JPS5912333B2 - Exhaust gas desulfurization and denitrification method - Google Patents
Exhaust gas desulfurization and denitrification methodInfo
- Publication number
- JPS5912333B2 JPS5912333B2 JP51024985A JP2498576A JPS5912333B2 JP S5912333 B2 JPS5912333 B2 JP S5912333B2 JP 51024985 A JP51024985 A JP 51024985A JP 2498576 A JP2498576 A JP 2498576A JP S5912333 B2 JPS5912333 B2 JP S5912333B2
- Authority
- JP
- Japan
- Prior art keywords
- exhaust gas
- rate
- gas
- absorption
- nox
- 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.)
- Expired
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Description
【発明の詳細な説明】
本発明は硫黄酸化物（ＳＯｘ）及び窒素酸化物ＮＯｘを
含む一般燃焼排ガス、例えばボイラー、加熱炉、焼結炉
、焙焼炉、転炉、溶解炉、焼却炉などから排出される燃
焼ガスなどからＳＯｘ及びＮＯｘを同時に除去する湿式
排煙脱硫脱硝方法に関する。Detailed Description of the Invention The present invention is applicable to general combustion exhaust gases containing sulfur oxides (SOx) and nitrogen oxides (NOx), such as boilers, heating furnaces, sintering furnaces, roasting furnaces, converters, melting furnaces, incinerators, etc. The present invention relates to a wet flue gas desulfurization and denitration method for simultaneously removing SOx and NOx from combustion gas etc. discharged from a combustion engine.
近年、環境保全上の見地から、各種工場などの排ガス中
のＳＯｘ及びＮＯｘを除去するための技術開発が進めら
れている。In recent years, from the standpoint of environmental conservation, technological development has been progressing to remove SOx and NOx from exhaust gas from various factories.
このような技術としては、排ガス中に含まれるＳＯｘ及
びＮＯｘを個別に除去する種々の脱硫プロセス及び脱硝
プロセスが知られており、また排ガス中に含まれるＳＯ
ｘ及びＮＯｘを同時に除去する排ガス脱硫脱硝プロセス
もいくつか提唱されている。As such technologies, various desulfurization processes and denitrification processes are known that individually remove SOx and NOx contained in exhaust gas, and
Several exhaust gas desulfurization and denitrification processes have been proposed that simultaneously remove x and NOx.
本発明者等も、ＳＯｘ及びＮＯｘによる大気汚染公害を
排除するため、ＳＯｘ及びＮＯｘを含む排ガスからＳＯ
ｘ及びＮＯｘを同時に除去するプロセスについて鋭意研
究開発を進め、ここに全く新規な湿式排ガス脱硫脱硝方
法を提供するものである。In order to eliminate air pollution caused by SOx and NOx, the present inventors also discovered that
We have conducted extensive research and development into a process that simultaneously removes x and NOx, and hereby provide a completely new wet exhaust gas desulfurization and denitrification method.
本発明の要旨は、硫黄酸化物及び窒素酸化物を含む排ガ
スをアルカリ金属、アルカリ土類金属又はアンモニウム
の水酸化物又は炭酸塩と、チオ尿素又はアルカリ金属、
アルカリ土類金属若しくはアンモニウムのチオ硫酸塩と
、銅イオン及び鉄イオンのうちの少なくとも一つの金属
イオンとを含み、且つ、前記水酸化物又は炭酸塩と排ガ
ス中の亜硫酸ガスとの反応で生成する亜硫酸塩濃度が０
．１モル／を未満である、水性洗浄液で洗浄することに
ある。The gist of the present invention is to convert exhaust gas containing sulfur oxides and nitrogen oxides into hydroxides or carbonates of alkali metals, alkaline earth metals or ammonium, thiourea or alkali metals,
It contains a thiosulfate of an alkaline earth metal or ammonium and at least one metal ion selected from copper ions and iron ions, and is produced by the reaction of the hydroxide or carbonate with sulfur dioxide gas in exhaust gas. Sulfite concentration is 0
．． The purpose is to wash with an aqueous washing liquid having an amount of less than 1 mol/ml.
本発明の脱硫脱硝方法において、ＳＯｘ及びＮＯｘを含
む排ガスは、適当な洗浄装置、例えば段塔、スクラバー
、充填塔などでアルカリ金属、アルカリ土類金属又はア
ンモニウムの水酸化物又は炭酸塩と、チオ尿素又はアル
カリ金属、アルカリ土類金属若しくはアンモニウムのチ
オ硫酸塩と、銅イオン及び鉄イオンのうちの少なくとも
一種の金属イオンとを含む水性洗浄液と気液接触させて
排ガス中のＳＯｘを亜硫酸塩として吸収し、ＮＯｘを窒
素ガス（Ｎ２）に還元して脱硫脱硝する。In the desulfurization and denitration method of the present invention, exhaust gas containing SOx and NOx is treated with hydroxides or carbonates of alkali metals, alkaline earth metals, or ammonium in a suitable cleaning device, such as a plate column, a scrubber, or a packed column. SOx in exhaust gas is absorbed as sulfite by bringing it into gas-liquid contact with an aqueous cleaning solution containing urea or thiosulfate of alkali metal, alkaline earth metal, or ammonium and at least one metal ion selected from copper ions and iron ions. Then, NOx is reduced to nitrogen gas (N2) for desulfurization and denitration.
