JPH07213903A - Exhaust gas purifying catalyst - Google Patents
Exhaust gas purifying catalystInfo
- Publication number
- JPH07213903A JPH07213903A JP6035195A JP3519594A JPH07213903A JP H07213903 A JPH07213903 A JP H07213903A JP 6035195 A JP6035195 A JP 6035195A JP 3519594 A JP3519594 A JP 3519594A JP H07213903 A JPH07213903 A JP H07213903A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- noble metal
- tio
- platinum
- tio2
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 17
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 33
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 76
- 229910052697 platinum Inorganic materials 0.000 abstract description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 7
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 6
- 239000000843 powder Substances 0.000 abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 abstract description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010948 rhodium Substances 0.000 abstract description 4
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 abstract description 3
- 229910052763 palladium Inorganic materials 0.000 abstract description 3
- 229910052703 rhodium Inorganic materials 0.000 abstract description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000011369 resultant mixture Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000969 carrier Substances 0.000 description 3
- 229910052878 cordierite Inorganic materials 0.000 description 3
- 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 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000010757 Reduction Activity Effects 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 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】本発明は希薄燃焼エンジンから排
出される窒素酸化物（ＮＯx）を効率よく浄化すること
のできる排ガス浄化用触媒に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an exhaust gas purifying catalyst capable of efficiently purifying nitrogen oxides (NO x ) discharged from a lean burn engine.
【０００２】[0002]
【従来の技術】近年、ディゼルエンジンから排出される
多量の窒素酸化物は、人体に有害であり、かつ光化学ス
モッグや酸性雨の発生源となり、その削減が望まれてい
る。2. Description of the Related Art In recent years, a large amount of nitrogen oxides discharged from a diesel engine is harmful to the human body and becomes a source of photochemical smog and acid rain, and its reduction is desired.
【０００３】また、ガソンエンジンにおいても燃費向上
のために希薄燃焼システムが実用化されている。しか
し、窒素酸化物の除去には依然として問題が残されてい
る。Also, in the Gason engine, a lean burn system has been put into practical use for improving fuel efficiency. However, there are still problems in removing nitrogen oxides.
【０００４】そこで、近年、炭化水素の存在下で、Ｃ
ｕ、Ｐｔ等の金属を担持させたゼオライトやアルミナ等
の触媒がＮＯx除去に有効であるとして注目されている
（例えば、特開昭６３−１００９１９号公報）。しかし
ながら、これらの触媒は、耐熱性、耐久性、ＮＯx浄化
性能の不足等で実用化には十分とはいえない。Therefore, in recent years, in the presence of hydrocarbons, C
Attention has been paid to catalysts such as zeolite and alumina that support metals such as u and Pt for removing NO x (for example, Japanese Patent Laid-Open No. 63-100919). However, these catalysts are not sufficient for practical use due to lack of heat resistance, durability, NO x purification performance and the like.
【０００５】また、アンモニアによる選択的接触還元で
用いられているＶ2Ｏ5／ＴｉＯ2ＷＯ3／Ｖ2Ｏ5／ＴｉＯ
2等の触媒は、炭化水素によるＮＯx還元活性をまったく
示さない。Further, V 2 O 5 / TiO 2 WO 3 / V 2 O 5 / TiO used in the selective catalytic reduction with ammonia.
Catalyst 2 or the like, show no the NO x reduction activity by hydrocarbons.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、これら従来
技術の課題を解消し、低温から高効率でＮＯxを除去で
き、また耐熱性に優れ、さらに水蒸気共存下においても
優れたＮＯx浄化性能を示す排気ガス浄化用触媒を提供
することを目的とする。DISCLOSURE OF THE INVENTION The present invention solves these problems of the prior art, is capable of removing NO x with high efficiency from a low temperature, has excellent heat resistance, and is excellent in NO x purification even in the presence of steam. An object is to provide an exhaust gas purifying catalyst that exhibits performance.
