JP3436567B2 - Exhaust gas purification catalyst and method for producing the same - Google Patents
Exhaust gas purification catalyst and method for producing the sameInfo
- Publication number
- JP3436567B2 JP3436567B2 JP15239093A JP15239093A JP3436567B2 JP 3436567 B2 JP3436567 B2 JP 3436567B2 JP 15239093 A JP15239093 A JP 15239093A JP 15239093 A JP15239093 A JP 15239093A JP 3436567 B2 JP3436567 B2 JP 3436567B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- exhaust gas
- denitration
- ammonia
- oxidation 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.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims description 290
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 238000000746 purification Methods 0.000 title claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 98
- 230000003647 oxidation Effects 0.000 claims description 90
- 238000007254 oxidation reaction Methods 0.000 claims description 90
- 239000007789 gas Substances 0.000 claims description 71
- 239000010410 layer Substances 0.000 claims description 51
- 229910021529 ammonia Inorganic materials 0.000 claims description 49
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 48
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 36
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 31
- 229910000510 noble metal Inorganic materials 0.000 claims description 24
- 239000010948 rhodium Substances 0.000 claims description 22
- 239000000835 fiber Substances 0.000 claims description 21
- 239000010936 titanium Substances 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000010304 firing Methods 0.000 claims description 13
- 239000012784 inorganic fiber Substances 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 229910052703 rhodium Inorganic materials 0.000 claims description 10
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052878 cordierite Inorganic materials 0.000 claims description 9
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- 239000010937 tungsten Substances 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052680 mordenite Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 6
- 239000011247 coating layer Substances 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 239000000969 carrier Substances 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 18
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 18
- 239000004372 Polyvinyl alcohol Substances 0.000 description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Description
【０００１】[0001]
【産業上の利用分野】本発明は、排ガス浄化触媒および
その製造方法に係り、特に酸性ガス（ＮＯｘ）を含有す
る排ガスの浄化触媒およびその製造方法であって、脱硝
装置で使用されたアンモニアのうち装置後流に排出され
るリークアンモニア濃度を上昇させることなく、高い反
応率を得るための排ガス浄化触媒およびその製造方法に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an exhaust gas purifying catalyst and a method for producing the same, and more particularly to an exhaust gas purifying catalyst containing acidic gas (NOx) and a method for producing the same. The present invention relates to an exhaust gas purifying catalyst for obtaining a high reaction rate without increasing the concentration of leaked ammonia discharged to the downstream of the apparatus, and a method for producing the same.
【０００２】[0002]
【従来の技術】燃焼排ガスの脱硝に従来用いられてきた
のは、図３に示すような脱硝装置であった。図３におい
て、燃焼装置４からの燃焼排ガスは煙道１０を経て、脱
硝装置５に流入して、処理され、処理後の排ガスは空気
予熱器６で熱回収され、集塵機７で脱塵されたのち、煙
突８より排出される。この装置は、煙道中の４００℃前
後の適当な温度域でアンモニアをアンモニア導入部９か
ら注入することにより、注入したアンモニア（ＮＨ3)を
還元剤として窒素酸化物（ほとんどＮＯであるが、ＮＯ
2 、Ｎ2 Ｏ他の成分も存在するためＮＯｘという）を窒
素（Ｎ2)と水蒸気（Ｈ2 Ｏ）に分解している。この際、
該反応における反応速度および反応率を向上させるため
に脱硝触媒を利用している。そのため、ＮＯｘの分解率
を向上させるには、ＮＨ3 注入時のＮＨ3 ／ＮＯｘモル
比（以下、ＮＨ3 ／ＮＯｘモル比という）を向上させれ
ばよいのであるが、ＮＨ3 ／ＮＯｘモル比を０．８より
大きくした場合、未反応アンモニアが、排ガスに混入し
てくる。このような状態で、排ガスを大気中に放出した
場合、アンモニアによる二次公害、アンモニアと硫酸と
の反応により生成する酸性硫安によるプラントの腐食と
いった問題を生じるので、通常、ＮＨ3 ／ＮＯｘモル比
を１より低い状態で運転している。2. Description of the Related Art A denitration apparatus as shown in FIG. 3 has been conventionally used for denitration of combustion exhaust gas. In FIG. 3, the combustion exhaust gas from the combustion device 4 flows into the denitration device 5 through the flue 10 and is treated. The treated exhaust gas is heat-recovered by the air preheater 6 and dedusted by the dust collector 7. After that, it is discharged from the chimney 8. This device injects ammonia from the ammonia introduction part 9 in an appropriate temperature range around 400 ° C. in the flue, and uses the injected ammonia (NH 3 ) as a reducing agent to generate nitrogen oxides (almost NO, but NO.
2 , N 2 O and other components also exist, so NOx is decomposed into nitrogen (N 2 ) and water vapor (H 2 O). On this occasion,
A denitration catalyst is used to improve the reaction rate and reaction rate in the reaction. Therefore, in order to improve the degradation rate of NOx is, NH 3 injection NH 3 / NOx molar ratio at the time (hereinafter, referred to as NH 3 / NOx molar ratio) but it is the it is sufficient to improve, NH 3 / NOx molar ratio When the ratio is larger than 0.8, unreacted ammonia is mixed in the exhaust gas. When exhaust gas is released into the atmosphere in such a state, problems such as secondary pollution by ammonia and corrosion of the plant by acidic ammonium sulfate generated by the reaction between ammonia and sulfuric acid occur. Therefore, the NH 3 / NOx molar ratio is usually used. Is operating in a state lower than 1.
【０００３】上記の問題点を解決するために、脱硝装置
内の上流（入口）側に脱硝反応用の触媒を設置し、下流
（出口）側に白金、パラジウム等を担持した酸化触媒を
設置して
２ＮＨ3 ＋３／２Ｏ2 → Ｎ2 ＋３Ｈ2Ｏ … （１）
という反応でアンモニアを分解するという構造も考えら
れている（例えば、特開平１−１８０２２１号公報、特
開平２−１９１５２７号公報）。該発明によれば、ＮＨ
3 ／ＮＯｘモル比を１よりかなり低い状態で運転した場
合に発生する低濃度のリークアンモニアに対しては充分
効果があるであろうが、高脱硝率を得るために、ＮＨ3
／ＮＯｘモル比を１以上で運転した場合には効果的では
ない。というのは、排ガス中に残留するアンモニア（リ
ークアンモニアという）の発生は低減できるが、酸化触
媒がＮＨ3 を分解する際に、
２ＮＨ3 ＋５／２Ｏ2 → ２ＮＯ＋３Ｈ2Ｏ … （２）
で示される反応も必ず起こるため、ＮＯｘの発生により
脱硝装置全体としては期待されたほどの脱硝率を得られ
ないからである。そのため、上記の方法は、リークアン
モニア濃度が余り高くない領域つまりＮＨ3 ／ＮＯｘモ
ル比が１よりかなり低い場合においてのみ有効で、ＮＨ
3 ／ＮＯｘモル比を高くした場合（例えば１以上の場
合）、脱硝率の改善を阻害し効果がほとんどなかった。In order to solve the above problems, a catalyst for denitration reaction is installed on the upstream side (inlet) of the denitration apparatus, and an oxidation catalyst carrying platinum, palladium, etc. is installed on the downstream side (outlet). 2NH 3 + 3 / 2O 2 → N 2 + 3H 2 O (1) is also considered as a structure for decomposing ammonia (for example, JP-A-1-180221 and JP-A-2-191527). . According to the invention, NH
Although it may have a sufficient effect on the low-concentration leaked ammonia generated when operating at a 3 / NOx molar ratio much lower than 1, it is necessary to use NH 3 in order to obtain a high denitration rate.
It is not effective when operated at a NOx / NOx molar ratio of 1 or more. The generation of residual ammonia (called leak ammonia) in the exhaust gas can be reduced, but when the oxidation catalyst decomposes NH 3 , it is represented by 2NH 3 + 5 / 2O 2 → 2NO + 3H 2 O (2) This is because the reaction always occurs, and the NOx removal rate cannot reach the expected NOx removal rate as a whole due to the generation of NOx. Therefore, the above method is effective only in the region where the leak ammonia concentration is not very high, that is, when the NH 3 / NOx molar ratio is considerably lower than 1.
When the 3 / NOx molar ratio was increased (for example, 1 or more), improvement in the denitration rate was hindered and there was almost no effect.
【０００４】そこで、脱硝触媒と酸化触媒とを別々に造
り、これらを脱硝装置内に積層・充填することにより、
脱硝反応後のリークアンモニアを効率よく分解する方法
も考えられている（例えば、特開昭６２−６５７２１号
公報、特開昭６２−２０４８３１号公報）。この方法
は、積層段数を増すことによって、ＮＨ3 とＮＯｘをい
ずれも低減させ得る方法として優れている。しかし、排
ガス組成に対応した脱硝触媒と酸化触媒の割合変更によ
る使用条件の変化への対応や、長時間使用後の劣化触媒
を交換する際の作業性が積層段数に比例して困難になる
ため、あらかじめ設定された条件でしか対応できないも
のであった。また、酸化性能が高く劣化しにくいＰｔ、
Ｐｄ、Ｒｈのいずれか１種以上からなる貴金属（以下貴
金属という）触媒を酸化に使用した場合、酸化速度が非
常に早いため、ＮＨ3 のＮＯｘへの酸化が過剰に発生し
やすい。そのため、きわめて厳密な反応条件に制御しな
いと、ＮＨ3 によるＮＯｘ還元反応よりもＮＨ3 の酸化
が促進され、排ガス中のＮＯｘ濃度がむしろ増加するこ
とさえ起こり得るという問題点もあった。Therefore, by separately producing a denitration catalyst and an oxidation catalyst and stacking and filling them in a denitration device,
A method for efficiently decomposing leaked ammonia after the denitration reaction has also been considered (for example, JP-A-62-65721 and JP-A-62-204831). This method is excellent as a method that can reduce both NH 3 and NOx by increasing the number of stacked layers. However, it is difficult to respond to changes in usage conditions by changing the ratio of denitration catalyst and oxidation catalyst corresponding to the exhaust gas composition, and workability when replacing a deteriorated catalyst after long-term use is proportional to the number of stacking layers. , It was something that could only be handled under preset conditions. In addition, Pt, which has high oxidation performance and does not easily deteriorate,
When a noble metal catalyst (hereinafter referred to as a noble metal) composed of at least one of Pd and Rh is used for the oxidation, the oxidation rate is very fast, and thus excessive oxidation of NH 3 to NOx is likely to occur. Therefore, if not controlled very precise reaction conditions, promotes the oxidation of NH 3 of the NOx reduction reaction by NH 3, the NOx concentration in the exhaust gas was also a problem that even possible to increase rather.
【０００５】また、脱硝触媒上に貴金属触媒を担持する
触媒構造も考えられており（特開昭５４−８２３９２号
公報、および特開昭６３−２９４９４６号公報）、耐Ｓ
Ｏｘ性やＮＯ2 の分解に効果があるといわれている。し
かし、本発明が対象としている高ＮＨ3 ／ＮＯｘモル比
下では、つぎのような現象が発生することがわかった。
（１）脱硝触媒の近傍に酸化触媒が存在し、その酸化触
媒によってＮＯｘ還元用のＮＨ3 が脱硝触媒に供給され
る前に分解されるため、脱硝反応が阻害される。
（２）酸化触媒はＮＨ3 を酸化・分解する際にＮＯｘを
必ず発生する。Further, a catalyst structure in which a noble metal catalyst is supported on a denitration catalyst has also been considered (JP-A-54-82392 and JP-A-63-294946), and S-resistant.
