JPH01176429A - Flue gas desulfurization method accompanied by dehalogenation - Google Patents
Flue gas desulfurization method accompanied by dehalogenationInfo
- Publication number
- JPH01176429A JPH01176429A JP62332354A JP33235487A JPH01176429A JP H01176429 A JPH01176429 A JP H01176429A JP 62332354 A JP62332354 A JP 62332354A JP 33235487 A JP33235487 A JP 33235487A JP H01176429 A JPH01176429 A JP H01176429A
- Authority
- JP
- Japan
- Prior art keywords
- exhaust gas
- gas
- flue gas
- ammonia
- desulfurization
- 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.)
- Pending
Links
- 239000003546 flue gas Substances 0.000 title claims abstract description 27
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 23
- 230000023556 desulfurization Effects 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000005695 dehalogenation reaction Methods 0.000 title 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007789 gas Substances 0.000 claims abstract description 36
- -1 ammonium halide Chemical class 0.000 claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 10
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 4
- 230000003009 desulfurizing effect Effects 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 abstract description 12
- 229910000039 hydrogen halide Inorganic materials 0.000 abstract description 9
- 239000012433 hydrogen halide Substances 0.000 abstract description 9
- 239000007787 solid Substances 0.000 abstract 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 239000000292 calcium oxide Substances 0.000 description 5
- 235000012255 calcium oxide Nutrition 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- 108091006629 SLC13A2 Proteins 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は各種のボイラーないしは焼結炉から排出される
燃焼排ガスを対象とする排煙脱硫法の改良に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an improvement in a flue gas desulfurization method for flue gases discharged from various boilers or sintering furnaces.
［従来の技術とその問題点コ
ボイラー排ガスないしは焼結炉排ガスなどの燃焼排ガス
には、硫黄酸化物及び窒素酸化物の外に、かなりの量の
ハロゲン化水素が、典型的には塩化水素が含まれている
。このため、燃焼排ガスをそのまま乾式又は湿式の排煙
脱硫装置で処理した場合には、排煙脱硫の副生品として
回収される硫酸乃至は石膏中に、ハロゲン化水素が混入
して副生品の品質を低下させる不都合がある。
・
このような不都合を回避するための方法として、従来は
排ガスを脱硫装置に供給するのに先立って、生石灰（ｃ
ａｂ）に接触させる方法が採用されている、この方法に
よれば、例えば排ガス中の塩化水素は生石灰と反応して
捕捉され、生石灰は塩化カルシウム（ｃａＣ１ｚ）の形
に転化するが、塩化カルシウムは潮解性で吸湿性が極め
て強いため、生石灰充填層の圧力損失が増大してしまう
難点があった。また、塩化カルシウムは生石灰への再生
が効かず、しかも水によく溶けるのでその処分にも問題
もあった。[Prior art and its problems] Combustion exhaust gases, such as coboiler exhaust gas or sintering furnace exhaust gas, contain, in addition to sulfur oxides and nitrogen oxides, significant amounts of hydrogen halides, typically hydrogen chloride. It is. For this reason, if combustion flue gas is directly treated in a dry or wet flue gas desulfurization equipment, hydrogen halide may be mixed into the sulfuric acid or gypsum recovered as a by-product of flue gas desulfurization. This has the disadvantage of reducing the quality of the product.
・ As a method to avoid such inconveniences, conventionally, before supplying the exhaust gas to the desulfurization equipment, quicklime (c
According to this method, for example, hydrogen chloride in the exhaust gas is captured by reacting with quicklime, and the quicklime is converted into calcium chloride (caC1z), but calcium chloride is Since it is deliquescent and extremely hygroscopic, it has the disadvantage of increasing pressure loss in the quicklime packed bed. Additionally, calcium chloride cannot be recycled into quicklime, and it is highly soluble in water, so there were problems with its disposal.