【０００７】[0007]
【課題を解決するための手段】本発明者等は、上記目的
を達成すべく鋭意検討の結果、炭化水素の存在下におい
て、全く浄化性能を示さないアンモニア脱硝触媒（Ｖ2
Ｏ5／ＴｉＯ2、ＷＯ3／Ｖ2Ｏ5／ＴｉＯ2）に貴金属を担
持することにより、上記目的が達成されることを見出
し、本発明に至った。Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that an ammonia denitration catalyst (V 2
The inventors have found that the above object can be achieved by supporting a noble metal on O 5 / TiO 2 , WO 3 / V 2 O 5 / TiO 2 ), and have completed the present invention.
【０００８】すなわち、本発明の排気ガス浄化用触媒
は、Ｖ2Ｏ5／ＴｉＯ2またはＷＯ3／Ｖ2Ｏ5／ＴｉＯ2を
触媒担体として用い、これに貴金属を担持させたことを
特徴とする。That is, the exhaust gas purifying catalyst of the present invention is characterized in that V 2 O 5 / TiO 2 or WO 3 / V 2 O 5 / TiO 2 is used as a catalyst carrier and a noble metal is supported on the catalyst carrier. To do.
【０００９】本発明では、アンモニア脱硝触媒として用
いられているＶ2Ｏ5／ＴｉＯ2、ＷＯ3／Ｖ2Ｏ5／ＴｉＯ
2を触媒担体として用いる。この触媒担体は、従来公知
の方法で調製することができる。例えば、酸化チタン粉
末をメタバナジン酸アンモニウム水溶液やメタバナジン
酸アンモニウムとパラタングステン酸アンモニウムとの
混合溶液に浸漬した後、水を蒸発させ、乾燥、焼成する
ことにより、Ｖ2Ｏ5やＶ2Ｏ5とＷＯ3をＴｉＯ2上に担持
することができる。In the present invention, V 2 O 5 / TiO 2 and WO 3 / V 2 O 5 / TiO used as ammonia denitration catalysts are used.
2 is used as catalyst carrier. This catalyst carrier can be prepared by a conventionally known method. For example, by immersing titanium oxide powder in an aqueous solution of ammonium metavanadate or a mixed solution of ammonium metavanadate and ammonium paratungstate, evaporating water, drying, and firing, V 2 O 5 and V 2 O 5 are obtained. WO 3 can be supported on TiO 2 .
【００１０】本発明では、これら触媒担体に貴金属を担
持させる。貴金属としては、白金、パラジウム、ルテニ
ウム、ロジウム等が例示される。この担持される貴金属
の量は、特に限定されないが、好ましくは触媒中、０．
１〜１０重量％である。In the present invention, a noble metal is supported on these catalyst carriers. Examples of the noble metal include platinum, palladium, ruthenium, rhodium and the like. The amount of the noble metal to be supported is not particularly limited, but is preferably 0.
It is 1 to 10% by weight.
【００１１】この触媒担体への貴金属の担持方法は、触
媒担体を各種貴金属塩の水溶液に浸漬した後、水を蒸発
させる、いわゆる蒸発乾固法が挙げられる。また、従来
公知のアルミナ担体上への貴金属担持と同様にして吸着
含浸でも行うことができる。さらには、酸化チタン粉末
上にＶ2Ｏ5やＶ2Ｏ5とＷＯ3を担持すると同時に、貴金
属を担持する方法でもよい。As a method for supporting the noble metal on the catalyst carrier, there is a so-called evaporation-drying method in which the catalyst carrier is immersed in an aqueous solution of various noble metal salts and then water is evaporated. Further, adsorption impregnation can be carried out in the same manner as the conventionally known support of noble metal on an alumina carrier. Further, a method of supporting V 2 O 5 or V 2 O 5 and WO 3 on the titanium oxide powder and at the same time supporting a noble metal may be used.
