamber 14 to be processed, and is configured to accommodate the alkali-containing liquid 15 in the lower portion. The to-be-processed gas discharge chamber 17 is provided in the upper side of the to-be-processed gas introduction chamber 14, and is connected to the to-be-processed gas discharge port 13. The gas discharge port 13 to be treated is protruded from the upper portion of the side wall of the reaction tank 11, and the gas to be treated which has been subjected to the desulfurization treatment in the alkali-containing liquid chamber 16 is discharged from the gas to be treated chamber 17.

被處理氣體導入室14和含鹼劑液室16，藉由橫截反應槽11之第1隔壁18而被分隔。此外，被處理氣體導入室14和被處理氣體排出室17，藉由橫截反應槽11之第2隔壁19而被分隔。The gas to be treated chamber 14 and the alkali containing solution chamber 16 are separated by the first partition wall 18 that crosses the reaction vessel 11. Further, the gas to be treated chamber 14 and the gas to be treated chamber 17 are separated by the second partition wall 19 that crosses the reaction vessel 11.

第1隔壁18兼作被處理氣體導入室14的底面。在第1隔壁18，設有朝下方延伸而到達比含鹼劑液15的液面21還下方之複數個氣體下降管22，氣體下降管22將被處理氣體導入室14與含鹼劑液室16連通。是故，被導入至被處理氣體導入室14的被處理氣體，會透過複數個氣體下降管22而被供給至收容於含鹼劑液室16之含鹼劑液15中。在氣體下降管22的下側設有複數個小的開口，從氣體下降管22噴出的被處理氣體會被分散至含鹼劑液15中。The first partition wall 18 also serves as the bottom surface of the gas to be introduced into the process chamber 14. The first partition wall 18 is provided with a plurality of gas downcomers 22 extending downward to reach below the liquid surface 21 of the alkali containing liquid 15, and the gas downcomer 22 connects the gas to be treated chamber 14 and the alkali containing liquid chamber. 16 connected. Therefore, the gas to be treated introduced into the gas introduction chamber 14 to be treated is supplied to the alkali-containing liquid 15 contained in the alkali-containing liquid chamber 16 through the plurality of gas downcomers 22 . A plurality of small openings are provided on the lower side of the gas downcomer 22, and the gas to be treated discharged from the gas downcomer 22 is dispersed in the alkali containing solution 15.

第2隔壁19兼作被處理氣體排出室17的底面。在第2隔壁19，設有朝下方延伸，貫通被處理氣體導入室14的水平方向中央部而到達含鹼劑液室16之連通管25，連通管25將含鹼劑液室16與被處理氣體排出室17連通。是故，於含鹼劑液室16內已受脫硫之被處理氣體，會從含鹼劑液室16內的液面21上的空間亦即空間部26，透過連通管25到達被處理氣體排出室17，從被處理氣體排出口13被排出。　　另，亦可設計成省略被處理氣體排出室17或連通管25，而以連通至空間部26之方式來設置被處理氣體排出口13，空間部26兼作如圖1所示般的被處理氣體排出室17。The second partition wall 19 also serves as the bottom surface of the gas to be treated chamber 17. The second partition wall 19 is provided with a communication pipe 25 that extends downward and penetrates the horizontal center portion of the process gas introduction chamber 14 and reaches the alkali solution-containing liquid chamber 16, and the communication pipe 25 treats the alkali-containing agent liquid chamber 16 and is treated. The gas discharge chamber 17 is in communication. Therefore, the gas to be treated which has been desulfurized in the alkali containing liquid chamber 16 passes through the communication pipe 25 to the gas to be treated from the space on the liquid surface 21 in the alkali containing liquid chamber 16, that is, the space portion 26. The discharge chamber 17 is discharged from the gas discharge port 13 to be treated. Alternatively, the processed gas discharge chamber 17 or the communication pipe 25 may be omitted, and the processed gas discharge port 13 may be provided to communicate with the space portion 26, and the space portion 26 also serves as a gas to be treated as shown in FIG. The chamber 17 is discharged.

在被處理氣體導入路12內，設有將經由配管31的工業用水對被處理氣體噴霧之工業用水供給管32。工業用水，被用作為將被處理氣體加濕之加濕液，將被處理氣體加濕、冷卻。於被處理氣體導入路12內被噴霧的加濕液不限於工業用水，例如為水等，凡是可將被處理氣體加濕之液體則無特別限制。另，配管31及工業用水供給管32，未必一定要設置。此外，在被處理氣體導入路12內及被處理氣體導入室14內，除工業用水供給管32以外亦可設有供給加濕液之其他構件。In the gas-introducing path 12 to be treated, an industrial water supply pipe 32 for spraying the industrial gas through the pipe 31 to the gas to be treated is provided. Industrial water is used as a humidifying liquid that humidifies the gas to be treated, and humidifies and cools the gas to be treated. The humidifying liquid sprayed in the gas introduction path 12 to be treated is not limited to industrial water, and is, for example, water. The liquid which can humidify the gas to be treated is not particularly limited. Further, the piping 31 and the industrial water supply pipe 32 are not necessarily provided. Further, in the gas to be treated pipe 12 and the gas to be treated chamber 14 to be treated, other members for supplying the humidifying liquid may be provided in addition to the industrial water supply pipe 32.

在反應槽11，設有將含鹼劑液15攪拌之攪拌機27。攪拌機27，以規定的旋轉速度旋轉，將被收容於含鹼劑液室16中之含鹼劑液15攪拌。In the reaction tank 11, a stirrer 27 for stirring the alkali containing liquid 15 is provided. The agitator 27 is rotated at a predetermined rotational speed to agitate the alkali-containing solution 15 contained in the alkali-containing solution chamber 16.

(氧供給管) 　　在反應槽11的含鹼劑液室16的底部鄰近，舖設有氧供給管38的一端。氧供給管38的另一端，連接至反應槽11的外部的氧供給源(未圖示)。又，氧藉由氧供給管38被供給至含鹼劑液室16中收容之含鹼劑液15中。　　被供給至含鹼劑液15中的氧，會和溶解於含鹼劑液15中的鹼劑及硫氧化物反應。藉由氧和鹼劑和硫氧化物之反應而產生的生成物的一部分，會析出至含鹼劑液15中而成為析出物。以下，將懸濁有析出物的含鹼劑液(以高濃度含有析出物的含鹼劑液)稱為漿體。　　另，氧供給管38，可從氧供給源供給含氧之液體或氣體至含鹼劑液15中，惟由經濟的觀點看來較佳是供給空氣。(Oxygen Supply Pipe) One end of the oxygen supply pipe 38 is laid in the vicinity of the bottom of the alkali-containing agent liquid chamber 16 of the reaction tank 11. The other end of the oxygen supply pipe 38 is connected to an oxygen supply source (not shown) outside the reaction tank 11. Further, oxygen is supplied to the alkali-containing liquid 15 contained in the alkali-containing liquid chamber 16 by the oxygen supply pipe 38. The oxygen supplied to the alkali containing solution 15 is reacted with an alkali agent and sulfur oxide dissolved in the alkali containing solution 15. A part of the product produced by the reaction of oxygen and an alkali agent and sulfur oxides is precipitated in the alkali-containing agent liquid 15 to form a precipitate. Hereinafter, an alkali-containing solution (an alkali-containing solution containing a precipitate at a high concentration) in which a precipitate is suspended is referred to as a slurry. Further, the oxygen supply pipe 38 can supply an oxygen-containing liquid or gas from the oxygen supply source to the alkali-containing liquid 15, but it is preferable to supply the air from the viewpoint of economy.

(第1抽出部、第1區域) 　　在內部收容漿體之含鹼劑液室16的側壁底部，設有連接至泵浦34之配管33。泵浦34，透過配管33將漿體從含鹼劑液室16內抽出。在泵浦34的出口側連接有配管35的一端，配管35的另一端連接至詳細後述之混合槽36。是故，從含鹼劑液室16被抽出的漿體，會透過配管33、泵浦34、配管35而被收容於混合槽36。　　配管33、泵浦34及配管35構成第1抽出部。此外，含鹼劑液室16內當中，設有配管33之位置的鄰近為第1區域，漿體從此第1區域藉由第1抽出部被抽出。(1st Extraction Portion, First Region) A pipe 33 connected to the pump 34 is provided at the bottom of the side wall of the alkali-containing agent liquid chamber 16 in which the slurry is housed. The pump 34 draws the slurry from the alkali containing liquid chamber 16 through the pipe 33. One end of the pipe 35 is connected to the outlet side of the pump 34, and the other end of the pipe 35 is connected to a mixing tank 36 which will be described later in detail. Therefore, the slurry extracted from the alkali containing solution chamber 16 is accommodated in the mixing tank 36 through the pipe 33, the pump 34, and the pipe 35. The pipe 33, the pump 34, and the pipe 35 constitute a first extraction portion. Further, in the alkali containing solution chamber 16, the position where the pipe 33 is provided is adjacent to the first region, and the slurry is extracted from the first region by the first extracting portion.

配管33的相對於泵浦34側的端部而言相反側的端部，不限定於連接至含鹼劑液室16的側壁底部之構成，凡為設於可抽出含鹼劑液室16內的漿體的位置之構成則無特別限制。但，若要在含鹼劑液室16內也可抽出高氧化性環境的漿體，配管33的端部較佳是設於含鹼劑液室16的底部(比供給被處理氣體之氣體下降管22還靠近供給氧之氧供給管38的區域)。含鹼劑液室16的底部，漿體中的氧的濃度高，為高氧化性環境，因此氧化性物質或6價硒的濃度雖高，但對於抽出不含還原物而煤塵亦少之良好的石膏而言是特別合適的區域。從此處抽出的漿體，與能夠還原漿體之流體(詳細後述)共同混合使用，藉此能夠同時達成氧化性物質或6價硒的減低。　　另，配管33，亦可設於含鹼劑液室16的底部當中的底面部分，但更佳是設於側壁部分。此外，為了於攪拌機27停止時配管33更不易因沉積石膏而閉塞，並且可抽出良好品質的石膏，特佳是將配管33的下端對齊攪拌機27停止時之漿體沉降高度。The end portion of the pipe 33 on the opposite side with respect to the end portion on the pump 34 side is not limited to the configuration of the bottom portion of the side wall connected to the alkali containing liquid chamber 16, and is provided in the extractable alkali containing liquid chamber 16 The composition of the position of the slurry is not particularly limited. However, if a slurry of a highly oxidizing environment is also extracted in the alkali containing liquid chamber 16, the end of the pipe 33 is preferably provided at the bottom of the alkali containing liquid chamber 16 (downper than the gas supplied to the gas to be treated) Tube 22 is also adjacent to the region of oxygen supply tube 38 that supplies oxygen. The bottom of the alkali-containing agent liquid chamber 16 has a high concentration of oxygen in the slurry and is highly oxidizing. Therefore, although the concentration of the oxidizing substance or the hexavalent selenium is high, the coal dust is not good for extracting the reducing substance. A particularly suitable area for gypsum. The slurry extracted therefrom can be used in combination with a fluid capable of reducing the slurry (described later in detail), whereby the reduction of the oxidizing substance or the hexavalent selenium can be simultaneously achieved. Further, the pipe 33 may be provided in the bottom portion of the bottom portion of the alkali containing liquid chamber 16, but it is more preferably provided in the side wall portion. Further, in order to prevent the pipe 33 from being closed by deposition of gypsum when the agitator 27 is stopped, and it is possible to extract gypsum of good quality, it is particularly preferable to align the lower end of the pipe 33 with the slurry sedimentation height when the agitator 27 is stopped.

(第2抽出部、第2區域) 　　另一方面，在反應槽11，抽出能夠將藉由泵浦34被抽出的漿體予以還原之流體的配管37的一端，係設於被處理氣體導入室14的側壁當中相對於設有被處理氣體導入路12之位置而言相反側的位置。配管37的另一端，延伸至詳細後述之混合槽36的內部。是故，從被處理氣體導入室14抽出的被處理氣體，會透過配管37被供給至收容於混合槽36內的漿體。　　也就是說，第1實施形態中，從被處理氣體導入室14抽出而透過配管37被供給至混合槽36之被處理氣體，為能夠將漿體還原之流體。此外，配管37構成第2抽出部。此時，被處理氣體導入室14內當中設有配管37之位置的鄰近為第2區域，能夠將漿體還原之流體亦即被處理氣體從此第2區域被抽出。(Second extraction portion, second region) On the other hand, one end of a pipe 37 for extracting a fluid capable of reducing the slurry extracted by the pump 34 in the reaction tank 11 is provided in the gas introduction chamber to be treated The position of the side wall of 14 is opposite to the position where the gas introduction path 12 to be processed is provided. The other end of the pipe 37 extends to the inside of the mixing tank 36 which will be described later in detail. Therefore, the gas to be treated extracted from the gas introduction chamber 14 to be treated is supplied to the slurry contained in the mixing tank 36 through the pipe 37. In other words, in the first embodiment, the gas to be treated which is taken out from the gas to be treated chamber 14 and supplied to the mixing tank 36 through the pipe 37 is a fluid capable of reducing the slurry. Further, the pipe 37 constitutes a second extraction portion. At this time, the position in which the pipe 37 is provided in the gas-introducing chamber 14 to be processed is adjacent to the second region, and the fluid to be treated, that is, the gas to be treated, is extracted from the second region.

