JP4012011B2 - Desulfurization method and desulfurization apparatus for recovering SO2 as CaSO4 by coexisting NO2 in a gas to be treated - Google Patents

Desulfurization method and desulfurization apparatus for recovering SO2 as CaSO4 by coexisting NO2 in a gas to be treated Download PDF

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JP4012011B2
JP4012011B2 JP2002246125A JP2002246125A JP4012011B2 JP 4012011 B2 JP4012011 B2 JP 4012011B2 JP 2002246125 A JP2002246125 A JP 2002246125A JP 2002246125 A JP2002246125 A JP 2002246125A JP 4012011 B2 JP4012011 B2 JP 4012011B2
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JP2004081975A (en
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正毅 定方
旭常 徐
将輝 西岡
徳彦 松島
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National Institute of Japan Science and Technology Agency
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    • 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
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    • 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

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Description

【０００１】
【発明の属する技術分野】
本発明は、被処理ガス、例えば排ガス中のＳＯ２をＣａＳＯ４として分離回収する脱硫方法および脱硫装置におけるＣａＳＯ４の回収率を改善した前記被処理ガスの脱硫方法および脱硫装置、特に被処理ガス中に１０〜４８０ｐｐｍのＮＯ ２ を共存させることを特徴とする被処理ガス中のＳＯ２をＣａＳＯ４として分離回収する脱硫方法および脱硫装置に関する。
【０００２】
【従来の技術】
ＳＯ２は環境及び人の健康に重大な影響がある物質であり、石炭の燃焼プロセスなどから発生するＳＯ２は大きな社会問題である。そのために、従来から、ＳＯ２を吸収除去するシステムが研究されている。その一つにＣａＯを用いた吸収除去方法がある。このＣａＯを用いたＳＯ２の吸収除去は、ＳＯ２の拡散と、固体反応によるＣａＳＯ４／ＣａＳＯ３の形成の過程を経て行われる。従って、ＣａＯの粒子の特性、すなわち、表面積、孔径、孔容積等が前記吸収除去に大きな影響がある。市販のＣａＯはＳＯ２を吸収除去の特性に関しては、カルシウム利用率が良いとは言えない。
【０００３】
また、サンダー等（Ｓａｎｄｅｒｓ ｅｔ ａｌ．）は、フライアッシュと消石灰との混合スラリーを用いるとＳＯ２の吸収除去特性が改善されることを報告している（Ｓａｎｄｅｒｓ ｅｔ ａｌ．，Ｉｎｄ．Ｅｎｇ．Ｃｈｅｍ．Ｒｅｓ．１９９５，３４（４），３０２−３０７）。その報告の中で、ＳＯ２の吸収除去特性の改善は、カルシウムと珪酸アルミナとの水和反応により生成する珪酸カルシウム水和物の存在にあり、反応性の違いは珪酸カルシウム水和物の構造にあると説明している。他に、γ−アルミナ−ＣａＯ吸着剤（Ｓｖｏｂｏｄａ ｅｔ ａｌ．）、ＣａＯ、硫酸カルシウム、及びフライアッシュからのスラリーを約１００℃で熟成した後、乾燥して得た吸着剤（Ｈｉｒｏａｋｉ ｅｔ ａｌ．）（エトリンゲイトが形成されていると考えられている。特公平３−５９７３７号公報にも類似の技術が開示されている。）等が提案されているが、それらの吸着剤の調製方法は水の使用量が比較的多く、水利の良くない地域においての利用性が悪いこと、および水を取り除くのに長時間および／または多くのエネルギーが必要であること、およびＳＯ２吸着剤の調製時における吸着特性を改善する組成の形成は工程の管理が難しいなどのことから、ＳＯ２吸着剤の製造装置を脱硫装置に直結するような脱硫装置の設計が難しいという不都合があった。
【０００４】
これに対して、本発明者等は、ＣａＯとフライアッシュとを水中混合して吸着剤を調製するプロセスにおける水和のプロセスのメカニズムを知ることにより、前記原料からより実用プロセスとなり得るような活性なＳＯ２吸着特性を示す脱硫剤を製造する研究を鋭意進めて来た（Ｅｎｅｒｇｙ ＆ Ｆｕｅｌｓ，Ｖｏｌ．１３，Ｎｏ５，１０１５−１０２０，１９９９．文献Ａ）。しかし、ここでは該脱硫剤を調製するのに使用する水の量は、Ｈ２Ｏ／（キャリヤー粒子＋Ｃａ（ＯＨ）２）の重量比が１．５と比較的多いものであり、このような水の使用の条件では、水資源の少ない地域においては脱硫方法としての利用するにはまだ改善が必要である。更に、その際、廃棄物をできるだけ少なくするために、副生物の利用性の向上と、添加する脱硫剤の利用効率の改善が重要なことであった。そこで、本発明者等は、前記技術を更に進めて乾式脱硫プロセスを、ほぼ実用レベルで設計できる脱硫剤を研究し、比較的大きな粒径を持ちＳＯ２の吸収脱硫成分であるＣａ（ＯＨ）２を表面に被覆できるキャリヤー粒子を用いることにより、ＳＯ２の吸収脱硫成分であるＣａ（ＯＨ）２のＣａの利用率を向上させ、かつ効率良く、利用性の高いＣａＳＯ４を副生品として分離・回収できる脱硫方法および脱硫装置発明を完成し発表している（特開２００２−１１３３２６号公報）。また、本発明者は〔Ｆｕｅｌ， ７８／９，１０８９−１０９５（１９９９）〕において、脱硫プロセスにおけるガス中に存在するＮＯｘの連鎖反応による効果を発表しているけれども、大粒径のキャリヤー粒子表面に微粒子のＣａ（ＯＨ）２を被覆したＳＯ２脱硫剤を用いて、被処理ガス中のＳＯ２をＣａＳＯ４として分離回収する脱硫方法における、ＣａＳＯ４の回収率に対する効果については全く検討されていない。
【０００５】
【発明が解決しようとする課題】
本願発明の課題は、大粒径のキャリヤー粒子表面に微粒子のＣａ（ＯＨ）２を被覆したＳＯ２脱硫剤を用いて有用な副製品であるＣａＳＯ４をより高率に回収できる脱硫方法および脱硫装置を提供することである。前記脱硫剤を用いる脱硫方法および脱硫装置においは、Ｃａ（ＯＨ）２を被覆した大粒径のキャリヤー粒子表面で被処理ガス中のＳＯ２と反応して生成するＣａＳＯ４が、キャリヤー表面から効率よく剥離されることがＣａＳＯ４をより高率に回収するために重要である。
前記剥離の効率の向上にはどのようなファクターが関連するか不明であったが、前記脱硫剤を用いる脱硫方法の改善のために、前記本発明者らが発表した脱硫処理におけるＮＯＸ（Ｘは１から２）共存効果に着目して、１０〜４８０ｐｐｍのＮＯ２を共存させたところ、ＣａＳＯ４の回収特性が改善されることを見出し、前記課題を解決することができた。
【０００６】
【課題を解決するための手段】