【００１２】このような本発明の排気ガス浄化用触媒
は、酸素過剰雰囲気の排気ガス中の窒素酸化物を炭化水
素の存在下で還元するための触媒である。Such an exhaust gas purifying catalyst of the present invention is a catalyst for reducing nitrogen oxides in exhaust gas in an oxygen excess atmosphere in the presence of hydrocarbons.
【００１３】[0013]
【作用】Ｖ2Ｏ5／ＴｉＯ2またはＷＯ3／Ｖ2Ｏ5／ＴｉＯ
2触媒は、炭化水素によるＮＯx還元活性を示さない。ま
た、Ｃｏ、Ｃｕを上記の触媒に担持しても、ほとんど活
性を示さない。しかし、貴金属を担持することにより、
Ｃｕ／ゼオライト触媒よりも低温から高効率でＮＯxを
浄化することができる。さらに、耐熱性に優れ、水蒸気
共存下においてもその活性を保持することができる。Function: V 2 O 5 / TiO 2 or WO 3 / V 2 O 5 / TiO
2 catalyst does not show the NO x reduction activity by hydrocarbons. Further, even when Co and Cu are carried on the above catalyst, they hardly show activity. However, by supporting a noble metal,
It is possible to purify NO x with higher efficiency from a lower temperature than the Cu / zeolite catalyst. Furthermore, it has excellent heat resistance and can retain its activity even in the presence of steam.
【００１４】[0014]
【実施例】以下、実施例等に基づいて本発明を具体的に
説明する。EXAMPLES The present invention will be specifically described below based on Examples and the like.
【００１５】実施例１ メタバナジン酸アンモニウム３．８５９ｇを純水８００
ｍｌに溶解した。この溶液にＴｉＯ2粉末１００ｇを浸
漬し、マグネチックスタラーで撹拌しながら加熱し、蒸
発乾固させた。その後、１２０℃、１２時間乾燥し、次
いで５００℃、３時間焼成してＶ2Ｏ5／ＴｉＯ2触媒担
体を得た。 Example 1 80059 pure water was added with 3.859 g of ammonium metavanadate.
Dissolved in ml. 100 g of TiO 2 powder was immersed in this solution, heated with stirring with a magnetic stirrer, and evaporated to dryness. Then, it was dried at 120 ° C. for 12 hours and then calcined at 500 ° C. for 3 hours to obtain a V 2 O 5 / TiO 2 catalyst carrier.
【００１６】次に、上記Ｖ2Ｏ5／ＴｉＯ2４９．５ｇ
に、白金０．５ｇを含有するジニトロジアミン白金水溶
液を加え、マグネチックスタラーで撹拌しながら加熱
し、蒸発乾固させた。その後、１２０℃、１２時間乾燥
し、次いで５００℃、３時間焼成を行い、Ｐｔ１ｗｔ％
担持Ｖ2Ｏ5／ＴｉＯ2触媒を得た。Next, 49.5 g of the above V 2 O 5 / TiO 2
To the above, an aqueous dinitrodiamine platinum solution containing 0.5 g of platinum was added, and the mixture was heated with stirring with a magnetic stirrer and evaporated to dryness. After that, it is dried at 120 ° C. for 12 hours, then baked at 500 ° C. for 3 hours, and Pt 1 wt%
A supported V 2 O 5 / TiO 2 catalyst was obtained.
【００１７】実施例２ 実施例１で用いた白金０．５ｇを含有するジニトロジア
ミン白金水溶液に代えて、白金１．５ｇを含有するジニ
トロジアミン白金水溶液を用いた以外は実施例１と同様
の方法によってＰｔ３ｗｔ％担持Ｖ2Ｏ5／ＴｉＯ2触媒
を得た。 Example 2 The same method as in Example 1 except that an aqueous dinitrodiamine platinum solution containing 1.5 g of platinum was used instead of the aqueous dinitrodiamine platinum solution containing 0.5 g of platinum used in Example 1. A Pt 3 wt% supported V 2 O 5 / TiO 2 catalyst was obtained.
