JPH04265122A - Purifying method of waste gas - Google Patents
Purifying method of waste gasInfo
- Publication number
- JPH04265122A JPH04265122A JP3045730A JP4573091A JPH04265122A JP H04265122 A JPH04265122 A JP H04265122A JP 3045730 A JP3045730 A JP 3045730A JP 4573091 A JP4573091 A JP 4573091A JP H04265122 A JPH04265122 A JP H04265122A
- Authority
- JP
- Japan
- Prior art keywords
- exhaust gas
- catalyst
- nitrogen oxides
- tio2
- ammonia
- 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
- 238000000034 method Methods 0.000 title claims description 22
- 239000002912 waste gas Substances 0.000 title abstract 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 106
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 56
- 150000004045 organic chlorine compounds Chemical class 0.000 claims description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 8
- 150000004826 dibenzofurans Chemical class 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 229910003082 TiO2-SiO2 Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 229910052707 ruthenium Inorganic materials 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 5
- 229910052863 mullite Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000011218 binary composite Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】この発明は、焼却炉等から排出さ
れた排ガス中に含有されている、窒素酸化物、および、
ポリ塩化ジベンゾダイオキシン、ポリ塩化ジベンゾフラ
ン等の有機塩素化合物を除去して、排ガスを浄化するた
めの方法に関するものである。[Industrial Application Field] This invention is directed to nitrogen oxides contained in exhaust gas discharged from incinerators, etc.
The present invention relates to a method for purifying exhaust gas by removing organic chlorine compounds such as polychlorinated dibenzodioxins and polychlorinated dibenzofurans.
【０００２】0002
【従来の技術】産業廃棄物や都市ごみを処理するための
焼却炉等から発生する排ガス中には、窒素酸化物（ＮＯ
ｘ） と共に、微量ではあるが極めて毒性の強いポリ塩
化ジベンゾダイオキシン（ＰＣＤＤｓ） 、ポリ塩化ジ
ベンゾフラン（ＰＣＤＦｓ） 等の有機塩素化合物が含
有されている。このような有害な窒素酸化物および有機
塩素化合物の、排ガス中からの除去は、公害防止上、極
めて重要である。[Prior Art] Nitrogen oxides (NO
In addition to x), organic chlorine compounds such as polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), which are extremely toxic, are contained in trace amounts. Removal of such harmful nitrogen oxides and organic chlorine compounds from exhaust gas is extremely important in terms of pollution prevention.
【０００３】排ガス中からの窒素酸化物の除去方法とし
て、例えば、特公昭５４−２９４１９号公報には、排ガ
ス中に還元剤としてのアンモニアを添加し、このように
アンモニアが添加された排ガスを、窒素酸化物還元用触
媒に接触させることにより、排ガス中の窒素酸化物を還
元して除去する方法が開示されている。[0003] As a method for removing nitrogen oxides from exhaust gas, for example, Japanese Patent Publication No. 54-29419 discloses that ammonia as a reducing agent is added to exhaust gas, and the exhaust gas to which ammonia has been added is A method is disclosed in which nitrogen oxides in exhaust gas are reduced and removed by contacting with a catalyst for reducing nitrogen oxides.
【０００４】排ガス中からの有機塩素化合物の除去方法
として、例えば、特開昭６３−２９０３１４ 号公報に
は、排ガスを、セラミック担体に担持させた白金等の有
機塩素化合物酸化用触媒と、３００ 〜９００ ℃の温
度で接触させることにより、排ガス中の有機塩素化合物
を酸化させて除去する方法が開示されている。[0004] As a method for removing organic chlorine compounds from exhaust gas, for example, Japanese Patent Application Laid-Open No. 63-290314 discloses that exhaust gas is treated with a catalyst for oxidizing organic chlorine compounds such as platinum supported on a ceramic carrier, and A method is disclosed in which organic chlorine compounds in exhaust gas are oxidized and removed by contacting at a temperature of 900°C.
