JPH0487622A - Treatment of nox gas - Google Patents
Treatment of nox gasInfo
- Publication number
- JPH0487622A JPH0487622A JP2203353A JP20335390A JPH0487622A JP H0487622 A JPH0487622 A JP H0487622A JP 2203353 A JP2203353 A JP 2203353A JP 20335390 A JP20335390 A JP 20335390A JP H0487622 A JPH0487622 A JP H0487622A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- nox
- ammonia
- nox gas
- catalyst
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 42
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000007789 gas Substances 0.000 description 43
- 239000003054 catalyst Substances 0.000 description 18
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
Abstract
Description
【発明の詳細な説明】
Ａ、産業上の利用分野
本発明はＮＯｘガスの処理方法に関し、特にディーゼル
機関およびガスタービン原動機の排気ガス中のＮＯｘガ
スの処理方法に関する。DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to a method for treating NOx gas, and particularly to a method for treating NOx gas in exhaust gas from diesel engines and gas turbine prime movers.
Ｂ０発明の概要
本発明はＮＯｘガスの処理方法において、アジ化ナトリ
ウムを触媒としてＮＯｘガスをアンモニアと反応させる
ことにより、
ＮＯｘガスを低減することを可能とする。B0 Summary of the Invention The present invention makes it possible to reduce NOx gas by reacting NOx gas with ammonia using sodium azide as a catalyst in a method for treating NOx gas.
Ｃ３従来の技術
従来、Ｎ Ｏｘガス処理は排煙脱硝技術として実用化さ
れている。排煙脱硝方法としては乾式法と湿式法に大別
され、最も進んでいるのは乾式法の選択接触還元法であ
る。この方法の利点としては次の３点が挙げられる。C3 Prior Art Conventionally, NOx gas treatment has been put to practical use as a flue gas denitrification technology. Flue gas denitrification methods are broadly divided into dry methods and wet methods, and the most advanced dry method is the selective catalytic reduction method. This method has the following three advantages.
（１）システムが簡単である。(1) The system is simple.
（２）高脱硝率が可能である。(2) High denitrification rate is possible.
（３）ＮＯｘが無害なＮ、とＨ，０に分解され排出処理
等が不要である。(3) NOx is decomposed into harmless N, H, and 0, eliminating the need for discharge treatment.
この選択接触還元法では還元剤としてアンモニア、炭化
水素、−酸化炭素が使用されている。この中でアンモニ
アは酸素が共存していても選択的にＮＯｘと反応するが
他の還元剤は酸素と反応する。このため特にディーゼル
およびガスタービン原動機の場合は酸素が共存していて
も選択的にＮＯｘと反応するアンモニアガスが用いられ
ている。In this selective catalytic reduction method, ammonia, hydrocarbons, and carbon oxides are used as reducing agents. Among these, ammonia selectively reacts with NOx even in the presence of oxygen, while other reducing agents react with oxygen. For this reason, particularly in the case of diesel and gas turbine engines, ammonia gas is used, which selectively reacts with NOx even if oxygen is present.
また、この反応に使用する触媒としてはＰｔなどの貴金
属系やＡ １ ｙｏ３． Ｔ ｉ Ｏｔなどに担持させ
た各種金属酸化物などが挙げられる。ディーゼルおよび
ガスタービン原動機の燃焼で生成するＮＯｘの成分はほ
とんどがＮｏでありＮＯ，は５％程度である。このため
Ｎｏをアンモニアガスと混合させて、この混合気体を触
媒上で接触還元させてＮ、とＨｙ Ｏに分解している。In addition, the catalyst used for this reaction may be a noble metal such as Pt or A 1 yo3. Examples include various metal oxides supported on T i Ot and the like. The component of NOx generated by combustion in diesel and gas turbine prime movers is mostly No, and NO is about 5%. For this purpose, No is mixed with ammonia gas, and this gas mixture is catalytically reduced on a catalyst to be decomposed into N and Hy 2 O.
Ｄ６発明が解決しようとする課題
しかしながら、上記反応式で示した選択的接触還元法で
は次に示すような問題点があった。D6 Problems to be Solved by the Invention However, the selective catalytic reduction method shown in the above reaction formula has the following problems.