本発明の第１は、（１）ＳＯ２を含む被処理ガスにＮＯ ２ を１０〜４８０ｐｐｍ共存させ、大粒径のキャリヤー粒子表面に微粒子のＣａ（ＯＨ）２を被覆したＳＯ２脱硫剤を前記ＳＯ２を含む被処理ガスと流動層を形成した状態で反応塔中で接触させ、前記脱硫剤とＳＯ２とを反応させながら前記被処理ガスと共に前記反応塔中を上昇させ、該反応塔の上部から前記ＳＯ２とキャリヤー粒子表面の微粒子のＣａ（ＯＨ）２との反応により形成されたＣａＳＯ４を前記キャリヤー粒子および被処理ガスと共に第１の気体−固体分離器に流動させ、前記第１の気体−固体分離器中で前記キャリヤー粒子表面のＣａ（ＯＨ）２とＳＯ２との反応により形成され剥離したＣａＳＯ４を含む気体から該キャリヤー粒子を沈降させて分離し、該ＣａＳＯ４を含む気体を前記第１の気体−固体分離器上部から第２の気体−固体分離器に流動させ、第２の気体−固体分離器において被処理ガスから前記ＣａＳＯ４を分離・回収することを特徴とする被処理ガス中のＳＯ２をＣａＳＯ４として分離回収する脱硫方法である。好ましくは、（２）被処理ガス中にＮＯ ２ を１０〜４８０ｐｐｍ共存させて被処理ガス中のＳＯ２をＣａＳＯ４として分離回収する脱硫方法が、排ガス中にＮＯ ２ が含まれていないか、含まれていても不十分な場合外部からＮＯ ２ を供給することを特徴とする前記（１）記載の被処理ガス中のＳＯ２をＣａＳＯ４として分離回収する脱硫方法であり、一層好ましくは、（３）被処理ガス中にＮＯ２ が１０〜４８０ｐｐｍ含まれていなく、１０〜４８０ｐｐｍのＮＯ２を共存させて被処理ガス中のＳＯ２をＣａＳＯ４として分離回収する脱硫方法において、被処理ガス中にＮＯが存在する場合には、被処理ガス中のＮＯの少なくとも一部をＮＯ２に変換する処理手段を経由させて、またＮＯおよびＮＯ２が存在しない場合にはＮＯの少なくとも一部をＮＯ２に変換する処理手段の前にＮＯを供給するか、ＮＯ２を外部から処理ガス中に供給し、被処理ガス中に１０〜４８０ｐｐｍのＮＯ ２ を共存させて、被処理ガスを大粒径のキャリヤー粒子表面に微粒子のＣａ（ＯＨ）２を被覆したＳＯ２脱硫剤が存在する反応塔に供給することを特徴とする前記（１）または（２）に記載の被処理ガス中のＳＯ２をＣａＳＯ４として分離回収する脱硫方法であり、より一層好ましくは、（４）ＮＯの少なくとも一部をＮＯ２に変換する処理手段が３００℃〜４００℃においてメタノール、ｔ−ブチルパーオキサイドを霧化圧入することにより酸化するものであることを特徴とする前記（３）に記載の被処理ガス中のＳＯ２をＣａＳＯ４として分離回収する脱硫方法である。
【０００７】
本発明の第２は、（５）大粒径のキャリヤー粒子表面に微粒子のＣａ（ＯＨ）２を被覆したＳＯ２脱硫剤が被処理ガスの供給により流動層を形成する反応塔１、前記反応塔１に大粒径のキャリヤー粒子表面に微粒子のＣａ（ＯＨ）２が被覆されたＳＯ２脱硫剤を供給する脱硫剤供給装置、ＳＯ２を含む被処理ガス中に１０〜４８０ｐｐｍのＮＯ２を共存させる装置、１０〜４８０ｐｐｍのＮＯ２を共存させたＳＯ２を含む被処理ガスを吹き込む被処理ガス吹き込み装置、前記脱硫剤をＳＯ２を含む被処理ガスと流動層を形成する状態で反応塔中で接触させ、前記脱硫剤とＳＯ２とを反応させながら前記被処理ガスと共に前記反応塔中を上昇させ、該反応塔の上部から前記ＳＯ２とキャリヤー粒子表面の微粒子のＣａ（ＯＨ）２との反応により形成されたＣａＳＯ４を前記キャリヤー粒子および被処理ガスと共に吹き込まれ、前記キャリヤー粒子を前記キャリヤー表面で形成され・脱離したＣａＳＯ４を含む被処理ガスから前記キャリヤー粒子を沈降させて分離する第１の気体−固体分離器および前記第１の気体−固体分離器から前記ＣａＳＯ４を含む被処理ガスが吹き込まれ、吹き込まれた被処理ガスから該ＣａＳＯ４を分離する第２の気体−固体分離器を持つことを特徴とする被処理ガス中のＳＯ２をＣａＳＯ４として分離回収する脱硫装置であり、好ましくは、（６）ＳＯ２を含む被処理ガス中に１０〜４８０ｐｐｍのＮＯ２を共存させる装置が、ＳＯ２をＣａＳＯ４として分離回収する被処理ガスを流動層を形成する反応塔１に供給する前に配置され、前記被処理ガス中のＮＯ ２ を１０〜４８０ｐｐｍにする外部からＮＯおよび／またはＮＯ２を供給する装置および／またはＮＯをＮＯ２に変換するコンバーターを含むことを特徴とする前記（５）に記載の被処理ガス中のＳＯ２をＣａＳＯ４として分離回収する脱硫装置であり、より好ましくは、（７）流動層を形成する反応塔１とＣａＳＯ４を含む被処理ガスから前記キャリヤー粒子を沈降させて分離する第１の気体−固体分離器とで循環型流動層を形成していることを特徴とする前記（５）または（６）に記載の被処理ガス中のＳＯ２をＣａＳＯ４として分離回収する脱硫装置である。
【０００８】
【本発明の実施の態様】
本発明をより詳細に説明する。
Ａ．第１図は、本発明のＳＯ２を含む被処理ガスにＮＯおよび／またはＮＯ２を１０〜４８０ｐｐｍ共存させ、特に被処理ガスにＮＯ ２ を１０〜４８０ｐｐｍ共存させ大粒径のキャリヤー粒子表面に微粒子のＣａ（ＯＨ）２を被覆したＳＯ２脱硫剤を前記ＳＯ２を含む被処理ガスと流動層を形成した状態で反応塔中で接触させ被処理ガス中のＳＯ２をＣａＳＯ４として分離回収する脱硫装置の概念図である。１は、多孔板（ＰＰ）を備えた流動層形成反応塔である。前記反応塔１の前記多孔板ＰＰの下方には、例えばボイラーＢからの被処理ガス（被処理気体）に１０〜〜４８０ｐｐｍのＮＯおよび／またはＮＯ２を共存させた被処理ガスを供給する装置、例えば送風ポンプが接続されている。被処理ガスにＮＯおよび／またはＮＯ２共存させるために、前記被処理ガスを供給する装置の前にＮＯおよび／またはＮＯ２を供給する装置、および／または被処理ガス中に共存したＮＯの少なくとも一部をＮＯ２に変換する装置ＣＶおよび前記変換を促進する酸化剤を吹き込む酸化剤供給手段（ＯＤ）が設けられている。
【０００９】
多孔板ＰＰの上方にはＳＯ２脱硫剤供給装置９、ここでは、脱硫剤の製造装置が反応塔１に直結している。脱硫剤および反応塔以降の装置類は本発明者らが既に提案している前記特開２００２−１１３３２６号公報に詳細に記載されている。前記公報に記載の技術的説明は、大粒径のキャリヤー粒子表面に微粒子のＣａ（ＯＨ）２を被覆したＳＯ２脱硫剤をＳＯ２を含む被処理ガスと流動層を形成した状態で反応塔中で接触させ被処理ガス中のＳＯ２をＣａＳＯ４として分離回収する脱硫方法および脱硫装置において「被処理ガスにＮＯおよび／またはＮＯ２共存させる」という本発明の技術的特徴、特に被処理ガスにＮＯ ２ 共存させること、を除いては、本発明と密接に関連することであるから、本発明の技術的説明の一部をなすものとして理解すべきである。
【００１０】
【実施例】
ここでの説明は、本発明の理解をし易くするだけのものであり、本発明を限定するものではない。
実施例１
被処理ガスとして、ＳＯ２含有量が１５００ｐｐｍ、ＣＯ２含有量が１２％、Ｏ２含有量が８％のものを試料とした。脱硫剤としては、キャリヤー粒子として、下記の表１に記載の化学組成を持ち、平均粒径１３７μｍ、表面積１２６ｍ２／ｇのフライアッシュを用い、これに、Ｃａ（ＯＨ）２を（キャリヤー粒子＋Ｃａ（ＯＨ）２）との重量比が１．５となるように被覆したものを用いた。これを、Ｃａ／Ｓ比が１．７となるように供給し、ガス空塔速度０．７５ ｍ／ｓ、反応器（循環型流動層形成反応塔）温度３５０℃、気相滞留時間１．５秒（ｓ）、圧力損失１ｋＰａ（脱硫剤粒子充填率に相当）とした。
【００１１】
【表１】

Figure 0004012011
【００１２】
表２に記載のＮＯまたはＮＯ２を共存（ｐｐｍ）させて脱硫した時と、これらＮＯＸが共存しなかった時の脱硫特性（％）を表２に示す。ＮＯまたはＮＯ２の共存効果を比較すると、同じ共存量において、ＮＯ２の共存効果の方が大きいことが表２から理解される。このことから、ＮＯをＮＯ２に変換するコンバーターＣＶを設けることが、ＳＯ２をＣａＳＯ４として分離回収する脱硫法において顕著な改善をもたらすことは明らかである。またＮＯおよび／またはＮＯ２の共存量が５０ｐｐｍ〜３００ｐｐｍ以上ではこれらの共存効果はほぼ飽和しており、被処理ガス中に共存すべき最低濃度は１０ｐｍｍであるが上限はない。
