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WO2004020077A1 - Procede et appareil de desulfuration d'un gaz a traiter dans lequel est introduit no et/ou no2 avec recuperation de so2 sous forme de caso4 - Google Patents

Procede et appareil de desulfuration d'un gaz a traiter dans lequel est introduit no et/ou no2 avec recuperation de so2 sous forme de caso4 Download PDF

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Publication number
WO2004020077A1
WO2004020077A1 PCT/JP2003/010699 JP0310699W WO2004020077A1 WO 2004020077 A1 WO2004020077 A1 WO 2004020077A1 JP 0310699 W JP0310699 W JP 0310699W WO 2004020077 A1 WO2004020077 A1 WO 2004020077A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
treated
reaction
desulfurization
separating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2003/010699
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English (en)
Japanese (ja)
Inventor
Masayoshi Sadakata
Xuchang Xu
Masateru Nishioka
Norihiko Matsushima
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Japan Science and Technology Agency
Original Assignee
Japan Science and Technology Agency
Japan Science and Technology Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Japan Science and Technology Agency, Japan Science and Technology Corp filed Critical Japan Science and Technology Agency
Publication of WO2004020077A1 publication Critical patent/WO2004020077A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • B01D53/83—Solid phase processes with moving reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/508—Sulfur oxides by treating the gases with solids