（１）アンモニアガスによる還元触媒性能が劣化する。(1) The performance of the reduction catalyst caused by ammonia gas deteriorates.
特に還元触媒は排気されるガス成分によっても劣化する
ため、交換等を必要としてその操作が面倒であるばかり
でなく、触媒に要する費用も割高となっている。In particular, since the reduction catalyst deteriorates due to the exhaust gas components, it is not only difficult to operate as it requires replacement, but also the cost required for the catalyst is relatively high.
（２）使用温度の範囲が制限される。(2) The operating temperature range is limited.
即ち、高温（１０００℃程度）では触媒酸分の焼結が進
行し、結晶の相転移により触媒性能が劣化する。また、
３２０℃以下ではアンモニアガスと水分がＳＯｘを含む
排気ガスと反応して酸性硫安などの化合物を生じ、脱硝
性能の低下を生じる。That is, at high temperatures (approximately 1000° C.), sintering of the catalyst acid proceeds and the catalyst performance deteriorates due to crystal phase transition. Also,
At temperatures below 320° C., ammonia gas and moisture react with exhaust gas containing SOx to produce compounds such as acidic ammonium sulfate, resulting in a decrease in denitrification performance.
これらのことから、従来の還元法の使用温度の範囲は３
２０〜４５０℃であった。従って使用温度範囲が制限さ
れると共に常温での使用が困難であった。For these reasons, the operating temperature range for the conventional reduction method is 3.
The temperature was 20-450°C. Therefore, the temperature range in which it can be used is limited, and it is difficult to use it at room temperature.
（３）処理装置全体の小型化が困難である。(3) It is difficult to downsize the entire processing device.
このことは、上記反応式からＮＯｘの還元反応は等モル
であるため、脱硝率に合わせてＮＯｘ量にほぼ等しいア
ンモニアガスを排気ガス中へ注入しなければならず、そ
のためアンモニアガスボンベ、触媒等が大型となり装置
全体の小型化が困難なためである。This means that from the above reaction equation, the reduction reaction of NOx is equimolar, so ammonia gas that is approximately equal to the amount of NOx must be injected into the exhaust gas in accordance with the denitrification rate, and therefore the ammonia gas cylinder, catalyst, etc. This is because the size of the device makes it difficult to downsize the entire device.
従って本発明はこのような問題点を解決するために創案
されたものであって、
アジ化ナトリウムを触媒としてＮＯｘガスをアンモニア
と反応させることにより、
ＮＯｘガスを低減でき、かつアンモニアによる触媒性能
の劣化を防止し、常温での使用を可能とすると共に処理
装置全体の小型化を可能とすることを目的とする。Therefore, the present invention was devised to solve these problems. By reacting NOx gas with ammonia using sodium azide as a catalyst, NOx gas can be reduced, and the catalyst performance can be improved by ammonia. The purpose is to prevent deterioration, enable use at room temperature, and downsize the entire processing device.
Ｅ１課題を解決するための手段及び作用本発明者らは上
記問題点を解決すべく鋭意研究した結果、ｐｔなどの貴
金属系および各種金属酸化物などの触媒に代えてアジ化
ナトリウムを触媒として用い、ＮＯｘガスをアンモニア
と反応させることにより、高いＮＯｘガス処理率を達成
できることを見い出し、ＮＯｘガスの処理方法を完成し
た。E1 Means and Action for Solving Problems The present inventors have conducted intensive research to solve the above problems, and as a result, we have found that sodium azide is used as a catalyst in place of noble metal catalysts such as PT and various metal oxides. discovered that a high NOx gas treatment rate could be achieved by reacting NOx gas with ammonia, and completed a NOx gas treatment method.
即ち、本発明に係るＮＯｘガスの処理方法は、アンモニ
ア及びアジ化ナトリウムを溶解した水溶液にＮＯｘガス
を導入し、該ＮＯｘガスと前記アンモニアを反応させて
、前記ＮＯｘガスを還元除去することを、その解決手段
としている。That is, the method for treating NOx gas according to the present invention includes introducing NOx gas into an aqueous solution in which ammonia and sodium azide are dissolved, and causing the NOx gas and the ammonia to react to reduce and remove the NOx gas. This is the solution.
以下、本発明について更に詳細に説明する。The present invention will be explained in more detail below.