【００１３】
【表２】
Figure 0004012011
【００１４】
実施例２
ＮＯ、ＮＯ２の共存量がそれぞれ４８０ｐｐｍにおける脱硫率（Ｃａ／Ｓ）の効果を実験した結果を表３に示す。
前記実験を、被処理ガスとして、ＳＯ２含有量が１５００ｐｐｍ、ＣＯ２含有量が１２％、Ｏ２含有量が８％のを試料を、脱硫剤として、実施例１で用いたものと同じ化学組成、平均粒径および表面積を持つフライアッシュを用い、これに、のＣａ（ＯＨ）２を（キャリヤー粒子＋Ｃａ（ＯＨ）２）との重量比が１．５になるように被覆したものを用いて、実施した。表３の結果から、脱硫率に対するＮＯおよびＮＯ２の共存の効果が明らかであり、ＮＯ２の共存による脱硫率の向上への効果は、ＮＯの共存による脱硫率の向上への効果に比べて安定していることも分かった。このことは、ＮＯ２の共存は脱硫反応の安定した反応に効果があることが理解される。
【００１５】
【表３】
Figure 0004012011
【００１６】
実施例３
ここでは、大粒径のキャリヤー粒子表面に微粒子のＣａ（ＯＨ）２を被覆したＳＯ２脱硫剤を用いた場合における、キャリヤー粒子表面の微粒子のＣａ（ＯＨ）２とＳＯ２との反応により形成されたＣａＳＯ４をキャリヤー粒子表面から脱離する特性に対するＮＯ（４８０ｐｐｍ）およびＮＯ２（４８０ｐｐｍ）の共存効果を、粒子飛沫量の経時変化として表４と図２に示す。
【００１７】
【表４】
Figure 0004012011
【００１８】
粒子飛沫量＝（飛沫した粒子のうちのＣａの量ｇ／分）÷（供給した脱硫剤のＣａ量ｇ／分）である。ＮＯ（□）およびＮＯ２（▲）の添加により、飛沫粒子が増えている〔ＮＯもＮＯ２も共存しない場合は（◆）で示した。〕。このことはＮＯもＮＯ２の共存により脱硫剤が有効にはたらき、効率よく石膏が得られていることを意味する。ＮＯの場合は、経時と飛沫量の関係を示す上記結果を見ると、変動が大きく、飛沫量が安定していない、換言すれば安定な反応が進行していなく、制御性あまり良くない。これに対して、ＮＯ２の共存の場合には飛沫量が非常に安定している。このことから、ＮＯ２の共存下でＳＯ２含有被処理ガス中のＳＯ２をＣａＳＯ４として分離回収する脱硫法がより効果的であることが理解される。
【００１９】
【発明の効果】
以上述べたように、本発明は、ＳＯ２を含む被処理ガスにＮＯおよび／またはＮＯ２を１０〜４８０ｐｐｍ共存させ、大粒径のキャリヤー粒子表面に微粒子のＣａ（ＯＨ）２を被覆したＳＯ２脱硫剤と接触させてＳＯ２をＣａＳＯ４として分離回収する脱硫方法を確立し、ＳＯ２を高効率で有用な副生物であるＣａＳＯ４として回収可能にし、実用的な環境改善手段を供給した点で、社会に貢献すること多大であることは明らかである。
【図面の簡単な説明】
【図１】本発明の脱硫装置の概念図
【図２】ＳＯ２含有被処理ガス中へのＮＯおよびＮＯ２の共存のＳＯ２をＣａＳＯ４として分離回収特性と粒子飛沫の量の経時変化の相関
【符号の説明】
１ 流動層形成反応塔 ２ 第１の気体−固体分離器 ３ 第２の気体−固体分離器
４ 被処理ガス吹き込み部 ５ 分離キャリヤー粒子の還流管
６ ＣａＳＯ４を含む気体の移送管 ７ 処理済み被処理ガス
８ 回収ＣａＳＯ４を含む固体反応物取り出し配管
９ ＳＯ２脱硫剤供給部（ＳＯ２脱硫剤製造・供給装置）
ＣＶ ＮＯ２コンバーター ＯＤ 酸化剤供給手段
Ｂ ボイラー（被処理ガス発生源）[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a desulfurization method for separating and recovering a gas to be processed, for example, SO 2 in exhaust gas as CaSO 4 and a desulfurization method for the gas to be processed and a desulfurization apparatus in which the recovery rate of CaSO 4 in the desulfurization apparatus is improved. The present invention relates to a desulfurization method and a desulfurization apparatus for separating and recovering SO 2 in a gas to be treated as CaSO 4 , characterized in that 10 to 480 ppm of NO 2 coexists.
[0002]
[Prior art]
SO 2 is a substance that has a significant impact on the environment and human health, and SO 2 generated from coal combustion processes is a major social problem. Therefore, conventionally, a system for absorbing and removing SO 2 has been studied. One of them is an absorption removal method using CaO. The absorption removal of SO 2 using CaO is performed through the process of diffusion of SO 2 and formation of CaSO 4 / CaSO 3 by solid reaction. Therefore, the characteristics of CaO particles, that is, the surface area, the pore diameter, the pore volume, and the like have a great influence on the absorption removal . Commercially available CaO cannot be said to have a good calcium utilization rate with respect to the property of absorbing and removing SO 2 .
[0003]
Sanders et al. (Sanders et al., Ind. Eng. Chem.) Reported that SO 2 absorption and removal characteristics are improved when a mixed slurry of fly ash and slaked lime is used. Res. 1995, 34 (4), 302-307). Among the reports, the improvement of SO 2 absorption and removal characteristics lies in the presence of calcium silicate hydrate produced by the hydration reaction between calcium and alumina silicate, and the difference in reactivity is the structure of calcium silicate hydrate. It is explained that. In addition, γ-alumina-CaO adsorbent (Svobo et al.), CaO, calcium sulfate, and a slurry from fly ash were