JPH03293035A - Catalyst for removal of nox - Google Patents
Catalyst for removal of noxInfo
- Publication number
- JPH03293035A JPH03293035A JP2092824A JP9282490A JPH03293035A JP H03293035 A JPH03293035 A JP H03293035A JP 2092824 A JP2092824 A JP 2092824A JP 9282490 A JP9282490 A JP 9282490A JP H03293035 A JPH03293035 A JP H03293035A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- nox
- removal
- distribution
- reducing agent
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 23
- 239000011148 porous material Substances 0.000 claims abstract description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002485 combustion reaction Methods 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 10
- 239000000969 carrier Substances 0.000 abstract description 3
- 239000000567 combustion gas Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ＬＮＧ、ＬＰＧなどのガス燃料の燃焼排ガス
中に含まれるＮＯＸ成分を分解除去させるために、γ−
アルミナ、ジルコニア、酸化チタンの一種又は複数種か
ら成る多孔状の担体に、イリジウム、白金、ロジウムの
一種又は複数種を担持させたＮ帆除去用触媒に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention uses γ-
This invention relates to a catalyst for removing N sails in which one or more of iridium, platinum, and rhodium is supported on a porous carrier made of one or more of alumina, zirconia, and titanium oxide.
従来、上記ＮＯｘ除去用触媒を利用するに際して、燃焼
排ガス中の０２との反応で触媒が短期間で失活すること
を防止するために、ＣＯ，ＮＨ４，Ｈ２等の還元剤と燃
焼排ガスを高温下で混合し、還元剤の作用で０２を除去
した燃焼排ガスに触媒を作用させていた。Conventionally, when using the above NOx removal catalyst, in order to prevent the catalyst from being deactivated in a short period of time due to reaction with 02 in the combustion exhaust gas, reducing agents such as CO, NH4, H2 and the combustion exhaust gas were heated at high temperature. A catalyst was applied to the combustion exhaust gas which was mixed at the bottom and 02 was removed by the action of a reducing agent.
しかし、０２除去のためにガスを昇温させるために、運
転経費が高くなり、また、還元剤供給装置、燃焼ガスと
還元剤の混合装置、ガスを反応のために高温にする装置
、未反応の還元剤を処理する装置が必要なために、設備
が高価で大型になり、殊に家庭用などの小型燃焼機器に
おいて実用できない欠点があった。However, operating costs are high because the temperature of the gas is raised to remove 02, and there is also a need for a reducing agent supply device, a mixing device for combustion gas and reducing agent, a device for heating the gas to a high temperature for reaction, and Since a device for processing the reducing agent is required, the equipment becomes expensive and large, which has the disadvantage that it cannot be put to practical use, especially in small-sized combustion equipment for household use.
本発明の目的は、還元剤を必要とせずに、かつ、低温下
において、ＮＯＸと０２を含む燃焼排ガスのＮＯ０除去
を、長期にわたり良好に実現できる、−段と優れたＮＯ
８除去用触媒を提供する点にある。An object of the present invention is to provide an extremely superior NO0 solution that can effectively remove NO0 from combustion exhaust gas containing NOx and O2 over a long period of time without requiring a reducing agent and at low temperatures.
The present invention provides a catalyst for removing No. 8.
本発明の特徴構成は、ガス燃料の燃焼排ガス中に含まれ
るＮＯ８成分を分解除去させるために、γ−アルミナ、
ジルコニア、酸化チタンの一種又は複数種から成る多孔
状の担体に、イリジウム、白金、ロジウムの一種又は複
数種を担持させたＮＯＸ除去用触媒において、
前記担体を、その細孔径分布が５０〜１００人及び５０
０〜１０００人において分布極大を有するように形成し
たことにあり、その作用効果は次の通りである。The characteristic configuration of the present invention is to decompose and remove NO8 components contained in the combustion exhaust gas of gas fuel.