It is said to be effective in Ox property and decomposition of NO 2 . However, it was found that the following phenomenon occurs under the high NH 3 / NOx molar ratio targeted by the present invention. (1) Since an oxidation catalyst exists near the denitration catalyst and NH 3 for NOx reduction is decomposed by the oxidation catalyst before being supplied to the denitration catalyst, the denitration reaction is inhibited. (2) The oxidation catalyst always produces NOx when oxidizing and decomposing NH 3 .
【０００６】以上の問題点のために、脱硝触媒表面で脱
硝反応が起こる際のＮＨ3 ／ＮＯｘモル比は、脱硝触媒
装置入口の煙道ガスでの値よりもかなり低下し、それに
比例して脱硝率も脱硝触媒のみの場合よりも低下してし
まうという問題点を有する。Due to the above problems, the NH 3 / NOx molar ratio when the denitration reaction occurs on the surface of the denitration catalyst is considerably lower than the value in the flue gas at the inlet of the denitration catalyst device, and in proportion thereto There is also a problem that the denitration rate is also lower than in the case where only the denitration catalyst is used.
【０００７】[0007]
【発明が解決しようとする課題】従来技術は燃焼排ガス
中のＮＯｘをできるだけ高い割合で除去できるような高
ＮＨ3 ／ＮＯｘモル比の状態で運転した場合、脱硝装置
からのリークアンモニアによる二次公害が発生したり、
リークアンモニアと排ガス中のＳＯｘとによる酸性硫安
に基づく腐食の発生や、還元剤としてのアンモニアの酸
化により発生するＮＯｘのため脱硝率の向上が阻害され
るという問題があった。In the prior art, when operating in a state of high NH 3 / NOx molar ratio capable of removing NOx in the combustion exhaust gas at the highest possible ratio, secondary pollution due to ammonia leaked from the denitration device. May occur,
There is a problem that the increase in the denitration rate is hindered by the occurrence of corrosion due to acidic ammonium sulfate due to leaked ammonia and SOx in the exhaust gas, and the NOx generated due to the oxidation of ammonia as a reducing agent.
【０００８】本発明の目的は上記従来技術の問題点を解
決し、リークアンモニアが少なく、かつ高い脱硝率を得
ることができる排ガス浄化触媒およびその製造方法を得
ることにある。An object of the present invention is to solve the above-mentioned problems of the prior art, and to obtain an exhaust gas purifying catalyst and a method for producing the same, which can reduce the amount of leaked ammonia and can obtain a high denitration rate.
【０００９】[0009]
【課題を解決するための手段】上記目的を達成するため
本願の第１の発明は、排ガス中の窒素酸化物を還元剤と
してのアンモニアを用いて接触還元するとともに、未反
応のアンモニアを分解する排ガス浄化触媒において、チ
タニア、コーディエライト、ゼオライト、アルミナおよ
びシリカから選ばれた一種以上の多孔触媒担体表面に、
酸化触媒層として白金（Ｐｔ）、パラジウム（Ｐｄ）、
ロジウム（Ｒｈ）から選ばれた一種以上の貴金属からな
る触媒層を形成させ、かつ、その層上に脱硝触媒層とし
てチタン（Ｔｉ）、モリブデン（Ｍｏ）、タングステン
（Ｗ）、バナジウム（Ｖ）から選ばれた一種以上の酸化
物からなる触媒層を設けたことを特徴とする排ガス浄化
触媒に関する。To achieve the above object, the first invention of the present application is to catalytically reduce nitrogen oxides in exhaust gas by using ammonia as a reducing agent and decompose unreacted ammonia. In exhaust gas purification catalysts, titania, cordierite, zeolite, alumina and
And one or more porous catalyst carrier surface selected from silica,
As the oxidation catalyst layer, platinum (Pt), palladium (Pd),
A catalyst layer made of one or more noble metals selected from rhodium (Rh) is formed, and titanium (Ti), molybdenum (Mo), tungsten (W), vanadium (V) is formed on the layer as a denitration catalyst layer. The present invention relates to an exhaust gas purifying catalyst, which is provided with a catalyst layer made of one or more selected oxides.
【００１０】第２の発明は、上記第１の発明において、
ゼオライトとして水素置換型モルデナイトを用いたこと
を特徴とする排ガス浄化触媒に関する。第３の発明は、
排ガス中の窒素酸化物を還元剤としてのアンモニアを用
いて接触還元するとともに、未反応のアンモニアを分解
する排ガス浄化触媒において、白金（Ｐｔ）、パラジウ
ム（Ｐｄ）、ロジウム（Ｒｈ）から選ばれた一種以上の
貴金属触媒成分を含有する多孔担体表面を、チタン（Ｔ
ｉ）、モリブデン（Ｍｏ）、タングステン（Ｗ）、バナ
ジウム（Ｖ）から選ばれた一種以上の酸化物からなる脱
硝触媒層で被覆したことを特徴とする排ガス浄化触媒に
関する。A second invention is the same as the first invention,
The present invention relates to an exhaust gas purification catalyst characterized by using hydrogen-substituted mordenite as zeolite. The third invention is
An exhaust gas purifying catalyst that catalytically reduces nitrogen oxides in exhaust gas using ammonia as a reducing agent and decomposes unreacted ammonia is selected from platinum (Pt), palladium (Pd), and rhodium (Rh). The surface of the porous carrier containing one or more noble metal catalyst components is coated with titanium (T
(i), molybdenum (Mo), tungsten (W), vanadium (V) The present invention relates to an exhaust gas purifying catalyst, which is coated with a denitration catalyst layer made of one or more oxides selected from vanadium (V).
【００１１】第４の発明は、上記第３の発明において、
多孔担体が水素置換型モルデナイトであることを特徴と
する排ガス浄化触媒に関する。第５の発明は、排ガス中
の窒素酸化物をアンモニアを用いて接触還元するととも
に、未反応のアンモニアを分解する排ガス浄化触媒の製
造方法において、多孔触媒担体表面に、酸化触媒貴金属
成分と脱硝触媒成分および粒状多孔担体よりなるスラリ
ーを含浸した後焼成し、この焼成体表面に脱硝触媒成分
を担持したのち焼成することを特徴とする排ガス浄化触
媒の製造方法に関する。A fourth invention is based on the third invention.
The exhaust gas purifying catalyst is characterized in that the porous carrier is hydrogen-substituted mordenite. A fifth aspect of the present invention is a method for producing an exhaust gas purifying catalyst, which comprises catalytically reducing nitrogen oxides in exhaust gas with ammonia and decomposing unreacted ammonia, wherein an oxidation catalyst noble metal component and a denitration catalyst are formed on the surface of the porous catalyst carrier. The present invention relates to a method for producing an exhaust gas purifying catalyst, which comprises impregnating with a slurry comprising components and a granular porous carrier, followed by firing, supporting a denitration catalyst component on the surface of the fired body, and then firing.
【００１２】第６の発明は、排ガス中の窒素酸化物をア
ンモニアを用いて接触還元するとともに、未反応のアン
モニアを分解する排ガス浄化触媒において、チタン（Ｔ
ｉ）、モリブデン（Ｍｏ）、タングステン（Ｗ）、バナ
ジウム（Ｖ）から選ばれた一種以上の酸化物からなる脱
硝触媒内に、少なくともアルカリ土類金属元素、アルミ
ニウムおよびシリコンの３元素を含有する無機繊維を含
み、かつ、該繊維上に白金（Ｐｔ）、パラジウム（Ｐ
ｄ）、ロジウム（Ｒｈ）から選ばれた一種以上の貴金属
からなる酸化触媒層を形成させたことを特徴とする排ガ
ス浄化触媒に関する。A sixth invention is an exhaust gas purifying catalyst for catalytically reducing nitrogen oxides in exhaust gas with ammonia and decomposing unreacted ammonia.
Inorganic containing at least three elements of alkaline earth metal elements, aluminum and silicon in a denitration catalyst composed of one or more oxides selected from i), molybdenum (Mo), tungsten (W) and vanadium (V). It contains fibers, and platinum (Pt), palladium (P
d), an exhaust gas purifying catalyst having an oxidation catalyst layer formed of one or more noble metals selected from rhodium (Rh).
【００１３】第７の発明は、排ガス中の窒素酸化物をア
ンモニアを用いて接触還元するとともに、未反応のアン
モニアを分解する排ガス浄化触媒において、チタン（Ｔ
ｉ）、モリブデン（Ｍｏ）、タングステン（Ｗ）、バナ
ジウム（Ｖ）から選ばれた一種以上の酸化物からなる脱
硝触媒層内に無機繊維を含み、かつ該繊維上にチタン、
シリカまたはアルミニウムから選ばれた一種以上の酸化
物またはゼオライトのコーティング層が形成され、かつ
該コーティング層上に白金（Ｐｔ）、パラジウム（Ｐ
ｄ）、ロジウム（Ｒｈ）から選ばれた一種以上の貴金属
からなる酸化触媒を担持したことを特徴とする排ガス浄
化触媒に関する。A seventh invention is an exhaust gas purifying catalyst for catalytically reducing nitrogen oxides in exhaust gas with ammonia and decomposing unreacted ammonia.
i), molybdenum (Mo), tungsten (W), vanadium (V) containing an inorganic fiber in the denitration catalyst layer consisting of one or more oxides selected, and titanium on the fiber,
A coating layer of one or more oxides or zeolites selected from silica or aluminum is formed, and platinum (Pt), palladium (P) is formed on the coating layer.
d), an exhaust gas purifying catalyst, which carries an oxidation catalyst composed of one or more noble metals selected from rhodium (Rh).
【００１４】[0014]
【作用】本発明で使用する脱硝触媒は、ＮＨ3 を還元剤
とし、主に
４ＮＯ ＋ ４ＮＨ3 ＋ Ｏ2 → ４Ｎ2 ＋６Ｈ2Ｏ … （３）
２ＮＯ ＋ ４ＮＨ3 ＋ Ｏ2 → ３Ｎ2 ＋６Ｈ2Ｏ … （４）
といった反応によりＮＯｘ、特にその主成分であるＮＯ
を無害化している。逆に考えれば、脱硝触媒は、ＮＯｘ
を酸化剤にしてＮＨ3 を無害化するＮＨ3 除去触媒とし
ても利用できる。The denitration catalyst used in the present invention uses NH 3 as a reducing agent and mainly contains 4NO + 4NH 3 + O 2 → 4N 2 + 6H 2 O (3) 2NO + 4NH 3 + O 2 → 3N 2 + 6H 2 O ... (4) causes NOx, especially NO which is the main component thereof.
Is made harmless. In other words, the NOx removal catalyst is NOx.
Can also be used as an NH 3 removal catalyst that detoxifies NH 3 by using oxidant.