aged at about 100 ° C. and dried (Hiroaki et al.). (It is considered that an ettringate is formed. A similar technique is also disclosed in Japanese Patent Publication No. 3-59737), but the method for preparing these adsorbents is water. Relatively low usage, poor availability in poor water areas, and long time and / or lots of energy required to remove water, and adsorption during preparation of SO 2 adsorbent forming a composition for improving the properties since such is difficult to manage the process, it is difficult to design a desulfurization unit, such as a direct drive apparatus for producing sO 2 sorbent to the desulfurization apparatus There is an inconvenience to say.
[0004]
On the other hand, the present inventors know the mechanism of the hydration process in the process of preparing the adsorbent by mixing CaO and fly ash in water, so that the activity that can be made more practical from the raw material. a SO 2 came extensive studying of manufacturing a desulfurizing agent showing adsorption characteristics (Energy & Fuels, Vol.13, No5,1015-1020,1999 . Document a). However, the amount of water used to prepare the desulfurization agent is relatively high at a weight ratio of H 2 O / (carrier particles + Ca (OH) 2 ) of 1.5. Under the conditions of water use, improvement is still necessary for use as a desulfurization method in areas where water resources are scarce. Furthermore, at that time, in order to reduce waste as much as possible, it is important to improve the utilization of by-products and the utilization efficiency of the added desulfurizing agent. Therefore, the present inventors further studied the desulfurization agent capable of designing the dry desulfurization process at an almost practical level by further advancing the above technology, and Ca (OH), which has a relatively large particle size and is an SO 2 absorption desulfurization component. By using carrier particles that can coat 2 on the surface, the utilization rate of Ca in the Ca (OH) 2 that is an absorption desulfurization component of SO 2 is improved, and CaSO 4 that is efficient and highly available is used as a by-product. A desulfurization method and desulfurization apparatus invention that can be separated and recovered have been completed and disclosed (Japanese Patent Laid-Open No. 2002-113326). In addition, the present inventor has announced in [Fuel, 78/9, 1089-1095 (1999)] the effect of the chain reaction of NO x present in the gas in the desulfurization process. The effect on the recovery rate of CaSO 4 in the desulfurization method in which SO 2 in the gas to be treated is separated and recovered as CaSO 4 using an SO 2 desulfurization agent coated with fine particles of Ca (OH) 2 on the surface has been completely studied. Not.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a desulfurization method and desulfurization capable of recovering CaSO 4 which is a useful by-product at a higher rate by using a SO 2 desulfurization agent in which fine particles of Ca (OH) 2 are coated on the surface of a carrier particle having a large particle diameter. Is to provide a device. Desulfurizing method and desulfurizing apparatus odor using the desulfurizing agent, CaSO 4 which reacts with SO 2 in the processed gas at the carrier particles surface with a large particle size coated with Ca (OH) 2 is, from the carrier surface Efficient peeling is important for recovering CaSO 4 at a higher rate.