另，能夠將從第2抽出部被抽出的漿體予以還原之流體，不限定於被處理氣體。只要是可從反應槽11、或從和反應槽11連通的反應槽11的外部抽出之流體，且能夠將從第1抽出部被抽出的漿體予以還原之流體則無特別限制。例如，亦可從含鹼劑液室16中的泡沫層28抽出泡沫流體，而用作為能夠將漿體還原之流體。針對從泡沫層28抽出泡沫流體而用作為能夠將漿體還原之流體的例子後述之。Further, the fluid capable of reducing the slurry extracted from the second extraction portion is not limited to the gas to be treated. The fluid that can be withdrawn from the reaction vessel 11 or from the outside of the reaction vessel 11 that communicates with the reaction vessel 11 and that can reduce the slurry extracted from the first extraction portion is not particularly limited. For example, the foam fluid may also be withdrawn from the foam layer 28 in the alkaline containing liquid chamber 16 and used as a fluid capable of reducing the slurry. An example of a fluid that can be used to reduce the foam from the foam layer 28 is described later.

當使用被處理氣體作為能夠將漿體還原之流體的情形下，配管37的設置處，只要是能夠抽出被供給至收容於含鹼劑液室16的含鹼劑液15中之前的被處理氣體之位置則無特別限制。例如，當為反應槽11內的情形下，配管37亦可設於被處理氣體導入室14的任意位置、或氣體下降管22內的任意位置。此外例如當為和反應槽11連通的反應槽11的外部的情形下，亦可設於和反應槽11連通的被處理氣體導入路12的任意位置、或透過被處理氣體導入路12連通至反應槽11而成而連絡從生成被處理氣體的外部裝置至被處理氣體導入路12之連絡路(未圖示)內的任意位置。　　此外，被處理氣體導入室14內的被處理氣體，是藉由被處理氣體導入室14內的自體壓力而經由配管37被供給至混合槽36內的漿體中，但亦可設置壓縮機等來供給。In the case where the gas to be treated is used as the fluid capable of reducing the slurry, the piping 37 is provided as long as it can be extracted before being supplied to the alkali-containing liquid 15 contained in the alkali-containing liquid chamber 16. There is no special restriction on the location. For example, in the case of the inside of the reaction tank 11, the pipe 37 may be provided at any position of the gas to be introduced into the process gas 14 or at any position in the gas drop pipe 22. Further, for example, in the case of the outside of the reaction tank 11 that communicates with the reaction tank 11, it may be provided at any position of the gas-introducing gas introduction path 12 that communicates with the reaction tank 11, or may be communicated to the reaction through the gas-introducing path 12 to be processed. The groove 11 is formed to be connected to any position in the connection path (not shown) from the external device that generates the gas to be processed to the process gas introduction path 12. Further, the gas to be treated in the gas to be introduced into the process gas 14 is supplied to the slurry in the mixing tank 36 through the pipe 37 by the self-pressure in the gas to be introduced into the process gas 14, but a compressor may be provided. Waiting for supply.

(混合槽) 　　在反應槽11的外部，設有混合槽36。　　配管35的一端連接至混合槽36，另一端連接至將漿體從含鹼劑液室16抽出之泵浦34。是故，漿體會藉由泵浦34而被供給至混合槽36。　　此外，配管37的一端連接至混合槽36並且延伸至混合槽36的內部，另一端連接至被處理氣體導入室14的側壁。是故，被處理氣體會透過配管37而被供給至混合槽36。(Mixing tank) A mixing tank 36 is provided outside the reaction tank 11. One end of the pipe 35 is connected to the mixing tank 36, and the other end is connected to a pump 34 that draws the slurry from the alkali containing liquid chamber 16. Therefore, the slurry is supplied to the mixing tank 36 by the pump 34. Further, one end of the pipe 37 is connected to the mixing tank 36 and extends to the inside of the mixing tank 36, and the other end is connected to the side wall of the gas introduction chamber 14 to be treated. Therefore, the gas to be treated is supplied to the mixing tank 36 through the pipe 37.

例如，700MW的鍋爐廢氣中，廢氣中的SO₂ 的濃度為700ppm的情形下，作為配管37，係設置1根4英吋(10.16cm)直徑的PVC(聚氯乙烯；poly vinyl chloride)管，將流經配管37的被處理氣體的流量訂為300～600Nm³ / h-wet。For example, in a 700 MW boiler exhaust gas, when the concentration of SO ₂ in the exhaust gas is 700 ppm, as a pipe 37, a 4-inch (10.16 cm) diameter PVC (polyvinyl chloride) pipe is provided. The flow rate of the gas to be treated flowing through the pipe 37 is set to 300 to 600 Nm ³ /h-wet.

在混合槽36中設有將漿體與被處理氣體混合之攪拌機41，以規定的旋轉速度旋轉。The mixing tank 36 is provided with a stirrer 41 that mixes the slurry with the gas to be treated, and rotates at a predetermined rotational speed.

又，配管49的一端連接至混合槽的上部。配管49的另一端，連接至含鹼劑液室16的側壁上部(和比泡沫層28還上方的空間部26相對應之側壁部分)。是故，在混合槽36內和漿體充分地氣液接觸而受脫硫後之被處理氣體，會從混合槽36內的上部透過配管49被供給至含鹼劑液室16內的空間部26。Further, one end of the pipe 49 is connected to the upper portion of the mixing tank. The other end of the pipe 49 is connected to the upper portion of the side wall of the alkali containing liquid chamber 16 (the side wall portion corresponding to the space portion 26 above the foam layer 28). Therefore, the gas to be treated which is sufficiently desulfurized by contact with the slurry in the mixing tank 36 is supplied from the upper portion of the mixing tank 36 to the space portion in the alkali containing liquid chamber 16 through the pipe 49. 26.

混合槽36，只要是將第1抽出部抽出的漿體、與第2抽出部抽出的流體予以混合而做成混合物者則無特別限制。在混合槽36內，高氧化性環境之漿體，藉由比漿體還低氧化性環境之被處理氣體而被還原，氧化性物質或6價硒會被減低。The mixing tank 36 is not particularly limited as long as it is a mixture of the slurry extracted from the first extraction portion and the fluid extracted from the second extraction portion. In the mixing tank 36, the slurry of the highly oxidizing environment is reduced by the gas to be treated in a lower oxidizing atmosphere than the slurry, and the oxidizing substance or the hexavalent selenium is reduced.

針對此混合槽36內之還原反應詳細說明之。　　在含鹼劑液室16內產生的脫硫反應中需要溶氧，因此從氧供給管38供給氧。不過，藉由氧而引起之氧化反應若進展過度，則4價硒(Se⁴⁺ )會被氧化而產生6價硒(Se⁶⁺ )，並且氧化性物質會增加。是故，含鹼劑液室16內的漿體，其6價硒或氧化性物質容易增加，特別是氧供給管38的鄰近為高氧化性環境因此6價硒或氧化性物質的濃度高。但，含鹼劑液室16的底部的漿體，雖氧化性物質或6價硒的濃度高，但含有不含還原物而煤塵亦少之良好的石膏。　　另一方面，在反應槽11內、或和反應槽11連通的反應槽11的外部，存在能夠將第1抽出部抽出的漿體予以還原之流體。The reduction reaction in this mixing tank 36 will be described in detail. Since oxygen is required to be dissolved in the desulfurization reaction generated in the alkali containing solution chamber 16, oxygen is supplied from the oxygen supply pipe 38. However, if the oxidation reaction caused by oxygen progresses excessively, tetravalent selenium (Se ⁴⁺ ) is oxidized to produce hexavalent selenium (Se ⁶⁺ ), and the oxidizing substance increases. Therefore, in the slurry containing the alkali agent liquid chamber 16, the hexavalent selenium or the oxidizing substance is liable to increase, and in particular, the vicinity of the oxygen supply pipe 38 is in a highly oxidizing atmosphere, and thus the concentration of the hexavalent selenium or the oxidizing substance is high. However, the slurry of the bottom portion of the alkali-containing solution chamber 16 has a high concentration of an oxidizing substance or hexavalent selenium, but contains a gypsum which does not contain a reducing substance and has a small amount of coal dust. On the other hand, in the reaction tank 11 or outside the reaction tank 11 that communicates with the reaction tank 11, there is a fluid capable of reducing the slurry extracted by the first extraction unit.

鑑此，第1實施形態中，被處理氣體的一部分從被處理氣體導入室14內被抽出，與收容於混合槽36內的高氧化性環境的漿體混合。被處理氣體比漿體還低氧化性環境，因此高氧化性環境的漿體會在混合槽36內被還原。其結果，在混合槽36內6價硒被還原成4價硒，氧化性物質被減低。此外，在此時的混合槽36內會產生脫硫反應，因此被供給至混合槽36內的被處理氣體，會在漿體中起泡而充分地受脫硫後，透過配管49到達含鹼劑液室16內的空間部26。　　是故，第1實施形態之脫硫裝置，於混合槽36內令還原反應和脫硫反應充分地產生，藉此能夠以簡易的構成實現抑制氧化性物質或6價硒生成、及優良的脫硫性能。In the first embodiment, a part of the gas to be treated is extracted from the gas to be treated chamber 14 and mixed with the slurry in a highly oxidizing atmosphere accommodated in the mixing tank 36. The gas to be treated is also less oxidizing than the slurry, so that the slurry of the highly oxidizing environment is reduced in the mixing tank 36. As a result, in the mixing tank 36, the hexavalent selenium is reduced to tetravalent selenium, and the oxidizing substance is reduced. Further, since the desulfurization reaction occurs in the mixing tank 36 at this time, the gas to be treated supplied into the mixing tank 36 is bubbled in the slurry and sufficiently desulfurized, and then passes through the pipe 49 to reach the alkali. The space portion 26 in the solution liquid chamber 16. Therefore, in the desulfurization apparatus of the first embodiment, the reduction reaction and the desulfurization reaction are sufficiently generated in the mixing tank 36, whereby the formation of the oxidizing substance or the hexavalent selenium can be suppressed with a simple configuration, and excellent desorption can be achieved. Sulfur performance.

圖2為相對於混合槽36內之被處理氣體的供給量而言之氧量的關係的一例示意圖表。　　700MW的鍋爐廢氣中，當廢氣中的SO₂ 的濃度為700ppm的情形下，作為配管37，係設置1根4英吋(10.16cm)直徑的PVC(聚氯乙烯；poly vinyl chloride)管，而測定令流經配管37的被處理氣體的流量變化時之混合槽36內的氧量，揭示於圖2。　　按照圖2，可知藉由令被處理氣體的流量變化，可相互轉移到比圖表中的虛線還上方的區域亦即氧存在之氧化性環境、及比虛線還下方的區域亦即氧不存在之還原性環境。FIG. 2 is a schematic diagram showing an example of the relationship between the amount of oxygen and the amount of the gas to be treated in the mixing tank 36. In a 700 MW boiler exhaust gas, when the concentration of SO ₂ in the exhaust gas is 700 ppm, as a pipe 37, a 4 inch (10.16 cm) diameter PVC (polyvinyl chloride) pipe is provided. The amount of oxygen in the mixing tank 36 when the flow rate of the gas to be treated flowing through the pipe 37 is changed is measured in Fig. 2 . According to FIG. 2, it can be seen that by changing the flow rate of the gas to be processed, it is possible to shift to a region above the dotted line in the graph, that is, an oxidizing environment in which oxygen exists, and a region below the dotted line, that is, oxygen does not exist. Reducing environment.