【０００５】[0005]
【発明が解決しようとする課題】上述した特公昭５４−
２９４１９号公報に開示された方法によれば、排ガス中
から窒素酸化物のみを除去することができ、また、特開
昭６３−２９０３１４ 号公報に開示された方法によれ
ば、排ガス中から有機塩素化合物のみを除去することは
できる。しかしながら、上記何れの方法も、窒素酸化物
および有機塩素化合物の両者を共に排ガス中から除去す
ることはできない。
この結果、排ガス中から、窒素酸化物および有機塩素化
合物を除去するためには、従来、窒素酸化物還元用触媒
を有する脱硝用反応器、および、有機塩素化合物酸化用
触媒を有する有機塩素化合物除去用反応器を、それぞれ
別個に設け、排ガスを、脱硝用反応器と有機塩素化合物
除去用反応器とに順次通し、先ず、脱硝用反応器の触媒
によって窒素酸化物を除去した後、有機塩素化合物除去
用反応器の触媒によって有機塩素化合物を除去しなけれ
ばならず、このために、設備が大型化し、且つ、触媒の
コストが上昇する問題があった。[Problem to be solved by the invention]
According to the method disclosed in JP-A No. 29419, only nitrogen oxides can be removed from the exhaust gas, and according to the method disclosed in JP-A-63-290314, organic chlorine can be removed from the exhaust gas. Only compounds can be removed. However, none of the above methods can remove both nitrogen oxides and organic chlorine compounds from exhaust gas. As a result, in order to remove nitrogen oxides and organic chlorine compounds from exhaust gas, conventionally, a denitration reactor with a catalyst for reducing nitrogen oxides and an organic chlorine compound removal reactor with a catalyst for oxidizing organic chlorine compounds have been used. The exhaust gas is sequentially passed through the denitrification reactor and the organic chlorine compound removal reactor. First, nitrogen oxides are removed by the catalyst in the denitration reactor, and then the organic chlorine compounds are removed. The organic chlorine compound must be removed using a catalyst in a removal reactor, which causes problems in that the equipment becomes larger and the cost of the catalyst increases.
【０００６】従って、この発明の目的は、焼却炉等から
排出された排ガス中に含有されている、有害な、窒素酸
化物および有機塩素化合物を、従来のような、窒素酸化
物除去用および有機塩素化合物除去用のそれぞれ別個の
触媒を必要とせず、１種類の触媒によって共に効率的に
除去し、従来よりも小型の設備によって、経済的に排ガ
スを浄化するための方法を提供することにある。[0006] Therefore, an object of the present invention is to remove harmful nitrogen oxides and organic chlorine compounds contained in exhaust gas discharged from incinerators, etc. using conventional methods for removing nitrogen oxides and organic chlorine compounds. The object of the present invention is to provide a method for economically purifying exhaust gas by eliminating the need for separate catalysts for removing chlorine compounds, efficiently removing them using one type of catalyst, and using equipment that is smaller than conventional ones. .
【０００７】[0007]
【課題を解決するための手段】本発明者等は、上述した
問題を解決すべく鋭意研究を重ねた。その結果、Ｔｉ，
Ｓｉ，Ａｌ およびＺｒからなる群から選択された少な
くとも１種の金属の酸化物からなる基体の表面上に、Ｐ
ｔ，Ｐｄ，Ｒｕ，Ｍｎ，Ｃｕ，Ｃｒ およびＦｅからな
る群から選択された少なくとも１種の金属またはその酸
化物を担持させた触媒に、還元剤としてのアンモニアが
添加された排ガスを、特定の温度範囲で接触させれば、
排ガス中に含有されている窒素酸化物および有機塩素化
合物を、１種類の触媒によって共に効率的に除去し、従
来よりも小型の設備によって、経済的に排ガスを浄化し
得ることを知見した。[Means for Solving the Problems] The present inventors have conducted extensive research in order to solve the above-mentioned problems. As a result, Ti,
P on the surface of a substrate made of an oxide of at least one metal selected from the group consisting of Si, Al and Zr.
Ammonia as a reducing agent is added to a catalyst on which at least one metal selected from the group consisting of t, Pd, Ru, Mn, Cu, Cr, and Fe is supported, and ammonia is added to the exhaust gas in a specific manner. If you make contact within the temperature range,
It has been discovered that both nitrogen oxides and organic chlorine compounds contained in exhaust gas can be efficiently removed using one type of catalyst, and that exhaust gas can be economically purified using equipment that is smaller than conventional ones.