［問題点を解決するための手段］
本発明は燃焼排ガスを乾式法で脱硫するに当って、その
前処理として排ガス中のハロゲン化水素にアンモニアを
作用させ、面体のハロゲン化アンモニウムを生成させる
ことで排ガスがらこれを分離する工程を組み込んだ排煙
脱硫法を提供する。[Means for Solving the Problems] The present invention involves, when desulfurizing combustion exhaust gas by a dry method, ammonia is applied to hydrogen halide in the exhaust gas as a pretreatment to generate ammonium halide of the face piece. The present invention provides a flue gas desulfurization method that incorporates a process of separating this from flue gas.
すなわち、本発明に係る排煙脱硫法は、（ａ）燃焼排ガ
スを乾式の排煙脱硫装置に導入するのに先立って、その
排ガスにアンモニアガスを混合して排ガスに含まれるハ
ロゲン化水素を固体のハロゲン化アンモニウムに転化さ
せる工程、（ｂ）工程（ａ）で生成されたハロゲン化ア
ンモニウムを排ガスから分離して中和槽に供給する工程
、（ｃ）前記の中和槽にてハロゲン化アンモニウムを苛
性ソーダで中和してアンモニアガスを回収し、このアン
モニアガスを工程（ａ）でに循環する工程、及び（ｄ）
工程（ｂ）でハロゲン化アンモニウムから分離された排
ガスを乾式又は湿式脱硫装置に導入して脱硫する工程を
包含する。That is, in the flue gas desulfurization method according to the present invention, (a) prior to introducing the combustion flue gas into a dry flue gas desulfurization device, ammonia gas is mixed with the flue gas to solidify the hydrogen halide contained in the flue gas. (b) separating the ammonium halide produced in step (a) from the exhaust gas and supplying it to the neutralization tank; (c) converting the ammonium halide in the neutralization tank neutralizing with caustic soda to recover ammonia gas, and circulating this ammonia gas in step (a), and (d)
The method includes a step of introducing the exhaust gas separated from the ammonium halide in step (b) into a dry or wet desulfurization device to desulfurize it.
本発明に於いて、排ガスに混合されるアンモニアの量は
、排ガスに含まれるハロゲン化水素をモル数で上廻るこ
とが必要であるが、余り過剰のアンモニアを注入すると
、アンモニアが排煙脱硫装置からリークする心配がある
。従って、−船釣には次式で規定される範囲で、排ガス
へのアンモニア注入量（モル数）が選定される。In the present invention, it is necessary that the amount of ammonia mixed with the exhaust gas exceeds the hydrogen halide contained in the exhaust gas by the number of moles, but if too much ammonia is injected, the ammonia There is a risk of leaks from the Therefore, for boat fishing, the amount (number of moles) of ammonia to be injected into the exhaust gas is selected within the range defined by the following formula.
排ガス中の＜ＮＨ３注入量＜ 排ガス中のＨＸ十ＨＸ
（モル数） ＮＯｘ＋ＳＯｘ （モ
ル数）但し、ＨＸはハロゲン化水素を、ＮＯｘは窒素酸
化物を、ＳＯＸは硫黄酸化物をそれぞれ示す。<NH3 injection amount in exhaust gas < HX 10HX in exhaust gas
(Number of moles) NOx+SOx (Number of moles) However, HX represents hydrogen halide, NOx represents nitrogen oxide, and SOX represents sulfur oxide.
