JPH06114235A - Flue gas dentrification method using on-site ammonia - Google Patents
Flue gas dentrification method using on-site ammoniaInfo
- Publication number
- JPH06114235A JPH06114235A JP5024257A JP2425793A JPH06114235A JP H06114235 A JPH06114235 A JP H06114235A JP 5024257 A JP5024257 A JP 5024257A JP 2425793 A JP2425793 A JP 2425793A JP H06114235 A JPH06114235 A JP H06114235A
- Authority
- JP
- Japan
- Prior art keywords
- ammonia
- hydrogen
- nitrogen
- flue gas
- gas denitration
- 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.)
- Granted
Links
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- Treating Waste Gases (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、事業用火力発電所、
コージェネ発電装置、ゴミ焼却炉などの固定発生源から
放出される大量の窒素酸化物（ＮＯｘ）を除去する排煙
脱硝法に関し、より詳細には、アンモニアを還元剤とし
て用いる接触還元排煙脱硝法に関する。This invention relates to a commercial thermal power plant,
TECHNICAL FIELD The present invention relates to a flue gas denitration method for removing a large amount of nitrogen oxides (NOx) emitted from a fixed generation source such as a cogeneration power generator and a refuse incinerator, and more specifically, a catalytic reduction flue gas denitration method using ammonia as a reducing agent. Regarding
【０００２】[0002]
【従来の技術】上記のような固定発生源から放出される
ＮＯｘを除去する排煙脱硝法においては、還元剤アンモ
ニアとして、コストが安いことを第一の理由に、液体ア
ンモニア（ボンベ入り）あるいはアンモニア水（２５
％）が使用されている。2. Description of the Related Art In the flue gas denitration method for removing NOx released from a fixed source as described above, liquid ammonia (with a cylinder) or Ammonia water (25
%) Is used.
【０００３】[0003]
【発明が解決しようとする課題】しかし、排煙脱硝法で
は、毒性が強く（許容濃度：５０ppm ）、しかも臭気の
強いアンモニアガスを大量に輸送、貯蔵する必要があ
る。そのため、これが万一漏れたときには危険性が大き
いことから、特に都市部においては使用が困難になりつ
つある。また、液体アンモニアあるいはアンモニア水
は、コストが高い（１３０〜１５０円／ｋｇ）という問
題もある。However, in the flue gas denitration method, it is necessary to transport and store a large amount of ammonia gas, which is highly toxic (allowable concentration: 50 ppm) and has a strong odor. For this reason, it is becoming difficult to use, especially in urban areas because it is highly dangerous if it should leak. Further, liquid ammonia or ammonia water has a problem that the cost is high (130 to 150 yen / kg).
【０００４】この発明の目的は、アンモニアの大量輸
送、貯蔵に起因する上記のような問題を克服し、しかも
コスト的に有利に排煙脱硝をなし得る方法を提供するこ
とにある。An object of the present invention is to provide a method capable of overcoming the above-mentioned problems caused by the mass transportation and storage of ammonia and at the same time effecting flue gas denitration in a cost effective manner.
【０００５】[0005]
【課題を解決するための手段】この発明による排煙脱硝
法は、固定発生源から放出される窒素酸化物を還元除去
するに当たり、オンサイトすなわち現場でアンモニアを
合成しこれを還元剤として使用することを特徴とするも
のである。In the flue gas denitration method according to the present invention, in reducing and removing nitrogen oxides emitted from a fixed source, ammonia is synthesized on-site, that is, in situ, and used as a reducing agent. It is characterized by that.
