JPH02214524A - Method for removing nitrogen oxide - Google Patents
Method for removing nitrogen oxideInfo
- Publication number
- JPH02214524A JPH02214524A JP1038102A JP3810289A JPH02214524A JP H02214524 A JPH02214524 A JP H02214524A JP 1038102 A JP1038102 A JP 1038102A JP 3810289 A JP3810289 A JP 3810289A JP H02214524 A JPH02214524 A JP H02214524A
- Authority
- JP
- Japan
- Prior art keywords
- exhaust gas
- nox
- gas
- gaseous
- reaction
- 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
- 238000000034 method Methods 0.000 title claims abstract description 42
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 21
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract 7
- 239000007789 gas Substances 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 239000003054 catalyst Substances 0.000 abstract description 10
- 230000002829 reductive effect Effects 0.000 abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 abstract 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000010531 catalytic reduction reaction Methods 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000002250 progressing effect Effects 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RRKTZKIUPZVBMF-IBTVXLQLSA-N brucine Chemical compound O([C@@H]1[C@H]([C@H]2C3)[C@@H]4N(C(C1)=O)C=1C=C(C(=CC=11)OC)OC)CC=C2CN2[C@@H]3[C@]41CC2 RRKTZKIUPZVBMF-IBTVXLQLSA-N 0.000 description 1
- RRKTZKIUPZVBMF-UHFFFAOYSA-N brucine Natural products C1=2C=C(OC)C(OC)=CC=2N(C(C2)=O)C3C(C4C5)C2OCC=C4CN2C5C31CC2 RRKTZKIUPZVBMF-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- BMNDJWSIKZECMH-UHFFFAOYSA-N nitrosyl bromide Chemical compound BrN=O BMNDJWSIKZECMH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment 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］
この発明は、石炭、石油、天然ガスなどの燃焼ボイラ、
各種加熱炉、産業廃棄物や都市ごみなどの焼却炉、さら
には固定の内燃機関や、自動車エンジンのような移動の
内燃機関などの各種排ガス中に含まれる窒素酸化物（Ｎ
ＯＸ）を無触媒下で乾式で効果的に除去する方法に関す
る。[Detailed Description of the Invention] [Industrial Application Field] This invention is applicable to combustion boilers for coal, oil, natural gas, etc.
Nitrogen oxides (N
The present invention relates to a method for effectively dry removing OX) without a catalyst.
［従来技術およびその問題点］
排ガス中のＮＯｘを除去する方法としては、すでに様々
なものが提案され、現実に多くの実用装置が稼動してい
る。ＮＯｘの除去技術は大きくは乾式法と湿式法に分け
られる。前者はさらに触媒法と無触媒法に分けられ、触
媒法の実用装置が最も多く稼動している。とりわけ、還
元剤としてアンモニア（ＮＨａ）を使用するいわゆるＮ
Ｈ，選択触媒還元法が主流である。ＮＨ３選択触媒還元
法は排ガス中に酸素（０２）が存在している状態でも、
ＮＯｘを効果的に還元除去できるので、比較的有利な方
法である。[Prior art and its problems] Various methods have already been proposed for removing NOx from exhaust gas, and many practical devices are actually in operation. NOx removal techniques can be broadly divided into dry methods and wet methods. The former is further divided into catalytic and non-catalytic methods, and the catalytic method has the most practical equipment in operation. In particular, the so-called N
H, selective catalytic reduction method is mainstream. The NH3 selective catalytic reduction method works even when oxygen (02) is present in the exhaust gas.
This is a relatively advantageous method because NOx can be effectively reduced and removed.
それでも、触媒費、装置費などに多額の費用を要し、そ
のため安価で運転容易な方法の開発が望まれている。Even so, a large amount of cost is required for catalysts, equipment, etc., and therefore there is a desire to develop a method that is inexpensive and easy to operate.
還元剤としてＮＨ，以外に一酸化炭素（ＣＯ）あるいは
水素（Ｈ２）を使用する触媒法がある。There is a catalytic method that uses carbon monoxide (CO) or hydrogen (H2) in addition to NH as a reducing agent.