此外，圖3為相對於混合槽36內之被處理氣體的供給量而言之氧量及氧化還原電位的關係的一例示意圖表。如同圖2的情形般，測定令被處理氣體的流量變化時之混合槽36內的氧量及氧化還原電位(Oxidation-Reduction Potential；ORP)，揭示於圖3。圖3中虛線表示混合槽36內的ORP，實線表示混合槽36內的溶氧量。　　按照圖3，可知藉由令被處理氣體的流量變化，能夠達成ORP200mV以下。當ORP成為200mV以下的情形下，也就是說，當圖3中被處理氣體的導入量為400Nm³ /h-wet以上的情形下，混合槽36內的溶氧量為0附近或其以下，可知氧化性環境的漿體會被還原，成為還原性環境或趨近還原性環境之狀態。In addition, FIG. 3 is a schematic diagram showing an example of the relationship between the amount of oxygen and the oxidation-reduction potential with respect to the supply amount of the gas to be processed in the mixing tank 36. As shown in Fig. 2, the amount of oxygen and the Oxidation-Reduction Potential (ORP) in the mixing tank 36 when the flow rate of the gas to be treated is changed is shown in Fig. 3. The dotted line in Fig. 3 indicates the ORP in the mixing tank 36, and the solid line indicates the amount of dissolved oxygen in the mixing tank 36. According to Fig. 3, it can be seen that the ORP of 200 mV or less can be achieved by changing the flow rate of the gas to be processed. When the ORP is 200 mV or less, that is, when the introduction amount of the gas to be treated in FIG. 3 is 400 Nm ³ /h-wet or more, the dissolved oxygen amount in the mixing tank 36 is around 0 or less. It can be seen that the slurry in the oxidizing environment is reduced to a reducing environment or a state close to a reducing environment.

(測定部) 　　在混合槽36，設有測定混合槽36內的混合物的氧化還原電位之測定部亦即ORP測定部50。ORP測定部50，只要是能夠測定混合槽36內的混合物的氧化還原電位之物則無特別限制。ORP測定部50測定出的氧化還原電位，被送至詳細後述之控制部(未圖示)。(Measurement Unit) The ORP measurement unit 50, which is a measurement unit that measures the oxidation-reduction potential of the mixture in the mixing tank 36, is provided in the mixing tank 36. The ORP measuring unit 50 is not particularly limited as long as it can measure the oxidation-reduction potential of the mixture in the mixing tank 36. The oxidation-reduction potential measured by the ORP measuring unit 50 is sent to a control unit (not shown) which will be described later in detail.

(分離回收部) 　　在混合槽36的側壁，設有連接至泵浦43之配管42。在混合槽36被混合的漿體與被處理氣體之混合物，從混合槽36內透過配管42藉由泵浦43被抽出。又，在泵浦43的出口側連接有配管44的一端，在配管44的另一端連接有固液分離機46。固液分離機46，將從混合槽36內抽出的混合物固液分離，將固體成分予以分離回收。固液分離機46為分離回收部。(Separation and Collection Unit) A pipe 42 connected to the pump 43 is provided on the side wall of the mixing tank 36. The mixture of the slurry and the gas to be treated which are mixed in the mixing tank 36 is taken out from the mixing tank 36 through the pipe 42 by the pump 43. Further, one end of the pipe 44 is connected to the outlet side of the pump 43, and a solid-liquid separator 46 is connected to the other end of the pipe 44. The solid-liquid separator 46 solid-liquid separation of the mixture extracted from the mixing tank 36, and separates and collects the solid component. The solid-liquid separator 46 is a separation and recovery unit.

(排水處理裝置) 　　在固液分離機46的後段，連接有排水處理裝置。藉由固液分離機46而固體成分被回收後之回收殘液，會經由連接至固液分離機46之配管45而被供給至排水處理裝置。排水處理裝置，可從回收殘液除去氮化合物或COD(化學需氧量；Chemical Oxygen Demand)成分、6價硒等而排出作為排水。(Drainage Treatment Apparatus) A drainage treatment apparatus is connected to the rear stage of the solid-liquid separator 46. The solid residue is recovered by the solid-liquid separator 46, and the residual liquid is recovered and supplied to the wastewater treatment device via the pipe 45 connected to the solid-liquid separator 46. The wastewater treatment device can remove nitrogen compounds, COD (Chemical Oxygen Demand) components, and hexavalent selenium from the recovered residual liquid to be discharged as drainage.

(鹼劑導入部) 　　從配管45分歧出的配管47，連接至反應槽11的含鹼劑液室16。在配管47，於途中設有導入石灰石等鹼劑之鹼劑導入部48。鹼劑導入部48，將鹼劑導入至固液分離後的回收殘液的一部分，做出可再次利用作為含鹼劑液室16中的含鹼劑液15。　　另，配管47及鹼劑導入部48，未必一定要設置。(Alkaline agent introduction unit) The pipe 47 branched from the pipe 45 is connected to the alkali-containing agent liquid chamber 16 of the reaction tank 11. In the pipe 47, an alkali agent introduction portion 48 into which an alkali agent such as limestone is introduced is provided in the middle. The alkali agent introduction unit 48 introduces an alkali agent into a part of the recovered residual liquid after the solid-liquid separation, and makes it possible to reuse it as the alkali-containing agent liquid 15 in the alkali-containing agent liquid chamber 16. Moreover, the piping 47 and the alkali agent introduction part 48 are not necessarily provided.

(控制部) 　　如前述般，ORP測定部50測定出的混合槽36內的混合物的氧化還原電位會被送至控制部(未圖示)。　　控制部，基於此氧化還原電位來控制設於配管37之未圖示的閥等，而能夠將從被處理氣體導入室14抽出的被處理氣體的量(能夠將漿體還原之流體的量)調整成任意量。　　另，控制部，除去從被處理氣體導入室14抽出的被處理氣體的量以外，還能控制從含鹼劑液室16抽出的漿體的量。控制部，控制泵浦34、或是設於配管33，35之未圖示的閥等，而能夠將從含鹼劑液室16抽出的漿體的量調節成任意量。(Control Unit) As described above, the oxidation-reduction potential of the mixture in the mixing tank 36 measured by the ORP measuring unit 50 is sent to a control unit (not shown). The control unit controls the amount of the gas to be treated (the amount of the fluid capable of reducing the slurry) that can be extracted from the gas to be treated chamber 14 by controlling the valve or the like (not shown) provided in the pipe 37 based on the oxidation-reduction potential. Adjust to any amount. Further, the control unit can control the amount of the slurry extracted from the alkali containing solution chamber 16 in addition to the amount of the gas to be treated which is extracted from the gas to be treated chamber 14. The control unit controls the pump 34 or a valve (not shown) provided in the pipes 33 and 35, and can adjust the amount of the slurry extracted from the alkali-containing solution chamber 16 to an arbitrary amount.

控制部，較佳是控制抽出的被處理氣體的量而使ORP測定部50測定之氧化還原電位會成為200mV以下，更佳是控制使成為0mV以上150mV以下。The control unit preferably controls the amount of the gas to be treated to be 0.2 VV or less, and more preferably 0 mV or more and 150 mV or less, as measured by the ORP measuring unit 50.

依以上方式調整了混合槽36內的混合物的ORP後，固體成分藉由固液分離機46被分離回收。After the ORP of the mixture in the mixing tank 36 is adjusted as described above, the solid component is separated and recovered by the solid-liquid separator 46.

按照以上說明的本發明第1實施形態之脫硫裝置，能夠以簡易的構成實現抑制氧化性物質或6價硒的生成、及優良的脫硫性能。According to the desulfurization apparatus of the first embodiment of the present invention described above, it is possible to suppress the formation of an oxidizing substance or hexavalent selenium and excellent desulfurization performance with a simple configuration.

〈脫硫方法〉　　接著，一面參照圖1一面說明使用了上述脫硫裝置100之脫硫方法。此處，第1實施形態之脫硫方法，至少具備接觸工程、第1抽出工程、第2抽出工程、混合工程、分離回收工程。以下，針對各工程依序說明。<Desulfurization Method> Next, a desulfurization method using the above-described desulfurization apparatus 100 will be described with reference to Fig. 1 . Here, the desulfurization method of the first embodiment includes at least a contact engineering, a first extraction project, a second extraction project, a mixing project, and a separation and recovery project. Hereinafter, each project will be described in order.

(接觸工程) 　　接觸工程，是將含有硫氧化物的被處理氣體，導入至收容於反應槽11內之含鹼劑液15中，對含鹼劑液15供給氧，令含鹼劑液15中析出藉由硫氧化物和氧(溶氧)和含鹼劑液15中的鹼劑之反應而產生的生成物。(Contact Engineering) In the contact process, the gas to be treated containing sulfur oxides is introduced into the alkali-containing liquid 15 contained in the reaction tank 11, and oxygen is supplied to the alkali-containing liquid 15, and the alkali-containing liquid 15 is supplied. A product produced by a reaction between sulfur oxides and oxygen (dissolved oxygen) and an alkali agent in the alkali containing solution 15 is precipitated.

圖1所示例子中，首先，含有硫化合物的被處理氣體被導入至設於反應槽11之被處理氣體導入路12。被導入至被處理氣體導入路12的被處理氣體，和從工業用水供給管32噴霧出的工業用水接觸。工業用水為將被處理氣體加濕、冷卻之加濕液。若被處理氣體接觸加濕液，則被處理氣體會被加濕而能夠抑制裝置內的乾燥所造成之水垢(scale)的發生。In the example shown in FIG. 1, first, the gas to be treated containing a sulfur compound is introduced into the gas to be treated 12 provided in the reaction tank 11. The gas to be treated introduced into the gas introduction path 12 to be treated is brought into contact with the industrial water sprayed from the industrial water supply pipe 32. The industrial water is a humidifying liquid that humidifies and cools the gas to be treated. When the gas to be treated contacts the humidifying liquid, the gas to be treated is humidified, and the occurrence of scale due to drying in the apparatus can be suppressed.

接著，被加濕的被處理氣體，經由被處理氣體導入室14流進氣體下降管22。流進氣體下降管22的被處理氣體，到達含鹼劑液室16，從位於收容於含鹼劑液室16內的含鹼劑液15的液面21的下方之氣體下降管22的位於下端鄰近之複數個孔噴出。從氣體下降管22的位於下端鄰近之複數個孔噴出的被處理氣體會成為氣泡狀，在含鹼劑液15中分散，一面和含鹼劑液氣液接觸一面上昇。Then, the humidified gas to be treated flows into the gas downcomer 22 through the gas to be treated chamber 14 . The gas to be treated flowing into the gas downcomer 22 reaches the alkali containing liquid chamber 16, and is located at the lower end of the gas downcomer 22 located below the liquid surface 21 of the alkali containing liquid 15 contained in the alkali containing liquid chamber 16. A plurality of holes are ejected in the vicinity. The gas to be treated which is ejected from the plurality of holes adjacent to the lower end of the gas drop pipe 22 is bubble-like, is dispersed in the alkali-containing agent liquid 15, and rises while being in contact with the liquid containing the alkali agent.

像這樣，由被處理氣體的氣體不連續相、與含鹼劑液的液連續相所構成之氣液接觸層亦即泡沫層28，會形成於含鹼劑液15的液面21上。氧從氧供給管38被供給至含鹼劑液15，因此泡沫層28中，被處理氣體所含有之硫氧化物會和含鹼劑液15中的氧及鹼劑反應。一連串的流程中，被處理氣體中的SO₂ 等硫氧化物會溶解於含鹼劑液中，藉此從被處理氣體中被除去。In this manner, the gas-liquid contact layer composed of the gas discontinuous phase of the gas to be treated and the liquid continuous phase containing the alkali-containing liquid, that is, the foam layer 28, is formed on the liquid surface 21 of the alkali-containing liquid 15. Oxygen is supplied from the oxygen supply pipe 38 to the alkali-containing agent liquid 15, and therefore, the sulfur oxide contained in the gas to be treated in the foam layer 28 reacts with the oxygen and alkali agent in the alkali-containing agent liquid 15. In a series of processes, sulfur oxides such as SO ₂ in the gas to be treated are dissolved in the alkali-containing agent liquid, thereby being removed from the gas to be treated.

硫氧化物和氧和鹼劑之反應中，被處理氣體中含有之SO₂ 等硫氧化物會和鹼劑及氧反應，藉由反應而產生之生成物的一部分會析出至含鹼劑液15中。　　例如，當硫氧化物含有SO₂ ，作為鹼劑使用了石灰石(CaCO₃ )，會發生下記(1)式的反應。也就是說，下記(1)式的反應中，會產生生成物亦即石膏(CaSO₄ ・2H₂ O)，其一部分會作為析出物而析出至含鹼劑液15中。另一方面，硫氧化物會從被處理氣體被除去。 In the reaction between the sulfur oxide and the oxygen and the alkali agent, the sulfur oxide such as SO ₂ contained in the gas to be treated reacts with the alkali agent and oxygen, and a part of the product produced by the reaction is precipitated to the alkali-containing liquid 15 in. For example, when sulfur oxide contains SO ₂ and limestone (CaCO ₃ ) is used as an alkaline agent, the reaction of the following formula (1) occurs. In other words, in the reaction of the following formula (1), gypsum (CaSO ₄ · 2H ₂ O), which is a product, is formed, and a part thereof is precipitated as a precipitate to the alkali-containing liquid 15 . On the other hand, sulfur oxides are removed from the gas to be treated.

