JPH03202124A - Treatment of gas containing nitrogen oxide - Google Patents
Treatment of gas containing nitrogen oxideInfo
- Publication number
- JPH03202124A JPH03202124A JP1340626A JP34062689A JPH03202124A JP H03202124 A JPH03202124 A JP H03202124A JP 1340626 A JP1340626 A JP 1340626A JP 34062689 A JP34062689 A JP 34062689A JP H03202124 A JPH03202124 A JP H03202124A
- Authority
- JP
- Japan
- Prior art keywords
- fluidized bed
- gas
- electrode
- nitrogen oxide
- container
- 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
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000007789 gas Substances 0.000 title claims abstract description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229920000768 polyamine Polymers 0.000 claims abstract description 8
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 7
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 17
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- MDAXKAUIABOHTD-UHFFFAOYSA-N 1,4,8,11-tetraazacyclotetradecane Chemical compound C1CNCCNCCCNCCNC1 MDAXKAUIABOHTD-UHFFFAOYSA-N 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000243 solution Substances 0.000 abstract description 5
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010935 stainless steel Substances 0.000 abstract description 4
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 4
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 239000010949 copper Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 235000010333 potassium nitrate Nutrition 0.000 abstract description 2
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 7
- -1 Nitrate ions Chemical class 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- LBFUKZWYPLNNJC-UHFFFAOYSA-N cobalt(ii,iii) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明（よ Ｎｏ、 ＮＯｅ、ＮａＯ等の一般にＮＯ
，で表わされる窒素酸化物を含むガスの処理方法に関す
る。さらに詳しく（ヨ 環状ポリアミン金属錯体の電
極触媒作用を利用して、常温下で、酸素過剰のガス雰囲
気でｋ 窒素酸化物をアンモニアあるいは窒素まで還元
し無害化する処理方法に関する。[Detailed description of the invention] Industrial application field of the present invention (generally NO, such as NO, NOe, NaO, etc.)
This invention relates to a method for treating gas containing nitrogen oxides represented by . More specifically, it relates to a treatment method for reducing nitrogen oxides to ammonia or nitrogen to render them harmless at room temperature in an oxygen-rich gas atmosphere by utilizing the electrocatalytic action of a cyclic polyamine metal complex.
従来の技術
窒素酸化物（Ｎ０％−）ζ上 家庭風 工業用を問わず
石油ストーブ、ガスコンロ、ボイラー、自動車等の燃焼
器から出る排ガス中に数１０ｐｐｍから数１１０００ｐ
ｐを含まれている。ＮＯｘは人体に有害であるばかりで
なく、Ｎ２０などはＣＯ２と並んで地球の温暖化の原因
の一つで環境保全上も有害なものである。工業的にはア
ンモニアと酸化へ”プシ゛ウム等の金属酸化物よりなる
脱硝触媒を用いる湿式処理が大型の装置を使って行なわ
れている。Conventional technology Nitrogen oxides (N0%-) ζ Above Several tens of ppm to several 11,000 ppm are present in the exhaust gas emitted from combustors of kerosene stoves, gas stoves, boilers, automobiles, etc., whether for home use or industrial use.
Contains p. Not only is NOx harmful to the human body, but N20 and the like are also harmful to the environment, as they are one of the causes of global warming along with CO2. Industrially, a wet process using a denitrification catalyst made of ammonia and a metal oxide such as psium oxide is carried out using large-scale equipment.
また 燃焼の当量点付近の排ガスについてはいわゆる三
元触媒と呼ばれるＣＯとＮＯつと炭化水素（ＨＣ）を同
時に浄化する白金族の触媒を用いて浄化が行なわれてい
る。Furthermore, exhaust gas near the combustion equivalence point is purified using a so-called three-way catalyst, a platinum group catalyst that simultaneously purifies CO, NO, and hydrocarbons (HC).