しかし、これらの方法は、排ガス中に０２が存在する場
合には、ＣＯあるいはＨ２がＮＯｘと反応するよりも０
２と優先的に反応するために多大の還元剤を必要とし、
実用的な方法ではない。ボイラ排ガスなど０２を含むガ
ス系では、ＮＯｘを選択的に還元除去できることが最も
重要な条件である。However, in these methods, when 02 is present in the exhaust gas, the amount of 0
Requires a large amount of reducing agent to react preferentially with 2,
It's not a practical method. In a gas system containing 02 such as boiler exhaust gas, the most important condition is that NOx can be selectively reduced and removed.
自動車のガソリンエンジンの排ガス処理では、排ガス中
に０２がほとんどなく、逆に還元剤としてのＣＯＳＨ２
、炭化水素が過剰に含まれているため、三元触媒と呼ば
れる白金触媒に排ガスを通すだけでＮＯｘ除去が達成さ
れる。しかし、この場合でも、白金触媒が高価であるこ
とや、同触媒が有鉛ガソリン車には適用できないなどの
問題が残っている。鉛は触媒毒であるため、日本では無
鉛ガソリンが普及しているが、世界的にはガソリンの無
鉛化は進んでおらず、有鉛ガソリン車に対するＮＯｘ除
去対策が望まれるところである。In the exhaust gas treatment of automobile gasoline engines, there is almost no 02 in the exhaust gas, and on the contrary, COSH2 as a reducing agent.
Since the exhaust gas contains an excess of hydrocarbons, NOx removal can be achieved simply by passing the exhaust gas through a platinum catalyst called a three-way catalyst. However, even in this case, problems remain, such as the high cost of platinum catalysts and the inability to apply them to leaded gasoline vehicles. Since lead is a catalyst poison, unleaded gasoline is popular in Japan, but lead-free gasoline is not progressing around the world, and measures to remove NOx from leaded gasoline vehicles are desired.
現在、その処理対策が最も困難とされているのは、ヂー
ゼルエンジンの排気ガスである。これは、排ガス中に０
２が存在し、ＮＯｘ濃度も高いためで、有効な対策は皆
無と言ってよい。Currently, it is diesel engine exhaust gas that is considered to be the most difficult to treat. This means 0 in the exhaust gas.
2 exists and the NOx concentration is high, so it can be said that there are no effective countermeasures.
したがって、ＮＨ３による選択触媒還元法をこの種の移
動発生源に適用することは、技術的にも経済的にも問題
がある。Therefore, the application of selective catalytic reduction with NH3 to this type of mobile source is technically and economically problematic.
一方、無触媒の条件下、１０００℃付近の高温排ガス中
にＮＨ３を注入して脱硝するいわゆる無触媒脱硝法が知
られている。ただし、この方法は最適温度域が狭く、脱
硝率も５０％以下であり、実用上は限定された用途にし
か用いられていない。On the other hand, a so-called non-catalytic denitrification method is known in which NH3 is injected into high-temperature exhaust gas at around 1000° C. to denitrate the exhaust gas under non-catalytic conditions. However, this method has a narrow optimum temperature range and a denitrification rate of less than 50%, so it is practically used only for limited purposes.
湿式法についてもまた多くの研究例があるが、はとんど
実用化されていない。これは、ＮＯｘが各種水溶液のい
ずれに対しても極めて低い反応性しか示さず、また水に
対する溶解度も低いためである。勿論、湿式法では排水
処理の問題があり、排ガスが降温するのに伴って白煙が
発生する可能性もあるため、湿式法は乾式法はど普及し
ていないこともある。There are also many examples of research on wet methods, but they have hardly been put into practical use. This is because NOx exhibits extremely low reactivity with any of various aqueous solutions and also has low solubility in water. Of course, the wet method has problems with wastewater treatment, and white smoke may be generated as the temperature of the exhaust gas decreases, so the wet method is not as popular as the dry method.
以上述べたように、排ガス脱硝における従来技術では、
乾式法で０２を含む排ガス処理が可能なＮＨ３還元法の
研究が進んでいるが、まだ多くの問題を残している。理
想的な脱硝法は、触媒を使用せず、乾式法でしかも比較
的低い温度域で高い脱硝率が得られる方法であり、この
ような方法の開発が強く要望せられている。As mentioned above, in the conventional technology for exhaust gas denitrification,
Research is progressing on the NH3 reduction method that can treat exhaust gas containing 02 using a dry method, but many problems still remain. The ideal denitrification method is a dry method that does not use a catalyst and can achieve a high denitrification rate at a relatively low temperature range, and there is a strong demand for the development of such a method.