It was unclear what factors were associated with the improvement in the efficiency of the exfoliation. However, in order to improve the desulfurization method using the desulfurization agent, NO x (X 1 to 2) Focusing on the coexistence effect, it was found that when 10 to 480 ppm of NO 2 was allowed to coexist, the recovery characteristics of CaSO 4 were improved, and the above problems could be solved.
[0006]
[Means for Solving the Problems]
In the first aspect of the present invention, (1) an SO 2 desulfurization agent in which 10 to 480 ppm of NO 2 coexists in a gas to be treated containing SO 2 and the surface of a large carrier particle is coated with fine Ca (OH) 2 is used. The gas to be treated containing SO 2 is contacted in a reaction tower in a state where a fluidized bed is formed, and the reaction tower is raised together with the gas to be treated while reacting the desulfurizing agent and SO 2. CaSO 4 formed by the reaction of the SO 2 and fine particles of Ca (OH) 2 on the surface of the carrier particles is flowed to the first gas-solid separator together with the carrier particles and the gas to be treated from above the first gas-solid separator. 1 gas - from gas containing CaSO 4 that releases peeling is formed by reaction of the Ca (OH) 2 and SO 2 of the carrier particles surface with the solid separator in allowed to settle the carrier particles are separated, the C Wherein the gas containing SO 4 first gas - solid separator top from the second gas - to flow to the solid separator, a second gas - the CaSO 4 to separate and recover from the gas to be treated in the solid separator This is a desulfurization method for separating and recovering SO 2 in a gas to be treated as CaSO 4 . Preferably, (2) the desulfurization method in which 10 to 480 ppm of NO 2 coexists in the gas to be treated and SO 2 in the gas to be treated is separated and recovered as CaSO 4 is NO 2 in the exhaust gas, a and, more preferably contained said, characterized by also supplying the externally et NO 2 if insufficient optionally (1) desulfurization process for separating and recovering a SO 2 in the treated gas according as CaSO 4 , (3) NO 2 is not contained 10~480ppm to be treated in the gas, in the desulfurizing method for separating and recovering the SO 2 in the treated gas coexist NO 2 of 10~480ppm as CaSO 4, to be treated when the nO is present in the gas, by way of the processing means for converting at least a portion of nO in the treated gas to nO 2, also when the nO and nO 2 is not present in the nO Either deliver NO before the processing means for converting a portion to NO 2 even without supplies NO 2 in the treated gas from the outside, coexist NO 2 of 10~480ppm in the gas to be treated, the The process gas according to (1) or (2), wherein the treatment gas is supplied to a reaction tower having a SO 2 desulfurization agent in which fine particles of Ca (OH) 2 are coated on the surface of carrier particles having a large particle size. It is a desulfurization method in which SO 2 in the process gas is separated and recovered as CaSO 4 , and more preferably, (4) the treatment means for converting at least a part of NO into NO 2 is methanol, t- The desulfurization method for separating and recovering SO 2 in the gas to be treated as CaSO 4 according to the above ( 3) , wherein butyl peroxide is oxidized by atomizing and pressing.
[0007]
The second aspect of the present invention is: (5) a reaction tower 1 in which a SO 2 desulfurization agent in which fine particles of Ca (OH) 2 are coated on the surface of a carrier particle having a large particle size forms a fluidized bed by supplying a gas to be treated; A desulfurization agent supply device for supplying an SO 2 desulfurization agent in which fine particle Ca (OH) 2 is coated on the surface of a carrier particle having a large particle size to the tower 1, and 10 to 480 ppm of NO 2 in a gas to be treated containing SO 2. An apparatus for coexisting, a process gas blowing apparatus for blowing a process gas containing SO 2 coexisting with 10 to 480 ppm of NO 2 , and a reaction tower in a state where a fluidized bed is formed with the process gas containing SO 2 and the process gas containing SO 2 The reaction gas is brought into contact with the desulfurizing agent and SO 2 to react with the gas to be treated, and is raised in the reaction tower. From the upper part of the reaction tower, the SO 2 and fine particles of Ca (OH) 2 on the surface of the carrier particles are introduced. With Insufflated CaSO 4 formed by response together with the carrier particles and the gas to be treated, is separated by settling the carrier particles from the treated gas containing said CaSO 4 to the carrier particles detached are formed, at the surface of the carrier first gas - solid separator and the first gas - solid treated gas containing CaSO 4 from the separator is blown, the second gas to separate the CaSO 4 from the processing gas blown - solid A desulfurization apparatus for separating and recovering SO 2 in a gas to be treated as CaSO 4 characterized by having a separator, preferably (6) 10 to 480 ppm of NO 2 in the gas to be treated containing SO 2 The coexisting device is disposed before supplying the gas to be treated for separating and recovering SO 2 as CaSO 4 to the reaction tower 1 forming the fluidized bed, The apparatus according to ( 5) above, comprising a device for supplying NO and / or NO 2 from the outside to adjust NO 2 in the gas to be treated to 10 to 480 ppm and / or a converter for converting NO to NO 2 More preferably, the desulfurization apparatus separates and recovers SO 2 in the gas to be processed as CaSO 4 , and (7) the carrier particles are precipitated from the gas to be processed including the reaction tower 1 forming the fluidized bed and the CaSO 4. A circulating fluidized bed is formed with the first gas-solid separator to be separated, and SO 2 in the gas to be treated according to (5) or (6) is separated and recovered as CaSO 4 Desulfurization equipment.