排ガスのＳＯｘ及びＮＯｘ濃度、ＮＯｘ組成、他のガス
成分の組成並びに濃度による制限は特にないが、排ガス
中のＮＯは予じめＮＯ□、 Ｎ２Ｏ３又はＮ２０゜など
に酸化した後前記洗浄液で洗浄するのが好ましい。There are no particular restrictions on the concentration of SOx and NOx in the exhaust gas, the composition of NOx, and the composition and concentration of other gas components, but NO in the exhaust gas is oxidized in advance to NO□, N2O3, or N20°, and then cleaned with the cleaning solution described above. is preferable.
このような酸化剤としては従来公知の化合物、例えば二
酸化塩素、オゾン、過酸化水素、硝酸などを用いること
ができる。As such an oxidizing agent, conventionally known compounds such as chlorine dioxide, ozone, hydrogen peroxide, and nitric acid can be used.
洗浄液中の前記水酸化物又は炭酸塩は、下記式（１）〜
（４）で示される反応に従って排ガスの脱硫を行う。The hydroxide or carbonate in the cleaning liquid has the following formula (1) ~
The exhaust gas is desulfurized according to the reaction shown in (4).
２ＭＯＨ＋Ｓ０２＝Ｍ２ＳＯ３＋Ｈ２０・・・・・・（
１）Ｍ′（ＯＨ）２＋５０２−Ｍ′Ｓ０３＋Ｈ２０・・
・・・・（２）Ｍ２ＣＯ３＋５０２−Ｍ２ＣＯ３＋５０
２ ・・・・・・（３）Ｍ′ＣＯ３＋ＳＯ２＝Ｍ′
ＳＯ３＋ＣＯ２・・・・・・（４）上式において、Ｍは
ナトリウム、カリウムなどのアルカリ金属又はアンモニ
ウムを表し、Ｍ′はカルシウム、マグネシウムなどのア
ルカリ土類金属を表す。2MOH+S02=M2SO3+H20・・・・・・(
1) M'(OH)2+502-M'S03+H20...
...(2) M2CO3+502-M2CO3+50
2 ・・・・・・(3) M'CO3+SO2=M'
SO3+CO2 (4) In the above formula, M represents an alkali metal such as sodium or potassium or ammonium, and M' represents an alkaline earth metal such as calcium or magnesium.
即ち、亜硫酸ガス（８０２）は亜硫酸塩として洗浄液に
吸収される。That is, sulfur dioxide gas (802) is absorbed into the cleaning liquid as sulfite.
もつとも実際には燃焼排ガス中に多量に含まれる炭酸ガ
ス（ＣＯ２）が循環洗浄液中に溶解しているので洗浄液
中に補給された前記水酸化物又は炭酸塩は洗浄液中で溶
存ＣＯ２と反応して重炭酸塩（ＭＩ−（Ｃ０３又はＭ′
〔ＨＣＯ３〕２）となって排ガス中の８０２と反応して
亜硫酸塩となる。However, in reality, carbon dioxide gas (CO2), which is contained in large amounts in combustion exhaust gas, is dissolved in the circulating cleaning liquid, so the hydroxide or carbonate replenished into the cleaning liquid reacts with the dissolved CO2 in the cleaning liquid. Bicarbonate (MI-(C03 or M'
It becomes [HCO3]2) and reacts with 802 in the exhaust gas to become sulfite.
洗浄液中の前記水酸化物又は炭酸塩の濃度には特に限定
がない。There is no particular limitation on the concentration of the hydroxide or carbonate in the cleaning solution.
本発明プロセスの脱硝機構は必ずしも明確ではないが、
洗浄液中に含まれるチオ尿素又はチオ硫酸並びに銅及び
鉄イオンのうちの少なくとも一種の金属イオンが排ガス
中の窒素酸化物と成る種のコンプレックス化合物を形成
し、これに更にチオ尿素又はチオ硫酸塩が反応してＮＯ
ｘをＮ２に還元するものと想定される。Although the denitrification mechanism of the present invention process is not necessarily clear,
Thiourea or thiosulfate and at least one metal ion among copper and iron ions contained in the cleaning solution form a complex compound that becomes nitrogen oxides in the exhaust gas, and thiourea or thiosulfate further forms a complex compound that becomes nitrogen oxides in the exhaust gas. React and say NO
It is assumed that x is reduced to N2.
例えば、二酸化窒素（ＮＯ２）を含む排ガスをチオ尿素
又はチオ硫酸塩のみを含む洗浄液で洗浄した場合に脱硝
率は約４０％程度であるが、この洗浄液に更に銅イオン
を添加した場合の脱硝率は約９０係に達する。For example, when exhaust gas containing nitrogen dioxide (NO2) is washed with a cleaning solution containing only thiourea or thiosulfate, the denitration rate is approximately 40%, but when copper ions are further added to this cleaning solution, the denitration rate is approximately 40%. reaches about 90 units.