［問題点の解決手段］
この発明による排ガス中のＮＯｘ除去法は、極めて簡単
な手段および方法でありながら多大の効果を奏するもの
で、低濃度のＮＯｘから高濃度のＮＯｘまで完全に処理
無害化することができる。[Means for solving the problem] The method for removing NOx from exhaust gas according to the present invention is an extremely simple means and method, but has great effects, and can completely treat and detoxify everything from low-concentration NOx to high-concentration NOx. can do.
具体的には、この発明による方法は、処理すべき排ガス
中に臭素ガス（Ｂ ｒ２）をＮＨ３ガスを添加すること
を特徴とするものである。Specifically, the method according to the invention is characterized in that bromine gas (Br2) and NH3 gas are added to the exhaust gas to be treated.
このように排ガス中にＢｒ２ガスとＮＨ，ガスを添加す
ることの効果は劇的なものであって、ＮＯｘの低濃度領
域から高濃度領域まで８０％以上という高効率でＮＯｘ
の除去が達成される。The effect of adding Br2 gas, NH, and gas to the exhaust gas is dramatic, with a high efficiency of over 80% from the low NOx concentration region to the high NOx concentration region.
is achieved.
特に顕著な効果ないし特徴とするところは、つぎのとお
りである。第１に、従来の乾式ＮＨ３選択触媒還元脱硝
法とは異なり、触媒を全く必要とせず、完全に気相中で
ＮＯｘの還元除去反応が進行する。第２には、ｏ２が多
量に存在する排ガス系で選択的にＮＯｘが還元除去され
る。Particularly notable effects or features are as follows. First, unlike the conventional dry NH3 selective catalytic reduction denitrification method, no catalyst is required, and the NOx reduction reaction proceeds completely in the gas phase. Secondly, NOx is selectively reduced and removed in the exhaust gas system where a large amount of O2 exists.
第３には、前述の乾式ＮＨ３選択触媒還元脱硝法が通常
３００′℃以上４５０℃位の反応温度を必要とするのに
対して、この発明の方法では常温ないしは７０℃以上の
温度域でＮＯｘの還元除去が達成できる。Thirdly, while the dry NH3 selective catalytic reduction denitrification method described above usually requires a reaction temperature of 300'C to 450C, the method of this invention can reduce NOx in the temperature range of room temperature to 70C or more. Reductive removal of can be achieved.
このような観点から、この発明によるＮＯｘ除去方法は
、従来の方法とは全く技術思想を異にするものであると
言える。その反応機構は完全には解明されていないが、
次のような反応を経過するものと考えられる。From this point of view, it can be said that the NOx removal method according to the present invention has a completely different technical idea from conventional methods. Although the reaction mechanism is not completely elucidated,
It is thought that the following reaction occurs.
ＮＯ＋ｌ／２ Ｂ ｒ２ ＮＯＢ ｒ−・−−−−
（１）ＮＯＢｒ＋ＮＨ３→
Ｎ２ ＋ ＨＢ ｒ ＋ Ｈ２０・”−−（２）ＨＢｒ
＋ＮＨ３→ＮＨ４Ｂｒ・・・・・・・・・（３）上記反
応式（１）はＮｏとＢｒ２の反応を示し、これは氷点以
下の温度域でも進行するものである。そして、こうして
生成したＮ０Ｂｒは、反応式（２）で示すように、ＮＨ
３によって還元される。この時、ＨＢｒも同時に生成さ
れるが、これは反応式（３）で示すように過剰のＮＨ３
と反応し、ＮＨ４Ｂｒを生成する。したがって、全体で
は、（１） 、（２） 、 （１）式を加算することに
よって、つぎの（４）式が得られる。NO+l/2 B r2 NOB r-・----
(1) NOBr+NH3→ N2 + HB r + H20・”--(2) HBr
+NH3→NH4Br (3) The above reaction formula (1) shows the reaction between No and Br2, which proceeds even in a temperature range below the freezing point. Then, the N0Br generated in this way is converted into NH
It is reduced by 3. At this time, HBr is also produced at the same time, but this is due to excess NH3 as shown in reaction formula (3).
reacts with and produces NH4Br. Therefore, in total, the following equation (4) is obtained by adding equations (1), (2), and (1).