【０００８】この発明は、上記知見に基づいてなされた
ものであって、この発明の方法は、焼却炉等から排出さ
れた、窒素酸化物、および、ポリ塩化ジベンゾダイオキ
シン、ポリ塩化ジベンゾフラン等の有機塩素化合物を含
有する排ガス中に、還元剤としてのアンモニアを連続的
または間欠的に添加し、このようにアンモニアが添加さ
れた排ガスを、Ｔｉ， Ｓｉ，Ａｌ およびＺｒからな
る群から選択された少なくとも１種の金属の酸化物から
なる基体の表面上に、Ｐｔ，Ｐｄ，Ｒｕ，Ｍｎ，Ｃｕ，
Ｃｒ およびＦｅからなる群から選択された少なくとも
１種の金属またはその酸化物を担持させた触媒に、１５
０ 〜３４０ ℃の温度で接触させることにより、前記
排ガス中に含有されている前記窒素酸化物を還元して除
去し、同時に、前記排ガス中に含有されている前記有機
塩素化合物を酸化して除去することに特徴を有するもの
である。The present invention was made based on the above findings, and the method of the present invention is capable of treating nitrogen oxides and organic compounds such as polychlorinated dibenzodioxins and polychlorinated dibenzofurans discharged from incinerators, etc. Ammonia as a reducing agent is added continuously or intermittently to the exhaust gas containing chlorine compounds, and the exhaust gas to which ammonia has been added is treated with at least one selected from the group consisting of Ti, Si, Al and Zr. Pt, Pd, Ru, Mn, Cu,
15 on a catalyst supported with at least one metal selected from the group consisting of Cr and Fe or an oxide thereof.
By contacting at a temperature of 0 to 340 °C, the nitrogen oxides contained in the exhaust gas are reduced and removed, and at the same time, the organic chlorine compounds contained in the exhaust gas are oxidized and removed. It is characterized by the fact that
【０００９】[0009]
【作用】この発明においては、排ガス中に還元剤として
のアンモニアを添加し、このようなアンモニアが添加さ
れた排ガスを、１５０ 〜３４０ ℃の温度で、以下に
述べる触媒に接触させる。この結果、排ガス中の窒素酸
化物は還元除去され、同時に、排ガス中の有機塩素化合
物酸化用触媒は酸化除去される。[Operation] In this invention, ammonia as a reducing agent is added to the exhaust gas, and the exhaust gas to which such ammonia has been added is brought into contact with the catalyst described below at a temperature of 150 to 340°C. As a result, nitrogen oxides in the exhaust gas are reduced and removed, and at the same time, the catalyst for oxidizing organic chlorine compounds in the exhaust gas is oxidized and removed.
【００１０】触媒として、Ｔｉ，Ｓｉ，ＡｌおよびＺｒ
からなる群から選択された少なくとも１種の金属の酸化
物からなる基体の表面上に、Ｐｔ，Ｐｄ，Ｒｕ，Ｍｎ，
Ｃｕ，Ｃｒ およびＦｅからなる群から選択された少な
くとも１種の金属またはその酸化物を担持させた触媒を
使用する。このような触媒によれば、ＮＯｘ，ＳＯｘ，
ＨＣｌ，ＣＯおよびハロゲンガス等の存在する環境下に
おいて、ガス中に添加されたアンモニアによる、窒素酸
化物の還元除去と、そして、ポリ塩化ジベンゾダイオキ
シン、ポリ塩化ジベンゾフラン等の有機塩素化合物の酸
化除去とを、同時に長期にわたって効率よく行うことが
できる。[0010] Ti, Si, Al and Zr are used as catalysts.
Pt, Pd, Ru, Mn, Pt, Pd, Ru, Mn,
A catalyst on which at least one metal selected from the group consisting of Cu, Cr and Fe or an oxide thereof is supported is used. According to such a catalyst, NOx, SOx,
Reduction and removal of nitrogen oxides using ammonia added to the gas in an environment containing HCl, CO, halogen gas, etc., and oxidation removal of organic chlorine compounds such as polychlorinated dibenzodioxins and polychlorinated dibenzofurans. can be carried out simultaneously and efficiently over a long period of time.