【００１５】一方、貴金属を触媒成分に用いた場合、Ｎ
Ｈ3 酸化速度が大きすぎるという欠点を生じるため、Ｎ
Ｈ3 を含んだ排ガスとの接触を制限することが重要にな
る。また、脱硝率を向上させるためには、ＮＨ3 酸化に
伴ない必ず発生するＮＯｘガスをできるだけ高い濃度で
還元・分解する必要がある。そこで、本願の特許請求の
範囲の請求項１〜請求項５の発明においては、以下に示
す過程でＮＯｘとＮＨ3 のいずれをも高い割合で除去す
ることができる。
（１）脱硝触媒層を表層（ガス側）にして酸化触媒層と
脱硝触媒層を積層する。
（２）特に、排ガスと直接接触する触媒の最外層は脱硝
触媒層にし、酸化触媒は脱硝触媒層を拡散して到達した
ガス（触媒内部拡散ガスという）のみを酸化する。つま
り、反応速度の相対的に遅い脱硝触媒を表層においてＮ
Ｏｘを分解し、ＮＯｘはほとんど含まれていないがＮＨ
3 を含む該触媒内部拡散ガスを酸化触媒により酸化す
る。
（３）ＮＨ3 を酸化する際に発生したＮＯｘは、触媒内
部から排ガス中へ放出されて希薄な濃度になる場合に、
必ず脱硝触媒層を通過するため、ＮＨ3 が過剰となって
いる脱硝触媒層で還元・分解する。
（４）ＮＨ3 濃度が低下すると、酸化触媒層へ拡散して
くるＮＨ3 量も比例して減少し、そのため酸化触媒層か
ら脱硝触媒層へのＮＯｘの供給量も減少するため、触媒
の自己制御により、広い使用条件で安定的に利用可能と
なる。On the other hand, when a noble metal is used as the catalyst component, N
Since the disadvantage is that the H 3 oxidation rate is too high, N 3
It is important to limit contact with the exhaust gas containing H 3 . Further, in order to improve the denitration rate, it is necessary to reduce / decompose the NOx gas, which is always generated with the NH 3 oxidation, at a concentration as high as possible. Therefore, in the inventions of claims 1 to 5 of the claims of the present application, both NOx and NH 3 can be removed at a high rate in the following process. (1) An oxidation catalyst layer and a denitration catalyst layer are laminated with the denitration catalyst layer as a surface layer (gas side). (2) In particular, the outermost layer of the catalyst that is in direct contact with the exhaust gas is the denitration catalyst layer, and the oxidation catalyst oxidizes only the gas that has reached through diffusion of the denitration catalyst layer (called catalyst internal diffusion gas). In other words, the NOx removal catalyst having a relatively slow reaction rate is not
Decomposes Ox and contains almost no NOx, but NH
The catalyst internal diffusion gas containing 3 is oxidized by an oxidation catalyst. (3) When NOx generated during the oxidation of NH 3 is released from the inside of the catalyst into the exhaust gas and becomes a lean concentration,
Since it always passes through the denitration catalyst layer, it is reduced and decomposed in the denitration catalyst layer where NH 3 is excessive. (4) When the NH 3 concentration decreases, the amount of NH 3 that diffuses into the oxidation catalyst layer also decreases in proportion, and therefore the amount of NOx supplied from the oxidation catalyst layer to the denitration catalyst layer also decreases, so that the catalyst self The control enables stable use under a wide range of use conditions.
【００１６】なお、アンモニア分解時に発生するＮＯｘ
を効果的に分解するには、酸化触媒層の全面あるいはほ
とんどを脱硝触媒が覆っていることが不可欠である。と
いうのは、酸化触媒は脱硝触媒に比べて反応速度が非常
に大きく、表面に酸化触媒が露出した場合、アンモニア
分解時のＮＯｘ生成により、脱硝率を低下させるからで
ある。また、この際、酸化触媒層と脱硝触媒層をそれぞ
れ複数もつ多層構造にしても同様の効果が得られるが、
製作行程の複雑化とそれに伴う製造コストの上昇に比べ
て脱硝性能およびＮＨ3 分解性能の向上はほとんどみら
れないので有効とはいえない。NOx generated during ammonia decomposition
In order to effectively decompose the above, it is indispensable that the denitration catalyst covers the entire surface or almost all of the oxidation catalyst layer. This is because the oxidation catalyst has a much higher reaction rate than the denitration catalyst, and when the oxidation catalyst is exposed on the surface, NOx is generated during the decomposition of ammonia to reduce the denitration rate. At this time, the same effect can be obtained even if a multilayer structure having a plurality of oxidation catalyst layers and a plurality of denitration catalyst layers is provided.
It cannot be said to be effective because the denitration performance and the NH 3 decomposition performance are hardly improved as compared with the complexity of the manufacturing process and the accompanying increase in the manufacturing cost.
【００１７】また、本願の特許請求の範囲の請求項６〜
請求項７の発明においては、図８に示すように、まず、
以下に示す過程でＮＯｘとＮＨ3 のいずれもを高い割合
で除去可能となる。
（１）酸化触媒を担持した繊維を脱硝触媒層に混合し、
脱硝触媒と酸化触媒とをある程度隔離するすることによ
り、脱硝触媒へのＮＨ3 の供給を十分に確保する。
（２）高比表面積の担体上に担持することで、酸化触媒
自体は高活性となる。また、反応速度の相対的に遅い脱
硝触媒の接触面積を酸化触媒に比べて極めて大きくする
ことで、脱硝性能を確保する一方、過剰なＮＨ3 を含む
ガスは、酸化触媒により酸化する。
（３）ＮＨ3 を酸化する際に発生したＮＯｘは、該酸化
触媒近傍に必ず存在し、かつ、ＮＨ3 が過剰となってい
る脱硝触媒層で還元・分解する。
（４）ＮＨ3 濃度が低下すると、酸化触媒へ拡散してく
るＮＨ3 量も比例して減少し、そのため酸化触媒層から
脱硝触媒層へのＮＯｘの供給量も減少するため、触媒の
自己制御により、広い使用条件で安定的に利用可能とな
る。Further, claims 6 to 6 of the claims of the present application
In the invention of claim 7, as shown in FIG.
Both NOx and NH 3 can be removed at a high rate in the process shown below. (1) Mixing fibers supporting an oxidation catalyst into a denitration catalyst layer,
By separating the denitration catalyst and the oxidation catalyst to some extent, a sufficient supply of NH 3 to the denitration catalyst is secured. (2) By supporting it on a carrier having a high specific surface area, the oxidation catalyst itself becomes highly active. Further, by making the contact area of the denitration catalyst, which has a relatively slow reaction rate, extremely larger than that of the oxidation catalyst, the denitration performance is secured, while the gas containing excess NH 3 is oxidized by the oxidation catalyst. (3) NOx generated during the oxidation of NH 3 is always present in the vicinity of the oxidation catalyst and is reduced and decomposed in the denitration catalyst layer in which NH 3 is excessive. (4) When the NH 3 concentration decreases, the amount of NH 3 that diffuses into the oxidation catalyst also decreases in proportion, and therefore the amount of NOx supplied from the oxidation catalyst layer to the denitration catalyst layer also decreases, so the catalyst self-controls. As a result, it can be stably used under a wide range of use conditions.
【００１８】なお、アンモニア分解時に発生するＮＯｘ
を効果的に分解するには、脱硝触媒のみが存在する部分
のガス接触面積が酸化触媒のガス接触面積よりきわめて
大きくかつ分散していることが不可欠である。というの
は、酸化触媒は脱硝触媒に比べて反応速度が非常に大き
いため、例えば、酸化触媒が脱硝触媒表面全体へ単分子
層状態で均質に分散された場合のような酸化触媒の高分
散状態では、触媒全面で、ＮＯｘが大量に発生し、脱硝
率が低下するからである。NOx generated during ammonia decomposition
In order to effectively decompose the catalyst, it is essential that the gas contact area of the portion where only the denitration catalyst exists is much larger than the gas contact area of the oxidation catalyst and dispersed. Because the reaction rate of the oxidation catalyst is much higher than that of the denitration catalyst, for example, the highly dispersed state of the oxidation catalyst, such as when the oxidation catalyst is uniformly dispersed in a monolayer state over the entire surface of the denitration catalyst, Then, a large amount of NOx is generated on the entire surface of the catalyst, and the denitration rate decreases.
【００１９】該酸化触媒を、脱硝反応をできるだけ阻害
せずに使用するには、脱硝触媒中に、島状に疎らに酸化
触媒を分散させることが重要であり、そのためには、添
加する繊維量を制限することが望ましい。本発明の脱硝
触媒は、例えば化石燃料を燃焼させる際に発生するＮ
Ｏ、ＮＯ2等の窒素酸化物に対して、ＮＨ3 を還元剤と
して、Ｎ2 およびＨ2 Ｏに分解する作用を有するチタン
（Ｔｉ）、モリブデン（Ｍｏ）、タングステン（Ｗ）、
バナジウム（Ｖ）から選ばれた一種以上の酸化物からな
る脱硝触媒層とＯ2 によりＮＨ3 を酸化・分解する白金
（Ｐｔ）、パラジウム（Ｐｄ）、ロジウム（Ｒｈ）から
選ばれた一種以上の貴金属を触媒成分とする酸化触媒層
を内部に有する。In order to use the oxidation catalyst without inhibiting the denitration reaction as much as possible, it is important to disperse the oxidation catalyst in an island-like manner in the denitration catalyst. It is desirable to limit The denitration catalyst of the present invention is an example of N generated when burning fossil fuel.
Titanium (Ti), molybdenum (Mo), tungsten (W) having a function of decomposing into nitrogen oxides such as O and NO 2 by using NH 3 as a reducing agent into N 2 and H 2 O,
A denitration catalyst layer composed of one or more oxides selected from vanadium (V) and one or more selected from platinum (Pt), palladium (Pd), and rhodium (Rh) that oxidize and decompose NH 3 by O 2 . It has an oxidation catalyst layer containing a noble metal as a catalyst component therein.
【００２０】図１に示す本発明の脱硝触媒では、触媒層
が二つの領域で構成されている。煙道ガス側（表層とい
う）の領域１は、ＮＨ3 と煙道ガス中のＮＯｘとの反応
でＮＯｘを除去する機能をもつ。一方、担体側（下層と
いう）の領域２は、脱硝反応後領域１から拡散してくる
ＮＨ3 を含んだ触媒内部拡散ガスを酸化する機能を有す
る。In the denitration catalyst of the present invention shown in FIG. 1, the catalyst layer is composed of two regions. Region 1 on the flue gas side (referred to as the surface layer) has a function of removing NOx by a reaction between NH 3 and NOx in the flue gas. On the other hand, the region 2 on the carrier side (referred to as the lower layer) has a function of oxidizing the catalyst internal diffusion gas containing NH 3 diffused from the region 1 after the denitration reaction.
【００２１】本発明の実施に用いられる無機繊維として
は、Ｅガラスなどの無アルカリガラスの数〜１０μｍの
単繊維を使用する。繊維長は触媒ペーストを作製する際
の他の原料との混合時の取扱いやすさを考慮して、数１
０μｍ〜数mm程度の長さに切断したものでもよい。この
繊維に対して、比表面積が１００m2／ｇ以上のシリカ、
チタニアまたはアルミナのスラリーをスプレー法により
スクリーンの表面に膜状に形成してもよい。この場合、
均質膜を形成しやすいように、例えば、ポリビニールア
ルコール等の有機結合剤を上記混合物に添加してもよ
い。As the inorganic fibers used in the practice of the present invention, non-alkali glass such as E glass having a number of 10 to 10 μm is used. The fiber length is several 1 in consideration of the ease of handling when mixing with other raw materials when preparing the catalyst paste.
It may be cut into a length of about 0 μm to several mm. Silica with a specific surface area of 100 m 2 / g or more,
A slurry of titania or alumina may be formed into a film on the surface of the screen by a spray method. in this case,
An organic binder such as polyvinyl alcohol may be added to the mixture to facilitate formation of a homogeneous film.