発明部く解決しようとする課題
しかしなが転 従来 酸素が過剰に存在する場合は ア
ンモニアを用いる脱硝方法以外はＮｏ、をＮ２まで還元
し無害化する有効な方法は見つかっていない。工業用の
燃焼器については大型の装置を設置して脱硝を行うこと
は比較的容易である。しかし 石油ストーブ、ガススト
ーブ等の家庭用の燃焼法 あるいは自動車等では触媒を
入れた反応器の他に薬品の補給装置および補給容器が必
要となる。また 触媒を２００℃以上の高温に保持して
おく必要があり、加熱装置あるいは保温装置が必要で機
器の高コスト化 大型化 高重量化を避けられないとい
う問題があった
本発明（よ 上記問題を解決しようとするもので、燃焼
機器の大型化 高重量化を伴うことなくガス中のＮＯう
をＮ ＨａあるいはＮ２にまで還元 無害化する経済的
に有利な方法を提供するものである。However, there is a problem to be solved by the invention department. Conventionally, when oxygen is present in excess, no effective method has been found to reduce NO to N2 and render it harmless, except for the denitrification method using ammonia. For industrial combustors, it is relatively easy to install large-scale equipment and perform denitrification. However, in household combustion methods such as kerosene stoves and gas stoves, and in automobiles, chemical replenishment equipment and replenishment containers are required in addition to the reactor containing the catalyst. In addition, it is necessary to maintain the catalyst at a high temperature of 200 degrees Celsius or higher, and a heating device or heat insulating device is required, which increases the cost, size, and weight of the equipment. The aim is to provide an economically advantageous method for reducing NO gas in gas to N2Ha or N2, making it harmless, without increasing the size and weight of combustion equipment.
課題を解決するための手段
本発す」ハ 上記問題を解決するもので、環状ポリア
ミン金属錯体 好適に（よ コバルトテトラアザ錯体（
Ｃｏ［Ｉ４］ａｎｅＮ４）あるいはニッケルテトラアザ
錯体（Ｎｉ［１４］ａｎｅＮ４）を含む溶液と金属鏡
金属臥 あるいはそれらの合金粉末を含む流動層に接し
て電解用の電極を設ζす、電解を行いながら窒素酸化物
を含むガスを該流動層中に通じること玄ガス中のＮＯｘ
をＮＨＩあるいはＮ２まで還元す衣薬品の補給 処理装
置の加熱が不要な経済的に有利な窒素酸化物含有ガスの
処理方法を提供するものである。Means for Solving the Problems The present invention proposes a method for solving the above problems, preferably using cyclic polyamine metal complexes (cobalt tetraaza complexes).
A solution containing Co[I4]aneN4) or nickel tetraaza complex (Ni[14]aneN4) and a metal mirror
An electrode for electrolysis is installed in contact with a fluidized bed containing a metal bed or an alloy powder thereof, and a gas containing nitrogen oxides is passed into the fluidized bed while electrolysis is being performed.
Replenishment of coating chemicals that reduce nitrogen oxides to NHI or N2 The present invention provides an economically advantageous method for processing nitrogen oxide-containing gases that does not require heating of processing equipment.
作用
大環状ポリアミンを含む溶液と金属鋺 金属級あるいは
それらの合金粉末を含む流動層中に通じた被処理ガス中
のＮＯ，Ｌｉ 大環状ポリアミン金属錯体を含む溶液
中に溶けて、硝酸イオンあるいは亜硝酸イオンになる。Action: A solution containing a macrocyclic polyamine and a metal spatula.NO, Li in the gas to be treated passed through a fluidized bed containing a metal-grade powder or an alloy powder thereof.Nitrate ions or becomes nitrate ion.
流動層と接するように配置した電極（カソード）に１か
ら２ボルトの電圧を印加しこの溶液を電気分解すると、
この胤 溶液中に含まれている大環状ポリアミンおよび
金属凱金属銀、あるいはそれらの合金粉が電極触媒の作
用をして硝酸イオン（ＮＯｓ −）、亜硝酸イオン（Ｎ
。When a voltage of 1 to 2 volts is applied to an electrode (cathode) placed in contact with the fluidized bed and this solution is electrolyzed,
The macrocyclic polyamine, metallic silver, or their alloy powder contained in this solution acts as an electrode catalyst to produce nitrate ions (NOs -) and nitrite ions (N
.
２−）は次のような反応を経て還元を受けて容易にＮＨ
３あるいはＮ２に変換される。2-) undergoes the following reaction and is easily reduced to NH
3 or N2.
Ｎ０ａ−→ ＮＯ２−−＋ ＮＯ−→ ＮＨ２ＯＨ−
＋ ＮＨｓ （４）ＮＯａ−→ ＮＯ２−→ Ｎｏ
−→ Ｎ２０ ＋Ｎａ （ｂ）電解の副産物とし
てＮＨ３あるいはＮ２の他に水が得られる。この水（戴
アノードで電気分解されて酸素を発生ずる。N0a-→ NO2--+ NO-→ NH2OH-
+ NHs (4) NOa-→ NO2-→ No
-→ N20 +Na (b) In addition to NH3 or N2, water is obtained as a byproduct of electrolysis. This water is electrolyzed at the anode to generate oxygen.
