WO2015079721A1 - 排ガス処理触媒 - Google Patents

排ガス処理触媒 Download PDF

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Publication number
WO2015079721A1
WO2015079721A1 PCT/JP2014/060381 JP2014060381W WO2015079721A1 WO 2015079721 A1 WO2015079721 A1 WO 2015079721A1 JP 2014060381 W JP2014060381 W JP 2014060381W WO 2015079721 A1 WO2015079721 A1 WO 2015079721A1
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Prior art keywords
catalyst
exhaust gas
oxide
gas treatment
oxidation
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PCT/JP2014/060381
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English (en)
French (fr)
Inventor
増田　具承
耕次 東野
将利 勝木
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Mitsubishi Heavy Industries Ltd
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Mitsubishi Heavy Industries Ltd
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Priority to US15/038,656 priority Critical patent/US20160303549A1/en
Publication of WO2015079721A1 publication Critical patent/WO2015079721A1/ja
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Definitions

  • the present invention relates to an exhaust gas treatment catalyst.
  • NO x carbon monoxide [CO]
  • methane methane
  • ethane are contained in exhaust gas discharged from various industrial equipment such as automobile engines, gas engines, aircraft, gas turbines for power generation, chemical plants, and various factories.
  • Volatile organic compounds [VOC] such as saturated hydrocarbons removed and unsaturated hydrocarbons such as ethylene are included.
  • an expensive oxidation catalyst using platinum [Pt] is used as an exhaust gas treatment facility.
  • Patent Document 1 Patent No. 4993908
  • precious metal is included in the preceding denitration catalyst, denitration and partial oxidation of VOC are performed, and the precious metal catalyst in the latter stage is used.
  • An exhaust gas treatment system for oxidizing and decomposing CO has been proposed.
  • Such an exhaust gas treatment system has a problem that the catalyst cost is high as described above because a noble metal catalyst using platinum [Pt] is actually applied to both the denitration catalyst and the oxidation catalyst.
  • Patent Document 2 Japanese Patent Laid-Open No. 7-213908
  • Patent Document 3 Japanese Patent Laid-Open No. 2000-130216
  • Patent Document 4 Japanese Patent Laid-Open No. 2009-202107
  • Patent Document 6 Japanese Patent No. 4801461
  • Patent Document 5 Japanese Patent Application Laid-Open No. 2012-245444
  • platinum [Pt] is not employed in the CO oxidation reaction after denitration, but the denitration reaction itself does not propose an improvement in cost.
  • an object of the present invention is to provide an exhaust gas treatment catalyst capable of removing CO ⁇ VOC in addition to reducing NOx without causing an increase in catalyst cost.
  • the present inventors have intensively studied a two-way catalyst (multi-way catalyst) capable of removing CO / VOC in addition to denitration performance, and have arrived at the present invention.
  • the exhaust gas treatment catalyst according to the present invention includes titanium oxide, tungsten oxide and vanadium oxide, and copper oxide and / or Cu / zeolite coat catalyst. It has the ability to remove nitrogen oxides and CO / VOC to reduce the product catalytically in the presence of ammonia.
  • the exhaust gas treatment catalyst according to the present invention includes, in one embodiment, 0.2 to 0.75 wt% of copper oxide.
  • a Cu / zeolite catalyst can be included together with the copper oxide or in place of the copper oxide.
  • the Cu / zeolite coat catalyst is preferably contained in an amount of 50 g to 200 g / m 2 as a catalyst coat amount on the substrate. That is, the Cu / zeolite-coated catalyst can be prepared by coating Cu / zeolite on a catalyst base material.
  • an exhaust gas treatment catalyst capable of removing CO / VOC in addition to reducing NOx without causing an increase in catalyst cost.
  • the CO oxidation catalyst employed in the exhaust gas treatment system constructed by using the exhaust gas treatment catalyst according to the present invention is a graph showing the C 2 H 4 reduction rate. It is a graph which shows CO removal rate about the Example of the exhaust gas treatment system constructed
  • exhaust gas treatment system constructed by using the exhaust gas treatment catalyst according to the present invention it is a graph showing the C 2 H 4 removal rate.