【００２２】また、該繊維（上記処理の有無に関わら
ず）を塩酸、硫酸または硝酸を含む鉱酸に浸漬すること
により、繊維表面のアルカリ土類金属元素を溶出させ、
多孔質な繊維表面に改質できる。その際、該鉱酸と上記
のシリカ、アルミナ、またはチタニアスラリーを混合し
て塗布してもよい。なお、繊維の添加量が多くなると、
繊維自体は脱硝活性がないため、単位重量当たりの触媒
活性は繊維添加量に比例して低下する。そこで、本発明
では、添加量を１ wt ％以上２０ wt ％以下にすること
にした。Further, the alkaline earth metal element on the surface of the fiber is eluted by immersing the fiber (with or without the above treatment) in a mineral acid containing hydrochloric acid, sulfuric acid or nitric acid,
Can be modified to have a porous fiber surface. At that time, the mineral acid and the above silica, alumina, or titania slurry may be mixed and applied. In addition, when the amount of fiber added increases,
Since the fiber itself has no denitration activity, the catalytic activity per unit weight decreases in proportion to the amount of fiber added. Therefore, in the present invention, the addition amount is set to 1 wt% or more and 20 wt% or less.
【００２３】また、酸化触媒を無機繊維上に担持する
際、比表面積が１００m2／ｇ以上のシリカ、チタニアま
たはアルミナのスラリーと酸化触媒とを混合した後、該
混合物を該繊維上にコーティングしたものも使用可能で
はあるが、担持した場合よりも貴金属触媒の利用率が悪
いので効率的ではない。図４は上記の操作で得られた触
媒の模式である。この図からあきらかなように、酸化触
媒は無機繊維表面に固定され、できる限り脱硝触媒表面
へのＮＨ3 吸着を阻害しないようになっている。この
際、酸化触媒担体となる無機触媒表面にコーティング層
を設けることにより、担体の比表面積を改良し、より少
量の酸化触媒で高い酸化活性を得ることができる。When the oxidation catalyst is supported on the inorganic fiber, a slurry of silica, titania or alumina having a specific surface area of 100 m 2 / g or more is mixed with the oxidation catalyst, and then the mixture is coated on the fiber. Although the materials can be used, they are not efficient because the utilization rate of the noble metal catalyst is lower than that when they are supported. FIG. 4 is a schematic diagram of the catalyst obtained by the above operation. As is clear from this figure, the oxidation catalyst is fixed on the surface of the inorganic fiber so as not to hinder the adsorption of NH 3 on the surface of the denitration catalyst as much as possible. At this time, by providing a coating layer on the surface of the inorganic catalyst that serves as the oxidation catalyst carrier, the specific surface area of the carrier can be improved, and a high oxidation activity can be obtained with a smaller amount of the oxidation catalyst.
【００２４】酸化触媒用貴金属の担持方法についても、
今回は、単純に塩化物を焼成しただけで行なっている
が、無電解鉱金の手法を用いて、塩化物を担持した後、
ヒドラジンやホルマリン等で還元して、貴金属として担
持してもよい。Regarding the method of supporting the noble metal for the oxidation catalyst,
This time, it is done by simply firing chloride, but after supporting chloride using the electroless gold method,
It may be supported as a noble metal by reducing with hydrazine or formalin.
【００２５】[0025]
【実施例】以下、本発明を実施例に基づいて説明する。
なお、すべてハニカム形状の触媒で実験を行なっている
が、容易に触媒活性比較できるためであり、本発明の適
用を特にハニカム形状に限定するものではない。
実施例１
脱硝触媒層には酸化物触媒（組成：Ｔｉ／Ｍｏ／Ｖ＝８
３／５／２（原子比）、比表面積１２０m2／ｇ）を用
い、貴金属触媒成分としてＰｔを用いた。触媒担体とし
て高比表面積コーディエライト（比表面積１２０m2／
ｇ）製ハニカムを用いた。塩化白金水溶液を用いてハニ
カム表面に含浸し、５００℃で２時間焼成した（この状
態を、Ｐｔ担持酸化触媒という）。さらに、酸化物脱硝
触媒スラリー（結合剤：ポリビニルアルコール（ＰＶ
Ａ）２％、水分濃度５０ wt ％）に該Ｐｔ担持酸化触媒
をディッピングした後、５００℃で２時間焼成した。焼
成後の触媒断面を観察したところ、脱硝触媒層が約０．
５mmの厚さでＰｔ担持酸化触媒層を覆った状態であっ
た。EXAMPLES The present invention will be described below based on examples.
It should be noted that although all the experiments were carried out with honeycomb-shaped catalysts, the catalyst activity can be easily compared, and the application of the present invention is not particularly limited to honeycomb-shaped catalysts. Example 1 An oxide catalyst (composition: Ti / Mo / V = 8) was formed in the denitration catalyst layer.
3/5/2 (atomic ratio) and a specific surface area of 120 m 2 / g) were used, and Pt was used as a noble metal catalyst component. High specific surface area cordierite as catalyst carrier (specific surface area 120m 2 /
g) Honeycomb was used. The surface of the honeycomb was impregnated with an aqueous solution of platinum chloride and fired at 500 ° C. for 2 hours (this state is referred to as Pt-supported oxidation catalyst). Furthermore, oxide denitration catalyst slurry (binder: polyvinyl alcohol (PV
The Pt-supported oxidation catalyst was dipped to A) 2% and water concentration 50 wt%), and then calcined at 500 ° C. for 2 hours. When the cross section of the catalyst after calcination was observed, it was found that the denitration catalyst layer had a density of about 0.
The Pt-supported oxidation catalyst layer was covered with a thickness of 5 mm.
【００２６】実施例２
塩化白金１ wt ％、ＰＶＡ２ wt ％および水分３０ wt
％を高比表面積コーディエライト（比表面積１２０m2／
ｇ）粉末に加えて混練したペーストを用いて、押し出し
成形によりハニカム化した後、５００℃で２時間焼成
し、高比表面積酸化触媒を製造する。この触媒を実施例
１で用いた酸化物脱硝触媒スラリーにディッピングした
後、５００℃で２時間焼成した。Example 2 Platinum chloride 1 wt%, PVA 2 wt% and water content 30 wt
% High surface area cordierite (specific surface area 120 m 2 /
g) A paste obtained by kneading in addition to the powder is used to form a honeycomb by extrusion molding and then firing at 500 ° C. for 2 hours to produce a high specific surface area oxidation catalyst. This catalyst was dipped in the oxide denitration catalyst slurry used in Example 1 and then calcined at 500 ° C. for 2 hours.
【００２７】実施例３
脱硝触媒層には実施例１と同一の酸化物触媒を用い、貴
金属触媒成分としてＰｄを用いた。触媒担体として高比
表面積コーディエライト（比表面積１２０m2／ｇ）製ハ
ニカムを用いた。塩化パラジウム水溶液を用いてハニカ
ム表面に含浸し、５００℃で２時間焼成した（この状態
を、Ｐｄ担持酸化触媒という）。さらに、実施例１と同
一の酸化物脱硝触媒スラリー（結合剤：ＰＶＡ２％、水
分濃度５０ wt ％）に該Ｐｄ担持酸化触媒をディッピン
グした後、５００℃で２時間焼成した。Example 3 The same oxide catalyst as in Example 1 was used for the denitration catalyst layer, and Pd was used as the noble metal catalyst component. A honeycomb made of high specific surface area cordierite (specific surface area 120 m 2 / g) was used as a catalyst carrier. The surface of the honeycomb was impregnated with an aqueous palladium chloride solution and fired at 500 ° C. for 2 hours (this state is referred to as Pd-supported oxidation catalyst). Furthermore, the same oxide denitration catalyst slurry as in Example 1 (binder: PVA 2%, water concentration 50 wt%) was dipped with the Pd-supported oxidation catalyst, and then calcined at 500 ° C. for 2 hours.
【００２８】実施例４
脱硝触媒層には酸化物触媒（組成：Ｔｉ／Ｍｏ／Ｖ＝８
３／５／２（原子比）、比表面積１２０m2／ｇ）を用
い、貴金属触媒成分としてＰｔを用いた。触媒担体とし
て高比表面積Ａｌ2Ｏ3 （比表面積１２０m2／ｇ）製ハ
ニカムを用いた。塩化白金水溶液を用いてハニカム表面
に含浸し、５００℃で２時間焼成した（この状態を、Ｐ
ｔ担持酸化触媒という）。さらに、実施例１と同一の酸
化物脱硝触媒スラリーに該Ｐｔ担持酸化触媒をディッピ
ングした後、５００℃で２時間焼成した。なお、アルミ
ナの代わりにシリカまたはチタニアを用いても同様の浄
化触媒が得られた。Example 4 An oxide catalyst (composition: Ti / Mo / V = 8) was formed in the denitration catalyst layer.
3/5/2 (atomic ratio) and a specific surface area of 120 m 2 / g) were used, and Pt was used as a noble metal catalyst component. A honeycomb made of a high specific surface area Al 2 O 3 (specific surface area 120 m 2 / g) was used as a catalyst carrier. The surface of the honeycomb was impregnated with an aqueous solution of platinum chloride and fired at 500 ° C. for 2 hours.
t-supported oxidation catalyst). Furthermore, the Pt-supported oxidation catalyst was dipped in the same oxide denitration catalyst slurry as in Example 1, and then calcined at 500 ° C. for 2 hours. A similar purification catalyst was obtained by using silica or titania instead of alumina.
【００２９】実施例５
脱硝触媒層には酸化物触媒（組成：Ｔｉ／Ｍｏ／Ｖ＝８
３／５／２（原子比）、比表面積１２０m2／ｇ）を用
い、貴金属触媒成分としてＲｈを用いた。塩化ロジウム
水溶液を用いて実施例１と同一のハニカム型コーディエ
ライト担体表面に含浸し、５００℃で２時間焼成した
（この状態を、Ｒｈ担持酸化触媒という）さらに、酸化
物脱硝触媒スラリー（結合剤：ＰＶＡ２％、固体濃度５
０ wt ％）に該Ｒｈ担持酸化触媒をディッピングした
後、５００℃で２時間焼成した。Example 5 An oxide catalyst (composition: Ti / Mo / V = 8) was formed in the denitration catalyst layer.
3/5/2 (atomic ratio) and specific surface area 120 m 2 / g) were used, and Rh was used as a noble metal catalyst component. The surface of the same honeycomb type cordierite carrier as in Example 1 was impregnated with an aqueous solution of rhodium chloride and calcined at 500 ° C. for 2 hours (this state is referred to as Rh-supported oxidation catalyst). Agent: PVA 2%, solid concentration 5
The Rh-supported oxidation catalyst was dipped in an amount of 0 wt%) and then calcined at 500 ° C. for 2 hours.
【００３０】実施例６
塩化白金１ wt ％、ＰＶＡ２ wt ％および水分３０ wt
％を水素置換型モルデナイト（比表面積１２０m2／ｇ）
粉末に加え混練したペーストを用いて、押し出し成形に
よりハニカム化した後、５００℃で２時間焼成し、高比
表面積酸化触媒を製造する。この触媒を実施例１で用い
た酸化物脱硝触媒スラリーにディッピングした後、５０
０℃で２時間焼成した。Example 6 Platinum chloride 1 wt%, PVA 2 wt% and water content 30 wt
% Hydrogen-substituted mordenite (specific surface area 120 m 2 / g)
A paste obtained by kneading in addition to the powder is used to form a honeycomb by extrusion molding and then firing at 500 ° C. for 2 hours to produce a high specific surface area oxidation catalyst. After dipping this catalyst into the oxide denitration catalyst slurry used in Example 1, 50
It was calcined at 0 ° C. for 2 hours.