アノードせ酸素と一緒に生成したプロトンはカソードに
おいてＮ０ａ−の還元に利用される。Protons generated together with oxygen at the anode are utilized for reducing N0a- at the cathode.
ガスの処理量に応じて適宜水を外部から供給するだけで
連続的にかつ安定にＮＯ，を還元することができる。実
際に（よ 排ガス中に数％の割合で含まれている水で十
分であり補給をほとんど必要としない。NO can be continuously and stably reduced simply by supplying water from the outside as appropriate depending on the amount of gas to be processed. In fact, only a few percent of water contained in the exhaust gas is sufficient and almost no replenishment is required.
実施例
以下、本発明の実施例により説明する。本発明の電極触
媒にＬｉ Ｎｉ、 Ｃｏ、 Ｃｕ、 Ｃｒ、 Ｈｇ等
の遷移金属原子あるいはＰｔ、 Ｒｈ等の白金族原子を
取り囲むようにアミンの窒素原子が配位した環状ポリア
ミン金属錯体が用いられる。中でＬ サイクラム（ｃｙ
ｃｌａｍ）と呼ばれるシクロアミンが金属原子に配位し
た錯体が用いられる。中心金属がコバルトあるいはニッ
ケルである構造式ｌから４に示されるニッケル（ＩＩ）
−テトラアザ錯体（ｎｉｃｋｅｌ （１１）−１ｅｔ
ｒａ−ａｚａｃｏｍｐｌｅｘｅｓ）あるいはコバルト（
ＩＩ）・テトラアザ錯体（ｃｏｂａｌｔ（Ｉ Ｉ）−ｔ
ｅｔｒａａｚａｃｏｍｐｌｅｘｅｓ）がありこのヘ 構
造式１および２で示されるサイクラム金属錯体が好適に
用いられる。EXAMPLES The present invention will be explained below using examples. For the electrode catalyst of the present invention, a cyclic polyamine metal complex in which nitrogen atoms of an amine are coordinated to surround a transition metal atom such as LiNi, Co, Cu, Cr, or Hg or a platinum group atom such as Pt or Rh is used. Inside L Cyclam (cy
A complex in which a cycloamine called Clam is coordinated to a metal atom is used. Nickel (II) represented by structural formulas 1 to 4 in which the central metal is cobalt or nickel
-tetraaza complex (nickel (11)-1et
ra-aza complexes) or cobalt (
II) Tetraaza complex (cobalt(II)-t
cyclam metal complexes represented by structural formulas 1 and 2 are preferably used.
構造式
％式％
これらのテトラアザ金属錯体ば ボスニッチらによ リ
、 インオーカ゛ニフクケミストリー、 第４ 巻
１１０２ ページ、 １９６５ 年 （Ｂｏｓｎｉ
ｃｈ、 Ｂ ｅｔ、ａｌ、、 Ｉｎｏｒｇ、
Ｃｈｅｍ、、 １９６５．４．１１０２）に報告されて
いる方法により容易に台底することができる。Structural formula % Formula % These tetraaza metal complexes are described by Bosnich et al., Inorganic Chemistry, Vol. 4, p. 1102, 1965.
ch, B et al,, Inorg,
Chem., 1965.4.1102).
これらの金属錯体（上 約１から５ ｍｍｏｌ／１ｉｔ
ｒｅの水溶液として流動層中に添加されも 水溶液には
金属錯体のほかＫＮＯ３等の支持電解質が０．１Ｍ程度
添加されてもよＬｌ 流動層は 金属鍜 金属鉱ある
いはそれらの合金の粉末と、金属錯体の水溶液と被処理
ガスとで構成される。These metal complexes (approximately 1 to 5 mmol/1it
In addition to metal complexes, about 0.1M of supporting electrolyte such as KNO3 may be added to the aqueous solution in the fluidized bed as an aqueous solution of re. It consists of an aqueous solution of a complex and a gas to be treated.