【００１１】好ましい触媒は、ＴｉＯ２−ＳｉＯ２ ま
たはＴｉＯ２− ＺｒＯ２の２元系複合酸化物、３Ａｌ
２Ｏ３・２ＳｉＯ２ を含有する酸化物の表面上にＴｉ
Ｏ２が被覆された酸化物、または、ＴｉＯ２−ＳｉＯ２
−Ａｌ２Ｏ３ 、ＴｉＯ２−ＳｉＯ２−ＺｒＯ２の３元
系複合酸化物を基体とし、この基体の表面上に、上述し
た、Ｐｔ，Ｐｄ，Ｒｕ，Ｍｎ，Ｃｕ， ＣｒおよびＦｅ
からなる群から選択された少なくとも１種の金属または
その酸化物を担持させた触媒である。[0011] Preferred catalysts include binary composite oxides of TiO2-SiO2 or TiO2-ZrO2, 3Al
Ti on the surface of the oxide containing 2O3.2SiO2
Oxide coated with O2 or TiO2-SiO2
A ternary complex oxide of -Al2O3, TiO2-SiO2-ZrO2 is used as a base, and the above-mentioned Pt, Pd, Ru, Mn, Cu, Cr and Fe are deposited on the surface of this base.
A catalyst supporting at least one metal selected from the group consisting of:
【００１２】特に、基体を、３Ａｌ２Ｏ３・２ＳｉＯ２
即ちムライトを含有する酸化物の表面上にＴｉＯ２が
被覆された構造とすれば、ムライトの表面上に被覆され
たＴｉＯ２により、基体の表面に微細な凹凸が形成され
るので、Ｐｔ等の触媒成分を担持させて高活性を得るの
に必要な表面積を十分に確保することができ、且つ、ム
ライトの表面上を被覆するＴｉＯ２によって、優れた耐
酸性が付与される。In particular, the substrate is made of 3Al2O3.2SiO2
In other words, if the surface of the oxide containing mullite is coated with TiO2, the TiO2 coated on the surface of the mullite will form fine irregularities on the surface of the substrate, so the catalyst components such as Pt will A sufficient surface area can be secured to obtain high activity by supporting TiO2, and the TiO2 coating on the surface of mullite imparts excellent acid resistance.
【００１３】触媒の形状は、円柱状、円筒状、板状、リ
ボン状、ハニカム状、ペレット状等、一体成形された任
意の形状のものを選ぶことができる。特に、第２図に断
面図で示すような、断面が格子状のハニカム構造体から
なる触媒Ａ、または、第３図に断面図で示すような、断
面がコルゲート状のハニカム構造体からなる触媒Ｂが好
ましい。触媒をこのようなハニカム構造体によって構成
すれば、排ガス中に存在するダストが触媒に付着するこ
とはなく、従って、ダストの付着による圧力損失の増大
や性能の低下等が生ぜずに、安定した操業を行うことが
できる。[0013] The shape of the catalyst can be selected from any integrally formed shape, such as columnar, cylindrical, plate-like, ribbon-like, honeycomb-like, and pellet-like. In particular, the catalyst A consists of a honeycomb structure with a lattice cross section as shown in the cross section in FIG. 2, or the catalyst A consists of a honeycomb structure with a corrugated cross section as shown in the cross section in FIG. B is preferred. If the catalyst is configured with such a honeycomb structure, the dust present in the exhaust gas will not adhere to the catalyst, and therefore, there will be no increase in pressure loss or deterioration of performance due to the adhesion of dust, and a stable Operations can be carried out.