A NOX removal catalyst in which one or more of iridium, platinum, and rhodium is supported on a porous carrier made of one or more of zirconia and titanium oxide, wherein the carrier has a pore size distribution of 50 to 100. and 50
The reason is that it is formed to have a distribution maximum between 0 and 1000 people, and its effects are as follows.
γ−アルミナ、ジルコニア、酸化チタンの一種又は複数
種から成る多孔状の担体に、イリジウム、白金、ロジウ
ムの一種又は複数種を担持させたＮＯｘ除去用触媒に、
いかなる物性を付加すれば、還元剤を必要とせずに、か
つ、低温下において、ＮＯＸと０２を含む燃焼排ガスの
ＮＯ８除去を、長期にわたり良好に実現できるかについ
て、検討しかつ実験で確認した結果、従来では技術認識
が全くなかった担体の細孔径分布に工夫を加えることが
有効であり、特に、第２図に例示するように、担体の細
孔径分布が５０〜１００人及び５００〜１０００人にお
いて分布極大を有するものであると効果が大きい事実を
新しく見出したのであり、その点について実験例により
以下に詳述する。A NOx removal catalyst in which one or more of iridium, platinum, and rhodium is supported on a porous carrier made of one or more of γ-alumina, zirconia, and titanium oxide,
The results of our study and experimental confirmation of what physical properties could be added to effectively remove NO8 from combustion exhaust gas containing NOx and 02 at low temperatures without the need for a reducing agent over a long period of time. It is effective to add some innovation to the pore size distribution of the carrier, which has not been technically recognized in the past.In particular, as illustrated in FIG. We have newly discovered the fact that the effect is greater when the distribution has a maximum, and this point will be explained in detail below using experimental examples.
実験例１ （第３図参照）
Ｎ広濃度５００ｐｐｍの燃焼排ガスの０□濃度を変化さ
せ、反応温度３０℃、５Ｖ１００Ｏ（ｈ−’ ）で燃焼
排ガスを従来及び本発明のＮＯＸ除去用触媒で処理し、
Ｎへ分解率の時間的変化を調べた。Experimental Example 1 (See Figure 3) The 0□ concentration of combustion exhaust gas with a wide N concentration of 500 ppm was changed, and the combustion exhaust gas was treated with the conventional and present NOX removal catalysts at a reaction temperature of 30°C and 5V 100O (h-'). death,
The temporal changes in the decomposition rate to N were investigated.
その結果、従来の触媒は】時間以内に失活したが、本発
明の触媒はＯ２濃度が高くても長時間にわたり十分なＮ
ＯＸ分解能を発揮した。As a result, the conventional catalyst was deactivated within 2 hours, but the catalyst of the present invention was able to maintain sufficient N for a long period of time even at high O2 concentrations.
Demonstrated OX resolution.
実験例２（第４図参照）
Ｎｏ、濃度５００ｐｐｍの燃焼排ガスを、５Ｖ１００Ｏ
（ｈ−’ ）で本発明のＮＯＸ除去用触媒で処理し、温
度変化に伴うＮＯＸ分解率の変化を調べた。Experimental example 2 (see Figure 4) No, combustion exhaust gas with a concentration of 500 ppm was heated at 5V100O.
(h-') was treated with the NOX removal catalyst of the present invention, and changes in NOX decomposition rate due to temperature changes were investigated.
その結果、室温程度で十分なＮＯ８分解能が得られた。As a result, sufficient NO8 decomposition ability was obtained at about room temperature.
実験例３
ＮＯＸ濃度５００ｐｐｍ、 Ｎ２濃度５０％、残量がＨ
ｅのガスを対象にして、反応温度３０℃、５Ｖ１００Ｏ
（ｈ−’ ）で従来及び本発明のＮＯＸ除去用触媒（表
面積１２０ｍ”／ｇ）で処理した。Experimental example 3 NOX concentration 500 ppm, N2 concentration 50%, remaining amount H
Targeting gas e, reaction temperature 30℃, 5V100O
(h-') was treated with the conventional and present NOX removal catalysts (surface area 120 m''/g).