第１図番上 本発明で用いたガス処理装置の一例の概略
図である。８０８４３０ステンレス製の容器ｌの中に
表面をＨｇ Ｃ１ｅでアマルガム化した粒径が０．１ｍ
ｍから０．５ｍｍの銅粉末１００容量部に対して、構造
式２のニッケルサイクラムが１ｍＭ、 ＫＮＯ３を０
．１Ｍ含む水溶液５０容量部を混合し流動層２を形成す
る。絶縁用の厚さ１００ミクロンのポリプロピレン不織
布４で包み込んだ電解用のニッケル鍍金した８０３３０
４ステンレス製の電極３が流動層中に入れられている。FIG. 1 is a schematic diagram of an example of a gas treatment apparatus used in the present invention. 808430 in a stainless steel container
The surface is amalgamated with Hg C1e and the particle size is 0.1m.
For 100 parts by volume of copper powder with a diameter of 0.5 mm from
．． A fluidized bed 2 is formed by mixing 50 parts by volume of an aqueous solution containing 1M. Nickel plated 80330 for electrolytic use wrapped in 100 micron thick polypropylene non-woven fabric 4 for insulation
4 A stainless steel electrode 3 is placed in the fluidized bed.
電極３は中空のパイプでできていも電極３のリング状に
加工された流動層２と接触する部分３ａに法 被処理ガ
スが電極３のパイプ内を通って流動層２中に供給できる
よう小さな穴３ｂが開けられている。被処理ガスが中空
の電極３内を通って供給されないとき（よ 流動層２中
の水溶液のみがポリプロピレン不織布４、およびパイプ
の穴３ｂを通して電極パイプ内に入ってくるように設計
されている。また 水の補給はこの電極パイプを通して
行えるようになっている。Although the electrode 3 is made of a hollow pipe, the ring-shaped part 3a of the electrode 3 that contacts the fluidized bed 2 is made small so that the gas to be treated can pass through the pipe of the electrode 3 and be supplied to the fluidized bed 2. Hole 3b is drilled. When the gas to be treated is not supplied through the hollow electrode 3, the design is such that only the aqueous solution in the fluidized bed 2 enters the electrode pipe through the polypropylene nonwoven fabric 4 and the hole 3b of the pipe. Water can be supplied through this electrode pipe.
被処理ガスを電極３のパイプから流動層２中に供給し金
属錯体の溶けた水溶液と銅粉末とを流動させながら、容
器１がカソードとなるように容器１と電極３の間に約１
〜２ボルトの電圧を印加し電解する。処理済みのガスは
排気パイプ５より容器１の外部に排出される。排液バイ
ブロ（よ 水溶液の抜き取り用および、容器内敵 電極
銅粉末の洗浄用に設けられている。The gas to be treated is supplied from the pipe of the electrode 3 into the fluidized bed 2, and while the aqueous solution containing the metal complex and the copper powder are flowing, a gap of about 1.5 mm is placed between the container 1 and the electrode 3 so that the container 1 serves as a cathode.
Electrolyze by applying a voltage of ~2 volts. The treated gas is discharged to the outside of the container 1 through the exhaust pipe 5. Drainage vibro (equipped for draining aqueous solution and cleaning copper powder inside the container).
〈実施例１〉
５６ｐｐｍの一酸化窒素（ＮＯ）を含む乾燥空気を毎分
５リツトルの割合で、表面をＨｇ Ｃ１２でアマルガム
化した銅粉末的２０ｇと、 １ｍＭの構造式２で表わさ
れるニッケルサイクラムと０．１ＭのＫＮＯａを溶かし
た水溶液１００ｍ１を混合した流動層中に供給しｔも
電極３と容器ｌを市販の単２乾電池（試験中の電圧的
１．６〜１．１ボルト）につなぎ電解を行なった パイ
プ５から排出される処理済みのガス中のＮＯ×濃度を島
津製作所製の化学発光式分析計で測定し１゜
ガスを通じて約２分後にＮＯＸ濃度は０．５ｐｐｍまで
減少し、１７時間処理後においてもＮｏ、濃度はｌｐｐ
ｍ以下であっ１． この迎 水の補線水溶液の抜取り
は行なわなかった また 試験後の水溶液を分析したと
ころアンモニアはほとんど検出されなかった
なれ 以上の処理はすべて室温下で行なわれ処理装置あ
るいは被処理ガスの加熱はしていなし１比較例として、
ニッケルサイクラムを含まない水溶液と銅粉末よりなる
流動層を用いて同様の処理を行なったとこム 処理３０
分後において処理済みのガス中のＮＯｘの濃度がｌｐｐ
ｍを絨毛１時間後には１０ｐｐｍに達した
〈実施例２〉
４．４６ｐｐｍの一酸化窒素（ＮＯ）を含む乾燥空気を
毎分１０リツトルの割金型 表面をＨｇＣ−〇−
１〇−
１２でアマルガム化した銀粉末的２０ｇと、 １ｍＭの
構造式１で表わされるコバルトサイクラムと０゜１Ｍの
ＫＮＯ２を溶かした水溶液１５０ｍ１を混合した流動層
中に供給し？、 電極３と容器１を市販の単２乾電池
（試験中の電圧的１．６〜１．３ボルト）につなぎ電解
を行なっｔラ バイブ５から排出される処理済みのガ
ス中のＮＯ×濃度を島津製作所製の化学発光式分析計で
測定した
ガスを通じて約２分後にＮＯ，濃度は０．３５ ｐｐ
ｒｎまで減少し、１７時間処理後においてもＮＯ×濃度
は０．５ ｐ ｐｍ以下であっｔラ この肌 水の補
線 水溶液の抜取りは行なわなかった また 試験後の
水溶液を分析したところアンモニアが検出された 処理
は室温下で行なりｔも
比較例として、コバルトサイクラムを含まない水溶液と
銀粉末よりなる流動層を用いて同様の処理を行なったと
こ＆ 処理２時間後において処理済みのガス中のＮＯｘ
の濃度が０．５ｐｐｍを絨毛５時間後には２ｐｐｍに達
しｔも
発明の効果