【０００６】この発明の好適な実施態様においては、Ｐ
ＳＡなどの空気分離で得た窒素と水の電解で得た水素と
を１０気圧未満の圧力、２００〜４００℃の温度で反応
させてアンモニアを合成し、合成混合物から水素を低エ
ネルギーの膜分離法などにより除去し、残ったアンモニ
アと窒素の混合ガスを排煙脱硝に使用し、分離した水素
をアンモニア合成工程に再循環する。In a preferred embodiment of the present invention, P
Nitrogen obtained by air separation such as SA and hydrogen obtained by electrolysis of water are reacted at a pressure of less than 10 atm and a temperature of 200 to 400 ° C. to synthesize ammonia, and hydrogen is separated from the synthesis mixture by low energy membrane separation. The remaining mixed gas of ammonia and nitrogen is used for flue gas denitration, and the separated hydrogen is recycled to the ammonia synthesis step.
【０００７】この発明のもう１つの好適な実施態様にお
いては、ＰＳＡなどの空気分離で得た窒素とメタノール
の改質反応で得た水素とを１０気圧未満の圧力、２００
〜４００℃の温度で反応させてアンモニアを合成し、合
成混合物から水素を除去し、残ったアンモニアと窒素の
混合ガスを排煙脱硝に使用し、分離した水素をアンモニ
ア合成工程に再循環する。In another preferred embodiment of the present invention, nitrogen obtained by air separation such as PSA and hydrogen obtained by the reforming reaction of methanol are mixed at a pressure of less than 10 atm.
The reaction is carried out at a temperature of ˜400 ° C. to synthesize ammonia, hydrogen is removed from the synthesis mixture, the remaining mixed gas of ammonia and nitrogen is used for flue gas denitration, and the separated hydrogen is recycled to the ammonia synthesis process.
【０００８】なお、メタノールの改質反応で得た水素
は、不純物として炭素ガスなどを含むので、ＰＳＡ、膜
分離などの方法により精製される。Since hydrogen obtained by the reforming reaction of methanol contains carbon gas and the like as impurities, it is purified by a method such as PSA or membrane separation.
【０００９】このアンモニア合成装置はオンサイトで
水、電気というクリーンなエネルギーを使用するもので
ある。This ammonia synthesizer uses on-site clean energy such as water and electricity.
【００１０】また、アンモニア合成に用いる窒素と水素
の比率は、限定はされないが、Ｎ2／Ｈ2 ≦１／３とす
るのが好ましい。The ratio of nitrogen to hydrogen used for ammonia synthesis is not limited, but it is preferable that N 2 / H 2 ≦ 1/3.
【００１１】[0011]
【実施例】つぎにこの発明の実施例を幾つか挙げる。EXAMPLES Next, some examples of the present invention will be described.
【００１２】実施例１ 図１のフローシートにおいて、ＰＳＡで得た窒素を３０
０℃に昇温し（１．９気圧）、水の電解で得た水素を同
じく３００℃に昇温し（１．９気圧）、該窒素と水素と
を９気圧に圧縮し、これらをＮ2 ／Ｈ2 ＝１／３で３０
０℃で反応させてアンモニアを合成した。合成混合物か
ら水素を膜分離法により除去し、残ったアンモニアと窒
素の混合ガスを脱硝装置に送って排煙脱硝に使用した。
また、分離した水素をアンモニア合成工程に再循環し
た。Example 1 In the flow sheet of FIG.
The temperature was raised to 0 ° C. (1.9 atm), the hydrogen obtained by electrolysis of water was similarly raised to 300 ° C. (1.9 atm), the nitrogen and hydrogen were compressed to 9 atm, and these were N 2 2 / H 2 = 1/3, 30
Ammonia was synthesized by reacting at 0 ° C. Hydrogen was removed from the synthesis mixture by a membrane separation method, and the remaining mixed gas of ammonia and nitrogen was sent to a denitration device and used for flue gas denitration.
Also, the separated hydrogen was recycled to the ammonia synthesis step.
【００１３】実施例２ 窒素と水素とをＮ2 ／Ｈ2 ＝１／１２で反応させた点を
除いて、実施例１と同じ操作を行った。Example 2 The same operation as in Example 1 was carried out except that nitrogen and hydrogen were reacted at N 2 / H 2 = 1/12.