Ｎ Ｏ＋ ｌ／２ Ｂ ｒ ２ ＋ ２ Ｎ Ｈａ→Ｎ
２ ＋ Ｈ２０＋ Ｎ Ｈ４Ｂ ｒ・・・・・・（４）
反応機構的には、下記式（５） （６）で示すように、
容易にＮ２とＮ２０を生成する性質を有するＮＨ４Ｎｏ
２の存在を中間体として考えねばならないかもしれない
。N O+ l/2 B r 2 + 2 N Ha→N
2 + H20+ N H4B r...(4)
In terms of reaction mechanism, as shown in the following formulas (5) and (6),
NH4No, which has the property of easily generating N2 and N20
We may have to consider the existence of 2 as an intermediate.
ＮＯＢ ｒ＋ＮＨ３＋Ｈ２０→
ＮＨ４ＮＯ２＋ＨＢ ｒ・・・・・・・・・（５）ＮＨ
４ＮＯ２→Ｎ２ ＋２Ｈ２０・・・・・・（６）これら
の反応は、２０℃付近のいわゆる常温から数１００℃に
達する温度までの非常に広い温度域で起こる。ただし、
低温度域での脱硝反応はＮ０Ｂｒの生成、中間生成物と
してのＮＨ４Ｎｏ２の生成は起るが、ＮＨ４ＮＯ２のＮ
２およびＨ２０への分解速度が遅いかもしれない。NOB r+NH3+H20→ NH4NO2+HB r・・・・・・・・・(5)NH
4NO2→N2 +2H20 (6) These reactions occur in a very wide temperature range from so-called normal temperature around 20°C to temperatures reaching several 100°C. however,
In the denitrification reaction in the low temperature range, N0Br is produced and NH4No2 is produced as an intermediate product, but N of NH4NO2
The rate of decomposition to 2 and H20 may be slow.
ＮＨ４ＮＯ２の効果的な分解は５０℃以上、好ましくは
７０℃以上である。高温度域でのＮ。Effective decomposition of NH4NO2 is at temperatures above 50°C, preferably above 70°C. N in high temperature range.
Ｘ除去率の低下は、下記式（７） （８）で示すような
ＮＨ３の酸化による還元剤の不足ないしは新たなＮＯｘ
の生成によるものと思われる。The decrease in the X removal rate is due to the lack of reducing agent due to oxidation of NH3 or the addition of new NOx, as shown in equations (7) and (8) below.
This is thought to be due to the generation of
４ＮＨ３＋３０２→
２Ｎ２ ＋６Ｈ２０・・・・・・・・・・・・（７）４
ＮＨ３＋５０２→
４ＮＯ＋６Ｈ２０・・・・・・・・・・・・（８）すな
わち、高温度域では還元反応速度は早くなるが、ＮＨ，
不足のために全体としてはＮＯＸ除去率は低下する。4NH3+302→ 2N2 +6H20・・・・・・・・・・・・(7)4
NH3 + 502 → 4NO + 6H20 (8) In other words, the reduction reaction rate becomes faster in the high temperature range, but NH,
Due to the shortage, the NOX removal rate decreases as a whole.
Ｂｒ２ガスおよびＮＨ３ガスの添加量は、（４）式から
れかるように、Ｎｏ１モルに対しＢｒ２は１７２モル、
ＮＨ３は２モル必要である。ただし、ＮＨ３の１モルは
Ｂｒ２１／２と反応し、ＮＨ４Ｂｒを生成するため、純
粋にＮｏ還元のために消費されるＮＨ３ｆｉは１モルで
ある。As can be seen from equation (4), the amounts of Br2 gas and NH3 gas added are 172 mol of Br2 per 1 mol of No.
2 moles of NH3 are required. However, since 1 mole of NH3 reacts with Br21/2 to produce NH4Br, 1 mole of NH3fi is consumed purely for No reduction.