その結果、従来の触媒によるＮＯＸ除去率は１０％であ
ったが、本発明の触媒によるＮＯ８除去率は９９．０％
であった。As a result, the NOx removal rate with the conventional catalyst was 10%, but the NO8 removal rate with the catalyst of the present invention was 99.0%.
Met.
要するに、担体の細孔径分布を上述のように設定すると
、０２が存在しても還元剤を必要とせずに、かつ、低温
化において、Ｎ０１除去を長期にわたり良好に実現でき
る。In short, if the pore size distribution of the carrier is set as described above, even if 02 is present, NO1 removal can be achieved satisfactorily over a long period of time without requiring a reducing agent and at low temperatures.
従って、前述の従来技術のように、０□除去に起因して
運転及び設備経費が高（なると共に設備が大型化する不
都合な事態を無くすことができ、例えば家庭用などの小
型燃焼機器においてＮＯＸ除去用触媒を実用できるよう
になった。Therefore, it is possible to eliminate the inconvenient situation in which operation and equipment costs are high (and the equipment becomes large) due to 0□ removal, as in the prior art described above. Removal catalysts can now be put to practical use.
その結果、使用対象設備の経済性や小型化において有利
で実用価値の高い、−段と高性能な燃焼排ガスのＮＯ８
除去用触媒を提供できるようになった。As a result, we have produced a NO8 combustion exhaust gas with much higher performance, which is advantageous and has high practical value in terms of economy and miniaturization of the equipment used.
Now we can provide removal catalysts.
次に実施例を説明する。 Next, an example will be described.
γ−アルミナ、ジルコニア、酸化チタンの一種又は複数
種から成る比表面積１００〜１７０ｍ３／ｇの多孔状の
担体に、イリジウム、白金、ロジウムの一種又は複数種
を０．０１〜１０重量％の含有率で担持させ、担体を、
その細孔径分布（細孔径と細孔容積の相関）か第２図の
ように５０〜ＩＣｌ０人及び５００〜１０００人におい
て、望ましくは７０人程度及び７００人程程度おいて分
布極大を有するように形成し、ＬＮＧ、ＬＰＧ、石炭系
ガスなどのガス燃料の燃焼排ガス中に含まれるＮＯ３成
分を、０２か存在しても、低温下で分解除去できるＮＯ
Ｘ除去用触媒を形成する。A porous carrier with a specific surface area of 100 to 170 m / g consisting of one or more of γ-alumina, zirconia, and titanium oxide contains one or more of iridium, platinum, and rhodium at a content of 0.01 to 10% by weight. The carrier is
The pore size distribution (correlation between pore size and pore volume) should be such that it has a distribution maximum in 50 to 1000 people and 500 to 1000 people, preferably around 70 and 700 people, as shown in Figure 2. The NO3 component contained in the combustion exhaust gas of gas fuels such as LNG, LPG, and coal-based gas can be decomposed and removed at low temperatures even if 02 is present.
Form a catalyst for X removal.
担体の細孔径分布を５０〜１００人及び５００〜１００
０人において分布極太を有するようにするに、４
アルミナ担体の場合について例示すると、第１図に示す
ようになる。The pore size distribution of the carrier is 50-100 and 500-100.
An example of the case of 4 alumina carriers in which the distribution is extremely thick for 0 people is as shown in FIG. 1.
つまり、硝酸アルミニウムなどのアルミニウム塩水溶液
をアンモニア添加によりゲル化して、含水率ｌＯ〜１５
％に脱水し、適量の添加剤を脱水物に混入して、その混
合物を１００℃以下で乾燥し、乾燥物を４００〜７００
℃で焼成して、添加剤の蒸発により細孔を形成する。添
加剤の種類及び添加量の選定が細孔径分布の調整のポイ
ントである。In other words, an aluminum salt aqueous solution such as aluminum nitrate is gelled by adding ammonia, and the water content is 10~15.
%, mix an appropriate amount of additives into the dehydrated product, dry the mixture at 100°C or less, and dry the dried product to 400-700°C.