[0008]
[Embodiments of the present invention]
The present invention will be described in more detail.
A. Figure 1 is NO and / or NO 2 in the treated gas containing SO 2 in the present invention coexist 10 ～480Ppm, especially the NO 2 in the gas to be treated to the carrier particles surface with a large particle size is 10~480ppm coexist contacting in a reaction column in a state in which the SO 2 desulfurizing agent coated with Ca (OH) 2 fine particles to form a fluidized bed and treated gas containing SO 2 separation and recovery of SO 2 in the treated gas as CaSO 4 It is a conceptual diagram of a desulfurization apparatus. 1 is a fluidized bed forming reaction tower equipped with a perforated plate (PP). An apparatus for supplying a gas to be processed in which 10 to 480 ppm of NO and / or NO 2 coexist in a gas to be processed (gas to be processed) from the boiler B, for example, below the porous plate PP of the reaction tower 1 For example, a blower pump is connected. To NO and / or NO 2 coexist in the gas to be treated, at least of NO coexisted the device for supplying NO and / or NO 2 in front of the device for supplying a gas to be treated, and / or to be treated in the gas device CV and blow can Komu oxidant supply means an oxidant that promotes the conversion into a NO 2 (OD) is provided partially.
[0009]
Above the perforated plate PP, an SO 2 desulfurization agent supply device 9, here, a desulfurization agent production device, is directly connected to the reaction tower 1. The desulfurization agent and the apparatus after the reaction tower are described in detail in the above-mentioned JP-A No. 2002-113326 already proposed by the present inventors. Technical Description according to the publication, the reaction tower in a state in which the SO 2 desulfurizing agent to the carrier particle surfaces with a large particle size were coated microparticles of Ca (OH) 2 to form a fluidized bed and treated gas containing SO 2 In the desulfurization method and desulfurization apparatus in which SO 2 in the gas to be treated is separated and recovered as CaSO 4 and brought into contact therewith, the technical feature of the present invention , in particular, the gas to be treated is made to coexist with NO and / or NO 2 Except for coexisting with NO 2 , it is closely related to the present invention and should be understood as part of the technical description of the present invention.
[0010]
【Example】
The description here is only to facilitate understanding of the present invention and is not intended to limit the present invention.
Example 1
As a gas to be treated, a sample having an SO 2 content of 1500 ppm, a CO 2 content of 12%, and an O 2 content of 8% was used as a sample. As the desulfurizing agent, as carrier particles, fly ash having the chemical composition shown in Table 1 below and having an average particle size of 137 μm and a surface area of 126 m 2 / g was used, and Ca (OH) 2 was added to (carrier particles + Ca What was coated so that the weight ratio with (OH) 2 ) would be 1.5 was used. This was supplied so that the Ca / S ratio was 1.7, the gas superficial velocity was 0.75 m / s, the reactor (circulating fluidized bed forming reaction tower) temperature was 350 ° C., and the gas phase residence time was 1. The pressure loss was set to 5 seconds (s), and the pressure loss was 1 kPa (corresponding to the desulfurization agent particle filling rate).
[0011]
[Table 1]
Figure 0004012011
[0012]
Table 2 shows the desulfurization characteristics (%) when NO or NO 2 listed in Table 2 coexists with desulfurization (ppm) and when NO X does not coexist. When comparing the coexistence effect of NO or NO 2 , it can be seen from Table 2 that the coexistence effect of NO 2 is larger at the same coexistence amount. From this, it is clear that the provision of the converter CV that converts NO to NO 2 brings about a significant improvement in the desulfurization method in which SO 2 is separated and recovered as CaSO 4 . Also these coexistence effect in amount coexistence more 50ppm~300ppm of NO and / or NO 2 is almost saturated, the lowest concentration should coexist in the gas to be treated is a 10pmm no upper limit.
[0013]
[Table 2]
Figure 0004012011
[0014]
Example 2
Table 3 shows the results of experiments on the effect of desulfurization rate (Ca / S) when the coexistence amounts of NO and NO 2 are 480 ppm, respectively.
The same chemistry as that used in Example 1 was used for the experiment, using as a gas to be treated a sample having an SO 2 content of 1500 ppm, a CO 2 content of 12%, and an O 2 content of 8% as a desulfurization agent. composition, using fly ash having an average particle size and surface area, with which this weight ratio of Ca to (OH) 2 and (carrier particles + Ca (OH) 2) of coated so that 1.5 And implemented. From the results of Table 3, the effect of coexistence of NO and NO 2 on the desulfurization rate is clear, and the effect of improving the desulfurization rate due to the coexistence of NO 2 is compared with the effect of improving the desulfurization rate due to the coexistence of NO 2. I also found it stable. This means that the coexistence of NO 2 is effective for a stable reaction of the desulfurization reaction.
[0015]
[Table 3]
Figure 0004012011
[0016]
Example 3
Here, in the case where an SO 2 desulfurization agent in which fine particle Ca (OH) 2 is coated on the surface of a large particle particle is used, it is formed by the reaction of fine particle Ca (OH) 2 on the carrier particle surface with SO 2. Table 4 and FIG. 2 show the coexistence effect of NO (480 ppm) and NO 2 (480 ppm) on the property of desorbing the CaSO 4 that has been released from the carrier particle surface as time-dependent changes in the amount of particle droplets.
[0017]
[Table 4]
Figure 0004012011
[0018]
Particle splash amount = (Ca amount g / min of splashed particles) ÷ (Ca amount g / min of supplied desulfurization agent). The addition of NO (□) and NO 2 (▲) increases the amount of splash particles [when neither NO nor NO 2 coexist is indicated by (♦). ]. This means that NO and NO 2 coexist and the desulfurization agent works effectively, and gypsum is obtained efficiently. In the case of NO, looking at the above results showing the relationship between time and the amount of droplets, the fluctuation is large and the amount of droplets is not stable, in other words, a stable reaction does not proceed and controllability is not very good. In contrast, in the case of coexistence of NO 2 is the amount of splash is very stable. Therefore, it is understood desulfurization method of separating and recovering SO 2 of SO 2 containing treated gas as CaSO 4 in the presence of NO 2 is more effective.