所謂含鹼劑液含有的鹼劑，為中和酸之中和劑，例如可舉出碳酸鈣、氫氧化鈉等。此外，作為含鹼劑液的溶媒，可舉出水。The alkali agent contained in the alkali-containing agent liquid is a neutralizing acid neutralizing agent, and examples thereof include calcium carbonate and sodium hydroxide. Moreover, as a solvent of an alkali containing agent liquid, water is mentioned.

被除去了硫氧化物的被處理氣體，會經由含鹼劑液室16的上部的空間部26、連通管25及被處理氣體排出室17，從被處理氣體排出口13排出。The gas to be treated from which the sulfur oxide has been removed is discharged from the gas discharge port 13 to be processed through the space portion 26 of the upper portion of the alkali containing liquid chamber 16, the communication pipe 25, and the gas to be treated chamber 17.

(第1抽出工程) 　　然後，第1抽出工程，是從反應槽11(含鹼劑液室16)內的第1區域，抽出高濃度地含有脫硫反應中產生而析出的生成物之含鹼劑液(以下稱為漿體)。第1區域，為比後述第2區域還高氧化性環境之區域。　　圖1所示例子中，含鹼劑液室16內的側壁底部鄰近的區域為第1區域。此時，第1抽出工程，從含鹼劑液室16內的側壁底部鄰近的區域，藉由泵浦34經由配管33將漿體抽出。被抽出的漿體，經由配管35被收容於混合槽36內。但，本發明完全不限定於圖1所示之構成。(1st extraction process) The first extraction process is to extract a high-concentration alkali-containing product which is produced by the desulfurization reaction and is precipitated from the first region in the reaction tank 11 (the alkali-containing liquid chamber 16). Liquid (hereinafter referred to as slurry). The first region is a region having a higher oxidizing environment than the second region described later. In the example shown in Fig. 1, the region adjacent to the bottom of the side wall in the alkali containing liquid chamber 16 is the first region. At this time, in the first extraction process, the slurry is taken out by the pump 34 through the pipe 33 from the region adjacent to the bottom of the side wall in the alkali containing liquid chamber 16. The extracted slurry is housed in the mixing tank 36 via a pipe 35. However, the present invention is not limited to the configuration shown in Fig. 1 at all.

第1抽出工程，亦可從含鹼劑液室16內的側壁底部以外的區域抽出漿體。抽出漿體之區域，亦即第1區域，只要是可於含鹼劑液室16內抽出漿體之區域則無特別限制。但，含鹼劑液室16的底部，漿體中的氧的濃度高，為高氧化性環境，因此氧化性物質或6價硒的濃度雖高，但對於抽出不含還原物而煤塵亦少之良好的石膏而言是特別合適的區域。從此處抽出的漿體，與能夠還原漿體之流體(詳細後述)共同混合使用，藉此能夠同時達成氧化性物質或6價硒的減低。In the first extraction process, the slurry may be withdrawn from a region other than the bottom of the side wall in the alkali containing liquid chamber 16. The region where the slurry is withdrawn, that is, the first region, is not particularly limited as long as it is a region in which the slurry can be extracted in the alkali-containing liquid chamber 16. However, in the bottom of the alkali-containing agent liquid chamber 16, the concentration of oxygen in the slurry is high, and it is a highly oxidizing environment. Therefore, although the concentration of the oxidizing substance or the hexavalent selenium is high, there is little coal dust for the extraction without the reducing substance. A particularly suitable area for good gypsum. The slurry extracted therefrom can be used in combination with a fluid capable of reducing the slurry (described later in detail), whereby the reduction of the oxidizing substance or the hexavalent selenium can be simultaneously achieved.

(第2抽出工程) 　　另一方面，第2抽出工程，是將被導入至反應槽11的被處理氣體的一部分，從被處理氣體導入室14的第2區域抽出。第2區域，為可將第1抽出工程中抽出的漿體予以還原的環境之區域。　　圖1所示例子中，被處理氣體導入室14內的側壁鄰近為第2區域。此時，第2抽出工程，從被處理氣體導入室14內的側壁鄰近的區域，藉由配管37將被處理氣體導入室14內的被處理氣體的一部分抽出。被抽出的被處理氣體，被供給至收容於混合槽36內之漿體中。被處理氣體比漿體還低氧化性環境，因此能夠將漿體還原。但，本發明完全不限定於圖1所示之構成。(Second Extraction Project) On the other hand, the second extraction project is a part of the gas to be treated which is introduced into the reaction tank 11, and is extracted from the second region of the gas introduction chamber 14 to be processed. The second area is an area of an environment in which the slurry extracted in the first extraction project can be reduced. In the example shown in Fig. 1, the side wall in the gas introduction chamber 14 to be treated is adjacent to the second region. At this time, in the second extraction project, a part of the gas to be treated in the gas to be introduced into the process gas is extracted from the region adjacent to the side wall in the gas introduction chamber 14 to be treated by the pipe 37. The extracted gas to be treated is supplied to the slurry contained in the mixing tank 36. The gas to be treated is also less oxidizing than the slurry, so that the slurry can be reduced. However, the present invention is not limited to the configuration shown in Fig. 1 at all.

第2抽出工程，只要能夠從反應槽11、或是和反應槽11連通的反應槽11的外部抽出能夠將第1抽出工程中抽出的漿體予以還原之流體則無特別限制。是故，第2抽出工程，作為能夠將第1抽出工程中抽出的漿體予以還原之流體，亦可抽出被處理氣體的一部分以外之流體。此外，第2抽出工程中抽出能夠將漿體還原之流體之區域，也就是說第2區域，亦可為被處理氣體導入室14內的側壁鄰近以外之區域，亦可為反應槽11內的被處理氣體導入室14以外之區域，亦可為和反應槽11連通的反應槽11的外部。The second extraction project is not particularly limited as long as the fluid capable of reducing the slurry extracted in the first extraction process can be extracted from the reaction vessel 11 or the reaction vessel 11 that communicates with the reaction vessel 11 . Therefore, the second extraction project can extract a fluid other than a part of the gas to be treated as a fluid capable of reducing the slurry extracted in the first extraction process. Further, in the second extraction project, a region in which the fluid capable of reducing the slurry can be extracted, that is, the second region may be a region other than the side wall in the gas to be introduced into the process gas, or may be in the reaction vessel 11. The area other than the gas to be introduced into the process chamber 14 may be the outside of the reaction tank 11 that communicates with the reaction tank 11.

當抽出被處理氣體的情形下，第2抽出工程，較佳是將被導入至含鹼劑液15中之前的被處理氣體的一部分抽出。另，第2抽出工程，亦可將被導入至反應槽11之前的被處理氣體的一部分抽出，亦可將被導入至反應槽11後的被處理氣體的一部分抽出。是故，第2抽出工程，能夠從氣體下降管22內、從被處理氣體導入室14內或從被處理氣體導入路12內、或是從透過被處理氣體導入路12連通至反應槽11而構成而連絡從生成被處理氣體的外部裝置至被處理氣體導入路12之連絡路(未圖示)內，抽出被處理氣體。When the gas to be treated is extracted, the second extraction process preferably extracts a part of the gas to be treated before being introduced into the alkali-containing solution 15 . Further, in the second extraction project, a part of the gas to be treated before being introduced into the reaction tank 11 may be extracted, or a part of the gas to be treated introduced into the reaction tank 11 may be taken out. Therefore, the second extraction project can be communicated from the gas downcomer 22, from the gas to be treated chamber 14 or from the gas to be treated channel 12, or from the gas to be treated gas introduction path 12 to the reaction vessel 11 In the configuration, the contact gas is extracted from the external device that generates the gas to be processed to the connection path (not shown) of the gas to be treated 12 to be extracted.

(混合工程) 　　混合工程，是將第1抽出工程中從第1區域抽出的漿體、與第2抽出工程中從第2區域抽出的能夠將漿體還原之流體予以混合。　　圖1所示例子中，混合工程，是將從被處理氣體導入室14內抽出的被處理氣體的一部分供給至收容於混合槽36內之從含鹼劑液室16內抽出的漿體中，並起泡，藉此將它們混合。此外，混合工程，較佳是令設於混合槽36之攪拌機41以規定的旋轉速度旋轉，以促進漿體與被處理氣體之混合。　　混合工程中，高氧化性環境之漿體，藉由比漿體還低氧化性環境之被處理氣體而被還原，氧化性物質或6價硒會被減低。此外，混合工程中與漿體混合了的被處理氣體，藉由在漿體中氣液接觸而受到脫硫，透過配管49被導入至含鹼劑液室16中的空間部26。(Mixed Project) The mixing process is a process of mixing the slurry extracted from the first region in the first extraction project with the fluid capable of reducing the slurry extracted from the second region in the second extraction process. In the example shown in Fig. 1, the mixing process is to supply a part of the gas to be treated extracted from the gas to be introduced into the processing chamber to the slurry which is taken out from the alkali containing solution chamber 16 and accommodated in the mixing tank 36. And foaming, thereby mixing them. Further, in the mixing process, it is preferred that the agitator 41 provided in the mixing tank 36 is rotated at a predetermined rotational speed to promote mixing of the slurry with the gas to be treated. In the mixing process, the slurry of the highly oxidizing environment is reduced by the gas to be treated in a lower oxidizing atmosphere than the slurry, and the oxidizing substance or the hexavalent selenium is reduced. Further, the gas to be treated which is mixed with the slurry in the mixing process is desulfurized by gas-liquid contact in the slurry, and is introduced into the space portion 26 in the alkali-containing solution chamber 16 through the pipe 49.

(測定工程) 　　此外，測定工程，較佳是測定混合工程中獲得的混合物的氧化還原電位。　　圖1所示例子中，在混合槽36內設有測定氧化還原電位之ORP測定部50，測定工程，測定混合槽36內的(漿體與被處理氣體之)混合物的氧化還原電位。然後，詳細後述之控制工程，較佳是基於測定出的氧化還原電位，控制第1抽出工程中抽出的漿體的量。(Measurement Engineering) Further, in the measurement engineering, it is preferred to measure the oxidation-reduction potential of the mixture obtained in the mixing process. In the example shown in Fig. 1, an ORP measuring unit 50 for measuring an oxidation-reduction potential is provided in the mixing tank 36, and the oxidation-reduction potential of the mixture (of the slurry and the gas to be treated) in the mixing tank 36 is measured. Then, in detail, the control project described later preferably controls the amount of the slurry extracted in the first extraction project based on the measured oxidation-reduction potential.

(分離回收工程) 　　分離回收工程，從混合工程中被混合的漿體與流體之混合物，將固體成分予以分離回收。　　圖1所示例子中，分離回收工程，從在混合槽36內被混合的漿體與被處理氣體之混合物，藉由固液分離機46將固體成分予以分離回收。另，固體成分從混合物被分離回收後之回收殘液，會經由連接至固液分離機46的出口側之配管45而被供給至排水處理裝置，在排水處理裝置受到排水處理(排水處理工程)。(Separation and recovery project) The separation and recovery project separates and recovers the solid components from the mixture of the slurry and the fluid mixed in the mixing process. In the example shown in Fig. 1, the separation and recovery process separates and recovers the solid component from the mixture of the slurry and the gas to be treated which are mixed in the mixing tank 36 by the solid-liquid separator 46. In addition, the residual liquid recovered from the mixture after the solid component is separated and recovered is supplied to the wastewater treatment device via the pipe 45 connected to the outlet side of the solid-liquid separator 46, and is subjected to drainage treatment in the wastewater treatment device (drainage treatment project). .

(排水處理工程) 　　排水處理工程，從藉由固液分離機46而固體成分(析出物)被分離回收後之回收殘液，除去氮化合物或COD、6價硒等。排水處理是在設於外部之排水處理裝置進行。　　藉由固液分離機46而固體成分被分離回收後之回收殘液，會經由配管45而被供給至排水處理裝置。此回收殘液，其氧化性物質或6價硒的量被減低，因此不必設置新的排水處理裝置，或是能夠減低排水處理的負荷。(Drainage Treatment Project) The wastewater treatment process removes the residual liquid from the solid component (precipitate) by the solid-liquid separator 46, and removes nitrogen compounds, COD, hexavalent selenium, and the like. The drainage treatment is carried out in a drainage treatment device provided outside. The recovered residual liquid after the solid component is separated and recovered by the solid-liquid separator 46 is supplied to the wastewater treatment device via the pipe 45. Since the amount of the oxidizing substance or the hexavalent selenium is reduced in the recovered residual liquid, it is not necessary to provide a new drainage treatment device, or it is possible to reduce the load of the drainage treatment.