銅イオンの代りに鉄イオンを添加した場合にもほぼ同様
な結果が得られるが、ニッケルイオン、マンガンイオン
などを添加した場合の脱硝率は約４０係と金属イオンの
添加効果が認められない。Almost similar results are obtained when iron ions are added instead of copper ions, but when nickel ions, manganese ions, etc. are added, the denitrification rate is about 40 times, and no effect of metal ion addition is observed.
従って、本発明プロセスの脱硝方法は銅又は鉄イオンの
存在下に排ガスをチオ尿素又はチオ硫酸塩で洗浄するこ
とによってはじめて約９０％という高い除去率で排ガス
中のＮＯｘを除去することができ、しかも前記金属イオ
ンは触媒的に作用するので実質的に消耗が無いという特
長をもつ。Therefore, the denitrification method of the present invention can remove NOx in the exhaust gas with a high removal rate of about 90% only by cleaning the exhaust gas with thiourea or thiosulfate in the presence of copper or iron ions. Moreover, since the metal ions act catalytically, they have the advantage that they are virtually never consumed.
洗浄液中のチオ尿素又はチオ硫酸塩及び前記金属イオン
の濃度、洗浄液ｐＨ並びに温度には特に限定はないが、
非常に高い脱硝率を得るためには、約ｌＱＱｐｐｍ以上
のチオ尿素又は約１５０ｐＩｎ以上のチオ硫酸塩及び約
３０ｐ−以上の前記金属イオンを含むのが好ましく、ま
た洗浄液のｐＨを約４〜９にするのが好ましい。There are no particular limitations on the concentration of thiourea or thiosulfate and the metal ions in the cleaning solution, the pH and temperature of the cleaning solution,
In order to obtain a very high denitrification rate, it is preferable to contain about 1QQppm or more of thiourea or about 150 pIn or more of thiosulfate and about 30 p- or more of the aforementioned metal ions, and the pH of the cleaning solution should be about 4 to 9. It is preferable to do so.
前記金属イオンは硫酸塩、塩化物その他の塩の形態で又
はキレート化合物若しくは錯化合物の形態、その他任意
の形で洗浄液中に溶解又は懸濁させることができる。The metal ions can be dissolved or suspended in the cleaning liquid in the form of sulfates, chlorides or other salts, in the form of chelates or complexes, or in any other arbitrary form.
なお、本発明の脱硫脱硝方法では、排ガス中の亜硫酸ガ
スとアルカリ金属、アルカリ土類金属又はアンモニウム
の水酸化物又は炭酸塩との反応で循環洗浄液中に生成す
る亜硫酸塩がチオ尿素又はチオ硫酸塩と共にＮＯｘをＮ
２に還元する反応を行う。In addition, in the desulfurization and denitration method of the present invention, the sulfite generated in the circulating cleaning solution by the reaction between sulfur dioxide gas in the exhaust gas and the hydroxide or carbonate of alkali metal, alkaline earth metal, or ammonium is thiourea or thiosulfate. NOx with salt
Perform the reaction to reduce to 2.
この場合の反応機構は、前記したように、チオ尿素又は
チオ硫酸塩と銅、鉄及びビスマスイオンのうちの少なく
とも一種の金属イオンが排ガス中の窒素酸化物と成る種
のコンプレックス化合物を形成し、これに更にチオ尿素
又はチオ硫酸塩と共に前記亜硫酸塩が反応して窒素酸化
物を窒素に還元するものと想定される。The reaction mechanism in this case is, as described above, that thiourea or thiosulfate and at least one metal ion among copper, iron, and bismuth ions form a complex compound that becomes nitrogen oxide in the exhaust gas, It is assumed that the sulfite further reacts with thiourea or thiosulfate to reduce nitrogen oxides to nitrogen.
なお、本発明者らは先に前記吸収液において亜硫酸塩濃
度が０．１モル／を未満では充分な脱硝効果が得られな
いと判断して、吸収液中における亜硫酸塩濃度は０．１
モル／を以上でなければならないとして特許出願（特願
昭５０−５３１５１号、特開昭５１−１２９８６６号公
報参照）したが、その後の研究により寧ろ亜硫酸塩濃度
は０．１モル／を未満で充分であり、それ以上存在して
いても脱硝率などに及ぼす効果は飽和してしまい、実質
的に意味のないことを見出し、本発明をするに至ったの
である。The present inventors previously determined that a sufficient denitrification effect could not be obtained if the sulfite concentration in the absorption liquid was less than 0.1 mol/h, so the sulfite concentration in the absorption liquid was set to 0.1 mol/min.
Although a patent application was filed (see Japanese Patent Application No. 50-53151 and Japanese Unexamined Patent Publication No. 51-129866) stating that the sulfite concentration should be less than 0.1 mol/ They discovered that this is sufficient, and that even if more than that amount exists, the effect on the denitrification rate is saturated and is essentially meaningless, leading to the present invention.
以下に本発明の詳細な説明する。The present invention will be explained in detail below.