【００３１】実施例７
触媒担体として、水素置換型モルデナイト（比表面積１
２０m2／ｇ）製ハニカムを用い、後は実施例１と全く同
じ条件で白金を含浸・焼成後、脱硝触媒スラリーにディ
ッピングし、焼成した。
実施例８
表面の脱硝触媒層が強固に酸化触媒担持担体に付着する
ように、実施例１と同様のコーディエライト担体を、塩
化白金を１ wt ％、酸化物脱硝触媒とコーディエライト
が等量含まれたスラリー（結合剤：ポリビニルアルコー
ル（ＰＶＡ）２％、水分濃度５０ wt ％）にディッピン
グ後、５００℃で２時間焼成し、その後、実施例１と同
一条件で脱硝触媒スラリーにディッピング後焼成した。Example 7 As a catalyst carrier, hydrogen-substituted mordenite (specific surface area 1
A honeycomb made of 20 m 2 / g) was used. After that, platinum was impregnated and fired under the same conditions as in Example 1. Then, the catalyst was dipped in a denitration catalyst slurry and fired. Example 8 A cordierite carrier similar to that used in Example 1 was used, 1 wt% of platinum chloride, oxide denitration catalyst and cordierite, etc. were used so that the denitration catalyst layer on the surface firmly adhered to the oxidation catalyst supporting carrier. After dipping into a slurry (binder: polyvinyl alcohol (PVA) 2%, water content 50 wt%) contained in an amount, calcined at 500 ° C. for 2 hours, and then dipping into a denitration catalyst slurry under the same conditions as in Example 1. Baked.
【００３２】比較例１
実施例１で用いたものと同一のハニカム型高比表面積コ
ーディエライト担体を実施例１の酸化物脱硝触媒スラリ
ー液にディッピング後、５００℃で焼成した。
比較例２
塩化白金１ wt ％、ＰＶＡ２ wt ％および水分３０ wt
％を酸化物触媒（組成：Ｔｉ／Ｍｏ／Ｖ＝８３／５／２
（原子比）、比表面積１２０m2／ｇ）に添加して混練
後、得られたペーストを押し出し成形によりハニカム化
し、５００℃で２時間焼成することにより触媒化した。Comparative Example 1 The same honeycomb type high specific surface area cordierite carrier as that used in Example 1 was dipped in the oxide denitration catalyst slurry liquid of Example 1 and then calcined at 500 ° C. Comparative Example 2 Platinum chloride 1 wt%, PVA 2 wt% and water content 30 wt
% Oxide catalyst (composition: Ti / Mo / V = 83/5/2
(Atomic ratio), specific surface area of 120 m 2 / g) and kneaded, and the obtained paste was made into a honeycomb by extrusion molding, and calcined at 500 ° C. for 2 hours to catalyze.
【００３３】図２に実施例１、２、３、４、５、６、
７、８および比較例１、２で作製した脱硝触媒による脱
硝実験結果を示す。燃料に石炭を用いた燃焼装置の排ガ
スで実験を行なった。燃焼排ガスの組成はＳＯ2 ：５０
０ ppm、ＮＯｘ濃度：２００ ppm、Ｏ2 濃度：３．０％
で残りは窒素ガスであった。脱硝実験は温度３５０℃、
ガス流速１７ｍ／ｈの条件下で行ない、触媒入口のＮＨ
3 流量を制御することにより、触媒入口ガス中のＮＨ3
／ＮＯｘモル比を０．６〜１．５まで変化させて、それ
ぞれの定常状態における脱硝率およびリークアンモニア
濃度を求めた。FIG. 2 shows Examples 1, 2, 3, 4, 5, 6,
7 shows the denitration test results using the denitration catalysts produced in Examples 7 and 8 and Comparative Examples 1 and 2. The experiment was conducted with the exhaust gas of the combustion device using coal as the fuel. The composition of combustion exhaust gas is SO 2 : 50
0 ppm, NOx concentration: 200 ppm, O 2 concentration: 3.0%
The rest was nitrogen gas. The temperature of denitration experiment is 350 ℃,
The gas flow rate of 17 m / h was used and NH at the catalyst inlet was used.
3 By controlling the flow rate, NH 3 in the catalyst inlet gas
The / NOx molar ratio was changed from 0.6 to 1.5, and the denitration rate and the leak ammonia concentration in each steady state were obtained.
【００３４】その結果、比較例２以外はいずれの場合
も、脱硝率はほぼ同じ値を示した。一方、ＮＨ3 ／ＮＯ
ｘモル比が０．８以上１．４以下の場合、実施例１、
２、３、４、５、６、７、８および比較例２で作製した
触媒はＮＨ3 濃度にほとんど変化は見られないが、比較
例１で作製した触媒は急激にリークアンモニア濃度が高
くなっている。これは、本発明の実施例として作製した
触媒はすべて脱硝性能とアンモニア分解性能のいずれも
充分であるが、比較例１はアンモニア分解性能に、比較
例２は脱硝性能において、実施例よりもかなり劣ってい
るからである。As a result, in all cases except Comparative Example 2, the denitration rate showed almost the same value. On the other hand, NH 3 / NO
When the x molar ratio is 0.8 or more and 1.4 or less, Example 1,
The catalysts prepared in 2, 3, 4, 5, 6, 7, 8 and Comparative Example 2 show almost no change in the NH 3 concentration, but the catalyst prepared in Comparative Example 1 has a sharply increased leak ammonia concentration. ing. This is because all of the catalysts prepared as Examples of the present invention have sufficient denitration performance and ammonia decomposing performance, but Comparative Example 1 has a better ammonia decomposing performance and Comparative Example 2 has a better denitrifying performance than the Examples. Because it is inferior.
【００３５】なお、実施例１と実施例８の触媒について
１，０００時間試験後の触媒重量変化および触媒性能を
比較した。実験結果を表１に示す。The catalysts of Examples 1 and 8 were compared in weight change and catalyst performance after 1,000 hours of test. The experimental results are shown in Table 1.
【００３６】[0036]
【表１】 [Table 1]
【００３７】触媒性能は両方とも変化はないが、触媒重
量変化は実施例８の方が少ない。このことから、製造コ
ストは上昇するものの、脱硝触媒成分、酸化触媒成分お
よび担体成分の割合を徐々に変化させる中間層を設ける
ことにより、触媒の耐久性が向上することがわかる。以
上の結果から、本発明によれば広いＮＨ3 ／ＮＯｘモル
比範囲で、リークアンモニアが非常に少なく脱硝率の高
い触媒を得ることが可能となる。Both catalyst performances did not change, but the catalyst weight change was less in Example 8. From this, it is understood that the durability of the catalyst is improved by providing the intermediate layer that gradually changes the ratios of the denitration catalyst component, the oxidation catalyst component and the carrier component, although the manufacturing cost increases. From the above results, according to the present invention, it is possible to obtain a catalyst having a very small amount of leaked ammonia and a high denitration rate in a wide NH 3 / NOx molar ratio range.
【００３８】以下、本発明を無機繊維に酸化触媒を担持
した実施例９〜１９を用いて詳細に説明する。なお、触
媒はすべてハニカム型であるが、これは触媒活性を比較
評価するためであり、本発明の適用を特にハニカム形状
に限定するものではない。
実施例９
脱硝触媒には酸化物触媒（組成：Ｔｉ／Ｍｏ／Ｖ＝８３
／５／２（原子比）、比表面積１２０m2／ｇ）を用い、
貴金属触媒成分としてＰｔを用いた。無機繊維として５
４ wt ％ＳｉＯ2 −１９ wt ％ＣａＯ−２０ wt ％Ａｌ
2 Ｏ3 −５ wt％Ｂ2 Ｏ3 その他２ wt ％からなる直径
９μｍ、長さ１００μｍのＥガラス繊維を用いた。塩化
白金水溶液を用いて繊維表面に含浸し、５００℃で２時
間焼成した（この状態を、Ｐｔ担持酸化触媒という）。
さらに、酸化物脱硝触媒ペースト（結合剤：ポリビニル
アルコール（ＰＶＡ）２％、水分濃度３０ wt ％）に該
Ｐｔ担持酸化触媒を５ wt ％混合し、ハニカム型に押し
出し成形した後、５００℃で２時間焼成した。なお、該
Ｐｔ担持酸化触媒へのＰｔ担持量は２ wt ％、全触媒に
対しては１，０００ ppmであった。The present invention will be described in detail below with reference to Examples 9 to 19 in which an inorganic fiber carries an oxidation catalyst. Although the catalysts are all of the honeycomb type, this is for the purpose of comparatively evaluating the catalytic activity, and the application of the present invention is not particularly limited to the honeycomb shape. Example 9 An oxide catalyst (composition: Ti / Mo / V = 83) was used as the denitration catalyst.
/ 5/2 (atomic ratio), specific surface area 120 m 2 / g),
Pt was used as the noble metal catalyst component. 5 as inorganic fiber
4 wt% SiO 2 -19 wt% CaO-20 wt% Al
E glass fiber having a diameter of 9 μm and a length of 100 μm and made of 2 O 3 -5 wt% B 2 O 3 and 2 wt% was used. The fiber surface was impregnated with an aqueous solution of platinum chloride and calcined at 500 ° C. for 2 hours (this state is referred to as Pt-supported oxidation catalyst).
Further, 5 wt% of the Pt-supported oxidation catalyst was mixed with an oxide denitration catalyst paste (binder: polyvinyl alcohol (PVA) 2%, water concentration 30 wt%), and the mixture was extruded into a honeycomb shape, and then at 500 ° C. for 2 hours. Burned for hours. The amount of Pt supported on the Pt-supported oxidation catalyst was 2 wt% and 1,000 ppm for all catalysts.
【００３９】実施例１０
実施例９と同じＥガラス繊維を、高比表面積チタニア
（比表面積１２０m2／ｇ）スラリー（結合剤：ＰＶＡ２
％、水分濃度５０ wt ％）に浸漬、乾燥した後、塩化白
金水溶液を用いて繊維表面に含浸し、５００℃で２時間
焼成する。このようにして得られた酸化触媒を実施例１
と同じ酸化物脱硝触媒ペーストに５ wt ％混合した後、
ハニカム型に押し出し成形した後、５００℃で２時間焼
成した。なお、該Ｐｔ担持酸化触媒へのＰｔ担持量は２
wt ％、全触媒に対しては１，０００ ppmであった。Example 10 The same E glass fiber as in Example 9 was added to a high specific surface area titania (specific surface area 120 m 2 / g) slurry (binder: PVA2).
%, Water concentration 50 wt%) and dried, and then impregnated on the fiber surface using an aqueous solution of platinum chloride and calcined at 500 ° C. for 2 hours. The oxidation catalyst thus obtained was used in Example 1.
After mixing 5 wt% with the same oxide denitration catalyst paste as
After extrusion molding into a honeycomb shape, firing was performed at 500 ° C. for 2 hours. The amount of Pt supported on the Pt-supported oxidation catalyst was 2
wt%, 1,000 ppm for all catalysts.