(鹼劑導入工程) 　　此外，鹼劑導入工程，較佳是將石灰石等鹼劑導入至藉由固液分離機46而固體成分被分離之回收殘液當中的一部分，而做出可再次供給至含鹼劑液室16內之含鹼劑液15。　　圖1所示例子中，設有從連接至固液分離機46的出口側之配管45分歧出的配管47，鹼劑導入工程，是將石灰石等鹼劑藉由設於配管47的途中之鹼劑導入部48而導入至回收殘液的一部分。被導入了鹼劑之回收殘液的一部分，會透過配管47被收容於含鹼劑液室16內，用作為含鹼劑液15。(Alkaline agent introduction process) Further, in the alkali agent introduction process, it is preferable to introduce an alkali agent such as limestone into a part of the recovered residual liquid separated by solid components by the solid-liquid separator 46, and to supply it again. The alkali containing agent liquid 15 in the alkali containing liquid chamber 16. In the example shown in Fig. 1, a pipe 47 branched from a pipe 45 connected to the outlet side of the solid-liquid separator 46 is provided, and an alkali agent introduction process is an alkali agent such as limestone which is provided on the middle of the pipe 47. The agent introduction unit 48 is introduced into a part of the recovered residual liquid. A part of the recovered residual liquid into which the alkali agent has been introduced is stored in the alkali-containing solution chamber 16 through the pipe 47 and used as the alkali-containing agent liquid 15.

(控制工程) 　　接著，針對上述的控制工程，舉出控制方法的具體例詳細說明之。　　如前述般，控制工程，是基於測定工程中測定出的氧化還原電位，來控制1抽出工程中抽出的漿體的量。　　圖1所示例子中，在混合槽36內設有ORP測定部50，控制工程，基於控制部(未圖示)接收到的從ORP測定部50送來之混合槽36內的混合物的氧化還原電位，而控制第2抽出工程中抽出的被處理氣體的量(能夠將漿體還原之流體的量)。　　另，控制工程，除了第2抽出工程中抽出的被處理氣體的量以外，還能控制第1抽出工程中抽出的漿體的量。(Control Engineering) Next, a specific example of the control method will be described in detail with respect to the above-described control project. As described above, the control project is based on the oxidation-reduction potential measured in the measurement project to control the amount of the slurry extracted in the 1 extraction process. In the example shown in Fig. 1, the ORP measuring unit 50 is provided in the mixing tank 36, and the control project is based on the redox of the mixture in the mixing tank 36 sent from the ORP measuring unit 50 received by the control unit (not shown). At the potential, the amount of the gas to be treated (the amount of the fluid capable of reducing the slurry) extracted in the second extraction process is controlled. Further, in addition to the amount of the gas to be treated which is extracted in the second extraction project, the control project can also control the amount of the slurry extracted in the first extraction project.

控制工程，較佳是控制抽出的被處理氣體的量而使測定工程中ORP測定部50測定之氧化還原電位會成為200mV以下，更佳是控制使成為0mV以上150mV以下。In the control project, it is preferable to control the amount of the gas to be treated, and the oxidation-reduction potential measured by the ORP measuring unit 50 in the measurement process is 200 mV or less, and more preferably controlled to be 0 mV or more and 150 mV or less.

按照以上說明的本發明第1實施形態之脫硫方法，能夠以簡易的構成實現抑制氧化性物質或6價硒的生成、及優良的脫硫性能。According to the desulfurization method of the first embodiment of the present invention described above, it is possible to suppress the formation of an oxidizing substance or hexavalent selenium and excellent desulfurization performance with a simple configuration.

[第2實施形態] 　　圖4為本發明第2實施形態之噴射鼓泡方式的脫硫裝置示意模型圖。圖5為圖4所示脫硫裝置的主要部位擴大圖，揭示溢流壩60及其鄰近之構成。以下，雖針對第2實施形態說明，但對於和第1實施形態相同的構件標記相同符號，並省略重複說明。[Second Embodiment] Fig. 4 is a schematic view showing a defoaming apparatus of a jet bubbling method according to a second embodiment of the present invention. Fig. 5 is an enlarged view of a main part of the desulfurization apparatus shown in Fig. 4, showing the structure of the overflow dam 60 and its vicinity. In the following, the same components as those in the first embodiment are denoted by the same reference numerals, and the description thereof will not be repeated.

如圖4及圖5所示，第2實施形態之脫硫裝置200，係替換圖1所示第1實施形態之脫硫裝置100中的配管37，而具備溢流壩60及配管71。是故，若將第2實施形態之脫硫裝置200與第1實施形態之脫硫裝置100比較，則第2抽出部(第2抽出工程)相異，此外，省略圖示之控制部(控制工程)亦相異。在第2實施形態之脫硫裝置200與第1實施形態之脫硫裝置100中，除第2抽出部及控制部以外為同一。　　以下，針對脫硫裝置200的第2抽出部(第2抽出工程)及控制部(控制工程)詳述之。As shown in FIG. 4 and FIG. 5, the desulfurization apparatus 200 of the second embodiment is provided with a relief dam 60 and a piping 71 instead of the piping 37 in the desulfurization apparatus 100 of the first embodiment shown in FIG. Therefore, when the desulfurization apparatus 200 of the second embodiment is compared with the desulfurization apparatus 100 of the first embodiment, the second extraction unit (second extraction project) is different, and the control unit (not shown) is omitted. Engineering) is also different. In the desulfurization apparatus 200 of the second embodiment and the desulfurization apparatus 100 of the first embodiment, the same is true except for the second extraction unit and the control unit. Hereinafter, the second extraction unit (second extraction project) and the control unit (control project) of the desulfurization apparatus 200 will be described in detail.

(第2抽出部、第2抽出工程、第2區域) 　　第2實施形態中，在含鹼劑液室16內的側壁鄰近，設有從比含鹼劑液15的液面21還下方的位置延伸至液面21的上方之溢流壩60。形成於含鹼劑液15的液面21上之構成泡沫層28之泡沫流體，會溢流過溢流壩60，而流入至含鹼劑液室16的側壁側。另一方面，位於泡沫層28的下部之含鹼劑液15，會被溢流壩60攔住，因此不會流過溢流壩60的上方(不會溢流)，而不會流入至含鹼劑液室16的側壁側。(Second extraction portion, second extraction project, and second region) In the second embodiment, a position lower than the liquid surface 21 of the alkali-containing solution 15 is provided adjacent to the side wall in the alkali-containing solution chamber 16. The overflow dam 60 extends above the liquid level 21. The foam fluid constituting the foam layer 28 formed on the liquid surface 21 of the alkali containing liquid 15 overflows the overflow dam 60 and flows into the side wall side of the alkali containing liquid chamber 16. On the other hand, the alkali-containing agent liquid 15 located at the lower portion of the foam layer 28 is stopped by the overflow dam 60, so that it does not flow over the overflow dam 60 (no overflow), and does not flow into the alkali-containing base. The side wall side of the solution liquid chamber 16.

針對溢流壩60參照圖5進一步詳細說明。　　第2實施形態的溢流壩60，具備側板61、及具有開口部62a之底板62。此外，在溢流壩60的下部設有上昇流抑止板63。The overflow dam 60 will be described in further detail with reference to FIG. 5. The overflow dam 60 of the second embodiment includes a side plate 61 and a bottom plate 62 having an opening 62a. Further, an upflow suppression plate 63 is provided at a lower portion of the overflow dam 60.

側板61，延伸至比含鹼劑液15的靜止液面還上方，攔住含鹼劑液15，而令泡沫流體從泡沫層28溢流。是故，側板61，較佳是延伸至比含鹼劑液15的靜止液面還上方，且比泡沫層28的上端還下方。具體而言，側板61，較佳是延伸至比靜止液面(標準液面高度)還50mm以上上方，更佳是延伸至100mm以上300mm以下上方。　　此處所謂靜止液面，為被處理氣體從氣體下降管22噴出之前的靜止的液面。另，靜止液面位於比液面21還稍上方。The side panel 61 extends above the stationary liquid level of the alkali containing liquid 15 to hold the alkali containing liquid 15 to allow the foam fluid to overflow from the foam layer 28. Therefore, the side plate 61 preferably extends above the stationary liquid level of the alkali containing liquid 15 and below the upper end of the foam layer 28. Specifically, the side plate 61 preferably extends over 50 mm or more from the stationary liquid surface (standard liquid level), and more preferably extends above 100 mm to 300 mm. Here, the stationary liquid surface is a stationary liquid surface before the gas to be treated is discharged from the gas downcomer 22. In addition, the stationary liquid surface is located slightly above the liquid level 21.

另，於排煙脫硫裝置200停止時，泡沫層28中的固形物沉積於溢流壩60的底板62，藉此可能會於排煙脫硫裝置200運轉時損及溢流機能。鑑此，底板62，在圖5所示例子中係傾斜配置，而具有開口部62a。藉由設置開口部62a，泡沫層28中的固形物會被排出至溢流壩60外，而能夠抑制沉積。　　開口部62a的形狀雖無特別限制，但例如為直徑25mm以上50mm以下的圓形形狀。圖5所示例子中，是設有1個開口部62a，但亦可設有複數個開口部62a。In addition, when the flue gas desulfurization apparatus 200 is stopped, the solid matter in the foam layer 28 is deposited on the bottom plate 62 of the overflow dam 60, whereby the overflow function may be damaged when the flue gas desulfurization apparatus 200 is operated. As a result, the bottom plate 62 is disposed obliquely in the example shown in FIG. 5 and has an opening 62a. By providing the opening portion 62a, the solid matter in the foam layer 28 is discharged to the outside of the overflow dam 60, and deposition can be suppressed. The shape of the opening 62a is not particularly limited, but is, for example, a circular shape having a diameter of 25 mm or more and 50 mm or less. In the example shown in Fig. 5, one opening 62a is provided, but a plurality of openings 62a may be provided.

上昇流抑止板63，設於開口部62a的下方。上昇流抑止板63，能夠抑制於含鹼劑液室16的側壁鄰近藉由攪拌機27而產生之溢流壩60外的含鹼劑液15的上昇流，通過開口部62a而流入至底板62的上方(往溢流壩60內混入)。此外，上昇流抑止板63，還能抑制從氧供給管38供給的氣體通過開口部62a而流入至底板62的上方。The upward flow suppressing plate 63 is provided below the opening 62a. The rising flow suppressing plate 63 can prevent the side wall of the alkali-containing agent liquid chamber 16 from being adjacent to the upward flow of the alkali-containing agent liquid 15 outside the overflow dam 60 generated by the agitator 27, and flows into the bottom plate 62 through the opening portion 62a. Above (mixed into the overflow dam 60). Further, the upward flow suppressing plate 63 can suppress the gas supplied from the oxygen supply pipe 38 from flowing into the upper side of the bottom plate 62 through the opening 62a.

又，將溢流過溢流壩60的泡沫流體予以抽出之配管71的一端，係設於含鹼劑液室16的側壁。配管71的另一端，延伸至混合槽36的內部。是故，經由含鹼劑液室16內的溢流壩60而被抽出的泡沫流體，會透過配管71被供給至收容於混合槽36內之漿體中。Further, one end of the pipe 71 for discharging the foam fluid overflowing the overflow dam 60 is provided on the side wall of the alkali containing liquid chamber 16. The other end of the pipe 71 extends to the inside of the mixing tank 36. Therefore, the foam fluid extracted through the overflow dam 60 in the alkali containing liquid chamber 16 is supplied to the slurry accommodated in the mixing tank 36 through the pipe 71.

也就是說，第2實施形態中，從含鹼劑液室16透過配管71被抽出而供給至混合槽36的泡沫流體，為能夠將漿體還原之流體。此外，第2實施形態中，溢流壩60與配管71構成第2抽出部。此時，含鹼劑液室16內當中設有配管71之位置的鄰近，亦即藉由溢流壩60與含鹼劑液室16的側壁而被區隔出之區域，為第2區域。第2抽出部，從第2區域抽出能夠將漿體還原之流體亦即泡沫流體。另，雖亦能不設置溢流壩60而直接從配管71抽出泡沫流體，但可能會有位於泡沫層28的下部之含鹼劑液15大量混入之情形，因此較佳是設置溢流壩60來圍住泡沫流體。此外，泡沫流體是由氣液二相所構成，但氣體的比率高，因此設置溢流壩60，會比直接從配管71抽出更容易確保有效的液量，因此較佳。In other words, in the second embodiment, the foam fluid that is taken out from the alkali-containing agent liquid chamber 16 through the pipe 71 and supplied to the mixing tank 36 is a fluid capable of reducing the slurry. Further, in the second embodiment, the overflow dam 60 and the pipe 71 constitute a second extraction portion. At this time, the vicinity of the position where the pipe 71 is provided in the alkali-containing agent liquid chamber 16, that is, the region partitioned by the overflow dam 60 and the side wall of the alkali-containing agent liquid chamber 16, is the second region. The second extracting unit extracts a fluid which is a fluid capable of reducing the slurry from the second region. Further, although the foaming fluid can be directly withdrawn from the piping 71 without providing the overflow dam 60, there may be a case where the alkali-containing liquid 15 located in the lower portion of the foam layer 28 is mixed in a large amount, and therefore it is preferable to provide the overflow dam 60. To enclose the foam fluid. Further, since the foam fluid is composed of two phases of gas-liquid, but the ratio of the gas is high, it is preferable to provide the overflow dam 60, which is easier to ensure an effective liquid amount than directly withdrawing from the pipe 71.