  • exhaust gas treatment system constructed by using the exhaust gas treatment catalyst according to the present invention it is a graph showing the C 3 H 8 REJECTION.
  • Exhaust gas treatment catalyst according to the present invention includes titanium oxide, tungsten oxide and vanadium oxide, and copper oxide and / or Cu / zeolite coat catalyst, and contains nitrogen oxide in the exhaust gas. Nitrogen oxide removal ability and CO / VOC removal ability to reduce catalytically in the presence of ammonia.
  • the exhaust gas treatment catalyst according to the present invention includes titanium oxide, tungsten oxide and vanadium oxide (first component), and copper oxide and / or Cu / zeolite coat catalyst (second component). It is said.
  • first component titanium oxide
  • second component copper oxide and / or Cu / zeolite coat catalyst
  • ammonia [NH 3 ] is added to exhaust gas discharged from a chemical plant such as a gas turbine, a diesel engine, a gas engine, or a nitric acid plant having a large load fluctuation.
  • a chemical plant such as a gas turbine, a diesel engine, a gas engine, or a nitric acid plant having a large load fluctuation.
  • the nitrogen oxide in the exhaust gas is reduced. It can be reduced to harmless nitrogen and water by reduction in the presence of ammonia.
  • Such an exhaust gas treatment catalyst can be obtained by impregnating a base material composed of a first component with a second component, and firing after drying. Further, the catalyst for removing nitrogen oxides / VOC may be obtained by adding a solvent to the first component and the second component, kneading, extrusion molding, and baking after drying.
  • tungsten oxide and vanadium oxide are 3 parts by weight or more and 25 parts by weight or less and 0.1 part by weight or more and 6 parts by weight or less, respectively, with respect to 100 parts by weight of titanium oxide. By setting it as such a weight ratio, nitric oxide in exhaust gas can fully be denitrated.
  • the total amount of the components constituting the second component is set to 1.0 wt% or more and 1.5 or less with respect to the total amount of the first component and the second component. Further, when the copper oxide is used as the second component, it contains 0.2 to 0.75 wt% of this, and in addition, 0.25 to 1.3 wt% of manganese oxide and 0.25 wt. Of chromium oxide. It can be contained up to 1.3 wt%.
  • a Cu / zeolite catalyst may be used together with or instead of copper oxide.
  • the Cu / zeolite coat catalyst is preferably contained in an amount of 50 g to 200 g / m 2 as a catalyst coat amount on the substrate. That is, in this form, it can implement as a form of the catalyst which coated the catalyst base material with the Cu / zeolite coat catalyst.
  • an exhaust gas treatment system can be constructed using the exhaust gas treatment catalyst according to the present invention.
  • Such an exhaust gas treatment system can be constructed by, for example, installing the exhaust gas treatment catalyst according to the present invention in the upstream and installing a CO oxidation catalyst having CO oxidation catalytic ability in the downstream.
  • a catalyst in which silver is supported on a double oxide can be used as the CO oxidation catalyst having CO oxidation catalytic ability.
  • yttrium manganate As the double oxide, a known double oxide, for example, yttrium manganate [YMnO 3 ] can be preferably used.
  • Yttrium manganate can be produced, for example, by firing a mixture of yttrium nitrate, manganese nitrate and citric acid.
  • by-products such as YMn 2 O 5 , Y 2 Mn 2 O 7 , Y 2 O 3 , and Mn 2 O 3 may be mixed.
  • YMn 2 O 5 , Y 2 Mn 2 O 7 , Y 2 O 3 , and Mn 2 O 3 may be mixed.
  • Yttrium manganate can also be produced by pulverizing, mixing, and firing Y 2 O 3 and MnO 2 as raw materials.
  • the CO oxidation catalyst can be obtained by mixing Ag with yttrium manganate obtained as described above or a known carrier such as alumina and supporting Ag. For example, it can be produced by introducing a carrier powder containing yttrium manganate into a solution of a soluble silver compound and firing the resulting slurry.
  • the CO oxidation catalyst can also be obtained by mixing Ag powder or Ag compound powder and carrier powder and baking.
  • the CO oxidation catalyst can be manufactured by applying a known catalyst forming method such as forming into a honeycomb shape.