【００４０】実施例１１
実施例９と同一の酸化物脱硝触媒、繊維を用い、貴金属
触媒成分としてＰｄを用いた。塩化パラジウム水溶液を
用いてハニカム表面に含浸し、５００℃で２時間焼成し
た（この状態を、Ｐｄ担持酸化触媒という）。さらに、
実施例１と同一の酸化物脱硝触媒ペースト（結合剤：Ｐ
ＶＡ２％、水分濃度３０ wt ％）に該Ｐｄ担持酸化触媒
を５ wt ％添加、混合した後、ハニカム型に押し出し成
形した。成形後、５００℃で２時間焼成した。なお、該
Ｐｄ担持酸化触媒へのＰｄ担持量は２ wt ％、全触媒に
対しては１，０００ ppmであった。Example 11 The same oxide denitration catalyst and fiber as in Example 9 were used, and Pd was used as the noble metal catalyst component. The surface of the honeycomb was impregnated with an aqueous palladium chloride solution and fired at 500 ° C. for 2 hours (this state is referred to as Pd-supported oxidation catalyst). further,
The same oxide denitration catalyst paste as in Example 1 (binder: P
5 wt% of the Pd-supported oxidation catalyst was added to and mixed with 2% of VA and a water concentration of 30 wt%, and then extrusion-molded into a honeycomb mold. After molding, it was baked at 500 ° C. for 2 hours. The amount of Pd supported on the Pd-supported oxidation catalyst was 2 wt%, which was 1,000 ppm for all catalysts.
【００４１】実施例１２
実施例９と同一の酸化物脱硝触媒、繊維を用い、貴金属
触媒成分としてＲｈを用いた。塩化ロジウム水溶液を用
いてハニカム表面に含浸し、５００℃で２時間焼成した
（この状態を、Ｒｈ担持酸化触媒という）。さらに、実
施例９と同一の酸化物脱硝触媒ペースト（結合剤：ＰＶ
Ａ２％、水分濃度３０ wt ％）に該Ｒｈ担持酸化触媒を
５ wt ％添加、混合した後、ハニカム型に押し出し成形
した。成形後、５００℃で２時間焼成した。なお、該Ｒ
ｈ担持酸化触媒へのＲｈ担持量は２ wt ％、全触媒に対
しては１，０００ ppmであった。Example 12 The same oxide denitration catalyst and fiber as in Example 9 were used, and Rh was used as the noble metal catalyst component. The honeycomb surface was impregnated with an aqueous rhodium chloride solution and fired at 500 ° C. for 2 hours (this state is referred to as an Rh-supported oxidation catalyst). Furthermore, the same oxide denitration catalyst paste as in Example 9 (binder: PV
5 wt% of the Rh-supported oxidation catalyst was added to and mixed with A2% and a water concentration of 30 wt%, and then extrusion-molded into a honeycomb mold. After molding, it was baked at 500 ° C. for 2 hours. The R
The amount of Rh supported on the h-supported oxidation catalyst was 2 wt% and 1,000 ppm for all the catalysts.
【００４２】実施例１３
実施例９と全く同じ原料、手法を用い、Ｐｔ担持酸化触
媒の添加量を１ wt ％にし、塩化白金水溶液の濃度を薄
くすることにより、Ｐｔ担持酸化触媒へのＰｔ担持量を
０．０１ wt ％、全触媒に対するＰｔ濃度を１ ppmにし
た触媒を得た。
実施例１４
高比表面積（比表面積１２０m2／ｇ）アルミナスラリー
（結合剤：ＰＶＡ２％、水分濃度５０ wt ％）を用いた
以外は実施例１０と全く同じ条件で触媒を試作した。な
お、該Ｐｔ担持酸化触媒へのＰｔ担持量は２ wt ％、全
触媒に対しては、１，０００ ppmであった。Example 13 Using exactly the same raw materials and method as in Example 9, the addition amount of the Pt-supported oxidation catalyst was set to 1 wt% and the concentration of the platinum chloride aqueous solution was reduced to support Pt on the Pt-supported oxidation catalyst. A catalyst having an amount of 0.01 wt% and a Pt concentration of 1 ppm based on the total catalyst was obtained. Example 14 A catalyst was experimentally manufactured under exactly the same conditions as in Example 10 except that a high specific surface area (specific surface area 120 m 2 / g) alumina slurry (binder: PVA 2%, water concentration 50 wt%) was used. The amount of Pt supported on the Pt-supported oxidation catalyst was 2 wt%, which was 1,000 ppm for all catalysts.
【００４３】実施例１５
水素置換型モルデナイト（比表面積１２０m2／ｇ）スラ
リー（結合剤：ＰＶＡ２％、水分濃度５０ wt ％）を用
いた以外は実施例１０と全く同じ条件で触媒を試作し
た。なお、該Ｐｔ担持酸化触媒へのＰｔ担持量は２ wt
％、全触媒に対しては、１，０００ ppmであった。
実施例１６
繊維をあらかじめ、ｐＨ１に調整した塩酸に１時間浸漬
させた後、実施例９と全く同じ処理を行なったところ、
Ｐｔ担持酸化触媒へのＰｔ担持量は２ wt ％、全触媒に
対しては、１，０００ ppmであった。Example 15 A catalyst was experimentally produced under exactly the same conditions as in Example 10 except that a hydrogen-substituted mordenite (specific surface area 120 m 2 / g) slurry (binder: PVA 2%, water concentration 50 wt%) was used. The amount of Pt supported on the Pt-supported oxidation catalyst was 2 wt.
% And 1,000 ppm for all catalysts. Example 16 The fiber was immersed in hydrochloric acid adjusted to pH 1 in advance for 1 hour and then treated in exactly the same manner as in Example 9,
The amount of Pt supported on the Pt-supported oxidation catalyst was 2 wt%, and was 1,000 ppm for all the catalysts.
【００４４】実施例１７
繊維をあらかじめ、ｐＨ１に調整した塩酸に１時間浸漬
させた後、実施例１３と全く同じ処理を行なったとこ
ろ、Ｐｔ担持酸化触媒へのＰｔ担持量は０．０１wt
％、全触媒に対しては、１ ppmであった。
実施例１８
実施例１０と全く同じ原料、手法を用い、Ｐｔ担持酸化
触媒の添加量を１ wt％にし、塩化白金水溶液の濃度を
薄くすることにより、Ｐｔ担持酸化触媒へのＰｔ担持量
を０．０１ wt ％、全触媒に対するＰｔ濃度を１ ppmに
した触媒を得た。
実施例１９
繊維をあらかじめ、ｐＨ１に調整した塩酸に１時間浸漬
させた後、実施例１０と全く同じ処理を行なったとこ
ろ、Ｐｔ担持酸化触媒へのＰｔ担持量は２ wt ％、全触
媒に対しては、１，０００ ppmであった。Example 17 The fiber was immersed in hydrochloric acid adjusted to pH 1 in advance for 1 hour, and then the same treatment as in Example 13 was carried out. The amount of Pt supported on the Pt-supported oxidation catalyst was 0.01 wt.
% And 1 ppm for all catalysts. Example 18 By using exactly the same raw material and method as in Example 10, the amount of Pt-supported oxidation catalyst added was set to 1 wt% and the concentration of the platinum chloride aqueous solution was reduced, so that the amount of Pt-supported Pt-supported oxidation catalyst was reduced to 0. A catalyst having 0.01% by weight and a Pt concentration of 1 ppm with respect to the total catalyst was obtained. Example 19 The fiber was immersed in hydrochloric acid adjusted to pH 1 for 1 hour in advance, and then, the completely same treatment as in Example 10 was performed. As a result, the Pt-supported oxidation catalyst had a Pt loading of 2 wt%, based on all the catalysts. Was 1,000 ppm.
【００４５】比較例３
実施例９で用いたものと同一の原料（酸化物脱硝触媒ペ
ーストとＥガラス繊維と塩化白金水溶液）を混合したペ
ーストをハニカム型に押し出した。なお、Ｐｔが１，０
００ ppmになるように塩化白金をペースト混合時に添加
した。焼成条件は実施例１と同じである。
比較例４
実施例１０で用いた無機繊維、脱硝触媒ペーストおよび
塩化白金を混合後、押し出し成形によりハニカム化し、
５００℃で２時間焼成することにより触媒化した。塩化
白金の添加量はＰｔで１，０００ ppmになるよう添加し
た。Comparative Example 3 A paste obtained by mixing the same raw materials as those used in Example 9 (oxide denitration catalyst paste, E glass fiber and platinum chloride aqueous solution) was extruded into a honeycomb shape. Note that Pt is 1,0
Platinum chloride was added at the time of mixing the paste so that it would be 00 ppm. The firing conditions are the same as in Example 1. Comparative Example 4 The inorganic fibers used in Example 10, the denitration catalyst paste and platinum chloride were mixed and then extruded into a honeycomb structure,
It was catalyzed by firing at 500 ° C. for 2 hours. The amount of platinum chloride added was such that Pt was 1,000 ppm.
【００４６】比較例５
実施例１３で用いたものと同一の原料（酸化物脱硝触媒
ペーストとＥガラス繊維と塩化白金水溶液）を混合した
ペーストをハニカム型に押し出した。なお、Ｐｔが１ p
pmになるように塩化白金をペースト混合時に添加した。
焼成条件は実施例１と同じである。
比較例６
実施例１０で用いた無機繊維、脱硝触媒ペーストおよび
塩化白金を混合後、押し出し成形によりハニカム化し、
５００℃で２時間焼成することにより触媒化した。塩化
白金の添加量はＰｔで１ ppmになるよう添加した。
比較例７
実施例９で用いたものと同一の脱硝触媒ペーストをハニ
カム型に押し出した。他には何も添加していない。焼成
条件は実施例１と同じである。Comparative Example 5 A paste obtained by mixing the same raw materials as used in Example 13 (oxide denitration catalyst paste, E glass fiber and platinum chloride aqueous solution) was extruded into a honeycomb shape. Note that Pt is 1 p
Platinum chloride was added at the time of mixing the paste so that it became pm.
The firing conditions are the same as in Example 1. Comparative Example 6 The inorganic fibers used in Example 10, the denitration catalyst paste and platinum chloride were mixed and then extruded into a honeycomb structure,
It was catalyzed by firing at 500 ° C. for 2 hours. The amount of platinum chloride added was Pt to 1 ppm. Comparative Example 7 The same denitration catalyst paste used in Example 9 was extruded into a honeycomb shape. Nothing else was added. The firing conditions are the same as in Example 1.
【００４７】図５に実施例９から１９、図６に比較例
３、４、５、６および７で作製した脱硝触媒による脱硝
実験結果をそれぞれ示す。燃料に石炭を用いた燃焼装置
の排ガスで実験を行なった。燃焼排ガスの組成はＳ
Ｏ2 ：５００ ppm、ＮＯｘ濃度：２００ ppm、Ｏ2 濃
度：３．０％で残りは窒素ガスであった。脱硝実験は温
度３５０℃、ガス流速１７ｍ／ｈの条件の下で行ない、
触媒入口のＮＨ3 流量を制御することにより、、触媒入
口ガス中のＮＨ3 ／ＮＯｘモル比を０．６〜１．５まで
変化させて、それぞれの定常状態における脱硝率および
リークアンモニア濃度を求めた。FIG. 5 shows the results of the denitration experiments using the denitration catalysts produced in Examples 9 to 19 and Comparative Examples 3, 4, 5, 6 and 7, respectively. The experiment was conducted with the exhaust gas of the combustion device using coal as the fuel. The composition of combustion exhaust gas is S
O 2 : 500 ppm, NOx concentration: 200 ppm, O 2 concentration: 3.0%, and the balance was nitrogen gas. The denitration experiment was performed under the conditions of a temperature of 350 ° C. and a gas flow rate of 17 m / h.