配管71的設置處，只要是能夠抽出溢流過溢流壩60的泡沫流體之位置則無特別限制，但較佳是設於比含鹼劑液15的液面21(標準液面高度)還上方，且比泡沫層28的上端還下方之含鹼劑液室16的側壁。具體而言，配管71，較佳是設於從含鹼劑液15的靜止液面(標準液面高度)起算100mm下方至200mm上方之含鹼劑液室16的側壁的範圍內。The arrangement of the piping 71 is not particularly limited as long as it can extract the position of the foam fluid overflowing the overflow dam 60, but is preferably provided at a level 21 (standard liquid level) higher than that of the alkali containing liquid 15 The upper side, and the side wall of the alkali containing liquid chamber 16 below the upper end of the foam layer 28. Specifically, the pipe 71 is preferably provided in a range from the side of the alkali-containing liquid chamber 16 below 100 mm to 200 mm from the stationary liquid surface (standard liquid level) of the alkali-containing liquid 15 .

另，構成泡沫層28之泡沫流體，包含脫硫反應中生成而析出的析出物、及含鹼劑液、及脫硫反應中受脫硫的被處理氣體，又，還包含被處理氣體中含有的煤塵等雜質。包含這樣各種成分之泡沫流體，透過配管71被供給至混合槽36。Further, the foam fluid constituting the foam layer 28 contains a precipitate which is formed and precipitated in the desulfurization reaction, an alkali-containing agent liquid, and a gas to be treated which is subjected to desulfurization in the desulfurization reaction, and further contains a gas to be treated. Impurities such as coal dust. The foam fluid containing such various components is supplied to the mixing tank 36 through the pipe 71.

第2實施形態中，脫硫裝置200具備複數個溢流壩60。圖4及圖5中為便於理解發明，僅圖示1個溢流壩60，其他則省略圖示。　　圖6A為第2實施形態之脫硫裝置的構成示意概略截面圖。另，圖6A中為便於理解發明，針對反應槽11的側壁及溢流壩60以外之構成係省略圖示。　　如圖6A所示，溢流壩60，沿著圓筒狀的反應槽11的側壁而等間隔地設有4個。溢流壩60不限於4個，能夠設置任意數量。複數個溢流壩60較佳是等間隔地配置。In the second embodiment, the desulfurization apparatus 200 includes a plurality of overflow dams 60. In FIGS. 4 and 5, in order to facilitate understanding of the invention, only one overflow dam 60 is illustrated, and the other illustrations are omitted. Fig. 6A is a schematic cross-sectional view showing the configuration of a desulfurization apparatus according to a second embodiment. In addition, in FIG. 6A, in order to facilitate understanding of the invention, the structure other than the side wall of the reaction tank 11 and the overflow dam 60 is abbreviate|omitted. As shown in FIG. 6A, the overflow dam 60 is provided at four equal intervals along the side wall of the cylindrical reaction vessel 11. The overflow dam 60 is not limited to four, and any number can be set. The plurality of overflow dams 60 are preferably arranged at equal intervals.

此外，圖6B為第2實施形態之脫硫裝置的變形例的構成示意概略截面圖。圖6B中亦為便於理解發明，針對反應槽11的側壁及溢流壩60以外之構成係省略圖示。　　如圖6B所示，溢流壩60，沿著直方體形狀的反應槽11的側壁而等間隔地設有4個。此時，於反應槽11的水平方向截面，溢流壩60亦可設於反應槽11的四隅，但較佳是設於長方形形狀亦即截面的各邊的中點鄰近。當溢流壩60設於中點鄰近的情形下，相較於四隅的情形，泡沫流體的流動會變得良好，會更加促進泡沫層28與含鹼劑液15之交替，因此較佳。In addition, FIG. 6B is a schematic cross-sectional view showing a configuration of a modification of the desulfurization apparatus of the second embodiment. In FIG. 6B, in order to facilitate the understanding of the invention, the configuration of the side wall of the reaction vessel 11 and the overflow dam 60 is omitted. As shown in FIG. 6B, the overflow dam 60 is provided at four equal intervals along the side wall of the reaction vessel 11 having a rectangular parallelepiped shape. At this time, the overflow dam 60 may be provided in the horizontal direction of the reaction tank 11, and the overflow dam 60 may be provided in the four sides of the reaction tank 11, but it is preferably provided in a rectangular shape, that is, a midpoint of each side of the cross section. When the overflow dam 60 is disposed adjacent to the midpoint, the flow of the foam fluid becomes good as compared with the case of the four crucibles, and the alternating between the foam layer 28 and the alkali containing liquid 15 is more promoted, and thus it is preferable.

(控制部、控制工程) 　　第2實施形態中，控制部，是基於混合槽36內的混合物的氧化還原電位，來控制泵浦34、或是設於配管33，35之未圖示的閥等，而能夠將從含鹼劑液室16抽出的漿體的量調節成任意量。　　另，控制部，除了從含鹼劑液室16抽出的漿體的量以外，還能控制從含鹼劑液室16抽出的泡沫流體的量。控制部，控制設於配管71之未圖示的閥等，而能夠將從含鹼劑液室16內的泡沫層28抽出的泡沫流體調整成任意量。(Control Unit, Control Project) In the second embodiment, the control unit controls the pump 34 or a valve (not shown) provided in the pipes 33 and 35 based on the oxidation-reduction potential of the mixture in the mixing tank 36. The amount of the slurry extracted from the alkali containing solution chamber 16 can be adjusted to an arbitrary amount. Further, the control unit can control the amount of the foam fluid extracted from the alkali containing solution chamber 16 in addition to the amount of the slurry extracted from the alkali containing solution chamber 16. The control unit controls the valve (not shown) provided in the pipe 71, and can adjust the foam fluid extracted from the foam layer 28 in the alkali-containing liquid chamber 16 to an arbitrary amount.

控制部，較佳是控制抽出的漿體的量而使ORP測定部50測定之氧化還原電位會成為200mV以下，更佳是控制使成為0mV以上150mV以下。The control unit preferably controls the amount of the extracted slurry to have an oxidation-reduction potential measured by the ORP measuring unit 50 of 200 mV or less, and more preferably controlled to be 0 mV or more and 150 mV or less.

按照以上說明的本發明第2實施形態之脫硫方法，能夠以簡易的構成實現抑制氧化性物質或6價硒的生成、及優良的脫硫性能。According to the desulfurization method of the second embodiment of the present invention described above, it is possible to suppress the formation of an oxidizing substance or hexavalent selenium and excellent desulfurization performance with a simple configuration.

在此，針對第2實施形態之脫硫裝置200中，藉由控制從含鹼劑液室16抽出的漿體的量而能夠減低氧化性物質一事，舉出具體例進一步詳細說明之。　　圖7為相對於含鹼劑液的氧化還原電位而言之氧化性物質的濃度的關係示意圖，揭示pH=4(實線)的情形、與pH=5(虛線)的情形。　　按照圖7，可知含鹼劑液中的氧化性物質的濃度，會因氧化還原電位而變化。由圖7得知，若氧化還原電位為200mV以下則氧化性物質變得幾乎不存在。Here, in the desulfurization apparatus 200 of the second embodiment, the amount of the slurry extracted from the alkali-containing solution chamber 16 can be controlled to reduce the oxidizing substance, and a specific example will be described in further detail. Fig. 7 is a view showing the relationship between the concentration of the oxidizing substance with respect to the oxidation-reduction potential of the alkali-containing solution, and the case of pH = 4 (solid line) and pH = 5 (dashed line). According to Fig. 7, it is understood that the concentration of the oxidizing substance in the alkali-containing agent liquid changes depending on the oxidation-reduction potential. As is clear from Fig. 7, when the oxidation-reduction potential is 200 mV or less, the oxidizing substance hardly exists.

另一方面，圖8為藉由第2實施形態之脫硫裝置200進行脫硫時，相對於從含鹼劑液室16抽出的漿體的量而言之混合槽36內(混合物中的含鹼劑液)的氧化還原電位的關係示意圖。此時，700MW的鍋爐廢氣中，以廢氣中的SO₂ 的濃度為700ppm之條件進行脫硫。　　由圖8得知，藉由控制從含鹼劑液室16抽出的漿體的量，能夠使氧化還原電位成為200mV以下，其結果，可知氧化性物質會變得幾乎不存在。On the other hand, Fig. 8 shows the inside of the mixing tank 36 with respect to the amount of the slurry extracted from the alkali containing liquid chamber 16 when the desulfurization apparatus 200 of the second embodiment performs desulfurization. Schematic diagram of the relationship between the redox potential of the alkaline agent solution. At this time, 700 MW of boiler exhaust gas was desulfurized under the condition that the concentration of SO ₂ in the exhaust gas was 700 ppm. As can be seen from Fig. 8, the oxidation-reduction potential can be made 200 mV or less by controlling the amount of the slurry extracted from the alkali-containing solution chamber 16, and as a result, it is understood that the oxidizing substance hardly exists.

(第2實施形態的效果、作用機制) 　　話說回來，構成泡沫層28之泡沫流體中，如前述般係含有煤塵，但藉由減低泡沫層28中含有的煤塵，可知會獲得抑制裝置內的水垢發生之效果。是故，第2實施形態中，除第1實施形態之效果外，更發揮抑制裝置內的水垢發生之效果。以下講述可獲得此效果之作用機制。(Effects and Mechanisms of the Second Embodiment) In the foam fluid constituting the foam layer 28, coal dust is contained as described above. However, by reducing the coal dust contained in the foam layer 28, it is known that the scale in the suppression device is obtained. The effect that occurs. Therefore, in the second embodiment, in addition to the effects of the first embodiment, the effect of suppressing the occurrence of scale in the apparatus is exhibited. The mechanism of action for obtaining this effect is described below.

煤塵是非常微細的粒子，因此具有因其微細的形狀而引起之浮遊性。是故，被捕捉於泡沫層28中的煤塵，會在氣泡泡沫的表面附著滯留。　　此處，習知的脫硫裝置中，漿體(含鹼劑液)的抽出是僅從含鹼劑液室的底部，因此絕大部分的泡沫流體不會直接被排出至外部，是故微細的煤塵隨著脫硫處理會必然地在泡沫層中濃度升高，成為高濃度。成為了高濃度的煤塵，會以濃縮於氣泡泡沫之狀態下存在，其一部分藉由被處理氣體的流動而被剝落，附著於脫硫裝置的下游的構件表面，成為水垢發生的原因。此外，從氣泡泡沫被剝落的高濃度的煤塵，會和朝向被處理氣體排出口之被處理氣體的流動同行，而有排出至脫硫裝置外之氣體的煤塵濃度變高之情形。　　鑑此，第2實施形態中，被捕捉於泡沫層28中的煤塵，雖會在氣泡泡沫的表面附著滯留，但會藉由配管71等而被抽出。其結果，能夠減低泡沫層28的氣泡泡沫的表面的煤塵的濃度，第2實施形態中能夠抑制來自於煤塵之水垢的發生，此外，伴隨此能夠減低排出至排煙脫硫裝置外之氣體(受清淨化後之氣體)的煤塵濃度。Coal dust is a very fine particle and therefore has a floating property due to its fine shape. Therefore, the coal dust trapped in the foam layer 28 adheres to the surface of the bubble foam. Here, in the conventional desulfurization apparatus, the slurry (the alkali-containing liquid) is extracted only from the bottom of the alkali-containing liquid chamber, so that most of the foam fluid is not directly discharged to the outside, so that it is fine. The coal dust will inevitably rise in the foam layer as the desulfurization treatment becomes a high concentration. The high-concentration coal dust is present in a state of being concentrated in the bubble foam, and a part thereof is peeled off by the flow of the gas to be treated, and adheres to the surface of the member downstream of the desulfurization device, which causes scale formation. Further, the high-concentration coal dust which is peeled off from the bubble foam may be in the same manner as the flow of the gas to be treated which is directed to the gas discharge port to be treated, and the concentration of the coal dust which is discharged to the gas outside the desulfurization device becomes high. In the second embodiment, the coal dust trapped in the foam layer 28 adheres to the surface of the bubble foam, but is extracted by the pipe 71 or the like. As a result, the concentration of the coal dust on the surface of the bubble foam of the foam layer 28 can be reduced, and in the second embodiment, the occurrence of scale from the coal dust can be suppressed, and the gas discharged to the exhaust gas desulfurization device can be reduced. The concentration of coal dust from the cleaned gas).