【００１４】上述した触媒に接触させる排ガスの温度は
、１５０ 〜３４０ ℃の範囲内に限定すべきである。
排ガスの温度が１５０ ℃未満では、有機塩素化合物の
酸化反応が不十分になってその除去効率が低下し、更に
、排ガス中のＳＯｘ，ＨＣｌ 等により、触媒が劣化す
る問題が生ずる。一方、排ガスの温度が３４０ ℃を超
えると、触媒によって、逆に、排ガス中に添加されたア
ンモニアからの窒素酸化物の発生が顕著になる問題が生
ずる。[0014] The temperature of the exhaust gas brought into contact with the above-mentioned catalyst should be limited to a range of 150 to 340°C. If the temperature of the exhaust gas is less than 150° C., the oxidation reaction of the organic chlorine compound becomes insufficient and its removal efficiency decreases, and furthermore, there is a problem that the catalyst deteriorates due to SOx, HCl, etc. in the exhaust gas. On the other hand, if the temperature of the exhaust gas exceeds 340° C., a problem arises in that the catalyst causes significant generation of nitrogen oxides from ammonia added to the exhaust gas.
【００１５】１５０ 〜３４０ ℃の範囲内の温度の排
ガス中に、ＮＨ３／ＮＯｘ（モル比） が１以上となる
ように、アンモニアを添加すれば、窒素酸化物の除去効
率を高めることができる。このような割合で、排ガス中
にアンモニアを添加しても、排ガス中の未反応の余剰な
アンモニアは、その量が過多（約２００ｐｐｍ以上）で
ない限り、上述した触媒によって窒素および水に分解し
て除去されるので、問題が生ずることはない。[0015] If ammonia is added to the exhaust gas at a temperature within the range of 150 to 340°C so that the NH3/NOx (molar ratio) is 1 or more, the removal efficiency of nitrogen oxides can be increased. Even if ammonia is added to the exhaust gas at such a ratio, the unreacted surplus ammonia in the exhaust gas will be decomposed into nitrogen and water by the catalyst described above, unless the amount is excessive (approximately 200 ppm or more). Since it is removed, there is no problem.
【００１６】排ガス中へのアンモニアの添加は、連続的
に行っても、または、間欠的に行ってもよい。排ガス中
へのアンモニアの添加を間欠的に行っても、上述した触
媒に吸着されたアンモニアによって、排ガス中に含有さ
れている窒素酸化物の還元を行うことができる。[0016] Ammonia may be added to the exhaust gas continuously or intermittently. Even if ammonia is added intermittently to the exhaust gas, the nitrogen oxides contained in the exhaust gas can be reduced by the ammonia adsorbed on the catalyst described above.
【００１７】第１図は、この発明方法の１実施態様を示
す概略工程図である。第１図に示すように、この発明の
方法においては、先ず、混合室１において、排ガス中に
、アンモニア（ＮＨ３）を、連続的または間欠的に添加
しそして混合する。そして、このようにアンモニアが添
加された排ガスを、前述した触媒が設けられた、窒素酸
化物および有機塩素化合物同時除去用反応器２に、１５
０ 〜３４０ ℃の温度で導く。この結果、排ガス中の
窒素酸化物および有機塩素化合物は、反応器２内の前述
した触媒によって、同時に除去される。FIG. 1 is a schematic process diagram showing one embodiment of the method of the present invention. As shown in FIG. 1, in the method of the present invention, first, in a mixing chamber 1, ammonia (NH3) is continuously or intermittently added to exhaust gas and mixed. Then, the exhaust gas to which ammonia has been added is transferred to a reactor 2 for simultaneous removal of nitrogen oxides and organic chlorine compounds, which is equipped with the catalyst described above.
Conducted at temperatures between 0 and 340°C. As a result, nitrogen oxides and organic chlorine compounds in the exhaust gas are simultaneously removed by the aforementioned catalyst in the reactor 2.