  • the Ag particles are preferably 10 nm to 20 nm in size.
  • the exhaust gas treatment catalyst according to the present invention was prepared. This will be described as a first embodiment.
  • a honeycomb catalyst (3.3 mm) containing 10 parts by weight of tungsten oxide (WO 3 ) and 4 parts by weight of vanadium oxide (V 2 O 5 ) per 100 parts by weight of titanium oxide (TiO 2 ) according to a known production method. Pitch, wall thickness 0.5 mm).
  • Manganese nitrate hexahydrate 46 g and copper nitrate trihydrate 152 g are dissolved in 1 L of water, and the prepared solution is impregnated with the above-described titanium oxide-tungsten oxide-vanadium oxide catalyst for 1 minute to contain after firing. Impregnation was performed so that manganese oxide was contained in an amount of 0.75 wt% and copper oxide was contained in 0.75 wt%. Subsequently, the titanium oxide-tungsten oxide-vanadium oxide catalyst supporting copper nitrate and chromium nitrate was dried and calcined at 500 ° C. for 5 hours. The obtained catalyst was used as a 1.5% Mn 2 O 3 + CuO-impregnated honeycomb catalyst.
  • the Cu / zeolite-coated catalyst was prepared by mixing the copper ion-exchanged zeolite catalyst powder with alumina sol and silica sol to prepare a slurry solution.
  • the substrate was composed of the first component (cell number 80 cpsi, pitch 2.84 mm, wall thickness 0. 41 mm) was coated so that the catalyst coating amount would be 100 g / m 2, and after hot-air drying treatment, calcined at 500 ° C. ⁇ 5 hr to prepare a Cu / zeolite-coated catalyst.
  • the coating amount is preferably 50 to 200 g / m 2 from the viewpoint of pressure loss of the catalyst and suppression of ammonia oxidation of the reducing agent used in the denitration reaction.
  • the term “honeycomb catalyst” is omitted. From this result, although the NOx removal performance decreases when the Cu impregnation amount is 1.5 wt% or more, the NOx removal performance is obtained when it is 0.75 wt% or less (1.5 wtCu + Cr impregnated honeycomb catalyst, 1.5 wtCu + Mn impregnated honeycomb catalyst). It can be seen that the improvement in the oxidation performance of CO and C 2 H 4 is remarkable. In this way, by using a catalyst having excellent CO and VOC oxidation performance, it is possible to reduce the amount of platinum-based oxidation catalyst mainly for the oxidation of CO to be installed in the downstream.
  • the Cu / zeolite-coated catalyst can improve the denitration performance at low temperature and is excellent in the oxidation performance of CO and C 2 H 4 , denitration, oxidation of CO and VOC can be performed at a low temperature of 350 ° C. or less. It was found to be suitable for the required process.
  • the CO oxidation catalyst was prepared as follows, and its catalytic ability was verified in advance.
  • a carrier powder made of yttrium manganate [YMnO 3 ] was added to an aqueous silver nitrate solution so that the amount of Ag would be 3 atomic% based on the number of Y atoms, and stirred for 30 minutes.
  • the obtained slurry was coated on the surface of cordierite honeycomb having a size of 150 mm ⁇ ⁇ 300 mm in length. This was dried at 120 ° C. for 3 hours and then calcined in air for 1 hour.
  • the obtained base material had a supported amount of yttrium manganate of 40 g / L, and the supported amount of Ag was 0.69 g / L in terms of metal.
  • the size of Ag particles supported on yttrium manganate was 10 nm to 20 nm. This was used as an Ag-based CO oxidation catalyst.
  • the CO oxidation catalyst prepared as described above is an Ag-based catalyst which is used as an oxidation catalyst for GTCC and is expected to have CO oxidation performance at a low cost.
  • the performance evaluation results of this CO oxidation catalyst are shown in FIGS. From this result, it was confirmed that this CO oxidation catalyst was excellent in the C 2 H 4 reduction effect and excellent in CO oxidation performance.
  • the Pt-type catalyst used as a comparison object is a commercially available Pt-type oxidation catalyst, and a 1.0 wt% platinum (Pt) catalyst coated on a metal carrier at 100 g / m 2 was used.