ＮＨ４Ｂｒは白色結晶であって、バグフィルタ−などの
集塵機、水洗塔での捕集が可能であり、電気分解反応に
よってＮＨ３とＢｒ２への転換がなされる。勿論、排ガ
ス処理量が少なく、ＮＨ４Ｂｒの生成量が小さい場合に
は、これを冷却捕集するだけで、必ずしもＮＨ４Ｂｒの
再利用を行なう必要はない。再生利用の必要性の有無は
経済性の問題である。NH4Br is a white crystal that can be collected using a dust collector such as a bag filter or a water washing tower, and is converted into NH3 and Br2 through an electrolysis reaction. Of course, if the amount of exhaust gas to be processed is small and the amount of NH4Br produced is small, it is not necessary to recycle NH4Br by simply cooling and collecting it. Whether or not there is a need for recycling is an economic issue.
［発明の効果］
この発明によるＮＯｘ除去法は、上述の如く全く新しい
概念と現象に基づくもので、単に排ガス中にＢｒ２ガス
およびＮＨ３ガスを添加するだけで、はぼ完全なＮＯｘ
除去が達成される。[Effects of the Invention] The NOx removal method according to the present invention is based on a completely new concept and phenomenon as described above, and by simply adding Br2 gas and NH3 gas to the exhaust gas, almost complete NOx removal can be achieved.
Elimination is achieved.
したがって、従来のＮＯｘ除去方法および装置に比較し
て大幅な簡略化がなされ、そのためその経済効果は非常
に大きい。またこの方法は単純な方法であるだけに、各
種燃焼排ガスを始めとして、内燃機関など従来処理困難
とされ放置されていた排ガスのＮＯｘ除去法として、多
種に渡る用途に適用することができる。Therefore, it is greatly simplified compared to conventional NOx removal methods and devices, and therefore its economic benefits are significant. Furthermore, since this method is a simple method, it can be applied to a wide variety of applications, including various types of combustion exhaust gases, as well as NOx removal methods for exhaust gases such as internal combustion engines, which have traditionally been difficult to treat and have been left untreated.
〔実 施 例］ 次に、この発明を実施例および比較例を以て説明する。〔Example] Next, the present invention will be explained using Examples and Comparative Examples.
実施例１および２
第１図に実験装置を示す。本装置は大きくＢ「２発生器
（１）と反応塔（２）に分けられる。Ｂｒ２発生器（１
）は、−直径３０ｍ５、高さ５１０５ｍのパイレックス
製の垂直管（３）と、その内部に充填された平均粒径２
ｍｍの球形ガラスピーズ（４）と、管（３）全体を被う
温水ジャケット（５）とで構成されている。ガラスピー
ズ（４）は、高さ３３１■にわたって充填されており、
Ｂｒ２発生器（１）は温水ジャケット（５）によって７
０℃に加熱保温されている。Examples 1 and 2 Figure 1 shows the experimental apparatus. This equipment is roughly divided into a B2 generator (1) and a reaction column (2).
) is a Pyrex vertical pipe (3) with a diameter of 30 m5 and a height of 5105 m, and the inside of it is filled with particles with an average diameter of 2
It consists of spherical glass beads (4) with a diameter of 1.2 mm and a hot water jacket (5) that covers the entire tube (3). The glass beads (4) are filled to a height of 331 cm,
Br2 generator (1) is connected to 7 by hot water jacket (5)
It is heated and kept at 0°C.
この構造のＢｒ２発生器（１）においてＢｒ２を発生さ
せるために、ＨＢｒによってｐＨを０゜５に維持したＮ
ａＢｒ０水溶液をＢｒ２発生器（１）の頂部へ流入した
。この時のＮａＢｒ０濃度は０．０３％、水溶液流量は
１．３１７時とした。処理すべき実験用排ガスとしては
、ボンベ詰めＮｏを空気で濃度８０ｐｐｍに希釈したガ
スを用いた。希釈用ガスは空気の代わりに窒素ガスでも
よい。この実験用排ガスをＢｒ２発生器（１）の底部へ
導入した。ガス流量は２１７分であった。Ｂｒ２発生器
（１）の頂部から出た実験用排ガスを反応塔（２）の頂
部へ送った。Ｂｒ２発生器（１）から反応塔（２）への
途中に、水ミストを除くためのりん酸バブラー（６）を
設置し、さらにその下流側にＮＯｘ分析計（７）を設置
した。In order to generate Br2 in the Br2 generator (1) with this structure, N
The aBr0 aqueous solution was flowed into the top of the Br2 generator (1). At this time, the NaBr0 concentration was 0.03%, and the aqueous solution flow rate was 1.317 hours. As the experimental exhaust gas to be treated, a gas obtained by diluting bottled No. 1 with air to a concentration of 80 ppm was used. The diluting gas may be nitrogen gas instead of air. This experimental exhaust gas was introduced into the bottom of the Br2 generator (1). The gas flow rate was 217 minutes. The experimental exhaust gas leaving the top of the Br2 generator (1) was sent to the top of the reaction column (2). A phosphoric acid bubbler (6) for removing water mist was installed on the way from the Br2 generator (1) to the reaction tower (2), and a NOx analyzer (7) was further installed downstream of the phosphoric acid bubbler (6).