実施例 ｌ 液容量１ｔの吸収瓶を用いて、ＮＯ１５０ｐｐｍ。Example l NO150ppm using an absorption bottle with a liquid capacity of 1t.
ＳＯ２１，３００ｐ−及びＣＯ２１０係を含む空気混合
ガスを、あら力・じめＣｔＯ２ガスを添加してガス中の
ＮＯを酸化したのち１０１７ｍ１ｎの割合で通気洗浄し
た。An air mixture gas containing SO21,300 p- and CO210 was first added with CtO2 gas to oxidize NO in the gas, and then was vented and cleaned at a rate of 1017 m1n.
吸収瓶の入口及び出口ガス中のＮＯｘ及びＳＯｘ濃度を
、それぞれ、化学発光法及び溶液導電率法による機器で
測定したところ、脱硝率９０％、脱硫率９９．５％であ
った。When the NOx and SOx concentrations in the inlet and outlet gases of the absorption bottle were measured using equipment based on the chemiluminescence method and the solution conductivity method, respectively, the denitrification rate was 90% and the desulfurization rate was 99.5%.
このときの吸収液組成は以下の通りであった。The composition of the absorption liquid at this time was as follows.
Ｎａ２Ｓ２Ｏ３３００ｐｐｍ
ＣＵＣｔ ５ Ｑｐｐｍ（Ｃｕとして）Ｎａ２
ＣＯ３３０００ｐｐ［ｌｌ
Ｎａ２ＳＯ３５００Ｑｐｐｍ
また吸収液のｐＨはＮａＯＨ水溶液を添加して実験中ｐ
Ｈ６，５に保った。Na2S2O3300ppm CUCt 5 Qppm (as Cu) Na2
CO33000pp[ll Na2SO3500Qppm The pH of the absorption liquid was adjusted to pH during the experiment by adding NaOH aqueous solution.
It was kept at H6.5.
実施例 ２
減容量１ｔの吸収瓶を用いて、ＮＯ２０ｏｐｌ）Ｉ［ｌ
。Example 2 Using an absorption bottle with a reduced volume of 1 t, NO20 opl) I[l
.
８０２６００１１１）Ｉ［ｌ及びＣＯ□１０係を含む空
気混合ガスを、あらかじめ０３ガスを添加してガス中の
ＮＯを酸化したのち１０ｔ／ｍｉｎの割合で通気洗浄し
た。802600111) 03 gas was added to the air mixed gas containing 10 parts of I[l and CO□10 to oxidize NO in the gas, and then the air was cleaned at a rate of 10 t/min.
吸収瓶の入口及び出口ガス中のＮＯｘ及びＳＯｘ濃度を
、それぞれ、化学発光法及び溶液導電率法による機器で
測定したところ、脱硝率８９．５％、脱硫率９８．５％
であった。When the NOx and SOx concentrations in the inlet and outlet gases of the absorption bottle were measured using equipment using the chemiluminescence method and the solution conductivity method, respectively, the denitrification rate was 89.5% and the desulfurization rate was 98.5%.
Met.
このときの吸収液組成は以下の通りであった。The composition of the absorption liquid at this time was as follows.
Ｃａ５２０３ １，００ Ｑｐｐｍ
ＣＵＣｔ ３００ｐｐｍ（Ｃｕとして）ＣａＣＯ３
１％
ＣａｓＯ３５００ｐＩＭｎ
また吸収液のｐＨはＣａＣＯ３を添加して実験中ｐＨ５
に保った。Ca5203 1,00 Qppm CUCt 300ppm (as Cu) CaCO3
1% CasO3500pIMn The pH of the absorption solution was adjusted to pH 5 during the experiment by adding CaCO3.
I kept it.
実施例 ３ 減容量１ｔの吸収瓶を用いて、ＮＯ１０ｏｐＩ）ｍ。Example 3 Using an absorption bottle with a reduced capacity of 1 t, NO10opI)m.
５Ｏ２６００１）Ｐ及びＣＯ２１０係を含む空気混合ガ
スを、あらかじめ０３ガスを添加してガス中のＮＯを酸
化したのち１０ Ａ／ｍｉｎの割合で通気洗浄した。03 gas was added in advance to an air mixture gas containing 5O26001)P and CO210 to oxidize NO in the gas, and then the air was cleaned at a rate of 10 A/min.
吸収瓶の入口及び出口ガス中のＮＯｘ及びＳＯｘ濃度を
、それぞ札化学発光法及び溶液導電率法による機器で測
定したところ、脱硝率８９％、脱硫率９８．５％であっ
た。The NOx and SOx concentrations in the inlet and outlet gases of the absorption bottle were measured using instruments using the Fold chemiluminescence method and the solution conductivity method, respectively, and the denitrification rate was 89% and the desulfurization rate was 98.5%.
このときの吸収液組成は以下の通りであった。The composition of the absorption liquid at this time was as follows.