【００１４】実施例３ 窒素と水素とをＮ2 ／Ｈ2 ＝１／４８で反応させた点を
除いて、実施例１と同じ操作を行った。Example 3 The same operation as in Example 1 was carried out except that nitrogen and hydrogen were reacted at N 2 / H 2 = 1/48.
【００１５】実施例１〜３のエネルギー比較を表１に示
す。Table 1 shows the energy comparison of Examples 1 to 3.
【００１６】[0016]
【表１】 また、窒素と水素との比Ｎ2 ／Ｈ2 を変化させ、この比
とエネルギーの関係を図２のグラフに示す。[Table 1] Further, the ratio N 2 / H 2 between nitrogen and hydrogen was changed, and the relationship between this ratio and energy is shown in the graph of FIG.
【００１７】実施例４ 図３のフローシートにおいて、ＰＳＡまたは膜分離で得
た窒素を３００℃に昇温し（１．９気圧）、メタノール
の改質反応で得た水素（不純物として炭素ガスなどを含
む）をＰＳＡまたは膜分離で処理して不純物を除き、精
製水素を上記と同じく３００℃に昇温し（１．９気
圧）、該窒素と水素とを９気圧に圧縮し、これらをＮ2
／Ｈ2 ＝１／３で３００℃で反応させてアンモニアを合
成した。合成混合物から水素を膜分離法により除去し、
残ったアンモニアと窒素の混合ガスを脱硝装置に送って
排煙脱硝に使用した。また、分離した水素をアンモニア
合成工程に再循環した。Example 4 In the flow sheet of FIG. 3, PSA or nitrogen obtained by membrane separation was heated to 300 ° C. (1.9 atm) and hydrogen obtained by a reforming reaction of methanol (such as carbon gas as an impurity). Are treated with PSA or membrane separation to remove impurities, the purified hydrogen is heated to 300 ° C. (1.9 atm) in the same manner as above, and the nitrogen and hydrogen are compressed to 9 atm. 2
/ H 2 = 1/3 was reacted at 300 ° C. to synthesize ammonia. Removing hydrogen from the synthesis mixture by a membrane separation method,
The remaining mixed gas of ammonia and nitrogen was sent to a denitration device and used for flue gas denitration. Also, the separated hydrogen was recycled to the ammonia synthesis step.
【００１８】実施例５ 窒素と水素とをＮ2 ／Ｈ2 ＝１／１２で反応させた点を
除いて、実施例４と同じ操作を行った。Example 5 The same operation as in Example 4 was performed, except that nitrogen and hydrogen were reacted at N 2 / H 2 = 1/12.
【００１９】実施例６ 窒素と水素とをＮ2 ／Ｈ2 ＝１／４８で反応させた点を
除いて、実施例４と同じ操作を行った。Example 6 The same operation as in Example 4 was carried out except that nitrogen and hydrogen were reacted at N 2 / H 2 = 1/48.
【００２０】実施例４〜６のエネルギー比較を表２に示
す。Table 2 shows the energy comparison of Examples 4 to 6.
【００２１】[0021]
【表２】 また、窒素と水素との比Ｎ2 ／Ｈ2 を変化させ、この比
とエネルギーの関係を図４のグラフに示す。[Table 2] Further, the ratio N 2 / H 2 of nitrogen to hydrogen was changed, and the relationship between this ratio and energy is shown in the graph of FIG.
【００２２】[0022]
【発明の効果】この発明によれば、固定発生源から放出
される窒素酸化物を還元除去するに当たり、オンサイト
でアンモニアを合成しこれを還元剤として使用するの
で、この方法はアンモニアの大量輸送、貯蔵を必要とす
る従来法と比較して極めて安全である。According to the present invention, in reducing and removing nitrogen oxides released from a fixed source, ammonia is synthesized on-site and used as a reducing agent. Therefore, this method is used for mass transport of ammonia. It is extremely safe compared with the conventional method that requires storage.