反応塔（２）の直前で還元剤としてＮＨ３を注入した。NH3 was injected as a reducing agent just before the reaction column (2).
ＮＨ３ガスとしては窒素ガスで希釈したものを用いた。As the NH3 gas, one diluted with nitrogen gas was used.
この時のＮＨ，濃度は実験用排ガス基準で１６０１）Ｉ
）■であった。At this time, the NH concentration was 1601) I based on the experimental exhaust gas standard.
)■ It was.
反応塔（２）は、直径１０■、高さ４００ｍ麿のパイレ
ックス製の垂直管（８）と、その外面に巻装された温度
制御可能なリボンヒータ（９）と、管（８）内に充填さ
れた直径３■、長さ５ＩＩＩのラシヒリング（１０）と
で構成されている。そして反応塔（２）を通る排ガスを
リボンヒータ（９）によって均一に加熱した。The reaction tower (2) consists of a Pyrex vertical tube (8) with a diameter of 10 cm and a height of 400 m, a temperature-controllable ribbon heater (9) wrapped around the outside of the tube, and a It consists of a filled Raschig ring (10) with a diameter of 3 mm and a length of 5 III. Then, the exhaust gas passing through the reaction tower (2) was uniformly heated by a ribbon heater (9).
反応塔（２）の底部から出た処理排ガスを、同塔下流側
に設けられた氷水による冷却槽（１１）を通して、水分
その他を除去した。さらにこれの下流側でＮＯｘ分析計
（１２）によって出口側処理排ガス中のＮＯｘ濃度を測
定した。The treated exhaust gas discharged from the bottom of the reaction tower (2) was passed through an ice water cooling tank (11) provided on the downstream side of the tower to remove moisture and other components. Furthermore, on the downstream side of this, the NOx concentration in the outlet-side treated exhaust gas was measured using a NOx analyzer (12).
実験結果を第１表に示す。実施例１と２の反応条件の相
違は反応温度のみであり、他の条件は全て同一である。The experimental results are shown in Table 1. The only difference in the reaction conditions between Examples 1 and 2 is the reaction temperature, and all other conditions are the same.
上記実験条件を、後述する表２にまとめて示す。The above experimental conditions are summarized in Table 2 below.
第１表から明らかなように、Ｂｒ２ガスとＮＨ３ガスの
添加によって低い反応温度域でも高い脱硝率が得られた
。As is clear from Table 1, by adding Br2 gas and NH3 gas, a high denitrification rate was obtained even in a low reaction temperature range.
実施例３
実施例１の装置を用いて、第２表に示す条件で脱硝を行
なった。その結果、脱硝率は９０％であった。この実験
を３時間連続して実施した。Example 3 Denitration was carried out using the apparatus of Example 1 under the conditions shown in Table 2. As a result, the denitrification rate was 90%. This experiment was conducted continuously for 3 hours.
この間、脱硝率９０％は維持された。During this period, the denitrification rate of 90% was maintained.
冷却槽（１１）の内壁に白色析出物の生成が認められた
。そこで、この白色析出物をＸ線回折解析したところ、
第２図の結果が得られ、ＮＨ４Ｂ「の結晶であることが
確認された。また、この物質中のＮＯ３−の確認をブル
シン吸光法で行ない、ＮＯ２−の確認をナフチルアミン
吸収法で行なったが、これらイオンはいずれも検出でき
なかった。Formation of white precipitates was observed on the inner wall of the cooling tank (11). Therefore, when we analyzed this white precipitate by X-ray diffraction, we found that
The results shown in Figure 2 were obtained, and it was confirmed that it was a crystal of NH4B.Also, NO3- in this substance was confirmed by brucine absorption method, and NO2- was confirmed by naphthylamine absorption method. , none of these ions could be detected.