（ＮＨ４）２Ｓ２０３ｓ、ｏ ｏ ｏｐｐｍＣｕＣｔ
５０ｐｐｍ（Ｃｕとして）（ＮＨ４）２
ＣＯ３５％
（ＮＨ４）２Ｓ０３ ７００ｐｐＩｎまた吸収液の
ｐＨはＮ）−Ｉ４０Ｈを添加して実験中ｐＨ８に保った
。(NH4)2S203s, o o oppmCuCt
50ppm (as Cu) (NH4)2
CO35% (NH4)2S03 700ppIn The pH of the absorption liquid was maintained at pH 8 during the experiment by adding N)-I40H.
実施例 ４ 減容量１ｔの吸収瓶を用いて、ＮＯ２３’００ｐｐｍ。Example 4 NO23'00ppm using an absorption bottle with a reduced capacity of 1 ton.
Ｓ ０２１，３０ Ｑｐｐｍ及びＣＯ２１０係を含む空
気混合ガスを、１０ ｔ／ｍｉｎの割合で通気洗浄した
。An air mixed gas containing S 021,30 Qppm and CO210 was aerated and cleaned at a rate of 10 t/min.
吸収瓶の入口及び出口ガス中のＮＯｘ及びＳＯｘ濃度を
、それぞれ、化学発光法及び溶液導電率法による機器で
測定したところ、脱硝率８５係、脱硫率９９．２％であ
った。When the NOx and SOx concentrations in the inlet and outlet gases of the absorption bottle were measured using equipment using a chemiluminescence method and a solution conductivity method, respectively, the denitrification rate was 85% and the desulfurization rate was 99.2%.
このときの吸収液組成は以下の通りであった。The composition of the absorption liquid at this time was as follows.
Ｃａ５２０３ １，００ Ｑｐｐｍ十＋
Ｃｕ −ＥＤＴＡ ５０ｐＩ１ｍ（Ｃｕとし
て）ＣａｃＯ３３００ｐＦ’
ＣａｓＯ３４００ｐＩ）Ｉｌｌ
また吸収液のｐＨはＣａ（ＯＨ）２を添加して実験中ｐ
Ｈ５に保った。Ca5203 1,00 Qppm 10+ Cu -EDTA 50pI1m (as Cu)CacO3300pF' CasO3400pI)Ill The pH of the absorption solution was adjusted to p during the experiment by adding Ca(OH)2.
I kept it at H5.
実施例 ５ 減容量１ｔの吸収瓶を用いて、ＮＮＯ４５０ｐｐ。Example 5 Using an absorption bottle with a reduced capacity of 1 ton, NNO450pp.
ＳＯ□３，０００ｐｐＩｎ及びＣＯ□１０係を含む空気
混合ガスを、あらかじめＣｔＯ２ガスを添加してガス中
のＮＯを酸化したのち１０１７ｍ１ｎの割合で通気洗浄
した。An air mixed gas containing 3,000 ppIn of SO□ and 10 parts of CO□ was preliminarily added with CtO2 gas to oxidize NO in the gas, and then was vented and cleaned at a rate of 1017 m1n.
吸収瓶の入口及び出口ガス中のＮＯｘ及びＳＯｘ濃度を
、それぞれ、化学発光法及び溶液導電率法による機器で
測定したところ、脱硝率８９係、脱硫率９９．５％であ
った。When the NOx and SOx concentrations in the inlet and outlet gases of the absorption bottle were measured using equipment using a chemiluminescence method and a solution conductivity method, respectively, the denitrification rate was 89% and the desulfurization rate was 99.5%.
このときの吸収液組成は以下の通りであった。The composition of the absorption liquid at this time was as follows.
Ｎａ２５２ｏ３ｓ、ｏ ００１）Ｉ”
ＦｅＣ４６０Ｑｐｐｍ（Ｆｅとして）
Ｎａ２ ＣＯ３０，５％
Ｎａ２ＳＯ３３，０００ｐｐｍ
また吸収液のｐＨはＮ ａ ２ ＣＯ３を添加して実験
中ｐＨ６，５に保った。Na252o3s, o 001)I'' FeC460Qppm (as Fe) Na2CO30.5% Na2SO33,000ppm The pH of the absorption liquid was maintained at pH 6.5 during the experiment by adding Na2CO3.
実施例 ６ 減容量１ｔの吸収瓶を用いて、Ｎ０１００Ｏｐｐｌ。Example 6 Using an absorption bottle with a reduced capacity of 1 ton, N0100 Oppl.
ｓｏ２６ｏｏｐｐｍ及びＣＯ２１０係を含む空気混合ガ
スを、あらかじめＣｔｏ２ガスを添加してガス中のＮＯ
を酸化したのち１０１７ｍ１ｎの割合で通気洗浄した。Cto2 gas is added in advance to the air mixture gas containing so26ooppm and CO210 to remove NO in the gas.
was oxidized and then washed through ventilation at a rate of 1017 m1n.
吸収瓶の入口及び出口ガス中のＮＯｘ及びＳＯｘ濃度を
、それぞれ、化学発光法及び溶液導電率法による機器で
測定したところ、脱硝率８８係、脱硫率９８．９％であ
った。When the NOx and SOx concentrations in the inlet and outlet gases of the absorption bottle were measured using equipment using a chemiluminescence method and a solution conductivity method, respectively, the denitrification rate was 88% and the desulfurization rate was 98.9%.