本発明に係る方法は特に理論にこだわるつもりはないが
、アンモニア水にアジ化ナトリウムを溶解し、この水溶
液とＮＯｘガスとの反応でＮＯｘをＮ２＋Ｈ２０に化学
的に変えることをその原理とする。Although the method according to the present invention is not intended to be particular about theory, its principle is to dissolve sodium azide in aqueous ammonia and chemically convert NOx into N2+H20 through a reaction between this aqueous solution and NOx gas.
即ち、この反応は次の２つの式から説明される。That is, this reaction is explained by the following two equations.
４ Ｎ Ｏ＋ ４ Ｎ Ｈ３＋ ０２ → ４Ｎ
２＋６Ｈ２０（ＮａＮｓ）
・・・・・・（１）
２ＮＯ２＋４ＮＨ３＋０２ → ３Ｎ２＋６Ｈ２０
（Ｎ ａ Ｎ３）
・・・・・・（２）
アジ化ナトリウムは上記（１）及び（２）式の反応を促
進する触媒として作用する。このアジ化ナトリウムの触
媒作用によりＮＯｘガスの成分であるＮｏとＮＯ２を酸
素の存在下でＮ２とＮ２０に分解する。4 N O+ 4 N H3+ 02 → 4N
2+6H20 (NaNs) ・・・・・・(1) 2NO2+4NH3+02 → 3N2+6H20
(N a N3) (2) Sodium azide acts as a catalyst to promote the reactions of formulas (1) and (2) above. Due to the catalytic action of this sodium azide, No and NO2, which are components of NOx gas, are decomposed into N2 and N20 in the presence of oxygen.
こうして処理されたＮ２を処理ガスとして排出する。The N2 treated in this way is discharged as a treatment gas.
なお本発明に係る処理方法を好適に実施し得る装置とし
てスクラバ一方式による装置等が挙げられる（特願平第
２−２９２５５号、特願平第２−６８９０５号、特願平
第２−６８９０６号）。Incidentally, as an apparatus that can suitably carry out the treatment method according to the present invention, there can be mentioned an apparatus with one type of scrubber, etc. issue).
Ｆ、実施例
以下、本発明に係るＮＯｘガスの処理方法の詳細な説明
を図面と共に実施例に基づいて説明する。F. Examples Hereinafter, a detailed explanation of the NOx gas treatment method according to the present invention will be explained based on examples together with drawings.
第１図において、１はスクラバ一方式の反応筒、２は混
合気体（ＮＯｘ、酸素等）を導入する導入管、３はらせ
ん状に形成されたハネ、４は混合気体の吹き出し口、５
はＮ２の排気口、６はＮＯｘ濃度分析計をそれぞれ示す
。In Fig. 1, 1 is a scrubber-type reaction cylinder, 2 is an introduction pipe for introducing a mixed gas (NOx, oxygen, etc.), 3 is a spiral shaped wing, 4 is a mixed gas outlet, 5
6 indicates an N2 exhaust port, and 6 indicates a NOx concentration analyzer.
■ まず、アンモニア（２８％）水２００ｍ／にＮａＮ
、を１．５ｇ溶解し、この水溶液をスクラバ一方式中の
反応筒１に注入した。■ First, add ammonia (28%) to 200 m of water with NaN
, was dissolved, and this aqueous solution was injected into the reaction column 1 in one type of scrubber.
■ 次に、この水溶液中にＮＯｘガス（７３０ｐｐｍ）
を導入し、ＮＯｘガス脱硝反応を行った。■ Next, NOx gas (730 ppm) is added to this aqueous solution.
was introduced to perform a NOx gas denitrification reaction.
■ 更にこの反応により発生する気体をＮＯｘ濃度分析
計６（島津製作所製：島津ポータプルＮＯｘ分析計Ｎ０
Ａ−３０５形）で測定した。■ Furthermore, the gas generated by this reaction is measured using a NOx concentration analyzer 6 (manufactured by Shimadzu Corporation: Shimadzu Portable NOx Analyzer N0).
A-305 type).