比較例１〜９
実施例１の装置を用いて、ガス組成と反応温度だけを変
え、その他の条件を実施ｆ！Ｎ１１と同じくし、ＮＯｘ
除去率を測定した。その結果を第３表に示す。なお、こ
の表では実施例１の条件と異なる条件のみを示す。Comparative Examples 1 to 9 Using the apparatus of Example 1, only the gas composition and reaction temperature were changed, and other conditions were carried out f! Same as N11, NOx
The removal rate was measured. The results are shown in Table 3. Note that this table shows only conditions different from those of Example 1.
同表から明らかなように、Ｂｒ２ガスとＮＨ３ガスを共
に添加しなければ、高い脱硝率は得られない。As is clear from the table, a high denitrification rate cannot be obtained unless both Br2 gas and NH3 gas are added.
第１表 （以下余白） ４、Table 1 (Margin below) 4,
第１図はこの発明の実施例を示すフローシート、第２図
はＸ線回折解析図である。
以上FIG. 1 is a flow sheet showing an example of the present invention, and FIG. 2 is an X-ray diffraction analysis diagram. that's all
Claims (1)
添加することを特徴とする窒素酸化物除去方法。A method for removing nitrogen oxides, which comprises adding bromine gas and ammonia gas to the exhaust gas to be treated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1038102A JPH02214524A (en) | 1989-02-16 | 1989-02-16 | Method for removing nitrogen oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1038102A JPH02214524A (en) | 1989-02-16 | 1989-02-16 | Method for removing nitrogen oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02214524A true JPH02214524A (en) | 1990-08-27 |
Family
ID=12516111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1038102A Pending JPH02214524A (en) | 1989-02-16 | 1989-02-16 | Method for removing nitrogen oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02214524A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5234477A (en) * | 1992-04-28 | 1993-08-10 | Shell Oil Company | Method of reducing NOx emissions in gasoline vehicles |
| US5351482A (en) * | 1992-04-28 | 1994-10-04 | Shell Oil Company | Method of maintaining catalytic converter activity in gasoline vehicles |
| CN1111078C (en) * | 1999-12-30 | 2003-06-11 | 赵善茂 | Complex utilization method for boiler fume |
| JP2006043536A (en) * | 2004-08-02 | 2006-02-16 | Central Glass Co Ltd | Method for decomposing nitrogen compound |
| CN112495365A (en) * | 2020-11-22 | 2021-03-16 | 浙江盛旺环境工程有限公司 | Medium-low temperature vanadium titanium-based SCR denitration catalyst and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4958074A (en) * | 1972-10-09 | 1974-06-05 |
-
1989
- 1989-02-16 JP JP1038102A patent/JPH02214524A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4958074A (en) * | 1972-10-09 | 1974-06-05 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5234477A (en) * | 1992-04-28 | 1993-08-10 | Shell Oil Company | Method of reducing NOx emissions in gasoline vehicles |
| US5351482A (en) * | 1992-04-28 | 1994-10-04 | Shell Oil Company | Method of maintaining catalytic converter activity in gasoline vehicles |
| CN1111078C (en) * | 1999-12-30 | 2003-06-11 | 赵善茂 | Complex utilization method for boiler fume |
| JP2006043536A (en) * | 2004-08-02 | 2006-02-16 | Central Glass Co Ltd | Method for decomposing nitrogen compound |
| JP4498053B2 (en) * | 2004-08-02 | 2010-07-07 | セントラル硝子株式会社 | Method for decomposing nitrogen compounds |
| CN112495365A (en) * | 2020-11-22 | 2021-03-16 | 浙江盛旺环境工程有限公司 | Medium-low temperature vanadium titanium-based SCR denitration catalyst and preparation method thereof |
| CN112495365B (en) * | 2020-11-22 | 2022-07-29 | 浙江盛旺环境工程有限公司 | Medium-low temperature vanadium titanium-based SCR denitration catalyst and preparation method thereof |
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