このときの吸収液組成は以下の通りであった。The composition of the absorption liquid at this time was as follows.
チオ尿素 １５０ｐ声
ＣｕＣｔ ５０ｐｐｍ（Ｃｕとして）Ｃａ Ｃ
Ｏ３１％
ＣａＳＯ３５，００Ｑｐｐｍ
また吸収液のｐＨはＣａ Ｃ０３を添加して実験中ｐＨ
６，５に保った。Thiourea 150pCuCt 50ppm (as Cu) Ca C
O31% CaSO35,00Qppm The pH of the absorption solution was adjusted during the experiment by adding CaC03.
I kept it at 6.5.
実施例 ７
減容量１ｔの吸収瓶を用いて、Ｎ０２００ｐ＾５Ｏ２１
，３００泗及びＣＯ２１０係を含む空気混合ガスを、あ
らかじめＣｔＯ２ガスを添加してガス中のＮＯを酸化し
たのち１０１７ｍ１ｎの割合で通気洗浄した。Example 7 Using an absorption bottle with a reduced capacity of 1 t, N0200p^5O21
.
吸収瓶の入口及び出口ガス中のＮＯｘ及びＳＯｘ濃度を
、それぞれ、化学発光法及び溶液導電率法による機器で
測定したところ、脱硝率９３係、脱硫率９８．８％であ
った。When the NOx and SOx concentrations in the inlet and outlet gases of the absorption bottle were measured using equipment using a chemiluminescence method and a solution conductivity method, respectively, the denitrification rate was 93% and the desulfurization rate was 98.8%.
このときの吸収液組成は以下の通りであった。The composition of the absorption liquid at this time was as follows.
チオ尿素 ｓｏｏｐｐｍ
ＣｕＣｔ ６００ｐｐｍ（Ｃｕとして）（Ｎ
Ｈ４）２００３ ０．５係
（ＮＨ４）２ ＳＯ３４，０００ｐｐｍ
また吸収液のｐＨは（ＮＨ４）２ＣＯ３を添加して実験
中ｐＨ５に保った。Thiourea sooppm CuCt 600ppm (as Cu) (N
H4) 2003 0.5 (NH4)2 SO3 4,000 ppm The pH of the absorption liquid was maintained at pH 5 during the experiment by adding (NH4)2CO3.
実施例 ８
液容量１１の吸収瓶を用いて、ＮＯ１００ｐ＾ＳＯ□２
，０００ｐｐＩ［ｌ及びＣＯ２１０係を含む空気混合ガ
スを、あらかじめ０３ガスを添加してガス中のＮＯを酸
化したのち１０ ｔ／ｍｉｎの割合で通気洗浄した。Example 8 Using an absorption bottle with a liquid capacity of 11, NO100p^SO□2
,000 ppI[l and CO210] was added in advance to 03 gas to oxidize the NO in the gas, and then the air was cleaned at a rate of 10 t/min.
吸収瓶の入口及び出口ガス中のＮＯｘ及びＳＯｘ濃度を
、それぞれ、化学発光法及び溶液導電率法による機器で
測定したところ、脱硝率８９％、脱硫率９８．９％であ
った。When the NOx and SOx concentrations in the inlet and outlet gases of the absorption bottle were measured using equipment based on the chemiluminescence method and the solution conductivity method, respectively, the denitrification rate was 89% and the desulfurization rate was 98.9%.
このときの吸収液組成は以下の通りであった。The composition of the absorption liquid at this time was as follows.
チオ尿素 ８，０００ｐｐｍ
ＣｕＣ１５Ｑｐｐｍ（Ｃｕとして）
ＣａＣＯ３４％
ＣａＳＯ３２，００Ｑｐｐｍ
また吸収液のｐＨはＣａ（ＯＨ）２を添加して実験中ｐ
Ｈ８に保った。Thiourea 8,000ppm CuC15Qppm (as Cu) CaCO34% CaSO32,00Qppm The pH of the absorption solution was adjusted by adding Ca(OH)2 during the experiment.
I kept it at H8.
実施例 ９
液容量１ｔの吸収瓶を用いて、Ｎ０２２５０ｐｌ）Ｉｌ
ｌ。Example 9 Using an absorption bottle with a liquid capacity of 1 t, N02250 pl) Il
l.
ＳＯ□ｉ、３ｏｏｐｐｍ及びＣＯ２１０係を含む空気混
合ガスを、１０１−／ｍｉｎの割合で通気洗浄した。An air mixed gas containing SO□i, 3 ooppm and CO210 was aerated and cleaned at a rate of 101-/min.
吸収瓶の入口及び出口ガス中のＮＯｘ及びＳＯｘ濃度を
、それぞれ、化学発光法及び溶液導電率法による機器で
測定したところ、脱硝率８８係、脱硫率９８．６％であ
った。When the NOx and SOx concentrations in the inlet and outlet gases of the absorption bottle were measured using equipment using a chemiluminescence method and a solution conductivity method, respectively, the denitrification rate was 88% and the desulfurization rate was 98.6%.