By controlling the NH 3 flow rate at the catalyst inlet, the NH 3 / NOx molar ratio in the catalyst inlet gas was changed to 0.6 to 1.5, and the denitration rate and the leak ammonia concentration in each steady state were obtained. It was
【００４８】その結果、比較例３、４以外はいずれの場
合も、脱硝率はほぼ同じ値を示す。一方、ＮＨ3 ／ＮＯ
ｘモル比が０．８以上１．４以下の場合、比較例５、６
および７以外にＮＨ3 濃度はほとんど変わらない。この
ことは、本願発明の実施例として作製した触媒はすべて
脱硝性能とアンモニア分解性能のいずれも充分である
が、比較例３および４は脱硝性能において、比較例５お
よび６はＮＨ3 分解性能において本願発明の実施例より
もかなり劣っており比較例７と同等であることがわか
る。As a result, in all cases except Comparative Examples 3 and 4, the denitration rate shows almost the same value. On the other hand, NH 3 / NO
When the x molar ratio is 0.8 or more and 1.4 or less, Comparative Examples 5 and 6
Other than and 7, NH 3 concentration is almost unchanged. This means that all of the catalysts produced as Examples of the present invention have sufficient denitration performance and ammonia decomposing performance, but Comparative Examples 3 and 4 are denitrifying performance, and Comparative Examples 5 and 6 are NH 3 decomposing performance. It can be seen that it is considerably inferior to the example of the present invention and is equivalent to the comparative example 7.
【００４９】なお、実施例９、１０、１６および１９の
触媒について１，０００時間試験後の触媒性能をＮＨ3
／ＮＯｘ比が１．５の条件で比較してみた。実験結果を
表２に示す。The catalyst performance of the catalysts of Examples 9, 10, 16 and 19 after 1,000-hour test was measured by NH 3
The comparison was made under the condition that the / NOx ratio was 1.5. The experimental results are shown in Table 2.
【００５０】[0050]
【表２】
脱硝触媒性能はいずれも変化はないが、リークＮＨ3 濃
度は実施例９、１０、１６、１９の順に低くなってい
る。このことから、製造コストは上昇するものの、表面
に高比表面積酸化物を塗布したり、無機繊維の酸洗処理
を行なうことによって、触媒の耐久性が向上することが
わかる。[Table 2] The NOx removal catalyst performance did not change, but the leak NH 3 concentration decreased in the order of Examples 9, 10, 16, and 19. From this, it is understood that although the manufacturing cost increases, the durability of the catalyst is improved by applying a high specific surface area oxide on the surface or performing pickling treatment on the inorganic fiber.
【００５１】また、実施例９、１０、１６、１９および
比較例７の圧壊強度を測定した。結果を図７に示す。繊
維の有無で圧壊強度がかなり違うことがわかる。以上の
結果から、本願発明によれば広いＮＨ3 ／ＮＯｘモル比
範囲で、リークアンモニアが非常に少なく、脱硝率の高
い排ガス浄化触媒を得ることが可能となる。The crush strength of Examples 9, 10, 16, 19 and Comparative Example 7 was measured. The results are shown in Fig. 7. It can be seen that the crush strength is significantly different depending on the presence or absence of fibers. From the above results, according to the present invention, it is possible to obtain an exhaust gas purifying catalyst with a very low NH 3 / NOx molar ratio range, a very small amount of leaked ammonia, and a high denitration rate.
【００５２】[0052]
【発明の効果】本発明によれば、従来、不可能であった
高ＮＨ3 ／ＮＯｘモル比運転が可能になる。そのため、
従来の脱硝触媒と同等の脱硝率で充分な場合、高ＮＨ3
／ＮＯｘモル比運転を行なうことにより、触媒装置容積
をより小型化することが可能になる。According to the present invention, a high NH 3 / NOx molar ratio operation, which has hitherto been impossible, can be performed. for that reason,
When a denitration rate equivalent to that of conventional denitration catalyst is sufficient, high NH 3
By performing the / NOx molar ratio operation, it becomes possible to further reduce the catalyst device volume.
【００５３】また、広いＮＨ3 ／ＮＯｘモル比範囲で高
い脱硝率を安定的に得られるため、負荷変動の大きい燃
焼装置であっても脱硝率の制御が容易である。また、本
発明によれば、Ｅガラス等の安価な汎用ガラス繊維を酸
化触媒の担体として用いることにより、広いＮＨ3 ／Ｎ
Ｏｘモル比範囲で、リークアンモニアの非常に少ない脱
硝率の高い触媒を得ることが可能となる。Further, since a high denitrification rate can be stably obtained in a wide NH 3 / NOx molar ratio range, it is easy to control the denitrification rate even in a combustion device with large load fluctuations. Further, according to the present invention, by using inexpensive general-purpose glass fiber such as E glass as a carrier for the oxidation catalyst, a wide NH 3 / N ratio can be obtained.
In the Ox molar ratio range, it becomes possible to obtain a catalyst with a high denitration rate with very little leaked ammonia.
【００５４】また、無機繊維を添加することにより、圧
壊強度が向上するため、耐久性向上に効果がある。Further, the addition of the inorganic fiber improves the crushing strength, which is effective in improving the durability.
【図１】本願発明の脱硝触媒の構造概念図。FIG. 1 is a structural conceptual diagram of a denitration catalyst of the present invention.
【図２】本願発明の実施例１〜８の触媒と従来触媒の性
能比較図。FIG. 2 is a performance comparison diagram of the catalysts of Examples 1 to 8 of the present invention and a conventional catalyst.
【図３】排ガス脱硝装置の概略図。FIG. 3 is a schematic diagram of an exhaust gas denitration device.
【図４】本願発明の実施例９〜１９の脱硝触媒の構造概
念図。FIG. 4 is a structural conceptual diagram of denitration catalysts of Examples 9 to 19 of the present invention.
【図５】本願発明の実施例９〜１９の脱硝触媒の性能を
示す図。FIG. 5 is a graph showing the performance of the denitration catalysts of Examples 9 to 19 of the present invention.
【図６】比較例３〜７の触媒の性能を示す図。FIG. 6 is a diagram showing the performance of the catalysts of Comparative Examples 3 to 7.
【図７】本願発明の実施例触媒と比較例の圧壊強度比較
図。FIG. 7 is a comparison diagram of crushing strength of the example catalyst of the present invention and the comparative example.
【図８】本願発明の実施例触媒の動作メカニズムを示す
図。FIG. 8 is a view showing an operation mechanism of the catalyst of the embodiment of the present invention.
１…脱硝触媒層、２…酸化触媒層、３…触媒担体層、４
…燃焼装置、５…脱硝装置、６…空気予熱器、７…集塵
機、８…排ガス煙突、９…ＮＨ3 導入部、１０…煙道。1 ... Denitration catalyst layer, 2 ... Oxidation catalyst layer, 3 ... Catalyst carrier layer, 4
... combustion apparatus, 5 ... denitration apparatus, 6 ... air preheater 7 ... dust collector, 8 ... exhaust chimney, 9 ... NH 3 introducing portion, 10 ... flue.
フロントページの続き (72)発明者 向井 利文 広島県呉市宝町３番36号 バブコック日 立株式会社 呉研究所内 (72)発明者 貞方 知彦 広島県呉市宝町３番36号 バブコック日 立株式会社 呉研究所内 (72)発明者 矢代 克洋 広島県呉市宝町３番36号 バブコック日 立株式会社 呉研究所内 (72)発明者 浜田 幾久 広島県呉市宝町３番36号 バブコック日 立株式会社 呉研究所内 (56)参考文献 特開 平５−146634（ＪＰ，Ａ) 特開 昭59−82930（ＪＰ，Ａ) 特開 昭55−155745（ＪＰ，Ａ) 特開 昭54−20983（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 21/00 - 38/74 B01D 53/86,53/94 Front page continuation (72) Inventor Toshifumi Mukai 3-36 Takaracho, Kure-shi, Hiroshima Babcock Hiritsu Co., Ltd. Kure Laboratory (72) Tomohiko Sadakata 3-36 Takaracho, Kure-shi, Hiroshima Babcock Hiritsu Kure Co., Ltd. In-lab (72) Inventor Katsuhiro Yashiro 3-36 Takara-cho, Kure-shi, Hiroshima Babcock Hiritsu Co., Ltd. In Kure Lab (72) Inventor Ikuhisa Hamada 3-36 Takara-cho, Kure-shi, Hiroshima Babcock-Hiritsu Co., Ltd. (56) References JP-A 5-146634 (JP, A) JP-A 59-82930 (JP, A) JP-A 55-155745 (JP, A) JP-A 54-20983 (JP, A) ( 58) Fields surveyed (Int.Cl. 7 , DB name) B01J 21/00-38/74 B01D 53 / 86,53 / 94
Claims (7)
アンモニアを用いて接触還元するとともに、未反応のア
ンモニアを分解する排ガス浄化触媒において、チタニ
ア、コーディエライト、ゼオライト、アルミナおよびシ
リカから選ばれた一種以上の多孔触媒担体表面に、酸化
触媒層として白金（Ｐｔ）、パラジウム（Ｐｄ）、ロジ
ウム（Ｒｈ）から選ばれた一種以上の貴金属からなる触
媒層を形成させ、かつ、その層上に脱硝触媒層としてチ
タン（Ｔｉ）、モリブデン（Ｍｏ）、タングステン
（Ｗ）、バナジウム（Ｖ）から選ばれた一種以上の酸化
物からなる触媒層を設けたことを特徴とする排ガス浄化
触媒。1. In an exhaust gas purification catalyst for catalytically reducing nitrogen oxides in exhaust gas using ammonia as a reducing agent, and for decomposing unreacted ammonia, titania, cordierite, zeolite, alumina and silane. A catalyst layer made of one or more noble metals selected from platinum (Pt), palladium (Pd) and rhodium (Rh) is formed as an oxidation catalyst layer on the surface of one or more porous catalyst carriers selected from Rica, Further, a catalyst layer made of one or more oxides selected from titanium (Ti), molybdenum (Mo), tungsten (W) and vanadium (V) is provided on the layer as a denitration catalyst layer. Exhaust gas purification catalyst.
素置換型モルデナイトを用いたことを特徴とする排ガス
浄化触媒。2. The exhaust gas purifying catalyst according to claim 1, wherein hydrogen-substituted mordenite is used as the zeolite.
アンモニアを用いて接触還元するとともに、未反応のア
ンモニアを分解する排ガス浄化触媒において、白金（Ｐ
ｔ）、パラジウム（Ｐｄ）、ロジウム（Ｒｈ）から選ば
れた一種以上の貴金属触媒成分を含有する多孔担体表面
を、チタン（Ｔｉ）、モリブデン（Ｍｏ）、タングステ
ン（Ｗ）、バナジウム（Ｖ）から選ばれた一種以上の酸
化物からなる脱硝触媒層で被覆したことを特徴とする排
ガス浄化触媒。3. In an exhaust gas purifying catalyst for catalytically reducing nitrogen oxides in exhaust gas using ammonia as a reducing agent and decomposing unreacted ammonia, platinum (P
t), palladium (Pd), rhodium (Rh), the surface of the porous carrier containing one or more noble metal catalyst components, titanium (Ti), molybdenum (Mo), tungsten (W), vanadium (V) An exhaust gas purification catalyst coated with a denitration catalyst layer made of one or more selected oxides.
型モルデナイトであることを特徴とする排ガス浄化触
媒。4. The exhaust gas purifying catalyst according to claim 3, wherein the porous carrier is hydrogen-substituted mordenite.