■ その測定結果を表１に示す。表１に示すようにアン
モニア水にアジ化ナトリウムを溶解した水溶液にＮＯｘ
ガス（７３０ｐｐｍ）を導入することにより４００ｐｐ
ｍまでＮＯｘガスを低減できたことがわかる。なお、こ
の値は大気汚染防止法で定められている窒素酸化物排出
基準値を大幅に下回るものである。■ The measurement results are shown in Table 1. As shown in Table 1, NOx was added to an aqueous solution of sodium azide dissolved in ammonia water.
400pp by introducing gas (730ppm)
It can be seen that NOx gas was reduced by up to m. Note that this value is significantly lower than the nitrogen oxide emission standard set by the Air Pollution Control Law.
表１ アンモニア水及びアジ化ナトリウムを用いたＮＯ
ｘガスの処理方法
Ｇ９発明の効果
本発明は上述のように構成されているので、次に記載す
る効果を奏する。Table 1 NO using ammonia water and sodium azide
x Gas Processing Method G9 Effects of the Invention Since the present invention is configured as described above, it produces the following effects.
（１）本発明に係る方法によれば、触媒としてアジ化ナ
トリウムを用いることにより、アンモニアとＮＯｘガス
の反応を促進でき、窒素酸化物排出基準値に比し著しく
ＮＯｘを低減できる。(1) According to the method of the present invention, by using sodium azide as a catalyst, the reaction between ammonia and NOx gas can be promoted, and NOx can be significantly reduced compared to the nitrogen oxide emission standard value.
（以下余白）
（２）本発明に係る方法によれば、各種金属触媒を用い
ないので、アンモニアによる触媒性能の劣化を防止でき
、これにより長時間、安定的にＮＯｘガスの処理を行う
ことができる。(Blanks below) (2) According to the method of the present invention, since various metal catalysts are not used, deterioration of catalyst performance due to ammonia can be prevented, and as a result, NOx gas can be treated stably for a long period of time. can.
（３）本発明に係る方法によれば、各種金属触媒を必要
としないことから処理装置全体を小型化でき、その操作
も簡便化できると共にコストの低減につながる。(3) According to the method according to the present invention, since various metal catalysts are not required, the entire processing apparatus can be downsized, its operation can be simplified, and costs can be reduced.
（４）本発明に係る方法によれば、室温でＮＯｘガスの
還元反応が可能となり、加熱するための装置等が不要と
なりＮＯｘガスの処理を容易に行うことかできる。(4) According to the method according to the present invention, the reduction reaction of NOx gas can be carried out at room temperature, and a heating device or the like is not required, making it possible to easily process NOx gas.
第１図はスクラバ一方式ＮＯｘガス処理装置を示す概略
構成図である。
１・・・スクラバ一方式による反応筒、２・・・ＮＯｘ
ガス導入管、３・・・らせん状に形成されたハネ、４、
・・ＮＯｘガス吹き出し口、５・・・処理ガスの排気口
、６・・・ＮＯｘｍ度分析計。FIG. 1 is a schematic configuration diagram showing a one-type scrubber NOx gas treatment apparatus. 1... Reaction tube with one type of scrubber, 2... NOx
Gas introduction pipe, 3...spiral shaped spring, 4,
...NOx gas outlet, 5...processing gas exhaust port, 6...NOxm degree analyzer.
Claims (1)
液にＮＯ＿ｘガスを導入し、該ＮＯ＿ｘガスと前記アン
モニアを反応させて、前記ＮＯ＿ｘガスを還元除去する
ことを特徴とするＮＯ＿ｘガスの処理方法。(1) A method for treating NO_x gas, which comprises introducing NO_x gas into an aqueous solution in which ammonia and sodium azide are dissolved, and reacting the NO_x gas with the ammonia to reduce and remove the NO_x gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2203353A JP2864689B2 (en) | 1990-07-31 | 1990-07-31 | NOx gas treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2203353A JP2864689B2 (en) | 1990-07-31 | 1990-07-31 | NOx gas treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0487622A true JPH0487622A (en) | 1992-03-19 |
| JP2864689B2 JP2864689B2 (en) | 1999-03-03 |
Family
ID=16472626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2203353A Expired - Lifetime JP2864689B2 (en) | 1990-07-31 | 1990-07-31 | NOx gas treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2864689B2 (en) |
-
1990
- 1990-07-31 JP JP2203353A patent/JP2864689B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2864689B2 (en) | 1999-03-03 |
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