以上のように 本発明によれば 薬品の補線処理装置の
加熱をすることなく、ガス中のＮｏにをＮＨ３あるいは
Ｎ２まで、きわめて経済的に有利な方法で還元すことが
できる。また 本発明の窒素酸化物含有ガス処理方法（
！、家庭用の石油ストン、ガスストーブの排気ガス処理
に用いられる他に 道路トンネノｋ 地下道路等の各種
トンネルにおける自動車排気ガス中に含まれる低濃度の
窒素酸化物を除去するのにも有効に用いることができる
。また 工業用ボイラーの脱硝にも有効に用いることが
できる。<Example 1> Dry air containing 56 ppm of nitric oxide (NO) was added at a rate of 5 liters per minute to 20 g of copper powder whose surface was amalgamated with Hg C12 and 1 mM of nickel cyclizer represented by structural formula 2. 100 ml of an aqueous solution containing ram and 0.1M KNOa was fed into a mixed fluidized bed.
The electrode 3 and the container 1 were connected to a commercially available AA battery (voltage 1.6 to 1.1 volts during the test) and electrolysis was performed.The NOx concentration in the treated gas discharged from the pipe 5 was determined by Shimadzu Corporation. Measured with a chemiluminescence analyzer manufactured by Komatsu, Ltd., the NOx concentration decreased to 0.5 ppm after about 2 minutes through 1° gas, and even after 17 hours of treatment, the NOx concentration remained at 1 ppm.
m or less 1. The auxiliary aqueous solution of this pick-up water was not sampled, and when the aqueous solution was analyzed after the test, almost no ammonia was detected. As a comparison example,
Similar treatment was carried out using a fluidized bed consisting of an aqueous solution containing no nickel cyclam and copper powder. Treatment 30
After 1 minute, the concentration of NOx in the treated gas is lpp
The concentration of m in the villi reached 10 ppm after 1 hour (Example 2) Dry air containing 4.46 ppm of nitric oxide (NO) was heated at 10 liters per minute to the surface of the split mold with HgC-〇-1〇-12. 20g of amalgamated silver powder and 150ml of an aqueous solution containing 1mM of cobalt cyclam represented by structural formula 1 and 0.1M of KNO2 were mixed and fed into a fluidized bed. Electrode 3 and container 1 were connected to a commercially available AA battery (voltage: 1.6 to 1.3 volts during the test), electrolysis was performed, and the NOx concentration in the treated gas discharged from t-Lab Vibe 5 was determined. After about 2 minutes, the NO concentration was 0.35 pp through the gas measured with a Shimadzu chemiluminescence analyzer.
The NOx concentration was below 0.5 ppm even after 17 hours of treatment.The aqueous solution was not sampled.Also, when the aqueous solution was analyzed after the test, ammonia was detected. The treatment was carried out at room temperature, and as a comparative example, the same treatment was carried out using a fluidized bed consisting of an aqueous solution containing no cobalt cyclam and silver powder. of NOx
According to the present invention, the concentration of 0.5 ppm in the villus reaches 2 ppm after 5 hours, which is more than the effect of the invention. Up to N2 can be reduced in a very economically advantageous manner. In addition, the nitrogen oxide-containing gas treatment method of the present invention (
! In addition to being used to treat exhaust gas from household petroleum stones and gas stoves, it is also effectively used to remove low concentrations of nitrogen oxides contained in automobile exhaust gas from various tunnels such as underground roads. be able to. It can also be effectively used for denitrification of industrial boilers.