【００１８】実施例３ 実施例１で用いた白金０．５ｇを含有するジニトロジア
ミン白金水溶液に代えて、白金２．５ｇを含有するジニ
トロジアミン白金水溶液を用いた以外は実施例１と同様
の方法によってＰｔ５ｗｔ％担持Ｖ2Ｏ5／ＴｉＯ2触媒
を得た。 Example 3 The same method as in Example 1 except that an aqueous dinitrodiamine platinum solution containing 2.5 g of platinum was used instead of the aqueous dinitrodiamine platinum solution containing 0.5 g of platinum used in Example 1. A Pt 5 wt% supported V 2 O 5 / TiO 2 catalyst was obtained.
【００１９】実施例４ 実施例１で用いた白金０．５ｇを含有するジニトロジア
ミン白金水溶液に代えて、白金３．５ｇを含有するジニ
トロジアミン白金水溶液を用いた以外は実施例１と同様
の方法によってＰｔ７ｗｔ％担持Ｖ2Ｏ5／ＴｉＯ2触媒
を得た。 Example 4 The same method as in Example 1 except that an aqueous dinitrodiamine platinum solution containing 3.5 g of platinum was used instead of the aqueous dinitrodiamine platinum solution containing 0.5 g of platinum used in Example 1. A Pt 7 wt% supported V 2 O 5 / TiO 2 catalyst was obtained.
【００２０】実施例５ 実施例１で用いた白金０．５ｇを含有するジニトロジア
ミン白金水溶液に代えて、白金４．５ｇを含有するジニ
トロジアミン白金水溶液を用いた以外は実施例１と同様
の方法によってＰｔ９ｗｔ％担持Ｖ2Ｏ5／ＴｉＯ2触媒
を得た。 Example 5 The same method as in Example 1 except that the dinitrodiamine platinum aqueous solution containing 0.5 g of platinum used in Example 1 was replaced with a dinitrodiamine platinum aqueous solution containing 4.5 g of platinum. A Pt 9 wt% supported V 2 O 5 / TiO 2 catalyst was obtained.
【００２１】実施例６ 実施例１で用いた白金０．５ｇを含有するジニトロジア
ミン白金水溶液に代えて、パラジウム２．５ｇ含有する
硝酸パラジウム水溶液を用いた以外は実施例１と同様の
方法によってＰｄ５ｗｔ％担持Ｖ2Ｏ5／ＴｉＯ2触媒を
得た。 Example 6 Pd of 5 wt% was prepared in the same manner as in Example 1 except that an aqueous palladium nitrate solution containing 2.5 g of palladium was used instead of the aqueous dinitrodiamine platinum solution containing 0.5 g of platinum used in Example 1. % Supported V 2 O 5 / TiO 2 catalyst was obtained.
【００２２】実施例７ 実施例１で用いた白金０．５ｇを含有するジニトロジア
ミン白金水溶液に代えて、ロジウム２．５ｇを含有する
硝酸ロジウム水溶液を用いた以外は実施例１と同様の方
法によってＲｈ５ｗｔ％担持Ｖ2Ｏ5／ＴｉＯ2触媒を得
た。 Example 7 The same procedure as in Example 1 was repeated except that an aqueous rhodium nitrate solution containing 2.5 g of rhodium was used in place of the dinitrodiamine platinum aqueous solution containing 0.5 g of platinum used in Example 1. An Rh 5 wt% supported V 2 O 5 / TiO 2 catalyst was obtained.