  • the oxidation reaction rate was calculated, and the exhaust gas treatment system according to the embodiment in which the above honeycomb catalyst (1.5 wt% Cu + Cr impregnated honeycomb catalyst) was installed in the upstream and the CO oxidation catalyst was installed in the downstream,
  • the results are shown in FIGS.
  • the thing using the form using the Pt-type catalyst mentioned above about FIG. 6, 7 as a CO oxidation catalyst is also shown.
  • the exhaust gas treatment system constructed using the 1.5 wt% Cu + Cr impregnated honeycomb catalyst is an exhaust gas treatment system with improved CO and VOC oxidation performance.
  • an Ag-based CO oxidation catalyst having excellent CO oxidation performance it is inferior to the form using platinum [Pt], becomes a Pt-free raw material in the exhaust gas treatment system, and the catalyst cost is greatly reduced. It turns out that it is possible.

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Abstract

チタン酸化物、タングステン酸化物及びバナジウム酸化物、並びに銅酸化物及び／又はＣｕ／ゼオライトコート触媒を含み、排ガス中の窒素酸化物をアンモニアの存在下で接触的に還元処理する窒素酸化物除去能及びＣＯ・ＶＯＣ除去能を備えることとした。

Description

排ガス処理触媒
　本発明は、排ガス処理触媒に関する。
　各種産業機器、例えば、自動車用エンジン、ガスエンジン、航空機用、発電用ガスタービン、化学プラント、各種工場等から排出される排ガス中には、ＮＯx、一酸化炭素［ＣＯ］、メタン、エタンを除いた飽和炭化水素及びエチレン等の不飽和炭化水素等の揮発性有機化合物［ＶＯＣ］が含まれている。
　ＮＯｘ低減に加え、ＣＯ・ＶＯＣを除去するためには、排ガス処理設備として、白金［Ｐｔ］を用いた高価な酸化触媒が使用されている。
　例えば、特許文献1（特許第４９３９０８２号）では、排ガス処理設備におけるＣＯ排出量低減を目的として、前段の脱硝触媒に貴金属を含め、脱硝及びＶＯＣの部分酸化を行い、後段の貴金属系触媒にて、ＣＯを酸化分解させる排ガス処理システムが提案されている。
　このような排ガス処理システムは、脱硝触媒及び酸化触媒の両方に、実際上白金［Ｐｔ］を用いた貴金属触媒を適用するため、前記したように、触媒コストが高いとの課題があった。