いて接触還元するとともに、未反応のアンモニアを分解
する排ガス浄化触媒の製造方法において、多孔触媒担体
表面に、酸化触媒貴金属成分と脱硝触媒成分および粒状
多孔担体よりなるスラリーを含浸した後焼成し、この焼
成体表面に脱硝触媒成分を担持したのち焼成することを
特徴とする排ガス浄化触媒の製造方法。5. A method for producing an exhaust gas purification catalyst, which comprises catalytically reducing nitrogen oxides in exhaust gas with ammonia and decomposing unreacted ammonia. And a method for producing an exhaust gas purifying catalyst, comprising impregnating with a slurry comprising a granular porous carrier, followed by firing, supporting a denitration catalyst component on the surface of the fired body, and then firing.
いて接触還元するとともに、未反応のアンモニアを分解
する排ガス浄化触媒において、チタン（Ｔｉ）、モリブ
デン（Ｍｏ）、タングステン（Ｗ）、バナジウム（Ｖ）
から選ばれた一種以上の酸化物からなる脱硝触媒内に、
少なくともアルカリ土類金属元素、アルミニウムおよび
シリコンの３元素を含有する無機繊維を含み、かつ、該
繊維上に白金（Ｐｔ）、パラジウム（Ｐｄ）、ロジウム
（Ｒｈ）から選ばれた一種以上の貴金属からなる酸化触
媒層を形成させたことを特徴とする排ガス浄化触媒。6. An exhaust gas purifying catalyst for catalytically reducing nitrogen oxides in exhaust gas with ammonia and decomposing unreacted ammonia, wherein titanium (Ti), molybdenum (Mo), tungsten (W), vanadium ( V)
In the denitration catalyst consisting of one or more oxides selected from
At least one noble metal selected from platinum (Pt), palladium (Pd), and rhodium (Rh) containing inorganic fibers containing at least three elements of alkaline earth metal elements, aluminum and silicon, and on the fibers. An exhaust gas purifying catalyst, wherein an oxidation catalyst layer is formed.
いて接触還元するとともに、未反応のアンモニアを分解
する排ガス浄化触媒において、チタン（Ｔｉ）、モリブ
デン（Ｍｏ）、タングステン（Ｗ）、バナジウム（Ｖ）
から選ばれた一種以上の酸化物からなる脱硝触媒層内に
無機繊維を含み、かつ該繊維上にチタン、シリカまたは
アルミニウムから選ばれた一種以上の酸化物またはゼオ
ライトのコーティング層が形成され、かつ該コーティン
グ層上に白金（Ｐｔ）、パラジウム（Ｐｄ）、ロジウム
（Ｒｈ）から選ばれた一種以上の貴金属からなる酸化触
媒を担持したことを特徴とする排ガス浄化触媒。7. In an exhaust gas purifying catalyst for catalytically reducing nitrogen oxides in exhaust gas with ammonia and decomposing unreacted ammonia, titanium (Ti), molybdenum (Mo), tungsten (W), vanadium ( V)
Including inorganic fibers in the denitration catalyst layer consisting of one or more oxides selected from, and a coating layer of one or more oxides or zeolites selected from titanium, silica or aluminum is formed on the fibers, and An exhaust gas purifying catalyst, wherein an oxidation catalyst made of one or more noble metals selected from platinum (Pt), palladium (Pd), and rhodium (Rh) is carried on the coating layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15239093A JP3436567B2 (en) | 1993-06-23 | 1993-06-23 | Exhaust gas purification catalyst and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15239093A JP3436567B2 (en) | 1993-06-23 | 1993-06-23 | Exhaust gas purification catalyst and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0716462A JPH0716462A (en) | 1995-01-20 |
| JP3436567B2 true JP3436567B2 (en) | 2003-08-11 |
Family
ID=15539474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15239093A Expired - Fee Related JP3436567B2 (en) | 1993-06-23 | 1993-06-23 | Exhaust gas purification catalyst and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3436567B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009025185A1 (en) | 2007-08-22 | 2009-02-26 | Mitsubishi Heavy Industries, Ltd. | Exhaust gas treatment catalyst, and exhaust gas treatment system |
| WO2014120645A1 (en) * | 2013-01-29 | 2014-08-07 | Johnson Matthey Public Limited Company | Ammonia oxidation catalyst |
| WO2018065354A1 (en) | 2016-10-03 | 2018-04-12 | Umicore Ag & Co. Kg | Catalyst article and method for the abatement of ammonia and nitrogen oxides |
| WO2019048373A1 (en) | 2017-09-07 | 2019-03-14 | Haldor Topsøe A/S | Method for preparation of a novel eri-molecular sieve |
| WO2019048372A1 (en) | 2017-09-07 | 2019-03-14 | Haldor Topsøe A/S | Novel eri-molecular sieve |
| WO2019048375A1 (en) | 2017-09-07 | 2019-03-14 | Haldor Topsøe A/S | Catalyst comprising a novel molecular sieve belonging to the eri family and use of the catalyst |
| WO2020039074A1 (en) | 2018-08-24 | 2020-02-27 | Umicore Ag & Co. Kg | Method for the preparation of a molecular sieve of the cha-type |
| WO2022214655A1 (en) | 2021-04-09 | 2022-10-13 | Umicore Ag & Co. Kg | One-pot synthesis of transition metal-promoted chabazites |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04136158U (en) * | 1991-06-08 | 1992-12-17 | 東京シート株式会社 | armrest |
| JP2006205091A (en) * | 2005-01-28 | 2006-08-10 | Takuma Co Ltd | Denitration catalyst and exhaust gas treating method |
| WO2009141889A1 (en) * | 2008-05-20 | 2009-11-26 | イビデン株式会社 | Honeycomb structure |
| JP5175797B2 (en) * | 2008-05-20 | 2013-04-03 | イビデン株式会社 | Honeycomb structure |
| US8524185B2 (en) * | 2008-11-03 | 2013-09-03 | Basf Corporation | Integrated SCR and AMOx catalyst systems |
| JP5732297B2 (en) * | 2011-03-31 | 2015-06-10 | エヌ・イーケムキャット株式会社 | Ammonia oxidation catalyst, exhaust gas purification device, and exhaust gas purification method |
| US9011809B2 (en) * | 2011-03-31 | 2015-04-21 | N.E. Chemcat Corporation | Ammonia oxidation catalyst, exhaust gas purification device using same, and exhaust gas purification method |
| JP5755160B2 (en) * | 2012-02-17 | 2015-07-29 | 田中貴金属工業株式会社 | Ammonia decomposition catalyst and method for producing the same |
| US9227176B2 (en) * | 2012-11-30 | 2016-01-05 | Johnson Matthey Public Limited Company | Ammonia oxidation catalyst |
| JP6215361B2 (en) * | 2013-02-14 | 2017-10-18 | ハルドール・トプサー・アクチエゼルスカベット | Method and catalyst for simultaneous removal of carbon monoxide and nitrogen oxides from flue gas or exhaust gas |
| DE102013015117A1 (en) * | 2013-09-12 | 2015-03-12 | Johnson Matthey Catalysts (Germany) Gmbh | Catalyst and method for nitrogen oxide reduction in an exhaust gas |
| JP6618342B2 (en) * | 2015-12-07 | 2019-12-11 | 日揮触媒化成株式会社 | Zeolite kneaded product using kumbai powder, method for producing the same, and method for producing zeolite extrudate using the zeolite kneaded material |
| JP6921261B1 (en) * | 2020-03-26 | 2021-08-18 | 株式会社キャタラー | Exhaust gas purification catalyst device |
-
1993
- 1993-06-23 JP JP15239093A patent/JP3436567B2/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009025185A1 (en) | 2007-08-22 | 2009-02-26 | Mitsubishi Heavy Industries, Ltd. | Exhaust gas treatment catalyst, and exhaust gas treatment system |
| WO2014120645A1 (en) * | 2013-01-29 | 2014-08-07 | Johnson Matthey Public Limited Company | Ammonia oxidation catalyst |
| JP2016511684A (en) * | 2013-01-29 | 2016-04-21 | ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃ Ｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ | Ammonia oxidation catalyst |
| WO2018065354A1 (en) | 2016-10-03 | 2018-04-12 | Umicore Ag & Co. Kg | Catalyst article and method for the abatement of ammonia and nitrogen oxides |
| WO2018065353A1 (en) | 2016-10-03 | 2018-04-12 | Umicore Ag & Co. Kg | Catalyst article and method for the abatement of ammonia and nitrogen oxides |
| WO2019048373A1 (en) | 2017-09-07 | 2019-03-14 | Haldor Topsøe A/S | Method for preparation of a novel eri-molecular sieve |
| WO2019048372A1 (en) | 2017-09-07 | 2019-03-14 | Haldor Topsøe A/S | Novel eri-molecular sieve |
| WO2019048375A1 (en) | 2017-09-07 | 2019-03-14 | Haldor Topsøe A/S | Catalyst comprising a novel molecular sieve belonging to the eri family and use of the catalyst |
| WO2020039074A1 (en) | 2018-08-24 | 2020-02-27 | Umicore Ag & Co. Kg | Method for the preparation of a molecular sieve of the cha-type |
| US11667536B2 (en) | 2018-08-24 | 2023-06-06 | Umicore Ag & Co. Kg | Method for the preparation of a molecular sieve of the CHA-type |
| WO2022214655A1 (en) | 2021-04-09 | 2022-10-13 | Umicore Ag & Co. Kg | One-pot synthesis of transition metal-promoted chabazites |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0716462A (en) | 1995-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3436567B2 (en) | Exhaust gas purification catalyst and method for producing the same | |
| RU2278281C2 (en) | Device for and method of processing of waste gases formed when engine operates on lean mixtures by selective catalytic reduction of nitrogen oxides | |
| US7833932B1 (en) | Compositions and methods for treating exhaust gases | |
| US9339800B2 (en) | Methods for treating engine exhaust | |
| US5384110A (en) | Exhaust gas cleaner and method of cleaning exhaust gas | |
| KR101542754B1 (en) | Exhaust gas purification system for the treatment of engine exhaust gases by means of a scr catalyst | |
| EP1985353B1 (en) | Exhaust gas purification catalyst for automobile, exhaust gas purification catalyst system and purifying process of exhaust gas | |
| EP2368628A1 (en) | Catalyst for a DeNOx-application and a process for selective catalytic reduction of nitrogen oxides | |
| JP2006326495A (en) | Exhaust-gas cleaning catalyst | |
| JP5609208B2 (en) | Exhaust gas purification device | |
| JP4203926B2 (en) | Method and apparatus for removing nitrous oxide, etc. from exhaust gas | |
| US20030101718A1 (en) | Method and device for the catalytic conversion of gaseous pollutants in the exhaust gas of combustion engines | |
| JP3327054B2 (en) | Exhaust gas purification catalyst | |
| JPH05293385A (en) | Catalyst structural body and its production | |
| JPH105591A (en) | Catalyst for cleaning of waste gas and device for cleaning waste gas with same | |
| JP3546908B2 (en) | Ammonia purification catalyst device | |
| KR20220016466A (en) | Exhaust gas treatment system for ultra-low NOx and cold start | |
| JP3285206B2 (en) | Exhaust gas purification catalyst and method for producing the same | |
| JP2009273989A (en) | Exhaust gas cleaning device | |
| TWI361103B (en) | ||
| JPH05329334A (en) | Catalyst for purifying exhaust gas and method for purifying exhaust gas | |
| JPH09150039A (en) | Apparatus and method for purifying exhaust gas | |
| WO2020149313A1 (en) | Catalyst for exhaust gas purification use | |
| JPH06142523A (en) | Waste gas purifying material and waste gas purifying method | |
| RU2772861C2 (en) | Catalytic product for exhaust gas treatment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080606 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090606 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100606 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110606 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120606 Year of fee payment: 9 |
|
| LAPS | Cancellation because of no payment of annual fees |