このときの吸収液組成は以下の通りであった。The composition of the absorption liquid at this time was as follows.
チオ尿素 ４ＱＱｐｐｍ
Ｃｕ”−ＥＤＴＡ ５ ｏｐｐｍ（Ｃｕとして
）Ｃａ ＣＯ３１％
ＣａｓＯ３５，ＯＯＯＩＩＩ）Ｉｎ
また吸収液のｐＨはＣａＣＯ３を添加して実験中ｐＨ５
に保った。Thiourea 4QQppm Cu"-EDTA 5 oppm (as Cu) Ca CO3 1% CasO35, OOOIII) In Also, the pH of the absorption liquid was adjusted to pH 5 during the experiment by adding CaCO3.
I kept it.
実施例 １０
液容量１ｔの吸収瓶を用いて、Ｎ０２４００１］＾Ｓ
０２１，３００ｐｐｍ及びＣＯ２１０係を含む空気混合
ガスを、Ｌｏｔ／ｍｉｎの割合で通気洗浄した。Example 10 Using an absorption bottle with a liquid capacity of 1 t, N024001]^S
An air mixed gas containing 0.21,300 ppm and CO210 was vented and cleaned at a rate of Lot/min.
吸収瓶の入口及び出口ガス中のＮＯｘ及びＳＯｘ濃度を
、それぞれ、化学発光法及び溶液導電率法による機器で
測定したところ、脱硝率８６係、脱硫率９９．３％であ
った。The NOx and SOx concentrations in the inlet and outlet gases of the absorption bottle were measured using equipment using a chemiluminescence method and a solution conductivity method, respectively, and the denitrification rate was 86% and the desulfurization rate was 99.3%.
このときの吸収液組成は以下の通りであった。The composition of the absorption liquid at this time was as follows.
チオ尿素 ８．０００１１迦
ＣｕＳＯ４６０ｏｐｐｍ（Ｃｕとして）
Ｎａ２ ＣＯ３０，５％
Ｎａ２５ｏ３１０，００ ｏｐｐｍ
また吸収液のｐＨはＮａ２ ＣＯ３を添加して実験中ｐ
Ｈ６，５に保った。Thiourea 8.00011 CuSO460oppm (as Cu) Na2CO30.5% Na25O310.00oppm The pH of the absorption solution was adjusted to pH during the experiment by adding Na2CO3.
It was kept at H6.5.
実施例 １１ 液容量１ｔの吸収瓶を用いて、ＮＮＯ４５０ｐｐ。Example 11 NNO450pp using an absorption bottle with a liquid capacity of 1 t.
ｓｏ２６ｏｏｐｐｍ及びＣＯ２１０係を含む空気混合ガ
スを、あらかじめＣｔＯ２ガスを添加してガス中のＮＯ
を酸化したのち１０１７ｍ１ｎの割合で通気洗浄した。CtO2 gas is added to the air mixture gas containing so26ooppm and CO210 to remove NO in the gas.
was oxidized and then washed through ventilation at a rate of 1017 m1n.
吸収瓶の入口及び出口ガス中のＮＯｘ及びＳＯｘ濃度を
、それぞれ、化学発光法及び溶液導電率法による機器で
測定したところ、脱硝率８８％、脱硫率９８．７％であ
った。When the NOx and SOx concentrations in the inlet and outlet gases of the absorption bottle were measured using equipment based on the chemiluminescence method and the solution conductivity method, respectively, the denitrification rate was 88% and the desulfurization rate was 98.7%.
このときの吸収液組成は以下の通りであった。The composition of the absorption liquid at this time was as follows.
チオ尿素 １５０ｐｐｍ
ＦｅＳＯ４６００ｐｐｍ（Ｆｅとして）
（ＮＨ４）２ＣＯ３０，５係
（ＮＨ４）２Ｓ０３ ５，０００ｐｐ［Ｉｌまた吸収液
の田は（Ｎ）Ｌｌ ）２ ＣＯ３を添加して実験中ｐＨ
６，５に保った。Thiourea 150ppm FeSO4600ppm (as Fe) (NH4)2CO30,5 (NH4)2S03 5,000pp [IlAlso, the absorption liquid (N)Ll)2CO3 was added to adjust the pH during the experiment.
I kept it at 6.5.
実施例 １２
液容量１１の吸収瓶を用いて、ＮＯ４００１］ｆｌｌｌ
ｌ。Example 12 Using an absorption bottle with a liquid capacity of 11, NO4001]flll
l.
５Ｏ２６００１）Ｉｌ［＋及びＣＯ２１０係を含む空気
混合ガスをあらかじめＣｔＯ２ガスを添加してガス中の
ＮＯを酸化したのち１０ｔ／ｍｉｎの割合で通気洗浄し
た。CtO2 gas was added in advance to an air mixture gas containing 5O26001)Il[+ and CO210 to oxidize NO in the gas, and then the mixture was cleaned through ventilation at a rate of 10 t/min.