　なお、脱硝触媒については、特許文献２（特開平７－２１３９０８）、特許文献３（特開２０００－１３０２１６）、特許文献４（特開２００９－２０２１０７）、特許文献６（特許第４８０１４６１号）等幾多の先行技術がある。しかし、いずれも触媒コストの低減といった観点で、十分な対応をしているものではなかった。特許文献５（特開２０１２－２４５４４４）では、脱硝後のＣＯ酸化反応で、白金［Ｐｔ］を採用していないものの、脱硝反応自体に関しては、コスト上の改善を提案するものではなかった。
特許第４９３９０８２号公報 特開平７－２１３９０８号公報 特開２０００－１３０２１６号公報 特開２００９－２０２１０７号公報 特開２０１２－２４５４４４号公報 特許第４８０１４６１号公報
　前記事情に対して、本発明は、触媒コストの増大を招くことなく、ＮＯｘ低減に加え、ＣＯ・ＶＯＣを除去することを可能とする排ガス処理触媒を提供することを目的とする。
　本発明者らは、脱硝性能に加え、ＣＯ・ＶＯＣを除去することを可能とする二元触媒（多元触媒）について鋭意検討を重ね、本発明に想到したものである。
すなわち、前記目的を達成するため、本発明に係る排ガス処理触媒は、チタン酸化物、タングステン酸化物及びバナジウム酸化物、並びに銅酸化物及び／又はＣｕ／ゼオライトコート触媒を含み、排ガス中の窒素酸化物をアンモニアの存在下で接触的に還元処理する窒素酸化物除去能及びＣＯ・ＶＯＣ除去能を備えている。
　また、本発明に係る排ガス処理触媒は、その一実施の形態で、銅酸化物を０．２～０．７５ｗｔ％含む。なお、この排ガス処理触媒では、前記銅酸化物と共に、又は前記銅酸化物に代えてＣｕ／ゼオライト触媒を含むこととすることができる。Ｃｕ／ゼオライトコート触媒は、基材に対する触媒コート量として、５０ｇ～２００ｇ／ｍ２含むことが好適である。すなわち、Ｃｕ／ゼオライトコート触媒は、Ｃｕ／ゼオライトを触媒基材にコートして調製することができる。
　本発明によれば、触媒コストの増大を招くことなく、ＮＯｘ低減に加え、ＣＯ・ＶＯＣを除去することを可能とする排ガス処理触媒が提供される。
本発明に係る排ガス処理触媒の実施例について、ＮＯｘ低減率を示すグラフである。 本発明に係る排ガス処理触媒の実施例について、ＣＯ低減率を示すグラフである。 本発明に係る排ガス処理触媒の実施例について、Ｃ２Ｈ４低減率を示すグラフである。 本発明に係る排ガス処理触媒の実施例について、Ｃ３Ｈ８低減率を示すグラフである。 本発明に係る排ガス処理触媒の実施例について、ＨＣＨＯ低減率を示すグラフである。 本発明に係る排ガス処理触媒を用いて構築される排ガス処理システムで採用されるＣＯ酸化触媒の実施例について、ＣＯ低減率を示すグラフである。 本発明に係る排ガス処理触媒を用いて構築される排ガス処理システムで採用されるＣＯ酸化触媒の実施例について、Ｃ２Ｈ４低減率を示すグラフである。 本発明に係る排ガス処理触媒を用いて構築される排ガス処理システムの実施例について、ＣＯ除去率を示すグラフである。 本発明に係る排ガス処理触媒を用いて構築される排ガス処理システムの実施例について、ＨＣＨＯ除去率を示すグラフである。 本発明に係る排ガス処理触媒を用いて構築される排ガス処理システムの実施例について、Ｃ２Ｈ４除去率を示すグラフである。 本発明に係る排ガス処理触媒を用いて構築される排ガス処理システムの実施例について、Ｃ３Ｈ８除去率を示すグラフである。
　以下、本発明に係る排ガス処理触媒についてさらに詳細に説明する。
　本発明に係る排ガス処理触媒
　本発明に係る排ガス処理触媒は、チタン酸化物、タングステン酸化物及びバナジウム酸化物、並びに銅酸化物及び／又はＣｕ／ゼオライトコート触媒を含み、排ガス中の窒素酸化物をアンモニアの存在下で接触的に還元処理する窒素酸化物除去能及びＣＯ・ＶＯＣ除去能を備える。