此外，第2實施形態中，係有效利用泡沫流體。含鹼劑液室16中的漿體為高氧化性環境而高pH，因此氧化性物質或6價硒多，但泡沫層28中的泡沫流體為低氧化性環境而低pH，且無氧化性物質，主體為有利於排水處理之4價硒。積極地利用具備這樣的性質之泡沫流體，藉此便能減低排水處理裝置的負荷。Further, in the second embodiment, the foam fluid is effectively utilized. The slurry in the alkali-containing agent liquid chamber 16 is a highly oxidizing environment and has a high pH, so that the oxidizing substance or the hexavalent selenium is large, but the foaming fluid in the foam layer 28 is a low oxidizing environment and has a low pH, and has no oxidizing property. Substance, the main body is 4-valent selenium which is beneficial for drainage treatment. The foam fluid having such a property is actively utilized, whereby the load of the drainage treatment device can be reduced.

[第3實施形態] 　　圖9為本發明第3實施形態之噴射鼓泡方式的脫硫裝置示意模型圖。以下，雖針對第3實施形態說明，但對於和第2實施形態相同的構件標記相同符號，並省略重複說明。[THIRD EMBODIMENT] Fig. 9 is a schematic view showing a defoaming apparatus of a jet bubbling method according to a third embodiment of the present invention. In the following description, the same members as those in the second embodiment are denoted by the same reference numerals, and the description thereof will not be repeated.

如圖9所示，第3實施形態之脫硫裝置300，除圖4所示第2實施形態之脫硫裝置300之外，還具備配管81、泵浦82、配管83、固液分離機84、配管85。是故，若將第3實施形態之脫硫裝置300與第2實施形態之脫硫裝置200比較，則第3實施形態中相異處在於具備第3抽出部(第3抽出工程)、及副分離回收部(副分離回收工程)，這點以外則相同。　　以下，針對脫硫裝置300的第3抽出部(第3抽出工程)及副分離回收部(副分離回收工程)詳述之。As shown in FIG. 9, the desulfurization apparatus 300 of the third embodiment further includes a pipe 81, a pump 82, a pipe 83, and a solid-liquid separator 84 in addition to the desulfurization device 300 of the second embodiment shown in FIG. , piping 85. When the desulfurization apparatus 300 of the third embodiment is compared with the desulfurization apparatus 200 of the second embodiment, the third embodiment differs in that the third extraction unit (the third extraction unit) and the sub-unit are provided. The separation and recovery unit (sub-separation recovery project) is the same except for this point. Hereinafter, the third extraction unit (third extraction project) and the sub-separation recovery unit (sub-separation recovery project) of the desulfurization apparatus 300 will be described in detail.

(第3抽出部、第3抽出工程) 　　在構成第1抽出部之配管33，分歧設有連接至泵浦82之配管81。泵浦82，透過配管81將漿體從配管33抽出。此漿體，為泵浦34從含鹼劑液室16抽出之漿體的一部分。　　在泵浦82的出口側連接有配管83的一端，配管83的另一端連接至固液分離機84。是故，透過從配管33分歧出的配管81而被抽出之漿體，其固體成分會藉由固液分離機84而被分離回收。針對此分離回收後述之。(Third Extraction Unit, Third Extraction Project) The piping 81 that is connected to the pump 82 is branched and branched in the piping 33 constituting the first extraction unit. The pump 82 draws the slurry from the pipe 33 through the pipe 81. This slurry is part of the slurry that pump 34 is withdrawn from the alkaline containing liquid chamber 16. One end of the pipe 83 is connected to the outlet side of the pump 82, and the other end of the pipe 83 is connected to the solid-liquid separator 84. Therefore, the solid material that has been extracted by the pipe 81 branched from the pipe 33 is separated and recovered by the solid-liquid separator 84. The separation and recovery are described later.

配管81、泵浦82及配管83構成第3抽出部。此外，圖9所示例子中，漿體是藉由第3抽出部而從配管33的往配管81之分歧位置被抽出。另，配管81，只要是在含鹼劑液室16與混合槽36之間則亦可設於任一處。換言之，只要是能夠將第1抽出工程中抽出的漿體的一部分，於混合工程中供混合之前予以抽出則無特別限制。The pipe 81, the pump 82, and the pipe 83 constitute a third extraction portion. Further, in the example shown in Fig. 9, the slurry is taken out from the branching portion of the pipe 33 to the branch 81 by the third extracting portion. Further, the pipe 81 may be provided at any position as long as it is between the alkali-containing agent liquid chamber 16 and the mixing tank 36. In other words, there is no particular limitation as long as it is possible to extract a part of the slurry extracted in the first extraction project before being mixed in the mixing process.

此外，配管81，亦可連接至含鹼劑液室16。也就是說，亦可透過配管81將收容於含鹼劑液室16內之漿體藉由泵浦82抽出，經由配管83供給至固液分離機84。此時，反應槽11(含鹼劑液室16)的設有配管81之位置的鄰近為第3區域，漿體從此第3區域藉由第3抽出部被抽出。Further, the pipe 81 may be connected to the alkali containing liquid chamber 16. In other words, the slurry contained in the alkali-containing solution chamber 16 can be extracted by the pump 82 through the pipe 81 and supplied to the solid-liquid separator 84 via the pipe 83. At this time, the vicinity of the position where the pipe 81 is provided in the reaction tank 11 (the alkali containing solution chamber 16) is the third region, and the slurry is extracted from the third region by the third extracting portion.

(副分離回收部、副分離回收工程) 　　藉由第3抽出部而被抽出的漿體，會透過連接至泵浦82的出口側之配管83，被供給至固液分離機84。固液分離機84，將藉由第3抽出部而被抽出的漿體固液分離，將固體成分予以分離回收。固液分離機84為副分離回收部。藉由固液分離機84而固體成分被回收後之回收殘液，透過配管85、配管47回到含鹼劑液室16。　　被供給至固液分離機84之漿體，不同於被供給至固液分離機46之混合物，其未混有構成泡沫層之泡沫流體。也就是說，被供給至固液分離機84之漿體中煤塵少。是故，藉由固液分離機84而被分離出的固體成分中混入之煤塵少，因此可獲得非常高品質的石膏。按照副分離回收部(副分離回收工程)，除藉由固液分離機46而從泡沫流體分離回收出的石膏，亦即煤塵的含有量多之相對低品質的石膏以外，還可藉由固液分離機84另行回收泡沫流體的含有量少，亦即煤塵的含有量少之高品質的石膏。(Separate Separation and Recovery Unit, Sub Separation and Recovery Project) The slurry extracted by the third extraction unit is supplied to the solid-liquid separator 84 through the pipe 83 connected to the outlet side of the pump 82. The solid-liquid separator 84 solid-liquid separation of the slurry extracted by the third extraction unit, and separates and collects the solid component. The solid-liquid separator 84 is a sub-separation and recovery unit. The solid residue is recovered by the solid-liquid separator 84, and the residual liquid is recovered, and is returned to the alkali-containing solution chamber 16 through the pipe 85 and the pipe 47. The slurry supplied to the solid-liquid separator 84 is different from the mixture supplied to the solid-liquid separator 46, which is not mixed with the foam fluid constituting the foam layer. That is, the amount of coal dust which is supplied to the slurry of the solid-liquid separator 84 is small. Therefore, the amount of coal dust mixed in the solid component separated by the solid-liquid separator 84 is small, so that gypsum of very high quality can be obtained. According to the sub-separation and recovery unit (sub-separation and recovery), the gypsum separated and recovered from the foam fluid by the solid-liquid separator 46, that is, the relatively low-quality gypsum containing a large amount of coal dust, may be solidified. The liquid separator 84 separately recovers a high-quality gypsum having a small content of the foam fluid, that is, a small amount of coal dust.

另，習知的脫硫裝置中，僅有從含鹼劑液室的下部抽出之漿體會被固液分離，而被回收作為石膏。此時，如前述般微細的煤塵幾乎不會被排出，因此含鹼劑液中及泡沫層中的煤塵會成為高濃度。是故，從含鹼劑液室抽出的漿體中，煤塵會以高濃度存在，因此會讓來自於此漿體之石膏的品質低落。當煤塵的主體為未燃燒碳的情形下該傾向會變得顯著，導致色相惡化。　　不過，第3實施形態中，是從泡沫層28抽出泡沫流體而排出，藉此被送至固液分離機84之漿體中的煤塵的濃度會降低，因此石膏的品質會提升。Further, in the conventional desulfurization apparatus, only the slurry extracted from the lower portion of the alkali-containing liquid chamber is separated by solid-liquid and recovered as gypsum. At this time, since the fine coal dust is hardly discharged as described above, the coal dust in the alkali-containing agent liquid and the foam layer becomes a high concentration. Therefore, in the slurry extracted from the alkali-containing liquid chamber, the coal dust is present in a high concentration, so that the quality of the gypsum from the slurry is lowered. When the main body of the coal dust is unburned carbon, the tendency becomes remarkable, resulting in deterioration of the hue. However, in the third embodiment, the foam fluid is taken out from the foam layer 28 and discharged, whereby the concentration of the coal dust sent to the slurry of the solid-liquid separator 84 is lowered, so that the quality of the gypsum is improved.

按照以上之第3實施形態，能夠另外回收煤塵的含有量少之石膏，因此可獲得高品質的石膏。此高品質的石膏，亦能和含有煤塵之相對低品質的石膏適當混合來利用。此外，第3實施形態中亦如同第2實施形態般，藉由固液分離機46而固體成分被回收後之回收殘液，其氧化性物質或6價硒會被減低，能夠將此回收殘液的一部分或全部送往排水處理裝置。According to the third embodiment described above, it is possible to separately collect gypsum having a small amount of coal dust, and thus it is possible to obtain high-quality gypsum. This high quality gypsum can also be suitably mixed with a relatively low quality gypsum containing coal dust. Further, in the third embodiment, as in the second embodiment, the solid residue is recovered by the solid-liquid separator 46, and the oxidizing substance or the hexavalent selenium is reduced, and the residue can be recovered. A part or all of the liquid is sent to the drainage treatment device.