[0019]
【The invention's effect】
As described above, in the present invention, SO and NO 2 and / or NO 2 coexist in a gas to be treated containing SO 2 , and the surface of large carrier particles is coated with fine particles of Ca (OH) 2. Established a desulfurization method that separates and recovers SO 2 as CaSO 4 by bringing it into contact with 2 desulfurizing agent, enables SO 2 to be recovered as CaSO 4 which is a highly efficient and useful by-product, and provided practical environmental improvement means. In terms, it is clear that contributing to society is enormous.
[Brief description of the drawings]
FIG. 1 is a conceptual diagram of a desulfurization apparatus according to the present invention. FIG. 2 is a graph showing changes over time in the separation and recovery characteristics and the amount of particle droplets when SO 2 in the coexistence of NO and NO 2 in a SO 2 -containing gas is CaSO 4 . Correlation [Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Fluidized bed formation reaction tower 2 1st gas-solid separator 3 2nd gas-solid separator 4 To-be-treated gas blowing part 5 Separation carrier particle reflux pipe 6 Gas transfer pipe containing CaSO 4 7 Treated Process gas 8 Solid reactant extraction pipe 9 containing recovered CaSO 4 SO 2 desulfurization agent supply unit (SO 2 desulfurization agent production / supply device)
CV NO 2 converter OD Oxidant supply means B Boiler (treated gas generation source)

Claims (7)

ＳＯ２を含む被処理ガスにＮＯ ２ を１０〜４８０ｐｐｍ共存させ、大粒径のキャリヤー粒子表面に微粒子のＣａ（ＯＨ）２を被覆したＳＯ２脱硫剤を前記ＳＯ２を含む被処理ガスと流動層を形成した状態で反応塔中で接触させ、前記脱硫剤とＳＯ２とを反応させながら前記被処理ガスと共に前記反応塔中を上昇させ、該反応塔の上部から前記ＳＯ２とキャリヤー粒子表面の微粒子のＣａ（ＯＨ）２との反応により形成されたＣａＳＯ４を前記キャリヤー粒子および被処理ガスと共に第１の気体−固体分離器に流動させ、前記第１の気体−固体分離器中で前記キャリヤー粒子表面のＣａ（ＯＨ）２とＳＯ２との反応により形成され剥離したＣａＳＯ４を含む気体から該キャリヤー粒子を沈降させて分離し、該ＣａＳＯ４を含む気体を前記第１の気体−固体分離器上部から第２の気体−固体分離器に流動させ、第２の気体−固体分離器において被処理ガスから前記ＣａＳＯ４を分離・回収することを特徴とする被処理ガス中のＳＯ２をＣａＳＯ４として分離回収する脱硫方法。An SO 2 desulfurizing agent in which 10 to 480 ppm of NO 2 coexists in a gas to be treated containing SO 2 and fine particles of Ca (OH) 2 are coated on the surface of carrier particles having a large particle diameter flows with the gas to be treated containing SO 2. contacting in a state of forming a layer in a reaction column, wherein while the desulfurizing agent and the SO 2 is reacted to increase the in the reaction column together with the process gas, the SO 2 and the carrier particle surface from the top of the reaction column The CaSO 4 formed by the reaction of the fine particles of Ca (OH) 2 with the carrier particles and the gas to be treated is flowed to the first gas-solid separator, and the CaSO 4 is allowed to flow in the first gas-solid separator. from gas containing CaSO 4 that releases peeling is formed by reaction of the Ca (OH) 2 and SO 2 of the carrier particle surface to precipitate the carrier particles are separated, before the gas containing the CaSO 4 The upper part of the first gas-solid separator is flowed to the second gas-solid separator, and the CaSO 4 is separated and recovered from the gas to be treated in the second gas-solid separator. A desulfurization method in which SO 2 in the process gas is separated and recovered as CaSO 4 . 被処理ガス中にＮＯ ２ を１０〜４８０ｐｐｍ共存させて被処理ガス中のＳＯ２をＣａＳＯ４として分離回収する脱硫方法が、排ガス中にＮＯ ２ が含まれていないか、含まれていても不十分な場合外部からＮＯ ２ を供給することを特徴とする請求項１に記載の被処理ガス中のＳＯ２をＣａＳＯ４として分離回収する脱硫方法。Desulfurization process for separating and recovering the NO 2 in the gas to be treated is 10~480ppm coexist with SO 2 in the treated gas as CaSO 4 is, does not contain any NO 2 in the exhaust gas, also contain non desulfurization process for separating and recovering a SO 2 as CaSO 4 of the treated gas according to claim 1, characterized in that to supply sufficient if externally et NO 2. 被処理ガス中にＮＯ２ が１０〜４８０ｐｐｍ含まれていなく、１０〜４８０ｐｐｍのＮＯ２を共存させて被処理ガス中のＳＯ２をＣａＳＯ４として分離回収する脱硫方法において、被処理ガス中にＮＯが存在する場合には、被処理ガス中のＮＯの少なくとも一部をＮＯ２に変換する処理手段を経由させて、またＮＯおよびＮＯ２が存在しない場合にはＮＯの少なくとも一部をＮＯ２に変換する処理手段の前にＮＯを供給するか、ＮＯ２を外部から処理ガス中に供給し、被処理ガス中に１０〜４８０ｐｐｍのＮＯ ２ を共存させて被処理ガスを大粒径のキャリヤー粒子表面に微粒子のＣａ（ＯＨ）２を被覆したＳＯ２脱硫剤が存在する反応塔に供給することを特徴とする請求項１または２に記載の被処理ガス中のＳＯ２をＣａＳＯ４として分離回収する脱硫方法。In the desulfurization method in which 10 to 480 ppm of NO 2 is not contained in the gas to be treated, and SO 2 in the gas to be treated is separated and recovered as CaSO 4 in the presence of 10 to 480 ppm of NO 2 , NO 2 is contained in the gas to be treated. Is present, it is passed through a processing means for converting at least part of NO in the gas to be treated into NO 2 , and when NO and NO 2 are not present, at least part of NO is converted to NO 2 . Either NO is supplied before the processing means for conversion or NO 2 is supplied into the processing gas from the outside , and 10 to 480 ppm of NO 2 coexists in the processing gas to make the processing gas a large particle particle. and CaSO 4 with SO 2 in the treated gas according to supplied to the reaction tower SO 2 desulfurizing agent coated with Ca (OH) 2 fine particles are present in claim 1 or 2, characterized in the surface Desulfurization process for separating and recovering Te. ＮＯの少なくとも一部をＮＯ２に変換する処理手段が３００℃〜４００℃においてメタノール、ｔ−ブチルパーオキサイドを霧化圧入することにより酸化するものであることを特徴とする請求項３に記載の被処理ガス中のＳＯ２をＣａＳＯ４として分離回収する脱硫方法。