本発明の一実施例を添付図面にそって説明すると、ボイ
ラー又は焼結炉から排出され、ライン１を流れる塩化水
素含有燃焼排ガスには、ライン２から上に述べた量のア
ンモニアガスが混合される。この混合ガスはサイクロン
又はマルチクロン等の気−同分離装置３に送られるが、
この間に排ガスに含まれる塩化水素のほぼ１００％はア
ンモニアと反応し、塩化アンモニウムの微粉が生成され
る。また、排ガス中に二酸化硫黄が含まれている場合に
は、二酸化硫黄のアンモニアと反応して硫酸アンモニウ
ムの微粉が生成される。これらの微粉の殆どは気−同分
離装置３で排ガスから分離され、排ガスは集塵器４に供
給される。気−同分離装置３で排ガスから分離できなか
った微粉は集塵器で除去され、実質的に微粉を含まない
排ガスは、炭素質吸着剤が移動床を形成している吸着塔
５に導入されて脱硫処理を受けた後、煙突から大気に放
出される。ライン１に注入されるアンモニア量が上記の
式で規定される範囲内にある限り、煙突にアンモニアが
リークすることはない。An embodiment of the present invention will be described with reference to the accompanying drawings. Hydrogen chloride-containing flue gas discharged from a boiler or sintering furnace and flowing through line 1 is mixed with ammonia gas in the above-mentioned amount from line 2. Ru. This mixed gas is sent to a gas separation device 3 such as a cyclone or multiclone,
During this time, nearly 100% of the hydrogen chloride contained in the exhaust gas reacts with ammonia, producing fine powder of ammonium chloride. Furthermore, if the exhaust gas contains sulfur dioxide, the sulfur dioxide reacts with ammonia to produce fine powder of ammonium sulfate. Most of these fine powders are separated from the exhaust gas by the gas separator 3, and the exhaust gas is supplied to the dust collector 4. Fine particles that could not be separated from the exhaust gas by the gas separator 3 are removed by a dust collector, and the exhaust gas that does not substantially contain fine particles is introduced into an adsorption tower 5 in which a carbonaceous adsorbent forms a moving bed. After undergoing desulfurization treatment, it is released into the atmosphere through the chimney. As long as the amount of ammonia injected into line 1 is within the range defined by the above formula, no ammonia will leak into the chimney.
尚、図中の６は吸着塔５の底部から排出された不活化吸
着剤を、再生塔８の頂部に搬送するためのコンベアを、
また７は再生塔底部から排出された再生吸着剤を、吸着
塔の頂部に搬送するためのコンベアを示す。そして、不
活化吸着剤の再生時には、比較的高濃度で二酸化硫黄を
含有する脱離ガスがライン９に得られるが、この脱離ガ
スから硫酸又は石膏などの副生品が回収される。In addition, 6 in the figure is a conveyor for conveying the inactivated adsorbent discharged from the bottom of the adsorption tower 5 to the top of the regeneration tower 8.
Further, 7 indicates a conveyor for conveying the regenerated adsorbent discharged from the bottom of the regeneration tower to the top of the adsorption tower. When the inactivated adsorbent is regenerated, a desorption gas containing relatively high concentration of sulfur dioxide is obtained in line 9, from which by-products such as sulfuric acid or gypsum are recovered.
一方、気−同分離装置３及び集塵器４で集められた塩化
アンモニウム乃至は硫酸アンモニウムなどの微粉は中和
槽１０に供給される。この中和槽に於いて、塩化アンモ
ニウムや硫酸アンモニウムなどは、ライン１１から添加
される苛性ソーダにより、
ＮＨ４Ｃｌ ＋ ＮａＯＨ−＋ ＮａＣ１＋ Ｈ，Ｏ
＋ ＮＨ。On the other hand, fine powder such as ammonium chloride or ammonium sulfate collected by the gas separator 3 and the dust collector 4 is supplied to the neutralization tank 10. In this neutralization tank, ammonium chloride, ammonium sulfate, etc. are converted into NH4Cl + NaOH- + NaC1+ H,O by caustic soda added from line 11.
+NH.
（ＮＨ，）、Ｓ０４＋２ＮａＯＨ→ Ｎａ、Ｓｏ４＋２
Ｈ，０４２ＮＨ。(NH,), S04+2NaOH→ Na, So4+2
H,042NH.
の如く中和され、中和に際して発生するアンモニアガス
はブロア１２を介してライン１に混合される。また、中
和反応で生成される塩化ナトリウム、硫酸ナトリウム、
硫酸水素ナトリウムなどは中和槽１０からライン１３に
溢流し、槽内沈澱物はライン１４からスラリーとして排
出される。The ammonia gas generated during the neutralization is mixed into the line 1 via the blower 12. In addition, sodium chloride, sodium sulfate, produced in the neutralization reaction,
Sodium hydrogen sulfate and the like overflow from the neutralization tank 10 into the line 13, and the precipitate in the tank is discharged from the line 14 as slurry.