【００１８】[0018]
【実施例】次に、この発明を、実施例により比較例と対
比しながら更に詳細に説明する。ムライトを含む酸化物
の表面にＴｉＯ２が被覆された、ＴｉＯ２の含有量が６
０ｗｔ．％である、第３図に示すコルゲート状のハニカ
ム構造体からなる基体Ｂを調製した。基体Ｂの各部の寸
法は、次の通りである。
幅方向ピッチ（ａ） ： ３．７ｍｍ 長さ方
向ピッチ（ｂ） ： ７．５ｍｍ 波状壁の厚さ（
ｃ） ： ０．４ｍｍ 側壁の厚さ（ｄ）
： ０．５ｍｍ 開口率
： ７７％上述した基体ＢにＰｔ（２．５ｇ
／触媒１リットル）を担持させた。かくして、その表面
がＴｉＯ２によって被覆されたムライトからなる基体の
表面上に、Ｐｔが担持された、コルゲート状の触媒を調
製した。EXAMPLES Next, the present invention will be explained in more detail by examples and in comparison with comparative examples. The surface of the oxide containing mullite is coated with TiO2, the content of TiO2 is 6
0wt. %, a substrate B consisting of a corrugated honeycomb structure shown in FIG. 3 was prepared. The dimensions of each part of the base body B are as follows. Width direction pitch (a): 3.7mm Length direction pitch (b): 7.5mm Thickness of wavy wall (
c): 0.4mm Side wall thickness (d)
: 0.5mm aperture ratio
: 77% Pt (2.5 g
/1 liter of catalyst) was supported. In this way, a corrugated catalyst was prepared in which Pt was supported on the surface of a substrate made of mullite whose surface was coated with TiO2.
【００１９】上述した触媒を使用し、第１図に示した工
程図に従って、この発明の方法により、窒素酸化物（Ｎ
Ｏｘ）およびポリ塩化ジベンゾダイオキシン（ＰＣＤＤ
ｓ） を下記のように含有する排ガス中から、窒素酸化
物（ＮＯｘ） およびポリ塩化ジベンゾダイオキシン（
ＰＣＤＤｓ） を除去した。
ＮＯｘ 含有量 ： １３０ 〜 １８０ｐｐｍ
ＰＣＤＤｓ 含有量 ： ２０００ 〜４０００ｎｇ
／Ｎｍ３Using the above catalyst and following the process diagram shown in FIG. 1, nitrogen oxides (N
Ox) and polychlorinated dibenzodioxins (PCDD
Nitrogen oxides (NOx) and polychlorinated dibenzodioxins (
PCDDs) were removed. NOx content: 130-180ppm
PCDDs content: 2000 ~ 4000ng
/Nm3
【００２０】第１表に、排ガス温度、還元剤と
してのアンモニアの添加量〔ＮＨ３／ＮＯｘ（モル比）
］、ＮＯｘ 除去率、ＮＯｘ 増加率およびＰＣＤＤｓ
除去率を示す。Table 1 shows exhaust gas temperature, amount of ammonia added as a reducing agent [NH3/NOx (molar ratio)]
], NOx removal rate, NOx increase rate and PCDDs
Indicates removal rate.
【００２１】[0021]
【００２２】第１表において、Ｎｏ． １〜５は本発明
の実施例であり、Ｎｏ． ６は、触媒に接触させる排ガ
スの温度が本発明の範囲を超えて高い比較例である。第
１表から明らかように、触媒に接触させる排ガスの温度
が本発明の範囲を超えて高い比較例Ｎｏ． ６の場合は
、排ガス中のＮＯｘ が逆に増加した。これに対して、
本発明実施例のＮｏ． １〜５の場合は、何れも、ＮＯ
ｘ およびＰＣＤＤｓ を、排ガス中から共に効率的に
除去することができた。In Table 1, No. 1 to 5 are examples of the present invention, and No. 1 to 5 are examples of the present invention. No. 6 is a comparative example in which the temperature of the exhaust gas brought into contact with the catalyst is higher than the range of the present invention. As is clear from Table 1, in Comparative Example No. 1, the temperature of the exhaust gas brought into contact with the catalyst was higher than the range of the present invention. In the case of No. 6, NOx in the exhaust gas increased on the contrary. On the contrary,
No. of the embodiment of the present invention. In the case of 1 to 5, NO
Both x and PCDDs could be efficiently removed from the exhaust gas.