第１図は本発明の一実施例の処理方法を適用したガス処
理装置の構成国である。FIG. 1 shows the constituent countries of a gas treatment apparatus to which a treatment method according to an embodiment of the present invention is applied.
Claims (3)
属銀、あるいはそれらの合金粉末を含む流動層に接して
電解用の電極を設置け、電解を行いながら窒素酸化物を
含むガスを前記流動層中に通じることを特徴とする窒素
酸化物含有ガスの処理方法。(1) An electrode for electrolysis is installed in contact with a fluidized bed containing a solution containing a cyclic polyamine metal complex and metallic copper, metallic silver, or their alloy powder, and a gas containing nitrogen oxide is flowed while electrolyzing. A method for treating a nitrogen oxide-containing gas, characterized in that it passes into a layer.
の電極として用いることを特徴とする請求項１記載の窒
素酸化物含有ガスの処理方法。(2) The method for treating nitrogen oxide-containing gas according to claim 1, characterized in that at least a part of the container containing the fluidized bed is used as an electrode for electrolysis.
るコバルトテトラアザ錯体（Ｃｏ［１４］ａｎｅＮ＿４
）あるいは構造式２で表わされるニッケルテトラアザ錯
体（Ｎｉ［１４］ａｎｅＮ＿４）であることを特徴とす
る請求項１記載の窒素酸化物含有ガスの処理方法。 構造式 ▲数式、化学式、表等があります▼・・・（１）、 ▲数式、化学式、表等があります▼・・・（２）、 Ｃｏ［１４］ａｎｅＮ＿４：Ｎｉ［１４］ａｎｅＮ＿４(3) The cyclic polyamine metal complex is a cobalt tetraaza complex (Co[14]aneN_4
) or a nickel tetraaza complex (Ni[14]aneN_4) represented by Structural Formula 2. The method for treating a nitrogen oxide-containing gas according to claim 1. Structural formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (1), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (2), Co[14]aneN_4: Ni[14]aneN_4
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1340626A JPH03202124A (en) | 1989-12-29 | 1989-12-29 | Treatment of gas containing nitrogen oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1340626A JPH03202124A (en) | 1989-12-29 | 1989-12-29 | Treatment of gas containing nitrogen oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03202124A true JPH03202124A (en) | 1991-09-03 |
Family
ID=18338778
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1340626A Pending JPH03202124A (en) | 1989-12-29 | 1989-12-29 | Treatment of gas containing nitrogen oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03202124A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100809666B1 (en) * | 2005-01-31 | 2008-03-05 | 재단법인서울대학교산학협력재단 | Redox active porous metal-organic framework coordination polymer and its use for producing Ag nanoparticles |
| CN101822939A (en) * | 2010-04-29 | 2010-09-08 | 上海电力学院 | Absorption liquid of NO in coal-fired flue gas, preparation method and application thereof |
| CN101844033A (en) * | 2010-06-10 | 2010-09-29 | 上海电力学院 | Method and device for removing NO from coal smoke |
| ITRM20110665A1 (en) * | 2011-12-13 | 2013-06-14 | Shap Technology Corp Ltd | METHOD AND ELECTROCHEMICAL PLANT FOR FUMES TREATMENT |
-
1989
- 1989-12-29 JP JP1340626A patent/JPH03202124A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100809666B1 (en) * | 2005-01-31 | 2008-03-05 | 재단법인서울대학교산학협력재단 | Redox active porous metal-organic framework coordination polymer and its use for producing Ag nanoparticles |
| CN101822939A (en) * | 2010-04-29 | 2010-09-08 | 上海电力学院 | Absorption liquid of NO in coal-fired flue gas, preparation method and application thereof |
| CN101844033A (en) * | 2010-06-10 | 2010-09-29 | 上海电力学院 | Method and device for removing NO from coal smoke |
| ITRM20110665A1 (en) * | 2011-12-13 | 2013-06-14 | Shap Technology Corp Ltd | METHOD AND ELECTROCHEMICAL PLANT FOR FUMES TREATMENT |
| WO2013088391A1 (en) * | 2011-12-13 | 2013-06-20 | Wweelab S.R.L. | Electrochemical plant for the treatment of fumes |
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