C. to form pores by evaporation of the additives. Selection of the type and amount of additives is the key to adjusting the pore size distribution.
尚、細孔径分布の確認は、水銀を細孔に圧入して、入り
込む圧力から細孔径を算出するだめの水銀圧入式ポロシ
メータなどで行なう。The pore size distribution is confirmed using a mercury intrusion porosimeter, which injects mercury into the pores and calculates the pore size from the pressure of the mercury.
触媒の用途は、給湯器、調理器具、暖房器、乾燥器、ボ
イラ、エンジン、加熱炉、発電所等の家庭用や業務用の
燃焼機器における燃焼排ガスのＮ０８除去、その他いか
なるものでもよい。The catalyst may be used for removing N08 from combustion exhaust gas in household or commercial combustion equipment such as water heaters, cooking appliances, space heaters, dryers, boilers, engines, heating furnaces, power plants, and the like.
第１図は本発明における担体の製法を例示するフローシ
ートであり、第２図は担体の細孔径分布を説明するグラ
フである。
第３図及び第４図は実験結果を示すグラフである。FIG. 1 is a flow sheet illustrating the method for producing a carrier according to the present invention, and FIG. 2 is a graph illustrating the pore size distribution of the carrier. FIGS. 3 and 4 are graphs showing the experimental results.
Claims (1)
除去させるために、γ−アルミナ、ジルコニア、酸化チ
タンの一種又は複数種から成る多孔状の担体に、イリジ
ウム、白金、ロジウムの一種又は複数種を担持させたＮ
Ｏ＿Ｘ除去用触媒であって、 前記担体を、その細孔経分布が５０〜１００Å及び５０
０〜１０００Åにおいて分布極大を有するように形成し
てあるＮＯ＿Ｘ除去用触媒。[Claims] In order to decompose and remove NO_X components contained in the combustion exhaust gas of gas fuel, iridium, platinum, and rhodium are added to a porous carrier made of one or more of γ-alumina, zirconia, and titanium oxide. N carrying one or more types of
A catalyst for O_X removal, wherein the carrier has a pore diameter distribution of 50 to 100 Å and 50 Å.
A NO_X removal catalyst formed to have a distribution maximum in the range of 0 to 1000 Å.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2092824A JPH03293035A (en) | 1990-04-06 | 1990-04-06 | Catalyst for removal of nox |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2092824A JPH03293035A (en) | 1990-04-06 | 1990-04-06 | Catalyst for removal of nox |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03293035A true JPH03293035A (en) | 1991-12-24 |
Family
ID=14065184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2092824A Pending JPH03293035A (en) | 1990-04-06 | 1990-04-06 | Catalyst for removal of nox |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03293035A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5821190A (en) * | 1995-05-18 | 1998-10-13 | N.E. Chemcat Corporation | Catalyst comprising iridium, alkaline metal, alkaline earth or rare earth metal, and metal carbide or metal nitride |
| WO2002040152A1 (en) * | 2000-11-17 | 2002-05-23 | Osaka Gas Company Limited | Catalyst for purifying methane-containing waste gas and method of purifying methane-containing waste gas |
-
1990
- 1990-04-06 JP JP2092824A patent/JPH03293035A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5821190A (en) * | 1995-05-18 | 1998-10-13 | N.E. Chemcat Corporation | Catalyst comprising iridium, alkaline metal, alkaline earth or rare earth metal, and metal carbide or metal nitride |
| WO2002040152A1 (en) * | 2000-11-17 | 2002-05-23 | Osaka Gas Company Limited | Catalyst for purifying methane-containing waste gas and method of purifying methane-containing waste gas |
| JPWO2002040152A1 (en) * | 2000-11-17 | 2004-03-18 | 大阪瓦斯株式会社 | Catalyst for purifying methane-containing exhaust gas and method for purifying methane-containing exhaust gas |
| US7364712B2 (en) | 2000-11-17 | 2008-04-29 | Osaka Gas Company Limited | Catalyst for purifying methane-containing waste gas and method of purifying methane-containing waste gas |
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