【００２３】[0023]
【発明の効果】以上説明したように、この発明によれば
、焼却炉等から排出された排ガス中に含有されている、
有害な窒素酸化物および有機塩素化合物は、１種類の触
媒によって共に効率的に除去され、従って、従来よりも
小型の設備によって、経済的に排ガスを浄化することが
できる工業上有用な効果がもたらされる。[Effects of the Invention] As explained above, according to the present invention, the
Harmful nitrogen oxides and organic chlorine compounds are both efficiently removed by one type of catalyst, and therefore, an industrially useful effect is brought about in which exhaust gas can be purified economically with equipment that is smaller than before. It will be done.
【図１】この発明方法の１実施態様を示す概略工程図で
ある。FIG. 1 is a schematic process diagram showing one embodiment of the method of the present invention.
【図２】この発明方法に使用される触媒の形状の一例を
示す断面図である。FIG. 2 is a sectional view showing an example of the shape of a catalyst used in the method of the present invention.
【図３】この発明方法に使用される触媒の形状の他の例
を示す断面図である。FIG. 3 is a sectional view showing another example of the shape of the catalyst used in the method of the present invention.
１ 混合室
２ 窒素酸化物および有機塩素化合物同時除去用反応
器Ａ 触媒
Ｂ 触媒1 Mixing chamber 2 Reactor A for simultaneous removal of nitrogen oxides and organic chlorine compounds Catalyst B Catalyst
Claims (3)
、および、ポリ塩化ジベンゾダイオキシン、ポリ塩化ジ
ベンゾフラン等の有機塩素化合物を含有する排ガス中に
、還元剤としてのアンモニアを連続的または間欠的に添
加し、このようにアンモニアが添加された排ガスを、Ｔ
ｉ，Ｓｉ，ＡｌおよびＺｒからなる群から選択された少
なくとも１種の金属の酸化物からなる基体の表面上に、
Ｐｔ，Ｐｄ，Ｒｕ，Ｍｎ，Ｃｕ，Ｃｒ およびＦｅから
なる群から選択された少なくとも１種の金属またはその
酸化物を担持させた触媒に、１５０ 〜３４０ ℃の温
度で接触させることにより、前記排ガス中に含有されて
いる前記窒素酸化物を還元して除去し、同時に、前記排
ガス中に含有されている前記有機塩素化合物を酸化して
除去することを特徴とする排ガスの浄化方法。Claim 1: Adding ammonia as a reducing agent continuously or intermittently to exhaust gas containing nitrogen oxides and organic chlorine compounds such as polychlorinated dibenzodioxins and polychlorinated dibenzofurans, which is discharged from an incinerator or the like. and the exhaust gas to which ammonia has been added in this way is
On the surface of a substrate made of an oxide of at least one metal selected from the group consisting of i, Si, Al and Zr,
The exhaust gas is brought into contact with a catalyst supporting at least one metal selected from the group consisting of Pt, Pd, Ru, Mn, Cu, Cr, and Fe or an oxide thereof at a temperature of 150 to 340°C. A method for purifying exhaust gas, comprising reducing and removing the nitrogen oxides contained therein, and oxidizing and removing the organic chlorine compounds contained in the exhaust gas at the same time.
・２ＳｉＯ２ を含有する酸化物の表面上にＴｉＯ２が
被覆された酸化物からなっている、請求項１記載の方法
。2. The substrate of the catalyst is 3Al2O3
- The method according to claim 1, comprising an oxide in which TiO2 is coated on the surface of an oxide containing 2SiO2.