Methanol in at least processing means for converting part of the NO 2 is 300 ° C. to 400 ° C. NO, the according to claim 3, characterized in that the oxidation by atomizing press-t- butyl peroxide A desulfurization method in which SO 2 in a gas to be treated is separated and recovered as CaSO 4 . 大粒径のキャリヤー粒子表面に微粒子のＣａ（ＯＨ）２を被覆したＳＯ２脱硫剤が被処理ガスの供給により流動層を形成する反応塔１、前記反応塔１に大粒径のキャリヤー粒子表面に微粒子のＣａ（ＯＨ）２が被覆されたＳＯ２脱硫剤を供給する脱硫剤供給装置、ＳＯ２を含む被処理ガス中に１０〜４８０ｐｐｍのＮＯ２を共存させる装置、１０〜４８０ｐｐｍのＮＯ２を共存させたＳＯ２を含む被処理ガスを吹き込む被処理ガス吹き込み装置、前記脱硫剤をＳＯ２を含む被処理ガスと流動層を形成する状態で反応塔中で接触させ、前記脱硫剤とＳＯ２とを反応させながら前記被処理ガスと共に前記反応塔中を上昇させ、該反応塔の上部から前記ＳＯ２とキャリヤー粒子表面の微粒子のＣａ（ＯＨ）２との反応により形成されたＣａＳＯ４を前記キャリヤー粒子および被処理ガスと共に吹き込まれ、前記キャリヤー粒子を前記キャリヤー表面で形成され・脱離したＣａＳＯ４を含む被処理ガスから前記キャリヤー粒子を沈降させて分離する第１の気体−固体分離器および前記第１の気体−固体分離器から前記ＣａＳＯ４を含む被処理ガスが吹き込まれ、吹き込まれた被処理ガスから該ＣａＳＯ４を分離する第２の気体−固体分離器を持つことを特徴とする被処理ガス中のＳＯ２をＣａＳＯ４として分離回収する脱硫装置。Reaction column 1 SO 2 desulfurizing agent coated with particles of Ca (OH) 2 to the carrier particle surface with a large particle size to form a fluidized bed by the supply of the gas to be treated, the carrier particles surface with a large particle size into the reaction tower 1 A desulfurization agent supply device for supplying an SO 2 desulfurization agent coated with fine particles of Ca (OH) 2 on the surface, a device for allowing 10 to 480 ppm of NO 2 to coexist in a gas to be treated containing SO 2 , and 10 to 480 ppm of NO 2 A treatment gas blowing apparatus for blowing a treatment gas containing SO 2 coexisting with the gas, a desulfurization agent and a treatment gas containing SO 2 in contact with each other in a reaction tower in a state of forming a fluidized bed, and the desulfurization agent and SO 2 is raised in the reaction tower together with the gas to be treated while reacting with 2, and formed from the upper part of the reaction tower by the reaction of the SO 2 with fine Ca (OH) 2 on the surface of the carrier particles. SO 4 is blown together with the carrier particles and the gas to be treated, and a first gas that settles and separates the carrier particles from the gas to be treated containing CaSO 4 formed and desorbed on the surface of the carrier. A gas to be treated containing CaSO 4 is blown from a solid separator and the first gas-solid separator, and a second gas-solid separator is provided for separating the CaSO 4 from the blown gas to be treated. A desulfurization apparatus for separating and recovering SO 2 in a gas to be treated as CaSO 4 . ＳＯ２を含む被処理ガス中に１０〜４８０ｐｐｍのＮＯ２を共存させる装置が、ＳＯ２をＣａＳＯ ４ として分離回収する被処理ガスを流動層を形成する反応塔１に供給する前に配置され、前記被処理ガス中のＮＯ ２ を１０〜４８０ｐｐｍにする外部からＮＯおよび／またはＮＯ２を供給する装置および／またはＮＯをＮＯ２に変換するコンバーターを含むことを特徴とする請求項５に記載の被処理ガス中のＳＯ２をＣａＳＯ４として分離回収する脱硫装置。The apparatus in which 10 to 480 ppm of NO 2 coexists in the gas to be treated containing SO 2 is disposed before supplying the gas to be treated for separating and recovering SO 2 as CaSO 4 to the reaction tower 1 forming the fluidized bed , 6. The apparatus according to claim 5 , further comprising: a device for supplying NO and / or NO 2 from the outside to adjust NO 2 in the gas to be treated to 10 to 480 ppm and / or a converter for converting NO to NO 2 . A desulfurization apparatus that separates and recovers SO 2 in the gas to be treated as CaSO 4 . 流動層を形成する反応塔１とＣａＳＯ４を含む被処理ガスから前記キャリヤー粒子を沈降させて分離する第１の気体−固体分離器とで循環型流動層を形成していることを特徴とする請求項５または６に記載の被処理ガス中のＳＯ２をＣａＳＯ４として分離回収する脱硫装置。A circulation type fluidized bed is formed by the reaction tower 1 forming a fluidized bed and the first gas-solid separator for separating and separating the carrier particles from the gas to be treated containing CaSO 4. desulfurization apparatus for separating recovered as CaSO 4 and SO 2 in the treated gas according to claim 5 or 6.
JP2002246125A 2002-08-27 2002-08-27 Desulfurization method and desulfurization apparatus for recovering SO2 as CaSO4 by coexisting NO2 in a gas to be treated Expired - Fee Related JP4012011B2 (en)

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PCT/JP2003/010699 WO2004020077A1 (en) 2002-08-27 2003-08-25 METHOD AND APPARATUS FOR DESULFURIZATION COMPRISING INCORPORATING NO AND/OR NO2 IN GAS TO BE TREATED, TO RECOVER SO2 AS CaSO4
CNB038201127A CN1331568C (en) 2002-08-27 2003-08-25 Method and apparatus for desulfurization comprising incorporating NO and/or NO2 in gas to be treated, to recover SO2 as CaSO4

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