【００２３】実施例８ メタバナジン酸アンモニウム３．８５９ｇとパラタング
ステン酸アンモニウム１．１２６ｇを純水８００ｍｌで
溶解した。この溶液にＴｉＯ2粉末１００ｇを浸漬し、
マグネチックスタラーで撹拌しながら加熱し、蒸発乾固
させた。その後、１２０℃、１２時間乾燥し、次いで５
００℃、３時間焼成してＷＯ3／Ｖ2Ｏ5／ＴｉＯ2触媒担
体を得た。 Example 8 3.859 g of ammonium metavanadate and 1.126 g of ammonium paratungstate were dissolved in 800 ml of pure water. Immerse 100 g of TiO 2 powder in this solution,
It was heated with stirring with a magnetic stirrer and evaporated to dryness. Then, it is dried at 120 ° C for 12 hours, and then 5
The mixture was calcined at 00 ° C. for 3 hours to obtain a WO 3 / V 2 O 5 / TiO 2 catalyst carrier.
【００２４】次に、上記ＷＯ3／Ｖ2Ｏ5／ＴｉＯ2４７．
５ｇに、白金２．５ｇを含有するジニトロジアミン白金
水溶液を加え、マグネチックスタラーで撹拌しながら加
熱し、蒸発乾固させた。その後、１２０℃、１２時間乾
燥し、次いで５００℃、３時間焼成を行い、Ｐｔ５ｗｔ
％担持ＷＯ3／Ｖ2Ｏ5／ＴｉＯ2触媒を得た。Next, the above WO 3 / V 2 O 5 / TiO 2 47.
An aqueous dinitrodiamine platinum solution containing 2.5 g of platinum was added to 5 g, and the mixture was heated with stirring with a magnetic stirrer and evaporated to dryness. After that, it is dried at 120 ° C. for 12 hours, then baked at 500 ° C. for 3 hours, and Pt is 5 wt.
% Supported WO 3 / V 2 O 5 / TiO 2 catalyst was obtained.
【００２５】実施例９ メタバナジン酸アンモニウム１．８０ｇを純水８００ｍ
ｌで溶解した。この溶液に白金２．５ｇを含有するジニ
トロジアミン白金水溶液を加え十分に混合した。さら
に、この溶液にＴｉＯ2粉末４６．１ｇを浸漬し、マグ
ネチックスタラーで撹拌しながら加熱し、蒸発乾固させ
た。その後、１２０℃、１２時間乾燥し、次いで５００
℃、３時間焼成し、Ｐｔ５ｗｔ％担持Ｖ2Ｏ5／ＴｉＯ2
触媒を得た。 Example 9 1.80 g of ammonium metavanadate was added to 800 m of pure water.
Dissolved in 1. An aqueous dinitrodiamine platinum solution containing 2.5 g of platinum was added to this solution and mixed sufficiently. Further, 46.1 g of TiO 2 powder was dipped in this solution, heated with stirring with a magnetic stirrer, and evaporated to dryness. Then, it is dried at 120 ° C. for 12 hours, and then 500
Calcination at 3 ° C. for 3 hours, Pt 5 wt% supported V 2 O 5 / TiO 2
A catalyst was obtained.
【００２６】比較例１ 白金を担持しないこと以外は、実施例１と同様にしてＶ
2Ｏ5／ＴｉＯ2触媒を得た。 Comparative Example 1 V was prepared in the same manner as in Example 1 except that platinum was not supported.
A 2 O 5 / TiO 2 catalyst was obtained.
【００２７】比較例２ 白金を担持しないこと以外は、実施例８と同様にしてＷ
Ｏ3／Ｖ2Ｏ5／ＴｉＯ2触媒を得た。 Comparative Example 2 W was prepared in the same manner as in Example 8 except that platinum was not supported.
An O 3 / V 2 O 5 / TiO 2 catalyst was obtained.