Definitions

  • the gas to be treated for example the gas to be treated which has improved recovery of C a S 0 4 to SO 2 in the field if the exhaust gas in the C a SO 4 and to separate and recover the desulfurization method
  • Contact Yopi desulfurization apparatus the desulfurization process and the desulfurization apparatus, 1 0 ppm to as least to be treated in the gas, especially, preferred properly is to be treated in the gas, characterized that you coexist 1 0 0 ppm NO and Z or N 0 2 3 0 2 . a S 0 4 and then on the desulfurization process you and desulfurization apparatus for separating recovered.
  • So 2 is a substance that has a significant impact on the environment and human health, and SO 2 generated from the coal burning process is a major social problem. Therefore, systems that absorb and remove so 2 have been studied.
  • One of them is an absorption removal method using C a O.
  • the C a O absorption removal of SO 2 with is performed through the diffusion of so 2, the process of formation of C a SO 4 / C a S 0 3 by solid reaction. Therefore, the characteristics of the C a O particles, that is, the surface area, pore size, pore volume, etc., have a great influence on the adsorption reaction.
  • Commercially available Ca II does not have a good calcium utilization in terms of SO 2 absorption and removal properties.
  • the present inventors have found that the mechanism of the hydration process in the process of mixing CaO and fly ash in water to prepare an adsorbent makes it possible to reduce the amount of the raw material.
  • We have been keenly researching the production of desulfurizing agents that exhibit active SO 2 adsorption properties that can be used in practical processes (Energy & Fuels, Vol. 13, No. 5, 1015-1020, 1999. Reference A).
  • the amount of water used to prepare the desulfurizing agent is such that the weight ratio of H 2 O / (carrier particles + C a (OH) 2 ) is relatively large at 1.5.
  • water resources are low.
  • the method is to provide a desulfurization device.
  • the desulfurization method and desulfurization apparatus using the desulfurizing agent are to provide a desulfurization device.
  • the first of the present invention the 3_Rei 2 of the process gas by the NO Oyopi or N 0 2 to 1 0 ⁇ 5 0 0 0 ppm coexisting in the exhaust gas. a desulfurization process of separating and recovering as a a S 0 4.
  • the NO and Z or N 0 2 to be processed gas containing a so 2 is 1 0 ⁇ 5 0 0 0 ppm coexist
  • the wire carrier rear particle surface of large diameter C a (OH) 2 fine particles coated the S o 2 desulfurizing agent are contacted in a reaction column at a state of forming a fluidized bed and treated gas containing the so 2, wherein the reaction column together with the pre-Symbol subject gas while reacting the desulfurizing agent and SO 2 medium was elevated to said C a SO 4 that I Ri formed in the reaction with the C a (OH) 2 fine particles from the upper portion of the reactor the S ⁇ 2 and Canon rear surface of the particles Canon Li Ya particles Contact Yo Pi to flow to the first gas primary solids separator together with the process gas, the reaction with the C a (OH) 2 and S 0 2 of the Kiyariya particle surface in the first gas one solid body separator in Ri precipitated the wire carrier Li Ya particles from a gas containing C a S 0 4 which are formed, detached and
  • a second aspect of the present invention is a reaction tower 1 in which a SO 2 desulfurizing agent having large-sized carrier particles coated with fine particles of Ca (OH) 2 forms a fluidized bed by supplying a gas to be treated,
  • the surface of large carrier particles C a (OH) 2 is desulfurizing agent supply device for supplying the SO 2 desulfurizing agent coated particulate, device coexist NO Oyopi or N 0 2 to be treated in a gas containing S 0 2, NO and _ or N 0 2 to S 0 2 coexisted the blowing including treated gas to be treated gas blowing device, the contact in a reaction column with the desulfurizing agent in a state of forming a fluidized bed and treated gas containing S o 2 Then, the desulfurizing agent and so 2 are allowed to react with each other and rise in the reaction tower together with the gas to be treated, and from the upper part of the reaction tower, the so 2 and C a (OH) 2 of the fine particles on the surface of the carrier particles
  • the apparatus coexist NO and / or N 0 2 to be treated in a gas containing so 2, to form a fluidized bed gas to be treated to separate and recover in the S 0 2 and C a S o 4 reaction is arranged before the test sheet to the tower, the NO and / or N 0 2 to 1 0 to 50 0 NO and externally to ppm Z or N 0 2 supplies device and / or NO in the gas to be treated NO wherein characterized in that it is intended to include co Nbata be converted to 2 so 2 of the treated gas is desulfurizer of separating and recovering as a C a 30 4, yo Ri preferably, the reaction tower to form a fluidized bed in a 1 and a S 0 4 first gas primary solids separator for separating precipitated the wire carrier rear particles from a gas to be treated containing
  • the S_ ⁇ 2 of the each of the treated gas characterized in that you are forming a circulating fluidized bed is a C a S 0 4 and to desulfur
  • FIG. 1 is a conceptual diagram of the desulfurization device of the present invention.
  • the apparatus includes: 1 a fluidized bed forming reaction tower 1, a first gas-solid separator 2, a second gas-solid separator 3, a gas injection section 4, a reflux line 5 for separation carrier particles, a S 0 4 transfer pipe 6 of a gas containing the treated gas to be treated 7, recovered C a S 0 4 solid reaction Monotori out pipe 8 including, SO 2 desulfurizing agent supplying section (SO 2 desulfurizing agent manufacturing. supply device) 9, N 0 2 co Nbata CV, acid agent supplying means OD, the boiler (treated gas generating source) B main constituent.
  • Figure 2 is a 3 0 2 when allowed to coexist NO and N 0 2 to S 0 2 containing treated gas. showing a correlation time course of a S 0 4 the characteristic of separating and recovering by the quantity of particles splash.
  • FIG. 1 is a conceptual diagram of a desulfurization apparatus for separating and recovering as follows. 1 is a fluidized bed formation reactor equipped with a perforated plate (PP).
  • PP perforated plate
  • a boiler Apparatus for supplying a gas to be treated (the gas to be treated) in 1 0 ⁇ 5 0 0 ppm of NO contact and / or N 0 gas to be treated was 2 coexist from B, blower pump is connected, for example.
  • a device for supplying NO and Z or NO 2 before the device for supplying the gas to be treated, and NO that coexists in the gas to be treated or the least even that have ⁇ D is provided to blow the oxidizing agent that promotes the N 0 2 converts the device CV and the conversion part.
  • a SO 2 desulfurizing agent supply device 9 in this case, a desulfurizing agent production device is directly connected to the reaction tower 1.
  • the desulfurizing agent and the equipment after the reaction tower are described in detail in the above-mentioned Japanese Patent Application Laid-Open No. 2002-113336, which has already been proposed by the present inventors. State technical description according to the publication, in which the so 2 desulfurizing agent in wire carrier re yer particle surface of the large particle size coated with C a (OH) 2 fine particles to form a fluidized bed and treated gas containing so 2 3 0 2 in the treated gas is contacted in a reaction column.
  • Particle droplet amount (Ca amount of droplets g / min) ⁇ (Ca amount of supplied desulfurizing agent g Z minutes).
  • NO ( ⁇ ) and N 0 2 ( ⁇ ) Added by the of Ri the case [NO which has increased splash particles N 0 2 yet such coexist indicated by ( ⁇ ). ].
  • NO also N 0 by the second coexisting Ri desulfurizing agent effectively works and Conoco, which means that the O efficiency rather gypsum is obtained.
  • the above results showing the relationship between aging and the amount of droplets show that the fluctuation is large and the amount of droplets is not stable, in other words, a stable reaction has not progressed, and the controllability is better. Absent.
  • the present invention relates to SO in which NO and / or NO 2 is present in the gas to be treated containing SO 2 in an amount of 10 to 500 ppm, and the surface of large-size carrier particles is coated with fine particles of Ca (OH) 2.
  • 2 Establish a desulfurization method to separate and recover SO 2 as Ca 4 by contacting with a desulfurizing agent, and make it possible to recover so 2 as Ca SO 4 , a highly efficient and useful by-product. It provides the above-mentioned highly available environmental improvement technology, which greatly contributes to society.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