吸収瓶の入口及び出口ガス中のＮＯｘ及びＳＯｘ濃度を
、それぞ札化学発光法及び溶液導電率法による機器で測
定したところ、脱硝率８４％、脱硫率９９．８１％であ
った。The NOx and SOx concentrations in the inlet and outlet gases of the absorption bottle were measured using equipment using the Fold chemiluminescence method and the solution conductivity method, respectively, and the denitrification rate was 84% and the desulfurization rate was 99.81%.
このときの吸収液組成は以下の通りであった。The composition of the absorption liquid at this time was as follows.
チオ尿素 ８００ｐＩＩＩＩＩＦｅ＋＋”−
ＥＤＴＡ ３００ＩＦ（Ｆｅとして）Ｃａ ＣＯ３
６％
ＣａＳＯ３６，００ｏｐｐｔｎ
また吸収液のｐＨはＣａ（ＯＨ）２を添加して実験中ｐ
Ｈ８に保った。Thiourea 800pIIIFe++”-
EDTA 300IF (as Fe) Ca CO3
6% CaSO36,00opptn Also, the pH of the absorption liquid was adjusted to pH during the experiment by adding Ca(OH)2.
I kept it at H8.
実施例 １３ 液容量１１の吸収瓶を用いて、ＮＯ２０Ｑｐｐｍ。Example 13 NO20Qppm using an absorption bottle with a liquid capacity of 11.
Ｓ ０２３，０００ｐｐｍ及びＣＯ□１０係を含む空気
混合ガスを、あらかじめＣｔＯ２ガスを添加してガス中
のＮＯを酸化したのちＬｏｔ／ｍｉｎの割合で通気洗浄
した。An air mixed gas containing 023,000 ppm of S and 10 parts of CO was mixed with CtO2 gas to oxidize NO in the gas, and then was vented and cleaned at a rate of Lot/min.
吸収瓶の人口及び出口ガス中のＮＯｘ及びＳＯｘ濃度を
、それぞれ、化学発光法及び溶液導電率法による機器で
測定したところ、脱硝率９２係、脱硫率９９．７％であ
った。When the concentration of the absorption bottle and the NOx and SOx concentrations in the outlet gas were measured using equipment using a chemiluminescence method and a solution conductivity method, respectively, the denitrification rate was 92% and the desulfurization rate was 99.7%.
このときの吸収液組成は以下の通りであった。The composition of the absorption liquid at this time was as follows.
チオ尿素 ｓｏｏｐｐｍ
ＣｕＣ７５０ｐｐｍ（Ｃｕとして）
Ｃａ ＣＯ３１％
ＣａＳＯ３４，０００ｐＦ’
また吸収液のｐＨはＣａＣＯ３を添加して実験中…５に
保った。Thiourea sooppm CuC750ppm (as Cu) CaCO31% CaSO34,000pF' The pH of the absorption solution was maintained at 5 during the experiment by adding CaCO3.
Claims (1)
金属、アルカリ土類金属又はアンモニウムの水酸化物又
は炭酸塩と、チオ尿素又はアルカリ金属、アルカリ土類
金属若しくはアンモニウムのチオ硫酸塩と、銅イオン及
び鉄イオンのうちの少なくとも一つの金属イオンとを含
み、且つ、前記水酸化物又は炭酸塩と排ガス中の亜硫酸
ガスとの反応で生成する亜硫酸塩濃度が０．１モル／を
未満である、水性洗浄液で洗浄することを特徴とする排
ガス脱硫脱硝方法。1. Exhaust gas containing sulfur oxides and nitrogen oxides is treated with hydroxides or carbonates of alkali metals, alkaline earth metals or ammonium, thiourea or thiosulfates of alkali metals, alkaline earth metals or ammonium, and copper ions. and at least one metal ion of iron ions, and the concentration of sulfite produced by the reaction of the hydroxide or carbonate with sulfite gas in the exhaust gas is less than 0.1 mol/. An exhaust gas desulfurization and denitrification method characterized by cleaning with an aqueous cleaning solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51024985A JPS5912333B2 (en) | 1976-03-10 | 1976-03-10 | Exhaust gas desulfurization and denitrification method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51024985A JPS5912333B2 (en) | 1976-03-10 | 1976-03-10 | Exhaust gas desulfurization and denitrification method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS52108366A JPS52108366A (en) | 1977-09-10 |
| JPS5912333B2 true JPS5912333B2 (en) | 1984-03-22 |
Family
ID=12153263
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP51024985A Expired JPS5912333B2 (en) | 1976-03-10 | 1976-03-10 | Exhaust gas desulfurization and denitrification method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5912333B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR8903470A (en) * | 1988-07-15 | 1990-03-06 | Mo Tabachnaya Fabrika Yava | COMPOSITION AND PROCESS FOR ABSORPTION OF NITROGEN OXIDE FROM TOBACCO SMOKE, FILTER TO PURIFY TOBACCO SMOKE FROM NITROGEN OXIDE AND IMPREGNATION PROCESS FROM A BASE OF A FILTER |
-
1976
- 1976-03-10 JP JP51024985A patent/JPS5912333B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS52108366A (en) | 1977-09-10 |
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