　すなわち、本発明に係る排ガス処理触媒は、チタン酸化物、タングステン酸化物及びバナジウム酸化物（第１の成分）、並びに銅酸化物及び／又はＣｕ／ゼオライトコート触媒（第２の成分）を含むこととしている。これらの成分からなることにより、排ガス中の窒素酸化物をアンモニアの存在下で接触的に還元処理する窒素酸化物除去能に加え、ＣＯ酸化能及びＶＯＣ除去能を獲得している。また、このような成分からなる触媒であることにより、負荷変動が大きいガスタービン、ディーゼルエンジン、ガスエンジン、又は硝酸プラント等の化学プラントから排出される排ガスにアンモニア［ＮＨ３］を添加して当該触媒に接触させることで、窒素酸化物を還元して無害な窒素及び水に分解することができる。とりわけ、第２の成分を有することで、ガスタービンコンバインドサイクル発電［ＧＴＣＣ］における低負荷時のように、排ガス中の窒素酸化物に対する二酸化窒素の割合が大きい場合でも、排ガス中の窒素酸化物をアンモニア存在下で還元して無害な窒素及び水に分解することができる。
　このような排ガス処理触媒は、第１の成分からなる基材に、第２の成分を含浸させ、乾燥後に焼成して得ることができる。また、窒素酸化物・ＶＯＣ除去用の触媒は、第１の成分及び第２の成分に溶媒を加えて混練し、押し出し成型し、乾燥後に焼成して得ることもできる。 
　前記第１の成分については、チタン酸化物１００重量部に対して、タングステン酸化物及びバナジウム酸化物をそれぞれ３重量部以上２５重量部以下及び０．１重量部以上６重量部以下とする。このような重量比とすることで、排ガス中の一酸化窒素を十分に脱硝することができる。 
　第１の成分と第２の成分の合計量に対して、第２の成分を構成する成分の合計量を、１．０ｗｔ％以上１．５以下とする。また、第２成分は、銅酸化物を用いる場合、これを０．２～０．７５ｗｔ含み、これに加えて、マンガン酸化物を０．２５～１．３ｗｔ％、クロム酸化物を０．２５～１．３ｗｔ％含有することができる。なお、銅酸化物と共に、又は銅酸化物に代え、Ｃｕ／ゼオライト触媒を用いることもできる。Ｃｕ／ゼオライトコート触媒は、基材に対する触媒コート量として、５０ｇ～２００ｇ／ｍ２含むことが好適である。すなわち、この形態では、Ｃｕ／ゼオライトコート触媒を触媒基材にコートした触媒の形態として実施することができる。
　さらに、本発明に係る排ガス処理触媒を用いて、排ガス処理システムを構築することができる。このような排ガス処理システムは、例えば、本発明に係る排ガス処理触媒を前流に設置し、ＣＯ酸化触媒能を有するＣＯ酸化触媒を後流に設置することで構築することができる。
　本発明に係る排ガス処理触媒を用いて構築される排ガス処理システムでは、ＣＯ酸化触媒能を有するＣＯ酸化触媒として、例えば、銀を複酸化物に担持したものを用いることができる。
　複酸化物としては、公知の複酸化物である、例えば、マンガン酸イットリウム［ＹＭｎＯ３］を好適に用いることができる。
　マンガン酸イットリウムは、例えば、硝酸イットリウムと硝酸マンガンとクエン酸とからなる混合物を焼成して製造することができる。この場合、ＹＭｎ２Ｏ５、Ｙ２Ｍｎ２Ｏ７、Ｙ２Ｏ３、Ｍｎ２Ｏ３等の副生物が混在することもある。しかし、そのような副生物が担体として含まれていても支障はない。
　また、マンガン酸イットリウムは、原料としてＹ２Ｏ３、ＭｎＯ２を粉砕・混合し、焼成することによっても製造することができる。
　ＣＯ酸化触媒は、以上のようにして得られたマンガン酸イットリウム単独又はアルミナ等の公知の担体と混合し、Ａｇを担持することによって得ることができる。例えば、可溶性銀化合物の溶液中に、マンガン酸イットリウムを含む担体粉末を導入して、得られるスラリーを焼成することにより製造することができる。また、ＣＯ酸化触媒は、Ａｇ粉末又はＡｇ化合物粉末と担体粉末とを混合し、焼成しても得ることができる。その他、ＣＯ酸化触媒は、ハニカム形状に成形する等、公知の触媒成形方法を適用して製造することができる。