【００２８】比較例３ 実施例１で用いた白金０．５ｇを含有するジニトロジア
ミン白金溶液に代えて、銅２．５ｇを含有する酢酸銅水
溶液を用いた以外は実施例１と同様の方法によってＣｕ
５ｗｔ％担持Ｖ2Ｏ5／ＴｉＯ2触媒を得た。比較例４ 実施例１で用いた白金０．５ｇを含有するジニトロジア
ミン白金水溶液に代えて、コバルト２．５ｇを含有する
硝酸コバルト水溶液を用いた以外は実施例１と同様の方
法によってＣｏ５ｗｔ％担持Ｖ2Ｏ5／ＴｉＯ2触媒を得
た。 Comparative Example 3 The same procedure as in Example 1 was repeated except that the dinitrodiamine platinum solution containing 0.5 g of platinum used in Example 1 was replaced with an aqueous solution of copper acetate containing 2.5 g of copper. Cu
A 5 wt% supported V 2 O 5 / TiO 2 catalyst was obtained. Comparative Example 4 Co5 wt% was carried in the same manner as in Example 1 except that an aqueous cobalt nitrate solution containing 2.5 g of cobalt was used instead of the aqueous dinitrodiamine platinum solution containing 0.5 g of platinum used in Example 1. A V 2 O 5 / TiO 2 catalyst was obtained.
【００２９】比較例５ ＳｉＯ2／Ａｌ2Ｏ3モル比３０のＨ型ＺＳＭ−５（ＰＱ
製）を酢酸銅水溶液に浸漬し、アンモニア水でｐＨ＝１
０．５に調整してイオン交換を行った。これを１２０
℃、１２時間乾燥し、５００℃、３時間焼成してＣｕ／
ＺＳＭ−５触媒を得た。Ｃｕの交換率は１２５％であっ
た。 Comparative Example 5 H-type ZSM-5 (PQ having a SiO 2 / Al 2 O 3 molar ratio of 30)
(Made by the manufacturer) is immersed in an aqueous solution of copper acetate, and pH is set to 1 with ammonia water.
Ion exchange was performed by adjusting to 0.5. This is 120
℃ / 12 hours, dried at 500 ℃ 3 hours Cu / Cu
A ZSM-5 catalyst was obtained. The exchange rate of Cu was 125%.
【００３０】性能試験例１ 実施例１〜８および比較例１〜５で得られた各触媒をコ
ージェライト質ハニカム担体（直径１インチφ、長さ２
インチ、２００セル／インチ2）に２ｇ／個担持した。
このハニカム触媒を以下の条件によりＮＯ最大浄化率
（％）とＮＯ最大浄化率を示す温度（℃）で評価した。 Performance Test Example 1 Each of the catalysts obtained in Examples 1 to 8 and Comparative Examples 1 to 5 was used as a cordierite honeycomb carrier (diameter 1 inch φ, length 2).
Inch, 200 cells / inch 2 ) was loaded at 2 g / piece.
The honeycomb catalyst was evaluated under the following conditions at the NO maximum purification rate (%) and the temperature (° C.) at which the NO maximum purification rate was shown.
【００３１】ガス組成：Ｃ3Ｈ6＝３００Ｏｐｐｍ（メタ
ン換算）、ＮＯ＝１０００ｐｐｍ、Ｏ2＝５％、Ｎ2＝残
部 ＳＶ：７００００ｈｒ-1 評価温度：室温〜６００℃まで２０℃／ｍｉｎで昇温 結果を表１に示す。Gas composition: C 3 H 6 = 300 Oppm (converted to methane), NO = 1000 ppm, O 2 = 5%, N 2 = balance SV: 70,000 hr −1 Evaluation temperature: Raised from room temperature to 600 ° C. at 20 ° C./min The temperature results are shown in Table 1.
【００３２】[0032]
【表１】 [Table 1]
【００３３】性能試験例２ 実施例３、６〜８および比較例５で得られた触媒を、コ
ージェライト質ハニカム担体（直径１インチφ、長さ２
インチ、２００セル／インチ2）に２ｇ／個担持した。
このハニカム触媒を、以下の条件によりＮＯ最大浄化率
（％）とＮＯ最大浄化率を示す温度（℃）で評価した。 Performance Test Example 2 The catalysts obtained in Examples 3, 6 to 8 and Comparative Example 5 were used as cordierite honeycomb carriers (diameter 1 inch φ, length 2).