ｉＯ２ 、ＴｉＯ２−ＺｒＯ２ 、ＴｉＯ２−ＳｉＯ２
−Ａｌ２Ｏ３ およびＴｉＯ２−ＳｉＯ２−ＺｒＯ２の
うちの何れか１つの複合酸化物からなっている、請求項
１記載の方法。3. The substrate of the catalyst is TiO2-S
iO2, TiO2-ZrO2, TiO2-SiO2
The method according to claim 1, comprising a composite oxide of any one of -Al2O3 and TiO2-SiO2-ZrO2.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3045730A JP2542290B2 (en) | 1991-02-18 | 1991-02-18 | Exhaust gas purification method |
| US07/791,571 US5294419A (en) | 1990-11-30 | 1991-11-12 | Method for removing nitrogen oxides and organic chlorine compounds from combustion waste gas |
| CA002055521A CA2055521A1 (en) | 1990-11-30 | 1991-11-14 | Method and filter for removing nitrogen oxides and organic chlorine compounds from combustion waste gas |
| EP91120455A EP0488331B1 (en) | 1990-11-30 | 1991-11-28 | Method and filter for removing nitrogen oxides and organic chlorine compounds from combustion waste gas |
| DE69125103T DE69125103T2 (en) | 1990-11-30 | 1991-11-28 | Process and filter for the removal of nitrogen oxides and organic chlorine compounds from waste gases from combustion plants |
| KR1019910021762A KR950004139B1 (en) | 1990-11-30 | 1991-11-29 | Removing method and filter of nitrogen oxide and organic chlorine compound from fuel gas |
| TW081100949A TW199111B (en) | 1990-11-30 | 1992-02-11 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3045730A JP2542290B2 (en) | 1991-02-18 | 1991-02-18 | Exhaust gas purification method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04265122A true JPH04265122A (en) | 1992-09-21 |
| JP2542290B2 JP2542290B2 (en) | 1996-10-09 |
Family
ID=12727440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3045730A Expired - Lifetime JP2542290B2 (en) | 1990-11-30 | 1991-02-18 | Exhaust gas purification method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2542290B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5783160A (en) * | 1995-01-27 | 1998-07-21 | Toyota Jidosha Kabushiki Kaisha | Method for purifying combustion exhaust gas |
| EP0953376A1 (en) * | 1998-04-29 | 1999-11-03 | Institut Francais Du Petrole | Method to control the injection of hydrocarbons in the exhaust pipe of an internal combustion engine |
| EP1260765A1 (en) | 1999-11-25 | 2002-11-27 | Shiina, Keiji | Combustion additive to reduce dioxin emissions |
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|---|---|---|---|---|
| US2975025A (en) * | 1957-11-05 | 1961-03-14 | Engelhard Ind Inc | Method of selectively removing oxides of nitrogen from oxygen-containing gases |
| JPS5730532A (en) * | 1980-07-31 | 1982-02-18 | Mitsubishi Electric Corp | Dry type deodorizer |
| JPS6265721A (en) * | 1985-05-08 | 1987-03-25 | Nippon Shokubai Kagaku Kogyo Co Ltd | Method for purifying waste gas |
| JPH02280816A (en) * | 1989-03-17 | 1990-11-16 | Didier Werke Ag | Method for removing or reducing halogenated aromatic compound from waste gas of incinerator for waste |
| JPH038415A (en) * | 1989-06-07 | 1991-01-16 | Masakatsu Hiraoka | Treatment of exhaust gas |
-
1991
- 1991-02-18 JP JP3045730A patent/JP2542290B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2975025A (en) * | 1957-11-05 | 1961-03-14 | Engelhard Ind Inc | Method of selectively removing oxides of nitrogen from oxygen-containing gases |
| JPS5730532A (en) * | 1980-07-31 | 1982-02-18 | Mitsubishi Electric Corp | Dry type deodorizer |
| JPS6265721A (en) * | 1985-05-08 | 1987-03-25 | Nippon Shokubai Kagaku Kogyo Co Ltd | Method for purifying waste gas |
| JPH02280816A (en) * | 1989-03-17 | 1990-11-16 | Didier Werke Ag | Method for removing or reducing halogenated aromatic compound from waste gas of incinerator for waste |
| JPH038415A (en) * | 1989-06-07 | 1991-01-16 | Masakatsu Hiraoka | Treatment of exhaust gas |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5783160A (en) * | 1995-01-27 | 1998-07-21 | Toyota Jidosha Kabushiki Kaisha | Method for purifying combustion exhaust gas |
| EP0953376A1 (en) * | 1998-04-29 | 1999-11-03 | Institut Francais Du Petrole | Method to control the injection of hydrocarbons in the exhaust pipe of an internal combustion engine |
| EP1260765A1 (en) | 1999-11-25 | 2002-11-27 | Shiina, Keiji | Combustion additive to reduce dioxin emissions |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2542290B2 (en) | 1996-10-09 |
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