【００２３】また、ＰＳＡなどの空気分離で得た窒素と
水の電解またはメタノールの改質反応で得た水素とを反
応させてアンモニアを合成するので、脱硝をコスト的に
極めて有利に実施できる。Further, since nitrogen is obtained by air separation such as PSA and hydrogen obtained by electrolysis of water or reforming reaction of methanol to synthesize ammonia, denitration can be carried out extremely advantageously in terms of cost.
【００２４】また、アンモニア合成反応後の未反応水素
を混合ガスから分離して、残りの窒素混入アンモニアガ
スを還元剤に使用するので、純アンモニアを用いる方法
と比較して大幅な省エネルギー化を図ることができる。Further, since unreacted hydrogen after the ammonia synthesis reaction is separated from the mixed gas and the remaining nitrogen-containing ammonia gas is used as the reducing agent, a large energy saving is achieved as compared with the method using pure ammonia. be able to.
【図１】この発明の実施例１を示すフローシートであ
る。FIG. 1 is a flow sheet showing a first embodiment of the present invention.
【図２】Ｎ2 ／Ｈ2 比とエネルギーの関係を示すグラフ
である。FIG. 2 is a graph showing the relationship between N 2 / H 2 ratio and energy.
【図３】この発明の実施例４を示すフローシートであ
る。FIG. 3 is a flow sheet showing Example 4 of the present invention.
【図４】Ｎ2 ／Ｈ2 比とエネルギーの関係を示すグラフ
である。FIG. 4 is a graph showing the relationship between N 2 / H 2 ratio and energy.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 篠原 力男 大阪市此花区西九条５丁目３番28号 日立 造船株式会社内 (72)発明者 藤本 良男 大阪市此花区西九条５丁目３番28号 日立 造船株式会社内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Rikio Shinohara 5-3-8 Nishi-Kujo, Konohana-ku, Osaka City Hitachi Shipbuilding Co., Ltd. (72) Yoshio Fujimoto 5-28-3, Nishikujo, Konohana-ku, Osaka Issue Hitachi Shipbuilding Co., Ltd.
Claims (4)
還元除去するに当たり、オンサイトでアンモニアを合成
しこれを還元剤として使用することを特徴とする排煙脱
硝法。1. A flue gas denitration method characterized by synthesizing ammonia on-site and using this as a reducing agent in reducing and removing nitrogen oxides released from a fixed generation source.
素とを１０気圧未満の圧力、２００〜４００℃の温度で
反応させてアンモニアを合成し、合成混合物から水素を
除去し、残ったアンモニアと窒素の混合ガスを排煙脱硝
に使用し、分離した水素をアンモニア合成工程に再循環
することを特徴とする請求項１記載の排煙脱硝法。2. Nitrogen obtained by air separation and hydrogen obtained by electrolysis of water are reacted at a pressure of less than 10 atm and a temperature of 200 to 400 ° C. to synthesize ammonia, and hydrogen is removed from the synthesis mixture, 2. The flue gas denitration method according to claim 1, wherein the residual mixed gas of ammonia and nitrogen is used for flue gas denitration, and the separated hydrogen is recycled to the ammonia synthesis step.
反応で得た水素とを１０気圧未満の圧力、２００〜４０
０℃の温度で反応させてアンモニアを合成し、合成混合
物から水素を除去し、残ったアンモニアと窒素の混合ガ
スを排煙脱硝に使用し、分離した水素をアンモニア合成
工程に再循環することを特徴とする請求項１記載の排煙
脱硝法。3. Nitrogen obtained by air separation and hydrogen obtained by a reforming reaction of methanol are pressurized to a pressure of less than 10 atm and a pressure of 200 to 40.
The reaction is carried out at a temperature of 0 ° C. to synthesize ammonia, hydrogen is removed from the synthesis mixture, the remaining mixed gas of ammonia and nitrogen is used for flue gas denitration, and the separated hydrogen is recycled to the ammonia synthesis process. The flue gas denitration method according to claim 1, which is characterized in that.