［発明の効果］
以上のとおり、本発明の方法によれば、アンモニアガス
を使用して燃焼排ガス中に含まれる実質的にすべてのハ
ロゲン化水素を、排煙脱硫処理前に除去することができ
、しかも排煙脱硫に炭素質吸着剤を使用する乾式脱硫装
置を採用すれば、脱ハロゲン化水素に必要なアンモニア
量より過剰のアンモニアを排ガスに注入しても、そのア
ンモニアガスは排ガスの脱硫脱硝に有効に利用できる利
点がある。[Effects of the Invention] As described above, according to the method of the present invention, substantially all hydrogen halides contained in combustion exhaust gas can be removed using ammonia gas before flue gas desulfurization treatment. Moreover, if a dry desulfurization equipment that uses a carbonaceous adsorbent is used for flue gas desulfurization, even if excess ammonia is injected into the flue gas than the amount of ammonia required for dehydrohalogenation, the ammonia gas will still be used for desulfurization and denitrification of the flue gas. There are advantages that can be used effectively.
第１図は本発明方法の一実施例を示すフローシートであ
る。FIG. 1 is a flow sheet showing one embodiment of the method of the present invention.
Claims (1)
方法に於いて、 （ａ）前記の燃焼排ガスを排煙脱硫装置に導入するのに
先立って、アンモニアガスを排ガスに混合して排ガスに
含まれるハロゲン化水素を固体のハロゲン化アンモニウ
ムに転化させる工程、 （ｂ）工程（ａ）で生成されたハロゲン化アンモニウム
を排ガスから分離して中和槽に供給する工程、 （ｃ）前記の中和槽にてハロゲン化アンモニウムを苛性
ソーダで中和してアンモニアガスを回収し、このアンモ
ニアガスを工程（ａ）でに循環する工程、及び （ｄ）工程（ｂ）でハロゲン化アンモニウムから分離さ
れた排ガスを乾式又は湿式脱硫装置に導入して脱硫する
工程、 を包含する排煙脱硫法。[Claims] 1. In a method for desulfurizing flue gas by supplying it to a dry flue gas desulfurization device, (a) prior to introducing the flue gas into the flue gas desulfurization device, ammonia gas is added to the flue gas. (b) A step of separating the ammonium halide produced in step (a) from the exhaust gas and supplying it to the neutralization tank. (c) neutralizing ammonium halide with caustic soda in the neutralization tank to recover ammonia gas, and circulating this ammonia gas in step (a); and (d) in step (b). A flue gas desulfurization method that includes the step of introducing flue gas separated from ammonium halide into a dry or wet desulfurization device to desulfurize it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62332354A JPH01176429A (en) | 1987-12-28 | 1987-12-28 | Flue gas desulfurization method accompanied by dehalogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62332354A JPH01176429A (en) | 1987-12-28 | 1987-12-28 | Flue gas desulfurization method accompanied by dehalogenation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01176429A true JPH01176429A (en) | 1989-07-12 |
Family
ID=18254022
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62332354A Pending JPH01176429A (en) | 1987-12-28 | 1987-12-28 | Flue gas desulfurization method accompanied by dehalogenation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01176429A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0445527U (en) * | 1990-08-13 | 1992-04-17 | ||
| JP2004535911A (en) * | 2001-02-26 | 2004-12-02 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニー | Gas processing using NOx-specific reactants |
| CN107398156A (en) * | 2017-08-25 | 2017-11-28 | 钢研晟华科技股份有限公司 | A kind of system and technique for sintering flue gas pollutant synthesis emission reduction |
-
1987
- 1987-12-28 JP JP62332354A patent/JPH01176429A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0445527U (en) * | 1990-08-13 | 1992-04-17 | ||
| JP2004535911A (en) * | 2001-02-26 | 2004-12-02 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニー | Gas processing using NOx-specific reactants |
| CN107398156A (en) * | 2017-08-25 | 2017-11-28 | 钢研晟华科技股份有限公司 | A kind of system and technique for sintering flue gas pollutant synthesis emission reduction |
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