11‧‧‧反應槽11‧‧‧Reaction tank

12‧‧‧被處理氣體導入路12‧‧‧Processed gas introduction route

13‧‧‧被處理氣體排出口13‧‧‧Processed gas discharge

14‧‧‧被處理氣體導入室14‧‧‧Processed gas introduction room

15‧‧‧含鹼劑液15‧‧‧Alkaline solution

16‧‧‧含鹼劑液室16‧‧‧Alkaline-containing liquid chamber

17‧‧‧被處理氣體排出室17‧‧‧Processed gas discharge chamber

18‧‧‧第1隔壁18‧‧‧1st next door

19‧‧‧第2隔壁19‧‧‧2nd next door

21‧‧‧液面21‧‧‧ liquid level

22‧‧‧氣體下降管22‧‧‧ gas down tube

25‧‧‧連通管25‧‧‧Connected pipe

26‧‧‧空間部26‧‧‧ Space Department

27‧‧‧攪拌機27‧‧‧Mixer

28‧‧‧泡沫層28‧‧‧Foam layer

31‧‧‧配管31‧‧‧Pipe

32‧‧‧工業用水供給管32‧‧‧Industrial water supply pipe

33‧‧‧配管33‧‧‧Pipe

34‧‧‧泵浦34‧‧‧ pump

35‧‧‧配管35‧‧‧Pipe

36‧‧‧混合槽36‧‧‧Mixed tank

37‧‧‧配管37‧‧‧Pipe

38‧‧‧氧供給管38‧‧‧Oxygen supply tube

41‧‧‧攪拌機41‧‧‧Mixer

42‧‧‧配管42‧‧‧Pipe

43‧‧‧泵浦43‧‧‧ pump

44‧‧‧配管44‧‧‧Pipe

45‧‧‧配管45‧‧‧Pipe

46‧‧‧固液分離機46‧‧‧ solid liquid separator

47‧‧‧配管47‧‧‧Pipe

48‧‧‧鹼劑導入部48‧‧‧Alkaline agent introduction

49‧‧‧配管49‧‧‧Pipe

50‧‧‧ORP測定部50‧‧‧ORP Measurement Department

60‧‧‧溢流壩60‧‧‧ overflow dam

61‧‧‧側板61‧‧‧ side panels

62‧‧‧底板62‧‧‧floor

62a‧‧‧開口部62a‧‧‧ Opening

63‧‧‧上昇流抑止板63‧‧‧Upflow suppression board

71‧‧‧配管71‧‧‧Pipe

81‧‧‧配管81‧‧‧Pipe

82‧‧‧泵浦82‧‧‧ pump

83‧‧‧配管83‧‧‧Pipe

84‧‧‧固液分離機84‧‧‧ solid liquid separator

85‧‧‧配管85‧‧‧Pipe

100‧‧‧脫硫裝置100‧‧‧Desulfurization unit

200‧‧‧脫硫裝置200‧‧‧Desulfurization unit

300‧‧‧脫硫裝置300‧‧‧Desulfurization unit

[圖1]本發明第1實施形態之噴射鼓泡方式的脫硫裝置的一例示意模型圖。　　[圖2]相對於混合槽內之被處理氣體的供給量而言之氧量的關係的一例示意圖表。　　[圖3]相對於混合槽內之被處理氣體的供給量而言之氧量及氧化還原電位的關係的一例示意圖表。　　[圖4]本發明第2實施形態之噴射鼓泡方式的脫硫裝置的一例示意模型圖。　　[圖5]圖4所示脫硫裝置的主要部位擴大圖。　　[圖6A]本發明第2實施形態之脫硫裝置的構成示意概略截面圖。　　[圖6B]本發明第2實施形態之脫硫裝置的變形例的構成示意概略截面圖。　　[圖7]相對於含鹼劑液的氧化還原電位而言之氧化性物質的濃度的關係示意圖。　　[圖8]相對於漿體的供給量而言之混合槽的氧化還原電位的關係示意圖。　　[圖9]本發明第3實施形態之噴射鼓泡方式的脫硫裝置的一例示意模型圖。Fig. 1 is a schematic model view showing an example of a jet bubbling type desulfurization apparatus according to a first embodiment of the present invention. FIG. 2 is a schematic diagram showing an example of the relationship of the amount of oxygen with respect to the supply amount of the gas to be processed in the mixing tank. FIG. 3 is a schematic diagram showing an example of the relationship between the amount of oxygen and the oxidation-reduction potential with respect to the supply amount of the gas to be treated in the mixing tank. Fig. 4 is a schematic view showing an example of a jet bubbling type desulfurization apparatus according to a second embodiment of the present invention. Fig. 5 is an enlarged view of a main part of the desulfurization apparatus shown in Fig. 4. [ Fig. 6A] Fig. 6A is a schematic cross-sectional view showing the configuration of a desulfurization apparatus according to a second embodiment of the present invention. [ Fig. 6B] Fig. 6B is a schematic cross-sectional view showing a configuration of a modification of the desulfurization apparatus according to the second embodiment of the present invention. Fig. 7 is a graph showing the relationship of the concentration of an oxidizing substance with respect to the oxidation-reduction potential of the alkali-containing agent liquid. Fig. 8 is a graph showing the relationship between the oxidation-reduction potential of the mixing tank with respect to the amount of slurry supplied. Fig. 9 is a schematic view showing an example of a jet bubbling type desulfurization apparatus according to a third embodiment of the present invention.

Claims

一種脫硫方法，其特徵為，具備：　　接觸工程，將含有硫氧化物的被處理氣體，導入至收容於反應槽內之含鹼劑液中，對該含鹼劑液供給氧，令前述含鹼劑液中析出藉由前述硫氧化物和前述氧和前述含鹼劑液中的鹼劑之反應而產生的生成物；及　　第1抽出工程，從前述反應槽內的第1區域，抽出含有前述含鹼劑液與前述析出的生成物之漿體；及　　第2抽出工程，抽出前述反應槽內的、或是從和前述反應槽連通之第2區域，抽出能夠將前述漿體還原之流體；及　　混合工程，將前述第1抽出工程中抽出的前述漿體、與前述第2抽出工程中抽出的前述流體予以混合；及　　分離回收工程，從該混合工程中混合的前述漿體與前述流體之混合物，將固體成分予以分離回收。A method for desulfurization, comprising: contacting a project, introducing a gas to be treated containing sulfur oxides into an alkali-containing agent liquid contained in a reaction tank, and supplying oxygen to the alkali-containing agent liquid to cause the above-mentioned a product produced by the reaction between the sulfur oxide and the alkali agent in the alkali agent solution is precipitated in the alkali solution; and the first extraction process extracts the first region in the reaction tank a slurry of the alkali-containing agent liquid and the precipitated product; and a second extraction process, extracting a second region in the reaction tank or communicating with the reaction tank, and extracting a fluid capable of reducing the slurry And the mixing process, mixing the slurry extracted in the first extraction project and the fluid extracted in the second extraction project; and separating and recovering the slurry and the fluid mixed from the mixing process The mixture is separated and recovered.

如申請專利範圍第1項所述之脫硫方法，其中，更具備：　　測定工程，測定前述混合工程中獲得的混合物的氧化還原電位；及　　控制工程，基於該測定工程中測定出的氧化還原電位，來控制前述第1抽出工程中抽出的前述漿體的量、及前述第2抽出工程中抽出的前述流體的量之至少一方。The desulfurization method according to the first aspect of the invention, further comprising: a measurement project for measuring an oxidation-reduction potential of the mixture obtained in the mixing process; and a control project based on the oxidation-reduction potential measured in the measurement project At least one of the amount of the slurry extracted in the first extraction process and the amount of the fluid extracted in the second extraction process is controlled.

如申請專利範圍第2項所述之脫硫方法，其中，前述控制工程，控制使得前述測定工程中測定之氧化還原電位成為未滿200mV。The desulfurization method according to claim 2, wherein the control project controls the oxidation-reduction potential measured in the measurement project to be less than 200 mV.

如申請專利範圍第1項至第3項中任一項所述之脫硫方法，其中，前述第1抽出工程，從前述反應槽的底部抽出前述漿體。The desulfurization method according to any one of the preceding claims, wherein the first extraction project extracts the slurry from a bottom portion of the reaction vessel.

如申請專利範圍第1項至第3項中任一項所述之脫硫方法，其中，前述第2抽出工程，抽出前述接觸工程中被導入前述含鹼劑液中之前的前述被處理氣體的一部分。The desulfurization method according to any one of the first to third aspect, wherein the second extraction project extracts the gas to be treated before being introduced into the alkali-containing agent liquid in the contact process portion.

如申請專利範圍第1項至第3項中任一項所述之脫硫方法，其中，前述接觸工程，在收容於前述反應槽內之前述含鹼劑液中將前述被處理氣體起泡，一面形成泡沫層一面令前述生成物析出，　　前述第2抽出工程，從前述泡沫層抽出前述流體。The desulfurization method according to any one of the above-mentioned items of the present invention, wherein, in the contact engineering, the gas to be treated is foamed in the alkali-containing agent liquid contained in the reaction tank, The product is deposited while forming a foam layer, and the fluid is extracted from the foam layer in the second extraction process.

如申請專利範圍第6項所述之脫硫方法，其中，更具備：　　第3抽出工程，抽出漿體；及　　副分離回收工程，從該第3抽出工程中抽出的前述漿體將固體成分予以分離回收；　　前述第3抽出工程，　　　將前述第1抽出工程中抽出的前述漿體的一部分，於前述混合工程中與前述流體混合之前予以抽出，或是，　　　從前述反應槽內的第3區域，抽出含有前述含鹼劑液與前述析出的生成物之漿體。The method for desulfurization according to claim 6, wherein the method further comprises: a third extraction project, extracting the slurry; and a sub-separation recovery project, wherein the slurry extracted from the third extraction project gives the solid component Separating and recovering; in the third extraction project, a part of the slurry extracted in the first extraction process is extracted before mixing with the fluid in the mixing process, or from a third region in the reaction tank A slurry containing the alkali-containing solution and the precipitated product is extracted.

一種脫硫裝置，其特徵為，具備：　　反應槽，具有：被處理氣體導入路、及從該被處理氣體導入路供含有硫氧化物的被處理氣體導入之被處理氣體導入室、及設於該被處理氣體導入室的下側而供含鹼劑液收容於其下部之含鹼劑液室、及將被導入至前述被處理氣體導入室的前述被處理氣體供給至收容於前述含鹼劑液室的前述含鹼劑液中之氣體下降管；及　　氧供給管，對收容於前述含鹼劑液室之前述含鹼劑液中供給氧；及　　第1抽出部，從前述含鹼劑液室內的第1區域，抽出含有前述含鹼劑液與藉由前述硫氧化物和前述氧和前述含鹼劑液中的鹼劑之反應而產生的生成物當中析出至前述含鹼劑液中的析出物之漿體；及　　第2抽出部，抽出前述反應槽內的、或是從和前述反應槽連通之第2區域，抽出能夠將前述漿體還原之流體；及　　混合槽，將前述第1抽出部抽出的前述漿體、與前述第2抽出部中抽出的前述流體予以混合；及　　分離回收部，從該混合槽中被混合的前述漿體與前述流體之混合物，將固體成分予以分離回收。A desulfurization apparatus comprising: a reaction gas introduction path; and a gas to be introduced into the process gas introduced into the process gas introduction path to introduce a gas to be treated containing sulfur oxides; The alkali-containing liquid chamber in which the alkali-containing liquid is contained in the lower portion of the gas-introducing liquid-introducing chamber, and the gas to be treated introduced into the gas-introducing chamber to be processed are supplied to the alkali-containing agent. a gas lowering pipe in the alkali-containing agent liquid in the liquid chamber; and an oxygen supply pipe for supplying oxygen to the alkali-containing agent liquid contained in the alkali-containing agent liquid chamber; and a first extracting portion from the alkali-containing agent liquid In the first region of the chamber, the product containing the alkali-containing agent solution and the reaction between the sulfur oxide and the oxygen and the alkali agent in the alkali-containing agent solution is extracted and precipitated into the alkali-containing agent solution. a slurry of the precipitate; and a second extraction portion that extracts a second region in the reaction tank or that communicates with the reaction vessel, and extracts a fluid capable of reducing the slurry; and a mixing tank The slurry extracted by the first extraction portion and the fluid extracted from the second extraction portion are mixed; and the separation and recovery portion is mixed with the slurry and the fluid mixed from the mixing tank to apply a solid component Separate and recycle.

如申請專利範圍第8項所述之脫硫裝置，其中，更具備：　　測定部，測定前述混合物的氧化還原電位；及　　控制部，基於該測定部測定出的氧化還原電位，來控制前述第1抽出部抽出的前述漿體的量、及前述第2抽出部抽出的前述流體的量之至少一方。The desulfurization apparatus according to claim 8, further comprising: a measuring unit that measures an oxidation-reduction potential of the mixture; and a control unit that controls the first one based on an oxidation-reduction potential measured by the measuring unit At least one of the amount of the slurry extracted by the extraction unit and the amount of the fluid extracted by the second extraction unit.

如申請專利範圍第9項所述之脫硫裝置，其中，前述控制部，控制使得前述測定部測定之氧化還原電位成為200mV以下。The desulfurization apparatus according to claim 9, wherein the control unit controls the oxidation-reduction potential measured by the measurement unit to be 200 mV or less.

如申請專利範圍第8項至第10項中任一項所述之脫硫裝置，其中，前述第1抽出部，從前述含鹼劑液室的底部抽出前述漿體。The desulfurization apparatus according to any one of claims 8 to 10, wherein the first extraction unit extracts the slurry from a bottom portion of the alkali-containing solution chamber.

如申請專利範圍第8項至第10項中任一項所述之脫硫裝置，其中，前述流體為前述被處理氣體，　　前述第2抽出部，從前述被處理氣體導入路或前述被處理氣體導入室抽出前述被處理氣體。The desulfurization apparatus according to any one of the preceding claims, wherein the fluid is the gas to be treated, and the second extraction unit is from the gas to be treated or the gas to be treated. The introduction chamber extracts the aforementioned gas to be treated.

如申請專利範圍第8項至第10項中任一項所述之脫硫裝置，其中，前述流體，為泡沫流體，其構成形成於前述含鹼劑液室收容的前述含鹼劑液的液面上之泡沫層，　　前述第2抽出部，從前述含鹼劑液室抽出前述泡沫流體。The desulfurization apparatus according to any one of claims 8 to 10, wherein the fluid is a foam fluid constituting the alkali-containing liquid contained in the alkali-containing liquid chamber. In the foam layer on the surface, the second extraction portion extracts the foam fluid from the alkali-containing solution chamber.

如申請專利範圍第13項所述之脫硫裝置，其中，更具備：　　第3抽出部，抽出漿體；及　　副分離回收部，從該第3抽出部抽出的前述漿體將固體成分予以分離回收；　　前述第3抽出部，　　　將前述第1抽出部抽出的前述漿體的一部分，於前述混合槽與前述反應槽之間予以抽出，或是，　　　從前述反應槽內的第3區域，抽出含有前述含鹼劑液與前述析出的生成物之漿體。The desulfurization apparatus according to claim 13, further comprising: a third extraction unit that extracts the slurry; and a sub-separation recovery unit that separates the solid components from the slurry extracted from the third extraction unit In the third extraction unit, a part of the slurry extracted from the first extraction unit is extracted between the mixing tank and the reaction tank, or is extracted from the third region in the reaction tank. a slurry of the alkali-containing solution and the precipitated product.