Inch, 200 cells / inch 2 ) was loaded at 2 g / piece.
The honeycomb catalyst was evaluated at the maximum NO purification rate (%) and the temperature (° C.) showing the maximum NO purification rate under the following conditions.
【００３４】ガス組成：Ｃ3Ｈ6＝３００Ｏｐｐｍ（メタ
ン換算）、ＮＯ＝１０００ｐｐｍ、Ｏ2＝５％、Ｈ2Ｏ＝
１０％、Ｎ2＝残部 ＳＶ：７００００ｈｒ-1 評価温度：室温〜６００℃まで２０℃／ｍｉｎで昇温 結果を表２に示す。Gas composition: C 3 H 6 = 300 Oppm (methane conversion), NO = 1000 ppm, O 2 = 5%, H 2 O =
10%, N 2 = balance SV: 70,000 hr −1 Evaluation temperature: Table 2 shows the results of temperature increase from room temperature to 600 ° C. at 20 ° C./min.
【００３５】[0035]
【表２】 [Table 2]
【００３６】性能試験例３ 実施例３、６〜８および比較例５で得られた触媒を、コ
ージェライト質ハニカム担体（直径１インチφ、長さ２
インチ、２００セル／インチ2）に２ｇ／個担持した。
このハニカム触媒を８００℃で１時間熱処理し、その
後、以下の条件によりＮＯ最大浄化率（％）とＮＯ最大
浄化率を示す温度（℃）で評価した。 Performance Test Example 3 The catalysts obtained in Examples 3, 6 to 8 and Comparative Example 5 were used as cordierite honeycomb carriers (diameter 1 inch φ, length 2).
Inch, 200 cells / inch 2 ) was loaded at 2 g / piece.
This honeycomb catalyst was heat-treated at 800 ° C. for 1 hour, and then evaluated at the maximum NO purification rate (%) and the temperature (° C.) showing the maximum NO purification rate under the following conditions.
【００３７】ガス組成：Ｃ3Ｈ6＝３００Ｏｐｐｍ（メタ
ン換算）、ＮＯ＝１０００ｐｐｍ、Ｏ2＝５％、Ｎ2＝残
部 ＳＶ：７００００ｈｒ-1 評価温度：室温〜６００℃まで２０℃／ｍｉｎで昇温 結果を表３に示す。Gas composition: C 3 H 6 = 300 Oppm (converted to methane), NO = 1000 ppm, O 2 = 5%, N 2 = balance SV: 70,000 hr −1 Evaluation temperature: Raised from room temperature to 600 ° C. at 20 ° C./min The temperature results are shown in Table 3.
【００３８】[0038]
【表３】 [Table 3]
【００３９】[0039]
【発明の効果】本発明は、炭化水素を還元剤として、ア
ンモニア脱硝で実用化されているＶ2Ｏ5／ＴｉＯ2また
はＷＯ3／Ｖ2Ｏ5／ＴｉＯ2触媒を触媒担体とし、これに
貴金属を担持することにより、特異的に低温から効率よ
くＮＯxを除去することができる。また、耐熱性に優
れ、水蒸気共存下でも優れた浄化活性を保持する。従っ
て、本発明の触媒は排気ガス浄化用触媒として好適であ
る。INDUSTRIAL APPLICABILITY The present invention uses a hydrocarbon as a reducing agent and a V 2 O 5 / TiO 2 or WO 3 / V 2 O 5 / TiO 2 catalyst which has been put to practical use in ammonia denitration as a catalyst carrier. By supporting a noble metal, NO x can be efficiently removed from a low temperature specifically. Further, it has excellent heat resistance and retains excellent purifying activity even in the presence of steam. Therefore, the catalyst of the present invention is suitable as an exhaust gas purifying catalyst.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｄ 53/36 １０２ Ｈ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location B01D 53/36 102 H
Claims (1)
ＴｉＯ2を触媒担体として用い、これに貴金属を担持さ
せたことを特徴とする排気ガス浄化用触媒。1. V 2 O 5 / TiO 2 or WO 3 / V 2 O 5 /
A catalyst for purifying exhaust gas, characterized in that TiO 2 is used as a catalyst carrier and a noble metal is supported on the catalyst carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03519594A JP3506392B2 (en) | 1994-02-09 | 1994-02-09 | Exhaust gas purification catalyst using only hydrocarbons as reducing agents |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03519594A JP3506392B2 (en) | 1994-02-09 | 1994-02-09 | Exhaust gas purification catalyst using only hydrocarbons as reducing agents |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07213903A true JPH07213903A (en) | 1995-08-15 |