　なお、Ａｇ粒子は、１０ｎｍ～２０ｎｍの大きさとすることが好適である。
　本発明に係る排ガス処理触媒を調整した。これを実施例１として説明する。
　周知の製法により、１００重量部のチタン酸化物（ＴｉＯ2）当たり、１０重量部の酸化タングステン（ＷＯ3）、４重量部の酸化バナジウム（Ｖ2Ｏ5）を含有するハニカム触媒（３．３ｍｍピッチ、壁厚０．５ｍｍ）を調製した。
　硝酸銅三水和物１５２ｇを１Ｌの水に溶かし、調整した溶液に上述したチタン酸化物－酸化タングステン－酸化バナジウム触媒を１分間含浸させることにより、焼成後の含有増加量として、酸化銅が１．５ｗｔ％含まれるように、含浸した。続いて、硝酸銅を担持したチタン酸化物－酸化タングステン－酸化バナジウム触媒を乾燥した後、５００℃で５時間焼成した。得られた触媒を１．５％ＣｕＯ含浸ハニカム触媒とした。
　硝酸銅三水和物１５２ｇ及び硝酸クロム九水和物６６ｇを１Ｌの水に溶かし、調整した溶液に上述したチタン酸化物－酸化タングステン－酸化バナジウム触媒を１分間含浸させることにより、焼成後の内割の含有量として、酸化銅が０．７５ｗｔ％、酸化クロムが０．７５ｗｔ％含まれるように、含浸した。続いて、硝酸銅及び硝酸クロムを担持したチタン酸化物－酸化タングステン－酸化バナジウム触媒を乾燥した後、５００℃で５時間焼成した。得られた触媒を１．５％ＣｕＯ＋Ｃｒ２Ｏ３含浸ハニカム触媒とした。
　硝酸マンガン六水和物４６ｇ及び硝酸銅三水和物１５２ｇを１Ｌの水に溶かし、調整した溶液に上述したチタン酸化物－酸化タングステン－酸化バナジウム触媒を１分間含浸させることにより、焼成後の含有増加量として、酸化マンガンが０．７５ｗｔ％、酸化銅が０．７５ｗｔ％含まれるように、含浸した。続いて、硝酸銅及び硝酸クロムを担持したチタン酸化物－酸化タングステン－酸化バナジウム触媒を乾燥した後、５００℃で５時間焼成した。得られた触媒を１．５％Ｍｎ２Ｏ３+ＣｕＯ含浸ハニカム触媒とした。
　硝酸マンガン六水和物１３７ｇ及び硝酸銅三水和物２２９ｇを１Ｌの水に溶かし、調整した溶液に上述したチタン酸化物－酸化タングステン－酸化バナジウム触媒を１分間含浸させることにより、焼成後の含有増加量として、酸化マンガンが２．２５ｗｔ％、酸化銅が２．２５ｗｔ％含まれるように、含浸した。続いて、硝酸銅及び硝酸クロムを担持したチタン酸化物－酸化タングステン－酸化バナジウム触媒を乾燥した後、５００℃で５時間焼成した。得られた触媒を４．５％Ｍｎ２Ｏ３+ＣｕＯ含浸ハニカム触媒とした。
　Ｃｕ／ゼオライトコート触媒は、銅イオン交換したゼオライト触媒粉末を、アルミナゾル、シリカゾルと混合し、スラリー溶液を調製し、第一成分からなる基材（セル数８０ｃｐｓｉ、ピッチ２．８４ｍｍ、壁厚０．４１ｍｍ）に対して触媒コート量１００ｇ／ｍ２になるようコートし、熱風乾燥処理後、５００℃×５ｈｒにて焼成し、調製し、Ｃｕ／ゼオライトコート触媒とした。なお、触媒の圧損及び脱硝反応に使用される還元剤のアンモニア酸化抑制の観点より、コート量は，５０～２００ｇ／ｍ２が望ましい。
　性能試験
　Ｃｕ含浸ハニカム触媒及びＣｕ／ゼオライトコート触媒に関する脱硝性能及びＣＯ・ＶＯＣ酸化性能を図１～５に示す。表1に試験条件を示す。
Figure JPOXMLDOC01-appb-T000001
  
　なお、図中「ハニカム触媒」の語は省略している。この結果より、Ｃｕの含浸量が、１．５ｗｔ％以上では，脱硝性能が低下するものの、０．７５ｗｔ％以下（１．５ｗｔＣｕ＋Ｃｒ含浸ハニカム触媒、１．５ｗｔＣｕ＋Ｍｎ含浸ハニカム触媒）であれば、脱硝性能の低下はなく、ＣＯ及びＣ２Ｈ４の酸化性能の向上が顕著であることがわかる。