L'invention concerne un procédé de désulfuration caractérisé en ce qu'il consiste à introduire 10 à 5000 ppm de NO et/ou de NO2 dans un gaz à traiter contenant du SO2, à réaliser un contact entre un agent de désulfuration du SO2, constitué de particules support de grand diamètre revêtues de particules fines de Ca(OH)2, le gaz à traiter se trouvant à l'état de couche fluidisée dans une tour de réaction, à les faire s'élever tout en réagissant, à leur permettre de s'écouler vers un premier séparateur gaz-solide via le sommet de la tour de réaction, à précipiter et à séparer les particules support d'un gaz contenant du CaSO4, formé par la réaction entre le Ca(OH)2 disposé sur la surface des particules support et le SO2, s'étant détaché par parcelles, tout en permettant au gaz contenant le CaSO4, provenant du dessus du premier séparateur gaz-solide, de s'écouler vers un second séparateur gaz-solide, et à séparer et récupérer le CaSO4 du gaz traité dans le second séparateur gaz-solide.
PCT/JP2003/010699 2002-08-27 2003-08-25 Procede et appareil de desulfuration d'un gaz a traiter dans lequel est introduit no et/ou no2 avec recuperation de so2 sous forme de caso4 Ceased WO2004020077A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002-246125 2002-08-27
JP2002246125A JP4012011B2 (ja) 2002-08-27 2002-08-27 被処理ガス中にＮＯ２を共存させてＳＯ２をＣａＳＯ４として回収する脱硫方法および脱硫装置

Publications (1)

Publication Number Publication Date
WO2004020077A1 true WO2004020077A1 (fr) 2004-03-11

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2003/010699 Ceased WO2004020077A1 (fr) 2002-08-27 2003-08-25 Procede et appareil de desulfuration d'un gaz a traiter dans lequel est introduit no et/ou no2 avec recuperation de so2 sous forme de caso4

Country Status (3)

Country Link
JP (1) JP4012011B2 (fr)
CN (1) CN1331568C (fr)
WO (1) WO2004020077A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102000492B (zh) * 2010-11-26 2013-02-27 中冶赛迪工程技术股份有限公司 喷射石灰浆循环流化床半干法脱硫装置
CN117401705A (zh) * 2023-11-02 2024-01-16 重庆钢铁股份有限公司 一种脱硫灰资源化利用方法及其应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1986006711A1 (fr) * 1985-05-14 1986-11-20 Gordon Dale Jones Procede et dispositif d'extraction d'oxydes d'azote et de soufre contenus dans des gaz de combustion
JPH05337325A (ja) * 1992-06-08 1993-12-21 Hokkaido Electric Power Co Inc:The 排ガスの乾式脱硫法
JP2002113326A (ja) * 2000-10-10 2002-04-16 Japan Science & Technology Corp 新規脱硫剤による副生物分離可能な脱硫方法および脱硫装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1986006711A1 (fr) * 1985-05-14 1986-11-20 Gordon Dale Jones Procede et dispositif d'extraction d'oxydes d'azote et de soufre contenus dans des gaz de combustion
JPH05337325A (ja) * 1992-06-08 1993-12-21 Hokkaido Electric Power Co Inc:The 排ガスの乾式脱硫法
JP2002113326A (ja) * 2000-10-10 2002-04-16 Japan Science & Technology Corp 新規脱硫剤による副生物分離可能な脱硫方法および脱硫装置

Also Published As

Publication number Publication date
JP4012011B2 (ja) 2007-11-21
CN1678384A (zh) 2005-10-05
CN1331568C (zh) 2007-08-15
JP2004081975A (ja) 2004-03-18

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