| JP3506392B2 JP3506392B2 (en) | 2004-03-15 |
Family
ID=12435086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03519594A Expired - Fee Related JP3506392B2 (en) | 1994-02-09 | 1994-02-09 | Exhaust gas purification catalyst using only hydrocarbons as reducing agents |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3506392B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100455271B1 (en) * | 1997-10-30 | 2005-02-28 | 삼성전기주식회사 | Catalyst for purifying exhaust gas of automobiles and method for manufacturing the same |
| WO2009025185A1 (en) * | 2007-08-22 | 2009-02-26 | Mitsubishi Heavy Industries, Ltd. | Exhaust gas treatment catalyst, and exhaust gas treatment system |
| US10717074B2 (en) * | 2016-06-21 | 2020-07-21 | Haldor Topsoe A/S | Method for preparation of a monolithic catalyst for the reduction of nitrogen oxides, VOC and carbon monoxide in an off-gas |
| CN117019143A (en) * | 2023-07-21 | 2023-11-10 | 中节能(山东)催化剂有限公司 | Denitration, decarbonization and deamination three-effect composite catalyst and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102896002B (en) * | 2012-10-10 | 2014-10-29 | 浙江海亮环境材料有限公司 | Method for preparing titanium dioxide-tungsten trioxide (TiO2-WO3) composite powder |
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1994
- 1994-02-09 JP JP03519594A patent/JP3506392B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100455271B1 (en) * | 1997-10-30 | 2005-02-28 | 삼성전기주식회사 | Catalyst for purifying exhaust gas of automobiles and method for manufacturing the same |
| WO2009025185A1 (en) * | 2007-08-22 | 2009-02-26 | Mitsubishi Heavy Industries, Ltd. | Exhaust gas treatment catalyst, and exhaust gas treatment system |
| JP2009045586A (en) * | 2007-08-22 | 2009-03-05 | Mitsubishi Heavy Ind Ltd | Exhaust gas treatment catalyst and exhaust gas treatment system |
| EP2179792A1 (en) * | 2007-08-22 | 2010-04-28 | Mitsubishi Heavy Industries, Ltd. | Exhaust gas treatment catalyst, and exhaust gas treatment system |
| EP2179792A4 (en) * | 2007-08-22 | 2011-08-03 | Mitsubishi Heavy Ind Ltd | EXHAUST GAS TREATMENT CATALYST AND EXHAUST GAS TREATMENT SYSTEM |
| US8202481B2 (en) | 2007-08-22 | 2012-06-19 | Mitsubishi Heavy Industries, Ltd. | Exhaust gas treatment catalyst and exhaust gas treatment system |
| US10717074B2 (en) * | 2016-06-21 | 2020-07-21 | Haldor Topsoe A/S | Method for preparation of a monolithic catalyst for the reduction of nitrogen oxides, VOC and carbon monoxide in an off-gas |
| CN117019143A (en) * | 2023-07-21 | 2023-11-10 | 中节能(山东)催化剂有限公司 | Denitration, decarbonization and deamination three-effect composite catalyst and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| JP3506392B2 (en) | 2004-03-15 |
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