　このようにＣＯ及びＶＯＣ酸化性能の優れた触媒を用いることにより、後流に設置されるべきＣＯの酸化を主眼とする白金系酸化触媒量の低減が可能になる。
　また、Ｃｕ／ゼオライトコート触媒は、低温での脱硝性能向上ができ、かつＣＯ及びＣ２Ｈ４の酸化性能に優れているため、温度３５０℃以下の低温において、脱硝、ＣＯ及びＶＯＣの酸化が要求されるプロセスには適していることがわかった。
　本発明に係る排ガス処理触媒を用いて構築される排ガス処理システムに関し、窒素酸化物除去能及びＣＯ・ＶＯＣ除去能を備えた排ガス処理触媒として、ＣＯ及びＶＯＣの酸化性能向上効果が実施例１で確認された１．５ｗｔ％Ｃｕ＋Ｃｒ含浸ハニカム触媒を適用した場合の効果を推算した。
　なお、ＣＯ酸化触媒は、以下のようにして調製し、予めその触媒能について検証した。
　硝酸銀水溶液中に、Ａｇの量がＹの原子数を基準にして、３原子％となるように、マンガン酸イットリウム［ＹＭｎＯ３］からなる担体粉末を投入し、３０分間撹拌した。得られたスラリーを１５０ｍｍ□×長さ３００ｍｍのコージュライト製ハニカム表面にコートさせた。これを１２０℃で３時間乾燥した後、空気中で１時間焼成した。得られた基材のマンガン酸イットリウムの担持量は４０ｇ／Ｌであり、Ａｇの担持量は、金属換算で０．６９ｇ／Ｌであった。マンガン酸イットリウムに担持されているＡｇ粒子の大きさは、１０ｎｍ～２０ｎｍであった。これをＡｇ系のＣＯ酸化触媒とした。
　以下の表２に示した試験条件にて、上述のように調製したＣＯ酸化触媒について、性能評価を行った。
Figure JPOXMLDOC01-appb-T000002
  
　上述のように調製したＣＯ酸化触媒は、ＧＴＣＣ用酸化触媒として使用され、低コストでＣＯ酸化性能が期待されているＡｇ系触媒である。このＣＯ酸化触媒の性能評価結果を図６、７に示す。この結果より、このＣＯ酸化触媒は、Ｃ２Ｈ４低減効果において優れており、ＣＯ酸化性能においても優れていることが確認された。
　なお、比較対象となっているＰｔ系触媒は、市販のＰｔ系酸化触媒であり、１．０ｗｔ％白金（Ｐｔ）の触媒をメタル担体に１００ｇ／ｍ２コートしたものを用いた。
　以上の結果をもとに、酸化反応速度を算出し、前流に上述のハニカム触媒（１．５ｗｔ％Ｃｕ＋Ｃｒ含浸ハニカム触媒）、後流にＣＯ酸化触媒を設置した形態に係る排ガス処理システムについて、性能を試算(ハニカム触媒ＡＶ　＝１２Ｎｍ／ｈｒ、ＳＶ＝１２，０００ｈｒ－１、ＣＯ酸化触媒　ＳＶ＝１２０，０００ｈｒ－１）した。その結果を、図８～図１１に示す。
　なお、ＣＯ酸化触媒として、図６、７について前述したＰｔ系触媒を用いた形態によるものも示している。
　この結果より、１．５ｗｔ％Ｃｕ＋Ｃｒ含浸ハニカム触媒を用いて構築される排ガス処理システムは、ＣＯ及びＶＯＣの酸化性能が向上した排ガス処理システムであることがわかる。すなわち、ＣＯ酸化性能に優れたＡｇ系のＣＯ酸化触媒を適用することにより、白金［Ｐｔ］を用いた形態と遜色がなく、排ガス処理システムにおいて、Ｐｔフリー原料となり、触媒コストが大幅に削減することが可能であることがわかった。 

Claims (3)

  1. 　チタン酸化物、タングステン酸化物及びバナジウム酸化物、並びに銅酸化物及び／又はＣｕ／ゼオライトコート触媒を含み、排ガス中の窒素酸化物をアンモニアの存在下で接触的に還元処理する窒素酸化物除去能及びＣＯ・ＶＯＣ除去能を備えた、排ガス処理触媒。
  2. 　銅酸化物を０．２～０．７５ｗｔ％含む、請求項１記載の排ガス処理触媒。
  3. 　Ｃｕ／ゼオライトコート触媒を、基材に対する触媒コート量として、５０ｇ～２００ｇ／ｍ２含む、請求項１記載の排ガス処理触媒。
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