率をＮ2 ／Ｈ2 ≦１／３とすることを特徴とする請求項
１〜３のうち１記載の排煙脱硝法。4. The flue gas denitration method according to claim 1, wherein the ratio of nitrogen and hydrogen used for ammonia synthesis is N 2 / H 2 ≦ 1/3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5024257A JP2992666B2 (en) | 1992-08-19 | 1993-02-12 | Flue gas denitration using on-site ammonia |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22043592 | 1992-08-19 | ||
| JP4-220435 | 1992-08-19 | ||
| JP5024257A JP2992666B2 (en) | 1992-08-19 | 1993-02-12 | Flue gas denitration using on-site ammonia |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06114235A true JPH06114235A (en) | 1994-04-26 |
| JP2992666B2 JP2992666B2 (en) | 1999-12-20 |
Family
ID=26361754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5024257A Expired - Lifetime JP2992666B2 (en) | 1992-08-19 | 1993-02-12 | Flue gas denitration using on-site ammonia |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2992666B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004099076A2 (en) * | 2003-05-05 | 2004-11-18 | Eaton Corporation | Methods and apparatus for small-scale synthesis of ammonia |
| WO2007012908A1 (en) * | 2004-05-05 | 2007-02-01 | Eaton Corporation | Adsorption based ammonia storage and regeneration system |
| JP2010500362A (en) * | 2006-08-10 | 2010-01-07 | ユニバーシティ オブ サザン カリフォルニア | Process for producing methanol, dimethyl ether, synthetic hydrocarbons and their products from carbon dioxide and water (steam) in the air as the only raw material |
| EP2589426A1 (en) * | 2011-11-02 | 2013-05-08 | Ammonia Casale S.A. | Method for removing nitrogen oxides from combustion fumes with on-site generation of ammonia |
| WO2016133133A1 (en) * | 2015-02-17 | 2016-08-25 | 味の素株式会社 | Production system and production method for nitrogen-containing products and products selected from fermented/cultured products |
| JP2017077547A (en) * | 2015-10-22 | 2017-04-27 | 株式会社タクマ | Denitration method in incineration facility and system thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479255B (en) * | 2019-09-17 | 2020-09-01 | 山东大学 | Rhodium catalyst for nitrogen reduction synthesis of ammonia and preparation method and application thereof |
-
1993
- 1993-02-12 JP JP5024257A patent/JP2992666B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004099076A2 (en) * | 2003-05-05 | 2004-11-18 | Eaton Corporation | Methods and apparatus for small-scale synthesis of ammonia |
| WO2004099076A3 (en) * | 2003-05-05 | 2005-05-12 | Eaton Corp | Methods and apparatus for small-scale synthesis of ammonia |
| WO2007012908A1 (en) * | 2004-05-05 | 2007-02-01 | Eaton Corporation | Adsorption based ammonia storage and regeneration system |
| JP2010500362A (en) * | 2006-08-10 | 2010-01-07 | ユニバーシティ オブ サザン カリフォルニア | Process for producing methanol, dimethyl ether, synthetic hydrocarbons and their products from carbon dioxide and water (steam) in the air as the only raw material |
| EP2589426A1 (en) * | 2011-11-02 | 2013-05-08 | Ammonia Casale S.A. | Method for removing nitrogen oxides from combustion fumes with on-site generation of ammonia |
| WO2016133133A1 (en) * | 2015-02-17 | 2016-08-25 | 味の素株式会社 | Production system and production method for nitrogen-containing products and products selected from fermented/cultured products |
| CN107406266A (en) * | 2015-02-17 | 2017-11-28 | 味之素株式会社 | Production system and production method for the product selected from nitrogenous product and fermented and culture product |
| US10941427B2 (en) | 2015-02-17 | 2021-03-09 | Ajinomoto Co., Inc. | Production system and method of production for product selected from nitrogen-containing product and fermented and cultured product |
| JP2017077547A (en) * | 2015-10-22 | 2017-04-27 | 株式会社タクマ | Denitration method in incineration facility and system thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2992666B2 (en) | 1999-12-20 |
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